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fiziks

Forum for CSIR-UGC JRF/NET, GATE, IIT-JAM/IISc,

JEST, TIFR and GRE in

PHYSICS & PHYSICAL SCIENCES

(IIT-JAM/JEST/TIFR/M.Sc Entrance)

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Thermal & Statistical Mechanics

1. Kinetic theory of gases..(1-29)

1.1 Basic assumption of kinetic theory

1.1.1 Pressure exerted by a gas

1.2 Gas Law for Ideal gases:

1.2.1 Boyles Law

1.2.2 Charles Law

1.2.3 Avogadros Law

1.2.4 Grahams Law of Diffusion

1.2.5 Ideal Gas Equation:

1.3 Kinetic Interpretation of Temperature

1.4 Maxwell-Boltzmann Distribution Law

1.4.1 The Distribution in term of Magnitude

1.4.2 To Determine Value of in term of Temperature T

1.4.2 Average Velocity

1.4.3 Root Mean Square Velocity

1.4.4 Most Probable Velocity

Questions and Solutions

2. Real Gases.(30-43)

2.1 Andrews Experiment on Carbon Dioxide

2.2 van der Waals Equation of State.

2.3 Correction in Ideal Gas Equation to Achieve van der Waals Gas Equation of State.

2.3.1 Correction for Finite Size

2.3.2 Correction for Intermolecular Attraction

2.3.3 Maxwell Equal Area

2.3.4 Critical Point

2.3.5 van der Waals Equation of State and Virial Coefficient

Questions and Solutions

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3. Basics of Thermodynamics and Laws of Thermodynamics(44-79)

3.1 Mathematical Formulations of thermodynamics.

3.1.1 Some important Formulas

3.2 Fundamental Concept

3.2.1 System

3.2.2 Isolated System

3.2.3 Thermodynamical State

3.2.4 State Function

3.2.5 Intensive and Extensive Properties

3.3 The Ideal Gas:

3.4 Laws of Thermodynamics

3.4.1 Zeroth law of Thermodynamics:

3.4.2 First law of Thermodynamics:

3.4.3 Work Done during Different Process.

3.4.4 Specific Heat

3.4.5 Heat Capacity of Ideal Gas:

3.4.6 Molar Heat Capacity

3.4.7 Coefficient of Volume Expansion or Expansivity

3.4.8 Isothermal Elasticity and Isothermal Compressibility

3.5 Different Types of Thermo Dynamical Process and use of First Law of

Thermodynamics

3.5.1 Isochoric Process:

3.5.2 Isobaric Process

3.5.3 Isothermal Process

3.5.4 Adiabatic Process

Questions and Solutions

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4. Second Law of Thermodynamics and Entropy...(80-110)

4.1 Second Law of Thermodynamics

4.2 Heat Engines

4.2.1 Heat Reservoir

4.2.2 Efficiency of Heat Engine ()

4.2.3 Carnot Cycle

4.3 Entropy

4.3.1 Inequality of Clausius

Questions and Solutions

5. Maxwell relation and Thermodynamic Potential..(111-142)

5.1 Maxwell relations

5.2 Different types of thermodynamic potential and Maxwell relation

5.2.1 Internal Energy

5.2.2 Enthalpy

5.2.3 Helmholtz Free Energy

5.2.4 Gibbs Energy

5.3 Application of Maxwell Relation

5.3.1 First T dS Equation

5.3.2 Second T dS Equation

5.3.3 Third T-dS Equation:

5.3.4 First Energy Equation

5.3.5 Second Energy Equation

Questions and Solutions

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6. Phase Transition and Low Temperature Physics...(143-167)

6.1 Third Law of Thermodynamics and Attainable of Low Temperature

6.2 Production of Low Temperature and Joule Kelvin Expansion:

6.3 Phase Transition

6.3.1 First Order Phase Transition

6.3.2 Equilibrium Between Two Phases

6.3.3 Clapeyron-Clausius Equation

6.3.4 Liquid-Vapour Phase Transition

6.3.5 Properties of First Order Phase Transition

6.3.6 Second Order Phase Transition:

Questions and Solutions

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Chapter - 1

Kinetic Theory of Gases

1.1 Basic Assumption of Kinetic Theory:

1. Any infinitely small volume of a gas contains a large number of molecule.

2. A gas is made up identical molecule which behaves as rigid, perfectly elastic, hard

sphere.

3. The molecules continuously move about in random directions. All directions of motion

are equally probable.

4. The size of the molecules is much less than the average distance between them.

5. The molecule of a gas exert no force on each other except when they collide.

6. The collision between molecules and with walls are perfectly elastic.

7. The direction of molecular velocities are assumed to be distribute uniformly.

8. The molecules move with all speeds ranging from 0 to .

9. The time of collision is much less than the time between collisions.

1.1.1 Pressure Exerted by a Gas

Suppose there are n molecules per cubic meter each of mass m, and its is assumed that ni

no. of molecule have velocity vi .

Mathematically

ni = n and vi2 = vix2 + viy2 + viz2

where vix viy and viz are x, y, z component of velocity of gases.

vi2

From assume of kinetic theory of gases v ix2 = viy2 = viz2 =

3

suppose molecules are kept in the cubic container of parameter L .

A molecule moving in the x direction will have momentum mvix normal to face of the

cube before collision

Pix = mv ix ( mvix ) = 2mvix

Force acting on the wall by molecule is f ix = = ==

t 2L L

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mn v 2

Pressure exert on the wall of container by molecule Pix = i3 ix

L

so that pressure in the x direction expected by all group

m

Px = Pix = ni vix2

L3

Average value of v2 is given by

n v 2

i ix n v 2

i ix

v x2 = i

= i =1

n i n

v2

for isotropic system v 2

x = v 2

y = v 2

z =

3

So Px can be written as

2

m 1m 1 mn v

Px = 3 n v x2 , P = Px = n v2 P=

L 3 L3 3 V

1

PV = mN v 2

3

where V is volume of the container and v 2 is average value of square of velocity.

1.2.1 Boyles Law

At constant temperature (T ) , the pressure ( P ) of a given mass a gas is inversely

1

P

V

1.2.2 Charles Law

At constant pressure ( P ) the volume of a given mass of a gas is proportional to its

temperature (T)

V T

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1.2.3 Avogadros Law

At the same temperature and pressure, equal volume of all gases contain equal number of

molecules (N).

N1 = N2

1.2.4 Grahams Law of Diffusion

When two gases at the same pressure and temperature are allowed to diffuse into each

other, the rate of diffusion (r) at each gas is inversely proportional to square root at

density of gas ()

r1 2

=

r2 1

Daltons Law of Partial Pressure: The sum of pressure exerted (P) by each gas occupying

the same volume as that of the mixture (P1, P2, P3,.)

P = P1 + P2 + P3 +.

1.2.5 Ideal Gas Equation:

Consider a sample of an Ideal gas at pressure P, volume V and temperature T the gas

follows the equation

PV = nRT

Where n is number of molecules and R is proportionality constant known as gas constant

R = 8.314 J/mol/K

R 8.314

Boltzmann constant K is ratio between R to Avogadro number NA k B = =

N A 6.03 1023

k B = 1.3 10 23 J / K

Example: Find the maximum attainable temperature of ideal gas in each process given

by p = p0 V 2 ; where p 0 , and are positive constants, and V is the volume of one

mole of gas.

Solution: P = P0 V 2 (i)

Number of mole of gas = 1

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RT

We know PV = nRT P = put in (i)

V

RT P0V V 3

= P0 V 2 T = (ii)

V R R

dT P 3V 2

For T maximum, =0 0 =0

dV R R

P0 2 P0

V = put in (ii) one will get Tmax = P0

3 3 3

Example: Two thermally insulated vessel 1 and 2 are filled with air. They are connected by a

short tube with a value. The volume of vessels and the pressure and temperate of air in

them are (V1 , P1 , T1 ) and ( V2 , P2 , T2 ) respectively. Calculate the air temperate and

pressure established after opening of value if air follow Ideal gas equation.

P1V1

Solution: For vessel (1) P1V1 = n1 RT1 n1 =

RT1

P2V2

For vessel (2) P2V2 = n2 RT2 n2 =

RT2

After opening the value let pressure volume and temperature is P, V, T

PV = nRT

V = V1 + V2

P1V1 P2V2

n = n1 + n2 = +

RT1 RT2

Hence system is isolated then

Energy of (1) + energy of (2) = energy of composite

3 3 3

n1 KT1 + n2 KT2 = (n1 + n2 )KT

2 2 2

n1T1 + n2T2 = (n1 + n2 ) / T .

n1T1 + n2T2

T=

n1 + n2

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P1V1 (P V )

T1 + 2 2 T2

RT1 RT2 ( PV

1 1 + P2V2 )

= T = T1T2

1 1T2 + P2V2T1

P1V1 P2V2 PV

+

RT1 RT2

PV = nRT P= P=

V V1 + V2

Example: A horizontal cylinder closed from one end is rotated with a constant angular velocity

about a vertical axis passing through the open end of the cylinder. The outside air

pressure is equal to p 0 , the temperature to T , and the molar mass of air to M . Find the air

pressure as a function of the distance r from the rotation axis. The molar mass is assumed

to be independent of r .

Solution: Force equation of dr element.

dF = (dm )r 2 if S is cross section area then

dF dm 2 S

dP = = r dm = 2 dP

S S r

Also we know

dm

P(Sdr ) = RT

M

M, T

RT S

PS (dr ) = dP P0 S

M r 2 r

r P dP This end is

M 2 rdr = RT open in air

0 P0 P

M 2 r 2 P

= RT ln

2 P0

M 2 r 2

P = P0 e 2 RT

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1 2

Example: Prove that PA = mN v 2 and E = k BT = kBT in two dimension.

2 2

Solution: A molecule moving in the x direction will have momentum mvix normal to face of the

cube before collision

Pix = mvix ( mvix ) = 2mvix

Force acting on the wall by molecule is f ix = = ==

t 2L L

mni vix2

Pressure exert on the wall of container by molecule Pix =

L3

So that pressure in the x direction expected by all group

m

Px = Pix = 3

ni vix2

L

Average value of v 2 is given by

n v 2

i ix nv 2

i ix

v x2 = i

= i =1

n i n

v2

For two dimensional system v 2

+ v 2

= v 2

and v 2

x = v 2

y =

2

x y

So Px can be written as

2

m 1 m 1 mn v

Px = 2 n v x2 , P = Px = n v2 P=

L 2 L2 2 A

1

PA = mN v 2

2

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1.3 Kinetic Interpretation of Temperature

According to assumption of Kinetic theory of gases, there is only translation motion of

the molecule and there is not any potential acting between them, so

Average energy E of gases are equivalent to Average translation energy of a molecule

1

E = m v2

2

1 2 1 2

Pressure at P as P = mn v 2 = n m v 2 = n E

3 3 2 3

2 2 N

PV = Vn E PV = N E where n = number density

3 3 V

3 RT 3 R

E = and E = T

2 NA 2 NA

3

E = K BT where k B is Boltzman constant

2

So average kinetic energy is given by

3

E = k BT where T is absolute temperature.

2

Example: It is possible to treat electromagnetic radiation in container whose wall is mirrors, as a

gas of particle (photons) with a constant speed c and whose energy is related to their

momentum p which is directed parallel to their velocity by E = pc .Show that if

1

container is full of radiation the equation of state is PV = E

3

1 1 1 G G

Solution: Pressure P = nm v 2 = n mv v = n p v

3 3 3

For Photon v = c and velocity is parallel to momentum, so

1 1N

P = n Pc P= pc

3 3V

1 1

PV = Npc PV = E

3 3

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1.4 Maxwell-Boltzmann Distribution Law: z

Distribution of Molecular velocity in perfect gas. dv

gas where molecules have no vibrational or rotational y

energies.

In the equilibrium state of the molecules have complete x

random motion and probability that a molecule has a given velocity component is

independent of other two components.

In given figure dv is volume element in velocity space for a molecule at velocity

G

v (v x , v y , v z ) .

v 2 = v x2 + v y2 + v z2

We need to calculate number of molecules simultaneously having component in the range

v x to v x + dv x , v y to v y + dv y and v z to v z + dv z

selected at random has velocities in a given range is a function purely at the magnitude of

velocity and the width of the interval.

So fraction of molecule having velocity component in the range v x to v x + dv x , v y to

= f (v x ) f (v y ) f (v z )dv x dv y dv z

dN

N

where dN is number of molecule having between velocity v to v + dv and N is total

number of molecules.

dN = N f (v x ) f (v y ) f (v z )dv x dv y dv z

Number of molecule having velocity vx to vx + dvx, vy to vy + dvy and vz to vz + dvz is same

as number of molecule having velocity v to v + dv.

So N f (v x ) f (v y ) f (v z )dv x dv y dv z = N F (v 2 ) dv x dv y dv z

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G

F is some function of v (magnitude of velocity) and for fixed value of v , F ( v 2 ) is

2

constant.

So dF (v 2 ) = 0 is equivalent to d [ f (v x ) f (v y ) f (v z )] = 0

f ( vx ) dvx f ( v y ) f ( vz ) + f ( v y ) dv y f ( vx ) f ( vz ) + f ( vz ) dvz f ( vx ) f ( v y ) = 0

f (v x ) f (v y ) f (v z )

dv x + dv y + dv z = 0 (i)

f (v x ) f (v y ) f (v z )

v 2 = constant v x2 + v y2 + v z2 = v 2

vxdvx + vydvy + vzdvz = 0 (ii)

by method of Lagranges method of undetermined multiplies multiply by 2 in equation

(ii) and add in equation (i)

f (v x ) f (v y ) f (v z )

+ 2 v x dv x + + 2 v y dv y + + 2 v z dv z = 0

f (v x ) f (v y ) f (v z )

hence v x , v y and v z are independent

f ( vx ) f ( vy ) f ( vz )

+ 2 vx = 0 + 2 vy = 0 + 2 vz = 0

f ( vx ) f ( vy ) f ( vz )

f (v x ) = Ax e vx f (v y ) = Ay e v y f (v z ) = Az e vz

2 2 2

1 n +1

e v dv =

2

v n

n +1

( ) 2

0

2 2

e vx dvx = 1 = Ax 2 e vx dvx = 1

2 2

Ax

0

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1/ 2 1/ 2 1/ 2

Ax = Similarly, Ay = Az =

1/ 2 1/ 2 1/ 2

f (v x ) = v x2

, f (v y ) = v 2y

, f (v z ) = e vz

2

e e

3/ 2

dN

e (v x + v y + v z )dv x dv y dv z

2 2 2

=

N

where < v x < , < vy < , < vz <

1.4.1 The Distribution in Term of Magnitude

v 2 = v x2 + v y2 + v z2 which is equation of sphere and dv x dv y dv z can be replace by 4v 2 dv

3/ 2

dN

f (v )dv =

2

= 4e v v 2 dv 0<v<

N

1.4.2 To Determine Value of in Term of Temperature T.

Mean square velocity v 2 ( ) can be calculated by

v f (v )dv

2 2

3/ 2 3/ 2

1

4 v 4

v 2

4

e dv 5/ 2

0 2 5/ 2

3/ 2

1 3 1 3 1

4 v2 =

2 5/ 2

2 2 2

Now average energy of temperature T equivalent to

3 1

k BT = m v 2

2 2 T1

3 1 31 m T2

kBT = m = =

2 2 2 2 k BT f (v )

3/ 2 (

m vx2 + v 2y + vz2 )

m

So f ( vx , v y , vz ) = e 2 k BT

dvx dv y dvz

2 k BT v

T1 < T1

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3/ 2 mv 2

m

f ( v ) dv = 4

2

ve 2 k BT

dv

2 k BT

1.4.2 Average Velocity

3/ 2 mv 2

m 8k B T

v = vf (v ) dv = 4 e

2 k BT

v 3dv =

0 2 k BT m

1.4.3 Root Mean Square Velocity

1/ 2

[v ]2 1/ 2

= v 2 f (v )dv

0

1/ 2 1/ 2

m 3/ 2 mv

2

3k BT

= 4 e 2 kBT v 2 dv =

2 k BT 0

m

df 2k B T

1.4.4 Most Probable Velocity v p : = 0 vp =

dv m

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1

Example: For Maxwellian gas find the v

v

3/ 2 1/ 2

8k BT 1 m 1 2m

Solution: v =

m

v

= 4

2 k BT

0 v f ( v ) dv = kBT

1 4

= v

v

Example: If vx and vy are x and y component of velocity then find the average value of

(av x + bv y )2

(av x + bv y )2 = a 2 v x2 + b 2 v y2 + 2 ab v x v y

= a 2 v x2 + b 2 v y2 + 2ab v x v y

3/ 2 (

m vx2 + v 2y + vz2 )

m

vx = ve

2 k BT

dvx dv y dvz = 0

2 k BT

x

3/ 2 (

m vx2 + v 2y + vz2 )

m k BT

= ve dvx dv y dvz =

2 2 2 k BT

v

2 k BT

x x

m

k BT

Similarly, v y = 0 v y2 =

m

(av x + bv y )2 = a 2 v x2 + b 2 v y2 + 2 ab v x v y

+ b2 B + 0 = B ( a 2 + b2 )

k BT kT kT

= a2

m m m

Example: Write down expression of energy distribution function for Maxwellian gas between E

and E + dE . Hence find E down E 2 .

1 2 dE

Solution: E= mv , dv =

2 (2mE )1/ 2

3/ 2 mv 2

m

f ( v ) dv = 4 e 2 k BT

v 2 dv put value of v and dv

2 k BT

E

2 1

f ( E ) dE = e k BT

E1/ 2 dE 0< E <

( k BT )

3/ 2

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3

E = Ef (E ) dE E = k BT

0

2

E 2 = E 2 f ( E ) dE ,

0

E

2 1

2 2 5 3 15

=E . ( k BT ) . . = . ( k BT )

2 2 2

E e k BT

E1/ 2 dE =

( k BT )

3/ 2

0 2 2 2

Example: Write down expression of energy distribution function for Maxwellian gas between E

and E + dE in two dimensional system . Hence find E .

1 2 dE

E= mv , dv =

2 (2mE )1/ 2

2/2 mv 2

m

f ( v ) dv = 2 e 2 k BT

vdv put value of v and dv

2 k BT

E

1

f (E )dE = e K BT dE 0<E<

(k BT )

E = Ef (E ) dE E = k BT

0

Example: Using the Maxwell distribution function, calculate the mean velocity projection v x

the mean value of the modulus of the modulus of this projection vx if the mass of

each molecule is equal to m and the gas temperature is T .

1/ 2

m

m 2

vx

2 k BT

vx N e dvx

v dN

Solution: We know Mean Velocity = v x = x =

2 k BT =0

N N

1/ 2

m 2 kBT vx2

m

x 2k BT e

v N dvx

Mean speed vx =

N

1/ 2

m 2 kBT vx2

m

2 v x N e dvx

vx =

0

2k BT vx =

2 k BT

N m

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MCQ (Multiple Choice Questions)

Q1. Consider a Maxwellian distribution of the velocity of the molecules of an ideal gas. Let

vmp and vrms denote the most probable velocity and the root mean square velocity,

vrms

respectively. The magnitude of the ratio is

vmp

3

(a) (b) 2/3 (c) 2/3 (d) 3 / 2

2

Q2. For temperature T1 > T2 , the qualitative temperature dependence of the probability

distribution F (v ) of the speed v of a molecule in three dimensions is correctly

represented by the following figure

T2

T1

F(v)

F(v)

T1 T2

(a) (b)

v v

T1

F(v)

F(v)

T2 T1

T2

(c) (d)

v v

Q3. The speed v of the molecules of mass m of an ideal gas obeys Maxwells velocity

distribution law at an equilibrium temperature T . Let (v x , v y v z ) denote the components of

2

(

(a) 2 2 k B T / m ) (

(b) 2 + 2 k B T / m )

(c) ( + ) k B T / m (d) ( ) k BT / m

2 2

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Q4. The speed v of the molecules of mass m of an ideal gas obeys Maxwells velocity

distribution law at an equilibrium temperature T . Let (v x , v y v z ) denote the components of

the velocity and k B the Boltzmann constant. The average value of ( vx v y ) , where

2

2

k T

(a) 0 (b) 2 B

m

2 2

k T 2k T

(c) B

2

(d) B

2

2m m

Q5. The statistical energy distribution underlying an ideal gas law gives the number of

molecules with kinetic energies between E and E + dE as N (E )dE . Which one of the

following expressions can be used to obtain average kinetic energy over the collection of

N molecules?

1 1 +

(a) EN (E )dE (b) N (E )dE

N 0 N

1 1

(c)

N N (E )dE

0

(d)

N

E dE

dN

Q6. The plots of Maxwells distribution fraction

dv T1

versus speed (c) for a given sample of a gas at three

dN

different temperatures T1 ,T2 and T3 respectively, dv I T2

are shown in the above diagram. If the areas on the II

III

T3

c-axis under three curve I, II and III be denoted by

AI , AII and AIII respectively, then which one of the v

following is correct?

