REDOX TITRATION

Redox TITRATION
A redox titration is a type of titration based on a redox
reaction between the analyte and titrant. It may involve
the use of a redox indicator and/or a potentiometer.
The main redox titration types are:

Redox titration Titrant

Iodometry, Iodimatry, Iodatmetry Iodine (I2)
Bromatometry Bromine (Br2)
Cerimetry Cerium(IV) salts
Permanganometry Potassium permanganate (K2MnO4)
Dichrometry Potassium dichromate
Match up 2 pairs of REDUCING and OXIDISING
agents. Then write a balanced equation with state
symbols for at least one of the reactions.

F2 Cl2 Br2 l2

Br - I-
F- Cl-
A
B
Endpoint vs Equivalence Point

Endpoint Equivalence Point

The point at which the titrant is

Point where the indicator changes
chemically equivalent to the
colour
analyte in the sample

Comes after the equivalence point Comes before the endpoint

Weak acids can have only one Weak acids can have multiple
endpoint equivalence point
Sample Calculation from Experimental Data
A standardized 4 M solution of KMnO4 is titrated against a 100
mL sample of an unknown analyte containing Fe2+. A student
conducts the redox titration and reaches the endpoint after adding
25 mL of the titrant. What is the concentration of the analyte?
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12B
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 REDOX Titrations 1
C
REDOX titration of IODINE using starch as the
endpoint indicator
 Put these 12 stages and equations in order
1 for a redox titration to measure the purity of C
iodine in a sample
When all of the iodine has reacted with thiosulphate the colour changes
from black to clear. This is the endpoint of the titration

Record the volume of thiosulphate that has reacted

Add the starch indicator to the solution (do not add too early otherwise
the starch breaks down)

Iodine combines with starch to form a black complex (not a chemical

reaction)

Calculate mass of iodine using

Mass = Mr x moles

Record the mass of iodine sample

 Put these 12 stages and equations in order for a
redox titration to measure the purity of iodine in a C
sample
Divide mass of iodine calculated from the titration by the original mass
the x100% to calculate percentage purity

Calculate moles of iodine that reacted using the stoichiometry of the

reaction between thiosulphate and iodine

2S2O32-(aq) + I2(aq)  S4O62-(aq) + 2I-(aq)

Calculate moles of thiosulphate that has reacted using

Moles = concentration (M) x volume (dm 3)

React iodine with thiosulphate to produce iodide and tetrathionate

 Put these stages and equations in order for a
redox titration to measure the purity of iodine in a C
sample
Mark scheme

Record the mass of iodine sample

React iodine with thiosulphate to produce iodide and tetrathionate

Add the starch indicator to the solution (do not add too early otherwise
the starch breaks down)

Iodine combines with starch to form a black complex (not a chemical

reaction)

When all of the iodine has reacted with thiosulphate the colour changes
from black to clear. This is the endpoint of the titration

Record the volume of thiosulphate that has reacted

Put these stages and equations in order for a
redox titration to measure the purity of iodine C
in a sample
Mark scheme
Calculate moles of thiosulphate that has reacted using
Moles = concentration (M) x volume (dm 3)

Calculate moles of iodine that reacted using the stoichiometry of the

reaction between thiosulphate and iodine

Calculate mass of iodine using

Mass = Mr x moles

Divide mass of iodine calculated from the titration by the original mass
the x100% to calculate percentage purity

2S2O32-(aq) + I2(aq)  S4O62-(aq) + 2I-(aq)

 Extension

Explain how chlorine gas could be included in this

method to identify the amount of iodide ions in the
sample. What extra reaction would there be?

Include a symbol equation with state symbols in

your answer.
 Unit 2 – Group 2/7 elements
Redox titrations
B4 Mid End
C Can I describe the stages of a REDOX titration
to calculate percentage titration?

Can I calculate REDOX titrations?

B
A Can I combine redox half equations?
 TESTING FOR HALIDES – AgNO3

CHLORIDE BROMIDE IODIDE

ADD SILVER NITRATE SOLUTION

WHITE PRECIPITATE OF SILVER CHLORIDE AgCl

CREAM PRECIPITATE OF SILVER BROMIDE AgBr
YELLOW PRECIPITATE OF SILVER IODIDE AgI
 TESTING FOR HALIDES – AgNO3

CHLORIDE BROMIDE IODIDE

ADD DILUTE AMMONIA SOLUTION

WHITE PRECIPITATE OF SILVER CHLORIDE - SOLUBLE

CREAM PRECIPITATE OF SILVER BROMIDE - INSOLUBLE
YELLOW PRECIPITATE OF SILVER IODIDE - INSOLUBLE
 REDOX Titrations 2
B
REDOX titration of HALIDE IONS is a multi step process

