PHYSICAL

CHEMISTRY - I
STATES OF MATTER & IONIC
EQUILIBRIUM
 Unit 1: Gaseous state
What are gases?
The simplest state of matter is a gas, a form of matter that fills any container it occupies. The
state of a pure gas can be specified by giving its volume, V, amount of substance (number of
moles), n, pressure, p, and temperature, T.

Pressure is defined as force divided by the area to which the force is applied. The SI unit of
pressure, the pascal (Pa), is defined as 1 newton per meter-squared:

Temperature, T, is the property that indicates the direction of the flow of energy through a
thermally conducting, rigid wall.

Volume, we can measure the volume the of the container in which the gas is contained.

Amount, or number of moles

The relationship which connects the above four variables is known as equation of state of the system.
The equation of state of a gas at low pressure was established by combining a series of empirical
laws.

1. Boyle’s Law: At constant T, the volume of definite 3. Gay Lussac’s Law: The pressure of a given mass of
mass of gas is inversely proportional to its pressure. a gas at constant volume is directly proportional to its
Kelvin Temperature.

4. Graham’s Law of Diffusion: The rate of diffusion or

effusion of a gas is inversely proportional to the
2. Charles Law: The volume of a given mass of a gas square root of its density or molar mass.
at constant pressure is directly proportional to its
kelvin temperature.

Herein, K2 is a constant and its value depends on the

nature, mass and pressure of the gas.
Equation of State

The results of Boyle and Charles

law were combined into an
expression which represents the
relationship between p, V and T of a
given mass of gas. This expression
was defined as equation of state.
 • Universal Gas constant (R): From the
The value of K depends on the amount of gas law, the unit of R can be defined in
gas. terms of (p x V)/(n x T)

V is an extensive property (mass

dependent), whereas P and T are intensive
properties (independent of mass).
Therefore, the dimensions of R are energy
Therefore, K = nR, where n is the amount of
gas and R is a universal constant
per mole per kelvin.
(independent of all variables). Hence, we can say that R represents
amount of work (or energy) that can be
Therefore, the general gas law is:
obtained from one mole of a gas when its
pV = nRT temperature is raised by 1 kelvin.
 Gas laws and ideal gases

• All gases do not obey gas laws under all conditions of Temperature and Pressure.
• Real obey these laws under limited conditions of low pressure and high temperature.
• However, these laws are important to postulate hypothetical ideal gases.
• Therefore, ideal gas can be defined as a gas which follows equation of state under
all conditions of temperature and pressure.
• Thus, equation of state is also known as ideal gas law.
 Calculating the value of Gas constant

• As real gases do not obey ideal gas law, the Gas constant (R) can
not be calculated using P, V and T data for real gases.
• However, experimentally it was observed that real gases
approaches ideal behaviour when the P is very low i.e p → 0
• Hence, extrapolation method on data of real gases can be used to
determine ideal gas properties.
• By measuring the volume of real gas at different Pp at constant
temperature, a graph between pV and p can be obtained.
• On extrapolating this graph to p = 0, it is possible to determine the
value of pV for one mole of gas behaving ideally.
• The value of (pV)p → 0 is independent of the nature if gas. Thus we
would obtain same value for all gases.
• Experimentally, the value of (pV)p → 0 is found to be 22.711 dm3bar at 273.15 K
temperature.
• Thus, assuming p = 1 bar, then V= 22.711dm3. Therefore, volume occupied by 1 mole of
an ideal gas at standard temperature (T = 273.15 K ) and 1 bar pressure is 22.711dm3
 Kinetic theory of gases
A theoretical model was developed based on the structure of the gas, which can correlate
the experimental facts. This Kinetic theory of gases is based on certain postulates:

1. A gas consist of large number of tiny 4. The molecules are perfectly elastic i.e. there
spherical molecules. The molecules of a gas occurs no loss of energy when the molecules
is identical in size, shape and mass. collide with each other or the walls of the
vessel.
2. The volume occupied by the molecules is
very small compared to the volume occupied 5. There exists no intermolecular forces of
by the gas. attraction or repulsion between the
3. The gas molecules are in constant random molecules.
motion. During this motion, the molecules 6. At any point, a given molecule can have
collide with other molecules as well as with energy ranging from a very small or very
the walls of the container. large value. However, the average kinetic
energy remains constant for a given
temperature.
Derivation of Kinetic gas equation
Graham’s law of diffusion and effusion
 Root Mean square speed
The root mean square (rms) speed is defined as the average of the squares of the speed.

