Acid-Base Indicators

Rem: We’ve looked at pH titration curves obtained when an aqueous solution of an acid is
added to an aqueous solution of a base. We considered the following four cases:
- Strong acid-strong base
- Weak acid-strong base
- Strong acid-weak base
- Weak acid-weak base
We will now use these four curves to help us understand why different indicators are required
for different types of titrations.
An acid-base indicator is either a weak acid or a weak base. Most indicators are weak acids
(HIn), whose dissociation in aqueous solution can be represented as follows:
HIn(aq) ⇌ H+(aq) + In-(aq)
The molecule, HIn, and its conjugate base, In-, have different colours in aqueous solution. For
methyl orange, these are: red and yellow respectively.
HIn(aq) ⇌ H+(aq) + In-(aq)
red yellow

When [H+(aq)] is sufficiently large, equilibrium shifts far left and red colour dominates.
If [H+(aq)] is very low, equilibrium lies far right and yellow colour dominates. Thus, indicator
changes colour according to pH of the solution in which it is put.
The stage at which [HIn(aq)] = [In-(aq)], indicator colour is orange. pH at which this stage is
reached is determined using the equilibrium constant, KIn, for methyl orange as follows:
KIn = [H+(aq)] [In-(aq)] / [HIn(aq)] = 2.00 x 10-4 mol/dm3
When [HIn(aq)] = [In-(aq)], the expression becomes:
KIn = [H+(aq)] = 2.00 x 10-4 mol/dm3. This gives pH of 3.70 for this stage.
So, methyl orange will change colour at pH = 3.70.
Note: this pH value is the same as the value of pKIn for methyl orange. Therefore, pH at
which different indicators will change colour can be determined from their pKIn values.
pH Range of Indicators
As a ‘rule of thumb’ the red colour of methyl orange will first dominate when [HIn(aq)] is ten
times [In-(aq)], and the yellow colour dominates when [In-(aq)] is ten times [HIn(aq)].
Approximate pH at which each colour dominates is, thus, calculated as follows:
When [HIn(aq)] = 10[In-(aq)]:
[H+(aq)] [In-(aq)] / 10[In-(aq)] = 2.00 x 10-4mol/dm3
[H+(aq)] = 2.00 x 10-3mol/dm3
Thus, pH at which red colour first dominates is 2.70.
Similarly, pH at which yellow colour first dominates is 4.70.
Therefore, ‘pH range’ of methyl orange is: 2.70 to 4.70
The exact pH range for methyl orange is 3.10 to 4.40. This means: at pH values below 3.10,
methyl orange is red. At pH values above 4.40, methyl orange is yellow.
Between 3.10 and 4.40, methyl orange is orange.
Table below shows pKIn values, pH ranges and colour of several common indicators
Indicator pKIn pH Range Colour
HIn(aq) In-(aq)
Methyl Orange 3.70 3.10 – 4.40 red yellow
Bromophenol Blue 4.00 2.80 – 4.60 Yellow Blue
Bromothymol Blue 7.00 6.00 – 7.00 yellow Blue
Phenol Red 7.90 6.80 – 8.40 Yellow Red
Phenolphthalein 9.30 8.20 – 10.00 Colourless Red
Choice of Indicator
A good indicator shows complete colour change on addition of one drop of acid from the
burette. This is necessary in order to accurately determine the end point of the titration.
Therefore, there must be minimum pH change equivalent to pH range of the indicator in
order for the indicator to successfully determine the end point.

Strong Acid – Strong Base Titration

How suitable are methyl orange and phenolphthalein indicators for a strong acid-strong base
titration?
Figure below shows pH titration curve for 25cm3 of 1.00mol/dm3 NaOH(aq) titrated with 1.00
mol/dm3 HCl(aq). pH ranges of methyl orange and phenolphthalein have also been included.

