Department of Chemistry

Faculty of Applied Sciences

Umm Al-Qura University

Practical Physical Chemistry

(Physical chemistry II)

Prepared by

Dr. Ahmed Fawzy Saad

Prof. Dr. El-Sayed M. Mabrouk

Dr. Hanaa Shokry

Department of Chemistry
Faculty of Applied Sciences
Umm Al-Qura University
1434 2013

CONTENTS

Subject

Page

1. PREFACE

2. I. CHEMICAL KINETICS

3. INTRODUCTION

4. Catalytic Decomposition of Hydrogen Peroxide.

18

5. Experiment: Determination of the rate of hydrogen peroxide

decomposition catalyzed by manganese dioxide.

18

6. Hydrolysis of Ethyl Acetate in Acid Medium.

20

7. Experiment: Determination of the order of reaction and rate constant of

hydrolysis of ethyl acetate in acid medium.

20

8. Saponification of ethyl acetate in alkaline medium.

23

9. Experiment: Determination of the saponification rate constant of ethyl acetate

in alkaline medium.

23

10. Persulfate-Iodide Reaction.

26

11. Experiment: Determination of the rate constant and half-life period of the
Persulphate - iodide reaction.

26

12. Hydrogen Peroxide - Hydrogen Iodide Reaction.

29

13. Experiment I: Determination of the order of the reaction between hydrogen

peroxide and hydrogen iodide.

30

14. Experiment II: Determination of the rate constant and the energy of activation
of the reaction between hydrogen peroxide and hydrogen iodide.

33

15. Halogenation of Acetone in Solution.

36

16. Experiment: Investigation of the reaction between acetone and iodine.

36

17. Autocatalytic Reaction between Potassium Permanganate and Oxalic Acid.

18. Experiment: Investigation of the reaction between potassium permanganate
and oxalic acid.
40

39

Subject

Page

19. II. THERMOCHEMISTRY

42

20. INTRODUCTION

43

21. Heat Capacity.

46

22. Experiment: Determination of the heat capacity of the calorimeter.

46

23. Experiment II: Determination of the heat capacity of different solutions of NaCl.

48

24. Heat of Solution.

50

25. Experiment: Determination of heat of solution of ammonium chloride

(as endothermic reaction) at infinite dilution.
26. Heat of Neutralization.

50
53

27. Experiment: Determination of the heat of neutralization of hydrochloric acid

and sodium hydroxide.

53

28. Hess's law.

56

29. Experiment: Application of Hess's law.

57

30. III. PHASE EQUILIBRIA

59

31. INTRODUCTION

60

32. Two Components System.

60

33. Composition Temperature diagrams.

60

34. Experiment: Determination of critical solution temperature of water-phenol system. 62

35. Three Components System.

64

36.Experiment: Construct the binodal curve for the system ethyl acetate ethyl
alcohol-water.

66

PREFACE
The necessity claimed to originate a simple course of practical physical
chemistry (Physical chemistry II, Code No. 402342, to be studied in the fifth
level) in particularly chemical kinetics, thermochemistry and phase
equilibria. So that the experiments have been chosen to be convenient the
students which starting a laboratory course. The experiments simplified to
can be made by the humble resources and the simple experiment. For
better understanding, every experiment has been supplied with a
theoretical idea to help the student to prepare a short report about the
different subjects.
Our best thanks to Dr. Omer A. Hazazi, Chairman of chemistry
department, faculty of applied sciences, Umm Al-Qura university for the
facilities presented in our department and providing all our requirements.
All members of our department are also acknowledged.

The Staff

I
CHEMICAL KINETICS

INTRODUCTION

Chemical kinetics deals with the rates of chemical processes. Any chemical
process may be broken down into a sequence of one or more single-step processes
known either as elementary processes, elementary reactions, or elementary steps.
An important point to recognize is that many reactions that are written as a single
reaction equation in actual fact consist of a series of elementary steps. This will
become extremely important as we learn more about the theory of chemical
reaction rates.
Chemical kinetics is the quantitative study of chemical systems that are
changing with time. (Thermodynamics, another of the major branches of physical
chemistry, applies to systems at equilibrium - those that do not change with time).
Chemical kinetics is conventionally regarded as a topic in physical chemistry.
In this guise it covers the measurement of rates of reaction, and the analysis of the
experimental data to give a systematic collection of information which summarizes
all the quantitative kinetic information about any given reaction. This, in turn,
enables comparisons of reactions to be made and can afford a kinetic classification
of reactions. The sort of information used here is summarized in terms of
the factors influencing rates of reaction,
the dependence of the rate of the reaction on concentration, called the order
of the reaction,
the rate expression, which is an equation which summarizes the dependence
of the rate on the concentrations of substances which affect the rate of
reaction,
this expression involves the rate constant which is a constant of
proportionality linking the rate with the various concentration terms,
7

 this rate constant collects in one quantity all the information needed to
calculate the rate under specific conditions,
the effect of temperature on the rate of reaction. Increase in temperature
generally increases the rate of reaction. Knowledge of just exactly how
temperature affects the rate constant can give information leading to a
deeper understanding of how reactions occur.

Chemical kinetics is not just an aspect of physical chemistry. It is a unifying

topic covering the whole of chemistry, and many aspects of biochemistry and
biology. It is also of supreme importance in both the chemical and pharmaceutical
industries. Since the mechanism of a reaction is intimately bound up with kinetics,
and since mechanism is a major topic of inorganic, organic and biological
chemistry, the subject of kinetics provides a unifying framework for these
conventional branches of chemistry. Surface chemistry, catalysis and solid state
chemistry all rest heavily on knowledge of kinetic techniques, analysis and
interpretation. Improvements in computers and computing techniques have resulted
in dramatic advances in quantum mechanical calculations of the potential energy
surfaces and in theoretical descriptions of rates of reaction. Kinetics also makes
substantial contributions to the burgeoning subject of atmospheric chemistry and
environmental studies.

Rate of reaction
When we talk about the rate of a chemical reaction, what we mean is the rate
at which reactants are used up, or equivalently the rate at which products are
formed. The rate, therefore, has units of concentration per unit time, mol dm-3 s-1
(for gas phase reactions, alternative units of concentration are often used, usually
units of pressure Torr, mbar or Pa). To measure a reaction rate, we simply need
8

to monitor the concentration of one of the reactants or products as a function of

time. There is one slight complication to our definition of the reaction rate so far,
which is to do with the stochiometry of the reaction. The stoichiometry simply
refers to the number of moles of each reactant and product appearing in the
reaction equation. For example, the reaction equation for the well-known Haber
process, used industrially to produce ammonia, is:
N2 + 3H2 = 2NH3
N2 has a stochiometric coefficient of 1, H2 has a coefficient of 3, and NH3 has a
coefficient of 2. We could determine the rate of this reaction in any one of three
ways by monitoring the changing 3 concentration of N2 , H2 , or NH3. Say we
monitor N2 and obtain a rate of -d[N2] / dt = x mol dm-3 s-1. Since for every mole
of N2 that reacts, we lose three moles of H2 , if we had monitored H2 instead of N2
we would have obtained a rate -d[H2] / dt = 3x mol dm-3 s-1. Similarly, monitoring
the concentration of NH3 would yield a rate of 2x mol dm-3 s-1. Clearly, the same
reaction cannot have three different rates, so we appear to have a problem. The
solution is actually very simple: the reaction rate is defined as the rate of change of
the concentration of a reactant or product divided by its stochiometric coefficient.
For the above reaction, the rate (usually given the symbol ) is therefore
v

d[ N 2 ]
1 d [ H 2 ] 1 d [ NH 3 ]

dt
3 dt
2 dt

Note that a negative sign appears when we define the rate using the concentration
of one of the reactants. This is because the rate of change of a reactant is negative
(since it is being used up in the reaction), but the reaction rate needs to be a
positive quantity.

