ENGINEERING

CHEMISTRY LAB
MANUAL

As per VTUR-15

For Ist Year B. Tech Students (Common to All Branches)

Department of Chemistry Faculty Members

1
2
 Syllabus

Cycle- 1

1. Determination of alkalinity in water sample

2. Determination of toxic metals from simulated E-waste

3. Conductometric titration of mixture of weak and strong acids Vs strong
base

Cycle -2

1. Estimation of copper in samples from plating industry effluents by EDTA

method.

2. Estimation of Ferrous Ion by Potentiometric Titration

3. Determination of dissolved oxygen in water sample (WINKLER’S
METHOD)

Cycle-3

1. Estimation of nickel in an alloy by complexometric titration

2. pH Metry – Determination of Strength of HCl with NaOH
3. Determination of iron content by spectrophotometer

3
Table-I

Titre values and different alkalinities

S.No. Result of titration of [P] Hardness causing ions

and [M]
OH- CO3 2-
HCO3 –
1. [P] = O O O [M]

2. [P] = [M] [P] or [M] O O

3. [P] = ½ [M] O 2[P] or [M] O

4. [P] > ½ [M] 2[P] – [M] 2 [M] – 2 [P] O

5. [P] < ½ [M] O 2 [P] [M – 2(P)]

Table – II

Water Sample Vs Standard HCl

S. Volume Burette readings ml) Concordant volume of HCl(ml)

No of water
sample Phenolphthalein Methyl orange [P] [M]
(ml) end point [P] end point [M]
1. 20

2. 20

3 20

Calculation:

If the data satisfies the condition [P] > ½ [M]

i.) Volume of HCl required for [OH- ] alkalinity = 2[P] – [M]

= 2 X ….. - …….

= …….ml
2-
ii.) Volume of HCl required for [CO3 ] alkalinity = 2[M] – 2 [P]
= 2 X … - 2 X …..
= ……ml
iii.)[HCO3-] is not present

4
Expt. No. 1 Date:

ESTIMATION OF ALKALINITY OF WATER SAMPLE

Aim:

To determine the type and amount of alkalinity present in 1 litre of the given water
sample. Standard solution of hydrochloric acid of strength 0.1 N is given.

Principle:

Alkalinity is caused by the presence of hydroxide, carbonate and bicarbonate. There

are five alkalinity conditions possible in a given sample of water, hydroxide only, carbonate
only, bicarbonate only, combination of carbonate and hydroxide or carbonate and
bicarbonate. The various alkalinities can be estimated by titrating with a standard acid using
phenolphthalein and methyl orange indicators successively.

Determination of alkalinity:

Alkalinity is a measure of ability of water to neutralize the acids. OH-, CO32-, HCO3-
can be estimated separately by titration against standard acid using Phenolphthalein
and methyl orange as indicators.

The titration of water sample against a standard acid up to phenolphthalein end point
(P) marks the completion of reaction (i) and (ii) only. The amount of acid used thus
corresponds to OH- plus one half of the normal CO32- present. On the other hand, titration of
the water sample against a standard acid to methyl orange end point (M) marks the
completion of reaction (i) , (ii) and (iii) . Hence the total amount of acid used represent to the
total alkalinity. Thus

P = OH- + ½ CO32-

M = OH- + CO32- + HCO3-

i.) Phenolphthalein end point

Hydroxide alkalinity is completely neutralized and carbonate alkalinity is partially
neutralized during phenolphthalein end point.
OH- + H+ H2O

CO3 2-
+ H+ HCO3 –

ii) Methyl Orange end point

Bicarbonate neutralized occurs during methyl orange end point

HCO3 – + H+ CO2 + H2O

5
 1. Calculation of OH- alkalinity

Volume of HCl (V1) = ……..ml

Strength of HCl (N1) = 0.1 N

Volume of water sample (V2) = 20 ml

Strength of water sample (OH-) alkalinity (N2) = ?

According to volumetric law: V1 N1 = V2 N2

N2 = V1 N1/ V2

N2 = …..ml X 0.1 N / 20

= …..N

Amount of OH- content present in 1 litre of water sample in terms of CaCO3 equivalent

= {Strength of water sample X eq. wt of CaCO3}

i.e. OH- alkalinity in terms of CaCO3 equivalent = …… N X 50 X 1000 ppm

Alkalinity due to OH- ion = ………ppm

2. Calculation of CO32-alkalinity

Volume of HCl (V1) = ……..ml

Strength of HCl (N1) = 0.1 N

Volume of water sample (V2) = 20 ml

Strength of water sample (CO3 2- ) alkalinity (V2) = ?

