Thermodynamics (311-364)

PHYSICS-IC THERMODYNAMICS
THERMODYNAMICS
* Heat Capacity, Water equivalent, Specific heat
* Three phases of Matter, Latent Heat
* Thermodynamic system, Work, Heat, Zeroth law of
9 *
*
Thermodynamics
Isothernal Process, Adiabatic Process
Heat engine and Refrigrator, Second law of thermodynamics
9.1. Introduction : 9.2. Heat and temperature :

Thermodynamics deals with the relation of heat Heat is a form of energy called thermal energy.
energy to mechanical work and other forms of When we bring a hot body in thermal contact
energy. One aspect of this relationship is conversion with a cold body, then temperature of the hot body
of mechanical work into heat. When we rub our decreases and temperature of the cold body increases.
palms they become warm. This is due to the The energy of the hot body decreases and that of the
conversion of mechanical work performed in rubbing cold body increases. This transfer of energy takes
our hands together into heat. Earlier Count Rumford place until the two bodies attain a common
in 1798 found that a large amount of heat was temperature, showing that the two bodies are at the
produced by friction and the heat produced by friction same thermal condition.
was proportional to the work done. Sir Humphrey So heat flows from a body at higher temperature
Davy in his experiment rubbed two blocks of ice in to a body at lower temperature. This leads to the
vacuum and found that they melted due to heat definition of heat .
generated by friction. It can be concluded that the Definition of Heat : The energy which is transferred
heat is generated when the mechanical work is between a system and its surroundings, as a result
performed on the body. The ice blocks are made to of temperature difference only, is called heat.
melt by the heat generated or by directly heating So heat can be taken as cause and the
them. This shows that both work and heat are the temperature as effect.
two forms of energy. Later James Joule and others Unit : joule in SI, Calorie in CGS system.
showed that heat lost or gained in any process could Dimensional formula : [ML2T–2].
be accounted for an equal amount of work done. Definition of Temperature :
Temperature is defined as the thermal
The study of energy relations and the manner condition of a body which determines its ability to
in which energy changes take place are based on transfer heat to other bodies.
two general laws, the first and the second law of a) Temperature is the measure of degree of hotness
thermodynamics. First law represents the connection or coldness of a body.
between heat and mechanical work, while the second b) Temperature determines the direction of net flow
law depicts the manner in which this energy change of heat.
takes place. Unit : Kelvin (K) in absolute scale.
Thermodynamics deals with the macroscopic Dimensional formula [K] or [  ].
(large scale) properties and does not go into the UNITS OF HEAT
microscopic level. It is an experimental science and Various units of heat are obtained by choosing
the laws have been developed by observations and different units of mass and temperature. The most
experimental facts. commonly used unit is calorie.
THERMODYNAMICS PHYSICS-IC
Calorie : It is the unit of measuring heat. Calorie Def : The specific heat of a material is defined as
is generally defined as the amount of heat required the quantity of heat required by unit mass of the
by one gram of water to rise its temperature by 1°C. material to rise its temperature by one degree.
In fact, one gram of water does not require the Let  Q be the quantity of heat required to rise
same amount of heat to rise the temperature by 1°C the temperature of the body of mass 'm' through  t.
at all ranges of temperature. When one gram of  Q  mass of the body "m"
water is heated from 0°C to 100°C, the mean value  temperature rise "  t"
of the amount of heat required for 1°C rise of
 Q  m  t
temperature is found to be the same as it requires
 Q = sm  t
between 14.5°C and 15.5°C. Hence mean calorie is
defined as where "s" is the constant depending upon the
nature of the substance.
Def : "The amount of heat required by one gram of
's' is called the specific heat of the material of
water to rise, its temperature from 14.5°C to 15.5°C
the body.
(or 58.1oF to 59.9oF) at a pressure of 1 atm."
Q
9.3. HEAT CAPACITY (OR) THERMAL s 
m . t
CAPACITY (H)
C.G.S. unit Cal / g 0C
Different substances have different capacities
S.I. unit J kg–1 K–1
of heat. They can be distinguished by the quantity
known as "Heat capacity" or "thermal capacity". 1 Cal/g0C = 4186 J/kg K » 4200 J/kgK
The dimensional formula [M0L2T–2K–1]
Def : The quantity of heat required to rise the
temperature of a body through one degree is called Specific heat depends only on nature of the
heat capacity(H) of that body. substance. It does not depend on mass of the
substance.
When same quantity of heat is given to bodies
of same mass but of different substances, it is Relation between Heat Capacity(H) and Specific
observed that the rise in temperature is different for heat (S)
different substances. So the heat capacity of a body When a quantity of heat  Q is given to a body
depends on the nature of the substance and also on of mass “m”, let the rise in temperature of the body
mass of the body. be  t.
Let  Q be the quantity of heat given to the Q
Then H  ...............(1)
substance and let the rise in its temperature be  t. t
Q Q
Heat capacity H  But specific heat s  ...............(2)
t m.t
units in C.G.S. system : Cal/0C From (1) and (2)
S.I. unit : JK–1  Q  m st
1 Cal/0C = 4200 J/K mst
Dimensional formula : [ML2T–2K–1] H
t
9.4. SPECIFIC HEAT (OR) SPECIFIC HEAT
 H  ms
CAPACITY (S) :
The nature of the substance in absorbing heat Hence the heat capacity of a body is equal to
to rise its temperature is given the name specific heat the product of mass of the body and specific heat of
(or) specific heat capacity of the substance. the material of the body.
Note : (i) The specific heat of the material of the  m 2  m1 s1

body is also defined as the heat capacity per
unit mass of the body.  water equivalent of the given body is m1s1
gram and it is numerically equal to the heat capacity
(ii) When specific heat of a substance varies with
of the body in Cal 0C–1 .
temperature then heat energy given to the sub-
stance is Units : CGS system : gram, SI unit : kg
Note : Heat capacity in Cal 0C–1 is numerically equal
t2
to water equivalent in grams
Q   ms dt Ex : (i) If heat capacity of a body is Q Cal/0C then
t1
its water equivalent is Q gram.
(iii) Specific heat is independent of mass of the body (ii) Water equivalent of a given body,
where as heat capacity depends on mass of Heat capacity of the given body
the body. W=
Specific heat of water
(iv) Specific heats of some solids and liquids
Problem: 9.1
Substance Specific heat Substance Specific heat Find the water equivalent of a copper block
capacity capacity of mass 200g. The specific heat of copper is
(CGS units) (CGS units) 0.09 cal/goC.
Copper 0.093 Alcohol 0.6 Solution:
Glass 0.2 Benzene 0.41 Water equivalent W = ms = 200 × 0.09 = 18g
Iron 0.11 Glycerine 0.6 *Problem 9.2
Lead 0.03 Water 1.0 A lump of iron of mass 2 kg is heated from
ice 0.5 40°C to 1000°C. If the heat supplied is 192 k cal,
9.5. WATER EQUIVALENT OF A BODY find its thermal capacity. Find also the specific
“The water equivalent of a body is defined as heat of iron.
the mass of water which absorbs the same quantity Solution : Heat supplied
of heat as is done by the given body for the same Q  192 k cal = 192 x 103 x 4.2 J ;
rise in temperature.” or
The mass of water whose thermal capacity is mass m = 2 kg ; rise in temperature
equal to that of a given body is called water equiva- t  1000 - 40 = 960°C.
lent of that body.
a) Thermal capacity of the lump of iron =
Let a quantity of heat Q1 be given to a body
of mass “m1”.  Q 192  10 3  4.2
  840 J / K
Let the rise in temperature of this body be t1 . t 960
If the specific heat of the body is s1 then b) Specific heat of iron s =
Q1  m1s1t1 DQ 84 0
Let a quantity of heat Q2 be given to water = = 4 20 J kg - 1 K - 1
mD t 2
of mass m2 to produce same rise in temparture t1
* Problem: 9.3
\ DQ2 = m2 ´ s 2 ´ Dt1
Two spheres of radii in the ratio 1:2, have
But the specific heat of water, s2 = 1 cal/gram 0C
specific heats in the ratio 2:3. If their densities
As Q1  Q2 are in the ratio 3:4, find the ratio of their thermal
m1s1t1  m2  1  t1 capacities.
313
Solution : Thermal capacity of a body = ms. Given ; m = 1000 g, s = (3t2 + t)

The ratio of thermal capacities 20 20
4 3 t2
m1s1 v1r 1s1
p r1 r 1s1  2

 Q   1000 3t  t  10 dt  t  3
2
3
= = 3 10 10
m2 s2 v2r 2 s2 4 3
p r2 r 2 s2  20 2   3 10 2 
3   20 3   10   8200  1050
ær1 ö÷3 ær 1 öæ s1 ö÷ æ1 ö 3 æ öæ ö  2   2 
= ç ÷ ç ÷ç
÷ ÷=
ç ÷ ç ÷ç ÷ çç ÷ ç ÷ ç 3 ÷ç 2 ÷= 1
÷
çè r2 ø÷ èç r 2 øè
÷ç s2 ø÷ è 2 ø ÷çç 3 ÷
÷ ççè 4 øè ÷
ø 16 = 7150 cal
Problem: 9.4 Problem: 9.6
A lead piece of mass 25g gives out 1200 The specific heat of many solids at low
calories of heat when it is cooled from 900C to temperatures varies with absolute temperature
100C. What is its i) Specific heat ii) thermal T according to the relation S = AT3, where A is a
capacity and iii) Water equivalent. constant. What is the heat energy required to
Solution : raise the temperature of a mass m of such a solid
Mass of lead piece (m) = 25 g = 0.025 kg from T = 0 to T = 20 K
Amount of heat given out = 1200 calories Solution :
Amount of heat energy given out 20 20
(dQ) = 1200 × 4.2J
 m  AT  dT  4  10 mA
3 4
Q  mS dT 
The fall in temperature 0 0
(dT) = (90 – 10)0 C = 800 C = 80K
9.6. CALORIMETRY
1 dQ The branch of science which deals with the
(i) Specific heat S 
m dT measurement of heat is called calorimetry. The
apparatus used for this purpose is called calorimeter.
1 1200  4.2 A perfect calorimeter completely prevents heat flow
 
0.025 80 into or out of the system contained within it. Suppose
two or more materials at various temperatures are
5040
= = 2520 J kg- 1 K - 1 placed together within a calorimeter. The materials
2 will share thermal energies until the thermal
(ii) Thermal capacity = ms = 0.025 × 2520 equilibrium is established. At thermal equilibrium
= 63J K–1 all the materials reach the same temperature.
63 Because no energy flows into or out of the container,
(iii)Water equivalent = W= kg
4200 the law of conservation of energy leads to the
Problem: 9.5 principle of calorimetry.
The specific heat of a substance varies as 9.7. PRINCIPLE OF METHOD OF MIXTURES
(3t2 + t)× 10–3 cal/g-0C. What is the amount of
(PRINCIPLE OF CALORIMETRY) :
heat required to raise the temperature of 1 kg of
If two bodies at two different temperatures
substance from 100C to 200C ?
are brought into thermal contact, then heat is lost
Solution : For small change in temperature dt, heat by the hot body and heat is gained by the cold body
required, until they attain thermal equilibrium (common
t2
temperature). If heat is not lost by any other process,
dQ = msdt \ Q= ò msdt heat lost by hot body = heat gained by cold body
t1
Explanation : Consider a hot body of mass m1 , Final temperature (t) = 300C

specific heat s1 at t1OC is kept in thermal contact with Fall in termperature of A = 60 - 30 = 300C
another cold body of mass m2 , specific heat s2 and
Rise in temperature of B = 30 - 20 = 100C
at temperature t2.
Heat lost by the liquid A = m1S1 (t1 – t)
Let t3 be the common temperature attained.
Heat lost by hot body = m1s1 ( t1 - t3) = m1 × 0.5 × 30 cal
Heat gained by cold body = m2s2 (t3 - t2) Heat gained by the liquid B = m2S2 (t – t2)
 m1s1 ( t1 - t3) = m2s2 (t3 - t2) = m2 × 0.3 × 10 cal
m1s1t1 – m1s1t3 = m2s2t3 – m2s2t2 Heat lost by the liquid A = heat gained by the
(or) t3 (m1s1 + m2s2) = m1s1t1 + m2s2t2 liquid B
m1 s1t1 + m2 s2t2 m1 × 0.5 × 30 = m2 × 0.3 × 10 or

\ Common temperature, t3 =
m1 s1 + m2 s2 m1 0.3´ 10 1
*Problem 9.7 = = = 1: 5 .
m 2 0.5´ 30 5
10 litres of hot water at 70°C is mixed with
an equal volume of cold water at 20°C. Find the 9.8 DETERMINATION OF SPECIFIC
resultant temperature of the water. (Specific heat HEAT OF A SOLID
of water = 4200 J/kg K) Description : Calorimeter is a cylindrical vessel
Solution : made with copper or aluminium. Its outer surface is
polished to prevent the loss of heat due to radiation.
m1s1t1 + m2 s2t2
Resultant temperature, t = . It is placed in a wooden box and the space between
m1s1 + m2 s2 them is filled with a non-conducting material like
Here, m1 = m2 = 10kg, since mass of 1 litre of cotton or felt to prevent the loss of heat due to
water is 1 kg. conduction. Calorimeter is closed with a non
t1 = 700C; t2 = 200C and s1 = s2 = 4200J/kgK conducting lid to minimise the loss of heat due to
convection.
10 ´ 4200´ 70 + 10 ´ 4200´ 20
t= = 45°C. The wooden box is provided with a lid. The
10 ´ 4200 + 10´ 4200 stirrer and the thermometer can be inserted through
Problem 9.8 the holes provided for them.
A liquid of specific heat 0.5 cal/g0c at 600C,
is mixed with another liquid of specific heat 0.3
cal/gm0c at 200C. After mixing, the temperature
of the mixture becomes 300C. In what
Thermometer Stirrer
proportion by weight are the liquids mixed ?
Solution :
Lid
Mass of liquid A = m1
Mass of liquid B = m2 Calorimeter
0
Specific heat of A(S1) = 0.5 cal/gm c Cotton (or)
0 Wool
Specific heat of B(S2) = 0.3 cal/gm c
Initial temperature of A(t1) = 600C
Initial temperature of B(t2) = 200C Fig. 1
Thermometer Temperature of the hot solid = t20C

Resultant temperature = t30C
Steam Specific heat of calorimeter = sc
Specific heat of water = sw
Specific heat of solid = s
Solid pieces
Amount of heat gained by calorimeter
= m1sc (t3 – t1)
W ater Amount of heat gained by water =
(m2 – m1)sw(t3 – t1)
Amount of heat lost by the solid =
(m3 – m2)s (t2 – t3)
Fig. 2 According to principle of method of mixtures,
Procedure : Heat lost by the solid = Heat gained by the
An empty and dry calorimeter provided with a calorimeter and water.
stirrer of the same material is cleaned and its mass (m3 – m2) s (t2 – t3) = m1sc(t3 – t1) +
'm1' is determined. Water is filled in the calorimeter (m2 – m1) sw (t3 – t1)
upto two-thirds of its volume and its mass 'm2' is [m1sc + (m2 - m1)sw ](t3 - t1)
s=
determined. Now the calorimeter is kept in the (m3 - m2 )(t2 - t3 )
wooden box. The initial temperature of the Using this relation, the specific heat of a solid
calorimeter and water t10C is noted . can be determined.
The solid whose specific heat is to be determined Precautions :
is taken in the form of small pieces and heated in 1) The outer surface of the calorimeter should be
Regnault's steam heater. The solid is taken into small well polished
pieces so that the surface area is more and hence the
2) Calorimeter should be placed in a wooden box
exchange of heat is quick.After attaining the
stuffed with cotton or wool.
maximum steady temperature,the temperature of the
3) The solid should be transferred quickly from
solid t20C is noted. Now the solid is allowed to fall
heater to the calorimeter.
into the calorimeter quickly. The calorimeter is
4) A screen should be placed between the
removed away from the heater. The contents in the
calorimeter and the heater.
calorimeter are stirred well and the resultant
temperature t30C is noted. The mass of the calorimeter 9.9 Determination of specific heat of a liquid :
along with the water and solid 'm3' is determined. The specific heat of a liquid can be determined
The observations are as follows. using a calorimeter. The mass of a well polished
Mass of empty calorimeter with stirrer = m1 empty calorimeter "m1" is determined. The liquid
Mass of calorimeter + stirrer + water = m2 whose specific heat (sL) is to be determined is taken
in the calorimeter up to 1/3 of its volume and its mass
Mass of calorimeter + stirrer + water + solid = m3
"m2" is determined. It is kept in the wooden box
Initial temperature of the calorimeter and and the initial temperature t10C is measured. The
water = t10C substance of known specific heat "s" is taken in the
form of small pieces and heated seperately in a steam 0.100  378  100  0.100  4200  X  0.100  378  X
40 
heater. The steady temperature of the substance t20C 0.100  378  0.100  4200  0.100  378
is noted. The hot substance is transferred to the
37800 + 4578 X
calorimeter quickly. The contents are stirred well 40 =
and the resultant temperature t30C is noted. The 4956
calorimeter is taken out of the wooden box and its 4578X = 198240 –37800
mass "m3" is determined along with liquid and = 160440
substance. Let 'sL' is the specific heat of the liquid. 160440
X= = 35.05°C.
The heat gained by calorimeter = m1sc (t3 – t1) 4578
The heat gained by liquid = (m2 – m1) sL (t3–t1) Problem 9.10
Total heat gained A copper calorimeter of a mass 300 g contains
= m1sc(t3–t1) + (m2 – m1) sL (t3 – t1) 500 g of water at a temperature of 200C. A 500 g
of copper block at 1000C is dropped into the
Heat lost by hot body = (m3 – m2)s (t2 – t3) calorimeter. If the resultant temperature is 250C,
Heat gained by calorimeter and contents= then find the specific heat of copper.
Heat lost by hot body Solution :
m1sc(t3–t1) + (m2– m1) sL (t3–t1) = (m3–m2) s (t2–t3) Mass of copper calorimeter (m1) = 300 g
 specific heat of liquid "sL" = 0.3 kg
Specific heat of copper = S1
(m3  m2 ) s(t2  t3 )  m1sc (t3  t1 ) Change in temperature of the calorimeter = 25 - 20
= (m2  m1 )(t3  t1 ) = 50C
or specific heat of liquid "sL" Heat gained by the calorimeter = m1S1 D t1
(m3  m2 ) s(t2  t3 ) m1sc = 0.3 × S1 × 5 = 1.5S1
= (m  m )(t  t )  m  m Mass of water (m2) = 500 gm = 0.5 kg
2 1 3 1 2 1
Thus s L, the specific heat of the liquid is Specific heat of water (S2) = 4186 J kg-1K-1
calculated. Change in temp of the water = 25 - 20 = 50C
Heat gained by the water = m2S2 × 5
*Problem 9.9 = 0.5 × 4186 × 5 = 10465J
Copper pieces of mass 100 g at temperature
Mass of the copper block (m3) = 500 g = 0.5kg
100°C are dropped into water of mass 100 g in a
Specific heat of copper = S1
calorimeter of mass 100 g. If the resultant
Change in temperature of the block = 100 - 25
temperature is 40°C find the initial temperature
= 750C
of water. (Specific heat of water = 4200 J/kg K,
Heat lost by the copper block = m3S1 × 75
specific heat of copper = 378 J/kg K).
= 0.5 × S1 × 75 = 37.5S1J
Solution : According to the method of mixtures,
m1 = 100 g = 0.100 kg; s1 = 378 J/kgK; t1 Heat lost by copper = Heat gained by the
=1000C; m2 = 100g = 0.100kg; s2 = 4200J / kgK; calorimeter + Heat gained by the water
m3 = 100g = 0.100kg; s3 = 378J/kgK, t = 400C; t2 = 37.5 S1 = 1.5 S1 + 10465
t3 = X. Substituting in 10465
36S1 = 10465 or S1 = = 290.7
m1s1t1 + m2 s2t2 + m3s3t3 36
t=  Specific heat of copper = 290.7 J kg-1 K-1.
m1s1 + m2 s2 + m3s3
9.10. LATENT HEAT

Thermometer
The amount of heat absorbed or given out by Delivery tube
unit mass of a substance during the change of

Wool Steam
state is called latent heat. Steam
trap
generator
Thermometer
Latent heat, L = Q/m cal/g or J/kg
Stirrer
Latent heat of fusion of ice is 3.35 × 105 Jkg–1 or Lid

Calorimeter
80 cal g–1
Latent heat of vaporization of water is 2.26 × 106 J kg–1 Bad
Conductor
Wooden
enclosure
or 540 cal g–1.

