A sample of sodium hydrogen carbonate was tested for purity

using the following method. A 0.400g of the solid sample was

dissolved in 100.0 mL of water and titrated with 0.200 M
hydrochloric acid using methyl orange indicator. The volume of
acid required for complete neutralization was 23.75 mL.

i)Write the equation for the titration reaction.

ii) Sketch and label the titration curve for the titration above.
Iii) Determine the purity of sodium hydrogen carbonate in the
sample.
• NaHCO3(s) + HCl(aq) ==> NaCl(aq) + H2O(l) + CO2(g)
mol = molarity x volume in dm3, mol acid = 0.200 x 23.75/1000
= 4.75 x 10-3 mol HCl
from equation HCl:NaHCO3 is 1:1 by ratio
so mol HCl = mol NaHCO3 = 4.75 x 10-3
mass NaHCO3 = 4.75 x 10-3 mol x 84 g/mol = 0.399 g
% purity of NaHCO3 = 0.399 x 100/0.40
• = 99.75%
Magnesium oxide is not very soluble in water, and is difficult to
titrate directly. Its purity can be determined by use of a 'back
titration' method. A 4.06 g of impure magnesium oxide was
completely dissolved in 100.00 cm3 hydrochloric acid, of
concentration 2.00 mol dm-3. The excess acid required 19.70
cm3 sodium hydroxide (0.20 mol dm-3) for neutralisation.

i) Name the analyte and titrant for the above titration.

ii) Write equations for the two neutralisation reactions.
iii) Calculate the % purity of magnesium oxide.
= 97.29% (w/w)

Initial amount of acid:

mole of acid = 2.00 mol/dm3 x (100/1000) dm3
= 0.20 mol
1 mole HCl = 1 mole NaOH (back titration)
So, remaining/excess acid during back titration:
mole of excess acid = 0.2 mol/dm3 x (19.7/1000) dm3
= 3.94 x 10-3 mol
Then, mole of acid reacted with MgO
= (0.20 mol – 3.94 x 10-3 mol) , = 0.196 mole HCl

Mole of MgO
2 mole HCl = 1 mole MgO (initial)
0.196 mole = ?
mole of Mg(OH)2 = ½ x mole acid
= ½ x 0.196
= 0.098 mol MgO
Mass of MgO
Gram MgO = mole x molar mass
= 0.098 x (24.31+15.99)
= 3.95 g

% purity of MgO
% MgO = Weight of MgO x 100
Weight of sample
= 3.95 x 100
4.06
Back titration

Back titration is required in some chemical analysis as shown in

chemical equation below. Draw the titration curve for the above
titration.

2HNO3 + CaCO3 Ca(NO3) 3 + CO3 + H2O

HNO3 + NaOH NaNO3 + H2O
Complexometric titration
The Tl in a 11.760 g sample of rodenticide was oxidized to a trivalent state and
treated with an unmeasured excess of Mg(EDTA) solution. The reaction is

Tl3+ + MgY2- → TlY- + Mg2+

The free Mg2+ required 13.34 mL of 0.0256 M EDTA.

i) Calculate the parts per million (ppm) of Tl2SO4 in the sample.

ii) Name a suitable indicator for the EDTA titration.

iii) Name one other application of titration with EDTA solution.

mole EDTA = (13.34/1000) L x 0.03560 mol/L
= 4.7490 x 10-4 mole
= 4.7490 x 10-4 mole Tl

1 mole Tl2SO4 contains 2 mole Tl

Therefore 4.7490 x 10-4 mole Tl equivalent to:
= 4.7490 x 10-4 mole Tl
2
= 2.3745 x 10-4 mol Tl2SO4

Mass of Tl2SO4 = 2.3745 x 10-4 mol x 504.8 g/mol

= 0.1199 g.

Therefore ppm Tl2SO4 (ppm) = 0.1199 x 1000mg

9.76/1000 kg
= 12285 ppm .
• Eriochrome Black T

• To determine hardness of water sample

Write one limitation for each Mohr and Volhard method.

Mohr
The solution must be neutral. The sample should not be too acidic or basic.
2. Acidic (pH < 6)- indicator (CrO42- ) failed to function ….
3. Basic (pH > 10.3), silver (I) begins to coprecipitate as silver (I) oxide.
4. End point detection maybe difficult. Need correct concentration of chromate
indicator.

Volhard
More difficult than Mohr Method because AgCl is more soluble
than AgSCN precipitate in extreme pH conditions.
Therefore, at the end point, the following reaction occurs in the back titration.
AgCl(ppt) + SCN- = AgSCN(ppt) + Cl-
Redox titration

One of the methods to analyse the pollution level in water sample is by COD
analysis.

i) Name the oxidizing agent used in COD determination.

Potassium dichromate

ii) In a COD analysis, a sample solution turned green after the reflux process. Justify
two reasons for this green colour.

