CHEMISTRY

ORGANIC
INCLUDING

PORTIONS

CERTAIN

PHYSICAL

OP

CHEMISTRY
FOR

MEDICAL,

PHARMACEUTICAL,

BIOLOGICAL

AND

STUDENTS

(with

:^
HOWARD
Professor

D:

BY

HASKINS,

of Biochemistry^ Medical

^brmerly

THIRD

exercises)

practical

DepartriMnt^ University of Oregon

Associate

Professor of Organic

Medical

Departments

ISSUE,

NEW

JOHN
London:

Chemistry
Beserve

Western

THOROUGHLY

EDITION,
TOTAL

A.B., M.D.

SIX

and

Biochemistry

University

REVISED

THOUSAND

YORK

WILEY

"

CHAPMAN

"

1917

SONS,
HALL,

Inc.
Limited

COPTBIQHT,

H.

1907,

BT

1917,

bt

HASKINS

D.

AND

J.

J.

MACLEOD

R.

Copyright,

HOWARD

D.

HASKINS

Of
BRAUNWORTH

BOOK

CO.

MANUPACTURCRa

BROOKLYN.

N.

V.

TO

PREFACE

rearranged
have

(e.g.,

It

will

of

consideration

been

Numerous

extent.

the

physical

chemistry

and

author

and

written
re-

colloids).

greatly

suggestions

partly

cases,

some

pressure

the

topics

in

and,

osmotic

gratify

has

matter

made.

been

amplified,

been

has

subject

discussion

The

EDITION

considerable

to

revisions

the

edition

this

In

THIRD

to

criticisms

receive

for

from
any

who
are

using

this

text-book.

Howard

Oregon.

Portland,

Nov.

1,

1916.

D.

Haskins.

PREFACE

The.

author

book,

striving

book,

and

has

chemistry

students

should

compoimds

reliable
as

It

sciences.

of

text-book

give

(of

1,

standpoint

the

from

entire

reference

more

of

belief

is

any

physiology,

the

for

that

of

all

that

iy

the

organic
into

enter

biochemistry,

1912.

medical

of
use

chemistry

importance)

the

an

the

and

H.

July

the

our

organic

study

it

revise

to

complete

medical

of

EDITION

endeavored

make

to

more

student

SECOND

TO

D.

cology.
pharma-

Haskins.

the

the

Among
medical

in
of

science

of

the

physico-chemical

of

the

of

many

and

sugars

and
of

and

physical

to

student

As

of

be

and
best

the

is

in

taught

the

proportion

of

laws

subject

The

application

illustration

chemistry

explaining
of

for

the

the

and

in
of

macology
phar-

organic
The

the

daily

medical

the

to

in

curriculum

mode

the

increasing

the

medical

absorbs

student's
which

course

by

classes

college

certainly

medical

in

in

importance

regular

included
recent

teaching

schools.^

the

the

tion
solu-

is, therefore,

included

already

of

essential.

chemistry

greater

medical

chemistry,

is

of

parts

of

the

almost

is

and

theories

knowledge

chemistry

these

of

coming

of

pharmacy

purin

the

constituents,

chemistry;

covery
dis-

The
of

new

to

least

at

or

govenj,

revolutionized

clinical

into
and

fluids,

processes.

the

as

has

catalysis,

and

which

urinary

well

as

chemistry
enter

constitution

the

of

and

study

laws

the

to

which

tissues

chemical

fats,

biological

and

animal

advances

recent

relating

physiological

many

the

substances

organic

composition

bodies,

those

are

the

influence,

of

important

most

various

the

EDITION

FIRST

TO

PREFACE

Airhenius
of

action

importance

student.

certain

of
of

great

and

much

bearing

no

on

physicochemical

antitoxins,
a

organic

too

time,
has

of

in

knowledge

etc.,
of

is

an

physical

PREFACE

vi

immense
It

much

importance
with

was

which

have
the

of

of

book

present

and

for chemical

text-books

book

of the

description of

work

his

has
often

giving

the

attention

is

employed

for

substances

analysis follows, and

the

that

where

are

not

they

can

the book

Those

is desirable

included

in this

includes

body

as

the

of medical

been

four

hours

chosen
of

call

and

arranged

laboratory work

so

per

on

to

physical
attention

are

inserted

studied

along

remainder

of

groups

possible, there

as

ous
Numer-

for

these
about

to occupy

week

is

some

group,

the text, and

accompany

of

theories

biologicalimportance.

practicalexercises
have

of

representative of each
or

ter
chap-

applied

the various

organic substances, and, where

chosen,

chapter

facts

be

he

methods

the

The

description of

part

which

to

chapter

conveniently

most

this

as

to

organic compounds.

the

with

it

which

chemistry

etc.

and

to

purifying

in

then

determinations

osmosis, solution,

of

given

bio-chemistry

in

and

attention

in

first portion

is to

It

fairlyfull description of

weight

molecular

what
some-

preparatory

principles of physical chemistry

the

of

In

greatest diflSculties.

the

of

usually followed

investigator

closest

with

elementary

to

the

his

meets

of

sake

arranged in

investigation.

that

give

to

methods

science

the

For

students.

purity

further

their

to

of

the

is

that

considerable

testing,the

and

from

manner

medical

on

written.

was

simplest

physical chemistry

bearing

simplicity,the subject-matter
different

is of

which

in the

presenting

organic

essential

an

is omitted

him.

to

idea

the

facts

the

manner

that

and

work,

future

his

thirty-

vii

PREFACE

for

given

and

the

of

be

and

The

the

at

is

left

them

compoimds

benzene

the

are

have

cyclic

of

omitted

it

shall

he

not

or

complicated

also

exercises

completeness,

student.

the

more

may

advanced

more

whether

by

performed

few

sake

the

teacher

the

to

session.

week

tives
deriva-

discretion

the

of

teacher.
the

Appendix

the

work

In
how

arranged

so

experiments
The

and

he

without

any

all

his

students

that
a

organic

grasp

principles

otherwise
will

of

and

chemistry

be

work.
whom

such

as

J.
1907.

work

others

to

is,
is

subject

rarely

acquire.

Haskins.
R.

him

also,

required

the

D.
J.

which,

value

of

H.

April,

and

experience

imderstanding

accuracy

methods

chemical

laboratory

Beck-

organic

of

inmiense

Our

analysis

pure

idea

an

We

with

obtain,
of

those

students.

our

of

is

apparatus.

preparing

the

doubt,

do

elementary

an

acquires

cannot

expensive
of

student

into

future

also

as

it may

experiments

cryoscopic

showing

institution

own

of
of

use

conducting

the

insight

an

which

get

by

our

required

is

apparatus,

compounds,

in

work

doing

by

the

schedule

members

the

involving

that

mann's

all

in

class

the

that

laboratory

believe

and

of

found

be

will

MACLEOD.

of

'

CONTENTS

G
I.

CHAPTER

PAGE

The

Nature

and

Composition

of

and

Identification

of

Analysis

Molecular

28

Weight
Osmotic

IV.

Determination.
Pressure.

The

Empirical
of

Survey
of

Fatty

of

40

98

VI.

Chemistry

Organic

Compounds

Hydrocarbons.

sion.
Ten-

100

101
115

CHAPTER
Saturated

Isomerism

I-V

CHAPTER
Preliminary

tions.
Solu-

V.

Structural.

and

Chapters

of

Surface

Solutions

CHAPTER

FoRMULiE,

Nature

Ionization.

Colloidal

Viscosity.

Synopsis

Substances

III.

CHAPTER

Synopsis

II.

CHAPTER
Elementary

1
.

CHAPTER
Purification

Compounds.

Organic

VII.

Methane

ix

Series

117

CONTENTS

CHAPTER

VIII.
PAQB

Halogen

Substitution

Products

of

CHAPTER
Ethers

the

Paraffins

124

IX.
132

."

CHAPTER
Primary

X.-

Alcohols

136

CHAPTER

XI.

Aldehydes

146

CHAPTER
Acids

Fatty
IN

Ethereal

and

XII.

Salts.

Further

Chemistry

Physical

157

CHAPTER
Secondary

Observations

Certain

and

XIII.

Monacid

Other

Alcohols.
189

Ketones

CHAPTER
DiACiD

Alcohols

and

XIV.

Dibasic

Acids

CHAPTER
Triacid

Alcohols,

Fats,

and

193

XV.

Soaps

CHAPTER

199

XVI.
212

Hydroxy-acids

CHAPTER
Carbohydrates

and

Derivatives.

Compounds.)

227

Glucosides

CHAPTER
Nitrogen

XVII.

(Also

XVIII.

Phosphorus

and

Arsenic
255

xi

CONTENTS

XIX.

CHAPTER

PAGB

Acros

Amino

Acid

and

266

Amides

CHAPTER

Complex

Ibodes.

Acid

Including

XX.

Amino

284

Hydrocarbons

XXI.

and

CHAPTER
Sulphur

Their

Bi-cyclic

and

XXIII.

Compounds.

CHAPTER

Aromatic

Halogen

Aromatic

Hydroxy

XXV.

333

XXVI.

336

XXVII.

Acids

356

CHAPTER
Aromatic

316

Compounds

CHAPTER
Aromatic

XXIV.

Derivatives

CHAPTER

Nitrogen

309

Hydrocarbons

CHAPTER
Aromatic

299

306

The

Derivatives

XXII.

Derivatives

CHAPTER
Cyclic

Compounds,

Polypeptides

CHAPTER
Unsaturated

Imido

a^jd

Derivatives

XXVIII.
374

xii

CONTENTS

XXIX.

CHAPTER

PAQB

SULPHUB

ArSENIC

AND

DERIVATIVES

391

CHAPTER
Dyes

QuiNONES,

XXX.

Indicators

and

398

CHAPTER
Compounds

Aromatic

XXXI.

Condensed

Having

CHAPTER

409

XXXII.

Compounds

Heterocyclic

Synopsis

Rings

414

Compounds

Aromatic

op

423

CHAPTER

Alkaloids

Drug

and

XXXIII.

Principles

425

APPENDIX.
Note

to

II.

443

Tables

Reference
I.

Instructor

the

Specific Gravity
of

Weight
Various

and
Gas

Pure

of Alcohol

Percentage

Temperatures

in

and

of

c.c.

under

445

Moist

Nitrogen

Various

Pressures

at
447
.

III.

and

Specific Gravity

Percentage

of

NaOH

Solution
IV.

in

Aqueous
448

'

and

Specific Gravity

Percentage

of

KOH

in

Aqueous

Solution
V.

Acetic
Various

VI.

Vapor

449

Acid,

Specific

and

Gravity

Freezing-point

VIII.
IX.

of

Tension

Dissociation
Dissociation
Power

at

Concentrations

450

and

Water

of

40%

KOH

at

Temperatures
VII.

Various
450

Constants

Constants

of Certain

Acids

of

Certain

of Certain
to

Cause

Organic
Bases

Hydrolysis

Acids

451
451
452

xiii

CONTENTS

ILLUSTRATIONS.
PAOK

Fig.

1.

Melting-point

Apparatus

10
^

2.

Sublimation

3.

Fractional

4.
5.

Gattermann

"

Distillation

14

after

Apparatus

Column

Fractionating
Steam

after

Apparatus

Gattermann.

15

"

Gattermann

after

15

"

Distillation

Apparatus

^after

"

Gattermann

16
....

6.

Distillation

Vacuum

Apparatus

^after

"

Gattermann.

17
.

7.

Boiling-point

8.

Hcnometer

9.

WestphaPs

Flask

18
23

balance

10.

Hydrometer

11.

CJombustion

12.

Calcium

23
24

furnace
Chloride

30

and

Potash

Absorption

Apparatus

"

after

Gattermann

31

13.

Mixing

Tube

32

14.

Nitrogen

15.

Victor

"

Meyer's

Gattermann

^after

Burette

37

Density

Vapor

Walker

Apparatus

"

after
45

".

16.

Pfeffer's

17.

Beckmann's

Osmotic

Pressure

49

Apparatus
Thermometer

and

Apparatus

^after
"

Walker

61

18.

Flashing-point

19.

Ethyl

20.

Aldehyde

21.

Acetyl

22.

Tartaric

Bromide

Acid

after

"

Apparatus
Models,

122

Gattermann

126

Fischer

after

"

Remsen

"

Apparatus

Apparatus
Chloride

after

Apparatus

after

"

Illustrating

152

Gattermann

167

Stereoisomerism..

223
.

23.

Sodium

Ammonium

Crystals

Racemate

"

25*

Ethylene
Collie's

HoUe224

man

24.

after

Bromide

Benzene

Apparatus
Model*

after
"

,,,,.,,",,,,,.....;

Gattermann

301
324

ORGANIC

CHEMISTRY

CHAPTER

THE

AND

NATURE

COMPOSITION

ORGANIC

OF

COMPOUNDS

Definition

of

Organic

chemical
into

compounds

of
have

the

On

iron

carbon

as

for

carbon

and

these

notion

is
in

by
by

in
its

owes

the

agency

was

obtained
1

About

"

150,000.

the

oxides

old-time

could

vegetable

urea

the

the

to

of

shown

strictly

chemistry.

inorganic

first

group

of carbon

of

treat

activity.

of

istry
chem-

not

carbon

vital

so-called

consideration

of

compounds

on.

so

Organic

origin

we

the

chemistry

to

pounds
com-

number

is, however,

carbonates

untenable

1828,

the

customary

organic

that

organisms,

is

the

name

only

who,

it

is

and

for

chemistry.
it

the

carbon,

apart

ist
chem-

Thus

great

element

definition

This

accurate,

beUef

of

branch:

that

all

group,

the

is set

branch

special

compounds.

The

the

compoimds

is

of

of

however,

ganic
inor-

the

element.

sulphur

the

containing

by

comprising

particular

group,

accoimt,

classified

are

group

some

compoimds
of

groups,

various

The

Chemistry.

or

That

by
main

be

duced
pro-

animal
such

Wohler,

organic

ana

conntitucnt

of

intent

being

Since

that

have

IxHui

but

thousands

from

of

in

been

never

and

three, four, or

vhIoucom,

are

llydn"Ko",
Oxygtui,
Nitn"geu"

H,

''

''

(),

**

''

N.

''

''

''

**

*'

''

atonuo

Phosphorus, r,
S.
Sulphur,
iiuportaut

iu

Hr, I).

iu

the

i)xy)4:eu

chemical

The

their

wt.

in

nature,

organic

pounds
com-

with

one,

The

elements.
in

organic

pounds,
com-

and

weights

atomic

12, valence

U",

''

IL

14.

''

III

and

V.

aU

''

III

and

V.

32.

''

II, IV

contain

the

of nuxst
W

can

IV.

''

1,

presence

tiv^ls, the

elements

elements
detected

being incorporated

sum

is K^sj;?
than

of
one

of

presence

it is detected

oomjx"{Nitiou of the
the

VI.

halogens

quite readily

ones
priiieipal

the (H^venta^e
by fuuliuiij:
iiixd observing that

and

of these

The
experiments tknt follow.
bo dlivetly doteruuue^l:
cannot

of all the other

organic

laboratory.

In

present

eoiupouiuls

""rganleeoiup"HUuls

t"ysimple

to

follows:

as

Cy

{(X

known

five other

Carbon

Some

fact, a great

in combination

even

in^portant elements
together with

uu)st

In

Detection.

exist

may

without

laboratory

discovered

in the

Their

carbon

the

compounds

Ihhmi created

Elements

of

vital processes.

the

have

have

two,

ammonium

i)repared

evaporating an
iso-cyanate, his
latter salt (p. 278).
organic compounds

simply

recrystallize the

to

asHistance

chomiHtH

by

of

date

proportion

chemistry

urine

Holution

acjuoouH

any

ASIC

the

per

pound
com-

cents

himdred.

charred

the

up

divide
To

the

NaOH

color

indicates

solution

of

N.

solution;

FeCla

HgCl2, is caused
If

is

sodium

of

HNO3

to

(precipitate of

AgNOs
iodine

bromine

and

detected

by conducting

little CS2
and

close

exp.

1).

(for
the

this

tube

If it is desired

best
tube

are

drop

to

that

asbestos

is held

the

with

to

AgBr,

or

the

into

N, S,

for

melted

the

boiling

In

halogens

Sodium

Formula

ferrocyanide

is formed

=Na2Fe(CN)5(NO).

by

be

may

with

this

test

be

can

containing
short

in

through

this treatment.

in
a

in

as

liquid

contained

test-tube

tube

pad.

filtrate

and

bent

excess

testing

acid

in

thrust

organic

concentrated

test-tube

sodium

verticallyby being

in

of

nitric
a

by

sufficient

Agl).

mixture

or

is due

an

then

stopper having

detect
on

and

vapor

heat
a

if a

volume

the

drops of

examining

HCN)

free by

set

test

liquid

the

AgCl,

lead

acid.

few

off, prolonged

all the

remove

add

sulphocyanide.

tested

one-tenth

driven

H2S

or

be

formed

not

may

it with

of

(HCN

necessary

(itis

used), halogens

boiling some

by

method

this

by

in

fresh

is removed

of

formed

of

acetic

add

HCl;

Prussian

precipitate

or

the presence

is not

of

To

color, which

red

by

sulphocyanide

compound

with

of

reddish-violet

with

acidify

drop

minutes,

drops

S.

of

discoloration

NeutraUze

S.

to

few

presence

and

brownish-black

add

few

appearance

nitroprusside;^

solution

acetate

The

D.

and

two

precipitate

To

the

to

mixture

HCl.

or

sodium

points

this

Boil

solution

FeS04

and

C, and

B,

strongly alkaline, then

acidify with

greenish-blue

pestle. Filter

portions A,

until

solution.

cool, and

(Jolor

into

freshly made

of

of FeCla

blue

with* the

mass

filtrate

add

drops

an

CHEMISTRY

ORGANIC

it is
test-

hole

in

ORGANIC

(3)
in

Put

CI.

dry

soak

and

powder

with

Mix

P.

half

When

and

of

the

Add

filtrate

alkaline, then

add

formed

by

the

then

add

the

HCl

until

add

NH4OH

solution

and

fine yellow precipitate

Having

thus

in the

and

MgCU

add

350

crystals
c.c.

Ammonium

75

gm.

water

with

C.P.

NH4OH.

HNO3

and

of

8%

is

made

and

70

of

the

powdered
aid

of

Pour
675

c.c.

to

as

gm.

this

of water

To

water

ammonium
bath

until

are

ent
pres-

he is investigating,
its

Dissolve

follows:
in

NH4CI

thorough

more

1300

55

gm.

of water

c.c.

hydroxide.

solution

is made

ammonium

heat,

phates,
phos-

phosphorus

elements

that

ammonium

molybdate

The

of
a

what

proceeds

mixture

^Magnesia
of pure

determined

next

strongly

appears.

organic compound

chemist

filter.

until strongly

volume
in

an

precipitate.

HNO3

heat

little

and

until

of the

mass

into

neutral

white

equal
2

it in

mixture.^

oxidation

cause

an

until the

resulting solution

half of the filtrate add

molybdate

the

give

(1 part Na2C03

crucible

magnesia

compound^

the other

acid,

should

cool, dissolve

the

pour

dish.

evaporating

of

AgNOa.

with

alone

mixture

in

Heat

white.

water

To

with

dry nucleoprotein (or dry yeast)

parts of fusion

twenty

is almost
hot

Test

soda-lime

some

parts KNO3).

+2

dissolved.

tube

the
Treat

mortar.

it

as

slight turbidity.

(4)

in

with

test

Break

strongly.

mass

until

chloroform

much

as

heat

the

HNO3

control

only

and

up,

soda-lime

powdered

pure

test-tube, add

will

strong

little

COMPOUNDS

and

into

while

molybdate
add

(when

mixture

of

solve
Dis-

follows:

as

in 250

cool)
300

35

c.c.

stirringvigorously.

c.c.
c.c.

of
of

of C.P.

ORGANIC

He

examination.
of

amounts

the

is

empirical

with

the

known,

structure

certainty

the

under
free

from

admixture

is necessary
chief

tests

The

atoms

p.

98).

by

for

at

methods

any

this
of

purity

This

will be

done

each

element

of

in the

in

one

pound.
com-

the

stance
sub-

i.e.,

pure,

substances.
to

molecule,

explain

total
as

as

is

that

chapter
the

It

well

as

substance

gives merely

then

the

absolutely

the

the

absolute

of

purification

the

formula

with

other

pound
com-

with

stage, therefore,

which

empirical
of

us

of

molecular

in failiu'e unless
be

examination

endeavors

chemist

the

construction

will end

work

which

synthetic

estabhshed

has

simpler

identical

are

examination,

chemical,

all this

But

that

are

of

same

his

its

atoms

molecules

If

how

causing

the

having

compound.

he

its

he

treated

to

as

(synthesis),he

united

under
that

the

stance
sub-

one

when

is, how

of

structure

calculate

therefore

clue

the

molecular

than

finally, by

properties

considers

get

in

to

compound

that

And,

his

as

to

up,

data

formula;

of the

order

its

more

same

substance

substance

this

become

to

shows

the

these

built

the

produce

to

from

together.

substances,
is

able

in

is

linked

determines

reactions

reagents

molecule

he

have

may

studies

then

But

percentage

contained

elements

formula.

the

estimates

various

and
He

weight.

first

the

substance,

CHEMISTRY

the

tained.
ascer-

follows.

number

C6H12O6

of

(see

CHAPTER

PURIFICATION

II

AND

IDENTIFICATION

OF

SUBSTANCES

PURIFICATION

The

main
in

methods

distillation,

that
to

The

by

cold

in

solution.

By

perfectly

manner

and

invaluable,
for

suitable

used

it

solvent.

each
are

be
a

of

be

to

will

it
Put

purified
different

water,

as

purification

carrying

to
to

its

slight

remains
this

in

crystallization

crystallization

as

separation

add

of

obtained

be

can

the

cooled,

dextrose

acetaniUde

pure

hot

in

below).

exp.

Inasmuch

is

repeated

the

trose
dex-

two

is

because

while

water,

For

from

these

solution

out

ble
solu-

solvent.

separated
of

the

is

usually

same

mixture

crystalUzes

solubility

(see

the

the

method

not

are

be

can

this

of

resulting

the

acetanilide

in

extent

dissolving
when

water;

in

basis

acetanilide

example,

dialysis.

substances

equal

stance
sub-

organic

an

crystallization, sublimation,

and

different

an

separating

are

extraction

Crystallization.
fact

of

state

pure

SUBSTANCES

OF

well

small
into

detail

ether,
7

specific

quantities

(those

for

compounds

of

the

test-tubes;
most

tions
direc-

select

Carefully

several

solvent

alcohol,

organic

(1)

out.

method

stance
suband

commonly

chloroform,

benzol,

ORGANIC

petroleum
Discard

the

hot

when

hold

dissolves

exert

no

the

certain

action

the

using

funnel
funnel

stemmed
stem

and

water

before

too

small

may

occur.

(5) Cool

the
the

cold

with

(With

funnel

resorted

in

the

in

the

in

hot

to.

beaker

of

long-

out

separate

be

may

the substance.

plaited filter,

stem.

volume

having

liquid.

creeping of crystals and

If

slowly.^

crystals

with

or

temperature

solvent

may

filtrate

redissolve

quickly,

boiUng

at

it.) He^tting the

beaker

when

short

filtration

twice

capacity

solution

should

it whatever.

on

crystals

block

(4) Collect

solvent

liquid through

with

solvent

readily,but

The

of the chosen

hot

acid).
readily.

the

substance

in

saturate

quantity

(3) Filter

substance
Choose

cooUng.

on

(2) Completely
a

the

the

impurity

solvent

glacial acetic

remaining.

deposits crystals
either

dissolve

that

of

each

which

and

ether, acetone,

those

Heat

CHEMISTRY

aid

the

rapid cooling by wrapping

are

With

liquid

deposited
heat, and

of
the

beaker

very

vent
pre-

with

towel.
the

(6) Cover

into

liquid

the

watch-glass

(7) Do

not

or

and

often

piece
from

disturbing the

disturb

the

beaker
is

be induced

to form

of

filter-paper

falling back
crystallization.

glass plate completes

If their appearance

formed.
may

condensation-drops

prevent

to

with

beaker

until

the

covering.

crystals have

greatly delayed they

by scratching

the inner

"

5, 6, and

crystalsis

7 may

be

disregarded except when

to be studied.

the form

of the

PURIFICATION

with

of the beaker

wall

glass rod,

crystal of the substance

(8) If the

in the

cold

about

by

into

the

is not

substance

SUBSTANCES

OF

'*

sowing

liquid.

sufficientlyinsoluble

solvent, crystallizationmay
in

evaporation

slow

''

by

or

be

brought
covered

loosely

crystallizationdish.
the

(9) Collect

crystals

wash

Uquid), and
cold

them

crystalsin

the

they contain

of

water

beaker

and

heat

Completely
cool

hot, and
has

formed,
until

the

At

and

through.

Save

they

in

Fehling's reagent

salt.

The

volumes

KOH

gm.

is of

latter

7%
and

red

mixture

When

Filter

good

of dextrose

FehUng's

be

may

consists

being

35

gm.

held

made
of

and

of

Rochelle
when

forms
precipitate

an

be

carried
After
of

(see below).

in solution

be freshly

solution.^

determination

solution

alkaline

an

ess
proc-

longer

no

crystals.

white

desiccator

crystals

the

with

pure

while

Dissolve

filtration.

by

boiled

CuS04

of

crop

crystals

deep-blue color, and

of dextrose

pad.

the

reagent should
of

asbestos

from

the

melting-point

hydroxide, the

an

crystallizations should

dried

are

when

into

recrystallize. Repeat

when

three

on

the

them

filtrate

least

25

pure

water

furnished.

is

separate

water

of distilled

c.c.

it with

which

gives reduction

the

of

desiccator,except

boiUng

to

rapidly.

Httle

20

satiu'ate

acetanilide

and

the

Httle

of the

surface

crystallization.

Put

Experiment.

in

with

the

(reject

solvent.

(10) Dry

suction-filter

crept above

crystals that have

the

on

by

means

of

cupric

of Rochelle

prepared by mixing equal

alkali

salt in

solution

100

c.c.

it is boiled with
in it.

containing
The
even

reagent
a

trace

10

ORGANIC

To

test

point

is

purity of the crystals their

the

determined.

melting-point
the

quite sharply

that

follow.

(up

higher

280").

For

still

engraved
be

the

on

and

Make

by heating

in

end

one

powdered
in

of

into

each.

chloral

desiccator.

All temperatures

into

hydrate
Gentle

such

that

cm.
a

scratching

given in this book

are

and

seal

tube

with

thus

and

been

has

about

long, is

lengths of 6-8

Put

red,

it out.

tube

feet

or

until

is

diameter

in

nrni.

mm.

flame

drawing

capillary
1.

of 10

section

2-cm.

then

Break

thoroughly

glass tube

obtained.

tals
crys-

melting-point

diameter

Fig.

the

desiccator.

Experiment.

tubes

The

The

stem.

powdered

higher

with

one

0-

peratures
tem-

used.

is

be

should

for

80"

for

paraffin

thermometer

in

used

be

may

is used

to

temperatures

dried

crystals

successive

for several

of water

acid

should

The

melting-point (below

low

Sulphuric

scale

become

solvents), the

different

constant

bath

in

crystals melt

1".

to

described

Pure

0.5"

from

remains

having

making

lization
when, after repeated crystal-

pm-e

(preferably

substances

be

will

within

be considered

determinations.

of

melting-

completely, i.e.,they

and

completely melted

melting-point

method

The

determination

experiments

may

CHEMISTRY

some

dried
a

centigrade.

file

12

ORGANIC

CHEMISTRY
m

midway

thermometer
in

mercury

the

surface

of

the

reading

of the

formula
of

is

the

T)

thermometer

glass is

point of

pure

the

most

For

careful

of

The

crushed

of its

mm.

rapid
when

until
the

of
which

the

H,

The

tube

near

is

the

the

L(T

corrected

t)

"

of

cury
mer-

melting-

is essential.

should

be

desirable.

same

thickness

Tested

used.

0-50", 50-100",

be

be

of

sifted

the

The

set

100-150"

melting-point

of wall

the

as

wall

20"

below

be

such

the

through

filled for

the

melting-point
to

as

not

cause

is heated

Such
"

an

Konstitution

as

"

3
be

reached,
3"

over

by

apparatus

corrected

is

minute.

bath

double

thermometer

melting-points marked

per

in

about

only

initial heating may

The

melting-point 0.5"

greater accuracy.

fine-mesh

particles gives variation

be

should

desirable.

Meyer^s Analyse und

ungen.

size

should

air about

liquid insures
1

bath

than

expansion

things

as

range,

should

temperature

heating

the

in

The

and

of the

stem

determining melting-points

length, solidly packed.

minute,

per

of

the

crystals

melting-point.

correction

thermometer.

variation

as

screen,

the

surface

formula:

thickness

limited

about

of the

in

number

0.2", would

have

bulb

of the

work

standard

-The

is cooler

The

the

is 132.6".

of

for

should

tube

of

0.000154.

to

thermometers

graduated

coefficient

the

the

thread
the

accurate

of

'

" in

reading (which

that

by

urea

attention

thermometers

fact

make

degrees

above

observed

mercury

The

(0.000154).
in

the

calculated

be

(this is

formula).

the

and

quickly

in

column

of

and

can

this

measure

to

of the

first thermometer

from

in the

( =1/

account

on

bulb,

Also

he added

must

meniscus

air temperature

mercury

H2SO4

of the
that

bath;

the

below).

height

of the

stem

the

the

between

rise

ring
Stirof

means

well
can

as

be

the
con-

quoted from
der organischQH Verbind*
are

PURIFICATION

by taking

structed

in it

suspending
the

beaker

As

stirrer

spiralat the end

the
When

steadily.

air

An

of

when

substance

covered

of

walls

the

at

can

impurity
the

is

condenses

exp.,

p.

is

employed

temperature

which

the

substance

simple distillation

sufiices.

of volatilizable

distillation has
described

in

to

the

itself

will

dish

is

upper
on

the

for

substances,

vaporize

not
a

When

temperature

readily vaporizes),

When,

resorted

stem

mainly

sohd

(i.e.,at

liquidsis
be

the

359).

useful

that

material

slightly

advantage.

to

to

has

the

into

and

distilled

of

The

passes

method

be

state

this, the

purification of liquids. Certain

however,

at

This

(see

funnel

cotton.

vapor

funnel

limes
sub-

containing

over

with

apparatus

of the

Distillation.

the

imtil

gradually

rection.
cor-

filter-paper which

inverted

loosely plugged

chamber

the

with

is

diameter

heated

cool

dish

evaporating

or

follows

as

stir

certain

to

solid

out

1.

oil temperature

substance

the

is carried

Fig.

calculate

to

from

in

the

below

pin-hole perforations.

smaller

being

only 3-7"

readily

pend
Sus-

test-tube.

purification applicable

method

is

of

large

melting-point,

the

it is unnecessary

it passes

watch-glass

several

approaches

Uquid.
in

shown

as

fill

and

same

coiled

the

into

5 cm.,

the

of the

is sublimation.

The

vapor.

depth with

cm.) and

Pour

depth of

test-tube

the

temperature

substances

solid

in

secured, hence

method

its

to

loosely the inside

temperature

is

fit

to

thermometers

the

cm.).

piece of gold-plated wire,

use

of

(17-20 by

(20x3

(liquidvaseline)

nine-tenths

for

beaker

large test-tube

albolene

test-tube

tall Jena

13

SUBSTANCES

OF

dealt
to.

however,

ture
mix-

fractional

with,
This

method

following experiment.

is

Certain

14

CHEMISTRY

ORGANIC

mixtures
in the

alcohol, or

Experiment.
shown

resolved

up

Into

of

cork

insert

hang

it

below

^^'

first flask

the
while

the

asbestos

having
Flask

nmnber

between

88"

that

distills

all the

fraction, and

For

hole

88".

over

the

the

second

and
over

water.)
of the

condenser

dry

cloth

collect

all

dry

registers

flask

distillate

and

distillate

second

and

each

all the

the

and

or

below

the

splashed
Have

labeled.

coming

In
over

temperature
outside

inch

that

of the

it to

an

diameter.

in

distilling between

three

is to

The

catch
flask

last

above

93".

(Do

Measure

the

amount

residue

the

tube.

change

one

93".

and

bath.

water

ready and

Now

the

side

be

to

f asks

83"^.
with

be

enough

on

in

is in

of the

not

must

low

flask

i.e.,opposite

vapor,

Heat

bulb

the

opening

thermometer

pad

the

distill

nor

collect

distillingflask

83"

neck

78"^ and

between

In

bulb

dry receiving

clean

four

The

boiling hquid.

the

by

the

the
hole

in

Select

thermometer,

that

so

of

stream

300

drop

fit

will

Through

tightly.

about

capillary tubes.

that

cork

as

distilling flask

alcohol, and

70%

short

some

apparatus

funnel

as

benzol.

and

the

through

c.c.

distillation,such

distillation

diagram.
pour

constituents

their

alcohol

methyl

Set

the

in

into

by fractional

state

pure

and

water

be

cannot

in the

flask.

the
ceives
re-

not

of

Drain

tube.

distillation use

smaller

distilling

PURIFICATION

15

SUBSTANCES

OF
-

flask

or

small

shown

as

flask with

in the

diagram.

nimiber

and

one

receiving flask
reaches
of flask

80"

two

number
as

before.

reaches

80"

When

as

the
the

add

three

flask, and

the

tents
con-

the
perature
tem-

number

pad

the

liquid in

to

the

flask

distilling
ture
temperaFig.

Determine

table

4.

88".
the

per

cent

of alcohol

in these

by taking the specificgravity of each

Westphal's
the

perature
tem-

temperature

distill until the

reaches

fractions

first

replace

asbestos

the

to

When

83"

number

fluid in

receiver; also change the

the

distillingflask
as

into
the

flask

by

one

the

when

rises to

again
flask

distillate.

two

distillingflask,and

it the

latter

the

pour

number

into

attached

3.

use

the

for

column

Pour

Fig.

flask

bulbed

balance

(see p. 24), and

(p. 445).

By

comparing

repeated

three
with
with

fractionating

16

ORGANIC

of

number

one,

and

nimiber

four.

only
78-79".

secure

boil

with
Vacuum

the

mixture, which

even

at

200"

mixed,

of

course,

distinct

at

first fraction
at

over

90%

least

(by

can

out

by bubbling

kept

at

tem-

5.

be
with

obtained

in

the

tillate,
dis-

large quantity

substances
at

pressure

substances

means

do

that

100"

of
not

till
dis-

will not

steam.

is

distillation

in
the

flask

alcohol

coming

is

By this

Those

vapor

particularly when

of

the

redistill the

at

flask

into

simply

carried

is sometimes

(see Fig. 5).

a

it is

contain

of at least 100".

perature

have

water

distillate

FiQ.

water

the

into

of alcohol.

through

that

brought

case,

should

Distillation
steam

in this

and
This

volume)

of

most

As, however,

is of value

is

alcohol

the

practically all

that

CHEMISTRY

order

substance.

temperature

it is desirable
to

prevent

Many
below

in

employed
to

lower

any

substances
their

certain

cases,

the

ing-point
boil-

decomposition
decompose

boiling-points.

The

PURIFICATION

distilling apparatus
for

of
the
fine
in

the

heated

stopper,

is open

bubbles

of

commotion
is

reduction

which

keep

air

in the

the

this

tube

the

flask

The

ing
receivA

suction-pump.

apparatus

to

being

about

pressure

face
sur-

through

of

bumping.
a

except
the

passing

contents

with

(atmospheric

usually lower

the

pre^cent

connected

below

dips

air; through

the

to

17

air-tight

up

liquid and,

of pressure

mercury

closed

tube

and

flask

will

is

finely pointed

SUBSTANCES

OF

boiling-point

of

30

of

mm.

mm.)

760

high-boihng

'

substance

by

is

pump

The

ordinary

usually quite satisfactory

of purity of

test

distillation,a
same

material

boiling-point

completely

likely to

substance

boihng-point.

of

over

An

for

suction-

lowering

the

distills is

stancy
con-

(see Fig. 6).

pressure

the

100".

nearly

be

pure

at

each

that

substance.

If,

that

after

repeated

is

obtained

time

and

temperature,

tional
frac-

which
which
it

has

distills
is

most

18

ORGANIC

Experiment.
either
side

CHEMISTRY

The

boiling-point flask

long-necked

tube

distilhng flask

off very

coming

or

high

has

to

the
the

of

of

the

The
as

the vapor

those

c.c.

the

interpose
asbestos

for
the

column,

of

flask

should

used

the

passes

up

whole

length
being

thermometer

be

of the

on

long tube

When

kind

same

determination

until
least

in

the

the

in

Heat

freely

passes

with

remained

has
Take

the
is

small
denser,
con-

tion
distillaconstant

reading

necessary

an

place

the

Continue

temperature.

correction

and

into

to

diameter).

air-condenser

position.

flask;

flask

the

inch

one

temperature

No

the

(it is advisable
and

gauze

an

five minutes.

boiling-point.

into

gauze

hole

a
as

vapor

note

wire
the

having

receiving flask

chloroform

pure

between

pad
a

for at

an

'

support

flame.

such

tube, heating

the

specified for melting-point

20

Attach

outside

thermometer

the

thermometer

Put

In
.

sufficientlyto permit this.

(p. 12).

descends

mercury

lowered

of the

7.

cork, then

stem

ping
slip-

from

chamber

(see Fig. 7)

point

proper

tube

the

with

dented

at the

apparatus

the

so

neck, while

blast-flame

flask

panded
ex-

end

lower

been

prevent

is fitted

slightly

the

fit the

to

into

the

cork,

the

near

tube

open

latter

to

the

of which

at

Fig.

has

which

up

into the neck

as

be

ordinary distillingflask

an

an

should

as

the

except

20

ORGANIC

could

which

occur

that
for

the

760

mm.

the

when

since

apparent

in the

pressure

has

barometer

point under
The

standard
the

and

scale

760

mm.

apparatus

liquid that

barometer

used

be

can

to

apparatus

boil

to

regulate the
distills at

the

latter

metal

other
760

at

If the

asbestos

method
mixture

from
with

pressure.

involved

be

salt
more

in

moisture

eliminate

the

examination.

Now

boiling-point

standard

to

the

the

pressure

temperature

boiling-point of

the

It

by

solvent

that

be

from

extracted
latter

the

with

extracted

rapidly.
in

CaCh),

readily extracted.
that

substance

in

In

many

the

water

then, of
The

has

than

by saturating the
or

is

be

substance

diminished

extraction

be

organic solvent

the

(as NaCl

feasible

immiscible

is
is to

extracted
of

may

pad.

most

shaking

that

flask with

compound

organic

an

the

the asbestos

on

infrequently

solubility

with
it will

rests

substance

greatly

be

to

0.1"); then

to

mixture

will

it

absolutely

an

liquid of known

solubility in the

the

cases

is under

extraction.

by

If the

greater

arranged

of

amount,

absorb

to

high boiling-point,shield

organic

an

water,

may

changes of

liquid distills will be

aqueous

water.
a

get the boiling-

to

the

corresponding

separating
is

an

mm.

air-tight distillingapparatus

the

(read

Not

of

second

cylinder that

Extraction.

(761.9

mm.

liquid has

or

temperature

the

15", the

is

demonstrate

be

can

that

so

pressure
a

which

the

mm.

inclined

not

liquid that

previously determined

at

and

is stable

by connecting

which

as

be 762

are

pressure.

(as benzene), the

in

room

accurately determining the boiling-pointof

After

is

pressure

of the

scale), in order

brass

made

barometer

of the

must

apparatus

bered
remem-

be

must

barometric

mercury

change of boiling-point for definite

pure

barometer

of the

be

It must

pressure.

example, if the temperature

For

if the

correction

temperature,

0".

at

atmospheric

as

small

CHEMISTRY

tion
solucourse

principle
soluble

PURIFICATION

in

two

in

the

of

ratio

its solubilities

instance, if

For

is twice

for

solution.

in aqueous

much

and

small

of

large, volume

of

ratio

the

ether

will

in

result

carried

three

out

of ether

will

contain

will remain

several

sive
succes-

solvent

of

If

is

with

single extraction

with

solubilities

the

three

the

if the

with

original
but

solution;

remain

of

volumes

of

aqueous

times

after

(as above), extracting

two

will

one-twenty-seventh

that

one-seventh

in

remaining

amount

then

volume

ether

solvent.
to

one

solution

one-third

by shaking thoroughly

once

water,

portions

efficient than

more

in the

in

two

solvents.

two

aqueous

equal

an

the

in

It follows

with

extractions

are

with

as

of the substance

two-thirds

ether

the

length of time, the

proper

very

in

solution

shaking the

in

compound

soluble

as

itself between

distributes

liquids

21

SUBSTANCES

OF

only
is

shaking

of

volumes

equal

ether.
If

the

solvent

trace

of

water,
the

remove

recovered

that

one

takes

The

substance

distillation

If necessary,

be

it may

20

c.c.

c.c.

of

Measure

used

to

extracted

is

of

the

purified further

by

into

of saturated

by

with

treatment

minutes.

of the funnel

into

separating

tightly, and
off the

Draw

the

carefully pour

salicylic acid

ether, stopper

for ten
and

be

solvent.

Experiment.

20

than

more

evaporation

or

crystalhzation, distillation,or
different

up

should

drying agent

water.

by

solvent.

is

ether

dry

out

flask.

solution
shake
bottom

through
Return

the

nel
funand

ously
vigorlayer,
mouth

the aqueous

22

CHEMISTRY

ORGANIC

solution

to

continue

as

of

the

above.

with

drop

of dilute

reaction

with

saturated

by

Na2S04.
the

After

ether

into

ether, using
flames

no

the
the

Now

by).
to

the

that

crystalline residue

especially

the

on

well-known

colloids

chloride

from

placed in
the

water:

the

egg

let

purification
It

depends
diffuse

to

dialyzer suspended
chloride

paper,

separate

sodium

containing these
in

running

pure

diffuses

out,

leaving

protein in the dialyzer.

When

OF

the substance

methods,

its

for

solution

IDENTIFICATION

this

and

parchment

Thus,

protein

sodium

of

crystalloids can
or

cannot.

egg

balance

appreciable

an

biochemistry.
that

(have

is obtained.

membranes

whereas

is

fact

animal

through

in

pour

of the

bath

evaporating dish,
Note

dried

time,

steam

Dialysis is occasionally employed

purposes,

bined
com-

of

some

transfer

an

evaporate.
of

or

given

the

distill off most

bath

water

solution

ether

quantity

hot

compare

amount

for

tion
por-

aqueous

color

intense
Treat

dry flask, and

the

FeCla, and

small

third

of

c.c.

the

stood

it has

near

ether

with

extract

with

acid.

salicylic

ether

ether, and

of

c.c.

extract

about

color

faint

Also

20

Test

ether.

solution

add

funnel,

the

has

identification

purpose

its

color, odor, and

determinations

are

been

purifiedby
be

may

physical
taste

SUBSTANCES

attempted.

properties

boiling-point,crystalline form

are

of
"

its

For

studied;

carefully noted,

are

made

the above

and

melting-point,

including

measure-

IDENTIFICATION

of the angles of the crystals,

ment

density

"

action

gravity,

data

thus

known

specific

or

polarized light, spectroscopic

on

refractive

appearance,

23

SUBSTANCES

OF

obtained

and

power,

solubilities.

compared

are

with

The

those

of

mentioned,

the

substances.

Aside

from

first five properties

the

useful

universally

most

for

one

is specificgravity.
considered

this will be

c^

The

of identification

purposes

of determining

method

Descriptions

next.

of the

=S3"

^11

J
Fig.

methods

several

different
of

volumes

of

liquids

methods:

1.

liquid

the

successively determined

in

called

The

picnometer.

fluids at the
1

The

Translated
MuUiken.
Lassar-Cohn.

by

Practical

of

found

by

weight

of equal

w^ater

may

be

special stoppered bottle

of

temperature

Methods

must

be

of

Organic

both

reported.
try.
Chemis-

Schober.
of Pure

Identification

Laboratory

also, Arbeitsmethoden

The

and

be

may

of weighing

moment

Gatierman.

be

larger laboratory manuals.^

specific gravity

The

9.

properties will

other

ascertaining

of
in the

found

Fig.

8.

ftir

Manual

Organic Compounds.
of

Organic

Chemistry;

organisch-chemische Laboratorien.

24

ORGANIC

The

comparison

convenient

holds

exactly 10, 25,

15"

in the
2.

for

form

be
of

as

0", 4",

or

of pure

gm.

Further

15".

is

balance

WestphaVs

representing

gravity.

used

are

boiled

details

This

liquid at

instrument
Riders

The

t:

is

in the
is

on

instrument

for

and

that

empirically

determining

mark

with

long

figures that

It

; this sinks

stem

of the latter

certain

indicate

specific

being the standard.

15"

at

the

specific

15".

at

water

pure

is another

level

one

tion
observa-

of

liquid, so that the surface

stem,
i\

with

water

in the

temperature

glass float having

place

hydrometer

graduated
gravity,

balance, each

of

gives the specificgravity

the

compared
3.

this

decimal

instrument

of the

water

explained

are

useful

very

on

different

which

one

finding specific gravity (see Fig. 9).

sizes

The

below.

experiment

different

ard
stand-

the

is

picnometer

50

or

(see Fig. 8).

taken

water

may

most

at

the

of

temperature
for

CHEMISTRY

mark
read

are

the

on

off at

specific gravity (see

the

Fig. 10).
The
with

urinometer

specificgravity

by weighing

very

The
be

for

hydrometer

use

urine.

The

while

is

it in the

immersed
little

quantity

of

liquid in

which

them

crystals

placing
in

they

a
are

in

an

found

reweighing

This

method

it

has

organic chemistry.
or

small

solids

accurately

picnometer
insoluble

be

can

air, then

application

by

solid

in water.

specific gravity of
determined

of

weighed

filled with

(see

exp.

can

some

below).

IDENTIFICATION

OF

Experiments,
ether.

accurately

will hold

deduct
the

(a) Specific gravity of petroleum

Weigh

which

from

air.

the

in

between

the

the

and

gravity

of water

amount

by the

cooling and
difference

The

gives the
divided

whether

of

weight

by

the

the

weight

of

(25 gm.) gives the specific

with

compared

as

this

When

weigh.

by

fluid.

of the

the

air is left in

observe

bottle

strip

indicated

and

the

weights

two

petroleum ether,
equal

into

re

as

stopper,

fillwith

catch

to

no

and

temperature

contraction

consequent

that

so

weight of

Wrap

neck

15";

at

and

stopper

the

gently,

off

drawn

been

water

for the

gm.

the

stopper

the

note

thermometer

an

0.027

Remove

bottle, wipe

air has

of pure

gm.

filter-paperabout

weighed,

dry picnometer

empty

an

(boiling at 60-70").

overflow, insert
the

25

weight

ether

folded

of

just

the

contained

petroleum

25

SUBSTANCES

the

specificgravity report

15".

at

water

In

ing
record-

of obser-

temperature

18"
for

vation;

that

means

18"

at

Also
with

example,
the

is 0.67

petroleum

when
the

the
urea

to

into
cause

contains

stopper
the
the
Now

ether, insert
The

of the

petroleum

the

dry

15".

at

ether

the

ether

must

and
the

Tap
the

neck

stopper

crystals.

picnometer
to

with
as

be

little test-

urea

ether.

adhering

fill the

Weigh

urea.

pure

petroleum
air

of

ether

balance.

Westphal

which

water

specific gravity

(b) Specific gravity of

tube

with

compared

0.67

"Sr-^

specific gravity of petroleum

determine
the

ether

pour

move
Rethe

picnometer

crystals

to

be

lodged.
dis-

petroleum

more

before, and

reweigh.

the

temper-

at

same

26

ORGANIC

ature

before.

as

this
the

of

has

of

(exp. a)

previous

been

the

bottle

this

sum

the

urea

immersed

in

petroleum

of

the

the

weight

Divide

this

by

ether;

the

result

the

centimeters,

of

an

equal quantity

of

the

The

specific gravity.
about

it

data

of

of

petroleum
in

(in grams)

that

so

the

weight

figure gives the

of

is

urea

investigation is known

to

as

its

Generally

boiling-

the

dealing

When
exists

determine

Tabellen

with

doubt

any

Such

Biedermann

by Carnelly.

about

the

specific

or

be

Landoldt

and

tion
determina-

accurate

an

melting-point

liquid it
the

found

of the

nature

in

the

of

and

substance.

substance,

at several

different

Physikalisch-chemische

Bornsteirij Chemiker-Kalendar

Melting(yearly^editions),

the

advisable, if there

is

specificgravity

may

tables

by

tabulated

boiling-points, melting-points,
etc.

to

by comparing

properties with

specific gravity will definitely locate

difference

of

generally be identified

can

gathered

gravities,

to

deduct

displaced.

specific gravity

under

substance

chemists

lists

to

1.33.

If the

the

the

weight

this

by

add

displacement

the

of water,

urea

containing

ether

the

rather

or

divided

used

urea

ether;

indicates

the

petroleum

bottle

petroleum

much

then

specific gravity

cubic

how

with

urea,

of the

weight

weight

former)

filled

from

is

find

the

of the

weight

the

find the

one

To

in

ing
deduct-

by

displaced by

insoluble

being

weight

the

tube

urea

picnometer.

ether

(the latter
ether

the

in

m'ea

the

Reweigh

weight from

petroleum
the

CHEMISTRY

and

by

Boiling-Point Tables

CHAPTER

III

ELEMENTARY

estimation

The

in

of

of

carbon

in

is

principle

The

difficultly fusible
about

1.5

than
is

the

copper

furnace

the

end;

cm.

of the

oxide

hold

to

analyzed
^

The
boat

be

capillary
bulb

is

tube

next

substance

it

be

of
is

tube

and

placed

in

in

the

the

with

tip

of

little
the

boat.
28

tube

another

the

coarse

20

next

cm.

oxide

cupric

If

be

to

platinum

CuO.

is

(of wire

substance

little

glass

from

cm.

then

fine

of

spiral

it occupies

The

with

mixed
a

to

the

by

in

in

sealed

in

until

place.

placed

being

or

spiral;

cm.

is charged

roll

down

pushed

intimately

may

instead

the

to

of

85

oxide

end

other

latter

heated;

pushed

of

longer

cm.

length

short

tube

diameter
10

cupric

occupied

is

mixed

analyzed

the

the

tube

the

into

is

be

this

coarse

spiral

copper

be

it is to

and

that

as

glass

inside

should

bustion
com-

The

same

in

an

follows:

of

the

hydrogen.
out

of

in

water.

the

and

tube

moderately

35-40

short

exactly

is inserted

is poured

and

which

as

form)

of

in

length.

gauze

dioxide

tube

This

combustion

for

end-products

glass having

cm.

good

the

is carried

combustion

ent
pres-

combustion

by

carbon

of

detection

the

oxide,

hydrogen

and

is made

cupric

being
method

carbon

the

compound

presence

for

ANALYSIS

or

lain
porce-

liquid

bulb

having

broken

off

when

is

to

long
the

(wire form) in the

A

below.
wire

short

tube

the

stopper

end

at the

rubber

for

apparatus

of

is

combustion

glass tube

the

passing through

or

the

oxygen.

the

directly

ucts
prodwith

the

at

stopper

of

mixture
with

collects

connected

some

Through

air

incoming

end

fine oxide

which

absorption apparatus

The

Each

is connected

the

purifying

has

finally

stopper.

the

nearest

glass tube, which

passes

with

is closed

the

and

added.

be

may

ment
experi-

spiral (which

copper

is inserted

cupric oxide

coarse

in the

described

manner

attached)

loop

29

ANALYSIS

ELEMENTARY

other

end.
When

be

might

clinging

substance, and

In

while

case

an

this

the

with

is

collected

in

removed

for

chloride

of air

stream

Pure

be

can

of

the

in

its presence.

that
and

rapidity

when

the

absorption apparatus

end

of

It may
trace

the

spUnter of wood
add
air

to
or

the

the

point.

much

ess.
proc-

better

readily, because
of

outgoing
an

combustion
of

from

stream

ember

the

on

the

glow brightly.

understanding

oxygen

it must

completion

causes

to

end,

fe very

completeness
oxygen,

takes

combustion

oxidize

not

With

is indicated

process

do

several

tube

that

at

for the

however,

oxygen,

for substances

used

other

If moisture

the

tube

the

by warming

copper

passing through.

toward

tube

the

to

matter

any

is heated

ordinary calcium

time,

the

or

unmixed

dry air

of

stream

glass

tube

whole

first

organic

any

the

to

the

place of the absorption apparatus.

has
be

the

for

of

is used

oxide, the fine oxide

horn's

service

removal

complete

insure
that

is in

tube

stream

of the

through

process

the

to

whole

ELEMENTARY

(see Fig. 11).

apparatus

solution

strong

of the

most

last traces
U-tube

pieces

of carbon

dioxide; then

Fig.

tube;

along

with
also
insure

To

of the
it the
any

through

be

as

tubes

the

gas

into

the

fine copper

combustionit aids

organic substances, and

carries

dioxide

and

material

steam

that

drying

the

air

is

sometimes

sulphuric acid.

In

this

case

H2SO4

(see Fig. 12).

removes

oxide

the

volatilized

absorbent

another

through

12.

passes

carbon

thorough

bubbled
used

dry

it reaches

when

oxidation

the

The

the

removes

chloride, which

soda-

containing
which

of NaOH,

removes

through

passes

drying-tower

containing calcium

moisture.

then

through

which

potash,

dioxide;

or

small

or

It first bubbles

caustic

carbon

U-tube

large
lime

of

31

ANALYSIS

in the

place

of

the

calcium

duced,
pro-

has

not

finally
must

also

chloride

32

ORGANIC

been

coarse

the

tube

the

and

calcium
the

the

straight calcium

The

details

is

tus
appara-

of the

removed;
here

up

chloride

method

of the

bon
car-

finally in bubbling

solution

picked

of moisture

amount

of

end

the

absorption

and

dioxide

carbon

the

tion;
oxida-

passing through

In

of the

potash

caustic

the

containing

oxygen

is absorbed,

the

bulbs

or

tube

with

it reaches

water-vapor.

chloride

water

through

air

of

contact

completes

when

stream

consists

dioxide
the

oxide, which

copper

thus

into

them

brings

oxidized, and

the

CHEMISTRY

tion
absorp-

the

sUght

is removed

tube

by

(see Fig. 12).

given in the following

are

experiment.
Experiment.
acid.

.Combustion

After

combustion-tube

the

Fig.

and

stopper

pull

the

out

oxide
Put

into
the

Weigh

short

desiccator

several
funnel

into

air-tank, quickly
clean

dry beaker,
the fine

out

replace the

spiral into

the

remove

stopper.

desiccator.

weighing-bottle containing about

days.

pour

the

acid

the

that

Through
saUcyUc

(see Fig. 13) ; add

carefully through

above,

finallypour
and

salicyUc

pure

the

nearest

beaker

charged

been

has

directed

as

spiral,and
and

salicylic

of

13.

oxide

another

beakers

of

end

coarse

accurately

gm.

stemmed

the

at

the

out

pour

0.2

heated

thoroughly

the

analysis

funnel

the crystals of salicyUc acid

some

into

acid

in such
are

clean

of

stood

has

the
a

carried

in

short-

the

ing-tube
mix-

fine oxide

way

that

along

all

with

the

CuO

half

full,insert

into

firmly
mixed,

the

shake

the

rinse

all the

oxide

tube.

Replace

oxide.

Replace

purifying
The

the

and

tube

remains

Reweigh

the

and

with

lowest

increasing
Do

heat

not

weigh
the

the

tube
attach

them

chloride

in

tube.

brought

to

contains
the

the

(remove

this

heating

having

of the

the

When
turn

down

fine

counted
whole

not

go

(three
tube

to

coarse

oxide

end

calcium
has

so

fast

in

two

dull red

that

watch

bulbs.

they

seconds)
heat

very

that

ually,
grad-

closely, and

if bubbles

here

potash

been

Stop the air-stream.

is heated,

the

and

tiles,start

tube,

of the

far end.

biu*ners

the

ordinary

with

and

chloride

weighing),

covered

been

size.

meantime

the

heat, the part of the tube

at the

rapidly through
should

the

other

oxide

and

the

of

cium
cal-

ually
grad-

very

its calcium

before

plugs

When

beginning

with

place

dull red

the

time

absorption-tube

chloride
bulb

In

the
at

number

in

fine oxide.

the

potash

of

near

burner

one

flames

calcium

caustic

end

possible,then

flame

the

near

air-stream.

end

at the

tube, starting

the

air-

the

weighing-bottle.

Begin lightingthe bm-ners

chloride

coarse

with

other

the

at

the

the

start

until

combustion-

in

pour
connect

stopper,

apparatus,

CaCU

tube.

spiral and

the

shaking

by

to the

transferred

been

bustion-tube;
com-

portions of fine oxide

small

has

well

the

into

contents

per
stop-

When

mixing-tube

the

and

tube

vigorously.

very

quickly empty

successively with

the

stopper ; hold

is

tube

the

When

mixing-tube.

the

and

33

ANALYSIS

ELEMENTARY

pass

bubbles

The

cannot

too

be

easily

Finally, bring the

(never hotter)

When
.

34

CHEMISTRY

ORGANIC

bubbles

but

complete;
for

to

cease

do

not

Then

the

of

the

is

cool

to

biu*ners

tiles.

tube

combustion

for

an

point
tubes

before

minutes
to

of

dioxide.
the
for
the

cooling

plugs, and

When
Do

plugs.
tube

Before

in the

is

the

potash

passed

heated
it.

through

bulbs

balance
after

should

The

not

be

room

calcium
tus.
appara-

for another
while

hour

an

KOH

dry

solution

used

on

removing

the

is used
for

carbon

tubes, put

place of the absorption

be

this

rapidly

and

attach

to

point.
at

more

the

combustion-tube

analysis, it should
air

forget

if

first fifteen

vapor

in

end

absorption

the

cool, reweigh

not

the

cool

to

end,

water;

the

absorption

by

the

at that

air-stream

all water-

the

allow

hour.

chloride

two

tube

of the

of

During

the

pass

tube

air-stream

out

oxygen

Disconnect

one

to

reweighing.

out

sweep

clear

to

as

so

used, change

proper

each

condensed

If

is

the

Examine

heating

tube

used) while

from

present, vaporize it by careful

oxygen

the

of

oxygen

begin
the

remove

practically

(which will give the

air-stream

gradually turning down

but

is

heating

(fifteen if

bubbles).

of

rate

slow

the

continue

thirty minutes

passing

combustioil

pass,

for

in
than

more

combustions.

The

increase

tube

indicates

the

combustion.

therefore

the

Per

the

weight

of the
of

weight
One-ninth

per

burned

substance
formula

in

of

cent

the
of

calcium

can

be

obtained

wt.

of H2O

produced

water

this

hydrogen

chloride

is

hydrogen;

present

by

the

produced

100

H
9 Xwt.

of substance

in

the

following

cent

by

burned

ORGANIC

36

combustion

when

off;

CHEMISTRY

again turned

to

on

is

remove

all the

present

in

air-stream

the

complete

is
the

products from

tube.

// halogens
analyzed
with

the

spiral

silver

reduced

the

the

are

and

absorption tubes,
sulphur
The

tube.
and

in the

used

their

prevents

of the

tube

as

combines

be absorbed.

is

is

lead

present

cupric oxide

phosphorus

or

place of

passing into

they would

place

be

to

in

silver

phosphorus

sulphur

is held

be

must

where

or

the

takes

chromate

substance

spiral. The

copper

halogens

When

the

in the

fully oxidized,

sulphate

or

in

an

phosphate

of

lead.
To

estimate

the

the

of dried

stream

is used

for

and

combustion

for

contained

oxygen

The

begun.

the

top) having
as

caustic

longer collect
full

dioxide
is shut
the

is

and

at the

of

out

the

tube

the

40%

When

carbon

is cleared

of

red

at
to

solution

of

the

only

the carbon

no

latter
carbon

dioxide

is carried
to

is

bottom

and

(i.e., when

tube)

and

case

bubbles

top of the burette

up

by the

glass cock

air,

heating is

in this

in

14).

combustion

completed

the

with

filled with

of the

of

nitrogen

before

mercury

caustic

gradually
is

until

some

passing

off and

tube

tube

(see Fig.

potash

remains

the

out

closed

(a burette

valve,

clearing

absorption apparatus

burette

instead

gas,

for

provided

etc., produced

gases,

in the

gas

act

the

above

employed,

dioxide

carbon

removing

be

can

stance
organic sub-

described

that

as

substances

nitrogenous
a

tube

same

alone

nitrogen

heat.

dioxide

by heating

out

is

nitrogen,

When

bustion
com-

passed again
as

shown

by

ELEMENTARY

the

of

constancy

burette.

The

volume

the

except

stand

to

of

potash

caustic

of combustion
is allowed

37

ANALYSIS

for

to

reservoir

in

the

to

exactly the

that

the

with

the

mid-level

of

trogen
ni-

bulb

at

the

gas.

reading

barometric

The

as

against the

thermometer

burette,

in the apparatus.

up

by placing

is found
a

room

off.

the

of

temperature

to

come

and

read

is

gas

burette

The

meters
centi-

of cubic

of
The

level

bm-ette,

number

the

ducts
pro-

brought

is

same

the

in

the

potash

caustic

The

all the

nitrogen.

temperatiu'e, the alkali being leveled

in

gas

absorbs

hour

an

the

(corrected for temperature)

must

results

be

of

the

are

by referring

speciallyprepared tables,

which

in

give

to
at various

the

pressure

Table

of

VI,

the

at

p.

water

the

450).

moist

and

447).

p.

14.

sponding
corre-

of

c.c.

nitrogen collected

hydroxide

Fig.

temperatures

(see Appendix,

pressure

the

grams

nitrogen

of

amount

for

The

analysis

computed

then
to

taken.

also

over

In

under
order

that

temperature

burette,

various

pressures

to

the

table

the

metric
baro-

use

alkali,add

difference
and

in the

gas

to

between

the

of

40%

potassium

of

observation

vapor

(see

38

ORGANIC

An

CHEMISTRY

method

easier

of

Kjeldahl

method, by which

substance

is converted

with

sulphuric

pure

can

ammonia

thus

calculated.

readily be
do

give

not

Kjeldahl

method.

employed

in biochemical

fully described
on

that

in

from

of all the
the

After

the

the

extensively
will

be

found

greatest
smaller

figures,

express

the

number
The

molecule.
this.
contain

or

Alcohol

52.05%

of the

sum

the

the
of

is

compound

determined,

i), and
nearest
atoms

following

C,

of

use

whole
of

the

(as the
of these

element

in

one

and

of

to

example

H,

each

number,

each

by

of

them

found

each

make

found

13.13%

be

may

number

smallest

was

per

present.

percentage

divisor

common

is calculated

weight, divide

its atomic

resulting figures by

the

composition

for the

divide

by

element

elements

other

percentage

follows:

to

by

laboratory manuals

hundred

one

provisionalformula

one

can

compounds

is

directly, but

estimated

is not

by deducting

as

of

subject.

Oxygen

cents

of the

amount

estimation

analysis and

many

of

substance

method

This

the

amount

the

organic

nitrogen

correct

and

measured

the

organic
few

sulphate

into

From

the

in

heating

alkaU,

neutraUzed,

is thus

contained

nitrogen

with

distilled
acid.

by

ammonium

The

Uberated

which

this latter

ammonia

treated

standard

of

quantity

acid.

is the

nitrogen in the organic

the
into

be

then

produced

estimation

nitrogen

will

trate
illus-

analysis
34.82%

O.

Then
iln

many

be used.

cases

some

other

common

divisor will have

to

52.05

13.13^

34.82-^16=

4.337

12

H-

39

ANALYSIS

ELEMENTARY

4.337

-^

2.176

1.993
=

13.130-2.176=6.030

1=13.130

2.176

2.176

-^2.176

1.000
=

Therefore

substance

any

becomes

atoms

weight;
becomes
formula.

the
then

necessary

in
the

the

molecule

value

possible

however,

would,

having

of

to

formula

is
write

finding
thus

be

same

shown

by

out

correct

the

It
number

the

discovered,
the

The

C2nH6nO".

determine

to

by

C2H6O.

be

may

composition

percentage

of

formula

the

molecular

so

that

empirical

it

IV

CHAPTER

MOLECULAR

DETERMINATION.

WEIGHT

IONIZATION.

molecular
from
This

acetic.

or

any

and

estimating

of

weight
and

be

to

the

64.6%.
is

having

ascertained

see

what

in

silver

formula

107

only

then

CHOAg,

the

silver

one

this

proportion

this
per

salt
be

will

the

monobasic),

Suppose

CH2O,

silver

is

acid
with

agrees

acetate.

formula

the

such

atomic

it is monovalent,

that

that

that

(showing

occurs

and

107.9

be

it, this

that

knowing

Now,

acid,

its

in

of silver

amoimt

acids

to

might

forming

By

tives.
deriva-

its

of

simple

be

can

easily appUed

its formula

thereof.

silver

analysis

example,

analysis,

multiple

found

for

substance

is most

Take,
By

of

quantitative

method

bases.

as

DERIVATIVES

weight
a

ANALYSIS

BY

DETERMINATION

WEIGHT
OF

and

VISCOSITY.

SOLUTIONS

MOLECULAR

deduced

TURE
NA-

PRESSURE.

TENSION.'

SURFACE

COLLOIDAL

The

OSMOTIC

SOLUTIONS.

OF

THE

salt

to

of

Ag

cent

acetate
we

can

of silver
have

the

must

be

XlOO

=78.8.

Obviously

CH2O

cannot

be

the

136.9

formula

correct
as

107

the

for

formula,

acetic
the

acid.
per

cent

If

we

of

take

C2H302Ag

silver

will

be

XlOO

=64.6%;

therefore

166.9
40

C2H4O2

is the

correct

WEIGHT

MOLECULAR

the

formula.

In

have

found

been

form

to

be

to

the

WEIGHT

order

understand

to

weight

determinations,

review

relate
and

later, gases
behavior

are

of the

The

of

atO^

constant.

liters at

In

making

remembered

that

273", and

therefore

absolute

the
273".

volume
with
2.

of

Boyle^s

the pressure.

see

ception
con-

known

and
factorily
satis-

more

every

degree

absolute
for

any

by

of rise of temperature.

of

liter at

it

should
of

above

temperature

temperature
law

0"

remains

pressure

of stating the
constant

expands

temperature

is that

its

provided
gas

if the

273",

follows:

is that

be
0"

is
0"

plus
the

pressure) varies directly

temperature.
the

provided

law:

constant,
as

(at

its absolute

istry
chem-

clear

as

calculations

the

way

gas

we

well

volume

temperature

Another

shall

law:

each

for

occupy

As

are

Dalton^s

or

occupying

gas

in

study

laws

gas

unchanged,

its volume

Thus
will

important

remains

briefly

points

that

so

to

molecular

physico-chemical

are

us

of

of solutions.

Gay-Lussdc^s

pressure

VAPORS

advisable

their

alike,

enable

nature

three

in

laws, which

will

readily tested,

be

subjects.

much

gas

AND

subject

it will

solutions

very

the

the

these

to

GASES

fundamental

the

of

some

that

2T7

compounds

fully the physico-chemical

and

solutions

of

1.

suitable

most

OF

nature

to

chlorplatinates

for this purpose.

MOLECULAR

In

of bases, their

case

41

DETERMINATION

the

volume

Thus,

of

temperature

gas

if 1 liter of gas

varies

mains
re-

inversely

be compressed

42

ORGANIC

into

the

of

space

CHEMISTRY

liter, the

0.5

has

pressure

been

doubled.

Avogadro^s

3.

and

of temperatm-e
of all gases
The

relative
under

gases,

the

molecules

molecular

its

ascribe

to

oxygen

has

times

heavier

of

it

0"

than

and

of

weight this
of 22.4

But

if
gas

(at 0" and

corresponding

weight is called
consequence
compress

we

of 1

of

mole

Uter, it will have

22.4x760
(i.e.,

pressure

by applying
weight.

of

we
a

the
As

Such

volume

weight

or

pressiu'e

at

if

that

0" to the

of 22.4

In

mole.

follow

it must
gas

volume

atmospheres

Hg).

mm.

If, therefore,
and

of any

of

its molecular

to

gram-molecule

number

ular
figures for the molec-

the

to

of

weight

the

mm.).

760

gen
hydrovolume

will also occupy

Boyle's law

has

equivalent

of gas

of

grams

take

we

being sixteen

molecular

we

be

Similarly,

2.

pressure

is the

amount

liters

in grams

Hg

mm.

other

any

Two

hydrogen.

760

of

the

chosen,

atoms,

of 32,

weight

therefore

hydrogen;
grams

molecular

thus

two

weight

we

readily

gas

contains

molecular

the

standard,
can

gases

is

molecule

liters.

22.4

other

If, then,

the

as

gas

Hydrogen

since

at

one

and

weights of the

hypothesis).

of

weights

ascertained.
and

of

weight

of different

of temperature

relative

the

represent

ditions
con-

of molecules.

volumes

equal

conditions

same

(Avogadro's

the

number

of

same,

equal volumes

pressure,

same

weights

must

pressure,

take

the

contain

the

under

hypothesis:

know
known

above
an

the

volume,

weight of
laws

to

example,

temperature,
gas,

determine
suppose

it is easy
its molecular

that

0,2

much

known

weight

how

closed

neck

neck

the

at

rubber

heavy

in

suspended

expansion

should

tube

this

be

containing

and

from

by
bulb

The

having

(the

long

stopper;

burette.

gas

tube

bulb-Uko

two-thirds

upper

with

asbestos

Uquid

with

tube

in it
in

cut

by

two

and

of

paper)

boiling-point
of

temperature

cork

by

Bleier

air-displacement,
the

measured

apparatus

by

estimation

means

the

suction-pump.

and
the

Kohn,

by

increase

being
of

constant)
a

thermometer

bent

air-pressure

in

the
as

registers

has

apparatus

(the

pressure

the

in

boiling-point

to

the

manometer.

mercury

By

(start the heating

this

due

be

to

glass tube

which, instead

of

inner

again).

thermometer

of

the

(this will have

i.e., the

modification

tube

outer

suspend

water

the

temperature,

excellent

^An

made

When

gradually).

constant

boil the

Now

the

together

hang

insert

and

steam-vent.

cork

also

of

water;

wired

then

steam-chamber

very

of

means

of this

means

bulb

the

full of distilled

two-thirds

into

wrapped

Fill

Experiment.

an

apparatus

is connected

vaporization

the

finding

substance.

the

in

rubber

end

some

above

40"-50"

with

its closed

at

by

figure, consists

above

tube, which

wide

in the

by

side

tubing

of

vapor.

continued

top

passes

purposes

volume

closed

to

shown

as

bulb

elongated

in

changes

apparatus/

an

is

displaced

substance

The

the

is

the

when

of

vapor

air

the

is ascertained

of

much

general

which

in

Meyer,

Victor

of

for

method

useful

more

is that

CHEMISTRY

ORGANIC

44

apparatus

of

of

been

measuring

volume

of gas

vaporization
Before

is

making

is lowered

by

MOLECULAR

the

WEIGHT

water,'

burette

and

cork

reservoir
variation

from

apparatus

is

it.

Remove

in

air

in

the

inner

tube

extends
the

into

main

and

in

Fig. 15)
bulb

glass
known

and

of

the

When

air

in

the

raising the

'

Boiling-point

mm.

mm.

determine

99.8",

whether

level

of

and

the

remains

apparatus

liquid in the

fill the

burette

exactly

reservoir

after

cock

735
at
at

760

mm.

mm.

the

(either
barometric

mm.

745

having

with

99.4",
100".

the

to

(as

750

burette).
the

cock

brought
outer

cock

pressure
at

volume

constant

the

at

99.3",

15.

wait

two-way

Fig.

communication

into
of

740

ing
havbefore

the

constant,

means

pure

to

by

burette

of

filling). Fit the

indicated

by

of

minutes

surrounding

steam

sealed

tightly, and

few

little

weighed

stopper

now

shown

as

(the bulb

after

has

and

neck

weight
been

The

by

containing

chloroform

the

fits

tube

the

no

place

which

tube,

the

is

stopper

branch

extra

tube

narrow

of

there

estimation.

an

the

temperature

glass rod,

the

755

of

in the

minutes,

5-10

making

position (supported

the

at

for

for

If

gas

rubber

and

burette

level.

same

level

the

tightly with

in the

the

with

tube

tube

water

ready

the

to

of the

the

this

column

come

inner

exactly

to

entire

the

Bring

stopper.

side

the

connect

45

DETERMINATION

mm.

the

air
of
is

by
the

99.1",

99.0",

at

46

ORGANIC

burette

or

CHEMISTRY

Then

tubing connection).
the

burette

Victor

close

conmiunicates

Meyer

glass wool
tube

to

air is

pushed

been

put

into

injury.

When

the

few

moments,

into

burette

level

the

cock

of the

rod.

Some

bottom

of

and

Level

in

the

absolutely

the

that

so

air of the

forms

that

rubber

bottom

burette.

with

remains

close

the

the

Vapor

the

the

cock,

the

to

pulling

over

the

in

bulb

by

prevent

water

the

tube

has

in

only with

the

drop

Now

system.

inserted

specially

one

of the

the
hot
the

up

reservoir.
for

constant

biu'ette.

After
^

sufficient

allowing

the

time

of

exactly

the

(see

37), correcting

p.

and
p.

air

the

(22.4 L.) by
of

weight

the

gives the
and

the

also

and

0"

of

760

this

(see

mm.

divide

cubic

for

pressure,

22,400

centimeters

quotient

vaporized;

figures

same

barometric

the

gram-molecule

in

burette

temperature,

multiply
of

the

calculation

chloroform

weight

measure

estimations

at

number

the

nitrogen

and

the

displaced, and

air

for

volume

make

To

43).

the

to

convert

into

in

as

way

(see Appendix)

aqueous

cooUng,

displaced

volume

same

for

express

of

the

by

of
the

product
the

stance,
sub-

molecular

weight.
NATURE

THE

In

their

different
laws

OF

to

SOLUTIONS.

physical properties

from

methods

must

be

In

gases.

in

substances

other

OSMOTIC

than

adopted
substance.

to

solutions

attempting

to

are

apply

solution, it is evident

those

used
the

measure

We

PRESSURE

measiu'e

in the

case

pressure

the

very

gas

that

of gases
of the

pressure

solved
disof

OSMOTIC

of

impossible

to

by

gas

means

dissolved

only

substance

is that

of

refuse

but

substance
the

at

was

diffuses
start

until the

energy

manifested

but

in

much

diffusion

the

the

of

solvent

directions.

both

two

directions;
dissolved

membrane

into

this process

what'
tinues
con-

sides of the membrane

concentration.

same

this

tion
solu-

solvent

the

The

dialysis is

of

process

less permeable

solute

readily

Such

this

apparatus

kind

it is

In

properly

a
can

pressure

be

in

called

both
permeable
semi-

constructed

used

different

is

prevented;

through

passes

is

membrane
of

through

membrane

membrane

membrane.

pressure.

if, however,
used,

of

If

parchment

The

is that

both

much

separate

in

the

tainer.
con-

solvent, the

solvent, and

liquidson

solutions

diffusion

through
pure

become

to

separate.

fact

the

of solutions.

pure

membrane

the

important

more

from

remain

to

through

passes

partition

of its

example,

record

however,

behavior
for

substance

some

liquids

as

walls

membranes,

membrane,

for

can

the

viously
ob-

is

of

means,

manometer

the

it

pressure

same

against

of

is arranged

paper,

the

about

permeable

the

by

use

learned

be

the

measure

solution

making

By
can

the

of

but

manometer,

which

pressure

47

PRESSURE

from

to

strate
demondiffusion

pressure.

The
is
of

best
film

copper

example
of

copper

of

semi-permeable

ferrocyanide.

ferrocyanide
it may

be

is too

Since

fragile to

deposited

in

the

membrane
this
exist
pores

film
supported,
un-

of

48

CHEMISTRY

ORGANIC

cell

porous

is used

as

following method

the

and

(such

batteries),

for electric
be

may

used

in preparing

it.

long and

inch

one

inside

rubber

perforated
a

cell, about

fine-grained porous

in

is sucked

acid, then

sulphate, and

and

outside

the

filled with
and

3%

the

cell

in

is

exposed

to

The

potassium

ferrocyanide in the

When
tion
solu-

inside

thoroughly
which

it

is

solution

sulphate

of copper
with

reacts

of the

pores

the

porous

gelatinous precipitateof copper

ferrocyanide is deposited. After standing for
pot,

day
If

that

are

ferrocyanide solution

sulphate.

copper

cell

The

then
after

water

is maintained

filled.

are

water,

potassium

outside

the

of

distilled

with

washed

suction

completely

are

The

through

the pores
of the
again. By this means
thoroughly cleaned, and air is removed.
clean, the cell is placed in a concentrated
of copper
until the pores

passes

suction-pump.

the water

placed

then

pores;

with

which

stopper, through

cell is set in water, and

inches

is closed

diameter,

glass tube connecting with

the

four

so

fine

the cell is washed

a

cell is

solution

of

suspended

cell and
so

cause

in water.

cane

sugar

cell

niount

by

up

is

placed inside and the

in water, water

of

means

in it to

will pass

very

vertical
rubber

glass tube

When

in the volume

the system

considerable

of the solution

is in

with

stopper, fluid will

height.

however, the liquidin the cell is put under

increase

into the

of fluid in this to increase

the volume

that, by connecting

the

is

If,

pressure,

prevented.

equilibrium because

the

OSMOTIC

pressure

is

volume,

exactly

diffuses

in.

the

regulated

so

by

the column

The

atmosphere.
thus

No

determined

mm.
one

pressure

demonstrated

osmotic

be

mospheres
at-

constituting

mercury

with

manometer

as

of

as

760

pressure,

of

out

in

Large

reported

are

diffuses

can

height

of mercury.

pressures

solvent

pressure

the

measuring

change

prevent

connecting
the

apparatus,

to

as

much

as

By

49

PRESSUEE

called

is

pressure.

membrane

prepared

has

that

is

absolutely

that

semi-permeable,

been

ever

permeable
is, imA

all solutes.

to

carefully prepared membrane

is

truly

semi-permeable
and

solutions

sugar

to

loidal
col-

to

solutions.
The
as

of

law

stated

modified

by

pressure

van't

by Morse,
The

of

osmotic

osmotic

substance

in

Hoff

and

is

lows:
fol-

as

pressure

tion
solu-

dilute

Fig.

is the
pressure

exist

in
as

the

same

solvent.

same

that

the

substance

would

the

form

gas

at

the

solution, and

if

volume
If this law

isolutions,it would

of

as

that

could
mean

16.

of

amount

be

exert, if it could

the
it

confined

were

by

occupied
applied

that

the

ture
tempera-

same

to

the

to
pure

concentrated

osmotic

pressure

50

CHEMISTRY

ORGANIC

of all

of

gram-molecule
of

volume
calculate

what

22.4

the

laws

those

that

obey
are

tenth

cane

this,

the

Molecular

of osmotic
not

we

can

Solutions

1%

which

accurately

most

pressure

stance
sub-

calculated

solution

: x.

concentrated

more

the

pressure

be

may

to

dissolved

Thus,

atmospheres

are

of

any

sugar

than

to

According

1.

be

one-

at

32"

has
of 544
be

should

osmotic

an

540.6

is

to

solutions.

to

the

to

osmotic
absolute

tions
by observa-

proved

of

of 510

mm.

