Lectures on Thermodynamics 1

Chapter: 5

PRODUCTION OF VERY LOW TEMPERATURE

Introduction
The production of very low temperature is intimately linked with the liquefaction of
gases because all experiments in the region of very low temperature involve the gases in
the liquid or solid form. The following are the methods employed to produce very low
temperature.
(i) Method of freezing mixture (By adding salt to ice).
(ii) Cooling by evaporation of a liquid under reduced pressure.
(iii) By the adiabatic expansion of gas.
(iv) Joule Thomson effect.
(v) Regenerative cooling.

5.1 Adiabatic Expansion

During an adiabatic process the gas is perfectly insulated from surrounding i.e., the
gas can neither give het nor take heat from the surrounding. When the gas expands
adiabatically against some external pressure, it has to do the work at the cost of its internal
energy. As the internal energy of gas is a function of its temperature, during the adiabatic
expansion the temperature of gas must fall. If a highly compressed gas is allowed to expand
suddenly then there is large amount of fall in temperature so the cooing effect will be large.
If P and T be the pressure and temperature of a perfect gas then during adiabatic process:

PV = constant
CP
where  = .
CV
RT
For a perfect gas PV = RT or, V=
P
PRT
 = const.
P
or, RP1–T = constant.
Constant
or, P1–T =
R
or, TP1– = constant
2 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila

1–
or, TP   = Constant . . . . (i)
If T1 and P1 are the initial temperature and pressure of a given mass of gas while T2 and P2
are its final temperature and pressure of gas, then
1– 1–
 T1 P1   = T2 P2   . . . . (ii)
1–
P1
 Final temperature T2 = T1    . . . . (iii)
P2
Example:
If CO2 gas at room temperature is compressed to a pressure of 150 at m is suddenly
released to atmospheric, the final temperature is
1.3–1
1 
T2 = 300 1.3 = 96 k [where  = 1.3]
150
Here initial temperature (T1) = (27 + 273) = 300 K
Initial pressure (P1) = 150 atm , Final pressure (P2) = 1 atm
This temperature 96 K is so low that the expanding CO2 gas gets even solidified, usually
known as dry ice. The machine utilizing the above principle is called gas expansion
machine.
5.1 Method of freezing mixture
The earliest method for production of temperatures much lower than that of ice is adding a salt
to ice. When a salt (for example, NaCl) is added to ice, the freezing mixture is formed. The salt
is dissolved by the water adhering to ice and more ice melts. The heat necessary for this process
viz. heat of solution and the latent heat necessary for melting ice is extracted from the mixture
itself. As a result, the temperature of the mixture falls down. This is the principle involved in
freezing mixtures. The process cannot go indefinitely. The lowest temperature that can be
attained by the method of freezing mixture is definite and depends upon the salt used and is
known as eutectic temperature. See Table 1.
Table 1
Salt Amount of salt in Eutectic temperature
100gm of mixture
MgSO4 19.0 gm 3.9 C
KCl 19.7 gm 11.1 C
NH4Cl 18.6 gm 15.8 C
NaNO3 37.0 gm 18.5 C
NaCl 22.0 gm 21.2 C
CaCl2 29.8 gm 55.0 C
 Lectures on Thermodynamics 3

5.2 Thermodynamics of Refrigeration

Cooling by evaporation under reduced pressure
A refrigerator is a device which transfers heat from lower temperature to a higher
temperature with the aid of some external work. The working substance which under goes
cyclic changes in the refrigerator is called the refrigerant and the process is known as
refrigeration.

