KTG Thermodynamics

Kinetic Theory Of Gases And Thermodynamics
KINETIC THEORY OF GASES SYNOPSIS
GAS LAWS
Boyle’s Law
It states that at constant temperature the volume of a given mass of ideal gas is inversely propor
tional to its pressure.
V  1 / P or PV = constant
or P1V1  P2 V2 (For constant m and T)
Charle’s Law
It states that if the pressure remains constant, then the volume of a given mass of a ideal gas increases
or decreases by 1/273.15 of its volume at 0°C for each 1°C rise or fall of temperature. Mathematically,
 t   273.15  t 
Vt  V0  1    V0  
 273.15   273.15 
If we put 273.15 + t = T and 273.15= T0, then
Vt V0 V
 or  constant
T T0 T
So charles’ law can also be stated as follows:
At constant pressure, the volume of a given mass of a gas is directly propotrional to its absolute temperature.
Gay Lussac’s Law
• It states that if the volume remains constant, then the pressure of the given mass of a gas increases
or decreases by 1/273.15 of its pressure at 0°C for each 1°C rise or fall of temperature. Mathematically,
 t   273.15  t  Pt T P
Pt  P0  1    P0   or,  
 273.15   273.15  P0 T0 or T constant
So Gay Lussac’s law can also be stated as follows:
At constant volume, the pressure of a given mass of a ideal gas is directly proportional to its absolute temperature.
Ideal Gas Equation
P1V1 P2 V 2
• For n moles of a ideal gas, PV  nRT or 
T1 T2
For 1 mole of a gas, PV = RT
Universal gas constant:
• It signifies the work done by the gas per mole per kelvin.
R  8.31 Jmol 1K 1 =1.98 cal/mole-k
Boltzmann’s constant:
• It is the gas constant per molecule of a gas.
If NA is Avogadro’s number, then
R
kB   1.38  1023 J molecule 1 K 1
NA
RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC * RCC 1
Ideal Or Perfect Gas
• A gas which obeys gas laws strictly is an ideal or perfect gas. The molecules of such a gas are of
point size and there is no force of attraction between them. The actual real gases obey the ideal gas
equation only approximately at low pressures and high temperatures.
ASSUMPTIONS OF KINETIC THEORY OF GASES
• All gases consist of molecules. The molecules are rigid, elastic spheres identical in all respects for a
given gas and different for different gases.
• The size of a molecule is negligible compared with the average distance between two molecules.
• The molecules are in a state of continuous random motion, moving in all directions with all possible
velocities.
• During the random motion, the molecules collide with one another and with the walls of the vessel.
• The colliosions are perfectly elastic and there are no forces of attraction or repulsion between them.
• Between two collisions, a molecule moves in a straight path with a uniform velocity.
• The collisions are almost instataneous.
• The molecular density remains uniform throughout the gas.
THE PRESSURE OF AN IDEAL GAS
• Consider an ideal gas consisting of N molecules in a container of volume V. The container is a cube

with edges of length d. Consider the collision of one molecule moving with a velocity v towards
the right hand face of the cube. y
• The molecule has velocity components vx, vy and vz. But in
this article we shall use mt to represent the mass of
one molecule. As the molecule collides with the wall v
elastically its x- component of velocity is reversed, while its y
d m
and components of velocty remain unaltered. Because the vx
x-component of the momentum of the molecule is mv x
before the collision and –mvx after the collision, the change x x
d d
in momentum of the molecule is
px  mv x  ( mv x )  2 mv x
• Cubical box with sides of length d containing an ideal gas. The molecule
shown moves with velocity v.
• A molecule makes an elastic collision with the wall of the container.
Its x component of momentum is reversed, while its y component –Vx
remains unchanged. In this construction, we assume that molecule
moves in the xy plane.
• Impulse = Change in momentum of molecule.
F t  p x  2mvx
where F is the magnitude of average force exerted by the wall on
Vy V
the molecule in time t . For the molecules to collide twice with the
same wall, it must travel a distance 2d in the x- direction. Therefore,
the time interval between two successive collisions with same wall is
2d Vx
t  .
vx
• Over a time interval that is long compared with t , the average force exerted in the molecules for
each collision is
2mvx 2mvx  mvx2
F  
t 2 d / vx d
mvx2
According to Newton’s third law, the average force exerted by the molecule on the wall, .
d
• Each molecule of the gas exerts a force on the wall. We find the total force exerted by all the
molecules on the wall by adding the forces exerted by the individual molecules. For N molecules of
gas, each of mass m,
m 2
Fwall 
d
 
vx1  vx22  ....  v x2N
This can also be written,
Nm 2 2 v 2  vx22  ....  vx2N
 Fwall  v x where, v x  x1
d N
Since, the velocity has three components vx , v y and vz we can havee
2 2 2 2 2 2 2 2
v  v x  v y  v z (as v  v x  v y  v z )
As all directions are equally probable
2 2 2 2 1 2
v x  v y  vz  vx  v
3
2
 
N  mv 
Therefore, Fwall 
3  d 
 
 Pressure on the wall
2
Fwall Fwall 1  N
P  2   3 mv 
A d 3  d 

2
1  N  2 2  N  1 
   mv     mv 
3 V  
3  V  2 

2
1 mN 2 2  N   1 
P  v     mv 
3 V 
3  V  2 

AVERAGE KINETIC ENERGY OF A GAS
• Let M be the molecular mass and V the molar volume of a gas. Let m be the mass of each molecule.
Then
• Mean K.E. per mole of a gas,
1 3 3 3
E M  2  PV  RT  k B N AT
2 2 2 2
• Mean K.E. per molecule of a gas,
1 3
E m 2  k BT
2 2
This is the kinetic interpretation of temperature. That is, the temperature of a gas is a measure of the
averagae kinetic energy of a molecule.
1 3 RT
• K.E of 1 gram of gas   2  .
2 2M
Avogadro’s Law
• It states that equal volume of all gases under similar conditions of temperature and pressure contain
equal number of molecules.
AVOGADRO’S NUMBER:
• It is the number of particle present in one mole of a substance. Its most accepted value is,
NA = 6.0225 × 1023 mole–1
Graham’s Law Of Diffusion
• It states that the rate of diffusion of a gas is inversely proportional to the square root of its density.
r1 2

r2 1
Dalton’s Law Of Partial Pressures
• It states that the total pressure exerted by a mixture of non reacting gases occupying a given volume
is equal to the sum of the partial pressures which gas would exert if it alone occupied the same
volume at the given temperature.
P = P1 + P2 + P3 + .....
SPEED OF GAS MOLECULES
Average Speed
• It is defined as the arithmetic mean of the speeds of the molecules of a gas at a given temperature.
1  2  3  .....   n

n
8k B T 8 RT 8PV
  
m M   massof gas  .
Root Mean Square Speed
• It is defined as the square root of the mean of the squares of the speeds of the individual molecules
of a gas.
12   2 2  3 2  .....   n 2
rms 
n
3k BT 3RT 3PV 3P
rms    
m M mass of gas 
Most Probable Speed
• It is defined as the speed possessed by the maximum number of molecules in a gas sample at a
given temperature.
2k BT 2 RT 2 PV
mp   
m M massof gas
RELATION BETWEEN  ,  rms AND  mp :
•   0.92 rms
mp  0.816rms
rms :  : mp  1.73:1.60 :1.41
Clearly, rms    mp
MAXWELL’S LAW
(The distruibution of molecular speeds)

a) The vrms gives us a general idea of molecular speeds in a gas at a given temperature. This doesn’t
mean that the speed of each molecule is vrms.
b) Maxwell derived an equation giving the distribution of molecules in different speeds as follow
3/ 2 mv 2
 m  2

dN  4 N   ve 2 kT
dv
 2 kT 
Where dN = Number of molecules with speeds between v and v + dv.
dN
c) Graph between ( number of molecules at
dv
dN At a particular
particular speed) and v ( speed of these temperature
dv
dN
molecules). From the graph it is seen that Number
dv of molecules
at a particular
is maximum at most probable speed. speed
v (m/s)
3RT 8 RT 2 RT
  
