IONIC EQUILIBRIA

Theory
Arrheni
us
Bronste
d-Lowry
Lewis
Lux
Flood

Usanovi
ch

Acid
Furnish H+ in
water
Proton donor
Electron-pair
acceptor
O2 acceptor
react with
base, give
cations,
accept
anions or
electrons

Base
Furnish OH
in water
Proton
acceptor
Electron pair
donor
O2 donor
react with
acid, give
anions,
accept
cations or
give
electrons

Relative Strengths of Acids and

Bases:
ratio of [H+] or [OH ] supplied by
the acids
or bases

Rel strength of acids

C1Ka1
C2Ka2

Autoionization of water:
increases with temperature
Kw H3O

OH

At 25 0C, Kw 1 x10 14 pH pOH 14

Hydrolysis of Salts
Kw
Kw
Ka
Kb
Kb of conj base
Ka of conj acid

Weak
3.
Weak

Weak

4.
strong

strong

For monovalent salts:

of type 1:
B H2O BOH H
C
C h
Kh

BOH

0
C h

Source of
Anion

Nature of
aqueous solution

Weak

Acidic

Strong

Basic

0
C h
2

hC
Kw

KB C 1 h

Kw

Kb C

KwC
Kb

H C h

of Type 2
A H2O HA OH
C
0
0
C h

C h C h
2

C h
K
Kh w
Ka C 1

Kw
KaC

K
K C
OH C h C w w

KaC
Ka
K K
Kw
H
w a

C
OH

of Type 3:
B A H2O BOH HA
C
C
0
0
C h C h

Source
of
Cation
1.
Strong
2.

Depends on
which is greater:
Ka or Kb
neutral

C h

Kh

C h
K
w
KbKa C 1
h

BOH HA
B

A 1

h
Kw

h
1 h
KbKa

Kw
KbKa

HA

Ch

A
C C h

hC

C C h + C
H C 1 h
A

hC 1
HA

Ka h
H
Ka h

1 h

KwKa
Kb

Buffer solutions
can resist change in pH
pH can be obtained from HendersonHasselbach equation

salt
acid
salt
pOH = log10 K b log
base
pH = log10 K a log

Solubility Equilibria
For: AxBy s xAy yBx
Ksp Ay

Al OH 3 H2O 2
Ans.
3. The self-ionization constant of pure
K HCOOH2

To find pH:

Ka

2.

Ans.
What is the conjugate acid of

B x

xs

ys y

HCOO

formic acid
has
6
been estimated as 10 at room
temperature. What % of formic acid
molecules in pure formic acid are
converted to formate ion? The
density of formic acid is 1.22 g/mL.
Ans. 5 x 10 3
4. Calculate pH of 10 8 N HCl
Ans. 6.96
5. A solution of HCl has a pH = 5. If 1
mL of it is diluted to 1 L, what will be
the pH of resulting solution?
Ans. 6.96
6. An aqueous solution contains 10 %
ammonia by mass and has a density
of 0.99 g/mL. Calculate the [H+] and
[OH ] in this solution. Kb for
ammonia is 1.8 x 10 5 .
Ans. [OH ] = 0.01
[H+]
=9.77x 10- 13
pH= 12.01
7. Calculate the [Cl ], [Na+], [H+] and
[OH ] and pH of resulting solution
obtained by mixing 50 mL of 0.6 N
HCl and 50 mL of 0.3 N NaOH.
Ans.

Na+ 0.15M
Cl
H

pH 0.8239
OH 6.67x1014

Precipitation occurs if Q > Ksp

Questions to Review:
1. What is the conjugate base of

Al OH 3 H2O 2

8. What is the pH of 1 M solution of

acetic acid. To what volume will 1 L of
this solution be diluted so that pH of
the resulting solution will be twice the
original value? Ka = 1.8 x 10 5 .
Ans. 54,358 L

9. The Ka for formic acid and acetic acid

are 2.1 x 10 4 and 1.8 x 10 5
respectively. Calculate the relative
strength of acids.
Ans. 3.4156
10. How many times is the [H+] in the
blood (pH =
7.36 ) greater than that in the spinal
fluid (pH = 7.53)?
Ans.
H

H

blood

1.479

spine

11. Calculate the composition of an

acidic buffer
solution of NaA and HA of total
molarity 0.29 having pH = 4.4 and Ka
= 1.8 x 10 5 .
Ans. Ac 0.0903
HAc 0.1997
12. A 0.1 M solution of weak acid HA is
1%
dissociated at 25 0C. What is its Ka?
If this solution is 0.2 M in NaA, what
will be the new degree of dissociation
of HA and pH?