Hot surrounding, at
higher temp. T1
Q1
Q1 = (Q2 + W)

Working
substance W = (Q1  Q2)

Q2

A cold body at lower

temprature T2

Figure 1 : Outline of a refrigerator

The outline of a refrigerator is shown in Figure 1. A refrigerator is a device in which the

refrigerant takes in heat Q2 from a cold body, certain work W is done on it by some external
agency (e. g. electricity) and rejects heat Q1 = Q2 + W to the hot surrounding.
4 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila

Figure 2: Cooling by evaporation under reduced pressure

The schematic diagram of a refrigeration cycle is shown in Figure 2. The refrigerant in the
form of a liquid is stored in the liquid storage at a temperature equal to that of the
condenser whose temperature is equal to the hot source. The refrigerant from the liquid
storage passes through the throttling value suffering an adiabatic expansion and cools to a
lower temperature. Then it passes through the evaporator where it gets evaporated at a
constant temperature and pressure absorbing required latent heat from the object to be
cooled.
This vapour then passes through the compressor where heat of compression is
rejected at a constant pressure by passing the vapour through the condenser maintained at
low temperature so that the working substance leaves the condenser as sub-cooled liquid
and reversible cycle starts. In this way very low temperature is produced by a refrigerator.

Coefficient of Performance of a Refrigerator

In a refrigerator, it is desired to extract a large amount of heat from a cold body with
the expenditure of some external work. The heat extracted is known as output and the
work as input. The efficiency of a refrigerator is known as coefficient of performance. It's
abbreviated form is 'cop'.
It is defined as the ratio of the amount of heat absorbed from the cold reservoir to the
work done in running the machinery.
i.e., coefficient of performance
Amount of heat absorbed from the cold reservoir
=
Work done in running the machinery
 Lectures on Thermodynamics 5
If Q2 be the heat absorbed from cold reservoir and Q 1 is the heat rejected to the hot
reservoir, then
Q2 Q2
= =
W Q1 – Q 2
But in a Carnot's cycle 
Q1 T1
 =
Q2 T2
where T1 is the temperature of hot reservoir and T2 is the temperature of cold reservoir.
T2
then  =
T1 – T2
If  is the efficiently of a Carnot engine operating between the same two temperature then
T2 T1 – T2
=1– =
T1 T1
1 T1
 =
 T1 – T2
1 T1
or, –1= –1
 (T1 – T2)

1 –  T1 – T1 + T2
or, =
 T1 – T2
1– T2
or, = =
 T1 – T2
1–
 The coefficient of performance  =

The coefficient of performance of no refrigerator working between two reservoirs can be
higher than that of Carnot's refrigerator 'cop' of actual refrigerator very from about 2 to 6.

5.3 Cooling in Joule-Thomson Expansion

When a gas escapes adiabatically through a porous plug from region of constant high
pressure to a region of constant low pressure, the cooling is produced. The phenomenon is
called Joule-Thomson effect or adiabatic throttling. The change in temperature depends
upon the nature of the gas as well as initial temperature and difference in pressure. The
fall in temperature is due to the decrease in the internal energy of the gas. The internal
energy decreases because an amount of work is done against the intermolecular attraction.
This experiment can be summarized as;
(i) All the gas show cooling effect at ordinary temperature except hydrogen and helium.
At very low temperature, even hydrogen and helium are cooled.
(ii) The fall in temperature is directly proportional to the difference of pressure on the
two sides of the porous plug.
(iii) The fall in temperature decreases per unit difference of pressure as the initial
temperature of the gas increases.
6 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila
(vi) The fall in temperature becomes zero at a particular temperature called the
temperature of inversion. The cooling is produced below this temperature, but
heating is produced above this temperature.

