4.

The Third and zero Law of Thermodynamics

4.1 Introduction to the Third Law of Thermodynamics

q The third law of thermodynamics states that as the temperature of a system approaches absolute
zero (0 Kelvin or -273.15 degrees Celsius), the entropy of the system also approaches a minimum
value.

q The Third Law of Thermodynamics states that as the temperature of a system approaches absolute
zero, the entropy of the system approaches a minimum value. In other words, at absolute zero (-
273.15 degrees Celsius or 0 Kelvin), the entropy of a perfect crystalline substance is zero. This law
provides a baseline for measuring entropy, as it establishes the minimum possible entropy for a
system.

q Entropy is a measure of the disorder or randomness in a system. The third law of thermodynamics
suggests that at absolute zero, a perfectly ordered crystal lattice would have zero entropy. However,
achieving absolute zero is not practically possible.

q This law also implies that it is impossible to reach absolute zero through any finite number of
processes. As the temperature decreases, the rate at which the temperature approaches absolute
zero slows down. Therefore, the third law of thermodynamics helps us understand the behavior of
materials at extremely low temperatures and provides insights into the behavior of matter under
extreme conditions.

q The third law of thermodynamics is a fundamental principle in the field of thermodynamics, which
deals with the study of energy and its transformations.

q Here are some key points to further understand the third law of thermodynamics:

q Absolute Zero: The third law states that as the temperature of a system approaches absolute zero,
the entropy of the system approaches a minimum value. Absolute zero is the lowest possible
temperature, corresponding to 0 Kelvin or -273.15 degrees Celsius. At this temperature, all molecular
motion ceases, and a system is in its lowest energy state.

q Entropy: Entropy is a measure of the disorder or randomness in a system. It is a thermodynamic

property that quantifies the distribution of energy within a system. The third law suggests that at
absolute zero, a perfectly ordered crystal lattice would have zero entropy because there is no
randomness or disorder present.

q Unattainability of Absolute Zero: The third law also implies that it is impossible to reach absolute
zero through any finite number of processes. As the temperature decreases towards absolute zero,
the rate at which the temperature approaches absolute zero slows down. This phenomenon is known
as the "approach to absolute zero." It means that no matter how close we get to absolute zero, we
can never actually reach it.
q Importance in Low Temperature Physics: The third law of thermodynamics has significant
implications in the study of materials at extremely low temperatures. It helps us understand the
behavior of matter under extreme conditions, such as superconductivity and superfluidity. These
phenomena occur at temperatures close to absolute zero and are based on the principles of
quantum mechanics and the third law.

q Connection to Other Laws: The third law of thermodynamics is related to the first and second
laws of thermodynamics. The first law states the conservation of energy, while the second law
deals with entropy and the direction of energy flow. The third law provides an additional
constraint on the behavior of systems at low temperatures.

q Overall, the third law of thermodynamics provides essential insights into the behavior of matter
at extremely low temperatures and helps us understand the limits and properties of materials
under extreme conditions.

q The relationship between entropy and the third law of thermodynamics is based on the concept
that as the temperature of a system approaches absolute zero, the entropy of the system
approaches a minimum value.

q Entropy is a thermodynamic property that quantifies the disorder or randomness in a system. It

is a measure of the distribution of energy within a system.

q The third law of thermodynamics suggests that at absolute zero, a perfectly ordered crystal
lattice would have zero entropy because there is no randomness or disorder present. This
implies that the entropy of a system decreases as the temperature approaches absolute zero.

q The third law establishes a connection between the behavior of a system at low temperatures
and its entropy. It states that as a system is cooled down, the entropy tends to reach a minimum
value, which corresponds to a perfectly ordered state. This minimum value of entropy is often
referred to as the "ground state" or "zero-entropy state."

q The third law of thermodynamics also implies that it is impossible to reach absolute zero
through any finite number of processes. As the temperature decreases towards absolute zero,
the rate at which the temperature approaches absolute zero slows down. This phenomenon is
known as the "approach to absolute zero." It means that no matter how close we get to
absolute zero, we can never actually reach it.

