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Rajshahi University of Engineering & Technology

Rajshahi-6204

Lab Manual
Department of Chemistry

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 Lab Manual
For
Undergraduate Students of Various Engineering Departments

First edition

• Effective from UG Session 2017 – 2018

Mailing address
Head
Department of Chemistry
Rajshahi University of Engineering & Technology
Rajshahi- 6204, Bangladesh
Phone: +88-0721-750834
Fax: +88-0721-750834
Email: [email protected]

Department of Chemistry
October 2017

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 CONTENTS

Chapter Name of Chapter Page

Chapter-I General Information 6 – 13

Safety in the undergraduate chemistry laboratories 6

Personal Protective Equipment (PPE) 7
Good Practiced Rules 7
Solution 7
Composition or concentration of solution 8
Standards solution 9
Titration 9
Equivalence point and end point 10
Indicators 10
Primary standard substance 12
Significant figures 12
Precision and accuracy 12
Absolute error and relative error 13
Data collection and reporting 13

Chapter-II Inorganic Laboratory Experiments 14 – 32

Determination of the strength of supplied sodium hydroxide solution 15

by standardized hydrochloric acid solution
Determination of the strength of supplied potassium permanganate 18
solution by a standard solution of sodium oxalate/oxalic acid
Determination of the strength of supplied sodium thiosulfate solution 21
iodometrically by a standard solution of potassium dichromate
Determination of iron in ore titrimetrically by standardized solution of 24
potassium permanganate
Determination of calcium in limestone as CaO 26
Determination of copper in crystalline copper sulfate 29
Determination of chloride ion (Cl-) gravimetrically in a soluble sample 31

Chapter-III Organic Chemistry Experiments 33 – 38

Systematic analysis and identification of unknown organic 34

compounds. 34
Preliminary examination 34
Solubility test 35
Result and discussion 35
Elementary analysis 36
Test of elements 36
Detection of functional groups

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Chapter-IV Physical Chemistry Experiments 39 – 50

Determination of pH of given solution 40

Determination of heat of neutralization of strong acid with strong base 42
calorimetrically
Determination of heat of solution of supplied sample in water 44
calorimetrically
Determination of the rate constant and justification of the order of a 45
chemical reaction
Determination of equilibrium constant using distribution coefficient 48

Chapter-V Industrial and Environmental Chemistry Experiments 51 – 59

Determination of acidity of supplied water sample 52

Determination of alkalinity of a given water sample 53
Determination of the amount of dissolved oxygen by Winkler method 54
Determination of corrosion rate of mild steel (MS) in hydrochloric 56
(HCl) acid solution
Determination of corrosion rate of mild steel (MS) in hydrochloric 57
(HCl) acid solution containing Cu2+ ion

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 Chapter-I

General Discussion

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Safety in the undergraduate laboratories

Safety means freedom from unacceptable risk. To those who have suffered personal loss, injuries and even death
in laboratory incidents that were preventable, we may use the knowledge from these incidents to teach the next
generation of scientists about laboratory and chemical safety.

Safety is the term consisting of some precautionary measures that are taken by the people at the time of performing
a job inside the laboratory to check or avoid any accident, injury, danger and hazard.
Safety : Freedom from unacceptable risk.
Hazard : A situation that may give rise personal or environmental injury.
Danger : A state or condition in which personal injury is reasonably foreseeable.
Risk : Combination of probability of injury and degree of injury.
Accident : Unplanned or undesired event that may cause to death, illness, injury, damage or loss
of life, wealth and environment or their combination.

Incident of mixing acid and water: John was doing an experiment that required the use of dilute sulfuric acid. The
instructor said that students should mix 1 part of concentrated sulfuric acid with 4 parts of water and that everyone
should always add acid to water and not water to acid. John was not paying attention when the instructions were
given and he added water to acid. There was a violent popping noise, the beaker became hot, and a mist formed
over the solution, and some solution splattered out onto his skin and his partner’s skin.
What lessons can be learnt from this incident?
These notes are directed to all users of undergraduate chemistry laboratories.

General Guidelines for Safety

1. No undergraduate may perform an experiment to which the student has not been specifically assigned.
Other than in project courses, no undergraduate experiment of any kind may be performed in the absence
of an instructor, demonstrator or technician.
2. Learn the location of escape routes and of all safety equipment (showers, eye wash station, fire
extinguishers, fire alarm, telephone, etc.) before you start to work in any room. Know how to use the
equipment.
3. Smoking, eating or drinking is not permitted. Nothing should be placed in the mouth. Pipetting by mouth
is absolutely forbidden.
4. Regard all chemicals as potentially hazardous. Treat with special caution those chemicals that the
laboratory manual cites as toxic, poisonous or otherwise dangerous. Do not attempt to clean up any spills
yourself - inform the demonstrator of the problem as soon as possible.
5. Compressed gas cylinders should always be securely anchored to a wall or heavy bench. If a large
cylinder tips over and the valve snaps off, the cylinder becomes a jet-propelled missile which has
sufficient power to penetrate a brick wall.
6. If you are in doubt as to the safety of a procedure, don't do it until you have sought professional advice.
7. All accidents, however minor, must be reported to the person in charge of the lab immediately.
8. Practice good housekeeping - a clean work space is much safer than a messy one. The dangers of spilled
acids and chemicals and broken glassware created by thoughtless actions are too great to be tolerated.
Clean up your work space, including wiping the surface and putting away all chemicals and equipment,
at the end of the laboratory period.
9. Wash out all the laboratory equipment after use and submit them to the lab in charge.

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Personal Protective Equipment (PPE)

Personal protective equipments means all attires and equipment (including clothing affording protection against
the weather), which is intended to be worn or held by a person at work and which protects him against one or
more risk to his health. It also helps person to work confidently against risk.

Purposes of PPE
The purposes of PPE are as follows
✓ To protect the people in working place.
✓ To maintain safe operation of the experiment.
✓ To reduce accidents.
✓ To enhance the awareness of process safety.

Classification of PPE

Class Examples of PPE

Head protective equipment Safety helmets and hats
Eye protective equipment Safety spectacles, eye shield, safety goggles, welding
filter/goggles, welding helmets etc.
Face protective equipment Plastic face shield, metal screen face shield, welding helmets
etc.
Ear protective equipment Insert type ear protector: ear plug
Muff type ear protector: ear muff
Respiratory protective equipment Chemical cartridge respirator, gas mask, nose mask, air-line
respirator, cotton mask etc.
Hand and finger protective equipment Rubber gloves, leather gloves, PVC gloves, linen gloves etc.
Foot protective equipment Safety shoes
Special clothing Apron (compulsory)

Good Practiced Rules

1. Carefully read the experiment before coming to the laboratory. An unprepared student is a hazard to
everyone in the room.
2. Dispose of excess reagents as directed by your instructor or laboratory demonstrator. Never return
reagent to bottles.
3. Always pour acids into water when mixing. Otherwise the acid can spatter, often quite violently.
4. Avoid breathing fumes of any kind.
a. To test the smell of a vapor, collect some in a cupped hand.
b. Work in a hood if there is the possibility that noxious or poisonous vapours may be produced.
5. Be careful when heating liquids. Flammable liquids such as ethers, hydrocarbons, alcohols, acetone, and
carbon disulfide must never be heated over an open flame.
6. Test tubes being heated or containing reacting mixtures should never be pointed at anyone. If you observe
this practice in a neighbor speak to them or the instructor.
7. Do not force rubber stoppers onto glass tubing or thermometers. Lubricate the tubing and the stopper
with glycerol or water.
8. Finally, and most importantly, THINK about what you’re doing. Plan ahead. If you give no thought to
what you are doing, you predispose yourself to an accident.

Solution

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Solution is a homogeneous mixture of two or more different substances in molecular level. For example, when a
certain amount of NaCl is added to a glass of water and slightly stirred with a stick it form a homogeneous mixture
which is a solution. The higher amount of component in the solution is known as solvent and the lower amount
component is known as solute in case of solution of solid in liquid. Here NaCl is solute and water is solvent.

Figure 1: Solution
Composition or concentration of solution

The concentration of a solution is defined as the amount of solute present in a given amount of solvent/solution.
Concentration of a solution can be expressed in different terms. Such as molarity, molality, normality, mole
fraction, percentage etc.

Molarity

Molarity of a solution is defined as the number of moles of solute per litre of the solution.
1 mole solute + solvent = 1 litre solution (1 molar).
1 mole H2SO4(98 g) + solvent (water) = 1 litre H2SO4 solution (1 molar).
w × 1000
molarity =
M × V (ml)
Here,
w = amount of the solute in g
M = molecular weight of solute in g/mole
V = volume of the solution in mL

Molality

Molality of a solution is defined as the number of moles of solute per kilogram(1000 g) of solvent.
1 mole solute+ 1 kilogram (1000 g) solvent = 1 molal solution (volume is inconsiderate).
1 mole H2SO4(98 g) + 1 kilogram (1000 g) solvent (water) = 1 molal H2SO4 solution.
w × 1000
molality =
M × W (g)
Here,
w = amount of the solute in g
M = molecular weight of the solute in g/mole
W = amount of the solvent in g

Normality

Normality of a solution is defined as the number of gram-equivalents of solute per litre of the solution.
1 gram-equivalents solute + solvent = 1 litre solution (1 Normal).
1 gram-equivalents H2SO4(49 g) + solvent (water) = 1 litre H2SO4 solution (1 Normal).

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 w × 1000
normality =
E × V (mL)
Here,
w = amount of the solute in g
E = equivalent weight of the solute g/gram-equivalent
V = volume of the solution in mL

Advantages of the use of equivalent system for the preparation of standard solution

The most important advantage of the equivalent system is that the calculations of volumetric analysis are rendered
very simple, since at the end point the number of equivalents of the substance titrated is equal to the number of
equivalents of the standard solution employed. We may write:

Number of gram − equivalents

Normality =
Number of litres of solution

Hence, number of gram-equivalents = number of litre of solution × normality.

If the volume of solutions of two different substances A and B which exactly react with one another are V A and
VB ml, respectively, then these volumes severely contain the same number of gram-equivalents of A and B. Thus:
Number of gram − equivalents of A = Number of gram − equivalents of B

Number of gram − equivalents of A Number of gram − equivalents of B

VA × = VB ×
VA VB
VA × normality of A = VB × normality of B
VA × SA = VB × SB
In practice VA, VB and SA (normality of standard solution) are known, hence the normality of the analyte (unknown
solution), SB can be readily calculated.

Standard solution

A standard solution is a reagent or solution of known concentration. Standard solutions are used in titrations and
in many other chemical analyses. The strength of a testing solution is determined by reacting it with the standard
solution. Standard solutions play a central role in all titrations. Therefore, we must consider the desirable
properties for such solutions, how they are prepared, and how their concentrations are expressed. The ideal
standard solution for a titrimetric method will
1. be sufficiently stable so that it is necessary to determine its concentration only once;
2. React rapidly with the analyte so that the time required between additions of reagent is minimized;
3. React more or less completely with the analyte so that satisfactory end points are realized;
4. Undergo a selective reaction with the analyte that can be described by a balanced equation.

Titration

Titration is a concentration determining analytical method of a solution. It can be defined as the method by which
the concentration of a test solution is determined by reacting it with a standard solution. Titrations are widely used
in analytical chemistry to determine the strength of acids, bases, oxidants, reductants, metal ions and many other
species. There are different types of titrimetric methods. Volumetric titrations involve measuring the volume of a
solution of known concentration that is needed to react completely with the analyte. In Gravimetric titrations, the
mass of the reagent is measured instead of its volume. In coulometric titrations, the “reagent” is a constant direct
electrical current of known magnitude that consumes the analyte. Titrations are based on a reaction between the
analyte and a standard reagent known as the titrant. The reaction is of known and reproducible stoichiometry.

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Back titration: It is sometimes necessary to add an excess of the standard titrant and then determine the excess
by back titration with a second standard titrant. Here the equivalence point corresponds to the point where the
amount of initial titrant is chemically equivalent to the amount of analyte plus the amount of back titrant. Back
titrations are often required when the rate of reaction between the analyte and reagent is slow or when the reagent
lacks stability.

Equivalence point and end point

The equivalence point in a titration is a theoretical point reached when the amount of added titrant is chemically
equivalent to the amount of analyte in the sample. For example, the equivalence point in the titration of sulfuric
acid with sodium hydroxide is reached after introducing 2 moles of base for each mole of acid.

H2SO4 + 2NaOH → Na2SO4 + 2H2O

We cannot determine the equivalence point of a titration experimentally. Instead, we can only estimate its position
by observing some physical change associated with the condition of chemical equivalence. The position of this
change is called the end point for the titration. We try very hard to ensure that any volume or mass difference
between the equivalence point and the end point is small. Such differences do exist, however, as a result of
inadequacies in the physical changes and in our ability to observe them. The difference in volume or mass between
the equivalence point and the end point is the titration error.

Indicator: An indicator is often added to the analyte solution in order to give an observable physical change at or
near the equivalence point. We shall see that large change in the relative concentrations of the analyte and titrant
occurs in the equivalence point region. These concentration changes cause the indicator to change in appearance.
Typical indicator changes are appearance or disappearance of color, change in color and the appearance or
disappearance of turbidity.

Common types of acid base indicators: Numerous organic compounds serve as indicator for neutralization
titrations. The majority of acid base indicators possess structural properties that permit classification into perhaps
half a dozen categories.

Azo indicator: Most azo indicators exhibit color change from red to yellow with increasing basicity (pH), their
transition ranges are generally on the acidic side of neutrality. The most commonly encountered examples are
methyl orange and methyl red. The behavior of the former is described by the equation given below.

- H
O3S N N N(CH 3)2
+

-
+ H2O O3S N N N(CH 3)2
- H
O3S N N N(CH 3)2 +
+ H3O

Methyl orange

Phthalein indicator: Most Phthalein indicators are colorless in moderately acidic solutions and exhibit a variety
of colors in alkaline media. These colors tend to fade slowly in strongly alkaline solutions which are an
inconvenience in some applications. As a group, the Phthalein indicators are sparingly soluble in water but readily
dissolve in ethanol to give dilute solutions of the indicators. The best Phthalein indicator is phenolphthalein whose
structure can be represented as mentioned below.

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HO OH HO OH O O-

O
+ H2O OH O + H+
O + H+ O

O- O-

Colorless Colorless Red

Phenolphthalein: 3,3-bis[4-hydroxyphenyl-[3H]isobenzofuranone

+ _
HO OH HO O O O

+
SO 3 + H2O _
+ H+ _ +H
SO 3 SO 3

Red Yellow Red

Phenol red

1 2 3

5
4
Figure 2: Titration

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Primary Standards substance

A primary standard is a highly purified compound that serves as a reference material in all volumetric titrimetric
methods. The accuracy of such methods is critically dependent on the properties of these compounds. Important
requirements for a primary standard are:
1. High purity, established methods for confirming purity should be available
2. Stability in air.
3. Absence of hydrate water so that the composition does not change with variations in relative humidity.
4. Ready availability at modest cost.
5. Reasonable solubility in the titration medium.
6. Reasonable large formula weight so that the relative error associated with weighing is minimized.