N2 =V1 N1/ V2

N2 = …..ml X 0.1 N / 20

= …..N

Amount of CO32- content present in 1 litre water sample, in terms of CaCO3 equivalent

= Strength of water sample X eq. wt of CaCO3

i.e. CO3 2- alkalinity in terms of CaCO3 equivalent = ……N X 50 X 1000 ppm

Alkalinity due to CO3 2- ion = ……… ppm

6
 From the two titre values the different alkalinities are calculated
When
P = M, → Hydroxide alkalinity

2P = M, → Carbonate alkalinity

P = 0, → Bicarbonate alkalinity
P < 1/2 M, → Carbonate and bicarbonate alkalinity
CO3 2- = 2P
HCO3 – = M – 2P
P > 1/2 M, → Hydroxide and carbonate
CO3 2-= 2 (M-P)
OH- = 2P-M
Alkalinity values are expressed in terms of milligrams per litre as calcium carbonate.

Procedure:

Titration-I (With Phenolphthalein Indicator)

The burette is washed and rinsed with given hydrochloride. Then the burette filled
with 0.1 N hydrochloric acid. 20 ml of water sample is pipette out in a clean conical flask. A
drop of phenolphthalein indicator is added. Pink colour is observed. This solution is titrated
against the standard acid until pink colour is disappeared. The end point is noted. This titre
value corresponds to phenolphthalein end point (P).

Titration-II (With Methyl Orange Indicator)

Few drops of methyl orange indicator are added to the same solution after the
phenolphthalein end point. The titration is continued until the solution becomes red orange
and the total titre value is noted. This titre value corresponds to methyl orange end point (M).
The titration is repeated for concordant values.

From the titre values the amount of each alkalinity present in the water sample calculated.

Result:

Water sample contains the following alkalinity

i.) Hydroxide alkalinity = …….ppm

ii.) Carbonate alkalinity =……....ppm

iii.) Bicarbonate alkalinity =……....ppm

7
 TITRATION –I

Standardisation of EDTA

(Std. zinc sulphate Vs EDTA)

S.No Volume of Burette Readings (ml) Volume of Concordant

Std. ZnSO4 EDTA (ml) Value(ml)
Initial Final
(ml)

CALCULATION:

Volume of ZnSO4 Solution V1 = 20 ml

Strength of ZnSO4 Solution N1 = 0.01 N (given)

Volume of EDTA Solution V2 = ml

Strength of EDTA Solution N2 = V1 N1/V2

Strength of EDTA Solution N2 =

N2 =

= N

8
Expt. No. 2 Date:

DETERMINATION OF TOXIC METAL CONTENT FROM

SIMULATED E-WASTE

Aim:
To determine the amount of lead (toxic metal) from simulated E-waste

Principle:

Electronic wastes present severe environmental and health challenges for all the
countries in general and to India in particular. Electronic wastes can contain more
than a thousand assorted substances, many of which are lethal. These may be in the form of
heavy metals such as Hg, Pb, Cd, Cr etc. In this analysis of lead content, separation of lead
from E waste is the objective of the present experiment. Usually lead will be obtained in the E
waste elution along with Cd mostly and Bi to a little extent. The Bi, Pb, and Cd are
determined in the combined filtrate. These are diluted to a known volume and aliquots
used in the subsequent titrations. The bismuth content is determined by titration with
standard EDTA at pH 1-2 using xylenol orange as indicator; then, after adjustment of
the pH to 5-6 with hexamine, the combined Pb plus Cd can be titrated with EDTA. 1-10-
Phenanthroline is then added to mask the cadmium, and the liberated EDTA is titrated
with standard lead nitrate solution; this gives the cadmium content and hence the lead
content is obtained by difference. In the present experiment Lead and cadmium are provided
as if they are present in E-waste effluent and for simplicity sake cadmium is separated from
this solution and only lead has to be determined.

Procedure:

Titration 1: standardization of EDTA

Pipette out 20 mL of standard zinc sulphate solution into a clean conical flask. Add 10
mL of hexamine solution till the pH is basic and few drops of xylenol orange
indicator. Titrate the mixture in conical flask against EDTA taken in the burette until colour
changes from red to yellow. Repeat the titration to get concordant value. From the strength
of zinc sulphate solution calculate the strength of EDTA.

