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Gaseous State and Thermodynamics

FUNDAMENTAL ASSUMPTIONS OF KINETIC THEORY OF GASES Section - 1

1. All gases consist of molecules which are considered as rigid, perfectly elastic, solid spheres. These
molecules are extremely small i.e., the volume occupied by the molecules of the gas is taken negligible
as compared to the volume of the containing vessel.
2. The molecules are in a continuous random motion. They are moving in all directions with all possible
velocities. There is no particular direction of motion of the particles.
3. The molecules during their motion collide with one another and also with the walls of the vessel. At
each collision, their velocities change both in magnitude and direction; however in the steady state,
molecular density remains uniform throughout the gas and does not change with time.
4. No forces of attraction or repulsion are exerted on a gas molecule by other molecules or by the
container except during collisions. This means, the energy of the gas is purely kinetic.
5. The collisions among the molecules or with the walls of container are purely elastic. A collision is said
to perfectly elastic if the energy of the molecules remains same before and after the collision.
6. Molecules travel in a straight line with a uniform velocity in between the collisions. The average distance
travelled by the molecules between the successive collisions is called as mean-free path of a molecule.
The time spent during a collision is assumed to be negligibly small as compared with the time taken by
the molecule in traversing a mean-free path.

Note : A gas which satisfies all of above set of assumptions of kinetic theory of gases under all conditions of
temperature and pressure is called as an ideal gas or perfect gas.

A real gas shows appreciable deviations from the perfect gas. At low temperature and high pressure, gases
show deviation from the ideal behaviour.
Evidences In Support of Molecular Motion
Diffusion :
The phenomenon of diffusion presents a remarkable evidence of molecular motion of matter. The particles
of one substance diffuse into another against gravity due to the molecular motion. H2 diffuses into CO2 when
a jar filled with H2 is held mouth to mouth over a jar filled with CO2, though H2 is lighter than CO2.

Evaporation :
The phenomenon of evaporation is related with the motion of molecules. The molecules of liquid are quite
free to move about. At any temperature, all the molecules don’t move with the same velocity, some move
faster than the others. Evaporation involves the escape of fast moving molecules (having speed greater than
average speed). This results in lowering of average speed, which in turn results in lowering of temperature,
and thus producing a cooling effect.

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Brownian Motion :
Botanist Robert Brown observed the irregular motion of plane spores floating in water. Such motions are
called as Brownian Motion. Here the motion of each particle is due to inequality of the impact of surrounding
molecules on it. For example: motion of smoke particles in air is a case of Brownian motion. This
supports the view that the molecules of a substance are in constant motion.

Ideal gas equation :

For n moles of an ideal gas at pressure P, absolute temperature T occupying a volume V, the following
equation holds:
PV = nRT (R : Ideal gas constant)
The gas equation can also be written in the following form.
PM = dRT
where M is the molecular weight and d is the density of the gas at pressure P and absolute temperature T.
Pressure Exerted by a Gas
Consider a container of volume V occupied by a gas.
Let m = mass of the gas in the container
N = number of molecules in the container
If m0 is the mass of one molecule,
m = m0N
If N0 is the Avogadro number and M is the molecular weight of the gas,
M = m0N0
If the molecules are moving speeds c1, c2, c3, ................., cN ;
then the root mean square speed of the gas is defined as :

c12 +c 22 + c32 + .........+cN

2
c2 = crms =
N
The pressure exerted by the gas is :

1 m0 N 2 1 2 m N
P crms or P  crms where  = density of gas = 0
3 V 3 V
Root Mean Square Velocity (crms)
crms can be calculated with any of the following results.

3P 3 RT 3kT
crms =  
 M m0

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Vidyamandir Classes Gaseous State and Thermodynamics

For the same gas at two different temperatures T1 and T2, crms will be different.
crms 1 T
 1 (as Crms  T)
crms  2  T2

c rms (1) T1 M 2
=
c rms (2) T 2M 1

Average Speed : (cav)

c1  c2  c3  .....  cN
cav =
N

8RT
cav =
pM

Kinetic Energy of Molecules

Degrees of Freedom :
The degrees of freedom of a dynamical system are defined as
the total number of independent quantities required in order to
describe the position or motion of the system completely.

Mono-atomic gas molecule :

The molecules of a mono-atomic gas (He, Ne, Ar) consist of
one atom only. It is capable of only translatory motion in free
space which has three compo nent s namely: X, Y
and Z directions. Hence it will have three degrees of freedom
per molecule.

Di-atomic gas molecule :

Each molecule of a diatomic gas (H2, N2, O2, Cl2, etc.) consists of two atoms. In the given diagram, a
diatomic molecule A2 (A-A) is shown. A2 is capable of translatory motion in space and thus possess three
degrees of freedom. Beside this the molecule may rotate about YY’ axis (perpendicular to the molecular
axis and the plane of the paper) or ZZ’ axis (perpendicular to the molecular axis and the plane of the paper).
Rotation about molecular axis (XX’) is neglected (because the size of atom is negligible). Thus due to
rotational motion, the molecules have two degrees of freedom. Hence a diatomic molecule has five
degrees of freedom.
Note : A triatomic molecule (CO2, H2O, SO2 etc) has six degrees of freedom (three of them for translatory and
three for rotational motion).

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Kinetic Energy of Translation per molecule :

The average kinetic energy or kinetic energy per molecule due to translatory motion is also known as mean
KE of translation.
1 1 1
m0 c12  m0 c22  .....  m0 cN
2
2 2 2 1 2  3  1 m c2 
(KE) mean =  m0 crms  0 rms 
N 2 23 
3  PV  3
=    kT as PV = NKT
2 N  2
3
 (KE)mean = kT
2
3 3
KE of translation per mole = (KE)mean N0 = kN 0T  RT
2 2
3  3
KE of translation in n moles of a gas = n  RT  = PV
2  2

Equipartition of Energy
The Law of equipartition of energy states that for a dynamical system in thermal equilibrium, the total energy
of the system is equally divided amongst the various degrees of freedom.
The share of each degree of freedom is 1/2 kT.

For monoatomic gas :

Total energy per molecule = 3/2 kT
Total energy per mole = 3/2 RT

For diatomic gas :

Total energy per molecule = 5/2 kT
Total energy per mole = 5/2 RT

For triatomic gas :

Total energy per molecule = 3kT
Total energy per mole = 3RT

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Vidyamandir Classes Gaseous State and Thermodynamics

Illustration - 1 Calculate the root mean square speed of argon atoms at room temperature (25°C). At
what temperature will the root mean square speed will be half that value ?

SOLUTION :
MAr = 0.040 Kg and R = 8.3 J/mol/K Crms 1 T
 1
Crms  2  T2
3 RT 3  8.3 273  25
Crms = 
M 0.040 1 T1
 
= 430.7 m/s 2 298

For the same gas : T1 = 74.5 K

=  198.5 C

Illustration - 2 Calculate the pressure of Hydrogen in a cylinder of capacity 10 lt given that the total
kinetic energy of translation is 7.5 × 103 J. What is the total kinetic energy of molecules in the cylinder ?
(1 atm pressure = 105 N/m2)

SOLUTION :
The total KE of translation in n moles for a  P = 5 × 105 N/m2
diatomic gas is : 5
Total KE for diatomic gas = PV
3 3 2
nRT  PV
2 2 5
 KE = × 5 × 105 × 10 × 10–3 J
3 2
Hence 7.5 × 103 J = P (10 × 10–3m3 )
2 = 12500 J

Illustration - 3 An Oxygen storage tank has a capacity of 0.05 m3. The gas pressure is 100 atm. at 27°C.
Determine :
(a) the total KE of translation of molecules, (b) the average KE of translation of molecules and
(c) the total KE.

