17

ACID STRENGTH
•   HCl is a strong acid because it ionizes completely in water.
HCl + H2O H3O+ + Cl-

Ka = [H3O+] [Cl-] / [HCl] = 1 X 107

•   Ka is called the acidity constant or the acid dissociation constant. Thus a
large Ka value means that a great deal of ionization has occurred and much
H3O+ has been produced. This means that the acid is a strong acid.

•   The term pKa can also be used to denote the strength of an acid.
pKa = - log Ka

Thus for HCl, pKa = -log (1 X 107) = -7 and HCl is a strong acid.
Acetic acid, CH3CO2H; Ka = 1.8 X 10-5 ; pKa = 4.74. Acetic acid is a weak acid.
Problem: Which is the stronger acid: formic acid, HCO2H (pKa = 3.7) or picric
acid, C6H3N3O7 (pKa = 0.3)? Write equations for their ionization.

Problem: The pKa of water is 15.74 and that of ethanol is 16.00. Which is the
stronger acid? Write a possible reaction that could occur when the two substances
are mixed?

Problem: On which side (products or reactants) does the following equilibrium

rest?
CH3CO2H + OH- CH3CO2- + H2O
pKa = 4.74 pKa = 15.7
 18

Factors affecting acidity (4)

1. The electronegativity of the atom bonded to H.
Increasing acid strength

CH4 < NH3 < H2O < HF

Non acids hydrofluoric acid
Consider the stability of the conjugate base in each case.
HF H+ + F-

H2O H+ + OH-

The conjugate base F- is more stable than the conjugate base OH- because F is
more electronegative than O and is thus better able to accommodate a negative
charge.

Likewise, since N is more electronegative than C, the conjugate base NH2- is more
stable than the conjugate base CH3-. So NH3 is more acidic than CH4. In fact, CH4
and other alkanes, as well as NH3, are not called acids.

2. Increasing acid strength

HI > HBr > HCl > HF

HI H+ + I- vs. HF H+ + F-

Rationale: here the large size of the I- can easily disperse the negative charge over
its large surface. However the small size of the F atom means that the negative
charge on F- is localized or concentrated in a smaller region of space. This makes I-
a weaker base than F-, so HI is a stronger acid than HF.

3. Inductive effects; resonance effects

Note the acidity of the following compounds.
Increasing acidity

CH3CH2OH < CH3CH(F)OH < CH3CO2H < FCH2CO2H

Consider the stabilization of the ethoxide ion due to the electron withdrawing
inductive effect of the F atom.

An electron withdrawing inductive

effect that stabilizes the conjugate base
 19

Also consider resonance stabilization of the fluoroacetate ion, FCH2CO2-.

H
H O
O
F C C In addition we can see the
F C C electron withdrawing inductive
O
O effect, this helps this helps to
H
H displace the negative charge as
here there is a resonance effect shown. This stabilizes the base
greatly and makes the present
acid a relatively strong acid.

4. Hybridization of carbon has an effect on acidity.

Ka pKa
-60
CH4 1 x 10 60

H2C = CH2 1 x 10-44 44

H C C H 1 x 10-25 25

The above data shows that the three hydrocarbons are essentially non acidic.
However, of the three, acetylene, C2H2, is the strongest acid.
Consider what happens if CH4 acts as an acid and loses a proton. The resulting
methyl anion is a very strong base as the lone pair is in an sp3 orbital that extends
far from the nucleus and thus can easily be donated to a positive species such as
H+. As a result CH4 is not acidic.
Sketch:

Compare with the anion that results when acetylene loses a proton, The resulting
acetylide anion has a lone pair of electrons in a sp hybrid orbital which is relatively
close to the carbon nucleus. So the lone pair is less easily donated, the anion is less
basic and as a result C2H2 is more acidic than CH4.
Sketch:
 20

BASE STRENGTH (IMPORTANT)

•   The usual strong bases are NaOH and KOH. They are often in aqueous
solution where the basic species is the hydroxide ion, OH-.
•   Other stronger bases are:
1. Sodium alkoxides such as
a) sodium methoxide, written as NaOCH3, or CH3ONa
where the basic species is the methoxide anion, CH3O-.
b) sodium ethoxide, NaOCH2CH3, or CH3CH2ONa, or C2H5ONa.
where the basic species is the ethoxide ion, CH3CH2O-.

2. Sodium amide, NaNH2, where the basic species is the amide ion, NH2-.
NH2- is a stronger base than CH3O-. (N is less electronegative than O).
Example: NaNH2 + HCO2H

3. Alkyllithium and alkylsodium compounds.

a) methylsodium, CH3Na, where CH3- , the methyl anion, is a very strong base.

b) ethyllithium, CH3CH2Li, where CH3CH2-, the ethyl anion, is a very strong base.

4. Sodium hydride, NaH i.e. Na+H- The hydride ion is a very strong base.

Problems: Write the products expected in each of the following reactions; then
write the net ionic equation using the arrow pushing technique.
NaNH2 + CH3OH
 21

CH3Na + CH3CO2H

NaH + H2O

Add all missing lone pairs in the following reaction. Identify the Lewis acid and
Lewis base. Write the arrow pushing mechanism.
H F H F

H N B F H N B F
+
H F H F

CH3CH2OH + H2SO4 CH3CH2OH2+ + HSO4-

ethanol ethyl oxonium ion
(protonated ethanol)
Add all missing lone pairs to each reactant and product.
Identify the Bronsted acid and Bronsted base. Write the arrow pushing mechanism.
O

An acceptable structure for H O S O H

sulfuric acid is shown.
O
 22

PROBLEMS TO TRY:

From the following text, author, publisher, chapter and pages of the spiral
bound Chem 221 Manual sold at the bookstore.
Text: Organic Chemistry, 3rd Edition
Author: Janice Gorgynski Smith,
Publisher: McGraw Hill, N.Y. 2011.
Pages in the 221 Manual: pp. 43 – 46; #1.40; 1.43 a) c)0; 1.44; 1.45; 1.52(b, c,
d); 1.59-1.60; 1.63; 1.64; 1.66; 1.67; 1.68; 1.70; 1.81; 1.85; 1.91.
 23

ALKANES AND CYCLOALKANES,

ALKANES
•   A large family of saturated hydrocarbons; formula CnH2n+2, n≥1
•   A homologous series exists where successive members differ by CH2 in their
formulae.