Arrangement for determining the
latent heat of vaporization
Liquids with low latent heat of vaporization are
Fig - 5
called volatile liquids. Ether and Petrol are examples
of volatile liquids. These liquids evaporate quickly Let S c, S w and L be the specific heat of
as their latent heats are small at normal pressures and calorimeter, specific heat of water and the latent heat
ordinary temperatures. of steam respectively.
Heat lost by the steam during condensation
(i) To convert the value from CGS to S.I the
=(m3 – m2) L
multiplication factor is 4200. Heat lost by condensed steam (water) during
1 cal = 4200 J the fall in temperature =  m3  m2  sw  t3  t2  .
g kg
The total heat lost by steam.
9.11. DETERMINATION OF LATENT = (m3 – m2) L + (m3 – m2) Sw (t3 – t2)
HEAT OF VAPOURISATION OF Heat gained by the calorimeter = m1Sc(t2 –t1)
WATER Heat gained by the water = (m2 – m1) Sw(t2 – t1)
The mass m 1 of an empty clean and dry Total heat gained by calorimeter and water =
calorimeter with stirrer is determined using a common  m1sc   m2  m1  sw   t2  t1 
balance. Water is taken in the calorimeter upto two
thirds of its volume and its mass m2 is determined. From the principle of method of mixtures,
The calorimeter is placed in its enclosure and the Heat lost by the steam = Heat gained by the
initial temperature t10C is no ted using t he calorimeter and water
thermometer. Steam generated in the steam heater (m3 – m2) L + (m3 – m2) Sw (t3 – t2)
enters the steam trap. If any water drops are present, = m1Sc(t2 – t1) + (m2 – m1)Sw(t2 – t1) or
they are collected at the bottom of the steam trap.
The dry steam comes out through the nozzle. The [m1Sc  (m2  m1 )Sw ](t2  t1 )
L  sw (t3  t2 )
dry steam at temperature t30C is passed into the (m3  m2 )
calorimeter continuously until its temperature rises
by about 50C. Using this formula, the latent heat of steam can
be determined.
Now the calorimeter is taken out, stirred well
and the final temperature "t 2" is noted. The Precautions :
calorimeter is taken out of the enclosure, allowed to 1) The dry steam should be collected in the
cool and its, mass m3 is determined. calorimeter
2) During the process of mixing the steam with Heat lost by the calorimeter
the water in the calorimeter, the mixture should = 83.72 × 15 = 1255.8J
be stirred well. Mass of water = 0.48 kg
3) steam should be passed into the calorimeter, Specific heat of water = 4186 J kg-1 K-1
until the rise of temperaturer of water is about 50C. Fall in temperature of water = 350C-200C=150C
Problem 9.11 Heat lost by water = 0.48 × 4186 × 15 =
1g steam at 100 0 C is passed in to an 30139.2J
insulating vessel having 1g of ice at 00C. Find the Let 'm' be the mass of ice added,
equlibrium temperature of the mixture,
Heat gained by ice during melting = mL
neglecting heat capacity of the vessel.
Solution : = m × 0.335 × 106J
Heat available on steam (changes from steam Heat gainerd by molten ice (water) during rise
to water) = mL = 1 × 540 = 540 cal in temperature
Heat gained by ice to change into water at 00C = m × 4186 × (20 – 0) = m × 83720J
and then rise its temperature to 1000C  Heat gained by the ice = Heat lost by the
= miceL ice+ mwater Sw  T calorimeter and water
= 1 × 80 + 1 × 1 × (100 – 0) = 180 cal. m × [0.335 × 106 + 83720]
The above calculations show that some part = 1255.8 + 30139.2 = 31395J
of steam will condense to change the ice into m[335000+83720] = 31395
water at 1000C. Let 'x' is the mass of steam
condensed, then 31395
m= = 0.07498 kg .
x × 540 = 180 418720
180 1 Problem 9.13

or x = = g A calorimeter of heat capacity 62.8 J K -1
540 3
contains 0.2 kg of water at 250C. How much mass
Final contents of the mixture : ice = 0g
of steam at 1000C should be added to increase
1 4 1 2 the temperature of the calorimeter to 500C?
water = 1   g , steam = 1   g . Solution :
3 3 3 3
Heat capacity of the calorimeter = 62.8 J K-1
Final temperature of the mixture = 1000C
Rise in temperature of the calorimeter
Problem 9.12 = 500C-250C = 250C
A calorimeter of heat capacity 83.72 J K -1 Heat gained by the calorimeter
contains 0.48 kg of water at 350C. How much
= 62.8 × 25J = 1570J
mass of ice at 00C should be added to decrease
Mass of water = 0.2 kg
the temperature of the calorimeter to 200C.
Solution : Specific heat of water = 4186 J/kg K
Heat capaicity of the calorimeter, Heat gained by the water = 0.2 × 4186 × 25
ms = 83.72 J K-1 = 20930 J
Fall in the temperature of the calorimeter, heat lost by steam during condensation = mL
0 0 0 = m × 2.26 × 106J
D T = (35 C-20 C) = 15 C
Heat lost by condensed steam (during fall of msLs + mss(100 - t) = mcLc + mcs(t-0)
the temperature) where ms is the mass of steam, Ls is the latent
= m × 4186 × ( 1000C – 500C) heat of steam, s is the specific heat of water, mc is the
= m × 4186 × 50 = m 209300 J mass of ice and Lc is the latent heat of ice.
 heat lost by steam = heat gained by the Here, ms = 20g; Ls = 540 cal/g, s = 1 cal/g 0C;
calorimeter and water mc = 100g; Lc = 80 cal/g
m × 2.26 ×106 + m × 209300 20 × 540 + 20 × 1 (100 -t) = 100× 80 + 100 ×1 × t
= 1570 + 20930 = 22500 10800 + 2000 - 20t = 8000 + 100t
m [ 2469300] = 22500 120t = 4800
22500 t = 40OC.
m= = 0.009112 kg
2469300
*Problem 9.16
Problem 9.14 How much steam at 100oC is to be passed
Calculate the quantity of heat required to into water of mass 100 g at 20 oC to raise its
convert 10-2 kg of ice at 00C to steam at 1000C. temperature by 5oC? (Latent heat of steam is 540
(Given Lice = 0.335 × 106 Jkg–1, cal/g and specific heat of water is 1 cal/gOC)
Lsteam = 2.26 × 106 Jkg–1, Solution :
Specific heat of water = 4186 J kg-1 K-1). Heat lost by steam = heat gained by water
Solution : msLs + mss (100 - t) = mws (t - 20)
Quantity of heat required to convert ice into where ms is the mass of steam, Ls is the latent
water at 00C (Q1) = mLice heat of steam, s is the specific heat of water and mw is
=10–2 × 0.335 × 106 = 3350J the mass of water .
Quantity of heat required to raise the temperature Here, Ls = 540 cal/g; s = 1 cal/gOC; mw = 100g,
of water from 00C to 1000C. t = 20 + 5 = 250C
(Q2) = mSw (t2 – t1) = 10–2 × 4186 × 100 ms× 540 + ms×1(100 - 25) = 100 × 1 (25 - 20)
= 4186 J 500
Quantity of heat required to convert water into ms x 615 = 500 \ ms = = 0.913 g.
615
steam at 1000C
9.12 THREE PHASES OF MATTER
(Q3) = mLsteam = 10–2 × 2.26 × 106 = 22600J
Total amount of heat required (Q) = The substances can exist in three states,
(phases) called solid, liquid and gaseous phases at
Q1 + Q2 + Q3
different temperatures and pressures. Any phase of
= 3350 + 4186 + 22600 = 30136 J.
a substance can be changed into another phase by
*Problem 9.15 heating or cooling it.
20g of steam at 100OC is passed into 100g of The process of converting one phase of a
ice at 0OC. Find the resultant temperature if substance into another phase of the substance is called
specific latent heat of steam is 540 cal/g., specific “phase change”.
latent heat of ice is 80 cal/g and specific heat of For example when ice (in solid phase of water)
water is 1 cal/goC. is heated, it melts at 00C and converts into water
(liquid phase). If heat is taken out of water or water
Solution: Let the resultant temperature of the
is cooled it freezes at 00C and converts into ice.
mixture be tOC. In the method of mixtures, Heated
heat lost by steam = heat gained by ice 
ice   water .
Cooled
The process of changing the solid phase into FSuperheated

(Water + vapour) E steam
the liquid phase is known as melting. The process 1000C
Temperature
D
of changing the liquid phase into solid phase is
called freezing or fusion. B (ice + water) Water
00C C
The constant temperature at which the solid ice
phase of a substance changes into a liquid phase is A Heat
called the melting point of the substance.
Length of BC  Latent Heat of fusion of ice
When heat is supplied to ice, it is used to
Length of DE  Latnet Heat of Vapourisation of water
overcome the intermolecular forces holding the
molecules of the ice. Hence no heat is available to Length DE > Length of BC ( that is always Lv > Lf)
increase the average kinetic energy of the molecules 1
Slope of AB  ms
of the ice. Therefore there is no rise in temperature . solid
The absorbed heat energy is hidden in the form of 1
work and hence it is called the latent heat. The Slope of CD  ms
Liquid
temperature doesnot change till the substance Initially temperature of ice is less than 00C. The
changes its phase completely. region AB represents the rise of temperature of ice
Similarly if water (liquid phase) is heated, it to 00C. Here slope of AB is inversely proportional to
boils at 1000C at normal pressure and converts into specific heat of ice. The region BC represents the
steam (gaseous phase of water). If heat is taken out change of state of ice into water at constant
of the steam (gaseous phase) or steam is cooled it temperature . This temperature is melting point of
condenses at 1000C at normal pressure and converts ice (00C). The region CD represents the rise of
into water (liquid phase). temperature of water from 00C to 1000C. Slope of
Heated
this graph is inversly proportional to specific heat of

water  steam . water. The region DE represents the change of state
Cooled
of water into steam. Here also slope of the graph is
The process of changing the liquid phase
zero i.e. temperature remains constant. This
into the gaseous phase is known as vapourisation.
temperature is boiling point of water (1000C).
The process of changing the gaseous phase
5
into liquid phase is called as condensation.
The temperature at which the liquid phase of 1 2
a substance changes into gaseous phase is known as Solid Liquid Vapour
boiling point of the substance at normal pressure. 3 4
The temperature doesnot change till the 6

substance changes its phase completely.
Fig - 15
When heat is supplied to water, it is completely 1  Melting  Heat supplied to the sysytem
used to over come the inter molecular forces holding
2  Vapourisation or Boiling  Heat supplied to the
the molecules of the water. So there is no rise in
sytem
temperature. The heat energy absorbed is hidden in
the form of work and hence it is called Latent Heat. 3  Soldification or Freezing  Heat given out by
During melting or boiling the heat absorbed by the system
the substance is used in increasing the inter molecular 4  Condensation  Heat given out by the system
distances. The phase changes of water are shown in 5  Sublimation  Heat supplied to the system
the figure for its temperature versus heat absorbed 6  Hoar frost  Heat given out by the system
Problem 9.17 9.13. MELTING POINT

A solid material is supplied with heat at a For pure substances i.e., crystalline substances
constant rate. The temperature of the such as ice, naphthalene, etc., the melting and
material is changing with the heat input as freezing points coincide, whereas in the case of
shown in figure. Study the graph carefully amorphous substances like iron, glass, wax, etc.,
and answer the following questions : fusion and solidification take place over a short range
(i) What do the horizontal regions AB and CD of temperature, so that their melting and freezing
represent ? points are not fixed with definiteness. Since the
(ii) if CD = 2AB, what do you infer ? melting and freezing points vary with different
(iii) The slope of OA > the slope of BC. What substances, it is often used to differentiate substances.
does this indicate ?
(iv) What does the slope DE represent ? 9.14. EFFECT OF PRESSURE ON MELTING
POINT
The melting point of a substance changes when
the pressure changes. A theoretical relation between
the increase in pressure and the change in the melting
point known as the Clausius -Clapeyron relation can
be derived on the basis of thermodynamics. It is
Solution : dP L

(i) In the regions AB and CD the temperature of dT T(v2  v1 )
the material remains constant. So AB represents where v2 and v1 are the volumes per unit mass of the
fusion and CD represents vapourisation. liquid and solid respectively at temperature T, dp/dT
(ii) CD = 2AB or Q4 = 2Q2, it shows that latent the ratio of the change of pressure with the change
heat of vapourisation is twice that of latent of of the freezing point and L the latent heat of fusion.
fusion.
From this relation it can be readily deduced that
(iii) Let S1 and S2 be the specific heats of solid and the melting point of a few substances, which
liquid states respectively, then increase in volume on solidification (or contract
Q1 = mS1 D T1 on melting) like ice, iron, antimony, etc., is
lowered by increase of pressure, whereas the
1 1 melting point of most substances, which contract
or S1 = =
æD T ö m ´ slope of OA on solidification (or expand on melting) like wax,
m çç 1 ÷ ÷
çè Q1 ø÷
÷ copper, etc., is raised by increase of pressure.
1 Calculations show that in the case of ice the melting
Similarly S2 = point is lowered by about 0.0073° C per atmosphere
m ´ slope of BC
increase of pressure, whereas in the case of paraffin
Since slope of OA > slope of BC, \ S1 < S2 . wax, the melting point increases by about 0.04° C
(iv) If S3 is the specific heat of vapour state (region per atmosphere.
DE), then Examples of the lowering of the melting point of
1 ice with increase of pressure
S3 =
m ´ slope of DE A) Regelation
1 1 The phenomenon of melting of ice due to excess
or Slope of DE = mS = heat capacity . pressure and its resoldification after the removal of
3 the excess pressure is called regelation.
Example : is essentially an unstable phenomenon, since the

introduction of the smallest quantity of the solid or
even of impurity as dust particles, or any mechanical
disturbances, such as shaking, stirring, etc., is enough
to start solidification. When once the solidification
Ice block
has started, the liquid continues to solidify and its
temperature rises to the normal freezing point with
Wire the latent heat evolved and remains there till the entire
mass has solidified.
Fig - 18 Problem 9.18

When a piece of wire loaded at both ends with When a small ice crystal is placed into
equal weights is slung across a block of ice as shown supercooled water, it begins to freeze
instantaneously. What amount of ice is formed
in the figure, it is found that the wire cuts its way
from 1 kg of water supercooled to –80C ?
through the ice without however dividing the block
into two pieces. The reason is that due to the pressure Solution :
the ice immediately below the wire melts which mL = m1s. 
enables the wire to sink through; but once the m × 80 = 1000 × 1 × 8
pressure is released, the water above the wire m = 100 g.
solidifies into ice again. It may be noted that the latent Problem 9.19
heat required to melt the ice below the wire comes The melting point of ice is 00C at 1 atm. At
from that evolved by the water solidifying above it. what pressure it will be –10C ?
Hence, a copper wire will cut through the ice more Solution :
quickly than an iron wire, because copper is a better
Here D T = (- 1- 0)= - 1, T = 273 + 0 = 273K
conductor of heat than iron.
æ 1 ö÷
B) Supercooling and V2 - V1 = ççç1- ÷
÷´ 10- 3 m 3 (given)
Most liquids, if cooled in a pure state in a è 0.9 ø
perfectly clean vessel, with least disturbance, can be L = 80 cal/g
lowered to a temperature much below the normal DP L
freezing point, without solidifying. This is known We have, D T = T (V - V )
2 1
as supercooling or superfusion. Thus, if a test tube
containning distilled water is cooled slowly without DP 80´ 4.2 ´ 103
stirring the water, the temperature is found to fall 3 =
or (- 1) 273æ ö
çç1 - 1 ÷ - 3
to 4 degrees below 0°C without any ice being ÷´ 10
çè 0.9 ø÷
formed. Water can be cooled in this way even up to
–10°C with a little care, and upto –12°C when \ D P = 132 ´ 10 5 N / m 2 132 atm
covered with a layer of oil. Naphthalene, sulphur,
phosphorous, antimony, etc., have also been or P2 - P1 = 132 atm
supercooled far below their normal solidification \ P2 = 132 + P1 = 133atm .
points.
The phenomenon of supercooling does not 9.15. BOILING POINT
really go counter to the fact that a liquid solidifies at The temperature at which a liquid converts
a definite temperature, which is its freezing point. It into vapour is called boiling point.
i) Boiling and condensing occur at the same A substance boils at a temperature at which its
temperature. saturated vapour pressure is equal to the external
ii) As long as the change of phase takes place, the pressure. If, at a particular temperature, the
temperature remains constant. saturated vapour pressure of a solid substance
is greater than the external atmospheric
iii) All liquids show increase in volume on
pressure, then the liquid, even if formed, will
vapourisation.
immediately vapourise, which gives the
iv) The boiling point of liquid increases with impression of the absence of the liquid state and
increase in pressure and decreases with of the direct passage of the solid to the vapour
decrease in pressure. state. If, however, the external pressure is
v) The boiling point of water is 1000C at 1 atm sufficiently raised, the solid can be melted into
and 1300C at 2 atm. liquid. Thus, camphor which sublimes under
vi) In pressure cooker, the cooking occurs at 2 atm no rmal pressure, can be melted under
pressure and water will boil at a temperature of sufficiently high external pressure.
1200C. (d) A substance sublimes only when the boiling
vii) On the top a mountain, egg does not boil since point at atmospheric pressure is less than the
with decrease of the pressure, boiling point of melting point. By increasing the external
water decreases. pressure the boiling point can be raised above
viii) Steam at a temperature greater than 1000C is the melting point, the substance will melt first
known as superheated steam. and then vaporise in the usual way.
9.16. SATURATED AND UNSATURATED 9.18. TRIPLE POINT

