If only the salt s cation affects

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End Lecture 8 pH, the solution is acidic

Is NH4Cl acidic or basic in water?
Start Lecture 9
Acid Base Reactions
Lewis Acid Base
Acid-Base Properties of Salts

Syllabus Learning Outcomes : 6, 7

Dr. Michael Love (1) © 2007 21

If only the salt s cation affects

3 4

If only the salt s cation affects

pH, the solution is acidic pH, the solution is acidic
Is NH4Cl acidic or basic in water? NH4Cl(aq) → NH4+(aq) + Cl-(aq)
NH4Cl(aq) → NH4+(aq) + Cl-(aq) Answer: (b) React cation, NH4+, with H2O
Answer: (a) React anion, Cl-, with H2O NH4+ + H2O → NH3 + H3O+
Cl- + H2O → HCl + OH- acid base base acid
base acid acid base NH4+ is a weak acid, and NH3 is a weak base.
Because Cl- is the conjugate base of a very
strong acid (HCl), Cl- does not affect pH. NH4+ gives an acidic solution
or Ka(NH4+) > Kb(Cl-) so solution is acidic
Cl- gives a neutral solution, no effect on pH

If only the salt s anion affects If only the salt s anion affects
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pH, the solution is basic pH, the solution is basic

Calculate the pH of 0.10 M Na2CO3, Kb=2.1 x 10-4. Calculate the pH of 0.10 M Na2CO3, Kb=2.1 x 10-4.
Answer: (a) Cation: Na+ + H2O → neutral
(b) Anion: CO32- + H2O → weak base
CO32- + H2O ↔ HCO3- + OH-
base acid acid base
Step 1. Set up ICE table for weak base
[CO32-] [HCO3-] [OH-]
initial
change
equilib

1
 If only the salt s anion affects If only the salt s anion affects
7 8

pH, the solution is basic pH, the solution is basic

Calculate the pH of 0.10 M Na2CO3, Kb=2.1 x 10-4. Calculate the pH of 0.10 M Na2CO3, Kb=2.1 x 10-4.
Answer: (a) Cation: Na+ + H2O → neutral Step 2. Solve equilibrium expression
(b) Anion: CO32- + H2O → weak base
[HCO3-][OH-] x2
CO32- + H2O ↔ HCO3- + OH-
Kb= 2.1x10-4 = ―――――― = ―――
base acid acid base [CO32-] 0.10-x
Step 1. Set up ICE table for weak base
[CO32-] [HCO3-] [OH-] 100*Kb<0.1, so 0.10-x ≈ 0.10, giving
initial 0.10 0 0 x= [HCO3-]= [OH-]= 0.00458M
change -x +x +x pOH= 2.33, and pH= 11.66
equilib 0.10 - x x x 0.1M Na2CO3 is a basic solution.

If neither the salt s cation nor If neither the salt s cation nor
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anion affects pH, the solution is anion affects pH, the solution is
neutral, pH=7 neutral, pH=7
Is 0.1M NaCl acidic or basic in water? Is 0.1M NaCl acidic or basic in water?

Answer: (a) We did Na+ and Cl−, before.

Neither Na+ nor Cl− affect pH (Na+ from

NaOH and Cl− from HCl).

0.1M NaCl is neutral in water.

If both the salt s cation and If both the salt s cation and
11 12

anion affect pH, the larger of Ka anion affect pH, the larger of Ka
and Kb determine pH and Kb determine pH
Is 0.1M NH4Bz acidic or basic in water? Is 0.1M NH4Bz acidic or basic in water?
Answer: Look up Ka(NH4+) and Kb(Bz−)
(a) Ka for NH4+ = 5.6x10-10
(b) Kb for Bz− = 1.6x10-10
Ka(NH4+) > Kb(Bz−)

NH4Bz makes weakly acidic aqueous

solutions.

