Heat and Thermodynamics 91

Heat and Thermodynamics

10.1 Heat.
The energy associated with configuration and random motion of the atoms and molecules
with in a body is called internal energy. Heat is energy in transit which is transferred from one
body to the other due to temperature difference between them.
(1) As Heat is energy it is a scalar quantity. Dimension = [ML2 T2]; Unit = Joule [SI] while
practical unit is calorie; 1 calorie = 4.186 Joule ~ 4.2 Joule.
(2) Calorie is defined as amount of heat required to raise the temperature of 1 gm of water
through 1C (more specifically from 14.5 to 15.5C)
(3) When mechanical energy (work) is converted into heat, the ratio of work done (W) to
W
heat produced (Q) always remains the same and constant i.e. constant J or W JQ . This
Q
constant J is called mechanical equivalent of heat and has value 4.2 J/cal. J is not a physical
quantity but a conversion factor.
10.2 Temperature.
Temperature is defined as degree of hotness or coldness of a body and its measurement is
called thermometry.
(1) Temperature is one of seven fundamental quantities with dimension [ ]. It is a scalar
physical quantity with S.I. unit kelvin (K).
(2) Temperature determines the direction of flow of heat.
(3) Two bodies are said to be in thermal equilibrium if and only if they are at same
temperature. In this situation heat in the two bodies may or may not be equal.
(4) Scales of temperature
(i) Celsius scale (ii) Fahrenheit scale (iii) Reaumer scale (iv) Kelvin scale.
TC T 32 TR TK 273
F
100 180 80 100
(5) Difference in temperature on Celsius scale or Kelvin scale are same i.e. ToC = T K
10.3 Specific Heat.
92 Heat and Thermodynamics
When heat is given to a body and its temperature increases, the heat required to raise the
temperature of unit mass of a body through 1C (or K) is called specific heat of the material of
the body.
Q
Q = m C T C = m T ; where Q = heat required, m = mass of body, T = Rise in
temperature, C = specific heat
(i) Dimension = [L2T21];
Joule calories
(ii) Units = [in SI]; (Practical Unit)
kg- Kelvin gm C

(iii) Specific heat is found to be maximum for hydrogen 3.5 cal. / gm C then for water
1 cal. / gm C 4200J / kg K . for all other substances specific heat is lesser than
1 cal. / gm C and is minimum for radon and actinium (~ 0.022 cal/ gm C).

(iv) Specific heat of a substance depends also on the state of substance i.e. solid, liquid or
gas.
SP. heat of ice 0.5 cal gm1C1, water 1 cal gm1C1, steam 0.47 cal gm1C1
Q
(v) As T = , greater the specific heat of substance lesser will be the change in
mC
temperature. Now as specific heat is very large (1 cal/gm C), by absorbing or releasing large
amount of heat its temperature changes by small amount. This is why it is used in hot water
bottles or as coolant in radiators. This is also how the sea moderates the climate of nearby costal
land.
(vi) Molar specific heat or molar heat capacity : Molar specific heat of a substance is defined
as the amount of heat required to raise the temperature of one gram mole of the substance
Cal 1 1
through a unit degree. It is represented by (capital) C. Unit = or J mole k ;
mole- o C
Dimension = [L2T21]
(vii) Dulong and Petit law : Average molar specific heat of all metals at room temperature is
constant, being equal to 3R = 6 cal-mol 1k1 = 25 J mole1 k1. Where R is a gas constant for one
mole of the gas.
(viii) Variation of specific heat of a solid with temperature : At T = 0K, Cv tends to zero. with
rise in temperature Cv increases and becomes constant = 3R only at some particular
temperature.
10.4 Heat Capacity or Thermal Capacity.
It is defined as the amount of heat required to raise the temperature of the (whole) body
through 1C or 1K.
We know that amount of heat energy required (Q) to raise the temperature of mass (m) of a
body through temperature range ( T) is Q = m C T. If T = 1, then Q = mC.
Unit = Joule/ Kelvin or calorie/centigrade;
Dimension : [ML2 T21]
 Heat and Thermodynamics 93

10.5 Water Equivalent.

Water equivalent of a body is defined as the mass of water which would absorb or evolve the
same amount of heat as is done by the body in rising or falling through the same range of
temperature.
We know Q = m C T (i)
If same amount of heat is required to raise the temperature of w gram of water through the
same range.
Q = W 1 T (ii)
From equation (i) and (ii) W = mC

10.6 Latent Heat (L).

Latent heat of a substance is the amount of heat energy required to change the state of unit
mass of the substance from solid to liquid or from liquid to gas/ vapour without any change in
temperature.
Unit = Joule/Kg or cal/gm;
Dimension = [L2 T2]
Latent heat of fusion of ice = 80 cal/gm.
Latent heat of vaporisation of water = 540 cal/gm.
10.7 Specific Heat of a Gas.
We may define specific heat of a gas as the amount of heat energy required to raise the
temperature of one gram of a gas through a unit degree. But in gases amount of heat spent in
their expansion also, apart from raising the temperature. Hence specific heat of gas shall not
have a single value. Its value depends upon the condition under which the gas is heated.
(1) Limits of specific heat of a gas : If the gas is enclosed in a cylinder fitted with an air
Q
fight and friction less piston. It can be heated in different modes. We know that C =
mT
(i) Gas is compressed suddenly it means Q = 0, So C = 0
(ii) Gas is heated isothermaly and its expansion takes place it mean T = 0, So C =
(iii) Gas is heated and there will be some net rise in temperature it means T = Positive, So
C = +ve
(iv) Gas is heated and expanded in such away that there will be net fall in temperature it
means
T = Negative So C = ve
Hence we conclude that specific heat of a gas can have any positive value ranging from zero
to infinity further the specific heat of a gas can be negative. The exact value of specific heat of
gas shall depends upon the mode of heating of the gas.
(2) Two principal specific heats of a gas :
94 Heat and Thermodynamics
(i) Specific heat of a gas at constant volume (cv) : It is defined as amount of heat
energy required to raise the temperature of one gram of gas through 1C or 1K, when volume of
the gas is kept constant. Unit = cal gm1K1 or J gm1K1.
(ii) Specific heat of a gas at constant pressure (cp) : It is defined as amount of heat
energy required to raise the temperature of one gram of gas through 1C or 1K, when
pressure of gas is kept constant. Unit = cal gm 1K1 or J gm1K1.
Instead of considering one gram of the gas, if we consider one gram mole of the gas, then
the specific heats are called molar specific heats of the gas.
Cp = molar specific heat of gas at constant pressure
Cv = molar specific heat of gas at constant volume.
Unit of Cp and Cv = cal / mol Kelvin.

