Chemical Equilibrium

Chapter 5
1
CM1502
CM 1502 2
Chemical Equilibrium
1. Introduction
2. Equilibrium Constant
3. Reaction Quotient
4. Calculations involving Equilibrium Constant and Reaction
Quotients.
5. Equilibrium Constant in Pressure
6. Le Chateliers Principle
3
Kinetics applies to:
the speed of a reaction,
the concentration of product that appears (or of reactant that
disappears) per unit time.
Rate laws can have a complicated dependence on concentrations,
unrelated to the reaction stoichiometry and depend on reaction
mechanism
Equilibrium applies to:
the extent (yield) of a reaction,
the concentration of reactant and product that has appeared
after the reaction is set to run at a given temperature for an
unlimited time until no further change occurs
Equilibrium constant expressions can be deduced directly
from the reaction stoichiometry and do not depend on the
reaction mechanism.
k
K
CM 1502 4
At equilibrium: rate
forward
= rate
reverse

A system at equilibrium is dynamic on the molecular
level; no further net change is observed because
changes in one direction are balanced by changes in
the other.
Concentration of reactants and products not
necessarily equal.
Reactants
A
Products
B
2 moles of A is converted into B per second,
2 moles of B is converted into A per second.

CM 1502
5

N
2
O
4
(g, colourless) 2NO
2
(g, brown)


Reaching equilibrium on the macroscopic and
molecular levels.
A system is at equilibrium when its composition
doesn't change any more over time.
CM 1502
6
Approach Equilibrium from different Sides
H
2
+ I
2
2HI
From reactants
From products
*

pure H
2
+ pure I
2
(1:1)
pure HI
pure H
2
+ pure I
2
+ pure HI
(1:1:1)
equilibrium mixture of
H
2
, I
2
, HI
= same value = K
c

eqilibrium
n
eqilibrium
m
] [reactants
[products]
The equilibrium was approached from both the reactant and the
product side and a mixture of both, all three resulted in the same
relative composition.

CM 1502 7
Equilibrium constant (K
c
):




For a reaction at equilibrium aA + bB cC + dD




b a
d c
[B] [A]
[D] [C]
The Equilibrium Constant
K
c
=
K
c
=
eqilibrium
n
eqilibrium
m
] [reactants
[products]
CM 1502 8
Do Equilibrium Constants have
Units?
Equilibrium constants have no real units, because the
equilibrium constant for aA + bB cC + dD is exactly
expressed as:



where [A], etc are the concentrations at an agreed reference
state (which is 1 molL
-1
for solutes).

Because of the divisions, units (molL
-1
) of [A] and [A], etc
cancel and K
c
is truly dimensionless.
b o a o
d o c o
c
) ([B]/[B] ) ([A]/[A]
) ([D]/[D] ) ([C]/[C]
K =
CM 1502 9
Writing an Equilibrium Constant
NH
3
+ O
2
N
2
+ 1H
2
O


4NH
3
+ 3O
2
2N
2
+ 6H
2
O


K
C
(b) = (K
C
(a))
4


An equilibrium constant belongs to the specific chemical
equation with its specific stoichiometry.
0.75
2 3
1.5
2
0.5
2
C
] ][O [NH
O] [H ] [N
(a) K =
3
2
4
3
6
2
2
2
C
] [O ] [NH
O] [H ] [N
(b) K =
10
Combining Equilibrium Constants
Multiple equilibria

N
2
(g) + O
2
(g) 2NO(g)


2NO(g) + O
2
(g) 2NO
2
(g)


N
2
(g) + 2O
2
(g) 2NO
2
(g)





