B.Sc.

(Hons) Semester-II
CHB-201 (Section-B)
Batch: N(E), LTC-102
Dr. Manivannan S
Assistant Professor
Dept. of Chemistry, BHU

Physical Chemistry-I (Credits: 2)

1. Gaseous and Liquid States
2. Thermodynamics
3. Chemical Kinetics
Physical Chemistry:
• Quantitative and theoretical study of the properties
and structure of matter, and their relation to the
interaction of matter with energy.

• # This course serves as an introduction to chemical

thermodynamics, giving you an understanding of basic
principles, laws and theories of physical chemistry the
are necessary for chemistry, biochemistry, pre-medical,
general science and engineering students.

• # You will develop the ability to solve quantitative

problems, and learn to use original thought and logic in
the solution of problems and derivation of equations.

• # You will learn to apply mathematics in chemistry in

such a way that the equations paint a clear picture of
the physical phenomena

Introduction &
Course Overview
 1. Gaseous and Liquid States: Kinetic theory of gases and ideal gas laws, collisions in
a gas: collision number, collision diameter and mean free path, behavior of real gases:
Van der Waal’s equation and its applicability, the critical state: critical constants and their
determination, law of corresponding states, Surface tension of liquids: capillary action,
measurement of surface tension, viscosity of liquids and its measurement, temperature
effect on surface tension and viscosity.
2. Thermodynamics: Thermodynamic quantities (w, q, ΔU and ΔH) for isothermal and
adiabatic reversible expansion of ideal gases, variation of heat of reaction with
temperature (Kirchhoff’s equation), Joule-Thomson effect, Joule-Thomson coefficient of

Syllabus
real (van der Waals) gases, Second Law of Thermodynamics: entropy, entropy changes
for an ideal gas, entropy changes at constant pressure and volume, entropy change in
spontaneous processes, physical significance of entropy, Carnot cycle, free energy and
maximum work functions, conditions for spontaneous changes and equilibrium, Maxwell
relations, Gibbs-Helmholtz equation, van’t Hoff equation, reaction isotherm.
3. Chemical Kinetics: Zero, first and second order kinetics, determination of rate
constant and order of reactions, effect of temperature on rate constant, Arrheninus
equation, collision and activated complex (transition state) theories of rate of reactions.
Books Recommended
• 1. Physical Chemistry, P. C. Rakshit, 5th Edition (1988), 4th Reprint (1997), Sarat Book House,
Calcutta.
• 2. Principles of Physical Chemistry, B. R. Puri, L. R. Sharma and M. S. Pathania, 44th Edition (2009),
Vishal Publishing Co., Jalandhar.
• 3. Physical Chemistry, K. J. Laidler and J. M. Meiser, 3rd Edition, (1999) Houghton Mifflin Comp.,
New York, International Edition.

3
 Hints on how to study in physical chemistry courses
• Summarize each set of notes on one page in an
organized form that helps to isolate all key points: “nerd
notes”
• Download all available handouts, including equation
sheets
• Start working on problems with the equation sheets
a.s.a.p. and do not fall behind

Studying • Physical Chemistry is not a “memory-based”, learn-by-

rote discipline, but is centered upon problem-based

Physical
learning.
• However, you must practice solving problems, deriving

Chemistry
equations, etc. to become proficient.
• Review assigned and in-class problems
• Try the problems with your solutions manual
• Attend tutorials
• View animations and use other web resources
• Book consultation times after you have attempted most
of the problems

4
 Physical Chemistry includes numerous
disciplines:

Thermodynamics - relationship between

energy interconversion by materials, and
the molecular properties

What is Kinetics - rates of chemical processes

Physical Quantum Mechanics - phenomena at the

molecular level

Chemistry? Statistical Mechanics - relationships

between individual molecules and bulk
properties of matter

Spectroscopy - non-destructive
interaction of light (energy) and matter, in
order to study chemical structure

Photochemistry - interaction of light and

matter with the intent of coherently
altering molecular structure

5
Unit-1 Gaseous
and Liquid
States

6
Unit-1a Gaseous State

7
 Kinetic Theory of Gases and Ideal Gas Laws
• The kinetic theory of gases is a simple, historically significant model of the thermodynamic behavior
of gases, with which many principal concepts of thermodynamics were established.

• The model describes a gas as a large number of identical submicroscopic particles (atoms or molecules), all
of which are in constant, rapid, random motion.

• Their size is assumed to be much smaller than the average distance between the particles. The particles
undergo random elastic collisions between themselves and with the enclosing walls of the container.

• The basic version of the model describes the ideal gas and considers no other interactions between the
particles.

• The kinetic theory of gases explains the macroscopic properties of gases, such as volume, pressure, and
temperature, as well as transport properties such as viscosity, thermal conductivity and mass diffusivity.

• The model also accounts for related phenomena, such as Brownian motion.

• The temperature of the ideal gas is proportional to the average kinetic energy of its particles.

• Ex: The size of helium atoms relative to their spacing is shown to scale under 1950 atmospheres of pressure.

• The atoms have a certain, average speed, slowed down here two trillion-fold from that at room temperature.

8
 • The gas consists of very small particles.
• This smallness of their size is such that the sum of
the volume of the individual gas molecules is negligible

The application compared to the volume of the container of the gas.

• This is equivalent to stating that the average distance

of kinetic theory separating the gas particles is large compared to their size, and
that the elapsed time of a collision between particles and the

to ideal gases
container's wall is negligible when compared to the time
between successive collisions.

makes the
• The particles have the same mass.
• The number of particles is so large that a statistical treatment of

following the problem is well justified. This assumption is sometimes

referred to as the thermodynamic limit.

assumptions: • The rapidly moving particles constantly collide among

themselves and with the walls of the container. All these
collisions are perfectly elastic, which means the molecules are
perfect hard spheres.
• Except during collisions, the interactions among molecules are
negligible. They exert no other forces on one another.

9
What are the 5 assumptions of the kinetic theory of gases?

The kinetic-molecular theory of

gases assumes that ideal gas molecules

(1) are constantly moving;

(2) have negligible volume;

(3) have negligible intermolecular forces;

(4) undergo perfectly elastic collisions; and

(5) have an average kinetic energy proportional

to the ideal gas's absolute temperature.

10
The
Gaseous Solid Liquid Gas
State Holds Shape Shape of the Container
Shape of the Container
Fixed Volume Free Surface
Volume of the Container
Fixed Volume

11
The Gas Laws
• The word gas comes from gaos, a Dutch form of the word Chaos.
• Gases were the last substances to be understood chemically.
• Solids and liquids were easy to identify and differentiate, but the idea of different kinds of “ayres” came only slowly.
• Carbon dioxide was not prepared from limestone until 1756.
• Hydrogen was discovered in 1766: nitrogen, in 1772:and oxygen, in 1781.
• Although gases were late in being identified, they were the first substances whose physical properties could be explained
In terms of simple laws.
• It is fortunate that when matter in this most elusive state is subjected to changes.
• In temperature and pressure, it behaves according to rules much simpler than those that solids and liquids follow.
• Moreover, one of the best tests of the atomic theory is its ability to account for the behavior of gases.
• Given any trapped sample of gas we can measure its mass, its volume, its pressure against the walls of a container, its
viscosity, its temperature and its rate of conducting heat and sound.
• We can also measure the rate at which it effuses through an orifice into another container, and the rate at which it diffuses
through another gas.
• In this chapter we shall show that these properties are not independent of one another, that they can all be related by a
simple theory which assumes that gases consist of moving and colliding particles.

12
 1) Pressure and Temperature

How are 2) Pressure and Volume

each of
the 4) Temperature and Volume

following
related? 3) Pressure and Amount of Gas

5) Volume and Amount of Gas

13
 Amount of Gas:
-Increasing the number of particles increases
collisions, which increases pressure.
-Removing particles reduces pressure.

Factors Volume:

Affecting
-Increasing the volume will decrease the
pressure of a gas since collisions are less likely.
-Decreasing the volume has the opposite effect.

Pressure Temperature:
-Increasing the temperature increases the speed
of the molecules, which leads to more collisions
and greater pressure.
-Decreasing the temperature has the opposite
effect.

14
 Units of Pressure

Pressure is force per unit area (P = F/A)

atm = atmospheres
kPa = kilopascals
torr = torr
mmHg = millimeters of mercury
psi = pounds per square inch

1 atm = 101.325 kPa = 760 torr = 760 mmHg = 14.7 psi

Units can easily be converted from one to another by using

dimensional analysis.
Barometer, Evangelista Torricelli (1608-1647)
-It was the pressure at the bottom of the Mercury column Example: 0.89 atm = 760 torr = 676.4 torr 1 atm
that mattered, and not the total weight of Mercury;
-thus the height of the Mercury in a barometer tube is
15 independent of the size or shape of the tube.
 Boyle’s Law
“If the temperature is constant, as pressure of a gas increases the volume decreases”

PV = K P1V1 = P2V2

Pressure on Year: 1662

Gas, Pa + h
⚫ When devising vacuum pumps for removing air from vessels, he noticed a property
familiar to anyone who has used a hand pump for inflating a tire or football, or who
Gas has squeezed a balloon without braking it: As air is compressed, it pushes back with
increase vigor.
Atmospheric Pressure on
Pressure, Pa
Burette h ⚫ Boyle called this the “Spring of the air”, and measured it with the simple device
Gas, Pa + h
shown in Figure
Atmospheric
Pressure, Pa
J-tube ⚫ (a) When the height of the column is equal in the open and closed parts of the
tube, the pressure exerted on the gas sample is equal to atmospheric pressure.
Mercury ⚫ (b) The pressure on the gas is increased by adding Mercury to the tube.
reservoir
h Mercury ⚫ (c) The gas burette, a device employing the same principle as the J-tube
Vgas V’gas apparatus. The gas is at atmospheric pressure.
Mercury
⚫ (d) The pressure on the gas is increased by raising the Mercury reservoir.
⚫ In (a) and (b) the cross section of the J-tube is assumed constant. So the height
Flexible
tube
of the gas sample is a measure of volume. In (c) and (d) the volume of the gas is
Mercury

(a) (b) (c) (d) measured by the calibrated burette.

16
 Avogadro Number
• Avogadro’s number tells us the number of particles in 1 mole (or mol) of a substance. These particles
could be electrons or molecules or atoms. The value of Avogadro’s number is
approximately 6.022140857×1023 mol−1.

What is Avogadro’s Number?

⚫ The number of units in one mole of any substance is called Avogadro’s number or Avogadro’s constant.
⚫ It is equal to 6.022140857×1023.
⚫ The units may be electrons, ions, atoms, or molecules, depending on the character of the reaction and the nature of
the substance.
So, if you wanted to know the number of particles in 3 moles of a substance, the value would be:
= 3 x 6.023 x 1023
= 1.81 x 1024 particles

17
 What is so important about
Avogadro’s constant?
⚫ It creates a bridge between the macroscopic world and the microscopic world by relating the amount of
substance to the number of particles.
⚫ It also provides the relationship between other physical constants and properties.
⚫ Some of them are:

•The relationship between the gas constant R and the Boltzmann constant kB: R=kBNA
•The relationship between the Faraday constant F and the elementary charge e: F=NAe
•The relationship between atomic mass unit u and molar mass constant Mu: 1u=Mu/NA

In chemistry, we always take a macroscopic approach to measuring stuff. We measure the total volume of a
substance, or the temperature, or the mass of a substance and general things along those lines.

But if we look at this from the atomic level, knowledge of velocity and momentum of particles are important. The
atomic mass is important. Avogadro’s number connects both of these.

18
“As the temperature of an enclosed gas increases, the pressure increases at constant volume”

How was Avagadro’s Number Determined?

⚫ Avagadro grew up during the important period of development of chemistry.
⚫ Chemists such as John Dalton and Joseph Louis Gay-Lussac began to understand the basic
properties of atoms and molecules, and they debated how these infinitesimally small particles
behaved.
⚫ Gay-Lussac’s law of combining volumes particularly interested Avagadro.
⚫ Tinkering around with the consequences of this law, Avogadro expected that with the goal for
this to be valid, equivalent volumes of any two gases at a similar temperature and weight must
hold an equivalent number of particles.
⚫ And the only way to confirm that this law could be true was if there was a difference between
atoms and molecules and that some elements, such as Nitrogen, actually exist as molecules (N2
rather than simply N).
⚫ Given, Avogadro didn’t have words such as “molecule” to explain his theory, and his ideas met
opposition from John Dalton, among others.
⚫ It took another chemist Stanislao Cannizzaro to bring Avogadro’s ideas the attention that
it deserved.
⚫ By the time those ideas gained traction, Avogadro had already passed away.
“Because Avogadro’s law was so critical to the advancement of chemistry, chemist Jean Baptiste
Perrin named the number in his honour”.

19
 ⚫ In the atomic level substances are measured as per atomic mass unit.

⚫ The Atomic mass unit is defined as the 1/12th weight of the mass of one

Significance carbon atom.

of
⚫ For example, the atomic mass unit of Hydrogen is 1.00794 amu.

⚫ Now to calculate the ability of a single particle (atom, electron, molecule)

Avogadro’s to say, carry out a reaction isn’t possible.

Number
So instead, chemists came up with a way to link the atomic mass
unit and the gram.
1 amu = 1.66 x 10-24 grams

Using this, we are able to convert between measurement in grams and the
invisible unit of measurement of the atomic mass unit. And hence, this is the
significance of Avogadro’s number.

20
 Avogadro's law

-Avogadro's law states that "equal volumes of all gases, at the same temperature and pressure, have the same number of molecules."

-For a given mass of an ideal gas, the volume and amount (moles) of the gas are directly proportional if the temperature and pressure are Year: 1812
constant.

⚫ In practice, real gases show small deviations from the ideal behavior and the law
holds only approximately but is still a useful approximation for scientists.

V is the volume of the gas;

n is the amount of substance of the gas (measured in moles);
k is a constant for a given temperature and pressure.

-This law describes how, under the same condition of temperature and pressure, equal
volumes of all gases contain the same number of molecules.

-For comparing the same substance under two different sets of conditions, the law can
be usefully expressed as follows:

▪ The equation shows that, as the number of moles of gas increases, the volume of the
gas also increases in proportion.

▪ Similarly, if the number of moles of gas is decreased, then the volume also decreases.

▪ Thus, the number of molecules or atoms in a specific volume of ideal gas is

21 independent of their size or the molar mass of the gas.
 Charles’s Law
“If the pressure is constant, as temperature of a gas increases the volume increases”
*Temperature must be in Kelvin for all gas laws*

*To get from °C to K, add 273

V/T= K V1/T1 = V2 /T2 Year: 1787

⚫ We know that air expands on heating, thereby decreasing its density. For this reason, balloons rise
Scale when inflated with warm air.
⚫ About 100 years after Boyle derived his law Jacques Charles (1746-1823), in France, measured the effect
of changing temperature on the volume of an air sample.
⚫ This measurement can be made quite easily with the device shown in the Figure.

Air in Capillary Tube ⚫ Experimental determination of the relationship between volume and temperature of a gas.
⚫ The apparatus consists of a small capillary tube and a thermometer mounted on a ruled scale and
immersed in a hot oil bath.
⚫ As the system cools, the oil rises in the tube, and the length of air space and the temperature are
measured at intervals.
⚫ For a tube of constant bore, the length of the air space is a measure of the gas volume.
Hot Oil of Known ⚫ So long as the bottom of the air space in the capillary is maintained at the same depth below the
Temperature surface of the oil bath, the pressure in the capillary will be constant.

22
 P/T= K P1/T1= P2/T2
Gay- Year: 1802
Lussac’s *To get from °C to K,

Law
“As the temperature of an enclosed gas add 273
increases, the pressure increases at constant
volume”
 PV/T= K P1V1/T1 = P2V2/T2

Combined “The combined gas law allows you to do

calculations for situations in which only the
Gas Law amount of gas is constant”
 PV = nRT

-The moles of gas is no longer a constant and is now represented by “n”.

Ideal Gas There is also a gas constant, “R”.
-The gas constant depends on the unit for pressure.
Law
R = 0.0821 L*atm/mol*K R = 8.31 L*kPa/mol*K
Ideal vs. Real Gases

In order to behave as an This is impossible, Real gases differ Checkpoint:

ideal gas, gases could not however, under certain most from an Why are real
have any volume and conditions real gases can ideal gas at low and ideal gases
could be behave very similarly to temperatures and different under
attracted to other gas an ideal gas. high pressures. these
molecules. conditions?

26
 In a mixture of gases, the total pressure is the sum of the
partial pressures of the gases at constant temperature.

Dalton’s
Law of Ptotal= P1 + P2 + P3 + ...

Partial
Pressure
Kinetic explanation of Dalton's law: "Every gas is a vacuum to every other gas".
-This is the way Dalton stated what we now know as his law of partial pressures.
-It simply means that each gas present in a mixture of gases acts independently of the others.
-This makes sense because of one of the fundamental tenets of KMT theory that gas molecules have
negligible volumes.
-So Gas A in mixture of A and B acts as if Gas B were not there at all.
-Each contributes its own pressure to the total pressure within the container, in proportion to the
fraction of the molecules it represents.
 Diffusion: The tendency of molecules to move toward areas of
lower concentration until the concentration is uniform
throughout.

Graham’s
Law Effusion: A gas escapes through a tiny hole in a
container Year: 1840

Gases of lower molar mass diffuse and effuse faster than gasses of
higher molar mass.
 Graham’s Law of Diffusion
⚫ A few of the physical properties of gases depend on the identity of the gas.
⚫ One of these physical properties can be seen when the movement of gases is studied.
⚫ In 1829 Thomas Graham used an apparatus similar to the one shown in the figure below to study the diffusion of
gases the rate at which two gases mix.
⚫ This apparatus consists of a glass tube sealed at one end with plaster that has holes large enough to allow a gas
to enter or leave the tube.
⚫ When the tube is filled with H2 gas, the level of water in the tube slowly rises because the H2 molecules inside the
tube escape through the holes in the plaster more rapidly than the molecules in air can enter the tube.
⚫ By studying the rate at which the water level in this apparatus changed, Graham was able to obtain data on the
rate at which different gases mixed with air.

⚫ Graham found that the rates at which gases diffuse is inversely proportional to the square root of their
densities.
⚫ This relationship eventually became known as Graham's law of diffusion.
⚫ To understand the importance of this discovery we have to remember that equal volumes of different
gases contain the same number of particles.
⚫ As a result, the number of moles of gas per liter at a given temperature and pressure is constant, which
means that the density of a gas is directly proportional to its molecular weight. Graham's law of diffusion
can therefore also be written as follows.
⚫ Similar results were obtained when Graham studied the rate of effusion of a gas, which is the rate at which
the gas escapes through a pinhole into a vacuum.
⚫ The rate of effusion of a gas is also inversely proportional to the square root of either the density or the
molecular weight of the gas.
29
 Graham’s Law of Effusion
⚫ Graham's law of effusion can be demonstrated with the apparatus in the figure below.
⚫ A thick-walled filter flask is evacuated with a vacuum pump.
⚫ A syringe is filled with 25 mL of gas and the time required for the gas to escape
through the syringe needle into the evacuated filter flask is measured with a stop watch.

⚫ As we can see when data obtained in this experiment are graphed in the figure
below, the time required for 25-mL samples of different gases to escape into a
vacuum is proportional to the square root of the molecular weight of the gas.

⚫ The rate at which the gases effuse is therefore inversely proportional to the
square root of the molecular weight.

⚫ Graham's observations about the rate at which gases diffuse (mix) or effuse
(escape through a pinhole) suggest that relatively light gas particles such as
H2 molecules or He atoms move faster than relatively heavy gas particles
such as CO2 or SO2 molecules.

30
 Amagot’s Law of Partial Volume

According to Amagat's law of partial volume, the total volume of a non-reacting mixture of gases at constant
temperature and pressure should be equal to the sum of the individual partial volumes of the constituent gases.

Vtotal= V1 + V2 + V3 + ...

= xi V Here, V = total Volume

V1, V2, V3,... = Partial Volume

xi = Mole fraction

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 Derivation of Kinetic Gas Equation
What Is Kinetic Theory Of Gases?
⚫ The kinetic theory of gases describes gas as a large number of submicroscopic particles such
as atoms and molecules, all of which are in random and constant motion.
⚫ The randomness arises from the particle's collisions with each other and with the walls of
the container. Vy
V
⚫ Consider a cubical container of length ‘l’ filled with gas
y
molecules each having mass ‘m’ and let ”N” be the total
number of gas molecules in the container.
x
Vx
⚫ Due to the influence of temperature, the gas molecules move z 90°
in random directions with a velocity ‘v.’
Vz

⚫ The pressure of the gas molecules is the force exerted by the gas molecule per
unit area of the wall of the container and is given by the equation P= 𝑭/𝑨
32
 ⚫ Let us consider a gas molecule moving in the x-direction towards face A. mv
⚫ The molecule hits the wall with a velocity Vx and rebounds back with the same velocity
Vx, and will experience a change of momentum which is equal to
-mv
Δp=−2mVx
⚫ For a total of N number of gas molecules in the container, all such change in momentum is given by
Δp=−2NmVx
-The force is given by the equation
F=Δp/t
Therefore,
F=−2NmVx/t

33
⚫ Gas molecules will hit the wall “A” and will travel back across the box, collide with the opposite face
and hit face “A” again after a time “t” which is given by the equation

t=2l/Vx
-Substituting the value of “t” in the force equation, we get the force on the molecules as

F=−2NmVx/(2l/Vx)

Fmolecules= −2NmVx/(2l/Vx) = −NmVx2/l

34
 Therefore, the force exerted on the wall is Fwall=NmVx2/l
Now, the pressure P is given by the equation

P = Force on the wall/Area = NmVx2/l/(l2) = NmVx2/l3

Hence, PV = NmVx2 (1)

Since Vx, Vy and VZ are independent speed in three directions and if we consider the gas molecules in bulk, then

Vx2 = Vy2 = Vz2

Hence,

V2 = 3Vx2
Substituting the above condition in eq (1), we get PV = NmV2/3
35
 Therefore,

PV = 1/3 mNV2
This equation above is known as the kinetic theory equation.

The velocity “V” in the kinetic gas equation is known as the root-mean-square velocity and is given by the
equation

Vrms = √V12+ V22 + V32 ……..+ Vn2 /N

We use this equation to calculate the root-mean-square velocity of gas molecules at any given
temperature and pressure.

36
 Collisions in a Gas: Molecules Velocity Distribution

What is Happening During the Collisions?

⚫ All the sub microparticles of the gases in a particular time will be having “different velocities” in a box.

⚫ Hence, those particles will be having different “Kinetic Energies”.

⚫ It is due to the continuous collisions between the atoms and molecules, all of which are in random and constant
motion.

⚫ As an impact their velocities are keep changing……

Vy
V
y

x
Vx
z 90°

37 Vz
 In 1859,Maxwell and Boltzmann explained the molecules velocities distribution based on
the probability theory…as shown in the given picture

⚫ From the above figure, we could learn the followings;

Molecules Fraction (%)

⚫ (i) Molecules (%) fraction which are having various velocities.

Most Probable
Velocity (M.P.V) ⚫ (ii) Molecules which are having too less velocity as well as too
Mean Average high velocity are having too less molecules (%) Fraction.
Velocity (A.V)
Root Mean Square ⚫ The peak maximum of the graph is indicative of the most possible
Velocity (RMSV) velocity hence, at a particular temperature, we could learn that
Molecules (%) fraction is very high at most possible velocity. Hence it
Velocity can be referred as Most Possible Velocity, “u”.
Maxwell’s Velocity Distribution

⚫ When we increase the Temperature, distribution of the system is almost equal, but the peak maximum become more flatten. Which
represents, when the temperature got increased, velocity distribution between the molecules is more uniform.

⚫ When we increase the Temperature, molecules (%) fraction of the molecules which are having velocity also increased.

⚫ We obtain all the above details from the comparison between the 273 K (T1), 1273 K (T2), 2273 K (T3)
38
 Types of Molecular Velocities

⚫ There are four types molecular velocities;

⚫ (i) Most Probable velocity (MPV), “u”.

⚫ (ii) Average Velocity (AV), “v”.

⚫ (iii) Mean square velocity (MS), “c2”.

⚫ (iv) Root mean square velocity (RMS), “c”.

⚫ Let's see one by one in detail…..

39
 Most Probable velocity (MPV), “u”.

⚫ At a particular Temperature, velocity gained by the maximum no of molecules is

referred as the Most Probable Velocity.

⚫ The following equation will help us to calculate the “u”

Where,
𝟐𝑹𝑻 R = Gas Constant
𝒖= T = Temperature,
𝑴 M = Molar Mass

40
 Average Velocity (AV), “v”.

⚫ In a given gas, all the molecules average velocity is known as Average Velocity.
⚫ Lets consider, in a gas n1, n2, n3……….are u1, u2, u3……molecules velocity,
respectively.

