Practical Book On Engineeirng Chemistry

PRACTICAL BOOK ON
ENGINEERING CHEMISTRY
(CH 191 and CH 291)
For B.Tech, BE
As per New Revised Syllabus of WBUT
Dr. Pijus Kanti Khatua

M. Sc., Ph. D
Department of Applied Science
Haldia Institute of Technology
Haldia, West Bengal
Debashree Singh
M. Sc.
Department of Applied Science
Haldia Institute of Technology
Haldia, West Bengal
2
i
Preface
Purpose and Structure of the Book
This book provides a comprehensive, thorough, and up-to-date application of Practi-
cal Book on Engineering Chemistry(CH-191 and CH-291) as per West Bengal
University of Technology - WBUT. Endeavour has made to cover the syllabus exhaus-
tively and present the subject matter in a systematic and lucid manner. More than 100
Short and long answer type questions have been incorporated in the text book for better
understanding of the students and better representation during viva-voce. Most of the
question has been taken from both theory and practical related WBUT, which should
take students familiar with the standard and trend of questions set in the examinations.
General Features of the Book Include:

• Simplicity of presentation of experiments
In teaching-learning process to make the book easily teachable and readable, why
choose complicated examples when simple ones are as instructive or even better.
• Independence of parts and blocks of chapters
to provide flexibility in tailoring courses to specific needs.
• Self-contained presentation
All formula, structures, grafics, figures are placed where it is exactly needed would
exceed the level of the book and a reference is given instead.
• Contain huge number of question answer
To ensure an enjoyable teaching and learning huge number of question and answer
has included that will help not only for knowledge gathering as well as for viva-voce
also.
Furthermore, we designed the book to be a single, self-contained, authoritative,
and convenient source for studying and teaching laboratory engineering chemistry,
eliminating the need for time-consuming searches on the Internet or time-consuming
trips to the library to get a particular reference book.
In written this book I have been help from several books in the bibliography. So, I
acknowledgement them gratefully.
We express our sincerest gratitude to our Prof. Subhash Chandra Bhattacharya, Prof.
Nitin Chattopadhaya, Jadavpur University and specially Dr. Dipak Kumar Jana, Mr.
Anupam De of HIT for their constant encouragement.
We also thank our collogues: , Dr. Dipak Kumar jana for their constant inspiration also
Mr.Sibaprasad Maity, Dr.Gora Das, Dr. Suparna Rana, Dr. Dipankar Pramanik, Dr.
Diptanshu Chakraborty, Dr. Santanu Mishra and Dr. Rajib Kumar Dubey for their
constant cooperation.
We feel great for receive from our parents, family members, relatives for their blessings
and being a constant source of inspiration.
We shall feel great to receive constructive criticisms for the improvement of the book
from the experts as well as the learners.
ii
We thank the Platinum Publishers, Kolkata for their sincere care in the publication of
the book.
P. K. Khatua
pkkjuchem@yahoo.co.in
D. Singh
debashree.15@redif f mail.com
iii
Syllabus
Practical Book on Engineering Chemistry
For CH-191(ICE, AEIE, EE, ECE)
and CH-291(ME, PE, CHE, CE, CSE, ITE, BTE FTE)
CONTENTS
Topic:
1. To Determine the alkalinity in a given water sample
2. Red ox titration (estimation of iron using permanganometry)
3. To determine calcium and magnesium hardness of a given water sample separately
4. To determine the value of the rate constant for the hydrolysis of ethyl acetate catalyzed by
hydrochloric acid
5. Heterogeneous equilibrium (determination of partition coefficient of acetic acid between n
butanol and water)
6. Viscosity of solutions (determination of percentage composition of sugar solution from viscos-
ity)
7. Conductometric titration for determination of the strength of a given HCl solution by titration
against a standard NaOH solution.
8. pH metric titration for determination of strength of a given HCl solution against a standard
NaOH solution
9. Determination of dissolved oxygen present in a given water sample
10. To determine chloride ion in a given water sample by Argentometric method (using chromate
indicator solution)
iv
Contents
1 Experiment name: To Determine the alkalinity in a given water sample 1

1.1 Aim of experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.3 Chemicals required . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.9 Question for viva-voce . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2 Experiment name: Redox Titration- Estimation of iron(gm/lit)in supplied

Mohr salt solution by permanganomerty 17
2.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3 Chemicals Required . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.4 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3 Experiment name:Complexometric Titration (Estimation of Calcium and Mag-

nesium Hardness separately using EDTA Titration) 25
3.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.4 Apparatus Required . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.7 Precuation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4 Experiment name:To determine the value of the rate constant for the hydrol-
ysis of ethyl acetate catalyzed by hydrochloric acid 37
4.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
v
vi CONTENTS

4.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5 Heterogeneous equilibrium (determination of partition coefficient of acetic

acid between n-butanol and water) 49
5.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
5.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
6 Experiment name:Viscosity of solutions (determination of percentage compo-

sition of sugar solution from viscosity) 57
6.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
6.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
6.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
7 Experiment name:Conductometric titration for determination of the strength

of a given HCl solution by titration against a standard NaOH solution. 67
7.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
7.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
7.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
7.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
7.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
8 Experiment name:. pH-metric titration for determination of strength of a

given HCl solution against a standard NaOH solution. 81
8.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
8.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
CONTENTS vii
8.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
8.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
8.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
9 Determination of dissolved oxygen present in a given water sample 91

9.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
9.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
9.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
9.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
10 Experiment name:To determine chloride ion in a given water sample by Ar-

gentometric method (using chromate indicator solution) 99
10.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
10.5 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
10.6 Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
10.7 Precaution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
10.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
11 Important general question for viva-voce 109
12 Different essential tables 117
13 Some important figures 119
14 Some important equipments and apparatus 125

viii CONTENTS
Chapter 1
Experiment name: To Determine

the alkalinity in a given water
sample
1.1 Aim of experiment

( determination of the alkalinity of given water sample)
1.2 Theory
Alkalinity is a measure of the capability of water to absorb H+ ions without significant change
of pH. In other words, alkalinity is a measure of the acid buffering capacity of water. The
determination of alkalinity of water is necessary for controlling the corrosion, to calculate the
amount of lime and soda needed for water softening; in conditioning the boiler feed water, etc.
Alkalinity of a sample of water is due to the presence of OH- (hydroxide ion), HCO-3 (bicarbonate
ion) and CO2- 3 (carbonate ion) or the mixture of two ions present in water. The possibility of
OH and HCO-3 ions together is not possible since they combine together to form CO2-
-
3 ions.
OH- + HCO-3 → CO2-

3 + H2 O
The alkalinity due to different ions can be estimated separately by titration against standard
acid solution, using selective indicators like phenolphthalein and methyl orange.
i) OH- + H+ → H2 O
ii) CO2- +
3 + H → HCO3
-
iii) HCO-3 + H+ → H2 O + CO2
The neutralization reaction upto phenolphthalein end point shows the completion of reactions (i)
and (ii) (OH- and CO2- 2- -
3 ) and (CO3 and HCO3 ) only. The amount of acid used thus corresponds
to complete neutralization of OH- plus half neutralization of CO2-
3 . The titration of water sample
using methyl orange indicator marks the completion of the reactions (i), (ii) and (iii). The amount
of acid used after phenolphthalein end point corresponds to one half of normal carbonate and all
1
2 CHAPTER 1. DETERMINE THE ALKALINITY IN A GIVEN WATER
the bicarbonates. Total amount of acid used represent the total alkalinity due to all ions present
in water sample.
1.3 Chemicals required

1.3.1. Dry Na2 CO3
1.3.2. Concentrated 12(N) HCl
1.3.3. Phenolphthalein and methyl orange indicator
1.4 Apparatus
1.4.1. Distilled water
1.4.2. Burette
1.4.3. Pipette
1.4.4. Conical flask
1.4.5. Volumetric flask
1.4.6. Measuring cylinder
1.4.7. Beakers
1.5 Procedure
³ ´
1.5.1. Preparation of Std. Na2 CO3 10 N solution:
³ ´
Equivalent weight of Na2 CO3 is 53. Hence in order to prepare 250 ml of 10 N solution,
1.325 gm Na2 CO3 is required. Weight out 1.325 gm of AR quality oxalic acid into a clean
250 ml volumetric flask. Wash the entire quantity of solid into the flask by careful addition
of distilled water. Hold the flask firmly and shake carefully. When the entire solid has
dissolved, makeup the volume to the mark.
Let the weight of oxalic acid taken = W gm.
Strength of oxalic acid
µ ¶
W N
= ×
1.325 10
.
Table 1.1: Weighing of Na2 CO3

Initial Final Weight Weight to be Strength
³ ´
weight(gm) weight(gm) taken(gm) taken(gm) N
10
- - - 1.325 -
1.5.2. Preparation of 250 ml of HCl solution:

Take 2.08 ml of concentrated HCl and mix with 248 ml of distilled water to make the
solution 250 ml. Then mix the solution properly.
1.5. PROCEDURE 3
1.5.3. Standardization of HCl solution by primary standard Na2 CO3 solution:

Pipette out 10 ml of Na2 CO3 solution³ ´in a conical flask, add 2 drops of methyl orange
N
indicator, fill up the burette with 10 HCl solution and titrate till the color of the
solution changes from yellow to red.
Table 1.2: Standardization of HCl solution by standard Na2 CO3 solution

No. Volume Burette reading of Volume Strength Strength
of of HCl solution(ml) of of of
observation Na2 CO3 HCl Na2 CO3 HCl
(ml) Initial Final (ml) (N) (N)
1. - - - - - -
2. - - - - - -
3. - - - - - -
4. - - - - - -
Let, the strength of HCl = S2

As we know,
V1 × S1 = V2 × S 2
Therefore,
V1 × S1
S2 = × (N)
V2
Here,
V1 = Volume of standardNa2 CO3 solution

S1 = Strength of standard Na2 CO3 solution
V2 = Volume of HCl solution
S2 = Strength of HCl solution
1.5.4. Analysis of water sample:

i) Pipette 20 ml of the sample of water into a 100 ml
³ conical
´ flask and 2 drops of phenolph-
N
thalein indicator was added and titrated against 10 HCl till the color of the solution
changes from pink to colorless. Corresponding burette reading indicates the phenolph-
thalein end point (V1 ).
ii) Again pipette out 20 ml of the water sample in a conical flask, add 2 drops of methyl
orange
³ ´ indicator. Color of the solution becomes yellow. Continue the titration against the
N
10 HCl solution till the color changes to red. This burette reading corresponds to the
methyl orange end point (V2 ).
Table 1.3: Analysis of water using phenolphthalein indicator

No. Volume Burette reading of Volume Mean volume Strength
of of sample HCl solution(ml) of HCl of HCl of
observation taken required required HCl
V3 (ml) Initial Final (ml) V4 (ml) (S2 )(N)
1. 20 - - - - -
2. 20 - - - - -
3. 20 - - - - -
4. 20 - - - - -
5. 20 - - - - -
Table 1.4: Analysis of water using methyl orange indicator

No. Volume Burette reading of Volume Mean volume Strength
of of sample HCl solution(ml) of HCl of HCl of
observation taken required required HCl
V5 (ml) Initial Final (ml) V6 (ml) (S2 )(N)
1. 20 - - - - -
2. 20 - - - - -
3. 20 - - - - -
4. 20 - - - - -
1.6 Calculation
1.6.1. Phenolphthalein alkalinity
As we know,
V3 × S3 = V4 × S 2
Therefore,
V4 × S2
S3 = × (N)
V3
Here,
V3 = Volume of water sample taken = 20ml
S3 = Strength of phenolphthalein alkalinity in water sample
V4 = Mean volume of HCl solution
So, Strength in terms of CaCO3 equivalent
= S3 × Eq. Wt of CaCO3
V4 × S2
= × 50 (g/L)
20
= A (say) (g/L)
Therefore, Phenolphthalein alkalinity (P) = A × 1000 mg/L
1.6.2. Methyl orange alkalinity
As we know,
V5 × S4 = V6 × S 2
1.7. PRECAUTION 5
Therefore,
V4 × S2
S3 = × (N)
V3
Here,
V5 = Volume of water sample taken = 20 ml

S4 = Strength of methyl orange alkalinity in water sample
V6 = Mean volume of HCl solution
So, Strength in terms of CaCO3 equivalent
= S4 × Eq. Wt of CaCO3
V5 × S2
= × 50 (g/L)
20
= B (say) (g/L)
Therefore, methyl orange alkalinity (M) = B × 1000 mg/L
1.7 Precaution
1.7.1. All the glass apparatus should be washed thoroughly with distilled water before use
1.7.2. The burette and pipette should be rinsed with solution to be taken in it.
1.7.3. There should not be any leakage in the burette.
1.7.4. The conical flask should be placed on white paper or board to identify the color change
at the end point
[N.B.: During writing precaution write your own passive voice.]
1.8 Conclusion
The results are reported using the following five different parameters:
1.8.1. Phenolphthalein alkalinity (P) = 0; that means the volume of acid used till the completion
of reaction (i) and (ii) is 0. This can only happen when both OH- and CO2- 3 ions are not
present in water. Alkalinity is present due to HCO-3 ion only which can be determined
using methyl orange indicator and called methyl orange alkalinity (M).
1.8.2. P = 12 M; indicates that only CO2- 3 ions are present. Using phenolphthalein indicator
-
neutralization reaches upto HCO3 but using methyl orange indicator the complete neu-
tralization of HCO-3 takes place.
1.8.3. P > 12 M; implies OH- ions are also present along with CO2-3 ions. Upto phenolphthalein
alkalinity OH ions will be neutralized completely where as CO2-
-
3 will be neutralized upto
HCO-3 ion. But using methyl orange indicator HCO-3 will be completely neutralized along
with OH- and CO2- 3.
1.8.4. P < 12 M; indicates that beside CO2- -

3 ions HCO3 ions are also present. The volume of
acid required for the neutralization upto phenolphthalein end point correspond half neu-
tralization of CO2-
3 . Neutralization using methyl orange indicator corresponds to HCO3
-
obtained from CO2- -
3 and HCO3 originally present in the water sample.
1.8.5. P = M; indicates only OH- ions are present.
1.9 Question for viva-voce

1.9.1. What is oxide? How many types of oxide present? Give example.
Ans. The binary compound of any element with oxygen is called. e.g.CO2 , ZnO2 , CaO,
NO.During writing formula the other element except oxygen should written first then
oxygen and we should use the term ”oxide” e.g. carbon dioxide, zinc oxide, calcium oxide,
nitric oxide etc. On the basis of properties oxides are classified mainly into four parts:
a) Acidic oxide
b) Basic oxide
c) Amphoteric oxide
d) Neutral oxide
e) Per Oxide
f) Mixed oxide
g) Poly oxide
h) super oxide
i) sub oxide.
Acidic oxide: The non-metallic oxide which react with alkali or base or basic oxide pro-
duce salt and water are called acidic oxide. Example CO2 , SO2 , NO2 .
b) Basic oxide: The metallic oxide which react with acid or acidic oxide produce salt
and water are called basic oxide. Example Na2 O, K2 O, CaO,MgO.
c) Amphoteric oxide: Oxides which have both acidic and basic properties are called
amphoteric oxide. Example Al2 O3 , PbO, ZnO.
d) Neutral oxide: Oxides which does not have both acidic and basic properties and
those oxides do not react with acid or base are called neutral oxide. Example CO3 , NO,
H2 O.
e) Per oxide: Oxides which have more oxygen than normal oxides produce hydrogen
peroxide when react with cold and dilute acid or more clearly which have peroxide group(-
O-O-)called peroxide. Example Na2 O2 , BaO2 .
f ) Mixed oxide: Oxides which produce by the combination of oxides of same or differ-
ent metal. Example Fe3 O4 (mixture of FeO and Fe2 O3 ), Mn3 O4 (mixture of MnO and
Mn2 O3 ), Pb3 O4 (mixture of PbO and PbO2 ),
g) Poly oxide: Oxides which have more oxygen than normal oxides do not produce hy-
drogen peroxide when react with cold and dilute acid called poly oxide. Example KO2 ,
PbO2 .
h) Super oxide: Impure oxides which have more oxygen than normal oxides produce
hydrogen peroxide and oxygen during hydrolysis or more clearly which have superoxide
group(O-O)called peroxide. Example KO2
i) Sub oxide: Oxides which have less oxygen than normal oxides called suboxide. Ex-
ample C3 O2 .
1.9.2. What is Acid?

Ans. The hydrogen containing compounds which dissociate in water give H3 O+ ion and
the hydrogen atom of those compounds are replaced partly or completely by metal or
1.9. QUESTION FOR VIVA-VOCE 7
metal like substances produce salt and water, called acid. Example HCl, H2 SO4 , HNO3 .
1.9.3. What is base?

Ans. The Metallic oxides or hydroxides or group of elements which reacts with acid
produce salt and water, called base. Example NaOH, CaO, Al(OH)3 , Zn(OH)2 , Fe(OH)3 .
1.9.4. What is alkali?

Ans. Base (Metallic oxides or hydroxides or group of elements) which dissolve and dissoci-
ate in water give OH- ion, reacts with acid produce salt and water, called alkali. Example
NaOH, CaO, KOH are alkali as well as base. Al(OH)3 , Zn(OH)2 , Fe(OH)3 these com-
pounds are base but these compounds are not soluble in water as a result are not alkali.
1.9.5. Give the Arrhenius, Born Stead and Lowry concept of acid and alkali.
Ans. The Arrhenius concept of acid base depends on mainly electrolytic-dissociation. Ac-
cording to this electrolytic-dissociation theory acids are those hydrogen containing com-
pounds which dissociate in water give H3 O+ ion. Example HCl, H2 SO4 , HNO3 and
alkalis are those compounds which dissolve and dissociate in water give OH- ion, . Exam-
ple NaOH, Ca(OH)2 , KOH.
1.9.6. All alkalis are base but reverse is not true- explain.
Ans. The Metallic oxides or hydroxides or group of elements which reacts with equivalent
amount of acid whose metal ion replace hydrogen atom of acid produce salt and water,
called base. Example NaOH, CaO, Al(OH)3 , Zn(OH)2 , Fe(OH)3 . Bases (Metallic oxides
or hydroxides or group of elements) which dissolve and dissociate in water give OH- ion,
called alkali. Example NaOH, KOH are alkali as well as base. CaO, MgO are metallic
oxides which dissolve and dissociate in water give OH- ion so, these are base as well as
alkali. On the other hand Al(OH)3 , Zn(OH)2 , Fe(OH)3 these compounds are base but
these compounds are not soluble in water as a result are not alkali. For this reason it is
called all alkalis are base but reverse is not true.
1.9.7. What is hydroxide?

Ans. The hydroxides are oxides of metal or metal like substances which may or may not
dissolve and dissociate in water. Example NaOH, KOH.
1.9.8. Give some examples of base which does not contain any metal?
Ans. Examples are Ammonia (NH3 ), Pyridine(C5 H5 N), Methyle ammine (CH3 NH2 ).
1.9.9. How water becomes alkaline?

Ans. The Metallic oxides or hydroxides or group of element like carbonate, bicarbonate,
silicates and some other salts which dissolve and dissociate in water give OH- ion or re-
spective anion make water alkaline. Example NaOH, KOH CaO, MgO,Na2 CO3 , NaHCO3
are metallic hydroxide and oxides which dissolve and dissociate in water give OH- ion and
make water alkaline.
1.9.10. Describe strong base weak base. Give example.

Ans. Strong base: Base which dissolve and completely dissociate in water called strong
bases as a result in solution concentration of OH- ion is maximum. Examples NaOH, KOH
CaO, MgO.
Weak base: Bases which dissolve slightly, incompletely dissociate in water and the ions
remain in equilibrium with undissociated base called weak bases as a result in solution
concentration of OH- ion is minimum. Examples NH4 OH, Cu(OH)2 .
1.9.11. What is acidity of base?

Ans. Acidity of base is the power of that base by which it replaces the hydrogen atom
from that acid. In a word it is the number of hydrogen atom that is replaced by metal
or metal like element of base. Examples NaOH, KOH have basicity one CaO, MgO have
basicity two.
1.9.12. Describe different types of expression for strength of base.

Ans. Different types of expression for strength of base are
a) Monoacidic base, it replaces one hydrogen atom from the acid. Example NaOH, KOH.
b) Diacidic base, it replaces two hydrogen atom from the acid. Example Ca(OH)2 ,
Mg(OH)2 .
c) Triacidic base, it replaces three hydrogen atom from the acid. Example Al(OH)3 ,
Fe(OH)3 .
1.9.13. Describe different types of alkalinity.

Ans. There are mainly three types of alklinity
a) hydroxides alklinity.
b) carbonate alklinity.
c) bicarbonate alklinity.
1.9.14. What will happen when same concentrations of NaOH and NaHCO3 solution are mixed?
Ans. As NaHCO3 solution is acidic salt or bi-salt it reacts with equivalent amount of
NaOH form neutral salt. NaHCO3 + NaOH → Na2 CO3 + H2 O
1.9.15. What is neutralization reaction?

Ans. Equivalent amount of an acid react completely with exactly equivalent amount of
base produce salt and water is called neutralization reaction. HCl+NaOH → NaCl+H2 O.
1.9.16. What is titration?

Ans. The process of determination of unknown strength of any solution with the help
of known strength of other solution by using neutralization reaction is called titration
As we know,
V1 × S1 = V2 × S 2
Therefore,
V1 × S1
S2 = × (N)
V2
Here,
V1 = Volume of standard solution
S1 = Strength of standard solution
V2 = Volume of unknown strength of any solution
S2 = Strength of unknown strength of any solution
1.9.17. Give the principle of acid base titration.

Ans. Equivalent amount of an acid react completely with exactly equivalent amount of
base produce salt and water is called neutralization reaction. The process of determination
of unknown strength of any solution with the help of known strength of other solution by
using neutralization reaction is called titration.
Let us consider a titration reaction among known strength of oxalic acid with unknown
strength of NaOH
As we know,
VA × SA = VB × S B
Therefore,
VA × SA
SB = × (N)
VB
Here,
VA = Volume of standard oxalic acid solution

SA = Strength of standard oxalic acid solution
VB = Volume of unknown strength of sodium hydroxide solution
SB = Strength of unknown strength of sodium hydroxide solution
1.9.18. What is indicator?

Ans. The small amount of specific chemical compound which indicate the end point or
neutralisation point by change in its colour with the variation of pH value of the solution
during volumetric analysis is called indicator. Example a) Phenolphthalein, b) Phenolph-
thalein and c) Litmus paper.
1.9.19. What is indicator action?

Ans. Any acid base indicator or pH indicator is either weak organic acid or base. The
unionised compound has one colour and the ion produced by its dissociation has another
colour. In general, for acid base indicators equilibrium may be expressed as-
HIn(Colour I) ¿ H+ + In− (Colour II)
Its equilibrium constant is given by:
[H+ ][In- ]
KIn =
[HIn]
[KIn ][HIn]
[H+ ] =
[In- ]
[HIn]
log[H+ ] = log[KIn ] + log
[In- ]
[HIn]
pH = pKIn + log -
[In ]
Where,
KIn = indicator constant and −logKIn = pKIn
Consider the above equilibrium, if the solution is acidic, the increase in − H+ ion concen-
tration shifts the equilibrium towards left and hence the colour will be due to the unionised
molecule(HIn). On the other hand, if the solution is alkaline, then − H+ ion will be taken
up by − OH- ions. The decrease in concentration of − H+ ion shifts the equilibrium
towards right and more of the indicator will ionise. Hence the colour of the solution will
be due to − In- . Thus the indicator has one colour in the acidic solution and different
colour in the alkaline solution. In any given solution, the actual colour depends upon the
ratio, [HIn ]
- .
[In ]
1.9.20. Give name of different kinds of acid base indicator and their colour change in acid base
medium.
Ans. Different kinds of acid base indicators are-
a) Phenolphthalein
b) Methyl orange
c) Bromophenol blue
d) Methyl red
e) Phenol red
f) Thymolphthalin blue
Indicator pH range Color in acid solution Color in alcaline solution

Thymol blue(acid) 1.2 - 2.8 Red Yellow
Bromophenol blue 3.1 - 4.6 Yellow Purple
Methyl orange 3.1 - 4.5 red Yellow
Methyl red 4.2 - 6.3 Red Yellow
Bromothymol blue 6.0 - 7.6 Yellow Blue
Phenol red 6.4 - 8.2 Yellow Red
Cresol red(base) 7.0 - 8.1 Yellow Red
Thymol blue(base) 8.1 - 9.6 Yellow Blue
Phenolphthalein 8.0 - 9.8 Colorless Pink
Thymolphthalin blue 9.3 - 10.5 Colorless Blue
1.9.21. What is selection of indicator- explain.