K
c
(1) =
[N
2
][O
2
]
[NO]
2
= 2.3 x 10
-19

K
c
(2) =
[NO]
2
[O
2
]
[NO
2
]
2
= 3 x 10
6

K
c
(overall) =
[N
2
][O
2
]
2

[NO
2
]
2
= 6.9 x 10
-13

= K
c
(1) x K
c
(2)
11
Write their K
c
Expressions

1. CH
3
COOH
(aq)
+ H
2
O
(l)
CH
3
COO
-
(aq)
+ H
3
O
+
(aq)

2. Hg
(l)
+ Cl
2(g)
HgCl
2(s)



3. CaCO
3(s)
CaO
(s)
+ CO
2(g)



COOH] [CH
] O ][H COO [CH
K
3
3 3
C
+
=
] [Cl
1
K
2
C
=
] [CO K
2 C
=
*
CM 1502




Solids and liquids are not included in K
c
.
Reaction Quotient (Qc)
] COO ][CH [NH
COOH] ][CH [NH
Q
3 4
3 3
c
+
=
The ratio of concentration terms written for a given reaction (non equilibrium)
is called the reaction quotient (Qc)
NH
4
+
+ CH
3
COO- NH
3
+ CH
3
COOH (in water)
] COO ][CH [NH
COOH] ][CH [NH
K
3 4
3 3
c
+
=
(non equilibrium system)
(equilibrium system)
CM 1502 13
Figure 17.5 Reaction direction and the relative sizes of Q and K.
Equilibrium:
no net change
reactants products
Reaction
Progress
reactants products
Reaction
Progress
CM 1502 14
*
CM 1502
15
H
2
+ I
2
2HI
Begin with 1 molL
-1
of HI, and let reaction reach
equilibrium with H
2
and I
2
at 25C (K
c
= 25). What will
be the final concentrations?
H
2
I
2
HI
initial 0 0 1
change +x +x -2x
equilibrium x x 1-2x
Forward reaction
Calculations involving K
c
CM 1502 16
Insert into K
c
equation:





Final concentrations: [HI] = 0.72, [H
2
] = [I
2
] = 0.14.
Put into K
c
expression for final check.
0.14 x 1 7x 5x 2x 1 5
x
2x 1
25
x
2x) (1
(x)(x)
2x) (1
] ][I [H
[HI]
K
2
2 2
2 2
2
c
= = = =

= =
4H
2
+ 4I
2
8HI
Begin with 1 molL
-1
of HI, and let reaction reach equilibrium
with H
2
and I
2
at 25C (K
c
= 25
4
= 390625). What will be the
final concentrations?
H
2
I
2
HI
initial 0 0 1
change +4x +4x -8x
equilibrium 4x 4x 1-8x
0.14 ] [I ] [H and 0.72 [HI]
0.0357 x 20x 8x 1 5
4x
8x 1
390625
4x
8x 1
390625
(4x)
8x) (1
(4x) (4x)
8x) (1
] [I ] [H
[HI]
K
2 2
8
8
8
4 4
8
4
2
4
2
8
c
= = =
= = =

= =
Typically,
equations are
written with
smallest integer
values.
CM 1502 17






CM 1502 18
N
2
O
4
2NO
2

Begin with 1 molL
-1
of N
2
O
4
, and let reaction reach
equilibrium with NO
2
at 500K (K
c
= 46). What will be the final
concentrations?
N
2
O
4
NO
2
initial 1 0
change -x +2x
equilibrium 1-x 2x
CM 1502 19
Insert into K
c
equation:





(the other solution, x = -12.425, is unphysical)
Final concentrations: [N
2
O
4
] = 0.075, [NO
2
] = 1.85.
Put into K
c
expression for final check.
0.925
8
53.4 46
8
46 * 4 * 4 46 46
x
0 46 46x 4x 46x 46 4x
46
x 1
(2x)
] O [N
] [NO
K
2
2 2
2
4 2
2
2
c
=
+
=
+
=
= + =
=

= =
Quadratic Equation
2a
4ac b b
x
2

=
20
K
P
and K
c
For gases, instead of K
c
one usually uses K
P
:


For any component X, with ideal-gas law PV = nRT, one gets


For the above example:
b a
d c
c
[B] [A]
[D] [C]
K =
b
B
a
A
d
D
c
C
P
P P
P P
K =
[X]RT RT
V
n
P
X
X
= =
c
b)] (a - d) [(c
b b a a
d d c c
b
B
a
A
d
D
c
C
P
K RT) (
(RT) [B] (RT) [A]
(RT) [D] (RT) [C]
P P
P P
K
+ +
= = =
c
n
K (RT) =
Gas constant = R = 0.0821 L atm mol
-1
K
-1
K
P
CM 1502 21
K
P
has units?
Equilibrium constants have no real units, because the
equilibrium constant for aA + bB cC + dD is exactly
expressed as:



where P
A
, etc are the concentrations at an agreed
reference state (which is in 1 bar (= 1 atm) (NOT Pa) for
gases).