SOLUTION :
(a) Total KE of translation = 3/2 PV (c) The total KE (for diatomic gas) = 5/2 nRT
5 5
= 3/2 (100) x 10 x 0.05 = 7.5 × 10 J = 5/2 PV
(b) Average KE = 3/2 kT = 3/2 (1.38 × 1023) KE = 5/2 (100) × 105 (0.05)
(300) = 6.21 × 1021 J = 1.25 × 106 J.

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Illustration - 4 Find the number of Hydrogen molecules in 1 cm3 if the pressure is 200 mm Hg and the root
mean square velocity of hydrogen is 2400 m/s in these conditions.

SOLUTION :
200 1 m0 N 2
P = 200 mm Hg × 1.01 × 105 N/M2 Substituting these values P  crms
760 3 V
3 PV
V = 1 cm3 = 106 m3 N
2
m0 crms
M
m0 = N N0 = 6.023 × 1023 200 1.01  105  1 10 6  6.023 10 23
0 N  3 
760 0.002  2400  2400
= 4.17 × 1018 molecules.

Illustration - 5 What is the energy of the rotational motion of the molecules contained in 1 Kg of nitrogen
at a temperature of 7°C ?

SOLUTION : 2
n = moles = 1000/28 Rotational Energy = nRT
2
T = 273 + 7 = 280 K
1000
For a diatomic gas, 2 degrees of freedom are for =  8.3  280 J = 8.3  104 J
28
rotational motion.

Illustration - 6 A vessel A with a capacity of V1 = 3 lt contains gas at a pressure of P1 = 2 atm and a vessel
B with a capacity of V2 = 4 lt contains the same gas at a pressure of 1 atm. The temperature is 0°C in A and
27°C in B. What will be the pressure in the vessels if they are connected by a tube ?

SOLUTION :
The vessels are initially at temperatures : where x = 3 or 5 according to whether the gas
T1 = 273 K and T2 = 300 K is monoatomic and diatomic.
 T = final temperature = 283.2K
Let n1 and n2 be the moles in A and B respectively.
 n1  n2  RT
Initial total energy = Final total energy Final pressure = P =
V1  V2
x x x
n1 RT 1  n 2 RT 2   n1  n 2  RT  6 4  283.2
2 2 2  P  = 1.43 atm.

 272 300  7
Note : It may be useful to remember the following :
PV  P V nT n T
P 1 1 2 2 and T= 11 2 2
V1  V2 n1  n2

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GAS LAWS Section - 2

Before moving ahead let us recapitulate important gas laws.
Boyle’s Law :
At a certain temperature, the pressure of a given quantity of any gas varies inversely with the volume.
1
P (for given n and T)
V
PV = constant
If P1 is the pressure when volume is V1 and P2 is the pressure when the volume is V2 (T is constant), then:
P1V1 = P2V2

Charles’ Law :
At a constant pressure the volume of a given quantity of any gas varies directly with the absolute temperature.
V  T (for given n and P)
V/T = constant
If V1 and V2 are volumes of a gas at T1 and T2 and the pressure is kept constant, then:
V1 V2

T1 T2

It states that equal volumes of all gases at the same temperature and pressure contain equal numbers of
molecules.
If volume V1 of one gas contains N1 molecules and volume V2 of another gas contains N2 molecules at same
pressure and temperature conditions, then:
V1 V2

N1 N2
Dalton’s Law of partial pressures :
The total pressure of a mixture of non-reacting gases is equal to the sum of partial pressures of each gas. The
partial pressure of a gas is defined as the pressure it would exert if it were alone in the container at same
temperature.
If PT is the total pressure, p1, p2, p3, ......... are the partial pressures of a number of gases in the container,
then according to Dalton’s Law of partial pressures:
PT = p1 + p2 + p3 + ...........
If n1, n2, n3, be the respective number of moles of the gases :
RT
PT   n1 2 .....
V

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Boltzmann Constant (k) :

In the gas equation PV = nRT, the values of R can be taken as:
R = 8.314 J/mol/K = 0.082 l-atm/mol/K = 2 cal/mol/K
If N0 is the Avogadro number then, k = R/N0 is known as Boltzmann constant.
k = 1.38 × 10–23 J per molecule per degree kelvin .

Gas equation in terms of k :

R
PV = nRT = n N0 N T = n N0 kT
0
PV = NkT N = nN0 = number of molecules

Illustration - 7 10 gm of oxygen are subjected to a pressure of 3 atm. at a temperature of 10°C. Heating

at a constant pressure, the gas is expended to 10 lt. Find :
(a) the volume of the gas before expansion (b) the temperature of gas after expansion
(c) the density of gas before expansion (d) the density of gas after expansion.

SOLUTION :
nRT1 10  0.0821 283 mass 10
(a) V1   = 2.42 L (c) density = d1 =  = 4.13 g/L
P1 32  3 V1 2.42

(b) As pressure is constant : mass 10

(d) density = d2 =  = 1 g/L
V1 V2 V V2 10
  T2  2 T1 = 1169.4 K
T1 T2 V1

Illustration - 8 A vertical cylinderical tank 1 m high has its top end closed by a tightly fitted frictionless
piston of negligible weight. The air inside the cylinder is at an absolute pressure of 1 atm. The piston is
depressed by pouring mercury on it very slowly. How far will the piston descend before mercury spills over the
top of cylinder ? The temperature of the air inside the cylinder is maintained constant.
SOLUTION :
P1 = initial air pressure = 1 atm = 76 cm Hg
P2 = final air pressure = (76 + x) cm Hg
V1 = initial volume = 100 A
V2 = final volume = (100  x) A
76 (100 A) = (76 + x) (100  x)A
Let A = area of cross-section of cylinder.
7600 = 7600  76x + 100x  x2
As the temperature is constant,  x = 24 cm
Use P1 V1 = P2 V2 for air inside the cylinder.  The piston descends by 24 cm.

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Vidyamandir Classes Gaseous State and Thermodynamics

Illustration - 9 An air bubble is released from the bottom of a lake at a depth of 11 m. The temperature at
the bottom is 4°C and that at the surface is 12°C. What is the ratio of the bubble’s radius at the surface to its
radius at bottom ? Assume density of water = 1000 Kg/m3, atmospheric pressure = 75 cm of Hg and density
of mercury = 13600 Kg/m3.

SOLUTION :
Let P1 = pressure at the bottom of lake P1 = 75 + 80.88 = 155.88 cm Hg.
= P2 (pressure at surface)
PV PV
+ P (due to water column) Using 1 1  2 2 for the air inside the bubble
T1 T2
Taking cm of Hg as the unit of pressure,
where V1,V2, are the bottom and surface ;
P1 = 75 cm Hg
T1 and T2 are temperatures at bottom and surface
Pressure of water column of height h = h rw g
155.88  V1 75V2
P = Hwg 
273  4 273  12
 h  h 
P   w  ( ) g   w  cm of Hg. V2 r2 1/ 3
  Hg  Hg   Hg   2.138,   2.138  1.288
    V1 r1

1100  1
= cm Hg = 80.88 cm Hg
13.6

Illustration - 10 A vessel containing 1 gm of oxygen at a pressure of 10 atm and a temperature of 47°C. It

is found that because of a leak, the pressure drops to 5/8 th of its original value and the temperature falls to
27°C. Find the volume of the vessel and the mass of oxygen that has leaked out.