5.4 Van der Waals' Gas in Joule Thomson Effect

In Joule Thomson expansion in porous plug experiment suppose one gm mole off a
real gas is allowed to expand through a pressure P1 and volume V1 to a pressure P2 and
volume V2. During this process, suppose that the temperature also changes from T1 to T2
due to Joule-Thomson effect.
The net external work done by the gas = P2V2 – P1V1. Now an internal work is also
done by the gas in overcoming the force of molecular attraction. In case of a vander Waals'
gas, the attractive force between the molecule of the gas is equivalent to an internal
a
pressure , where a is a constant.
V2
When the gas expands from a volume V1 to V2 the internal work done by it is given by
V2 V2
a a a
 P dV = 
V2
dV = –
V1 V2
V1 V1
Hence the total work done by the gas
a a
W = (P2V2 – P1V1) + – . . . . (i)
V1 V2
[External work done + Internal energy]
Now Van der Waals' equation of state for one mole of a real gas is.
P + a  (V  b) = RT
 V2
a ab
or, PV + – Pb – 2 = RT
V V
a
or, PV = RT + Pb – . . . . (ii)
V
Neglecting ab being very small
 V2 
a  a a a
 W = RT2 + P2b – – RT + P1b –  + –
 V2  1 V1 V1 V2
2a 2a
 W = R(T2 – T1) + b(P2 – P1) + – . . . . (iii)
V1 V2
Since in equation (ii) a and b are very small we may take approximately.
PV = RT
RT
or, V=
P
 Lectures on Thermodynamics 7
RT1 RT2
 V1 = ; V2 =
P1 P2
Substituting these values in equation (iii) we get,
2aP1 2aP2
W = R(T2 – T1) + b(P2 – P1) + –
RT1 RT2
If T1 and T2 are very nearly equal.
We may write, T1 – T2 = dT and substituting T for T1 and T2.
2a
W = – RdT – b(P1 – P2) + (P – P2)
RT 1
2a
= (P1 – P2)  
RT – b – RdT . . . . (iv)

If Cv is the specific heat of the gas at constant volume, then heat lost by the gas to do
the work W is CvdT i.e., W is equivalent to CvdT cals.
2a
Hence, CvdT = (P1 – P2)  
RT – b – RdT
2a
or, (Cv + R)dT = (P1 – P2)  
RT – b
or, CpdT = (P1 – P2) (2a/RT – b)
(P1 – P2)  2a 
or, dT =
Cp RT – b . . . . (v)

Thus the cooling at any temperature is directly proportional to the fall in the
pressure.
dT 1  2a
= – b
P1 – P2 Cp RT 
We also see that the fall in temperature per unit pressure difference decreases as the
initial temperature T increase from equation (v). Following conditions can be explained.
Cases:
2a
(i) Here P2 < P1 i.e., P1 – P2 is a positive quantity. Those dT will be positive if  
RT – b is
positive
2a 2a
i.e., > b or T <
RT Rb
2a
i.e., cooling will takes place if the initial temperature of gas is less than .
Rb
2a
(ii) Since P1 – P2 is a positive quantity so dT will be zero when  
RT – b = 0
2a
i.e., T =
Rb
8 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila
As dT = 0 so ther will be no change in temperature i.e., neither cooling nor heating is
produced. So this value of temperature is called temperature of inversion and is
denoted by Ti.
2a
(iii) Here P1 – P2 is positive, so dT will be negative only when  
RT – b < negative
2a
or, <b
RT
2a 2a
or, < T since = Ti
Rb Rb
 Ti < T
Hence heating will take place if the temperature of the gas is greater than the
temperature of inversion.
The temperature of inversion of hydrogen and helium are much below the room
temperature (–80° and –240°C) and hence at ordinary temperature these gases show
a heating effect.

5.5 Distinction between Joule Expansion, Joule Thomson Expansion and Adiabatic
Expansion
In Joule expansion, the system is isolated mechanically from the external system and
hence net external work done on the gas is zero. For this process dQ = 0
According to first law of thermodynamics
dQ = dU + dW
or, dU = 0
In Joule's expansion dU = 0, a real gas will always show some cooling effect.
In Joule Thomson expansion, the system is not isolated mechanically from the
external systems and both the piston can move keeping the pressure P 1 and P2 constant.
The net external work done by the gas in passing through the plug W = P 2V2 – P1V1. For
this process dQ = 0.
Applying first law of thermodynamics.
dQ = dU + dW
or, 0 = dU + P2V2 – P1V1
or, dU = P1V1 – P2V2
In Joule-Thomson expansion, there may be cooling effect or a heating effect
depending upon whether P2V2 is greater or smaller than P1V1.
In adiabatic expansion, the system is not mechanically isolated form the external
system. The expanding gas performs external work against the pressure of the atmosphere.
For this process dQ = 0.
W =  PdV
Applying first law of thermodynamics,
dQ = dU + dW
 Lectures on Thermodynamics 9

or, dU = –  PdV
In adiabatic expansion, there will be always a large fall of temperature due to external
work.