VAPOURS Triple point is a point in the phase diagram
(a) When the pressure exerted by a vapour is representing a particular pressure and temperature
maximum it is called saturated vapour, when at which the solid, liquid and vapour can co-exist
pressure exerted is not maximum, it is called (or will be in equilibrium). or
unsaturated vapour.
A point on the phase diagram that represents
(b) Saturated vapours do not obey the gas laws and all the three phases of matter in equilibrium is called
saturated vapour pressure of a liquid is
tripple point.
independent of volume occupied. But
unsaturated vapours obey the gas laws. A substance can exist in all the three phases –
(c) At boiling point of a liquid, saturated vapour solid, liquid and vapour under suitable conditions of
pressure is equal to atmospheric pressure at that temperature and pressure.
place. With the help of a phase diagram (P–T graph)
the behaviour of matter in different phases can be
9.17. SUBLIMATION
studied.
(a) Sublimation is the process of change from a
For water, the temperature and pressure
solid to the vapour state without attaining the
intermediate liquid state and the reverse process corresponding to the triple point are 273.16 K and
of direct conversion of vapour to solid is called 4.58 mm of Hg (610.42Pa) respectively.
hoar frost. Triple point of water : The solid (ice) and
(b) Under normal conditions of pressure, solids like liquid (water) phases are in equilibrium at a
camphor, iodine, arsenic, etc., do not melt when temperature called the melting point or fusion point.
heated, but "sublime". Similarly the temperature at which the liquid phase
(c) The phenomenon of sublimation can be (water) and vapour phase (steam) are in equilibrium
explained as follows. is called the boiling point. Similarly the temperature
at which the solid phase (ice) and vapour phase Note :

(steam) are in equilibrium is called sublimation point. (i) At triple point the value of latent heat is zero.
All these temperatures change with pressure. So a (ii) If the temperature at triple point is kept constant
phase diagram is obtained as shown in figure. pressure increases slightly then the phase is
M liquid.
Pressure
(iii) If the pressure at triple point is kept constant

Ice
N
l
and temperature increases vapour state exists

in e
Liquid e
lin
am and when temperature decreases solid state
610.24 Pa ste
Solid
(or) exists.
4.58mm P
of Hg e (iv) If temperature at triple point is kept constant and
n lin Vapour
a tio pressure is increased then liquid state exists and
Q lim
sub
when pressure is decreased vapour state exists.
273.16 K Temperature
9.19. THERMODYNAMIC SYSTEMS
Fig - 19
To study the relation between the heat and
1) Steam line : In the diagram the curve PN is
mechanical work, a system is required. This relation
called the steam line. Along the curve the steam and
can be studied by studying the changes in the
water are in equilibrium. It shows the variation of
properties of a system due to exchange of energy in
boiling point of water with pressure. Any slight
the form of work.
deviation either in pressure or in temperature from
any point on the curve we miss one of the phases A system is defined as a region in space. The
bounded by the curve. region may contain a collection of large number
of atoms or molecules with in a real or imaginary
As the slope of the curve is positive, it shows
boundary.
that the boiling point increases with increase of
pressure. This can be observed in pressure cookers. Ex : A gas or vapour enclosed in a cylinder having a
movable piston.
2) ice line : The curve PM is called the ice line.
Along the curve, the ice and water are in equilibrium. Surroundings :
The curve shows the variation of melting point of The medium or matter or vacuum that
ice with pressure. Any deviation of pressure or surrounds the system which may participate in the
temperature from the point on the curve results the process of exchange of matter or energy or both
existance of one phase. As the slope of the curve is with the system.
negative, it shows that the melting point of ice Thermodynamic variables or coordinates.
decreases with increase of pressure. This can be The state of a thermodynamic system can be
observed in regelation. represented by specifying its pressure "P", volume
3) Sublimation line or Hoarfrost line : The curve "V", temperature "T", mass, internal energy U and
PQ is called the sublimation line or hoarfrost line. entropy S, which are called thermodynamic variables
Along the curve the ice and steam are in equilibrium. or thermodynamic coordinates of the system. All the
The curve shows the variation of sublimation point thermodynamic variables can be expressed in terms
with pressure. Any small deviation of pressure or of pressure, volume and temperature.
temperature from the point on the curve results the 9.20. TYPES OF SYSTEMS :
existance of one phase.
There are three types of systems
All the three lines PM, PN and PQ meet at a
1) Closed system
single point called triple point of water. At the
corresponding temperature and pressure, the three 2) Open system and
phases of water coexist. 3) Isolated system
1. Closed system : a) There is an exchange of matter with the

The closed system is the one which can surroundings.
exchange only energy with its surroundings, but b) The mass within the system does not necessarily
no exchange of matter with the surroundings. remain constant, it may change depending upon
a) The matter within the system remains the same mass inflow and mass out flow.
and constant, though its volume can change c) There is an exchange of energy also.
against flexible boundary.
1) Open vessel : Consider some water in an open
b) The typical nature and chemical composition
vessel made up of good conductor of heat. When
of the matter may change. That is, a liquid may
evaporate, a gas may condense or a chemical the vessel is heated by an external source, water
reaction may occur between two or more absorbs heat, due to exchange of heat energy and
components of the system. begins to convert into steam on boiling. During the
Examples : formation of steam, work is performed against the
molecular forces of attraction. As the steam escapes,
i) Cylinder fitted with a movable piston.
the matter exchanges with the surroundings. So this
Consider a given mass of a gas in a conducting
can be considered as an open system.
cylinder fitted with a frictionless and movable piston.
2) Air compressor : Low pressure air enters the
When the piston is pushed inside, the volume of the
compressor and high pressure air leaves it and this
gas decreases, the pressure of the gas increases, and
high pressure air is used to inflate the automobile tyres.
some work is done on the gas. Hence the temperature
The air enters a cylinder fitted with a piston at
of the gas increases. As the cylinder is conducting,
low pressure. The piston is made to move to
the heat energy is exchanged with the surroundings
compress the air by supplying energy from the
keeping the temperature constant. But there is no
surroundings. The work is performed on the air to
exchange of matter with the surroundings.
increase the pressure and temperature. By the
movable exchange of heat energy with the surroundings the
compressor is kept cool.
gas piston
As the high pressure air leaves the compressor
the exchange of matter with the surroundings takes
Walls and piston are place. This is an example of open system.
good conductors of heat.
ii) Pressure cooker : Consider some water in a 3. Isolated system :
pressure cooker with a closed lid made up of good An isolated system is one which can not
conductor of heat. When the pressure cooker is heated exchange energy or matter with its surroundings.
by an external source, water absorbs heat due to a) A system is thermally insulated from the
exchange of heat energy and begins to convert into surroundings
steam on boiling. During the formation of steam, work b) There is no exchange of energy from the
is performed against the molecular forces of
surroundings
attraction. Here the pressure increases but volume
remains same and there is no exchange of matter due Examples :
to closed lid. Pressure cooker can be considered as a 1. The universe can be considered as an isolated
closed system during cooking. system since there is no exchange of matter or
2. Open system : energy with the surroundings.
An open system is the one which can 2. The fluid contained by a thermosflask. There is
exchange energy as well as matter with the no exchange of thermal energy. It is designed
surroundings. so that heat energy can not enter or leave the
flask either by conduction or by convection or path :

by radiation. There is no exchange of matter. The locus of the series of points representing
3. All adiabatic systems are isolated systems. the states through which the system passes is called
9.21. THERMODYNAMIC EQUILIBRIUM the path.
The system in thermodynamic equilibrium Consider a system constituted by gas enclosed
should satisfy the following three equilibria in the piston cylinder assembly. At any instant, the
condition of the system is described by pressure,
1. Mechanical equilibrium :
volume and temperature and mass "m" of the gas.
When there is no unbalanced force within the
When all such properties have definite values the
system or between the system and surroundings,
system is said to be in an equilibrium state. With the
then the system is said to be in the mechanical
equilibrium. variables as co-ordinates, the state of the system in
thermodynamic equilibrium can be represented by a
In the system the pressure of the gas remains same
point in a co-ordinate axes system.
2. Chemical equilibrium :
When the system does not tend to undergo
chemical reaction or no transfer of matter from one
part to the other part, then it is said to be in chemical P
equilibrium. A B
The system does not undergo any spontaneous C
change of internal structure. B1
C1 F
There is no transfer of matter such as diffusion.
3. Thermal equilibrium : V
When the temperature within the system is
equal to that of the surroundings then the system
is said to be in thermal equilibrium with the Let P1, V1 and T1 represent the initial state A of
surroundings. the system. When a small amount of heat is transferred
Thermodynamic equilibrium : to the system, the piston moves outwards changing
If a system is simultaneously in a state of the variables to P2, V2 and T2 to a new state 'B'. This
mechanical equilibrium, chemical equilibrium and change of state depends upon the amount of heat
thermal equilibrium, then the system is said to be absorbed. These two states are represented by the two
in thermodynamic equilibrium. points A and B on the P–V graph.
In the thermodynamic equilibrium t he If the heat absorbed is infinitesimally small, these
thermodynamic variables of the system do not change two points are very close on the graph. Let the system
with time. undergoes a change of state from state A to state F
Any change in one of the variables results in a passing through several such intermediate states by
change in the other thermodynamic variables of the absorbing different amounts of heat. All the states
system. can be represented by the points A, B, C, F, very
9.22. STATE, PATH, PROCESS close on the P–V graph. Hence ABCF is the path
for the change from state A to state F.
Equation of state :
A relation among the values of any of the three 9.23. PROCESS :
thermodynamic variables for the system is called The complete description of change of state
its equation of state. along with the path is called a process.
It is said that the system undergoes a process the gas are infinitesimally small. These small changes
along the path represented by the graph ABCF by make the differences in pressure ( P),volume ( V)
absorbing some amount of heat. and temperature (  T) between the gas and
surroundings are nearly equal to zero, keeping the
If the system is made to undergo another change
system almost in thermodynamic equilibrium. In an
of state again from A to F but with different
ideal quasi-static process, the system is said to be in
intermediate states along B1,C1 the system absorbs thermodynamic equilibrium with the surroundings
different amount of heat. As such the path AB1,C1, in each state during a process.
F is different.
An ideal quasi-static pro cess is purely
So the heat absorbed depends upon the path of hypothetical. However any process taking place very
the process. slowly can be considered as a quasi-static process
9.24. DIFFERENT TYPES OF PROCESSES: provided sudden changes are not involved.
1) Quasi Static process : Otherwise, if all the weights are removed at once
A quasi static process can be defined as an the gas expands suddenly and sets the gas into turbulent
infinitesimally slow process in which the system motion. During the expansion, the changes in pressure,
rem ains in thermal and mechanical volume and temperature are rapid. The gas undergoes
(thermodynamic) equilibrium with surroundings at several intermediate states which are not in
each and every intermediate stage. thermodynamic equilibrium. Finally the gas attains
Consider the expansion of a given mass of a thermodynamic equilibrium with definite pressure,
gas in a closed conducting cylinder fitted with a volume and temperature. But during the process the
smooth frictionless piston as shown in the figure. A system deviates from the thermodynamic equilibrium.
few small weights are placed on the piston. Due to Any process can be analysed by assuming it as
the weight the piston moves down performing work a combination of a series of closely occurring
on the gas. The volume decreases and pressure quasistatic processes.
increases. After attaining the thermodynamic
2) Cyclic process :
equilibrium, with the surroundings, the state of the
gas is defined by its pressure P, volume V and A process in which the system after passing
temperature T. through various stages of pressure, volume and
temperature changes, returns to its initial state is
defined as cyclic process.
gas P
P P1V1T1
P2V2T2
V A >
T B
> P3V3T3
If the small weights are removed one by one, B1 C
the piston rises slowly. The gas expands performing V
external work on the piston. The volume increases
and attains a new value for the volume and pressure Consider a gas enclosed in a cylinder fitted with
in a short time, and attains a new thermodynamical a smooth and frictionless piston. Let the initial state
equilibrium with the surroundings after exchange of of the gas A is given by the variables P1, V1 and T1 .
heat energy. But the new state differs (deviates) from Now let the gas expands by a process to reach a
the previous state by a very small value. state B given by P2, V2 and T2. Then the gas is again
If the weights removed are infinitesimally small, made to expand by another process to reach the state
the changes in pressure, volume and temperature of ‘C’ given by P3, V3 and T3 by absorbing energy. Now
the gas is compressed along the path CB1A to initial In this reverse process, work is performed on
volume V1 by another different process to reach the the gas and the equal amount of heat is given out to
initial state A. During this process energy is rejected the surroundings in each intermediate equilibrium
to the surroundings in the form of work. states. Thus the gas is compressed from volume V2
a) The gas may undergo any number of processes to volume V1 and the same amount of heat which
changing their states. was absorbed in the direct process is given out
( Q1 ). The work done on the system is - D W1 .
b) The change in any thermodynamic variable of
The system traces the same path but in reverse
the system is zero. direction DCBA. During the complete cycle the net
c) The heat given to the gas during the process is amount of heat exchanged is zero and the net amount
found in the form of net external work. of work done is zero.
3) Reversible process : i. The process must be a quasistatic.
A process that can be retraced back in the ii. The process must be very slow.
opposite direction in such a way that the system
iii. The process should take place very slowly so
passes through the same states as in the direct
that the system is always in thermodynamical
process, and finally the system and surroundings
equilibriumm in any intermediate state.
return to their original states, with no other change
anywhere else is called a reversible process. iv. The net heat is not utilised in performing the
net work.
Consider a process in which the thermo-
dynamical equilibrium state A of a system changes v. There should not be any loss of heat energy
to another equilibrium state B. During this process due to frictio n, viscosit y, conductio n,
the system may undergo several intermediate convection, or radiation.
equilibrium states. Consider a process in which a Example :1. The process of change of state from
closed system is capable of exchanging energy in ice into water is a reversible process. Ice is converted
the form of heat and in the form of work. Let the into water at 00C by supplying heat under normal
initial thermodynamical state A is changed to another pressure. In the reverse process of conversion of
equilibrium state D. During this process the system water into ice at 00C , heat is to be taken out of water
undergoes several intermediate equilibrium states at the same rate under normal pressure,very slowly.
which are very close. In each state the system absorbs
some quantity of heat (Q1 ) and performs some Example :2. The process of change of state from
work W1 . Similarly by absorbing different amounts water to steam, heat is supplied to water at 1000C
of heat and performing different works the gas under normal pressure very slowly. In the reverse
(system) expands from volume V1 to volume V2. And proces steam is condensed into water by taking same
the path of the process is ABCD. The system is made amount of heat at 1000 C very slowly under normal
to proceed from state D to state A in reverse direction pressure at the same rate.
with same ease. All the changes occuring in direct Irreversible process :
process are exactly reversed passing through same A process that can not be retraced back in
intermediate states. opposite direction is called an irreversible process.
A B A B In the irreversible process the sytem does not
> >
C C pass through the same intermediate states as in the
D D direct process, even if the same initial state is reached.
Let A and B be the two thermodynamic
V1 V2 V1 V2 equilibrium states of a system undergoing a process.
Heat given out = Q1 Heat given out = Q1 During this process the system may undergo several
Work done by the gas = W1 Work done on gas = W1 intermediate states of equilibrium. If this process is
made to proceed in reverse direction, the system does thermal contact with Z seperately. Due to exchange
not pass through the same intermediate states as in of heat energy between systems X and Z they attain
the direct process. thermal equilibrium showing that these two are at
There is a loss of heat due to some dissipative same temperature T. Similarly system Y and system
forces like friction and viscosity. This loss of heat Z attain thermal equilibrium due to exchange of heat
can not be recovered back. The system may finally energy. The systems Y and Z attain the same
attain its initial state, even then it is irreversible. temperature T.
Example :1. In the process of rubbing our hands, The adiabatic wall between the systems X and
heat is produced, increasing the temperature of the Y is replaced by another diathermic wall and the
hands. The mechanical work done against friction is combination is sepeated from the system Z as shown
converted into heat. But in the reverse process, we in fig 2(iii). It is observed that no further changes in
can not make the hands to move in the same way on their temperatures showing that there is no exchange
heating them. of heat energy between the systems X and Y. As
they are at same temperature the two systems X and
Example: 2. Consider a process of mixing up two Y are said to be in thermal equilibrium.
gases, which do not react with each other. The two
gases exist in two different equilibrium states. In the
ADIABATIC
WALL
process of mixing them at constant temperature in a X Y
IC
DIATHERM
WALL
cylinder, the mixture attains a new state in X Y X Y
thermodynamic equilibrium. The pressure of the DIATHERMIC
WALL
mixture is greater than the individual pressures and Z
possess same volume. In the reverse direction the Fig 2(i) Fig 2(ii) Fig 2(iii)
gases can not be separated to their initial conditions
by decreasing the pressure. Thus the temperature is defined as "the property
Example :3. The exchange of heat between the two which determines whether a system is in thermal
bodies at different temperature is an irreversible equilibrium or not with the neighbouring system".
process. Heat flows from a body at higher temperature If the two systems are at different temperatures they
to a body at low temperature and attain a common are not in thermal equilibrium.
temperature. But the heat energy can not flow in the The property of thermal equilibrium is used in
reverse direction. the measurement of temperature.
9.25.ZEROTH LAW OF THERMODYNAMICS 9.26. JOULES LAW AND MECHANICAL
Def : If two systems are in thermal equilibrium with EQUIVALENT OF HEAT
a third system seperately then they must be in STATEMENT OF JOULE'S LAW :
thermal equilibrium with each other".
Whenever work is done against friction, heat is
Consider two systems X and Y seperated from generated. The amount of heat generated (H) is
each other by an adiabatic wall which does not allow directly proportional to the work done (W).
the heat energy to pass through. The systems are not
If w is the amount of mechanical work done
influenced by each other or influenced by the
surroundings. So they are in separate state of and H is the amount of heat produced, then
equilibrium with different temperatures T1 and T2 W  H or W = JH
Fig 2(i). When this combination is arranged on Here J is constant of proportionality
another system Z with a diathermic wall which which is known as Joule's constant or
allows the heat energy to pass through as shown in Mechanical equivalent of heat
the fig 2(ii). Now the two systems X and Y are in
If H = 1, than J = W
So, Joule's mechanical equivalent of heat is *Problem 9.21

