pH and Buffers

The definition of acids has evolved over time:

Arrhenius → Bronsted-Lowry → Lewis

Arrhenius definition:
Acids when dissolved in water increase the concentration of H+ ions e.g. HCl
Bases when dissolved in water increase the concentration of OH- ions e.g. NaOH
However, this definition is limited to aqueous solutions. A more general definition is given by:
Bronsted-Lowry definition:
Acids donate H+ ions (also called ‘protons’) to other species.
Bases accept H+ ions/ protons from other species.
In other words, a transfer of H+ ions/ protons is involved between acids and bases.
e.g. HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)
HCl is acting as a Bronsted-Lowry acid, H2O is acting as a Bronsted-Lowry base.

Also, the Bronsted-Lowry definition is not restricted to aqueous solutions.

e.g. HCl (g) + NH3 (g) NH4Cl (s)
HCl - Bronsted-Lowry acid; NH3 - Bronsted-Lowry base.

Amphiprotic substances can act as either an acid or a base:

e.g. HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

H2O is acting as a base in the first reaction but as an acid in the second thus it is amphiprotic.

Lewis definition:
An acid is an electron pair acceptor, a base is an electron pair donor.
e.g. NH3 (g) + BF3 (g) NH3BF3 (g)
The N atom of NH3 has a lone pair of electrons which it can donate to the B atom of BF3.
Therefore, BF3 is acting as a Lewis acid (it accepts the e- pair), NH3 is acting as a Lewis base (it
donates the e- pair).

e.g. NH3 (g) + AlCl3 (s) NH3AlCl3 (s)

AlCl3 - Lewis acid, NH3 - Lewis base

Therefore, it can be seen that the definition of acids and bases expands as you go from:
Arrhenius → Bronsted-Lowry → Lewis

N.B.: In aqueous solutions, H+ ions exist as the H3O+ or hydronium ion:

H+ (aq) + H2O (aq) H3O+ (aq)
i.e. Acids actually form the hydronium ion in aqueous solution/ water:
e.g. HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

Conjugate Acid/ Base Pairs

When an acid ionizes/ reacts it also produces another species which is part of the original
molecule. This is called its conjugate base. Similarly when a base ionizes, it produces a
conjugate acid. This is how a conjugate acid-base pair is created.

e.g. HNO2 + H2O NO2- + H3O+

acid base conj. base conj. acid

HNO2 and NO2- form a conjugate acid/ base pair (HNO2 is the acid; NO2- is its conj. base)
H2O and H3O+ also form a conjugate acid/ base pair (H2O is the base; H3O+ is its conj. acid).

Basicity/ Proticity of an Acid

This refers to the number of H+ ions donated by an acid.
Monobasic acid – donates 1 H+ ion e.g. HCl, HNO3
Dibasic acid – donates 2 H+ ions e.g. H2SO4
Tribasic acid – donates 3 H+ ions e.g. H3PO4

Basicity must be taken into account when calculating the pH of an acid.

Basicity can be determined by reaction of the acid with a known base such as NaOH.
e.g. 0.02 mol of an acid, HnY were neutralized by 0.06 mol of NaOH. What is the formula of the
acid?
HnY : NaOH
0.02 : 0.06
1:3
The acid must be tribasic as it must produce 3 H+ ions to react with all of the OH- ions of NaOH,
therefore the value of n is 3 and the formula of the acid is: H3Y.

Strengths of acids/ bases

Strong acids – ionize completely; equilibrium lies significantly to the right; a high
concentration of H+ ions is produced
e.g. HCl H+ + Cl-

Weak acids – ionize partially; equilibrium lies significantly to the left; a low concentration of
H+ ions is produced

e.g. CH3COOH CH3COO- + H+

Strong bases – ionize completely; equilibrium lies significantly to the right; a high concentration
of OH- ions is produced
e.g. NaOH Na+ + OH-

Weak bases – ionize partially; equilibrium lies significantly to the left; a low concentration of
OH- ions is produced
e.g. NH3 + H2O NH4+ + OH-

The ionic product of water (Kw)

The dissociation of water can be represented as: Note: It is also depicted as
the self-ionizaion of water:
H2O (l) H+ (aq) + OH- (aq)
2H2O H3O+ + OH-
The equilibrium expression for the above reaction is:
+ - + - Therefore: Kw = [H3O+][OH-]
K = [H (aq)][OH (aq)] = [H (aq)][OH (aq)]
[H2O (l)]

(Note: The concentration of a pure solid or liquid is generally not included in equilibrium
expressions.)

