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Chapter 2

Families of Carbon
Compounds
Functional Groups,
Intermolecular Forces,
& Infrared (IR)
Spectroscopy
Created by
Professor William Tam & Dr. Phillis
Chang Ch. 2 - 1
About The Authors
These Powerpoint Lecture Slides were created and prepared by
Professor William Tam and his wife Dr. Phillis Chang.

Professor William Tam received his B.Sc. at the University of Hong


Kong in 1990 and his Ph.D. at the University of Toronto (Canada) in
1995. He was an NSERC postdoctoral fellow at the Imperial College
(UK) and at Harvard University (USA). He joined the Department of
Chemistry at the University of Guelph (Ontario, Canada) in 1998 and
is currently a Full Professor and Associate Chair in the department.
Professor Tam has received several awards in research and teaching,
and according to Essential Science Indicators, he is currently ranked
as the Top 1% most cited Chemists worldwide. He has published four
books and over 80 scientific papers in top international journals such
as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem.

Dr. Phillis Chang received her B.Sc. at New York University (USA) in
1994, her M.Sc. and Ph.D. in 1997 and 2001 at the University of
Guelph (Canada). She lives in Guelph with her husband, William, and
their son, Matthew. Ch. 2 -
1. Hydrocarbons
Hydrocarbons are compounds
that contain only carbon and
hydrogen atoms
Alkanes
hydrocarbons that do not
have multiple bonds
between carbon atoms
e.g.

pentane cyclohexane
Ch. 2 - 3
Alkenes
contain at least one
carboncarbon double bond

e.g.

propene cyclohexene

Ch. 2 - 4
Alkynes
contain at least one
carboncarbon triple bond
e.g. H C C H

ethyne 1-pentyne

2-pentyne

Ch. 2 - 5
Aromatic compound
contain a special type of
ring, the most common
example of which is a
benzene ring
CH3 COOH

e.g.

benzene toluene benzoic acid

Ch. 2 - 6
1A. Alkanes
The primary sources of alkanes are
natural gas and petroleum
The smaller alkanes (methane through
butane) are gases under ambient
conditions
Methane is the principal component of
natural gas
Higher molecular weight alkanes are
obtained largely
H by refining petroleum
H H
H Methane
Ch. 2 - 7
1B. Alkenes
Ethene and propene, the two simplest
alkenes, are among the most
important industrial chemicals
produced in the United States
Ethene is used as a starting material
for the synthesis of many industrial
compounds, including ethanol,
ethylene oxide, ethanal, and the
polymer Hpolyethylene
H
C
C
H H Ethene
Ch. 2 - 8
Propene is the important starting
material for acetone, cumene and
polypropylene
Examples of naturally occurring
alkenes

-Pinene An aphid alarm


(a component of pheromone
turpentine) Ch. 2 - 9
1C. Alkynes
The simplest alkyne is ethyne (also
called acetylene)
H C C H
Examples of naturally occurring
alkynes
O Br Cl
C C C C C CH3
Capillin O
(an antifungal agent)
Br Dactylyne
(an inhibitor of
pentobarbital
metabolism)
Ch. 2 -
1D.Benzene

All C C bond lengths are the


same (1.39 ) (compare with CC
single bond 1.54 , C=C double
bond 1.34 )

Extra stabilization due to


resonance aromatic Ch. 2 -
3 Dimensional structure of
benzene

-electrons
above and
below ring

Planar structure
All carbons sp2 hybridized
Ch. 2 -
The lobes of each orbital above
and below the ring overlap with
the lobes of orbitals on the
atoms to either side of it
the six electrons associated with
these orbitals (one electron from
each orbital) are delocalized
about all six carbon atoms of the
ring

Ch. 2 -
2. Polar Covalent Bonds

Li F
Lithium fluoride has an ionic bond
H H
H C C H
H H
Ethane has a covalent bond. The
electrons are shared equally between
the carbon atoms Ch. 2 -
electronegativity



C C C O
2.5 3.5

equal sharing unequal sharing



of e of e
(non-polar bond) (polar bond)

Ch. 2 -
Electronegativity (EN)
The intrinsic ability of an atom
to attract the shared electrons
in a covalent bond

Electronegativities are based


on an arbitrary scale, with F the
most electronegative (EN =
4.0) and Cs the least (EN = 0.7)
Ch. 2 -
element
(EN) H
(2.1)
Li Be B C N O F
(1.0) (1.6) (2.0) (2.5) (3.0) (3.5) (4.0)

Increasing EN
Na Mg Si P S Cl
(0.9) (1.2) (1.8) (2.1) (2.5) (3.0)
K Br
(0.8) (2.8)
Rb I
(0.8) (2.5)
Cs
(0.7)

