Standardization of Sodium Thiosulphate

(Na2S2O3 . 5H2O) Solution with Standard

Potassium Dichromate (K2Cr2O7) Solution
0

10

20

30

40

50
 Objective
 To know the strength (in normality or
molarity) of a secondary standard sodium
thiosulphate (Na2S2O3) solution
against a primary standard potassium
dichromate (K2Cr2O7) solution by
oxidation-reduction titration.

Septem 18, 2022 Experiment 5 2

 K2Cr2O7 vs Na2S2O3
 Primary standard  Secondary standard
substance substance
 Oxidizing agent  Reducing agent
 Orange solid  White solid
 Mol. wt. 294  Mol. wt. 248
 Gram equiv. wt. 49  Gram equiv. wt. 248

Septem 18, 2022 Experiment 5 3

 Theory
 Methods:
 Oxidation-Reduction (Redox) Titration

Septem 18, 2022 Experiment 5 4

 Concept of Redox Reactions
 Classical Concept
 Modern Concept

Classical Concept Modern Concept

Reactions Oxygen or Hydrogen Electron Oxidation

any non- or any Number or
metal metal Valency
Oxidation addition removal loss increase

Reduction removal addition gain decrease

Septem 18, 2022 Experiment 5 5

 Classical Concept- Oxidation
 (1) Reactions involving addition of
oxygen or of any non-metal element
(except hydrogen), e.g.
 2C + O2  2CO

 4Fe + 3O2  2Fe2O3

 H2 + F 2  2HF

Septem 18, 2022 Experiment 5 6

 Classical Concept- Oxidation
 (2) Reactions involving removal of
hydrogen or of any metal, e.g.
 2H2O  2H2 + O2
 (3) Reactions involving increase of
valency of a metal, e.g.
 2FeCl2 + Cl2  2FeCl3

Septem 18, 2022 Experiment 5 7

 Classical Concept- Reduction
 (1) Reactions involving removal of oxygen
or of any non-metal element (other than
hydrogen), e.g.
 CuO + H2  Cu + H2O
 (2) Reactions involving addition of
hydrogen or of any metal, e.g.
 O2 + 2H2  2H2O

Septem 18, 2022 Experiment 5 8

 Classical Concept- Reduction
 (3) Reactions involving decrease of valency
of a metal, e.g.
 2FeCl3 + H2S  2FeCl2 + HCl + S

Septem 18, 2022 Experiment 5 9

 Modern Concepts
 According to electronic interpretation-

 Oxidation is a process which involves

the loss of one or more electrons,
 Reduction is a process which involves
the gain of one or more electrons.

Septem 18, 2022 Experiment 5 10

 Examples of oxidation-
Na  Na+ + e
H2  2H+ + 2e

Al  Al+3 + 3e
Fe+2  Fe+3 + e
2Cl-  Cl2 + 2e
In the above examples, Na, H2, Al, Fe+2,
Cl- are said to be oxidized. Such
equations in which electrons are lost are
known as oxidation half-reactions.
Septem 18, 2022 Experiment 5 11
 Examples of reduction-
Cl2 + 2e  2Cl-

Fe+3 + e  Fe+2
2H+ + 2e  H2

In the above examples, Cl2, Fe+3, H+ are

said to be reduced. Such equations in
which electrons are gained are known as
reduction half-reactions.

Septem 18, 2022 Experiment 5 12

 Redox Reactions…
For example- formation of sodium chloride from
sodium and chlorine.
2Na(s) + Cl2(g)  2NaCl(s)
Two half-reactions are:
2Na  2Na+ + 2e (oxidation half reaction)
Cl2 + 2e  2Cl- (reduction half reaction)

------------------------------------------------------
2Na + Cl2  2NaCl
Septem 18, 2022 Experiment 5 13
 Oxidizing Agents
 Oxidizing agent - the reactant that gains
electrons.
 The oxidizing agent (e - acceptor) becomes
reduced by gaining electrons and its
oxidation number decreases.
 If a substance gains electrons easily, it is
said to be a strong oxidizing agent.
 Example: K Cr O (medium), I , CuSO ,
2 2 7 2 4
KMnO4 (strong) etc.
Septem 18, 2022 Experiment 5 14
 Reducing Agents
 Reducing agent - the reactant that gives up
electrons.
 The reducing agent (e - donor) becomes
oxidized by losing electrons and its oxidation
number increases.
 If a substance gives up electrons easily, it is
said to be a strong reducing agent.
 Example: Na2S2O3 (moderate strong), KI,
FeSO4, Na2C2O4, etc.
Septem 18, 2022 Experiment 5 15
 Iodimetry and Iodometry
 When an analyte that is a reducing agent is
titrated directly with a standard iodine
solution, the method is called "iodimetry“.
 When an analyte that is an oxidizing agent is
added to excess iodide to produce iodine, and
the iodine produced is determined by titration
with sodium thiosulfate, the method is called
"iodometry".

Septem 18, 2022 Experiment 5 16

 Theory (contd.)