Ans. On the basis of their pH range, the indicators which can be used in acid-alkali
titrations are:
Sl. No. Type of titration Suitable pH indicator
1. Strong acid Vs. Strong base Any indicator
2. Weak acid Vs. Strong base Phenolphthalein
3. Strong acid Vs. Weak base Methyl orange or methyl red
4. Weak acid Vs. Weak base No indicator is satisfactory
1.9.22. What will happen when Methyl orange and Phenolphthalein solution are separately added
to 10 ml 1(N) sodium carbonate solution and titrate against 1(N) HCl solution?
Ans. The reaction between sodium carbonate solution and HCl solution is given below:
Na2 CO3 + HCl = NaHCO3 + NaCl

NaHCO3 + HCl = NaCl + H2 O
We see it is a two step reaction. Phenolphthalein indicator show its color change and indi-
cate the end point after 1st step(half neutralization)reaction hare the solution is alkaline
(as it shows its color change at pH 8.0 - 9.8). Not second step reaction. According to the
reaction to complete half neutralization reaction we need 5 ml. of 1(N) HCl solution but
methyl orange show its color change after completion of full neutralization reaction that
ultimate solution become acidic(as it shows its color change at pH 3.1 - 4.5)
1.9.23. Calculate the phenolphthalein and total alkalinity of a 40 ml water sample required 10.6
M H SO to reach the end point by Phenolphthalein indicator and 30.4 ml M H SO
ml 50 2 4 50 2 4
by methyl orange indicator.
Ans. From equivalent point I(by Phenolphthalein indicator), require volume of acid 10.6
ml and for equivalent point II(by methyl orange indicator), require volume of acid 30.4 ml
So, it is clear that equivalent point II > equivalent point I but equivalent point I6=0
Therefore, bicarbonate and carbonate ions are present in the water sample.
Now, 10.6 ml. required for phenolphthalein alkalinity.
So, phenolphthalein alkalinity
100
= × V × (M) gm of CaCO3 per 40 ml. of water sample.
1000
1 M
= × 10.6 × ( ) gm of CaCO3 per 40 ml. of water sample
10 50
= 0.0212 gm of CaCO3 per 40 ml. of water sample
= 0.0212 gm × 1000 mg of CaCO3 per 40 ml. of water sample
= 21.2 mg of CaCO3 per 40 ml. of water sample
= 530 mg of CaCO3 per litre of water sample
Now, 30.4 ml. required for methyl orange alkalinity. So, 10.6 + 30.4 = 41 ml. required
for total alkalinity. So, total alkalinity
100
= × V × (M) gm of CaCO3 per 40 ml. of water sample
1000
1 M
= × 41 × ( ) gm of CaCO3 per 40 ml. of water sample
10 50
= 82 mg of CaCO3 per 40 ml. of water sample
1.9.24. 100 ml of a water sample require 10 ml 50 M H SO to reach the end point by using methyl
2 4
orange indicator but shows no colour change with Phenolphthalein. Comment about the
alkalinity and find the amount.
Ans. From equivalent point I(by Phenolphthalein indicator), require volume of acid = 0.0
ml. and for equivalent point II(by methyl orange indicator), require volume of acid = 10
ml. So, it is clear that equivalent point II > equivalent point I but equivalent point I = 0
Therefore, only bicarbonate ions are present in the water sample.
Now, 10 ml. required for methyl orange alkalinity. So, only bicarbonate alkalinity = total
alkalinity
100
= × V × (M) gm of CaCO3 per 100 ml. of water sample
1000
1 M
10 50
M H SO as titrant to reach the end point by using

1.9.25. A water sample is treated with 50 ml 50 2 4
Methyl orange and Phenolphthalein. Calculate carbonate and bicarbonate alkalinity in
the sample.
Sample Require volume of titrant Require volume of titrant

No. to reach the end point by to reach the end
using Phenolphthalein(ml) pointby using Methylorange(ml)
1. 5 7.75
2. 0 6.35
3. 4.1 4.1
Ans. Sample No.1: From equivalent point I(by Phenolphthalein indicator), require
volume of acid = 5 ml. and for equivalent point II(by methyl orange indicator), require
volume of acid = 7.75 ml. So, it is clear that equivalent point II > equivalent point I but
equivalent point I 6= 0
Therefore, bicarbonate and carbonate ions are present in the water sample.
Now, 5 ml. required for phenolphthalein alkalinity.
So, 2 times equivalent point I = 2 × 5 = 10 ml. required for carbonate alkalinity
So, carbonate alkalinity
100
= × V × ( M ) gm of CaCO3 per 50 ml. of water sample
1000
1 M
10 50
Now, Bicarbonate alkalinity = equivalent point II(by methyl orange indicator) - equivalent
point I (by Phenolphthalein indicator) = 7.75 -5 =2.75 ml.
So, bicarbonate alkalinity
100
1000
1 M
10 50
= 0.0055 × 1000 mg of CaCO3 per 50 ml. of water sample
= 110 mg of CaCO3 per litre of water sample.
Sample No.2: From equivalent point I(by Phenolphthalein indicator), require volume of
acid = 0.0 ml. and for equivalent point II(by methyl orange indicator), require volume of
acid = 6.35 ml. So, it is clear that equivalent point II > equivalent point I but equivalent
point I = 0
Therefore, only bicarbonate ions are present in the water sample.
Now, 10 ml. required for methyl orange alkalinity. So, bicarbonate alkalinity
100
1000
1 M
10 50
Sample No.3: From equivalent point I(by Phenolphthalein indicator), require volume of
acid = 4.1 ml. and for equivalent point II(by methyl orange indicator), require volume of
acid = 4.1 ml. So, it is clear that equivalent point II = equivalent point I
Therefore, only carbonate ions are present in the water sample.
Now, for total alkalinity = Phenolphthalein alkalinity + methyl orange alkalinity = 4.1 +
4.1 = 8.2 ml. So, carbonate alkalinity
100
1000
1 M
10 50
1.9.26. What effects occur by alkaline water in different corners of industry?

Ans. Water Is a polar solvent as well as universal solvent. For this unique character water
is used in different corner of daily life and in industry also for washing clothes in laundry,
boiler and to prepare medicine, aqueous based resin adhesives. Water required for those
purpose are highly pH sensitive. Alkaline water having higher pH than pure water so, it
undergoes many reactions and creates major problems.
1.9.27. What is the importance of this experiment in the aspect of engineering?

Ans. In the basic engineering (like Mechanical, Chemical, electrical, Civil)application we
need to deal water in a boiler, paper, cotton, polymer as well as concrete preparation. It
is essential and mandatory to know the alkalinity of water. Knowledge of this experiment
will help us to determine the alkalinity of water sample and if the alkalinity of water is
out of tolerance then it should be removed from water by any chemical treatment.
1.9.28. Give the chemical formula and structures of different acid base indicator.
Ans. Phenolphthalein is a chemical compound with the formula C20 H14 O4 and is
often written as ”HIn” or ”phph” in shorthand notation. Often used in titrations, it turns
colorless in acidic solutions and pink in basic solutions. If the concentration of indicator
is particularly strong, it can appear purple. In strongly basic solutions, phenolphthalein’s
pink color undergoes a rather slow fading reaction and becomes completely colorless above
13.0 pH.
IUPAC name: 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one.
Molecular formula: C20 H14 O4
Structure of Phenolphthalein
Phelophththalein in acid and base
Methyl orange is a pH indicator frequently used in titrations. It is often used in titrations

because of its clear and distinct colour change. Because it changes colour at the pH of a
mid-strength acid, it is usually used in titrations for acids. Unlike a universal indicator,
methyl orange does not have a full spectrum of colour change, but has a sharper end point.
IUPAC name: Sodium 4-[(4-dimethylamino)phenyldiazenyl]benzenesulfonate.
Molecular formula: C14 H14 N3 NaO3 S
Structure of Methyl orange
Methyl Orange in acid and base

Chapter 2
Experiment name: Redox

Titration- Estimation of
iron(gm/lit)in supplied Mohr salt
solution by permanganomerty
(Estimation of Iron(gm/lit)in supplied Mohr salt solution by Using Permanganometry)
2.2 Theory
In a chemical reaction, if one substance is oxidized the other is reduced. In other words, oxidation
and reduction occurs simultaneously. Oxidation is defined as the process of one or more electrons
and reduction is the gain of electron or electrons by atoms or ions. The reagents undergoing
reduction is called oxidizing agent (oxidant), the reagent which undergoes oxidation is called
reducing agent (reductant). In a redox titration, a reducing agent is titrated against an oxidizing
agent or vice-versa. In this titration, potassium permanganate is the commonly used oxidizing
agent which is titrated against a reducing agent like ferrous ammonium sulfate.
Potassium permanganate oxidizes ferrous ion into ferric ion in acid medium in cold for its higher
standard reduction potential and is itself reduced to colorless manganous ion. But with decrease
in H+ conc. i.e. increase in pH of the medium, the potential falls and the oxidizing power
decreases.
Reduction half cell reaction; MnO-4 + 8H+ + 5e- → Mn+2 + 4H2 O
Oxidation half cell reaction; 5Fe+2 → 5Fe+3 + 5e-
Overall reaction; MnO-4 + 8H+ + 5Fe+2 → Mn+2 + 4H2 O + 5Fe+3
Reduction potentials for
17
18 CHAPTER 2. REDOX TITRATION
MnO-4 → Mn+2 ; E0 = 1.51 Volt

5Fe+3 → 5Fe+2 ; E0 = 0.77 Volt
1
Cl → Cl- ; E0 = 1.36 Volt
2 2
Permanganate also oxidizes Cl- present in the medium to Cl2 . So, excess MnO-4 is consumed.
To prevent this the titration is carried out in presence of Zimmermann- Reinhardt (Z.R)solution
consisting of MnSO4 , H3 PO4 and H2 SO4 .
Function of MnSO4 :
It supplies excess of (M n)+2 ; as a result the formal potential of MnO-4 /Mn+2 system falls below
1.36 V ; consequently MnO-4 can no longer oxidise Cl- to Cl2 .
0.059 Mn+2
E = E0 − log
5 MnO-4 × [H+ ]8
0.059 Mn+2
E = E0 − log
n MnO-4
Function of H3 PO4 :
It removes yellow F e+3 by forming colourless soluble complex ion, [Fe(HPO4 )]+ ;as a result
(i) the standard reduction potential of Fe+3 /Fe+2 system decreases and the formal potential
falls below 0.77 V to permit quantitative oxidation of Fe+2 by MnO-4 ,
(ii) sharp detection of the end point becomes possible.
Function of H2 SO4 :
It maintains the proper acidity of the solution and thereby prevents the precipitation of Man-
ganese phosphate in the Z.R. solution.
2.3 Chemicals Required

2.3.1. Dilute sulfuric acid
2.3.2. Ferrous ammonium sulfate solution (NH4 )2 SO4 .FeSO4 .6H2 O
2.3.3. Given (KMnO4 ) solution
2.3.4. Zimmermann Reinhardt solution (MnSO4 + conc.H2 SO4 + H3 PO4 )
2.4 Apparatus
2.4.2. Burette
2.4.3. Pipette
2.4.7. Beakers
2.5. PROCEDURE 19
2.5 Procedure
2.5.1. Preparation of Std. oxalic acid solution ³ ´
N solution,
Equivalent weight of oxalic acid is 63. Hence in order to prepare 250 ml of 10
1.575 gm oxalic acid is required. Weight out 1.575 gm of AR quality oxalic acid into a
clean 250 ml volumetric flask. Wash the entire quantity of solid into the flask by careful
addition of distilled water. Hold the flask firmly and shake carefully. When the entire
solid has dissolved, makeup the volume to the mark.
µ ¶
W N
= ×(
1.575 10
Table 2.1: Weighing of oxalic acid

³ ´
10
- - - 1.575 -
2.5.2. Determination of strength of given Potassium permanganate solution

Take 5 ml of oxalic acid solution in a conical flask. Add 30 ml of 2(N)H2 SO4 . Heat
to about 800 C. Run in the permanganate solution, with constant stirring and see that
the temperature of the solution may not fall below 600 C during titration. Stop addition
of KMnO4 solution when just one drop imparts pink colour to the whole mass of the
solution. Note that the pink colour after lasting for 30 seconds may disappear again. Note
the volume of KMnO4 solution added. Repeat the titration thrice at least.
Table 2.2: Determination of strength of KMnO4 solution

No. Volume of Burette reading of Volume Strength Strength
of oxalic KMnO4 solution(ml) of of of
observation acid KMnO4 oxalic KMnO4
(ml) Initial reading Final reading (ml) acid(N) (N)
1. - - - -
2. - - - -
3. - - - -
4. - - - -
5. - - - -
2.5.3. Standarisation of Mohr salt solution by std. given KMnO4 solution

Take 5 ml of ferrous ammonium sulfate solution in a conical flask. Add about to 2.5
ml of Zimmermann Reinhardt mixture. Dilute to 50 ml with distilled water. Run the
permanganate solution from the burette till a faint pink colour develops through the whole
mass of the solution. Here Potassium permanganate acts as a self indicator.
Table 2.3: Standardisation of ferrous ammonium sulfate

No. Volume of Burette reading of Volume Strength Iron
of Mohr salt KMnO4 solution(ml) of of present
observation solution KMnO4 KMnO4 (gm)
(ml) Initial reading Final reading (ml) (N) per lit
1. - - - - - -
2. - - - - - -
3. - - - - - -
4. - - - - - -
5. - - - - - -
2.6 Calculation
Let, the exact strength of KMnO4 solution as determined by experiment = S(N).
Also let the volume of KMnO4 solution required to oxidize 5 ml of ferrous iron solution = V ml
Since,
1000 ml of1 (N) KMnO4 solution ≡ 1 (N) Mohr salt solution = 56 gm of iron
1 ml of 1 (N) KMnO4 solution = 0.056 gm of iron
V ml of S ( N ) KMnO 4 solution = 0.056 × S × V gm of iron
Now,
5 ml of Mohr salt solution contain 0.056 × S × V gm of iron
0.056 × S × V × 1000
1000 ml of ferrous iron solution contain gm of iron
5
2.7 Precaution
1.7.1. Titration is carried out at room temperature
1.7.2. All the apparatus should be washed with distilled water before use
1.7.3. Rinse the burette with a solution of KMnO4 to be taken in the burette
1.7.4. Rinse the pipette with a solution to be taken in the conical flask
1.7.5. Wash the conical flask with distilled water after every titration
[N.B.: During writing precaution write your own passive voice].
2.8 Conclusion
1.8.1. Potassim permanganate is a self indcator in this redox titration traction
1.8.2. Manganous ion Mn2+ is an example of AUTO catalyst in the reaction of between Potassim
permanganate and Oxalic acid. Reaction-
MnO-4 + C2 H2 O4 + 6H+ + 3e-1 = Mn2+ + 2CO2 + 4H2 O

1.8.3. Iron present in water in different forms and concentrations may cause some problem in
laboratory reaction as well as industry also but if we know the concentration of the Iron
in the form of water soluble salt we can take necessary action to remove the iron. This is
one important method which helps us to estimate the iron present per litre in any form of
aqueous solution.

2.9.1. Give the molecular formula of Potassium permanganate, Mohr salt, Phosphoric acid, Man-
ganus sulphate.
Ans. The molecular formula of Potassium permanganate, Mohr salt, Phosphoric acid,
Manganus sulphate KMnO4 ; (NH4 )2 SO4 .FeSO4 .6H2 O; H3 PO4 ; MnSO4 respectively.
2.9.2. Why is this titration reaction termed permanganometry?

Ans. In this titration reaction the titer is potassium permanganate that is why the reac-
tion is termed permanganometry.
2.9.3. Why is the titration called redox titration?

Ans. In the term redox, red stands for reduction and Ox stands for oxidation. In this reac-
tion simultaneous reduction and oxidation take place means one compound (here KMnO4
)undergoes reduction and another compound (here iron)undergoes oxidation.
2.9.4. What do you mean by oxidation and reduction?

Ans. According to the old concept oxidation means addition of oxygen or other elec-
tronegative elements (like F, Cl2 , Br2 , I2 ete.)to any element or compound or elimination
of hydrogen or other electropositive elements (like metal)from any element. According
to the modern concept oxidation means loss of electron from any element or compound
and thereby increased in oxidation number and reduction means gain of electron to any
element or compound and thereby decreased in oxidation number.
2.9.5. In this reaction which one is oxidant and which one is reductant?
Ans. In this titration reaction potassium permanganate acts as an oxidant or oxidizing
agent and iron present in Mohr salt acts as a reductant or reducing agent.
2.9.6. Give the Nernst’s equation for this redox reaction.

Ans. The Nernst equation for this reaction is
0.059 Mn+2
E = E0 − log .
n MnO-4
2.9.7. What is the full form of Z-R solution?

Ans. The full form of Z-R is Zimmermann-Reinhardt Solution.
2.9.8. Name of the chemicals are present in Z-R solution? What are their functions?
Ans. MnSO4 , concentrated H2 SO4 and concentrated H3 PO4 these chemicals are present
in Z-R solution.
2.9.9. What are the standard reduction potentials of

(i) Mn2+ /MnO-4
(ii) Fe3+ /Fe2+ and
(iii) Cl/Cl- system?
Ans. the standard reduction potentials of system
(i)MnO-4 /Mn2+ is 1.56 V
(ii) Fe3+ /Fe2+ is 0.77 V and

(iii) 21 Cl2 /Cl- is 1.36 V
2.9.10. In this permanganometry titration which is an indicator you have used?

Ans. In this permanganometry titration we have not used any foreign indicator. Here
KMnO4 acts as a self indicator and at the end point the final colour change will be colorless
to light pink.
2.9.11. Give one example of a self indicator.

Ans. KMnO4 acts as a self indicator and at the end point the final colour change will be
colorless to light pink.
2.9.12. Give one example of auto catalyst.

Ans. Mn2+ is an example of auto catalyst in the titration reaction between Potassium
permanganate and Oxalic acid. In this reaction with addition of one or two drops of
Potassium permanganate from the burette to the acid the whole solution become pink.
After continuous stirring for a time the solution colour will be colorless. Here one of the
products (Mn2+ ) enhances the oxidation of oxalic acid. Reaction-
MnO-4 + C2 H2 O4 + 6H+ ¿ Mn2+ + 2CO2 + 4H2 O
2.9.13. What is the oxidation state of manganese in Potassium permanganate and Manganous
ion?
Ans. The oxidation state of manganese in Potassium permanganate is +7 Let, the oxi-
dation state of Mn in KMnO4 be x, oxidation state of K in KMnO4 be +1 and oxidation
state of O in KMnO4 be -2 So,
(+1) × 1 + (+x) × 1 + (-2) × 4 = 0

Or, (+1) + (+x) + (-8) = 0
Or, (+x) − 7 = 0
Or, x = +7
2.9.14. What is the molecular formula of Mohr salt? What is the function of water molecule in
Mohr salt?
Ans. FeSO4 , (NH4 )2 SO4 , 6H2 O. The function of six water molecule in Mohr salt is the
water of crystallization. The presence of this definite number of water molecules brings
the exact crystal geometry of the lattice.
2.9.15. Mohr salt is an example of i) Simple salt ii) double salt iii) complex salt?
Ans. Mohr salt is an example of double salt as we get all the ions in aqueous medium.
2.9.16. Is potassium permanganate solution primary or secondary standard? Explain.

Ans. Potassium permanganate solution is secondary standard solution as its strength
change time to time.
2.9.17. Give another example of redox titration for the estimation of iron?
Ans.The common example of redox titration for the estimation iron is dichromometry
using Potassium dichromate. The redox reaction is given below.

Reduction reaction: Cr2 O2- + -
7 + 14H + 6e = 2Cr
3+ + 7H O
2
Oxidation reaction: Fe2+ − e- = Fe3+
The overall reaction is- Cr2 O2- +
7 + 14H + 6Fe
2+ = 2Cr3+ + 6Fe3+ + 7H O.
2
2.9.18. How the strength of Potassium permanganate is to be determined?

Ans.The strength of Potassium permanganate(oxidizing agent) is determined by using
standard oxalic acid or sodium oxalate(reducing agent)solution. Filled up potassium per-
manganate in a cleaned burette and make up the volume. Then known volume(5 or 10 ml)
of standard oxalic acid or sodium oxalate is taken in a conical flask add distilled water(40
to 60 ml) followed by Standard[4 to 6(M)]sulphuric acid solution(10-12 ml)and heat the
solution at a temperature 600 C. Maintain this temperature and titrate with potassium
permanganate.
2.9.19. Give two example of redox indicator.

Ans. i) Barium diphenyl amine sulphonate(BDAS)
ii) Phenolpthalen

Ans. Iron present in water in different forms and concentrations may cause some problem
in laboratory reaction as well as industry. If we know the concentration of the salt present
in water having iron we can take necessary action to remove the iron. This is one method
which helps us to estimate the iron present per litre in any solution.
Chapter 3
Experiment
name:Complexometric Titration
(Estimation of Calcium and
Magnesium Hardness separately
using EDTA Titration)

(To determine calcium and magnesium hardness of a given water sample separately.)
3.2 Theory
Complexometry involves the estimation of metal ions titrimetrically through complex formation
with a strong multidentate chelating ligand. Ligands having more than one co-ordinate centres
are known as chelating ligands. They give extra stability to a metal complex due to chelate
effect-the stability increases with the number of points . They give extra stability to a metal
complex due to chelate effect-the stability increases with the number of points of attachments of
the ligand to a metal ion. In this titration, Ethylene diamine tetra-acetic acid(EDTA) is used as
a chelating ligand. The total hardness of water is due to dissolved calcium salts and magnesium
salts and expressed as part of CaCO3 equivalent per million part of water(ppm). The total
hardness is conveniently determined by resin, i.e.,disodium hydro ethylene diamine tetra acetate
dehydrate Na2 H2 C10 H12 O8 N2 , 2H2 O(m.wt.=372.25) generally formulated as Na2 H2 Y, 2H2 O,
using Erichrome black T indicator(EBT).
Between pH 7 to 11, Erichrome black T is blue colour. Addition of metallic salt produce in
this staged a brilliant change in color from blue to wine red.
When the wine red complex is treated with disodium salt of EDTA, the complex between the
metal and EDTA is formed rapidly. The wine red becomes blue due to the formation of free
indicator itself. According to the equation-
M In + Na(HEDTA) = Na2 (MEDTA) + In H2
25
26 CHAPTER 3. DETERMINATION OF HARDNESS OF WATER

3.3.1. 0.01(M) EDTA solution
3.3.2. Buffer of pH = 10 (Mixture of NH4 Cl and NH4 OH)
3.3.3. EBT indicator
3.3.4. 2(N) NaOH solution
3.3.5. Murexide indicator
3.4 Apparatus Required

3.4.2. Burette
3.4.3. Pipette
3.4.7. Beakers
3.5 Procedure
3.5.1. Weighing of EDTA for the preparation of 1 litre 0.01(M) EDTA solution
Table 3.1: Weighing of EDTA for the preparation of 1 litre 0.01(M) EDTA solution
weight(gm) weight(gm) taken(gm) taken(gm) 0.01 (M)
- - - 3.72 -
3.5.2. Determination of Total hardness of water by EDTA solution

Take 25 ml of the given water sample in a clean conical flask. To this add 1 ml buffer
solution of pH = 10 and then add 1 to 2 drops of EBT indicator. Then titrate against
EDTA solution from burette until the color changes from wine red to blue with 1 drop of
EDTA solution.
3.6. CALCULATION 27
Table 3.2: Determination of Total Hardness of water by EDTA solution

No. Volume of . Burette reading of Volume of Mean Volume Total
of water EDTA solution EDTA of EDTA hardness
sample solution solution in
observation taken(ml) Initial Final (ml) (ml) ppm.
1. 25 - - -
2. 25 - - -
3. 25 - - -
4. 25 - - -
5. 25 - - -
3.5.3. Determination of calcium hardness of water by EDTA solution

Take 25 ml of sample water in a conical flask. To this add 1 ml of 2(N) NaOH solution and
then add 1 drop of murexide indicator. Then titrate against EDTA solution from burette
until the color changes from pink to purple with 1 drop of EDTA solution.
Table 3.3: Determination of calcium Hardness of water by EDTA solution

No. Volume of . Burette reading of Volume of Mean Volume Calcium
of water EDTA solution EDTA of EDTA hardness
sample solution solution in
observation taken(ml) Initial Final (ml) (ml) ppm.
1. 25 - - -
2. 25 - - -
3. 25 - - -
4. 25 - - -
5. 25 - - -
3.6 Calculation
Let, the burette reading of EDTA = V ml
1000 ml of 1(M)EDTA = 1000 ml of1(N) CaCO3

= 100 gm of CaCO3
1 ml of 1(M) EDTA = 10-1 gm of CaCO3
V ml of 0.01(M) EDTA = 10-1 V 0.01 gm ofCaCO3
= V × 10-3 gm of CaCO3
Hence,
25 ml sample water contains V × 10-3 gm of CaCO3

Therefore,
V × 10-3 × 106 V × 103

106 ml sample water contains gm of CaCO3 = ppm
25 25
3.7 Precuation
3.7.1. Use distilled water for washing and rinsing of glass apparatus.
3.7.2. Prepare EDTA solution in double distilled water.
3.7.3. Add one to two drops of indicator in each time before starting titration.
3.7.4. Maintain pH = 10 during the titration by adding buffer.
3.7.5. Correctly observe the end point.
3.8 Conclusion
3.8.1. Hard water creates some major problem in laboratory as well as industry mainly in boiler
and laundry.
3.8.2. During the preparation and processing of aqua based adhesive and polymer such type of
hardness creating soluble salt has a great role but it has a tolerable limit. If we know the
hardness of water then we can take necessary action to remove the salt responsible for
hardness of water.This is the best method by which we can measure the total as well as
calcium hardness of water.

3.9.1. ”Hardness” - this term is normally used in case of which liquid?
Ans. ”Hardness” - this term is normally used in case of WATER only.
3.9.2. What is hard water and soft water?

Ans. Water, in which on application of small amount of soap does not create lather easily
is called hard water. The hardness creating salts reacts with sodium stearate, sodium
palmitate or sodium oleate and gets precipitated from the water and Water in which on
application of small amount of soap creates lather easily is called soft water.
3.9.3. What is the cause of hardness of water?

Ans. The Hardness of water is due to the presence of some salts (Chloride, sulphate and
bicarbonate salts of calcium, magnesium) in water.
3.9.4. What is temporary and permanent hardness of water?

Ans. The presence of bicarbonate salts of calcium, magnesium in water is called tempo-
rary hardness and the presence of chloride and sulphate salts of calcium, magnesium in
water is called permanent hardness.
3.9.5. How can you remove temporary and permanent hardness of water?
Ans.Temporary hardness is due to the presence of bicarbonate salts of calcium, magnesium
and can be removed by (i) Boiling of water:
Ca(HCO3 )2 = CaCO3 + CO2 + H2 O
(ii) Clark method that is boiling of water with calcium hydroxide:

Ca(HCO3 )2 + Ca(OH)2 = 2CaCO3 + H2 O
Permanent hardness is due to the presence of chloride, sulphate salts of calcium, magne-
sium and can be removed by-
(i) Lime-soda process:
In this process lime and soda is mixed with water then after filtration we get soft water.

CaSO4 + Na2 (CO)3 = 2CaCO3 + Na2 (SO)4
(ii)permutit or Zeolite(sodium allumino silicate)process:
2Na+ Z- + Ca2+ = Ca2+ (Z)-2 + 2Na+

2Na+ Z- + Mg2+ = Mg2+ (Z)-2 + 2Na+
(iii) Ion exchange process:

In this process two columns containing both cation and anion exchange resin. The cation
exchange resin removes all cation giving H+ and anion exchange resin removes all anion
giving OH- . as a result water is free from all types of ions and get soft. (iv) Calgon(sodium
hexameta phosphate) process:
2CaSO4 + Na2 [Na4 P6 O18 ] = 2Na2 SO4 + Na2 [Ca2 P6 O18 ]
(ii) Clark method that is boiling of water with calcium hydroxide.
3.9.6. What is soap?