SOLUTION :
The pressure, temperature and number of moles n1 RT1
volume of vessel = V 
of oxygen in the vessel change due to leak while P1
the volume remains fixed.
Hence using PV = nRT
mass leaking out = 1  n2 (32)
we have : = 1  2/3
P1 P = 1/3 gm.
 2
n1T1 n2T2
1 0.082  320
320 5 1 1  V = 0.082 L
n2     moles 32 10
300 8 32 48

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Illustration - 11 A bulb of 500 cm3 is joined by a narrow tube of another bulb B of 250 cm3 and the whole
system is initially filled with air at S.T.P. and sealed. If the temperature of the bulb A is now raised to 100°C
and that of B is kept constant, find :
(a) the new pressure in the system.
(b) mass of air which is transferred from one bulb to another during heating.
(density of air at S.T.P. = 1.29 g/l)

SOLUTION :

(a) Let P be the final pressure of air in the bulbs. As the bulbs are connected, pressure will be equal in both bulbs.
Let TA and TB be the final temperatures of the bulbs.
 TA = 373 K, TB = 273 K

If P0 , T0 are the S.T.P. conditions, then :

Initial moles in the system = Final moles in the system
P0VA P0VB PVA PVB
  
RT0 RT0 RTA RTB
Using P0 = 1 atm, T0 = 273 K,
 500 250  1
P    500  250 
 373 273  273
P = 1.22 atm.
(b) M = molecular weight of air
M = (dSTP) (22.4)
= 1.29  22.4
= 28.896 gm.
Mass transferred = moles  M
 PV PV 
= B  0 B   M
 RTB RT0 
250  103
= (1.22  1)  28.896
0.082  273
 mass transferred = 0.0709 gm.

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Vidyamandir Classes Gaseous State and Thermodynamics

Illustration - 12 A thin tube sealed at both ends, is 100 cm long. It lies horizontally, the middle 0.1 m
containing mercury and the two ends containing air at standard atmospheric pressure. If the tube is turned to
a vertical position, by what amount will the mercury be displaced ?

SOLUTION :

Let P0, V0 be the pressure and volume of the air columns initially.
Let P1, P2 be the final pressures in cm of Hg and V1, V2 be the final volumes.
Applying Boyle’s Law on both air columns, we get :
P0 V0 = P1 V1 and P0 V0 = P2 V2
PV P (45)
 P1  0 0  0
V1 45  x
PV P (45)
and P2  0 0  0
V2 45  x

Balancing forces on Hg columns in vertical position, we get :

P (below Hg column) = P(above Hg column ) + 10 cm
P2 = P1 + 10 (if P1, P2 are in cm of Hg)

Substituting to get :

45 P0 45 P0
+ 10 =
45 + x 45 x

Using P0 = 76 cm Hg, we get :

x2 + 684 x  2025 = 0
On solving, x = 2.95 cm.

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THERMODYNAMICS Section - 3

Temperature :
It may be defined as that thermal property which attains the same value for all bodies placed in thermal
contact with each other.
Heat Energy :
The transfer or flow of internal energy caused by the difference of temperatures between two bodies is
called as Heat Energy.
Zeroth Law of thermodynamics :
It two bodies A and B are in thermal equilibrium with another body C, then they are also in thermal equilibrium
with each other.
Thermodynamical system :
It is a collection of an extremely large numbers of atoms or molecules so that they together have some
pressure (P), volume (V) and temperature (T). Examples: a gas, vapour, steam, vapour in contact with the
liquid.

Work Done and Internal Energy

Work Done By a Gas During Expansion
Let us consider an ideal gas enclosed in a perfectly insulated cylinder
fitted with a non-conducting and frictionless piston. Let P be the pressure
exerted by the gas and V be the volume of the gas at any particular
instant. Let A be the area of crossection of the piston.
The force exerted by the gas on the piston = P A
If the piston moves through an infinitesimal distance dx, this force can
be assumed constant, and the work done (dW) is given as :
dW = (PA) dx = P dV
(A dx = dV = infinitesimal change in volume)

W =  PdV

 W =0

(b) If pressure is kept constant,

V2 V2
W  PdV  P  dV  P V2  V1 
V1 V1

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Vidyamandir Classes Gaseous State and Thermodynamics

 W = PV for constant pressure and we also have W = PV2 – PV1 = nRT2 – nRT1
W = nRT for constant pressure

Work Done From P-V Diagram

An ideal gas contained in a cylinder fitted with a massless and rictionless
piston can be considered as a thermodynamical system. Its state can be
represented by variables (P, V, T ). If P and V are known, T can be
calculated (PV = nRT).

The system’s state at any instant of time can be specified by two variables (P, V). The relation between
pressure P and volume V can be studied on a pressure - volume (P-V) graph known as indicator diagram or
a P-V diagram.
On such a graph, each equilibrium state of a thermodynamical system can be represented by a point whose
x-coordinate represents volume (V) and y-coordinate represents pressure (P).
A process can be represented by a curve on the P-V diagram. If the gas goes from initial state A (P1,V1) to
the final state B (P2, V2), the work done W is given by :
W = area under the curve AB above the X-axis (shaded portion)
Internal Energy
Internal energy (U) of a system is the total of all kinds of energy
possessed by the atoms and other particles that comprise the system.
The change in internal energy U depends only on the temperature
difference of initial and final states and not on the process between the
states.

First Law of Thermodynamics

If some heat is supplied to a system capable of doing some work, the quantity of heat absorbed by the
system is the equal to the sum of external work done by the system and increase in its internal energy.
If Q is the heat gained by the system, W is the work done against external pressure and U is the change
in internal energy, then
 heat energy given    increase in   work done 
 to the system   internal energy    by the system 
     
Q = U + W.

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In Thermodynamics :
1. Work done by a system is taken as positive (+). Work done on the system is taken as
negative (–).
2. Heat gained by a system is taken as positive (+) and the heat lost by the system is taken as
negative (–).
3. Increase in internal energy is taken as positive (+) and decrease in internal energy is taken as
negative (–).

Specific Heat of a Gas

The specific heat of gas is defined as the amount of heat required to raise the temperature of unit mass of
substance through 1K. Its unit in S.I. system is J/Kg/K. When the unit mass is 1 mole, the specific heat is
known as molar specific heat and its units are J/mol/K or cal/mol/K.
Molar specific heat = molecular weight (specific heat in J/gm/K)
In gases, on giving heat to the gas, besides temperature, its pressure and the volume may also change. Thus
specific heat of a gas depends upon the conditions under which the heat is given to the gas. Hence we will
define two principal types of specific heats of a gas.

Specific Heat at constant volume (Cv) :

Cv of a gas is defined as the amount of heat required to raise the temperature of 1 mole of that gas through
1K, provided that the volume of the gas remains constant. It is also known as molar specific heat at
constant volume.
In general, if n moles of a gas are heated at constant volume to increase the temperature by T,
Heat required = Q = n Cv T

Specific Heat at constant pressure (Cp) :

Cp of a gas is defined as the amount of heat required to raise the temperature of 1 mole of that gas through
1°K, provided that the pressure of the gas remains constant. It is also known as molar specific heat at
constant pressure.
In general, if n moles of a gas are heated at constant pressure resulting in a temperature rise by T,
Heat required = Q = n Cp T

Note : Cp is greater than Cv (Cp > Cv).

