ACID BASE

EQUILIBRIA
Contents
Definition of Acid and Base :
Arrhenius
Brnsted-Lowry , conjugate acid-base pairs
Lewis
Strength of Acid and Base :
Strong acid weak acid
Strong base weak base
Ionization of Acid and Base
Concepts of pH, pOH, pK
a
, pK
b

Dissociation Constant : K
a
, K
b
, K
w

Learning Outcomes
Able to differentiate and calculate acid
dissociation constants for weak and strong
acids (applicable to bases)
Calculate pH and pOH
Arrhenius Definition
Arrhenius base contains significant OH
-
ion
Arrhenius acid never contains H
+
ion, instead it contains
H atom covalently bonded that ionize in water
E.g: Arrhenius acid HCl, HNO
3
, HCN
E.g: Arrhenius base NaOH, KOH, Ba(OH)
2

Acid
a substance that contains
hydrogen and dissociates(ionizes)
in water to yield H
3
O
+
Base
a substance that contains the
hydroxyl group and dissociates in
water to yield OH
-
Whenever an acid dissociates (ionizes) in water,
solvent molecules participate in the reaction
HA (g or aq) + H
2
O(l) 4 A
-
(aq) + H
3
O
+
(aq)
The H
3
O
+
is
called
hydronium ion
The terms hydrogen
ion = proton = H
+
are
used interchangeably
Arrhenius Definition
Strong acids: dissociate/ionize completely into
ions in water.
Eg:HNO
3
(aq)+ H
2
O(l) 4 H
3
O
+
(aq) + NO
3
-
(aq)

Weak acids: dissociate/ionize very slightly into
ions in water.
Eg: HCN(aq) + H
2
O (l) C H
3
O
+
(aq) + CN
-
(aq)

This classification correlates with classification of
electrolytes:
strong electrolytes dissociate/ionize completely, and
weak electrolytes dissociate/ionize partially.
Arrhenius Definition
Brnsted-Lowry Acid-Base Definition
Acid
proton donor.
Any species that donates an H
+

such as HCl, HNO
3
, H
3
PO
4

All Arrhenius acids are

Brnsted-
Lowry acids
Base
proton acceptor.
Any species that accepts an H
+
,
must contain lone pair of electrons to
bind the H
+
, such as NH
3
, CO
3
2-
, F
-
and
OH
-
Brnsted-Lowry bases are not
Arrhenius bases, but all Arrhenius bases
contain Brnsted-Lowry base OH
-
.
-
HCl (g) + H
2
O (l) H
3
O
+
(aq) + Cl
-
(aq)
HCl acts as a Brnsted-Lowry acid ( it donates a
proton to H
2
O)
H
2
O acts as a Brnsted-Lowry base ( it accepts a
proton from HCl)


Brnsted-Lowry Acid-Base Definition
NH
3
(aq) + H
2
O (l) C NH
4
+
(aq) +OH
-
(aq)
H
2
O acts as an acid, it donates the H
+

NH
3
acts as a base, it accepts H
+
.
Thus, H
2
O is ampotheric: it acts as a base in
one case and as an acid in the other.

Brnsted-Lowry Acid-Base Definition
NH
3
(aq) + H
2
O (l) C NH
4
+
(aq) +OH
-
(aq)

Brnsted-Lowry Acid-Base Definition
Example
Determine acid and base in the following reactions:

1. HCO
3
-
(aq) + HF (aq) C H
2
CO
3
(aq) + F
-
(aq)
2. HCO
3
-
(aq) + OH
-
(aq) C CO
3
2-
(aq) + H
2
O (aq)
3. SO
3
2-
(aq) + NH
4
+
(aq) C HSO
3
-
(aq) + NH
3
(aq)
4. HSO
3
-
(aq) + NH
3
(aq) C SO
3
2-
(aq) + NH
4
+
(aq)


Answer
Acid Base
1. HF (aq) HCO
3
-
(aq)
2. HCO
3
-
(aq) OH
-
(aq)
3. NH
4
+
(aq) SO
3
2-
(aq)
4. HSO
3
-
(aq) NH
3
(aq)
Conjugate Acid-Base Pairs
Consider the reaction of acid HA:
HA (aq) + H
2
O(l) A
-
(aq) + H
3
O
+
(aq)
Forward reaction: HA is the acid, H
2
O is the base
Reverse reaction: H
3
O
+
is the acid, A
-
is the base
HA and A
-
: differ in the presence or absence of a
proton (base)
a conjugate acid-base pair.
Add H
+