Because of the divisions, units (bar) of P
A
and P
A
, etc
cancel and K
P
is truly dimensionless.
b
o
B B
a
o
A A
d
o
D D
c
o
C C
P
/P (P /P (P
/P (P /P (P
K
) )
) )
=
*
CM 1502 22
Le Chatelier's Principle
If a system in a state of equilibrium is disturbed, it
will undergo a change that shifts its equilibrium
position in a direction that reduces the effect of the
disturbance.
There are 4 types of stress/changes:
- amount of reactants and/or products
- pressure
- temperature
- catalyst

CM 1502 23
Le Chateliers Principle
Q depends on the amount of the reactants and
products, the pressure and the temperature.

The Q is always the same for a reaction, whether
a catalyst is present or not.

K is only dependent on T.

CM 1502 24
1. Change Amounts of Reactants
and/or Products
Adding product makes Q > K

Removing reactant makes Q > K

Adding reactant makes Q < K

Removing product makes Q < K

Reactants Products

CM 1502 25
2. Change Pressure
Only affects gases

- System will move in the direction that has the least
moles of gas when P is increased.

- Because partial pressures (and concentrations)
change, new equilibrium pressures (and
concentrations) must be reached.

- K remains the same.




26
The position of the equilibrium i.e. the concentrations of the
reactants and products, can be manipulated.
N
2
O
4
(g, colourless) 2NO
2
(g, brown)

At equilibrium at room T
Cool Heat

3. Change in Temperature
Only temperature changes can alter K.
The direction of the shift depends on whether the
reaction is exothermic or endothermic.
If forward reaction is exothermic (H -ve) then reverse
reaction is endothermic (H +ve).


27
Exothermic
When H < 0 (negative)
The reaction releases heat
Think of heat as a product
Raising temperature,
increases the product,
push towards reactants (left)
and Q and K decrease.
Decreasing temperature,
decreases the product,
push towards products
(right) and Q and K increase.
Endothermic
When H > 0 (positive)
The reaction absorbs heat
Think of heat as a reactant
Raising temperature,
increases the reactant,
push towards products
(right) and Q and K increase.
Decreasing temperature,
decreases the reactant,
push towards reactants (left)
and Q and K decrease.

CM 1502 28
Exothermic H < 0:
In (K
2
/K
1
) = (-(- ve)/R) - ve

K
2
/K
1
= exp(- ve)

K
2
/K
1
= < 1

K
2
< K
1

Increase T, K decreases.
(1/T
2
1/T
1
) is - ve when T
2
> T
1
Endothermic H > 0:
In (K
2
/K
1
) = (-(+ ve)/R) - ve

K
2
/K
1
= exp(+ ve)

K
2
/K
1
= > 1

K
2
> K
1

Increase T, K increases.
The vant Hoff Equation-the effect of T on K
ln
K
2

K
1

= -
H
o
rxn

R
1
T
2

1
T
1

-
R = universal gas constant
= 8.314 J /mol*K
K
1
is the equilibrium constant at T
1

K
2
is the equilibrium constant at T
2

CM 1502
*
CM 1502 30
Acid-Base Equilibrium
1. Arrhenius theory
2. Brnsted-Lowry and Lewis
3. Acid base strength
4. Autoionisation of water
5. pH scale and pK
w
6. Relationship between K
a

and K
b
7. Measure pH


8. Calculate pH, K
a
and K
b
9. Hydrolysis of salts
CM 1502 31
Arrhenius Theory
Acid:
- Has H in its formula.
- Substance that dissociates in water to produce hydronium
ions (H
3
O
+
).
- Acid + water H
3
O
+


Base:
- Has OH in its formula.
- Substance that dissociates in water to produce hydroxide
ions (OH
-
).
- Base + water OH
-


1859 1927
CM 1502 32
Limitation of Arrhenius definition

- substance can act as acid or base without H or OH in
their formula e.g. NH
3
common base.