Thus: Kw = [H+][OH-] This is called the ionic product of water

At 25oC Kw is a constant:
Kw = 1.0 x 10-14 (at 25oC)

When [H+] = [OH-], a solution is said to be neutral

When [H+] > [OH-], the solution is said to be acidic
When [OH-] > [H+], the solution is said to be basic/ alkaline

The pH scale
- A scale ranging from 0 to 14 which indicates the acidity or alkalinity of a solution.

pH = –log [H+] Similarly, pOH = –log [OH-]

pH + pOH = 14
e.g. (1) What is the pH of a 0.1 M H2SO4 solution?
H2SO4 2H+ + SO42-
0.1 mol of H2SO4 produce 0.2 mol H+ (Mole ratio H2SO4 : H+ = 1 : 2)
pH = –log [H+] = -log(0.2) = 0.7

e.g. (2) What is the pH of a 0.1 M NaOH solution?

NaOH Na+ + OH-
0.1 mol of NaOH produce 0.1 mol OH- (Mole ratio NaOH : OH- = 1 : 1)
pOH = –log [OH-] = -log(0.1) = 1
pH = 14 – pOH
= 14 – 1 (Alternatively, we can find [H+] using: [H+][OH-] = 1.0 x 10-14
= 13 then calculate pH using: pH = -log[H+])

The equilibrium constant Ka – A measure of acidity

Consider the dissociation of an acid, HX:

HX (aq) H+ (aq) + X- (aq)

Writing the equilibrium expression for the dissociation:
Ka = [H+][X-]
[HX]

Ka – Referred to as the Acid Dissociation Constant

- Predicts the strength of acids

The higher/ greater the ionization of an acid, the higher the concentration of H+ therefore the
higher the Ka value. The higher the Ka value, the stronger the acid.

The equilibrium constant Kb – A measure of basicity/ alkalinity

Consider the dissociation of a base, B:

B (aq) + H2O (l) BH+ (aq) + OH- (aq)

Writing the equilibrium expression for the dissociation:
Kb = [BH+][OH-] = [BH+][OH-]
[B][H2O] [B]

Kb – Referred to as the Base Dissociation Constant

- Predicts the strength of bases

The higher/ greater the ionization of a base, the higher the concentration of OH- therefore the
higher the Kb value. The higher the Kb value, the stronger the base.

We can also convert Ka and Kb to pKa and pKb:

pKa = –log Ka pKb = –log Kb

However, the higher the pKa/ pKb value, the weaker the acid/ base.
The lower the pKa/ pKb value, the stronger the acid/ base.

e.g. Consider the following:

Methanoic acid, HCOOH Ka = 1.77 x 10-4 pKa = -log(1.77 x 10-4) = 3.75
Propanoic acid, C2H5COOH Ka = 1.34 x 10-5 pKa = -log(1.34 x 10-5) = 4.87
HCOOH is the stronger acid of the two, as it has the higher Ka value but the lower pKa.

pKa + pKb = 14
Ka x Kb = Kw i.e. KaKb = 1.0 x 10-14 (at 25oC)

Calculation of the pH of weak acids/ bases utilizes Ka/ Kb values:

e.g. (3) Calculate the pH of a 0.3 M solution of acetic acid (CH3COOH) if its Ka is 1.8 x 10-5.

CH3COOH CH3COO- + H+
Let the no. of mol of H+ formed be x.
(We use ‘x’ because CH3COOH is partially ionized and we do not know how much of it
dissociates to form H+)
 CH3COOH CH3COO- H+
Initial conc./ M 0.3 0 0
Change in conc./ M -x +x +x
Equil. conc./ M 0.3 – x x x

Ka = [CH3COO-][H+]
[CH3COOH]
Ka = (x)(x) = x2
(0.3 – x) (0.3 – x)
Assumption: Since x is very small, (0.3 – x) ≈ 0.3
Ka = x2
0.3
1.8 x 10-5 = x2
0.3
x = 2.3 x 10-3
[H+] = 2.3 x 10-3 M
pH = -log[H+]
= -log(2.3 x 10-3)
= 2.64

A similar method is applied when calculating the pH of bases:

Let the no. of mol of OH- ions formed be ‘x’, calculate x using the Kb expression, use the value
of x to calculate pOH, then calculate pH.
e.g. (4) Calculate the pH of a 0.3 M solution of ammonia (NH3) if its Kb is 1.8 x 10-5.