According

cane

sugar

Hg, and

calculation

to

it

(practically agreeing with

Hg

mm.

interest

solution

pressure

Hg.

mm.

so

1%

following:

like the
14.2"

this is

osmotic

law, the

proportional

That

temperature.

of
of

laws

gas

Gay-Lussac's

to

should

pressure

at

of the

application

the

be

it will

pressure,

gas

made

been

has

comparison

pressure

finding), thus

the

in

substance

sufficient
is meant

to
a

The

Morse,
than

because
c.c.

L.

of

in which

solution

pressure

1000

in 1000

should
1000

gm.

gm.

of

in

molecular

amount

an

solution, while

by

of

weight

weight
solvent
normal

gram-molecular weight of

the

be

the

is meant

dissolved

grams

make

is dissolved
2

solution

gram-molecular

By

of

of

of

gram-molecular.

Since

test

of

22.4

pressure

basis

be.

will

the

be

must

compressed

the

proportion:

solution::

is

pressure

solution

the

from

the

solution

1%

On

0"

at

when

gas

Uter.

in

this

because

atmospheres,^

of

solutions

weight-normaP

stance
sub-

of solvent.
22.28
water

atmospheres
at

0"

has

according
volume

to

greater

52

ORGANIC

have

the

found

be

Osmotic

the

of

solvent

proportional
osmotic

to

the

decrease

to

of

The

through
having

lower

the

involve

the

in

the

but

will

be

taken

liquid of lower
The
the

possible
to

is
to

also

from

the

raised

by

the

the

contact

with

vapor

the

pressure

the

if

pure

solution

the

beaker,

one

If it

the

were

cutting the

air of the
on

solution

increasing hydrostatic

to

beaker

one

time

pressure

of the

water,

jar by the

distillation.

same

is then

tion.
is,by the solu-

from

in

of
not

the

air of the
that

more

does

jar that

liquid

seen

aqueous

the

solution

at

the

that

off from

to

diffuse

difference

pass

water

changing

without

water,

of

equivalent

subject

actually

to

be

of

an

pressure,

without

pressure

liquid off

vapor

culated
calfound

Thus

in

set

are

from

transfer

other

effect

and

will

up

that

so

was

can

membrane.

tightly closed, vapor

that

was

into

pass

experiment

an

both

another, and

to

as

beaker

one

than

been

solvent

pressure,

of

use

is put

water

in

in

that

pure

so

vapor

pressure

tion
solu-

pressure

has
This

pressure

the

clearly by considering
vapor

apparatus.

membrane,

of vapor

pressure,

pressure.

of

tendency

pressure

of osmotic

solution

osmotic

an'

vapor

lowering

of vapor

its vapor

in

measured

been

pressure.

vapor

freezing-point of

Increase

closely with

agree

has

boiling-pointhigher

pressure

from

This

the

solvent.

pure

to

dissolved, the

is lowered.

lower, and

of the

the

is

explains why

is

is

is related

substance

pressure

This

pressure.

case.

pressure

When
the

osmotic

same

to

CHEMISTRY

jar, and
the

pure

could

pressure

be

until

OSMOTIC

finally it equaled

therefore, that

seen,

into

liquids

two

regards
that

the

is due

of

the

that

while

vapor

taken

the

by

up

the

membrane.

do

not

become

distillation.

If

accept

we

dissolved
of

pores

It

through
been

has

of

pores

fine

an

the

by

the

can

(but the
true

osmotic

be

is

the

used

pressure
pressure

and

is

side

of

pores

simply

membrane

acts

solute

of

as

from

longer tenable.

no
an

osmotic

brane
mem-

When

only

of

the

eter
diam-

to

about

reduced

be

the

means

osmotic

demonstrate

will

the

through

partially blocking

to

of

membrane.

that

been

no

molecules

of the

is

pores

have

we

diffuse

not

of

form

other

porcelain plate by

capillarieshas

brane
mem-

capillary

the

why

pores,

prepared

unglazed

O.S/x,the plate
of

the

the

theory,

molecules

the

osmotic

process

non-gelatinous precipitate.

of

pressure

that

recently shown
be

can

theory

sieve, preventing

passing

do

of the

method

theory the

this

this

in

equilibrium

an

the

perfect semi-permeable

old-time

The
a

substance

osmotic

condenses,

the

and

wet,

difficulty in understanding
the

the

to

as

solution

is in

on

According

x)ther

an

the

the

vapor

solution

bring

to

improbable

in

to the

as

solvent

The

be

liquids.

two

passing through

membrane.

the

will

at all

on

through
the

It

each

establishing of

solvent

in

used

about

pressure

theories

recent

supposes

of

It is not

of the

and

be

with

equilibrium

to the

water;

cease.
can

pressure

pressures

of the

passage

would

by exerting

vapor

One

pure

equilibrium brought

cup,

of the

of the

pressure.

vapor

apparatus
the

that

distillation

consequence

53

PRESSURE

fraction

solution).

But

54

ORGANIC

the

diameter

of

times

1000

solutes,

that

solvent

into

This

By

using

rubber, the

about
the

the
of

case

the

with

cell in

water

not

would

pass

to

we

be

had

into

be

great

so

the

the
same

as

cell
as

solutions

two

them

between

by

same

when

Pressure.

solution

the

that

outside
that

of

placing

cane

sugar
pressure

because

case,

strength

IS,

of

the osmotic

of the

it.

This

the

relative

water

solution

fact leads

by seeing whether
are

the

Osmotic

previous

until

they

but

all membranes.

cell,then

only

te ascertained

can

membranes

solution,instead

the

be

to

apply

it in

in

well

may

theory;

in the
in

membrane

solution

placed

important conclusion, viz.:

an

some

sugar

ever
what-

anything

It

Measuring

cane

of solutions

through

not

for

that contained

than

would

came

this

with

experiment

weaker

occurs

solve
dis-

that

demonstrated.

prove

of

pores.

for example,

as,

solutions.

aqueous

Methods

Biological

capillary

be

action

other

membranes

pressure

not

of

certainly does

theory

in the

does

first
and

the

those

can

that

by

by using solvents

osmotic

mode

accordance

in

like
sieve-

no

membrane

have

to

solvents

osmosis

that

true

is

on

take

not

and

such

the

membrane,

experiment

an

to

of most

supposes

membrane

the

non-porous

with

Such

500

membrane

of

known

are

membrane,

in
made

of

out

that

rubber

there

some

the

substance

theory does

account

by

through

passes

passing

side.

from

molecules

that

is favored

dissolving in the
then

of the

it is evident

that

theory

the

is

capillaries

involved.

action
A

these

diameter

the

so

CHEMISTRY

separated from

us

to

strengths of
osmosis

each

curs
oc-

other

semi-permeable membrane.*

This

is true

solvent

only

for solutions of diffusible substances

(water).

in the

O"MOTIC

In the
we

of the

case

determine

cell.

If, however^

the

this

occurred, by
the

have

structure

analogous

same

the
and
a

corpuscle

and

if it be

number

of

the

is called

than

that

is called
This

the

the

in

graduated

in

At

measured.

in and
a

in

the

in

either

in

globin,
haemo-

direction

the

corpuscle,
placed
the

puscle,
cor-

be hypotonic.

to

is stronger

will diffuse
Such

shrink.

in

will distend

which

water

corpuscle will

Such

in

is said

solution

then

fluid inside

corpuscle

solution

the

volume

inside

the

in

contained

that

Such

of the

and

of

out

solution

corpuscle

fluids

may

of

means

are,

to

it of urea,

NaCl
in

however,

at

solution
the

remains
increase

of

space

by

small,

alcohols,
This

urea.

after

in osmotic

the

accurately

end

for

isotonic

by

into

volume

permeable

salts, and

give

to

as

each

of

centimeters

is drawn

its

closed

is then

spite of

also

consists

seven

Blood

mixed.

alkalies,ammonium

isotonic

This

so

syringe, and

pipette

corpuscles

is widened

be

observed

obtained

be

hsematocrit.

tube

be

may

may

capillary tube, about

the

an

corpuscle

quantitative expression

the

of

end

The

acids, and
why

water

and

corpuscle be

the

than

called

narrow

the

capillary by

The

salts

occur

fluid

the
If

volume

volume

one

which

in the

instrument

an

long.

with

contents,

microscope,

change

using

unchanged

the

puscles
cor-

hypertonic.
change

under

remain

solution.

that

corpuscle, so

it allows

of

will

its fluid

the

of

we

will

corpuscle be placed

of

distended

envelope

osmosis

ultimately burst.

may

The

no

will diffuse

if osmosis

blood-corpuscles

red

is contained

as

we

fluid containing in solution

is weaker

water

If the

the

then

which

then
and

in

molecules

isotonic

solution

placed

permeable
semi-

fluids,then

became

sac

inside

some

fluid,tell

solution

of

sac

membrane;

salts.

not

is isosmotic

an

the

this.

to

contains

corpuscle

fluid which

the

of

case

it, but

corpuscle,

other

some

described,

pressure

the

of

one

semi-permeable

diffuse through
Now

the

closed

whether

seeing
In

like

in

sac

reverse.

acts
to

employed

this

the

by measuring

filled with

could, by suspending

or

fact

we

membrane

had

ferrocyanide cell above

copper

could

55

PRE^SVkE

free

explains
the

tion
addi-

pressure.

56

ORGANIC

CHEMISTRY

accurately fitting,metal
The

tube

rotated

The

is then

In

mark

which

volume

and

fluid

The

two

of

taken
fluids

mixed

by

closed

and
as

be
been

are

spring.

rapid centrifuge and

the

to

column

of

same

fluid

the

molecular

end.

outer

stands

corpuscles

fine

the

into

the

exact

longer, then

with

wire.

that

of

corpuscles

and

is then
same

solution
that

means

their

volume

is

they
of

column

puscles
cor-

have

must

examination

be

tube.

the

at

the

If the

under

the

tube

The

that

plasma.

fluid

the

that

column

the
know

we

of

part of the tube

know

we

of

of blood

amount

graduations
wide

with

concentration

blood-corpiiscles,which

isotonic

is mixed

corpuscles stand

then

alone,

the

platinum

If

blood

The

off from

of

the

the

the

sucked

blood

be

of

then

increased, and
If

is

tonic.
hypo-

solution

shorter, the

hypertonic.

Isosmotic

solutions

provided

the

Solutions

of

tenth

cells

are

of

salts,acids and

osmotic

greater

other

substances,

effect

as

following

molecule

since
;

each

(as,

bases)

than
ion

comparison

isosmotic.

are

sugar

Potassium

(not ionized)
nitrate

solutions
has

the

is made

1 .00

67

1
.

Sodium

chloride

69

1
.

Calcium

chloride

have

(p. 65)

Cane

one-

organic compounds

substances
pressure

solutes.

the

to

cells

same

concentration

of most

ionizable

the

to

impermeable

are

gram-molecular)

Solutions

isotonic

corresponding

(except metallic

the

in

thrown

are

determine.

to

centrifuged.

with

also

the

is read

means

for

isotonic

drop

it is desired

must

which

at

tube

another

level

corpuscles

position by

noted.

equal

an

is

the

graduation

is then

placed horizontally

that

so

in

plates held

40

2
.

of
same

in

the

OSMOTIC

These

figures

substances.
that

The

osmotic

same

solution
In

the

of

case

into

living cells

solution

epithelium;

the

on

in

hypotonic

up,

because

the

permeable

to

With

Membrane.

examine

does

noticeably

red

Pressure

beet,

NaCl

mount

shrinks

on

the

hypertonic

solution

having

caused

Osmotic

Pressure

Shown

by

that

the

of the

fi;om the wall

away

drop

observe

substance

slide,

add

Now

shave

razor

some

slice and

the

on

Effects in

sharp

red

(2)

swell

not

not

are

microscopically.

of saturated

the

to

passing in.
(1) Osmotic

and

noticeably

tadpole placed

(3%)

epithelial cells

Experiments.

slices from

for

tonic
hyper-

injury

no

hand,

solution

water

thin

in

shrinks

being

other

necessary

permeability;

(as 8%)

sucrose

be

to

seems

immersed

hours, there

twenty-four

Vegetable

when

tadpole

sucrose

it

selective

account

the

example,
in

the

gram-molecular

0.169

means

of salt has

solution

as

pressure

NaCl

for

1.69

of sugar.

take

to

coefficient

the

of

coefficients

isotonic

gram-molecular

0.1

the

are

57

PPESSURE

cell,

plasmolysis.
Animal

an
.

air space,

open

the

where

the

down

to

Cross

three

long

over

shell
egg

of

an

this

at

the

joins

shell ;

the

middle

the

strips back
another

bind
of

them
the

egg

down
with

on

themselves

rubber

band.

the

to
a

it

shell

Coat

hold
the

shell.
inches

them

rubber
and

the

five

paper

stretch

and

an

point, removing

membrane

membrane,

contains

egg

strips of parchment

the

with

large end

The

Membrane.

on

to

beyond

band,
them

bands

bend
fast
with

ORGANIC

58

melted

paraffin

parchment
the

end

glass tube
needle

the

and

wire

shell

nicked

be

may

the

will

have

into

the

swollen

tie

about

glass rod

so

that

the

the

bent

sharply

top

of

the

(c) Drop
filled

solution.
grows

in

up

small

with
On

making

of

the

U-tube

forms,
of

with

solidified

water

melted

fill one

with

standing
of

area

beaker

ferrocyanide

passage

other

On

thread

sulphate.

copper

when

the

membrane

the

Mem-

of CuS04,

small

potassium

by

portion

in the

Inorganic

an

crystal

ferrocyanide

defined

midway

by

the

solution.

ferrocyanide

half

contents

white

egg

fasten

solution,

CuS04.

forms

the

distilled

egg

and

distended

it toward

Fill

with

position,

in

the

shell

break

to

force

to

in

middle,

solution, cool, and

agar

egg

narrow

across

copper

becomes

(6)

the

lying

through

long

crystal hangs

solution.
which

the

Shown

Pressure

thread

tube

hole

the

or

the

long

drill

tube

time

some

sufficiently

(a) Select

to

down

run

tube.

(3) Osmotic
brane.

the

fastening

standing

upright

membrane;

egg

put

small

carefully

Immerse

After

water.

be

can

To

paraffin,

and

and

before

membrane.

egg

melted

tube

membrane.

attach

egg

by applying

down

through

the

The

position.

the

to

support
of

in

them

keep

to

gives

opposite

CHEMISTRY

limb

potassium
several

days

ferrocyanide

copper

agar.

of

lump
saturated

standing
plant-like

CaCU

into

potassium
membrane
forms.

test-tube
carbonate

develops

and

60

CHEMISTRY

ORGANIC

Depression of
Freezing-point.
water

l.SG'^

"

benzol

5.00"

"

phenol

7.20"

For

"

These
the

figures

of solutions

depression

The

of

substance,
tube,

so

tubes.

with
The

flannel

is

suspended

thermometer.
the

freeze,
^

Some

The

substances

seems

to vary

of

depression

of 1.84
4.85

always

with

or

to 5.15.

In

in

an

round

inner

the

Beckmann
not

does
for

an

test-

mometer.
ther-

give

solute
ab-

ordinary

demonstrating

which

exactly those

1.85.

freezing-

loop of wire

modifications

of

two

heat-conduction).

at

certain

not

in

test-

the

wrapped

as

only

the

larger

does

temperature

with

give

from

bulb

is used

are

constant

the

of temperature

or

contain

to

contained

been

thermometer

in

constants

indicating a

has

diagram.

the

It

difference

salt

terminat
de-

Beckmann's.

as

placed

is stirred

in the

readings

is

diminish

to

This

from

freezing-point

somewhat

and

water

freezing-mixture

tube

an

osmotic

air-jacket between

jar (which

represented

as

in

test-tube

iced

earthenware

the

is known

an

outer

of

The

to

calculated

large test-tube,

form

to

The

mixture

which

suspended

as

therefore,

commonly

made

of

(or C) of

atmospheres.

is

in

are

consists

constants

freezing-point.

apparatus

This

the

correspond,

of 22.4

pressure

pressure

the

called

are

They

solvents.

osmotic

3.90"

acid

acetic

two

tions
soluit may

given above.

freezing-point of water,
The

constant

for benzol

MOLECULAR

be

used

WEIGHT

tell the

to

solutions

two

used

of the

this

within

the

which

the

adjustment

is

bring

the

if

the

is

so

the

which

is

upper

end

tube,
to

the

to

to

as

fall to

the

column
tube.

other

the

of

inverted, and,

be

added
For

latter

inner

the
comes

water,

the
or

of
the

then

in the

tube

solution

low
be-

by tapping,

the

making
the

with

that

the

at

used,

be

the

stand
scale

solvent

to

from

Should

the

freezing-point

and

in

of mercury
on

the

bottom

mercury

3.5"

cury
mer-

thermometer

disconnected

meniscus

the

reservoir,

become

thermometer

of the

with

the

ture
tempera-

the

with

connected
of

the

that

to

the

top of the

at

so

that

end

cause

adjusted

iced

in

within

tapped

cus
menis-

of the

mercury

upper

the

make

found

meniscus

thermometer

at

it be

be

is

used

bulb

much

too

scale, then

fingers

thermometer

(high up)

placed

is

and

there

scale

crystallizes. To

or

water,

the

must

solvent

the

thermometer

so

column

mercury

it stands

freezes

Before

which

at

temperatures

freezing-point determinations,

for

at

different

boil.

61

DFTFlfMINATION

more

must

mercury

can

tube.

actual
of the
under

little

thermometer

above

freezing-point
apparatus
examination
the

bulb

is

tion
determina-

partly
so

of

that
the

filled
the
ther-

62

ORGANIC

directly in

the

with

proceeded
stands

at

fluid

is

The

diagram.

This

bent

with

is

difference

Since

this

the

point

of

which

on

that

demonstrate

is

for

constant

when

pure

given solvent,

any

should

depends,

be

the

used) is frozen.

method

water

in

A.^

C, for

the

experiment

shown

as

solvent

the

of

means

obtained

designated by

constancy

mercury

whenever

reading

then

cooling,

by

loop

other

of

motion

from

is

cooling

During

is taken

the

(or whatever

following

has

the

performed
the

value

to

given

it above.

to

Weigh

Experiment.

dry

in

If this be
of ice

of

thermometer

the

water

true

freezing-point
and

the

point

.047, 2

+ .047

2.047

it would

is obtained.

3.9"

at

For

2.047

A
=

the

if

100

formation

fore,
theretrace

is added

of
to

degree centigrade
the

example,

is

in

excessive.

only

of A

from

3.9", that

at 0".

be

each

for

deducting

was

this

solution,and

1.25%

solutions

supercooling
=

because
of the

reading

by

of water

of

than

aqueous

supercooling, and

of

is necessary

pure

its molecular

dissolve

the volume

lessens

For

present.

one-tenth

the supercooling is not

that

depression is greater

observed

the

taken

correction

(pure water)
the

ice is

be
a

so,

to

of

quantity

(i.e.,6 gm.);

grams

should

Care

out

corresponding

urea

weight

into

reading

compared

water

in

rise

to

larger test-

meniscus

level.

kept constantly
wire,

The

the

constant

platinum
and

until

mercury,

quickly
in the

placed

described.

before

as

removed

is

and

the

placed

level, begins

lowest

tube

the

freezing-mixture

tube,

is

its

to

when

again,

until

freezing-mixture

fallen

having

is then

tube

The

(see Fig. 17).

mometer

the

CHEMISTRY

of the

freezing-point
the

suppose
solution

at

2",

1.9,then 1.9(2 X. 0125)

1 .853

corrected

A.

MOLECULAR

distilled

of

gm.

point

of

this

with

that

the

constant?

of

Also

calculate

supercooling,

for

correspond

it

Does

water.

pure

freezing-

molecular

the

to

weight

urea.

In

determining

substance

the

solvent

weighed

quantity

weighed

for

how

freezing-point
were

1000

of solvent

gm.

know

been

that

being

the

by

is

A,

the

by

the

words,

actual

/weight

the

as

of

"

molecular

have
than

difference

from

In

other

represented

of

solution

the

to

IS

.,

that

i-

of

gram-

(or rather
dissolved

in

solution

1000

gm.

containing
of

solvent).

where

X"

of solvent

solution

gram-molecule
m="

"

;;

weight

must

substanceX
.

this,

less

observed,

used

per

than

extent

the

strength

be

freezing-

thermometer.

depression

to

the

amount

to

grade
centi-

quantity
find

we

less

"

would

gram-molecule

proportional

recorded

to

if

in

is,

degrees
solution

our

"

tion.
examina-

solvent

many

of

taken,

less than

dissolved,

this

under

our

most

accurately

an

gram-molecular

point actually lowered

we

for

any

accurately

an

dissolve

through

lowered

in

substance

what

words,
the

this

the

choose

all

it, and,

of the

quantity
Knowing

other

of

of

of

weight

molecular

first

must

we

suitable

the

Compare

water.

solution, corrected

of

63

DETERMINATION

WEIGHT

equals

the

weight

of

sub-

stance

used

grams,

j,

in grams;

when

L, the weight of solvent

solved, gives

decimal

in

fraction

64

what

expressing

in

dissolved
the
in

1000

1%

must

be

dissolved

multiplied by

molecular

in

weight

For

culate
cal-

to

the

the

example,

solution

cane-sugar

molecular

The

therefore,
amount

XlOOO.

=-:X"

is

substance

(the
m

the

equals

of

solvent;

of

gm.

of the

1 gm.

of solvent),

gm.

equation

of

part

gram-molecule

1000, and

the

of

weight

about

is

0.054".

therefore, is

sugar,

Q^

X"^^

"

According

=344.

1000

the

to

formula

.054

100

The

of blood

and

blood

of human

342.

of urine

the

In

is much

of

case

if

less;

into the water, the

being thrown

determined.

sometimes

are

0.55".

is about

diluted, therefore

before

be

it should

C12H22O11,

is

CHEMISTRY

ORGANIC

drowning

blood

the

killed

were

person

would

That

be lessened.

not

IONIZATION

The

method

substances,
in

the

though

even

of

aqueous

salts

C.

acids

and

are

this

included
let

of sodium

sodium

Weigh

is better) the

chloride

normal

depression

Practically all
bases
this

when

in

category.

the

sion
depres-

gram-molecular

chloride.

Experiment.
twentieth

Weight

in

by

all

soluble

determine

us

to

readily

give

than

of freezing-point produced
solution

be

substances

most

solution

demonstrate

they

greater

and

applicable

solvents.

certain

freezing-point

metallic

To

however,

not,

above-mentioned

solutions
of

is

in

grams

molecular
and

(one-

one-tenth

out

of

weight

dissolve,

as

in

pure

the

65

IONIZATION

of

case

in

urea,

the

Determine

of

c.c.

that

Knowing

is A

solution, it is

easy

molecules

liter {X)

per

for

how

be

to

3.35),

gram-

many

will

of 3.35

found

gram-molecular

calculate

to

be

(viz.,about

1.86

water.

freezing-point

It will

than

1.86

the

of

apparatus.

considerably greater

distilled

pure

depression

Beckmann's

in

100

represent,

thus:
1.86

To

ascertain

sodium

the

then

law?

The

classes
which

conductors

be

the

to

the

above

law

of those

be

have

do

not

conclusion
solutions

called
of

must

ions, and
molecules

possible for

the

that
into

that

do

two

substances
to

be

bad

which

up

the

duct
con-

molecules
smaller

when

this

to

in

parts,
tion
dissocia-

place that

conduct

'

than

chemists

into

takes
to

led

has

it is only
ions

electrolytes.

of molecules

of

certain

it

obey

not

determination

the

number

split

"

solutions

from

solution

the

of

found

which

conduct,

that

by

conductors

good

greater

is furnished

"

substances

to

the

non-electrolytes whereas

"

which

such

gives

from

of those

will be

of electricity

electricity appear,

the

This

1.8.

question

Solutions

.discovery, viz.,

those

by

conductivities

electrical

found

of A, to

accordingly

must

we

the

of

pressure

of this deviation

cause

solutions.

obey

solutions

is the

the

of

osmotic

atmospheres

answer

comparing

1.8.

atmospheres.

40

What

This

actual

X;

solution

22.4

about

will

1::3.35

chloride

multiply
us

it is

electricity.

66

In

fact,

whole

our

of electricity in

is

charged

which

the

in

that

these

molecules

they show
ions,

into

and
ions

the

other

about

independent

much

effect

of

as

Each
the

on

split

tricity
positive elec-

much

These

if

ion

they

has

as

pressure,

vapor

depression

yield

electrical

an

that

has

tend

ions

freezing-point

of

their

up

called

anions,

with

cations
anions

are

example
and
the

or

collecting

cathode
with

and

metals.

The
of

Experiment.

solution, and

and

which

anode
around

the

acid

an

Put
add

immerse

portion

electrical

few

is not

the

cations.

drops

in the

of

salts, for

gen
hydro-

dependent

current.

NaCl

strong

some

of

include

cations

ionization

are

electricity, and

negative

SO4, CI, etc.; the

beaker,

poles

called

are

ions,

Those
or

into

positive electricity. Examples

OH

passage

two

charges.

those

charged

are

the

positive element

and

through

dissociation
at

electrical

element

negative
Anions

collect

the

around

is passed

current

undergone

to

collect

to

solution.

solution

in

solution

molecule
and

tendency

electricity.

molecules.

pressure

When

the

as

When

ever,
solution, how-

carries

negative

the

each

either.

in

less

or

of which

set

were

osmotic

greater

one

wander

suspended

are

electricity,

neutralize

so

appreciate

not

sis.
hypothe-

of substance

negative

molecules

do

we

this

on

molecule

every

positive and

intact

other

up

that

conduction

the

is based

solutions

with

of

conception

It is supposed

on

CHEMISTRY

ORGANIC

of

liquid

solution

phenolphthalein
a

pair of battery

68

CHEMISTRY

ORGANIC

The

SO4

ion

The

sign S0"4.
the

of

valence

number

of

charges

two

carry

be

electricity and

negative
with

therefore

must

represented by the
the ion usually agrees

charges of electricitythat

of unit

it carries.
coefficient

The
what

ions.

ions

two

this

it cannot

has

in

solution
the

the

dilution:

the

dissociation.^

Experiment.

To

cupric bromide
time, and
a

pure

of

color

that

as

blue

In

color

due

solution

equilibrium

molecules

are

ions

tion
solu-

1.67,

salt

When

whether

it is

greater

solution

drops

For

color

exactly the
What

acetate.

is

to?

an

electrolyte there

between

molecules

of

continually
uniting

are

example,

of

at

the

is

and

condition

ions.

dissociating, and
to

form

molecules.

N
1

upon

diluting solutions

by
and

acid

or

largely

very

saturated

obtained

1%

changes.

blue, determine

exceed

1.9.

gradually

cupric sulphate, nitrate

the

of

of

c.c.

those

for

dilution, the

the

water

the

note

color

same

add

of

that

depends

greater

yield only

it may

NaCl

dissociation

of

split

1.82, KNO3

of

and

become

2, but

concentration

2.18

indicates

can

ions

two

coefficient

amount

undergoes

is

the

2.11, Na2C03

The

greater than

than

In

KCl

K2SO4

be

more

number.

that

molecules

For

splitting into

have

molecules

of the

proportion
into

up

therefore

of dissociation

"

500

HCl

is

completely dissociated.

The
taneously
simulRe-

69

IONIZATION.

actions

between
fast

as

ionize

in the

amounting

ions

as

chemical

slowly because

react

To

Experiment.

AgNOa

; to

of

di^ociation

of

several

high

too

form

hydroxyl

or

the

used
of

solution

the

as

when

solvent.

phenol in benzol

8%

of

freezing-point indicating
is twice

such

called

that

tendency
contain
chloroform

For

gives

example,
depression

molecular

case

would

substances
and

groups,

an

188,which

ation
associ-

or

This

stead
in-

fests
frequently mani-

most

organic

cyanogen

is

benzol

or

In

weight.

molecules

when

dissolved,

boiling-point method

or

c.c.

C2H5Br.

fusion

molecules.

few

other

is
a

pounds
com-

of ions.

add

to the

occurs

molecular

complex

itself

of absence

there

22")

at

organic

substance

of the

freezing-point

give
to

when

Most

and

NaBr,

(H ions

per

test-tubes

two

add

one

Occasionally,

the

reactions.

the

Even

water

gm.

cause
be-

molecules

more

up

in pure

0.0000001

to

rapidly,

equilibrium;

ions present

OH

only

facilitates

used

are

effort to restore

and

of H

trace

electrolytes proceed

for

by

of

weight
the

formula,

CeHsOH.

condition

The

associate.

represented by
is

methyl

alcohol.

2H2O,

(H20)2, and

(H20)3

liquid

dihydrol), and

water

that

"

in order

acid and

that

is

ice is

is, their molecules

is

of water

(H20)4.^

Next

(HCN)6.

think

that

Uquids polymerize,

Many

supposed

to

Liquid hydrocyanic
of association
The

are

mixture

are

the

greater

also

present.

of these

trihydrol,while

Some

three

steam

is

be

acid

formic

polymchemists

(but mainly

monohydrol.

70

ORGANIC

erization

of

dissociation

the
of

solvent, the

Add

phthalein solution

drop

one

color

in the

25

Dilute

because

develops
place

to

few

with

dissociation.

The

of water.

Three

Salts

1.

base

with

dissolved

in the

latter

in

of salts

the

by

strong acid.

takes

undergo

also hydrolytic

by

are

the

action

hydrolyzed:

combination

of

weak

hydrolysis is illustrated

The

following equation:
=FeCl20H

FeCls+HOH
Salts

2.

no

pink color

water,

is induced

classes

formed
a

is

hydroxide

only electrolyticdissociation,but

not

there

and

of the

phenol-

DISSOCIATION

when

salts

the

alcohol.

HYDROLYTIC

Many

be

ethyl alcohol,

NH4OH;
water,

ionization

dilute

of

drops

of neutral

c.c.

of concentrated

change.

will

greater

electrolyte.

an

Experiment.

then

CHEMISTRY

formed

from

+ (H+Cl).

strong

base

and

weak

and

weak

acid:

+HOH

KCN

acid

formed

Salts

3.

(K +0H)

from

weak

+HCN.
base

+HOH

CH3COONH4
The

condition

by

the

fraction

of the
above

of

the

NH4OH

solutions

+CH3COOH,
is not

fully

equations, because

only

solute

is

hydrolyzed

in

sented
reprea

tain
cer-

each

SURFACE

In

case.

one-thirtieth

of aniUne

solution

to aniline

of

of the

because

(while the basic

product

few

OH

ions).

alkahne

because

so

OH

many

and

ionization

solution

if both

base

and

effect of the

few

of

the

weak

reaction
set

of

liberated

acid

from

ions

the

yields

hardly ionizes
neutral
the

is neutralized

acid

by that of the correspondingly few

is

equally weak, because

are

free
but

class

salt of class 3 will be

acid
H

base

in

furnishes

salt

acid.

acid

strong

of

strong

ions, but

1 is acid

hydrolysis

solution
the

at all.

hydrochloric

of the
of

of the molecules

2.6%

salt of class

solution

gram-molecular

hydrochloride about

hydrolyzed

are

71

TENSION

OH

ions

from

the

base.

Dissolve

Experiment.
in

of distilled

c.c.

solution

each

Test

of

with

phenylhydrazine

litmus

molecules
in

another.

molecules

attraction
called

surface

that

the

they

to

there

not

the
is

below

the
and

counterbalancing

no
a

definite

pressure

Surface

an

is

elastic
of such

up

pressure

crowds

tension

powders
take

other
an-

ing
neutraliz-

molecules

stretching of
readily

one

surface, however,

The

Fine

to

attractions

results

together.

surface.
do

by

there

the

hydrochloride.

attracted

are

the

tension.

closer

then,
at

as

above

molecules

liquid

At

sides, but

the

pare
pre-

TENSION

attracted

are

manner

paper.

directions, these

all

one

at

of

citrate

potassium

similar

In

water.

SURFACE

The

little

moisture

the

alent,
equivbrane
mem-

nature

(as

72

ORGANIC

sulphur)

float

rest

membrane.
results

when

such

bile

salts

Uquid

buoyed

also

with

contact

the

as

water,
will

but

up,

is manifested

in

comes

on

is lowered,
in the

ticles
par-

if

as

same

dissolved

be

not

tension

Surface

the

tension

are

the

water;

on

exactly

surface

particles will

sink.
the

surface
the

If

"

sprinkled

when

the

on

CHEMISTRY

wherever

supporting

vessel.
The

effect

the

in

of
of

case

small

oily

an

out

in

The

small

drops
that

to

is, the

small,

of surface
of

pipette,

bag-like
weight

becomes

tension

which

surface

been

and
must

the

For

instrument
have

must

form

correction

must

be

been

be

it suffices

have

made
to

count

very

effect

the

the

at

tip

may

what
some-

falls

to

the

overcome

it

suspended.

be

determined

estimations
of

certain

for
the

its

when

drops delivered

standardized;
and

is

drop

assumes

drop

accurate
must

slowly

it

holding

of the

the

exactly spherical while

liquid

large

least surface,

forms

drop

drops.-

the

modify

enough

great

of

the

size

The

by finding the weight

of

be

in

shape.

tension

stalagmometer.

to

has

spread

causes

the

will

When

it grows

as

has

Unless

gravity

it appears

tain
cer-

dropped

it will not

tension

that

spherical.

tension.

small, but

The

form

pull of

is

spherical,while

Surface

the

assume

under

liquid

gather together into

almost

are

noticeable

little water

will

flattened.

the

of

paraffined surface,

or

drops

are

liquid

If

film, but

is very

amounts

circumstances.
on

tension

surface

also

from
the

tip

diameter
the

drops

typical shape.
temperature.
number

of

dinarily
Or-

drops

by

produced

emptying

with

compare

the

from

the number

The

liquid.

of

Number
"

for

density

is

follows:

as

of

drops

"

of

the

calculation

"

Number

temperature.

same

for the

dynes

as

the

of

drops

to

delivered

of water

drops

made

formula

tension

cm.=-"

of
at

be

must

and

stalagmometer,

instrument

Allowance

73

TENSION

SURFACE

water
"X

the

of

of the

face
sur-

Dynes

per

.^

specific gravity

liquid

X73.
The

is the

73

factor

dynes, determined

in

water

for
in

centimeter

one

surface

tension

Une

the

at

of pure

water

surface

of the

length.

due

to

surface

tension.

plate is suspended

in

water,

the

Capillarity is
the

glass for

the

water.

This

into

surface

the
does

by raising

with

the
the

to

portion

surface

in

in

is much

The

weight

of

the

the

of
of

portion

will

wet

surface
in

surface

of
the

tension

tends

pull

to

This

area.

it

curves

upward

on

surface

along

this

than

the

is

with

surface

is

the

plus the

glass plate.

dependent

water

the

flat

the

on

of

area

lay

of water
raised

water

contact

curved

surface

less

film

glass

junction of the surface

of

area

of

possible

the

the

that

vertical

of the

at

increase

an

surface, and

least

water

the

region if it could

this

area

The

force

The

curved

of

the

the

glass, so
glass.

length

to

increase

an

liquid

above

amounts

But

totjal surface.
combats

distance

some

If

the

on

the

glass.

called

the

meniscus.
If

of

number

diameters
seems

are

glass tubes

placed
to

be

in

of

different

v/ater, the

different

in

the

effect
various

internal
of

larity
capiltubes.

74

CHEMISTRY

ORGANIC

In

wide

tube
this is

meniscus;

is

there

exactly the

of the

glass wall.

raised

slightly, because

to

there

the

will

In

tube

is

number

meniscus

to

balance

of water

must

be

the

In

of

amount

line

of

case

of

The

in

height of the

for

in

the

is

absolute

the

diameter

of

ether, chloroform,
phenol

and

tension;

dissolved

in water

as

Hquid,

weights

of

be

can

and

on

the

column
with

they lower

hand
the

the
tube

corrected
that

so

the

liquidsraised.
calculated,

if

Many

ethyl alcohols,
aniline, pyridine,

organic acids, have

other

be

may

same

be

must

sequence
con-

height.

the

of

the

glycerol, acetone,
certain

the

in

comparing

methyl

each

of

capillary is known.

the

in

column

liquid

when

tension

surface

organic liquids,such

when

surface

they
tension

low
are

of

water.

Experiments.

and

and

reading

will be of

made

and

water

action

height

of water
The

closed
en-

requisite weight.

of

the

is

tion
propor-

considerable

specific gravity of the

The

the

to

capillarytube,
column

in

small, and

tension

surface

water

of

the

for

is raised

curve

capillary bore

extremely

water.

comparison

surface

having

by measuring

liquid

get the

to

the

lines of contact,

weight

water

pull, therefore, a

available

water

relative

is used

tube

contact

determined
of

raised

water

the

the

of

diminished

vertical

sufficient

with

as

the

tube
amount

greatly

of

be

not

the

of

being in the

narrower

formation
effect

same

only difference

glass plate, the

in the

the

only

another

(1) Fill
with

0.1%

test-tube

solution

with

of castile

water,

soap;

on

76

ORGANIC

5.

the

Compare

CHEMISTRY

relative

chloroform, alcohol,
the
a

using

placing

results

multiply

air; this

As

of fact

about

each

the

liquids.

If

in

these

surface

while

it is least
tension

than

that

at

salts

which

are

solid-liquidinterface

of

ists
ex-

immiscible

two

in

substance

of

there

81)

p.

is

are

liquid-

the

quantitatively,

same,

is stated

It

that

the

solid-liquid interface
at

the

is

air-liquid interface,

particles.

raise

substances

pended
sus-

axe

face
SurUquid-liquid interface.
of considerable
importance

they

particle.

the

of colloidal

Inorganic
dissolved

each

at

effects

case

surface,

particles

water,

interfaces.

tension

in

in

is not

various

surfaces.
in contact

(emulsoid colloids, see

tension

greater

is

particles

about

much

if

contact

suspension

liquid interface
Surface

of

other

are

liquid-liquidinterface

hydrated

liquid phase

present

is

liquid,there
plane

face.
air-liquid inter-

the

there

Also,

particle.

the

at

water

by suction

part in contact

liquid comes

vessel

supporting

in the

in the

it

in

bore.

comparing

that

there

the

solid-liquid interface.

at

Before

called

be

may

matter

the

the

medium-sized

liquid is

instance, wherever

with

ured
meas-

reading by the specificgravity

of the

surface
the

For

each

having

liquid dry

it in another.

ether,

liquid raised

of
of

one

of

Uquid.

The
with

tube

in

tube

before

of the

column

capillary
the

after

water,

height of the

graduated

After

and

tensions

surface

the
are

lower

tension

surface

dissolved, while
it.

At

of

the

most

liquid-liquid

77

VISCOSITY

interfaces,however,
lower

the

surface

Gases

are

tension

of the

soluble

more

tension, and

all substances

the

in

of

degree

the

example,

alcohol, and

ether

is

respectively, while

liquids are

73,

is almost

surface

CO2

portional
pro-

tension.

in 1

surface

surface

low

For

of water,

c.c.

1.713, 4.33, and

the

and

22

solubiUty

at 0"^ of

solubiUty

solvent.

liquids of

the

(inversely) to

(including salts)

7.33

tensions

c.c.

these

of

dynes.

16

VISCOSITY

The

viscosity of

friction.
the

The

molecules

of
the

observing
of

time

liquid to

pass

with

the

of water

in the

account

must

of

column

may

with

moving

the

liquid

this

friction

nearer

time

be

taken

hence

of

the

wall

in
the

that

the

one

is not

the

calculation

weight

of

the

fore,
and, there-

pressure

center

liquid as

each

in this

way,

rate

faster

moves

The

depend

rate

the

upon

successive

gives

tact
con-

layer

next

tube.

will

these

this

the

layer

of the

whole

between
of

that

moving,

it is to the

another

volume

layer of liquid in

calculating viscosity. When

past

paring
com-

of flow.

rate

that

measurement

and

specific gravity of

the

increase

the

by

quantity

equal

an

made

certain

In

apparatus.

same

of friction

amount

be

may
a

of

another.

one

required by

slowly, and

of the

of flow

adhesion

the

thi;ough a capillaxy tube

suppose

the

to

its internal

upon

to

for

required

liquid increases

increases
We

is due

the

liquid, because

the

is

friction

of

measurement

liquid depends

layers,
basis

for

liquid particles push

work

must

be

done.

78

ORGANIC

and

the

work

of

amount

the

upon

CHEMISTRY

internal

friction.
the

Specific viscosityis
that

liquid to

of another

standard.

as

as

unity, the

dependent

is

necessary

viscosity of

of the

ratio

has

liquid that

chosen

been

compared

with

specificviscosity (at 25")

of 5%

For

example,

water

ethyl

alcohol

is 1.161, and

It will

of the

The

be

not

absolute

in

for different

The

viscosity.

ture
temperacoefficients

The

viscosity for temperature

different

are

Uquids.
series

homologous
the

to

The

in

increase

since

reported.

controlled

be

viscosity of organic liquids belonging

The

(see

in molecular

increase

proportion

as

portion
pro-

physiological
of

reciprocal

viscosity.

lessened,

viscosity is

the

an

weight.

is of great

is the

Fluidity

to

in

increases

104)

p.

viscosity of the blood

importance.
In

tion
determina-

the

must

determined,

be

always

for change

discuss

liquid

of the

diminishes

should

is 1.044.

acetate

of a liquid.
viscosity

its viscosity is

temperature

ethyl

to

necessary

temperature

when

of 5%

the

fluidity is increased.

and

water,

of

liquid

the

into

suction-pump

with

the
.

the
excess

the

and

draw

it
the

into

liquid flowing

finger (as

in

suction

cosity
vis-

from

tube

and

disconnect

and

by sealing
with

the

draw

pipette);

large tube

of

of the

c.c.

small

the

back

using

of liquid in the

by

mark;

upper

Ostwald

an

about

this pour

large tube

bulb, fillingabove
prevent

do

To

pipette.

in

alcohol

absolute

viscosity

the

(1) Compare

Experiments.

end
off

pipette.

79

COLIjOIDS

releasing the

Now

that

instant
and

the

stop the

finger

start

meniscus

reaches

when

watch

stop-watch

it reaches

the

upper

the

mark

at

the

mark
the

on

capillary tube.
Use

2.

viscosimeter

chemical

Try this with

cup

to

catch

the

raises

50

let the
the

oil by

for

time

viscosity number

raise the

Now

fall.

plunger

lever

the

the

gives

the
which

start

stop the

out

Dividing

water

liquid

under

instant

flowed

has

c.c.

tion
determina-

the

same

same

of the

c.c.

press

the

at

Each

graduate

outflow,
and

plunger

set

cup,

the

when

watch;
and

viscosity

mercial
com-

oil at the

an

200

put

for

simple apparatus.

20").

at

follows:

as

is

later with

(preferably

is made
the

and

used

is

as

Scott's

work;

water

temperature

into

such

time

the

watch
for the

figure for the

oil.

of the

of the

temperature

oil 20"

and

make

determination.

another

COLLOIDS

of

Dispersion
sodium

chloride

call

we

and

dissolves

also

the

the

may

testing

secured

be

produced
is

182-184.)

oil

for

by determining
the

from

used,

exactly 20".

vegetable

and

oil
care

by
is

the

valuable

viscosity of the
to

work

NaCl,
tributed
dis-

The
at

In

solvent.

the

adulteration

saponification.
taken

of

uniformly

are

of

mass

what

it forms

molecules

ions

When

Liquid.

water,

The
CI

and

Na

throughout
*In

in

solution.

true

in

Substances

soap

Ostwald
a

evidence
solution

meter
viscosi-

temperature

of

(See Shennari, Organic Analysis, 2xid edition,page:^

80

the

solution

does
of the
On

shaking
the

is

becomes

deposited

remain

Uquids

into

water

drops

In

film

about

present

as

other

Intermediate
solids

the

but

than

smaller
or

somewhat

the

these

as

is

sion.
emul-

an

emulsion

that

drop,

so

In

cream

emulsion,

it is

agent.

it is
the

the

kept

fat

is

microscopic

by films.
these

the

smallest
The

suspended.

and

or

the

molecular

is another

type

of colloidal

tions.
solu-

in

solution

are

solution,

true

particles in

colloidal
Some

dispersions

coarse

colloidal

largest molecules

opaque

ture
mix-

emulsifying

an

is characteristic

emulsion.

permanently

use

particles in

larger than

enough

Such

long

solutions, there

true

dispersion that
The

As

liquids in Uquids,

dispersions of

of

by shaking with

permanent

between

and

time.

stance
sub-

case

fine

mixture

drops.

drops being enclosed

solid
the

be

broken

the

permanent

This

standing,

on

In

the

solution.

droplets.

to

with

through

the

may

long

be

necessary

for,

bottom.

may

form

from

separate

for

all

all of

particles

to

forms

and

suspended

order

generally

of

dispersion

suspension.

however,

not

minute

remain

scattered

the

the

suspension,

Insoluble

of

that

(as talcum)

in uniform

at

suspended

powder

clear

substances

is

be

to

is temporary,

liquid

This

substance

molecular

only

particlesare

seem

condition

to

is

insoluble

an

fine

liquid,and

some

of

persion.
dis-

molecular

substance.

water

the

there

and

ionic

solution

true

ionize

not

is both

there

In

are

CHEMISTRY

ORGANIC

sion
suspen-

particles remain
colloidal

opalescent, but

solutions

others

are

81

COLLOIDS

practically

clear

as

distinguishing
and
solutions
the

the

Uquid,

differences

solutions

true

while

are

in all colloidal

there

dissolved

with

are

no

the

in

faces
sur-

These

substance.

factor

important

the

tions
solu-

of contact

surfaces

solutions

of the

an

colloidal

is the fact that

in true

of

One

between

particles have

of contact
surfaces

solutions.

true

as

behavior

of

colloids.
There

"

emulsoids.

phase.
of the

of

particles

emulsoid

particles

Suspensions
nature,

same

particles. In

and

that

so

suspensoid

they

and

Emulsions

although

nature,

in

suspended
emulsion

solvent

The

in

which

in the

colloidal

breaks

infinitelysmall

that

case

the

of colloidal
emulsoid

Suspensions,
are

becoming

particles
emulsions,

heterogeneous

homogeneous.

up

and

no

dispersed.

the

solvent,
The

substance, and

Uquid
in

are

an

have

are

molecularly

solutions

same

particles in

particles.
liq^uid

of

into

the

liquid particles

they

readily take

latter, instead

the

of

particles.
of

not

Uquid

particles become

dissolves

up

be quite clear,

solid

are

consist

liquid

however,

the

that

both

liquids.

affinity for the

so

emulsoids

tinctly
dis-

are

invariably

are

may

of

free

Uquid

size of the

they

practically insoluble,

are

Emulsoids,

solutions
be

to

seem

in the

suspensions

solid

essentially

are

however,

appearance,

the

in

are

differingonly

the

in

are

suspensoids

different, since
turbid, but

colloids, suspensoids and

Suspensoid

while

phase,

kinds

two

are

water

dispersed,

particles.
we

the

may

In
say

hydrated.

and

mixtures, while

colloidal
true

solutions

solutions

are

82

ORGANIC

In

CHEMISTRY

the

following classification

the

diameter

of the

dispersion

tures
mix-

particles is indicated.
DISPERSIONS

HOMOGENEOUS

Ionic

of

dispersions
dispersions

Molecular

0.1-1.0

nn^

DISPERSIONS

MICRO-HETEROGENEOUS

Emulsoids

0-100

mm

Suspensoids

COARSE

HETEROGENEOUS

DISPERSIONS

greater than

100

nn

Suspensions

greater than

100

mm

must

forms

of

against getting the idea that

warn

dispersion

another.

It

brought

into

is believed
colloidal

the

on

colloidal.

mainly
colloidal
a

solution

true

p.

that
is

It

MM

the

avoid

to

In

in

looking

is one-millionth

cases

that,
a

to

is in
if

in

colloidal
substance

comes
be-

typical

there

solution,

true

first

standing

on

some

portion which

supposed

phasis
em-

distinctively

as

solution, and

84).

be
ditions.
con-

Thus, silicic acid, when

extremely large molecules,

^

throw

to

one

spontaneously change

may

of substance

with

can

proper

colloidal,finallychanging

gel (see

trace

under

state, and

solution.

is in

prepared,

solution

these

from

all substances

it is better

colloidal

true

colloidal

that

particular substances

certain

upon

rigidly separated

are

Therefore,

be

mm

Emulsions

We

to

0-100
.

may

brium
equilition.
soluhas

molecularly dispersed

part of

millimeter.

"

84

ORGANIC

Illustrations
colloidal

of

and

solutions

they

electrolytes.

be

redissolved, so
also
or

have

lower

certain

Experiment.

indicates

running

tap
the

of

tube

it into

dryness

to

volume

on

of

To

few

in the

c.c.

other
A

dissolve

of emulsoids
the

colloidal
a

solution

sol, and

gel. If the solvent

hydrogel
In

Filter
it in hot
:

are

dyes,

equal

an

Dissolve

solution.

shake.

pour

evaporate

add

rest

add

of

jelly.

hot

water.

anmionium
off

the

pre--,

water.

silicic acid, tannin,

gelatin, albumin

and

proteins.

is called

; to the

of dilute gelatin solution

many

with

and

with

Illustrations

well, the

becomes

dish

and

5%

warm

tube

the

dish

chloride

cipitated gelatin, and

soaps,

of

gelatin liquefies;

evaporating

sulphate crystals,

usually
solvent.

Shake

solution

water-bath

can

They

pure

c.c.

Cool

evaporating

an

the

until

magnesium

residue

the

the

water;

the

than

viscidity.

residue

solutions

test-tube.

amounts

precipitation by

after

about

ize,
gelatin-

to

reversible.

are

tension

into

frothing

the

Emulsoid

Pour

gelatin solution

part

they

salts.

surface

tend

by small

evaporation

soluble

reversibly

alcohol

(as AS2S3).

viscid,they

that

and

(as Fe(0H)3),

coagulated

After

gold,

colloidal

are:

metals

are

not

are

of

Waxm

of

of metals

sulphides

Emulsoid

suspensions

hydroxides

colloidal

are

CHEMISTRY

structure
some

be

may
or
cases

in the

when

when

in the

is water

used.

When

framework
the

structure

the
a

liquid

gelatinized state
terms

hydrosol

solution

develops
is

condition

in

'^

and

gelates,''

the

liquid.

sponge-Uke, Uquid

85

COLLOIDS

throughout.

interspersed

being

colloids

typical
of the

of that

one-tenth

of

cane

by

Crystalloids

membrane.

gels, passing along the

readily

as

diffuse

however,

Prussian

pour

ammoniacal

some

blue

ammonia

water

solved).

Let

the

Cu

solution

session

out;
tube

empty

and

note

is agar

quickly.

the

slight extent.
is

trace

other

pour

(to
add

precipitate is just

the

stand
the

the

condition

the

loidal
col-

of

the

in, rinse

agar

agar.

redismore;

end

the

of the

or

while

agar,
At

not.

hour

an

one

solution

sulphate

tubes, leaving the

In

which

blue?
will

but

paper,

not
as

an

diffuse

through

animal

membrane

crystalloidspass

colloids

It may

of the

Into

solution

hydroxide

the

Certain

containing

into

does

gel
loids,
Col-

liquid.

solution;

penetrates

Colloids

parchment

in

colloidal

of the

state.

gelatinous partition such

or

soft

gel

tubes

colored

Dialysis.

in

copper

suspension

into

test-tubes

copper

the

gether,
to-

slowly into gels.

two

until

be

may

solvent

the

concentrated

c.c.

about

easily permeable

an

diffuse

very

solution

agar-agar

and

liquid pathways

Take

Experiment.

that

of

Diffusion

they diffuse

as

of

diffusion

of

rate

solution

separated

but

1%

gel substance.

sugar.

the

bringing

by

almost

separate

as

one-hundredth

only

is

cases

rapidly diffusing electrolytes,and

most

tested

solid

The

Colloids.

of

Diffusion

the

in

droplets imprisoned

is held

Uquid

the

gelatin)

(e.g., 13%

other

In

be

substance

said

are

that
in

to

in these
true

through

dialyze
cases

solution

it

to

there

main-

86

ORGANIC

tained

in

equilibrium

substance;
the

then

colloidal
fast

as

substance

the

continuous

to

to

By

and

there

10%

then

is

filters,results
the

size

Prussian
smallest

filter disks

this

true

solution

the

gel by

slow

filter-

of

filter

from
exposure
in

obtained

be

filter holds

the

passes

concentrations

size of the

pojes.

the

est
small-

having
back

all

almost

that

enable

one

to

in the

order

of

solutions
the

largest, and

set

of

these

with

particles. In

has

of

that

so

can

obtained

are

their

blue

more

place.

hardening

list of colloidal
of

that

impregnating pieces

particles. Working

into

gradation in the

pores;

colloidal

arrange

take

gelatin produces

size

go

dialyzer membrane,

formaldehyde,

The

would

gelatin of different

10%,

which

expected

molecularly dispersed part

Ultra-filtration.

be

dialysiswould

with

coUoidally dissolved

the

with

it would

the

as

through

paper

CHEMISTRY

following
dextrin

list
the

particles

Prussian

blue.

Colloidal
Casein

ferric

hydroxide

(about 44 /x/x).

(in milk).

CoUargol (about

20

mm)-

1 per

cent

gelatin.

1 per

cent

haemoglobin.

Serum

albumin.

Albumoses.
Dextrin.

As

rule

emulsoid

suspensoid particlesare

particles.

much

larger than

87

COLLOIDS

Optical Properties.

140

magnifications)

(2250

power

diameter.

in

iiix

These

in

aggregations
the

using

used, but
of

from

an

arc

it is focused
under

directly
colloidal
rays

is

Ught

darkened

cannot

be

be

seen;

detected,
these

in colloidal
diffract

to

so

3-5

fifx

much

they

called

light than

those

that

case

weaker

times
been

of

the

of

light by
The

on

have

other

seen

as

In

that

small

ticles
par-

light

be

cause

in

into

they

haze

of light

The

particles

greater
colloidal

gold

size of alcohol

as

power

tions,
solu-

small
and

as

ether

detected.

emulsoids

action

Tyndall

submicrons.

so

colloidal

particlesof
10

the

of

can

amicro?is.

of metals

(about

the

are

but

solutions

molecules) have
In

particles are

sion
diver-

passes

called

some

This

scattering

are

The

that

light,so

that

light

the

solutions

some

of

points

separate

solution

objective.

tiny specks

or

Those

background.

the

within

light is polarized.

dots

as

from

special condenser,

sunbeam

is

instead

Ught

principle as

in the

The

room.

of

microscope.

same

observed

appeax

to

the

on

loidal
col-

obtained

side

one

the

the

the

particles, when

dark

of

lens

through

up

phenomenon
dust

the

of

microscope

point

particles diffract

pass

of

to

named

be

beam

passed through

is

seen.

been

can

is from

intense

An

pensions
sus-

be

existence

the

solution

illumination

below.

that

so

of

ultramicroscope.

the

lamp

have

body

most

therefore,

can,

highest
a

in

particles

evidence

Visual

the

detect

can

particles

microscopic

microns.

by

The

emulsions

and

of

microscope

in

the

particles exert

diffracting the

so

light, that

88

ORGANIC

they

be

cannot

diameter

least

amicrons.

30

haze

Diluting

soluble

into

aggregated

in the

larger clumps, and

of

the

observed

(Brownian)

to trace

zigzag

to

their

solution
Surface

of

motion.

lessens
Tension

suspensoid

surface

tension

however,

colloidal

the

Brownian

affect

have

the

pure

it

(e.g.,dextrin, gelatin, egg

be

and

taken

gum

This

soap).

(olive oil soap) has

dilution, thus
tension.
solutions

is

0.004%
The

changed

in

purpose

marked
has

tension

ions, OH

lower

acid,

tannic

difference

solution

surface

by

others

albumin,
the

increase

.some

suspensoids

from

same

liquid. Emulsoids,

of for

advantage
emulsoids

practically the

arabic), and

(e.g.,starch

fats, resins

Suspensions

tension;

surface

it

and

largely

viscosity of

the

Solutions.

solutions

the

is

movement.

of Colloidal

as

in

motion

premanency

particles

Increase

have

The

course.

suspension

soap

large

Submicrons

of

can

particles

large particles is oscillatory. The

and

the

particles are

of

trolytes
pf elec-

appear

Colloidal

Particles.

constantly in motion

due

change

can

presence

alcohol)

(as

ultra-microscope.

Motion

been

the

cases,

some

solutions

gelatin)

In

bumin,
al-

the

take

to

some

0.01%

or

amicrons.

to

(or, in
are

Heating

in

hydrosols.

agar

amicrons

cause

may

observed

and

glycogen,

starch

submicrons

been

have

place of submicrons.

3%

tions
solu-

light, and, therefore, have

of

solution

their

emulsoid

Most

mm-

Submicrons

gelatin,

unless

submicrons

as

seen

is at

show

CHEMISTRY

behavior
of

tinguishi
dis-

Venetian

effect

in

high

very

low

face
sur-

of

emulsoid

ions, and

by

89

COLLOIDS

salts/

Rise

sioUi

Surface

of

all colloidal

decreases

temperature
tension

take

effects

solutions, since there

liquid presented

surface

the

to

surface

is

within

place
surface

each

of

ten-

of the

particle in

solution.

the

this

important

How

will be

solutions

is divided

of 0.0314

area

of uniform

understood

into

sphere of substance

cm.),

of colloidal

by noticing
when

exposure

fine

one

sq.

consideration

of surface

increase

enormous

is in

particles. A
in

mm.

to the

size,corresponding

(surface

into

up

particles

size of the

suspensoid particles (0.1/x),will acquire

of 314

area

purified,that is,freed
the

surface

higher,
in

and

smaller

about

it

becomes

viscosity but

sUghtly

solvent.

pure

silver

compoimd

viscid

than

becomes

difference
into

Traces

Suspensoid solutions
different

3.85%

solution

found

was

water.

great

emulsoid

increased

pure

agar) show

some

is

particles.

Most

particles

particles divide

the

Solutions.

the

face
sur-

substances,

higher, the

Viscosity of Colloidal
have

est
larg-

solution

dissolved

the

and

increases

colloidal

of other

tension
as

potential

If

cm.

sq.

stance
sub-

compact

diameter

if broken

the

to

Some

viscosity in

be

from
of

only

emulsoids
low

that

of

colloidal

1%
(as

more

agar-

concentrations.

solutions, if stronger than

1%,

have

viscosity.
of acid

emulsoids.

viscosity;

for

or

of alkali increase
There

example,

is

point

the
of

viscosity of
maximum

with

gelatin solution

HCl

is secured

the
N

maximum

viscosity
^

with

when
256
.

90

ORGANIC

is present.

The

CHEMISTRY

maximum

NaOH

viscosity with
N

is the same,
Increase
in

But

but

is obtained

of

temperature

the

increase

in

below

is present.

lessens

albumin

that

the

viscosity.

solutions

been

viscosity has

sUghtly

atiu'e

of

case

when

observed
which

at

marked

at

heat

temper-

coagulation

"

occurs.

Osmotic

has

Pressure

been

demonstrated

with

merciu'y

The
be

the

that

For

these

was

used

effect of

there

the

as

molecule

agglomerate
different

pressure,

Uquids

crystalloid.

and

the

of

Weight

of

particle
of

colloidal

different

at

Whenever
the

larger

cannot

because

Colloids.

calculated

be

the

number
be

colloidal

particle can

the

difficulty
applies to

same

sides

pressure

solution.

same

centration
con-

number

be

may

become

clumps

The

into

together

is variable
in

osmotic

causing

these

same

colloidal

the

that

so

both

on

brane
mem-

osmotic

is lessened.

Molecular

weight

of

times

colloidal

pressure

in

aggregated

molecules

the

the

effect

membrane,

ex^,ctly the

Apparently

same

dialyzing

to
25.6

was

neutralized, since

was

was

in

mm.

found

albumin

egg

mm.

22

gelatin was

osmotic

impurities

membrane.

exerts

1.5%

the

of them
the

of

tions.
solu-

12

gave

solution

6%

determinations
as

until

dialyzed

solution

1.5%

pressure

colloidal

'some

in

of

pressure

and

mm.,

mm.

and

pressure,

osmotic

3%

in

Haemoglobin

Osmotic

Colloids.

of

not

The

true

from
of

the

molecular
osmotic

molecules

determined.
molecular

in

the

Exactly

weight

deter-

92

ORGANIC

(effectof
emulsoids
if

ions)

OH

would

CHEMISTRY

favor

Some
found

be

would

there

mutual

tissues, emulsoids

If

of

Many

the

just

are

in

present

they

the

the

charges

the

that

particles, so

the colloidal

masses

large enough
Brownian

to

separate

been

Emulsoids

eliminated.

mutual

cause

be

also, there

must

of the

colloids.

Experiment.

Arsenic

pouring

boiling

equal volume
Continue

hot
of

surface

add
be

of

the passage

of

in

solution
that

of the H2S

case,

proportions

drop

arsenious
at

arsenious
been

masses

this

In

colloidal
of

has

The

electrical

opposite

of colloidal

c.c.

are

repulsion has

relative

prepared

water

clumps

the

bringing

gradually,

saturated
cold

tension

precipitate.

proper

or

change

agglomeration

of electrical

the

sulphide may

This

precipitation.

To

sulphide solution

as

in

factor

when

steadily until they

out

aids

oppositely

other, and

The

together after the

two

The

as

mum
maxi-

larger colloidal

progresses

movement

can

mixtures,

the

necessarily be formed.

must

portions
pro-

positive

neutrahzed.
lowers

such

many

each

are

condition

electrical

about

in

precipitation occurs.

particles attract

meet

as

of

suspensoids

two

mixed

are

electrified

ment
environ-

and
being electro-positive,

sign

charges

negative

H2S.

natural

their

Colloids.

of

that

most

neutral,
electrically

animal

some

electrical

opposite

sign

that

electro-negative.

Precipitation

in

view

electricallyneutral.

be

emulsoids,

are

others

and

vegetable

never

dyes

an

be

to

sufficiently purified. In
in

the

time,

solution
acid

saturated

until the mixture

by
into
with

retains

93

COLLOIDS

colloidal

5%

containing

addition.

each

after

Finally

when

the

and

of AS2S3

contains

mixture

13

ions

of

anions,
as

arsenious

as

H,

ions

ferric

as

K,

The

of

Thus

0.7 gram-

and

acid

of

hydrochloric

of

action

0.0038

acid

ions, and

precipitating

precipitating ions

remain

see

have

have
the

on

colloidal

are

not

free H2S

by passing hydrogen

aid of

p.

held

by

the

colloidal

95)

while

the

precipitated by small

of the

yellow liquid is

are

other

in solution.

the odor

the

ions.

proportional

sulphide.

Emulsoids

with

is

quence
conse-

explained

reason

power

acetic

solution

(adsorption,

masses

ions

of the

concentration

degree
The

for the

occurs

In

the
their

charge;

neutralized.

thus

of

particles attract

electrical

precipitating
solution

arsenious

precipitated by

are

colloidal

are

concentration

same

same

are

opposite

an

gram-molecular
the

sign; electro-positive

precipitated by cations,

charges

molecular

precipitated

are

sulphide,

The

the

cured
se-

parts by weight

24

hydroxide,

precipitation

to

portions
pro-

electro-negative colloids,

carrjdng

above.

the

CI, SO4, while

Mg.

electrical

precipitate

regulate

Suspensoids

opposite electrical

colloids, as

minutes

few

parts of Fe203.

Precipitation by Salts.

by

iron

precipitation is

Maximum

just right.

decided

It is difficult to

obtained.

will be

dialyzed

hydroxide (Merck's
Fe203) ; let it stand

ferric

gas

after

secured.
a

thorough

through

If there

centrifuge.

shaking.
the

is any

Now

solution.

quanti-

remove

An

precipitateremove

the
opaque

this

94

ORGANIC

the

effect

on

added

to

lower

76); and,

p.

"the colloidal

to form

balance

the
that

in

shows

will

generally

referred

very

to

explanation

offered

salts

abstract

soUd

is true

being
of

also

fine

by
Acids

salts

added;

are

salting-out

the

the

latter

of the

For

loidal
col-

reduced

to

suspensoid

impart

become

similar

negative
a

the

acquire
fibers

carbonate).
or

charge,

as

adsorption (see below)

are

tated
precipi-

suspensoids.

completely

positive charge;
of

few

Suspensions

kaolin,

manner

of

electro-negative.

suspensions, very

most

lamp-black

substances

example,

asbestos

particles in

the

to

of

hydrated

are

insoluble

most

and

cotton

in

due

is

The

process.

from

electrolytes

even

this

water

electricity.

diminish

large

concentrations

as

can

undoubtedly
ions.

when

such

powders,

it, or

creases
electrolyte in-

occurs

electro-positive (e.g., barium

some

the

with

is that

water
of

charges

filter-paper,wool,
This

it

trolyte,
elec-

an

easily precipitated.

are

with

contact

restore

solution,

phase, and, therefore, become

particles,which

negative

as

that

particles,so

to

as

with

more

emulsoids
soluble

of

so

particles.

of

amounts

to

of

about

particles must

in

seen

Salts

interfaces

emulsoid

an

be

Addition

size of the

Precipitation

act

the

is

solvent,

tension

is treated

only amicrons,

the

In

surface

If

potential.

ultra-microscope.

the

the

an

faces
inter-

interface.

larger clumps

submicrons

the

Uquid-Uquid

particlesis lessened,

together

come

particlesand

at

since

the

at

air-Uquid

tension

surface

(see

the

at

have

electrolyte

an

concentrates

colloidal

the

it does

as

When

solution.

solution, it

between

just

latter, however,

the

electrolytes;

of

ties

CHEMISTRY

this

the

tralize
neu-

effect

is

positive

95

COLLOIDS

Colloidal

Adsorption.

electrical

opposite

charges, and

the

is described

process

is called

For

if

example

is mixed

with

have

Fe(0H)3

ions

and

protein

ical
physand

adsorbed.

are

electrical

opposite

charges.

(electro-positivesuspensoid)

(electro-negative emulsoid),
iron

This

not

condensation;

faintly alkaline

but

them,

suspensoid particles,particularly

to

colloids

if the

having

adsorption.
besides

adsorb

Emulsoids

surface

as

substances

Other

hold

combination.

by entering into chemical

union

ions

particlesattract

solution

adding

on

of

protein
both

salt

completely precipitated.

are

"

To

Experiment.
of water, then

c.c.

after each

is

with

282)

ing
sulphate, shak-

filtrate

NaOH

supposed

are

the

surface

proportionate

substances

hydroxide

for

protein

solution

and

CuS04.

of enzyme

rate

ferric

70

gelatinous precipitate

the

test

(the substance
on

add

serum

sodium

powdered

p.

drop of dilute

substrate

of colloidal

addition, until

(biiu'et test,

Enzymes

of blood

c.c.

c.c.

Filter, and

forms.

the

15

add

and

solution

10

action
to

adsorb

impossible

the

emulsoids.

is to be

that
of

be

to

the

acted

on)

particular

moment

degree of adsorption.

to

enzymes,

to

separate

so

denses
con-

particle, and

enzyme

at any

The

that

Other

it is practically
in

enzymes

pure

condition.
The

plays
the

humus
an

soil

of the

important

soil is

an

emulsoid

colloid; it

part in holding soluble

salts in

by adsorption.

Dyes adsorb

to the

fibers of cloth

(see p. 407).

96

ORGANIC

Crystalloids,
insoluble

high

tension

particles probably

the

the

of

adsorption

charcoal

animal

is

It is used
rate

hot

the

in

that

cold

the

since

least

at

in

acetic

acid

the

mixture

coming
has

proportion
should

adsorbs

substance
In

some

is

manufacture
the

Colloids.

suspensoid

preventing

dislodging

been

substance

the

is

more

lactose

reaction
what

tannin

of the

tions
solu-

dissolved

the

readily.

too

paper

tain
cer-

Some

filtered,because
the

adsorbed,

when

adsorbed.

follows

takes

being

tion.
adsorp-

place

in

the

first adsorbed

hide, and

When

later

solution, it
or

to

exerts

hindering

adsorption

emulsoid

an

the

suspensoid by electrolytes.
be due

recovered

forming

compounds.

Protective

to

be

acid, the

equilibrium

an

leather;

tissue substance

insoluble

to

to

undoubtedly

of

versible,
re-

may

be

may

acetic

all of the

chemical

cases

This

to

be

not

is

in its stead.

not

cases

is less

instance, lactose

For

easily adsorbable

some

adsorbed

charcoal

also

by shaking,

substance

with

being adsorbed

tion.
by adsorp-

liquid. Adsorption

part.

to

agents

decolorizingUquids.

amount

charcoal

In

solution

for

by treating the
and

effective

most

adsorbed

adsorbed

has

total

sity
inten-

Finely powdered

from

extensively

but

than

removed,

for the

adsorption is increased

of

by heating;
in

of the

one

The

liquid.

accounts

process.

of substances

for removal

The

in

to

liquid-solidinterfaces

the

at

adsorb

colloids

and

enzymes,

particles suspended

surface

about

CHEMISTRY

is added

protective action,

precipitation
This

of the

to

effect

emulsoid

of

the

is beUeved
on

the

sus-

97

COLLOIDS

pensoid,

that

so

the

(a)

Experiment,

add

solution

three

sodium

N/20

nitrate,
Into

character

of

both

into
which

and

note

Photographic
of

the

therapeutic

silver

preparation,

silver
of

Swelling

tissues, also
other

other

they

acids
water

the

Colloids.

proteins)

that

and

swell.

and

imbibed.

the
In

alkalies

is

certain
increase

the

as

ions

it is not

changes

it

to

antiseptically.

act

power

vents
pre-

colloidal

acts

Ag

no

plant

gels (as starch,

have

tage
advan-

taking

albumin

Many

obtained.

gelatin, which

however,
ions

(milky)

salt.

being

action,

rate

same

of precipitate.

collargol

which

There

bacterial

silver

gelatin.

is

by

of

silver

gelatin.

solution

absence

tained.
ob-

is

c.c.

the

of

c.c.

c.c.

at

made

agent,
in

solution

are

of the

agent.

ordinary

and

action

protective

The

toxic;

and

carefully

plates

precipitation

protective

about

glycogen

N/20

c.c.

opalescent

An

resembles
dilute

Now

and

simultaneously

beaker.

NaCl

c.c.

and

nitrate

precipitate

put

acid

put

acid

curdy

silver

of N/20

c.c.

nitric

drops

nitric

drops

another

Empty

test-tube

one

To

chloride;

(b) Into

of

the

acquires

emulsoid.

an

so

latter

of

agar,

and

gelatin, and

taking

optimum

greatly

animal

up

water,

tions
concentra-

the

amount

CHAPTER

FORMULAE

EMPIRICAL

AND

STRUCTURAL.

ISOMERISM

A
of

of

KNOWLEDGE

the

assign

to

us

the

number

the

molecule.

This

But

it often

happens

with

of

than
formula

"

the

atoms)

the

the

substance
bodies

groups

made

simpler

of

has
the

atoms
to

groups

build
to

up

been

body

be

is necessary
relations

substance

unite, i.e.,by

of

the
of

grouping

is called

formula

by

acting

decompose

molecule
as

same

is evident,

identified;

is composed

98

It

which

gained

the

empirical

is ascertained

can

the

tear

knowledge

some

fewer

the

(i.e., the

reagents

that

must

we

the

same

no

the

formula

Such

with

the

having

which

It

substances

are

isomers.

another

one

formula.

simple

words,

in

indicated.

are

structural

it into

is

to

atoms

there

having

detailed

more

namely,

formula,

various

on

that

formula.

have

bodies

in

present

organic

example,

called

are

indicating

empirical

may

compounds

formula

therefore,

the

have

we

formula

several

Such

as

element

properties

CgHirOa-

empirical

each

that

For

eighty-two

it

to

is called

formula.

empirical

substance,

of

.atoms

different

very

of

and

composition

percentage

weight

molecular
enables

seen,

the

in

After

apart.
what

to

of,
by

an

simpler
attempt

causing

synthesizing

other

the

the
sub-

100

CHEMISTRY

ORGANIC

SYNOPSIS

Determination

CHAPTERS

OF

of

Chemical

the

I-V.

Character

of

an

Organic

Compound
1.

2.

3.

4.

Purification.
a.

Methods.

6.

Tests

of

purity.

Identification.

properties.

a.

Physical

h.

Elementary

Empirical

formula.

a.

Elementary

h.

Molecular

Structural
a.

analysis.
determination.

weight

formula.

Reactions
and

6,

analysis.

detect

to

of

groups

Synthesis

of

the

Physical

the

atoms

relative
in

the

Osmotic

2.

Electrolytic

3.

Hydrolytic

4.

Surface

5.

Viscosity.

6.

Colloids

molecule.

molecule.

Chemistry

1.

placing

Topics

pressure.

dissociation.
dissociation.

tension.

(including

adsorption).

of

atoms

CHAPTER

SURVEY

PRELIMINARY

substances

to

of

each

organic

utterly

fail, and
of

one

inorganic
compounds
element,

except

element

has

In

substances

is natural,
the

those

know

which

our

studies

there

may

be

in

with

sulphm*

consider

thus

these

as

in

Each

CS2,

101

all

We

and

tion
classifica-

of

with

e.g.,

our

another.

one

elements

etc.

and
other

carbon

namely,
other

one

inorganic

organic

as

the

on

substances,

combined,

the

elements.

basis

along

several

are

In

another

consider

into

in

their

convert

element

our

in

properties

may

organic

carbon

carbon

CO2,

select

look
over-

of

chemistry,

contain
From

that

we

should

viz.,

to

chemical

the

we

we

those

the

convertible

simplest

very

element.

into

of

did

compounds.

element

we

one

characteristics

impossible

above,

to

probably

organic

fixed

we

reactions

substances,

organic

being, therefore,

and

separately,
moreover,

compounds

as

that,

properties

it is

own

remarked

as

so

by substituting

its

compounds.

we

one

that

great

other

into

of

essential

important

most

chemistry

is

organic

various

is

inorganic

transmutability

the

relationships

the

should,

their

CHEMISTRY

their

substance

with

contrast

of

remember

attempt

As

it

number

Their

another.

as

idea

general

ORGANIC

study

to

individually,
a

hand,

OF

attempting

Before

possess

VI

chemistry
with

with
do

which
oxygen

ever,
not, how-

compounds,

the

102

ORGANIC

CHEMISTRY

simplest organic compounds

carbon

is combined

In

union

hydrogen

member

lowest

including hydrocyanic
acid, HCNO,

with

the

considered

derived

as

hydrocarbons

to

subdivide

series

It

of

shall

we

or

are

(4) C,H2"-6
fourth
be

of these

fourth

hydrocarbons
If, now,
of
we

we

series
found

that

that

groups

find

fourth

groups

do

of the

second

and

directlycombine

for

the

6.)
the

it is to

the

first

great majority

belong.

four

shall

of which

is at least

investigate the behavior

these

hydrocarbons

(2) C.H2"
of the

proportion

general formulae

(3) C"H2n-2

case

If

groups.

series, four

follows

enabled

are

of its

(1) C"H2n+2

will, moreover,

acid,

we

all the

that

as

may

and

several

into

The

groups

that

so

several

into

tically
Prac-

compounds

in terms

find

so-

these.

variable,

importance.

(in the
and

from

hydrogen

themselves
of

four

is

the

carbon,

group

the

the

forms

carbon

hydrocarbons

express

are

carbon

hydrogen,
remaining

in

to

cyanic
and

quantitative relationship between

The

we

acid, HCN,

pounds
com-

hydro[gen] carbons).
hydrocarbons (i.e.,
all

be

of

group

ammonias.

union

called

cyanogen

sulphocyanic acid, HCNS)

substituted
In

nitrogen.

forms

of

which

in

with

or

nitrogen, carbon

with

is the

(which

with

those

being

towards

groups

members

that

third

with

do;

the

and

bers
mem-

hydrobrom'c
of

readily react,

not

of the

the

first and

whereas

indeed, that

those
these

reagent by addition, i.e.,

PRELIMINARY

without

chemical

further

subdivide

Of

the

many

substitution.
four

our

(1st and

saturated

4th) and

two

saturated

members

of the

odor, whereas
of the

those

4th
and

compounds^

of the

chemical

reagents,

4th

hence

group

that

aromatic

an

The

bers
mem-

styled aromatic

the

the

that

fact

toward

resistant

called

3d.)

found

not.

very

are

be

often
of

are

they

do

viz.,

two,

(2d and

have

group

account

1st

into

it will

1st

therefore,

may,

unsaturated

groups

are

on

members

We
groups

of the

group

103

SURVEY

paraffins {parum

affinis).
On

account

ampUfy

our

make

properties, then,
into

the

or

aliphatic

aromatic

3d), and

first three

of the

Compounds

may

we

paraffins (1st group),

(2d and

compounds

(4th) .2
up

their

classification

unsaturated
bodies

of

fatty

of

division

groups

organic

chemistry.
The
various
in

and

compounds

derivatives
of each

hydrocarbons

general, analogous,

which

they

understand

we

derivatives
shall

we

derivatives
of the

the
of

be

infer

reactions

be;

study the hydrocarbons

find many

already

of their
met

Only unsaturated

The

member

of

of the

are,

groups

by

reactions

If

important

most

each

in

other

further, when

of the other

compounds

group,

what

approximately
of all the

and

the

we

groups,

the

members
come
we

to

shall
those

quite

similar

to

form

addition

products.

named

from

with.

groups

the

hydrocarbon
to

will

these

by

differ somewhat.

may

chemistry

one

able
and

group

although

produced

are

of

formed

are

each,

compounds
also
e.g.,

sometimes

methane

can

group,

benzene

the
group,

lowest
etc.

104

ORGANIC

From
that

we

shown

these

preliminary

must

first of all take

the

some

one

Let
formula

of these

take

the

C"H2n

+2.

us

important

The

following

it

can

element
bonds
may

methane

is

the

Pentane,

C5H12

Propane,

CsHs

Hexane,

CsHm

be

noticed

the

that

each

differs

all form

They

hydroxide

is

us

with
as

of methane

has

C2H5OH.
series

H, and

write

that

considered

(cf.

each

of

the

an

structural

we

have
atom

of

monovalent

of these

combining

same

increase
this

to

words,

atoms

that

the

understand

other

in

fom*

exactly the

as

is

four; that,

therefore

again by

ethane

be

To

CH2.

that

combine

has

kind

same

Iwmologous

an

it should

why

is by

remember

such

of

one

series).

consider

of

called

the

alcohol

or

the

from

another

one

and

CH3OH,

series

general

list of the most

C2H6

complexity

valence

have

Ethane,

nitrogen oxides

mu^t

of

C4H10

formula

of

derivatives

Butane,

thus

Let

to

members.

derivatives, differingfrom

Such

the

paraffins. They

preceding it by CH2.

the

members

its various

CH4

It will

CH2;

and, having

group,

members:

Methane,

of

one

study carefully

two

or

it will be evident

remarks

of

relationship

another, then

one

CHEMISTRY

'

valence

value.
formula

We
for

follows:
H

H"

C"

I
H

H.

When

methane

two

hydrogen
valence

molecules

of each

atom

bonds

unite

same
can

C"

C"

H.

four

that

we

bonds

valence

value, it will be obvious

exist:

liberated

the

H
of the

and

represented in the formula

as

H"

each

together

fuse

disappears

Since

105

SURVEY

PRELIMINARY

that

write

can

of C

only

only

one

the

has

propane

structural

one

111
formula

it,viz.,H

for

"

"

H
have

two

we

propane,

of the

atom

add

may.

chain

or

an

CH3
the

to

of the

one

we

may

of the

extra

it either

to

But

member

next

viz., butane, for, in adding

H.