When we heat the gas at constant volume, the heat is supplied to raise the temperature of gas only. When we
heat the gas at constant pressure, the volume of the gas apart from temperature of the gas rises. When the
gas expands, it does some external work for increasing the volume. So in this case, the heat is supplied :
(a) to raise the temperature of the gas (b) to do the mechanical work for expansion

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Vidyamandir Classes Gaseous State and Thermodynamics

As a result more amount of heat is required to increase the temperature of the gas through the same amount
when the pressure is kept constant. Hence Cp is always greater than the value of Cv.

Cp Cp
The ratio of is denoted by  i.e.  = ( >1)
Cv Cv

Specific Heat Relation :

Consider n moles of an ideal gas. If its temperature is raised by T at constant volume, then the heat
transferred is n Cv T, where Cv is the specific heat at constant volume.
W = 0 (as no volume change is there)
By first law of thermodynamics :
Q = U + 0  n Cv T = U . . . . (i)
Next, let us heat the same gas at constant pressure. The heat Q required to change the temperature by T
will be n Cp T, where Cp is the specific heat at constant pressure.
W = P V where V is the change in volume.
By first law of thermodynamics :
Q = U + P V  n Cp T = U + P V . . . . (ii)
From (i) and (ii), we get :
n Cp T = n Cv T + P V
From gas equation :
PV = nR T  n Cp T = n Cv T + nR T
 Cp = Cv + R  Cp  Cv = R

R R
CV  and CV 
 1  1

Cp and Cv for Gases :

Consider 1 mole of a gas heated to raise the temperature by 1°C. When the gas is heated at constant
volume, all heat is converted to increase in internal energy. The work done is zero, i.e. Cv = U for 1°C (or
1 K) rise in temperature for 1 mole of a gas.

JEEMAIN.GURU

For mono-atomic gas :

3
Internal energy per mole = RT
2

3 3 3
Cv = V = R  T  1  RT  R
2 2 2

3 5 Cp 5
 Cv = R and Cp = R (as Cp  Cv = R)    
2 2 Cv 3

For di-atomic gas :

5
Internal energy per mole = RT
2
5 5 5
Cv = U = R  T  1  RT  R
2 2 2
5
 Cv = R
2

7 Cp 7
 Cp = R (as Cp  Cv = R)   = 
2 Cv 2

Illustration - 13 One mole of oxygen is heated at constant pressure from 0°C. What must be the quantity of
heat that should be supplied to the gas for the temperature to be doubled ? If the same heat is supplied to the
gas at constant volume, what will be the final temperature ?

SOLUTION :
T 1 = 0 + 273 = 273 K = 7930.6 J
Temperature is to be doubled If heating is done at constant volume :
 T 2 = 2T1 = 546 K Q = n Cv T
Q at constant pressure = n Cp T nR
Q =   1 ΔT
7 
Hence Q = n Cp T = n  R   T
2  1  8. 3
7  7930.6 = 1.4  1 (273)
 Q = 1   8.3  (546  273)
2  T = 655 K

JEEMAIN.GURU

Vidyamandir Classes Gaseous State and Thermodynamics

Illustration - 14 When water is boiled under a pressure of 2 atm., the heat of vapourisation is 2.20 × 106
J/Kg and the boiling point is 120°C. At this pressure 1 Kg of water has a volume of 10–3 m3 and 1 Kg of
steam has a volume of 0.824 m3.
(a) Compute the work done when 1 Kg of steam is formed at this temperature.
(b) Compute the increase in the internal energy.

SOLUTION :
(a) Work done = P (V) (at constant pressure) (b) U = Q  W
 W = 2 atm  (0.824  0.001) m3 U = m L  W
 W = 2  1.013  105 N/m2  0.823 m3  U = 1 kg  2.20  106 J/kg  166.74 kJ
= 166.74 kJ = (2200  166.74) = 2033.26 kJ

Illustration - 15 The temperature of 3 kg of krypton gas is raised from 20°C to 80°C.

(a) If this is done at constant volume, compute the heat added, the work done and the change in internal
energy.
(b) Repeat if the heating process is at constant pressure.
(for mono-atomic gas Kr, Cv = 0.0357 cal/g/K, Cp = 0.0595 cal/g/K)

SOLUTION :
(a) At constant volume : (b) At constant pressure :
W =0 Q = m Cp T = 3000 × 0.0595 × 100
Q = m Cv T = 3000  0.0357  100 ; = 17.85 kcal
T = 80  (20) = 100°C W = P (V2  V1) = nR (T2  T1)

Q = 10.7 kcal  3000 

W =   8.3  100 J = 30 kJ
U = Q  0 = 10.7 × 103 × 4.18 J  83.8 
U = n Cv T = 44.8 kJ
= 44.8 kJ

State Function]

Note : (i) It can be verified that Q = U + W.

(ii) Q is usually measured in calories and U and W are measured in Joules.

JEEMAIN.GURU

Illustration - 16 A system is taken from state i to the state f (refer to the

fig.). Along path “i a f ”, it is found that Q = 50 cal, W = 20 cal. Along the
path “i b f ”, Q = 36 cal. Calculate :
(a) W along the path “i b f ”
(b) If W =  13 cal for curved path “ f i ”, what is Q for this path ?
(c) Taking Ui = 10 cal, what is Uf ?
(d) If Ub = 22 cal, what is Q for the process “ i b” and for the process
“b f ” ?

SOLUTION :
Path “ i a f ”
Q = 50 cal ; W = 20 cal
 U = Q  W
U = 50  20 = 30 cal
 Uf  Ui = 30 cal.
As internal energy change is a State function, U will be same for any path from i to f.
(a) Path “ i b f ”
W = Q  U
W = 36  (Uf  Ui) = 36  (30) = 6 cal
(b) Path “ f i ”
Q = U + W = (Ui  Uf) + W
= (30) + (13) =  43 cal.
(c) Uf  Ui = 30 cal
 Uf = Ui + 30 = 40 cal
(d) Process “i b”
Q = U + W
Q = (Ub  Ui) + (W)ibf
{(W)ib = (W)ibf because (W)bf = 0}
Q = (22  10) + 6 = 18 cal
(d) Process “b f ”
Q = U + W
Q = (Uf  Ub) + 0 = 40  22 = 18 cal.

JEEMAIN.GURU

THERMODYNAMIC PROCESSES Section - 4

In a thermodynamic process, the initial and final states are important, but the manner in which the system is
taken from initial to final state must also be taken into account. Hence it is important to distinguish between
the following processes.

Isothermal process :
An isothermal process is one in which the temperature remains constant.
A gas under going an isothermal process should remain in perfect thermal contact with a constant temperature
heat reservoir. The gas obeys Boyle’s Law, during an isothermal process, i.e. PV = constant
As the temperature remains constant internal energy of the system remains constant.
i.e., U = 0 (for isothermal process)
From Ist Law : Q = W

(a) Isothermal Expansion :

 If the gas expands, it takes heat from the heat
reservoir and does positive work, i.e. in equation
Q = W, both Q and W are positive.
 The process takes place slowly. As the pressure
on the piston is reduced, the gas tries to
expand.
 In expansion, it tends to cool down, but the heat
reservoir gives heat input to keep temperature
constant.

(b) Isothermal Compression :

 If the gas is compressed isothermally, it gives heat
to the reservoir and the work done is negative, i.e.,
in the equation Q = W, both Q and W are
negative.
 To do a perfectly isothermal process, pressure is
increased in very small steps. As the gas is
compressed slowly, its temperature tends to rise,
but the reservoir extracts the heat from the
system to keep the temperature constant.