9
 TITRATION –II

Estimation of Lead in E-waste

(E-waste solution Vs EDTA)

S.No Volume of Burette Readings

E- waste solution (ml) Volume of EDTA Concordant
(ml) (ml) Value (ml)

Initial Final

CALCULATION:

Volume of E-waste Solution V1 = 20 ml

Strength of E-waste Solution N1 = ?

Volume of EDTA Solution V2 = ml

Strength of EDTA Solution N2 =

N1 =

N1 =
Strength of E-waste Solution = -------------- N

The amount of lead present in the E-waste solution = Eq. Wt of Lead (207.2) x ………… N

= ……. g

10
Titration 2: Estimation of Lead

Pipette out 20 mL of the E-waste solution into a clean conical flask. Add 10 ml of n-
hexamine solution till the pH is basic and few drops of xylenol orange indicator. Titrate the
mixture in conical flask against EDTA taken in the burette until colour changes from red to
yellow. Repeat the titration to get concordant value. Calculate the strength of lead solution by
using strength of EDTA and amount of lead present in the E-waste solution.

Result:

The amount of lead present in 1 litre of the E-waste solution = ……. g

11
TABLE

Titration of mixture of acids (HCl and CH3COOH) Vs NaOH

S. No Volume of NaOH added Conductance

(ml) (mho)

10

CALCULATION FOR STRENGTH OF HCl

Volume of HCl taken V1 = 20 ml

Strength of HCl, N1 = ?

Volume of NaOH, V2 = A (first titre value from the graph)

Strength of NaOH, N2 = 0.1N

According to the law of Volumetric analysis V1N1 = V2N2

N1 = V2N2/V1 = A x 0.1 / 20

The strength of HCl = ------------ N.

The amount of HCl present in 1 litre of the given solution =

Strength of HCl x Eq. wt. of HCl

= --------- N x 36.5

= --------- g.

12
Expt No. 3 Date:

CONDUCTOMETRIC TITRATION OF MIXTURE OF WEAK AND

STRONG ACIDS Vs STRONG BASE

AIM

To determine, the amount of the strong acid (HCl) and the weak acid (CH3COOH)
present in one litre of the given solution, by titrating against a strong base (NaOH),
conductometrically.

Principle

The conductivity of the solution depends on the number of ions (concentration) and
the mobility of the ions. When sodium hydroxide is added slowly to a mixture of strong and
weak acids, the strong acid gets neutralized first. The replacement of the highly
mobile hydrogen ions (H+) by the less mobile sodium ions (Na+) causes decrease in
conductance until the end point is reached

HCl + NaOH  NaCl + H2O

After the complete neutralization of HCl, further addition of NaOH results in

neutralization reaction with the weak acid. During the reaction, acetic acid forms
sodium acetate and water.

CH3COOH + NaOH  CH3COONa +H2O

Since sodium acetate is a stronger electrolyte than acetic acid, the conductance
increases marginally until the complete neutralization of acetic acid. After complete
neutralization, there is sudden increase in conductance. This is due to increase in number of
ions and the presence of fast moving OH- ions.

MATERIALS REQUIRED

Conductivity meter (with cell), burette (50 ml), pipette (20 ml), beakers (100 ml),
stirrer /glass rod, mixture of acids solution, NaOH solution.

PROCEDURE

Take 20 ml of the mixture of acids solution in a 100 ml beaker and add 20ml of
conductivity water. Clamp the conductivity cell in the beaker, so that the cell is dipped in the

13
CALCULATION FOR STRENGTH OF CH3COOH

Volume of CH3COOH taken V1 = 20 ml

Strength of CH3COOH, N1 = ?

Volume of NaOH, V2= B - A (second titre value from the graph)

Strength of NaOH, N2 = 0.1N

According to the law of Volumetric analysis V1N1 = V2N2

N1 = V2N2/V1 = (B - A) x 0.1 / 20

The strength of CH3COOH = ------------ N.

The amount of CH3COOH present in 1 litre of the given solution

= Strength of CH3COOH x Eq. wt. of CH3COOH

= --------- N x 60

= --------- g.

14
acid solution and note the initial reading in the conductivity meter. The burette is filled with
the standard NaOH solution. Add 0.5 ml of NaOH solution from the burette, and stir
the contents thoroughly. Measure the conductivity of the solution. Continue the addition
of NaOH solution (1 ml each time). Stir the solution thoroughly, and measure the conductivity
of the solution, after each addition of 1 ml NaOH solution. The conductivity decreases until
the first end point is reached. Then the conductivity increases slowly until the second end
point. After the second end point, the conductivity suddenly increases. Take at least five
readings after the second end point.