Very few compounds meet or even approach these criteria and only a limited number of primary-standard
substances are available commercially. As a consequence, less pure compounds must sometimes be used in place
of a primary standard. The purity of such a secondary standard must be established by careful analysis.

A secondary standard is a compound whose purity has been determined by chemical analysis. The secondary
standard serves as the working standard material for titrations and for many other analyses.

Significant figures

We often indicate the probable uncertainty associated with an experimental measurement by rounding the result
so that it contains only significant figures. By definition, the significant figures in a number are all of the certain
digits plus the first uncertain digit. For example, when you read the 50-mL burette section shown in Figure 3, you
can easily tell that the liquid level is greater than 30.2 mL and less than 30.3 ml. You can also estimate the position
of the liquid between the graduations to about 0.02ml. So, using the significant figure convention, you should
report the volume delivered as 30.24mL, which has four significant figures. Note that the first three digits are
certain, and the last digit (4) is uncertain.

System of taking burette reading A burette section showing the liquid level and meniscus

Precision and accuracy

Precision describes the reproducibility of measurements, in other words, the closeness of results that have been
obtained in exactly the same way. Generally, the precision of a measurement is readily determined by simply
repeating the measurement on replicate samples. Three terms are widely used to describe the precision of a set of
replicate data: standard deviation, variance, and coefficient of variation. These three are functions of how much
an individual result xi differs from the mean, called the deviation from the mean di.

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 𝑑𝑖 = |𝑥𝑖 − 𝑥̅ |

Accuracy indicates the closeness of the measurement to the true or accepted value and is expressed by the error.
Figure 4illustrates the difference between accuracy and precision. Note that accuracy measures agreement
between a result and the accepted value. Precision, on the other hand, describes the agreement among several
results obtained in the same way. We can determine precision just by measuring replicate samples. Accuracy is
often more difficult to determine because the true value is usually unknown. An accepted value must be used
instead. Accuracy is expressed in terms of either absolute or relative error.

Figure 4: Illustration of accuracy and precision using the pattern of darts on a dartboard.

Absolute error and relative error

The absolute error of a measurement is the difference between the measured value and the true value. The sign
of the absolute error tells you whether the value in question is high or low. If the measurement result is low, the
sign is negative; if the measurement result is high, the sign is positive.

Absolute error, E = xi − xt

Where, xi is the measured value and xt is the true or accepted value of the quantity.

The relative error of a measurement is the absolute error divided by the true value. Relative error may be expressed
in percent, parts per thousand, or parts per million, depending on the magnitude of the result.
xi − xt
Relative error, Er = × 100%
xt

Data collection and reporting

Collection of data is an art. If the data collection is better, the corresponding data analysis and reporting will be
better. So collection of data is very important. Collection of data highly influences the final result. For this reason,
during performing an experiment in the laboratory one should be very careful in the collection of data. One can
follow the following tips for data collection.
✓ You must carefully observe the scale and capacity of the measuring devises.
✓ You must remember the rules of significant figure during data collection.
✓ The collection of data must be clear and precise.
✓ Data must be collected in a fair notebook.
✓ In the data collection page, the name of experiment and date must be present.
✓ All the data collected may be or may not be taken in data analysis or calculation. The outliers must be
avoided. Otherwise the final result will be biased.
After data collection, calculation and analysis, you must produce a report with result and conclusion.

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 Chapter-II

Inorganic Laboratory Experiments

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Name of experiment: Determination of the strength of supplied sodium hydroxide solution by
standardized hydrochloric acid solution
Introduction
According to Bronsted-Lowry’s acid-base theory, acid is the chemical species (either molecule or ion) which
donates proton to other chemical species and base is the chemical species (either molecule or ion) which can
accepts proton from an acid.

Na2CO3 + 2HCl → 2NaCl + H2O + CO2 HCl is an acid

NaOH + HCl → NaCl + H2O Na2CO3 and NaOH are base

The chemical reaction involved in acid-base titration is known as neutralization reaction. The reaction occurs
between H3O+ ions and OH- ions to form water. In acid-base titrations, solutions of alkali are titrated against
standard acid solutions. The estimation of an alkali solution using a standard acid solution is called acidimetry.
Similarly, the estimation of an acid solution using a standard alkali solution is called alkalimetry.

Chemicals Apparatus
Na2CO3 (anhydrous)
Burette (50 mL)
Hydrochloric acid
Pipette (10 mL or 25 mL)
Methyl orange indicator
Volumetric Flask (250 mL)
Phenolphthalein indicator
Erlenmeyer conical flask
Squeezer or Wash bottle
Thermometer, Funnel
Electronic balance
Dropper

Principle
Hydrochloric acid is a secondary standard substance as it absorbs moisture from air and it cannot be obtained
perfectly free from water. Therefore it is necessary to standardize it against a primary standard substance. Sodium
carbonate can be used for this purpose. This experiment involves two successive steps:

(i) Standardization of hydrochloric acid against a standard solution of sodium carbonate and

(ii) Standardization of sodium hydroxide against the freshly standardized hydrochloric acid.

If V1 ml of S1 N-hydrochloric acid is required for the titration of V 2 ml sodium hydroxide solution, the
concentration of sodium hydroxide solution can be calculated by using the formula given below: S 1V1 = S2V2,
where S2 is the concentration of sodium hydroxide solution.

Selection of indicator
It has been observed that the neutralization of a weak base (0.1N- aqueous ammonia) with a strong acid (0.1N-
hydrochloric acid) gave the following neutralization curve (Fig. 1).

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Figure 1: Neutralization curves of 100 mL 0.1M aqueous ammonia and 0.1M hydrochloric acid.

Form the neutralization curve it is evident that the equivalence point is at pH 5.3, which implies that neither
thymolphthalein (8.3-10.5) nor phenolphthalein (8.3-10.0) can be employed in the titration of 0.1N-aqueous
ammonia. Therefore, it is necessary to use an indicator with a color change interval on the slightly acidic side (3-
6.5) such as methyl orange (3.1-4.4), methyl red (4.2-6.3), bromophenol red (5.2-6.8) or bromocresol green (3.8-
5.4) etc. Similarly, it has been noticed that the neutralization of a strong acid (N-normal hydrochloric acid) by a
strong base (N-normal sodium hydroxide) resulted in a neutralization curve as shown in figure 2. From the figure,
it is clear that the equivalence point lies in the region of pH from 3.3 to 10.7.

Figure 2: Neutralization curves of 100 mL of HCl with NaOH solution of same concentration.

This implies that any indicator can be used for the titration of strong acid vs strong base as most of the indicators
show rapid colour change within this region.

Preparation of standard 0.10N sodium carbonate solution

Sodium carbonate formula: Na2CO3; Molecular weight: 105.99 g/mol; Equivalent weight: 52.995 g/ g eqv.

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 1
Normality = No. of gram equivalent X
Volume of solution in L
Mass in g 1
Or N = X
Equivalent mass Volume of solution ( L)

Mass in g = Normality (equivalent L-1) X Equivalent mass (g equiv-1)X Volume of solution (L)

= 0.1× 52.995 × (100/1000) = 0.53 g.

Therefore, 0.53 g of anhydrous sodium carbonate has to be dissolved in water in a volumetric flask and to be
diluted up to 100 mL.

Accurate concentration of sodium carbonate solution

Mass of Na2CO3 taken

= X 0.1
Mass of Na2CO3 should be taken

Preparation of standard 0.1N-hydrochloric acid solution: 9 ml of pure concentrated hydrochloric acid (36%,
w/v) to be poured into a litre of volumetric flask or into a litre measuring cylinder containing 500 ml of distilled
water from a burette and then to be made up to the litre mark with distilled water by subsequent shaking. This
will give a solution of approximately 0.1 N.

Experimental Procedure

Wash the supplied apparatus successively with chromic acid, tap water and distilled water. Place 0.1N-
hydrochloric acid which has been standardized by means of standard sodium carbonate in the burette. Transfer 25
mL of the sodium hydroxide solution into a 250-mL conical flask with the aid of a pipette, dilute the solution with
a little water and add 1-2 drops of methyl orange as indicator. A yellow color will be appeared in the solution.
Titrate the resulting yellow solution with the freshly standardized hydrochloric acid solution by the slow addition
of hydrochloric acid from the burette. At the end point a pink color will be observed. Repeat the titrations until
duplicate determinations agree within 0.05 mL of each other.

Experimental Data

Standardization of hydrochloric acid solution

Volume of Burette reading (volume of HCl

No. Average or Conc. of HCl
Na2CO3 solution), mL Conc. of std.
of mean value soln.
solution, Initial Final solution (N)
obs. Difference (mL) (N)
(mL)
1
2
3
Standardization of sodium hydroxide solution

Volume of Burette reading (volume of HCl

No. Average or Conc. of
NaOH solution), mL Conc. of std.
of mean value NaOH solution
solution, Initial Final solution (N)
obs. Difference (mL) (N)
(mL)
1
2
3

Result: The concentration of the supplied sodium hydroxide solution was found to be of ……… N.

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Name of experiment: Determination of the strength of supplied potassium permanganate solution
by a standard solution of sodium oxalate / oxalic acid

Introduction

This is a redox titration that means the chemical reaction includes oxidation-reduction reaction. A redox reaction
is accompanied by the transfer of electrons from one species to another. A redox reaction is sub-divided into two
half reactions. One is oxidation and another is reduction. In oxidation reaction, electron is released with
simultaneous increase in oxidation number, while in reduction reaction, electron is received with simultaneous
decrease in oxidation number. For example,
2Na0 + Cl20 = Na+ + Cl-
2Fe3+ + Sn2+ = 2Fe2+ + Sn4+
6KI + 14HCl + K2Cr2O7 = 2CrCl3 + 3I2 + 8KCl + 7H2O
2KMnO4 + 5H2C2O4 + 3H2SO4 = K2SO4 + 2MnSO4 + 10CO2 + 8H2O

The chemical species which donates electron is called reducing agent and the chemical species which accepts
electrons is called oxidizing agent.

2Na - 2e = 2Na+ (oxidation reaction, Na is reducing agent )

Cl2 + 2e = 2Cl- (reduction reaction, Cl2 is oxidizing agent )
Sn2+ - 2e = Sn4+ (oxidation reaction)
2Fe3+ + 2e = 2Fe2+
(reduction reaction)
C2O42- - 2e = 2CO2 (oxidation reaction)
MnO4-+ 8H+ + 5e = Mn2+ + 8H2O (reduction reaction)

Theory

Potassium permanganate is a strong oxidizing agent and was first introduced by F. Margueritte for the titration of
Fe (II). In an acid solution, the reduction reaction can be represented by the following equation:

MnO4-+8H+ +5e- → 2Mn2+ + 4H2O…………………………………..……………………….…….(1)

The standard potential in acid solution, Eo, has been calculated to be 1.51 volts; hence the permanganate ion in
acid solution is a strong oxidizing agent. Sulfuric acid the most suitable acid, as it has no action upon permanganate
in dilute solution. With hydrochloric (reducing agent) acid, the following reaction takes place:

2MnO4 - + 10 Cl- + 16H+ → 2Mn2+ + 5Cl2 + 8H2O ……………..…………………………………(2)

This reaction implies that some permanganate may be consumed in the formation of chlorine. This may result in
positive error. Thus HCl cannot be used in case of acidification of permanganate solution.

HNO3 also cannot be used for acidification of oxalic acid solution because nitric acid always contains some nitrous
acid which dangerously affects the stability of oxalic acid as follows:
Potassium permanganate react with nitrous acid and nitric acid

2KMnO4 + 5HNO2 + HNO3 → 2Mn(NO3)2 + 2KNO3 + 3H2O

Potassium permanganate reacts with nitrous acid and nitric acid to produce manganese (II) nitrate, potassium
nitrate and water but sulfuric acid has no such parasitic reaction upon permanganate solution.
Potassium permanganate is not a primary standard substance because

1. It is not possible to obtain the substance perfectly pure and completely free from manganese dioxide.

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 2. Ordinary distilled water is likely to contain reducing substances (traces of organic matter), which will
react with the potassium permanganate to form manganese dioxide. The presence of the latter is very
objectionable because it catalyzes the auto-decomposition of the permanganate solution on standing:

4MnO4- + 2H2O (containing organic reducing agent) = 4MnO2 + 3O2 + 4 OH- (3)
Permanganate is inherently unstable in the presence of manganese (II) ions:

2MnO4- +3Mn2+ + 2H2O =5MnO2 + 4H+ (4)

This reaction is very slow in acid solution, but very rapid in neutral solution. This is why dissolving weighed
amounts of the purified solid in water rarely makes up potassium permanganate.

Oxalic acid is a primary standard as this reagent is readily obtained as pure and anhydrous, and the ordinary
material has a purity of at least 99.9 per cent. This substance reacts as a reducing agent in presence of an oxidizing
agent and is oxidized by releasing its electrons.

The oxidation half reaction is: C2O42- → 2CO2+ 2e- (5)

Multiplying equation (1) with two 2 and equation (5) with five 5 and adding the resultant equations we have

2MnO4- + 5C2O42- +6H+ = 2Mn2+ + 10 CO2 + 8 H2O (6)

The molecular reaction can be represented as

2KMnO4 + 5 H2C2O4 + 3H2SO4 = 2MnSO4+ K2SO4 + 10 CO2 + 8 H2O (7)

Thus potassium permanganate solution can be standardized using an acidic solution of oxalic acid.
If V1 mL of KMnO4 solution of concentration S1(N) is required to titrate V2 mL of oxalic acid of concentration
S2(N), the concentration of KMnO4 can be calculated by using the equation S1V1 = S2V2.

Preparation of 0.1N (100 ml) standard solution of oxalic acid

Formula: C2H2O4.2H2O; 1 mole = 126.066 g
Mass of oxalic acid to be taken can be calculated as follows:
1
Normality = No. of equivalent ×
Volume of solution in L
Mass 1
Normality = ×
Equivalent wt Volume of solution in L

Mass (g) = Normality × Eqv. wt. × Volume of solution in L

= 0.1N × 63.033g/N × (100 mL/1000 mL) = 0.63033 g.

Preparation of 0.10 N potassium permanganate solution

Dissolve about 3.2 g of KMnO4 in 1 L of deionized water using a large beaker. Cover that beaker with a watch-
glass and heat to boiling using a hot plate in the hood. Keep the solution at a gentle boil for about 1 hr. Let the
solution stand overnight. Remove MnO2 by filtering through a filter crucible. Transfer the solution to a clean
amber glass-stoppered bottle; store in the dark when not in use.

Permanganate solutions are heated first to destroy reducible substances (traces of organics remaining in deionized
water). After cooling, the solution is filtered through a glass filtering crucible to remove manganese dioxide
impurities. If the solution is kept in the dark and is not acidified, its concentration will remain stable for several
weeks.