-The oxidising agent/potassium dichromate added to the sample prior to reflux is

not sufficient.
-Volume of sample is large
Redox titration

A 0.2500 g of brass sample is analysed in the laboratory for its copper

content. Copper(ll) is reduced to copper(l) by iodide ion. The liberated
iodine, l2 is then titrated with Na2S2O3 solution. As much as 22.45 mL of
0.105 M Na2S2O3 is required for titration of the liberated iodine.
i) Name an indicator suitable for the above titration and state the colour
change at the end point.
ii) Explain why the indicator must be added near the end point.
iii) Estimate the percentage of copper the brass sample.

2Cu2+ + 4I-  2Cul + l2

l2 + 2S2O32-  2I- + S4O62-
i) Starch
Dark blue to colorless

ii) The starch used for end-point detection tends to hydrolyze or

decompose in strong acid, and so the end point may be affected.
Therefore, starch is added before the end point, (after the solution in
pale yellow).
mol of S2O3- = 22.45 x 10-3 L x 0.105 mol/L = 2.358 x 10-3

mol of I2 = ½ mol S2O3- = ½ x 2.358 x 10-3 = 1.179 x 10-3

mol Cu2+ = 2 mol I2= 2 (1.179 x 10-3) = 2.358 x 10-3

mol Cu = mol Cu2+ = 2.358 x 10-3

mass Cu =2.358 x 10-3 x 64= 0.1509

Cu = mass of Cu x 100 = 0.1509 g x 100 = 60.36%

Sample 0.2500 g
Precipitation titration

Describe two ways whereby end point in an argentometric titration can

be detected.

Indicator Reacted With Titrant And Formed Colored Compound.

Indicator Get Adsorbed Onto Surface Of Precipitate Thus Changed
Color At End Point
A 6.740 g of an unknown iron(II) salt was dissolved in a mixture of water and
dilute sulphuric acid and made up to 250 mL. A 25.0 mL of this solution was titrated
against 0.040 M potassium dichromate(VI) solution and 23.60 mL was needed to
reach the end point. The balanced equation for the reaction is:

6Fe2+ + Cr2O72− + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O

i) Name the type of reaction in the titration.

ii) Identify the oxidizing and reducing agent from the reaction.

iii) State a suitable indicator for the above titration. Indicate the colour change using
this indicator.
i) Redox reaction

ii) Fe2+ : Reducing agent

Cr2O72- : Oxidizing agent

iii) Ferroin / (Diphenylamine sulfonate). Pale blue to red/brown /

(green to violet)
6Fe2+ = 1 Cr2O72-
Mole Cr2O72- in 25 mL = 23.6 /1000 x 0.04
= 0.000944 mole
Mole Cr2O72- in 250 mL= 0.000944 X 10
= 0.00944 mole
Mole Fe2+ in 250 mL = 0.00944 x 6
= 0.05664 mole
Mass of Fe2+ = 0.0564 x 56
= 3.172 g.
% Fe = 3.172/6.74 x 100
= 47.1%
The following procedure was done to determine the hardness of
a water sample taken from a stream. A 10 mL buffer was added
to 25.0 mL of the water sample to increase the pH to 10. The
sample was then titrated with 12.60 mL 0.0195 M EDTA to the
end point.

i) Calculate the water hardness in ppm CaCO3.

•
i) Name a suitable indicator for this titration.

i) Justify why the pH of the water should be adjusted to 10.

MAVA / 1 = MBVB / 1 A = Ca B = EDTA

MA = 0.0195 x 12.6 / 25
= 0.00983 M

Concentration of Ca as ppm CaCO3

= 0.00983 x MW CaCO3 x 1000
= 0.00983 x 100 x 1000
= 983 ppm CaCO3
A 5.0 mL sample of a pesticide containing chlorine was diluted to 25.0
mL. Then nitric acid was added to 10.0 mL of this diluted solution to
convert all the chlorine into soluble chloride ion. A 50.0 mL 0.215 M
silver nitrate was added to the sample to precipitate all the chloride.
The excess silver nitrate was then titrated with 15.80 mL 0.227 M
potassium thiocyanate by Volhard’s method.
i) Explain how the end point is observed in this titration.
ii) Write the chemical equation of the titration.
iii) Calculate the concentration of chlorine (%w/v) in the pesticide.
• At the end point a small excess of thiocyanate ion reacts with
the indicator, Fe3+ to from a red coloured complex, [Fe(SCN)]2+

• Ag+(aq) + SCN-(aq)  AgSCN(s)

