Expt. No.

4
Date:
Determination of Calcium in Portland Cement
(Permanganometry)
Aim: To determine the amount of Calcium (as oxide) present in the given sample of
Portland Cement by using a standard solution of Potassium permanganate

Apparatus: Burette, Pipette, Conical flasks, Beakers, Volumetric flask, Measuring jar,
Distilled water bottle, Burette stand, Glazed tile and Fischer clamp.

Chemicals Required: Cement, Hydrochloric acid, Ammonium hydroxide, Ammonium

oxalate, Potassium Permanganate, Oxalic acid, Sulphuric acid and Distilled Water

Theory: Metals like calcium, copper, lead and zinc form sparingly soluble oxalates and
they can be determined by dissolving the washed precipitate in dilute sulphuric acid and
titrating with a standard potassium permanganate. This method is widely used for the
determination of calcium.
Calcium present in a solution is precipitated as its oxalate by the addition of
ammonium oxalate solution to a dilute hydrochloric acid of cement followed by 1:1
ammonia solution for neutralising the acid. The calcium oxalate precipitate is filtered
using Whatmann No. 42 filter paper and thoroughly washed with water. The calcium
oxalate precipitate is dissolved in dilute sulphuric acid, heated to 70-800 C and titrated
against a standard solution of potassium permanganate for the Determination.

Cement  HCl  CaCl 2  Excess HCl

Excess HCl  NH 4 OH  NH 4 Cl  H 2 O (Neutralisation)
CaCl 2  (NH 4 ) 2 C 2 O 4  CaC 2 O 4  NH 4 Cl
CaC 2 O 4  H 2SO 4  CaSO 4  H 2 C 2 O 4
2KMnO4  5H 2 C 2 O 4  3H 2SO 4  K 2SO 4  2MnSO4  8 H 2 O  10CO 2

In the above reaction, all the reactants and products are colourless except
potassium permanganate. Hence, after the completion of the reaction of peroxide with
permanganate the excess trace amount of permanganate imparts a pink colour to the
solution taken as the end point of the reaction.

Part – I: Standardisation of Potassium permanganate solution

Procedure: 10.0 ml of standard oxalic acid solution is pipetted out into a clean conical
flask carefully. To this 10.0 ml of 10N sulphuric acid solution and 40.0 ml of distilled
water are added with measuring jar. The contents of the conical flask are heated to 70-
800 C (when the solution just starts to boil) the hot solution is titrated with constant
thorough shaking with potassium permanganate solution from the burette until the colour
of the solution changes from colourless to pale pink by the addition of one drop of
potassium permanganate solution, which is the end point of the reaction. A number of
titrations are carried out until 2 or 3 concurrent readings are obtained. The results are
tabulated neatly in Table - I

Table – I
Standardisation of Potassium Permanganate Solution

S. Vol. of Burette Reading (ml) Volume of

No (COOH)2 KMnO4 Soln.
solution Taken Initial Final consumed (ml)
(ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of standard oxalic acid solution = N1 (Given)
Volume of oxalic acid solution = V1 = 10.0 ml
Normality of KMnO4 solution = N2 = ?
Volume of KMnO4 solution = V2 = ml

By the law of Equivalence (At the endpoint): V1N1=V2N2

V1  N1
Normality of KMnO4 solution (N 2 )  = ________
V2

Part – II: Determination of Calcium as Calcium oxide present in 100.0 ml of the

given solution

a) Preparation of Cement Solution:

About 5.0 g of Portland cement is accurately weighed transferred into a 600.0 ml
beaker. A solution of 1:4 Hydrochloric acid is added and covered with a watch glass.
The contents of the beaker are heated to boiling. The solution is filtered using a
Whatmann No. 42 filter paper and the residue on the filter paper is washed several times
with Hydrochloric acid. The filtrate and washings are boiled and ammonical with 1:4
ammonia solution. The precipitate formed is allowed to settle down and the solution is
filtered. The precipitate is washed with hot water. The filtrate and washing is diluted to
1000.0 ml. The solution is boiled and from the hot solution, calcium is precipitated as
calcium oxalate by adding a saturated solution of Ammonium oxalate. The boiling is
continued for ten minutes after which the precipitate is allowed to settle. A drop or two
of ammonium oxalate solution is added to the supernatant solution to ensure that all the
calcium present has been converted as its oxalate. The solution is filtered using
Whatmann No. 42 filter paper and the precipitate of calcium oxalate is completely onto
the filter paper. The precipitate is washed number of times with cold water. A hole is
pierced in the filter paper and the bulk of the precipitate is transferred into a 100.0ml
volumetric flask with little quantity of hot water. Hot solution of 1:8 sulphuric acid is
added on the filter paper to ensure the completer transfer of the precipitate and finally the
paper is washed with hot water. If necessary a small quantity of hot dilute sulphuric acid
for complete dissolution of the precipitate. The contents of the 100.0ml volumetric flask
are diluted up to the mark with distilled water and mixed well for complete
homogenisation.

Procedure:
10.0 ml of the above prepared cement solution is pipetted out into a clean conical
flask carefully. To this 10.0 ml of 10N sulphuric acid solution and 40.0 ml of distilled
water are added with measuring jar. The contents of the conical flask are heated to 70-
800 C and the hot solution is titrated with constant thorough shaking with potassium
permanganate solution from the burette in the cold until the colour of the solution changes
from colourless to pale pink by the addition of one drop of potassium permanganate
solution, which is the end point of the reaction. A number of titrations are carried out
until 2 or 3 concurrent readings are obtained. The results are tabulated neatly in Table-II

Table – II
Determination of Calcium as Calcium Oxide
S. Vol. of Cement Burette Reading (ml) Volume of
No solution Taken KMnO4
(ml) Initial Final consumed (ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of KMnO4 solution = N2 (From part I) =
Volume of KMnO4 solution = V2 A = ml
Normality of Cement solution = N3 = ?
Volume of Cement solution = V3 = 10.0 ml

By the law of Equivalence (At the endpoint): V2AN2 = V3N3

V A  N2
Normality of Cement solution (N 3 )  2 = ________
V3
Molecular Weight 40.0
Equivalent Weight of Calcium in Cement =   20.0
2 2

Amount of Calcium present in 100 ml of the given solution

N  20.0
 3 Grams = _________ Grams
10
1000.0 ml of 1.0N KMnO4 solution = 28.0 g of CaO
1.0ml 1.0N KMnO4 solution = 0.028 g of CaO
 Suppose 10.0 ml of cement solution consumes „X‟ ml of 0.10N KMnO4 then the
amount of calcium oxide present in 100.0ml of the solution -
10.0  X  0.028
 Grams of CaO
0.10
RESULT: The amount of Calcium present as Calcium oxide in 100 ml
of the given solution of the given sample of Portland cement = __________ g

Flask No. Amount of Amount of % Error

H2O2 H2O2
given (g) reported (g)

Precautions:
1. In the standardisation of KMnO4 and in the Determination of Calcium
oxide content in the sample of Portland cement the contents of the conical
flask should not be heated for a ling time as decomposition may occur.
2. All the other apparatus should be cleaned with tap water and wipe the
work bench dry with a waste cloth after completing the experiment.
3. The cement solution should be prepared accurately without any wastage

Note: It is an important experiment, as it helps in construction work. A person

can be drawn to the court of law for faulty usage of sand, gravel and
cement in construction.

Indicator: KMnO4 (Self Indicator)

Expt. No. 5
Date:
Determination of Hydrogen Peroxide
(Permanganometry)
Aim: To determine the weight and volume strength of Hydrogen Peroxide using a
standard solution of Potassium permanganate

Apparatus: Burette, Pipette, Conical flasks, Beakers, Volumetric flask, Measuring jar,
Distilled water bottle, Burette stand, Glazed tile and Fischer clamp.