Rate laws
The rate law is an expression relating the rate of a reaction to the
concentrations of the chemical species present, which may include reactants,
products, and catalysts. Many reactions such as: a A + b B + c C P, follow a
simple rate law, which takes the form
Rate = = k [A]a[B]b[C]c
i.e. the rate is proportional to the concentrations of the reactants each raised to
some power. The constant of proportionality, k, is called the rate constant. The
power a particular concentration is raised to is the order of reaction with respect to
that reactant. Note that the orders do not have to be integers. The sum of the
powers is called the overall order. Even reactions that involve multiple elementary
steps often obey rate laws of this kind, though in these cases the orders will not
necessarily reflect the stoichiometry of the reaction equation. For example,
H2 + I2 2HI;

= k [H2] [I2]

Elementary processes always follow simple rate laws, in which the order with
respect to each reactant reflects the molecularity of the process (how many
molecules are involved). For example,
Unimolecular decomposition:

A B;

= k [A]

Bimolecular reaction:

A + B P;

= k [A][B]

A + A P;

= k [A][A] = k [A]2

We can carry out experiments to determine the orders with respect to each
reactant and then try out various trial reaction mechanisms to see which one fits
best with the experimental data. At this point it should be emphasized again that
for multi-step reactions, the rate law, rate constant, and order are determined by
experiment, and the orders are not generally the same as the stoichiometric
coefficients in the reaction equation. A final important point about rate laws is that
overall rate laws for a reaction may contain reactant, product and catalyst
10

concentrations, but must not contain concentrations of reactive intermediates

which appear in rate laws for the individual elementary steps.

The units of the rate constant

A point which often seems to cause endless confusion is the fact that the units
of the rate constant depend on the form of the rate law in which it appears i.e. a
rate constant appearing in a first order rate law will have different units from a rate
constant appearing in a second order or third order rate law. This follows
immediately from the fact that the reaction rate always has the same units of
concentration per unit time, which must match the overall units of a rate law in
which concentrations raised to varying powers may appear. The good news is that
it is very straightforward to determine the units of a rate constant in any given rate
law. Below are a few examples:
(i)

Consider the rate law; = k [H2] [I2]. If we substitute units into the
equation, we obtain
(mol dm-3 s-1) = [k] (mol dm-3) (mol dm-3)
where the notation [k] means the units of k. We can rearrange this
expression to find the unit of the rate constant, k, as follows:
[k] = (mol dm-3 s-1) / (mol dm-3) (mol dm-3) = mol-1 dm3 s-1

(ii) We can apply the same treatment to a first order rate law, for example
= k [CH3N2CH3].
(mol dm-3 s-1) = [k] (mol dm-3)
[k] = (mol dm-3 s-1) / (mol dm-3) = s-1
(iii) As a final example, consider the rate law
= k [CH3CHO]3/2
(mol dm-3 s-1) = [k] (mol dm-3)3/2
[k] = (mol dm-3 s-1) / (mol dm-3)3/2 = mol-1/2 dm3/2 s-1
11

An important point to note is that it is meaningless to try and compare two rate
constants unless they have the same units.

Integrated rate laws

A rate law is a differential equation that describes the rate of change of a
reactant (or product) concentration with time. If we integrate the rate law then we
obtain an expression for the concentration as a function of time, which is generally
the type of data obtained in any kinetic experiment. In many simple cases, the rate
law may be integrated analytically. Otherwise, numerical (computer-based)
techniques may be used. Four of the simplest rate laws are given below in both
their differential and integrated form.

In the above [A]0 and [B]0 represent the initial concentrations of A and B, i.e. their
concentrations at the start of the reaction.

12

Half lives
The half life, t1/2 , of a substance is defined as the time it takes for the
concentration of the substance to fall to half of its initial value. We can obtain
equations for the half lives for reactions of various orders by substituting the values
t = t1/2 and [A] = [A]0 into the integrated rate laws. We obtain
Zeroth order reaction;

t1/2 = [A]0 / 2k

First order reaction;

t1/2 = ln 2 / k

Second order reaction;

t1/2 = 1 / k [A]0

Determining the rate law from experimental data

A kinetics experiment consists of measuring the concentrations of one or more
reactants or products at a number of different times during the reaction. We will
look at the methods that allow us to use the experimental data to determine the
reaction orders with respect to each reactant, and therefore the rate law.

(i) Isolation method

The isolation method is a technique for simplifying the rate law in order to
determine its dependence on the concentration of a single reactant. Once the rate
law has been simplified, the differential or integral methods may be used to
determine the reaction orders. The dependence of the reaction rate on the chosen
reactant concentration is isolated by having all other reactants present in a large
excess, so that their concentration remains essentially constant throughout the
course of the reaction.
As an example, consider a reaction A + B P, in which B is present at a
concentration 1000 times greater than A. When all of species A has been used up,
the concentration of B will only have changed by 1/1000, or 0.1%, and so 99.9% of
the original B will still be present. It is therefore a good approximation to treat its
13

concentration as constant throughout the reaction. This greatly simplifies the rate
law since the (constant) concentrations of all reactants present in large excess may
be combined with the rate constant to yield a single effective rate constant. For
example, the rate law for the reaction considered above will become:
= k [A]a [B]b k [A]a [B]0b = keff [A]a

with

keff = k [B]0b

When the rate law contains contributions from a number of reactants, a series of
experiments may be carried out in which each reactant is isolated in turn.

(ii) Differential methods

When we have a rate law that depends only on the concentration of one
species, either because there is only a single species reacting, or because we have
used the isolation method to manipulate the rate law, then the rate law may be
written
= k [A]a

(*)

log = log k + a log[A]

A plot of log against log[A] will then be a straight line with a slope equal to the
reaction order, a, and an intercept equal to log k. There are two ways in which to
obtain data to plot in this way.
1. We can measure the concentration of the reactant [A] as a function of time
and use this data to calculate the rate, = - d[A]/dt , as a function of [A]. A
plot of log vs. log [A] then yields the reaction order with respect to A.
2. We can make a series of measurements of the initial rate 0 of the reaction
with different initial concentrations [A]0. These may then be plotted as
above to determine the order, a. This is a commonly used technique known
as the initial rates method.

14

(iii) Integral methods

If we have measured concentrations as a function of time, we may compare
their time dependence with the appropriate integrated rate laws. Again, this is most
straightforward if we have simplified the rate law so that it depends on only one
reactant concentration. The differential rate law given in Eq. (*) will give rise to
different integrated rate laws depending on the value of a. The most commonly
encountered ones are:
Zeroth order integrated rate law:

[A] = [A]0 kt

A plot of [A] vs. t will be linear, with a slope of -k.

First order integrated rate law:

ln [A] = ln [A]0 kt

A plot of ln [A] vs. t will be linear with a slope of -k.

Second order integrated rate law:

1/[A] = 1/[A]0 + 2kt

A plot of 1/[A] vs. t will be linear with a slope of 2k.

If none of these plots result in a straight line, then more complicated integrated
rate laws must be tried.

