Chapter 2

Families of Carbon Compounds Functional Groups, Intermolecular Forces, & Infrared (IR) Spectroscopy

Ch. 2 - 1

1. Hydrocarbons

Hydrocarbons are compounds comprised of carbon and hydrogen atoms Alkanes hydrocarbons that do not have multiple bonds between carbon atoms
e.g. pentane cyclohexane

Ch. 2 - 2

 Alkenes contain at least one carboncarbon double bond

e.g. propene cyclohexene

Ch. 2 - 3

 Alkynes contain at least one carboncarbon triple bond

e.g. H C C H 1-pentyne

ethyne

2-pentyne
Ch. 2 - 4

 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 - 5

Quick test
NH2 O Whats the molecular formula of this compound? F

33%

33%

33%

1. C9H12FNO 2. C9H16FNO 3. C9H14NOF

C9 H1 4N O

C9 H1 2F N

C9 H1 6F N

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

H H H H

Methane

Ch. 2 - 7

1B. Alkenes

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 all p orbitals above and below the ring The six electrons associated with these p orbitals (one electron from each orbital) are delocalized

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

Quick test
H C H

Does diphenylmethane have a dipole moment?

33%

33%

33%

A. Yes B. No C. Impossible to tell

24

A.

B.

C.

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

Is the indicated functional group primary, secondary or tertiary?

33% 33% 33%

A. Primary B. Secondary C. Tertiary

y ar y Pr im da r co n Se Te rti ar y

6. Alcohols

ROH

Examples
OH CH3OH , OH , OH ,

(1o)

(2o)

(3o)

(aromatic) (phenol)
Ch. 2 - 30

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

Ethane

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

Ch. 2 - 31

CH3CH2

7. Ethers

ROR

Examples
~100o O Acyclic

O Cyclic
Ch. 2 - 32

8. Amines

RNH2
H N (1o) H3C H H3C

H N (2o) CH3 H3C

CH3 N (3o) CH3

N H (cyclic)

N (aromatic)

Ch. 2 - 33

9. Aldehydes and Ketones

O R H R O R

(aldehydes)
O H , O ,

(ketones)
O O H ketone aldehyde
Ch. 2 - 34

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

121

H
108
o

H
Ch. 2 - 35

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 - 36

11. Nitriles

RCN
2

H3C

Ethanenitrile (acetonitrile)

Propenenitrile (acrylonitrile)

Benzenecarbonitrile (benzonitrile)

Ch. 2 - 37

What functional group is located at the indicated point in the structure below?
20% 20% 20% 20% 20%

A. Aldehyde B. Ketone C. Ester D. Ether E. Acid

A. B. C. D. E.

12. Summary of Important Families of Organic Compounds

Ch. 2 - 39

Ch. 2 - 40

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 - 41

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

Ch. 2 - 42

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 Sodium acetate

CH3CHO
CH3CO2H CH3CO2Na

-121
16.6 324

20
118 dec
Ch. 2 - 43

13B. Intermolecular Forces (van der Waals Forces) The forces that act between molecules are not as strong as those between ions These intermolecular forces are van der Waals forces

Dipole-dipole forces Hydrogen bonds Dispersion forces

Ch. 2 - 44

 Dipole-dipole forces Dipole-dipole attractions between polar molecules

d
+

O d-

dipole-dipole attraction
H H d
+

H Cl d
-

C H

H d
+

C H

Cl d

Ch. 2 - 45

 Hydrogen bonds

Dipole-dipole attractions between hydrogen atoms bonded to small, strongly electronegative atoms
Hydrogen bonds: much stronger than the dipoledipole interactions

Ch. 2 - 46

 Hydrogen bonds
d+H d H
+

d-O

d+H d H
+

d-O

hydrogen bond
H d+ d+ H d H d+

d+ H d

+H

Nd

+H

Nd
Ch. 2 - 47

 Hydrogen bonds

Calculations indicate that in the absence of hydrogen bonding, water would have a bp near -80C

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 a small

temporary dipole will occur

Ch. 2 - 49

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 - 50

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 C H d 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 - 51

13C. Boiling Points

The boiling points of liquids are pressure dependent, and boiling points are always reported as occurring at a particular pressure

Ch. 2 - 52

Examples
CH3 CH3 NO2 OH
t

Bu

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

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

1 atm = 760 torr = 760 mmHg

Ch. 2 - 53

13D. Solubilities

A general rule for solubility is that like dissolves like in terms of comparable polarities

Ch. 2 - 54

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

H3C
hydrogen bond

+ d d O H +H

H + d O d
Ch. 2 - 55

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

Hydrophilic group
OH

Decyl alcohol
O A typical detergent molecule

O S O
Ch. 2 - 56

O Na

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

Ch. 2 - 57

14. Summary of Attractive Electric Forces

Ch. 2 - 58

15. Infrared Spectroscopy

Ch. 2 - 59

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 - 60

Ch. 2 - 61

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) 28532962 30103095 16201680 675730 960975

Intensity (ms) (m) (v) (s) (s)

~3300 21002260

(s) (v)
Ch. 2 - 62

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 - 63

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 - 64

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 - 65

16. Interpreting IR Spectra

IR spectrum of octane

Ch. 2 - 66

IR spectrum of toluene

Ch. 2 - 67

16B. IR Spectra of Hydrocarbons

IR spectrum of 1-heptyne

Ch. 2 - 68

IR spectrum of 1-octene

Ch. 2 - 69

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 - 70

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 - 71

Carboxylic Acids IR spectrum of propanoic acid

Ch. 2 - 72

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 - 73

Amines IR spectrum of 4-methylaniline

Ch. 2 - 74

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 - 75

diethylbenzene

methanol

acetone

aniline

diethylbenzene