3.

The Second Law of Thermodynamics

3.1 Introduction to the Second Law of Thermodynamics

q The second law of thermodynamics states that the total entropy of an isolated system can never
decrease over time, and is constant if and only if all processes are reversible. In simpler terms, it
implies that natural processes tend to move towards a state of greater disorder or
randomness.The

q second law of thermodynamics is a fundamental principle in physics that helps us understand

how energy behaves in the universe.

q This law states that in any natural process, the total entropy of an isolated system will always
increase or remain the same. Entropy is a measure of the disorder or randomness in a system.
So, the second law tells us that the disorder or randomness of a closed system will either stay
the same or increase over time.

q In simpler terms, it means that things tend to naturally move from a state of order to a state of
disorder. For example, if you leave a hot cup of coffee in a room, it will eventually cool down
and reach the same temperature as the room. This is because the heat energy from the coffee
spreads out and becomes more evenly distributed in the room, increasing the overall disorder or
entropy.

q The second law of thermodynamics also explains why certain processes are irreversible. Once
something becomes more disordered, it is highly unlikely to spontaneously become ordered
again without external intervention.

q Overall, the second law of thermodynamics helps us understand how energy flows in the
universe and why certain processes occur in the direction they do.

q The second law of thermodynamics states that the total entropy of an isolated system will
always increase or remain the same over time. Entropy is a measure of the disorder or
randomness in a system. This law implies that in any natural process, the overall disorder or
randomness of a closed system will either stay the same or increase. In simpler terms, things
tend to naturally move from a state of order to a state of disorder. It also explains why certain
processes are irreversible and why it is highly unlikely for a disordered system to spontaneously
become ordered again without external intervention.

q The Second Law of Thermodynamics states that the total entropy of an isolated system can
never decrease over time, and it tends to increase in natural processes.

q Reversible Cyclic Heat Engines Process

q Cyclic TD Process: is just a sequence of energy transferring TD process that repeat themselves in
the same order.Cyclic Process are important because, they allow us to run through the same
 energy transferring process again and again, instead of limiting us doing the same process once
or for few number of cycles.Reversible cyclic Heat engines (Carnot Cycle engines) : are machines
or systematic devices that are used to convert heat energy in to some useful continuous
mechanical /electrical work or other forms of energy.

q With an intention to improve the efficiency of steam engines and get more continuous
mechanical work as an out put, a French engineer Sadi Carnot made both a hypothetical and
theoretical investigation on reversible cyclic heat engines.The result of his hypothetical and
theoretical investigation on reversible cyclic heat engines leads to the foundation of new TDs
state function and the formulation of the second law of TDs.
 q“The efficiency of any cyclic reversible heat engines
depends only on the temperature of the reservoirs . it is
independent of the nature of the engine, working substance
or the type of the work performed.”

3.2 The mathematical expression and the equivalent statements of the

Second laws of thermodynamics

One of the mathematical expressions of the second law is given by:

dS=dq/dT

where dS is the change in entropy, dq is the heat added to the system, and dT is the temperature.
Equivalently, it can be stated as the entropy of an isolated system never decreases.

The second law of thermodynamics can be expressed mathematically in different ways. Here are some
alternative equivalent statements of the second law:

1. Clausius Statement::

∮ δQ/T ≤ 0

This statement states that it is impossible to construct a device that operates in a cycle and extracts heat
from a single reservoir and converts it entirely into work.

2. Kelvin-Planck Statement::

It is impossible for any device that operates in a cycle to receive heat from a single reservoir and
produce an equivalent amount of work without any other effects.

3. Entropy Statement::

ΔS ≥ 0

This statement indicates that the total entropy of an isolated system always increases or remains
constant, but never decreases. Entropy is a measure of the disorder or randomness in a system.

4. Caratheodory Statement::
 Every equilibrium state of a closed system is characterized by certain parameters, and it is possible to
construct a function, called entropy, which increases or remains constant during any reversible process
and does not decrease during any irreversible process.

These different expressions of the second law of thermodynamics all convey the same fundamental
concept that certain processes are irreversible, and the overall entropy of an isolated system tends to
increase or stay the same.