Plot the graph between the volume of NaOH added and the conductance. From the
graph the first (A) end point and the second (B) end point noted. From the end points the
amount of HCl and CH3COOH can be calculated.

RESULTS

1. The amount of HCl present in one litre of the given solution = ................g.

2. The amount of CH3COOH present in one litre of the given solution = ................g.

15
 TITRATION –I

Standardisation of EDTA

(Std.ZnSO4 Vs EDTA)

S.No Volume of Std. Burette Readings (ml) Volume of

ZnSO4 (ml) EDTA (ml) Concordant
Initial Final Value (ml)

CALCULATION:

Volume of ZnSO4 Solution V1 = 20 ml

Strength of ZnSO4 Solution N1 = 0.01 N (given)

Volume of EDTA Solution V2 = ml

Strength of EDTA Solution N2 = ?

According to the law of volumetric analysis,

V1 × N1 = V2 × N2

Strength of EDTA Solution N 2=

N1=

= N

16
 Expt No. 4 Date:

ESTIMATION OF COPPER IN SAMPLES FROM PLATING INDUSTRY

EFFLUENTS BY EDTA METHOD
AIM
To estimate the amount of Copper present in 1 litre of the given solution being
supplied with standard solution of ZnSO4 of strength 0.01 N and 0.01M EDTA solution is
provided.

PRINCIPLE:

Industrial waste water from electroplating industries has to be treated properly and if
feasible metals may be recovered. There are two general options available for
the electroplaters and these may be either (i) modify the process with zero discharge or (ii)
treat the waste water and make the discharge free from pollutants. In this aspect when
these industries set up treatment of waste water they need a simple method to find out
the
estimation of copper in waste water. Cu2+ ions are determined by the complexometric method
using EDTA. Electroplaters have a number of options for cost effectively bringing a facility
into compliance with water pollution control regulations.
The reactions are,

Cu2+ + HD2- → CuD + H+

Purple

CuD- + EDTA → Cu- EDTA + HD2-

Dark green

PROCEDURE TITRATION – I

STANDARDISATION OF EDTA

Burette is filled with EDTA solution. Pipette out 20ml of std. ZnSO4 into a
clean conical flask. To this 5 ml of ammonia buffer solution and 2 drops of EBT
indicator are added. The solution turns wine red colour and it is titrated against EDTA taken
in the burette. Continue the titration until the end point is the appearance of steel blue colour.
Repeat the titrations to get the concordant value. From the volume of EDTA consumed,
strength of EDTA solution is calculated.

17
 TITRATION –II

Estimation of Copper in water effluent

(Effluent water Vs EDTA)

S.No Volume of
effluent water Burette Readings (ml) Volume of EDTA Concordant
(ml) (ml) Value (ml)
Initial Final

CALCULATION:

Volume of copper Solution V1 = 20 ml

Strength of copper Solution N1 = ?

Volume of EDTA Solution V2 = ml

Strength of EDTA Solution N2 =

According to the law of volumetric analysis,

N1=
Strength of copper in effluent water = -------------- N

Amount of Copper present in given effluent water

= Eq.Wt of Cu X strength of copper in effluent water

= 63.54 X -----------

= g

18
TITRATION – II

Burette is filled with EDTA solution. Pipette out 20ml of effluent water solution into
a clean conical flask. To this 5 ml of ammonia buffer solution and 2 drops of Fast Sulphon
Black F indicator are added. The change of purple colour into dark green colour is the end
point. Repeat the titrations to get the concordant value. From the volume of EDTA
consumed, strength of copper in effluent water is calculated.

Structure of EBT Structure of Fast Sulphon Black F

(Chemical formula: C10H16N2O8) (Chemical formula: C30H20N4O11S3)

RESULT

The amount of Copper present is 1 litre of the given water sample = ---------------g

19
Graph (a): Volume of K2Cr2O7 Vs emf (b) Volume of K2Cr2O7 Vs ΔE/ΔV

STEP: 1

TABLE – I

Titration of K2Cr2O7 Vs Ferrous ion solution

S. No Volume of K2Cr2O7 (ml) EMF

(volts)

1
2
3
4
5
6
7
8
9
10

20
Expt. No. 5 Date:

ESTIMATION OF FERROUS ION BY POTENTIOMETRIC

TITRATION

AIM

To estimate the amount of ferrous ion (Fe2+) present in 1 litre of the given solution by
potentimetrically. A standard solution of potassium dichromate of strength 0.1N provided.