NH3 + H2O NH4+ + OH-

Let the no. of mol of OH- formed be x.
(We use ‘x’ because NH3 is partially ionized and we do not know how much of it dissociates to
form OH-)
NH3 NH4+ OH-
Initial conc./ M 0.3 0 0
Change in conc./ M -x +x +x
Equil. conc./ M 0.3 – x x x
Kb = [NH4+][OH-]
[NH3]
Kb = (x)(x) = x2
(0.3 – x) (0.3 – x)
Assumption: Since x is very small, (0.3 – x) ≈ 0.3
Kb = x2
0.3
1.8 x 10-5 = x2
0.3
x = 2.3 x 10-3
[OH-] = 2.3 x 10-3 M
pOH = -log[OH-]
= -log(2.3 x 10-3)
= 2.64
pH = 14 – pOH = 14 – 2.64 = 11.36

Buffers
Buffers are solutions that can resist significant changes in pH upon addition of small
amounts of acid or base.
Buffers are comprised of either:
A weak acid and its salt (where the salt is actually the conjugate base of the acid)
e.g. CH3COOH and CH3COO-Na+, called an ethanoic acid/ sodium ethanoate buffer
A weak base and its salt (where the salt is the conjugate acid of the base)
e.g. NH3 and NH4Cl, called an ammonia/ ammonium chloride buffer

How a buffer works:

e.g. When a small amt. of acid (i.e. H+) is added to an ethanoic acid/ sodium ethanoate buffer:

CH3COO- + H+ CH3COOH
The CH3COO- ions (the conj. base) in the buffer react with/ neutralize the added H+ ions,
preventing the large decrease in pH that would have occurred if the buffer had not been present.
When a small amt. of base (i.e. OH-) is added to the buffer:

CH3COOH + OH- CH3COO- + H2O

The CH3COOH molecules (the acid) in the buffer react with/ neutralize the added OH- ions,
preventing the large increase in pH that would have occurred if the buffer had not been present.
(N.B.: As seen above, a buffer works according to Le Chatelier’s Principle.)

Similarly, when a small amount of acid is added to the NH3/ NH4Cl buffer, it is neutralized by
the base component of the buffer i.e. NH3 so the pH is controlled:

NH3 + H+ NH4+
When a small amount of base is added to the buffer, it is neutralized by the acid component i.e.
NH4+, again controlling the pH:

NH4+ + OH- NH3 + H2O

Buffers are important in both physiological systems and many chemical reactions.
e.g. enzymes require a very narrow pH range for proper functioning.

Buffers in physiological systems

The pH of blood is maintained in a narrow pH range: 7.35 – 7.45
If blood pH is altered significantly, several harmful effects can occur:
 The rupture of cell membranes
 Loss in the structure of proteins
 Dissipation in enzyme activity

One of the most important buffer systems in the blood is a carbonic acid/ bicarbonate system:

H+ + HCO3- H2CO3 CO2 + H2O

If the blood is too acidic, the buffer equilibrium shifts to the right; HCO3- (bicarbonate) removes
H+ and ultimately produces and expels CO2 (g) (i.e. exhalation occurs).
If blood pH is too high (alkaline), the system retains more CO2 (inhalation occurs), shifting
equilibrium to the left and increasing the production of H+ so as to counteract the increase in
alkalinity.
Therefore, by adjusting the rate of respiration the body can maintain blood pH levels
within the desired range.

Calculating the pH of a buffer (Use of the Henderson-Hasselbalch equation)

Consider the equilibrium: HX (aq) H+ (aq) + X- (aq)

Ka = [H+][X-]
[HX]

Rearranging: [H+] = Ka [HX]

[X-]

Taking log10: log10[H+] = log10 Ka [HX]

[X-]
i.e. The Henderson-
log10[H+] = log10 Ka + log10 [HX]
Hasselbalch equation
[X-]
is derived from the Ka
Dividing by -1: –log10[H+] = –log10 Ka – log10 [HX] expression of any
[X-] weak acid, HX.

pH = pKa + log10 [X-]

[HX]

pH = pKa + log10 [Base] (Henderson-Hasselbalch equation)

[Acid]

From the equation, it can be seen that the pH of a buffer depends on:
(i) Ka (ii) The ratio of [X-]:[HX] (i.e. [Base]:[Acid])
Since Ka for any buffer systems is constant, to improve buffering capacity a larger
concentration of both HX (acid) and X- (base) is required.