"

of the

varieties

"

end

ones,

series,

group

to

central

HH"

C"

HH

C"

H,

H"

or

C"

C"

C"

C"

III
H
and
vary

the

in

properties

accordingly;
when

atom

of

the

extra

union

with

CH3
two

words,
group

it makes

is tacked

atoms

will

ence
differ-

a
on

corresponding body

in other

the

III
H"

to

(as is the

case

106

ORGANIC

with

the

three

central

When

the

when

at the

therefore

contains

isomerism

apphes

not

of propane
such

but

"

By

branched

only

all its

to

the

using models

instead

Normal

still

p.

as

of

represent

223).

of methane

By

wood),

the

monovalent

removing
and

the

occupying

an

joining the

thus
of

core

four

solid

we

hedron
tetra-

angles of

combining

affinities,

the

by

in

representing

caps

points

demonstrated:

angles being covered

tin

these

Isobutana

clearly

more

(made
these

chlorides,

e.g.,

Propane

butane

consider

which

as

may

considered

be

of formulae

Ethane

be

tives
deriva-

methyl

derivatives,

this

Now,

etc.

^H

can

the

iso-compound

an

may

of

center

chain.

to

atom).

iso-compound;

an

Such

with

one

end

an

the

is called

^for butane

"

also

hydroxides,

in

it is normal.

to

on

of

case

occurs

resulting body
end

when

the

in

(as

substitution

chain

and

atom),

atoms

the

CHEMISTRY

model

atoms
cap

two

from

midal
pyra-

(see Fig. 22,

two

tetrahedra

models

by

the

108

ORGANIC

applies

the

to

CHEMISTRY

hydrocarbons:

derivatives, oxides

for

down,

so

whereas

and

yield

to

the

of

extent

started

further

(or alcohol)

various

substances

oxidation

with.

hydroxide

be

cannot

organic hydroxide
as

cohols)
(al-

hydroxides

inorganic

an

product

ultimate
an

(ethers), and

halogen

these, however, the analogy breaks

Beyond

has

each

and

We

oxidized

according

the

of

nature

an

oxidized,

be

can

is

the

to

the

hol
alco-

therefore, classify

may,

our

thus:

derivatives

Halides.
Oxides

ethers.

or

Hydroxides
Oxidation

contact

with

of

we

the

the

paraffins

brought

are

chlorine, substitution

atoms

have

may

of alcohols.

products

When

Halides.

alcohols.

or

of

Thus,

occurs.

taking

monochlormethane,

trichlormethane

or

one

into
more

methane,

dichlormethane,
and

(chloroform)

tetrachlorme-

thane.

connection

In

products
they

acid, the

of the

acid

hydrocar]bon

minus

general

tel*m

for

specific

names

ethyl

as

the

(C2H5-), propyl

alkyls

or

Halogen
of the

with
atoms

atoms

from

been
its

(C3H7-),

so
a

The
the

alkyl, and

and

with

that

halogen

atoms.

methyl

are

out

replaced by

is

groups

alkyl is, therefore, analogous

element

pointed

derived

of

one

stitution
sub-

monohalogen

be

having

all such

for

the

it should

considered

be

may

with

(CH3-),
An

on.

monovalent

NH4-.
may

of the

likewise

displace one

alkyl radicle

when

or

more

this latter

PRELIMINARY

is

in combination

already

CCI3CHO,

of

the

ing
substitut-

trichloraldehyde,
combines

oxygen

element,

monovalent

oxide, Na20,

is

Since

(or ethers).

atoms

other

some

being CH3CHO.

aldehyde

Oxides
two

with
chloral

Thus,

group.

109

SURVEY

oxide

alkyl

lowest

as

with

in sodium

v/ill have

the

CHav
.

formula

To

yO.

this group

belong

the

ethers,

CH3/
ether

common

being

yO.
C2H5/

methane

of

When

(or alcohols)

Hydroxides

replaced by

is

of the

one

hydroxyl, OH,

atoms

methyl

alcohol

is

Thus

formed.

"

becomes

"

H
H

"

and

OH,

"

it does

which

matter

not

of

the

H
H

is thus

atoms

being always
The

the

alcohol, CHb"
we

however,

to

three

exist
p.

its

alcohol, ethyl

we

the

atoms

may

that
or

to

from

propane,

analogous

butane

when

106);

alcohol

conditions

of propane

hydrogen

such, and

and

the

form

encounter

we

atom

for ethane

to

come

(see

propane

resulting compound

CH2OH.

which

those

the

same.

is true

same

When

replaced,

is
add

formed
the

OH

is in combination
one

resulting product,

in
as

union
we

with
have

with
from
group

with
two
seen,

no

CHEMISTRY

ORGANIC

exhibit

will
have

different

forms

two

group

in the

CH3"

CH2"

of

propyl alcohol.

is attached

one

Consequently

properties.
the

at

these

end

other

the

in

CH2OH;

Of

we

OH

the

chain,

of the

it is attached

OH
in the

middle

of the

chain,
CH3

is

former

called

CH3.

"

latter

alcohol, the

primary

CH

"

The

secondary alcohol.
In

the

radicle

butane,

end

the

at

of the

we

may

have

chain, CH3

(primary butyl alcohol);

CH2OH
C

of

case

in the

atom

of the

center

hydroxyl

CH2

"

CH2

"

attached

or

with

chain

the

"

to

other

one

/OH
attached

atom

ondary

alcohol);

butyl

the

hydroxyl

that

is not

it, CH3

to

CH2

"

or^

"

"

C!H"f
^CHs

third

possibility
"

be

attached

to

directly combined

with

any

radicle

may

(sec-

atom

other

CH3
thus

atom,

CHs^C

"

(tertiary butyl alcohol).

OH

CH3
There
alcohols

The

varieties

of

these

1.

Primary,

2.

Secondary,

3.

Tertiary, containing

essential

is that
In

therefore, three

are,

when

all these

containing

the

containing the

chemical
oxidized
alcohols

the

group
group

CH2OH

"

group

difference

one

"

between

they yield different

only

CHOH

"

hydroxyl

"

OH

"

these

products.
radicle

is

PRELIMINARY

they

present;
monovalent

such

elements

chemistry, however,

we

Just

is

NaOH

(thus

inorganic

in

as

hydroxides

have

may

of

hydroxides

sodimn

as

CH3OH).

with

analogous

with

analogous

are

HI

SURVEY

with

/OH
hydroxyls,

two

alcohols

with

C!a"r

e.g.,

so

hydroxyls,

two

e.g.,

CH2

alcohols

are

OH

e.g.,

CH

hydroxyl

containing

three

which

analogous

with

general, have

the

OH

CH2"

groups,

have

Simi-

OH.

"

CH2"

larly,there

we

may

"

OH,

are

OH

CH2"

/OH

Al^OH.
^OH
Alcohols,
of

power

acids

neutrahzing

to

with

reacts

form

salts.
in

HCl

Thus,

accordance

equation NaOH+HCl=NaCl+H20;

the

taking

in

hydroxides

hydroxide

sodimn
with

like

an

alkyl hydroxide

and

(alcohol) instead

of

an

have
R0H+HC1=RC1
+
alkaUije hydroxide, we
with
H2O
(R
alkyl) ^ They can react in this way
as
organic acids, the resulting body being known
ethereal
salt or ester (see p. 173).
These
organic
an
=

salts differ

widely from

metalUc

salts in their

ical
chem-

behavior.
An

as

alcohol

with

Alcohols, however,

are

only

are

metallic hydroxides.

one

not

hydroxyl
really basic

group

in the

is called

same

sense

112

ORGANIC

it

monacid,^ because
of

monobasic

called

are

of

Oxidation

is

only

(p. 110), the division

and

tertiary alcohols

of their

behavior

alcohols

Primary
and

A.

alcohols

When

oxidized,

one

becomes

replaced

formed.

But

the

by

tioned
men-

difference

aldehydes

break

oxidized,

that

acids

methyl

of the

up

and

hydroxyl,
body

to

breaks

up,

ketones.

that

so

would

tend

two

cannot

giving

radicle

methyl

having

atom

is

alcohol, CH3OH,

CH2(OH)2

such

consider

must

we

of the

atoms

by

formula

directly attached
immediately

been

yield ketones.

products

Aldehydes.

the

has

compounds.

lower

oxidation

having

(glycerol).

oxidation

yield on

aldehydes,
therefore,'

are,

(glycol)

alcohols, when

Tertiary
The

most

acids.

Secondary
into

oxidation

tri-

primary, secondary,

is warranted

on

alcohol

As

into

the

far

alcohol

of Alcohols.

Products

groups

called

are

diacid

one

triacid

one

such

by

are

molecule

one

two

three

alcohols

and

importance

with

those

there

with

those

monacid

numerous;

with only

react

can

acid;

diacid^

The

add.

CHEMISTRY

body
to

be

hydroxyls
exist, and

ofif water,

it

thus:

/0|Hl, leaving

body

having

the

formula

/H
H

C^

"

The

the bQst

This

is

terms

monatomic

designationwould

an

aldehyde,

and

monohydric

be

and

are

monohydroxylic.

the

also

group

used;

but

113

SURVEY

PRELIMINARY

/H
is known

C^

"

this

of

portion
B.

it absorbs

called

and

forms
is called

which

the

by

+0=H"

of

atom

an

thus:

H-COONa,

metal,

an

the

form

can

may

only

called

atom,

ethereal

an

ethyl formate.

are

groups

lowest

simplest

the

to

this

of

Such

an

salt ; it is monobasic.

one

The

dibasic.

is

salt,

Instead

replace

being

replaced

form

to

formate.

-00002116,

carboxyl

If two
acid

radicle

be

can

group

metal

sodium

resulting compound

salt, thus:
acid

carboxyl

monovalent

alcohol

acid)

(Formic

aldehyde)

^O

of this

atom

characteristic

C"

^0

The

group

/OH

"""

(Formic

the

having

carboxyl

is the

/H
H"

oxidized

compounds:

of organic

group

body

(from carb[onyl hydrjoxyl), and

acid

Each

carbonyL
is further

aldehyde

an

oxygen

COOH,

group

is

CO

The

group.

corresponding aldehyde.

When

Acids.

aldehyde

group

has

hydrocarbon

the

as

present, the
dibasic

diacid

resulting

acid

alcohol

sponding
corre-

is oxalic,

COOH

having

the

formula

Like

dibasic

acids

in

COOH.

general,
one

of

these
which

acids

form

can

only

one

two

series of salts,in

carboyxl

group

reacts,

COOK

I
COOH

(acid potassium

oxalate), and

in the

other,

114

ORGANIC

CHEMISTRY

COOK

both,

(neutral potassium oxalate).

Tribasic

COOK
acids

organic
C.

also

When

Ketones.

oxidized, it
which

forms

is called

The

that

in

ketone

nitrogen

OF

contain

one

and

complex

are

of

ammonia

several

are

as

the

amido-

atoms

may

be

imido-group.

CH3

CN,

"

of

NH3

or

or

tertiarybases.

(NH4)

quaternary

Several

be

Or
in

we

replaced by

Two

the

is

hydrogen
called

the
be

may

compounds

have

NH4OH

which

atoms

such
may

cyanide.

NH2,

hydrogen

we

derivatives.

ammonia

group

so

trites.
ni-

are

hydrogens

displaced,

as

in

bases.

organic

amino-acids

methyl

amino-group.

three

and

KCN,

as

displaced, leaving NH,

All

ammonium

importance

most

may

displaced, leaving only N;

The

taining
con-

aldehyde

an

compounds,

kinds
of

atom

called

the

hydroxyls

compounds

have

Many

organic radicle,leaving the

of

+H2O.

CH3

more

inorganic cyanides,

hydrogen

called

ALCOHOLS,

or

derivatives

have

we

There

an

"

(Acetone)

organic cyanides,

One

CO"

CH3"

groups.

cyanogen

have

CO

"

group.

The

As

group

is

carboxyl.

alcohol

are

+0

carbohydrates

The

the

having

DERIVATIVES

hydroxy-acids

besides

alcohol

secondary

alcoliol)

OTHER

important.

ketone:

CH3

propyl

(Secondary

less

are

body

a
a

CHOH"

CH3"

exist, but

nitrites

contain

are

of

both

importance.
the

NH2

and

the

116

ORGANIC

Triacid

c,

4.

CHEMISTRY

Oxidation

j Aldehydes,

products

( Acids.

d,

Hydroxy-acids.

e,

Carbohydrates.
derivatives,

Nitrogen
a.

Cyanogen

b.

Ammonia

combinations.
combinations

NH2;
c.

Nitrites.

d.

Amino-acids,

(amido-group,
etc.).

NH,

imido-group,

similar

acid

and

amides,

other

compounds.

derivatives.

Sulphur

5.

alcohols.

hexacid

to

B.

Unsaturated

cC

hydrocarbons.
^

1.

Ethylenes,

2.

Acetylenes

^^^

Cnii2n("C=C").'^
C"H2"_2

C^eC

"

).

"

C.i

A.

Benzene

derivatives

(seejBynopsis,

will

explained

later, the

As

class

of

the

we

be

about

nothing

scientific

derivatives
certain

chain
atoms

in

other

as

of the

chain).

S,

fatty
the

or

cyclic

of

really

and

the

C.

the

place

chain

of

avoid

chapter.

structure),
of

heterocylic
one

it

compounds

organic

as

To

in this

(not closed-chain

compounds

and

aromatic,

compounds

(closed

bons
hydrocar-

intermediate

an

after

of

acyclic

takes

423).

synopsis

these

isocyclic

aromatic

N,

is

classification

as

which

in

p.

group

309)

the

inserted

fatty compounds

benzene

p.

between

say

more

groups

and

(see

terpenes

compounds

confusion
2

be

naturally

would

CnH2n-6.

hydrocarbons,

Benzene

and

Compounds.^

Aromatic

II.

or

more

atoms),
(closed
of

the

CHAPTER

SATURATED

VII

HYDROCARBONS.

THE

METHANE

SERIES.

(CH4)

Methane
in

elements

the

(2) By

hydrogen

AI4C3

be

can

carbon
p.

produced
of

stream

of

tips

an

304).

disulphide

+8Cu
of

action

the

and

(CS2)

allowing

mixture

of

copper:

+2H2S

the

from

passing

and

(H2S),

heated

on

CS2

(3) By

carbon

producing

act

by

(see acetylene,

sulphide

to

CH4

glowing

the

arc-light

electric

of

elements

between

hydrogen

synthesized

ways

quantity

from

directly

them

several

small

(1)

be

can

12H0H

CH4

water

+4CU2S.

aluminium

on

=3CH4

carbide

+4A1(0H)3.
I-

PARAFFINS

THE

Having

obtained

members

other

producing
then

OR

reacting

CH:
(Methyl

methane,

of

the

halogen

its
on

MARSH-GAS

these

series

SERIES,

we

it

substitution
with

metals,

thus

(Ethane)

117

by

first

products

I+Nal+|Na+I|CH3=CH3CH3+2NaI,
iodide)

build

may

from

CnHin+2.

up

of

the
all
and

118

ORGANIC

CHEMISTRY

CH3iI+Na+iNa+i;C2H5
i

(Methyl

iodide)

also with

(Ethyl

iodide)

(Propane)

thus

methyl,

zinc

CH3CH2CH3"+2NaI;

=2CH3

2CH3|I +Zn;(CH3)2

CH3

"

+Znl2,

(Zinc methyl)

2C2H5|r+zi^;
(CH3)
The

product

the

with

an

CH3+Znl2.

"

for

general

poses
pur-

substitution

proper

hydrogen,^

nascent

derivative

CH2

"

prepared

decomposing

with

acid

an

be

paraffins may
(1) by

2CH3

(2) by heating

or

of soda-lime:

excess

CH3l+2H=CH4+HI,
iodide)

(Methyl

CHa

COONa

"

(marsh-gas), CH4,

Methane
a

arising from

gas

of
so-called

in

.of natiu*al

and

C2H"

*The

of

part

with

with the

are

In

on,

also

Its

such

for

in

acid
the

alcohol

(H2SO4)
above
and

as

as

the

one

of

production by
be

brought

of

water

filter-paper

formed.
reactions

three

with

copper

cooling

(2)

inoculating

pieces

(1)

position
decom-

(3)

can

copper-zinc couple (made

powdered

of

trace

hydrogen.
iodide

then

and

zinc
of

from

going

by

suspended

hydrogen

nascent

obtained
one

C4H10

where

matter

laboratory

small

water

gas.

of vegetable

the

containing

is

matter

in nature

in coal-mines, and

fire-damp

decomposition
about

+Na2C03.

occurs

stagnant

vegetable

constituents

the

CH4

acetate)

(Sodium

as

+NaOH

closed
the

parts

vessel).

drop of H2SO4

may

be

by heating together

In

of

powdered

the

presence

couple readily yields

reaction

couple,drop by drop.

this

as

mixture

of

the

nascent

methyl

is brought into contact

SATURATED

119

HYDROCARBONS
*

(cellulose)with
It

sewage.

hence,

forms

the

danger

and

the

Natural

only

hypotheses

it is the

animal

or

action

the

95%

it

There

also
and

that

carbides

of

two

are

oiFnatural

other

metalUc

on

(i.e.,

hydrogen

decomposition

the

and

matter,

safety-

Davy

methane;

monoxide.

of

mines
coal-

in

explodes) is high.

production

result

of water

it

carbon

to

as

the

nitrogen, ethane,

of

trace

flames

air,

kindling temperatiu*e,

about

has

Uttle

that

its

at which

gas

contains

bare

having

of

necessity for using

temperature

with

explosive mixture

an

in

contained

microorganisms

Fortunately

lamp.
the

the

one

gas,

vegetable

it is due

to the

(cf aluminium
.

carbide

Coal

reaction).

contains

gas

30

to

of

40%

methane.
Water
that

is

is the

gas

used, because

monoxide

poison
of

the

(produced

from

monoxide,

but

other

of

coal

as

oil) contains
large

is also

gerous,
dan-

very

carbon

monoxide.

with

the

blood.

oil and

crude

of carbon

content

globin
haemo-

interfering with
the

The

of

nearly

Pintsch

gas.

the
water

has

steam

gas

little

carbon

methane

and

very

amount

gas

hydrocarbons.

Methane
When

thus

composition

same

of

combining

power

from

gas

10%

to

by

large

Coal

blood,

the

prepared

acts

oxygen-carrying
gas

of its

(about 30%).
containing

This

poisonous illuminating

most

mixed

is

colorless, odorless,

with

chlorine

and

exposed

sunlight it explodes:
CH4

+4CI2

ecu
(Carbon

stable

+4HC1,
tetrachloride)

to

gas.

direct

120

ORGANIC

when

or

to diffused

exposed

of

monochlor-

trichlor-

(CHCI3),

The

flame.
10

By

retort.

usual

(C4H10)
The

other

butane

of

and

specificgravity,

the
we

ascend

liquids

the

Methane,

-164"

Ethane, CjHe
Propane,

CaHg

Butane, C4H10

Pentane, C5H12..
Hexane,

to

water

over

also

and

is

temperatures.
sofids.

number
a

of

Above
carbon

regular gradation

lowest

series:

the

or

butane

the

to

the

highest

boiling-point,

melting-point

increase

series.
Boiling-point.

CH4

the

the

paraffin

of

fitted

inflammability,

ordinary

at

from

iron

an

air.

There

formula.

gm.

instead

methane

its

10

in

used

small

delivery tube

indicates

the

be

acetate

mix

(CsHg),

are

physical properties

members

heat

propane

gases

name

in the

and

with

paraffins

the

atoms

as

also

(CCU).

with

and

Test

manner.

are.

dish

mortar

evolved

the

(C2H6),

(CH2CI2),

sodium

some

could

of

means

lightness compared

Ethane

test-tube

retort, collect

in the

of

in

ture
mix-

tetrachloride.

soda-Ume,

large

dichlor-

evaporating

an

of

gm.
A

retort.

its

in

Cool, powder

with

the

carbon

Dehydrate

heating it

forms

tetrachlor-methane

and

last is also called

by

sunlight it

(CH3CI),

Exi"ERiMENT.

CHEMISTRY

Specific gravity.

0.415

(at -164")

84.1"

0.446

(at 0")

44.5"

0.535

(at 0")

1"

0.600

(at 0")

36.3"

0.627

(at 14")

69"

0.6603

(at 20")

Melting-point.

-184"
-

172.1
45

CeHn

4"

Tetradecane,

C14H30

252"

0.775

(at 4")

Hexadecane,

CieHs*.

287"

0.7758

(at 18")

18"

317"

0.777

(at 28")

28"

Octodecane,

CisHss.

SATURATED

The

heat

combustion

of

than

this

that

is the

heat

of

the

of

lower

next

of

large calories

158

combustion

of

molecule

gram

about

is

paraffin hydrocarbon
greater

121

HYDROCARBONS

hydrocarbon;

value

of

the

CH2

group.

The
with

mainly

in

also

contains

contains

The

fractions

lower

soda

caustic

sulphuric acid,
between

40"

naphtha),

and

that

between

Gasoline

and

of

C7H1G,

CeHu,

gasoline there

products

and

CgHig.

(70-90"), naphtha
benzine
also

as

the

to

form

of the
an

in the
^

solvent

in

experiment

tional
frac-

rhigolene

(80-120") and
gasoline, called
industrial

in many

paraffins from

contain

mixture
manner

below,

Carefully distinguishfrom

is kerosene.

careful

benzene

gasoline

no

hydrocarbons

lower

(or

(40-70"), gasoline

the

should

explosive

flashing-point,tested
described

the

low-boiling

gas),

(a

contains
It

C16H34.

vapor

would

as

water.

300"

by

High-boiMng

Kerosene

processes.

C9H20

used

with

gasoline

From

ether

tained
ob-

mostly mixtures

are

(80-110"), hgroin

(120-150").

benzine,^ is

and

obtained,

18.3"), petroleum

thus

steam;

is

150"

distillation, cymogene
(b. pt.

oils

with

150"

its

be

can

crude

to

solution, and

and

distillate

cial
commer-

treatment

distilled

are

for

the

of

successive

purified by

are

fornia
Cali-

carbons.
hydro-

subjected

Some

distillation.

fractional

is

petroleum

purposes,

suitable

products

secure

petroleum

benzene

some

met

are

derivatives.

sulphur

few

methane

American

petroleum.

petroleum
To

series after

of the

members

in

with

air.

similar

to

tells

us

lamp
Its
that

whether

(p. 318).

122

it

ORGANIC

contains

CHEMlSTRl'

gasoline.

any

The

point is regulated by law, varying

and

countries
after

tar,

from

about

kerosene

strongly

is
the

cooling

38"

the

liquid

that

49".

removed,

is

distillate

(with

steam),

lubricating
soUd.

by

Vaseline

special

and

kerosene,

and

of

gasoline

of

kerosene,

hydrogen

is greater

than

because

various

selected

and

of

the

of

of

waxy

made

are

oil.

sylvania
Penn-

54%

naphtha,
'

oils.

that

tilled
dis-

grades
white

crude

16.5%

lubricating

The

fuel

value

equal weight

an

greater

of

percentage

present.

Experiment.

Place

the

flashing-point apparatus

(see Fig. 18) containing

in
of

Suspend

that

the

bulb

Heat

the

beaker

and

test

match.
the

the

of
the

18.

flash

in

the

kerosene.

Bubble

with

vapor

the

air

lighted
when

temperature

fire

the

so

frequent intervals,

at

takes

full

thermometer

slowly.

the

of kerosene

c.c,

two-thirds
a

is

oil

Note

vapor

20

large beaker

water.

through

Fig.

By

fractionally

petrolatum

yields

17%

distilled.

paraffin is

from

petroleum

is

the

liquid

process

residual

(paraffin oil) and

out

giving

Purified

oil.

The

States

paraffin is separated;

pressed

is

in different

to

filter-pressingit, crude

flashing-

minimum

oil

(the burning

perature
tem-

is 40-50"

above

ing-po int)

There

106).
formulse

are

These
as

many

isomers

iso-compounds
having

branched

of
are

the

paraffins (see

represented

chains

of

carbon

in

p.

their

atoms

VIII

CHAPTER

PRODUCTS

SUBSTITUTION

HALOGEN

OF

THE

PARAFFINS

If

only

by

replaced

of

CI

CH3"

e.g.,

The

derived

methyl

chloride

or

methyl

bromide

or

bromide

and

mixture

(2)

All

the

CH3CI;

monobrommethane,

CHsBr;

the

proper

following

with

it

and

by

exposing

sunUght.
by

halogen

acting
acid,

CH3CI

in

njethyl

on

accordance

+H2O,

=CH3Br

+H2O,

CH3OH+HI1

=CH3l

+H2O.

method

methyl

chloride

methane

from

CH3;0H+H;Br

(3) Another
on

(1) The

equations:

CHaiOH+HjCl

action

CH3I.

produced

secured

be

are:

monochlormethane,

diffused

may

with

alcohol
with

to

sists
con-

radicle,

methane

from

bromine

or

it

alkyl

an

Preparation.

be

can

chlorine

mixing
the

of

Methods

General

because

monoiodomethane,

or

is called

compound

to

is

108).

p.

halides

iodide

Unked

atom

(see

alkyl

methyl

the

atom,

hydrocarbon

(or alkyl halogenide),

halogen

the

of

atom

halogen

halide

alkyl

an

hydrogen

one

alcohol

of

obtaining
of

124

PCI3,

them

PBr3,

is

and

by
PI3:

the

125

PRODUCTS

SUBSTITUTION

HALOGEN

'

3CH30H+PCl3=3CH3Cl+P(OH)3,

In

3CH30H+PBr3

=3CH3Br+P(GH)3,

3CH3OH+PI3

=3CH3l

exactly similar

manner

ethyl halides

the

Some

of the

under

the

the

causes

skin

to

result

very

inflammable.

is

It

local

the

skin.

The

of

be

can

heat

as

or

by

tion
evapora-

from

the
is

vapor

as
a

glass

Its

also

administered

anaesthetic,! being

rapid

latter.
used

is

anaesthesia

enough

freezing the
It

in

up

for

abstraction
in

readily liquefied,

C2H5CI,

put

is used

liquid on

is

"23.7".

at

12.2".

at

tubes, and

spraying

CH3CI,

is

It

(monochlorethane),

Ethyl chloride

metal

Important Alkyl Halides.

Uquid boiling

liquid boiling

ethyl alcohol.

from

ordinary conditions.

the

methods

last two

(monochlormethane),

chloride

Methyl
gas

More

the

to

derived

be

can

+P(0H)3.

general
by

vapor

inhalation.

(monobromethane),

Ethyl bromide

liquid resembling

chloroform

physiological

effect.

37.4"

737

under

gravity is
any

of the

the

action

bromide,
^

In

this
For

excellent

1.468

It

boils

13".

It

general methods,
of
as

in the

book
full

brief

and
be

may

ethyl sulphuric

(at 37.1"-

38.37"

at

but

odor, density, and

pressure),

mm.

at

in

is

C2H5Br,

its

obtained

is best
acid

specific
by

prepared by
potassium

on

following experiment.
pharmacological

information

pharmacology text-books

on

these

statements

points

by Cushny

and

are

consult

by

Sollmann.

quent.
frethe

126

ORGANIC

CHEMISTRY

Into

Experiment.

250,

sulphuric acid; add

of

concentrated

of

ethyl alcohol, shaking

of

iced

having

condenser

rapid
the

water

flask

50

gm.

of

in

place the flask

condenser.

Fill

of

the

bath

of

cold

heating

and

that

Watch
sucked
turn

up

the

Decant

the

into

adapter
most

any

so

flask

of the

air

water

c.c.

up

Use

into

bromide,

the

to the

one-third
below

the

receiving flask in

distillate

and

continue

comes

receiver

over.

be

not

If this is threatened

condenser.
that

38
set

attach

rapidly
of

contents

the

and

this

Heat

as

Cool

Put

adapter dip

Place

water.

c.c.

19.

the

have

55

attached.

potassium

sand-bath

water.

long

as

Meanwhile

Erlenmeyer

an

full of ice-water
surface

on

c.c.

time.

condenser.

powdered

Fig.

then

the

quickly

water, add

adapter

an

of

stream

again.

55

put

same

running

cool

and

water,

the

at

it in

by holding

flask

the

flask

c.c

can

from

enter

the

it.

ethyl bromide,

HALOGEN

then

add

Wash

ice-water

several

the

the

bromide

the

out

dry

calcium

an

this

bottom

layer into

chloride, cork
place.

cool

After

day

receiving flask

boiUng-point.
picnometer

C2H5OH

CH3

"

CH3

alcohol)

"

10

or

"

CH2

(Ethyl

HSO4

+KBr

(Ethyl

Other
are

methane,
methane,

by

the

CH2CI2

CH2I2;

brommethane,

following

+H2O,

HSO4
acid)

+KHSO4.

CHzBr

(Acid potassium
sulphate)

bromide)

(besides the alkyl halides)

halogen derivatives

illustrated

"

"

following compounds

dibrommethane,

dichlor-

; diiodo-

CH2Br2

trichlormethane,

CHBra;

small

sulphuric

CH3

in

The

c.c.

the

Note

specific gravity

Place

water.

explain the reactions

+H2SO4

CH2

water-bath.

cold

in

the

holding
will

equations

(Ethyl

Take

let it stand

distill from

so

or

Add

flask.

dry

flask.

the

funnel, and

tightly, and

fractionating flask,using

empty

cork

shake

sodimn

dilute

separating

water.

Finally

with

to

the

Decant

manner.

bromide

ethyl

run

small

agitate.

in

127

PRODUCTS

solution; do not, however,

Transfer

and

times

washed

carbonate

in

SUBSTITUTION

CHCI3;

triiodomethane,

CHI3;

triand

tetrachlormethane, CCI4.
Of

the

many

paraffins the
of methane
Chloroform

having

compounds
three

are

trihalogen

the

only

ones

derived

thus

of

boiling-pointis 6 1

"

1.498 at 15", 1.5039

odor
at 73 1

at

and
mm.

^^.

the

products

substitution

importance.

(trichlormethane), CHCI3,
pleasant

from

sweetish
Its

is

taste.

liquid
Its

specific
gravity is

It is sUghtly soluble in

128

ORGANIC

water,

liter of water

one

while,

for

the

on

take

can

CHEMISTRY

other

substances.

many

Chloroform

less safe

than

it

be

used

or

gas-light is

lamp
should

stable

acid, and
These

impurities

when

chloroform

or

other

halogen

p.

69).

to

the

The

The

of

of its

to

acts

by the
the
be

chlorinate
action

mixture,
used

put

150

ture
mois-

furnishing

(COCI2).

precipitate

solution.

substitution

no

of

alcohol

since

Pure

products
silver

ions

halogen

(see

chloroform,

to

decomposition.

prevents

ing
preparation is given in the follow-

(from bleaching-powder)
and

acetone,
calcium

chloroform

is

from

the

product

hydroxide present

produced.

Alcohol

in

may

of acetone.

Experiments*
flask

precipitate with

0.6%,

of the

instead

It is not

phosgene

nitrate

Chlorine

experiment.

thus

furnish

addition

extent

method

they

with

contact

gives

silver

nitrate, because

vapor

readily detected,

them

give

only

light,air,and

or

with

immediately

not

where

chlorine, hydrochloric

be

containing

shaken

in

to

chloride

can

inflammable,

produced.

impurities,

much

Chloroform

come

exposure

ful
use-

very

anaesthetic

are

solvent

considered

available.

oxy

it is not

an

to

good

is

decomposition,

carbon

chloroform

do

as

some

poisonous

as

gases

compound,
causes

the

night

noxious

as

Since

allowed

be

not

flame,

ether.
at

liter of chloroform

one

is

of chloroform,

gm.

It is

anaesthetic, but

general

can

hand,

of water.

3 gm.

up

dissolving 8

(1) Preparation.
gm.

hypochlorite) and

of
450

bleaching
c.c,

of

Into

powder

water, and

liter

(calcium
mix

them

SUBSTITUTION

HALOGEN

Add

thoroughly.
and

acetone

with
as

for

long

droplets

distillate to
and

chloroform

of

the

wash

with

it

chloroform

the

Run

calcium

chloride, cork, and

the

can

be

sealed
will

equations
CHs

2CCI3

CO

"

"

up

CO

"

distilled
water

CHs

be

+6C1

CCI3

+Ca(0H)2

nitrate
nitrate

"

CO

"

solution
the

is 2.885

at

so.

following

(CH3COO)2Ca.
test-tube

three

at

146"

with

appears,

chloroform.

15".

It has

751

at
at

been

hexagonal plates.

is

stand,

liquid

cooling it

medicine.

crystals having

Its odor

it

specific gravity

(triiodomethane), CHI3,

crystalline solid, the

silver

is

On

as

silver

later.

Its

used

this

add

Let

mm.

8".

in

times

wash-water

of

the

Remove

precipitate forms

+3HC1,

CH3

half

precipitate

no

solid, melting

Iodoform

The

(tribrommethane), CHBr3,

boils

or

redistilled,but

vigorously.

last

washed

whether

Bromoform

becomes

; if

add

Wash

pipette.

to

of

=2CHCl3

shake

testing the

observing
which

and

water

manner,

day

bottles.

of chloroform

c.c.

with

portions

dry flask, add

(2) To

the

form
chloro-

off the

let it stand

sample

the

explain the reaction:

CHs

"

in

with

small

not

as

Transfer

into

yield is small, it need

flask

steam

appear

several

water.

As

Pass

condenser.

of

c.c.

condenser,

separating funnel, draw

16

the

with

(p. 16).

of

end

the

at

water

of

Connect

water.

distillation

steam
as

of

c.c.

mixture

generating flask and

steam

slowly

35

129

PRODUCTS

pecuUar

is
the
and

yellow
form

of

charac-

130

CHEMISTRY

ORGANIC

teristic.
It

4.008.

melts

at

119".

is used

in

surgery

It

being probably

action

is manufactured

It

and

iodine

30

alcohol, heat

in

to

the

crystals.

carbonate

the

then
alkali

conversion

(2) Make

the

alcohol

are

formed.

size

This

of

iodoform

and

reaction, besides

contain

is not
its

part

the
of

characteristic

iodoform

in this

group
a

"

the

action

by slow

of

tion
producNalO;
of

the

formate.

sodium

and

in

alcohol,

evaporation
considerable

CO

"

provided
On

group.

odor,
is often

compounds

other
,

carboxyl

manner

ing-point
melt-

being given by alcohol, is

CH3

strong

it
the

wash

of

action

crystals

hexagonal

add

change

the

of iodoform

given by aldehyde, acetone,

that

by

loosely covered

made.

the

iodal

yellow solution

set it aside

and
of

into

present

to

doubtless

by

add

brown,

desiccator,

be

are

iodal, Cla-CHO,

of

in

of

c.c.

iodine, shaking

solution

may

involved

reactions

cooling, filter and

After

determination
The

add

become

has

of

sodium

of

70-80", and

to

being dried

After

method

gm.

powdered

liquid

sodium

pale yellow.

of

of

action

following experiment:

water,

warm

gm.

the

Its

water-bath

If

frequently.
just enough

by

the

in

is freed.

which

carbonate.

of

c.c.

time

iodine

(1) Dissolve

in

antiseptic, the

an

acetone

is illustrated

Experiments.
carbonate

as

to

from

potassium

preparation

little at

due

is

specificgravity

Its

the
used

the

account

production
as

test

CO
of
of
for

IX

CHAPTER

ETHERS

oxides

alkyl

The
of

methyl

as

C2H5

"

method

"

CHs

jNa +I|

ethylate)

is
is

ether

Ethyl

liquid, boiling
and

pressure)

(Methyl

iodide)

(Ethyl

ether

Methyl

ether,

35"

having

O"

is unimportant.
ether.

(33.6"

734

at

is

ether

Pure

barometric

mm.

of

specific gravity

+NaI.

C2H5

ether)

(Ethyl

common

at

+NaI,

CHs

ether)

C2H5"

and

gas

the

by

shown

is

O"

CH3"

OjNa +IIC2H5

"

(Sodium

atom,

ethyl

CH3;

"

sist
con-

oxygen

an

synthesis

iodide)

(Methyl

methylate)

C2H5

of

equations

following

(Sodium

"

to

They

C2H5.

"

CH3

ethers.

linked

CH3

ether,

general

radicles

organic

two

called

are

0.718

at

25"
15.6"

and

0.7079

It

at

dissolves

to

certain

-j^.

about
for
and
To

6.5%)

(about

extent

11%
some

alcohol
obtain

of

time

water.

absolute

it

water;

If

ether

is

be

abstracted

ether,
132

from
it

is

takes

also

allowed

to

both

bromide

magnesium

over

will

in

it

necessary

by

up

stand
water

the
to

salt.
treat

133

ETHERS

the

ether

(Na

with

+ H2O

when

metallic

NaOH

abstracts

rapidly evaporated,

freeze

if the

water

vessel

latter

surrounded

heavier

air

than

and

heat

in

The

ether.

is

vapor

therefore

should

to

small

falls.

consequently

and

inflammable,

very

distill

enough

is contained

the

by

then

vaporizes readily, and,

It

H)

and

sodium

is

It

be

kept

great

"

from

away

number

flame.

of substances.

anaesthetic, being
administered.
and

ether

It is

of the

Because

of

use

how

of C.P.

proportions.

is allowed

In

to

(see

flow

To

pare
pre-

slowly

127) contained

p.

will

hole

the

condenser,

the

third

in

introduce
the

make

have

an

ether

the

of

extra

is connected

bulb

The

liquid.

with

For

in which
tube

generator

into
in
clear

of the

which

better

flask,

contains
is
is

arrangement

it is necessary
boil

When

with
and

ethylsulphuric

this
to

cork,

thermometer

extending

flask.

Fit

c.c.

thermometer,

the

the

165

connecting

funnel
of

into

vapor.

flask

tube

holds

dropping

mix

of alcohol.

bent

the

alcohol

form

c.c.

another

is for

immersed
to

admit

is to

alcohol.

ethyl

210

holes, into the mouth

three

One

flask

liter Jena

with

H2SO4

pierced with

the

chloroform

this is done:

Experiment.

in

when

following experiment

The

an

properly

sulphuric ether.

ethylsulphuric acid

flask.

as

sulphuric acid in its production,

called

it, ethyl alcohol

when

safe

in certain

it is sometimes

heated

extensively used

is liberated

mixed

for

solvent

reasonably

Heat

are

is

Ether

acid
to

alcohol, which

to the

all

bottom
is

of

ready,

134

ORGANIC

the

place

flask

condenser.

Heat

use

until

rapidly
the

of

alcohol

from

with

connect

receiving flask in

the

which

the

the

funnel,

in

Run

process.
or

the
cold

126).
has

be
very

from

vapor

p.

it must

point

acid

ethylsulphuric

the

140", at

of

rest

and

adapter (cf.ethyl bromide,

an

temperature
for

sand-bath

Submerge

and

bath

on

CHEMISTRY

the

kept
little

alcohol

"

flask.

At

vapor

diminishes,

centimeters
the

at

vicinity
been
in

cork
a

flames

Keep

of

into

it with

dilute

Redistill

tightly.

The

reaction

NaOH

water,

day

tion
solusmall
the

pour

chloride, and

calcium

after

distillate

several

with

the

the

or

following equations

using

so,

will

explain

CaHsOH
(Ethyl

CaHsOH

off

flask, add

dry

Watch

sufficient

draw

water;

from

away

When

separating funnel, then

cubic

few

receiving flask.

the

of

water-bath.

the

time.

of ether

amount

alcohol,

more

secured, wash

portions
ether

add

constantly.

apparatus
has

the

intervals, i.e.,when

-hH2S04

C2H5

alcohol)

HSO4

+H2O,

(Ethylsulphuric

HSO4: C2H5=

"

C2H5+H2SO4.

O"

C2H5"

"

acid)

"

(Ether)

Mixed

linked

to

ether, CH3
synthetic
for

contain

ethers

the
"

same

"

process

"

different

atom,

oxygen

C2H5.

They

similar

simple ethers, thus

CHs

two

to

may

that

organic radicles
as

be

methyl
formed

described

0|Na+IiC2H5
=

CH3"

0"

C2H5

+NaL

ethyl

by
above

135

ETHERS

It

methyl
of

is

interesting
ethyl

dimethyl

diethyl
The

boiling

ether,
ethers
with

ether

to

that

note

(11")

is

(C2H5)20
are

alkali

very

or

between

intermediate

(CH3)20

ether,

of

boiUng-point

the

(-23.6"),

and

that
that

of

(34.6").
stable,
dilute

not

acid.

being

affected

by

CHAPTER

ALCOHOLS

PRIMARY

the

Among

monacid

the

alcohol

carbon

Alcohols,

an

by

however,

oxygen

the

following

(1)

formula

of

ber
num-

of

atom

an

in

of

carbons.
hydro-

the

alcohol

primary
be

obtained
That

hydrocarbons.
is

hydroxyl

proved

+H|C1
alcohol)

(Methyl

(cf.

of

same

cannot

the

present

reactions

OH

Alcohols
of

is

atom

CH3

the

oxides

hydroxides.

are

oxidation

the

formula

the

attaching

not

are

alkyl hydroxide'.
direct

from

pounds
com-

C^H2^+20.

They
is

derived

by

organic

empirical

containing

atoms,

thus:

oxygen,

be

can

hydrocarbon

paraflSn
of

The

alcohols.

the

are

of

classes

important

most

CH3CI

(Methyl

KOH+Hia

+HOH

chloride)

KCl+HOH),

3CH30H+PCl3=3CH3Cl+P(OH)3

(2)

(Phosphorus
trichloride)

(cf.

(Phosphorous
acid)

3HOH+PCl3=3HCl+P(OH)3),

CH30H+H2S04=CH3HS04+HOH

(3)

(cf.
(4) CH3OH

K0H+H2S04=KHS04+H0H).
+ CH3

"

(Acetic

(cf.

KOH

+CH3-

COOH

acid)

CH3

"

COO

(Methyl

COOH

=CH3136

"

CH3

+ HOH

acetate)

COOK

+HOH).

by

137

ALCOHOLS

PRIMARY

striking similarity between

The

and

alcohol

the

and

KOH

is clearly shown

H2O)

reaction

of

alcohols

shows

further

of the

of the

three

other

that

+Na

HOH

+Na

that

+H

mcthylate)

NaOH

with

CHsONa
(Sodium

(cf

sodium

linking from

atoms

reactions.

particular hydrogen

one

hydrogen

CH3OH

and

different

these

by

potassium

has

latter

of

reactions

typical of all hydroxides (viz.,

most

The

atom

the

+H)

Finally, the
doubt

by

by

action

the

of

structure

of
"

its

synthesis from

strong hydroxide

.....

bases;

not

are

It is to

be

of

atom

with

few

is reactive,being
The

heat

that

of

of
the

just what
in the
^The
atoms

alcohol
higher
in the

stable

of

should

into

an

expect

hand,

by

all.

hydroxyl
pound;
com-

into

enters

the

alcohol

reagents.

many

alcohol

is less than
This

hydrocarbon.
since

at

the

of
and

in

hydrogen

one

whereas

affected

corresponding

we

of

behavior

reagents,

combustion

other

slightly,if

molecule

very

readily

dissolved

the

on

change

chemical

the

paraffin is

the
reaction

the

that

bases, because

when

very

hydrocarbon

alters

greatly

ionize

they

noted

the

ions

Alcohols,

172).

p.

halide

strong

are

hydroxyl

many

(see

water

alkyl

an

=CH30H+KC1.

hydroxides

furnish

they

yond
be-

is settled

-."".

CHaCl+KOH

Inorganic

alcohol

an

there

is

is oxygen

molecule.
alcohols

alcohol

the

are
more

hardly

affected,

vigorous

the

is the

fewer

sodium

the

action.

138

ORGANIC

CHEMISTRY

MONACID

These

to

the

alcohol

has

wood

p.

162).

alcohol.

distillation

left

ofif from

alcohol

methyl

from

after

of

ordinary

fermented

formed

by

beet

with
If

ammonia

water,

chloride, CaCb
affected

Treatment

and

distillation

be

1|^

is 0.7931

oxalic

water

the

is

not

is driven

alcohol

free,

purification.

boils at 66" and

(at

calcium

this

acetone

the

The

alcohol.

with

formed;

sets

can

by boihng

methyl

pure

treated
is

crys-

acid.

decomposed

the
and

(CH3)2C204,

100", but

completes

alcohol

it is

its

gravity
specific

0.7913).

Its

melt-

15.6

-93.9".

to

with

Methyl

ing-point

be

-40113011

by heating

off.

oxalate

yielding

alcohol

crude

the

spirits. A

with

then

can

free

acid, acetone,

wood

treatment

purified crystals

suffice to

not

acetic

crude

methyl

compound,

talhne

the

of

constituents

other

does

distillation

Fractional

at

(see

destructive
residue

produced

molasses.

sugar

be

distillate

called

distilled

been

the

is therefore

the

is

the

carbinol), HCH2OH

of wood

by

crease
regular in-

series.

distillation

secured

vinasse, which
alcohol

of the

from

is obtained

ning
begin-

boiling-point from

(methanol,

alcohol

also

and

of

group

series

is

There

highest members

destructive

is

It

homologous

an

specificgravity

crude

The

important

most

of

CH3OH,
the

ALCOHOLS,

alcohol.

methyl

Methyl

by

form

They

with

or

the

comprise

alcohols.

lowest

PRIMARY

that
higher than
Electrolytes dissolved
is

of
in

ethyl alcohol,
methyl

alcohol

and

molecule,
has

theory
alcohol

these

of formic

acid

Another

theory

of fruit juices
or

of malted

grain,

is inhibited
about
from

17%
2 to

8%
wines

alcohol.

Brandy

whiskey by
these

distillation

contain

40

disagreeable and

oil, may

be

pleasant

taste

present

in

distilling100
of

c.c.

when

water);

the

into
odor.

hquor

can

of the
100

The

of specificgravities (see
Commercial

Preparation.
the

cheapest

ground

or

forms

mashed

of wine,

which

by-products,

fusel-

for instance

of

compounds
of

amoimt

of

alcohol

with

distillate

of

liquors

Many

by

50

c.c.

been

has

The

is determined.

by referring to tables

Appendix,

p.

alcohol

of starch, potato
raw

adding

by

grain; both

liquor (diluted
c.c.

15%.

8 to

readily estimated

be

is found

of alcohol

contain

ethereal

collected, its specific gravity

percentage

liquors

of alcohol
that

converted

reaches

by distillation

injurious, as

and

content

of fermented

60%

to

grapes,

tion
Fermenta-

these

from

is obtained

from

contain

Wines

made

are

fermentation

barley.

Malt

volume).

has

theory

in its favor*

wine

alcohol

the

require aging in order

are

from

of alcohol.

Stronger

No

by

as

termedia
the first in-

as

evidence

sugar,

beer

as

when

(by

acid

obtained

are

containing

when

mixture).

reaction

pyruvic

experimental

beverages

produce

not

equimolecular

an

of yeast action.

product
Alcoholic

from

free in the

advances

yet sufficient

will

acetaldehyde (even

and

set

tenanced
discoun-

is rather

yeast

acid, nor

gradually

are

that

fact

lactic

and

proved,

This

results.

alcohol

ethyl

been
the

from

mixture

thus

not

by

as

CHEMISTRY

ORGANIC

140

material

445).
is

made

from

or

corn.

The

is heated

until

the

starch

is

and

contains

the

into

mixture

The

maltose, and,

sugar

furnishes

yeast

also

ferments

be

can

grinding the
the

is

diluted,

very

high

The
called

called

obtained

by this

crude

animal

alcohol
The

Malt

certain

300

yeast

no

from

yeast

and

is

cells

ferments

can

Ferments

(95%)

(90%

This
.

obtained

by

are

13%)

over

is distilled

fractionating column.

alcohol) is filtered through

removes

product

being ordinary
some

obtainable
contains

impm-ities.

many

is apt to contain

alcohol

fractionation

(not

of fermentation

redistilled,the

stage.

to

extract

dextrose

bacteria.

containing

charcoal, which

is

the

into

solution

process

strongest

careful

(up

pressure

intracellular

certain

distillate

is then

by

sand, subjecting

quartz

extract

alcoholic

apparatus

an

cells

enzymes.

weak

The

this

from

These

yeast

filtrate contains

Similar

zymase.

obtained

often

in

trose
dex-

alcohol.

into

ferment

the

maltose

inverts

changes dextrose

dioxide.

finally filtering
This

cules,
mole-

the

decomposes

from

verts
in-

splits or

dextrose

two

carbon

fine

and

it

that

with

through porcelain.
cells, but

into

extracted

to

atmospheres),

that

starch

of about

extent

ferment

and

latter

mass

ferment

alcohol

into

It

Malt

changes

the

to

60-62".

solution

molecule

maltose

and

The

at

sugar

The

dextrin.

the

in

kept

yeast is added.

and

be

is

ferment, diastdse, which

into

20%,

the

cooling malt

After

cooked.

thoroughly

is added

141

ALCOHOLS

PRIMARY

by
4.5%

allowing barley

to

aldehyde.
the

by

most

weight

germinate

to

142

CHEMISTRY

ORGANIC

of

Commercial

water.

one-half

about

of

digesting alcohol

quick-lime and

with

is secured

and

More

but

production,

alcohol

used,

material

is the

bushel

one

Europe

of

exposed

when

it takes
the

to

used

from
facture
manu-

material

is

gallon.

per

is almost

alcohol

Absolute

air.

of

moisture

up

for

starch

corn

raw

five cents

absolute

Chemically

because

unknown,

sodium

are

country

of the

cost

low, less than

Properties.

absolute

of the process

cost

of the

exclusive

distilling

metallic

potatoes

by

gallons being secured

The

com.

said to be very

with

in this

2.7

then

nearly

by treating

distilling. In

contains

It is obtained

of water.

1%

(CaO+H20=Ca(OH)2).
alcohol

alcohol

absolute

rapidly

so

alcohol

has

15 56"

of 0.79365

specificgravity
and

boils

it boils

less odor

much

by weight, and
Alcohol

Alcohol

has

with
volume

in

wood
added

with

It

render

or

is

alcoholic

of

compounds

denatured

alcohol
to

colorless

effect

or

Commercial

alcohol

service
flame.
and
an

to

99%
15".

at

the

as

lowest

78.15"

at

solvent.

When

mixed

contraction

of

intoxicant;

the

Hquors, however,
besides

the

is alcohol

substances

nauseous

it unfit

has

preparation,

is of great

part to other

Methylated

alcohol

any

observed.

are

detrimental
due

by weight

rise of temperature

water,

It has

specificgravity of 0.798

Alcohol
burns

pressure

-112".

at

alcohol.

coramon

containing 95.57%

mm.

mm.

{dehydrated alcohol) contains

boiling-point of
760

solidifies

It

than

alcohol

absolute

at
-^y

(corrected) (at 734

77.7").

at

0.79357
q,

78.3"

at

15"

'

at

drink.

alcohol.
to

have
In

is

the

which
been
United

PRIMARY

States

parts of wood

10

benzine,
of

parts

crude

used.

are

alcohol

pyridine

100

can

be

parts of

or

alcohol

per

alcohol

Such

and

of wood

else 2 parts

or

143

ALCOHOLS

and
of

parts

alcohol,

duty-free

sold

or

in

countries.

many

Experiment.
500

crumbled

extend

flask, pass

or

into

down

the

baryta water,
the

soda-lime.

of

tower

which

after

without.

from

apparatus

copious

bent

second

to

as

so

some

tube

few

or

the

enter

cannot

days,
is

BaCOs

of

precipitate

in its

hole

with

it stand

Let

tightly fits

just reaching the

CO2

put
some

containing

is connected
Thus

add

that

bottle

tip of the tube

bottle

baryta

flask

or

glass tube

small

cork

latter; through

of the

surface
cork

Through

yeast.

bottle

large bottle

glucose solution, and

10%

of

c.c.

the

Into

obtained.
with

Experiments
in

test-tube

stand

(with absolute

alcohol

(2) Take
being

100-c.c.

c.c.

When

52

c.c.

at

to

of alcohol

temperature

20", and

instead

let

it

becomes

CUSO4

blue

no

c.c.

color

appears).

place.

graduate, and

cool
96.3

takes

the

10

and

CUSO4

anhydrous
hour;

what

(1) Shake

alcohol.

one

Explain
each

with

(corked)

bluish

95%

of 100

note

read

and
of

the

48

of water,

c.c.

20", mix
maximum

off the

in

them

ture,
tempera-

(about

volume

c.c).

miscible

mixed
a
liquids are
volume
is generally noticed, usually
(sometimes
an
increase). Heat
may
absorbed
or
given off.

change
a

in

decrease

be

either

144

CHEMISTRY

ORGANIC

(3) Put
as

10

bottom

acid.

of alcohol

c.c.

layer

Throw

in

5-

the

the

liquid in

acid

(probably

oxidation

Propyl

of

due

to

is

alcohol
"

CH2

of

fire will

occur

alcohol

in

and

intense

of alcohol).
alcohol

primary

sium
crystalsof potas-

production, and

ozone

add

sulphuric

of the

of contact

zone

derivative

formula, CH3

of small

Flashes

permanganate.

test-tube, and

of concentrated

c.c.

number

in

having

the

CH2OH.

"

is CH3CH2-CH2CH20H.

Normal

butyl alcohol

Primary

isobutyl alcohol

is CH3

"

CH

"

CH2OH.

CHs
with

As

hydrocarbons

the

lowers

"

CH2

"

CH2

"

CH2

isoamyl alcohol, called

Primary
CH

is

amyl alcohol
CH3

"

chain

boiling-point.

Normal

CH3

of the

branching

the

"

CH2

"

"

CH2OH.

isobutyl carbinol,

; this is the

CH2OH

main

is

constituent

CH3
of fermentation
alcohols

alcohol.

amyl

contained

are

in

Both

fusel-oil

of

these

and

in

liquors, especially recently distilled

whiskey.
the

same

There

are

structural

three

and

brandy

alcohols

and

having

/H

CH3CH2/
chemical

certain

formula,
CHav

Their

isoamyl

amyl

\CH2OH.

physical properties

except that their action

on

are

identical,

polarized lightis different.

One

the

it to

rotates

the
inactive

of

right

third

does

not

four

are

and

normal

is

There

is

is called

and

also

hols;
alco-

amyl

amyl

another

alcohol

group,

/CH3

\CH2OH.

secondary

isoamyl

tertiary

CH3\

amyl

alcohols,

two

alcohols.

isoamyl

two

active

rotation

primary

CH3/
There

the

cause

CH3\

left, another

the

to

are

There

the

containing

light

these

"

alcohol.^

amyl

alcohol

beam

the

rotates

145

ALCOHOLS

PRIMARY

alcohol

/OH

)"C"(
\CH2

CH3/
which

used

been

has

isobutyl

alcohol,

optically

active
of

Solubility
render

carbon

readily,

of
For

primary

the

isoamyl
The

name

the

atoms

and

amyl

alcohol

discussion

of

parts

of

in

dissolve

this

form

of

the

the

alcohol

with
and

parts

isomerism,

see

fewer

alcohol.

the
mix

100

tends

group

water;

alcohols

butyl

and

alcohol.

soluble

more

propyl

30

in

primary

alcohol

hydroxyl

soluble

compound

alcohol,

isoamyl

alcohols.

while

propyl

(primary)

ethyl

Methyl,

parts

under

hypnotic

normal

contains

oil

Fusel

the

hydrate.

amylene

to

as

CH3,

"

water

only
of

p.

water.

214.

CHAPTER

XI

ALDEHYDES

If
is

alcohol

primary

be

product

aldehyde:

an

CH3

"

CH2OH
of

Two

atoms

the

alcohol

+0

indicated

follows

CH3

"

but,

atom,
such

be

is to

contains

no

noticed

chloride,

be

the

place

chlorine

one

CH3

rule

in

"

CH

the

to

organic

unstable

that

to

bon
car-

same

compounds,

persist

"

There

hydrate,

CH2OH
are

and

H2O

be

can

other

any

CHO

"

mentally.
experi-

proved

hydroxyl-contain-

treated

with

of

hydroxyl

each

group

phosphorus
group

pentais taken

atom:

+PC16
three

mesoxalic

or

aldehyde

the

This

hydroxyl.

compound

by

accurately

more

CH3

attached

is too

If alcohol

ing

al{cohol)

name

is

from

off.

splits
It

removed

the

+0

is the

combination

been

CH2OH

as

+H2O.

reaction

become

hydroxyls

Two

hence

The

CHO

"

have

molecule,

as

CH3

hydrogen

dehyd{rogenatus).

first

the

oxidized,

CH3

well-known
and

CH2CI

exceptions

glyoxylic
146

acid.

+POCI3
to

this

+HC1.
rule

"

chloral

148

ORGANIC

CHEMISTRY

(3) Phenylhydrazine
by

removing

with

combine

can

of

carbonyl

the

hyde
alde-

an

group,

hydrazone being formed.

(4) Aldehydes
violet-red

color

of fuchsin

which

acid.

This

to

has

is due

chloral

in the

aldehyde

character

strong

solution.

40%

bUng

air

about

50";

passed through
asbestos:
also

in

which

not

the

used

has

polymer

multiple

of
same

Thus

(H

"

is

air

and

bub-

kept

at

is.

vapor

containing platinized
It
alcohol

part
and

disinfection

in

is

special

limited,

of air is

occurs;

for

is

formalin

prepared by

of

It

so

that

of the

alcohol

escapes.

This
is

of rooms,

but

form

polymers.

satisfactory.
has

Formaldehyde

the

supply

formaldehyde

to

be

can

very

has

tests.

gas.

alcohol, which
tube

combustion

oxidized

is

the
of the

H.CH20H+0=H.CHO+H20.

incomplete
lamp

is

group

for other

HCHO,

mixture

heated

the influence

produced by burning methyl

lamp
is

the

of

case

compounds

Commercial

methyl

then

the

of these

Formaldehyde

through

Dextrose

in

as

densation
con-

(methanal),
in water.

of

formation

under

appears

solution

by sulphurous

(and the heat) used

Formaldehyde
soluble

the

cause

contain

not

of both

case

reagents

is very

to

because,

test

hydrate, it does

however,

to

(see acetaldehyde)

give this

not

added

decolorized

been

reaction

hydrate)

when

appear

products
does

chloral

(except

CH0)3.

that

tendency

molecular
of

the

to

weight which

is

original substance,

an

even

and

it

ter.
composition as the lat(trioxymethylene) is
paraformaldehyde

percentage

Its

graphic representation is

149

ALDEHYDES

O
I

0"

/C"

Cv

Paraformaldehyde
which,
candles

or

With

for

is

(paraform)
is sold

It

the

in

white

stance,
sub-

is converted

heated,

being

on

formaldehyde.

tablets

of

form

into

disinfectingpurposes.
does

formaldehyde

ammonia,

do

form

not

other

simple

addition

compound

as

but

complex

substance,

hexamethylentetramine

(see

p.

264).
is

Formaldehyde
used

therefore

extensively

It is used

It is very
membranes.

efficient

an

either

as

irritatingto

substances, and
prepare
converts

for

tissues
a

solution

gas

the

solution

dilute

The

germicide,

for

the

is

and

disinfecting
or

and

eyes

also

is
poses.
pur-

in dilute

tion.
solu-

mucous

hardens

buminou
al-

used

consequently

histological
of

aldehydes,

to

examination.

gelatin into

produced

by

hard

It

insoluble

mass.

Glutol

is

substance

formaldehyde
dry powder
surfaces.
of slow

gelatin.

on

it is used
It is said

liberation

of

as

In

the

the

action

form

surgical dressing

of

of
for

raw

antisepticbecause
formaldehyde.

to

act

as

an

150

(1)

Experiments.
concentrated

the

with

; with

containing

solution

as

H2SO4.

in

(2) Set

containing
until

add

drops

of

in about
:

maldehyd
for-

5000

mixing

between

the

evaporating

dish

several

days

forms

zone

of

drops of

few

top layer, avoiding

It

to

the

gas

secured,

volatiUzes

add

10

Uttle

away

of milk

acid

Heat

the

and

hand

the

(4) Add

containing

one

the

over

mixture
of

drops

Make

easily slip into

until

red

hot

this several

Cool

of

layer
red

5
zone

produced
is used

alcohol.

as

test

for

5%

c.c.

violet

dish

the

of

small

this

with

At

c.c.

the

wire

solution.

peat
Re1

drop

pipette

concentrated

Why

procedure?

of
wire

copper

liquid,add

develops.

by

to

Heat

the

in

color.

spiral of
tube.

ferric

motion.

alcohol

solution, and

resorcinol

acid.

it into

plunge
times.

of

rotary

the

dish

of concentrated

drop

methyl

will

and

c.c.

acquires

test-tube.

bottom

nostrils,as

or

flame, holding the

maintaining

that

as

careful

Be

eyes

test-

large evaporating

10

in

0.5%

the

and

water

odor.

the

in

formaldehyde

chloride.

90"

completely, passing

fuiiies into

c.c.

hydrochloric

about

dry

of it in

some

irritating.

is very
To

is obtained.
a

heat

Note

gas.

get strong

(3)

Leave

solid, paraformaldehyde,

formaldehyde
not

an

formalin.

of

c.c.

this is

tube.

desiccator

white

When

in

centimeters

pipette run

violet

cubic

layers.

two

of

few

test-tube

solution

milk

of

c.c.

To

in

H2SO4

ferric chloride
5

CHEMISTRY

ORGANIC

run

phuric
sul-

maldehyd
is forThis

quantities of methyl

151

ALDEHYDES

(ethanal, aldehyde),

Acetaldehyde
be

obtained

by

the

by

heated

in

similar

oxidation

The

platinum.

the

in

and

has

paraldehyde,
metaldehyde,

soUd.
It

is

structural

their

(see

p.

molecules
"

forming
chloride

be

made

"

has
and

starch
and

made
the

that

100

from

influence

Experiments.
flask

suggested

synthesized

be

under

CH"

sugar

by plants
of

c.c.

from

the
to

together,
Zinc

aldoL

^O

C^H

CH2"
the

is due

production

and

CO2

the

of lime-water

Preparation.
30

(see

of

sugar

condensation
p.

(1) Mix
c.c.

latter

H2O.

by

of

condensation

to

formaldehyde,

and

in

hypnotic.

to fuse

formaldehyde

of water

ference
dif-

CH3"

-^

polymerization

being
can

been

is

^0

It

difference

in relation

product,

O"

2CH3"

formula

the

group

will effect this change

C^H

the

Paraldehyde
can

and

124",

difference

CH3

condensation

is,

ers,
polym-

stereomeric

at

20".

the

at

that

is

214), that
of

boils

at

into

have

supposed

the rest of the molecule.

Aldehyde

of 0.780

Both

formulae

in space

arrangement

described

as

boiling

and

acid

sulphuric

changed

liquid

(CHs -0110)3.
in

be

can

generally

Acetaldehyde

specificgravity

Acetaldehyde

is

dichromate,

below.

experiment

the

20.8"

potassium

or

of

induced

vapor,

oxidation

use

can

formaldehyde

as

ethyl alcohol

of

effected,however, by
sodium

manner

CHa-CHO,

232).
in

C.P.

large

H2SO4.

152

Fit

cork

two

with

condenser,

funnel.
about

and

ice-water.

Now

boiling-point.
slow

(100

stream,

add

through
of

dissolved

of dichromate

gm.

Fig.

mixed

and
flame

as

If

stream.

the

with

added,

redistill

through

large

the

as

In

funnel.

in 100

is

Connect

of water,

c.c.

Remove

well

making

in

the

started.

the
to

the

solution

Save

the

the

again

has

aldehyde
the

30", using

been

portion

of

tests

condenser

diagram.

condenser

If

slacken

distilling,heat

redistilling tilt
heated

the

dichromate

sodium

all of the

for

in

funnel, in

the

alcohol).

ceases

shown

it water

of

distillate.

distillate

with

to

gauze

uncondensed,

When

nel
fun-

20.

distillation

aldehyde

below.

upward,

c.c.

through

flame.

crude

given

53
as

soon

passes

vapor

the

with

wire

over

ping
drop-

flask

receiving

flask

solution

for

Connect

liquid.
the

tube

bent

dropping

tip of the

place

the

Heat

other

the

the

above

cm.

condenser,

the

the

Have

for the

holes, one

having

connecting

CHEMISTRY

ORGANIC

Circulate
reservoir

with

or

drop-

153

ALDEHYDES

ping funnel, which

wash-bottle.

dips into the ether

Put

25

of

c.c.

dry

in the

ether

first

into

each
I

wash-bottle.

aldehyde

of the

passes

into

aldehyde
the ether

mixture.

in

bath

placed

bubble

it

ammonia

gas

flask),which

has

into

dry.

be

the

of water,

and

crystals in

obliquely,

then

bottom

seal with

NaaCraOz

+4H2SO4

times

distilling.

Put

and

up,

sealing
30

fill with

ether,

pure

adding 3^

bottle, hold

been

will

ammonia

product

cured
(se-

soda-lime.

dissolving some

sample

and

cork

by

freezing-

crystals with

this

From

obtained

H2SO4,

the

of

tower

crystals of aldehyde

equal weight

50%

Filter, wash

let them
may

an

in

fer
trans-

over,

in

it.

When

is

passing through

finally appear.
and

of ice- water.

beaker, which

of white

mass

absorbs

passed

have

at

will, only

water

all

Now

by

and

ether, which

by heating NH4OH
dried

condense

not

the

to

seems

to

will

alcohol

bottles

the ether

Keep

aldehyde

most

while

30",

the

As

hyde
alde-

of it in
as

much
of

some

the

bottle

anmionia

gas;

wax.

+Cr2(S04)3

+Na2S04

+4H2O,
CH3

CHs

"

CH2OH

CHO

+0

+NH3

CH3

CH3

"

CHO

+H2O,

Cf"

OH.

^NH2
(2) Aldehyde
distillate

to

test-tube; boil
(6) Add
centimeters

tests,
c.c.

of dilute

Uttle

of the

Fehling's solution

CU2O

is

small

portion

anomoniacal

AgN03

until

another
of

(a) Add

crude
in

precipitated.
to

few

solution

cubic
in

154

CHEMISTRY

ORGANIC

clean

perfectly

of silver is

mirror

(c)
add

To

solution

of

Add

convenient

almost

solution

Schiff's

appears.

and

chlorine

of

is very

the

is
is

It

into

gas

Aldehyde

days.

products

shake,

reagent

acetaldehyde.

of

by passing dried
several

orized.
decol-

for this test.^

use

derivative

for

until

(trichloraldehyde),CCls-CHO,

Chloral

(fuchsin) solution

acid

aldehyde

some

to

rosaniline

sulphurous

color

violet-red

gradually.

deposited.

of dilute

c.c.

heat

and

test-tube;

HCl

chlorination.

produced

absolute

and

alcohol
the

are

The

ine
chlor-

final

first

product

/OC2H5
chloral

is

alcoholate,

is liberated

from

Chloral

is

alcohol.

with

by the action

oily Uquid, boiUng

an

of

specificgravity

Chloral

at

it

chloral

it forms

water

1.512

When

reactions.

aldehyde
with

this

tion
addi-

an

Chloral

of concentrated

acid.

sulphuric

chloral

of

compound

CCl3-CH"^

20".

and

It

ing
hav-

gives

into

comes

the

contact

hydrate crystals.

CClaCf-OH,

hydrate,

97.7"

at

is

believed

to

"

have

considered
with
1

an

the

let it stand
of water

reagent

and

until

general
for

in

10

c.c.
or

It

the

SO2

of water.

Dilute

bottle well

be

typical

gas

Cork

may

aldehyde

believing that

colorless.

dark-colored

of

carbon

same

rule.

by saturating with

light yellow

keep in

the

to

compound

reason

of rosaniline

gm.

the

addition
One

water.

Prepare

of 2.2

to

contrary

atom,

attached

hydroxyls

two

solution

tightly and
with

200

stoppered.

c.c.

156

CHEMISTRY

ORGANIC

the

finally chloral

air, until

crystals

hydrate

are

formed.

Chloral

have

been

synthetized
which

the

tendency

the

circulation.

Such

of chloral

derivatives

Many

Substitutes.

the

with

chloral

of

object

hydrate

has

correcting
to

depress

are:

Butyl-chloral hydrate (croton chloral),

CH3

"

CHCl

Chloralformamide,

"

CCI2

-^CHCOH)

2.

(chloralamide)

/OH

is

of chloral

combination

hydrate with

formamide.

HCONH2.

(chloral+ glucose), CgHnClaOe.

Chloralose

Hypnal

(chloral+ antipyrin)

Dormiol

(chloral condensed

with

amylene

Isopral, trichlorisopropylalcohol,

yOH

"
.

"

hydrate)

CHAPTER

ACIDS

FATTY

AND

XII

SALTS.

ETHEREAL

OBSERVATIONS

PHYSICAL

IN

FURTHER

CHEMISTRY

ACIDS

Acids

defined

are

dissolved

in

weak

acids

acids

method

by

is

which,
such

67).

Most

they

are

acetic

HCN

of

acid)

production

only

acids

+2H2O

the

because

common

They

series
are

displaceable

substance
from

means

to

the

be

(see

ment
experi-

formate)

COONH4.

"

acetate)

this

at

point

fats

of acids

hydrogen
to

the

introducing

H2O

hydrolyzed,

the

original substance.
157

called

are

contain

some

(in combination

monobasic,

conform

They

Hydrolysis

different

studied

this

of

group.

contain

COONH4,

CH3

be

to

acids,

one

(see

carboxylic

of

(Ammonium

glycerol).

acids

+2H2O

CH3CN

members

therefore

cyanide

(Ammonium

fatty

organic

acids

organic

to

as

way

inorganic

of

of

hydrolysis

under

The

when

group.

general

with

majority

carboxyl

the

p.

feebly;

compared

The

in

(see

but

as

173).

p.

ions

dissociate

acids

dissociate

water,

hydrogen

furnish

substances

as

result

i.e., they
in

atom

general
into

being

the
a

with

contain
the

acid

formula^
molecule

product

of

quite

158

CHEMISTRY

ORGANIC

They

C"H2n02.
of

aldehydes

they

end

dation
oxi-

alcohol

methyl

by oxidation

obtained

be

can

the

of

products

alcohols, of the

primary

series, since

the

are

of

H.CHO+0=H.COOH.
The

OH

the

by

of carboxyl

reaction

be

can

(see

PCI3

with

proved

be

to

and

136

pp.

hydroxyl
146),

thus:

3CH3

"

+PCI3

COOH

It would

be

the formic

acid

unexplained

some

of the

true

acids

lower

an

series

similar

the

the

For

atoms.

is not

contrary

of carbon
than

steadily

increase

statement

on

acids

of

leading.
fatty is mis-

of carbon

number

odd

+H3PO3.

term

acids

number

melting-point

less carbon

atoms

acid

next

the
have

having

atom.

(methanoic

acid

Formic

of these

reason

COCl

the

melting-points, but

having

each
one

the

call this

to

series, since

in

increase

with

desirable

boiUng-points

The

3CH3

acid), H-COOH,

is

liquid.
(1)

It

be

can

The

CHO
acid

by oxidation

peroxide

by hydrogen
H

made

+H2O2

+KOH

then

can

in alkaline

be liberated

of formaldehyde
solution:

COOK
from

+2H2O.
the potassium

formate.

(2) Moist
220", forming

CO

is absorbed

sodium
CO

+NaOH

by soda-lime

formate:
=

"

GOONa.

at

190"-

ACIDS

F4TTY

(3) Moist

AND

CO2

bicarbonate

in

coming

forms

potassium

ETHEREAL

potassium

159

SALTS

with

contact

formate

and

metallic

potassium

2K+2CO2+H2O

(4) Oxalic

=HC00K+KHC03.

acid

when

decomposes

heated

to formic

with

acid

glycerol (glycerine)

and

carbon

dioxide

(see exp.).
Formic

acid

nettles.

It

appUed
it

solidifies

skin.

at

8.3".

Its

strong

reducing

red

Formic

low

the

structural

metal
H

formula,

the

aldehyde
being

carbonyl
carbon
than

and

dioxide
acetic

sulphuric
carbon

acid

it is

monoxide

Into

treated

half -liter

an

acid.
its bulb

bath.

add

hour);
Suspend

is in the
Connect

has
gm.

thermometer

liquid.
with

full

it

con-

acid

It

oxidizes

with

group,
to

acid

stronger

concentrated
evolution

of

3).

flask

50

The

the

with

decomposed,

glycerol (which
for

is

formic

(1) Prepare
a

mercury

that

both.
It

(see exp.

Experiments.

water.

When

acid.

at

It is

and

shows

to

common

20".

at

overlapping

group

melts

(see exp.).

0"

101";

at

and

silver

C=0,

"

stinging

boils

temperature,

agent, reducing

to

in

blistei:swhen

acid

specific gravity is 1.2187

compounds

tains

ants, and

irritant, causing

is very
the

to

in

occurs

Heat

put
been
of

50

acid

as

lows:
fol-

c.c.

of

hydrous
an-

heated

at

170"

crystallized oxalic
in

the

cork,

gradually

condenser.

on

Carbon

so
a

that
sand-

dioxide

160

is

ORGANIC

and

evolved,

115"

reaches
add

150".

If

to

(p. 302)
acid

Dilute

of 200

has
with

been

from

lead

acid

copper

until

lead

Heat

is

about

again

overheated,

acid

acrolein

able
disagree-

very

of the

the meantime

manner,

distillate to

solution

and

hydroxide

the

To

evaporation.

proceed

as

rest

with

formic
When

the mixture.

longer dissolves, filter

no

and

hydroxide

lead

to half of the

Add

ide
hydrox-

copper

prepare

hydroxide, warming

up

distillate for formic

rest

solution.

nitrate

for slow

away

to

perature
tem-

slightly alkaline, diluting

similar

In

hydroxide

copper

the

prepared by treating CuS04

KOH

filtering.

the

In

c.c.

acid.

which

of the

When

mixture

the

is

produced,
some

below.

as

mixture

distill at about

to

liquid).

the

of oxalic

gm.

the

Test

volume

add

of

begins

150", cool

50

will be

gas.

acid

formic

(temperature

50", then

CHEMISTRY

and

of the
the

set

acid

copper

formate.

C3H5(OH)3

(COOH)2

(Glycerol)

acid)

(Oxalic

+H2O

C3H5(OH)20CHO

+CO2

(Monoformin
or
glyceryl
monoformate)

+H2O

C3H5(OH)20CHO

COOH

"

acid)

(Formic

(2)

Warm

gray

precipitate of

the

50", add

to

c.c.

Filter and

vigorously.
a

few

in

acid

formic

for

Test

+C3H5(OH)3.

boil

mercury

the

(Glycerol)

distillate
and

HgO,

filtrate

one

as

lows:
fol-

shake
minute

develops:

HgO+H.COOH=Hg+C02+H20.
(3) Into

acid; add

test-tube

slowly

put 3
c.c.

of

c.c.

of undiluted

H2SO4.

Cork

formic

quickly

FATTY

ACIDS

cork

through

with

tube

the

end

AND

which

which

of

centimeters

of dilute

test-tube.

The

of blood

to

vessel

alcohol

ways

yield

to

addition

the

in

producing

acetic

undergoes

no

open

attack

to

oxygen

an

acid.

the
The
it is

change;

transferring the

of

to

oxygen

alcohol.
alcohol

Pure

does

not

acid

when

dilute
This
of

itself

platinum

oxidized

contained

atmospheric

catalyticagent, merely

the

drop

various

are

be

may

alcohol, oxidizing it and

carbon-

to

by adding

laboratory,

to

the

causes

spongy

in another

cherry-red tint.

There

the

In

platinum

spongy

cubic

little distilled water.

acid.

acetic

few

changed

is made

ethyl alcohol

which

by

is

delivery-

solution

has

acid, CH3COOH.

Acetic

dip into

which

solution

haemoglobin

bent

haemoglobin

haemoglobin

161

SALTS

passes

is to

monoxide-haemoglobin,
The

ETHEREAL

exposed

alcoholic

this way

that

wine

too

from

life of

or

much

cider

time

consequently the above

process

This

is done

meet

air

by allowing

solution

of

commerce,
to be

has
to

pheric
atmos-

matter

It is in

vinegar.

would,

produce

to

the wine

into

air

matter.

{Mycoderma

organism.

to

if the

so

latter

converted

becomes

demands

to

the

Nitrogenous

this

the

vinegar

does

the

alcohol.

of wine

exposure

occupy

the

for

into acetic

nitrogenous
in

water

pure

platinum, transfers

spongy

the

to

oxygen

air, but

growth

derived

with

converted

contains

of the

microorganism

is necessary

the

to

solution

is because

diluted

become

spontaneously

aceti) which, like

Mere

alcohol

or

ever,
how-

sufficient
and

accelerated.

percolate slowly

162

ORGANIC

previously

shavings

of heat

amount

this

the

through

used

be

of air, which

alcoholic

for

frequently

the

glucose is added

should

solutions

in such

acid, besides

various

obtain

To

The

this

hard

known

as

is

low

temperature

(200") in

air

is excluded,

and

acid.

and

latter

This

the
the

acetic

distillation

second

and

evaporated;

then

freed

of

hydrochloric
which

is then

as

the

several

so

as

distilled.

to

acetic

alcohol

with
calcium

liberate

This

tarry

pyroligneous

contains

impurities by heating
acid

The

of

of these

neutralized

resulting

at

acid

substances,

methyl

and
the

is

which

from

besides

fraction, which

acid, being

what

is heated

mixtm*e

For

condensed.

organic

(0.5%) and

acetone

fractional

of

other

of acetic

to

retort

vapors

contains,

various

(4-10%),

5%

It

liquid known

watery

10%.

over

employed.

not

iron

resulting distillate consists

material

be

subjected

an

the

of alcohol

state, fermentation

pure

distillation.

destructive

may

bodies.

wood

is supplied.

fermenting

amount

liquids is,however,

purpose

in this

beer, and

by

about

aromatic
in

barrels

wine

or

not, however,

acid

acetic

of alcoholic

By

cider

resulting vinegars contain

The

the

process

obtained

these.

to

oxidation;

besides

e.g.,

alcohol

some

the

solutions

purpose,

slight

sides, and

for

oxygen

the

enter

in their

beech

mycoderma

vinegar.

strong

perforations

Other

the

generated during

is

sufficiencyof

way

in

currents

creates

with

sown

them

soaking

filled with

barrels

freely perforated

through

by

CHEMISTRY

ticularly
par-

(1-2%).
are

rated,
sepa-

most

of

quickUme
is

acetate

treated
acetic

with

acid,

first distillate contains

164

CHEMISTRY

ORGANIC

red;

boiling

on

colored

precipitate separates

out.

Filter; the filtrate is colorless.

(3) Cool
tube

by

the

crystals with

the
the

keeping

thermometer

at which

temperature

all its reactions

In

enabled

formula

to

acetic

acid, it

the structural

out

how

exactly

III

and

steps

we

have

C2H4O2.

the

of clearness

of

the

tabulated

illustrate

we

for

argument

will

statement

tical
practions
reac-

at

elementary

to

when

by the
with

(see Chapter
the

possess

pirical
em-

of the

formula,

structural

given before

be

an

analysis

comprehension

the

this

clearly just

working

are

by

of

our

they bear

is arrived

found

formula
sake

how

determination

weight

40),

p.

which,

in

the

ascribe

to

indicate
To

that

with

conforms

advantageous,

formula

suppose

molecular

For

us

substance

unknown
and

structural

chemist, let

formula.

the

Note

nearly all the

be

describing these reactions, to

of

motion.

chemists
may

mometer.
ther-

heat

Since,

perform

test-

melts.

acid

acetic

have

that

acid

the

shall

exercises, we

large

the
in

CH3COOH.

formula

structural

in

ice-water, stirring with

of

means

Melt

hand,

acid

glacial acetic

some

the

tailed
de-

discussion.