Note : Ratio of two principle specific heat C p Cv , the value of depends upon an
atomicity of the gas.
In case of Cv, volume of the gas is kept constant and heat is required only for
raising the temperature of one gram mole of the gas through 1C or 1K. No heat,
what so ever, is spent in expansion of the gas.
In case of Cp, as pressure of the gas is kept constant, the gas would expand on
heating. Therefore some heat is spent in expansion of the gas against external
pressure. This is in addition to the amount of heat energy required for raising the
temperature of one gram mole of the gas through 1C or 1K.
Hence more heat energy is required to raise the temp. of one gram male of the
gas through 1C or 1K, when heated at constant pressure. Hence Cp > Cv and Cp
Cv = R.
10.8 Degrees of Freedom.
The total number of co-ordinates or independent quantities required to completely specify
the position and configuration of a dynamical system is called the degrees of freedom of that
system.
Or the total number of possible independent ways in which the position and configuration of
a mechanical system may change is called the degree of freedom of that system.
Or the total number of independent ways in which the particles of a system can take up
energy is called the degree of freedom of that system.
If A is the number of particles in a system and R is the number of independent relations
between them, then the number f of degrees of freedom is given by f = 3 A R
10.9 Various Laws for Gases.
(1) Boyle's law : At a constant temperature, the volume of the given mass of gas is
inversely proportional to its pressure.
1
P or PV = constant or P1V1 = P2 V2. This law is perfectly obeyed V
V
at high temperature and low pressure of a gas.
(2) Charle's law : At constant pressure the volume of a given mass of
gas is directly proportional to its absolute temperature.
P
 Heat and Thermodynamics 95

V V V
V T 1 2 V1T2 V2T1
constant V
T T1 T2
T1 1 = T2 2
At constant pressure the volume of a given man of gas increases by
1/273 of its volume of 0C for 1C rise in its temperature.
1 T
Vt V0 1 t
273
(3) Gay Lussac's law : Gay Lussac's law on kelvin scale states that
volume remaining constant, the pressure of the given mass of a gas is T
P1 P2
directly Proportional to its kelvin temperature. P T .
T1 T2
It states that the volume remaining constant, the pressure of a given
man of a gas increases or decrease by 1/273.15 of its pressure at 0C
1 t P
for each 1C rise or fall in temperature Pt P0 1
273.15
(4) Dalton's law of partial pressure : The total pressure exerted by the mixture of in
active gases in a vessel is equal to the sum of partial pressure due to individual gases P = P1 + P2
+P3 .
(5) Avogadro's law : It states that equal volumes of all gases under identical conditions of
temperature and pressure, contain the same number of molecules. If
P1 P2 , V1 V2 andT1 T2 then n1 = n2

(6) Graham's law of diffusion : It states that the rates of diffusion of two gases are
1
inversely proportional to the square roots of their densities r
; Where r = Rate of diffusion,

= density of gas.
(7) Ideal gas equation : It is an equation which relates to the pressure, volume and
temperature of the given state of an ideal gas.
PV = RT for 1 mole of gas PV = nRT for n mole of gas
PV = rT for 1 gram of gas PV = nrT for n gram of gas
PV = KT for 1 molecule of gas PV = nKT for n molecule of gas
R = universal gas constant; r = specific gas constant; k = Boltzmann's constant ; P =
pressure
V = volume; T = temperature
10.10 Gas Constant.
(1) Universal gas constant
From equation PV = nRT
PV volume
Pressure workdone
R
nT No.ofmoles temperatur
e temperatur
No.ofmoles e

(i) Thus universal gas constant signifies the work done by (or on) a gas per mole per kelvin
(ii) Dimension : [ML2T21]
96 Heat and Thermodynamics
Joule calories 2 calories
(iii) Value : 8.31 = 1.98 = 0.8221
mole kelvin mole kelvin mole kelvin

litre atmosphere
mole kelvin

(2) Specific gas constant : When gas quantity is 1 gm, then gas constant used is called
R
specific gas constant. If M is the molecular weight and R is universal gas constant, then r
M
Since the value of M is different for different gases. Hence the value of gas constant for 1
gram of a gas is different for different gases.
(3) Boltzmann's constant: When 1 atom of gas is taken account then the constant is
called Boltzmans constant.
For N atoms (6.023 1023) gas constant = R
R 8.31Joulemole1k 1 Joule
For 1 atom gas constant = k 23
= 1.38 10 23 ; Dimension :
N 6.023 10 kelvin
[ML2T21]
10.11 Characteristics of Ideal Gas or Perfect Gas.
It is that gas which strictly obeys the gas laws
(1) The size of the molecule of a gas is zero i.e. each molecule of a gas is a point mass with
no dimensions.
(2) There is no force of attraction or repulsion amongst the molecules of the gas.
All real gases are not perfect gases as they do not obey gas law perfectly. However at
extremely low pressure and high temperature some real gases like hydrogen, oxygen, nitrogen,
helium etc. obey the gas laws a fair degree of accuracy and hence behave as nearly perfect
gases.
10.12 Assumptions of Kinetic Theory of Gases.
(1) A gas consists of a very large number of molecule which are the perfect elastic spheres
and are identical in all respects for a given gas and are different for different gases.
(2) The molecules of a gas are in a state of continuous, rapid and random motion. They
move in all directions with different speeds, ranging from zero to infinity and obey Newton's laws
of motion.
(3) The size of gas molecule is very small as compared to the distance between them. Hence
volume occupied by the molecule is negligible in comparison to the volume of the gas
(4) The molecule do not exert any force of attraction or repulsion on each other, except
during collision.
(5) The collisions of the molecular with them selves and with the walls of the vessel are
perfectly elastic. As such the momentum and kinetic energy of the molecules are conserved
during collisions.
 Heat and Thermodynamics 97
(6) There is no concentration of the molecules at any point inside the container i.e molecular
density is uniform through out the gas.
(7) A molecule moves along a straight line between two successive collisions and the
average straight distance covered between two successive collisions is called the mean free path
of the molecules.
(8) The collisions are almost instantaneous i.e the time of collision of two molecule is
negligible as compared to time interval between two successive collision.
10.13 Pressure Due to an Ideal Gas.
1 mn 2
P v rms [P = pressure, V = volume, m = mass of each molecule, n = no. of molecules
3 V
in gas]
1M 2
P v rms [ vrms= Root mean square velocity, M = Total mass of the gas, M = m n]
3V
1 M
P v2rms [ density of the gas]
3 V
Relation between pressure and kinetic energy : Mean Kinetic energy of unit volume of
1 1 2
gas E v2rms and P v2vrms. From above two equations P E
2 3 3
That means the pressure exerted by an ideal gas is numerically equal to two third of the
mean kinetic energy of translation per unit volume of the gas.
10.14 Root Mean Square Velocity.