Buffering capacity – the quantity of strong acid or base that could be added to the buffer before
its pH changes significantly
Effective pH range – the pH over which the buffer can most effectively act; this is generally the
pKa ± 1 e.g. if pKa = 6.3, effective pH range = 5.3 – 7.3

Buffer Calculations:
Calculating the pH of a buffer

e.g. (1) Calculate the pH of a buffer containing 0.50 M ethanoic acid and 0.20 M sodium
ethanoate. Ka (CH3COOH) = 1.7 x 10-5

pH = pKa + log10 [Base]

[Acid]
= pKa + log10 [CH3COO-Na+]
[CH3COOH]

= –log(1.7 x 10-5) + log(0.20)

(0.50)
= 4.37

Preparing buffers
e.g. (2) What amount of NH3 and NH4Cl can be used to form a buffer whose pH is 9.00?
Kb (NH3) = 1.8 x 10-5

KaKb = Kw = 1.0 x 10-14

Ka(1.8 x 10-5) = 1.0 x 10-14
Ka = 5.56 x 10-10

pH = pKa + log10 [Base]

[Acid]

pH = –log (5.56 x 10-10) + log10 [NH3]

[NH4Cl]

9.00 = 9.26 + log [NH3]

[NH4Cl]
-0.26 = log [NH3]
[NH4Cl]

[NH3] = 10-0.26
[NH4Cl]
 [NH3] = 0.55 or 0.55
[NH4Cl] 1
i.e. [NH3] : [NH4Cl] = 0.55 M : 1 M

Therefore 0.55 M NH3 and 1 M NH4Cl can be used to prepare a buffer of pH 9.00.

Note: Once the concentrations of the buffer components are found, equal volumes of these
components are added together to obtain a particular desired volume of buffer solution.
e.g. To make up 1 L of a buffer solution, 500 mL each of the acid and base components are
added together. To make up 200 mL of a buffer solution, 100 mL each of the acid and base
are required. Additionally, different volumes of buffer solutions made up would contain
different actual number of moles of acid and base, depending on the volume of each that
was added together to make up the buffer.

Calculating the change in pH of buffers

e.g. (3) A buffer is made by adding 0.3 M CH3COOH and 0.3 M CH3COO-Na+. The pKa of the
buffer is 4.74. Calculate the pH of this buffer solution after 0.02 mol of NaOH are added.

The added NaOH will react with the CH3COOH in the buffer:

CH3COOH + OH- CH3COO- + H2O

CH3COOH OH- CH3COO-
Initial conc./ M 0.3 0 0.3
Addition 0.02
Equil. conc./ M 0.28 0 0.32

pH = pKa + log10 [CH3COO-] Note: [CH3COOH] decreased as 0.02 mol

[CH3COOH] reacted with 0.02 mol of the OH- ions.
[CH3COO-] increased as 0.02 mol were
pH = 4.74 + log (0.32) = 4.80
produced during the rxn.
(0.28)

When calculated, the original pH of the buffer was actually 4.74. Note that by comparing the two
pH values, it can be seen that there is no significant change in pH after the 0.02 mol of NaOH are
added. The pH increased slightly, by 0.06 units. So the buffer was effective in controlling pH.
If a small amount of acid is added to the buffer instead, then we would expect the pH to decrease
slightly, but it would still be close to 4.74.

Buffer Capacity
pH range of a buffer = pKa ± 1
pH = pKa + log10 [Base]
[Acid]
When pH = pKa + 1 (i.e. the maximum possible value of the range):
(pKa + 1) = pKa + log10 [Base] i.e we have substituted the
[Acid] max. possible pH value of
1 = log10 [Base] the buffer into the
[Acid] Henderson-Hasselbalch
equation and found the max.
[Base] = 101 = 10 possible [base]:[acid] ratio
[Acid]
Buffer capacity is therefore reached when the ratio of [Base]:[Acid] is 10:1
i.e. If the ratio is greater than 10:1, then the buffer capacity is exceeded and the buffer is no
longer effective.

e.g. (4) Refer to e.g. (3). Is the buffer capacity exceeded when the 0.02 mol of NaOH are added?

