CH-208 II Analytical Chemistry II Dr.

Saad nadeem 1
CH-208 II Analytical Chemistry II Dr. Saad nadeem 2
CH-208 II Analytical Chemistry II Dr. Saad nadeem 3
REVERSE REACTION
→ reciprocal K

CH-208 II Analytical Chemistry II Dr. Saad nadeem 4

ADD REACTIONS
→ Multiply Ks

CH-208 II Analytical Chemistry II Dr. Saad nadeem 5

The equilibrium constant for the reaction H2O  H+ + OH- is called Kw (= [H+][OH -])
and has the value 1.0 x 10-14 at 25oC.
Given that KNH3 = 1.8 x 10-5 for the reaction NH3(aq) + H2O  NH4+ + OH- , find K for
the reaction NH4+  NH3(aq)+ H+

CH-208 II Analytical Chemistry II Dr. Saad nadeem 6

TEST YOURSELF

For the reaction

Li+ + H2O  Li(OH) (aq) + H +, KLi = 2.3 x 10-14.
Combine this reaction with the Kw reaction to find the
equilibrium constant for the reaction
Li + + OH-  Li(OH) (aq).

(Answer: 2.3)

CH-208 II Analytical Chemistry II Dr. Saad nadeem 7

 ADD REACTIONS→ Multiply Ks
Given the following equilibrium constants:
CaCO3(s) → Ca2+ (aq) + CO32- (aq) K1 = 10-8.4
HCO3(s) → H+(aq) + CO32- (aq) K2 = 10-10.3
Calculate the value of K for the reaction
CaCO3(s) + H+(aq) → Ca2+ (aq) + HCO3- (aq)

8
 LE CHATELIER’S PRINCIPLE
Every change in one of the factors of an equilibrium
occasions a rearrangement of the system in such
direction that the factor in question experiences a
change in the sense opposite to the original change.

HENRI LOUIS
LE CHÂTELIER

Born: October 8, 1850, Paris, France

CH-208 II Analytical Chemistry II Dr. Saad nadeem 9
Died: September 17, 1936 (age 85 years)
To see what this statement means, let’s see what happens when we change the
concentration of one species of the following reaction in water:

In one particular equilibrium state of this system, the concentrations are [H+] = 5.0
M, [𝐶𝑟2 𝑂72− ] = 0.10 M, [Cr3+] = 0.0030 M, [Br-] = 1.0 M, and [𝐵𝑟𝑂3− ] = 0.043 M.
Suppose that the equilibrium is disturbed by adding dichromate to the solution to
increase [𝐶𝑟2 𝑂72− ] from 0.10 to 0.20 M.
In what direction will the reaction proceed to reach equilibrium?
10
When the temperature of a system is changed, so is the equilibrium constant.

The term 𝑒 ∆𝑆°/𝑅 is independent of T (at least over a limited temperature range
in which ∆𝑆 ° is constant).

The term 𝑒 ∆𝐻 increases with increasing temperature if ∆𝐻 ° is positive and

° /𝑅𝑇

decreases if ∆𝐻 ° is negative.

Therefore:
1. The equilibrium constant of an endothermic reaction (∆𝐻 ° = + ) increases
if the temperature is raised
2. The equilibrium constant of an exothermic reaction (∆𝐻 ° = − ) decreases
if the temperature is raised.
CH-208 II Analytical Chemistry II Dr. Saad nadeem 11
 LE CHATELIER’S PRINCIPLE A: ➔
B: 
CO2 + H2 → H2O(g) + CO C: ==
a drying agent is added to absorb H2O

H2(g) + I2(g) → 2HI(g) Some nitrogen gas is added

CH-208 II Analytical Chemistry II Dr. Saad nadeem 12

 LE CHATELIER’S PRINCIPLE
A: ➔
NaCl(s) + H2SO4(l) → Na2SO4(s) + HCl(g) B: 
reaction is carried out in an open container C: ==

H2O(l) → H2O(g)
water evaporates from an open container

CH-208 II Analytical Chemistry II Dr. Saad nadeem 13

 LE CHATELIER’S PRINCIPLE
A: ➔
B: 
AgCl(s) → Ag+(aq) + Cl–(aq) C: ==
some NaCl is added to the solution