q In summary, the third law of thermodynamics establishes a relationship between entropy and
temperature. It states that as the temperature approaches absolute zero, the entropy of a
system approaches a minimum value, indicating a state of perfect order. This law helps us
understand the behavior of matter at extremely low temperatures and the limits of entropy in
such systems.
 q The impossibility of reaching absolute zero Kelvin temperature is due to the behavior of matter
at extremely low temperatures and the principles of thermodynamics. Here are a few reasons
why it is impossible:

q Third Law of Thermodynamics: The third law of thermodynamics states that it is impossible to
reach absolute zero temperature through any finite number of processes. As the temperature
approaches absolute zero, the rate of temperature decrease becomes increasingly slow. This
means that it would require an infinite number of steps to reach absolute zero, which is not
feasible in practice.

q Entropy: Entropy is a measure of the disorder or randomness in a system. According to the third
law of thermodynamics, at absolute zero temperature, a system should have zero entropy.
However, achieving absolute zero would require removing all thermal energy from the system,
resulting in a perfectly ordered state with no randomness. This is not possible due to quantum
mechanical effects and the residual entropy associated with them.

q Quantum Mechanical Effects: At very low temperatures, quantum mechanical effects become
significant. One such effect is called "zero-point energy," which is the lowest possible energy
that a quantum mechanical system can have. Even at absolute zero, quantum systems still
possess zero-point energy and exhibit quantum fluctuations. These fluctuations prevent the
system from reaching a state of absolute zero temperature.

q Cooling Limitations: Cooling a system to extremely low temperatures becomes increasingly

difficult as the temperature decreases. Traditional cooling methods, such as refrigeration
techniques, rely on removing heat energy from the system. However, as the temperature gets
closer to absolute zero, the remaining heat energy becomes harder to extract, and the cooling
process becomes less efficient.

q In summary, the impossibility of reaching absolute zero Kelvin temperature is due to the slowing
rate of temperature decrease, the existence of residual entropy, the presence of quantum
mechanical effects, and the limitations of cooling techniques. These factors prevent a system
from ever reaching absolute zero temperature.

4.2 The mathematical expression and equivalent statements of the Third law
thermodynamics

 The Third Law of Thermodynamics can be mathematically expressed as:

lim(T->0) S(T) = 0

 where lim represents the limit, T is the temperature, and S(T) is the entropy of the system at
temperature T. This equation states that as the temperature approaches absolute zero (T->0),
the entropy of the system approaches zero.
  This equation represents the limit as the temperature T approaches absolute zero, the entropy S
of the system approaches zero. It signifies that as the temperature decreases towards absolute
zero, the entropy of the system decreases and reaches a minimum value of zero.

 The mathematical expression of the Third Law of Thermodynamics represents a limit, where T
represents the temperature and S(T) represents the entropy of the system at temperature T.
The expression states that as the temperature (T) approaches absolute zero (0), the entropy of
the system (S(T)) also approaches zero.

 In simpler terms, the Third Law of Thermodynamics states that as a system's temperature
approaches absolute zero, its entropy (a measure of disorder or randomness) approaches zero
as well. This means that at absolute zero temperature, a system should have zero entropy,
indicating a state of perfect order and minimal molecular motion.

 The alternative Equivalent Statements of the Third Law of Thermodynamics are:

1. "The entropy of a perfect crystal at absolute zero temperature is zero."

This statement emphasizes the behavior of a perfect crystal at absolute zero temperature, where the
entropy is zero. It implies that a perfectly ordered crystal lattice has no randomness or disorder at
absolute zero.

2. "It is impossible to reach absolute zero temperature through any finite number of processes."

This statement emphasizes the impossibility of achieving absolute zero temperature using a finite
number of steps or processes. It highlights the fact that the rate of temperature decrease becomes
increasingly slow as it approaches absolute zero.

3. "At absolute zero temperature, a system should have zero entropy."

This statement emphasizes the relationship between temperature and entropy. It states that at absolute
zero temperature, the entropy of a system should be zero. It highlights the connection between the
absence of thermal energy and the absence of disorder or randomness in the system.