1. React halide ions (e.g. Cl-) with silver (Ag+) ions to get a faint
coloured precipitate.
Ag+(aq) + Cl- (aq)  AgCl(s)

2. To find out when ALL of the Ag+ and Cl- has reacted an extra
stage is added

3. The excess Ag+ is reacts with chromate (Cr2O72-) to form a brick

red precipitate. This shows that all of the Ag+ and Cl- has reacted

2Ag+(aq) + Cr2O72-(aq)  Ag2Cr2O7(s)

 REDOX Titration calculation 1 B
25 cm3 of seawater was diluted to 250 cm3 in a graduated volumetric
flask. A 25 cm3 aliquot of the diluted seawater was pipetted into a
conical flask and a few drops of potassium chromate(VI) indicator
solution was added.
 On titration with 0.1 mol dm-3 silver nitrate solution, 13.8 cm3 was
required to precipitate all the chloride ion. [Atomic masses: Na = 23, Cl =
35.5]
(a) Give the ionic equation for the reaction of silver nitrate and chloride
ion.
(b) Calculate the moles of chloride ion in the titrated 25cm3 aliquot.
(c) Calculate the molarity of chloride ion in the diluted seawater.
(d) Calculate the molarity of chloride ion in the original seawater.
(e) Assuming that for every chloride ion there is a sodium ion, what is
the theoretical concentration of sodium chloride salt in g dm-3 in
seawater?
REDOX Titration calculation 1 Mark scheme B
(a) Ag+(aq) + Cl-(aq) ==> AgCl(s) (sodium ions and nitrate ions etc. are
spectator ions)
(b) from equation: moles silver nitrate (AgNO3) = moles chloride ion (Cl-)
moles = molarity AgNO3 x volume of AgNO3 in dm3
= 0.100 x 13.8/1000 = 1.38 x 10-3 mol Cl- (in 25.0 cm3 aliquot)
(c) moles in 1 dm3 of diluted seawater = 1.38 x 10-3 x 1000/25 = 0.0552
(scaling up to 1000 cm3)
So molarity of chloride in diluted seawater is 0.0552 mol dm-3
(d) Now in the titration 25.0 cm3 of the 250 cm3 was used,
so the molarity of chloride ion in the original seawater must be scaled
up accordingly.
molarity of chloride ion in seawater = 0.0552 x 250/25.0 = 0.552 mol
dm-3
(e) Mr(NaCl) = 23 + 35.5 = 58.5
concentration of NaCl in g dm-3 = molarity x formula mass = 0.552 x 58.5
-3
 REDOX Titration calculation 2 B
0.12 g of rock salt was dissolved in water and titrated with 0.1 mol dm-3
silver nitrate until the first permanent brown precipitate of silver
chromate was seen.
19.7 cm3 was required to titrate all the chloride ion. [Atomic masses: Na
= 23, Cl = 35.5]
(a) How many moles of chloride ion was titrated?
(b) What mass of sodium chloride was titrated?
(b) What was the % purity of the rock salt in terms of sodium chloride?
 
REDOX Titration calculation 2 Mark scheme B

Q11 ANSWERS (a) moles = molarity AgNO3 x volume in dm3 = 0.100 x

19.7/1000 = 1.97 x 10-3 mol Cl- ion
[AgNO3:NaCl or Ag+:Cl- is 1:1, see Q10(a)/(b)] f. mass NaCl = 23 + 35.5 =
58.5
(b) mass = mol x formula mass = 1.97 x 10-3 x 58.5 = 0.1152 g NaCl
(c) % purity = 0.1152 x 100/0.12 = 96.0 % in terms of NaCl (3sf)
 
 REDOX Titration calculation 3 B
5.0 g of a solid mixture of anhydrous calcium chloride(CaCl2) and sodium
nitrate (NaNO3) was dissolved in 250 cm3 of deionised water in a
graduated volumetric flask. A 25 cm3 aliquot of the solution was
pipetted into a conical flask and a few drops of potassium chromate(VI)
indicator solution was added.
On titration with 0.1 mol dm-3 silver nitrate solution, 21.2 cm3 was
required to precipitate all the chloride ion. [Atomic masses: Ca = 40, Cl =
35.5]
(a) Calculate the moles of chloride ion titrated.
(b) Calculate the equivalent moles of calcium chloride titrated.
(c) Calculate the equivalent mass of calcium chloride titrated.
(d) Calculate the total mass of calcium chloride in the original 5.0 g of
the mixture.
(e) The % of calcium chloride and sodium nitrate in the original mixture
REDOX Titration calculation 3 Mark scheme B

