Solutions for Calculation problems for polyprotic acids

1. Calculate the pH
a) in a 0.1 M hydrogen sulphide solution
b) in a 0.1 M sodium sulphide solution and
c) in a 0.1 M sodium hydrogen sulphide solution.
1/a) H2S solution: c = 0.10 M
Ka1 = 9.10108
Ka2 = 1.201015
[H+] = K a c = (9.1 10 8 ) 0.1 = 9.539 105 M
pH = -log[H+] = -log(9.539 105) = 4.020
1/b) Na2S solution: c = 0.10 M
K
10 -14
K a K b = KW that is K b1 = W =
= 8.333
K a2 1.20 10 -15
In this case cweak base Kb, that is the equation to use is:
c [OH ]
[OH ] = K b
[OH ]
[OH ] 2 = K b (c [OH ])
[OH ] 2 + ( K b [OH ]) - ( K b c) = 0

By solving the equation, [OH ] =

- K b K b2 + 4 ( K b c)
2

-2

= 9.8510-2 M

pOH = -log[OH ] = -log(9.8510 ) = 1.066

pH = 14-1.066 = 12.934
1/c) NaHS solution: c = 0.1 M
[H+] = K a11 K a2 =

9.1 10 8 1.20 10 15 = 1.045 1011 M

pH = -log[H+] = -log(1.045 1011) = 10.98

2. What is the pH of a sodium hydrogen carbonate solution?

[H+] = K a11 K a2 =

4.30 10 7 5.60 10 11 = 4.907 109 M

pH = -log[H+] = -log(4.907 109) = 8.31

3. What is the pH of a 0.2 M carbonic acid solution?

H2CO3 solution: c = 0.20 M
Ka1 = 4.30107;
Ka2 = 5.601011

[H+] = K a c = (4.3 10 7 ) 0.2 = 2.932 102 M

pH = -log[H+] = -log(2.932 102) = 3.533

4. What is the pH of the buffer solution that was prepared by mixing 100.00 cm3 of 0,40
mol/dm3 NaH2PO4-solution and 50 cm3 of 0.50 mol/dm3 Na2HPO4 solution?
c NaH 2 PO4 = 0.400 M

V(NaH2PO4) = 100 cm3

c Na2 HPO4 = 0.500 M

V(Na2HPO4) = 50 cm

Ka2 = 6.17108
c
[H+] = K a2 weak acid =
c weak base

6.17 10 8

n(NaH2PO4) = 0.04 mol

n(Na2HPO4) = 0.025 mol

0.04
= 9.872 108 M
0.025

pH = log [H+]
pH = log 9.872 108
pH = 7.005
5. We added 0.5; 1.0; 1.5 and 2.0 equivalent of base to a 0.10 mol/dm3 H2CO3 solution.
What is the pH of the solution at the different degrees of titration if we neglect the
change in the volume of the solution.

a) At the beginning of the titration:

[H+] = K a c = (4.3 10 7 ) 0.1 = 2.074 104 M
pH = -log[H+] = -log(2.074 104) = 3.683
b) after the addition of 0.5 equivalent of base:
Ka1 = 4.30107
c
0 .5
[H+] = K a1 weak acid = 6.430 10 7
= 4.30 107 M
c weak base
0 .5
pH = log [H+]
pH = log 4.30 107
pH = 6.366
c) after the addition of 1.0 equivalent of base:
[H+] = K a11 K a2 =

4.30 10 7 5.60 10 11 = 4.907 109 M

pH = -log[H+] = -log(4.907 109) = 8.31

d) after the addition of 1.5 equivalent:
c
0 .5
[H+] = K a 2 weak acid = 5.60 10 11
= 5.60 1011 M
c weak base
0 .5
pH = log [H+]

pH = log 5.60 1011

pH = 10.25
e) after the addition of 2.0 equivalent of base:
K
10 -14
K a K b = KW that is K b1 = W =
= 1.786 104 M
-11
K a2
5.60 10
In this case cweak base >>> Kb, that is the equation to use is:
[OH] = K b c weak base = (1.786 10 4 ) 0.1 = 4.226 10-6 M
pOH = -log[OH-] = -log(4.226 10-6) = 2.374
pH = 14.00 pH = 14.00 2.374 = 11.626

6. We would like to prepare a buffer solution with pH = 8.50. We have the following
solutions: 0.200 mol/dm3 NaH2PO4 solution and 0.200 mol/dm3 Na2HPO4 solution.
How should we mix the two solutions to get the buffer with pH = 8.50?
pH = 8.50 pH = log[H+]
[H+] = 3.162 109 M
n
[H+] = K a 2 acid
n salt
3.162 109 = 6.17 10 8

nacid
nsalt

nacid
= 0.05125
n salt
At this stage you have to choose any volume from the buffer to continue the calculation.
For example I take 5.00 L of the buffer. The total concentration of the solution will be
0.200 mol/dm3. So:
n = 0.200 5.00 = 1 mol (this is the molar amount of phosphate that is the sum of the
molar amount of the two forms of phosphate in the solution)
nacid + nsalt = 1.00
nsalt = 1.00 - nacid