(iv) Half lives method

Another way of determining the reaction order is to investigate the behaviour
of the half life as the reaction proceeds. Specifically, we can measure a series of
successive half lives. t = 0 is used as the start time from which to measure the first
half life, t1/2(1). Then t1/2(1) is used as the start time from which to measure the
second half life, t1/2(2), and so on.
Zeroth order:

t1/2 = [A]0 / 2 k

Since at t1/2(1), the new starting concentration is [A]0, successive half lives
will decrease by a factor of two for a zeroth order reaction.
First order:

t1/2 = ln 2 / k
15

There is no dependence of the half life on concentration, so t1/2 is constant

for a first order reaction.
Second order:

t1/2 = 1 / k [A]0

The inverse dependence on concentration means that successive half lives

will double for a second order reaction.

Experimental techniques
Experimental techniques have been developed to monitor reactions over
timescales varying from hours or days all the way down to a few femto-seconds
(1 fs = 10-15 s). While it is relatively simple to monitor the kinetics of a slow
reaction (occurring over minutes to hours or longer), highly specialized techniques
are required in order to study such fast reactions. Whatever the details of the
experimental arrangement, any kinetics experiment essentially consists of mixing
the reactants and initiating reaction on a timescale that is negligible relative to that
of the reaction, and then monitoring the concentration (s) of one or more reactants
and/or products as a function of time. Because rate constants vary with
temperature, it is also important to determine and control accurately the
temperature at which the reaction occurs.

(i) Techniques for mixing the reactants and initiating reaction

For slow reactions, occurring over minutes to hours, reaction is usually
initiated simply by mixing the reactants together by hand or with a magnetic stirrer
or other mechanical device. For fast reactions, a wide range of techniques have
been developed.

16

(ii) Techniques for monitoring concentrations as a function of time

For slow reactions, the composition of the reaction mixture may be analyzed
while the reaction is in progress either by withdrawing a small sample or by
monitoring the bulk. This is known as a real time analysis. Another option is to use
the quenching method, in which reaction is stopped a certain time after initiation
so that the composition may be analyzed at leisure. Quenching may be achieved in
a number of ways such as: sudden cooling, adding a large amount of solvent, rapid
neutralization of an acid reagent, removal of a catalyst and addition of a quencher.
The composition of the reaction mixture may be followed in any one of a
variety of different ways by tracking any chemical or physical change that occurs
as the reaction proceeds as follows:
For reactions in which at least one reactant or product is a gas, the reactions
progress may be followed by monitoring the pressure, or possibly the
volume.
For reactions involving ions, conductivity or pH measurements may often be
employed.
If the reaction is slow enough, the reaction mixture may be titrated.
If one of the components is colored then colourimetry may be appropriate.
Absorption or emission spectroscopy is common (more on these later).
For reactions involving chiral compounds, polarimetry (measurement of
optical activity) may be useful.
Other techniques include mass spectrometry, gas chromatography,
NMR/ESR, and many more.

17

(iii) Temperature control and measurement

For any reaction with a non-zero activation energy, the rate constant is
dependent on temperature. The temperature dependence is often modelled by the
Arrhenius equation,
k = A exp (-Ea/RT)
where k is the rate constant (min-1), Ea is the activation energy for the reaction (cal.
/ mole), T is the absolute temperature (K), R is the gas constant (cal. / mole. K),
and A is a constant known as the pre-exponential factor. This temperature
dependence means that in order to measure an accurate value for k, the temperature
of the reaction mixture must be maintained at a constant, known value. If
activation energies are to be measured as part of the kinetic study, rate constants
must be measured at a series of temperatures. The temperature is most commonly
monitored using a thermocouple, due to its wide range of operation and potential
for automation; however, standard thermometers are also commonly used.
There are numerous ways in which the temperature of a reaction mixture may
be controlled. For example, reactions in the liquid phase may be carried out in a
temperature-controlled thermostat, while reactions in the gas phase are usually
carried out inside a stainless steel vacuum chamber, in which thermal equilibrium
at the temperature of the chamber is maintained through collisions of the gas
molecules with the chamber walls. High temperatures up to 1300 K may be
obtained using conventional heaters. Low temperatures may be achieved by
flowing cooled liquid through the walls of the reaction vessel, and very low
temperatures may be reached by using cryogenic liquids such as liquid nitrogen
(~77 K) or liquid helium (~ 4 K). Extremely low temperatures (down to a few
Kelvin) such as those relevant to reactions in interstellar gas clouds may be
obtained by preparing the reactant gases in a supersonic expansion.

18

Catalytic Decomposition of Hydrogen Peroxide

Theory :
Inhibitor free hydrogen peroxide solutions decompose spontanouosly librating
oxygen in accordance with the following equation:
H2O2 (aq) = H2O (aq) + O2 (g)
The decomposition rate is markedly accelerated by solids such as manganese
dioxide or colloidal platinum, which act as catalysts. The course of reaction may be
followed either by titrating the peroxide with potassium permanganate in acid
medium, or by collecting the oxygen gas evolved.

Experiment:
Determination of the rate of hydrogen peroxide decomposition catalyzed by
manganese dioxide.

Procedure :
1. Prepare 250 ml of 0.1 N KMnO4 and 100 ml of 0.1 N H2O2 solution (Tenvolume hydrogen peroxide is approximately 3%). Thermostat the peroxide
solution at 25 oC. Add about 0.03 g manganese dioxide and record the time.
2. After about 3 minutes pipette out 10 ml of the decomposing mixture into a
flask containing about 10 ml of about 2.0 N sulfuric acid and titrate rapidly
with potassium permanganate recording the main time of titration.
3. Repeat the above step at increasing time intervals extending for about 80
minutes, i.e. 5, 8, 13, 20, 30, 45, 60 and 80 minutes.

19

Calculations:
1. Tabulate the results in the following order:
t,

(a-x),

log (a-x)

where, t is the main time of titration in minutes and (a-x) the amount of
undecomposed peroxide expressed in volume (ml) of KMnO4.
2. Plot log (a-x) against t to identify the order of reaction, then deduce the
value of k (reaction rate constant) and t1/2 (half-live time).

Results:
t

(a-x)

3
5
8
12
20
30
45
60
80

20

log (a-x)

Hydrolysis of Ethyl Acetate in Acid Medium

Theory:
Ethyl acetate hydrolyzes in water to give ethanol and acetic acid in
accordance with
CH3COOC2H5 + H2O = CH3COOH + C2H5OH
The reaction does not proceed at any measurable rate in pure water but is highly
catalyzed by hydrogen ions. Although, more than one molecular species are
involved, the reaction is kinetically of the first order since water is usually present
in a large excess. For a first order reaction, the rate constant k may be expressed as
k

2.303
a
log
t
(a x)

where a is the original concentration and (a-x) the concentration after time t.

Experiment:
Determination of the order of reaction and rate constant of hydrolysis of ethyl
acetate in acid medium.

Procedure :
1. Prepare 100 ml of 0.1 N HCl and 250 ml of 0.1 N NaOH solutions.
2. Transfer the whole amount of acid into a bottle + about 10 ml ethyl acetate.
3. After about 5 minutes withdraw 10 ml of the solution + 10 ml distilled
water. Titrate the solution rapidly with 0.1 N NaOH using phenolphethalin
as an indicator.
4. Repeat at increasing time intervals making a total about ten determinations
over a period extending for about 80 minutes.

21

5. Carry out one similar determination after a sufficiently long time, say 24
hours when hydrolysis is complete; or alternatively, run out 10 ml of the
ester solution into a small flask containing some water and fitted with an air
condenser. Boil in a water bath for about one hour to affect complete
hydrolysis. Wash the condenser into the flask and titrate with 0.1 N NaOH.

