Page 1 Introduction and First Law of Thermodynamics

First law of Thermodynamics

S I R
C E
R IN
y P
B
Page 2 Introduction and First Law of Thermodynamics

CHEMISTRY
(T HERMODYNAMICS )

TERMS USED IN THERMODYNAMICS

System, Surrounding and Boundary : A system is defined as a specified part of the universe or
specified portion of the matter which is under experimental investigation and the rest of the universe,
i.e., all other matter which can interact with the system, is surrounding.

Boundary: Anything which separates system and surrounding is called boundary.

(i) Adiabatic and diathermic : The terms diathermic wall and adiabatic wall are used for con

I R
ductor and non-conductor of heat boundaries respectively.

(ii) Real and imaginary

E S
(iii) Rigid and non-rigid

IN C
P R
TYPES OF SYSTEM :There are three types of system
A.
B y
Isolated system : This type of system has no interaction with its surrounding. Neither
matter nor energy can be exchanged with surroundings.
B. Closed system : This type of system can exchange energy in the form of heat, work or
radiations but not matter with its surrounding.
C. Open system : This type of system can exchange matter as well as energy with surroundies.
(i). Homogeneous system : A system is said to be homogeneous when it is completely
uniform throughout. A homogeneous system is made of one-phase only. Examples are : a pure single
solid, liquid or gas, mixture of gases and a true solution
(ii). Heterogeneous : A system is said to be heterogeneous when it is not uniform
throughout, i.e., it consists two or more phases. Examples are : ice in contact with water, two or more
immiscible liquids, insoluble solid in contact with a liquid, a liquid in contact with vapour, etc.
THERMODYNAMIC PROPERTIES : These are of two types :
1.Intensive properties : The properties which do not depend upon the quantity of matter present
in the system or size of the system are called intensive properties. Pressure, temperature,
density, specific heat, surface tension, refractive index, viscosity, melting point, boiling point,
volume per mole, concentration, etc., are the example of intensive properties of the system.
2.Extensive properties : The properties whose magnitude depends upon the quantity of matter
present in the system are called extensive properties.
Page 3 Introduction and First Law of Thermodynamics

Extensive properties follow addition property but intensive propreties are non additive.
 The product , sum and ratio of properties are also intensive properties.
Extensive property when expressed per mol or per gram becomes intenisve property.
A A
Let A and B be two extensive properties, then and are intensive variables.
B B

In t e ns ive p r o p e rt ie s E xt e n siv e p r o p e r tie s

M ola r ity He a t c a pa c ity
M ola lity Mas s
C on c e ntr a tio n Vo lu m e
D en sit y Nu m b e r o f m ole s
T e m pe r a tur e Ent ha lp y
P r es su re Ent ro py
M ole f r a c tion Int er na l e n er g y
M ola r en tha lp y Gib bs fr e e e n rg y
M ola r en tr opy
M ola r in te rn a l e ne r gy

I R
R e fr a c tiv e in de x
S p ec if ic he a t

S
V isc os it y

E
S u rf a c e te ns ion

C
D ie le ctr ic c ons ta nt

IN
EM F

P R
y
State of System

B
When the total mass, temperature, volume, number of moles and composition have definite values,
the system is said to be in a definite state. when there is any change in any one of these properties,
it is said that the system has undergone a change of state.
State function or State Variables : Fundamental properties which determine the state of a system are
referred to as state variables or state function or thermodynamic parameters. The change in the
state properties depends only upon the initial and final states of the system, but is independent of the
manner in which the change has been brought about. In other words, the state properties do not
depend upon a path followed.
Following are the state variable that are commonly used to describe the state of the thermodynamic
system :
1. Pressure (P) 2. Themperature (T)
3. Volume (V) 4. Internal energy (E)
5. Enthalpy (H) 6. Entropy (S)
7. Free energy (G) 8. Number of moles (n)

Path Functions : The value of these functions are dependent on the path followed in bringing about
In the change. e.g.Heat and work
Note :- (i) In adiabatic process, E = W, so here W is a state function..
(ii) In isochoric process E = Q , so here Q is a state function.
(iii) H and E are path functions whereas H and E are state functions..
Page 4 Introduction and First Law of Thermodynamics

Thermodynamic Processes : When the thermodynamic system changes its state, the path followed
in order to do so is called a process. The various types of the processes are :
A. Isothermal process : The process is termed isothermal if temperature remains fixed, i.e.,
operation is done at constant temperature. This can be achieved by placing the system in constant
temperature bath, i.e., thermostat. For an isothermal process dT = 0, i.e., heat is exchanged with the
surrounding and the system is not thermally isolated.

S I R
V

C E
B.

R IN
Adiabatic process : If a process is carried out under such condition that no exchange of heat

P
takes place between the system and surrounding, the process is termed adiabatic. The system is

y
thermally isolated,i.e., dQ = 0. This can done by keeping the system in an insulated container, i.e.,

B
thermos flask. In adiabatic process, the temperature of the system varies.

Isothermal

 The slope of adiabatic curve is  time the slope of isothermal curve.

C. Isobaric process : The process is known as isobaric in which the pressure remains constant
throughout the change, i.e., dP = 0.

D. Isochoric process : The process is termed as isochoric in which volume remains constant
throughout the process i.e., dV = 0.
E. Cyclic process : When a system undergoes a number of different processes and finally
returns to its initial state, it is termed as cyclic process. For a cyclic process dE = 0 and dH =0.
Page 5 Introduction and First Law of Thermodynamics

Isobaric process Isochoric process

F. Reversible process : A process which occurs infinitesimally slowly, i.e., opposing force is
infinitesimally smaller than driving force and when infinitesimal increase in the opposing force can
reverse the process, it is said to be reversible process. A reversible process is an ideal process and

R
cannot be realised in practice. Both system and surroundings return to their original state in a
reversible process.

S I
E
G. Irreversible process : When the process goes from initial to final state in single step in finite

C
time and cannot be reversed, it is termed as irreversible process. An irreversible process is

IN
spontaneous in nature. All natural processes are irreversible in nature.

R
WORK (W)

y P
Work is the mode of transfer of energy between system and surrpundings.Work associated
with change in volume of a system against external pressure is called mechanical work
M e c h a n i c

Work (w) is a path-dependent function.

a

B
 Pext (V2 – V2) =  Pext V
l w o r k =

Work done on the system, w = +ve

Work done by the system, w = –ve

HEAT
It may be defined as the quantity of energy which flows between a system and its surroundings
due to temperature difference.
(i) Heat absobed by the system, Q = +ve
(ii) Heat released by the system, Q = –ve
Unit of Heat and Work : The unit of heat is calorie (cal)..

SI unit of heat is joule (J).

1 Joule = 0.2390 cal
1 calorie = 4.184 J
1 kcal = 4.184 kJ
1 litre-atm = 101.3 J.
= 1.013 × 109 erg = 24.206 cal
Page 6 Introduction and First Law of Thermodynamics
INTERNAL ENERGY (U)
Total of all possible kinds of energy of a system is called its internal energy*.
U = UKinetics + UPotential + UElectronic + Unuclear + .....
Characteristics of Internal Energy :
(i) Internal energy of a system is an extensive property.
(ii) Internal energy is a state function i.e. U = Ufinal – Uinitial
(iii) There is no change in internal energy in a cyclic process.
* For a given system , U can be represented as a function of T and V.
U = f (T, V)

 U   U 
dU =   . dT +   dV
 T  v  V T
* For isochoric process : dV = 0

 U 
dU =   dT
 T  v
dU = Cv . dT
S I R
U   C v .dT
C E
For an ideal gas

R IN
 U 
  0
y P
B
 V  T
because for ideal gas When there are no interactions between the molecules, the internal energy is
independent of their separation and hence independent of the volume of the sample.

 U 
  0
 V  T
Perfect gas  U 
  0
 V  T

 U 
  0
 V  T

Attractions dominate

Volume,V
Page 7 Introduction and First Law of Thermodynamics

dU = Cv . dT
U   C v .dT
ZEROTH LAW OF THERMODYNAMICS
Two systems in thermal equilibrium with a third system are also in thermal equilibrium with each other.

