Fiziks: Basic Properties and Tools of Thermodynamics

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Institute for NET/JRF, GATE, IIT‐JAM, M.Sc. Entrance, JEST, TIFR and GRE in Physics
Chapter - 3
Basic Properties and Tools of Thermodynamics
3.1 Mathematical Formulations of Thermodynamics
Y  Y  X 1 , X 2 ,...... X n 
then differential dY is said to be exact and one can write

dY   ci dX i
i
dY  c1dX 1  c2 dX 2  ....
 Y   Y   Y 
dY    dX 1    dX 2  .......     dX i
 X 1   X 2  i  X i 
and its corresponding ci X i are said to be conjugate to each other.
It is given that df  Adx  Bdy  Cdz If f is perfect differential then
 A   B 
   
 y  x , z  x  y , z
 B   C 
   
 z  x , y  y  x , z
 A   C 
    ,
 z  x , y  x  y , z
3.1.1 Some Important Formulas
 2Y  2Y
1. 
X k X l X l X k
 X   Y 
2.    
 Y  z  X  z
 X   X   Y 
3.      
 Z Y  Y  Z  Z  X
 X   X   Z 
4.       
 Y  Z  Z Y  Y  X
 X   X   W 
5.      
 Y  Z  W  Z  Y  Z
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 X   X 
6. dX    dY    dW
 Y W  W Y
 X   X   X   W 
       
 Y Z  Y W  W Y  Y Z
3.2. System
A system can be any object, region of space etc, selected for study System
and set apart (mentally) from everything else. All other thing except
system is identified as surrounding. The system of interest in
thermodynamics are finite and macroscopic rather than microscopic.
System boundary
The imaginary envelope which encloses a system and separate it
Surroundings
from its surrounding is called the boundary of the system.
3.2.1 Open system: When Heat and Mass flowing across the Vopors
boundary the system is identified as open system
For boiling water without a lid, heat is transferred into the air and
at same time steam (which is matter) also mixed into the air.
Heat open
System
3.2.2 Closed system: When Heat can be exchanged across the

boundary but Mass can not flow across the boundary the system
is identified as closed system. Example is electric bulb.
Heat closed
System
3.2.3 Isolated System: It cannot exchange either matter or energy
with the surrounding. Example: Thermal flask, Universe.
Isolated System
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3.3 Thermodynamical State

A thermodynamic state is a set of values of properties of a thermodynamic system that
must be specified to represent the system.
Thermodynamic state is the macroscopic condition of a thermodynamic system as
described by its particular thermodynamic parameter, such as temperature ( T ), pressure
( P ), volume ( V ) and density   .
3.3.1 State function
State function also called “State variable” are those thermodynamic variables that
describe the momentary condition of thermodynamic system. For a continuous process,
such variable are exact differential also fully determined by their initial and final
thermodynamic states, which is also known as thermodynamic property.
A thermodynamic system can be completely defined when certain parameters (State
Variable) are completely defined. These system parameters are called thermodynamic
properties. The position (state) of a system can be shown on a property diagram.
For example, the system comprises of Ideal gas confined in a cylinder with a frictionless
piston. When the system gets heat the gas expands and piston moves out i.e., pressure
will change from P1 to P1 and volume expands from V1 to V2 .
Property diagram of Ideal gas in P  V diagram when it is heating.

1
 P1
P
P2 2 Heating
V2
V1 V System
Property Diagram of Ideal gas when it is cooling. If we cool the system the piston will
move in opposite direction and gas is compressed .
1
 P1
P
P2 2 Cooling
V2
V1 V System
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When piston is compressed then pressure increased from P2 to P1 and volume decrease
from V2 to V1 . P and V here are properties of system parameters.

Thermodynamic properties are macroscopic properties, they are mainly
(i) Pressure ( P ) : Pressure is the force applied perpendicular to the surface of an object
per unit area over which that force is distributed. The SI unit of pressure N / m2
(ii) Volume V  : Volume is the quantity of three-dimensional space enclosed by a closed
surface, for example, the space that a substance or shape occupies or contains. Volume is
often quantified numerically using the SI derived unit, the cubic meter. The volume of a
container is generally understood to be the capacity of the container; i.e., the amount
of fluid (gas or liquid) that the container could hold
(iii) Temperature T  : Temperature is a physical quantity expressing hot and cold. It is a
proportional measure of the average kinetic energy of the random motions of the
constituent particles of matter (such as atoms and molecules) in a system.
(iv) Entropy  S  : Entropy is the measure of randomness of a system.
If heat Q is transferred to a system at temperature T , entropy increases and if Heat is

