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 - 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 1-pentyne

ethyne

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 by refining petroleum
H 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 polyethylene
H 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 (a component of turpentine)

An aphid alarm pheromone

Ch. 2 - 9

1C. Alkynes

The simplest alkyne is ethyne (also called acetylene)

H C C H

Examples of naturally occurring alkynes

O C C C C C CH3 O Br Dactylyne (an inhibitor of pentobarbital metabolism)
Ch. 2 - 10

Br

Cl

Capillin (an antifungal agent)

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 - 11

3 Dimensional structure of benzene

p-electrons above and below ring

Planar structure All carbons sp2 hybridized

Ch. 2 - 12

The lobes of each p orbital above and below the ring overlap with the lobes of p orbitals on the atoms to either side of it the six electrons associated with these p orbitals (one electron from each orbital) are delocalized about all six carbon atoms of the ring

Ch. 2 - 13

2. Polar Covalent Bonds

Li

F
H H

Lithium fluoride has an ionic bond

C C H H

Ethane has a covalent bond. The electrons are shared equally between the carbon atoms

Ch. 2 - 14

electronegativity
d
+

O
3.5

2.5

equal sharing of e (non-polar bond)

unequal sharing of e (polar bond)

Ch. 2 - 15

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 - 16

element (EN)
Li Be (1.0) (1.6) Na Mg (0.9) (1.2) K (0.8) Rb (0.8) Cs (0.7)

H (2.1)

Increasing EN
Ch. 2 - 17

Increasing EN

B C N O F (2.0) (2.5) (3.0) (3.5) (4.0) Si P S Cl (1.8) (2.1) (2.5) (3.0) Br (2.8) I (2.5)

Cl

2.5

3.0

2.5

3.0

Si
1.8

2.1

2.5

2.5
Ch. 2 - 18

3. Polar and Nonpolar Molecules

Dipole distance between the = moment the charges charge m=rQ

Dipole moments are expressed in debyes (D), where 1 D = 3.336 1030 coulomb meter (Cm) in SI units
Ch. 2 - 19

d Cl

>
H H d
+

C H

net dipole (1.87 D)

Ch. 2 - 20

Molecules containing polar bonds are not necessarily polar as a whole, for example

(1) BF3 (m = 0 D)

F B

(2) CCl4 (m = 0 D) Cl
o

120

F F (trigonal planar)

Cl

Cl

Cl (tetrahedral)
Ch. 2 - 21

Dipole moment of some compounds

Dipole Compound Moment 9.0 H2O Dipole Moment 1.85

Compound NaCl

CH3NO2 CH3Cl
CH3Br CH3I

3.45 1.87
1.79 1.64

CH3OH CH3COOH
NH3 CH4

1.70 1.52
1.47 0

CHCl3

1.02

CCl4

0
Ch. 2 - 22

3A. Dipole Moments in Alkenes

1,2-Dichloroethene
H C Cl C Cl Cl H

cis-

1,2-Dichloroethene
H C C H Cl

trans-

resultant dipole moment

(m = 1.9 D)

(m = 0 D)
Ch. 2 - 23

Physical properties of some cis-trans isomers

Compound m.p. (oC) -80 -50 -53 m.p. (oC) 60 48 (m) 1.90 0

cis-1,2-Dichloroethene trans-1,2-Dichloroethene cis-1,2-Dibromoethene

112.5 1.35

trans-1,2-Dibromoethene

-6

108

0
Ch. 2 - 24

4. Functional Groups
Alkane
CH3H Methane

Alkyl Group
CH3 Methyl

Abbrev. Bond-Line Model

Me-

CH3CH2H Ethane
CH3CH2CH2H Propane

CH3CH2 Ethyl
CH3CH2CH2 propyl

Et-

Pr-

CH3CH2CH2CH2H Butane

CH3CH2CH2CH2 Butyl

BuCh. 2 - 25

CH3 CH3CH2 CH3CH2CH2 CH3CHCH3

Methyl Ethyl Propyl Isoprypyl

These and others can be designated by R

General formula for an alkane is RH

Ch. 2 - 26

4B. Phenyl and Benzyl Groups

Phenyl group
or or C6H5 or

or

Ph

or

Ar

Benzyl group
CH2 or or C6H5CH2 or Bn
Ch. 2 - 27

5. Alkyl Halides or Haloalkanes

RX (X = F, Cl, Br, I)