M M M
RT RT RT
 1.73  1.6  1.41
M M M
DEGREE OF FREEDOM
The degree of freedom are the minimum number of informations required to know about the
system.For thermodynamic system (moving paticles), these are the total number of independent
terms of energy. The independent possible motions are translational, rotational and vibrational, so
there are three types of degrees of freedom.
(i) Translational degrees of freedom : The maximum number of translational degrees of freedom can
be three.
1 2 1 2 1 2
These are mvx , mv y , mvz .
2 2 2
(ii) Rotational degrees of freedom : The maximum number of rotational degrees of freedom can be
three. These are
1 1 1
I xx2 , I y y2 , I z z2
2 2 2
(iii) Vibrational degrees of freedom :
Their numbers depend on atoms in the molecule and their arangement. These degrees of freedom
are considered at a very high temperature.
Note : At room temperature only translational and rotational degrees of freedom are taken into
account.
General expression of degrees of freedom
f = 3N – k
Where, N = number of particles in the system (number of atoms in a molecules)
k = Number of independent relations between the particles.
1. Monoatomic gas:
It has assumed that the molecules of a gas are negligible in size, so moment of inertia and hence
rotational kinetic energy of monoatomic gas molecules about the axis passes through itself will be
zero.
The degrees of freedom of monoatomic gas molecules are due to three independent translational
1 2 1 2 1 2
motions along x, y and z axis. The degree of freedom are mvx , mvy , mvz .
2 2 2
2. Diatomic (or) Linear polyatomic gas:
In diatomic gases the molecues are assumed to be in the shape of dumbbells; y
two atoms of negligible size at some separation. In addition to translational Ix , Iy  0
motion, the molecule, can rotate about an axis, so the degrees of freedom of Iz = 0
diatomic gas molecules are due to translation and due to rotation both. If
x
the line joining the two atoms (particles ) is taken as the z-axis, then
z
moment of ineria and hence rotational kinetic energy about z-axis becomes
zero. The molecule has three degree of freedom of translational and two
degree of freedom of rotation these are
1 2 1 2 1 2 1 1
mvx , mv y , mvz , I xx2 , I y y2 .
2 2 2 2 2
Note : If vibrational degrees of freedom are taken into account, then total number of degrees of
freedom of diatomic molecule becomes 7 at high temperature. These are
1 2 1 2 1 2 1 1 1 1
mvx , mv y , mvz , I xx2 , I y y2 ,  v2 , kr 2
2 2 2 2 2 2 2
1 2 1
Here  v corresponds to kinetic energy of vibration (µ is the reduced mass) and kr 2 corresopnds
2 2
to potential energy of vibration (k is the force constant, r is the separation between the atoms).
3. Triatomic or non linear polyatomic gas: y
A non linear molecule has non zero moment of inertia about any
axis, so there are three translational and three rotational degrees
of freedom. Total number of degrees of freedom are six. There are
1 2 1 2 1 2 1 1 1
mvx , mv y , mvz , I xx2 , I y y2 , I zz2
2 2 2 2 2 2
z
Degrees of freedom of different gases at room temperature
Atomicity Degree Of
Example Figure
Of Gas Freedom of ‘f’
Monochromatic He, Ne, Ar 3 translational
Diatomic 3 translational
H2, N2, O2,
(OR) + 2 rotational
CO, CO2
Linear polyatomic =5
Triatomic 3 translational
H2O, SO2
(non-linear) + 3 rotational
=6
LAW OF EQUIPARTITION OF ENERGY

According to this law, for a system in thermal equilibrium, the total energy of a dynamic system is
equally distributed among its various degrees of freedom. The energy associated with each degree
of freedom. is kT/2 per molecule or RT/2 per mole.
Cv ,Cp and γ for different gases
1. Monoatomic gas
Degrees of freedom, f = 3
RT 3RT
K.E. per mole, E  U  3  
2 2
U 3R
Molar specific heat at constant volume Cv  
T 2
5R
Molar specific heat at constant pressure C p  Cv  R 
2
Cp 5R / 2 5
Ratio of specific heat,      1.66
Cv 3R / 2 3
2. Diatomic Gas
Degrees of freedom, f = 5
RT 5RT
K.E. per mole U  5  
2 2
Molar specific heat at constant volume,
U 5 R
Cv  
T 2
Molar specific heat at constant pressure,
7R
C p  Cv  R 
2
Ratio of specific heat
Cp 7R / 2 7
    1.4
Cv 5R / 2 5
3. Triatomic or polyatomic
Degrees of freedom f = 6
RT
K.E. per mole U  6   3RT
2
Molar specific heat at constant volume,
U
Cv   3R
T
C p  Cv  R  4 R
Ratio of sp. heat,
Cp 4R 4
    1.33
Cv 3R 3
4. For a molecule with f degrees of freedom
K.E. per mole,
RT fRT
Uf 
2 2
Molar specific heat at constant volume
U fR
Cv  
T 2
fR f 
C p  Cv  R   R  R   1
2  2 
Ratio of specific heat,
f 
R   1
C 2  2
 p   1
Cv f  R / 2 f
Specific Heat Capacity Of Solids
We can use the law of equipartition of energy to determine specific heats of solids. Consider a solid
of N atoms, each vibrating about its mean position, devoid of other motion. An oscillation in one
1
dimension has average energy of 2  k BT  k BT .
2
In three dimensions, the average energy is 3kBT. For mole of solid, N = NA, and the total energy is
U = 3kBT × NA = 3RT
Now at constant pressure, Q  U  PV  U
Q U
since for a solid V is negligible. Hence, C    3R
T T
Specific Heat Capacity Of Water
We treat water like a solid. For each atom average energy is 3kBT. Water molecule has three atoms,
two hydrogen and one oxygen. So it has
Q U
U  3  3k B T  N A  9 RT and C    9R
T T
MEAN FREE PATH
The mean free path of a gas molecule may be defined as the average distance travelled by the
molecule between two successive collisions.
2
1 4 5
3
Let 1 , 2 ,...........n be the distance travelled by a gas molecule during n collisions, then the mean
free path of gas molecule is given by,
1  2  ...........  n

n
During the collision, a molecule of a gas moves in a straight line with constant velocity. The statistical
study of heat gives the mean free path as following
1

2 nd 2
Where d is the diameter of molecule, n is the number molecules per unit volume.
Mean free path depends on nature of molecule (4) and with increease in n (i.e., density) it decreases.
At NTP the mean free path for air molecules is 0.01 µm.
If we take one mole of a gas, then
PV = nRT = nNKT
n N 
P
V KT
1 KT
Hence,   2
2 d P
BROWNIAN MOTION
It provides a direct evidence for the existence of molecules and their motion. The zig-zag motion of
gas molecules is Brownian motion because it occurs due to random collosion of molecules. But this
motion cannot be seen. However, the zig-zag motion of pollen grains (  10 15 m) can be seen under
a microscope.
VANDER WAAL’S EQUATION FOR REAL GAS

Real gases do not obey gas laws and gas equations strictly at high pressures and low temperatures.
Real gases show considerable deviations from equation of ideal gas
 a 
 P  2  V  b   RT for 1 mole of gas, where a and b are constants
 V 
 an2 
Another form  P  2  V  nb   nRT , where n is number of moles of real gas.
 V 
Note:
1. If n1 moles of CV1 , n2 moles of CV2 ..... are mixed, then by conserevation of energy
U1  U 2  ......  U
n1CV1 T  n2CV2 T  ......  (n1  n2  ...)CVmix T
n1CV1  n2 CV2  ......