In any acid-base reaction:


HNO
2
(aq)+ H
2
O (l) NO
2
-
(aq) + H
3
O
+
(aq)
Acid Base
Conjugate
base
Conjugate
acid
Remove H
+

Conjugate Acid-Base Pairs
Acids such as HCl , HNO
3
, or H
2
SO
4
ionize in water to form a
hydrated proton and a species called the conjugate base of
the acid;
HCl (aq) H
+
(aq) + Cl
-
(aq)
Acid
Conjugate base
of HCl
- Conjugate base of HCl results from the loss of one proton.
Conjugate Acid-Base Pairs
Bases such as NH
3
react with water to form a hydrated
hydroxide ion and a species called the conjugate acid of
base.
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)
Base
Conjugate acid
of NH
3

Conjugate acid of NH
3
results from the gain of one proton.
Conjugate Acid-Base Pairs
In NH
3
and H
2
O
NH
3
(aq) + H
2
O (l) NH
4
+
(aq) + OH
-
(aq)
Base
Acid
Conjugate
acid
Conjugate
Base
Add H
+

Remove H
+

NH
3
NH
4
+

base Conjugate acid
Add H
+

H
2
O OH
-

Acid Conjugate Base
Remove H
+

Note:
Conjugate Acid-Base Pairs
a) What is the conjugate base of the following acids:
HClO
4
; HCO
3
-

- remove one proton ( H
+
) from the formula.
ClO
4
-
; CO
3
2-

b) What is the conjugate acid of the following bases:
CN
-
; H
2
O ; HCO
3
-

- add one proton to the formula
HCN ; H
3
O
+
; H
2
CO
3
Note: Hydrogen Carbonate ion, HCO
3
-
is amphoteric: a
substance that can act as an acid or as a base.
Example
Example
Determine the conjugate acid-base pairs in the
following:

1. HCO
3
-
(aq) + HF (aq) C H
2
CO
3
(aq) + F
-
(aq)
2. HCO
3
-
(aq) + OH
-
(aq) C CO
3
2-
(aq) + H
2
O (aq)
3. SO
3
2-
(aq) + NH
4
+
(aq) C HSO
3
-
(aq) + NH
3
(aq)
4. HSO
3
-
(aq) + NH
3
(aq) C SO
3
2-
(aq) + NH
4
+
(aq)
Answer
Acid Base Conj. acid Conj. Base

HF (aq) HCO
3
-
(aq) H
2
CO
3
(aq) F
-
(aq)
HCO
3
-
(aq) OH
-
(aq) H
2
O (l) CO
3
2-
(aq)
NH
4
+
(aq) SO
3
2-
(aq) HSO
3
-
(aq) NH
3
(aq)
HSO
3
-
(aq) NH
3
(aq) NH
4
+
(aq) SO
3
2-
(aq)
Other example: HSO
3
-

Acid
HSO
3
-
(aq) + H
2
O(l) SO
3
2-
(aq) + H
3
O
+

Remove H
+

Add H
+

Base
HSO
3
-
(aq) + H
2
O(l) H
2
SO
3
(aq) + OH
-
(aq)
Add H
+

Remove H
+

Conjugate pairs in acid-base reactions
Lewis Acid-Base Definition
OH
-
, H
2
O , an amine - are electron-pair donors
A base in the Brnsted-Lowry ( a proton acceptor)
also base in the Lewis (an electron pair donor )
In the Lewis theory: a base can donate its electron
pair to species other than H
+

Acid
Electron pair acceptor

Base Electron pair donor

Lewis Acids with Electron-Deficient Atoms:
Eg: Reaction between NH
3
and BF
3
.
BF
3
has a vacant orbital in its valence shell- acts as
an electron pair acceptor (a Lewis acid) toward
NH
3
.

NH
3
donates the electron pair.