N2 + 3 H2 → 2 NH3
a catalyst is added to speed up this reaction

CH-208 II Analytical Chemistry II Dr. Saad nadeem 14

LE CHATELIER’S PRINCIPLE A: ➔
B: 
C: ==
Br2(g) → 2 Br (g)
Pressure increased

CH-208 II Analytical Chemistry II Dr. Saad nadeem 15

 REACTION QUOTIENT, Q

K is thus the special value that Q has when the reaction is at equilibrium

CH-208 II Analytical Chemistry II Dr. Saad nadeem 16

 REACTION QUOTIENT, Q

K is thus the special value that Q has when the reaction is at equilibrium

CH-208 II Analytical Chemistry II Dr. Saad nadeem 17

 REACTION QUOTIENT, Q
Phosgene (COCl2) is a poisonous gas that dissociates at high temperature into two
other poisonous gases, carbon monoxide and chlorine. The equilibrium constant
Ka = 0.0041 at 600°K. Find the equilibrium composition of the system after 0.124
atm of COCl2 is allowed to reach equilibrium at this temperature.

COCl2⇌CO(g)+Cl2(g)

CH-208 II Analytical Chemistry II Dr. Saad nadeem 18

 “K” IS DIMENSIONLESS!
•Concentrations in mol/liter (M)
•Pressures in atmospheres (atm)
•Ignore pure solids and Liquids
•Ignore solvents

The activities of pure solids and liquids are equal to 1. They do not affect
the reactant amount at equilibrium in the reaction
CH-208 II Analytical Chemistry II Dr. Saad nadeem 19
 Equilibrium calculation EXAMPLE

I2(s) + 5Br2(aq) + 6H2O → 2IO3- + 10 Br- + 12H+

K = 1 x 10-19

0.001 mol Br2

0.005 mol IO3-
0.02 mol Br-
1.00 mol H+
Solid I2
What will be the concentrations at equilibrium?
CH-208 II Analytical Chemistry II Dr. Saad nadeem 20
1. If a reaction is at equilibrium and products are added (or
reactants are removed), the reaction goes to the left.

2. If a reaction is at equilibrium and reactants are added (or

products are removed), the reaction goes to the right.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 21

THERMODYNAMICS and Equilibrium

CH-208 II Analytical Chemistry II Dr. Saad nadeem 22

 SOLUBILITY PRODUCT Ksp

Ksp = equilibrium constant

of a reaction that
forms a precipitate

CH-208 II Analytical Chemistry II Dr. Saad nadeem 23

SOLUBILITY PRODUCT Ksp

CH-208 II Analytical Chemistry II Dr. Saad nadeem 24

SOLUBILITY PRODUCT Ksp

Ksp = [Ca2+]3[PO43-]2 = 1.0 x 10-26

= (3x)3(2x)2 = 1.0 x 10-26

CH-208 II Analytical Chemistry II Dr. Saad nadeem 25
SOLUBILITY PRODUCT Ksp

COMMON ION EFFECT

C+S CuSO4(aq)

CuI

(I) in sea
water
CH-208 II Analytical Chemistry II Dr. Saad nadeem
already 26
 SOLUBILITY PRODUCT Ksp
Initially some H3PO4 was
present already in water
COMMON ION EFFECT

Ksp = 1.0 x 10-26

27
CH-208 II Analytical Chemistry II Dr. Saad nadeem
CH-208 II Analytical Chemistry II Dr. Saad nadeem 28
 SOLUBILITY PRODUCT Ksp I¯

SEPARATION BY PRECIPITATION

Which will form a precipitate first?

Higher or lower Ksp?
A

B
C

29
CH-208 II Analytical Chemistry II Dr. Saad nadeem
 SOLUBILITY PRODUCT Ksp I¯

SEPARATION BY PRECIPITATION

Starting with 0.01 M of each,

can you precipitate 99.99% of Hg22+
without losing any Pb2+ By adding some I-?

CH-208 II Analytical Chemistry II Dr. Saad nadeem 30

if we can lower [𝐻𝑔22+ ] to 0.010% of 0.010 M = 1.0 x 10-6 M without
precipitating Pb2+.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 31

Will this concentration of I- cause 0.010 M Pb2+ to precipitate? That is, is the
solubility product of Pb2+ exceeded?