nacid
= 0.05125
1 nacid
0.05125 0.05125 nacid = nacid
0.05125 = 1.05125 nacid
nacid = 0.04875 mol

nsalt = 1 0.04875 = 0.95125 mol

V(NaH2PO4) =

0.04875
= 0.244 dm3
0 .2

V(Na2HPO4) =

0.95125
= 4.756 dm3
0 .2

7. What is the pH of the solution that was prepared by dissolving 3.71 g Na2CO3 in 250.0
cm3 of 0.1 mol/dm3 H2CO3 solution?
V= 250.0 cm3
c = 0.100 mol/dm3
n(H2CO3) = c V = 0.250 0.1 = 0.0250 mol
m(Na2CO3) = 3.71 g
M(Na2CO3) = 106.0 g/mol
3.71
n(Na2CO3) =
= 0.035mol
106
+
H2CO3
0.025 mol

CO32 =
0.035 mol

2 HCO3

A reaction takes place between carbonic acid and carbonate ions; the whole amount of the
carbonic acid reacts:
n( CO32 )excess = 0.035 0.025 = 0.010 mol
n( HCO3 ) = 2 0.025 = 0.050 mol
This will be a buffer system:
n(HCO 3- )
0.01
[H+] = K a 2
= 5.60 10 11
= 2.80 1010 M
20.05
n(CO 3 )
pH = -log[H+]
pH = 9.553
8. We titrate 10.0 cm3 of a 0.100 M phosphoric acid solution with a 0.10 M sodium
hydroxide solution. What is the pH of the solution after the addition of 0.5; 1.4; 2.7
and 3.5 equivalent of base?
V(H3PO4) = 10.0 cm3
c(H3PO4) = 0.100 mol/dm3
n(H3PO4) = 0.001 mol
c(NaOH) = 0.100 mol/dm3
a) after the addition of 0.5 equivalent of base:

H 3 PO4 + OH H 2 PO4 + H 2 O

n(H3PO4) = 0.001 mol

Half-equivalent of base: its molar amount will be half of the molar amount of phosphoric
acid.
n(NaOH) = 0.0005 mol
As a result of the reaction: n(H3PO4) = 0.0005 mol
n(NaH2PO4) = 0.0005 mol
0.0005
V ( solution) = 10 +
= 15cm 3
0 .1
The concentration of the acid and the salt:
0.0005
c( H 3 PO4 ) =
= 0.0333 mol/dm3
0.015
0.0005
c( NaH 2 PO4 ) =
= 0.0333 mol/dm3
0.015
[H+] = K a1

c H 3 PO4
c NaH 2 PO4

7.59 10 3

0.0333
= 7.59 103 M
0.0333

pH = 2.12
b) 1.4 equivalent of base: its molar amount will be 1.4 times the molar amount of
phosphoric acid.
n(NaOH) = 0.0014 mol
As a result of the reaction: n(Na2HPO4) = 0.0004 mol
n(NaH2PO4) = 0.0006 mol
0.0014
V ( solution) = 10 +
= 24cm 3
0 .1
The concentration of the acid and the salt:
0.0004
c( Na 2 HPO4 ) =
= 0.01667 mol/dm3
0.024
0.0006
c( NaH 2 PO4 ) =
= 0.025 mol/dm3
0.024
[H+] = K a 2

c NaH 2 PO4
c Na 2 HPO4

6.17 10 8

0.025
= 9.253 108 M
0.01667

pH = 7.034
c) 2.7 equivalent of base: its molar amount is 2.7 times the molar amount of phosphoric
acid.
n(NaOH) = 0.0027 mol
As a result of the reaction: n( PO43 ) = 0.0007 mol
n(Na2HPO4) = 0.0003 mol

V ( solution) = 10 +

0.0027
= 37cm 3
0 .1

The concentration of the acid and the salt:

0.0007
c( Na 3 PO4 ) =
= 0.01892 mol/dm3
0.037
0.0003
c( Na 2 HPO4 ) =
= 0.08108 mol/dm3
0.037
This will be a basic buffer:
K a 3 K b1 = KW

[OH] = K b1

KW
10 -14
that is K b1 =
=
= 5.618 103 M
-12
K a 3 1.78 10

c Na 2 HPO4
c Na 3 PO4

5.618 10 3

0.01892
= 1.311 103 M
0.08108

pOH = 2.882
pH = 14- pOH = 14-2.882 = 11.118
e) ) 3.5 equivalent of base: its molar amount is 3.5 times the molar amount of phosphoric
acid.
n(NaOH) = 0.0035 mol
n(NaOH)excess = 0.0035 0.001 3 = 0.0005 mol
Besides the excess of NaOH (which is a strong base) we will have a weak base, Na3PO4.
So the amount of NaOH will determine the pH of the solution.

V ( solution) = 10 +

c(NaOH) =

0.0035
= 45 cm3 = 0.045 dm3
0 .1

0.0005
= 0.0111 mol/dm3
0.045

pOH = log[OH]
pOH = log0.0111
pOH = 1.954
pH = 14-pOH = 12.046