- is limited to aqueous systems (many substances act
as acids or bases in non-aqueous solvents) e.g. in
organic solvent methanol.

*
33
Brnsted-Lowry
Acid:
- a substance which can donate a proton (H
+
).
- Proton donor
- must have a removable (acidic) proton.

Base:
- a substance which accepts a proton (H
+
).
- Proton acceptor.
-must have a pair of non-bonding electrons
(to accept proton)


CM 1502
Essentially, it is proton transfer from the acid to the base.
An acid-base reaction rather than an acid reaction or a
base reaction.
CM 1502 34
HCl H
2
O
+
Cl
-
H
3
O
+

+
(acid, H
+
donor) (base, H
+
acceptor)
NH
3
H
2
O
+
NH
4
+

OH
-

+
(base, H
+
acceptor) (acid, H
+
donor)
Conjugate acid Conjugate base
Conjugate acid
Conjugate base
CM 1502 35
If it can be either acid or base
...it is amphiprotic.
(amphoteric)
Acid Base
CO
3
2-
HCO
3

H
2
CO
3


SO
4
2-
HSO
4

H
2
SO
4


OH
-
H
2
O H
3
O
+
conjugate base
of the acid
conjugate acid
of the base
36
Lewis Acids
Lewis acids are defined as electron-pair acceptors.
Atoms with an empty valence orbital can be Lewis acids.
AlCl
3
is another common Lewis acid.
Lewis bases are defined as electron-pair donors.
CM 1502
HA
(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ A
-
(aq)


K = = K
a
[HA]
] ][A O [H
-
3
+
Acid Strength
Acid dissociation constant (K
a
) is the measure of acid
strength (in H
2
O solution).
Strong acids ~100% dissociation, higher [H
3
O
+
], K
a
>>1
Weak acids, lower [H
3
O
+
], K
a
<<1
CM 1502 38
39
Polyprotic Acids
Have more than one proton to donate.
Polyprotic acids dissociate in a stepwise manner.
H
3
PO
4(aq)
+ H
2
O
(l)
H
2
PO
4
-
(aq)
+ H
3
O
+
(aq)
H
2
PO
4
-
(aq)
+ H
2
O
(l)
HPO
4
2-
(aq)
+ H
3
O
+
(aq)
HPO
4
2-
(aq)
+ H
2
O
(l)
PO
4
3-
(aq)
+ H
3
O
+
(aq)
K
a1
=
[H
3
O
+
][H
2
PO
4
-
]
[H
3
PO
4
]
K
a2
=
[H
3
O
+
][HPO
4
2-
]
[H
2
PO
4
-
]
K
a3
=
[H
3
O
+
][PO
4
3-
]
[HPO
4
2-
]
K
a1
> K
a2
> K
a3
Generally, easiest to lose the first proton, then
second, then third.
= 7.2x10
-3

= 6.3x10
-8

= 4.2x10
-13

H
3
PO
4
: triprotic acid
CM 1502 40
Polyprotic Acids
If the difference between the K
a
for the first
dissociation and subsequent K
a
values is 10
3
or more,
the pH generally depends only on the first dissociation.
CM 1502 41
Base Strength
Standard: H
2
O is the acid
Base dissociation constant (K
b
) is the measure of base strength
(in H
2
O solution)

K =
] [B
] [HB][OH
-
-
= K
b
B
-
(aq)
+ H
2
O
(l)
HB
(aq)
+ OH
-
(aq)

42
Autoionization of Water
In pure water, same number of molecules act as bases
and as acids. Hence, [H
3
O
+
] = [OH
-
]. This is referred to as
autoionization of water.

K
w
= [H
3
O
+
][OH
-
], called ion product constant for water.