4. "As the temperature approaches absolute zero, the rate of temperature decrease approaches
zero."

This statement emphasizes the behavior of temperature decrease as it approaches absolute zero. It
states that as the temperature gets closer to absolute zero, the rate of temperature decrease becomes
slower and slower, eventually approaching zero.

These alternative statements provide different perspectives on the Third Law of Thermodynamics,
highlighting the absence of entropy at absolute zero, the impossibility of reaching absolute zero through
finite processes, and the behavior of temperature decrease as it approaches absolute zero.

Here are the equivalent Alternative Statements of the Third Law of Thermodynamics:
a) It is impossible to reach absolute zero temperature by any finite number of processes.

This statement implies that it is not possible to cool a system down to absolute zero through a finite
number of cooling processes. As the temperature approaches absolute zero, the system's entropy
decreases, but it never reaches zero.

b) The entropy of all perfect crystalline substances approaches zero as the temperature approaches
absolute zero.

This statement implies that as the temperature of a perfect crystalline substance decreases towards
absolute zero, its entropy also decreases and approaches zero. Perfect crystalline substances have a
highly ordered structure, and as the temperature decreases, the disorder or randomness in their atomic
arrangement decreases, resulting in lower entropy.

4.3 Sample practice problems related to the Third law thermodynamics

Here are some sample practice problems related to the Third Law of Thermodynamics along with their
solutions:

1: A system undergoes an isothermal process at a temperature of 10 K. The initial entropy of the system
is 100 J/K. Calculate the final entropy of the system when it reaches absolute zero.

Solution: According to the Third Law of Thermodynamics, the entropy approaches zero as the
temperature approaches absolute zero. Therefore, at absolute zero (0 K), the final entropy of the system
is 0 J/K.

2: A substance has an initial entropy of 50 J/K at a temperature of 20 K. If the substance is cooled to a

temperature of 5 K, calculate the change in entropy.

Solution: Using the Third Law of Thermodynamics, we know that as the temperature approaches
absolute zero, the entropy approaches zero. Therefore, the change in entropy can be calculated as
follows:

Change in entropy = Final entropy - Initial entropy

= 0 J/K - 50 J/K

= -50 J/K

The change in entropy is -50 J/K, indicating a decrease in entropy as the substance is cooled.

3: A system has an initial entropy of 80 J/K at a temperature of 30 K. If the temperature is increased to

100 K, calculate the change in entropy.

Solution: In this case, as the temperature increases, the entropy is expected to increase. The change in
entropy can be calculated as follows:
 Change in entropy = Final entropy - Initial entropy

= S(100 K) - S(30 K)

Since the specific values of entropy at different temperatures are not provided, the exact change in
entropy cannot be determined without specific data.

4: A gas undergoes an adiabatic process from an initial temperature of 300 K to a final temperature of
100 K. If the initial entropy of the gas is 200 J/K, calculate the final entropy.

Solution: In an adiabatic process, there is no heat transfer, so the entropy change is solely due to the
change in temperature. Using the Third Law of Thermodynamics, we know that entropy approaches zero
as the temperature approaches absolute zero. Therefore, the final entropy can be calculated as follows:

Final entropy = Initial entropy + Change in entropy

= 200 J/K + (0 J/K - 200 J/K)

= 0 J/K

The final entropy of the gas is 0 J/K.

5: A solid is heated from 10 K to 50 K. If the initial entropy of the solid is 80 J/K, calculate the change in
entropy.

Solution: The change in entropy can be calculated using the formula:

Change in entropy = Integral (Cp / T) dT

Since the specific heat capacity (Cp) of the solid is not given, we cannot determine the exact change in
entropy without additional information.

6: A system undergoes an irreversible process at a constant temperature of 25 K. If the initial entropy of

the system is 150 J/K, calculate the final entropy.

Solution: In an irreversible process, the entropy change cannot be determined without additional
information about the specific process or the system. Therefore, the final entropy cannot be calculated
without further data.

7: Calculate the change in entropy when a perfect crystalline substance is cooled from 100°C to absolute
zero.