Strong acid-strong base pH curve

Note: pH range of each indicator falls within the steep section of the curve, where a large pH
change occurrs on addition of just one drop of acid. This means both indicators will change
colour at the end point and therefore both are suitable indicators to use in this titration.
Weak Acid – Strong Base Titration
How suitable are methyl orange and phenolphthalein indicators for a weak acid-strong base
titration?
Figure below shows pH titration curve for 25cm3 of 1.00mol/dm3 NaOH(aq) titrated with 1.00
mol/dm3 CH3COOH(aq). pH ranges of methyl orange and phenolphthalein have been included.
 Weak acid-strong base pH curve

Note: only pH range of phenolphthalein falls within the steep section of the curve. So,
phenolphthalein is suitable but methyl orange is not.

Strong Acid – Weak Base Titration

Figure below shows pH titration curve for 25cm3 of 1.00mol/dm3 NH3(aq) titrated with 1.00
mol/dm3 HCl(aq). pH ranges of methyl orange and phenolphthalein have been included.

Strong acid-weak base pH curve

Note: only pH range of methyl orange falls within the steep section of the curve. So, methyl
orange is suitable but phenolphthalein is not.
Weak Acid – Weak Base Titration
Figure below shows pH titration curve for 25cm3 of 1.00mol/dm3 NH3(aq) titrated with 1.00
mol/dm3 CH3COOH(aq). pH ranges of methyl orange and phenolphthalein have been included.

Weak acid-weak base pH curve

Note: there is no prominent steep section to the curve. So, neither indicator is suitable.
In fact, the end point of a titration of a weak acid and a weak base cannot be determined
using an acid-base indicator. The end point of such a titration is best determined by
measuring the temperature changes (thermometric titration) or electrical conductivity
changes (conductometric titration).
Titration Curves With Diprotic Acids
A diprotic acid is an acid that produces two H+ ions per acid molecule, e.g. sulphuric acid,
H2SO4 and carbonic acid, H2CO3.
A diprotic acid dissociates in water in two stages:
1. H2X(aq) ⇌ H+(aq) + HX-(aq)
2. HX-(aq) ⇌ H+(aq) + X2-(aq)
Because of successive dissociations, titration curves of diprotic acids have two equivalence
points, as shown below.

Diprotic acid-strong base pH curve

Equations for acid-base reactions occurring between a diprotic acid, H2X, and a base sodium
hydroxide, NaOH, are as follows:
From the beginning of the reaction to the first equivalence point:
H2X + NaOH → NaHX + H2O
From the first equivalence point to the second equivalence point:
NaHX + NaOH → Na2X + H2O
From the beginning of the reaction through to the second equivalence point (overall):
H2X + 2NaOH → Na2X + 2H2O
At first equivalence point, all H+ ions from the first dissociation have reacted with NaOH.
At the second equivalence point, all H+ ions from both reactions have reacted (twice as many
as at the first equivalence point).
Therefore, the volume of NaOH added at the second equivalence point is exactly twice that at
the first equivalence point.
Choosing The Best Indicator
Bromothymol blue (pKIn = 7.00) is a particularly good indicator for a strong acid-strong base
titration.
Questions
1. The equation for the reaction between hydrochloric acid and ammonia is: HCl(aq) + NH3(aq) → NH4Cl(aq)
A 25cm3 sample of 0.0200 mol/dm3 HCl(aq) was placed in a conical flask. Aqueous ammonia was added gradually
from a burette and the pH was measured after each addition, until the pH no longer changed. The pH curve for this
titration is shown below:
 (a) state how the curve suggests that ammonia is weak base.
(b) use information given to calculate the concentration of ammonia solution.
pH ranges for the 3 indicators are: Thymol blue - 1.2 to 2.8; Methyl red - 4.2 to 6.3; Thymolphthalein - 9.3 to 10.5
Explain which of these three indicators is the most suitable for this titration
2. (a) Calculate the pH at 298K of an aqueous solution of CH3COOH of concentration 0.100 mol/dm3.
[Ka = 1.74 x 10-5 mol/dm3 at 298K]
(b) Sketch the pH titration curve for the addition of 50.0cm3 of 0.100mol/dm3 NaOH(aq) to 25.0cm3 of 0.100
mol/dm3 CH3COOH(aq).
(c) State two difference in the pH curve that would be obtained if the titration were repeated using 25.0cm3 of
0.0500mol/dm3 CH3COOH(aq) instead of 25.0cm3 of 0.100 mol/dm3 CH3COOH(aq).

