HEAT & THERMODYNAMICS

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 Contents
5. Thermometry, Expansion &
Calorimetry 365-414
5.1 Introduction 366
5.2 Temperature 366
5.3 Thermal expansion of solids 370
5.4 Expansion of liquids 373
5.5 Expansion of gases 376
5.6 Heat and calorimetry 382
5.7 Special heat 382
5.8 Heat capacity or thermal capacity 385
5.9 Water equivalent 385
5.10 Change in phase 386
5.11 Latent heat 387
5.12 Law of mixture or law of calorimetry 389
Review of formulae & important points 392
Exercise 5.1 - Exercise 5.6 393-404
Hints & solutions 405-414
6. Kinetic Theory of Gases 415-456
6.1 Introduction 416
6.2 Gas laws 416
6.3 Ideal gas 418
6.4 Kinetic theory of gases 423
6.5 Translational kinetic energy 424
6.6 Grahams law of diffusion 425
6.7 Daltons law of partial pressure 426
6.8 The distribution of molecular speed 426
6.9 Degrees of freedom 429
6.10 Law of equipartition of energy 431
6.11 Mean free path 432
6.12 Phases and phase diagrams 433
6.13 Vapour pressure 436
6.14 Dew point 437
6.15 Humidity 437
Review of formulae & important points 438
Exercise 6.1 - Exercise 6.6 439-448
Hints & solutions 449-456
7. Laws of Thermodynamics 457-526
7.1 Thermodynamical terms 458
7.2 Internal energy 458
7.3 Internal energy of an ideal gas 458
7.4 Work in volume change 459
7.5 Work done in cyclic process 460
7.6 First law of thermodynamics 461
Contents
7.7 Reversible process 464
7.8 Thermodynamical processes 464
7.9 Change in internal energy 469
7.10 Polytropic process 470
7.11 Weakness of first law and need of 477
second law
7.12 Second law of thermodynamics 478
7.13 Entropy 478
7.14 Heat engine 479
7.15 Carnot reversible heat engine 479
7.16 Refrigerator or heat - pump 482
Review of formulae & important points 485
Exercise 7.1 - Exercise 7.6 486-508
Hints & solutions 509-526
8. Heat Transfer 527-570
8.1 Modes of heat transfer 528
8.2 Thermal conduction 528
8.3 Steady state and temperature gradient 528
8.4 Rate of flow of heat : heat current 529
8.5 Thermal resistance 529
8.6 Determination of thermal conductivity 530
8.7 Combination of metallic rods 532
8.8 Redial flow of heat 533
8.9 Cylindrical flow of heat 534
8.10 Formation of ice on ponds 534
8.11 Application of conductivity in daily life 539
8.12 Convection 539
8.13 Phenomenon based on convection 539
8.14 Radiation 541
8.15 Spectral absorptive power 541
8.16 Spectral emissive power 541
8.17 Emissivity 542
8.18 Black body 542
8.19 Kirchhoffs law 542
8.20 Prevost theory of heat exchange (1792) 543
8.21 Stefan -boltzmann law 543
8.22 Newtons law of cooling 543
8.23 Wiens displacement law 547
8.24 Solar constant 547
Review of formulae & important points 548
Exercise 8.1 - Exercise 8.6 549-560
Hints & solutions 561-570
 Chapter 5
Thermometry, Expansion & Calorimetry
382

5.7 SPECIAL HEAT

It is defined as the amount of heat required to raise the temperature of unit mass of a
substance through 1 K (1 C). Suppose Q amount of heat is supplied to m amount of
substance, the rise in temperature of substance is DT , then specific heat is given by
Q
c =
m DT
or we can write, Q = mcDT
Units of specific heat
(i) In CGS system, the unit of Q is calorie, m is gram and DT in C. Therefore unit of
c in this system becomes
c = cal/g C
(ii) In SI system, the unit of Q is Joule, m in kg and DT in kelvin. Therefore in this
system unit of specific heat becomes J/kg-K.
1. Specific heat of water is 1cal/g-C or 4200 J/kg-K.
2. Specific heat of ice is 0.5 cal/g-C or 2100 J/kg-K.
3. The maximum value of specific heat is 3.5 cal/gC for hydrogen.
4. The minimum value of specific heat is 0.022 cal/gC for radon.
The specific heat of a substance is not constant at all temperature. Therefore specific
heat used in the above formula is the mean value of specific heats. When c varies
considerably with temperature, then for small change in temperature dT, we can write
dQ = mcdT
T2