𝒏𝟏𝒖𝟏+𝒏𝟐𝒖𝟐+𝒏𝟑𝒖𝟑+⋯
Therefore, Average Velocity, v =
𝒏𝟏+𝒏𝟐+𝒏𝟑+⋯

𝟖𝑹𝑻 Where,
v= R = Gas Constant
π𝑴 T = Temperature,
M = Molar Mass
41
 Mean square velocity (MS), “c2”
⚫ In a given gas, all the molecules’ velocities mean square is known as Mean Square
Velocity.
⚫ Let's consider, in a gas n1, n2, n3……….are u1, u2, u3……molecules velocity,
respectively.
2 𝒏𝟏𝒖𝟏+𝒏𝟐𝒖𝟐+𝒏𝟑𝒖𝟑+⋯
Therefore, Mean Square Velocity, c =
𝒏𝟏+𝒏𝟐+𝒏𝟑+⋯

2 𝟑𝑷𝑽
From the kinetic gas equation, c =
𝑴
Where,
By using the equation, PV = RT R = Gas Constant
𝟑𝑹𝑻 T = Temperature,
Final equation can be derived as c
2 = M = Molar Mass
𝑴
42
 Root mean square velocity (RMS), “c”

⚫ In a given gas, all the molecules’ velocities root mean square is known as Root
Mean Square Velocity.
⚫ Let's consider, in a gas n1, n2, n3……….are u1, u2, u3……molecules velocity,
respectively.
𝒏𝟏𝒖𝟏+𝒏𝟐𝒖𝟐+𝒏𝟑𝒖𝟑+⋯
Therefore, Mean Square Velocity, c = √
𝒏𝟏+𝒏𝟐+𝒏𝟑+⋯

𝟑𝑷𝑽 𝟑𝑷 𝟑𝑹𝑻
From the kinetic gas equation, c= = =
𝑴 ρ 𝑴
Where,
𝑴 R = Gas Constant
Here, ρ is the density. ρ = T = Temperature,
𝑽 M = Molar Mass
43
V = Volume
 Observations

𝟐𝑹𝑻 𝟖𝑹𝑻 𝟑𝑹𝑻 𝟑𝑷𝑽 𝟑𝑷 𝟑𝑹𝑻

𝒖= v= c2 = c= = =
𝑴 π𝑴 𝑴 𝑴 ρ 𝑴

⚫ All type of velocities are having….

⚫ (1) directly proportional to Temperature, T.

⚫ (ii) Indirectly proportional to the Molar Mass, M.

44
 Relationship between Various Velocities

𝟐𝑹𝑻 𝟖𝑹𝑻 𝟑𝑹𝑻

𝒖= v= c=
𝑴 π𝑴 𝑴

𝟐𝑹𝑻 𝟖𝑹𝑻 𝟑𝑹𝑻

u: v: c = = =
𝑴 π𝑴 𝑴

𝟖
u: v: c = 𝟐= = 𝟑
π

u: v: c = 𝟏. 𝟒𝟏 = 1.60 = 𝟏. 𝟕𝟑
45
 Comparison between Root Mean Square Velocity (c) with other Velocities

u: v: c = 𝟏. 𝟒𝟏 = 1.60 = 𝟏. 𝟕𝟑

u:c = 𝟏. 𝟒𝟏: 𝟏. 𝟕𝟑
𝟏.𝟒𝟏
(1) Therefore u= 𝒄 = 𝟎. 𝟖𝟏𝟔 𝒄
𝟏.𝟕𝟑

v:c = 𝟏. 𝟔𝟎: 𝟏. 𝟕𝟑
𝟏.𝟔𝟎
(2) Therefore v= 𝒄 = 𝟎. 𝟗𝟐𝟓 𝒄
46
𝟏.𝟕𝟑
 Table: At 298 K some of the gases molecular velocity (RMSV, c) are listed in the table below

Gas Velocity ms-1 Gas Velocity

ms-1
Hydrogen, H2 1930 Carbon Monoxide, CO 515
Deuterium, D2 1360 Oxygen, O2 482
Methane, CH4 680 Carbon Dioxide, CO2 410
Ammonia, NH3 669 Sulphur Dioxide, SO2 340
Nitrogen, N2 515 Chlorine, Cl2 323

⚫ From the table, it can be learned that when Molar Mass increases, Molecular Velocity
decreases… (indirectly proportional).

47
Exercise

48
 1. Derive the various velocities of Oxygen Molecule at 25 °C?

𝟑𝑹𝑻 −𝟏
RMS c = 𝒎𝒔
𝑴
−𝟏 −𝟏
Here, R= gas constant = 𝟖. 𝟑𝟏𝟒 𝐉𝐊 𝐦𝐨𝐥
Here, T= Temperature = 25 °C = 298 K. ( 0°C = 273 K)
−𝟑 −𝟏
Here, M= Molar Mass of Oxygen = 𝟑𝟐 𝐱 𝟏𝟎 𝐤𝐠 𝐦𝐨𝐥

𝟑 𝒙 𝟖.𝟑𝟏𝟒 𝒙 𝟐𝟗𝟖 −𝟏 −𝟏
c =
−𝟏
− 𝒎𝒔 = 𝟒𝟖𝟐 𝒎𝒔 u = 𝟎. 𝟖𝟏𝟔 𝒄 = 𝟎. 𝟖𝟏𝟔 𝒙 𝟒𝟖𝟐 𝒎𝒔
𝟑𝟐 𝒙 𝟏𝟎 𝟑
= 393.3 ms-1
−𝟏
v = 𝟎. 𝟗𝟐𝟓 𝒄 = 𝟎. 𝟗𝟐𝟓 𝒙 𝟒𝟖𝟐 𝒎𝒔
= 445.8 ms-1
49
 2. At 27 °C, what is the RMS, c of Methane? At what temperature Oxygen will be having
such RMS value?

For Methane, −𝟏 −𝟏
R= gas constant = 𝟖. 𝟑𝟏𝟒 𝐉𝐊
𝟑𝑹𝑻 −𝟏
RMS c = 𝒎𝒔 𝐦𝐨𝐥
𝑴

T= Temperature = 27 °C = 300 K.
−𝟑 −𝟏
M= Molar Mass of Methane = 𝟏𝟔 𝐱 𝟏𝟎 𝐤𝐠 𝐦𝐨𝐥

𝟑 𝒙 𝟖.𝟑𝟏𝟒 𝒙 𝟑𝟎𝟎 −𝟏 −𝟏
c = − 𝒎𝒔 = 𝟔𝟖𝟑. 𝟖 𝒎𝒔
𝟏𝟔 𝒙 𝟏𝟎 𝟑

−𝟏
c = 𝟔𝟖𝟑. 𝟖 𝒎𝒔 ;T=?
−𝟑 −𝟏
For Oxygen, M= Molar Mass of O2 = 𝟑𝟐 𝐱 𝟏𝟎 𝐤𝐠 𝐦𝐨𝐥

𝟑 𝒙 𝟖.𝟑𝟏𝟒 𝒙 𝑻
=
𝟑 𝒙 𝟖.𝟑𝟏𝟒 𝒙 𝑻 −𝟏
Lets take square root,
683.8 =
𝟑𝑹𝑻 −𝟏
c = 𝒎𝒔 −
𝟑𝟐 𝒙 𝟏𝟎 𝟑
𝒎𝒔 4.676 x 105 −
𝑴 𝟑𝟐 𝒙 𝟏𝟎 𝟑
−

600 K
𝟐
𝟒.𝟔𝟕𝟔 𝒙 𝟏𝟎𝟓 𝒙 𝟑.𝟐 𝒙 𝟏𝟎
Therefore, T = =
𝟑 𝒙 𝟖.𝟑𝟏𝟒

Hence at 600 K (327 °C) Oxygen gas will be having Methane’s RMS value.
50
 3. At standard Temperature and Pressure, calculate Hydrogen’s RMS, c . Density of
Hydrogen is 0.0893 kg m-3.

𝟑𝑷𝑽 𝟑𝑷 𝟑𝑹𝑻 −𝟏 1 atm = 101.325 kPa

c= = = 𝒎𝒔 = 760 torr = 760
𝑴 ρ 𝑴
mmHg = 14.7 psi
P= Standard Pressure = 1.013 x 105 Nm-2

ρ= density = 0.0893 kg m-3

𝟑 𝒙 𝟏.𝟎𝟏𝟑 𝒙 𝟏𝟎𝟓 −𝟏 −𝟏
c = 𝒎𝒔 = 𝟏𝟖𝟒𝟓 𝒎𝒔
𝟎.𝟎𝟖𝟗𝟑

51
 Kinetic Energy of Ideal Gases
𝐍𝐦𝐜𝟐
From the Kinetic Gas Equation, PV = …….eqn (1)
𝟑
If we consider an one mole of Ideal gas, then “ Nm” can be considered as it Molar Mass, “M”.
𝟐
𝑴𝐜
Therefore, PV = …….eqn (2) Comparing eqn (5) and eqn (6)…..
𝟑
Average Kinetic Energy ( K.E) one mole of gas is…. 𝟐.𝑲.𝑬
= RT …….eqn (7)
𝑴𝐜𝟐 𝟑
Therefore, K.E = …….eqn (3)
𝟐 𝟑
Or K.E = 𝑹𝑻 …….eqn (8)
Or, 2 k.E = Mc2…….eqn (4) 𝟐
𝟑
Substituting eqn (4) into eqn (2)….. Here, 𝑹 is a constant
𝟐
PV =
𝟐.𝑲.𝑬
…….eqn (5)
Therefore, K.E α 𝐓 …….eqn (9)
𝟑
It means Kinetic energy is having direct proportional
Therefore equation for one mole of Ideal Gas is….
relationship with the Temperature. Proposed by
52 PV = RT …….eqn (6) Maxwell first.
Exercise

53
 1. Calculate the kinetic energy of a 22 g of CO2 gas at 27 °C?

Here, Mass of CO2 = 22 g = 22 x 10-3 kg

Here, M= Molar Mass of CO2 = 44 x 10-3 kg mol-1

−
𝟑
𝑴𝒂𝒔𝒔 𝟐𝟐 𝒙 𝟏𝟎
Therefore, No of Moles = = − = 0.5
𝑴𝒐𝒍𝒂𝒓 𝑴𝒂𝒔𝒔 𝟒𝟒 𝒙 𝟏𝟎 𝟑
𝟑
Kinetic Energy (K.E) for one mole = 𝑹𝑻 J
𝟐
𝟑
Therefore, Kinetic Energy (K.E) for 0.5 mole = 𝟎. 𝟓 𝑹𝑻 J
𝟐
𝟑
K.E= 𝟖. 𝟑𝟏𝟒
𝟒
𝒙 𝟑𝟎𝟎 J = 1870 J
54
 Collision Diameter, σ

◆ When two gas molecules approach one another, they

cannot come closer beyond a certain distance.

◆ The closest distance between the centres of the σ

two molecules taking part in a collision is called the collision Diameter.
◆ It is denoted by σ.
◆ Whenever the distance between the centres of two molecules is σ, a collision occurs.
◆ The collision diameter is obliviously related to the mean free path of molecules.
◆ The smaller the collision or molecular diameter, the larger is the mean free path.

55
 Collision Number/Frequency, Z
◆ No. of collisions occurred per second between the molecules
present in a 1 mL of gas, is known as Collision Number, Z.

◆ It is also referred as Collision Frequency.

According to kinetic gas theory concern regarding

Collision diameter, equation can be derived as follows….
σ

Z = √2 π σ2 v N (for one gas molecule)

Hence, for all gas molecules which involves in collision. Where,

v = Average velocity
Z = √2 π σ2 v N2 σ = Collision diameter/molecule’s diameter
N = Avagadro Number
56
 Mean Free Path, λ
◆ The average distance, a gas molecule can travel within the two successive collisions is known as Mean free path, λ.
◆ Mathematical expression can be derived as follows,

miss
◆ Assume molecules are rigid spheres of radius r. hit
σ
Collision
◆ Only one moves, with the speed v. diameter
◆ It will collide with another molecule when their hit hit
centers are at distance σ. hit
◆ i.e. in dt it collides if there are other molecules with miss
miss
centers inside this cylinder. Collision Cross
section = π σ2

Where,
𝟏 𝟏 𝑲𝑻 k = Boltzmann Constant = R/N
λ= = = σ = Collision diameter/molecule’s diameter, T = Temperature, R = Gas constant,
𝒁 𝟐 𝝅 𝝈𝟐 𝑵 𝟐 𝝅 𝑷 𝝈𝟐 P = Pressure, N = Avagadro Number, Z = Collision No, v = Average velocity

57
 𝟏 𝟏 𝑲𝑻
λ= = =
𝒁 𝟐 𝝅 𝝈𝟐 𝑵 𝟐 𝝅 𝑷 𝝈𝟐

◆ Directly proportional to Temperature.

◆ Inversely proportional to Pressure and Collision diameter.

At NTP some of the gases collision diameter and mean free path

Gas Collision diameter Mean free path

Hydrogen 2.74 x 10-10 11.2 x 10-8
Helium 2.18 x 10-10 18.2 x 10-8
Nitrogen 3.75 x 10-10 5.95 x 10-8
Oxygen 3.61 x 10-10 6.43 x 10-8

58
Exercise

59
 1. Calculate the mean free path of Oxygen at 298k and 1 atm. Collision
diameter of Oxygen is 3.61 Å.

𝟏 𝟏 𝑲𝑻
Mean free path, λ = = =
𝒁 𝟐 𝝅 𝝈𝟐 𝑵 𝟐 𝝅 𝑷 𝝈𝟐
𝑹 𝟖.𝟑𝟏𝟒
K = = P = 1 atm = 1.013 x 105 Nm-2
𝑵 𝟔.𝟎𝟐𝟑 𝒙 𝟏𝟎𝟐𝟑

σ = 3.61 Å = 3.61 x 10-10 m; T = 298 k

𝟖.𝟑𝟏𝟒 𝒙 𝟐𝟗𝟖
λ = −
𝟔.𝟎𝟐𝟑 𝒙 𝟏𝟎𝟐𝟑 𝒙 𝟏.𝟒𝟏𝟒 𝒙 𝟏.𝟎𝟏𝟑 𝒙 𝟏𝟎𝟓 𝒙 𝟑.𝟏𝟒𝟑 𝒙 𝟑.𝟔𝟏 𝒙 𝟏𝟎 𝟏𝟎 𝟐
𝒎
−𝟖
λ= 𝟕. 𝟎𝟏𝟒 𝒙 𝟏𝟎 𝒎

60
 Behavior of Real Gases or Non-Ideal Gases

◆ Based on gases' pressure (P), volume (V) and temperature (T) they can be categorized as follows;
(i) Ideal Gases (ii) Real Gases
◆ Gases which obey the Ideal gas equation, PV = nRT are Ideal gases and those do not obey are known as Real Gases.
◆ Based on the Kinetic behaviours of the gases several postulates have been derived.
◆ In which, following two postulates are considered as key factor for the deviation of Real gases from Ideal gases.
-(i) Volume occupied by the Ideal gas molecules are negligible in comparison with the total volume.
-(ii) Ideal gas molecules do not show any molecular interaction with each other.

-above two postulates are matches well for the Real gases at (i) low pressure (ii) high temperature
On contrary, at (i) high pressure (ii) low temperature Real gases deviate from the Ideal gases.

Therefore, from the experiments of converting gases into liquids and solids, following results have been learned.
(i) Molecules at gas states will be having minimum volume.
(ii) There is a operational intermolecular attractive forces between the gas molecules.

61
 (a) Verification of the Postulate 1

Increase P Increase P

⚫ An ideal gas is composed of randomly moving minute particles, which undergo elastic
collisions.
⚫ Real gases are the ones which do not follow the ideal relations of gas law.
⚫ The deviation of real gas from ideal gas behavior occurs due to the assumption that, if
pressure increases the volume decreases.
⚫ The volume will approach a smaller number but will not be zero because the molecules
will occupy some space that cannot be compressed further.

62
 (b) Verification of the Postulate 2

Ideal vs. Real Gases

Ideal Gas Real Gas

-High Temperature -Low Temperature
-low pressure -High pressure

Intermolecular
Interaction

63
 (a) Verification of the Postulate 2

⚫ The experimental observation of gases correctly corresponds to its theoretical model.

⚫ The difficulty arises when we test the extent to which the relationship, pV = nRT, the ideal gas equation, is followed to
depict the actual pressure-volume-temperature relation of gases.
⚫ To have a check on this point, let us plot pV versus V graph.
⚫ At constant temperature the pV relation will be constant.
⚫ The pV versus p graph will be a straight line parallel to x axis.

Looking at the graph,

⚫ It is seen that at constant temperature the pV vs p plot is not a straight line for real
gases.
⚫ There is significant deviation from the ideal behavior.
⚫ In the case of hydrogen and helium, if the value of p increases then pV also increases.
⚫ In other cases for example methane and carbon dioxide, initially there is a negative
deviation from the ideal behaviour, the increase in pressure decreases the value of
pV and reaches a minimum value.
⚫ After it reaches the minimum point, pV value starts increasing and crosses the line
for the ideal gas and then shows positive deviation continuously.
Figure shows the graph constructed
⚫ So it can be said that the “Real gases do not follow the Ideal gas from actual data for some gases at
equation at all temperature and pressure”. 273 K.

64
 “If the temperature is constant, as
pressure of a gas increases the
volume decreases”

◆ The deviation of Real gas from Ideal gas behavior is also seen
Year: 1662
when pressure Vs. volume graph is plotted.
◆ The graph of pressure Vs. volume should coincide for the
experimental data that is the real gas, and the theoretical data
that is calculated according to Boyle’s law.
◆ It has been observed, at high pressure the measured volume
of the gas is more than the calculated volume.
◆ But at low pressure the calculated and the measured volumes
approaches each other.
◆ So, it can be stated that the Real gases does not follow the
Charles law, Boyle’s law, Avagadro law perfectly under all
conditions of temperature and pressure.

65
Van der Waal’s Equation and Its
Applicability
• Van der Waals equation was derived by Johannes Diderik van der
Waals in the year 1873.
• The equation is basically a modified version of the Ideal Gas Law
which states that gases consist of point masses that undergo
perfectly elastic collisions.
• However, this law fails to explain the behavior of real gases.
• Therefore, Van der Waals equation was developed, and it helps us
define the physical state of a real gas.

• -More significantly, the Van der Waals equation takes into

consideration the molecular size and molecular interaction forces
(attractive and repulsive forces).
• Sometimes, it is also referred to as Van der Waals equation of state.
• He has introduced two corrections to the Ideal Gas equations..
(i) Volume Correction and (ii) Pressure Correction

66
 What is Van der Waal’s Forces
Definition: Van der Waals forces include attraction and repulsions between atoms, molecules, and surfaces, as well as
other intermolecular forces.
They differ from covalent and ionic bonding in that they are caused by correlations in the fluctuating
polarizations of nearby particles (a consequence of quantum dynamics).

67
 What is Van der Waal’s Equation?
“Van der Waals equation is an equation relating the relationship between the pressure, volume, temperature, and
amount of real gases”

For a real gas containing ‘n’ moles, the equation is written as;
𝒂𝒏𝟐
𝑷+ 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽𝟐
Where, P, V, T, n are the pressure, volume, temperature and moles of the gas. ‘a’ and ‘b’ constants specific to each gas.

The equation can further be written as;

𝑹𝑻 𝟐 𝒂 𝒂𝒃
1. Cube Power of Volume: V3-(b + )𝑽 + 𝑽 − =𝟎
𝑷 𝑷 𝑷
2. Reduced equation (Law of Corresponding states) in terms of critical constants:

𝟑 𝑷 𝑽 𝑻
π+ 𝟑ψ − 𝟏 = 𝟖𝑻 : where π = ,ψ = 𝒂𝒏𝒅 𝑻 =
ψ𝟐 𝑷𝒄 𝑽𝒄 𝑻𝒄
68
 Van der Waal’s Equation Derivation
⚫ Van der Waals equation derivation is based on correcting the pressure and volume of the ideal gases given by
Kinetic Theory of Gases.
⚫ Another derivation is also used that is based on the potentials of the particles.
-Nonetheless, both derivations help us establish the same relationship.

Van der Waals Equation of State for Real Gases – Derivation

Kinetic theory of ideal gases assumes the gaseous particles as –

-Point masses without any volume,

-Independent having no interactions and
-Undergo perfectly elastic collisions.

In practice, Van der Waals assumed that, gaseous particles –

1.Are hard spheres.

2.Have definite volume and hence cannot be compressed beyond a limit.
3.Two particles at close range interact and have an exclusive spherical volume around them.
69
 Volume Correction
⚫ Actual “Volume” of the gas molecules can be considered as the “Space” where the gas molecules are freely moving.
⚫ As the particles have a definite volume, the volume available for their movement is not the entire container volume but less.
⚫ Volume in the ideal gas is hence an over-estimation and has to be reduced for real gases.
Volume of the real gas VR = Volume of the container/ideal gas (VI) – Correction factor(b): VR = VI – b.
If the particles are independent, then,
𝟒
Total volume of the particle = number of particle x volume of one particle = (n 𝟑 𝝅𝒓𝟑) Two Sphere Model

But, the particles are not independent, they do interact.

Van der Waal considered two hard-sphere particles can come as close as to touch each other
and they will not allow any other particle to enter in that volume as shown in the diagram.

The two sphere model, has a total radius of ‘2r’ (r is the radius of the sphere particle) and
𝟒 𝟒
Volume of 𝝅𝟐𝒓𝟑 = 8 × 𝝅𝒓𝟑 = 8 x volume of single particle.
𝟑 𝟑
Then, each of the two particles has a sphere of influence of 4 times the volume of the particle.
𝟒
Volume correction for each particle is not volume of the particle but four times of it = b = 4 x 𝝅𝒓𝟑
𝟑
𝟒
Volume correction for ‘n’ particles = nb = 4n x 𝝅𝒓𝟑 Volume (V) of the real gas = Vi – nb
𝟑
70
 Pressure Correction
⚫ Gaseous particles do interact.
Molecular Interaction
⚫ For inside particles, the interactions cancel each other.
⚫ But the particles on the surface and near the walls of the container do not have particles above the surface and on the walls.
⚫ So, there will be net interactions or pulling of the bulk molecules towards the bulk that is away from the walls and surface.
⚫ The molecules experiencing a net interaction away from the walls will hit the walls with less force and pressure.
⚫ Hence, in real gases, the particles exhibit lower pressure than shown by ideal gases.

The reduction in pressure “α” square of the particle density in the bulk α (particle density/volume)2
𝒏𝟐 𝒏𝟐
α 𝑽𝟐 = α 𝑽𝟐; where, a is the proportionality constant.
𝒏𝟐
Pressure of the real gas, Pi = Pr + α 𝑽𝟐
Substituting the pressure and volume correction in the ideal gas equation, we get Van der Waals equation for real gases as;
𝒏𝟐 𝒏𝟐
𝑷𝒓 + α 𝟐 𝑽𝒊 − 𝒏𝒃 = 𝒏 𝑹𝑻 𝒐𝒓 𝒊𝒏 𝒈𝒆𝒏𝒆𝒓𝒂𝒍 𝑷 + α 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽 𝑽
Here, ‘a’ and ‘b’ are Van der Waals constants and they contain positive values. The constants are the characteristic of the individual gas. When gas is ideal
or that it behaves ideally then both the constant will be zero. Generally, “a” constant help in the correction of the intermolecular forces while the “b”
71
constant helps in making adjustments for the volume occupied by the gas particles.
 Van der Waal’s Constants

𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

⚫ (i) Units
Both Pressure (P) and Volume (V) are determining factors for the units of the Van der Waals equation.

𝑷𝑽𝟐 𝒏𝟐
(a) is the constant for the Pressure correction, can be represented as 𝟐 . Pi = Pr + α
𝒏 𝑽𝟐
𝑷𝒓𝒆𝒔𝒔𝒖𝒓𝒆 𝒙 (𝑽𝒐𝒍𝒖𝒎𝒆)𝟐
Therefore, unit for the constant “a” =
(𝑴𝒐𝒍𝒆)𝟐
= Nm-2 x (m3)2 mol-2
= Nm4 mol-2 (S.I. unit) = Nm-2 (dm3)2 mol-2

(b) is the constant for the Volume correction, can be represented as m3 mol-1 (S.I. unit) = (dm)3 mol-1.

72
Molecular Interaction
 Ideal Gas Equation and Van der Waal’s
Equation Comparison
Ideal gas equations is given as PV = nRT
𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

At constant temperature, a decrease in pressure (P) do increases the volume (V).

Hence at low pressures, the volume will be larger.
𝒏𝟐
So, the correction factor in high pressure 𝜶 𝟐 becomes very small and negligible.
𝑽

At high Temperature, Again the volume of the gas will be larger compared to the volume of the molecules (n, b).
Hence, the volume correction also will be small and negligible.

As the correction factor becomes negligible,

pressure and volume of the real gases will be equal to that of ideal gases.