Examples: b.p.oC Structures

CH4, Methane -168

C2H6, Ethane -89

C3H8, propane -42

C4H10, Butane
n-butane 0

isobutane -12

C5H12, Pentane
n-pentane 36

C6H14, Hexane
n-hexane 69

C7H16, Heptane C8H18, Octane

n-heptane 98 n-octane 128

C9H20, n-Nonane 151 C10H22, n-Decane 174

 24

OCCURRENCE OF ALKANES
COMMERCIAL SOURCES: NATURAL GAS AND PETROLEUM DEPOSITS

NATURAL GAS
•   Mainly CH4 with some C2H6, C3H8, C4H10.
•   These alkanes are separated by liquefaction and then by boiling.

PETROLEUM
•   One source is the oil sands in Alberta. Supercritical CO2 may be pumped
into the oil/sand mix so as to make the mixture light (less dense). The oil
then easily rises to the surface.

•   It consists of liquid alkanes and aromatic hydrocarbons. There could be as

many as 130 different hydrocarbons in a given sample.

•   It must be refined so as to isolate its components.

•   Refining essentially consists of distilling petroleum into fractions of

different boiling ranges.

Petroleum ether, C5 – C7, b.p. 20-60oC

Gasoline, C5 – C11

Kerosene (jet fuel), C11 - C14

Fuel oil, C14 - C25

Lubricating oils, greases (cyclic)

Asphalt

Cracking and Reforming

C11 – C14 catalyst C3 – C5 catalyst C7 – C10

400-500oC branched alkanes

high octane fuel
 25

NOMENCLATURE OF ALKYL GROUPS

Alkane, CnH2n+2 Alkyl group, CnH2n+1 Alkyl/Common Name

CH4 methyl, CH3- CH3Cl, methyl chloride

N.B.The dash following CH3 implies the presence of a bond to another atom.

C2H6 ethyl, CH3CH2- CH3CH2Br, ethyl bromide

C3H8 n-propyl, CH3CH2CH2- CH3CH2CH2I, n-propyl iodide

or n-C3H7- n-C3H7I

isopropyl, CH3CHCH3 CH3CHCH3, isopropyl chloride

Cl

•   One can write the above structure as CH3CH(Cl)CH3

•   Also, one can write the condensed form of isopropyl as (CH3)2CH-
•   Thus (CH3)2CHBr is isopropyl bromide.

Name the following compounds:

CH3F ______________________________________

CH3CH2Cl ______________________________________

(CH3)2CHF _______________________________________

CH3CH2CH2Br ________________________________________

FCH2CH2CH3 ________________________________________

CH3CH(I)CH3 ___________________________________________

•   N.B. The letter R can be used to represent any or all alkyl groups.
•   Thus RCl represents all alkyl chlorides such as CH3Cl, C2H5Cl etc.
•   The formula RX can represent all alkyl halides such as RCl, RBr, and RI.
 26

C4H10 Butane

CH3CH2CH2CH3, n-butane
A straight chain isomer

CH3CH2CH2CH2- CH3CH2CH2CH2F
n-butyl group n-butyl fluoride

CH3CHCH2CH3 CH3CHCH2CH3

Br
sec-butyl group sec-butyl bromide

(CH3)2CHCH3, isobutane
A branched chain isomer

(CH3)2CHCH2- (CH3)2CHCH2OH
isobutyl group isobutyl alcohol

(CH3)3C- (CH3)3CI
tert-butyl group tert-butyl iodide

Definition of iso: There is a one carbon branch at the next to last carbon in the
chain and the point of attachment of the substituent is at the opposite end of the
chain. Warning: the understanding of “iso” has been a difficult point over the
years.
 27

Primary, secondary, and tertiary alkyl halides

CH3CH2CH2Br is a primary alkyl bromide.

•   The carbon bearing bromine is called a primary carbon (1oC) as it is attached
directly to only one other carbon. The methyl carbon is also a primary carbon.
The carbon in the middle is a secondary carbon (2oC) as it is bonded directly
to two other carbons.

Primary hydrogens (1oH) and secondary hydrogens (2oH).

•   The 1oC bearing Br has two 1oH.

•   The 1oC of the CH3 group has three primary hydrogens.

•   The middle secondary carbon has two secondary hydrogens.

Examples:
CH3CH(Br)CH2CH3 The C attached to the Br is aso directly attached to two
carbons so the C is a secondary carbon (2oC) and this is a
secondary alkyl bromide.

(CH3)3CF The C attached to the F atom is also attached to three carbons

so it is a tertiary carbon (3oC). This is a tertiary alkyl fluoride.
 28

C5H12, Pentane Write the possible structural/constitutional isomers.

C6H14, Hexane Write the possible constitutional isomers.

C7H16, Heptane 9 isomers C8H18, Octane 18 isomers

C9H20, Nonane 35 isomers C10H22, Decane 75 isomers
Obviously with such a vast amount of compounds a better nomenclature
system is needed; the I.U.P.A.C. systematic system is used most often.
29