Chemicals Required: Potassium Permanganate, Hydrogen peroxide Mohr's salt,

Sulphuric acid and Distilled Water

Theory: Hydrogen peroxide H2O2 is usually available in the form of solution containing
about 3.0%. 6.0%, 12.0% and 30.0% of hydrogen peroxide. It is usually marketed in
volume strength of 10.0, 20.0, 40.0 and 100.0 concentrations. This terminology is based
on the volume of oxygen liberated when the solution decomposes by boiling. Thus 1.0ml
of 20.0 volume strength of hydrogen peroxide will yield 20.0 ml of oxygen measured at
STP (00 C and 760mm)

Potassium permanganate is an oxidising agent and hydrogen peroxide is a

reducing agent with the formula H2O2. Solution strengths of hydrogen peroxide can be
determined volumetrically using a standard solution of potassium permanganate after
acidifying with sulphuric acid. These two react in sulphuric acid medium as per the
following reactions.
2H 2 O 2  2 H 2 O  O 2 SLOW 
H 2 O 2  2 H 2 O  O FAST
In Sulphuric acid medium Hydrogen peroxide is converted into oxygen and water. The
reaction between Hydrogen peroxide and Potassium permanganate proceeds as per the
reaction

H 2 O 2  O 2  2H   2e -
2KMnO4  3H 2SO 4  K 2SO 4  2MnSO4  3 H 2 O  5(O)
5H 2 O 2  5(O)  5H 2 O  5O 2
2KMnO4  5H 2 O 2  3H 2SO 4  K 2SO 4  2MnSO4  8 H 2 O  5O 2

The above reaction clearly shows that manganese in potassium permanganate is

reduced from Mn7+ to Mn2+ and hydrogen peroxide is oxidised to oxygen and is a
REDOX reaction. All the reactants and products are colourless except potassium
permanganate, hence after the completion of the reaction of peroxide with permanganate
the excess trace amount of permanganate imparts a pink colour to the solution at the end
point of the reaction.
Part – I: Standardisation of Potassium permanganate solution

Procedure: 10.0 ml of standard Mohr‟s salt or Ferrous sulphate solution is pipetted out
into a clean conical flask carefully. To this 10.0 ml of 10N sulphuric acid solution and
40.0 ml of distilled water are added with measuring jar. The contents of the conical flask
are titrated with constant thorough shaking with potassium permanganate solution from
the burette until the colour of the solution changes from colourless to pale pink by the
addition of one drop of potassium permanganate solution, which is the end point of the
reaction. A number of titrations are carried out until 2 or 3 concurrent readings are
obtained. The results are tabulated neatly in Table - I

Table – I
Standardisation of Potassium Permanganate Solution

S. Vol. of Fe2+ Burette Reading (ml) Volume of

No solution Taken KMnO4 Soln.
(ml) Initial Final consumed (ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of standard Mohr‟s Salt solution = N1 (Given)
Volume of Mohr‟s salt solution = V1 = 10.0 ml
Normality of KMnO4 solution = N2 = ?
Volume of KMnO4 solution = V2 = ml

By the law of Equivalence (At the endpoint): V1N1=V2N2

V1  N1
Normality of KMnO4 solution (N 2 )  = ________
V2
Part – II: Determination of the amount of Hydrogen peroxide present
in 100.0 ml of the given solution and also to determine the volume strength

Procedure:
The hydrogen peroxide solution given in the 100.0 ml volumetric flask is diluted
up to the mark with distilled water and mixed thoroughly for complete homogenisation.
10.0 ml of this solution is pipetted out into a clean conical flask carefully. To this 10.0 ml
of 10N sulphuric acid solution and 40.0 ml of distilled water are added with measuring
jar. The contents of the conical flask are titrated with constant thorough shaking with
potassium permanganate solution from the burette in the cold until the colour of the
solution changes from colourless to pale pink by the addition of one drop of potassium
permanganate solution, which is the end point of the reaction. A number of titrations are
carried out until 2 or 3 concurrent readings are obtained. The results are tabulated neatly
in Table-II
Table – II
Determination of Hydrogen Peroxide

S. Vol. of H2O2 Burette Reading (ml) Volume of

No solution Taken KMnO4
(ml) Initial Final consumed (ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of KMnO4 solution = N2 (From part I) =
Volume of KMnO4 solution = V2 A = ml
Normality of H2O2 solution = N3 = ?
Volume of H2O2 solution = V3 = 10.0 ml