transferred from body then entropy decreases.
dQ Q
The change in entropy  dS   or S 2  S 2  Q
T T
dQ dQ
dS  is used for reversible process But for irreversible process dS 
T T
(v) Internal Energy U  : Internal energy of a system which comprises of Potential
energy, kinetic energy, vibration energy, rotational energy etc. of the system particles.
For an ideal gas internal energy is only function of temperature, U  f T 
Internal energy will also defined Specific heat at constant volume which is given by
 dU 
CV   
 dT V
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Hence internal energy is point function then their change are measured by difference in
initial and final state only. U  U 2  U1 . For close path  dU  0
1
P
2
V
(vi) Enthalpy  H  - Enthalpy of a gas o a fluid is defined as H  U  PV where U is
dH
Specific heat at constant pressure CP 
dT
H  H1  H 2
Change in enthalpy H 2  H1  U 2  P2  P2   U1  P1  V1  of fluid.
For ideal gas U  f T  and PV  RT
So for Ideal Gas, enthalpy is also only function of temperature i.e., H  f T 
(vii) Helmtloltz Free Energy  F  The Helmholtz free energy is given by 1 2
F  U  TS is the measure of potential between any two points during a

process (Chemical or flow) which tells about possibility of the process on
forward direction. The Helmholtz free energy is measurement of Available energy for
work
(viii) Gibbs Energy  G  - Gibbs energy determines the spontaneity of a process.
G  H  TS
G  H  T S (For isothermal) process of
H
G  0 Non spontaneous  H  T S or  S
T
H
G  0 Spontaneous or  S
T
H
G  0 Spontaneous or  S
T
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3.3.2 Mathematical condition for state function

If f  x, y  is state function (thermodynamic property) or path independent then with
variable x and y then
 f   f   f   f 
df    dx    dy  df  Mdx  Mdy where M    N  
 x  y  y  x  x  y  y  x
 M   N 
If f  x, y  is exact differential, then     .
 y  x  x  y
1 P
Example: If f T , V     dT    dV then prove that f T ,V  is path independent or
T  T 
State function or thermodynamic property.
1 P
Here M ,N  and x  T and y  V
T T
 M      1    N      P   P
         0 and          2
 y  x  V   T  T  x  y  T   T  V T
 M   N 
Since,      , the given expression is not an exact differential, and hence not
 y  x  x  y
a thermodynamic property,
V  P
Example: If function f  P,V  is defined as f  P, V     dP    dV then prove that
T  T 
f  P,V  is thermodynamic property or State function.
V  P
f  P, V     dP    dV
T  T 
V R p R
M  and N   x  P and y  V
T p T V
 M     V   1
       
 y  x  V  T   p T
 N     P   1
       
 x  y  P  T  V T
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 M   N 
Since,     , the given expression is an exact differential, and hence
 y  x  x  y
thermodynamic property or state function
3.4 Intensive and extensive properties
Intensive properties: It is a physical property of a system that does not depend on the
system size or the amount of material in system. It is scale invariant.
Example: Chemical potential, density, viscosity, resistivity, specific heat capacity,
pressure, elasticity, magnetization, velocity, acceleration, temperatures, etc.
Extensive Properties: It is additive for independent non-interacting subsystem. It is
directly proportional to the amount of material in the system.
Example: Energy, Entropy, Gibbs energy, mass momentum, volume, change, weight,
f df
Note: If f and g are arbitrary intensive variable, then fg , , and f  g will also be
g dg
intensive variables.
If F and G are two arbitrary extensive variables, then F  G will be an extensive
F dF
variable, but and will be intensive.
G dG
F dF
If F is extensive variable and f is intensive variable, the f F , and will be
f df
extensive variables.
3.5 Reversible and irreversible process. The process in which the system and
surroundings can be restored to the initial state from the final state without producing any
changes in the thermodynamics properties of the universe is called a reversible process,
dQ
otherwise the process is irreversible. dS  is used for reversible process But for
T
dQ
irreversible process dS 
T
3.6 Quasi static process: A quasi-static process is a thermodynamic process slow
enough that system to remain in internal equilibrium. The volume of a system changes at
a slow rate enough to allow the pressure to remain uniform and constant throughout the
system. Any reversible process is also a quasi-static one, but the converse is not true.
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3.7 Thermodynamic equilibrium In thermodynamic equilibrium there are no

net macroscopic flows of matter or of energy, either within a system or between systems.
In thermodynamic equilibrium the system will have uniform temperature.
3.8 Equation of State: In thermodynamics, an equation of state is a thermodynamic
equation relating state variables which describe the state of matter under a given set of
physical conditions, such as pressure, volume, temperature  P, V , T  , or internal energy.
3.8.1 Equation of State for Ideal Gas

The Ideal gas law in the equation of state of a hypothetical Ideal gas. It is derived from
kinetic theory and satisfies the Boyle’s and Charles’ law.
The state of an amount (number of mole n ) of ideal gas is determined by its pressure
 P  , volume V  and temperature T  .
The Ideal gas equation of state for n mole is given by PV  nRT , where R is gas
constant and is equal to 8.314 J  K 1mole 1
3.8.2 Equation of state for Real gases (van der Waal equation)
The state of an amount of Real gas (number of mole n ) is determined by its pressure
 P  , volume V  and temperature T  .
 n2 a 
2 
 P  V  nb   nRT
 V 
3.9 Heat Exchanged ( Q ): When two systems with different temperatures are put in
contact, heat flows spontaneously from the hotter to the colder system. There are
different parameter which is helpful to determine Heat exchange of system mainly
comprises Fluid and Gas.
3.9.1 Specific Heat
Heat capacity of a body is numerically equal to quantity of heat required to raise its
temperature by 1 unit
Q
C
T
The specific heat of a material is numerically equal to quantity of heat required to raise
the temperature of unit mass of that materials through 1 unit
dQ
C
mdT
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3.9.2 Heat Capacity of Ideal Gas