Interestingly, all real gases behave like ideal gases at low pressures and high
temperatures.
73
 Merits of Van der Waal’s Equation of State
𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽
𝒂
⚫ Here, 𝟐 is explaining the intermolecular interactions between the gas molecules, also referred as “Fusion
𝑽
Pressure”.
-H2, He gases are having very less “a” value
-Hence, there is less Van der Waals force is operating-liquidification is difficult.
-But, for Cl2, NH3, SO2, CO2 are having very high “a” value-can be easily converted into liquid.

⚫ By using the constants, inversion temperature,Ti is calculated. Because,

𝟐𝒂
Ti =
𝑹𝒃
⚫ By using the constants, critical gas constant values can be calculated.
Critical Volume, Vc = 3b
𝒂
Critical Pressure, Pc =
𝟐𝟕𝒃𝟐
⚫ From the critical constants, Van der Waal’s constants “a” and “b” can be derived as follows;
𝑽
b = 𝒄; 𝒂 = 𝟑𝑷𝒄 𝑽𝟐𝒄
𝟑
74
 Demerits of Van der Waal’s Equation

1.The equation gives more accurate results of all real gases only above critical temperature.

2.The results are acceptable below the critical temperature.

3.The equation completely fails in the transition phase of gas to the liquid below a critical temperature.

In any case, Van der Waals theory helps us to develop an approximation for real gases at high

pressures and also predict the behavior of non-ideal gases.

75
 Van der Waal’s Equation Applicability for
Various Situations: One Mole of Ideal Gas
𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

𝒂
Van der Waals equation for one mole of a gas is 𝑷+ 𝑽 − 𝒃 = 𝑹𝑻……(1)
𝑽𝟐

𝒂 𝒂𝒃
Or, 𝑷𝑽 − 𝑷𝒃 + − = 𝑹𝑻……(2)
𝑽 𝑽𝟐
𝒂𝒃
-Here, mostly value will be lower in most of the cases hence, we could eliminate it,
𝑽𝟐
𝒂
𝑷𝑽 − 𝑷𝒃 + = 𝑹𝑻……(3)
𝑽
For an Ideal Gas, Pi Vi = RT ……..(4)

Here, Pi and Vi are pressure and volume of an Ideal gas, respectively.

𝒂
Therefore, 𝑷𝑽 − 𝑷𝒃 + = 𝑷𝒊𝑽𝒊……(5)
𝑽

Equation (5) is the Van der Waals equation to be used for one mole of a Ideal Gas.
76
 i. Low Pressure
𝒂
Van der Waals equation for One mole of Ideal Gas = 𝑷𝑽 − 𝑷𝒃 + = 𝑷𝒊𝑽𝒊 …..(1)
𝑽

𝒂
-at the low pressure, factor which is indicative of molecular interactions, value will be higher than the Pb
𝑽
hence, we could eliminate Pb from equation (1),

𝒂
𝑷𝑽 + = 𝑷𝒊𝑽𝒊 …..(2)
𝑽

𝒂
Or, 𝑷𝑽 = 𝑷𝒊𝑽𝒊 − …..(3)
𝑽

-So at low pressure, the value of the PV will be less than that of PiVi.

77
 ii. High Pressure
𝒂
Van der Waals equation for One mole of Ideal Gas = 𝑷𝑽 − 𝑷𝒃 + = 𝑷𝒊𝑽𝒊 …..(1)
𝑽

𝒂
-at the high pressure, factor which is indicative of molecular interactions, value
𝑽
𝒂
will be lower than the Pb hence, we could eliminate from equation (1),
𝑽

𝑷𝑽 − 𝑷𝒃 = 𝑷𝒊𝑽𝒊 …..(2)

Or, 𝑷𝑽 = 𝑷𝒊𝑽𝒊 + 𝑷𝒃 …..(3)

-So at high pressure, the value of the PV will be higher than that of PiVi
-Same can be learned from the figure. Figure shows the graph
constructed from actual data for
some gases at 273 K.

78
 iii. High Temperature
𝒂
Van der Waals equation for One mole of Ideal Gas = 𝑷𝑽 − 𝑷𝒃 + = 𝑷𝒊𝑽𝒊 …..(1)
𝑽

For an Ideal Gas, Pi Vi = RT ……..(2)

𝒂
-at the high Temperature, Volume (V) will be very high hence, both factors; and Pb
𝑽
are negligible in equation (1),

𝑷𝑽 = 𝑷𝒊𝑽𝒊 …..(3)

-So at high Temperature, the value of the PV will be equal to PiVi

-Besides, Real gases behave like Ideal gases.
Year: 1662
-As well as obeys Boyle Law
“If the temperature is constant,
as pressure of a gas increases the
volume decreases”
79
 iv. For Hydrogen Gas
𝒂
Van der Waals equation for One mole of Ideal Gas = 𝑷𝑽 − 𝑷𝒃 + = 𝑷𝒊𝑽𝒊 …..(1)
𝑽

-The molecular mass and the size of the H2 are less.

𝒂 𝒂
Hence, the factor which is responsible for the molecular interactions also less, so can be negligible in
𝑽 𝑽
equation (1),

𝑷𝑽 − 𝑷𝒃 = 𝑷𝒊𝑽𝒊 …..(2)

Or, 𝑷𝑽 = 𝑷𝒊𝑽𝒊 + 𝑷𝒃 …..(3)

-So for H2 gas, the value of the PV is higher than the PiVi.

-He gas also having the same behavior.

80
 Other Gas Equations

⚫ Van der Waal’s equation is highly useful to explain the behavior of the “Real Gases”.

⚫ But at high pressure and low temperature, there are deviations….

⚫ Because, Van der Waals constants (a,b) are not behaving as a constants at all temperature and

pressure.

⚫ They are behaving as a constants for certain conditions only and Van der Waals equation can be

applied those circumstances only.

⚫ So, based on the parallel research, several other gas equations have been proposed and used.

⚫ Lets briefly discuss about them….

81
 1. Berthelot Equation
In 1878, D. Berthelot has corrected the Van der Waal’s equation as follows,

𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

𝒂
Berthelot equation = 𝑷 + 𝟐 (𝑽 − 𝒃) = 𝑹𝑻 …..(1)
𝑻𝑽

-Here the constants “a”, “b” are almost similar to the Van der Waal’s equation.

-Even though, dimension of “a” is having “T” in it.

-As an impact, the calculated Molar Masses of the gases were more accurate than the Van der Waal’s equation.

82
 2. Clausius Equation

In 1880, R. Clausius has proposed that depending on the Temperature, constant “a” do fluctuate.
Based on this he has given the modified version.

𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

𝒂
Clausius equation = 𝑷+ (𝑽 − 𝒃) = 𝑹𝑻 …..(1)
𝑻(𝑽+𝑪)𝟐

-Here the constant “C” is the new constant. Though it have satisfactory values, not suitable for all gases.

83
 3. Dieterici Equation
In 1899, C. Dieterici has corrected the Van der Waal’s equation as follows,

𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

Dieterici equation = 𝑷 𝑽 − 𝒃 = 𝑹𝑻. 𝒆−𝒂/𝑹𝑻𝑽 …..(1)

-this equation explains the effect of pressure on molecular interaction forces.

-Suitable for very high pressure systems.

84
 4. Onnes and Kammerling Equation
In 1901, H.K Onnes and H.K Kammerling proposed a new gas equation for the behavior Real gases.
They propose PV/RT ratio as 1 + correction factors.
Correction factor can be written based on (i) Volume and (ii) Pressure.

𝑷𝑽 𝑩 𝑪 𝑫
(1) For Volume =𝟏+ + + + ⋯ (1)
𝑹𝑻 𝑽 𝑽𝟐 𝑽𝟑

(2) For Pressure 𝐏𝐕 = 𝑹𝑻 + 𝑩𝑷 + 𝑪𝑷𝟐 + 𝑫𝑷𝟑 … (2)

-Force constants, B, C, D are depends on temperature.
-at low temperature all of the correction factors are Zero, then PV = RT
-but at high pressure, force constants, B, C, D are not same for all the gases.
Therefore, in equation (2), RT=A be substituted as follows…

𝐏𝐕 = 𝑨 + 𝑩𝑷 + 𝑪𝑷𝟐 + 𝑫𝑷𝟑 … (3)

-Here, factor “A” is always positive and directly proportional to Temperature.
-Second factor “B” is at low temp = negative value
Raising temp = Zero
High temp = positive value
At what temp, B value become Zero means that temp is known as “Boyle Temperature, T B”
85 At Boyle Temperature, gases do obey “Boyle Law”.
 5. Beate and Bridgeman Equation

In 1927, J.A Beate and O.C Bridgeman has derived the following equation,

𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

β γ δ
Dieterici equation = 𝑷𝑽 = 𝑹𝑻 + + + + ⋯(1)
𝑽 𝑽𝟐 𝑽𝟑

-Force constants, β, γ, δ are depends on temperature.

86
 The Critical State/Critical
Phenomenon/Liquification of Gases
Def: Is the state in which an object is present as mixture of two phases.

At constant Temperature (T), a graph/line/isotherm showing the

variations of Volume (V) and Pressure (P) is described as
“Equivalent Thermal Lines” or “Equivalent Isotherm”.

For the ideal gas, the PV value is a constant. Hence, as shown in

the figure “Rectangular Hyperbola” will be the resultant
graph/isotherm and which is a characteristic of the Ideal Gas.

87
 Andrews Isotherm & Critical Temperature

In 1869, T. Andrews has analyzed the equivalent

isotherms of CO2 gas at different temperatures and
derived important conclusions.

88
 Andrews Isotherm: Conclusions from the
Graph (i)
(i) At 321 K (48 °C), isotherm of the CO2 is almost like the Ideal Isotherms of CO2 at various
Gas (Rectangular Hyperbola). temperatures
(ii) At 304 K (31 °C), in the point “F” the line is deforming into a
horizontal line, and it is indicative of the following;
- When there is a change in Pressure, Volume has decreased a lot.
- This deformation is responsible for the conversion CO2 to Gas into
Liquid.
(iii) When temperature is too low ((21.5° C) 294 K and (13.1° C) 286 K),
horizontal behaviour is still increasing.
(iv) The I to J region is the indicative of compression of CO2 gas into
liquid.
(v) Liquification is starts at the point “I”.
-At constant pressure, line “IJ” is indicative of the
conversion gas into liquid.
-At point “J” liquification is completed.
-After the point “J”, while increasing the pressure; there is
volume decrement and line “JD” is indicative of it.
(vi) There is a parabola highlighted in the figure, in there both gas and
liquid are in their equilibrium. Out of this parabola, they do exist either
liquid
89 or gas.
 Andrews Isotherm: Conclusions from the
Graph (ii)
(vii) Isotherm “ABC” is the boundary between the Liquid and Gas. Isotherms of CO2 at various temperatures
-Besides, at the point “E” such boundary has disappeared.
-Point “E” is indicative of that the CO2 gas is its critical state.
-Hence, point “E” is referred as a “Critical Point”.
(viii) The isotherm which pass through the “Critical Point” is called as
“Critical Isotherm”.
- For CO2, (304 K, 31 °C) is referred as the Critical Temperature of
the CO2.
-Hence, Critical Temperature is the characteristic behavior of a gas,
and it can be described as follows;

Def: To convert gas into liquid, temperature of the gas should

be lowered/chilled to certain temperature and such
temperature is known as “Critical Temperature”, Tc.

90
 Andrews Isotherm: Critical Temperature, Tc
- Above to the Critical Temperature, Tc of gas, it can't Isotherms of CO2 at various temperatures
be converted into liquid even at high pressure.
- At Tc, the Pressure required to convert the gas into
liquid is known as “Critical Pressure”, Pc.
- At Tc and Pc, Volume of a one mole of gas is known as
“Critical Volume, Vc.
- Andrew’s observations and conclusions for CO2 is
applicable for other gas also.

91
 Van der Waal’s Equation Applicability:
Critical State
𝒏𝟐
Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽

𝒂
Van der Waals equation for one mole of a gas is 𝑷+ 𝑽 − 𝒃 = 𝑹𝑻……(1)
𝑽𝟐

𝒂 𝒂𝒃
Or, 𝑷𝑽 − 𝑷𝒃 + − = 𝑹𝑻……(2)
𝑽 𝑽𝟐
𝑽𝟐
-Here, multiply with (if we multiply with same value on both side, net value will be equal),
𝑷
𝒂𝑽 𝒂𝒃 𝑹𝑻𝑽𝟐
𝑽𝟑 − 𝒃𝑽𝟐 + − = ……(3)
𝑷 𝑷 𝑷

Re-arranging the eqn (3) based on power order of “V”

𝑹𝑻 𝒂𝑽 𝒂𝒃
𝑽𝟑 − 𝟐
+𝒃 𝑽 + − = 𝟎……(4)
𝑷 𝑷 𝑷

Here, there are total three “V” values (V3, V2,V). For eqn (4), all the three “V” will be real solutions or out
of three values, two may be real solutions and one may be ideal solution.
92
 Van der Waal’s Equation Applicability:
Critical State (cont..)
⚫ In total, three “V” values were derived from the Van
der Waals equation for the critical state.

⚫ Lets try to explore the “V” values from critical

isotherm of CO2.

⚫ At 321 K (48 °C), for each “P” value, there is only

one “V” value.

⚫ At 294 K (21 °C), for single “P” value (P2), there are
two “V” value (C, B).

⚫ But, the third “V” value derived from the Van der
Waal’s equation has been not identified from the
Andrews experiment.

93
 Thompson’s Explanation: Critical State
⚫ In 1871, Thompson has explained about the issue of missing third “V”.
⚫ He has determined the Van der Waals constants a, b through his experiment and
inserted in the eqn (4), Vander Waal’s eqn for the critical state.
𝑅𝑇 𝑎𝑉 𝑎𝑏
𝑉3 − + 𝑏 𝑉2 + − = 0……(4)
𝑃 𝑃 𝑃
⚫ Then, he has calculated “V” values in the known “T” at various “P”
⚫ And derived the P-V diagram for CO2’s critical isotherm.
⚫ Both Andrew’s and Thompson’s graph looks like some extent but below “Tc” there
is a deviation.
⚫ In Thomson’s experiment, “AE” region is not horizontal actually it is “curved line”
and continuous too.
⚫ For example, “EDCBA” is a continuous curved line.
⚫ In this curved line, at constant “P” value (P1), as well as below the critical pressure, “Pc” there are three “V” values have been marked
with the “A”, “C” and “E”.
⚫ While increasing the T, all of these curved lines (A-C-E) becomes smaller or all of the three “V” have become single/merged at critical
temperature, “Tc”.
⚫ Hence, three “V” values (3 real or 2 real + 1 imaginary solutions) derived from Van der Waal’s equation is fulfilled.
⚫ Here, volume of the liquid becomes equal to the volume of the gas.
⚫ As well as the boundary between the liquid and gas become disappeared- means object is in its critical state.
⚫ At critical state, T, P and V are referred as Tc, Pc and Vc.
⚫ At critical state, we can learn that all the three “V” values are same.
𝑅𝑇 𝑎𝑉 𝑎𝑏
𝑉3 − + 𝑏 𝑉2 + − = 0……(4)
𝑃 𝑃 𝑃
94
Therefore, by using the Thomson’s method, it is possible to calculate the Van der Waals constants at the critical state.
 First Method: Determination of Van der Waal’s Constants at Critical State

⚫ At critical state, three solutions of Van der Waal’s equation -dividing eqn (11) by eqn (10),
are equal to the volume “V” as follows, 𝟑 𝑽𝒄 𝒂𝒃 𝑷𝒄
= x ……..(12)
i.e., V=Vc …….. (5) 𝟑𝑽𝟐𝒄 𝑷𝒄 𝒂
Or, (V-Vc)3 = 0 …….. (6) Critical Volume, Vc = 3b….(13)
Expanding the eqn (6), V3-3V2 Vc + 3V 𝑉𝑐2 - 𝑉𝑐3 = 0 …..(7) Applying eqn (13) in eqn (10),
𝒂
eqn (4) can be rewritten for critical state (P= Pc ; T=Tc), 𝟑 𝒙 𝟑𝒃 = ……..(14)
𝟐
𝑷
𝒂 𝒄
𝑽𝟑 −
𝑹𝑻
+ 𝒃 𝑽𝟐 +
𝒂𝑽 𝒂𝒃
− = 𝟎……(4) 𝑶𝒓, 𝑷𝒄 = ……..(15)
𝑷 𝑷 𝑷
𝟐𝟕𝒃𝟐
𝑽𝟑 −
𝑹𝑻𝒄
+ 𝒃 𝑽𝟐 +
𝒂𝑽𝒄 𝒂𝒃
− = 𝟎……(8) Applying eqn (13) and (15) in eqn (9),
𝑷𝒄 𝑷𝒄 𝑷𝒄 𝑹𝑻𝒄
𝟑 𝒙 𝟑𝒃 = 𝒂
+ b ……..(16)
equations (7) and (8) can be compared and powers of “V” 𝟐𝟕𝒃𝟐
can be equalized,
𝟐𝟕𝑹𝑻𝒄𝒃𝟐
𝟖𝒃 = ……..(17)
𝑹𝑻𝒄 𝒂 𝒂
3Vc = + 𝒃…..(9); 3𝑽𝟐𝒄 = ....(10); 𝟖𝒂
𝑷𝒄
𝒂𝒃
𝑷𝒄 𝒕𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆, 𝑻𝒄 = ……..(18)
95 𝑽𝟑𝒄 = ....(11); 𝟐𝟕𝑹𝒃
𝑷𝒄
 Another Method: Determination of Van der Waal’s Constants at Critical
State

𝒏𝟐 Dividing eqn (9) by (8),

Van der Waals equation is 𝑷+ 𝜶 𝟐 𝑽 − 𝒏𝒃 = 𝒏 𝑹𝑻
𝑽
Van der Waals equation for one mole of a gas is 𝟐 𝟑
=𝑽 ……(10), 𝟑𝑽𝒄 − 𝟑𝒃 = 𝟐𝑽𝒄……(11), 𝑽𝒄 = 𝟑𝒃…..(12)
𝒂 𝑽𝒄−𝒃
𝑷+ 𝑽 − 𝒃 = 𝑹𝑻……(1) 𝒄
Applying eqn (12) in eqn (8),
𝑽𝟐
𝒂 𝑹𝑻
Rewritten as, 𝑷+ = ……(2) 𝑹𝑻𝒄 𝟐𝒂 𝑹𝑻𝒄 𝟐𝒂
𝑽𝟐 (𝑽−𝒃) 𝟐 = ……(13), = ……(14),
𝑹𝑻 𝒂 𝟑𝒃−𝒃 𝟑𝒃 𝟑 𝟒𝒃𝟐 𝟐𝟕𝒃 𝟑
Therefore, 𝑷 = − 𝟐 ……(3) 𝟖𝒂
(𝑽−𝒃) 𝑽 Therefore, Tc = ……(15)
𝟐𝟕𝑹𝒃
Applying eqn (12) and (15) in eqn (3),
-at critical state, following behavior can be observed,
𝒅𝑷 𝒅𝟐𝑷
𝒊 =𝟎 ……(4) ; 𝒊𝒊 =𝟎 ……(5) Pc =
𝑹𝑻𝒄 𝒂
− 𝟐 ……(16), Pc =
𝑹 𝒙 𝟖𝒂 𝒂
− 𝟐 ……(17),
𝒅𝑽 𝑻 𝒅𝑽𝟐 𝑻 𝑽𝒄−𝒃 𝑽𝒄 𝟐𝟕𝑹𝒃 𝟑𝒃−𝒃 𝟗𝒃
𝟖𝒂 𝒂 𝟒𝒂 𝟑𝒂
-from the eqn (3), Pc = − 𝟐 ……(18), Pc = − ……(19),
𝟐𝟕𝒃 𝟐𝒃 𝟗𝒃 𝟐𝟕𝒃𝟐 𝟐𝟕𝒃𝟐
𝒅𝑷 −𝑹𝑻 𝟐𝒂 𝒅𝟐 𝑷 𝟐𝑹𝑻 𝟔𝒂 𝒂
𝒊 = + ……(6); 𝒊𝒊 = − ……(7) Therefore, Pc = ……(20)
𝒅𝑽 𝑻 𝑽−𝒃 𝟐 𝑽𝟑 𝒅𝑽𝟐 𝑻 𝑽−𝒃 𝟑 𝑽𝟒
𝟐𝟕𝒃𝟐
At critical state, T = Tc; V = Vc. Applying equations (4) and (5) into Hence, Van der Waal’s constants “a, b” values are known
equations (6) and (7),
for a gas means, by using them critical gas constants (Tc,
𝑹𝑻𝒄 𝟐𝒂 𝟐𝑹𝑻𝒄 𝟔𝒂 Vc, Pc) can be calculated.
𝒊 𝑽𝒄−𝒃 𝟐 = 𝑽𝟑 ……(8); 𝒊𝒊 𝑽𝒄−𝒃 𝟑
= 𝑽𝟒 ……(9)
𝒄 𝒄
96
 Determination of Critical Volume, Vc
⚫ In 1886, Cailetet and Mathias has observed that a plot of average
density value of an object’s liquid and vapor pressure versus
temperature will give a straight line. Based on this behavior, Vc is
determined.
⚫ At various temperatures, density of a liquid and its vapor pressure
values are measured.
⚫ Subsequently, obtained values are plotted against temperature.
⚫ At the point “C”, both straight are met with each other and it is
referred as “Critical Density”. Temperature at this point is known as
Critical Temperature, Tc.
⚫ Point “C” is not sharp enough to measure the value hence, straight
line (C-D) drawn towards density (x-axis).
⚫ Point of intersection at the x-axis is referred as “Critical
Density” and at this point the density of a gas and liquid are equal.
⚫ Critical Volume, Vc can be obtained by dividing molar mass of as gas
by “Critical Density” derived from the plot.

𝒎𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒎𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔

𝒅𝒆𝒏𝒔𝒊𝒕𝒚, ρ = ……(1), c𝒓𝒊𝒕𝒊𝒄𝒂𝒍 𝒗𝒐𝒍𝒖𝒎𝒆, 𝑽𝒄 = 𝒄𝒓𝒊𝒕𝒊𝒄𝒂𝒍 𝒅𝒆𝒏𝒔𝒊𝒕𝒚 ……(2)
𝒗𝒐𝒍𝒖𝒎𝒆
97
 Law of Corresponding State/Reduced
Equation of State
⚫ In 1881, Van der Waals has proposed that for a gas, if its pressure (P), volume (V) and temperature (T) values are represented in
terms of their critical pressure (Pc), critical volume (Vc), and critical temperature (Tc) then a most significant common law can be derived
and it is known as “Law of Corresponding States”.
Lets have, P/Pc = π; V/Vc = ψ; T/Tc = θ
Here, π = Reduced Pressure, ψ = Reduced Volume, θ = Reduced Temperature. Furthermore, P = π Pc; V = ψ Vc; T = θ Tc
𝑎
Van der Waals equation for one mole of a gas is 𝑃+ 𝑉 − 𝑏 = 𝑅𝑇……(1)
𝑉2
𝑎
Substituting the above values in eqn (1), 𝜋 𝑃𝑐 + 𝜓 𝑉𝑐 − 𝑏 = 𝑅 𝜃𝑇𝑐……(2)
𝜓2 𝑉𝑐2

𝑎 8𝑎
But, Pc = ; 𝑉𝑐 = 3𝑏 ; Tc = substituting these values in eqn (2),
27𝑏2 27𝑅𝑏
𝑎 𝑎 8𝑎 2 1
𝜋 + 𝜓 3𝑏 − 𝑏 = 𝑅 𝜃 ……(3); (½ + ½ = 1? or, = ?)
27 𝑏2 𝜓2 9𝑏2 27 𝑅𝑏 4 2
𝑎 𝜋+ 3 𝑎 3
𝜓2 b 3𝜓 − 1 = 8 𝜃 27 𝑏 ….(4)
𝜋+ 3𝜓 − 1 = 8 𝜃……(5)
27 𝑏2 𝜓2
-eqn (5) is known as “Law of Corresponding States”. This equation do not have “R”, “a” and “b” constants.
-Hence, this equations is suitable for all objects. Also called as “Reduced Equation of State”.
98 “If, two objects are having the similar “π” and “θ”, then their “ψ” values will be equal and objects are said to be in law of
corresponding states.
 Compressibility Factor, Z
⚫ Behavior (deviation) of Real gases from the Ideal gases can be
demonstrated by Compression or Compressibility Factor, Z.

𝑃𝑉
i.e., Z =
𝑛𝑅𝑇
(i) For an Ideal Gases, Z = 1, Furthermore, it is independent of T
and P.
(ii) For Real Gases, there are some deviations in their Z-values.
- Furthermore, it is dependent of T as well as P.
- Deviation of Z-value from the “1” is the measure of
behaviour (deviation) of real gases in comparison with the
Ideal Gases.
- Some of the gases P-values are plotted against Z-
values.