\ Q = mcdT
T1
Here T1 and T2 are the initial and final temperatures.
Dulong and Petits Law (1819)
At near about room temperature the molar specific heat of most of the solids is equal to
3R or 6 cal/mol-K at constant volume.
In case of solids, the significant motion of atoms are vibratory motion. During vibration,
the kinetic energy (Ek) of an atom changes periodically into potential energy (EP) and
vice-versa. So the average values of Ek and Ep are equal.
For each form of energy there are three degrees of freedom. Therefore a molecule has six
degrees of freedom (3 for kinetic + 3 for potential). According to law of equi-partition of
kT
energy, each degree of freedom possesses energy per atom. Therefore total energy
2
associated with one mole of a substance at a temperature T is given by;
kT 3
Ek = 3 = kT
2 2
kT 3
EP = 3 = kT
2 2
\ Average vibrational energy per atom
= Ek + E p = 3kT
The internal energy (due to vibration) of one mole of an atom of the solid is given by
U = (3kT ) N
= 3(kN)T
= 3RT (kN = R)
dU
Also, we have CV =
dT
d (3RT )
=
dT
or CV = 3R
dU
Proof of formula CV = , will be discussed in the next chapter..
dT
 THERMOMETRY, EXPANSION AND CALORIMETRY 383
Variation of specific heat of solid with temperature
The figure shows the variation of molar specific heat (CV) as a function of temperature.
It can be easily understand that at higher temperature the molar specific heat of all solids
is close a value 3R.

Specific heat of gas

Limit of specific heat of gas : Consider a gas of mass m and volume V at a pressure P.
(i) Suppose gas is compressed suddenly without supplying heat :
Let the temperature of the gas rises by DT .
DQ
\ c =
m DT
But DQ = 0 , \ c = 0.
(ii) Heat is supplied to the gas and it is allowed to expand in such a way that there is no
rise in temperature. i.e., DT = 0

DQ
\ c =
m DT
Fig. 5.24 DQ
= =
m 0
Thus the specific heat of a gas may varies from zero to infinity. It may have any
positive or negative value. The exact value depends on the conditions of pressure
and volume when heat is being supplied. Out of the many specific heats of a gas,
two are of prime significance.
1. Molar specific heat at constant volume CV
It is the amount of heat required to raise the temperature of 1 mole of a gas through
1 K (1 C) at constant volume. If QV is the heat given to n moles of a gas at constant
volume and change in temperature be DT , then

Qv
CV =
n DT

or QV = nCv DT
2. Molar specific heat at constant pressure CP
It is the amount of heat required to raise the temperature of 1 mole of a gas through
1K (1C) at constant pressure. If QP is the heat given to n moles of a gas at
constant pressure and change in temperature be DT , then

QP
CP =
n DT

or QP = nCP DT

Relation between CV and CP : Mayers formula

Heat supplied to a gas at constant volume entirely used to raise its temperature. When a
gas is heated at constant pressure, it expand to keep pressure constant and therefore
some mechanical work is to be done in addition to raise the temperature of the gas. Hence
more heat is required at constant pressure than that at constant volume. Thus for one
mole of a gas, we have
 384 MECHANICS, HEAT, THERMODYNAMICS & WAVES
CP CV = Work done
= PDV (1)
At constant pressure, we have
PV1 = RT (2)
and PV2 = R (T + 1) (3)
where V1 is the volume of gas at temperature T and V2 is the volume of gas at temperature
(T + 1). Subtracting equation (2) from (3), we get
P (V2 - V1 ) = R
or PDV = R
Substituting this value in equation (1), we get
CP - CV = R Mayers formula
Fig. 5.25

Note:
1. Substance which expand on heating, PDV is positive and therefore,
CP - CV = +ve or CP > CV . If any substance contracts on heating, PDV will be
negative and therefore, CP - CV = -ve or CP < CV .