By the law of Equivalence (At the endpoint): V2AN2 = V3N3

V A  N2
Normality of H2O2 solution (N 3 )  2 = ________
V3

Molecular Weight 34.02

Equivalent Weight of H2O2 =   17.015
2 2
Amount of Hydrogen Peroxide present in 100 ml of the given solution
N  17.01
 3 Grams = „X‟ Grams
10

Volume of Oxygen liberated by ’X’ grams of Hydrogen peroxide at STP (0O C and
760 mm):

234.02 g of H2O2 liberates 22,400mlof oxygen at STP

34.02 g of H2O2 liberates 11,200mlof oxygen at STP
1g of H2O2 liberates 11,200/34.02 ml of oxygen at STP = 329 ml
Hence, „X‟ g of H2O2 liberates X329 ml of oxygen at STP

RESULT: The amount of Hydrogen peroxide Present in 100 ml of the

given solution = __________ g

Flask No. Amount of Amount of % Error

H2O2 H2O2
given (g) reported (g)

Volume of Oxygen liberated by the Hydrogen peroxide present in 100

ml of the given solution at STP (0O C and 760 mm) = _______ ml

Precautions:
1. All the apparatus should be cleaned with tap water and wipe the work
bench dry with a waste cloth after completing the experiment.
2. Hydrogen peroxide solution should be freshly prepared and the bottle
should be placed back in the refrigerator otherwise the contents will
decompose.

Indicator: KMnO4 (Self Indicator)

Expt. No. 6
Date:
Determination of Zinc
(Complexometry)
Aim: To determine the amount of Zinc present in 100.0 ml of the given solution
titrimetrically using a standard solution of EDTA.

Apparatus: Burette, Pipette, Conical flasks, Beakers, Volumetric flask, Measuring jar,
Distilled water bottle, Burette stand, Glazed tile and Fischer clamp.

Chemicals Required: Zinc Sulphate, Disodium salt of EDTA, Ammonium hydroxide

and ammonium chloride buffer, Eriochrome Black-T indicator and Distilled Water

Theory: Zinc can be determined titrimetrically using a standard solution of EDTA and
Eriochrome Black-T as indicator. The indicator is yellow at pH=6.0 blue at pH=8-12 and
orange at pH=13.0. The titrations can be carried out at pH=10 by adding ammonium
chloride buffer solution using Eriochrome Black-T as indicator. The metal forms a wine
red complex with the indicator and turns to a clear blue colour at the end point.
2 2 2 
Zn H Y  ZnY  2H
2
NaOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COONa
(Di Sodium Salt of Ethylene Diamine Tetra Aceticacid)

[Zn-EBT] complex + EDTA  [Zn-EDTA] complex+ EBT

(WINE RED) Colourless Colourless (BLUE)

Part – I: Standardisation of EDTA solution using a standard solution

of Zinc Sulphate Heptahydrate

Procedure: 10.0 ml of standard zinc sulphate solution is pipetted out into a clean conical
flask carefully. To this 20.0 ml of distilled water and 3 to 4 ml of ammonium hydroxide-
ammonium chloride buffer solution (pH=10.0) and 2-3 drops of Eriochrome Black-T
indicator are added. The contents of the flask are titrated with EDTA solution from the
burette until the colour changes from wine red to clear blue colour. by the addition of one
drop of EDTA solution. A number of titrations are carried out until 2 or 3 concurrent
readings are obtained. The results are tabulated neatly in Table - I
 Table – I
Standardisation of EDTA solution using a standard solution of zinc sulphate
heptahydrate

S. Vol. of Burette Reading (ml) Volume of

No ZnSO4.7H2O EDTA Soln.
solution Taken Initial Final consumed (ml)
(ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of standard ZnSO4.7H2O solution = N1 (Given)
Volume of ZnSO4.7H2O solution = V1 = 10.0 ml
Normality of EDTA solution = N2 = ?
Volume of EDTA solution = V2 = ml