Increasing EN
Ch. 2 -


C N C Cl
2.5 3.0 2.5 3.0



H C Si C
2.1 2.5 1.8 2.5

Ch. 2 -
3. Polar and Nonpolar Molecules

Dipole distance between the


=
moment the charges charge

=rQ
Dipole moments are expressed in
debyes (D), where 1 D = 3.336
1030 coulomb meter (Cm) in SI
units
Ch. 2 -


Cl

>
C net dipole
H (1.87 D)
H
H
+

Ch. 2 -
Molecules containing polar bonds
are not necessarily polar as a
whole, for example

(1) BF3 ( = 0 D) (2) CCl4 ( = 0 D)


Cl
F
o C
120 Cl
B Cl
F F Cl
(trigonal planar) (tetrahedral)
Ch. 2 -
Dipole moment of some
compounds
Compoun Dipole Compoun Dipole
d Moment d Moment
NaCl 9.0 H2O 1.85
CH3NO2 3.45 CH3OH 1.70
CH3Cl 1.87 CH3COOH 1.52
CH3Br 1.79 NH3 1.47
CH3I 1.64 CH4 0
CHCl3 1.02 CCl4 0
Ch. 2 -
3A. Dipole Moments in Alkenes

cis- trans-
1,2-Dichloroethene 1,2-Dichloroethene
H H H Cl

C C C C

Cl Cl Cl H
resultant dipole
moment
( = 1.9 D) ( = 0 D)
Ch. 2 -
Physical properties of some cis-
trans isomers
m.p. m.p.
Compound ()
(oC) (oC)
cis-1,2-Dichloroethene -80 60 1.90
trans-1,2-
-50 48 0
Dichloroethene
cis-1,2-Dibromoethene -53 112.5 1.35
trans-1,2-
-6 108 0
Dibromoethene
Ch. 2 -
4. Functional Groups
Alkane Alkyl Group Abbrev. Bond-Line Model

CH3H CH3 Me-


Methane Methyl

CH3CH2H CH3CH2 Et-


Ethane Ethyl

CH3CH2CH2H CH3CH2CH2 Pr-


Propane propyl

CH3CH2CH2CH2H CH3CH2CH2CH2 Bu-


Butane
Butyl Ch. 2 -
CH3 Methyl

CH3CH2 Ethyl
These and
others can
be
CH3CH2CH2 Propyl
designated
by R
CH3CHCH3 Isoprypyl

General formula for an alkane is


RH
Ch. 2 -
4B. Phenyl and Benzyl Groups
Phenyl group

or or C6H5

or Ph or or Ar

Benzyl group
CH2
or or C6H5CH2

or Bn Ch. 2 -
5. Alkyl Halides or Haloalkanes
RX (X = F, Cl, Br, I)

Examples
Attached to Attached to Attached to
1 carbon atom 2 carbon atoms 3 carbon atoms
C C C

C Cl C Br C I
a 1o chloride a 2o bromide a 3o iodide
Ch. 2 -
6. Alcohols
ROH

Examples
OH
OH OH,
CH3OH , ,

(1o) (2o) (3o) (aromatic)


(phenol)
Ch. 2 -
Alcohols may be viewed
structurally in two ways:
As hydroxyl derivatives of
alkanes
As alkyl derivatives of water
ethyl
group
CH3CH2 H
CH3CH3 109.5o O 104.5o O
H hydroxyl H
group
Ethane Ethyl alcohol Water
(ethanol)
Ch. 2 -
7. Ethers
ROR

Examples

~100o

O
O
Acyclic Cyclic
Ch. 2 -
8. Amines
RNH2
H H CH3
N N N
H3C H H3C CH3 H3C CH3
o o o
(1 ) (2 ) (3 )

N N
H
(cyclic) (aromatic) Ch. 2 -
9. Aldehydes and Ketones

O O

R H R R
(aldehydes) (ketones)

O O O O

H, , H

ketone aldehyde
Ch. 2 -
Aldehydes and ketones have a
trigonal planar arrangement of
groups around the carbonyl
carbon atom
o
O
121 121o

H H
108o

Ch. 2 -
10.Carboxylic Acids, Esters, and
Amides
O O O

R OH R OR R Cl
(carboxylic (ester) (acid
acid) chloride)

O O O

R NR2 R O R
(amide) (acid
anhydride) Ch. 2 -
11.Nitriles
RCN
2
2 1 1
3
H3C C N C N C N

Ethanenitrile Propenenitrile Benzenecarbonitrile


(acetonitrile) (acrylonitrile) (benzonitrile)