3.3 Sample practice problems related to the Second law of thermodynamics

Here are 10 Sample practice problems related to the Second Law of Thermodynamics given below
which maily focus on:

- Calculating the change in entropy for a given process.

- Determining the direction of heat flow based on entropy change.

- Analyzing the efficiency of heat engines based on the second law.

Here are 10 sample practice problems related to the Second Law of Thermodynamics, along with their
solutions:

1. Problem: A refrigerator operates between two reservoirs at temperatures of 5°C and 25°C. Determine
the maximum coefficient of performance (COP) for the refrigerator.

Solution: The maximum coefficient of performance (COP) for a refrigerator is given by COP = Tc/(Th -
Tc), where Tc is the temperature of the cold reservoir and Th is the temperature of the hot reservoir.
Plugging in the values, we get COP = 5/(25 - 5) = 0.25.

2. Problem: A heat engine operates between two reservoirs at temperatures of 1000°C and 25°C.
Calculate the maximum theoretical efficiency of the heat engine.

Solution: The maximum theoretical efficiency of a heat engine is given by η = 1 - (Tc/Th), where Tc is
the temperature of the cold reservoir and Th is the temperature of the hot reservoir. Plugging in the
values, we get η = 1 - (25/1000) = 0.975.

3. Problem: A heat pump is used to heat a room by extracting heat from the outside environment at 0°C.
If the room is to be maintained at 20°C and the heat pump has a COP of 4, calculate the temperature of
the heat source.

Solution: The coefficient of performance (COP) for a heat pump is given by COP = Th/(Th - Tc), where
Th is the temperature of the heat source and Tc is the temperature of the cold reservoir. Rearranging
the equation, we get Th = Tc + (COP * Tc). Plugging in the values, we get Th = 0 + (4 * 0) = 0°C.

4. Problem: A steam power plant operates at a boiler temperature of 600°C and a condenser
temperature of 30°C. Calculate the maximum theoretical efficiency of the power plant.
 Solution: The maximum theoretical efficiency of a heat engine operating between two reservoirs is
given by η = 1 - (Tc/Th), where Tc is the temperature of the condenser and Th is the temperature of the
boiler. Plugging in the values, we get η = 1 - (30/600) = 0.95.

5. Problem: A Carnot engine operates between two reservoirs at temperatures of 400°C and 100°C. If
the engine absorbs 2000 J of heat from the high-temperature reservoir, calculate the work output of the
engine.

Solution: The work output of a Carnot engine is given by W = Qh - Qc, where Qh is the heat absorbed
from the high-temperature reservoir and Qc is the heat rejected to the low-temperature reservoir.
Plugging in the values, we get W = 2000 J - (1000 J) = 1000 J.

6. Problem: A heat engine operates with an efficiency of 40% and absorbs heat at a rate of 500 J/s.
Determine the rate at which work is produced by the engine.

Solution: The rate of work produced by a heat engine is given by W = η * Qh, where η is the efficiency
of the engine and Qh is the rate of heat absorbed. Plugging in the values, we get W = 0.4 * 500 J/s = 200
J/s.

7. Problem: A heat pump is used to cool a room by extracting heat from the room and rejecting it to the
outside environment. If the room is at 30°C and the outside environment is at 40°C, determine the
minimum power input required to cool the room at a rate of 500 J/s.

Solution: The power input required by a heat pump is given by P = Qc / COP, where Qc is the rate of
heat rejected and COP is the coefficient of performance. Plugging in the values, we get P = 500 J/s / COP.

8. Problem: A heat engine operates between two reservoirs at temperatures of 500 K and 300 K. If the
engine has a work output of 1000 J, determine the heat input and heat rejection of the engine.

Solution: The heat input of a heat engine is given by Qh = W + Qc, where Qh is the heat input, W is the
work output, and Qc is the heat rejected. Plugging in the values, we get Qh = 1000 J + Qc.

9. Problem: A refrigerator operates between two reservoirs at temperatures of -10°C and 30°C.
Determine the coefficient of performance (COP) for the refrigerator.