FIRST LAW OF THERMODYNAMICS :

It is based upon the law of conservation of energy.The total energy of the universe is constant.
When a system is changed from initial state to the final state, it undergoes a change in the internal
energy from Uin to Uf . Thus, U can be written as :
U = Uf – Uin
The change in internal energy can be brought about in two ways :
(i) Either by allowing the heat to flow into the system (absorption) or out of the system (evolution)
(ii) By doing work on the system or the work done by the system.
U = q + w
Enthalpy (H):

S I R
Heat content of a system at constant pressure is called enthalpy denoted by ‘H’
Enthalpy function can be written as H = U+ PV.

C E
 Enthalpy of a substance depends on Temperature and state of substance.

R
From first law of thermodynamics ;
IN
P
Q = U + PV ......(i)
Change in heat Q = U + PV + VP

B y
Heat change at constant pressure can be give as
Q = U + PV ......(ii)

At constant pressure heat can be replaced by enthalpy

H = U + PV ......(iii)

At constant volume, V = 0; thus equation (ii) can be written as

Q = U
 H = Heat change or heat of reaction at constant pressure

U = Heat change or heat of reaction at constant volume.

(i) In case of solids and liquids participating in a reaction,

H  E (PV  0)

(ii) Difference between H and E is significant when gases are involved in a chemistry reaction.
H = E + PV
H = E + ngRT
Here,
ng = Number of gaseous moles of products – Number of gaseous moles of reactants.
Page 8 Introduction and First Law of Thermodynamics
For a given system Enthalpy can be represented as a function of T and P
H = f (T, P)

 H   H 
dH =   . dT +   dP
 T  P  P  T
 For isobaric process : dP = 0

 H 
dH =   dT
 T  P
dH = CP . dT
H   C P .dT
 For an ideal gas

 H 
  0

R
 P  T
dH = CP . dT
S I
H   C P .dT
C E
IN
HEAT CAPACITY

one degree.
P R
Heat capacity is defined as the amount of heat required to raise the temperature of the system by

Heat Capacity (C) =

B
dq
dT y
Heat capacity is an extensive property as the amount of heat required (q) to raise the temperature
by T depends on the mass of the substance.

Molar heat capacity is the heat capacity per mole of the substance and it is an intensive property.
Its unit is JK-1mol-1.

Specific heat capacity is the heat capacity per unit mass of the substance and it is also an intensive
property. Its unit is J K-1 Kg-1
Following two types of heat capacities are used-
 U 
(i) Heat capacity at constant volume (CV) =   and thus U   C v .dT
 T V

 H 
(ii) Heat capacity at constant pressure(CP) =   and thus H   C .dT
 T  P P

 Cp - Cv =PV = R
Cp 2
    1 , where f is the degree of freedom for a given gas
Cv f
Page 9 Introduction and First Law of Thermodynamics
N o r m a l T e m p e r a tu r e H i g h T e m p e r a tu r e

G as Cv Cp  Cv CP 

He 3 5 5 3 5 5
R R = 1 .6 7 R R = 1.6 7
2 2 3 2 2 3

H2 5 7 7 7 9 9
R R  1 .4 R R  1 .2 9
2 2 5 2 2 7

CO2 5 7 7 13 15 15
R R  1 .4 R R  1 .1 5
2 2 5 2 2 13

SO2 3R 4R 4 6R 7R 7
 1 .3 3  1 .1 7
3 6

CH4 3R 4R 4 1 2R 13 R 13
 1 .3 3  1 .0 9
3 12

Heat capacity of mixtures:- let n1 and n2 moles of two non-reacting gases A and B are mixed than
n1 C v 1  n2 (C v ) 2
Cv mix 
n1  n2
Change in Enthalpy with temperature
S I R
C E
T2

C
IN
For a finite change , qp = H = p dT

R
T1

P
 if Cp is independent of T in the range T1 to T2, then H = Cp(T2 - T1)
If Cp depends on temperature as

y
p
= a + bT + cT2 + .......
C

B
T2

 (a  bT  cT  ......)dT
2
where a , b, c .. are constants then H =
T1

Example:1. 10 dm3 of O2 at 101.325 kPa and 298 K is heated to 348 K. Calculate the heat
absorbed, H and U for this process at (i) Costant pressure (ii) at constant volume .
Given Cp = 25.72 + 0.013(T/K) - 3.86 x 10-6
PV 102.325  10
Solution:- No. of moles of gas (n) =   0.409
RT 8.314  298
(a) at constant pressure
T2
 
T2 2 3
T 6 T
qp = H = n
T1
C p dT n
= 

25.72T  0.013
2
 3.8610
3
....
T1
after substituting the values we get qp = H = 603.59 J

U = H - nRT = 603.59 - 0.409 x 8.314 x 50 = 433.57 J

(b) at constant volume

T2 T2 T2 T2

qv = U = n  C v dT  n  (C p  R ) dT   n C p dT -  nR dT
T1 T1 T1 T1

= 433.57 J
Page 10 Introduction and First Law of Thermodynamics
H = U + nRT = 603.59 J
 This question also proves that q is a path function because the value of heat is different
in both cases whileU and H which are state functions have same values.

THERMODYNAMICAL ANALYSIS OF VARIOUS PROCESSES

(1) Isothermal Process :

In an isothermal expansion, heat is allowed to flow into or out of the system so that temperature
remains constant throughout the process of expansion.
E = 0

According to first law of thermodynamics,

E = q + w

R
Since, for isothermal process, E = 0, hence
q = –w

S I
E
Work done in reversible isothermal expansion :

w =  2.303 nRT log

V2

IN C P
 - 2.303 nRT log 1

R
V1 P2

y P
Work done in irreversible isothermal expansion :
The work done when volume changes from V1 toV2 is given by

Maximum work : B
w = – Pext ×dV = –Pext (V1 – V2)

Maximum work is done by the gas on surrounding when Pext = P gas

(2)Adiabatic Expansion :
In adiabatic expansion, no heat is allowed to enter or leave the system, hence, q = 0. According to
first law of thermodynamics,

E = q + w, we get E =w.
Reversible adiabatic expansion :
PV = constant
R P2V2  P1V1
Work done = C . T = C(T2 – T1) = (  – 1) (T2 – T1) =
 1
nR
For n moles = (  – 1) (T2 – T1)
Irreversible adiabatic expansion :
 RT RT 
w   Pext (V2  V1 )   Pext  2  1 
 P2 P1 
 Page 11 Introduction and First Law of Thermodynamics

P1T2 P2T1
w = C (T2 – T1) = – RPext ( )
P2 P1

Note:- Work done in any process is the area under the P-V curve.
Expansion Compression

Adiabatic
P Isothermal
P
Isothermal

Adiabatic

V
V

S I R
When initial and final volume are same for both the processes then
(i) For expansion Wisothermal > Wadiabatic

C E
IN
(ii) For compression Wadiabatic > W isothermal

P R
 Magnitude of Work done in a reversible expansion is more than irreversible expansion
T1 P2 T2 P1

y
whereas work done in reversible compression is lesser than work done in irreversible

B
P P
compression.It therefore follows that the temperature decrease in an irreversible expansion
1 2
i
will be less than the corresponding temperature decrease in reversible expansion.where as
temperature rise will be more in irreversible compression than the reversible one.

