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Solutions for the problems about „Calculation of pH in the case of monoprotic

acids and bases”

1. What is the pH of a 0.1 M acetic acid solution?

Acetic acid is a weak acid with Ka = 1.86 × 10–5 and in this case cweak acid >>> Ka,
that is the equation to use is:
[H+] = K a ⋅ c weak acid = (1.86 × 10 −5 ) × 0.1 = 0.0013638 M
pH = -log[H+] = -log(0.0013638) = 2.865

2. What is the pH of a 0.1 M ammonia solution?

Ammonia is a weak base with Kb = 1.75 × 10–5 and in this case cweak base >>> Kb,
that is the equation to use is:
[OH–] = K b ⋅ c weak base = (1.75 × 10 −5 ) × 0.1 = 0.0013229 M
pOH = -log[OH-] = -log(0.0013638) = 2.878
pH = 14.00 – pH = 14.00 – 2.878 = 11.122

3. What is the pH of a 0.1 M sodium acetate solution?

Sodium acetate is a weak base, a conjugate base of acetic acid, so:


K 10 -14
K aacetic acid × K bacetate = KW that is K bacetate = aceticW acid = = 5.376 × 10-10
Ka 1.86 × 10 -5
In this case cweak base >>> Kb, that is the equation to use is:
[OH–] = K b ⋅ c weak base = (5.376 × 10 −10 ) × 0.1 = 7.332 × 10-6 M
pOH = -log[OH-] = -log(7.332 × 10-6) = 5.135
pH = 14.00 – pH = 14.00 – 2.878 = 8.865

4. What is the concentration (in g/dm3 units) of an ammonia solution which has a
pH of 11.100?

Ammonia is a weak base with Kb = 1.75 × 10–5.


pH = 11.100 that is pOH = 14.00 – pH = 2.900
[OH-] = 10–pOH = 10–2.9 = 1.2589 × 10-3 M
c − [OH − ]
[OH − ] = K b ⋅ weak base −
[OH ]
c weak base − 1.2589 × 10 −3
1.2589 ×10 −3 = 1.75 ×10 −5
1.2589 × 10 −3
1.584 × 10-6 = 1.75 × 10-5 × (cweak base – 1.2589 × 10-3)
1.584 × 10-6 = 1.75 × 10-5 cweak base – 2.203 × 10-8
1.606 × 10-6 = 1.75 × 10-5 cweak base
cweak base = 0.091773 M
So, we have 0.091773 mol ammonia in 1 L solution, that is 1.56 g ammonia (m =
n × M.W. = 0.091773 mol × 17 g/mol) in 1 L solution. The concentration is 1.56
g/L.

5. A monobasic organic acid has a pK of 4.875. The pH of a saturated solution


of this acid is 3.700. Calculate the solubility of this organic acid in mol/dm3
units.

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pH = 3.700, so [H+] = 10–pH = 10–3.7 = 1.9953 × 10-4 M
pK = 4.875, so Ka = 10–pK = 10–4.875 = 1.3335 × 10-5
c − [H + ]
[H + ] = K a ⋅ weak acid +
[H ]
− 1.9953 × 10 −4
cweak
1.9953 × 10 −4 = 1.3335 × 10 −5 acid
1.9953 × 10 −4
3.981 × 10 = 1.3335 × 10 (cweak acid – 1.9953 ×10-4)
-8 -5

3.981 × 10-8 = 1.3335 × 10-5 cweak acid – 2.661 ×10-9


4.247 × 10-8 = 1.3335 × 10-5 cweak acid
cweak acid = 0.003185 M

6. What is the pH and the degree of dissociation in a a) 0.1 M; in a b) 0.01 M and


in a c) 0.001 M acetic acid solution, respectively?

a) Acetic acid is a weak acid, so:


+ c weak acid − [H + ]
[H ] = K a ⋅
[H + ]
However, if the cweak acid = 0.1 M, we can use the simpler form of the formula:
[H + ] 2 = K a ⋅ c weak acid
[H+] = 1 .86 × 10 −5 × 0 .10
[H+] = 1.3638×10-3 M
pH = -log[H+] = -log(1.3638×10-3) = 2.865
[H + ]
In this case [H+] = [acetate ion], so α = = 0.0136 = 1.36 %
c weak acid
b)Acetic acid is a weak acid, so:
c − [H + ]
[H + ] = K a ⋅ weak acid +
[H ]
[H + ]2 = K a (c weak acid − [H + ])
[H + ]2 + ( K a × [H + ]) - ( K a × c weak acid ) = 0
- K a ± K a2 + 4 × ( K a × c weak )
By solving the equation, [H + ] = acid
=4.22077×10-4
2
M
pH = -log[H+] = -log(4.22077×10-4) = 3.375
+ [H + ]
In this case [H ] = [acetate ion], so α = = 0.0422 = 4.22 %
c weak acid
c) Here again we do not have enough difference in the order of magnitude to
c − [H + ]
[H + ] = K a ⋅ weak acid +
[H ]
[H + ]2 = K a (c weak acid − [H + ])
[H + ]2 + ( K a × [H + ]) - ( K a × c weak acid ) = 0
- K a ± K a2 + 4 × ( K a × c weak )
By solving the equation, [H + ] = acid
= 1.274×10-4 M
2
pH = -log[H+] = -log(1.274×10-4) = 3.904

