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 HEAT & THERMODYNAMICS
2. THERMODYNAMICS
It is the study of interelations between heat and other forms
of energy
Thermodynamic System : A collection of large number of
molecules of matter (solid, liquid or gas) which are so
arranged that these posses certain values of pressure,
volume and temperature forms a thermodynamic system.
• The parameters pressure, volume, temperature, internal
energy etc which determine the state or condition of system
are called thermodynamic state variables.
In thermodynamics we deal with the thermodynamic systems
as a whole and study the interaction of heat & energy during
the change of one thermodynamic state to another.
2.1 Thermal Equilibrium
The term ‘equilibrium’ in thermodynamics implies the state
when all the macroscopic variables characterising the
system (P, V, T, mass etc) do not change with time.
• Two systems when in contact with each other come to
thermal equilibrium when their temperatures become same.
• Based on this is zeroth law of thermodynamics. According
to zeroth law, when the thermodynamics systems A and B
are separately in thermal equilibrium with a third
thermodynamic system C, then the systems A and B are in
thermal equilibrium with each other also.
2.2 Heat, Work and Internal Energy
Internal Energy is the energy possessed by any system
due to its molecular K.E. and molecular P.E. Here K.E & P.E
are with respect to centre of mass frame. This internal
energy depends entirely on state and hence it is a state
variable. For 1 real gases internal energy is only by virtue
of its molecular motion.
nf RT
Units for ideal gases where
3
n = number of moles
f = Degree of fredom
R = Universal Gas Constant
T = Temperature in Kelvin
Internal Energy can be change either by giving heat energy
or by performing some work.
Heat Energy is the energy transformed to or from the system
because of the difference in temperatures by conduction,
convection or radiation.
The energy that is transferred from one system to another
by force moving its point of application in its own direction
is called work.
dx
System
Fs = PsA
Work done by the system   F dx
  Ps Adx
  Ps dV
Where Ps Pressure of system on the piston. This work done
by system is positive if the system expands & it is negative
if the system contracts.
• Work and Heat are path functions whereas internal energy
is a state function.
• Heat & work are two different terms through they might
look same.
2.3 Important Thermodynamics Terms
State Variables : P, V, T, moles
They can be extensive or intestive.
Equation of State : The equation which connects the
pressure (P), the volume (V) and absolute temperature (T)
of a gas is called the equation of state.
PV = constant (Boyle’s Law)
V
= constant (Charle’s Law)
T
 PV = NRT
Thermodynamic Process : A thermodynamic process is
said to take place when some changes occur in the state of
a thermodynamic system, i.e., the thermodynamic
parameters of the system change with some important time.
Types of these thermodynamic process are Isothermal,
Adiabatic, Isobaric and Isocboric
Quasi Static Process : A thermodynamic process which is
infinitely slow is called as quasi-static process.
• In quasi static process, system undergoes change so slowly,
that at every instant, system is in equilibrium, both thermal
and mechanical, with the surroundings.
 Study Materials
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 HEAT & THERMODYNAMICS

• Quasi-static process is an idealised processed. We generally 2.5.1 Isothermal Process

assume all the processes to be quasistatic unless stated.
Description : A thermodynamic process in which
Indicator P-V, Diagram : A graph between pressure and
temperature remains constant
volume of a gas under thermodynamic operation is called
P-V. diagram. Condition : The walls of the container must be perfectly
conducting to allow free exchange of heat between gas
P and its surroundings.
The process of compression or expansion should be slow
a
so as the provide time for exchange of heat.
b
These both conditions are perfectly ideal.
d c
v Equation of State : T = Constant or Pv = Constant
Indicator Diagram :
a Isobaric
b Isothermal P P
c Adiabatic
d Isochoric
• Area under P – V diagram gives us work done by a gas.
st v
2.4 1 Law of Thermodynamics T

Let Q = Heat supplied to the system by the surroundings

W = Work done by the system on the surroundings P
Slope of P  V at any point.
U = Change in internal energy of the system. V

First law of thermodynamics states that energy can neither U = 0 (Temperature remains constant)
be created nor be destroyed. It can be only transformed v2
from the form to another.
W=  P dV
g
Mathematically : Q = U + Q v2

Sign Conventions : v2
nRT dV
• When heat is supplied to the system, then Q is positive =  V V [Using PV = nRT)
and when heat is withdrawn from the system, Q is v2

negative.
v2
• When a gas expands, work done by the gas is positive & = nRT l n v
when a gas contracts then w is negative 1

• U is positive, when temperature rises and U is negative, First Law of Thermodynamics

when temperature falls.
Q = U + W
Remember here we always take work done by the system.
In chemistry, work done on the system is considered. Hence v2
st
there is some different look of 1 law of Thermodynamics in  Q = nRT l n v
1
chemistry.
Q + W = U Remarks : All the heat supplied is used entirely to do work
against external sorroundings. It heat is supplied then the
where Q, U have same meanings but W stands for work
gas expands & if heat is withdrawn then the gas contracts.
done on the system
Practical Examples :
2.5 Application of the First of Law of Thermodynamics
Melting of ice at 0°C
st
Here we see how 1 Law of Thermodynamics is applied to
Boiling of H2O at 100°C
various thermodynamic processes.
 HEAT & THERMODYNAMICS