Ans. 5x105

pH 5.3

13. Two buffers X and Y of pH 4.0 and

6.0
respectively are prepared from acid
HA and salt NaA. Both buffers are
0.50 M in HA. What would be the pH
of the solution obtained by mixing
equal volumes of two buffers? Ka
(HA) = 1 x 10 5
Ans. 5.7033
14. How much of 0.3 M NH4OH should
be mixed
with 30 mL of 0.2 M solution of NH4Cl
to give buffer solutions of pH = 8.65.
Ans. 4.963 mL

15. For a 0.50 M aqueous solution of

sodium
cyanide (Ka of HCN = 5 x 10 10 ) ,
calculate
a. hydrolysis constant
c.
pH
b. degree of hydrolysis
Ans. Kh 2x105

6.32x103 , pH 11.5
16. Calculate the pH at the equivalence
point
when a solution of 0.1 M acetic acid is
titrated with a solution of 0.1 M
NaOH.
Ans. 8.72
17. Calculate the hydrolysis constant of
the salt
containing nitrite ions. Ka for HNO 2
= 4.5
x 10 10
Ans. 2.22x105

18. Calculate the % hydrolysis in 0.003

M aq
solution of NaOCN. (Ka for HOCN =
3.33
x 10 4 M)
Ans. 0.01%
19. Find the mass of NH4Cl dissolved in
500 mL
to have pH = 4.5. K b for NH4OH =
1.8 x 10 - 5
Ans. 48.1 g
20. The dissociation constant of aniline,
acetic
acid and water at 25 0C are 3.83 x 10
10
, 1.8 x 10 5 and 1.00 x 10 14
respectively. Calculate the degree of
hydrolysis and pH of aniline acetate
in a decinormal solution.
Ans. 0.5474 pH 4.66

21. The [Ag+] in a saturated solution of

Ag2CrO4 at 25 0C is 1.5 x 10 4 M.
Determine the Ksp of Ag2CrO4 at 25
0
C.
Ans. 1.6875x10 12
22. The solubility of Mg(OH)2 in pure
water is 9.57
x 10 3 g/L. Calculate the pH of its
saturated solution. Assume 100 %
ionization.
Ans. 10.5185
23. What is the maximum concentration
of equimolar solutions of ferrous
sulfate and sodium sulfide so that
when mixed in equal volumes, there
is no precipitation of iron sulfide. KSP
= 6.3 X 10 18
Ans. M = 5.02 x 10 9
24. What is the minimum volume of
water required to dissolve 1 g of
calcium sulfate at 298 K. for CaSO4,
Ksp = 9.1 x 10 6 .
Ans. 2.43 L
25. A solution contains a mixture o Ag+

to maintain a pH of 7.4? Ka of H2CO3

in blood is 7.8 x 10 7 .
Ans. 78.37 mL
2. Given a solution that is 0.5 mol/L in
acetic acid. To what volume must 1 L
of this solution be diluted in order to
a. double the pH
b. double the [OH ]
Ans. a. dilution factor =
4
3.72x10
b. dilution factor
=4

2H2O H3O OH
3. Kw for
changes
from
10 14 at 25 0C to 9.62 x 10 14 at 60
0
C. What is
the pH of water at 60 0C? What
happens to its
neutrality?
Ans. pH = 6.51
water is still neutral

Hg22
(0.10 M) and
(0.1 M) which are
separated by selective precipitation.
Calculate the maximum
concentration of I at which one of
them gets precipitated almost
completely. What % of that metal ion
is precipitated. Given: Ksp (AgI ) =
8.5 x 10 17 and Ksp (Hg2I2) = 2.5 x
10 26 .
Ans. max [I ] = 5 x 10 13
% Ag+ ppted = 99.83
Additional Exercises
1. The pH of blood stream is maintained
by a proper balance of H2CO3 and
NaHCO3 concentrations. what
volumes of 5 M NaHCO3 solution
should be mixed with a 10 mL sample
of blood which is 2 M in H2CO3 in order

Double Titration
Example:
1. Titration of NaHCO3 + Na2CO3
with HCl

Reaction 1
Na2CO3 HCl NaHCO3 NaCl

nHCl 0.1 0.0112 0.00112 nNa2CO3

nNaHCO3
Reaction 2
NaHCO3 HCl NaCl H2CO3

nHCl 0.1 0.0288 0.00288 total nNaHCO3

original nNaHCO3 0.00288 0.00112 0.00176

In the sample,
0.00176
MNaHCO3
0.0704
0.025
0.00112
MNa2CO3
0.0448
0.025

Reaction 1
Na2CO3 HCl NaHCO3 NaCl
NaOH HCl NaCl H2O
nHCl 0.05 0.0185 0.00095
nNa2CO3 nNaOH
Reaction 2
NaHCO3 HCl NaCl H2CO3
nHCl 0.01 0.05 0.0005
nNaHCO3 nNa2CO3
nNaOH 0.00095 0.0005 0.000425
In the sample,
MNaOH

2.

Titration of NaOH + Na2CO3 with

HCl

MNa2CO3

0.000425
0.017
0.025
0.0005

0.02
0.025