Page 19 of 59
Procedure

Dry about 1.5 g of primary standard grade oxalic acid at 110ºC for 1 hr. and cool in a desiccator. Weigh accurately
0.63033 g of oxalic acid and dissolve it in a 100 mL volumetric flask with occasional shaking, then make up to
the mark with distilled water by subsequent shaking. This will give a solution of Ca. 0.10 N. Take the supplied
permanganate solution in burette and make up to zero mark. Take 10 ml of freshly prepared standard oxalic acid
solution by pipette. Acidify the solution with 10 mL of 1M sulfuric acid. Allow the solution to cool at room
temperature. Start titration rapidly at the ordinary temperature until the first pink color appears throughout the
solution, and allow to stand until the solution is colorless. Warm the solution to 80-90oC and continue titration to
a permanent faint pink color. At the end point the faint pink color will persist for 30 sec. Measure the volume of
permanganate required for titration from burette. Carry out two or three more readings for the confirmation of the
end point until the readings agree with ± 0.05 mL from each other.

End Point

A useful property of potassium permanganate solution is its intense purple color, which is sufficient to serve as
indicator for most titrations. As little as 0.01 mL of a 0.02M solution imparts a perceptible color to 100 mL of
water. If the permanganate solution is very dilute, diphenylamine sulphonic acid or the 1,10-phenanthroline
complex of iron (II) provides a sharper end point.

The permanganate end point is not permanent because excess permanganate ions react slowly with the relatively
large concentration of manganese (II) ions present at the end point:

2MnO4- + 3Mn2+ + 2H2O → 5MnO2 (s) + 4H+

The equilibrium constant for this reaction is about 10 47, which indicates that the equilibrium concentration of
permanganate ion is vanishingly small even in the highly acidic media. Fortunately, the rate at which this
equilibrium is approached is so slow that the end point fades only gradually over a period of 30s.

Sodium Oxalate

Sodium oxalate is widely used for standardizing permanganate and cerium (IV) solutions. In acidic solutions, the
oxalate ion is converted to the un-dissociated acid. Thus the reaction with permanganate ion can be depicted as

2MnO4-+ 5H2C2O4+ 6H+ = 2Mn2+ + 10CO2(g) + 8H2O

Carbon dioxide is also the product with cerium (IV).

The reaction between permanganate and oxalic acid is complex and proceeds slowly even at elevated temperature
unless manganese (II) is present as a catalyst. Thus, when the first few milliliters of standard permanganate is
added to a hot solution of oxalic acid, several seconds elapse before the color of the permanganate disappears. As
the concentration of manganese (II) builds up, however the reaction proceeds more and more faster as a result of
autocatalysis.

It has been found that when solutions of sodium oxalate are titrated at 60 to 90ºC, the consumption of
permanganate is 0.1 to 0.4% less than theoretical, probably due to the air-oxidation of a fraction of the oxalic acid.
This small error can be avoided by adding 90 to 95% of the required permanganate to a cool solution of oxalate.
After the added permanganate is completely used up as indicated by the disappearance of color, the solution is
heated to about 60ºC and titrated to a pink color that persists for about 30s. The disadvantage of this procedure is
that it requires knowledge of the approximate concentration of the permanganate solutions so that a proper initial
volume of it can be added. For most purposes, the direct titration of the hot oxalic acid solution provides perfectly
adequate data (usually 0.2 to 0.3 % high).

Page 20 of 59
Precautions

1. Promptly wash any permanganate that spatters on the walls of the beaker into the bulk of the liquid with
a stream of water.
2. Finely divided MnO2 will form along with Mn2+ if the permanganate is added too rapidly and will cause
the solution to acquire a faint brown discoloration. Precipitate formation is not a serious problem so long
as sufficient oxalate remains to reduce the MnO 2 to Mn2+; the titration is simply discontinued until the
brown color disappears. The solution must be free from MnO2 at the end point.
3. The surface of permanganate solution rather than the bottom of the meniscus can be used to measure
titrant volumes. Alternatively backlighting with a flashlight or a match permits reading of the meniscus
in the conventional manner.
4. A permanganate solution should not be allowed to stand in a burette any longer than necessary because
partial decomposition to MnO2 may occur. Freshly formed MnO2 can be removed from a glass surface
by washing with 1M H2SO4 containing a small amount of 3% H2O2 or with a dilute solution of sodium
bisulfide (NaHSO3). The solution is prepared by dissolving 1 g NaHSO3 in 400 ml water.

The following reaction occurs during reaction of manganese dioxide with sulfuric acid:

2MnO2 + H2O2 + H2SO4 = 2MnSO4 + 2H2O

Reactions of permanganate ion in strongly alkaline solution:

MnO4- + e- = MnO42- (rapid reaction)

MnO42- + 2H2O + 2e- = MnO2 + 4OH- (slow reaction)
Reactions of permanganate ion in moderately alkaline solution:

MnO42- + 2H2O + 3e- = MnO2 + 4OH-

Manganese dioxide is a brown solid.

Name of experiment: Determination of the strength of supplied sodium thiosulfate solution

iodometrically by a standard solution of potassium dichromate

Why sodium thiosulfate is a secondary standard substance?

Sodium thiosulfate pentahydrate (Na2S2O3.5H2O) is an efflorescent substance, which can lose its hydrated water
with respect to change in relative humidity in air. Thus it is a secondary standard substance.

Chemicals Apparatus
Sodium thiosulfate(Na2S2O3.5H2O) Burette with stand and clamp
Potassium dichromate (K2Cr2O7) Pipette
Potassium Iodide (KI) Volumetric Flask (100 mL)
Sulfuric acid Erlenmeyer conical flask (250 ml)
Starch solution Squeezer
Sodium carbonate or chloroform Electronic balance and Dropper

Principle

Thiosulfate ion is a moderately strong reducing agent that has been widely used to determine oxidizing agents by
an indirect procedure that involves iodine as an intermediate.

With iodine, thiosulfate ion is oxidized quantitatively to tetrathionate ion, the half reaction being

2S2O32- ⇄ S4O62- + 2e- (1)

Page 21 of 59
The quantitative aspect of the reaction with iodine is unique. Other oxidants oxidize the tetrathionate ion, wholly
or in part, to sulfate ion. The scheme used for determining oxidizing agents involves adding an unmeasured excess
of potassium iodide to a slightly acidic solution of the analyte. Reduction of the analyte produces an amount of
iodine that is stoichiometrically related to the number of moles of analyte. The liberated iodine is then titrated
with a standard solution of sodium thiosulfate, Na 2S3O3, one of the few reducing agents that is stable toward air-
oxidation. An example of this procedure is the determination of sodium hypochloride in bleaches. The reactions
are:

OCl- +2I- + 2H+ → Cl-+ I2 + H2O (excess) (2)

I2 + 2S2O32- → 2I- + S4O62- (3)

The quantitative conversion of thiosulfate ion to tetrathionate ion shown in the above equation (3), requires a pH
somewhat lower than 7. If strongly acidic solutions must be titrated, air-oxidation of the excess iodide must be
prevented by blanketing the solution with an inert gas, such as carbon dioxide or nitrogen.

More commonly, titrations involving iodine are performed with a suspension of starch as an indicator. The deep
blue colour of starch solutions containing iodine is believed to arise from the absorption of iodine into the helical
chain of β-amylose, a molecular component of most starches.

Starch irreversibly decomposes in solutions containing large concentrations of iodine. Therefore, in titrating
solutions of iodine with sodium thiosulfate, as in the indirect determination of oxidants, addition of the indicator
is delayed until the titration is nearly complete (indicated by a change in color from deep red to faint yellow).
Redox titrations involving iodine are of the following two types: (i) iodometry (ii) iodemetry

The indirect titration of iodine liberated in chemical reaction referred to as iodometry, which involve the reaction
as given below:

2I- ⇄ I2 (s) + 2e- (4)

The above equation refers to a saturated aqueous solution in the presence of solid iodine; this half-cell reaction
will occur, for example, towards the end of a titration of iodine with an oxidizing agent such as potassium
permanganate, when the iodide ion concentration becomes relatively low. Near the beginning or in most
iodometric titration, when an excess of iodide ion is present the tri-iodide ion is formed
I2 (aq) + I- ⇄ I- (5)
Since iodine is readily soluble in a solution of iodide. Therefore the half-cell reaction is better written as
I-3 + 2e- ↔ 3I- (6)
and standard reduction potential is 0.5355V . Iodine or tri-iodide ion is therefore a much weaker oxidizing agent
than potassium permanganate, potassium dichromate, cerium (IV) sulfate etc.

The liberation of iodine can be achieved by the reaction of strong oxidizing agent such as potassium dichromate
in acid medium in the following reaction:

Cr2O72- + 14H+ + 6I- → Cr3+ + 3I2 + 7H2O (7)

Orange Green
The iodine thus liberated oxidizes reducing agents like sodium thiosulfate quantitatively and rapidly by getting
itself reduced in the following way:
2- (8)
3I2 + 6S2O3 6I- + 3S4O62-
Therefore, if a strong oxidizing agent is treated in acid solution with a large excess of iodide ion, the latter react
as a reducing agent and the oxidant will be quantitatively reduced. In such case, an equivalent amount of iodine
is liberated and is then titrated with a standard solution of a reducing agent, which is usually sodium thiosulfate.

Page 22 of 59
If V1 mL of Na2S2O3 solution of concentration S1(N) is required to titrate V2 mL of K2Cr2O7 of concentration
S2(N), the concentration of Na2S2O3 can be calculated by using the equation S1V1 = S2V2.

Procedure
Preparation of 0.1N sodium thiosulfate

Boil about 1L of distilled water for 10 to 15 min. Allow the water to cool to room temperature; then add about 25
g of Na2S2O3.5H2O and 0.1 g of Na2CO3. Stir until the solid dissolves. Transfer the solution to a clean glass or
plastic bottle and store in a dark place.

Preparation of 0.1N-potassium dichromate

For most purposes reagent grade potassium dichromate is sufficiently pure (99.9%) to permit the direct preparation
of standard solutions; the solid is simply dried at 150 to 200 oC before being weighed. Powder finely about 6.0 g
of the A. R. product in a glass or agate mortar, and heat for 30-60 min in an air oven at 140-150ºC. Allow to cool
in a desiccator. Weigh out accurately about 4.9 g of the dry potassium dichromate into a weighing bottle and
transfer the salt quantitatively to a 1-litre volumetric flask, using a small funnel to avoid loss. Dissolve the salt in
the flask in water and make up to the mark and shake well.

Working Procedure

Measure out 10 mL of potassium dichromate solution by pipette in a 250 mL conical flask, acidify the solution
with 1 mL of concentrated H2SO4, add 10 ml of 10% Na2CO3 solution and about 0.5 g of solid KI salt or 10 mL
of 10 % aqueous KI solution in to the conical flask. Cover it with a watch glass and keep in dark for 5 min to
complete the liberation of iodine. After 5 minute, wash the watch glass and the inner surface of conical flask with
distilled water to dissolve iodine if present. Titrate the brown solution of iodine with sodium thiosulfate from
burette until the color changes from brown to faint yellow. Add 1 ml (10 drop) of starch solution and titrate again.
After the addition of 1 to 2 drop of thiosulfate, the deep blue color of starch will disappear at the end point
producing a green color of chromium (III) ion. Add 1 drop of ammonium thiocyanate/potassium thiocyanate
solution, confirm the end point by the non-appearance of deep blue color otherwise continue titration. Repeat the
titrations until a constant end point is observed.

Experimental data: For titration of sodium thiosulfate solution

No. Pipette Burette reading (0.10N Na2S2O3 Average or Conc. of std. Conc. of
of reading solution) in mL mean value solution (N) Na2S2O3 soln.
obs. (mL) Initial Final Difference (mL) (N)
1
2
3
4

Result: The concentration of the supplied sodium thiosulfate solution was found to be of ………N.

Page 23 of 59
Name of experiment: Determination of iron in ore titrimetrically by standardized solution of
potassium permanganate

Principle
The estimation of iron in ore or in water can be measured volumetrically by titration with standard potassium
permanganate solution in acid medium.
The reaction involved in this experiment is:
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 8H2O
Or 10FeSO4 + 2KMnO4 + 8H2SO4 → 5Fe2(SO4)3 + K2SO4 + 2MnSO4 + 8H2O
From the above equation we can write,
1000 ml 5.0 N KMnO4 solution ≡ 5×55.85 g of iron (as Fe2+)
1 ml 1.0 N KMnO4 solution ≡ 5×55.85 = 0.05585 g of iron (as Fe2+)

By knowing the volume of potassium permanganate from burette required for the titration of iron solution, the
composition of iron in the supplied sample can be calculated by the equation:
1 mL 1.0 N KMnO4 solution = 0.05585 g of Fe
Iron in ore or in water may contain both Fe2+ and Fe3+ ions, therefore it is essential to reduce the sample of iron
(Fe3+) in to Fe2+ ions prior to titration.

Discussion

Naturally iron exists as ore. The common ores of iron are hematite (Fe2O3), magnetite (Fe3O4), limonite
(2Fe2O3.3H2O) and spathic iron ore (FeCO3). Steps in the analysis of these ores are (1) dissolution of the sample
or sample preparation, (2) reduction of the sample to the ferrous state, i.e., pre-reduction of iron (III), and (3)
titration of iron (II) with a standard oxidant.

An insight into the pre-reduction of iron

Tin (II) chloride is the most satisfactory reductant for iron (III)
2Fe3+ + Sn2+ → 2Fe2+ + Sn4+ (2)
(The only other common species reduced by this reagent are the high oxidation states of arsenic, copper, mercury,
molybdenum, tungsten and vanadium).
The excess reducing agent is eliminated by the addition of mercury (II) chloride:
(3)
Sn2+ + 2HgCl2 → Hg2Cl2 (s) + Sn4+ + 2Cl-

The slightly soluble mercury (I) chloride does not reduce permanganate, nor does the excess mercury (II) chloride
deoxidizes iron (II). Care must be taken to prevent the occurrence of the alternative reaction:
(4)
Sn2+ + 2HgCl2 → Hg(l) + Sn4+ + 2Cl-

Because, elementary mercury reacts with permanganate and causes the results of analysis to be high. The
formation of mercury which is favored by an appreciable excess of tin (II), is prevented by careful control of this
excess and by the rapid addition of excess mercury (II) chloride. A proper reduction is indicated by the appearance
of a small amount of a silky white precipitate after the addition of mercury (II). Formation of a gray precipitate at
this juncture indicates the presence of metallic mercury; the total absence of a precipitate indicates that an
insufficient amount of tin (II) chloride was used. In either event, the sample must be discarded.

Discussions on the titration of iron (II)

The reaction of iron (II) with permanganate is smooth and rapid. The presence of iron (II) in the reaction mixture
however induces oxidation of chloride ion by permanganate, a reaction that does not ordinarily proceed rapidly
enough to cause serious error. High results are obtained if this parasitic reaction is not controlled. Its effects can

Page 24 of 59
be eliminated through removal of the hydrochloric acid by evaporation or by introduction of Zimmermann-
Reinhardt reagent, which contain manganese (II) ions in a fairly concentrated mixture of sulfuric acid and
phosphoric acid.

The oxidation of chloride ion during a titration is believed to involve a direct reaction between this species and
the manganese (III) ions that form as an intermediate in the reduction of permanganate ion by iron (II). The
presence of manganese (II) in the Zimmermann-Reinhardt reagent is believed to inhibit the formation of chlorine
by decreasing the potential of manganese (III)/manganese (II) couple. Phosphate ion is believed to exert a similar
effect by forming stable manganese (III) complexes. Moreover, phosphate ions react with iron(III) to form nearly
colorless complexes so that the yellow color of the iron (III)/ chloro-complexes does not interfere with the end
point.