Ans. Soaps are sodium salts of higher fatty acids like stearic acid, palmitic acid and
oleic acid.
3.9.7. What reaction takes place between hard water and soap? Or why more soap is required
in hard water?
Ans. The hardness creating salts reacts with soap(like sodium stearate, sodium palmitate
or sodium oleate) and gets precipitated from the water. That is why more soap is required
and after removal of all hardness creating salts lather is formed Reaction:
2Na-Stearate + CaCl2 / or SO4 → Calsium(stearate)2 + 2NaCl or Na2 SO4 .
3.9.8. Why hard water is not used in laundry and boiler?

Ans. In laundry if water is hard water:
i) More washing soap is necessary which is not economically sustainable
ii) The produced Ca or Mg stearate, palmitate or oleate is precipitated in the form of
gelatinous compound which damage cloths
iii) Hard water makes stain on the clothes mainly on white clothes.
In boiler if water is hard water:
i) During heating of hard water in boiler hardness creating salt gets precipitated as insolu-
ble carbonates and sediment form commercially called scaling. To transform heat through
this layer to boil the water consume unwanted fuel which is economically profitable.
ii) The thickness of scaling may or may not be uniform causing uneven expansion of boiler
may cause bursting of boiler.
iii)At high temperature and pressure calcium or magnesium.
chloride(in hard water) react with steam produce HCl which corrode the wall of the boiler.
MgCl2 + 2H2 O(steam) = Mg(OH)2 + 2HCl.
3.9.9. How hardness of water is expressed?

Ans. Hardness of water is expressed in terms of ppm. The amount of hardness creating
salt is converted to the equivalent calcium carbonate and ultimately express per million
volume or weight of water.
3.9.10. What is ppm?

Ans. ppm is Parts per million. It is the amount of hardness creating salt expressed in
terms of equivalent amount of CaCO3 present per million mass or volume of water.
3.9.11. A water sample is written as 20 ppm. - what do you mean?

Ans. It is the amount of hardness creating salt expressed in terms of equivalent amount
(20gms) of CaCO3 present per million mass or volume of water.
3.9.12. What is complex salt? Give example.

Ans. A complex salt is a salt which is not fully ionized in solution. It has two spheres-
i) primary or ionisable sphere and ii) secondary or non-ionisable sphere. So it is different
from other salts and we do not get all the ions.
Example: K4 [Fe(CN)6 ]; where outside of the third bracket is primary or ionisable sphere
and inside the third bracket is secondary or non-ionisable sphere. So in solution we get
only and ion but not or ions.
3.9.13. Why the term complexometry is used?

Ans. In this titration reaction the reaction proceeds through complex formation that is
why the reaction is termed complexometry.
3.9.14. What are the differences between complex salt and double salt?
Ans. A complex salt is a salt which is not fully ionized in solution. It has two spheres-
i) primary or ionisable sphere and ii) secondary or non-ionisable sphere. So it is different
from other salts and we do not get all the ions. Example: K4 [Fe(CN)6 ]; where outside of
the third bracket is primary or ionisable sphere and inside the third bracket is secondary
or non-ionisable sphere. So in solution we get only and ion but not or ions. A double salt
is a salt which is combination of two salts and gets fully ionized in solution. Example: ;
- -
where It is fully ionised. So in solution we get K+ , and [Fe(CN)6 ]ion but not Fe or (CN)
ions. A double salt is a salt which is combination of two salts and gets fully ionized in
solution. Example: FeSO4 , (NH4 )2 SO4 , 6H2 O; where It is fully ionised. So in solution
we getFe2+ , SO4 and NH4 + .
3.9.15. What is ligand? Give example.

Ans. An ion or molecule attached to a metal atom by coordinate bonding. In coordi-
nation chemistry, a ligand is an ion or molecule (functional group) that binds to a central
metal atom to form a coordination complex. The bonding between metal and ligand gen-
erally involves formal donation of one or more of the ligand’s electron pairs. The nature
of metal-ligand bonding can range from covalent to ionic. Another important thing, the
metal-ligand bond order can range from one to three.
3.9.16. What is chelate complex? Give example.

Ans. If any ligand has more than one donor or coordination center and it is attached
to the metal with it’s at least two coordination center consequently, it forms a complex
structure just like a crab’s claw is called chelate complex.
3.9.17. What is the EDTA? Give structure?

Ans. Ethylenediaminetetraacetic acid, widely abbreviated as EDTA
3.9.18. EDTA is a primary or secondary standard solution?

A. EDTA is a secondary standard solution because chemical compounds have to fulfill a
number of requirements before they can be classified and used as a primary standard: A
primary standard in chemistry is a reliable, readily quantified substance. Features of a
primary standard includs: 1. High purity 2. Stability (low reactivity) 3. Low hygroscop-
icity and efflorescence 4. High solubility (if used in titration) 5. High equivalent weight
6. Non-toxicity 7. Ready and cheap availability as EDTA and particularly the sodium
salts of EDTA which are frequently used do not fulfill the first requirement. Therefore the
solution of EDTA has to be standardised against a known and accepted primary standard.
3.9.19. Why is EDTA called cheating ligand and resin?

Ans. As EDTA is a ligand having more than one donor or coordination center(actually 6)
and it is attached to the metal with those coordination center consequently form a complex
structure just like a crab’s claw. For this reason is EDTA is called chelating ligands.
3.9.20. What do you mean by monodentate, bidentate, tridentate, tetradentate, pentadentate,

hexadentate and ambdentate ligand? Give example of each.
Ans. Monodentate ligand: Ligands which have one donor or coordination center, can
attach to the central atom in one places. A good example of this is Cl- ,
Bidentate ligand: Ligands which have two donors or coordination centers, can attach to
the central atom in two places. A good example of this is S2- Oxalate (oxalato) Ethylene-
diamine, Acetylacetonate (Acac).
Tridentate ligand: Tetradentate ligand: Ligands which have three donors or coordina-
tion centers, can attach to the central atom in three places. A good example of this is
Diethylenetriamine (dien), 2,2’;6’,2”-Terpyridine (terpy), Triazacyclononane (tacn).
Tetradentate ligand: Tetradentate ligand: Ligands which have four donors or coordi-
nation centers, can attach to the central atom in four places. A good example of this is Tri-
ethylenetetramine (trien), Tris(2-aminoethyl)amine (tren), Tris(2-diphenylphosphineethyl)amine
(np3).
Pentadentate ligand: Ligands which have five donors or coordination centers, can attach
to the central atom in five places. A good example of this is Ethylenediaminetriacetate.
Hexadentate ligand: Ligands which have six donors or coordination centers, can attach
to the central atom in six places. A good example of this is Ethylenediaminetetraacetate
(EDTA), 2,2,2-crypt.
Ambidentate ligand: Unlike polydentate ligands, ambidentate ligands can attach to
the central atom in two places. A good example of this is thiocyanate, SCN- , which can
attach at either the sulfur atom or the nitrogen atom. Such compounds give rise to link-
age isomerism. Polyfunctional ligands, see especially proteins, can bond to a metal center
through different ligand atoms to form various isomers.
Bridging ligand: A bridging ligand links two or more metal centers. Virtually all inor-
ganic solids with simple formulas are coordination polymers, consisting of metal centres
linked by bridging ligands. This group of materials include all anhydrous binary metal
halides and pseudohalides. Bridging ligands also persist in solution. Polyatomic ligands
such as carbonate are ambidentate and thus are found to often bound to two or three
metals simultaneously. Atoms that bridge metals are sometimes indicated with the prefix
µ (mu). Most inorganic solids are polymers by virtue of the presence of multiple bridging
ligands.
Table 3.4: Examples of common ligands: Ligands are arranged from top to bottom
by field strength i.e. weak field ligands to strong field ligand:
Ligand formula (bonding Charge Most common Remark(s)
atom(s) in bold) denticity
Iodide (iodo) I- monoanionic monodentate -
Bromide (bromido) Br- monoanionic monodentate -
Sulfide (thio or S2- dianionic monodentate -
less commonly (M=S),or
”bridging thiolate”) bidentate
Thiocyanate S-CN- monoanionic monodentate ambidentate (see also
(S-thiocyanato) isothiocyanate, below)
Chloride (chlorido) Cl- monoanionic monodentate also found bridging
Nitrate (nitrato) NO-O-2 monoanionic monodentate -
Azide (azido) NN-2 monoanionic monodentate -
Fluoride (fluoro) F- monoanionic monodentate -
Hydroxide OH- monoanionic monodentate often found as
(hydroxo) OH- a bridging ligand
Oxalate (oxalato) [O-C(=O)-C(=O)-O]2- dianionic bidentate -
Water (aqua) H-O-H neutral monodentate monodentate
Nitrite O-N-O- monoanionic monodentate ambidentate
(nitrito) (see also nitro)
Isothiocyanate N=C=S- monoanionic monodentate ambidentate
(isothiocyanato) (see also nitro)
Acetonitrile CH3 CN neutral monodentate -
(acetonitrilo)
Pyridine C5 H5 N neutral monodentate -
Ammonia NH3 neutral monodentate -
(ammine or
less commonly
”ammino”)
Ethylenediamine en neutral bidentate -
2,2’-Bipyridine bipy neutral bidentate easily reduced
to its (radical)anion
or even to its dianion
1,10-Phenanthroline phen neutral bidentate -
Nitrite (nitro) N-O-2 monoanionic monodentate ambidentate
(see also nitrito)
Triphenyl PPh3 neutral monodentate can bridge between
phosphine metals (both
to metals bound C,
or one to C
and one to N)
Cyanide (cyano) CN- monoanionic monodentate -
Carbon monoxide CO neutral monodentate can bridge between metals
(carbonyl) (both metals bound to C)
Table 3.5: Other generally encountered ligands (alphabetical)

In this table other common ligands are listed in alphabetical order
Ligand formula Charge Most Remark(s)
(bonding common
atom(s) denticity
in bold)
Acetylacetonate CH3 − C(O)− monoanionic bidentate In general bidentate,
(Acac) CH2 − C(O) − CH3 bound through both
oxygens, but sometimes
bound through the ,
central carbon only,
Alkenes R2 C=CR2 neutral compounds with a
C-C double bond
Benzene C6 H6 neutral - and other arenes
1,2-Bis(diphenylphosphino) Ph2 PC2 neutral bidentate -
ethane (dppe) H4 PPh2
1,1-Bis C25 neutral - Can bond to 2
(diphenylphosphino) metal atoms
methane H22 P2 at once, forming dimers
Corroles - - tetradentate -
Crown - neutral primarily for
ethers - alkali and alkaline
- earth metal cations
Cryptates - neutral - -
Cyclopentadienyl (Cp) [C5 H-5 ] monoanionic Although monoanionic,
by the nature of
its occupied MO’s, it
is capable of acting
as a tridentate ligand.
Diethylenetriamine (dien) C4 H13 N3 neutral tridentate related to TACN,
but not constrained
to facial complexation
Dimethylglyoximate (dmgH- ) - monoanionic - -
Ethylenediaminetetraacetate (HOOC-CH2 )2 tetra-anionic hexadentate actual ligand
(EDTA) N-(CH2 )2 − is the tetra-anion
N(CH2 −
COOH)2
Ethylenediamine - trianionic pentadentate actual ligand
triacetate - is the trianion
Ethyleneglycol-bis (HOOC-CH2 )2 tetra-anionic octodentate -
(oxyethylenenitrilo) N-(CH2 )2 − O−
-tetraacetate (EGTA) (CH2 )2 − O − (CH2 )2 −
N(CH2 − COOH)2
Glycinate monoanionic bidentate other α -amino
(Glycinato) acid anions are
- comparable (but chiral)
Heme - dianionic tetradentate macrocyclic ligand
Nitrosyl NO+ cationic - bent (1e) and linear
(3e) bonding mode
Oxo O dianion monodentate sometimes bridging
Pyrazine N2 C4 H4 neutral ditopic sometimes bridging
Scorpionate ligand - - tridentate -
Sulfite SO-3 monoanionic monodentate ambidentate
Triethylenetetramine (trien) - neutral tetradentate -
Terpyridine C15 H11 N3 neutral tridentate -
3.9.21. Which indicator is used during total(by Calcium and Magnesium ) hardness measurement?
Ans. EBT(Eriochrome Black T).
3.9.22. What is the colour of EBT in hard water?

Ans. The colour of metal(present in hard water) EBT complex is wine red colour.
3.9.23. What is the colour of Murexide in hard water? What is the structure of Murexide?
Ans. The colour of metal(present in hard water) murexide complex is light pink
in colour. The IUPAC name of murexide is ammonium 2,6-dioxo-5-[(2,4,6-trioxo-1,3-
diazinan-5-ylidene)amino]-1,2,3,6-tetrahydropyrimidin-4-olate. The structure of Murexide
is-
Structure of murexide
3.9.24. Why NH4 OH and NH4 Cl is used before addition of EBT in hard water?
Ans.When ph is low the metal EBT complex is unstable and the colour is not a prominent
wine red. By adding NH4 OH and NH4 Cl the pH value is raised to 10 where the metal
EBT complex is stable.
3.9.25. Which indicator is used during only calcium hardness measurement?

Ans. Murexide indicator
3.9.26. Why 2 (N) NaOH solution is added before addition of Murexide in hard water?
Ans. In determining the Ca hardness, 2(N) NaOH solution is added to the water sample.
Here the Mg ions are precipitated by addition of 2(N) NaOH solution and it is titrated
against EDTA using murexide indicator. Necessary condition to be maintained while
doing the titration is to keep the pH at about 10.
3.9.27. Why EDTA replaces Eriochrome black T, murexide and form metal-EDTA complex?
Ans. AS EDTA is a stronger ligand than Eriochrome black T and murexide, so it replaces
calcium and magnesium and forms metal-EDTA complex.
3.9.28. EBT and EDTA which one is the stronger ligand?

Ans. EDTA is stronger ligand than EBT.
Ans. Hard water creates some major problem in laboratory as well as industry mainly
in boiler, aqua based adhesive and polymer but it has a tolerable limit. If we know the
hardness of water then we can take necessary actions to remove the salt responsible for
the hardness of water. This is the best method by which we can measure the total as well
as calcium hardness of water.
3.9.30. What is the full form of EBT? Give its structure.
Ans. The full form of EBT is Eriochrome Black T. The IUPAC name of Eriochrome Black
T is ”sodium -4-[(1-hydroxynaphthalen-2-yl- hydrazinylidene]-7-nitro-3-oxo Y-naphthalene-
1-sulfonate”.
The structure of EBT(Eriochrome Black T) is-
Structure of Eriochrome black T
3.9.31. What is the structure of metal-EDTA complex? Give the structure.

Ans. The metal-EDTA complex structure is octahedral. The structure is-
Octahedral metal EDTA structure

Chapter 4
Experiment name:To determine

the value of the rate constant for
the hydrolysis of ethyl acetate
catalyzed by hydrochloric acid

(To determine the value of the rate constant for the hydrolysis of ethyl acetate catalyzed by
hydrochloric acid)
4.2 Theory
Rate of first order reaction is directly proportional to the first power of the concentration of the
reactant. A first order reaction may be represented as,
A → Products) (4.1)
For which the rate,

−dCA
= k CA (4.2)
dt
Where, k is the rate constant (unit: time-1 ) and CA is the molar concentration of A at time t.
Integration of the rate equation with proper limits at t = 0, CA = C0 and t = t, CA = Ct ,
converting the logarithmic term to base 10 (i.e., log 10) one obtains,
2.303 C
k= log10 0 (4.3)
t C
The hydrolysis of ethyl acetate gives ethyl alcohol and acetic acid
CH3 COOC2 H5 + H2 O → CH3 COOH + C2 H5 OH
The reaction is catalyzed by dilute hydrochloric acid and is a reaction of first order as the
concentration of water is in large amount and does not change significantly during the reaction.
37
38 CHAPTER 4. DETERMINATION OF RATE CONSTANT
It is pseudo unimolecular reaction. The rate constant is determined by using the following kinetic
equation of first order
2.303 a
k= log10 (4.4)
t a-x
Where, a = initial concentration
a-x = concentration after time t.
The values of a, a-x and t are taken from experimentally determined values. In an actual exper-
imental solution of known concentration of ethyl acetate and HCl are mixed together and kept
on water bath at room temperature. Known volumes of the reaction mixtures are withdrawn at
interval of 5-10 minutes, added to chilled water in a conical flask and titrated against standard
NaOH solution using phenolphthalein as an indicator. The volume of NaOH used corresponds
to the total acid formed i.e. HCl and acetic acid by the hydrolysis in the reaction mixture. The
final reading is noted after keeping the remaining reaction mixture on water bath for 24 hours
or keeping it in hot water at 500 − 600 C for an hour.
2.303 V∞ − V0
k= log10
t V∞ − Vt
Where,
V0 = Volume of NaOH used at time t = 0
Vt = Volume of NaOH used at time t
V∞ = Volume of NaOH used for a sample of the reaction mixture kept on water bath at 500 −600 C
for an hour. Then a = V∞ − V0 and a-x = V∞ − Vt

4.3.1. Standard oxalic acid;C2 H2 O4 , 2H2 O
4.3.2. Sodium hydroxide solution; NaOH
4.3.3. Hydrochloric acid; HCl
4.3.4. Ethyl acetate; CH3 COOC2 H5
4.3.5. Phenolphthalein indicator

4.4.1. Burette
4.4.2. Pipette
4.4.6. Beakers
4.4.7. Funnel
4.5. PROCEDURE 39
4.4.8. Thermometer
4.4.9. Stop watch
4.4.10. Wash bottle
4.5 Procedure
4.5.1. Preparation of 250 ml 0.1(N) oxalic acid solution ³ ´
N solution,
Let, the weight of oxalic acid taken = W gm.
µ ¶
W N
= ×
1.575 10
Let, the weight of oxalic acid taken = W gm
Initial Final Weight Weight to Strength

³ ´
weight(gm) weight(gm) taken(gm) be taken(gm) N
10
- - - 1.575 -
Therefore, strength of oxalic acid

µ ¶
W N
= ×
1.575 10
4.5.2. Preparation of 500 ml 0.1(N) NaOH solution

Weigh about 2 gm of sodium hydroxide pellets and dissolve in small amount of distilled
water. Then, dilute the solution to 500 ml and mix the solution uniformly.
4.5.3. Standardization of NaOH solution
Pipette out 10 ml of the standard oxalic acid solution in a 250 ml conical flask. Add 1
drop of phenolphthalein indicator to it. Fill the burette with NaOH solution. Perform the
titration until the colorless solution turns pink. Repeat the titration to get at least three
concordant readings.
Table 4.2: Standardization of NaOH solution by standard oxalic acid solution

No. Volume of . Burette reading of Volume of Strength Strength
of oxalic NaOH solution NaOH of oxalic of NaOH
acid solution acid solution
observation (ml) Initial Final (ml) (N) (N)
1. - - - -
2. - - - -
3. - - - -
4. - - - -
Calculation of strength of NaOH solution

As we know,
V1 × S1 = V2 × S 2
Here,
V1 = Volume of standard oxalic acid solution(burette reading)

S1 = Strength of standard oxalic acid solution in Normality
V2 = Volume of NaOH solution taken(ml)
S2 = Strength of NaOH solution in Normality(Let)
4.5.4. Preparation of 250 ml of 0.5 (N) HCl acid

Pipette out 10 ml of the HCl acid solution in a 250 ml conical flask. Add 1 drop of
phenolphthalein indicator to it. Fill the burette with NaOH solution. Perform the titration
until the colorless solution turns pink. Repeat the titration to get at least three concordant
readings.
Table 4.3: Standardization of HCl solution by standard NaOH solution

No. Volume of . Burette reading of Volume of Strength Strength
of HCl NaOH solution NaOH of NaOH of HCl
acid solution solution solution
observation (ml) Initial Final (ml) (N) (N)
1. - - - -
2. - - - -
3. - - - -
4. - - - -
Calculation of strength of NaOH solution

As we know,
V3 × S2 = V4 × S 4
4.5. PROCEDURE 41
Here,
V4 = Volume of HCl acid solution(burette reading)

S4 = Strength of HCl acid solution in Normality(Let)
V3 = Volume of NaOH solution taken(ml)
S2 = Strength of NaOH solution in Normality
4.5.5. Procedure of hydrolysis of ester
4.5.6. Take 10 ml of 0.5 ( N) HCl in a dry 250 ml; conical flask and keep it on water bath at
room temperature, also take ethyl acetate in another conical flask and keep it on water
bath at the same temperature.
4.5.7. Rinse the burette and fill the burette with 0.1 (N) NaOH solutions and take 3-4 conical
flask containing small pieces of clean ice.
4.5.8. Pipette out 5 ml of ester and add it to the conical flask containing 100 ml of 0.5 (N) HCl
solutions.
4.5.9. Shake well and pipette out 10 ml of the reaction mixture in a conical flask containing
ice cold water, titrate this against 0.1 (N) NaOH solution using phenolphthalein indicator
appearance pink of color is the end point. The volume of NaOH used against the sample
at the start of the reaction is taken as V0 .
4.5.10. Note the time of draining out of 10 ml of solution onto the flask and if it is 10 sec then
the mixture should be added to the ice water 5 minutes than 10 mins.
4.5.11. Pipette out 10 ml of solution and add it into the conical flask containing chilled water
after 10 mins. Titrate it against 0.1 (N) NaOH solutions. This is Vt after 10 mins.
4.5.12. Repeat the procedure every after 10 mins for at least four readings there should be an
increase of 5 mins for every reading i.e., the interval of 10, 20, 30 and 40 mins. Finally
remove the flask from water bath and place it on a water bath at 50 − 600 C for an hour.
Then pipette out 10 ml of this mixture and titrate against 0.1(N) NaOH and this is V∞ .
Table 4.4: Recording of data for acid catalyzed hydrolysis of ethyl acetate
No. Time Burette reading of Volume of
V∞ −V0 V∞ −V
of in NaOH solution NaOH V∞ − Vt V∞ −Vt log10 V −V 0
t t
observation (min.) solution
Initial Final (ml)
1. - - - - - - -
2. - - - - - - -
3. - - - - - - -
4. - - - - - - -
4.6 Calculation
2.303 a
k= log10
t a-x
2.303 V∞ − V0
k= log10
t V∞ − Vt
When time = 10 min,
2.303 V∞ − V0
k= log10 min-1
10 V∞ − Vt
Calculate the values of k at intervals of time. The mean value of k gives the value of rate constant
k
4.7 Precaution
4.7.1. The temperature of the thermostat should be maintained within ±0.50 C throughout the
experiment since the rate of the reaction is very sensitive to temperature changes.
4.7.2. Start the stopwatch when ethyl acetate has been half discharged into conical flask con-
taining acid.
4.7.3. Freeze each reaction aliquot in ice cold and then perform the titration.
N.B.: During writing precaution write your own passive voice.
4.8 Conclusion

4.9.1. What is rate law?
Ans. The quantity of a reactant species consumed or the quantity of a product species
formed in unit time in a chemical reaction is called the rate of the reaction. Rate law
correspond to the slowest step (RDS) in a complex reaction. Consider a reaction A → B
Amount of A consumed
Rate of reaction =
Time taken
Amount of B produced
or, Rate of reaction =
Time taken
rate depends on nature of the reactants, surface area, pressure,temperature,
catalyst, inhibitor etc.
4.9.2. What is law of mass action?

Ans. According to the law of mass action (Guldberg and Wage-1867))The rate of any
chemical reaction at any instance is directly proportional to the product of the active mass
of the reacting species. Active mass means molar concentration.
Consider a reaction A → B
With respect to reactant:
Rate of reaction =
Time taken
d[A]
= − ∝ [A]
dt
d[A]
or, − = kR [A]
dt
With respect to product:
Amount of B produce
Rate of reaction =
Time taken
d[B]
= + ∝ [B]
dt
d[B]
or, + = kP [B]
dt
4.9.3. What is rate constant?
Ans. Consider a reaction A → B
Rate of reaction =
Time taken
d[A]
= − ∝ [A]
dt
d[A]
or, − = kR [A]
dt
Consider another reaction A + B → C + D
Rate of reaction ∝ [A][B] = kR [A][B]
Where, [A] and [B] are the molar concentration of A and B species respectively
kR is the rate constant or specific reaction rate. rate constant is depend only on
temperature.
4.9.4. How rate is measured?
Ans. In order to determine the rate of reaction, a reactant of product species whose con-
centration is measurable is selected. The progress of the reaction is followed by studying
the concentration of the selected species at different interval of time. It is done by with-
drawing a small amount of reaction mixture, freezing it and then analyzing it. Freezing is
done by cooling the reaction mixture to stop the reaction or decrease the rate of reaction.
However there are two methods for measuring the rate of reaction.
a) Calculation of average rate of reaction
b) Calculation of Instantaneous rate of reaction
4.9.5. What is order and molecularity?
Ans. Order: The order of a reaction is the sum of the exponents(power) of the concen-
tration term in the rate of equation.
For a generalized reaction equation
aA + bB + cC → Product
dC
Rate = −
dt
= k[A]α [B]β [C]γ
The order of the reaction is given as η = α + β + γ.

The reaction is α order with respect to A, β order with respect to B, γ order with respect
to C and so on.
Molecularity: Though many chemical reactions follow simple rate laws, in reality they
may occur through a sequence of step. Each step of the process is called the elementary
process. The number of reacting species that take part in an elementary reaction process is
called the molecularity of that step and the molecularity of overall reaction is meaningless.
For a simple or one step reaction the molecularity is simply the sum of the number of
reacting species as presented by the balanced chemical equation
For a generalized reaction equation
aA + bB + cC → Product
The molecularity of the reaction is given as molecularity = a + b + c.