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

C C
Cl

C
Br

C
I

a 1o chloride

a 2o bromide

a 3o iodide
Ch. 2 - 28

6. Alcohols

ROH

Examples
OH CH3OH , OH , OH ,

(1o)

(2o)

(3o)

(aromatic) (phenol)
Ch. 2 - 29

Alcohols may be viewed structurally in two ways: As hydroxyl derivatives of alkanes As alkyl derivatives of water
ethyl group
CH3CH3
109.5o

CH3CH2 O

Ethane

O 104.5o H H hydroxyl group Water Ethyl alcohol (ethanol)

Ch. 2 - 30

7. Ethers

ROR

Examples
~100o O Acyclic

O Cyclic
Ch. 2 - 31

8. Amines

RNH2
H N (1 )
o

H H H3C N (2 )
o

CH3 CH3 H3C N (3 )

o

H3C

CH3

N H (cyclic)

N (aromatic)

Ch. 2 - 32

9. Aldehydes and Ketones

O R H R O R

(aldehydes)
O H , O ,

(ketones)
O O H ketone aldehyde
Ch. 2 - 33

Aldehydes and ketones have a trigonal planar arrangement of groups around the carbonyl carbon atom
121
o

121

H
108
o

H
Ch. 2 - 34

10. Carboxylic Acids, Esters, and Amides

O R OH (carboxylic acid) O R NR2 (amide) R R O OR (ester) R O Cl

(acid chloride) O

O R (acid anhydride)

Ch. 2 - 35

11. Nitriles

RCN
2

H3C

Ethanenitrile (acetonitrile)

Propenenitrile (acrylonitrile)

Benzenecarbonitrile (benzonitrile)

Ch. 2 - 36

12. Summary of Important Families of Organic Compounds

Ch. 2 - 37

Ch. 2 - 38

13. Physical Properties and Molecular Structure

13A.Ionic Compounds: Ion-Ion Forces

The melting point of a substance is the temperature at which an equilibrium exists between the wellordered crystalline state and the more random liquid state
Ch. 2 - 39

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 the disorderly open structure of a liquid
Ch. 2 - 40

The boiling points of ionic compounds are higher still, so high that most ionic organic compounds decompose before they boil

Ch. 2 - 41

Physical properties of selected compounds

Structure CH3CH3 CH3CH2Cl CH3CH2OH mp (oC) -172 -138.7 -114 bp (oC) (1 atm) -88.2 13.1 78.5

Compound Ethane Chloroethane Ethyl alcohol

Acetaldehyde
Acetic acid

CH3CHO
CH3CO2H

-121
16.6 324

20
118 dec
Ch. 2 - 42

Sodium acetate CH3CO2Na

13B. 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 - 43

 Dipole-dipole forces Dipole-dipole attractions between polar molecules

d
+

dipole-dipole attraction
H H Cl d
-

H H

H H

Cl d

Ch. 2 - 44

 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 -1 energies of about 4 38 kJ mol ) are weaker than ordinary covalent bonds but much stronger than the dipoledipole interactions
Ch. 2 - 45

 Hydrogen bonds
d+H d+ H d-O

d+H d H
+

dO

hydrogen bond
H
+H

Nd

H
+H

Nd
Ch. 2 - 46

 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 gas at 25C
Ch. 2 - 47

 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 - 48

 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 a consequence, a small temporary

dipole will occur

Ch. 2 - 49

 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 - 50

 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 are more tightly held and are much less polarizable
Ch. 2 - 51

dd-

stronger + d d d d d+ dispersion forces dd+ d + + d- I d d- I d + +

I
d-

C I

I
d+

d d+

dd-

I
d-

C I

d+ + d I d+ + d d+

d- F d+

weaker dispersion forces

d
+

d- F d+

C F

F
d+

C F

F
d+

d-

d-

Ch. 2 - 52

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 - 53

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

d H
H
-

d- H H

d d d d d
-

dH H
H

H
+H

d+

d d+ + d+ d d
-

H H

Hd+

d+

larger surface area stronger dispersion forces

H H C d d C H H H C C C H + d+ d H H+ + H
-

d H HH d

d- H
H

- d d d d d-

H H

H H d H d H
+

+H

d d+ + d+ d d

H H

Hd+

smaller surface area weaker dispersion forces

Pentane (bp

36oC)