Solution: The coefficient of performance (COP)

Certainly! Here are a few more sample practice problems related to the Second Law of
Thermodynamics:

10. Problem: A carnot engine operates between two reservoirs at temperatures of 500°C and 100°C. If
the engine absorbs 2000 J of heat from the high-temperature reservoir, calculate the heat rejected to
the low-temperature reservoir.
 Solution: The heat rejected to the low-temperature reservoir by a Carnot engine is given by Qc = Qh -
W, where Qc is the heat rejected, Qh is the heat absorbed from the high-temperature reservoir, and W
is the work output. Plugging in the values, we get Qc = 2000 J - (1000 J) = 1000 J.

11. Problem: A heat pump is used to maintain a room at a temperature of 25°C by extracting heat from
the outside environment at -10°C. If the heat pump has a COP of 3, calculate the rate at which heat is
supplied to the room.

Solution: The rate at which heat is supplied to the room by a heat pump is given by Qh = COP * Qc,
where Qh is the rate of heat supplied and Qc is the rate of heat extracted from the outside environment.
Plugging in the values, we get Qh = 3 * Qc.

12. Problem: A refrigerator operates between two reservoirs at temperatures of 0°C and 20°C. If the
refrigerator requires a power input of 400 J/s, calculate the rate at which heat is extracted from the cold
reservoir.

Solution: The rate at which heat is extracted from the cold reservoir by a refrigerator is given by Qc =
P / COP, where Qc is the rate of heat extracted, P is the power input, and COP is the coefficient of
performance. Plugging in the values, we get Qc = 400 J/s / COP.

13. Problem: A heat engine operates at a boiler temperature of 800°C and a condenser temperature of
100°C. If the engine has a work output of 500 J, calculate the heat input and heat rejection of the
engine.

Solution: The heat input of a heat engine is given by Qh = W + Qc, where Qh is the heat input, W is the
work output, and Qc is the heat rejected. Plugging in the values, we get Qh = 500 J + Qc.

14. Problem: A heat pump is used to cool a room by extracting heat from the room and rejecting it to
the outside environment. If the room is at 25°C and the outside environment is at 40°C, determine the
coefficient of performance (COP) for the heat pump.

Solution: The coefficient of performance (COP) for a heat pump is given by COP = Qc / W, where Qc is
the rate of heat rejected and W is the rate of work input. Plugging in the values, we get COP = Qc / W.

15. Problem: A refrigerator operates between two reservoirs at temperatures of 10°C and 30°C. If the
refrigerator requires a power input of 500 J/s, calculate the rate at which heat is extracted from the cold
reservoir.

Solution: The rate at which heat is extracted from the cold reservoir by a refrigerator is given by Qc =
P / COP, where Qc is the rate of heat extracted, P is the power input, and COP is the coefficient of
performance. Plugging in the values, we get Qc = 500 J/s / COP.

These practice problems should give you a good understanding of the concepts related to the Second
Law of Thermodynamics and help you strengthen your problem-solving skills in this area.

3. 4 Review Multiple Choice Questions on the Second law of thermodynamics

Multiple-choice questions may focus on:

- Understanding the implications of the second law in different scenarios.

- Applying mathematical expressions and principles related to entropy change.

- Identifying reversible and irreversible processes based on entropy considerations.

Here are some multiple-choice questions related to the Second Law of Thermodynamics along with brief
answers:

CH-3 THE SECOND LAW OF THERMODYNAMICS (10 MCQS)-46

1. Which of the following statements best describes the Second Law of Thermodynamics?
a) The internal energy of the universe is constant.

b) Energy can be neither created nor destroyed.

c) When an isolated system undergoes a spontaneous change, the entropy of the system
will increase.

d) At absolute zero, the entropy of a perfect crystal is considered to be zero.