4.9.6. What is pseudo first order reaction? Give examples.
Ans. There are some reactions which follow the first order rate law, although more
than one reactants are involved in the reaction. Such reactions are known as pseudo first
order or pseudo unimolecular reaction. These reactions are truly second order reaction but
follow first order kinetics and hence are termed as pseudo first order or pseudo unimolecular
reaction. Some common examples are a) Inversion of cane sugar, b) Hydrolysis of an ester
in an acid medium.
4.9.7. What are the differences between order and molecularity?
Order Molecularity
i) It is the sum of the exponents i) It is the number of molecules
to which the concentration terms or ions taking part in a single
are raised in the rate equation step chemical reaction equation
ii) It may be a whole number ii) It is always a whole number,
or a fraction never a fraction
iii) It may be zero or negative iii) It is always positive and never zero
iv) It is an experimental iv) It is purely a theoretical value
value determined from determined from the balanced
rate of equation single step reaction
v) Order is same for the v) Molecularity of a complex reaction
whole reaction, no matter it has no meaning. It is expressed
is simple or complex one for each elementary step
4.9.8. Give examples of each- (i)Zero order reaction (ii) first order reaction (iii) second order
reaction.
Ans. examples of
(i)Zero order reaction
a) Dissociation of HI on gold
b) Dissociation of NH3 on tungsten(W), molybdenum(Mo) or platinum(Pt)
c) Photochemical combination reaction between H2 + Cl2 = 2HCl
(ii) first order reaction
a) Dissociation or decomposition of N2 O5 to N2 O4 + 21 O2
b) Dissociation or decomposition of acetone, azo compounds
c) Dissociation or decomposition of H2 O2 to H2 O + 12 O2
d) Example of pseudo-unimolecular reaction
(iii) second order reaction.
a) Conversion of ozone into oxygen at 373 K
b) Thermal decomposition of CH3 CHO vapour at 791 K
c) Thermal decomposition of N2 O to H2 O2 .
4.9.9. Give the temperature dependence rate equation.

Ans. Temperature dependence rate equation which is also known as Arrhenius equation
is
- Ea
k = A.e RT
Ea
lnk = lnA −
RT
Where, k is rate constant

A is a constant called frequency factor because it gives the frequency of collision of the
reacting molecules.
Ea is called energy of activation
R is universal gas constant
and T is absolute temperature.
4.9.10. What is temperature coefficient of reaction?

Ans. For most chemical reaction temperature has a marked effect on the rate of the
reaction. In homogeneous thermal reaction, for every 100 rise in temperature, the rate of
the reaction becomes almost doubled and in many cases is trebled, i.e., the temperature
coefficient become 2 to 3. The temperature is the ratio of velocity of a reaction at tem-
peratures differing by 100 . The standard temperature for the reaction is 350 C. Thus the
two temperature 250 C and 350 C
k
Temperature coefficient = (t + 10) ≈ 2 to 3.
kt
4.9.11. Give the unit of-

(i)Zero order reaction
(ii)first order reaction
(iii) second order reaction.
Ans. Consider a reaction A → B
With respect to the reactant:
Rate of reaction =
Time taken
Concentration of reactant
= − ∝ [A]n
Time
[A]
or, − = k[A]n
t
Where n is the order of the reaction.
[A]
or, = k
t[A]n
[A]
or, k =
t[A]n
[A]1-n
or, k =
t
Now unit of-
i)Zero order reaction:
[A]1-0
k =
t
[A]
k =
t
(ML)
k =
S
k = ML-1 S-1
Unit of zero order is ML-1 S-1

ii)first order reaction:
[A]1-1
k =
t
[A]0
k =
t
1
k =
S
k = S-1
Unit of first order is S-1

iii) second order reaction.
[A]1-2
k =
t
[A]-1
k =
t
(ML)
-1
k =
S
k = LM-1 S-1
Unit of second order is LM-1 S-1 .
4.9.12. Why zero order reaction is called a complete reaction?

Ans. From the equation
C = kt + C0
if we plot C vs t, we see that with increase in time initial concentration gradually decreases
and at a time it will be meet to the X axis where reaction will be completed.
4.9.13. Why first order reaction is called an incomplete reaction?

C = C0 e- kt
the reaction will never be completed because c will be zero only at infinite time. That is
why first order reaction is called an incomplete reaction.
4.9.14. What is half life period?

Ans. The time necessary for decomposition or disintegration of one half of the original
amount of a substance is called its half life period.
4.9.15. Infinite time is necessary for completion of a first order reaction-explain.

C = C0 e-kt
the reaction will never be completed because c will be zero only at infinite time. That is
why it is said infinite time is necessary for completion of a first order reaction. For example
we know disintegration of radioactive element follow first order kinetics. Scientists thought
that those radioactive elements were produced with the born of the earth yet radioactive
element still present in the earth.
4.9.16. How half life period is related with initial concentration of the reactant for first order
reaction?
Ans. From the equation of first order reaction
t 1 = 0.693
λ
2
Thus for a given reaction at a particular temperature the period of half life decomposition
is independent of initial concentration.
4.9.17. How many types of theory for chemical reaction-explain.

Ans. There are two theories for chemical reaction a) collision theory and b) activation
theory
collision theory: The collision theory based on the concept of Arrhenius (1889):
1. The reactant species (molecules, atoms or ions or free radicals) must come close to each
other and must have effective collision with one another(between the reacting species).
2.Reacting species must be properly oriented at the time of collision. Effective collision
will take place only between those colliding species which have a certain minimum amount
of energy, called threshold energy. Reacting species having energy less than the threshold
energy will not bring about chemical change.
Activation theory: From collision theory it is known that the molecules must have
threshold energy or energy beyond that before undergoing chemical changes. In other
words molecules must be in an energy rich or activated state before they can react. The
sum of activation energy and energy of the reactant is called threshold energy. Energy dif-
ference between activated complex and energy of the reactant is called activation energy.
The energy difference between energy of the product and energy of the reactant is called
energy or enthalpy of reaction. For exothermic reaction energy of the product > energy
of the reactant so, energy or enthalpy of reaction is negative. For endothermic reaction
energy of the product < energy of the reactant so, energy or enthalpy of reaction is Positive.

Ans. In chemical, biotechnology, food technological processing there are some reactions
whose kinetics and rate constant are important to determining the actual path of the reac-
tion and mechanism. With the help of this process of determination of rate constant will
help us to find out the actual path of the reaction. Also rate constant of any reaction(such
as enzyme catalytic reaction) helps us to find out the rate at varying temperature as it is
highly dependent on temperature.
Chapter 5
Heterogeneous equilibrium
(determination of partition
coefficient of acetic acid between
n-butanol and water)

(Determination of Partition Co-efficient of Acetic Acid between Water and n-butanol)
5.2 Theory
The Nernst distribution law states that at constant temperature, when different quantities of a
solute are allowed to distribute between two immiscible solvents in contact with each other, then
at equilibrium the ratio of the concentration of the solute in two solvent layers is constant. When
a solute is shaken in two immiscible liquids, then the solute is found to be distributed between
the liquids in a definite manner, if the solute is soluble in each of the solvent. According to the
Nernst distribution law, the distribution co-efficient at a particular temperature is given by
C
K = C1 .
2
Where, C1 and C2 represents the concentration of solute in solvent 1 and 2 respectively, when
in solution phase solute molecules are in same state of association. Now, if water and n-butanol
are taken as the pair of two immiscible solvents and acetic acid as the solute then as acetic
acid retains its normal molecular weight in both the solvents, so the expression for partition
co-efficient will be
Concentration of acetic acid in organic layer
K=
Concentration of acetic acid in organic layer

5.3.1. Standard oxalic acid;C2 H2 O4 , 2H2 O
5.3.2. Sodium hydroxide solution; NaOH
49
50 CHAPTER 5. DETERMINATION OF PARTITION COEFFICIENTT
5.3.3. Acetic acid; CH3 COOH

5.3.4. n-Butanol; CH3 CH2 CH2 CH2 OH

5.4.1. Burette
5.4.2. Pipette

5.4.6. Beakers
5.4.7. Wash bottle

5.4.8. Glass stopper bottle
5.5 Procedure
³ ´
5.5.1. Preparation of 250 ml N oxalic acid solution
10 ³ ´
N solution,
solid has dissolved, makeup the volume to the mark. Let, the weight of oxalic acid taken
= W gm. Strength of oxalic acid
µ ¶
W N
= ×
1.575 10

³ ´
10
- - - 1.575 -
Let, the weight of oxalic acid taken = W gm

Therefore, strength of oxalic acid =
µ ¶
W N
= ×
1.575 10
5.5. PROCEDURE 51
Table 5.2: Composition of materials in each bottle

Bottle 1 Bottle 2
20 ml acetic acid 40 ml acetic acid
490 ml water 480 ml water
490 ml n-butanol 480 ml n-butanol
5.5.2. Preparation of composition of n-butanol, water and acetic acid in each bottle
In bottle 1, 20 ml acetic acid, 490 ml water and 490 ml n-butanol was added.
Similarly in bottle 2, 40 ml acetic acid , 480 ml water and 480 ml n-butanol was added.
After addition each stoppered bottles were shaken for one hour and allowed to stand till
the two liquid layers separated.
5.5.3. Determination of strength of given NaOH solution with standard oxalic acid solution using
phenolphthalein indicator.
Take 5 ml of oxalic acid solution in a conical flask. Add 10 ml of distilled water to increase
the volume that is why we can see the colour change properly. Add one to two drops of
phenolphthalein indicator and titrate against NaOH solution from the burette. Take the
reading and repeat the titration thrice at least.
Table 5.3: Determination of strength of given NaOH solution with standard oxalic acid
of oxalic NaOH solution(ml) of of of
observation acid NaOH oxalic NaOH
(ml) Initial Final (ml) acid(N) (N)
1. - - - - - -
2. - - - - - -
3. - - - - - -
4. - - - - - -
5.5.4. Standardization acetic acid in aqueous layer and n-butanol layer by NaOH solution
Definite volume of aqueous layer and organic layer from each of the two bottles were taken
out and standardized against NaOH solution using Phenolphthalein as indicator.
Table 5.4: Standardization acetic acid in aqueous layer and n-butanol layer by NaOH
solution
Bottle Layer Volume Burette reading of Volume Strength
No taken of Standard NaOH(ml) of of
layer NaOH acetic
taken(ml) Initial Final solution(ml) acid (N)
1 Organic layer 5 - - - -
1 ,, 5 - - - -
1 ,, 5 - - - -
1 Aqueous layer 5 - - - -
1 ,, 5 - - - -
1 ,, 5 - - - -
2 Organic layer 5 - - - -
2 ,, 5 - - - -
2 ,, 5 - - - -
2 Aqueous layer 5 - - - -
2 ,, 5 - - - -
2 ,, 5 - - - -
5.5.5. Determination of partition co-efficient
Table 5.5: Determination of partition co-efficient

Bottle No Value of partition co-efficient Mean value
C
1 K = C1 .
2
C
2 K = C1 .
2
Partition co-efficient of acetic acid = - - - - - - - - - - -
5.6 Calculation
Calculate the strength of acetic acid in different layers from two different bottle of
solutions As we know,
V1 × S1 = V2 × S2
Here,
V1 = Mean volume of standard NaOH solution (burette reading)

S1 = Strength of standard NaOH solution in Normality
V2 = volume of layer of the solution(containing acetic acid) taken(ml)
S2 = Strength of acetic acid solution in Normality
5.7. PRECAUTION 53
5.7 Precaution
5.7.1. Stoppered bottles must shake for one hour and allowed to stand till the two liquid layers
are separated.
5.7.2. During pipettes of any solution after pushing pipette in solution make a limit switch by
using the left hand thumb and index finger with the mouth of stopper bottles
5.7.3. During withdrawing aliquot one layer must not be contaminated with the other
5.7.4. Pipette which is used during the experiment must be cleaned
5.8 Conclusion
If a solute is mixed with two different immiscible solvents without any reaction except association
or dissociation at constant temperature and at equilibrium the concentration ratio of the solute
in two solvents is constant at that temperature irrespective of their ratio of mixing

5.9.1. Why is the term partition used here?
Ans. As the two immiscible liquids(here n-Butanol and water)are separate from each
other and there is an imaginary or real partition between them -that is why the term
partition is used here,
5.9.2. Give the name of two immiscible solvents.

Ans. Any oil and water is the pair of two immiscible liquids due to their polarity differ-
ence. Here two immiscible liquids are n-butanol and water.
5.9.3. Give another pair of immiscible liquid with common solvent.

Ans. Benzene(C6 H6 ) and water with common solute Iodine(I2 )
5.9.4. Why they are immiscible give reason.

Ans. Any oil and water is the pair of two immiscible liquid and they are immiscible
mainly due to their polarity difference
5.9.5. Give the structure of n-Butanol and Isobutanol

Ans. The structure of n-Butanol CH3 CH2 CH2 CH2 OH and Iso-butanol CH3 CH(OH)CH2 CH3
5.9.6. Why water remains at the lower part in n-butanol and water mixture?
Ans. Due to Higher density of water than n-Butanol, water remains at the lower part in
n-Butanol and water mixture.
5.9.7. What is Nernst’s distribution law?

Ans. Nernst’s distribution law state that ”at constant temperature when a solute is
added to two immiscible liquid solvent in contact with each other, the solute gets dis-
tributed between the two solvents and at equilibrium the concentration ratio of the solute
in two solvents is constant at that temperature”.
5.9.8. Give the molecular formula of acetic acid. Is acetic acid an weak or strong acid?
Ans. The molecular formula of acetic acid is CH3 COOH. Acetic acid is an weak acid
as it is not dissociate completely and there is an equilibrium between dissociated ion and
undissociated acetic acid.
5.9.9. Why is acetic acid more miscible with n-butanol than water?
Ans. As water is a highly polar compound so there is only polar-polar interaction between
water and COOH of CH3 COOH. In n-butanol there is polar hydroxylic group and nonpo-
lar hydrocarbon chain. for this reason there is both polar-polar interaction between -OH
of CH3 CH2 CH2 CH2 OH and COOH of CH3 COOH as well as nonpolar-nonpolar interac-
tion between hydrocarbon chain of CH3 CH2 CH2 CH2 OH and hydrocarbon part(CH3 ) of
CH3 COOH.
5.9.10. Give the conditions of validity of Nernst’s distribution law.

Ans. The conditions of validity of Nernst’s distribution law are -
i)The same molecular species should be present in both solvents.
ii)The temperature should be kept constant.
iii) The solution should be dilute.
iv) The two solvents are immiscible or only very sparingly miscible and the mutual solu-
bility of the two solvents should not be affected by the solute.
v)The concentration should be compared after the establishment of the equilibrium.
5.9.11. Give the mathematical expression of partition coefficient in case of

(a) No association or dissociation
(b) Association and
(c) Dissociation of the molecule.
Ans. In case of no association or dissociation: the Partition coefficient
C
KD = C1
2
Where, KD , C1 and C2 are partition or distribution coefficient, concentration of solute in
solvent 1 and concentration of solute in solvent 2.
In case of dissociation: Consider a solute A which dissolves in solvent I without any
change but dissociate in solvent II to species B and C (fig.). Let C1 be the concentration
of the solute in solvent I and C2 the total concentration in solvent II. Suppose α is the
degree of dissociation of the solute A in phase II. Then the equilibrium concentration of
the various species in phase II would be as shown:
A ¿ B + C
C2 (1 − α) ¿ C2 α + C2 α
Evidently, the concentration of the undissociated molecules of A in the second phase is

C2 (1 − α). Therefore, the distribution law equation in this case becomes
C
KD = C (11−α)
2
Similarly, in the solute dissociates in both the solvents, then the distribution law becomes
C (1−α )
KD = C2 (1−α1 )
2 2
In case of association: Consider a solute A which dissolves in solvent I without any
change but it undergoes association in solvent II to give molecules (A)n . The equilibrium
between the associated and the single molecules in phase II would be as shown:
nA ¿ (A)n
Applying the law of chemical equilibrium to the equilibrium(in phase II)between the as-
sociated and single molecules,
(A)n ¿ nA
Therefore, distribution law equation in this case becomes
]n
K = [([A
A)n ]
Where, [A] is the concentration of the single molecule and [(A)n ] is the concentration of
associated molecules. Let, the total concentration of the solute A in phase I = C1 and the
total concentration of the solute in phase II = C2 . If the solute exists largely as associated
molecules in phase II, which is generally true except in case of very dilute solutions, the
concentration of the associated molecules, [(A)n ] may be taken as equal to the concentra-
tion of the solute in phase II, i.e.,
[(A)n ] = C2
[A]n = K × [(A)n ]
p
[A] = n K × [(A)n ]
p
= Constant × n [(A)n ]
Substituting the value of [(A)n ] from equation (2), we have

p
[A] = Constant × n C2
Since, the distribution law is valid only for the concentration of similar species in the two
phases, hence,
C1
= Constant
A
C1
p
n C = Constant
2
= KD
5.9.12. What do you mean by solubility?

Ans. At a given temperature the amount of solute requires to prepare 100 grams of
solvent saturated that amount of solute is known as the solubility of that solute in that
solvent at that temperature.
5.9.13. Give one example of each where solubility

(i) increase
(ii) decrease and
(iii) remain unchanged during increasing in temperature of solution.
Ans. The solubility
i) increase, during increasing in temperature of solution in case of KNO3
ii) decrease during increasing in temperature of solution in case of Na2 SO4 after 400 C
temperature.
and iii) remains unchanged during increase in temperature of solution in case of NaCl
5.9.14. If the experiment of determination of partition coefficient is carried out at two different
temperatures 300 C and 600 C. Is the partition coefficient value will be same or different
at two different temperatures?
Ans. At two different temperatures the solubility of acetic acid(or any other solute) in
different solvent may or may not be same. So their concentration ratio also may or may
not be same.
5.9.15. What do you mean by colligative properties.

Ans. Colligative properties are those properties which depend upon the number of solute
particles(molecules or ions) and not upon the nature of the solute.
Example: i) relative lowering of vapour pressure
ii) elevation of boiling point
iii) depression of freezing point.
iv) osmotic pressure.
5.9.16. During titration of any weak acid (say acetic acid) with strong base (say standard. NaOH)
which indicator will you prefer?
Ans. Phenolphthalein indicator because a weak acid will react with a strong base to form
a basic (pH > 7) solution. As Phenolphthalein indicator shows its colour change at pH
8.3 - 10.0. for this reason we will use Phenolphthalein indicator.

Ans. If a solute is mixed with two different immiscible solvents without any reaction
except association or dissociation at constant temperature and at equilibrium the concen-
tration ratio of the solute in two solvents are constant at that temperature irrespective
to their ratio of mixing. Knowledge of this experiment helps in extraction of valuable
material in crude oil and in the chemistry of emulsion like cosmetics, perfumes.
Chapter 6
Experiment name:Viscosity of
solutions (determination of
percentage composition of sugar
solution from viscosity)

(Determination of percentage composition of sugar solution from viscosity )
6.2 Theory
Due to internal friction, when a fluid passes through one another, it experiences a resistance to
its flow which is known as viscosity. The coefficient of viscosity is a measure of the resistance
and defined as the tangential force per unit area required to maintain unit difference of velocity
between two layers unit distance apart. Its unit in CGS system is dyne.sec.cm-2 . When a
homogeneous fluid of volume ’V’ flows through a capillary tube of length ’l’, radius ’r’, in time
’Θ’, under a driving force ’P’, the co-efficient of viscosity is given according to Poisseuille’s formula
by
ΠPr4 θ
η =
8Vl
The experimental determination of viscosity is rather different. If η1 and η2 are the viscosity
of two different liquids of density ρ1 and ρ2 respectively which are successively allowed to fall
through the same length h of capillary e.g. between the marks of an Ostwald viscometer, the
pressures are given by hρ1 g and hρ2 g and thus η1 and η2 are given by
Πhρ1 gr4 θ1
η1 =
8Vl
and,
Πhρ2 gr4 θ2
η2 =
8Vl
57
58 CHAPTER 6. DETERMINATION OF PERCENTAGE COMPOSITION
P = Pressure difference between two ends. Then

η2 ρ2 θ2
=
η1 ρ1 θ1
Now,
ρ2 θ2 × η1
η2 =
ρ1 θ 1

6.3.1. Supplied sugar solution(5 %, 10%, 15% and unknown)

6.4.1. Thermostate
6.4.2. Viscometer (Ostwald)
6.4.3. Beckmann thermometer
6.4.4. Pipette
6.4.5. Specific gravity bottle
6.4.8. Beakers
6.4.9. Funnel
6.4.10. Stand with clamp
6.4.11. Stop watch
6.4.12. Wash bottle
6.4.13. Tissue paper
6.4.14. Weighing balance
6.5 Procedure
6.5.1. Measurement of density of a solution
First the weighing of dry specific gravity bottle then filled specific gravity bottle with
water and with supplied sugar (5 %, 10%, 15% and unknown)solution one by one and take
the weight. The density of the solution can be determined by following way.
Room temperature = ——— 0 C
Density of water at that temperature = ——— gm/cc
we know
Wt
Density(ρ) =
V
6.5. PROCEDURE 59
So,
Wt1
ρ1 =
V
and
Wt2
ρ2 =
V
Now,
ρ2 Wt2 × V
=
ρ1 Wt1 × V
ρ2 Wt2
Or, =
ρ1 Wt1
Wt2 × ρ1
Or, ρ2 =
Wt1
Viscosity of water at that temperature = ——— Poise
Table 6.1: Measurement of density of a solution by using specific gravity bottle

Wt. of dry Name of Wt. of sp. Wt. of Density
and clean sp. materials Gravity only (gm/cc)
gravity bottle taken bottle with materials
(gm) (gm) materials (gm)
distilled water W2 Wt.W = W2 − W1 supplied
Wt.x% ×ρW
x% Sugar solution W3 Wt.x% = W3 − W1 Wt.W
Wt.y% ×ρW
W1 y% Sugar solution W4 Wt.y% = W4 − W1 Wt.W
Wt.z% ×ρW
z% Sugar solution W5 Wt.z% = W5 − W1 Wt.W
Wt.Un% ×ρW
unknown% Sugar W5 Wt.Un% = W6 − W1 Wt.W
solution
Table 6.2: Density of sugar solution at different concentrations

Concentration x% y% z% Un%
Density (gm/cc) - - - -
6.5.2. Measurement of time by stopwatch and determination of Viscosity co-efficient

The viscometer was cleaned thoroughly and clamped vertically in a stand. Then a fixed
amount of sugar solution was taken in it by sucking up and allowed to fall freely between
the two marks and time was noted and repeated for three times. For 5%, 10%, 15% and
unknown solution the same was repeated.
Table 6.3: Measurement of time by stopwatch and determination of Viscosity co-efficient

Materials Number of Time Mean Density Viscosity
observation required (sec.) time (sec) (gm/cc) (Poise)
1 -
Pure water 2 -
3 -
1 -
x% Sugar solution 2 -
3 -
1 -
y% Sugar solution 2 -
3 -
1 -
z% Sugar solution 2 -
3 -
1 -
Un% Sugar solution 2 -
3 -
6.6 Calculation
6.6.1. Density measurement of sugar solution at different concentrations we know
Wt.
Density(ρ) =
V
Wt.x%
So, ρx% =
V
Wt.W
and ρW =
V
ρ Wt.x% × V
Now, x% =
ρW Wt.W × V
ρ Wt.x%
Or, x% =
ρW Wt.W
Wt.x% ρW
Or, ρx% =
Wt.W
6.7. PRECAUTION 61
6.6.2. Viscosity measurement of sugar solution at different concentrations we know η1 and η2 are
given by
Πhρx% gr4 θx%

ηx% =
8Vl
ΠhρW gr4 θW
and, ηW =
8Vl
P = Pressure difference between two ends.
ηx% ρx% θx%
=
ηW ρW θW
ρx% θx% ηW
Now, ηx% =
ρW
6.7 Precaution
6.7.1. The viscometer must be cleaned and rinsed.
6.7.2. The viscometer should be clamped in a vertical position and its height must remain con-
stant each time when it is clamped.
6.7.3. Exactly same volume of the two liquids should be used.
6.7.4. The viscometer should not be disturbed during measurement of time of flow.
6.8 Conclusion
In industry or in our daily life we have to measure the concentration of different solutions. There
are many ways to measure the concentration or percentage composition such as gravimetric
method and volumetric method. Viscosity measurement is a such type of important method by
which we can measure the concentration or percentage composition of any unknown solution.

6.9.1. What is fluid?
Ans. A substance that has no fixed shape and able to flow easily.
6.9.2. How many types of flow are there in fluid?

A. Steady flow: When all the time derivatives of a flow field vanish, the flow is considered
to be a steady flow. Steady-state flow refers to the condition where the fluid properties
at a point in the system do not change over time. laminar flow over a sphere is steady
in the frame of reference that is stationary with respect to the sphere. Turbulent flows:
Turbulent flows are unsteady by definition. A turbulent flow can, however, be statistically
stationary. In a frame of reference that is stationary with respect to a background flow,
the flow is unsteady.
6.9.3. What is density?

Ans. The density of a substance is its mass per unit volume. The symbol most often
used for density is ?. Mathematically, density is defined as mass divided by volume - ,
where ? is the density, m is the mass, and V is the volume Its CGS unit is gm/cc.
6.9.4. How relative density is measured with the help of specific gravity bottle?
Ans. Relative density, or specific gravity is the ratio of the density (mass of a unit volume)
of a substance to the density of a given reference material. Specific gravity usually means
relative density with respect to water.
Measurement: A pycnometer (from Greek:(puknos) meaning ”dense”), also called py-
knometer or specific gravity bottle, is a device used to determine the density of a liquid.
A pycnometer is usually made of glass, with a close-fitting ground glass stopper with a
capillary tube through it, so that air bubbles may escape from the apparatus. This device
enables a liquid’s density to be measured accurately by reference to an appropriate working
fluid, such as water or mercury, using an analytical balance[citation needed]. If the flask
is weighed empty, full of water, and full of a liquid whose relative density is desired, the
relative density of the liquid can easily be calculated. The particle density of a powder,
to which the usual method of weighing cannot be applied, can also be determined with a
pycnometer. The powder is added to the pycnometer, which is then weighed, giving the
weight of the powder sample. The pycnometer is then filled with a liquid of known density,
in which the powder is completely insoluble. The weight of the displaced liquid can then
be determined, and hence the relative density of the powder.
6.9.5. What is viscosity?

Ans. Viscosity is due to the friction between neighboring particles in a fluid that are
moving at different velocities. When the fluid is forced through a tube, the fluid generally
moves faster near the axis and very slowly near the walls; therefore, some stress (such as a
pressure difference between the two ends of the tube) is needed to overcome the friction be-
tween layers and keep the fluid moving. For the same velocity pattern, the stress required
is proportional to the fluid’s viscosity. A liquid’s viscosity depends on the size and shape
of its particles and the attractions between the particles. B. The dynamic (shear) viscosity
of a fluid expresses its resistance to shearing flows, where adjacent layers move parallel to
each other with different speeds. It can be defined through the idealized situation known
as a Coquette flow, where a layer of fluid is trapped between two horizontal plates, one
fixed and one moving horizontally at constant speed . (The plates are assumed to be very
large, so that one need not consider what happens near their edges.) C. If the speed of the
top plate is small enough, the fluid particles will move parallel to it, and their speed will
vary linearly from zero at the bottom to at the top. Each layer of fluid will move faster
than the one just below it, and friction between them will give rise to a force resisting their
relative motion. In particular, the fluid will apply on the top plate a force in the direction
opposite to its motion, and an equal but opposite one to the bottom plate. An external
force is therefore required in order to keep the top plate moving at constant speed. D.
The magnitude of this force is found to be proportional to the speed and the area of each
plate, and inversely proportional to their separation.
6.9.6. What is the relation of density and viscosity?