From the Figure, it can be learned that for a Hydrogen gas Z-value is keep raising since beginning whereas,
for other gases, initially decreasing and then increased.
99
 Co-efficient of Compressibility, β
Def: At constant Temperature, ratio between the given Volume and ratio of change in Pressure with
respect to Volume of the system is referred as Co-efficient of Compressibility, β.

Mathematically it can be represented as follows,

1 𝛿𝑉
i.e., β = -
𝑉 𝛿𝑃 𝑇
- In the equation, negative (-ve) sign is purposely given, because β-value must be
positive (+ve).
- Due to the reason that all of the known objects’ Volume is decreasing while increasing the
Pressure.
- Unit is given as P-1.

100
 Co-efficient of Thermal Expansion, α

Def: At constant Pressure, ratio between the given Volume and ratio of change in Temperature with respect to Volume of
the system is referred as Co-efficient of Thermal Expansion, α.

Mathematically it can be represented as follows,

1 𝛿𝑉
i.e., α=
𝑉 𝛿𝑇 𝑃

- Unit is given as T-1.

101
 Relationship Between (α, β)
V = f (T, P) ……(1)

δ𝑽 δ𝑽
Therefore, dV = 𝒅𝑻 + dP ……(2)
δ𝑻 𝑷 δ𝑷 𝑻

𝟏 δ𝑽 𝟏 δ𝑽
We have, α = and β = - lets use these values in eqn (2),
𝑽 δ𝑻 𝑷 𝑽 δ𝑷 𝑻

dV = α V dT – β V dP ……(3)

at constant Volume, dV = 0

Hence, 0 = α V (dT)V – β V (dP)V ……(4)

Or, α V (dT)V = β V (dP)V ……(5)

α δ𝑷
102
= 𝑽 …..(6)
β δ𝑻
Unit-1b Liquid State

103
 Liquid State: Introduction
S. Properties Solid Liquid Gas
No
1 Volume Determined Determined No

2 Shape Clear Clear No

Shape Shape
3 Binding Force Strong Less Too Low
⚫ Objects do exist in Solid, Liquid and Gaseous states. 4 Compression No Less Too High
⚫ In which, we have studied the Gaseous state in the previous Possibility
section.
⚫ In order to understand the Liquid state well, it is essential 5 Density Too High High Less
to recall the Gaseous state and compare with the Liquid 6 Diffusion Behaviour Too Less Slow Speed
state. 7 Mobility No Controlled Un-
⚫ In general, Liquid state is considered as intermediate controlled
between the Solid and Gas State.
8 Structure of Closely Weak Weak
⚫ Because the molecules are not well organized in comparison
Molecules Packed
with the solid as well as it is not present as not-organized
as of Gas. 9 Mixing Behaviour Too Less Less Mix with
⚫ In some characters it is like gas and in some characters, it all ratios
is quite matching with the solid’s behavior. 10 Collision Distance Too Less Less High
⚫ It can be understood from the following Table.
104

1. Vapour Pressure
Def: The vapor pressure of
water is the pressure at which the
gas phase is in equilibrium with the
liquid phase.
105
Properties of Liquid
2. Surface Tension
Surface Tension: "The property of
the surface of a liquid that allows it to
resist an external force, due to the
cohesive nature of its molecules." ...
The cohesive forces between liquid
molecules are responsible for the
phenomenon known as surface
tension.
3. Viscosity
Viscosity is a measure of a fluid's
resistance to flow. It describes the
internal friction of a moving fluid. A
fluid with large viscosity resists
motion because its molecular
makeup gives it a lot of internal
friction.
 Surface Tension of Liquids
⚫ Liquid’s surface is always being a strongly tied diaphragm.
⚫ Hence, the surface try to minimize its surface area and it is referred as surface tension as well.
⚫ Surface Tension is aroused due the molecular interactions between the liquid molecules.
⚫ Following examples are representative of the surface tension;

Def: On liquid’s surface, both vertical as well as parallel/horizontal direction, force operating
over a unit line is referred as “Surface Tension” and its unit is Nm-1
106
 Surface Tension: Explanation Based on Molecular
Theory
⚫ Liquid’s molecules do interact as well as attract with each other.
⚫ A molecule do attract other molecules within certain boundary and such distance is known as
“attractive distance”
⚫ Hence, “attractive sphere” can be drawn by considering a molecule as center and
“attractive distance” as a radius.
⚫ Net force experienced by the center molecule is zero since, all the other molecules present in
the “attractive sphere” pulls the center molecule towards it.

⚫ Let’s consider molecule “A” in the figure, its net force is “Zero”.

⚫ Let’s consider molecule “B”,

-part of its attractive sphere is exposed on surface of the liquid.
- there are no molecules hence, molecules present in the bottom/liquid pulls down.
- hence, the net force is operating towards down
- due to this downward force, the static energy of the surface molecules is high
in comparison with the inner/bottom molecules.
- in order to release its static energy, the surface molecules tend behave like a
diaphragm.
-Thereby the liquid tends to minimize its surface area and it is referred as surface
tension as well.
107
 Measurement of Surface Tension, Capillary Action
There are several methods available for the measurement of the surface tension in which following two
methods we are going study in detail:
1. Capillary Rise Method
2. Drop Weight Method
Capillary action (sometimes capillarity, capillary motion, capillary effect,
or wicking)
-is the process of a liquid flowing in narrow spaces without the assistance of,
or even in opposition to, external forces like gravity.
-The effect can be seen in the drawing up of liquids between the hairs of a
paint-brush, in a thin tube, in porous materials such as paper and plaster, in
some non-porous materials such as sand and liquefied carbon fiber, or in
a biological cell.
-It occurs because of intermolecular forces between the liquid and
surrounding solid surfaces.
-If the diameter of the tube is sufficiently small, then the combination
of surface tension (which is caused by cohesion within the liquid)
and adhesive forces between the liquid and container wall act to propel the
liquid.
108
 1. Capillary Rise Method
Principle:
-Let’s assume that density as “ρ” in which liquid’s Surface Tension, “γ” to be
measured.
-Let’s assume that liquid is taken in a container and a “capillary tube” with radius “r”
is inserted.
-Due to the capillary action, liquid level has raised with the hight “h”.
Hence, total force which is required to raise the liquid = Surface Tension X Perimeter of the tube

= γ X 2 π r …..(1) Gravitational force which pulls the liquid down = Weight of the “liquid Batch”
= m g …..(2) = V ρ g …..(3) = π r2 h ρ g …..(4) Where, m = mass of the liquid batch, V = volume of the liquid batch. V
= π r2 h since liquid batch area is tubular.
At equilibrium, upward force = downward force

2 π r γ = π r2 h ρ g …..(5) Therefore, γ = r h ρ g/2 …..(6)

Procedure: -Hare’s apparatus is used to measure the density.
-Liquid’s batch height “h” is measured using the cathetometer. -By substituting these values in equation (6), Surface
-capillary tube’s radius “r” is measured by travelling microscope.
109
Tension, γ is measured.
Exercise

110
 1. Calculate the height of the water which raised through 2 x 10-4 radius capillary
tube. Surface tension of the water is 7.2 X 10-2 N. m-1.

Surface Tension, γ = r h ρ g/2……(1)

Height of the Liquid Batch, h = 2 γ/r ρ g……(2)

Here,
Surface tension of the water = γ = 7.2 X 10-2 N m-1
Radius of the capillary tube = r= 2 x 10-4 m

Density of water = ρ = 1000 kg m-3

Gravitational force = g = 9.8 m s-1

𝟐 𝒙 𝟕.𝟐 𝒙 𝟏𝟎−𝟐
Therefore, h = 𝒎 = 0.0734 m
𝟐 𝒙 𝟏𝟎−𝟒 𝒙 𝟏𝟎𝟎𝟎 𝒙 𝟗.𝟖
111
 2. Drop Weight Method
This method is the widely used one and more convenient in comparison with the Capillary Rise Method.

Principle:
“Weight of a single drop of liquid, which is falling from the vertically placed capillary
tube is almost directly proportional to the Surface Tension of the liquid, γ.
γ𝟏 𝑾𝟏
i.e., γ ∝ W…..(1) Or = …..(2)
γ𝟐 𝑾𝟐

Where, γ1 and γ2 = surface tension of the liquids, W1 and W2 = weight of the liquids.

- stalagmometer is used to count the specific volumed drops which are falling from the capillary tube.
- Let’s assume that specific volumed (V m3) two liquid’s drops falling from the same stalagmometer and gave n1 and n2
no.of drops.
𝑽
𝑾𝟐 = …..(4)
- Their average weights will be as follows; 𝑽
𝑾𝟏 = ρ …..(3) ρ
𝒏𝟐 𝟐
𝒏𝟏 𝟏
Where, ρ1 and ρ2 are densities of the two liquids and are determined by the Pyknometer. Applying eqn (3) and (4) in eqn (2),
γ𝟏 𝑽 𝒏𝟐 𝒏𝟐 ρ𝟏 Therefore, surface tension of the one liquid/standard is
= ρ x = …..(5) known means other/unknown liquid’s surface tension can
112 γ𝟐 𝒏𝟏 𝟏 𝑽ρ𝟐 𝒏𝟏 ρ𝟐
be easily calculated.
 Procedure for Drop Weight Method

- Stalagmometer is first washed with cromic acid mixture and dried.

- Subsequently, water (standard) is sucked and filled up to the level of “Zero”.
- Pinch cock setup is attached to enable/control the liquid drop fall.
- 20 drops are allowed per minute to fall.
- Later, stalagmometer is washed, dried and filled with the sample liquid (unknown) up to the mark
“Zero”.
- No.of falling drops are noted down.
- Now let’s assume n1 is the no. of water (standard) drops felt down and n2 is the no. of sample’s
(unknown) drops felt down.
- By considering ρ1 as water’s density and ρ2 as the sample liquid’s density then,

γ𝟏 𝒏𝟏 ρ𝟐
γ𝟐 =
𝒏𝟐 ρ𝟏
Where, γ1 is the surface tension of the water (standard)
113
Exercise

114
 1. At 293 K, for 10 mL stalagmometer gave 29 water drops and 86 ether drops. Densities of ether and water are
720 kg m-3 and 1000 kg m-3, respectively. Surface tension of the water is 7.2 X 10-2 Nm-1 . Calculate the surface
tension of the ether.

γ𝟏 𝒏𝟏 ρ𝟐
𝑺𝒖𝒓𝒇𝒂𝒄𝒆 𝒕𝒆𝒏𝒔𝒊𝒐𝒏 𝒐𝒇 𝒆𝒕𝒉𝒆𝒓, γ𝟐 =
𝒏𝟐 ρ𝟏
Here,
Surface tension of the water = γ1 = 7.2 X 10-2 N m-1
Density of water = ρ1 = 1000 kg m-3
Density of Ether = ρ2 = 720 kg m-3

No. of Water drops = n1 = 29

No. of Ether drops = n2 = 86

𝟕.𝟐 𝒙 𝟏𝟎−𝟐 𝒙 𝟕𝟐𝟎 𝒙 𝟐𝟗

Therefore, γ2 = = 1.75 x 10-2 Nm-1
𝟏𝟎𝟎𝟎 𝒙 𝟖𝟔

115
 Factors Affecting Surface Tension
Surface tension is caused by the effects of intermolecular forces at the interface. Surface tension depends
on the nature of the liquid, the surrounding environment, and temperature. Liquids, where molecules have large
attractive intermolecular force, will have large surface tension.
1. Impurities:
(a) Soluble Impurities:
-If the impurities are soluble then the surface tension may
increase.
-The surface tension of the liquid will decrease when
impurities are less soluble.
-For example, Camphor is less soluble in water, hence it
decreases surface tension of the water.
-On the other hand, the surface tension of the liquid will
increase when the impurities are more soluble.
-For example, the salt is more soluble in water, hence it
increases the surface tension of the water.
(b) Insoluble impurities: Insoluble impurities such as dirt, oil,
grease, etc. will decrease the surface tension of a liquid.
116
2.Temperature:
-The molecular attraction between liquid molecules
becomes weak when we increase temperature.
-Hence, the surface tension of liquid decreases as
we increase the temperature of the liquid.
-The temperature at which the surface tension of
the liquid becomes Zero is called the “Critical
Temperature” of that liquid.
Note: In many applications wish to decrease or
increase the surface tension. This can be done by
changing factors that affect surface tension. For
example, surfactants are added in water so that
dirt can be easily from clothes.
 Viscosity
Introduction:
-When we enter our finger into the liquid, we are
experiencing some barrier.
-In oils, we are experiencing such barrier more.
-It means, liquids are producing friction against the
motion.
-Such Frictional Force is referred as viscous force
and it belongs to the Viscosity property of the liquid.

Viscous Force:
-Let’s consider that a liquid is flowing in a tube.
-Liquid layer at the center will be having high velocity.
-Layer touching/close to the tube will be having almost zero
velocity.
-Hence, while moving from center to wall of the tube, velocity is
decreasing.
-these layers are travelling one over the other, thereby
generating a friction for the moving object.
117 -Such friction is responsible for the Viscous force.
 Co-efficient of Viscosity, η
Introduction:
-Newton has derived the basic equation for the friction between the liquids.
-And this equation is known as Newton’s Viscosity Law.
-When liquid is flowing in a tube at constant force, the operating viscous force is “F” will be:
(1). Directly proportional to the area (A) of the two layers (F ∝ A)
(2). Directly proportional to the relative velocity as well [F ∝ (V1-V2)]
𝟏
(3). Inversely proportional to the distance between the subsequent layers (F ∝ )
𝒍

…..(2) Here, η is referred as Viscosity Number and it is

𝑨 (𝑽𝟏−𝑽𝟐) η 𝑨 (𝑽𝟏−𝑽𝟐)
Therefore, F ∝ …..(1) F =
𝒍
𝒍 a constant which depends on the liquid.

Here, (V1-V2)/l is indicative of that velocity is dependant of the distance between the layers and it is referred
as velocity gradient.
𝑭
(𝑽𝟏−𝑽𝟐) −𝟏
A = 1 m2; =𝟏𝒔 ; 𝒉𝒆𝒏𝒄𝒆, 𝑭 = η.
η
𝑨(𝑽𝟏−𝑽𝟐)
Therefore, = …..(3) 𝒍
𝒍 𝒕𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆 𝒄𝒐 − 𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒕 𝒐𝒇 𝒗𝒊𝒔𝒄𝒐𝒔𝒊𝒕𝒚 𝒊𝒔 𝒅𝒆𝒇𝒊𝒏𝒆𝒅 𝒂𝒔 𝒇𝒐𝒍𝒍𝒐𝒘𝒔;
Definition: Is the operational force required per unit area to maintain a unit relative velocity between two
layers of fluid which are unit distance apart.
Unit: SI unit is Ns m-2 = Pa S (Pascal second)
Note: Co-efficient of Viscosity is an opponent term for the liquid’s flow.
118
 Measurement of Co-efficient of Viscosity, η:
Ostwald Method
➢ To determine the Co-efficient of Viscosity of a liquid, Pois-cuille equation (4) is used a lot.
➢ This equation offers the relation between the Co-efficient of Viscosity and speed of that liquid flow in a capillary
tube.

π𝒓𝟒 𝒕𝑷 Where, r = radius of the capillary tube, t = time of flow, P = pressure = hρg,
η =
𝟖𝑽𝒍
…..(4) V = volume of the liquid, l= length of the tube, η = Viscosity Number

π𝒓𝟒 𝒕 𝒉 ρ 𝒈 Where, h = hight of the liquid batch, ρ = density of the liquid, g = gravitational force
η = …..(5)
𝟖𝑽𝒍
➢ To determine the self Co-efficient of Viscosity of a liquid, all the parameters in the eqn (5) to be determined.
➢ Even though, in general it is determined by comparison with the water.
➢ Therefore, Co-efficient viscosity of water must be known at the various temperature.
➢ In practical, we are having the more accurate values of water at different temperature.
➢ Hence, unknown liquid’s value can be easily determined.
➢ Therefore, to determine the relative co-efficient of viscosity, both water and unknown sample are allowed to flow
in a capillary tube and time taken should be noted down.
➢ For a water and unknown liquid it should t1, η1 and t2, η2 , respectively
➢ Lets introduce these values in the eqn (5),
η𝟏 ρ𝟏 𝒕𝟏
= …..(5) Where, ρ1 and ρ2 are density of the water and unknown liquid, respectively
119 η𝟐 ρ𝟐 𝒕𝟐
 Procedure for Ostwald Viscometer
- Ostwald Viscometer is first washed with cromic acid mixture and dried.
- Subsequently, 20 mL of water (standard) is sucked and filled up in “A”.
C
- In the X-end water is sucked and brought up to “B”-level “O”.
- Subsequently, water is allowed to flow through the capillary tube “CD” and O
time t1 should be noted down. B
- Later, Ostwald Viscometer is washed, dried and filled with the 20 mL of D
sample liquid (unknown) in “A” up to the mark “O”.
- Subsequently, unknown sample is allowed to flow through the capillary tube
“CD” and time t2 should be noted down. X
- Now, co-efficient of viscosity water, n1 can be known from the standard
parameters. A
- Thereby, unknown sample’s co-efficient of viscosity, n2 can be determined
by using the following equation;
η𝟏 ρ𝟐 𝒕𝟐
η𝟐 =
ρ𝟏 𝒕 𝟏
Where, η1 is the co-efficient of viscosity of the water (standard)
120
 Let's see some liquids Surface Tension, γ and Co-efficient of Viscosity, η

S. Liquid Surface Tension, N m-1 Co-efficient Viscosity.

No Pa s
1 Water 7.275 x 10-2 1.002 x 10-3
2 Ethanol 2.227 x 10-2 1.119 x 10-3
3 Benzene 2.290 x 10-2 6.490 x 10-4
4 Glycerol 6.520 x 10-2 8.300 x 10-1
5 Mercury 5.200 x 10-2 1.570 x 10-3

121
Exercise

122
 1. Viscosity no of water is 1.002 X 10-3 Pa s . At 293 K, for 20 mL water has taken 58 s to flow in a capillary tube.
The same volume of Benzene has taken 46 s, therefore calculate the co-efficient of viscosity for Benzene.
Densities of Water and Benzene are 1000 kg m-3 and 800 kg m-3, respectively.

η 𝟏 ρ𝟐 𝒕 𝟐
𝑪𝒐 − 𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒕 𝒐𝒇 𝑽𝒊𝒔𝒄𝒐𝒔𝒊𝒕𝒚, η𝟐 =
ρ𝟏 𝒕 𝟏
Here,
Viscosity No of water = η1 = 1.002 X 10-3 Pa s
Density of water = ρ1 = 1000 kg m-3
Density of Benzene = ρ2 = 800 kg m-3

Time for Water = t1 = 58 s

Time for Benzene = t2 = 46 s

𝟏.𝟎𝟎𝟐 𝒙 𝟏𝟎−𝟑 𝒙 𝟖𝟎𝟎 𝒙 𝟒𝟔

Therefore, η2 = = 6.352 x 10-4 Pa s
𝟏𝟎𝟎𝟎 𝒙 𝟓𝟖

123
 Factors Affecting Co-efficient of Viscosity, η
1. Pressure, 2. Temperature, 3. Liquid’s Shape, 4. Liquid’s Size, 5. Molecular Interaction Force.

1. Pressure: 2. Temperature:
-Liquid’s viscosity is increasing while increasing the pressure -Liquid’s viscosity is decreasing while increasing the
because, while increasing the pressure liquid’s molecules Temperature.
come close to each other. - From the several experiments, when we raise the
- Hence, no.of pores i.e., distance between the molecule is liquid’s temperature by 1 °C, viscosity do decrease
decreasing. by 2 %.
-Therefore, mobility of the liquid become difficult hence -Relationship between temperature and viscosity can
flow become less, means viscosity increases. be mathematically represented as follows;
3. Liquids Shape: 𝑨. 𝒆𝑬 Where, A and R are constants. E =
-Depending upon the mass enhancement of the Liquid η= Kinetic energy for the viscous
molecule, viscosity is increasing. 𝑹𝑻 movement (shear force).
- For example alcohols with low molecular weight do flow
fast.whereas alcohols with high molecular weights do appear
5. Molecular Interaction Force:
as oil and having high viscous in nature. -Due to the Hydrogen Bonding interactions Water do
have high viscous value.
4. Liquids Size: -similarly, glycerol is having more no. of –OH groups
(3) hence, more hydrogen bonding and more viscosity
-Depending upon the branches of the molecule, viscosity is
124
increasing.
125
 BSc. Sem-II, CHB-201_Unit-2 _Thermodynamics

Thermodynamics: Thermodynamic quantities (w, q, ΔU and ΔH) for isothermal and adiabatic reversible expansion of ideal
gases, variation of heat of reaction with temperature (Kirchhoff’s equation), Joule-Thomson effect, Joule-Thomson coefficient
of real (van der Waals) gases, Second Law of Thermodynamics: entropy, entropy changes for an ideal gas, entropy changes
at constant pressure and volume, entropy change in spontaneous processes, physical significance of entropy, Carnot cycle,
free energy and maximum work functions, conditions for spontaneous changes and equilibrium, Maxwell relations, Gibbs-
Helmholtz equation, van’t Hoff equation, reaction isotherm.

Dr. S. Manivannan
Dept of Chemistry
Banaras Hindu University

126
 Thermodynamics = Thermo (Heat) + Dynamics (Motion)

Heat flow from one Melt down gradually and Water gets heated and Cool down gradually and
end to another end achieves room temperature finally started to boil achieves room temperature
⚫ “Thermodynamics is the science that describes how thermal energy is converted from one form to other and how it affects the matter”
⚫ It deals with energy change accompanying all types physical and chemical processes.
⚫ It depends on three fundamental laws (Zero, First and Second).
⚫ There are several natural processes happening and are representative of these laws.
⚫ And none of the natural process is against the thermodynamics.
⚫ Most of the important generalizations of physical chemistry such as “Van’t Hoff law of dilute solutions”, “Raoult’s Law of Vapour pressure
lowering”, “distribution law”, “law of chemical equilibrium” “phase rule” and the “laws of electrochemistry” can be deduced from the
thermodynamics.
⚫ It helps to predict whether a given process, or a chemical reaction is feasible under the given conditions of temperature, pressure and
concentration.
⚫ The law of thermodynamics apply to behavior of assemblies of a vast number of molecules and not to individual molecule.
⚫ For example, thermodynamics predicts that hydrogen and oxygen gases would react at ordinary temperature to yield Water. But it does
not tell whether the reaction will be fast or slow.
127
 Terms Used Thermodynamics
⚫ To have better understanding of Thermodynamics it is essential to understand the frequently used “terms”.
⚫ Let's discuss them one by one….
System:
A system may be defined as any specified portion of matter
under study which is separated from the rest of the universe with a bounding
surface. A system may consist of one or more substances.

Surroundings:
The rest of the universe which might be in a position to exchange
energy and matter with the system is called surroundings. In simple cases,
surroundings generally imply air, or a water-bath in which a system under
examination is immersed.

Boundary or Wall:
It separates the system from the surroundings.
(1) Rigid Wall: No change in structure and location.
(2) Impermeable Wall: Matter cannot be transferred.
(3) Permeable Wall: Both Matter and Energy can be transferred.
(4) Adiabatic Wall: If there is no force outside of the system, Matter and
Energy cannot be transferred. Ex: Thermo Flask
(5) Diathermal Wall: If there is no force outside of the system, Matter is not
transferred but Energy (Heat) is transferred. Ex: Metal Container.
128
 Thermodynamic Systems
Types of System:
There are three types of system, lets see them in detail….
(1) Open System: A system which can exchange matter as well as energy with its
surroundings is said to be an open system.
ex: 1. water in an open container, 2. Vaporization of water from the
lake.

(2) Closed System: A system which can exchange energy but not matter is called a
closed system.
ex: Solution in a closed container.

(3) Isolated System: A system which can exchange neither energy not matter with
its surroundings is called an isolated system.
ex: Coffee in a Thermoflask.
(4) Homogenous System: A system is said to be homogenous when it is completely Surroundings
Surroundings Thermostat Heat
uniform throughout.
ex: 1.gas phase
H2 + I2 2HI
2. liquid phase Vapour Vapour
CH3COOC2H5 + H2O CH3COOH + C2H5OH Heat
Vapour

Water Water
(5) Heterogenous System: A system is said to be heterogenous when it is not Water System
completely uniform throughout.
System Closed System
129 Open System Isolated System
ex: 2 KClO3 (Solid) 2 KCl (solid) + 3 O2 (gas)
 Thermodynamic System’s Properties

There are two different types of system’s properties, lets see them in detail….

(1) Extensive Property: An extensive property of system is that which depends on the amount of substance or substances present in
the system.
ex: Mass, Volume and Energy

(2) Intensive Property of a system is that which is independent on the amount of substance present in the system.
ex: Temperature, Pressure, Density, Concentration, Viscosity, Refractive Index, Surface Tension, and Specific Heat

130
 Thermodynamic Processes and Their Types

“The operation by which a system changes from one state to another state is called process”

-Whenever a system changes from one state to another state it is accompanied by change in energy.
-In case of open systems, there may be change of matter as well.