The rms speed is directly proportional to the T and inversely proportional to the square root
of the molar mass.
Thus, at a given T, lighter gases (H2 and He) moves faster then the heavier ones (N2 and O2).

There is no effect of change in P or V on the rms speed of the molecule at a given

temperature….. Since, PV is constant at a fixed T (Boyle’s law)
 Average Kinetic Energy
Acc. To one of the postulate of KTG,

Using Kinetic gas equation,

Therefore, average kinetic energy can be given as

 Real Gases
• Real gases do not obey gas exactly under all conditions of T and P.

• This deviation of real gases from ideal behaviour can be more clearly understood by plotting ratio of observed
molar volume Vm to the ideal molar volume Vm, ideal ( = RT/p)

• This ration is called Compression factor Z,

• For ideal gas, Z =1 and is independent of T and p.

• At very low pressures, all the gases shown have Z ≈ 1 and behave nearly perfectly.

• At high pressures, all the gases have Z > 1 signifying that repulsive forces are now dominant.

• At intermediate pressures, most gases have Z < 1, indicating that the attractive forces are reducing the molar
volume relative to that of a perfect gas.
• Z is always greater than for H2
• For N2, Z > 1 in high p region and Z < 1 for
low p region.
• For CO2 there is a large dip in the beginning.
• For gases that can be easily liquified, Z value
dips sharply below the average line in the low p
region.
• Therefore, the nature of deviation depends on
the nature of gas.
• However, T also plays a critical role in
determining the shape of the curve for a
particular gas.
• Z is always greater than for H2
• For N2, Z > 1 in high p region and Z < 1 for
low p region.
• For CO2 there is a large dip in the beginning.
• For gases that can be easily liquified, Z value
dips sharply below the average line in the low p
region.
• Therefore, the nature of deviation depends on
the nature of gas.
• However, T also plays a critical role in
determining the shape of the curve for a
particular gas.
 Cause of deviation from ideal behaviour
• The real gases do not follow ideal gas law due to the following assumptions:
1. The volume occupied by the molecules is negligible compared to the total volume occupied by the gas.
2. The molecules exert no forces of attraction upon one another.

• Evidence of molar volume: The molecules of gases do occupy a certain volume. This can be proved from the fact
the gases can be liquified and solidified at low temperature and high pressure. As the temperature decreases the
thermal energy of the molecule is decreased and applying high pressure brings the molecules closer favouring the
process of liquification and solidification.

• Evidence of molecular attraction: The molecules of gases has weak forces of attraction called van der Waals
attraction, otherwise the gases could never be liquified or solidified.
 Van der Waals Equation
• Van der Waals introduced the correction terms for those two invalid assumptions in the ideal gas equation.
• Correction for Volume: Lets say Vi represents the ideal volume where molecules of an ideal gas can move freely.
However, in real gases the volume occupied the molecules of the gases is not available, therefore the free volume is
total volume minus the volume occupied by the molecules.
Let’s say b is the effective volume occupied by 1 mole of gas.
Here, b is the excluded volume or co-volume. The numerical value of b is 4 times the volume occupied by
the gas molecule.
If we consider only bimolecular collision, the volume
occupied by the volume of sphere 2r represents excluded
volume per pair.
 Van der Waals Equation
• Correction for forces of attraction: Molecule A is symmetrically surrounded by
the molecules and experiences no net forces of attraction. Whereas, molecule B is
about to strike the surface of the vessel and contributes to the total pressure. The
molecule B experience a net force of attraction towards the centre of the vessel. As
a result the momentum or the velocity of the molecule decreases. Therefore the
force exerted by the molecule B on the walls of the vessel would be less than that
expected.

• Thus, the total pressure of a real gas would be less than the ideal gas.
 Van der Waals Equation
• Correction for forces of attraction: Molecule A is
symmetrically surrounded by the molecules and
experiences no net forces of attraction. Whereas,
molecule B is about to strike the surface of the vessel and
contributes to the total pressure. The molecule B
experience a net force of attraction towards the centre of
the vessel. As a result the momentum or the velocity of
the molecule decreases. Therefore the force exerted by
the molecule B on the walls of the vessel would be less
than that expected.