If f is degree of freedom of Ideal gas, then from equi-partition law of energy, the total
sum of energy is equivalent to sum of kinetic energy associated with each degree of
freedom
3.9.3 Molar Heat Capacity
Molar heat capacity is defined as the energy required to raise the temperature of one
mole of Ideal gas by one Kelvin at constant volume.
f
U N A KT , where N A is Avogadro number
2
dU f fR
 N AK 
dT 2 2
Rf
CV  , for Ideal gas
2
f 
C P  C V  R  R  1
2 
 is defined as ratio of heat capacity at constant pressure to heat capacity at constant
volume.
Cp  2
  1  
Cv  f 
3.9.4 Latent Heat: The heat required to convert a solid into a liquid or vapor, or a liquid
into a vapor, without change of temperature. Latent heat can be understood as heat energy
in hidden form which is supplied or extracted to change the state of a substance without
changing its temperature. Examples are latent heat of fusion and latent heat of
vaporization involved in phase changes, i.e. a substance condensing or vaporizing at a
specified temperature and pressure.
A specific latent heat L expresses the amount of energy in the form of heat Q required to
completely effect a phase change of a unit of mass (m) , usually 1kg , of a substance as
an intensive property, then
Q  mL
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3.10 Work Done during Process

Suppose due to heat supplied Q to a system, the system
Q
expands and applies pressure P on piston of area A while
is displaced by dx dx
 Area A
Work done by system dW  Fdx  Fdx  PAdx Piston cylinder system
Total work W   PAdx or W   PdV where Adx  dV
volume swept by piston.

Work done when process is occurred between A to B is the area
B
under the PV curve i.e., W   PdV P B
A
If work is done by the system, it has positive sign and if work is done
on the system, it has negative sign.
A
valid for a reversible pressure only as integration can be done only for
V
a continuous path. Otherwise W  PV irreversible process.
Sign convention:
Work done(  W ) by the system is positive but work done on the system is negative,
Heat (  Q ) absorbed by system is positive and heat rejected by the system is negative.
Q2  -ve  W1  +ve 
W2  -ve 
Q1  +ve 
System
Example: A non flow quasi – static (reversible) process occurs for which P   3V  16 
bar, where V is volume in m3 . What is the work done when V changes from 2m3 to
6 m3 ?
Solution: P   3V  16  bar   3V  16  105 N / m 2
6
V2  6 V2  6  3V 2 
W
1 2  V1 2 PdV W
1 2  V1 2  3V  16   5
10 dV    2  16V   10
5
 2
 3   3 
    62  22   16  6  2   105     32  64  105
 2   2 
  48  64  10  16  10 Nm or J
5 5
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Example: The equation of state for one mole of a non-ideal gas is given by
 B
PV  A 1   , where the coefficient A and B are temperature dependent. If the
 V
volume changes from V1 to V2 in an isothermal process, find the work done by the gas.
 B  A AB 
Solution: PV  A 1    P    2 
 V V V 
1 1
V2 2 V
A AB V
W  PdV   dV   2 dV  A ln 2  AB    
V1
V V1
V V1  V1 V2 
Example: The pressure P of a fluid is related to its number density  by the equation of
state
P  a  b 2
where a and b are constants. If the initial volume of the fluid is V0 , Find the work done
on the system when it is compressed, so as to increase the number density from an initial
value of  0 to 2  0 .
n n2 n
Solution: P  a  b 2  P  a b 2  
V V V
dV V2 dV n n
W   P  dV  an  bn 2 
V2
, where V1  , V2 
V1 V V1 V 2 0 2 0
 W   n  a ln 2  b 0    0V0  a ln 2  b0  ,  n  0V0
Work done on the system  W   a ln 2  b0  0V0
3.11 Thermodynamical coefficient for Gases

Coefficient of Volume Expansion or Expansivity   the ratio of the increase of
length, area, or volume of a body per degree rise in temperature to its length, area,
or volume, respectively, at some specified temperature, commonly 0° C, the pressure
being kept constant also called expansivity.
1  V 
  