(a) AI > AII > AIII (b) AI = AII = AIII

(c) AI < AII < AIII (d) AII < AI < AIII

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Q7. Temperature of an ideal gas is increased such that the most probable velocity of

molecules increase by a factor of 4. By what factor will the rms velocity increase?

3

(a) (b)2 (c)4 (d)16

2

Q8. A gas at thermal equilibrium satisfying Maxwells velocity distribution

Given v = average speed of the molecules

v p = most probable speed

Q9. A hypothetical speed distribution for a sample of N gas particles is shown below.

Here P (v ) = 0 for v > 2v0 . How many particles have speeds between 1.2v0 and 1.9v0 ?

P(v )

a

0 V0 2V0

Speed V

N 7N 2N

(a) (b) (c) (d) None of these

5 15 21

Q10. A parallel beam of nitrogen molecules moving with velocity v m/s impinges on a wall at

an angle to its normal. The concentration of molecules in the beam n cm3. The pressure

exerted by the beam on the wall assuming the molecules to scatter in accordance with the

perfectly elastic collision law is given by

(a) 2nmv 2 cos (b) nmv 2 cos

(c) 2nmv 2 sin (d) nmv 2 sin

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Q11. If The mass of each molecule is equal to m then The temperature of a gas will the number

of molecules, whose velocities fall within the given interval from v to v + dv be the

greatest

mv 2 mv 2 mv 2 mv 2

(a) T = (b) T = (c) T = (d) T =

kB 2k B 3k B 4k B

Q12. Using the Maxwell distribution function, the mean value of the modulus of the modulus

of this projection in x direction .e. v x if the mass of each molecule is equal to m and

k BT k BT 2 k BT

(a) 0 (b) (c) (d)

m m m

1

Q13. Making use of the Maxwell distribution function, if the mean value of the reciprocal

v

temperature T ,if the mass of each molecule is equal to m .then which one of the following

is correct.

1 1 1 4 1 2 1 4

(a) = (b) = (c) = (d) =

v v v v v v v v

Q14. If the root mean square velocity of hydrogen molecules exceeds their most probable

velocity by v m/s then temperature is given by

mv 2 mv

(a) T = (b) T =

( ) ( )

2 2

kB 3 2 kB 3 2

mv mv

(c) T = (d) T =

kB ( 3 2 )

2

kB ( 3 2 )

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Q15. In the case of ideal gaseous in three dimensional the temperature at which the velocities

of the molecules v1 m / s and v 2 m / s are associated with equal values of the Maxwell

distribution function F (v )

m ( v22 v12 ) (

m v22 + v12 )

(a) T = (b) T =

4k B ln v2 / v1 4k B ln v2 / v1

(c) T =

(

m v22 v12 ) (d) T =

(

m v22 + v12 )

4k B ln v1 / v2 4k B ln v1 / v2

Q16. A gas consists of molecules of mass m and is at a temperature T in three dimension.

Making use of the Maxwell velocity distribution function, the corresponding distribution

of the molecules over the kinetic energies E is given by .

3/ 2 3/ 2

1 1

E E

(a) f ( E )dE = e k BT

E .dE (b) f ( E )dE = 2 e k BT

E .dE

k BT k BT

3/ 2 3/ 2

1 1

E E

(c) f ( E )dE = e k BT

E.dE (d) f ( E )dE = 2 e k BT

E.dE

B

k T

B

k T

Making use of the Maxwell velocity distribution function, the corresponding distribution

of the molecules over the momentum p is given by

p2 p2

1 2 mk BT 1 2 mk BT

(a) f ( p ) = e pdp (b) f ( p ) = e pdp

2mk B

T B

mk T

p2 p2

1 2 mk BT 1 2 mk BT

(c) f ( p ) = e dp (d) f ( p ) = e dp

2mk B T mk B T

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MSQ (Multiple Select Questions)

Q18. Consider the following statements related to kinetic theory of gases are correct:

(a) The molecules of a gas are all alike in size and shape and are hard, smooth, spherical

particles.

(b) The size of the molecules is very small compared to the volume occupied by the gas.

(c) The molecules exert no appreciable force on one another except during a collision.

(d) The collisions of the molecules with the walls of the containing vessel are inelastic.

Q19. Consider the following statements. Which of the following is correct?

(a) The root mean square velocity of molecules of a gas having Maxwellian distribution

of velocities, is higher than their most probable velocity, at any temperature.

(b) A very small number of molecules of a gas which posses very large velocities

increase the root mean square velocity without affecting the most probable velocity

(c) Most probable velocity is lowest among the most probable velocity, average velocity

and root mean square velocity.

(d) Mean square velocity is equal to square of mean velocity

Q20. Consider a collision between an oxygen molecule and a hydrogen molecule in a mixture

of oxygen and hydrogen kept at room temperature. Which of the following are possible?

(a) The kinetic energies of both the molecules increase.

(b) The kinetic energies of both the molecules decrease.

(c) The kinetic energy of the oxygen molecule increases and that of the hydrogen

molecule decreases.

(d) The kinetic energy of the hydrogen molecule increases and that of the oxygen

molecule decreases.

Q21. Consider a mixture of oxygen and hydrogen kept at room temperature. As compared to a

hydrogen molecule an oxygen molecule an oxygen molecule hits the wall

(a) with greater average speed (b) with smaller average speed

(c) with greater average kinetic energy (d) with smaller average kinetic energy

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Q22. Which of the following quantities is zero on an average for the molecules of an ideal gas

in equilibrium?

(a) any component of momentum (b) magnitude of momentum

(c) x component of velocity (d) speed

Q23. The average momentum of a molecule in a sample of an ideal gas depends on

(a) temperature (b) number of moles

(c) volume (d) mass of molecule

Q24. Which of the following quantities is the same for all ideal gases at the same temperature?

(a) The kinetic energy of 1 mole (b) The kinetic energy of 1 g

(c) The number of molecules in 1 mole (d) The number of molecules in 1 g

Q25. Which of the following is correct for ideal gas in two dimensional system

E n

(a) The energy distribution is f ( E ) exp E the value of n = 1 for two

k BT

dimensional function.

(b) The average kinetic energy is equal to k BT

3k BT

(c) The rms velocity of the gas is

m

k BT

(d) The most probable velocity of the gas is

m

Q26. Keeping the number of moles, volume and temperature the same, which of the following

are not the same for all ideal gases?

(a) rms speed of a molecule (b) density

(c) pressure (d) average magnitude of momentum

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NAT (Numerical Answer Type)

Q27. At temperature 0C the rms speed of gaseous hydrogen molecules equal to

that of oxygen molecules at 47 0 C .

Q28. Temperature of an ideal gas is increased such that the most probable velocity of

molecules increase by a factor of 4. The rms velocity increase by the factor

Q29. If density of hydrogen gas is 0.1 kg/m 3 and atmospheric pressure is 1.0 10 5 N/m 2 , then

root mean square speed of hydrogen molecule ism/sec

Q30. The temperature in Kelvin, at which the average speed of H 2 molecules will be same as

Q31. Consider a Maxwellian distribution of the velocity of the molecules of an ideal gas three

dimension. Let vmp and vrms denote the most probable velocity and the root mean square

vrms

velocity, respectively. The magnitude of the ratio is.(Answer must be up to

vmp

Q32. Consider a Maxwellian distribution of the energy of the molecules of an ideal gas in three

dimensions. Let Eav and Erms denote the average energy and the root mean square

Erms

energy, respectively. The magnitude of the ratio is.(Answer must be up to

Eav

one decimal point).

Q33. Consider a Maxwellian distribution of the velocity of the molecules of an ideal gas in two

dimension. Let vav and vrms denote the average velocity and the root mean square

vrms

velocity, respectively. The magnitude of the ratio is.(Answer must be up to

vav

two decimal point)

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Solutions

MCQ (Multiple Choice Questions)

Ans. 1: (a)

2 k BT 3k BT v 3

Solution: For Maxwellian distribution vmp = , vrms = rms =

m m vmp 2

Ans. 2: (a)

Solution: Area under the f (v ) curve is conserved and the mean velocity shift towards right for

higher temperature.

Ans. 3: (b)

Solution: Ideal gas obeys Maxwell velocity distribution law at equilibrium temperature. Then

average value of ( vx v y )

2

Now (v x y )

2

= 2 v x2 + 2 v y2 2 v x v y

k BT

v x = 0, v y = 0 and vx2 = = v y2 = vz2

m

( v vy )

2

Then x = 2 v x2 + 2 v y2 2 v x v y

( v x vy )

2

=2

k BT

m

k T

(k T

+ 2 B = 2 + 2 B

m m

)

Ans. 4: (b)

Solution: Ideal gas obeys Maxwell velocity distribution law at equilibrium temperature. Then

average value of ( vx v y )

2

( v v )

2

Now x y = 2vx2 vy2

2

k T

k T

( v v )

2

a v 2

x = B = v y2 = v z2 ,Then x y = B

2

m m

Ans. 5: (a)

Ans. 6: (b)

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dN

Solution: By Maxwells distribution law the area, of graph between versus velocity v is

dv

same at all temperature. Hence, A I = AII = AIII

Ans. 7: (c)

3RT

Solution: vrms = (i)

m

2 RT

Most probable velocity v p =

m

From Equation (i) and (ii)

vrms and v p both proportional T

Ans. 8: (d)

Ans. 9: (b)

Solution: Since, total probability is one, hence area of the figure should be one

1

av 0 + a(2v 0 v 0 ) = 1 P(v )

2

a

3 2

av 0 = 1 a =

2 3v 0

2 7N 0

now area between v = 1.2v0 to v = 1.9v0 = (1.9v 0 1.2v 0 ) = V0 2V0

3v 0 15 Speed V

Solution: Momentum transfer in one collision = 2mv cos

Number of molecules collision per second = n (vA )

dp

= nv(2mv cos )A

dt mt

F = 2nmv 2 cos

F / A = P = 2nmv 2 cos

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Ans. 11: (c)

3/ 2 mv 2

m

Solution: f (v ) = e 2 k BT

4v 2

2k BT

Here v = constant but T is variable.

df (v )

Then for f (v) maximum. =0

dT

m

3/ 2 mv 2

3 / 2 2 kBT 2

f (v ) = T e 4v

2k B

df (v ) mv 2 3 5 / 2 mv 2

= 0 , T 7 / 2 = T T =

dT 2k B 2 3k B

Ans. 12: (d)

1/ 2 1/ 2

m m

m 2 m 2

0 vx vx

vx N 2 kBT dvx +

2 k BT 2 k BT

e vx N e dvx

Solution: vx =

0

2 k BT = vx =

2 k BT

N m

Ans. 13: (b)

1

1 v (dN )

0 1 dN 1 m

3/ 2

m 2

v

Solution: = = = e 2 k BT

4v 2 dv

v N 0 v N 0 v 2k BT

1 2m 4

= =

v k BT v

Ans. 14: (a)

2k BT 3k BT 3k BT 2k BT

Solution: v p = and vrms = vrms v p = v =

m m m m

v m mv 2

= T T =

( 3 2 ) kB kB ( 3 2 )2

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Ans. 15: (a)

3/ 2

m

Solution: F (v) = e mv / 2 kBT 4 v 2

2 k BT

Let temperature T at which for v1 and v2 , F ( v ) are same.

3/ 2 3/ 2

m mv12 / 2 k BT m 2

e 4 v =

2

e mv2 / 2 kBT 4 v22

2 k BT 2 k BT

1

m ( v22 v12 )

T=

4k B ln ( v2 / v1 )

3/ 2 mv 2

m

Solution: f (v) = e 2 k BT

4v 2 dv

2k BT

1 2E dE

K .E . = E = mv 2 v = Differentiate: dE = mvdv vdv =

2 m m

3/ 2

m

E

2 E dE

f ( E )dE = e k BT

4 .

2k BT m m

3/ 2

1

E

f ( E ) dE = 2 e k BT

E .dE

k BT

mv 2

m 2 k BT

Solution: In two dimensional f (v) = e 2vdv

2k BT

mv 2

1 p2 m 2 k BT

K .E. = mv =

2

dp = mdv putting the value in f (v) = e 2vdv

2 2m 2k B

T

p2 p2

m 2 mkBT p dp 1 2 mkBT

f ( p ) = e 2 f ( p ) = e pdp

2k BT m m mk BT

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MSQ (Multiple Select Questions)

Ans. 18: (b) and (d)

Solution: Kinetic theory of gases are based on the following assumptions:

(i) All gases are made up of tiny elastic particles known as molecules.

(ii) the volume of the molecule is negligible.

(iii) The collision between the molecules is elastic.

(iv) They exert no force on each other.

Ans. 19: (a), (b) and (c)

dN

Solution:

dC

C av

C rms

C mp

Ans. 20: (c) and (d)

Solution: Momentum will transferred from one molecule to other as higher momentum will

change to lower momentum and vice versa .

Ans. 21: (b)

Ans. 22: (a) and (c)

Ans. 23: (a) and (d)

Ans. 24: (a) and (c)

Ans. 25: (b) and (d)

E

Solution: For two dimension f ( E ) exp n=0

k BT

Ef ( E )dE

average energy is 0

= k BT

f ( E )dE

0

2 k BT k BT

for two dimensional system vrms = vmp =

m m

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Ans. 26: (a), (b) and (d)

Solution: Only pressure is not function of mass.

Ans. 27: 2530 C

3RT

Solution: Vrms =

m

3RT0 3RTH m

= = TH = H (T0 )

m0 mH m0

m H = 2amu, m0 = 32 amu

2

so, TH = (320 )

32

= TH = (20 273) C = 2530 C

0

TH = 20 K

Ans. 28: 4

3RT 2 RT

Solution: v rms = and v p =

m m

vrms and v p are both proportional to T

Ans. 29: 1710 m/s

Solution: By kinetic theory of gases the pressure exerted by the gas on the wall of container is

given as

1

Pressure P = d v 2

3

Here, P = 1 10 5 N/m 2 , d = 0.1 kg/m 3 .

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3P

So, by Eq. (i) v =

d

3 1 105

vrms = = 3 10 6 m/s = 1710 m/s

0.1

Ans. 30: TH = 22 K

The average speed of a molecule of gas at constant temperature T is given as

8 RT v T M

v av = H = H N

M vN M H TN

given, vH = vN

TN M H = TH M N

TH M H 2

= =

TN M N 28

1 1

TH = TN = (273 + 35 )

14 14

TH = 22 K

Ans. 31: 0.8

2k BT 3k BT v 2

Solution: For Maxwellian distribution v mp = , vrms = mp =

m m vrms 3

Ans. 32: 1.8

3k BT 15

Solution: Eav = Erms = .k BT

2 2

15

2.7

= 2 =

Erms

= 1.8

Eav 3 1.5

2

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mv 2

m k BT

Solution: v = vav = vf (v)dv = v.e 2 kBT 2 vdv =

0

2 kBT 0 8m

mv 2

m 2k T

v 2

= v f (v)dv =

2

v 2 .e 2 kBT 2 vdv = B

0

2 k BT 0 m

2kBT

vrms =

m

2kBT

In two dimension system vrms =

m

2

vrms

= 1 = 1.4 = 2.25

vav .62

8

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Chapter - 2

Real Gases

2.1 Andrews Experiment on Carbon Dioxide

Andrews experiment investigated the behaviour of CO2 and analyse the Pressure

The observations are following:

1. Above a temperature of about (T = 480 C ) the CO2 resemble that of Ideal gas.

increases, which is indication from the ideal gas character.

3. At 31.40 C a Kink is observed which suggests the gas can be liquified under

compression.

4. As temperature is lower further the kink spread into a horizontal line, i.e.

compression produces liquification.

From A to B , CO2 behave as a gas. At the point P D

K J

B the liquification of the gas just starts. The gas

gas

P

liquid

that liquid and vapour coexist. At C , the gas is condensation 480 C

C B 0

F A 31.40 C

completely in the liquid phase. 21.50 C

Q 13.1 C

From C to D the slop is very steep since a liquid V

is almost incompressible.

Conclusion: The temperature at which it becomes possible to liquefy a gas under

compression is known as critical temperature (TC ) [In Andrew experiment

A gas can be liquified only if it cooled upto or below its characteristic critical

temperature.

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There exist a continuity of liquid and gaseous states, i.e. they are two distinct stages at a

continuous physical phenomenon.

2.2 van der Waals equation of state.

The van der Waals equation for real gases are given by

a

P + 2 (V b ) = RT for 1 mole of gas and

V

n2 a

P + (V nb ) = nRT for n mole of gas.

V2

1. Gas molecules have finite size

2. There are weak interaction force, which depends only upon distance between them.

3. The molecular density is small and the number of collisions with the walls of the

container are exactly the same point and finite size molecular.

2.3 Correction in Ideal Gas equation to achieve van der Waals gas equation of state.

2.3.1 Correction for finite size: if V is volume available for one mole of gas (volume of

container). If size of molecule take into account then (V b) is volume available for real

gas which is less than V . b is popularly known as covolume which is dependent

on the nature of gas.

Example: If Vm is molecular volume of real gas then prove that b = 4NVm if N is total number

of molecule in container.

d = 2r

The volume available to first molecule = V Vm

The volume available to second molecule = V Vs r r

Where Vs volume of exclusion i.e. around any

V s = 4

(2 r )3

4 d 3 Volume of exclusion 3

molecule, a spherical volume is Vs = will Vs = 8Vm

3

be denied to every other molecule.

4 ( 2r )

3

Volume of exclusion Vs =

3

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th

Similarly volume available to N molecule = V - (N - 1)Vs

Average volume available for each molecule

1 N N ( N 1) Vs N N

V =

N

V ( i 1)V

i =1

s =V

2N

=V

2

Vs = V 8Vm = V 4 NVm

2

(V - b) = V - 4 N Vm so b = 4NVm

A molecule in the equally in all direction so that there is no resultant force on it.

But for outermost layer close to surface there will be net inward force. So whenever a

molecule strikes the walls of container, the momentum exchange will be less than for

Ideal gas.

There forces are cohesive in nature and proportional to number of molecule.

a a

So for real gas change in pressure is . So for real gas pressure will be P+ 2

V2 V

a

So gas equation reduce to P + 2 (V b ) = RT

V

RT a

Then P= 2

V b V

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2.3.3 Maxwell Equal Area

2

James Clerk Maxwell replaced the isotherm

between a and c with a horizontal line positioned so that P e

1 c

the areas of the two hatched regions are equal (means a

b

PV d

area of adb and bec are equal). The flat line portion of

the isotherm now corresponds to liquid-vapor 0

VL 1 2 VG 3 4

equilibrium. As shown in figure.

The portions a d and c e are interpreted as metastable states of super-heated liquid

and super-cooled vapor respectively. The equal area rule can be expressed as:

VG

PV (VG VL ) = PdV

VL

where PV is the vapor pressure (flat portion of the curve), VL is the volume of the pure

liquid phase at point a on the diagram, and VG is the volume of the pure gas phase at

point c on the diagram. The sum of these two volumes will equal the total volume V .

Example One mole of a certain gas is contained in a vessel of volume V . At a temperature

T1 the gas pressure is p1 atm and at a temperature T2 the pressure is p2 atm. Find the Van

der Waals parameters for this gas.

Solution: it is given no of mole n = 1

a

P1 + 2 (V b ) = RT1 (i)

V

a

P2 + 2 (V b ) = RT2 (ii)

V

from (i) and (ii)

V 2 (T1 P2 T2 P1 )

a=

(T2 T1 )

R(T2 T1 )

b =V

(P2 P1 )

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Example: Under what pressure will carbon dioxide of molar mass M have the density at the

temperature T . If given gas is obeying for a Van der Waals gas.

M

Solution: Assume M is molar mass of the carbon dioxide and V is the volume so =

V

Van der wall equation (for one mole gas):

a

P + 2 (V b ) = RT

V

2 a M RT 2a RT 2a

P + 2

b = RT P= 2 P= 2

M M M M b M

b

2.3.4 Critical Point

The van der Waals equation of state for a gas is given by

a

P + 2 (V b ) = RT

V

where P, V and T represent the pressure, volume and temperature respectively, and a

and b are constant parameters. At the critical point, where all the roots of the above

cubic equation are degenerate means all roots are equal.

In another way mathematically For the critical isotherm is the point of inflection point

On basis of above definition one can find the critical volume Vc , critical pressure Pc and

For Van der Waals equation

a

P + 2 (V b ) = RT

V

RT a

P= 2 (i)

V b V

P

=0 for extremum point

V T

P RT 2a

= + 2 = 0 at V = Vc , T = Tc (ii)

V T (V b ) V

2

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P

2

V T

2 RT 6a

=0 at V = Vc , T = Tc (iii)

(V b )

3

V3

8a

Vc = 3b Tc =

27 Rb

a

Put value of Vc and Tc one can get Pc =

27b 2

RTc 8

= = c c which is popular known as critical coefficient for van der Waals gas.

Pc vc 3

2.3.5 van der Waals Equation of State and Virial Coefficient

According to virial theorem the equation of state is given by

pV = + + + ..... (i)

V V2

Where , and are first second and third virial coefficient .

For the Ideal gas = RT and other coefficient are zero.