5.6 Boyle’s Temperature

According to Boyle’s law and Charle’s law, the equation of state for a perfect gas is
PV = RT . . . . (i)
The Boyle law (PV = constant) is suitable only under ideal conditions (high temperature
and low pressure). It is found experimentally in certain gas such as N2, O2, CO2 that the
value of the product PV decreases initially with increases in pressure, becomes minimum at
a particular pressure and then increases with the increase in pressure. But for hydrogen
the product PV increase steadily with increase in pressure.
A modification was therefore necessary in Boyle's formula. After a long investigation, the
following expression is given for certain temperature.
PV = A + BP + CP2 + DP3 + . . . . . . . (ii)
Where, A, B, C and D etc are constant for a given temperature depending upon the
nature of gas and are called viral coefficients. A is known as 1st virial coefficients. Similarly
B and C are second and third and so on.
At very low pressure, the second, third and other virial coefficients are negligible
 A = RT. equation (ii) reduces to equation (i) and so the Boyle's law is applicable.
The value of B also varies in a similar manner. Its value is negative at low temperature but
gradually increases to zero and becomes positive as the temperature increases. The
temperature at which coefficient B is zero is called the Boyle temperature represented by
TB; because at this temperature Boyle's law holds over a wide range of pressure provided
the constant C,D are negligible.
Thus at Boyle's temperature
d
B= (PV) = 0
dP
PV = A = constant
Now a vander Waals' equation of state for a real gas is
P – a  (V – b) = RT . . . . (iii)
 V2
where a and b are called vander Waals' constants.
a ab
PV – Pb + – = RT
V V2
a ab
or, PV = RT + Pb – + . . . . (iv)
V V2
But PV = RT
RT
or, V=
P
10 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila
aD abP2
or, PV = RT + Pb – +
RT R2T2
a ab
or, PV = RT + b – P + 2 2 P2 . . . . (v)
 RT RT
Comparing this with equation (ii) we get
a  ab
A = RT, B = b – ,C= 2 2 . . . . (vi)
 RT RT
At Boyle temperature, P = TB and B = 0
a
or, 0=b–
RT
a
or, TB =
Rb
As Boyle temperature depends upon a and b and value of a and b are different for different
as. So Boyle temperature is different for different gas. e.g., for nitrogen its value is 50°C, for
hydrogen in 164°C for He, is –250°C.

(i) Below Boyle Temperature

The value of PV first decreases with increases in P, reaches a minimum value and
then begins to increase from equation (ii)
PV = A + BP + CP2 + DP3 + . . . .

Figure
At high pressure, the terms CP2,
DP3 etc are more effective and are positive hence PV
increase which increase in pressure P after reaching a minimum.
(ii) Above Boyle temperature
The product PV increases which increase in P from beginning as coefficient B is
positive above Boyle temperature.
(iii) At Boyle temperature
 Lectures on Thermodynamics 11
The product PV is practically constant for a long range of pressure.

5.7 Critical Temperature

The isothermals of carbondioxide at various temperature was obtained by Andrew are show
in the figure. At 13.1°C the portion AB represents the gaseous state of CO2 and from A to B,

Figure

the gas obeys Boyle's law. From B to C there is enormous decrease in volume with slight
increase in pressure. The portion BC represents the change of CO2 from gas to liquid state.
At C gas has been liquefied completely.
There is no decrease in volume (curve CD). At temperature 21.5°C the curve is
similar but, the horizontal portion FG is less than at 13.1°C. Similarly at temperature
31.1°C the horizontal portion of curve vanishes indicating that the gas cannot be liquefied
by decreasing volume and increasing pressure. The curve at 32.5°C and 48.1°C has the
same behavior but the portion of large compressibility decreases. It is clear that
carbondioxide liquefied only at a temperature below 31.1°C this temperature is called
critical temperature. The temperature below which the gas can be liquefied by the
application of pressure alone is called critical temperature (Tc). The corresponding pressure
and volume of point P are called the critical pressure (Pc) and critical volume (Vc).