2. BUFFER SOLUTIONS
What is a Buffer Solution?
Many expts especially in biochemistry, are done in aqueous solutions of fairly constant pH. It
is impossible to make a solution whose pH is unaffected by addition of even small amounts of
acid or base. But it is possible to make a solution whose pH remains almost unchanged when
small amounts of acid or base are added. Such a solution is called a buffer solution.
Two most common ways of making a buffer solution include:
1. To mix a weak acid with its conjugate base
2. To mix a weak base with its conjugate acid.
Buffer Made from A Weak Acid and Its Conjugate Base
Common example: ethanoic acid and sodium ethanoate. Salt of weak acid must be soluble in
water, this is why sodium & potassium salts are commonly used to make buffer solutions.
In this mixture the acid is partially dissociated, whereas the salt is fully dissociated as shown:
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
CH3COONa(aq) → CH3COO-(aq) + Na+(aq)
This mixture produces a buffer solution with pH < 7. Exact pH depends on concentration of
both acid and its conjugate base, and can be calculated as follows:
Calculating pH of a Buffer Solution
If we use a buffer solution made by mixing equal volumes of 1.00 mol/dm3 ethanoic acid and
1.00 mol/dm3 sodium ethanoate at 298K, assuming that dissociation of acid is negligible, then
concentration of CH3COOH at equilibrium = 0.500mol/dm3. Note: since dissociation of acid
is negligible, concentration of ethanoate ions at equilibrium is, thus, entirely from sodiumsalt.
Therefore, concentration of ethanoate ions at equilibrium is also 0.500mol/dm3.
Note: concentration of both acid and salt in the mixture is half of concentrations used because equal
volumes of each solution were mixed, making total volume of mixture twice that of the original
volume of each solution used.
At 298K:
Ka = [CH3COO-(aq)][H+(aq)] / [CH3COOH(aq)] = 1.74 x 10-5 mol/dm3.
Rearranging this equation and substituting values for [CH3COOH(aq)] and [CH3COO-(aq)]
gives:
[H+(aq)] = (1.74 x 10-5 x 0.500) / 0.500 mol/dm3
 = 1.74 x 10-5 mol/dm3
This gives a pH for the buffer solution of 4.76
How Buffer Action Works
Using ethanoic acid and sodium ethanoate example: when a small amount of acid is added to
this buffer solution, most H+(aq) ions added react with CH3COO- ions to form CH3COOH
molecules:
CH3COO-(aq) + H+(aq) → CH3COOH(aq)
when little base is added to this buffer soln, most OH-(aq) ions added react with CH3COOH (aq)
molecules:
CH3COOH(aq) + OH-(aq) → CH3COO-(aq) + H2O(l)
A new equilibrium mixture is established in which concentrations of both CH3COOH(aq) and
CH3COO-(aq) will have changed slightly from their original values. Thus, there will be change
in pH, but this will be minimal.
To show that pH has changed very little, we use the expression for Ka of the acid:
Ka = [CH3COO-(aq)][H+(aq)] / [CH3COOH(aq)]
Rearranging this equation gives:
[H+(aq)] = Ka x [CH3COOH(aq)] / [CH3COO-(aq)]
Note: there is a relatively large number of CH3COOH molecules in the solution, because
dissociation of the acid is very small, thus change in [CH3COOH(aq)] will be negligible.
Change in [CH3COO-(aq)] will also be negligible because there is a relatively large number of
CH3COO- ions present, resulting from total dissociation of CH3COONa.
This means that, ratio [CH3COOH(aq)] / [CH3COO-(aq)] will remain fairly constant.
If this ratio remains fairly constant, then [H+(aq)] also remains fairly constant because, at a
given temperature, Ka, is constant.
If [H+(aq)] remains fairly constant, then the pH remains fairly constant.
To summarise, a buffer solution of a weak acid and its conjugate base maintains a fairly
constant pH because the ratio of [CH3COOH(aq)] to [CH3COO-(aq)] remains fairly constant
when small amounts of either acid or base are added.
To demonstrate effect of adding a small amount of acid on pH of a buffer solution, calculate
pH of buffer both before and after adding acid.
Earlier, under calculating pH of a buffer solution, pH of a buffer solution made by mixing
equal volumes of 1.00 mol/dm3 ethanoic acid and 1.00 mol/dm3 sodium ethanoate at 298K
was calculated as 4.76.
Assuming we mixed 500cm3 of each solution to make 1dm3 of buffer solution, amounts of
CH3COOH and CH3COO- in this solution will both be equal to 0.500mol.
If we take 1dm3 of this solution and we add 1.00 x 10-2 (0.0100) mol of acid to it, assuming
that volume of the solution does not change:
0.0100 mol of HCl will provide 0.0100 mol of H+ ions. These will react with the CH3COO-
ions in the buffer in a 1:1 molar ratio:
CH3COO-(aq) + H+(aq) → CH3COOH(aq)
Amount of CH3COOH present will now have increased from 0.500 to 0.510 mol.
Amount of CH3COO- present will now have decreased from 0.500 to 0.490 mol.
Thus, new concentrations of acid and base present are:
[CH3COOH(aq)] = 0.510mol/dm3
[CH3COO-(aq)] = 0.490mol/dm3
New hydrogen ion concentration is given by:
[H+(aq)] = Ka x [CH3COOH(aq)] / [CH3COO-(aq)]
 = 1.74 x 10-5 mol/dm3 x 0.510 mol/dm3/ 0.490 mol/dm3
= 1.81 x 10-5 mol/dm3.
New pH = -log[1.81 x 10-5] = 4.74 (to 3 sgf)
pH has changed by 0.02 units from 4.76 to 4.74.
To understand the magnitude of how effective the buffer solution is, in controlling pH,
consider adding 0.0100mol of H+ ions to 1dm3 of deionised water.
pH at 298K of deionised water is 7.00, so:
[H+(aq)] = (1.00 x 10-7 mol + 0.0100 mol) = 1.00001 x 10-2 mol/dm3
New pH: pH = -log(1.00001 x 10-2) = 2.00
pH has dropped by 5 units compared to 0.02 units with the buffer solution. A very big
difference! This is how effective a buffer solution is in controlling pH.