Virial coefficient for Van der Waals gas

To put van der Waals equation in virial form we first rewrite it as

1

b a

pV = RT 1

V V

Using binomial theorem, we have

1

b b b2

1 = 1 + + + ....

V V V2

Hence

RTb a RTb 2

pV = RT + + + ..... . (ii)

V V2

As will be noted, van der Waals equation has only three virial coefficients and a

comparison with equation (i) yields

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= RT , = RTb a and = RTb 2

At the Boyle temperature, the second virial coefficient is zero. Hence,

RTB b a = 0

a

or TB =

Rb

From the preceding, section we recall that the critical temperature of a gas obeying van

der Waals equation of state is

8a

TC =

27 Rb

on comparing these expressions, we get

27

TB = TC = 3.375 TC

8

that is, the Boyle temperature, on the basis of Van der Waals equation, is 3.375 times the

critical temperature.

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MCQ (Multiple Choice Questions)

Q1. A gas behaves as an ideal gas at:

(a) very low pressure and high temperature

(b) high pressure and low temperature

(c) high temperature and high pressure

(d) low pressure and low temperature

a

Q2. In the van der Waals equation, the terms 2 and ( b ) are introduced to account for the:

V

(a) inter-molecular attraction and the total volume occupied by the gas

(b) molecular size and the size of the containing vessel

(c) inter-molecular attraction and the volume of the molecules

(d) inter-molecular attraction and the force exerted by the molecules on the walls of the

container

Q3. Critical temperature is defined as the:

(a) lowest temperature at which the gas can be liquefied at constant pressure

(b) lowest temperature at which the gas can be liquified by increase of pressure alone

(c) highest temperature at which the gas can beliquified by increase of pressure alone

(d) highest temperature at which the gas can be liquified at constant pressure

Q4. The work performed by one mole of a Van Der Waals gas during its isothermal

expansion from the volume V1 to V2 at a temperature T is given by .

V2 b 1 1 V2 b 1 1

(a) RT ln + a (b) RT ln + a

V1 b V2 V1 V1 b V1 V2

V1 b 1 1 V1 b 1 1

(c) RT ln + a (d) RT ln + a

V2 b V1 V2 V2 b V2 V1

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Q5.

D

P

A E

C

B

13.1o C

V

Consider the above graph in respect of van der Waals equation of state. Which portion of

the graph cannot be explained?

(a) AB (b) BC (c) DE (d) BCD

MSQ (Multiple Select Questions)

Q6. Which of the following are important in case of a van der Waals gas?

(a) Short range attraction (b) Long range repulsion

(c) Short range repulsion (d) Long range attraction

Q7. Which of the important results of Andrews experiment are correct

(a) There exists a temperature called critical temperature, above which a gas cannot be

liquefied, however great the applied pressure is.

(b) There exists a temperature called critical temperature, below which a gas cannot be

liquefied, however great the applied pressure is.

a

(c) For van der Waal gases critical temperature is .

27 Rb

(d) Oxygen, nitrogen and hydrogen are permanent gases and they cannot be liquefied.

a

Q8. In the equation of state for real gases P + 2 (V b ) = RT

V

(a) The critical points are point of inflection.

(b) Critical volume is given by Vc = 3b

a

(c) Critical pressure is given by Pc =

27b 2

8a

(d) critical temperature is given by Tc =

27 Rb

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NAT (Numerical Answer Type Questions)

Q9. If the value of van der Waals constant b for a real gas is 32 cm 3 / mol, then the

= 6.02 10 23 ) (Answer must be upto one decimal)

RT

Q10. van der Waals equation predicts that the critical coefficient of a gas c has the

PcVc

value..(Answer must upto one decimal point )

RT a

Q11. If equation of state is given by P = exp then critical volume

V b RTV

Vc = .. b .

RT a

Q12. If equation of state is given by P = exp then critical volume

V b RTV

a

Tc = .. .

Rb

RT a

Q13. If equation of state is given by P = exp then critical coefficient

V b RTV

RTc

= ........

PV

c c

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Solutions

MCQ (Multiple Choice Questions)

Ans. 1: (a)

Solution: The relation between PV and P is given as

PV = A + BP + CP 2 + DP 2 + (i)

A, B, C are virial constant A > B > C > D . If P is very high then PV constant.

So, for ideal gas P should be small and T should be large.

Ans. 2: (a)

Solution: The ideal gas equation is PV = RT whereas gas equation, for real gases is given by

a

van der Waals which is P + 2 (V b ) = RT where, the factor b is due to volume

V

a

occupied by the molecules itself and 2 is due to molecular attractive force.

V

Ans. 3: (c)

Ans. 4: (a)

Solution: We know van der Waals gas equation:

a

P + 2 (V b ) = RT (i)

V

W = dW = pdV

RT a

from (i): P= 2

V b V

V2

RT a

then W = 2 dV

V1

V b V

V2 b 1 1

W = RT ln + a

V1 b V2 V1

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Ans. 5: (d)

D

Solution: The Van der Waals equation is given as

P

a A E

P + 2 (V b ) = RT C

V

B

13.1o C

where a, b are constant.

V

The graph drawn is shown as the curve ABCDE . This does not agree with the

experimental isothermals for CO2 as obtained by Andrews However the portion DE has

been explained as due to super cooling of vapours and the portion AB due to super

heating of the liquid. But the portion BCD cannot be explained because it shows

decrease in volume with decrease in pressure.

Ans. 6: (c) and (d)

a

Solution: van der Waals equation P + 2 (V b ) = RT , where a, b are constant. In this case

V

short range of repulsion and long range of attraction is important.

Ans. 7: (a) and (d)

Solution: From the result of Andrews experiment we can define critical temperature as a

temperature above which a gas cannot be liquefied however great the applied pressure is

All gases are real gas so they can be liquefy

8a

For van der Waals gases, critical temperature is given by Tc =

27 Rb

Ans. 8: (a), (b), (c) and (d)

Solution: The van der Waals equation is given as

a

P + 2 (V b ) = RT

V

P d2P

= 0 and 2 = 0 (point of inflection ) thus, we get Vc = 3b

V T dV T

8a a

and Tc = Pc = Thus, Vc = 3b

27 Rb 27b 2

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NAT (Numerical Answer Type Questions)

Ans. 9: 1.3

Solution: The van der Waals constant b is given as b = four times the actual volume of the

molecules.

b

volume of one molecule =

4N

32

volume of one molecule = = 1.3 10 23 cm 3

4 6 10 23

8a a

Solution: For van der Waal Gases Tc = , Vc = 3b , Pc =

27 Rb 27b 2

RTc 8

=

PcVc 3

Ans. 11: 2

RT a

Solution: P = exp critical point are point of inflection so at critical points

V b RTV

P d2P

= 0 and 2 = 0 (point of inflection)

V T dV T

So Vc = 2b

RT a

Solution: P = exp critical point are point of inflection so at critical points

V b RTV

P d2P

= 0 and 2 = 0 (point of inflection )

V T dV T

a

Vc = 2b, Tc =

4bR

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Ans. 13: 3.7

RT a

Solution: P = exp critical point are point of inflection so at critical points

V b RTV

P d2P

= 0 and 2 = 0 (point of inflection)

V T dV T

a a

Vc = 2b, Tc = and Pc = 2 2

4bR 4e b

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Chapter 3

Basics of Thermodynamics and Laws of Thermodynamics

3.1 Mathematical Formulations of Thermodynamics.

y = y ( x1 , x2 ,......xn )

dy = ci dxi

i

y y y

dy = dx1 + dx2 + ....... = dxi

x1 x2 i xi

2 y 2 y

1. =

xk xl xl xk

x y

2. =

y z x z

x x y

3. =

z y y z z x

x x z

4. =

y z z y y x

x x w

5. =

y z w Z y z

x x

6. dx = dy + dw

y w w y

x x x w

= +

y z y w w y y z

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3.2 Fundamental Concept

3.2.1 System: A system can be any object, region of space etc, selected for study and set apart

(mentally) from everything else. Which then become surrounding.

The system of interest in thermodynamics are finite and macroscopic rather than

microscopic. The imaginary envelope which encloses a system and separated it from its

surrounding is called the boundary of the system.

3.2.2 Isolated system It can not exchange either matter or energy with the surroundings.

If exchange of matter is allowed the system is said to be open; if only energy and not

matter is closed (but not isolated).

3.2.3 Thermodynamical state

A thermodynamic state is a set of values of properties of a thermodynamic system that

must be specified to reproduce the system.

Thermodynamic state is the macroscopic condition of a thermodynamic system as

described by its particular thermodynamic parameter. Such as temperature (T) pressure

(P) volume (V) density ( ) .

3.2.4 State function state function also called State variable thermodynamic variables

describe the momentary condition of thermodynamic system

For a continuous process, such variable are exact different also fully determined by their

initial and final thermodynamic states.

Example includes entropy, pressure, temperature, volume, etc.

3.2.5 Intensive and extensive properties

Intensive properties:-it is a physical property of a system that does not depend on the

system size or the amount of material in system. It is scale invariant.

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Example: Chemical potential, density, viscosity, resistivity, specific heat capacity, pressure,

elasticity, magnetization, velocity, acceleration, temperatures, etc.

Solution: Extensive properties:- It is one that is additive for independent non-interacting

subsystem. It is directly proportional to the amount of material in the system.

Example energy, Entropy, Gibbs energy, mass momentum, volume, change, weight,

f df

Note: If f and g are arbitrary intensive variable then fg , , and f + g will also

g dg

intensive variable.

If F and G are also two arbitrary extensive variable then F + G will an extensive variable

F dF

but and will be intensive.

G dG

F dF

If F is extensive variable and f is intensive variable the f F and and is extensive

f df

variable.

3.3 The Ideal Gas:

The Ideal gas law is the equation of hypothetical Ideal gas. It is derived from kinetic

theory and satisfied Boyles and Charless law.

The state of an amount of ideal gas is determined by its pressure (P) volume (V) and

temperature (T).

The Ideal gas equation of state for n mole is given by PV = nRT

Where R is gas constant and given by 8.314 J. K-1 mole-1

3.4 Laws of Thermodynamics

3.4.1 Zeroth Law of Thermodynamics: If two systems 1 and 2 are separately in thermal

equilibrium with third 3 they must be in thermal equilibrium with one another.

3.4.2 First Law of Thermodynamics: Energy is conserved when heat is

taken into account. W

Mathematically If Q amount of heated to the system and if system

dU

will do W amount of work then change in internal energy is

dU given by W

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dU = Q W

obviously heat exchange and work is dependent on path and internal energy is state

function.

U is a mathematical abstraction that keeps account of the exchange of energy that be fall

the system.

The term Q means the amount of that amount of energy added to or

P B

remove by conduction of heat or by thermal radiation.

W is amount of energy gained or lost as result of work.

3.4.3 Work Done during Different Process. A

B

W = PdV

A

If work is done by the system it has positive sign, and if work is done on the system it has

negative sign.

3.4.4 Specific Heat:

Heat capacity of a body is numerically equal to quantity of heat required to raise its

temperature by 1 unit.

C=

T

The specific heat of a material is numerically equal to quantity of heat required to raise

the temperature of unit mass of that materials through 1unit

d

C=

mdT

3.4.5 Heat Capacity of Ideal Gas: if f is degree of freedom of Ideal gas then from

equipartition of energy total sum of energy is equivalent to sum of kinetic energy

associated with each degree of freedom

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3.4.6 Molar Heat Capacity: heat capacity defined as the energy required to raise the

temperature of one mole of Ideal gas by one Kelvin at constant volume.

f

U = N A KT where NA is Avogadro number

2

dU f fR

= N AK =

dT 2 2

Rf

CV = , for Ideal gas

2

f

C P = C V + R = R + 1

2

is defined as ratio of heat capacity at constant pressure to constant volume.

Cp 2

= = 1 +

Cv f

1 V

3.4.7 Coefficient of Volume Expansion ( ) or expansivity =

V T P

P 1

3.4.8 Isothermal Elasticity ET = V and Isothermal compressibility T =

V T ET

Example: Find the isothermal compressibility of a Van der Waals gas as a function of volume

V at temperature T .

1 V

Note: By definition, = .

V p T

a

Van der Wall equation: P + 2 (V b ) = RT (i)

V

If process is isothermal: T = constant

a a

dP + 3 dV (V b ) + P + 2 (dV ) = 0

V V

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dP a a

3 (V b ) + P + 2 = 0

dV V V

dP

=

(

P + a /V 2 a

+ 3 =

)

PV 3 + aV + a (V b ) ( )

dV (V b ) V V 3 (V b )

1 V 3 (V b ) V 2 (V b )

= =

(

V PV 3 + aV + a(V b ) ) PV 3 aV + a(b V ) [( ) ] (ii)

V 2 (V b )

=

[

RTV 3 2a(V b )

2

]

3.5 Different Type of Thermodynamical Process and Use of First Law of

Thermodynamics.

3.5.1 Isochoric Process: When volume remain constant during the process the process is said

to be isochoric process.

dW = PdV dV = 0 dW = 0

P

In an isochoric process work done during the process is zero. B

dU = Q W W = 0 A

V

dU = Q = nCV dT

3.5.2 Isobaric Process: When pressure of the system remain constant during the process.

Work done during the process is given by

B

PdV = P(V

A

B VA )

P A B

= nR (TB T A )

= nR T

V

where T is change in temperature during the process.

Q = dU + W = nCV T + nRT = n ( CV + R ) T

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Q = nCP T CV + R = CP (for the ideal gas)

Heat exchange during the process for n mole of gas is equal to nC p T where C p is

3.5.3 Isothermal Process: when temperature remains constant during the process then system

is said isothermal process.

In isothermal process change in internal energy is zero A

because T = 0

P

VB

dV VB

W = PdV = nRT W = nRT ln

VA

V VA B

during the isothermal process heat exchange

V

VB

Q = W = nRT ln

VA

3.5.4 Adiabatic Process: When there is not any heat exchange during the process then process

is said to be adiabatic process.

Adiabatic process is defined by

PV = constant P

So TV 1 = constant

V

P1 T = constant

CP

where =

CV

work done during adiabatic process W = PdV

VB

k

PV = k dW = dV = k V dV

V VA

VB

V +1 V 1 VA1

k =k B

+ 1 V

A

1

=

1 1

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For n mole Ideal gas

nR (TB TA )

W=

1

For Adiabatic process Q = dU + W

Hence Q = 0 dU = W

So in adiabatic process change in internal energy is equal to minus of work done i.e.

nR (TA TB )

dU =

1

Sign convention: Work done by the system is positive, work done on the system is

negative, heat absorbed by system dQ is positive. Heat reject by the system is negative.

Example: n mole of certain ideal gas at temperature T0 were cooled isochorically so that the gas

pressure reduced n times. Then as a result at the isobaric process the gas expanded till its

temperature get back to initial value. Find the total amount of heat absorbed by the gas in

the process.

Solution: Let at state A, the pressure, volume, temperature is P0 , V0 , T0 , n is number of mole.

According to question:

P0

isochoric isochoric Vc

P0V0 P0 V0 n

T0 n TB T0

(A ) ( B) (C )

P0V0 P0V0 T0

= TB =

T0 nTB n

P0 V0 P0 Vc

= = Vc = nV

n TB n T0

In process A to B

T

dQ = nCv T = nCv 0 T0

n

In process B to C

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T T

dQ = nCv T + PdV = nCv T0 0 + nR T0 0

n n

Total heat absorbed by gas

dQ ( A B ) + dQ ( B C )

T T T 1

= nCv 0 T0 + nCv T0 0 + nR T0 0 = nRT0 1

n n n n

Example: A sample of an ideal gas is taken though the cyclic process abca as shown in figure. It

absorbed 50 J of heat during part ab, no heat during bc and reject 70 J of heat during ca,

40 Jule of work is done on the gas during part bc.

(a) Find the internal energy of the gas at b and c if it is 1500 J at a.

(b) Calculate the work done by the gas during the part ca.

Solution: (a) during a b V = constant

Q = dU = 50 J

U a = 1500J so at U b = 1550J P

b

Work b c = - 40 J

U b = 1550 J U c = 1590 (no heat at bc)

U = 1500 1590 = 90 J V

Q = 70 J

W = Q U

= 70 + 90 = 20 J

Example: A sample of an Ideal gas has pressure P0, volume V0 and temperature T0. It is

isothermally expand to twice its original volume. It is then compressed at constant

pressure to have the original volume V0. Finally, the gas is heated at constant volume to

get the original temperature.

(a) Show the process in VT diagram.

(b) Calculate the heat absorbed in the process.

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Solution: (a)

2V0 b

V

c a

V0

(b) Hence the process is cyclic then change in internal energy in cycle is zero. So heat

supplied in the cycle is equal to work done.

Work done during A B is isothermal, so

2V0

WAB = nRT0 ln = nRT0 ln 2

V

b c isobaric, so work done is PdV.

PaVa = PbVb

P0V0a = Pb 2V0

P0

Pb =

2

P0 PV

Wb c = (V0 2V0 ) = 0 0

2 2

Wc a is isochoric Wc a = 0

Total work done is given by

P0V0

nRT0 ln 2 +

2

1

= nRT0 ln 2 Ans.

2

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MCQ (Multiple Choice Questions)

Q1. The first law of thermodynamics is a statement of

(a) conservation of heat (b) conservation of work

(c) conservation of momentum (d) conservation of energy

Q2. If heat is supplied to an ideal gas in an isothermal process,

(a) the internal energy of the gas will increase

(b) the gas will do positive work

(c) the gas will do negative work

(d) the said process is not possible

Q3. Figure given below shows two processes A and B on a system. Let Q1 and Q2 be the

P

A

B

V

(a) Q1 > Q2 (b) Q1 = Q2 (c) Q1 < Q2 (d) Q1 Q2

Q4. Refer to figure in Let U1 and U 2 be the changes in internal energy of the

P

A

B

V

(a) U1 > U 2 (b) U1 = U 2 (c) U1 < U 2 (d) U1 U 2

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Q5. Consider the process on a system shown in figure given below. During the process, the

work done by the system P

(c) first increases then decreases (d) first decreases then increases

(A) If heat is added to a system, its temperature must increase.

(B) If positive work is done by a system in a thermodynamic process, its volume must

increase.

(a) Both A and B are correct (b) A is correct but B is wrong

(c) B is correct but A is wrong (d) Both A and B are wrong

Q7. An ideal gas goes from the state i to the state f as shown in figure below. The work

done by the gas during the process P f

T

(a) is positive (b) is negative

(c) is zero (d) cannot be obtained from this information

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Q8. Consider two processes on a system as shown in figure below.

P

B

A

T

The volumes in the initial states are the same in the two processes and the volumes in the

final states are also the same. Let W1 and W2 be the work done by the system in the

(a) W1 > W2 (b) W1 = W2 (c) W1 < W2

Q9. A gas is contained in a metallic cylinder fitted with a piston. The piston is suddenly

moved in to compress the gas and is maintained at this position. As time passes the

pressure of the gas in the cylinder

(a) increases (b) decreases (c) remains constant

(d) increases or decreases depending on the nature of the gas.

7

Q10. The pressure and density of a gas = change adiabatically from (P1 , d1 ) to (P2 , d 2 ) .

5

d2 P2

If = 32 , then the value of

d1 P1

1 1

(a) 32 (b) 128 (c) (d)

32 128

Q11. The pressure P volume V and temperature T for a certain material are related

by P =

(AT BT ) where 2

A, B are constants. The work done by the materials if the

V

temperature changes from T to 2T while the pressure remains constant?

(a) AT BT 2 (b) AT 2BT 2

(c) AT 3BT 2 (d) 2 AT 3BT 2

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Q12. The specific heat (c ) of a substance is found to vary with temperature (T ) as c = + T 2 .

Where T is Celsius temperature. At what temperature does the specific heat of the

substance becomes equal to the mean specific heat of the substance in a temperature

range between 0 and T0 ?

T0 T0 T0 T0

(a) (b) (c) (d)

2 2 3 3

Q13. The equation of state of a gas is given as P(V b ) = nRT where b is a constant, n is the

number of moles and R is the universal gas constant. When 2 moles of this gas undergo

reversible isothermal expansion from volume V to volume 2V , what is the work done

by the gas?

(a) 2 RT In [(V b ) / (2V b )] (b) 2 RT In [(2V b ) / (V b )]

Q14. If (1) represents isothermal and (2) represents adiabatic, which of the graphs given above

in respect of an ideal gas are correct?

(2) (1) (2)

(1) (1)

T T P

(2)

V P V

I II III

(a) I and II (b) II and III (c) I and III (d) I, II and III

Q15. What is the minimum attainable pressure of an ideal gas in the process given by

T = a + bV 2 , where a, b are constants and V is the volume of one mole of ideal gas?