(1) C2H3O2
(2) C2H3O

(3) CHs"

production
(4) CHa"
to

CHsNa

"

acid.

H, proof: monobasic

"

OH,

(OC)"
of CH4
COO"

forming

proof: phosphorus
OH,

methyl

from

an

H,
an

group

chloride

tion.
reac-

proved

by

acetate.

proof:
acetate.

the

addition

of

CO2

ACIDS

FATTY

AND

the

(5) Synthetically by
from

cyanide

(1) In testing the

found

shall

have

with

monacid

salts

will

found

to

itself.

contain

In

the

from

the

that

atoms

formula

as

H.

"

be

may

anion

molecule,

four

structural

sociates
dis-

an

the

be
acid

acid

and

of the

C2H3O2

the

the

of

conveniently

employed

divided

to

tralize
neu-

into metallic

Pb(C2H302)2,

taste,

in medicine

with

lead

lead

acetate.

lead
on

oxide

the

In

account

nearly

sugar

of

astringent.

When

as

forms

In

insoluble

boiled

clear.

used

Lead

peculiar

lead.

distilled water

The

precipitating reagents

lead

and

acetates
are

It

is

it is mixed
as

carbonic

lead

for

acetate,

densely opalescent

the

of

of

presence

are

"

acetates

is known

compound

the

acetate

is formed.
are

an

potassium

of its possessing

is known
as

acetates

laboratory.

account

on

the

extensively

are

the

in

"

and

C2H302Na)

purposes

sweetish

acid

Sodium

(C2H3O2K;
various

acetic

of

salts

numerous.

very

that

that

one

will

organic.

Metallic

basic

in

others

are

than

hydrogen, H',

words,

hydroxides

less

atom

we

crystalline

analysis

remainder

the

other

the acid

used

of

substance

neutralizing it

on

indicate

represented

be

different

and

methyl

the cyanide

evaporating,

cation

this
on

which

one

by

represented
C2H30'2.

and

facts
a

of
and

acid,

it

obtained,

These

The

hydrolysis of

reaction

bases

be

into

must

of

up

acid.

acetic

to

165

SALTS

building

the

and

CH4,

ETHEREAL

basic

acid,
tions
solu-

carbonate

the
are

tions
solu-

able
valu-

extensively

166

ORGANIC

for this purpose

employed
is

acetate

well-known

these

All

acetates

the
Ethereal

that

for

example,
of

Acetic

importance

and

far

are

acid

acetic

in

another

By

same

of the

already

with

met

hydroxyl is, as
Thus,
the
=

in

when

or

3C2H30C1+H3P03.

alcohol

and

acetyl group.
an

of the

atoms

the

from

others.

show

that

connected

with

can

which

this
one

have

we

Tliis

replaceable by

seen,

acid

is treated

hydroxyl
as

in the

gens.
halo-

with

3C2H3O2H

ensues:

by CI, just

group
case

PCI3,
+PCI3
is evidently

of water

=3HC1+P(0H)3.

therefore

certain

C2H3O

pone
post-

must

under

we

The

3HOH+PCI3
We

able
consider-

alcohols, being hydroxyl.

acetic

substituted

radicle

shall

we

resulting group,

reaction

following

of

are

one

intimately

have

we

salts

considerably

be

the

atoms,

in the

as

organic acid

that

of reactions

must

atom

alcohol

replaceable,

I), or,

or

solving
dis-

acid.

is

numerous,

seen

differs

set

reagent.

till later.

have

we

the

ethereal

their consideration

Copper

studying

(OH)

group

salts, by
the

(2) So

I^

by halogens (CI, Br,

Since

as

in acetic

Acid.

hydroxyl

ethereal

C2H3O2.

is used

hydroxides

of

its

saw

biochemistry.

simply prepared by

most

are

Salts

in

salt and

metallic

we

case

CHEMISTRY

conditions
OH.
An

that

assume

be

acetic

caused

to

acid

split up

The

former

of these

acid

radical

of this kind

can

into

is called

the

is called

acyL
Acetyl chloride, C2H3OCI,

acid

chlorides

belongs

to

(or acyl halogenides) and

the
may

class
be

of

pre-

FATTY

ACIDS

the

by

pared

experiment

funnel

Put

by

25

the

As

condenser-tube
to

the

side

flask.

tube.

excluded

in

the

dropping
flask

receiver,
with

chloride

the

the

following

this

of

20

gm.

immersed

flask

to

con-

filtering flask

(see Fig. 21), and

filtering flask

of
in

to

the

bath

to

the

attach
calcium

carefully

acid

through

trichloride,

phosphorus
a

be

must

Add

manner.

dropping

21.

fit

cork
the

the

moisture

All

funnel

being

acid

glacial acetic

Suspend

Attach

cork.

tube

of

c.c.

Pio.

denser.

in

fractionating

167

SALTS

described

method

ExPBHiMENT.
into

ETHEREAL

AND

of

ice-water.

1G8

ORGANIC

When

it has

50".

Keep

the

evolution

under
active

the

at

temperature

of HCl

volatile

of water

presence

the

in the

it

the air it

In

as

presented
re-

=C2H300H+HC1.
is sufficient

being
be

bottles.)

hydroxy

of the

kept

in

this

cause

exposed

is

to

suffocating and

very

(It should

similarly

to

acetyl chloride

when

disagreeable.
reacts

to

acetyl chloride.

readily decomposes,

fumes, the fumes

The

bath

fluid, boiling at 51".

moisture

that

so

apparatus

atmospheric

reaction,

until

point

the

of

40"-

at

following equation:

CzHaOiCl+HlOH
The

this

water

distill the

colorless

bath

warm

(having the

ceases

Bring

boiling and

It is
the

cooled, substitute

hood).

CHEMISTRY

tightly stoppered
of alcohols

1 group

acetyl chloride, thus:

with

C2H30lCl+H:OC2H5=C2H300C2H5+HCl,
(Ethyl

"

the

ethereal

salt

the

alcohol

used

chloride

acetyl
detection

of

substance

invaluable

an

alcoholic

hydroxyl;

treated

acetate,

contains

acid

formed.

being
is

when

ethereal

an

acetic

of

acetate)

we

hydroxyl

this

On

account

for

reagent
if

we

conclude
other

find

that
the

than

of

radicle

the

that

acetyl chloride

with
may

the

with

the

forms

stance
sub-

hydroxyl

carboxyl.

of

To

Experiment.

slowly
Cool
the

the
odor

c.c.

of

neutralize

and

of

acetate.

alcohol

of absolute

acetyl chloride.

mixture

ethyl

c.c.

HCl
with

add

is evolved.

NaOH.

Note

FATTY

The

ACIDS

above

is found

this

of

acid

acetic

molecule

the

C2H3O

OH.

the

be

made

of water,

thus

can

fact

that

C2H3O/

being

with

the

of

loss of

acetic

anhydride
with

For

anhydride.

acetic

acetyl chloride

on

molecules

C2H30;OH
body

writing

corroboration

two

unite

to

C2H30v

purposes

by acting

Further

C2H3OOJH

resulting

practical

therefore,
justify our

"

in

169

SALTS

ETHEREAL

experiments

formula

the

AND

be

may

prepared
sodium

anhydrous

acetate, thus:
C2H300iNa

C2H30\^
"0+NaCl.
C2H3O/
^^

It is
to

C2H3O

CI

fluid

giving

it sinks

water,

the

hydroxyl

thereby

of

attached

C2H5IOH

bottom

the

of

in

into

acid

place of the

OC2H

other

attack

hydroxyl
becoming

groups

OH

Its

acid.

it to

causes

acetyl

Added

vessel, but

acetic

and

alcohols

the

of

one

vapor.

acetic

group

compounds,

suffocating

reconverted

re-form

to

the

to

gradually becomes
readiness

off

^,

thus:

group,

C2H5OOC2H3+C2H3OOH.
(Ethyl

I Ov

(Acetic acid)

acetate)

^OC2H3
Like

acetyl chloride, it
for

ascertaining whether

hydroxyl
such

groups

therefore

may

not

in

it contains

carboxyl, and
(see

p.

substance

if so,

206).

how

be

ployed
emtains
con-

many

170

ORGANIC

(3) There
radicle

remains

C2H3O

is

the

by
sodium

with

must

different

and

value
with

Further
the

methyl

the

be

C2HCI2O
The

"

ethereal
acetic
the

acids

the

acid

belong

by
the

to

+CI2

C2HCI2O

OH

+CI2

C2CI3O

0H+HC1,

OH

"

with

+HC1,
+HC1.

the

as

acid

retain

the

power

of forming

The

etc.

than

stronger

increases

OH

"

products

acid, such

much

products

acid:

salts, anhydrides,

power

also

substitution

OH

are

bination
com-

CH3.

=C2H2C10

of acetic

in

separately replaced by chlorine

resulting substitution

properties

of

are

exists

which

atoms

C2H3OOH+CI2
"

120)

p.

of this is furnished

tri-chloracetic

C2H2CIO

anhydrous

atoms

them

methyl,

as

and

+CH4.

carbon
of

is furnished

CH4,

exp.,

NazCOs

two

one

forming

di'y or

mono-

that

three

can

thus

atoms,

the

corroboration

group

heating

hydrogen

fact that

by

(see

the acetyl

this

to

methane,

soda-Hme

that

how

that

+NaOH

mean

clue

obtained

are

acetate

find out

to

us

composed.

CsHaOONa
This

for

observation

carbonate

CHEMISTRY

chlor-

acid, and

acetic

of chlorine

the number

atoms.

(4)

If

methyl

we

group,

CCH3OOH,
these
C

of the

its

from

The

having

molecule;

acid

acetic
formula

COCH3OH,

is correct?

of CH3

rest

represent

or

must

and

containing
be

than
for the

of

carbon
one

other

of

prevents

linking
C

written
which

CH3COOH:

valence
more

as

to

to

the

satisfy

172

CHEMISTRY

ORGANIC

THE

CAUSE

THE

OF

STRENGTHS

RELATIVE

BASES)

(AND

It is

important
the

obviously

etc.,

by

alkali, and
far

words

difference

fraction

of

ionized.

of

of any

anion

In

the

the

acide.

of

case

solutions

of

case

of

We

may

an

solution

The

into

effective
becomes

(see
acids

strong

in this

equimolecular

solution

depends

on

and

66).

p.

much

than

way

of
the

that

state

acid

an

with

positive ion)

ionizes

of

of

cation

molecule

therefore

that

fact

of it which

the
the

This

ive,
alkali is effect-

or

ionize

of

rest

other

being proportional

portion

called

often
the

of

acidity of

in

(which being charged

hydrion

or

H2SO4,

HCl,

as

be

solution

normal

alkaU.

or

greater proportion of acid

in

acid

fraction

is that

will

acid

stronger,

are

solution, acids

electricity is
an

with

acetic, lactic,etc.

as

this

acid

an

In

hydrogen

titration
any

acids

"

strength of the acid

the

to

acids

fraction

value

the

of

such

This

strength is explained by the

in

certain

volume

reactive

such

than

"

by

stitutes
con-

alkali.

or

of

yet

more

acid

an

solution

equal

an

it is that

what

gauged

normal

are

only

be

cannot

neutraUzed
any

of

strength

indicators:

of

understand

to

ACIDS

OF

the

weak
active

tration
concen-

of the hydrogen ions.

In

the

dissociation
its

of

case

in

bases,

solution

equivalent (K,NH4)

occurs.

It is the

(hydroxions)
Amines,

p.

which

260).

e.g.,

into

cations

and

into

concentration
determines

and

NH4OH,

of the

metal

KOH

anions
of the

their

of

or

hydroxyl

hydroxyl

ions

strength (cf.

ACIDS

FATTY

In

of

solution

AND

(a) undissociated

the two

in

less dissociation
the

therefore, there

This

the

depends

the

this

for

conductivity.
of

in

1.3%

solution

NaOH
but
the

decinormal

only

1.4%

tables,

in

decinormal

Corresponding

of

hydrogen

"

C2H5,

constituent
oxygen

to

the

atom

with

ionized,

are

(Consult

inorganic chemistry

organic acids

is

ethyl

acetate

from

which

it is

are

in the

in

replaced by

Thus

radicles
as

ESTERS.

salts of

of

carboxyl

radicle.

CH3COO

91%

decinormal

In

NH4OH.

SALTS.

derivatives

are

electrical

451).

p.

ETHEREAL

there

value

compared

molecules

the

of

84%

the

of

solution

acid.

acetic

tion
solu-

of

as

is

it

of

obtain

HCl

ionized,

tions,
dilu-

Since

measurement

are

tions.
por-

dissociation

may

decinormal

tween
be-

dissociation

conductivity
of

acid,

different

68).

p.

in

than

proportion

that

it, we

by

In

molecules

the

(see

in

proportion

(a) in

of

every

at

vary

amount

electrolyte dissolved

H',

dissociated

the

remembered

electrical

on

of

acid

In

certain

and

dilution

with
that

acid.

course,

be

will

contains

amount

acetic

of

case

exist

will, of

it

for

known

the

must

(c)

different,there being much

undissociated

the

increases

The

hydrochloric

of

case

acid

(b) cations

CH3COO'.

will be very

cases

exist:

H*, and

of

acetic

CHa-COOH,

of

(c) anions

there

example,

of

173

SALTS

(b) cations

solution

(a) undissociated
and

for

HCl,

HCl,

CI'.

of

anions

ETHEREAL

linked
ethers

some

has
seen

which

the
that

carbon
hydroformula
the

together through
(see

p.

132).

the

On

two
an

this

174

ORGANIC

such

account

salts,or

compounds
acids

nitrate,C2H5ONO2,
included

have

in

been

this

looser

ethereal

sense,

pounds
com-

organic radicles,as ethyl

ethyl sulphate, ("2115)2804,

but

group;

considered

only those

present

In

with

and

called

usually

are

brieflyesters.

more

of mineral

are

CHEMISTRY

since

elsewhere,
salts in

such
shall

we

these

as

study

organic acids

which

at
are

in combination.

Inorganic salts
of
these

acid

an

immediately

are

and

being ionized, the

immediately

unites

base

water:

form

to

(B- +OH0

Esters

+Z0

+(H-

however,
remains

only slowly

acts

point
do

that

out

iThis

equation

represented

in

this the

on

salts

of

will
reaction.

serve

ethereal

from

being usually
latter

as

not

with

solution, and
an

at

great importance

organic acids
in

salts

also in their

but

former

the

it is of

dissociation

undergo

not

(Ester)

solution, the

in

connection

this

for

alcohol, is

an

of formation

ease

entirely dissociated
In

the

(H+Z0=RZ+H2O.

dissociability in solution,

so.

of

+H2O.1

molecule, and

distinguished

in their

only

ion

readily formed,

being

(Acid)

are

acid

the

(Alcohol)

Inorganic

thus

not

as

of

(Salt)

reacting hydroxide,

R.OH

not

(B- +Z0

of

ion

hydroxyl

(Acid)

are,

ionized, but
acid

the

tions
solu-

when

for, both

mixed,

are

hydrogen

with

(Base)

the

base

formed

example

of

to

how

all
to

metals
about
ions

are

FATTY

the

ACIDS

extent

same

solution

of

whereas

in

Na*

CH3COO'

and

Mass

One

salt

directly mixed,
a

balance

ions

(i.e.,between
is because

exist in the
and

formation.

of

formation

of

and

reaction

is

slight

This

in other

one;

of water

mixture, it decomposes

until

water).

reversible

excess

are

is established

constituents

acid

an

proceeds

slow, yet

the four

the

to

comes

the

into

ester

alcohol, thus:

CH3COOC2H5+HOH
Such

illustrations

The

alcohol

an

although

words, whenever
acid

notable

acid, alcohol, salt, and

the

into

occurs.

when

between

ions,

free

no

dissociation

acetate

of the

is ester

action
ethereal

an

of sodium

one

are

in

Thus

salts.

there

acetate

175

SALTS

inorganic

as

ethyl

Action.

msiss

ETHEREAL

AND

reversible

equations by

CH3COOH+C2H5OH.

reactions
two

sign of

place of the

in

arrows

in

represented

often

are

equality.
mixture

The
when

part of

0.669

provided
acid

reaction

the

is most

marked,

and

until

hydrolysis
and
is not

acid

is

to

formation

cause

to

action

mass

pronounced

As

figure in
of the
as

for

the

action

verse
re-

water

up

and

the

reaction,
to

water

that

acid

the

and

ester

slows

esterification.

really static;

and

production,

ester

of the

beginning
alcohol

both

is present,

gram-molecule

one

slight.

very

begins

as

of

equilibrium

of ester

the

At

forcing

ester

finallythe

with

action

being

action

molecule

gram

alcohol.

mass

accumulate,
reverse

of

point

started

we

of both

action

to

comes

of

The

and

the

the

cause

alcohol

equilibrium
the

reverse

176

ORGANIC

action

are

thus

going

when

the

tion

The

increase

yield

ethereal

of

is true

with

alcohol

is used.
above

of the

the

be

law
the

of

product

by

side, is equal
reaction
C

to

the

acid

same

when

more

by titrating the
been

has
of

action

that

states

gram-molecules

of

the

extensively
action.

mass

mass

formation

one

side

of these

on

the

In

therefore

of the

the

the
case

per

tion,
equa-

other
of

the

equation:

alcohol

the

followed

constant.

have

we

acid

the

of the

product

some

hol
alco-

progress

of

on

not

increases

conversely,
of

the

on

of

amount

of acid

number

substances

divided

above

given

reaction

fundamental

liter of the

present and

studying the laws

in

employed

gram-

alcohol

the

can

acid, the

residual

The

ester

and

amount

Since

of

depends

amount

given

cule
gram-mole-

one-third

salt, and,

of

equiUbrium

formed

With

in the

the

esterifica-

thus

of acid

amo^mts

for

as

ceases

acid.

and

temperature.

an

and

water

apparently

also

case

and

ester

two-thirds

of ester

amount

the

this

water,

of alcohol

relative

but

occurs,

about

and

ester

molecule

on

In

contains

of

the

equilibrium point

same

is reached.

mixture

both

of

mixed, hydrolysis

are

equal degree,

an

balance.

gram-molecule

to

constantly

on

maintaining

If

CHEMISTRY

C
where

ester

represents

'

water

gram-molecules

liter of

per

the

reacting substances.
It will be

alcohol

evident

remains

that

if

we

constant,

increase

then

acid
ester

while
must

FATTY

ACIDS

increase, which
acid

enough
converted
alcohol

leads

into

ester,

is added,
will

same

molecule

be

of ethyl alcohol

96.6%

when

conversely,
remaining

For

example

acid

and

if

more

the

constant,
one

gram-

eight gram-molecules

equiUbrium

to

come

of

gram-molecule

become

that

if

if

that

will

alcohol

interact, they

of

conckision

acid

true.

177

SALTS

the

all the
or,

the

acetic

of

to

us

added,

is

ETHEREAL

AND

ethyl

is

acetate

formed.
does

Temperature
marked

degree,

ultimate
the

rise in

reaction

hydrolyzed
25".

at

been

of acid

and

doubles

rate

acids

by
found

about

if

The
For
some

Acetic
alcohol

amount

example the
alcohols

than

of

ester

per

cent

acids is

and

acid+methyl

55"

as

alcohol

increase

cane

sugar

fast

as

and

alcohols

as

acids,

amounts

limit of esterification
rate

is much
such

secondary

produced
of

the
Thus

for each

it is for

for

of

rate

before

equimolecular

the

than

for primary

the

five times

be used, the

acetic

as

On

velocity of the

At

different

that

alcohol

acids

such
and

the

only slightly;i but

varies
for

rule

studying

By

it. has

by

produced.

is reached.

the

degrees in temperature).

of ten
is

increases

any

the

takes

equilibrium

temperature

(as

it

to

influence

not

salt

that

time

of chemical

condition

constant

greatly influences

it

reaction, i.e., the

ethereal

of

hand,

the

it does

that

so

amount

other

affect

not

can

gram-molecule

greater
as

zoic,
ben-

alcohols.

be

greatly

of ester formed

follows:

67.5, benzoic

acid+methyl

64.5.

Acetic

acid

+ethyl alcohol 66.9, benzoic

acid

+ethyl

alcohol

67.

Acetic

acid

+amyl

68.9, benzoic

acid

-famyl

alcohol

70.

alcohol

178

ORGANIC

increased
the

by

plished. By

in

some

this

the

also

can

salt

accom-

it

as

is

crystallization),

or

be

during

be

can

ethereal

distillation

higher yields

formed

water

cases

removing

(e.g., by

much

the

removing

reaction, and

formed

CHEMISTRY

obtained

(see

exp.,

181).

p.

of

Preparation
methods

for

with

sulphuric

formed
acid

and

being

acid:

then

"

+Hi

with

HSO4

C2H6

"

heating

By

with

alcohol

first

is

first

acid, sulphuric

OOC

thus:

+H2O,

CH3

then

+H2SO4.

and

acid
acid

an

gas:

which

formed,

alcohol

chloride

is
the

with

reacts

(a) CHaCOjOH
(6)

acid

hydrochloric

probably

acid

HSO4

of the

mixture

alcohol

C2H5"
2.

ing:
follow-

and

(cf.ether, p. 134),
"

the

are

acid

the

usual

more

ethylsulphuric

+H|00CCH3

HSO4

salts

of the

reacts

re-formed

(a) CsHslOH

(6) C2H6I

mixture

The

Salts.

ethereal

preparing

heating

By

1.

Ethereal

+HiCl

CHsCOfa

CH3CO

+HJOC2H6

"

CI +H2O.

CH3COO

"

+HCL

C2H5

'"

3. Or

the

second

itself used

for

treating an

alcohol

of
or

the

an

acid.

benzoyl

(see

can

be

stage of this reaction

production
with
In

p.

an

this

359)

produced,

ethereal

of

acid

chloride

latter

or

of

be

can

salts
an

the

manner

derivatives
and

(6)

many

by

dride
anhy-

acetyl
stances
sub-

these, being readily

180

ORGANIC

is the

action^ which
their

reactions,which
but

When
and

If

will

be

found

HCl

and

that

produce

whereas

only

the

feeble

of that

Now

it has

of

acid

which

leads

power

depends
acids

hydrogen
By
method

us

this

their
to

about

acid

in

tion
reac-

ether

on

and

hydrolysis

employed.
have

acids

of acetic

Appendix,
acids

only
452).

p.

tivity
conduc-

electrical

the

is

directly

accelerating (catalytic)power,
conclusion

the

amount

words,

the

catalytic

the

we

relative

which

number

the

on

solution

therefore,
the

that

of dissociation

in other

existingin

gauging

of

ence
accelerating influ-

th6,t the
of

it

tion,
greatest accelera-

the

in

be

acetate,

organic

thus

acids

acid

the

the

means,

for

the

different

the

(see table

undergo;
ions

with

solutions

to

tion.
reac-

into

acceleration

only 19%

found

been

proportional

the

is

of HCl

dilute

enters

commonest

influence;

of oxalic

0.4%

the

greatly

HNO3

acid

the

quantities of methyl

varies

produced

lyzer,
cata-

chemical

the

quantities of

similar

to

Neither

sulphuric

as

the

pseudo-catalyst

equimolecular

added

of

catalytic agents

into

agent

recovered,

production, it is

(Some

enter

chemical

is

place without

reactions.)

ions

the

nor

take

of

more

catalysts.

slowly.

more

much

consisting in acceleration

as

would

retardation

molecule

other

than

duce
pro-

enzymes

have

Enzymes

defined

Catalysis is

which

by

means

actions.

powerful action

cause

CHEMISTRY

of

(see p. 172).

have

practical

strengths of acids

(see p. 184).
Further, if

we

of

add
the

dilute
same

solutions
mineral

of
acid

varying
to

centrations
con-

methyl

ACIDS

FATTY

proportional

is important
dilute

and

acids
the

with

the

methyl

acid,

same

acid

the

kept

the

at

allowed

(1)

three-hole

cork;

Heat

running

in

until

135".

correspond
with

small

solution

Add

litmus.
to

of

of

of the

amount

latter.

In

this
be

course

the

action
of

length

time

hole

its

the

and

80

the

approximately
the

to

distillate

in

Separate
acetic

the

top layer is

the

with

ether

cold

of

tillation
dis-

receiving

sodium
no

acid,

alcohol

rate

portions of saturated
until

begin

constant

of acid

the

the

mixture

mixture

inflow

the

Regulate

and

in

is

of glacial acetic

c.c.

of

bulb

funnel

dropping

135", then

is at

Uquid

Use

condenser,

that

flask

H2SO4.

suspend

with

so

the

medium-sized

of C.P.

c.c.

temperature

Wash

to

solution

and

slowly by the dropping

the

about

flask

that

is added,

of the

same

connect

of alcohol

c.c.

keeping
to

strong

quantity

must

into

one

thermometer

liquid.

at

Put
10

by

another

funnel, by

of 80

and

of alcohol

insert

acid

similar

the

the

for

of

for

below).

Experiments.
c.c.

of

temperature

same

proceed

to

(see exp.

10

in

solutions

two

only

acetate

made

be

can

actually present

comparison

methyl

It

By comparing

unknown

an

estimate

an

of

quantity

having

acetate

holds

acids.

occurring in

amount

law

added.

decinormal)

all for weak

known

hydrolysis

of

rate

this

hydrolysis

of

when

the

(less than

at

amount

occurs

of

not

181

SALTS

strength of acid
that

note

solutions

that

the

to

to

ETHEREAL

found

it will be

acetate

is

AND

bonate
car-

longer acid

separating

funnel.

solution

20

of

gm.

182

ORGANIC

of

calcium

chloride

(The

ester

with

the

funnel.

the

or

20

of

c.c.

the

calcium

ethyl

water).

at

(2) Determine
acetate

into

on

(HCl).

Into

methyl

acetate

to

one

add

of

known

20

c.c.

each

an

beginning
tightly with

flask

and

shake.

of each

mixture

c.c.

NaOH,

then,

shaking and

titrate

liberation

40"

the

initial

titration.

The

stronger

hydrolysis.

strength

of

the

unknown

with

the

known,

leave

for

the

flask

the

for

quickly

successively

in

acid

we

must

known

find

(due

this

to

by

greater

the

out

to

second

the

strength;

each

is found

solution

an

hours;

from

c.c.

causes

acid

in

four

calculate

To

flasks

them

or

as

the

at

the

from

solution

each

keep

three

titration

of

for

As

by hydrolysis)

amount

hydrolysis

add

tration;
concen-

Cork

and

increase

acid

deducting

of

other

acidity of

cooling, take

The

again.

of acetic

the

stoppers

about

solution

of unknown

experiment.

rubber

HCl

using phenolphthalein

gives

the

of

c.c.

pipette;

the

to

each
5

put

of

c.c.

but

at

and

20

methyl

of

with

accurately

(say 0.4%);

incubator
after

flasks

dilute

This
of

specific

strengths of acid

more

decinormal
indicator.

the

hydrolysis

small

pipette

strength
of HCl

let it

bath, noting

water

by different
of two

possible titrate

with

of

rate

measured

cork
as

the

with

dry-

IT).

influenced

as

Separate

acetate

boiling-point (77*^). Determine

gravity (0.905

shake.

chloride, cork, and

Redistill

so.

and

water

in 17 parts of
Put

solid

day

in

is soluble

flask:,add
stand

CHEMISTRY

exact

by

parison
com-

the

limit

do

this

containing this acid in the incubator

forty-eight hours,

then

titrate

again.

The

ACIDS

FATTY

titration

end

the

at

titration,gives
number

of
that

acid

methyl
the

but

call

The

observed

three

the

Take

Now

solution

the

value

of the

of

the

in

acid

HCl)

(after four

the

solution,
C".
the

during

content

is X.

gave

known

in

the

-X

tion
solu-

(c.c).

=24.9

hours)

(c.c); therefore

12.1

in

solution

known

incubation

hours'

reckon

constant

each

for

the

of

can

we

other

"

constant

is the
acetic

the

f-^ =)

C=log

(0.43435%

was

Find

this

A;

hydrolysis

by

HCl.

initial

less the

decinormal

of

particular experiment.

increase

called

in

HCl

increase

four

or

value

liberated

manner

formula

the

in

period,

by 0.4%
of

cent

this

centimeters

be

can

following

of

183

SALTS

ETHEREAL

acid

an

cubic

acetate

per

AND

solution

known
24.9

The

=12.8:

-12.1

C'-'o^fllD-^S'SWith

solution

the unknown

(c.c.) A

"

17.9

C-'o^lil)-"*'Now

the

cent

per

^? yf

\ C

Therefore

In

this

per

) (per

of known

cent

in the

of HCl

particular

unknown

cent

HCl

in

known)

(0.43435)
(--^)

case

exactly half the strength of

the
the

=0.21544.

unknown
known

was

solution.

of

184

ORGANIC

The
to

of

rate

of

with

acids

of acid

present

furnish

their

157) that

the
stomach

easily

of the

quantity
Most

ions

(see

in

present

p.

effect.

practically no

ing
for determin-

gastric juice

forgotten, however,

of

acid

were

or

Decinormal
and

results.

acetate

has

various

oxidation

only

pure

mixtures.

cyanide, and

FATTY

instead
of

of

of

acidity

least

at

This

ion

ment
experi-

of

day.

decinormal
will

give

concentrations.

ACIDS

(propanoic acid), CII3-CII2COOII,'

acetic
of

titration

increase

c.c.

strength

ing
give interestused

for

proceeded

OTHER

Propionic acid

be

third

rough idea of the relative

resembles

the

tartaric, oxalic,

acids

may

directly the
the

of

hydrochloric
Make

acetate.

procedure

solutions

Ethyl

hydrolysis
in

be if

relative

the

acids, repeating the

trichloracetic

Compare

Determine

3.

several

methyl

ence
pres-

change

can

it would

what

the

that

present.

Experiment

2.

contents)

(as in stomach

hydrolysis from

rate

acid

of HCl

be

not

of salts

after

of

contents.

It must

of

solutions

is available

the method
cent

per

tion.
solu-

hydrogen

has

presence

In consequence,

in the

by this method.

few

so

relation

present

estimation

made

be

can

organic acids

dilute

accurate

an

definite

ions

hydrogen

Therefore
ionizable

bears

hydrolysis

number

the

CHEMISTRY

acid.

It

can

be

prepared

propyl alcohol, by hydrolysis

by the action

of CO2

on

of

by
ethyl

sodium-ethyl.

FATTY

addition

In

AND

ACIDS

it

be

can

made

185

SALTS

ETHEREAL

reduction

by

lactic

of

acid, thus:
CHa

"

CHOH

COOH

+2HI

(Lactic acid)

hydriodic

The
and

acid

acids.

of

CH2

group

reduction.

But

hydrogen

place

of

the

molecule.

Greek

and

will

carbon
to

apply

thus, the
the
for

Butyric

next

group

second

CH3

CHCl

"

necessary
group:

is in the
/?
"

tion,
posi-

position, and
is

COOH

is

CH2CI-CH2-COOH

acid,

many

carboxyl

the

rule

how

matter

no

two

by using

have

to

COOH

is in

group

is done

the

the

to

example,

propionic
propionic

from

sary,
neces-

these

contain, it is

may

backwards

count

on;

acids,

acid

the

atoms

becomes

order

In

/3.

all

to

This

in the

or

group

It

the

take

may

CH3

chlor-

are

distinguish between

to

positions in the
that

there

halogen
acid.

propionic

letters, a

acids

in the

either

therefore,

_j_j^

hydrogen,

nascent

to chloracetic

Corresponding
propionic

furnishes

brings about

this

_j_jj^q

(^jj^ (.jj^ (^qqjj

so

a-chlor-

fi-chlor-

add.
acid

CH3

"

CH2

"

CH2

"

is

COOH,

normal

butyric acid.
Isobutyric add

or

acid has

methylpropanoic

the for-

CHsv
"CH

mula

"

Normal

COOH.

butyric

acid

CH3/
is fermentation

burger
be

butyric

cheese, rancid

prepared

hydrolysis

by
of

occurs

butter, and

oxidation

propyl

acid, and

of

sweat.

butyl

cyanide.

alcohol

Butter

in
It

and

Limmay

by

contains

186

ORGANIC

6%

about

CHEMISTRY

butyrin, which

of

butyric acid

(see

obtained

hydrolysis

(see

by

exp.,

the

acid.

acid

soluble

it

readily be

can

later in

acid

Butyric

The

these
while

acid;
acid

into

made

in

sour

the

latter

and

third

variety

+H2O

be

described

cane

sugar

milk:

with

as

taric
tar-

variety

one

^'inverts"

the

variety

producing

lactic

the

lactic

converts

=C6Hi206+C6Hi206,

sugar)

(Dextrose)

CH3

"

CH2

fermentation,

butyric acids, may

hydrochloric
or

H2)

acid

"

CH2

absent
cause

the

"

acid)

COOH

+2CO2

production
in

the

stomach

of lactic
when

and
the

gastric juice is deficient

altogether.
the

+2H2.

acid)

with

occur

of

(Lsevulose)

=2C3H603,

(Butyric

and

account

Isevulose; another

(Lactic

(CO2

or

estimation

an

from

with

C6H12O6

in amount

butyric

this

to

manner

tile.
vola-

butyric acid:

(Cane

Similar

On

monosaccharides,

C12H22O11

2C3H6O3

little

very

butyric

and

solution, acidified

sugar

dextrose

into

ferments

cause

of

water

by making

also be

can

microorganisms

sugar

in

acids.

in the

acid, is inoculated
of

be

experiment (see p. 207).

an

follows:

identified

can

free

setting

fatty

acids

volatile

of the

and

contains

volatile

other

therefore

can

resulting hydrolysis

is soluble

Oleomargarine

of

saponification of butter

or

(butyrin)

Butyric

acid

butter, with

of

ester

the

glycerol ester

Microorganisms

207).

p.

fermentation
of

200)

p.

is the

flatulence

The

gases

present

formed
in

such

188

ORGANIC

non-volatile

are

of

calcium

The

called

remedy
of

iodine.

insoluble.

and
acid

palmitic

CHEMISTRY

is

62.6",

salt

sajodin;

of

The

and

of

melting-point
acid

stearic

monoiodo-behenic
it

is

used

is
acid

for

tion
administra-

69.2*^.
is

CHAPTER

AND

SECONDARY

XIII

CERTAIN

OTHER

ALCOHOLS.

SECONDARY

MONACID

KETONES

ALCOHOLS

AND

OXIDATION

THEIR

PRODUCTS

Secondary
in

CH3

of

the

contain

CH3,

secondary

CHOH

"

"

formed,

CH3

"

but

CHOH

as

None

alcohol.

propyl

of

CHOH,

group

importance.

any

is oxidized

aldehyde

an

ketone:

+0

CHs

the

alcohol

secondary

is

alcohols

secondary

When
is not

alcohojs

CHs

"

CO

"

CH3

+H2O

or

aldehyde,
of

is in

ketone

an

the

atom

ketone

it

at

is

up

can

the

give the

chain
fuchsin

the

of
to

be

is

atom

end

attached

that

being

oxygen

one

identical

points

diflference

the

ketones

spUtting
ketones

only

aldehyde

carbon

Some

all essential

an

inner

test
189

but

carbon

(see

p.

the

attached

chain,

oxidized,
of

in

with

while

carbon

an

case

to

in

atom.

this

involves

atoms.

Some

154), particularly

190

ORGANIC

those

that

ketones

have

form

CH3

Ketones

do

in

the

same

hydrazones.

forming

but

phites
sul-

(cf. aldehydes).

ketones

aldehydes,

Many
acid

with

acid

with

polymerize,

not

molecule.

the

compounds

reacts

with

as

in

CO

hydrocyanic

Phenylhydrazine
manner

"

addition

with

and

CHEMISTRY

tion
condensa-

they form

products.
reaction

The

ketones

CH3

of

is similar

"

CO

"

CHs

derivative
contain

is

that

to

+PCI5

"

CCI2

CHs

"

+P0Ci3.

and

produced,

therefore

The

with

aldehydes:

CH3

is

formed;

hydroxyl.

pentachloride

with

acid

hydrochloric

No

phosphorus

ketone

does

ketone

important

most

dichlor

not

is

acetone.
Acetone

(dimethylketone

is

CHs"

acetate

CO"

can

also be

propyl alcohol.
acetyl chloride

plest
sim-

CO

-CHs.

It

'^he

distillation

dry

300":

Ov

^^^"Ca
It

is the

by

about

at

propanone)

being CHs-

commercially

produced

of calcium

formula

its

ketone,

or

obtained
Its

CHs

CO

CHs

+CaC03.

by oxidation

synthesis

proves

the

from

zinc

structural

of

secondary

methyl
formula

acetone.

I/CH3 '

[CHsCOiCl
+

iCHsCOjCl

Zn!"
I^CHs
=2CH3CO.CH3+ZnCl2.

and
for

ALCOHOLS

SECONDARY

Acetone

in

is present

especiallyin
a

useful

solvent.

Nascent

the

is

hydrogen

liquid, boiling

It does

not

the

number

of carbon

and

formic

iodoform

ditions,
con-

0.812

acid

an

0*^.

at

pyl
pro-

ing
contain-

but

atoms,

acids.

56.3"

at

secondary

to

is

It

acetic

to

gives the

Acetone

test.

(1) Make

Experiments.
instead
The

involved

of the

are

of iodoform

preparation
the

iodoform,

using

tone
ace-

(see p. 130).

of alcohol

reactions

in the
case

oxidize

carbonic

or

of

it into

converts

alcohol.
same

certain

of diabetes.

cases

specificgravity

191

KETONES

under

urine

severe

It

(corrected), with

AND

intermediate

as

alcohol; in this

from

compound

nature

same

is

triiodoacetone,

in

dilute

CI3COCH3.

(2)
add

Dissolve

20%

and

H2SO4,

acid

(see

(3) Shake
saturated

c.c.

wash.

of acetone

of KOH,

of acetone.
and

Test

strongly

on

acid

the distillate for

acetone

with

of

sodium

bisulphite;

compound

"

of

c.c.

of acetone

cool;

appear.

samples.

CCI3, is

It is formed

useful

trichlor-tertiary-

acetone,

/O"
C^^
^CH3

chloroform

It is

filtrate

remains

of

Save

butyl-alcohol), CH3
product

the

(chloroform

Chloretone

color

pink

H2SO4;

163).

p.

solution

and

distill.

crystals of the addition

Filter

acetone

until

Filter, make

warming.
acetic

of

c.c.

solution

KMn04

with

an

addition

by the interaction

in the presence

hypnotic.

of

an

excess

192

ORGANIC

the

Brometone,

produced

analogous
instead

from

As

and

aCids

Some

acids.

carboxyl

tion,
prepara-

is

bromoform,

it is used

remedy

importance,

contain

both

the

it may

in

occur

acid,

and

typifies these,
since

car-

Aceto-acetic

groups.

CH3COCH2COOH,

p.

and

acetone

chloretone.

to

bromine

corresponding

of bromides.

Ketone

bonyl

CHEMISTRY

is

urine

the

of

(see

218).
(pyroracemic

acid

Pyruvic
ketone

acid

of

importance.

CHs-COCOOH.

It

shows

is

acid)
Its

is

formula

tendency

strong

another

to

polymerize.
Tertiary alcohols,

compounds

containing

alcohol.

The

that

be

said

most

alcohols

having

example

waxes

monacid

contain

esters

alcohols,
of

of carbon

alcohol, CH3(CH2)i4CH20H.

the

importance.

no

Cetyl

monacid

atoms

; for

alcohol, CsoHeiOH.
of the

some

alcohol

is not

in ester

bination,
com-

free.

Cetyl palmitate

p.

other

of

alcohol, C26H53OH.

but

(see

are

into

than

atoms

Ceryl

waxes

ovarian

of

decompose

carbon

fewer

large number

Melissic
In

oxidized,

tertiary alcohols

need

Little

except

when

cyst.

has

Lanolin

been

found

contains

in

the

some

wax

fat

of

an

esters

211).

Myricyl

palmitate,

chief constituent

CaoHeiOOC-CieHsi,

of beeswax.

is the

XIV

CHAPTER

They

contain

alcohols

comparable

are

alcohol,

glycol

(ethandiol),

the

hydroxyl

two

only

groups.

The

Ca(0H)2.

to

and

diacid

ACIDS

ALCOHOLS

DIACID

DiACiD

DIBASIC

AND

ALCOHOLS

DIACID

of

one

simplest

importance,

is

CH2OH

The

method

of

prep-

CH2OH
aration

the

attached

to

produced

from

with

saturated
in

the

p.

301).

of

with

sulphuric

action

of

AgOH

CH2:Br

acid.

The

silver

the

the

is

latter

ethylene

ethylene

glycol

hydroxide

is

bromide,
(see

experiment

bromide

ethylene

the

by

heating

in

not

are

Ethylene

by

forming

described

From

groups

atom.

alcohol

bromine,

manner

obtained

carbon

same

ethyl

excess

an

hydroxyl

both

that

shows

can

be

CH2OH

'"""'"+""
'

CH2IB?

"AglOH

+2AgBr.

CH2OH

-.rr.l

i
"

is

Glycol

It

taste.

of

1.128

It

at

forms

colorless

boils

at

glycerol-like
195"

and

has-

liquid,
a

of

ish
sweet-

specific gravity

0^
two

classes

of
193

ethereal

salts, according

194

ORGANIC

whether

to

one

Sunilarly there

CHEMISTRY

both

or

two

are

hydroxyls

sodium

replaced.

are

alcoholates

of

glycol:

CHsONa

monosodium

glycolate,^ and

CH2OH
CHaONa

disodium

glycolate*

CHsONa
oxidation

The
because

of

groups.

There

products

the

two

glycol

of

presence
are

of

are

numerous

primary

two

aldehydes

alcohol

CH2OH

glycolicaldehyde,

and

CHO
CHO

glyoxal.

CHO

Oxidation

of

first gives

the

rise

glycollicadd,

to

CH2OH

this

will

be

considered

under

hydroxy-

COOH
acids

(see

p.

Oxidation

212).

of

glyoxal

gives

CHO

glyoxylic add;

this

is really

dihydroxy-

COOH

acid,

as

acids

are

will be

monobasic.

Distinguish from

(p. 213).

seen

later

(see

Complete
the

p.

219).
oxidation

glycoUates derived

from

These
of

two

glycol

glycollicacid

196

and

oxalate);
acid.

When

oxahc

acid

is

carbon

monoxide,

heated

in the

carbon

dioxide

all

more

solutions

of

172).

series

is

between

the

increased, acid

dioxide, and
acid

heated, it first loses its

and

water,
of

presence

it

(see

acid

If
and

Sulphuric
carbon

monoxide,

Potassium
oxidizes

dioxide,
acid.

159).

p.

carbon

to

water.

solution

formic

some

of

water

into carbon

glycerol, formic

formed

are

decomposes

water

of

contains

interposed

decomposes

then
crystallization,

warm

this

p.

sulphuric

is decreased.

power

acid

(see

little

strongest

corresponding

atoms

of

the

with

solution

its

of C

acids

of

carboxyls

of

organic acids

number

the

product

one

the

than

ions

other

As

is

because

acids,

hydrogen
most

acid

(and

hydroxide

treating the

Oxalic

organic

and

formate

potassium

CHEMISTRY

ORGANIC

in

permanganate

it to carbon

dioxide

and

2KMn04

+5(COOH)2

+3H2SO4

IOCO2

+K2SO4

+2MnS04+8H20.
Oxalic

acid

forms

classes

two

of

salts, acid

and

COOH
neutral.

Acid

potassium

oxalate^

occurs
,

COOK
in

plants, particularly
and

Slum,

oxalates

sodium

of

oxalates

metals

oxalate

sorrel.

are

frequently

are

Ammonium^
soluble;

potas^
all

practically insoluble.
occurs

in

the

urine

other
cium
Calas

crystalline sediment.
Oxalic
suicidal

acid

is

purposes.

poisonous

and

has

been

used

for

ALOCOHLS

DIACID

200
in

Set

the

acid

one

third

its

50

in

of

gm.

has

original volume.

Cool

Recrystallize, using

100".

to

cane

sugar.

ceased, evaporate

evaporating

an

acid.

dish
and

the

collect

little

as

about

to

hot

water

possible.
(2)

Heat

dry crystals

some

test-tube, loss
as

add

oxalic

of

large flask

of fumes

mixture

crystals.
as

and

evolution

the

in

HNO3

fume-closet

When

of

c.c.

197

ACIDS

DIBASIC

(1) Preparation

Experiments.

Heat

AND

of

of

water

of

crystallization

by drops collecting on

shown

acid

oxalic

the

in

occurs,

part of the

cool

tube.

(3) Decompose

on

evolved

the

test

p.

3) and

oxalic

some

for

gases

CO

acid

CO2

with

(baryta

(haemoglobin

H2SO4;
water,

solution,

on

as

as

p.

161)'.
(4) To
of

H2SO4,

acid solution

of oxalic

c.c.

then

warm,

add

potassium

add

few

drops

permanganate

solution, it is decolorized.

/COOH
acid, CH2"r

Malonic

"

mainly

in

bringing

about

CH2"
Succinic

is
,

certain

importance

organic syntheses.

COOH

acid,

of

is

normal

succinic

COOH

CH2"
acid

and

propionic
CH2CN

be

may

"

produced

by hydrolysis of j3-cyan-

acid:

CH2

"

COOH

+2H2O

CH2"

COOH

+NH3.

CH2"
If caustic

potash

siimi succinate

is used

would

be

to

effect

formed.

COOH

hydrolysis,potas-

CHEMISTRY

ORGANIC

198

If

hydrolyzed,

be

acid

a-cyanpropionic

isosuccinic

is formed:

acid

+NH3.

CH3CHCNCOOH+2H20=CH3
/COOH
r/

\COOH
These

acids

two

give

acid

succinic

Normal

and

anhydride

succinic

COOH

"

CH2

"

different

CH2

"

reactions.
heated

when
water:

COOH

COv

CH2"

"0+H20.

CO^

CH2"
(Succinic

breaks

into

up

and

acid

propionic

anhydride)

heated

when

acid, however,

Isosuccinic

yields

235",

to

above

130",

carbon

dioxide:

COOH

+CO2.

/COOH

CH3

"

CH"^

is, indeed,

It

dioxide

being

peroxide
HOOC

It

is

an

at

split

off from

(cf

acetozone
.

(CH2)
oxidizing

2CO"

agent,

"

attached

remain

of

352)
O"

and

that
the

carbon

carboxyls.

the

peroxide)

O"

to

temperatures,

one

p.

chemistrj^

organic

high

atom

(disuccinyl

Alphozone

CH2

in

cannot

groups

carbon

same

"

rule

general

carboxyl

twQ

CH3

is

an

organic

OC

(CH2)

is said

to

2COOH.
be

antiseptic.

CHAPTER

TRIACID

XV

ALCOHOLS,

AND

FATS,

TRIACID

SOAPS

ALCOHOLS

CH2OH

(glycerine

Glycerol

propanetriol)

or

is the

CHOH,
CH2OH
triacid

only

fats

in

acid,
ing

alcohol

glycerol

closed

The

with

with

the

of

alkaU.

peratiu'e
becomes
combined

glycerol

is

glycerol

diminished

The

1.24.
steam

is

crude
and

prepared

vacuum

by
199

into

solution
is

The

to

is then

its

glycerol

as

low

specific
is

of

and

ated
evapora

tem-

gravity

purified

distillation.
treatment

also

liquid

salts

remove

at

is

containing

soap,

solution

until

ble
insolu-

goes

Glycerol

pressure,

possible,

as

in

hard

purified

lime.

forming

manufacture.
of

and

glycerol

acid.

in

170-180")

remaining

separation

hydrolyz-

water

acids,

the

soap

dilute

under

fatty

oleic

accomplished

(at

with

while

glycerol,
The

fats

is

occurs

and

By

This

sulphuric

of

acids

acids.

free.

calcium

by-product
after

these

autoclave

or

The

precipitated

4-5%

set

salts,

solution.

left

of

Glycerol

fatty

heating

combines

calcium

is

by

boiler

lime

with

esters

fats, glycerol

conmaercially
a

importance.

combination

in

as

of

by
C.P.

distilled

200

ORGANIC

glycerol with

CHEMISTRY

and

charcoal

with

distillation

in

steam

vacuo.

Glyceryl butyrate

OOC

will

of

gravity
low

1.265

and

as

with
a

replaced by

cific
spe-

hygroscopic.
by cooling

melt

17".

at

It is useful

water-vapor.

or

three

chlorine

trichlorhydrin

hydrolyzed
ethyl

to

of the

be

hydroxyl

form

to

as

to

is

It

solvent

di-,

mono-,

or

trichlor-

CH2CI

CH2CI

CHOH,

CHOH,

CHCl

CH2OH

CH2CI

CH2CI.

heated

with

water

Glycerol

by producing

can

to

170",

be

it is

obtained

successively acetic

isopropyl alcohol, propylene,

dichloride,

be

can

groups

CH2CI

glycerol.

alcohol

acid, acetone,

glycerol:

is

It

obtained

be

can

respectively:

hydrin

from

15".

at

has

preservative agent.

One, two,

If

liquid, hav"
and

290"

at

(0"); these

temperature

volatile

COOH.

fully presently.

more

colorless, syrupy

Crystals of glycerol
a

considered

be

It boils

taste.

sweet

"

CH2OH

glycerol is

Pure

ing

fats

+3C3H7

CHOH

C3H7

"

other

The

3H2O

C3H7+

"

OOC

CH2"

CH2OH

C3H7

"

"OOC

CH

hydrolysis

on

butyric acid, thus:

glycerol and
CH2"

yields

butyrin

or

trichlorhydrin, and,

pylene
pro-

finally,

TRIACID

CH3

ALCOHOLS,

CH2OH

"

CH3COOH

-"

(Alcohol)

CHa

-"

CHOH

"

"

(Acetic

acid)

CH3

-"

CO

"

CH3

(Acetone)

CH3

CH=CH2

"

-*

CH2CICHCICH2CI

-"

dichloride)

(Trichlorhydrin)

CH2OH

-*

"

(Propylene)

CH3CHCICH2CI
(Propylene

201

SOAPS

CH3

-"

alcohol)

(Isopropyl

-*

AND

FATS,

"

CHOH

"

CH2OH.

(Glycerol)

forms

Glycerol
is

salts

with

nitroglycerine

and

cold

is

the

water;

by mixing

acids.

mixture

ceased, the
of

nitric

the

into

poured

oil.

Its

when

formula

and

water.

other

or

and

may

Nobel
absorb
formed.
are

suddenly
of

formation

is CH

heated

"

NO2

NO2.

"

much

as

discovered

that

nitroglycerine;
Such

has

as

75%

It

with

of the

cordite

as

ex-

the

earth

nitroglycerol,

gelatinous

explosives

dioxide,

infusorial

nitrocellulose
a

as

NO2

with

impregnated

contain

latter.

(p. 247)

being

mass

and

will

ballistite

in this way.

dynamite

gun-cotton,

0"

0"

of

is

prepared

little wood

Nitroglycerol

is

pulp,

strong

from
and

large volume

percussed,

or

consists

Dynamite

prepared
Gelatin

action

nitrogen, nitric oxide, carbon

material

is

It

nitroglycerine separates

CH2"

plodes

nitrate
tri-

glycerol with

When

CH2"

heavy

The

nitroglycerol.

or

yellow, oily liquid, made

sulphuric

acid.

nitric

resin, collodion
nitroglycerol.

poison, causing

violent

202

and

headache

ORGANIC

CHEMISTRY

lowering

of

it is used

solution

alcoholic

is similar

Tetranitrol

blood-pressure.
as

In

medicine.^

nitroglycerol,chemically and

to

It is the

1%

tetranitrate

of

the

tetracid

macologic
pharalcohol

erythrol.

Glycerol

glyceryl acetates

forms

This

anhydride.

acetic

fully under

wjien treated

be

will

considered

with
more

fats.
COOH

On

oxidation

glycerol yields glycericadd, CHOH,

CH2OH
COOH

and

add, CHOH.

tartronic

These

studied

are

with

COOH
the

hydroxy-acids (see pp.

Glycerophosphoric
of

acid

CH2OH

"

CHOH

brown.
The

in

will

fumes

been

odor

blacken

moistened

molecule

one

with

of

c.c.

glycerol,

until

(acrolein) (see
a

strip

ammoniacal

with

glycerol with

dish

evaporating

an

the

Note

of

combined

(1) Heat

KHSO4

of

221).

CH2(H2P04).

Experiments.
gm.

consists

acid

orthophosphoric

and

219

of

it turns

302).

p.

that

paper

silver

has

nitrate

solution.

(2) Repeat
other

some

the

fat.

acrolein

(3)

To
1

the

This

Glycerol in combination

test.

few

experiment, using

same

lard

also

or

gives

"

cubic

centimeters

is nitrite action

(cf.amyl

of NaOH

solution

nitrite,
p. 265).

204

ORGANIC

Mixed
been

of

esters

proved

to

CHEMISTRY

obtained;

be

glycerol can

have

some

naturally.

occur

CH2"

OOCC15H31

CH-OOCC17H35

I
CH2
is

mixed

OOC'Ciyllss

ester.

following mixed

The
in beef

and

fat

mutton

contains
and

volatile

are

solubky

oleo-palmito-stearin.
of

esters

namely,

acids.

contain

oleomargarine)
these

glycerol

caproic

caprylic, and

detected

dipalmito-stearin,dipalmito-

olein, palmito-distearin, and

Butter

been

have

esters

only

fatty acids
butyric,

Artificial
small

very

that

capric,

butters

(as

amounts

of

acids.
also

Butter

contains

dihydroxystearic
It will be

oils that

are

Cod-liver

esters

acids.

of interest
used

to

give the composition

of the

in- medicine

conmionly

most

contains

oil

myristic, lauric and

of

of

glycerides

stearic, oleic, myristic, erucic, and

palmitic,
Other

two

saturated
un-

acids, also cholesterol.

oil contains

Croton

tiglic,crotonic, formic, acetic,

butyric, valeric, myristic, and

palmitic, stearic,and
Castor
and

oil is

stearic,and
Olive

also
and

some

chieflyof

acids, and

olein

esters

of

to

the

of

ricinoleic

also

sebacic,

acids.

extent

palmitic

phytosterol.

esters

contains

dihydroxystearic

oil has

acids, besides

oleic acids.

composed

isoricinoleic

lauric

and

of

70%,

and

arachidic

tains
con-

acids,

ALCOHOLS,

TRIACID

Fat

values

by finding the melting-point and

and

fat

gravity, a
the

aid

The

values

analytical

certain

determining

By

Values.

205

SOAPS

AND

FATS,

generally be identified

can

tables

the

of

referred

cific
spe-

for

compiled
will

to

be

now

the

with

purpose.

brieflyexplained

in order.

Reichert'Meissl

(1) The
butter

When
so

acid

or

estimated

cubic

in

the

distilled
the

below,

distillate

readily
value

decinormal

of

from

as

volatile

be

can

centimeters

fat.

fied
saponi-

Reichert-Meissl

The

of

the

the

is

then

and

distillate

the

titration.

by

contained

acid

in

number

the

acid

experiment

solution

in

in

present

fatty substance

fat

the

the

in

acid

other

any

free

to

as

described

is

soluble

of volatile

amount

indicates

number

five

of

grams

fatty substance.
(2) The
of

decinormal

acid

The

present.

total

(3) The

it with

heating

of alcoholic

normal);
with
1

half
very

Analysis

of

is

used

being

of

amount

neutraUze

to

with

mixtiu'e

expressed

of

acid

the

as

free

grams
milli-

as

free acids

present,

KOH
the

accurately

an

solution

resulting

normal

Oils,Fats,

and

and

Waxes,

is diluted

this

on

by

saponified by

measured

find

to

book

is

of known

soap

HCl

satisfactory

free

by the saponification number.

quantity of fat (2-4 gm.)

weighed

value

amount

is indicated

combined,

the

titration

of fat.

gram

one

acid

required

of iKOH
in

determines

This

by

ether

phenolphthalein

KOH,

indicator.

an

fat is found

fat in alcohol

of the

solution

of

number

acid

how

quantity

strength (half
and

titrated

much

KOH

subject

J, Lewkoioitsch.

is

Chemical

206

CHEMISTRY

ORGANIC

KOH

of
for

each

combined
of

gram

this is the

the

Then

unneutralized.

remains

with
taken

fat

is

grams
in milli-

amount

fatty acid

as

readily calculated;

saponification number.

(4) The

ester

of

rMmber

the

fat represents

acid, being the saponification number

acid

bined
com-

less the

number.

(5) The

iodine

unsaturated

acid

forms

299)

soap

This

value

by

up

(6) The

100

is

hydroxyl

as

of

group

the

iodine

The

the

of

amount

acid

(see

p.

of iodine

grams

of fat.

acetic

the

estimates

number

glycerol is treated

molecule

one

expressed

grams

acetyl
If

content.

with

compound

taken

the

(e.g.,oleic) present.

addition

an

estimates

number

with

acid

is

(see

attached

p.

hydroxyl

acetic

anhydride
for

produced

each

169);:

oc-CH^i

CH21OH

'

I
CHOH+O

\
OCCH3

CH2OH

CH3

"

COOH

+CH2

"

OOC

CH3

CHOH

CH2OH
(Glyceryl

The

reaction

groups

are

triacetate
latter

for
a

manner
can

be

"

can

be

pushed

until

monacetate)

all of the

hydroxyl

displaced, giving, as the products, glyceryl

acid

and

acetic

each

molecule

fat which

of

contains

acetylated,''and

(three molecules
glycerol).
some

In

of
a

hydroxyl

by estimating

the

the

similar
groups

acetic

TRIACID

acid

in

the

ALCOHOLS,

fat, the

The

with

combination

hydroxyl

acetyl number
of

hydrolysis
and

fat

hydroxy-acids

number.

Such

contained

in castor

acetic

(e.g.,

mainly

acid

The

after
tially
Par-

diglyceride)

responsible for this

is ricinoleic

acid

(p. 304)

oil, also dihydroxy-stearic acid,

in castor

and

acid

esters

CH3(CH2)7(CHOH)2(CH2)7COOH,
in butter

milligrams

acetylated fat.

are

an

of

the

of

calculated.

of the

gram

hydrolyzed

number

acids

or

be

can

the

207

SOAPS

alcohol,

neutralize

to

one

the

content

is

required

of KOH

AND

FATS,

viscosity number
for the

purpose

olive

oil, since

the

lower

viscosity.

which

is present

oil.

(see
of

79)

p.

be

may

detecting

mined
deter-

adulteration

of
,

Experiments.

with

putting
gravity

0.926

adhering
(it having

the

will

"

butter

gm.

There

either

sink

20

c.c.

flame, shaking
about

five

rotate

to

walls.

cooL

Heat

the

The

bring
again

soap

Into

down
for

solution

of

c.c.

glycerol.

prevent

minutes

to

remain

or

butter, 2

of

be

of specific

will

0.918

60%

with

complete,

^ip

small

off
the

adhering

minutes,

should

tion,
solu-

foaming.
boiled

few

flask

KOH

is

fat

15") ;

at

300-c.c.

excessive

any

float

suspended.

Heat

water

cessively
suc-

air bubbles

no

of about

number.

saponification is almost
and

in alcohol

oleomargarine

specificgravity

a.

specific gravity

oleomargarine by
must

The

fat.

of filtered

and

of

little of each

(2) Reichert-Meissl

put 5

that

15".

at

the

to

the

(1) Compare

of filtered butter

oils have

cheaper vegetable

be

then

In

and
flask

to

the

partly

clear.

Add

208

ORGANIC

90

is dissolved.

soap

zinc

some
on

powder

take

100

it

transfer

the

titrate

number.

less than

with

by 1.1;

this

For

butter

The

experiment

24.

distillate;

little

this

KOH
of cubic

the

value

Reichert-

should
be

may

not

repeated

oleomargarine.

(3) Acid
and

add

or

dissolve

Now

pink.

decinormal

(5-10 gm.) in

of the

some

with

decinormal

KOH

after

mixing.

If the

to

faint

until

remains

turbid

bath

(with

saponification.
the

Hence
In

acid.
with

Many

the

the

action

resulting products
of the

with

decomposed

are

formed.

means

flame

"

fats
is

soap

during

no

it).
When

butter
titrate

which

pink,

slightly
of

quantity

becomes

water

alcohol

ether-alcohol,and

mixture

it in

titration,warm

KOH

weighed

of

solution, then

phenolphthalein
of

more

equal volumes

Mix

number.

ether;

drop

near

and

phenol-

number

gives

plished
accom-

decinormal

the

in

pipette

a
a

with

Distill

be

the

with

Add

and

distillate

Filter

Multiply

of alkali

centimeters

of

the

H2SO4

5%

c.c.

filtrate

and

slightly pink.

Meissl

110

beaker.

solution

phthalein
until

to

until

distillingshould

The

of

c.c.

of

c.c.

thirty minutes.

in

shake

pieces of pumice.^

Collect

flask.

graduated

50

small

or

and

water

Add

sand-bath.

be

distilled

hot

of

c.c.

CHEMISTRY

origin

strictest
of

the

an

word

To

prevent

on

alcohol

of

bumping.

ci

alkali,

the

term

tion
saponificaester, the

an

and

loosely as

hydrolysis.
1

aid

sense,

alkali

an

being
use

the

salt

mous
synony-

TRIACID

Soaps

Ordinary

sodium

is soft soap,

the

by

glycerol that
is hard

soap
''

by

is

lead,

of

is

by

freed
which
"

out

or

olive

from

in

slightly yellow
and

copper,

been

glycerol
in

if

Calcium,

the

genuine,

free

no

the

Sodium

of

soap,

color.

to

contains

described

contains

It

soap.

changed

freed

Venetian

other

many

sium
Potas-

green

is
It

manner

oil.

potassium

saponification.

has

occur

oleate.

indigo.

the

in

Castile

experiment.

It

addition

soap,

salting

is made

of

color

yellow

that

called

conmionly

its

countries

many

green

acids

mixtures

are

soaps

the

of

209

SOAPS

palmitate, stearate, and

soap
In

AND

FATS,

salts

metallic

are

in fats.
or

ALCOHOLS,

alkali.

mercury,

form

insoluble

resin, sodium

resinate

metals

soaps.

Cheap

are

soaps

acting similarly
The

solution.

Add

with

see

p.

of the

The

only
effect

Sodium

salts of soap,
stearate

particles. Various

by

This

first

using

in

be

can

the

of

to

dilute

also

aids

oleate

and

palmitate

explains why
vaseline

vaseline

is adsorbed.

decided

mechanically
least.

furnish

in

the

can
a

The

colloidal
these

to

in

soluble

most

the

vaseline
with

dissociation,

on

adsorb

removal

soap

now

appears;

is the

hydrolyzes

to

concentrated

dilution

due

demonstrated

slight red

substances

treating the

soap;

largely

salts

and

facilitating their
process.

the

of

lather

dirt.

hydrolyzed

is

soap

large quantity of water, and

develops (for
68).

of

phenolphthalein

red

removing

soap.

dissociation

This

solution, and

dilute

true

dissociation

follows:

soap

with

action

cleansing

hydrolytic

as

to

made

ticles,
par-

washing

be removed

fat, and

then

210

CHEMISTRY

ORGANIC

The
some

be

to

alkali

free

of

to

washed

; while

fat.

adsorption

the

saponify

extent

the

solution

soap

oleate

Saponification,
all of

are

them

surface

acts

sify
emul-

to

and

emulsification,
in

factors

the

to

acts

the

on

grease

sodium

the

probably

cleansing

process.

of

gm.

50

lard
of

c.c.

hour
a

tallow, add

or

alcohol;
boil

tube, and

of

test-tube

attach

water;

While

water.

saturated

drop

if

no

separate

as

To

(2)

of the

same

fatty acids

the

water,

soap)
and
'^

the

50

an

of

c.c.

volume

Sodium

of
will

soap

finally solidify.
add

hydrochloric

rise to the top.

and

acid.

Collect

thoroughly

filter paper,

with

soap

calcium

lead

solutions
''of

soap

colloidal

with

crystalhze

the

The

colloidal

other

same

solution

metallic

soap

(calcium
sulphate,

copper

salts.

Explain

water.

solution

state;

aid of heat

with

treating

(lead soap)

acetate

of

by

chloride

equal

filter,wash

insoluble

with

hardness

In

half

alcohol.

(3) Make
solution

fluid

with

an

solution

air condenser

out,

NaCl.

between

press

hot

from

on

and

oily drops separate

of

fatty acids separate and

Free

KOH

half

add

soap

60%

10

with

Dilute

top layer and

about

boiling

After

hot

solution

of

upright

an

saponification is complete.
hot

flask

c.c.

moderately.

shaking

by

test

into

Put

(1)

Experiments.

at
a

least

part of the

concentrated

gelatinizes on

behavior

of

the

soap

solution

is in
made

cooling (hydrogel).
solution

is said

to

CHAPTER

XVI

HYDROXY-ACIDS

Hydro3cy-acids
(COOH)

marked

therefore

defined

be

attached

atom

by

but

alcohols,

to

of

one

hydroxyl.

however,

which

in

the

and

They

is

atoms

called

often

are

may

hydrogen

carbon

are

They

properties.

hydroxy-acids,

acids

as

acid

arid

(OH)

properties,

alcohol

the

than

acid

not

are

alcohol

acid

The

groups..

more

both

contain

placed
re-

oxy-

acids.
The

simplest

hydroxy-formic

possible
acid,
COOH

H.

(Formic

will

It

hypothetical

acid)

COOH.

(Hydroxy-formic

that

carbonic

lowest

The

HO

-^

observed

be

be

wpuld

hydroxy-acid

this

acid)

is

identical

with

the

acid, H2CO3.

typical hydroxy-acid

is

hydroxyacetic

/OH
acid,

CH2"(^
under

viously

Glycollic acid
ways,

many

or

glycoUic

acid

(mentioned

pre-

glycol).
(ethanolic
starting

acid)

with

be

may

either

an

prepared

alcohol

or

in
an

acid:

(1) By
p.

oxidation

of

glycol

or

glycol aldehyde

(see

194).
(2) By

forming

the

cyanogen
212

derivative

of methyl

213

HYDROXY-ACIDS

alcohol, or, what

formaldehyde,

is the
then

thing, the cyanhydrin of

same

hydrolyzing:

/H

/CN

H.C"^+HCN=H.CH"^^.
of
(Cyanhydrin
formaldehyde)

/CN

/COOH

CH2"^Q
jj

+2H2O

CH2"^

(3) By boiling monochloracetic

+NH3.

acid

with

water

/OH

=CH2":^

CH2CICOOH+H2O

(4) By
nitrous

treating

aminoacetic

acid

+HC1.

(glycoeoU) with

acid:

CH2^cb0H +HNO2

CH2"^oOH
+^^^

+^"

(GlycoeoU)

methods

These

in

axe

general applicable

other

to

hydroxy-acids.
Glycollic acid
carboxyl

of

virtue

by

esters

(as also other

either

for

group;

hydroxy-acids)
the

example,

hydroxyl
ethyl

forms
or

the

gly collate,^

OTT

CHa^^COO

^^^
"

glycollic

C2H5'

acetate,

/OOC.CH3

CH2^^"

COOH

Glycollic acid
It

It is
J

forms

"

is found

in green

needle

stronger acid than

crystals, melting
acetic

Distinguish glycoUates from

glycol(p.194).

grapes

the

acid.

When

and

where.
else-

at

80".

heated

glycotetes derived

from

214

ORGANIC

in

with

combines

iOH

itself,losing water,
called

anhydride

an

forms

OC

HjO

"CH
COOiH

HOi

/Ooa
CH2":

has

neither

alcoholic

Just

acids.

pionic acids,

as

and

are

there

propionic acid and

properties.

there

called

conmionly

monochlorpro-

two

are

/3, so

"CH2+2H20.

acidic

nor

acids

Hydroxypropionic
lactic

thus

and

it

210",

at

glycollid:

CH2"

This

dioxide

carbon

of

atmosphere

an

CHEMISTRY

are

a-hydroxy-

an

jS-hydroxypropionic

The

acid.

/3 acid,

/OH

CH2^"
shows

(see

CH2"

by its reactions

300).

p.

acid.

It is

Lactic

that

It is therefore

in three

the

amyl

identical
kind
1

to

forms

alcohols

the molecule.

ethylene

described

isomers.

as

As

(p. 144), these

formulae.

lactic

acid,

that

positions in space

are

with

some

isomers

Isomerism

is called

now

physical phenomena

relative

ethylene

/OH
CH^^" COOH,

Stereochemistry {stereosmeaning
and

the

"

structural
be

called

to

a-hydroxypropionic

proper,

CH3

of

it is related

unimportant.

acid

is known

COOH,

have
the

of

stereoisomerism.^

ical
solid) treats of those chem-

supposed

to be

occupied by the

caused

atoms

by

within

215

HYDROXY'ACIDS

understand

To

of the

atoms

and

not

main

on

angle

is situated

CH3,

The

of

being placed in

as

at the
atom

or

and

H,

Models

group.

ing
helpful in understand-

will be

COOH

solid

of each

apex

represent a-lactic acid, write the

To

OH,

an

in space,

ordinary formulae.

thought

pasteboard

or

this.

is

tetrahedron,

of which

of wood

in

as

of the

conceive

to

being arranged

as

plane
atom

of

center

molecules

one

carbon

the

this it is necessary

.the

at

groups

the

of

corners

tetrahedron, thus:
OH

COOH

CH,

effect

the

Try

of

It will

possible ways.
different

two

when

the

is held
be

seen

tetrahedron
a

that

'* The

by

would

truth

of

interested
other.

off
in

those

be

this
the

statement

various

that

observing

are

that

to

combination

bne

other

the

only in the

be

can

case

two

most

his hands

are

of

The
mirror

pounds
com-

four
these

of

clearly shown

possible arrangements
identical.

possible

having

as

If

corners.

will

mirror

in the

represented

the

at

groups

writing down

marking

mirror, the image

is true

only

and

two

possible.^ Further,

representing

This

arrangement.

in all

groups

that

are

correspond exactly

to

different

found

be

arrangements

before

these

interchanging

and

student

images

then

will

be

of each

216

CHEMISTRY

ORGANIC

the

are

groups

possible and

stereoisomerism

metrical
central

carbon

It has

atom.

containing
the
rotates

it to

the

acid

is the

found

been

is also

acid

acid, but

shown
and

substance
acids

of racemic

action
that

is called

physiological

Certain

active

optically

which

action

of

degree
few

constituent

two

each

trolactic
dex-

other

in

their

polarized light. Optically active substances

on

have

*A

neutraUze

acid

of

such

molecules;
The

racemic.'^

not

It has

equal quantities
acid

laevolactic

nary
Ordi-

it does

been

of

rotates

acid.

polarized light; it is opticallyinactive.

consist

atom

laevolactic

affect

to

pounds
com-

Dextrolactic

of dextrolactic

a-lactic

an

its

metric
asym-

carbon

represented by models,

As

an

that

right, laevolactic

mirror-image

lactic

be

to

polarized light.^

the

it to

left.

said

unsjma-

present;

asymmetric

an

of

plane

acid

occur.

of groups

is therefore

atom

carbon

rotate

cannot

regards the kind

as

is

arrangement

one

representing lactic acid is

tetrahedron

The

only

same,

contain

action
the

on

animal

bases

have

other

atoms

ferent
dif-

been

than

asymmetric

an

organism

have

organic compounds

asymmetric

quaternary

show

may

pared
pre-

carbon.

atom,

as

CeHs

/CH,

CeHs-CH^-^NC
Br

C3H5/
The
of

pentavalent
a

been

has

atom

conceived

of

as

at the

center

pyramid.
substances

Racemic

might

better

be

called

speaking,

contain

molecular

combination

the

are

not

always mixtures; thed,Z-mixtures

conglomerates.
two

active

(cf.tartaric

The

molecules

acid).
.

racemic, properly
in

some

sort

of

217

HYDROXY-ACIDS

according
acting

whether

to

it is the

(see nicotine^

cocaine,

432, and

p.

433).

p.

Dextrolactic

beef

in

fermentation

because

it

extract.

It

Its salts

paralactid.

the

is

It

product

the

of

acidi

Micrococcus

acid) is obtainable

mentatio
by ferIcevo-

acidi

Micrococcus

the

by

of dextrose

flesh.

Isevorotatory.

are

(Hactic

acid

Laevolactic

is also

called

also

in

occurs

by

dextrose

of

is

(d-lactic acid)

acid

addy

sarcolactic

present

is

that

I isomer

or

atropine,

430,

p.

lactici.
Racemic

(d-, Z-lactic acid) is

acid

lactic

syrupy

15"

liquid having
It

specific gravity

than

is stronger
than

to which

it is related.

lactic

acid

sugar

becomes

1.2485

It is the
When

fermentation.
converted

lactic

ethylene

and

propionic

product

of

milk

sours,

lactic acid

into

at

and

organic acids,

most

stronger

of

-j^.

much

acids,

ordinary

by

milkorganisms
micro-

C12H22O1I

=4C3H603.

-'-H2O

(Lactic acid)

(Lactose)

No

in

matter

produced

lactic

way

by synthesis, the
The

racemic.

what

law

of

synthesis

calls

as

many

molecules

having

as

the

contains
Penicillium

It

can

be

dextrolactic

glaucum

lactate, because

the

in

the

for

the

shown

acid
a

mold

is

artificially

synthetic acid

probability

chemical

laevo.

acid

by

solution

as

is always

applied

formation

of

to

just

dextro-arrangement
that

d, Z-lactic acid

growing

the

mold

of d, Z-ammonium

destroys

the

Isevolactic

218

ORGANIC

acid.

On

the

lactate

acid

of

solution

crystals
heated

an

anhydride
acid

to 150"

10

H2SO4.

In

of

CH3

the

blood

or

c.c.

CH3

to

pionic
pro-

concentrated

of

CHO

with

Heat
for

+H

aldehyde

(see p. 160)
"

lactic

of

c.c.

distillate
acid

"

COOH.

(i3-oxybutyric acid),

acid

CH(OH)
of

mix
5

the

COOH

pathologically

laevo-

the

acid

condenser.

for formic

/3-Hydroxybutyric

is

and

with

lactic

retort

Test

CHOH

since

(cf glycollicacid,'p.

reduces

water,

(see p. 153) and

"

crystallization of

185).

p.

flame.

CH3

tain
con-

dry air,lactic acid changes

lactid

acid

Connect

smoky

to

(see

c.c.

shown

first.

in

called

Experiment.

acid,

fractional

by

formed

are

Hydriodic

214).

be

it may

strychnine lactate,

When
to

hand

other

Isevolactic
a

CHEMISTRY

CH2

"

importance,

COOH,

since

urine, especially

in

Isevorotatory, its specific rotation

it may

in

occur

diabetes.

is

It

(p. 245)

being

-24.12".
It will be
acid

noticed

that

the

ketone

acid

(/3-ketobutyricacid) corresponds

alcohol

acids, just

alcohols

CH3.

as

(see also

CHOH.

CH2-

ketones
p.

COOH

CH3CO.CH2.COOH

acid

the

to

correspond

to

above
ary
second-

(cf. CH3

"

CHOH

"

CH3)

(cf.CH3CO.CH3).

j8-Hydroxybutyric
acetoacetic

162)

acetoacetic

acid

can

by hydrogen

be

readily oxidized

peroxide.

to

220

ORGANIC

COOH

"

CHEMISTRY

C"
^O

+HOH

COOH

"

C^OH
\0H

or

CH(0H)2C00H.
It

is

like

reducing agent

(as chloral

aldehydes

hydrate).
(1) To

Experiments.
of

acid

oxahc
evolution

when

filtrate is

add

of

c.c.

of

amalgam;
filter.

ceased,

of glyoxylic acid

COOH

tion
solu-

strong

sodium

gm.

has

gas

solution

dilute

20

The

COOH

COOH
(Oxalic acid)

"

CHO
(Glyoxylic

(Nascent

acid)

hydrogen)

(2) To

solution) add
then

of

c.c.

gradually;

cholalic

of

is unknown.

color
the

valuable

Glycocholic

C2oH3i(CHOH)

acid

due

obtained,

molecule.

protein

is

trihydroxy-acid

cholic

C20H31

the

acid

its combinations

(CH20H)2

important
with

of

acids,

of bile.

formula:

"

CO"

HN

"

the

iological
phys-

glycin

taurochohc

constituents
the

portion
is

or

COOH.

[CaoHs^CHOH)]

This

has

heat

test.

taurin, glycocholic and

niost

is

solution,
and

mix

H2SO4;

in

acid, (CH20H)2

since

the

of

(egg-white

glyoxylic acid

the

contained

constitution

formula

solution

concentrated

example

An

with

of

c.c.

proteins give this

Most

The

albumin

bluish-violet

trytophan

to

of

c.c.

CH2COOH.

and
are

221

HYDROXY-ACIDS

Tatirocholic

is

acid

C2oH3i(CHOH)

is

Glycui*onic acid

aldehydic

an

CH0(CH0H)4C00H,
dextrose.

when

the

in

it is needed
such

substances,

urine

acid

closely related

is

the

in
The

free

alkaline

the

mixture;

that

so

It is not

(see

p.

these

are

acid, gly-

(like other

occasionally
a

COOH.

to

group

prolonged
a

fermentable.

It

reduce

aldehydes),

heating

mistake

may

urine

contains

reducing

It

differing only

of its combinations

some

that

concluding

abnormal

dilute

CH2OH

solutions

copper

from

body

It is excreted

monosaccharides,

particularly after

more

in

and

acid

with

in

as

with

indol.

the

free; this is dextrorotatory.

to

of

change

same

glycuronates;

heating

is set

the

animal

the

or

paired

By

of

arrangement

to combine

drugs

as
as

Isevorotatory.
curonic

by

(CH2)2S03H.

tetrahydroxy-acid,

being

groups

is formed

It

dextrose

the

alcohol

secondary

NH.

(CH20H)2CO"

of

the

be made

gives the pentose

sugar.

reactions

230).
Acids.

Monohydroxydibasic
COOH

Tartronic

acid,

CHOH,

has

been

supposed

to

take

COOH

part

in

the

physiological synthesis

particularly in birds
Malic

acid

is

(see

p.

290).

hydroxysuccinic acid,
CH(OH)"

COOH

CH2

COOH*

of

uric

acid,

"

222

ORGANIC

is

It

contained

CHEMISTRY

in

fruits,

sour

and

apples

e.g.,

cherries.
is used

Agaric Acid

as

remedy.

Its formula

is

Ci4H27(OH)(COOH)2.
Dihydroxydibasic

Acids.

COOH

I
acid, C\
I

Mesoxalic

OH
is the

third

exception

to

OH

COOH
the

rule

the

same

oxylic

that

carbon

acid

there
in

CH(OH)"

COOh'

p.

216)

of

stereoisomerism,
that

than
models

it

of tetrahedra
be

will

It

tartaric acids
are

sides

of

are

groups

being

at

an

is

that

lactic

shown

noticed
that

are

fact

acid.

in the

causes

connecting

With

and

lines and

OH,
are

of

pairs

tetrahedron

on

while

each
that

kevo-

and

H,

opposite

of the

centers

vertically opposite
of the

aid

the

Arrange

diagonally opposite,

angle

stand
under-

of dextro- smd

OH

the

species

diagram.

case

the groups,

(see

atoms

difficult to

more

in the

by straight

line

they

This

clearly understood.

as

connected

carbon

asymmetric

of

be

can

gly-

exceptions.

COOH

molecule.

the

to

and

hydrate

CH(OH)"

two

are

attached

dihydroxysuccinic acid,

is

acid

other

two

be

cannot

chloral

atom,

being the

Tartaric

Here

hydroxyls

two

hedra;
tetra-

the COOH

other,

both

points

for-

223

HYDROXY'ACIDS

ward.