v12 v22 v3 2 ................ 3P

3RT 3
.vsound
vrms M
n
From the Above formulae it is clear that
(1) vrms depends only on the temperature
P RT
(2) At constant temperature constant. Therefore vrms does not depends on
M
pressure as well as volume.
10.15 Kinetic Energy of Ideal (Mono Atomic) Gas.
3
(1) Mean kinetic energy of 1 mole of gas E RT .
2
3
(2) Mean kinetic energy of 1 molecule of gas E KT .
2
3
(3) Mean kinetic energy of 1 gram of gas E rT
2
These expressions are valid only for monoatomic gases. Which have 3 degree of freedom.
General expression (if gas posses f degree of freedom)
98 Heat and Thermodynamics
f f f
E RT [for 1 mole of gas], E kT [for 1 molecule of gas], E rT [for 1 gm. of gas]
2 2 2
10.16 Real Gases.
The Real gases are those which does not obeys the Boyle's Charle's and gas law. To explain
the behaviour of real gases following two corrections are applied in the gas equation PV = RT
(1) Volume correction : According to kinetic theory of ideal gases the volumes of molecule
is presumed to be negligible where as the molecule occupy some volume due to their finite size
(1010m) consequently the whole volume of the container is not available for free kinetic motion
of gas molecule as some fraction of it is occupied by the molecules themselves. Hence the
effective volume of gas is = (V b)
(2) Pressure correction : According to ideal gas theory, the inter molecular forces among
the molecules are zero, But at high pressure and low temperature the inter molecular distances
decreases and consequently the intermolecular attractive forces becomes effective. As a result
of this the molecule do not exert as much force as they could exert in the absence of attractive
force. Hence the effective pressure would be greater than the observed pressure (P).

a
Hence the effective pressure of gas is = P 2
V
Equation for real gas : (Vander waal's equation)

a an 2
P 2
V b RT for 1 mol. of Gas; P 2 V nb nRT for n mol. of Gas
v V

Here 'a' and 'b' are constants called Vander waal's constant.
Unit : a Newton m4 ; b m3; Dimension : [a] = [ML5T2] ; [b] = [L3]
The value of constants 'a' and 'b' depends upon the nature of gas

8a 27R 2Tc 2 R T
Vc 3b, Tc , Pc , b c
2TRb 64Pc 8 Pc
Pc Vc 3
or R, Here Pc = critical pressure, Tc = critical temperature, Vc critical
Tc 8
volume.
10.17 Various Information in Tabular Form.

f f
cv R c p 1 R
2 2 2 f f f
Gas A f = 3A- cp / cv 1 E RT E KT E rT
R f 2 2 2
Rest. R
1 1
monoato
mic He, 3 5 5 3 3 3
1 3 R R (1.66) RT KT rT
Ne, Ar, Kr, 2 2 3 2 2 2
Xe and Rn
 Heat and Thermodynamics 99

Diatomic
5 7 7 5 5 5
O2, H2, 2 5 R R (1.4) RT KT rT
HCl. 2 2 5 2 2 2
Triatomic
(Non- 4
3 6 3R 4R (1.33) 3RT 3KT 3rT
linear) 3
H 2O
Triatomic
7 9 9 7 7 7
(linear) 3 7 R R (1.28) RT KT rT
CO2, BeCl2 2 2 7 2 2 2

10.18 Maxwell's Law of Equi-Partition of Energy.

According to this law, for any dynamical system in thermal equilibrium, the total energy is
distributed equally amongst all the degrees of freedom, and the energy associated with each
1
molecule per degree of freedom is KT , and hence a constant.
2
f KT
f
Total energy in f degree of freedom = KT ; Energy per degree of freedom = 2 =
2 f
1
KT .
2
10.19 Some Important Definition of Thermodynamics.
(1) Thermodynamics : Thermodynamics is a branch of science, which deals with the study
of transformation of heat energy into other forms of energy and viceversa.
(2) Thermodynamical system : It is the name given to an assembly of an extremely large
number of particles (Atoms or Molecules). It may exist in the form of a solid, a liquid or a gas or a
combination of two or more states.
(3) Surrounding : Any thing outside the thermodynamical system, which has a direct effect
on the system is called surrounding of the system.
Example: Gas, enclosed in a cylinder fitted with a piston forms the thermodynamical system but
the atmospheric air around the cylinder, movable piston, burner etc. are all the surroundings.
(4) Thermodynamic state and thermodynamic variables : Thermodynamic variables
are the physical quantities like Pressure (P), Volume (V), and Temperature (T) etc. are used to
describe the thermodynamics state of the system.
(5) Equation of state : The mathematical relation between these parameters is called the
equation of state of thermodynamic system.
Example: For n moles of an ideal gas, the equation of state is PV nRT .
(6) Thermodynamic processes : A Thermodynamical process is said to take place when
some changes occur in the state of a thermodynamic system i.e., thermodynamic parameters of
system change with time. Some important thermodynamical processes are : Isothermal process,
Adiabatic process, Isobaric process, Isochoric or Isovolumic process, Cyclic or Noncyclic process
and Reversible or Nonreversible process.
100 Heat and Thermodynamics
(7) Indicator diagram or P-V diagram : Indicator diagram represents the variation of
volume V of a system with the pressure P of the system usually V is
Y
plotted along xaxis and P is along yaxis. A (V , P )
1 1
P
As shown in the fig. Point A (V1P1 ) represents initial state and point
B (V2P2) represent final state and the various points on the curve AB (V2, P2)
B
represent the intermediate states of the system in going from A to B
X
V
10.20 Zeroth Law.
According to this law ''If system A and B are each in thermal equilibrium with a third system
C then A and B are in thermal equilibrium with each other''. Zeroth law came to light much later
than first and second laws of thermodynamics. Because the concept of temperature is
fundamental to the both the laws of thermodynamics, the law that establishes temperature as a
valid concept should have place before I and II and hence it is called Zeroth law.
10.21 Joule's Law.
Whenever heat is converted into mechanical work or mechanical work is converted into
heat, then the ratio of work done to heat produced always remains constant.
W
W Q or J , This is Joule's law. Here J = Mechanical equivalent of heat.
Q
Example in which mechanical work is converted into heat
(1) When water in a stream falls from height h, then its potential energy is converted into
heat and temperature of water rises slightly.
W = JQ mgh = J ms t ; where m = mass of the water, s = specific heat of water, t = Rise
in temperature
o
t gh Js C