At 25
0
C, K
w
= [H
3
O
+
][OH

] = 1.0 x 10
-14
K
w
= [H
3
O
+
]
2
= [OH
-
]
2
[H
3
O
+
] = [OH
-
] =
[H
3
O
+
] = [OH
-
] = = 1.0 10
7
M


H
2
O(l) + H
2
O(l) H
3
O
+
(aq) + OH
-

(aq)
w
K
14
10 x 1.0

CM 1502
43
Relationship between K
a
and K
b
of a conjugate Acid-Base Pair
K
a
=
[HA]
] ][A O [H
-
3
+
K
b
=
K
a
K
b
=

HA
(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ A
-
(aq)

A
-
(aq)
+ H
2
O
(l)
HA
(aq)
+ OH
-
(aq)

] [A
] [HA][OH
-
-
[H
3
O
+
][OH

] = K
w
CM 1502 44
T (C) Kw
0 0.114 x 10
-14

10 0.292 x 10
-14

20 0.681 x 10
-14

25 1.01 x 10
-14

30 1.47 x 10
-14

40 2.92 x 10
-14

50 5.47 x 10
-14

60 9.61 x 10
-14

45
pH scale
The range of [H
3
O
+
] and [OH
-
] is from ~10 to 10
-15
molL
-1
.
Thus, instead of having 10
-x
, it is convenient to use a
logarithmic scale.

pH is defined as the negative base-10 logarithm of the
hydronium ion [H
3
O
+
] concentration. (p -log
10
)

pH = log [H
3
O
+
]

Reverse operation [H
3
O
+
] = 10
-pH
large x, -log x small
opposite directions
Other p Scales
pOH = log [OH

]
pK
w
= log K
w
= 14

pK
a
= log K
a
pK
b
= log K
b


CM 1502
CM 1502 46
Figure 18.6
The relations among [H
3
O
+
], pH, [OH
-
], and pOH.
Therefore, in pure water,
pH = pOH = log (1.0 10
7
)
= 7.00 NEUTRAL

An ACID has a higher [H
3
O
+
]
than pure water and [OH
-
], so
its pH is < 7.

A BASE has a higher [OH
-
]
than pure water and [H
3
O
+
],
so its pH is > 7.

-log
10
-log
10
47
Why does pH + pOH = 14?

K
w
= [H
3
O
+
][OH

] = 1.0 10
14
,

we know that (or if log each sides of equation),
log [H
3
O
+
] + log [OH

] = log K
w
= 14.00

or, in other words,
pH + pOH = pK
w
= 14.00
*
CM 1502
CM 1502 48
Acid base properties of
salt solutions
Acid + Base Salt + Water
e.g. NaOH(aq) + HCl(aq) NaCl(aq) + H
2
O

Aqueous solutions of salts can be neutral, acidic
or basic. SALTS ARE NOT ALWAYS NEUTRAL!

Strong acid + Strong base Neutral solutions
Weak acid + Weak base Neutral, Acidic, Basic solutions
Strong acid + Weak base Acidic solutions
Weak acid + Strong base Basic solutions
WHY?
CM 1502 49
Hydrolysis of Salts
Salt hydrolysis refers to the situation when a salt is
dissolved in water and its constituent ion reacts with water.

When salts such as NH
4
Cl are dissolved in aqueous
solutions, an acidic solution is obtained i.e. pH < 7
Cation Hydrolysis: If an ion from the salt associates with the
OH
-
entity of the H
2
O => acidic solution

When salts such as Na
2
CO
3
, NaAc (acetate) are dissolved
in aqueous solutions, a basic solution is obtained i.e. pH > 7
Anion Hydrolysis: If an ion from the salt removed a H
+
from
the H
2
O => basic solution



CM 1502 50
Cation Hydrolysis
Salts from strong acids and weak bases.

E.g. AlCl
3
, the Cl
-
does not undergo anion hydrolysis but
Al
3+
has weak acid properties and react with the OH
-
entity
of H
2
O => acidic solution!

General case: M
n+
+ 2H
2
O H
3
O
+
+ MOH
(n-1)+

[H
3
O
+
][MOH
(n-1)+
]
[M
n+
]
K
a
=
CM 1502 51
Anion Hydrolysis
Salts from weak acids and strong bases.