2.5.2 Adiabatic Process

cons tan t  1 1 
Description : When there is not heat exchange with =  r 1  r 1 
1 r  V2 V 
surroundings
1

Conditions : The walls of the container must be perfectly Also we know

non-conducting in order to prevent any exchange of heat
between the gas and its surroundings. P1 V1r  P2 V2r  cons tan t

The process of compression or expansion should be rapid

so there is no time for the exchange of heat. 1  P2 V2 r P1 V1r 
   
1  r  V2r 1 V1r 1 
These conditions are again ideal condition and are hard to
obtain
P2 V2  P1 V1 nR  T1  T2 
Equation of State : W = 
r
1 r r 1
Pv = constant
r –1 First Law of Thermodynamics
or TV = constat
Q = UT + W
r
or PT 1 r
 cons tan t Substituting the values

Indicator Diagram We get Q = 0

Q = 0 is as expected
P Remarks : It gas expands adiabatically then its temp
decreases & vice vers a
isotherm Practical Example
• Propagation of sound waves in the form of compression &
v rarefaction
• Sudden bursting of a cycle tube.

 rp 2.5.3 Isochoric Process

Slope of adiabatic curve 
V
Description : Volume remains constant
• As shown in graph adiabatic curve is steeper than Condition : A gas being heated  or cooled inside a rigid
isothermal curve. container.

nfRDT nR  T2  T1  P2 V2  P1 V1 P
U    Equation of State : V = constant or = constant
2 r 1 r 1 T
Work Done by Gas : If a gas adiabatically expands from V1
to V2 P P P

V2
dV
W = V
V1
r

V2
v T T
dV
= cons tan t  Vr
V1
n f R T
U =
2
 PV r  cons tan t 
 
  p  cons tan t  n R  T2  T1 
 V r
 =
r 1
V2
 V  r 1  P2 V2  P1 V1 nR T
= cons tan t    U = 
 1 r V 1 r 1 r 1
 HEAT & THERMODYNAMICS

Work First Law of Thermodynamics

W = O as gas does not expands Q = U + W
First Law of thermodynamics
nfRT
Q = U + W  Q =  nRT
2
n f R T
 Q= ...(7)  fR 
2  Q =   R  T ...(10)
 2 
Remarks : Since we have studied earlier, that when heat is
supplied to any process. its temp increases according to Remarks : Similar to CV, we can define molar heat capacity
relation at constant pressure

Q = nCT Q 
 CP = nT  ...(11)
P
Q
 C=
nT From equation 10 & 11
Now this C depends upon external conditions for gases.
fR
We get CP = R ...(12)
Q  2
Here it is refered as nT  ...(8)
v From equation 9 & 12

i.e. Molar heat capacity at constant volume fR

Replacing by CV we get
Comparing equation 7 and 8 2
CP = CV = R ...(13)
fR
We getCv = ...(9) which is also called as Mayer’s Relation.
2
• Similar to molar specific heat at constant pressure and molar
2.5.4 Isobaric Process specific heat at constant volume, we can define molar
Description : When pressure remains constant specific heat for any process.
Condition : When in one container, the piston is free to For example :
move and is not connected by any agent. C adiabatic = 0
Equation of State : P = constant C isothermal = 

V Basically gas does not possess a unique specific heat.

= constant Mainly we have CP & CV
T
Indicator Diagram : Specific Heat at Constant Volume : It is defined as the
amount of heat required to raise the temperature of 1g of a
P P gas through 1C°, when its volume is kept constant. It is
denoted as CV.
Specific Heat at Constant Pressure : It is defined as the
amount of heat required to raise the temperature of 1g of a
v T gas through 1C° keeping its pressure constant. It is denoted
as CP.
nf RT • Please Note CP, CV means Molar heat Capacity & CP, CV
U = same as always means specific heat capacity
2
• CV = MCV & CP = MCP where M stands for molar mass of any
W =  PdV  PV sample.
(as pressure is constant) R
• CP  CV 
= PV2 – PV = nRT M
 HEAT & THERMODYNAMICS

2.5.5 Melting Process 2.7 Heat Engines

In any case first law is always applicable It is a device that converts heat energy into mechanical
energy.
Q = mLf as learned earlier.
Key Elements :
W=0
• A source of heat at higher temperature
(In the change of state from solid to liquid we ignore any
expansion or contraction as it is very small) • A working substance

According to first law of thermodynamics • A sink of heat at lower temperature.