5.8 Relation between Boyle Tem, Temperature of Inversion, Critical Temperature

We have temperature of inversion
2a
Ti = . . . . (i)
Rb
12 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila
The Boyle Temperature
a
TB = . . . . (ii)
Rb
8a
And critical temperature (Tc) = . . . . (iii)
27Rb
Here Ti = 2TB
Ti 2a 27Rb
Now, = × = 6.75
Tc Rb 8a
 Ti = 6.75 TC
i.e., Ti = 2TB = 6.75 TC
Thus Ti > TB > TC
8 9 8
or, TC = = T
27 Rb 27 B
27
or, TB = T
8 C

5.9 Regenerative Cooling

The cooling produced in Joule-Thomson expansion of a gas depends on the difference of pressure on the
sides of the porous plug and the initial temperature for most of the gases, the Joule-Thomson cooling is
very small. For example: at a temperature of 20°C when the pressure on the two sides are 50 atmospheres
and 1 atmosphere respectively, the air cools only by 11.7°C. In order to increase the cooling, the pressure
difference was increased; but the cooling did not increase very much. For example, at a temperature of
20°C when the pressure on two sides were kept 210 atmospheres and 1 atmosphere, the air was cooled
only by 42°C. However, the cooling effect can be intensified by employing the process called the
regenerative cooling.

Principle:
In this process a portion of the gas which suffers Joule-Thomson expansion and becomes cooled
is employed to cool other portions of the incoming gas before the later reaches the nozzle to suffer Joule-
Thomson expansion. After suffering the Joule-Thomson expansion at the nozzle, the incoming gas
becomes further cooled. By continuous repetition of this process the temperature of the gas coming out of
the nozzle falls continuously till the gas starts liquefying on the low pressure side. The commutative
process used to cool the gas continuously is called the regenerative cooling.

Experimental Arrangement:
The schematic arrangement of regenerative principle is shown in the figure. The gas is
compressed to a high pressure in the compressor. The heat of compression evolved is. removed by
passing the gas through spiral contained in the water cooled jacket A. The gas next enters the inner tube of
regenerator R and suffers Joule-Thomson expansion at the nozzle V so that it cools by a small amount.
This cooled gas returns by the outer tube and absorbs heat from the incoming high pressure gas before it
reaches the compressor at the same temperature as the incoming gas at R. The gas is again compressed,
cooled by A and re-enters at R. As time passes, the gas approaching V becomes more and more cooled till
the Joule-Thomson cooling at V is sufficient to liquefy the gas. A portion of the escaping gas then
condenses inside the Dewar flask F. At this stage, the temperature of the whole apparatus becomes steady
 Lectures on Thermodynamics 13
and the temperature of the low pressure gas in R which is less than the temperature of the adjacent high
pressure gas at every point of the inner tube. Thus, the low pressure gas extracts heat from the incoming
gas.

Figure

5.10 LIQUEFACTION OF GASES

Liquefaction of oxygen: It was found that gases like oxygen, nitrogen, hydrogen, carbon
monoxide, etc. even when subjected to a pressure of 3000 atmospheres, could not be
liquefied. The cause of this failures was explained by Andrew’s discovery of critical
temperature for various gases. It was shown that a gas when above a temperature (called
critical temperature) cannot be liquefied, however high a pressure it may be subjected to.
It was found that critical temperature of oxygen is –118° C. Oxygen, therefore, must be
cooled to a temperature below this particular temperature if it was to be liquefied. The
apparatus used by Kamerlingh - Onnes is shown in figure.
14 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila

Figure

It consists of three compressor machines A, B and C worked by three pumps P1, P2 and P3 respectively.
Machine A is used to liquefy methyl chloride (CH3Cl) whose critical temperature is 143°C. Hence, i9t
can be liquefied by a pressure of a few atmospheres at a room temperature. The gas is brought to room
temperature by making it flow through a spiral surrounded by water jacket. Liquid methyl chloride is
made to flow round a spiral in B and finally is connected to the suction side of the compressor P1. Liquid
methyl chloride evaporates in B under reduced pressure and this results in a fall of temperature to about
–90°C in this chamber.