Calculations :
1. In any titration the amount (expressed in volume, ml) of alkali consumed
(Vt) is equivalent to the amount of HCl in 10 ml (VHCl) plus the amount of
acetic acid librated (x). After complete hydrolysis, the amount of alkali
consumed (V) is equivalent to the amount of HCl in 10 ml (VHCl) plus the
amount of acetic acid equivalent to all ester (a). The remaining ester
concentration after time t is therefore (a-x).
2. Plot log (a-x) against t and identify the order of reaction.
3. From the graph, calculate the rate constant k and the half-live time t1/2.

22

Results:

t, min

Vt = x + VHCl

V = a + VHCl

V - Vt = a - x

log(a-x)

5
15
25
35
45
55
65
80

Vt is the volume of alkali consumed at different time intervals (from step 3) and V is the
volume of alkali consumed after boiling (after completion of hydrolysis), x is the amount
of acetic acid librated and a is the amount of acetic acid equivalent to all ester.

23

Saponification of Ethyl Acetate in Alkaline Medium

Theory :
In the presence alkali ethyl acetate undergoes saponification in accordance
with
CH3COOC2H5 + OH- = CH3COO- + C2H5OH
The rate of saponification is directly proportional to both concentrations of ester
and alkali, and the reaction therefore, is a second order one, i.e.
1
x
k .
t a (a x)

where a and b are the initial concentrations of ester and alkali, respectively (a = b
in this case) and k is the reaction rate constant.

Experiment:
Determination of the saponification rate constant of ethyl acetate in alkaline
medium.

Procedure :
1. Prepare the following solutions:
100 ml of exactly 0.1 N Na2CO3,
100 ml of about 0.1 N HCl,
100 ml of exactly 0.1 N NaOH.
2. Standardize the acid against the carbonate and the hydroxide against the
acid.
3. By appropriate dilution prepare 100 ml of exactly 0.025 N HCl and 100 ml
of each of exactly 0.05 N and 0.025 N NaOH.
4. Prepare 100 ml of exactly 0.05 N ethyl acetate (density is 0.901 g/ml).
24

5. By means of a pipette, transfer 50 ml of 0.05 N ethyl acetate into a clean dry

flask and 50 ml of 0.05 N NaOH, record the mixing time (note that the
mixture will become 0.025 N with respect to each of alkali and ester).
6. Withdraw 10 ml portion of the reacting mixture, record the time (about 20
minutes from the start) and run immediately into a flask containing about
100 ml distilled water and exactly 10 ml of 0.025 N HCl. Titrate back the
excess HCl with 0.025 N NaOH using phenolphethalin as an indicator.
7. Repeat step (6) at increasing time intervals making a total about eight
titrations over a period extending for about 90 minutes.

Calculations :
1. If a is the amount of HCl equivalent to the original concentration of alkali
which equivalent to the consumed alkali titrant and consumed ester (0.025)
and x the amount of alkali equivalent to the excess HCl after time t, (a-x)
gives, hence, the amount of each of alkali and ester remaining (the two are
equal).
2. Tabulate the results in the following order:
t,

x,

(a-x),

x/(a-x)

3. Plot x/(a-x) against t to identify the order of reaction.

4. Knowing the original concentration a, the reaction rate constant k in (dm3
mol-1 min-1) may be calculated from the slope of the curve obtained.

25

Results:
t

(a-x)

20
30
40
50
60
70
80
90

26

x / (a-x)

Persulphate-Iodide Reaction
Theory:
The reaction between potassium persulphate and potassium iodide may be
expressed as
K2S2O8 + 2 KI = 2 K2SO4 + I2
The rate of reaction is determined by the concentration of both persulphate and
iodide. However, if potassium iodide is present in a large excess its concentration
may be regarded as constant and the reaction is kinetically of the first order.
Reactions in which more than one molecular species are involved and still satisfy
the first order equation are sometimes called pseudo-first (unimolecular) reactions.

Experiment:
Determination of the rate constant and half-life period of the persulphateiodide reaction.

Procedure :
1. Prepare the following solutions
100 ml of exactly 0.01 N K2Cr2O7 ,
250 ml of about 0.01 N Na2S2O3 . 5 H2O ,
50 ml of 0.2 M KI ,
50 ml of exactly 0.025 M K2S2O8 .
and thermostat the iodide and persulphate solutions at 25 oC.
2. Standardize the thiosulphate against the dichromate. (Dissolve about 2 g KI
in 10 ml water, then add 10 ml of dilute HCl. Dilute to about 100 ml, add 25

27

ml of 0.01 N K2Cr2O7 , leave for sometimes, then titrate the librated iodine
against the thiosulphate solution using starch as indicator).
3. In a dry bottle mix up quickly the iodide and persulphate solutions; register
the time and thermostat. The reacting mixture therefore, is initially 0.1 M
with respect to KI and 0.0125 M with respect to K2S2O8 .
4. After about 3 minutes pipette out 25 ml of the mixture into a conical flask
containing some distilled water and starch solution. Record the time of
dilution and titrate the librated iodine with the thiosulphate.
5. Follow the reaction by carrying out in the same way about eight titrations
over a period extending for about 90 minutes.

Calculations :
1. Calculate the amount of persulphate (x) decomposed at the end of each
interval expressing it as millimole of K2S2O3 per liter of mixture.
2. Tabulate the results in the following order:
t,

x,

a-x,

log(a-x),

where, t is the time in minutes, x is the amount of persulphate decomposed

(= millimoles of I2 librated = millimoles of K2S2O3 consumed) and a is the
initial concentration per liter of the original mixture (0.0125 M).
3. Plot log (a-x) against t, and deduce the values of k and t1/2 of the reaction.

28

Results:
t

(a-x)

3
5
8
12
20
30
45
60
80

29

log (a-x)

Hydrogen Peroxide - Hydrogen Iodide Reaction

Theory:
The overall reaction between H2O2 and HI which represented by the equation
H2O2 + 2 HI = 2 H2O + I2
is kinetically of second order -not, as might be expected, third order. The suggested
mechanism is probably as
H2O2 + I- = H2O + IO-

(slow),

IO- + 2 H+ + I- = H2O + I2

(fast)

The rate-determining step is the slow stage, Rate [H2O2][I-] (first order with
respect to both [H2O2] and [I-]). The order of the reaction with respect to H2O2 can
be studied conveniently by choosing conditions such that there is practically
constant excess of HI. Then, the rate of the reaction depends only on [H2O2] and
temperature and, hence, the kinetics then follows the first order law, Rate
[H2O2].
This is achieved experimentally by continually adding small volumes of
sodium thiosulphate solution to remove the iodine as soon as it is liberated and to
regenerate iodide according to the reaction
2S2O3-- + I2 = S4O6-- + 2INote that: by using a large volume of solution and adding small amounts of
concentrated thiosulphate solution, one can neglect the small increase of volume of
the solution and take the concentration of I- ions as constant.
The course of the reaction can readily be followed by timing the appearance
of iodine (indicated by starch solution) after the addition of a small known volume
of thiosulphate solution. The amount of iodine librated by the reaction at a series of
times corresponds to the volume of thiosulphate added. The total amount of iodine
30

librated at infinite time can be determined from a standardization of the hydrogen

peroxide used. Thus, it is possible to determine the concentration of hydrogen
peroxide at any time, since 1 mol of iodine is librated for every mol of hydrogen
peroxide destroyed.
The order of the reaction with respect to HI can be determined by determining
the first order velocity constant of the reaction with different concentrations of HI.
Generally, the rate equation of the overall reaction is
Rate = k [H2O2]a [HI]b
where, k is the rate constant, a and b are the order with respect to H2O2 and HI,
respectively.
The rate of this reaction can be determined by allowing the reaction to proceed
in the presence of thiosulphate and determining the time taken between mixing of
the reactants and the appearance of iodine. The reciprocal of the time interval is a
measure of the rate of reaction.