V  T  P
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3.11.1 Isothermal Elasticity: The Ratio of the change in pressure acting on volume to
the fractional change in volume. Isothermal Elasticity can be compare to Bulk modulus of
Ideal gases
 P 
kT  V  
 V T
3.11.2 Isothermal compressibility: The inverse of Isothermal Elasticity is identified as
Isothermal compressibility
1 1  V 
T    
kT V  P T
3.11.3 Adiabatic Elasticity: The Ratio of the change in pressure acting on volume to the
fractional change in volume in such a way that heat is not allowed to exchanged
 P 
kS  V  
 V S
3.11.4 Adiabatic compressibility: The inverse of Adiabatic elasticity is identified is
1  V 
Adiabatic compressibility  S    
V  P  S
Example: Find the isothermal compressibility T of a van der Waals gas which is given
 
V  b   RT as a function of volume V at temperature T .
a
by equation of state  P  2
 V 
1  V 
Note: By definition, T     .
V  p T
Solution: We know bulk modulus of a gas is given by

 a 
van der Wall equation:  P  2 V  b   RT (i)
 V 
If process is isothermal: T  constant
 a   a 
 dP  3 dV V  b    P  2 dV   0
 V   V 
 dP a   a 
  3 V  b    P  2   0
 dV V   V 
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dP

P  a / V 2   a   PV 3  aV   aV  b
dV V  b V 3 V 3 V  b 
1 V 3 V  b   V 2 V  b 
T     (ii)
V    PV 3  aV   a V  b    PV 3  aV   a  b  V  
 
Put values of P from (i) in (ii)
V 2 V  b 
T 
 RTV 3  2a V  b 2 
 
3.12 Conservation of energy base of first law of thermodynamics
Energy can neither be created nor destroyed; rather, it can only be transformed or
transferred from one form to another.
Consider a system of Ideal gas with boundary in which the process is reversible
Case -1 -when boundary of system is rigid
When system is rigid volume cannot be changed, when heat energy Q is supplied to a
system, the activity of its constituent particles increases because of this energy.
The level of increased energy is measured in terms of internal energy of the system
n
particles. So, Q   U i , here U i is internal energy of i th system particles. The level of
i 1
activity is measured in terms of temperature. If body is cooled, the reverse of this

happens. In nutshell we can say that Q has been converted into U or vice versa. So
energy is conserved.
In this case heat is converting into internal energy and vice versa .
Case -2 when when boundary of system is not rigid and made of conductor
Suppose heat supplied Q into a system, then pressure developed on such that boundary
of system expands by volume dV then mechanical work done is given by W   PdV .
The heat exchanged Q is equal to work done W similarly if boundary of system
contracted then work done on the system and Heat will flow out of system. In this case
heat is converting into mechanical energy and vice versa.
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Case 3: When boundary not rigid but made of insulator.

In this case heat cannot be exchanged but if boundary of system is expand such that it
cool the gases so internal energy will decrease similarly if boundary will compressed then
temperature of gas increase so internal will increased energy
Example: When 0.15 kg of ice at 00 C is mixed with 0. 3kg of water at 500 C in a
container, the resulting temperature is 6.70 C . Calculate the heat of fusion of ice.
( Cwater  4186 Jkg 1 K 1 )
Solution: Heat lost by water mCw  f  t 

w
  0.30 kg   4186 Jkg 1 K 1  50.00 C  6.70 C   54376.14 J
Heat required to melt ice  m2 L f   0.15 kg  L f
Heat required to raise temperature of ice water to final temperature  mI Cw  f  t 

I
  0.15 kg   4186 Jkg 1 K 1  6.70 C  00 C   4206.93 J
Heat lost = Heat gained

54376.14 J   0.15 kg  L f  4206.93 J  L f  3.34  105 Jkg 1
Example: If one mole of a monatomic gas    5 / 3 is mixed with one mole of a
diatomic gas    7 / 5  , then value of  for the mixture. Assume volume of container is
constant and no heat can be exchanged

3R 5R
Solution: (b): For a monatomic gas CV1  for diatomic gas, Cv2 
2 2
n1  1, n2  1
From conservation of energy n1CV1T  n2CV2 T   n1  n2  CV T

3R 5R
n1CV1  n2CV2 1
 1
CV   2 2  2R
n1  n2 11
C 3R
CP  CV  R  2 R  R  3R  mixture  P   1.5
CV 2 R
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MCQ (Multiple Choice Questions)

Q1. Calorie is defined as the amount of heat required to raise temperature of 1 g of water by
1 C and it is defined under which of the following condition?

(a) From 14.5 C to 15.5 C at 760 mm of Hg .
(b) From 98.5 C to 99.5 C at 760 mm of Hg .
(c) Form 13.5C to 14.5C at 76 mm of Hg .
(d) From 3.5C to 4.5C at 76 mm of Hg .