U = Q – W Working :

U = mLf • The working substance goes through a cycle consisting of

several processes.
Remark : The heat given during melting is used in
increasing the internal energy of any substance • In some processes it absorbs a total amount of heat Q1 from
the source at temperature T 1.
2.5.6 Boiling Process
• In some processes it rejects a total amount of heat Q2 to the
Here sink at some lower temperature T2.
Q = mLV • The work done by the system is a cycle is transferred to the
environment via some arrangement.
W = P[V2 – V1]
Schematic Diagram
(Pressure is constant during boiling and it is equal to
atmospheric pressure) W
 U = Q – W
U = mLf – P(V2 – V1)
Source or Q1 Working Q2 Sink or
2.5.7 Cyclic Process Hot Reservoir Substamnce Cold Reservoir

A cyclic process is one is which the system returns to its

T1 T2
initial stage after undergoing a serves of change
Example Indicatgor Diagram First Law of Thermodynamics
P  Energy is always conserved
A  Q1 = W + Q 2 ...(14)
Thermal Efficiency of a heat engine is defined of the ratio
B
of net work done per cycle by the engine to the total amount
V of heat absorbed per cycle by the working substance from
the source. It is denoted by .
U = mLV O
W = Area under the loop. W
= Q ...(15)
Q = W as per First Law of thermodynamics 1

Here W is positive if the cycle is clockwise & it is negative Using equation 14 and 15 we get
if the cyclic is anti clockwise.
Q2
2.6 Limitations of the First Law of Thermodynamics  = 1 Q ...(16)
1

• The first law does not indicate the direction in which the
change can occur.
• The first law gives no idea about the extent of change
• The first law of thermodynamics gives no information about
the source gives no information about the source of heat.
i.e. whether it is a hot or a cold body.
Ideally engines shuld have efficiency = 1
Remarks : The mechanism of conversion of heat into work
varies for different heat engines.
• The system heated by an external furnace, as in a steam
engine. Such engines are called as external combustion
engine.
 HEAT & THERMODYNAMICS

• The system is which heat is produced by burning the fuel Though all the statements are the same in their contents,
inside the main body of the engine. Such an engine is called the following two are significant.
as Internal Combustion Engine. Kelvin Pnek Statement : No process is possible whose
2.8 Refrigerator and Heat Pumps sole result is the absorption of heat from a reservoir and the
complete conversion of the heat into work.
A refrigertor or heat pump is a device used for cooling
Calcius Statement : No process is possible whose sole
things.
result is the transfer of heat from a colder object to a hotter
Key Elements : object.
• A cold reservoir at temperature T 2. Significance : 100% officiency in heat engines or infinite
• A working substance. CoP in refrigerators is not possible.
• A hot reservoir at temperature T1 2.10 Reversible and Irreversible Process
Working
Reversible Process : A thermodynamic process taking a
• The working substance goes through a cycle consisting of system from initial state i to final state f is reversible, if the
several process. process can be turned back such that both, the system and
• A sudden expansion of the gas from high to low pressure the surroundings return to their original states, with no
which cool it and converts it into a vapour-liquid mixture. other change anywhere else in the universe.
• Absorption by the cold fluid of heat from the region to be Conditions for reversibility :
cooled converting it into vapour. 1. Process should proceed at an extremely slow rate, i.e.,
• Heating up of the vapour due to external work done on the process is quasistatic so that system is in equilibrium with
working substance. surroundings at every stage.
• Release of heat by the vapour to the sorroundings bringing 2. The system should be free from dissipative forces like
it to the initial state and completing the cycle. friction, inelasticity; viscosity etc.
Sychematic Diagram. Examples : No process exactly reversible, though a slow
expansion of an ideal gas is approximately reversible.
W
Irreversible Process : A process which does not satisfy
any of the conditions for reversible is called an irreversible
Hot Reservoir Q1 Q2 Cold Reservoir process.
T1 T2
Causes :
• Spontaneous process
First Law of Thermodynamics
• Presence of friction, viscosity and such dissi-ptive forces
Q2 + W = Q 1 ...(17)
Significance of Reversibility :
Coefficient of Performance of refrigerator () is defined as
• Main concern of thermodynamics is the efficiency with
the ratio of quantity of heat removed per cycle from contents
which the heat is converted into Mechanical Energy.
of the refrigerator (Q2) to the energy spent per cycle (W) to
remove this heat • Second Law of Thermodynamics rules out the possibility
of a perfect heat engine with 100% efficiency.
Q2 • It turns out that heat engine based on idealised reversible
 ...(18)
W processes achieves the highest possible efficiency.
Using equation 17 and 18 we get
2.11 Carnot Engine
Q2 Sadi Carnot devised on ideal cycle of operation for a heat

Q1  Q 2 engine called as carnot cycle.