 CVmix 
n1  n 2  ....
and C Pmix  CVmix  R
2. If n1 moles of  1 and n2 moles of  2 .... are mixed then by conservation of energy we havee
U1  U 2  ......  U
n1CV1 T  n2CV2 T  ......  (n1  n2  ...)CVmix T
 R   R  R
n1    n2    ...  ( n1  n2  ...)
 1  1    2 1   mix  1
n1 n (n  n  ...)
 2  ....  1 2
1  1  2 1  mix  1
n1 n2 n1  n2
For two gases,   1    1  ....    1
1 2 mix
THERMODYNAMICS SYNOPSIS
INTRODUCTION
 It is the branch of physics that deals with the conversion of heat into other forms of energy.
 Thermodynamics is a macroscopic science.
 The state of a gas in thermodynamics is specified by macroscopic variables such as pressure, volume,
temparature, mass and composition.
System
 A particular portion of matter or a restricted region of space under investigation is called system.
 If the state of a system is represented by pressure (P), volume (V), temperature (T) and Entropy (S)
then it is called a thermodynamic system.
TYPES OF SYSTEMS:
 Open system: It is the system in which both heat and matter can be exchanged with surroundings.
Ex.: Plants, Animals etc.,
 Closed system: It is the system in which only heat is exchanged with the surroundings.
Ex.: An electric vapour lamp, gas trapped in a cylinder piston arrangement with conducting walls.
 Isolated system: It is the system in which neither heat nor matter is exchanged with surroundings.
Ex.: Thermos Flask.
 Adiabatic wall is an insulating wall that does not allow heat energy to pass through it.
 Diathermic wall is a conducting wall that allows heat to pass through it.
Thermal Equilibrium
If two bodies are at the same temperature then they are said to be in thermal equilibrium. When
bodies are in thermal equilibrium, no exchange of heat takes place.
Thermodynamic Equilibrium
A system is said to be in thermodynamic equilibrium when it is in a state of thermal,mechanical and
chemical equilibria.
ZEROTH LAW OF THERMODYNAMICS

If two bodies A and B are in thermal equilibrium independently with a third body C, then the bodies
A and B will also be in thermal equilibrium with each other.
 The zeroth law clearly suggests that when two systems A and B are in thermal equilibrium, there
must be a physical quantity that has the same value for both. This thermodynamic variable is
temperature.
 Therefore, zeroth law of thermodynamics leads to the concept of temperature (T).
 Temperature is a measure of the degree of hotness or coldness of a body.
 Temperature determines the direction of flow of heat when two bodies are placed in thermal contact.
 Heat always flows from the body at higher temperature(hot body) to the body at lower
temperature(cold body). It is analogous to electric current in electricity.
 Temperature is a scalar quantity. Its S.I unit is kelvin (K) and C.G.S unit is degree celsius (°C). Its
dimensional formula is M0L0T0K1 or M0L0T0  1.
PARAMETERS OF THERMODYNAMIC LAWS
Heat
 It is the thermal energy exchanges between two systems due to the temperature difference.
 Its SI unit is joule and C.G.S unit is calorie.
Its dimensional formula is [ML2 T–2]
 Calorie:
It is the quantity of heat required to raise the temperature of 1 g of water by 1°C.
 Standard(Mean) Calorie:
It is the quantity of heat required to raise the temperature of 1 g of water from 14.5 °C to 15.5 °C.
Its value is, 1 calorie = 4.186 J  4.2 J .
 Heat is measured by using calorimeter.

 Heat is a path dependent quantity.
Internal Work
It is the work done by one part of a system on its another parts.
Ex.: The work done by a gaseous system against intermolecular forces.
External Work
When the work is done by (or on)the system on (or by) the surroundings, then it is called external
work.
 P-V GRAPH OR INDICATOR DIAGRAM:
The graph drawn between pressure of a gas on y-axis and its volume on x-axis is called indicator
diagram. This graph is usefull to calculate external work done by the system during thermodynamic
change.
Work Done By A Gas During Change In Volume

 When a gas expands, then for a small change (Quasi-statically) in volume dv, small workdone is
dw = pdv = Area of narrow strip as shown in figure. Here pressure P is almost constant.
If the volume changes from v1 to v2, the total external work done is
v2
w   p dv =Area under P-V curve.

v1
Pressure
V1 dv V2 Volume
 Area under p-v graph is equal to the external work done during the process.
 If the volume changes from V1 to V2 at constant pressure(isobarically)
V2
W  P  dv  P V2  V1 
V1
Pressure
P
V1 V2 Volume
 Work is a path dependent quantity

 SIGN CONVENTION:
 If the work is done by the system, then work done is (+ve). (dv  0  w  o)
V
 If work is done on the system, then it is (–ve).
(dv  o  w  o)
V
 In a cyclic process(the system finally reaches the same initial state), workdone is equal to the area
enclosed by the cycle.
It is +ve if the cycle is clockwise.
It is –ve if the cycle is anticlockwise.
P P
W = +ve W = –ve

V V
Relation Between Work & Heat (Joule’s Law)
The amount of heat poduced is directly proportional to the amount of mechanical work done.
H  W or W  JH
W
J , where J = Mechanical equivalent of heat.
H
Mechanical Equivalent Of Heat (J)
 It is the amount of work necessary to produce unit amount of heat engegy.
 J is not a physical quantity. It is simply a conversion factor between mechanical work and its
equivalent heat energy.
 VALUES OF ‘J’:
The value of J depends on the units of work W and heat H.
When W is in Joules, H is in Cal, then J  4.186 J/cal  4.2 J/cal .
When W and H both are expressed in joules, J = 1.
Applications Of Joule’s Law
 The height from which ice is to be dropped to melt it completely is
JL
h
g
where L = Latent heat of ice.
 The rise in temperature of water when it falls from a height h to the ground is,
gh
 
Js
where ‘s’ is specific heat of water
 When a bullet of mass m moving with a velocity v is stopped abruptly by a target and all of its heats
energy liberated is retained by bullet, then the increase in temperature is.
v2
 
2 Js
If the bullet absorbs x% of heat liberated, then rise in its temperature is
x  v2 
   
100  2 Js 
 When a block of ice of mass M is dragged with constant velocity on a rough horizontal surface of
coefficient of friction µ, through a distance d, then the mass of ice melted is,
 Mgd
m
JL
Where, m = mass of ice melted.
In order to melt all the ice, the block completely the blcok should be dragged through a distance
JL
d
g
d
Now, the time taken to melt completely is given by t 
v
 When a block is dragged on a rough horizontal surface of coefficient of friction µ, then the rise in
temparature of block is,
 gd
 
Js
 If a bullet at a temperature lesser than its melting point just melts when abruptly stopped by an
obstacle and if all the heat produced is absorbed by the bullet then
1
J ( ms  mL)  mv 2
2
Where L= Latent heat of material of the bullet
s = Specific heat
 = rise in temperature before it melts.
 A metal ball falls freely on the ground from a height ‘h1’ and bounces to height ’ h2’. If the ball absorbs
all the heat energy generated, the rise in temperature of the ball is
g ( h1  h2 )
 
Js
 When a body rotating with angular speed  is suddenly stopped, if it asborbs all the heat generated,
then rise in temperature of body is
I 2
 
2 Jms
Where, I = M.I. of body.
 A drilling machine drills a hole to a metal plate. The machine is operated by a torque  with constant
angular speed  and drills the hole in a time t. If the heat generated is completely absorbed by the
plate, then the rise in temperature of the plate is
t
 
Jms
Where, m = mass of the plate
s = specific heat of the plate
Internal Energy
It is the energy possessed by the system due to molecular motion and molecular configuration.
Internal energy of a system is a function of thermodynamic variables.
 Internal Potential Energy:
The energy present in a system on account of its molecular and atomic configurations is called internal
potential energy.
 Internal Kinetic Energy:
The energy present in a system on account of translatory motion of its molecules due to random
motion and vibrations of atoms is defined as internal kinetic energy.
 Internal energy of a given mass of gas depends on its state described by specific values of pressure,
volume and temperature. It does not depend on how this state of the gas came about.Therefore,
internal energy is independent of path along which system is carried. It is a point(state) function.
 The change in internal energy depends upon the initial and final states only.
U  U final  U initial
 For an ideal mono atomic gas since there are no inter atomic forces there is no potential energy.
Internal energy of this gas is only translational kinetic energy of atoms. According to kinetic theory
3
the internal energy is U  KT
2
Where K = Boltzmann's constant.