In an adiabatic process, no heat enters or leaves the
system. Such a situation is achieved by heavily insulating
the system.
From Ist Law of thermodynamics : Q = U + W

JEEMAIN.GURU

Gaseous State and Thermodynamics Vidyamandir Classes

In adiabatic process Q = 0
 U+W=0
The gas in this process obeys the relation :
PV = constant ( = Cp /Cv)
 
 P1V1 = P2V2

Note : The adiabatic curve in P-V diagram is much steeper than the isothermal curve.

(a) Adiabatic Expansion :

As the pressure on the piston is reduced, the gas pushes the piston
upwards. Due to the expansion, the temperature of the system falls down.
The molecules of the gas lose speed after colliding with a receding (moving
away) piston. The loss in the speed causes a fall in the temperature. The
gas does positive work and its internal energy decreases. In the equation
of Ist law :
U + W = 0, U is negative and W is positive.
(internal energy of the gas is being converted into work done)

(b) Adiabatic Compression :

As the pressure on the piston is increased, it moves downwards
compressing the gas. Due to compression, the temperature of the gas
rises. The molecules of the gas gain speed after colliding with an incoming
piston. The gain in speed causes a rise in temperature. Work is done on
the gas and its internal energy increases.
In the equation : U + W = 0, U is positive and W is negative.

Isochoric process :
A process in which the volume remains constant is known
as isochoric process.
For an isochoric process, an ideal gas is taken in a container
with rigid walls so that neither expansion nor compression occurs.
The gas obeys the relation : P  T
In isochoric process, W = 0. So from Ist Law of
thermodynamics : Q = U.
(a) If heat is given to the gas, its temperature and pressure rise.
Its internal energy also rises. U and Q are both positive.

JEEMAIN.GURU

Vidyamandir Classes Gaseous State and Thermodynamics

(b) If heat is taken out from the gas, its temperature and pressure fall.
Its internal energy also decreases. Q and U are both negative.

Isobaric process :
A process in which the pressure is kept constant is called as isobaric
process.
For isobaric process, the external pressure on the piston is kept
constant.
The gas obeys Charles’ Law : V  T
The work done : W = P (V2  V1)
= n R (T2  T1)

(a) Isobaric Expansion :

If heat is given to the gas, isobaric expansion occurs. The volume
and the temperature both rise. The gas expands doing positive
work.
In equation :
Q = U + W, all the three terms :
Q, U and W are positive in the isobaric expansion.

(b) Isobaric Compression :

If heat is taken out of the gas, isobaric compression occurs.
The temperature falls and the gas contracts causing negative work.
In the equation :
Q = U + W, all three terms :
Q, U and W are negative in the isobaric compression.

Expressions for U, W, and Q for Different Processes

Internal Energy Change : (U)
U = nCv T for every process.
It is state function and depends only on the difference of initial and
final temperatures.
nR
U = n Cv T = T
 1

JEEMAIN.GURU

Process Work Done : (W) Heat Exchange : (Q)

V2 V
Isothermal Process : W  2.303 nRT log10 Q  2.303 nRT  og10 2
V1 V1

PV  P V nR T1  T2 
Adiabatic Process : W 11 2 2  Q = 0
 1  1

Isochoric Process : W=0 Q = n Cv T (use definition of Cv)

Isobaric Process : W = P V = P (V2  V1) Q = n Cp T (use definition of Cp)
W = nR (T2  T1)

Relations for Thermodynamic Processes (State Variables P, V, T)

Isochoric process :
P1 P2
Volume remains constant.  P  T  
T2 T2
Isothermal process :
Temperature remains constant  P  1/V  P1 V1 = P2 V2
Isobaric process :
V1 V2
Pressure remains constant.  V  T  
T2 T2

No heat transfer takes place.
P1 V1 = P2 V2 T1 V1  1 = T2 V2  1 T1 P11   = T2 P21  

Illustration - 17 An ideal gas undergoes an isothermal expansion at 0°C from 0.010 m3 to 0.200 m3. For 5
moles of gas, compute the work done, the heat added, and the change in internal energy.

SOLUTION :
Let V1 = 0.01 m3 ; V2 = 0.2 m3 ;
T1 = T2 = 273 K ; n = 5 moles
V2
W = 2.303 nRT1 log 10 V
1
W = 2.303  5  8.3  273 log10 20 = 33.946 J.
As U = 0 for isothermal process, Q = W = 33946 J.

JEEMAIN.GURU

Vidyamandir Classes Gaseous State and Thermodynamics

Illustration - 18 A gasoline engine takes in 5 moles of air at 20°C and 1 atm., and compresses it adiabatically
to 1/10th of the original volume. Find the final temperature and pressure. Assume air to be diatomic. Also
find the work done and change in internal energy.

SOLUTION :
Let P1 = 1 atm. n = 5 moles T1 = 293 K
 V2 = V1/10
Using P1 V1 = P2 V2
 1
 V1 
 P2 = P1   = 1 (10)1.4 = 25.12 atm.
 V2 

Using T1V1  1 = T2V2  1

 1
 V1 
 T2 = T1   = 293(10)0.4 = 736 K
 V2 

nR  T1  T2  5  8.3   293  737 

Work done = 
 1 0. 4
=  46 kJ
U = Q  W = 0  W = 46 kJ

Illustration - 19 How much work is done by an ideal gas is expanding isothermally from an initial
volume of 3 L at 20 atm to a final volume of 24 L ?
SOLUTION :
In isothermal process at temperature T :
V2
W = 2.303 nRT log10 V
1
V2
W = 2.303 (P1V1) log10 V (using P1V1 = nRT)
1
24
= 2.303 (20  3) log10 L atm.
3
= 2.303  60  log10 8 (101) J
= 1.26  104 J

JEEMAIN.GURU

Gaseous State and Thermodynamics Vidyamandir Classes

Illustration - 20 In a cylinder, 2.0 moles of an ideal monoatomic gas initially at 1.0 × 106 Pa and 300 K
expands until its volume doubles. Compute the work done if the expansion is :
(a) isothermal (b) adiabatic (c) isobaric

SOLUTION :
Let P1 = 1× 106 Pa = 106 N/m2 ;
T1 = 300 K ; n = 2 moles
and Final volume = 2 (initial volume)
 V2 = 2 V1

(a) Wisothermal = 2.303 nRT log (V2 /V1)

= 2.303 × 2 × 8.3 × 300 log10 2 = 3452 J
nR  T1  T2 
 1
For adiabatic process: T1V1 –1 = T2 V2 –1
5 / 31
 V2  1
T2 = T1 =     1  300   
 V1  2
 T2 = 189 K

nR  T1  T2  2  8.3   300  189 

W=  1 5
1
3
= 2764 J
(c) W(isobaric) = P (V2  V1)
P1 V1 = nRT1
nRT1 2 x 8.3 x 300
 V 1= =
P1 106
 V1 = 4.98 × 10–3 m3
and W = P (V2  V1) = P (2V1  V1) = P V1
 W = 106 × 4.98 × 103 J = 4980 J.

JEEMAIN.GURU

Illustration - 21 2.0 moles of an ideal gas are carried round a cycle as

shown. If the process b  c is isothermal and Cv = 3 cal/mol/K.
Determine:
(a) work done
(b) change in internal energy
(c) heat supplied to the system during processes
a  b b  c and c  a.