Preparation of reagent solutions

The following solutions suffice for about 100 titrations

Tin (II) chloride (SnCl2), 0.25M: Dissolve 60 g of iron free SnCl2.2H2O in 100 mL of concentrated HCl; warm if
necessary. After the solid has dissolved, dilute to 1L with distilled water and store in a well stoppered bottle. Add
a few pieces of mossy tin to help preserve the solution.

Mercury (II) chloride, 5 % (w/v): Dissolve 50 g of HgCl2 in 1L of DW(distilled water).

Zimmermann-Reinhardt reagent: Dissolve 300 g of MnSO 4.4H2O in 1 L DW. Cautiously add 400 mL
concentrated sulfuric acid and 400 mL 85 % H3PO4, and dilute to 3 L with DW.

Working procedure

Sample Preparation

Weigh out accurately 2.0 g of the finely ground ore and dissolve it in 100 mL of dilute hydrochloric acid in a
conical flask carrying a short funnel in the neck. Warm gently and continue the heating until the residue is free
from colored material. Rinse down the funnel and the neck of the flask with distilled water, cool and filter the
liquid through a hardened quantitative filter paper into a 250 mL volumetric flask. Wash with very dilute
hydrochloric acid and allow the washings to pass into the flask. Remove the funnel and make up to the mark with
continuous shaking.

Reduction of iron and titration

Take 10 mL of iron containing solution by pipette and heat to boiling. Add concentrated SnCl2 solution (0.25 M)
drop wise while hot till the yellow color fades. Add dilute SnCl2 solution drop wise till the last tint of yellow color
vanishes (white or greenish color will be appeared). Cool the solution at room temperature under tap water and
rapidly add 10 mL of 5% HgCl2 solution by cylinder, silky white precipitates will be appeared. Keep the reaction
mixture undisturbed for 2 to 3 minutes. Add 5 mL of (Z-R) reagent by cylinder and tantamount of distilled water.
Titrate the reduced solution with freshly standardized KMnO4 solution. Repeat the titration with two other 10 mL
portions of the solution. Calculate the percentage of iron in the ore.

Calculation

The amount of iron (Fe) present in the given sample can be calculated as follows-

1 mole of MnO4- ≡ 5 moles of Fe

1L 1M MnO4- ≡ 5×55.85 g Fe

1mL 1M MnO4- ≡ 5×0.05585g Fe

Page 25 of 59
p mL 0.02 M MnO4- ≡ 5×0.05585x0.02×p g Fe = z g Fe

Let z g Fe was found to obtain from 10 mL of analyte

Then% of Fe in the given sample (for liquid sample) = z/10 %

(N.B. The strength potassium permanganate should be standardized.)

Zimmermann and Reinhardt’s solution

Mechanism of action

The MnSO4 lowers the reduction potential of the MnO4—Mn (II) couple and thereby makes it weaker oxidizing
agent. Therefore the tendency of permanganate ions to oxidize chloride ion is reduced. It has been stated that the
function of Mn (II) Sulfate is to supply an adequate quantity of Mn (II) ions to react with any local excess MnO4-
.The Mn (III) is probably formed in the reduction of permanganate ion to Mn (II).

The Mn (II) and also the phosphoric acid exert a depression effect upon the potential of the Mn (III)- Mn (II)
couple so that Mn (III ) is reduced by Fe(II) ion rather than by chloride ion. The phosphoric (V) acid combines
with the yellow Fe (III) to form a complex [Fe(HPO4)]+, thus rendering the end point more visible. The phosphoric
acid lowers the reduction potential of Fe (III) - Fe(II) system by complexation and thus tends to increase the
reducing power of Fe(II) ion. Under this conditions MnO4- ion oxidizes Fe (II) ion rapidly and reacts only slowly
with chloride ion.

Name of experiment: Determination of calcium in limestone as CaO

Objective

The main objective of this experiment is to acquire knowledge how to determine the percentage of CaO in natural
minerals like limestone, to be used as raw material for industrial production of cement or lime.

Principle

Calcium in limestone or in other sample can be determined volumetrically by converting the sample into soluble
ion by an acid and then precipitating the calcium ion as calcium oxalate precipitate under controlled pH with the
addition of ammonium oxalate. After purification, the calcium oxalate precipitate is decomposed in dilute sulfuric
acid. The liberated oxalic acid is then titrated with freshly standardized 0.02M potassium permanganate solution.
From the volume of burette reading, the amount of calcium ion is determined by the equation given below: 1 mL
0.02 M KMnO4 ≡0.002 g Ca

Discussion

In common with a number of other cations, calcium is conveniently determined by precipitation with oxalate ion.
The solid calcium oxalate is filtered, washed free of excess precipitating reagent and dissolved in dilute acid. The
oxalic acid liberated in this step is then titrated with standard permanganate or other oxidizing reagent. This
method is applicable to samples that contain magnesium and the alkali metals, but most other cations must be
absent since they either precipitate or co precipitate as oxalates and cause positive errors in the titration.

The composition of limestone

Limestones are composed principally of calcium carbonate: dolomite limestones contain large amounts of
magnesium carbonate as well. Calcium and magnesium silicates occur in smaller amounts, along with the
carbonates and silicates of iron, aluminum, manganese, titanium, sodium and other metals. Hydrochloric acid is

Page 26 of 59
the most effective solvent for most limestones. Only silica which does not interfere with the analysis, remaining
un-dissolved. Iron and aluminum, in amounts equivalent to that of calcium do not interfere. Small amounts of
manganese and titanium can also be tolerated with the process described below.

Working Procedure

Sample preparation

Dry the unknown sample for 1 to 2 hr at 110ºC, and cool in a desiccator. If the material is readily decomposed in
acid, weigh 0.25 to 0.30 g samples (0.15 – 0.2 g of calcium carbonate) into 250 mL beakers. Add 10 mL of water
to each sample and cover with a watch glass. Add 10 mL of concentrated HCl drop-wise, taking care to avoid
losses due to spattering as the acid is introduced.

If the limestone is not completely decomposed by acid, weigh the sample in a small porcelain crucible and ignite.
Raise the temperature slowly to 800ºC to 900ºC and maintain this temperature for about 30 min. After cooling,
place the crucible and its contents in a 250 mL beaker and add 5 mL of water and cover with a watch glass.
Introduce 10 mL of concentrated HCl drop-wise, and then heat to boiling. Remove the crucible with a stirring rod
and rinse it thoroughly with water, combine the washings with the solution containing the sample.

Precipitation of calcium oxalate

Add 5 drops of saturated bromine water to oxidize any iron in the sample and boil gently in a hood for 5 min to
remove the excess bromine. Dilute the sample solution to about 50 mL, heat to boiling, and add 100 mL of hot
6% (w/v) ammonium oxalate solution. Add 3 to 4 drops of methyl red, and precipitate calcium oxalate by slowly
adding 6M ammonia solution. When the indicator just begins to change colour, add the ammonia at a rate of one
drop every 3 to 4 second. Continue until the solution turn to the intermediate yellow-orange colour of the indicator
(pH 4.5 to 5.5). Allow the solutions to stand for no more than 30 min ** and filter; medium porosity filtering
crucibles of Gooch crucibles with glass mats are satisfactory. Wash the precipitates with several 10 mL portions of
cold water. Rinse the crucibles to remove residual ammonium oxalate and return them to the beakers in which the
calcium oxalate was formed.

Titration

Add 100 mL of water and 50 mL of 3M sulfuric acid to the beaker containing the precipitated calcium oxalate
and the crucible. Heat to 80 to 90ºC and titrate with 0.02M potassium permanganate solution. The temperature
should be above 60ºC throughout the titration, reheat if necessary. At the end point of titration, the solution
becomes pink in color.

Report the percentage of CaO in the unknown.

Reactions involving in this process

5CaCO3 + 10HCl = 5(Ca2++2Cl-) + 5CO2 + 5H2O ------------------------------------------------(1)

5(Ca2++2Cl-) + 5(NH4)2C2O4 = 5CaC2O4 (yellow ppt.) + 10NH4Cl +excess (NH4)2C2O4 ----(2)

5CaC2O4 (yellow ppt.) + 5H2SO4 = CaSO4 (ppt.) + 5H2C2O4-------------------------------------(3)

2KMnO4 + 3H2SO4 + 5H2C2O4= 2MnSO4 + K2SO4 + 10 CO2+8H2O -------------------------(4)

From the reactions, the % of Ca as CaO can be calculated as follows-

2 mole KMnO4 ≡ 5 mole H2C2O4 ≡ 5 mole of Ca

1 mole KMnO4 ≡ 5/2 mole Ca

Page 27 of 59
1 mole KMnO4 ≡ 100 g Ca

1 L 1 M KMnO4 ≡ 100 g Ca

1000 mL 1 M KMnO4 ≡ 100 g Ca

1 mL 1 M KMnO4 ≡ 0.1 g Ca

1 mL 0.02 M KMnO4 ≡ 0.002 g Ca

p mL 0.02 M KMnO4 ≡ (0.002×p) g Ca

Again

1 mole of Ca = 1 mole of CaO

40 g of Ca = 56 g of CaO

(0.002×p) g Ca = (0.002×p) × (56/40) g CaO.

Weight of the sample (CaCO3) = 0.25 g

[(0.002 × p) × (56/40)]
% of CaO in the sample = × 100
0.25

Precautions

(1) The calcium oxalate precipitate formed in a neutral or ammoniacal solution is likely to be contaminated with
calcium hydroxide or a basic calcium oxalate, either of which leads to low results. The formation of these
compounds is prevented by adding the oxalate to an acidic solution of the sample and slowly forming the
precipitate by the drop wise addition of ammonia. The coarsely crystalline calcium oxalate that is produced under
these conditions is readily filtered. Losses resulting from the solubility of calcium oxalate are negligible above
pH 4, provided washing is limited to freeing the precipitate of excess oxalate.

(2) Co-precipitation of sodium oxalate becomes a source of positive error in the determination of calcium
whenever the concentration of sodium in the sample exceeds that of calcium. The error from this source is
eliminated by re-precipitation.

(3) Magnesium if present in high concentration, may precipitate as the oxalate and contaminate the analytical
precipitate. An excess of oxalate ion helps prevent this interference through the formation of soluble oxalate
complexes of magnesium. Prompt filtration of the calcium oxalate can also help prevent interference because of
the pronounced tendency of magnesium oxalate to form supersaturated solutions from which precipitate formation
occurs only after an hour or more.
**
The period of standing can be longer if the analyte contains no Mg 2+.

Name of experiment: Determination of copper in crystalline copper sulfate

Page 28 of 59
Objectives of this experiment

For practice in this estimation, the students may determine the percentage of copper in A. R. copper sulfate
(CuSO4.5H2O).

Principle

The amount of copper (II) in a sample can be determined in presence of iodide solution. The copper (II) ion
oxidizes the iodide ion to liberate iodine. The iodine is then titrated with a standard 0.10M sodium thiosulfate
solution.
The reactions involved are:

2CuSO4 +4KI = Cu2I2 + I2 +2K2SO4 (i)

-
2Na2S2O3 +I2 = 2Na2S4O6 +2I (ii)
The iodine liberated in the above reaction (i) is volatile and tend to escape into the atmosphere, because molecular
iodine is less soluble in water. This results in measurement error. To avoid the loss of iodine, some excess of
potassium iodide is to be added (generally 4% by weight, in order to force the reaction to completion). The excess
iodide ion reacts with the liberated iodine and produce non-volatile and more water soluble tri-iodide ion. From
the burette reading, the amount of copper can be calculated by the equation given below

1mL 0.1 M S2O32- = 0.006354 g of Cu

Preparation of reagents

(1) Preparation of 0.10 M sodium thiosulfate: Boil about 1 L of distilled water for 10 to 15 min. Allow the
water to cool to room temperature; then add about 25 g of sodium thiosulfate pentahydrate and 0.10 g of
sodium carbonate. Stir until the solid has dissolved. Transfer the solution to a clean glass or plastic bottle
and store in dark place.
(2) Preparation of starch solution: Rub 1 g of soluble starch and 15 mL of water into a paste. Dilute to about
500 mL with boiling water, and heat until the mixture is clear. Cool and store in a tightly stoppered bottle.
For most titrations 3 to 5 mL of indicator is used (sufficient for about 100 titrations).

Procedure

Weigh out accurately about 3.0 g of the salt, dissolve it in water and make up to 250 mL in a volumetric flask and
Shake well. Pipette 50 mL of this solution into a 250 mL conical flask, add a few drops of dilute sodium carbonate
solution (10%, w/v) until a faint permanent precipitate remains. Dissolve the precipitate by means of one or two
drops of acetic acid. Then add 0.5 g of potassium iodide (or 10 mL of 10% solution, w/v) cover the vessel with a
watch glass and keep in dark for about 5 min. Wash the watch glass and the inner side of the vessel with distilled
water and titrate the liberated iodine with freshly standardized 0.10M sodium thiosulfate solution. When the color
of iodine becomes fade-yellow (straw color), add 2 mL of starch solution, and continue the addition of thiosulfate
until the blue color commences to fade. Then add about 1 g of potassium thiocyanate or ammonium thiocyanate,
preferably as a 10% aqueous solution: the blue color will instantly become more intense. Complete the titration
as quickly as possible. The end point is detected by the appearance a colorless solution or a white precipitate of
cuprous iodide. Repeat the titration with two other 50 mL portions of the copper sulfate solution. Record the mL
of thiosulfate solution required to react with the analyte completely from burette reading. Repeat the titration two
or more times to confirm the burette reading. Calculate the percentage of copper in the supplied sample.

Calculation

The percentage of copper in the supplied sample is calculated using equation (i) & (ii) as

Page 29 of 59
2CuSO4 = I2 = 2Na2S2O3.

From the above equation we have,

1L 1M S2O32- = 1mole of Cu

1L 1M S2O32- = 63.54 g of Cu

1mL 0.1 M S2O32- = 0.006354 g of Cu

p mL 0.1M S2O32- = (0.006354×p) g of

(0.006354×p)
% of Cu = X 100
volume of titrant

Where, p represents the volume of sodium thiosulfate solution in mL.

Precautions

(1) For accurate result, the solution should have a pH of 4.0 -5.5, preferably < 4.0 to prevent the formation of
basic copper species that reacts slowly and incompletely with iodide ion. This should be achieved by the
successive addition of sodium carbonate and acetic acid solutions.
(2). Parallax error must be avoided during the time of measuring the burette reading.

(3) The titration of iodine by thiosulfate tends to yield slightly low results, owing to the adsorption of small but
measurable quantities of iodine upon solid CuI. The adsorbed iodine is released only slowly, even when thiosulfate
is present in excess; transient and premature end point results. This difficulty is largely overcome by the addition
of thiocyanate ion. The sparingly soluble copper (I) thiocyanate replaces part of the copper iodide at the surface
of the solid.