2. CP - CV = R holds good for all ideal gases.

3. For one gram of a gas, we have cV and cPand we can write CV = McV and
CP = McP . Also, cP - cV = r
R
Here r = which is different for different gases.
M
 Chapter 7
Laws of Thermodynamics

7.8 THERMODYNAMICAL PROCESSES

Any process may have own equation of state, but each thermodynamical process must
obey PV = nRT.
1. Isobaric process
If a thermodynamic system undergoes physical change at constant pressure, then
the process is called isobaric.
(i) Isobaric process obeys Charles law, V T
dP
(ii) Slope of P ~ V curve, = 0.
dV
(ii) Specific heat at constant pressure Fig. 7.21
5R 7R
CP = for monoatomic and CP = for diatomic
2 2
(iv) Bulk modulus of elasticity: As P is constant, DP = 0
DP
and B = =0
DV
-
V
(v) Work done: W = PDV = nRDT
(vi) First law of thermodynamics in isobaric process
Q = DU + W = DU + PDV = DU + nRDT Fig. 7.22
= nCV DT + nR DT = n(CV + R)DT
= nCP DT
(vii) Examples: Boiling of water and freezing of water at constant pressure etc.
2. Isochoric or isometric process
A thermodynamical process in which volume of the system remain constant, is
called isochoric process.
(i) An isochoric process obeys Gay - Lussacs Law, P T
dP
(ii) Slope of P V curve, =
dV
(ii) Specific heat at constant volume
3R 5R
CV = for monoatomic and CV = for diatomic Fig. 7.23
2 2
(iv) Bulk modulus of elasticity : As V is constant, DV = 0
DP
\ B = = `
-DV

V
(v) Work done : W = PDV = 0
(vi) First law of thermodynamics in ischoric process
Q = DU + W = DU+ 0
or Q = DU
= nCVDT
3. Isothermal process
A thermodynamical process in which pressure and volume of the system change
at constant temperature, is called isothermal process.
(i) An isothermal process obeys Boyles law PV = Constant.
(ii) The wall of the container must be perfectly conducting so that free exchange
of heat between the system and surroundings can take place.
(iii) The process must be very slow, so as to provide sufficient time for the
exchange of heat.
 LAWS OF THERMODYNAMICS 465
(iv) Slope of P V curve:
For isothermal process
PV = Constant
After differentiating w.r.t. volume, we get
dP
P +V = 0
dV
dP -P -P
or = or tan q =
dV V V
(v) Specific heat at constant temperature:
As DT = 0,
Fig. 7.24 DQ
\ C = =
n DT
(vi) Isothermal elasticity: Bulk modulus at constant temperature is called isothermal
elasticity. It can be
defined as
DP dP
Eiso = B = =
-DV -
dV
V
dP V
From above = P
- dV

V

\ Eiso = P
Vf

(vi) Work done : W = PdV

Vi

nRT
By PV = nRT P =
V
Vf
dV
\ W = nRT V

Vi

V
= nRT lnV V
f
i

Vf
or W = nRT ln
Vi

Vf
Here V is called expansion ratio.
i

Vf Pi
Also PiVi = PfVf, \ = Pf
Vi

Vf Pi
\ W = nRT ln = nRT ln

Vi Pf

(viii) First law of thermodynamics in isothermal process.