2. ____________ are machines or systematic devices that are used to convert heat energy in
to some useful continuous mechanical or to other forms of energy.
A) Air Pump B) Ventilator C) Refrigerator D) Carnot engine
3. _____________ is a thermodynamic state function which measures the energy degradation
or the loss of the capacity to do some kind of work by the system during a particular
thermodynamic process.
A) Enthalpy B) Gibb’s Free Energy C) Entropy D) Internal Energy
4. ___________________ are devices that are used for removing heat from cold temperature
reservoir towards hot temperature reservoir by using an externally supplied either
electric power (mechanical work done as input).
A) Carnot heat engine B) Reverse Heat Engine C) Internal Combustion Engine D)
None of the above
5. Which one of the following is a remarkable result we got from the theoretical
investigation of the thermal efficiency of Carnot cycle engines?
(A)The thermal efficiency to be only depends on the temperatures of the heat
reservoirs
(B)The thermal efficiency to be depends on the technological advancement of the
engine.
(C) The thermal efficiency to be only depends on the thermal energy of the heat
reservoirs
 (D)The thermal efficiency to be depends on the nature of the working substance (i.e
petrol, diesel or natural gas)
(E)A and C are the correct answer
(F) None of the above
6. Which one of the following statement is true?
(A)It is possible to practically attain an absolute zero kelvin temperature
(B)It is due to the poor technology and the nature of the working substance which
makes the thermal efficiency of heat engine to be less than 1 or 100%.
(C) It is possible to construct a device that operates in a cycle with greater than 1 or
100% thermal efficiency
(D)The major objective of the second law of thermodynamics is that to determine the
energy flow direction for a given TD process.
(E)It is possible for a device operating in a cyclic manner to completely covert heat into
either continuous mechanical, electrical or chemical work.

7. Which one of the following is not under the category of reverse heat engines?
(A)Heat pump
(B)Air Conditioner
(C) Carnot Cycle engine
(D)Refrigerator
(E)All of the above
8. Which one of the following is different from the others?
(A)Petrol Engine
(B)Steam engine
(C) Heat Pump
(D)Carnot Cycle engine
Which one of the following is not true about Carnot Cyclic Heat Engine?
Which one of the following is not true about reversible cyclic heat engine?
Second and Third Law of Thermodynamics and Entropy

9. Carnot cycle is a reversible cycle

(A)True

(B)both are correct

(C) false

(D)both are incorrect

10. A reversible cycle has following processes

(A)4 isothermal processes

 (B)4 adiabatic process

(C) 2 isothermal and 2 adiabatic processes

(D)none of the mentioned

11. The correct sequence of the processes taking place in a carnot cycle is…….

(A)adiabatic- adiabatic- isothermal- isothermal

(B)adiabatic- isothermal- adiabatic_ isothermal

(C) isothermal-isothermal adiabatic –adiabatic

(D)isothermal -adiabatic isothermal-adiabatic.

12. The reversed heat engine takes hit from a………. temperature body then discharges it to
a…………. temperature body and …………….an inward flow of network.

