1 How is ethauol for alcoholic driuks made?

2 what is the differeuce oetweeu a fossil fuel aud a reuewaole fuel?

3 what does 'distillatiou' meau?
4 what does '0F0' staud for?
5 hame the two t]pes of radiatiou ou either side of the visiole spectrum.
Thro0gho0t the ceot0r|es, chem|sts have syothes|sed oew s0bstaoces aod
|ovest|gated the|r propert|es |o the search Ior more 0seI0| mater|a|s. |o the receot
past, orgao|c chem|sts have deve|oped a broad raoge oI or|g|oa| aod exc|t|og
mater|a|s, s0ch as pharmace0t|ca|s, reIr|geraots, so|veots aod p|ast|cs.
ha|ogeooa|kaoes are |mportaot start|og mater|a|s Ior maoy syothet|c ro0tes. Th|s |s
beca0se they are read||y cooverted |oto a|coho|s aod other I0oct|ooa| gro0ps - yo0
w||| become Iam|||ar w|th maoy oI these compo0ods d0r|og yo0r Advaoced |eve|
work. For ceot0r|es, a|coho|s have beeo w|de|y koowo aod 0sed. veo ch|mpaozees
recogo|se how to get a b0zz Irom the j0|ces oI rott|og Ir0|t! Today, commoo a|coho|
(ethaoo|) |s seeo as a poteot|a| rep|acemeot I0e| Ior dw|od||og s0pp||es oI cr0de o||.
Advaoces |o modero chem|stry have seeo the deve|opmeot oI soph|st|cated
techo|g0es Ior the aoa|ys|s oI chem|ca| compo0ods. Techo|g0es s0ch as |oIrared
spectroscopy aod mass spectrometry are oow 0sed to determ|oe the str0ct0re oI
orgao|c mater|a|s. They are a|so emp|oyed |o Ioreos|c sc|eoce as ao a|d to so|ve
cr|mes, aod |o |aw eoIorcemeot to check the a|coho| coos0mpt|oo oI dr|vers.
|o th|s mod0|e, yo0 w||| st0dy the phys|ca| propert|es aod chem|ca| react|oos oI two
I0oct|ooa| gro0ps: a|coho|s aod ha|ogeooa|kaoes. The chem|ca|s koowo as
p|ct0re oI the ozooe ho|e (dark b|0e) over Aotarct|ca |o 2005, the ozooe |ayer
protects the p|aoet Irom 0|trav|o|et rad|at|oo, b0t has beeo d|sr0pted by 0F0s
re|eased by h0maos. Yo0 w||| a|so d|scover how to aoa|yse a spectr0m |o order to
determ|oe the mo|ec0|ar mass aod I0oct|ooa| gro0ps |o ao 0okoowo orgao|c
compo0od.
1

Nak|og aod 0s|og a|coho|
2

Propert|es oI a|coho|s
3

0omb0st|oo aod ox|dat|oo oI a|coho|s
4


a|coho|s
5

|otrod0ct|oo to ha|ogeooa|kaoes
6

8eact|oos oI ha|ogeooa|kaoes
7

ha|ogeooa|kaoes aod the eov|roomeot
8

Perceotage y|e|d
9

Atom ecooomy
10

|oIra-red spectroscopy
11

|oIra-red spectroscopy: I0oct|ooa|
gro0ps
12

Nass spectrometry
13

Nass spectrometry |o orgao|c
chem|stry
14

Nass spectrometry: Iragmeotat|oo
patteros
15

8eact|oo mechao|sms
1.1 1 Mak|aq aa6 cs|aq a|cehe|
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
0escr|he the |a6cstr|a| pre6cct|ea ef ethaae| frem heth scqars aa6 etheae.
0ct||ae the cses ef ethaae| aa6 methaae|.
Mak|aq ethaae|
Ethano| can be made by two d|fferent chem|ca| processes:
the hydrat|on of ethene, O
2
H
4
,
the fermentat|on of sugars.
k6rat|ea ef etheae
Ethano| |s manufactured |ndustr|a||y by the cata|yt|c hydrat|on of ethene, O
2
H
4
, us|ng
steam |n the presence of a phosphor|c ac|d cata|yst, H
3
PO
4
. The react|on |s carr|ed out
at h|gh temperature and moderate pressure and can be operated cont|nuous|y.
148
The react|on |s revers|b|e and so convers|on of ethene |s |ncomp|ete. Each t|me the
reagents pass through the reactor, on|y 5% of the ethene |s converted |nto ethano|. Any
unreacted gases are recyc|ed and passed through the reactor aga|n. Overa||, a 95%
convers|on |s ach|eved.
|ermeatat|ea
Fermentat|on |s another method for manufactur|ng a|coho|. Oarbohydrates are converted
|nto ethano| and carbon d|ox|de. Sugar or starch |s usua||y used as the carbohydrate
source. Ethano| so|ut|on produced |n th|s way has a concentrat|on of up to 14% a|coho|
by vo|ume.
Fermentat|on |s carr|ed out |n so|ut|on at re|at|ve|y |ow temperatures, |n the presence of
yeast. The react|on |s cata|ysed by an enzyme |n the yeast ca||ed zymase. The react|on |s
s|ow at temperatures be|ow 25 O, wh||e at temperatures above 37 O, the enzyme starts
The tox|c|ty of the a|coho| a|so ||m|ts the concentrat|on of the ethano| that can be made
by fermentat|on. Th|s |s because the enzyme ceases to funct|on above an a|coho|
concentrat|on of about 14%.
Fermentat|on of carbohydrates to ethano| |s anaerob|c - |t does not requ|re oxygen. lt |s
therefore |mportant that fermentat|on |s carr|ed out |n the absence of a|r. Such cond|t|ons
prevent the ox|dat|on of ethano| to undes|rab|e compounds such as ethana| or ethano|c
yeast
2Ch
8
Ch
2
0h(aq) C
G
h
12
0
G
(aq) 2C0
2
(g)
87 C
F|gure 3 Fermentat|on of the sugar g|ucose
F|gure 2 Fermentat|on |n act|on
h
2
C Ch
2
h
8
F0
4
h
2
0
8OO C GO atm
(g) (g) Ch
8
Ch
2
0h(l)
F|gure 1 Hydrat|on of ethene
lxam|aer t|p
8ometimes a louger questiou will ask
]ou to compare the two differeut
methods for makiug ethauol.
Nake sure ]ou kuow the reageuts,
couditious aud equatious for ooth
processes.
You ma] also oe asked aoout the
advautages aud disadvautages of the
processes. lmportaut poiuts here would
euerg] requiremeuts aud atom
ecouom] (see spread 2.2.9}.
0ses ef a|cehe|s
lthaae| |a a|cehe||c 6r|aks
When we hear Lhe word alcohol, we auLomaLically Lhinl o alcoholic drinls. However, eLhanol
has many uses aparL rom alcoholic beverages. LLhanol can be used in perumes, aLershaves and
net|y|ateJ s||ts and is being developed as an
alLernaLive or peLrol Lo uel cars.
LLhanol used in alcoholic beverages is made via Lhe ermenLaLion process. ln Lhe brewing indusLry,
barley, waLer and hops are combined LogeLher wiLh yeasL Lo produce beers and lagers o varying
also help Lo prevenL Lhe acLion o bacLeria, which may spoil Lhe beer-maling process.
SpiriLs such as whisly, vodla and gin have a higher alcohol conLenL Lhan beer and are produced
in a disLillery. Here, Lhe ermenLed drinl is disLilled by slowly heaLing Lhe alcohol-waLer mixLure.
1he alcohol boils o asLer Lhan waLer and is Lhen allowed Lo condense. 1he disLillaLe will now
have a higher alcohol conLenL Lhan Lhe original liquid. 1his is Lhe meLhod used by ScoLLish
disLilleries or Lhe producLion o whisly.
lthaae| as a fce|
1he vasL ma|oriLy o eLhanol produced in Lhe USA is used or uel. Up Lo 10% eLhanol is blended
wiLh peLroleum Lo increase Lhe ocLane raLing o Lhe uel. 1he resulLing uel burns more cleanly.
or Lhe economy and Lhe environmenL.
149
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
Mak|aq aa6 cs|aq a|cehe|s
F|gure 4 Hops prov|de beer w|th both
lthaae| |a meth|ate6 sp|r|ts
MeLhylaLed spiriLs consisLs o eLhanol mixed wiLh small
amounLs o meLhanol and a coloured dye. 1hese exLra
ingredienLs male Lhe eLhanol mixLure Loxic and
undrinlable. MeLhylaLed spiriLs is exempL rom Lax and
so is ar cheaper Lhan Lhe eLhanol used in alcoholic
drinls. MeLhylaLed spiriLs is used as a solvenL or
removing painL or inl sLains rom cloLhing, and as a uel
in spiriL burners and camping sLoves.
0ses ef methaae|
MeLhanol can be used as a clean-burning uel. lL is oLen
used as an addiLive in high-perormance racing cars.
MeLhanol LasLes and smells lile eLhanol. However, iL is
exLremely Loxic and ingesLion o small quanLiLies o
meLhanol can lead Lo severe organ damage and deaLh.
1here have been a number o media sLories o people
dying as a resulL o drinling meLhanol.
MeLhanol is also an imporLanL eedsLocl or Lhe
chemical indusLry and can be easily converLed inLo
meLhanal and eLhanoic acid.
F|gure 5 A|coho| fue| on sa|e |n Braz||
Nete
B] law, the alcohol couteut of a driuk
The ABV (alcohol o] volume} shows
the perceutage of the driuk that is pure
alcohol. Here are some commou ABV
values.
Tequila = 40
Vodka = 88
wiue = 11-14
0ider = 4-8
Alcopops = 5
Beer = 8.5
0cest|eas
1 ln the product|on of a|coho|,
suggest poss|b|e d|sadvantages
of the hydrat|on of ethene
compared w|th fermentat|on.
2 Ethene |s obta|ned from crude
o||. Name the processes that are
used to obta|n ethene.
3 Why |s the product|on of ethano|
us|ng e|ther cane sugar or sugar
beet as a raw mater|a| of |ong-
term |nterest?
4 Suggest why a country such as
Braz|| wou|d make ethano| by
fermentat|on rather than
hydrat|on.
5 Wr|te an equat|on for the
combust|on of methano|.
F|gure 6 H|gh-performance rac|ng car
be|ng refue||ed
150
1.1 2 |repert|es ef a|cehe|s
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
lxp|a|a, |a terms ef h6reqea hea6|aq, the water se|ch|||t aa6 the re|at|e| |ew e|at|||t ef
a|cehe|s.
C|ass|f a|cehe|s |ate pr|mar, secea6ar aa6 tert|ar a|cehe|s.
|hs|ca| prepert|es
|,d|oen oonds
between the -O-H groups of ne|ghbour|ng mo|ecu|es. Hydrogen bond|ng |s d|scussed |n
more deta|| |n spread 1.2.13.
Ve|at|||t aa6 he|||aq pe|at
Hydrogen bonds are the strongest type of |ntermo|ecu|ar forces. The re|at|ve|y h|gh
me|t|ng and bo|||ng po|nts of a|coho|s resu|t from the presence of hydrogen bonds
between the a|coho| mo|ecu|es.
lxam|aer t|p
A vcIatiIe chemical evaporates readil]
iuto the atmosphere at room
temperature aud pressure. Nake sure
]ou uuderstaud the meauiug of the
word volatilit]!
The presence of hydrogen bonds |n a|coho| mo|ecu|es resu|ts |n a|coho|s hav|ng a |ower
vo|ati|ity than a|kanes of s|m||ar mo|ecu|ar mass. Th|s |s |||ustrated by the d|fferent bo|||ng
po|nts of a|kanes and a|coho|s shown |n Tab|e 1.
k|kaae Me|ecc|ar
mass
8e|||aq
pe|at /`C
k|cehe| Me|ecc|ar
mass
8e|||aq
pe|at /`C
-|'- `` o' -|'. `` o'
,.,- 44 4` -|'. 4o o
..|- 'o `.' ,.,. o` '
,-|- ` `o ..|. 4 !!o
'-\- oo o' ,-|. oo !`o
Tab|e 1 Oompar|ng bo|||ng po|nts of a|kanes w|th a|coho|s
!e|ch|||t
A|coho|s d|sso|ve |n water because hydrogen bonds form between the po|ar -O-H
groups of the a|coho| and water mo|ecu|es, as shown |n F|gure 2.
F|gure 2 Hydrogen bond|ng between ethano| and water
C C
h
h h
h
h
0
h h 0
h
+
+
-
hydrogen bond
C C
h
h h
h
h
0
h C C
h
h h
h
h
0
h
+
+
-
hydrogen bond
F|gure 1 Hydrogen bond|ng between ethano| mo|ecu|es
Vo|at|||ty is the ease that a liquid turus
iuto a gas. Volatilit] iucreases as ooiliug
poiut decreases.
151
So|ub|||ty dec|eases as the cha|n |ength |nc|eases:
a |arger part of the a|coho| mo|ecu|e |s made up of a non-po|ar hydrocarbon cha|n,
the hydrocarbon cha|n does not form hydrogen bonds w|th water mo|ecu|es.
depends on the number of a||,| groups attached to the carbon carry|ng the a|coho|
group, O-OH.
|r|mar a|cehe|
The -OH group |s attached to a carbon atom w|th no a|ky| groups or bonded to one a|ky|
group.
Methano| and butan-1-o| are both pr|mary a|coho|s.
Methano| has an -OH group attached to a carbon w|th no a|ky| groups.
Butan-1-o| has an -OH group attached to a carbon w|th one OH
3
OH
2
OH
2
- a|ky|
group.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
|repert|es ef a|cehe|s
C 0h
h
h
h
C
h
h
0h Ch
8
Ch
2
Ch
2
Methanol
Butan1ol
F|gure 3 Structures of the pr|mary a|coho|s methano| and butan-1-o|
Iert|ar a|cehe|
The -OH group |s attached to a carbon atom bonded to |||ee a|ky| groups.
2-methy|butan-2-o| |s a tert|ary a|coho| see F|gure 5}.
2-methy|butan-2-o| has an -OH group attached to a carbon w|th a tota| of |||ee a|ky|
groups: two OH
3
- groups and one OH
3
OH
2
- group.
0cest|eas
1 Name and c|ass|fy each of the fo||ow|ng a|coho|s:
(a} OH
3
OH
2
OH
2
OH, (b} OH
3
OH
2
OHOH}OH
3
,
(c} O
2
H
5
}
3
OOH, (d} OH
3
OH
2
OH
2
OHOH}OH
3
.
2 Draw the four structura| |somers of O
4
H
10
O that are a|coho|s. Name each a|coho| and
c|ass|fy each structure as a pr|mary, secondary or tert|ary a|coho|.
3 Show how hydrogen bonds act between methano| and water. Exp|a|n why methano|
|s more so|ub|e than pentan-1-o| |n water.
!ecea6ar a|cehe|
The -OH group |s attached to a carbon atom bonded to |wo a|ky| groups.
Propan-2-o| |s a secondary a|coho| see F|gure 4}.
Propan-2-o| has an -OH group attached to a carbon w|th |wo OH
3
- a|ky| groups.
C
0h
h
Ch
8
h
8
C
F|gure 4 Structure of the secondary
a|coho| propan-2-o|
C Ch
8
Ch
8
Ch
2
Ch
8
0h
F|gure 5 Structure of the tert|ary a|coho|
2-methy|butan-2-o|
lxam|aer t|p
lt is importaut that ]ou cau classif] au
alcohol as primar], secoudar] or
tertiar]. You cau theu decide how the
alcohol will react with au oxidisiug
ageut (see spread 2.2.8}.
0|sappear|aq a|cehe|
wheu 50 cm
8
of ethauol is mixed with
50 cm
8
of water iu a 100 cm
8