Examine the ratio of [Base]:[Acid] :-

[CH3COO-] : [CH3COOH]
0.32 : 0.28
1.14 : 1
Since the ratio of [CH3COO-] : [CH3COOH] does not exceed 10:1, the buffer is acting within its
capacity.

Alternatively, we can consider the effective pH range:

pH range of the buffer = pKa ± 1 = 4.74 ± 1 = 3.74 – 5.74
The pH of the buffer after the 0.02 mol of NaOH were added was calculated to be 4.80 which
falls within the pH range, therefore the buffer capacity has not been exceeded.
e.g. (5) Given that the Ka for NH4+ is 5.7 x 10-10,
(a) Calculate the pH of a buffer that is 0.02 M in NH3 and 0.03 M in NH4Cl
(b) What is the pH of the solution after adding 1.00 mL of 0.10 M NaOH to 100 mL of
this buffer?
(c) Has the buffer capacity been exceeded?

(a) pH = pKa + log10 [NH3]

[NH4+]

= –log(5.7 x 10-10) + log (0.02)

(0.03)
= 9.07
(b) 100 mL of buffer = 50 mL of NH3 soln. + 50 mL of NH4Cl soln.
Mol of NH3 = 50 x 0.02/ 1000 = 0.001 mol
Mol of NH4Cl = 50 x 0.03/ 1000 = 0.0015 mol
Mol of NaOH added = 1.00 x 0.10/ 1000 = 0.0001 mol
NH4+ OH- NH3
Initial mol 0.0015 0 0.001
Addition 0.0001
Equil. mol 0.0014 0 0.0011

[NH3] = 0.0011/ 101 x 1000 = 0.011 M Rxn: NH4+ + OH- NH3

[NH4+] = 0.0014/ 101 x 1000 = 0.014 M

pH = pKa + log10 [NH3]

[NH4+]

= –log(5.7 x 10-10) + log (0.011)

(0.014)
= 9.14
(c) After the addition of NaOH:
[NH3] : [NH4+]
0.011 M : 0.014 M
0.8 : 1
Since the ratio of [NH3] : [NH4+] does not exceed 10:1, the buffer capacity has not
been exceeded.
Titration curves
- show where the equivalence point of the titration is
- help to select a suitable indicator(s) for the titration

Strong Acid-Strong Base titration

Graph 1

There are four regions of the curve:

Initial pH – low, since we are starting with the acid; (high, if we start with the base)
Between the initial pH and the equivalence point – pH increases as we are adding base to the
acid; some acid reacts with (neutralizes) the base and some acid remains in the solution.
Equivalence point – equal no. of mol of acid and base react; complete neutralization occurs; pH
is 7 because a neutral salt is formed
After the equivalence point – pH is highest as excess base remains; (pH would be lowest if we
had started off with base and added acid to it, because then excess acid would be present at the
end of the titration instead [See diagram below])

Suitable indicators for these titrations: phenolphthalein, methyl orange, bromocresol green

Calculation of pH for a Strong Acid-Strong Base titration

e.g. (1) Calculate the pH when the following quantity of 0.10 M NaOH solution has been added
to 50.0 mL of 0.10 M HCl solution: (i) 49.0 mL (ii) 51.0 mL

(i) no. of mol of HCl = 0.10 x 50.0/ 1000 = 0.005 mol

no. of mol of NaOH = 0.10 x 49.0/ 1000 = 0.0049 mol
H+ + OH- H2O [Titration equ.]
H+ OH-
Initial mol 0.005 0
Addition 0.0049
Final mol 0.0001 0

Total volume of solution = 50.0 + 49.0 = 99.0 mL Note: If a dibasic acid is

+ used e.g. H2SO4, the no. of
99.0 mL contain 0.0001 mol H
mol of H+ in the table must
[H+] = 0.0001/ 99.0 x 1000 = 0.001 M be doubled.
 pH = -log[H+] Note: All of the OH- ions were
neutralized but the H+ ions were
= -log(0.001) in excess, therefore the resulting
= 3.00 solution has an acidic pH.