Q2. Explain if the following quantities can be used as properties:
(a)  PdV (b)  VdP (c)   PdV  VdP  (d)   PdV  VdP 
Q3. Refer to figure, let U1 and U 2 be the changes in internal energy of the system in the
processes A and B . Then P
A
B
V
(a) U1  U 2 (b) U1  U 2 (c) U1  U 2 (d) U1  U 2
Q4. For an ideal gas The change in internal energy in a constant pressure process form
C
temperature T1 and T2 is equal to (where   P )
CV
nR nR  1
(a) T2  T1  , (b) T2  T1  (c) nR T2  T1  (d) nR   1T2  T1 
 1  1 
Q5. Which of the following is not a thermo dynamical state function.
(a) Enthalpy ( H ) (b) internal energy (U )
(c) Heat exchanged (Q) (d) Helmholtz free energy ( F )
Q6. Which of the following thermodynamical property is measurement of Spontaneity.
(a) Enthalpy ( H ) (b) internal energy (U )
(c) Gibbs free energy (G ) (d) Helmholtz free energy ( F )
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Q7. Consider the process on a system shown in figure given below. During the process, the
work done by the system P
V
(a) continuously increases (b) continuously decreases
(c) first increases then decreases (d) first decreases then increases
Q8. The pressure P , volume V and temperature T for a certain material are related
by P 

AT  BT 2 
, where A, B are constants. The work done by the materials, if the
V
temperature changes from T to 2T while the pressure remains constant?
(a) AT  BT 2 (b) AT  2 BT 2
(c) AT  3BT 2 (d) 2 AT  3BT 2
Q9. A block of ice at-10 C is slowly heated and converted to stream at 100 C . Which of the
following curves represents the phenomenon qualitatively?
(a) T (b)
T
Heat supplied Heat supplied
(c) (d)
T T
Heat supplied Heat supplied

Q10. The specific heat c  of a substance is found to vary with temperature T  as, c     T 2 ,
where T is celsius temperature. At what temperature does the specific heat of the
substance becomes equal to the mean specific heat of the substance in a temperature
range between 0 and T0 ?
T0 T0 T0 T0
(a) (b) (c) (d)
2 2 3 3
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Q11. The equation of state of a gas is given as PV  b   nRT , where b is a constant, n is the
number of moles and R is the universal gas constant. When 2 moles of this gas undergo
reversible isothermal expansion from volume V to volume 2V , what is the work done
by the gas?
(a) 2 RT In V  b  / 2V  b  (b) 2 RT In 2V  b  / V  b 
(c) 2 RT In V  b  / 2V  (d) 2 RT In 2V  / V  b 

Q12. What is the minimum attainable pressure of an ideal gas in the process given by
T  a  bV 2 , where a, b are constants and V is the volume of one mole of ideal gas?
(a) ab (b) R ab (c) 2 R ab (d) a/b

(R is the universal gas constant)
Q13. If the number of degree of freedom of a molecule in a gas is n then the ratio of specific
heats is given by:
1 1 2 2n
(a) 1  (b) 1  (c) 1  (d)
n 2n n 2n  1
Slope of isothermal curve
Q14. The ratio, is equal to:
Slope of adiabatic curve
1
(a) 1 (b)  (c) (d) 2

Q15. Which of the following graphs correctly represents the variation of isothermal
compressibility ( T ) with P for an ideal gas at constant temperature?
(a) (b) 

P P
(c)  (d) 
P P
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Q16. A given quantity of an ideal gas is at pressure P and absolute temperature T . The
isothermal bulk modulus of the gas is
1 1
(a)  P (b) P (c) (d). 
P P
MSQ (Multiple Select Questions)
Q17. Which of the following is not thermodynamic property
(a) work done (b) heat exchanged (c) internal energy d) entropy
Q18. Which of the following statement is correct?
(a) Thermodynamic property is path independent.
(b) If f  x, y  is thermodynamic property it must be exact differential.
(c) Work done (W ) , Internal energy (U ) and heat exchanged is (Q) is thermo
dynamical properties
(d) Entropy ( S ) internal energy (U ) and helmohtz free energy F is thermodynamic
properties
Q19. Which of the following is/are correct statement(s)?
Cp 8  5
for    
(a) The value of
C p  CV 
for helium is
3  3
3R
(b) The value of specific heat capacity at constant volume for helium is
2
C  CV  1  7
for    
p
(c) The value of
C
p  CV 
for H 2 is
6  5
7R
(d) The value of heat capacity at constant pressure is
2
Q20. Two thermally insulated vessels 1 and 2 are filled with air and connected by a short tube
equipped with a valve. The volume of the vessels, the pressures and temperatures of air in
them are known as V1 , p1 , T1 and V2 , p 2 , T2  . The pressure established after the opening of
the valve is given by
P1V1  P2V2 P1 / V1  P2 / V2
(a) P  (b) P 
V1  V2 1/ V1  1/ V1
TV T V T T P V  P1V1 
(c) P  1 1 2 2 (d) T  1 2 2 2
V1  V2 P1V1T2  P2V2T1
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Q21. An ice cube of mass 0.1 kg at 0 C is placed in an isolated container which at 227  C .
The specific heat C of the container varies with temperature T according to the
empirical relation C  A  BT , where A  100 cal/kg  K and B  2 102 cal/kg  K 2 . If
the final temperature of the container is 27  C , . (Latent heat of fusion of water