measuriug c]liuder the total volume is
oul] 98 cm
8
.
ls this magic? where has the missiug
2 cm
8
goue?
wheu water aud ethauol are mixed
together, h]drogeu oouds form oetweeu
water aud ethauol molecules. These
draw the molecules closer together thau
iu pure ethauol or pure water, reduciug
the volume.
Heat is also geuerated as the h]drogeu
oouds form oetweeu water aud ethauol
molecules.
152
1.1 3 Cemhcst|ea aa6 ex|6at|ea ef
a|cehe|s
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
0escr|he the cemhcst|ea ef a|cehe|s.
0escr|he the ex|6at|ea ef pr|mar aa6 secea6ar a|cehe|s.
0ct||ae the res|staace te ex|6at|ea ef tert|ar a|cehe|s.
Ihe cemhcst|ea ef a|cehe|s
ln a p|ent|fu| supp|y of oxygen, a|coho|s burn comp|ete|y to form carbon d|ox|de and
water. Th|s equat|on be|ow shows the comp|ete combust|on of ethano|.
O
2
H
5
OH|} + 3O
2
g} 2OO
2
g} + 3H
2
O|}
0x|6at|ea ef a|cehe|s
Pr|mary and secondary a|coho|s can be ox|d|sed us|ng an ox|d|s|ng agent.
+
/Or
2
O
7
2-
.
Th|s ox|d|s|ng m|xture can be made from potass|um d|chromate, K
2
Or
2
O
7
, and su|fur|c
ac|d, H
2
SO
4
.
green.
|r|mar a|cehe|s
to produce an a|dehyde.
The equat|on |n F|gure 2 shows the ox|dat|on of the pr|mary a|coho| propan-1-o| to
form the a|dehyde propana|.
We use the symbo| [O| to represent the ox|d|s|ng agent, as shown |n the equat|on be|ow.
F|gure 1 Ethano| burn|ng
ox|d|sed, pass|ng through the a|dehyde stage, to form a carboxy||c ac|d. Th|s |s shown |n
the equat|on for F|gure 3.
|0j C C C
h
h
h
h
h
h
h
0h C C C
h
h
h
h
h
0
h
h
2
0
K
2
Cr
2
0
7
/ h
2
S0
4
+
Froan1ol
+
Froanal
This symbol reresents
an oxidising agent
0istil immediately
F|gure 2 Ox|dat|on of propan-1-o| to the a|dehyde propana|
|0j C C C
h
h
h
h
h
h
h
0h 2 C C C
h
h
h
h
h
0
0h
h
2
0
Froan1ol
+
Froanoic acid
+
K
2
Cr
2
0
7
/ h
2
S0
4
Rellux
F|gure 3 Ox|dat|on of propan-1-o| to the carboxy||c ac|d propano|c ac|d
When prepar|ng a|dehydes |n the |aboratory, you w||| need to d|st|| off the a|dehyde
from the react|on m|xture as |t |s formed. Th|s prevents the a|dehyde be|ng ox|d|sed
further to a carboxy||c ac|d.
F|gure 4 Ox|dat|on react|ons of three
potass|um d|chromate so|ut|on H
2
SO
4
/
K
2
Or
2
O
7
}. The d|chromate |s reduced
when |t reacts, form|ng a green so|ut|on.
Pr|mary and secondary a|coho|s can be
ox|d|sed, form|ng carboxy||c ac|ds and
ketones respect|ve|y. Tert|ary a|coho|s are
not ox|d|sed and do not react
153
When mak|ng the carboxy||c ac|d, the
react|on m|xture |s usua||y heated under
before d|st||||ng off the product.
The apparatus needed to carry out d|st|||at|on
F|gures 5 and 6, respect|ve|y.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
Cemhcst|ea aa6 ex|6at|ea ef a|cehe|s
lxam|aer t|p
dichromate from orauge to greeu is
ofteu tested iu examiuatiou papers.
lxam|aer t|p
A popular questiou iu exams is to oe
asked for the structural isomers of
0
4
H
9
0H that are alcohols. You are theu
asked for the products formed wheu
each isomer is heated with excess
Rememoer.
primar] - aldeh]de, theu caroox]lic
acid;
secoudar] - ketoue;
tertiar] - nc reactiou.
Iert|ar a|cehe|s
Tert|ary a|coho|s are |es|s|an| to ox|dat|on. The ox|d|s|ng agent rema|ns orange |n co|our.
0cest|eas
1 Wr|te equat|ons for the comp|ete combust|on of pentan-1-o| and 2-methy|hexan-1-o|.
2
(a} 2-methy|hexan-1-o|, (b} 3-methy|pentan-2-o|.
3 What do you understand by the word ?
|0j C C C
h
h
h
h
0h
h
h
C C
h
h
h C C
h
h
h
0
h
h
C
h
h
h h
2
0
Butan2ol
+
Butanone
+
K
2
Cr
2
0
7
/ h
2
S0
4
heat
F|gure 7 Ox|dat|on of butan-2-o| to the ketone butanone
!ecea6ar a|cehe|s
Ketones canno| be ox|d|sed further.
The equat|on |n F|gure 7 shows the ox|dat|on of the secondary a|coho| butan-2-o| to form
the ketone butanone.
F|gure 6
condens|ng of a so|vent. A condenser |s
attached vert|ca||y above the react|on
evaporat|on
F|gure 5 D|st|||at|on apparatus
lxam|aer t|p
lf ]ou couuect a coudeuser the
wroug wa] arouud, the water
of the coudeuser aud it will uot
alwa]s euters lower thau it
leaves.
is the coutiuual ooiliug aud
coudeusiug of a reactiou mixture to eusure
that the reactiou takes place without the
154
1.1 4
a|cehe|s
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .

0escr|he e||m|aat|ea ef k
1
0 frem a|cehe|s te ferm a|keaes.
An ester |s formed when an a|coho| |s warmed w|th a carboxy||c ac|d |n the presence of
an ac|d cata|yst.
The react|on |s known as .
Ooncentrated su|fur|c ac|d |s often used as the ac|d cata|yst.
ln the react|on shown |n F|gure 1, methano| reacts w|th propano|c ac|d to produce the
ester methy| propanoate.
lxam|aer t|p
wheu uamiug au ester, the aIcchcI
provides the aIkyI part of the uame aud
the carbcxyIic acic provides the
aIkancate part.
peutau-1-ol aud ethauoic acid
peut]l ethauoate
ln the react|on, the O-H bond |n the a|coho| |s broken and water |s formed. The water
mo|ecu|e comes from the OH of the carboxy||c ac|d group and the H |n the a|coho|
group, as h|gh||ghted |n green |n F|gure 2.
Ch
8
Ch
2
C00Ch
8
Ch
8
Ch
2
C00h
h C
h
h
h0 C C C
h
h
h
h
h
0
0h
C C C
h
h
h
h
h
0
0 C
h
h
h
h
2
0
Ch
8
0h h
2
0
Methanol
Froanoic acid
Methyl roanoate
+ +
+ +
F|gure 1
C C C
h
h
h
h
h
0
0 h
C C C
h
h
h
h
h
0
0 Ch
8
0 h
Ch
8
h 0
h
+
F|gure 2
F|gure 3 S|mp|e |aboratory preparat|on
of an ester. The a|coho| and carboxy||c
ac|d are heated |n the presence of H
2
SO
4
heat
water
Test tube
Mixture ol
ethanol,
ethanoic acid
and sulluric
acid
Clam
is the reactiou of au
alcohol with a caroox]lic acid to
produce au ester aud water.
lsters
The ester respons|b|e
for the sme|| of
orange |s octy|
ethanoate.
C
0
0
0ctyl ethanoate, Ch
8
C00(Ch
2
)
7
Ch
8
Penty| ethanoate
prov|des a banana
sme||.
C
0
0
Fentyl ethanoate, Ch
8
C00(Ch
2
)
4
Ch
8
F|gure 4
Sweet-sme|||ng esters
155
|repar|aq aa ester
F|gure 3 shows how you can make a sma|| samp|e of an ester |n the |aboratory qu|ck|y
and eas||y.
ln a bo|||ng tube, add 1 cm
3
of the carboxy||c ac|d to 1 cm
3
of the a|coho|. Oarefu||y
add|ng a few drops of concentrated su|fur|c ac|d.
Pour the product |nto a beaker of co|d water.
ester.
0eh6rat|ea ef aa a|cehe|
An a|coho| can be dehydrated to form an a|kene |n the presence of an ac|d cata|yst.
Th|s |s an examp|e of an e||m|na||on react|on.
Ooncentrated phosphor|c ac|d, H
3
PO
4
, or concentrated su|fur|c ac|d, H
2
SO
4
, are
su|tab|e ac|d cata|ysts.
40 m|nutes.
The equat|on for the dehydrat|on of ethano| to ethane |s shown |n F|gure 5.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
a|cehe|s
lxam|aer t|p
lu au elimiuatiou reactiou,
1 molecule 2 molecules.
lxam|aer t|p
wheu au alcohol is deh]drated the
atoms lost are.
au 0H group from oue caroou atom;
aud
au H atom from the adjaceut caroou
atom.
The douole ooud forms oetweeu these
two caroou atoms.
The dehydrat|on of cyc|ohexano| to cyc|ohexene |s shown |n F|gure 6. You may carry out
th|s react|on as part of your AS pract|ca| course.
F|gure 5 Dehydrat|on of ethano| to form ethene
h
2
0
C C
h
h
h
h
0h
h
h
2
S0
4
C C
h
h
h
h
+
Conc.
heat
F|gure 6 Dehydrat|on of cyc|ohexano| to form cyc|ohexene
C
C
C
C
C
C
h h
h
h
h
0h
h h
h
h
h
h
C
C
C
C
C
C
h h
h
h
h h
h
h
h
h h
8
F0
4
h
2
0
Cyclohexanol Cyclohexene
+
Conc.
heat
0cest|eas
1 Wr|te an equat|on for the react|on between ethano| and pentano|c ac|d. Name the
organ|c product formed.
2 Draw the d|sp|ayed formu|a for the product of the react|on between butan-2-o| and
ethano|c ac|d.
3 Butan-2-o| can be dehydrated us|ng concentrated phosphor|c ac|d, to produce three
poss|b|e a|kenes that are |somers. Draw the d|sp|ayed formu|ae and name the a|kenes
formed.
0ahydrat|on is au elimiuatiou reactiou
iu which water is removed from a
saturated molecule to make au
uusaturated molecule.
156
1.1 5 |atre6cct|ea te ha|eqeaea|kaaes
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
0escr|he the strcctcre, qeaera| fermc|a aa6 cses ef ha|eqeaea|kaaes.
0escr|he aa6 exp|a|a the aatcre ef the carhea-ha|eqea hea6 aa6 |ts scscept|h|||t te
acc|eeph|||c attack.