As

models

with

for

identical

the

active

Place

the

of

equal quantities
inactive

acid.

By

it will

which

cannot

to

that

at

the

base

The

racemic

the

by
2

formula

tartaric

acid

is mesotartaric

above,

or

neutralization
molecular
on

the

acid, while
to that

of

optical
the

corresponds

top

arrangement

of dextro

however,
crystals,

model,

since

one,

the

tar taric.^

are

represented

4C4H6O6+2H2O.

It will further

possiblein the

acid

This

diagram

groups

corresponds

sepa-

22.

the

of laevotartaric

be

other
an-

Meso-tartaric

acid.

acids.

inner

an

of the

arrangement

the

that

is

acids

acid

studying

properties

laevo-tartaric

is, however,

LsBvo-tartaric

seen

mixture

There

optically active

be

is

acid).^

tartaric

the

acid.

in solution

when

Fig.

into

mirror;

and

acid.

rated

before

of dextro-

lactic

(cf. racemic

made

be

about.

model

add

these

acid,

cannot

dextrotartaric

to

tartaric

Dcxtro-tartaric

model

the

laevotartaric

image corresponds
Racemic

acids

tartaric

by turning

lactic

for

models

case

be

noted

that

of lactic acid.

an

acid

of this

variety is not

224

ORGANIC

Racemic

and

acid
is

in

tartar,

this

salt

insolubility
It

is

used

in

baking-powders.
sodium

being

the

Tartaric

acid

of
is

acid

carbon

dioxide

which

acid

by using

dilute

brown

It is easy

and

170".

gives

On

off

an

It

on

from

the

sium
potastartrate,

the

proper

forms

large

further

heating
odor

of

like

it

caramel.

soluble.

Dextrotartaric

by

at

best

which

calcium

acid.

sulphuric

fied.
puri-

from

as

of

crude

the

saltj

is obtained

is liberated

its

mixture

by precipitation

the

of

when

manufacture

some

or

wine

This

of tartar

cream

liberates

crystals, melting

acid

alcohol.

bitartrate

amount

turns

dilute

and

bicarbonate

bicarbonate.

from

out

is

bitartrate

because

separates
in

It

When

Baking-powder

dissolved

in

widely

dextrorotatory.
potassium

as

is called

argol,

or

differ

HO0C(CH0H)2C0OK.

tartrate,

relative

is

acid

grape-juice

produced

acids

solubility.

tartaric

Ordinary
contained

mesotartarie

and

melting-point

CHEMISTRY

boiling

acid
with

hydroxide

solution.

separating

racemic

can
an

be

converted

excess

The

two

lactic

acid

of

into

racemic

strong

sodium

methods

into

the

given
active

for

acids

225

HYDROXY-ACIDS

applicable also

are

discovered

third

slow

By

to racemic

method

sodium

ammonium

be

be

called

is very

two

racemate,

obtained, which

can

which

(below 28")

evaporation

from

their

and

right-handed

acid.

tartaric

of

Pasteur

interesting.
of

solution

classes

crystals

of

might

appearance

left-handed

crystals

(see Fig. 23).

crystals

The
These
furnishes

picked

be

can

mirror-images

are

another.

one

mechanically

out

dextrotartaric

of

acid, the other

set

one

laevotartaric

acid.
salt is sodium

Rochelle

potassium
COONa

CH(OH)"

This

has
as

+4H2O.

CH(OH)"

COOK

the

of

in

tartrate,

power

Fehling^s

tion,
in solu-

holding Cu(0H)2

solution.

is

It

used

as

cathartic.
Tartar

emetic

It is used

as

is

potassium

antimonyl

CH(OH)"

COOK

CH(OH)"

COO(SbO).

tartrate,

medicine.

(1) Heat

Experiments.

test-tube, stirring it with

the

melting-point.

continue
odor

an

Certain

heating.
like scorched
other

acids

citric,
malic, tannic, and

acid

acid

turns

thermometer
brown

in

Note

thermometer.
the

Remove
The

tartaric

some

and

and
emits

sugar.^
act

in

gallic.

the

same

way,

particularly

226

ORGANIC

(2)

Prepare

Sb203

and

filtrate

for

antimony

of

the

filtrate

(3)

After

and
a

boil.

to

reading

and

tartaric

the

Acid,

C(OH)

(having

molecule

easily

Other

acid

Organic

forms

in

currants,

crystallization)
cines.
medi-

valuable

are

which

Cu(0H)2

NaOH

by

crystals

large

of

water

Citrates

has
salt

(cf. Rochelle

in

solution).
that

hydroxyacids
are

leic

of

redissolve

precipitated

Fehling^s

is present

It

lemons.

soluble.

Citrates
been

of

power

COOH

and

is

rotary

Acids.

COOH,

"

gooseberries,

and

polariscope

"

CH2"

one

rest

COOH

CH2"

Citric

the

acid.

Monohydroxytribasic

the

evaporation.

the

of

determine

of

slow

by

add
of

some

aside

Set

of

gm.

water,

test

H2S.

description

of

c.c.

crystals

secure

solution

50

Filter
with

its manipulation,

strong

Dissolve

in

tartrate

gm.

emetic.

tartar

acid

potassium

CHEMISTRY

are

acid

dihydroxystearic

mentioned

(p. 207)

where
else-

and

ricino-

(p. 304).

good

description

Chemistry,

also

can

in

be
Mathews'

found

in

Cohen's

Physiological

Practical

Chemistry.

228

ORGANIC

CHEMISTRY

monosaccharides,

disaccharides,

polysaccharides,^

Monosaccharides
From

carbohydrates.
contains

in

its

molecules.
molecules

that

be

can

as

monosaccharides

pentoses,

while

ketoses

of carbon

charides
disac-

their

ion

atoms

present,

dioses, trioses, tetroses,

containing

those

are

saccharide
mono-

RIDES

called

those

are

complex

and

hexoses, heptoses, octoses, and

Aldoses

charide
monosac-

low.

OS A CCHA

are

trisac-

many

acids, but

number

simplest

have

into

and

charide
monosac-

three

resolved

weak

ON

the

to

two

result.

molecule

extremely

are

According

of

Monosaccharides

very

concentrations

linking

Polysaccharides

molecules.
act

the

are

disaccharides

molecules,
charide

the

tnsaccharides

having

nonoses.

aldehyde

an

ketone

group,

group.

"H20H

Glycol aldehyde,

be considered

may

diose.

CHO

Glycerose

be

can

glycerol (or lead

aldehyde
carbon

and

mild

by

gly cerate); it is

ketone, and

they

atoms,

obtained

are

since

trioses

oxidation
niixtm*e

of

contains

three

each

CHOH

-"

CH2OH

CHOH

CO

CHO

CH2OH
(Glycerol)

(Glyceric

an

CH2OH

CH2OH

of

CH2OH
aldehyde)

(Dihydroxyacetone)

(Glycerose)
^

These

are

saccharoses, and

also

called

monosaccharoses, disaccharoses,tri-

polysaccharoses.

CARBOHYDRATES

AND

229

GLUCOSIDES

CH2OH
CHOH

Tetrose,

obtained

be

can

by poljaneriza-

CHOH

CHO
tion

glycol aldehyde.

of

ketose

also

tetrose

occurs.

chief

The
The

pentoses

are

following formulae

their

represent

CH2OH
HO"

C"

HO"

HO"

C"

H"

C"

OH

HO"

C"

CHO

is obtainable

means

from

Xylose
bran

sometimes

On
fom*

main

these
are

of

are

in

urine

ketose

having

three

and
that

possible, so
Seven

obtained

by

of

abnormal

are

known.

asymmetric
mirror

eight
these

is

an

as

pentoses

the

similar

arabinose

Racemic

the

arrangements

obtainable.

be

wood.

Several

account

by boiling gum-arabic with

can

or

present

constituent.

(Z-xylose)

({2-arabinose)

acid.

OH

CHO

dilute

tion:
rela-

C"

Arabinose

isomeric

C"

H"

Z-xylose.

CH2OH

and

d-arabinose

aldose
are

atoms,

images

of

pentoses
known

at

present.
Both

and

arabinose
form

and
osazones

xylose reduce
with

Fehling's

tion
solu-

phenylhydrazine (the

230

of

nature

the

If

having

HOiCH

is

by

explained

with

yeast.

pure

be

will

below.

strong HCl,

(furf urol)

aldehyde

an

is produced

CHjOHl

"

^TT

be

reactions, which

experiment

chain

will

fermented

color

is boiled

closed

reaction

in the

pentose

osazone

certain

give

illustrated

CHEMISTRY

Neither

presently).

They

ORGANIC

^TT

CH"

III

CH

"CHO=CH

CCHO+3H2O
\

/
.

(Pentose)

f\^
(Furfurol)

of the

Most
have

Several

and

phloroglucin, a
add

Now
a

color

red

small

the

is

the

time,

of arabinose

obtained;

d and

alcohol

as

long

examine

it dissolves.

as

spectroscopicappearance

Heat

seen.

colored
as

until

with

once

band
until

alcohol, and

amyl

some

becomes

heat

absorption

an

in
Add

warm.

at

di-

tose.
pen-

of water

c.c.

and

lines will be
add

methyl

solution, and

when

precipitate forms,

shake;
same

c.c.

little at

HCl

of

c.c.

spectroscope,

between
a

To

test.

dimethyl-

C6H12O5,

Pentose
add

test-tube

monosaccharides

of

digitoxosey C6H12O4,

as

rhamnose,

Experiment.
a

products.

digitalose, C7H14O5,

methyltetrose,
pentose,

in natural

glucosides,

far considered

thus

derivatives

methyl

in

occur

found

been

not

monosaccharides

and

above.

gives the

CARBOHYDRATES

The

hezoses

The

"

the

are

chief

laevulose; the
is

AND

first two

prime

tance.
impor-

dextrose, galactose, and

are

aldoses, while

are

the

last

ketose:

CH2OH

11

HO"

C"

HO"

C"

HO"

H"

C"

HO"

C"

C"

OH

HO"

C"

I
H"

HO"

C"

OH

C"

H"

HO"

CHO

The

have

eight main

image

(Lsevulose

of the

(d-fructose))

fore
there-

atoms,

hol
alco-

secondary

mirror

possible.

make

images

Twelve

of

these

alcohol

secondary
are

chemical

The

in

d-glucose only

from

aldoses

it is called

of its

arrangement

secondary

the

group.

and

Z-hexoses
for

name

d-fructose
alcohol

the

are

laevulose

because
groups

the
is the

d-glucose.

ketose

hexoses

being

importance
been

CH2OH

their

fourth

of the

is fructose, and

Six

OH

C"

C=0

asymmetric

hexoses

laevorotatory.

in

four

differs

mirror

as

H"

studied.

been

arrangement

same

C"

arrangements

aldose

d-Mannose

The

OH

together with

groups

have

C"

(d-galactose)

aldoses

sixteen

CHO

(d-glucose)

Dextrose

CH2OH

CH2OH

have

of

sugars

ones

231

GLUCOSIDES

are

known,

laevulose.

the

Two

only

methyl

one

of

hexoses

prepared.

Condensation

of the

aldehyde

and

ketone

trioses

232

in

ORGANIC

glycerose

results

CHEMISTRY

in

the

production

of

ketose,

d, I fructose, thus:
CH2OH

CH2OH

CHOH

CHOH

CHO

HCHOH

CHOH

CHOH

CO

I
CO

CH2OH
(Glyceric

aldehyde)

(Dihydroxyacetone)
~^

^^e^^)

CH2OH
(Ketohexose)

The
weak

condensation
alkali yields the

All
when

the

synthetic

glycerol (from fat)

at

least under
Dextrose

that

in

means.

the

converted

animal
into

body
hexose,

circumstances.

certain

is the

chemical

be

may

optically inactive

are

sugars

believe

by

product.

same

produced by purely

Physiologists

induced

formaldehyde

of

aldehyde

of the hexacid

alcohol

sor-

CH2OH

bitolj(CHOH)

4,

and

be

can

into

converted

the latter

CH2OH

by

reduction.

Dextrose

be

can

oxidized

to

the

COOH

dibasic

acid

saccharic

add,

(CHOH)

4.

The

can

be

alcohol

COOH

dukitol,
to

stereoisomer

galactose, and

this

of sorbitol)

aldehyde

monosaccharide

oxidized
can

CARBOHYDRATES

AND

233

GLUCOSIDES

COOH

I
be

oxidized

further

mudc

to

Sim-

acid, (CH0H)4.
COOH

ilarlythere
to

the

other

of the

and

the

ment
arrange-

the

as

saccharides
mono-

related.
is

monobasic

of

arrangement

same

same

groups

are

(p. 221)

d-glucose, the

as

corresponding

the

have

alcohol

they

acid

Glycuronic

groups

acids

secondary
to which

having

acids

hexoses.

alcohols

These

and

alcohols

are

aldehyde

acid,

the

CHOH

also

group

being

present.
There

certain

are

such

proper;

called

are

has

sugar

that
with

combined

derivative

combined

proteins

been

found

contain
the

hydrate
carbo-

cule
protein moleThis

glucoproteins.
in

most

to

cases

CH2OH
\

(CH0H)3
be

an

generally glucosamine,

aminohexose,

CHNH2
CHO
sometimes

in

combination
in

protein

(see exp.

may

from

nucleoproteins.

be

detected

the

of

certain

proteins

possibilityof the

other

th^n
The

physiologicalimportance.
now

by

The

is

found

sugar

in

group

color

reactions

formation

of

below).

question

The

^-Xylose

galactosamine.

be briefly considered.

acids (see p. 267).

When

glucoproteins is

chemistry, of

Proteins
we

reason

of

the

readily splitup

great

very

problem
into

(fti purely chemical

trose
dex-

will

amino-

grounds,

234

we

ORGANIC

that

see

six carbon

it is

be

can

Such

undoubtedly

acid

of

production

the

production

of

therefore

COOH,

alanin.

COOH,

lactic acid.

COOH,

glycericacid.

CHO,

glycericaldehyde.

CHO,

dextrose-like

from
the

in

lactic

densation.
con-

animal

dextrose,

into dextrose;

serin.

dextrose

demonstrated,

in

out

COOH,

glutaminic acid

and

in

finally

quite likely that serin is also

It is

into lactic acid and

convertible

glyceric

to

by aldol

sugar

carried

result

i.e.,dextrorotatory glucose.

The

dextrose-like

synthesis when

would

organism

into

acid, the latter

glyceric aldehyde, and

to

or

into dextrose.

lactic

to

reduced

converted

be

can

changed

containing three

amino-acids

converted

be

can

be

can

acid, which
this

possible that

atoms

Alanin

CHEMISTRY

alanin, glycocoU, aspartic

animal

acid

aldose.

has

body

being noted

been
as

imentally
exper-

mediate
inter-

an

product.
To

Experiment.

add

protein

egg

a-naphthol

in

pipette add

does

not

of

c.c.

but

C.P.
forms

as

to

color

violet
cause

is Molisch's

stand

does

not

slightmixing
test

and

of

strong

saturated

is

containing substances.*

H2SO4,
a

so

bottom

until

the

given by

of

solution

of

then

that

with

The

all

the

to

ring forms.

tap the
two

acid

the

is due

violet

appear,
of

solution

layer.

of contact

zone

reagents ; let the tube

If the

of

(acetone-free);

the

at

c.c.

drop

alcohol

mix,

greenish color

tube

layers.

so

This

carbohydrate-

236

ORGANIC

This

be

can

CHEMISTRY

converted

by

with

treatment

warm

CH2OH

(CH0H)3

hydrochloric

acid

into

glucosone,

When

CO
CHO

glucosone

is treated

with

using zinc

dust), fructose

convert

aldose

an

and

Dextrose

lose is

This

has

linking

all have

is called
been

molecule

and

asymmetric
designated

as

of

case

d-glucose.

This

two

and

that

so

and

C"

been

will be illustrated

H"

HO"

C"

H"

OH

C"

C"

OH

C"

HO"

C"

C"

OH

HO"

C"

a-d-glucose

ble,
possigated
investi-

by d-glucose :

CH2OH

O
HO"

is

Z-arabinose, d-galactose, lactose

This

C atom

become

has

C-H

C"

which

hyde
of the alde-

H"

rotary

lactone-like

This

OH.

This

the

stereoisomers
/3.

; laevu-

multirotation.

or

CH2OH
HO"

stand.

to

mutarotation

to hold

comes

in the

that

explained by supposing

in the sugar

group

different

from

allowing the solution

after

can

we

dextrorotatory

are

freshly dissolved

phenomenon

Thus

(as by

ketose.

galactose

when

they show

and

is formed.

Isevorotatory. They

power

now

into

hydrogen

nascent

jS-d-glucoee

CARBOHYDRATES

The

variety, immediately

solution, has
the

and

changes
of

jS, and

both

in

52.5";

The

two

into
and

solutions.

The

other

the

to

partly changes

partly changes

/5 in the
from

change

is believed

the
take

to

form,

the

aldehyde, CH20H(CHOH)4CH(OH)2.

There

is

supposed

be

to

sugar

believed
and

to

does

active

of two

or

thymol
curonic

the

reduce

after

the

phenylhydrazine

positive. The

Maltose

is

main
i-Glu-

dioxide.

carbon

reducing

the

optically

(dextrose, laevulose,

sugar

urine

of chloral

(see

Fehling's

this

bodies

are

solution,it
of

may

fermentation

most

in

gly-

bismuth

the

(uric

acid

and

yet be positive

antipyrin, salol,

rhubarb, benzosol, sulphonal,

is the

menthol,

excreted

substances

delicate

is

slightly

reagent

While

221).

p.

administration

test

solution

hydrate, camphor,

these

FehUng's

of

reduce

may

non-saccharine

many

kairin, senna,
The

for

test

combination

creatinin) that
urine

and

antipyrin because

excludes

of

by yeast, the

lactose) in the urine, reduction

acid

response

fitsonly the d-form.

administration

or

in the

a-d-glucose molecules,

ferment, possibly because

sufficient,for

after the

tests.

fermented

are

but

jS-d-glucose molecules.

of two

enzyme

pentose,

with

up

not

making

In

test

be made

being alcohol

products

not

aldehyde

hexoses

These

cose

to

an

lactone

explaining the

solution

isomaltose

not

of this present

trace

thus

equilibrium mixture,
the

being

glucose

place through

intermediate

hydrated

this

of the

of

form

one

a.

concentrated'

of

case

to

to

40%

when

equilibrium

60%

solution

specific rotation

/3

110",

of

each

standing

solution

preparing

(p. 245)

solution

one

other

come
a

On

finallycome

the

the

in

glucose is

to

19".

variety

/3

after

specific rotation

237

GLUCOSIDES

AND

and

or

pentine,
tur-

trional.

the

most

test, if positive,is generally

con-

238

If lactose

elusive.
will not

boiling

in the

and

test

from

urine

has

because

reducing

dextrose, but

0.2%

added

it with

heating

urine

to

alkali

acid.

produces formic
Normal

by the special

dextrose

Chloroform

by Isevorotation.

preservative gives reduction

after

(hydrolysis).

differentiated

be

specialpentose

in dextrotation

by increase

of lactose

case

can

distinguished by

be

can

present, fermentation

be

alone

pentose

dilute HCl

with

Laevulose

ketose

or

These

occur.

test, and

as

CHEMISTRY

ORGANIC

equivalent

power

one-fifth

less than

to

of this is due

to dextrose.

(glucose,

Dextrose

and

fruits
diabetic

candies, cheap

from

latter.

sweet

It

to

Calcium
is

only

Experiments.
and

strong solution

by

making

glucose

tains
con-

slightly
is

of the

cane

sugar.

hydrolysis

slowly.
sugar) is contained

soluble.

in

rarely in urine.

and

rotary

compound

and

tion.
concentra-

with

The

is

power

tevulose

corresponding

easily soluble.

(1) Prepare
laevulose

of

methyl alcohol
as

temperature

on

of water

lactose, by

crystallize. Its

forms

glucose compound

dextrose

from

fruits, in honey,

greatly dependent
that

sweet

so

It ferments

is difficult

for

molecule

if crystallizedfrom

(fructose, fruit

Laevulose

of

glucose is crystalline; if crystallized

is obtained

Galactose

urine

the

crude

This

It is not

anhydrous.

in many

glucose is made

it contains

water

in

acid ; it is used

etc.

Pure

but
crystallization,

many

dilute

syrup,

dextrin.

of the

Commercial

with

boiling starch

it is

and

plants, in honey,

patients.

is present

sugar)

grape

as

sugar

follows:
add

crystals from

osazone

0.25

To
gm.

10

c.c.

of

of

phenyl-

CARBOHYDRATES

hydrazine

hydrochloride
in

acetate, heat
and

thoroughly with cold

acetic
from

The

yellow

the

crystals on

sodium

for

later make

the

the

filter,wash

acidulated

with

recrystallize
filter-paper,

melting-point

of

osazones

hour,

an

crystals under

water

or

of

gm.

bath

water

acetone

239

alcohol, dry the crystals in

little 80%
and

0.5

between

acid, press
a

and

the

Collect

microscope.

GLUCOSIDES

boiling

Examine

cool.

AND

important

cator,
desic-

determinations.^
have

sugars

the

following melting-points :

P'^^^^'M
Lsevulose

Lactose

200''

Maltose

206"

(2) Ketose
add

of

c.c.

heat

the

later

The

test.

To

25%

HCl.

mixture.

brown

(4

the

one-fifth

Add

red

and

little resorcin
color

and

develops,

in alcohol.

is soluble

its volume

dissolved

in

some

of alkaline
and

100

On

dextrose

solution

bismuth

reagent

bismuth

10%

of

cooling

153) with

of

gm.

c.c.

p.

(see

tests

(6) To

minutes.

solution

laevulose

is red.

salt

five

of

deep

Rochelle

gm.

c.c.

aldehyde

solution.

nitrate
boil

solution

(3) (a) Try

dextrose

precipitate,which

alcoholic

add

204"-205"

suband

NaOH),

black

precipitate

out.

separates

*A

quicker

and

crystals

is

0.5

glacial acetic

sugar

c.c.

as

follows:

solution, and

crystals appear
heat 20-30

satisfactoryway

more

To

0.5

acid;

heat

in 5-10

minutes, then

in

c.c.

osazone

phenylhydrazine (base) add

after
a

of securing

mixing add

10

boiling water-bath;

minutes.
cool before

For

lact- and

examining.

c.c.

of

the

glucosazone

maltosazone,

240

ORGANIC

Several

known,

CHEMISTRY

heptoses and

but

they

and

octoses

two

nonoses

are

unimportant.

are

DISACCHARIDES

These

the

are

monosaccharide

two

of

molecule

of
and

molecules, with

of water,

dextrose

cane

and

elimination

being

sugar

of

maltose

tion
combina-

dextrose

of

a-d-glucose

two

=Ci2H220ll+H20.

C6H12O6+C6H12O6

By

the

of

union

the

tevulose, lactose

and

galactose,

molecules

theoreticallyof

result

the

hydrolysis

monosaccharides

constituent

are

easily obtained:
C12H22O11
Dilute

mineral

about

this

Yeast

+H2O
acids

and

none

Therefore

lactose

while

sugar

cane

Inversion
to

the

case

of

p.

452),

bismuth

does

not

inversion.

hydrolyzes
effect

an

maltose

cane
on

sugar

lactose.

with

ferment

yeast,

do.

maltose

hydrolysis
and

of dilute

mineral

ions, just

hydrogen

of esters

acids

(p. 180) (see

is
in

as

dix,
appen-

'

lactose

solutions; pure

reagents.
for

has

of

called

hydrolyzes

that

and

(invertases) bring
is

that

that

catalytic action

inversion,

which

by the action

due

Maltose

ferments

invertase

an

another

but

slowly,

and

hydrolysis,

produces

quickly

=C6Hi206+C6Hi206.

however,
Therefore

reduce
cane
cane

alkaline
sugar

does

sugar

of all the

and

not.

After

reduces

these

Fehling's solution

quantitativeestimation

copper

can

sugars

be

used

treated

of in

this

reduced

10

chapter.

is

solution

FehUng^s

of

c.c.

241

GLUCOSIDES

AND

CARBOHYDRATES

by
0.048

dextrose.

gram
''

0.051

tevulose.

0.0676

"

lactose

0.074

"

maltose.

0.0475

"

cane

(+H2O).
(after conversion

sugar

into

invert-sugar)
.

acid

solution

of copper

(Barfoed's reagent) is
oxide

cuprous

acidified

acetate

reduced

not

disaccharides, but

by

with

acetic

quickly

is

to

reduced

so

by monosaccharides.
Maltose

and

hydrazine,

lactose

each

while

cane

and

cane

order
sugar

to
as

the

is

with

osazones

having

no

such

(see

explain
shown

by

the

non-aldehydic

""

C"

has

been

CH2OH
HO"

C"

C"

I
C"

OH

HC"

OH

O
C"

vided
pro-

HOC"

0\
\

CH2OH

action

in these

its behavior

CH2OH

H"

239),

combination

for it :

p.

guarded against.

following formula

HO"

phenyl-

characteristic

melting-point

forms

sugar

hydrolysis
In

these

of

crystalline form

form

\CH

two

of
actions,
re-

suggested

242

Both

by

CHEMISTRY

ORGANIC

the

the

and

aldehyde

ketone

linking together of their C

The

disaccharides

other

have

tied

are

groups

up

atoms.

following

the

mulae:
for-

Maltose.

CH;

CH2OH
HO"

H"

C"

C"

C"

OH

HO"

H"

""

C"

OH

O
HO"

C"

HO"

H"

(a-d-glucose

H"

C"

H"

C-

H"

C"

HO"

H"

OH

C"

HO"

-0

disaccharides

shows

the

least; maltose
solution

C"

""

C"

OH

C"

C"

OH

(i-gluGose)

all

are

greatest
and

H"

(d-galactose

These

OH

H"

C"

CH.

O
HO"

Lactose.

CH2OH
HO"

C"

a-d-glucose)

Lactose

C"

rotary

lactose

contains

dextrorotatory.

manifest
and

lactose

power,

tose
Malthe

multirotation.

jS lactose

in

equilib-

244

ORGANIC

210''-220''

160''; at

Sit

with

loss

of

15"

at

saturated

Its rotary

dissolving

is

soluble,

197

with

sugar;

of

bases.
somewhat

by

lessened

of

gm.

100

specific gravity

is influenced

power

salts, but

or

has

caramel

into

extremely

saccharates

it

alkalies

is

solution

It forms

1.329.

it is converted
It

water.

ghi. of water
this

CHEMISTRY

by
of

presence

centration;
con-

acids,

practically uninfluenced

it is

by temperature.
(milk

Lactose

contained

sugar

the

urine

of

in

milk.

heated

it

It

and

pregnant

microorganisms
When

occasionally
nursing

forms

crystalline and

of

of

crystallization. It
lactose, which

amorphous
forms

compounds

is not

influenced

of

the

It

with

treatment

the

acid

It

rotation

varies

Isomaltose

osazone

dilute

obtained

is the

not

lower

as

Lactose

specific rotation
ature.
temper-

or

product

of

the

(in malt), ptyalin

obtained

from

starch
action

acids, the
stage before

at

in

fine needles.-

concentration

ferment

with

by
of

glucose is
Its

and

(gallisin)is distinguished from

it does
has

Its

mineral

crystalUzes
with

be

(in pancreatic juice) upon

be

being stopped

formed.

in that

also

molecule

anhydrous.

diastase

amylopsin

can

CeHioOs.

by concentration

ferments

(in saliva), or
starch.

much

C12H22O11+H2O,

Maltose,
action

is

bases.

with

tain
Cer-

women.

contains
can

in

occurs

lactocaramel,

is

the

into lactic acid.

lactose

convert

Lactose
water

is

sugar), C12H22O11+H2O,

yeast, and

melting-point (150").

specific

ture.
tempera-

maltose
that

its

CARBOHYDRATES

from

lactose

When

the

and

solutions

water

sugar

with

cane

50

of

c.c.

20%

The

is

as

of

the

to

mark.

with

(a)

(6) To

100

c.c.

heat

in

in

the

[a\D of the

uated
grada

ing
boiltralize,
neu-

this

Examine

(corresponding
in

of pure

Cool, almost

tion
concentra-

polariscope.^

important

sodium

sugars

Ught is used

(anhydrous)

4-52.5"

Lsevulose

Cane

+52.5
66

sugar

Invert

04"

+ 137

(+H2O)

Lactose

93.0"

(anhydrous)

Maltose

54

sugar

20

"

+81.0"

Galactose
(

Test

acid, and

(at 20") when

Dextrose

(3)

dissolved

gm.

solution)

in

solution

minutes.

30

solution

solution

(10

c.c.

of citric

solution

follows

100

sugar

specific rotation

10%

in

scopically.
micro-

polariscope (see p. 226)

fill up

the

to

the

for

invert-sugar

239).

p.

cooled, examine

solution

to make

1 gm.

water-bath
and

10%

cane

flask add

(footnote,

melting-point determinations.

(2) (a) Examine

enough

have

crystals

osazone

maltose

from

Make

in

Produce

(1)

Experiments.

245

GLUCOSIDES

AND

"

cane

means

rotation

to

before

sugar

(solutions of experiment 2,

the

left.)

and
and

after

6) with

inversion

FehUng's

solution.
the

(4) Try

ketose

test

(see

p.

239)

on

cane

sugar.
100
"

."

For

..

X rotation

observed

/w

calculation,%

sugar

["|Dx decimeters

tube

length'

246

ORGANIC

test. To

(5) Galactose
add

lactose

Now
3

If

10

and

on

stirring. Add

stand

material

and

examine

and

d-glucose
saccharose,

of

none

of

Invertase

d-fructose,
as

in

being free.

It

an

osazone.

and

sugar

ketose

the

hours.

together

hydrolyzes it,

yeast

cool.

out, let the

give

cane

and

of

groups
nor

utes.
minabout

twenty-four

linked

reduce

gives

It

of water

after

it to

few

to

separate

CO

the

not

hydrolyzes

Emulsin

boil for

c.c.

d-galactose

does

therefore

strong solution of

raffinose,consists

trisaccharide

The

water-bath

acid

crystals of mucic

no

of

c.c.

of HNO3

c.c.

evaporate

while

c.c.

CHEMISTRY

galactose.
ments.
it fer-

therefore

specific

Its

test.

is +104",

rotation

POLYSACCHARIDES

have

These

of

formula

complex
being

each

the

molecules,
unknown

an

empirical

multiple

of

CeHioOs.

(CeHioOs)^:

Cellulose,
molecular

high

being the
entirely
few

an

best

paper

be

acid, its surfaces

renders
paper

the
is made

paper

are

treated

is

acids

tough

in this way.

able

of
to

momentarily

become

plants,
almost

changed

to

by
and

copper

dissolve
with

solution

only
lies
alkaoxide

it.

If

sulphuric

amyloid,

dried.

when
If

composed

is affected

solution

of

Cotton-fiber,

paper

agents ; concentrated
anmioniacal

all

filter-paper are

Cellulose

(Schweitzer's reagent)
unsized

to

fiber.

woody

Ordinary

cellulose.

chemical
and

the

the

cellulose.
of

mainly
a

of

flax, and

hemp,

is essential

weight,

basis

(C6H702(OH)3)a:,

or

which

Parchment
of cellulose

CARBOHYDRATES

in

sulphuric

glucose

acid

Experiments.
in

paper

with

little cold

200

(1) Dissolve

of

some

and

with

test

this

for

beaker

of water,

Allow

the

of

and

wash

out

dry out;

to

paper

tralize
Neu-

hour.

an

solution

cellulose

80%

in

blotting-paper

only,

moment

boil for

solution.

piece

dilute

H2SO4,

hydrolyzed

Fehling's

(2) Immerse
H2SO4

and

of filter-

scraps

concentrated

of water,

c.c.

some

and

cellulose.

by hydrolysis of the

produced

are

boiled, dextrin

and

diluted

be

247

GLUCOSIDES

AND

large

transfer

to

the

thoroughly.

acid

it will be

found

in

made

be

to

tough.
(3) Detection
wood.

Coat

solution

of

lignin ^

sheet

of aniline

of

in

paper

white

cheap

with

paper

yellow, lignin

if it turns

HCl;

from

is present.
Esters

of cellulose
that

reagents
acetic

attack

cellulose

is treated

of

just

nitroglycerol

as

from

range

in
on

explodes

to

is

produced

explosive.
a

removing
a

of

(as

groups

By

gelatinous
the

slowly.
present

pentosans

and

with

glycerol.
cellulose.
is trinitro-

dissolving
mass

that

substance

cellulose in wood;

aromatic

formed,

are

from

solvent, the
This

in the

to trinitrocellulose.

physical condition

more

substance

contain

is

mononitro-

acetone

left in such

action

acid

nitric

(nitrocellulose,pyroxylin)
It

cotton

with

sulphuric acid, nitro-celluloses

Guncotton

the

by

hydroxyl

alcoholic

presence

then

formed

anhydride).

When

These

be

can

bodies.

is

gun-

obtained;

guncotton
it burns
is used
it is

is
and
in

supposed

248

ORGANIC

smokeless

dioxide, and
The

The

powders.

Collodion

is

of

and

ether

explosion

monoxide

carbon

and

water-vapor.
lower

two

of the

products

hydrogen,

nitrogen,

are

CHEMISTRY

nitrates

solution

of these

alcohol.
in

them

contained

are

nitrates

Celluloid
with

camphor

in celloidin.

is

in

mixture

made

the

solving
dis-

by

aid

of

little

alcohol.
"

An

artificial silk

fine filaments

calcium

made

being

and

which

sulphide,

by

method,

is

is treated

with

considerable

silk,is

fibers.

as

left.
of

others.

obtained

be

and

solution

NaOH

openings

one

The

cellulose

into

an

acid

After

with

from

silk

wood

solution
bath

the

viscose

is made

from

The

latter

is macerated
is

for

squirted through

which
of

is produced

silk

pulp.

and

CS2,

of

Almost

groups.

Artificial

Viscose

being

solution

these, called

quantities

Large

trinitrocellulose,

thread.

the. NO2

removes

the

can

time.

fine

cellulose

as

into

is treated

methods,

supplanting

cellulose

pure

very

other

two

of

means

spun

fabric

cellulose,resembling

pure

as

produced by

nitrocellulose

the

woven

be

can

precipitates the

artificial silk

are

now

produced.
Mix

Experiment.
c.c.

absorbent

cotton

then

out

wash

in the

the

of water,

quantity

temperature.

room

with

into

an

syrupy

glassy

piece

mixture

c.c.

acid

evaporating

out

press

When

of ether
dish

cool, immerse
for half

mixture
from

and
and

the
the

water,

dry,

shake

alcohol,
allow

pour

to

of

the

cotton.

Test

dry

the

and

minute,
large

and

dry

at

of

part
the

compare

and
of

it

liquid
A

evaporate.

inflammabihty

cotton,

10

some

with

cotton

liquid (collodion) is obtained,

skin.

and

HNO3

of C.P.
it is

When

H2SO4.

of C.P.

later

another
with

treated
un-

CARBOHYDRATES

(amylum),

Starch

(CeHioOs)^,

part of all vegetable food.

Starch

plants.
covered

with

substance

which

within
Starch

the

from

plants

and

starch
action

the

to

than

agents

of

stance
sub-

the

by

sation
conden-

of

processes

is made

is insoluble

in cold

into

goes

to

from

of

amount

solution

boiled, it

forms

or

potatoes.

or

When

water.

solution
the

corn

gelatinous

water

present.

containing also tiny

masses

suspension.
It

is

precipitated from
alcohol, and

of
salts

(as Na2S04

boiled

starch

and
is

solution

by

NaCl).

further, the
alone

converts

bread

is

probably

by

the

again.

acid

into

dextrin;

color

the

is lost

Natural

black

about

carries

being

40".

iodine
until

starch

the

forming
from
the

the

glucose.

takes

Starch

adsorption, thus
drives

of

ferments

by
of

product

dextrin.

solution

maltose, while hydrolysis

mineral

starch

mainly
heat

that

end

certain

platinum

by

temperature

dilute

by boiling with

cool

at

is first formed, then

Dextrin

dilute

tration
concen-

with

readily hydrolyzed

(catalytic action)

low

by

saturation

(diastase, ptyalin, etc.) and

so

spherocrystals,

probably synthesized by

are

starch

colloidal

ferent
dif-

in

grains.

according

It is

as

polymerization.

apparently
mass,

chemical

formaldehyde

Ordinary
Starch

sizes

are

resistant

cellulose

and

plant

specially modified

more

and

ferments

water,

in

is

large

in the

and

forms

grains

layer of

comprises

It exists

different

granules, having

249

GLUCOSIDES

AND

this
mixture

contains

Heat

crust

on

iodine,

up
a

ess
proc-

blue

stance;
sub-

substance,
becomes
two

dif-

250

ferent

materials,
of the

(60-80%
hot

iodine, while

less

are

intermediate

The

complexity,

color

blue

brown
a

no

red

color

test.

by

insoluble

in alcohol.

saturating

by

ammonium

their

reaches

concentration
much

as

The

dextrins

are

as

for the

192-196"
them

glucose.

to

90%

prepared
gummy

labels.

It

as

Most

sulphate.
the

is

precipitated

salts, such
when

the

dextrins

lower

precipitation.

dextrorotatory,

higher

dextrins

alcohol

75%;
for

is

are

with

sodium

gives

reddish

or

It forms

precipitated by

are

require

and

order

first

simpler

making

solutions

and

amylo-dextrins

dextrins

Most

sulphate

dextrins

for

the

red

dextrin

of heat.-

is used

in

the

Conmiercial

means

solution, which

second

color),while

starch.

starch

The

erythro- and

of

bluish

starch

from

iodine, the

there

erythrodextrins,

maltodextrins.

(a mixture

gives
give

with

than

are,

amylodextrins,

achroodextrins, and

that

are

(stereoisomers).

between

during digestion

with

Both

probable

bodies

complex

color

blue.

amyloses

substances

formed

maltose
of

of

ble
insolu-

an

little

deep

It is

ferments.

large number

Dextrins

amylose

gelatinizes with

gives

amylose gives

hydrolyzed by
very

substance

amylopectin, which

Amylopectin

water.

soluble

weight of the starch) and

substance,

is

CHEMISTRY

ORGANIC

dextrins.

Diastatic

the

Acid

ferments

{a)D

being

hydrolyzes

change

them

to maltose.

Glycogen,
present

in animal

liver acts
up

(CeHioOs)^,

in the

as

form

resembles

tissues,mainly

storehouse
of

for

glycogen

dextrin.
in the

liver.

carbohydrates,

the

sugar

It

that

is

The

storing

comes

to

252

ORGANIC

cines.

CHEMISTRY

large number

studied.

The

of

derived

sugar

have

glucosides
from

them

is

been

generally

glucose.
is used

Phloridzin, C21H24O10,
diabetes
and

glucose
glucin,

p.

to

It

animals.

in

produce
splits

imental
exper-

into

up

(see also phloro-

phloretin, C15H14O5

348).

Arbutin,

C12H16O7,

is

glucoside, hydrolyzing

to

comparatively

simple

dextrose

hydro-

and

quinone.

CuHigOg,

Gaultherin,
in the

is

wii;itergreenplant;

hydrolyzes

and

it to dextrose

is used

Salicin, CisHigO?,
dextrose

to

an

contained

glucoside

ferment

accompanying
methyl
in

salicylate.
it

medicine;

saligenin (p. 354).

and

lyzes
hydro-

Its struc-

/OCeHiiOs
tural

is CeHX

formula

Amygdalin,

peach-pits,

The

etc.

emulsin,

ferment

acids, hydrolyzes

it to

and

(see p. 351).

benzaldehyde

Its structural

in bitter

is found

C20H27NO11,

as

almonds,
well

glucose, hydrocyanic
is said

formula

to

acid,

be:

0-

CH(CH0H)2CH

OCH

(CHOH)
O

CeHs"

CH"

CN

CHOH

"

2CH-

CH2

CHOH

as

"CH2OH.

CARBOHYDRATES

Digitalin, C35H56O14,

hydrolyzes

talis,
principle of digi-

active

an

253

GLUCOSIDES

AND

C22H30O3,
dextrose, digitaligenin,

to

digitalose,C7H14O5.

and

the

Digitoxiiiy C34H54O11,

digitalis, yields

of

and

C22H32O4,

alcohol,

hydrolysis

C40H66O19,

and

mannose.

the

by

mustard

strophanthus,
methyl

rhamnose.
.the

action

splits

and

digitoxigenin,

from

Sinigrin, C10H18NS2KO10,

the

glucoside

strophanthidin, C27H38O7,

to

mustard,

active

digitoxose, C6H12O4.

Strophanthine

hydrolyzes

by

chief

white

mustard

parahydroxytolyl

oil

black
in

trose,
oil,*dex-

sinalbin,

manner

mustard

of

present

mustard

similar

In

of

ferment

into

up

KHSO4.

C30H44N2S2O16,

of

glucoside

yields dextrose,
sinapin bisul-

and,

phate.
contained

in

produced.

those

It
The

indoxyl.
is

different

Saponins.

is

of

present

is

indigo

is

glucose

urine

in

which

and

(p. 417)

compound.
A

number

large
into

and

of

glucosides

sub-class.

this

They

form

solutions

that

saponin

contained

in

foam

are
are
on

(cf. soaps).

shaking

Digitonin

C54H92O28;

is
it

sphts

molecules

two

Artificial

example,
group

which

from

combination

indican

non-nitrogenous

and

glucoside

the

plants

together

grouped

is

CmHitOgN,

Indican,

each

glucosides

into

digitogenin, C30H48O6,

of glucose and

simpler

are

galactose.

compounds;

methyl glucoside of d-glucose

attached

glucose.

up

to

of

digitalis,

the

has

aldehyde

for

the CH3
group

of

254

ORGANIC

(1)

Experiments.

234)

on

(2)

sugar

solution

of

Hydrolyze

with

dilute
with

CHEMISTRY

some

H2SO4,

Fehling's

Try
a

Molisch's

(see

test

p.

glucoside.
glucoside
neutralize,

solution.

solution
and

by
examine

ing
boil-

for

CHAPTER

NITROGEN

XVIII

DERIVATIVES.
ARSENIC

COMPOUNDS)

DERIVATIVES

NITROGEN

These

into

fall

derivatives,

and

compounds,

by

prepared

by

amide

of

+KICN

C2H5CN

(Ethyl

p.

thus

273),

"

CONH2

Experiment.

acetamide

as

soon

top

as

add

immediately.

Cork
Heat

of

water)

acid

an

(Methyl

cyanide)

dry

250-c.c.

and

with

connect

with

255

gm.
a

small

with

dry

of

phorus
phos-

dry

rod.

the

of

more

gm.

of

gm.

15

quickly
10

wide-mouth

10

put

about

quickly

add

+H2O.

CN

"

flask)

Mix

possible

layer.

of

CH3

(extraction
and

+KC1,

(see exp.):

Into

pentoxide.
As

sium
potas-

cyanide)

(removal

(Acetamide)

flask

be

can

with

halides

alkyl

chloride)

CH3

Jena

cyanides

Organic

anhydrolysis
(see

nitro

(3)

anmionias,

as

CaHsjCl
(Ethyl

cyanogen

(4) nitrites.

treatment

cyanide,

(1)

classes:

Derivatives.

Cyanogen

also

four

substituted

(2)

AND

PHOSPHORUS

(ALSO

oxide

condenser

smoky

flame.

256

CHEMISTRY

ORGANIC

Collect

the

Shake

small

the

the

Transfer

to

product

separates

of

in

COOH;

to

called

CHa-CN

is acetonitrile
it

from

as

+2H2O

(see
CH3

p.

"

Use

pipette.
(p. 171).

be

can

alkyl

the
for

example,

acid

acetic

171)

COOH

the

remove

nitriles;

exp.,

layer.

top

cyanides

because

more

running

consequence

acid

are

CH3CN

organic

no

with

dry

clean

cyanides
obtained

cool

test-tube, and

group

hydrolyzed

of water,

until

KOH

synthesis of acetic acid

for

CN

The

sohd

now

test-tube.

its volume

solution

narrow

half

carefully with

cyanide
the

cyanide

large clean

of

pieces

dissolves, keeping
water;

in

with

distillate

add

then

distillate

the

be

can

+NH3(i.e.,
CH3COONH4.)

hydrocyanic add,

HCN,
be

hydrolyzed

it

can

is

extremely weak;

its

of

that

ten-thousandth
but

is used

This
CN

in

also

reaction

dissociation

of

the

N=C

is

mixture

metallic

it

power

is less than

one

poisonous,

the

carbon

that

is linked

There

chain.

to

nitrogen

the

or

of

atom

it is the

which

in

carbon

carbon

isonitriles.

methyl isocyanide.
think
of

cyanides

Chloroform

the

to

acid

It is very

isocyanides

are

chemists

Some
a

group

These

chain.

CH3"

CN

constant

that

shows

directly

regards

because

remedy.

as

As

acid.

acetic

of

cyanides, however,

atom

acid.

formic

solution

2%

is linked

are

be

to

be called formonitrile

may

when

that
and

HCN
are

hydrocyanic

mainly
heated

HNC,

acid
that

and

may

the

isocyanides.

with

alkah

and

primary

gives rise

amine

cyanide

NH2

+R"

isocyanide

When

an

formic

acid

CH3

"

in

formed

NC

+2H2O

since

the

Note

the
the

soon

of alcoholic

chloroform,

KOH.

Warm
odor

disagreeable
this

much

odor

is

in

water

of

detected,
the

sink,

Cyan-compounds.
be

C^N

HO"

(thiocyanic)

in the

HN=C=0,

or

or

monochloracetic
than

stronger
than

stronger

sulphur

has

placing
re-

cyan-acetic acid, CH2CNCOOH,

to

much

acid

cyanic acid molecule.

e.g.,

analogous

even

of

drops

gether
to-

poisonous.

may

Cyan-acidS)

is

few

as

with

are

Sulphocyanic

acid

c.c.

Mix

reaction.

of both.

mixture

are

and

amide

an

+HCOOH.

CH3NH2

peculiar

mixture

acid

As

fumes

Cyanic

Other

iso-

test-tube

isocyanide.

dilute

of

vapor

+3HC1.

NC

R"

Isocyanide

of aniline, and

gently.
the

disagreeable

hydrolyzed,

is

are

Experiment.

c.c.

the

to

CHCI3

257

DERIVATIVES

NITROGEN

the

acid.

the

simple

Such
acid

an

and

monochlor

corresponding

acid.
Substituted
as
are

ammonia

These

Ammonias.

in

which

one

replaced by organic

ammonias,

Nf-H,

or

more

groups.

contain

the

be

may

considered

hydrogen

Primary

group

atoms

substituted

NH2,

called

258

ORGANIC

the

amido

CHEMISTRY

amino

or

Secondary

group.

substitutea

N^R,

ammonias,

the

contain

imido

NH.

group,

R
R
substituted

Tertiary

N^R,

ammonias.

have

all

the

\r
of ammonia

hydrogen
These

action

the

by

called

all

are

displaced.

CzHsBr

of

ammonia

+NH3

C2H5NH2

+C2H5Br

"

hydrobromide)

(Diethylamine

(CzHs) 2NH

CzHsBr

"

(Triethylamine

The

is removed

HBr

with
Amines

three

with

salts

form

molecule, N

five.

to

HBr.

hydrobromide)

above

the

by treating

"

pounds
com-

KOH.

acid

entire

HBr,

hydrobromide)

(C2H5) 3N

pared
pre-

HBr,

(C2H5)2NH

are

alkyl halides:

on

(Ethylamine

C2H6NH2

They

amines.

acids

changing

the

on

its valence

of alkaloids

salts

The

by adding

from

of similar

are

nature.

amines

Some

have

CH2

diamine, NH2"
The
acid

CH3

amines
amide

"

CONH2

may

with

"

CH2"

also

sodium

+Br2

NH2

two

be

prepared by treating

CH3

(Acetamide)

forms

(see exp.) :

"

NH2

+2NaBr

(Methylamine)

+Na2C03

(Br

ethylene

NH2.

hypobromite

+4NaOH

as

groups,

hypobromite

with

+2H2O.

NaOH.)

an

260

ORGANIC

mixture

if

CHEMISTRY

to

necessary

of

evolution

free

secure

gas.

Nascent
an

hydrogen

alkyl cyanide into

an

amine,
CH3CN

+4H

(Methyl

CH3

bases,

cyanide)

(Ethylaminc)

decomposed

are

reaction

C2H5

"

is formed

it breaks

down,

+HNO2

(Ethylamine)

"

amines

Many

NO2

material.

protein
odor, and

their

dissolved

in

ions.

strongly basic

more

There

linked

are

groups

to

hydroxide
This

is

almost

taken

strong

very

equal

saponifying
as

is

to

power

100,

that

to litmus.

the

of

Many

nitrogen;

these

(C2H5)4NOH
its

of sodium

When

amines

are

hydroxide.

ammonium

in which

base;

in

bases, i.e.,they give

compounds.

ammonium

of

ammonia

bases

quaternary

are

alkaline

than

+C2H5OH.

decomposition

they form

water

hydroxyl

to

are

vapors

is

nitrite)

resemble

Amines

this

NO2,

"

ammonium

from

result

liberating nitrogen

+H2O

N2

is

nium
ammo-

first,but

(Ethyl

NH3(C2H5)

This
An

NH3(C2H5)

ammonia

acid.

nitrous

importance.

derivative

that

unstable

NH2

by

considerable

of

nitrite

rise

CH2NH2.

"

amines, particularly the primary

Many

so

converts

four

organic

stituted
really sub-

are

Tetraethyl

nium
ammo-

(cf. NH4OH).
saponifying

power

hydroxide.

{affinityconstant)

of

LiOH

is

If the
be

NITROGEN

261

DERIVATIVES

KOHandNaOH=98

(C2H5)4NOH=79
NH40H=

Mefhylamine,
mine

are

brine.

They

from

used

hold

to

They

is

the

used

amines

is left after
of

beet

by

trimethylamine

This

be

can

HCl
amine

is
tillate
dis-

methyl

obtained

with

treatment

tillation
dis-

preparing

produce

to

latter

herring-

sugar.

salts.

as

commercially
the

in

destructive

by

that

molasses

the

chloride, because

acid

obtained

residue

trimefhyla-

contained

are

also

are

the

alcohol

and

dimethykmine,

gases.

of

from

hydrochloric

HC1+3HC1

(CH3)3N"
Choline

is

=3CH3C1+NH4C1.

substituted

trimethylhy droxyethyl

ammonium

/CH2

hydroxide,

ammonium

"

hydroxide

CH2OH

(CH,).N"Qj.
It

will be

alcohols.
Choline
atoms

of

noticed
It

is of

that

the

related

to

primary

physiological importance.

is oxidized

both

it is also

to

betaine

alcohol

and

groups,

/CH2CO

(CH3)3N\

by

removal

the

basic

of the

hydroxyl

262

ORGANIC

Analogous

CHEMISTRY

choline

to

and

betaine

is

carnitine

{novaine)

yCH2CH2CH(OH).CO

(CN3)3N".

\o
The

lecithins

salts of choline.

are

(distearyllecithin) contains
acids

phoric
the

in

stearic

combination

The
and

with

chief

one

glycerophos-

choline, having

formula:

CH2

OOCigHss

CH"

(Stearic acid)

OOC18H35

/OH

PO^"

O"

CH2"
(Glycerol)

Lecithin

0"

(Phosphoric

is

important

an

C2H4N(CH3)30H

acid)

(Choline)

constituent

of nerve-tissue, of bile, and

of

the

of yolk

of egg,

envelope

of red

blood-corpuscles.
compounds.

of
acid

glycerol, and
one

one

obtained

radicle
of the

of

one

from

stearic

linoleic

nitrogenous

methyl
Muscarine

of

One

group

is

acid

acid

part

brain
and

of

instead

nitrogen,

importance

tissue.

It

from

contains

unsaturated

an

series, C17H30COOH,
differs

radicles, and

is cephalin, which

of

class

phosphoric

containing
are

these

this

alcohol, generally

fatty acid

They

to

contain
an

radicles

choline.

biochemistry.
been

with

more

or

more

or

generally

belong

Phosphatides

combination

in ester

also

lecithins

The

Phosphatides.

choline

in
has
the
acid

while
in

the

having

of three.

closely related

to

choline.

'

It baa

NITROGEN

been

suggested that

choline

to

263

DERIVATIVES

it is the

considered

as

aldehyde

corresponding

alcohol:

an

(CH,).N"^"^"""+='"'
Sbme

chemists

combined

with

in chloral

as

is

p.

that

so

basic

CHO

the

it is

substance

It is very

425).

toadstools

in

other

water,

that

really

is

group

CH(0H)2

"

hydrate.

Muscarine

(see

believe

classed

poisonous

as

and

{Agaricus muscarius)

loid
alka-

an

is

and

tained
consome

plants.

Many
mine,

ptomaines

dimethylamine,

diethylamine,

bases.

trimethylamine,

Methylaethylamine,

butyl-

triethylamine, propylamine,

amylamine,

amine,

amine

are

choline

and

muscarine,

occur

ptomaines.

as

and

Cadaverine

Cadaverine

putrescine

is

/CH2

"

CH"":-,
^CH2

"

has

Putrescine

ptomaines.

diamine

are

CH2

"

CH2

the

formula,

CH2"

CH2"

NH2

CH2"

NH2

"

NH2
NH2

I
CH2"
*

Ptomaines

toxic

organic bases

nitrogenous

on

is very

are

to

apt
and

by canned

are

contain
the

meats,

cause

etc.

matter.

formed

death

in

Many
certain

of

them

cases

are

of

of

teria
bac-

tissue

animal

Decomposing

ptomaines.
of

by the action

highly

poisoning

264

ORGANIC

choline,

like

Neurine,

CHEMISTRY

is

ptomaine-containing

oxygen,

=CH2

"CH
OH
is

Urotropine

is obtained

and

Acid

(CH2)6N4"

hexamethylentetramine,
by

solutions,

concentration,

the

even

act

action

of ammonia

those

of

low

very

maldehyd
for-

ion

maldehyde
liberating for-

urotropine,

on

on

Piperazine (spermine) is diethylendiamine,

/CH2

CH2\

"

KcH.-CH""Piperazine
the

acts

and

the

to

derivatives
will

they
this

be

of

in

or

and

other

no

as,

vided
pro-

tion.
concentra-

piperazine

are

arsine

tion
substitu-

the

are

it may

example,

Since

(AsHs)
be

organic acids

are

for

acid,

purpose.

place,

there

arsenic,

same

ammonias

(PHs)

that

state

to

phosphorus
is

phosphine

uric

lysidin

for the

substituted

mentioned

connection

which

used

are

for

in sufficient

lycetoly and

Sidonaly

Analogous

solvent

is present

former

derivatives

as

well

in

ing
contain-

cacodylic acid,

dimethylarsenic acid,

/CH,
0-=AseCH,.

\0H
Nitro

nitro

Compounds.
linked

group

nitroethane,
of

the

have

Nitroparaffins

"

directly

CH3-CH2
benzenes

"

to

NO2.
are

much

of

the

The
more

of the

chain,
nitro

e.g.,
pounds
com-

important

than

those

are

the

of

265

DERIVATIVES

NITROGEN

and

paraffins,

will

considered

be

later.
The

Nitrites.

Both

used

are

valuable
to

that

its

and

is

These

called

nitrous

nitrous

acid

organic

being

esters,

comes

nitrites

formed

by

on

chiefly

consists

It

very

similar

is

but

202),

p.

is

action

physiological
(see

importance.

nitrite

Amyl

evanescent.

very

nitrite.

isoamyl

of

and

NO,

O"

are

medicines.

as

nitroglycerol

of

NO,

"

"

remedy;

quickly
of

CsHn

nitrite,

amyl

C2H5"

Nitrite,

Ethyl

often

are

action

the

of

alcohols.

on

"

Prepare

Experiment.

Mix

in

and

alcohol
Set

flask

by

drop,

into

in
5

in

nitrite
nitrite

the

the

and

chloride
of

of

c.c.

vascular

C.P.

add

Add

funnel.

flask

out,

and

decant

Note
inhalation

the

alcohol,

the

some

when

Dry
color,

(flushing

dropping
decant

layer;

again.

liquid.

aqueous

throbbing).

shake;

amyl
nitrite.

from

top

follows:

sodium
to

H2SO4

forms

as

fermentation

powdered

ice- water;

distill.

cautious

of

c.c.

finely

nitrite

separates
from

20

of

gm.

separating

mixture

and

flask

Amyl

funnel.

effect

15

the

drop

off

small

nitrite

amyl

water

to

Separate

odor,
of

the

amyl

more

with

it

the

calcium
and
the

the
face

CHAPTER

AMINO

XIX

AND

ACIDS

ACID

AMINO

Amino

NH2

amido

or

amido

or

chloracetic

AMIDES

ACIDS

acids

acids

are

containing

Corresponding

group.

is

CH2C1-C00H,

acid,

to

an

mono-

aminoacetic

acid, CH2NH2COOH.
The

NH2

"

called

COOH,

unknown.

is

decided

acid

amino

simplest

salts

in

be

of

one

into

urea

of

the

forerunners

by

heating

"

into

It

bonates.
car-

considerable
believed
be

can

tube

sealed

of

it is

urea.

the

dry

NH3

Dry

the

CO2

generator

CO

"

at

to

changed
ature
temper-

and
in

as

by

obtained
and

dry NH3
cylinder

+H2O.

by
266

by

simultaneously
or

dropping

into

graduate.

through
marble

putting
HCl

carbamate

described
it

bubbling

adding

NH2

ammonium

previously

by

"

(Urea)

Prepare

contained

is

NH2

dry C02^

bubbling

or

converted
is

carbamate)

Experiment.

CO2

it in

COONH4

(Ammonium

showing

135-140":

NH2

alcohol

of

acid

free

unstable,

because

physiology,

acid,

The

carbamate

Ammonium

importance

are

become

to

aminoformic

acid.

carbamic

The

tendency

is

(see

Secure
p.

H2SO4.
chips
funnel.

into

153).
When

bottle

268

ORGANIC

The

amino

and

Proteins
in the

act

character

basic

givas the

group

molecule.

CHEMISTRY

other

some

to

organic

the

pounds
com-

manner.

same

acid,

Glycocoll (glycin) is aminoacetic

/NH2
CH2^^-"
It

dilute

with
be

can

acid
it

acid
the

(see p. 360), and

bile

the

In

choUc

with

of

strong

monochloracetic

on

acid

benzoic

with

It

water.

excess

an

act

hours.

twenty-four

combines

to

baryta

or

allowing

by

hydroxide

for

acid

sulphuric

prepared

ammonium

ing
glue (or gelatin) by boil-

from

produced

be

can

COOH.

hippuric

form

to

acid

body

animal

to form

of

one

acid.

acids, glycochoUc

/NHCHa
glycocoll, CH2"r

Methyl
It

cosin.
acid

and

can

be

called

is

"

sar-

synthesized

monobromacetic

from

methylamine:
CH3

/NH"

=CH2"^

CH2Br.COOH+2CH3NH2

/CH3

It

is

of

product

decomposition

of

and

creatin

of

caffeine.

CH3

Alanin,

pionic

acid.

acid

by

with

sarcosin.

Serin

"

It

treatment

is

CH
can

"

NH2
be

"

made

with

hydroxyalanin,

a-chlorpropionic

from

ammonia.

"

CH2OH

a-aminopro-

is

COOH,

It

"

CHNH2

is isomeric

"

COOH.

ACIDS

AMINO

ACID

AND

acid,

is a-aminoisovaleric

Valin

CH3

269

AMIDES

^CHCHNHaCOOH.

CH3
is

Leucin

a-aminoisobutylacetic acid, or

a-amino-

isocaproic acid,
/NH2

CH3\

NCH"
CHz-rCH"
CH3/' (Isobutyl)

This
a

in the

occur

may

product

of

of

diseases.

It is
portant
im-

an

tryptic digestion.

/NH2
"CH

"

CH"r

is contained
,

CH3/
in certain

acid)

protein, being

CaHsx
Isoleucin,

(Aminoacetic

in certain

product

decomposition
end

urine

COOH.

\COOH

proteins.

Aspartic acid

(asparaginic acid)

is aminosuccinic

acid,

/NH2

It is obtainable
Glutaminic

CH^

COOH

CH2

COOH

from
acid

asparagin and

from

protein.

(glutamic acid) is a-aminoglutaric

acid,

/NH2

/CH^^"

COOH

CH

'\CH2"
Gelatin
furnish

and
a

considerable

Phenylalanin
acids

caseinogen

derived

and
from

can

"

COOH
be

proportion

tyrosin

are

split

up

so

as

to

of this acid.

aromatic

mono-amino-

proteins (see p. 371).

The

amino

270

ORGANIC

acids

considered

CHEMISTRY

thus

far

the

have

amino

in

group

the a-position.

Lysin is ac-diaminocaproic acid,

NH2

It is

CH2

"

"

of the

one

mineral

CH2

"

CH2

CH2

"

/NH2
CH^ r^r\r\TT'

of protein when

products

with

boiled

acid.
is "5-diamino

Omithin

valeric

acid,
/NH2

NH2

Arginin

"

CH2

"

CH2

is related

a-aminovaleric

"

CH2

"

CH"^

_,

5-guanidin-

ornithin, being

to

acid.

/NH2

^^-^\nH-t-CH2.CH2.CH2.CH/^^^
_

-2

"

v^-n2

"

v"Il2

\COOH

(Guanidin)
(a-Amino

It

be

can

hydrolyzed

to

and

urea

valeric

acid)

ornithin, thus

/NH2

^^"^\nH"

CH2

"

CH2

"

CH2

CH/^^'
.

+H2O

\COOH

/NH2

NH2

NH2

\y

+NH2CH2CH2CH2CH"

NlIOOH

(Ornithin)

O
(Urea)

ferment, arginase, found

also

bring about

mainly

in the

liver,can

this hydrolysis.

Lysin and 'arginin are

called

hexone

bases

(hexone

AMINO

refers
the

ACIDS

their

to

ACID

AMIDES

six

carbon

hexone

base

possessing
Another

molecule).

C6H9N3O2,

AND

271

in

atoms

is

histidini

/3-imidazol a-aminopropionic

probably

acid,
CH
HN

NH2

CH=C"
It is

that

these
in

combination

in

nothing

all

besides

of
are

advisable

seems

derived

this

pyrrolidine (a heterocyclic compound,

the above

obtained, togetherwith
products

of

proteins.

They

tically
prac-

bases.

in

mention

The

contain

to

seem

(see p. 418), also

to

present

are

molecules.

protein

hexone

It is

414).

p.

bases

heterocycUc compound

is tryptophan
It

(see

hexone

simplest proteins, protamineSy

Another

COOH.

CH"

heterocyclic compound

beheved

now

CH2"

place

amino
are

a-amino

an

p.

from

they

because

acids, as
or

acid.

derivatives

two

415)

prolin

teins
pro-

sition
decompo-

a-pyrrolidine-

carboxylic acid,
H2C

CH2

HaCl^^CH"COOH,
NH
and

7-hydroxy-a-pyTrolidine-carboxylic

Optical activityof
Alanin,
ornithin,

the

acid

or

hydroxyprolin.

decomposition products of

valin, isoleucin, glutaminic

arginin,

and

lysin

are

teins:
pro-

acid,

dextrorotatory.

Serin, leucin, cystin, aspartic acid, histidin, phenyl-

alanin, tyrosin, tryptophan, prolin, and

are

Isevorotatory.

prolin
hydroxy-

272

ORGANIC

CHEMISTRY

DERIVATIVES

SULPHUR

OF

ACIDS

AMINO

Cysteia is a-amino-/3-thiolactic acid:

/SH
cmmolecules

Two

/NH2
CH^^" COOH.

"

combine

form

to

molecule

one

of

cystin.
NH2

CH"f

CH2"

S"

COOH
has

Cystin

the

formula

CH2"

S"

NH2

ch/

COOH
and

Cystein

cystin occur

proteins.
Cystin crystals
Reduction

of

is

Taurin

decomposition products

as

pathological

in

occur

may

cystin gives cystein

of

urine.

its product.

as

^-aminoethylsulphonic acid,

^NH2
CH2~-'
It is found
cholic

in bile combined

acid.

It has

SO3H.

"

with

cholic

synthesized

been

acid

ethylsulphonic
the

CH2

"

(see

306),

p.

acid

from
as

as

tauro-

jS-hydroxy-

indicated

by

following equations:

CH2(0H)

CH2

"

SO3H
CH2CI

+2PCI5
"

CH2SO2CI

(ChlorethylBulphon

CH2CI

"

CH2

"

SO2CI

+H2O

CH2CI

"

chloride)

CH2SO3H

(Chlorethylsulphonic

CH2CI

"

CH2

"

SO3H

+2NH3
=

CH2NH2

+2HCL

+2POCI3

+HC1.
acid)

"

CH2

"

SO3H

(Taurin)

+ NH4CI.

AMINO

AND

ACIDS

ACID

The

next

is that
acid
so

of the

chlorides,

there

of CI,
Acid

amides

CH3

acetyl

be

may

heating

(2) By

sidered
con-

Just

as

there

are

chloride, CH3COCI,
the position

occupying

made

acid

an

CHb

acid

an

in several

in

anmionia:

CONH2

ways

with

chloride

NH2

constantly

while

amides.

be

to

CH3-CONH2.

C0|C1 +H

"

compounds

amides, NH2

(1) By treating

into

acid

acetamide,

as

amido

e.g.,

acid

are

273

AMIDES

AMIDES

of

group

ACID

+HC1.
of

atmosphere

an

bubbUng

dry ammonia

monia
am-

gas

acid:

the

CHa

COIOH

(3) By

+HJNH2

treating

with

ester

an

CHs

"

CONH2

+H2O.

ammonia

CONH2

COOC2H5

+2NH4OH

COOC2H5

-[-2C2H5OH

+2H2O.

CO.NH2
(Oxamide)

(Diethyloxalate)

(4) By

the

heating

generally

in

sealed

salt

ammonium
tube

(the

of

the

acid,

being anhy-

process

drolysis)

CH3

"

COONH4

(Ammonium

Acid
nitrous

amides

CHs

are

accelerated

by
by

CONH2

decomposed
water,

hydrogen

+H2O.

(Acetamide)

acid, nitrogen being

hydrolyzed

acetate)

the

by

the

liberated.
action

ions.

This

action
Amides

being
can

of
are

greatly
be

taken

274

ORGANIC

of to determine

advantage
solutions

dissolved

in these

acid

amides

method

prepared by

on

ethyl

melt

82"

at

odor,

It

in

To

bath,

add

few

cubic

reaction

until

water-bath

slightlyacid
a

Volhard

(so

as

to

or

drop

diluted

with

the

smear

be

adhering

the

to

of the

any

the

of the

on

boiUng

shows
hot

tube).

into

funnel

hot

With

substance

eight inches

upper

alkaline

while

mass

water

with

water

through

walls

acid

(about

weak

to 80-90"

strip of filter-paperremove
may

shows

bomb-tube

diluted

drop

heat

Pour

oh

carbonate

Now

reaction.

tube

not

pentoxide

to 40-50"

dish

of water

to litmus.

ties.
impuri-

glacial acetic

anamonium

centimeters

of

(see p. 255).

of

gm.

stirring, until

while

generally has

crystallization from

cyanide

40

powdered

crystals, which

phosphorus

with

evaporating

an

It

purified by

Experiment.
heated

223".

also

can

hydroxide

slight admixture

to

methyl

it into

gm.)

colorless

the

by

It

(see exp.).

It forms

Heating

converts

other

The

prepared

of ammonium

due

be

can

chloroform.

55

above

distill at

and

mouse-like

is

action

the

acetate.

liquid.

crystalhne substances.

given

be

electricity. Salts

CH3-CONH2,

Acetamide,
fourth

is

solid

are

simpler

The

somewhat.

ionize

HCONH2,

Formamide,

(p. 172).

conduct

formamide,

as

of

concentration

hydrion

acids

dijfferent

of

amides,

CHEMISTRY

that
of the

tube.
Seal

the

tube

carefully. The

practice. Experiment
First

cover

the

tube

first
with

soot

sealing

with
in

of bomb-tubes

waste
a

smoky

pieces
flame

requires
of

at

tubing.
the

point

276

ORGANIC

glycocoll, is

of

biuret

CHEMISTRY

interest

of

the

with

connection

in

(p. 280).

test

CONH2

Oxamide,

od

by the third meth

is prepared

CONH2
Connect

Experiment.
tube

bent

at

flask the
the

which

driven

is

oil.

in

the

flask

containing only

oil-bath
the

oil-bath

passing
to

alcohol

disconnect
the

flask

into

obtained.

portion
add
a

in

very

time

dilute

until

reaction,

see

of

p.

282)

or
:

the

Treat
white

flask,
Cool

with

each

precipitate

and

the

wash

sample.

Put

some

strong alkah, and

ammonia.
with

Take
cold

violet

color

of

distillate

appears

boil,

another

NaOH,

sulphate solution

copper

reddish

first

flame.

and

Save

test-tube, treat

the

of the
most

the

Filter

test-tube, add

evolution

the

noting

from

hydroxide.

alcohol-

the

When

remove

precipitate thoroughly.
oxamide

begin heating the

125-130".

oxalate.

is

condenser.

teniperature

diethyl

ammonium

with

the

residue

first

in the

allow

and

been

second

the

While

to

acid

The

100^.

alcohol.

the

flask;

oxamide

flask

disappeared

this

contain

strong

over,

of oxalic

thermometer

100", then

to

slowly

has

second

both

of

rise

Place

to

of alcohol.

while

gauze,

second

the

ond
sec-

almost

c.c.

gm.

at

oven

wire

on

Heat

is

oil-bath.

an

Connect

vapor

in

50

the

crystallization has

of

by heating

50

glass

In

reach

to

put

also

put

water

supported

placed

flask

with

end.

each

at

long enough

flask

the

off

flask

is

Into each

second

the

from

is

tube

bottom.

Into

right angle

flasks

two

and

drop

at

(biuret

ACIDS

AMINO

COOH

COOC2H5

+2C2H5OH

COOH

+2H2O,

COOC2H5
CONH2

COOC2H5

+2NH40H=

+2C2H5OH+2H2O.

CONH2

COOC2H5

Asparagin is the

mono-amide

CH2"
formula

being
and

the dextro

It

variety; the
the

while

dextro

kind

commoner

tastes

It

sweet.

vegetables, particularly asparagus,

beans, beets, and

is

having the

both

as

COOH

the laevo

in many

Glutamin

occm-s

(Isevo)is tasteless
is found

aspartic acid, its

of

CONH2

CH(NH2)"

peas,

277

AMIDES

ACID

AND

the

wheat.

mpno-amide

of

acid,

glutaminic

formula

/NH2

yCH^

COOH

"

^^'\CH2
The

most

important

acid

C0NH2'
amide

of all is carbamide.

(carbamide), NH2-CONH2,

Urea

of carbamic

acid.

is the

It is also the

diamide

acid

amide

of carbonic

acid:

/OH

/NH2

o=c"

o=c"

-"

\)H
The
its

relationshipof
preparation
in

sealed

^NH2
to carbamic

urea

from
tube

ammonium
at

0=C"
(AsuDOiuum

carbamate)

+H2O.

^NHa
(Urea)

by

ing
by heat-

of 135":

/NH2

=0=C"
^0NH4

is shown

carbamate

temperature

/NH2

acid

278

ORGANIC

CHEMISTRY

relationship to

Its

production

acid

carbonic

chloride

carbonyl

from

is evidenced

/CI

0=C"

+2HC1,

^NHa

chloride)

ethyl carbonate

from

and

ammonia:

/OC2H5

/NH2

+2NH3=0=C"

0=C"

+2C2H5OH.

^NH2

^OC2H5
(Ethyl

That
and

carbonate)

it bears

its amide

its

ammonia:

+2NH3=0=C"

(Carbonyl

its

/NH2

^Cl
also

and

by

relationshipto cyanic acid, HCNO,

preparation

both

from

is converted

cyanamide

N^C

cyanamide,

these.

of

into

is

NH2,

"

proved by
hydrolysis

By

urea.

/NH2
CN

NH2

+ H2O

0-=C"

_"

\NH2
Mere

evaporation

of

is sufficient

cyanate

solution

to

convert

(see exp.); this involves

(Ammonium

The

change

reaction.

of

cyanate

point,

until

when
i.e.,

5%

/NH2

iso-cyanate)

equiUbrium

changes

change:

^NH2

changes

urea.

urea

^0=C"

isocyanate
become

iso-

into

salt

intramolecular

decinormal

ammonium

the

NH4

^N"
cf
^0

of

On

which

the

it reaches
has

been

is

solution

of

standing

on

at

urea

to

of the

95%

other
the

until

hand

ammonium
it reaches

cyanate
urea

an

has

solution

equilibrium point,

same

changed

reversible

to

cyanate.

ACIDS

AMINO

advocated

Physiologistshave
origin of

the

ammonium

(3) from

or

of

derivation

the

hydrolysis of

bacterial

and

of the

large

the

of

laws

and

carbamate

urea

by

-"

0^C"

H2O)

of

portion of the

be

acted

the

becomes
to

Arginin

which

is present

in many

hydrolyzed by

organs,

being

urea

has

ammonia

changed

is

arginase,

ferment,
of the

one

is

power

the

and

carbamate,

may

products

270).

p.

Urine
30

be

and

source

possessing that
then

by

ammonia

that

so

organs), and

many

may

become

monoamino-acids

The

ferments

used

not

are

proteins probably

carbonate

ammonium

urea.

(see

of
in

which

(deamidization)

presence

demonstrated

acids

manner:

by ferments

on

split off (the

been

following

(Urea)

carbamate)

amino

for synthesis of

in

urea

o-=c"

-"

^NH2

(Ammonium

carbonate)

tissues

/NH2
H2O)

\ONH4

certain

the

converted

anhydrolysis:

of

\ONH4

then

are

monium
am-

accordance

/NH2

/ONH4

0=C"
(Ammonium

of these

ence
pres-

blood,

in

formed

are

process

in the

acid

carbonic

blood

In the

proteins of the food.

action; both

mass

liver into

in the

of

amount

carbonate
with

the

the

enters

result of fermentative

the

as

from

likely that

most

Ammonia

follows:

as

the

to

carbamate,

ammonium
seems

to

as

it is derived

that

It

system mainly

portal venous

of the

is

urea

corresponding

body,

cyanate.

hypotheses

main

(2) from

carbonate,

(1) ammonium

three

animal

279

AMIDES

synthesis, namely,

of

methods

above

the

in

urea

ACID

AND

gm.

contains
of

urea

large quantity

being excreted

twenty-four

hours

in

colorless

needles

at

132"

on
or

in the

mixed

diet.

rhombic

(corrected melting-point

very

soluble

cold

alcohol.

Bacterial

in water

fermentation

and

hot

of

20

urea,

urine
It

prisms.

of

to

in

man

crystallizes
It

is 132.6").

melts
It

alcohol, less soluble

of urine

converts

urea

is
in

into

280

ORGANIC

ammonium

carbonate,

decomposed

of

with

hence

urine.

alkalies

accomplish

can

CHEMISTRY

An

acids

or

.NH2

Of

the

by

course

from

the

CO2

is

Bunsen's

and

estimation

action

of estimation

while
This

acid

action

of

the

'basis

is

methods

of

of

quantitative

satisfactory method

most

is that in which
and

the

by

is liberated

NH3

reaction

The

urea.

hypochlorite

NH/

of alkali

Folin's

of

water,

"C03.

IH2O

liberated.

ing
boil-

NH4V
=

(NH4)2C03,

also

urease,

hydrolysis:

^NH2

odor

superheating with

or

fHaO

C0"

ammoniacal

enzyme

similar

the

Sodium

is used.

urease

hypobromite

decompose

urea,

liberating nitrogen:
CO(NH2)2
This

+3NaBrO

is made

reaction

+3NaBr

N2

of

use

method

for

urea

liberates

free

nitrogen (see

heated

substances,
gives
soda

or

strongly,

biuret^ NH2

reddish-violet

"

potash containing

linked

oxaniide)

or

through

260)

clinical

acid

also

CO

"

NH

"

CO

reaction
trace

reaction

is

which

NH2,

"

with

of copper

caustic

sulphate

given by

containing

together either
a

other

yields, among

urea

ide, in fact by all substanpes

CONH2

usual

Nitrous

p.

color

(biuret reaction). This

of

the

=2N2+C02+3H20.

CO(NH2)2+2HN02
When

in

estimation.

+2H2O.

+CO2

two

oxam-

groups

directly (as in

single nitrogen (as in biuret)

AMINO

ACIDS

AND

ACID

/C0NH2\

/
carbon

or

atomf

281

AMIDES

in

as

)^^ through

CH2, \

COCONHzX
or

CO

more

NH

"

(as

groups

in

CONH2

take

may

groups,

proteins give
Urea

acts

nitrate

extraction

of

urine

by

treatment

oxalate

with
nitrate

certain

particularly

being

method

it is

precipitated from

for

by evaporation)

The

nitric acid.

by treating

All

common

the

urine,

(p. 275).
toward

base

(previously concentrated

the

from

from

urea

the

one

(p. 296).

reaction

In

of

of

glyeinamide

and

salts.

CONH2

"

place

monacid

weak

characteristic

the

in

as

the biuret

as

acids, the

the

.)"

|
NH

CH2-NH2

one

^^^ttt

the

is liberated

urea

latter

with

barium

as

follows:

carbonate.

.(1) Synthesize

Experiment.
Heat

25

iron

dish

until

little at

frothing
cool

c.c.

into

on

of cool
an

a
a

small

an

in

iron

evaporating

for

dish.

sulphate

Add
that

of water.

to

has

over.

Cool

Transfer

the
it to

residue
a

small

and

to

metallic
with

plaited

ter
fil-

the

filtrate 25

been

dissolved

Evaporate

water-bath, stirringfrequently

it is

hour

an

through

the

When
the

out

oxid^ of
When

well.

plate.

cyanate
Filter

water.

quantity

of red

gm.

separating

mass,

of ammonium

gm.

on

pour

the

70

an

(do this under

fuse

to

time, stirring

Digest this crude

lead.

in

begins

in

cyanide

potassium

gradually

ceases

powder

100

it

add

hood), then
lead

powdered

of

gm.

urea

to

dryness
ing
crust-

prevent

powder

flask, add

it in
100

tar.
mor-

c.c.

of

282

ORGANIC

alcohol, attach
for fifteen

to

evaporating

in

similar

dish.

to

some

of the solution

of colorless

glass

the

(6) In

gently

for

Cool;

add

20%

NaOH

very

dilute

reaction

oc/

melt

of

of

alcohol

When

it is

few

on

cool,

crystals or

of concentrated
with

water,

is obtained.

cover-

scope.
micro-

then

urea,

heat

is being evolved.

equal

an

finally

drop
violet

is called

of

amount

small

solution.

This

drop

one

Place

dry

then

it

under

(NH3)

gas

sulphate

(see above)

alcohol

the

examine

some

while

copper

NH2

more

nitric acid.

solution, and

color

pinkish

into

drop

one

crystals and

c.c.

alcohol

glass slide; mix

minute

Test

Put

(a)

test-tube

hot

below.

concentrated

over

c.c.

bulk.

form.
as

tests,
on

25

small

very

crystals should

solution

boil

Evaporate

urea

(2) Urea

Use

and

condenser,

Filter off the

manner.

water-bath

urea

reflux

minutes.

an

CHEMISTRY

of
or

biuret

the

NH2

Nco

HNH^

^NH2

(Urea)

(Urea)

CO"

=NH2"

NH"

CO"

NH2

+NH3.