Ans. Poiseleius equation is -
πPr4 θ
η =
8Vl
Where a homogeneous fluid of volume ’V’ flows through a capillary tube of length ’l’,
radius ’r’, in time ’Θ’, under a driving force ’P’ from the equation it is found that density
and viscosity are directly proportional.
6.9.7. What is the expression of viscosity?

Ans. Newton gave the equation-
Viscosity coefficient is a measure of viscosity is given by-
dv
F ∝ −A
dr
dv
F = −ηA
dr
Where, F is opposing force per unit area of liquid act opposite to the flow of liquid.
η coefficient of viscosity and has dimension ML-1 T-1
and, dv is velocity gradient
dr
viscosity acts as in opposite direction of the fluid flow.That is why the negative terms is
used.
J. L. Poiseuillie give the equation in 1844 and it is termed as Poiseuillie equation.
πPr4 θ
η =
8Vl
When a homogeneous fluid of volume ’V’ flows through a capillary tube of length ’l’, radius
’r’, in time ’Θ’, under a driving force ’P’
6.9.8. Why the negative sign is used in the viscosity expression?
Ans. From Newton’s law it is found that viscosity acts as in opposite direction of the
fluid flow.
dv
F ∝ −A
dr
dv
F = −ηA
dr
That is why the negative sign is used.
6.9.9. What is viscosity coefficient?

Ans.From Newton’s law it is found that viscosity acts as in opposite direction of the fluid
flow.
dv
F ∝ −A
dr
dv
F = −ηA
dr
η coefficient of viscosity viscosity and has dimension ML-1 T-1
6.9.10. How many types of viscosity are there? Give the name and expression of each type of
viscosity.
Ans. There are four type of viscosity: Shear viscosity, Relative viscosity, Specific viscosity
and Intrinsic viscosity.
6.9.11. Density and viscosity are extensive or intensive property? Explain.

Ans. Intensive property. As it does not depend on mass and depends on nature of the
fluid.
6.9.12. Give the Poiseulle’s equation of viscosity.

Ans. J. L. Poiseuillie gave the equation in 1844 and it is termed as Poiseuillie equation.
πPr4 θ
η =
8Vl
Where, F is opposing force per unit area of liquid act opposite to the flow of liquid.
η coefficient of viscosity viscosity and has dimension ML-1 T-1
and, dv is velocity gradient
dr
viscosity acts as in opposite direction of the fluid flow.That is why the negative terms are
used.
6.9.13. What is the effect of temperature on viscosity of

(i) liquid and
(ii) gas?
Ans. In case of liquid, the viscosity decreases with rise in temperature as with rise in
temperature volume increases, mass fixed so density and viscosity decreases. In case of
gas, the viscosity increases with rise in temperature as with rise in temperature randomness
of gas molecule as well as number of collision as well as collision frequency increases so
viscosity increases.
6.9.14. In this practical what type of viscosity is measured?

Ans. Relative viscosity.
6.9.15. What is velocity gradient and rate of shear?

Ans. The dynamic (shear) viscosity of a fluid expresses its resistance to shearing flows,
where adjacent layers move parallel to each other with different speeds. It can be defined
through the idealized situation known as a Coquette flow, where a layer of fluid is trapped
between two horizontal plates, one fixed and one moving horizontally at constant speed
. (The plates are assumed to be very large, so that one need not consider what happens
near their edges.) If the speed of the top plate is small enough, the fluid particles will
move parallel to it, and their speed will vary linearly from zero at the bottom to at the
top. Each layer of fluid will move faster than the one just below it, and friction between
them will give rise to a force resisting their relative motion. In particular, the fluid will
apply on the top plate and a force in the direction opposite to its motion, and an equal
but opposite one to the bottom plate. An external force is therefore required in order to
keep the top plate moving at constant speed. The magnitude of this force is found to be
proportional to the speed and the area of each plate, and inversely proportional to their
separation. The ratio is called the rate of shear deformation or shear velocity, and is the
derivative of the fluid speed in the direction perpendicular to the plates. Isaac Newton
expressed the viscous forces by the differential equation This formula assumes that the
flow is moving along parallel lines and the axis, perpendicular to the flow, points in the
direction of maximum shear velocity. This equation can be used where the velocity does
not vary linearly with , such as in fluid flowing through a pipe. Use of the Greek letter mu
(µ) for the dynamic stress viscosity is common among mechanical and chemical engineers,
as well as physicists. However, the Greek letter eta (η) is also used by chemists, physicists,
6.9.16. What are the dimension and unit of viscosity?

Ans. Poise (symbol: P)Named after the French physician Jean Louis Marie Poiseuille
(1799-1869), this is the cgs unit of viscosity, equivalent to dyne-second per square cen-
timetre. It is the viscosity of a fluid in which a tangential force of 1 dyne per square
centimetre maintains a difference in velocity of 1 centimetre per second between two par-
allel planes 1 centimetre apart.Even in relation to high-viscosity fluids, this unit is most
usually encountered as the centipoise(cP), which is 0.01 poise. Many everyday fluids have
viscosities between 0.5 and 1000 cP
6.9.17. What is the name of the instrument by which you measure the viscosity?
Ans. Ostwald Viscometer
Q Do you know the name of another type of viscometer?
Ans. Brookfield viscometer, Canon-Fenske viscometer, Ubbelohde viscometer,B4 ,B6 Cup
etc.
6.9.18. Why the viscosity measurement is carried out in a thermostat?

Ans. As viscosity varies with temperature so to carry out the experiment at constant
temperature thermostat is essentially required.
6.9.19. Why the Ostwald viscometer is always kept in a vertical position?

Ans. In Poiseleius equation Pressure difference which is the driving force of fluid flow can
be expressed as P = hρg. Again, we know the value of gravitational force change with an
angle so to keep g constant for each experiment the Ostwald viscometer is always kept in
a vertical position.
6.9.20. How percentage composition of any solution can be measured from viscosity and percent-
age graph?
Ans. After drawing the viscosity of given percentage composition of solution in a graph
paper we get a straight line by connecting the points. The viscosity of unknown solution
is fit on the viscosity axis and comes to the straight line where it meets, then comes down
to the percentage composition axis. The cross section point is the percentage composition
of unknown solution.
6.9.21. Why during filling up of liquid in Ostwald viscometer to the upper mark level just top of
the lower bulb every time?
Ans. As pressure is related with height in case of vertical flow of liquid so with change in
height(h) pressure will also change. So to keep pressure constant in each experiment during
filing up the liquid in Ostwald viscometer we have to careful about the height of liquid level.
6.9.22. Why a capillary tube is taken in the Ostwald viscometer?

Ans. To avoid the turbulence flow and to allow only the streamline flow a capillary tube
is taken in the Ostwald viscometer as in a capillary tube only streamline flow is possible.
6.9.23. What is Reynolds number?

Ans. The Reynolds number can be defined for several different situations where a fluid
is in relative motion to a surface.These definitions generally include the fluid properties
of density and viscosity, plus a velocity and a characteristic length or characteristic di-
mension. For flow in a pipe of diameter, experimental observations show that for ”fully
developed” flow, laminar flow occurs when and turbulent flow occurs. In the interval be-
tween 2300 and 4000, laminar and turbulent flows are possible and are called ”transition”
flows, depending on other factors, such as pipe roughness and flow uniformity.

Ans. In industry or in our daily life we have to measure the concentration of different
solutions. There are many ways to measure the concentration or percentage composition
such as gravimetric method and volumetric method. Viscosity measurement is such a
type of important method by which we can measure the concentration or percentage
composition of any unknown solution. In case of many polymer the the molecular weight
is measured by using the viscosity of the polymer and is called viscosity average molecular
weight. This can be done by measuring the specific viscosity of a polymer in different
concentration in a particular solvent to which it does not react. Then by plotting the
graph of specific viscosity vs concentration of the polymer and extrapolating to the Y
AXIS we will get the intrinsic viscosity. Ultimately by using Mark-Kahn-Hawing equation
we will get the viscosity average molecular weight.
Chapter 7
Experiment
name:Conductometric titration
for determination of the strength
of a given HCl solution by
titration against a standard
NaOH solution.

(Conductometric titration for determination of the strength of a given HCl solution by titration
against a standard NaOH solution.)
7.2 Theory
The monobasic acid HCl being a strong electrolyte undergoes complete ionization and produces
a large number of cations and anions in solution. Moreover ionic conductance of H+ ions being
highest (I0 + ' 350). Thus the initial conductance of a solution will be very high. When this
H
acid is gradually titrated against a base NaOH, being added from burette, the following reaction
will occur.
H+ + Cl- + Na+ + OH- → Na+ + Cl- + H2 O
The salt, a strong electrolyte remains in the solution in completely ionized form, while water
being a very weak electrolyte (and in presence of H+ ions its ionization is still smaller) remains
partially ionized. Thereby H+ ions are gradually replaced by equivalent amount of Na+ ions
which have relatively much lower ionic conductance than that of H+ ions. Thus the conductance
of resulting solution will decrease steeply. This trend will continue until all the H+ ions are
replaced by Na+ ions i.e. equivalent point is reached. At equivalent point only NaCl is present.
Beyond equivalent point when further amount of alkali is added Na+ and OH- of excess alkali
67
68 CHAPTER 7. CONDUCTOMETRIC TITRATION
remain in the solution unutilized. Consequently the conductance of the solution increases due
to the presence of newly added Na+ and OH- ions (I0 - ' 200). The point of intersection of
OH
curve representing the variation of conductance with the volume of alkali added, corresponding
to the minimum conductance and consequently equivalence point. The volume of alkali added
corresponding to the equivalent point represents the volume of alkali required for neutralization
of acid.

7.3.1. Standard oxalic acid
7.3.2. 0.5(N) NaOH solution
7.3.3. 0.1(N) HCl solution
7.3.6. Standard KCl solution

7.4.1. Conductivity meter
7.4.2. Conductivity cell
7.4.3. Pipette
7.4.6. Beakers
7.4.8. Wash bottle
7.4.9. Tissue paper
7.5 Procedure
³ ´
7.5.1. Prepare 250 ml of N standard oxalic acid solution: Equivalent weight of oxalic acid is
10 ³ ´
63. Hence in order to prepare 250 ml of 10 N solution, 1.575 gm oxalic acid is required.
Weight out 1.575 gm of AR quality oxalic acid into a clean 250 ml volumetric flask. Wash
the entire quantity of solid into the flask by careful addition of distilled water. Hold the
flask firmly and shake carefully. When the entire solid has dissolved, makeup the volume
to the mark.
µ ¶
W N
= ×
1.575 10
7.5. PROCEDURE 69

³ ´
10
- - - 1.575 -
³ ´
7.5.2. Prepare 250 ml of an approximately N 2 NaOH solution and standardize it against oxalic
acid solution using phenolphthalein as indicator. ³ ´
Equivalent weight of NaOH is 40. Hence in order to prepare 250 ml of N 2 solution,
approximately 5 gm NaOH is required. Weight out approximately 5 gm of AR quality
NaOH into a clean 250 ml volumetric flask. Wash the entire quantity of solid into the
flask by careful addition of distilled water. Hold the flask firmly and shake carefully.
When the entire solid has dissolved, makeup the volume to the mark. Let the weight of
NaOH taken = W gm. Strength of NaOH
µ ¶
W N
= ×
5 2
Table 7.2: Determination of strength of NaOH solution

of oxalic NaOH solution(ml) of of of
observation acid oxalic oxalic NaOH
(ml) Initial Final NaOH(ml) acid(N) (N)
2. - - - - - -
3. - - - - - -
4. - - - - - -
5. - - - - - -
7.5.3. Prepare 250 ml of an approximately ( 10 N )HCl solution: In order to prepare 250

N ) HCl solution take 2.833 ml(approx.)concentrated 12 (N) HCl into a clean 250
ml of ( 10
ml volumetric flask. Wash the entire quantity of HCl into the flask by careful addition
of distilled water. Hold the flask firmly and shake carefully. When the entire HCl has
7.5.4. Rinse the conductivity cell with de-ionized water:Rinsing of the conductivity cell
with de-ionized water two to three times and clean the cell carefully with tissue paper.
7.5.5. Standardization of conductivity cell:Pipette out 25 ml of 0.1 (N) KCl solution into the
conductivity cell and immerse the electrodes in the cell carefully that both the electrodes
are completely immersed within the solution. Join the cell with the conductive bridge and
Push the button for standardization.
7.5.6. Set up of conductivity cell:Pipette out 25 ml of HCl solution into the conductivity cell
and immerse the electrodes in the cell carefully that both the electrodes are completely
immersed within the solution. Join the cell with the conductive bridge and measure the
conductivity very carefully.
7.5.7. Measurement of conductance:Add NaOH solution from a burette dropwise to a definite

number of drops(10 or 20 drops) and starrer the solution carefully for proper neutralization
reaction.Repeat the process until you have at least six points beyond the end points.
7.5.8. Graph plotting and determination of end point:Draw the curve by plotting the
conductance(Y-axis) against the drops of alkali added(X-axis), find the end point by ex-
trapolating the two straight line. The cross-section point of the two lines is the end point
and calculate the strength of the HCl solution.
Table 7.3: Conductometric Titration of HCl solution against NaOH solution

No of Volume of Drops of Conductance
observation HCl taken (ml) NaOH added (S)
1. 25 0 -
2. - 10 -
3. - 20 -
4. - 30 -
5. - 40 -
6. - 50 -
7. - 60 -
8. - 70 -
9. - 80 -
7.6 Calculation
Let the number of drops of alkali required to neutralized 25 ml of HCl solution = x
We know, 20 drops = 1 ml
X
Therefore, x drops = 20 ml
As we know,
V1 × S1 = V2 × S2
V1 × S1
S2 =
V2
Here,
V1 = Volume of standard NaOH solution (ml)

V2 = volume of HCl acid taken( 25 ml)
S2 = Strength of HCl acid solution in Normality?
7.7 Precaution
7.7.1. Conductivity cell must be thoroughly washed with de-ionized water.
7.7.2. Ensure that there are no air bubbles in the burette.
7.8. CONCLUSION 71
7.7.3. During titration, the beaker should be constantly swirled.

7.7.4. For each titration, use same number of drops of NaOH solution.
7.7.5. Wash the Conductivity cell thoroughly with de-ionized water.
7.8 Conclusion
7.8.1. Where volumetric analysis is not possible as well as where indicator is not applicable this
instrumental method is helpful to determine the strength of acid or base.
7.8.2. In case of weak acid base titration where no any indicator is applicable this instrumental
method is helpful to determine the strength of acid or base.
7.8.3. In case of micelle formation by any surfactant the CMC(critical micelle concentration)
values can be understood by using this method.

7.9.1. What is conductance?
Ans. Ohms law of resistance etc. which are applicable for electronic conductor are
equally valid for electrolytic conductors. In case of electrolytic solution the general term
used is conductance. Conductance (L) is the reciprocal of resistance(R).Thus we can write
that conductance of an electrolyte is
1
L=
R
; Where resistance measures the obstruction to the flow of current, conductance measures
the ease of the flow of current.
7.9.2. Why is the term conductometry used here?

Ans. Here, this acid base titration reaction can be done by measuring the conductance
measurement.
7.9.3. What is specific conductance, equivalent conductance and molar conductance? What ate
their relation?
Ans. Ohms law of resistance etc. which are applicable for electronic conductor are equally
valid for electrolytic conductors. Thus, we can write that resistance of an electrolyte as-
l
R = ρ
A
In case of electrolyte l is the distance between two electrodes and A is the cross section
area of each electrode. Rho is called specific resistance of a solution placed between two
electrodes, unit distance apart and which are of unit area.
specific conductance(κ): It is the conductance of a solution placed between two elec-
trodes which are unit distance apart and unit cross section area. Its unit is mho cm- . So,
specific conductance of a solution is the conductance of the solution enclosed in a unit
cube. Dilution decreases the specific conductance as with dilution number of ions per unit
cube decrease. Specific conductance
1
κ =
ρ
1
= L
A
Equivalent conductance (λc): It is the conductance of a solution containing ONE
EQUIVALENT of an electrolyte placed between two electrodes which are unit distance
apart and unit cross section area. Its unit is mho cm2 /gm-eqiv. or S cm2 (equv.)-1 . So,
Equivalent conductance of a solution is the conductance of the solution containing ONE
EQUIVALENT of an electrolyte enclosed in a unit cube. Equivalent conductance
1000
(λc) = κ( )
C
C is the concentration of the solution in gm equivalent per lit.
Molar conductance(λm): It is the conductance of a solution containing ONE MOLE of
an electrolyte placed between two electrodes which are unit distance apart and unit cross
section area. Its unit is mho cm2 /gm-mole or S cm2 (mole)-1 . So, Molar conductance
of a solution is the conductance of the solution containing ONE MOLE of an electrolyte
enclosed in a unit cube.
Molar conductance-
1000
(Λm ) = κ( )
M
M is the concentration of the solution in gm mole per lit.
Molar conductance
(Λm ) = (p × q) × Equivalent conductance(Λc)
(p and q is the valency of cation and the number of cation respectively).
7.9.4. What is the reaction and which indicator is used during the titration among
(i) strong acid(HCl) and strong base(NaOH)
(ii) strong acid(HCl) and weak base(NH4 OH)
(iii) weak acid(CH3 COOH) and strong base(NaOH)
(iv) weak acid(CH3 COOH) and weak base(NH4 OH).
Ans. i) Strong acid (HCl) and strong base (NaOH);
Reaction:
HCl + NaOH = Na+ + Cl- + H2 O
Indicator; any type Indicator is applicable

ii) Strong acid (HCl) and weak base (NH4 OH);
Reaction:
HCl + NH4 OH = NH+ -

4 + Cl + H2 O
Indicator; Methyle orange indicator
iii) Weak acid(CH3 COOH) and strong base(NaOH);
Reaction:
CH3 COOH + NaOH = Na+ + CH3 COO- + H2 O

Indicator; Phenolphthalein indicator

iv) Weak acid (CH3 COOH) and weak base (NH4 OH);
Reaction:
CH3 COOH + NH4 OH = NH+ -

4 + CH3 COO + H2 O
Indicator; No indicator, only by conductometry, pH-metry, surface tension etc.
7.9.5. Give the conductance vs concentration curve for (i) strong electrolyte and (ii) weak elec-
trolyte.
Ans. The conductance vs concentration curve for (i) strong electrolyte and (ii) weak
electrolyte are given below.
Conductance concentration graph(Strong and weak electrolytes)
7.9.6. What is transport number? What is the ionic mobility value H+ and OH- ?
Ans. Although equivalent amount of cation and anion are discharged during electrolysis,
their velocity may be different. So, current carrying capacity of cation and anion may be
different. Fraction of the total current carried by an ion is known as its transport number.
Thus if Q is the total current pass, out of which q+ and q- are those carried by cation and
anion respectively. Their transport number t+ and t- are-
q+
t+ =
Q
q-
and t- =
Q
Total transport number
t+ + t- = 1
7.9.7. Velocity of Li+ is the smallest among alkali metals ion in aqueous solution; but in
ORGANO aqueous solution it is the highest-Why?
Ans. Li+ is the smallest in size among the alkali metals ion. So it may be expected
that its velocity should be high. But in aqueous solution velocity follows the order
Li+ < Na+ < K+ < etc. This is due to hydration. Water is polar solvent. Due
to its smaller size and high charge density Li+ ion is highly associated by water molecules
and velocity is the lowest.
7.9.8. Will transport number of Cl- in HCl and in NaCl be same?

Ans. From the expression of transport number we know that it is also depends upon the
counter ion.
- V-Cl
tCl (HCl) =
(V+ -
H + VCl )
V-Cl
and t-Cl (NaCl) =
(V+ -
Na + VCl )
As , V+ +
H and VNa not same so transport number will be different.
7.9.9. Why in this v shaped curve after the end point the slope of the curve is less steeper than
first one (acid in cell)?
Ans. As, the ionic mobility of H+ '(300)and OH- '(250)are different so, ion conductance
is also different. Before the end point high conducting H+ ions replace by low conducting
Na+ ion and after end point conductance increase due to excess OH- ion . As H+ ion
conductance is more than OH- ion conductance after the end point the slope of the curve
is less steeper than first one.
7.9.10. How the end point is determined from conductance vs volume Graph?
Ans. From the graph where two straight line intersect each other with a minimum con-
ductance value (both H+ + OH- ion concentration is nil there is only salt and water) is
the end point(neutralization point). From the intersecting point we should draw a line on
X axes(number of drops). From the point on X axes we will get the number of drops as
well as the volume of added alkali.
7.9.11. During conductomeric titration which indicator you have used?

Ans. No, here we need not require any indicator. This advantage of the titration reaction
where without any indicator we can determine the strength of any unknown acid or base.
7.9.12. At the end point there is no HCl and NaOH - yet there is some conductance of the solution
- why?
Ans. From the graph where two straight line intersect each other with a minimum con-
ductance value (both H+ + OH- ion concentration is nil) is the end point(neutralization
point)but there is only saltNa+ + Cl- . As we know all salts are strong and gets fully
ionized in solution also carry current.
7.9.13. What is a strong and weak acid base? Give examples.

Ans. Strong acid: Acids which are fully ionized in aqueous solution are called strong
acid. Example: HCl, H2 SO4 and HNO3 etc.
Strong Base: Bases which are fully ionized in aqueous solution are called strong base.
Example: NaOH, KOH and CaO etc.
Weak acid: Acids which are not fully ionized in aqueous solution and remain in equilib-
rium with undissociated acid are called weak acid. Example: CH3 COOH, HCOOH etc.
Weak Base: Bases which are not fully ionized in aqueous solution and remains in equi-
librium with undissociated base are called weak base. Example: NH4 OH, ZnOH2 etc.
7.9.14. What is Kohlrausch’s law?

Ans. Kohlrausch’s law states that ”At infinite dilution, when the ionization is complete,
each ion makes a definite contribution towards equivalent conductance of the electrolyte,
irrespective of the nature of the other ion(counter ion) with which it is associated”. This
means the equivalent conductance at infinite dilution of an electrolyte is the sum of the
contribution form of the ions(the cations and anions).
Thus,
λ∞ = λ+ + λ-
∞ ∞
Where, λ∞ is the equivalent conductance at infinite dilution ; λ+ -

∞ and λ∞ are the contri-
bution of equivalent conductance of cations and anions respectively at infinite dilution of
the same electrolyte.
7.9.15. What is the relation between temperature and conductance?

Ans. The equivalent conductance increases with increase in temperature. The varia-
tion of equivalent conductance at infinite dilution or limiting equivalent conductance with
temperature can be given as
λt = λ25 [1 + α(t - 25)]
∞ ∞
Where, λt∞ and λ25 0 0

∞ are the equivalent conductance at infinite dilution at t C and 25 C
respectively. α is the temperature coefficient given as α = λ1∞ ( dλ∞ ). The temperature
dt
coefficient for H+ is 0.014 deg-1 and for OH- is 0.018 deg-1 and generally for all ions
except H+ and OH- is taken to be 0.02 deg-1 .
7.9.16. Why conductometer cell is always cleaned by tissue paper after washing with distilled
water?
Ans.During measurement of conductance we should care full about the strength of sup-
plied solution. distilled water is purest but due to presence of dissolve carbon dioxide its
pH is less than 7. Now small amount of water from uncleaned conductometer cell is mixed
to the supplied solution its strength will be change and the result will be erroneous
7.9.17. Neutralization is an exothermic or endothermic process?