defined as the amount of work required to be done Hailstones fall from a certain height. If they
to produce a unit quantity of heat. melt completely on reaching the ground, find the
Significance : height from which they fall. (g = 10 ms-2, L = 80
Whenever heat is gained or lost by a system calorie/g and J = 4.2 J/calorie.)
during some process, the gain or loss of heat can be Solution : On reaching the ground, a hailstone of mass
taken to be equivalent to some amount of mechanical M loses potential energy which is converted into heat
work done. In this way heat is included as a form of energy required to melt it. In SI, potential energy lost
energy (thermal energy) in the solutions of the law = heat energy required for melting the hailstone
of conservation of energy.
Mgh = ML Þ gh = L
If H is measured in calories and W in joules,
L
then J = 4.186 J cal–1 h = , h = 80´ 4.2 ´ 1000
If W is measured in ergs then g 10
J = 4.186 x 107 erg cal–1 = 33.6 ´ 1000m = 33.6 km.
Note :
*Problem9.22
i. J is not a physical quantity. It is a conversion A boy weighing 42 kg eats bananas whose
factor to convert units of work from one system energy is 980 calories. If this energy is used to go
to another. to height h find the value of h.(J=4.2J/calorie)
ii. The value of J = 1 in SI where both W & H are
Solution :Energy gained by the boy in eating bananas
measured in Joules.
= 980 calories = 980 ´ 4.2 J.
iii. In SI we write H = W since H and work are
measured in Joules If m is the mass of the boy, the potential energy
gained by the boy in going up through a height h is
*Problem 9.20 mgh. In SI,
A 10kW drilling machine is used for 5 energy = potential energy
minutes to bore a hole in an aluminium block of 980 × 4.2 = mgh
mass 10 x 103 kg. If 40% of the work done is
980×4.2 = 42×9.8×h
utilised to raise the temperature of the block, find
the rise in temperature of the aluminium block ? 980´ 4.2
h= = 10m
(Specific heat of Aluminium = 0.9 Jkg-1k-1) 42´ 9.8
*Solution : *Problem9.23
Work done by the drilling machine in 5 minutes =W A lead bullet of mass 21 g travelling at a
W = power x time = 10 x 103 x 5 x 60 = 3 x 106J speed of 100 ms-1 comes to rest in a wooden
The energy utilised to raise the temperature of the block. If no heat is taken away by the wood, find
40 the rise in temperature of the wood. (Specific heat
6
block = 40% of W = 3 x 10 ´ = 12 ´ 105 J of lead = 0.03 calorie/g °C.)
100
Solution : kinetic energy of the bullet = heat gained
Heat gained by aluminium block = mass x by the bullet
specific heat x increase in temperature. 1 2
12 ´ 10 5 = (10 ´ 10 3 )´ 0.9 ´ D t mv = msD t
2
12´ 10 5 v2 (100)2
\ Dt = = 133.3°C Dt = = = 39.680c
0.9´ 10 4 2s 2 ´ 0.03´ 4.2 ´ 1000
9.27. INTERNAL ENERGY OF A SYSTEM(U) done is W1. The amount of heat Q1 given to the system
“The internal energy of a system is defined as and the work done W 1 depend on the path of the
the sum of all the energies contained in the system process. The value of (Q1 – W1) is calculated.
in equilibrium”.
The internal energy of a gas is the sum of kinetic P
B
energy and intermolecular potential energies of the A >
C
molecules of the gas. >
F
Internal energy of the gas D>
U  PE  KE [For a real gas]
V
U  KE [ For an ideal gas]
Now the same system is made to undergo different
KE arises due to the translational, vibrational
process to change from its same initial state A to same
and rotational kinetic energies of molecules of the gas
final state ‘F’ along different path ACF and ADF as
PE arises due to the intermolecular forces of shown. During these processes the heat energies
attraction among the molecules. absorbed are Q2 and Q3 and work performed are W2
Note : andW3. It is observed that Q1, Q2, Q3 are different and
W1, W2, W3 are different as they are dependent on the
i) At absolute zero, the translational kinetic energy
paths. However the values (Q1 – W1), (Q2 – W2) and
 3  (Q3 – W3) are found to be same.
 KE T  2 KT is zero, but the matter still has
So (Q – W) in a process is a function which
internal energy due to vibrational motion and depends only on initial and final states and
rotational motion of the number of atoms with independent of its path. And it is called the internal
in the molecules. This is called zero point energy of the system.
energy. vii) Change in internal energy is zero in cyclic
ii) Internal energy of a system depends upon the process, in isothermal changes of an ideal gas,
parameters of the system. reversible and irreversible process provided the
iii) For a given gas, translational K.E depends only system reaches to the intial state.
on its absolute temperature. It has a definite
9.28. WORK DONE BY AN IDEAL GAS
value for a definite thermodynamic state.
DURING EXPANSION :
iv) Absolute internal energy of a system is not Consider a system, say an ideal gas contained
measurable But we can measure change in in a cylinder provided with a frictionless piston 'CD'
internal energy (dU) of the system as shown in the figure. On the piston both the system
v) When temperature of a system increases, dU is and surroundings exert force. Let 'A' be the area of
+ve. When temperature of the system decreases, cross section of the piston. Let "P" be the pressure
dU is -ve. When temperature of system remains exerted by the gas on the piston. The force exerted
constant, the change in internal energy dU = 0 by the gas on the piston F = PA. Suppose the piston
vi) dU depends only on initial and final states of is moved away through a very small distance "dx".
the system. This is independent of the path C C1
followed by the system. So it is treated as point
function gas
dU = Uf - Ui P
Explanation : Let the equilibrium state ‘A’ of a F
system be changed to a final equilibrium state ‘F’, D D1
by a process along the path “ABF” as shown. The dx
heat energy given to the system is Q1 and the work
Fig. 5
Then the work done by the gas Case (i) : When Pressure remains constant the graph
dW = F dx = PAdx is as in figure.
But A dx = change in volume = dV The work done by the gas = Area ABCD
\ work done by the gas W = P dV = AD × DC = P(V2–V1)
If the pressure remains constant the total work  The area ABCD = workdone by the gas.
done W = P (V2 – V1)
If the volume changes under a variable pressure, A B
from V1 to V2 then the total work done by the gas is P
V2
W   PdV
V1
D C
The integral is evaluated if the pressure is known O
V1 V2
as a function of volume.
As the gas expands from V 1 to V 2 t he V
Case (ii) : When Pressure is varying and the gas is
temperature also changes from T1 to T2 in absolute
in expansion stage the graph is as in the figure.
scale. If 'n' is the number of moles of the gas P
considered,
from the gas law PV = n RT, A
As V and T change at constant pressure the

E F
equation becomes P B
P(V2–V1) = nR(T2– T1) if P is constant D C

O V
H G
 work done dW = nR(T2– T1) V1 V2
dV
*Problem 9.24
A gas expands from 10 litre to 20 litre at a  Area of the strip EFGH is equal to the work
constant pressure of 2 atmospheres. What is the done during a small change of volume dV.
work done by the gas during the expansion? Area of the small strip EFGH = HG  EH
(1 atmosphere = 1.013 x 105Pa) Solution : = dV  P = P dV
P = 2 atmospheres = 2 x 1.013 x 105 Total workdone W = Area enclosed by the
= 2.026 x 105 Nm-2 graph with x-axis = Area ABCDA
V1= 10 litre = 10 x 103 cm3 = 10-2 m3 ; Note :
V2= 20 litre = 2 x 10-2m3.
(i) Positive work : When gas expands the final
Work done = P(V2 - V1) = 2.026 x 105 volume V2 is greater than the initial volume V1. then
(2 x 10-2- 1 x 10-2) = 2.026 x 103 J. the change in volume V2 –V1 is positive. The work
9.29. PV DIAGRAM – GRAPHICAL done by the system is positive.
Y
REPRESENTATION OF WORK :
A
The work done by a system can be found out
by drawing a P-V graph. The volume is taken along P
the x–axis and the pressure is taken along y – axis.
B
The graph is called PV diagram (formerly indicator D C X
diagram). The area of P-V graph with respect to O V1 V2
volume axis gives work done. V
(ii) Negative work :When the gas is compressed compression curve (WAEB> WBFA), the area of
the final volume is less than the initial volume. The the loop (workdone) is positive.
change in volume is negative. The work is done on (iii) If the enclosed loop is traced in the anticlock
the system and the work done is negative. wise direction, the expansion curve lies below
Y the compression curve (WBFA < WAEB) , the area
of the loop (workdone) is negative.
A
9.30. FIRST LAW OF THERMODYNAMICS:
P
Statement : "If the quantity of heat supplied to a
B system is capable of doing work, then the quantity
D C
O
V1
X of heat absorbed by the system is equal to the sum
V2
V
of the increase in the internal energy of the system,
(iii) Work in cyclic process : The given graph shows and the external work done
a cyclic process. by it".
Y
Consider some amount
A of gas enclosed in a cylinder
E having thermally insulated B
P walls fixed wit h a dx
F B frictionless movable piston
A
D C
X
made of thermally insulated
O V1 V2 mat erial. But it has a
V
The system changes from state A to B along conducting bottom.
Let 'A' be the initial Conductor
the path AEB and back to 'A' along the path BFA.
The work done W1 during the path AEB is position of the piston and U1
positive. be the initial internal energy
HEAT Q
 W1 = Area AEBCDA of the gas. Let an amount
The work done W2 during the path BFA is of heat 'dQ' be added to the gas through the
negative. conducting bottom.
 –W2 = Area BCDAFB The total initial thermal energy of the gas = U1+dQ
 Net work done W = W1 – W2. The gas absorbs heat energy and expands
The work done pushing the piston to a new position 'B'. The work
= Area of AEBCDA – Area of BCDAFB done by the gas in displacing the piston through a
= Area of loop AEBFA small distance dx is dW.
As this is positive the net work done in the
The internal energy of the system increases to
cyclic process is equal to the area of loop.
U2 by absorbing the heat ‘dQ’ . Some of the internal
Even though the two states A and B are same
energy is utilised in performing external work done
the workdone is different for different paths. So the (dW) in pushing the piston away. The internal energy
work done depends on the path along which the changes to U3 .
process changes as shown in the graph. The total energy after pushing = (U3 + energy
Thus for a cyclic process, converted into work)
(i) Work done in complete cycle is equal to the According to law of conservation of energy
area of the loop representing the cycle. U1 + dQ = U2 = U3 + dW
(ii) If the closed loop is traced in the clockwise  dQ = (U3 - U1) + dW
direction, the expansion curve lies above, the (U3 – U1) is the change in internal energy dU.
334
If an infinitesimally small amount of heat 'dQ' Heat absorbed during melting process, dQ = mL
is added to the system (gas), corresponding change According to the first law of thermodynamics,
in internal energy is 'dU' and the work done by the dQ = dU + dW or mL = dU + dW
gas is 'dW'.
case 1. Where there is no change in volume dV = 0
Then dQ = dU + dW.
dW = P dV = Px O = O (where P is the presure)
This is the mathematical statement of first
dQ = dU + O dQ = dU
law of thermodynamics.
 mL = dU
Sign convention : case 2. When the volume increases change in
If the heat energy dQ is added to the system volume = dV
(gas) it is taken as positive (+dQ). the work done dW = PdV ( + Ve)
If the heat is given out (released) by the system
dQ = dU + dW
it is taken as negative (–dQ).
If the work is done by the system (gas) it is taken mL = dU + p.dV
as positive (+dW).  dU = mL – P.dV
If the work is done on the system (gas) by case - 3. When the volume decreases ( as in the case
surroundings it is taken as negative (–dW). of ice)
The increase in internal energy is taken as the decrease in volume dV.
positive (+dU). The work done dW = P.dV ( –ve)
The decrease in internal energy is taken as dQ = dU + dW
negative (–dU).
mL = dU – p.dV
Significance and limitations : dU = mL + P.dV
1) This law introduces the concept of internal So, the internal energy changes during the
energy. melting process.
2) This law is applicable to all the three phases of
(b) Boiling Process
matter (i.e., solid, liquid and gas).
When a liquid is heated sufficiently, it changes
3) This law is applicable to any process in nature.
into vapour at a constant temperature (called boiling
4) This law doesnot give any information about point) . When water is heated at normal atmospheric
the direction of heat flow, between the hot and pressure, it boils at 100oC. The temperature remains
cold body, when they are in thermal contact. unchanged during the boiling process.
5) This law tells that it is impossible to get work Consider the vapourisation of liquid of mass m.
fro m any machine without giving it an Let Vw , Vs be the volumes of the water and steam
equivalent amount of heat energy. respectively.
(iii) Applications of first law thermodynamics Then, the work done in expanding at constant
(a) Melting Process temperature and pressure P,
When a substance melts, the change in volume dW = PdV = P (Vs–Vw)
(dV) is very small and can, therefore, be neglected. Let L be the latent heat of vaporisation, i.e., the
The temperature of a substance remains unchanged heat required to change a unit mass of water to vapour
during melting process. phase (steam) at constant temperature .
Consider the melting of a mass 'm' of the solid.  Heat absorbed during boiling process,
Let L be the latent heat of fusion i.e., the heat required dQ = mL
to change unit mass of a solid to liquid phase at Let Uw and Us be the internal energies of the
constant temperature. water and steam respectively.
335
Change in internal energy dU = Us – Uw The change in internal energy = Internal work done
According to the first law of thermodynamics,
8400
dQ = dU + dW = 8400 J = kCal = 2 kCal.
4200
 mL = (Us – Uw) + P (Vs– Vw)
or Us – Uw = mL – P(Vs – Vw)  40 kCal = 2 kCal+External work done
Knowing all the quantites on right hand side, The external work done = 40 - 2 = 38 kCal
we can calculate the gain in the internal energy. 9.31. SPECIFIC HEAT OF GASES :
* Problem 9.25 When heat is supplied to a solid or a liquid, it
produces an increase in the temperature only without
When heat energy of 1500J is supplied to a
causing any practical change in its volume or
gas the external work done by the gas is 525J
pressure. Accordingly, a solid or a liquid undergoes
what is the increase in its internal energy
a definite rise in temperature, when supplied with a
Solution : Heat enrgy supplied Q=1500J given amount of heat. However it is not true with
External work done w=525J gases. When a gas is heated, the volume and pressure
By 1st law of thermo dynamics Q = U+w also change with increase in temperature.
 U  Q  w =1500 – 525 = 925J. If a gas is heated, the heat energy will be required
not only to increase the temperature of the gas but
*Problem 9.26
also to do mechanical work in overcoming external
When 1g of water at 100°C is converted into
pressure during expansion. The specific heat of a
steam at 100°C,. it occupies a volume of 1671 cc
gas depends upon the conditions under which it is
at normal atmospheric pressure. Find the increase
being heated.
in internal energy of the molecules of steam.
Thus it is not meaningful to talk about the
Solution :
specific heat of a gas unless the conditions are
(1 atmosphere = 1.013 x 105 Nm-2 ; mentioned.
volume of 1gm of water, V1 = 1cc = 10-6m3;
9.32 SPECIFIC HEAT OF A GAS AT
Volume of steam = 1671 cc = 1671 x 10-6 m3
CONSTANT PRESSURE : CP
External work done dW = P(V2 - V1)
At constant pressure, the quantity of heat
= 1.013 x 105 (1671 x 10-6 - 1 x 10-6)
necessary to increase the temperature of unit mass
= 1.013 x 105 x 1670 x 10-6
of a gas through one degree is called specific heat
= 1.013 x 167 = 169.2 J. of the gas at constant pressure.
Specific latent heat of vaporisation of steam = If ' Q' is the quantity of heat required to rise
540 cal/g. So, heat supplied to convert 1g of water the temperature of "m" mass of gas through ' t' at
into steam, D Q = 540 x 4.2J = 2268J By first constant pressure.
law of thermodynamics
Q
D U = D Q - D W = 2268 - 169.2 = 2098.8J cP 
m t
*Problem 9.27
Calculate the external work done by the CGS unit : Cal / g 0C
system in kCal, when 40 k Cal of heat is supplied SI unit : J kg–1 K–1
to the system, 8400 J of internal work is done. Molar specific heat of a gas at constant
Solution : pressure : Cp
Heat supplied to the system at constant pressure At constant pressure, the quantity of heat
= change in internal energy + External work done. necessary to increase the temperature of one mole
of a gas through one degree is called molar specific If 'm' is the mass of the gas and 'M' is its molecular
heat or molar heat capacity of the gas at constant m
pressure, CP weight then n 
M
Let 'Q' is the quantity of heat required to M Q
then CV  = M cV
rise the temperature of 'n' moles of gas through 't' m T
at constant pressure. Then C.G.S unit : Cal / mole 0C
SI unit : J mole–1 K–1
Q
CP 
n T 9.34. LIMITS OF SPECIFIC HEAT OF A GAS
If 'm' is the mass of gas considered and 'M' is Consider mass 'm' of a gas. Let Q units of heat
m raise the temperature of the gas through T . Then
its molecular weight then n 
M the specific heat of the gas is given by
M Q Q
 CP  = M cP c [ Q  mc T]
m T mT
C.G.S. unit Cal / mole 10C Consider a gas enclosed in a cylinder fitted with
SI unit J mole–1 K–1 an air-tight and frictionless piston.
i) Let the gas be suddenly compressed. In this case,
9.33. SPECIFIC HEAT OF A GAS AT no heat is supplied to the gas. But there is an
CONSTANT VOLUME : cV increase in the temperature of the gas.
At Constant volume, the quantity of heat
necessary to increase the temperature of unit mass Q
c  0 [ Q  0]
of a gas through one degree is called the specific mT
heat of the gas at constant volume. It is denoted ii) Let the gas be heated and allowed to expand.
by cV. Suppose the ‘fall in temperature due to
If 'Q' is the quantity of heat required to rise expansion’ is equal to the ‘rise in temperature
the temperature of 'm' mass of gas at constant volume due to heat supplied’.
through 't' then
Q
 c   [ T  0]
Q m0
 cV 
m t iii) Let the gas be heated and allowed to expand.
0
C.G.S unit : Cal / g C suppose, in this case, the ‘fall in temperature
SI unit : J kg–1 K–1 due to expansion’ is less than the ‘rise in
temperature due to heat supplied’. The net effect
Molar specific heat of a gas at constant volume :CV.
will be a rise in the temperature of the gas.
At constant volume, the quantity of heat
necessary to increase the temperature of one mole  Q 
So, Tis positive. Thus c   is positive.
of a gas through one degree is called "Molar  m T 
specific heat" or molar heat capacity of the gas at iv) Let the gas be heated and allowed to expand
constant volume CV. such that the ‘fall in temperature due to
If 'Q' is the quantity of heat required to rise expansion’ is more than the ‘rise in temperature
the temperature of 'n' moles of a gas through 't' at due to heat supplied’. The net effect will be a
constant volume. decrease in the temperature of the gas.
DQ  Q 
CV = So T is negative. Thus, c   is negative
nD T  m T 
9.35. CP IS GREATER THAN CV : respectively. Let the gas be heated at constant