[Refer to Graph 1 above; at pH 3.00, we have not yet reached the equivalence point]

(ii) no. of mol of HCl = 0.005 mol [From part (i)]

no. of mol of NaOH = 0.10 x 51.0/ 1000 = 0.0051 mol
H+ + OH- H2O [Titration equ.]
H+ OH-
Initial mol 0.005 0
Addition 0.0051
Final mol 0 0.0001

Total volume of solution = 50.0 + 51.0 = 101.0 mL

101.0 mL contain 0.0001 mol OH-
[OH-] = 0.0001/ 101.0 x 1000 = 0.001 M

pOH = -log[OH-]
= -log(0.001)
= 3.00
pH = 14 – pOH Note: All of the H+ ions were
neutralized but the OH- ions
= 14 – 3.00 were in excess, therefore the
= 11.00 resulting solution has a basic pH.

[Refer to Graph 1 above; at pH 11.00, we have gone past the equivalence point]
Weak Acid-Strong Base titration
Similar titration curve as for Strong Acid-Strong Base titration:

Graph 2

Initial pH – use Ka to calculate pH as we are starting with a weak acid

Between initial pH and equivalence point – pH increases as we are adding base to the acid;
some acid reacts with (neutralizes) the base and some acid remains in the solution; use Ka to
calculate the pH of the solution.
Equivalence point – equal no. of mol of acid and base react; complete neutralization occurs but
pH is not 7, it is > 7 because a basic/ alkaline salt is formed; use Kb to calculate the pH of
the solution at this point
After equivalence point – pH is highest as excess base remains

Suitable indicator for this titration: phenolphthalein

Calculating pH for a Weak Acid-Strong Base titration
e.g. (2) Calculate the pH of a solution formed when 45.0 mL of 0.10 M NaOH is added to 50.0
mL of 0.10 M CH3COOH. (Ka = 1.8 x 10-5)

no. of mol of CH3COOH = 0.10 x 50.0/ 1000 = 0.005 mol

no. of mol of NaOH = 0.10 x 45.0/ 1000 = 0.0045 mol

CH3COOH + OH- CH3COO- + H2O [Titration equ.]

CH3COOH OH- CH3COO-
Initial mol 0.005 0 0
Addition 0.0045
Final mol 0.0005 0 0.0045

Total volume of solution = 50.0 + 45.0 = 95.0 mL

[CH3COOH] = 0.0005/ 95.0 x 1000 = 0.0053 M
[CH3COO-] = 0.0045/ 95.0 x 1000 = 0.0474 M
But CH3COOH & CH3COO- exist in the solution in the following equilibrium:

CH3COOH CH3COO- + H+ [Equilibrium equ.]

Ka = [CH3COO-][H+]
[CH3COOH]

[H+] = Ka [CH3COOH] Using the Ka expression,

[CH3COO-] the H+ conc. must be
found in order to calculate
= (1.8 x 10-5)(0.0053) the pH of the solution.
(0.0474)

= 2 x 10-6 M

pH = -log[H+]
= -log(2 x 10-6)
= 5.70

[Refer to Graph 2 above; at pH 5.70, we have not yet reached the equivalence point]
Calculating the pH at the equivalence point
e.g. (3) Calculate the pH at the equivalence point in the titration of 50.0 mL of 0.10 M
CH3COOH with 0.10 M NaOH. (Kb = 5.6 x 10-10)

no. of mol of CH3COOH = 0.10 x 50.0/ 1000 = 0.005 mol

It will take 50.0 mL of NaOH to reach the equivalence point.

CH3COOH + OH- CH3COO- + H2O [Titration equ.]

CH3COOH OH- CH3COO-
Initial mol 0.005 0 0
Addition 0.005
Final mol 0 0 0.005

Total volume of solution = 50.0 + 50.0 = 100.0 mL

[CH3COO-] = 0.005/ 100.0 x 1000 = 0.05 M

CH3COO- is a weak base:

CH3COO- + H2O CH3COOH + OH- [Equilibrium equ.]

Let no. of mol of OH- ions formed be x.
CH3COO- CH3COOH OH-
Initial conc./ M 0.05 0 0
Change in conc./ M -x +x +x
Equil. conc./ M 0.05 – x x x

Kb = [CH3COOH][OH-]
[CH3COO-] i.e. The titration
produced CH3COO- at
Kb = (x)(x) = x2 the end-point which is
(0.05 – x) (0.05 – x) itself a weak base.
Therefore a Kb
Assumption: Since x is very small, (0.05 – x) ≈ 0.05 calculation must be used
Kb = x2 to obtain the [OH-] and
0.05 thus the pH of the weak
base, CH3COO-, which is
5.6 x 10-10 = x2 the pH at the end-point of
0.05
the titration.
x = 5.3 x 10-6
[OH-] = 5.3 x 10-6 M
pOH = -log[OH-]
= -log(5.3 x 10-6)
= 5.28
pH = 14 – pOH
= 14 – 5.28
= 8.72 [Refer to Graph 2; pH 8.72 is the exact pH at the equivalence point]