Ideally heat pumps should have  =  Engine used for realising this ideal cycle is called as carnot
heat engine.
2.9 Second Law of Thermodynamics
Constructions : The essential parts of an ideal heat engine
There are number of ways in which this law can be stated. or Carnot heat engine are shown in figure.
 HEAT & THERMODYNAMICS

Consider one gram mole of an ideal gas enclosed in the

cylinder. Let V1, P1, T1 be the initial volume, pressure and
temperature of the gas. The initial state of the gas is
represented by the point Aon P–V. diagram, We shall assume
Cylinder
Ideal that all the four processes are quasi-static and non
Gas dissipative, the two conditions for their reversibility.
Steps
Source at Insulating Sink at
Temp. T1 Pad Temp. T2 1. Isothermal Expansion :
The cylinder is placed on the source and gas is allowed to
(i) Source of heat : The source is maintained at a fixed higher expand by slow outward motion of piston. Since base is
temperature T1, from which the working substance draws perfectly conducting therefore the process is isothermal.
heat. The source is supposed to possess infinite thermal
Now
capacity and as such any another of heat can be drawn
from it without changing its temperature. U1 = O
(ii) Sink of heat : The sink is maintained at a fixed lower
V2
temperature T2, to which any amount of heat can be rejected q1 = W1 = RT1l n . V = Area ABmKA
by the working substance. It has also infinite thermal 1

capacity and as such its temperature remains constant at q1  Heat absorbed by gas
T2, even when any amount of heat is rejected to it.
w1  work done by gas
(iii) Working substance : A perfect gas acts as the working
substance. It is contained in a cylinder with non-conducting 2. Adiabatic Expansion :
sides but having a perfectly conducting-base. This cylinder The cylinder is now removed from source and is placed on
is fitted with perfectly non-conducting and frictionless the perfectly insulating pad. The gas is allowed to expand
piston. further from B(P2, V2) to C (P3, V3). Since the gas is thermally
Apart from these essential parts, there is a perfectly insulated from all sides, therefore the processes is adiabatic
insulating stand or pad on which the cylinder can be placed. q2 = 0
It would isolate the working substance completely from the
surroundings. Hence, the gas can undergo adiabatic R  T2  T1 
U 2 
changes. r 1
The Carnot cycle consists of the following four stages :
R  T3  T1 
1. Isothermal exdpansion W2  = Area BCNMB
r 1
2. Adiabatic expansion
3. Isothermal Compression :
3. Isothermal compression
The cylinder is now removed from the insulating pad and is
4. Adiabatic compression.
placed on the sink at a temperature T 2. The piston is moved
The cycle is carried out with the help of the Carnot engine slowly so that the gas is compressed until is pressure is P4
as detailed below : and volume is V4.
U3 = 0
P

V4
Pressure (P)

A(V1, P1) W2  RT2 l n

V3 = – Area CDLNC
B(V 2, P 2)
Q1 T1
D(V4, P4) V4
C(V 3, P 3) q 3  RT2 l n
T2
V3
Q2

O K L M N
X q3 = Heat absorbed in this process
Volume (V) w3 = Work done by Gas
 HEAT & THERMODYNAMICS

4. Adiabatic Compression : Q1 T1

The cylinder is again placed on the insulating pad, such Q 2 T2
that the process remains adiabatic. Here the gas is further
compressed to its initial P1 and V1. T2
 Carnot  1 
T1
R  T1  T2 
U 4  Division
r 1
• Carnot engine - depends only upon source temperature nd sink
R  T2  T1  temperature.
W4  = – area DAKLD
r 1 • Carnot engine =1 only when T 2 = 0 K or T 1 =  which is
impossible to attain.
q4 = 0
w4 = work done by the gas • If T2 = T1   =  Heat cannot be converted to mechanical
energy unless there is same difference between the
Analysis : temperature of source and sink.
Total work done by the engine per cycle.
2.12 Carnot Theorem
= W1 + W2 + W3 + W4
Statement :
= W1 + W3
(a) Working between two given temperatures, T 1 of hot
V2 V reservoir (the source) and T2 of cold reservoir (the sink, no
W = RT1l n  RT2 l n 4 engine can have efficiency more than that of the Carnot
V1 V3
engine.
Q1 = Total heat absorbed = q1 (b) The efficiency of the Carnot engine is independent of the
nature of the working substance.
V2
= RT1l n ...(19) Engine used for realising this ideal cycle is called as carnot
V1
heat engine.
Q2 = Total heat released = –q3 Proof :
[q3 = Heat absorbed & not heat released] Step - 1 : Imagine a reversible engine R and an irreversible
engine-I working between the same source (hot reservoir T1)
V3
= RT2 l n ...(20) and sink (cold reservoir T2).
V4
Step - 2 : Couple two engines such that I acts like heat
We can see that for heat engine engine and R acts like refrigerator.
W = Q 1 – Q2 Step - 3 : Let engine I absorb Q1 heat from the source deliver
1 1
= Area under ABCDA work W and release the balance Q1 – W to the sink in one
cycle.
Efficiency of Carnot Engine
W1
W Q
  1 2
Q1 Q1 Q1 Q1–W1
1
Now steps 2 is adiabatic 2 step 4 is also adiabatic T1
Q1 Q 1–W
T2
R
 T1 V2r 1  T2 V3r 1

and T1 V1r 1  T2 V4r 1 Step - 4 : Arrange R, such that it returns same heat Q, to
the source, taking Q 2 from the sink and requiring work
V2 V3 W = Q1 – Q2 to be done on it.
  ...(21)
V1 V4 Step - 5 : Supppose R < I (i.e.) If R were to act as an
engine it would give less work output than that of I (i.e.)
From equation 19, 20 and 21 we get 1
W < W for a given Q1 and Q1 – W > Q1 – W
1
 HEAT & THERMODYNAMICS

Step - 6 : In totality, the I-R system extracts heat (r1 – W) – • There is no force of attraction or repulsion amongst the
1 1
(Q1 – W ) = W – W & delivers same amount of work in one molecules of an ideal gas.
cycle, without any change in source or anywhere else. This
3.2.2 Real Gas
is against second Law of Thermodynamics. (Kelvin - Planck
statement of second law of thermodynamics) All gases are referred to as real Gases.