Lewis Acid-Base Definition
N
H
H
H
B
F
F
F N
H
H
H B
F
F
F
Lewis base Lewis acid
Lewis acid - molecules have an incomplete octet of
electrons.
Eg. Cations Fe
3+
interacts with cyanide ions;


Fe
3+
ion has vacant orbitals - accept the electron
pairs donated by the CN
-
ions.
Lewis Acid-Base Definition
Fe
3+
+ C N 6
C N Fe
6
3-
Note: Lewis acids and bases do not need to contain
protons.
Therefore, the Lewis definition is the most general
definition of acids and bases.
Lewis acids generally have an incomplete octet (eg.
BF
3
).
Transition metal ions are generally Lewis acids.
Lewis acids must have a vacant orbital (into which the
electron pairs can be donated).
Lewis Acid-Base Definition
Metal Cation as Lewis Acid
Definitions Comparison
Theory
Arrhenius
Brnsted-Lowry
Lewis
Acid Base
Forms H
3
O
+
ions in
water
Forms OH
-
ions in
water
Proton donor
HCl + H
2
O H
3
O
+
+ Cl
-

Proton acceptor
NH
3
(aq) + H
2
O
NH
4
+ OH
-

Electron pair acceptor
B
F
F
F
Electron pair donor
N
H
H
H
Strength of Acid and Base:
Objectives
Strength of acid-base
Strong acid - strong base / weak acid - weak
base
Strength in conjugate acid base determine
the direction of acid-base reaction
Water auto-ionization
Concept of pH
Variation in Acid Strength
Strong acids: Ionize completely into ions in water.
Eg: HNO
3
(aq)+ H
2
O(l) 4 H
3
O
+
(aq) + NO
3
-
(aq)

Weak acids: ionize very slightly into ions in water.
Eg: HCN(aq) + H
2
O (l) C H
3
O
+
(aq) + CN
-
(aq)

This classification correlates with classification of
electrolytes:
strong electrolytes dissociate/ionize completely
weak electrolytes dissociate/ionize partially.
Strong Acids
Hydrohalic acids
HCl,
HBr,
HI
Oxoacids
(number of O exceeds no. of
ionisable H atoms by two or more)
HNO
3
H
2
SO
4

HClO
4
HClO
3
HCl (aq) + H
2
O (l) H
3
O
+
(aq) + Cl
-
(aq)
HNO
3
(aq) + H
2
O (l) H
3
O
+
(aq) + NO
3
-
(aq)
Strong acid will fully dissociate/ionize in water
Weak acids
Hydrohalic acids
HF
Acids in which H is not bonded
to O or to halogen
HCN
H
2
S
Oxoacids
(in which no. of O equals or exceed
by one the no. of ionizable H)
HClO,
HNO
2

H
3
PO
4
Organic acids
(general formula RCOOH)
CH
3
COOH
C
6
H
5
COOH
Example
HF
(aq)
+ H
2
O
(l)
C H
3
O
+

(aq)
+ F
-

(aq)
CH
3
COOH
(aq)
+ H
2
O
(l)
C H
3
O
+

(aq)
+ CH
3
COO
-

(aq)
HNO
2 (aq)
+ H
2
O
(l)
C H
3
O
+

(aq)
+ NO
2
-

(aq)

Weak acid will partially ionize in water
Strong Base
Soluble
compounds
containing O
2-

or OH
-
The cations are
usually those of
the most active
metals
M
2
O or MOH;
Where M= Group IA
metal
(Li, Na, K, Rb, Cs)

MO or M(OH)
2
;
Where M= Group IIA
metal
(Be, Mg, Ca, Sr, Ba)

Ionic hydrides
and nitrides
H
-
(aq) + H
2
O (l) H
2
(g) + OH
-
(aq)
N
3-
(aq) + 3 H
2
O (l) NH
3
(aq) + 3OH
-
(aq)
Weak Bases
Compounds with
an electron-rich
nitrogen are weak
bases
(none are
Arrhenius bases).
The common
structural
feature is an
N atom that
has a lone
pair
Ammonia
: NH
3

Amines
such as
CH
3
CH
2
: NH
2
C
5
H
5
N:
Relative Strengths of Acid-Base
Some acids are better proton donors than others.
The stronger the acid, the weaker its conjugate base.
Some bases are better proton acceptors.
The stronger the base, the weaker its conjugate acid
The strength of an acid tells the strength of its conjugate
base.
Strong acids: completely transfer their protons 100%
dissociation Their conjugate bases have a negligible
tendency to be protonated.
(E.g: HCl + H
2
O H
3
O
+
+ Cl
-
)
Consider the proton transfer in this:

HA(aq) + H
2
O (l) H
3
O
+
(aq) + A
-
(aq)
If HA is a stronger acid than H
3
O
+
;
HA will transfer its proton to H
2
O ; equilibrium lies to
the right
If H
3
O
+
is a stronger acid than HA (if HA is a weak
acid);
equilibrium lies to the left
In every acid-base reaction, the position of the
equilibrium favors transfer of the proton from the
stronger acid to the stronger base to form the
weaker acid and the weaker base.
Example: CN
-
reacts with water as follows:
CN
-
(aq) + H
2
O(l) HCN (aq) + OH
-
(aq)
A Cl
-
ion does not react with water to form HCl.
Which acid is stronger, HCl (aq) or HCN (aq)? Why?
HCl and HCN are the conjugated acids of the bases Cl
-
and
CN
-
.The information provided tells us that Cl
-
is a weaker
base than CN
-
.CN
-
accepts a proton from H
2
O to form HCN.
Principle: The weaker a base, the stronger its conjugated
acid, can conclude that HCl is a stronger acid than HCN
Example
Predict the product of the following acid-base reactions
and also predict whether the equilibrium lies to the left
or to the right of the equation:
1. Cl
-
(aq) + H
3
O
+
(aq)
2. H
2
PO
4
-
(aq) + H
2
O (l)
3. HS
-
(aq) + HC
2
H
3
O
2
(aq)
4. HCO
3
-
(aq) + OH

(aq)
5. NH
4
+
(aq) + H
2
PO
4
-
(aq)
HCl (aq) + H
2
O(aq) Lies to the left
HPO
4
2-
(aq) +H
3
O
+
(aq)Lies to the
left
H
2
S (aq) + C
2
H
3
O
2
-

Lies to the
right
CO
3
2-
(aq) + H
2
O (l)

Lies to the
right
NH
3
(aq) + H
3
PO
4
(aq)
Lies to the left
Autoionization of water
Water ionises into H
+
and OH
-
(v. small extent).
This process is called the autoionization of water.
The Ion-Product Constant for Water, K
w

We can write an equilibrium constant expression for the
autoionization of water: 2H
2
O(l) H
3
O
+
(aq) + OH
-
(aq)



Because H
2
O(l) is a pure liquid, the expression can be
simplified:
| || |
| |
2
2
eq
O H
OH O H
K
3
+
=
| | | || |
w eq
K OH O H K O H = =
+
3
2
2
The Ion-Product Constant for Water, K
w

K
w
is called the ion-product constant.
At 25C the ion-product of water is always:


In neutral solution: [H
3
O
+
] = [OH
-
]
In acidic solution : [H
3
O
+
] exceeds [OH
-
]
In basic solution : [OH
-
] exceeds [H
3
O
+
]
Note: The ion -product constant K
w
is unaffected by
whether a solution is acidic or basic.
| || |
+
= = OH O H K
w 3
14
10 1
Calculate the concentration of H
3
O
+
(aq) in a
solution in which [OH
-
] is 2.0 x 10
-9
M at
25C.
| || |
| |
| |
M 10 x 5.0
10 x 2.0
10 x 1.0
OH
10 x 1.0
H
10 x 1.0 OH H
6
9
14 14
3
14
3

+
+
= = =
=
O
O
Example
The pH scale
Express H
+
in terms of pH.
For [H
+
] = 1.0 x 10
-3
M.
pH = -log (1.0 x 10
-3
) = -(- 3.00 ) = 3.00
pH = -log [H
+
] = -log [H
3
O
+
]
Basic
[H
+
] (M)
<1.0x10
-7
=1.0x10
-7
>1.0x10
-7
[OH
-
] (M)
>1.0x10
-7
=1.0x10
-7
<1.0x10
-7
pH value
<7.00
=7.00
>7.00
Acidic
Neutral
Acidic Neutral Basic
[H
3
O
+
]
1 10
-7
[OH
-
]
1 10
-7