Q12 ANSWERS (a) mole Cl- = moles Ag+ [=AgNO3, see Q10(a)/(b)]
mole Cl- = molarity AgNO3 x vol AgNO3 = 0.100 x 21.2/1000 = 2.12 x 10-3
mol Cl-
(b) Since calcium chloride is CaCl2, mol CaCl2 = mole Cl-/2  = 2.12 x 10-3/2
= 1.06 x 10-3 mol CaCl2
(c) Mr(CaCl2) = 40 + (2 x 35.5) = 111
mass = mol x f. mass = 1.06 x 10-3 x 111 = 0.1177 g CaCl2
(d) Since 1/10th of original solution titrated, original mass of CaCl2 in
mixture = 10 x 0.1177 g = 1.177g CaCl2 (1.78g 3sf)
(e) Therefore % = 1.177 x 100/5.0 =  23.5% CaCl2(3 sf)
and % NaNO3 = 100 - 23.5  = 76.5% (3 sf)
Extension – what is the purity of Magnesium Oxide? B
4.06 g of impure magnesium oxide was completely dissolved in 100 cm3
of hydrochloric acid, of concentration 2.00 mol dm-3 (in excess).

The excess acid required 19.7 cm3 of sodium hydroxide (0.200 mol dm-3)
for neutralisation.

(a) write equations for the two neutralisation reactions.

(b) calculate the moles of hydrochloric acid added to the magnesium
oxide.
(c) calculate the moles of excess hydrochloric acid titrated.
(d) calculate the moles of hydrochloric acid reacting with the
magnesium oxide.
(e) calculate the moles and mass of magnesium oxide that reacted with
the initial hydrochloric acid.
(f) hence the % purity of the magnesium oxide
(a)(i) MgO(s) + 2HCl(aq) ==> MgCl2(aq) + H2O(l)
Mark scheme B
(a)(ii) NaOH(aq) + HCl(aq) ==> NaCl(aq) + H2O(l)

(b) moles of hydrochloric acid added to the magnesium oxide = 2 x

100/1000 = 0.20 mol HCl

(c) moles of excess hydrochloric acid titrated = 19.7 ÷ 1000 x 0.200 =

0.00394 mol HCl

(d) moles of hydrochloric acid reacting with the magnesium oxide = 0.20
- 0.00394 = 0.196 mol HCl

(e) mole MgO reacted = 0.196 ÷ 2 = 0.098 {1: 2 in equation (i)}

the formula mass of MgO = 40.3
therefore mass of MgO reacting with acid = 0.098 x 40.3 = 3.95 g

(f) % purity = 3.95 ÷ 4.06 x 100 = 97.3% MgO

 Unit 2 – Group 2/7 elements
Redox titrations
B4 Mid End
C Can I describe the stages of a REDOX titration
to calculate percentage titration?

Can I calculate REDOX titrations?

B
A Can I combine redox half equations?
Balancing metal redox equations
Ag + Sn  Ag + Sn
+ 2+ A
1. Write half equations for each metal

Ag+ + e-  Ag Sn – 2e- Sn2+

2. Multiply each half equation so that they both have the
same number of electrons

2Ag+ + 2e-  2Ag Sn – 2e- Sn2+

3. Combine the half equations by adding so that the
electrons cancel out
2Ag+ + 2e-  2Ag
+
Sn – 2e-  Sn2+
2Ag+ + Sn  2Ag + Sn2+
Balancing metal redox equations
A
Balance and combine these halide redox equations. Show
clearly all your working.

 H2SO4 + H+ + e-  SO2 + H2O

 Br - - e-  Br2

 H2SO4 + H+ + e-  H2S + H2O

 I- - e-  I2
Balancing metal redox equations
A
Balance and combine these halide redox equations. Show
clearly all your working.

 H2SO4 + 2HBr  Br2 + SO2 + 2H2O

 H2SO4 + 8HI  4I2 + H2S + 4H2O

Balancing metal redox equations
A
Mark scheme
The bromide ions are strong enough reducing agents to
reduce the concentrated sulphuric acid. In the process the
bromide ions are oxidised to bromine.

The bromide ions reduce the sulphuric acid to sulphur

dioxide gas. This is a decrease of oxidation state of the
sulphur from +6 in the sulphuric acid to +4 in the sulphur
dioxide.

You can combine these two half-equations to give the overall

ionic equation for the reaction:
Balancing metal redox equations
A
Mark scheme
Iodide ions are stronger reducing agents than bromide ions are.
They are oxidised to iodine by the concentrated sulphuric acid.

The reduction of the sulphuric acid is more complicated than

before. The iodide ions are powerful enough reducing agents to
reduce it
first to sulphur dioxide (sulphur oxidation state = +4)
then to sulphur itself (oxidation state = 0)
and all the way to hydrogen sulphide (sulphur oxidation state =
-2).
The most important of this mixture of reduction products is
probably the hydrogen sulphide.
 Unit 2 – Group 2/7 elements
Redox titrations
B4 Mid End
C Can I describe the stages of a REDOX titration
to calculate percentage titration?

Can I calculate REDOX titrations?

B
A Can I combine redox half equations?