Example: 2 5 moles of an ideal gas at 293K are expanded isothermally from an initial pressure of
0.4053 MPa to a final pressure of 0.1013 MPa against a constant external pressure of 0.1013 MPa.
Calculate q,W, U and H. Calculate the corresponding values if the above process is carried out
reversibly.
Solution For an isothermal expansion against constant pressure work done
 nRT nRT  1 1 
w = -Pext(V2 -V1) =  Pext      Pext nRT   
 p1 p2   p1 p2 
substituting the given values w = -9.136 kJ
Since the process is isothermal i.e. T = constant , so U = 0, H = 0 and q =  w
If the process is carried out reversibly than for reversible isothermal expansion we have
P1
w = - 2.303 nRT log
P2
w = -16.889 kJ

Example: 3 A sample of a fluorocarbon was allowed to expand reversibly and adiabatically to

twice its volume. In the expansion the temperature dropped from 298.15 K to 248.44 K. Assume the
gas behaves perfectly estimate the value of CV.
Page 12 Introduction and First Law of Thermodynamics
Solution: According to the equation of state of adiabatic process
TV  1  constant
 1
T1  V2 
 
T2  V1 
after substituting the values 1.2  (2)  -1  log1.2  (  1) log 2    1.262
R R
Now C v    3.816R  31.7 JK -1 mol 1
  1 0.262

(3)Free Expansion :- It is an irreversible process in which expansion takes place agsinst zero pressure i.e.
Pext=0
in free expansion w = PextdV = 0
Real gases experience a temperature change during free expansion. For an ideal gas, the temperaturE
doesn’t change, and the conditions before and after adiabatic free expansion satisfy.
PiVi  Pf V f

S I R
where p is the pressure, V is the volume, and i and f refer to the initial and final states.

E
Since initial and final states are same so H = U = 0 amd thus q = -w =0

 For an adiabatic process H = U

IN C
P R
Calculation of temperature in adiabatic process:-

nCv(T2-T1) = Pext 
B 
y
For an irreversible adiabatic expansion work done w = P(V2-V1) = nCv(T2-T1)
 nRT1 nRT2 
 , from this equation final temperature can be calculated.
 p1 p2 

Example: 4 An ideal monoatomic gas (Cv = 1.5 R) initially at 298 K and 1.013 MPa pressure expands
adiabatically and irreversibly until it is in equillibrium with a constant external pressure of 0.1013 Mpa.
What is the final temperature of the gas ?
 nRT1 nRT2 
Solution:- For an adiabatic irreversible process nCv(T2-T1) = Pext   
 p1 p2 

T T  T T 
n 1.5R(T2  T1 )  nRPext  1  2   1.5(T2  T1 )  Pext  1  2 
 p1 p2   p1 p2 
On substituting the values we get T2 = 190.7 K
Page 13 Introduction and First Law of Thermodynamics

 V2  nb 
For any real gas expression of q for isothermal revrsible change q  nRT ln 
 V1  nb 

2  1 1
For any real gas expression of U for isothermal revrsible change U  n a  
 V2 V1 
For any real gas expression of w for isothermal revrsible change
 V  nb   1 1 
(  w )  nRT ln  2   n 2 a   
 V1  nb   V 2 V1 
For any expansion process we know that

V1  V2  V1 nb  V2 nb  - V1 nb  - V2 nb
 V2 V1 - V1 nb  V2 V1 - V2 nb
(V2  nb) V2 I R
 V1 (V2  nb)  V2 (V1  nb)

S
E
Thus 

C
(V1  nb) V1

IN
So we can conclude that q real > qideal i.e. for same change in volume heat absorbed by a real gas

R
is greater than the heat absorbed by an ideal gas.

y P
JOULE-THOMSON EFFECT
For an ideal gas there is no attraction or repulsion between the gas molecules if this gas expands

B
adiabatically into vaccum no cooling is produced in the process which menas that there is no change in
internal energy it depends only on temperature.
Where as a real gas on expansion from high to low pressure gets cooled on the side
of lower pressure. The greater the difference in the pressure higher will be difference in temperature.

Thus when a gas expands adiabatically from a region of high pressure to low
pressure it gets cooled and this phenomenon is known as Joule-thomson effect.
Most of the gases are found to undergo cooling on expansion except Helium & Hydrogen.
If the initial pressure and volume are P1 and V1 and final values are P2 and V2 respectively than

Total work done by gas (w) = P1V1 - P2V2

Since q =0 , the work done by the gas lowers its internal energy and hence temperature falls.

Thus from first Law of Thermodynamics

U = w = P1V1 - P2V2

 E 2  E1  P1V1  P2V2  ( E 2  P2V2 )  ( E1  P1V1 )  0

H 2  H 1  0  H  0

i.e.Joule - Thomson effect occurs at constant Enthalpy and thus it is isenthalpic .

Page 14 Introduction and First Law of Thermodynamics

Joule - Thomson Coefficient ()

dT 1  2a 
     b
dP C p  RT 
if  >0, than gas cools on expansion and
if <0, than gas warms on expansion
Inversion temperature
It is defined as the temperature below which a gas cools on expansion and above which it
warms on expansion.
2a
Ti 
Rb
 is zero at inversion temperature.
 has positive value below Ti and negative value above Ti.

MOLAR HEAT CAPACITY FOR A POLYTROPIC PROCESS

In a polytropic process PVx = constant.(K)
S I R
E
then by ideal gas equation KV1-x = nRT

C
Differentiatine w.r.t. temperature(T)

IN
R
dV
K(1  x)V  x  nR


dV

y P dT
nR

B
dT P(1  x)

Now, Molar heat capacity(C) =

dq d (dU  w) d ( nC v dT  pdV )
= =
nR
= nCv (1  x )
dT dT dT
nR nR
C =  1  1 x
Page 15 Introduction and First Law of Thermodynamics
“Boost your Basics”
Q.1. One mole of a gas is heated at constant pressure to raise its temperature by 1°C. The work done in
joules is :
(A) –4.3 (B) –8.314 (C) –16.62 (D) Unpredictable
Q.2. Identify the intensive property from the following :
(A) Volume (B) Mass (C) Enthalpy (D) Temperature
Q.3. Which one of the following is an extensive property ?
(A) Enthalpy (B) Concentration (C) Density (D) Viscosity
Q.4. For a cyclic process, the condition is :
(A) E = 0 (B) H = 0
(C) E > 0 and H > 0 (D) Both E = 0 and H = 0
Q.5. For the reaction of one mole zinc dust with one mole sulphuric acid in a bomb calorimeter, U and w
correspond to
(A) U < 0, w = 0 (B) U < 0, w < 0

R
(C) U > 0, w = 0 (D) U > 0, w > 0
Q.6.
S I
The work done in ergs for a reversible expansion of one mole of an ideal gas from a volume of 10 litre

E
to 20 litre at 25°C is :
(A) 2.303 × 8.31 × 107 × 298 log2
(C) 2.303 × 0.0821 × 298 log 0.5
IN C (B) 2.303 × 0.0821 × 298 log 2
(D) 2.303 × 2 × 298 log 2
Q.7.
P R
What is the change in internal energy when a gas contracts from 377 ml to 177 ml under a constant

y
pressure of 1520 torr, while at the same time being cooled by removing 124 J heat?

B
[Take : (1 L atm) = 100 J ]
(A) –24 J (B) – 84 J (C) – 164 J (D) –248 J
Q.8. The value of H – U for the following reaction at 27°C will be :
2NH3(g)  N2(g) + 3H2(g)
(A) 8.314 × 273 × (–2) (B) 8.314 × 300 × (–2)
(C) 8.314 × 273 × (–2) (D) 8.314 × 300 × 2

Q.9. For an endothermic reaction, where H represents the enthalpy of reaction, the minimum value for the
energy of activation will be :
(A) Less than H (B) Zero (C) Equal to H (D) More than H

3
Q.10. H and U for the reaction, S(s) + O (g)  SO3(g) are related as :
2 2
(A) H = U – 0.5 RT (B) H = U – 1.5 RT
(C) H = U + RT (D) H = U + 1.5 RT

Q.11. The word ‘standard’ in standard molar enthalpy change implies :

(A) Temperature 298 K (B) Pressure 1 atm
(C) Temperature 298 K and pressure 1 atm (D) All temperatures and all pressure
Page 16 Introduction and First Law of Thermodynamics
Q.12. Which one of the following statements is false ?
(A) Work is a state function
(B) Temperature is a state function
(C) Work appears at the boundary of the system
(D) Change in the state is completely defined when the initial and final are specified.

Q.13. Which one of the following equations does not correctly represent the first law of thermodynamics for
the given process ?
(A) Isothermal process : q=–w
(B) Cyclic process : q=–w
(C) Isochoric process : U = q
(D) Adiabatic process : U = –w
(E) Expansion of gas into vacuum : U = q

Q.14. In which of the following pairs, both properties are intensive ?