ka|eqeaea|kaaes
Ha|ogenoa|kanes are compounds |n wh|ch a ha|ogen atom has rep|aced at |east one of
the hydrogen atoms |n an a|kane cha|n.
ln the past, ha|ogenoa|kanes have been used as refr|gerants, aeroso| prope||ants,
degreas|ng agents and dry-c|ean|ng so|vents. However, they are no |onger used |n
aeroso|s because of the|r damag|ng effect on the ozone |ayer. We w||| d|scuss |n
further deta|| the env|ronmenta| effects of ha|ogenoa|kanes |n spread 2.2.7.
Ha|ogenoa|kanes are a|so |mportant |n organ|c synthes|s and can be used to prepare
many usefu| mater|a|s.
Ha|ogenoa|kanes have the genera| formu|a O
n
H
2n+1
, where represents the ha|ogen
atom.
Nam|aq the ha|eqeaea|kaaes
Ha|ogenoa|kanes conta|n on|y s|ng|e bonds, and the|r names are based on the a|kane
homo|ogous ser|es.
The pos|t|on of the ha|ogen on the cha|n |s |nd|cated.
lf there |s more than one ha|ogen atom |n the compound, they are ||sted a|phabet|ca||y.
'
. .'..
c ...
...
Tab|e 1
lxamp|e
For the ha|ogenoa|kane 3-bromo-2-ch|oropentane shown |n F|gure 2:
F|gure 1 Ha|ogenoa|kanes were once
used extens|ve|y |n aeroso| prope||ants
the name |s based on oen|ane.
there |s a o|omo group on the ||||d carbon and a c||o|o group on the second carbon.
the name |s 3-bromo-2-ch|oropentane.
C C C
h
h
C
h
Br
h
Cl
C
h
h
h
h
h
h
F|gure 2 3-bromo-2-ch|oropentane
157
keact||t ef the ha|eqeaea|kaaes
Ha|ogenoa|kanes conta|n a po|ar carbon-ha|ogen bond. The po|ar|ty ar|ses from the
d|fferent e|ec||onea||.|||es of the carbon and ha|ogen atoms.
Ha|ogen atoms are mo|e e|ectronegat|ve than carbon atoms.
The bonded e|ectron pa|r |s attracted more towards the ha|ogen atom than towards
the carbon atom.
The resu|t |s a oo|a| bond.
The d|agram |n F|gure 3 |||ustrates the po|ar|ty |n a mo|ecu|e of bromomethane.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
|atre6cct|ea te ha|eqeaea|kaaes
lxam|aer t|p
coudeusiug of a reactiou mixture to
eusure that the reactiou takes place
dr].
C F
C Br
C
C Cl
Folarity
decreases
- +
- +
- +
- +
F|gure 4 Po|ar|ty of the carbon-ha|ogen bond decreases down the group
C Br
h
h
h
+ -
F|gure 3 Po|ar|ty of the
carbon-ha|ogen bond |s shown
us|ng the symbo|s + and -
H
2
O, OH
-
and NH
3
.
Ha|ogenoa|kanes react w|th nuc|eoph||es |n subst|tut|on react|ons.
The nuc|eoph||e rep|aces the ha|ogen atom |n the ha|ogenoa|kane, form|ng a
compound conta|n|ng a d|fferent funct|ona| group.
k6re|s|s ef ha|eqeaea|kaaes
When ha|ogenoa|kanes react w|th an aqueous so|ut|on of hot hydrox|de |ons, a
nuc|eoph|||c subst|tut|on react|on occurs. The product of th|s react|on |s an a|coho|.
Aqueous sod|um hydrox|de |s common|y used, but any aqueous hydrox|de |s su|tab|e
for th|s react|on. Th|s react|on |s ca||ed hydro|ysis.
The equat|on for the hydro|ys|s of 1-ch|oropropane |s shown be|ow:
OH
3
OH
2
OH
2
O| aq} + OH
-
aq} OH
3
OH
2
OH
2
OH aq} + O|
-
aq}
1-ch|oropropane propan-1-o|
0cest|eas
1 Name the fo||ow|ng ha|ogenoa|kanes and draw the|r fu|| d|sp|ayed formu|ae:
(a} OH
3
OH
2
OH
2
OHO|OH
3
,

(b} OH
3
OH
2
OH
2
OH
2
OHOH
3
}OH
2
OH
2
O|,
(c} OH
3
OHBr}OH}OH
2
OH
3
,

(d} OH
3
OH
2
OH
2
OH
2
OH
2
.
2 Exp|a|n why a carbon-ch|or|ne bond |s po|ar.
3 Why are ha|ogenoa|kanes attacked by nuc|eoph||es?
The e|ectronegat|v|ty of the ha|ogens dec|eases down the group, resu|t|ng |n a decrease
lxam|aer t|p
Rememoer that a n0cIecphiIe is a
reactaut that attacks au electrou
electrou pair.
Nau] uucleophiles coutaiu au
electrouegative atom with a loue pair of
electrous.
Hydro|ys|s is a reactiou with water or
aqueous h]droxide ious that oreaks a
chemical compouud iuto two
compouuds.
158
1.1 6 keact|eas ef ha|eqeaea|kaaes
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
0escr|he the h6re|s|s ef ha|eqeaea|kaaes as a acc|eeph|||c schst|tct|ea react|ea.
0escr|he the mechaa|sm ef acc|eeph|||c schst|tct|ea |a the h6re|s|s ef pr|mar
ha|eqeaea|kaaes w|th het aceecs a|ka||.
lxp|a|a the rates ef pr|mar ha|eqeaea|kaae h6re|s|s |a terms ef the re|at|e hea6
eatha|p|es ef carhea-ha|eqea hea6s.
Ncc|eeph|||c schst|tct|ea react|eas
ln nuc|eophi|ic substitution, an atom or group of atoms |s rep|aced by a nuc|eoph||e an
e|ectron pa|r donor}.
Dur|ng hydro|ys|s, the ha|ogen atom |s rep|aced by the hydrox|de |on. The subst|tut|on
takes p|ace as fo||ows:
The hydrox|de |on, OH
-
, has a |one pa|r of e|ectrons. These are attracted and donated
n0c|eoo||||c attack.
The donat|on of the e|ectron pa|r |eads to the format|on of a new cova|ent bond
between the oxygen atom of the hydrox|de |on and the carbon atom.
move to the ha|ogen, form|ng a ha||de |on.
The mechan|sm for the nuc|eoph|||c subst|tut|on of 1-|odopropane by hydrox|de |ons |s
shown |n F|gure 1.
kate ef h6re|s|s ef pr|mar ha|eqeaea|kaaes
The rates of hydro|ys|s for d|fferent ha|ogenoa|kanes can be determ|ned us|ng the
fo||ow|ng exper|ment.
The ha|ogenoa|kane |s heated w|th aqueous s||ver n|trate, w|th ethano| added.
Water |n the m|xture behaves as the nuc|eophi|e.
The ethano| acts as a common so|vent, ensur|ng that the ha|ogenoa|kane and
aqueous s||ver n|trate m|x together and react.
As the hydro|ys|s react|on takes p|ace, ha||de |ons form. The fo||ow|ng equat|on shows
the hydro|ys|s of 1-ch|orobutane:
OH
3
OH
2
OH
2
OH
2
O|aq} + H
2
O|} OH
3
OH
2
OH
2
OH
2
OHaq} + H
+
aq} + O|
-
aq}
The aqueous s||ver n|trate, AgNO
3
aq} reacts w|th any ha||de |ons present, form|ng a
prec|p|tate of the s||ver ha||de. The equat|on be|ow shows the o|ec|o||a||on of s||ver
ch|or|de:
Ag
+
aq} + O|
-
aq} AgO|s}
C
h
C
2
h
5
h
0h
-
The carbon-iodine
bond breaks as the
two electrons in the
covalent bond move
to the iodine, lorming
an iodide ion,
-
.
Two electrons
lrom the hydroxide
ion, 0h
-
, lorm a
covalent bond with
the carbon atom.
+ -
F|gure 2 Our|y arrows are used to
represent the movement of e|ectron pa|rs
huc|aoph|||c subst|tut|on is a t]pe of
suostitutiou reactiou iu which a
uucleophile is attracted to au electrou-
douates a pair of electrous to form a
uew covaleut ooud.
C C
2
h
5
h
h
0h
-
C
2
h C
5
h0
h
h

-
+
- +
F|gure 1 Mechan|sm for nuc|eoph|||c subst|tut|on - the cur|y arrows represent
the movement of a pa|r of e|ectrons to form or break a cova|ent bond
159
The rate of hydro|ys|s can be found by ca|cu|at|ng 1/t|me taken for the prec|p|tate to
occur.
ln order to perform a contro||ed test, |t |s |mportant:
to use equa| amounts, |n mo|, of each ha|ogenoa|kane,
to use ha|ogenoa|kanes w|th the same cha|n |ength,
to use a water bath to ensure a constant temperature.
Th|s |s the procedure:
You measure each ha|ogenoa|kane |nto a separate test tube, wh|ch |s then p|aced |n a
water bath at 50 O.
You put a so|ut|on of ethano|, water and aqueous s||ver n|trate |nto another test tube.
Th|s test tube |s p|aced |n the same water bath.
Once a|| the tubes have reached the same temperature, you add equa| vo|umes of
each m|xture to each ha|ogenoa|kane.
You t|me how |ong |t takes for each prec|p|tate to form.
ka|eqeaea|kaae |rec|p|tate Ce|ecr ef prec|p|tate
.'..- ^.,, .'|- ,-.,||-
...- ^c,, .- ,-.,||-
...- ^',, ,-.. ,-.,||-
Tab|e 1 Formu|ae and co|ours of s||ver ha||des
|e|ar|t s hea6 eaerq
Two factors can affect the rate of hydro|ys|s:
|o|a|||,
so the O
+
atom shou|d attract the nuc|eoph||e most read||y and g|ve the fastest
react|on.
Sond en||a|o, - the carbon-|od|ne bond |s the weakest amongst the
ha|ogenoa|kanes, so the O- bond shou|d be broken the most eas||y and g|ve the
fastest react|on.
8ea6 eatha|p|es
The strengths of the carbon-ha|ogen bonds are shown |n Tab|e 2.
ln the hydro|ys|s of ha|ogenoa|kanes:
bond entha|py |s mo|e |mportant than bond po|ar|ty,
the rate of react|on |nc|eases
fastest} as the carbon-ha|ogen bond entha|py weakens.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
keact|eas ef ha|eqeaea|kaaes
F|gure 3 Hydro|ys|s of ha|ogenoa|kanes
|n a water bath |n the presence of
aqueous s||ver n|trate
8ea6 8ea6 eatha|p
/kI me|
-1
.' -4o
.. -`4`
.c -`o`
. -`4`
Tab|e 2 Bond entha|p|es for O-ha|ogen
0cest|eas
1
(a} nuc|eoph||e,
(b} subst|tut|on.
2
Wr|te a ba|anced equat|on for th|s react|on and name the a|coho| formed.
3 Out||ne the mechan|sm for the hydro|ys|s of 1-ch|oropentane by hydrox|de |ons.
1lluorobutane 1chlorobutane 1bromobutane 1iodobutane
Rate ol hydrolysis increases
Slowest Fastest
F|gure 4 Rates of hydro|ys|s of ha|ogenoa|kanes
lxam|aer t|p
Nau] exam questious ask ]ou to predict
what happeus to the rate of the reactiou
if the halogeuoalkaue is chauged.
Rememoer that the rate of reactiou
depeuds ou the streugth of the
caroou-halogeu ooud.
160
1.1 7 ka|eqeaea|kaaes aa6 the
ea|reameat
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .

aa6 |I|l.