The following types of processes are known.

(1) Isothermal Process

(2) Adiabatic Process
(3) Reversible Process
(4) Irreversible Process
(5) Cyclic Process
(6) Isochoric Process
(7) Isobaric Process
Let’s see them in detail….

131
 Processes and Their Types Explained
(1) Isothermal Process:
-A process is said to be isothermal if the temperature of the system remains constant during each stage of the
process. In order to do that either heat is supplied from the surroundings or liberated from the system.

(2) Adiabatic Process:

-A process is said to adiabatic if no heat enters or leaves the system during any step of the process. In order to
do that an Insulator is used. But there may be a fluctuation in temperature.

(3 and 4) Reversible Process & Irreversible Process:

-A process carried out infinitesimally slowly so that the driving force is only infinitesimally greater than the opposing
force, is called reversible process.
-Any process which does not take place in the above manner, i.e., a process which does not take place infinitesimally
slowly, is said to be an irreversible process.
132
 Processes and Their Types Explained (Cont.…)
-Features of the Reversible process process are as follows;
-A reversible process cannot be realized in practice because it would require infinite time for its completion.
-Having several steps and slowly progressing.
-In each step, system will be in equilibrium with surroundings.
-Hence, almost all the processes occurring in nature or laboratory are irreversible.
- A reversible process, therefore, remains, imaginary and theoretical.
(5) Cyclic Process:
-A process carried out to enable the system to undergo several states and comeback again to the initial state is
said to be cyclic process.
-the above path is referred as cycle. Ex: Carnot cycle.
(6) Isochoric Process:
-A process is said to isochoric if no change in volume of the system during the process. But there may be a
fluctuation in pressure. Ex: N2 (gas) + 3 H2 (gas) 2 NH3 (gas) (change in pressure)
(7) Isobaric Process
A process is said to isobaric if no change in pressure of the system during the process. But there may be a
133
fluctuation in volume.
 Thermodynamic Functions
-To explain the system’s properties, pressure, volume, moles, temperature, heat and work are sufficient.
-But still, deriving and using the new thermodynamic functions are good.
- Some of the thermodynamic functions are summarized in the table.

S. No Name Symbol Definition

1 Internal Energy U dU = dq-dw
2 Enthalpy H H = U + PV
3 Heat accepting capacity at constant Volume Cv Cv = (∂U/∂T)V
4 Heat accepting capacity at constant Pressure Cp Cp = (∂H/∂T)P

5 Entropy S dS = dq(rev)/T
6 Work function A A = U-TS
7 Free Energy G G = H-TS
8 Chemical Pressure μ μ = (∂G/∂n)T, P, nj j ≠ i
134
 State and Path Functions
State Functions:
-If a constant’s values are dependent of only a system’s initial and
final states means those functions are known as State functions.
-these values are not dependent of path of the change and can be
referred as “Path Independent Functions”
Ex: Internal energy, Enthalpy, Entropy, Work function and
Free energy.

Path Functions:
-Properties which are dependent of how the change/path has
occurred in the system is known as “Path Functions”
Ex: Work done, Consumed heat.
135
 Thermodynamic Equilibrium
-A system in which the macroscopic properties (Pressure, Volume and Mass) do not undergo any change with time is
said to be in thermodynamic equilibrium.
-Suppose a system is heterogenous, i.e., it consists of more than one phase.
-Then, if it is in equilibrium, the macroscopic properties in the various phases remain unaltered with time.
- The thermodyanamic equilibrium implies the existence of three kinds of equilibria in the system:
1. Thermal equilibrium, 2. mechanical equilibrium, 3. chemical equilibrium

-A system is said to be in thermal equilibrium if there is no flow of heat from one portion of the system to another.
This is possible if the temperature remains the same throughout in all parts of the system.

-A system is said to be in mechanical equilibrium if no mechanical work is done by one part of the system on another
part of the system. This is possible if the pressure remains the same throughout in all parts of the system.

-A system is said to be in Chemical equilibrium if the composition of the various phases in the system remains the
same throughout.
136
 Zeroth Law of Thermodynamics

Def: The zeroth law of thermodynamics states that if two thermodynamic systems (A and B) are each in thermal equilibrium with a third
system (C), then they are in thermal equilibrium with each other. Accordingly, thermal equilibrium between systems is a transitive relation.
Explanation:
-Let’s consider two objects A and B. In which A, stays in high temperature, T2 and B, stays in low temperature T1.
- Consider now both system A and B are now connected with “diathermal wall”.
- Heat do flow from higher to lower and continues up to both become equal in T (thermal equilibrium).
- Now let’s consider of making thermal contact between A, B with the third object C.
- Meanwhile, assume that there is no contact between A and B.
- Later some time, A and C will be in thermal equilibrium. Besides B and C also will be in thermal equilibrium.
- Even though A and B are not in thermal contact still A and B also will be in thermal equilibrium.
- Thermometers are designed based Zeroth Law.

137
 Heat, Work and Energy
- “Energy” is defined as the system’s ability to carryout the work. Hence, energy will accept unit of the work.
- Energy is the essential thing for the all living hood in the earth.
- Sun is fulfilling the energy requirement of the earth and stored in many ways.
- During the photosynthesis, starch is stored by the plants by converting the Sun’s energy into chemical energy.
- Plants got buried centuries ago transforms into “Coal”
- Sun’s energy can be converted into other possible energy and several work can be done. (Solar energy Harvesting)

138
 Types of Energy
- Let’s see some types of Energy in here:
1. Kinetic Energy: Energy produced due to the movement of the object.
2. Potential Energy: In a filed, energy gained by the object with respect to its position in the field.
-Ex:(a) Ball in higher place, (b) Electrified particle in an electric field.
3. Chemical Energy: Because of the chemical bonds, chemical is having an energy.
4. Nucleus Energy: An atom is having energy due to its type of nucleous.
5. Light Energy
6. Electric Energy
7. Mechanical Energy, 8. Heat Energy, 9. Magnetic Energy

139
 Types of Energy (Cont.)
- All types of energy is based on two different factors:
1. Capacity factor
2. Intensify factor
-capacity factor is depending on the objects quantity but intensify factor is not.
-When two object differ in intensify factor means energy is transformed from one object to another.
-i.e., Energy is transformed from the object with higher Intensify factor to lower one.
- in Chemistry, energy transformations plays vital role. During the chemical rection, chemical energy is transformed.
-For ex: energy is confined in the “Coal” but it is coming out only we do burn, liberating the heat energy.
-S.I Unit for energy is Joule. Kilo Joule (KJ) is used as unit of high energy. 1 KJ = 1000 J.
-Following table is representative of various energies both factors:

S. No Name of the Energy Definition Intensify Factor Capacity Factor

1 Kinetic Energy ½ mc2 Velocity (C) Mass (m)

2 Mechanical Energy -F dh Force (F) Difference in distance (dh)

-pdV Pressure (P) Difference in Volume (dV)
3 Electric Energy -nFE Potential Difference (E) Current flow (nF)
4 Potential Energy mg dh Gravitational force (g dh) Mass (m)
5 Magnetic Energy HdM Field Strength Magnetic rotational force
140
(dM)
 Internal Energy
- Every substance is associated with a definite amount of energy which depends on its chemical nature, as well as upon its
temperature pressure and volume and it is known as its “Internal Energy”.
- The exact magnitude of this energy is not known because the chemical nature includes such interminant factors as the
(a) translational, (b) rotational, and (c) vibrational movements of the molecules, (d) the way the molecule are put
together, (e) the nature of individual atoms, (f) the arrangement and no.of atoms, (g) energy possessed by nucleus, etc.
- But one thing is certain that the internal energy of a substance or system is definite quantity, and it is function of only of
the state (i.e., chemical nature, composition, temperature, pressure and volume) of the system at the given moment

- An objects Internal Energy is mentioned as “U”

- Its value is dependent of object’s quantity.
- Internal Energy’s (U) exact magnitude is not easy to determine but difference in internal energy (ΔU) can be easily
calculated.
- ΔU is dependant of initial and final state of the system.
- And it is state or path independent function,
- Therefore,
𝜕𝑼 𝜕𝑼 𝜕𝟐 𝑼 𝜕𝟐 𝑼
U = f(T, V) hence, (i) dU = dT + dV (ii) = (iii) ‫ = 𝑼𝒅 ׯ‬0
𝜕𝑻 𝑽 𝜕𝑻 𝑻 𝜕𝑽𝜕𝑻 𝜕𝑻𝜕𝑽

141 - Like the other energies, Internal energy can be converted into the Heat energy.
 First Law of Thermodynamics
The first law of thermodynamics is a version of the law of conservation of energy,
adapted for thermodynamic processes, distinguishing two kinds of transfer of
energy, as heat and as thermodynamic work, and relating them to a function of a
body's state, called Internal energy.

- First law states that energy can neither be created nor destroyed although it can be transformed from one form to
another.
- This is also known as law of conservation of energy.
- Thus, whenever energy in one form disappears an equal amount energy in some other form must appear.
- The law is based on the cumulative experience of ages that it is impossible to construct a perpetual motion machine,
- i.e., the machine which can produce energy without expenditure of energy.

-Perpetual motion is the motion of bodies that continues forever in an

unperturbed system.

-A perpetual motion machine is a hypothetical machine that can do work

infinitely without an external energy source.

-This kind of machine is impossible, as it would violate either the first or

142 second law of thermodynamics or both.
 First Law of Thermodynamics (cont.)
- The total energy of the isolated system is always constant.
- Energy of the universe is constant.
- Total energy of the System + Surroundings is constant.
- Algebraic sum of the isolated system’s energy transformations is “Zero”.
- It is now known that energy can be produced by the destruction of the Mass, the two quantities being related by the
expression E = mc2 where, E is energy produced by the destruction of mass, m and c is the velocity of light. The
modified law, therefore, states that the total mass and energy of an isolated system remains unchanged.
- First law of thermodynamics can be mathematically expressed as follows;

(a) dU = q - w Or ΔU = Q - W

(b) dU = q - PdV Or ΔU = Q - PΔV

(c) dU = ∂q - ∂w

where, dU = minor change in internal energy

∂q = small amount of consumed heat
∂w = small amount of work done
143
 First Law of Thermodynamics (cont.)
Derivation of ΔU = q – w

- Let’s consider a system’s initial (A) internal energy as UA and final state’s (B) internal energy as UB.
- Now system’s energy is flowing from initial (UA)A low energy to higher enegy (UB)B.
- To reach this change, system is consuming heat, “q” from the surroundings and doing the work, “w”.
- Since, heat is consumed system’s energy is increasing.
- But because of the work done, energy is decreasing.
- Therefore, internal energy of the system, ΔU is,

ΔU = (UB - UA) = q – w …(1)

Eqn (1) is the mathematical form of the first law.

Symbol Explanation,
1. when heat is consumed “q” will have +Ve sign
2. When heat is liberated “q” will have –Ve sign
3. When system is not doing anything means, “w” will have +Ve sign
4. When system is doing work means, “w” will have -Ve sign
5. during expansion, “w” will have +Ve sign
144
6. during contraction, “w” will have –Ve sign.
 Change in Heat at Constant Volume (q)v
Mathematical expression of the First Law, ΔU = q – w …(1)

Therefore, q = ΔU +w ……(2)

Let’s consider that there is an expansion in a system,

W = P ΔV ….(3) Here, P = Pressure, ΔV = increase in volume

Therefore, q = ΔU + P ΔV…..(4)

When we carryout process at the constant volume, there is no change in the volume,
i.e., ΔV = 0.

Hence, Mechanical work, w = P x 0 = 0.

Therefore, (q)v = ΔU + 0….(5), (q)v = ΔU….(6)

Hence at constant volume, all the heat consumed by the system is utilized only to rise the ΔU.
145
 Change in Heat at Constant Pressure (q)p-Enthalpy (H)
Def: Thermodynamic quantity equivalent to the total heat content of a system.
It is equal to the internal energy of the system plus the product of pressure and volume.
-the change in enthalpy associated with a particular chemical process.
-most compounds have negative enthalpies of formation.

-Although the internal energy represents the total energy of a system, and the first law of thermodynamics is
based on the concept of internal energy.

-It is not always the best variable to work with.

- Equation, q = ΔU + P ΔV shows that the change in the internal energy is exactly equal to “q” if the
volume of the system remains constant for a particular process.

- However, the experimental condition of constant volume can be difficult to guarantee for many
processes.
-Constant pressure, considering that many experiments occur exposed to the atmosphere, is
often an easier experimental parameter.

146
 Change in Heat at Constant Pressure (q)p-Enthalpy (H) (Cont.1)
Let’s consider a system being transformed from one phase to another phase. Furthermore, let’s assume that there is volume
change (ΔV). Here,

ΔV = (VB – VA) …(1)

Mechanical work, w = P ΔV = (VB - VA) ……(2)

Mathematical expression of the First Law, ΔU = q – w …(3), Therefore, q = ΔU + w ……(4)

But, ΔU = (UB – UA), w = P ΔV = P(VB - VA) ……(5)

Hence, q = (UB – UA) + P(VB - VA) ……(6),

q = (UB – UA) + PVB - PVA) ……(7), q = (UB + PVB) – (UA + PVA) ……(8)

Here, (U + PV) is referred as system’s Enthalpy, H and it indicative of the total energy stored in system.

Means, H = U + PV ….(9), therefore, HB = UB + PVB ….(10), HA = UA + PVA ….(11)

147
Therefore, HB – HA = ΔH …(12), (UB – UA) + P(VB - VA) = ΔH …(13), i.e., ΔH = ΔU + P ΔV …(14)
 Significance of Enthalpy (H)
The heat liberated or consumed during a chemical reaction can be taken as the reaction temperature.
If so, difference between the heat of the reactants (HR) and Heat of the products (HP) is referred as
Total heat of the system (ΔH). i.e., ΔH = HP – HR

“ΔH is referred as a Enthalpy of the reaction”.

Similar to Internal Energy (U), Enthalpy (H) also an “Extensive Property” Furthermore, Enthalpy is dependent of initial and
final state hence, it is “State Function” too.

𝜕𝑯 𝜕𝑯 𝜕𝟐𝑯 𝜕𝟐𝑯
Therefore, H = f(T, P) hence, (i) dH = dT + dP (ii) = (iii) ‫ = 𝑯𝒅 ׯ‬0
𝜕𝑻 𝑷 𝜕𝑷 𝑻 𝜕𝑻𝜕𝑷 𝜕𝑷𝜕𝑻

-Reaction’s internal energy is ΔU at constant Volume.

-the ΔU’s value is equal to either energy change consumed or liberated from the reaction
-Hence, the total heat energy change (ΔH) is equal to the ΔU.
Means when a reaction is proceeding at constant Volume, ΔH = ΔU.
-When reaction is proceeding at the constant pressure,
the ΔH of the reaction is the sum of ΔU and work done (P ΔV)
148
Hence, ΔH = ΔU + P ΔV
 Endothermic & Exothermic Reactions
-Interpretation of the statement that ΔH for a chemical process is the difference between the total enthalpies of the
products (Hp) minus the total enthalpies of the reactants (HR).

ΔH = HP - HR
(a) An exothermic reaction, since the total energy of the system is going down (meaning that energy is given off).
(b) An endothermic reaction, since the total energy of the system is going up (meaning that the energy is entering the
system).

(a) An exothermic reaction, (b) An endothermic reaction,

Reactants Products + Heat Reactants + Heat Products

Here, ΔH = HP – HR = -Ve value, Because HR > HP Here, ΔH = HP – HR = +Ve value, Because HP > HR
149
Ex: CH4 + 2 O2 CO2 + 2 H2O + 890 kJ Ex: C + H2O + 131 kJ CO + H2
C + O2 CO2 + 393.5 kJ C + 2 S + 92 kJ CS2
 Derivation of Relationship between the ΔU and ΔH
-Let’s consider a reaction preceding at constant Pressure,

ΔH = ΔU + P ΔV ….(1)
- here, reaction is occurring in between the solid and liquid phases hence, the aroused volume change, ΔV is so small. So, for these type
reactions, P ΔV is negligible.
ΔH = ΔU ….(2)
But, in a reaction if gaseous phase is involved means, ΔV-value is significantly considerable.
-let’s fix “V” as volume of one mole of gas for a gas phase reaction.
-and “Δn” is difference between the total moles of products and reactants.

i.e., Δn = Gaseous product’s Total Moles – Gaseous reactant’s total moles ….(3)
Hence, volume change can be written as follows;
𝑃𝛥𝑉
ΔV = V Δn …(4), multiply eqn (4) with Pressure on both side, P ΔV = P V Δn…(5), Hence, PV = …. 6
𝛥𝑛
Equation for the one mole of an Ideal Gas, PV = RT ….(7)
𝑃𝛥𝑉
Comparing eqn (6) and eqn (7), = 𝑅𝑇 … . 8 , Therefore, P ΔV = RT Δn ….(9)
𝛥𝑛
Applying eqn (9) in eqn (1), ΔH = ΔU + RT Δn ….(10)
Significance:
-by using the eqn (10), if ΔH-value at constant volume is known means, ΔH-value at constant pressure can be calculated.
-Several reaction are occurring at constant pressure only hence; such reactions are more studied.
150
Exercise

151
 1. At 300 K, calculate the ΔH of the following reaction. 2 CO2 (g) + O2 (g) 2 CO2 (g). ΔU = -563.5 kJ for this
reaction.

ΔH = ΔU + RT Δn

Here, ΔH = ?

ΔU = -563.5 kJ = -563500 J, R = Gas Constant = 8.314 J K-1 mol-1, T = Temperature = 300 K

For the 2 CO2 (g) + O2 (g) 2 CO2 (g) reaction

Δn = nP – nR = 2 – (2+1) = 2 - 3 = 1

ΔH = -563500 + 8.314 x 300 (-1) J

= -(563500 + 8.314 x 300 x 1) J

= -(563500 + 2494.2) J

= -565994.2 J

152 ΔH = -566 kJ
 Reversible and Irreversible Processes
⚫ Reversible Process
- The system changes so that the system and surroundings
can be returned to the original state by exactly reversing
the process.
- This maximize the work done by a system on surroundings.
- Change from initial to final state occurs by an infinite
number of infinitesimal changes.
⚫ Irreversible Process
-irreversible processes cannot be undone by exactly
reversing the change to the system or cannot
followed in reverse.
-Also, any spontaneous process is irreversible.
-change from initial to final state occurs by a finite
number incremental steps.

⚫ Although both the reversible and irreversible reactions

having the same starting and ending points when the volume is
V1 to V2, the pressure for an irreversible reaction is lowered
from the start, since there was an abrupt change.

153
 q, w, ΔU and ΔH values in an Isothermal Process
Ideal gas reversible expansion
Isothermal Process:
-A process is said to be isothermal if the temperature of the system remains constant during each stage of the process. In
order to do that either heat is supplied from the surroundings or liberated from the system.
-Let’s begin with the mathematical expression for the first law, -ideal gas equation for the “n” moles,
𝑛𝑅𝑇
PV = nRT, P = ….(7),
𝑉
ΔU = q - w ….(1), 𝑛𝑅𝑇
Therefore, w = pdV = dV….(8),
𝑉
for an Ideal gas Internal energy, U = f (T,V) ….(2),
Integrating eqn (8) in the suitable boundaries at constant temperature,
-hence at constant temperature there won't be any change in Internal
𝑉 𝑑𝑉 𝑉
energy, i.e., ΔU = 0….(3), w = nRT‫ 𝑉׬‬2 ….(9), w = nRT ln 𝑉2….(10)
therefore, 1 𝑉 1

𝑉
0 = q – w ….(4), or q = w ….(5) w = 2.303 nRT log 𝑉2….(11)
1

means at the isothermal process, 1

Based on Boyle’s law, V ∝ hence,
𝑃
Absorbed Heat (q) = Work done (w)
𝑃1
w = 2.303 nRT log ….(12)
𝑃2
154 -During the Ideal gas reversible expansion, dV work done,
W = P dV …(6)
q, w, ΔU and ΔH values in an Isothermal Process (cont..)
Change in Enthalpy, ΔH = H2 – H1 ….(13)

Besides, H = U + PV ….(14)

Therefore, ΔH = (U2 + P2 V2) – (U1 + P1 V1)….(15)

ΔH = (U2 – U1) – (P2 V2 - P1 V1)….(16)

At constant temperature, ΔU = 0 and for the ideal gas, P2 V2 = P1 V1

Hence, ΔH = 0 + 0 = 0 ….(17)

Therefore, at constant temperature for the Ideal gas reversible expansion,

ΔU = 0 = ΔH
𝑉2
155
w = q = 2.303 nRT log = 2.303 nRT log 𝑃𝑃1
𝑉1 2
Exercise

156
 1. At 27 °C, 16 g of O2 isothermally expanding from 20 lit to 40 lit in a reversible manner. Calculate the work
done, consumed heat, internal energy and enthalpy of the reaction. Follow the ideal expansion.

𝑽𝟐
w = q = 2.303 nRT log J
𝑽𝟏

Here, n = mass/molar mass = 0.016/0.032 = 0.5

R = 8.314 JK-1 mol-1

T = 27 °C = 300 K; V1 = 20 lit; V2 = 40 lit

𝟒𝟎
Therefore, w = q = 2.303 x 0.5 x 8.314 x 300 log J
𝟐𝟎

= 2.303 x 0.5 x 8.314 x 300 log 2 J

= 2.303 x 0.5 x 8.314 x 300 x 0.3010 J

W = q = 864.5 J

ΔU = ΔH = 0 J
157
 q, w, ΔU and ΔH values in an Adiabatic Process
Ideal gas reversible expansion
Adiabatic Process:
-A process is said to adiabatic if no heat enters or leaves the system (q = 0) during any step of the process.
In order to do that an Insulator is used. But there may be a fluctuation in temperature.
-Let’s begin with the mathematical expression for the first law, - For an ideal gas, internal pressure is Zero.
hence, dU = CV dT + 0 dV ….(3)
ΔU = q - w ….(1), ΔU = 0 - w ….(2), or -ΔU = w….(3), dU = CV dT ….(4)

Integrating eqn (4) in the suitable boundaries,

-it means internal energy is utilized to carryout the work.
-and the internal energy is again dependent of temperature hence, 2 2
during the Adiabatic process temperature will go down/fluctuate. ‫׬‬1 𝑑𝑈 = 𝐶𝑉 ‫׬‬1 𝑑𝑇 ….(5),
(U2- U1) = ΔU = CV (T2 – T1) …(6)
(a) Measurement of Internal energy:
U = f (T,V) ….(1),
w = -ΔU = n CV (T2 – T1) = n CV (T1 – T2) …(7)
𝜕𝑈 𝜕𝑈
Therefore, dU = dT + dV ….(2)
𝜕𝑇 𝑉 𝜕𝑉 𝑇
Here,
𝜕𝑈
𝜕𝑇 𝑉
= Molar heat capacitance, CV;
𝜕𝑈
158 𝜕𝑉 𝑇
= internal pressure
 q, w, ΔU and ΔH values in an Adiabatic Process (Cont.)
(b) Measurement of Enthalpy: - When a gas is expanding reversibly in a Adiabatic process,

Change in Enthalpy, ΔH = H2 – H1 ….(1) q=0

Besides, H = U + PV
ΔU = n CV (T2 – T1)
Therefore, ΔH = (U2 + P2 V2) – (U1 + P1 V1)….(2)
ΔH = n Cp (T2 – T1)
ΔH = (U2 – U1) – (P2 V2 - P1 V1)….(3)
w = n CV (T1 – T2)
Therefore, ΔH = ΔU + n R(T2 – T1)….(4)
(for the ideal gas, PV = n RT)
- To measure above values, we need initial (T1) and final (T2)
ΔH = n CV (T2 – T1) + n R(T2 – T1)…..(5) temperature of the system.

ΔH = (CV + R) + n (T2 – T1)……(6)
ΔH = n CP (T2 – T1)……(7)
(because CV + R = CP)
- But When an Ideal gas is expanding or contracting only
Volume and Pressure values are known.
- Hence, to find out the final temperature of the system,
additional equations need to be derived.