Neutral
[H
3
O
+
]
1
[OH
-
]
1 10
-14

Acidic
1 10
-1

1 10
-2
1 10
-3
1 10
-4
1 10
-5
1 10
-6
1 10
-13

1 10
-12
1 10
-11
1 10
-10
1 10
-9
1 10
-8
[OH
-
] [H
3
O
+
]
1 10
-6
1 10
-5
1 10
-4
1 10
-3
1 10
-13

1 10
-8
1 10
-9
1 10
-10
1 10
-11
1 10
-12
1 10
-14

Basic
1 10
-2
1 10
-1

1
Example

Given [OH
-
] = 2.0 x 10
-3
, calculate [H
+
] (or [H
3
O
+
])
and pH at 25C.




pH = -log ( 5.0 X 10
-12
)
= 11.3
| |
| |
M
OH
K
H
W
12
3
14
10 0 . 5
10 0 . 2
10 0 . 1

+
=

= =
The concentration of OH
-
can be expressed as pOH


Example:
A solution has a pH of 5.6 . Calculate the hydrogen
ion concentration.
pH = -log [H
+
], log [H
+
] = -5.6
[H
+
] = 2.5 10
-6
M
Other p scale
pOH = -log [OH
-
]
pH + pOH = pK
w
=

-log K
w
= 14.00
OCalculate [H
+
] for a solution with pOH of 4.75
pOH is defined as log [OH
-
]
The pH and the pOH are related: pH + pOH = 14.00
pH = 14.00 - pOH = 14 - 4.75 = 9.25
pH = 9.25
log [H
+
] = -pH = -9.25
[H
+
] = 5.6 x 10
-10
M.
Example
Acid-base indicator
pH paper
pH meter
Methods for measuring pH
Strong Acids
Strong acids are strong electrolytes and they ionize
completely in solution.
HNO
3
(aq) + H
2
O (l) H
3
O
+
(aq) + NO
3
-
(aq)

Example
What is the pH of a 0.04 M solution HClO
4
?
HClO
4
is completely ionized: [H
+
] = 0.04 M
Hence, pH= -log (0.040) = 1.40

Strong Bases
Most ionic hydroxides are strong bases (eg. NaOH,
KOH and Ca(OH)
2
.)

Strong bases are strong electrolytes and dissociate
completely in solution:
NaOH (aq) Na
+
(aq) + OH
-
(aq)

The pOH of a strong base is given by the initial
molarity of the base.
Example
What is the pH of a 0.011 M solution of Ca(OH)
2
?

Ca(OH)
2
is a strong base.
Ca(OH)
2
Ca
2+
+ 2OH
-

0.011M 0.011M 2 0.011M
pOH = -log (0.022) = 1.66
pH + pOH = 14.00
pH = 14.00 - pOH = 14.00 - 1.66 = 12.34
Acid Dissociation Constant, K
a
HA (g or aq) + H
2
O(l) C A
-
(aq) + H
3
O
+
(aq)






Stronger acid 4 larger K
a
Weaker acid 4Smaller K
a
4lower % HA ionizes
| || |
| |
| || |
| | HA
or
HA
+ +
= =
A H
K
A O H
K
eq eq
3
| || |
| | HA
+
=
A O H
K
3
a
K
a
values for weak acids
Acid K
a
% HA dissociated

1 M HClO
2
1.12 x10
-2
10 %

1 M CH
3
COOH 1.8 x10
-5
0.42 %

1 M HCN 6.2 x10
-10
0.0025 %
Solving Problems Involving Weak-Acid
Equilibria
1. Given equilibrium concentrations, find K
a
.
2. Given K
a
and other info, find other equilibrium
concentration.


HA (aq) + H
2
O(l) H
3
O
+
(aq) + A
-
(aq)
Ionization is incomplete and some significant
amount of undissociated acid remains at equilibrium.
[HA]
] [A ] [H
K
a
+
=
Problem-Solving Approach : Problems
Involving Weak-Acid Equilibria
1. Write the balanced equation and K
a
expression
2. Define x as unknown concentration that changes
during the reaction.
3. Construct a reaction table that incorporates the
unknown.
4. Make assumptions that simplify the calculations.
5. Substitute the values into the K
a
expression and solve
for x
6. Check that the assumptions are justified.
HA (aq) + H
2
O (l) H
3
O
+
(aq) + A
-
(aq)
If f is the formal concentration of acid , x be the
equilibrium concentration of H
3
O
+
. Then,
HA (aq) + H
2
O (l) H
3
O
+
(aq) + A
-
(aq)
f - x x x

x f
x
[HA]
] [A ] O [H
K
2
3
a

= =
+
Problem-Solving Approach : Problems
Involving Weak-Acid Equilibria
The equation can be solved using quadratic eqn.