 8 104 cal/kg , Specific heat of water  103 cal/kg  K ). Then which of the following is
correct?
(a) Heat gained by ice is 8000cal
(b) Heat gained by water is 2700cal
(c) Heat lost by container is 10700cal
(d) The mass of container is 0.495
NAT (Numerical Answer Type)

 5   3 
Q22. One mole of diatomic gas,  CV  R  and one mole of a monatomic gas,  CV  R 
 2   2 
are mixed. The value of  for the mixture is, (where  is the ratio of two specific heats
of the gas…………..
Q23. 10 grams of ice at 0 0 C is added to a beaker containing 30 grams of water at 250 C .
What is the final temperature of the system is …………. 0C , when it comes to thermal
equilibrium? (The specific heat of water is 1 cal / gm / 0C and latent heat of melting of ice
is 80 cal / gm )
Q24. 2 kg of ice at  20 C is mixed with 5 kg of water at 20 C in an insulating vessel having
a negligible heat capacity. The final mass of water remaining in the container is ……...
kg . It is given that specific heats of water and ice are 1 kcal / kg C and 0.5 kcal / kg C
while the latent heat of fusion of ice is 80 kcal / kg .
Q25. Steam at 100 C is passed into 1.1 kg of water contained in a calorimeter of water
equivalent 0.02 kg at 15 C till the temperature of the calorimeter and its contents rises at
80 C . The mass of the steam condensed is …………gram.
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
Q26. If relation between pressure P and volume V of ideal gas is given by P  then find
V2
the value of  such that work done by the gas is 3 jule if volume expand from 1 L to 2 L
Q27. 1 mole of ideal gas expanded from 1L to 2 L as pressure P varies as temperature T by
xR 2
the process P   T 2 is then value of x ………

Q28. A non – flow reversible (quasi-static) process can be written down by an equation
P  V 2  8 / V  bar the work done if volume changes from 1m3 to 3m3 .is   105 Joule
then value of  is given by ………( Answer must be nearest integer )
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Solutions
MCQ (Multiple Choice Questions)
Ans. 1: (a)
Solution: (a) : 1 calorie is the amount of heat required to raise temperature of 1 gram of water
from 14.50 C to 15.50 C of Hg. Hence correct option is (a).
Ans. 2: (c)
Solution:   PdV  VdP    d  PV   PV
Thus, it is an exact differential and thus a Thermodynamic property.
Ans. 3: (b)
Solution: Internal energy is point function
Ans. 4: (b)
Solution: Hence internal energy is path independent then for ideal gas it is always for
U  nCV T  nCV T2  T1 
CP R 1
 and CP  CV  R , CV  and CV  nR T  T 
CV  1  1 2 1
Ans. 5: (c)
Ans. 6: (c)
Ans. 7: (a)
Solution: Since, work done is the area enclosed under the curve, so from the figure, work done
continuously increases
Ans. 8: (c)
AT  BT 2
Solution: Here, P  , where, A, B are constants.
V
Then the work done dW is given as,
dW  PdV (i)
Now, PV  AT  BT 2
 PdV  d  AT  BT 2   AdT  2BT .dT (ii)
by equation (i) and (ii)
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dW  AdT  2 BTdT
  A  2 BT dT  AT  BT 
2T
2 2T
Work done  T
T

 A2T  T   B 2T   T 2
2
  AT  3BT 2
Ans. 9: (a)
Solution: The change of ice at 100 C into steam at 1000 C occurs in four stages: It is
represented by curve (a). First stage – The temperature of ice changes from of ice
changes from 100 C to 00 C .
II stage – Ice at 00 C changes in water at 00 C . The state changes as heat is supplied.
III stage – Water at 00 C changes into water at 1000 C .
IV stage – Water at 1000 C changes into stem at 1000 C .
1000 C
Water IV
Steam
III
00 C Ice II
I Water
100 C
Ans. 10: (c)
Solution: The amount of heat required to increase the temperature of unit mass is called specific
heat.
Q  mcT , where m  mass of substance
T  increment in temperature
and c    T 2 (i)
1  T03 
T T0
0    T dT  T0 T0  3 
1 0 1
The mean specific heat c   cdT  2
T0 0 T0
BT02
c  
3
BT02 BT02 
By question, c  c       BT 
2
 BT 2  T  0
3 3 3
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Ans. 11: (b)

Solution: PV  b   nRT
Work done = dW  PdV
nRT 2V nRT
W   PdV , where P  W   dV
V b V V b
dV
 nRT  ln  2V  b   ln V  b  
2V
 nRT 
V V b
 2V  b 
Since, n  2  W  2 RT ln 
 V  b  
 