Weak Base - Strong Acid titration

Initial pH – use Kb to calculate pH as we are starting with a weak base

Between initial pH and equivalence point – pH decreases as we are adding acid to the base;
some base reacts with (neutralizes) the acid and some base remains in the solution; use Kb to
calculate the pH of the solution.
Equivalence point – equal no. of mol of acid and base react; complete neutralization occurs but
pH is not 7, it is < 7 because an acidic salt is formed; use Ka to calculate the pH of the
solution at this point
After equivalence point – pH is lowest as excess acid remains
Suitable indicator for this titration: methyl orange
Past paper question:
A 0.100 M NaOH solution is used to titrate 50.0 mL of 0.100 M acetic acid. Calculate the pH of
the solution at the following four points:
(a) Before any NaOH is added.
(b) After 40.0 mL of NaOH has been added.
(c) After 50.0 mL of NaOH has been added.
(d) After 50.2 mL of NaOH has been added.
(Ka of acetic acid = 1.8 x 10-5; Kw = 1.0 x 10-14)

(a) CH3COOH CH3COO- + H+

CH3COOH CH3COO- H+
Initial conc./ M 0.1 0 0
Change in conc./ M -x +x +x
Equil. conc./ M 0.1 – x x x

Ka = [CH3COO-][H+]
[CH3COOH]

Ka = (x)(x) = x2
(0.1 – x) (0.1 – x)
Assumption: Since x is very small, (0.1 – x) ≈ 0.1
Ka = x2
0.1
1.8 x 10-5 = x2
0.1
x = 1.34 x 10-3
[H+] = 1.34 x 10-3 M
pH = -log[H+]
= -log(1.34 x 10-3)
= 2.87
(b) Mol of CH3COOH = 0.1 x 50/ 1000 = 0.005 mol
Mol of NaOH added = 0.1 x 40/ 1000 = 0.004 mol
 CH3COOH + OH- CH3COO- + H2O
CH3COOH OH- CH3COO-
Initial mol 0.005 0 0
Addition 0.004
Final mol 0.001 0 0.004

[CH3COOH] = 0.001/ 90 x 1000 = 0.011 M

[CH3COO-] = 0.004/ 90 x 1000 = 0.044 M
Ka = [CH3COO-][H+]
[CH3COOH]
[H+] = Ka [CH3COOH]
[CH3COO-]

= (1.8 x 10-5)(0.011)
(0.044)

= 4.5 x 10-6 M

pH = -log[H+]
= -log(4.5 x 10-6)
= 5.35

(c) Mol of NaOH added = 0.1 x 50/ 1000 = 0.005 mol

CH3COOH + OH- CH3COO- + H2O

CH3COOH OH- CH3COO-
Initial mol 0.005 0 0
Addition 0.005
Final mol 0 0 0.005

[CH3COO-] = 0.005/ 100 x 1000 = 0.05 M

CH3COO- + H2O CH3COOH + OH-

CH3COO- CH3COOH OH-
Initial conc./ M 0.05 0 0
Change in conc./ M -x +x +x
Equil. conc./ M 0.05 – x x x
 Kb = [CH3COOH][OH-]
[CH3COO-]
Kb = (x)(x) = x2
(0.05 – x) (0.05 – x)
Assumption: Since x is very small, (0.05 – x) ≈ 0.05
Kb = x2
0.05
5.56 x 10-10 = x2
0.05
x = 5.27 x 10-6
[OH-] = 5.27 x 10-6 M
pOH = -log[OH-]
= -log(5.27 x 10-6)
= 5.28
pH = 14 – pOH
= 14 – 5.28
= 8.72

(d) Mol of NaOH added = 0.1 x 50.2/ 1000 = 0.00502 mol

CH3COOH + OH- CH3COO- + H2O

CH3COOH OH- CH3COO-
Initial mol 0.005 0 0
Addition 0.00502
Final mol 0 0.00002 0.005 (negligible)

[OH-] = (0.00002/ 100.2) x 1000 = 0.0002 M

pOH = -log[OH-]
= -log(0.0002)
= 3.7
pH = 14 – pOH
= 14 – 3.7
= 10.3