(R is the universal gas constant)

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Q16. One mole of an ideal gas is takes from an initial state (P, V , T ) to a final state

(2P, 2V , 4T ) by two different paths as shown in the Fig. 1 and 2 given above. If the

changes in internal energy between the final and the initial states of the gas along the

paths I and II are denoted by U I and U II respectively, then:

V

C (2 P, 2V , 4T ) C 2 P, , 4T

2

A(P, V , T ) B C

C (2 P, 2V , 4T )

P P

P

B , 2V , T A

2 B (P , V , T )

V V

Fig. 1 (Path I) Fig. 2 (Path II)

shown by the path A B C A in the P V P 30

diagram given then The work done by the system in going N

2 20 C

B

m

from the state A to the state B is:

10

(a) 35 3.0 J (b) 35 3.5 J

1 2 3 4 5 6

(c) 50 3.5 J (d) 50 5.0 J

V m3 ( )

Q18. A system absorbs 1.5 10 3 J of energy as heat and produces 500J of work. The change

in the internal energy of the system will be:

(a) 1500 J (b) 100 J (c) - 1500 J (d) 1000 J

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Q19. A given amount of heat cannot be completely converted into work. However it is possible

to convert a given amount of work completely into heat. This apparently contradictory

statement results from the:

(a) zeroth law of thermodynamics (b) first law of thermodynamics

(c) second law of thermodynamics (d) third law of thermodynamics

Q20. If the number of degrees of freedom of a molecule in a gas is n then the ratio of specific

heats is given by:

1 1

(a) 1 + (b) 1 +

n 2n

2 2n

(c) 1 + (d)

n 2n 1

Slope of isothermal curve

Q21. The ratio is equal to:

Slope of adiabatic curve

1

(a) 1 (b) (c) (d)2

Q22. One mole of a perfect gas expands adiabatically. As a result of this, its pressure,

temperature and volume change from P1 , T1 , V1 , to P2 , T2 and V2 respectively. if molar

specific heat at constant volume is CV , then the work done by the as is:

V V

(a) 2.303P1V1 log 2 (b) RT1 log 2

V1 V1

P12V12 P22V22

(c) (d) CV (T1 T2 )

R(T2 T1 )

Q23. For a diatomic gas having 3 translational and 2 rotational degrees of freedom, the energy

is given by:

5 3 1

(a) k BT (b) k BT (c) kBT (d) k B T

2 2 2

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Q24. The maximum attainable temperature of ideal gas in each of the following processes

p = p0 e V is

P0 P0 2P0 2 P0

(a) Tmax = (b) Tmax = (c) Tmax = (d) Tmax =

e R 2e R e R 3e R

Q25. A horizontal cylinder closed from one end is rotated with a constant angular velocity

about a vertical axis passing through the open end of the cylinder. The outside air

pressure is equal to p 0 , the temperature to T , and the molar mass of air to M . Find the air

pressure as a function of the distance r from the rotation axis. The molar mass is

assumed to be independent of r .

M 2 r 2 M 2 r 2 M 2 r 2 M 2 r 2

(a) P = P0 e 2 RT

(b) P = P0 e 2 RT

(c) P = P0 e RT

(d) P = P0 e RT

Q26. A thermally insulated vessel containing a gas whose molar mass is equal to M and the

ratio of specific heats C p / CV = moves with a velocity v . If vessel is suddenly

( 1) ( 1) Mv 2

(a) T = Mv 2 (b) T =

R 2R

2 ( 1) ( 2 1)

(c) T = Mv 2 (d) T = Mv 2

R R

Q27. Gaseous hydrogen contained initially under standard conditions in a sealed vessel of

volume V0 was cooled by T . The amount of heat will be lost by the gas if initial

P0V0 T P0V0 T

(a) Q = (b) Q =

T0 ( 1) T0 ( 1)

(c) Q = (d) Q =

T0 T0

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Q28. A given quantity of gas is taken from the state A C reversibly, by two paths, A C

directly and A B C as shown in the figure. During the process

P

A

A C the work done by the gas is 100 J and the heat absorbed is

150 J . If during the process A B C , the work done by the gas

is 30 J , then which one of following is correct? B C

(a) heat absorbed in A B C 20 J V

(b) heat absorbed in A B C 80 J

(c) heat reject in A B C 20 J

(d) heat reject in A B C 80 J

Q29. Let Q be the heat exchange in a quasistatic reversible thermodynamic process. Then

which of the following is correct?

(a) Q is a perfect differential if the process is isothermal

(b) Q is a perfect differential if the process is isochoric

(c) Q is always a perfect differential

(d) Q cannot be a perfect differential

Q30. Let W be the work done in a quasistatic reversible thermodynamic process. Which of

the following statements about W is correct?

(a) W is a perfect differential if the process is isothermal

(b) W is a perfect differential if the process is adiabatic

(c) W is always a perfect differential

(d) W cannot be a perfect differential

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MSQ (Multiple Select Questions)

Q31. The pressure p and volume V of an ideal gas both increase in a process.

(a) Such a process is not possible

(b) The work done by the system is positive

(c) The temperature of the system must increase.

(d) Heat supplied to the gas is equal to the change in internal energy.

Q32. In a process on a system, the initial pressure and volume are equal to the final pressure

and volume.

(a) The initial temperature must be equal to the final temperature.

(b) The initial internal energy must be equal to the final internal energy.

(c) The net heat given to the system in the process must be zero.

(d) The net work done by the system in the process must be zero.

Q33. Refer to figure below. Let U1 and U 2 be the change in internal energy in processes

A and B respectively, Q be the net heat given to the system in process A + B and

W be the net work done by the system in the process A + B .

P

A

B

V

(a) U1 + U 2 = 0 (b) U1 U 2 = 0

(c) Q W = 0 (d) Q + W = 0

Q34. The internal energy of an ideal gas decreases by the same amount as the work done by

the system.

(a) The process must be adiabatic. (b) The process must be isothermal.

(c) The process must be isobaric. (d) The temperature must decrease.

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Q35. Which of the following is correct statement statements?

Cp 8 5

(a) The value of for helium is for =

(C p + CV ) 3 3

3R

(b) value of specific heat capacity at constant volume for helium is

2

(C CV ) 1 7

for =

p

(c) The value of for H 2 is

(C p + CV ) 6 5

7R

(d) value of heat capacity at constant pressure is

2

Q36. The first law of thermodynamics, U = Q W , indicates that when a system goes

from its initial state to a final state which of following is correct statement

(a) U is the same for every path

(b) Q the same for every path in isochoric process

(c) W is the same for every path in adiabatic process

(d) W and Q are the same for every path

Q37. Two thermally insulated vessels 1 and 2 are filled with air and connected by a short tube

equipped with a valve. The volumes of the vessels, the pressures and temperatures of air

in them are known (V1 , p1 , T1 and V2 , p 2 , T2 ) . The pressure established after the opening of

the valve is given by

P1V1 + P2V2 P1 / V1 + P2 / V2

(a) P = (b) P =

V1 + V2 1 1

+

V1 V1

T1V1 + T2V2 T1T2 (P2V2 + P1V1 )

(c) P = (d) T =

V1 + V2 P1V1T2 + P2V2T1

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Q38. Two moles of certain ideal gas at a temperature T0 cooled isochorically so that the gas

pressure reduced n times. Then, as a result of the isobaric process, the gas expanded till

the temperature got back to the initial value.

(a) the work is given by RT0

Q39. A diatomic gas at S T P is expanded to thirty-two times its volume under adiabatic

conditions. the resulting temperature in .. 0 K ( answer must be in two decimal

points)

Q40. The quantity of heat required to raise the temperature of one gram molecule through one

degree for a mono atomic gas at constant volume is .. R (where R is gas

constant )

1

Q41. A gas expands adiabatically at constant pressure such that its temperature T . The

V

Cp

value of = of the gas is

CV

5 3

Q42. One mole of diatomic gas CV = R and one mole of a monatomic gas CV = R

2 2

are mixed. The value of for the mixture is, (where is the ratio of two specific heats

of the gas..

Q43. For a ideal gas having 3 translational and 2 rotational degrees of freedom at constant

temperature T , the internal energy is k BT

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Q44. The minimum attainable pressure of ideal gas in the process T = T0 + V 2 where T0 and

are positive constants, and V is the volume of one mole of gas is R T0 the value of

is given by .

Q45. The volume of one mole of an ideal gas with the adiabatic exponent is varied

according to the law V = a / T , where a is a constant. Find the amount of heat obtained

by the gas in this process if the gas temperature increased by T .

Q46. Ten grams of ice at 0C is added to a beaker containing 30 grams of water at 25C. What

is the final temperature of the system is . 0C when it comes to thermal

equilibrium? (The specific heat of water is 1 cal/gm/C and latent heat of melting of ice is

80 cal/gm)

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Solutions

MCQ (Multiple Choice Questions)

Ans. 1: (d)

Ans. 2: (b)

Solution: dQ = dW sign dQ is positive so dW is positive the gas will do positive work .

Ans. 3: (a)

Solution: Change in internal energy in both the path is same and P

A

area under the path A is more than path B so work done in

the path A is more than path B .From first law of

B

thermodynamics Q1 > Q2 V

Ans. 4: (b)

Solution: Internal energy is point function

Ans. 5: (a)

Solution: work done is area under the curve so from the figure continuously increases

Ans. 6: (c)

Solution: From first law of thermodynamics sign of dQ = dU + dW is not dependent only on

change on temperature rather it can be compensated by sign of internal energy and work

done .but work done is positive if volume expand .

Ans. 7: (c)

Solution: This is isochoric process so work done is zero

(d) Nothing can be said about the relation between W1 and W2 .

Ans. 8: (c)

Solution: The process is isobaric, so work done is nRdT so change in temperature in B is more

than A so W1 < W2

Ans. 9: (c)

Solution: After some time the system will be in mechanical equilibrium, so pressure will remain

constant.

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Ans. 10: (b)

Solution: If there is no exchange of heat between a system and its surrounding the process is

known as adiabatic. The gas equation for adiabatic change is given as

1

, P (density )

PV = constant since, volume

density

P2 d 2

P1 = kd1 P2 = kd 2 =

P1 d1

since,

d2

d1

= 32

p2

p1

= (32) = 2 5

7/5

( ) 7/5

= 128

Solution: Here,

AT BT 2

P=

V

where, A, B are constants.

The work done dW is given as

dW = PdV (i)

Now, PV = AT BT 2

PdV = d (AT BT 2 )

PdV = AdT 2 BT .dT (ii)

by equation (i) and (ii)

dW = AdT 2 BT .dT

[ ] [ ]

2T

2T 2

work done = = AT BT 2 T

T

= AT 3BT 2

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Ans. 12: (c)

Solution: The amount of heat required to increase the temperature of unit mass is called specific

heat.

Q = mcT

where m = mass of substance

T = increment in temperature

and c = + T 2 (i)

T03

T T0

1 0 1 1

The mean specific heat c = cdT = ( + T )dT = +

2

0T

T0 0 T0 0

T0 3

BT02

c = +

3

BT02 BT 2

By question c = c + = + BT 2 0 = BT 2 T = 0

3 3 3

Ans. 13: (b)

Solution: P(V b ) = nRT

Work done = dW = PdV

nRT 2V nRT

W = PdV where P = W = dV

V b V V b

2V dV

= nRT = nRT log ( 2V b ) log (V b )

V V b

2V b

Since, n=2 W = 2 RT log

(V b )

Ans. 14: (d)

Solution: Slope of adiabatic curve = slope of isothermal curve. This is shown by every

curve given in question. Hence, all curve represent the ideal gas.

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Ans. 15: (c)

PV

Solution: We have T = a + bV 2 = a + bV 2

R

aR V 2 Rb aR

P= + ,P = + VbR

V V V

dP

To find minimum pressure put =0

dV

d aR

+ VbR = 0

dV V

aR a

+ Rb = 0 V2 =

V2 b

d 2P

Again differential Eq. (i) twice, we get 2

is +ve for V 2 ,

dV

P is minimum at V 2 .

By Eqs. (i) and (ii), we get

aR

Pmin = + bR a / b = 2 R ab

a/b

Ans. 16: (a)

Solution: The change in internal energy dU is independent of the path, i.e., if initial and final

states of change are same then dU will be same.

Ans. 17: (a)

Solution: The work done is given as A

50

= PdV

= area of the triangle + area of the rectangle p

1

= (50 20 ) (5 2 ) + (20 3) 20 B

2 C

1

= 30 3 + 20 3 = 105 J

2

2 5

V

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Ans. 18: (d)

Solution: The first law of thermodynamics is given as

Q = dU + W

Here, Q = 1.5 10 3 = 1500 J

W = 500 J

so, dU = Q W = 1000 J

Ans. 19: (b)

Ans. 20: (c)

Solution: We know that energy associated with each degree of freedom of one mole gas is given

1

= RT

2

n

Hence if there is n degree of freedom, then U = RT where R universal gas

2

constant.

We know that specific heat at constant volume is given as

dU n

CV = CV = R (i)

dT 2

n n

By Mayors formula C P CV = R = R + R C P = 1 + R

2 2

CP 2

= = 1+

Cv n

Ans. 21: (c)

Solution:

P P

V V

isothermal curve adiabatic curve

The ideal gas equation is written as PV = RT

For isothermal T is constant differentiate above equation w.r.t. V we get

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d

(PV ) = 0 dP = P slope of isothermal curve = P

dV dV V V

differentiating this w.r.t. V we get V dP + PV 1 dV = 0

dP P P

= slope of adiabatic curve = (ii)

dV V V

Slope of isothermal curve 1

dividing equation (ii), we get =

Slope of adiabatic curve

Ans. 22: (d)

Solution: Specific heat: The rate of change of internal energy w.r.t. temperature at constant

volume is called specific heat at constant volume.

dU

CV = (i)

dT V

by first law of thermodynamics Q = dU + W (ii)

For adiabatic Q = 0 so above equation (ii) becomes

dU + W = 0

CV (dT ) + W = 0 CV (T2 T1 ) + W = 0 W = CV (T1 T2 )

Solution: The energy associated with each degree of freedom at temperature T is given as

1

E= k BT , k B is Boltzmanns constant

2

Here, total number of degrees of freedom= number of degree of rotational freedom +

1

translational freedom 3 + 2 = 5 thus, total energy = 5 k BT

2

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Ans. 24: (a)

RT

Solution: P = P0 e V = P0 e V

V

P0 V

T = Ve .(i)

R

( )

dT P

For maximum temperature, = 0 0 e V Ve V = 0

dV R

1 P0

This gives V = . Putting this value of V in equation (i), gives T =

e R

Ans. 25: (b)

Solution: Force equation of dr element.

dF dm 2 A

dF = ( dm ) r 2 , dP =

= r and dm = 2 dP

A A r

where A is area of cross section

Also we know

dm

P ( Adr ) = RT M, T

M

P0 S

RT A

PA(dr ) = dP r

M r 2 This end is

r P dP open in air

M 2 rdr = RT

0 P0 P

2 2

M r

M 2 r 2 P

= RT ln P = P0 e 2 RT

2 P0

Ans. 26: (b)

Solution: Suppose number of moles of gas = n

1

Directional kinetic energy of gas = (nM )v 2

2

When vessel sudden stop, then after long time this directional kinetic energy of gas is

converted into random kinetic energy when thermodynamic equilibrium will be achieved

and then

1

(nM )v 2 = nCV T T =

( 1) Mv 2

2 2R

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Ans. 27: (a)

Solution: Suppose initial temperature is T1 and final is (T1 T ) then

P1V P2V

Ui = ; Uf =

1 1

V0

U = (P2 P1 )

1

nRT1 PV

PV

1 = nRT1 P1 = also nR = 1 0

V T1

nRT2

P2 =

V0

V0 nRT2 nRT1 nR

U = = (T )

1 V V 1

P1V0 T P1 = P0

U = here

T1 ( 1) T1 = To

P0V0 T

U =

T0 ( 1)

U = increase in potential energy

Q = U + W since vessel is sealed then W = 0

0 0 T

PV

Q = U =

T0 ( 1)

Solution: During path AC dU = Q W = 150 100 = 50 J

Hence internal energy is point function dU will same in all path

In path ABC , Q = dU + W = 50 + 30 = 80 J .

Ans. 29: (b)

Solution: Heat exchange is perfect differential in isochoric process.

Q = dU

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Ans. 30: (b)

Solution: W is a perfect differential if the process is adiabatic

W = d U

Ans. 31: (b) and (c)

Solution: If volume increase then workdone is positive and from PV = nRT if volume and

pressure increase then temperature will increase.

Ans. 32: (a) and (b)

Solution: from PV = nRT if pressure and volume of initial point and final point is same then

temperature is same ,so internal energy will also same

Ans. 33: (a) and (c)

Solution: U1 = U 2 = 0 because internal energy is path independent so Q W = 0

Solution: Q = dU + W and dU = nCV dT , dU is negative so temperature decreases.

If dU = W so Q = 0

Ans. 35: (b), (c) and (d)

Solution: The ratio of C p and CV is known as coefficient of adiabatic expansion. Hence,

Cp

=

CV

5 1 Cp 3

(a) so, for helium = = , =

3 5 C p + CV 8

1+

3

R 3R 5

(b) CV = = for =

1 2 3

7 C p CV

(c) for hydrogen = =

5 C p + Cv

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7

C p CV C p / CV 1 1 C p CV 1

1 5

= = = =

C p + CV C p / CV + 1 +1 7

+1

C p + CV 6

5

R 7R

(d) CP = =

1 2

Ans. 36: (a), (b) and (c)

Solution: The internal energy U is a state function. Hence, it does not depend on path whereas

both Q and W depend on path. Thus, Q is same for every path.

Ans. 37: (a) and (d)

Solution: vessel 1 2

? V2 + V2

V1 , P1 , T1 V2 , P2 , T2 P

T

When value is opened and thermodynamics equilibrium is attained then, number of moles

will be constant. Then

P1V1 P2V2 P(V1 + V2 )

+ =

RT1 RT2 RT

P1V1 P2V2 P(V1 + V2 )

+ = (i)

T1 T2 T

Also we know, in whole system:

Q = 0 = U + W

Q = 0 because vessel is insulated. And also

W = 0 because gas does not work on atmosphere because vessel closed

then U system = 0 then

n1CV T1 = n2 CV T2 n1 T1 = n2 T2

P1V1

(T T1 ) + P2V2 (T T2 ) = 0 (ii)

T1 T2

T= put in (i) P =

P1V1T2 + P2V2T1 V1 + V2

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Ans. 38: (a) and (c)

Solution:

n=2 V = constant

T0 P

P0 Pf = 0

2

P

isochoric

isobaric P

Initial (P0 ; T0 ;V ) 0 ; T1 ;V 0 ; T0 ;V

2 2

Here PV = nRT

P0V = 2 RT0

2 RT0

V=

P0

Isochoric process:

P1 T1

=

P2 T2

P0 T T0

= 0 T1 =

P0 / 2 T1 2

Isobaric process:

V1 T1

=

V2 T2

V T0 / 2

= V1 = 2V

V2 T0

In whole system: from initial to final position:

Q = U + W

here U = 0 final temperature is zero.

W = 0 +

P0

[V ] = P0V = P0 2 RT0

2 2 2 P0

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NAT (Numerical Answer Type)

Ans. 39: 68.25 K

5

Solution: For diatomic gas =

2

Adiabatic equation TV 1 = constant

1

V

T2 = T1 1

V2

here, V1 = V , V2 = 32V , T1 = 273K

273 273 273

T2 = T2 = = = 68.25 K

(32 ) 1

(32)

5

2

1

(32)

3

2

Solution: The quantity of heat required to increase the temperature at constant volume through

0C for per degree of freedom

( Q )V = nCV dT

1

CV = R n = 1, dT = 1

2

1

So, (Q )V = 1 R 1 = 0 .5 R

2

Ans. 41: 1.5

Solution: We know that for adiabatic expansion TV 1 = constant

1

Given that T TV 1/ 2 = constant

V

by equation (i) and (ii),

1 1 3

1 = = 1 + , = = 1.50

2 2 2

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Ans. 42: 1.5

n1cV1 + n2 cV2 n1cP1 + n2 cP2 cp

Solution: cV = and cP = =

n1 + n2 n1 + n2 cV

5R 7R 3R 5R

n1 = 1, cV1 = , cP1 = n1 = 1, cV1 = , cP1 =

2 2 2 2

Ans. 43: 2.5

Solution: The energy associated with each degree of freedom at temperature T is given as

1

E= k B T is k B Boltzmanns constant

2

Here, total number of degrees of freedom= number of degree of rotational freedom +

1

translational freedom 3 + 2 = 5thus, total energy = 5 k B T

2

Ans. 44: 2

Solution: T = T0 + V 2

We know PV = nRT = RT

If V is increasing, T will increase and hence P will increase. Hence calculation of Pmin :

PV

T= put in (i)

R

PV

R

= T0 + V 2 , P = R T0V 1 + V [ ]

dP T

= 0 , R T0V 2 + = 0 V = 0 put in (ii)

dV

T0

[

in P = R T0V 1 + V ]

Pmin = 2 R T0

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Ans. 45: 2

a

Solution: V = number of mole n = 1

T

a

T=

V

we know Q = dU + W

R

U = dU = CV T = T (i)

1

W = PdV W = PdV (ii)

PV = nRT = RT

RT aR

P= = 2 put in (ii)

V V

1 1

V

V2 aR 1 2

W = 2

dV = aR = aR

V1 V V V1 V1 V2

a a

W = R = R[T ]

V1 V2

Q = U + W

RT 1 +1

= RT = RT

1 1

R T ( 2 )

Q =

1

Ans. 46: 0

Solution: The amount of heat required to melt the ice of mass 10gm at 00C is

Q = m L = 10 80 = 800Cal . Where L is the latent heat of melting of ice and m is the

mass of the ice. The amount of heat available in water of mass 30gm at 250C is

Q = m Cv T = 30 1 25 = 750Cal

Since the heat available is less than the heat required to melt the ice therefore ice will not

melt as a result the temperature of the system will be at 00C only

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Chapter 4

Second Law of Thermodynamics and Entropy

4.1 Second Law of Thermodynamics

Statement: It is impossible to transfer total heat into work in a cyclic process in the

absence of other effect (by Lord Kelvin).