CH-208 II Analytical Chemistry II Dr. Saad nadeem 32

 Complex Formation

If anion X- precipitates metal M+, it is often observed that a high

concentration of X- causes solid MX to re-dissolve.

The increased solubility arises from formation of complex ions,

such as 𝑀𝑋2− , which consist of two or more simple ions bonded to
one another.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 33

 Notation for Complex Ion Formation Constants

The stepwise formation constants, (Ki) are

The overall, or cumulative, formation constants (βi ):

CH-208 II Analytical Chemistry II Dr. Saad nadeem 34

 Effect of Complex Ion Formation on Solubility
If Pb2+ and I- only reacted to form solid Pb2+, then the solubility of Pb2+ would
always be very low in the presence of excess I- :

high concentrations of I- cause solid Pb2+ to dissolve

The species PbI2+(aq) in Reaction 6-14 is dissolved PbI2, containing two iodine
atoms bound to a lead atom. Reaction 6-14 is not the reverse of Reaction 6-12,
in which the species is solid PbI2.
CH-208 II Analytical Chemistry II Dr. Saad nadeem 35
 Effect of I- on the Solubility of Pb-1
Find the concentrations of PbI+ , PbI2(aq),𝑃𝑏𝐼3− ,𝑃𝑏𝐼42− in a solution saturated
with PbI2(s) and containing dissolved I- with a concentration of (a) 0.001 0 M
and (b) 1.0 M.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 36

 TEST YOURSELF
Find [Pb2+], PbI2(aq), and [PbI3- ], in a saturated solution of PbI2(s)
with [I2] = 0.10 M.
(Answer: 7.9 x 10-7, 1.1 x 10-5, 6.6 x 10-6 M)

CH-208 II Analytical Chemistry II Dr. Saad nadeem 37

 BrO3¯

SOLUBILITY PRODUCT Ksp

SEPARATION BY PRECIPITATION

When (BrO3—) is added to a solution containing equal concentrations

of Ag+ and Pb2+, which will precipitate first and why?

Ksp = 5.49 x 10-5 for AgBrO3 A

Ksp = 3.23 x 10-5 for Pb(BrO3)2 B
C

CH-208 II Analytical Chemistry II Dr. Saad nadeem 38

Consider the following equilibria in aqueous solution: H.W

(a) Calculate the numerical value of the equilibrium constant for the reaction
.
(b) Calculate the concentration of AgCl(aq) in equilibrium with excess
undissolved solid AgCl.
−
(c) Find the numerical value of K for the reaction 𝐴𝑔𝐶𝑙2− ՞ 𝐴𝑔𝐶𝑙 𝑠 + 𝐶𝑙
 H.W

Fe(III) precipitates from acidic solution by addition of OH- to form

Fe(OH)3(s). At what concentration of OHwill [Fe(III)] be reduced to 1.0
x 1010 M? If Fe(II) is used instead, what concentration of OH- will reduce
[Fe(II)] to 1.0 x 1010 M?
 H.W

Is it possible to precipitate 99.0% of 0.010 M Ce3+ by adding

oxalate (𝐶2𝑂42− ) without precipitating 0.010 M Ca2+?
 Gas – Solution Equilibrium KH

The (solubility)/amount of dissolved gas in a liquid is proportional

to its partial pressure above the liquid
[dissolved gas] = KHP, where KH is the Henry’s law constant.
CO2 dissolves in water:

CO2(g) + H2O <==> H2CO3 (aq) KH = 3.4 x 10-2

At a CO2 pressure of 3 x 10-4 atmospheres,

what is the concentration of the carbonic acid in the water?

CH-208 II Analytical Chemistry II Dr. Saad nadeem 42

WATER EQUILIBRIUM Kw

CH-208 II Analytical Chemistry II Dr. Saad nadeem 43

 WATER EQUILIBRIUM Kw

pH

CH-208 II Analytical Chemistry II Dr. Saad nadeem 44

Calculate the concentrations of H+ and OH- in pure water at 25oC.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 45

What is the concentration of OH- if [H+] = 1.01 x 10-3 M?