Henderson-Hasselbalch Equation
The Henderson-Hasselbalch equation can also be used to calculate pH of a buffer solution
For a weak acid, HA, and its conjugate base, A-, the following equation applies:
[H+(aq)] = Ka x [HA(aq)] / [A-(aq)]
Note: concentrations in the equation are concentrations at equilibrium. However, it is
reasonable to take the original concentrations, for reasons earlier discussed.
Original concentration of A- = [salt], provided that a sodium or potassium salt has been used.
The equation can now be rewritten as
[H+(aq)] = Ka x [acid(aq)] / [salt(aq)]
Taking the logarithm to base ten of both sides of this equation, we get:
log[H+(aq)] = logKa + log[acid(aq)] / [salt(aq)] or
- log[H+(aq)] = - logKa - log[acid(aq)] / [salt(aq)] or
pH = pKa - log[acid(aq)] / [salt(aq)] or
pH = pKa + log[salt(aq)] / [acid(aq)]
The last equation is the most common form of the Henderson-Hasselbalch equation.
If we use Henderson-Hasselbalch equation to calculate pH of our solution containing
ethanoic and ethanoate ions, both of concentration 0.500mol/dm3, we obtain:
pH = pKa + log[salt(aq)] / [acid(aq)]
= 4.76 + log(0.500/0.500) = 4.76
pKa = - log Ka = - log(1.74 x 10-5) = 4.76
This is the same answer as we obtained earlier.
Buffer Made from A Weak Base and Its Conjugate Acid
Most common example: ammonia and ammonium ion. Ammonium ion is usually supplied as
ammonium chloride. This mixture provides a buffer solution with pH greater than 7.
Equilibrium equation is:
NH4+(aq) ⇌ NH3(aq) + H+(aq)
This mixture provides relatively high concentrations of both NH3 molecules and NH4+ ions.
The buffer works in a similar manner to weak acid-conjugate base system. Addition of acid
results in added H+ ions reacting with ammonia, NH3, molecules as follows:
NH3(aq) + H+(aq) → NH4+ (aq)
Addition of base results in added OH- ions reacting with ammonium, NH4+, ions as follows:
NH4+(aq) + OH-(aq) → NH3(aq) + H2O(l)
Because there is relatively high concentration of both NH3 molecules and NH4+ ions, the ratio
of [NH3(aq)] to [NH4+(aq)] remains relatively constant when we add small amounts of either
acid or base. This results in pH remaining fairly constant because it is given by the equation:
 pH = pKa + log([NH3(aq)]/[NH4+(aq)]
pKa is constant at a given temperature, so, pH of the solution depends on the ratio [NH3(aq)] to
[NH4+(aq)].
How To Make a Buffer Solution With A Required pH
1. To make a buffer solution with a pH less than 7, use a mixture of a weak acid with its
conjugate base.
2. To make a buffer solution with a pH greater than 7, use a mixture of a weak base with its
conjugate acid.