• Thus, the total pressure of a real gas would be less than

the ideal gas.
This correction term depends on two factors:
1. No. of molecules per unit volume of the
vessel: When the no. of molecules is more the
net force of attraction with which molecule B
is dragged is larger, therefore large decrease in
the velocity of molecule B with which it hit
the walls of the container. Therefore the
correction term is larger.
If n is the number of moles of gas present in an
container, and V is the volume of the container,
then no. of molecules per unit volume is given as -
This correction term depends on two factors:
2. No. of molecules colliding with the container per
unit time: Larger this number, larger is the
decrease in the rate of change of momentum.
Therefore, the correction term will have a larger
value. The no. of molecules striking the container is
directly dependent on the number of molecules per
unit volume.

If n is the number of moles of gas present in an

container, and V is the volume of the container, then no.
of molecules per unit volume is given as -
Here, a is the proportionality constant that
accounts for the forces of attraction
between the molecule.
 Therefore we have,

The unit of is same as that of pressure.

Therefore the S.I unit of a is given as Pa m6 mol-2
When the substitute the pressure and volume
correction term in the ideal gas equation, we get
the equation for Van der Waals equation:

The constants a and b are called Van der Waals

constant and their value depends on the nature of
the gas.
The Van der Waals equation for 1 mole of the gas
can be given by
 Molecular Interactions in real gases
• Repulsive forces between molecules assist
expansion and attractive forces assist
compression.
• Repulsive forces are significant only when
molecules are almost in contact: they are
short-range interactions. This is the case at
high pressure, when many molecules occupy
a small volume.
• Attractive intermolecular forces have a
relatively long range. They are important
when the molecules are close together but not
necessarily touching. Furthermore, attractive
forces are ineffective when the molecules are
far apart.
• At Low P, when the sample occupies a large
volume, the molecules are so far apart for most of
the time that the intermolecular forces play no
significant role, and the gas behaves virtually
perfectly.
• Mathematically, at low p, volume is large, and b
can be ignored in comparison to Vm

Since
• At moderate pressures, when the average
separation of the molecules is only a few molecular
diameters, the attractive forces dominate the
repulsive forces. In this case, the gas can be
expected to be more compressible than a perfect gas
because the forces help to draw the molecules
together.
• At high p, when the average separation of the
molecules is small, the repulsive forces dominate,
and the gas can be expected to be less compressible
because now the forces help to drive the molecules
apart.
• Mathematically, at high p, the volume is small, and
b cannot be ignored. However, the term can
be considered negligible compared to p.
At high T and low p, when the Vm will also be
sufficiently large and the term will be
negligible. At this stage b will be also be
negligible compared to Vm and the equation is
reduced to ideal gas equation
Hydrogen and Helium:
The value of a is very small for these gases
as they are difficult to liquefy. Therefore,
ignoring the term the Van der Waals
gas equation can be written as

Hence, the Z > 1 and it increase with

increase in the value of p.

The Van der Waals gas equation is an

improvement over the ideal gas equation.
However, its generality is lost as it contains
two constants whose value depends on the
nature of the gas.
 Other Equation of State for Real Gases
1. Berthelot’s Equation: This equation is almost same as Van der Waals equation, however the constant a and b are
Berthelot’s constant. This equation was found to be more accurate than van der Waals equation for determining the
molar masses of the gases.

2. Dieterici Equation: The exponential factor was introduced in the equation to account for the effect of molecular
attraction on the pressure.

3. Virial Equation: It is the most general equation of state for real gases. All these 3 equation of states can be
approximately expressed in this one common form.

Here, B, C… are temperature dependent constants known as second, third etc virial coefficient.
• Determination of second virial coefficient, B:
Rearranging the virial equation we get-

• Extrapolating graph between

vs the to = 0, gives the value of B

• If there were no higher terms, the slope of the plot

will be equal to the value of C
Van der Waals equation to Virial Equation
 Virial Equation in terms of Pressure

A1, A2,… are virial coefficient and are

dependent on temperature
The final form of the virial equation in terms of P: Slope of Z vs p curve can be obtained by
differentiating the equation keeping the T constant

At p = 0, all the higher terms are dropped and the

above equation is reduced to
Therefore, the initial slope of the given plot is

• If the initial slope is + and size

effect (b) will dictate the behaviour of the gas
• If the initial slope is – and attractive
forces will dominate.