In another way it is also stated that it is impossible for heat to be transferred by a cyclic

process from a body to one warmer than itself without producing other changes at same

time.

4.2 Heat Engines

A machine that can convert heat into work is said to be heat engine.

It is a system that performs the conservation of heat or thermal energy to mechanical

work.

Hot reservoir T1

Q1

W = Q1 Q2

Q2

Cold reservoir T2

4.2.1 Heat Reservoir

It is an effectively infinite pool of thermal energy of a given, constant temperature. Ideal

its heat capacity is large enough that when it is in thermal contact with another system, its

temperature remains constant.

All heat engines have mainly three essential components.

1. A source: This is a hot region which is a part of the surrounding from which

energy flows by heat transfer. Popularly it is known as hot reservoir. Example is a

nuclear reactor, furnace.

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2. The working agent: This under goes change at state as part of a continuous cycle

e.g. steam-water.

3. A sink: This is a respectively cold region which is part or the surrounding into

which heat is rejected by heat transfer e.g. cooler.

4.2.2 Efficiency of Heat Engine ():

work done by the system

=

heat given into the system

Hence the process is cyclic dU = 0.

dQ = dW

Heat given to system is Q1 and heat rejected by system is Q2.

Q1 Q2

=

Q1

4.2.3 Carnot Cycle: It is theoretical thermodynamics cycle proposed by Nicolas, Leonard Sadi

Carnot.

It can be shown that it is most efficient cycle for converting a given amount of thermal

energy into work.

A system undergoing a Carnot cycle is called a Carnot heat engine.

Stages of the Carnot cycle: (P1 ,V1 )

P 1

(P2 ,V2 )

2

(P4 ,V4 ) T1

4

(P3 ,V3 ) 3 T2

V

1. Reversible isothermal expansion of the gas at hot temperature, T1 (isothermal heat

addition). During this step (1 to 2) the gas is allowed to expand and it does work

on the surrounding. The gas expansion is propelled by absorption of quantity Q1

at heat from the high temperature T1.

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2. Reversible adiabatic expansion of the gas. For this step (2 to 3) on figure, the gas

continues to expand, working on surrounding. The gas expansion causes it to cool

to the cold temperature T2.

3. Reversible isothermal compression of the gas at the cold temperature T2

(isothermal heat rejection). The process is shown by 3 4. Now the

surroundings do work on the gas, causing quantity Q2 of heat to flow out of the

gas to the low temperature reservoir.

4. Adiabatic compression of the gas (4 to 1). During this step, the surrounding do

work on the gas, compressing it and cause the temperature to rise to T1. At this

point the gas in the same state as at start at step 1.

Efficiency of Carnot engine:

W

=

Q1

W is the work done during cycle and Q1 is heat given to system.

W = W1 + W2 + W3 + W4

V2

W1 = work done during process 1 to 2 for isothermal process = nRT1 ln

V1

change in internal energy during the process dU = 0

V

Q1 = W1 = nRT1 ln 2 (From first law of thermodynamics)

V1

W2 is work done during process 2 to 3 in adiabatic process.

nR (T2 T1 )

dQ = 0 W2 =

1

W3 = work done during process 3 to 4 isothermal compression.

V

W3 = nRT2 ln 4

V3

Q2 = W3 dU = 0 (isothermal process)

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W4 , the work done during the adiabatic process 4 to1 , is given by

nR (T1 T2 )

W4 =

1

W2 = W4

V V

W = nRT1 ln 2 + nRT2 ln 4

V1 V3

V

Q1 = nRT1 ln 2

V1

V

ln 4

= = 1+ 2 3

W T V

.(i)

Q1 T1 V2

ln

V1

From the figure, (P1 ,V1 )

TV 1

= T2V3 1 .(ii) P 1

1 2

(P2 ,V2 )

T2V4 1 = TV 1

.(iii) 2

(P4 ,V4 )

1 1

T1

Dividing equation (ii) by (iii) gives 4

V2

1

V

1 (P3 ,V3 ) 3 T2

= 3

V1 V4 V

V2 V3

= .(iv)

V1 V4

From equations (i) and (iv)

T2

= 1 .(v)

T1

Q2 T2

For Carnot cycle, =

Q1 T1

Q2

This gives = 1 .(vi)

Q1

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Example: An ideal gas engine operator in a cycle which when represent on a P-V diagram is a

rectangle. If we call P1 , P2 and the lower and higher pressures respectively and V1 , V2 as

lower and higher volume respectively.

(a) Calculate the work done in complete cycle

(b) indicate in which parts of the cycle heat is absorbed and in which part librated.

(c) Calculate the quantity of heat following into the gas in one cycle

(d) show that efficiency of the engine is

1

=

P2 V1

+

P2 P1 V2 V1

( P2 ,V1 ) ( P2 ,V2 )

Heat absorbed = nC p T A B

= nR (T2 T1 ) = 2 2 PV

( PV 2 1)

1 1

=

P2 (V2 V1 )

D

( P1 ,V1 )

C

( P1 ,V2 )

1 V

In process B-C isochoric process

W B c = 0

dQ = dU

nCv T

n V

RT = 2 ( P1 P2 )

1 1

P1 < P2 heat rejected

In process C-D isobaric process

WC D = P1 (V1 V2 )

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Heat exchange during the process

QC D = P1 (V1 V2 )

1

V1 < V2 so heat is rejected

WD A = 0

nRT V1 ( P2 P1 )

nCv T = = heat absorbed.

1 1

(a) Work done = P2 (V2-V1) + P1(V1 V2)

W = (P2 P1) (V2 V1)

V1

(b) Heat absorbed P2 (V2 V1 ) + (P P )

1 1 2 1

(c) Heat flowing into the cycle

P2 (V2 V1 ) V2

+ ( P1 P2 ) + P1 (V1 V2 ) + V1 ( P2 P1 )

1 1 1 1

1

= (V2 V1 )( P2 P1 ) + ( P P ) (V2 V1 )

1 1 1 2

1

= (V2 V1 )( P2 P1 ) ( P P )(V V )

1 1 2 1 2 1

1

( P2 P1 )(V2 V1 ) = (P2 P1 )(V2 V1 )

1 1

dQ = dW

W

=

( P2 P1 )(V2 V1 )

(d) Efficiency =

Qabsorbed P2 (V2 V1 ) V1 ( P2 P1 )

+

1 1

1

Therefore, =

P2 V1

+

P2 P1 V2 V1

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4.3 Entropy

Entropy is an extensive thermodynamic property that is measure of a systems thermal

energy per unit temperature that is unavailable for doing useful work. Thermodynamic

entropy is a non-conserved state function. For Isolated systems entropy never decreases.

In statistical mechanics, entropy is a measure of the number of ways in which a system

may be arranged, often taken to be a measure of disorder (the higher the entropy the

higher the disorder).

The infinitesimal change in the entropy ( dS ) of a system is the infinitesimal transfer of

heat energy (Q) to a closed system driving a reversible process, divides by temperature

(T) of the system.

Q

S =

T

Q

It has unit Joule/Kelvin or dS =

T

Law of thermodynamics and entropy:

According to first law of thermodynamics

Q = dU + PdV

From definition of Entropy

Q

S = Q = T S TdS

T

TdS = dU + pdV

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4.3.1 Inequality of Clausius

Consider an irreversible cyclic engine working between T1 and T2. If reversible engine is

operating between same temperature then from Carnot theorem.

Efficiency of irreversible (ir) will always smaller than efficiency of reversible

engine( r ).

irr . < rev.

<

Q1irr Q1rev

Q2irr Q2rev

1 < 1

Q1irr Q1rev

Q2irr T

1 irr

< 1 2

Q1 T1

Q2irr Q1irr

>

T2 T1

F0 irreversible cyclic Engine

Q1irr Q2irr

<0

T1 T2

Q

or T <0

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Example: Two Carnot Engines A and B are operated in series. The first one A receives heat at

900 K and rejects to a reservoir at temperature T K. The second engine, B, receives the

heat rejected by the first Engine and in then rejects to a heat reservoir at 400 K.

Calculate the temperature T for the situation.

(a) The work outputs of the two engines are equal

(b) The efficiency of the two engines are equal.

For Engine A take in heat Q1 at temperature T1 and rejected heat Q at temperature T; and

the engine B taken in heat Q at temperature T and reject heat Q2 at temperature T2.

Solution: (a) WA = Q1 Q WB = Q Q2

WA = WB Q1 Q = Q Q2

Q1 Q2

=2

Q

Q1 T1 Q2 T2

= and =

Q T Q T

Q1 + Q2 T1 + T2 T +T

= 1 2 =2 T = 650 K

Q T T

Solution: (b) A = B

T T

1 = 1 2

T1 T

1

T = (T1 T2 ) 2 T = 600 K

Example: Calculate the charge in isothermal expansion from an initial volume Vi to volume V f

TdS = dU + PdV

For isothermal process dU = 0

PdV

dS =

T

nRT

P=

V

Vf

dV Vf

dS = nR = nR ln

Vi

V Vi

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Example: A mass of liquid at a temperature T1 is mined with an equal mass of the same liquid at

a lower temperature T2. the system is thermally insulated.

(a) compute the entropy-change

(b) show that it is necessarily positive.

Solution: Let c be the specific heat of the liquid. On the mining equal mass m of the same liquid

at temperature T1 and T2 let (T1 > T2).

Let T be the equilibrium temperature at minute.

mc (T1 T ) = mc (T T2 )

T1 + T2

T=

2

T

Q

S 1 =

T1

T

Entropy change of hotter liquid to cool from T1 to T

T

dT T

S1 = mc = mc ln

T1

T T1

T

S 2 = mc ln

T2

S = Entropy change of the system.

S = S 1 + S 2

2

T1 + T2

T2 T + T2 2

= mc ln = mc ln 1 = 2mc ln T T

T1T2 2

1 2

TT

1 2

(b) we know arithmetic mean is greater than geometric mean.

AM > G.M .

T1 + T2

So > T1T2 So S > 0

2

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Example: Compute the change in entropy when ice melt into steam. It is given that L1 is latent

heat of fusion, c is specific heat at water and L2 latent heat at vaporization.

Solution: Assume T1 be the Kelvin temperature at which ice melts into water and T2 the Kelvin

temperature at which water is boiled to steam.

S1 is entropy change when ice is converted into water

mL1

S1 =

T1

T2

dT

S 2 = mc

T1

T

T2

S 2 = mc ln

T1

mL2

S 3 =

T2

mL1 T mL

Total change in entropy S = S1 + S 2 + S3 = + mc ln 2 + 2

T1 T1 T2

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MCQ (Multiple Choice Questions)

Q1. Two Carnot engines A and B are operating between the same source and the same sink.

Engine A uses an ideal gas as the working fluid while engine B uses Van der Waals gas

as the working fluid. Which one of the following is correct?

(a) The efficiency of engine A is less than that of engine B

(b) The efficiency of engine A is equal to that of engine B

(c) The efficiency of engine A is more than that of engine B

(d) No comparison can be made

Q2. A heat engine converts a given quantity of heat into work with maximum efficiency

during which one of the following processes?

(a) Isobaric process (b) Isochoric process

(c) Isoenthalpic process (d) Isothermal process

Q3. If heat Q is added reversibly to a system at temperature T and heat Q is taken away from

it reversibly at temperature T , then which one of the following is correct?

Q Q

(a) =0

T T

Q Q

(b) >0

T T

Q Q

(c) <0

T T

Q Q

(d) = change in internal energy of the system

T T

Q4. The temperature of water (mass, m ) increases from T1 to T2 . If c is the specific heat

capacity of water, then the total increase in entropy of water is given by:

T

(a) mc(T2 T1 ) (b) mc log e 1

T2

T

(c) mc(T1 T2 ) (d) mc log e 2

T1

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Q5. Consider the following that take place in Carnot cycle:

1. Adiabatic expansion

2. Adiabatic compression

3. Isothermal expansion

4. Isothermal compression

The correct sequence of the above processes is:

(a) 1, 3, 4, 2 (b) 3, 1, 2, 4

(c) 3, 1, 4, 2 (d) 1, 3, 2, 4

Q6. The change in entropy of the melting of 1kg of ice at 0 0 C is

(a) 3.66 J / K (b) 15 .31 J / K

Q7. Which one of the following reversible cycles, represented by right angled triangles in a

T-S diagram, is the least efficient?

(a) T (b) T

B

3T0

2T0 B

T0 T0

A C A C

S S

S0 2S 0 S0 3S 0

(c) T (d) T

3T0 B C 2T0 B C

T0

T0 A

A

S S

S0 2S 0 S0 3S 0

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Q8. One mole of an ideal gas is carried from temperature T1 and molar volume V1 to T2 , V2 .

Then the change in entropy is given by

V2 T2

(a) S = R ln (b) S = CV ln

V1 T1

T2 V T2 V

(c) S = Cv ln R ln 2 (d) S = Cv ln + R ln 2

T1 V1 T1 V1

Q9. Consider an engine working in a reversible cycle and using an ideal gas with constant

heat capacity C p as the working substance. The cycle consists of two processes at

Then the efficiency of this engine in terms of p1 , p2 is given by

1 1

p p

(a) = 1 2 (b) = 1 2

p1 p1

1

p p 1

(c) = 1 2 (d) = 1 2

p1 p1

Q10. An insulated chamber is divided into two halves of volumes. The left

half contains an ideal gas at temperature T0 and the right half is

evacuated. A small hole is opened between the two halves, allowing the

gas to flow through and the system comes to equilibrium. No heat is

exchanged with the walls.

(a) During the process work done is zero but change in entropy of gas as well as universe

S = 0

(b) During the process work done is not zero but change in entropy of gas S = 0 and

change in entropy of universe S > 0

(c) During the process work done is zero but change in entropy of gas as well as

universe S > 0

(d) During the process work done is not zero but change in entropy of gas S > 0 as

well as universe S > 0

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Q11. Each of the two isolated vessels, A and B of fixed volumes, contains N molecules of a

perfect monatomic gas at a pressure P . The temperatures of A and B are T1 and T2 ,

respectively. The two vessels are brought into thermal contact. At equilibrium, the

change in entropy is

3 2 + 22 3

(a) k B ln 1 (b) k B ln 2

2 412 2 1

3 (1 + 2 )2

(c) k B ln (d) 2NkB

2 41 2

Q12. In diagram 1 Carnot cycle is represented in PV diagram while in Diagram II 1 Carnot

cycle is represented in TS diagram

Diagram I Diagram II

(P V ) (T S )

T1 1

A

P 4 T

2 D B

T2 3 C

V S

Which one of the following is correct?

(a) 1 and A is isothermal expansion and heat is given into the system

(b) B is adiabatic compression

(c) In process 3 heat is rejected by system

(d) Work done during 4 and B are same in magnitude and opposite to sign

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Q13. Consider the following statements regarding the characteristics of entropy are correct

(a) Entropy is a measure of disorder.

(b) Entropy changes during a reversible adiabatic process.

(c) Entropy of a system decreases in all irreversible processes.

(d) Change in entropy for a complete reversible thermodynamic cycle is zero

Q14. Consider the following statements regarding transition of a system from one

thermodynamic state another which of the following is correct

(a) The heat absorbed by it along any reversible path independent of the path.

(b) The change of entropy of the system in a reversible : process is independent of the

path.

(c) The change of entropy of the system in a irreversible process is also independent of

the path.

(d) The heat absorbed by it along any irrereversible path independent of the path.

Q15. The temperature entropy diagrams of two engines A and B working between the same

temperature T1 and T2 of the source and the sink respectively are shown in the given

figures. B

A T1

Temperature

T1

Temperature

T2 T2

S1 S1 S2

S2

Entropy Entropy

The efficiency of A :

(a) is less than that of B

(b) is equal to that of B

(c) is greater than that of B

(d) and B cannot be compared on the basis of data given in the diagrams

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Q16. Which of the the following statements are correct

(a) The entropy change during a reversible adiabatic process is zero

(b) Entropy is a state function

(c) The entropy of a thermally isolated system never decreases

(d) The entropy change during an reversible adiabatic process is zero.

Q17. An ideal gas is expanded adiabatically from ( P1 , V1 ) to ( p2 , V2 ) . Then it is compressed

P

which of the following is correct? P1 A

adiabatic

(a) the P V indicator diagram is given by fig

1 P2 C

( PV 1 1 ) + P2 (V2 V1 )

B

(b) the work done in the cycle is W = 2 2 PV

1

V1 V2 V

(c) heat will absorb in isochoric process

V2

1

V1

(d) the efficiency of the cycle is = 1

p1

1

p2

Q18. Consider an arbitrary heat engine which operates between reservoirs, each of which has

the same finite temperature-independent heat capacity c . The reservoirs have initial

temperatures T1 and T2 , where T2 > T1 , and the engine operates until both reservoirs have

the same final temperature T3 . Then which of the following statements are correct

T32

(a) The change of entropy is given by ln .

T1T2

( )

2

(d) The maximum work done is given by Wmax = c T1 T2

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Q19. Which of the statements are correct?

(a) A mole of an ideal gas undergoes a reversible isothermal expansion from volume V1

entropy of the universe .

(b) A mole of an ideal gas undergoes a reversible isothermal expansion from volume V1

to 2V1 .Then change in entropy of the gas is RT ln 2 and change in entropy of the

universe is RT ln 2

(c) A mole of an ideal gas undergoes free isothermal expansion from volume V1 to

2V1 .Then change in entropy of the gas is RT ln 2 and there is no change in entropy

of the universe

(d) A mole of an ideal gas undergoes free isothermal expansion from volume V1 to

2V1 .Then change in entropy of the gas is RT ln 2 and change in entropy of the

universe is RT ln 2

Q20. A body of constant heat capacity CP and a temperature Ti is put into contact with a

Tf

(a) Change of entropy of the body is C p ln

Ti

C p (Ti T f )

(b) The change of entropy of the heat source is

Tf

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Q21. n mole of an ideal gas is originally confined to a volume V1 in an insulated container of

volume V1 + V2 . The remainder of the container is evacuated. The partition is then

removed and the gas expands to fill the entire container. If the initial temperature of the

gas was T Insulated container

(b) The temperature remain constant T

V1 V2

V +V

(c) The work done during the process is nRT ln 1 2

V1

V +V

(d) The change entropy of gas in the process is nR ln 1 2

V1

V +V

The change in entropy of universe during the process is nR ln 1 2

V1

1

Q22. A Carnot engine has an efficiency of . On reducing the sink temperature by 65 C , the

6

1

efficiency becomes . The source temperature is given by . 0 K

3

Q23. A Carnot engine whose low-temperature reservoir is at 27 0 C has an efficiency

37.5%.The high-temperature reservoir is . 0C

Q24. In the given T S diagram, the efficiency is given by .. % (Answer must be in two

decimal point). Temperature (K)

B

200

100 C

A

500 1000

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Q25. An ideal gas is confined to a cylinder by a piston. The piston is slowly pushed in so that

the gas temperature remains at 20 0 C . During the compression, 730 J work is done on

the gas. the entropy change by the gas is .. J / K

Q26. 10 g of ice at 0C is slowly melted to water at 0C. The latent heat of melting is 80 cal/g.

The change in entropy is nearly . cal / K

Q27. If a capacitor of 1F charged to a potential of 300V is charged, a resistor kept at room

Q28. One kg of H 2O at 0o C is brought in contact with a heat reservoir at 100o C . When the

water has reached 100 o C Then the change in entropy of the universe is J / K

(specific heat of water CH 2O = 4.18 J / g )

Q29. A reversible engine cycle is shown in the following T -S diagram. The efficiency of the

engine is .. % 2T1

T1

T

S1 2S1 3S 1

S

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Solution

MCQ (Multiple Choice Questions)

Ans. 1: (b)

Solution: The efficiency of a Carnot working between temperature limits T1 and T2 is given as

T2

= 1

T1

T2 absolute temperature of sink

Since, efficiency does not depend on -working substance hence the efficiency of both

engines A and B are same

Ans. 2: (c)

Solution: The first law of thermodynamics

dQ = dU + PdV

The maximum efficiency can be obtained, if process is isoenthalpic.