T = Absolute temperature of gas.
For ideal di or tri atomic gases, molecules can rotate and atoms in a molecule vibrate. For such gases
internal energy is
U = Translational KE + Rotational Energy + Vibrational energy.
3
= KT  Rotational Energy + Vibrational energy..
2
At absolute zero temperature (T = 0 K), U is non-zero. This energy is called zero point energy.
 The internal energy of ideal gas depends only on its tempertere T and is independent of other variables
pressure p, volume v. When T increases U also increases and vice versa.
 Internal energy of real gases depends upon temperature, pressure and volume.
 Change in internal energy is zero in a cyclic process. Because final and initial coincided.
 Real gases consist of both kinetic energy and potential energy due to intermoleculer forces.
 According to the kinetic theory of gases, internal energy of a gas depends on :
1) atomicity 2) no. of moles 3) temperature.
It is given by,
f
U nRT
2
Where, f = no. of degrees of freedom.

n = no. of moles
R = Universal gas constant.
T = absolute temperature.
 In case of gases, change in internal energy is,
f
U  nRT = nCv T
2
 When a box containing a gas is given velocity, then the KE of box as a whole is not included to
internal energy of gas.
FIRST LAW OF THERMODYNAMICS

 All the heat added to a system is partly utilized to do the external work and remaining to increase its
internal energy.
 The differential form of first law of thermodynamics is
dQ = dU + dW, where
dQ = heat added,
dU = Increase in internal energy.
dW = work done
Here dU is state dependent but dQ & dW are path dependent quantities.
But, dw = pdv
 dQ  du  p.dv
for bulk changes, Q  U   pdv
Significance And Limitations Of First Law

 It defines the property of system called internal energy.
 It is a consequence of law of conservation of energy.
 This law is applicable to any process in nature.
 This law is applicable to all the three phases of matter.
 First law of thermodynamics doesnot indicate the direction of heat transfer.It does not tell any thing
about the conditions under which heat can be transformed into work.
Sign Convention:
 When heat is added (flows into) to the system dQ is + ve (+dQ)
 When heat is taken (flows out) from the system dQ is –ve (–dQ)
 When gas expands work is done by the gas, dw is positive (+dW)
 When gas compresses work is done on the gas, then work done by the gas dw is negative. (–dW)
 When internal energy of system increases dU is +ve (+dU)
 When internal energy of system decreases dU is –ve (–dU)
Specific Heat
The ammount of heat energy required to rise the temperature of a unit mass of a substance through
1°C (or 1 K) is called specific heat of the substance.
1  dQ 
s  
m  dT 
dQ  msdT
Q  m  sdT
If s is temperature independent, then
Q  msT
S.I. unit of s is, J Kg–1 K–1.
C.G.S. unit is, cal g–1 (°C)–1.
1 cal g–1 (°C)–1 = 4200 J kg–1 K–10.
Dimensional formula of specific heat is, ML2T–2 (mol)–1 K–1.
Specific Heat Of A Gas
 A gas will have two specific heats.
a) Specific heat at constant volume (cv)
b) Specific heat at constant pressure (cp)
 Specific heat depends only on the nature of material and temperature.
 Water has largest specific heat among solids and liquids.
 Among solids, liquids and gases specific heat is maximum for Hydrogen.
 Specific heat slightly increases with increase of temprature.
 In liquids specific heat is minimum for Mercury.
 The value of specific heat may lie between 0 and  .
 Specific heat of water is maxium at 15°C and minimum at 37°C.
 Specific heat of all substances is zero at 0 K.
 Substances with highest specific heat are bad conductors of heat and with low specific heat are good
thermal and electrical conductors.
 The substance with large specific heat warms up slowly and cools down slowly.
 Specific heat of gas at constant pressure (cp):
It is the heat required to rise the temperature of 1 g of gas by 1°C at constant pressure,
1  dQ 
cp   
m  dT  p
dQ p  mc p dT
Q p  mc p T , if cp is constant.
Qp  m  c p dT , if cpdepends on temperature.
 Specific heat of gas at constant volume (cv):

It is the heat required to rise the temperature of 1 g of gas by 1°C at constant volume.
1  dQ 
 cv   
m  dT v
dQv  mcv dT
Qv  mcv T , if cv is constant.
Qv  m  cv dT ,
if cvdepends on temperature.
 S.I. unit of both cp , cv is J/Kg/K
C.G.S. unit is cal/g/ (°C)
MOLAR SPECIFIC HEATS OF C P & C V OF A GAS
When the above specific heats cp , cv are defined per 1 mole of gas, then they are said to be molar
specific heats and represented by CP , CV. These are
1  dQ 
Cp   
n  dT  p
1  dQ  1  dU 
 , (1 law)
st
Cv     
n  dT v n  dT 
S.I. unit of both molar specific heat is J/ mol/K
 Cp is greater than CV and,
Cp
  (C , C are molar specific heats )
Cv p V
Cp – CV=R, where R is universal gas constant

R = 8.314 J/mol/K  2 cal/mol/K
R R
Cp  and Cv 
 1  1
 c p  cv  r
Where r is specific gas constant and cp, cv are expressed in J/Kg/K.
 For a gas having f degrees of freedom,
f   f 
Cv    R , C p   1   R
2  2
2
 1
f
CV, CP & VALUES OF DIFFERENT GASES
Sr. Atomicity CP
CP CV
No. Of Gas CV
5 3 5
1. Monoatomic R R  1.67
2 2 3
7 5 7
2. Diatomic R R  1. 4
2 2 5
Tri non-linear & 4
3. 4R 3R  1.33
polyatomic 3
9 7 9
4. Trilinear R R  1.29
2 2 7
  value is always greater than one. It depends upon the atomicity of a gas. It decreases with
increase in atomicity.  is maximum for monoatomic gas.
Of Mixture Of Gases
When n1 moles of a gas with specific heat at constant volume CV1 is mixed with n2 moles of another
gas of specific heat at constant volume CV 2 then
n1cv1  n2 cv2
(Cv )mixture 
n1  n2
(Cp )mixture  (Cv )mixture  R
n1c p  n2 c p
1 2

n1  n2
C p(mixture)
γ mixture 
C v(mixture)
n1  n2 n n
Also   1  2
mixture  1 1 1  2 1
 At constant pressure,fraction of heat absorbed that is converted into internal energy is
dU Cv 1
 
dQ Cp γ
 At constant pressure,fraction of heat absorbed that is converted into external workdone is
dW R 1
  1
dQ Cp γ
THERMODYNAMIC PROCESSES
Quasi–Static Process
 A quasi static process can be defined as an infinitesimally slow process in which the system remains
in thermal and mechanical (themodynamic) equillibrium with the surroundings at each and every
intermediate stage. i.e., temperature, pressure are almost constant during infinitesimal small change
in the state of gas. It is an ideal process. In practice it does not occur.
Isothermal Process
 In this process, the pressure and volume of gas change, but temperature remains constant. Hence
internal energy is also constant. i.e., dT = 0, dU = 0.
 The system is in thermal equilibrium with the surroundings.
 It takes place in a thermally conducting vessel. Hence heat exchanges between system and
surroundings.
 In this process, dQ = dQ
 It is a slow process.
 It obeys the Boyle’s law i.e. PV = Constant
 Specific heat is infinity.
 Indicator diagram
P
Work
V
 Slope of isothermal curve,
dP P
tan   
dV V
 The isothermal elasticity ,
dp
 p
dv v
 The workdone during the isothermal change at temperature T for n moles of gas is
V   p1 
W  2.303nRT log10  2  = 2.303 nRT
T log10  
 V1   p2 
 Isothermal process is ideal. In nature, no process is perfectly isothermal. But we can say melting of
ice, boiling of water are approximately isothermal. In these two processes internal energy increases
even temperature is constant.
Adiabatic Process
 The pressure, volume and temperature of a gas change but total heat remains constant i.e.,
dQ = 0 (Q = constant).
 There should not be any exchange of heat between the system and surroundings.All the walls of the
container and the pistion must be perfectly insulating.
 It is a quick process.
 The internal energy changes certainly as temperature changes.
 In the adiabatic process P, V & T are related as
PV  = constant
TV  1 =constant
P 1 T  =constant
 In this process specific heat is zero.
 Indicator diagram is
Work
V
 Slope of adiabatic curve
dP P
tan    
dV V
 The slope of adiabatic curve is  times to that of the isothermal curve.
 The adiabatic elasticity of gas is  p.i.e  times isothermal elasticity..