If f>>x, then
x
2
~ K
a
f
x =
If x is < 5% of the initial concentration, we can use
the assumption.
If x is > 5% of the initial concentration, it maybe
best to solve the quadratic equation.
f K
a
Problem-Solving Approach : Problems
Involving Weak-Acid Equilibria
Percent ionisation is another method to assess acid
strength.
% ionisation

The higher the percent ionisation, the stronger the
acid.
x100
[HA]
] O [H
initial
eqm 3
+
=
Problem-Solving Approach : Problems
Involving Weak-Acid Equilibria
A student prepared 0.10 M solution of formic acid HCHO
2
.
The pH= 2.38 at 25C.

1. Calculate K
a
2. Percentage of ionisation.
Example
| || |
| |
| |
| |
| | M H
H
H pH
HCHO
CHO H
K
a
3
2
2
10 2 . 4
38 . 2 log
38 . 2 log
+
+
+

+
=
=
= =
=
Calculate K
a









HCHO
2
(aq)

H
+
(aq) + CHO
2
-
(aq)
Example
| || |
| |
| | | | | | M H H H pH
HCHO
CHO H
K
a
3
2
2
10 2 . 4 , 38 . 2 log , 38 . 2 log
+ + +

+
= = = =
=

Answer
HCHO
2
(aq) C H
+
(aq) + CHO
2
-
(aq)

Initial

Change

Eqm

(0.10 4.2 10
-3
)M ~ 0.10 M


-4.2 10
-3
M
0.10 M 0 0
+4.2 10
-3
M +4.2 10
-3
M
4.2 10
-3
M
4.2 10
-3
M (0.10 - 4.2 10
-3
)M
( )( )
( )
4
3 3
10 8 . 1
10 . 0
10 2 . 4 10 2 . 4


=

=
a
K
The percent
ionisation of a weak
acid decreases as its
concentration
increases. 1.0
2.0
3.0
4.0
5.0
0.05 0.10 0.15
P
e
r
c
e
n
t

i
o
n
i
s
e
d

Acid concentration (M)
| |
| |
% 2 . 4 % 100
10 . 0
10 2 . 4
% 100 %
3
2
=

=
=

+
initial
m equilibriu
HCHO
H
ionisation
Calculate the percentage of HF (K
a
= 6.8 x 10
-4
)
molecules ionised in:

a. 0.10M HF solution
b. 0.010 M HF solution
Example
Acids have more than one ionizable H atom
Example: Sulfurous acid, H
2
SO
3
.
H
2
SO
3
(aq) C H
+
(aq) + HSO
3
-
(aq) K
a1
= 1.7 x 10
-2

HSO
3
-
(aq) C H
+
(aq) + SO
3
2-
(aq) K
a2
= 6.4 x 10
-8


K
a2
is much smaller than K
a1
; easier to remove the first
proton from polyprotic acid than the second
K
a1
is much larger than K
a2
; can estimate the pH by
considering only K
a1
.
Polyprotic Acid
Example
CO
2
dissolved in water at 25C and 0.1 atm to form H
2
CO
3
with
conc. 0.0037 M.
What is the pH ?

CO
2
(aq) + H
2
O(l) C H
2
CO
3
(aq)
[H
2
CO
3
] = 0.0037 M

H
2
CO
3
is a polyprotic acid:
H
2
CO
3
(aq) C H
+
(aq) + HCO
3
-
(aq) k
a1
= 4.3 10
-7

HCO
3
-
(aq) C H
+
(aq) + CO
3
2-
(aq) k
a2
= 4.710
-11

ANSWER = 4.40
Weak Bases
There is an equilibrium between the base and the
resulting ions
Weak base + H
2
O(l) C conjugate acid + OH
-
(aq)
Eg: NH
3
(aq) + H
2
O C NH
4
+
(aq) + OH
-
(aq)
The base-dissociation constant , K
b
, is defined as