Worked Example 1
Make a buffer solution of pH 5.00 at a temperature of 298K. Thus, we apply no. 1 above.
To make this solution we need hydrogen ion concentration, [H+(aq)], of 1.00 x 10-5 mol/dm3.
The hydrogen ion concentration of a buffer solution of a weak acid and its conjugate base is
calculated using the formula: [H+(aq)] = Ka x [acid(aq)] / [salt(aq)]
If we use ethanoic acid for our weak acid, we know: Ka = 1.74 x 10-5mol/dm3(for ethanoic acid)
We now substitute our own values into the equation:
1.00 x 10-5 = 1.74 x 10-5([acid]/[salt])
This gives the value for ([acid]/[salt]) of (1.00 x 10-5/ 1.74 x 10-5) = 0.575 (to 3 sig fig)
So, if we were supplied with an ethanoic acid solution of concentration 0.575 mol/dm3 and a
sodium ethanoate solution of 1.00mol/dm3, we could make a buffer solution of pH 5.00 by
mixing equal volumes of the two solutions. This would give us a solution in which the acid
concentration is 0.2875mol/dm3 and salt concentration is 0.500mol/dm3.
(0.2875/0.500) = 0.575.
Worked Example 2
In what proportions should we mix 0.100mol/dm3 solutions of ammonia and ammonium
chloride to obtain a buffer of pH 9.80? Here, we apply no. 2 above
Equation for dissociation of ammonium ion, NH4+, in aqueous solution is:
NH4+(aq) ⇌ NH3(aq) + H+(aq)
Ka = [NH3(aq)][H+(aq)]/[ NH4+(aq)] = 5.62 x 10-10mol/dm3
[NH3(aq)] /[ NH4+(aq)] = 5.62 x 10-10mol/dm3/[H+(aq)]
[H+(aq)] = 10-pH = 10-9.80 = 1.58 x 10-10 mol/dm3
[NH3(aq)] /[ NH4+(aq)] = 5.62 x 10-10mol/dm3/1.58 x 10-10 mol/dm3
[NH3(aq)] /[ NH4+(aq)] = 3.56
Therefore, we’ve to mix solutions by volume in the ratio of 3.56[NH3(aq)] to 1[ NH4Cl(aq)].
Controlling pH of Blood
The human body works within a narrow range of pH values, e.g. pH of arterial blood plasma
is in the range of 7.35 to 7.45. If pH of blood plasma were to change significantly, the way
the whole body functions would be affected particularly if it were to fall.
pH of blood in cells is controlled by a mixture of buffers. The most important one is the
carbonic acid-hydrogen carbonate buffer mixture.
In this mixture, carbonic acid molecule, H2CO3, is the weak acid, hydrogen carbonate ion,
HCO3-, is the conjugate base of H2CO3.
The equilibrium equation for this buffer is:
H2CO3(aq) ⇌ HCO3-(aq) + H+(aq)
Under normal circumstances, amount of HCO3- ions present in blood is about 20 times that of
H2CO3. Because normal metabolism produces more acids than bases, this is consistent with
the needs of the body.
Any increase in concentration of hydrogen ions in blood (for instance, by production of lactic
acid in muscles), results in the equilibrium shown above moving to the left because added H+
ions react with HCO3- ions producing more H2CO3 molecules.
Various respiratory and metabolic factors can also cause blood pH to rise, e.g. overuse of
diuretics increases amount of urine excreted from the body. If urine contains large amounts of
acids, then pH of blood will increase. If this happens, equilibrium will shift to the right as
H2CO3 molecules ionise to increase H+ ion concentration and restore pH to its original level.
This is the most important buffer because it is coupled with the respiratory system of the
body. Carbonic acid is not particularly stable, and in aqueous solution it decomposes to form
carbon dioxide and water:
H2CO3(aq) ⇌ CO2(aq) + H2O(aq)
