Marching towards absolute zero temperature.

Motivation

Application of first law and second law of thermodynamics to reactive systems become difficult due to
the non-availability of a standard reference entropy value of various substances. There is a need to
have a reference entropy value for all substances for evaluating the efficiency of a reactive system.
Third law of thermodynamics provides a base value for the entropy.
The third law of thermodynamics was formulated during the early part of twentieth century. The initial
work was done primarily by W. H. Nernst [1864-1941] and Max Planck [1858-1947].

Attaining low temperature

1. Below 5 K is possible by Joule Kelvin expansion, by producing liquid helium.

2. Still lower temperature can be attained by adiabatic demagnetization of a paramagnetic salt.
3. Temperature as low as 0.001 K has been achieved by magnetic cooling.

Magnetic Property

4. Diamagnetic: substance is repelled by magnet

5. Paramagnetic: substance attracted by magnet, such as Iron, Gadolinium sulphate

Adiabatic Demagnetization of a paramagnetic salt:

• Gadolinium sulphate is used here.

• Salt is hung by a fine nylon thread inside the salt tube such that it does not touch the sides.

• Fig: 1.39 Adiabatic demagnetization of a paramagnetic salt

 • The salt is first cooled slightly below 1 K by surrounding it with liquid helium boiling under
reduced pressure.
• Next, the salt is exposed to a strong magnetic field of about 25000 Gauss. Heat produced due
to magnetization of the salt is transferred to the liquid helium without causing an increase in
salt temperature.
• With the magnetic field still present, the inner chamber containing the salt is evacuated of
gaseous helium.
• Finally, the magnetic field is removed. The molecules disalign themselves, which require
energy. This energy is obtained by the salt getting cooler in the process.
• Repetition of the process lowers down the temperature of the salt. Temperature as low as
0.001 K have been achieved so far.

Measurement of temperature

In the neighborhood of absolute zero, all ordinary methods of temperature measurement fail. Curie’s
law gives the most convenient method for measurement of at low temperature (approximately).

1.275

where is the magnetic susceptibility of the salt

T is the absolute temperature
c is the Curie’s constant.

The fundamental features of all cooling process are that the lower the temperature achieved, the
harder it is to go still lower.

Interpretations of adiabatic demagnetization:

• Final temperature Tf ∞ Ti (initial temperature)

• First demagnetization produces a temperature half that at start

• Second demagnetization produces a temperature

• Third demagnetization produces a temperature

• rth demagnetization produces a temperature

Infinite number of adiabatic demagnetizations will be required to attain absolute zero temperature.
FOWLER-GUGGENHEIM STATEMENT OF THIRD LAW:

It is impossible by any procedure, no matter how idealized, to reduce any condensed system to the
absolute zero of temperature in a finite number of operations.
Any isothermal magnetization from 0 to H (magnetic intensity) such as k - i1, f1 - i2 etc. is associated
with the release of heat, i.e., a decrease in entropy (Fig. 1.40).

Fig. 1.40 T-H and T-S diagrams of a paramagnetic substance to show the equivalence of
three statements of the third law

The processes i1 - f1, i2 - f2, i3 - f3 etc. represent reversible adiabatic demagnetizations with temperatures
getting lower and lower. Repeated cycles of isothermal magnetization and adiabatic demagnetization
would bring about a very low temperature. It is seen that [S(T, H) - S(T,0)] decreases as the
temperature decreases, i.e., ΔSIII < ΔSII < ΔSI. Thus, entropy change associated with an isothermal
reversible process of a condensed system approaches zero. It is called Nernst-Simon statement of
third law of thermodynamics.

NERNST-SIMON STATEMENT:

The entropy change associated with any isothermal reversible process of a condensed system
approaches zero.

Another statement of third law can be given like this:

It is impossible by any procedure, no matter how idealized, to reduce the entropy of a system to
zero-point value in a finite number of operations.
Physical and chemical facts which substantiate the third law:

1. For any phase change that takes place at low temperature, Clausius-Clayperon equation hold
good,

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2. From third law of thermodynamics, , since vf - vi is not zero. It shows that

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3. This is substantiated by all known sublimation curves.

6.
Fig. 1.41 The temperature dependence of the change in the Gibbs function and in
the enthalpy for an isobaric process

ΔG = ΔH - TΔs 1.278

4. At low temperature, TΔS is very small.

∴ ΔG = ΔH 1.279

5. Which confirms that .

6. From the Gibbs-Helmholtz equation

1.280
 7. (Fig. 1.41)

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8. Similarly, using Gibbs Helmholtz equation containing U and F

1.282

9.

∴ Cp = Cv = 0 as T → 0 1.283
Solved Problems

Example 1: Two reversible heat engines A and B are arranged in series, A rejecting heat directly to
B. Engine A receives 200kJ at a temperature of 421°C from a hot source, while engine B is in
communication with a cold sink at a temperature of 4.4°C. If the work output of A is twice that of B
find (a) the intermediate temperature between A and B, (b) the efficiency of each engine, and (c) the
heat rejected to the cold sink.