CuI (s) + SCN- → CuSCN (s) + I-

Accompanying this reaction is the release of the adsorbed iodine, which thus becomes available for titration. The
addition of thiocyanate must be delayed until most of the iodine has been titrated to prevent interference from a
slow reaction between the two species, possibly

2SCN- + I2 → 2I- (SCN)2

Thus, potassium thiocyanate is usually added just before the end point is reached to displace the adsorbed iodine.
Note that the net stoichiometry of the react is 1:1 since 2 moles of copper requires 2 moles of thiosulfate.

Starch / iodine solutions (mechanism of color change)

Starch which forms a blue complex with tri-iodide ion, is a widely used specific indicator in redox reactions
involving iodine as an oxidant or iodide ion as a reductant. A starch solution containing a little tri-iodide or iodide
ion can also function as a true redox indicator. In the presence of excess oxidizing agent, the concentration ratio
of iodine to iodide is high, giving a blue color to the solution. With excess reducing agent, on the other hand,
iodide ion predominates and the blue color is absent. Thus the indicator system changes from colorless to blue in
the titration of many reducing agents with various oxidizing agents. The color change is quite independent upon
the potential of the system at the equivalence point

Name of experiment: Determination of chloride ion (Cl-) gravimetrically in a soluble sample

Principle

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 The chloride content of a soluble salt can be determined by precipitation of the anion as silver chloride
Ag+ + Cl- → AgCl (s)

The precipitate is collected in a weighed filtering crucible and washed; its weight is determined after it has been
dried to constant weight at 110ºC. The solution containing the sample is kept somewhat acidic during the
precipitation to eliminate possible interference from anions of weak acids (e. g. CO32-) that form sparingly soluble
silver salts in a neutral environment. A moderate excess of silver ion is needed to diminish the solubility of silver
chloride, but an excess is avoided to minimize co-precipitation of silver nitrate.

Silver chloride forms first as a colloid and is subsequently coagulated with heat. Nitric acid and the small excess
of silver nitrate promote coagulation by providing a moderately high electrolyte concentration. Nitric acid in the
wash solution maintains the electrolyte concentration and eliminates the possibility of peptization during the
washing step; the acid subsequently decomposes to give volatile products when the precipitate is dried.

In common with other silver halides, finely divided silver chloride undergoes photodecomposition:

2 AgCl (S) → 2 Ag (s) + Cl2 (g)

The elemental silver produced in this reaction is responsible for the violet colour that develops in the precipitate.
In principle, this reaction leads to low results for chloride ion. In practice, however, its effect is negligible provided
direct and prolonged exposure to sunlight is avoided.

If photodecomposition of silver chloride occurs before filtration, the additional reaction tends to cause high results.
3 Cl2 (aq) + 3H2O + 5Ag+ → 5 AgCl (s) + ClO3- + 6H+

Some photodecomposition of silver chloride is inevitable as the analysis is ordinarily performed. It is worthwhile
to minimize exposure of the solid to intense sources of light as far as possible.

Iodide, bromide and thiocyanate, if present, precipitate along with silver chloride and cause high results.
Additional interference can be expected from tin and antimony, which are likely to precipitate as oxy-chlorides
under the conditions of the analysis.

Reagents

1. Pure solid NaCl 3. 6M NH3 solution 5.0.2M AgNO3 solution

2.Concentrated HNO3 4. 6 M HNO3 solution

Procedure

Preparation of crucible

Clean three sintered-glass or porcelain filtering crucibles by allowing about 5 mL of concentrated HNO 3 to stand
in each for about 5 min. Use a vacuum to draw the acid through the crucible. Rinse each crucible with three
portions of tap water, and then discontinue the vacuum. Next, add about 5 mL of 6M NH3 and wait for about 5
min before drawing it through the filter. Finally, rinse each crucible with six to eight portions of distilled or
deionized water. Provide each crucible with an identifying mark. Bring the crucibles to constant weight by heating
at 110ºC while the other steps in the analysis are being carried out. The first drying should be for at least 1 hr;
subsequent heating periods can be somewhat shorter (30 to 40 min)

Transfer the unknown to a weighing bottle and dry it at 110ºC for 1 to 2 hr; allow the bottle and contents to cool
to room temperature in a desiccator. Weigh individual samples by difference into 400-mL beakers. Dissolve each
sample in about 100 mL of distilled water to which 2 to 3 mL of 6 M HNO 3 has been added.

Slowly and with good stirring add 0.20M AgNO3 to each of the cold sample solutions until AgCl is observed to
coagulate; then introduce an additional 3 to 5 mL. Heat almost to boiling and digest the solids for about 10 min.

Page 31 of 59
Add a few drops of AgNO3 to confirm that precipitation is completed. If additional precipitate forms, add about
3 mL of AgNO3 into a waste container. Cover each beaker and store in a dark place for at least 2 hr and preferably
until the next laboratory period.

Decant the supernatant liquids through weighed filtering crucibles. Wash the precipitates several times with a
wash solution consisting of 2 to 5 mL of 6 M HNO3 per liter of distilled water and decant these washings through
the filters. Quantitatively transfer the AgCl from the beakers to the individual crucibles with fine streams of wash
solution; use rubber policemen to dislodge any particles that adhere to the walls of the beakers. Continue washing
until the filtrates are essentially free of Ag+ ion.

Dry the precipitate at 110ºC for at least 1 hr. Store the crucibles in a desiccator while they cool. Determine the
weight of the crucibles and their contents. Repeat the cycle of heating, cooling and weighing until consecutive
weights agree to within 0.20 mg. Calculate the percentage of Cl- in the sample.

Washing of the crucibles

Upon completion of the analysis, remove the precipitates by gently tapping the crucibles over a piece of glazed
paper. Transfer the collected AgCl to a container for silver wastes. Remove the last traces of AgCl by filling the
crucibles with 6M NH3 and allowing them to stand.

Weight of AgCl Precipitate W = W2 – W1

Where,
W1 = Weight of filter paper before filtration
W2 = Weight of filter paper after filtration of AgCl solution

Molecular weight of AgCl = 108 + 35.5 = 143.5

143.5 g AgCl contains 35.5 g of Cl
𝑊 ×35.5
W g AgCl contains = X (say)
143.5

𝑋
% Cl- ion in supplied sample = × 100 %
𝑦

Where, y = Weight of sample

Notes

1. Consult with the instructor concerning an appropriate sample size.

2. Determine the approximate amount of AgNO3 needed by calculating the volume that would be required if the
unknown were pure NaCl.
3. Use a separate stirring rod for each sample and leave it in its beaker throughout the determination.
4. To test the washings for Ag+ ion, collect a small volume in a test tube and add a few drops of HCl. Washing is
just complete when little or no turbidity develops.

================================

Page 32 of 59
 Chapter-III:
Organic Laboratory Experiments

Systematic analysis and identification of unknown organic compound

Preliminary examination

a. Physical state : (i) Solid (ii) Crystalline or amorphous

b. Color : .............................
c. Odor : .............................

Page 33 of 59
Solubility test
At the molecular level, solubility is controlled by the energy balance of intermolecular forces between solute-
solute, solvent-solvent and solute-solvent molecules. Intermolecular forces come in different strengths ranging
from very weak induced dipole–induced dipole interactions to much stronger dipole-dipole forces (including the
important special case, hydrogen bonding). However there is a simple, very useful and practical empirical rule
that is quite reliable, that simple rule is “like dissolves like” and it is based on the polarity of the systems i.e. polar
molecules dissolve in polar solvents (e.g. water, alcohols) and non-polar molecules in non-polar solvents (e.g. the
hydrocarbon hexane). This is why ionic compounds like table salt (sodium chloride) or compounds like sugar
dissolve in water but do not dissolve to any great extent in most organic solvents. The polarity of organic
molecules is determined by the presence of polar bonds due to electronegative atoms (e.g. N, O etc.) in polar
functional groups such as amines (-NH2) and alcohols (-OH). Since the polarity of an organic molecule is related
to the presence of polar bonds that are found within functional groups, the solubility characteristics of an organic
compound can provide experimental evidence for the presence (or absence) of several important organic
functional groups.

In this experiment, solubility of organic compounds will be tested in different solvents such as H 2O, NaOH,
NaHCO3 and HCl. The solubility of the organic compounds in these solvents may provide a general idea of the
functional group as well as general characteristics of the sample. Approximately 6 drops or 6mg (if solid) of a
compound 1 were used and 6mL of distilled water were added in the test tube. The mixture was obs erved
if the compound 1 will dissolve in H 2O and if it is soluble, the compound 1 determined belonging to Group
A (see table 1).

If compound 1 is insoluble in H 2O, a new sample was obtained and tested to 6mL of 5% NaOH in
a new test tube. Determine further the solubility of compound 1 to 6mL 5% NaHCO3, if the compound 1 dissolved
both in NaOH and NaHCO3, the compound was determined belonging to Group B1. If compound 1 is soluble in
NaOH and insoluble in NaHCO3, the compound was determined belonging to Group B2. If insoluble in 5% NaOH,
new sample of compound 1 was obtained and tested to 6ml 5% HCl. If soluble in HCl, the compound determined
belonging to Group C and if ins oluble, the compound was determined belonging to Group D. Same
procedure was done to the other compounds 2, 3, 4 & 5. The five compounds were then classified from the
characteristics given in each group.

Table 1: Classification of organic compounds

Classification General Characteristics

A May be alcohols, ketones, amines, carboxylic acids
with < 5 carbon atoms
B1 May be carboxylic acids with more > 5 carbon atoms.
Phenols with electron withdrawing groups.
B2 Phenols
C Amines
D Hydrocarbons, alkyl halides, alcohols, aldehydes,
ketones with greater than 5 carbon atoms.
Results and discussion
Table 2: Solubility test of a given unknown sample
Compound Observation Classification
H2O 5% NaOH 5% NaHCO3 HCl
1 Insoluble Insoluble - Insoluble D

Page 34 of 59
 2 Insoluble Soluble Insoluble - B2
3 Soluble - - - A
4 Insoluble Soluble Soluble - B1
5 Insoluble Insoluble - Soluble C

Five compounds were tested in different solvents such as H2O, NaOH, NaHCO3 and HCl. The compounds were
determined each of their classification and characteristics.

In water solubility, a soluble organic compound will form a homogeneous solution with water, while an insoluble
organic compound will remain as a separate phase. In 5% NaOH solubility, it will be indicated by the formation
of a homogeneous solution, a color change, or the evolution of gas or heat. If s oluble, then your organic
compound is beha ving as an organic a cid. The most common organic a cids are carboxylic a cids
and phenols. While in 5% NaHCO 3 solubility, if a compound is soluble then it is behaving as a strong organic
acid. If not, then it is a weak organic acid. The most common weak organic acid is phenol. Typically, only a
carboxylic acid will react with NaHCO3. The solubility in 5% HCl will determine an organic base. Amines are
the most common organic base.

If the compound would be ins oluble in all solutions is a large (>5-6 carbon atoms) neutral
compound.

The compound 1 was insoluble to water, 5% NaOH and HCl which indicated that compound 1 was a non-polar
compound because all the solvents used in the experiment were polar. Compound 2 was insoluble in water and
soluble in 5% NaOH, but it was insoluble in 5% NaHCO 3 that indicated that the compound was weak organic
acid belonging to Group B2 and classified as phenol. Compound 3 was soluble to water that indicated the
compound was a polar compound belonging to Group A. The Compound 4 was insoluble in water but soluble in
both NaOH and NaHCO3 that determined the compound was strong acid belonging to Group B and classified as
benzoic acid. Compound 5 was insoluble in water and NaOH but soluble in HCl. The compound was determined
as an organic base compound classified as diphenylamine belonging to Group C.

Result of solubility test

Solvent Water 5% NaHCO3 5% NaOH 5% HCl CHCl3 Class of compound

Solubility

Physical constant: Melting point of the supplied sample was found ………… oC.

Elementary analysis

Preparation of stock solution: Place a small piece of clean and dry Na in a fusion tube with the help of a spatula.
Heat the lower part of the tube gently until the Na melts. Add a little amount of the sample directly to the molten
Na. Heat the tube carefully first then strongly until the entire end of the tube is red hot and maintain it at this
temperature for 1-2 minutes. Then dip the heated fusion tube into water in a mortar. Crush the whole mixture with
a pestle. Filter the mixture. The filtrate obtained is known as stock solution (SS) and subjected to the detection of
N, S and X (halogens).

Reactions
C + N (in organic compound) + Na → NaCN
S (in organic compound) + 2Na → Na2S
X (in organic compound) + Na → NaX
C + N + S (in organic compound) + Na → NaCNS
Na (excess/unreacted in fusion) + H2O → NaOH

Page 35 of 59
Test for elements

Sl. Experiment Observation Inference

1. Test for nitrogen: Take 2-3mL of stock A deep (Prussian) blue color or Nitrogen is
solution in a test tube and add 2-3 mL freshly precipitate present
prepared FeSO4 solution. Heat the solution to
boil. After cooling add 2-3 drops of conc.
H2SO4.
2 Test for sulfur: Acidify 2-3mL of stock A black precipitate of lead sulfide Sulfur is present
solution in a test tube with acetic acid and add
2-3 drops of lead acetate solution to it.
3 Test for nitrogen and sulfur (if present A blood red coloration Both nitrogen and
together): Acidify 2-3mL of stock solution in Sulfur are present.
a test tube with dilute HCl and add 1-2 drops
of FeCl3 solution to it.
4 Test for halogens: Boil 2-3 mL of stock a. A white curdy ppt. easily Chlorine is
solution with dilute HNO3 and add 2-3 drops soluble in NH4OH solution and present.
of AgNO3 solution to it. insoluble in dilute HNO3.

b. Light yellow ppt. difficulty Bromine is

soluble in NH4OH solution and present.
insoluble in dilute HNO3.
c. Yellow ppt. insoluble in both
NH4OH solution and dilute HNO3. Iodine is present.

Detection of functional groups

Sl. Experiment Observation Inference

Test for unsaturation (Bromine solution test) The red color of the
bromine solution is
Dissolve small amount of sample in 2 mL CCl4. Add 1-2 discharged.
drops of 2% bromine solution in CCl4 and shake well. Unsaturation
1 Test for unsaturation (Bayer test): present.
Dissolve small amount of sample in 2 mL water or The violet color of
acetone. Add 1-2 drops of 2% KMnO4 solution and shake KMnO4 solution is
well. discharged.
The sample is
Test for carboxylic acid group and phenolic group
The blue litmus turns to acidic (phenol or
a. Litmus test: Add blue litmus to the aqueous solution of red. acid).
the sample.
2 b. NaHCO3 test: Add a small sample in slightly warm CO2 gas is evolved Carboxylic acid
aqueous solution of NaHCO3. which turns quick lime group is present.
c. FeCl3 solution test: Add 1-2 drops of FeCl3 solution to muddy.
an aqueous solution of the sample. Violet, blue or green Phenol group is
coloration. present.