Solution: According to the Third Law of Thermodynamics, the entropy of a perfect crystalline substance
at absolute zero is zero. Therefore, the change in entropy is given by:

ΔS = S_final - S_initial

ΔS = 0 - S_initial
 ΔS = -S_initial

8: Determine the entropy change when a system at 300 K is cooled to 10 K.

Solution: Since the Third Law of Thermodynamics states that entropy approaches zero at absolute zero,
we can assume that the entropy at 10 K is negligible compared to the entropy at 300 K. Therefore, the
change in entropy can be approximated as:

ΔS ≈ S_final - S_initial

ΔS ≈ 0 - S_initial

ΔS ≈ -S_initial

9: A sample of an ideal gas undergoes an isothermal compression from 1 bar to 10 bar at a temperature
of 273 K. Calculate the change in entropy of the gas.

Solution: Since the process is isothermal, the temperature remains constant. According to the Third Law
of Thermodynamics, the entropy change of an ideal gas during an isothermal process is given by:

ΔS = nR ln(V_final/V_initial)

where n is the number of moles of the gas, R is the ideal gas constant, V_final is the final volume, and
V_initial is the initial volume. By substituting the given values into the equation, you can calculate the
change in entropy.

4.4 Review Multiple Choice Questions the Third law thermodynamics

Here are some multiple-choice questions on the Third Law of Thermodynamics, along with their
answers:

1. The Third Law of Thermodynamics states that the entropy of a perfect crystal at absolute zero is:

a) Zero

b) Infinity

c) Constant

d) Unknown

Answer: a) Zero

2. The Third Law of Thermodynamics is also known as:

a) Law of Conservation of Energy

b) Zeroth Law of Thermodynamics

 c) First Law of Thermodynamics

d) Second Law of Thermodynamics

Answer: b) Zeroth Law of Thermodynamics

3. The Third Law of Thermodynamics is based on the concept of:

a) Heat transfer

b) Entropy

c) Temperature

d) Pressure

Answer: b) Entropy

5. The Third Law of Thermodynamics implies that absolute zero is:

a) The lowest possible temperature

b) The highest possible temperature

c) A temperature that cannot be reached

d) None of the above

Answer: a) The lowest possible temperature

6. The Third Law of Thermodynamics is a consequence of:

a) The Law of Conservation of Energy

b) The Law of Conservation of Mass

c) The Law of Conservation of Momentum

d) The Law of Conservation of Entropy

Answer: d) The Law of Conservation of Entropy

7. The Third Law of Thermodynamics is used to calculate:

a) Heat transfer

b) Work done

c) Change in entropy
 d) Change in temperature

Answer: c) Change in entropy

10. The Third Law of Thermodynamics is most closely related to which other law of thermodynamics?

a) First Law

b) Second Law

c) Zeroth Law

d) None of the above

Answer: c) Zeroth Law

11. The Third Law of Thermodynamics helps in determining the:

a) Heat capacity of a system

b) Heat transfer rate

c) Enthalpy change

d) Absolute entropy of a substance

Answer: d) Absolute entropy of a substance

12. The Third Law of Thermodynamics can be used to calculate the change in entropy of a system by
integrating the equation:

a) ΔS = Q/T

b) ΔS = Cp ln(T2/T1)

c) ΔS = Cp ln(P2/P1)

d) ΔS = Cp ln(V2/V1)

Answer: b) ΔS = Cp ln(T2/T1)

13. The Third Law of Thermodynamics is based on the assumption that the entropy of a system at
absolute zero is:

a) Zero

b) Infinity

c) Constant
 d) Unknown

Answer: a) Zero

15. The Third Law of Thermodynamics is a consequence of which principle?

a) Principle of Equilibrium

b) Principle of Conservation of Energy

c) Principle of Entropy

d) Principle of Mass Conservation

Answer: c) Principle of Entropy

16. The Third Law of Thermodynamics states that it is impossible to reach absolute zero temperature
through any finite number of:

a) Isothermal processes

b) Adiabatic processes

c) Reversible processes

d) Irreversible processes

Answer: d) Irreversible processes

18. The Third Law of Thermodynamics is used to determine the entropy change of a substance at a given
temperature by comparing it to the entropy of the substance at:

