REVERSE REACTION

 reciprocal K
ADD REACTIONS
 Multiply Ks
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)+ OH+

Solution
The third reaction can be obtained by reversing the second
reaction and adding it to the fi rst reaction:
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)
ADD REACTIONS
 Multiply Ks

-8.4

-8.4

K1.K2
 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
 LE CHATELIER’S PRINCIPLE A: 
B: 
CO2 + H2  H2O(g) + CO C: ==
a drying agent is added to absorb H2O
Shift to the right.
Continuous removal of a product will force any reaction to the right

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

No change; N2 is not a component of this reaction system.

 LE CHATELIER’S PRINCIPLE
A: 
NaCl(s) + H2SO4(l)  Na2SO4(s) + HCl(g) B: 
reaction is carried out in an open container C: ==
Because HCl is a gas that can escape from the system,
the reaction is forced to the right.
This is the basis for the commercial production of hydrochloric acid.

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

Continuous removal of water vapor forces the reaction to the right,

so equilibrium is never achieved
 LE CHATELIER’S PRINCIPLE A: 
B: 
AgCl(s)  Ag+(aq) + Cl–(aq)
C: ==
some NaCl is added to the solution
Shift to left due to increase in Cl– concentration.
This is known as the common ion effect on solubility.

N2 + 3 H2  2 NH3
a catalyst is added to speed up this reaction
No change.
Catalysts affect only the rate of a reaction;
they have no effect at all on the composition of the
equilibrium state
 LE CHATELIER’S PRINCIPLE A: 
B: 
C: ==
Br2(g)  2 Br (g)
Pressure increased
shift to left
To reduce number of molecules or atoms
 REACTION QUOTIENT, Q

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

K is thus the special value that Q has when the reaction is at equilibrium
REACTION QUOTIENT, Q
THERMODYNAMICS and Equilibrium
HABER-BOSCH:

N2 + 3 H2  2 NH3 + E
“K” IS DIMENSIONLESS!
•Concentrations in mol/liter (M)
•pressures in atmospheres (atm)
•ignore solids
•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
 Equilibrium calculation EXAMPLE

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?

 Equilibrium calculation EXAMPLE

0.001 mol Br2

First calculate Q to know the direction
0.005 mol IO3-
0.02 mol Br-
1.00 mol H+
Solid I2

So which way does it go?

 Equilibrium calculation EXAMPLE

0.001 mol Br2

0.005 mol IO3-
0.02 mol Br-
Make an ICE table
1.00 mol H+
Solid I2

Solve for x
 SOLUBILITY PRODUCT Ksp

Ksp = equilibrium constant

of a reaction that forms
a precipitate
SOLUBILITY PRODUCT Ksp
SOLUBILITY PRODUCT Ksp

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

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

SOLUBILITY PRODUCT Ksp

COMMON ION EFFECT

C+S
 SOLUBILITY PRODUCT Ksp

COMMON ION EFFECT

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

= (3x)3(0.10 + 2x)2 = 1.0 x 10-26
SOLUBILITY PRODUCT Ksp I¯

SEPARATION BY PRECIPITATION

Which will form a precipitate first?

Higher or lower Ksp?

A

B
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+?
if we can lower [Hg2 2+ ] to 0.010% of 0.010 M = 1.0 x 10-6
M without precipitating Pb2+.

To see if any Pb2+ should precipitate, we need to know the

concentration of I- in equilibrium with precipitated Hg2I2 (s)
plus the remaining 1.0 x 10-6 M Hg2 2+ .
Will this concentration of I- cause 0.010 M Pb2+ to precipitate? That is,
is the solubility product of Pb2+ exceeded?

Q = [Pb2+][I-]2 = (0.010) (6.8 x 10-12)2

= 4.6 x 10-25 , Ksp (for Pb2+)

The reaction quotient, Q = 4.6 x 10-25 , > Ksp for Pb2+ = 7.9 x 10-9.
Therefore, Pb2+ will not precipitate.

The separation of Pb2+ and Hg2 2+ is feasible.

We predict that adding I- to a solution of Pb2+ and Hg2 2+ will

precipitate virtually all Hg2 2+ before any Pb2+ precipitates.

 Complex Formation

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

high concentration of X- causes solid MX to redissolve.