Hence the assertion q1 > qR is wrong. All real gas near the ideal gas behaviour at low pressures
and temperatures high enough, where they cannot be
• Similar argument can be put up for the second statement of
liquified.
carnot theorem, (ie) Carnot efficiency is independent of
working substance. 3.2.3 Ideal Gas Laws
 We use ideal gas to else are calculating but the relation. Avogadro Hypothesis : Equal volumes of all gas under
identical conditions of pressure and temperature would
Q1 T1 contain equal number of molecule.

Q 2 T2 will always hold true for any working substance
Perfect Gas Equation :
used in a carnot engine. PV = nRT

3. KINETIC THEORY OF GASES SRT

and P
M
In this topic, we discuss the behaviour of gases and how
are the various state variable like P, V, T, moles, U are inter- where n = Number of moles.
related with each other r = Universal Gas constant = NxkB
where ND = Avagadro No.
3.1 Molecular Nature of Matter
kB = Boltzman constant
Same as Atomic Theory given by Delton. According to
R = 8031 J/mol K.
him, atoms are the smallest constituents of elements. All
atoms of one element are identical, but atoms of different R = 1.98 Cal/mol K.
element are different. Boyle’s Law : When temperature of a given mass of gas is
In solids : Atoms tightly packed, interatomic spacing about kept constant, its pressure varies inversely as the volume
of gas.
Å . Interatomic force of attraction are strong.
(i.e.) PV = constant
In liquids : Atoms are not as rigidly fixed as in solids.
Interatomic spacing is about the same 2Å. Interatomic for a Charles Law : When pressure of a given mass of kept
attraction are relative weaker. constant, volume of the gas varies directly as the
temperature of the gas.
In Gases : Atoms very free. Inter atomic spacing is about
tens of Angstroms. Interatomic forces are much weaker in (i.e.) V T
gases than both in solids and liquids. Dalton’s Law of Partial Pressures : The total pressure of a
mixture of ideal gases is the sum of partial pressures exerted
In this chapter, we mainly focus on gases.
by the individual gases in the mixture.
3.2 Molecular Nature of Matter P–V = (n1 + n2 + n3 + ...)RT

3.2.1 Ideal Gas RT

 P = (n1 + n2 + n3 + ...)
V
That gas which strictly obeys the gas laws, (such as Boyle’s
Law, Charles, Gay Lussac’s Law etc.) P = P1 + P2 + ......
Characteristics
n1 RT
• The size of the molecule of an ideal gas is zero. where P1 = Pressure of gas
V
 HEAT & THERMODYNAMICS

Neviation of Real Gas from Ideal Gas : volume occupied by the molecules is negligible in
comparison to the volume of the gas.
Ideal Gas 4. The molecules do not exert any fore of attraction or
1
repulsion on each other, except during collision.
T1
5. The collisions of the molecules with themselves and with
T2 T1 > T2 > T3 > the walls of the vessel are perfectly elastic. As such, that
momentum and the kinetic energy of the molecules are
T3 conserved during collisions, though their individual
velocities change.
0 200 400 600 800 6. There is not concentration of the molecules at any point
P (atm)
inside the container i.e. molecular density is uniform
throughout the gas.
1.6
7. A molecule moves along a straight line between two
1.4
successive collisions and the average straight distance
P 1.2
covered between two successive collisions is called the
1.0 T1 mean free path of the molecules.
T1 > T2 > T3
0.8 8. The collisions are almost instantaneous, i.e., the time of
T1 collision of two molecules is negligible as compared to time
0.6
interval between two successive collisions.
0.4 T2 T2
T3
3.4 Pressure of an Ideal Gas and its Expression
0.2
T3 Pressure exerted by the gas is due to continuous
0
20 60 100 140 160 220 bombardment of gas molecules against the walls of the
V container.
Expression :
1.2 Consider a gas enclosed in a cube of side 1. Take the axes
P1 > P2 > P3
1.0 to be parallel to the sides of the cube, as shown in figure. A
T 0.8
molecule with velocity (x, y, z) hits the planar wall parallel
P1 2
to yz-plane of area A (= l ). Since the collision is elastic, the
0.6 molecule rebounds with the same velocity; its y and z
P2 components of velocity do not change in the collision but
0.4
P3 the x-component reverses sig. That is, the velocity after
0.2 collision is (–x,vz, vy). The change in momentum of the
0 molecule is : –mx – (mx) – 2mx. By the principle of
0 100 200 300 400 500 conservation of momentum, the momentum imparted to the
V
wall in the collision = 2mx.