Ch. 2 -
12. Summary of Important Families
of Organic Compounds

Ch. 2 -
Ch. 2 -
13.Physical Properties and
Molecular Structure
.Ionic Compounds: Ion-Ion Forces
The melting point of a substance
is the temperature at which an
equilibrium exists between the
well-ordered crystalline state and
the more random liquid state

Ch. 2 -
If the substance is an ionic
compound, the ionion forces
that hold the ions together in the
crystalline state are the strong
electrostatic lattice forces that act
between the positive and negative
ions in the orderly crystalline
structure

A large amount of thermal energy


is required to break up the orderly
structure of the crystal into theCh. 2 -
The boiling points of ionic
compounds are higher still, so
high that most ionic organic
compounds decompose before
they boil

Ch. 2 -
Physical properties of selected
compounds
Compound Structure mp ( C)
o
bp (oC)
(1 atm)

Ethane CH3CH3 -172 -88.2

Chloroethane CH3CH2Cl -138.7 13.1

Ethyl alcohol CH3CH2OH -114 78.5

Acetaldehyde CH3CHO -121 20

Acetic acid CH3CO2H 16.6 118


Sodium
CH3CO2Na 324 dec
acetate
Ch. 2 -
B. Intermolecular Forces (van der
Waals Forces)
The forces that act between
molecules are not as strong as
those between ions
These intermolecular forces, van
der Waals forces, are all electrical
in nature
Dipole-dipole forces
Hydrogen bonds
Dispersion forces Ch. 2 -
Dipole-dipole forces
Dipole-dipole attractions
between polar molecules

O
O

dipole-dipole attraction

H H
H Cl H Cl
C C
H H Ch. 2 -
Hydrogen bonds
Dipole-dipole attractions
between hydrogen atoms
bonded to small, strongly
electronegative atoms (O, N, or
F) and nonbonding electron
pairs on other such
electronegative atoms

Hydrogen bonds (bond


dissociation energies of about 4
-1
38 kJ mol ) are weaker than
ordinary covalent bonds butCh. 2 -
Hydrogen bonds
H H
O O
H H

hydrogen bond



H H

H N H N

H H

Ch. 2 -
Hydrogen bonds
Hydrogen bonding explains why
water, ammonia, and hydrogen
fluoride all have far higher
boiling points than methane (bp
161.6C), even though all four
compounds have similar
molecular weights

One of the most important


consequences of hydrogen
bonding is that it causes water
to be a liquid rather than a Ch.
gas 2-
Hydrogen bonds
Calculations indicate that in the
absence of hydrogen bonding,
water would have a bp near
80C and would not exist as a
liquid unless the temperature
were lower than that
temperature

Ch. 2 -
Dispersion forces (London
forces)
The average distribution of
charge in a nonpolar molecule
over a period of time is uniform
At any given instant, however,
because electrons move, the
electrons and therefore the
charge may not be uniformly
distributed
Electrons may, in one instant,
be slightly accumulated on one
part of the molecule, and, as
Ch.a
2-
Dispersion forces (London
forces)
This temporary dipole in one
molecule can induce opposite
(attractive) dipoles in
surrounding molecules

These temporary dipoles


change constantly, but the net
result of their existence is to
produce attractive forces
between nonpolar molecules
Ch. 2 -
Two important factors
determine the magnitude of
dispersion forces
The relative polarizability of
electrons of the atoms
involved
The electrons of large
atoms such as iodine are
loosely held and are
easily polarized, while
the electrons of small
atoms such as fluorine Ch. 2 -

stronger

dispersion forces




I
I




C I
C I

I I
I I

weaker
dispersion forces
F F

C F
C F

F F
F F
Ch. 2 -
The relative surface area of
the molecules involved
The larger the surface
area, the larger is the
overall attraction
between molecules
caused by dispersion
forces

Ch. 2 -
e.g. Pentane vs. Neopentane (both C5H12)




H H H



H H H H H C H
H H larger
C H
surface H
H H C H
area H
C C
H H H H stronger
dispersion H H H
forces








H H H H H H H

H H smaller
surface area H C H
H H weaker C H
H
H H dispersion
H C H
H H C C
forces


Neopentane H H H
Ch.2 -
Pentane (bp 36oC) (bp 9.5 C)
o

13C. Boiling Points
The boiling point of a liquid is the
temperature at which the vapor
pressure of the liquid equals the
pressure of the atmosphere above
it

the boiling points of liquids are


pressure dependent, and boiling
points are always reported as
occurring at a particular pressure
Ch. 2 -
Examples
CH3 t
Bu
CH3

NO2

OH
o
bp: 245 C / 760 mmHg bp: 260oC / 760 mmHg
o
(74 C / 1 mmHg) (140oC / 20 mmHg)