(Biuret)

If the

heating has

point,
(HCN0)3,
of

insoluble

is formed;
molecule

one

continued

compound,

this results
of

biuret

from

with

beyond
cyanuric
the
one

tain
cer-

acidy

tion
combinaof

urea,

being eliminated.

2NH3

Veronal
urea

an

been

or

is

urea

derivative, being diethylmalonyl-

diethylbarbituric acid.

CHAPTER

IMIDES.

ACID

XX

COMPLEX
INCLUDING

contain

acid

acid

They

yNH.

by

formed

are

CO^

amides

dibasic

illustrated

NH,

group

COv

CH2"
from

POUNDS,
COM-

IMIDES

the

CH2"

succinimide,

IMIDO

POLYPEPTIDES

ACID

These

AND

AMINO

by

being

loss

of

amide

the

ammonia,

of

necessary:

CH2CONH2

CH2CO.

CH2CONH2

CH2C0^

^NH+NHs.
(Succinamidc)

OTHER

(Succinimide)

AMINO

AND

COMPOUNDS

IMIDO

/NH2
NH=C"'

Guanidin,

be

may

considered

as

an

^NH2
derivative

imido

carbamide.

and

of
It

and

urea,

be

can

might

synthesized

be

called

imido-

cyanamide

from

ammonia:

/NH2
CN

NH2

"

+NH3

NH=C"(
.

^^^
^NH2

(Cyanamide)

(Guanidin)

It

is

because

strongly

more

of

the

basic

changing

than
of

284

the

urea,

undoubtedly

carbonyl

linking

of

AMINO

IMIDO

AND

285

COMPOUNDS
.

the

for

urea

basic

naturally

NH

Methyl-

group.

/NH2
guanidiriy HN=C"r
Of

(p. 263).
of

are

the

and

creatin

/NH2

derivatives

acid,

/CH3

A:;H2

be

can

ptomaine

creatinin,

methylguanidinacetic

is

NH=C^
Creatin

as

importance

more

guanidin, namely,
Creatin

occurs
,

"

COOH.

cyanamide

from

synthesized

and

sarcosin:

CH3

/NH"

CNNHz+CHz^^-"

COOH

(Cyanamide)

(Sarcosin)

yNH2

NH=C"^/CH3

Creatin

is present

tissue.

It

with

Heating

sarcosin, and
dilute

acid

urine

baryta

it is

water

other

changes
of

dbtained

be

can

some

appearance

though

in considerable

reported

in

from

meat

the

urea,

Heating

creatinin.

in

cular
mus-

extract.

it into

converts

As
is

urine

rule

with
the

pathological,

occurring nortnally in the

as

is creatin

less

CO

/CH3

NH=C"

is
gm.

always present

of water:

molecule

/NH

1.5

quantity

of children.

Creatinin

This

COOH.

substances.

it to

creatin

\CH2"

^N^

CH2

in normal

human

being excretecj

in

twenty-four

urine, about
hours.

The

286.

ORGANIC

excreted

amount

the

much

total

the

from

for

quantity

creatinin-containing food

when

(flesh) is debarred
fixed

CHEMISTRY

each

diet

individual,

nitrogen

the

how

matter

no

of

content

be

to

seems

urine

may

vary.

Creatinin

readily

crystallizesin

soluble.

converted,

and

Fehling's
it holds

these

oxide

cuprous

solution, however,
is

Uric

is

molecules

the

of

is

in
An

hydrogen

atom

the

of

account

testing for
alkaline

sugar

bismuth
creatinin.

by

and

chloride

mercuric

ical
entering into chem-

reagents

creatinin.
of

unite

In uric acid

urea.

by

linking
NH2

chain, each
and

It reduces

on

reduced

not

derivative

urea

carbon

union

mislead

becomes

solutions, but

solution;

precipitated by

with

acid

in

may

by zinc chloride, these

union

it

copper

is concentrated.

urine

Creatinin

solution

alkaline

It is

prisms.

part, into creatin.

other

properties it

if the

alkaline

In

least in

at

monocUnic

becoming

group

NH

to

mediate
inter-

an

losing

in order

two

to

one

effect

HN.

"

"C=0.
HN^

"

This

is the

presence

is shown

skeleton

of two

by

the

of uric acid

urea

of the

uric

molecules

nature

of the

resulting from

acid

and

of

formula.

The

carbon

chain

decomposition products
oxidation

and

ysis:
hydrol-

AMINO

NH"

AND

287

COMPOUNDS

IMIDO

CO

I. CO

C"

NH

" C0+H20+0
NH"

C"

NH'
cold

(Uric acid) [treated with

HNOs]
\

CO

NH"

NH2"

"C0.

C0+

=C0

NH2''

NH"

CO

(Alloxan)

II.

NH"

CO

CO

CO+0

NH"

CO

warm

NH"

III.

(Parabanic

(Parabanic

CO

CO

CO

acid)

acid)

NH"

+H2O

NH"

CO

NH"

CO

CO

+C0:

CO

[treated with
HNOj]

(Alloxan)

CO

NH"

COOH.

NH2

[treated with

(Urea)

alkali]

(Oxaluric

acid)

CO

NH"

COOH

/NH2
IV.

+H2O

CO

C0"

+1

^NH2
NH2
(Oxaluric

The

acid

COOH.

COOH
acid)

[boiled with

presence

water]

of the

(Urea)

pyrimidin ring,

(Oxalic acid)

N"

C, in uric

N"

is
by Traube^s synthesis, which
treated
are
Cyanacetic acid and urea

is shown

as

lows:
folwith

288

POCI3;
and

CHEMISTRY

ORGANIC

urea

the

latter

takes

its

cyanacetyl

to form

place

(1) CH2COOH+NH2CO.NH2
(Cyanacetic

the

from

hydroxyl

removes

urea

acid,
:

(Urea)

acid)

CN

CH2"
=C0

+H2O.

I
NH"

C"

NH2

O
(Cyanacetyl

Treating cyanacetyl
within

the

alkali

with

urea

molecule, resulting

in

C=0

HN"

(2) 0=C

CH2

I
C=NH

HN"
This

is treated

with

giving

HNO2,

C=0

HN"

(3) o=C

C-=NOH.

I
HN"

By

reduction

I
C=NH

this becomes
0=0

HN"

C"

0=C

I
HN"

I
NH2,

II
C"

NH2.

causes

the

monoamino-dioxy-pyrimidin,

urea)

shifting

formation

of

which

when

acted

by CCIOOC2H5+KOH

on

(Ethyl

HN"

(4)

0=C

C"

190", alcohol
urate)

later
acid

180"-

to

(as potassium

CO

I
C"

I
HN"

NK.

"C=0+C2H50H.

II
C"

NH^

synthesis conclusively

proves

the

structure

of

acid.

Another
to

(at least
and

interesting synthesis,
which

one

in

may

in

occur

birds), is effected

trichlorlactamide

The

groups

acid

molecule, but

H2O.

150", then

to

this

(5) o=C

urea

By heating

is split off, leaving uric

uric

NH2
of urethane.

(dry)

HN"

This

COOC2H5,

NK"

C"

pjrriniidinderivative
salt

chlorcarbonate)

Jl

HN"

potassium

gives

C=0

281

COMPOUNDS

IMIDO

AND

AMINO

in

the

animal

body,

by heating together

parenthesis do
unite

ogous
it is anal-

because

to

not

form

enter

into

NH4CI,

the

HCl,

uric
and

290

ORGANIC

CHEMISTRY

COv

/NH"
Dialuric
the

acid,

CO^^

of birds

case

yCHOH,

be

to

synthesis of uric acid

the

combination

By

the

of

addition

'ic acid

is

by the liver.

It is formed

acid

molecule

urea

in the

body

tartronic

another

produced

NH"

with

urea

of

intermediate

an

in

appears

by

(p. 221).
this,

to

CO

C0"

(HOH)

C"

+NHs-(H)

CO

C(0)

NH"

NH^(H)

(Dialuric acid)

(Urea)

CO

NH"

=C0

C"

NH.

"CO

II

NH"

+ 2H20.

NH^

C"

(Uric acid)

has

been

not

Uric

heated

and

in

mammals

of

case

proved.

acid has

glycocoU

the

in

synthesis

Analogous

been

synthesized by heating together

On

urea.

the other

sealed

tube

with

of

uric

acid.

Tautomerism

only

in the

form

(the

lactam

state)but

state), in which

II
N"

acid

Uric
to

also in another

the three

yields glycocoll.

HCl

corresponding

N=C"

HO"

hand, uric acid when

atoms

the

OH

C"

II
C"

NH

"C-OH^^-

N/^^

above

form
are

exists

in

not

formula

(the

lactim

hydroxyls:

292

ORGANIC

CHEMISTRY

CH"

/NH"

CO

AUantoin,

oxidation

of

It

occurs

dogs, and

at

Purin

bodies.

contain

the

times

NH2^

uric

acid

by

the

urine

in

in human

double-ring

from

potassium

manganate
per-

calves

of

and

urine.

.acid and

Uric

results

yCO,

CO

\NH"
careful

NH.

all the

bodies

purin

nucleus

N"

C"

N"
C.
'

0"

N"

ring is the

main

The

N'

pyrimidin

nucleus, therefore, is pyrimidin

as

is shown

bodies

uric acid.

(1)

N"

(2) C
(3) N"

discuss

attached

urea

relationship of
at each

atom

the

8.

It

of the

be

can

purin

positions

prepared

(6)

NH"

CO

(5)" N(7)v

CH

C"

"C(8)

1
(4)"

purins
the

relationshipto

N(9)^

II

from

and

urea

and

"CH

(Hypoxanthin)
(6-oxypurin)

pyrimidins

chemistry

NHv

II

nucleus)

(Purin

The

purin

to

an

2, 6, 7, and

numbered

with

the

below:

itself has

Purin

The

secondary ring.^

ring;

We

are

heterocyclic.

at

this point because

of them

proteins.

the typical heterocyclic compounds.

They

show

no

prefer
of their

similarityto

NH"

CO

CO

C"

293

COMPOUNDS

NH

NH"

CO

CO

C"

N(CH3)

"CH

NH

IMIDO

AND

AMINO

"CH

"N
N

C"

(CH3)N

dimethylxanthin)
(Theobromine,
6-dioxypurin)
(3, 7Hdimethyl-2,

(Xanthin
(2, 6-dioxypurin)

CO

(CH3)N"

(CHa)

N^

C"

CO

^CH
N

C"

(CH3)N"

(1, 3, 7-triincthyl-2, 6-dioxypuriii)

(Caffeine, theine, trimethylxanthin)

NH"

CO

CO

C^NH.

N^

=C"

NH.

CH

C"

NH

NH^

C"

NH"
(Uric

"co

II

acid) (2, 6, 8-trioxypurin)

H2N"

C"

NH

"CH

There

are

caffeine

and

(Guanin)
(2-amino-6-oxypurin)

purins

nuclein

as,

(heteroxanthin)

are

and

also

called

besides

purins

methyl

xanthin,

methyl
,

1, 7

dimethyl

methyl guanin.
alloxuric,xanthin,

or

bodies.

Caffeine

excreted

of

theobromine,

(paraxanthin)

xanthin

The

number

xanthin

methyl

"C

N"

-C^N
(Adenin)
(G-aminopurin)

CO

"CH

II
N-

NH"

and

in the

theobromine
urine

when

taken

partly unchanged

as

food

and

are

partly

294

ORGANIC

and

monomethyl

as

40%

of

urine

as

caffeine

the

increase

excreted

some

that

on

each

acids
and

tissues

of

of

xanthin,

are

contains

acid.

tea

or

purin bodies, and

is free of

and

have

do

other

not

pm'ins
by

fixed

quantity

the

In

of

case

their

origin in the

both

those

the

of

food.
xanthin

It

is

and

therefore

solution

hypoin meat

meat

extract

chiefly creatin,

acid.

sarcolactic

cocoa.

the

purin bodies, the

daily is

(dimethylxanthin)

Theobromine

coffee

organic constituents

its

in

It is believed

muscle, and

in

35-

investigators

The

purins, mainly

found

as

and

(cf. creatinin).

of the

the

Beef

of

nucleoproteins,

those

Some

extract.

tea

purin bodies

the

nucleic

that

purins excreted

individual

manmials

number

that

diet

uric

as

Only

appear

excretion.

mainly

of

amount
for

bodies.

acid

xanthins.

theobromine

assertion

uric

are

dimethyl

and

pm-ine

in

agree

CHEMISTRY

called

is found
an

in

olate
choc-

alkaloid

(see

425).

p.

Caffeine

loidal

or

principlein

caffeine

and

theine

are

and
as

coffee

is the

alka-

theobromine

Both

medicines.

Repeat,

test

(see p. 291)

substituting bromine

for HNO3.

water

Pyrimidin
nucleic

The

used

little caffeine.

acids

tea

Try the murexide

Experiment.
on

(trimethylxanthin)

or

acid

derivatives.

cytosin.

important

derived

are

by hydrolysis whether

by post-mortem
most

These

by

the

autolysis of animal
are

from

action

of

tissue.

uracil, thymin

and

AMINO

AND

NH"

C=0

0=C

CH.

NH"
is 5

Thymin

295

COMPOUNDS

dioxypyrimidin,

is 2, 6

Uracil

IMIDO

CH

2, 6 dioxypyrimidin,

methyl

NH"

C=0

0=C

C"

CH3.

II

NH"

CH

Cytosin is 6 amino

oxypyrimidin,

N"

C"

0=C

CH

II

NH"
As

illustration

an

which

one

of

protein

of the

consist
and

four

has

of
been

it has

been

obtained

gland.

guanin,

adenin,

assigned

the

C43H57N
Leucomaine

found
and

in

the

is

leucomaines.

formula

tissues.
of

nucleo-

hexose
with

(p. 231)
cule
mole-

one

and

to

cytosin.

5O30P4.

living animal
group

tioned
men-

beUeved

is

thymin

applied

creatinin

It

of four

term

from

molecules

acid

be

might

acid

nucleic

linking together

phosphoric

each
To

of

CH

thymus

the

NH2

to

basic
The

compounds

substances

purin
are

the

bodies
chief

296

ORGANIC

CHEMISTRY

DIPEPTIDES

Because

of the

of

fact

AND

POLYPEPTIDES

that

the

include

proteins

ucts
prod-

decomposition

amino-acids

(as alanin,

glycocoU, leucin, tyrosin, aspartic acid, etc.) and

the

been

the

hexone

bases,

of the

structure

of

of the

aii

of acid

bodies

carboxyl

proposed

protein molecule

amino

of these
of OH

it has

as

gether
to-

of the removal

body

amino

one

of another

group

chaining

means

of the

group

amino

by

explain

to

and

(cf. formation

amides), thus:
OH

/
NH2

CH2

"

CO

"

NH

CH2

"

"

COOH

(Glycylglycin)

or

complicated chain,

more

-NH

"

CH

CO-NH

"

CH

"

above

theory

of

gives the

the

biuret

the

basis

the

best

test

being

test

On

is

Compounds
three, and

bodies

C3H6CH2NH2
(Lysin)

supposed

be

to

applied

to

the

many

to
are

to

only

part

been

even

combine
called

up

to
in

the

CONH
the

universality

problem

in

peptides.

manner;

281)

these

of the

attacked.

which

eighteen molecules
this

p.

groups.

being vigorously
synthesized

cules
mole-

protein

proteins (see

of this hypothesis

have

of
of

explanation

as

due

constitution

synthesis of protein is now

made

CO^-NH"

formula.

This

of the

CH

acid)

(Aspartic

the

course

of the

CO-NH

CH2COOH

C4H9
(Leucin)

Of

"

as:

have

two,
been

synthetic

AND

AMINO

molecules

If two

for

dipeptide;
NH2

"

Polypeptides

CH2

"

CH2

"

include

"

CO"

NH

up

from

CH2

than

more

two

CH2CO"

NH

CH2

formula

"

COOH),

Certain

polypeptides,
of

hydrolysis

proteins.

show

They

by the

been

the

molecular

as

to

duced
pro-

by partial

complex

bitter.

those

those

obtained
more

composed

are

by

hydrolyzed

with

peptides
polyin

peptones

They

reagents, and

same

that

Those

The

taste

optical activity

are

and

resemblances

certain

actions.

same

and

leucin

synthesized, the

identical

synthetically,have

test.

etc.

1213.

weight

their

been

has

C48H80O19N18

being

three

of

composed

glycocoll molecules

fifteen

cules;
mole-

tripeptides (as diglycylglycin,

NH

polypeptide

COOH.

"

tetrapeptides, pentapeptides, hexapeptides,

A

is

glycylglycin,

CO"

built

compound

united, the

example,

are

they
NH2

have

297

COMPOUNDS

IMIDO

are

cipitated
pre-

give the biuret

of amino

acids

of the

occurring in proteins

trypsin.

Their

solutions

are

colloidal.

Fischer,

E.

who

this

line

this

comparatively

of

only kind

is

doing

such

synthesis, is inclined

of

simple method

brilliant
to

doubt

of

work

in

whether

linking is the

Unking existing in protein

molecules.

PROTEINS

Proteins

yield
hexone

on

are

complex nitrogenous compounds

complete
bases

hydrolysis mainly

(p. 270), and

ammonia.

amino

They

that

acids,
vary

298

CHEMISTRY

ORGANIC

and

bases

contained

has

not

only about
of

cent

proportion of the different

in the

widely

20%

the

other

2%;

has

on

be

to

seems

is

Most

proteins contain

they

form

colloidal
has

not

in

formula

the

acids.

acid

proteins

nourishment.

proper

(cystin),

of

Since

P.

some

lowest

on

iron

haemoglobin.
amino

amino

per

been

16,000, calculating
of

is 16.5

weight

weight

and

gelatin

solutions, molecular

possible molecular

composition,

in

none

to

there

aromatic

the

essential

most

determination

hand

and

globin
haemo-

e.g.,

leucin, but

of

little of

very

Tryptophan

molecules;

less than

glycocollin gelatin

Gelatin

which

in their

acids

amino

successful.

basis

molecule;

the

of

that

supposing

is

haemoglobin

of

the

The

there

this

over

percentage
is

atom

one

corresponds

to

the

C758Hi203O218Ni95FeS3
The

most

important

classes

of

histones, albumins,

proteins

derived
alkali

metaproteins, proteoses

certain
and

classes

of

vegetable

nucleoproteins),

proteins, acid

(coagulated

proteins

proteins (chro-

and

glucoproteins

tamines,
pro-

globulins, phospho-

proteins, scleroproteins, compound

moproteins,

are

and

peptones), and

and

proteins called

glutelins

prolamines (or gliadins).

lodothjrrin (thyroiodin) is

portion

of

the

compound

the

iodin-containing

protein, thjrreoglobulin,

present in thyroid tissue.

Oxyproteic

acid, C43H82N14O31S,

protein.

It is found

increased

in

some

in the

is

urine, and

pathological

derivative

may

conditions.

be

of

greatly

300

CHEMISTRY

ORGANIC

ETHYLENES

Ethylenes

olefins, C"H2", form

or

homologous

an

series.

member

only
coal

with
of

C2H4

that

H3PO4

the

best

is

in
to

use

obtained.

Insert

placed

of

pass

Woulfif

the

At

bottle

the
out

three-holed

cork.

the

entire

; the

10

of

wash-bottles

as

having H2SO4,

of the

vapor

flask, and
this

raise the

10

c.c.

partly filled with

bromine
the

last bottles
and

bromine

flask

170-175"

of the

in the

safety-tube) containing
each

c.c.

heating

start

of

is

mometer
ther-

is inmiersed

bulb

first bottle
a

that

gas

funnel, also

series

any

reaches

Put

of

of

Begin

sand-bath.

pressure

dropping

(it is
H2SO4,

of

the

mixture

of

instead

H2SO4

for

(having

catches

temperature
thereafter.

of C.P.

Use

loosely corked

over.

used

solution, and

alkali

dilute

be

with

mixture

water.

can

that

so

bottle

NaOH

having

c.c.

stoppers

in the diagram

dilute

83

rubber

Connect

Woulfif

and

flask.

the

because

shown

liter flask heat

carbonizing), using

apparatus

liquid.

In

(1)

little sand

the

position
decom-

by

by heat, C2H6HSO4

acid

ethyl sulphuric

of alcohol

c.c.

avoiding

It

explosive

an

+H2SO4.

stated

forms

in
burns

and

colorless

is obtained

It

oxygen.

Experiments.
of 30

is

Ethylene

yellow flame.

mixture

It

2%).

is the

is contained

and

importance,

of

(about

gas

with

gas), CH2=CH2,

(ethene, olefiant

Ethylene

is

that
when

the

maintained

safety-tube

liquid, and

may

attach

of the

piece

UNSATURATED

tubing.

of

evolved

By

(Von
lost

then
the

through

of

acid

sulphuric
the

latter).

ethylene
The

until

bromine

benzoic

hyde,

as

by

the

acids

aldehyde

fiask

is

malonic

of

and

acetone

oxidation

compounds

the

is

stand
then

in

flask,
alcohol

85

c.e.

of

ice-water.
the

bj formic

theoe

the

decolorized.

and

sul

flame.
hjdrox\

aldehyde

icetophenone
of

safety-

to

remove

phenols

pink

production

almost

hydrated

of

former

steady

decolorized
other

bisulphite

(bccauM;

unsatunted

up

into

mixture

of

c.c.

should

re"igent

by

slowly

of
in

the

the

bromine

bottles

Baejers

sugalB

some

Keep
the

Disconnect
"Von

(100

^) until

Lower

funnel,

droppmg

carbonate

of

running

the

solutions

precipitate

appears.

begin

bubble

of

sodium

reagent

brov. nish

dioxide

and

and

tube

mixture

301

"

this

and

Baeyer

and

manganese

tube

through

permanganate

test-tube
18

of

means

ethylene

potassium
color

HYDROCARBONS

benzalde

gh

cerol

stances)

ns

and

well

302

CHEMISTRY

ORGANIC

the

Wash

funnel, and
Draw

bromide

ethylene

finally shake
bromide

ofif the

chloride, and

with

After

cork.

Also

take

bromide

day

or

easily solidified,melting

is

coal

(2) Bubble

into

gas

Von

calcium

distill,
noting
at

specific gravity (2.1785

the

solution.

dry

so

129.5"

but

ing
separat-

NaOH

flask, add

a
a

boiling-point (130.3",

the

it with

into

in

water

at

730

mm.).

20").

The

9.5".

at

Baeyer's

reagent,

above.

as

(propenol), CH2=CHCH20H,

Allyl alcohol
unsaturated

alcohol

CH2=CH

propene,

is called

allyl. This

aldehyde
from

CH3.

alcohol

OH
CH"

carbon
hydro-

cerol.
gly-

from

made

is

tube

0.3

with

Dip the end

Heat

Finally

the

test

Schifif's reagent
oxidation

CHO

CH2=CH"

c.c.
a

dry

of 85%

the

in 2

glycerol

solution

+2H2O.

mix

phosphoric
bent

to

acid.

in

c.c.

Fit
tube.
small

high temperature.
power

tests).
acrylic acid,

CH2=CH.C00H.

delivery

of water

c.c.

for reducing

(aldehyde
it becomes

test-tube

and

stopper

of this tube

test-tube.

is produced

(Acrolein)

In

glycerol and

It

CH"

Experiment.

By

be

alcohol.

202)

p.

(Glycerol)

the

the

Its radicle,C3H6,

can

above

the

from

glycerol (see

OH

CH2"

"

to

(acrylic aldehyde), CH2=CHCH0,

Acrolein

the

corresponding

isan

and

with

UNSATURATED

Crotonic
Oleic

is

acid

the

It has

is CH3CH

acid

CHCOOH.

member

303

HYDROCARBONS

of the

acrylic acid

series.

formula,

CH3(CH2)7CH=CH(CH2)7COOH.
is

It

contained

combination

in

glyceryl trioleate, in
oil, and

whale

in

crystals, melting

14".

C18H34O2
(Oleic

reaction

is

hydrogen

of

of

in

tube;

shake

(see

301).

p.

with

(2) Shake
the

ether

oleic
so

becomes

acid

that

Erucic

and

the

facilitate

acetic

color

little

with

yellow.

shake.

The

In

this

some

the

with

the

in

acids.

drops

two

of ether

Von

process

(generally

results

in

of

oleic

test-

Baeyer's

reagent

little bromine

water;

Add

few

bromine

is lost.

oils,as cod-liver oil.

drops

is taken

acid, CH3(CH2)7CH=CH(CH2)iiCOOH,

is present in

cially
commer-

reaction

potash

centimeters

ether

some

of

catalyzer

caustic

cubic

acid)

fats.

(1) Dissolve

few

to

palmitic and

Experiments.
acid

addition

by

advantage

solid

used, and

with

Fusion

formation

converts

hydrogenation of oils,by which

into

is

gas

taken

nickel) is employed
olein.

acid

forms

C18H36O2.

(Stearic

now

converted

are

+2H

acid)

in the process

they

oil and

acid

about

brought

as

thus:

hydrogen,

This

Oleic

Hydriodic

acid ; this is

it into stearic
of

fats.

animal

glycerol

in olive

oils, as

many

at

with

of
up,

304

ORGANIC

acid

an

takes

acid.

Its

It has

the

and
in

Br

becoming

taking

hard

solid

it has

molecule

tetrabromstearic
in linseed

oil.

from

the

substance, hence

its

up

oxygen

air
use

paints.
Ricinoleic

acid,

CH3(CH2)5CH(OH)
is

Its

one.

to

now

acid, but

is contained

ester

of

power

of

producing

atoms,

glyceryl

oleic

to

instead

Unkings

four

up

similar

somewhat

double

two

is believed

acid, C17H31COOH,

Linoleic

be

CHEMISTRY

"

in castor

present

CH2

"

CH=CH(CH2)7COOH,

oil in combination

with

glycerol.

ACETYLENES

These
which

hydrocarbons,
members

few

Small
and

passed

between

*'

cheaply by the
C2Ca

When

with

used

light, and
colorless

The
action

+2H2O

is used
gas

in acetone.

of

gas

methane
when
is made

of water

of

stream

poles of

It is formed

back."

snaps

of

quantity

time.

same

carbon

the

only important

C2H2

on

electric

an

an

is
arc-

formed

being
a

from

hydrogen

Bunsen

at

burner

easily and

most

calcium

carbide,

+Ca(0H)2.

special burner, it gives

as

of

ber.
mem-

synthesized directly

are

when

hydrogen

light, a small
the

is the

quantities

carbon

series

known.

are

CH^CH,

Acetylene,

form

CJl2n-2y

illuminating

unpleasant odor.

gas.

It is very

brilliant
It

is

soluble

UNSATURATED

Experiments.
in

(1)

cork.

By

Baeyer's

with

used

for

(2)

of

inside

ammonia

the

to

strike
The

dissolve
add

0.5
2

the

of

c.c.

then

1.5

dilute

to

gm.

25

c.c.

Then

tube

such

the

of

as

acetylene;

is

is

copper

concentrated

chloride

red

beaker

precipitate

formed.

producing

thus

cuprous

gas

causing

hydroxylamine

gm.

Von

secured.

inverting

of

C2CU2,

of

bent

carbide

the

glass

solution

stream

chloride

cuprous

into

Light

experiment,

back,

fit

on

is

test

by

acetylide,

Repeat

hole

obtained.

with

over

copper

the

acetylene

the

funnel

acetylene

hydrogen.
is

dropping

drop

bide
car-

two-holed

other

platinum-tipped

flame

moistened
in

until

Test

the

calcium

with

the

burning

brilliant

cork

water

Bubble

reagent

connect

the

Let

slowly.

very

into

of

gm.

suspend

and

tube.

10

bottle,

or

water,

delivery

Put

hole

one

containing

is

flask

dry

305

HYDROCARBONS

burner

Bunsen

acetylene.

prepared

easily
sulphate

ammonium

in

as

little

follows

water,

hydroxide,

hydrochloride,

and

XXII

CHAPTER

DERIVATIVES

SULPHUR

Sulphur

"

of

and

alcohols

cohols.

The

they

are

CH3

"

(cf

ethers

acid

acid

in

organic

dialkyl

are

with

as

nitric

looked

hydroxyl

group

may

an

The

as

upon

phonic
sul-

sulphuric

is replaced

/C2H5
S02"^
\0H

S02"^"
\0H
(Sulphuric

acid)

(Ethylsulphonic

by

an

CH2(OH)-CH2-S03H,
(see

p.

sulphone

obtained

is

Three

aliphatic

if

replaced

be

group

are

the

acid),

synthesis

of

272).

SO3H

they

acid)

into

enters

(isethionic

acid

j3-Hydroxyethylsulphonic

acids

group:

/OH

taurin

acid, sulphonic

be

acids

which

When

sulphides.

CH3-S03H.

thioal-

or

is SO3H.

group

Sulphonic

as

mercaptans

CH3-SH+30

formed,

are

ethers,

CH3OCH3)

called

are

oxidized,

hols
alco-

(cf. CH3OH),
.

Sulphur

in

oxygen

sulphtir alcohols

CHsSH
CH3

place

the

forming

ethers,

or

take

may

sulphones

used

as

the

by
are

hypnotics.
306

hydroxyl

an

of

organic

of

the

radicle.

importance,

cause
be-

oil.

CHEMISTRY

ORGANIC

308

It

is contained

Allyl

thiourea

(allyl sulphocarbamide,

/NH2
mine),
^'

S==Cc

remedy.

"

in

glucosidal combination

horse-radish.

and

black mustard

in

\nH.CH2CH=CH2

is
,

thiosina-

used

as

CHAPTER

CYCLIC

These
and

fatty
one

or

typical
either

aromatic

two

closed

aromatic

(saturated)
the

compounds.^
carbon

their

full

have

or

respond

to

(cf. benzene,

have

of

ethylene

the

like
do

not

instead

of

written

cyclic

of

as

the

Von

compounds);

CH2\
I
y"CH2;

series.

Baeyer's

reagent.

them

chains

(and
for

as

and

aromatic

"

compounds

komocyclic,
309

those

quite

Thus,

they

Therefore,
of

formulae

have

are

called

are

CH2V

y"CH2,
"

an

cyclopropane,

cyclopentane,

from

they

example,

CH2
Cyclic

their

hence

CH2

formula

composed

as

Unkings,

CH2
*

unsatura-

behave

they

methane

double

closed

causes

general

different

indeed,

representing
with

satisfied

for

tests

the

quite

series;

reduce

chain

open

with

properties

members

the

atoms

COMPOUNDS

hydrocarbons

CnHgn

which

linking

to

from

321).

p.

CYCLIC

Certain

their

obviously

double

tain
con-

differing

that

valence

They

chains,
in

the

between

group

compounds

compound

tion

transitional

the

have

COMPOUNDS

BICYCLIC

AND

form

XXIII

etc.

CH2
been

classed

together

310

ORGANIC

They
the

given the

are

methane

also

same

names

the

series,with

called

the

as

and

of

members

prefix cyclo.

polymethylenes,

compounds
Certain

CHEMISTRY

They

'

the

are

individual

trimethylene, pentamethylene,

are

of these

cyclic compounds

been

have

etc.

found

in petroleum.
There

Cycloses.
derivatives

the

of

cyclic alcohols

ring).

The

are

important

most

it is not

urine, being
d

and

It

sugar.

I and

these
C

to

are

of the

is inosite.

of these

has

hexahydroxycyclohexane,

empirical formula

same

attached

cycloses (OH

or

hydroxy

of

cyclic hydrocarbons;

Inosite, C6H12O6,
the

number

from

as

the hexoses

in animal

occurs

this

and

tissues

in

optically inactive;

source

dl varieties

however,

of inosite

skid

are

to

occur

in plants.

COMPOUNDS.

BICYCLIC

the

In

(and

in

volatile

These

oils obtained

various

hydrocarbons

TERRENES

other

having
called

are

(see

directly with

or

therefore

compounds,
respects and

many

the

class

of

closed

chain

many

of

301), and
molecules

general
but
be

may

they

them

carbon
can

atoms.

be

By

converted

Von

combine

they
of HCl.

to

are

CioHie.

decolorize

differ from

since

trees

there

properties

considered

cyclic compounds
of

products)

They

p.

two

the

possess

coniferous

empirical formula

terpenes

Baeyer's reagent
one

from

natural
the

CAMPHORS

AND

They
of

saturated
un-

these

belong

in
to

they

contain

mild

oxidation

into

cymene

(paramethylisopropyl benzene) (see p. 332), and

by further oxidation into paratoluic acid (see p. 362).

CYCLIC

Thus

AND

show

they

compounds,

BICYCLIC

distinct

although

311

COMPOUNDS

relationship to

they

not

are

aromatic
aromatic

true

compounds.
The

of medical

and

following

commercial

CioHie,

below,
Its

and

is

of

constituent
formula

It is

oil

given

dextrorotatory.

chloric
hydropinene

C10H17CI,
it

is

camphor,

the

of these

155".

it forms

since

which,

is

with

hydrochloride,

and

structural

opticallyactive.

combined
acid

principal

the

boiling-point

When

value,

bodies

many

the

has

turpentine,

include

camphors

important

are

Pinene,
of

and

terpenes

resembles

known

ficial
arti-

as

HC

camphor

(see

Artificial
converted
Oil
obtained

into

true

which

crude

is

oxidation

readily
alcohol

tine,
turpen-

by
and

pine

distillation

steam

fir)there

oils.

of linseed
from
and

the

air.

nitric

bicycliclike pinene,

Pinene

it takes

acid

into

its formula

can

resinous

be

hastens
up

It

160",
the

oxygen

converted

terpin.

being

wood

boils at
It

0.85.

oil,because

of

obtained

are

Turpentine

specific gravity of

tive
By destruc-

constituting rosin.

or

(pine

turpentine and

tains,
con-

separated by

distillation
wood

is

bark

oil

to

residues
distillation,

has

phor.
cam-

by incisingthe

in addition

and

can

of turpentine

of fir-trees ; the

waste

CH3CH

camphor

be

low)
be-

exp.

is

by
not

312

ORGANIC

CHEMISTRY

CHa
C"

H2C

OH

Ky^^^

/CH3.

CH-C(OH)^^jj^
taking

By
is

up

which

formed,

molecule

is

of water,

terpin hydrate

crystalline substance

used

as

medicine.

Experiments.
Into

10

of

c.c.

free of water

freshly distilled

(treat with

contained

in

gas

of

mixture
the

by

until

Make

tilling)
dis-

ing
freez-

of

crystals
HCl

the

dried

crystals

turpentine

some

Is there

reagent.

distilUng with
camphor

tree,

worked

on

by
and

NaCl

filter and

terpene

the

Its

on

ketone
ketone

In solution

Von

is

it is

structure

so

having
it is

that
the

linking?
by

of the

wood

recently

has

produced

now

commercial

group,

Baeyer's

obtained

gum

finely chopped

chemical

out, and

with

of unsaturated

This

steam

processes

contains

evidence

CioHieO.

Camphor,

below.

kept cool

HCl

is

them.

(2) Shake

before

chloride

appear.

Collect

H2SO4.

examine

been

dry

retort

flask

camphor.

tiu-pentine that

calcium

hydrochloride

heating
C.P.

in

bubble

mixture,
pinene

artificial

(1) Prepare

by

thetic
syn-

scale.

Camphor

it may

be

formula

dextrorotatory.

as

called
shown

CYCLIC

313

COMPOUNDS

BICYCLIC

AND

CH3

.1
CO

CH2

I
CH3

"

CH3

"

I
CH

CH2
Borneol
to

is

secondary

terpene

alcohol

CHOH

instead

having

camphor

CH2

ing
correspondof

the

CO

group.

is convertible

Camphor
thymol)
warming
into

by the loss
with

camphor)

has

of

group

Camphor

crystals.

secondary

of

Camphor

monobromide

be

to

can

oxidized

of the

one

is

camphoric

(oxy-

in the

group

It is

camphor.

By

sublimes, the

Hydroxycamphor

alcohol

of

it is converted

176.4", and

at

(isomer

hydrogen.

It melts

forming

remedies.

of

atoms

pentoxide

sublimate

CH2

of two

carvacrol

phosphorus

cymene.

into

place
newer

CioHisBrO.
acid.

CH3
COOH

CH2
CH3

"

CH3

"

Menthol
a

is

is

secondary

given

unsaturated
substance

COOH

CH

CH2

monocyclic
alcohol

below.

melting

at

CHOH!

group

Like

Unkings.

terpene alcohol

Menthol

42", and

of oil of peppermint.

is

Its formula
it

camphor,
a

ing
contain-

contains

white

is the

Its solution

no

crystalline

chief

uent
constit-

is Isevorota-

314

ORGANIC

tory.

It is useful

combination

CHEMISTRY

as

with

medicine.

It is excreted

glycuronic acid

in

(p. 221).

CH3
CIT

\
H2C

CH2

I /H

C"(

H2C

"CH3.
CH3

(cineol) is

Eucalyptol
from

oil of

liquid

camphor-like

Its formula

eucalyptus.

tained
ob-

is

CHa
C-

"O

H2c/\:h2
H2C"v

JCH2

CH3

CH

"
CH3

oil contains

Sandalwood

primary

alcohols,

tricyclic. They

Polyterpenes have

Caoutchouc

substance.

certain

the
two

formula,
or

ALLIED

SUBSTANCES

or

Rubber

isomeric

unsaturated

being bicyclic and

one

have

two

"

rubber

is the

tropical plants.

TO

other

C15H24O.

terpene

more

the

rings.

TERPENES

contains
hardened

terpene-like

milky

Synthetic rubber,

juice

of

having

CHAPTER

THE

studied

posed
of

of

of

are

represented

the

in the

that

compounds,
represented

We

into

come

of

opened.

belonging

bodies

and

They

may

substance

fatty

of
this
be

all
called

substances

of

methane.

are

indeed

may

Many

quite

upon

of

the

analogous
316

with

the

agreeable

still

known.

derivatives

just

derivatives
those

be

aromatic

an

are

CeHe,

are

readily

called

as

"

which

of

represented

be

easily

substances

of

they

name

benzene,

etc.

readily

nomenclature

presence

looked

acid,

were

group

the

can

cannot

chemical

this

is

acid

organic

that

it

chains,

members

the

"

older
to

by

of

group

chains

account

on

aroma,

closed
the

In

corresponding

indeed

group,

composed

bodies

to

now

largest

the

is
the

with

chain

an

cyclic

chain

closed

closed

of

sented
repre-

the

and

closed

anhydride

an

few

is, however,

connection

containing
their

be

to

It

the

In

atom.

have

bodies
in

hydroxy-acids,

of

chains.

link

that

e.g.,

converted

the

remembered

opened;
be

each

so

com-

as

atoms.

derivatives,

aromatic

derivatives

paraffin
be

by

carbon

of closed

have

we

formulae

their

anhydrides

of the

case

in

of

purin

composed

that

substances

the

as

and

as

will

the

chains

such

lactones,

only

all

open

them,

HYDROCARBONS

AROMATIC

Nearly
far

XXIV

as

as

of
all

the

derivatives
of
of

benzene

methane,

AROMATIC

THE

useful

them

are

have

very

There
groups

fatty series, few

them,

of

simple

of

however,
mercially
Com-

great value.
in which

reactions
and

the

the

give

fatty
"

two
very

results:

different

concentrated

1. With

with

reduction

nitro

aromatic
which

compounds,

yield amino-

unaffected

are

CgHsIh +HOINO2

a.

the

hydrogen

nascent

Paraffins

derivatives.

acid

nitric

readily form

hydrocarbons
on

the

physiological actions.

aromatic

the

possessing much

many

of very

are

four

are

"

foods;

as

pronounced
they

the

UnUke

properties.

same

and

reactions

similar

undergoing

317

HYDROCARBONS

HNO3.

by

C6H5NO2

+H2O.

(Nitrobenzene)

(Benzene)

6. CoHsNOz

+6H

C6H5NH2

+2H2O.

(Aniline)

sulphonic

(see p. 306).

acids

acid

sulphuric

concentrated

With

2.

Paraffins

are

they

form

unaffected

by H2SO4.

CeHsjH +HOj

"

SO3H

C6H5SO3H

sulphonic

(Benzene

do

of

When

more

side
as

methyl

substituted
4.

or

readily

not

case

be

and

Chlor-

3.

side

chain

to form

or

brom-benzene
with

react

+H2O.

are

very

KOH,

benzene
chains
chains

CI

stable

whereas

chloride, etc., hydroxyl

for the

acid)

in

and
the

readily

can

(see p. 137).

substitution
of carbon
become

simply carboxyl.

product

atoms

oxidized

is

with

one

oxidized, the

in such

way

318

ORGANIC

CHEMISTRY

BENZENE

the

At

we

must

benzene, since, as

has

been

substance

aromatic

outset

the

of

evidence

having

as

there

in

retorts

of

bases

small

The

blackness).
fractional

as

follows

also

are

oil
or

200",
method

is

tar

mixture

phenols,
also

tains
con-

(hence

its

separated partly

are

partly

tar is distilled into

chemical

by
four

fractions,

heavy
of

oil

oil (above

oil sinks

150").

(210-270").
270").
it contains

in water;

large

naphthalene.

United

the

to

(150-210").

creosote

(4) Anthracene

distilled

the

off from

suspension

and

densed
con-

ammonia

The

bodies, and

products

densed
con-

(3) Heavy

In

is
The

given

The

in

distillation

(2) Carbolic

amount

which

bodies, several

(1) Light oil (fractionup

The

artificial gas,

condensers.

of basic

tar

crude

The

means.

of

vapor

in water.

quantity

is heated

coal

coal-tar.

particles of carbon

by

gas

neutral

hydrocarbons,

and

the

that

dissolved

are

nish
fur-

must

correctlyrepresented

preparation

constitute

pyridine

We

When

speciallyarranged

vapors

and

the
with

out

passes

mother

is the

chain.

in

retorts

gas

is

(benzol), CcHe.

Benzene

in

closed

bodies.

of

structure

noted, this

its formula

that

the

study

into

heavy

part of the
^

is

coal-tar

fractions, the

two

the

and

States

Different

oil

above

phenols
from

benzine

and

commonly

more

light

oil to

200".

By

naphthalene

(see p. 121).

about
this
pass

THE

into

over

at

the

light oil.

residue

it is called
The
acid

then

benzene

and

benzene

can

large

purified by
alkaU
the

is in
its

of

further

by

treatment

and

reduction

of

tube.

aromatic

acid

it will

soda-

with

is

remembered,

be

for the

employed

tillation
dis-

(1) By

aromatic

an

preparation

=Na2C03

+C6H6.

(C2H2)

through

passing acetylene
This

method

of

out

illustrates

of

synthesis
C6(OK)6,
benzene

in

resulting

occurs

and

distillation

can

with

be
zinc

This

in

plished.
accom-

of CO.

is

converted
dust

red-

formation

the

in

potassium carbonyl.

be

can

current

synthesis of

how

fatty hydrocarbons

(3) By heating potassium

by

ing
finally by freez-

(2) By

of

tillation
dis-

H2SO4

concentrated
and

the
The

fractional

obtained:

CeHsCOONa+NaOH

hot

of

most

Uquid portion.

which,
that

analogous with

tillation
dis-

contained.

are

with

be

also

dilute

by subsequent

purified by

off the

salt

with

light oil that

be

may

methane

carbon,

of

amount

treatment

homologues

pouring

Benzene

is obtained.

270*^,anthracene

thiophene (C4H4S),

remove

lime,

is

with

then

it and

is continued

pitch.

light oil
and

319

If distillation

contains

It

to

above

temperature

The

HYDROCARBONS

AROMATIC

derivative

into
the

of

benzene

presence

of

water.

Benzene

boiling
Its

at

is

80.3''

colorless

liquid

of

(corrected) (at 80.12"

melting-point

is

5.5".

Its

aromatic
at 757.3

odor,
mm.).

specific gravity is

320

CHEMISTRY

ORGANIC

0.8736

at

It

-Jo-'

determinations
and

with

it takes

benzoic

put into

and

dry

condenser

what

At

while

(3) Shake
Von

(cf preparation of methane,

fractionating flask (an

boiUng-point.

the

and

the

warm

Baeyer's

the
are

ually.
grad-

chloride

cool in

crystallization occurs.

with

few

heat

dry calcium

dry test-tube

and

condenser

Note

airPut

ing-mixture
freez-

Remove

test-tube

with

the

thermometer.

remain

temperature

constant

melting?
specific gravity of

the

15^

of

gm.

quicklime,

powdered

stirringthe crystals with

(2) Determine
at

of

and

crystals

25

thoroughly

small

point does

benzene

gm.

do).

mixture

the

50

until

fingers while

of water.

the distillate with

will

the

Mix

with

distillate into

from

(1)

0.1%

of

extent

redistill from

the

solvent

good

the

to

0.03%

retort

Connect
Treat

and

is

It

only

about

up

acid

120).

p.

is inflammable

water.

in water

Experiments.

and

weight

substances.

It is soluble
and

for molecular

Benzene

(see p. 60)

immiscible

for many

used

be

can

the

cubic

reagent.

some

pure

balance.

Westphal

of benzene

centimeters
Does

it act

From

its

Uke

an

with
urated
unsat-

compound?
Structure

CeHe,

one

Uke

of Benzene.

would

those

expect
of

to

find

acetylene

or

empirical formula,
benzene

giving

other

unsaturated

actions
re-

of

existence

the

Such,

atoms.

does

addition

is not

combine

with

it is not

agents ; it does

compounds

for

the

bonds

between

formula

there

are

must

with

there

of benzene:

is

be

can

in

shown

simplest is
bromine,

of the

one

12

Our

us

is to

Cf
.

be

H,

H,

Perhaps

fact
the
with

benzene

the kind
different

that

replaced

is

thus:

atoms

by

of

heat

Unking

from

with

some

that

in

do

that
in

CH2"

have

we

then

can

C=CH.
than

in

by

compound,

which

combustion
we

this

the

group

of

replaced.

formed

that

To

CHa"

is

zene
monobromben-

the

etc.

another

distinctly greater

quite

products

atoms

whether

dipropargyl,CeHe, CH=C"

therefore

for

atoms,

hydrogen

suppose

see

the

atoms

important

treat

we

is identical

of

replace
Br

Ce

let

H,

replacement
3

hydrogen

formed

12

Further,

thus

atoms.

ways.

hydrogen

Numbering

problem

must

six

formula

monobrombenzene,

of

If

tions.
reac-

containing

This

variety

the

carbon

one

etc.

follows:

as

by bromine.

has

only

monochlorbenzene,

one

all these

monosubstitution

the

of

the

of potassium

as

all the

represent

ing
oxidiz-

carbonate.

sodium

carbon

the

isomers

no

solution

represented

similarly combined

as

toward

sensitive

readily give

be

cannot

carbon
Benzene

case.

evident, therefore, that

is

benzene

double

the

halogens, i.e.,form

containing

permanganate

It

the

decolorize

not

indicating

between

however,

products;

Unsaturated

reactions

say,

bonds

double

readily

not

is to

that

hydrocarbons,'

321

HYDROCARBONS

AROMATIC

THE

This

benzene;

benzene

ordinary unsaturated

must
pounds.
com-

322

ORGANIC

be

CHEMISTRY

replaced by Br,

meanwhile

replaced

by
acid,

the

originally present being

Br

by

This

H.

monobrombenzene

treating

resulting compound

the

be

can

plished
accom-

nitric

with

having

the

formula

Let

C6H4BrN02.

us

that

suppose

H
2

the

by

By

the

an

amino

NO2
action

CeH

(see

p.

acid

ft

it

becomes

group

376), and

the

is

Br

substance

our

(aniline).

(p. 384)

(see

is

salt is formed,

hydrobromic

NO2

for

HHHH

of aniline

diazonium

the

formula

(NH2)

salt

The

H.

then

NH2

replaced

CeBrNOaHHHH.

of nascent

group,

replaced by

thus:

group,

is

with

which

by

ing
treat-

the

acid

nitrous

with

treatment

385) yields

p.

By

monobrom-

benzene
and

in which

the

Br

yet this is found

with

that

in

atom

stands

be

identical

to

monobrombenzene

in

of H,

place

in

properties

which

Br

in

was

place

of

atoms

H.

similar

By
be

may

reactions

replaced

monosubstitution

the

by

one

product

the

one,

ing
result-

always

being

various

the

same.

fact

This

the C
for

then

atoms

there

varieties

of

the

upon

makes

it evident
as

Unked

would

On

this account

engineer before
that

the

an

in the

is linked

became
atoms

two

chain

chain,

or

depending
to

been

which

mechanical

chemist, conceived

must

three

(cf.alcohols, p. 109).

had

who

sent
repre-

open

products,

atom

Kekul6,
he

in

necessarily be

particular C

substituting group

cannot

we

together

monosubstitution

the

notion

that

be

the

represented

as

324

ORGANIC

Collie
tion

has

benzene.
the

the

to

as

made

of

spatial relations
represents

tetrahedron,

attached

are

extremely interesting sugges

an

model

His

center

CHEMISTRY

at

an

model
Such

to

angle

each
of

an

the

serving

simultaneously,

and

an

of

The

for support

permits

tetrahedra

atom

at

as

neighboring

center

tetrahedron.

arrangement

in

atoms

bons
car-

is

atom

25.

through

the

is mechanical

kinds, (1) the

axes

and

each

bands, while

by

Fig.

attached

the

of

can

(2) the

rest

face

not

of

the

(see Fig. 25)

rotation

rotate

on

three

of
their

two
own

pairs

of

THE

tetrahedra
the

rotate

can

model.

rotation

conforms

very

benzene

molecule

in vibration.
made

This
well

passing through

axes

possibility of double
to

the

conceived

must

be

those

rotations

the

successively

to

correspond

to

formulae

By

the

on

of the

center

325

HYDROCARBONS

AROMATIC

idea
as

model
the

that
a

the

system
can

be

following

h/Nh
H

HH.

H
H

The
two

first and
sets

of H

last
atoms.

would

indicate

Possibly

this

that

there

are

explains why,

326

in
a

CHEMISTRY

ORGANIC

of certain

substitution

the

tendency

of successive

l^" NO2

be

represents

and
the

from

evident

three

only

of

ring

of disubstitution

kinds

possible

are

following formulae, where

substituting group

some

instead

this conception

three

are

three

That

products.

atoms

i^'"NO2.

O2N"
with

there

fact that

is the

will

and

perfect harmony

In

there

instance, nitric acid forms

for

ones;

is

for H,
H

alternate

displace

to

groups

/V/N.

/\

/\

^\/\

\/

\/*\/
X

x/'^x/N/
X

(ortho)

(meta)

/\

\/

\/

The

substituting
as

that
with

or

two

in
a

the
^

second
The

the

replace neighboring hydrogens

may

formulae

carbon

such

exhibiting the

groups

(para)

marked

of the

atoms

abbreviations

and
0, m,

or

intervening, as in
the
and

be

ring intervenes,

first arrangement

meta,

A;

third
p,

are

are

para.^

C.

called
For

so
as

ranged
ar-

in B

Bodies

ortho,
certain

used for these terms.

THE

and

meta,
these

which

unknown

an

groups

to transform

necessary

which

side

contains

chains

yields.

does

as

for

tell to

to

product
a

which

be

can

hydrogen

atom

the

two

other

third
y

produced

In

next

to

its

which

it

simple

belongs.

This

isomeric

of

by

it is

stitution
disubis done

compounds

replacing still another

a

different

group

Suppose
ortho

an

of

some

ring by

groups.

group.

attached

of benzene

of the

unknown

therefore, how

see,

class

number

pler
sim-

arrangement

to

what

the

of

study

the

simpler substance
us

it is

belongs

that

same

the

It remains

possible

by

the

of

of the known

one

forms, it being considered

substance

which

to

substance

it into

it

ortho, which

is

ascertain

To

para.

of benzene

products

definitelyestablished

been

327

HYDROCARBONS

simple disubstitution

of the
has

AROMATIC

to

compound

from
this

represent

might

we

have

x,

or

carbon

one

removed

atom

from

it.

; that

is to

say,

there

be

might

two

products

trisubstitution
would
a

meia

yield the

compound

might

positions; thus, between

beyond

but

next

to

removal

on

disubstitution

same

which

them

occupy

the

two
as

in

of

In

product.
three
a;'s

B,

or

as

different
in

A,

or

separated

328

ORGANIC

from

them

by

CHEMISTRY

carbon

of

atoms

ring

the

C,

in

as

thus:

/%
X

\y

K^X

.^yX
y

That

is to

say,

which
In

there

yield

the

i.e.,next

to

trisubstitution

could

an

product

product.

only

occupy

only

converted

be

could

that

tion,
posi-

one

is

there

therefore

x;

ucts
prod-

trisubstitution

disubstitution

same

compound

para

three

are

one

into

it, thus:
X

To

take

example

an

There

are

six diamino-

yNH2
acids

benzoic

with

C6H^^NH2

formula

the

\COOH
By

removal

of

the

carboxyl

yield diaminobenzenes

which

be

meta;

two

diaminobenzene
be

ortho;

and

which

the

remaining

one

fore
there-

variety of
which

yields yet

(melting-point 140")

these

in properties

must

yield another

(melting-point, 102")

diaminobenzene
be

others

identical

are

63"), and

(melting-point

of

three

group

which

must

another
must

para.

For

convenience

of

description

it is

customary

number

to

carbon

the

329

HYDROCARBONS

AROMATIC

THE

benzene

the

in

atoms

ring

thus:

attached

are

similar

three

When

the

to

(e.g.,three

groups

ring, only three

benzene

(positions 1,

possible, symmetrical

are

(1, 3, 4), and

unsymmetrical
Analogous

the

to

is the

with

addition.

by

benzene

nickel, the

powdered

This

C6H12.

forming

and

vapor

it is

compound;

does

is

is

times
some-

is mixed

not

passed

each

on

to

act

like

over

carbon,
aromatic

an

(p. 309).

cyclohexane

OF

BENZENE

boiling-point 110",

(toluol), CeHsCHs,

Toluene

This

hydrogen

adds

IIOMOLOGUES

5),

paraffin hydrocarbons

mixture

the

and

letter 0.

When

"

of

CeHs.

group,

designated by the Greek

Reaction

isomers

adjacent (1, 2, 3).

alkyl radicles

phenyl

hydroxyls)

20"

specific gravity
light oil

from

by

treating

methyl

iodide

0.8656

at

-j^,

can

be

can

be

prepared

mixture

of

monobrombenzene

or

with

separated

synthetically
and

(cf synthesis of paraffins,

sodium

117).

p.

CeHsBr
This

methyl

+CH3I

reaction
benzene.

+2Na

Nal

-f-NaBr

clearly illustrates
By

oxidation

its

the

-hCcHsCHs.
structure

CH3

as

group

CHEMISTRY

ORGANIC

330

becomes

carboxyl, benzoic

therefore

formed.

stitution

139.2",

para

is

tion

the

138";

0.8766,

ortho

of

0.8655,

meta

from

first toluic

they give

there

141.9",

adds,

at

oil.

then

/CH3

\o
] m,

^COOH

C6H4\

and

as

is

fat-solvent, is

02116,

which

used

is

oxidation

instead

acid, CeHsCOOH,

of

ip

histologicalwork

of the

xylenes
on

The

m.

in

mixture

the

with

Isomeric

CeHs

extensively

^COOH
xylol, which

The
oxida-

CqR4\

phthalic adds,

of

-j^

By

/COOH
and

meta

0.8635.

para

of

three

are

is

hght

disub-

are

specific gravity

prepared

be

can

they

benzene,

boiling-point

The

xylenes

of

products

them.

ortho

Since

C6H4(CH3)2.

Xylenes,

being

CeHsCOOH,

add,

xylenes.

ethyl

benzene,

yields

toluic

benzoic

phthalic

or

acid.

C6H3(CH3)3,

Mesitylene,

boiling-pomt

164.5",

9 8".

specificgravity
light oil, and

0.8694

at

likewise

can

interesting and

important

mixture

of acetone

exp.

below).

enter

into

molecule

Three

be

obtained

contained

by

in
most

synthesis, viz., by
and

acetone

sulphuric acid
molecules

no

tilling
dis-

(see

doubt

synthesis, the sulphuric acid removing

of water
into

condense
formula

the

is also
-jo")

ring

from
as

each

and

represented

causing
in the

them

to

following

332

coming

it

Test

until

gradually
in

secured
add

the

about

aromatic

of
of

c.c.

few

color

test,

at

least

cork

under

sublimate

the

is
cool
in

mesitylene

the
of

some

test-tube;

When

the

and

crystals

tube.

Most

derivatives

their

conditions

of

this

standing.

on

is

Cymene

of
tube.

of

and

reaction

the

drops

chloroform

hydrocarbons

give

of

dry

coating

part

upper

solution

thin

in

aromatic

small

few

chloride

fraction

the

cium
cal-

with

the

Notice
Place

aluminum

anhydrous

heat

follows

as

Collect

150".

above

over

odor.

distill.

and

chloride,

it

dry

layer,

oily

the

Separate

water.

of

CHEMISTRY

ORGANIC

paramethylisopropyl

benzene,

CfiH

It

be

can

with

obtained

of

constituent

and

turpentine),

(from

oil

of

certain

thyme.

ethereal

CioHieO,

camphor,

warming

pentoxide,

phosphorus

CioHie

by

or

by

with

oils,

treating
chlorine.
as

oil

pinene,
It

of

is

eucalyptus

CHAPTER

AROMATIC

Of

by

HIO3)

(I2 with

have

to

necessary

of

prepared
bromine.

or

it

difficulty,

greater

agent

action

prolonged

By

be

can

oxidizing

an

only

product

chlorine

with

prepared

is

lodobenzene

being

with

benzene

treating

is

there

substitution

brombenzene

and

"

explained,

monohalogen

Chlor-

benzene.

already

As

of

kind

DERIVATIVES

HALOGEN

Benzene.

one

XXV

present
than

more

one

hydrogen

replaced

by

0-,

and

m-f

all

the

the

takes
instead

such

readily

into-

decompose

to

contrast

the

halogen
It
of

will

be

aromatic

following

the

the

(or
CeBre).

sunlight,

tion
addi-

products,
These

CeHeBre.
acid

halogen

benzene

halogen

and

tri-

derivatives

substitution

advisable

(or

substitution
and

indeed,

=3HCl+C6H3Cl3.

CgHgCIg

In

of

products

substitution

of

CeHeCU

as

CeCle
direct

in

are

hexachlor-

replaced,

place

there

course

products;

formed,

being

reaction

obtained,

be

may

products,
are

of

p-disubstitution

atoms

becomes

molecule

and

halogen,

benzene

brom-)
If

the

benzene

the

of

atom

for

compounds

products
the

student

(p. 423)

pages.
333

to

of the
of

look

frequently

paraffins,

benzene

over

in

the

are

sis
synop-

studying

the

334

ORGANIC

stable and

very

be

to

atoms

amido

an

Of

do

readily give

not

alkyl

etc., as
There

Toluene.

formula

readily yields

CI

CI

the
That

this is

oxidized

it

formed

when

three

The

their

the

CI

with

in

the

odors.
heated

this

respect
be

must

C6H5CH2CI.
when

fact that

It is

chlortoluenes

and

do

give

They
with

not

hydroxides,

like

etc.

chlorbenzene,
in direct

present

nucleus

benzene

that

halogen.

called

when

atom

respect

boiling temperature

at

the

are

aromatic

atom

behave

They
that

CI

bodies

other

agreeable

have
up

sunlight with

in direct

or

with

acid, CeHsCOOH.

is treated

toluene

the

and

suggest

chain, thus

benzoic

yields

in this

facts

by

the

odor

heated

when

is proved

really so

with

these, called

of

These
side

is in the

atom

do.

It behaves

fatty derivative.

group,

bodies

atom

hydroxides, cyanides, etc.

like

cyanide

disagreeable

very

its

up

halogen

halides

One

C7H7CI.

benzyl chloride, has

four

are

their

up

replaced by hydroxyl,

group,

empirical

CHEMISTRY

so

tion
connec-

itself,thus:

/CH3
CfiH

three

The

they

When
but

side

COOH,

the

chain

substituted

i.e., a

ortho,

are

oxidized

are

CH3

the

formed,

varieties

accelerated

chlorbenzoic

or

some

other

the

presence

acid

halogen-carrier.

removed,
into

being

They

cold, and

reaction
of

para.

converted

acid.

in the

chlorine, the

by

is not

becomes

by treating toluene
light, with

CI atom

benzoic

and

meta,

are

pared
pre-

in diffused

being

antimony

thus

greatly

trichloride

AROMATIC

In

the

HALOGEN

same

of

products
in

either

the

similar

the

di-

the

or

and

trihalogen

substitution

toluene,

phenyl

substitution

other

with

way

335

DERIVATIVES

methyl

products

exhibit

isomerism.

Phenyl

is

the

name

given

to

the

radicle

occur

The

groups.

toluene

of

may

stitution
sub-

CgHs.

XXVI

CHAPTER

AROMATIC

One

or

body

of

more

displaced

by

called

acid

called

with

phenol
the

table

into

contact

sodium

with

therefore,

and

from

water

with

therefore,

combined

in

the
and
the
the

other

(H2CO3

phenol

metals.

paraffin
hand,

or

and

(see

p.

such

even

are

decompose
336

comes

those

CO2+H2O)
can

OH

"

from

by

union

By

group

properties

are

only

be

can

that

tained
ob-

of

They

the
are,

and

water

which

formed

CoHsONa

solution

of

in

salts, called

e.g.,

of

brought

dryness.

to

presence

hydroxyl

in

phenol

the

be

alkali

with
the

the

H*

shown

as

phenolates

alcoholates,
can

quite different

than

Such

acid.

power

When

formed,

are

evaporating

stable

acids,

hydroxides,

phenoxides,

bolic
car-

few

acid

the

451).

p.

are

is

solution

organic

alkaline

dissolving

hydroxide

On

weak

of

them

pyrogalhc

in

Compare

phenolate.

differ

that

(appendix,

or

by

by

indicates

that

phenolates

of

monohydroxybenzene

liberated.

are

manifest

some

trihydroxybenzene,

acidity

resultmg

Phenols

that

be

may

the

OH,

"

phenol.
so

benzene

of

atoms
group

thus,

acid,' and

ions

properties,

acids;

Their

the

hydroxyl

bemg

faintly

COMPOUNDS

HYDROXY

thus

decomposed
acting
with
to

on

cohol
al-

phenyl,
possess

it has

when

137).
weak
more

acids

as

strongly

phenolates,

bonic
car-

acid

liberat-

AROMATIC

ing the

phenol.

The

decinormal

solution

of carbonic

acid

In

other

alcohols

(cf tertiary alcohol

"OH

oxidation

II

with

ethers

they form

(see

removed

by

for

as

into

them

The

112).

p.

from

by shaking

acid

carbolic

in

the

tions.

benzene

It

below).

exp.

also be

It may

sulphonate

is

benzene

by boihng
CeHsNa
(Benzene

with

diazonium

same

phenols.

This

the

with

important

carbolic
a

solution

oil fraction
of

resulting solution
acid

and

purified by
caustic

alkaU,
being

redistilled

recrystalliza-

potash

=C6H50H+K2S03,
sulphonate)

salt with

diazonium

NO3

be

can

the

on

prepared by fusing potassiiun

C6H5SO3K+KOH
(Potassium

acids

divide
therefore, sub-

triacid

precipitated by sulphuric

(see

salts,

PHENOLS

is extracted

of coal-tar

then

Using

may,

di-, and

mon-,

or

group

(carbolicacid), CeHsOH.

substance

or

OH

alcohols, we

MONACID

Phenol

ethereal

and

PCI5.

with

treatment

classification

the

"

OH

yield aldehydes, ketones,

not

tertiary

like

group

/Vc"

phenol), thus:
do

only 0.0037, that

behave

phenols

respects

but

being 0.174.

of

is

phenol

for

dissociation

percentage
of

337

COMPOUNDS

HYDROXY

+H2O
nitrate)

CeHsOH

water

+HNO3

(see p. 385)
+N2.

338

ORGANIC

Experiments.
oil
2

(1)

in

c.c*

ether, add

10

five minutes.

pipette and

the

filtrate

filter

to

steam-bath

of the

the

from

awaj''

and

residue

it for

test

(2) Prepare phenol from

made
of

(hot) solution

water

down

the

with

100

then

add

of

10

put
wall

sodium

blue

to

of

showing
procedure
acid

Transfer

p.

16).

sodium

extract

from

half-Uter

of

(8.5

The

free

cut

up

shake

Dry

the

flame

if

flask.

sodium
Distill

possible,a

into

strips),
This
nitrous

the

diazonium
to

salt.

40-50"

distill with

over

in

steam

into

the

the

distillate

with

several

separated
sulphate
off the

steam-bath

paper

ing
contain-

acid.

Saturate

and

dehydrated
corked

then

passes

steam.

ether.

c.c.

diluted

well

nitrous

flask, heat

phenol

the

in 40

gm.

solution

starch

hour,

an

chloride

over

days in

water,

salt into

aniline

for half

portions

running

the

with
with

with

diazotizingy because

water-bath

(see

of

flow

to

dilute

mixture

the

c.c.

and

is called

to

in 50

H2SO4

starch-potassium-iodide

presence

changes

freshly

well

iodide, dry it,and

the

odor

Mix

solution

(soak filter-paperin boiled

potassium

the

Into

of C.P.

Cool

drop

color

Note

aniline.

beaker.

nitrite
a

Evaporate

aniline, allowing it

of water.

c.c.

pipette,

dish.

ether

phenol (see tests, 3).

c.c.

of

c.c.

of the

water) until

gives

of 12

with

layer with

flame.

layer with

shake

evaporating

an

shake

filter. Acidulate

wet

ether

and

bottom

cool, and

HCl,

heavy
Dissolve

NaOH

off the
a

from

manner:

5%

through

Remove

transferring it
a

of

c.c.

Draw

with

vigorously.

on

phenol

Extract

(carbolic oil) in the following

for
a

CHEMISTRY

denser
con-

small

ethereal

for several

ether

(away

being safest);

340

ORGANIC

will
the

liquefy and
bottle.

in

CHEMISTRY

form

It mixes

all proportions.

5%

phenol
of

solution

50%

oily layer

an

with

glycerol, alcohol

The

easiest

is

solution

in

extensively used

in

produced

intestine

in

the
the

on

thus

phenol
unites
the

with

urine

potassium

in

Phenol

phenol

is
It

protein;

the
and

blood

excreted

be

is

organisms
micro-

of

in the
to

tity
quan-

proper

action

groups

sulphate,

potassium

as

the

is absorbed

produced

ether

antiseptic.

an

by

aromatic

the

of

prepare

glycerol.

as

surgery

and

to

way

by diluting

bottom

the

at

into

sulphate,

C6H5OSO2OK.
It

also

can

combine

uncombined
taken
The

suicidal

salts and

The

fatty ethers
halide
"

to

be

may

act

on

CeHsOjNa
chief

They
true

are

+IIC2H5

from

members

phenyl.

aromatican

alkyl

"

"

+NaI.

C2H5

of this class

are

anisole

(phenyl

phenetoU

Uquids having pleasant

both

since

ethers,

by allowing

CeHs

ethyl ether,

The

CeHs.

the

aromatic

reaction

"

(a)

aromatic

true

obtained

ether) and

methyl

phenolate

The

(") the
"

products.

phenyl

as

and

ethers

classes:

two

phenyl ether, CeHs

as

(1) the

are

of

are

-02115, and

CgHs-O
such

phenol

ethers, such

aromaUc'fatty

is often

It

poisonous.

(2) the substitution

ethers

Phenol

intent.
of

derivatives

ethereal

is

alkali

with

with

glycuronic acid.

with

ethers
a

halogen
They

be

cannot
cannot

may,

ethyl ether)
odors.

prepared
easily be

however,

(phenyl

be

by

The
this

displaced
obtained

AROMATIC

by heating phenol
aluminium

is

with

and

is

some

intact.
the

form

Tribromphenol,

Mononitrophenol,

acid

on

and

is

the

of

phenol

OOCCH3,
action

of

+HC1.

replaced

are

remains

hy'ijlroxyl
group
discussed

being

C6H2Br30H,

here,

the

the

of

most

later.

above).

(see exp.

water

C6H4(N02)OH,

prepared by

few

precipitated by

is

bromine

only

considered

these

In

phenol.

be

may

of dilute

action

ortho
nitric

phenol.

Trinitrophenol, C6H2(N02)30H,

prepared

"

OOCCH3

"

large class,but

others

treating phenol with

para

+H2O

by the

phenyl^ CeHs,

be

will

of the

important

or

of

radicle, but

compounds

CeHs

hydrogens

They

CeHg

"

prepared

products

substitution

by

"

phenol:

on

CeHfiOiH +CliOCCH3

more

CeHs

Phenyl acetate, CeHs

salts.

acetyl chloride

or

as

of these

type

one

such

dehydrating agent

CeHs

+H0

ethereal

The

341

chloride:

CeHsOjH
The

COMPOUNDS

HYDROXY

by allowing strong
(see

exp.

below).

symmetrically attached

OgNr

nitric
The

to the

picric acid, is

or

acid

NO2

to

act

groups

benzene

on
are

ring, thus:

/v-OH
^NOg.

V
N02

It forms
and

yellow prismatic crystals,has

is very

poisonous.

In

watery

bitter taste,

solution

it stains

342

ORGANIC

silk and

yellow, and

wool

fibers

staining elastic
in
and

Like

cells.

gland

three

by

evidently
H

dissociabiUty into
of the

rest

the

By

molecule

acid

Picric

ammonium

has

of

of the

its

ions

(cations) and

(see

exp.

of

in water

nitrates, as

substitution
in

groups

anions

of the

below).
action

acid

This

drinking

bums.

on

nitrates

on

is the basis

estimating small

for

sively
exten-

are

acidity, i.e.,its

phenolsulphonic

methods

explosive

an

negative NO2

production of picricacid results.

one

is

The

increases

for

granules

salts

anaesthetic

an

action

the

histology

zymogen

nitroglycerol,it

atoms

picric acid

also

in

for this purpose.

employed
of

is used

and

and

potassium

its

CHEMISTRY

of

quantities of

purposes.

C6H4(OH)S03H+3HN03=C6H2(OH)(N02)3
+H2SO4+2H2O.
Experiments.
of

gm.
10

C.P.
of

gm.

add

30

Uquid

with

into

of

fuming

the

the

Wash

acidulated

with

Warm

petroleum

and

will

with

drops

in

little

slowly

boil until

with

the

down

result.

to

Cool,

and

filter

water,

and

water,

crystals

10

subsided,

quantity

of

hot

of H2SO4:

=C6H2(N02)3(OH)

gently
ether

has

boiling

considerable

C6H5OH+3HONO2

(2)

Avoid

crystalline mass

suction.

acid

explosion

an

recrystallizefrom
water

nitric

yellow.

since

action

the

Put

add

flask, and

When

phenol.

becomes

dryness,
dilute

HNO3

gm.

picric acid.

(1) Prepare

picric acid

test-tube;

+3H2O.
with

c.c.

colorless solution

of

is

AROMATIC

HYDROXY

(no ionization). Pour

secured
into water

and

picric acid dissolved

the

(3) Immerse
cloth

in

Wash

them

the

; the water

shake

petroleum

becomes

in it

acid

solution

thoroughly

with

ether

yellow from

(ionization).
silk, and

pieces of woolen,

picric

S43

COMPOUNDS

for

minutes.

fifteen

running

cotton

Which

water.

dyed?

are

(seep. 382).

Aminophenols

(see p. 393).

acids

Phenolsulphonic

/CH3

with

accordance
from

the

and

meta,
tricresol
in

the

as

acids

obtain

to

as

less

are

used

with

soap,

phenol

as

water

acid,

(p. 340).
and

Lysol

is said

but

less

on

excreted

sulphuric

emulsion

an

produced

be

may

phenol

with

is called

micro-organisms

of

case

to

be

irritating.
of

cresols.

antiseptic properties and

possess

poisonous than

for

of

is also

with

of cresols

substances

These

Cresol

combination

the

forms

of cresols

(chiefly para)

in

in

cresols, viz., ortho,

mixture

by the action

strongly germicidal

Creolin

three

The

Cresol

mixture

theory

cresylic acid.

urine

exactly
is

corresponding toluene-sulphonic

intestine

the

it is

ing
start-

para.

or

protein.
in

the

In
.

possible,by

toluidines,

or

CgH4"C

(hydroxy toluenes),

Cfesols

phenol.

They

are

extensively

disinfecting purposes.

Parahydroxytolyl
of sinalbin

oil, obtained

mustard

(p. 253), is

by

drolysi
hy-

thiocyanate deriva-

/OH
tive of para

Thymol

cresol, CeH4"r
pinto-

and

carvacrol

are

isopropyl

cresols.

344

ORGANIC

this

That

is

CHEMISTRY

by

is shown

so

the

that

fact

they

can

yCHs
converted

be

both

into

CoR^k

cymene,

/CHs

^CHs
of

OH).

removal

of

phenols,

and

(by

They

might

reactions

considered

be

therefore

Thymol

hydroxycymenes.

the

give

also

as

isopropylmetacresol,

is

CH3

/^\
/CH3
CeHseOH

^CsHt

carvacrol

and

(1)
(3)
(4)

HC

CH

or

HC

\c/

isopropylorthocresol,

is

CH3

/^\
/CH3

CcHsf OH
^C3H7

Thymol

(1)
(2)
(4)

HC

COH

HC

CH

or

^"c

is contained

in

oil of

antiseptic, being less poisonous

melting-point

spite of the

In

extent

of about
Carvacrol

agent.
Aristol
is

of

an

(thymol

its

fact

0.1%

crystals
that
it is

thyme

than

is contained

is 49.4"

iodide) is dithymol

antiseptic powder.

an

The

(corrected).
only

efficient
in oil

is

phenol.

it dissolves
an

and

to

the

preservative

of

caraway.

di-iodide.

It

COMPOUNDS

HYDROXY

AROMATIC

PHENOLS

DIACID

These

in

gradation
169".
rise

melting-points,

(Not all
in

have

0, m,

this account

on

quinol)

ferric chloride

With

becoming

consistent

manner.)

them

119", and

show

all

They

and

(especially hydroin

developers

as

is

reducing properties,
of

some

used

are

this

in

less marked

or

104",

There

para.

compounds

melting-point

more

and

ortho, meta,

are

345

photography.

they all give color reactions

by

partiallyoxidized.
pyrocatechol

Orthodihydroxybenzene,

(1, 2-phenOH

diol, pyrocatechin,

catechol),

H
be

can

with

by fusing orthophenol-sulphonic

made

caustic

introducing
of

atom

It

potash.
methyl

radicle

hydroxyl

group,

one

is soluble
in

in

place

of

acid

By

water.

hydrogen

guaiacol (monomethyl

/0CH3\
ether
This
tar

of

latter

by

be

also

can

distillation

and

separated

or

the

treatment

benzosol,

and

of

from

beech-wood

crystallization,and

used, particularly
in

) is obtained.

pyrocatechol, C!6H4"C

as

one

phthisis.

guaiacol

of

its

Guaiacol

carbonate,

is

times
some-

compounds,
benzoate,
or

duotal,

346

CHEMISTRY

ORGANIC

(CeHi 001130)200,
remedies
The

been

also

have

much

used

as

tuberculosis.

for

constituents

important

most

of

creosote

are

/CH3

guaiacol

creosolSyCeHa^OH

and

^OCHs
(1, 3-phendiol,

resorcinol

Metadihydrozybenzene,
OH

C
H"

0-

is

resorcin)

made

fusing

by

oh'

H
acid

metabenzene-disulphonic
It is soluble

in water,

fluorescein
nitrite
turn

(see
blue

exp.,

pigment,

with

have

phthaUc
and

372),

p.

potash.

caustic

its solutions

heated

When

taste.

and

with

ish
sweet-

acid

it forms

with

sodium

lacmoid, solutions

of which

acids.

red with

Paradihydroxybenzene,

hydroqtiinol

(hydroqui-

OH

H"

C"

H
is extensively

none,quinol, 1,4-phendiol),
H"

OH
used

in

photography.

C"

348

ORGANIC

CIIEMISTRY

PHENOLS

TRIACID

{pyrogallic acid, 1, 2, 3-phentriol) is

Pyrogallol

{adjacent,

1, 2, 3

and

C6H3(OH)3,

see

(see

The

absorbs

monoxide

gas

is

benzene,
potash
coside
with

and

on

produced

by
as

the

carbon

some

It is

oxidation.

developer

in

raphy.
photog-

3, 5-phentriol)
,

{symmetrical) trihydroxy-

is obtained

the

by

phloretin,which

is

split off

caustic

of

action

the

from

phloridzin (see p. 252) by boiling

the

glu-

latter

acids.

alcohoUc

is also

solution

employed
as

reagent, mixed

with

dryness, it gives

the
a

acid

along

When

with

vanillin

{Giinzberg's

indicator

an

acid.

reagent) for free mineral

to

it is

that

air, so

with

along

1, 3, 5

Phloroglucinol
in

alkaline

made

(phorogludriy 1,

Phloroglucinol

is easily

analysis (see exp. below).

in gas

extensively employed

C6H3(OH)3,

the

from

acetates

are

when

solution

oxygen

and

Carbonates

and

needle-shaped crystals

fine

for this purpose

used

also

(Pyrogallol)

in water.

greedily

(1)
(2)+C02.

CoHafOH

(Gallic acid)

soluble

/OH

J^^Ij

It forms

tion
by the dry distilla-

below)

exp.

,^".

C..H

trihydroxbenzene,

be prepared

can

of gallic acid

329)

p.

drop

of this

solution,is evaporated

deep-red

stain

if mineral

acid

is present.

Hydroxyhydroquinol
benzene.

is

asymmetrical

tri-hydroxy-

AROMATIC

Experiments.

gallic acid
carbon

solution;

10

and

shake

the

of

1 gm.

of the

water) with

full of water;
rises to

the

open

the

take

dropping funnel,

Connect
with

stem

tubing being

and

the

cock, whereupon
of the

place

tightly,

minutes.

few

burette, the burette

is obtained.

(after fillingthe

funnel

chloride

solution, cork

vigorously for

stem

ferric

color

pyrogallol into
NaOH

dry

apparatus;

dilute

with

blue-black

of strong

c.c.

of

gm.

pyrogallol sublimes.

and

latter

intense

an

(2) Put
add

the

sublimation

or

is evolved

of

some

retort

dioxide

Test

heat

(1) Carefully
in

349

COMPOUNDS

HYDROXY

has

that

oxygen

water

been

absorbed.
Level
then

read

from

finding

the
air

funnel

how

in the

water

the

replace

to

By

the

up

burette
the

much

how

completely,

the

funnel,
was

to

fill

unabsorbed

of

volume

quired
re-

absorbed.

was

is needed

water

more

the

water

that

oxygen

much

and

burette

(N2) is easily determined.

(3) Test

with

ferric

AROMATIC

solutions

chloride;
ALCOHOLS

Besides

the

above,

of benzene

instead

replacing

benzene
The

possess

Thus,

reactions

we

in
one

which
of

is

example

obtained.

are

also
the
the

KETONES)

have

hydroxy

hydroxyl

with

side

In their reactions

entirely from

all the

properties of fatty primary

alcohol

can

phenols
be

the

chain.