(2) The kinetic energy of a bullet fired from a gun gets converted into heat on striking the
target. By this heat the temperature of bullet increases by t.
1
W = JQ mv2 = J m s t; where m = mass of the bullet, v = velocity, t = Rise in temp, s
2
= Specific heat
2 o
t C
2Js
If temperature of bullet rises upto the melting point of the bullet and bullet melts then
v2 o
t L s C
2J

(3) If ice-block falls down through some height and melts partially then its potential energy
= J Heat required in melting
mgh
W = JQ mgh = J mL m = kg [where m = mass of ice block, m = mass
JL
which melts]
 Heat and Thermodynamics 101
JL
If iceblock completely melts down then mgh = J mL h meter
g
10.22 Internal Energy.
Internal energy (U) of a system is the energy possessed by the system due to molecular
motion and molecular configuration. The energy due to molecular motion is called internal kinetic
energy (UK) and due to molecular configuration is called internal potential energy (UP). Thus
U UK UP

(1) For case of ideal gas or perfect gas there is no intermolecular attraction between the
molecule so U P 0 . Hence ideal gas consists only internal kinetic energy U U K for ideal
3 3
gas and U K nRT with U K nR T
2 2
(2) Change in internal energy is a point function. It is not a path function and depends only
initial and final states of the system i.e., U U f U i
(3) In a cyclic process initial and final states are same so T 0 . Hence U 0 (Always)
R (P f Vf Pi Vi )
(4) In case of gases whatever be the process U n cv T = n T
1 1

10.23 Heat.
It is the energy that is transferred between a system and its environment because of
temperature difference between them.
(1) It's S.I unit is Joule and practical unit is calorie. 1 calorie = 4.2 Joule.
(2) It is a path function Example. Heat required to change the temperature of a given gas at
a constant pressure is different from that required to change the temperature of same gas
through same amount at constant volume.
(3) In case of solid and liquids Q mL for change in state Q mst for change in temp.
Q n cv T for constant volume and Q n c p T for constant pressure.

(4) In solids thermal energy is present in the form of vibrational energy of molecule.
(5) In liquids thermal energy is present in the form of translatory energy of molecules.
(6) In gases thermal energy is present in the form of kinetic energy due to random motion of
molecules.

10.24 Work.
Work can be defined as the energy that is transferred from one body to the other owing to a
force that acts between them. The amount of workdone by a system as it expands or contracts is
given by
Vf
W dW PdV
Vi

(1) Like heat it is a scalar physical quantity.

102 Heat and Thermodynamics
(2) In indicator diagram or PV diagram the area under PV curve represents workdone it is
positive if volume increases and negative if volume decreases.
(3) In a cyclic process work done is equal to area under the cycle and is positive if the cycle
is clockwise and negative if anticlockwise.
(4) Work done in different processes.
Constant
Process Workdone
Quantity
(i) Isochoric 0 as V 0 Volume
(ii) Isobaric P(Vf Vi ) or nR(T f Ti ) Pressure
Vf Pi
(iii) Isothermal nRT loge or nRT log e Temperature
Pf
Vi
n R (T f Ti )
(iv) Adiabatic Heat (Q)
(1 )

10.25 First Law of Thermodynamics.

It is a restatement of conservation of energy in thermodynamical process. According to this
Law Heat given to a system (Q) is equal to the sum of increase in its internal energy (U) and
the workdone (W) by the system against the surrounding Q U W .
It makes no distinction between work and heat as according to it the internal energy (and
hence temperature) of a system
(1) May be increased either by adding heat to it or doing work on it or both.
(2) This law which is basically the law of conservation of energy, applies to every process in
nature
(3) This law applies equally to all the three phases of matter.
(4) Sign convention :
(i) When heat is supplied to a system Q ()
(ii) When heat is drawn from the system Q ()
(iii) When gas expands work done by gas W ()
(iv) When gas compressed work done on the gas W ()
(v) When temperature increases, internal energy increases U ()
(vi) When temperature decreases, internal energy decreases U ()
(5) Q and W are the path function but U is the point function.
(6) In the above given equation all three quantities Q, U and W must be expressed either
in Joule or in calorie.
(7) Limitations:
(i) It does not indicate the direction in which the change can occur.
 Heat and Thermodynamics 103
Example: (a) When two bodies of different temperature are in contact, then heat always flows
from higher to lower temp. not in opposite direction although first law of thermodynamics is not
violated.
(b) On striking the target the kinetic energy of bullet converted into heat energy but heat
energy cannot be converted back into mechanical energy of the bullet enabling it to fly back.
(ii) It gives no idea about the extent of heat exchange but in practical experiences
mechanical work can easily converted into heat but there are severe restrictions in the reverse
process.
10.26 Isothermal Process.
A change in pressure and volume of a gas without any change in its temperature, is called
an isothermal change. In such a change there is a free exchange of heat between the gas and its
surroundings.
(1) Essential conditions for perfect isothermal change:
(i) The walls of the container must be perfectly conducting, to allow free exchange of heat
between the gas and its surroundings.
(ii) The process of compression or expansion should be so slow so as to provide time for the
exchange of heat.
(2) Example of isothermal process :
(i) Melting process is a isothermal because it takes place at constant temp ice melts at 0 oC.
(ii) Boiling process is also an isothermal process.
(3) In all isothermal processes Boyle's law is obeyed PV = constant. This is known as the
equation of an isothermal change.
(4) Indicator diagram : Obtained curves are called isothermal curve or isotherm . Slope of
dP P
isotherm .
dV V
(5) S .
(6) Q W . For ideal gas U T , so for constant temperature U 0 .
Vf Vf
nRT
(7) Workdone in isothermal process : W P dV V
dV
Vi Vi

Vf Vf pi
W n RT loge 2.303n RT log10 nRT loge 2.303n RT log10 pi
pf pf
Vi Vi
p
(8) Bulk modulus of elasticity p .
V / V
(9) Workdone in an isothermal process by indicator diagram can be calculated by the area
between the PV curve and volume axis.