Solution:
Example 2: A reversible heat engine operates between temperature T 1 and T (T1>T). The energy
rejected from this engine is received by s second reversible heat engine at the same temperature T.
the second engine rejects energy at a temperature T 2 (T2<T1). Show that (a) temperature T is the
arithmetic mean of temperature T1 and T2 if the engine produce the same amount of work output, and
(b) temperature T is the geometric mean of temperatures T 1 and T2 if the engine produces the same
cycle efficiency.
Example 3: A reversible engine works between three thermal reservoirs, A, B and C. the engine
absorbs an equal amount of heat from the thermal reservoirs A and B kept at temperature T A and TB
respectively, and rejects heat to the thermal reservoir C kept at temperature T C. The efficiency of the
engine is times the efficiency of the reversible engine, which works between the two reservoirs A and

C. prove that

Solution:
Example 4: A gas is flowing through a pipe at the rate of 2kg/s. Because of inadequate insulation,
the gas temperature decreases from 800°C to 790°C between two sections of the pipe. Neglecting
pressure losses, determine the rate of energy dissipation (degradation) due to this heat loss.
Take To = 300°K, Cp = 1.1 kJ/kg
For the same temperature drop of 10°C, when the gas cools from 80°C to 10°C, due to heat loss,
when would have been the rate of energy degradation. What inference you can draw from this.

Solution:

Considering section 1-1 and 2-2 of the pipe.

Given
Pressure drop Δp = 0
Rate of flow of gas = 2kg/s,
Sp. Heat at constant pressure of gas, Cp = 1.1
kJ/kg-K
Surrounding temperature, T0 = 300K
Temperature at section 1-1,
T1 = 800°C = (800 + 273) K = 1073K
Temperature at section 2-2,
T2 = 790°C = (790 + 273) K = 1063K
Due to inadequate insulation, heat is lost
through the wall of the pipe.
Heat loss,

Keeping the same temperature difference of 10°C both in part I and part II of the problem, it is seen
that the rate of energy degradation is less at low inlet-outlet temperatures. Hence energy loss at low
temperature is qualitatively different from energy loss at low temperatures. Energy at 800°C is
qualitatively superior to energy at 70°C.
Example 5: An ideal gas is flowing through an insulated pipe at the rate of 3.0 kg/s. there is a 10%
pressure drop from inlet to exit of the pipe. Find the energy loss. Take R = 0.287 kJ/kgK, T o = 300K.

Solution:

We have,
Kinetic energy change between sections A-A and B-B = 0
Potential energy change between sections = 0
Change of enthalpy between the section, dh = 0
Applying equation per unit mass flow, we get,
Example 6: Water at 90°C flowing at the rate of 2 kg/s mixes adiabatically with another stream at
30°C flowing at the rate of 1 kg/s. Estimate the rate of entropy generation and rate of energy loss
due to mixing. Take T0 = 300 K.

Solution:
Let Tf be the final temperature of the mixture. Since the mixing is occurring adiabatically, no heat
transfer takes place outside the system. However, heat transfer takes place between the fluids only
due to the temperature.
Example 7: An air pre-heater is used to cool the products of combustion from a furnace for heating
air to be used for combustion. The rate of flow of product is 12.5 kg/s and product cool from 3000C
to 2000C. Rate of air flow is 11.5 kg/s. Initial air temperature is 400C.
Find
(a) Initial and final availability of the products.
(b) What is the energy loss of the process?
(c) If the heat transfer from the products took place reversibly through heat engines what would be
the final temperature of the air?
(d) What power would be developed by the heat engine.

Take
T0 = 300K, Cpg = 1.09 KJ/kg-K, Cpg =1.005 KJ/kg-K
neglecting pressure drop for fluid and heat transfer to the surroundings.

Solution:

Availability of gas at the point of entry to the heat exchanger

Availability of gas at exit,

Therefore decrease in availability of gas,

Similarly, for air

Let the final temperature of air be

Since there is no heat transfer outside the heat exchanger, heat given by the gas is taken by the air.

Availability of air at the outlet,

Availability of gas at the inlet,

Energy loss of the gas = Energy gain of Air + Energy destruction

Part C

Heat is transformed from gas to air reversibly through large number of heat engines.
Therefore entropy generation rate is zero.

Part D
Example 8: Air is flowing through an isolated duct, the pressure and temperature measurements of
the air at two stations are given below

Established the direction of flow of air in the duct. Assume air as an ideal gas having C p = 1.005 and
R = 0.287 KJ/kg

Solution:

Let us assume that air is flowing along the direction P to Q.

Applying Tds equation,

Tds = dh - vdp 1
Since the duct is insulated, no heat transfer takes place between the system and surrounding.
Now,

Tds = CpdT - vdp

or,

Since air is assume to be an ideal gas

PV = RT 3
From equation (3)

From equation (2) and (4) we get,

According to the 2nd law of thermodynamics,

SQ - Sp not less than zero.

Therefore SQ - Sp cannot occur.
Hence, flow can occur only from station Q to P.