Initial mol AgNO3 = 0.215 x 50/1000 = 0.01075 mol
Excess mol AgNO3 = mol KSCN = 0.227 x 15.80/1000
= 0.003587 mol
Mol AgNO3 reacted with chloride = 0.01075 – 0.003587
= 0.007163 mol
Mol chloride = Mol AgNO3 = 0.007163
Mass of chloride = 0.007163 x 35.5 x2 = 0.5086 g
Mass of chloride in the whole sample = 0.5086 x 25 mL / 10 mL = 1.2715 g
% Cl = 1.2715 g / 5.0 mL x 100%
= 25.43 %
The chlorine content in a bleaching solution was determined by pipetting 10.0 mL of the
bleaching solution and diluting it 10 times in a 100 mL volumetric flask. A 10 mL sample of the
diluted bleaching solution was transferred into a 250.0 mL conical flask and treated with excess
iodide. The liberated iodine was titrated with the standardized 0.050 M sodium thiosulphate
solution and titration was continued until the blue colour just disappear which required 30.00
mL sodium thiosulphate to reach end point

Cl2 + 2I- = 2Cl- + I2

I2 + 2S2O32- = 2I- + S4O62-

i) Determine the percentage (%w/v) of Cl2 in the bleaching solution.

ii) The above titration is usually performed in neutral or mildly alkaline (pH 8) to weakly acid
solutions. State what happen when the pH is too alkaline.

iii) Explain why is iodine solutions are prepared by dissolving I2 in concentrated KI.
Mol S2O3 = 0.05 x 30 / 1000 = 1.5x10-3 mol
Mol I2 = 1.5x10-3 mol S2O3 x 1 mol I2 = 7.5 x10-4 mol
2 mol S2O3
Mol Cl2 = 7.5 x10-4 mol I2 x 1 mol Cl2 = 7.5 x10-4 mol
1 mol I2
Mass Cl2 = 7.5 x10-4 mol x 71 g / mol = 0.05325 g
Mass Cl2 in original bleach solution = 0.05325 g x 100 mL =0.5325 g
10 mL
(%w/v) = 0.5325 g x100
10 mL
= 5.325%
ii) I2 will disproportionate to hypoiodate and iodide.

iii)
Iodine is not sufficiently soluble in water to produce a useful standard reagent.

It is quite soluble in solutions that contain an excess of iodide, however as a

consequence of the formation of the triiodide complex. the rate at which iodine
dissolves in iodide solutions increases as the concentration of iodide ion
becomes greater.

For this reason iodine is always dissolved in a very concentrated solution of

potassium iodide and diluted only after dissolution is complete.
In a COD determination experiment, mercuric sulphate is added to a 15.0
mL sample of waste water and refluxed with 10.0 mL of 0.0417 M potassium
dichromate. When cooled the mixture is titrated with 0.1020 M Fe(II) solution
which required a volume of 9.75 mL to reach end point.

Given: 3[O2] = 3[C] = 2[Cr2O72-] and 1[Cr2O72-] = 6[Fe2+]

i) What is the purpose of adding mercuric sulphate?

i) Name the oxidising agent used

i) Calculate the COD of the waste water in ppm O2.

• To remove the chloride ions
• Potassium dichromate
Mol of Cr2O72- = (0.0417 mol/L x 0.01 L)
= 4.17 x 10-4 mol
Excess amount of Cr2O72- refer to Fe(II)
Mol of Fe(II) = (0.1020 mol/L x 9.75 X 10-3 L)
= 9.945 X 10-4 mol

Use stoichiometry 1mol [Cr2O72-] = 6 mol [Fe 2+]

Mole of excess Cr2O72- = 1 x 9.945 X 10-4 mol

6
= 1.6575 10-4 mol

Mole of Cr2O72- reacted with waste water

Mole of Cr2O72- reacted = initial – excess
= 4.17 x 10-4 mol -1.6575 x 10-4 mol
= 2.5125 x 10-4 mol
Mole of carbon

Use stoichiometry: 3 mol [C] = 2 mol [Cr2O72-]

Mole of [C] = 3/2 x mole of Cr2O72-
= 3/2 (2.5125 x 10-4)
= 3.7688 x 10-4

Mole of oxygen
Use stoichiometry: 3mol [O2] = 3 mol [C]
Mol of O = 3.7688 x 10-4
Mass of O2 = 3.7688 x 10-4 x 32 g
= 0.01206 g or 12.06 mg
ppmof O2 = 12.06 mg = 804 ppm
0.015 L
Complete the table below (i, ii, iii, iv, v and vi) for the three methods in precipitation titration.
Note: DCF is dichlorofluorescein.

(i) Fajan’s Method (ii)

Titration reaction: - Titration reaction:
Ag+ + Cl- ⇌ AgCl(s) (iii)
Indicator reaction: Indicator reaction: Indicator reaction:
(iv) AgCl. Ag+ + DCF- ⇌ Fe3+ + SCN- ⇌ FeSCN2+
AgCl.Ag+:DCF-
Colour at the end Colour at the end point: Colour at the end point:
point: (v) (vi)
Orange-red
i- Mohr’s method
ii- volhard’s method
iii- Ag+ + SCN-⇌AgSCN(s)
iv- 2Ag+ + CrO42-⇌ Ag2CrO4(s)
v- pink
vi- red