Ans. 3: (a)

Solution: For a reversible process the change in entropy is zero.

dS = 0

Q1 Q

=0

T1 T

Ans. 4: (d)

T2 Q

Solution: The change in entropy of a system is given as dS =

T1 T

If Q amount of heat is given to water then T1 change in temperature dT is given as

Q = mcdT

T2 mcdT T

dS = = mc log e 2

T1 T T1

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Ans. 5: (c)

Solution:

A 1 B

AB isothermal expansion

BC adiabatic expansion 2

P 4

CD isothermal compression C

D 3

DA adiabatic compression V

Ans. 6: (c)

Solution: The change in entropy is given as

Q

dS =

T

here, Q = mL, L is latent heat

= 1000 80 Q = 80000 cal

Q = 80000 4.2 J (ii)

T = 273 K

80000 4.2

so, dS = J / K = 12.3 10 2 J / K

273

Ans. 7: (d)

W

Solution: Efficiency =

Q1

T

In a)

B

1 3T0

W = (3T0 T0 )(2 S0 S0 ) = T0 S0

2

1

Q1 = (3T0 )(2 S 0 S0 ) = 1.5T0 S 0

2 T0 A C

W S

= = 66% S0 2S 0

Q1

(a )

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In (b) T

1

W= (2T0 T0 )(3S0 S0 ) = T0 S0 B

2 2T0

1

Q1 = (2T0 )(3S0 S0 ) = 2T0 S0

2 T0

A C

W

= = 50% S

Q1 S0 3S 0

( b)

In (c) T

1

W= (3T0 T0 )(2 S0 S0 ) = T0 S0

2 3T0 B C

Q1 = (3T0 )(2 S0 S0 ) = 3T0 S0

W T0

= = 33% A

Q1 S

S0 2S 0

(c)

In (d) T

1

W= (2T0 T0 )(3S0 S0 ) = T0 S0

2 2T0 B C

Q1 = (2T0 )(3S0 S0 ) = 4T0 S0

T0

W A

= = 25%

Q1 S

S0 3S 0

(d )

Ans. 8: (d)

1 1

Solution: From dS = ( dU + PdV ) = ( Cv dT + PdV ) and PV = RT

T T

T2 V

We obtain S = Cv ln + R ln 2

T1 V1

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Ans. 9: (a)

Solution: In the cycle, the energy the working substance absorbs from the source of higher

temperature is Qab = C p (Tb Ta ) .The energy it gives to the source of lower temperature

P1 a b

Qreject Tc Td

= 1 = 1 P2

c

Qab Tb Ta d

V

form the equation of state pV = nRT and the adiabatic equations

1

P2

2 d = PV

PV 1 a , 2 c = PV

PV 1 b we have = 1

P1

Ans. 10: (c)

Solution: After a hole has been opened, the gas flows continuously to the right side and reaches

equilibrium finally. During the process, internal energy of the system E is unchanged.

Since E depends on the temperature T only for an ideal gas, the equilibrium

temperature is still T0 so from first law of thermodynamics work done is zero but process

Ans. 11: (c)

T1 + T2

Solution: Final temperature of each vessel at equilibrium is T =

2

T

CV dT

T

CV dT 3 (1 + 2 )2 3K B

S = + = k B ln where CV = for monatomic gas

T1

T T2

T 2 412 2

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MSQ (Multiple Select Questions)

Ans. 12: (a), (c) and (d)

Solution:

T1 1 A

P T

4 2 D B

T2 3 C

V S

Path 1: Expansion of constant temperature and heat is absorbed because dQ = + ve hence

S will increase Corresponding to A.

Path 2: Adiabatic expansion means S is constant Corresponding to B.

Path 3: Isothermal compression dQ = ve so heat will reject S is decrease corresponding

to C.

Path A and path B are isoentropic process so work done is dependent on points but

direction of both the case will opposite .

Ans. 13: (a) and (d)

Solution: Entropy is function of no of microstate which will measurement of disorderness

For thermodynamic process dS 0 and for reversible process dS = 0 .

Ans. 14: (b) and (c)

Solution: The entropy is point function and perfectly differential so it is path independent

Ans. 15: (a)

Solution: The efficiency is defined as

H 1 H 2 T1 T2

= =

H1 T1

Ans. 16: (a), (b), (c) and (d)

Solution: Entropy:

where Q amount of used heat in reversible adiabatic process Q = 0

Q

It is a state function and is defined as dS = is exact differential so it is state function

T

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If this taken in by a system then change in entropy is positive and so entropy of the

system increases.

The entropy change during an reversible adiabatic process is zero.

Ans. 17: (a), (b) and (d)

p1 A

Solution: (a) The cycle is shown in the figure adiabatic

p2 B

W = v PdV = PdV + P (V V )

AB

2 1 2

V1 V2

Because AB is adiabatic and an ideal gas has the equations pV = nkT and C p = Cv + R ,

we get

1

PdV = Cv dT = Cv (T2 T1 ) = ( PV 1 1)

2 2 PV

AB AB 1

(c) During the CA part of the cycle the gas absorbs heat which is isochoric

1

Q = TdS = Cv dT = Cv (T1 T2 ) = V1 ( P2 P1 )

CA CA 1

(d) Hence, the efficiency of the engine is

V2

1

W V1

= = 1

Q P1

1

P2

Ans. 18: (a), (c) and (d)

Solution: (a) The increase in entropy of the total system is

cdT T3 cdT T2

S =

T3

+ = c ln 3 0

T1 T T2 T T1T2

(d) The maximum amount of work can be obtained using a reversible heat engine, for

which S = 0 .

(

Wmax = c (T1 + T2 2T3min ) = c T1 + T2 2 T1T2 = c ) ( )

2

T1 T2

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Ans. 19: (a) and (d)

Solution: In the process of isothermal expansion, the external work done by the system is

2V1 2V1 dV

W = PdV = RT = RT ln 2

V1 V1 V

Because the internal energy does not change in this process the work is supplied by the

heat absorbed from the external world. Thus the increase of entropy of the gas is

Q W

S1 = = = R ln 2

T T

The change in entropy of the heat source S 2 = S1 thus the total change in entropy of

the universe is S = S1 + S 2 = 0 .

If it is a free expansion, the internal energy of the system is constant. As its final state is

the same as for the isothermal process, the change in entropy of the system is also the

same. In this case, the state of the heat source does not change, neither does its entropy.

Therefore the change in entropy of the universe is S = R ln 2 .

Ans. 20: (a), (b) and (c)

Solution: We assume Ti T f (because the change of entropy must be zero when Ti = T f ). The

C p dT Tf

S1 =

Tf

= C p ln

Ti T Ti

The change of entropy of the heat source is

Q C p (Ti T f )

S 2 = =

Tf Tf

T Tf

S = S1 + S 2 = C p i 1 + ln

Tf Ti

when x > 0 and x 1 , the function f ( x ) = x 1 ln x > 0 .

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V +V

The change in entropy of universe during the process is nR ln 1 2

V1

Ans. 21: (a), (c) and (d)

Solution: This is a process of adiabatic free expansion of an ideal gas. The internal energy does

not change; thus the temperature does not change, that is, the final temperature is still T .

From first law of thermodynamics the work done is zero . hence the process is

irreversible and entropy is state function so one can choose path isothermal reversible

V +V

process . so change in entropy in isothermal is nR ln 1 2 which is equal to change

V1

in entropy of gas as well as universe .

Ans. 22: 390

Solution: If T2 is Sink temperature and T1 Source temperature

T1 T2

Then, efficiency is given =

T1

1 T 5

Case 1: = 1 2 T2 = T1

6 T1 6

T2

= 1

T1

1 T 65 1 T 65

= 1 2 = 1 2 +

3 T1 3 T1 T1

1 5 65

= 1 + T1 = 65 6 = 390 0K

3 6 T1

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Ans. 23: 207

Solution: If T is temperature of source, T is the temperature of the smk then efficiency

T 37.5 300

= 1 2 = 1

T1 100 T1

300 37.5 200 75 300 8

= 1 = T1 = = 480

T1 100 200 5

Ans. 24: 33.33

Temperature

W B

Solution: = 200

Q1

1 100

W = . ( 200 100 )(1000 500 ) = 25000

C

A

2

1

Q1 = 50,000 + 500 100 = 75,000 J 500 1000

2

W

= = 33.33%

Q1

Ans. 25: 1.85

Solution: If Q amount of heat is taken by or given to (a) system at temperature T then change

in entropy is given as

Q

dS =

T

By first law of thermodynamic

Q = dU + W

According to question, since temperature is constant so no change in internal energy

dU = 0

and work of 730J is done on the system Q = 730 J

From first law of thermodynamics, Q = 0 + ( 730) Q = 730 J

and T = 273 + 20 = 293 K

Q 730

dS = = = 1.85J / K

T 293

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Ans. 26: 2.9

Solution: The entropy is defined as

Q

dS =

T

Here, Q = ML = 10 80 = 800 cal and T = 0 + 273 = 273 K

800

So, dS = cal/K = 2.9 cal/K

273

Ans. 27: 1.5

1

Solution: The energy stored in capacitor = CV 2

2

Q CV 2

So, change in entropy is given dS = dS =

T 2T

Here, C = 10 6 F , V = 300Volt , T = 27 + 273 = 300 K

10 6 (300)

2

10 6 9 10 4

So, change in entropy dS = = = 1.5 10 4 J / K

2 300 2 300

Ans. 28: 184

Solution: We assume the process is a reversible process of constant pressure. The change in

373 dT 373

entropy of the water is S H 2O = mCH 2O = mCH 2O ln

273 T 273

we substitute m = 1kg , and CH 2O = 4.18 J / g into it, and find

S H 2O = 1305 J / K

Q 100

S ha = = 1000 4.18 = 11121J / K

T 373

Therefore the change of entropy of the whole system is S = S H 2O + Sha = 184 J / K

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Ans. 29: 33

1

Solution: W = ( 2T1 T1 ) (3S1 S1 ) = T1S1

2

1

Q= ( 2T1 T1 ) (3S1 S1 ) + T1 (3S1 S1 ) = T1S1 + T1 2 S1 = 3T1S1

2

W T1S1

= = = .33 = 33%

Q 3T1S1

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Chapter - 5

Maxwell relation and Thermodynamic Potential

5.1 Maxwell Relations

F = F ( x, y ) and if it is perfect differential then dF = Mdx + Ndy

F F

Where M = and N = then M and N will satisfy the condition

x y y x

M M

=

y x x y

Maxwell relations are relationship between two derivatives of thermodynamic variables,

and energy due to the equivalence of potential second derivative under a change of

d 2F d 2F

operation order = where F is thermodynamic potential and x and y are two of

dx dy dy dx

its natural independent variables.

Maxwell relations are extremely important for two reasons.

First they show us that derivative of thermodynamic parameters are not all independent.

This can serve as a consistency check in both experiments and in theoretical analysis.

Maxwell relations provide a method for expressing some derivative in other ways. This

enables as to connect difficult to measure quantities to those which are readily accessible

experimentally.

The measurement of entropy and chemical potential can not be directly measurable in lab

but with the help of Maxwell relation there thermodynamic property can be determine

theoretically.

For Maxwell relation.

Let us Legendre the independent variable as x , and y such that

U = U(x,y), S = S(x, y) V = V(x, y)

U U

So dU = dx + dy

x y y x

S S

dS = dx + dy

x y y x

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V V

dV = dx + dx

x y y x

from first law of thermodynamic

dU = TdS PdV

U S V

= T P

x y x y x y

U S V

= T p

y x y x y x

Hence U, V,and S are perfect differential.

U U

Then =

y x y x x y x y

V V

=

y x y x x y x y

S S

=

y x y x x y x y

U T S S P V V

= + T P ---(1)

y x y x y x x y y x y x y x x y y x y x

Similarly

U T S S P V V

= + T P ---(2)

x y x y x y y x x y x y x y y x x y x y

P V P V T S T S

= (A)

x x y x y x x y x y y x y x x y

Maxwell first relation:- put x = T , y = V

S P

=

V T T V

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Maxwell Second Relation:- put x = T , y = P

S V

=

P T T P

Maxwell Third Relation:- put x = S , y = V

T P

=

V S S V

Maxwell Fourth Relation:- put x = S , y = P

T V

=

P S S P

Thermodynamic potential is a scalar function used to represent the thermodynamic state

of system. The concept of thermodynamic potentials was introduced by Pierre Duhem in

1886.

One main thermodynamic potential that has a physical interpretation is the internal

energy. It is energy of configuration of a given system of conservative forces. Expression

for all other thermodynamic energy potentials are drivable via Legendre transformation.

5.2 Different Types of Thermodynamic Potential and Maxwell Relation

Thermodynamic potentials are different form of energy which can be used in different

thermodynamic process .thermodynamic potentials are path independent variables so they

are perfect differential

If F is unique thermodynamic potential defined by variables x and y as F = F ( x, y ) and

if it is perfect differential then dF = Mdx + Ndy

F F

Where M = and N = then M and N will satisfy the condition

x y y x

M M

=

y x x y

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5.2.1 Internal Energy :- U and second from the first laws of thermodynamics

dU = TdS - PdV

from Legendre transformation

U U

= T, = P from given relation one can derive Maxwell

S V V S

T P

relation =

V S S V

5.2.2 Enthalpy (H) the enthalpy is defined as H = U + PV

dH = dU + PdV + VdP

from Laws of thermodynamics

TdS = dU + PdV

dH = TdS + VdP

from Legendre transformation

H H

=T =P

S P P S

The Enthalpy H is Extensive quantity, which can not be measured directly. Thus change

in enthalpy is more useful.

H is positive in endothermic reaction and negative in exothermic reaction.

T V

From above relation one can derive Maxwell relation =

P S S P

H of a system is equal to sum of non-mechanical work done on it and the heat supplied

to it.

5.2.3 Helmholtz Free Energy (F) the Helmholtz free energy is defined F = U TS

dF = dU TdS SdT

From laws of thermodynamics dU = TdS PdV

dF = TdS PdV TdS SdT

dF = PdV SdT

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From Legendre transformation

F F

= P, = S

V T T V

P S

From above relation one can derive Maxwell relation =

T V V T

The free Energy F, which is available energy for work in reversible isothermal process.

5.2.4 Gibbs Energy: G is defined as G = H TS.

G = U + PV TS

dG = dU + PdV VdP TdS SdT

TdS PdV + PdV + VdP TdS SdT

dG = VdP SdT

from Legendre transformation

G G

=V and = S

P T T P

V S

From above relation one can derive Maxwell relation =

T P P T

Gibbs free energy is popularly as free enthalpy.

The Gibbs free energy is Maximum amount of nonexpanding work that can be exacted

from a closed system.

The maximum will activated when the system is in reversible process.

Gibbs free energy is also treated as chemical potential.

In thermodynamics, chemical potential, as partial molar free energy, is a form of potential

energy that can be absorbed or relived during a chemical reaction.

The chemical potential of a species in the minute can be defined the slope of the energy

at system with respect to a change in the no of moles.

dG

=

dN V

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Example: Prove that internal energy U is given by

(F /T )

(a) U =

(1/ T )

V

(G / T )

(b) H =

(1 / T ) P

Solution: (a) F = U TS =U = F + TS

F

S =

T V

F F 2 (F / T ) (F / T )

U = F +T = F T = T =

T V T V T V 1 / T V

(G / T )

Solution: (b) H =

(1 / T ) P

G = H TS

G

S =

T p

G 2 G

H = G T = T

T P T T P

(G / T )

=

(1 / T ) P

5.3 Application of Maxwell Relation

5.3.1 First T dS equation

Let T, and V are independent variable S = S (T, V)

S S

dS = dT + dV

T V V T

S S S P

TdS = T dT + T dV put =

T V V T V T T v

P

T dS = C v dT + T dV .

T V

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5.3.2 Second T dS Equation

Let T and P are independent variable S = S (T, P).

S S

TdS = T dT + T dP

T P P T

From Maxwell relation

S V

=

P T P

V

TdS = C P dT T dP

T P

5.3.3 Third T-dS Equation:

Let P,V are independent variable S = S (P,V)

S S

dS = dP + dV

P P V V

S S

TdS = T dP + T dV

P V V V

S T S T

= T dP + T dV

T V P V T P V P

T T

= CV dP + C P dV

P V V P

5.3.4 The First Energy Equation

Let T and V are independent variable U = U(T, V)

U U

dU = dT + dV

T V V T

From first law of thermodynamics.

dU = TdS PdV

U S

= T P

V T V T

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S P

Using Maxwell relation T =T

V T T V

U P

= T P

V T T V

U U

dU = dT + dV

T V V T

U

= C v dT + dV

V T

U P

= T P

V T T V

P

dU = C v dT + T P dV

T V

5.3.5 Second Energy Equation

dU = TdS PdV

U S V

= T P

P T P T P T

Using Maxwell relation

S V

=

P T T P

U V V

= T P This is popularly known as second energy

P T T P P T

equation

Application of second energy equation

If U is function of independent variable of T and P.

U = U (T , P )

U U

dU = dT + dP

T P P T

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U V V

dU = dT T + P dP

T P T P P T

Example: From relation dU = TdS PdV

T P

Derive Maxwell relation =

V S S V

U U

Solution: dU = TdS PdV = P, =T

V S S V

Hence U is exact differential

U U

=

S V S v V S V S

P T

=

S V V S

Example: A real gas which obey van der Waals equation of state are kept in container which

has temperature T0 and volume V0. if volume of container changes to V such that

temperature of gas become T what is change in entropy?

Solution: Assume CV is specific heat of constant volume

For van der Waals gas

(V b ) = RT

a

P + 2

V

From first T dS equation

P

TdS = CV dT + dV

T V

P R

=

T V V b

T V

dT R

dS = CV T T + V (V b)dV

0 0

T V b

S = CV ln + R ln + S0

T0 V0 b

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where S 0 is integration constant

Example: For Vander wall gases, prove that

U a

= 2 where U is internal energy.

V T V

Solution: From first energy equation

U P

= T P -----(i)

V T T V

(V b ) = RT

a

P + 2

V

RT a

P= 2

V b V

P R P

= put the value of in equation (i)

T V (V b ) T V

U a

= 2

V T V

Example: Prove that

C 2P

(a) V = T 2

V T T V

C 2V

(b) P = T 2

P T T P

S

Solution: (a) we know CV = T

T v

CV 2 S 2 S

=T =T

V T V T V T T V T V

using Maxwell relation

S P 2 S 2 P

= one can get T = T

V T T V T V T V T T V

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CV P

2

= T 2

V T T V

S

(b) C p = T

T p

C P S S

=T =T

P T P T P T T P T P

Use Maxwell relation

S V

=

P T T P

C P 2V

= T 2

P T T P

Example: If p is thermal expansivity at constant pressure and KT isothermal compressibility

S

(i) = V p

P T

P p

(ii) =

T V K T

TV 2 P

(iii) C P CV =

KT

Solution: From Maxwell relation

S V

=

P T T P

1 V

=

V T P

S 1 V S

= V , = V

P T V T P P T

P S

(ii) =

T V V T

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P V T

= 1

T V P T V P

1 V

P 1 V T P

= =

T V V T 1 V

P T V P V P T

P

=

T V K T

S S CV S

dS = dT + dV dS = dT + dV

T V V T T V T

S CV S V C P CV S

= + = +V P

T P T V T T P T T V T

Use Maxwell relation

C P CV P C P CV

= + V P = + V P P

T T T V T T KT

T V p2

C P CV =

KT

Example: Prove that

P V

(a) CP CV = T

T V T P

(b) For the Vander Waals gas prove that

2a

CP CV = R 1 +

RTV

Q Q

Solution: (a) CP CV =

T P T V

S S

= T T ---- (A)

T P T V

S = S (T , V )

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S S S S S V

dS = dT + dV = +

T V V T T P T V V T T P

S

Put the value of in equation (A)

T P

S S V S S V

CP CV = T +T T CP CV = T

T V V T T P T V V T T P

P V S P

=T =

T V T P V T T V

(b) For van der Waals gas

a

P + 2 (V b ) = RT ---- (B)

V

a RT

P+ 2 = differentiate w.r.t. to T

V (V b )

P R

=

T V V b

Differentiate (B) with respect to V

2a V RT V R

3 = 2 +

V T P (V b ) T P V b

R

V V b

=

T P RT

2a

(V b )

2

V3

P V

Substituting the value in equation

T V T P

R R

S V

CP CV = T CP CV = T

(V b) V b

2a

V T T P RT

3

(V b ) V

2

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R

=

2a (V b )

2

1 3

V RT

1

R 2a 2a

CP CV = 2

= R 1 , CP CV = R 1 +

2a V RTV RTV

1 3

V RT

P V

Example: From CP CV = T

T V T P

Prove C P CV = TE 2V where E is bulk modulus of elasticity and is coefficient of

volume expansion.