2
[H + ]
In this case [H+] = [acetate ion], so α = = 0.127 = 12.7 %
c weak acid
7. What is the pH in a 0.010 M solution of a moderately weak acid if the Ka = 1.5
× 10–1 ?
In the case of this moderately weak acid we do not have enough difference in the
c 0.010
order of magnitude as = = 0.066 . So the following formula should
K a 1.5 × 10 −1
be used:
+ c weak acid − [H + ]
[H ] = K a ⋅
[H + ]

[H + ]2 = K a (c weak acid − [H + ]) [H + ]2 + ( K a × [H + ]) - ( K a × c weak acid ) = 0

[H + ] 2 + (1.5 × 10 −1 × [H + ]) - (1.5 × 10 −1 × 0.010) = 0


- K a ± K a2 + 4 × ( K a × c weak )
By solving the equation, [H + ] = acid
= 9.41 × 10–3 M
2
pH = -log[H+] = -log(9.41× 10–3) = 2.026

8. A windscreen washing liquid contains ammonia in 2.00 g/dm3 concentration.


What is the pH of this liquid?

1 L solution contains 2.00 g of NH3, that is 0.11737 mol of NH3 (n =


m 2g
= = 0.11737 mol). So the concentration of ammonia is:
M.W. 17 g/mol
0.11737 mol
cammonia = = 0.11737 M
1L
In this case, cweak base >>> Kb, so [OH–] = K b ⋅ c weak base = 1.75 × 10 −5 ⋅ 0.11737 =
0.001433 M
pOH = -log[OH–] = -log(0.001433) = 2.844,
pH = 14.00 – pOH = 11.156

9. 20.00 cm3 of 0.1 M ammonia solution is titrated with 0.25 M HClO4. What is
the added volume of titrant and the pH at 75% degree of titration? (6 cm3,
8.766)

The molar amount of ammonia: n = c × V = 0.1 M × 0.020 L = 0.002 mol


At 100 % titration, nHClO4 = nNH3 = 0.002 mol
At 75 % titration, nHClO4 = 0.75 × nNH3 = 0.0015 mol HClO4.
We know the concentration (0.25 M) of the HClO4 solution, so, the volume can be
calculated:
n 0.0015 mol
V= = = 0.006 L = 6 mL
c 0.25 M
At 75 % titration, we have a buffer, NH3 and NH4Cl together. 75 % of the original
NH3 amount is converted to NH4Cl, and 25 % is remained as NH3. So, using the
equation for buffers:
n 0.25 × n total 0.25
[OH-] = Kb ⋅ weak base = Kb ⋅ =1.75 × 10-5 ⋅ = 5.83 × 10-6 M
n salt 0.75 × n total 0.75

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pOH = -log[OH–] = -log(5.83 × 10-6) = 5.234,
pH = 14.00 – pOH = 8.766

10. The concentration of a monochloro acetic acid solution is 0.001 M. What are
the pH and the degree of dissociation in this solution? Ka = 1.2×10-3

Monochloro acetic acid is a weak acid and we do not have enough difference in
the order of magnitude so the following formula should be used:
c − [H + ]
[H + ] = K a ⋅ weak acid +
[H ]
The cweak acid = 0.001 M and Ka = 1.2×10-3
0.001 − [H + ]
[H + ] = 1.2 × 10 −3 ⋅
[H + ]
[H + ] 2 + (1.2 × 10 −3 × [H + ]) - (1.2 × 10 −3 × 0.001) = 0

By solving the equation,

- 1.2 × 10 -3 ± (1.2 × 10 −3 ) 2 + 4 × (1.2 × 10 -3 × 0.001)


[H + ] =
2

[H+] = 6.490 × 10–4 M

pH = – log[H+] = – log (6.490 × 10–4)

pH = 3.188
[H + ]
In this case [H+] = [monochloro acetate ion], so α = = 0.649 = 64.9 %
c weak acid

11. Calculate the pH when we add:


a) 0 mL b) 9 mL c) 20 mL d) 25 mL NaOH solution whose concentration is
0.06 M to a 10 mL sample of acetic acid. The concentration of the acetic acid
is unknown (Ka= 1.86 × 10–5). First, calculate the concentration of the acetic
acid if we know that 20 mL of NaOH is consumed up to the equivalence point.
What kind of indicator would you use for this titration?