10.27 Adiabatic Process.

104 Heat and Thermodynamics
A change in pressure and volume of a gas in which temperature also changes but no heat is
allowed to enter into or escape from the gas is called an adiabatic change.
(1) Two essential conditions :
(i) The walls of container must be perfectly non-conducting in order to prevent any
exchange of heat between the gas and its surrounding.
(ii) The process of compression or expansion should be sudden so that there is no
time for the exchange of heat. Both these conditions are difficult to be realised strictly in
practice. Therefore perfect adiabatic changes are practically impossible.
(2) Examples of nearly perfect adiabatic changes :
(i) Sudden compression or expansion of a gas in a container with perfectly nonconducting
walls.
(ii) Sudden bursting of the tube of a bicycle tyre.
(iii) Propagation of sound waves in air and other gases.
(iv) Expansion of steam in the cylinder of steam engine.
(3) Adiabatic law or Poissions law PV const.or TV -1 const.or P 1 T constant
.
(4) The curve drawn on indicator diagram is called an adiabatic curve. Slope of adiabatic
dP P
curve
dV V

Hence, Slope of adiabatic curve = slope of isothermal curve.

(5) Specific heat = 0
(6) U W
nR[T f Ti ] P f Vf Pi Vi
(7) Work done : W n C v (Ti T f ) .
(1 ) 1

(8) Bulk modulus of Elasticity = P

(9) By calculating the area between PV curve and volume axis we can calculate the work
done in adiabatic process.
10.28 Isobaric Process.
It occurs at constant pressure

(1) Here P = constant so W P V P[Vf Vi ] n R [T f Ti ] P

(2) From first law of thermodynamics Q U P V ; where

V Vf Vi

Here heat given to a system is used to increase internal energy and V

also in doing work against external surroundings.

(3) Q n C p T and U n Cv T .
(4) For state change Q mL .
 Heat and Thermodynamics 105

V1 V2
(5) In isobaric process Charle's law is followed V T
T1 T2
(6) Bulk modulus of elasticity = 0.
(7) Example : (i) Conversion of ice into water (Melting process)
(ii) Boiling process [It is isothermal and isobaric process]
10.29 Iso Choric Process.
It occurs at constant volume
(1) Since V 0 therefore W 0
(2) Q U [As W 0]

P1 P2
(3) Gay Lussac's law is obeyed in this process P T .
T1 T2

nR T P f Vf Pi Vi
(4) Q U nCv T i.e., heat supplied to the system is stored as its
1 1
internal energy and hence temperature of the system will change
(5) Bulk modulus of elasticity K
f
(6) Specific heat Cv R
2
10.30 Indicator Diagram for Comparison.

Expansion P
Compression
Isobaric Adiabatic

Isothermal
Isothermal
Isobari
c
Adiabatic

V V
O
10.31 Reversible and Irreversible Process. O

(1) Reversible process

For Expansion: It is a process which can Forbe Compression
made to proceed in two opposite
WIsobaricease,
directions with the same > WIsothermal W
> the system andAdiabatic
so that > WIsothermal >Wpass
the surrounding Isobaric through exactly the
same intermediate state asWin the
adiabatic
direct process.
Necessary conditions : (i) The process should proceed at an extremely slow rate so that
system remain in mechanical, thermal and chemical equilibrium.
(ii) The system should be free from dissipative forces like friction, inelasticity, viscosity,
electrical resistance etc. This is because energy spent against such forces cannot be recovered.
Reversibility is an idealized concept which can never be attained.
Some examples of approximately reversible process are:
(a) Electrolysis (Provided the resistance offered by electrolyte is zero).
(b) Slow compression and extension of spring.
106 Heat and Thermodynamics
(2) Irreversible process : It is a process which cannot be made to proceed in the reverse
direction with the same ease and the system does not pass through the same intermediate
states in the direct and reverse processes there always occurs some loss of energy because
energy spent in working against the dissipative forces is not recovered back.
Example: Every process in nature is irreversible process.
(i) Rusting of iron.
(ii) Mixing of two substances like water and alcohol.
(iii) Most of the chemical reactions are irreversible.
10.32 Cyclic and Non-Cyclic Processes.
A cyclic process consists of a series of changes which return the system back to its initial
state. In noncyclic process the series of changes involved do not return the system back to its
initial state.
(1) Work done in noncyclic process depends upon the path chosen or the series of changes
involved and can be calculated by the area covered between the curve and volume axis on PV
diagram.
(2) Work done in cyclic process is numerically equal to the area enclosed by the loop
representing the cycle.
(3) If the cyclic path traced in the clockwise direction the area comes out to be positive,
indicating that network is done by the system and vice-versa.
10.33 Second Law of Thermodynamics.
(1) Clausius statement : It is impossible for a self acting machine unaided by any external
agency, to transfer heat from colder reservoir to hot reservoir. In other words heat can not by
itself flow from a colder to a hotter body.
(2) Kelvin-Planck statement : It is impossible for an engine working during a cyclic
process to extract heat from a reservoir and convert completely into work. In other words, 100%
conversion of heat into work is impossible
Important points :
(i) Whole of heat can not be converted into work.
(ii) If work (mechanical energy) is to be obtained constantly from a machine then some
energy will have to be discharged to the sink also.
(iii) The efficiency of any engine can never be 100%.
10.34 Heat Engine.
(1) The device, used to convert heat energy into mechanical energy, is called a heat engine.
(2) For conversion of heat into work with the help of a heat engine, the following conditions
have to be met with :
(i) There should be a body at higher temperature T1 from which heat is extracted. It is
called the source.
(ii) Body of the engine containing working substance.
 Heat and Thermodynamics 107

