CHAPTER 3: ACIDS AND BASES

Acids and Bases

Bronsted-Lowry definition:
Acid is a substance that donates a proton.
Base is a substance that accepts a proton.
Conjugate acid: product that results when a base gains a proton.
Conjugate base: product that results when an acid loses a proton.
Examples:
2 H2O

H2O H OH H2O H2O

strongest acid strongest base conjugate base conjugate acid
in water in water
Is H3O+ the strongest acid? No!!! just the strongest acid in water.
In fact H3O+ is formed when a stronger acid than H3O+ is dissolved
in water.
Example:

H2O H Cl H3O Cl
base acid conjugate acid conjugate base
hydronium is chloride is
weaker acid than HCl weaker base than H2O
The stronger the acid, the weaker its conjugate base.
The conjugate base of a strong acid is a weak (stable) base.
The conjugate base of a weak acid is a strong base.
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There are weaker acids than H3O+? Yes!!!

H2O H NH3 H2O NH4

stronger acid stronger base weaker base weaker acid
than amonium than water than NH3 than H3O+
Acid dissociation constant (Ka): measures the strength of an acid.
Ka = Keq x [solvent] pKa = - log Ka
small pKa ---> strong acid; large pKa ---> weak acid

Can we predict the strength of different compounds?

The most important factor is the kind of Element that is linked

to Hydrogen

Acidity Trends according to the position of the element linked to H

in the periodic chart.

The acidity increases from left to right due to increased

electronegativity.

The acidity increases from the top to the bottom due to increased
polarizability (ability to deform the electron density in the atom).
Larger atoms polarize easier because the valence electrons () are
farther away from the nucleus ().
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 Order of Acidity
CH4 NH3 H 2O HF
pKa = 50 pKa = 36 pKa = 15.7 pKa = 3.2

SiH4 PH3 H 2S HCl

pKa = 7 pKa = 7

GeH4 AsH3 H2Se HBr

pKa = 3.9 pKa = 9

H2Te HI
pKa = 2.6 pKa = 10

Water an acid? Yes, when it is compared to other compounds with

larger pKas.

Methane an acid? (possibly the weakest acid of all, obviously

because of its extremely large pKa).

Can CBr4 act as a Bronted-Lowery acid? Dont say YES just

because there are 4 Bromine atoms.
Where is the H+ that can be donated? Remember your
definitions!!!! Not all is just about memorizing a trend.
OK? Compende? Capici?

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The second factor in importance deals with Induction,
specifically Electron withdrawing effect. Induction is the
shifting of electrons in a bond as a result of the electronegativity
of nearby atoms.

For instance:
O
CH4 CH3Cl CH3SCH3 CH3CN
pKa = 50 pKa = 43 (aprox) pKa = 35 pKa = 25

O O O
CH3CCH3 CH3NO2 CH3CCH2CCH3
pKa = 20 pKa = 10 pKa = 9

O
CH3SH CH3OH CH3COH
pKa = 10.4 pKa = 15 pKa = 4.8

O O O O
ICH2COH BrCH2COH ClCH2COH FCH2COH
pKa = 3.15 pKa = 2.86 pKa = 2.81 pKa = 2.66

O O
Cl2CHCOH Cl3CCOH
pKa = 1.29 pKa = 0.65

O O O
ClCH2CH2CH2COH CH3CHCH2COH CH3CH2CHCOH
Cl Cl
pKa = 4.52 pKa = 4.06 pKa = 2.84
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The third factor in importance is the Resonance.
For instance:
Resonance stabilizes the conjugate base

OH O O O O

pKa = 10

OH O

pKa = 18

Other factors to consider:

The hybridization of the carbon attached to hydrogen.

electonegativity and acidity increases

CH3CH3 CH2 CH2 CH CH

sp3 sp2 sp
pKa = 50 pKa = 44 pKa = 25

CH3CH2 CH2 CH CH C

the stronger the acid the weaker its conjuate base and viceversa

Protonation increases acidity. The Trend remains the same!

NH3 H2O now protonate both NH4+ H3O+
pKa = 36 pKa = 15.7 pKa = 9.3 pKa = 1.7
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 pKa of different compounds
pKa acids conjugate bases

2 CF3SO3H CF3SO3
10 HI I
9 HBr Br
7 HCl Cl
2 CH3SO3H CH3SO3
1.7 H3O+ H2O
2.8 ClCH2CO2H ClCH2CO2
3.2 HF F
4.8 CH3CO2H CH3CO2

7.14 O2N OH O2N O

10 OH O

15 CH3OH CH3O

15.7 H2O HO

25 CH CH CH C

35 H2 H

36 NH3 H2N
40 CH3NH2 CH3NH
44 CH2 CH2 CH2 CH

50 CH3CH3 CH3CH2

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Arrange the following compounds in order of decreasing acidity
(strongest first).

CH3CH2OH ClCH2COOH BrCH2COOH FCH2COOH CH3CO2H

A B C D E

__ > __ > __ > __ > __

Arrange the following ions in order of decreasing basicity
(strongest first).

NH2 - OH - SH - CH3- I-

__ > __ > __ > __ > __

Given the following order of basicity:
NH2 > CH3O > OH > CH3CO2
amide methoxide hydroxide acetate

a. Write a chemical equation between hydroxide and ammonia.

Indicate with a solid arrow if the equilibrium favors reactants ( ) or products (
).

b. Write a chemical equation between methoxide and water.

Indicate with a solid arrow if the equilibrium favors reactants ( ) or products (
).

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 Lewis Acids and Bases

Lewis definition (broader):

Acid is a substance that accepts 2 electrons. Electrophile
incomplete cation positive
octet dipole
H
B O N O O C O
H H

Cl CH3 O
Al C C
Cl Cl CH3 CH3 H H

Base is a substance that donates 2 electrons. Nucleophile

Neutral Molecules with Anions
lone pair of electrons

H2O Br Br OH HS I Cl

(CH3)3P O e- CH C O H
CH3CCH3 CH3CO
CH3SCH3 C N (CH3)2N

The donated pair of electrons is shared in a newly formed covalent

bond.

For example:

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 H2S + BF3 H2SBF3
Lewis Base Lewis Acid Complex
Nucleophile Electrophile

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