PRINCIPLE

Potentiometric titrations depend on measurement of EMF. between

reference electrode and an indicator electrode. When a solution of ferrous ion is titrated with a
solution of potassium dichromate, the following redox reaction takes place.

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

During this titration Fe2+ is converted into Fe3+, whose concentration increases. At the
end point, there will be a sharp change due to complete removal of all Fe 2+ ions. The cell is
set up by connecting this redox electrode with a calomel electrode as shown below:

Hg/Hg2Cl2(s), KCl//Fe2+, Fe3+/Pt

A graph between EMF measured against the volume of K2Cr2O7 added is drawn and
the end point is noted from the graph.

MATERIALS REQUIRED

1. Potentiometer 2. Pt electrode 3. saturated Calomel Electrode 4. standard K2Cr2O7

solution. 5. given ferrous ion solution.

PROCEDURE:

20 ml of the given ferrous ion solution is pipette out into a clean 100 mL
beaker. About 10 mL of dil.H2SO4 is added to it. A platinum electrode (Pt) is dipped
into the solution. This electrode is then coupled with a saturated calomel electrode and
the cell is introduced into Potentiometric circuit. The standard K2Cr2O7 solution is taken in
the burette and added gradually.

21
STEP: 2

TABLE –I I

Titration of K2Cr2O7 Vs ferrous ion solution

S.No Volume of EMF (V) ∆E (V) ∆V (mL) ∆E /∆V

K2Cr2O7 (mL) Volts/mL
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

22
TITRATION – I

First a preliminary titration is carried out by adding standard K 2Cr2O7 solution

in portions of 1 mL and the emf of the cell is measured after each addition. The
addition of K2Cr2O7 is continued even after the end point and the range at which end point
lies if found out by plotting the volume of K2Cr2O7 added against emf (Graph a).

23
CALCULATION

Calculation of strength of ferrous ion solution

Volume of ferrous ion solution, V1 = 20 ml

Strength of ferrous ion solution, N1 = ?

Volume of K2Cr2O7 V2 = -----ml

Strength of K2Cr2O7 N2 = 0.1 N

According to the law of volumetric analysis,

V1 × N1 = V2 × N2

N1=

N1=

∴Strength of ferrous ion solution = N

The amount of ferrous ion present in 1 litre of the given solution= N × 55.85 (eq. Wt. of Fe)

= g.

24
TITRATION – II

Another fair titration is carried out by adding standard K2Cr2O7 solution in portions of
0.2 mL near the end point and emf of the cell is measured after each addition. The addition of
K2Cr2O7 is continued even after the end point for further 1 mL. The accurate end point
is determined by plotting ∆E/∆V vs volume of K2Cr2O7 added (Graph b). From the end point,
the strength of ferrous ion solution and hence its amount can be calculated.

RESULT:

The amount of ferrous ion present in 1 litre of the given solution = g.

25
 TITRATION –I

Standardisation of Sodium thiosulphate

(Std.K2Cr2O7 Vs Sodium thiosulphate)

S.No Volume of Burette Readings (ml) Volume of Concordant

K2Cr2O7 (ml) Sodium
Initial Final thiosulphate (ml) Value(ml)

CALCULATION I:

Volume of K2Cr2O7 Solution V1 = 20 ml

Strength of K2Cr2O7 Solution N1 = 0.01 N

Volume of Sodium thiosulphate Solution V2 = ml (Concordant Value)

Strength of Sodium thiosulphate Solution N2 =

N2=

Strength of Sodium thiosulphate Solution = N

26
Expt.No. 6 Date:
ESTIMATION OF DISSOLVED OXYGEN (DO) IN WATER
SAMPLE (WINKLER’S METHOD)
AIM:

To determine the amount of dissolved oxygen (DO) in water sample by Winkler’s

method. A standard solution of K2Cr2O7 of strength 0.01 N is given.PRINCIPLE:

Oxygen is dissolved in pure water to a definite proportion. The oxygen content may
decrease because of the presence of organic impurities (because of aerobic oxidation). The
oxygen content in pure water may be 7-9 mgs/ lit at a temperature range of 25°C - 35°C.
The amount of dissolved oxygen in water is estimated using Winkler’s reagent
(Potassium bromide + Potassium bromate). Water sample is collected carefully in a
stoppered flask. Manganese sulphate solution in presence of alkali iodide is added to water
in an iodine flask. The following reaction occurs.