(iii) There should be a body at lower temperature T2 to which heat can be rejected. This is
called the sink.
Working of heat engine :
Engine derives an amount Q1 of heat from the source.
A part of this heat is converted into work W Source Engine Sink

Remaining heat Q 2 is rejected to the sink. T E T

1 2
Q Q
Thus Q1 W Q2 1 2

or the work done by the engine is given by

WQ Q
W Q1 Q2 1 2

Efficiency of heat engine : Efficiency of heat engine () is defined as the fraction of total
heat, supplied to the engine which is converted into work.
W Q1 Q2 Q
or 1 2
Q1 Q1 Q1

10.35 Carnot Engine and Carnot Cycle.

(1) Carnot engine : Carnot engine is an ideal heat engine. It consists of the following parts.
(i) Source : It is a reservoir of heat energy with a
conducting top maintained at a constant temperature
T1K . Source is so big that extraction of any amount of
heat from it does not change its temperature.
(ii) Body of heat engine : It is a barrel having
perfectly insulating walls and conducting bottom. It is
fitted with an air tight piston capable of sliding within the
barrel without friction. The barrel contains some quantity
of an ideal gas.
(iii) Sink : It is a huge body at a lower temperature
T2 having a perfectly conducting top. The size of the sink is so large that any amount of heat
rejected to it does not increase its temperature.
(iv) Insulating stand : It is a stand made up of
perfectly insulating material such that the barrel when
placed over it becomes thoroughly insulated from the
surroundings.
(2) Carnot cycle : As the engine works, the
working substance of the engine undergoes a cycle
known as Carnot cycle. The Carnot cycle consists of the
following four strokes :
(i) First stroke (Isothermal expansion) : In this
stroke the barrel is placed over the source. The piston is
108 Heat and Thermodynamics
gradually pushed back as the gas expands. Fall of temperature, due to expansion, is
compensated by the supply of heat from the source and consequently temperature remains
constant. The conditions of the gas change from A(P1, V1 ) to B(P2 V2 ) . If W1 is the work done
during this process, then heat Q1 derived from the source is given by

V2
Q1 W1 Area ABGE RT loge
V1
(ii) Second stroke (Adiabatic expansion) : The barrel is removed from the source and is
placed over the insulating stand. The piston is pushed back so that the gas expands adiabatially
resulting in fall of temperature from T1 to T2 . The conditions of the gas change from B(P2 , V2 )
to C(P3 , V3 ) . If W2 is the work done in this case then
R
W2 Area BCHG (T1 T2 )
1
(iii) Third stroke (Isothermal compression) : The barrel is placed over the sink. Piston is
pushed down thereby compressing the gas. The heat generated due to compression flows to the
sink maintaining the temperature of the barrel constant. The state of the gas changes from
C(P3 , V3 ) to D(P4 , V4 ) . If W3 is the work done in this process and Q2 is the heat rejected to
the sink, then

V3
Q2 W3 Area CDFH RT2 loge
V4
(iv) Fourth stroke (Adiabatic compression) : The barrel is placed over the insulating
stand. The piston is moved down thereby compressing the gas adibatically till the temperature of
gas increases from T2 to T1 . The state of gas changes from D(P4 , V4 ) A(P1, V1) . If W4 is the
work done in this process, then
R
W4 Area ADFE (T1 T2 )
1

Heat converted into work in Carnot cycle : During the four strokes, W1 and W2 are the
work done by the gas and W3 and W4 are the work done on the gas. Therefore the net work
performed by the engine
W W1 W2 W3 W4 Area ABGE + Area BCHG Area CDFH Area ADFE = Area ABCD
Thus net work done by the engine during one cycle is equal to the area enclosed by the
indicator diagram of the cycle. Analytically
V2
W R(T1 T2 )loge
V1
Efficiency of Carnot engine : Efficiency () of an engine is defined as the ratio of useful
heat (heat converted into work) to the total heat supplied to the engine. Thus
 Heat and Thermodynamics 109

V2
R(T1 T2 ) loge
W Q1 Q2 V
1 T1 T2 Q2 T
or or 1 1 2
Q1 Q1 V2 T1 Q1 T1
RT1 loge
V1
Some important points regarding Carnot engine :
(i) Efficiency of an engine depends upon the temperatures between which it operates.
(ii) is independent of the nature of working substance.
(iii) is one only if T2 0 . Since absolute zero is not attainable, hence even an ideal engine
cannot be 100% efficient.
(iv) is one only if Q2 0 . But 1is never possible even for an ideal engine. Hence Q2 0
.
(v) Thus it is impossible to extract heat from a single body and convert the whole of it into
work.
(vi) If T2 T1 , then 0 .
(vii) In actual heat engines, there are many losses due to friction etc. and various processes
during each cycle are not quasi-static, so the efficiency of actual engines is much less than that
of an ideal engine.
10.36 Conduction.
Conduction is the phenomenon of transfer of heat through one part of the body to another,
from particle to particle in the direction of fall of temperature without any actual movement of
the particles.
When one end of a solid is heated, the atoms or molecule of the solid at the hotter end
starts vibrating with greater amplitude. The disturbance is transferred to the neighbouring
molecules. This result in the rise of temperature. Thus the heat energy is passed along the rod
from molecule to molecule without changing their equilibrium position along the bar.
(1) When one end of a metal rod is heated, heat flows by conduction from the hot end to the
cold end. In this process, each cross-section of the rod receives some heat from the adjacent
cross section towards the hot end. A part of the heat received is spent in raising the temperature
of the cross section. Another part of heat is lost to the surrounding and the rest of the heat is
conducted away to the next cross section towards the colder end.
As temperature of every cross section of the rod goes on increasing, the rod is said to be in
variable state
(2) In variable state of the rod both the properties i.e. specific heat and thermal conductivity
of material play their roles one in raising the temperature and other in transmission of heat
respectively.
(3) Thermal diffusivity : It is a measure of rate of change of temperature (with time) when
the body is in variable state. It is the ratio of thermal conductivity to thermal capacity per unit
volume of the material h K c .
110 Heat and Thermodynamics
(4) Steady state : After some time from variable state, a situation comes when
temperature of every cross section of the rod become constant. It means there is no absorption
of heat. The heat that reacts any cross section is transmitted to the next. This state of the rod is
called steady state.
In steady state, temperature of each part of the rod is constant but not same. The
temperature decreases as we move away from the hot end of the rod. Specific heat has no role
to play in the steady state. Thermal conductivity alone is effective in steady state.
(5) Law of conduction : In steady state passing through a bar of length L and cross section
( 1 2 )t
A in the time t when its ends are at temperatures 1 and 2 ( 1) is given by Q KA
L
Important points :
d
(i) Quantity is called temperature gradient. Unit = o
C / meter; Dimension = [L1 ] .
dx
(ii) K is the constant of proportionality and it is called the coefficient of thermal conductivity
or simply thermal conductivity. It is a measure of the ability of a substance to conduct heat
through it.
Watt cal cal 3 1
Unit = or o or ; Dimension : [MLT ].
meter Kelvin cm sec C m sec o C
(iii) Generally, metals are good conductor of heat, silver being the best. Non metal like
wood, glass are poor conductors with low value K.
1
(iv) The inverse of thermal conductivity is known as thermal resistivity
K
(v) Conductivity of pure metal decreases with increase in temperature and conductivity of
alloys increases with increase in temperature.
Calories
(vi) For copper value of K = 0.92 .
cm o C sec
L 1 2
(vii) Thermal resistance : R
KA (Q / t)
Greater the thermal resistance, better will be the insulation and poorer will be the
conduction.
Kelvin o o
C sec C sec
Units : or or ; Dimension [M 1L2T 3 ] .
Watt calorie Joule
10.37 Ingen Hauzs Experiment.
Ingen Hauzs experiment bars are coated with wax and one of their ends is put in boiling
water, then in steady state the square of length of the bar over which wax melts is directly
K
proportional to the thermal conductivity of the metal i.e. constant or
L2
K 1 : K 2 : K 3 .............. L12 : L 22 : L 3 2.............
 Heat and Thermodynamics 111

