School of Chemistry, University of KwaZulu-Natal, Howard College Campus, Durban

CHEM191
Tutorial 1: Buffers

Preparing a Buffer

1. How many moles of NH4Cl must be added to 1.0 L of 0.05 M NH3 to form a
buffer whose pH is 11.00? (Assume that the addition of NH4Cl does not change
the volume of the solution.)
Solution
Analyze: Here we are asked to determine the amount of NH4+ ion required to prepare a
buffer of a specific pH.
Plan: The major species in the solution will be NH4+, Cl–, and NH3. Of these, the Cl– ion
is a spectator (it is the conjugate base of a strong acid). Thus, the NH4+–NH3 conjugate
acid-base pair will determine the pH of the buffer solution.

The equilibrium relationship between NH4+ and NH3 is given by the base-dissociation
constant for NH3:

The key to this exercise is to use this Kb expression to calculate [NH4+].

Solve: We obtain [OH–] from the given pH:

pOH = 14.00 – pH = 14.00 – 11.00 = 3.00
[OH-] = 1.0 x 10-3 M

Because Kb is small and the common ion NH4+ is present, the equilibrium concentration
of NH3 will essentially equal its initial concentration:
[NH3] = 0.05 M

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Show working here!!!!

[NH4] = 0.0009 M

Thus, in order for the solution to have pH = 11.00, [NH4+] must equal 0.0009 M. The
number of moles of NH4Cl needed to produce this concentration is given by the product
of the volume of the solution and its molarity:

(1.0L) ( 0.0009 ) = 0.0009 mol

2. Leave out.

Calculating the pH of a buffer

Acidic Buffers

3. What is the pH of a buffer that is 0.12 M in lactic acid (HC3H5O3) and 0.10 M in
sodium lactate? For lactic acid, Ka = 1.4  10–4.

Solution
The initial and equilibrium concentrations of the species involved in this equilibrium are

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Because Ka is small and a common ion is present, we expect x to be small relative to
either 0.12 or 0.10 M. Thus, our equation can be simplified to give

4. Suppose you have a solution which is 0.20 M in acetic acid (HAc) and 0.10 M in
sodium acetate (NaAc). What will be the pH of this solution?

Solution

The values of x may often be neglected if they can be shown to be negligibly

small. Compare the concentrations to the Ka value. In this case the concentrations
of the weak acid and its conjugate base are known to the 10-2 place and the Ka is
to the 10-5 place. Since the difference in magnitude is greater than 100 (actually

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1000 times different), both of this x quantities may be neglected. This simplifies
the algebraic expression to:

Solving for x gives the hydronium ion concentration:

To find the pH, take the negative log the hydronium ion concentration:
pH = -log[H3O+] = -log[3.6 x 10-5] = 4.44

Alkaline Buffers

5. Suppose you have a alkaline buffer consisting of 0.20 M aqueous

ammonia (NH3) and 0.10 M ammonium chloride (NH4Cl). What is the pH
of the solution?

Solution

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Insert the above expressions into the mass action equilibrium expression:

The x quantities often may be neglected. Compare the magnitude of the

concentrations of NH3 and NH4+ to the magnitude of Kb. In this case the
magnitudes of the concentrations are known to the 10-2 magnitude and the Kb is
known to the 10-5 magnitude. Since the difference in magnitude is greater than
100 (difference is 1000), the x quantities shown in bold may be neglected. This
simplifies the expression to the expression shown:

Solve this expression for x which will provide the hydroxide ion concentration:

To find the pH, first find the pOH by taking the negative log of the hydroxide ion
concentration:

pOH = -log[OH-] = -log(3.6 x 10-5) = 4.44

Next, subtract the pOH from 14.00 to find the pH:

pH = 14.00 - pOH = 14.00 - 4.44 = 9.56

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Calculating pH Changes in Buffers

6. A buffer solution is 1.0 M in acetic acid and in sodium acetate. Calculate the
change in pH upon adding 0.1 mole of gaseous hydrochloric acid to 1000 mL of
this solution. Assume that the volume does not change when the HCl is added.
The acid dissociation constant, Ka for CH3COOH is 1.8 x 10-5.