Mn2++2OH-→ Mn (OH)2
↓
(White
ppt)

Mn (OH)2 + 1/2O2 → Mn O
(OH)2 ↓
Yellow brown ppt

The precipitate dissolves in concentrated sulphuric acid and KI is added. The

liberated iodine is titrated against Na2S2O3 solution. Freshly prepared starch solution is
added to the conical flask, when it is nearing the end point. The end point is the
disappearance of blue colour.

MnO(OH)2 + 2KI + 4H2SO4→ I2 + Mn(SO4)2 +

3H2O

2Na2S2O3+I2→ Na2S4O6
+2NaI

Sodium thiosulphate can be standardized using potassium dichromate. The

liberated iodine is titrated against thiosulphate. Starch is added near the end point,
reason is Iodine release is difficult. The end point is disappearance of blue colour leaving
behind pale green colour.

27
 TITRATION –II

Estimation of Dissolved oxygen

(Tap Water Vs Sodium thiosulphate)

S.No Volume of Burette Readings (ml) Volume of Sodium Concordant

sample water thiosulphate (ml) Value (ml)
Initial Final
(ml)

CALCULATION II:

Volume of Sodium thiosulphate Solution V1 = ml

Strength of Sodium thiosulphate Solution N1 = N (calculation I)

Volume of Water sample V2 = 20 ml

Strength of Water sample (or)

Strength of Dissolved oxygen in water N2 =V1 N1/ V2

N2=

= ---------------- N

Amount of Dissolved oxygen in 1 lit. of sample water

= Eq.Wt of O2 X 1000 X Normality

= 8 x 1000 x ----------- N

= mg / lit

28
REAGENTS REQUIRED:

1. Sodium thiosulphate (0.01N) 2. potassium Iodide 10% 3. potassium dichromate (0.01N),

4.starch 5. dil. H2SO4 6. con.H2SO4 7.manganese Sulphate 8. alkaline potassium iodide 9.
burette, pipette, iodine flask.

PROCEDURE:

TITRATION – I

STANDARDISATION OF SODIUM THIO SULPHATE

Burette is filled with sodium thiosulphate. 20 ml of standard K2Cr2O7 is pipetted out

into a clean conical flask. To this 5 ml of dil. sulphuric acid and 5 ml of 10%
potassium iodide are added. This is titrated against sodium thiosulphate solution. When
the solution becomes straw yellow colour, starch indicator is added and then titration is
continued. The end point is the colour change from blue to light green colour. The titration is
repeated to get concordant value.

ESTIMATION OF DISSOLVED OXYGEN:

100 ml of water sample taken in the iodine flask, 2ml of alkali iodide (KI) and 2 ml of
manganese sulphate solution are added and stoppered. Iodine flask is shaken and kept
for about 20 minutes for setting the precipitate. Then 2-3 drops of con.H2SO4 are added to get
a clear yellow solution due to iodine liberation. 20 ml of this solution is measured in
a measuring jar and transferred to a conical flask. This is titrated with sodium thiosulphate in
the burette. Starch is added nearing the end point. End point is the disappearance of
blue colour. From the titre value the amount of dissolved oxygen in the water sample is
calculated.

RESULT

Amount of DO present in sample water = ------------ mg / lit.

29
 TITRATION –I

Standardisation of EDTA

(Std. NiSO4 Vs EDTA)

S.No Volume of Burette Readings (ml) Volume of Concordant

Std. NiSO4 EDTA (ml) Value (ml)
Initial Final
(ml)

CALCULATION:

Volume of NiSO4 Solution V1 = 20 ml

Strength of NiSO4 Solution N1 = 0.01 N (given)

Volume of EDTA Solution V2 = ml

Strength of EDTA Solution N2 = V1 N1/V2

Strength of EDTA Solution N2 =

N2 =

= N

30
Expt. No. 7 Date:

ESTIMATION OF NICKEL IN AN ALLOY BY COMPLEXOMETRIC

TITRATION

Aim:
To estimate the amount of Nickel present in 1 litre of the given alloy solution. A standard
solution of 0.01N Nickel sulphate and an approximately 0.01N EDTA solution are supplied.