 The workdone by the system during the adiabatic expansion is
nR
W (T –T )= nCv(T1–T2) =  nCv T
 1 1 2
Cp p1v1  p2 v2
=n (T1–T2) =
  1
 It takes place in a non conducting vessel. Hence no exchange of heat takes place between and
surroundings.
 Adiabatic expansion causes cooling and compression causes heating.
 Eg:- Sudden bursting of tube of bicycle tyre, Propagation of sound in gases
 In this process, dU = –dW.
Comparison Between
Isothermal And Adiabatic Curves
 When expanded to the same volume from the same initial state.
1 1 - Isothermal
2 - Adiabatic
2
V
V1 V2
Work done :W1>W2
Final pressure :P1>P2
Final temperature :T1>T2
 When compressed to the same volume from the same initial state.
P
2 1 - Isothermal
2 - Adiabatic
1
V
V1 V2
Work done :W1<W2
Final pressure :P1<P2
Final temperature :T1<T2
 When expanded to the same pressure from the same initial state.
P
1 - Isothermal
2 - Adiabatic
2 1
V
V1 V2
Work done :W1>W2
Final pressure :V1>V2
Final temperature :T1>T2
 When compressed to the same pressure from the same initial state.
P
1 - Isothermal
2 2 - Adiabatic
1
V
V1 V2
Final pressure :V1<V2
Final temperature :T1<T2
Isochoric Process (OR) Isometric Process
 It is a process in which the volume of the system remains constant.
i.e., V = 0 for such process W = 0
 In this process, the increase in internal energy is maximum where as the work done is zero.
 In this process Q  U
P
 It obeys Gay-Lussac's law, K
T
P
V
dP
 Slope of isometric curve, 
dV
f
 Specific heat is, CV  R
2
 Bulk modulus of elasticity, K  
Isobaric Process
 It is a process in which the pressure of the system remains constant. i.e., P  0
 It obeys Charle's law ,
V
K
T
P
Work
V
V1 V2
 Slope of isobaric curve,
dP
0
dV
 Specific heat is,
f 
C p    1 R
2 
 Bulk modulus of elasticity, K = 0.

 Work done in isobaric process is given by,
W  P(V2  V1 )
W  nR(T2  T1 )  nRT
 Ex.:- Boiling of water into steam.
Polytropic Process
In this process the gas obeys an additional law in the form of PV x = constant,
(where x is +ve or –ve constant) along with ideal gas equation PV = nRT
T
 In this process external Work done is,
 nRT
W=
x 1
 In this process Specific heat,
R R
C= 
 1 x  1
Comparison Of P–V Curves
Of Various Processes
K=0
Isobaric
Isochoric
K=P
Isothermal
K = P
Adiabatic
K =
V
Free Expansion
Figure shows an insulated cylinder divided into two parts by a thin massless
fixed piston. Volume of left compartment is filled with an ideal gas and
the right compartment is vacuum.If we release the piston, gas fills the
whole space of the cylinder rapidly. In this expansion. No heat is supplied
to the gas as walls are insulated.
Q  0
No work is done by the gas, W  0
and hence internal energy remains constant.
U  0 , T is constant
Such an expansion is called "free expansion".
SECOND LAW OF THERMODYNAMICS
(Different Processes )
 Claussius statement:
It is impossible for a self acting machine unaided by any external agency to transfer heat from a cold
reservior to a hot reservior. In other words heat can’t flow by itself from a colder to a hotter body.
 Kelvin-Planck Statement:
It is impossible for any heat engine to convert all the heat absorbed from a reservoir completely into
useful work. In other words 100% conversion of heat into work is impossible.
 These two statements of the second law are equivalent to each other. Because, if one is voilated, the
other is also automatically.
Reversible Process
 A process which can be retraced back in such away that the system passes through the states as in
direct process and finally the system acquires the initial conditions, leaving no change anywhere
else,is called reversible process. Any quasi-static process can be reversible.
CONDITIONS FOR A PROCESS TO BE REVERSIBLE
(a) There should be no loss of energy due to conduction, convection or dissipation of energy against
any resistance, like friction, viscosity etc.
(b)No heat should be converted into magnetic or electric energy.
(c) The system must always be in thermal,mechanical and chemical equilibrium with the
surroundings.(i.e the process must be quasi-static)
 Examples : In practice, there is no
reversible process. But approximately we can give the following examples.
i) The process of change of state from ice into water is a reversible process.
ii) The process of change of state from water to steam.
iii) The gradual extension and compression of an elastic spring is approximately reversible.
iv) The electrolysis process is reversible if internal restance is negligibly small.
v) Slow compression and expansion of an ideal gas at constant temperature.
Irreversible Process
 In this process the system doesnot pass through the same intermediate states as in the direct process.
 All the processes occurring in nature are irreversible.
 Examples
1) Work done against friction
2) Joule heating effect
3) Magnetic hysterisis
4) Diffusion of gas
5) Disolving of salt in water
6) Sudden expansion or compression of gas
7) Rain fall
8) Rusting of iron
HEAT ENGINE
 The device, used to convert heat energy into mechanical energy is called a heat engine.
 For conversion of heat into work with the help of a heat engine the following conditions required.
i) There should be a reservoir at constant higher temperature ‘ T1 ’ from which heat is extracted. It is
called the source.
ii) Working substance which undergoes to thermodynamic cyclic changes(ex: ideal gas).
iii)There should be a reservoir at constant lower temperature ‘ T2 ’ to which heat can be rejected. This
is called the sink.
 The source and sink should have very high thermal capacity.
 Working of heat engine -
a) Schematic diagram of heat engine
Source Engine Sink
T1 T2
Q1 Q2
W = Q1- Q2
b) Engine derives an amount ‘ Q1’ of heat from the source.

c) A part of this heat is converted into work ‘W’.
d) Remaining heat ‘Q2’ is rejected to the sink.
Thus Q1 = W + Q2
or the work done by the engine is given by, W = Q1 – Q2
e) The energy Q2 is unavailable in the universe, which causes increase in entropy of universe.
 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.
Mathematically,
W Q1 Q 2
Q2
  or   1
Q1 Q1 Q1
 According to this , efficiency is 100% if Q2 = 0, i.e. no heat is rejected to the cold reservoir or sink that
is the entire heat absorbed must be converted to mechanical work , which according to Second law
of Thermodynamics is impossible.
CARNOT (OR REVERSIBLE OR IDEAL)

HEAT ENGINE
 When the working substance is an ideal gas and it is subjected to cyclic process consisting of isothermal
expansion, adiabatic expansion, isothermal compression and adiabatic compression, then such heat
engine is called Carnot engine. The cyclic process is called Carnot cycle.
 Carnot Cycle
 Carnot cycle consists of the following four stages :
(i) Isothermal expansion (process AB),
(ii) Adiabatic expansion (process BC),
(iii) Isothermal compression (process CD),
and
(iv) Adiabatic compression (process DA).
The P-V diagram of the cycle is shown in the figure :
In process AB heat Q1 is taken by the working substance at constant P
temperature T1 and in process CD heat Q2 is liberated by the A T1 B
working substance at constant temperature T2. The net work done Q1
is area enclosed by the cycle ABCDA. After doing the calculations D
T2 Q2 C
for different processes we can show that :
V
Q2 T2
Q1 = T1
Therefore, efficiency of the Carnot engine is,
Q2 T
  1  1 2
Q1 T1
As T2 is always less than T1, implies always   1 . i.e., the value of  can never be equal or greater
than 1. When the temperature of sink T2 = 0 K, then  can be 1 or 100%. But it is impossible.
 For carnot engine  is independent of the nature of working substance. It depends on only the
temperatures of source and sink.
 For Carnot engine the source and sink should have infinite thermal capacities.
 The efficiency of an irreversible engine is always less than or equal to that of reversible engine when
operated between the same temperature limits.
 Always ir  r but,  ir can not be greater than r .
REFRIGERATOR
(Hot Reservoir) ( Cold Reservoir)

Source Engine Sink
T1 T2
Q1 Q2
W = Q 1 – Q2
The refrigerator is just the revesrse of heat engine In refrigerator the working substance extracts an
amount of heat Q2 from the cold reservoir (Sink).
at a lower temperature T2. An amount of external work W is done on the working substance and
finally an amount of heat Q1 is rejected to the hot reservoir at a higher temperature T1. Hence
refrigetator is also known as a heat pump.
 Coefficient of performance of a refrigerator,
Q2 Q2
=  = [ W = Q1 – Q2]
W Q1  Q2
Q2 T2 T2
 For Carnot refrigerator Q = T . Thus ,  
1 1 T1  T2
 The relation between efficiency of a heat engine ( ) and coefficient of performance of a refrigerator
() working between the same temperature limits is
1 
=