(A) number of moles, temperature (B) Density, volume
(C) Temperature, density
I R
(D) Pressure, volume

S
C E
IN B

PR U

By
A
Q.15. From the given graph interpret which of the following is correct ?

(A) Cv(A) > Cv(B)

(B) Cp(A) >Cp(B)
(C) Cv(A) = Cv(B)
(D) Cv(A)<Cv(B)

Q.16. The molar heat capacity(Cm) of an ideal gas -

(A) Cannot be negative (B) Must be equal to either Cv or Cp
(C) must be between Cv <Cp (D) may have any value between   to  
Q.17. When a gas is subjected to adiabatic expansion, it gets cooled due to :
(A) Fall in temperature (B) Loss in kinetic energy
(C) Decrease in velocity (D) Energy spent in doing work

Q.18. During isothermal expansion of an ideal gas, its :

(A) Internal energy increases
(B) Enthalpy decreases
(C) Internal energy and heat enthalpy remains unaltered
(D) Enthalpy reduces to zero
Page 17 Introduction and First Law of Thermodynamics
Q.19. 1 mole of gas occupying 3 litre volume is expanded against a constant external pressure of 1 atm to a
volume of 15 litre. The work done by system is :
(A) 1.215 × 103 J (B) 12.15 × 103 J (C) 121.5 × 103 J (D) None of these

Q.20. One mole of a gas in the state A (P1, V1, T1) is subjected to adaibatic expansion to attain state B
(P2, V2, T2). The work done by the gas is :

(A) –
b g
R T1  T2
(B)
b g
nR T2  T1
(C)
b g
R T2  T1
(D)
bP V  P V g
2 2 1 1

 1  1  1  1

Q.21. Consider following statements :

I : When the system returns to its original condition, the overall change in a state function is zero
II : When a gas expands, work energy is released, hence work done is negative and is done by the
system.
III : C(s) + CO2(g)  CO(g)
in this ng = zero hence, no work is done. Select correct statements :
(A) I, II, III (B) I, II (C) II, III (D) I, III

Q.22. Numerical value of work done is maximum in case of :

S I R
E
(A) C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l) (B) C(s) + CO2(g)  2CO(g)
(C) 2Fe(s) + 4H2O(g)  Fe3O4(s) + 4H2(g)

IN C (D) NH4Cl(s)  NH3(g) + HCl(g)

R
Q.23. If W = -20 kJ the negative sign indicates that the :

y P
(A) Expanding system gains work energy and does work on the surroundings
(B) Expanding system loses work energy and does work on the surroundings

B
(C) Expanding system gains work energy and does work on the system
(D) Expanding system loses work energy and work is done by the surroundings.

Q.24. Which of the following has the highest enthalpy content and which the lowest at a given temperature ?
I : H2O(s); II : H2O(l); III : H2O(g)
Highest Lowest
(A) I II
(B) I III
(C) III I
(D) II III

Q.25. A gas is cooled and loses 50 J of heat. The gas contracts as it cools and work done on the system
equal to 20 J is exchanged with the surroundings. Hence, U is :
(A) 70 J (B) –30 J (C) 30 J (D) – 70 J

Q.26. From the figure representing enthalpy change of various transition as Vapour
indicated, a substance has maximum enthalpy when present in :
(A) Solid state (B) Liquid state Hvap
(C) Gaseous state (D) Equal in all states Liquid
Hfusion
Solid
Page 18 Introduction and First Law of Thermodynamics
Q.27. When 1 mole of CO2(g) occupying volume 10 L at 100°C is expanded under
adiabatic condition, temeperature falls to 150 K. Hence, final volume is :
(A) 20 L (B) 5 L (C) 80 L (D) 40 L

Q.28. Water and alcohols have unusaually large entropies of vaporisation. This is because of :
(A) Larger molecular weight (B) Larger density
(C) Extensive hydrogen bonding (D) Lower free energy

Q.29. Out of boiling point (I), entropy (II), pH (III) and density (IV), Intensive properties are:
(A) I, II (B) I,II, III (C) I, III, IV (D) All of these

Q.30. What is U for the process described by figure. Heat supplied during the process q = 100 kJ.

S I R
C E
(A) + 50 kJ
R
(B) – 50 kJ
IN (C) –150 kJ (D) + 150 kJ

y P
Q.31. An ideal gas is taken around the cycle ABCDA as shown in figure. The net work done during the cycle
is equal to :

P2 B
B D
P
P1
C
V1 V2
V

(A) zero (B) positive (C) negative (D) we cannot predict

Q.32. One mole of an ideal monoatomic gas expanded irreversibly in two stage expansion.
State-1 (8.0 bar, 4.0 litre, 300 K)
State-2 (2.0 bar, 16 litre, 300 K)
State-3 (1.0 bar, 32 litre, 300 K)
Total heat absorbed by the gas in the process is :
(A) 116 J (B) 40 J (C) 4000 J (D) None of these

Q.33. An insulated container of gas has two chambers separated by an insulating partition. One of the chambers
has volume V1 and contains ideal gas at pressure P1 and temperature T1. The other chamber has volume
V2 and contains ideal gas at pressure P2 and temperature T2. If the partition is removed without doing
any work on the gas, the final equilibrium temperature of the gas in the container will be-
Page 19 Introduction and First Law of Thermodynamics

T1T2 (P1V1  P2 V2 ) P1V1T1  P2 V2 T2

(A) P V T  P V T (B) P1V1  P2 V2
1 1 2 2 2 1

P1V1T2  P2 V2 T1 T1T2 (P1V1  P2 V2 )

(C) P1V1  P2 V2 (D) P V T  P V T
1 1 1 2 2 2

Q.34. An adiabatic cylinder fitted with an adiabatic piston at the right end of cylinder, is divided into two equal
halves with a monoatomic gas on left side and diatomic gas on right side, using an impermeable movable
3
adiabatic wall . If the piston is pushed slowly to compress the diatomic gas to th of its original volume.
4
The new volume of monoatomic gas would be
25 3
 4  21 7 4
(A) Vnew = Vinitial ×   (B) Vnew = Vinitial ×  
3 5

21
 3  25
S I R 3

E
(C) Vnew = Vinitial ×   (D) Vnew = Vinitial ×

C
4 4

IN
Q.35. Which of the following graph represents a cyclic process different from remaining three?

P
PR P

By
V P

(A) (B) (C) (D)

1
T V V T

Q.36. A real gas is subjected to an adiabatic process from (2 bar, 40 lit., 300K) to (4 bar, 30 lit., 300 K)
against a constant pressure 4 bar the enthalpy change for the process is
(A) Zero (B) 6000 J (C) 8000 J (D) 10000 J

Q.37. An ideal gas is expanded reversibly so that the amount of heat transferred to the gas is equal to the
decrease of its internal energy. Then the equation of process in the variable T & V.
(A) T V(1–)/ 2 = const (B) T V(–1)/ 2 = const
(C) V T(–1)/ 2 = const (D) T V2(–1) = const

Q.38. In a constant pressure process for 5 mole of an ideal monoatomic gas, the temperature of gas increased
from 300 K to 500 K. Which of the following is incorrect regarding the process?
(A) Hsys = 2500 R (B) Usys = 1500 R (C) q = 3500 R (D) w = –1000 R
Page 20 Introduction and First Law of Thermodynamics
Q.39. The equation of state for one mole of a gas is
PV = RT + BP
where B is a constant, independent of temperature. The internal energy of fixed amount of gas is function
of temperature only. If one mole of the above gas is isothermally expanded from 12 L to 22 L at a
constant external pressure of 1 bar at 400 K, then the change in enthalpy of the gas is approximately.
[Given : R = 0.083 L-bar/K-mol, B = 2 L/mol]
(A) 0 (B) –3.32 J (C) –332 J (D) – 166 J