(A)high, low, receives

(B)low, high, receives

(C) high,low,gives

(D)low , high , gives

13. Example of reverse heat engine is………….

(A)heat pump

(B)refrigerator

(C) both of the mentioned

(D)none of the mentioned

14. The efficiency of all reversible heat engines operating between the same heat reservoirs
is…….

(A)Same

(B)independent of the nature of the working substance

(C) independent of the amount of working substance

(D)all of this

15. Efficiency of reversible heat engine is…..

 (A)1-(T1/T2) (B) 1-(T2/T1) (C) (T1/T2)-1 (D) (T2/T1)-1

16. Integral of DQ/T of a reversible heat engine is given by…

(A)Si-Sf

(B)Sf-Si

(C) Si+ Sf

(D)-Si-Sf

17. Entropy is a……….

(A)path function, intensive property

(B)path function, extensive property

(C) point function intensive property

(D)point function extensive property

18. For reversible process,

(A)dS=dQ/T

(B)dS>dQ/T

(C) dS<dQ/T

(D)none of the mentioned

19. For irreversible process,

(A)dS=dQ/T

(B)dS>dQ/T

(C) dS<dQ/T

(D)none of the mentioned

20. The entropy of an isolated system can never,

(A)increase

(B)decrease

(C) be zero
 (D)none of the mentioned

21. The enthalpy of a substance is defined as

(A)H=U-PV

(B)H= U+PV

(C) H=-U+PV

(D)H=-U-PV

22. In a constant volume process, internal energy change is equal to

(A)heat transferred

(B)work done

(C) zero

(D)none of the mentioned

23. Enthalpy is an intensive property of a system.

(A)True

(B)both are correct

(C) false

(D)both are incorrect

24. For an Ideal gas , Enthalpy becomes………….

(A)H=U-RT (B) H=-U-RT (C) H=U+RT (D) H=-U+RT

25. heat transferred at constant pressure ………….the enthalpy of a system

(A)Decreases

(B)Increases

(C) first decreases then increases

(D)first increases then decreases

26. The enthalpy and internal energy are the function of temperature for

(A)all gases
 (B)steam

(C) water

(D)ideal gas

27. In Carnots heat engine……………. is used as working substance.

(A)Petrol

(B)ideal gas

(C) diesel

(D)ammonia

28. The enthalpy of a substance is defined as

(A)H=U-PV

(B)H= U+PV

(C) H=-U+PV

(D)H=-U-PV

29. Efficiency of carnot s ideal heat engine is always

(A)Zero

(B)equal to 1

(C) greater than 1

(D)less than 1

30. In an atto engine heat is observed by the working substance at constant…………

(A)pressure

(B)volume

(C) temperature

(D)entropy

31. Entropy of the system always………… in a reversible system

(A)increases
 (B)decreases

(C) remains constant

(D)zero

32. Entropy of a system always …………in an irreversible system

(A)increases

(B)decreases

(C) remains constant

(D)zero

33. All the natural processes occurring in the universe are

(A)irreversible

(B)reversible

(C) both (a) and (b)

(D)none of this

34. The entropy of the universe is always tending towards

(A)Minimum

(B)Zero

(C) Maximum

(D)none of this

_______

35. Efficiency of carnot s heat engine is always…………

(A)less than 1

(B)greater than 1

(C) equal to 1

(D)zero
36. The working substance is atto engine is………..

(A)petrol vapour and air

(B)petrol

(C) oil and air

(D)oil

37. Otto cycle is perfectly………

(A)Irreversible and reversible

(B)Reversible

(C) Irreversible

(D)none of the above

38. In atto engine working substance is

(A)Air

(B)oxygen 1

(C) oil vapour

(D)none of this

39. In atto engine……….. vapour is used as a fuel

(A)heavy oil

(B)ethanol

(C) petrol

(D)oil

40. The working substance in a diesel engine is

(A)Air

(B)Petrol

(C) oil and air

(D)oil
41. The practical efficiency of diesel engine is about

(A)55 %

(B)45 %

(C) 50%

(D)none of the above

42. The diesel engine heat is observed by the working substance at

(A)constant volume

(B)constant pressure

(C) constant temperature

(D)none of the above

43. A heat engine:

(A)converts heat input to an equivalent amount of work

(B)converts work to an equivalent amount of heat

(C) takes heat in, does work, and loses energy heat

(D)uses positive work done on the system to transfer heat from a low temperature
reservoir to a high temperature reservoir

(E)uses positive work done on the system to transfer heat from a high temperature
reservoir to a low temperature reservoir

44. A heat engine that in each cycle does positive work and loses energy as heat, with no
heat energy input, would violate:

(A)the zeroth law of thermodynamics

(B)the first law of thermodynamics

(C) the second law of thermodynamics

(D)the third law of thermodynamics

(E)Newton's second law

45. A Carnot cycle:

 A) is bounded by two isotherms and two adiabats on a p-V graph

B) consists of two isothermal and two constant volume processes

C) is any four sided process on a p-V graph

D) only exists for an ideal gas

E) has an efficiency equal to the enclosed area on a p-V diagram

46. A Carnot engine operates between 200°C and 20°C. Its maximum possible efficiency is:

A) 90% B) 100% C) 38% D) 72% E) 24%

CH-5 ENTHALPY AND GIBBS FREE ENERGY CHANGE (10 MCQS) -

13
1. When a chemical reaction occurs in nature, it tries to satisfy two opposing
tendencies:

(A) Minimization of energy and Maximization of entropy

(B) Minimization of entropy and Maximization energy

(C) __________

(D) __________

Answer:

2. Which of the following is correct for a spontaneous reaction at any

temperature?

(A) ∆H=−ve, ∆S=+ve, ∆G=−ve

(B) ∆H=−ve, ∆S=−ve, ∆G=−ve

(C) ∆H=+ve, ∆S=+ve, ∆G=−ve

(D) ∆H=−ve, ∆S=+ve, ∆G=+ve

 Solution : Correct option is (A). For a spontaneous reaction at any
temperature ΔH=−ve, ΔS=+ve, ΔG=−ve. We know that, ΔG=ΔH−TΔS and
for spontaneous processes, the change in Gibbs free energy is negative.
This is possible at all temperatures when enthalpy change is negative and
entropy change is positive.