H H C d C H d H H C C C H + d+ d Neopentane + H H H +
-

d H HH d

d-

(bp

9.5oC)

Ch. 2 - 54

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 - 55

Examples
CH3 CH3 NO2 OH
t

Bu

bp: 245 C / 760 mmHg (74 C / 1 mmHg)

o

bp: 260 C / 760 mmHg (140oC / 20 mmHg)

1 atm = 760 torr = 760 mmHg

Ch. 2 - 56

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 soluble to large extents Ch. 2 - 57

e.g. MeOH and H2O are miscible in all proportions

H3C
hydrogen bond

+ d d O H +H

H + d O d
Ch. 2 - 58

 Hydrophobic means incompatible with water Hydrophilic means compatible with water
Hydrophobic portion

Hydrophilic group
OH

Decyl alcohol

O O S O
Ch. 2 - 59

O Na

A typical detergent molecule

13E. 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 carbon atoms or more are insoluble

Ch. 2 - 60

14. Summary of Attractive Electric Forces

Ch. 2 - 61

15. Infrared Spectroscopy

Ch. 2 - 62

The position of an absorption band (peak) in an IR spectrum is specified in units of wavenumbers ( ) 1 DE = h = E

( = wavelength in cm) (E = energy) ( = frequency of radiation)

c =
hc DE =
Ch. 2 - 63

Ch. 2 - 64

Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v = variable

Group Alkyl CH (stretching) Alkenyl CH (stretching) C=H (stretching) cis-RCH=CHR trans-RCH=CHR Alkynyl CH (stretching) CC (stretching)

Freq. Range (cm-1)

Intensity

28532962
30103095 16201680 675730 960975 ~3300 21002260

(ms)
(m) (v) (s) (s) (s) (v)
Ch. 2 - 65

Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v = variable

Group Aromatic ArH (stretching) - monosubstituted - o-disubstituted - m-disubstituted - p-disubstituted

Freq. Range (cm-1) Intensity ~3300 690710 730770 735770 680725 750810 800860 (v) (very s) (very s) (s) (s) (very s) (very s)

Ch. 2 - 66

Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v = variable

Group Freq. Range (cm-1) Alcohols, Phenols & Carboxylic Acids OH (stretching) - alcohols & phenols 35903650 (dilute solutions) - alcohols & phenols 32003550 (hydrogen bonded) - carboxylic acids 25003000 (hydrogen bonded)

Intensity

(sharp, v)
(broad, s) (broad, v)

Ch. 2 - 67

Characteristic IR absorptions
Intensity: s = strong, m = medium, w = weak, v = variable

Group Freq. Range (cm-1) Intensity 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. CN 22202260 (m) 2 - 68

16. Interpreting IR Spectra

IR spectrum of octane

Ch. 2 - 69

IR spectrum of toluene

Ch. 2 - 70

16B. IR Spectra of Hydrocarbons

IR spectrum of 1-heptyne

Ch. 2 - 71

IR spectrum of 1-octene

Ch. 2 - 72

16B. IR Spectra of Some Functional Groups Containing

Carbonyl Functional Groups

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

1690-1740 cm-1

1735-1750 cm-1

R OH (carboxylic acid) 1710-1780 cm-1

NR2 (amid)
Ch. 2 - 73

1630-1690 cm-1

Alcohols and phenols

The IR absorption of an alcohol or phenol OH group is in the 32003550 cm-1 range, and most often it is broad

Ch. 2 - 74

Carboxylic Acids IR spectrum of propanoic acid

Ch. 2 - 75

Amines
o

1 and 2 amines give absorptions of moderate strength in the 33003500 cm-1 region o 1 amines exhibit two peaks in this region due to symmetric & asymmetric stretching of the two NH bonds o 2 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 of amines
Ch. 2 - 76

Amines IR spectrum of 4-methylaniline

Ch. 2 - 77

RNH2 (1 Amine) Two peaks in 33003500 cm-1 region

R2NH (2 Amine) One peak in 33003500 cm-1 region

symmetric stretching

asymmetric stretching

Ch. 2 - 78

 END OF CHAPTER 2

Ch. 2 - 79