Q.40. One mole of Argon is heated using PV5/2 = constant. By what amount heat is absorbed during the
process, when temperature changes by T = 26 K.
(A) 100 J (B) 200 J (C) 180 J (D) 208 J

Q.41. A student is calculating the work during a reversible isothermal process, shown by 2 moles of an ideal
gas. He by mistake calculated the area as shown in the PV graph (Shaded area) equal to 49.26 litre atm.
Calculate the correct value of work (in litre atm) during the process.
(Given : R = 0.0821 litre atm/mol/K)

P(atm)
S I R
C E
R IN
P
2l V(ltr) 4l

y
(A) 49.26 (B) – 34.14 (C) – 78.63 (D) – 98.52

B
Q.42. Two moles of an ideal gas are held by a piston under 10 atm pressure at 273 K. The pressure is suddenly
reduced to 0.4 atm and the gas is allowed to expand isothermally. The work done and change in enthalpy
for the process-

(A) -4.5kJ, + 4.5kJ (B) 0, 0 (C) 0,-4.3 kJ (D) -4.3kJ,0

Q.43. A gas having pressure Pgas is contained in a cylinder fitted with a movable piston. If the gas is allowed to
eapand against a constant external pressure of 10 atm in such a way that the work done by the gas is
maximum, than value of Pgas is -
(A) 5 atm (B) 0.1 atm (C) 10 atm (D) Data insufficient

Q.44. An ideal gaseous sample at initial state i (P0, V0, T0 ) is allowed to expand to volume 2V0 using two
different process, in the first process the equation of process is 2PV2 = K1 and in second process the
equation of the process is PV = K2. Then

(A) Work done in first process will be greater than work in second process (magnitude wise)
(B) The order of values of work done cannot be compared unless we know the value of K1 and K2
(C) Value of work done (magnitude) in second process is greater in above expansion irrespective of the
value of K1 and K2.
(D) 1st process is not possible.
Page 21 Introduction and First Law of Thermodynamics
Q.45. An ideal monoatomic gas undergoes the process AB in which V  T . If q is the heat suppied and w
q
is the work done in the process than w 

  C (D) 2

1  2a 3ab 
Q.46. The Joule thomson coefficient for a gas is   C  RT  R 2T 2  What will be the inversion temperature
p  
of the gas (given a = 0.655atm-L-mol-2 & b = 0.05 Lmol-1)-
(A) 0K (B) 0.91K (C) 1.8 K (D) 11.98 K

Q.47. A diatomic gas undergoes isobaric expansion and the work done by the gas during expansion is 80 J. If
heat is given to gas during the process, than change in internal energy of the gas is -
(A) 200 J (B) 100 J (C) 250 J (D) 0

S I R
Q.48. One mole of Argon is heated using PV5/2 = constant. By what amount heat is absorbed during the
process, when temperature changes by T = 26 K.

C E
IN
(A) 100 J (B) 200 J (C) 180 J (D) 208 J

P R
Q.49. During an adiabatic process which of the following is true for a Vander Waal’s gas-

y
Cv R
(A) T (V  b)  const. (B) T C (V  b )  const .

B
R v

Cv
T 
(C) T.a (V  b)  const.
Cv R
R (D)   (V  b )  const .
a
Page 22 Introduction and First Law of Thermodynamics
“CHOOSE YOUR FAVOURITES”
(more than one correct )
Q.1. Which is / are correct statement.
(A) wadiabatic > wisothermal in an ideal gas compression from same initial state to same final volume
 Cp 
(B) The value of      remains constant for diatomic gas at all temperature
 C v 
(C) Temperature decrease in irreversible expansion is less than in reversible expansion.
(D) Temperature decrease in irreversible expansion is more than in reversible expansion.

Q.2. Which of following statement are true.

(A) (–w)rev – (–w)irrev > 0 for isothermal expansion.
(B) Heat absorbed in isothermal reversible process is greater than isothermal irreversible process.
(C) (w)irev > (w) rev for isothermal compression.
(D) Heat rejected in reversible isothermal process is greater in (n–1)th stage as compare to nth stage
work.

Q.3. Select the False statement(s):

S I R
(A) E = q + w for every thermodynamic system at rest in the absence of external field.
(B) q = 0 for every cyclic process

C E
IN
(C) In isothermal free expansion q = 0, w = 0, E = 0, H = 0

R
 H 

P
(D)   = V where V is molar volume of solid, liquid or gas.
 P T m m

Q.4.
B y
Select the correct option(s).
(A) Entropy change will be same for the adiabatic reversible and irreversible process if carried out from
same initial states to same final volume.
(B) A closed system having all adiabatic boundaries must be isolated system.
(C) Work done in a cyclic process may be zero
(D) Area enclosed by a cyclic process on PV diagram is same as that of TS diagram.

Q.5 Which of the following is true for reversible adiabatic process involving an ideal gas?
(A) Gas with higher  has high magnitude of slope in a P (y-axis) v/s T (x-axis) curve
(B) Gas with higher  has high magnitude of slope in a V (y-axis) v/s T (x-axis) curve
(C) Gas with higher  has high magnitude of slope in a P (y-axis) v/s V (x-axis) curve
(D) Gas with higher  has low magnitude of slope in a P (y-axis) v/s T (x-axis) curve

Q.6. Select the correct option.

(A) Adiabatic free expansion of a real gas having temperature less than inversion temperature results in
decrease in kinetic energy of gas.
(B) More heat is absorbed by an ideal gas if subjected to reversible isothermal process than an irreversible
isothermal process between same states.
(C) Final temperature of an ideal gas will be more for adiabatic reversible expansion process than
Page 23 Introduction and First Law of Thermodynamics
isothermal reversible expansion process if carried out from same initial state to same final pressure.
(D) On isothermal expansion of an ideal gas upto same final volume from same initial state, final pressure
will be more for irreversible process than reversible process.
Q.7. Which of the following is/are correct statement(s):
(A) In Adiabatic expansion heat is released.
(B) In adiabatic compression heat is released.
(C) In adiabatic compression heat is absorbed.
(D) H = nCpT is applicable to only reversible adiabatic process.
Q.8. 2 moles of an ideal monoatomic gas expand irreversibly and adiabatically from an intial pressure of 10
atm against a constant external pressure of 1 atm, until the temperature drops from initial value of 325
K to a final value of 275 K. Which of the foolowing is correct -
(A) w = +1247 J (B) U = -1247 J (C) Vfinal = 5.33 L (D) Vfinal = 17.63 L
Q.9.

R
Isothermal reversible expansion

I
p,V,T p1,V ,T
1

Adiabatic reversible expansion

E
p1, V2, T1
S
C
Adiabatic irreversible expansion
p2, V1, T2

IN
PR
Select the correct statement(s):
(A) T2>T (B) p2<p1 (C) V2<V1 (D) T2>T1

Q.10
By
1 moles of an ideal gas, [ = 1.5], are taken through a series of processes.

P
A D
adiabatic

B
isothermal C

V
Information-I The temperature at state 'A' is 300 K.
Information-II The reversible isothermal expansion from B to C doubles the volume.
Information-III The entropy change of the system from C to D is 4 n 16 Cal / K.
Select the correct option(s) using above information.
(A*) The entropy change of the system from D to A is – 3R n 8
(B*) The temperature at point D is 2400 K
(C*) The work done from A to B is – 600 Cal.
(D*) The work done from B to C is – 300 n 2 Cal.
Page 24 Introduction and First Law of Thermodynamics

Q.11. Select the correct statments-

(A) Molar internal energy is an intensive property.
(B) Heat capacity at constant presssure is an intensive property.
(C) less heat is absorbed by the gas in reversible isothermal expansion as compared to irreversible,
when expanded to same volume .
(D) heat becomes a state function for an isochoric process.

S I R
C E
R IN
y P
B
Page 25 Introduction and First Law of Thermodynamics

“FACE THE CHALLENGE”

(Subjectives)
o
Q.1. A given mass of a gas at 0 C ic compressed reversibly and adiabatically to a pressure 20 times the
intitial value. Calculate the final temperature of the gas ( = 1.42).