 Let  1 and  2 are the efficiencies of heat engines working between temperature limits T1, T2 and T2,
T3 respectively then the efficiency of heat engine working between temperature limits T1 and T3 is
  1  (1  1 )(1   2 ) .
Entropy (s)
 The thermodynamic coordinate or parameter that gives the measure of disorder is called entropy.
We cannot measure entropy, but we can measure change in entropy during thermodynamic change.
If ‘ds’ is the small change in entropy at temperature T, then
dQ
ds =
T
Where, dQ is exchange of heat between system and surroundings at temperature T.
Now the total change in entropy is,
dQ
s  
T
 Change in entropy during an isothermal change is,
Q W V 
s=   2.303nR log 10  2 
T T  V1 
 Change in entropy during phase change is
mL
s =
T
sdT
 Change in entropy during temperature change is s = m  , if s is temperature dependent.
T
 In a reversible process entropy increases if heat is absorbed and vice-versa.
 Entropy of the universe always increases if system undergoes an irreversible process.
 Entropy of universe can never be zero.
 At absolute zero temperature(0 K), entropy becomes zero. But it does not occur.
PRACTICE MCQS
7. Temperature remaining constant, the pressure
Kinetic Theory Of Gases of the gas is decreased by 20%. The percentage
1. A real gas behaves like an ideal gas if its change in volume is
a) pressure and temperature are both high a) increased by 20% b) decreased by 20%
b) pressure and temperature are both low c) increased by 25% d) decreased by 25%
c) pressure is high and temperature is low 8. A vessel has 96 g of oxygen at pressure P and
d) pressure is low and temperature is high temperature 500 K. A small hole is made in it
2. Fro the following P-T graph, what inference so that oxygen leaks out. How much oxygen
can be drawn? leaks out if the final pressure is P/2 and
a) V2  V1 temperature falls to 300 K?
a) 4 g b) 8 g
b) V2  V1 c) 16 g d) 32 g
9. The equation of state for 5 g of O2 at a pressure
c) V2  V1
P and temperature T, when occupying a
d) No inference can be drawn volume V, will be
3. How much should the pressure be increased a) PV = 5/32 RT b) PV = 5 RT
in order to decrease the volume of a gas by c) PV = 5/2 RT d) PV = 5/16 RT
5% at a constant temperature? 10. Two gases A and B having same pressure P,
a) 5% b) 5.26% volume V and temperature T are mixed. If mixture
c) 10% d) 4.26% has volume and temperature as V and T
4. A closed vessel A having volume V contains respectively, then pressure of the mixture will be
nitrogen at pressure P and temperature T. a) 4 P b) 3 P
Another closed vessel B, having the same c) 2 P d) P
volume contains helium at the same pressure P
11. The r.m.s. velocity of gas molecules is 300 m/sec.
but temperature 3T. The ratio of the masses of The r.m.s. velocity of molecules of gas with
nitrogen and helium in the vessels A and B is twice the molecular weight and half the
a) 3 : 1 b) 6 : 1 absolute temperature is
c) 7 : 1 d) 21 : 1 a) 300 m/sec b) 600 m/sec
5. In a vessel of volume V, these is a perfect gas
c) 75 m/sec d) 150 m/sec
at pressure P and absolute temperature T. The
12. At what temperature is the root mean square
mass of each molecule of gas in m and k is the
velocity of gaseous hydrogen molecules equal
boltzmann constant, then the density of the
to that of oxygen molecules at 47°C?
gas is
a) –73 K b) 3 K
m m mP mT c) 20 K d) 80 K
a) b) c) d)
kT V kT PT 13. The temperature of an ideal gas is increased
6. Figure shows two from 27°C to 127°C, then the percentage
flasks connected to increase in rms velocity of gas is
each other. Volume a) 11% b) 15.5%
of flask I is twice to c) 31% d) 37%
that of flask II. The system is filled with an 14. At what temperature is the root mean square
ideal gas at temperature 100 K and 200 K speed of an atom in an argon gas cylinder equal
respectively. If the mass of the gas in I be m to the rms speed of a helium gas atom at –20°C?
then what is the mass of the gas in flask II? (Atomic mass of Ar = 39.9 u, of He = 4.0 u)
a) m b) m/2 a) 2251 K b) 2351 K
c) m/4 d) m/8 c) 2424 K d) 2524 K
1. (d) 2. (a) 3. (b) 4. (d) 5. (c) 6. (c) 7. (c) 8. (c) 9. (a)