When a gas is heated at constant volume, no volume, so that its temperature increases
heat is spent in the expansion of the gas. The whole through ‘dT’. As the heat is supplied at constant
amount of heat is used to increase the temperature of volume, it is utilised to increase the internal
the gas; increasing the internal energy. energy of the gas
If (dQ)V is heat supplied to n moles of a gas at \ Heat supplied at constant volume
constant volume. (dQ)v = dU = 1´ Cv ´ dT
dU1 is the increase in internal energy
 dU = Cv dT..............(1)
dT1 is the rise in temperature
As the change in temperature is the measure of
n is the number of moles
change in internal energy dU = CvdT is same in any
CV is the molar specific heat at constant volume process as long as the change in temperature remains
Then (dQ)V = dU1 +0 = n CV dT1 ______ (1) same.
When a gas is heated at constant pressure, the Let the gas be heated at constant pressure to the
temperature of the gas increases and the volume also same increase in its temperature dT. It is utilised to
increases due to expansion. increase the internal energy (dU) and to do external
Therefore a part of the heat supplied, to the gas work (dW) in moving the piston through a small
is utilised to increase the temperature, increasing the distance dx against constant pressure P.
internal energy and the other part is utilised in Heat supplied at constant pressure = (dQ)P
performing work against the external pressure during \ (dQ)P = 1´ CP ´ dT = CP dT ....(2)
its expansion (dW)
From the first law of the thermodynamics, we
If (dQ)P is the heat supplied to the gas at constant
can write (dQ)P = dU + dW
pressure
dU2 is increase in internal energy \ C P dT = dU + dW. ........(3)
dT2 is the rise in temperature The work done to move the piston through a
dW is the work done during the expansion distance ‘dx’ is
n is the number of moles dW = (Force) dx = PA dx = Pdv .........(4)
CP is the molar specific heat at constant pressure Substituting (1) and (4) in Eq 3
 (dQ)P = n CP dT2 = dU2 + dW _________ (2) CP dT = CV dT + PdV. .......... (5)
If the rise in temperature is same dT1 = dT2 = dT But according to ideal gas equation PV = RT,
so internal energies dU1 = dU2 where R is the universal gas constant. Differentiating
From equations 1 and 2 PV = RT. (As P and R are constants),
nCp dT = nCvdT + dW P dV = R dT. .............. (6)
Substituting Eq. 6 in Eq. 5 we have
dW
Cp = Cv +  Cp > Cv CP dT = CV dT + RdT or
ndT
9.36. RELATION BETWEEN CP AND CV (C P - CV ) dT = RdT
Consider one mole of an ideal gas CP - CV = R ...........(7)
contained in a conducting cylinder provided Where CP and CV and R are expressed in SI unit
with a frictionless piston. Let ‘ A ‘ be the area i.e, J/mole K. If CP and CV are in Cal / mole 0C then
of the piston and ‘P’, ‘V’ and ‘T’ be pressure, R
volume and temperature of the gas, the equation (7) becomes CP – CV = ___(8)
J
Where J is the mechanical equivalent of heat from equation (1)

But CP= M cP and CV = M cV then the equation dU 3 RdT 3
(7) becomes M cP – M cV = R  CV    R ............ (2)
dT 2 dT 2
R
cP – cV = But CP – CV = R
M
\ CP = R + CV
R
But = r the specific gas constant
M 3 5
\ CP = R + R= R ...................... (3)
 cP – cV = r ___________ (9) 2 2
9.37. SPECIFIC HEAT OF GASES IN TERMS (ii) For a di_atomic gas the degrees of freedom is 5
OF UNIVERSAL GAS CONSTANT R Hence the internal energy for 1 mole of gas
Temperature is the measure of average kinetic
energy of the moelcules of a gas. The kinetic energy 5
U RT
of a molecule is the sum of translational kinetic 2
energy, vibrational kinetic energy and rotational  The change in internal energy
kinetic energy. According to the law of equipartition
5
of energy, the total energy is divided equally among dU  RdT .................(4)
the degrees of freedom of a molecule. 2
The average kinetic energy per molecule per Let a small quantity of heat dQ is transferred to
the gas at constant volume so that only the internal
1 energy increases by dU.
degree of freedom = KT
2 Hence dQ = dU
where K is the Boltzmann’s constant T is the Let the corresponding rise in temperature be dT.
average temperature.
 molar specific heat at constant volume
Consider one mole of gas containing NA number
(Avegadro number) of molecules. dQ dU
CV = = from equation (4)
The average internal energy of the gas per 1´ dT dT
1 1 dU 5 RdT 5
degree of freedom = KN AT = RT CV    R ...................(5)
2 2 dT 2 dT 2
(i) For a mono_ atomic gas the degrees of
freedom is 3. But CP = CV + R
3
 The internal energy U  RT  CP 
5
RR 
7R
2 ...........(6)
2 2
 The change in internal energy
3 (iii) For a triatomic gas the degrees of freedom may
 dU  RdT ....................(1) be 6 to 7
2
Let a small quantity of heat dQ is transfered to  The internal energy
the gas at constant volume so that only the internal
6 RT 7
energy is increased by dU. Hence dQ = dU. U  3RT \ dU = 2 RdT
Let the corresponding rise in temperature be dT. 2
 Molar specific heat at constant volume 7 RT
dQ dU or U   dU  3RdT
CV   2
1  dT dT
If the quantity of heat transferred to one mole Let  1 ,  2 ......be the corresponding ratio of
of gas is dQ to increase the internal energy
specific heats.
 dQ = dU. Their internal energes be U1, U2 .......
Let the corresponding rise in temperature be dT. The internal energy of the gas mixure U1 + U2
dU 3RdT + .....U.
CV  = =3R & CP = 3R + R = 4R Let the change in temperature for all gases be dT
dT dT
As dU = n CvdT
dU 7RdT 7R
and CV  = = n1CV1 dT + n2CV2 dT + ....... = (n1 + n2 + ....)CVmix dT - - (1)
dT 2dT 2
& CP 
7R
R
9R (n1CV + n2CV
1 2
+ ........)
\ CVm i x =
2 2 (n1 + n2 + ........)
For a monoatomic gas =
CPmix  CVmix  R
5
CP 2 R 5 \ Ratio of specific heats of mixture
     1.67
CV 3 R 3 CPmix
2 g mix =
7 CVmix
CP 2 R 7
For a diatomic gas  =    1.4 R
CV 5 R 5
As Cv 
2  1
For a triatomic or polyatomic gas The equation (1) reduces to
CP 4 R 4 R R
=    1.33 n1 .d T + n 2 d T + .......
CV 3R 3 g1 - 1 g2 - 1
9.38. EXPRESSION OF C P AND C V IN = (n1 + n2 + ..)

R1
dT
TERMS OFADIABATIC CONSTANT : g mix - 1
Consider the relation CP – CV = R ® (1) n1 n2 (n1  n2  ...)

Cp Hence   1    1  ........    1
1 2 mix
= g \ C p = g .C v ® (2)
C v
*Problem 9.28
from (1) & (2) g C v - C v = R Calcula1te the difference between the two
specific heats of nitrogen, given that the density
R of nitrogen at N.T.P is 1.25 g/litre and J = 4200 J/
\ Cv = (3)
g- 1 ® kcal. Express it in kcal/kgK.
gR Solution :
from (2) and (3) Cp =
g- 1 P
The difference in specific heats, r  .
9.39. MIXTURE OF GASES T
(i) Specific heat of gas mixture : P = 1.013 × 105 N/m2; T = 273 K;
Let n1, n2, ... be the number of moles of differ-  = density of the gas
ent gases
Let CV1 , CV2 ......be the corresponding specific 10- 3 kg 1.25´ 10- 3 kg
r = 1.25´ 3 3
= 3 -6 3
= 1.25kg / m3
heats of the gases at constant volume. 10 cm 10 ´ 10 m
Problem 9.30
1.013´ 105
\ r= = 296.8J/kg K The specific heats of an ideal gas at constant
1.25´ 273
pressure and constant volume are 525 J/kg0C and
296.8 315 J/kg0C respectively. What is its density at NTP
r= kcal / kgK = 0.07068kcal/kg K.
4200 Sol : Let M be the molecular mass of the gas.
Then M (CP – CV) = R or M (525 – 315) = 8.31 or
 The difference of specific heats = 0.0768
kcal/kg K. M = 0.0392
Now let  be the density of the gas at NTP..
*Problem 9.29
Then it implies that mass of 1m3 of gas is  kg.
The difference between the two specific heats
of hydrogen is 0.9816 kcal/ kgK. Calculate its  mass of 22.4 L or (22.4 x 10–3) m3 of gas
density at N.T.P ( J = 4200 J/ kcal) should be (r ´ 22.4 ´ 10 - 3 ) kg which should be equal
Solution :
to its molecular mass i.e.,
If the difference between the two specific heats
is given in the unit J/kmole K then take Cp – Cv = R r ´ 22.4 ´ 10- 3 = 0.0392 or r = 1.75 kg / m 3
where Cp and Cv are molar heat capacities. If the *Problem 9.31
difference between the two specific heats is given in Specific heat of oxygen at constant pressure
the unit J/kg K then take is 0.2174 kcal / kg K. If the ratio of its specific
Cp – Cv = R where Cp and Cv are principal heats is 1.4, find the universal gas constant given
specific heats. If the difference between the two that J = 4200J/kcal and molecular weight of
specific heats is given in the unit cal/kg K then take oxygen is 32.
R
r Solution : We have seen that Cp 
Cp  C v   1
J
Cp = Molar heat capacity at constant pressure
where Cp and Cv are principal specific heats and = Principal specific heat at constant pressure
r is specific gas constant. x Molecular weight.
In this problem, the difference is given in the
As specific heat of oxygen at constant pressure
unit keal/kgK
is given in kcal/kg K. we have to convert it into J/kg
r K by multiplying with J = 4200 J / Kcal.
  0.9816kcal / kgK. Cp = 0.2174 x 4200 x 32 J/kmole K
J
R 1.4R
R P  
But r     1 (1.4  1)
M T
0.2174x4200x32x0.4
P R   8348J / kmoleK.
 0.9816 1.4
JT
*Problem 9.32
its density
Five kg of air is heated at constant volume.
P 1.013x10 5 The temperature of air increases from 300K to 340
  K. If the specific heat at constant volume is 0.169
JTx 0.9816 4200  273  0.9816
kcal/kg K, find the amount of heat absorbed.
( P  1.013X105 N / m 2 Solution : m = 5kg, dT = 340-300 = 40K,
J  4200J / kcal , T  273K = 0.09 kg/m3 Cv= 0.169 kcal/kg K,
dQ Solution :
Principal specific heat at constant volume Cv = Number of moles n = 4
mdT
The amount of heat absorbed, dQ = mCvdT Change in temperature t  2
= 5 x 0.169 x 40 = 33.8 kcal. Heat energy absorbed dQ = 40 cal.
*Problem 9.33 Gas constant R = 2 cal/mole K
Find the change in internal energy in joule, Heat energy absorbed at constant pressure
when 5 gm of air is heated from 0C to 2C dQ = dU + dW per mole per kelvin.
(Cv = 0.172 kcal/kg K, J = 4200 J/kcal) But dU  Cv dT and dW  PdV
Solution : C p  Cv  R Multiply with n.dT
m = 5g = 5 x 10-3 kg,
nC p dT  n C v dT  nRdT
dT = T2  T1 = (273+2)-(273+0) = 2K
Heat energy absorbed at constant
nC p dT 
C v  0.172kcal / kg pressure by n moles of gas.
K = 0.172 x 4200 J/kg K. nC v dT  dU  Heat energy absorbed at constant
The change in internal energy = Heat supplied volume.
at constant volume. = mCvdT  dQ = dU + nRdT = 40 + 4 ´ 2´ 2 = 56 cal
= 5 x 10-3 x 0.172 x 4200 x 2 = 7.224J.
Heat energy absorbed at constant pressure when
*Problem 9.34
4 moles of air is heated through 20  56 cal .
Five moles of hydrogen when heated
through 20 K expand by an amount of 8.3 x 10- 9.40. DIFFERENT THERMODYNAMIC
3 3
m under a constant pressure of 105 N/m2. If Cv= PROCESSES
20 J/moleK, find Cp As a process is simply a change in the state of
Solution : Mayer's relation Cp – Cv = R the system and there are infinite ways for a system
Multiplying throughout by nT to change from one state to another state, certain
processes are identified by special names, e.g., an
nCp T  nCv T  nRT isochoric process, an isobaric process, an isothermal
process and an adiabatic process. Any process may
nT(Cp  C v )  PV ( nRT  PV) have its own equation of state, but each thermo-
dynamical process must obey PV = n RT.
Cv = 20 J / mole Kand D V = 8.3´ 10- 3 m3 ) 9.41. ISOBARIC PROCESS (OR) CONSTANT
5 x 20(Cp - 20) = 105 x 8.3 x 10-3 PRESSURE PROCESS
( n = 5, D T = 20K, P = 1´ 10 5
N / m2 ) The process in which a system undergoes a
change in volume and temperature at constant
Cp - 20 = 8.3 pressure by the exchange of heat energy with the
Cp = 28.3 J/mole K. surroundings is called isobaric process.
Problem 9.35 Let the gas be heated at constant pressure to the
Four moles of a perfect gas is heated to same increase in its temperature dT. It is utilised to
increase its temperature by 20C absorbs heat of increase the internal energy (dU) and to do external
40 cal at constant volume. If the same gas is heated work (dW) in moving the piston through a small dis-
at constant pressure find the amount of heat tance dx against constant pressure P.
supplied. (R = 2 cal/mol K). Heat supplied at constant pressure = (dQ)P
\ (dQ) P = 1´ CP ´ dT = C P dT (for 1 mole) 9.42. ISOCHORIC PROCESS OR

CONSTANT VOLUME PROCESS
From the first law of the thermodynamics, we
can write The process in which a system undergoes a
change in pressure and temperature at constant
(dQ)P = dU + dW volume by the exchange of heat energy with the
surroundings is called isochoric process.
\ C P dT = dU + dW.
Consider one mole of an ideal gas contained in a
 nCpdT = dU + dW (for n mole) conducting cylinder provided with a frictionless
P piston. Let ‘ A ‘ be the area of the piston and ‘P’, ‘V’
and ‘T’ be pressure, volume and temperature of the
A B gas, respectively. Let the gas be heated at constant
volume, so that its temperature increases through
‘dT’. As the heat is supplied at constant volume, it is
D C utilised only to increase the internal energy of the gas.
V
\ Heat supplied at constant volume
P - V graph for this process is a straight line
(dQ)v  dU  1  Cv  dT
parallel to volume axis. Area below the graph P
gives work done. As expansion takes place, the work
is done by the gas, and it is positive.
 dW  Area of ABCD = P.dV = nR . dT
V
Gas obeys Charles’s law ie = constant. O
T V Volume
Note : dQ = nCPdT (at constant pressure) P -V graph for the process is a straight line
dU = nCv dT parallel to pressure axis.
dW = pdV = nRdT (at constant pressure) \ Work done in an isochoric process, dw = 0
P
dU Cv 1 dU 100 Here gas obeys Charles law ie  constant.
  , Þ ´ 100 = % T
dQ C p  dQ g 9.43. CYCLIC PROCESS :
dW R g- 1 dW æg - 1ö÷ A process in which a system undergoes series
= = Þ ´ 100 = çç
dQ C p g , dQ çè g ÷100%
÷
ø÷
of changes and which returns the system back to
its initial state is known as a cyclic process.
i) For monoatomic gas, 1) In case of cyclic process, Internal Energy (U) is
dU dW constant Þ dU = Uf - Ui = 0
 100 = 60%,  100 = 40%
dQ dQ i.e., change in internal energy for a cyclic
process is zero and also dU a dT Þ dT = 0 ,
ii) For Diatomic gas,
i.e., temperature of system remains constant.
dU 500 dW 200 2) First law of thermodynamics for a cyclic process
 100 = %,  100 = %
dQ 7 dQ 7 is given by
iii) For Triatomic gas dQ = dU + dW Þ dQ = dW ( dU = 0)
dU dW i.e., heat supplied is equal to work done by the
 100 = 75%,  100 = 25%
dQ dQ system.
3) For a cyclic process, P–V graph is a closed curve The following conditions must be fulfilled to
and area enclosed by the closed path represents keep the temperature (for an isothermal process)
the work done. constant
If the cycle is clockwise, work done is positive a) The cylinder and the gas should be good
and if the cycle is anticlockwise, work done is conductors of heat.
negative. b) The cylinder should be in good thermal contact
P P with surroundings.
c) The surroundings should allow heat exchanges
A B A D with the cylinder gas system keeping the
Positive Negative temperature of gas essentially constant.
work work d) The process should be quasi-static
D C B C
V V e) The process must be slow allowing sufficient
9.44. FREE EXPANSION OF GAS : time for the system to compensate for the
changes, if any
Free expansion is an adiabatic process in which
no work is performed on or by the system. f) P - V graph of an isothernal process is a
rectangular hyperbola
Consider two vessels placed in a system which P
is enclosed with thermal insulation (asbestos -
covered). One vessel contains a gas and the other is
T = c o n s ta n t
evacuated. Both the vessels are connected as shown
in figure along with a stop - cock. When suddenly
the stopcock is opened, the gas rushes into the V
evacuated vessel and expands freely. This expansion The ideal gas equation for 'n' moles of gas is
of the gas against vaccum is called free expansion. PV = nRT.
Stop cock As the temperature remains constant along with
mass of gas in this process the equation becomes
Gas Vaccum PV = constant  P1 V1 =P2 V2 .
This is the equation of isothermal process
In this process the internal energy remains
Insulated constant.
Here, dW = 0 (Because walls are rigid)
The change in internal energy dU= 0.
dQ = 0 (Because walls are insulated)
From first law of thermodynamics dQ =O+dw
\ dU = Uf – Ui = 0 ( Because dW and dQ are zero)
So the heat energy exchanged is completely
Thus the final and initial internal energies are
converted into work form.
equal in free expansion.
Note : This is true in the case of isothermal process
9.45. ISOTHERMAL PROCESS of ideal gas only.
A process in which a system undergoes
physical changes in such a way that the temperature Example : 1
remains constant by the exchange of heat energy When water is heated at normal atmospheric
with the surroundings is known as isothermal pressure it boils at 1000C and converts into water
process. vapour (steam).
Consider certain mass of a gas in a conducting The temperature remains unchanged during the
cylinder fitted with a frictionless movable piston. boiling process so it is an isothermal process
Example 2 : Melting of a substance. b) For ‘n’ moles the work done