Results:
a)
c(acetic acid) = 0.12 mol/dm3

b) at the beginning of the titration: 0 ml of base was added (weak acid)


pH = 2.826

c) After the addition: 9 ml of base (buffer system) pH = 4.643

d) After the addition: 20 ml of base (weak base) pH = 8.666

e) After the addition: 25 ml of base (excess of strong base) pH = 11.933

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12. 10 mL of acetic acid, whose concentration is unknown is titrated with potassium
hidroxide.
a) Calculate the concentration of the acetic acid if the volume of potassium
hidroxide that is consumed up to the equivalence point is 16 mL. The
concentration of KOH is 0.075 M.
b) Calculate the pH after the addition of 10 mL of KOH.

Results:
a) c(acetic acid) = 0.12 M

b) It will be a buffer system: pH = 4.952

13. A 10 mL sample of acetic acid with 0.1 M concentration is titrated with sodium
hidroxide. The concentration of sodium hidroxide is 0.1 M as well. Decide whether it
is right or wrong to use an indicator whose pK=3.8? Support your opinion with
calculations!

a) At first, we assume that the indicator marked the equivalence point correctly. This
would mean that the same amounts of acetic acid and sodium hidroxide are present in
the solution.

n(acetic acid) = 10 × 0.1 = 1 mmol


n(acetic acid) = n(NaOH) = 1 mmol
This amount of NaOH is present in 10 mL of solution.

Then you should calculate the pH of this solution (which contains a weak base,
sodium acetate) to check your assumption about the indicator.
Ka = 1.86 × 10–5
1
csalt/weak base = = 0.05 M
20
K 10 −14
Kb= w = −5
= 5.376 × 10–10
K a 1.86 × 10

[OH–] = K b ⋅ c weak base = 5.185 × 10–6 M

pOH = -log[OH–] = -log(5.185 × 10–6) = 5.285

pH = 14.00-5.285 = 8.715 From this result you can see that at the equivalent point the
pH is 8.715, so the indicator was wrong.

b) Now, let’s see where the indicator marked the end-point.


Around pH 3.8, we still have a buffer system of acetic acid and sodium acetate.

n(acetic acid) = 1 mmol


n(NaOH) = y × 0.1 = 0.1y mmol

[H+] = 10–3.8 = 1.585 × 10–4 M

n weak
[H+] = Ka acid
=
n weak base (salt )

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1 − 0.1y
1.585 × 10–4 = 1.86 × 10–5 ×
0.1y
8.521 × 0.1y = 1 - 0.1y

0.9521y = 1

y = 1.05 mL Only this amount of sodium hidroxide is given to the acid when the
indicator signs!
So the mistake that you make by using the incorrect indicator is [(10-1.05)/10] × 100=
89.5 %

14. 20 mL of benzoic acid of unknown concentration is titrated with potassium


hydroxide whose concentration is 0.095 M. Calculate the pH at: a) 0 %; b) 25 %; c)
100 %; d) 150 % degree of titration. Up to the equivalence point 13.56 mL of KOH
solution is consumed. (Ka = 6.7 × 10–5)

a) n(KOH) = 13.56 × 0.095 = 1.2882 mmol


n(KOH) = n(benzoic acid) = 1.2882 mmol
1.2882
c(benzoic acid) = = 6.441 × 10–2 M
20
–5
Ka = 6.7 × 10

As we do not have the three orders of magnitude difference between the concentration and the
acidic ionization constant, the more complicated formula has to be used for the calculation of
the pH.

+ c weak acid − [H + ]
[H ] = K a ⋅
[H + ]
[H + ]2 = K a (c weak acid − [H + ])

[H + ]2 + ( K a × [H + ]) - ( K a × c weak acid ) = 0

+
- K a ± K a2 + 4 × (K a × c weak acid )
[H ] =
2

+
[H ] =
− 6.7 × 10 −5 ± (6.7 × 10 )
−5 2
+ 4 × 4.31547 × 10 −6
= 2.044 × 10–3 M
2

pH = -log[H+] = -log(2.044 × 10–3) = 2.689

b) n(KOH) = 0.25 × 13.56 × 0.095 = 0.32205 mmol


n(benzoic acid)sum = 1.2882 mmol

We get a basic buffer solution of:


n(benzoic acid)rest = 0.96615 mmol
n(potassium benzoate) = 0.32205 mmol

n weak 0.96615
[H+] = Ka acid
= 6.7 × 10–5 × = 2.01 × 10–4 M
n weak base (salt ) 0.3205

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c) n(potassium benzoate) = 1.2882 mmol
1.2882 × 10 −3
c(potassium benzoate) = = 3.838 × 10–2 M
33.56

The salt, potassium benzoate is a weak base, so first the basic ionization constant
should be calculated.