The larger the K
b
the stronger the base
] [NH
] ][OH [NH
K
3
4
b
+
=
Example
Calculate the concentration of OH
-
in a 0.15 M
solution of NH
3
. (K
b
= 1.8 x 10
-5
)
NH
3
(aq) + H
2
O(l) C NH
4
+
(aq) + OH
-
(aq)
0.15 -x x x


x = [NH
4
+
] =[OH
-
] = 1.6 x10
-3
M

5
3
4
b
10 x 1.8
x 0.15
(x)(x)
] [NH
] ][OH [NH
K

+
=

= =
Example
A solution is made by adding Sodium Hypochlorite,
NaClO, to water (2.0 L soln). The pH of solution is
10.50. How many moles of NaClO were added?
Note:
NaClO is an ionic compound, strong electrolyte.
NaClO - Na
+
+ ClO
-
ClO
-
(aq) + H
2
O

C HClO(aq) + OH
-
(aq)
K
b
= 3.3 x 10
-7
.
Unit in molarity
pOH + pH = 14
pOH = - log [OH
-
]
pH = - log [ H
+
]
Given: pH = 10.50 ; base. Whats the [OH
-
]
Knowing the [OH
-
] then we know the Molarity of ClO
-
.
4Molarity of NaClO 4 mole ( in the same volume: 2.0 L )
NaClO - Na
+
+ ClO
-
1 mole 1 mole 1 mole
Answer
ClO
-
(aq) + H
2
O(l) HClO(aq) + OH
-
(aq)
Let say we start with 1.0 M NaClO : conc. of ClO
-
is 1.0 M. Then,
ClO
-
(aq) + H
2
O(l) HClO(aq) + OH
-
(aq)
1 - x x x
x; concentration of OH
-
* If we dont know the ClO
-
. Let say ClO
-
: z
But we know the [OH
-
] 4 x . Then,
z - x x x

Answer
Given pH = 10.50
from : pH + pOH = 14.0
pOH = 14.0 - 10.50 = 3.50
pOH = - log [OH
-
]
[OH
-
] = 10
-3.50
= 3.2 x 10
-4
M
x = 3.2 x 10
-4
M
Answer
ClO
-
(aq) H
2
O(l) HClO(aq) OH
-
(aq)
Initial z - 0 0
Change -3.2 10
-4
- 3.2 10
-4
3.2 10
-4

final z - 3.2 10
-4
- 3.2 10
-4
3.2 10
-4

Tabulate in equilibrium table:
ClO
-
(aq) + H
2
O(l) HClO(aq) + OH
-
(aq)
M 0.31 z
10 x 3.3
10 x 3.2 z
) 10 x (3.2
] [ClO
] [HClO][OH
K
7
4
2 4
b
=
=

=
=

Z = [ClO
-
] = 0.31 M
4 NaClO = 0.31 M


Mol of NaClO = 0.31 (mol/ L) x (2 L)
= 0.62 mol

2L
Mol
0.31
Volume(L)
Mol
M Molarity, = = =
Answer
Relationship between K
a
and K
b

We need to quantify the relationship between
strength of acid and conjugate base.
NH
4
+
(aq) C NH
3
(aq) + H
+
(aq)
NH
3
(aq) +H
2
O(l) C NH
4
+
(aq) + OH
-
(aq)

] [NH
] ][OH [NH
K
] [NH
] ][H [NH
K
3
4
b
4
3
a
+
+
+
=
=
NH
4
+
(aq) C NH
3
(aq) + H
+
(aq)
NH
3
(aq) +H
2
O(l) C NH
4
+(aq) + OH
-
(aq)
H
2
O(l) C H
+
(aq) + OH
-
(aq)

When two reactions are added to give a third, the equilibrium
constant for the third reaction is the product of the equilibrium
constant for the two added reactions:
reaction 1+ reaction 2 = reaction 3
K
1
x K
2
= K
3

Relationship between K
a
and K
b

For a conjugate acid -base pair
w b a
w
3
4
4
3
b a
K K K
K ] ][OH [H
] [NH
] ][OH [NH
] [NH
] ][H [NH
K K
=
= =
|
|
.
|

\
|
|
|
.
|

\
|
=
+
+
+
+
Therefore , the larger the K
a
the smaller the K
b
. That is, the
stronger the acid, the weaker the conjugate base.
Taking negative logarithms:
pK
a
= -log (K
a
) and pK
b
= -log(K
b
)
then pK
a
+ pK
b
= pK
w




END of CHAPTER 13