a) Absolute zero

b) Room temperature

c) Boiling point

d) Melting point

Answer: a) Absolute zero

19. The Third Law of Thermodynamics is often used in the study of:

a) Chemical reactions

b) Heat engines

c) Phase transitions
 d) None of the above

Answer: c) Phase transitions

20. The Third Law of Thermodynamics helps in understanding the behavior of matter at:

a) High pressures

b) Low temperatures

c) High temperatures

d) Normal conditions

Answer: b) Low temperatures

1. Which of the following statements best defines the Third Law of Thermodynamics?

a) The entropy of a system approaches zero as the temperature approaches absolute zero.

b) Energy cannot be created or destroyed in a system.

c) Heat flows from a higher temperature to a lower temperature.

d) The pressure of a gas is inversely proportional to its volume at constant temperature.

Answer: a) The entropy of a system approaches zero as the temperature approaches absolute zero.

2. What is the mathematical expression of the Third Law of Thermodynamics?

a) Q = mcΔT

b) PV = nRT

c) ΔS = 0

d) ΔU = Q - W

Answer: c) ΔS = 0

3. Which of the following is an equivalent statement of the Third Law of Thermodynamics?

a) The entropy of all perfect crystalline substances approaches zero as the temperature approaches
absolute zero.

b) Energy is conserved in a closed system.

c) Heat always flows from a region of higher temperature to a region of lower temperature.

d) The pressure of a gas is directly proportional to its temperature at constant volume.

Answer: a) The entropy of all perfect crystalline substances approaches zero as the temperature
approaches absolute zero.

4. What is the significance of absolute zero in the Third Law of Thermodynamics?

a) It represents the lowest possible temperature.

b) It is the temperature at which all molecular motion ceases.

c) It is the temperature at which the entropy of a perfect crystalline substance is zero.

d) It is the temperature at which the pressure of a gas becomes zero.

Answer: c) It is the temperature at which the entropy of a perfect crystalline substance is zero.

5. Which of the following statements is true about the Third Law of Thermodynamics?

a) It only applies to ideal gases.

b) It states that entropy is conserved in a closed system.

c) It provides a baseline for measuring entropy.

d) It describes the relationship between heat and temperature.

Answer: c) It provides a baseline for measuring entropy.

6. Which law of Thermodynamics is also known as the "Law of Conservation of Entropy"?

a) First Law of Thermodynamics

b) Second Law of Thermodynamics

c) Third Law of Thermodynamics

d) Zeroth Law of Thermodynamics

Answer: c) Third Law of Thermodynamics

13. Which of the following statements is true about the Third Law of Thermodynamics?

a) It states that energy cannot be created or destroyed in a system.

b) It describes the relationship between heat and temperature.

c) It provides a baseline for measuring entropy.

d) It states that heat always flows from a higher temperature to a lower temperature.

Answer: c) It provides a baseline for measuring entropy.

14. True or False: The Third Law of Thermodynamics applies to all substances, regardless of their nature
or composition.

Answer: False

15. The Third Law of Thermodynamics is most applicable to which type of substances?

a) Perfect gases

b) Ideal solutions

c) Perfect crystalline substances

d) Amorphous materials

Answer: c) Perfect crystalline substances

16. The Third Law of Thermodynamics states that the entropy of a perfect crystalline substance
approaches zero as the temperature approaches:

a) Absolute zero

b) 0°C

c) The boiling point of the substance

d) The melting point of the substance

Answer: a) Absolute zero

17. What is the significance of the Third Law of Thermodynamics in relation to absolute zero?

a) It establishes the concept of thermal equilibrium.

b) It defines the concept of entropy.

c) It provides a baseline for measuring entropy.

d) It represents the lowest possible temperature.

Answer: c) It provides a baseline for measuring entropy.

18. True or False: The Third Law of Thermodynamics states that it is impossible to reach absolute zero
temperature.

Answer: False

20. True or False: The Zeroth Law of Thermodynamics states that heat always flows from a higher
temperature to a lower temperature.
Answer: False