Ans. Neutralization is an exothermic process.
7.9.18. Why the heat of neutralization value for any strong acid and strong base is same(13.7
Kcal)?
Ans. In the neutralization reaction between equivalent amount of strong acid vs. strong
base we see in each case one mole of water is produced and -13.7 k.cal heat is liberated
during formation of one mole of water.
Let,
Na+ + OH- + H+ + Cl- = Na+ + Cl- + H2 O; ∆H = −13.7 k. cal
K+ + OH- + H+ + NO-3 = K+ + NO-3 + H2 O; ∆H = −13.7 k. cal
2Na+ + 2OH- + 2H+ + SO2- + 2-
4 = 2Na + SO4 + 2H2 O; ∆H = −13.7 k. cal
7.9.19. Why the heat of neutralisation value is less than 13.7 K. cal. for acid and base neutrali-
sation where any one or both are weak?
Ans. In the neutralization reaction between equivalent amount of strong acid vs. strong
base we we see in each case one mole of water is produced and -13.7 k.cal heat is liberated
during the formation of one mole of water. If any one of the acid or base or both acid and
base are weak, some amount of heat is spent for the dissociation of weak acid or base or
both. As a result liberated heat is some what less than -13.7 k.cal.
7.9.20. What is the nature of graph in the titration among

(i) strong acid(HCl) and strong base(NaOH)
(ii) strong acid(HCl) and weak base(NH4 OH)
(iii) weak acid(CH3 COOH) and strong base(NaOH)
(iv) weak acid(CH3 COOH) and weak base(NH4 OH).
Ans.(i) strong acid(HCl) and strong base(NaOH):
Initially the conductivity of acid solution is high due to the presence of highly mobile
H+ ions. This is represented by point A on the curve. The conductivity cell is placed in
the acid solution taken in the beaker and the alkali in the burette. On gradual addition
of NaOH from the burette, highly mobile H+ ions are removed by the added OH- ions to
form nearly non-conducting water molecules.
Conductometric titration graph(strong acid Vs strong base)

Conductometric titration graph(strong acid Vs strong base)
H+ + Cl- + Na+ + OH- → Na+ + Cl- + H2 O
Hence, the conductivity of the solution decreases progressively, till the point B is reached.
On further addition of NaOH, the conductivity of the solution will rise along the curve of
BC, due to the addition of highly mobile OH- ions to the solution. At the minimum point
B, there is no excess of either acid or base and hence, it corresponds to the equivalence
point. The conductance at this point B is not zero because of presence of Na+ and Cl-
ion in the solution.
(ii) strong acid(HCl) and weak base(NH4 OH):

Initially the conductivity of acid solution is high due to the presence of highly mobile H+
ions. This is represented by point A on the curve.
Conductometric titration graph(Strong acid Vs weak base)
H+ + Cl- + NH+ - + -
4 + OH → NH4 + Cl + H2 O
The conductivity cell is placed in the acid solution taken in the beaker and the alkali in
the burette. On gradual addition of weak base from the burette, highly mobile H+ ions
are removed by the added OH- ions to form nearly non-conducting water molecules. After
the end point on farther addition of weak base the graph will be parallel to x axis as the
dissociation of weak base is really negligible. Actually after the equivalence point, con-
ductance virtually remains same as the weak base which is being added is feebly ionized
and, therefore, is not much conducting.
(iii) weak acid(CH3 COOH) and strong base(NaOH):
Acetic acid is a weak electrolyte has low conductivity, as represented by A. As NaOH

is added, the poorly conducting acid is converted into highly ionized salt, CH3 COONa
and consequently the conductivity goes up along AB, the deciding factor on this curve is
presence of Na+ ions.
Conductometric titration graph(Strong base Vs weak acid)
Conductometric titration graph(Strong base Vs weak acid)
CH3 COO- + H+ + Na+ + OH- → Na+ + CH3 COO- + H2 O

When the acid is neutralized, further addition of alkali causes a sharp rise in conductance
along BC due to the presence of highly mobile OH- ions. The intersection of AB and BC
represents the equivalence point.
CH3 COOH + NaOH → CH3 COO- + Na+ + H2 O
(iv) weak acid(CH3 COOH) and weak base(NH4 OH)
Initially a sudden drop of conductance as high conducting H+ ion is replaced by low

conducting metal ions but immediate after, the nature of the graph increases slowly due
to increase of concentration of salt.
CH3 COO- + H+ + NH+ - + -

4 + OH → NH4 + CH3 COO + H2 O
After the end point on further addition of weak base the graph will be parallel to x
axis as the dissociation of weak base is really negligible. After the equivalence point,
conductance virtually remains same as the weak base which is being added is feebly ionized
and, therefore, is not much conducting.
Conductometric titration graph( weak acid Vs weak base)

Ans. Here we need not require any indicator. This advantage of the titration reaction
In analytical work in laboratory or industry if, the supplied acid or base is colored or
black in color where use of any indicator is meaningless,with this experiment we can easily
determine the strength of the unknown acid base.
Chapter 8
Experiment name:. pH-metric

titration for determination of
strength of a given HCl solution
against a standard NaOH
solution.

pH metric titration for determination of strength of a given HCl solution against a standard
NaOH solution.
8.2 Theory
All pH meters have provision for standardizing the glass electrode in a buffer solution of known
pH. This is necessary because different electrodes have different asymmetry potentials. Once the
adjustment has been made so that the meter registers correctly known as the pH of the buffer
solution, the instrument gives the pH other solution without any calculation.
Measurements of pH are also employed to monitor the course of acid-base titrations. The
pH values of the solution at different stages of acid-base neutralization are determined and are
plotted against volume of acid/alkali added. When this acid is gradually titrated against a base
NaOH, being added from burette, the following reaction will occur.
H+ + Cl- + Na+ + OH- → Na+ + Cl- + H2 O
On adding a base to an acid, the pH rises slowly in the initial stages (pH range is used for only
dilute solution, not for concentrated solution) and then it changes rapidly at the end point. Then
it flattens out. The end point of the titration can be detected where the pH changes most rapidly.
However the shape of the inflexion point (i.e. where the pH changes abruptly) and symmetry of
the curve on its two sides depends upon the ionisability of the acid and the base used and on the
basicity of the acid and the acidity of the base.
81
82 CHAPTER 8. PH-METRIC TITRATION

8.3.1. Standard oxalic acid
8.3.2. ( N
5 ) NaOH solution
N ) HCl solution
8.3.3. ( 10
8.3.5. Buffer solution of pH 4, pH 7 and pH 9

8.4.1. pH meter with glass electrode and standard calomel electrode.
8.4.2. Pipette
8.4.3. Burette, Glass rod
8.4.6. Beakers
8.4.8. Wash bottle
8.4.9. Tissue paper
8.5 Procedure
8.5.1. Prepare 250 ml of standard oxalic acid solution ³ ´
N solution,
Let, the weight of oxalic acid taken = W gm.
Strength of oxalic acid-
µ ¶
W N
= ×
1.575 10

³ ´
10
- - - 1.575 -
8.5. PROCEDURE 83
³ ´
8.5.2. Prepare 250 ml of an approximately N 5 NaOH solution and standardize it against oxalic
acid solution using phenolphthalein as an indicator. ³ ´
Equivalent weight of NaOH is 40. Hence in order to prepare 250 ml of N 5 solution,
approximately 2 gm NaOH is required. Weight out approximately 2 gm of AR quality
NaOH into a clean 250 ml volumetric flask. Wash the entire quantity of solid into the
flask by careful addition of distilled water. Hold the flask firmly and shake carefully.
When the entire solid has dissolved, makeup the volume to the mark.
Let, the weight of NaOH taken = W gm.
Strength of NaOH
µ ¶
W N
= ×
2 5
Table 8.2: Determination of strength of NaOH solution

No. Volume Burette reading of Volume Strength Strength
of of NaOH solution(ml) of of of
observation oxalic NaOH(ml) oxalic NaOH
(ml) Initial Final (ml) acid(N) (N)
1. - - - - - -
2. - - - - - -
3. - - - - - -
4. - - - - - -
5. - - - - - -
8.5.3. Prepare 250 ml ( 10 N ) approximately HCl solution: In order to prepare 250 ml

N ) HCl solution take 2.833 ml(approx.)concentrated 12 (N) HCl into a clean 250
of ( 10
ml volumetric flask. Wash the entire quantity of HCl into the flask by careful addition
of distilled water. Hold the flask firmly and shake carefully. When the entire HCl has
8.5.4. Rinse the pH-metric electrode with de-ionized water: Clean the pH meter with
de-ionized water two to three times and clean the cell carefully with tissue paper.
8.5.5. Standardization of pH meter: Wash the electrodes with distilled water and standardize
the pH meter by using buffer solution of pH = 7, pH = 4 or pH= 9, now the selector switch
is put to a pH range of 7 - 14.Join the cell with the conductive bridge and push the button
for standardization.
8.5.6. Set up of pH meter: Pipette out 25 ml of HCl solution into the beaker and immerse
the electrodes in the acid solution carefully. Join the electrode with the pH-metric bridge
and measure the conductivity very carefully.
8.5.7. Measurement of pH: Add NaOH solution from the burette dropwise. Note the corre-
sponding value from the meter. Near the end point add very small amount of NaOH as
possible because change in pH will be very much appreciable because when the acid is
neutralized, further addition of such a small amount raises the pH to about 9 or 10.
Table 8.3: pH-metric Titration of HCl solution against NaOH solution.

No of Volume of HCl Drops of pH Temperature
observation taken (ml) NaOH added 0C
1. 25 0 -
2. - 20 -
3. - 40 -
4. - 60 -
5. - 80 -
6. - 100 -
7. - 120 -
8. - 140 -
9. - 160 -
8.5.8. Graph plotting and determination of end point: Draw the curve by plotting the
pH(Y-axis) against the drops of alkali added(X-axis), find the end point by extrapolating
a straight line from pH 7 on the curve and come down to the X-axis. The point on the
X-axis is the end point.
8.6 Calculation
Let the number of drops of alkali required to neutralized 25 ml of HCl solution = x
We know, 20 drops = 1 ml
X
Therefore, x drops = 20 ml
As we know,
V1 × S1 = V2 × S2
V1 × S1
S2 =
V2
Here,
V1 = Volume of standard NaOH solution (ml)

V2 = volume of HCl acid taken( 25 ml)
S2 = Strength of HCl acid solution in Normality?
8.7 Precaution
8.7.1. pH-metric cell must be thoroughly washed with de-ionized water.
8.7.2. Ensure that there are no air bubbles in the burette.
8.7.3. During titration, the beaker should be constantly swirled.
8.7.4. Electrodes must be immersed properly in the solution and sufficient time to be allowed for
the electrodes to assume the temperature of the solution.
8.8. CONCLUSION 85
8.7.5. For each titration, use same number of drops of NaOH solution.
8.7.6. Leave the selector in zero position when not in use and the electrode must be dipped in
to 3(M)
8.8 Conclusion
7.8.1. Where volumetric analysis is not possible as well as where indicator is not applicable these
instrumental methods are helpful to determine the strength of acid or base.
7.8.2. In case of weak acid base titration where no any indicator is applicable this instrumental
methods helpful to determining the strength of acid or base.
7.8.3. In case of micelle formation by any surfactant the CMC(critical micelle concentration)
values can be understood by using this method.

8.9.1. What is pH?
Ans. The negative logarithm of activity of H3 O+ ion of any solution is called pH of
the solution. pH is also called ”Potential of Hydrogen” or ”power of hydrogen” where
”p” is short for the German word for power, potenz and H is the element symbol for
hydrogen. The H is capitalized because it is the standard to capitalize element symbols.
It is mathematically defined as-
pH = − log a + (negative log of activity of proton)

H
. Activity has a relation with concentration.
Activity = f × concentration
For dilute solution Activity = Concentration [As fugacity(f) = 1 for dilute solution]
8.9.2. Give the mathematical expression of pH.

A. The mathematical expression of pH is -
pH = - log a + (negative log of activity of proton)

H
8.9.3. Give the pH expression for monobasic acid and buffer solution.
Ans. For monobasic acid
1 1
pH = pKa − log C
2 2
8.9.4. Why pH-meter cell is always deepen in concentrated (3M) KCl solution after doing work?
Ans.All pH probes are delivered with a plastic protection cap that can also be used for
storage. Pour a few drops of saturated KCl solution into the cap to ensure that the glass
membrane is kept hydrated and ready to use. For short - term storage, the pH probe can
be placed in a solution of 3.5 molar KCl or pH 4.0 or pH 7.0 pH buffer. Always rinse the pH
probe before use. As a general rule, pH probes (especially reference probes) should never
be stored in deionised water. Overnight, the probe should be stored in the corresponding
electrolyte solution, usually saturated KCl. For long - term storage (2 weeks or more), the
pH probe should be stored with its protection cap filled with storage solution and sealed
with Parafilm.
8.9.5. What is ionic product of water? What is its value at 250 C?

Ans. Pure distilled water undergoes self ionization and form H3 O+ and OH-
H2 O(l) + H2 O(l) = H3 O+ + OH-
Applying law of mass action,
[H3 O]+ [OH]-

Kd =
[H2 O]2
Where, KD is ionization(dissociation) constant of water and for pure water activity of

water is 1(one)
So,
[H3 O+ ][OH]-
KW =
1
KW = +
[H3 O ][OH]-
Its value at 250 C is KW = 10-14
8.9.6. Find the pH of

(i) 10-3 (M)
(ii) 10-7 (M)and
(iii)10-9 (M) HCl solution.
Ans.(i) 10-3 (M)HCl solution:
We know,
pH = −log[H+ ]
= − log10-3
= 3
(ii) 10-7 (M)HCl solution

As, concentration of acid is 10-7 (M). So we have to considered [H+ ] ion from water disso-
ciation also, as from water we get the same concentration of [H+ ].
Now, total [H+ ] = [H+ ] from acid and [H+ ] from water.
[H+ ] = 10-7 + 10-7

= 2 × 10-7
We know,
pH = − log[H+ ]
= − log 2 × 10-7
= −0.301 + 7
= 6.698
(iii)10-9 (M) HCl solution
As, concentration of acid is 10-9 (M). So we have to consider [H+ ] ion from water dissoci-
ation also, as from water we get concentration of [H+ ] = 10-7 which is greater than 10-9 .
Now, total [H+ ] = [H+ ] from acid and [H+ ] from water.
[H+ ] = 10-9 + 10-7

= 10-7 × (1.01)
We know,
pH = − log[H+ ]
= − log 1.01 × 10-7
= − 0.00432 + 7
= 6.995
8.9.7. What is pH scale and pH range?

Ans. The acidity or basicity of any solution can be expressed with scale of pH value
called pH scale. Its range o to 14
8.9.8. Why pH of pure water is 7?

We know,
KW = [H3 O+ ][OH]-
Its value at 250 C is KW = 10-14 ;
[H3 O+ ][OH]- = 10-14
As , [H3 O+ ] = [OH]-
2
[H3 O+ ] = 10-14
[H3 O+ ] = 10-7
Now, pH = − log[H3 O+ ] = 7
8.9.9. Why pH of distilled water is less than 7?

A. pH of distilled water is less than 7 because though distillation we get distilled water is
the purest in the sense that there is no soluble salt but contains trace amount of CO2 gas
which combines with water and form carbonic acid H2 CO3 .
8.9.10. Is -ve pH possible or not? If possible -how?

Ans. In case of high concentrated solution pH will be -ve. Let an HCl solution of 2 (M)
having pH -ve.
8.9.11. What is buffer solution? Give preparation and buffer action of different buffer solution.
Ans. pH of ordinary solution are highly sensitive towards addition of acid or base. In
analytical work we often require solutions which should maintain constant pH value. Such
solution whose pH remains almost constant during addition of small amount of acid or
base are called buffer solution. Buffer solution can be prepared by mixing of-
(I) A weak acid with its salt (e.g.CH3 COOH and CH3 COONa)
(II) A weak base with its salt(e.g. NH4 OH and NH4 Cl)
(III) Two acid salts of same acid(e.g. NaH2 PO4 and Na2 HPO4 ).
To understand the mechanism of buffer action let us consider a buffer made by mixing of
a weak acid HA with its salt BA. The salt is completely dissociated into B+ and A- the
acid HA remains equilibrium as-
HA H+ + A-
To this solution if we add some H+ ions it will combine with A- to give undissociated HA.
As H+ ion concentration remains same pH also remains unchanged. If some OH- is added
it will combine with H+ ion and form undissociated water molecule immediately the loss
of H+ ion will be compensated by farther dissociation of HA according to La-Chatelier
principle. As H+ ion concentration remains same pH also remains unchanged.(In the same
way we can explain action of basic buffer).
pH of any Acid buffer-
A- ]
pH = pKa + log [[HA ]
([A- ] is the concentration of salt)

pH of any basic buffer-
+
[B ]
pH = pKb + log [BOH ]
([B+ ] is the concentration of salt)
8.9.12. What is buffer capacity?

Ans. To compare efficiency of different buffer’s a term buffer capacity (β)has been
defined. It is equal to the equivalent of base required to raise the ph of a buffer solution
by unity(1). Let ’db’ equivalent of base raises the pH by dpH, then buffer capacity-
β = db
dpH
And buffer capacity will be maximum when [acid] = [salt]
8.9.13. What is neutralisation?

Ans. When equivalent amount of an acid reacts with an exactly equivalent amount of a
base consequently produce salt and water is called neutralization.
HCl + NaOH = H2 O + Na+ + Cl-
8.9.14. During pH-metric titration which indicator you have used?

Ans. No, here we need not require any indicator. This advantage of the titration reaction
8.9.15. a) NaOH is added to HCl( In cell )

b)HCl is added to NaOH( In cell ) then what will be the nature of the graph?
Ans. a) If NaOH is added to HCl( In cell ), it slowly rises with the addition of drops of
NaOH and then sudden jump occur after that again slowly rises.
pH-metric titration graph acid in cell
b) If, HCl is added to NaOH( In cell ), just a reverse pattern curve will be obtained.
pH-metric graph strong base in cell

8.9.16. How the end point is determined from pH vs volume Graph?
Ans. As we know the pH value for neutral compound solution is seven and at the end
point (neutralization point) both H+ andOH- ion concentration is nil there is only salt and
water so pH must be seven(7). From Y axis (i.e. pH 7) a line is to be drawn on the pH
curve and from the point on the pH curve we should draw another line on X axis (number
of drops). From the point on X axis we will get the number of drops as well as the volume
of added alkali.
8.9.17. Why sudden jump occurs at the end point in pH-metric curve?
Ans. Actually near pH seven the concentration of H3 O+ is really negligible and it is
nothing but equal to H3 O+ is obtained from dissociation of water. On the other hand
the concentration of OH- ion is high that is why a sharp jump occurs near the end point
in pH-metric curve.

Ans. Here we need not require any indicator. This advantage of the titration reaction
In analytical work in laboratory or industry if any supplied acid or base is colored one
or black in color where use of any indicator is meaningless, with this experiment we can
easily determine the strength of the unknown acid base.
Chapter 9
Determination of dissolved
oxygen present in a given water
sample

(Determination of dissolved oxygen present in a given water sample)
9.2 Theory
Dissolved oxygen is used as an indicator of water body. Dissolved oxygen is essential for the
survival of aquatic life in water. Depletion of dissolved oxygen in water supplies can encourage
the microbial reduction of nitrate to nitrite and sulfate to sulfite.
By Winkler’s Iodometric method dissolved oxygen (D.O) in water sample is determined. A
known volume of water sample containing D.O is allowed to react with excess amount of iodine
(I- ) in the presence of Mn(II) salt (MnSO4 ) in alkaline medium then manganese oxide(MnO2 )
is precipitated.
Mn2+ + 12 O2 + 2OH- → H2 O + MnO2
Therefore,
1 O ≡ 2[O] ≡ MnO
2 2 2
When the solution is acidified with dilute H2 SO4 , the precipitated MnO2 oxidizes iodide ions
(I- ) to iodine (I2 ).
MnO2 + 4H+ + 2I- → I2 + Mn2+ + 2H2 O
Therefore,
MnO2 ≡ I2
Then the liberated iodine can be estimated by titrating with standard sodium thiosulfate solution
using freshly prepared starch as an indicator.
91
92 CHAPTER 9. DETERMINATION OF DISSOLVED OXYGEN
I2 + 2S2 O2- - 2-
3 → 2I + S4 O6
2-
I2 + 2S2 O3
Therefore,
2S2 O2- 1
3 ≡ I2 ≡ MnO2 ≡ 2 O2 ≡ [O]

9.3.1. Sodium thiosulphate;Na2 S2 O3 , 5H2 O
9.3.2. Potassium dichromate; K2 Cr2 O7
9.3.3. Potassium iodide; KI
9.3.4. Sulfuric acid; H2 SO4
9.3.5. Manganese (II) sulfate; MnSO4
9.3.6. Sodium azide; NaN3
9.3.7. Ortho phosphoric acid; H3 PO4
9.3.8. sodium hydroxide; NaOH
9.3.9. starch; (C6 H10 O5 )n

9.4.2. Burette
9.4.3. Pipette
9.4.7. Beakers
9.4.8. Wash bottle
9.4.9. Glass stopper bottle.
9.5 Procedure
9.5.1. Preparation of 250 ml 0.01(M) sodium thiosulphate solution (Na2 S2 O3 , 5H2 O)
Weigh out approximately 0.0620 gm of sodium thiosulphate in a clean 250 ml volumetric
flask and dissolve in small amount of distilled water. Then make up to the volume of the
flask with distilled water.
9.5. PROCEDURE 93
9.5.2. Preparation of 100 ml standard 0.01(M) potassium dichromate solution (K2 Cr2 O7 )
Weigh out exact 0.2942 gm of A.R potassium dichromate and transfer it in a 100 ml
volumetric flask and add 50 ml distilled water to it. Dissolve the solid completely in
distilled water and then fill the mark with distilled water.
Therefore, strength of potassium dichromate
µ ¶ µ ¶
W M
= ×
0.2949 100
Table 9.1: Weighing of potassium dichromate

³ ´
weight(gm) weight(gm) taken(gm) be taken(gm) M
100
W1 W2 W2 − W1 = W 0.2942 -
9.5.3. Preparation of 100 ml 4(N) H2 SO4 solution

Pour 11 ml of concentrated sulfuric acid in a 50 ml of distilled water in a 100 ml volumetric
flask and then dilute the solution to 100 ml with distilled water and mix properly.
9.5.4. Preparation of 100 ml 20% potassium iodide solution

Dissolve 20 gm of potassium iodide in 100 ml distilled water.
9.5.5. Preparation of starch solution

Take 0.1 gm of starch and make a paste with little amount of water. Then pour the paste
with constant stirring to 100 ml of water and boil for 1 minute. Allow the solution to cool
at room temperature.
9.5.6. Standardization of sodium thiosulfate solution
Pipette out 25 ml of standard potassium dichromate solution in a conical flask. Add 25
ml of 4(N) H2 SO4 and 10 ml of 20 % KI solution to it. Cover the conical flask with a
watch glass and keep it in dark for 3 minutes. Then dilute the solution with 200 ml of
distilled water. Titrate the solution with the sodium thiosulfate solution running from
burette. When the colour of the solution becomes pale yellow, add 2 ml of the starch
solution. The solution will turn blue. Continue the titration until the color changes from
blue to colorless.
Table 9.2: Standardisation of sodium thiosulfate solution against standard potassium

dichromate solution
No. Volume of . Burette reading of Volume of Mean Volume
of Std. Na2 S2 O3 , 5H2 O (ml) Na2 S2 O3 , of Na2 S2 O3 ,
K2 Cr2 O7 5H2 O 5H2 O
observation solution(ml) Initial Final solution(ml) solution(ml)
1. 25 - - - -
2. 25 - - - -
3. 25 - - - -
4. 25 - - - -
calculation of molarity of sodium thiosulfate solution As we know,
V1 × S1 = V2 × S2
Therefore,
V4 × S2
S3 = × (N)
V3
Here,
V1 = volume of standard potassium dichromate solution (25 ml)

S1 = Strength of standard potassium dichromate solution in Molarity
V2 = Mean volume of sodium thiosulfate solution required(ml)
S2 = Strength of sodium thiosulfate solution in Molarity
9.5.7. Preparation of 100 ml of 50 % Manganese (II) sulphate solution

Dissolve 50 gm of manganese (II) sulphate solution in small amount of distilled water and
mix well. Then make up the volume to 100 ml.
9.5.8. Preparation of 50 ml Alkaline iodide azide solution
Weigh 2.5 gm of NaOH and dissolve in 50 ml of distilled water. Then dissolve 0.675 gm
of KI and 0.5 gm of sodium azide to the solution and mix well.
9.5.9. Determination of dissolved oxygen content by iodometric method
Take 300 ml water sample in a glass stoppered bottle. The bottle always well stoppered
to prevent any sample exposure to air. Now, add 1 ml of 50 % manganese (II) sulphate
(MnSO4 ) to water sample. Similarly, add 1 ml of alkaline iodide azide solution. Shake well
to mix uniformly. A brown precipitate will be formed. If precipitate is not formed then add
2 ml of 2 (N) NaOH solution to the water sample and allowed to settle down for 15 minutes.
Then add 2 ml of concentrated phosphoric acid to dissolve the precipitation. After the
complete dissolution of brown precipitate, iodine is released in the solution. Now pipette
out 100 ml of the solution in a conical flask and titrate the liberated iodine with sodium
thiosulfate solution running from the burette. When the colour of the solution becomes
pale yellow, add 2 ml of the starch solution. The solution will turn blue. Continue the
titration until the color changes from blue to colorless.
Table 9.3: Determination of dissolve oxygen content

of water Na2 S2 O3 , 5H2 O (ml) Na2 S2 O3 , of Na2 S2 O3 ,
sample 5H2 O 5H2 O
observation taken(ml) Initial Final solution(ml) solution(ml)
1. 100 - - - -
2. 100 - - - -
3. 100 - - - -
4. 100 - - - -
5. 100 - - - -
9.6. CALCULATION 95
9.6 Calculation
Let, the burette reading of EDTA = V ml
1000 ml of 1(M) thiosulphate solution ≡ 1000 ml of 1(M)of dissolved oxygen
1000 ml of 1(M) thiosulphate solution = 16 gm of dissolved oxygen

16
1 ml of 1(M) thiosulphate solution = gm of dissolved oxygen
1000
16 × V × M2
V ml of(M2 )thiosulphate solution = gm of dissolved oxygen
1000
16 × V × M2
Hence,100 ml sample water contains gm of dissolved oxygen
1000
(16 × V × M2 )
Therefore,1000ml sample water contains gm of dissolved oxygen
100
9.7 Precaution
9.7.1. Any sample contact with air should be avoided as per as possible. Exposure of air will
lead to higher results.
9.7.2. Exclude air bubbles carefully while replacing the stopper.
9.7.3. Use freshly prepared starch solution for the titration.
9.7.4. Add starch solution while approaching the end point. If the starch solution is added
in highly concentrated iodine solution, some iodine is absorbed since starch gives water
insoluble complex with iodine.
9.8 Conclusion
Oxygen is present in air( 20.60 %) as well as water also by different ways like gas diffusion
process, photosynthesis of aquatic plants, but at too low a concentration to sustain aquatic life.
Oxygen also is needed by virtually all algae and all macrophytes, like terrestrial animals, fish and
other aquatic organisms need oxygen to live. As water moves past their gills (or other breathing
apparatus), microscopic bubbles of oxygen gas in the water, called dissolved oxygen (DO), are
transferred from the water to their blood. Presence of oxygen in water acts as indicators in
various chemical and bio-chemical characteristics. For many chemical and bio-chemical reactions
oxygen has a great role like oxidation, biological oxygen demand(BOD) and chemical oxygen
demand(COD).

9.9.1. What is dissolved oxygen(DO) in water? How oxygen is dissolved in water? What is the
effect of dissolved oxygen in water?
Ans. Oxygen is present in air (20.60%) as well as water also by different ways like gas dif-
fusion process, the transfer is efficient only above certain concentrations. In other words,
oxygen can be present in the water by photosynthesis of aquatic plants, but at too low
a concentration to sustain aquatic life. Oxygen also is needed by virtually all algae and
all macrophytes, Like terrestrial animals, fish and other aquatic organisms need oxygen to
live. As water moves past their gills (or other breathing apparatus), microscopic bubbles
of oxygen gas in the water, called dissolved oxygen (DO), are transferred from the water
to their blood. Presence of oxygen in water acts as an indicators in various chemical and
bio-chemical characteristics and for many chemical reactions that are important to keep
the aquatic life in good condition in the lake.
9.9.2. What is solubility?