10.38 Heat Flow Through Slabs in Series.

Let there are two slabs are arranged in series as shown in the figure.
(i) Equivalent resistance : R R1 R2
2
Q A( 1 2 ) 1

(ii) Rate of heat flow : t l1 l
2 Q
A K1 A K2 A
K1 K 2
K1 K
1 2 2 l1 l2
l1 l2
(iii) Temperature of interface :
K1 K 2

l1 l2

(iv) Special condition : When length of two slabs are same (l1 l 2 l)

Q K 1 K 2 A( 1 2 )
(a) Rate of heat flow :
t (K 1 K 2 )l
K 1 1 K 2 2
(b) Temperature of interface :
K1 K 2

2K 1K 2
(c) Equivalent thermal conductivity : K
K1 K 2

10.39 Heat Flow Through Slabs in Parallel.

Net transmitted heat Q Q1 Q 2 1 2

1 1 1 Q1
(1) Equivalent resistance (R) : = Q1 A1 K1
R R1 R2

K 1 A1 K 2 A2 Q2 A2 K2 Q2
(2) Equivalent thermal conductivity K
A1 A2
L
10.40 Conductivity in Daily Life.
(1) Cooking utensils are provided with wooden handle.
(2) In winter, metallic handles of wooden door appear colder, because it is a good conductor.
Heat flows from our body to the handle.
(3) Saw dust is poorer conductor of heat than the wood of which it is made. This is due to air
trapped in saw dust.
(4) Eskimos make double walled houses of the blocks of ice. Air enclosed between the
double walls prevents transmission of heat from the house to the cold surrounding.
10.41 Growth of Ice on Ponds.
112 Heat and Thermodynamics
When atmospheric temperature falls below 0 o C the water in the lake will start freezing. If
the temperature of atmosphere is o
C then time taken in forming the ice layer of thickness x
L 2
t .x [ = density of ice, K = Thermal conductivity of ice, L = Latent heat of
2K
fusion]
And time taken in increasing the thickness from x1 to x2 t
L
2K

x2 2 x12
10.42 Convection.
It is the phenomenon of transfer of heat with the actual movement of particles of the body.
For example when we heat a liquid in a flask, the particles of the liquid at the bottom get heated,
become lighter and actually rise up. The cold liquid particles due to higher density come down
and receive the heat. This type of convection which results from difference is called natural
convection. However if a heated fluid is forced to convection.
(1) Natural convection takes heat from bottom to top while forced convection in any
direction
(2) Natural convection can not take place in a gravity free region such as freely falling lift or
orbiting satellite
(3) Natural convection plays an important part in ventilation.
10.43 Radiation.
The process in which heat is transferred directly from one body to another, without requires
any medium is called radiation. All bodies at all temperature and all times are emitting energy.
This energy is called radiant energy and is in the form of electromagnetic waves. The
electromagnetic waves of wave length ranging from 0.0001 mm to 1mm are called infrared
radiation or heat radiation.
When a body absorbs more heat radiation than emitted, its temperature rises and it is said
to be heated by radiation.
(1) It is fastest mode of heat transfer. Speed of energy propagation is 3 108 m/ s
(2) It does not affect the medium through which it passes
(3) They obey inverse square law
(4) They can be reflected and refracted according to the law of reflection and refraction of
light
(5) They also exhibit the interference, diffraction and polarization
(6) Thermal radiation are of longer wave length or smaller frequency and hence smaller
energy as compared to visible light. Thermal radiation wave length ( 8 107 meter to 4 104
meter) visible light wave length ( 4 107 meter to 8 107 meter)
(7) Thermal radiation are detected by thermocouple, thermopile and radio meter etc.
10.44 Some Definitions About Radiation.
(1) Reflectance, absorptance and transmittance
 Heat and Thermodynamics 113
Qr
(i) Reflectance (r) : r
Q where Q = Total radiation incident on
the body
Qa
(ii) Absorptance (a) : a Qr = Radiation reflected by the body
Q
Qa = Radiation absorbed by the body
Qt Qt = Radiation transmitted by the
(iii) Transmittance (t) : t
Q
By adding above three r a t 1 [because Qr Qa Qt Q]
If body does not transmit any heat radiation t 0 . Then r a 1 a = 1 r
If r is more, a is less and vice-versa. It means good reflectors are bad absorbers. r, a and t all
are the pure ratios so they have no unit and dimension
(2) Monochromatic emittance (Spectral Emissive power) : For a given surface it is defined
as the radiant energy emitted per sec per unit area of the surface within a unit wave length
around . It is represented by E
Energy Joule Watt
E . Unit : or , Dimension : [MT 3 L1]
Area time wavelength 2
m sec A o
m2 A o
(3) Total emittance or total emissive power : It is defined as the total amount of
thermal energy emitted per unit time, per unit area of the body for all possible wavelengths. It is