Hence, at 0 C
̊ the attractive forces dominates the
in case of methane and carbon dioxide

While molecular size effect dominate the

behaviour of hydrogen.
Plot of Z vs p for same gas at different temperatures:

• When temperature is low, the initial slope is –

therefore
• As the temperature is raised, the attraction becomes
smaller.
• At sufficiently high temperature, the initial slope
becomes positive and the attraction term is
sufficiently smaller than the volume term.
 Boyle temperature
• There may be a temperature at which Z → 1
with zero slope at low pressure or high molar
volume. At this temperature, which is called
the Boyle temperature, TB
• At TB the properties of the real gas do
coincide with those of a perfect gas as p → 0.
• In general, the temperature at which the initial
slope of Z vs p plot is zero is called Boyle’s
Temperature

• At TB real gases behaves ideally over a wide

range of pressure as the effect of size of
molecules and attractive forces roughly
compensate one another.
 Andrews Isotherm
• Thomas Andrew measured the p-V relationship of
carbon dioxide at various temperatures. These p-V plot
at a constant temperature are known as isotherm.
• It was observed that at
1. At high temperature (T4) isotherm resembles the
ideal gas behaviour.
2. At lower temperature (T1) the appearance of the
curve is entirely different.
 Andrews Isotherm
• From a to b, as the pressure increases the volume of
the gas decreases.
• At b, liquification begins and the volume decreases
rapidly as the pressure remains constant till all of the
gas is converted into liquid.
• At c, liquification is complete and the line cd shows
the variation of p with V for the liquefied gas.
• At any point X on the line bc,
• At higher temperature T2, similar types of curve is
obtained however the width of the horizontal line is
reduced
• At Tc, the horizontal portion is reduced to a single
point. At T > Tc there is no indication of liquification
 Andrews Isotherm
• Thus, for every gas there is a limit of temperature above which it can not be liquified no matter
what the temperature is.
• Critical Temperature (Tc), is the maximum temperature at which a gas can be liquified or the
temperature above which liquid cannot exist.
• Critical Pressure (Pc), is the minimum pressure required to cause the liquification of the gas
at Tc.
• Critical Volume (V c), is the volume occupied by 1 mole of the gas at Tc and Pc
• Point Y on the graph represents the critical state where temperature, Pressure and volume has
critical values.
• The isotherm corresponding to Tc is called critical isotherm.
 Characteristics of Critical Isotherm
• To the left of point Y, we have the liquid state
whereas to the right we have gaseous state.
• At point Y, transition from liquid to gas (or vice
versa) takes place and it is not possible to state
whether the substance is in liquid state or gaseous
state.
• Therefore, both the states becomes indistinguishable
at the critical point and surface of separation
between liquid and gas disappears.
• At this point various physical properties such as
density, refractive index, etc have identical values
for both the states.
 Continuity of States
• At the Tc, the boundary between the liquid phase and
gas phase disappears and the densities of the
substance in the two phases are the same.
• Continuity of State is the property of a transition
between two states of matter, as between gas and
liquid, during which there are no abrupt changes in
physical properties.
• Connecting the end points of the horizontal lines in
the isotherm we get a portion that separates liquid
phase from the gaseous phase and it is known as
surface of discontinuity.
• Within the curve the liquid and gas phase coexist,
therefore it is able to distinguish between gas and
liquid phase
 Continuity of States
• However, in practice it is not always possible to go
from one state to another state without any sharp
discontinuity.
• Increase the temperature of the gas keeping the
volume constant. The pressure rises along AL.
• Upon reaching point L, the pressure is kept constant
and gas is cooled this decreases the volume along the
line LD.
• Thus, we passed from A to D without the gradual
change as occurs along the line BC i.e. condensation
in the usual sense of the term did not occur.
• Point D represents highly compressed gaseous state
of the substance.
• Point D represents highly compressed gaseous state of
the substance.
• Therefore, the statement that line DC represents a liquid
state must be modified.
• At no time in this series of changes did the state point
pass through the two phase region. Thus, the
condensation in the usual term did not occur.
• This demonstration shows that these two states of matter
can be transformed into one another continuously.
• Overall, we refer to sates in region of point D as a liquid
states or highly compressed gaseous state depends
purely upon which viewpoint happens to be convenient
at the moment.
• If the point lies under the dome the liquid and gas phase can be
distinguished, since both are present in equilibrium and there is a
surface of discontinuity separating them.
• In the absence of this surface of discontinuity there is no fundamental
way of distinguishing between liquid and gas.
• The figure shows the isotherms calculated from Van
der Waals equation.

• The isotherm at high V region resembles ideal gas.