Inside the jacket B is placed a condenser coil through which ethylene passes from the
compressor P2 and is cooled to –90°C. It is thus liquefied as its critical temperature is
9.5°C. Liquid ethylene is then made to flow round the spiral in C and is allowed to
evaporate under reduced pressure by connecting it to the suction side of the compressor P2.
The temperature falls to about –160°C which is much below the critical temperature of
oxygen.

Through the spiral in C oxygen under pressure passes, which gets liquefies and is collected
in the vacuum flask. The lowest temperature by boiling liquid oxygen under reduced
pressure is –218°C.

Essential conditions for liquefaction of gases

 Lectures on Thermodynamics 15
The most essential condition for liquefaction of gases are:

(i) For liquefaction of a gas by pressure alone it must be cooled to a temperature below the
critical temperature.

(ii) For liquefaction of a gas by Joule-Thomson expansion it must be cooled to a

temperature below the temperature of inversion.

Worked Out Examples

Example 1:
For one mole of hydrogen, the vander Waals' constants are a = 0.245
litre2 × atoms
, b = 2.67 × 10–2 litre/mole calculate its temperature of
mol2
inversion. Given that R = 2 cal/mole K 1 atmosphere pressure = 106
dynes/cm2.
Hint:
The temperature of inversion T1 is given by
2a
Ti =
Rb
where, a = 0.245 × (1000000) × 106 dynes cm4 /mole2
= 0.245 × 1012 dynes cm4/mole2
b = 2.67 × 10–2 × 1000 cm3/mole
= 26.7 cm3/mole
R = 2 cal/mole K = 2 × 4.2 × 107 ergs/mole K
2 × 0.245 × 1012
Now, T1 = = 218.47 K
2 × 4.2 × 107 × 26.7
Example 2:
Calculate (i) the inversion temperature, (ii) critical expenditure and (iii)
Boyle temperature for nitrogen whose vander Waals' constant are
a = 1.39 atm litre2/mole2 R = 0.082 atm litre/mole degree
b = 0.0391 litre/mole
Hint:
The inversion temperature is given by
2a 2 × 1.39
(i) Ti = = = 867.07 K
Rb 0.082 × 0.0391
(ii) Critical expenditure is given by
8a 8 × 1.39
TC = = = 128.45 K
27Rb 27 × 0.082 × 0.0391
(iii) Boyle temperature is given by
16 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila
a 1.39
TB = = = 433.53 K
Rb 0.082 × 0.0391
Example 3:
Calculate the fall in temperature produced by adiabatic throttling process
of a gm mole of oxygen when the pressure is reduced by 50 atms. The initial
temperature of the gas is 27°C. Given for oxygen Cp = 7.03 cal/mole K.
Hint:
Here,
a = 1.32 litre2 × atms mole–2
= 1.32 × (10–3)2m6 × 105N/m2 mole–2
= 1.32 × 10–6 × 105 Nm4 mole–2
= 0.132 Nm4 mole–2
b = 8.12 × 10–2 litre/mole
= 3.12 × 10–2 × 10–3 m3 mole–1
= 3.12 × 10–5 m3 mole–1
T = 27°C = 300 K, Cp = 7.03 cal/mole K
= 4.2 × 7.02 Joules /mole K
The fall in temperature in adiabatic throttling or Joule Thomson expansion is given
by
dP  2a
dT = – b
Cp RT 
50 × 104 2 × 0.132
= – 3.12 × 10–5
7.03 × 4.2 8.3 × 300 
50 × 105 × 7.48 × 10–5
= = 12.7°C
7.03 × 4.2
Example 4:
Calculate the change in temperature when helium gas suffers Joule
Thomson expansion at –173°C, the pressure difference on the two sides of
the plug being 240 atmospheres. Does the gas show a heating effect or a
cooling effect in this expansion at –173°C. Give R = 8.3 J/K mole. For helium
vander Waals' constants.
Hint:
a = 0.034 /litre2 atmosphere mole–2
b = 0.0237 litre/mole
T1 = –173°C = 100K
dP = 240 atms = 240 × 105 N/m2
R = 8.3 Joule /K mole
a = 0.0341 /litre2 atmosphere mole–2
= 0.034 × (10–3)2 × 105 mole–2
 Lectures on Thermodynamics 17
= 0.0341 × 10–1 Nm4 mole–2
b = 0.0237 litre/mole = 0.0237 × 10–3 /mole
= 0.0237 × 10–3 m3/mole
For monatomic gas like helium
5 5
Cp = R = × 8.3 Joule /K mole
2 2
= 20.75 Joule/K mole
The fall in temperature in Joule Thomson expansion is given by
dP  2a
dT = – b
Cp RT 
240 × 105 2 × 0.0341 × 10–1
= – 0.0237 × 10–3
20.75  8.3 × 100 
= –17.90 K
Thus there is a rise in a temperature equal to 17.9 K.
Example 5:
The vander Waals' constant for hydrogen are
a = 0.247 atmos litre2 mole–2
= 0.247 × 105 × 10–6 m6N/m2 mole2
= 0.0247 Nm4 mole–2
b = 2.65 × 10–2 litre/mole
= 2.65 × 10–5 m3/mole = 2.65 × 10–5 m3/mole
22.4
R= atms litre/mole
273
22.4
K= × 1.01 × 105 × 10–3 mole/K
273
T = 100 K, R = 8.28 Joule mole–1 10–1
dP = 2 × 105 N/m2
(i) Calculate the temperature of inversion T1 = ?
(ii) Fall of temperature T = ? i.e., Joule Thomson cooling.
Hint:
(i) The temperature of inversion is given by
2a 2 × 0.0247
Ti = = = 225.13 K
Rb 8.28 × 2.65 × 10–5
7R
(ii) Here for a diatomic gas like hydrogen Cp =
2
The Joule Thomson cooling is given by
dP  2a
dT = – b
Cp RT 
18 Chapterer-5, Vijay Kumar Jha, Pigauna (Jaleshwar -11), Madhesh Province, Mithila
2 × 105
= (3.316 × 10–5)
28.98
2 × 3.316
=
28.98
 dT = 0.22 K