Experiment I:
Determination of the order of the reaction between hydrogen peroxide and
hydrogen iodide.

Procedure :
1. Prepare the following solutions
500 ml of 1.0 N H2SO4 ,
250 ml of 0.10 M KI ,
100 ml of 0.01 N Na2S2O3 . 5 H2O,
50 ml of 1 vol. H2O2 ,
Freshly prepared starch solution.
31

 To get the order with respect to H2O2:

2. In dry small flask bottom flasks make up the following series of mixtures
(volumes in ml):
Mixture
Solution

II

III

IV

1.0 N H2SO4

25

25

25

25

25

0.10 M KI

25

25

25

25

25

0.01 N Na2S2O3 . 5 H2O

Starch + distilled water

--

3. To each mixture add respectively and separately: 1, 2, 3, 4 and 5 ml of H2O2

(making a total volume of 60 ml), mix thoroughly and meanwhile start a
clock on. Determine the time period (t, sec.) indicated by the sudden
appearance of the blue color. The results are tabulated as follows:
VH2O2 (ml),

t,

1/t ,

log (1/t),

log VH2O2 .

4. At constant [I-], the rate law of the reaction can be written as follos:
Rate = = k [H2O2]a
Then,

log Rate = log k + a log [H2O2]

Considering the rate of reaction is measured as 1/t and [H2O2] is represented

by VH2O2
log (1/t) = log k + a log VH2O2
Plot log (1/t) against log VH2O2 . This gives a straight line, the slope of which
is a and the intercept is log k.

32

 To get the order with respect to HI:

5. In dry small flask bottom flasks make up the following series of mixtures
(volumes in ml):
Mixture
Solution

II

III

IV

1.0 N H2SO4

25

25

25

25

25

0.01 N Na2S2O3 . 5 H2O

H2O2

Starch + distilled water

23

18

13

6. To each mixture add respectively and separately: 5, 10, 15, 20 and 25 ml of

0.1 M KI solution (making a total volume of 60 ml), mix thoroughly and
meanwhile start a clock on. Determine the time period (t, sec.) between
addition of KI solution and the sudden appearance of the blue color. The
results are tabulated as follows:
VKI (ml),

t,

1/t ,

log (1/t) ,

log VKI .

7. Similarly,
log (1/t) = log k + b log VKI
Plot log (1/t) against log VH2O2 . This gives a straight line, the slope of which
is b and the intercept is log k.

33

Experiment II:
Determination of the rate constant and the energy of activation of the reaction
between hydrogen peroxide and hydrogen iodide.

Procedure:
1. Prepare 250 ml of the following solutions:
2.0 N H2SO4 ,
0.4 M KI solution ,
0.1 M Na2S2O3 . 5 H2O ,
1 vol. H2O2 ,
Freshly prepared starch solution.
2. Into a clean dry conical flask introduce 20 ml of the hydrogen peroxide
solution, add about 2 g solid potassium iodide and 10 ml of sulfuric acid.
Leave the mixture for about five minutes in a dark place, then titrate the
librated iodine with standard sodium thiosulphate solution, and, hence,
standardize the hydrogen peroxide solution.
Note that: the consumed volume of Na2S2O3 is equivalent to the librated I2 ,
equivalent to [H2O2] destroyed and equals a.
3. To 50 ml of potassium iodide solution in a dry bottle, add 20 ml of the
diluted sulfuric acid and place in a thermostat at about 25 oC. At the same
time have 20 ml of hydrogen peroxide solution and 10 ml of the starch
solution (in separate boiling tubes) at the same temperature.
4. Arrange the 50 ml burette containing the sodium thiosulphate solution above
the flask in the thermostat so that it will deliver directly into the solution,
add the starch and hydrogen peroxide solutions (with vigorously shaking)
34

and record the time at which a blue color appears, then add immediately 1
ml of the thiosulphate solution from the burette to discharge the color.
5. Continue the addition of 1 ml aliquots of sodium thiosulphate until the blue
color appears until the blue color takes five to six times the initial time to
reappear (it is essential that the reaction mixture be shaken continuously).
6. Repeat the experiment at various temperatures in the range 25 to 50 oC.
7. To determine the order of the reaction with respect to hydrogen iodide,
repeat the experiment (at 25 oC) now using half and double the amounts of
sulfuric acid and potassium iodide in the same total volume of the reaction
mixture.

Treatment of the experimental data and discussion :

1. The total amount of librated iodine at infinite time can also be determined
from the preliminary standardization. Thus, it is possible to determine the
concentration of hydrogen peroxide in mole per liter, [H2O2] at each time,
(a-x). Note that: x is the volume of Na2S2O3 added.
2. Plot a graph of ln [H2O2] (ln (a-x)) against t, at each temperature to obtain a
straight line with a slope of k (rate constant) at constant iodide ion
concentration (first order reaction) according to the equation:
ln [H2O2] = -k t + B
3. From the values of the rate constant at different temperatures, calculate the
activation energy of the reaction from the equation:
ln k = -Ea/RT + const.
by plotting the values of ln k against 1/T to get a straight line with a slope
of Ea/R, then calculate Ea (activation energy).

35

From the values of the rate constant at different iodide concentrations

determine the order of the reaction with respect to hydrogen iodide. The
overall reaction will be of a second order.

36

Halogenation of Acetone in Solution

Theory :
General acid catalysis was first established for the reaction between acetone
and iodine which can be represented by the equation
CH3 CO CH3 + I2 = CH3 CO CH2I + HI
The rate of such reaction is independent of the concentration of iodine (zeroorder reaction).

Experiment:
Investigation of the reaction between acetone and iodine.

Procedure:
1. Prepare the following solutions:
100 ml of 1.0 M H2SO4 ,
2.0 M acetone,
100 ml of 0.05 M I2 in 10% KI solution,
1.0 M sodium acetate,
250 ml of 0.02 M Na2S2O3 . 5 H2O ,
Freshly prepared starch solution.
2. Prepare the following four mixtures in four dry bottles (volumes in ml) kept
in a large water bath at room temperature

37

Mixture
Solution

II

III

IV

1.0 M H2SO4

20

20

25

20

0.05 M I2

20

25

20

20

Distilled water

50

45

45

45

3. To the first bottle add 10 ml of acetone and start (record) the time.
4. Remove 20 ml of the sample from the reaction mixture after 5 minutes
interval and run into 10 ml of sodium acetate solution to stop the reaction
and titrate the residual iodine against 0.01 M sodium thiothlfate using starch
indicator (till the solution becomes colorless).
5. Repeat the above titration at constant time intervals (5 min.).
6. Repeat the last three steps for the other mixtures.

Calculations:
1. Tabulate the volume of consumed sodium thiosulphate at different time
intervals for each.
2. Plot a graph of titre volume of sodium thiosulphate against time for each
mixture (you should obtain straight lines parallel to each other, i.e. k is
constant indicating that the reaction is zero order).
3. Determine the order of the reaction with respect to acetone, iodine and
sulfuric acid.
4. Investigate the effect of changing the concentration of: a) I2 , b) acetone
and c) acid on the rate of reaction.