By the law of Equivalence (At the endpoint): V1N1=V2N2

V  N1
Normality of EDTA solution (N 2 )  1 = ________
V2

Part – II: Determination of Zinc Sulphate heptahydrate present in

100.0ml of the given solution

Procedure:
Zinc Sulphate heptahydrate solution given in the volumetric flask is diluted up to
the mark and mixed well for complete homogenisation. 10.0 ml of this zinc sulphate
solution is pipetted out into a clean conical flask carefully. To this 20.0 ml of distilled
water and 3 to 4 ml of ammonium hydroxide-ammonium chloride buffer solution
(pH=10.0) and 2-3 drops of Eriochrome Black-T indicator are added. The contents of the
flask are titrated with EDTA solution from the burette until the colour changes from wine
red to clear blue colour. by the addition of one drop of EDTA solution. A number of
titrations are carried out until 2 or 3 concurrent readings are obtained. The readings are
tabulated in Table-II
 Table – II
Determination of percentage or the amount of available Chlorine in Bleaching
Powder

S. Vol. of Burette Reading (ml) Volume of EDTA

No ZnSO4.7H2O consumed (ml)
solution Taken Initial Final
(ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of EDTA solution = N2 (From part I) =
Volume of EDTA solution = V2 A = ml
Normality of ZnSO4.7H2O solution = N3 = ?
Volume of ZnSO4.7H2O solution = V3 = 10.0 ml

By the law of Equivalence (At the endpoint): V2AN2 = V3N3

V A  N2
Normality of ZnSO4.7H2O solution (N 3 )  2 = ________
V3

Molecular Weight 287.38

Equivalent Weight of ZnSO4.7H2O =   287.38
1 1

Amount of ZnSO4.7H2O present in 100 ml of the given solution

N  287.38
 3 Grams
10
Molecular Weight 65.38
Equivalent Weight of Zn =   65.38
1 1

Amount of Zn present in 100 ml of the given solution

N 3  65.38
 Grams
10

RESULT: The amount of ZnSO4.7H2O Present in 100 ml of the

given solution = __________ g

Flask No. Amount of Amount of % Error

ZnSO4.7H2O ZnSO4.7H2O
given (g) reported (g)
Precautions:
1. Before filling the burette with EDTA solution it should be rinsed properly
with distilled water and small quantity of EDTA solution respectively.
2. The conical flask should be thoroughly cleaned and rinsed with distilled
water before commencing each titration.
3. All the other apparatus should be cleaned with tap water and wipe the
work bench dry with a waste cloth after completing the experiment.

Note: Disodium salt of EDTA is used prepare the solution of

EDTA as pure EDTA does not soluble in water

Indicator: Eriochrome Black-T

HO
OH
N N SO3Na

NO2
Expt. No. 7
Date:
Determination of Total Hardness of Water
(Complexometry)
Aim: To determine the total hardness of the given water sample titrimetrically using a
standard solution of EDTA.

Apparatus: Burette, Pipette, Conical flasks, Beakers, Volumetric flask, Measuring jar,
Distilled water bottle, Burette stand, Glazed tile and Fischer clamp.

Chemicals Required: Zinc Sulphate, Disodium salt of EDTA, Ammonium hydroxide

and ammonium chloride buffer, Eriochrome Black-T indicator, Ground water sample and
Distilled Water

Theory: The most valuable application of EDTA titrations is the determination of

Hardness of water. Hardness of water is caused by the presence of bicarbonates,
carbonates, chlorides, sulphates and nitrates of calcium and magnesium. Temporary
hardness of water is caused by the presence of bicarbonates of these metals and can be
removed by boiling and require special methods as Permutit of Soda Lime or Ion
exchange processes. The hardness of water is usually expressed in terms of “ppm” (Parts
Per Million) – that means hardness caused by 1 part by weight of Calcium Carbonate in
1,000,000 parts of water. Hardness of water can be determined by complexometric
method using di sodium salt of EDTA solution titrimetrically.