159
 Additional Equations for Adiabatic Process
(a) Volume-Temperature, V–T Relationship

𝑽 𝑪𝑷
T2 = T1 [ 𝟏]γ-1 (γ = )
𝑽𝟐 𝑪𝑽

(b) Pressure – Volume, P–V Relationship

𝑽 𝑪𝑷
P2 = P1 [ 𝟏]γ (γ = )
𝑽𝟐 𝑪𝑽

(c) Pressure – Temperature, P–T Relationship

𝑷 𝑪𝑷
T2 = T1 [ 𝟏]γ-1/γ (γ = )
𝑷𝟐 𝑪𝑽

160
 Variation of Heat of Reaction (ΔH) with Temperature/
Kirchhoff’s Equation
-A reaction’s heat at constant pressure can be represented from the reactants and products molar enthalpy as follows; i.e.,
Integrating eqn (5) in the suitable boundaries,
Change in Enthalpy, ΔH = HP – HR ….(1)
𝐻 𝑇
here, HP = enthalpy of products, HR = enthalpy of reactants ‫ 𝐻׬‬2 𝑑𝛥𝐻 = ‫ 𝑇׬‬2 𝛥 𝐶𝑃 𝑑𝑇 ….(6),
1 1
𝑇
Let’s differentiate the eqn (1) with respect to the Temperature,
ΔH2 – ΔH1 = Δ CP ‫ 𝑇׬‬2 𝑑𝑇 ….(7),
1
𝑑 𝛥𝐻 𝑑 𝐻𝑃 𝑑 𝐻𝑅
= − ….(2) Because, when dT is less, Δ CP is a constant
𝑑𝑇 𝑑𝑇 𝑑𝑇
Therefore, ΔH2 – ΔH1 = Δ CP (T2 –T1)….(8),
𝑑 𝐻𝑃 𝑑 𝐻𝑅
But we know = 𝐶𝑃 𝑃 and = 𝐶𝑃 𝑅
𝑑𝑇 𝑑𝑇 Or, ΔH2 = ΔH1 + Δ CP (T2 –T1)….(9),
𝑑 𝛥𝐻 Eqn (9) is another form Kirchhoff’s equation.
Hence, = 𝐶𝑃 𝑃- 𝐶𝑃 𝑅 …..(3)
𝑑𝑇 -Based on eqn (4), Kirchhoff’s equation can be explained as follows;
𝑑 𝛥𝐻 “At constant pressure, Variation of heat of reaction is equal to the
Hence, = 𝛥𝐶𝑃 …..(4) difference between the products and reactants specific molar heat
𝑑𝑇 capacitance (CP)”
Here, 𝛥𝐶𝑃 = 𝐶𝑃 𝑃 - 𝐶𝑃 𝑅
Significance:
(1) Variation of Heat with respect to Temperature of the reaction.
Eqn (4) can be rewritten as follows, (2) By using the Kirchhoff’s equation, heat of the reaction is known at particular Temperature
then in another Temperature, heat of the reaction can be calculated.
161 𝑑 𝛥𝐻 = 𝛥CP dT ….(5) (3) Eqn (9) can be used when temperature difference is less. If not, integrated version, eqn (7)
should be used.
 Joule’s Law/Determination of Internal Energy/
Joule’s Experiment
Definition:
“Joule's second law states that the internal energy of an ideal gas is independent of its volume and pressure, depending
only on its temperature.”
𝜕𝑈 𝜕𝑈
Mathematically it can be represented as, = 0; is the internal pressure of a gas
𝜕𝑉 𝑇 𝜕𝑉 𝑇

Determination of Internal Energy, - Joule’s Experiment Or Proving Joule’s Law:

𝜕𝑈
-By using the measurable properties of object, it is not easy to determine the –value.
𝜕𝑉 𝑇
𝜕𝑈
-But, theoretically for Ideal gases, -value can be measured from the Joule’s experiment.
𝜕𝑉 𝑇
-Instrument used in the experiment is shown here.

Stirrer -Two gas containers (A, B) are connected by a volve (T).

Thermometer
-Container “A” is completely filled with air, but vacuum is applied in container “B”.

-Setup is kept in a water bath, stirred well and temperature is noted down (X).
T
-Now volve “T” is opened for expansion/diffusion of gas from “A” to “B”.
A B -Stirred well and temperature is noted down (Y).

-interestingly, there is no difference in temperature (X = Y).

162 Water bath
 Joule’s Law/Determination of Internal Energy/
Joule’s Experiment (Cont.)
Inferences of Joule’s Experiment:
-Gas is expanding in a vacuum hence, the gas not doing any work.
-Gas is spontaneously expanding, w = 0.
-Gas is not exchanging any of the heat with the surroundings. Therefore, q = 0.
-Let’s begin with the mathematical expression for the first law,

dU = q - w ….(1), dU = 0 - 0 ….(2), or dU = 0 ….(3), Significance and Limitations:

But U = f (T,V) ….(4),
(1) Joule’s experiment is suitable for ideal gas. Because
by differentiate, dU =
𝜕𝑈
dT +
𝜕𝑈
dV ….(5) internal pressure of the Ideal gas is Zero.
𝜕𝑇 𝑉 𝜕𝑉 𝑇
In the experiment, system is in equilibrium with the water
(2) For Real gases, mostly internal pressure value is very
bath, there is no temperature change. i.e., dT = 0
less, and it is having +Ve sign.
𝜕𝑈
Hence, dU = 𝜕𝑉 𝑇 dV = 0 ….(6) (3) In joule’s experiment, the water bath used is having
-in eqn (6), dV ≠ 0. hence, more specific molar heat capacitance. On contrary,
𝜕𝑈
= 0 ….(7) the gas used is having less specific molar heat
𝜕𝑉 𝑇 capacitance. Thereby the error is minimized.
From the eqn (7), it can be learned that internal energy of an ideal gas
is independent of its volume and pressure, depending only on its
163 temperature
 Joule, Thomson, and the birth of big science
https://carnotcycle.wordpress.com/2013/01/01/joule-thomson-and-the-birth-of-big-science/

William Thomson, later Lord Kelvin (left), James

Joule and the famous hand-operated pump. The Refrigerators, liquefied gases for
Joule-Thomson effect is named after them, as are industrial and domestic use, and air
the SI units of thermodynamic temperature The birthplace of big science.
conditioning systems. All these The cellar layout is
(kelvin) and energy (joule). technological advances resulted practically unaltered to this
directly from the discovery of the day, and the house is now
Joule-Thomson effect. owned and occupied by the
164 University of Salford.
https://www.corrosion-doctors.org/Biographies/JouleBio.htm
 Joule-Thomson Effect
Definition:
“In an Adiabatic process, expansion of a gas from high pressure to low pressure led
to a fluctuation in a Temperature”

Explanation:
-allowing a high pressurized gas through porous plug into either low pressurized or
vacuum, lead to fluctuation in Temperature.
-Since, in an Adiabatic process, there is no chance of exchanging the heat with the
surroundings
-For example; except Hydrogen and Helium, other gases become liquid by this
experiment.
-On contrary Hydrogen and Helium become hot by this experiment.
-For Real gases, internal pressure is not Zero.
-Molecular interactions are operating in between the gas molecules.
-Hence, during the expansion, energy is required to dominate/overcome the Van der Waal’s interactions.
-Hence, part of the energy from system being used for it.
-As an impact, there is a decrease/fluctuate in temperature.
-Hence, gas is liquified/condensed.

-Ideal gases do not have much molecular interactions as per the kinetic gas theory.
165 -Hence, when they do expand in vacuum by the adiabatic process, not exerting the Joule-Thomson effect.
 Joule-Thomson Experiment
Definition: n moles at Porous n moles at
“Demonstrating the Relationship between the decrease in Temperature P1, V1, T1 barrier P2, V2, T2
as well as decrease in Pressure during the adiabatic expansion of gas by an
experimental setup. Piston in A B C Piston out
P1>P2
Explanation:
-at the center of the heat insulated tube, porous plug, “B” is fixed.
-in both direction pistons, “A” and “C” is fixed as well. Adiabatic System
Net work done by the Gas = P2 V2 – P1 V1 …(3)
-to conduct the adiabatic process, tube is made as thermostatic.
It is an Adiabatic process, q = 0
-gas is filled between the piston, “A” and porous plug “B” its pressure is
“P1”. First Law, ΔU = q – w …(4),
Here q = 0; w = P2 V2 – P1 V1……(5)
-Now force is applied on piston “A” to move the gas in opposite direction.
Here decrease in volume is noted as “V1” ΔU = 0 - (P2 V2 – P1 V1 )……(6)
-compressed gas through the porous plug is pushing the piston “C” ΔU = (U2 – U1) = - P2 V2 + P1 V1 ……(7)
outward hence, increment in the volume is noted as “V2”
(U2 + P2 V2) = (U1 + P1 V1) ……(8)
-Pressure at the right side of the plug is noted as “P2”and P1>P2.
H2 = H1 ……(9) (H = U + PV)
Work done on the gas at the left side (A to B) = -P1 V1 ….(1) Or ΔH = 0 …(10)
166 Means, Joule-Thomson expansion is an
Work done by the gas at the right side (B to C) = P2 V2 ….(2) Enthalpy constant process
 Merits and Limitations of Joule-Thomson Experiment
Merits:
-Based on Joule-Thomson effect, liquification of gases are possible.
-there are two methods in use and are;
1. a gas chilled below its boiling temperature and liquified.
2. a gas is chilled below its critical temperature then pressure is increased to liquify it.
-Linde and Claude’s methods are working based on Joule-Thomson effect.

Limitations:
- To apply Joule-Thomson effect, initial temperature of the gas, should be lower than its inverse
temperature, “Ti”.

167
 Claud’s Method of Liquification of Gases
-In this method high pressurized gas is allowed to expand in an Adiabatic
Process. A
B P Air
-For this expansion, internal energy aroused from the molecular interactions
being utilized hence, there is a temperature drop/fluctuation. E
-This effect is associated with the Joule-Thomson effect for liquefying the
gas.
C
-a gas at 200 atm is passed through the tube, “ABC”.
-after reaching the junction “C”, part of the gas is preceding through piston,
“D” and part of the gas preceding through the capillary plug, “J”.
D
-gas present in the region/pump “D”, pushes the piston outside thereby work E
is done. Hence, energy is lost, and gas become cool. J
-partially cooled air is again going up and acting as a coolant for the incoming
gas in a tube.
Liquid Air
-Such cooled gas present in high pressure is precedes out through the
capillary plug, “J” and undergoes Joule-Thomson effect.
-Same process is repeating again and again, at the end gas got liquefied.
Fig. Claude’s apparatus for liquification of air
168
 Joule-Thomson Co-efficient, μJT
-based on definition, Def: In an Adiabatic process, ratio between
H = f (T,P) ….(1), temperature change and pressure change during the gas
expansion is referred as the Joule-Thomson Co-efficient,
Here, “H” is Enthalpy. It is a state function. Hence,
𝜕𝐻 𝜕𝐻 μJT.
dH is the exact differential, dH = dT + dP ….(2)
𝜕𝑇 𝑃 𝜕𝑃 𝑇
-let’s consider that μJT is constant between small
But
𝜕𝐻
= CP ….(3) boundaries of pressure, then the eqn (8) can be written
𝜕𝑇 𝑃
𝜕𝐻
Therefore, dH = CP dT + 𝜕𝑃 𝑇 dP ….(4) as,
Joule-Thomson effect is an Enthalpy constant process, dH = 0.
𝜕𝑯
𝜕𝐻
0 = CP dT + dP ….(5) 𝜕𝑷 𝑻
𝜕𝑃 𝑇
ΔT = - ΔP ….(9)
Or, CP dT = -
𝜕𝐻
𝜕𝑃 𝑇
dP ….(6) 𝑪𝑷
𝑑𝑇 𝜕𝐻
Therefore, 𝑑𝑃 = - 𝜕𝑃 𝑇
+ CP ….(7) Above equation is providing relation between
temperature lowering (ΔT) and pressure lowering
𝜕𝑇 𝜕𝐻
Or, =- /CP ….(8) (ΔP).
𝜕𝑃 𝐻 𝜕𝑃 𝑇

169 𝜕𝑇
Here, - = Joule-Thomson Co-efficient, μJT.
𝜕𝑃 𝐻
 Joule-Thomson Co-efficient, μJT for Various Gases
(a) Ideal Gases: (b) Real Gases:
𝜕𝑻 𝜕𝑻
=0 ≠ 0 i.e., μJT ≠ 0
𝜕𝑷 𝑯 𝜕𝑷 𝑯

𝜕𝑇
- The value of the 𝐻 will be having either +Ve or –Ve sign.
𝜕𝑃
- It means while decreasing the pressure, temperature may decrease = μJT ≠ -Ve.
- The sign of μJT is dependent of initial temperature of the gas which undergo Joule-
Thomson effect.
- Inversion temperature, “Ti” is defined as the temperature at which μJT changes its sign.
- When gas temperature is higher than “Ti”, μJT = -Ve.
- When gas temperature is lower than “Ti”, μJT = +Ve.

170
 Inverse Temperature, Ti
Definitions:
(1) The temperature at which Joule-Thomson effect is going to be cooling effect for gas is “Ti”.

(2) Below to a particular temperature, if a gas is liquified in an adiabatic process means that temperature is “Ti”
(3) The temperature at which μJT changes its sign is “Ti”.
Explanation:
-when a gas is subjected to a Joule-Thomson effect it is considerably liquefied.
-But H2 and He are the exceptional. Because they prefer to become heated rather cooling. At lower temperatures they
also liquefied.
-from these observation we could learn that each gas is having certain temperature, below to that Joule-Thomson
effect is always possible for liquefying. And it is “Ti”.

Significance:
2𝑎
(i) By using the Ti = equation, “Ti” can be calculated, and it is indicative of that to liquefy a gas, up to what
𝑅𝑏
temperature it should be chilled without having the Joule-Thomson effect.
(ii) A gas temperature should be lowered to “Ti” first, then subject to Joule-Thomson effect to enable more cooling,
then bring the temperature below to its critical temperature, “Tc”. Later sufficient pressure can be given to get
the liquid.
171
(iii) He (33 K), H2 (193 K) and N2 (650 K)
 Second Law of Thermodynamics
Limitations of First Law and need for the Second Law:
⚫ ALTHOUGH THE MATHEMATICAL AND CONCEPTUAL TOOLS PROVIDED BY THE ZEROTH AND FIRST LAWS OF
THERMODYNAMICS ARE VERY USEFUL, we need more.
⚫ There is a major question that these laws cannot answer: Will a given process occur spontaneously?
⚫ Nothing in the previous chapters addresses spontaneity, which is an important concept.
⚫ Thermodynamics helps to understand the spontaneity of processes but only once we add more of its tools.
⚫ These tools are called the second and third laws of thermodynamics.
⚫ First law states that if one type of energy is created means same amount of energy must be utilized.
⚫ Need for Second Law: First law didn’t talk about possibility of the reaction, extend of reaction, and direction of the reaction.
Examples to understand the Limitations of First Law:

A B PCl5 PCl3 + Cl2

⚫ Let’s consider that heat is exchanged between the
systems A and B.
⚫ Based on First law, if system A lose heat, q means system
B must receive same amount of q and vice-versa.
⚫ No information on which system is losing or gaining,
because temperature of the both systems should be
known.
⚫ Temperature drop from higher to lower is a
172
natural/spontaneous process.
⚫ Whether water do reverse back or not?
No information.
⚫ But it states that if the reverse
process do not consume the heat, then
the energy lost (drop in temperature) is
equal to the work done against the
gravitational force.
⚫ While PCl5 is decomposing, Z Joule
heat may liberate.
⚫ When PCl3 and Cl2 combine, exactly
Z J heat should be consumed as
per the first law.
⚫ But from the mixture of PCl5, PCl3
and Cl2 reaction direction can not
be predicted based on first law.
⚫ To know the direction of the
reaction, equilibrium constant
should be known.
 Statements of Second Law
Like First Law, Second Law also proposed based on several researchers' hands on experience. They proposed the
Second law in different forms and are given below;

Kelvin-Planck Statement
It is impossible for a heat engine to produce a network in a complete cycle if it
exchanges heat only with bodies at a single fixed temperature.
Clausius’s Statement
-It is impossible to construct a device operating in a cycle that can transfer heat from a colder body to warmer without
consuming any work.
-In other words, unless the compressor is driven by an external source, the refrigerator won’t be able to operate.
-Heat pump and Refrigerator works on Clausius’s statement.
Thomson’s Statement
-Spontaneously, all the natural processes would lead an equilibrium.
Other Statement
-the total energy of the universe being converted into irregular heat energy; hence it is continuously decreasing.
-work can’t be obtained from system by lowering its temperature.
-all the naturally occurring processes are irreversible.
-Entropy of the system and surrounding is a constant during the reversible process. But it is increasing in the irreversible
process.
-in a reversible process, total free energy of the system and surroundings is a constant. But it is decreasing in the
173
irreversible process.
 Spontaneous Processes
“The processes preceding without the assistance from the outside are referred as spontaneous or
natural processes”
Examples:

Heat flow
Concentration flow Gas mixing
Water flow Gas flow
Voltage flow

Conditions for Spontaneity:

-unidirectional
-might happen at any speed
-irreversible process
-always flow towards equilibrium
-Stops after reaching the equilibrium
-during the spontaneous processes ΔH is decreasing. means exothermic reactions are spontaneously happening
174
 Carnot Cycle
⚫ In 1824, a French military engineer named Carnot published an article that ultimately played a
major role in the development of thermodynamics.
⚫ It was ignored at the time. The first law of thermodynamics had not even been established yet,
and heat was still thought of as “caloric.”
⚫ It was not until 1848 that Lord Kelvin brought the attention of the scientific world to the work, 16 years after
Carnot’s early death at age 36.
⚫ However, the article introduced a lasting concept, the definition of the Carnot cycle.
⚫ Carnot was interested in understanding the ability of steam engines—known for almost a century by that time—to
perform work.
⚫ He was apparently the first to understand that there was a relationship between the efficiency of a steam engine
and the temperatures involved in the process.
⚫ Carnot realized that every engine could be defined as getting heat, qin, from some high-
temperature reservoir.
⚫ The engine performed some work, w, on the surroundings.
⚫ The engine then disposed of the leftover heat in a reservoir that has some lower temperature.
⚫ The engine is therefore emitting some heat, qout, into the low temperature reservoir.
Figure. A modern diagram of the type of
⚫ Although the engines of today are much different from those of Carnot’s time, every device we
engine that Carnot considered for his cycle.
have for performing work can be modelled in this fashion.
The high-temperature reservoir supplies the
⚫ Carnot proceeded to define the steps for the operation of an engine in such a way that the
energy to run the engine, which produces
maximum efficiency could be achieved.
some work and emits the remainder of the
⚫ These steps, collectively called the Carnot cycle, represent the most efficient way known to get
energy into a low-temperature reservoir.
work out of heat, as energy goes from a high-temperature reservoir to a low-temperature
The values of qin, w1, and qout are greater or
reservoir. less than zero with respect to the system.
⚫ The engine itself is defined as the system, as shown in the figure.
175
 Carnot Cycle (cont.)
The steps of a Carnot cycle are, for an ideal gaseous system:
A (P1 V1 T2)
A. Reversible isothermal expansion:
-In order for this to occur, heat must be absorbed from the high-temperature
reservoir.
-We shall define this amount of heat as q1 (labeled as qin in Figure. 1) and the
amount of work performed by the system as w1 = q2= RT2 ln 𝑉𝑉 2
… . . (1) B (P2 V2 T2)
1
(P4 V4 T1)
B. Reversible adiabatic expansion:
-In this step, q = 0, but since it is expansion, work is done by the engine.
The work is defined as w2 = CV (T2-T1) ….(2) (P3 V3 T1)
H G F
C. Reversible isothermal compression: E
-In order for this step to be isothermal, heat must leave the system.
-It goes into the low-temperature reservoir and will be labeled q3 (this is labeled as Figure. 2 A representation of the Carnot cycle
performed on a gaseous system. The steps are: (1)
qout in Figure. 1). The amount of work in this step will be called
Reversible isothermal expansion. (2) Reversible
w3 = -q1= RT1 ln 𝑉𝑉 4
… . . (3) adiabatic expansion. (3) Reversible isothermal
D. Reversible adiabatic compression:
3 compression. (4) Reversible adiabatic
-The system (that is, the engine) is returned to its original conditions. compression. The system ends up at the same
-In this step, q is 0 again, and work is done on the system. conditions it started at; the volume inside the
four-sided figure is representative of the p - V
176 -This amount of work is termed w4. w = q= R(T2 - T1) ln 𝑉𝑉 2
… . . (4) work performed by the cycle.
1
 Efficiency, η of Carnot Cycle
-Efficiency of the Carnot Cycle or mechanical heat efficiency, η is defined as at the high temperature ratio between
work done by the machine and absorbed heat.

𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑡ℎ𝑒 𝑚𝑎𝑐ℎ𝑖𝑛𝑒 𝑊 𝑉 𝑉

η= = … 1 𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 w1 = q2= RT2 ln 𝑉2 …(2) and w = q= R(T2 - T1) ln 𝑉2 . . 3
𝐴𝑏𝑠𝑜𝑟𝑏𝑒𝑑 ℎ𝑒𝑎𝑡 𝑞2 1 1
Substituting q2 and w- values in eqn (1),

𝑹 𝑻𝟐 −𝑻𝟏 𝒍𝒏 𝑽𝟐/𝑽𝟏 𝑻𝟐 −𝑻𝟏 -from the equation (6), when temperature T1 = 0 K; η = 1.

η= = ….(4)
𝑹 𝑻𝟐 𝒍𝒏 𝑽𝟐/𝑽𝟏 𝑻𝟐
-but condition of T1 = 0 K (-273 °C, absolute zero) and it is
impossible to reach.
Besides, in a cycle
Absorbed heat = total work done -hence, efficiency of the Carnot cycle is always less than 1.
(q2 – q1) = W
𝑞2 −𝑞1
η= ….(5)
𝑞2
From the equations (4) and (5),
𝑇2 −𝑇1 𝑞 −𝑞
177
η= = 2 1 ….(6)
𝑇2 𝑞2
 Entropy
“ In an isolated system, property which states that either chemical or physical change do happen spontaneously is
referred as Entropy”

Ice Melting: Spontaneous Process

Water Evaporation: Spontaneous Process

-Hence, new research on such spontaneous processes has

began and this new accelerating force was know as Entropy
change, ΔS.
-Clausius stated that during such processes, the degree of
randomness in the molecules do increase and Entropy is a
measurement of the degree of randomness of energy in a
system.
Examples: gallon of gas, prepared food, sunlight have low entropy. When these
-the lower the entropy the more ordered and less random
are “used” their entropy increases.
it is, and vice versa.
178
 Unit & Characteristics of Entropy
Units of Entropy:

ΔS = Entropy change
= Chane in heat/Temperature
= Joule/Degree
= JK-1
Here ΔS is an extensive property hence, it depends on the
Concentration flow
quantity of the object used. Gas flow
Therefore, SI Unit of ΔS = JK-1 mol-1

Characteristics of Entropy:

1. Similar to energy Entropy is also a state function.

2. Entropy is an exact differential Heat flow
3. It is an extensive property
4. Independent of path of the reaction
5. Depends on initial and the final state
6. It can be represented in terms of other
Degree of Randomness:
thermodynamic properties (P, V, T) From the examples: all the
spontaneous processes will be
179
having high degree of randomness.)
 Entropy Change in irreversible or Spontaneous Process
-When energy leaves a hot reservoir as heat, the entropy of the reservoir decreases. Hot Reservoir, Th
-When the same quantity energy enters a cooler reservoir, the entropy increases by a large amount.
-Hence, overall there is an increase in entropy and process is spontaneous.
-Let’s consider that the heat loss from the hot reservoir is “q” or “dq”
-since, the exchange of heat is too slow, we could consider that the exchange of heat as reversible process.
Now,
when [dq] leaves the hot source (dqh < 0), the Clausius inequality implies that
𝑑𝑞ℎ
ΔSsystem =- ……(1) Cold Reservoir, Ts
𝑇ℎ
when [dq] leaves the cold sink (dqh > 0), the Clausius inequality implies that

𝑑𝑞𝑐 𝑑𝑞 𝑑𝑞𝑐
ΔSsurroundings = ……(2); Overall, ΔSsystem + ΔSsurroundings = - ℎ + ……(3)
𝑇𝑠 𝑇ℎ 𝑇𝑠

1 1
ΔS = dqc ( + ) > 0 ……(4); Th > Ts, hence ΔSsystem + Δssurroundings > 0 …(5)
𝑇𝑠 𝑇ℎ

-Hence, cooling (the transfer of heat from hot to cold) is spontaneous.

-during the spontaneous process, system’s and surroundings entropy is increasing.
-Means, entropy of the universe is keep on increasing.
180
 Clausius Inequality
-For an reversible process,
ΔSsystem + Δssurroundings = 0 ….(1)

-For an irreversible process,

ΔSsystem + Δssurroundings > 0….(2)

-Hence, entropy change for the isolated system,

ΔSisolated ≥ 0 ….(3)

-here, symbol (=) represents the reversibility, whereas, symbol (>) represents the irreversibility.
-during the irreversible reaction, both forward and backward reaction must occur slowly.
-Hence, all the reactions happening between the time boundaries are irreversible reactions.
-During these reactions, entropy do increase.

-In this regard, Clausius considered this universe as a isolated system.

-Since, all the natural processes are irreversible, as an impact entropy is keep on increasing……
-Means spontaneous reactions are preceding in such a way that they could diminish the spontaneous change….
-Hence, heat is flow from hot to cold, water flow from top to bottom and the solute diffuse from high concentration to
lower one.