Ans. In common sentence the solubility is how much solute is soluble in any solvent but
in fact ”at a given temperature the amount of solute required to prepared 100 grams of
solvent into a completely saturated solution is known as the solubility of the solute in that
particular solvent at that temperature”.
9.9.3. Which law is applicable in case of solubility of gas in liquid? State the law.
Ans. Henry’s law is one of the most important gas laws given by William Henry in the
year 1803. It states: ”At a given temperature, the amount of a gas which dissolves in
a particular type and volume of liquid is directly proportional to the partial pressure of
the gas in equilibrium with that liquid.” An equivalent way of stating the law is that the
solubility of a gas in a liquid is directly proportional to the partial pressure of the gas
above the liquid.
To explain this law, Henry derived the equation:
C = kPgas
where;
C is the solubility of a gas(concentration) at a fixed temperature in a particular solvent
(in units of M or ml gas/L)
k is Henry’s law constant (often in units of M/atm)
Pgas is the partial pressure of the gas (often in units of Atm)
9.9.4. What is iodometric titration?

Ans. When iodine is produced by the addition of an oxidizing analyte to an excess of
iodide, the method is as iodometry. Thiosulfate (S2 O-2 3 )is commonly used in titration
reactions involving iodine, both for iodometric and iodimetric titration methods.
Iodometry is commonly used to analyse the concentration of oxidizing agents in water
samples, such as oxygen saturation in ecological studies or active chlorine in swimming
pool water analysis. To a known volume of sample, an excess but known amount of iodide
is added, which the oxidizing agents oxidizes iodide to iodine. Iodine dissolves in the
iodide-containing solution to give triiodide ions, which have a dark brown color.
The triiodide ion solution is then titrated against standard thiosulphate solution to give
iodide again using starch indicator:
I-3 + 2 e- ¿ 3I- ; (E0 = +0.5355 V)

Together with reduction potential of thiosulfate:
S4 O2- - 2- 0
6 + 2 e ¿ 2S2 O3 (E = +0.08 V)
The overall reaction is thus:
I-3 + 2S2 O2- 2- - 0

3 ¿ S4 O6 + 3I (E = +0.4555 V)
9.9.5. Why one molar sodium thiosulphate solution is prepared for iodometric titration. Though
the equivalent weight of sodium thiosulphate is half of moleculer weight?
Ans. The overall redox reaction between thiosulphate and iodine, first balance the atoms
and electrons in each half reaction then add the 2 half reactions up.
The iodine/sulfur/oxygen atoms in each reaction are balanced, and you have 2 electrons
either on the reactant or product side in both half reactions (no need to multiply either
reaction by another factor).
So just add them up like they are:
I2 + 2S2 O2- 2-
3 ¿ S4 O6 + 2I
-
The test for iodine is using starch to indicate the presence of the oxidizing agent (I2 in
this case). Iodine will react with starch to give a very dark blue color.
From the overall reaction we see that one molecule of iodine(I2 )is reduced to iodide(2I- )
by two moles of thiosulphate. So to get 2I- we need one moles of thiosulphate is required.
9.9.6. How sodium thiosulphate is standardized?
Ans. Standardization of Na2 S2 O3 solution
1. Pipette out 10 ml of 0.01 N potassium dichromate (K2 Cr2 O7 ) solution into a 250 ml
conical flask.
2. Add 30 ml distilled water.
3. Add 0.8 gm of sodium bicarbonate, 2 ml of 10 % KI solution, followed by 2 ml. of 5
(N) HCl solution.
4. Cover the conical flask and keep it in the dark for about 5 minutes. This is done to
avoid any side reaction from occurring which can generate more iodine (from iodide), by
exposure to light.
5. Titrate the liberated I2 against 0.01(N) sodium thiosulfate solution (taken from the
burette), till you get a straw yellow color.
6. Add approximately 1 ml of starch indicator solution. The solution will turn blue.
7. Continue the titration until the solution becomes colorless.
8. Note the titre value (volume of Na2 S2 O3 solution added) in ml.
9.Calculate the actual strength of Na2 S2 O3 solution used
9.9.7. What is the difference between iodimetry and iodometry?

Ans. When any compound that is a reducing agent is titrated directly with a standard io-
dine solution, the method is called ”iodimetry”. When any compound 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”.
9.9.8. How liberated iodine is back titrated by sodium thiosulphate?

Ans. i) Iodine (I2 ) is reduced to iodide (I- ).
I2 + 2e- ¿ 2I-
ii) Thiosuphate is oxidized to tetrathionate ion.
2S2 O2- 2-
3 ¿ S4 O6 + 2e
-
iii) To figure out the overall redox reaction, first balance the atoms and electrons in each
half reaction then add the 2 half reactions up.
The iodine/sulfur/oxygen atoms in each reaction are balanced, and you have 2 electrons
either on the reactant or product side in both half reactions (no need to multiply either
reaction by another factor).
So just add them up like they are:
I2 + 2S2 O2- 2-
3 ¿ S4 O6 + 2I
-
The test for iodine is using starch to indicate the presence of the oxidizing agent (I2 in
this case). Iodine will react with starch to give a very dark blue color.
9.9.9. Thiosulphate solution is a primary or secondary standard solution? Explain.

Ans. Secondary standard solution because it contains water of crystallization so it can
absorb or release water moreover, it tends over time to precipitate sulfur.
Na2 S2 O3 = Na2 SO3 + S
9.9.10. Why starch solution is added before end point when the colour of the solution become
straw yellow colour?
Ans. The iodine solution, which is a golden-brown colour , can be titrated against sodium
thiosulfate solution. The sodium thiosulfate solution is placed in the burette and, as it is
added to the conical flask, it reacts with the iodine and the colour of the solution fades.
When it reaches a pale yellow or straw yellow colour, a few drops of a freshly prepared
starch solution are added. The solution becomes blue-black. The thiosulfate solution
should now be added dropwise, with thorough swirling and the titration is continued until
it goes colourless.
9.9.11. Describe another method of dissolved oxygen measurement.

Ans. There are so many methods to determine the dissolved oxygen in water but most
common method to determine the dissolved oxygen in water is Winkler method. In this
process an water filled bottle is to be taken then necessary chemicals are added to it,
finally the dissolved oxygen is estimated iodometrically.
9.9.12. Starch indicator is not fit in Strongly acid medium- explain.

Ans. Starch, is a natural polymer having molecular formula (C6 H10 O5 )n . In presence of
strong acid it undergo hydrolysis which is not desirable.

Ans.In aqueous system many chemical, biological and biochemical process are directly
depends on dissolved oxygen in water. Oxygen is present in air( 20.60 %) as well as water
also by different ways like gas diffusion process, photosynthesis of aquatic plants, but at
too low a concentration to sustain aquatic life. Oxygen also is needed by virtually all
algae and all macrophytes, like terrestrial animals, fish and other aquatic organisms need
oxygen to live. As water moves past their gills (or other breathing apparatus), microscopic
bubbles of oxygen gas in the water, called dissolved oxygen (DO), are transferred from the
water to their blood. Presence of oxygen in water acts as indicators in various chemical
and bio-chemical characteristics. For many chemical and bio-chemical reactions oxygen
has a great role like oxidation, biological oxygen demand(BOD) and chemical oxygen de-
mand(COD).
Chapter 10
Experiment name:To determine

chloride ion in a given water
sample by Argentometric method
(using chromate indicator
solution)

(To determine chloride ion in a given water sample by Argentometric method (using chromate
indicator solution))
10.2 Theory
Chlorides are present in water usually as NaCl, MgCl2 and CaCl2 . Although chlorides are not
harmful as such, their concentrations over 250 ppm. impart a peculiar taste to the water thus
rendering the water unacceptable for drinking purposes.
By argentometric method, chloride ions in a water sample (neutral or slightly alkaline) can
be determined by titrating it against standard silver nitrate (AgNO3 ) solution using potassium
chromate (K2 CrO4 ) as an indicator. The pH should be in between 7 - 8. At higher pH, silver
ions are precipitated as silver hydroxide. At lower pH, potassium chromate indicator is converted
to potassium dichromate (K2 Cr2 O7 ).
Argentometric method is based on the precipitation titration in which silver nitrate solution
is released from the burette to the water sample which contains chloride ions and indicator.The
silver ions (from silver nitrate solution) react with chloride ions (from water sample) and chromate
ions (from indicator) to form white precipitate of silver chloride and red precipitate of silver
chromate.
Ag+ + Cl- → AgCl (White Precipitate)

2Ag+ + CrO2-
4 → Ag2 CrO4 (Red Precipitate)
Red colour formed because of the formation of silver chromate disappears initially as the solution
contains high concentration of chloride ions.
99
100CHAPTER 10. DETERMINE CHLORIDE ION IN A GIVEN WATER SAMPLE
Ag2 CrO4 + 2Cl- → 2AgCl + CrO2-

4
When the concentration of chloride ions has decreased, the red colour starts disappearing slowly
and slowly on shaking and a stage is reached when all the chloride ions have formed silver chloride.
One extra drop of silver nitrate at this point reacts with potassium chromate and reddish coloured
silver chromate is formed.
2AgNO3 + K2 CrO4 → Ag2 CrO4 + 2KNO3

10.3.1. Silver nitrate;AgNO3
10.3.2. Sodium chloride; NaCl
10.3.3. Potassium chromate; K2 CrO4

10.4.1. Burette
10.4.2. Pipette
10.4.6. Beakers
10.4.7. Wash bottle
10.5 Procedure
10.5.1. Preparation of potassium chromate indicator
5 gm of potassium chromate is dissolved in about 5 ml of distilled water. Few drops of
silver nitrate are added until a definite red precipitate is formed. It is allowed to stand
for 12 hours, filtered and diluted to 100 ml with distilled water.
³ ´
10.5.2. Preparation of 1000 ml 50 M standard sodium chloride (NaCl) solution
Weigh out about 1.17 gm of NaCl and transfer in a 1000 ml volumetric flask and add
small amount of distilled water to it. Dissolve completely the solid in distilled water and
fill the mark with distilled water and mix thoroughly.
Therefore, the strength of standard sodium chloride solution is
µ ¶
W W
= ×
1.17 50
10.5. PROCEDURE 101
M standard sodium chloride (NaCl) solution

Table 10.1: Preparation of 1000 ml 50
Initial weight Final weight Weight taken Weight to be taken Strength
(gm) (gm) (gm) (gm)
W1 W2 W = W2 − W1 1.17 -
10.5.3. Preparation of silver nitrate solution

Weigh about 3.4 gm of silver nitrate and dissolve in 50 ml of distilled water and then
dilute to 1000 ml in a dark bottle.
10.5.4. Standardization of silver nitrate solution

Pipette out 10 ml of standard sodium chloride solution in a conical flask. Add 5 drops
of potassium chromate indicator to it and titrate the solution with silver nitrate solution
running from the burette. A red color of silver chromate appears and again redissolves.
Continue the titration until a pinkish or reddish tinge persists in the yellow solution with
constant swirling of the liquid in the conical flask throughout the titration procedure. As
Table 10.2: Standardization of silver nitrate solution against standard sodium chloride
solution
of Sodium AgNO3 solution(ml) AgNO3 of AgNO3
chloride solution solution
observation taken(ml) Initial Final (ml) (ml)
2. 25 - - - -
3. 25 - - - -
4. 25 - - - -
5. 25 - - - -
we know,
V1 × S1 = V2 × S2
V1 × S 1
S2 =
V2
Here,
V1 = Volume of standard sodium chloride solution (25 ml)

S1 = Strength of standard sodium chloride solution(s) in molarity
V2 = Volume of silver nitrate solution required (x ml)
S2 = Strength of silver nitrate solution in Molarity
10.5.5. Determination of the amount of chloride ion in the given water sample
Pipette out 25 ml of the water sample in a conical flask. Add 5 drops of potassium
chromate indicator to it and titrate the solution with silver nitrate solution running from
the burette. A red color of silver chromate appears and redissolves. Continue the titration
until a pinkish or reddish tinge persists in the yellow solution with constant swirling of
the liquid in the conical flask throughout the titration procedure. As we know,
Table 10.3: Determination of the amount of chloride ion in the given water sample
of water AgNO3 solution(ml) AgNO3 of AgNO3
sample solution solution
observation taken(ml) Initial Final (ml) (ml)
2. 25 - - - -
3. 25 - - - -
4. 25 - - - -
5. 25 - - - -
V1 × S1 = V2 × S2
V1 × S 1
S2 =
V2
Here,
V1 = Volume of standard sodium chloride solution (25 ml)

S1 = Strength of standard sodium chloride solution(s) in molarity
V2 = Volume of silver nitrate solution required (x ml)
S2 = Strength of silver nitrate solution in Molarity
10.6 Calculation
Suppose y ml of the silver nitrate solution is required for the titration of the given water sample.
1000 ml of 1(M) silver nitrate solution ≡ 1000 ml of 1(N)Cl
= 35.5 gms. of Cl
35.5
1 ml of 1(M) silver nitrate solution = gm of Cl
1000
35.5 × y × V2
y ml of S2 (M)silver nitrate solution = gm of Cl
1000
= 35.5 × y × S2 mgof Cl
Hence,
25 ml sample water contain 35.5 × y × V2 mg of Cl
Therefore,
35.5 × y × S2 × 1000
1000 ml sample water contain mg of Cl
25
10.7 Precaution
10.7.1. Each apparatus should be washed with distilled water which is free of chlorine.
10.8. CONCLUSION 103
10.7.2. Carefully handle silver nitrate and avoid any skin contact since silver nitrate is corrosive
and leave black spots.
10.7.3. Add same amount of potassium chromate indicator each time.
10.7.4. Perform the titration with constant swirling of the liquid in the conical flask.
10.8 Conclusion
Chlorine is a strong oxidizing agent which leads also a great role in the toxicity of water specially
in case of contamination of eyes and skin swimming pool or during bathing. Chloride ion present
in water also changes the ph of water. Its high concentration water also corrodes the metal
when in contact such as in boiler, also for cloth during washing in laundry.This is one of most
important method by which we can measure the dissolved chlorine in water.

10.9.1. Which chemicals are responsible for chlorination in water?
Ans. The are so many compounds(Bleaching powder, DDT) or electrolytes(CaCl2 ,MgCl2 ,
KCl, NaCl) which are dissolved and dissociated in water produces chloride ion in water.
When these ions get oxidized from chlorine and water becomes chlorinated.
10.9.2. What is the nature or pH of chlorinated water?

Ans. The pH is a measure of the acidity of the water. The pH scale goes from 0 to 14,
where pH 7 is neutral. If the pH is above 7, the water is basic; if it is below 7 the water
is acid. Ph changes with the concentration of chlorine in water. The optimum pH for
swimming pool water is 7.4, since this is the same as the pH in human eyes and mucous
membranes. A pH of 7.4 also gives good chlorine disinfection.
A low pH gives: - aggressive water, which damages the mechanical components of the
pool - irritations of the eyes and mucous membranes - damage to the pool liner
A high pH gives: - poorer chlorine disinfection - skin irritation - lime precipitation -
cloudiness
The guideline pH figure is 7.2 to 7.6.
To lower the pH, use sodium bisulphate; to raise it use sodium carbonate.
10.9.3. What is solubility product?

Ans. At a given temperature the product of the concentration of the ion have a fixed
value That is called solubility product of that substance at that temperature. For strong
electrolyte the solubility product value is high as the substance gets fully ionise. In that
case at any given temperature ionic product can never reaches the solubility product
value. That is why no precipitation will appear.For weak electrolyte the solubility product
value is not so high as the substance does not gets fully ionise. In that case there is an
equilibrium between substance and produce ion. At any given temperature ionic product
may reaches the solubility product value cause precipitation.
Eg. Silver chloride is so insoluble in water (.0.002 g/L) that a saturated solution contains
only about 1.3 x 10-5 moles of AgCl per liter of water.
AgCl(s) ¿ Ag+ (aq) + Cl- (aq)

Strict adherence to the rules for writing equilibrium constant expressions for this reaction
gives the following result.
[Ag+ ][Cl- ]
Kc =
[AgCl]
(Water isn’t included in the equilibrium constant expression because it is neither con-
sumed nor produced in this reaction, even though it is a vital component of the system.)
The [Ag+ ] and [Cl- ] terms represent the concentrations of the [Ag+ ] and [Cl- ] ions
in moles per liter when this solution is at equilibrium. The third term [AgCl]is more
ambiguous. It doesn’t represent the concentration of AgCl dissolved in water because we
assume that AgCl dissociates into Ag+ ions and [Cl- ] ions when it dissolves in water. It
can’t represent the amount of solid AgCl in the system because the equilibrium is not
affected by the amount of excess solid added to the system. The [AgCl] term has to be
translated quite literally as the number of moles of AgCl in a liter of solid AgCl.
The concentration of solid AgCl can be calculated from its density and the molar mass
of AgCl.
5.56 gms AgCl 1 cm3 1000 ml 1 mole AgCl

× × × = 38.8 mol AgCl per lit.
1 cm3 1 ml 1 lit 143.34 gms AgCl
This quantity is a constant, however. The number of moles per liter in solid AgCl is the
same at the start of the reaction as it is when the reaction reaches equilibrium.
Since the [AgCl] term is a constant, which has no effect on the equilibrium, it is built
into the equilibrium constant for the reaction.
[Ag+ ][ Cl- ] = Kc [ AgCl]
This equation suggests that the product of the equilibrium concentrations of the [Ag+ ]
and [Cl- ] ions in this solution is equal to a constant. Since this constant is proportional
to the solubility of the salt, it is called the solubility product equilibrium constant for the
reaction, or KSP .
KSP = [Ag+ ][Cl- ]
The KSP expression for a salt is the product of the concentrations of the ions, with
each concentration raised to a power equal to the coefficient of that ion in the balanced
equation for the solubility equilibrium.
10.9.4. What do you mean by sparingly soluble salt? Give example.

Ans. There are some salt which are not completely soluble in water at ordinary tem-
perature, called sparingly soluble salt. The solubility product value of these salt is very
low. Some times product of concentration of produced ions exceeds the solubility product
value. Then precipitation occur example AgCl, Al3 SO4
10.9.5. What is the relation between solubility and ionic product of water?
Ans. In case of AgCl the relation between product of ions concentration and solubility
product is given by -
KSP = [Ag+ ][Cl- ]

At a given temperature -
i) If product of ions concentration is greater than solubility product of any sparingly
soluble salt then precipitation occur.
ii) If product of ions concentration is equal to the solubility product of any sparingly
soluble salt then no precipitation occur the solution is a saturated solution.
iii) If product of ions concentration is less than solubility product of any sparingly soluble
salt then no precipitation occurs.
10.9.6. When precipitation occur?

Ans. If product of ions concentration is greater than solubility product of any sparingly
soluble salt then precipitation occurs.
10.9.7. What happens when the ionic product of AgCl is- (i) less than (ii) equal and (iii) greater
than 1.2 × 10-10
Ans. (i) If product of ions concentration is less than solubility product (1.2 × 10-10 ) of
AgCl salt then no precipitation occurs.
(ii) If product of ions concentration is equal to the solubility product of (1.2 × 10-10 ) of
AgCl salt then no precipitation occurs, the solution is a saturated solution.
(iii) If product of ions concentration is greater than solubility product of (1.2 × 10-10 ) of
AgCl salt then precipitation occurs.
10.9.8. What happen when the ionic product of AgCrO4 is- (i) less than (ii) equal and (iii)
greater than 1.7 × 10−12
Ans. (i) If product of ions concentration is less than solubility product (1.7 × 10-12 ) of
AgCl salt then no precipitation occurs.
(ii) If product of ions concentration is equal to the solubility product of (1.7 × 10-12 ) of
AgCl salt then no precipitation occurs, the solution is a saturated solution.
(iii) If product of ions concentration is greater than solubility product of (1.7 × 10-12 ) of
AgCl salt then precipitation occurs.
10.9.9. What is common ion effect?

Ans. There are some salts which are not completely soluble in water at ordinary temper-
ature, called sparingly soluble salt. The solubility product value of these salt is very low.
Sometimes product of concentration of produced ions exceed the solubility product value.
Then precipitation occur example AgCl, Al3 SO4 . In the solution of such sparingly sol-
uble salt any one ion becomes common and the degree of dissociation of the salt decrease.
10.9.10. What precaution should be taken in case of turbid and colour water?
Ans. To remove the turbid and colour the water is a paste of Al(OH)3 prepared from
ammonium hydroxide and ammonium sulphate. Then by filtration we get the clear so-
lution of the sample.
10.9.11. Argentometric titration is what type titration?

Ans. Argentometric titration is a special type of titration where standard silver nitrate
solution get precipitate which helps to estimate the ions.
10.9.12. What is the effect of ph in argentometric titration?

Ans. ph has a great roll in the titration reaction. In the argentometric titration reaction
pH should be maintained in between 6.5 to 8 because chromate ion is the conjugate base
of chromic acid. When pH is high and more than 10 silver hydroxide is formed which
have brown colour and disturbed the end point. On the other hand when pH is low and
below 6.5 chromic acid is formed by the protonation of chromate ion. As a result chro-
mate ion concentration decreases which prevents the precipitation at the equivalent point.
10.9.13. Depending upon the nature of testing solution what modification of silver nitrate is to
be required?
Ans. In case of alkaline solution acetic acid is to be added then just excess amount of
calcium carbonate is to be added to make the solution neutral.
In case of acidic solution calcium carbonate is to be added to make the solution neutral.
10.9.14. What is the effect of ammonia during titration?

Ans. Presence of ammonium ions increase the pH of the solution more than 7.
as a result AgCl does not get precipitated at it form soluble complex.
AgCl + 2NH4 OH ¿ [Ag(NO3 )2 ]+ + Cl- + 2H2 O
10.9.15. What is the effect of temperature on this precipitation reaction?

Ans. We know that solubility product of AgCrO4 increases with temperature. As we
know with increase in solubility product more ion concentration is necessary to get precip-
itated. So, here more AgCl is required at higher temperature. That is why the titration
reaction is carried out at room temperature.
10.9.16. What should be the concentration of NaCl chloride for argentometric titration?
N ) to (( N )] is good for
Ans. A low concentration or dilut solution of NaCl range [( 100 20
argentometric titration otherwise AgCl undergoes rapid coagulation at higher concentra-
tion.
10.9.17. How solubility product measure?

Ans. Solubility Data, Conductivity method, Potentiometric method.
10.9.18. Explain and draw the graphical representation for argentometric titration curve.
Ans. The reaction of argentometric titration is the reaction mainly in between KCl and
KCl and AgNO3
The complete reaction is-
KCl + AgNO3 ¿ AgCl + K+ NO-3
On addition of AgNO3 the Cl− is replaced by NO-3 ion and the ion conductance of these
ions are almost same. Hence the conductance of ions do not change with the continuous
addition of AgNO3 . i.e. parallel to X axis. Then conductance increases gradually due to
dissociation of AgNO3
10.9.19. What is heat of solution and integral heat of solution?

Ans. Heat of solution: It is the enthalpy change when definite volume of solute is
dissolved in such a large volume of solvent that on farther dilution no heat change will
occur. integral heat of solution: It is the enthalpy change when definite volume of solute
is dissolved in definite volume of solvent.
10.9.20. Give the relation between solubility product and temperature. What is the name of the
equation.?
Ans. If K1 and K2 are the solubility product at two different temperature T1 and T2
then relation between solubility product and temperature is
K ∆H 1 1
ln( 2 ) = [ − ]
K1 R T2 T1
Where, ∆H is the heat of solution. The above equation is known Vant Hoff’s equation.

Ans.Chlorine is a strong oxidizing agent which leads also a great role in the toxicity of
water specially in case of contamination of eyes and skin swimming pool or during bathing.
Chloride ion presence in water also change the ph of water. Its high concentration water
also corrode the metal when in contact such as in boiler, also for cloth during washing in
laundry.
Chapter 11
Important general question for

viva-voce
11.1.1. What do you mean by quantitative analysis? Give different process of quantitative anal-
ysis.
Ans. The determination of amount of one or more element, compound or radical presence
in a definite volume of solution or in a definite weight of matter is known as quantitative
analysis. Normally, during quantitative analysis we calculate the amount in
(i) gms./lit.
(ii) normality(N)
(iii) molarity(M)
(iv) molalality(m)
(v) formality(f)
(vi) percentage(%) and
(vii) mole fraction(Xi ).
Mainly two processes of quantitative analysis are
(a) gravimetric method and
(b) volumetric method also named as titrimetric method.
11.1.2. What do you mean by gravimetric method of analysis? Give example.

Ans. In this method, the known volume of solution of experimental compound or
material is to be taken. Allowed to react with suitable reagent to produce precipitated
compound of pure and known composition at a particular atmosphere to determine the
particular component. Ultimately, after washing and drying of the precipitation weight
is to be taken. From which the component weight is found out. To find out the amount
of sulphate radical present in sodium sulphate the following step is to be done.
(a) Prepare a solution of sodium sulphate with water
(b) Pipette 25 ml solution of sodium sulphate in a 500 ml beaker
(c) add 100 ml distilled water and 15 ml(approx.) concentrated HCl and allowed to heat
(d) add sufficient amount BaCl2 and stirred with a glass rod in to the hot solution and
wait for 2 hours to reach the temperature at room temperature.
(e) filtrate, wash with distilled water and dry in a oven at a temperature 130 − 1400 C
(f) finally, weight should be taken, from which we will get the amount of sulphate radical
present in definite volume of solution.
109
110 CHAPTER 11. IMPORTANT GENERAL QUESTION FOR VIVA-VOCE
11.1.3. What do you mean by volumetric method of analysis? Give example.

Ans. In this method, the known volume of solution of experimental compound or
material is to be taken. Allowed to react with known strength of solution of suitable
reagent in presence of proper indicator by titrimetric method up to the colour change of
the indicator. Then apply
V1S1 = V2S2
Where,
V1 = Volume of a solution of known strength S 1

V2 = volume of other solution of unknown strength S 2
11.1.4. Give the name of apparatus generally used in different volumetric method of analysis.
Ans. Essential apparatus are -
11.1.4.1. Weighing balance

11.1.4.2. Weighing bottle
11.1.4.3. Volumetric flask
11.1.4.4. Funnel
11.1.4.5. Beaker
11.1.4.6. Conical flask
11.1.4.7. droppers
11.1.4.8. Watch glass
11.1.4.9. Glass tube and glass rod
11.1.4.10. Filter paper.
11.1.5. What is the standard solution and standard substance? Give example.
Ans. When the strength of any solution is known then the solution is known as standard
solution. The substances used to prepared a standard solution are known as standard
substances.
11.1.6. What is primary standard solution? Give example.
Ans. The chemical substances which are (i) easily available in pure state (ii)the chemical
composition remains unchanged (iii) stable in the laboratory atmosphere and the strength
of the solution remain same for a long period of time is called primary standard solution.
Example of primary standard solution (i) Oxidizing series: (a) potassium dichromate
(K2 Cr2 O7 ) (b) potassium iodate (KIO3 ) (c) potassium bromate (KBr3 ) etc. (ii) Oxi-
dizing series: a) oxalic acid dihydrate[(COOH)2 , 2H2 O] b) Sodium oxalate (Na2 C2 O4 )
c) Mercurous nitrate [Hg2 (NO3 )2 ]etc.
11.1.7. What is the secondary standard solution? Give example.
Ans. The chemical substances which are (i) easily available not in pure state (ii)the
chemical composition not fixed (iii) not stable in the laboratory atmosphere and the
strength of the solution change for a long period of time is called secondary stan-
dard solution. Example of secondary standard solution (a) potassium permanganate
(KMnO4 ) (b) Sulfuric acid (H2 SO4 ) (c) Sodium hydroxide (NaOH) (d) Sodium thiosul-
phate (Na2 S2 O3 ) etc.
111
11.1.8. What is normality? Give example.