P V

Solution: Let CP CV = T

T V T P

P = P(T , V )

P P

dP = dT + dV

T V V T

For constant pressure dP = 0

P P

dT = dV

T V V T

P P V

=

T V V T T P

2

P V

CP CV = T

V T T P

P 1 V

E = V and =

V T V T P

2

V P V 2 V E 2 2

CP CV = T = T V

V V T V T V

C P CV = TVE 2

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Example: If Helmholtz free energy for radiation is given by

8 5 K B4 T 4

F = V

45h 3 c 3

(a) What is radiation pressure

(b) If S entropy of system prove that specific heat at constant volume is given by

CV = 3S

F 8 5 K B4T 4

P = =

V T 45h 3c 3

F 32 5 K B4

(b) S = = VT 3

T V 45h 3 3

c

S 32 5 K B4 2 32 2 K B4 3

CV = T = T 3 VT = 3 VT

T V

3 3 3 3

45h c 45h c

CV = 3S

bS 3

Example: The internal energy E of a system is given by E = where b is constant and other

VN

symbols have their used meaning.

(a) Find the temperature of system

(b) Find Pressure of system

Solution: From first law of thermodynamics

bS 3

TdS = dU + PdV U =E= dU = TdS PdV

VN

U 3bS 2

(a) T = T=

S V VN

U bS 3 bS 3

(b) P = P = 2 P= 2

V S V N V N

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n U V

S = + 5 R ln + 2 R ln

2 n n

where n = number of moles, R = universal gas constant, U = internal energy

V = volume and = constant

(a) Calculate specific heat at constant pressure and volume

5

(b) Prove that internal energy is given by U = PV

2

Solution: (a) From first law of thermodynamics

1 P S 1

TdS = dU PdV , dS = dU dV =

T T U V T

n 5R 1 5

= U= nRT

2U T 2

U 5 7

CV = = nR CP = CV + R CP = nR

T 2 2

5 U 5 nRT

(b) U= nRT =

2 V 2 V

nRT

PV = nRT V=

P

U 5 5

= P U= PV

V 2 2

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3R

Example: Using the equation of state PV = nRT and the specific heat per mole C v = for

2

monatomic ideal gas

(a) Find Entropy of given system.

(b) Find free energy of given system

nRT 3R

dU = nCV dT , p= CV =

V 2

TdS = dU + PdV

dU p dT dV

dS = + dV or ds = nCV + nR

T T T V

3

S= NR ln T + N ln V + S0 where S0 is constant

2

(b) F = U TS

3nRT 3nRT

= ln T nRT ln V + F0 where F0 = T S 0 is again constant

2 2

Example: From electromagnetic theory Maxwell found that the pressure P from an isotropic

1 1U

radiation equal to the energy density i.e. P = where V is volume of the cavity

3 3V

using the first energy equation prove that

Energy density u is proportional to T 4 .

U S P

Solution: =T P =T P

V T V T T T

1 U

P= u u=

3 V

P 1 U U T U U

= = =

T V 3 T V V T 3V T V 3V

U T du 1

=u u= u

V T 3 dT v 3

du du dT

T = 4u = =4

dT u T

u T 4 =u = T 4 where is a constant.

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MCQ (Multiple Choice Questions)

S P T P

(a) = (b) =

V T T V V S S V

T V V S

(c) = (d) =

P V S P P T T P

Q2. Which one of the following thermo dynamical relations is used for certain adiabatic

changes, such as the sudden compression of a liquid or sudden -stretching of a rod?

S V S P

(a) = (b) =

P T T P T P V T

S P S V

(c) = (d) =

T P V T P T T P

Q3. Which one of the Maxwells thermodynamic relations given below leads to

Clausius-Clapeyron equation?

T P T V

(a) = (b) =

V S S V P S S P

S P S V

(c) = (d) =

V T T V P T T P

Q4. Which of the following is correct if is volume expansivity and other variables have

usual meaning in thermodynamics .

C C

(a) P = TV 2 (b) P = TV 2

P T P T

C TV C TV

(c) P = 2 (d) P = 2

P T P T

Q5. Which of the following can be derived by S = S (T ,V ) ?

P V

(a) TdS = CV dT + T dV (b) TdS = CP dT T dV

T V T P

P V

(c) TdS = CV dT T dV (d) TdS = CP dT + T dV

T V T P

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Q6. Which of the following can be derived by S = S (T , P) ?

P V

(a) TdS = CV dT + T dV (b) TdS = CP dT T dV

T V T P

P V

(c) TdS = CV dT T dV (d) TdS = CP dT + T dV

T V T P

Q7. For an isolated thermodynamically system, P, V , T ,U , S and F represent the pressure,

volume, temperature, internal energy, entropy, and Helmholtz free energy respectively.

Then the following relation is true

F F

(a) = S (b) = S

T V T P

U U

(c) =T (d) = P

S V V V

Q8. Which of the following thermodynamic relation will give the Maxwell relation

S V

= ?

P T T P

(a) dU = TdS PdV (b) dH = TdS + VdP

(c) dF = SdT PdV (d) dG = SdT + VdP )

Q9. Which of the following is not an exact differential?

(a) dQ where Q heat absorbed (b) dU where U is internal energy

(c) dS where S is entropy (d) dF where S is entropy

Q10. Which among the following sets of Maxwell relations is correct? (U-internal energy, H-

enthalpy, A-Helmholtz free energy and G-Gibbs free energy)?

U U H H

(a) T = and P = (b) V = and T =

V S S V P S S P

G G A A

(c) P = and V = (d) P = and S =

V T P S

T

S P V

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Q11. When a system is held at constant temperature and pressure in a state of equilibrium, then

it attains a minimum value of:

(a) internal energy (b) enthalpy

(c) Helmholtz energy (d) Gibbs free energy

Q12. Given that

H = the enthalpy of a system

T = absolute temperature and

S = entropy

G = H TS is the Gibbs function for the system

In the case of a reversible, isotherm and isobaric process:

(a) G = constant

(b) G > 0 and changes with T

(c) G < 0 and changes with S

(d) G changes with both T and S

Q13. The Gibbs function G in thermodynamics is defined is

G = H TS

where H is the enthalpy, T is the temperature and S is the entropy. In an isothermal,

isobaric, reversible process, G :

(a) remains constant, but not zero (b) varies linearly

(c) varies non-linearly (d) is zero

bS 3

Q14. The internal energy E of a system is given by E = , where b is a constant and other

VN

symbols have their usual meaning. The temperature of this system is equal to

2

bS 2 3bS 2 bS 3 S

(a) (b) (c) (d)

VN VN V 2N N

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Q15. The free energy of gas of N particles in a volume V and at a temperature T is

[

F = Nk B T ln a0V (k BT )

5/ 2

]

/ N , where a 0 is a constant and k B denotes the Boltzmann

constant. The internal energy of the gas is

3 5

(a) Nk B T (b) Nk B T

2 2

[

(c) Nk B T ln a 0V (k B T )

5/ 2

/N ] 3

2

Nk B T [

(d) Nk BT ln a0V / (k B T )

5/ 2

]

Q16. The entropy S of a thermodynamic system as a function of energy E is given by the

following graph

S C

B

A

E

The temperatures of the phases A, B and C , denoted by T A , TB and TC , respectively,

satisfy the following inequalities:

(a) TC > TB > T A (b) T A > TC > TB (c) TB > TC > T A (d) TB > T A > TC

Q17. The entropy of an ideal paramagnet in a magnetic field is given approximately by

S = S0 cU 2 where U is energy of the spin system and c is constant then which one is

correct plot between internal energy and temperature T where < T <

U

U

(a) (b)

T

T

U U

(c) T (d)

T

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Q18. A certain system is found to have Gibbs free energy given by

aP

G(p, T) = RT ln 5/2

(RT)

Where a and R are constants then specific heat at constant pressure ( c p ) is given by

3 5 7 9

(a) R (b) R (c) R (d) R

2 2 2 2

Q19. Helmholtz free energy is given by F = CT 4 where C is constant and T is temperature in

Kelvin then which one is correct relation between specific heat at constant volume Cv and

entropy S is given by

3

(a) CV = 2S (b) CV = 4S (c) CV = 3S (d) C v = S

2

Q20. If CV is the specific heat of the ideal gas then which of the following is correct of

Vander wall gases for same degree of freedom .

a

(a) dU = CV dT (b) dU = dV

V2

a a

(c) dU = CV dT dV (d) dU = CV dT + dV

V2 V2

Q21. For a Van der Waals gas the equation of the adiabatic curve in the variables T ,V ;

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MSQ (Multiple Select Questions)

Q22. If H is enthalpy and G is Gibbs free energy of the thermodynamic system then which of

the following is correct

(a) H = G TS (b) H = G + TS

G G

(c) H = T 2 (d) H = T 2

T T P T T P

Q23. Which of the following statements are correct .

U P

(a) The first energy equation is be given by = T P

V T T V

U

(b) The value of = 0 for Ideal gas

V T

U a

(c) The value of = 2 for Vander Waals gases .

V T V

U V

(d) The second energy equation is given by = T P

P T T P

Q24. Which of following is correct for heat capacity at constant pressure CP and volume CV

U V

(a) C p CV = p +

V T T P

R

(b) for van der waals gas C p CV =

1 2a (1 b / V ) / VRT

2

(c) van der Waals gas behave like a ideal as high temperature

(d) for Ideal gas c p cV = R

P V P V

(a) CP CV = T (b) CP CV = T

T V T P T V T P

2 2

P V P V

(c) CP CV = T (d) CP CV = T

V T T P V T T P

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Q26. If is volume expansivity of substance and T is isothermal compressibility S is

2

P V

adiabatic compressibility and it is given that CP CV = T then which

V T T P

T 2V T 2V

(a) CP CV = (b) CP CV =

T T

T 2V T 2V

(c) s T = (d) s T =

CP CP

Q27. Which of the following is correct if all variable have usual meaning in thermodynamics

S P C 2 P

(a) = (b) V = T 2

V T T V V T T V

S V C 2V

(c) = (d) P = T 2

P T T V P T T V

Q28. One mole of oxygen is expanded from a volume V1 to V2 at a constant temperature T . If

the The gas is assumed to be a Van der Waals gas

(a) the increment of the internal energy of the gas is zero

1 1

(b) the increment of the internal energy of the gas a

V1 V2

V2 b 1 1

(c) heat exchange during the process is RT ln + a

V1 b V2 V1

V2 b

(d) heat exchange during the process is RT ln

V1 b

a

Q29. The free energy for a photon gas is given by F = VT 4 , where a is a constant. The

3

entropy S and the pressure P of the photon gas are

4 a

(a) S = aVT 3 (b) , P = T 4

3 3

4 4 a 4

(c) S = aVT 3 (d) P = T

3 3

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Solutions

MCQ (Multiple Choice Questions) Solution

Ans. 1: (d)

Ans. 2: (a)

Solution: The sudden stretching of wire of compression of liquid is given by

S V

=

P T T P

Ans. 3: (c)

Solution: The rate of change of temperature pressure is given by Clausius-Clapeyron equation

dP L

which is given as = , L is latern heat

dT T (V2 V1 )

This can be derived by Maxwells first thermodynamical relation given as

S P

=

V T T V

Ans. 4: (a)

S V

Solution: from Maxwell relation =

P T T V

S V T S V

= = T

T P T P T T P P P T P T T T P P

C 2V 1 V CP

P = T 2 and = so = TV

2

P T T V V T P P T

Ans. 5: (a)

S S S P

Solution: dS = dT + dV from Maxwell relation = and

T V V T V T T V

T S

= CV

T V

P

TdS = CV dT + T dV

T V

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Ans. 6: (b)

S S S V

Solution: dS = dT + dP from Maxwell relation = and

T p P T P T T P

T S

= CP

T V

V

TdS = CP dT T dV

T P

Ans. 7: (a)

Solution: dF = SdT PdV

Ans. 8: (d)

Solution: dG = SdT + VdP

G G G G S V

= S and =V = P = T

T P P T P T P T T P T p T P

And. 9: (a)

Solution: Heat exchange is path dependent, so it is not perfect differential.

Ans. 10: (b)

H H

Solution: dH = TdS + VdP V = and T =

P S S P

Solution: The change in Gibbs free energy is given as

dG = VdP SdT

at constant P, dP = 0 at constant T, dT = 0 G constant

Ans. 12: (a)

Solution: Enthalpy H = PV + U

From laws of thermodynamics is given as

TdS = dU + PdV

so, G = U + PV TS

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dG = dU + d ( PV ) d (TS )

dG = VdP SdT

dG = VdP S dT (ii)

for isobaric dP = 0 , for isothermal dT = 0

so, equation (ii) becomes dG = 0

G = constant

Ans. 12: (d)

Ans. 13: (a)

Solution: Gibbs function is given as

G = H TS And The enthalpy H = U + PV

G = U + PV TS dG = dU + d (PV ) d (TS )

dG = dU + PdV + VdP TdS SdT

dG = VdP SdT

According to question the process is isobaric i.e., SdP = 0 isothermal i.e., dT = 0 . So

Equation (v) becomes as dG = 0 G = c

Ans. 14: (b)

E 3bS 2

Solution: TdS = dE + PdV dE = TdS PdV = T T =

S V VN

Ans. 15: (b)

Solution: F = Nk BT ln a0V (k B T ) [ 5/ 2

]

/ N , F = U TS , U = F + TS

F F F

dF = SdT PdV = S or S = U = F T

T V T V T V

a 0Vk B5 / 2

F = Nk B T ln C T ( 5/ 2

) where C =

N

F F

= Nk B ln CT

5/ 2

(

Nk B T

C 5 3/ 2

)

T T = Nk B T ln CT

5/ 2 5

Nk B T ( )

T V T V

5/ 2

CT 2 2

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F 5 F 5

T = F + Nk B T U = F T = Nk B T .

T V 2 T V 2

Solution: Now temperature of phase TA, TB , TC

dS 1 C

Now =

dE T S

B

dS

Now will be stops then it will be zero for B - phase A

dE

So TB =

E

And in C and A phases external energy of C phase is more so TC > TA

U 1 1

Solution: T = = i.e U=

S V 2cU 2cT

Ans. 18: (b)

G 5 ap

Solution: S = = R R ln 5/2

T p 2 (RT)

S 5

Cp = T = R

T 2

Ans. 19: (c)

F

Solution: S = = 4CT 3

T V

CV P

TdS = CV dT + PdV dS = dT + dV

T CV

S CV S

= CV = T CV = 3S

T V T T V

Ans. 20: (d)

U U U

Solution: U = U (T , V ) dU = dT + dV dU = CV dT + dV

T V V T V T

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U a a

= 2 so dU = CV dT + 2 dV

V T V V

Ans. 21: (b)

a

Solution: P + 2 (V b ) = RT and dU = CV dT + 2 dV

a

V V

For adiabatic process: dQ = 0 = dU + pdV

a RT a

CV dT dV = 2 dV

V b V

2

V

RT

CV dT = dV

V b

CV dT dV

=

RT V b

CV

ln Tk = ln(V b )

R

V b = (Tk )

CV / R

V b = T CV / R k CV / R

(V b )T C V /R

= k CV / R

T (V b )

R / CV

= cons tan t

MSQ (Multiple Select Questions)

Ans. 22: (b) and (c)

G

Solution: dG = SdT + VdP = S

T P

G G

G = H TS H = G + TS so H = G T H = T 2

T P T T P

Ans. 23: (a), (b) and (c)

Solution: The first law of thermodynamics is given as

dU + PdV = TdS

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U S S P

= T P From Maxwells second relation =

V T V T V T T V

U P

= T P

V T T V

U

For real gas PV = nRT so =0

V T

a U a

For Vander walls P 2 (V b ) = nRT so = 2

V V T V

U S V S P

=T P =

P T P T P T V T T V

Ans. 24: (a), (b), (c) and (d)

Solution: (a) From H = U + PV , we obtain,

H U V

= + P

T P T P T P

Let U = U T , V (T , P ) .

U U U U U V

dU = dT + dV = +

T V V T T P T V V T T p

H U U V

= + P +

T P T V V T T P

U V

Hence cP cV = P +

V T T P

a

(b) to find c p cv for a Van der Waals gas P + 2 (V b ) = RT

V

For the Van der Waals gas, we have

V R

=

T P RT 2a (V b )

V b V3

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R

Hence, c p cv =

1 2a (1 b / V ) / VRT

2

(c) and d) When V & T , cP cV R , which is just the result for an ideal gas.

Solution: S = S (T , V )

S S S S S V

dS = dT + dV T =T +

T V V T T P T V V T T P

P V

CP CV = T

T V T P

P = P (T , V )

P P

dP = dT + dV for constant pressure dP = 0

T V V T

P P V P V

Put = in CP CV = T one will

T V V T T P T V T P

2

P V

CP CV = T

V T T P

2

P V 1 V 1 V

Solution: CP CV = T it is known = and T =

V T T P V T P V p T

T 2V C P T

So CP CV = ,we know that = =

T CV S

T 2V T 2V T 2V

1 = s T = S s T =

CV T T CV CP

Ans. 27: (a), (b) and (d)

S P

Solution: from Maxwell relation =

V T T V

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S P T S P

= =T

T V T V T T V V V T V T T T V V

C 2 P

V =T 2

V T T V

S V

Similarly another Maxwell relation is given by =

P T T V

S V T S V

= = T

T P T P T T P P P T P T T T P P

C 2V

P = T 2

P T T V

Ans. 28: (b) and (d)

U a

Solution: (a) for Vander waals gas = 2

V T V

a a 1 1

U = = a

V1 V2 V1 V2

(b) We know

a

P + 2 (V b ) = RT

V

V2

RT a

P= and work done W = PdV

V b V 2 V1

V2 b 1 1

V2 2 V

RT a

W = dW = V V b dV V V 2 dV = RT ln V1 b + a V2 V1

1 1

V2 b 1 1 1 1 V2 b

Now Q = W + U = RT ln + a + a Q = RT ln

V1 b V2 V1 V1 V2 V1 b

Solution: dF = SdT PdV

F F

= S , = P

T V V T

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Chapter - 6

Phase Transition and Low Temperature Physics

6.1 Third Law of Thermodynamics and Attainable of Low Temperature

The third law of thermodynamics is some time stated as follows:

It is impossible for any process, no matter how idealized, to reduce the entropy of a

system to its zero point value in a finite number of

operations.

CP

Properties of material at low temperature Heat

Capacity CV

At T 0

CP = CV = 0

At T 0

T

S0

At T 0

1 V

Thermal expansion coefficient = =0

V T P

=0

6.2 Production of Low Temperature: The Joule Kelvin Expansion:

The Joule Kelvin Expansion is essentially a continuous steady state flow process in

which a compressed gas is made to expand adiabatically irreversibly through a porous

plug and do work.

p2

porous

plug wool

p1

p1

Constant

temperatur

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Let us assume that we start off with a gas of internal energy U1 and volume V1 . After

passing through the porous plug let find internal energy and volume of the gas by U 2 and

U 1 + P1V1 = U 2 + P2V2

H1 = H 2

Joule Kelvin expansion is isenthalpic process

H = H (T, P)

H H H

dH = dT + dP CP =

T P P T T P

H

dH = C P dT + dP dH = TdS + VdP

P T

H S

= T +V

P T P T

V

dH = C P dT + V T dP

T P

Hence H does not change dH = 0

H

The is defined

P H

T 1 V T2 V

== T V =

P H C P T P C P T T P

The equation defines a curve in the (T, P) plane and is known as the inversion curve

when = 0.

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T

T

H = H5

T1 A H = H4

H = H3

H = H2

T2 B Inversion curve

H = H1

P

P2 P1

Figure: Curves of constant enthalpy. The bold curve is the inversion curve. Inside it,

the gas is cooled on expansion. The temperature change T = T2 T1 produced in a

A series of isoenthalphs, i.e. curve with H (T , P ) = constant.

T < Ti and = Positive . There is heating effect of gases i.e. temperature and pressure

move in same direction.

T > Ti = Negative . There is cooling effect i.e. temperature and pressure move in

opposite direction.

2a

Example: (a) For van der Waals gas. Prove that inversion temperature Ti = where a and b

Rb

are parameter used in van der Waals gas.

(b) Why Hydrogen and helium shows heating effect as pressure increased at constant

enthalphy.

T 1 V

Solution: (a) = = T V

p H C p T P

For van der Waals gas

a V

P + 2 (V b ) = RT (V b )

R 2a

=

V T P P + a V3

V2

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V (V b )

=

T P 2a(V b )2

T 1 3

RTV

since b << V

1

V V b 2a V b 2a

= 1 1 = 1 1 +

T P T V RTV T V RTV

V b 2a V 2a

= 1 + . T V = b

T V RTV T P RT

1 2a

= b

C p RT

For inversion temperature

2a 2a

=0 =b Ti =

RTi Rb

(b) Since inversion temperature of Hydrogen and Helium is very small. For cooling effect

initial temperature must be smaller than inversion temperature, but for Helium and

Hydrogen inversion temperature is very small

so it is not possible to achieve initial condition lower than inversion temperature so

Helium and Hydrogen give heated effect.

T 1 V 1 V

= T V dT = T dP VdP

P H C P T P C T P

V T P V 1 P V

= 1 = =

T P P V V T T P T P T V P T

P V V T

V P

dP = dV

T P T V

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6.3 Phase Transition

A phase of a thermodynamic system and the state of matter has uniform physical

properties.

A phase transition is the transformation of thermodynamic system from one phase or

state of matter to another.