E.g. NaAc, the Na
+
does not undergo cation hydrolysis
but Ac
-
has basic properties and react with the H
+
entity of
H
2
O => basic solution!

General case: X
-
+ H
2
O HX + OH
-
[HX][OH
-
]
[X
-
]
K
b
=
CM 1502 52
Exception
Strong Acid and Strong Base
Salts formed from reactions of strong acid and strong
base, such as NaCl, NaNO
3,
when dissolved in aqueous
solutions, a neutral solution is obtained i.e. pH = 7.


Na
+
(aq) + H
2
O(l) NaOH(aq) + H
+
(aq)

The ions do not undergo hydrolysis.
Cl
-
(aq) + H
2
O(l) HCl(aq) + OH
-
(aq)
Cannot occur
X
X
CM1502 53
Exception
Weak Acid and Weak Base (BUFFERS)
Aqueous solution of the salts may be basic, acidic or neutral.
The pH depends on the relative K
a
and K
b
of the parent acid
and base.
Consider the case when K
a
= K
b
with salt: NH
4
CH
3
COO,
ammonium acetate.

NH
4
CH
3
COO(aq) NH
4
+
(aq) + CH
3
COO
-
(aq)
Both ions can undergo hydrolysis.



K
a
= K
b
=> The same concentration of H
3
O
+
as OH
-
is
produced => solution is NEUTRAL!
K
a
K
b
NH
4
+
(aq) + 2H
2
O(l) NH
4
OH(aq) + H
3
O
+
(aq)

CH
3
COO
-
(aq) + H
2
O(l) CH
3
COOH(aq) + OH
-
(aq)
CM1502 54
If the parent K
a
> K
b
: solution is acidic!
e.g. NH
4
F
K
b
(F
-
): 1.5 x 10
-11
< K
a
(NH
4
+
): 5.7 x 10
-10

So NH
4
+
hydrolyses to a greater extent than F
-

more H
3
O
+
is produced than OH
-
=> ACIDIC!
K
a
K
b
NH
4
+
(aq) + 2H
2
O(l) NH
4
OH(aq) + H
3
O
+
(aq)

F
-
(aq) + H
2
O(l) HF(aq) + OH
-
(aq)
CM1502 55
If the parent K
a
< K
b
: solution is basic!
e.g. NH
4
CN
K
b
(CN
-
): 1.6 x 10
-5
> K
a
(NH
4
+
): 5.7 x 10
-10

So CN
-
hydrolyzes to a greater extent than NH
4
+
more OH
-
is produced than H
3
O
+
=> BASIC!

K
a
K
b
NH
4
+
(aq) + 2H
2
O(l) NH
4
OH(aq) + H
3
O
+
(aq)

CN
-
(aq) + H
2
O(l) HCN(aq) + OH
-
(aq)
CM 1502 56
CM 1502 57
Ionic Equilibria in Aqueous systems
1. Buffer solutions
2. Indicators
3. Titrations
4. Solubility Equilibrium
5. Calculations involving Solubility and Solubility Product
6. The Common Ion Effect
7. Solubility and pH
8. Complex Ion Equilibrium
58
Buffer Solutions
A buffer solution is a solution which does not undergo
any significant change in pH when small amounts of
acid or base are added to it.

Resists changes in pH.

In order to neutralize the acid or base added, the buffer
solution must contain large and roughly equal
concentrations of both a weak acid and a weak base
(usually the acids conjugate base).

Weak acid +its salt, eg: HF+NaF

Weak base +its salt, eg: NH
3
+ NH
4
Cl

CM 1502
59
The Common Ion Effect
The shift of equilibrium position that occurs because of the
addition of an ion already involved in the equilibrium reaction
is called the common ion effect.
This effect makes a solution of NaF and HF
less acidic than a solution of HF alone.
60
Buffer with equal
concentrations of
conjugate acid and base
OH
-
H
3
O
+