The respiratory system removes carbon dioxide from the body. Aqueous carbon dioxide
exists in equilibrium with gaseous carbon dioxide:
CO2(aq) ⇌ CO2(g)
Combining these three reactions gives us:
CO2(g) + H2O(aq) ⇌ CO2(aq) + H2O(aq) ⇌ H2CO3(aq) ⇌ HCO3-(aq) + H+(aq)
When these equilibria shift to the left as a result of increase in hydrogen ion concentration,
concentration of carbon dioxide in blood increases. Carbon dioxide leaves the blood in the
lungs and is exhaled, thus maintaining normal pH of blood.
Buffers in Foods
A combination of various factors such as light, oxygen, heat, humidity and/or many kinds of
microorganisms (bacteria and fungi) spoil food. Spoilage is reduced by keeping certain foods
in the dark, in airtight containers and/or in refrigerators.
Spoilage of food by microorganisms depends greatly on its pH. Most microorganisms thrive
in pH which is close to neutral (6.6 – 7.5). Metabolism of these microorganisms is then
greatest and they multiply quickly. Most bacteria can survive at pH values as low as 4.4 and
as high as 9.0. Only specialised bacteria can survive outside this range.
An important factor in food spoilage is its buffer capacity. Buffer capacity is a measure of
the amount of acid or base required to change significantly the pH of the food.
The more protein there is in food, the higher is its buffer capacity. This is because amino
acids have both acidic and basic properties. Thus, it takes longer for pH of the food to change
enough for bacteria to start multiplying. Bacteria and moulds can also produce waste products
that act as poisons and toxins, causing ill-effects.
Questions
1. (a) explain what is meant by the term ‘buffer solution’.
(b) explain how an aqueous solution containing a mixture of methanoic acid, HCOOH, and potassium methanoate,
HCOOK, acts as a buffer.
(c) a buffer solution contains equal concentrations of metanoic acid and potassium methanoate. Explain the effect
on the pH of this solution of adding some solid potassium methanoate.
(d) calculate the pH, at 298K, of a buffer solution made by mixing equal volumes of 1.00 mol/dm3 methanoic acid
and 0.500 mol/dm3 potassium methanoate.
[Ka(HCOOH) = 1.79 x 10-4mol/dm3]
2. A student prepares two solutions:
Solution A is prepared by mixing 50cm3 of 0.100mol/dm3 CH3COOH(aq) with 25cm3 of 0.100mol/dm3 NaOH(aq).
Solution B is prepared by mixing 25cm3 of 0.200mol/dm3 CH3COOH(aq) with 50cm3 of 0.100mol/dm3 NaOH(aq).
Explain why solution A is a buffer solution but solution B is not.
3. A buffer solution was made by mixing 50cm3 of 0.200mol/dm3 aqueous ammonia, NH3(aq), with 50cm3 of aqueous
ammonium chloride, NH4Cl(aq). The pH of the resulting solution was 9.55. calculate the concentration of the
NH4Cl(aq) used.
[Ka(NH4+) = 5.62 x 10-10mol/dm3
4. Calculate the pH of a buffer solution containing 12.20g of benzoic acid (C6H5COOH) and 7.20g of sodium
benzoate (C6H5COONa) in 1.00dm3 of solution.
[pKa(C6H5COOH) = 4.20]
5. Like water, liquid ammonia undergoes self-dissociation:
 2NH3 ⇌ NH4+ + H+
(a) explain why ammonia can be classified as an amphoteric substance.
(b) For each of the following substances, indicate whether a solution of it in liquid ammonia will be ‘acidic’, basic’
or ‘neutral’.
(i) ammonium chloride, NH4Cl
(ii) sodium amide, NaNH2
(iii) potassium hydroxide, KOH

