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# 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 =

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

[H+] = K a11 K a2 =

## 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

## 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 =

## 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