Ans. 12: (c)
PV
Solution: We have, T  a  bV 2   a  bV 2
R
aR V 2 Rb aR
P  P  VbR (i)
V V V
dP
To find minimum pressure, put 0
dV
d  aR  aR a
   VbR   0   2  Rb  0  V 2  (ii)
dV  V  V b
d 2P
Again on differentiating equation (i) twice, we get 2
as positive for V 2 ,
dV
 P is minimum at V 2 .
By equations (i) and (ii), we get,
aR
Pmin   bR a / b  2 R ab
a/b
Ans. 13: (c)
Solution: We know that energy associated with each degree of freedom of one mole gas is given
1
as, U  RT
2
n
Hence, if there is n degree of freedom, then U  RT , where R  universal gas
2
constant.
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We know that specific heat at constant volume is given as

dU n
CV   CV  R (i)
dT 2
n  n
By Mayor’s formula, C P  CV  R  R  R  C P  1  R
2  2
CP 2
As,      1
Cv n
Ans. 14: (c)
Solution:
P P
V V
isothermal curve adiabatic curve
The ideal gas equation for 1 mole is written as, PV  RT
For isothermal process, T is constant, now on differentiating above equation w.r.t. V we
get,
d
PV   0  dP   P  (i)
dV dV V 
P
 slope of isothermal curve  
V
In case of adiabatic expansion, the gas equation is given as, PV   constant .
Differentiating this w.r.t. V we get V  dP  PV  1 dV  0
dP P P
     slope of adiabatic curve     (ii)
dV V  V 
Dividing equation (i) by (ii), we get,
Slope of isothermal curve 1

Slope of adiabatic curve 
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Ans. 15: (a)

1  V 
Solution: T    
V  P T
At a constant temperature, for a given mass of gas, PV  constant, according to Boyle’s
law.
 PV  constant  PdV  VdP  0
dV V 1  dV  1
or,   or   
dP P V  dP  P
1
or, T  or T P  1
P
Ans. 16: (b)
 P 
Solution: Bulk modulus kT  V   …..(i)
 V 
 P 
 PV  constant  PdV  VdP  0 kT  V  P
 V 
MSQ (Multiple Select Questions)

Ans. 17: (c), (d)
Solution: Thermodynamic property must be path independent.
Ans. 18: (a), (b), (d)
Solution: Work done and heat exchanged is path dependent function so they are not
thermodynamic property .
Ans. 19: (b), (c) and (d)
Solution: The ratio of C p and CV is known as coefficient of adiabatic expansion. Hence,
Cp
 
CV
5 Cp 1 5
(a) so, for helium    
3 C p  CV 1  3 8
5
R 3R  5
(b) CV   , for    
 1 2  3
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7 C p  CV
(c) for hydrogen   
5 C p  Cv
On dividing by CV , the numerator and denominator, we get as
7
C p  CV C p / CV  1   1 5  1 C  CV 1
    p 
C p  CV C p / CV  1   1 7 C p  CV 6
1
5
 R 7R
(d) CP  
 1 2
Ans. 20: (a) and (d)
Solution: 1 2
V1 V2
V1 , P1 , T1 V2 , P2 , T2 P
T
When valve is opened and thermodynamics equilibrium is attained then, number of moles
will be constant. Then,
P1V1 P2V2 PV1  V2 
 
RT1 RT2 RT
P1V1 P2V2 PV1  V2 

  (i)
T1 T2 T
n1CV T1  n2CV T2  n1T1  n2 T2
P1V1
T  T1   P2V2 T  T2   0 (ii)
T1 T2
T1T2 P2V2  P1V1  P V  P2V2

T putting in (i), we get P  1 1
P1V1T2  P2V2T1 V1  V2
Ans. 21: (a), (b), (c) and (d)
Solution: According to principal of calorimetry,
Heat lost by container dQ  mCdT  m  A  BT  dT
300
 BT 2 
Q
or  dQ  m   A  BT  dT  Q  m  AT 
300
0
500
 2  500
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  300    500  
300 2 2
 2 102 2 
or Q  m 100 T  T  or Q  m 100  300  500   
 2  500  100 
or Q  m  20000  1600 calorie
or Q  21600 m calories …. (i)

Heat gained by ice in melting  mL
 Q1  0.1 80000  8000 calorie
Heat gained by water of above ice  msT

 Q2  0.11000  27  2700 cal
 Total heat gained  8000  2700

Q1  Q2  10700 cal …. (ii)
 Heat lost = Heat gained or 21600 m  10700

10700
or m   0.495 kg
21600
 Mass of container  0.495 kg .
NAT (Numerical Answer Type)
Ans. 22: 1.5
n1cV1  n2 cV2 n1cP1  n2 cP2 cp
Solution: cV  and cP  , 
n1  n2 n1  n2 cV
5R 7R 3R 5R
n1  1, cV1  , cP1  and n1  1, cV1  , cP1 
2 2 2 2
Ans. 23: 0
Solution: The amount of heat required to melt the ice of mass 10 gm at 0 0 C is
Q  m  L  10  80  800Cal where L is the latent heat of melting of ice and m is the
mass of the ice. The amount of heat available in water of mass 30 gm at 250 C is
Q  m  Cv  T  30 1 25  750Cal
Since, the heat available is less than the heat required to melt the ice, therefore ice will
not melt, as a result the temperature of the system will be at 0 0 C only
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fiziks
Ans. 24: 6
Solution: Heat lost by water at 200 C  mcW T
H  5 1 20  100 Kcal
 After this, heat available  100  20   80 Kcal
This heat will now be gained by ice at 00 C to melt into water at 00 C . Let m kg of ice
melt.
 m  80  80  m  1 kg .
Out of 2 kg of ice, 1 kg of ice melts into water and 1 kg of ice remains unmelted in
container.
 Amount of water in container  5  1  6 kg .
Ans. 25: 130
Solution: Heat lost by steam  Heat gained by water  calorimeter
 mL  ms 100  80   1.12  s   80  15 
or, m 540  1 20    1.12  1 65
1.12 1 65 65
m  kg or m  0.13 kg  130 gram .
560 500
Ans. 26: 4
2L 2L   1  3
Solution: W   PdV   dV     1   3J    4
4  4
2
1L 1L V
Ans. 27: 0.75