During a phase transition of a given medium certain properties of the medium change,

often discontinuously, as a result of some external condition, such as temperature,

pressure and others.

Gibbs phase rule: It is proposed by Josiah Willard Gibbs, which is given by

F =CP+2

Where C is number of components, P is the number of phase in thermodynamic

equilibrium with each other and F is number of degree of freedom.

Phase: A phase is form of matter that is homogeneous in chemical composition and

physical state.

Typical phases are solid, liquid and gas. Two immiscible (or liquid mixture with different

compositions) separated by distinct boundary are countered as two different phase.

Components: The number of components is the number of chemically independent

constituents of the system, i.e. minimum number of independent species necessary to

define the composition of all phase of the system.

The number of degree of freedom (F ) in the context is the number of intensive variable

which are independent to each other.

6.3.1 First Order Phase Transition

Let us consider one component system in which system having only one kind of

constituent particles . for first order phase transition P T diagram are shown in fig 1 .

Depending on the system, at some values for temperature and pressure, the three phases

of the system may be found in equilibrium. In the P-T diagram, the line OA represents

equilibrium between solid and liquid phases, the line OB represents equilibrium between

solid and gas phases, and the line OC represents equilibrium between liquid and gas

phases. The point O where all the three phases are in equilibrium, is known as a triple

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point. The line OC terminates at the point C, called the critical point. Beyond this point,

the gas phase cannot be converted into the liquid phase. In figure 1, the point C is at the

apex of the P-V curve at the critical temperature Tc. For the temperature T > Tc, the gas

phase of the matter cannot be converted into the liquid phase, but for T < Tc, the gas

phase can in general be converted into the liquid phase.

A

Melting

Solid

Liqui C

Critical

P

O Saturation

Triple

Gas

B T

Figure 1: P-T phase of one component

6.3.2 Equilibrium Between Two Phases

Let us consider an isolated system having a matter which is existing in two phases,

denoted by 1 and 2, simultaneously in equilibrium with each other (Figure 2). Suppose V1

and V2 are volumes, N1 and N2 the number of particles, E1 and E2 the internal energies,

and S1 and S2 the entropies of the two phases, respectively. For each phase, entropy is a

function of its volume, number of particles (mass) and internal energy.

From these relations, it follows that

B

T1 = T2 thermal equilibrium E2

P1 = P2 mechanical equilibrium

A

1 = 2 chemical equilibrium E1

equilibrium, their temperatures, pressures and chemical Figure 2: Equilibrium of two

phases of an isolated

potentials must be equal. If the chemical potentials are expressed one component system

as functions of pressure and temperature, we have

1 (P, T ) = 2 (P, T )

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where P (= P1 = P2) and T (= T1 = T2) are the common pressure and temperature,

respectively, of the two phases in equilibrium. Thus, from above equation , we have

G1 (P, T )N 1 = G 2 (P, T )N 2

G1 G2

=

N1 N 2

where G1(P, T) and G2(P, T) are the Gibbs free energies, and N1 and N2 the number of

particles in the two phases, respectively. Since during the phase transition, the number of

particles is not changing (i.e., N1 = N2), we have

G1 (P, T ) = G 2 (P, T )

Hence, during the phase transition, the Gibbs free energy does not change. Gibbs energies

G1 and G2 of the two phases 1 and 2, respectively, can be exhibited as shown in figure 4.

G1 < G2 G1 > G 2

G1 = G2

P

1 2

T

Figure 3: Phase equilibrium curve (G1 G2) separating two phases 1 and 2.

When the two phases, denoted by 1 and 2, of the given matter are in equilibrium, we have

G1 (P, T ) = G 2 (P, T )

where G1 and G2 are Gibbs free energies of the two phases, respectively, and P (= P1 =

P2) and T (= T1 = T2) are the common pressure and temperature, respectively, of the two

phases. In the P-T diagram, along the phase-transition line, let us consider a point, where

the pressure is P + dP and the temperature is T + dT so that we have

G1 (P + dP , T + dT ) = G 2 (P + dP , T + dT )

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Using Taylor series expansion and neglecting the higher order terms, we have

G G G G

G1 (P, T ) + 1 dP + 1 dT = G2 (P, T ) + 2 dP + 2 dT

P T T P P T T P

Using above two equation we get

V1 dP V2 dP S1 dT + S 2 dT = 0

dP S 2 S1 S

= =

dT V2 V1 V

H L

S = =

T T

where H (= H 2 H 1 ) is the change in heat (enthalpy) which is the molar latent heat L.

thus, from equation an we have

dP L

=

dT TV

for V2 > V1, we have

G2 G1

(A)

P T P T

further, for S2 > S1, we have

G2 G1

(B)

T P T P

6.3.4 Liquid-Vapour Phase Transition

Let us consider a phase transition from a liquid state to a vapor one. If Vi and Vg,

respectively, denote the volume in the liquid and gas phases, and Lv is the heat of

vaporization (latent heat for the transition from liquid to vapour), the Clapeyro-Clausius

equation is

dP Lv

=

dT T (V g Vi )

Since in the phase transition, Vg is always greater than Vi and the heat of vaporization Lv

is positive and we have

dP

>0

dT

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It shows that the boiling point of a liquid increases with the increase in pressure.

Now, if the vapour pressure is low, i.e., Vg >> Vi, in comparison to Vg, and we have

dP L

= v

dT TVg

dP Lv P dP Lv dT

= =

dT RT 2 P R T2

ln[P (T )] =

Lv 1

+C

R T

where C is a constant of integration. At the critical point, we have P = Pc, T = Tc and

equation is

ln[Pc (Tc )] =

Lv 1

+C

R T

L 1 1

P(T ) = Pc (Tc ) exp v

R Tc T

Here, we have assumed that the heat of vapourisation Lv is independent of the

temperature. However, it depends on the temperature. Suppose it varies as

Lv = a bT , then for an ideal gas at low pressure, we have

dP (a bT ) dT

=

P R T2

ln[P(T )] = ln (T ) + C

a 1 b

RT R

where C is a constant of integration. At the critical point, we have P = Pc , T = Tc and

equation is

a 1 b

R Tc R

On subtracting equation from and rearranging, we have

P(T ) a 1 1 b Tc

ln = + ln

Pc (Tc ) R Tc T R T

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6.3.5 Properties of First Order Phase Transition

(1) Gibbs free energy is continuous

(2) First order derivative with respect to temperature and pressure have finite

discontinuity i.e. entropy ( S ) and pressures ( P) have finite discontinuity.

(3) Second and more higher order differential is infinite

1 2 1 2

g 2

T T T

phase transitions

P P

=

T V T S

Show that

2

CV dP

= TV

S dT

Solution: Let us take T and V as independent variables and write

S = S (T , V )

so that

S S

dS = dT + dV

T V V T

For an adiabatic process, it yields

S S V

=

T V V T T S

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Using first Maxwell relation, we obtain

S P V

=

T V T V T S

P

Since CV = T we can write

T V

P V P V P

CV = T = T

T V T S T V P S T S

P P

2

dP

= TV S = TV S

T V T S dT

where S is adiabatic compressibility.

Example: Calculate under what Pressure water would boil at 120 C. One gram of steam

occupies a volume of 1677 cm3. Latent heat of steam = 540 cal/g, J = 4.2 107 erg/cal.

atmospheric pressure = 1.0 106 dyne/cm3

dP L L dT

Solution: = dP =

dT T (V2 V1 ) (V2 V1 )

V2 = 1677 cm3/g V2 = 1 cm3/g

dP = 0.725 P2 P1 = .725

P2 = 0.725 + P1 = 1 + 0.725 = 1.725

Example: Liquid helium 4 has normal boiling point of 4.2 k. However at pressure at 1 mm of

mercury it boils at 1.2 k. Estimate the average latent heat of vaporization of helium in

this temperature range.

dP L L

Solution: = =

dT T (Vg Ve ) TVg

RT

PVg = RT Vg =

P

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dP L dP LP

= =

dT RT dT RT 2

T

P

P L 1 1

P T

dP L dT

P P = R T T 2 ln =

P0 R T0 T

0 0

P

R ln

P0

L=

1 1

T0 T

P0 = 746 mm T0 = 4.2 k

P1 = 1 mm T = 1.2

L = 93 J/mol.

Example: Liquid helium boils at temperature T0 when its vapour pressure is equal to P0 we now

pump on the vapour and reduce the pressure to much smaller value P. Assume that the

Latent heat L is approximately independent at temperature and helium vapour density is

much smaller than that of liquid, calculate the approximate temperature Tm of the liquid

in equilibrium with its vapour at pressure P.

Express your answer in terms of L, T0, P0, Pm and any other required constants.

dP L

Solution: = V = Vgas Vliq Vgas

dT TV

Pm T

dP LP dP L m dT

=

dT RT 2 P = R T T 2

P0 0

T0

Tm =

RT P

1 + 0 ln 0

L Pm

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Example: In the phase transition from a liquid state to a vapour state. The heat of vapourisation

Lv varies with temperature T as Lv = a bT 1 / 2 . Considering the gas as an ideal one at

low pressure, show that the pressure P (T ) at temperature T in terms of the critical

pressure Pc (Tc ) at critical temperature Tc is given by

P(T ) a 1 1 b 1 1

ln = + 2 1 / 2 1 / 2

Pc (Tc ) R Tc T R T Tc

Solution: Clapeyron-Clausius equation for the phase transition from liquid to vapour is

dP Lv

=

dT T (V g Vi )

where Lv is the heat of vapourisation and Vi and Vg , respectively, denote the volume is

dP L

= v

dT TV g

Using Lv = a bT 1 / 2 , we have

dP a bT 1 / 2

=

dT TV g

dP

=

(

a bT 1 / 2 P )

dT RT 2

=

(

dP a bT 1 / 2 P

dT =

)

a dT b dT

2

dT RT R T 2 R T 3/ 2

ln[P(T )] =

a 1 b 1

+ +C

R T R T 1/ 2

On subtracting equation above and rearranging, we have

P(T ) a 1 1 2b 1 1

ln = + 1 / 2 1 / 2

Pc (Tc ) R Tc T R T Tc

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S P

Derive Glausius-Clapeyron equation from Maxwell relation = .

V T T V

S P S P Q P

= T = T = T

V T T V V T T V V T T V

Q = Ldm

P L P L

T = =

T V Vvap Vliq T V T (Vvap Vliq )

(b) Draw Phase diagram for water and explain why water expand after freezing.

Phase diagram for water

The slope of solid liquid phase is negative.

So from Clausius:- P liquid

solid critical point

Clapeyron equation

P L gas

=

T sat T (Vliq Vsolid ) T

P

= ve Vliq Vsolid < 0 Vliq < Vsolid

T

so water expand on freezing

6.3.6 Second Order Phase Transition:

In some cases the state of matter does not change but the arrangement of its constituent

particle changes. This kind of phase transition is known as second order phase transition.

In the case of second order phase transition, no heat is evolved or absorbed. In second

order phase transition

1. Gibbs free energy is continuous

1 2

1 2

g g

T p

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2. First order differential of Gibbs energy with respect to temperature ie entropy are

changes smoothly

T p

T p

3. Second order differential of Gibbs energy with respect to temperature ie specific heat

and second order differential of Gibbs energy with respect to pressure ie isothermal and

isobaric expansivity have finite discontinuity at critical temperature.

Cp

T p

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4. The thermodynamic property which are determine by more than second order

derivative will be infinite at critical temperature,

P

75

50

solid

He

25

vapour

He

0 T

1 2 3 4 5

Figure: Phase diagram of helium

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MCQ (Multiple Choice Questions)

Q1. In phase transition of first order, there is a finitely discontinuity at the transition point of

(a) Gibbs free energy G

(b) The first-order derivatives of G

(c) The second -order-derivatives of G

(d) The higher -order-derivatives more than second order of G

(where G is the Gibbs function)

Q2. In phase transition of second order, there is a infinitely discontinuity at the transition

point of G is the Gibbs function

(a) Gibbs free energy G

(b) The first-order derivatives of G

(c) The second -order-derivatives of G

(d) The higher -order-derivatives more than second order of G

(where G is the Gibbs function)

Q3. Which of the following is finitely discontinuous at transition temperature for first order

transition?

(a) Gibbs free energy (b) Entropy

(c) Specific Heat (d) Volume expansibility

Q4. The Clausius-Clapeyron equation indicates that the increase of pressure increases the

melting point:

(a) in the case of all substances

(b) in the case of substances which expand on solidification

(c) in the case of substances which contract on solidification

(d) in the case of substances which neither expand nor contract on solidification

Q5. Consider the following statements in respect of first-order phase transition:

1. Clausius-Clapeyron latent heat equation holds well in the first-order phase transition.

2. There is change in entropy and volume in the first-order phase transition.

Which of the above statements is/are correct?

(a) 1 only (b) 2 only (c) Both 1 and 2 (d) Neither 1 nor 2

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Q6. The Joule-Thomson expansion produced cooling:

(a) at all initial temperatures and pressures

(b) above certain initial temperature

(c) above certain initial pressure

(d) below certain initial temperature

Q7. After Joule-Thomson expansion, the gas is:

(a) always heated

(b) heated or cooled depending upon the initial temperature of the gas

(c) neither heated nor cooled at any temperature

(d) always cooled

Q8. Match List I and List II and select the correct answer using the codes given below the

Lists:

List I List II

A Temperature of inversion in Joule- 1. U

=0

. Thomson effect is related to V T

B For perfect gases 2. T 1 2a

= b

. P H C P RT

C For a perfect gas Joule-Thomson 3.

(PV )T 0

. effect vanishes because P

T V = 0

. T

Codes:

A B C D

(a) 2 4 1 3

(b) 3 1 4 2

(c) 2 1 4 3

(d) 3 4 1 2

Q9. On the inversion curve, the Joule-Thomson coefficient is:

(a) positive (b) zero (c) negative (d) infinite

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MSQ (Multiple Select Questions)

Q10. Which of the following is correct statement about first order phase transition.

(a) The Gibbs free energy is continuous at transition temperature

(b) The entropy is finitely discontinues at transition temperature

(c) Pressure is infinitely discontinues at transition temperature

(d) Specific heat is infinitely discontinuous at transition temperature

Q11. Which of the following is incorrect statement about second order phase transition?

(a) The Gibbs free energy is continuous at transition temperature

(b) The entropy is finitely discontinues at transition temperature

(c) Pressure is infinitely discontinues at transition temperature

(d) Specific heat is infinitely discontinuous at transition temperature

Q12. Which of the following is finitely discontinuous at transition temperature for second

order transition?

(a) Gibbs free energy (b) Entropy

(c) Specific Heat (d) Volume expansibility

Q13. Which of the following is correct statement for phase transition?

(a) Clausius-Clapeyron latent heat equation holds well in the first-order phase transition.

(b) There is not change in entropy and volume at critical temperature in the second-order

phase transition.

(c) The change of phase when water transformed in Ice is first order transition

(d) The concept of superconductor and super fluid can be explain by second order

transition

Q14. Which is correctly matched for van der Waals gas?

2a

(a) Inversion temperature is given by Tinversion =

Rb

2a

(b) Boyle temperature is given by TBoyle =

Rb

8a

(c) Critical temperature is given by Tcritical =

27bR

a

(d) Boyle temperature is given TBoyle =

Rb

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Q15. Which of the following pairs are correctly matched?

(a) Law of liquefaction of gases triple point

(b) Law of liquefaction of gases critical temperature

(c) Cooling effect of gas inversion temperature

(d) Phase transition Boyle temperature

T

Q16. The Joule-Thomson coefficient = :

P H

(a) less than zero at all temperatures and pressures for ideal gas

(b) zero at all temperatures and pressures for ideal gas

(c) less than zero at all temperatures and pressures for real gas

(d) can have any value depending on pressure and temperature for real gases

Q17. Consider the following statements:

A gas can be liquefied by increasing the pressure

(a) Above the critical below critical temperature only.

(b) Only when the temperature of the enclosed gas in below the critical temperature.

(c) Only when the volume of the enclosed gas is below the critical volume.

(d) Ideal gas can not be liquefied.

Q18. Consider the following statements:

When a compressed real gas is allowed to pass through a narrow hole, the temperature

(a) Falls for some gases if T < Ti

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Solutions

MCQ (Multiple Choice Questions)

Ans. 1: (b)

G

Solution: In first order phase transition Entropy S = is discontinuous at transition

T P

point

Phase transition and low temperature physics.

Ans. 2: (d)

Ans. 3: (b)

G G

Solution: for first order phase transition G is continuous S = and V = is

T P p S

2G

finitely discontinuous and CP = T 2 is infinitely discontinuous

T P

Ans. 4: (c)

Solution: Clausius-Clapeyron equation is given as

dP L dP

= If V2 > V1 , is positive

dT T (V2 V1 ) dT

Ans. 5: (c)

Ans. 6: (d)

Solution: Cooling effect is produced when temperature is below a temperature known as

temperature of inversion.

Ans. 7: (b)

Solution: The drop of temperature dT in Joule.

Thomson effect is given as

P 2a

dT = b (i)

CP M RT

2a 2a

No change in temperature if b = 0 Ti =

RT Rb

Headoffice Branchoffice

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fiziks

InstituteforNET/JRF,GATE,IITJAM,JEST,TIFRandGREinPHYSICALSCIENCES

This temperature is known as temperature of inversion Equation (i)

2a 2a

dT > 0 if b > 0 T<

RT Rb

If temperature T of the gas is less than temperature of inversion then cooling effect is

observed otherwise heating effect.

Ans. 8 : (c)

Solution: (i) The temperature of inversion in Joule-Thomson effect is the temperature above of

which all gases show heating effect. Below of this all gases show colling effect and at the

temperature of inversion no effect. This is given as

T 1 2a

= b

P H C P RT

(ii) The internal energy of a perfect gas does not depend on volume this depends only on

temperature. Thus,

U U

= =0

V T P T

U a

For real gases = 2

V T V

(iii) For a perfect gas Joule-Thomson effect vanishes because

V

T V = 0

T

(iv) The pressure P and PV is related as

PV = A + BP + CP 2 + DP 3 +

A > B > C > D are virial constants.

The Boyles law is applied when P is very low hence when

PV = A

( PV ) = 0

P

So, deviation from Boyles law (PV )T 0

P

Headoffice Branchoffice

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fiziks

InstituteforNET/JRF,GATE,IITJAM,JEST,TIFRandGREinPHYSICALSCIENCES

Ans. 9: (b)

Solution: An isenthalpic curve is the locus of all points

representing equilibrium of same enthalpy.

temperature

inversioncurve

If temperature is not very high then such curves

pass through a maximum, called the inversion

cooling heating

point. The locus of all inversion points is called

T

the inversion curve. Since, towards the left of the

maximum of either curve of constant enthalpy, the

gas shows cooling effect, the region inside the P

pressure

inversion curve is the cooling region, for this

region gas shows cooling effect.

On the other hand, the region outside the inversion curve the gases show heating effect

and region is called region of heating.

The Joule-Thomson coefficient is defined as

T 1 V

= = T V

P H C P T P

On the inversion = 0

Thus, Joule-Thomson coefficient is zero.

Ans. 10: (a), (b) and (d)

G G

Solution: For first order phase transition G is continuous S = and V = is

T P p S

2G

finitely discontinuous and CP = T 2 is infinitely discontinuous

T P

Headoffice Branchoffice

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fiziks

InstituteforNET/JRF,GATE,IITJAM,JEST,TIFRandGREinPHYSICALSCIENCES

Ans. 11: (b), (c) and (d)

G G

Solution: For second order phase transition G is continuous S = and V = is

T P p S

2G

continuous and CP = T 2 is finitely discontinuous .

T P

Ans. 12: (c) and (d)

G G

Solution: For second order phase transition G is continuous S = and V = is

T P p S

2G

continuous and CP = T 2 is finitely discontinuous

T P

Ans. 13: (a), (b), (c) and (d).

Ans. 14: (a), (c) and (d)

2a a 8a

Solution: Tinversion = , TBoyle = and Tcritical =

Rb Rb 27bR

Ans. 15: (b) and (c)

Ans. 16: (b) and (d)

Solution: Joule-Thomson coefficient for ideal gas is zero

T

i.e., =0

P H

whereas for real gas it is given as

T 1 2a

= = b

P H C P RT

a, b are Vander Waals constant.

Ans. 17: (b) and (d)

Solution: When temperature of a gas is above a fixed temperature, known as critical

temperature, the gas cannot be liquid whatever the pressure is applied.

If temperature of the gas is equal to or smaller than the critical temperature, then it can be

liquefied.

Headoffice Branchoffice

fiziks,H.No.23,G.F,JiaSarai, AnandInstituteofMathematics,

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Email:fiziks.physics@gmail.com166

fiziks

InstituteforNET/JRF,GATE,IITJAM,JEST,TIFRandGREinPHYSICALSCIENCES

Ans. 18: (a) and (c)

Solution: The fall of temperature is given as

dP 2a

dT = b

C P RT

2a

Ti =

Rb

Thus, temperature T > Ti then heating effect,

Headoffice Branchoffice

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