Page 36 of 59
 Test for carbonyl (>C=O) group Orange red or yellow Carbonyl group
3 ppt. is formed. (=CO, aldehyde or
Add 2-3 drops of sample solution (in alcohol) to 2-3 mL
ketone) is present.
of 2, 4-dinitrophenyl hydrazine solution and shake well.
Test for alcohol (-OH) group: Opaque green-blue Alcohol is present.
4 coloration.
Dissolve the sample in acetone and add a few drops of
chromic acid. Then shake well.
Tests for nitrogen containing groups Very bad smell carbyl Primary amine
Test for primary amine (carbyl amine test) amine is produced. (aliphatic or
aromatic) is
Dissolve a small amount of sample in 2-3 mL alcoholic
present.
NaOH solution and add 4-5 drops of chloroform. Then
A red or orange dye is
5 heat it.
produced. Primary aromatic
Test for primary amine (nitrous acid test)
amine is present.
Dissolve a small amount of sample in 2-3 mL dilute HCl
acid and cool it and add 1 mL NaNO2 solution. Then add
a few drops of alkaline ᵦ-naphthol solution.
Test for simple amide and imide Characteristic smell of Simple amide and
NH3 which turns red imide is present.
Boil a small amount of sample with 10-20% NaOH
litmus blue, forms white
solution to hydrolyze.
smoke with HCl and
turns a paper wetted
6 Differentiation between amide and imide
with HgNO3 solution
Shake a small amount of sample with (saturated) alcoholic black. Imide is present.
KOH solution.
Insoluble white
crystalline ppt. of K-
salt.

Test for substituted amide Orange red coloration Mono-substituted

Boil a small amount of sample with 10-20% NaOH on the filter paper. amide is present.
solution and absorb the liberated gas with a filter paper
socked with dilute HCl and 10% NaNO3 solution. Add one
7 drop of alkaline ᵦ-napthol solution to the filter paper.
Boil a small amount of sample with dilute HCl for 5-7 Mono-substituted
minutes and cool it. Add more HCl and 2-3mL cold 10% Orange red color dye is amide is present.
NaNO3 solution. Add 2-3 drops of the resulting solution to produced.
2-3mL alkaline ᵦ-napthol solution.

Test for nitro (-NO2) group (when 1o amine is absent) Boil Orange red color dye is Nitro group
a small amount of sample with conc. HCl in presence of produced. (compound) is
Sn (tin) for about 5 minutes. Filter the solution and cool. present.
8 Add dilute HCl and 10% NaNO2 solution to the solution.
Add 2-3 drops of the resulting solution to 2-3mL alkaline
ᵦ-napthol solution.

Page 37 of 59
 Test for hydrocarbon Red colored needle- Aromatic
shaped crystalline ppt. is hydrocarbon is
Mix 2-3mL of saturated solution of the sample in
produced. present.
9 chloroform or absolute alcohol with 2-3mL of saturated
solution of the picric acid in chloroform or absolute
alcohol and gently heat it. After heating keep the solution
standing.

Conclusion

From the elementary and functional group analysis, it was found that the sample contains/does not contain the
elements nitrogen, sulfur, chlorine and bromine and functional groups amine, nitro, phenolic and/or carboxylic
acid group. The melting point of the sample was found ……….. oC. So from the supplied list of samples we can
say that the name of the sample is ……………… and the structure is ………………….. .

=================================

Page 38 of 59
 Chapter-IV

Physical Chemistry Experiments

Name of experiment: Determination of pH of given solution.

Introduction

Page 39 of 59
 pH means a measurement of hydrogen ion concentration or activity that is used to express the intensity or alkaline
condition. It is also an important factor in water analysis. Since it enters into the calculation of acidity, alkalinity
and processes like coagulation, disinfection and corrosion control. The pH of a sample can be determined
electrometrically or calorimetrically.

In many areas of chemistry it is very convenient to correlate the properties of the system with something related
to the hydrogen ion concentration. Thus, in a titration of an acid with base, one might try to follow the process
and determine the end point by any of a number of physical measurements. Properties that are closely dependent
on the hydrogen ion concentration would be most satisfactory. In a like manner, since some reactions, as was
discussed in chap. 16 are acid catalyzed; the reaction rate of such reactions can be correlated with the concentration
of the hydrogen ion.

Such applications are not strictly thermodynamic, and in these applications it is not clearly specified whether it is
hydrogen ion concentration that is needed or whether it is some effective hydrogen ion concentration. There seems
therefore little necessity to try to use the thermodynamically suggested activities or activity coefficients. The fact
that the activity of a single ion would be encountered emphasizes the impropriety of inserting this thermodynamic
concept.

A convenient form for the expression of hydrogen ion concentration was suggested in 1909 by Sorensen. He
introduced the term pH, and his original definition gave

pH = -log [H+] (1)

Hydrogen ion concentrations, as was shown in section 22.10, can be deduced for dilute solutions of acids from
conductance measurements, and with such data the pH , according to eq. 1 , can be obtained.

Most applications however, require a measure of something like the hydrogen ion concentration in solutions that
may be concentrated and that may contain a number of other ionic species. Conductance measurements are
therefore unsatisfactory, and one is led to consider some electrochemical cell whose emf might give a suitable
hydrogen ion index.

One might consider for example the cell

Pt‫׀‬H2 (1 atm)‫׀‬soln ‫ ׀׀‬Hg2Cl2 (satd)‫׀‬Hg2Cl2(s)‫׀‬Hg

in which the hydrogen electrode operates in the solution of interest and the cell is completed by a calomel electrode
connected through a salt bridge. The electrode reactions are:

Right electrode: 1/2Hg2Cl2 (s) + e- ↔ Hg + Cl- (satd)

Left electrode: 1
/2H2 ↔ H+ + e-

Overall reaction: 1/2H2 + 1/2Hg2Cl2 (s) ↔ H+ + Cl- (std) + Hg (2)

If the salt bridge is assumed to be effective and the chloride concentration and activity are fixed and included in a
constant e.m.f. term, one can write

ε = constant – (0.05915/1)log aH+ (3)

The measured e.m.f. , after the cell has been standardized by measurements on, for example, a 1-MHCl solution,
gives an identification of the hydrogen ion concentration or activity, the later being, as pointed out , not well
defined. Such a cell does give the information that would be needed, for example, to follow an acid base titration
or to correlate the rate of an acid catalyzed reaction and inconvenience of the hydrogen electrode, however, make
the hydrogen-calomel electrode unsuitable

Constitution of pH meter

Page 40 of 59
By far the most frequently used electrochemical device is the pH meter, which makes use of the combination of a
glass electrode and a calomel electrode. The emf of such assembly is found to depend on the acidity of a solution
in much the same way as the hydrogen calomel electrode. Thus one formally write for the pH meter the equation

ε = constant –0.05915 log aH+

or, – log aH+ = (ε – constant)/ 0.05915 (4)

The value of the constant term can be determined from a measurement on a solution of known hydrogen ion
concentration. The measured ε of a pH meter can then be inserted to give a numerical value for the right side of
the equation when some tested solution is used. The scale of pH meter can be arranged. Moreover to give directly
the right side of eq 1 rather than the value of ε Equation 1 suggest that this number will be a suitable hydrogen ion
index. It is convenient, therefore to drop the original Sorensen pH definition and instead to define pH as

pH = (ε – constant)/ 0.05915 (5)

where ε is the e.m.f. of the pH meter assembly.

Electrometric method for the determination of pH

Principle

This method involves the measurement of electromotive force (e.m.f.) of a solution of interest by a pH meter. The
pH meter consists of a cell comprising an indicator electrode (glass electrode) responsive to hydrogen ions and a
reference electrode (calomel electrode). The glass electrode generates a potential varying linearly with the pH of
solution in which it is immersed. It is a Nernstian concentration cell with potential controlled by the activities of
H+ on either side of a very thin glass membrane. The later is the bottom part of a bulb at the end of a glass tube
contained a reference solution of fixed a H+. The calomel electrode is usually located around the glass electrode
stem for sample operation.

The emf measured by pH meter is followed by the equation

RT aH+ (sample)
E = constant + ln = constant + 0.05915 pH at 20ºC
nF aH+ (standard)

Different buffer solutions can be prepared as follows

(a) pH 4 buffer solution: Dissolve 1.012 g (0.05 M) anhydrous potassium hydrogen phthalate in distilled water
and make up to 100 mL in volumetric flask at 25ºC.

(b) pH 7 buffer solution: Dissolve 1.361 g (0.10 M) anhydrous potassium hydrogen phosphate (KH2PO4) in
distilled water and make up to 100 mL in volumetric flask at 25ºC and 1.420 g (0.1 M) di-sodium hydrogen
phosphate (Na2HPO4) in distilled water and make up to 100 mL in volumetric flask at 25ºC and finally mix these
two solutions.

(c) pH 9 buffer solution: Dissolve 3.81 g (0.10 M) borax (Na2B4PO7.10 H2O) in distilled water and make up to
100 mL in volumetric flask at 25ºC.

Procedure

(i) Standardize the pH meter using a standard buffer solution of pH near that sample to be tested.
(ii) Rinse the electrode thoroughly with de-ionized distilled water and carefully wipe with a tissue paper.
(iii) Dip the electrode into the sample solution, swirl the solution and wait up to 1 min for steady reading.

Page 41 of 59
(iv) Check the electrode response by measuring the pH of another standard buffer solution having different pH.

Commences

1. Water having pH above 8 contain carbonates, with or without bicarbonate.

2. Water with pH value from 4.5-8.0 contain no carbonate but contain bicarbonate and carbonic acids. Natural
water falls under this category.
3. Water having pH range <4.5 contain carbonic acid but no carbonate and bicarbonates.
4. The desirable pH range for drinking water is 7.0-8.5.
5. pH in conjunction with total salinity, total alkalinity and temperature is used to determine whether a water is
corrosive in nature or having scale forming tendencies.
6. Knowledge of pH is essential in the selection of coagulants for water purification. For example, Al 2(SO4)3 is
effective in pH 6.7 while FeSO4 coagulates well at a high pH

Name of experiment: Determination of heat of neutralization of strong acid with strong base
calorimetrically.
Introduction

Generally the reactions taking place in the chemical sciences are breaking and making of chemical bonds. This is
accompanied by some heat effects. Formation of chemical bonds releases energy in the form of heat and hence
known as an exothermic reaction. The reaction which is accompanied absorption of heat is known as endothermic
reaction. Calorimetry is a scientific term dealing with the changes in energy of the system by measuring the heat
exchanged with the surroundings. In a broader sense it is defined to determine the heat released or absorbed in a
chemical reaction. A calorimeter is a device designed to measure heat of reaction or physical changes and heat
capacity. The device can be sophisticated and expensive or simple and cheap. A calorimeter consists of two
vessels, outer vessel and an inner vessel. The space between these vessels acts as a heat insulator and hence there
is very little heat exchange in between the inner and outer vessels. Thermometer measures the temperature of the
liquid in the inner vessel. The stirrer functions in such a way to stir the liquid to distribute the heat in the entire
vessel. The fibre rings in the calorimeter helps to hold the inner vessel hanging in the center of the outer vessel. It
also has an insulating cover or lid with holes for attaching the stirring rod and thermometer.

Figure: Calorimeter
The heat of neutralization of an acid is defined as the amount of heat evolved when one equivalent of an acid and
one equivalent of a base undergo a neutralization reaction to form water and a salt. Similarly the heat of
neutralization of a base is the amount of heat evolved when 1 g equivalent of the base is completely neutralized
by a strong acid in a dilute solution.

Page 42 of 59
The enthalpy of neutralization is defined as the amount of heat evolved for the complete reaction of one mole of
H+ coming from an acid with one mole of OH- from base. The overall reaction is

H+ + OH- → H2O
HCl + NaOH → NaCl + H2O + 57.3 KJ
+ - +
H + Cl + Na + OH -
→ Na+ + Cl- + H2O + 57.3 KJ
Principle

A known volume (V mL) of HCl solution of exactly known concentration (N normal) is allowed to neutralize
completely with a strong alkali in dilute solution in a calorimeter. The temperature change is then noted. With the
known volume of HCl solution, the heat of neutralization can be calculated.

HCl + NaOH → NaCl + H2O

+ - +
H + Cl + Na + OH -
→ Na+ + Cl- + H2O
Let,
The weight of calorimeter = m1 g
weight of total solution (acid and base solutions) = m2 g
Initial temperature = t1 oC
Final temperature = t2oC
Specific heat capacity of calorimeter (glass) = S1 JKg-1K-1
Specific heat capacity of solution = S2 JKg-1K-1
Temperature difference = (t1 – t2) oC
Amount of heat absorbed by calorimeter H1 = m1S1(t1 – t2) J
Amount of heat absorbed by solution H2 = m2S2(t1 – t2) J
Total heat released by the reaction H = (H1 + H2) J
Heat of neutralization H
∆H = V(litre)×N
J/equivalent
H
= KJ/equivalent
V(ml)×N

Equation
ΔH = (1/VS) (m1S1+ m2S2) (t2 - t1 )

Experimental Procedure
Take the calorimeter and check the cleanliness. Weight the calorimeter. Take 50mL of HCl solution into the
calorimeter and put the thermometer in the solution. Record the constant temperature of the acid solution. Then
add 50 mL of NaOH solution of same concentration as acid solution to it, record the temperature of the solution
at 30 second interval with continuous stirring of the solution. Continue temperature recording until constant.

Time, min 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Temp., oC
Plot a graph with temperature vs. time. The final temperature is obtained from the graph.
Result: The heat of neutralization determined was ………………. kJ/mole.

Name of experiment: Determination of heat of solution of supplied sample in water

calorimetrically
Introduction

Heat of solution is defined as the amount of heat or enthalpy released or absorbed when one mole of a substance
is dissolved in a sufficient amount of a suitable solvent. Here sufficient amount of solvent means the amount of

Page 43 of 59
solvent which is required for the solute to dissolve the total solute completely and also the temperature change of
the solution can be detected.

Solute + Solvent → Solution + ∆H (heat of solution)

Principle

When a substance is dissolved, heat may be either released or absorbed depending on the relative amounts of
energy which is used up in breaking down the crystal lattice on the one hand and the energy liberated during the
hydration of the solute on the other. The quantity of heat evolved is not constant but varies with the concentration
of the final solution.

HCl + 50 H2O = HCl. 50 H2O + x x = Integral heat of solution

HCl + 100 H2O = HCl. 100 H2O + y (y > x) y = Integral heat of solution
HCl + 150 H2O = HCl. 150 H2O + z (z > y) z = heat of solution
HCl + 200 H2O = HCl. 200 H2O + w (w = z) (z-y) and (y-x) heat of dilution

Experimental Procedure

Take the calorimeter and check the cleanliness. Weigh the calorimeter with a glass rod as a stirrer and a
thermometer and record it. Take 50 mL of distilled water in the calorimeter and put the thermometer in the
solution. Record the constant temperature of the water with the help of a thermometer. Then add 0.50 g of solid
KNO3 to it and start recording the temperature of the solution at 10 second interval with continuous stirring of the
solution. Continue temperature recording until constant.

Figure: Determination of heat of neutralization

Data collection table

Time, min 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Temp., oc

Plot a graph with temperature against time. The final temperature is obtained from the graph.