EDTA forms complexes with calcium and magnesium wht the pH of the solution is
around 9.5 – 10.5 and to maintain the pH between this range a buffer solution of
Ammonium hydroxide and ammonium chloride is used. The complexes of calcium and
magnesium with EDTA are colourless hence an indicator is necessary to locate the end
point. Eriochrome Black-T is used as indicator, which forma an unstable wine red
complex with Calcium and Magnesium. The calcium complex is first formed with
EDTA, but the colour change does not occur until all the magnesium is also converted
into a complex. It is thus possible to determine the total amount of these metals present in
the water sample and the total hardness of water can be calculated. Calcium itself does
not give a satisfactory end point colour change of the indicator unless the water sample
also contains magnesium. Assuming that the water sample contains only calcium, 2 or 3
drops of Magnesium-EDTA complex is added as a precautionary measure. When all the
calcium and magnesium are removed by EDTA, the free indicator imparts a blue colour,
the end point of the reaction.

NaOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COONa
(Di Sodium Salt of Ethylene Diamine Tetra Aceticacid)

[Ca/Mg-EBT] complex + EDTA  [Ca/Mg-EDTA] complex + EBT

(WINE RED) Colourless Colourless (BLUE)
 The disodium salt of EDTA solution can be standardised by using a standard
solution of zinc sulphate in presence of Ammonium Hydroxide – Ammonium chloride
buffer solution and Eriochrome Black-T as indicator.
2 2 2 
Zn  H2Y  ZnY  2H

Part – I: Standardisation of EDTA solution using a standard solution

of Zinc Sulphate Heptahydrate

Procedure: 10.0 ml of standard zinc sulphate solution is pipetted out into a clean conical
flask carefully. To this 20.0 ml of distilled water and 3 to 4 ml of ammonium hydroxide-
ammonium chloride buffer solution (pH=10.0) and 2-3 drops of Eriochrome Black-T
indicator are added. The contents of the flask are titrated with EDTA solution from the
burette until the colour changes from wine red to clear blue colour. by the addition of one
drop of EDTA solution. A number of titrations are carried out until 2 or 3 concurrent
readings are obtained. The results are tabulated neatly in Table - I

Table – I
Standardisation of EDTA solution using a standard solution of zinc sulphate
heptahydrate

S. Vol. of Burette Reading (ml) Volume of

No ZnSO4.7H2O EDTA Soln.
solution Taken Initial Final consumed (ml)
(ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of standard ZnSO4.7H2O solution = N1 (Given)
Volume of ZnSO4.7H2O solution = V1 = 10.0 ml
Normality of EDTA solution = N2 = ?
Volume of EDTA solution = V2 = ml

By the law of Equivalence (At the endpoint): V1N1=V2N2

V  N1
Normality of EDTA solution (N 2 )  1 = ________
V2
Part – II: Determination of Total Hardness of the given water sample
titremetrically using standard solution of EDTA solution

Procedure:
100 ml of the hard water sample is accurately measured into a clean conical flask.
To this 3 to 4 ml of ammonium hydroxide-ammonium chloride buffer solution (pH=10.0),
2 drops of 0.1M Mg-EDTA complex are added. The complex helps to get a clear end
point. Now add 2-3 drops of Eriochrome Black-T indicator and the contents of the flask
are titrated with EDTA solution from the burette until the colour changes from wine red
to clear blue colour by the addition of one drop of EDTA solution. A duplicate titration is
carried out and the average titre value is determined. The readings are tabulated in Table-
II

Table – II
Determination of percentage or the amount of available Chlorine in Bleaching
Powder

S. Vol. of Hard Burette Reading (ml) Volume of EDTA

No Water sample consumed (ml)
Taken (ml) Initial Final
1 10.0 0.0
2 10.0
3 10.0
Average Titre Value

Calculation:
1,000 ml of 0.01M EDTA = 1.0 g of CaCO3
Ta ml (average titre value) of a M EDTA =
Ta aM Ta  aM
  1 g of CaCO 3
1000 0.01 10

Ta  aM
„W‟ ml or g of water sample taken = g of CaCO 3
10

1,000,000 Ta  aM
1,000,000 ml or g of water =  g of CaCO 3
W 10
Where „W‟ is the amount of water taken, Ta is the average titre value and aM is the
molarity of EDTA solution

Precautions:
1. In the standardisation of EDTA solution, the burette should be rinsed
thoroughly with distilled wate and small quantity of EDTA solution
respectively.
2. After each titration the conical flask should be properly cleaned and rinsed
with distilled water before doing another titration
 3. It is enough to add 20.0 ml of distilled water to the contents of the conical
flask before commencing a titration.
4. All the other apparatus should be cleaned with tap water and wipe the
work bench dry with a waste cloth after completing the experiment.