Kw 10 −14
Kb= = −5
= 1.4925 × 10–10
Ka 6.7 × 10

In this case cweak base >>> Kb, that is the equation to use is:
[OH–] = K b ⋅ c weak base = (1.4925 × 10 −10 ) × 0.03838 = 2.395 × 10–6 M

pOH = -log[OH–] = -log(2.395 × 10–6) = 5.621

pH = 14.00-5.621 = 8.379

d) n(KOH) = 1.50 × 13.56 × 0.095 = 1.9323 mmol


n(benzoic acid)sum = 1.2882 mmol

n(potassium benzoate) = 1.2882 mmol


n(KOH)excess = 1.9323 - 1.2882 = 0.6441 mmol

As we have a weak base and a strong base in the system, it is the strong base, namely
the KOH solution in excess that determines the pH of the solution.

0.6441
c(KOH sol.) = = 1.597 × 10–2 M
40.34

pOH = -log[OH–] = -log(1.597 × 10–2) = 1.797

pH = 14.00-1.797 = 12.203 ≈ 12.20

15. 100 mL of formic acid whose concentration is 0.010 M is titrated by sodium


hydroxide solution of 0.100 M concentration. Calculate the pH: a) before the titration
b) after the addition of 8 mL; c) 9.90 mL of NaOH solution; d) at the equivalence
point. (Ka = 1.77 × 10–4)

a) c(formic acid) = 0.010 M


Ka = 1.77 × 10–4

As we do not have the three orders of magnitude difference between the concentration and the
acidic ionization constant, the more complicated formula has to be used for the calculation of
the pH.

c weak acid − [H + ]
[H + ] = K a ⋅
[H + ]
[H + ]2 = K a (c weak acid − [H + ])

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[H + ]2 + ( K a × [H + ]) - ( K a × c weak acid ) = 0

+
- K a ± K a2 + 4 × ( K a × c weak )
[H ] = acid

+
[H ] =
− 1.77 × 10 − 4 ± (1.77 × 10 )
−4 2
(
+ 4 × 1.77 × 10 − 4 × 0.010 ) = 1.244 ×10–3 M
2

pH = -log[H+] = -log(1.244×10–3) = 2.905

b) n(formic acid) = 100 × 0.010 = 1.00 mmol


n(NaOH) = 0.100 × 8 = 0.800 mmol

After the addition of 8.00 mL of NaOH solution, we get a basic buffer solution of
HCOONa/HCOOH.
n(formic acid) = 0.200 mmol
n(sodium formiate) = 0.800 mmol

n weak 0.200
[H+] = Ka acid
= 1.77 × 10–4× = 4.425 × 10–5 M
n weak base (salt ) 0.800

pH = -log[H+] = -log(4.425×10–5) = 4.354

c) n(formic acid) = 100 × 0.010 = 1.00 mmol


n(NaOH) = 0.100 × 9.90 = 0.990 mmol

After the addition of 9.90 mL of NaOH solution, we get a basic buffer solution of
HCOONa/HCOOH.
n(formic acid) = 0.010 mmol
n(sodium formiate) = 0.990 mmol

n weak 0.01
[H+] = Ka acid
= 1.77 × 10–4× = 1.7523 × 10–6 M
n weak base (salt ) 0.990

pH = -log[H+] = -log(1.7523 × 10–6) = 5.756

d) n(formic acid) = 100 × 0.010 = 1.00 mmol


n(NaOH) = 0.100 × 10= 1.00 mmol
n(sodium formiate) = 1.00 mmol

The salt, sodium formiate is a weak base, so first the basic ionization constant should
be calculated.

Kw 10 −14
Kb= = −4
= 5.649 × 10–11
K a 1.77 × 10

n (sodiumformiate) 1
c(sodium formiate) = = = 0.0091 M
V(solution ) 110

In this case cweak base >>> Kb, that is the equation to use is:

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[OH–] = K b ⋅ c weak base = (5.649 × 10 −11 ) × 0.0091 = 7.170 × 10–7 M

pOH = -log[OH–] = -log(7.170 × 10–7) = 6.144

pH = 14.00-6.144 = 7.856