This is because V is large compared to b and the term
.
• Similarly at high temperature (T3), the isotherm looks
like ideal gas.
• At lower temperature and smaller volumes, none of the
term can be neglected.
• At temperature Tc, the graph develops a point of
inflection.
• At still lower temperature, the graph shows a minimum
and a maximum.
• Thus, the curve at T2 predicts 3 value of volume at
pressure C. The corresponding plateau predicts many
volumes at pressure p1.
• The section AB and DE of the van der Waals isotherm
can be realized experimentally.
• If volume of the gas at T2 is gradually reduced the
pressure rises along the isotherm until point E is reached
at pressure p1.
• At this point condensation should occur, however, it
may happen that liquid does not form thus further
reduction in volume leads to increased pressure along
line ED.
• In region ED, pressure of gas exceeds equilibrium vapor
pressure of the liquid at p1 and T2. Thus this region
represents super cooled vapour.
• Similarly, if volume of liquid at temperature T2, is
increased the pressure falls until point A at pressure p1
is reached.
• At this point vapour should form, however, instead
further increase in volume produces reduction of
pressure along line AB.
• Along the line AB, liquid exists under the pressure that
corresponds to equilibrium vapor pressure of the liquid
at temperature below T2.
• Thus the points at AB represents the superheated liquid.
• The states of superheated liquid and supercooled gas are
metastable states
• These metastable states are highly unstable and a slight
disturbance can cause the system to revert
spontaneously into the stable state with two phase
present in equilibrium.
• Section BD of the isotherm can not be realized
experimentally.
• In BD region the slope of the curve is +ve, increasing
the volume of such a system would increase the pressure
and decreasing the volume will decrease the pressure.
• Thus, the system at BD is highly unstable, slight
disturbance under such conditions can lead to either
explosion or collapse of the system.
• These metastable states are highly unstable and a slight
disturbance can cause the system to revert
spontaneously into the stable state with two phase
present in equilibrium.
• Section BD of the isotherm can not be realized
experimentally.
• In BD region the slope of the curve is +ve, increasing
the volume of such a system would increase the pressure
and decreasing the volume will decrease the pressure.
• Thus, the system at BD is highly unstable, slight
disturbance under such conditions can lead to either
explosion or collapse of the system.
• Overall, the van der Waals loops, are unrealistic
because they suggest that under some conditions an
increase of pressure results in an increase of volume.
• For T < Tc, the calculated isotherms oscillate, and each
one passes through a minimum followed by a
maximum. These extrema converge as T → Tc and
coincide at T = Tc; at the critical point the curve has a
flat inflexion.
• An inflexion of this type occurs when both the first and
second derivatives are zero.
 Determination of critical constant
Hence, we can find the critical constants by
calculating these derivatives and setting
them equal to zero.
• These relations provide an alternative route to the determination of a and b from the
values of the critical constants. They can be tested by noting that the critical
compression factor, Zc, is predicted to be equal to

• If we compare this value of Zc, with the experimental values, it is found that the
agreement is very poor. This is because the Van der Waals equation is not accurate
enough to predict the behavior of the gas near its critical state.
 Law of Corresponding states
• We have seen that the critical constants are
characteristic properties of gases.
• We therefore introduce the dimensionless reduced
variables of a gas by dividing the actual variable by
the corresponding critical constant:

• Therefore, Van der Waals equation can be written in

a form which contains no constant characteristic of
an individual gas by substituting theses values

in van der Waals equation.

• In practice the reduced equation of state is not
directly used.
• The graph between Z and reduced pressure at
different reduced temperature is generally used.
 Maxwellian distribution of molecular speed

• We know that the root mean square speed is expressed as:

• The rms speed of the molecules of a gas is proportional to the square

root of the temperature and inversely proportional to the square root of
the molar mass.

• The higher the temperature, the higher the rms speed of the molecules.

• Also, at a given temperature, heavy molecules travel more slowly than light molecules.

• The above equation gives us the mean square speed of molecules. However, in an actual gas
the speeds of individual molecules span a wide range.

• The collisions in the gas continually redistribute the speeds among the molecules.
• Before a collision, a molecule may be travelling rapidly, but after a collision it may be
accelerated to a very high speed, only to be slowed again by the next collision.

• The way in which molecules of gas are distributed over a possible range of speed at a
temperature T was derived by J.C. Maxwell.

• dNu is the number of molecules having speeds between u and u+du in terms of total number
of molecules present (N).

• M is the molar mass and m is the mass of single gas molecule.