Q.2. Calculate E and H when 10 dm3 of He at NTP is heated in a cylinder to 1000C, assuming that the
gas behaves ideally.

Q.3. C a l c u l a work done (in atm lit. ) for the given cyclic process involving 1 mol of an
t e t h e m a g n i t u d e o f

ideal gas. [Given : R = 0.08 atm lit./mol/K]

20 lit.

300 400 600

S I R
E
T (K)

Q.4. In a cycle ABCA consisting of isothermal expansion AB, isobaric compression BC & adiabatic

IN C
PR
compression CA. Find the % (approximate) efficiency of cycle.
1

By
[Given : TA = TB = 400 K ; = 1.5, ln 2 = 0.693, 23 = 1.26 ]

P A

B
C
V0 2V 0 V
Q.5. Calculate the work which could be obtained from an isothermal reversible expansion of 1 mol Cl2 from
1 L to 50 L at 273 K using Van der Walls gas behaviour . ( a = 0.655 L2-atm mol-2, b= 0.055 Lmol-1).

Q.6. 20 dm3 of an ideal diatomic gas at 673 K and 0.7 MPa expands until pressure of the gas is 0.2 MPa.
Calculate q, w, U and H for the process if expansion is -
(i) Isothermal and reversible

(ii) Adiabatic and reversible

(iii) Isothermal and adiabatic

(iv) Against 0.2 MPa and isothermal

Page 26 Introduction and First Law of Thermodynamics
Q.7. One mole of an ideal monoatomic gas is subjected to the following sequence of steps:
(i) The gas is heated reversibly at constant pressure of 101.325 kPa from 298 K to 373K.

(ii) Next the gas is expanded reversibly and isothermally to double its volume.

(iii) Finally the gas is cooled reversibly and adiabatically to 308 K.

Calculate q, w, U and H for the overall process.

Q.8. The coefficient of compressibility of water at 293 K is 4.9 x 10-6 atm-1 over the range 1 to 25 atm.
Calculate the work done in the compression of 1 mol of liquid water from a pressure of 1 atm to 25 atm
at 293 k. Compare this with work involved when 1 mole of an ideal gas is compressed from 1 atm to 25
atm at 298 K.

Q.9. Calculate the heat absobed, H and U when one mole of nitrogen is heated from 298 K to 348 K at
constant volume condition. Considering:
(a) Cp = 29.13 JK-1mol-1 and
(b) Cp = 28.45 + 2.26  10-3T(K)

I R
Q.10. Calculate the work done when 1 mol of Zinc dissolves in HCL at 273 K in (i) an open beaker (ii) In a
closed beaker at 300 K.
S
C E
For a certain gas , the Wander Waals constants are a = 677.86 atm litre2 mol-2 and

IN
Q.11
b = 0.057 litre mol-1. What will be the maximum work performed in the expansion of 2 mol of the gas
from 4 to 40 L at 300 K?

P R
B y
Q.12. A system with an initial volume of 22.4 L is compressed adiabatically to half the volume. During this
process 1350 J of work is performed on the system and the temperature rises from 0oC to 160oC. What
is the change in internal energy?

Q.13. Pressure over 1000 ml of a liquid is gradually increases from 1 bar to 1001 bar under adiabatic conditions.
If the final volume of the liquid is 990 ml, calculate U and H of the process, assuming linear variation
of volume with pressure.

Q.14. A certain liquid has Hvap = 26.0 kJ mol-1. Calculate q, w,  andU when 0.50 mol is vaporized at
250 K and 750 Torr.

Q.15. A sample consisting of 1.0 mol CaCO3 (s) was heated to 800°C, when it decomposed. The heating was
carried out in a container fitted with a piston that was initially resting on the solid. Calculate the work
done during complete decomposition at 1.0 atm. What work would be done if instead of having a piston
the container was open to the atmosphere?
Q.16. Water is heated to boiling under a pressure of 1.0 atm. When an electric current of 0.50 A from a 12V
supply is passed for 300 s through a resistance in thermal contact with it, it is found that 0.798 g of water
is vaporized. Calculate the molar internal energy and enthalpy changes at the boiling point (373.15 K).

Q.17. A piston-cylinder device contains 2 kg of H2 and 14 kg of O2 at 150 K and 5000 kPa. Heat is now
transferred until the mixture expands at constant pressure until the temperature rises to 200 K. Determine
the heat transfer by treating the mixture as perfect gas.
Page 27 Introduction and First Law of Thermodynamics
Q.18 An ideal gas is carried through a thermodynamic cycle.
P
P2
B C

P1 D
A
V1 V2 V
1
P2 = 10 bar V1 = litre
n10
4
P1 = 1 bar V2 = litre
n10
Consisting of two isobaric and two isothermal processes as shown in figure. Calculate the network in the
entire cycle in litre bar.

Q.19. A frictionless and massless piston fitted cylinder with adiabatic wall contains 2 moles of an ideal gas at

I R
an initial temperature of 300 K. The piston has a mass on top of it as shown in the diagram. The

S
insulation in the bottom of the piston is removed and it is brought into contact with a constant temperature

E
bath of an unknown temperature. Heat flows into the system causing the gas to both expand and change

C
temperature. After the temperature has equilibrated, the work for this process is found to be,

IN
W = – 6.64 kJ.Calculate the temperature of the bath? [Given : R = 8.3 J/ mol-K]

P R
y
Vacuum Vacuum

B
m
m
gas gas
T’=300 K T

T T
Page 28 Introduction and First Law of Thermodynamics
“GO COMPREHENSIVE”

C-(1) An ideal gas (CP/CV = ) is expanded so that the amount of heat transferred to the gas is equal
to the decrease in its internal energy.

Q.1 What is the molar heat capacity of gas in this process?

(A) CV (B) – CV (C) CP (D) 2 CV

Q.2 What is the relationship between temperature and volume of gas in this process ?
(A) T · V2(–1) = constant (B) T · V–1 = constant
(C) T · V(–1)/2 = constant (D) T · V = constant

Q.3 What is the magnitude of work performed by one mole of the gas when its volume increases eight times
if the initial temperature of the gas is 300 K ? CV for the gas is 1.5 R. (R = 2 Cal/mol/K)
(A) 900 Cal (B) 450 Cal (C) 1247.7 Cal (D) 623.8 Cal

I R
C-(2) Heat changes in physical and chemical processes are measured with calorimeter. heat change

S
in the process is calculated as :

E
q = msT s = specific heat

Q.1.

IN C
What value of T should be used for the calorimetry experiment that gives the following graphical result?

P R 45

B y
Temperature

35

25

Time (min)

(A) 10oC (B) 25oC (C) 20oC (D) 35oC

Q.2. The enthalpy of fusion of ice is 6.02 kJ mol-1. The heat capacity of water is 4.18 Jg-1C-1. What is the
smallest number of ice cubes at )oC, each containing one mole of water , that are needed to cool 500 g
of liquid water from 20oC to 0oC?
(A) 1 (B) 7 (C) 14 (D) 125

Q.3. 1 mole Fe2O3 and 2 mole of Al are mixed at temperature 25oC and the reaction is compeleted to give:
Fe2O3(s) + 2Al(s) ® Al2O3(s) + 2 Fe(l) kJ
The combined specific heat of the products is 0.8 Jg K-1. The m.p. of irron is 1530oC. Will the heat
-1

released is sufficient to get iron welded?

(A) Yes (B) Iron will melt but not weld (C) NO (D) can’t say
Page 29 Introduction and First Law of Thermodynamics
C-(3) Work is the mode of transfer of energy. Pressure volume work is represented by following
relation
w = -Pext V
It has been observed that work done in a reversible process is greater than the work done in
irreversible process i.e. wrev. > wirr.
Graphically work is calculated by calculating the area under the P-V graph. On the basis of
above information answer the following :

Q.1. If w1, w2, w3 and w4 are work done in isothermal, adiabatic, isobaric and isochoric reversible processes
respectively then the correct sequence would be -

(A) w1>w2>w3>w4 (B) w3>w2>w1>w4 (C) w3>w2>w4>w1 (D)w3>w1>w2>w4

Q.2. P-V plots for two gases during adiabatic processes are given as

S I R
p re s su re

E
A

C
B
Plot A and plot B should correspond to:

R IN
P
V o lu m e

y
(A) H2 and O2 (B) He and Ar (C) O2 and He (D) O2 and F2

Q.3. B
Select the incorrect statment -
(A) The temperature decrease in reversible process is more than irreversible process
(B) Work done in reversible compression is less than the work done in irreversible process
(C) Maximum work in an isothermal expansion is obtained when Pext = Pgas
(D) The heat released in reversible process is less than irreversible process.