38

Results:
Time,
min

Volume of consumed sodium thiosulphate

I

II

5
10
15
20
25
30
35
40
45
50
Rate = k [acetone] [acid] [iodine]

39

III

IV

Autocatalytic Reaction between Potassium Permanganate and

Oxalic Acid
Theory:
The reaction between potassium permanganate and oxalic acid in presence of
acid takes place according to the following equation:
2 KMnO4 + 5 H2C2O4 + 3 H2SO4 = K2SO4 + 2 MnSO4 + 10 CO2 + 8 H2O
Such reaction is catalyzed by manganese ions formed during the reaction. The
progress of the reaction can be followed by estimating the residual permanganate
concentration from time to time. This is done by running the samples of the
mixture to excess of KI and then titrating the liberate iodine with standered
Na2S2O3 solution. A plot of titre value of sod thiosulphate against the time reveals
the autocatalytic effect of Mn2+ ions.
The order of the reaction with respect to potassium permanganate can be
determined from these curves by determining the time required for half change
(half-life method). If the order of the reaction is n, then the half-life of the reaction
t1/2 depends on the initial concentration [A]0 of the reactant according to the
equation:

log t1 2

log 2 n 1 1

(n 1) log[ A]0
(n 1)k A

A plot of log t1/2 versus log [A]0 gives a straight line of slope (n-1) then calculate n.

40

Experiment:
Investigation of the reaction between potassium permanganate and oxalic acid

Procedure:
1. Prepare the following solutions
1.0 M H2SO4 ,
0.1 M oxalic acid,
0.02 M potassium permanganate,
0.2 M manganese sulphate,
2. Prepare the following mixtures (volumes in ml) kept in a large water bath at
room temperature.
Mixture
Solution

II

III

IV

0.2 N Oxalic acid

80

80

80

80

2.0 M H2SO4

10

10

10

10

0.4 M MnSO4

Distilled water

15

25

13

138

0.1 N KMnO4

20

10

20

20

Total volume, ml

125

125

125

250

3. At time t0 add the required volume KMnO4 to the mixture and start
stopwatch.
4. Withdraw 10 ml of the reaction mixture at regular time intervals and run into
5 ml of 5% KI taken in a conical flask. For reaction mixtures I and II, the
time interval can taken as 60 sec., while for reaction mixtures III and IV, it
can be taken as 30 sec.
41

5. Cover the mouth of the conical flask and keep it in the dark for 5 min till the
iodine is fully liberated. Titrate the liberated iodine with stander sodium
thiosulphate solution using starch solution as the indicator.
6. The titre value of sodium thiosulphate is equivalent to the concentration of
potassium permanganate in the reaction mixture at that time.

Calculations:
1. Plot a graph of the time against the titre of sodium thiosulphate for each
mixture.
The addition of Mn2+ in mixtures III and IV causes the autocatalytic part of
the curve, evident in I and II, to discharge. Finally, using the curves of III
and IV, determine the order of the reaction.

42

Results:
Titre value (volume)
Time min

II

43

III

IV

II
THERMOCHEMISTRY

44

INTRODUCTION

Thermochemistry is a part science deals with the heat changes accompanying

chemical reactions. This subject is based largely on the law of conservation of
energy.
.
Heat changes in chemical reactions
Since different substances have different amount of energy, the total energy
of the products of a chemical reaction may be different from the total energy of the
reactants, so that, the process may be accompanied by an absorption or liberation
of energy in the form of heat. If at ordinary temperature heat is liberated in the
reaction the process is said to be exothermic reaction, but if heat is absorbed it is
described as an endothermic reaction.

Heat of reaction
Since many reactions normally occur at constant (atmospheric) pressure the
heat changes are usual record in terms of Qp. So that the heat of reaction is
defined as the change in the heat content (enthalpy) accompanying the reaction at
constant pressure. For exothermic reaction (Qp = - H) and for endothermic
reaction ( - Qp = H).
As examples:
1)

C(s) + O2 (g) = CO2 (g) + 94030 cal

(exo.)

or

C(s) + O2 (g) = CO2 (g) ; H = 94.03 kcal.

this means that the quantity of heat (Qp) evolved is equal to 94.03 kcal.
45

2)

H2 (g) + I2 (g) = 2 HI (g) - 11900 cal.

(endo.)

or

H2 (g) + I2 (g) = 2 HI (g); H = 11.90 kcal.

this means that the quantity of heat (Qp) absorbed is equal to 11.90 kcal.

46

Heat Capacity
Theory:
The heat capacity (C) of a substance (or specific heat) is defined as the
amount of heat needed to raise the temperature of one gram of a pure substance by
1 oC or 1 K.
The rnolar heat capacity (C') is defined as the amount of heat (by joules)
needed to raise the temperature of one mole (or molar solution) of a pure substance
by I oC or 1 K.

Experiment I:
Determination of the heat capacity of the calorimeter.

Equipment:
Calorimeter - Bekmann thermometer - graduated cylinder - beaker (250 ml) distilled water.

Procedure:
1. Weigh the empty calorimeter W1 .
2. Introduce exactly 100 ml of hot distilled water (60 "C.) in the calorimeter
and record tire temperature quickly as possible T1 .
3. At steady state (constant temperature over two minutes) record T2 .
4. Weigh the calorimeter with its contents W2 .
You can make a simple calorimeter as shown in the Figure below.

47

Calculations:
1. Calculate the weight of distilled water W3 = W2 -W1 .
2. Where Q the amount of heat absorbed by the calorimeter: the amount of heat
lost by water, hence;
Q = W3 x Cwater x T
where, T = (T1 T2).
3. The heat capacity of the calorimeter;
Cc = Q / T

Results:
W1

W2

W3 = W2 -W1

48

T1 (K)

T2 (K)

T = T1 T2

Experiment II:
Determination of the heat capacity of different solutions of NaCl.

Equipment:
Calorimeter - Bekmann thermometer - graduated cylinder - beaker (250 ml) distilled water solid NaCl.

Procedure:
1. Prepare (10 N) NaCl solution [585 g in 1000 m1].
2. Use the dilution law: N x V = N' x V' to prepare (2,4,6, and 8 N) NaCl
solutions.
3. Weigh the empty calorimeter W1 .
4. Introduce exactly 100 ml of hot (5N) NaCl solution (50 oC) in the
calorimeter and record the temperature quickly as possible T1 .
5. At steady state (constant temperature over two minutes) record T2 .
6. Weigh the calorimeter with its contents W2 .
7. The weight of NaCl solution, W3 = W2 - W1 .
8. Repeat steps (2 - 4) by using different concentrations of NaCl.

Recording Data:
Cs

W1

W2

W3 = W1 W2

49

T1 (K)

T2 (K)

T = T1 T2

Calculations:
1. Where Q the amount of heat absorbed by the calorimeter = the amount of
heat lost by solution, hence;
Qc = QNaCl
So that;
Cc x T = W3 x CNaCl
Cc = the heat capacity of calorimeter (from the previous experiment) and
T = T1 T2
2. Calculate CNaCl, where;
CNaCl = Cc x T/W3
3. Plot QNaCl against concentration, comment.
4. Calculate the molar heat capacity of NaCl from the relation
C = H' = Q x 1000/N x 100
it must be the same for all concentration, (calculate the average).
5. Plot log QNaCl against concentration and extrapolate the straight line to zero
concentration, then calculate C, at infinite dilution from the intercept.
6. Determine the heat capacity of 5 N NaCl.
7. Repeat this experiment by using NH4CI.