represented by E E d
0

Joule watt
Unit : or 3
2
m sec 2 , Dimension [MT ]
m
(4) Monochromatic absorptance or spectral absorptive power : It is defined as the
ratio of the amount of the energy absorbed in a certain time to the total heat energy incident
upon it in the same time, both in the unit wavelength interval around the wavelength . It is
represented by a . It is a dimension less and unit less quantity.

(5) Total absorptance or total absorpting power : a a d . It is also a unit less and
0
dimension less quantity.
(6) Perfectly black body : A body which absorbs all the radiation incident on it is called a
perfectly black body. It absorbs radiation of all wavelengths.
(i) As perfectly black body neither reflect nor transmits any radiation, therefore absorptance
of a perfectly black body is unity.
(ii ) As black body reflects no wave length, it appears black, whatever be the colour of
radiation incident on it.
(iii) When black body heated to a suitable high temperature, it emits radiation of all possible
wave lengths. The radiation given out by a perfectly black body are called black body radiations
or total radiations.
10.45 Kirchoffs Law.
114 Heat and Thermodynamics
The ratio of emissive power to absorptive power is same for all surfaces at the same
temperature and is equal to the emissive power of a perfectly black body at that temperature.
E Practical E Blackbody E E
EBlackbody or E Blackbody E a
aPractical aBlackbody a a
Practical Practical

It is clear that E is large, a is also large and vice-versa. Hence good emitter are good
absorber.
Application of Kirchoffs law :
(1) Sand is rough and black, so it is a good absorber and hence in deserts days will be very
hot. And according to Kirchoffs law good absorber is a good emitter. So nights will be cold.
(2) The silvered surface of a thermos flask is a bad absorber. It does not absorb much heat
from the surrounding. That is why ice inside the flask does not melt. Also, the silver surface is
bad emitter/radiation, therefore hot liquids inside the flask do not cool quickly.
(3) Fraunhofer lines are dark lines in the spectrum of the sun. when white light emitted from
the central part of sun (photo sphere) passes through its atmosphere (chromo sphere) radiation
of those wave lengths will be absorbed by the gases present there which they usually emit
resulting in dark lines in the spectrum of the sun
(4) Sodium vapours, on heating emit two bright yellow lines. These are called D1 and D 2
lines of sodium. When this is made to pass through sodium vapours at low temperature,
The continuous spectrum intercepted by two dark lines exactly in the same places as D1
and D 2 in accordance with Kirchoffs law.
10.46 Stefans Law or Stefan Boltzmann Law.
It states that the emissive power or intensity or heat energy radiated per second by unit
area of a perfectly black body is directly proportional to the fourth power of absolute
temperature of the body. E T 4 or E T 4
where is a constant of proportionality and is called Stefans constant.
5.67 104 erg
Its value is 5.67 108 W / m2 K 4 ;
sec cm2 K 4
Its dimension are [MT 3 4 ]
(1) For bodies, which are not perfectly black, Stefans law E e T 4 [e = Emissivity]
(2) Emissivity has no units and no dimension. Its value lies in between 0 and 1 i.e, 0 < e < 1
For black body e = 1
(3) If the body at temperature T is surrounded by a body at temperature T0, then Stefans
law may be put as

E e T 4 T0 4
Here e is taken as emissivity of both, the body and the enclosure.
10.47 Cooling by Radiation.
 Heat and Thermodynamics 115
If a body at temperature T is an environment of temperature T0(<T). The body is losing
Q1
energy by emitting radiation at a rate. eA T 4 and is receiving energy by absorbing energy
t
Q2
at a rate eA T0 4
t
Q Q1 Q2
So net rate of loss of energy by the body through radiation eA (T 4 T0 4 )
t t t
.....(i)
Now if m is the mass of the body and c its specific heat, the rate of loss of heat at
temperature T must be
dQ dT
mc ........(ii)
dt dt
dT dT eA 4
By equating (i) and (ii) equation mc eA (T 4 T0 4 ) [T T0 4 ]
dt dt mc
10.48 Newtons Law of Cooling.
The rate of cooling is proportional to temperature difference between the body and its
surrounding provided the temperature of the body is not very different from the surrounding.
This is called Newtons law of cooling. Rate of cooling
Rate of Cooling

Temperature difference

Temperature
If body cools by radiation from 1 to 2o C in
time t, then the average temperature of body can be
1 2
taken as let is the temperature of
2
1 2 1 2
surrounding then by Newtons law
t 2 Temp. Time
difference
10.49 Energy Distribution of Black Body
Radiation.
Lummer and pringshum performed experiments to study the distribution of energy with
wavelength. Each curve in the graph, represents the variation of monochromatic emittance (E)
with wave length ().
Observation from the graph :
1644
(1) At a given temperature energy is not uniformly distributed
among different wave lengths
(2) At a given temperature intensity of heat radiation increases
with wave length, reaches a maximum at a particular wavelength and
with further increase in wavelength it decreases
116 Heat and Thermodynamics
(3) With increase in temperature wavelength m corresponding to most intense radiation
decreases in such a way that m T constant
(4) For all wavelength an increase in temperature causes an increase in intensity.
Weins displacement law : According to this law, the wavelength ( m) of maximum
intensity of emission of black body radiation is inversely proportional to absolute temperature
(T ) of the black body

1
m or mT b
T
constant b is called Weins constant and has value 2.89 103
meter-kelvin.
(1) The Weins displacement law accounted for the change in colour of a body from red to
yellow and then white as its temperature is increased
(2) Temperature of sun can be calculated by this law. From the spectrum of the sun, analysis
of radiation emitted shows that m 4753 1010 meter

b 2.892 103
By Weins law T T 6050K
m 4753 1010