• According to this expression, the fraction dNu/N of molecules having speeds between u and
u+du for a gas of molar mass M depends only on Temperature.
• The above expression is called the Maxwell distribution of speeds and is derived in the
following Justification:
1. It includes a decaying exponential function, it implies that the fraction of molecules with
2
very high speeds will be very small because e−x becomes very small when x2 is large.
2. The factor M/2RT multiplying u2 in the exponent is large when the molar mass, M, is large,
so the exponential factor goes most rapidly towards zero when M is large. That is, heavy
molecules are unlikely to be found with very high speeds.
3. The opposite is true when the temperature, T, is high: then the factor M/2RT in the
exponent is small, so the exponential factor falls towards zero relatively slowly as u
increases. In other words, a greater fraction of the molecules can be expected to have high
speeds at high temperatures than at low temperatures.
• A factor u2 (the term after the e) multiplies the exponential. This factor goes to zero as u
goes to zero, so the fraction of molecules with very low speeds will also be very small.

• The remaining factors simply ensure that, when we add together the fractions over the entire
range of speeds from zero to infinity, then we get 1.
 Plot of Maxwell distribution of speed

• The most probable speed (corresponding to the peak of the distribution) increases with
temperature, and simultaneously the distribution becomes broader.
 Plot of Maxwell distribution of speed

• Graph is parabolic near the origin, since the

 Consequence of distribution of speed

• A direct consequence of distribution of speeds is that the average kinetic energy of a gas is
also constant for a given temperature.

dNi = number of molecules having speed ui.

Since dNi/N (fraction of molecules having speed ui+du) is constant at a given temperature,
therefore, it has a constant value.
Thus the average kinetic energy is also constant at a given temperature.
 Plot of Maxwell distribution of speed

• Graph is parabolic near the origin, since the factor u2 is

dominant in this region and the exponential function is
almost equal to unity.

• At higher values of u, the exponential factor is

dominating, and the function decreases rapidly.

• The exponential factor is called Boltzmann

factor.

• The consequence of above two contrasting behaviors (or

factors) makes the product function, a complete
distribution function, to have a maxima in the plot.
 • Diving this equation by du, we get fraction of
• F(u2)
is probability density for the distribution molecules in the speed range u and u+du per
of molecular speeds. unit width of interval.
• N is the total number of molecules in a
container.
• dNu is number of molecules out of N having
speeds in the range u and u+du.
• dNu /N is fraction of molecules having speeds • The above equation is plotted to give us the
between u and u+du which is directly maxwell Boltzmann distribution curve.
proportional to F(u2).
 Plot of Maxwell distribution of speed

• The probability that a molecule has a speed

between any two given values is given by
area under the curve between these two
values of speed (shaded area).

• Plot depicts the fact that chances of finding

the molecules with very low or very high
speeds are very small.

• The majority of molecules are those which

have speeds that are grouped around ump i.e.,
the peak of the curve at any temperature.
Effect of Temperature on nature of plot
Effect of mass of a gas on nature of plot
 Most probable speed

• Most probable speed, ump is the speed

possessed by maximum fraction of the
molecules.
• The expression of the ump can be derived
using the condition of maxima by setting the
first derivative equal to zero.
 Consequence of distribution of speed

• A direct consequence of distribution of speeds is that the average kinetic energy of a gas is
also constant for a given temperature.

dNi = number of molecules having speed ui.

Since dNi/N (fraction of molecules having speed ui+du) is constant at a given temperature,
therefore, it has a constant value.
Thus the average kinetic energy is also constant at a given temperature.
 Most probable speed

• Most probable speed, ump is the speed

possessed by maximum fraction of the
molecules.
• The expression of the ump can be derived
using the condition of maxima by setting the
first derivative equal to zero.
 Consequence of distribution of speed

• A direct consequence of distribution of speeds

is that the average kinetic energy of a gas is
also constant for a given temperature.

• This was one of the assumption of the kinetic

theory of gases.
 Molecular collision in a gas

• While considering the molecular collision we

assume that-
1. Molecules are rigid spheres
2. Molecules are non interacting.
3. All molecules move with the same
average speed.

• The closest distance between the centers of the

two molecules taking part in collision is called
the collision diameter. It is denoted by σ
• The collision cross section area for the rigid
molecule is given by

• This area is an imaginary sphere of radius

around the molecule within which the centre
of another molecule can not penetrate.
 Collision frequency
• Collision frequency, number of collisions
taking place per second per unit volume of the
gas.
• We consider the positions of all the molecules
except one to be frozen.
• Then we note what happens as one mobile
molecule travels through the gas with average
speed ū for unit time.
 Mean free path
• The mean free path is the average distance
travelled by the molecule between two
successive collisions.
Effect of T and P on mean free path and molecular collision
 Viscosity of gases
• Internal friction which opposes the relative
motion of adjacent layers of a fluid is known
as viscosity.