Results:
Item

Calc.

= Cc x T =

CNaCl

= Q / W3 =

CNaCl

= H = (Q x 1000) / (N x 100) =

50

Result

Heat of Solution
Theory:
When a solid solute dissolved in a suitable solvent an amount of heat evolved
or absorbed as a result of formation of solution. The quantity of heat depends on
the types of the two components and changes as the concentration of solution
change. Heat of solution may be defined according to the condition of the reaction
(temperature, pressure, saturated solution, dilutes solution, etc).
Heat of solution for saturated solution is the change in heat content when one
mole of solute dissolved in a volume of water (solvent) of the nearly saturated
solution. Heat of solution for infinite dilution is the change in heat content when
one mole of solute dissolved in a large amount of water (solvent) till infinite dilute
solution.

Experiment:
Determination of heat of solution of ammonium chloride (as endothermic
reaction) at infinite dilution.

Using suitable calorimeter to calculate the heat of solution for different

concentrations. The extrapolation of the straight line obtained from the plot of the
relation between the concentration and the heat of solution to Y axis, gives an
intercept which equals to the heat of solution at infinite dilution.

Equipment:
Calorimeter - Bekmann thermometer - graduated cylinder - beaker (250 ml)distilled water - ammonium chloride.
51

Procedure:
1. Weigh the empty calorimeter W1 .
2. Introduce exactly 100 ml of distilled water in the calorimeter and record the
temperature T1 .
3. Weigh the calorimeter with its water W2 , hence;
W3 (water) = W2 - W1
4. Add W4 of NH4Cl (5 g), hence;
W5 (solution) = W3 + W4
5. Shake or stir the closed calorimeter to dissolve the solid.
6. At steady state (constant temperature over two minutes) record T2 .
7. Repeat steps (2 - 6) with different weights of NH4CI as (8, 12, 16, 20 g).

Recording Data:
Cc

Csol

T1

T2

W1

W2

Calculations:
1. Calculate the molality of solution from the relation;
m = (W4/W3) x (1000 / M) molal
2. Calculate the absorbed heat by the solution (H1), where
H1 = Csol (NH4Cl, aq) x W5 x T ;
consider Csol = 3.975 cal/g for all concentrations.
3. Calculate the absorbed heat by calorimeter (H2),
H2 = Cc x T
4. The total heat absorbed: H3 = H1 + H2 .
52

W3

W4

W5

5. Heat of solution: H = H3 / n = H3 x M/ W4 .
6. Plot the relation between m and T; comment.
7. Plot the relation between m and H and determinate H at infinite dilution
and the molar heat of solution (H') at m = 1 .

Results:
Item

Calc.

M, molal

= (W4 / W3) x (1000 /M) =

H1

Csol x W5 x T =

H2

= Cc x T =

H3

= H1 + H2 =

= H3 x M / W4 =

For exothermic reaction use NaOH instead of NH4Cl.

53

Result

molal

Heat of Neutralization
Theory:
Heat of neutralization is defined as; the constant quantity of heat liberated
when one mole of strong acid is neutralized with one mole of strong base to
produce one mole of water. As an example;
HCl (aq) + NaOH (aq) = NaCl (aq) + H2O + Q
The reaction can be written as:
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) = Na+(aq) + Cl-(aq) + H2O; H = -13.733 cal/mol.
this indicates that the process is an exothermic reaction. Strictly speaking (aq)
implies that the reaction is taking place in such dilute solution that the addition of
further solvent causes no heat change, i.e. the heat of dilution is zero; this is
exactly true, however, only at infinite dilution. The constant quantity of heat a is
equal to the heat of formation of one mole of undissociated water from
combination of one mole of H+ and one mole of OH-, where
H+(aq) + OH-(aq) = H2O ; H = - 13.733 cal/mol.
The neutralization reactions of week acid or week base evolved not only heat
of neutralization but also heat of ionization. So the quantity of heat of reaction Q
will be either lower or higher than 13.733 cal/mol, according to the endothermic or
the exothermic ionization process.

Experiment:
Determination of the heat of neutralization of hydrochloric acid and sodium
hydroxide.

54

Equipment:
Calorimeter - Bekmann thermometer - graduated cylinder - beaker (250 rnl) distilled water - burette - pipette - conical flask - funnel - spatula - ph.ph. indicator.

Procedure:
1. Prepare 500 ml of 5N HCI and 500 ml of NaOH, thermostat the two solution
at room temperature T1 .
2. Titrate 50 ml NaOH (in a flask) against 5N HCI by using ph. Ph. as
indicator, determine V1 (HCl).
3. Weigh the empty calorimeter W1.
4. Place 50 ml of 5N NaOH in the calorimeter and record the temperature at
steady state T2.
5. Introduce quickly V1 (HCl) and justly record the temperature T3.
6. Weigh the calorimeter with its contents W2 .
7. The weight of NaCl solution, W3 = W2 W1.

Recording Data:
Cc

CNaCl

V1

W1

W2

W3

T1

T2

T3

Calculations:
1. Calculate T = [T3 - (T1 + T2) / 2]; T1 mal be = T2 .
2. Calculate the heat absorbed by 5N NaCl solution where,
H1 = CNaCl x W3 x T
consider (CNaCl = 3.895 cal), or use the heat capacity of 5N NaCl solution
55

(obtained from previous experiment).

3. The heat absorbed by the calorimeter;
H2 = Cc x T
where, Cc from Previous experiment.
4. Calculate heat of neutralization where;
H = H1 + H2
5. Calculate the number of water produced from neutralization reaction
(undissociated water) where;
n = (5 x 36.5 x V1) / 1000
6. Calculate the molar heat of neutralization;
H' = H / n

Results:
Item

Calc.

= T3 - (T1 + T2) / 2 =

H1

= CNaCl x W3 x T =

H2

= Cc x T =

= H1 + H2 =

= (5 x 36.5 x V1) / 1000 =

= H / n =

56

Result

Hesss Law
Theory:
Hess's law is a law stating that the heat given off or absorbed in a chemical
reaction is the same regardless of whether the reaction occurs in a single step or in
many steps. It is often called the law of constant heat summation and it is direct
consequence of the law of conservation of energy. The amount of heats of reaction
is dependent only on the initial and final states. As an example;
A -------- HI ----- B
H reaction = H1+ HII = HIII + HIV

HIII

HII

C ------- HIV ----- D

Experiment:
Application of Hess's law.

The reaction between HCl, H2O and NaOH can be runs in two different ways
as following;
I]

II]

a) H2O (L) + HCl conc. = HCl (aq) ;

H1

b) HCl (aq) + NaOH (s) = NaCl (aq) + H2O (L) ;

HII

a) H2O (L) + NaOH (s) = NaOH (aq) ;

HIII

b) NaOH (aq) + HCl conc. = NaCl (aq) + H2O (L) ;

HIV

Equipment:
HCl conc. NaOH (s) - distilled water thermometer.

57

Procedure (Run I):

1. Thermostat the compounds at room temperature.
2. Weigh (in a galas watch) 16 g of NaOH.
3. Introduce 95 ml of distilled water into the calorimeter and record the
temperature T1.
4. Insert 4 ml of conc. HCI and record the higher temperature T2.
5. At steady state (constant T about 2 min.) record T3.
6. Introduce the weighed NaOH and quickly cover the calorimeter and shake
carefully, record the higher temperature obtained T4.
7. At steady state record T5.