What is the concentration of OH- if [H+] = 1.01 x 10-5 M?

CH-208 II Analytical Chemistry II Dr. Saad nadeem 46
 Lewis Acids and Bases
A Lewis acid accepts a pair of electrons from a
Lewis base when the two form a bond:

The product of the reaction between a Lewis acid and a Lewis

base is called an adduct.

The bond between a Lewis acid and a Lewis base is called a

dative or coordinate covalent bond.
CH-208 II Analytical Chemistry II Dr. Saad nadeem 47
 ACIDS & BASES
Brønsted-Lowry

Acids donate proton (H+) ions to other ions or molecules,

which act as a base (proton acceptor).

In an operational sense:

• an acid is any substance that increases the concentration of

the H+ ion when it dissolves in water.

• a base is any substance that increases the concentration of

the OH- ion when it dissolves in water.
CH-208 II Analytical Chemistry II Dr. Saad nadeem 48
The Role of H+ and OH- Ions in Aqueous Solutions

To what extent does H2O dissociate to form ions?

At 25°C, the density of water is 0.9971 g/cm3,

or 0.9971 g/mL.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 49

The Role of H+ and OH- Ions in Aqueous Solutions

To what extent does H2O dissociate to form ions?

The concentration of the H+ and OH- ions formed
by the dissociation of neutral H2O molecules at this
temperature is only 1.0 x 10-7 mol/L.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 50

 The Role of H+ and OH- Ions in Aqueous Solutions
To what extent does H2O dissociate to form ions?
The concentration of the H+ and OH- ions formed by the
dissociation of neutral H2O molecules at this temperature is only
1.0 x 10-7 mol/L.

Accordingly, the ratio of the concentration of the H+ (or OH-) ion

to that of the neutral H2O molecules is 1.8 x 10-9.
CH-208 II Analytical Chemistry II Dr. Saad nadeem 51
The Role of H+ and OH- Ions in Aqueous Solutions

To what extent does H2O

dissociate to form ions?

At 25°C only about 2 parts per billion (ppb)

of the H2O molecules dissociate into ions.

CH-208 II Analytical Chemistry II Dr. Saad nadeem 52

CH-208 II Analytical Chemistry II Dr. Saad nadeem 53
 ACIDS & BASES

CH-208 II Analytical Chemistry II Dr. Saad nadeem 54

 Strong Acids and Bases

The complete dissociation of HCl into H+ and Cl - makes

HCl(g) extremely soluble in water.

Net
reaction:
CH-208 II Analytical Chemistry II Dr. Saad nadeem 55
 Weak Acids and Bases
weak acids, (HA), react with water by donating a proton to H2O:

Dissociation of weak acid:

which means exactly the same as

weak base, B, reacts with water by abstracting a proton from H2O:

CH-208 II Analytical Chemistry II Dr. Saad nadeem 56

CH-208 II Analytical Chemistry II Dr. Saad nadeem 57
Conjugated Acids and Bases
acid1 + base2 <===> acid2 + base1

Acid1 Base1 Acid2 Base2

Conjugated base to acid HCl

Conjugated acid to base H2O

CH-208 II Analytical Chemistry II Dr. Saad nadeem 58

CH-208 II Analytical Chemistry II Dr. Saad nadeem 59
What is Kb for the acetate ion? KW = Ka . K b

KW = 1.01 x 10-14

CH-208 II Analytical Chemistry II Dr. Saad nadeem 60

What is Ka for the methylamonium ion?

CH-208 II Analytical Chemistry II Dr. Saad nadeem 61

Polyprotic Acids and Bases

Polyprotic acids and bases are compounds that can donate or accept more
than one proton.

For example, oxalic acid is diprotic and phosphate is tribasic:

CH-208 II Analytical Chemistry II Dr. Saad nadeem 62

For a diprotic acid, we can derive relationships between
each of two acids and their conjugate bases:

Ka1 . Kb2 = KW
Ka2 . Kb1 = KW

CH-208 II Analytical Chemistry II Dr. Saad nadeem 64

CH-208 II Analytical Chemistry II Dr. Saad nadeem 65