3.3 Kinetic Theory Postulates
1. A gas consists of a very large number of molecules (of the
23
other of Avogadro’s number. 10 ), which are perfect elastic
spheres. For a given gas they are identical in all respects,
but for different gases, they are different.
2. The molecules of a gas are in a state of incessant random
motion. They move in all directions with different speeds.,
( of the order of 500 m/s) and obey Newton’s laws of motion.
3. The size of the gas molecules is very small as compred to
the distance between them. If typical size of molecule is 2
Å, average distance between the molecules is  20 Å. Hence
To calculate the force (and pressure) on the wall, we need
to calculate momentum imparted to the wall per unit time, if
it is within the distance x t from the wall. that is, all
molecules within the volume, Ax t only can hit the wall in
time T is 1/2A x t n where n is the number of molecules
per unit volume. The total momentum transferred to the
wall by these molecules in time t is :
Q = (2mx) (1/2 n Avxt)
The force on the wall is the rate of momentum transfer Q/t
and pressure is force per unit area :
2
P = Q/(A t) = nm x
HEAT & THERMODYNAMICS

Actually, all molecules in a gas do not have the same 1

velocity; there is a distribution in velocities. The above  PV  M  2 ...(23)
3
equation therefore, stands for pressure due to the group of
with equation 23 and Ideal gas equation
molecules with speed x in the x-direction and n stands for
the number density of that group of molecules. The total 1
nRT  M  2
pressure is obtained by summing over the contribution due 3
to all groups:
1
 nRT  Nm  2
P  nm 2
x
3

where  2x is the average of  2x . Now the gas is isotropic, n 3RT 1

  m 2
N 2 2
i.e. there is no preferred direction of velocity of the molecules
in the vessel. Therefore by symmetry, Also N = nNA

3 R 1
 2x   2y   z2   m 2
2 NA 2

1 1 3
    2x   2y   2z      2 Average KE of translation per molecule of the gas k BT
3
     3 2

where  is the speed and  2 denotes the mean of the squared 3.5 Kinetic Interpretation of Temperature

speed. Thus From above equations, we can easily see that KE of one
molecule is only dependent upon its Temperature.
1  KE of molecule will cease if, the temperature of the gas
P    nm 2
3 molecules become absolute zero.
 Absolute zero of a temperature may be defined as that
1 2 1M 1 2
P mn    S ...(22) temperature at which the root mean square velocity of the
2 2V 2
gas molecule reduces to zero.
M = Total mass of gas moleculus All the ideal gas laws can be derived from Kinetic Theory
V = Total volume fo gas molecules of gases.

3.4.1 Relation between Pressure and KE of Gas Molecules 3.6 Derivation of Gas Laws from Kinetic Theory

From equation 22 3.6.1 Boyle’s Law

1 2
P  S 2 We know that PV  NK
3 3

2 where K is the average kinetic energy of translation per

 P E
3 gas molecule. At constant temperature. K is constant and
 Pressure exerted by an ideal gas is numerically equal to two for a given mass of the gas. N is constant.
third of mean kinetic Thus, PV = constant for given mass of gas at constant
temperature, which is the Boyle’s Law.
3.4.2 Average KE per molecule of the Gas
3.6.2 Charle’s Law
From equation 22
We know 2
We know that PV  NK
3
1M 2
P 
3  For a given mass of gas, N is constant.
 HEAT & THERMODYNAMICS

3 r rms
Since K  k B T, K  T and as such PV  T.
2
3P 3P 1
If P is constant, V  T, which is the Charles’ Law. But as  rms  ,r or r 
  
3.6.3 Constant Volume Law
Therefore, if r1 and r2 are the rates of diffusion of two gases
2 of densities 1 and 2 respectively,
We know that PV  NK
3
r1 2
For a given mass of gas, N is constant. Since 
r2 1
3
K k B T, K  T The rates of diffusion of two gases are thus inversely
2
proprotional to the square roots of their densities which is
Thus, PV  T Graham’s Law of diffusion.
If V is constant, P  T, which the constant volume law.
3.6.7 Dalton’s Law of Partial Pressures
3.6.4 Ideal Gas Equation
The kinetic theory of gases attributes the gas pressure to
2 3 the bombardment of the walls of the containing vessel by
As PV  NK and K  k B T
3 2 molecules. In a mixture of ideal gases, we might therefore
expect the total pressure (P) to be the sum of the partial
2 3 
PV  N  k B T  or PV = Nk T pressures (p1, p2, ...) due to each gas, i.e.,
3 2  B