Procedure (Run II):

1. Thermostat the compounds at room temperature.
2. Weigh (in galas watch) 16 g of NaOH.
3. Introduce 100 rnl of distilled water into the calorimeter and record the
temperature T1.
4. Introduce the weighed NaOH and quickly cover the calorimeter and shake
carefully, record the higher temperature obtained T2.
5. At steady state (constant T about 2 min.) record T3.
6. Still 5 min. and insert 4 ml of conc. HCI and record the higher temperature
T4.
7. At steady state record T5.

58

Recording Data:
Run I
T1

T2

T3

Run II
T4

T5

T1

T2

T3

T4

T5

Calculations and Results (Run I):

H1

HII

Item
T1 = T2 T1
HW = T1 x VW (ml) x CW
T2 = T2 T3
Hc = T2 + Cc
HI = Hw + Hc
T3 = T4 T3
HW = T3 x VW (ml) x CW
T4 = T4 T5
Hc = T4 + Cc
HII = Hw + Hc
H1 + H2

=
=
=
=
=
=
=
=
=
=
=

Calc.
x
x
x
+
x
x
x
+
+

=
=
=
=
=
=
=
=
=
=
=

Calc.
x
x
x
+
x
x
x
+
+

Result
=
=
=
=
=
=
=
=
=
=
=

Calculations and Results (Run II):

Item
T1 = T2 T1
HW = T1 x VW (ml) x CW
H1
T2 = T2 T3
Hc = T2 + Cc
HI = Hw + Hc
T3 = T4 T3
HW = T3 x VW (ml) x CW
HII
T4 = T4 T5
Hc = T4 + Cc
HII = Hw + Hc
H
H1 + H2
Interpret your results
59

Result
=
=
=
=
=
=
=
=
=
=
=

III
PHASE EQUILIBRIA

60

INTRODUCTION

Two Components System

When two liquids are mixed together, one of the following cases may arise:
(a) The two liquids are completely miscible at all proportions yielding one
homogeneous liquid pha5e, for example alcohol and water.
(b) The two liquids are partially miscible yielding either one or two liquid
phases, depending on the conditions, for example phenol and water.
(c) The two liquids are practically immiscible yielding always two distinct
phases under ordinary conditions, for example carbon disulphide and water.

The mutual solubility of partially miscible liquids usually increases with

temperature. In this case, the solubility curve exhibits a maximum at the critical
solution temperature above which the two liquids become completely miscible at
all proportions. For Some liquid pairs such as ether and water, however, the mutual
solubility decreases with temperature, and the solubility curve shows a minimum at
the critical solution temperature below which the two liquids become completely
miscible at all proportions.

Composition-Temperature Diagrams
The temperature-composition diagram of the water-phenol system as shown
in the figure. Outside the area bounded by the curve ABC, there occurs one
unsaturated homogeneous liquid phase. Within that area, two liquid phases in
equilibrium with each other coexist; one is water saturated with phenol and the
other phenol saturated with water. Any point on the curve represents one saturated
61

homogeneous phase; the existence of the saturating phase should be assumed. As

the solubility curve is hardly affected by pressure, the system may be treated as a
condensed One of two components. For condensed systems the phase rule may be
expressed as
F=C-P+1
where F is the number of degrees of freedom, C the number of components and P
the number of phases. Outside the area enclosed by the curve, since P = 1,
therefore the number of degrees of freedom F is 2, which means that the
temperature and concentration, as variants, may be changed independently. For any
point on the curve, P = 2,therefore F is 1, meaning that concentration must change
with temperature. For the points enclosed within the curve, the situation iq the
same for any particular layer as for any point on the curve.

Temp

C
Composition

62

Experiment:
Determination of critical solution temperature of water-phenol system.

Procedure:
1. In a clean dry test tube (phenol tube) weigh accurately about 1 g phenol.
2. From a burette, add 0.5 ml of distilled water. Cover the tube with a cork
stopper carrying a thermometer and a stirrer, then place in a beaker
containing water to serve as bath.
3. Heat (or cool) gradually while the mixture is constantly stirred until the two
layers disappear forming one homogeneous layer. The two temperatures (t1
and t2), at which this occurs on passing from a lower (t1) to a higher (t2)
temperature and the reverse, are recorded. These two temperatures should be
nearly the same, and their mean gives the miscibility temperature of the
mixture used.
4. To the same mixture add the necessary volumes of water (0.5, 1, 1.5,) and
heat gradually, then determine the miscibility temperature of the new
mixture as described above.

Calculations:
1. Record the volume of water used for each composition.
2. Plot miscibility temperature against percentage water or phenol for the
various mixtures.
3. From the curve obtained find out the critical solution temperature and the
corresponding composition.

63

Results:

64

Three Components System

Theory:
With a system of three components, four variables are possible; the pressure,
temperature and two concentration terms (the concentration of the third component
will be automatically fixed). To simplify the study of the phase properties, the
system is treated as a condensed one at a constant temperature, in which case the
pressure and temperature as variables, are dispensed with. The phase rule
expression reduces hence to: F = C - P. Under such conditions, the phase
properties are best defined by using the triangular diagram. On an equilateral
triangle (as shown in figr.rre) the apexes A, B and C represent pure components
(100% each). A point on any one side represents a mixture of two components
only. A point P inside the triangle represents the composition of a mixture of A, B
and C of percentages respectively proportional to the lengths of the lines Pa, Pb
and Pc drawn parallel to the sides of the triangle. This contention is borne out by
the fact that in an equilateral triangle the sum of Pa + Pb + Pc (also for any point
other than P) is always equal to the length of any one side (corresponding to a total
of 100%).
If components A, B and C are completely miscible with each other at all
proportions, then any point inside the triangle represents a system of three
components and one phase; therefore F, the number of degrees of freedom, is 2,
which means that the concentrations of any two components can be varied with
respect to one another while that of the third component is maintained constant. If
components B and C form a pair of partially miscible liquids, a mixture of the two
composition X (as shown in the figure) will separate into two layers having the
composition determined by points b and a (compare the phenol-water system). If
65

component A is gradually added to the above mixture, the composition, will vary
following points on the line Ax. If A is completely miscible with both B and C, it
will distribute itself between the two layers and eventually a composition
corresponding to point M is reached where complete miscibility is observed.
Similarly, for any other mixture of A and B of composition between a and b, a
point is reached where there is complete miscibility. The line connecting the
various points is the bimodal curve b M a. Within this curve (immiscibility region)
any point represents a system with C = 3 and P = 2; therefore: F = l, which means
that changing the concentration of one component, the concentrations of both other
components must change. Outside the curve, is the region of complete miscibility
and is treated as explained before.

66

Experiment:
Construct the binodal curve for the system ethyl acetate ethyl alcohol-water.

Procedure:
1. Into five dry stopper bottles introduce the following volumes of ethyl acetate
and water.
Bottle

II

III

IV

Ethyl acetate, ml

10

Water, ml

10

The mixtures will appear turbid. Thermostat the bottles at 30 oC.

2. From a burette, run in ethyl alcohol in small quantities at a time into each of
the bottles in turn. shake well after each addition and thermostat again.
3. Continue addition of ethyl alcohol till turbidity just disappears on shaking.
(The final additions should be made drop by drop).

Calculations:
1. Calculate the percentage composition by weight of each mixture at the stage
when turbidity lust disappears.
Densities at 30 oC are
Ethyl acetate = 0.894 g/c.c.
Ethyl alcohol = 0.789 g/c.c.
Water = 0.996 g/c.c.
2. Tabulate the results and plot them on a triangular diagram. Join the points by
a smooth curve to obtain the binodal curve.

67

Results:

68