When a substance in solid phase is heated, it  V2 
absorbs heat and starts melting at a particular W = 2.3026 n RT log10  V 
1
temperature called melting point at normal pressure.
Now the heating is continued. It is observed that the But P1V1 = P2V2 for an isothermal change
temperature remains same, till the substance V2 P1
 =
compeltely converts into liquid. So this is an V1 P2
isothermal process
 P1 
9.46. WORKDONE IN AN ISOTHERAL  W = 2.3026 nRT log10  P 
2
PROCESS :
Consider one mole of an ideal gas enclosed in a c) If ‘m’ is the mass of gas considered and M is its
cylinder fitted with a smooth and frictionless piston. molecular weight then
The walls of cylinder, base and piston are good m  V2 
conductors having good thermal contact with the W = 2.3026 RT log10  V 
M 1
surroundings. For a gas of mass 1 gram, the work done is
Let the cylinder be placed on a source of heat at
R  V2 
temperature T. If the piston is now moved slowly W = 2.3026 T log10  V 
outwards, the gas expands, does some work and M 1
tends to cool but it absorbs required quantity of heat R

But = r the specific gas constant.
from the source to keep it at the same temperature. M
Now the gas expands at constant temperature  V2 
 W = 2.3026 r T log10  
T isothermally from volume V 1 to V 2 . Let the  V1 
corresponding pressures be P1 and P2.
9.47. ADIABATIC PROCESS:
At any instant let P be the pressure of the gas.
Consider the motion of the piston through an “A process in which a system undergoes
elementary distance dx. If A is the area of the piston physical changes in such a way that heat is neither
the work done ‘dW’ is given by allowed to enter the system from the surroundings
nor allowed to leave the system to the surroundings
dW = Force × dx = P.A.dx = P.dV is called an adiabatic process”
Where dV is the infinitesimally small increase in Consider certain mass of a gas in a thermally
the volume of the gas at that pressure. The total work insulated cylinder fitted with a frictionless movable
done during the expansion from V1 to V2 is Wiso.,
V2
pistion.
then, Wiso = V
1
P.dV The following conditions must be fulfilled to
RT bringout the process.
But from gas equation P =
V a) The gas should be contained in a cylinder made
V2 V2
RT dV of bad conductor fitted with a piston made of
Wiso =  dV = RT 
V
V V
V bad conductor.
1 1
V  b) The cylinder gas system must be well insulated

Wiso = RT loge  2  thermally.
 V1 
c) The gas should be worked with quickly enough
 V2 
a) Wiso = 2.3026 RT log10  V  process so as not to allow any time for
 1  co mpensating any possible changes in
This expression gives the work done for 1 mole. temperature.
In adiabatic compression, the temperature where dV is decrease in volume = A.dx

increases as work is done on the gas. In adiabatic The heat generated due to compression causes
expansion, the temperature decreases as the work is a rise in temperature dT. This heat energy is equal to
done by the gas. So the adiabatic change is associated CvdT, where Cv is molar specific heat of the gas at
with change in internal energy dU and work done dW. constant volume. This is equal to the change in
From the first law of thermodynamics inernal energy dU.
dU + dW = 0 ( dQ  0) dU = Cv.dT .............(2)
Example: In an adiabatic process, there is no exchange of heat.
1. If a gas is compressed suddenly in thermally  dQ = 0 .............(3)
insulted flask then pressure, volume and
According to first law of thermodynamics
temperature changes from P1, V1, T1 to P2, V2,
T2. This is an adiabatic process. dQ = dU + dW
2. A cycle tube bursts suddenly. The pressure falls Substituting the values from (1), (2), & (3) in
to atmospheric pressure and the volume above equation
increases. The temperature decreases. This is O = Cv.dT + P.dV .............(4)
an adiabatic expansion. From the ideal gas equation,
3. If coffee in a thermas flask is shaken well, then we have PV = RT.
temperature increases, even though heat is not
supplied. This is an adiabatic process. On differentiating both sides
P.dV + V.dP = R.dT
9.48. RELATIONS BETWEEN P, V AND T IN
AN ADIABATIC PROCESS PdV + VdP
(i) Relation between P and V dT =
R
Consider one mole of an ideal gas contained in
Substituting the above value in equation(4)
a thermally insulated cylinder fitted with a
we have
frictionless, movable and thermally insulated piston.
Let P,V and T be the pressure, volume and æPdV + VdP ö÷
Cv çç ÷+ PdV = 0
temperature at any instant. çè R ø÷
Let the gas in the cylinder be compressed
adiabatically so that the piston moves inwards Cv ( PdV + VdP) + RPdV = 0
through an infinitesimally small distance “dx”.
Cv ( PdV + VdP) + (C p - Cv ) PdV = 0
If “A” is the area of the piston, the force acting
on the piston F = PA. ( But C p - Cv = R )
Cv PdV + CvVdP + C p PdV - Cv PdV = 0
dividing the above equation throughout by
dx (Cv PV ) , we get
dP C p dV
+ = 0
P Cv V
é C ù
Work done dW = Force × distance dP
+g
dV
= 0 êQ g = p ú
dW = P.A.dx = P.dV ......(1) P V ê Cv úû
ë
Let the initial pressure and volume be Pi and

PV = constant
Vi respectively and the final pressure and volume be
Pf and Vf respectively. Then on integration with in æRT ög P g
the limits, P çç ÷ ÷ = Constant (or) T = Constant
çè P ø÷ Pg
vf pf
dV dP i.e., P1- g T g = Cons tan t
ò V =-
g ò P This is the relation between P and T for an
vi pi adiabatic process.
v p 9.49. WORK DONE IN AN ADIABATIC
g [log e V ]v f = - [log e P ]p f
i i CHANGE.
æ P ö÷ Consider one mole of an ideal gas contained
æV f ö÷ çç i ÷
g log e ççç ÷
÷= log e çç P ÷
in a cylinder having non conducting walls and
çè Vi ø÷ ÷
è f ø÷ provided with a non conducting and frictionless
piston. Let the pressure, and volume of the gas be
æV f ö÷g æP ö÷
ç
loge ççç ÷
÷ = loge çç i ÷ ÷ P and V at any instant. Suppose the piston moves
çè Vi ø÷ çè Pf ø÷
÷ through an infinitesimally small distance ‘dx’ at
constant pressure ‘P’.
V fg Pi The work done dW = P.A.dx = P.dV

=
Vig Pf where ‘A’ is the area of the piston and dV is the
g g infinitesimally small change in volume.
\ PV
i i = Pf V f The system changes from the initial state (P1,V1)
to the final state (P2,V2). The temperature changes
PV g = Constant. ...................(5)
from T1 to T2.
This is the relation between P and V during an The work done during the change
adiabatic process. V2
ii) Relation between V and T W =  dW   P.dV

RT V1
From the gas equation PV=RT and P  For an adiabatic change
V
Substituting this value in equation K
PV  = k ( a constant) \ P = g
= KV- g
V
PV = constant V2

æRT ö÷ g
\ çç
 Wadia   KV dv
÷V = constant
çè V ø÷ V1
V
V2
  V1  2
RTV g- 1 = constan t Wadia  K  V dv  K  
 1    V1
V1
\ TV g- 1 = Constan t K  1
Wadia  V2  V11 
This is the relation between V and T during an 1   
adiabatic process.
1 
iii) Relation between ‘P’ and ‘T’ Wadia  KV21  KV11 
1   
From the gas equation PV = RT
RT But P1V1  P2 V2  K
V
P 1 
 Wadia  P2 V2 V21  P1V1 V1 
Substituting this value in adabatic equation 1   1 
1 b) For an adiabatic process PV  = constant.

Wadia 
1 
 P2 V2  P1V1 
On differentiating
But from gas equation P 1 V 1 = RT 1 and P. . V  1 dV  V  dP  0
P2V2 = RT2
or  P dV  V.dP  0
1
 Wadia  (RT2  RT1 ) dP P
1   
dV V
R
Wadia 
1 
 T2  T1   dP 

P
The adiabatic slope   ...(2)
 dV  adia V
R
or Wadia    1  T1  T2   dP   dP 
From (1) and (2)     .
This expression gives the work done for a 1  dV  adia  dV  iso
mole of gas.
 The slope of adiabatic is greater than that of
For ‘n’ moles of gas isotherm.
nR
Wadia  (T1  T2 ) . P
 1
If ‘m’ is the mass of gas considered and M is its A iso
t her
molecular weight then dP P m
B
mR
Wadia = (T1  T2 )
M(  1)
adia
Work done if 1gram of gas is considered b atic
R C D E F
Wadia = (T1  T2 ) O V
M(  1) dVa dVi
R From the diagram
But = r , the specific gas constant.
M dP AB
slope of adiabatic at P = 
r dV CD
 Wadia    1 (T1  T2 ) dP AB
slope of isotherm at P = 
9.50. COMPARISION OF THE SLOPES OF AN dV EF
As CD < EF
ISOTHERMAL AND ADIABATIC P-V GRAPHS
slope of adiabatic is greater than that of the
P – V graph of a given mass of a gas during isotherm
isothermal change is called an isotherm”.
Comparision of work done :
P – V graph of a given mass of a gas during
Consider, an isotherm and an adiabatic for a
an adiabatic change is called an “adiabatic”
given mass of a gas having same initial state ‘A’.
a) For an isothermal process PV = constant.
a) Let the gas expands from V1 to V2 in both cases.
On differentiating P.dV + V dP = 0 AB is the isotherm.
dP P
  The workdoneduringtheüïï
dV V ý = Wiso
isothermalexpansion ïïþ
 dP  P
 Slope of isotherm     ...(1) Wiso = Area ABDEA.
 dV  iso V
P Problem 9.36
A
isot In a cyclic process shown in the figure an
her
> m B ideal gas is adiabatically taken from B to A, the
>
adia
batic C
work done on the gas during the process B  A
is 30 J, when the gas is taken from A  B the
heat absorbed by the gas is 20J. What is The
change in internal energy of the gas in the process
E D
V1 V2 A  B.
V
AC is the adiabatic
P A
The workdoneduring üïï 20 J
ý = Wadi
theadiabaticexpansion ïïþ
30 J B
Wadia = Area AC DEA.
Comparing the areas it is observed that the work V
done by the gas isothermally is greater than the work Sol: WBA  30J,QBA  0
done by the gas adiabatically
In this case the isotherm is above the adiabatic.  UBA   WBA  30J
b) Let the gas be compressed from V1 to V2 in both Now, DUAB = - DUBA = - 30J
cases. The initial state A is same in both the
Problem 9.37
processes
AB represents the isothermal compression. A gas undergoes a change of state during
which 100 J of heat is supplied to it and it does 20
The work doneduring üïï J of work. The system is brought back to its
ý = Wadi original state through a process during which 20
theisothermalcompressionïïþ
J of heat is released by the gas. What is the work
Wiso = Area ABEDA done by the gas in the second process ?
AC represents the adiabatic compression.
Sol : In a cyclic process U  0
P
C  Q  W
 (100–20) = 20 + W2
> ad
iab
B  W2 = 60 J
ati
c
>
is o
th e
rm A Problem 9.38
An ideal gas is taken through the cycle
E D A  B  C  A , as shown in the figure. If the
V2 V1 net heat supplied to the gas in the cycle is 5 J,
V
what is the work done by the gas in the process
The work doneduring üïï
ý = Wadi CA
theadiabaticcompressionïïþ
2 C B
Wadia = Area ACEDA 3
V(m )
Comparing the areas it is observed that the work
1 A
done on the gas adiabatically is greater than the work
done on the gas isothermally.
In this case the isotherm is below the adiabtaic. 10 P(N/m2)
Sol :  WAB  PV  10  2  1  10J Process 2 – 3 :

Q2–3 = –85 kJ; W2–3 = – 20 kJ
 WBC  0 (as V = constant)
U3 – U2 = Q2–3 – W2–3 = –85 – (–20) = –65 kJ
From first law of thermodynamics
Q  W  U
U3 = – 65 + 175 = 110 kJ
U  0 (process ABCA is cyclic) For the complete cycle :  Q   W. That is

 Q  WAB  WBC  WCA Q1–2 + Q2–3 + Q3–1 = W1–2 + W2–3 + W3–1
 WCA  Q  WAB  WBC  5  10  0 80 – 85 + 0 = 0 + (–20) + W3–1
= – 5J
\ Work done during adiabatic process,
Problem 9.39
W3–1 = 15 kJ
A perfect gas undergoes the following three
separate and distinct processes to execute a cycle Problem 9.40
i) constant volume process during which 80 kJ An ideal monoatomic gas is taken round the
of heat is supplied to the gas, cycle ABCDA as shown in the P-V digram.
ii) constant pressure process during whcih Compute the work done in this process.
85 kJ of heat is lost to the surroundings and
A B
20 kJ of work is done on it. 5P0
iii) adiabatic process which restores the gas
Pr essure  P
back to its initial stte.
3P0 C
Evaluate the work done during adiabatic D
process and the value of internal energy at 2V0 3V0 5V0 6V0
all the state points if initially its value is
Volume  V
95 kJ.
Solution :
Solution :
Let the foot of the perpendiculars drawn from
This example illustrates the application of non-
points A,B,C and D on the volume axis be named as
flow energy equation and the 1st law applied to a
A1,B1,C1 and D1 respectively.
cyclic process.
Evidently, the work done during the processes
Process 1 – 2 :
AB,BC,CD and DA will be respectively, given by,
Q1–2 = 80 kJ ; W1–2 = 0 the areas (+ABB1A1),(+BCC1B1), (–CC1D1D) and
U2 – U1 = Q1–2 – W1–2 (–DD 1A1A). Here, the work corresponding to
= 80 – 0 = 80 kJ expansion is positive, and that corresponding to
compression is negative.
U2 = 80 + 95 = 175 kJ
 Total work done
= area (+ABB1A1) + area (+BCC1B1) +
p =const
pressure
3 2 area (-CC1D1D) + area (-DD1A1A)

V=const = area (+ABCD)

pV  const
1 = (6V0 – 3V0) (5P0 – 3P0)
volum = (3V0)(2P0) = 6P0V0 units
*Problem 9.41 Problem 9.43

During an adiabatic process, if the pressure A gas is expanded to double its volume by
of an ideal gas is proportional to the cube of its two different processes. One is isobaric and the
temperature, find  . other is isothermal. Let W 1 and W 2 be the
Solution : respective work done, then find w1 and w2
For an ideal gas of one mole PV = RT3 Vf 
Sol : W1  Pi  Vf  Vi   PV
i i
V
 1
During an adiabatic process PT3  i 
3
P = KT  nRT  2  1  nRT
3  K  3 3 æV ö
 PV  P  W2 = nRTloge çç f ÷ ÷= nRT loge (2) = W1 loge (2)
P = K  Þ  3 P V çè Vi ø÷
÷
 R  R 
*Problem 9.44
P 2V3  cons tan t If a monoatomic ideal gas of volume 1 litre
at N.T.P is compressed adiabatically to half of its
PV3/2  cons tan t
volume, find the work done on the gas. Also find
Comparing it with the equation
the work done if the compression is isothermal.
PV   constant for an adiabatic process,
(   5 / 3)
we get   3 / 2
Solution :
*Problem 9.42
i) During an adiabatic process
When 5 moles of an ideal gas is compressed
isothermally, its volume decreases from 5 litre to 1
T1V11  T2 V2
1 litre. If the gas is at 27°C, find the work done
on the gas. V1 5
Here, T1  273K; V2  ; 
Solution : 2 3
In the case of 'n' moles, work done on the gas 5 5
3
-1 æV1 ö÷3- 1
V  \ 273 ´ V1 = T2 çç ÷ ç
W  nRT log e  2  è 2 ø÷
 V1  2/3
T2 = (2) ´ 273 = 431.6K
V 
W  nRTx2.3026x log10  2  number of moles,
 V1  1litre 1
n 
R = 8.314 J mole -1K-1 ; 22.4litre 22.4
T = 27 + 273 = 300 K ; V1 = 1 litre = 10–3m3 nR
Work done = (T1  T2 )
V 1  1
 V2  5litre  5  103 m3  2 
V1 5 8.314 8.34x3
æ ö
(273- 431.6)= (- 158.6) = - 89J.
1 5
= 22.4ç - 1÷÷ 22.4x2
 W  5x8.314x300x2.3026x log10   ççè
3 ø÷
5 ii) Work done during isothermal compression is
= 5 x 8.314 x 300 x 2.3026 x (-0.6990) æV ö
= -2.007 x 104J W = 2.3026nRT log10 çç 2 ÷ ÷
çè V1 ø÷
÷
1 2
; log T2 = 2.4742 - (0.7782)
n = number of moles = 7
22.4
T  273K;R  8.314J mol1K 1 = 2.4742 - 0,2209 = 2.2533.
V2 1 Anti log of 2.2533 = 178.7
  0.5
V1 2  T2 = 178.7K Þ t2 = 178.7 - 273 = - 94.3OC.
2.3026x8.314x273log10 (0.5) Problem 9.47
W 
22.4 Three samples of the same gas A, B and C
W = -70J
(  = 3/2) have initially equal volume. Now the
Problem 9.45 volume of each sample is doubled. The process is
Temperature of 1 mole of an ideal gas is adiabatic for A, isobaric for B and isothermal for
increased from 300 K to 310 K under isochoric C. If the final pressures are equal for all three
process. Heat supplied to the gas in this process samples, find the ratio of their initial pressures
is Q = 25 R, where R = universal gas constant. Solution :
What amount of work has to be done by the gas
Let the initial pressure of the three samples be
if temperature of the gas decreases from 310 K
PA, PB and PC then
to 300 K adiabatically? 3 3
Solution : Q  nCV T PA  V  2   2V  2 P
PB = P
5
25R = (1) (CV) (310–300) or CV  R PC (V) = P (2V)
2
3/2
i.e., gas is diatomic or   1.4  PA : PB : PC = (2) : 1 : 2  2 2 : 1: 2
Now work done in adiabatic process Problem 9.48
An ideal gas mixture filled inside a balloon
nR(T1 - T2 ) (1)(R)(310 - 300)
W= = = 25R expands according to the relation PV2/3=constant.
g- 1 1.4 - 1 What is the temperature inside the balloon
*Problem 9.46 Solution : PV2/3 = constant
A tyre pumped to a pressure of 6 atmosphere
suddenly bursts. Room temperature is 25 oC. PV2 / 3 cons tant
 