0ct||ae the re|e ef 'qreea' chem|str |a m|a|m|s|aq 6amaqe te the ea|reameat h premet|aq
a|teraat|es te C|Cs.
ka|eqea-ceata|a|aq pe|mers
A number of po|ymers conta|n|ng ha|ogens can be manufactured, |nc|ud|ng po|yv|ny|
the trade name .
bonds |n the |ong-cha|ned po|ymer structure.
chem|ca| attack. Th|s chem|ca| |nertness, a|ong w|th |ts heat res|stance, e|ectr|ca|
|nsu|at|ng propert|es and non-st|ck qua||t|es, make PTFE an exce||ent cho|ce for coat|ng
pans or meta| surfaces to prevent chem|ca| attack. lt |s even used as na|| po||sh!
PvO |s used |n many var|ed app||cat|ons such as dra|np|pes, p|ast|c w|ndow frames,
sports equ|pment, ch||dren's toys and packag|ng.
PvO |s made from the po|ymer|sat|on of ch|oroethene as shown |n F|gure 2.
C C
F
F
F
F
C C
F
F n
F
F
Foly(tetralluoroethene),
FTFE
Tetralluoroethene
n
F|gure 1
C C
Cl
h
h
h
Foly(chloroethene)
oly(vinyl chloride), FvC
C C
h
Cl
h
h
Chloroethene
(vinyl chloride)
n
n
F|gure 2 The po|ymer|sat|on of ch|oroethene to produce
PvO, wh|ch has many uses
Thomas M|dg|ey was born |n Pennsy|van|a, SA, |n 1889. A|though he tra|ned as a
mechan|ca| eng|neer, he had a keen |nterest |n chem|stry. He deve|oped |e||ae||,| |ead
as a petro| add|t|ve to |mprove the combust|on of fue|s. He a|so worked extens|ve|y w|th
ha|ogenoa|kanes.
ln 1929, M|dg|ey was cha||enged by h|s emp|oyers to deve|op a non-tox|c refr|gerant for
gases used were ammon|a, ch|oromethane and su|fur d|ox|de. nfortunate|y, these had
been used |n domest|c refr|gerators w|th fata| consequences. The gases often |eaked, and
many peop|e were reported to have d|ed |n the|r s|eep as a resu|t of breath|ng |n the fumes.
M|dg|ey deve|oped F|eon
2
F
2
, an
ln 1930, M|dg|ey famous|y demonstrated that the gas was non-tox|c by |nha||ng a |ungfu|!
Expanded po|ystyrene foams used to conta|n OFO bubb|es. The OFOs were used as
b|ow|ng agents to expand the foam, but have now been rep|aced w|th other gases, such
as carbon d|ox|de. See a|so spread 2.4.8 for more deta||s.
lf on|y M|dg|ey had known the damage h|s d|scover|es wou|d create many years |ater!
Irech|e w|th C|Cs
The stab|||ty of OFOs ar|ses from the strength of the carbon-ha|ogen bonds w|th|n the|r
structures - a property that had |ed M|dg|ey to suggest the|r use as refr|gerants many
years before. ln 1973, two chem|sts, Row|and and Mo||na, began to |ook |nto the |mpact
of OFOs on the Earth's atmosphere. They d|scovered that OFOs rema|n stab|e unt|| they
reach the stratosphere, where they break down |n the presence of u|trav|o|et rad|at|on to
form ch|or|ne rad|ca|s. These ch|or|ne rad|ca|s are thought to cata|yse the breakdown of
the ozone |ayer. Ozone absorbs much of the u|trav|o|et rad|at|on from the Sun,
prevent|ng th|s rad|at|on from reach|ng the Earth's surface. Th|s dep|et|on of the ozone
|ayer has a||owed harmfu| v rad|at|on to reach the |ower atmosphere, |ncreas|ng the
preva|ence of sk|n cancers.
Dep|et|on of the ozone |ayer |s d|scussed |n greater deta|| |ater |n spread 2.4.5.
Ihe wa ferwar6 - a|teraat|es te C|Cs
OFOs were or|g|na||y deve|oped as refr|gerants, prope||ants, b|ow|ng agents and so|vents
for the dry-c|ean|ng |ndustry. OFOs now present research sc|ent|sts w|th a cha||enge -
However, HOFOs can st||| dep|ete the ozone |ayer. A|though the|r dep|et|ng effect |s on|y
about one-tenth or |ess than that of OFOs, ser|ous damage |s st||| be|ng caused. HOFOs
0teae-fr|ea6| pre6ccts
Refr|gerator gases based on hydrocarbons are
current|y be|ng deve|oped that cause no damage to
the ozone |ayer. You may have seen prope||ants
|abe||ed ozone-/||end|,. These often conta|n
hydrocarbons such as butane. A|though these do not
care!
C
Cl
F h
F
F|gure 4 R-22 OHO|F
2
} - the ma|n
HOFO used today as a refr|gerant,
but st||| an ozone dep|eter and set
to be phased out by 2030
F|gure 3 Thomas M|dg|ey, 'Father of
refr|gerator
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
ka|eqeaea|kaaes aa6 the ea|reameat
0cest|eas
1
non-st|ck coat|ngs on fry|ng
pans?
2 Po|ych|oroethene}, po|yv|ny|
ch|or|de}, PvO |s a po|ymer of
ch|oroethene. Draw a mo|ecu|e of
ch|oroethene and draw two
repeat un|ts of po|ych|oroethene}.
3 State two uses of PvO.
161
162
1.1 8 |erceataqe |e|6
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
|erferm ca|cc|at|eas te 6eterm|ae the perceataqe |e|6 ef a react|ea.
|erceataqe |e|6
When wr|t|ng a fu||y ba|anced chem|ca| equat|on, |t |s assumed that a|| of the reactants
w||| be converted |nto products. lf th|s were the case, then the y|e|d wou|d be 100%.
However, |n pract|ca| work, y|e|ds of 100% are rare|y obta|ned for var|ous reasons:
the react|on may be at equ|||br|um and may not go to comp|et|on
other s|de react|ons may occur, |ead|ng to by-products
the reactants may not be pure
some of the reactants or products may be |eft beh|nd |n the apparatus used |n the
exper|ment
resu|t |n the |oss of some of the
product.
The percentage y|e|d can be
ca|cu|ated to measure the success
of a |aboratory preparat|on.
% y|a|d =
actual amouut, iu mol, of product
____________________________
theoretical amouut, iu mol, of product
100
lxam|aer t|p
lf ]ou are uusure aoout au] terms here,
theu look oack at spreads 1.1.O, 1.1.7
aud 1.1.9. There are mau] worked
examples iu these spreads aud further
iuformatiou aoout amouut of suostauce
aud the mole.
A student prepared some ethano|c ac|d, OH
3
OOOH, by heat|ng ethano|,
O
2
H
5
OH, w|th an ox|d|s|ng agent.
The equat|on for the react|on |s shown be|ow:
OH
3
OH
2
OH + 2[O| OH
3
OOOH + H
2
O
The student used a m|xture of su|fur|c ac|d and potass|um d|chromate as the
ox|d|s|ng agent.
She reacted 9.20 g of ethano| w|th an excess of su|fur|c ac|d and potass|um
d|chromate.
The student obta|ned 4.35 g of ethano|c ac|d.
What |s the percentage y|e|d of ethano|c ac|d?
Answer
1 Oa|cu|ate the amount, |n mo|, of ethano| that was used:
amount of ethano|, n =
mass, m
_____________
mo|ar mass, /
=
9.20
46.0
= 0.200 mo|
2 s|ng the equat|on, ca|cu|ate the amount, |n mo|, of ethano|c ac|d product
expected.
|ook|ng at the equat|on, you can see that one mo|e of ethano| reacts to
produce one mo|e of ethano|c ac|d.
So, 0.200 mo| of ethano| shou|d react to g|ve 0.200 mo| of ethano|c ac|d.
Th|s |s the ||eo|e||ca| amount of ethano|c ac|d product, |n mo|.
3 F|nd the ac|0a| amount, |n mo|, of ethano|c ac|d product made |n the
exper|ment.
amount of ethano|c ac|d made, n =
m
/
=
4.35
60.0
= 0.0725 mo|
4 s|ng your answers from steps 1 and 3, ca|cu|ate the percentage y|e|d.
% y|e|d =
actua| amount, |n mo|, of product
theoret|ca| amount, |n mo|, of product
100 =
0.0725
0.200
100
= 36.25%
Worked example 1
163
0cest|eas
1 3.925 g of 2-ch|oropropane reacted w|th an excess of aqueous sod|um hydrox|de.
2.955 g of propan-2-o| was formed, as shown |n the equat|on be|ow.
OH
3
OHO|}OH
3
+ NaOH OH
3
OHOH}OH
3
+ NaO|
Oa|cu|ate the percentage y|e|d of propan-2-o|.
2 Ethano| reacts w|th ethano|c ac|d to produce an ester and water, as shown |n the
equat|on be|ow.
O
2
H
5
OH + OH
3
OOOH OH
3
OOOO
2
H
5
+ H
2
O
5.5 g of ethy| ethanoate |s produced from 4.0 g of ethano| and 4.5 g of ethano|c ac|d.
Oa|cu|ate the percentage y|e|d of ethy| ethanoate.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
|erceataqe |e|6
lxam|aer t|p
hotice the importauce of workiug iu
moles.
the mass of propau-1-ol used was
8.00 g, greater thau the mass of
methauoic acid used, 2.50 g. 8o it
appears the propau-1-ol is iu excess.
80t there are rcre moles of
methauoic acid. Although less mass
of methauoic acid was used, its molar
mass is also less.
You will oul] kuow this o] couvertiug
grams iuto moles.
ln some quest|ons you have to ca|cu|ate the amount, |n mo|, of each reactant
||m|t|ng reagent. The theoret|ca| amount, |n mo|, of product |s
ca|cu|ated based on the amount, |n mo|, of the ||m|t|ng reagent. Th|s worked
examp|e uses th|s pr|nc|p|e.
A student prepared propy| methanoate, HOOOOH
2
OH
2
OH
3
, from propan-1-o|,
OH
3
OH
2
OH
2
OH, and methano|c ac|d, HOOOH. The equat|on for the react|on |s:
OH
3
OH
2
OH
2
OH + HOOOH HOOOOH
2
OH
2
OH
3
+ H
2
O
The student reacted 3.00 g of propan-1-o| w|th 2.50 g of methano|c ac|d |n the
presence of a su|fur|c ac|d cata|yst. He was d|sappo|nted to obta|n on|y 1.75 g of
propy| methanoate.
What |s the percentage y|e|d of propy| methanoate?
Answer
1 Oa|cu|ate the amount, |n mo|, of each reagent.
There |s a prob|em.
the ||m|t|ng reagent and wh|ch |s |n excess.
|n Step 2.
amount of propan-1-o|, n =
mass, m
_____________
mo|ar mass, /
=
3.00
60.0
= 0.0500 mo|
amount of methano|c ac|d, n =
m
/
=
2.50
46.0
= 0.0543 mo|
Once we know the ||m|t|ng reagent, we use th|s for step 2.
2 s|ng the equat|on, ca|cu|ate the amount, |n mo|, of propy| methanoate
product expected.
The equat|on te||s us that one mo|e of propan-1-o| reacts to form one mo|e of
propy| methanoate.
So, 0.0500 mo| of propan-1-o| shou|d react to form 0.0500 mo| of propy|
methanoate.