SOLUTION :
(a) Process a  b is clearly isobaric at P = 4 atm. Process b  c :
W = P (Vb  Va) = 4 (16.4  8.2) = 32.8L atm Isothermal, T = 0  U = 0
 Wa  b = 32.8 × 101 J = 3313 J Process c  a : U for complete cyclic process
is zero because it depends on initial and final
Process b  c is isothermal (given)
States i.e. temperature difference only.
Vc
W = 2.303 nRT log10 V (U)ab + (U)bc + (U)ca = 0
b
1200 + 0 + (U)ca = 0
Vc
W = 2.303 (Pb Vb) log10 V
b  (U)ca = 1200 cal.
8.2 (c) Using first law of thermodynamics:
W = 2.303 (4  16.4  101) log10
16.4 (Q)ab = (U)ab + Wab
Wb  c = 4592.5J
= (1200 + 3313/4.18) cal
Process c  a is isochoric (volume is constant) = 1992.5 cal
 Wc  a = 0 J
(Q)ab = 1992.5 cal
(b) Process a  b (Q)bc = (U)bc + Wbc
U = n Cv T = (0  4592.5/4.18) cal = 1098.7 cal
 PbVb PaVa   (Q)bc = 1098.7 cal.
U = nCv   PV = nRT
 nR nR  (Q)ca = (U)ca + Wca
Cv 3 = 1200 + 0 =  1200 cal
=  PbVb  PaVa  
R 0.0821  Q =  1200 cal.
(4  16.4  4  8.2) = 1200 cal.

JEEMAIN.GURU

Illustration - 22 Figure shows three processes for an ideal gas. The

temperature at “a” is 600K, pressure 16 atm and volume 1L.The volume at “b”
is 4 L. Out of two processes, ab and ac, one is adiabatic and other is isothermal.
The ratio of specific heats of the gas is 1.5.
(a) Which of the processes “ab” and “ac” is adiabatic ? Why ?
(b) Compute the pressure of the gas at “b” and “c”.
(c) Compute the temperature at “b” and “c”.
(d) Compute the volume at “c”.

SOLUTION :
(a) The process ab is adiabatic because it steeper
than ac.
(b) Pa = 16 atm Vb = 4 L Va = 1 L Ta = 600K
 Pa Va = Pb Vb
 1.5
V  1
Pb  Pa  a   16   
 Vb   4
 Pb = 2 atm.
As bc is isobaric, Pb = Pc = 2 atm.
(c) Tc = Ta = 600K because ac is isothermal.
Process “ ab ” (adiabatic)
Tb can be calculated using Ta Va  1 = Tb Vb  1
PaVa PbVb
or 
Ta Tb
 1 0.5
 
Hence Tb = Ta  Va  1
 600    300 K
 Vb  4

(d) Process “ac” (isothermal)

 Pa Va = Pc Vc
P V 16  1
 Vc = a a = =8 L
Pc 2

JEEMAIN.GURU

Vidyamandir Classes Gaseous State and Thermodynamics

Illustration - 23 6 grams of hydrogen gas at a temperature of 273K were isothermally expanded to five
times its initial volume and then isochorically heated so that the pressure in the final state becomes equal
to that in the initial state. Find the total amount of heat absorbed by the gas during the entire process.

SOLUTION :
Represent the processes on the PV diagram by the curve 1 to 2 (isothermal) and the line 2 to 3 (isochoric).
P1 = P3
For the process 1 to 2 (isothermal)
T2 = T1 = 273 ; V2 = 5 V1
Q = U + W = 0 + W
V2
 Q = 2.303 nRT1 log10
V1
6
  Q = 2.303   8.3  273  log10 5
2
= 10942.4 J
State 1 and state 3 are at the same pressure.
V1 V3 V3
   T3 = V T1 = 5  273 = 1365 K
T1 T3 1

Process 2 to 3 (isochoric)
Q = U + W
Q = n Cv T + 0

6 5
 Q =  R   T3  T2 
2 2
 Q = 7.5  8.3  (1365  273) J = 67977 J

Thus total heat absorbed

= Q 1  2 + Q2  3 = 78919.4 J

JEEMAIN.GURU

Gaseous State and Thermodynamics Vidyamandir Classes

Illustration - 24 One mole of a perfect gas, initially at a pressure and temperature of 105 N/m2 and 300K
respectively expands isothermally until its volume is doubled and then adiabatically until its volume is again
doubled. Find the final pressure and temperature of the gas. Find the total work done during the isothermal
Given  = 1.4. Also draw the P-V diagram for the process.

SOLUTION :
Let (P1 V1 T1) be the initial pressure, volume and
the temperature of the gas.
For isothermal expansion (1 to 2)
We have : V2 = 2V1
Using, P1 V1 = P2 V2
 P2 = P1(V1/V2) = P1/2 = 0.5 × 105 N/m2.
and T2 = T1 = 300 K
For adiabatic expansion (2 to 3) Hence final pressure and temperatures are
Using P2 V2 = P3 V3 and V3 = 2 V2 1.9 × 104 N/m2 and 227.35 K
 Work Done :
 V2 
 P3 = P2   = 0.5  105  (0.5)1.4 W = W1  2 + W2  3
 V3   W = 2.303 nRT1
4 2
= 1.9  10 N/m V2 nR T2  T3 
1 1 log10 
Also, T2 V2 = T3 V3 V1  1
 -1 0.4  W = R (2.303  300  log10 2) +
 v2  1
 T3 = T 2   = 300   = 227.35 K
 v3  4 R  300  227.35 
= 3233.56 J
0.4

JEEMAIN.GURU

SUBJECTIVE SOLVED EXAMPLES

Example - 1 A flask of volume 2l, provided with a stopcock contains oxygen at 300 K and atmospheric
pressure. The system is heated to a temperature of 400 K, with the stopcock open to the atmosphere. The
stopcock is then closed and the flask is then cooled to its original temperature.
(a) What is the final pressure of oxygen in the flask ? (b) How many grams of oxygen remain in the

SOLUTION :

Let V = 2 L (remains constant)

When the flask is heated open to the atmosphere its pressure remains the same at P atmosphere .
Hence using PV = nRT, we apply :
n1T1 = n2T2 for the heating process.
n1(300) = n2(400)
3n1 = 4n2
For the cooling process(taking place at constant volume and given moles)
P2 P P3
 3  P3  T3
T2 T3 T2

P 3
 P3  at  300   atm.
400 4
Loss of grams of O2 = (n1  n2)  32

 3 
=  n1  n1  32 = 8n1
 4 

P V  8 1 2 
= 8  at  = 0.6504 gm
 RT1  0.082  300

Self Study Course for IITJEE with Online Support Subjective Solved Examples 29
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Gaseous State and Thermodynamics Vidyamandir Classes

Example - 2 A tube closed at one end contains a mercury column 15 cm long inside it. The length of air
column trapped between the closed end and mercury is 40 cm when the tube is horizontal. Find the length of
air column if:
(a) the tube is made vertical with open end downwards.
(b) the tube is kept inclined at 60° with the vertical with open end downwards.(Patm = 75 cm Hg)

SOLUTION :

Let A be the crosssectional area and x be the length of Hg column. Let P1, P2 be the pressures in air column
in the vertical and inclined positions respectively.
Let y1, y2 be the lengths of the corresponding air columns.
Applying Boyle’s Law : P0 V0 = P1 V1 = P2 V2
Where P0 = atm. pressure,
V0 = 40 A, V1 = y1 A, V2 = y2 A
Balancing forces on Hg columns :
P1 + x = P and P2 + x cos 60° = P0
P0 V0 = P1 V1
75 (40 A) = (75  15) y1
 y1 = 50 cm.
P0 V0 = P2 V2
75 (40 A) = (75  15 cos 60°) (y2 A)
 y2 = 44. 4 cm

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Example - 3 An open glass tube is immersed in Hg in such a way that a length of 8 cm extends above
the Hg level. The open end of the tube is then closed and the tube is raised vertically up by 44 cm. What
will be the length of the air column above Hg in the tube now ?