Calculate the temperature of escaping air. PV RT
(  = 1.4.) 1 cons tant
or 1/ 3
  V  T3
Solution : V RT
From P11 T  P21 T2 Temperature increases with increase in volume.
Here, P1 = 6 atm P2 = 1 atm Problem 9.49
T1 = 273+25 = 298K;  = 1.4 An ideal gas expands isothermally from a
1.4
(6)(1-1.4)(298)1.4 = (1)(1–1.4) T2 volume V1 to V2 and then compressed to original
volume V1 adiabatically. Initial pressure is P1 and
(298)1.4 final pressure is P3. the total work done is W.
T21.4 1.4 0.4
 (298) 6 
60.4 Then what is its value and its conditions.
1 1.4 Solution : Slope of adiabatic process at a given state
 (298)1.4  1.4 (298)1.4 298 (P, V, T) is more than the slope of isothermal process.
T2   0.4   0.4
 2 The corresponding P - V graph for the two processes
 6  1.4 is as shown in figure.
(6) (6) 7
P = 2 × 106 × 0.2 loge 5

P3 C = 643775 J = 643.775 kJ
Considering process 2-3 which is at constant
P1
A
volume,
B i.e, V2 = V3 = 5 × 0.2 = 1m3
T3
p3 = p2 × = 400 × 103 × 300
T2 600
V2 V
V1 = 200 × 10 N/m2 = 0.2 MPa
3
W2–3 = 0 as volume remains constant.

In the graph, A,B is isothermal and BC is
adiabatic. For the polytropic process 3–1 = p3V3n = p1V1n
p1 2
WAB = positive (as volume is increasing) and loge loge
p3 0.2 2.3026
WBC = negative (As volume is decreasing) plus, n = = = = 1.433
V3 1 1.6094
loge loge
WBC  WAB V1 0.2
, as area under P - V graph gives
the work done.
Hence, WAB  WBC  W  0 p3 V3  p1V1 0.2  106  1  2  106  0.2
W3-1= 
n 1 1.433  1
From the graph itself, it is clear that P3 > P1
= –461894 J = –461.894 kJ
Problem 9.50 Net work done, Wn = W1–2 + W2–3 + W3–1
0.2 m3 of an ideal gas at a pressure of 2 MPa = 643.774 + 0 + (–461.894) = 181.88 kJ
and 600 K is expanded isothermally to 5 times
 Heat transfer during the complee cycle =
the initial volume. It is then cooled to 300 K at
181.88 kJ
constant volume and then compressed back
polytropically to its initial state. Determine the Problem - 9.51
net work done and heat transfer during the cycle. Draw the P-T and V-T diagrams of an
Solution : isochoric process of n moles of an ideal gas from
pressure P0, volume V0 to pressure 4P0, indicating
Considering process 1– 2 which is isothermal,
the pressures, and temperatures, of the gas, in
i.e., T1 = T2 = 600 K
the initial and the final states.
6
p2 = p1V1  2  10  0.2 Sol. From the equation of state for an ideal gas
V2 (5  0.2)
PV = nRT
= 400 × 10 N/m2 = 0.4 MPa
3
nRT
(a) P= i.e., P  T (  V = constant)
V
P0 V0
At P = P0 and V = V0, T  and
nR
4P0 V0
at P = 4P0, V = V0, T 
Work done, nR
V2 The graph is a striaght line (passing through the
W1–2 = p1V1 loge origin, when produced) shown in figure.
V1
2P0 V0
4P0 B and at V = 2V0, T2 
nR
Pressure  P 
P0 A 2P0 B
P0 V0 4P0 V0 Volum e  V 
nR nR V0 A
Temperature  T
P0 V0 4P0 V0 P0 V0 2P0 V0
(b) Since, temperature increases from to ,
nR nR nR nR
volume remaining constant, so, the graph of V - T Temperature  T
will be as shown in figure. From the graph of V versus T, the equation
 nR 
A B V    T or V = kT shows that the volume varies
V0  P0 
directly, as the temperature (Charles' law). So, the
Volume  V
graph is a straight line inclined to the (V - T) axis,
and passing through the origin (when produced) as
P0 V0 4P0 V0 shown in figure.
nR nR Problem - 9.53
Temperature  T
Draw the P – T and V – T diagrams for
Problem - 9.52 an isothermal process, corresponding to one
Draw the P - T and V - T diagrams for an isobaric mole of an ideal gas at an initial pressure and
process of expansion, corresponding to n moles of an volume P0 and V0 respectively, expanding to a
ideal gas at a pressure P0, from V0 to 2V0. volume 2V0 .
Solution : Solution :
For the graph of P versus T the variation is a The temperature T during the process is,
straight line normal to the pressure axis, the P0 V0
temperature varying from T1 to T2 as shown figure. evidently, given by T  (for one mole)
R
Also, for an isothermal process PV = constant
A B P0
P0
 P0 V0  P2  2V0  or P2 
P re ss u re  P  2
(a) The P - T graph is a stright line parallel to the
pressure axis, with pressure decreasing from P0 to
P0 V0 2P0 V0 P0/2 as shiwn in figure.
nR nR
Temperature  T 
P0 A
From the gas equation PV = nRT
Pressure  P 
 nR  B
we have, V   P  T or V  T P0
  0
2
P0 V0 P0 V0 / R
At V = V0, T1  Temperature  T
nR
(b) The V – T graph is also a straight line parallel 8P(V)   P '(6V  V ')  ..........(4)
to the volume axis, with volume increasing from V0
Dividing (4) by (3),
to 2V0 as shown in figure.
3/ 2
 6V  V'  8 6V 4 æ ö
çç g = 3 ÷
 V'   3/ 2 or V ' = 1 + 5 çè ÷
2 ø÷
2V0 A 5
Volume  V  10
B i.e., V'  V
V0 3
Substituting it in Eqn. (3),
P0 V0 / R  5V  3 
3/ 2
3 3
Temperature  T P'  P
 10V 
 P  1.84 P
2 2
Problem 9.54 10 8
A piston divides a closed gas cylinder into So P '  1.84 P; V '  V and (6V  V')  V .
3 3
two parts. Initially the piston is kept pressed such Problem 9.55
that one part has a pressure P and volume 5V
An ideal gas is compressed to half of the
and the other part has pressure 8P and volume
volume. How much work is done if the process
V; the piston is now left free. Find the new
of compression is (a) Isothermal (b) Adiabatic ?
pressure and volume for the isothermal and
In which of the two cases will the work done be
adiabatic process. (   1.5) . more ? How do you account for the difference ?
Final pressure will be same on both sides. Let (a) In case of isothermal change
it be P', with volume V', in the left side and (6V - V')
W = nRT loge (VF / VI )
in the right side.
So W1 = nRT loge [1/ 2} = - 0.6930 nRT ....(1)
(A) If the change is isothermal :
For the gas enclosed in the left chamber, (b) In case of adiabatic change,
P  5V  P'V'.....(1) nR[TF - TI ]
W= with TV 1  constt.
while for the gas in the right chamber, (1- g )
8P  V  P '(6V  V') .......(2) nRT1 é TF ù T V
 1
Solving these for V' and P', we get i.e., W = (g - 1) êê1 - T úú with TF   VI 
ë I û I  F
30 13
V'  V and P '  P nRT 2/3  5 
13 6 so W = [(5 / 3) - 1] [1- 2 ]  as   3 ; T1  T 
 
48
and (6V  V')  V 3
13 or WA = - nRT ´ 0.5874 = - 0.88nRT ....(2)
2
P 8P
L Negative sign means that work is done on the gas.
5V V
Comparing Eqns. (1) and (2) we find that for
same compression WA > W , i.e., more work is
P P
L required in adiabatic compression than in isothermal.
V (6V  V )
In adiabatic compression, temperature and
(B) If the change is adiabatic : For the gas in the left hence internal energy of the gas also increases and
chamber. so more work will be required in comparison to
P(5V)   P '(V ')  .............(3) isothermal compression in which temperature and
and for the gas in the right chamber, hence internal energy remains constant.
Problem 9.56 Problem 9.57

At 270C, two moles of an ideal monoatomic P - V diagram of a diatomic gas is a straight
gas occupy a volume V. The gas expands line passing through origin. What is the molar
adiabatically to a volume 2V. Calculate (a) final heat capacity of the gas in the process
temperature of the gas (b) change in its internal Solution :
energy and (c) the work done by the gas during
the process. (R = 8.31 J/mol K) P - V diagram of the gas is a straight line passing
through origin. Hence,
Solution : –1
P  V or PV = constant
(a) In case of adiabatic change, Molar heat capacity in the process
PVr  const. with PV = nRT PVn = constant is
So that T1 V1 1  T2 V2  1 [with  = (5/3)] R R
C= +
g - 1 1- n
i.e., 300  V2 / 3  T(2V)2 / 3 or
Here,   1.4 (for diatomic gas) & n = – 1
T  300 /(2)2 / 3  189K
R R
nR D T é R ù  C  or C  3R
(b) As D U = nCV D T = êasCV = ú 1.4  1 1 1
g- 1 êë (g - 1) úû
Problem 9.58
2 ´ 8.31´ (189 - 300) Find the molar heat capacity in a process of
DU = = - 2767.23 J
So æ5 ö÷
çç - 1÷
çè3 ø÷
a diatomic gas if it does a work of Q/4 when a
Negative sign means internal energy decreases. heat of Q is supplied to it
(c) According to first law of thermodynamics, Solution :
Q   U   W 5  2  dU 
and as for adiabatic change dU = CvdT =  R  dT (or) dT  from
2  5R
D Q = 0 Þ D W = - D U = 2767.23J first law of thermodynamics
9.51. POLYTROPIC PROCESS Q 3Q
dU = dQ – dW = Q – 
Each of the isochoric, isobaric, isothermal and 4 4
adiabatic processes are quasi-static in operation under Now molar heat capacity
ideal working conditions. For all these processes, the dQ Q´ 5R = 5RQ  10 R
C= =
relation between pressure and volume can be described dT 2(dU ) 2  3Q  3
by a single equation PV n  C where 'n' is a positive  
 4 
number. The value of index n remains constant
Problem 9.59
throughout in any particular process. The equation
PV n  C is called polytropic law, and the process in A monoatomic gas undergoes a process given
which the state of the system changes in accordance by 2dU + 3dW = 0, then what is the process
with this correlation is called a polytropic process. Sol : dQ = dU + dW
For a polytropic process PV n  constant
2dU dU 1
Specific heat of gas during polytropic process is  dQ  dU    nCv dT
3 3 3
R R
C= +
 γ -1 1- n  ( where  is adiabatic 1 3
 n. RdT 
nRdT
C 
1 dQ R

exponent of the gas) 3 2 2 n dT 2
5R
It is not isobaric as C is not equal to Q 1 W
2 C   U  W   Cv 
It is not adiabatic as c  0 T T T
It is not isothermal as c   so it is an polytropic For the given process
process. 9 P0
W  4V0  18PV
0 0 ( W= area of P – V graph)
Problem 9.60 2
Ideal monoatomic gas is taken through a Also, T  T2  T1
process dQ = 2dU. What is the molar heat
capacity for the process ? (where dQ is heat (6 P0 )(5V0 ) (3P0 )V0 27 PV
0 0
= - =
supplied and dU is change in internal energy) R R R
dQ 2dU 2nCv dT 3
Solution : C     2Cv  3R and Cv  R
ndT ndT ndT 2
W 3R 18PV 0 0
Problem 9.61 \ C = Cv + = +
DT 2 ç 0 0 ö÷
æ 27PV
The relation between U, P and V for an ideal gas ççè R ø÷ ÷
is U = 2 + 3PV. What is the atomicity of gas.
3R 2 R 13R
Sol : For an adiabatic process = + =
2 3 6
dQ = 0 = dU + dW
or 0 = dU + PdV –––– (1) 9.52. HEAT ENGINE
From the given equation "A device used to convert heat energy into
dU = 3 (PdV + VdP) useful mechanical work is called heat engine".
A heat engine consists of the following main
 0 = 3 (PdV + VdP) + PdV (from (1)
parts
or 4P (dV) + 3V (dP) = 0
(a) Source : It is a hot reservoir or a body which is
 dV   dP  at higher temperature T1 and can extract any
or 4    3  
 V   P  quantity of heat Q1 without any change in its
temperature. So, its thermal capacity is infinite.
On integrating, we get
In (V4) + In (P3) = constant (b) Sink: It is a cold reservoir or body at lower
or PV4/3 = constant temerature T2 which can take any amount of
heat Q2 rejected by the working substance

i.e.,   without any change in its temperature. So, its

thermal capacity is infinite.
i.e., gas is polyatomic.
(c) Working substance :In steam engine the
Problem 9.62 working substance is steam at high pressure.
One mole of a monoatomic ideal gas In diesel engine the working substance is
undergoes the process A  B in the given P - V mixture of fuel and air. It absorbs certain amount
diagram. What is the specific heat for this process ? of heat from the source, converts a part of it into
P
work and rejects the remaining heat to the sink.
6P0 B The working substance is taken through a cyclic
3P0 process. At the end of each cycle, the working
A
V
substance is brought to its original condition. So
V0 5V0
internal energy of the working substance does not
Solution : Specific heat change.
The block diagram of a heat engine is as shown. (i) The cylinder containing ideal gas is placed on
Working substance absorbs heat Q1 from the source the source and the gas is allowed to expand
and rejects heat Q2 to the sink. Here the amount of slowly at constant temperature TH absorbing heat
work done by system is W = Q1 – Q2. Let T1and T2 QH. This isothermal change is represented by
be the temperatures of source and sink. the curve AB in the indicator diagram.
ENGINE
Hot Q1 Q2 Cold A Isothermal Expansion
Working B
TH
Reservoir Reservoir
Adia
Substance P
Adia
at T1 at T2
bati
bati
c Co
c
Exp
mpr
ansi
essi
on
on
D
C
W TL
Isothermal Compression
Fig - 12
The efficiency of an engine is the ratio between VA VD VB VC
workdone (W) by the engine and the amount of V
(ii) The cylinder is then placed on the non-
heat absorbed(Q1) by the engine. conducting stand and the gas is allowed to
Efficiency of heat engine expand adiabatically till the temperature falls
W Q1  Q2 Q2 from TH to TL . This adiabatic expansion is
   1
Q1 Q1 Q1 represented by the curve BC.
Carnot designed ideal heat engine which (iii) The cylinder is next placed on the sink and the
converts heat energy into useful mechanical work. gas is compressed at constatn temperature TL
No heat engine can have efficiency more than the along path CD transferring a certain quantity of
efficiency of a Carnot engine operating between a heat Q L to the sink.
given pair of source and sink temperatures.
(iv) Finally the cylinder is again placed on the non-
Efficiency of Carnot's ideal heat engine is
conducting stand and the compression is
Q2 T continued so that the gas returns to its initial
  1  1 2
Q1 T1 stage along DA.
Note : The efficiency of the carnot's ideal heat engine The closed path ABCDA represents the so
is independent of nature of working substance. It called Carnot cycle and the four stages taken
depends only upon the temperatures of the source together represent a cyclic process.
and sink. The greater the difference between the two So, the working substance is brought back to
temperatures, higher is the efficiency of the carnot's initial state. The area of the loop ABCDA is equal to
engine. heat converted into work and is equal to Q1 – Q2.
(i) Efficiency is the same for all carnot's heat engines 9.53. CARNOT ENGINE :
working between temperatures T1 and T2
Carnot devised an ideal engine which is based
(ii)  is always less than one. on a reversible cycle of four o perat ions in
succession.
(iii) If T1 = T2 then  = 0
a) Isothermal Expansion
**Carnot Cycle [or Working of the Engine] :
b) Adiabatic Expansion
The working substance in a Carnot's engine is
taken through a reversible cycle consisting of the c) Isothermal Compression
following four steps : d) Adiabatic Compression
If T1 and T2 are absolute temperatures of source Coefficient of performance measures the

and sink, then Work done in Carnot cycle efficiency of any refrigerator. It is defined as the ratio
of the quantity of heat extracted per cycle from the
W = Area enclosed by cycle ABCD
contents of the refrigerator to the mechanical work
V  W done by the external agency to do so
Also W  RT1  T2  log e  B 
 VA  Q Q2 T2
 2  We can write 
Heat absorbed from source W Q1  Q 2 T1  T2
V  Note:
Q1  W1  RT1 loge  B 
 VA  (i)  value varies from 2 to 6
W (ii) In heat engine, efficiency can never exceed
Since, Efficiency,   Q 100%. But in the case of a refrigerator,the
V coefficient of performance may be much higher
RT1  T2  loge f
Vi T T T than 100%.
   1 2  1 2
V T1 T1 Problem 9.63
RT1 loge f
Vi The temperature - entropy diagram of a
So, Efficiency of Carnot Engine,
reversible engine cycle is given in figure. What is
Q2 T
  1  1 2 its efficiency
Q1 T1
Q1 Q 2 2T0
also In a Carnot cycle T  T
1 2
If an engine consists of a number of sources and T
 Q  Q T0
sinks, then 