Buffer after addition of H
3
O
+

H
2
O + CH
3
COOH H
3
O
+
+ CH
3
COO
-

Buffer after addition of OH
-

CH
3
COOH + OH
-
H
2
O + CH
3
COO
-

CH
3
COOH amount produced is
much smaller compared to initial
amount, so changes in pH is small.
CH
3
COO
-
amount produced is
much smaller compared to initial
amount, so changes in pH is small.
CM 1502
K
a
= 1.8 x 10
-5
K
b
= 5.6 x 10
-10

How does a buffer work
-------------------------------------------------------------------------------------------------------
61
HA(aq) + H
2
O(l) A
-
(aq) + H
3
O
+
(aq)
[H
3
O
+
][A
-
]
[HA]
K
a
=
Take the negative log of both sides:
Henderson Hasselbalch equation
[acid]
[base]
log
10
+ = a pK pH
[acid]
[base]
log
10
+ = a pK pH
62
Buffer Capacity
Buffer capacity is the ability to resist pH change.
It is the amount of H
+
or OH
-
ions that a buffer can
absorb without a significant change in pH.
Determined by the absolute or relative magnitudes of
[HA] and [A-].
The more concentrated the components of a buffer, the
greater the buffer capacity.
A buffer has the highest capacity
when the component
concentrations are equal.
CM 1502 63
[X
-
]
[HX]
[X
-
]
[HX]
Buffer Range
The range of should be 0.1 10 (1:10 or 10:1).

pH = pK
a
+ log
10





*
Therefore, pH = pK
a
1

Buffers have a usable range within 1 pH unit of the
pKa of the acid component.
64
Indicators
Acid-base indicators are buffers a weak acid and its
conjugate base, where each respectively have significantly
different visible colors.
HIn(aq) + H
2
O(l) H
3
O
+
(aq) + In
-
(aq)
RED
Solution acidic
BLUE
Solution basic
CM 1502
+ -
3
,
[H O ][In ]
[HIn]
a a In
K K = =
Taking logs of both sides and rearranging,
-
, 10
[In ]
log
[HIn]
a In
pH pK = +
solution
CM 1502 65
When an indicator is at the mid point of its color
transition range, then
-
,
[HIn] [In ]
a In
pH pK
=
=
= 1
RED BLUE
-
, 10
[In ]
log
[HIn]
a In
pH pK = +
solution
66
For a colour change to be observed,
(i) the acid colour of an indicator needs to be clearly developed which
occurs when ~90% or more of the indicator is in the HIn form, and
(ii) the alkaline colour of an indicator needs to be clearly developed
which happens when ~90% or more of the indicator is in the In
-
form.

Therefore range,

Acid colour: log
10
= -1 ( -0.95)


Alkaline colour: log
10
= 1 ( +0.95)




Acid colour
~90% HIn
~10% In
-
Alkaline colour
~10% HIn
~90% In
-
pH = pK
a,In
- 1 pH = pK
a,In
+ 1
= 0.11
= 9
-
, 10
[In ]
log
[HIn]
a In
pH pK = +
*
CM 1502
50% HIn
50% In
-
67
pH
Figure 19.5
A good indicator will change colour close to the end point of
the titration.
pH = pK
a,In
1
where an indicator
will change colour
pH range of the
solution where the
equivalence point
happens
=
Eq. point
pH = pK
a,In
+1
pH = pK
a,In
-1
CM 1502
68
Equivalence point: pH at which n
acid
= n
base
End point: pH at which indicator changes colour.
Acid-Base Titrations
Buffer
regions
Volume of base added
Volume of base added Volume of base added
Volume of base added
CM 1502
CM 1502 69
CM 1502 70
Strong Acid-Strong Base Titrations
A strong base added to strong acid :
Initially: calc. pH from [HA] = [H
3
O
+
]



Before equiv. point: pH from [H
3
O
+
] = (n
A
n
B
)/(V
A
+ V
B
)