The ||eo|e||ca| amount, |n mo|, of propy| methanoate product = 0.0500 mo|.
3 F|nd the ac|0a| amount, |n mo|, of propy| methanoate product made |n the
exper|ment.
amount of propy| methanoate made, n =
m
/
=
1.75
88.0
= 0.0199 mo|
4 s|ng your answers from steps 1 and 3, ca|cu|ate the percentage y|e|d.
% y|e|d =
actua| amount, |n mo|, of product
theoret|ca| amount, |n mo|, of product
100 =
0.0199
0.0500
100
= 39.8%
Worked example 2
A ||m|t|ng raagant is the suostauce iu a
164
1.1 9 ktem eceaem
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
etem eceaem,
precesses w|th a h|qh atem eceaem.
lxp|a|a that a66|t|ea react|eas hae aa atem eceaem ef 1, whereas schst|tct|ea
Carr ect ca|cc|at|eas te 6eterm|ae the atem eceaem ef a react|ea.
lxp|a|a that a react|ea ma hae a h|qh perceataqe |e|6 hct a |ew atem eceaem.
F|gure 1 Waste from chem|ca| synthes|s
|s often stored |n conta|ners for |ong
per|ods of t|me before be|ng sent to
lxam|aer t|p
lf au additiou reactiou produces a siugle
additiou product, the atom ecouom] is
100. AII of the reactaut molecules are
couverted iuto the desired product.
ktem eceaem
ln the prev|ous spread 2.2.8}, we d|scussed how percentage y|e|d |s used to assess the
oa|| of the
story. A react|on may not on|y produce the des|red product, but by-products as we||.
What do we do w|th the by-products?
By-products are often cons|dered as waste and have to be d|sposed of. Th|s |s cost|y
and poses potent|a| env|ronmenta| prob|ems.
By-products may be so|d on or used e|sewhere |n the chem|ca| p|ant. Th|s pract|ce |s
||ke|y to |ncrease |n the future, as we become |ncreas|ng|y concerned about preserv|ng
the Earth's resources and of m|n|m|s|ng waste.
Atom economy cons|ders not on|y the des|red product, but a|so a|| the by-products of
a|| the atoms
|nvo|ved. A react|on w|th a h|gh atom economy uses atoms w|th m|n|ma| waste.
We are now much more aware of our env|ronment. By us|ng
processes w|th a |||e| atom economy, chem|ca| compan|es can
|ed0ce the amount of waste produced. Th|s |s good news, espec|a||y
about 5-10% of the tota| expend|ture of a chem|ca| company goes
on waste treatment.
Ca|cc|at|aq atem eceaem
The react|on between propene and brom|ne |s shown |n F|gure 2. The des|red
product |s 1,2-d|bromopropane. Oa|cu|ate the atom economy.
To ca|cu|ate the atom economy you w||| need to:
ca|cu|ate the mo|ecu|ar mass of the des|red product,
d|v|de th|s by the sum of the mo|ecu|ar masses of a|| products.
ln th|s react|on, the des|red product |s the on|y product! So the atom economy |s
100%.
Worked example 1
F|gure 2 The react|on between propene and brom|ne
C C
C
h
h
h
h
h
h
Br
2
h C C C h
h
h
h
Br
h
Br
atom aconomy =
molecular mass of the desired product
sum of molecular masses of all products
100
165
ktem eceaem aa6 tpe ef react|ea
From the worked examp|es above, |t |s c|ear that the type of react|on used for a chem|ca|
process |s a major factor |n ach|ev|ng a h|gher atom economy.
Add|t|on react|ons have an atom economy of 100%.
React|ons |nvo|v|ng subst|tut|on or e||m|nat|on have an atom economy |ess than 100%.
Th|s |s not to say that we shou|d never carry out subst|tut|on or e||m|nat|on react|ons.
a|| the products of a
react|on.
lf the undes|red products are tox|c, then we have an even b|gger prob|em!
0cest|eas
1 2-|odopropane can be hydro|ysed us|ng aqueous sod|um hydrox|de to form the
product propan-2-o|. Wr|te a ba|anced equat|on for th|s react|on and ca|cu|ate the
atom economy.
2 The fo||ow|ng react|on was carr|ed out to produce a samp|e of but-2-ene.
OH
3
OH
2
OHOH}OH
3
OH
3
OH=OHOH
3
+ H
2
O
Oa|cu|ate the atom economy of the react|on.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
ktem eceaem
A student dec|des to prepare a samp|e of butan-1-o| by react|ng 1-bromobutane
w|th aqueous sod|um hydrox|de. The equat|on for the react|on |s g|ven |n F|gure 3.
Oa|cu|ate the atom economy of the react|on.
To ca|cu|ate the atom economy you w||| need to ca|cu|ate the mo|ecu|ar mass
of the des|red product and d|v|de th|s by the sum of the mo|ecu|ar masses of a||
products.
Mo|ecu|ar mass of des|red product: O
4
H
9
OH = 4 12.0} + 10 1.0} + 1 16.0}
= 74.0
A|| products: O
4
H
9
OH + NaBr
Mo|ecu|ar masses of a|| products = 74.0 + 23.0 + 79.9}
= 176.9
atom economy =
mo|ecu|ar mass of the des|red products
sum of mo|ecu|ar masses of a|| products
100 =
74.0
176.9
100
The react|on has an atom economy of 41.8%.
Th|s means the major|ty of the start|ng mater|a|s |s turned |nto waste.
Even |f the react|on proceeded w|th a 100% percentage y|e|d, more than ha|f
the mass of atoms used wou|d be wasted.
Worked example 2
F|gure 3 Preparat|on of butan-1-o| from 1-bromobutane
ha0h h C C C C
h
h
h
h
h
h
0h
h
h
haBr h C C C C
h
h
h
h
h
h
Br
h
h
1bromobutane Butan1ol
lxam|aer t|p
Nake sure ]ou show all of ]our
auswer wroug ]ou will still oe awarded
some marks provided that ]our method
is correct.
lxam|aer t|p
Rememoer that perceutage ]ield aud
atom ecouom] are differeut.
of couvertiug reactauts iuto products.
Atom ecouom] tells ]ou the proportiou
of desired products compared with all
the products formed.
166
1.1 10 |afrare6 spectrescep
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
!tate that ahserpt|ea ef |afrare6 ra6|at|ea cacses cea|eat hea6s te |hrate.
|6eat|f ahserpt|ea peaks |a aa |afrare6 spectrcm.
!tate that me6era hreatha|sers meascre ethaae| |ee|s h aaa|s|s cs|aq |afrare6
spectrescep.
|afrare6 ra6|at|ea aa6 me|ecc|es
A|| mo|ecu|es absorb |nfrared rad|at|on. Th|s absorbed energy makes bonds v|brate w|th
e|ther a stretch|ng or bend|ng mot|on, as shown |n F|gure 1.
F|gure 2 Schemat|c d|agram of an |nfrared spectrometer
Relerence cell
lor solvent only
Samle cell lor
solution ol samle
nlrared source
(electrically heated lilament)
haCl rism
(or dillraction
grating)
nlrared
detector
Chart recorder
Every bond v|brates at |ts own un|que frequency.
The amount of v|brat|on depends on:
the bond strength
the bond |ength
the mass of each atom |nvo|ved |n the bond.
Most bonds v|brate at a frequency between 300 and 4000 cm
-1
, |n the |nfrared part of
the e|ectromagnet|c spectrum.
The absorbed energ|es can be d|sp|ayed as an |nfrared spectrum. By ana|ys|ng th|s
spectrum, we can determ|ne deta||s about a compound's chem|ca| structure. ln
part|cu|ar, the spectrum |nd|cates the presence of funct|ona| groups |n the compound
under |nvest|gat|on.
ln a modern |nfrared spectrometer, a beam of |nfrared rad|at|on |s passed through a
samp|e of the mater|a| under |nvest|gat|on. Th|s beam conta|ns the fu|| range of
frequenc|es present |n the |nfrared reg|on. The mo|ecu|e absorbs some of these
frequenc|es and the emerg|ng beam |s ana|ysed to p|ot a graph of transm|ttance aga|nst
frequency. Th|s |s the |nfrared spectrum of the mo|ecu|e. The frequency |s measured
us|ng wa.en0moe|s, w|th un|ts of cm
-1
.
The C-h bond stretches
when it absorbs inlrared radiation.
The C-h bond bends
when it absorbs inlrared radiation.
C h
h
h
C
F|gure 1 Stretch|ng and bend|ng v|brat|ons resu|t|ng from the
absorpt|on of |nfrared rad|at|on
lxam|aer t|p
You will uot oe expected to draw this
diagram iu exams.
167
What 6ees the spectrcm |eek ||ke?
The mo|ecu|e's spectrum has a number of troughs, surpr|s|ng|y st||| ca||ed oea|s. Each
peak represents the absorbance of energy from |nfrared rad|at|on that causes the
v|brat|on of a part|cu|ar bond |n the mo|ecu|e under |nvest|gat|on.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
|afrare6 spectrescep
0cest|eas
1 What causes the bonds |n a
mo|ecu|e to v|brate?
2 Name the two ma|n types of
v|brat|ons of bonds caused by
|nfrared rad|at|on.
3 State two app||cat|ons for
|nfrared spectroscopy.
F|gure 3 A typ|ca| |nfrared spectrum show|ng absorpt|on peaks
1OO
5O
O
4OOO 8OOO 2OOO 15OO 1OOO 5OO
wavenumber/cm
1
The eak is characteristic ol a
vibration ol a articular grou
lxam|aer t|p
auswer ou the spectrum itself. lf ]ou do
this make sure that ]ou tell the
examiuer to look ou the spectrum with a
uote iu the auswer space. 0therwise the
examiuer might just thiuk that ]ou have
missed out the questiou.
lnrared specLroscopy has many everyday uses. lL is used exLensively in orensic science,
or example, Lo analyse painL ragmenLs rom vehicles in hiL-and-run oences. OLher
uses LhaL rely on inrared specLromeLry include.
lnrared specLromeLers are also used as one o Lhe main meLhods or LesLing Lhe breaLh
o suspecLed drunlen drivers or eLhanol.
Applications of infrared spectroscopy
F|gure 4 lnfrared spectra of the pure |||ega| drug hero|n b|ue} compared w|th that of an
unknown samp|e b|ack}. The samp|es match a|most perfect|y, |nd|cat|ng that the samp|e
conta|ns a h|gh percentage of hero|n. Spectra| ana|ys|s such as th|s can |dent|fy unknown
compounds |n m|xtures or from samp|es taken from c|oth|ng or equ|pment. Th|s techn|que |s
w|de|y used |n forens|c sc|ence
168
1.1 11 |afrare6 spectrescep: fcact|eaa|
qrecps
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .

ac|6.
We can use the |nformat|on generated from an |nfrared spectrum to |dent|fy the funct|ona|
groups |n a mo|ecu|e from a reference da|a s|ee|.
8ea6 |cact|eaa| qrecp Waeacmher /cm
-1

. ..'., -|-, ...\,. .. !```!```
.= .-',.-, -|.-, ...\,. .., -|-, .- !o4`!'`
.' .. ..,... .|' .' ... `o'``!``
' ...\,. .. `'`````` ,.-, ...,
'' -, .- `````'``
' ',..- ...-. ..'., ,'-. `````''` ,...,
Tab|e 1 Oharacter|st|c absorpt|ons for the funct|ona| groups requ|red |n AS/A2 chem|stry
At AS |eve| you on|y need to |dent|fy the presence of the fo||ow|ng funct|ona| groups b|ue
|n Tab|e 1}:
The O-H hydroxy|} group |n a|coho|s.
The O=O carbony|} group |n a|dehydes and ketones.
The OOOH carboxy|} group |n carboxy||c ac|ds.
You a|so need to be aware that most organ|c compounds produce a peak at
approx|mate|y 3000 cm
-1
due to absorpt|on by O-H bonds. You need to be carefu| that
you are not foo|ed |nto th|nk|ng that th|s |s an O-H absorpt|on peak.
k|cehe|s
The |nfrared spectrum of methano|, OH
3
OH, |s shown |n F|gure 1 be|ow.
lxam|aer t|p
Rememoer to use the iuformatiou giveu
iu the cata sheet iu ]our auswers. You
must quote values to help ]ou aual]se
the spectrum!
F|gure 1 lnfrared spectrum of methano|
1OO
5O
O
4OOO 8OOO 2OOO 15OO 1OOO 5OO
wavenumber/cm
1
Key eak
828O-85OOcm
1
The peak at 3230-3500 cm
-1
represents an O-H group |n a|coho|s.
169
k|6eh6es aa6 keteaes
The spectrum of propana|, OH
3
OHO, |s shown |n F|gure 2.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
|afrare6 spectrescep: fcact|eaa| qrecps
Here we have two character|st|c peaks:
The peak at 2500-3300 cm
-1
|s very broad and |nd|cates the presence of the O-H
group |n a carboxy||c ac|d.
The strong sharp peak at 1680-1750 cm
-1
represents the O=O group |n a carboxy||c
ac|d.
0cest|eas
1 An organ|c compound has an absorpt|on peak |n the |nfrared spectrum at 1700 cm
-1
.
There |s no peak at a wavenumber greater than 3000 cm
-1
.
What funct|ona| group must be present |n the compound?
2 State the approx|mate wavenumbers for the key |nfrared absorpt|ons for the fo||ow|ng
mo|ecu|es:
(a} pentan-2-o|, (b} 2-hydroxypentana|, (c} butano|c ac|d.
The peak at 1680-1750 cm
-1
represents a O=O bond |n a|dehydes and ketones.
Carhex||c ac|6s
The spectrum of propano|c ac|d, OH
3
OH
2
OOOH, |s shown |n F|gure 3.
1OO
5O
O
4OOO 8OOO 2OOO 15OO 1OOO 5OO
wavenumber/cm
1
Key eak
1G8O-175O cm
1
very broad
Key eak
25OO-88OO cm
1
F|gure 3 lnfrared spectrum of propano|c ac|d
1OO
5O
O
4OOO 8OOO 2OOO 15OO 1OOO 5OO
wavenumber/cm
1
Key eak
1G8O-175O cm
1
F|gure 2 lnfrared spectrum of propana|
170
1.1 12 Mass spectremetr
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
0ct||ae the ear| 6ee|epmeats |a mass spectremetr.
0ct||ae the cse ef mass spectremetr |a the 6eterm|aat|ea ef re|at|e |setep|c masses aa6 fer
|6eat|f|aq e|emeats.
|aterpret mass spectra ef e|emeats |a terms ef |setep|c ahca6aaces.
0ses ef mass spectremetr
Mass spectrometry |s a powerfu| too|.
lt can be used:
to |dent|fy unknown compounds,
to determ|ne the abundance of each |sotope |n an e|ement,
to ga|n further |nformat|on about the structure and chem|ca| propert|es of mo|ecu|es.
Mass spectrometry has a w|de range of |ndustr|a| and med|ca| app||cat|ons.
Examp|es of |ts use today |nc|ude:
mon|tor|ng the breath of pat|ents dur|ng surgery wh||st under anaesthet|c,
detect|ng banned substances such as stero|ds |n ath|et|cs,
ana|ys|ng mo|ecu|es |n space,
detect|ng traces of tox|c chem|ca|s |n contam|nated mar|ne ||fe.
kew a mass spectremeter werks
A mass spectrometer determ|nes the mass of a mo|ecu|e or |sotope by measur|ng the
mass-to-charge rat|o of |ons. A|though mass spectrometers d|ffer cons|derab|y |n the|r
operat|on, the same bas|c processes occur |ns|de the |nstrument.
The samp|e |s |ntroduced v|a a samp|e |n|et.
F|gure 1 Franc|s Aston. Aston |mproved
Thomson's ear|y mass spectrometer to
obta|n spectra w|th h|gher reso|ut|on. He
des|gned a mass soec||o|ao|, wh|ch
separated the |ons present |n a samp|e by
the|r mass. A|though Aston's work was
d|srupted by the outset of the F|rst Wor|d
War, he was awarded the Nobe| Pr|ze |n
Ohem|stry |n 1922 for h|s study of
natura||y occurr|ng |sotopes
F|gure 2 ||fe on Mars? The Beag|e 2
space probe carr|ed a mass spectrometer
as one of |ts |nstruments to |dent|fy
e|ements |n rock samp|es. nfortunate|y,
contact w|th Beag|e 2 was |ost wh||e
descend|ng to Mars on 25th December
2003 and the spectrometer was never
ab|e to ana|yse the p|anet! No-one knows
whether Beag|e 2 successfu||y |anded on
Mars or just crashed
specLromeLer in Lhe early parL o Lhe LwenLieLh cenLury.
paLh.
ln 1906, 1homson was awarded Lhe Nobel lrize in lhysics or his worl. 1homson also
carried ouL experimenLs in which he showed LhaL an aLom conLains elecLrons. ou can
1he riLish chemisL and physicisL lrancis AsLon carried ouL deLailed worl on Lhe mass
specLra o chemical elemenLs. lnspired by 1homson, AsLon wenL on Lo discover LhaL a
sample o neon conLains Lwo dierenL isoLopes,
20
Ne and
22
Ne. 1he exisLence o sLable
isoLopes o Lhe same elemenL was an imporLanL discovery - made possible by Lhe mass
specLromeLer.
lurLher developmenLs ollowed. ln 1920, A.|. LempsLer developed a magneLic
insLrumenLs based on LempsLer's model are sLill used exLensively Loday.
The history of mass spectrometry
171
Samp|e mo|ecu|es are converted |nto |ons by an |on|sat|on source.
Methods of |on|sat|on |nc|ude e|ectron |mpact, chem|ca| |on|sat|on, use of an
e|ectrospray and even |asers. These |on|sat|on sources vary depend|ng on the type of
|nstrument be|ng used.
The |ons are prope||ed |nto a mass ana|yser.
The |ons are separated accord|ng to the|r mass-to-charge rat|o. Methods of
||me o/ measurement of
how |ong |t takes for |ons of d|fferent mass to reach the detector}.
The |ons are detected. A mass spectrum |s generated by computer software and
d|sp|ayed on a screen or pr|nted.
Mass spectra ef e|emeats
One of the most |mportant uses of mass spectrometry |s to determ|ne the |sotopes
proport|ons of each |sotope |n the e|ement be|ng |nvest|gated. You can then ca|cu|ate the
|e|a||.e a|om|c mass of the e|ement.
A mass spectrum |s a graph show|ng re|at|ve or percentage abundance on the ,-ax|s
and mass : charge rat|o on the x-ax|s.
The mass to charge rat|o |n a|| mass spectra |s shown as m/z.
m |s the mass z |s the charge on the |on.
The mass spectrum of a samp|e of magnes|um |s shown |n F|gure 4.
Ke featcres ef the spectrcm
There are three peaks |n the spectrum, so there are |||ee |sotopes of magnes|um.
The |e|||s of the peaks g|ves the |e|a||.e ao0ndances of the |sotopes |n the samp|e.
These are g|ven as percentages |n F|gure 4.
The spectrum te||s us that:
79% |s magnes|um-24
10% |s magnes|um-25
11% |s magnes|um-26.
Re|at|ve atom|c mass =
24 79} + 25 10} + 26 11}
____________________________
100
= 24.32
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
Mass spectremetr
/
24 25 2G
7O
1O
11
F|gure 4 The mass spectrum of
magnes|um
0cest|eas
1 m/z = 6 and
had an abundance of 7.4%, the second peak was at m/z = 7 and had an abundance
of 92.6%.
2 A samp|e of stront|um has four |sotopes as shown |n Tab|e 1. Sketch a mass
spectrum for the stront|um samp|e and ca|cu|ate |ts re|at|ve atom|c mass.
|ea |erceataqe ahca6aace
o4
'
-
!
oo
'
-
'
o
'
-

oo
'
-
o`
Tab|e 1
Stront|um's four |sotopes
F|gure 3 Mass spectrometry - samp|e |s
|njected and |ts spectrum d|sp|ayed on
screen
lxam|aer t|p
lf ]ou are uusure what to do here, look
worked examples to show how relative
atomic mass cau oe calculated from
isotopic aouudauces.
Take care with uuits - relative atomic
mass doesu't have au]!
172
1.1 13 Mass spectremetr |a erqaa|c
chem|str
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
0se the me|ecc|ar |ea peak |a aa erqaa|c me|ecc|e's mass spectrcm te 6eterm|ae |ts me|ecc|ar
mass.

a spectra| 6atahase.
Mass spectremetr aa6 me|ecc|es
When an organ|c compound |s p|aced |n a mass spectrometer, some mo|ecu|es |ose an
e|ectron and are |on|sed. The resu|t|ng pos|t|ve |on |s ca||ed the mo|ecu|ar ion and |s
g|ven the symbo| M
+
.
Severa| d|fferent methods can be used for |on|sat|on but e|ectron |mpact |s the o|dest and
best estab||shed method. ln e|ectron |mpact, the mo|ecu|es be|ng tested are bombarded
w|th e|ectrons. lf an e|ectron |s d|s|odged from a mo|ecu|e, a pos|t|ve |on |s formed. W|th
ethano|, a O
2
H
5
OH mo|ecu|e |s |on|sed to form the mo|ecu|ar |on, O
2
H
5
OH
+
.
O
2
H
5
OH + e
-
O
2
H
5
OH
+
+ 2e
-
mo|ec0|a| |on
The mass of the |ost e|ectron |s neg||g|b|e.
The mo|ecu|ar |on has a mo|ecu|ar mass equa| to the mo|ecu|ar mass of the compound.
Th|s mo|ecu|ar |on can be detected and ana|ysed.
Excess energy from the |on|sat|on process can be transferred to the mo|ecu|ar |on,
mak|ng |t v|brate. Th|s causes bonds to weaken and the mo|ecu|ar |on can sp||t |nto
p|eces by fragmentation.
Fragmentat|on resu|ts |n a pos|t|ve fragment |on and a neutra| spec|es.
A poss|b|e fragmentat|on of the ethano| mo|ecu|ar |on wou|d be:
O
2
H
5
OH
+
OH
3
+ OH
2
OH
+
/|amen| |on
Fragment |ons are often broken up further |nto sma||er fragments.
The mo|ec0|a| |on and /|amen| |ons are detected |n the mass spectrometer.
The mo|ecu|ar |on, M
+
, produces the peak w|th the h|ghest m/z .a|0e |n the mass
spectrum. H|gh-reso|ut|on mass spectrometry can produce a spectrum w|th extreme|y
prec|se va|ues for M
+
, mak|ng accurate mo|ecu|ar mass determ|nat|on re|at|ve|y easy.
Me|ecc|ar mass 6eterm|aat|ea
The mo|ecu|ar mass of a mo|ecu|e can be determ|ned
us|ng mass spectrometry by |ocat|ng the M
+
peak. The
mass spectrum of ethano| |s shown |n F|gure 1.
The mo|ecu|ar |on peak |s |ocated at a m/z rat|o of 46.
Th|s |nd|cates that the mo|ecu|ar mass of the mo|ecu|e |s
46. The other peaks |n the spectrum are a resu|t of
fragmentat|on.
lxam|aer t|p
lu the mass spectrum, ]ou ma] see a
small peak, oue uuit oe]oud the
molecular iou, N
+
, peak. This is ofteu
referred to as the N+1 peak. The N+1
peak arises from the preseuce of the
isotope caroou-18, which makes up
1.11 of all caroou atoms. Dou't oe
fooled iuto thiukiug that this is the N
+

iou.
1OO
8O
GO
4O
2O
O
1O 15 2O 25 8O 85 4O 45
/
M eak at 4G. C
2
h
5
0h
F|gure 1 Mass spectrum of ethano|
No|acu|ar |on, N
+
is the positive iou
formed iu mass spectrometr] wheu a
molecule loses au electrou.
Fragmantat|on is the process iu mass
spectrometr] that causes a positive iou
to split iuto pieces, oue of which is a
positive fragmeut iou.
173
|raqmeatat|ea patteras
Mass spectrometry can be used to determ|ne the structure of an unknown compound
and, |n many cases, g|ve |ts prec|se |dent|ty.
A|though the mo|ecu|ar |on peak of two |somers w||| have
the same m/z va|ue, the fragmentat|on patterns w||| be
d|fferent.
Each organ|c compound produces a un|que mass
The mass spectra of two structura| |somers of O
5
H
12
,
pentane and 2-methy|butane, are shown |n F|gure 2. Each
spectrum has a mo|ecu|ar |on peak at m/z = 72 for O
5
H
12
+
.
However, the fragmentat|on patterns are very d|fferent.
A|though mass spectra can be ana|ysed by s|mp|y v|ew|ng
the spectra, modern mass spectrometers are often ||nked
to a spectra| database. When a mass spectrum for an
unknown samp|e |s produced, the spectra| database |s
scanned automat|ca||y unt|| a perfect match |s found. Th|s
unknown compound.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
Mass spectremetr |a erqaa|c chem|str
1OO
8O
GO
4O
2O
O
1O 15 2O 25 8O 85 4O 45
/
75 5O 55 GO G5 7O
Fentane
1OO
8O
GO
4O
2O
O
1O 15 2O 25 8O 85 4O 45
/
75 5O 55 GO G5 7O
2Methylbutane
0cest|eas
1 Wr|te a ba|anced equat|on show|ng the |on|sat|on of the
fo||ow|ng mo|ecu|es to form the mo|ecu|ar |on. ln each
case, state the ||ke|y m/z va|ue for the mo|ecu|ar |on
peak:
(a} propan-1-o|,
(b} butane,
(c} octane.
2 ln the spectra of compounds A and B |n F|gure 3,
|dent|fy the m/z va|ue for each mo|ecu|ar |on peak.
F|gure 3 Spectra A and B
F|gure 2 Mass spectra of the
|somers of O
5
H
12
, pentane and
2-methy|butane
1OO
8O
GO
4O
2O
O
1O 15 2O 25 8O 85 4O 45
/
75 5O 55 GO G5 7O
A
8O 85 OO O5 1OO
1OO
8O
GO
4O
2O
O
1O 15 2O 25 8O 85 4O 45
/
75 5O 55 GO G5 7O
B
8O 85 OO O5 1OO
174
1.1 14 Mass spectremetr:
fraqmeatat|ea patteras
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
!cqqest the |6eat|t ef the ma[er fraqmeat |eas |a a q|ea mass spectrcm.
0se me|ecc|ar |ea peaks aa6 fraqmeatat|ea peaks te |6eat|f strcctcres.
|6eat|f|aq fraqmeat |eas
When |ook|ng at a mass spectrum, fragment peaks appear a|ongs|de the more |mportant
mo|ecu|ar |on peak. However, these fragment peaks g|ve |nformat|on about the structure
of the compound.
Even w|th s|mp|e compounds, |t |s often |mposs|b|e to |dent|fy every peak |n the mass
Oommon peaks for a|ky| |ons are shown |n Tab|e 1.
m/r a|ce |ess|h|e |6eat|t
ef fraqmeat |ea
!' .'
`
-
`' .
`
'
'
-
4` .
`
'