10. (c) 11. (d) 12. (c) 13. (b) 14. (d)
15. If v be the velocity of sound in air and C be 21. One kg of a diatomic gas is at pressure of
the r.m.s. velocity of air molecules, then (  is 8 × 104 N/m2. The density of the gas is 4 kg/m3.
the ratio of sp. heats of gas at constant pressure What is the energy of a gas due to its thermal
and at constant volume) motion?
a) 3 × 104 J b) 5 × 104 J
a) v  C b) v  r C / 3
c) 6 × 104 J d) 7 × 104 J
c) v  C  / 3 d) v  C 2  / 3 22. Pressure of an ideal gas is increased by
keeping temperature constant. What is the
16. If masses of all molecules of a gas are halved
effect on kinetic energy of molecules?
and their speeds doubled then the ratio of
a) Increases
initial and final pressure will be
b) Decreases
a) 2 : 1 b) 2 : 1
c) No change
c) 4 : 1 d) 1 : 4
d) Cannot be determined
17. A container of volume V is having a gas of
23. At what temperature the kinetic energy of a
density P. Let C be the r.m.s. speed of the
gas molecule is half of the value at 27°C?
molecules of the gas. If the container moves
with velocity v, then pressure exerted by the a) 12.5°C b) 150°C
gas is c) 75 K d) –123°C
24. At which of the following temperatures
1 2 1 2 would the molecules of a gas have twice the
a) C b) (C  v)
3 3 average kinetic energy they have at 27°C?
2
a) 327°C b) 373°C
1 2 1 Cv c) 393°C d) 586°C
c) (C  v) d)   
3 3  2  25. A gas mixture contains of 2.0 moles of oxygen
18. A jar has a mixture of hydrogen and oxygen and 4.0 moles of neon at temperature T.
gases in the ratio 1 : 5 the ratio of mean kinetic Neglecting all vibrational modes, the total
energies of hydrogen and oxygen molecules is internal energy of the system is [R = universal
gas constant]
a) 1 : 16 b) 1 : 4
a) 4.5 RT b) 5.5 RT
c) 1 : 5 d) 1 : 1
c) 8.5 RT d) 11 RT
19. The average translatory energy and r.m.s. speed
26. The mean kinetic energy of one mole of gas
of molecules in a sample of oxygen gas at 300 K
per degree of freedom (on the basis of kinetic
are 6.21 × 10–21 J and 484 ms–1 respectively. The
theory of gases) is
corresponding values at 600 K are nearly
(assuming ideal gas behaviour) 1 3
–21 –1 a) kT b) kT
a) 12.42 × 10 J, 968 ms 2 2
b) 8.78 × 10–21 J, 684 ms–1
3 1
c) 6.21 × 10–21 J, 968 ms–1 c) RT d) RT
2 2
d) 12.42 × 10–21 J, 684 ms–1
27. The kinetic energy per g-mol for a diatomic
20. Helium gas is filled in a closed vessel (whose
gas at room temperature TK is
coefficient of thermal expansion is negligible).
When it is heated from 300 K to 600 K, then 3 1
average kinetic energy of helium atoms will be a) RT b) RT
2 2
a) half b) unchanged
5
c) two times d) 2 times c) RT d) 3 RT
2
15. (c) 16. (b) 17. (a) 18. (d) 19. (d) 20. (c) 21. (b) 22. (c) 23. (d)
24. (a) 25. (d) 26. (d) 27. (c)
28. If temperature of gas increases from 27°C to 35. A gas mixture consists of 2 moles of oxygen
927°C, the KE will be and 4 moles argon at temperature T. Neglecting
a) double b) half all vibrational modes, the total internal energy
c) one-fourth d) four times of the system is
29. The kinetic energy of translation of 20 g of a) 4 RT b) 15 RT
oxygen at 47°C is (molecular mass of oxygen c) 9 RT d) 11 RT
is 32 and R = 8.3 J/mol/K)
a) 2490 J b) 24090 erg Thermodynamics
c) 830 J d) 30 ergs
30. A vessel contains a mixture of 1 mole of oxygen FIRST LAW OF THERMODYNAMICS
and 3 moles of nitrogen at 27°C. The ratio of 36. 110 J of heat is added to a gaseous system
average rotational kinetic energy per oxygen whose internal energy increases by 40 J. The
molecule to hat of per nitrogen molecule is amount of external work done is
a) 1 : 1 b) 1 : 3 a) 70 J b) 150 J
c) (3 : 1) d) 8 : 21 c) 110 J d) 40 J
31. The temperature of argon, kept in a vessel is 37. If R is universal gas constant, the amount of
raised by 1°C at a constant volume. The total heat needed to raise the temperature of 2 moles
heat supplied to the gas is a combination of of an ideal monoatomic gas from 273 to 373 K
translational and rotational energies. Their when no work is done is
respective shares are
a) 100 R b) 150 R
a) 60% and 40% b) 40% and 60%
c) 300 R d) 500 R
c) 50% and 50% d) 100% and %
32. If two perfectly monoatomic gases at 38. The molar heat capacity in a process of a
temperature T1K and T2K and number of moles diatomic gas, if it does a work of Q/4 when
in the gases n1 and n2 respectively are mixed. heat Q is supplied to it is
Assuming there is no loss of energy, the 2 10
temperature of the mixture in kelvin is a) R b) R
5 3
n1T2  n2T1 n1T2  n2T1
a) b) 5 6
n1  n2 n1  n2 R c) d) R
3 5
n T  n2T2 n T  n2T2 39. Heat is supplied to a diatomic gas at constant
c) 1 1 d) 1 1 pressure. The ratio of Q : U : W is
n1  n2 n1  n2
33. A diatomic gas molecule has translational a) 5 : 3 : 2 b) 7 : 5 : 2
rotational and vibrational degrees of freedom. c) 2 : 3 : 5 d) 2 : 5 : 7
Then CP / CV is 40. A sample of ideal gas (  = 1.4) is heated at
a) 1.67 b) 1.4 constant pressure. If 100 J of heat is supplied
c) 1.29 d) 1.33 to the gas, the work done by the gas is
34. An insulated box containing a diatomic gas a) 28.57 J b) 56.54 J
of molar mass M is moving with a velocity v. c) 38.92 J d) 65.38 J
The box is suddenly stopped. The resulting 41. When an ideal gas (  = 5/3) is heated under
change in temperature is
constant pressure, then what percentage of
Mv 2 Mv 2 given heat energy will be utilised in doing
a) b) external work
2R 3R
a) 40% b) 30%
Mv 2 2 Mv 2 c) 60% d) 20%
c) d)
5R 5R
28. (d) 29. (a) 30. (a) 31. (d) 32. (c) 33. (c) 34. (c) 35. (d) 36. (a)
37. (c) 38. (b) 39. (b) 40. (a) 41. (a)
42. A system performs work W when an amount SPECIFIC HEAT, CP AND C V
of heat Q is added to the system and the 48. When an ideal monoatomic gas is heated at
corresponding change in the internal energy is constant pressure. fraction of heat energy
U . A unique function of the initial and final supplied which increases the internal energy
states (irrespective of the mode of change) is of gas, is
a) 3/5 b) 2/5
a) Q b) W c) 3/7 d) 3/4
c) U and Q d) U 49. If C p
and C v
denote the specific heats of
nitrogen per unit mass at constant pressure
43. When heat energy of 1500 joule, is supplied and constant volume respectively, then
to a gas at constant pressure 2.1 × 105 N/m2,
there was an increase in its volume equal to a) C  C  28 R b) C p  Cv  R / 28
p v
–3 3
2.5 × 10 m . The increase in internal energy
of the gas in joule is c) Cp  Cv  R / 14 d) Cp  Cv  R
a) 450 b) 525 50. Two moles of oxygen are mixed with eight
c) 975 d) 2025 moles of helium. The effective specific heat
of the mixture of constant volume is
44. 100 g of water is heated from 30°C to 50°C
ignoring the slight expansion of the water, the a) 1.3 R b) 1.4 R
change in its internal energy is (specific heat c) 1.7 R d) 1.2 R
of water is 4184 J/Kg/K) 51. A diatomic gas is heated at constant pressure.
a) 4.2 kJ b) 8.4 kJ What fraction of heat energy is used to increase
the internal energy?
c) 84 kJ d) 2.1 kJ
a) 3/5 b) 3/7
45. 1 cm 3 of water at boiling point absorbs c) 5/7 d) 5/9
540 calories of heat to become steam wit ha 52. Cp and Cv are specific heats at constant pressure
volume of 1671 cm 3 . If the atmospheric and constant volume respectively. It is observed
pressure = 1.013 × 105 N/m2 and the mechanical that Cp – Cv = a for hydrogen gas
equivalent of heat = 4.19 J/calorie, the energy
Cp – Cv = b for nitrogen gas
spent in this process in overcoming
The correct relation between a and b is
intermolecular forces is
a) a = 14 b b) a = 28 b
a) 540 cal b) 40 cal
c) 500 cal d) zero 1
b c) a  d) a = b
46. If heat of 110 J is added to a gaseous system 14
whose internal energy increases by 40 J, then 53. 310 J of heat is required to raise the temperature
the amount of external work done is of 2 mole of an ideal gas at constant pressure
from 25°C to 35°C. The amount of heat required
a) 180 J b) 70 J
to raise the temperature of the gas through the
c) 110 J d) 30 J same amount at constant volume is
47. The temperature of 5 moles of a gas at constant a) 384 J b) 144 J
volume is changed from 100°C to 120°C. The c) 276 J d) 452 J
change in internal energy is 80 J. The total heat 54. 40 gram of argon is heated from 40°C to 100°C
capacity of the gas at constant volume in joule/K (R = 2 cal/mole). Heat absorbed at constant
will be volume is
a) 8 b) 4 a) 100 cal. b) 80 cal.
c) 0.8 d) 0.4 c) 180 cal. d) 120 cal.
42. (d) 43. (c) 44. (b) 45. (c) 46. (b) 47. (b) 48. (a) 49. (b) 50. (c)
51. (c) 52. (a) 53. (b) 54. (c)
55. Two cylinders A and B fitted with pistons 61. 5.6 liter of helium gas at STP is adiabatically
contain equal amounts of an ideal diatomic
compressed to 0.7 liter. Taking the initial
gas at 300 K. The piston of A is free to move
while that of B is held fixed. The same amount temperature to be T1, the work done in the
of heat is given to the gas in each cylinder. If process is
the rise in temperature of the gas in A is 30 K,
then the rise in temperature of the gas in B is 9 3
a) RT1 b) RT1
a) 30 K b) 18 K 8 2
c) 50 K d) 42 K 15 9
c) RT1 d) RT1
DIFFERENT THERMODYNAMIC PROCESSES 8 2
56. A diatomic ideal gas is compressed adiabatically 62. An ideal gas at 27°C is compressed adiabatically
1 8 5
to of its initial volume. If the initial to of its original volume. If   , then the
32 27 3
rise in temperature is
temperature of the gas is Ti (in Kelvin) and the
a) 450 K b) 375 K
final temperatures is Ti , the value of  is
c) 325 K d) 405 K
a) 1 b) 2
63. In which process the PV indicator diagram is
c) 3 d) 4
a straight line parallel to volume axis
57. A gas for which  = 1.5 is suddenly compressed
a) Isothermal b) Isobaric
1
to th of the initial volume. then the ratio of c) Irreversible d) Adiabatic
4
the final to the initial pressure is 64. An ideal gas has volume V0 at 27°C. It is heated
a) 1 : 16 b) 1 : 8 at constant pressure so that its volume becomes
2 V0. The final temperature is
c) 1 : 4 d) 8 : 1
a) 54°C b) 32.6 °C
58. One mole of an ideal gas with  = 1.4, is
c) 327°C d) 150 K
adiabatically compressed so that its temperature
rises from 27°C to 35°C. The change in the 65. During an adiabatic process, the pressure of a
internal energy of the gas is (R = 8.3 J/mol. K) gas is found to be proportional to the cube of
a) –166 J b) 166 J its absolute temperature. The ratio Cp / Cv for
the gas is
c) –168 J d) 168 J
59. Identify the wrong statement 3 4
a) for isothermal process, T  0 a) b)
2 3
b) for isochoric process, V  0
c) for isobaric process, P  0 5
c) 2 d)
d) for cyclic process, W  0 3
60. One mole of O gas having a volume equal to 66. Which of the following is a true statement?
2
22.4 litres at 0°C and 1 atmospheric pressure a) the total entropy of thermally interacting
system is conserved
is compressed isothermally so that its volume
b) Carnot engine has 100% efficiency
reduces to 11.2 litres. The work done in this
c) total entropy does not change in a reversible
process is
process
a) –1672.5 J b) 1728 J d) total entropy in an irreversible process can
c) –1728 J d) –1572.5 J either increase of decrease
55. (d) 56. (d) 57. (d) 58. (b) 59. (d) 60. (d) 61. (a) 62. (b) 63. (b)
64. (c) 65. (a) 66. (c)
67. Two moles of helium 70. In the cyclic process shown on the V-P
gas are taken over diagram, the magnitude of the work done is
the cycle ABCDA, as
shown in PT
diagram, figure.
Assuming the gas to
be ideal, the work
done on the gas in taking it from A to B is
a) 300 R b) 400 R
c) 500 R d) 200 R
68. A cyclic process ABCA 2 2
as shown in V-T  P2  P1   V2  V1 
a)    b)   
diagram, figure, is  2   2 
performed with a