[CH3COOH] = 1.0M AND [CH3COO¯] = 1.0M

+ ¯
Ka = [H ][CH3COO ] =1.8 x 10-5
[CH3COOH]
Ka[CH3COOH]
[H+] = [CH3COO ¯]
-5
= (1.8 x 10 ) (1.0)
(1.0)

= 1.8 x 10-5M

pH = -log (1.8 x 10-5)

= 4.74

HCl(aq) → H+(aq) + Cl¯(aq)

0.1 mol 0.1 mol 0.1 mol

Originally there were 1.0 mol CH3COOH and 1.0 mol CH3COO¯ present in 1L of
the solution. After neutralization of the HCl acid by CH3COO¯, which we write as

CH3COO¯ (aq) + H+(aq) → CH3COOH(aq)

0.1 mol 0.1 mol 0.1 mol

The number of moles of acetic acid and the number of the moles of acetate ions
present are

CH3COOH: (1.0 + 0.1) mol = 1.1 mol

CH3COO_: (1.0 – 0.1) mol = 0.9 mol

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 Next we calculate the hydrogen ion concentration:

Ka[CH3COOH]
+
[H ] = [CH3COO ¯]
(1.8 x 10-5) (1.1)
=
0.9
= 2.2 x 10-5 M

The pH of the solution becomes

pH = − log (2.2 x 10-5)

= 4.66

Therefore the change in pH = 4.66 - 4.74 = -0.08

7. Calculate the pH of the solution resulting from the addition of 25.00 mL of

0.0924 mol dm-3 NaOH to 50.00 mL of 0.1045 mol dm-3 CH3COOH. The acid
dissociation constant, Ka for CH3COOH is 1.76 x 10-5.

n of base = 0.02500 x 0.0924 = 0.00231

n acid = 0.05000 x 0.1045 = 0.005225mol

CH3COOH + NaOH ⇌ CH3COO- + H2O

Start 0.005225 0.00231

React 0.00231 0.00231 0.00231

Final 0.002915 0.00 0.00231

Show full working here!!!

pH = 4.65

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8. A buffer solution is 0.20 M in acetic acid and in sodium acetate.
a) Calculate the change in pH upon adding 1.0 mL of 0.10 M hydrochloric
acid to 10 mL of this solution. The acid dissociation constant, Ka for
CH3COOH is 1.76 x 10-5.

Initial pH = -(logKa) = 4.75 ( show how you arrived at this!)

No. of moles of base = 0.0010 dm3 × 0.20 mol dm-3 = 0.0020 mol = no. moles of
acid
No. of moles of HCl = 0.0010 dm3 × 0.10 mol dm-3 = 0.00010mol

CH3COO- + H3O+ ⇌ CH3COOH + H2O

Start 0.0020 0.00010 0.0020

React 0.0001 0.00010 0.0001

Final 0.0019 0 0.0021

Show full working here !!!

pH = 4.71

∆pH = pH final – pH initial

= 4.71 – 4.75
= -0.04
b) Explain the effect of the addition of the acid in the solution in the question
above.
The weak base will react with the strong acid according to the following
reaction

CH3COO- + H3O+ ⇌ CH3COOH + H2O

The strong acid is converted into the weak acid CH3COOH and the pH will
decrease.

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9. What would be the pH of a solution prepared by mixing 25.00 mL of 0.1000 M
acetic acid and 25.00 mL of 0.0500 M sodium acetate?
Ka(CH3COOH) = 1.75 × 10-5.

No reaction occurring. After mixing,

25.00
[CH 3COO  ]  x 0.0500  0.0250 M
25.00  25.00
25.00
[CH 3COOH ]  x 0.1000  0.05000 M
25.00  25.00
Show working here!!

pH = 4.45

10. Calculate the pH of the solution prepared from adding 25.00 mL of

0.1010 mol dm-3 NaOH to 50.00 mL of a 0.1122 mol dm-3 CH3CH2COOH
solution (pKa CH3CH2COOH = 4.88).
Answer:
3
0.1122 mol 1 dm
Initial moles of CH3CH2COOH = 50.00 mL  3

1 dm 1 000 mL

= 5.61  10 mol
-3

3
0.1010 mol 1 dm
Initial moles of NaOH = 25.00 mL  3

1 dm 1 000 mL

= 2.525  10-3 mol

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Moles CH3CH2COOH + NaOH → CH3CH2COO- + Na+ + H2O

Initial 5.61  10-3 2.525  10-3

React 2.525  10-3 2.525  10-3

Form 2.525  10-3

Equilibrium 3.085  10-3 0 2.525  10-3

Therefore after this reaction is complete we have both CH3CH2COOH and CH3CH2COO- present.
We thus have a buffer.

Show working here!!!

pH = 4.79

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