C6H5CH2OH,

differ

benzyl

group

of

hydrogens

is benzyl alcohol,

phenyl carbinol.

pyrocatechol

AND

may

nucleus, is connected

best

which

color

(ALDEHYDES

derivatives
of

and

of resorcinol

prepared

and

by

such

cohols
al-

indeed
alcohols.

boiling

350

ORGANIC

benzyl chloride

for

CHEMISTRY

time

some

(cf synthesis of methyl

alcohol,

C6H5CH2ICI +HIOH
(Benzyl

The

CI

being in this

group,

and

OH.

with

almonds)

aldehyde

+2H

and

benzyl

salts,such

an

aldehyde

acetate

00CCH3),
There

one

first

of

those

(benzoic); ethers,

benzyl

as

(which, however,

are

bitter

(CeHsCH20-CH3),

ether

methyl

where

acid

an

with

agree

yields

then

easily obtained.

nucleus

(oil of

be

CH2OH.

"

alcohol

(CeHsCH2

treatment)

CeHs

oxidation

(benzaldehyde)

products

also

may

hydrogen:

of this

fatty alcohols:

are

aldehyde)

reactions

ethereal

with

nucleus, is easily

alcohol

Benzyl

CHO

"

(Benzoic

and

+HC1.

connected

the benzene

nascent

CeHs

as

CH2OH

"

case

treating benzoic

by

such

with

not

by

replaceable

The

CeHs

137)

p.

water

chloride)

side chain

made

(6-8 hours) with

or

are

substitution

obtained

not

of the

more

replaced,

also

are

by direct

chlorbenzyl

e.g.,

of the

atoms

alcohol,

CeH4ClCH20H.

Benzyl
from
form

alcohol, however,

for

aliphatic alcohols;
ester

an

with

differs in many

sulphuric

respects

instance, it does

not

Its boiling-point

acid.

is 206.5^
The

homologues of benzyl alcohol

(a) those

in

but

which
the

the

phenyl

alcoholic

higher fatty radicle, and

side

are

group

chain

(6) those

of two
remains
contains

in which

the

kinds:
changed,
unsome

alco-

AROMATIC

holic

side

chain

carbinol), but

one

nucleus

benzene

of

more

or

remains
(i.e.,

unchanged

remains

351

COMPOUNDS

HYDROXY

the

as

the

of

atoms

in

replaced by radicles,as

become

/CHa

tolyl carbinol, C6H4"

^-^.

alcohols, since

These
alcohol

be

can

group,

contain

they

oxidized

the

primary
and

aldehydes

to

acids.

is

CeHs-CHO,

almonds),
being

(benzaldehyde,

aldehyde

Benzoic

and

reactive

very

oxidation
the

of

action

Besides

amygdalin,

of the

the stone
is

glucoside

peach,

usually

Hydrocyanic

present

acid

C2oH27NOii^2H20

(see

employed

emulsin

"

the

(^^jj^ (^jjq +HCN

also be

benzoate

and

(Dextrose)

prepared by distillinga mixture

formate, and

with

C6H5CHCI2,
pressure

tion:
reac-

+2C6H12O6.

(Benzaldehyde)

can

sin
emul-

(Amygdalin)

It

on

"

amygdalin.

during the

produced

by

almonds,
The

262).

p.

by

obtained

in bitter

with

along

is also

be

can

contained

etc.

substance,

much

ferment

hydrolyzing

bitter

being produced

it

benzyl alcohol,

of

of

important

an

therefore

organic synthesis.

for

oil

water

by heating benzal
and

milk

of lime

of

ride,
chlounder

CeHsCs"

OM

Ci+H

C; H5

"

CHO

+2HC1

+H2O.

Ci+HliOH
Commercially
It is

an

oil of

it
a

is

made

from

benzyl

pleasant odor, boiling

at

chloride.
179"

and

352

having

specificgravity of

relatively insoluble
agent.

addition

products

with

acid

CH

(see
N

aldehyde

Like
with

Although

as

aldehydes,

substances

such

"

NH

"

is

with

It also

alcohol

with

air

containing

benzaldehyde

and

acid,

with

sium
potas-

some

of it

condense,
In

When

oxidizes

tact
con-

zoic
ben-

to

it combines

hydrogen

alcohol.

benzyl

form

readily

nascent

forms

zyl
of ben-

henzoiuj CgHs-CHOH-GOCgHs.

forming

bines
com-

and

solution

molecules

boiled, two

as

phenylhydrazine,

When

CeHs.

flavoring

other

sulphites.

388)

p.

in dilute

cyanide

to

it is used

acid

and

15".

at

alcohols, acids, ketones, etc.,

hydrazone
"

in water,

poisonous.

hydrocyanic

CoHs

1.0504

It is not

it forms

CHEMISTRY

ORGANIC

benzaldehyde

is treated

with

acetic

dride,
anhy-

benzoyl acetyl peroxide^

CeHs
is

The

produced.

"

CO"

formula
H

is
0

hydrogen

peroxide,

acetozone

(or benzozone)

"

strong germicidal powers

It

is used

aromatic

Any

and

KOH

reduction

quantities

Experiments.

in

small

and

"

CHs,

comparable

of

virtue

to

ide.
perox-

with

(1)

and

product being equal

the

(reduction) and

To

50

c.c.

orders.
dis-

strong

stand, undergoes oxidation

alcohol

flask add

being

have

to

intestinal

shaken

when

of

is called

believed

is

that

to

This

H.

"

therapeutically for

simultaneously,
of

"

by

aldehyde

allowed

OC

O"

O"

c.c.

of

acid

tion).
(oxida-

benzyl chloride

of water

and

gm.

nitrate, also

barium

boil

for

If

is still present,
of

and

ether,

Shake

pipette.

developed,

soluble

2C6H5

"

(2)
acid

To
a

2C6H5

"

with

in

Note

of benzaldehyde.

Add
color

beautiful

heating, because

on

water, but only slightly

the

of

+NO2

+N0

+BaCl2

CHO

little water

The

glass, and

c.c.

ether.

in hot

solution

and

let it stand

of

in acetic

crystallizeit
melt

benzaldehyde

until

hyde.
of benzalde-

drops

few

precipitateand

drop

+H2O.

phenylhydrazine

crystals of hydrazone

(3) Spread

ride
chlo-

few

layer

the

warm;

+Ba(N03)

Collect
alcohol.

and

water.

some

add

vent
pre-

portions of ether

odor

is soluble

CH2CI
=

bottom

the

and

add

Cool,

is intensified

which

in cold

benzyl

Evaporate

reagent

benzaldehyde

unchanged

three

the

and

Schiff's

some

is

with

oily drops

condenser

filter.
off

funnel.

separating
the

draw

reflux

to

hours.

two

(to

capillary tubes

some

Attach

bumping).

353

COMPOUNDS

HYDROXY

AROMATIC

152".

at

on

from

watch-

acid

crystals of benzoic

appear.

(4) Mix
alcohol

in

solution;

10

small

(5)

To

Add

10

c.c.

of 10%

c.c.

reflux

12

of

KCl^

condenser,

for

zoin,
Cool, filter off the crystals of ben-

solution

tube, and

cork

the

Note

the odor;

Cinnamic

flask.

hot

recrystallizefrom
a

and

benzaldehyde

heat, using

now

thirty minutes.
and

of

c.c.

of

keep

alcohol.

at

also test with

40"

CH=CH"

for

emulsin,

some

Schiff's reagent.

aldehyde has the formula

CgHs"

add

amygdalin

CHO.

hours.

354

ORGANIC

It is the

essential

cinnamic

aldehyde

ortho

displacing the

is

the

having

compound

and

alcohol

an

oil.

thetic
Syn-

natural

oil.

of cinnamon

constituent

Saligenin is both
an

CHEMISTRY

phenol;

it is

formula,

/OH
CcHx
CH2OH
It is combined

(see

dextrose

in

the

glucoside salicin

252).

p.

The

Ketones.

phenyl

and

ketones)

CO

group

fatty

be

may

(aromatic

groups

phenyl

attached

ketones),

linked

or

to

aromatic

(mixed

group

to two
a

fatty

These
those

with

are

analogous

prepared

by

methods

studied

in

connection

already

with

with

aliphatic

ketones, thus:
a.

By

distillingcalcium

benzophenone

or

CcHsCO

is

benzoate, diphenyl ketone'

produced:
CgHs.

O.

\C0+CaC03.

"Ca=
^

CeHslCOO

CcHs^
(Benzophenone)

b.

distillingsalts

By

acids, such
n

TT

as

of

salt of benzoic

/CH3

\C00M

p,

XT

and

one

aromatic

of toluic

acid

/CH3

"C0 +M.CO3.

^
^

CeHsCOOM

different

two

CeHs
(Phenyltolylketone)

The

metal.

salt

usually employed

is that

of calcium.

means

XXVII

CHAPTER

AROMATIC

ACIDS

ACIDS

MONOBASIC

acids

Aromatic
the

of

monobasic

and

value
will

oxidation

be

oxidation

By

1.

with

this

if

acid

dibasic

halogen
acid

benzoic
2.

By

is

it

when

hydrolysis

yields

benzene

exist,
the

Thus

series,

CeHsCHs,

monacid

their

only

chains

obtained.

alcohols

C6H5CH2CH2OH,
halogen

in

follows

contain

must

is

situated

the

derivative

substance

(phthalic)

their

chains.

It

side

etc., and

CeHsCHO,
the

chain.

CeHsCHsOH,

aldehydes,

and

side

two

the

of

benzene

aromatic

an

the

of

reactions,

any

C6H5C3H7,

C6H5C2H5,

side

follows

as

number

large

When

of

hydrocarbons

as

oxidation,

on

chain.

side

one

fatty

that

acid

benzoic

are

since,

product

numerous

of

single

from

by

which

of

important

most

commercial

oxidizable

h,aving

prepared

end

etc.

benzoic,

interest,

of

body

is

great

later, it is the

derivatives
can

of

is

animal

dibasic,
acid

physiological

the

in

benzene
It

much

of

explained

be

acid

This

CeHs-COOH.

monobasic,

those

with

analogous

general

being

paraffins,

representative

The

in

are

the

derivatives

side

chain,

where
all

yield

oxidized.
of

benzonitrile,
356

CeHsCN

(see

AROMATIC

p.

256).
the

The
CN

reagent

distillingpotassium

be obtained

can

for

group

357

ACIDS

an

benzene

by

benzene,

of

ing
substituteither

with

sulphonate

by

sium
potas-

cyanide,
C6H5SO3K
or

by heating

p.

386).
3.

+KCN

By

CI

is then

CeHsC

with
6.

boiling

boiled

(see

with

OJH

Cl+H

is the

369) with

with

toluene

is

(see

water

exp.

chlorine,
produced,
below)

C0H5COOH

+3HC1

+H2O.

OH

ordinary

conunercial

sublimation

By

p.

OH

CI

(see

Cu2(CN)2

benzotrichloride, CeHsCCla,

CI

5.

salt with

+H|OH.

treating

whereby

This

+K2SO3,

treating benzoyl chloride

By

which

diazonium

water, CeHsCO
4.

CeHsCN

or

method.
of

treatment

benzoin

gum

alkaUes.

heating

By

hydrochloric acid

CeHsC^NH

"

hippuric

(see

p.

360)

with

(hydrolysis):

CH2COOH

(Hippuric

acid

+H2O

acid)

.C.H.COOH+CH"^QQ
Benzoic
melt
is

at

acid
121.3"

forms

(corrected) and

slightly soluble

increases

with

needle-shaped crystals, which

in

cold

rise in

readily sublime.

water,

but

temperature

its

It

solubiUty

until,

at

90",

358

ORGANIC

contains

the water

beneath

the

further

raised

in

The

in the

soluble

employed

contain

their

as

is

those

of

in

solution

It is soluble
with

steam.

and

numerous,

acid.

are

of them

Most

with

in the

and

of Tolu

same

balsam

monium
am-

and

free acids

of

their

as

Gum

alcohol.

benzyl

as

way

Peru)
and

benzoic

constituents

esters

benzoin

than

other

of benzoic

add.

containing less cinnamic

balsam

and

(1) (a) ).

(see exp.

as

sodium

medicines.

important

acids, both

combination

in

very

prepared

are

(e.g.,balsam

cinnamic

liquid is

behaves

acid.

acetic

as

acid

of acetic

Balsams

is

salts

ethereal

those

are

salts

metallic
are

The

of

layers

two

volatilizes

are

is

in water.

the

Of

those

with

analogous

the

liquid layer

ether, and

layer

homogeneous

melted

derivatives

Its salts and

crystals

form

(p. 363)

not

the

temperature

tube,

lower

acid,

and

alcohol

are

closed

and

the

till,at 116",

manner.

of water
in

When

Salicylic acid

obtained.

acid, and

liquefy

water.

gradually mix

similar

of the

11.2%

undissolved

remain

that

CHEMISTRY

acid

balsams.

(1) Preparation

Experiments.
Put

into

of water,
reflux

flask

and

Cool, collect
hot

from
on

the

benzoic

200

the

water,

dried
acid

of

c.c.

small

condenser

cooling add

pieces

and
c.c.

boil
of hot

crystals
and

make

benzotrichloride,
of

the

crystals as follows:
add

c.c.

and

water
on

hours.

two

c.c.

Attach

pumice.

for

100

filter at

to

Before
once.

filter,recrystallize

ethyl benzoate
to

of alcohol

some

and

of the
about

test

dried
3

c.c.

of

concentrated

to

boil, notice
Save

benzoate.

(2)
excess

odor

of

potassium

with

Decolorize

filter,and

add

crystallizesout

few

HCl

to

maintain

to

drops

ethyl

acid.
and

Add

color.

alcohol.

of

Cool,

filtrate; benzoic

the

the

manganate
per-

pink

an

until

imperceptible.

is

required

as

of

solution

permanganate

benzaldehyde

begins

benzaldehyde

of

c.c.

it

as

odor

of benzoic

sample

just

Heat;

peppermint-like

together

Heat

of

H2SO4.
the

359

ACIDS

AROMATIC

acid

+0

CeHsCHO

(3) Sublime

CgHsCOOH.

benzoic

acid

from

impure

benzoic

acid, (see p. 13).

BENZOIC

Benzoyl

ACID

chloride, the

CeHsCOCl,

acid:

+HC1.

acid

by the action

the

by

or

of benzoic

action

stable

more

being decomposed

by

group

than

zoic
ben-

on

in

alcohols

of

acetyl chloride,

that
to

form

The

presence

of

caustic

facilitates

this

reaction.

It

reacts

hydroxyl

groups

insoluble

in water

Experiment.

in

in dilute

To

10

glycerol

the

tube, and

esters

alkaU
thus

with
of

the
zoic
ben-

greatly
with

the

dextrose, the resulting ester being

and

of

not

It resembles

it reacts

acid.

Cork

of chlorine

of PCI5

in the cold.

water

acetyl chloride, however,

drops

acid,

C6H6COOH+PCl6=C6H5COCl+POCl3
It is

hydroxyl

chloride

be obtained

can

benzaldehyde,

on

DERIVATIVES

and

c.c.

shake

of

c.c.

until

alkali.

10%
of
a

NaOH

benzoyl

add

chloride.

curdy precipitate

360

ORGANIC

forms, cooling
of water,

The

the

shake

tribenzoate

tube

and

from

substitution

variety.

be

can

corresponding

substituted

substitution

one

radicle

phenyl
the

of

same

as

benzene.

benzoic

aminobenzoic

aminobenzoic
while

the

acids
nitrobenzoic
is

Novocaine

acids

in

CH3

each

ethane

being the second

and

similar
An

important

are

It

acid

is present

in

being

produced

glycin

and

urine

when

the
in

benzoic
benzoic

urine

benzoic

hippuric

the
acid.
acid

of

It also
is

is

of

an

local

what
some-

acid, from
acid.

This

is

0^200011.

herbivorous

kidney

of

HCl.

derivatives.

benzoylaminoacetic acid, CgHsCONH

It

"

for cocaine.

anaesthetics

of

is

acid,

hydrochloride

group.

also benzoic

standpoint,

benzoic

N(C2H6)2

substitute

compound

The

394).

by substitution

sulpho-

para-aminobenzoic

CH2"

alypin, local

nature,

biochemical

as

of

stronger.
of

"

the
p.

than

are

substituting

anaesthetic, introduced
Stovaine

(see

diethylamine

group,

being

methods

nitrobenzoic

CH2

from

up

of the

acids, the

weaker

acid, C6H4(NH2)COO"
It is built

hydrogens

products

derivative

direct

or

acids, and

are

the

substitution

examples

are

and

by

acid, the

for the

ous,
numer-

are

by oxidizing

of the

more

glyceryl

ortho, meta,

an

made

chlorbenzoic

acids

acid

toluenes,

benzoic

used

The

acids, the

or

in

are

be

may

c.c.

alcohol.

65%

products of benzoic

They

10

Crystallize the

of hot

c.c.

there

Add

frequently.

filter.

15

for of each
para

CHEMISTRY

by

animals,

synthesis

appears

administered,

from

in human
or

when

foods

yielding

may

be

it in

the
in

prepared

361

ACIDS

AROMATIC

organism

ingested.

are

laboratory

the

by

It

several

methods:
1.

glycocoll and

Heating

closed

acid

160"

to

in

tube.

glycin dissolved

Shaking

2.

solution

with

CeHsCO

CI

3.

+H|HNCH2C00H

Heating

zamide

is

alcohol, and

having

is

ether, and

also

see

when

decomposes

acid

274)

p.

(ben-

NH

CH2COOH

+HC1.

in cold

long rhombic

187.5"

urine

water,

crystals,

(corrected). It is

by boiling with

readily decomposed

+HC1.

chloracetic

forms
of

below):

exp.

CH2COOH

relatively insoluble

melting-point

acetamide,

to

CeHsCO

acid

NH

CH2COOH

+C1

CeHsCONHjH

"

with

benzamide

(see

hydroxide

CeHsCO

analogous

Hippuric

in sodium

chloride

benzoyl

and

benzoic

acids

or

containing

alkalies,
it undergoes

fermentation.

(1) Synthesize

Experiments.
Shake
solution

of 2.5

gm.

chloride

mixture

has

filter,wash

glycocoll in

chloride
30

c.c.

and
of

Cool

whenever

Filter,and

acidulate

the

HCl.
with

filter-paper, and
Save

of

benzoyl

disappeared.

gets hot.

filtrate with

of

c.c.

10%

(keeping the flask corked) until the odor

NaOH
the

together

add.

hippuric

sample.

Collect

the

hippuric

little water,

press

recrystallize from
Test

part of it

as

hot

follows.

the

alkaline

acid

dry

of

on

between
water.

362

ORGANIC

the

(2) (a) Test

ether

petroleum
a

little

solubility of

acid

sublimes, while

Corresponding

in

becomes

Three

acids.

of

in

acid

(6)

Heat

acid

; benzoic

reddish.

there

toluene

to

acid).

test-tube

residue

the

hippuric

benzoic

(compare

dry hippuric

toluic

CHEMISTRY

four

are

these

(o-,m-,

basic
mono-

p-)

have

/CH3
formula

the

corresponding

the

has

fourth

The

obtained
with

the

called

with

nitric

acid.

CeHsCHzCOOH,

and
It

phenyl-acetic acid.

is

treating benzyl chloride, C6H5CH2CI,

by

and

cyanide

potassium

nitrile (CeHsCHaCN)

of

homologue

C6H6CH2COOH

this

hydrolyzing

the

ing
result-

+2H2O

C6H5CH2CN
A

ing
by oxidiz-

made

are

xylenes

formula

be

properly

might

and

C6H4"

is

+NH3.

phenyl-propionic

or

hydro-

acid, C6H5CH2CH2COOH.

cinnamic

unsatiu'ated

an

C6H5CH

being

formula

is

acid

Cinnamic

CHCOOH.

its

compound,

It is used

therapeutically.
acid

Mandelic

is

hydroxy

acid, its

formula

being

CeHsCHOHCOOH.

yields

Mesitylene

only

acid,

one

mesitylenic,

yCHs

CeHa^CHa

This

is of

importance

because

it

\COOH
converted

be

can

with

lime

into

(cf.benzene,

CgH^^^CHs+CaO
\COOH

by

metaxylene
p.

319)

C6Hy

distillation

'

+CaC03.

^CHs (m)

364

ORGANIC

(3) By

CHEMISTRY

fusing orthotoluene-sulphonic acid,

ortho-

cresol,

orthosulphobenzoic

or

In

potash.
of the

the

side

methyl

of the

of the

case

sulphonic

chain

group

acid

first two

with

bodies

occurs.

The

by hydroxy

1 has

caustic
oxidation

replacement
already been

explained (cf.p. 337).

(4) By converting orthoaminobenzoic

diazonium

salt and

boiUng

this

acid into the

with

(see

water

p.

384).
acid

SalicyUc
159"

at

(corrected).
but

water,

crystalUzes in

solutions
chloride.

It
of

is

in

so

readily

soluble

in

There

are

acids, which

The

also

salt,

value

in

the

prepared from

the

acids.

corresponding
do

They

not

ferric chloride.
and

meta

action.

para

have
The

position increases
so

employed

hydroxybenzoic

para

sulphonic-benzoic

salicylicacid, and
ortho

ties,
proper-

sodium

Its

medicinal

and

meta

be

can

or

with

react

great

ferric

fat-solvents.

it is therefore
etc.

hot

of rheumatism.

treatment

amino-

has
,

with

antiseptic

possess

odor,

no

in

Its aqueous

color

preserving wines, foods,

/COONa
C6H4\

cold.

violet

salicyUc acid

melts

and

soluble

readily

intense

an

and, having
for

is

only sparingly
give

Solutions

It

needles

that

acids
a

weaker

are

somewhat

different

introduction
the

sahcylic acid

acid

of
power

ological
physiin

OH
of the

stronger than

is much

than

acids

the

cule,
molezoic
ben-

acid.

Salicylicacid
many

of

which

forms
are

various

salts, the

important.

Methyl

salicylates,
salicylate,

AROMATIC

365

ACIDS

/OH
C6H4"f

is the

constituent

chief

of

oil of

It

wintergreen.

alcohol

methyl
acid.

be made

can

very

with

syntheticallyby

sulphuric acid

and

salicylic

salicylicacid

of

interestingcompound

ing
heat-

/OH
is

salicylate,C6H4"^

phenyl

It is produced
220"

(see

salol.

'

or

by heating salicylicacid

alone

to 200"-

3).

exp.

OH

.OH

2CcH4"(

COOH

C6H4"
^COOCeHs

or

by heating phenol and

of

phosphorus

salicylicacid

+CO2+H2O;

in the

presence

oxychloride:

/OH

3C6H4"

+POCI3

+3CCH5OH

^COOH
/OH
+H:"P04+3HC1.

=3CcH4":

^COOCcHs
Salol

is
in

in

odor
and

water

and

remain

phenol.

melting

unaffected

readily saponify
and

crystallinepowder,

white

and

when

the

of the

alkali will act

it has

been

It

dilute

acids.

and
it

will

till it reaches

the

antiseptics.

for intestinal

Alkalis

yield salicylate

salicylate liberated
as

matic
aro-

is insoluble

43".

internally

undecomposed

used

by

it, however,

Taken

phenol

at

somewhat

On

therefore

intestine,
by action

this account

antisepsis.

366

ORGANIC

Experiments.

Salicylic add,

of oil of

c.c.

20%

wintergreen

NaOH,

has

using

crystals

small

of

quantity

acid

in

into

alcohol, and

half

beaker

full

the

oil

collect
with

the

saUcylic

filter the

cold

of

of

HCl,
them

wash

c.c.

100

with

Dissolve

water.

hot

Uttle

"

filter,and

with

condenser, until

Cool, acidulate

on

(1) Saponify

by boiling

reflux

disappeared.

the

CHEMISTRY

solution

water.

Collect

chloride

solution

the

crystals.
salicyUc acid

some

produced.
ferric
and

the

odor

one-third

of

eight inches

into

c.c.

There
among

long

of

the

cold

iodomethyl

Try

phenol
salicylic

dry

test-tube

dry

test-tube

fit tKe

test-tube

Fill

on

several

it.

through
the

cork,
in

water

it

glass tubing

heat

it with
melts

soon

Decant

derivatives
as

salicylate, salophen

for

five

the

hot

Collect
water

some

and

sinks

water, and

off the

heating

remedies,

pour

beaker.

heat

Now

salicylic acid

material, and

newer

of

little

piece of small

removing

H2SO4;

the

in

heat

melted

drops.

are

and

passing

test-tube, when

dark-colored

salicylicacid, and

some

insoluble

(6) Mix

is

color

test.

solutions

follows:

as

having

and,

minutes,
the

salol

boil

gradually,

phenol

to

phenol is noticed.

full of
cork

liquid

alcoholic

soda-lime

some

violet-blue

similar

the

with

(3) Prepare
with

solution;

salicylic acid.

with

until

ferric

Compare

chloride
of

acid

in

Add

(a)

(2) Tests,

reddish

of

color

add
velops.
de-

salicylic acid

sanoform
or

as

or

di-

acetyl-para-

AROMATIC

of salicylicacid
More

anaesthetics

on

anaesthesin

OH

used

are

ester

of

methyl

of

ester

in

local

as

orthoforms,

aminohydroxyA

new

ortho-

(4)

which

the

of

positions

reversed.

been

proposed

place of orthoform;

of para-amino

act

the

surfaces,

prepared

has

in the

drugs wl^ch

/NH2 (1)
CeHs^OH
(2)
^COOCHs

NH2

AnflBsthesin

the

nirvanin.

been

and

are

is the

acid,
has

antipyrin.

raw

and

Orthoform

form

with

important

benzoic

salipyrin, a combination

salicylate,and

min6phenyl

367

ACIDS

benzoic

acid.

as

remedy

it is the

ethyl

is the

Nirvanin

to

be

ester

methyl

diethylglycocoll-aminosalicylicacid,
(1)

/NH.OCCH2N(C2H5)2

CeHs^OH

(3)

\COOCH3

(4)

/OOCCH3
Aspirin

is

acetyl-salicjdicacid, C!6H4"r

Novaspirin is

citric acid

derivative,

.COOH

C6H4\

^00CCH2v

/COOH

'

C6H4"
X
\00CCH2^
Both

for sodium

of

the

aspirins

salicylate.

are

yO
"C"

CH2

^OC-0

invaluable

substitutes

368

ORGANIC

is the

Betol

CHEMISTRY

/3-naphthol ester

of

salicylicacid,

'

C6H4(OH)COO.CioH7.

Dihydroxybemoic

B.

(3)
(4)

\0H

acid,

Protocatechuic

(1)

yCOOH

CeHa^OH

acid.

/COOH
Its

monomethyl

is vanillic

acid,

ether,

CeHs^OCHa,

which

is derived

employed

as

phloroglucin,
(see

p.

as

by

oxidation.

in the vanilla-bean, is extensively

flavoring agent.

It

is used,

with

indicator

free

mineral

acid

an

for

Synthetically it

402).

vanillin,the

yCHO
CeHa^OCHs,

corresponding aldehyde,

Vanillin,contained

from

also

can

be

prepared

/OCH3
with

by treating guaiacol, C!6H4\.

and

soda.

caustic

C.

acid

Trihydroxyhenzoic

is the

f COOH
OH

I OH
in

is contained
obtained

acid,

or

certain

(tannin), obtained
molecules

of

it is therefore

Tannic

with

dilute

from

gallicacid
a

is most

oak

by fermenting

condensation

acid will be

seen

gallnuts.

nutgall,

minus

one

com-

(1)

plants, but
tannin

boiling

by

important

(3)
(4) (+H2O).
(5)

OH

gallic acid, C6H2

pound

chloroform

This

readily
mineral

Tannic

consists

molecule

of

acid
two

of water;

product.
to bear

relation

to

gallic

acid

similar

that

to

monosaccharides

disaccharides

which

bear

to

+H2O

C14H10O9
(Tannic

The

369

ACIDS

AROMATIC

(Gallic acid)

acid)

following structural
for tannic

=207x1606.

formulae

have

been

posed
pro-

acid:

HO

OH

HO

OH
H

OH

and
H

OH

/\
COOH

HO
2

HO

"

Its constitution
That

prepared

is

by

\
oc

o"

is still under

gallic acid has

it above

to

\Z.

\0H

HOr

discussion.

the

structural

by

the

proved

fact

formula
that

it

given
can

acid

fusing bromprotocatechuic

be
with

KOH:

fCOOH

1 COOH
OH

OH

CfiH;

OH
!Br

Gallic
soluble

C2H2

"

OH

+KBr.

OH

+K|OH

acid

is almost

insoluble

in hot

water,

alcohol, and

in cold

ether;

water,
and

but
with

370

ORGANIC

CHEMISTRY
.

ferric

chloride

and

then

black

ink

acid

solution

it

ferrous
been

also

dioxide

Tannic
the

added.

of

acid

solution

being colloidal.

commercial

in

use

insoluble

and

tough

etc., in skin.
its

tanning,

astringent properties,
acid

of tannic
for

similar

are

has

in

as

been

have

to

it forms

the

protein,
of

account

on

rivative
de-

Many

prepared

stitutes
sub-

as

of

When

these

identical

are

Experiments.
tannic

acid
tannic

not

(1)
with
acid

classed

by

upon

yield gallic acid, while

The

Test

tannin

with

of

tannic

solutions

origin

having

are

acted

that

of coffee

acid, but
These

structure.

tannins.

vegetable

of

tannic

acid.

the

is

extensive

medicine.

substances

properties

some

(2) Add

with

tion
reac-

solution

process

employed,
in

same

very

in which

yield protocatechuic

and

gallic,

tannalbin, tannacol, tannigen,

as

many

chemical

KOH

than

acid

Tannic
It

dermatol

etc.

tannoform,
There

it,such

acid

bismuth.

gives the

It

compounds

is also

It

and

Airol

on

precipitate.

soluble

more

slightly dextrorotatory.

indigo
dries

this

gallic acid with

chloride.

slightly

yields pyrogallic

349).

p.

is much

ferric

with

(see

blue-

which

to

black

heavy

to

When

distilled,gallic acid
carbon

solution.

sulphate

oxidizes, giving

precipitate

gallicacid

by adding

combinations

are

give first

dark-green

of

has

When
and

form
is made

carmine
paper

its solutions

of

ferent
difgether
to-

molten
others
tea

and

acid.

gallic acid

ferric chloride.
solution

to

gelatin is precipitated.

some

tion;
gelatin solu-

372

ChEMISTRY

ORGANIC

which

latter, when
of

presence

3),

exp.

H2SO4,

as

red

being

of

body

The

and

meta-

It is also used

paraphthalic
iodine

phthalic anhydride
acid

an

as

acid

tion
solu-

cathartic.

acids

tensively
ex-

analysis,

in

now

(see

do

not

of

derivatives

form

nolphtha
phe-

antinosine,

medicines.

as

When

volumetric

colorless

the

used

structure

nosopheUj evdoxine, and

as

used

in

and

Certain

anhydrides.

are

complicated

alkaUne

(see p. 399).

in

phenol

yields phenolphthalein

indicator

an

in

with

heated

is acted

upon

by

phthaUc

acid

monia,
am-

imide, phthalimide,
C=0

C6H4^NH,
is formed.

(1) Heat

Experiments.
sublimation
is

O
some

(see

13);

the

phthalic anhydride

add

apparatus

p.

in

sublimate

phthalic anhydride.
To

(2)

some

of

quantity

then

100

of water

The

c.c.

fluorescence

/C0\

until

warm

resulting
transmitted

and

resorcinol

H2SO4,

to

and

deep

render

solution

of

light, but
to reflected

concentrated

of

c.c.

equal

an

red.

with

Dilute
with

alkaUne

NaOH.

fluorescein is pinkish

shows

marked

greenish

light:
yOH

yCO\

C6H4"^^^^0-f2C6H4"(^jj=C6H4"^
/^+2H20
C
/\
HO'H'iCG

CeHa'OH
o

(Fluorescein)

(3) Mix
and

AROMATIC

ACIDS

equal quantities

of

phenol,
This

water.

little C.P.

colored.

strongly
red

add

when

solution

phthalic anhydride
and

H2SO4,

into

Pour

373

becomes

phenolphthalein

of

of

large quantity

faintly alkaline

it is made

until

warm

/COx

+C6H4^^^^

2C6H5OH

"

(C6H40H)2+H20.

,"

(Phenolphthalein)

10

To

eosin.

(4) Prepare

of alcohol, then

c.c.

add,

has

bromine

enough

bromfluoresceln, the latter

After
wash

the
the

of the

crystalswith

forming

each

added

add
2

c.c.

addition.
form

to

di-

into solution, then

goes

as

it

crystallizes out.

an

hour, filter and

for

solution

solution

time,

little cold alcohol.

NaOH

add

is an

at

after

been

stood

has

mixture

eosin

Eosin

drop

is formed

tetrabromfluorescein

of fluorescein

gms.

shaking the mixture

of bromine,
When

2.5

; the

To

eosin

now

of characteristic

acid dye, being the potassium

red
or

little
solves,
discolor.

sodium

salt of tetrabromfluorescein,
Br

OH

Br

OH

c6H4"r

There

is

C6(COOH)6,
in

combination

hexabdsic

which
with

acid,

is present

aluminium.

viz.,

in the mineral

mellitic,
mellite

CHAPTER

AROMATIC

little

The

paraffins.
have

we

bodies,

aromatic

On
in

this

into

shaking

of pure

oily

an

absorbs

and

the

Its

+HNO3
is

shaking,

Mononitrobenzene

known

as

essence

210",

1.2033

first

cold

acids,

with

mixture

mononitrobenzene,

The

acid

sulphuric

C6H5NO2

+H2O

5", and

melting-point

its

at
--5-.

Experiment.
while

the

forms

produced:

boiling-point

specific gravity

the

obtained.

is

water

CeHe

in

sulphuric

liquid,

tives.
deriva-

COMPOUNDS

benzene

nitric

and

syntheses.

NITRO

By

prime

produced

nitrogenous

nitration

account

organic

many

other

the

of

of

are

readily

are

of

paraffins

those

hand,

other

they

converted

easily

step

the

on

importance

gen
nitro-

those

the

of

compounds

little

of

because

importance,
are

be

to

seen

and

bodies

aromatic

nitro

the

between

similarity

the

of

compounds
the

DERIVATIVES

NITROGEN

is very

There

XXVIII

70

To

80

c.c.

of

has
of mirbane.

H2SO4

c.c.

colorless

the

odor
It

374

is

in

HNO3.
of

bitter

poisonous.

flask
Cool

almonds

add,
thorand

is

AROMATIC

keeping
and

(a little

Add

oughly.

the

of

60", shaking
of

c.c.

Warm

gently with

when

the

Distill

air-condenser, and
odor

of the

the

If, on

proceed
nitric

almost

three

of
5

c.c.

of

benzene

subsides, boil for

into 250

c.c.

an

Note

alloWed

be

reaction

with

and

at

to

fuming
line
crystal-

(corrected)

90"

+H2O.
C6H4"(^^'

varieties

25

HNO3.

fuming

attach

dinitrobenzene,

of

meta

Prepare

beaker

is

+HNO3

exclusively the

in

flask

297".

Experiment.
Mix

the

hand,

product

C6H5NO2

Although

in

boiling-point.

(needles) melting

at

layer).

bottom

100"

above

boiling temperature
the

boiling

oil with

fractionating flask;

the

120

distillate.

substance
and

observe

other

at

acid

in

rises

temperature

with

the

chloride

dry calcium

water-bath.

the

kept

funnel, draw

wash

becomes

the
air-

bath

Cool, dilute

layer of acid, and

(the nitrobenzene

in

separating

for

vertical

hour

30"

below

minutes

30

an

of benzene,

c.c.

Attach

for

into

pour

bottom

water

on

heat

20

mixture

Take

occasionally.

water,

off the

the

of the

benzene.

the

tube;

time)

temperature

adding

condenser
at

at

shaking frequently.

work

375

DERIVATIVES

NITROGEN

form

that

C.P.

of cold

while
water.

is

H2SO4

Immediately
from

possible, it

are

pipette.
and

then

add
After
pour

Filter off the

is

produced.

dinitrobenzene
of

c.c.

this

(meta).
and
very

the
the

25

c.c.

slowly
action
mixture

precipitate,

376

ORGANIC

between

press

Make

there

easily
^

nitro

the

xylenes
In

manner.

attached

are

nitro

can

of the

sample

and

same

crystallize from

melting-point determination

Save

Toluene
the

and
filter-paper,
a

crystals.

CHEMISTRY

compounds

are

dried

nitric acid

alkyl

more

benzene

nucleus,

introduced

groups

the

into

in

more

it.

The

stable.

very

has

Trinitrotoluene

w^ith

react

be

groups

with

crystals.

fact, the

the

to

hol.
alco-

recently

into

come

use

as

an

explosive.

The

most

is that

AMINO

COMPOUNDS

important

reaction

with

aniline

compounds

whereby

hydrogen,

nascent

converted

of nitro

they

into

amino

compounds,

(phenylamine)

is the

representative

C6H5NO2

+6H

C6H5NH2

of

come
be-

which

+2H2O.

(Aniline)

aniline

Commercially,
nitrobenzene
acid

in

iron

an

apparatus,
and

with

iton

and, when

16"

at

colored

on

standing.

of water,

and

20

parts

of

in

alcohol.

aniline

described
blue

coloring

with

gives
in

matter

its

It is soluble

at

of water
25".

several
the
is

It

liquid

specific gravity
it becomes

in about
is soluble

30

parts

in about

readily soluble

important

by

color

tions,
reac-

below.

experiments

produced

lime

adding

pure

is

stirring

colorless

perfectly

not

part

one

It

is

It

hydrochloric

is over,

action

(corrected);
If

is 1.024.

the

mixing

by

filings and

aniline.

183.7"

at

produced

cylinder provided

distilling the

boiling

is

the

action

A
of

AROMATIC

NITROGEN

potassium

dichromate

this is the

same

stuff that
considered

CeHs.
combines

acids

C6H5NH2.HCI;
The

In

towards

electrical current

(see

p.

65).

in

respect

from

diminishes

but

group,

properties of NH2.
260), it

converts

compounds
Aniline

It

anil

name,

can

be

"

into

HCl

with

stronger

nitrous

liberation
amines

(CeHs)

amino

Whereas

+KOH

(NH2)

the
acid

of

basic
poses
decom-

nitrogen

(p.

into

diazonium

from

the

acid

in its salts

alkali

C6H5NH2

+KC1

+H2O.

by distilling
indigo (hence its

Spanish

for indigo).

substance

tin and

large flask, add

It is

an

in organic synthesis.

(1) Preparation of

of granulated
a

the

increase

caustic

being the

Experiments.
gm.

which
are

residues

liber-ated

extremely important

30

begome

not

Phenyl

260).

p.

aromatic

also be obtained

can

an

(p, 384).

with
by distilling

C6H5NH2

which

of

with

fatty amines

it does

properties of

fatty

is not

is,therefore, quite different

(cf.

basic

the

aniline

scarcely conducts

words,

some

ammonia

than

even

aniline

as

aliphatic amines,

bases,

form

water

It

e.g.,

C6H5NH2.H2SO4.

and

; in other

ionized
this

displaced by

is technically known

litmus

be

may

258), it directly

solution, however,

watery

alkaline

p.

C6H5NH2.HNO3;

hydrochloride

salt.

is

dye-

(aniline) salts,

form

to

AniUne

one

(see

(see 26);

first artificial

(in 1856).

bodies

all such

with

the

in which

NH3

acid

sulphuric
as

produced

as

Like

and

substance

was

377

DERIVATIVES

15

c.c.

aniline.

Put

of nitrobenzene

gradually (in portions

of

378

ORGANIC

CHEMISTRY

"

each)

c.c.

whenever

the

all the
for

of C.P.

HCl,

action

becomes

very

been

has

acid

with

dilute

50

ether

to

if the

NaCl

Add

for each

100

c.c.

portions of ether.

with

solid

potassium

(2)

few

water

changes

solution

it

to

blue.

the
add

with
Add

the
until
25

separating
the

flask

ether

the
gm.

funnel

extract

the

empty

ing-powder;

purple

Derivatives

of

solution

ammonia

of

appears,

(c) To

aniline

in

dichromate
aniline

some

filtered solution

color

solution

adding

then

c.c.

diluting with

potassium

in 0.5

aniline

of

Aniline.

of

KCIO3

appear;

drops

color

blue

to

(6) To

few

air-condenser.

an

drops

red;

(in water) add

solution

shake

Next

little

color

blue-violet

causes

H2SO4

Dry

aniline, using

adding

restores

ture,
tempera-

room

distillate

hydroxide.

(a) Dissolve

Tests,

H2SO4;

Now

fractionating flask, distill off the ether,

distill the

then

water-bath

steam,

the

in

; shake

three

liquid into

to

with
to

with

When

nitrobenzene.

Distill

clear.

comes

on

strongly alkaline; cool

boils.

mixture

distillate

cool

unchanged

until

flask

the

vigorous.

separating funnel, and

remove

NaOH

cool

air-condenser.

vertical

of water,

c.c.

into

pour

and

heat

added,

hour, using

one

50%

c.c.

100

of bleach-

develops.
The

include

homologues

/CH3
three

toluidines,

of

C6H4\

which

the

ortho

\NH2
and

para

varieties

are

important,

and

six

xylidines,

^(0113)2
C6H3C
due

to

this
,

differences

large number
in

the

relative

of

isomers

being

positions of the

380

ORGANIC

Thus

CHEMISTRY

iodide

methyl

produces

methyl

and

aniline

aniline:

dimethyl
4

CgHsNhIh+ICHs
I

Some

aniline

methyl

chloride

reacts

the

and

hydrochloride
being

first

is oxidized

aniline

Dimethyl

in the

cupric chloride
sodium

Methyl

carrier.

amines

the reaction.

is

with

by

prepared

methyl

formed,

portant
im-

most

alcohol,

which

then

above.

as

acid, and

by

commercially

mixed

these

heating

is also formed

is

aniline

of

of

base

quaternary

Dimethyl

=C6H5NHCH3HI

methyl

to

of

presence

chloride; the

copper

violet 2B

the

has

violet, by the action

potassium
salt

chlorate,acetic

acting

as

an

oxygen

following formula:

/C6H4N(CH3)2

C%";6H4N(CH,,)2
^C6H4=N(CH3)..

\ci
This

is

triphenylmethane dye;

is indicated

violet

Methyl
are

In
groups

is

relationship to fuchsin

hexamethylpararosaniline.

name

Both

pentamethylpararosaninile.

in commercial

present

Methyl

chemical

the

by

its

methyl

of these

violet.

violet is also called pyoktanin.

similar
may

replacement

manner

occur,

di-

and

with

phenyl

triphenylamine

being

produced.
CeHsNHCeHs,

Diphenylamine,

heating aniline
CeHsNH

with

H+HCINH2

aniline

is

obtained

hydrochloride

CeHs

to 200"

"w""i'"""'*"

C0H5NHC6H5

+NH4CI,

by
:

Dissolved

in

formation

of

sulphuric acid, it is

concentrated
detects

which

reagent

acid

nitric

of

traces

blue

deep

381

DERIVATIVES

NITROGEN

AROMATIC

color.

by

changed

is

It

to

tetra-phenylhydrazine.
With

acid

chlorides, aniline

analogous with

are

acid

the

CHaCOja+HiHNCoHs

anilideSy which

forms

(see p. 273)

amides

+HC1.

CHaCOHNCoHs

(Acctanilide)

One

these,

of

interest

therapeutic

great

very

antipyretic properties.
antifebrine, orangine

as

prepared

(antikamnia,

medicines

These

powders, etc.).

Acetanilide

circulatory depressant.

by heating aniline

with

in

drug

dies
reme-

entirely harmless, since acetanilide

not

are

active

the

its

of

account

on

is

It

headache

proprietary

many

is of

(phenylacetamide),

acetanilide

acts

is

easily
acid

glacial acetic

(see exp.):

CgHsNhIh +HdiOCCH3

CeHs

"

NH

"

+H2O.

OCCH3

(Acetanilide)

Experiment.

glgicialacetic

Mix

acid

in

glass tube

as

the

of reaction

water

acetic
of

c.c.

acid);

boil

On

and
It

for

at

two

hot

is very

114.2"

fit with

but

escape,

hours.

water.

water

Dilute

of

some

the

with

100

hot

crystallizes

out.

Save

(corrected).

long

once,

in

and

condenses

slightly soluble
hot

aniline

(this allows

filter at

and

crystallizes from
melts

flask;

condenser
to

of

cooling, acetanilide

Recrystallize from
Acetanilide

each

c.c.

small

reflux

boiling water

funnel.

10

using

sample.
in cold

colorless

Two

other

water

plates.
anti-

382

ORGANIC

pyretic drugs

of the

atom

to acetanilide.

closely related

are

of these, exalgin

one

CHEMISTRY

(methyl acetanilide)

amido

is

group

CeHsNCHaCOCHa.

In the

anilide),the acetyl

gen
hydro-

replaced by methyl,

other,

radicle

the

In

is

zoyl
(ben-

benzaniUde

replaced by

ben.

zoyl, CeHsNHOCCeHs.
and

Phenol

phenols,

amino

which

interest.

The

variety

para

ethyl ether

Its

in

is of

is known

amino-

the

prepared by reducing

are

nitrophenols.

exist

groups

the

mono-

therapeutic
paraphenet-

as

/OC2H5
idin,

and

C6H4\

glacial acetic

if this

with

treated

is

^^^^

\NH2

acid, acetaminophenetole

is formed,

/OC2H5
which

C6H4V
phenacetin
safest

"

(or acetphenetidin)

antipyretic.

melting-point
A
used
and

number
in

as

OCCH3

Phenacetin

and

is

is

substance, sparingly soluble

,

in medicine

is known

^^^^^

^^^^

\NH

in

perhaps

white

the

line
crystal-

water, and

with

of 135".
of

other

derivatives

phenetidin

are

medicine, particularlyholocain, lactophenin,

phenocoU.

is

Holocain

/OC2H5
CeHi

\Nff

^C

"

CII3.

Lactophenin is lactylphenetidin,
/OC2H5
C"H
^"^

\NH

"

OC

"

CHOH

"

CH3*

AROMATIC

(glycocoU phen-

aminoacetphenetidin

is

Phenocoll

383

DERIVATIVES

NITROGEN

etidin)
.

/OC2H5
CeH
6X14'

amino

and

Acid

(cf. reduction

obtained
p.

of

of benzoic

acid

nitrobenzene

to

variety of these

ortho

The

376).

nitro-

hydrochloric acid (nascent

tin and

derivatives

amino

hydrogen)

the

reducing

By

groups.

with

acids

benzoic

\NHOCCH2NH2'

may

be

aniUne,

is known

as

/COOH
acid^ C6H4\'

anthranilic

as

in

product

intermediate

an

by boiling indigo with

aniline
One

of the
is

compounds

amine

an

the

structural

aromatic

nitrogenous

derivative

of

alkali.

of pyrocatechol.

(adrenalin, suprarenin) has

Epinephrin

produced

preparation

caustic

important

most

is

It
.

the

ing
follow-

the

extract

formula:

Y
CHOH

I
CH2"

Epinephrin
from
is

the

is the

active

NHCHa

principle

suprarenal capsule,

injected into

the

circulation

important

effects

is rise

blood-pressure.

of

and

are

of

when
an

observed,
It

in

is

its solution

animal, several
chief

of

which

optically active,

38^4

CHEMISTRY

ORGANIC

{a)

is -50.4

51.4".

to

d. L

be

can

I.suprarenin is secured.
with
is

natural

now

the

reserve

to

synthetically
of
physiological action
compared with that of
for

suprarenin

The

suprareninis

Z. suprarenin

is advisable

It

product.

substance.

produced
racemic

term

to be identical

is found

Synthetic

epinephrin.

taric
tar-

which

obtained, from

This

conunercial

been

has

treating this with

prepared synthetically. By
acid, crystals

Suprarenin

weak

the

l. suprarenin.

DIAZO

acid

nitrous

hydroxyl

It

at low

of

are

converted

be

prepared
aniline
The
the

by

salt with

nitrous
salts

diazonium

linking

"

amino

hand, nitrous

different

compounds,

action.
called

so

The

azote

diazonium

in

organic

readiness

with

which

bodies.

other

ice-cold

an

They

solution

of

are
an

acid.
believed

are

to

contain

"

+HNO2

thesis
syn-

they

C6H5NH2HNO3

group;

importance

into

treating

other

together.

of the

account

on

with
and

nitrogen (nitrogen

two

great

very

of the

quite

diazo

linked

atoms

the

on

has

into

them

(French))

place

amines,

they contain

because

can

the

temperatures

converts

salts

takes

group

treated

are

260), nitrogen is evolved

p.

aromatic

the

acid

(see

COMPOUNDS

derivatives

fatty amino

When

with

DIAZONIUM

AND

C6H5N2NO3

(Benzene

diazonium

+2H20,
nitrate)

AROMATIC

If

diazonium

it

hammer,
follows

as

NITROGEN

Its

explodes.

it forms

water

this result

obtain

by

treating

salt

aniUne

with

nitrite,and

N2

with

reactions

important

a
are

equivalent

by

the

In

hydrogen.

salt is best

cold, acidified

alcohol

either

group

nitrogen:

diazonium

boiling (see

then

and

phenol

the

an

Boiling with

2.

struck

=C6H50H+N2+HC1*

C6H5N2CI+H2O

To

and

With

1.

dried

be

salt

385

DERIVATIVES

exp.

2,

p.

(
"

or

by

ether

phenyl ethyl

case

of the

C2H5)

"

an

338).

replacement

ethoxy

of

of sodium

quantity

causes

first

solution

pared
pre-

or

phenetole is formed:
C6H5N2CI+C2H5OH
second

in the

=C6H50C2H5+N2+HC1;
benzene

case

C6H5N2C1+C2H50H=
3.

acid

an

of the
the

solution
acid

causes

group

+CH3CHO

halogen acid

of

the

aldehyde:

or,

+N2
better

corresponding

replacement

of the

+HC1.

still,with

cuprous

N2

group

salt

by

halogen:
C6H5N2CI

4.

CoHe

vrith

Heating

and

Heating
by

C6H5N2CI

+HC1
with

cuprous

CeHsCl

+N2

+HC1.

cyanide replaces the

N2

cyanogen:

+Cu2(CN)2

CCH5CN

+Cu2"(+Nsw

386

ORGANIC

and

the

resulting nitrile
acid

benzoic

(see

Nascent

5.

CHEMISTRY

be

can

hydrolyzed

form

to

356).

p.

changes

diazonium

salt to

phenyl-

hydrazine (p. 388).

Other

sulphur

nitrate.

(1) Prepare

Put

50

flask; provide
and

Mix

10

in

water

ice-water, and

the

into

gas

aniline

for the

Test

dissolve

contains

which

5";

aniline

5 gm.

add

cooling.

Test

ethyl nitrite
ether.

c.c.

the

few

method

ethyl nitrite
for

HNO2

if necessary.

with
Let

the

complete
equal

an

cold

some

ether.

quickly

with

of

of

Bubble

solution

at

c.c.

concentrated

very

starch

is

iodide
a

as

HCl.

It

follows

absolute

slowly while

it stand

suction.

let it stand.

preparation
in 35

trate
ni-

once

and

keep

to

diazonium

hydrochloride
drops

tus.
appara-

benzene

in water

some

gas

until

0", then

Filter

in

of concentrated

c.c.

mixture
to

to

cold

of

standing

oxides.

nitrogen

Add

water.

is necessary

as

following reactions

troublesome

less

heat

cooled

(2) (a) Dissolve

with

c.c.

of the

50

nitrate

obtained.^

is

12

liquid a deUvery-tube

add

precipitate of

abundant

An

of

of alcohol

volume

erators,
gas-gen-

with

in the

AS2O3;

is secured.

solution

other

is connected

condenser-bottle

evolution

an

up

into

large test-tube

or

the funnel

the

to

nitrate

immerse

Through
HNO3

aniline

the

from

coming

trioxide
in

as

diazonium

cylinder standing in cold

graduate

arsenic

funnel-tube,

or

of

residues,

benzene

delivery-tube which

gm.

of

gm.

bottle

empty

hydrocarbon

also be effected.

etc., can

groups,

Experiments.

an

by

replacements

alcohol
Cool

to

shaking and

paper.

while, then

Add
add

more

cold

388

ORGANIC

It is used

color

as

in the

It
in water,

of

azo

into

the

partial reduction

been

It has
can

is soluble

is not

is present,
calculated

dye (see,

in

however,

that

number

the

theoreticallybe prepared

runs

millions.

d. Hydrazobenzene,

CeHsNH

; it is colorless.

derivative

diphenyl

is the

is

NHCeHs,

"

by reducing azobenzene
NH2"

zene.
nitroben-

of

crystals and

group

pink

Azobenzene

resulting solution

dyes that

azo

up

the

dyes.

many

by

orange-red

The

407).

(see p. 402)

latter

CgHs-N^^NCgHs.

forms
but

for free acid, giving

of the

presence

obtained

be

can

p.

indicator

an

Azobenzene,

c.

CHEMISTRY

tained
ob-

drazoben
Hy-

of hydrazine,

NH2.
is produced

Benzidine

action

of

from

latter

acids, the

strong

causing

Its formula

rearrangement.

by the

hydrazobenzene

molecular
intra-

is

NH2C6H4C6H4.NH2.

e.

Phenylhydrazine,

important
(see

zones

with

sugars

CeHsNH

derivative.

hydrazine
p.

352)

(see

235).

p.

of diazonium

with

salts

CeHsNsCl

+4H

It

aldehydes,

aniline
HCl.

To

add, while
Cool

of ice, then

in
add

the

forms
and

is obtained

It

most

hydraosazones

tion
reduc-

by

(see exp.) :
CeHsNH"

NH2

(Phenylhydrazine

Experiment.

is

NH2,

"

18

stirring, 100

freezing mixture
slowly from

HCl.

hydrochloride)

of

c.c.

"

freshly

c.c.

to

distilled

of concentrated

0", add

dropping

150

funnel

gm.

(have

NITROGEN

AROMATIC

of sodium

solution
until

testing

shows

the
the

For
5

in

tip dipping

the

of

60

hour.

dry

Add

plate, press
in

50

let it stand

the

thin

c.c.

one

fer
Trans-

phenylhydrazine

layer, and

set

away

out:

HCl

+HNO2

C6H5N2C1+4H=G6H5NHNH2HC1.

"

phenylhydrazine

Free

solution

and

ethereal

hydrazine
solidifies

poisonous.

are

itself for

as

Its

by
of

excess

After
the

ing
treat-

NaOH

dehydrating

ether;

phenyl-

liquid which

readily

cooling.
is

and

colorless

boils

at

It

becomes

salts,

It melts

sometimes

producing

dark

e.g.,

the

being neutralized

ordinary

at

19".

at

colored

going
under-

on

hydrochloride,

employed
osazone

oil

242", meanwhile

decomposition.

some

air.

an

ether.

behind

+2H2O.

extracted

extract, evaporate

Phenylhydrazine
temperature

be

with

shaking with

remains

on

C6H5N2CI

may

hydrochloride

the

acid

in

keep the temperature

and

out

2.

and

with

ice-cold

an

chloride

thoroughly

C6H5NH2

to

mixture

slowly

ice to

1.

the

paper

(blue color).

acid

Add

stannous

hydrochloride crystals
to

water),

through muslin, using suction.

porous

of

gm.

diazotizing the temperature

the
5".

below

Mix

Filter

to

of

c.c.

acid

the

of

drop

HCl.

0".

in 70

gm.

of free nitrous

During

of concentrated
at

(14

shaking,

starch-potassium-iodide

dilute

keep

must

solution

nitrite

with

of water.

c.c.

mixture), while

the

presence

test

389

DERIVATIVES

in

place

of

It is

exposure
are

solid

the

base

crystals,the hydrochloric

by sodium

acetate.

390

relationship

The
and
the

CHEMISTRY

ORGANIC

will

aniline

be

formulae

following

C6^5"N

CoHs-N
(Asoben*

aene)

bodies

evident

from

nitrobenzene

to

an

examination

of

CeHsNH

||

CeHsNOa
(Nitroben-

these

of

CeHs-NH

|
CeHs'NH
(Hydrazo-

bensene)

|
NH2
(Phenylhydrasine)

CeHsNHa
(^^^^"""

CHAPTER

AND

SULPHUR

XXIX

DERIVATIVES

SULPHUR

With

acids.

Sulphonic
form

+H2SO4

CeHsCHa

+H2SO4

^^+H2O.

(Toluene-sulphonic

It

is of

importance

behave

aniline),
attached

derivative

alone,

or

The

or

to

the
is

any

of

acids,

the

chlorides,
1.

easily formed

acids

so

that

of

which

their
with

be

C6H6S03Na+PCl5

the

sulphonic

water

phosphorus

reduced

form
to

acid

benzene

is used.

very

acids

is

phenol)

when

in

are

in

and

stable,

are

e.g.,

pentachlorsulphonic

mercaptans:

2.

salts

sulphonic
may

in

than

an

(as

(as

soluble

are

When

group

derivatives,

Treated
salts

this

amino

an

nucleus,

its other

acid)

paraffins.

group

benzene

more

CeHsSOaNa.
ide

hydroxyl

sulphonic

strong

from

toluene),

(as in

group

in

that

note

differently

quite

alkyl

to

they

acid)

C6H4^

respect

+H2O

(Benzene-8ulphonic

and

zenes
ben-

C6H5SO3H

the

acid

sulphuric

acids, thus

sulphonic
CeHe

DERIVATIVES

ARSENIC

C6H5SO2CI

C6H5S02C1+6H=C6H5SH+HC1+2H20.
(Thiopnenol)
391

+POCI3

+NaCl.

392

ORGANIC

must

possess

is in

immediate

The

structural

an

that

us

OH

"

formula
be

the

atom

benzene

ring.
acid

benzene-sulphonic

^Nqq

ttq

the

that

with
of

acids

sulphonic

and

group

connection

therefore

must

show

reactions

These

CHEMISTRY

acid,

sulphuric

or

H0\

by

yS02,

in which

phenyl

(cf.

hydroxyl

one

p.

306).

with

acid

+KOH

little at

add,

and

cooling

into

300

cooling

of cold

of

the

pasty

dry, and

mass

the

cold

be

may

the

(2) Weigh
five

times

iron

dish, add

as

the

dry

few

NaCl

with

drying
powder

cubic

to

out, drop

by

solution.
On

ice-water.

benzene

sulphonate

hastened

by strongly

in

into

test-tube

main

the

and

Uquid.
and

suction

crystals with

KOH.

much

Transfer

mixture

mixture

of

is attached

benzene, shaking

saturated

little saturated

complete

of

gm.

H2SO4

fuming

air-condenser

crystallinemass

the

it with

the

of

gm.

sodium

crystals of

some

emptying

wash

run

Crystallization

form.

phonic
benzene-sul,

+K2SO3.

addition.

solution

salt

the

standing,

Filter

c.c.

20

each

after

CeHsOH
75

an

time,

funnel, and

dropping

Keep

To

flask to which

small

drop,

(1)

Experiments.
a

yields phenol,

C6H5SO3K

in

other

important

are

hydroxide

potassium

replaced

several

give

They

reactions, the following of which

1. Fused

is

group

salt solution.
in

an

at

oven

(of 1);
Put

the

centimeters

Press
110".

weigh
in

KOH
of

out
an

water,

SULPHUR

and

fused

shake

HCl,
of

solution

benzene

in

phenol

the

same

Distilled

formed

with

p.

the

vious
pre-

338).

=C6H5CN

are

'

CgHZ

+K2SO3

=C6hZ

+KCN
^

'+K2SO3.
^

\CN

\SO3K

hydrolysis these

cyanides

be

can

converted

into

CCH5CN+2H2O

=CgH5COOH+NH3.

The

toluene-sulphonic

The

meta

is present

By
acid,

variety is
in many

the

acids

The

rare.

be

may

ortho

action

This

of

sulphuric

is

white

substance, readily soluble

valuable

solutions
Phenol

precipitant
on

and

para.

group

dyestuffs (see p. 407).

acid

salicylic

on

(1)

/COOH
CcH4\

salicyl-sulphonic acid,

formed.

or

sulphonic acid

\OSO3H

ethereal

and

acids

in

as

Keep

cyanidey cyanides

potassium

CeHsSOaK+KCN

By

the

treat

acidulate

water,

way

(see

phenol experiments
2.

in

ether, and

with

stirring with

sulphonate.

Dissolve

hour.

an

393

DERIVATIVES

slowly, while

sodium

the

for

with

add

Then

melt.

spatula,

ARSENIC

AND

^^
/

tt

\"

(2)

crystalline deliquescent
in

water, the solution

for

standing become
stilphonic groups

certain
colored
exist

being

proteins.

Its

red.
in

phenol-sul-

/SO3H
phonic acid, C6H4"f
cially known

as

(0 or p), which

aseptol and

used

as

is

commer-

disinfectant.

394

sodium

The

and

by the action

acid.

The

imide

and

is

salt

(in which

and

medicine

sulphuric acid
then

amino

called

is

NH)

and

septic;
anti-

properties it is used

as

by

acid

paraminobenzenesulphonic

action

sulphate

converted

becomes

the

By

groups.

aniline, aniline

on

this

of

preservative.

and

Sulphonic

is

sodium

Its

is intensely sweet,

of these

account

zoic
ben-

on

acid,

replaces
It

acid

saccharin

benzosulphinide.

Na

saccharin.

acid

substance

important

called

also

on

and

tion
fermenta-

arrest

sulphuric

of

of orthosulphobenzoic

the

to

Metasulphobenzoic

sulpho groups.

produced

soluble

is used

and

sulphocarbolate

stomach.

in the
Acid

sodium

is

it

of

salt

(phenolsulphonate),

is

CHEMISTRY

ORGANIC

of

is formed,

heating

into

sulphanilic acid,

or

/NH2

C6H4"C

by dehydration:

__,

/NH2
C6H5NH2

"

H2SO4

C6H4"

+H2O.
^^

Sulphanilic acid
sparingly

cold

in

so

ethyl-sulphonic

there

diazo

exists
group.

of
the

acid,

see

p.

dyes, in

sulphonic
Two

of

in hot

water,

Its solution

water.

differing from

reaction, thus

manufacture

is soluble

"

that

of

272).

It is

these

group

dyes,

only

is acid

taurin

large number
acid

but

in

(amino-

used
of

in the

which

along with

viz., methyl

ORGANIC

396

(6

+6

gm.

HCl

c.c.

Filter

NaCl.

of
and

crystalUze

color

Save
is

OO

add

sample

gives

if its alcoholic

acids.

the

is very

test

indicator

color

with

solution

be

p.

being

Applied

of the

crystals.

tion
solu-

in
It

violet

color

this

latter

It is

in
a

acid;

dryness,

to

with

free

manner

used

is thus

as

an

dye

gastric juice.

(methylthionin chloride)

sulphur

406).

mineral

free

evaporated

delicate.

blue

containing
(see

acid,

Its

in analysis of the

Methylene

red

some

C6H4NHC6H5

resulting residue, gives

mineral

dilute

violet

gm.

diphenyl-aminoazobenzene-sul/N2"

the

Uttle

acid, C6H4C

phonic

or,

To

20

precipitate

orange

water.

orange

the mixture

add

and

methyl

hot

is obtained.

Tropaeolin

solution

off the

from

Render

H2O).

c.c.

NaOH

methyl

of

solution

+20

with

alkaline

CHEMISTRY

the

thiazine

is

chromophore

group

derivative, its formula

(CH3)2N

^X^/-N(CH3)2.
CI

ARSENIC

AROMATIC

An

arsenic-containing derivative

phenol has
a

remedy

for

{arseno-henzol

of ortho

recently synthesized.

been

syphilis.
''

or

606

DERIVATIVES

Its

trade

It is used

name,

")" gives httle

aminoas

salvarsan

idea

of

its

is

It

composition.

397

DERIVATIVES

ARSENIC

AND

SULPHUR

hydrochloride

the

of

dihydroxy-

diamino-diarseno-(di-)benzene,

As-

-As

C6H3^_NH2

an

arsenic

organic

Another
of

OH

I^CeHs^

is

compound

monosodium

is

arsenate

-NH2

replaced

which

in

atoxyl,

by

aniline,

"

/NH2(1)
C6H4

\AsO(OH)

If

the

obtained.

sodium

be
Arsacetin

substituted
is

(4)'

(ONa)

sodium

by

H,
acetyl

arsanilic
arsanilate.

acid

is

CHAPTER

DYES

QUINONES,

best

The

known

of

INDICATORS

AND

may

be

regarded

them

is

benzoquinone

These

Quinones.

XXX

diketones.

as

HC
which

has

the

CH

11

formula

structural

quinoney

or

11

and
,

HC

CH

\co/
may

be

prepared

by

of

benzene,

but

Thus

is

^dth

not

usually

acid,

acid

or

by

HC

II

jj

+0=

The

as

quinones

+H2a

CH

C=0

preparation

preparation

its
to

its

for

reactions

doubt

\/

COH

little

aniline

hydroquinol

II

HC

CH

of

oxidizing

CH

\/

exception

oxidized.

when

C=0

CH

HC

by

oxidizing

COH

HC

acid,

p-sulphaniUc

however,

prepared,

derivatives.

meta

or

tives
deriva-

para

etc., all yield quinone

chromic

These

various

ortho

p-phenolsulphonic

p-amino-phenol,
It

oxidizing

its structural
are

of

yellow
398

from

(with

aniline)

the
leave

formula.
color

and

possess

DYES

QUINONES,

odor.

pungent
Kke

In

ketones, but

have

AND

behave

particulars they

some

in

399

INDICATORS

others

differently. They

very

oxidizing properties and

in

important

are

dye

chemistry.
INDICATORS

At

this

it

stage

briefly the theory

These

must

will

of the

convenient

be

of indicators.

action

acid

weak

possess

and

be, therefore, undissociated

but

dissociated

when

that

from

the

Taking

three

far their

in how

feeble

very
a

state, and

free

When

occurs

when

Thus,

we

happens

is this:

phenolphthalein
therefore

is of

titrate

acid

an

In

the

the

of alkaU

in

the

is present;

acid

that
this

phenolphthalein, forming
so

solution.

that the anion

necessary
trace

the

last

to

what
the

solution
the

at

salt.

acid

is

acid
trace

neutralize

combines

salt, which

imparts

color.

ide,
hydrox-

the

added

gradually neutralized, until

of

red

into

of

becomes

excess

sodium

presence

is

in

when

indicator,

as

us

of

nature

has

with

alkali

as

let

it is colorless.

is undissociated, and

colorless;

color

explained.

it is converted

when

phenolphthalein

using

thus

its anion

dissociated, however,

Dissociation

be

litmus,

undissociated

when

sociated
dis-

indicators,

it is undissociated

that

acid, so

used
and

can

This

(1) Phenolphthalein.

the

In

compound.

orange,

actions

free state,

different

commonly

most

phenolphthalein, methyl
see

in

have

must

properties,

salts.

as

undissociated

of the

basic

or

when

present

anion

the

state

discuss

to

then

with

the

ates,
dissoci-

its red color to the

400

ORGANIC

The

acid

than

be titrated

to

has

all been

formed

will

become

base

will

phenols

be

other

the

the latter
it.

such

be

On

the

phthalein
phenol-

the

Thus,

acid

carbonic

as

that

phenolphthalein

as

indicator

an

titrating. Phenolphthalein

used

alkali
also

can

ing
for titrat-

(carbonates)

dioxide

standard

the

from

absent

and

phenolphthalein.

feeble

carbon

this account

salt

solution.

with

employed

the

to

than

stronger

can

be

must

tint

titrated

hand,

much

so

pink

with

the

ing,
which, partially dissociat-

salt

cannot

of

some

will combine

the

before

otherwise,

hydrolyzed (see p. 70),

form

impart

distinctly stronger

neutralized,

liberated

thus

and

is

for

"^

be

must

phenolphthalein,

former

On

CHEMISTRY

for

used

be

for

practically all organic acids.

strong
is

used

base

The

then

employed,

will

requiring

to

the

effect

of

must

not,

ammonium

present

with

are

salts, and

acid

end

ammonia

decomposing
ammonia

when

used
a

ideal

the

the

be

Phenolphthalein

overcome.

present in
is

of

the

before

therefore, be

should

or

solution.
indicator
be

for

employed

weak

along

strong base.

(2) Methyl
much

is

will

it

that

excess

the

with

(hydrolysis), and

water

ammonia

as

it forms

feeble

so

be

salts

and

be

indefinite, an

water

such

base

be

Phenolphthalein
acids

feeble

be

also

must

salt which

the

by the

decomposed

will

phenolphthalein
reaction

if

Thus,

one.

neutralization

for

This

Orange.

stronger

acid

dissociates

readily

dissociated

(as

free

weak

acid)

sodium

salt of

and

it

phenolphthalein,

than
in

is the

it is

solution.

When

red, when

dissociated

un-

DYES

QUI NONES,

(as

is

water

prevented
acid

stronger
but

dissociates

more

occiu's,

so

this

titrating acid

therefore, for

and

unsuitable;
used

it is suitable
since

for

the

for

of the

the

acid

acts

nitrites

the

methyl

on

of

for

the

bases

According

weaker

benzene

having

changed

long

so

with
of

must,

chemically,

therefore

be

theory the
and

orange

and

For

suitable
un-

weak

Very

titrated.
color
is due

production

structure

CO).

for

especially useful

cannot

methyl

quinoid
to

as

Nitrous

organic acids.

recent

and

sociable
dis-

form

orange).

methyl

rearrangement
tomer

carbonates,

bases, including anamonia,

phenolphthalein

and

hand,

present.

(as anihne)
to

other

be

(i.e.,uncombined

orange

is

it cannot

hydrolyze

is therefore

orange

titration

organic

be

not

indicator

titrated, which

than

stronger

must

Methyl

being

orange;

immediately

not

is available
is

that

be

course,

acid

base

do

acid
before

methyl

the

On

acid

weak

excess

reasons

same

bright

by

this

salts

it will

salts, which
any

large

practically all bases

all of them

with

that

of

organic acids.

weak

for

in

present
dissociation

the

prevent

can

be

must

tion
dissocia-

affected
so

to

paler,

much

becomes

not

(NaH2P04),

phosphate
as

is

"

partially

orange

becomes

solution

orange

just

added, still more

the

that

Methyl

sodium
such

alkali is

red

amount

methyl

solution

the

if a trace

yellow.

it

and

the

of

trace

therefore

are

sufficient

in

acid, then

of

presence

solutions

is added

this

neutralize

the

in

dissociation

Its

yellow.

by

such

"

if alkali

and

is

salt) its anion

401

INDICATORS

AND

change

molecular
intra-

to

of

of

(a CH

group

example,

the

tau-

of
red

402

ORGANIC

salt

of

CHEMISTRY

phenolphthalein

alkali) is said

have

to

(in the

dilute

of

presence

following quinoid formula:

the

CH

\COONa

CH

VC6H4^0H.
with

this

Compare

formula

the

of

non-ionizing

phenolphthalein (p. 373).

It is

quinoid

structure

quinoid

substance

in the

acid
as

methyl

presence

is red

in the

gastric

indicators

value

with

that

methyl

with

give
acids)

mineral

dilute

distinct

indicator
mineral

to

mineral

making

when
acid

in the

(3) Litmus.
and

acid

methyl

This

presence

stands

orange

color

in

of

reaction

p.

be

is

(as

with

very

405).

The

however,

used

as

estimation

the
of

organic acids.

between
its

(contrary

dimethyl-

(p. 348),
can

that

true

titration

used

(see exp.
and

dimeth-

textbooks)

quantitative

is

accurate

when

organic acid solutions

only

it

class

same

red, and

phloroglucin-vanillin reagent
reacts

the

chemistry

even

of mineral

experience

Congo

orange,

aminoazobenzene

phthalein
phenol-

(p. 410) and

an

our

clinical

in

to

While

give

not

detection

red

Congo

organic acids,

statements

to

The

acid.

of both

case

belong

(p. 387).
will

of free

the

contents

ylaminoazobenzene
these

for

e.g.,

orange,

tautomeric

orange.

used

indicators

has

orange

in the

methyl

and
The

methyl

that

supposed

lein
phenolphtha-

properties.

In

the

404

CHEMISTRY

ORGANIC

butyric acid

with

methyl

(6) with

orange;

phenol-

phthalein.
(3) Acid
red)

and

(a) With

salts,

(both being one-tenth

4

with

of NaH2P04

c.c.

with

of acid

phosphate

Na2HP04

molecular),

of

c.c.

then

the
and

orange

mix

and

Na2HP04,

(6) Test

methyl

to

and

gram

(amphoteric).

Utmus

(both blue

paper

of NaH2P04

solutions

test

litmus

test

acidity
methyl

to

red.

solution

suffer

degrees

ion

be made

by

the

often

may

depends

This

of

Determination

the

on

color

of colors

from

solutions

of

thus

yellow
low

colors

from
similar

red
color

acid

solutions
with

with

changes

solutions

gives

equivalent

(see

exp.

By

gradation

to

using

basis

the

the

necessary
one

ing
rang-

give
while

HCl

^^r^

-^rr:

Tropaeolin

500

solutions

of

and

adding
for

tested

gives with

the

solution

shown

by

indicator
to

is found.

the

is
one

standard
has

try several
The

the

red

to

yellow

been

known

estimations.

added

intermediate

solutions
added.

indicators

to

It

before

final determination

To

indicator

an

of the

ion

indicators,

proper

colorimetric

be

same

red

orange,

"

from

to

colors

somewhat

solutions

methyl

of colors

standard

is secured

solution

which

various

1).

concentrations
a

of

series

to

methyl

100

00

gives

added

when

different

of

presence

N
with

of indicators.

use

yellow, still more*acid

to

dififerent indicators

rosolic

acidity,

acidity give

greater

the

red

to

the

that

in

change

acidity;

of

fact

of

concentration

is

which
be

may

the

right

simply

DYES

QUINONES,

said

color

of

question

have

to

standard

AND

and

matching;

the

same

that

solution

405

INDICATORS

ion

concentration

nearly

most

is

solution

the

the

as

resembles

it in

color.

(1) Select

Experiments.

piractically the

in three
10

For

series 1

For

series

c.c.

tubes

acid

^,

In each

each.

HCl.

lactic acid.

^^,

^^

NNN
"

J?

For

series

and

use

j^,

tube

indicated.

solution

j^,

them

Arrange

water.

and

use

having

clean

g.^, ^, and ^

use

distilled

with

series of four

of the

put

and

diameter,

same

thoroughly, rinsing
them

test-tubes

12

jN,..

^^,

^^,

lactic

^^^

acid.
To

tube

each

tropseolin 00
2

use

(dissolved

drops

of

methyl

.02%
In

order

concentrations
with
5

c.c.

and

to

different

at

widely.

Explain

why

alcohol) ;

for

series

solution
series

of dimeth-

mixing

note

the

ion

the

differing

the

gram

end-points
titrate

the

of

tion
titra-

successively

molecular

rosolic

drops

use

series.

indicators,

solution,using methyl red,

phthalein.

.05%

in each

illustrate

one-tenth

of

After

obtained

obtained

portions of

for

drops

50%

in

orange.

of colors

gradation
(2)

add

alcoholic

.05%

ylaminoazobenzene
of

series

of

NaH2P04

acid, and

titrations

phenoldiffer

so

406

CHEMISTRY

ORGANIC

DYES

Several
All

bodies

such

properties
chromophore
Most

the

to

azo

and
since

cases

are

the

must,

given

groups

of

of

dyeing

so-called

molecule

order

chromophore

The

CO

/\

/^co
and

\/
CO
y\

c=c

CO

ture
struc-

them

the

following give

CO

in the

group

groups:

constituents,

than

more

CH=CH

enable

to

impart

to

C='0,

environment

therefore, be

chromophore

itself

chromophore

in

true

above.

of

ings.
Unk-

independent

an

groups

certain

is

N)

The

double

contain

sufficient

dependent

color; the

impart

(N

compound.

they require
of

their

owe

them

groups

group

being

chromophore,
a

in

presence

chromophore

to

to

mentioned.

group.

The

color

supposed

are

been

already

have

of these

in

to

these

simple
tions
illustra-

DYES

QUINONES,

The

in

presence

substance

dye, the
other

such

groups,

rule, be attached

has

sulphonic acid
dye soluble

few

dyes

semi-colloids

very

small

solution

in

colloidal

solution.

be
for

of

electrical

of
fibers

(see

dye taken

p.
up

color

of

The

render

to

of

indicates

the

with

animal
in

tissues,
the

by

charges

the

portion that

that

is in

acquire
furnish

fibers, because

many

there

after

cases

of
is

a
an

the

the

tion
neutraliza-

precipitated

are

solution

that

is in true

electro-positive colloidal

or

In

because

its fibers

water

aration
prep-

examination.

substance

that

crystalloids.

are

stains

as

attracted, and

95).
from

colloids,

electricity. Dyes

adsorbed

particlesare

or

less
color-

orated,
fully elab-

emulsoid

others

in

electro-positive ions
ions

the

dialyze slowly, probably

is immersed

are

auxo-

properties.

microscopical

proportion

negative charges
particles

These

in

introduced

are

used

equilibrium

cloth

If

pound
com-

The

color

penetrate

can

can

tissues

of

dyes

some

and, therefore,
The

acidic

or

is often

group

diffusible

The

basic

auxochromes;

dye-stuff, when

semi-colloids, and

are

as

(and acidic).

solution

In

called

certain

dye.

intensifying

The

have

it

must,

producing

of

or

chromogens.
will

as

are

groups

effect of

the

chromogens,
other

NH2,

salt-forming properties.

confer

chrome

and

available

auxiliary

assisting or

constitute

to

chromophore-containing

it

groups

chromogen;

OH

as

to

render

to

these

is merely

of these

one

generally, sufficient

is not,

alone

of

substance

407

INDICATORS

AND

on

amount

particular

the
of

tration
concen-

equilibrium

be-

408

ORGANIC

fibers

the

tween

of

sort

result

under

dyes

are

acids,

dissociation

(see

fairly strong

the

but

substance

is

the

some

combination

with

dyes

in

the

of

cloth

steamed

hydroxide
cases

after

the

dye

the
may

adsorption.

acid

not

take

used

are

in

ing
adsorb-

or

tannic
of

acetates

conmionly

are

the

with

salt

acetate

and

leave

metal.
enter

colloidal

dyes

dyes

the

as

resulting

basic

iron

decompose
of

do

with

soaked

being
to

fibers

precipitating

and

the

colloid.

acid

For

of

process,

For

of

hydrolyze

ion

fibers

is capable

salts

not

Mordants

dyeing

chromium,
the

cotton

cotton

used.

do

goes

positive.
electro-

being

The

Uke

free

set

sodium

they

ionize.

behaves

the

largely

colloidal
In

acids;

substance.

dye

employed,
then

of

which

aluminium,

and

bases

hydrolytic

base

mostly

are

they

step

coating

acid

trolytes
elec-

undergo

particles

satisfactorily.

color

the

fibers

when

organic

The

the

of many

case

preUminary
the

ions

by

instance,

weak

70).

p.

dyes

(electro-negative)

up

for

therefore,

organic

appreciably,

the

adsorbed

be

of

solution,

Acid

In

adsorption

electro-negative

may

salts

and,

colloidal

into

have

same

present.

are

strong

recognized

in

conditions,

is the

this

solution;

that

particles

special

Basic

the

is obtained

Dyes

colloidg.1

or

and

as

processes.

CHEMISTRY

into

chemical

XXXI

CHAPTER

CONDENSED

HAVING

COMPOUNDS

AROMATIC

RINGS

connected

It

the

in

white

forms
and

218.1"

and

following

having

of

the

melting

tar-like

in

benzene

two

rings

manner:

crystals

contained

is

contains

(CioHg)

Naphthalene

coal-gas,

distillate

from

at

80",

odor.