-
' .
4
'
'
-
Tab|e 1 m/z va|ues for common a|ky| |ons
ln the mass spectrum for an a|coho|, you w||| often see a peak w|th an m/z va|ue of 17.
Th|s |s due to the OH
+
|on and corresponds to the -OH group |n the a|coho|. Some of the
rearrangements - you w||| not be expected to know these!
As we|| as be|ng used to |dent|fy the mo|ecu|ar mass of a mo|ecu|e, a mass spectrum
can a|so be used to work out some of the mo|ecu|e's structura| deta||. An unknown
a|kane has produced the mass spectrum shown |n F|gure 1. Some of the peaks have
been |abe||ed w|th the m/z rat|o.
lxam|aer t|p
lu examiuatious feel free to draw or
write uotes ou the spectra provided for
aual]sis. This is good techuique aud will
help ]ou solve proolems.
/
1OO
8O
GO
4O
2O
O
1O 2O 8O 4O 5O GO 7O 8O OO
57.
could be C
4
h
O
8G.
M molecular ion eak
Molecular mass is 8G
48.
could be C
8
h
7
2O.
could be C
2
h
5
F|gure 1 Mass spectrum for an unknown a|kane
175
The mass spectrum shown |n F|gure 2 has been produced from hexane. The equat|ons
|n F|gure 2 |||ustrate how the mo|ecu|ar |on cou|d be fragmented to form fragment |ons
w|th m/z va|ues of 57 and 43.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
Mass spectremetr:
fraqmeatat|ea patteras
0cest|eas
1 The spectrum |n F|gure 4 on the r|ght has been
produced from the a|kene pent-1-ene.
Suggest the |ons respons|b|e for the peaks |abe||ed A, B
and C.
2 F|gure 5 be|ow shows the mass spectrum of an a|kane.
(a} se the spectrum to |dent|fy the mo|ecu|ar |on peak
and hence the mo|ecu|ar mass and mo|ecu|ar
formu|a of the compound.
(b} The mo|ecu|e |s branched w|th one methy| group
attached to the ma|n cha|n at carbon two. Draw the
ske|eta| formu|a for th|s a|kane.
(c} Draw structures for the fragment |ons represented
by the peaks w|th m/z va|ues of 43, 57 and 71.
Ch
8
Ch
2
Ch
2
+
C
8
h
7
C C C C C C
h
h
h
h
h
h
h
h
h
h
h
h
h
h
+
+
Fragment ion
/ = 48
heutral
secies
0etected and shown
as eak in sectrum
Bond
breaks
Ch
8
Ch
2
Ch
2
Ch
2
+
C
2
h
5 C C C C C C
h
h
h
h
h
h
h
h
h
h
h
h
h
h
Bond
breaks
+
+
Fragment ion
/ = 57
heutral
secies
0etected and shown
as eak in sectrum
1O 15 2O 25 8O 85 4O 45 75 5O 55 GO G5 7O
/
1OO
8O
GO
4O
2O
O
k
8
6
F|gure 3 Mass spectrum of myog|ob|n.
Sc|ent|st exam|n|ng the mass spectrum of
myog|ob|n, the oxygen-storage prote|n of
red musc|e. The spectrum obta|ned from
the mass spectrometer |s d|sp|ayed on
the computer screen used for prote|n
ana|ys|s at Oxford n|vers|ty F|gure 2 Equat|ons exp|a|n|ng how some of the peaks ar|se |n the mass spectrum for hexane
F|gure 4 Mass spectrum of pent-1-ene
1O 2O 8O 4O 5O GO 7O
/
1OO
8O
GO
4O
2O
O
8O
F|gure 5 Mass spectrum of an a|kane
176
1.1 15 keact|ea mechaa|sms
8, t|e ea4 cf t||s sprea4, ,ca s|ca|4 |e a||e tc . . .
0escr|he the three cemmea mechaa|sms rec|re6 fer k! chem|str.
k! mechaa|sms
There are |||ee mechan|sms requ|red |n n|t F322 Oha|ns, Energy and Resources. You
shou|d be ab|e to draw and exp|a|n these mechan|sms and suggest a mechan|sm for
s|m||ar or unfam|||ar examp|es. You w||| be requ|red to produce mechan|sms for:
the react|on of an a|kane w|th a ha|ogen
the react|on of an a|kene w|th an e|ectroph||e
the react|on of a ha|ogenoa|kane w|th a nuc|eoph||e.
k|kaaes - ra6|ca| schst|tct|ea
A|kanes take part |n |ad|ca| s0os|||0||on w|th ha|ogens. ln exams, the react|on of o|om|ne
or c||o||ne w|th me||ane |s the one tested most often. However, you cou|d be tested on
the react|on of a ha|ogen w|th a |onger-cha|n a|kane, or even a cyc|oa|kane.
Descr|be, w|th the a|d of su|tab|e equat|ons, the mechan|sm for the react|on
between methane and brom|ne |n the presence of u|trav|o|et rad|at|on.
Answer
Ba|anced equat|on: OH
4
+ Br
2


OH
3
Br + HBr
|n|||a||on
radica|s are formed.
|trav|o|et rad|at|on prov|des the energy to break the cova|ent bond |n a
brom|ne mo|ecu|e, Br-Br. The bond breaks by .
ln|t|at|on: Br
2
2Br
||ooaa||on
ln the second stage, the products of the react|on are made.
Propagat|on: Br + OH
4
OH
3
+ HBr
OH
3
+ Br
2
OH
3
Br + Br
Not|ce the numbers of rad|ca|s are the same on each s|de of the equat|ons.
A brom|ne rad|ca| |s regenerated |n the second propagat|on step.
Brom|ne rad|ca|s cata|yse the propagat|on stage. A|though they are |nvo|ved |n
the react|on steps, they are no| used up |n the overa|| react|on.
7e|m|na||on
Term|nat|on: OH
3
+ Br OH
3
Br
Br + Br Br
2
OH
3
+ OH
3
O
2
H
6
Further subst|tut|on react|ons can take p|ace, as the bromoa|kane product can
react w|th further brom|ne rad|ca|s. A m|xture of products |s produced conta|n|ng
OH
3
Br, OH
2
Br
2
, OHBr
3
and OBr
4
.
Worked example
lxam|aer t|p
You must oe aole to draw each of these
mechauisms. You must also oe aole to
suggest mechauisms for similar or
uufamiliar examples.
Nechauisms are alwa]s oeiug asked ou
exam papers. You ueed to oe aole to
draw out the mechauisms showu ou
this douole-page spread. You must oe
aosolutel] precise with au] curl]
arrows.
A mechauism is t]picall] worth four
marks, aud if ]ou are luck], there ma]
oe two ou the paper - eight eas] marks
for those who have oeeu oothered to
learu them.
A rad|ca| is a species with au uupaired
electrou.
177
k|keaes - e|ectreph|||c a66|t|ea
A|kenes take part |n e|ec||oo||||c add|||on react|ons w|th e|ectrophi|es such as ch|or|ne,
brom|ne or hydrogen ha||des. ln exams, the react|on between o|om|ne or |,d|oen
o|om|de and e||ene |s tested most often. However, a|kenes w|th |onger carbon cha|ns or
cyc|oa|kenes cou|d be used w|th any ha|ogen, hydrogen ha||de or re|ated compound.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
keact|ea mechaa|sms
0cest|eas
1 Descr|be, w|th the a|d of
d|agrams, the mechan|sms for
the fo||ow|ng react|ons:
(a} ethane and ch|or|ne |n
u|trav|o|et rad|at|on.
(b} 1-|odobutane and hydrox|de
|ons.
(c} but-2-ene and brom|ne.
Descr|be, w|th the a|d of su|tab|e d|agrams, the mechan|sm for the react|on
between ethene and ch|or|ne.
Answer
ln th|s type of react|on the ha|ogen adds ac|oss the doub|e bond as shown |n
F|gure 1.
Ba|anced equat|on: O
2
H
4
+ O|
2
O
2
H
4
O|
2
Worked example
F|gure 1 The e|ectroph|||c add|t|on mechan|sm
C C
h
h h
h
Cl
Cl
C C
h
h
Cl
h
h
Cl
C C
h
h h
Cl
h
Cl
A carbocation
is lormed
when Cl
2
aroaches, the Cl-Cl bond becomes olar. A air ol electrons llows lrom the double bond
to the slightly ositive Cl
+
and a bond lormed.
1,2dichloroethane
-
+
ka|eqeaea|kaaes - acc|eeph|||c schst|tct|ea
Ha|ogenoa|kanes take part |n n0c|eoo||||c s0os|||0||on react|ons w|th nuc|eophi|es such
as OH
-
or H
2
O. ln exams, the react|on between |,d|ox|de |ons and any ha|ogenoa|kane
|s ||ke|y to be tested.
A nuc|aoph||a is au electrou pair douor.
Aqueous hydrox|de |ons, OH
-
, react w|th ch|oromethane |n a nuc|eoph|||c
subst|tut|on react|on. Descr|be, w|th the a|d of su|tab|e d|agrams, the mechan|sm
for th|s react|on.
Answer
ln th|s type of react|on the nuc|eoph||e OH
-
}

attacks the back of the carbon
atom, donat|ng an e|ectron pa|r, as shown |n F|gure 2. A new bond |s formed and
the carbon-ha|ogen bond breaks.
Ba|anced equat|on: OH
3
O| + OH
-
OH
3
OH + O|
-
Worked example
F|gure 2 The nuc|eoph|||c subst|tut|on mechan|sm
0h
-
C h h0
h
h
C Cl h
h
h
+ Cl
-
+ -
The nucleohile attacks the back ol the carbon atom donating an electron air.
This causes a new bond to lorm and the carbon halogen bond to break.
Au a|actroph||a is au electrou pair
acceptor.
1.1 k|cehe|s aa6 ha|eqeaea|kaaes scmmar
178