C-(4) For any given gas the change in internal energy follows the given differential equation -

 U   U 
dU    dT    dV
 T V  V  T
the expression for internal energy of a gas was found to be U = aV2 + bTV
Where a = 1 Jdm-6 and b = 0.5JK-1dm-3. If initial volume of the gas is 1Lthan-
Q.1. For an isothermal change the change in internal energy when volume increases by 0.5 L at 27oC
(A) Zero (B) 76.5 J (C) 65 J (D) 85.5 J
Q.2. For an ideal gas if temperature changes by 50oC and volume changes by 0.5 L than internal energy
will change by -
(A) 15 J (B) No change (C) 37.5 J (D) 2.5kJ
Q.3. For a real gas at 27 C, going through an adiabatic change the temperature changes by 10oC and
o

volume changes by 0.5 L, then change in internal energy will be-

(A) Zero (B) 35.5J (C) 85.5J (D)42.87J
Page 30 Introduction and First Law of Thermodynamics
“MATCH YOUR SKILLS”
Q.1. Column I gives the reaction of internal energy change dU and column II gives the gases with requisite
condition. [Assume CV to be independent of T]
Column I Column II

(A) dU = nCV dT (P) Ideal gas

dV
(B) dU = nCVdT + n2 a (Q) Vander Waal's gas
V2
dV
(C) dU = n2 a (R) Vander Waal's gas under isothermal condition.
V2

(S) Vander Waal's gas under isochoric condition.

Q.2. Column I Column II

(A) w = 0

S I R
(P) Isothermal free expansion

P2V2  P1V1
C E
IN
(B) w = (Q) Irreversible adiabatic expansion
 1

 p 
P R
y
 CV  R 2 
T2  T1 
B
p1 
(C)  Cp  (R) Adiabatic free expansion
 
 
(S) Reversible adiabatic expansion.

Q.3. Given a P-V curve for different types of gases. Match the following -

Column I Column II
(A) Curve-1 (P) CO2
(B) Curve-2 (Q) H2
(C) Curve -3 (R) He
(S) SO2
Page 31 Introduction and First Law of Thermodynamics

Q.4. from the given graph match the following

Column I Column II

(A) -2026 (P) TB

(B) -622.06 (Q) WAB

(C) 0 (R) Wtotal

S I R
(D) 121.8

C E
(S) U

Q.5.
IN
One mole of a certain gas obeys the equation of state P(V - b) = RT and has a constant molar heat

R
P
capacity CV. Parameter b is also a constant . Match the following on the basis of given information-

Column I(Process)

B y Column II(H)

(CV  R)
(A) Isothermal reversible process (P) P(V2  V1 )
R
(B) Isobaric reversible process (Q) Cp (T2 - T1) + b(P2 - P1)

CP
(C) Isochoric reversible process (R) (V  b) (P2  P1 )  b (P2  P1 )
R

(D) Adiabatic irreversible process (S) b (P2 - P1)

Page 32 Introduction and First Law of Thermodynamics
“ASSERTIONS AND REASONS”
(A) Asseration is true; reason is true; reason is a correct explanation for assertion.
(B) Asseration is true; reason is true; reason is not a correct explanation for assertion.
(C) Asseration is true; reason is false
(D) Asseration is false; reason is true

1. Assertion : The extensive property of a single pure substance depends upon the number of mole
of the substance present.
Reason : Any extensive property expressed per mole becomes intensive.

2. Assertion : The heat absorbed during the isothermal expansion of an ideal gas against vaccum
is zero.
Reason : The volume occupied by the molecules of an ideal gas is zero.

3. Assertion : Absolute values of internal energy of substances can not be determined.

R
Reason : It is impossible to determine exact values of constituent energies of the substances.

4. Assertion :
S I
In an isothermal process work done by the system equals the heat released by the
system.

C E
IN
Reason : Enthalpy change is zero for an isothermal process.

5. Assertion :

P R
H and E are state functions.

6.
Reason :

Assertion : B y
Values of H and E depends on initial and final state of the system.

A reversible process occures very slowly.

Reason : Driving force is infinitesimally smaller than opposing force in a reversible process.

 U 
7. Assertion :    0 for an ideal gas.
 V  T
Reason : There is no interaction between the molecules in an ideal gas.

8. Assertion : When Hydrogen gas at high pressure and room temperature expands adiabatically
into a region of low pressure, there is a decrease in temperature.
Reason : Hydrogen gas at room temperature is above its inversion temperature.

9. Asserton : When a gas at high pressure expands against vaccum, the work done is maximum.
Reason : Work done depends on external pressure and increase in volume.

10. Assertion : For a thermodynamic process Wrev > Wirr.

Reason : Temperature decrease in reversible process is more than in irreversible process.
Page 33 Introduction and First Law of Thermodynamics

“FEEL THE HEAT”

Q.1 Among the following, the state function(s) is (are) [JEE 2009]
(A) Internal energy (B) Irreversible expansion work
(C) Reversible expansion (D) Molar enthalpy

Q.2 Statement-1: There is a natural asymmetry between converting work to heat and converting heat to
work.
and
Statement-2: No process is possible in which the sole result is the absorption of heat from a reservoir
and its complete conversion into work.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.

R
(D) Statement-1 is false, statement-2 is true. [JEE 2008]

Q.3
S I
2O (l) (1 bar, 373 K)  H2O (g) (1 bar, 373 K), the correct set of thermodynamic

E
F o r t h e p r o c e s s H

C
parameters is
(A) G = 0, S = +ve (B) G = 0, S = –ve
(C) G = +ve, S = 0

R IN (D) G = –ve, S = +ve [JEE 2007]

Q.4
S (A  C ) = 50 e.u.
y P
A process A  B is difficult to occur directly instead it takes place in three successive steps.

S (C  D ) = 30 e.u.
S (B  D ) = 20 e.u. B
where e.u. is entropy unit.
Then the entropy change for the process S (A B) is
(A) +100 e.u. (B) –60 e.u. (C) –100 e.u. (D) + 60 e.u. [JEE 2006]

Q.5 The molar heat capacity of a monoatomic gas for which the ratio of pressure and volume is one.
(A) 4/2 R (B) 3/2 R (C) 5/2 R (D) zero [JEE 2006]

Q.6 One mole of monoatomic ideal gas expands adiabatically at initial temp. T against a constant external
pressure of 1 atm from one litre to two litre. Find out the final temp. (R = 0.0821 litre. atm K–1 mol–1)
T
(A) T (B) 5
1
( 2) 3
2 2
(C) T – (D) T + [JEE 2005]
3  0.0821 3  0.0821

Q.7 Two mole of an ideal gas is expanded isothermally and reversibly from 1 litre to 10 litre at 300 K. The
enthalpy change (in kJ) for the process is
Page 34 Introduction and First Law of Thermodynamics
(A) 11.4 kJ (B) –11.4 kJ
(C) 0 kJ (D) 4.8 kJ [JEE 2004]
Q.8 The enthalpy of vapourization of a liquid is 30 kJ mol and entropy of vapourization is 75 J mol –1 K.
–1

The boiling point of the liquid at 1 atm is

(A) 250 K (B) 400 K
(C) 450 K (D) 600 K [JEE 2004]

Q.9 One mol of non-ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K) to (4.0 atm, 5.0 L, 245 K)
with a change in internal energy (U) = 30.0 L-atm. The change in enthalpy (H) of the process in L-atm.
(A) 40.0
(B) 42.3
(C) 44.0
(D) not defined, because pressure is not constant [JEE 2002]

Q.10 Which of the following statement is false?