  
T source 
 
T sin k
S0 2S0
S
9.54. REFRIGERATOR
1 3
Refrigerator is a Carnot's ideal heat engine Solution: Q1=T0S0 + T0S0 = TS
working in the reverse direction. 2 2 0 0
Source : The substances kept inside the refrigerator. Q2=T0(2S0 – S0) = T0S0
Sink : The surroundings (room) of the refrigerator. Q3= 0
Here working substance is refrigerent. It absorbs W Q1  Q2 Q
a certain quantity of heat Q2 from the cold body or  =   1  2 = 1  T0 S0  1
Q1 Q1 Q1 3
sink at lower temperature T2 . A certain amount of T0 S 0 3
work W is performed by the compressor of the 2
refrigerator on the working substance. The quantity Problem 9.64
of heat Q1 is rejected to the hot body at temperature T1.
The block diagram of an ideal refrigerator will An inventor claims to have developed an
be as shown engine that during a certain time interval takes
REFRIGERATOR in 110 MJ of heat at 415 K, rejects 50 MJ of heat
Hot Q1 Q2 Cold at 212 K while manages to do 16.7 kWh of work.
Working
Reservoir Substance Reservoir Do you agree with the inventor's claim ?
at T1 at T2 Solution :
The claimed efficiency
W 16.7 kWh
hC = =
QH 110 MJ
W But as 1 kWh  103  (J / s)  (60  60 s)  3.6 MJ
16.7  3.6 Problem 9.67

So C   0.55  55% .............(1)
110 An ideal gas is taken through a cyclic
while maximum possible theoretical efficiency, thermodynamic process through four steps. The
TL TH  TL 415  212 amounts of heat involved in these steps are Q1 =
max  1   
TH TH 415 5960 J, Q2 = – 5585 J, Q3 = – 2980 J and QA =
 0.49  49% .......(2) 3635 J respectively. The corresponding works
From Eqns. (1) and (2) it is clear that claimed involved are w1 = 2200 J, W2 = –825 J, W3 = –
efficiency is greater than maximum possible 1100 J, and W4 respectively (i) Find the value of
theoretical efficiency ; so inventor's claim does not W4 (ii) What is the efficiency of the cycle ?
appear to be correct. Solution :
Problem 9.65 In a cyclic process dU = 0
The temperatures T1 and T2 of two heat Net heat absorbed by the system,
reservoirs in the ideal Carnot engine are 15000C
Q = Q1 + Q2 + Q3 + Q4
and 500 0 C respectively. Which of these,
increasing T1 by 1000C or decreasing T2 by = 5960 – 5585 – 2980 + 3645 = 1040J
1000C, would result in a greater improvement in Net work done W = W1 + W2 + W3 + W4
the efficiency of the engine?
Solution : = 2200 – 825 – 1100 + W4 = 275 + W4
As the efficiency of a heat engine is given by From 1st law of thermodynamics,
T2 T - T2 Q = dU + W or 1040 = 0 + 275 + W4
h = 1- = 1
T1 T1 \ W4 = 1040 – 275 = 765 J
so when T1 is increased by 100 0 C , Work done (W)
Efficiency of cycle =
(1600  500) 1100 Heat absorved(Q1  Q 4 )
1    59% .....(1)
(1600  273) 1873 275  765 1040
 
and when T2 is decreased by 100 0 C , 5960  3645 9605
1040
(1500  400) 1100 % efficiency = × 100 = 10.83%
2    62% .....(2) 9605
(1500  273) 1773
Problem 9.68
From Eqns. (1) and (2), it is clear that decreasing Find the efficiency of the thermodynamic
T2 results in greater improvement in the efficiency.. cycle shown in figure for an ideal diatomic gas.
Problem 9.66
A refrigerator, whose coefficient of 2P0 B
performance K is 5, extracts heat from the cooling
compartment at the rate of 250 J per cycle. Pressure  P
P0 A C
(a) How much work per cycle is required to
operate the refrigerator cycle ? (b) How much
heat per cycle is discharged to the room which V0 2V0
acts as the high temperature reservoir?
Volume  V 
(a) As coefficient of performance of a refrigerator Let n be the number of moles of the gas and the
is defined as K  Q L / W , temperature be T0 in the state A.
Q 250 Now, work done during the cycle
So W  L   50 J
K 5
(b) As Q H  Q L  W 1 1
W   2V0  V0  2P0  P0   P0 V0
so Q H  250  50  300 J 2 2
It means that it is not possible to get a continuous

For the heat  Q1  given during the process supply of work from a body by cooling it to a
A  B , we have temperature lower than that of the surroundings.
(b) Classius statement: " It is impossible for a
Q1  WAB  UAB self acting machine unaided by any external agency
WAB = area under the straight line AB to transfer heat from a body at lower temperature
to a body at higher temperature".
1 3P V It means that by itself heat cannot flow from a

2
 P0  2P0  2V0  V0   0 0
2 body at lower temperature to a body at a higher
Applying equation of state for the gas in the temperature.
state A and B. Kelvin's statement can be interpreted in many
ways and suggests that no heat engine can convert
P0 V0  2P0  2V0  whole of the heat energy supplied to it into useful
  TB  4T0
T0 TB work.
 5R  Second law of thermodynamics explains about
 U AB  nCV T  n    4T0  T0  the practical limit of conversation of heat energy into
 2 
useful work. Complete conversion of heat energy
15nRT0 15P0 V0 into mechanical work is impossible. If second law
 
2 2 of thermodynamics is not valid, all the heat absorbed
from a body is converted into work and there will be
3 15 an endless source of energy. But this is not possible.
Q1  P0 V0  P0 V0  9P0 V0
2 2 First law and second law of thermodynamics are not
Obviously, the processes B  C and C  A derived from one another. They are separate laws.
involve the abstraction of heat from the gas.
Assess your self
 Efficiency   of the cycle 1. "Heat flows from a hot body to a cold body".
Work done per cycle What is the law that governs this process ?
=
Total heat supplied per cycle A. Second law of thermodynamics. According to
1 it, heat can not be from a cold body to a hot
P0 V0 1
i.e., = 2 body on its own accord.

9P0 V0 18 2. How many number of specific heats can a
9.55. SECOND LAW OF THERMODYNAMI CS gas possess.
A. Depending upon the process of heating the
First law of thermodynamics gives the gases can have infinite number of specific heats.
equivalence between the mechanical work and heat
produced. It does not give any idea about the 3. State the zeroth law of thermodynamics in
conversion of heat into work or vice versa. It does mathematical form
not explain about the direction in which heat transfer A. f(PVT) = 0
takes place. Second law of thermodynmics is a where P,V,T are the thermodynamics variables.
fundamental law of nature which explains that heat
can flow only from hot body to cold body by itself. 4. State the differential form of first law of
There are several statements of this law. Two are the thermodynamics
most significant. A. dQ = dU + dW.
(a) Kelvin-Planck statement : "It is impossible dQ = The quantity of heat supplied to a system
by any thermodynamic process which results solely dU = The change in internal energy.
in the removal of heat from a heat reservoir and
convert it entirely into work." dW = Work done
5. " Heat can be completely converted into thermodynamics.

work" Explain. 13. If you place your hands on a wooden and a
A. According to first law of thermodynamics. metal chair at the same temperature, Lower
If heat is supplied to a system so that its than your body temperature, which of them,
temperature does not rise then dU = 0 do you find hotter.
Hence dQ = dW so heat can be transformed A. As the wooden chair is a bad conductor heat
into work completely. But according to second energy is not transferred quickly from body to
law of thermodynamics it is not possible the wooden chair hence it appears to be hot.
6. What is the equation to be followed by any But Heat energy is transferred quickly from the
thermodynamical process. body to the metal chair when touched as it is a
A. Any thermodynamical state may have its own good conductor.
equation of state, but each thermodynamical 14. When you place your hands on a wooden
process must obey and a metal chair at the same temperature ,
PV = nRT where n gives the number of moles. if your body temperature is lower what will
7. Should a quasistatic process be reversible ? be your inference.
A. No. It need not be a reversible. Any process A. Metal chair appears to be hot as heat energy is
can be analysed by assuming it to be the transferred to the body as the metal chair is a
composition of quasistatic processes good conductor. As wooden chair is a bad
8. Should a cyclic process be reversible ? conductor it appears to be cold.
A. No. The condition for cyclic process is that the 15. A sound wave is sent into a gas pipe. Does
system should reach the initial state only after its internal energy change?
the process. It does not depend on the path. Any
A. The propagation of sound wave through a pipe is
process can be made reversible by following
a quick process. It is an adiabatic change and the
same path in reverse direction.
temperature changes, changing the internal energy.
Reversible process need not be a cyclic process
16. What happens when a metal spring dissolves
9. Water is heated by using an immersion
in an acid?
heater. Can the process be reversed?
A. No. It is an irreversible process. By withdrawing A. The internal energy of the acid increases,
heat from water, heat can not be transferred to increasing the temperature
electricheater to make it hot. 17. When water boils at constant temperature
10. Is evaporation of water a reversible process of 100oC, is there any change in the internal
A. Conversion of the water phase into vapour phase energy?
is reversible. By boiling water, its phase can be A. When water changes into vapour phase it has
changed into vapour and it is a reversible process. more internal energy in the form of latent heat.
11. An ideal gas is allowed to expand at constant So the steam at 100oC has more internal energy
temperature in a quasistatic process. Can than water at 100oC
you reverse this process. 18. Which type of energy of the following given
A. Yes. This process can be reversed by making the to a system changes its internal energy. (a)
gas to follow the same path as in the expansion Electromagnetic (b) Electrical (C) Nuclear.
12. Suppose you keep your two hands on two A. All the three types increase the internal energy
bodies simulteneously and feel them equally 19. Give an example of decrease of internal
cold or hot. What is your inference energy at constant temperature
A. The hands and the bodies are same at A. When water freezes at 0oC volume increases.
temperature and hence they are in thermal As the work is done by the system, using its
equilibrium according to zeroth law of internal energy, the internal energy decreases.
20. A small bottle of an ideal gas is brought into 25 If the difference in the molar specific heats
a thermally insulated room and it is broken of a gas is equal to R what will be the
into pieces in the room. What happens to the difference in the molar specific heats if there
temperature of the room. are n moles.
A. If vacuum exists in the room free expansion takes A. R. As the work done is proportional to number
place. So the work done against vacuum is zero. of moles, this value does not change.
 dW = 0. As it is isolated dQ = 0 so No 26. Whether more work is done in isothermal
change in internal energy and hence no chnage expansion or adiabatic expansion.
in temperature. A. From the P-V graph the adiabatic is steeper than
21. When two ice blocks are rubbed against each isothermal. So the isothermal lies above the
other some ice melts in between the two adiabatic showing the area with respect to volume
which law can explain the process axis is more. So isothermal work done is more.
A. Heat is required to melt ice. The work done in 27. Why the adiabatic is steeper than an
rubbing is the mechanical energy is transformed isotherm in a P-V graph.
into heat energy, It is joules law. Ans. For adiabatic process PV   cons tan t
22. Two identical bodies at temperature T1 and dP P
T2 are brought into thermal contact. Under The gradient is   
dV V
what conditions they come to thermal Similarly for isothermal process PV = const
equilibrium at the mean temperature.
dP P
A. When they are in thermal equilibrium at the mean The gradient of isotherm 
temperature their thermal capacities are be equal. dV v
23. Equal masses of two liquids at different Hence the adiabatic is steeper than the isotherm
temperatures are mixed, if the resultant 28. In which process (isothermal or adiabatic)
temperature is equal to the mean of their there is greater change internal energy?
temperatures, what is your inference about A. For a given change in volume, the work done
their specific heats ? in adiabatic process is less hence the change in
A. When two liquids of equal mass 'm' at different internal energy is more
t1 and t2 and having different specific heats s1 29. Equal quantities of ice at OoC and steam at
and s2 are mixed. 100OC are mixed up. What will be the
Heat lost by hot liquid =Heat gained by cold resultant temperature.
liquid A. As latent heat of steam is greater than that of ice
t1  t 2 The heat required to melt ice and then to rise
common temperature t =
2 the temperature to 100oC is available.
Let t1 > t2
So the resultant temperature is 100oC.
 t t  t t  30. "You can not get some thing for nothing"
m.s1  t1  1 2   ms2  1 2  t 2 
 2   2  Do you think this statement is equivalent to
any law of thermodynamics.
t t  t t 
ms1  1 2   ms2  1 2   s1  s2 A. It is first law of thermodynamics. When dU = 0,
 2   2 
dQ = dW So the above result occurs.
24. Two liquids A and B have their specific heats
31. Why is it not possible to cool down a room
as SA and SB respectively If SB < SA, which
of the two would you use as coolent ? on a hot summer day by leaving the
A. The coolent must have greater specific heat so refrigerator open
that it absorbs more heat. Hence the liquid A is A. The room behaves as source when t he
preferred to B refrigerator is working normally When the
door is kept open the room behaves as sink. 11. Explain the reversible process.
Less heat is absorbed from sink and more heat 12. Explain the irreversible process.
is given out to the source. So the room is 13. Explain qualitatively the working of heat engine.
14. Explain qualitatively t he working o f a
heated up.
refrigerator.
This is vio lation o f second law of
15. Under what conditions a process can be
themodynamics as source and sink are same. considered to be a reversible process.
Long Answer Questions 16. What is an isothermal process. State the
conditions to be fulfilled by an isothermal
1. Obtain the relation between (a) P,V (b) V,T (c) process.
P,T during adiabatic change. 17. What is an adiabatic process. State the
2. Define the two molar specific heats of a gas conditions to be fulfilled by an adiabatic
and deduce the relation between them. process.
3. Describe the method of determination of specific Very Short Answer Questions
heat of a solid by the method of mixtures. 1. What is heat capacity ? What is specific heat ?
4. Describe how the value of latent heat of 2. State zeroth law of thermodynamics. What is
vapourisation of water is determined by method its significance ?
of mixtures. 3. Define Calorie and mean calorie ?
5. Explain the following processes 4. Define latent heat of fusion and latent heat of
(a) Quasi static process (b) Cyclic process vapourisation.
5. What is the principle used in determining the
(c) Reversible process (d) Irreversible process
specific heat of a substance.
6. Explain qualitatively the working of heat
6. What is the relation between the work and heat?
engines and refrigerators.
7. When a gas expands through V at constant
Short Answer Questions pressure P, what is the work done ?
1. State and explain t he first law of 8. What is the specific heat of gas in (a) an
thermodynamics isothermal change (b) an adiabatic process.
2. St ate and explain the second law of 9. A thermos flask containing a liquid is shaken
thermodynamics. vigorously. What happens to its temparature ?
3. Write down the expression for the work done 10. When can we treat a process as a a Quasi-static
by an ideal gas during isothermal change and process ?
explain. 11. What is the relation between total heat
4. Write down the expression for the work done absorbed and work done by a system in a
by an ideal gas during adiabatic change and cyclic process ?
explain.
12. When will be the efficiency of a heat engine
5. What is the difference between second law of
thermodynamics and the law of conservation maximum ?
of energy. 13. What are 'source and sink' in a heat engine ?
6. Show that Cp-Cv = R in the case of 1 mole of an 14. Briefly state the functioning of a heat engine.
ideal gas. 15. Briefly state the functioning of a refrigerator.
7. Write short notes on triple point of water. 16. Define the efficiancy of a heat engine and state
8. Explain how Cp of a gas is greater than Cv. its expression.
9. Explain Quasi static process. 17. Give a few examples of reversible process.
10. Explain the Cycilc process. 18. Give a few examples of irreversible process.

Thermodynamics (311-364)

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PHYSICS-IC THERMODYNAMICS

9.1. Introduction : 9.2. Heat and temperature :

Note : (i) The specific heat of the material of the  m 2  m1 s1

Solution : Thermal capacity of a body = ms. Given ; m = 1000 g, s = (3t2 + t)

Explanation : Consider a hot body of mass m1 , Final temperature (t) = 300C

m1 s1t1 + m2 s2t2 m1 × 0.5 × 30 = m2 × 0.3 × 10 or

Thermometer Temperature of the hot solid = t20C

9.10. LATENT HEAT

unit mass of a substance during the change of

Latent heat of fusion of ice is 3.35 × 105 Jkg–1 or Lid

or 540 cal g–1.

180 1 Problem 9.13

The process of changing the solid phase into FSuperheated

a substance changes into gaseous phase is known as Solid Liquid Vapour

boiling point of the substance at normal pressure. 3 4

The temperature doesnot change till the 6

Problem 9.17 9.13. MELTING POINT

Example : is essentially an unstable phenomenon, since the

Fig - 18 Problem 9.18

9.16. SATURATED AND UNSATURATED 9.18. TRIPLE POINT

at which the solid phase (ice) and vapour phase Note :

(iii) If the pressure at triple point is kept constant

and temperature increases vapour state exists

1. Closed system : a) There is an exchange of matter with the

flask either by conduction or by convection or path :

So, Joule's mechanical equivalent of heat is *Problem 9.21

As V and T change at constant pressure the

P(V2–V1) = nR(T2– T1) if P is constant D C

9.35. CP IS GREATER THAN CV : respectively. Let the gas be heated at constant

Where J is the mechanical equivalent of heat from equation (1)

9.38. EXPRESSION OF C P AND C V IN = (n1 + n2 + ..)

Consider the relation CP – CV = R ® (1) n1 n2 (n1  n2  ...)

\ (dQ) P = 1´ CP ´ dT = C P dT (for 1 mole) 9.42. ISOCHORIC PROCESS OR

Example 2 : Melting of a substance. b) For ‘n’ moles the work done

tends to cool but it absorbs required quantity of heat R

V  b) The cylinder gas system must be well insulated

In adiabatic compression, the temperature where dV is decrease in volume = A.dx

Let the initial pressure and volume be Pi and

ii) Relation between V and T W =  dW   P.dV

1 b) For an adiabatic process PV  = constant.

Sol :  WAB  PV  10  2  1  10J Process 2 – 3 :

U  0 (process ABCA is cyclic) For the complete cycle :  Q   W. That is

3 2 area (-CC1D1D) + area (-DD1A1A)

*Problem 9.41 Problem 9.43

P = 2 × 106 × 0.2 loge 5

W2–3 = 0 as volume remains constant.

Problem 9.56 Problem 9.57

If T1 and T2 are absolute temperatures of source Coefficient of performance measures the

16.7  3.6 Problem 9.67

It means that it is not possible to get a continuous

5. " Heat can be completely converted into thermodynamics.

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