farbex||c
ac|d
0|st|| kef|ax
kef|ax
hdre|s|s w|th Na0h(aq}
kef|ax
Nac|eeph|||c sabst|tat|ea
hdregea ha||des
f|ectreph|||c add|t|ea
heat w|th
ac|d cata|st
f||m|aat|ea
5team aad
ac|d cata|st
heat
hdrat|ea
e keteae Ne react|ea
ha|egeaea|kaaes
farbex||c ac|d
aad ac|d cata|st
heat
fster|f|cat|ea
flfs were ased as aerese|s,
refr|geraats aad |a
a|r cead|t|ea|ag as the
hare |ew tex|c|t
aad |ew react|r|t
ladastr|a|| ethaae| |s
made b hdrat|ea
ef etheae er b
fermeatat|ea ef sagars
kaaes
fsters
| 0|st||| kef|ax
0x|dat|ea as|ag ac|d|f|ed k
2
fr
2
0
I
|cehe|s - |rca4 0 N a|scrpt|ca at 111-11cm
-1
farbea|s - strcaq C 0 a|scrpt|ca at 111-1I1cm
-1
farbex||c ac|ds - strcaq C 0 a|scrpt|ca at 111-1I1cm
-1
aa4 er, |rca4 0-N a|sacrpt|ca at 11-1111cm
-1
lafrared
lr|mar a|cehe| 5eceadar a|cehe| r Ie t|ar a|cehe|
|keaes
kef|
e |dehde
179
1 Draw the fu|| structura| formu|a for:
(a} 2-bromopentane, (b} propan-2-o|,
(c} hexane-1,2-d|o|, (d} 2-ch|orohexan-3-o|.
2 There are two |ndustr|a| methods for the preparat|on of
ethano| - the fermentat|on of g|ucose and the d|rect
hydrat|on of ethene.
(a} Wr|te an equat|on for the preparat|on of ethano| from
g|ucose.
(b} Why does fermentat|on produce a max|mum ethano|
concentrat|on of 15%?
(c} State two advantages and two d|sadvantages of d|rect
hydrat|on compared w|th fermentat|on.
3 (a} What do you understand by the term .o|a|||||,?
(b} Why are the a|coho|s |ess vo|at||e than a|kanes of
s|m||ar mo|ecu|ar mass?
4 A|coho|s are so|ub|e |n water due to the|r ab|||ty to form
hydrogen bonds w|th water mo|ecu|es.
Draw a d|agram to show the hydrogen bond|ng between
water and a mo|ecu|e of propan-1-o|.
5 O
4
H
10
O has four structura| |somers that are a|coho|s.
(a} Draw the structures of these four structura| |somers
and c|ass|fy each as pr|mary, secondary or tert|ary.
(b} For |} one pr|mary, ||} one secondary and |||} one
tert|ary a|coho| from 5a}, descr|be the react|on, |f any,
}. Name
the organ|c products of each react|on.
6 (a} Wr|te a ba|anced equat|on for the react|on between
ethano| and butano|c ac|d.
(b} Name the organ|c product formed.
(c} G|ve a name for the type of react|on tak|ng p|ace and
|dent|fy the cata|yst for the react|on.
7 G|ve |wo uses of ha|ogenoa|kanes.
8 The hydro|ys|s of a bromoa|kane w|th hot aqueous a|ka|| |s
an examp|e of nuc|eoph|||c subst|tut|on. Exp|a|n the term
n0c|eoo||||c s0os|||0||on.
9 (a} Wr|te a ba|anced equat|on for the react|on of
2-bromopropane w|th aqueous hydrox|de |ons.
(b} What wou|d happen to the rate of the hydro|ys|s
react|on |f 2-bromopropane were rep|aced w|th
2-|odopropane? Exp|a|n your answer.
10 Descr|be the mechan|sm for the hydro|ys|s react|on that
takes p|ace between 3-ch|oropentane and aqueous
hydrox|de |ons. se cur|y arrows to show the mechan|sm.
11 se of OFOs has been dec||n|ng due to concern over the
poss|b|e effects on the env|ronment. lt |s thought that th|s
damage |s a resu|t of a ||ght-cata|ysed rad|ca| process
|nvo|v|ng ch|or|ne rad|ca|s.
(a} State one poss|b|e type of damage caused by OFOs to
the env|ronment.
(b} Exp|a|n what |s meant by a |ad|ca|.
(c} G|ve an equat|on for the format|on of a rad|ca| from the
2
F
2
.
12 Oompound A |s a hydrocarbon w|th a re|at|ve mo|ecu|ar
mass of 56. Oompound A conta|ns 85.63% carbon by
mass. Oompound A reacts w|th hydrogen brom|de to form a
s|ng|e monosubst|tuted compound B. Oompound B reacts
w|th hot aqueous sod|um hydrox|de to produce an a|coho|,
C. A|coho| C reacts w|th ethano|c ac|d |n the presence of an
ac|d cata|yst to form a sweet-sme|||ng ester D.
ldent|fy compounds A-D, show|ng d|sp|ayed formu|ae for
each structure.
13 The ha|ogenoa|kane A, O
4
H
9
Br, reacts w|th aqueous
sod|um hydrox|de to produce a|coho| B, O
4
H
9
OH. A|coho|
B reacts w|th concentrated phosphor|c ac|d to produce
water and a m|xture of three |somer|c a|kenes, C, D and E.
(a} Draw the four structura| |somers of O
4
H
9
Br.
(b} ldent|fy A, B, C, D and E, g|v|ng the|r fu|| d|sp|ayed
formu|ae.
(c} Wr|te an equat|on for the react|on between the
ha|ogenoa|kane A and aqueous sod|um hydrox|de.
State the type of react|on tak|ng p|ace.
(d} ln the react|on sequence above, what |s the funct|on of
the phosphor|c ac|d?
(e} Descr|be a chem|ca| test to show the presence of an
a|kene.
(f} lf the ha|ogenoa|kane A were a ch|oroa|kane, what
d|fference wou|d there be |n the rate of react|on w|th
aqueous sod|um hydrox|de? Exp|a|n your answer.
14 A student ana|ysed a compound us|ng |nfrared
spectroscopy and mass spectrometry. He found that the
compound gave a strong sharp lR absorbance at
1740 cm
-1
and peaks at m/z va|ues of 15, 29 and 72. The
compound had the fo||ow|ng compos|t|on by mass:
O, 66.63%, H, 11.18%, O, 22.19%.
(a} Oa|cu|ate the emp|r|ca| formu|a of the compound.
(b} What |nformat|on can the student ga|n from the
|nfrared absorbance?
(c} What |nformat|on |s g|ven by the peaks |n the mass
spectrum at 15 and 29?
(d} The mo|ecu|ar |on |s respons|b|e for the peak at
m/z = 72. se th|s |nformat|on and the emp|r|ca| formu|a
to deduce the mo|ecu|ar formu|a of the compound.
(e} Draw the ske|eta| formu|a for two poss|b|e structures of
the compound.
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
|ract|ce cest|eas
180
1 This question is about two alcohols, ethanol and
propan-2-ol, CH
3
CH(OH)CH
3
.
(a) Ethanol can be Iormed by Iermentation oI glucose,
C
6
H
12
O
6
.
(i) Write a balanced equation, including state symbols,
Ior the Iormation oI ethanol by Iermentation. |2|
(ii) Eermentation only occurs in the presence oI yeast.
State two other essential conditions. |2|
(iii) How would you know when Iermentation oI
glucose is complete? |1|
(b) Propan-2-ol can be Iormed by the hydration oI an
alkene in the presence oI a catalyst.
(i) Suggest a suitable catalyst Ior this reaction. |1|
(ii) This is an electrophilic addition reaction. What is
meant by the term electrophile? |1|
(c) A mechanism Ior the reaction in (b) is shown below.

Ch
8
h
+
C
h
h
h C
0
h h
8Iap 8
Ch
8
h C
h
h
h C
0
h
+ h
+
8Iap 1
Ch
8
C
h
C
h
h
8Iap Z
Ch
8
h
+
C C
h
h
h
h
+
h
0
h
+ +
-
(i) Add curly arrows` to the mechanism to show the
movement oI electron pairs in steps 1, 2 and 3. |3|
(ii) Suggest, with a reason, the role oI the H

. |1|
(d)
Write a balanced equation Ior the complete combustion
oI propan-2-ol. |2|
(e) Compound D, shown below, can be used as a solvent
Ior plastics and Iats and is also used in perIumery.

Comound
h
8
C C
0
0 Ch
Ch
8
Ch
8
Compound D can be prepared Irom propan-2-ol
and another organic compound. IdentiIy this other
compound. |1|
Total: 14
(Jan 07 2812)
2 Halogenoalkanes are used in the production oI
(a) 1-Bromo-2-methylpropane is used in the production
oI ibuproIen and can be prepared Irom the reaction
between 2-methylpropan-1-ol and HBr.
(CH
3
)
2
CHCH
2
OH HBr (CH
3
)
2
CHCH
2
Br H
2
O
A student reacted 4.44 g oI 2-methylpropan-1-ol with
an excess oI HBr. The student produced 5.48 g oI
1-bromo-2-methylpropane.
(i) Calculate the number oI moles oI (CH
3
)
2
CHCH
2
OH
used. |2|
(ii) Calculate the number oI moles oI (CH
3
)
2
CHCH
2
Br
collected. (CH
3
)
2
CHCH
2
Br, M
r
137 |1|
(iii) Calculate the percentage yield. Quote your answer
|1|
(b) Chloroethene, CH
2
CHCl, is polymerised to Iorm
poly(chloroethene) commonly known as PVC.
(i) Draw a section oI PVC showing three repeat units.
Put a bracket round one repeat unit. |2|
(ii)
because they are non-biodegradable. Increasingly,
they are disposed oI by combustion.
State the problem associated with the combustion
oI polymers such as PVC. |1|
(iii) State two ways in which chemists are trying to
minimise the damage to the environment caused by
the disposal oI halogenated plastics such as PVC.
|2|
(c)

F
C
Cl
F
Br
retardant.
When exposed to high temperatures, one oI the
produce Iree radicals.
Suggest, with a reason, which Chalogen bond is most
likely to be broken. |1|
Total: 10
(Jun 06 2812)
3 Acrolein, CH
2
CHCHO, and acrylic acid, CH
2
CHCOOH,
are both used in industry Ior the manuIacure oI plastic
resins and polymers. Both acrolein and acrylic acid can be
made Irom prop-2-en-1-ol, CH
2
CHCH
2
OH.
(a) (i) Draw the structures oI prop-2-en-1-ol and acrolein.
Clearly display the Iunctional groups in each
compound. |2|
(ii) Name the Iunctional group common to both
prop-2-en-1-ol and acrolein. |1|
1 This question is about two alcohols, ethanol and
propan-2-ol, CH CH(OH)CH
1.1 lxam|aat|ea cest|eas
181
Me6c|e 1
k|cehe|s, ha|eqeaea|kaaes aa6 aaa|s|s
lxam|aat|ea cest|eas
(b) Prop-2-en-1-ol can be oxidised to Iorm either acrolein
or acrylic acid.
(i) IdentiIy a suitable oxidising mixture. |2|
(ii) Write a balanced equation Ior the oxidation oI
prop-2-en-1-ol into acrolein. Use |O| to represent
the oxidising agent. |1|
(c) A sample oI prop-2-en-1-ol was oxidised and an
inIrared spectrum oI the organic product was obtained.

1OO
5O
O
4OOO 8OOO 2OOO 15OO 1OOO 5OO
wavenumber/cm
-1
By reIerring to your Data Sheet, decide whether
acrolein, CH
2
CHCHO, or acrylic acid,
CH
2
CHCOOH, was Iormed. |3|
(d) Acrylic acid reacts with prop-2-en-1-ol to produce an
ester.
(i) Complete the balanced equation Ior this reaction.
CH
2
CHCOOH CH
2
CHCH
2
OH . . . . . . |2|
(ii) Draw the structure oI the ester. Clearly display all
oI the Iunctional groups.
|2|
Total: 13
(Jun 05 2812)
4 In this question, one mark is available Ior the quality oI
spelling, punctuation and grammar.
(a) The rates oI hydrolysis oI chloroethane, bromoethane
and iodoethane are diIIerent.
Describe how you would monitor the reaction rates.
Explain why chloroethane, bromoethane and iodoethane
react at diIIerent rates.
Use suitable equations in your answer. |6|
Total: 6
(Jun 05 2812)
5 Butan-1-ol, CH
3
CH
2
CH
2
CH
2
OH, reacts with sodium.
(a) There are Iour structural isomers oI C
4
H
10
O that are
alcohols. One oI the isomers has been drawn Ior you.
Complete the table below to show the other structural
isomers.
h C h
0h
h h
h
C
h
h
C
h
h
C
butan-1-ol isomer 1 isomer 2 isomer 3
|3|
(b)
potassium dichromate(VI) to Iorm a carboxylic acid.
(i) State the colour change that you would see. |1|
(ii) Write a balanced equation Ior this oxidation oI
butan-1-ol to Iorm a carboxylic acid. Use |O| to
represent the oxidising agent. |2|
(iii) IdentiIy which oI the isomers, 1, 2 or 3, in (a) could
also be oxidised to Iorm a carboxylic acid. |1|
(c) Butan-1-ol reacts with hot concentrated sulIuric acid to
Iorm compound B.
(i) Compound B has an empirical Iormula oI CH
2

and a relative molecular mass oI 56. Use this
inIormation to deduce the molecular Iormula oI
compound B. Show your working. |2|
(ii) Write a balanced equation to show the conversion
oI butan-1-ol into compound B. |1|
(iii) One oI the isomers, 1, 2 or 3, in (a) also reacts with
hot concentrated sulIuric acid to Iorm compound B.
IdentiIy which isomer. |1|
(d) The ester CH
3
COOCH
2
CH
2
CH
2
CH
3
was Iormed by
reacting ethanoic acid with butan-1-ol.

8uIan1oI
+ h
8
C C
0
0h
Ch
8
Ch
2
Ch
2
Ch
2
0h
Catalyst
+h
2
0 h
8
C C
0
0 Ch
2
Ch
2
Ch
2
Ch
8
LsIar

r
= 11G
(i) State a catalyst Ior this reaction. |1|
(ii) In an experiment, 6.96 g oI the ester was produced
Irom 0.100 mol oI butan-1-ol. Calculate the number
oI moles oI ester produced. |1|
(iii) Calculate the percentage yield. |1|
Total: 14
(Jan 05 2812)
Answers to examination questions wi|| be found
on the Exam Caf CD.