Example 6:
Calculate the Boyle’s temperature and temperature of inversion for
nitrogen gas whose critical temperature is 126 K. [T. U. 2068]
Solution:
Here, Critical temperature(TC) = 126K
Example 7:
Calculate the change in temperature when helium gas suffers Joules-Thomson
expansion at –10°C. The pressure difference on two sides of the plug is 10
atmosphere and vander Waals' constant for the gas are
a = 0.0341 liter2atmos mole–2
b = 0.0237 litre/mole
R = 8.3 Joule/mole K
Hint:
Here,
dT = ?, T = –10°C = 263K
dP = 10 atmosphere = 10 × 105 N/m2
a = 0.0341 × (10–3)2 m6 × 105 N/m2 mole–2
= 0.0341 × 10–1 Nm4/mole2
b = 0.0237 × 10–3 × m3 /mole
The change in temperature due to Joule Thomson expansion is
dP  2a
dT = – b
Cp RT 
But for monatomic gas Cp = 5/2 R
5
 Cp = × 8.3 = 20.75 J /mole K
2
10 × 105 2 × 10–1 × 0.0341
 dT = – 0.0237 × 10–3
20.75  8.3 × 263 
 dT = 1.11 K

Short-answer questions
1. Why earlier attempts to liquefy Helium gas were unsuccessful?
 Lectures on Thermodynamics 19
Hint: Earlier attempts to liquefy helium gas were unsuccessful because critical
temperature for Helium is 5.3K and temperature of inversion 17K. Both these
temperatures were too low for workers in the field. It was K. Onnes who was able to liquefy
Helium in 1908 by the process of regenerative cooling.

The systematic study of liquefaction of gases started in 1823 when Faraday successfully liquefied
chlorine, CO,, hydrogen sulphide etc. only by cooling them and applying pressure. However-gases like
oxygen, nitrogen, hydrogen and helium etc. could not be liquefied even by applying very high pressure.
Hence, they were termed as permanent gases. Andrew's experiment on CO, in 1862 showed that a gas
must be cooled below its critical temperature before being liquefied under pressure. Real success was
obtained when Joule-Thomson effect is coupled with regenerative cooling.