2
Define Lewis acid & Lewis
13 14

Lewis acids and bases react

base H
•  New bond (Coordinate
Lewis acid: a substance

―
H ―B H covalent bond) forms
that accepts an electron

―
H using electron pair

―
H ―B H
pair from the Lewis base.

―
―
H H― H
B― •  Geometry changes
+

―
Lewis base: a substance after reaction (VSEPR

:
N― N―
that donates an electron H― H H― H model).

―
N―
pair

H H― H H

―
H

15 16

Lewis acids & bases react Lewis acids & bases react

hydronium ion has a coordinate covalent Ammonium ion has a coordinate covalent
bond bond

+ H +
H :

― ―
H N―
+
H H― H N―
:

+
―

+ H ―O H―
―

―
H
:

H + :O H
―

H
―

H H

17 18

Lewis acids & bases react Lewis acids & bases react
Metal ions form coordinate covalent Metal ions form coordinate covalent
bonds and complex ions bonds and complex ions
NH3 2+ NH3 2+
―

―
:

2+ N― 2+ N―
Zn + 4H― H H3N―Zn―NH3 Cu + 4H― H H3N―Cu―NH3
―

―
―

H H
NH3 NH3
Acid Base
OH2 3+
As a result, copper ion (a Lewis acid) can
―
:

Fe
3+
+ 3 : O― H Fe―OH2 react with ammonia (a Lewis base).
―

H
OH2

3
 19 20

Lewis acids & bases react in Many water-containing

biology complex ions hydrolyze
•  The heme group in hemoglobin
(undergo hydrolysis) to give acidic
interacts with O2 and CO. solutions.
•  The Fe ion in hemoglobin is a Lewis
acid
[Cu(H2O)4]2+ + H2O →
•  O2 and CO can act as Lewis bases
[Cu(H2O)3(OH)]+ + H3O+
•  CO has a strong (irreversible) binding
constant with hemoglobin, whereas O2
binds more weakly and reversibly.

21 22

Hydrolysis makes solutions of Fe3+, Al3+, Brønsted and Lewis theories explain
amphoteric nature of some metal hydroxides.
Cu2+, and Pb2+ acidic.

Cu2+―OH2 bond weakens this O―H bond

Al(OH)3(s) + 3 H+ → Al3+ + 3 H2O
allowing Here Al(OH)3 is a Brønsted base.
another H2O to
take H+,
(hydrolysis) Al(OH)3(s) + OH- → Al(OH)4-
−
Here Al(OH)3 is a Lewis acid. Al3+ ß :OH−
:

2+ ― O : +
Cu
:

H
: O―
―

H
―

H
H

23 24

Complex ion formation can CH3CO2H is an Acid

dissolve a precipitate
1. Electronegativity of O atoms takes e−,
AgCl(s) ↔ Ag+ + Cl- Ksp = 1.8 x 10-10 weakening O―H bond.
Ag+ + 2NH3 ↔ Ag(NH3)2+ Kform = 1.6 x 107 2. H atom in O—H can be taken by H2O to
―――――――――――――――― form H3O+.
AgCl(s) + 2NH3 ↔ Ag(NH3)2+ + Cl- Knet=
O
Knet = Ksp*Kform = 2.9x10-3, so some precipitate − +
=

dissolves
CH3― C―O H : O― H
―

4
 25 26

Basisity oxoanions  as − charge 

CH3CO2H CCl3CO2H
Acetic acid Trichloroacetic acid CO32- PO43-
NO3-
Ka = 1.8 x 10-5 Ka = 0.3
Least basic Most basic

• Trichloroacetic acid is stronger than

acetic acid because electronegative Cl As charge  , water interaction  , basicity 
in -CCl3 stabilizes ―O− anion more than
the H in -CH3.
These are both Bronsted and Lewis bases

27

Basisity oxoanions é as #Oê

Least basic Most basic

ClO3- < ClO2- < ClO-

As # oxygens é , strength of acid é,

basicity conjugate base ê. Recall that
HClO4 is a strong acid.