1 atm = 760 torr = 760


mmHg Ch. 2 -
13D. Solubilities
A general rule for solubility is that like
dissolves like in terms of comparable
polarities
Polar and ionic solids are usually
soluble in polar solvents
Polar liquids are usually miscible
Nonpolar solids are usually soluble
in nonpolar solvents
Nonpolar liquids are usually
miscible
Polar and nonpolar liquids, like oil
and water, are usually not solubleCh. 2 -
e.g. MeOH and H2O are miscible in all
proportions

H3C


O H
hydrogen
bond
H H
O

Ch. 2 -
Hydrophobic means
incompatible with water
Hydrophilic means
compatible with water
Hydrophil
Hydrophobic portion ic group

OH
Decyl alcohol
O
S O Na
O
O
A typical detergent molecule Ch. 2 -
E. Guidelines for Water Solubility
Organic chemists usually define a
compound as water soluble if at
least 3 g of the organic
compound dissolves in 100 mL of
water
Usually compounds with one to
three carbon atoms are water
soluble, compounds with four or
five carbon atoms are borderline,
and compounds with six carbonCh. 2 -
14. Summary of Attractive Electric Forces

Ch. 2 -
15.Infrared Spectroscopy

Ch. 2 -
The position of an absorption band
(peak) in an IR spectrum is

specified in units of wavenumbers
( ) 1 E = h
=
E
( = wavelength in cm)
(E = energy) = c
( = frequency of radiation)

E = hc

Ch. 2 -
Ch. 2 -
Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v =
variable
Group Freq. Range (cm Intensity
-

1
)
Alkyl
CH (stretching) 28532962 (ms)
Alkenyl
CH (stretching) 30103095 (m)
C=H (stretching) 16201680 (v)
cis-RCH=CHR 675730 (s)
trans-RCH=CHR 960975 (s)
Alkynyl
CH (stretching) ~3300 (s)
CC (stretching) 21002260 (v) 2 -
Ch.
Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v =
variable
Group Freq. Range (cm ) Intensity
-1

Aromatic
ArH (stretching) ~3300 (v)
- monosubstituted 690710 (very s)
730770 (very s)
- o-disubstituted 735770 (s)
- m-disubstituted 680725 (s)
750810 (very s)
- p-disubstituted 800860 (very s)

Ch. 2 -
Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v =
variable
Group Freq. Range (cm ) Intensity
-1

Alcohols, Phenols & Carboxylic Acids


OH (stretching)
- alcohols & 35903650 (sharp, v)
phenols
(dilute solutions) 32003550 (broad, s)
- alcohols &
phenols 25003000 (broad, v)
(hydrogen
bonded)
- carboxylic acids
(hydrogen Ch. 2 -
Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v =
variable
Group Freq. Range (cm ) Intensity
-1

Aldehydes, Ketones, Esters, Carboxylic Acids,


Amides
C=O (stretching) 16301780 (s)
Aldehydes 16901740 (s)
Ketones 16801750 (s)
Esters 17351750 (s)
Carboxylic Acids 17101780 (s)
Amides 16301690 (s)
Amines
NH 33003500 (m)
Nitriles Ch. 2 -
16.Interpreting IR Spectra
IR spectrum of octane

Ch. 2 -
IR spectrum of toluene

Ch. 2 -
6B. IR Spectra of Hydrocarbons

IR spectrum of 1-heptyne

Ch. 2 -
IR spectrum of 1-octene

Ch. 2 -
B. IR Spectra of Some Functional
Groups Containing
Carbonyl Functional Groups
O O O

R H R R R OR
(aldehyde) (ketone) (ester)
1690-1740 cm-1 1680-1750 cm-1 1735-1750 cm-1
O O

R OH R NR2
(carboxylic acid) (amid)
1710-1780 cm-1 1630-1690 cm-1 Ch. 2 -
Alcohols and phenols
The IR absorption of an alcohol or
phenol OH group is in the 3200
3550 cm-1 range, and most often it
is broad

Ch. 2 -
Carboxylic Acids
IR spectrum of propanoic acid

Ch. 2 -
Amines
1o and 2o amines give absorptions
of moderate strength in the 3300
3500 cm-1 region
1o amines exhibit two peaks in this
region due to symmetric &
asymmetric
stretching of the two NH bonds
2o amines exhibit a single peak
3o amines show no NH absorption
because they have no such bond
A basic pH is evidence for any class
Ch. 2 -
of amines
Amines
IR spectrum of 4-methylaniline

Ch. 2 -
RNH2 (1 Amine) R2NH (2 Amine)
Two peaks in One peak in
33003500 cm-1 33003500 cm-1
region region

symmetric asymmetric
stretching stretching

Ch. 2 -
END OF CHAPTER 2

Ch. 2 -