 Reactions
 (1) K2Cr2O7 + 14HCl + 6KI = 8KCl + 2CrCl3

 + 7H2O + 3I2
 (2) 2Na2S2O3 + I2 = S4O62- + 2I- + 4Na2+


Septem 18, 2022 Experiment 5 17

 Redox Half Reactions

For 1:

 (a) 6I- (aq.)  3I2 (aq.) + 6e (oxid. half reaction)

 (b) Cr2O72- (aq.) + 14H+ (aq.) + 6e 
 2Cr3+ (aq.) +7H2O (red. half reaction)

Septem 18, 2022 Experiment 5 18

 Redox Half Reactions …

 For 2:

 (a) 2S2O32-(aq.)  S4O62- + 2e (oxid. half reaction)

 (b) I2 (aq.) + 2e  2I-(aq.) (red. half reaction)

Septem 18, 2022 Experiment 5 19

 Indicator
 Starch is the indicator of titration involving
iodine because it forms an intense blue
complex with even a trace of iodine.
 Starch is not a redox indicator; it responds
specifically to the presence of I2, not to a
change in redox potential. The active fraction
of starch is amylose, a polymer of the sugar
α-d-glucose.
 In the presence of starch, iodine forms I 5−
chains inside the amylose helix and the color
turns dark blue.
Septem 18, 2022 Experiment 5 20
 iodine forms I5− chains inside
the amylose helix and the
color turns dark blue

Septem 18, 2022 Experiment 5 21

 Acid-base indicator vs. Redox indicator

Acid-base indicator Red-ox indicator

Complex organic compounds Complex organic compounds

Weak acid or base neutral

Usually colorless
Possess different colors

Indicate the end-point of a

Indicate the end-point of a
titration by change of color
titration by change of color
when all liberated iodine is
depending on pH
consumed by analyte.
Septem 18, 2022 Experiment 5 22
 Required Chemicals
1. 12% KI solution
2. NaHCO3
3. Conc. HCl acid
4. Standard K2Cr2O7 solution
5. Na2S2O3 solution
6. Starch solution

Septem 18, 2022 Experiment 5 23

 Preparation of the Solutions
 (1) 12% KI Solution
 12 g KI (white solid) dissolved in 100g
solution
 (2) NaHCO3- 1.0 g (white solid) for each
reading; it is used to remove excess of HCl
acid in the solution and to create a layer of
CO2 in the conical flask to reduce loss of
volatile I2.
 (3)
Septem Conc.
18, 2022 HCl- 4.0Experiment
ml for 5 each reading 24
 Preparation of the solutions…
 (4) K2Cr2O7: Mol. wt. 294, gram-equiv. wt. 49
(Mol. wt. divided by 6, the number of electrons it
gain), primary standard substance
 To make exactly 1N K2Cr2O7 soln. dissolve 49gm
solid in 1000ml
 To make exactly 0.1N K2Cr2O7 soln. dissolve
4.9gm solid in 1000ml
 To make exactly 0.1N K2Cr2O7 soln. dissolve
0.49gm solid in 100ml
Septem 18, 2022 Experiment 5 25
 Preparation of the solutions…
 Na2S2O3.5H2O: Mol. wt. 248, gram-equiv. wt. 248
(Mol. wt. divided by 1, since it gives up 1 electron
during oxidation), secondary standard substance.
 To make approx. 1N Na2S2O3 soln. dissolve 248 gm
solid in 1000ml
 To make approx. 0.1N Na2S2O3 soln. dissolve 24.8
gm solid in 1000ml
 To make approx. 0.1N Na2S2O3 soln. dissolve 12.4
gm solid in 500ml

Septem 18, 2022 Experiment 5 26

 Preparation of the Solutions…

 Starch solution: 1-2mL for each reading

 Preparation: Make paste of 1g soluble
starch with little water and pour it slowly in
100mL boiling water with stirring and
continue boiling for 1 minute. Add 1g boric
acid crystal in it to preserve for long time.

Septem 18, 2022 Experiment 5 27

 Procedure
 Take 4.0mL of 12% KI solution in a
conical flask and dilute to about 50 mL.
 Add about 1.0 gm of NaHCO3 and shake
the flask until the salt dissolves.
 Add about 4 mL conc. HCl acid and then
add 10 mL standard K2Cr2O7 solution by
means of a pipette in the same flask.

Septem 18, 2022 Experiment 5 28

 Procedure
4 mL 12% KI

4 mL of
46 mL of H2O Conc. HCl

1 gm NaHCO3 10 mL K2Cr2O7

Solution
Dissolve turns brown
NaHCO3 by due to I2
shaking, solution is

colorless

Septem 18, 2022 Experiment 5 29

 (~ 60 mL)

After 5 minutes

(~ 100 mL)
Septem 18, 2022 Experiment 5 30
 Procedure…
 Shake the flask and cover it with a watch
glass, allow the solution to stand for about
five minutes in the dark (inside the desk).
 Rinse the watch glass and dilute the
solution about 100mL.
 Titrate the liberated iodine with sodium
thiosulphate solution from a burette until
the brown color fades (light yellow).

Septem 18, 2022 Experiment 5 31

 Procedure…
 Add about 1 mL starch solution and
continue titration by adding sodium
thiosulphate solution from the burette
until one drop of the sodium thiosulphate
solution changes the color of the solution
from deep blue to light green.
 This is the end point. Note the burette
reading.

Septem 18, 2022 Experiment 5 32

 Change of Color
Brown Due to presence
of I2
Na2S2O3 solution
Light Due to presence
yellow of trace of I2
Starch solution
Intense Due to starch-I2
blue complex
Na2S2O3 solution
Light Due to presence of
Septem 18, 2022 green
Experiment 5
chromic (Cr3+) ions 33
 Procedure…

 The difference of the burette reading from

initial to final will be the volume of the
thiosulphate required with titration.
 Repeat the process at least twice.
 Calculate the strength of sodium
thiosulphate solution using the formulae
as shown below:

Septem 18, 2022 Experiment 5 34

 Calculations
 VNa2S2O3 x N Na2S2O3= VK2Cr2O7 x NK2Cr2O7

Results
 The strength of supplied Na2S2O3 solution
is……….. (N)

Septem 18, 2022 Experiment 5 35

  Observe Exp.5 video
 Step-1 for Exp.5
 Calculate the results

 The results of Step-1 is

used to calculate the
amount of copper ions in
Step-2 of Exp.6.