which is the ideal gas equation. 2 N1 2 N2

P  p1  p 2  ...  K1  K 2  ...
3 V1 3 V2
3.6.5 Avogadro’s Law

Consider two gases 1 and 2. We can write 2  N1 N 

or P  K1  2 K 2  ... 
3  V1 V2 
2 2
P1 V1  N1 K1 , P2 V2  N 2 K 2
3 3 In equilibrium, the average kinetic energy of the molecules
If their pressures, volumes and temperatures are the same, of different gases will be equal, i.e.,
then
3
K1  K 2  ...K  k BT
P1 = P2, V1 = V2, K1  K 2 . 2
Clearly, N1 = N2 Thus : Thus,
Equal volumes of all ideal gases existing under the same
2 3
conditions of temperature and pressure contain equal P  n1  n 2  ...  k B T    n1  n 2  ... k B T ...(24)
3 2 
number of molecules which is Avogadro’s Law or
hypothesis.
N1 N2
This law is named after the Italian physicist and chemist, where n1  V , n 2  V ...
1 2
Amedeo Avogadro (1776–1856).
Equation (24) represents Dalton’s Law of partial pressures
PV
Alliter : As PV  Nk B T, N  which states that :
k BT
The resultant pressure exerted by a mixture of gases or
If P, V and T are constants, N is also constant. vapours which do not interact in any way is equal to the
3.6.6 Graham’s Law of Diffusion sum of their individual (i.e., partial) pressures.
Figures shows a model explaning kinetic theory of gases. It
The rate (r) of diffusion of a gas through a porous pot or
has been constructed in accordance with theory on one
into another gas is determined by the rms speed of its
molecules, i.e., hand and real experimental observations on the other hand.
 HEAT & THERMODYNAMICS

N = Number of degrees of freedom of the system

1
mv2  K N = 3A– R
I PV = nRT 2 III
3
 kBT 3.8.1 Monoatomic Gases
2
Based on Based on combining The molecules of a monoatomic gas (like neon, argon,
experimental two mathematical
observations Based on models of a gas in helium etc) consists only of one atom.
of gases Newtonian boxes I and II
1  Nm  2  A=1
II P  v mechanocal
3 V  treatment of
R=0
gas as
collection of
particles  N=3
Here 3 degrees of freedom are for translational motion
2
PV  NK 3.8.2 Diatomic Gases
3
= NkBT A=2
Based on substituting Assuming the distance between the two molecules is fixed
and rearranging the expression
for K back into equation in box II then R = 1

The above piece of logic is tempting but false. This is due  N=3×2–1=5
to the reason that though the equation in box IV is useful, Here 5 degrees of freedom implies combination of 3
it does not tell us anything new, since it results from translational energies and 2 rotational energies.
combining equations in boxes II and III.
3.7 Internal Energy
As studied in thermodynamics, Internal Energy of any
substance is the combination of Potential Energies &
Kinetic Energies of all molecules inside a given gas.
• In real gas
Internal Energy = P.E of molecules + K.E of Molecules
Y Y
• In real gas
Internal Energy = K.E of Molecules A1
X X A1 A2
Here PE of molecules is zero as assumed in Kinetic theory A2
postulates; There is no interaction between the molecules
Z Z (i) (ii)
hence its interactional energy is zero.
(a) (b)
Y
3.8 Degree of Freedom
A1
The number of degrees of freedom of a dynamical system is
defined as the total number of coo-ordinates or independent A2 A3
X
quantities required to describe completely the position &
configuration of the system. Z
(c)
Example : If vibrational motion is also considered then [only at very
• A particle moving in straight line, say along X-axis need high temperatures
only x coordinate to define itself. It has only degree of N=7
freedom.
where 3 for translational
• A particle in a plane, needs 2 co-ordinates, hence has 2
degree of freedom. 2 for rotational

In general if 2 for vibrational

A = number of particles in the system 3.8.3 Triatomic Gas

R = number of independent relations among the particles
 HEAT & THERMODYNAMICS

Linear
dy
A=3 where  vibrational velocity
dt
R=2
 N=3×3–2=7 ky 2
and = Energy due to configuration
2
Non-Linear
According to Law of Equipartition

1
Energy per degree of freedom  k BT
2

1 1
  k B T  K B T  K B T is energy for
2 2

A=3 complete one vibrational mode.

R=2 3.10 Specific Heat Capacity

 N=3×3–3=6 With the knowledge of law of equipartition, we can predict
• Here again vibrational energy is ignored. the heat capacity of various gases.

3.8.4 Polyatomic Gas 3.10.1 Monoatomic Gas

A polyatomic gas has 3 translational, 3 rotational degrees Degree of freedom = 3.

of freedom. Apart from them if there v vibrational modes  Average Energy of a molecule at temperature T
then there will be additional 2v vibrational degrees of
freedom. 1 
 E  3  k BT 
 Total degree of freedom 2 
n = 3 + 3 + 2V = 6 + 2V Energy for one mole  E × NA
3.9 Law of Equipartition of Energy 3
 U  k B NA  T
Statement : According to this law, for any dynamical system 2
in thrmal equilibrium, the total energy is distributed equally
amongst all the degrees of freedom, and the energy 3
 U RT
associated with each molecule per degree of freedom is 2

1 In thermodynamics, we studied
k B T , where kB is Boltzman constant and T is temperature
2
Q  U
of the system. CV    [ W = O for constant v]
T  V T
k BT
Application : U  f where = Total degree of freedom. 3R
2  CV 
This law is very helpful in determining the total internal 2
energy of any system be it monoatomic, diatomic or any
5R CP 5
polyatomic. Once the internal energy is know we can very  CP  & r 
easy predict Cv & CP for such systems. 2 CV 3 .