181
 Entropy Change for an Ideal Gas
-Lets consider a reversible expansion of n mole of Ideal gas, and S = n Cv ln T + nR ln V + S0 ….(5)
assume that there is only expansion work is done.
Here, S0 is the integration constant and it cannot be derived only
from the thermodynamics.
based on First law, qrev = dU + pdV ….(1)
In addition for Ideal gas, V = RT/P. Besides, Cv = Cp – R.
-at T K, “qrev” is the heat taken by the system from the surroundings. Substituting all these values in eqn (5),
-Hence, the entropy change during the expansion, 𝑅𝑇
S = n (Cp – R) ln T + nR ln ( ) + S0
𝑃
𝑞 𝑑𝑈 + 𝑃𝑑𝑉 S = n Cp ln T – n R ln T + nR ln R + nR ln T − nR ln P + S0
dS = 𝑟𝑒𝑣 ……(2); hence, dS = ……(3)
𝑇 𝑇 S = n Cp ln T −nR ln P + S’0….. (6)
𝑛𝑅𝑇
- for n mole of ideal gas, P = and, dU = n Cv dT, (Here, S’0 = S0 + n R ln R)
𝑉
here Cv is the molar specific heat capacitance at (A) At constant Volume: (B) At constant Pressure:
constant volume. V = Constant P = Constant
𝑛𝑅𝑇 𝑇2 𝑇2
n Cv dT + 𝑉 𝑑𝑉 ΔSV = n Cv ln
𝑇1
ΔSP = n CP ln
𝑇1
dS =
𝑇 𝑇2 𝑇2
ΔSV = 2.303 n Cv log ΔSV = 2.303 n CP log
𝑑𝑇 𝑑𝑉 𝑇1 𝑇1
dS = n Cv nR ……(4)
𝑇 𝑉 - At constant volume, Temperature - At constant pressure,
of the ideal gas is increasing. Temperature is increasing.
𝑑𝑇 𝑑𝑉
182 On integration, ‫𝑆𝑑 ׬‬ = n Cv ‫ ׬‬+ nR ‫𝑉 ׬‬
𝑇 T2 > T1. ΔSV = +Ve T2 > T1. ΔSP = +Ve
 Physical Significance of Entropy/Entropy Change in Physical
Transformations
Entropy Changes in Physical Transformations:
-during processes such as melting, vaporisation as well as transformation of
one phase to another phase, change in entropy is occurring.
ΔS = (S2 – S1)
(A) Melting:
Δ𝐻𝑓 Trouton’s Rule:
ΔSf = -entropy changes of the liquids’ vaporisation at
𝑇𝑓 their boiling point is a constant. Its value is ~ 88
JK-1 mol-1.
(B) Vaporisation: Δ𝐻𝑉
Δ𝐻𝑉 ΔSV= = ~ 88 JK-1 mol-1
ΔSV= 𝑇𝑏
𝑇𝑏

(C) One Crystal to another:

Δ𝐻𝑡
ΔSt=
𝑇
(D) Sublimation:
Δ𝐻𝑆
ΔSS=
183 𝑇𝑆
 Free Energy
⚫ The basic definition of "energy" is a measure of a body's (in thermodynamics, the system's)
ability to cause change.
⚫ For example, when a person pushes a heavy box a few meters forward, that person exerts
mechanical energy, also known as work, on the box over a distance of a few meters forward.
⚫ The mathematical definition of this form of energy is the product of the force exerted on the
object and the distance by which the box moved (Work = Force × Distance).
⚫ Because the person changed the stationary position of the box, that person exerted energy
on that box.

⚫ The work exerted can also be called "useful energy", because energy was converted from one form into the intended purpose, i.e.
mechanical utilization.
⚫ For the case of the person pushing the box, the energy in the form of internal (or potential) energy obtained through metabolism was
converted into work in order to push the box.
⚫ The difference between the change in internal energy, which is ΔU, and the energy lost in the form of heat is what is called the "useful
energy" of the body, or the work of the body performed on an object.
⚫ In thermodynamics, this is what is known as "free energy".
⚫ In other words, free energy is a measure of work (useful energy) a system can perform at constant temperature. Mathematically, free
energy is expressed as: free energy A = U − TS

184
 Helmholtz Free Energy and Gibbs Free Energy
Total Entropy change of a isolated system, ΔSsystem + ΔSsurroundings ≥ 0
-If, ΔS = +Ve, it is spontaneous process, If, ΔS = 0, it is in equilibrium
-Hence, ΔS can be considered as a determinate for a spontaneous process. For this, we should measure ΔS of both system and surroundings.
-But the measurement is not possible in certain circumstances. Hence, based on the following two state functions ΔS can be understood well.
-They are 1. Helmholtz free energy (A), 2. Gibbs free energy (G)

Helmholtz free energy, A Gibbs free energy, G

-It can be defined as follows; -It can be defined as follows;
A = U – TS, here U and S are state functions hence, A too. G = H – TS, here H and S are state functions hence, G too.
-lets consider, a system is transforming from phase 1 (A1, U1, S1) to -lets consider, a system is transforming from phase 1 (G1, H1, S1) to
phase 2 (A2, U2, S2) at constant temperature. phase 2 (G2, H2, S2) at constant temperature.
A1 = U1 – TS1; A2 = U2 – TS2 G1 = H1 – TS1; G2 = H2 – TS2
Now change happened in the state A is, Now change happened in the state G is,
(A2 – A1) = (U1 – U2) – T(S1 – S2), ΔA = ΔU – TΔS (G2 – G1) = (H1 – H2) – T(S1 – S2), ΔG = ΔH – TΔS
Lets consider that, change occurred reversibly and “q” amount of heat At constant pressure,
was absorbed, ΔH = ΔU + P ΔV,
𝑞𝑟𝑒𝑣 therefore, ΔG = ΔU + P ΔV – TΔS, but ΔU – TΔS = ΔA
ΔS = (or) TΔS = qrev; ΔA = ΔU – qrev
𝑇 Besides, ΔA =–w
As per first law, ΔU = q – w (or) ΔU-q = -w
Therefore, ΔG = -w + P ΔV (or) -ΔG = w - P ΔV
Therefore, ΔA = -wrev (Or) -ΔA = wrev
- Here P ΔV is the expansion work. Hence decrement in function G.
- hence, maximum work can be done at the reversible process.
-hence, -ΔG is the net work done excluded from the expansion work (P ΔV).
-hence, -ΔA is the indicative of maximum work obtained from the system.
185 -hence, -ΔG = net work. G is referred as Gibbs free energy.
-hence, it is referred as “work function” or Helmholtz free energy.
 Conditions for Spontaneous Changes and Equilibrium/Free
Energy Change-Criteria for Spontaneity
𝑞𝑟𝑒𝑣 𝑑𝑈 + 𝑃𝑑𝑉
Entropy change of a isolated system, dS = = … . (1)
𝑇
𝑇
TdS = dU + PdV …(2) (or) TdS = dqrev …..(3)
-Entropy is a state function. Hence, there will be change in entropy for reversible and irreversible processes.
-But, heat absorbed at the reversible, qrev will be less in comparison with the entropy change (qrev < TdS)
means TdS > qrev …(4), hence eqn (2) can be rewritten as, TdS ≥ dU + PdV ….(5)
-here, symbol (=) represents the reversibility, whereas, symbol (>) represents the irreversibility (or) spontaneity.

Change in Helmholtz free energy, A Change in Gibbs free energy, G During a Process:

dA = dU – TdS, lets use this in the following dG = dU + PdV + VdP – TdS - SdT,
equation, lets use this in the following equation,
ΔG ˂0
-process is spontaneous
TdS ≥ dU + P ΔV…..(5) TdS ≥ dU + P ΔV…..(5)
ΔG = 0
dA ≤ – PΔV dG ≤ VdP – SdT -system is at equilibrium

At constant Volume, dA ≤ 0 At constant Temperature and Pressure, dG ≤ 0

Means, (∂A)T,V ≤ 0
-here, symbol (=) represents the reversibility,
whereas, symbol (<) represents the spontaneity.
186
ΔG > 0
Means, (∂G)T,P ≤ 0 -the process is not
-here, symbol (=) represents the reversibility, whereas, symbol (<) spontaneous
represents the spontaneity. Sometimes due to the
circumstances, condition may go
- Change in the Gibbs free energy [(∂G)T,P ≤ 0] is the determinate for wrong. As well as speed of the
the spontaneous reaction. reaction cannot be predicted.
 Matrix of Conditions Dictating Spontaneity

187
 He was one of the few
people to understand
Maxwell Relationships-(A) Gibbs’s work.

⚫ The equations involving partial derivatives of the thermodynamic energies can be taken a step further.
⚫ However, some definitions are necessary.
⚫ We have repeatedly made the point that some thermodynamic functions are state functions, and that changes in state
functions are independent of the exact path taken.
⚫ In other words, the change in a state function depends only on the initial and final conditions, not on how the initial
conditions became the final conditions.
(i). dU = TdS – PdV
-This is an extraordinarily powerful result.
-This differential for dU can be used to simplify the differentials for H , A , and G .
-But even more useful are the constraints it places on the variables T, S, P, and V due to the mathematics of exact differentials!

-at constant Volume, dV = 0. Hence, from the equation (i), -lets differentiate eqn (2), by keeping “V” as constant and with
𝜕𝑈 respect to “S”,
dU = TdS (or) = 𝑇….(1)
𝜕𝑆 𝑉 𝝏𝟐𝑼 𝝏𝑷
-at constant Entropy, dS = 0. Hence, from the equation (i), = …..(4)
𝜕𝑈 𝝏𝑽 𝝏𝑺 𝝏𝑺 𝑽
dU = - PdV (or) = −𝑃….(2) Internal energy “U” is a state function hence, independent of path
𝜕𝑉 𝑆
-lets differentiate eqn (1), by keeping “S” as constant and with 𝜕2𝑈 𝜕2𝑈
respect to “V”, = ; comparing eqn (3) and (4),
𝜕𝑆 𝜕𝑉 𝜕𝑉 𝜕𝑆
𝝏𝟐𝑼 𝝏𝑻
= …..(3) 𝝏𝑻 𝝏𝑷
𝝏𝑺 𝝏𝑽 𝝏𝑽 𝑺 = - …..(A)
188
𝝏𝑽 𝑺 𝝏𝑺 𝑽
 Maxwell Relationships-(B)
(ii). dH = TdS + VdP

-at constant Pressure, dP = 0. Hence, from the equation (ii), -lets differentiate eqn (6), by keeping “P” as constant and with
𝜕𝐻 respect to “S”,
dH = TdS (or) = 𝑇….(5)
𝜕𝑆 𝑃 𝝏𝟐𝑯 𝝏𝑽
-at constant Entropy, dS = 0. Hence, from the equation (ii), = …..(8)
𝜕𝐻 𝝏𝑷 𝝏𝑺 𝝏𝑺 𝑷
dH = VdP (or) = 𝑉….(6) Enthalpy “H” is a state function hence, independent of path
𝜕𝑃 𝑆
-lets differentiate eqn (5), by keeping “S” as constant and with 𝜕2𝐻 𝜕2𝐻
respect to “V”, = ; comparing eqn (7) and (8),
𝟐 𝜕𝑃 𝜕𝑆 𝜕𝑆 𝜕𝑃
𝝏𝑯 𝝏𝑻
= …..(7) 𝝏𝑻 𝝏𝑽
𝝏𝑺 𝝏𝑷 𝝏𝑷 𝑺 = …..(B)
𝝏𝑷 𝑺 𝝏𝑺 𝑷

189
 Maxwell Relationships-(C)
(iii). dA = -SdT - PdV

-at constant Volume, dV = 0. Hence, from the equation (iii), -lets differentiate eqn (10), by keeping “V” as constant and with
𝜕𝐴 respect to “T”,
dA = -SdT (or) = −𝑆….(9)
𝜕𝑇 𝑉 𝝏𝟐𝑨 𝝏𝑷
-at constant Temperature, dT = 0. Hence, from the equation (iii), = …..(12)
𝜕𝐴 𝝏𝑽 𝝏𝑻 𝝏𝑻 𝑽
dA = -PdV (or) = −𝑃….(10) Helmhotlz Free energy “A” is a state function hence, independent of
𝜕𝑉 𝑇
-lets differentiate eqn (9), by keeping “T” as constant and with path
respect to “V”, 𝜕2𝐴 𝜕2𝐴
𝝏𝑨𝟐
𝝏𝑺 = ; comparing eqn (11) and (12),
=- …..(11) 𝜕𝑉 𝜕𝑇 𝜕𝑇 𝜕𝑉
𝝏𝑻 𝝏𝑽 𝝏𝑽 𝑻 𝝏𝑺 𝝏𝑷
= …..(C)
𝝏𝑽 𝑻 𝝏𝑻 𝑽

190
 Maxwell Relationships-(D)
(iv). dG = VdP - SdT

-at constant Temperature, dT = 0. Hence, from the equation (iv), -lets differentiate eqn (14), by keeping “T” as constant and with
𝜕𝐺 respect to “P”,
dG = VdP (or) = 𝑉….(13)
𝜕𝑃 𝑇 𝝏𝟐𝑮 𝝏𝑺
-at constant Pressure, dP = 0. Hence, from the equation (iv), =- …..(16)
𝜕𝐺 𝝏𝑻 𝝏𝑷 𝝏𝑷 𝑻
dG = -SdT (or) = −𝑆….(14) Gibbs Free energy “G” is a state function hence, independent of path
𝜕𝑇 𝑃
-lets differentiate eqn (13), by keeping “P” as constant and with 𝜕2𝐺 𝜕2𝐺
respect to “T”, = ; comparing eqn (15) and (16),
𝟐 𝜕𝑃 𝜕𝑇 𝜕𝑇 𝜕𝑃
𝝏𝑮 𝝏𝑽
= …..(15) 𝝏𝑽 𝝏𝑷
𝝏𝑷 𝝏𝑻 𝝏𝑻 𝑷 = - …..(D)
𝝏𝑻 𝑷 𝝏𝑷 𝑻

Equations (A), (B), (C) and (D) are known as Maxwell Relationships
191
 Summary & Additional Relations

Besides from eqn (2) and (10), Besides from eqn (6) and (13), Besides from eqn (1) and (5),
Besides from eqn (1) and (5),
𝝏𝑨 𝝏𝑮
𝝏𝑼 𝝏𝑯 𝝏𝑼 𝝏𝑨 𝝏𝑯 𝝏𝑮 = …..(H)
= …..(E) = …..(F) = …..(G) 𝝏𝑻 𝑽 𝝏𝑻 𝑷
𝝏𝑺 𝑽 𝝏𝑺 𝑷 𝝏𝑽 𝑺 𝝏𝑽 𝑻 𝝏𝑷 𝑺 𝝏𝑷 𝑻

Equations (E), (F), (G) and (H) are known as additional Maxwell Relationships
192
 Gibbs-Helmholtz Equation
⚫ Gibbs-Helmholtz equation relates the enthalpy, entropy and free Other forms of Gibbs-Helmholtz equation:
energy change of the process at constant pressure and 𝜕𝐺
temperature as
H =G-T ……(A)
𝜕𝑇 𝑃
G = H – TS; ΔG = ΔH - TΔS….(1)
-lets consider, a system is transforming from phase 1 (G1, H1, T1, S1) 𝐺
to phase 2 (G2, H2, T2, S2) at constant temperature.
𝜕( ) 𝐻
𝑇
𝑃 = − … . . (𝐵)
-Change in free energy is represented as 𝜕𝑇 𝑇2
(G2 – G1) = ΔG = (H2 – H1) – T(S2 – S1), (Or) ΔG = ΔH – TΔS …(2)
𝜕𝐺 𝐺
But, = −𝑆 𝜕( )
𝜕𝑇 𝑃 𝑇
𝜕𝐺2 𝜕𝐺1 𝑃 = H….. 𝐶
Therefore, − = −(S2 − S1) 1
𝜕𝑇 𝑃 𝜕𝑇 𝑃 𝜕
𝑇
𝜕(𝐺2 −𝐺1) 𝜕Δ𝐺 Equations (A), (B) and (C) are other forms of Gibbs-
𝑃 = −Δ𝑆; = −Δ𝑆;
𝜕𝑇 𝜕𝑇 𝑃 Helmholtz equation.
𝜕Δ𝐺
(Or) Δ𝑆 = −
𝜕𝑇 𝑃
Substituting the value of Δ𝑆 in equation (2). -Gibbs-Helmholtz equation for the processes at constant
Volume;
𝜕Δ𝐺
ΔG = ΔH + T …(3)
𝜕𝑇 𝑃 𝜕Δ𝐴
Equation (3) is referred as Gibbs-Helmholtz equation. ΔA = ΔU + T …(4)
It is applicable for the processes occurring at CONSTANT 𝜕𝑇 𝑉
193
PRESSURE.
 Applications Gibbs-Helmholtz Equation
⚫ If ΔG (or) ΔA is known at two different temperatures, then ΔH (or) ΔU can be calculated.

⚫ If change in free is energy ratio is not affected by the Temperature, then by using the ΔG known at one temperature,
another temperature’s ΔG can be easily calculated.

⚫ ΔH value of the reversible batteries can be calculated. Because by using electro motive force and temperature of the
battery, the ratio change in electro motive force can be calculated.

⚫ By using this equation, Clausius-Clapeyron equation and Von’t-hoff equation can be derived.

194
 Verification of Gibbs-Helmholtz Equation
-Gibbs-Helmholtz equation for the standard condition,

𝜕Δ𝐺°
ΔG° = ΔH° + T
𝜕𝑇 𝑃
Standard electro motive force, E° can be calculated by using standard free energy change, ΔG° as follows,
ΔG° = - nFE°
𝜕Δ𝐸°
Hence, - nFE° = ΔH° - nFT
𝜕𝑇 𝑃

-at various temperatures, E° can be measured and by using the measurements ratio change in E° with respect to
𝜕𝐸°
temperature can be calculated.
𝜕𝑇

-Hence, by using above equation change in standard enthalpy (ΔH°) can be calculated.
-Through Thermochemistry experiments ΔH should be measured and compared.
Equality in both ΔH-values verifies Gibbs-Helmholtz equation.
195
 Van’t Hoff Equation
KP = 𝑒 −Δ𝐺°/𝑅𝑇 𝑜𝑟 ΔG° = - RT ln KP 𝑜𝑟 ΔG° = - RT ln KP + RT ln QP
This equation is known as the van’t Hoff reaction isotherm. And it is very important one which permits the calculation of ΔG° of the reaction
from the known value of the equilibrium constant Kp and vice-versa. QP is the pressure ratio.

Deriving The vant’ Hoff Equation: Significance of The vant’ Hoff Equation:

⚫ If you run the same reaction at different temperature, T1 and T2: ➢ If ΔH = 0, no heat is evolved or absorbed in the reaction,
𝑲𝟐 𝑲𝟐
Δ𝐻° Δ𝑆° Δ𝐻° Δ𝑆° ln = 0, i.e. = 1 or K1 = K2
𝑲𝟏 𝑲𝟏
ln K1 = – + ; ln K2 = – + i.e., the equilibrium constant does not change with temperature.
𝑅𝑇1 𝑅 𝑅𝑇2 𝑅
➢ If ΔH = +Ve, endothermic reaction,
-then subtraction yields:
Δ𝐻° 1 1 𝑲𝟐
ln K2 – ln K1 = ( – ) ln = +Ve, or K2 > K1
𝑅 𝑇1 𝑇2 𝑲𝟏
i.e., the equilibrium constant increases with the increase in
-Which equals: temperature.
𝑲𝟐 𝜟𝑯° 𝟏 𝟏
ln = ( – ) van’t Hoff equation ➢ If ΔH = -Ve, exothermic reaction,
𝑲𝟏 𝑹 𝑻𝟏 𝑻𝟐
𝑲𝟐
ln = -Ve, or K2 < K1
So, if you know the equilibrium constant at any temperature, and the 𝑲𝟏
standard enthalpy of reaction, you can determine the what K would be at any i.e., the equilibrium constant decreases with the increase in
196
other temperature. temperature.
 Van’t Hoff Reaction Isotherm
⚫ The Van't Hoff isotherm equation is used for estimating the equilibrium shift during a chemical reaction.
⚫ We can also derive the Van't Hoff isotherm equation using the Gibbs-Helmholtz equation which gives a relation between the change in
free energy with respect to the changing temperature.

KP = 𝑒 −Δ𝐺°/𝑅𝑇 𝑜𝑟 ΔG° = - RT ln KP 𝑜𝑟 ΔG° = - RT ln KP + RT ln QP

➢ When QP < Kp, ΔG < 0, Reaction proceeds towards the positive way.
➢ When QP = Kp, ΔG = 0, Reaction is in the equilibrium state.
➢ When QP > Kp, ΔG > 0, Reaction proceeds towards the opposite way.

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 2

198
Thanks for Your Kind Attention
For Queries Contact at
Chamber: F140/A, Phone: 8438922485,
email: smanivannan@bhu.ac.in

199
 Unit-3 Chemical Kinetics
3. Chemical Kinetics: Zero, first and second order kinetics, determination of rate constant and order of reactions, effect of
temperature on rate constant, Arrhenius equation, collision and activated complex (transition state) theories of rate of
reactions.

200
 ⚫ Chemical kinetics, the branch of
physical chemistry that is concerned with
Chemical understanding the rates of chemical reactions.
Kinetics ⚫ It is to be contrasted with thermodynamics, which
deals with the direction in which a process occurs
but tells nothing about its rate.
 Rate of Reaction

Chemical kinetics deals with the rates of chemical reactions. i.e How fast a chemical reaction occurs?
-Such studies help to understand the mechanism through which the reactants are converted to product.
-It is observed that some reactions occur with in a fraction of second, whereas some reactions take years together for completion.

Main concerns of chemical kinetics:

1. Reaction Rate: factors that determine the rate of the reaction, rate law.
2. Reaction Mechanism: the series of steps by which a reaction takes place.
3. Structure dependent of reactivity: the correlation between molecular structure and reaction potential.

Understanding of Rate of Reaction:

⚫ Rate of reaction is defined as the change in the amount of reactants or products per unit time.
⚫ Following the reaction between Zinc and hydrochloric acid;
Observations:

⚫ As Hydrogen gas being collected,

the mass of the product keep
increasing as the reaction progress.
⚫ Meanwhile, reactants
concentrations/mass use to
decrease.
 Factors Determining the Rate of a Reaction

Main Factors which influence reaction Rate:

1. Concentration of Reactants: Rates usually increase as reactant concentration increase.

2. Reaction Temperature: An increase in temperature increase the rate of the reaction.
3. Presence of Catalyst: (not all reactions have catalysts)
-A catalyst is a substance which increase the rate of a reaction without being consumed in the overall reaction.
-The concentration of the catalyst or its surface area (if insoluble) are variables which influence the rate
- Some catalysts are incredibly complex – like enzymes; and others are quite simple.
4. Nature of the reactants: corrosion: too slow, AgCl precipitate: So fast
5. Surface area of the insoluble reactant.
 Molecularity of the Reaction

Chemical reactions may be classified into two types:

1. Elementary Reactions: reaction which occurs in a single step.

2. Complex Reactions: reaction which occurs in two or more steps.

Molecularity of an Elementary Reaction:

- The molecularity of the elementary reaction is defined as the number of reactant molecules involved in a
reaction.

⚫ Unimolecular Reactions (molecularity = 1): A product

⚫ Bimolecular reactions (molecularity = 2): A + B products

⚫ Termolecular reactions (molecularity = 3): A + B + C products

Unimolecular Bimolecular Termolecular

 Rate Constant & Order of Reaction

RATE CONSTANT:
⚫ A rate constant is a proportionality constant that appears in a rate law.
⚫ For example, k is the rate constant in the rate law d[A]/dt = k[A].
⚫ Rate constant are independent of concentration but depend on other factors, most notably
temperature.

ORDER OF REACTION:
⚫ The number of molecules or atoms whose concentration changes during the reaction is called Order of
Reaction.
⚫ Or the number of molecules or atoms whose concentration determines the rate of reaction is called
order of reaction.

205
 Reaction Mechanisms

⚫ For unimolecular reaction, such as the decomposition of A B, the elementary step involves a single molecule
and a first order rate law describes the kinetic rate = k[A].