Principle:
Alloys are the mixture of two or more metals. Nickel in alloy can be calculated using a well
known complexing agent Disodium salt of Ethylene Diamine Tetra Acetic acid (EDTA) (Fig.
1). When EDTA is added to metal solution, it forms stable metal complexes. From
the volume of EDTA consumed the amount of metals ions can be calculated. Nickel
can be estimated by using EDTA as titrant and murexide as indicator. Murexide is the
ammonium salt of Purpuric acid. The color change in the direct titration of nickel at pH 8 is
from yellow to bluish violet.

Ni 2+ + Murexide (indicator) Ni- Murexide complex (yellow color)

Ni- Murexide complex (yellow color) + EDTA Ni- EDTA + Murexide

(Bluish violet color)

Murexide form complexes with nickel at pH 8. The pH range can be maintained by adding
ammonical buffer (NH4Cl + NH4OH)

Materials required:
1. EDTA solution 2. Std. Nickel sulphate solution 3. 1M Ammonium chloride solution.
4. ammonia buffer 5. murexide indicator 6. burette, pipette, conical flask

Procedure:

Titration I: Standardization of EDTA

Pipette out 20 ml of standard nickel sulphate solution into a clean conical flask. Add a pinch
of Murexide indicator and 5 ml of buffer solution. The solution becomes yellow colour and it
is titrated against EDTA taken in burette until color changes from yellow to violet.

31
 TITRATION –II

Estimation of Nickel in alloy sample

(Alloy sample Vs EDTA)

S.No Volume of alloy Burette Readings (ml) Volume of EDTA Concordant

sample (ml) (ml) Value (ml)
Initial Final

CALCULATION:

Volume of alloy Solution V1 = 20 ml

Strength of alloy Solution N1 = ?

Volume of EDTA Solution V2 = ml

Strength of EDTA Solution N2 =

N1 =

N1 =
Strength of Nickel alloy solution copper = -------------- N

Amount of Nickel present in given alloy solution

= Eq.Wt of Ni X strength of Nickel in alloy solution

= 58.69 x -----------

= g

32
(Nickel complexes rather slowly with EDTA and consequently EDTA solution must be added
drop wise near the end point.) Repeat the titration to get concordant value. From the strength
of Nickel sulphate solution calculate the strength of EDTA.

Titration II: Estimation of Nickel

Pipette out 20 ml of nickel alloy solution into a clean conical flask. Add a pinch of Murexide
indicator and 5 ml of buffer solution. The solution becomes yellow colour and it is titrated
against EDTA taken in burette until color changes from yellow to violet. Repeat the titration
to get concordant value. Calculate the strength of nickel solution by using strength of EDTA
and amount of nickel present in the given solution.

Result:
The amount of Nickel present in 1 litre of given alloy solution = -------------- g

33
 Fig: pH meter

TABLE – I
Titration of HCl (20 ml) Vs NaOH

S.No Volume of NaOH pH

1. 1
2. 2 Gradual Increase

3. 3
4. 4
5. 5
6. 6
7. 7 Endpoint
8. 8
9. 9
10. 10
11. 11
12. 12 Sudden Increase

13. 13
14. 14

34
Expt No. 8 Date:

pH METRY -DETERMINATION OF STRENGTH OF HCl WITH

NaOH
AIM

To determine the strength and amount of given HCl in 1 lit by pH metry. A standard
solution of NaOH of 0.1 N is provided.

PRINCIPLE
+
pH of a solution is related to H ions concentration by the following formula:

pH = -log [ H+]

Measurement of pH of the solution gives the concentration of H+ ions in the solution. When
+
NaOH is added slowly from the burette to the solution of HCl, the fast moving H ions are
+
progressively replaced by slow moving Na ions. As a result pH of the solution increases.

HCl +NaOH NaCl + H2O

+
The increase in pH takes place until all the H ions are completely neutralized (up to
the end point). After the end point further addition of NaOH increases pH sharply as there is
an excess of fast moving OH-ions.

MATERIALS REQUIRED

(i) pH meter, (ii)glass electrode, (iii) beaker, (iv) standard N/10 NaOH, (v)
approximately N/10 KCl, (vi) burette, pipette, glass rod etc.

PROCEDURE

The burette is filled with standard NaOH solution. Exactly 20 ml of the given HCl
solution is pipetted out into a clean beaker. It is then diluted by adding 20 ml of
distilled water. The glass electrode is dipped in it and connected with a pH meter.