SOLUTION :

Let A be the area of crosssection of the tube.

P0 = atm. pressure = 76 cm Hg
x = length of the air column in the final position.
P1 = air pressure (final)
As the tube is raised, the volume of the air column trapped between the closed end and Hg increases and
hence pressure drops. Due to drop in pressure,
Hg rises in the tube.
Height of Hg column = (8 + 44)  x = 52  x
Due to hydrostatic conditions : PA = PB
 P1 + (52  x) = Patm.
 P1 = 76  (52  x) = 24 + x
Applying Boyle’s Law on air column :
P0 V0 = P1 V1
 76 (8A) = (24 + x)(x A)
 76 (8) = 24 x + x2
On solving, we get :
x = length of air column = 15.42 cm

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Example - 4 A barometer tube contains some air above the Hg level

inside it. The atmospheric pressure is 76 cm of Hg. The Hg level in the
barometer tube is 74 cm high and the tube has a length of 100 cm above
Hg level outside the tube as shown. The tube is raised vertically upwards
by a distance of 10 cm. What is the height of Hg level inside the tube after
it has been raised ?

SOLUTION :
Let P1 and P2 be the initial and final pressures in the air column above Hg inside the tube. Let x be the height
of Hg column after the tube has been raised.

From Hydrostatic conditions :

P1 + 74 = Patm  P1 = 76  74 = 2 cm Hg.
P2 + x = Patm  P2 = 76  x.
Applying Boyle’s Law :
P1 (26 A) = P2 (110  x) A
where A is crosssectional area.
2 (26) = (76  x) (110  x)
x2  186 x + 8308 = 0
On solving, we get :
x = 74.53 cm.

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Example - 5 A cylinder fitted with a movable piston contains hydrogen at a pressure of 3.5 × 105 N/m2
and a temperature 366 K. Hydrogen expands adiabatically until the pressure in the cylinder falls to 0.7 ×105
N/m2. The piston is then fixed and the gas is heated until the temperature becomes 366 K. The pressure in the
cylinder is now found to be 1.1 × 105 N/m2. Determine the molar specific heats of hydrogen.

SOLUTION :
Represent the processes on P-V diagram by curve
1 to 2 (adiabatic) and the line 2 to 3 (isochoric).
Hence P1 = 3.5 × 105 N/m2
P2 = 0.7 × 105 N/m2
T1 = 366 K T2 = ?
5 2
P3 = 1.1 × 10 N/m T3 = 366 K
Process 2 to 3 (isochoric)
P2 P3
 T = T
2 3
P2 0.7
 T2 = P T3  1.1  366  232.90 K
3

Process 1 to 2 (adiabatic)
T1 P11   = T2 P21  

 T1   1 1  11 

1
1
         
 T2   5  7 5

  (log10 11 log10 7) = ( 1) log10 5

log10 5
  = log 5  log 7 - log 11  1.39
10 10 10

R R
Thus Cp = = 29.58 J mol1 K1 and Cv = = 21.28 J mol1 K1
 1  1

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Example - 6 The rectangular box shown in fig. has a partition which can slide without friction along
the length of the box. Initially each of two chambers of the box has one mole of a monoatomic ideal gas
( = 5/3) at a pressure of P0, volume V0 and temperature T0. The chamber on the left is slowly heated by an
electric heater. The walls of box and partition are thermally insulated. Heat loss through lead wires of heater
is negligible. The gas in the left chamber expands by pushing the partition until the final pressure in both
chambers becomes (243/32) P0. Determine :
(a) the final temperature of the gas in each chamber, (b) the work done by the gas in the right
chamber.

1/  3/ 5
 P0   32  8V
V1  V0    V0    0
 P1   243  27
SOLUTION :
and T0 V0  1 = T1 V1  1
Let P1, V1, T1 and P2, V2, T2 be the final pressure,
volume, temperature in the right and left chambers  1 2/3
V   27  9
respectively.  T1  T0  0   T0    T0
 V1   8  4
It is very important to observe that P1 = P2
because the partition is in equilibrium and V1 + In left chamber :
V2 = 2V0 because total volume remains same. 8 46
We have : V2 = 2V0 V1 = 2V0  V0  V0
The process in the left chamber is none of the 27 27
PV P0V0 P2V2
four standard processes, so we will use =  
T T0 T2
constant.
P2V2 243 46 207
The process in the right chamber is adiabatic.  T2 = T0   T0  V0
P0V0 32 27 27
243
We have P1 = P2 P 207 9
32 0 Hence the final temperatures are T0 and T0
16 4
Work done :
Considering adiabatic compression in right
chamber :
P0V0  PV
1 1
 W=
 1
In right chamber :
P0V0  243 8  15
We have : P0 V0 = P1 V1  W= 1     P0 V0
  1  32 27  8

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Example - 7 An ideal mono-atomic gas is confined in a

cylinder by a spring loaded piston of cross-section 8 × 10–3 m2.
Initially the gas is at 300 K and occupies a volume of 2.4 × 10–3
m3 and the spring is in its relaxed (unstretched, uncompressed)
state. The gas is heated by a small electric heater until the piston
moves out slowly by 0.1 m. Calculate the final temperature of
the gas and the heat supplied in joules by the heater. The force
constant of the spring is 8000 N/m, atmospheric pressure is
1 × 105 N/m2. The cylinder and the piston are thermally insulated.
The piston is massless and there is no friction between the piston
and the cylinder. Neglect heat loss through the lead wires of the
heater. The heat capacity of the heater coil is negligible. Assume
the spring to be massless.
SOLUTION :
The process taking place in the cylinder is none Applying PV/T = constant, we get :
of the four standard processes. 
Hence, we will use PV/T = constant. T1 P2 V2 300  2 105  3.2 103
T2  
Let (P1, V1, T1) and (P2, V2, T2) denote the initial P1 V1 105  2.4 103
and the final pressure, volume and temperature
= 800 K
respectively.
P1 = Patm = 105 N/m2 ; Heat supplied = Q = U + W
We have U = n Cv T
V1 = 2.4 × 10–3 m3 ;
PV 3
T1 = 300 K = 1 1  R  T2  T1 
RT1 2
Balancing forces on the piston :
105  2.4  103  3
kx =  500  600 J
We have : P2 = Patm + 300  2
A
W = work done against atmosphere + work
Here, x = 0.1 m ; A = 8 × 10–3 m3
done against spring
and k = 8000 N/m
W = Patm (V) + 1/2 kx2
5 5 5 2
 P2 = 10 + 10 = 2 × 10 N/m
 W = 105 (0.1 × 8 × 10–3) + 0.5 × 8000 ×
0.01
and V2 = V1 + x A = 3.2 × 103 m3
= 120 J
Hence Q = U + W = 600 + 120 = 720 J.

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Example - 8 Two moles of an ideal monatomic gas, initially at pressure p1 and volume V1, undergo an
adiabatic compression until its volume is V2. Then the gas is given heat Q at constant volume V2.
(a) Sketch the complete process on a P-V diagram
(b) Find the total work done by the gas, the total change in its internal energy and the final temperature of
the gas.
[Give your answers in terms of P1, V1, V2, Q and R.]