Ans. Number of equivalent weight present in one liter solution is known as normality.
It is expressed by (N). So,
Weight of solutes(grams)
normality(N) =
Eq. Weight(E) × No. of lit.(L)
11.1.9. What is molarity? Give example. Ans. Number of mole present in one liter solution is
known as molarity. It is expressed by (M). So,
molarity(M) =
Mol. Weight(M) × No. of lit.(L)
11.1.10. What is molalality? Give example.
Ans. Number of mole present in one kg or 1000 gms. solvent is known as molality. It
is expressed by (m). So,
molality(m) =
Eq. Weight(E) × No. of weight.(Kg.)
11.1.11. What is formality? Give example.
Ans. Number of formula weight present in one lit solution is known as formality. It is
expressed by (F). Some compounds (like NaCl, Na2 CO3 , CaCl2 ) are ionic in nature and
they are completely dissociate in water and produce cation and anion. As in aqueous
solution of these compounds has no existence of mole so for these compounds in there
solution the term mole, gram mole, molecular weight these terms are meaningless. For
these compounds instead of molarity formality is used. so,
formality(F) =
Formula Weight(M) × No. of lit.(L)
11.1.12. What is gms./lit? Give example.
Ans. Number of gms. present in one liter solution is known as gms./lit. It is expressed
by (M). So,
gms./lit =
No. of lit.of solvent(L)
11.1.13. What is percentage strength? Give example.
Ans. Percentage strength are two types -
(i) percentage strength
W
( ) = (N) × Equiv. Wt. × 0.1
V
= (M) × Mol. Wt. × 0.1
(M) × density of solution × molecular wt × 100
=
1000 + (m)
(ii) percentage strength
W (N) × Equiv. Wt × 0.1
( ) =
W density of solution
(M) × Mol. Wt × 0.1
=
density of solution
(m) × molecular wt. × 100
=
weight of solution
11.1.14. What is mole fraction? Give example.

Ans. Number of moles present of any component with respect to the total number of
moles is known as mole fraction. Let us consider two components A and B their number
of moles present nA and nB respectively. So mole fraction of A is expressed by (XA ).
So,
Number of moles of A(nA )
mole fraction(XA ) =
Number of moles of A(nA ) + Number of moles of B(nB )
mole fraction of B is expressed by (XB ).

So,
Number of moles of B(nB )
mole fraction(XB ) =
Number of moles of A(nA ) + Number of moles of B(nB )
Sum of all mole fraction i.e. XA + XB = 1
11.1.15. When normality and molarity are same? Give example.

Ans. When equivalent weight of any substance = to the molecular weight of the same
substance then normality and molarity are same. HCl, HNO3 , NaOH etc. but in case of
H2 SO4 molarity = 2× normality, as here, molecular weight = 2 × equivalent weight.
11.1.16. Among the normality, molarity, molalality and formality which one is temperature de-
pendent and why?
Ans. Only molality(m) is temperature independent because it is the weight of solute in
weight of solvent. Weight remains unchanged with change in temperature but in all other
cases they are temperature dependent as in all cases we take weight of solute in volume
of solvent.
11.1.17. What is the difference between molarity and formality? Explain with example.
Ans. Number of formula weight present in one lit solution is known as formality. It is
expressed by (F). Some compounds (like NaCl, Na2 CO3 , CaCl2 ) are ionic in nature and
they are completely dissociate in water and produce cation and anion. As in aqueous
solution of these compounds has no existence of mole so for these compounds in there
solution form mole, gram mole, molecular weight these terms are meaningless. For these
compounds instead of molarity formality is used.
11.1.18. What do you mean by meniscus of liquid?
Ans. Due to surface tension every liquid try to minimize its surface area. As results
the surface of liquid in a glass cylinder is not plane slightly curved. Depending upon the
contact angle it will be concave in water) or convex (in mercury). This curve surface is
called meniscus.
11.1.19. In case of transparent liquid and color liquid which meniscus should be taken in burette,
pipette and in measuring cylinder?
Ans. For transparent aqueous solution we should measure the lower meniscus and for
colour aqueous solution we should measure the upper meniscus.
11.1.20. What amount of
(a)Oxalic acid
(b)Na2 CO3
(c)KMnO4
(d)NaOH
(e)HCl
(f)H2 SO4
113
require to prepare 250 ml 0.01(N) solution of each respectively.

Ans.(a) 250 ml 0.01 (N) Oxalic acid:
MOxalic acid
We know equiv. weight of Oxalic acid =
Basicity
126
=
2
= 63
1000 ml 1(N) Oxalic acid solution contain = 63 gms. of Oxalic acid

1 ml 1(N) Oxalic acid solution contain = 63 × 1000 gms. of Oxalic acid
63 × 1000
250 ml 1(N) Oxalic acid solution contain = gms. of Oxalic acid
250
63 × 1000 × 0.01
250 ml 0.01(N) Oxalic acid solution contain = gms. of Oxalic acid
250
= 2.52 gms. of Oxalic acid
(b)250 ml 0.01 (N) Na2 CO3 :
MNa CO
We know equiv. weight of Na2 CO3 = 2 3
No. of cation × valency
106
=
1×2
= 53
1000 ml 1(N)Na2 CO3 solution contain = 53 gms. of Na2 CO3

1 ml 1(N)Na2 CO3 solution contain = 53 × 1000 gms. of Na2 CO3
53 × 1000
250 ml 1(N)Na2 CO3 solution contain = gms. ofNa2 CO3
250
53 × 1000 × 0.01
250 ml 0.01(N)Na2 CO3 solution contain = gms. of Na2 CO3
250
= 2.12 gms. ofNa2 CO3
(c)250 ml 0.01 (N) Potassium permanganate:
MKMnO
We know equiv. weight of Potassium permanganate = 4
No. of electrons gain
157.5
=
5
= 31.5
1000 ml 1(N) KMnO4 solution contain = 31.5 gms. of KMnO4

1 ml 1(N) KMnO4 solution contain = 31.5 × 1000 gms. of KMnO4
31.5 × 1000
250 ml 1(N) KMnO4 solution contain = gms. of KMnO4
250
31.5 × 1000 × 0.01
250 ml 0.01(N) KMnO4 solution contain = gms. of KMnO4
250
= 1.26gms. ofKMnO4
(d) 250 ml 0.01 (N) Sodium hydroxide:

We know equiv. weight of Sodium hydroxide = 40
1000 ml 1(N) NaOH solution contain = 40 gms. of NaOH

1 ml 1(N) NaOH solution contain = 40 × 1000 gms. of NaOH
40 × 1000
250 ml 1(N) NaOH solution contain = gms. of NaOH
250
40 × 1000 × 0.01
250 ml 0.01(N) NaOH solution contain = gms. of NaOH
250
= 1.6 gms. of Sodium hydroxide
(e) 250 ml 0.01 (N) Hydrochloric acid:

We know equiv. weight of Hydrochloric acid = 36.5
1000 ml 1(N) HCl solution contain = 36.5 gms. of HCl

1 ml 1(N) HCl solution contain = 36.5 × 1000 gms. of HCl
36.5 × 1000
250 ml 1(N) HCl solution contain = gms. of HCl
250
36.5 × 1000 × 0.01
250 ml 0.01(N) HCl solution contain = gms. of HCl
250
= 1.46 gms. of HCl
(f) 250 ml 0.01 (N) H2 SO4 :
MH SO
We know equiv. weight of Sulphuric acid = 2 4
Its basicity
98
=
2
= 49
1000 ml 1(N) H2 SO4 solution contain = 49gms. of H2 SO4

1 ml 1(N) H2 SO4 solution contain = 49 × 1000 gms. of H2 SO4
49 × 1000
250 ml 1(N) H2 SO4 solution contain = gms. of H2 SO4
250
49 × 1000 × 0.01
250 ml 0.01(N) H2 SO4 solution contain = gms. of H2 SO4
250
= 1.96 gms. of H2 SO4
11.1.21. During any volumetric analysis why we require minimum three readings?
Ans. If we take result of one experiment result may or may not be correct but the
average of three or four reading gives us minimum erroneous result.
11.1.22. What do you mean by neutralization?
Ans. Equivalent amount of any acid exactly react by equivalent amount of base, produce
salt and water is known neutralization.
11.1.23. What is indicator? Give example.
Ans. Indicators are normally organic compounds require very small quantity used in
115
Table 11.1: Some important chemicals, their equivalent weight and different normal
solution
Chemicals Mol. Half Eq.Wt.= Wt. for Wt. for Wt. for
Wt. cell Mol. wt. 1lit 500 ml 250 ml
e. no.
(N ) (N ) (N )
reaction 10 10 10
K2 Cr2 O7 294.20 Cr2 O2−
7 + 14H + 6e
+ − 294.2
6
4.903 2.4515 1.2257
→ 2Cr2+ + 7H2 O = 49.03
KMnO4 158.04 MnO− +
4 + 8H + 5e
− 158.04
5
= 3.1608 1.5804 0.7902
→ 2Mn2+ + 4H2 O 31.608
KIO3 214.006 IO− +
3 + 6H + 5e
− 214.006
5
4.280 2.140 1.070
→ 2I0 + 3H2 O = 42.80
KBrO3 167.011 BrO− +
3 + 6H + 5e
− 167.001
5
3.3402 1.6701 0.835
→ 2Br0 + 3H2 O = 33.402
253.80
I2 253.80 I2 + 2e− 2
12.690 6.345 3.1725
→ 2I− = 126.90
C2 H2 O4 , 253.80 C2 O2−
4 − 2e
− 126
2
6.300 3.150 1.575
2H2 O → 2CO2 = 63.00 6.300 3.150 1.575
C2 Na2 O4 134 C2 O2−
4 − 2e
− 134
2
6.700 3.350 1.675
→ 2CO2 = 67.00
Na2 S2 O3 248 2S2 O2−
3 − 2e
− 248
1
24.80 12.40 6.20
1 2−
5H2 O → 2 S4 O6 = 248.00
391.87
FeSO4 , 391.87 Fe2+ − e− 1
39.187 19.5935 9.7965
391.87
(NH4 )2 SO4 , → Fe3+ 1
39.187 19.5935 9.7965
6H2 O =391.87
249.64
CuSO4 , 249.54 Cu2+ + e− 1
24.954 12.477 6.2385
5H2 O → Cu+ = 249.54
166.01
KI 166.01 I− − e − → I0 1
= 166.01 16.601 8.3005 4.1502
acid base reaction as well as many other titration reaction show colour change at definite
pH and there by indicate the end of the reaction are called indicator.
Chapter 12
Different essential tables
12.1.1. Viscosityη(cp) and temperature table
Temp. Viscosity Temp. Viscosity Temp. Viscosity Temp. Viscosity

C C C C
η(cp) η(cp) η(cp) η(cp)
0 1.787 26 0.8705 52 0.5290 78 0.3638
1 1.728 27 0.8531 53 0.5204 79 0.3592
2 1.671 28 0.8327 54 0.5121 80 0.3547
3 1.618 29 0.8148 55 0.5040 81 0.3503
4 1.567 30 0.7975 56 0.4961 82 0.3460
5 1.519 31 0.7808 57 0.4884 83 0.3418
6 1.472 32 0.7647 58 0.4809 84 0.3377
7 1.428 33 0.7491 59 0.4736 85 0.3337
8 1.386 34 0.7340 60 0.4665 86 0.3297
9 1.346 35 0.7194 61 0.4596 87 0.3259
10 1.307 36 0.7052 62 0.4528 88 0.3221
11 1.271 37 0.6915 63 0.4462 89 0.3184
12 1.235 38 0.6783 64 0.4398 90 0.3147
13 1.202 39 0.6654 65 0.4335 91 0.3111
14 1.169 40 0.6529 66 0.4273 92 0.3076
15 1.139 41 0.6408 67 0.4213 93 0.3042
16 1.109 42 0.6291 68 0.4155 94 0.3008
17 1.081 43 0.6178 69 0.4098 95 0.2975
18 1.053 44 0.6067 70 0.4042 96 0.2942
19 1.027 45 0.5960 71 0.3987 97 0.2911
20 1.002 46 0.5856 72 0.3934 98 0.2879
21 0.9779 47 0.5755 73 0.3882 99 0.2848
22 0.9548 48 0.5656 74 0.3881 100 0.2818
23 0.9325 49 0.5561 75 0.3781
24 0.9111 50 0.5468 76 0.3732
25 0.8904 51 0.5378 77 0.3684
117
118 CHAPTER 12. DIFFERENT ESSENTIAL TABLES
gm.
12.1.2. Density of water ρ = cm3 at temperature 00 C to 39.90 C(increament by 0.10 C)
table
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0 0.999841 0.999847 0.999854 0.999860 0.999866 0.999872 0.999878 0.999884 0.999889 0.999895
1 0.999900 0.999905 0.999909 0.999914 0.999918 0.999923 0.999927 0.999930 0.999934 0.999938
2 0.999941 0.999944 0.999947 0.999950 0.999953 0.999955 0.999958 0.999960 0.999962 0.999964
3 0.999965 0.999967 0.999968 0.999969 0.999970 0.999971 0.999972 0.999972 0.999973 0.999973
4 0.999973 0.999973 0.999973 0.999972 0.999972 0.999972 0.999970 0.999969 0.999968 0.999966
5 0.999965 0.999963 0.999961 0.999959 0.999957 0.999955 0.999952 0.999950 0.999947 0.999944
6 0.999941 0.999938 0.999935 0.999931 0.999927 0.999924 0.999920 0.999916 0.999911 0.999907
7 0.999902 0.999898 0.999893 0.999888 0.999883 0.999877 0.999872 0.999866 0.999861 0.999855
8 0.999849 0.999843 0.999837 0.999830 0.999824 0.999817 0.999810 0.999803 0.999796 0.999789
9 0.999781 0.999774 0.999766 0.999758 0.999751 0.999742 0.999734 0.999726 0.999717 0.999709
10 0.999700 0.999691 0.999682 0.999673 0.999664 0.999654 0.999645 0.999635 0.999625 0.999615
11 0.999605 0.999595 0.999585 0.999574 0.999564 0.999553 0.999542 0.999531 0.999520 0.999509
12 0.999498 0.999486 0.999475 0.999463 0.999451 0.999439 0.999427 0.999415 0.999402 0.999390
13 0.999377 0.999364 0.999352 0.999339 0.999326 0.999312 0.999299 0.999285 0.999272 0.999258
14 0.999244 0.999230 0.999216 0.999202 0.999188 0.999173 0.999159 0.999144 0.999129 0.999114
15 0.999099 0.999084 0.999069 0.999054 0.999038 0.999023 0.999007 0.998991 0.998975 0.998959
16 0.998943 0.998926 0.998910 0.998893 0.998877 0.998860 0.998843 0.998826 0.998809 0.998792
17 0.998774 0.998757 0.998739 0.998722 0.998704 0.998686 0.998668 0.998650 0.998632 0.998613
18 0.998595 0.998576 0.998558 0.998539 0.998520 0.998501 0.998482 0.998463 0.998444 0.998424
19 0.998405 0.998385 0.998365 0.998345 0.998325 0.998305 0.998285 0.998265 0.998244 0.998224
20 0.998203 0.998183 0.998162 0.998141 0.998120 0.998099 0.998078 0.998056 0.998035 0.998013
21 0.997992 0.997970 0.997948 0.997926 0.997904 0.997882 0.997860 0.997837 0.997815 0.997792
22 0.997770 0.997747 0.997724 0.997701 0.997678 0.997655 0.997632 0.997608 0.997585 0.997561
23 0.997538 0.997514 0.997490 0.997466 0.997442 0.997418 0.997394 0.997369 0.997345 0.997320
24 0.997292 0.997271 0.997246 0.997221 0.997196 0.997171 0.997146 0.997120 0.997095 0.997069
25 0.997044 0.997018 0.996992 0.996967 0.996941 0.996914 0.996888 0.996862 0.996836 0.996809
26 0.996783 0.996756 0.996729 0.996703 0.996676 0.996649 0.996621 0.996594 0.996567 0.996540
27 0.996512 0.996485 0.996457 0.996429 0.996401 0.996373 0.996345 0.996317 0.996289 0.996261
28 0.996232 0.996204 0.996175 0.996147 0.996118 0.996089 0.996060 0.996031 0.996002 0.995973
29 0.995944 0.995914 0.995885 0.995855 0.995826 0.995796 0.995766 0.995736 0.995706 0.995676
30 0.995646 0.995616 0.995586 0.995555 0.995525 0.995494 0.995464 0.995433 0.995402 0.995371
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Chapter 13
Some important figures
Figure 13.1: Viscosity
119
120 CHAPTER 13. SOME IMPORTANT FIGURES
Figure 13.3: Pink to purple red(Violet).

Figure 13.2: Wine red to blue
Figure 13.5: Structure of murexide

Figure 13.4: EDTA
Figure 13.6: Structure of Eriochrome black

T
Figure 13.7: Metal EDTA structure
121
Figure 13.9: Structure of Phenolphthalein

Figure 13.8: Metal edta structure
Figure 13.10: Phelophththalein in acid and Figure 13.11: Structure of Methyl orange
base
Figure 13.12: Methyl Orange in acid and Figure 13.13: Methyl Orange in neutral,
base acid and base medium
Figure 13.15: Conductometric titration

Figure 13.14: Conductometric titration graph(Strong acid Vs weak base )
graph(Strong acid Vs strong base)
Figure 13.16: Conductometric titration Figure 13.17: Conductometric titration

graph(Strong base Vs weak acid) graph(Strong base Vs weak acid )
Figure 13.18: Conductometric titration

graph(weak acid Vs weak base ) Figure 13.19: pH-metric titration graph acid
in cell
123
Figure 13.20: pH metric curve acid in cell

Figure 13.21: pH-metric graph base in cell
Figure 13.23: pH strong base Vs weak acid

Figure 13.22: pH weak base Vs strong acid
Figure 13.24: pH-metric graph strong base

in cell
Chapter 14
Some important equipments and

apparatus
Figure 14.1: Wash bottle Figure 14.2: Wash bottle
Figure 14.3: Bulb pipette Figure 14.4: Bulb and measuring pipette
125
Figure 14.5: Measuring pipette
Figure 14.6: Burette
Figure 14.7: Burette reading
Figure 14.8: Beaker
Figure 14.9: Measuring cylinder
Figure 14.10: Funnel

127
Figure 14.11: Conical flask
Figure 14.12: Reagent bottle
Figure 14.13: Stopper reagent bottle
Figure 14.14: Separating funnel
Figure 14.16: Tissue paper

Figure 14.15: Dropper
Figure 14.17: Conductometric bridge

Figure 14.18: pH metric bridge
Figure 14.19: pH metric bridge
Figure 14.20: Ostwald viscometer
Figure 14.21: Different type viscometer

Figure 14.22: Specific Gravity bottle
Bibliography
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M. Thomas,(6th edition)Pearson education ltd., Singapore,2000.
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University press 2003.
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works association, 1992
[5] Laboratory Manual of physical chemistry; G. J. Janz, A. W. Davison, John Wiley and Sons
Inc, London,1956.
[6] Measurement of viscosiry and sucrose concentration in aqueous solution using portable brix
meter; E. Handayanto, T. Tanabe, J. Kawai, B. Gisika, ISSN:1410-9662. Vol. 13, No. 2,Edisi
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[7] Physical chemistry(Vol III); H. Chatterjee, Platinum Publishers,2015.
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Chemica Scandinavica, 1951, 774-780.
129
Index
Equivalent conductance, 72 EBT, 25, 35

Molar conductance, 72 EDTA, 31
Ohms law, 71 Equivalent weight, 113
Specific conductance, 71
Strong electrolytes, 77 First order, 44
Transport number, 73 Fluid, 61
Weak electrolytes, 78 Formality, 111
Gravimetric, 109
Acetic acid, 54
Acid, 7 Hard water, 28
Acid base reaction, 67 Hardness, 27, 30
Alkali, 7 Heat of neutralisation, 76
Alkalinity, 1 Heat of solution, 106
Argentometric, 99 Heterogeneous equilibrium, 49
Arrhenius, 7
Arrhenius equation, 45 Immiscible solvent, 53
Association, 54 Indicator, 2, 9, 10
Iodometric, 96
Base, 7 Ionic mobility, 68
Bleaching powder, 103 Ionic product, 104
Buffer capacity, 88
Buffer solution, 88 Kohlrausch’s law, 75
Butanol, 53
Ligand, 30, 32, 35
Capillary, 65
Mohr salt, 20
Chelate complex, 31
Molalality, 111
Chelating ligand, 25
Molarity, 111
Chloride ion, 101
Mole fraction, 112
Colligative properties, 56
Molecularity, 44
Common ion effect, 105
Murexide, 34
Complex salt, 30
Complexometry, 25 Nernst’s distribution law, 53
Conductance, 71 Nernst’s equation, 21
Conductometric, 67 Neutralization, 8
Crystal water, 22
Octahedral complex, 35
DDT, 103 Order, 43
Density, 53, 58, 60, 62 Oxalic acid, 2
Density temperature, 118 Oxidation, 17, 21
Dimension of viscosity, 63 Oxidation number, 97
Dissociation, 54 Oxidation state, 22
Dissolved oxygen, 91 Oxide, 6
130
INDEX 131
Partition coefficient, 49 Z-R solution, 18, 21

Periodic function, 99 Zero order, 44
Permanganometry, 17
pH, 81, 85
pH scale, 87
Poisseuille’s equation, 57
Potassium chromate, 100
Potassium dichromate, 92
Potassium permanganate, 19
ppm, 27, 30
Precipitation, 105
Primary Standard, 110
Primary standard, 2
Pseudo first order reaction, 44
Pseudo unimolecular, 38
Rate, 42
Rate constant, 37, 43
Redox, 17, 23
Reduction, 17, 21
Renolds number, 65
Second order, 45
Secondary Standard, 110
Self indicator, 19
Silver nitrate, 101
Soap, 29
Sodium carbonate, 2
Sodium chloride, 101
Sodium hydroxide, 68
sodium thiosulfate, 94
Sodium thiosulphate, 92
Solubility, 55, 96
Solubility product, 104
Sparingly soluble salt, 104
Specific gravity, 62
Standard solution, 110
Standardization, 39
Starch, 92
Std. reduction potential, 18
Strength, 3
Titration, 8
Unit of order, 45
Viscometer, 57
Viscosity, 57, 62
Viscosity temperature, 117
Volumetric, 110
Winkler, 91

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PRACTICAL BOOK ON

As per New Revised Syllabus of WBUT

Dr. Pijus Kanti Khatua

General Features of the Book Include:

1 Experiment name: To Determine the alkalinity in a given water sample 1

2 Experiment name: Redox Titration- Estimation of iron(gm/lit)in supplied

3 Experiment name:Complexometric Titration (Estimation of Calcium and Mag-

4.3 Chemicals Required . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

5 Heterogeneous equilibrium (determination of partition coefficient of acetic

6 Experiment name:Viscosity of solutions (determination of percentage compo-

7 Experiment name:Conductometric titration for determination of the strength

8 Experiment name:. pH-metric titration for determination of strength of a

9 Determination of dissolved oxygen present in a given water sample 91

10 Experiment name:To determine chloride ion in a given water sample by Ar-

11 Important general question for viva-voce 109

12 Different essential tables 117

13 Some important figures 119

14 Some important equipments and apparatus 125

Experiment name: To Determine

1.1 Aim of experiment

OH- + HCO-3 → CO2-

iii) HCO-3 + H+ → H2 O + CO2

1.3 Chemicals required

Table 1.1: Weighing of Na2 CO3

1.5.2. Preparation of 250 ml of HCl solution:

1.5.3. Standardization of HCl solution by primary standard Na2 CO3 solution:

Table 1.2: Standardization of HCl solution by standard Na2 CO3 solution

Let, the strength of HCl = S2

V1 = Volume of standardNa2 CO3 solution

1.5.4. Analysis of water sample:

Table 1.3: Analysis of water using phenolphthalein indicator

Table 1.4: Analysis of water using methyl orange indicator

V5 = Volume of water sample taken = 20 ml

So, Strength in terms of CaCO3 equivalent

Therefore, methyl orange alkalinity (M) = B × 1000 mg/L

[N.B.: During writing precaution write your own passive voice.]

1.8.4. P < 12 M; indicates that beside CO2- -

1.9 Question for viva-voce

1.9.2. What is Acid?

1.9.3. What is base?

1.9.4. What is alkali?

1.9.7. What is hydroxide?

1.9.9. How water becomes alkaline?

1.9.10. Describe strong base weak base. Give example.

1.9.11. What is acidity of base?

1.9.12. Describe different types of expression for strength of base.

1.9.13. Describe different types of alkalinity.

1.9.15. What is neutralization reaction?

1.9.16. What is titration?

1.9.17. Give the principle of acid base titration.

VA = Volume of standard oxalic acid solution

1.9.18. What is indicator?

1.9.19. What is indicator action?

HIn(Colour I) ¿ H+ + In− (Colour II)

Its equilibrium constant is given by:

Indicator pH range Color in acid solution Color in alcaline solution

1.9.21. What is selection of indicator- explain.

Na2 CO3 + HCl = NaHCO3 + NaCl

M H SO as titrant to reach the end point by using

Sample Require volume of titrant Require volume of titrant

1.9.26. What effects occur by alkaline water in different corners of industry?

1.9.27. What is the importance of this experiment in the aspect of engineering?

Phelophththalein in acid and base