(A) Work is a state function
(B) Temperature is a state function

S I R
(C) Change of state is completely defined when initial and final states are specified.

E
(D) Work appears at the boundary of the system. [JEE 2001]

SUBJECTIVE

IN C
R
Q.11 Onemole of an ideal gas is taken from a to b along two paths denoted bythe solid and the dashed l

y P
lines as shown in the graph below. If thework done along the solid line path isws and that along the
dotted line path is Wd, then the integer closet to the ratio Wd /Ws is- [JEE 2010]

Q.12. In a constant volume calorimeter, 3.5 g of a gas with molecular weight 28 was burnt in excess oxygen at
298 K. The temperature of the calorimeter was found to increase from 298 k to 298.45 K due to the
combustion process. Given that the heat capacity of the calorimeter is 2.5 kJK-1, the numerical value for
the enthalpy of combustion of the gas in kJmol-1 is ?
Page 35 Introduction and First Law of Thermodynamics
Q.13 For the reaction,
2CO(g) + O2(g)  2CO2(g); H = – 560 kJ mol–1
In one litre vessel at 500 K the initial pressure is 70 atm and after the reaction it becomes 40 atm at
constant volume of one litre. Calculate change is internal energy. All the above gases show significant
deviation from ideal behaviour. (1 L atm = 0.1 kJ) [Ans = -557 kJ/mol] [JEE 2006]

Q.14 One mole of a liquid (1 bar, 100 ml) is taken in an adiabatic container and the pressure increases steeply
to 100 bar. Then at a constant pressure of 100 bar, volume decreases by 1 ml. Find U and H
[JEE 2004]

Q.15 Two moles of a perfect gas undergoes the following processes : [JEE 2002]
(a) a reversible isobaric expansion from (1.0 atm, 20.0 L) to (1.0 atm, 40.0 L);
(b) a reversible isochoric change of state from (1.0 atm, 40.0 L) to (0.5 atm, 40.0 L);
(c) a reversible isothermal compression from (0.5 atm, 40.0 L) to (1.0 atm, 20.0 L);

(i) Sketch with labels each of the processes on the same P-V diagram.

I R
(ii) Calculate the total work (w) and the total heat change (q) involved in the above processes.
What will be the values of U, H and S for the overall process ?

S
(iii)

Q.16

C E
A sample of argon gas at 1 atm pressure and 27°C expands reversibly and adiabatically from 1.25 dm3

IN
to 2.50 dm3. Calculate the enthalpy change in this process. Cv.m.for argon is 12.48 JK–1 mol–1.
[JEE 2000]

P R
B y
Page 36 Introduction and First Law of Thermodynamics

“BOOST YOUR BASIC”

1.B 2.D 3.A 4.D 5.A 6.A 7.B 8.D 9.C 10.A 11.B 12.A 13.D 14.C
15.D 16.B 17.D 18.C 19.A 20.C 21.A 22.A 23.B 24.C 25.B 26.C 27.A 28.C
29.C 30.B 31.A 32.C 33.A 34.C 35.D 36.C 37.B 38.C 39.C 40.C 41.B. 42.D
43.C 44.C 45.A 46.B 47.A 49.A

“CHOOSE YOUR FAVOURITE”

1. A,C 2. A,B,D 3. B 4. C,D 5.C,D 6. A,B 7. A,C
8. B,D 9. B,C,D 10.A,B,C,D 11. A,D
“FACE THE CHALLENGE”
(Subjectives)
1.[T2 = 662.2 K] 2. [ E = 556.74J, H= 927.9 J] 3.[ 8]

4. 25% 5. [-8.3657 kJ mol-1]

R
6. (i)[ q=-w = 17.54 kJ,U (ii) [ q=0, U = w=-10.356 kJ, kJ]
(iii) [ q= U = w=  (iv) [q=-w= 10kJ, U =H=0]

S I
7. [q = 3708.59 Jmol-1,w = -3583.88 J mol-1, U = 124.71 Jmol-1, H = 207.85J mol-1]
8. [ w = 0.00279 J]
C E
9. [(a) 1040.8 J, 1456.5 J, (b) 1043.3 J, 1459 J]
10. [-2271.1 J & zero]
IN
11. [ w= -11.5 kJ]

R
12. [ 1350 J]

P
13. [U=501 J H = 99.5 kJ] 14. [w = -101.8 kJmol-1] 15. [ w = -8.9 kJ]
16. [H=+41KJmol , U = +38kJmol ]

y
-1 -1
17. [ 2091.49 kJ]

B
18. [Ans-3]

“GO COMPREHENSIVE”
C-(1) 1. B 2. C 3.A
C-(2) 1.C 2.B 3.A
C-(3) 1.D 2. C 3.A
C-(4) 1.B 2.C 3.C

“MATCH YOUR SKILLS”

Q.1 A(P,Q), BQ,CR Q.2 A  (P,R), BS, C Q Q.3.AR, B(P,Q),CS
Q.4.AQ, BR,CS, D P Q.5.AS, BP,CQ, D R
ASSERTIONS AND REASONS
1. B 2. C 3.A 4.D 5.D 6.C 7.A 8.D 9.D 10.B

“FEEL THE HEAT”

(Previous years JEE questions)
Q1. A,D Q.2 A Q.3 A Q.4 D Q.5 A Q.6 C
Q.7 C Q.8 B Q.9 C Q.10 A
Q.11. 2 Q.12. 9 kJ Q.13. –557 kJ/mol Q.14 U = 0.1 litre atm, H = 9.9 litre atm
Q.15 (ii) –w = q = 620.77 J, (iii) H = 0, U = 0, S = 0
Q.16 H = –114.52 J
Q.9. Select the correct alternate about entropy :
(A) Tlim

S=0 (B) Tlim
0
S= (C) Tlim
0
S=0 (D) S(liquid) > S(vapour)
Q.10. Which is not true about G ?
(A) G is a state function (B) Decrease in G, (–G) is equal t net work done
(C) If G is positive, reaction is spontaneous (D) G = G° if K = 1
Q.11. Which is not true about G ?
(A) G is state function (B) Decrease in G, (–G) is equal to net work done
(C) If G is positive, reaction is spontaneous (D) G = G° if K = 1
Q.12. An exothermic reaction with S = – ve, is :
(A) Spontaneous at all the temperature (B) Spontaneous at high temperature
(C) nonspontaneous at low temperature (D) Spontaneous at low temperature
Q.13. For the equilibrium at 298 K
2H2O H3O+ + OH¯
G° is approximately :
(A) 100 kJ (B) –80 kJ (C) 80 kJ (D) –100 kJ
Column I gives the reaction of internal energy change dU and column II gives the gases with requisite
condition. [Assume CV to be independent of T]
Column I Column II

(A) dU = nCV dT (P) Ideal gas

dV
(B) dU = nCVdT + n2 a (Q) Vander Waal's gas
V2
dV
(C) dU = n2 a (R) Vander Waal's gas under isothermal condition.
V2

Q.26 (S)correct?
Which of the following statement(s) is/are Vander Waal's gas under isochoric condition.
(A) The quantities E, H and G have the same dimension
(B) Gibb’s free energy of 10 gm ice at 0°C and 1.0 atm is less than the Gibb’s free energy of 10 gm
water at 0°C and 1 atm.
(C) Ssys = 0 for every adiabatic process in a closed system.
H sys
(D) For every reversible process, in a closed system, Ssys =
T
Standard enthalpies of formation of O3, CO2, NH3 and HI are 142.2, –393.2, –46.2 and +25.9 kJ
mol–1 respectively.The order of their increasing stabilities will be :
(A) O3, CO2, NH3, HI (B) CO2, NH3, HI, O3
(C) O3, HI, NH3, CO2 (D) NH3, HI, CO2, O3
Q.1
Which among of the following represents the reaction of formation of the product ?
(A) C(diamond) + O2(g)  CO2(g) (B) S(monoclinic) + O2(g) ® SO2(g)
(C) 2N2(g) + O2(g)  2N2O(g) (D) None of the above