SOLUTION :
(a) Figure displays the PV diagram of the gas Work done by the gas on heating at
undergone the given two processes. constant volume
Since the volume is held constant
 W2 = 0
The total work done by the gas is
2/ 3 
3 P1 V1   V1 
W = W1 + W2  1    
2   V2  

(ii) Total change in Internal Energy :

(b) Change in internal energy in adiabatic
(i) Total Work Done by the Gas : compression
Work done by the gas in adiabatic
U1 =  W1
compression
 V 2/3 
In an adiabatic process : 3 P1 V1 
U1   1   1
P1 V1  P2V2 2  V2  
W1 
 1 and U2 = Q (given)
For a gas undergoing adiabatic process : The total change in internal energy of the gas is
 
We have : PV
1 1  P2 V2 2/3
3 P1 V1  V1  
U = U1 + U2 =     1 Q
PV 
 1 1 
PV 
V
2  V2 
 
1 1 2
V2 (iii) Final temperature of the Gas :
 W1 
 1 Change in temperature in adiabatic
compression
PV   V  1  Since U = CV T,
W1  1 1 1  1 
   1   V2   U1
 
We get : T = C
2/3  V
3P V   V 
Hence, W1  1 1 1   1    V 2/3 
2   V2   3 P1 V1 
 T2 – T1 = 2 C  1   1
V  V2  
[For a monatomic gas,  = 5/3]

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 V 2/ 3 
3 P1 V1  Q = CV T = CV (T3 – T2)
  1   1
3   V2   2/3
2 n R  Q Q PV V 
2  T3 =  T2   1 1 1 
CV      n R n R  V2 
P1 V1  V 2 / 3 
 1   1 Since n = 2 mol, we get :
 T2 = n R  V2  
  2/3
Q p V  V1 
T3   1 1  
Change in temperature on heating the gas 3R 2R  V2 

Example - 9 Two moles of an ideal monatomic gas is taken through

a cycle ABCA as shown in the P–T diagram. During the process AB,
pressure and temperature of the gas vary such that PT = constant. If
T1 = 300 K, calculate
(a) the work done on the gas in the process AB and
(b) the heat absorbed or released by the gas in each of the processes.
Give answers in terms of the gas constant R.

SOLUTION :
In the process AB, we will have The negative sign implies that the work is done
on the gas.
PV = nRT and PT = K . . . . (i)
(b) The change in energy of the gas in the process
nRT 2 AB is
Eliminating P, we get : V 
K
3 
U AB  n CV T   2   R  T1  2T2 
dV 2nRT 2 
  . . . . (ii)
dT K
= 900 R
(a) The expression of work done by the gas is :
Now from the first law of thermodynamics,
W   P dV QAB = UAB + WAB = 1200 R – 900 R
TB = – 2100 R
  K   2nRT 
W     dT  The negative sign implies that the heat is released
TA
T  K 
in the process AB. The process BC takes place
[Using Equations (i) and (ii)] at constant pressure. Hence
T1 WBC = P V = (2P1) (VC – VB)
 WAB   2nR dT  nRT1 nRT1 
2T1 =  2 P1   P  2 P 
 1 1 
= 2 nT1R
= nRT1
=  2  2 (300 K) R = – 1200 R
= 2  300 R = 600 R

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Now, V
W AC  nRT ln A
3  VC
U BC  n CV   2  R  TC  TB 
2  (where T = 2T1)
= 3 (R) (2T1 – T1) = 3(R) 300 = 900 R = 2  R  2  300 log10 2
= 1200 R log10 2
The positive sign implies that the heat is absorbed
in the process BC. UCA = 0
The process CA takes place at constant QCA = UCA + WCA
temperature. Hence = 0 + 1200 R log10 2

Example - 10 A cubical box of side 1 metre contains helium gas (atomic weight 4) at a pressure of 100
2
N/s . During an observation time of 1 second, an atom travelling with the root-mean-square speed parallel
to one of the edges of the cube, was found to make 500 hits with a particular wall, without any collision
25
with other atoms.Take R  J/mol-K and k = 1.38 10–23 JK.
3
(a) Evaluate the temperature of the gas. (b) Evaluate the average kinetic energy per atom.
(c) Evaluate the total mass of helium gas in the box.
SOLUTION :
(a) We have :
1000 2  4  103 kg mol 1   160 K
Distance travelled by the atom in successive hit 
to one of the edges of the cube is l = 2m 
3  25 / 3 J 1 mol 1 
Number of hits with the wall in one second is
(b) The average kinetic energy per atom is
N = 500/s

3 3

KE  kT    1.38 1023 J K 1 160 K 
2 2

= 3.31  10–21 J
(c) Using the expression
m
Hence, distance travelled in one second, i.e. root PV  nRT    RT
M 
mean square speed of atom, is
PVM
Vrms = l N = (2 m) (500/s) = 1000 m/s We get : m 
RT
Since the root mean square speed of gaseous
atoms is given by vrms  3 RT / M , we get : 100 Pa  1 m3   4  103 kg mol 1 

v2 M
T  rms
 25 / 3 J K 1 mol 1 160 K 
3R = 3.0  10–4 kg

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Vidyamandir Classes Gaseous State and Thermodynamics

THINGS TO REMEMBER
1. (a) If the molecules are moving speeds c1, c2, c3, ................., cN ;
then the root mean square speed of the gas is defined as :

c12 +c 22 + c32 + .........+cN

2
c 2 = crms =
N
(b) crms can be calculated with any of the following results.
3P 3 RT 3kT
crms =  
 M m0

2. The pressure exerted by the gas is

1 m0 N 2 1 2 m N
P crms or P  crms where  = density of gas  0
3 V 3 V
3. Kinetic energ of a gas :
For monoatomic gas :
Total energy per molecule = 3/2 kT
Total energy per mole = 3/2 RT
For diatomic gas :
Total energy per molecule = 5/2 kT
Total energy per mole = 5/2 RT
For triatomic gas :
Total energy per molecule = 3kT
Total energy per mole = 3RT
4. (a) Work done
W =  PdV
(b) Work Done From P-V Diagram

W = area under the curve AB above the X-axis (shaded portion)

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5. Internal Energy
Internal energy (U) of a system is the total of all kinds of energy possessed by the atoms and other particles
that comprise the system. The change in internal energy U depends only on the temperature difference of
initial and final states and not on the process between the states.
U = Uf – Ui
6. First Law of Thermodynamics
 heat energy given   increase in   work done 
 to the system    internal energy    by the system 
     

Q = U + W.

R R
CV  and CV 
 1  1

8. Cp and Cv for Gases :

(a) For mono-atomic gas :
3 5
Cv = R and Cp = R
2 2

Cp 5
  
Cv 3

5
 Cv = R
2

7 Cp 5
 Cp = R   
2 Cv 3

9. Relations for Thermodynamic Processes (State Variables P, V, T)

Isochoric process :
P1 P2
Volume remains constant.  P  T  
T2 T2
Isothermal process :
Temperature remains constant  P  1/V  P1 V1 = P2 V2

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Isobaric process :
1 V2 V
Pressure remains constant.  V  T  T T
2 2
No heat transfer takes place.
P1 V1 = P2 V2 T1 V1  1 = T2 V2  1 T1 P11   = T2 P21  

10. Expressions for U, W, and Q for Different Processes

Internal Energy Change : (U)
U = nCv T for every process.
It is state function and depends only on the difference of initial and final temperatures.
nR
U = n Cv T = T
 1
Process Work Done : (W) Heat Exchange : (Q)

V2 V2
Isothermal Process : W  2.303 nRT log10 Q  2.303 nRT  og10
V1 V1

PV  P V nR T1  T2 
Adiabatic Process : W 11 2 2  Q = 0
 1  1

Isobaric Process : W = P V = P (V2  V1) Q = n Cp T (use definition of Cp)

W = nR (T2  T1)

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