• In a laminar flow of fluid in a cylinder, layers

touching the sides of the tubes are stationery
and velocity increases towards the center of
the tube. Thus there exists a velocity gradient
amongst different layers of a liquid.
Viscosity of gases
 Viscosity of gases
• In gases, molecules ceaselessly move between • Therefore, viscosity in gases arises due to
the layers and bring with them the component transfer of momentum across the layers of the
of linear momentum they possessed in their gas.
original layer.

• A layer is retarded by molecules arriving from

a more slowly moving layer because they have
a low momentum in the x-direction.

• A layer is accelerated by molecules arriving

from a more rapidly moving layer.

• We interpret the net retarding effect as the

fluid’s viscosity.
 Viscosity of gases
Let us consider a layer PP` moving with velocity
uz at a height z. Assuming:
Let the velocity gradient be 1. Flow velocity uz is very small compared to
mean gas velocity u.
2. Only molecules reaching PP` are those which
on an average have just made their last
collision at a distance λ from height z.
3. Number of molecules passing downwards or
upwards through a unit area per unit time
∗ū

4. N* is the number of molecules per unit

volume and ū is the average speed of gas
molecules.
 Viscosity of gases
Let us consider a layer PP` moving with velocity
uz at a height z. Assuming:
Let the velocity gradient be 1. Flow velocity uz is very small compared to
mean gas velocity u.
2. Only molecules reaching PP` are those which
on an average have just made their last
collision at a distance λ from height z.
3. Number of molecules passing downwards or
upwards through a unit area per unit time
∗ū

4. N* is the number of molecules per unit

volume and ū is the average speed of gas
molecules.
Viscosity of gases
Viscosity of gases
Viscosity of gases
Effect of Temperature and Pressure on viscosity
Effect of Temperature and Pressure on viscosity
 Effect of Temperature and Pressure on viscosity
There is no effect of pressure on the coefficient Experimentally, it is observed that the increase
of viscosity of gases. For most circumstances in viscosity is somewhat higher than the
near the conditions, we live in, pressure predicted by the relation established. The
doesn’t have much effect on viscosity. deviation is due to the existence of
intermolecular attraction which was not taken
The technique employed for measuring into account in the Kinetic Theory. A
viscosities of gases is based on Poiseuille’s satisfactory empirical relation between
formula for the rate of flow of a fluid through a viscosity and temperature has been put forward
tube of radius r: by in the form

where, C is a constant called Sutherland’s

constant.
where V is the volume flowing, p1 and p2 are
the pressures at each end of the tube of length
l, and p0 is the pressure at which the volume is
measured.
 Effect of Temperature and Pressure on viscosity
Dependence of viscosity on temperature can be
interpreted as rise in temperature leads to rise
in velocity which would result in greater
exchange of momentum in the flowing gas,
thereby making greater turbulence in the
flowing gas at higher temperatures.

viscosity of liquids show reverse phenomena

that it decreases with increase of temperature.
This happens because of the decrease in
intermolecular attractive forces with rise in
temperature.
 Law of Equipartition of Energy
A molecule has a certain number of degrees of
freedom, such as the ability to translate (the
motion of its center of mass through space),
rotate around its center of mass, or vibrate (as
its bond lengths and angles change).

Many physical and chemical properties depend

on the energy associated with each of these
modes of motion.

The equipartition theorem of classical

mechanics is a useful guide to the average
energy associated with each degree of freedom
when the sample is at a temperature T.
 Law of Equipartition of Energy
The law of equipartition of energy may be
stated as:
“If the energy of a molecule can be written in
the form of a sum of terms, each of which is
proportional to the square of either a velocity
component or a coordinate, then the
contribution of each of these terms to the
average energy is equal to (½)kT.”

or

For a collection of particles at thermal

equilibrium at a temperature T, the average
value of each quadratic contribution to the
energy is the same and equal to (½)kT
Law of Equipartition of Energy
 Law of Equipartition of Energy
Rotational motion: A linear molecule, such as
N2 and CO2, can rotate around two axes
perpendicular to the line of the atoms, so it has
two rotational modes of motion each
contributing a term (½)kT to the internal
energy.