PV P 2V 2 R2
Solution: P   T 2 PV  RT  T  and P   T 2  P    P 
R R2 V 2
V2 2 R2 R2 3
W   PdV   dV   x  0.75
V1 1 V
2
 4
Ans. 28: 17
Solution: P  V 2  8 / V 105 Nm 2
v1 3
V 3 
PdV  10  V  8 / V  dV  10   8log e V 
V2 3 V2 1
1W2   5 2 5
V1 1 V1 1
3  v1 1
 33  11 3
 105   8log   105  8.666  8.7889   17.455  105 Nm or Joules
 3 1
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Fiziks: Basic Properties and Tools of Thermodynamics

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Fiziks: Basic Properties and Tools of Thermodynamics

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fiziks

then differential dY is said to be exact and one can write

and its corresponding ci X i are said to be conjugate to each other.

It is given that df  Adx  Bdy  Cdz If f is perfect differential then

3.2.2 Closed system: When Heat can be exchanged across the

3.3 Thermodynamical State

Property diagram of Ideal gas in P  V diagram when it is heating.

from V2 to V1 . P and V here are properties of system parameters.

If heat Q is transferred to a system at temperature T , entropy increases and if Heat is

Change in enthalpy H 2  H1  U 2  P2  P2   U1  P1  V1  of fluid.

For ideal gas U  f T  and PV  RT

So for Ideal Gas, enthalpy is also only function of temperature i.e., H  f T 

(vii) Helmtloltz Free Energy  F  The Helmholtz free energy is given by 1 2

F  U  TS is the measure of potential between any two points during a

3.3.2 Mathematical condition for state function

variable x and y then

3.7 Thermodynamic equilibrium In thermodynamic equilibrium there are no

3.8.1 Equation of State for Ideal Gas

3.9.2 Heat Capacity of Ideal Gas

3.10 Work Done during Process

volume swept by piston.

 W   n  a ln 2  b 0    0V0  a ln 2  b0  ,  n  0V0

Work done on the system  W   a ln 2  b0  0V0

3.11 Thermodynamical coefficient for Gases

Solution: We know bulk modulus of a gas is given by

activity is measured in terms of temperature. If body is cooled, the reverse of this

Case 3: When boundary not rigid but made of insulator.

Solution: Heat lost by water mCw  f  t 

  0.30 kg   4186 Jkg 1 K 1  50.00 C  6.70 C   54376.14 J

Heat required to melt ice  m2 L f   0.15 kg  L f

Heat required to raise temperature of ice water to final temperature  mI Cw  f  t 

  0.15 kg   4186 Jkg 1 K 1  6.70 C  00 C   4206.93 J

Heat lost = Heat gained

Example: If one mole of a monatomic gas    5 / 3 is mixed with one mole of a

constant and no heat can be exchanged

From conservation of energy n1CV1T  n2CV2 T   n1  n2  CV T

MCQ (Multiple Choice Questions)

1 C and it is defined under which of the following condition?

(b) From 98.5 C to 99.5 C at 760 mm of Hg .

(c) Form 13.5C to 14.5C at 76 mm of Hg .

(d) From 3.5C to 4.5C at 76 mm of Hg .

Heat supplied Heat supplied

Heat supplied Heat supplied

(c) 2 RT In V  b  / 2V  (d) 2 RT In 2V  / V  b 

(a) ab (b) R ab (c) 2 R ab (d) a/b

the final temperature of the container is 27  C , . (Latent heat of fusion of water

NAT (Numerical Answer Type)

80 C . The mass of the steam condensed is …………gram.

then value of  is given by ………( Answer must be nearest integer )

by equation (i) and (ii)

Ans. 11: (b)

We know that specific heat at constant volume is given as

Ans. 15: (a)

MSQ (Multiple Select Questions)

P1V1 P2V2 PV1  V2 

n1CV T1  n2CV T2  n1T1  n2 T2

T1T2 P2V2  P1V1  P V  P2V2

or Q  m  20000  1600 calorie

or Q  21600 m calories …. (i)

Heat gained by water of above ice  msT

 Total heat gained  8000  2700

 Heat lost = Heat gained or 21600 m  10700

Ans. 27: 0.75