Remark : In case vibrational motion is also there in any 3.10.2 Diatomic Gases
system, say for diatomic molcule, then there should be When no vibration
energy due to vibrational as well given by
Degree of freedom = 5
2
1  dy  1 2
EV  m    ky 5
2  dt  2 Average energy for one mole = RT
2
 HEAT & THERMODYNAMICS

U 5 Therefore the atoms do not possess any translational or

 CV   R rotational degree of freedom.
T 2
On the other hand, the molecules do possess vibrational
7R
CP  motion along 3 mutually perpendicular directions.
2
Hence for 1 mole of a solid, threre are NA number of atoms.
C 7
r P  The energy associated with every molecule
CV 5
 1 
When vibration is present.  3  2  k B T   3K B T
 2 
There is only one mode of vibration between 2 molecules.
 U = 3 Rt for one mole
 Degree of freedom = 7
Q U
7  C   3R
 U  RT T T
2
• The above equation is called as Dulong & Petit’s Law.
7 • At low temperatures the vibrational made may not be that
 CV  R
2 active hence, heat capacity is low at low temperatures for
9 solids.
and CP  R
2 C
3R
9
and r
7
3.10.3 Polyatomic Gases
T
Degree of freedom 300 K
= 3 for translational 3.10.5 Specific heat capacity of Water
+ 3 for rotational
Water is treated like solid.
+ 2v for vibrational
Water has three atoms, 2 of hydrogen and one of oxygen
= 6 + 2v
 Total degree of freedom for every atom
if v = Number of vibrational modes
=3×2=6
RT  Total degree of freedom for every molecule of water
 U   6  2v  K
2 = 3 × 2 = 18
 CV = (3 + V)R
 1 
18  RT 
CP = (4 + V) R
 Q U  2 
C  
T T T
4V
and r
3 V C = 9R

3.10.4 Specific heat capacity of solids 3.11 Maxwell Law of Distribution of Molecular
• In solids, there is very less difference between heat capacity Assumptions of Maxwell Distribution
at constant pressure or at constant volume. Therefore we
• Molecules of all velocities between 0 to  are present.
do not differentiate between CP & CV for solids.
• Velocity of one molecule, continuously changes, though
Q U fraction of molecules in one range of velocities is constant.
 C 
T T Result
{As solids hardly expand or expansion is negligible} 3/ 2 mv 2
 M  
Now in solid the atoms are arranged in an array structure N V  4N   V2e 2k BT

and they are not free to move independently like in gases.  2k B T 
 HEAT & THERMODYNAMICS

Expression :
dN V
Where NV  Mean Free Path
dV

Where d N

V
= Total number of molecules
with speeds between V & V + dV
V  t

N = Total number of molecules.

NV
d

V
Vmp Vav Vrms

Based on this we define three types of speed f molecules of

gas Suppose the molecules of a gas are spheres of diameter d.
Focus on a single molecule with the average speed <v>. It
1/ 2

  1  will suffer collision with any molecule that comes within a

1/ 2
Vrms  V 2    V 2 dN  V  
N  distance d between the centres. In time t, it sweeps a
volume d2 <v> t wherein any other molecule will collide
3RT with it (as shown in figure). If n is the number of molecules
Vrms 
M per unit volume, the molecule suffers nd2 <v> t collisions
in time t. thus the rate of collisions is nd2 <v> or the time
Where M = Molecular Mass of Gas
between two successive collisions is on the average.
1  = 1/(n <v> d2)
N
Similarly Vav  V  VdN V
The average distance between two successive collisions,
called the mean free path 1, is :
8RT
 l = <v> = 1/(nd2)
M
In this derivation, we imagined the other molecules to be at
dN V rest. But actually all molecules are moving and the collision
But VMP is velocity at which 0 rate is determined by the average relative velocity of the
dv
molecules. Thus we need to replace <v> by <vr> in equation.
A more exact treatment.
3RT
 VMP 
M 1
l=
Physically VMP is velocity possessed by Maximum number  2nd 2 
of molecules. Result
Remarks : 1
l=
Vrms > Vav > VMP >  2nd 2 
3.12 Mean Free Path Remark : Mean free path depends inversely on the number
density and size of the molecule.
The path tranversed by a molecule between two successive
collisions with other molecule is called the free path 3.13 Brownian Motion

The irregular movement of suspended particles like tiny

Total distance travelled by a molecule
l dust particles or pollen grains in a liquid is called Brownian
No. of collisions it makes with other molecules.
Motion.
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