It

boiling

volatile

is

also

being

It

coal-tar.

at

stituent
con-

is

an

antiseptic.
(1)

Experiments.
sublimation

(2)

by

(see
The

p.

the
some

in

with

reaction

naphthalene

chloride

aluminium

dissolved

in

chloroform

332).
naphthols,

Alpha-naphthol
thol

naphthalene

some

apparatus.

Try

given

Heat

correspond

C10H7OH,

(melting-point

95")

122")

both

(melting-point

409

are

to

phenols.

and

beta-naph-

of

importance.

410

ORGANIC

of

Derivatives

introduced

in

it in

para

naphthalene

position 2, 3,

attached

have

naphthalene

position 1, 4,

have

groups

CHEMISTRY

7.

derivatives
the

to

8, while

or
or

group

/3 derivatives

Ortho,

have

and

meta

substituting

two

half

same

some

formula

of the

(as

positions 1, 2, 3, 4).

in

is

Epicarin

/3-naphthol-ortho-hydroxy-toluicacid,

/COOH
CeHss"

OH

CH2'OCioH7

benzoate,

^-Naphthol
of the

used
the

as

SLiid

of and

presence

in

fact

to

estimate

drinking

that

these

red

is

is used

other
an-

stances
sub-

This

are

to detect

of traces

amount

compound,

test

depends

azo-benzene-

acid, is produced.
diazonium

complex

the

water.

red

naphthylamine-sulphonic
Congo

All

CioH7-NH2

a-Naphthylamine

reagents.

the

on

/3-naphtholate.

beta-naphthylamineSf

nitrites,as

of

is

antiseptics.

are

Alpha-

OOCCeHs,

"

remedies.

newer

is bismuth

Orphol

C10H7

acid.

naphthylamine-sulphonic

derivative

Its formula

of

is

^^^^^|"CioH5N=N.C6H4.C6H4
color

Its

It forms

becomes
a

colloidal

Electrolytes
Santonin,
and

cause

in the

is

presence

solution, which
its molecules

C15H18O3,

is the inner

Its formula

blue

is

anhydride

probably.

a
or

to

of free

will not

dialyze.

aggregate.

naphthalene
lactone

acids.

derivative

of santonic

acid.

412

ORGANIC

One

of the

CHEMISTRY

is

of anthracene

derivatives

important

anthraquinone,
CH

CO

C14H8O2.

JCH

CH

CO

Dihydroxyanthraquinone

is the

important dye

very

alizarin, Ci4H602(0H)2:
CO

CH

CO

CH

This

formerly obtained

was

much

produced

now

Its

means.

of the
Aloin

may

COH

on

of

be

anthraquinone

(the position

by

synthetic

scale

is

derivative.
OH

Its formula

being uncertain)
OH

^/\^/\.

HC/

"v

HO-C
c

CH

x/
CO

^CH

y\

yC

one

organic chemistry.

C"

CO

CH

of the

It is

plant.

commercial

great achievements
is .an

cheaply

more

synthesis

from

CH3

/^^^

\/
C"

"

0"

CH(CHOH)3CHO

413

PHENANTHRENE

acid,

Chrysophanic

chrysarobin, C15H12O3,

Ci4H602(CH3)(OH)2,
derivatives

anthracene

are

therapeutic importance, chrysophanic

being

and
of

probably-

acid

and

monomethyl-dihydroxy-anthraquinone,

chyrsarobin monomethyl-trihydroxy-anthracene.
Emodin,

is

CisHioOs,

hydroxyanthraquinone.
Rhein, CisHsOe, is also

anthraquinone

an

yCOOH

CuH502f

OH

\0H
Isomeric

with

anthracene

chemists

of diphenyl,
CH

CH,

being

the

tive,
deriva-

(1)
(3)
(5)

is phenanthrene,

CuHio:

CH

CH

Some

3, 6, 7-tri-

2-monomethyl

think
two

in addition

that
benzene
to the

it may

be

derivative

rings being linked

direct

Unking,

written:
"CH=CH"

"

"

the

to

ula
form-

CHAPTER

XXXII

HETEROCYCLIC

compounds

Heterocyclic

but

compounds,

aromatic
other

COMPOUNDS

than

Pjrrrol

C
has

atoms

the

in

contain

the

related

are

this

ring;

formula

least

at

is

HC"

CH.

HC

CH

the

to
one

atom

generally
lodol

N.^
is

\/
NH

medicinal
1

derivative;

Heterocyclic

it is
of

compounds

tetraiodopyrrol.

minor

HC"

importance

CH

!
,

HC

CH

\/
S

pyrazole,
HC"

CH

HC

NH

\/
NH

imidazole,
N

HC"

HC

CH

\/
NH

and

furan,
HC"

CH

CH

HC

\/
O
414

are

thiophene,

Psrrrolidine is the

415

COMPOUNDS

HETEROCYCLIC

addition

hydrogen

is the

This

pyrrol, H2C-3" 1-CH2.

derivative

basis

of

of

certain

alkaloids.
2

H2C

CH2

NH

and

Prolin

hydroxy-prolin

pyrroUdine

are

acids

(p. 271).
haemoglobin)
rings

of

contain

to

four

pyrrol

molecules.
is

phenazone

or

which

pyrazolone,

its formula

(from

haematoporphyrin

supposed

are

in their

Antipyrin

and

haemin,

Haematin,

being

an

derivative

important
the

contains

pyrazole

ring,

HC

C"

CH3

CH3.
OCL^^N"
CeHs

N"

It is

an

melting

substance
of

Two

pyramidon
or

antipyretic

used

are

remedies:

as

and

tussol

mandelate.
is the

Furfuraldehyde
its formula

crystalline

dimethylamino-antipyrin,

or

antipyrin

is

113^.

at

derivatives

its

value, and

of

chief

derivative

of

furan;

is
HC=CH

HC=C^CHO.
Pyridine
and

Bases.

of

great

relationship to

These

importance

certain

ammonia

are

alkaloids

on

tives
deriva-

account

which

will

of

be

their

dis-

416

ORGANIC

cussed

CHEMISTRY

The

presently.

series

is

pyridine,

member

simplest

which

has

the

the

of

formula,

structural

CH

HC/'^CH
It

may

CH

therefore

considered

be

as

HC\^CH
N
with

benzene

There

(C5H5N).

pyridines

The

when

formed

on

is

another

readily

with

it

bases,

salts.

addition

halides,
treated

When

is

are

potash

acids

very

being

ammonia
to

warmed

mixes

It

solution

formed,

Uke

with
and

form

alkyl
if these

and

pungent

is evolved.

alkalinity

test

of

odor

an

C.

with
it

produced

tejtiary

(1) Dissolve

Experiments.

with

115"

other

combines

are

etc.

resulting

Like

caustic

odor

disagreeable

water;

the

at

products

with

pyridines.

high temperatures

liquid

boils

water,

directly

crystalline

be

colorless

alkaline.

strongly

at

nitrogen

coal-tar, and

in

methylamine,

It

tobacco-smoke.

by

distilled, being

are

one

methyl

contained

are

acrolein, ammonia,

Pyridine

several

are

bones

action

the

by

replaced

group

with

in

pyridine

some

litmus.

the

Notice

odor.

(2) Then

neutralize

the

solution

with

HCl,

add

few
a

drops

of

platinic

yellow precipitate

of

chloride

solution,

(C5H5N)2PtCU

and

forms.

boil;

CONDENSED

j^CH,
with

nucleus, condensed
be

may

represented

BENZENE

OF

DERIVATIVES

^6H4"

Indol,

contains

pyrrol

the

nucleus, and

benzene

the

thus:
CH

CH

is

Skatol

POUNDS
COM-

BENZENE

HETEROCYCLIC

PYRROL

417

COMPOUNDS

HETEROCYCLIC

methyl

indol, C6H4"

Indol

/CH.
\nh/

and

skatol

characteristic

odor

the

in

the

aromatic

are

volatile

with
C

C6H4"f

contain

They

the

are

duced
pro-

of bacteria

action

by the

in

on

They

protein.

steam.

oxidation

of indol

product
as

an

ethereal

in

bination
com-

sulphate,

S02(0K)
It

/CH

doxyl-sulphate.
urine

latter.

sulphuric acid

^0"

faeces, imparting

(tryptophan)

groups

with

in
the

to

intestine

is the

Indican

contained

are

is

It

in considerable

is

sometimes

quantity.

indoxyl glycuronic

acid.

potassium
in

present
The
The

urine

may

origin of

in-

the
also
these

418

ORGANIC

indol

bodies

is

Indigo

can

various

and

solution

this

chloroform.
be

can

thus

acid

Skatoxyl-sulphuric
skatol,

of

is

of

product

the

corresponding

CH

O"

SOzCOH).
COOH

in the

acid.

It

is

position
decom-

protein, being produced

in

tryptic digestion. It,

tion
estima-

^CH2CH(NH2)

/3-indol a-amino-propionic

gives

solution

C6H4"^^CH

Tryptophan,

bacteria

by-

chloroform

colorimetric

C6H4"^
^C"
/

is

removed

indigo

an

derivative

indigo by-

blue

with

the

made.

be

may

then

is
The

compared

strength, and

of known

into

de-^

after

estimate

To

it is converted

urine

with

shaking

indican

in.

sets

is

indigo

much

containing

reagents,

bowel-contents.

it; and

from

decomposition

in the

the

from

obtained
urine

ammoniacal
indican

absorbed

be

from

posited

CHEMISTRY

is

turn,

attacked

by-

indol.

intestines, giving rise to

It

glyoxylic acid (see p. 220).

with

color reaction

during

/C0\
Directly

related

dioxyindol, for
by

latter

of each

Indigo

can

blue

the

two

dye.

can

be

"CO,

obtained

molecules,

from

the

end

being eliminated, thus

produced
The

is isatin,C6H4"r

Indigo, structurally,is

isatin

molecule

be

indol

former

reduction.
of

atom

to

from

synthesis

isatin.
of

It is

indigo

on

the
bination
com-

oxygen
:

a
a

able
valucom-

420

ORGANIC

CHEMISTRY

I
I

!"
I

at 50" for ten

kept

bath

of

drops
add

chloroform

chloroform

the

shake.

green.

When

and

pipette,and

solvent

color

yellow

it is

deep

green

it into

run

in

the

Remove

bottle.

indigo is deposited

evaporates

the

bottom

sample

few.

Indigo dissolves

shake.

(blue solution).

layer with
As

Cool, add

and

NaOH

10%

first,then

appears

minutes.

the

on

wall.

CH

tertiary ammonia

(chinoline) is another

Quinoline
base.

COMPOUNDS

PYRIDINE-BENZENE

CONDENSED

be considered

It may

replaced by

been

has

group

CH

in which

naphthalene

as

CH

/\^ACH

HC

HC

C9H7N.

\/c\/^^
CH^N

It

is found

coal-tar.

in

and

particularly quinine
with

Quinoline

can

glycerol in

the

be

are

acrolein
with

and

atom

; removal

fm*ther

by

aniline

from

and

from
the

The

molecule

dehydration
forming
of the

tions
reac-

hydrated
is de-

of water

causes

bination
com-

acrolein-aniline

nitrobenzene
end

and

trated
concen-

glycerol

the
of

obtained.

is

below):

exp.

follows:

as

finally oxygen

hydrogen

(see

distilled

are

aniline

from

of nitrobenzene

acid

to acrolein

from

quinoline

synthesized

presence

sulphuric
involved

cinchonine,

hydroxide,

potassium

alkaloids,

certain

When

removes

chain

and

;
a

also

from

the

421

COMPOUNDS

HETEROCYCLIC

ring, resulting in the closing of the

benzene

pyridine ring.
CH

/\

HC

/"\9/\

HC

CH

CH

+0

+H2O

is

(Quinoline)

it.

liquid boiling

alkaloids

Many

240".

at

quinoline, pyridine

of

treatment

CH

(Acrolein-aniline)

Quinoline

CH

CH

CH

CH

CH2

used

substance

as

is said

antiseptic, and

an

H2SO4,

from

derivatives.

Oxyquinoline Sulphate (chinosol) (C9H7NO)

is

proper

deri\^ed

be

can

quinoline

are

By

to

non-toxic.

be

Synthesize quinoline.

Experiment.
flask mix
and

75

while

15

the

having

condenser

add

with

on

damp

vigorous, cool

is very

flask with
mixture

an

becomes

sand-bath.

Then

distill with

steam.

nitrobenzene

come

partially, render
NaOH

quiet,
dilute

heat

the

solution, and

no

again

the

reaction

flame.

three
c.c.

part

If the
of the
the

When
hours
of water

on

and

oily drops

more

stop the

mixture

the

bellows.

300

heat

Wrap

upper

for

with

When
over,

air-

an

and

cm.,

the
the

from

air stream

When

remove

H2SO4

with

sand-bath.

rag.

begins (sudden bubbling)

action

of

aniline,

of C.P.

gm.

liter

of

gm.

Connect

diameter

62

mixture.

gradually

flask very

24

nitrobenzene,

glycerol;

agitating

condenser
the

of

gm.

of

gm.

In

of

distilling. Cool

alkaline
distill with

with

strong

steam, thus

422

CHEMISTRY

ORGANIC

the

removing
distillate

phenol,

into

phenol

as

(see

338).

p.

in

warm

fixed

as

phenolate,

with

Diazotize

while

and

ether

the

last
aniline
under

experiment
cooled

the

H2SO4,
becomes

(the phenol

is set

quinoUne
the

liquid

dilute

with

Extract

steam.

the distillate with

in the

alkaline

bath, make

This

convert

distinctlyacid

it

distill with

to

directed

was

rendering

after

and

specially treated

is

aniline.

and

quinoline

quinoline

proceed just as

was

free),
from

done

phenol.
and

Thalline, C9H9(OCH3)NH,

C9H9(OH)N

Kairine,

that

C2H5,

"

used

been

have

(quinalgen) is
C9H5(OC2H5)NH(COC6H5)N.
Analgen

Kynurenic

are

as

antipyretics.
recent

more

acid, occurring in the

rivative
de-

quinoUne

urine

antipyretic,

of

dogs,

is

quinoline derivative,
CH

COH

HCi^^V;"

COOH;

L"
N

CH

it is

supposed

Atophan
importance.

is

to

derived

be
of

one

It is

the

tryptophan.

from

remedies

newer

that

is of

phenyl-quinoline-carboxylic acid,
CH

C"

COOH

hc^Wh
C

HC
CH

"

CeHs

HETEROCYCLIC

is the

Novatophan

ethyl

CH

CH

CH

because

alkaloids

The

at

it.

of quinoline:

of the derivation

formula

of the four

one

any

isomer

an

CH

It is of importance

methyl atophan.

of

ester

is

Isoquinoline, CgHrN,

from

423

COMPOUNDS

be written

may

positions

of many

the

at

with

sides of the

rings.
SYNOPSIS
Aromatic
A.

Benzene

hydrocarbons.

Benzene

derivatives.

1.

Halogen

2.

Hydroxy

Compounds

derivatives.
derivatives.

( Ethers.
,

p,

( Ethereal
nyr
/i\
(1) Monacid

-J

salts.
1

phenols

( Substitution
"
.

b.

(2)

Diacid

(3)

Triacid

Fatty

alcohol
'

products.

phenols.
phenols.
side-chain

and

compounds

Alcohols.

Aldehydes.
tives

'

Ketones.
Monobasic

acids

^^

( Ethereal
c.

Phenolic

3.

Dibasic

4.

Nitrogen

monobasic

acids.

acids.
derivatives.

(a)

Nitro

(6)

Amino

compounds,

(c) Diazo

compounds.

compounds.

salts.

deriva-

424

B.

C.

D.

ORGANIC

5.

Svlphur

6.

Arsenic

7.

Quinones.

derivatives.

derivatives.

Condensed

benzene

1.

Naphthalene,

2.

Anthracene.

3.

Phenanthrene,

Heterocyclic

rings.

compounds.

1.

Pyrrol

2.

Condensed

Alkaloids.

CHEMISTRY

and

pyridine

bases.

heterocycHc-bemene

(1)

Indol

(2)

Quinoline

(3)

Isoquinoline

and

rings.

derivatives.
and

derivatives.
and

derivatives.

XXXIII

CHAPTER

ALKALOIDS

AND

DRUG

PRINCIPLES

ALKALOIDS

In

broadest

its

includes
basic

all

application

nitrogenous

alkaloid

term

substances

organic

{alkaloid

character

in

the

that

Caffeine

alkali-like)

are

and

theobromine,

maines,
been

choline,

is that'alkaloids
which
of

them

quinoUne,

other

leucoall

have

ptomaines

of

in

which

all

contain

phenanthrene,

empirical

are

of

structure

pyridine,

nitrogenous

than

more

formulae

of

follows:

Coniine

CgHnN.

Nicotine

C10H14N2.

Sparteine

C15H26N2.

Theobromine

C7H8N4O2.

TheophylUne

C7H8N4O2.

Caffeine

C8H10N4O2.

Pelletierine

CsHisNO.
425

plant

chain
one

of
atom

tertiary
which

pyrrolidine,
or

acceptable

seems

closed

alkaloids
the

Those

derivatives

as

include

Most

bases.

The

definition

have

molecule.

and

muscarine,

recent

most

Many

and

alkaloids.

called

The

bases

purin

ucts
prodatoms.

in

the

ammonia

is known

quinoline,

are

iso-

purin.
the

chief

alkaloids

are

426

ORGANIC

CHEMISTRY

Pilocaxpidine

C10H14N2O2.

Hydrastinine

C11H13NO3.

Pilocarpine

C11H16N2O2.

Physostigmine

C15H21N3O2

Eseridine

C15H23N3O3.

Homatropine

C16H21NO3.

Sinipine

C16H25NO6.

Apomorphine

C17H17NO2.

Piperine

C17H19NO3.

Morphine

C17H19NO3.

Cocaine

C17H21NO4.

Hyoscine

C17H21NO4.

Atropine

C17H23NO3

Hyoscyamine

C17H23NO3

Codeine

C18H21NO3.

Lobeline

C18H23NO2.

Thebaine

C19H21NO3.

Cinchonine

C19H22N2O

Cinchonidine

C19H22N2O

Curarine

C19H2GN2O.

Sanguinarine

C20H15NO4.

Berberine

C20H17NO4.

Papaverine

C20H21NO4.

Quinii^e

C20H24N2O2

Hydrastine

C21H21NO6.

Strychnine

C21H22N2O2.

Narcotine

C22H23NO7.

Colchicine

C22H25NO6.

Gelseminine

C22H26N2O3.

Yohimbine

C22H28N2O3.

Brucine

C23H26N2O4.

Narceine

C33H27NO8.

(Eserine).

(Scopolamine).
Isomers.

Isomers.

(Isomer, Quinidine)

428

stable

nucleus

ORGANIC

CHEMISTRY

is found,

such
ether

isoquinoline. Methyl

or

may

be

broken

and

from

the

methoxy
the

(OCH3)

that

products

of

hydrolysis
and

droxyl, carboxyl
determined.

In

the

of the

molecule

shall

consider

We
known

in

regard

of

to the

in the

to

number

of

ascertained.

be

hydrolyzed,

and

can

be

examined.

Hy-

alkaloids

proved
of the

structure

readily

are

groups

few

some

now

the

can

been

has

the

ture
struc-

by synthesis.
that

facts

are

of alkaloids.

DERIVATIVES

PYRIDINE

It is necessary

be

carbonyl
case

hydriodic acid,

with

can

esters

are

of alkaloids

Unkings

formed

iodide

methyl

groups

Alkaloids

by heating

up

pyridine, quinoline

as

designate the positions

of groups

pyridine ring thus:

CH(7)

(/30HC/\:3H(^)
("OHC

CH(")
N

Piperidine is the

simplest derivative,
CH2

H2C

ca
NH

Pipeline
of

is contained

piperidine and

in pepper.

It is

tion
combina-

piperic acid, C12H10O4.

ALKALOIDS

is

Coniine

AND

DRUG

429

PRINCIPLES

dextro-a-propyl piperidine,
CHz

HaC/^CH

CH-CH2CH2CH3

H2C
NH
is

Nicotine

the

pyridine

attachment

pyridine being in the

2 of the

position

derivative

pyrrol

of

(see

methyl

414)

of

pyrrolidine

to

p.

position of the

j3

latter

and

former:
CH

HoC

1CH2

HC/\C
CH2

HC\/
N

CH

HC
N

and

Coniine

nicotine

both

are

volatile

both

are

very

hemlock-seed,

liquids having

and

nicotine

from

to litmus.

In

acid

malic

a-propyl piperidine
it

except

that

active

coniine

can

crystals of the

is
be

crystals containing
the first

is

synthesized;

of

laevorotatory.
from

tobacco

the

with

this the

natural
d

thetic
Syn-

coniine,

Optically

inactive.
from

are

nicotine

citric acid.

by securing

this

coniine, the

from

Both

of

first crop

dextroconiine.

only

synthesis (1886)

Nicotine

of

tobacco.

is identical

obtained

tartrate

is obtained

and

optically

odor, and

strong

Coniine

with

similarities;

marked

have

poisonous.

strongly alkaline
is combined

CHj

This

was

alkaloid.

Z-Nicotine

has

been

variety is separated by

430

ORGANIC

CHEMISTRY

crystallization of the
less toxic

than

Z-nicotine.

Sparteine is thought
but

its chemical
It is

to be

piperidine derivative,

has

structure

mined.
fully deter-

been

not

dextrorotatory.

artificial alkaloids

The

is much

d-Nicotine

tartrate.

and

a-

j3-eucaine

plex
com-

are

piperidine bodies.

CeHsCOOvC

CeHfiCOONX/OOCCHa
CH

^H

H.C

HoC

H:

CH,

HsC

s.

\c

c"

HsC^/
CH3

(a-eucaine)

(i9-eucaine)

eucaines

The

group

instead

of

an

of the

acid

and

less

is of
is

an

the
The

alkaloids

and

CHOH

"

radicle.

ing
hav"

COO

It dilates

persistentlythan

the

atropin.

DERIVATIVES

of the cocaine
derivatives.

invaluable

atropine

local
group

substance

and
This

pharmacological

great

basal

to

anaesthetic.

pyrrolidine

all

pupil.

jS-eucaine, having

attached

acid

PYRROLIDINE

The

to

differ from

affect the

not

radicle, CeHs

benzoic

quickly

more

It is not

the

they do

related

place

mandelic

the

pupil

in

in that

is

Euphthalmine
CH3

local anaesthetics, and

are

in action

cocaine

"CH,

atropine
class

used

to

dilate

for all of these

are

alkaloids
Cocaine

importance.

anaesthetic, while
are

of

group

members
the

of

pupil.

compounds

is

ALKALOIDS

This

tropine.
closed

carbon

PRINCIPLES

has,

as

will be

noticed,

431

secondary

chain:

This

double

is called

the

It may

DRUG

AND

BfsC

ring nucleus
nucleus.

tropan

be

looked

condensation

of

CH.

as

upon

CH

with

the
N
C

the

the

pyrrol

pyridine ring,

and

the

ing
neighbor-

two

in

atoms

ing
hav-

to

common

CH,

rings.

two

Tropic

acid has the formula

/CH2OH
CHOH

Atropine is the

tropine

alcohol)of tropic acid, its

H2C1

ester

formula

(tropine being

an

being,

iCHa

HC

CH

HsC

CHi

CH

OOC-C

Atropine
action

is

is what

H"^^*^^

opticallyinactive.
would

Its

be expected of d

physiological

Z-hyoscyamine.

432

ORGANIC

different

esters, atropine and

other

saponified. Atropine
Atropine

has

laevorotatory. d-Hyoscyamine
degree of physiological actioD.
is

Hyoscyamine
a

CHEMISTRY

been

has

its isomers

and

hyoscyamine
have

Like
be

can

synthesized.
marked
a
cological
pharma-

action.
is

Eumydrine
and

CH3

NO3

the latter
the

same

attaching

to the

artificial alkaloid

of

tropine and

less

called

consisting of tropic acid

C8H13NO2,

alcohol

an

It is used

If in

from

to

is

an

ester,

scopolin,
pyrrolidine. It
with

combined

laevorotatory.

more

atropine.

hyosdne,

derived

in

acid

pupil

the

persistently than

also

Scopolamine,

prepared by

mandelic

dilates

for

less toxic.

atropine, but is much

It

atropine,

It is used

to five.

an

and

of

atom

opine is

promptly

is

as

combination.

atropine,

methyl

purposes

condensation

ester

of

changing its valence

Homatr

the

nitrate

the

cause

analgesia.

tropine an

atom

of

CH2

group

of the

ondary
sec-

ringbe replaced by COOH,ecgonineisobtained:

H,Ci

-iCHa

HC

CH

CH,

.^H

H"C

COOH

CHOH
"

".

'

ALKALOIDS

433

PRINCIPLES

DRUG

this is derived

From

is the

cocaine, which

methyl

benzoyl ecgonine:

of

ester

AND

|CHt

HgCi

HC

CH.

CH=

H,C

^^COO-CHs

OOC-CcHg

exists both

Cocaine
a

marked

more

local

Its solution

anaesthetic.

methyl

Besides

toxic
has

cocaine

little effect

Other

be

are

sterilized

atropine in

to

resemblances

some

on

substitutes

formula

instead

CH2

than

cannot

valuable

in

action.

has

Tropacocaine
has

very

hydrolyzes readily, yielding

benzoylecgonine.

structure, there

pharmacological
but

similarity of cocaine

this

chemical

is

it

and

alcohol

Z,the latter having

as

Cocaine

action.

heat, because

by

d and

as

of

and
the

as

similar

to

CHCOOCH3.

cocaine,
It is less
It

strongly anaesthetic.

pupil.

for

cocaine, namely,

stovaine, and alypin (see p. 360) have

been

novocaine,

previously

mentioned.
Nicotine

is

pyrrolidine derivative

pyridine derivative

(see p. 429).

as

well

as

434

CHEMISTRY

ORGANIC

QUI

The

NE

NOLI

alkaloids

chief

The

alkaloids.

DERIVATIVES

of

this

class

following formula

CH2=CH-CH"

cinchona

been

has

suggested

^^^ cinchonine

CH2

CH"

the

are

probably

Quinine
has

the

mula,
for-

same

except that
H

at the

atom

marked

t h

tion
posi(X) is

replaced
m

the

by

an

group

(OCH3).
Cinchonine

is dextrorotato

quinine
laevorotatory.

Cin-

is the laevorotatory

chonidine

isomer
cinchonine.
is

dine

of

isomer

Euquinine,

ester, quinine

an

It

tasteless.

gives

full

Aristoquin is similar
carbonic

ester.

quinine,

but

the

Quinine

Its

it

has

quinine

to

Quini-

the
is

rotatory
dextro-

important

bitter.

It is very

medicine.

as

quinine.

of

ethyl carbonate, is
action.

euquinine.

action

is the
of

none

the

It is

diquinine
that

of

disadvantages

of

same

as

latter.

Quinine
double

and

salt, is

urea

very

hydrochloride,
soluble

injection, being
anaesthetic

locally.

and

crystalhne

is suitable

for subcutaneous

non-irritating and

even

430

ORGANIC

Papaverine
Hydrastine

CHEMISTRY

been

has

synthesized.
has

probably

but

similar

the

plicated
com-

more

formula:

OCH3

is

Narcotine

the

OCH3

group

Hydrastinine
of

stronger

believed

to

be

methoxyhydrastine,

taking the place of

is

hydrastine

alkaloid

an

with

nitric

physiologicalaction

at

prepared
acid.
than

formula

is

HaCk^

l(

=0
NH"
/

CH2

tion
oxidaa

much

hydrastine.

\0-C^^C^CH2
CH

by

It has

^^
CH

(X).

CH3,

Its

ALKALOIDS

the

side

DRUG

AND

being bent

chain

derivation

from

Narceine

has

437

PRINCIPLES

so

point

to

as

its

out

hydrastine,
similar

somewhat

formula, but

it

has

in. addition

methoxy

has

still

narcotine,

as

narcotine

formula.

hydrochloride

the

to

It is

is called

and

physiological
in

Cotarnine

them
of

is of

product

hydrastine.

isoquinoline half
the

stypticin,and

hydrastinine
both

action;

such

is much

are

as

way

less

of

Its
the
Its

phthalate

Morphine

and

is the

10%

weaker

in

of

the

lessen

to

similar

very

circulatory
haemorrhage.

DERIVATIVES

codeine, and

thebaine, all of

present in opium.
are

Derivatives

apomorphine,

peronine.
most

that

purposes

about

affect

produced
artificially

dionine, heroine

have

expensive.

morphine,

being alkaloids

morphine

valuable
we

morphine.

alkaloid

have.
Its

peutic
for thera-

Opium

derivatives

contains
are

much

physiological action.

Its constitutional

be:

oxidation

an

methoxyhydrastinine.

PHENANTHRENE

These

several

styptol.

Cotarnine

system

is

hydrastinine

corresponds

is called

and

group

complex formula,

more

C12H15NO4,

Cotamine,

formula

acid

groups,

Berberine

of

benzoic

formula

is

supposed by

some

to

ORGANIC

CHEMISTRY

C-OH

(X)

CH

Codeine

with
X.

CH3
Thus

is supposed
substituted
codeine
Codeine

to

for the

is the
has

been

by treating the latter with

of caustic

have

potash

the

of the

monomethyl

prepared

OH

from

at

group

ether

iodode

methyl

formula,

above

of

phine.
mor-

morphine
in the presence

Ci7Hi7NO(OH)2+CH3l+KOH

(Morphine)

=Ci7Hi7NO(OH)(OCH3)
(Codeine)

+KI+H2O.

ALKALOIDS

It

prepared by heating

is

and

potassium

alcohoUc

KOH

Both

codeine

and

supposed

is

OCH3

two

morphine

of

mixture

with

(see exp.).

attached

atoms

sulphate (K(CH3)S04)

methyl

morphine

Thebaine

439

PRINCIPLES

DRUG

AND

hydrogen

less

two

nucleus, and

phenanthrene

place of the

in

groups

have

to

the

to

laevorotatory.

are

hydroxyls

two

of

morphine.
action

the

By

molecule

concentrated,

of

of water

be

can

removed

mineral

acids,

from

morphine,

producing apomorphine:
C17H19NO3"

H2O

=Cl7Hi7N02.

(Morphine)

It

is

after

green

Other

derivatives

forward

morphine,
Heroine

the

apomorphine

threne
phenan-

methyl piperidine.

with

long standing.
of

have

morphine

been

recently

therapeutic agents.

as

hydrochloride

is the

Dionine

in

is condensed

nucleus

put

that

supposed

It turns

(Apomorphine)

of the

ethyl ether

of

Ci7Hi7NO(OH)(OC2H5)HCl.
is

an

ester, diacetyl morphine,

/OOCCH3

is the

Peronine

of

hydrochloride

of the

benzyl

ether

morphine
Ci7Hi7NO(OH)(OCH2C6H5)
(1)

Experiments.

sulphate

quinine

and

reagents, such

Test

as

HCl.

solutions

sulphate

phosphomolybdic

with

of

morphine
alkaloidal

acid, picric acid.

440

CHEMISTRY

ORGANIC

iodine

(2) Dissolve
the

of

Extraction

of

add

500

barely

lead

with

it twice

spontaneously,

character

of

it,and

few

of hot

c.c.

alkaloidal

taste

reagents

(4) Produce

in 50

Then

shaking.
and
20

0.6

heat

add

c.c.

in

of water,

all volatile
make

sUghtly

transfer

to

portions

small

the

line
crystal-

Remove

part of the residue

solution

the

test

with

on

alkaline

of

attach

benzene.

methyl

powdered
hours.

two

HCl

with

ammonia

Dry

and
the

KOH

Add

Cool,

and

shake

and

distill oflf

and

boiling water-bath.
with

phate
sul-

condenser

reflux

for

neutralize

morphine

alcohol, warming

excess

an

of

1 gm.

separating funnel,
of

tions
por-

chloroform

the

residue.

methyl

water-bath

materials

two

filter

chloroform

potassium

gm.

strongly alkaline,

until

about

to

through

Let

Dissolve

of pure

c.c.

more

(exp. 1).

codeine.

(pure alkaloid) and

the

examine

and

no

with

Dry

then

water

adding

if it is turbid

Dissolve

it.

cipitate
Pre-

by

evaporate

caffeine

the

this

time, until

dish.

evaporate

of

grams

minutes.

15

Filter

evaporating

10

shaking

Na2S04.

an

at

by

filter into

in

for

of chloroform.

c.c.

tion.
solu-

heat, keeping the Uquid

solution, and

anhydrous

little of

To

Filter, and

the

Extract

of 15

drop

notice

bisulphate

filtrate of

the

forms.

Cool

c.c.

again.

quinine

and

and

H2SO4,

alkaloid.

an

from

acetate,

precipitate
75

the

boiling temperature

at

tannin

10%

in dilute

of water,

c.c.

potassium

solutions.

quinine

fluorescence

(3)
tea

acid

tannic

iodide, and

solution, mercuric

iodide

potassium

with

combined

filter;
eral
sev-

ben-

ALKALOIDS

with

extracts

zene

water-bath.

HCl,

with

if necessary

drops

of the
of

but

two

faint

pink

This

color

of the

of

to

used

as

pears.
ap-

H2SO4

by

not

the

of

means

phine,
mor-

evaporating
and

warm,

be

yield considerable
obtained

be

can

on

and
a

allowing

solving
dis-

by

drop

slide.

DERIVATIVES

caffeine

elsewhere

is 1, 3-

and

(p. 293).

dimethyl-

2,

of theobromine.

prepared

theobromine,

6-

dioxypurin,
These

synthetically.

three
All

arjB

remedies.

Pilocarpine does
but

color

by

20%

evaporate

discussed

can

few

given also by morphine,

chloroform,

isomer, therefore,

alkaloids

containing

reddish-violet

synthesis should

xanthins,

Theophylline
an

of H2SO4

in

Crystals

methyl
been

adding

is obtained,

color

residue
of

PURIN

have

c.c.

curic
mer-

molybon

extracted

be

c.c.

little in

solution

The

2%

appears.

codeine.
a

blue

a
are

the

to

about

H2SO4;

given by codeine, but

test

method

impure

tests

cannot

is this:
add

add

formaline, and

dish

following

the

develop the color; (6) to

to

morphine

benzene.

with

ammonium

some

solution

solution

These

make

drops of C.P.

warm

drop

on

potassium

with

Also

paste of

drop of the alkaloid

solution

solution.

few

residue

part of the

of the

drop

(a) make

date

dryness

to

an

gently.

iodide
test:

chloride, filter into

evaporate

Dissolve

warming

Test

and

441

PRINCIPLES

calcium

dish,

evaporating

DRUG

AND

not

have

the

full

has the heterocyclic ring imidazol

purin nucleus,
(see p. 414).

442

CHEMISTRY

ORGANIC

CH

C2H5

"

CH

CH2

CH2

C"

"

OC

N^Hs.

"CH
0

It

HC"

It

dextrorotatory.

is

has

marked

logical
pharmaco-

action.

CERTAIN

THAT

ALKALOIDS

NOT

HAVE

BEEN

CLASSIFIED

The

indicates

following
of

structure

what

is

known

about

the

aconitine:

/OCCHa

is

Colchicine

formula:

the

given

/COOCH3

DRUG

PRINCIPLES

OF

UNKNOWN

STRUCTURE

"

Canfharidin,
from

either

Picrotoxin,

C10H12O4,
benzene

or

is

an

acid

cyclohexane.

CisHieOe.

Picropodophyllin,

C23H24O9

"

2H2O.

lactone,

derived

444

APPENDIX

specific
do

may

fifth

combustion

in

Group

II, Lessons

Group

V,

Lessons

5, 1, 2, 3,

4.

by

this

method

to

while
and

it

by

retain

studying

rote.

this

advice
since

chemistry,

Medical

textbook

use

as

as

to

some

should

students
for

be

student
formulae.

need

biochemistry,

pharmacology.

discouraged,

the

structural

studying

learning

the

be

hand,

students

of

idea

substances

that

student

the

giving

Many

"

ine

the

with

organic

advise

other
in

"

ending

character.

strongly

the

Student.

the

in

by

the

alkaloids,

means

basic

drilled

learn

and

formulae
on

proper

retained

amines

We

thoroughly

book

3.

distinctly

urged

2, 3, 4, 5,

4, 5, 1, 2,

of

62).

1, 2, 3, 4, 5.

Lessons

have

IV,

that,

be

ments
experi-

Group

empirical

to

the

2.

Formulce.

try

p.

3, 4, 5, 1,

indicating

the

(see

Lessons

case

The

and

III,

We

fourth

32),

Group

of

but

p.

take

to

thus

order,
I, Lessons

the

of

(see

have

Group

in

are

25),

p.

apparatus

course,

different

Spellings,

that

Beckmann

will, of

group

(see

analysis

the

use

may

Each

determinations

gravity

reference

physiology,

ology,
path-

REFERENCE

TABLES

TABLE

Specific

Gravity

Percentage

and

[According

to

445

Squibb.]

of

Alcohol

446

TABLES

REFERENCE

TABLE

The
for

table
alcohol

table
number

of

the

of

0.0002

by
are

lower

U.

S.

I"

of

Bureau
of

concentrations
to

by

0.0005;

Continued

for

0.0004-0.0006.

gives

Standards

alcohol

instance,

specific gravities

differing from
the

figures

those
for

in

this

95-100%

REFERENCE

TABLE

Milligrams
AT

of

Various

(Millimeters

Pure

II

Nitrogen

Temperatures
of

447

TABLES

Mercury)

in
and

1
under

c.c.

of

the

Various

Moist

Gas

Pressures

448

REFERENCE

TABLES

TABLE

Specific

Gravitt

and

Percentage

Solution

III

of

NaOH

in

Aqueous

TABLE

Specific

Gravity

and

449

TABLES

REFERENCE

Percentage
Solution

IV

op

KOH

in

Aqueous

450

REFERENCE

TABLES

TABLE

Acetic

Acid

TABLE

Vapor

Tension
OF

(Aqueous
Water

and

VI

Pressure
of

40%

in

KOH

Millimeters
at

Various

op

cury)
Mer-

tures.
Tempera-

452

TABLES

REFERENCE

IX

TABLE

Power

The

Certain

op

Acids

to

Inversion

Cause

Hydrolysis

Velocity
Velocity

Coefficients

Coefficients
Coefficients

Acid.

(Cane-

(Methylace(Acetamide).
tate).

sugar).

acid

Hydrochloric

Nitric

acid

Hydrobromic
acid

Sulphuric
Formic

1.000

1.000

1.000

1.000

0.916

0.955

1.114

0.983

0.972

0.536

0.541

0.547

0.0153

0.0131

0.00532

0.0040

0.00345

0.000747

0.0484

0.0430

0.0295

0.271

0.2304

0.245

0.754

0.6820

0.670

0.1746

0.169

0.00545

0.00496

0.00195.

0.0172

0.00797

acid
,

Acetic

acid
acid

Monochloracetic
Dichloracetic

acid
.

acid.

Trichloracetic

Oxalic

acid

1857

0
.

Succinic
Citric

acid
acid

01635
.

INDEX

alcohol,

Absolute

Acetaldehyde,

142

cyanhydriii,

Acetaminophenetole,
Acetanilide,

382

amides,

chlorides,

imides,

381

'*

161

'

freezing-point

of,

estimation

184

value,

Acids,

ble,
ta-

166

284

strength,

273

115,

183,

acid,

250

165

Acetates,
Acetic

Acid

147

274

Acetamide,

206

Achroodextrin,

151

Acetaldehyde

value,

Acetyl

205

113

,
**

450

aromatic,

356

It

"(

"(

ti

metallic

("

it

mol.

glacial,

**

163

aromatic,

dibasic

371

salts,

''

165

fatty,

157

nation,
determi-

wt.

ion

concentration

monobsic

aromatic,

'*

of,

by
salt,

silver

405
*

40

356

,
it

"

structural

of

proofs

'*

formula,
ft

it

specific

164

gravity

''

ble,
ta-

ft

Acetic

anhydride,

Acetic

ether,

Aceto-acetic

169,

206

acid, 192,

218

179

Acetyl
it

382

chloride,

Acyclic

compounds,

Airol,

95, 209, 407

251
222

acid,

222

268

absolute,
denatured

((

late,
salicy-

166

370

Alcohol,

paraminophenyl

116

383

acid,

Alanin,
166

302

293

Agaricinic

304

302

halogenides,

Agaric

166

304

group,

aldehyde,

Agar-agar,

206

169,

Acetylenes,

Acrylic

Adsorption,

Acetphenetidin,

Acetylene,

acid,

Adrenalin,

352

Acetylation,

427,
302

Adenin,

256
355

Acetozone,

172

442

AcryUc

Acyl

190

Acetophenone,

Acetyl

Aconitine,
Acrolein,

163

tests,

Acetonitrile,

of,

strength
,

450

Acetone,

etc.,

113

ft

dibasic,

monobasic,
,

142
or

methylat-

367

ed,

142

it

salicylic acid,

((

367

heat
f

453

of

combustion,

137

454

INDEX

Alcohol, ordinary, 141

specific gravity tables,
**

Alcohols, lOd
aromatic, 349
diacid, 193
monacid, diacid, etc.,
,

112

monacid

primary, 138
products of,

oxidation
,

Amido

112

primary,
secondary, 110, 189
tertiary, 110, 192
triacid,199

( (

group,
" (

113

tests, 147, 153

Aldehydes,

112, 146

* *
,

aromatic,

349

Aldohexose,
Aldol, 151
Aldol condensation, 151
Aldose, 228, 231
of
organic
Aliphatic division
chemistry, 103
Alizarin, 412
Alkaloidal
precipitants, 427
Alkaloid, extraction of, 440
Alkaloids, 425
231

determination

*'

of

chemical

structure

427

Alkyl cyanides, 256

hydroxides, 136
hahdes, 124
Alkyls, 108
Allantoin, 292
Alloxan, 287
Alloxuric
bodies, 293
Allyl alcohol, 302
( (

* *

**

isothiocyanate,307
radicle,302

258

aromatic

mixed

fatty,

379

acid, 219, 221

147
ammonia,
bisulphite, 147

( "

410

Aminoacetic

151

I I

308

114

group,

Amines,
Amines,

110, 186

Aldehyde,

* *

' '

445

AUyl sulphide, 307

sulphocarbamide,
thiourea, 308
Aloin, 412
Alpha naphthol, 409
Alpha naphthylamine,
Alphozone, 198
Alypin, 360
Amicrons, 87
Amido
acids, 266

of,

acid, 268
383
Aminoacetphenetidin,
Amino
acids, 114, 234, 266
387
Aminoazobenzene,
Aminobenzoic
acids, 360
Amino
compounds, aromatic, 376
acid, 272
jS-Aminoethysulphonic
Aminoformic
acid, 266
o-Aminoglutaric acid, 269
233
Aminohexose,
o-Aminoisobutylacetic acid, 269
382
Aminophenols,
acid, 268
o-Aminopropionic
Aminosuccinic
acid, 269
Aminoisovaleric
acid, 269
Ammonia
derivatives, 114
Anunonium
carbamate, 266
Ammonium

cyanate,

278

267
Amphoteric electrol3rte8,
Amphoteric reaction, 403
Amygdalin, 262, 351
Amyl alcohol, fermentation,
inactive, 145
normal, 144
Amylene hydrate, 146
Amyl nitrite,265
Amylodextrin, 250
( I

I "

It

i i

Amylopectin, 250
Amyloid,
Amylose,
Amylum,

246
250

249

Amyl valerate,187

'^

144

455

INDEX

336
tt

sulphur derivatives,391
Arsacetin, 397
Arsanilic
acid, 397
Arseno-benzol, 396
derivatives
Arsine, substitution
of, 264
Aseptol, 393
Asparagin, 277
Asparaginic acid, 269
Aspartic acid, 269
Aspirin, 367
Association
of liquids, 69

411

oil,318
Anthranilic
acid, 383
Anthraquinone, 412
Antifebrine, 381
Antikamnia, 381
Antinosin, 372
Anthracene

"

415

450

Arbutin, 252
Arginsise, 270
Arginin, 270
Aristol, 131, 344
Aristoquin, 434
Aromatic
acids, 356
alcohols, 349
amines, 376
bases
having nitrogen
in nucleus, 414
compounds,
103, 116,
" (

tt

ti

it

Atophan, 422
Atoxyl, 397
Atropine, 431
Autocatalysis, 219
407
Auxochromes,
Avogadro's hypothesis,
Azobenzene, 388

condensed

it

lute,
so-

42

' '

Barfoed's

Barometer,

reagent, 241
correction

for

perature,
tem-

20

compounds,

Aromatic

of

Baeyer's reagent, 301

Baking powder, 224
Ballistite,201
Balsams, 258
Balsam
of Peru, 358
of Tolu, 358

316
it

molecules

N atom,
216
Asymmetric
carbon
Asymmetric
atom, 216
Atomic
in
weight of elements
2
organic compounds,

415

Aqueous pressure,
Arabinose, 229
Arachidic
acid, 187

"

69

415

Antipyrin,
Antipyrin mandelate,
Apiol, 347
439
Apomorphine,

derivatives,

tt

66

Antipyretics,381,

354

374

salts,377

Anions,
Anisole, 340
Anozol, 131
Anthracene,

ketones,
nitrogen

tt

( t

compounds,

hydroxy

Aromatic

Ansesthesin, 367
Anaesthetics, 125, 128, 133
Analgen, 422
Analysis, elementary, 28
Anhydrides, 169, 198, 371
Anhydrolysis, 255
AniUdes, 381
Aniline, 376
derivatives
of, 378

compounds,
n

having
rings,
synopsis
of, 423
409

reactions

of, 317

Bases, strength of, 172

Bassorin, 251
Beckmann's
thermometer,
hquors.
Beer, see Malt
Beet

243
sugar,
Behenic
acid, 187

60

456

INDEX

Benzal

chloride, 351
Benzaldehyde, 351
Benzamide, 361
Benzanilide, 382
Benzene, 318
derivatives, 116, 816
It
diazonium
nitrate, 384
diazonium
sulphonic
acid, 395
disubstitution
ucts
prodof, 326
homologues of, 329
model. Collie's,324
preparation of, 320
ring. 323
structure
of, 320
sulphonic acid, 392
( t

1 1

Benzyl methyl ether, 350

Berberine, 437
Betaine, 261
Beta
naphthol, 409
Beta
410
naphthylamine,
Betol, 368
310
Bicyclic compounds,
for
Biological methods
molecular

It

tl

tl

" (

1 1

i i

tl

trisubstitution

tives,
deriva-

347

Benzidine,
Benzine, 121

388

Benzoates, 358
Benzoic
acid, 330, 356, 386
preparation of,358
tt
salts of, 358
substitution
ucts
prod359
of,
( (

( (

" (

( I

t (

Benzoic

aldehyde,

351

Benzoin, 352
Benzol, 318
Benzonitrile, 386
354
Benzophenone,
398
Benzoquinone,
Benzosol, 345
Benzosulphinide, 394
Benzotrichloride, 357
Benzoylacetyl peroxide, 352
Benzoylaminoacetic
acid, 360
Benzoyl anihde, 382
Benzoyl chloride, 359
Benzoylation, 359
Benzozone,

Benzyl
Benzyl

Bitter

almonds, oil of, 351

Biuret, 280
Biuret
reaction, 280, 296

Bleier

and

sity
denKohn,
vapor
44
determination,
Blood,
depression of freezingpoint, 64
Boiling-point determination, 18
**

at

760

19

mm.,

Bomeol, 313
Boyle's law, 41
Branched
chains, 105,
Brandy, 140
333
Bromobenzene,
192
Brometone,
129
Bromoform,
Bromural, 283
Brownian
motion, 88
Brucine, 435

123

Butane, 105, 120

Butter, 203, 204
Butyl alcohol, normal,
Butyl chloral hydrate,
Butyric acid, 185
Butyrin, 186, 200, 203
Butyrolactone, 219

144
156

Cacodylic acid, 264

Cadaverine, 263
Caffeine, 294, 441
312
Camphor,
311
artificial,
( I

352

acetate, 350

alcohol, 349
Benzyl chloride, 334

concentration,

54

328

Benzeugenol,

ing
test-

1 1

monobromide,

it

oil,347

Camphoric
Cane

sugar,

acid,

313

241,

243

313

457

INDEX

Cantharidin, 442
Caoutchouc, 314
Capillarity, 73
Capric acid, 187
Caprin, 203
Caproic acid, 187
Caproin, 203
Caprylic acid, 187
Caprylin, 203
Caramel, 244
Caraway, oil of, 344
Carbamic
acid, 266
Carbamide, 277
Carbinol, 138
Carbohydrates, 227
Carbolic
acid, 337
Carbolic
oil,318
Carbon
asymmetric,
atom,
detection
of, 3
estimation
of, 28
oxychloride, 128
tetrachloride, 120
113
Carbonyl group,
113
Carboxyl group,
Carboxylic acids, 157
Carnitine, 262

Chemical

Chinoline,
Chinosol,

420
421

Chloracetic

Chloral,

acids,

154

alcoholate, 154
Chloralamide, 156
Chloral
formamide, 156
Chloral
hydrate, 154
Chloralose, 156
Chloral

substitutes, 156
Chlorbenzene, 333, 385
Chlorbenzoic
acids, 334,
350
alcohol,
Chlorbenzyl

Chloretone,
216

((

("

as

((

313, 843
Castor
oil,204, 304
Catab'tic action, 161, 179, 240,

Cellulose
'*

Centric

91

formula,
Cephalin, 262
Ceryl alcohol, 192
Cetyl alcohol, 192
Cetyl palmitate, 192
Chemical
equilibrium, 175

(t

molecular

agent,

weight
determination, 44
Chlorpropionic acids, 185
Chlortoluenes, 334
Cholalic
acid, 220
Cholesterine, 315
Cholesterol, 315
ChoUc
acid, 220
Choline, 261
406
Chromophore
group,
Chrysarobin, 413
Chrysophanic
acid, 413
434
Cinchonidine,
Cinchonine, 420, 434
Cineol, 314
acid, 362
aldehyde,
oil,354

Cinnamon
323

reducing

Cinnamic

esters, 247
benzene

191

238

Cinnamic

nitrates, 247

of, 5

acetone,

1 1
,

360

191

Chlorhydrins, 200
Chlorine, detection
Chloroform, 127

Catalysis, 179
Cataphoresis,
Catechol, 345
Cathode, 66
Cations, 66
Celloidin, 248
CeUuloid, 248
Cellulose, 246

170

Chloral

t(

249

mined,
deter-

( i

Carvacrol,

how

structure,

353

Citrates, 226
Citric acid, 226
Closed

carbon

Cloves,
Coal

oil

gas,

chains, 309

of, 347

119

Cocaine, 433

458

INDEX

Codeine,
Cod

Cresols, 343
Cresylic acid, 343
Croton
chloral, 156
Crotonic
acid, 303
Croton
oil,204

438

liver oil,204

Coefficient

of

dissociation,68

Colchicine,442
Collargol,

97

Collie's benzene

Collodion,

model,

Crystallization,7

324

248

Colloidal

solutions, 79, 210, 407

Colloids, 79, 210, 249, 407
irreversible,83
precipitation of, 92
protective, 96
reversible, 84
swelling of, 97,211
Combustion
analysis, 28
analysis, modified
when
halogens
* *

* '

**

*'

**

II

present, 36
tt

modified

analysis,

ti

when

nitrogen

present,

35
modified

analysis,
when

sulphur

present,
i t

furnace,

Condensation,

231,

Conductivity,

Copper acetate, 166

Copper acetyhde, 305
Copper-zinc couple, 118
Cordite, 201
Cotarnine, 437
of tartar, 224

Creatin, 285
Creatinin, 285
Creohn, 343
Creosols, 346
Creosote,
Creosote

346

oil,318

41

try,
chemis-

organic

Denatured

410

formula,

of
1

216

Structural.

law,

Definition

60

Constitutional

Cream

Dalton's

234

429

Constants,

electrical,65

Conglomerates,
Congo red, 402.
Coniine,

**

30

rings, 409

benzene

Condensed

36

Cryoscopy, 59
Crystals, purity of, 10
Cyanacetic acid, 257
Cyan acids, 257
278
Cyanamide,
Cyanic acid, 257, 278
Cyanides, 114, 256
aromatic, 393
Cyanpropionic
acids, 197
309
Cychc compounds,
Cyclopentane, 309
Cyclopropane, 309
Cyclose, 310
Cymene,
310, 332
121
Cymogene,
Cystein, 272
Cystin, 272
Cytosin, 295

see

alcohol, 142
Depression of freezing-point by
solutions, 59
Dermatol, 370
Destructive
distillation,162
Developers, photographic,
Dextrin, 141, 249, 260
Dextroconiine, 429
Dextrolactic
acid, 217
Dextrose, 231, 238
Diabetes, 238
Diacid
phenols, 345
Dialkyl sulphides, 306
Dialuric
acid, 290
Dialysis, 22, 85
Diamino
dihydroxy
-

(di) benzene,
Dianthracene,

411

3%

345

diarseno

460

INDEX

Eosin, 373
Epicarin, 410
Epinephrin, 383

Equilibrium, chemical,
**

of

cules,
mole-

68

Erucic

303

Erythrodextrin,
Eseridine, 426
Eserine,

oil,314
372

347

It

acetamide, 347
carbinol, 347
iodide, 347
432
Eumydrine,
Euquinine, 434
Euthalmine, 430
Exalgin, 382
Extraction, 20
It

427

acid,

Eucalyptus

tt

Ergotinine, 427
Ergotoxine,

314

Eudoxine,
Eugenol,

175

and

ions

Eucalyptol,

250

426

174
Esterification,

Esters,
Ester

173

Fats,

value,

Ethanal, 151
Ethane, 104,
Ethene, 300
Ethereal

( (

vegetables, 204
Fatty acids, 157
volatile,204
compounds,
synopsis of,

206

1 1

120

178

,
"(
,

115

132

Fat

aromatic

"(

fatty,
mixed, 134
true aromatic, 340

340

Ethyl acetate, 182

alcohol, 139
amine, 260
benzene, 330
it
benzoate, 359
II
bromide, 125
n

tl

II

It

tl

It

tl

It

tl

Ethylene,
1 1

It

193, 300
bromide,

values, 205
FehUng's solution, 241
Fermentation, 237, 240
Fire damp,
118
Fischer, Emil, 297
Flashing point of oils,122
.

butyrate, 187
carbamate, 267
carbonate, 278
chloride, 125
cyanide, 255
ether, 132
glycollate, 213
nitrite,265
sulphonic acid, 306
sulphuric acid, 127

(I

tl

1 1

salts, 166,

Ethers, 109,

203

* *

193

Fluidity, 78
Fluorescein, 372
148
Formaldehyde,
Formaline, 148
274
Formamide,
Formic
acid, 158
series,168,
Formonitrile, 256
''

''

Formula,
Formulae,

calculation

Ethylenes, 300
Eucaine, a and

/3,430

centage
per-

38
tural,
struc-

98

Fractional

crjrstallization,218
Fractional
distillation,13
Freezing-point constants, 60
depression by solutions,
* *

59

II

from

composition,
empirical and

'^

preparation
of, 301
lactic acid, 214

187

Fructose, 231, 235,

Fruit

sugar,

238

Fuchsin, 379
Fuchsin, acid,

379

238

461

INDEX

Fuchsin

aldehyde reaction,

Furan, 414
Furfuraldehyde, 230,
Furfurol, 230, 415
Fusel oil,145

trioleate,203
tripalmitate, 203
tristearate,203

Glycin, 268
Glycinamide, 275
GlycQCoU, 220, 268, 360
Glycocholic acid, 220

251

233

88, 260

Glycogen,

acid, 368
GalUsin, 244
Gall-nuts, 368
Garlic, oil of,"07
Gas, coal, 119
laws, 41
natural, 119

Glycol,
' '

*'

193
228

aldehyde,

Glycolates, 194
Glycollates, 213
Gly collie acetate, 213
acid, 194, 212
it
aldehyde, 194
n

**

molecular

tribenzoate, 360

tl

Gallic

Gases,

200

1 1

tt

test, 246

Galactosamine,

Glyceryl butyrate,

415

Galactose, 231, 238, 246,

"

148

weight

41

of,

GlycoUid,

214

Gasoline, 121
Gasoline, fuel value, 122
Gastric juice, 184, 402
Gaultherin, 252
Gay-Lussac*s law, 41
Gelatine
dynamite, 201

Glycuronates, paired, 221

Glycuronic acid, 221, 233,

Gelose, 251
Gelseminine, 426
Glucoproteins, 233
Glucosamine, 233
Glucosazone, 235
Glucose, 231, 236, 238
d-Glucose, a and |8,236
Glucosides, 251
253
Glucosides, artificial,
Glucosone, 236
Glutamic
acid, 269
Glutamin, 277
Glutaminic
acid, 269
Glutaric
acid, 195
149
Glutol,
Glyceric acid, 202, 219, 234
aldehyde, 228, 234
Glycerine, 199
Glycerol, 199
Glycerophosphoric acid, 202
Glycerose, 228
' '

Glyceryl acetates, 206

Glyoxal,

194

GlyoxyUc acid, 194,

Gram

molecular

Gram

molecule,

Grape

sugar,

Green

237

soap,

219

solution, 50
42

238
209

Guaiacol, 345, 346

benzoate, 345
Guanidin, 284
Guanin, 293
Gum
Arabic, 251
**
benzoin, 358
Gums, 251
Gum
tragacanth, 251
Guncotton, 247
Gunzberg's reagent, 348,
Gutta
percha, 315
**

402

Hsematin, 415
Haematoporphyrin,
Haemin, 415
Haemoglobin, 298
Halides, 108
Halogens, detection
Halogen derivatives
124

415

of, 4, 5
of parafi"ns,

462

INDEX

Halogen

of benzenes,

derivatives

Hydrolysis,

333

Headache
Heat

of

medicines, 381
combustion, 121,

395

116,

acid, 373

Hexachlorbenzene, 333
Hexamethylentetramine,
Hexane, 104, 120, 123
Hexone
bases, 270
Hexoses, 231
Hippuric acid, 360

264

Hydrion, 172
Hydrocarbons,

316

((
,
" (
,
tt
,

aromatic,
cyclic,309
of, 102
groups
satiurated, 103,

344
Hydroxycymenes,
j8-Hydroxyethyl-sulphonic

unsaturated, 103,

acid, 212
Hydroxyformic
348
Hydroxyhydroquinol,
nature
of, 136
Hydroxy 1 group,
146
Hydroxyl, test for, 136,
Hydroxy prolin, 271, 415
acids, 214
Hydroxypropionic
343
Hydroxytoluenes,
Hyoscine, 426, 432
432
Hyoscyamine,
Hypertonic solutions, 55
Hypnal, 156
355
Hypnone,
Hypotonic solutions, 55
292
Hypoxanthin,

concentration,
404

nascent,

of

substances, 22,

26

1 1

ion

307

Identification

299

acid, 362
Hydrocinnamic
256
acid,
Hydrocyanic
Hydrogels, 84
of, 3
Hydrogen, detection
estimation
of, 28

118

acid,

306

Ichthyol,

117
" I

aromatic,

336

102

" (

Hydrometer,
Hydroquinol, 346
346
Hydroquinone,
Hydrosols, 84
Hydroxion, 172
Hydroxyacetic acid, 212
acids, 114, 212
Hydroxy
a"ids, 363
Hydrpxybenzoic
acid, 218
^-Hydroxybutyric
313
Hydroxycamphor,
compounds,
Hydroxy

Histidin, 271
Holocain, 382
Homatropine,
426, 432
acid, 371
Homogentisic
series,104
Homologous
of benzene, 329
Homologues
436
Hydrastine,
Hydrastinine, 436
Hydrazine, 388
388
Hydrazobenzene,
Hydrazones, 148, 235, 352

209

24

414

to

452

cause,

Hydroljrtic dissociation, 70,

Heptoses,
Heroine, 439
Heterocyclic compounds,

1 1

acids

of

power

137

240

Hexabasic

157

'*

Heavy oil,318
Hedonal, 283
Helianthin,

of oils,303

Hydrogenation

Illuminating gas,
Imidazole, 414
Imido
compounds,
Imido

group,

119

284

114

Indican, 253, 417,

Indicators, 399
Indigo, 418
Indigo red, 419

419

463

INDEX

Indigo, synthesis of, 419

white, 419
Indirubin, 419
Indol, 417
Indolaminopropionic acid, 418
Indoxylglycuronic acid, 417
Indoxylsidphuric acid, 417
"

' '

stereo-chemical,214

Isomerism,

Isomers, 98
Isonitriles,256
Isosmotic
solutions, 56
Iso-parafiins,123
Iso-pentane, 123
Isopral, 156

Ink, 370
Inosite, 310
Inversion, 240

Isopropylmetacresol, 344
Isopropylorthocresol,344
Isoquinoline,423

Invertases, 240

Isosuccinic

Invert

241, 245

sugar,

lodal, 130
Iodine, dextrin test, 250
glycogen test, 251

acid, 198
Isotonic coefficient,57
solutions, 55
Isovaleric acid, 187
*'

tt

starch
,

test, 249

427

Jervine,

Iodine

value, 206
lodobenzene, 333
Iodoform, 129
lodoformin, 131
131
lodoformogen,
414
13i;
lodol,
lodothyrin, 298
Ionization, 65

Kairine, 422
Kekul^, 322
Kerosene, 121

Ketohexose,

acid, 192
Ketones, 114, 189
aromatic,
Ketone

((

constants,

it

experiment, 342
of indicators, 399

Ions,
* *

451

Isatin, 418

f f

mixed

aromatic

fatty,

354

Ketose, 228, 231,

' '

electrical charge of, 66

Isoamyl

( (

65

Isethionic

354

1 1

232

acid, 306
alcohol, primary, 144
tertiary, 145

235

test, 239

Kjeldahl's method
estimation, 38
Koprosterol, 315
Kynurenic acid, 422

of

nitrogen

**

i t

acetate, 179

Iso-butane,
Isobutyl alcohol, 144
carbinol, 144
Isobutyric acid, 185
Isocholesterol, 315
Iso-compounds,
106, 123
Isocyanide reaction, 257
Isocyanides, 256
123

*'

Lacmoid, 346
Lactic
acid, 139, 214,
Lactid, 218
Lactocaramel, 244
Lactones, 219
Lactophenin,

234

382

Isoleucin, 269
Isomaltose, 237, 244

Lactosazone, 239
Lactose, 240, 242, 244
Lactylphenetidin, 382
Lsevolactic
acid, 217
Laevulose, 231, 235, 238
Lanolin, 192, 211

Isomerism, 98,

Lard,

Isocycliccompounds,

106

116

203

INDEX

464

Laurie
Lead

Metaldehyde,

acid, 187
II
,

i i

Metaxylene, 362
Methanal, 148
Methane, 104, 118
Methane
series, 117

165

of, 165

sugar

basic,

Lecithin,
Leucin, 269
Leucomaines, 295
Light oil,318
Lignin test, 247
262

Methoxyhydrastine,
Methyl, 108

acid,

Litmus,

402

304

Lobeline, 426
of freezing-point,
Lowering
Lubricating oil,122
Lycetol, 264
Lysidin, 264
Lysin, 270
Lysol, 343
Malic

acid,
Malonic
acid,

59

*'

**

''

* '

**

glycocoU,

**

guanidin, 285
guanin, 293
hexoses, 231
indol, 417

'^

197

**

' '

''

Uquors, 140
Maltodextrin, 250
Maltosazone, 239
Maltose, 141, 237, 240, 242,
Mandelic
acid, 362
Mannose, 231
243
Maple sugar,
see

gas,

"

Methane.

268

395,

orange,

244

135

isocyanide, 256

* '

Methylene
blue,
Methyl pentoses,

400

396
230

Methylphenylhydrazine,

235

Methylphenyl
ketone, 355
416
pyridines,
Methyl
salicylate,364
thionin
hydrochloride,
( "

series,117
gas
Mass
action, 175
Melissic alcohol, 192

Marsh

MeUite,

carbinol, 139
chloride, 125
cyanide, 255
ether, 132
ethyl ether,

Methyl

141

Marsh

acetate, 179

Methyl alcohol, 138

Methylamine, 261
Methylaniline, 378
Methylated alcohol, 142

221

Malt,

436

acetanilide, 382

Methyl
Methyl

Ligroin, 121
Linoleic

acid, 394

Metasulphobenzoic

acetate, 165

II

151

396
ft

373

acid, 373
Melting-point determination, 10
Menthol, 313
Mercaptans, 115, 306
Mesitylene, 330
preparation of, 331
Mesitylenic acid, 362
Mesotartaric
acid, 223
Mesoxalic
acid, 222
326
Meta
compounds,
MelUtic

' *

violet, 380
xanthins, 293
Victor, method,

II

Meyer,
Microns,
Milk

44

87

sugar,

244

representing formulae,

Models
106

Metadihydroxybenzene,

346

Models

to

represent

merism,
stereoiso-

223

Mole,
Molasses,
42

Molecular

243

dispersesolutions,80

465

INDEX

Molecular

weight:

Calculated

from

freezingpoint determination, 64

Calculated

osmotic

from

sure,
pres-

Naphtha, 121
Naphthalene, 409
Naphthols, 409
/3-Naphthol benzoate,
"

a-Naphthol-orthohydroxytoluic

50

Calculated

from

sity
den-

vapor

determination, 41
Determined
analysis
by

of

acid,

by

Molisch's
Monobasic

and

gases

of colloids,90

weight

test, 234, 254

acids, 40,

113

Monobromethane,
Monobromisovaleryl-urea,
125

Monochloracetic

acid,

283

170

Monochlorethane, 125
Monochlorhydrin, 200
125
Monochlormethane,
Monoformin, 160
336
Monohydroxybenzene,
acids, 363
Monohydroxybenzoic
Monohydroxy dibasic acids, 221
Monohydroxytribasic acids, 226
Monomethyldihydroxyanthraquinone,

gas,

Neo-pentane,
Neurine, 264

118

119
123

Neuronal, 283
Nicotine, 429
Nirvanin, 367
Nitriles,acid, 256
Nitrites, 265
Nitrobenzene, 374
Nitrobenzoic
acids, 360
Nitrocellulose, 247
264
Nitro-compoimds,
aromatic,
**

374

Nitroparafiins, 264
derivatives

Nitrogen

114,

of

fins,
paraf-

255

detection

( (

413

Monomethyltrihydroxyanthra-

i I
,

of, 3
estimation
by

bustion,
com-

36

quinone, 413
Mononitrobenzene,

374

by Kjeldahl's method, 38
tables, 447
Nitroglycerine, 201
Nitroglycerol, 201
Nitrophenols, 341
Nitrous
acid, action on amines,
estimation

Mononitrophenol,

341

227
Monosaccharides',
"
,

ti

general

tions
reac-

of, 235

Mordants,
Morphine,

Narceine, 437
Narcotine, 436
Nascent
hydrogen,
Natural

41

vapors,

MoleciUar

of

weight

acid,

410

depression

freezing-point,69

Molecular

410

Naphthylamines, 410
Naphthylamine-sulphonic

derivatives,40
Determination
of

410

408
437

Mucic

acid, 233
Multirotation, 236

Non-electrolytes,65

Murexide,

Nonoses,

291

Muscarine,
Mustard
oil,307, 343
Mutarotation, 236
Mycoderma
aceti, 161
262

Myristic acid, 187

260

240

Normal

compounds,
Nosophen, 372
262
Novame,
Novaspirin, 367
423
Novatophan,

106

466

INDEX

Novocaine,

Orthophthalic acid,

360

371

acid, 295
Nuclein
bodies, 293
Nucleoproteins, 295

Osazones, 235, 238, 245

melting-points of,
Osmotic
cell,48, 49

Octoses,

Osmotic

pressure

of

Osmotic

pressure

of

Nucleic

' '

Osmotic
240

almonds,

Oil of bitter

351

Osmotic

cinnamon, 354
cloves, 347
eucalyptus, 314
garlic,307
peppermint, 313
sassafrass, 347
thyme, 332
turpentine, 311
wintergreen, 365
Olefiant

haemoglobin,

of

pressure

gelatine,90

determination
pressure,
of, with red blood cells,55

Osmotic

effect

pressure,

Osmotic

of

perature
tem-

50

on,

effect of concentration
pressure,
of solution on, 51

Osone, 236
Oxalates, 196
Oxalic acid, 195
Oxaluric
acid, 287
Oxamide, 276
Oxy camphor, 313
of percentOxygen, calculation
age
of, 38
Oxyproteic acid, 298
Oxyquinoline sulphate, 421

Olefins, 300
acid, 303
Olein, 203
Oleomargarine,

colloids,90

Osmotic

300

gas,

46

pressure,

90

344

caraway,

239

Oleic

186

Oleo-palmito-stearin,204
Olive

oil,204
alkaloids, 435, 437
Opium
Optical activity, 216
composition
Palmitic
acid, 187, 303
Optical activity of protein dePalmitin, 203
products, 271
Palmito-distearin, 204
Orange II, 395
381
Papaverine, 435
Orangine powders,
Paper, 246
Orcein, 347
Parabanic
acid, 287
Orcin, 347
Para
326
compounds,
Orcinol, 347
definition
chemistry,
Organic
of, 1
Organic chemistry, preliminary
of, 101
survey
synopsis of,
Organic compounds,
115

Organic

substances, solvents

of,

Paradihydroxyfienzene,346
Paraffin, 122
derivatives,
oil,122
series,117
Paraffins, 104, 117
""

II
,

Ornithin,

Orphol,
Ortho

boiling-points, specific
gravities,etc.,
120

270
It

410

heat

of

combustion

compounds,

326

Orthodihydroxybenzene,
Orthoform,

107

II

367

345

i I
,

of, 121
ssoithesisof, 117

Paraformaldehyde,

148

468

INDEX

Piperidine,428

Putrescine, 263

Piperine, 428
Pleismolysis, 57
Polarization, 245

Pyoktanin, 380
415
Pyramidon,
Pyrazole, 414
Pyridine, 416
bases,

Polymerization, 148,
Polymers,

151

* '

148

Polymethylenes,
Polypeptides, 296

Pjrimidin derivatives,294

310

Polysacoharides, 228,

246

Polyterpenes, 314
Potassium

acetate, 165

(f

acid

antimonyl

* '

benzene

tartrate, 224
tartrate,

sulphonate,

337, 357,

tt

hydroxide,

393

specific
table, 449

gravity
phenol sulphate,
Pressure, osmotic, 46
tt

**

Primary

alcohols, 110,
amines, 257

'*

Prolin, 271,

Pyrrol,
Pyrrolidine,

a-PyrroUdine-carboxylic
Pyrrolidine derivatives,
Pyruvic acid, 140, 192

Quinalgen,

430

189

201

' '

Quinidine, 434
Quinine, 420, 434
bisulphate, 440
Quinine-urea hydrochloride,
Quinoid structure, 402
Quinol, 346
Quinoline, 420
Quinones, 398

Racemic
" (

acid.

((

lactic

Ptomaines,

263

Purification

of

180

substances, 7

bodies, 292
nucelus, 292
Purpuric acid, 291

Reduction

acid, 217

tests, 235

Reichert-Meissl

value, 205,

346

Resorcinol, 346
Reversible
reactions,176
Rhamnose,
Rhein, 413
Rhigoline,
Ricinoleic

434

substances, 216
tartaric
acid, 223

Resorcin,

Pseudo-catalyst,

422

' '

of-Propyl piperidine, 429

Protamines, 271
of dextrose
Protein, formation
from, 233
synthesis of, 296
Proteins, classes of, 298
Protocatechuic
acid, 368
Prussic
Hydrocyanic
acid, see

' '

acid,

271

Quantitative analysis,28, 40
Quaternary bases, 114, 260

Purin

415

415

''

Propylene,

247

414

186

Propane, 105, 120

Propene, 302
Propenol, 302
Propionic acid, 184
Propyl alcohol, 144
secondary,
* *

340

162

450

vapor,

Pyrimidin ring, 287

Pyrocatechin, 345
Pyrocatechol, 345
Pyrogallic acid, 348
Pyrogallol, 348
Pyroligneous acid,

Pyroxylin,

225

It

415

230

121

acid, 304

207

469

INDEX

Rochelle

chain, 106, 356

Sidonal, 264
248
Silk, artificial,
248
viscose,
Sinalbin, 253
Side

salt,225
Rosaniline, 379
of
Rotation
polarized

light,

' '

216

Rotatory

of sugars,

power

236,

Sinigrin, 253
Sinipine, 426

245
314

Rubber,

"

Saccharates, 244
Saccharic
acid, 232
Saccharin, 394
Saccharose, 241, 243
Safrol, 347
Sajodin, 188
Sahcin, 252
Salicylicacid, 363
**

**

Skatol,

'*
,

,
'*
,

ysis
anal-

* '
,
* '

Soaps,
Sodium
i t

""

Salol,365
366

Salvarsan, 396

" (

Sandalwood

it

oil,314

Santoninic

It

426

It

acid,

tt

410

Saponification,208
**

Saponin,

value,
acid,

green,

hard, 209
resin, 209
soft, 209
Venetian,

Sassafras

acetate, 165
220
amalgam,
hydroxide, specificgravity
table, 448
methyl, 131
methylate, 137
oleate, 209

phenylcarbonate, 363
potassium tartrate, 225
salicylate,364

Solute,
Solutions, 47, 69
((
colloidal,81
,

205

((

217

electrical

n
,

hydrocarbons,

103,
II

117

of, 65
isotonic, hypotonic,
hypertonic, 55
obedience
to gas laws,
50

fe...
Prints,7

246

Scopolamine, 432
Scopolin, 432
Secondary alcohols, 110,
* *

ity
conductiv-

oil,366

Schiff's reagent, 154

Schweitzer's
reagent,

209

209

Sarcosin, 268
Saturated

209

47

253

Sarcolactic

418

of, 209

* *

* '

396

417

Soap, castile,209
cleansing action
,

of, 32
SaUcyl-sulphonic acid, 393
SaUgenin, 252, 354
SaUpyrin, 367

Sanguinarine,
Sanoform, 366
Santonin, 410

six,"

Skatoxylsulphuric acid,
Smokeless
powder, 248

combustion

Salophen,

and

hundred

Six

Sorbitol, 232
Sparteine, 427, 430
Spatial representation

189

amines, 258

cules,
mole-

215

Selective

permeability, 57
Semipermeabte membrane,
Serin, 268

of

Specific gravity
47

determination,
23

''

''

of

23
liquids,

INDEX

470

Sulphur, derivatives

Specificgravity of solids,24
**

'*

Spermine,
Starch,
' *

tables,
448, 449,

445,
450

264

Suprarenin,

soluble, 88

Surface

acid, 187, 303

Stearin, 203
Stereochemical
isomerism,

formula,

Structural

formula

98

acetic

of

acid, proof of,

164

435

Strychnine,

Stypticin,437
Sublimation,
Submicrons,

13
87
'

ammonias:

Substituted

Secondary, 258
Tertiary, 258
Succinic
acid, 197
Succinic
anhydride,

198

284

Sucdnimide,
Sucrose, 241, 243
comparative
Sugars,
estimation
,
f f

",

reducing

Tertiary alcohols,110, 192

n
amines, 258
tt
bases, 114, 425
Tetrabromfluorescein, 373
120, 127
Tetrachlormethane,

ide,
hydrox-

260

of, 241

specificrotation

312

Tetrathylammonitun

of,241

power
tt

Tannacol, 370
Tannalbin, 370
Tannic
acid, 88, 368
Tannigen, 370
Tannins, 370
370
Tannoform,
Tartar
emetic, 225
Tartaric
acids, 222
Tartronic
acid, 202, 221, 290
Taurin, 272
Taurocholic
acid, 221
Tautomerism,
290, 401
Terpenes, 310
Terpin, 312
Terpin hydrate,

257

Primary,

384

214

214

Structural

306

tension, 71, 88
Suspensoids, 81
Synthesis, 6

Stearic

Stereoisomerism,
Sterins,315
Stovaine, 360
Strophanthin, 253

of, 3

ethers, 115,

249

of, 245

131

Tetra-iodo-methane,

of, 239
Sulphanilic acid, 394
Sulphobenzoic acids, 360
Sulphocyanic acid, 257

Tetra-iodo-pyrrol,414

Sulphonal, 307
Sulphones, 306
Sulphonic acids, 115,

Tetraphenylhydrazine,

((

tests

"(

'*
,

((

Tetramethoxybenzylisoquinoline,435
Tetranitrol, 202

306

aromatic,

391

chlorides,391

Sulphonmethane, 307
Sulphur alcohols, 115, 306
-containing amino
"t

272

paraffins,

306

detection
,

it

16
distillation,

Steam

115,
ti

of

Tetronal, 307
Tetrose, 229
Thalline, 422
Thebaine, 439

Theobromine, 294,
Theophylline, 441
acids,

Thio

alcohols, 306

Thiophene, 319,

414

441

381

471

INDEX

Thiophenol,

of colloids,86

Ultrafiltration

391

Ultramicroscope,

87

Thiosinamine, 308
oil of, 332, 344
Thyme,

Unsatiu*ated

Thymin,

295

UracU,

Thymol,
Toluene,

343

Urates, 291
Urea, 277
freezing-point
,

329

Toluene-fiulphonicacids,391,

393

hydrocarbons,

295

of molecular

acids, 362
Toluidines, 378

Toluol,
Tolyl carbinol,351

,
' '

,
' *

synthesis,287

341

acid, 170
Trichloraldehyde, 154
Trichlorhydrin, 200
Trichlorlactamide, 289
Trichlormethane,
120, 127
Trichlortertiary butyl
alcohol,
191

129

Urotropine,

326

Trinitrobenzene,
Trinitrocellulose,248

Vacuum

distillation,16

Valence

of

Valerianic

acid,
acid, 187

376

Vegetable bases,

Trioses,

Veratrine,

228
380

Veronal,

Triphenylmethane
dyes,
Trisaccharides, 228, 246
Tropacocaine, 433
Tropffiolin(X), 396
Tropic acid, 431
Tropine, 431
Tryptophan,
220, 271, 418

Victor

Turpentine,

Von

380

871

187

see

Alkaloids.

427

282

Meyer's
method, 44

vapor

density

Vinegar, 162
Viscosity,77
tt

of colloidal

solutions,

89
tt

number, 79, 207

Baeyer's reagent, 301

Tussol, 415

Tyrosin,269,

organic

368

Trional, 307

311

in

elements

weight of, 41
Vapors, molecular
Vapor tension table, 450
Vaseline, 122

Trinitrophenol, 341

Triphenylamine,

freezing-

264

Valin, 269
Vanilla, 368
VaniUic
acid,
Vanillin, 368

Trimethylamine, 261
Trimethylene, 310

of

point of, 64
Urinometer, 24

Valeric

191

Trinitrotoluene,

Urine, d^ression

compounds,
368

of, 290

348

Trihydroxybenzoic acid,

293

tautomerism

* *

Trichloracetic

Tricresol, 343
Trihydroxybenzene,

oxalate,281
specificgravity of, 25
synthesis of, 1, 278, 281

Urethane, 267
Uric acid, 286,

127

Tribrommethane,

Triiodoacetone,
Triiodomethane,

nitrate, 281

' '

251

gum,

Tribromphenol,

weight,

62
'*

329

Traube's

tion
determina-

' '

Toluic

Tragacanth,

103

Water-gas, 119

472

INDEX

Waxes,

192

Weight

normal

solutions,
balance,

Westphal's
Whiskey,

23

oil

Wintergreen,
alcohol,

turpentine,

ti

Xanthin,
((

Xylenes,

330

XyUdines,

of,

311

bodies,

293

233

365

fermentation

Yohimbine,

Zinc

293

331

378

229,

Yeast,

138

330,

330

Xylose,

140

Wood

meta,

Xylol,

140

Wines,

60

Xylene,

Zymase,

426

methyl,
141

131

by,

141