Calculation

The weight of calorimeter = m1 g

weight of total solution = m2 g
Initial temperature = t1 oC
Final temperature = t2oC

Page 44 of 59
 Specific heat capacity of calorimeter (glass) = S1 JKg-1K-1
Specific heat capacity of solution = S2 JKg-1K-1
Temperature difference = (t1 – t2) oC
Amount of heat absorbed by calorimeter H1 = m1S1(t1 – t2) J
Amount of heat absorbed by solution H2 = m2S2(t1 – t2) J
Total heat absorbed/released H = (H1 + H2) J
Heat of solution H
∆H = V(litre)×N
J/mole
H
= KJ/mole
V(ml)×N

Equation
ΔH = (1/VS) (m1S1+ m2S2) (t2 - t1 )

Result: The heat of solution of the supplied salt (KNO3) was determined as ……………

Name of experiment: Determination of the rate constant and justification of the order of a
chemical reaction
Introduction

Rate of reaction is defined as the change in concentration of any reactant or product per unit time.
A (Reactant) → Product(s)
According to the law of mass action, rate of the reaction, Where,
r ∞ [A] [A] is molar concentration of reactant A.
or, r = k. [A] k is a proportionality constant and it is called
rate constant of the reaction/ velocity constant
Order of reaction is defined as the sum of the powers of the concentration terms used in the rate law of the
reaction concerned. Let us consider the examples,

Reaction Rate law Order of reaction

A → Product(s) r = k. [A] 1 first
A+B → Product(s) r = k. [A].[B] 1+1 = 2 second
2A + B → Product(s) 2
r = k. [A] . [B] 2+1 = 3 third
A + 2B → Product(s) r = k. [A]. [B] 2
1+2 = 3 third
aA + bB → Product(s) a
r = k. [A] . [B] b
a+b = n nth

Principle

Consider a second order reaction as follows

A + B → Product(s)
Initially molar conc. of reactants (at time t = 0) a b 0
molar conc. of reactants after time t a-x b-x 2x

Rate of the reaction,

𝑑𝑥
= 𝑘. (𝑎 − 𝑥)(𝑏 − 𝑥)
𝑑𝑡
𝑑𝑥
𝑜𝑟, = 𝑘. 𝑑𝑡
(𝑎 − 𝑥)(𝑏 − 𝑥)

Page 45 of 59
 1 1 1
𝑜𝑟, { − }𝑑𝑥 = 𝑘. 𝑑𝑡
(𝑎 − 𝑏) (𝑏 − 𝑥) (𝑎 − 𝑥)
After integrating we get,
1
{− ln(𝑏 − 𝑥) + ln(𝑎 − 𝑥)} = 𝑘. 𝑡 + 𝐶 ……………………………….…………………(i)
(𝑎−𝑏)

Here C is a integral constant. When t = 0, x = 0, then

1
{− ln(𝑏 − 0) + ln(𝑎 − 0)} = 𝑘. 0 + 𝐶
(𝑎 − 𝑏)
1 𝑎
𝑜𝑟, 𝑙𝑛 = 𝐶
(𝑎 − 𝑏) 𝑏
Putting the value of C in equation (i) we get,
1 1 𝑎
{− ln(𝑏 − 𝑥) + ln(𝑎 − 𝑥)} = 𝑘. 𝑡 + 𝑙𝑛
(𝑎 − 𝑏) (𝑎 − 𝑏) 𝑏
1 1 𝑎
𝑜𝑟, 𝑘. 𝑡 = {− ln(𝑏 − 𝑥) + ln(𝑎 − 𝑥)} − 𝑙𝑛
(𝑎 − 𝑏) (𝑎 − 𝑏) 𝑏
2.303 𝑏(𝑎−𝑥)
𝑜𝑟, 𝑘. 𝑡 = 𝑙𝑜𝑔 ……………………..…………………………………………(ii)
(𝑎−𝑏) 𝑎(𝑏−𝑥)

When the concentrations of the reacting molecules/species are same (a = b), under these conditions,
𝑑𝑥
= 𝑘. (𝑎 − 𝑥)2
𝑑𝑡
𝑑𝑥
𝑜𝑟, = 𝑘. 𝑑𝑡
(𝑎 − 𝑥)2
After integrating we get,
1
= 𝑘. 𝑡 + 𝐶 ………………………………………………...………………(iii)
𝑎−𝑥
Here C is a integral constant. When t = 0, x = 0, then
1
= 𝑘. 0 + 𝐶
𝑎−0
1
𝑜𝑟, 𝐶 =
𝑎
Now putting the value of C in the above equation (iii) we get
1 1
= 𝑘. 𝑡 +
𝑎−𝑥 𝑎
1 1
𝑜𝑟, 𝑘. 𝑡 = −
𝑎−𝑥 𝑎
𝑥
𝑜𝑟, 𝑘. 𝑡 =
𝑎(𝑎 − 𝑥)
1 𝑥
𝑜𝑟, 𝑘 = 𝑡 . 𝑎(𝑎−𝑥) (iv)
If a chemical reaction is allowed to proceed for different periods of time and right hand side of the above equation
is found constant for each period of time, then the value is the value of the rate constant of the reaction represents
that the reaction is second order.

Required Chemicals

1. 0.2 N Ethyl Acetate solution.

2. 0.2 N Sodium Hydroxide (NaOH) solution.
3. 0.2 N Hydrochloric (HCl) acid solution.

Page 46 of 59
 4. Indicator, phenolphthalein and/or methyl orange, litmus paper (blue and red).

Experimental procedure

Preparation of 0.20 N Ethyl Acetate solution: Take 17.60 g of ethyl acetate ester in a clean and dry 1.0 L volumetric
flask and fill it up to the mark with distilled water.

Preparation of 0.20 N Sodium Hydroxide (NaOH) solution:Take 8.0 g of NaOH pellets in a clean and dry 1.0 L
volumetric flask and fill it up to the mark with distilled water.

Take 100 mL of 0.20 N NaOH solution in a 100 mL beaker and 100 mL of 0.2 N ester solution in a 250 mL
beaker. Mix the base solution to the ester solution quickly, shake gently and start the stop watch. Allow the
solution stand still for reaction. After 5 minutes, take 30 mL of the solution in a 250 mL conical flask and titrate
it against 0.20 N HCl solution (from burette) using phenolphthalein as indicator. Record the volume of 0.20 N
HCl solution from burette. The amount of HCl solution represents the amount of un-reacted NaOH solution
present in the 30 mL reaction solution. Similarly take 30 mL solution from the reaction solution after 10 min, 15
min, 20 min, and 25 min and titrate them against 0.2 N HCl solution as above.

CH3COOC2H5 + NaOH → CH3COONa + C2H5OH

NaOH + HCl → NaCl + H2O
Experimental data table

Obs. Time, Volume of Burette reading, ml 1 𝑥

a-x x 𝑘= . Comments
No. t min reaction soln. ml Initial Final Diff 𝑡 𝑎(𝑎 − 𝑥)
1 00 30
2 05 30
3 10 30
4 15 30
5 20 30
6 25 30

Calculation

1. When t = 00, a-x = a then x = a-(a-x) = 0, k = 0. Reaction does not start.

2. When t = 05, a-x = …….. then x = a-(a-x) = ……..., k = ……….
3. When t = 10, a-x = …….. then x = a-(a-x) = ……..., k = ……….
4. When t = 15, a-x = …….. then x = a-(a-x) = ……..., k = ……….
5. When t = 20, a-x = …….. then x = a-(a-x) = ……..., k = ……….
6. When t = 25, a-x = …….. then x = a-(a-x) = ……..., k = ……….

Result and discussion: The rate constant of the reaction was found constant for each period of reaction time and
the value was ……….. The value was calculated on the basis of a second order reaction. So the reaction
(hydrolysis of ethyl acetate by sodium hydroxide base) was a second order reaction.

Name of experiment: Determination of equilibrium constant using distribution coefficient

Introduction

Page 47 of 59
Equilibrium constant is defined as the ratio of concentration of products to that of the reactants of a reaction in
the equilibrium state of that reaction. This is derived from the law of mass action.

N2 + 3H2 ⇋ 2NH3 ………………………. (i)

KI + I2 ⇋ KI3 ………………………. (ii)

[NH3 ]2
Equilibrium constant for reaction (i) , K c =
[N2 ]. [H2 ]2

[𝐾𝐼3 ]
Equilibrium constant for reaction (ii) , K 𝑐 =
[𝐾𝐼]. [𝐼2 ]

If a solute x is distributed between two immiscible solvents A and B at a constant temperature and x is in the
same molecular state/condition in both solvents, then the distribution coefficient of the solute x is defined as

concentration of x in A
KD =
concentration of x in B
If C1 is the concentration of the solute in solvent A and C 2 is the concentration of the solute in solvent B, then

𝐶1
Distribution coeffient of the solute x, 𝐾𝐷 =
𝐶2

This law is known as Nernst distribution law and KD is known as distribution coefficient or partition coefficient
or distribution ratio.

Principle

When iodine is shaken with water and carbon tetrachloride in a reagent bottle, it is distributed between water
(aqueous phase) and carbon tetrachloride (organic phase) layers. The concentration of iodine in both layers can
be determined by titration against standard sodium thiosulfate solution.

2Na2S2O3 + I2 → Na2S4O6 + 2NaI

concentration of I2 in aqueous layer

Distribution coeffient of iodine, K D =
concentration of I2 in organic layer

An aqueous solution of KI of concentration of C is shaken with iodine in a bottle. Some CCl 4 is added to it and
shaken. On standing the mixture separates into two layers. The equilibria that are set up as like this-

KI + I2 ⇄ KI3 ← Aqueous layer

I2 ← Organic layer

The concentration of iodine in both layers can be determined by titration against standard sodium thiosulfate
solution.

Let, b is the concentration of iodine in CCl4 (organic) layer and a is the concentration of iodine in water layer
which is really the total of the concentration of free iodine and KI3.

Page 48 of 59
 concentration of I2 in aqueous layer, a
distribution coeffient of iodine, K D =
concentration of I2 in organic layer, b

Concentration of free I2 in aqueous layer, [I2 ] = KD × b

Hence concentration of KI3 in aqueous layer, [KI3 ] = a- KD × b
Concentration of KI in aqueous layer, [KI] = C – (a- KD × b)

Then the equilibrium constant for the reactionKI + I2 ⇄ KI3 can be determined by the following equation.

[KI3 ]
Equilibrium constant for reaction , K c =
[KI]. [I2 ]

Experimental Procedure

1. Take 50 mL distilled water in a reagent bottle and add 0.50 g of iodine. Then add 50 mL of carbon
tetrachloride and shake well with the stopper of the bottle. After 30 minutes, allow to stand and titrate 10
mL of solutions of each layers with standard sodium thiosulfate solution. Repeat this once. From the
average value of each layer’s iodine concentration, calculate the distribution coefficient of iodine as per
the above equation.
2. Take 50 mL distilled water in a reagent bottle and add 0.50 g of KI and 0.50 g of I2 in it. Shake well.
Then add 50 mL of CCl4 to it and shake continuously for 30 minutes. After that titrate 10 mL of
solutions of each layer with standard sodium thiosulfate solution. Repeat this once.

Table: Standardization of iodine distribution coefficient

Burette reading (volume of Average Conc. of

No. Conc. of Distribution
Volume of Na2S2O3 solution) (mL) or mean std.
of I2 coefficient,
solution (mL) value solution
obs. Initial Final Difference (M) KD
(mL) (M)
1 Aqueous
2 layer
3 Organic
4 layer

Table: Standardization of iodine

Burette reading (volume of Average Conc. of

No. Conc. of Equilibrium
Volume of Na2S2O3 solution) (mL) or mean std.
of I2 constant,
solution (mL) value solution
obs. Initial Final Difference (M) Kc
(mL) (M)
1 Aqueous
2 layer
3 Organic
4 layer

Calculation

concentration of I2 in aqueous layer, a

Distribution coeffient of iodine, K D =
concentration of I2 in organic layer, b

Concentration of free I2 in aqueous layer [𝐼2 ] = KD × b

Page 49 of 59
 Hence concentration of KI3 in aqueous layer [𝐾𝐼3 ] = a- KD × b
Concentration of KI in aqueous layer [𝐾𝐼] = C – (a- KD × b)

Then the equilibrium constant for the reaction- KI + I2 ⇄ KI3

[KI3 ]
Kc =
[KI]. [I2 ]

Result: Distribution coefficient, KD of iodine in water and carbon tetrachloride was found to be ……….. and
equilibrium constant of the reaction was ……………. .

=================================

Page 50 of 59
 Chapter-V
Industrial and Environmental
Chemistry Experiments

Name of experiment: Determination of acidity of supplied water sample

Introduction

Page 51 of 59
Acidity: Acidity is a measure as the power of water to neutralize hydroxyl ions and is expressed in terms of
calcium carbonate (CaCO3). Water attains acidity from industrial effluent, acid mine drainage, pickling liquors
and from humic acid.

Principle

Acidity of water can be determined by titration with sodium hydroxide solution. The amount of sodium hydroxide
required for the sample (pH below 4.5) to reach pH 4.5 (methyl orange end point) is a measure of mineral acidity
while the amount of sodium hydroxide required to reach pH 8.3 (Phenolphthalein end point) is a measure of total
acidity. Sample containing acidic waste (pH below 4.5) correspond to both mineral and CO 2 acidity.

Reaction

NaOH reacts with CO2 in water to form Na2CO3 and H2O as follows

CaCO3 → CaO + CO2

CO2+ H2O ⇋ H++ HCO3-
H++ HCO3-+ 2NaOH → Na2CO3+ 2H2O

From the above reaction we can write

1000 mL 2.0 N NaOH ≡ 100 g of CaCO3
100
1 mL 1.0 N NaOH ≡ = 0.05 g of CaCO3
1000×2.0

Total acidity of the water sample =

106
Volume of alkali titration (mL) × Normality × 0.05 × = .......... ppm.
Volume of sample (mL)
Total acidity is expressed as CaCO3.

Reagents

1. 0.02 N NaOH solution.

2. Phenolphthalein indicator.

Experimental procedure

Take 100 mL of a water sample in a tall cylinder to decrease the surface area of the sample and minimize the loss
of dissolved carbonic acid during titration. Now add few drops of phenolphthalein indicator and titrate the solution
very rapidly against 0.02 N NaOH solution with constant stirring until a faint pink color is obtained.

Total acidity of the water sample =

106
Volume of alkali titration (mL) × Normality × 0.05 × = ..........ppm.
Volume of sample (mL)
Total acidity is expressed as CaCO3.

Result: Total acidity of the supplied water sample was ............................... ppm.

Name of experiment: Determination of alkalinity of a given water sample

Introduction

Alkalinity

Page 52 of 59
It is the power of water to neutralize hydrogen ions and is expressed in terms of calcium carbonate (CaCO3).
Alkalinity of water is due to the presence of carbonate and hydroxide ions.

Principle

Alkalinity is determined by titration with 0.02 N H2SO4 solution using phenolphthalein and methyl orange as
indicators.
Reactions
2CaCO3 + H2SO4 → CaSO4 + Ca(HCO3)2
Ca(HCO3)2 + H2SO4 → CaSO4 + 2CO2 + 2H2O
Ca(OH)2 + H2SO4 → CaSO4 + 2H2O

From the above reactions we can write-

1000 mL 2.0 N H2SO4 solution ≡ 100 g of CaCO3
100
1 mL 1.0 N H2SO4 solution ≡ = 0.05 g of CaCO3
1000×2.0
Alkalinity of the water sample =
106
Volume of H2SO4 (mL) × Normality × 0.05 × = ..........ppm.
Volume of sample (mL)
Reagents

1. 0.02 N sulfuric acid solution.