TITRATION- 1

First a preliminary titration is carried out by adding standard NaOH solution in

portions of 1ml from the burette to the HCl solution taken in the beaker and pH of the

35
 TABLE – II
Titration of HCl Vs NaOH

Graph I Graph II

Calculation

Step I: Calculation of strength of HCl

Volume of HCl V1 = 20 ml
Strength of the HCl N1 = ……?
Volume of the NaOH V2 = …..(titre value)
Strength of NaOH N2 = 0.1 N
According to the law of volumetric analysis, V1N1 = V2N2 ; N1 = V2 N2
V1
= …..×….N
20
Strength of HCl present in 1 litre of the given solution = ……. N

Step II: Calculation of amount of HCl

The amount of HCl present in 1 litre of the given solution = N × eq. wt. of HCl (36.5)
= ---------- g

36
solution is noted for each addition. This process is continued until at least 5 readings
are taken after the end point, and the range at which the end point lies is found out by plotting
volume of NaOH added against pH (graph I).

TITRATION – II

Another titration is carried out by adding standard NaOH solution in portions of 0.1 ml
near the end point and pH of the solution is noted after each addition. The addition of
NaOH is continued even after the end point for further 1ml. The accurate end point is formed
by plotting ΔpH/ΔV against volume of NaOH added (graph II). From the end point,
the strength of HCl solution and hence amount of HCl can be calculated.

RESULT
1. Strength of the given HCl solution = …….. N
2. Amount of HCl present in 1 litre of the solution = …… g

37
 Schematic Diagram of Spectrophotometer

Table I

Preparation of various concentration of Fe3+ solution

Volume of Volume of Volume of Volume of distilled Concentration

Sl.
HNO3 NH4SCN H2O (to make equal
no iron solution of iron (ppm)
(ml) (ml) (ml) volume) (ml)

10

38
Expt No. 9 Date:

DETERMINATION OF THE FERRIC ION BY

SPECTROPHOTOMETRIC METHOD

AIM:

To determine the amount of iron content of an unknown solution by spectrophotometry

Principle:

Spectrophotometer is an instrument used to measure the intensity of the light absorbed by a

substance. The relationship between absorbance (A) and the concentration of the solution (C)
is given by Beer-Lambert’s law.

log Io/I = A = εCx

Where

Io = intensity of incident light

I = intensity of transmitted light

ε = absorption co-efficient

x = thickness of the cell

C = concentration of the solution

From the above equation, it is seen that, the absorbance (A) is

directly proportional to the molar concentration (C) and thickness of the cell (x).

In the determination of iron, ferrous iron solution is acidified with HNO3 to

convert Fe2+ into Fe3+. Fe3+ iron does not give any colour in solution. But, it gives blood red
colour when it reacts with potassium thiocyanate (KSCN) or ammonium thiocyanate
(NH4SCN) solution.
Fe3+ + 6NH4SCN  [ Fe(SCN)6]3- + 6NH4+

Complex, blood red colour

39
Graph: Calibration curve (absorbance Vs concentration)

Table II

Measurement of absorbance

Blank (distilled water): zero absorbance; λmax = 480 nm

S. No Concentration (ppm) Absorbance

1 1

2 2

3 3

4 4

5 5

6 6

7 Unknown solution

Amount of iron present in the given solution = --------- ppm (from calibration curve)

40
This complex has maximum absorption in the region, λ = 480 nm. A calibration
curve is drawn by measuring the absorbance of known solution. Then the absorbance
of unknown solution is measured, using which the concentration can be determined from the
calibration curve.

Materials required: 1. Spectrophotometer 2. ferrous ammonium sulphate 3. HNO3 4. 50 ml

standard flask 7 nos 5. graduate pipette 6. ammonium thiocyanate

Procedure:

1. Preparation of stock Fe3+ iron solution

A stock solution of Fe3+ is prepared by dissolving 0.0838 gms of ferrous ammonium sulphate
with 1 ml of conc. HNO3 in 1 litre of distilled water.

1 ml of stock solution = 10 ppm of iron

From the stock solution, various concentrated (1, 2, 3, 4, 5 & 6 ppm) (Table 1) solutions are
prepared.

2. Determination of iron content

The spectrophotometer is switched on and warmed up for 10 minutes. The monochromator is

adjusted for λ = 480 nm.

The blank solution (distilled water) is kept in the cell and absorbance is measured for which
the absorbance is zero and transmittance is 100.

Now the absorbance of all the standard solutions is similarly measured. Also the absorbance
of unknown solution is measured (Table II).

The calibration graph is drawn between the concentration and absorbance from which
the concentration of unknown solution measured.

Result:

Amount of iron present in the solution = ……….ppm

41