Note: Disodium salt of EDTA is used prepare the solution of

EDTA as pure EDTA does not soluble in water

Indicator: Eriochrome Black-T

HO
OH
N N SO3Na

NO2
Expt. No. 8
Date:
Determination of Chromium (VI) in Potassium Dichromate
Aim: To determine the amount Chromium (VI) present in the given solution Potassium
Dichromate by titrating against a standard solution of Ferrous Iron or Mohr‟s salt.

Apparatus: Burette, Pipette, Conical flasks, Beakers, Volumetric flask, Measuring jar,
Distilled water bottle, Burette stand, Glazed tile and Fischer clamp.

Chemicals Required: Potassium Dichromate, Ferrous Sulphate or Mohr‟s Salt,

Sulphuric acid, Phosphoric Acid, Diphenylamine and Distilled Water

Theory: Potassium Dichromate, K2Cr2O7 acts as an oxidising agent in presence of

sulphuric acid or Hydrochloric acid, oxidising Ferrous iron to Ferric iron and getting itself
reduced to a green chromic (Cr3+) salt. Mohr‟s Salt, (NH4)2SO4.FeSO4.6H2O is a
reducing agent. In presence of dilute acid medium the reaction between the two is as
follows.
K 2 Cr2 O 7  4H 2SO 4  K 2SO 4  Cr2 (SO 4 ) 3  4 H 2 O  3(O)
K 2 Cr2 O 7  8HCl  2KCl  2CrCl 3  4 H 2 O  3(O)
From either of these two equations, it is clear that the equivalent weight of Potassium
Dichromate is one sixth of it molecular weight. The reaction between Mohr‟s salt and
Potassium Dichromate in sulphuric acid medium is as follows.
K 2 Cr2 O 7  4H 2SO 4  K 2SO 4  Cr2 (SO 4 ) 3  4 H 2 O  3(O)
6FeSO 4  3H 2SO 4  3(O)  3Fe2 (SO 4 ) 3  3H 2 O
K 2 Cr2 O 7  6FeSO 4  7H 2SO 4  K 2SO 4  Cr2 (SO 4 ) 3  3Fe2 (SO 4 ) 3  7 H 2 O
As the reaction is between an oxidant and a reductant it is classified as a REDOX
reaction. Diphenylamine acts as an indicator to know the end pointof the reaction. It
imparts green colour to the ferrous solution due to the formation of chromic sulphate
which deepens to blue-green colour just before the end point and at the end point the
colour is intense purple or bluish violet. Diphenylamine is a weak organic base so it is
dissolved in concentrated sulphuric acid. As dichromate is a weak oxidising agent when
compared to permanganate, the reaction becomes slow before the end point. The addition
of syrupy phosphoric acid increases the rate of the reaction at the end point by removing
Ferric ions as Ferric phosphate from the sphere of reaction. According to the Lechatlier‟s
Principle, the equilibrium changes forward and the phosphoric acid reduces the reduction
potential of Fe2+ - Fe3+ by 0.15 – 0.30 volts, thereby reducing capacity increases when
compared to diphenylamine indicator. Once all the Ferrous iron has reacted with
dichromate, the excess trace amounts of dichromate will oxidise the indicator from the
bluish green to bluish violet due to formation of diphenyl benzidine.