⚫ For Bimolecular reaction, A + B C, the elementary step involves two molecules, and a second order rate law
describes the kinetic rate = k[A][B]. Or if 2A B the rate law is written rate = k[A]2

⚫ For Termolecular reaction, the elementary step involves three molecules, and a third order rate law describes the
kinetics: For 2A + B C , the rate = k[A]2[B]. Or if A + B + C D, the rate law = k[A][B][C]

206
 Equilibrium Explained

Figure: (a) A rock on the side of a mountain represents a simple physical system that is not at equilibrium.
(b) Now the rock is lying at the bottom of the mountain. The rock is at its minimum gravitational potential energy.
This system is at equilibrium.
Difference Between Order and Molecularity of the Reaction
 Relationship Between the Stoichiometric Equation, Order
and Molecularity of the Reaction
- In some reactions, order of reaction and no. of reactants may be same
- As well as molecularity of the reaction and no. of reactants may be same.
- Besides, order and molecularity also be same.
- But there is NO relationship among them.
- It can be understood from the following example;

Example: consider the following reaction;

2N2O5 4NO2 + O2 ;

-and this reaction belongs to first order kinetics as per the research.
-this reaction taking place with the following steps;

(i) N2O5 NO2 + NO3

(ii) NO2 + NO3 NO2 + O2 + NO
(iii) NO + N2O5 3NO2

- For the first step, molecularity is 1

- For subsequent steps it become 2.

 Zero Order Reaction

⚫ “when the reaction rate is independent of concentration of the reacting substance, it depends
on the zero power of the reactant and therefore is zero order reaction.
⚫ In this type of reaction, the limiting factor is something other than concentration, for example,
solubility or absorption of light in certain photochemical reactions.

⚫ Example:
Loss of color of multi-sulfa drug

Rate of the decomposition can be described mathematically as:

𝑥 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
K= = …..(1)
𝑡 𝑡𝑖𝑚𝑒

210
 First Order Reaction

⚫ First order reaction consists of one reactant.

A product

R = k [A]1
Rate constant for the first order reaction:: Example:

2.303 𝑎 N2O5 N2O3 + O2

K = .log …..(1)
𝑡 (𝑎 −𝑥)

Where, a = initial conc. of A in mol/lit

a – x = change in initial conc. of A in mol/lit in time interval of ‘t’

211
 Second Order Reaction

⚫ It is defined as reaction in which the rate depends on the concentration terms of two reactants each raised to the
power one.
⚫ Consider the following reaction

A+B products
the rate of the equation can be written as
−𝑑𝐴 −𝑑𝐵
K= = = K2[A]1[B]1
𝑑𝑡 𝑑𝑡
Where,
[A] and [B] are the concentration of A and B, respectively, and k2 is the specific rate constant for the second
order.
In other words, the rate of the reaction is first order with respect A, and again first order with respect to B.
So, the overall order of this reaction is second order.
 Half-Life Period, t1/2

Definition: Half-life is the time required for a quantity to reduce to half of its initial value. The term is
commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how
long stable atoms survive.

For the first order reaction,

2.303 𝑎
t= .log …..(1)
𝑘 (𝑎 −𝑥)
When, x = a/2, t = t1/2.
2.303 𝑎 2.303 𝑎
t1/2 = .log 𝑎 …..(2); = .log 𝑎 …..(3)
𝑘 (𝑎 − ) 𝑘
2 2

2.303 2.303 𝑥 0.3010

t1/2 = .log 2 …..(4); = …..(5)
𝑘 𝑘
0.6932
t1/2 = = constant …..(5)
𝑘

Hence, in the first order reaction, time required for a quantity

to reduce to half of its initial value is a constant.
 Measurement of the Rate of a Reaction:
1. Integration Method (Or) Hit and Trial Method

1). In this method, the values of ‘x’ at various time interval ‘t’ determined experimentally. (x = amount of reactant
decomposed)
2). These values substituted in rate constant equations of first, second and third order reactions
3). i) For first order reaction,
2.303 𝑎
k= .log …..(1)
𝑡 (𝑎 −𝑥)
ii) For second order reaction,

1 𝑥 2.303 𝑏(𝑎 − 𝑥)
k= …..(2): for equal concentration k= log …..(3): for unequal concentration
𝑡 𝑎(𝑎 −𝑥) 𝑡(𝑎−𝑏) 𝑎(𝑏 −𝑥)

iii) For third order reaction,

1 𝑥(2𝑎 −𝑥)
k= …..(4): for equal concentration
2𝑡 𝑎2 𝑎 −𝑥 2

4) The order of reaction (n) is determined by the equation which gives satisfactory constant value of velocity
constant (k)
5) This method is trial and error, but it is extensively used.
 Measurement of the Rate of a Reaction:
2. Half-Life Period Method

In this method, time (t) taken to complete a definite Then,

fraction of the reaction is calculated. 1 1 𝑡 𝑎
t1 ∝ and t2 ∝ and [ 1] = [ 2]n – 1
- If t = time required for completion of definite fraction 𝑎1𝑛 −1 𝑎2𝑛 −1 𝑡2 𝑎1
of reaction. Taking log,
- a = initial concentrations of a reactant. 𝒕 𝒕
Then, 𝒍𝒐𝒈𝟏𝟎 [𝒕𝟏] 𝒍𝒐𝒈𝟏𝟎 [𝒕𝟏]
i) For first order reaction, 𝒂𝟐𝟐 = n -1 ; 𝐧 = 𝟏 + 𝒂𝟐𝟐 …..(A)
𝒍𝒐𝒈𝟏𝟎 [𝒂 ] 𝒍𝒐𝒈𝟏𝟎 [𝒂 ]
𝟏 𝟏
1
t∝ i.e., ‘t’ is the independent on initial concentration.
𝑎0 To get the values of a1 & a2, plot graph of ‘x’ Vs. ‘t’.
And from the eqn (A) ‘n’ can be calculated.
1
i) For second order reaction, t∝
𝑎1

1
iii) For third order reaction, t∝
𝑎2
1
iv) General nth order reaction, t ∝ 𝑛 −1
𝑎
If, t1 & t2 are time required for completion of same
fraction of reaction with different initial concentrations
a1 & a2, respectively.
And ‘n’ is order of reaction.
 Measurement of the Rate of a Reaction:
3. Van’t Hoff’s Integration Method

This method involves determination of rates (dc/dt) by measuring the slopes of

concentration (c) Vs. time (t) curves.

For nth order reaction, we have,

−𝑑𝑐
Rate = = K. cn …….(1); C = concentration.

Concentration, C
𝑑𝑡

Reactant’s
For concentrations, C1 & C2, we have,
−𝑑𝑐1 −𝑑𝑐
=K. 𝐶1𝑛 …….(2); 2
= K. 𝐶2𝑛 …….(3);
𝑑𝑡 𝑑𝑡
Taking ratio of equation (2) and (3),
−𝒅𝒄𝟏
𝒅𝒕 𝑪𝟏 n
−𝒅𝒄𝟐 = ( ) ……. (4)
𝑪𝟐 Time, t
𝒅𝒕
Taking logarithm of eqn (4),

−𝒅𝒄𝟏 −𝒅𝒄𝟏 −𝒅𝒄𝟐

𝑪𝟏 𝒍𝒐𝒈 𝒅𝒕
−𝒍𝒐𝒈 𝒅𝒕
𝒅𝒕
log −𝒅𝒄𝟐 = n log ( ) ……. (5); n = ……. (A)
𝑪𝟐 𝒍𝒐𝒈 𝑪𝟏 −𝒍𝒐𝒈 𝑪𝟐
𝒅𝒕
 Measurement of the Rate of a Reaction:
4. Ostwald’s Isolation Method

α A + β B + γ C + …………………… product

Let’s consider this equation. Its rate equation can be written as,

Rate Constant ∝ [A]α[B]β[C]γ………

Hence, its reaction order, n = α + β + γ + ……………………

Now, if we take ‘A’ in less quantity and others in high quantity, rate of the reaction is dependent of ‘A’.
Now by using the any one of the previous method reaction order can be determined which is dependent of ‘A’, α-can be
obtained.

Similarly, for ‘B’ and ‘C’ can be measured.

Now if, we take all the reactant in less quantity,

Order of the reaction, n = α + β + γ + ……………………

 Measurement of the Rate of a Reaction:
5. Graphical Method

After the initiation of the reaction, concentrations of the reactant at t1, t2 and t3………are (a – x1), (a – x2) and (a – x3),
respectively.

Now, log (a -x) Vs. t = Straight line = FIRST ORDER REACTION

1/(a -x) Vs. t = Straight line = SECOND ORDER REACTION

1/(a -x)2 Vs. t = Straight line = THIRD ORDER REACTION

x Vs. t = Straight line = ZERO ORDER REACTION

log (dx/dt) Vs. log (a - x) = Straight line = nth ORDER REACTION (slope of the straight line = n)
 Steady State Principle

- Most of the reactions occurs with several steps.

- Each step of the reaction will be having each rate.
- The step which takes place very slowly is the rate determining step.
- Furthermore, slow step’s order will be the reaction’s order.

Example: consider the following reaction;

H2O2 + 2HI 2H2O + I2 ;

and this reaction is preceding with the following steps

(i) H2O2 + I- H2O + OI- (slow)

(ii) OI- + H+ HOI (fast)
(iii) HOI + H+ H2O + I2 (fast)

(i) + (ii) + (iii) H2O2 + 2H+ + 2I- 2H2O + I2

- For the above reaction, step (i) is slowly preceding.

- Hence, rate of step (i) is dependent of [H2O2] [I-] concentrations. So, its second order reaction.
- The intermediates (ex: OI-) formed during the multi-step reaction are the species having very less life time as well as just appear
and disappear during the reaction.
- Hence, during the reaction, concentrations of such species are less as well as constant.
- Therefore, the rate of intermediate species formation and deformation will be in equal, and it is referred as Steady State Principle.
 Effect of Temperature on the Rate of Reaction:
Temperature Co-efficient

Rise in Temperature:

1. Initiate the reaction.

2. Increase the rate of reaction.

(A) Temperature Co-efficient:

- It has been found that generally rate of reaction and rate constant increase with increase in temperature.
- For homogenous reaction, rate and rate (velocity) constant of reaction get approximately doubled or tripled for
every 10 °C rise in temperature.
-This is generally expressed in the form of temperature co-efficient.

“The ratio of rate constants of a reaction at two different temperatures which differ by 10 °C is called temperature
co-efficient”
𝒌(𝒕+𝟏𝟎)
Temperature Co-efficient = ~ 2 or 3
𝒌𝒕
Where,
kt = velocity constant at t °C, k(t + 10) = velocity constant at t °C

2HI H2 + I2 (Temperature co-efficient is 1.8)

 Arrhenius Equation

Arrhenius suggested as simple relationship between the 𝐸𝑎

rate constant (k) and the temperature
(or) 𝑙𝑛𝑘 = − + C …….(2)
𝑅𝑇2

E
− a Ea
Arrhenius equation, k = A. 𝒆 − 𝑹𝑻
+ C …… (3)
𝑹𝑻
k = A. 𝒆
Y-intercept = ln A Equations (1), (2) and (3) are known as Arrhenius Rate equations.
Here,
k = Rate constant
Slope = (-Ea/RT) A = Frequency co-efficient or Collision factor
ln k e = is the base of the natural logarithm (Euler’s number)
Ea = Activation energy
R = universal gas constant
0 1 / Temperature T = denotes the absolute temperature associated with the
reaction
𝟏 (in Kelvin, t °C + 273 = T K)
When Arrhenius plots the log k Vs. , straight was obtained.
𝑻 If the activation energy is expressed in terms of energy per
Hence, he proposed that ‘k’ and ‘T’ must have the following reactant molecule, the universal gas constant must be replaced
relationship; with the Boltzmann constant (kB) in the Arrhenius equation.
𝑑𝑙𝑛𝐾 𝐸𝑎
= …….(1)
𝑑𝑇 𝑅𝑇2
 Activation Energy, Ea

Energy of activation (Ea):

- According to the concept of activation, reactant does not pass

directly to product.
- Arrhenius suggested that, before react, colliding molecule must be
activated by absorbing minimum amount of energy called
“Activation Energy”.
- As temperature increased the number of such active molecules also
increases. Ex, Energy Barrier
- Thus “the minimum amount of energy required for the collision
between the molecules to be effective is called Energy of
activation.” E1
- For a reversible reaction, Van’t Hoff Isochore, EA
𝜕𝑙𝑛𝑘 Δ𝐸 𝑘
= 2 here, k = equilibrium constant = 1. Here k1 and K2 are rate E2
𝜕𝑇 𝑅𝑇 𝑘2
constants for the forward and backward reactions, respectively. ΔE
𝑘 EB
𝜕𝑙𝑛𝑘1 Δ𝐸 (𝐸1 − 𝐸2) 𝜕𝑙𝑛𝑘1 𝜕𝑙𝑛𝑘2 𝐸1 𝐸2 𝑑𝑙𝑛𝐾 𝑬𝒂
2 = = (or) − = − ; =
𝜕𝑇 𝑅𝑇2 𝑅𝑇2 𝜕𝑇 𝜕𝑇 𝑅𝑇2 𝑅𝑇2 𝑑𝑇 𝑅𝑇2
Hence, the term Ea, in the equation must be the indicative of energy and
Arrhenius called it as Activation Energy.
 Measurement of Activation Energy

- Energy of activation (Ea) can be calculated by Arrhenius equation as,

𝑑𝑙𝑛𝐾 𝐸𝑎 𝑘1 𝐸𝑎 𝑇 −𝑇
= (Or) 𝑙𝑜𝑔10 = [ 2 1]……(1)
𝑑𝑇 𝑅𝑇2 𝑘2 2.303 𝑅 𝑇1 − 𝑇2

By using the eqn (1) Ea can be calculated.

−𝐸𝑎 1
Besides, 𝑙𝑜𝑔10 𝑘 = + log A ……(2)
2.303 𝑅 𝑇

Eqn (2) resembles with y = mx + C

Hence, at different temperatures, k-values can be measured and
𝟏
Plot of log k Vs. 𝑻 can be plotted to get the straight line.
−𝐸𝑎
will be the slope of the straight line.
2.303 𝑅
Ea, can be derived from the slope.
Energy of activation (Ea) depends on the nature of reactants.
⚫ Slow reactions have high Ea.
⚫ Fast reactions have low Ea.
 Frequency co-efficient, A

According to collision theory, Frequency co-efficient, A is equal to the Collision no. Z.

For the complex reactions, A ∝ Z

Based on ARR theory,

ΔS∗
𝑹𝑻
A =
𝑵𝒉
𝒆 𝑹

Means “A” is dependent of activated complex entropy, ΔS*

Ea E
k = A . 𝒆− 𝑹𝑻 …… (1); taking ln, 𝒍𝒏𝒌 = 𝒍𝒏𝑨 − a …….(2)
𝑹𝑻
Ea
𝒍𝒏𝑨 = 𝒍𝒏𝒌 + …….(3)
𝑹𝑻

Ea
𝒍𝒐𝒈𝑨 = 𝒍𝒐𝒈𝒌 + …….(4)
𝟐.𝟑𝟎𝟑 𝑹𝑻

From the eqn (4) “A” can be calculated if k, Ea and T are known for a reaction.
 Simple Collision Theory (Or) Collision Theory for Bimolecular
Reactions
Collision Theory:- (Max Trautzb and William Lewis)
“Arrhenius proposed that reactants are transforming into activated
Ex, Energy Barrier
complex state by gaining the activation energy to convert as products”
but he didn’t explain that how reactant molecules gain such energy.
Here comes the collision theory for the explanation.
E1
1). This theory is based on the kinetic theory of the gases.
2). According to this theory, to occur chemical reactions, there should EA
be collision between reacting molecules.
3). However, all the collisions are not effective to produce chemical E2
ΔE
change.
4). Hence, COLLISION THEORY suggested that, before the formation EB
of the product colliding molecule must be activated by absorbing
minimum amount of energy called Activation Energy (Ea)
- during the collision energy is exchanged between the molecules.
- due to this, out of two molecules one will gain little excess energy
than the average energy.
-so that they can pass over energy barrier existing between
reactants and product.
5). If the reacting molecule colloids with insufficient energy, they
can’t pass over the energy barrier.
However, if the reacting molecule collides with sufficient energy, they
can pass over the energy barrier and get activated. And hence
converted into product.
 Collision Theory (Cont.)

-Let’s consider that ‘Z’ is the no. of collisions occurred per second in a - q-value can be obtained by using Maxwell and Boltzmann
mL of gas. distribution law
-assume that in each collision, single molecule is gaining the activation Now, in a mL of gas,
energy. Let’s consider, there are n0 of molecules, in which ‘n’ molecules
at temperature, T are having energy equal to or higher than
Rate of the reaction, activation energy,
−𝑑𝑛 E
= Z molecules mL-1 s-1 ………(1) 𝑛
=𝒆 − a
𝑹𝑻 ………..(3)
𝑑𝑡 𝑛0
Example: consider the following reaction;
If, we consider energy, E as reaction’s activation energy, Ea
2HI H2 + I2
𝑛 Ea
- For the above reaction ‘Z’ is determined as 1028 at 700 K.
q= =𝒆 − 𝑹𝑻
………..(4)
𝑛0
- At the same temperature, the no. of HI molecules
decomposing are only 1018. (decrement in value) Let’s substitute q-value in eqn (2),
- Which represents that no. of molecules gains the activation
are less in comparison with the occurred collision. Ea
−𝑑𝑛 − 𝑹𝑻
- Hence, only a fraction of collisions turned out be a useful
𝑑𝑡
= Z. 𝒆 ………..(5)
collisions.
- Let’s consider that fraction useful collisions as ‘q’ above equation is the rate equation derived for biomolecules
based on COLLISION THEORY.
Rate of the reaction, will become
−𝑑𝑛
𝑑𝑡
q
= Z ………..(2)
 Verification of Collision Theory

-In the method of determining the viscosity, molecules’ collision diameter, σ can be measured.
-by using the σ, collision no, Z can be derived as follows;

𝑘 𝐸𝑎 𝑇2 − 𝑇1
𝑇 𝑙𝑜𝑔10 𝑘1 = [ ]
Z = 6.5 x 104 σ2 n2 2
2.303 𝑅 𝑇1 − 𝑇2
𝑀

- by measuring the rate constant at two different temperatures, activation energy Ea can be determined.
- Later by using the following equation, rate constant at particular temperature can be calculated.

−𝑑𝑛 Ea
− 𝑹𝑻
= Z. 𝒆 ………..(5)
𝑑𝑡
Example: consider the following reaction;

2HI H2 + I2

- For the above reaction, at 558 K calculated k = 5.2 x 10-7 L mol-1 s-1.
- At the same temperature, measured k = 3.5 x 10-7 L mol-1 s-1.
- Here both calculated and measured k –values almost equal (focus only order).
- Hence, for this reaction, COLLISION THEORY found suitable.
 Drawback of Collision Theory

i) It is found suitable for bimolecular reactions only.

ii) It is essential to make some correction (Lindemann Hypothesis) to be applicable for
unimolecular reactions.
iii) For complex reactions, there is a huge difference in reaction rate between the calculated and
measured.
-ex: ethylene polymerization; measured k-values is 2000-fold higher than the calculated.
iv) Due to the fact that all of the activated complex molecules do not get converted into products,
this point makes the huge difference in the calculated and measured k-values.
v) Even for some bimolecular reactions there is difference in the calculated and measured k-values

Reason:
1. While deriving the rate equation based on the collision theory, molecules have been considered
as non-flexible spheres
2. Hence only their kinetic energy has been accounted for the exchange of energy during the
collision.
3. But rotational and vibrational energies have not considered these points may led to its drawback.
 Absolute Reaction Rate Theory, ARR Theory (Or) Transition State
Theory (Or) Activated Complex Theory
Transition State theory or Activated Complex Theory or Theory - Increased potential energy led to the formation of activated
of Absolute Reaction Rate:- (Polanyi and Erying 1935) complex. This activated complex is unstable and decomposes
- This theory is applicable to gas as well as liquid phase to form product or collapse back into reactants.
reaction.
- It is quite complicated theory.
- According to this theory, “Before reacting, molecules changes
into intermediate products, they form transition state or
activated complex which is unstable and decompose to form
product.”
- In this theory it is supposed that, as two reacting species
approach each other, their potential energy increases and
reaches to maximum. Example: consider the following reaction;

A+B X Products
(Reactants) (Activated Complex)

H I H I H I
+ +
H I
H I H I
 Activated Complex Theory (Cont.1)

According to the activated complexes, following Here, K = Boltzmann constant and h = blank constant.
postulates have been accepted: Let's consider that the activated complexes which responses to
1. Activated Complex is a separate entity, and it will be always the vibration and receiving the frequency no, ν are decomposing;
in equilibrium with the reactants. Rate of the reaction = ν [X ] ….(4)
Example: consider the following reaction;
Substituting eqn (1) and (3) in equation (4)
𝐾𝑇
Rate of the reaction = K* [A] [B] ……(5)
ℎ
A+B X Products “k” can be considered as rate constant of the reaction,
(Reactants) (Activated Complex) Rate constant = k [A] [B] ….(6), Comparing eqn (5) and (6),
𝐾𝑇
From the reaction equilibrium constant, K* for the activated k = K* ……(7), multiply the eqn (7) with Avagadro number, N;
ℎ
complex can be derived as, 𝑁𝐾𝑇 𝑅𝑇
[𝑋] k = K*; k = K*; here, NK = R = gas constant.
K* = or [X] = K* [A] [B] ……(1) 𝑁ℎ 𝑁ℎ
𝐴 [𝐵] Based on Thermodynamics,
Δ𝐺°
2. The maximum energy consumed during the conversion of RTlnK = -ΔG° …..(8), therefore, lnk = ….(9)
RT
reactants into activated complex is referred as activation Δ𝐺°
− RT
energy. Therefore k = 𝑒 …..(10)
3. Among the frequency no of the activated complex, one must Besides, ΔG° = ΔH° - T ΔS° ….(11)
be less stable, and it is responsible for the decomposition of
activated complex into the product. (ΔH° − T ΔS°) ΔH° ΔS°
−
- This vibration’s frequency no. may be very less, therefore, k = 𝑒 RT ;k= 𝑒 − RT
𝑒 R …..(12)
- And will be having the average energy of KT, Let’s use the eqn (12) for the activated complex, K*
- Let’s consider this vibration’s frequency no. as ν,
𝐾𝑇 ΔH° ΔS°
hν = Evibration = KT ….(2) (or) ν =
ℎ
…..(3) K* = 𝑒 − RT 𝑒 R …..(13)
 Activated Complex Theory (Cont.2)

Let’s substitute the value of k* in the eqn (7), Note:

ΔH° ΔS° ΔH* = Ea + RT (Δn - 1) …… (16)
𝑒 − RT
𝑅𝑇
k =
𝑁ℎ
𝑒 R …..(14) Here Δn is the difference in no. of molecules during the
The difference between the change in activated enthalpy, ΔH* formation of activated complex.
and activation energy, Ea is very less. Moreover, for solution Based on the ARR Theory,
both values are same. ΔH∗ ΔS∗
𝑅𝑇 −
k = 𝑒 RT 𝑒 R …..(14)
𝑹𝑻
ΔS° E
− a
𝑁ℎ

Therefore, k =
𝑵𝒉
𝒆 𝑹 𝒆 𝑹𝑻 …..(15) Let's substitute eqn (16) in the eqn (14),

𝑹𝑻
ΔS∗
Above eqn (15) is the rate equation derived based on ARR k =
𝑵𝒉
𝒆 𝑹 𝒆− (Δ𝒏 −𝟏) …..(17)
Theory. And it is applicable to all type of reactions.
For unimolecular reaction, Δn = 0

𝑹𝑻
ΔS∗ E
− a
k = 𝑵𝒉 𝒆 𝑹 𝒆 𝑹𝑻 𝒆 …..(18)

For bimolecular reaction, Δn = -1

𝑹𝑻
ΔS∗ Ea
− 𝑹𝑻
k = 𝒆 𝑹 𝒆 𝒆𝟐 …..(19)
𝑵𝒉
 Comparison Between the Collision Theory & ARR Theory

E Significance:
− a 1. i.e., rate constant is dependent of activated entropy, ΔS*.
Arrhenius equation, k = A. 𝒆 𝑹𝑻 …… (1)
2. For simple reactions, both concepts match with each other.
We have rate equation derived based on collision theory, 3. For complex reactions, which is involving the larger
E molecules, A-value, several fold < Z-value.
− a
k = Z. 𝒆 𝑹𝑻 …… (2) - it is since the some of the activated reactant species are
not involved in the reaction
Let’s compare eqn (1) and (2), - at this situation, probability or steric factor, P is used,
and its value is less than 1.
Frequency co-efficient, A = Collision co-efficient, Z. ……(3)
Now, A = PZ.
- Means, rate of the reaction is dependent of collision no.
- But we have rate equation based on ARR theory, 3. Entropy is decreasing, during the formation of the activated
complex.
𝑹𝑻
ΔS∗ E
− a -decrement is very high for the complex reactions.
k = 𝑵𝒉 𝒆 𝑹 𝒆 𝑹𝑻 …..(4) -hence for all reactions eqn (5) is found suitable.
Let’s compare eqn (1) and (4), In this aspect, ARR Theory is better than the Collision Theory.

𝑹𝑻
ΔS∗
A = 𝒆 𝑹 …..(5)
𝑵𝒉
 3

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