2. Phenolphthalein indicator.
3. Methyl orange indicator.

Experimental procedure

1. Take 100 mL of water sample in a conical flask. Add 2-3 drops of phenolphthalein as indicator to it and
titrate against 0.02 N H2SO4 solution until the pink color disappears. The quantity of 0.02 N H2SO4
solution implies the phenolphthalein alkalinity in the water sample. Phenolphthalein alkalinity as CaCO 3
is calculated in ppm as follows

Phenolphthalein Alkalinity of the water sample as CaCO3 =

106
Volume of H2SO4 (mL) × Normality × 0.05 × = ..........ppm.
Volume of sample (mL)

2. After obtaining the Phenolphthalein end point, add 2-3 drops of methyl orange as indicator to the same
solution and continue the titration against 0.02 N H2SO4 solution from the burette until the color changes
from yellow to orange. The quantity of 0.02 N H2SO4 solution implies the methyl orange alkalinity in
the water sample. Methyl orange alkalinity as CaCO3 is calculated in ppm as follows

Methyl orange alkalinity of the water sample as CaCO3 =

106
Volume of H2SO4 (mL) × Normality × 0.05 × = ..........ppm.
Volume of sample (mL)

Methyl orange alkalinity indicates the total alkalinity of the sample in terms of CaCO 3.

Result: Alkalinity of the supplied water sample was ............................... ppm.

Name of experiment: Determination of the amount of dissolved oxygen by Winkler method

Introduction

Page 53 of 59
One of the most useful titration’s involving iodine is that originally developed by Winkler to determine the amount
of oxygen in samples of water. The dissolved oxygen content is not only important with respect to the species of
aquatic life which can survive in water, but also a measure of its ability to oxidize organic impurities in water.
Despite the advent of oxygen selective electrode direct titration on water samples are still used extensively.

In order to avoid loss of oxygen from the water sample, it is fixed by its reaction with manganese (II) hydroxide,
which is converted rapidly and quantitatively to manganese (III) hydroxide:

4Mn(OH)2 +O2 +2H2O → 4Mn(OH)3 ↓(brown ppt.) (1)

The brown precipitate obtained dissolves on acidification and oxidizes iodide ions to iodine:

4Mn(OH)3.+ 4I- + 12H+→ 4Mn2+ + 2I2 +12H2O. (2)

The free iodine may then be determined by titration with sodium thiosulfate:

4S2O2-3 +2I2 → 2S4O62- +4I- (3)

Equation (1), (2) & (3) implies that 4 moles of thiosulfate is equal to 1 mole of dissolved oxygen.

The main interference in this process is due to the presence of nitrites (available in swage treatment water). This
is overcome by treating the original water sample with sodium azide, which destroys any nitrite when the sample
is acidified

HNO2 + HN3 → N2 +N2O + H2O

Chemicals

Manganese (II) Sulfate (pentahydrate solution): Prepared by dissolving 50g of manganese Sulfate in water and
making up to 100 mL.
Alkaline- iodide- azide solution: Prepared by dissolving 40g of sodium hydroxide, 20g of potassium iodide and
0.5g of sodium azide and making up to 100 mL.
85 % Phosphoric (V) acid.
Sodiumthiosulfate solution (M/80).
Starch solution as indicator.

Apparatus

Burette 50 mL , pipette 25 mL, conical flask 250 mL, reagent bottle 250 mL

Procedure

The water sample should be collected carefully by filling a 200-250 mL bottle to very top and stoppering it while
it is below the water surface. This should eliminate any further dissolution of atmospheric oxygen. By using a
dropping pipette placed below the surface of the water sample, add 1 mL of 50% manganese Sulfate solution and
in a similar way add 1 mL of alkaline potassium iodide solution. Re-stopper the water sample and shake well. The
manganese (III) hydroxide forms as a brown precipitate. Allow the precipitate to settle completely for about 15
minutes and add 2 mL of concentrated phosphoric acid (85%). Replace the stopper and run the bottle upside-
down two or three times in order to mix the contents. The brown precipitate will dissolve and release iodine in the
solution. If the brown precipitate has not completely dissolved then add a little more (a few drops) phosphoric (V)
acid.

Measure out a 100 mL portion of the solution with a pipette and titrate the iodine with approximately M/80
standard sodium thiosulfate solution adding 2 mL of starch solution as indicator as the titration proceeds before
the end point and after the titration liquid has become pale yellow in color.

Calculation

Page 54 of 59
The dissolved oxygen content expressed in mg/L and can be calculated using the following formula

1mL of M/80 thiosulfate = 0.1 mg of dissolved oxygen.

number of mL of M⁄80 thiosulfate solution × 0.1

Dissolved oxygen content (mg⁄L) = × 1000
mL of titrated water sample

Permanganate modification method

Reagents

1. 0.20 N KMnO4 solution: Dissolve 6.32 g in 1L of distilled water.

2. 20.17N K2C2O4 solution: Dissolve 20 g of K2C2O4 in 1L of distilled water.
3. Manganous sulfate solution: Dissolve 400 g of MnSO4.H2O in 1L of distilled water.
4. Alkaline potassium iodide solution: Dissolve 700 g of KOH and 150 g of solid KIin 1L of distilled water.
5. Concentrated sulfuric acid (99%)
6. 0.025N sodium thiosulfate solution: Dissolve 6.205 g of Na2S2O3 in 1L of distilled water.
7. 0.5% Starch solution.

Procedure

To the bottle containing 250 mL of sample, 0.7 mL of H2SO4 (conc.) and 1 mL of KMnO4 solutions are added.
The bottle is stoppered and shaked well for several times. If KMnO 4 is insufficient, it is added more. After the
color has persisted for 20 minutes, the excess of KMnO4 is destroyed by adding 1 mL of 20.17 N K2C2O4 solution.
Now 1 mL of manganous Sulfate solution and 5 mL of alkaline potassium iodide solution are added to the sample.
The bottle is stoppered and shaked well thoroughly. When the precipitate formed is settled, 1 lm of conc. H 2SO4
is added and the bottle is again stoppered and shaked well until the precipitate has completely dissolved. 200 mL
of content of the bottle is transferred to a 500 mL conical flask and titrated the iodine liberated by 0.025N sodium
thiosulfate solution using starch as indicator.

Calculation

From the above reactions we can write-

1000 mL 4.0 N Na2S2O3 solution ≡ 32 g of DO

32
1 mL 1.0 N Na2S2O3solution ≡ = 0.008 g of DO
1000×4.0
Dissolved Oxygen =
Volume of Na2S2O3 (mL) × Normality × 0.008 × 106/ Vol. of titrated sample (mL) = ----- PPM

In the titration of 200 mL of the sample using 0.025 N Na2S2O3 solution, that is ml of Na2S2O3 solution ≡ ppm
DO.

Preparation of 0.10 N sodium thiosulfate solution

Sodium thiosulfate pentahydrate (Na2S2O3.5H2O) is readily obtainable in a state of high purity, but there is always
some uncertain as to the exact water content because of the efflorescent nature of the salt and for other reasons.
The substance is therefore unsuitable as a primary standard. It is a reducing agent by virtue of the half-cell reaction:

2S2O32- S4O62- + 2e-

thiosulphate ion tetrathionate ion
Thus the equivalent weight of sodium thiosulfate is its molecular weight or 248.19

Preparation

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An approximately 0.1N solution is prepared by dissolving about 25g of crystallized sodium thiosulfate in 1L of
water in a volumetric flask.

Other reasons: Ordinary distilled water usually contains an excess of carbon dioxide, this may cause a slow
decomposition to take place with the formation of sulfur:

2S2O32- + H+ HSO3- + S
thiosulphate ion bisulphide ion
Moreover, decomposition may also be caused by bacterial action, particularly if the solution has been standing
for some time.

Name of experiment: Determination of corrosion rate of mild steel (MS) in hydrochloric (HCl)
acid solution
Introduction

Corrosion: Corrosion is gradual degradation/destruction/deterioration of metals and alloys by electrochemical

reaction with the environment. For example, rusting of iron exposed to atmosphere.

Corrosion rate is defined as the number of moles of metal dissolves as metal ion per unit time per unit area. When
MS steel sheet is immersed in HCl solution, following reaction occurs-

Fe + HCl → FeCl2 + H2

Where Cu2+ ion is an accelerating agent to accelerate the dissolution of iron.

Corrosion: Corrosion is gradual degradation/destruction/deterioration of metals and alloys by electrochemical

reaction with the environment. For example, rusting of iron exposed to atmosphere.

Principle: Iron (as Fe2+ ion) present in a solution can be measured volumetrically by redox titration with standard
potassium permanganate solution in acid medium. The reaction involved is as follows

5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 8H2O

Or 10FeSO4 + 2KMnO4 + 8H2SO4 → 5Fe2(SO4)3 + K2SO4 + 2MnSO4 + 8H2O

From the above equation we can write,

1000 ml 5.0 N KMnO4 solution ≡ 5×55.85 g of iron (as Fe2+)

5×55.85
1 ml 1.0 N KMnO4 solution ≡ = 0.05585 g of iron (as Fe2+)
1000×5
Apparatus: same as other experiment

Reagent

HCl, KMnO4, H2SO4, Z-R reagent, SnCl2 etc.

Experimental procedure

Take the supplied mild steel sample and remove the metal oxide as passive film from the both sides by rubbing
with sand paper. Accurately measure the total surface area of the specimen. Polish them to make the surfaces as
smooth as possible with sand paper and clean with tap water followed by ringing with distilled water. Immerse
the sample coupon in 200 ml supplied HCl acid solution for one (01) hour in such a way that the specimen remains
completely stand in the acid solution and do not lie flat on the container bottom. After completion of the immersion

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period remove the coupon from the solution and carefully scrub away the adhered corrosion product (if any) from
the surface with a camel brush into the respective solution.

Take 25 ml of this solution by pipette in a 250 ml conical flask. Add concentrated SnCl 2 solution drop wise till
the yellow color fades. Add 5 ml HgCl2 solution by measuring cylinder, silky white precipitate will appear. Add
10 ml of Zimmermann and Reinhardt’s (Z-R)* solution by measuring cylinder and tantamount of distilled water.
Then, titrate the solution with standard KMnO4 solution until a faint pink color of KMnO4appears that persists at
least for 30 seconds.

Fe - 2e → Fe2+ (corrosion)
Fe2+ - e → Fe3+ (oxidation)
2H+ + H2 (reduction)
→
2e
Fe3+ + Sn2+ → Fe2+ + Sn4+
SnCl2 + 2HgCl2 → SnCl4 + Hg2Cl2
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 8H2O
10FeSO4 + 2KMnO4 + 8H2SO4 → 5Fe2(SO4)3 + K2SO4 + 2MnSO4 + 8H2O

* Zimmermann and Reinhardt’s (Z-R) solution: This is sometimes termed as preventive solution. This solution
is prepared by dissolving 50 g of crystallized manganese (II) sulfate (MnSO 4.4H2O) in 250 ml water, adding a
cooled mixture of 100 ml concentrated sulfuric acid and 300 ml of water, followed by 100 ml of syrupy phosphoric
acid. The manganese sulfate lowers the reduction potential of MnO 4- - Mn2+ and thereby makes it weaker oxidizing
agent. The tendency of permanganate ion to oxidize chloride ion is thus reduced.

# 100 cm2 = 1 dm2.

Calculation
Amount of iron present in the given sample

= Volume of KMnO4 (ml) × Normality × 0.05585 ×1000 = ….......... mg of iron.

Corrosion rate in mdd (milligram per square decimetre per day)

Total amount of iron corroded (mg)
= = ……………mdd
Total surface area of MS sample (dm2) × time (day)

Name of experiment: Determination of corrosion rate of mild steel (MS) in hydrochloric (HCl)
acid solution containing Cu2+ ion
Introduction

Corrosion rate is defined as the number of moles of metal dissolves as metal ion per unit time per unit area. When
MS steel sheet is immersed in HCl solution, following reaction occurs

Fe + HCl → FeCl2 + H2

Where Cu2+ ion is an accelerating agent to accelerate the dissolution of iron.

Corrosion: Corrosion is gradual degradation/destruction/deterioration of metals and alloys by electrochemical

reaction with the environment. For example, rusting of iron exposed to atmosphere.

Principle

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Iron (as Fe2+ ion) present in a solution can be measured volumetrically by redox titration with standard potassium
permanganate solution in acid medium. The reaction involved is as follows

5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 8H2O

Or 10FeSO4 + 2KMnO4 + 8H2SO4 → 5Fe2(SO4)3 + K2SO4 + 2MnSO4 + 8H2O

From the above equation we can write,

1000 ml 5.0 N KMnO4 solution ≡ 5×55.85 g of iron (as Fe2+)

5×55.85
1 ml 1.0 N KMnO4 solution ≡ = 0.05585 g of iron (as Fe2+)
1000×5

Reagent

HCl, KMnO4, H2SO4, Z-R reagent, SnCl2 etc.

Apparatus

same as other experiment.

Experimental Procedure

Take the supplied mild steel sample and remove the metal oxide as passive film from the both sides by rubbing
with sand paper. Accurately measure the total surface area of the specimen. Polish them to make the surfaces as
smooth as possible with sand paper and clean with tap water followed by ringing with distilled water. Immerse
the sample coupon in 200 mL supplied HCl acid solution containing Cu2+ ion for one (01) hour in such a way that
the specimen remains completely stand in the acid solution and do not lie flat on the container bottom. If bubbles
appear on the sample surface, remove them with a glass rod by stirring. After completion of the immersion period
remove the coupon from the solution and carefully scrub away the adhered corrosion product (if any) from the
surface with a camel brush into the respective solution.

Take 25 mL of this solution by pipette in a 250 mL conical flask. Add concentrated SnCl2 solution drop wise till
the yellow color fades. Add 5 mL HgCl2 solution by measuring cylinder, silky white precipitate will appear. Add
10 mL of Zimmermann and Reinhardt’s (Z-R) solution by measuring cylinder and tantamount of distilled water.
Then, titrate the solution with standard KMnO4 solution until a faint pink color of KMnO4 persists for 30 seconds.

Fe - 2e → Fe2+ (corrosion)
Cu2+ + 2e → Cu (Reduction)
Fe2+ - e → Fe3+ (oxidation)
Fe3+ + Sn2+ → Fe2+ + Sn4+
SnCl2 + 2HgCl2 → SnCl4 + Hg2Cl2
5Fe + MnO4- + 8H+
2+
→ 5Fe3+ + Mn2+ + 8H2O
10FeSO4 + 2KMnO4 + 8H2SO4 → 5Fe2(SO4)3 + K2SO4 + 2MnSO4 + 8H2O

Calculation

Amount of iron present in the given sample

= Volume of KMnO4 (mL) × Normality × 0.05585 ×1000 = ….......... mg of iron.

Corrosion rate in mdd (milligram per square decimeter per day)

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 Total amount of iron corroded (mg)
= = ……………mdd
Total surface area of MS sample (dm2) × time (day)

=================== The End ===================

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