A nonlinear molecule, such as CH4 or water,

can rotate around three axes and, again, each
mode of motion contributes a term (½)kT to
the internal energy.
Law of Equipartition of Energy
 Law of Equipartition of Energy
Vibrational motion: A normal mode of If the vibrational motion is assumed to be
vibration is defined as the molecular motion in harmonic, then energy of each vibrational
which all the atoms in the molecule vibrate mode is given as
with the same frequency & all the atoms pass
through their equilibrium positions
simultaneously”.

Modes of vibration may result in the stretching

& bending of molecular bonds. Where μ is the reduced mass, kf is the force
constant, r0 is the equilibrium value of the
coordinate r and dr/dt is the change in the
internuclear distance with time.

Thus, average energy stored in a vibrational

motion is:
 Degree of freedom
Degree of freedom of a molecule may be Translational Degrees of Freedom:
defined as “the independent number of Translational motion of an atom or a molecule
parameters which must be specified to describe can be ascribed to the translation of its
the state or position of the molecule”. position, which is further described by three
coordinates viz. x, y & z .
For example, pressure, volume, temperature &
composition are used to describe the state of All the monoatomic or polyatomic gases have
the system three translational degrees of freedom.
For a gas having N molecules the system
would be described by specifying three
coordinates of each molecule i.e. a total of 3N
coordinates. Therefore, there are 3N
independent components of the motion, or
degrees of freedom available for describing
such a system.
 Degree of freedom
Rotational Degrees of Freedom: A linear
molecule can rotate around two axis, therefore-

A non-linear molecule can rotate about three

axis, therefore-
 Degree of freedom
Vibrational Degrees of Freedom: Number of
vibrational degrees of freedom can be
calculated by subtracting sum of rotational &
translational degrees of freedom from 3N.

For linear molecules- there are 3 translational

& 2 rotational degrees of freedom. Hence,
vibrational degrees of freedom for linear
molecules are 3N-5.

For non-linear molecules- there are 3

translational & 3 rotational degrees of
freedom. Hence, vibrational degrees of
freedom for non-linear molecules are 3N-6.
 Degree of freedom
Calculate degree of freedom for: He, H2, HCl, H2O, CO2, C6H6 and a protein molecule
containing 44700 atoms.
 Total Average Energy
The total average energy per molecule is sum Total energy for per mole gas-
of contribution from translational, rotational &
vibrational energies.
 Molecular basis of heat capacity
The kinetic theory of gases together with the
law of equipartition of energy provides
satisfactory prediction of specific heat
capacities of gases.

Specific heat capacity of a substance is the

amount of heat (in Joules) required to raise the
temperature of one gram of the substance by 1 If gas is assumed to be ideal
K. When the substance is one mole then it is
called molar heat capacity.
Also, for an ideal gas energy depends only on
There are two heat capacities: temperature-
1. Heat capacity at constant Volume (Cv)
2. Heat capacity at constant pressure (Cp)
Molecular basis of heat capacity
 Molecular basis of heat capacity
The experimental value of Cv for monoatomic This anomaly can be attributed to the fact that
gases is 12.5 JK-1mol-1 which is in excellent law when, we take quantum mechanical aspect
agreement with the predicted one (1.5R = 1.5 x of energy (esp. vibrational energy) into account
8.314 = 12.47 JK-1mol-1). an exponential factor comes into picture (a
function of temperature) which decrease the
For polyatomic gases, it can be seen that the magnitude of Cv.
experimental values are lower than the
predicted values.

For diatomic gases, experimental value for Cv

lies between 20.78 to 29.10 (more close to
20.78) but the predicted value is 29.10.

For non-linear molecules the experimental

values are very much lower than the predicted
ones.
Q1. Calculate γ at room temperature for He and methane gas assuming they are ideal gases.
Q2. The coefficient of viscosity of CO2 is 14.80 μPa s at 20oC. Calculate its collision diameter.
Q3. Calculate Boyle’s temperature for CO2, assuming it to be a van der Waals gas.
Q4. Calculate critical temperature of a van der Waals gas for which Pc is 100 atm and b is 50 cm3mol-1.
Q5. Calculate the pressure exerted by 1 mole of CO2 gas at 40oC confined to a volume of 0.107 dm3,
using the law of corresponding states, given the critical constants of the gas are Vm,c= 0.0957 dm3,
Tc= 304K and Pc= 73 atm.