As DT = 0, \ DU = 0
Q = DU + W = 0 + W
or Q = W
466 MECHANICS & THERMODYNAMICS

4. Adiabatic process
An adiabatic process is one in which pressure, volume and temperature of the
system change but heat will not exchange between system and surroundings.
(i) Adiabatic process must be sudden, so that heat does not get time to exchange
between system and surroundings.
(ii) The walls of the container must be perfectly insulated.
(iii) Adiabatic relation between P and V
According to first law of thermodynamics
dQ = dU + dW
For adiabatic process, dQ = 0, \ dU + dW = 0 ...(1)
For one mole of gas
dU = CVdT and dW = PdV
Substituting these values in equation (1), we have
CVdT + PdV = 0 ...(2)
For one mole of an idea gas,
PV = RT ...(3)
After differentiating equation (3), we get
PdV + VdP = RdT
PdV +VdP
or dT =
R
From equation (2)
PdV + VdP
CV
R + PdV = 0

or CV PdV + CVVdP + RPdV = 0
or (CV + R) PdV + CVVdP = 0
or CPPdV + CVVdP = 0
After rearranging, we get
CP dV dP
+ = 0
CV V P

CP
Substituting
CV
= g , we have

dV dP
or g + = 0 ...(4)
V P
Integrating equation (4), we get
dV dP
g
V P
+ = C

or glnV + ln P = C
or lnV g + lnP = C

or ln( PV g ) = C
or PV g = eC
or PV g = k
Adiabatic relation between V and T & P and T
For one mole of gas
RT
PV = RT, or P =
V
Substituting in PVg = k, we get
 LAWS OF THERMODYNAMICS 467

RT g
V = k
V
k
or V g -1T =
R
= new constant

RT
Also V =
P
g
RT
\ P = k
P
k
or P1-gT g =
Rg
= another constant

(iv) Slope of P V curve : We have PV g = k . On differentiating,

dP
we have P g V g-1 + V g = 0
dV
dP P
or = -g
dV V
Fig. 7.25
P
or tan q = -g
V

As slope of isothermal curve = -

P
V

\ Slope of adiabatic curve = g slope of isothermal curve.

Since g > 1, so slope of adiabatic always be greater than slope of isothermal
curve.
Q 0
(v) Specific heat : C = = =0
n DT n DT
Fig. 7.26 (vi) Adiabatic elasticity: Bulk modulus of gas at constant heat is called adiabatic
elasticity. If can be defined as
DP dP
Ead = B= =
-DV - dV

V V

dp
As = gP
dV
-
V
\ Ead = gP

As Eiso = P, \ Ead = g Eiso

Vf

(vii) Work done : W = PdV

Vi

g g
For adiabatic process PV g = i i = Pf V f = k
PV
or P = kV g
468 MECHANICS & THERMODYNAMICS

Vf
-g
\ W = kV dV
Vi
Vf
V 1-g
= k
(1 - g )
Vi
1
= [kV f 1-g - kVi1-g ]
(1 - g )
1
= [( Pf V f g )V f 1-g - ( PV g 1-g
i i )Vi ]
(1 - g )
1
= Pf V f - PV
i i
(1 - g )

i i - Pf V f )
( PV
or W =
(g - 1)

Also PiVi = nRTi and PfVf = nRTf

nR
\ W = [Ti - T f ]
g -1

(viii) First law of thermodynamics in adiabatic process

Q = DU + W
As Q = 0, \ DU = W
or Uf Ui = W
\ Uf = Ui W
Summary of four gas processes :
Fig. 7.28 shows four different processes : Isobaric, isothermal, adiabatic and isochoric.
Constant Process Some results
Path
quantity type U = Q W and U = nCV T for all paths
1 P Isobaric Q = nCP T ; W = PV
2 T Isothermal Q = W = nRT ln(V f / Vi ); DU = 0
3 PV g , TV g-1 Adiabatic Q = 0; W = -DU Fig. 7.28 P V diagram representing
4 V Isochoric Q = DU = nCV DT ; W = 0 four different processes for an ideal gas