3. BUFFER SOLUTIONS and pH CURVES

Buffer Action During Titration
Figure below shows a typical pH curve obtained when a weak acid is titrated against a strong
base.

Strong base- weak acid pH curve showing buffer range

In the region marked ‘buffer range’, change in pH as base is added is gradual. Over this range
there is a considerable concentration of both acid and conjugate base molecules. This mixture
is displaying buffer action.
Determining Ka from a pH Titration Curve
To determining Ka from a pH Titration Curve, an experiment involving a titration of an
aqueous solution of a weak acid in a conical flask is performed. From a burette, add a
standard solution of a strong base, e.g. sodium hydroxide. Measure pH of the solution after
each addition. Then plot a graph of pH against volume of base added. From the graph
determine the minimum volume of base required to completely react with all of the acid.
Then use the graph to determine pH at the half-equivalence point. This pH value is equal to
the pKa value of the weak acid. From pKa value, calculate Ka for the acid.
A typical pH titration curve is shown in fig B.
Volume at the equivalence point is 25cm3, thus volume at half-equivalence point is 12.5cm3.
pH when 12.5cm3 of base is added is 4.80.
Ka for the acid = 10-4.80 = 1.58 x 10-5 mol/dm3.
 Strong base-weak acid pH curve showing equivalence and half-equivalence points

Supporting Theory
Theoretical justification for determining Ka for a weak acid by the method shown above:
The mixture at half-equivalence point is a buffer solution (as stated above). pH of a buffer
solution is calculated using the equation:
pH = pKa + log([salt]/[acid])
At half-equivalence point:
[salt] = [acid], so [salt]/[acid] = 1
The logarithm to the base 10 of 1 (log 1) = 0.
So, the equation becomes:
pH = pKa
Alternative Method
This method has been called the ‘half-volume method’.
- Using a volumetric pipette, place 25.0cm3 of an aqueous solution of the weak acid into a
conical flask
- Add a few drops of phenolphthalein indicator
- Titrate against a solution of aqueous sodium hydroxide until the end point colour is
obtained
- Note the volume of sodium hydroxide solution required. This is the minimum volume
required to completely react with the acid
- Use a fresh 25.0cm3 sample of the same aqueous solution of the weak acid and the same
aqueous solution of sodium hydroxide, but this time do not add the phenolphthalein
- Add only half the volume of sodium hydroxide required to react with the acid
- Measure pH of this solution. This pH value is equal to the pKa value of the acid.
Checkpoint
1. A student carried out a titration by adding hydrochloric acid to ammonia solution. A sketch graph of pH against
volume of hydrochloric acid added is shown below:
 (a) name the type of solution formed in the region ringed on the sketch graph.
(b) explain how you deduced your answer to part (a).

2. The diagram shows the titration curve for a weak acid. Use the curve to determine the pKa value for the acid.
Explain how you arrived at your answer.