The increased solubility arises from formation of complex

ions, such as MX2 − , which consist of two or more simple
ions bonded to one another.
 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.
 Notation for Complex Ion Formation Constants

The stepwise formation constants, (Ki) are

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

 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 Pb2+(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.
 Effect of I2 on the Solubility of Pb21
Find the concentrations of PbI+ , PbI2(aq), PbI3 + , PbI4 2− 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.

Solution
(a) From Ksp for Reaction 6-12, we calculate

[PbI2+] = Ksp/[I-]2 = (7.9 x 10 -9)/ (0.001)2 = 7.9 x 10 -3 M

From Reactions 6-13 through 6-16, we then calculate the concentrations of the other
Pb[II] species:

[PbI+ ] = K1[Pb2+][I-] = (1.0 x 102)(7.9 x 10 -3)(1.0 x 10 -3)

= 7.9 x 10 -4M

[PbI2(aq)] = β2[Pb2+][I-]2 = 1.1 x 10 -5 M

[PbI3 − ] = β2[Pb2+][I-] 3 = 6.6 x 10 -8 M

[PbI4 2− ] = β2[Pb2+][I-] 4 = 2.4 x 10 -10 M

(b) If, instead, we take [I-] = 1.0 M, then analogous computations show that

[PbI2+] = Ksp/[I-]2 = (7.9 x 10 -9)/ (1)2 = 7.9 x 10 -9 M

From Reactions 6-13 through 6-16, we then calculate the

concentrations of the other Pb[II] species:

[PbI+ ] = K1[Pb2+][I-] = (1.0 x 102)(7.9 x 10 -9)(1.0)

= 7.9 x 10 -7M

[PbI2(aq)] = β2[Pb2+][I-]2 = 1.1 x 10 -5 M

[PbI3 − ] = β2[Pb2+][I-] 3 = 6.6 x 10 -5 M

[PbI4 2− ] = β2[Pb2+][I-] 4 = 2.4 x 10 -4M

[Pb]Total = [PbI2+] + [PbI+ ] +
[PbI2(aq)] + [PbI3 − ] + -2.06
[PbI4 2− ]

-3.49
When,
[I-] = 0.001 M,
[Pb]Total = 8.7 x 10-3 M

When,
[I-] = 1.0 M,
[Pb]Total = 3.2 x 10-4 M
 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
 Gas – Solution Equilibrium KH

The amount of dissolved gas in a liquid is

proportional to its partial pressure above the liquid

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?

𝐻2 𝐶𝑂3 −2 𝐻2 𝐶𝑂3
𝐾𝐻 = => 3.4 x 10 =
𝑃𝐶𝑂2 3 x 10−4
10-5 M
WATER EQUILIBRIUM Kw
WATER EQUILIBRIUM Kw

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

Solution:

Table 6-1 shows how Kw varies with temperature.

Its value at 25.0oC is 1.01 x 10-14.

The stoichiometry of equation tells us that H+ and OH- are produced

in a 1 : 1 molar ratio. Their concentrations must be equal.

Calling each concentration x, we can write

Kw = 1.01 x 10-14 = [H+][OH-] = [x][x] => x = 1.01 x 10-7 M

The concentrations of H+ and OH- are both 1.01 x 10-7 M in pure water.
What is the concentration of OH- if [H+] = 1.01 x 10-3 M?

Solution

Putting [H+] = 1.01 x 10-3 M into the Kw expression gives

Kw = 1.01 x 10-14 = [H+][OH-]

= [1.01 x 10-3 ][OH-]

[OH-] = 1.01 x 10-11 M

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

 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.
 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.

The concentration of H2O is 55.35 molar.

 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.
 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.
 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.
ACIDS & BASES
 Strong Acids and Bases

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

extremely soluble in water.

Net reaction:
 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:

 Conjugated Acids and Bases

acid1 + base2 <===> acid2 + base1

Acid1 Base1 Acid2 Base2

Conjugated base to acid HCl

Conjugated acid to base H2O
What is Kb for the acetate ion?

KW = Ka . Kb
KW = 1.01 x 10-14

A- + H2O  AH + OH-

Kb = 5.7 x 10-10
What is Ka for the methylamonium ion?

BH+  B + H+

Ka = 2.2 x 10-11
For a diprotic acid, we can derive relationships between
each of two acids and their conjugate bases:

Ka1 . Kb2 = KW

Ka2 . Kb1 = KW