constant mass of an c) ( P2  P1 )( V2  V1 ) d) ( P2 V2  P1V1 )
4
ideal gas. Which of the following graphs in
71. In the P-V diagram shown in figure, ABC is a
figure. represents the corresponding process
semicircle. The work done in the process ABC is
on a P-V diagram? a) zero
b) 4 J

a) b) c) J
2

d)  J
2
c) d) 72. A thermodynamic system is taken through the
cycle PQRSP process. The net work done by
the system is
69. A cyclic process ABCD is shown in the P-V
diagram. Which of the following curves
represent the same process?
a) 20 J b) –20 J
c) 400 J d) –374 J
73. Three moves of an ideal
monoatomic gas perform
a cycle as shown in figure.
a) b) The gas temperatures in
different states are
T1 = 400 K, T2 = 800 K,
T3 = 2400 K, T4 = 1200 K.
The work done by the gas during the cycle will
c) d) be
a) 20 kJ b) 30 kJ c) 40 kJ d) 80 kJ
67. (b) 68. (a) 69. (b) 70. (c) 71. (c) 72. (b) 73. (a)
HEAT ENGINE – REFRIGERATORS 80. An ideal gas heat engine operates in Carnot
cycle between 227°C and 127°C. It absorbs
1 6 × 104 cals of heat at higher temperature.
74. A reversible heat engine converts th of heat
6 Amount of heat converted to work is
it absorbs from source into work. When a) 4.8 × 104 cals b) 2.4 × 104 cals
temperature at which heat exhausts is 4
c) 1.2 × 10 cals d) 6 × 104 cals
a) 500 K b) 100 K 81. In a refrigerator, heat from inside at 270 K is
c) 0 K d) 600 K transferred to a room at 300 K. How many
calories of heat will be delivered to the room
75. An engine is supposed to operate between two
reservoirs at temperature 727°C and 227°C. The for each joule of electric energy consumed
maximum possible efficiency of such an a) 4.18 cal b) 2.38 cal
engine is c) 6.56 cal d) 1.80 cal
82. A refrigerator whose coefficient of performance
a) 1/2 b) 1/4
is 5 extracts heat from the cooling compartment
c) 3/4 d) 1
at the rate of 250 J/cycle. The electric energy
76. 200 cal of heat is given to a heat engine so that spent per cycle is
it rejects 150 cal of heat. If source temperature a) 250 J b) 350 J
is 400 K, then the sink temperature is
c) 300 J d) 50 J
a) 300 K b) 200 K 83. The coefficient of performance of a Carnot
c) 100 K d) 50 K refrigerator working between 30°C and 0°C is
77. A Carnot engine takes 3 × 106 cals of heat from a) 10 b) 1
a reservoir at 627°C and gives it to a sink at c) 9 d) 0
27°C. The work done by the engine is 84. A carnot engine, having an efficiency of  = 1/10
a) 4.2 × 106 J b) 8.4 × 106 J as heat engine, is used as a refrigerator. If the
c) 16.8 × 106 J d) 3 × 106 J work done on the system is 10 J, the amount
78. A Carnot engine working between 300 K and of energy absorbed from the reservoir at lower
600 K has a work output of 800 J per cycle. The temperature is
amount of heat energy supplied to the engine a) 99 J b) 90 J
from the source in each cycle is c) 1 J d) 100 J
a) 800 J b) 1600 J 85. A refrigerator with coefficient of performance
c) 3200 J d) 6400 J 1
release 200 J of heat to a hot reservoir. Then
79. A Carnot engine works between 600 K and 300 3
K. In each cycle of operation, the engine draws the work done on the working substance is
1000 J of heat energy from the source. The 100
a) J b) 100 J
efficiency of the engine is 3
a) 50% b) 70% 200
c) J d) 150 J
c) 20% d) 80% 3
74. (a) 75. (a) 76. (a) 77. (b) 78. (b) 79. (a) 80. (c) 81. (b) 82. (d)
83. (c) 84. (b) 85. (d)

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Kinetic Theory Of Gases And Thermodynamics

KINETIC THEORY OF GASES SYNOPSIS

Graham’s Law Of Diffusion

Dalton’s Law Of Partial Pressures

SPEED OF GAS MOLECULES

Root Mean Square Speed

RELATION BETWEEN  ,  rms AND  mp :

rms :  : mp  1.73:1.60 :1.41

Clearly, rms    mp

(The distruibution of molecular speeds)

Where dN = Number of molecules with speeds between v and v + dv.

LAW OF EQUIPARTITION OF ENERGY

VANDER WAAL’S EQUATION FOR REAL GAS

n1CV1 T  n2CV2 T  ......  (n1  n2  ...)CVmix T

n1CV1  n2 CV2  ......

and C Pmix  CVmix  R

n1CV1 T  n2CV2 T  ......  (n1  n2  ...)CVmix T

ZEROTH LAW OF THERMODYNAMICS

Its value is, 1 calorie = 4.186 J  4.2 J .

 Heat is measured by using calorimeter.

Work Done By A Gas During Change In Volume

w   p dv =Area under P-V curve.

 Work is a path dependent quantity

U  U final  U initial

Where K = Boltzmann's constant.

Where, f = no. of degrees of freedom.

FIRST LAW OF THERMODYNAMICS

for bulk changes, Q  U   pdv

Significance And Limitations Of First Law

Qp  m  c p dT , if cpdepends on temperature.

 Specific heat of gas at constant volume (cv):

Qv  mcv T , if cv is constant.

Cp – CV=R, where R is universal gas constant

CV, CP & VALUES OF DIFFERENT GASES

gas of specific heat at constant volume CV 2 then

(Cp )mixture  (Cv )mixture  R

 At constant pressure,fraction of heat absorbed that is converted into internal energy is

 At constant pressure,fraction of heat absorbed that is converted into external workdone is

 The slope of adiabatic curve is  times to that of the isothermal curve.

 The adiabatic elasticity of gas is  p.i.e  times isothermal elasticity..

 Bulk modulus of elasticity, K = 0.

 Ex.:- Boiling of water into steam.

Source Engine Sink

b) Engine derives an amount ‘ Q1’ of heat from the source.

CARNOT (OR REVERSIBLE OR IDEAL)

Therefore, efficiency of the Carnot engine is,

 Always ir  r but,  ir can not be greater than r .

(Hot Reservoir) ( Cold Reservoir)

 Change in entropy during phase change is

1. (d) 2. (a) 3. (b) 4. (d) 5. (c) 6. (c) 7. (c) 8. (c) 9. (a)

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