Part – I: Standardisation of Mohr’s salt solution using standard

Potassium Dichromate Solution

Procedure: 10.0 ml of standard Mohr‟s salt or Ferrous sulphate solution is pipetted out
into a clean conical flask carefully. To this 10.0 ml of sulphuric acid – phosphoric acid
mixture solution and 40.0 ml of distilled water are added with measuring jar. Two drops
of diphenylamine indicator are added and the contents of the conical flask are titrated
with constant thorough shaking with standard potassium dichromate solution from the
burette until the colour of the solution changes from colourless –pale green – dark green –
bluish green – purple violet. The colour change from bluish green to purple or bluish
violet colour should occur by the addition of one drop of dichromate solution A number
of titrations are carried out until 2 or 3 concurrent readings are obtained. The results are
tabulated neatly in Table - I

Table – I
Standardisation Mohr’s salt solution against a standard solution of Dichromate

S. Vol. of Fe2+ Burette Reading (ml) Volume of

No solution Taken K2Cr2O7 Soln.
(ml) Initial Final consumed (ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of standard K2Cr2O7 solution = N1 (Given)
Volume of K2Cr2O7 solution = V1 = ml
Normality of Mohr‟s Salt solution = N2 = ?
Volume of Mohr‟s Salt solution = V2 = 10.0 ml

By the law of Equivalence (At the endpoint): V1N1=V2N2

V  N1
Normality of Mohr‟s salt solution (N 2 )  1 = ________
V2

Part – II: Determination of the amount of Chromium (VI) present in 100.0 ml of

the given solution of Potassium Dichromate

Procedure:
Potassium Dichromate solution given in the 100.0 ml volumetric flask is diluted
up to the mark with distilled water and mixed thoroughly for complete homogenisation.
The burette is thoroughly cleaned with tap water, rinsed with small quantity of distilled
water and unknown dichromate solution from the volumetric flask respectively. Now fill
the burette with unknown dichromate solution. 10.0 ml of the standard Mohr‟s salt
solution (standardised in part I) is pipetted out into a clean conical flask carefully. To this
10.0 ml of sulphuric acid – phosphoric acid mixture solution and 40.0 ml of distilled
water are added with measuring jar. After adding two drops of diphenylamine indicator,
the contents of the conical flask are titrated with potassium dichromate solution from the
burette until the colour of the solution changes from colourless –pale green – dark green –
bluish green – purple violet by the addition of one drop of potassium dichromate solution.
A number of titrations are carried out until 2 or 3 concurrent readings are obtained. The
readings are tabulated in Table-II
Table – II
Determination of Ferrous Iron or Mohr’s Salt

S. Vol. of Std. Burette Reading (ml) Volume of

No Mohr‟s salt K2Cr2O7
solution Taken Initial Final consumed (ml)
(ml)
1 10.0 0.0
2 10.0
3 10.0
4 10.0
5 10.0

Calculation:
Normality of Mohr‟s salt solution = N2 (From part I) =
Volume of Mohr‟s salt solution = V2 A = 10.0 ml
Normality of K2Cr2O7 solution = N3 = ?
Volume of K2Cr2O7 solution = V3 = ml

By the law of Equivalence (At the endpoint): V2AN2 = V3N3

V A  N2
Normality of K2Cr2O7 solution (N 3 )  2 = ________
V3

Molecular Weight 104.0

Equivalent Weight of Cr(VI) in K2Cr2O7 =   17.33
6 6

Amount of Cr(VI) present in 100 ml of the given solution of K2Cr2O7

N  17.33
 3 Grams
10
RESULT: The amount of Cr(VI) Present in 100 ml of the
given solution = __________ g

Flask No. Amount of Amount of % Error

Cr(VI) given Cr(VI) reported
(g) (g)

Precautions:
1. The standard Potassium Dichromate solution and the diluted solution of
the unknown Potassium dichromate solution given in a 100.0ml volumetric
flask are to be taken in the Burette for part-I and Part-II
 2. All the other apparatus should be cleaned with tap water and wipe the
work bench dry with a waste cloth after completing the experiment.

Indicator: Diphenylamine (Organic Secondary Amine)

H
Diphenylamine

Diphenyl benzidine
H H
N N

Diphenyl benzidine
N N

Note:
The above method can be adopted to determine the Chromium present in Steel.
Cr(III) present in steel should be oxidised to Cr(VI) before the Determination.
Though the reaction is between the Ferrous Iron or Mohr‟s salt and Potassium
dichromate, it cannot be used to determine Ferrous Iron or Mohr‟s salt as Potassium
dichromate is a better primary standard than Ferrous Iron or Mohr‟s salt.