At equiv. point: n
A
= n
B
, [H
3
O
+
] = [OH
-
], pH = 7


After equiv. point: pH from [OH
-
] = (n
B
n
A
)/(V
A
+ V
B
)
HA + H
2
O A
-
+ H
3
O
+
71
Weak Acid-Strong Base Titrations
A strong base added to weak acid :
Initially: weak acid dissociation K
a
= [H
3
O
+
]
2
/[HA]

calc. pH from [H
3
O
+
] =

Before equiv. point: Use buffer equation
.[HA] K
a
CM1502
10
[base]
log
[acid]
a
pH pK = +
HA + H
2
O A
-
+ H
3
O
+
72
Weak Acid-Strong Base Titrations
At equiv. point: n
A
= n
B
, salt formed undergoes anion hydrolysis



Initial [A
-
] = n
B
/(V
A
+ V
B
)

K
b
= [OH
-
]
2
/[A
-
]

calc. pH from [OH
-
] =

After equiv. point: pH from [OH
-
] = (n
B
n
A
)/(V
A
+ V
B
)
] .[A K
-
b
CM 1502
A
-
+ H
2
O HA + OH
-
Initially: calc pH from [HA] = [H
3
O
+
]

Before equiv. point: [H
3
O
+
] = (n
A
n
B
)/(V
A
+ V
B
)

At equiv. point: n
A
= n
B
, salt formed undergoes cation hydrolysis


Initial [M
n+
] = n
A
/(V
A
+ V
B
)

K
a
= [H
3
O
+
]
2
/[M
n+
]
calc. pH from [H
3
O
+
] =

After equiv. point: Use buffer equation for bases.
73
Strong Acid-Weak Base Titrations
A weak base added to strong acid :
] .[M K
n
a
+
CM 1502
M
n+
+ 2H
2
O H
3
O
+
+ MOH
(n-1)+
CM 1502 74
Ksp is called the SOLUBILITY PRODUCT meaning product of
soluble species
Solubility Equilibrium
BaSO
4
(s) Ba
2+
(aq) + SO
4
2-
(aq)

K
sp
= [Ba
2+
][SO
4
2-
]
M
m
X
x
(s) mM
n+
(aq)+ xX
n-
(aq)

K
sp
= [M
n+
]
m
[X
n-
]
x

The definition of solubility product is applied to any sparingly
soluble ionic solid.
Example:
CM 1502 75
Solubility is the quantity of the ionic solid that dissolves in a given
quantity of solvent to give a saturated solution
(Units: gL
-1
; g / 100 cm
3
; mol dm
-3
; etc).
Solubility product is the equilibrium constant for the dissolution
reaction (no units).
Solubility vs. Solubility Product
If the solubility of a compound is known, one can calculate the
corresponding solubility product (and vice versa).
CM 1502 76
The main use of solubility products is to determine conditions
under which an electrolyte will dissolve or precipitate from
solution.
(i) [M
n+
]
m
[X
n-
]
x
(Q
sp
) < K
sp
:
soln. is unsaturated; M
m
X
x
(s) will dissolve.

(ii) [M
n+
]
m
[X
n-
]
x
(Q
sp
) = K
sp
:
soln. is saturated; no dissolution or precipitation of M
m
X
x
.

(iii) [M
n+
]
m
[X
n-
]
x
(Q
sp
) > K
sp
:
soln. is supersaturated; M
m
X
x
(s) will precipitate.
Dissolve or Not?
CM 1502 77
The solubility of a sparingly soluble salt is decreased by the
presence of a second solute having an ion in common with
the sparingly soluble salt.
The Common Ion Effect on Solubility
PbCrO
4
(s) Pb
2+
(aq) + CrO
4
2-
(aq)
CrO
4
2-
added
By Le Chateliers Principle, the position of equilibrium will
shift to the left, favouring the formation of the reactants, Q
> K => solubility of PbCrO
4
decreases!
CM 1502 78
K
stab
is the stability constant of a complex ion
(e.g. MX
6
4-
) used primarily in dilute aqueous solutions.

K
stab
of a complex ion is the equilibrium constant for the
formation of the complex ion in a solvent from its
constituent ions.

M
2+
(aq) + 6X
-
(aq) MX
6
4-
(aq)
Complex Ion Equilibrium

6 - 2
- 4
6
stab
] ][X [M
] [MX
K
+
=
Cr(NH
3
)
6
3+