3. For spontaneous reaction, ∆G is :

(A) Negative (-ve)

(B) Positive (+ve)

(C) Zero

(D) None of the above

Solution: Correct option is (A). For a spontaneous reaction, the sign on ΔG

must be negative. Gibbs free energy relates enthalpy, entropy and
temperature. A spontaneous reaction will always occur when ΔH is
negative and ΔS is positive. Hence, option A is correct.

4. In reaction ∆H and ∆S both are positive. In which of the following case, the
reaction would not be spontaneous?

(A) ∆H > TΔS

(B) TΔS > ∆H

(C) ∆H = TΔS

(D) All of the above

Solution : Correct option is (C)

 Gibbs free energy ΔG=ΔH−TΔS. When ΔG is negative (TΔS>ΔH), a process
or chemical reaction proceeds spontaneously in the forward direction.
When ΔG is positive (ΔH>TΔS), the process proceeds spontaneously in
reverse. When ΔG is zero, (ΔH=TΔS) the process is already in equilibrium,
with no net change taking place over time.

5. In a reaction ΔH and ΔS both are positive. In which of the following cases,

the reaction would not be spontaneous?

(A) ∆H > TΔS

(B) ∆H = TΔS

∆H
(C) ΔS = T

(D) All of the above

Solution: Correct option is (D)

In a reaction ΔH and ΔS both are positive. In the following cases, the

reaction would not be spontaneous

(A) ΔH>TΔS: The reaction is non spontaneous. Due to this ΔG>0

(B) ΔH=TΔS : The reaction is at equilibrium. Due to this ΔG=0

∆H
(C) ΔS= T : The reaction is at equilibrium. Due to this ΔG=0

But the reaction will be spontaneous when ΔH<TΔS. Due to this ΔG<0

6. The equilibrium constant for a reaction is 10. what will be value of △G° ? R
=8.314 JK−1mol−1 , T=300 K
 (A)

Solution: ΔG0 =−2.303RTlogK=−2.303×8.314×300log10=−5.744kJ/mol

7. For the reaction, 2Cl(g) → Cl2 (g), the signs of ΔH and ΔS respectively, are

(A) +, -

(B) +, +

(C) -, -

(D) -, +

Solution: Correct option is (C). Entropy is decreasing (−ve) in the reaction

as no. of molecules are decreasing which reduces the randomness of the
system. Further the reaction is exothermic since a bond is being formed,
i.e., △H is also −ve. Hence, option C is correct

8. The values of ΔH and ΔS for the reaction, C (graphite) + CO2(g) → 2CO(g)

are 170 kJ and 170JK−1 respectively. This reaction will be spontaneous at:

(A) 510K

(B) 710K

(C) 910K

(D) 1010K

Solution: Correct option is (D). For a spontaneous reaction, △G= negative

and at equilibrium △G=0 (i.e. when △H=T△S)

170× 10
⇒T= 170
=1000K
 Therefore, at this temperature, reaction is at equilibrium i.e. △G=0 and
above this temperature △G will be negative and reaction will be
spontaneous.

9. For a given reaction, ΔH=35.5 kJmol−1 and ΔS = 83.6 kJmol−1K-1. The reaction is
spontaneous at: (Assume that ΔH and ΔS do not vary with temperature)

(A) T > 425 K

(B) At any temperature

(C) T > 298 K

(D) T < 425 K

Answer: Correct option is (A). We are given that: ΔH= 35.5 kJmol−1 and ΔS
= 83.6 kJmol−1 K-1. The reaction is spontaneous if ΔG<0 and non-
spontaneous if ΔG>0. As we know that, ΔG=ΔH−TΔS and the reaction is
spontaneous when ΔG<0. So that,

ΔH−TΔS < 0

J
35500
∆H mole
⇒T> ∆S = J
= 425K
83600
mole . K

∴ T > 425K

Hence, the reaction will be spontaneous when the temperature is above

425K.

10. In which case, a spontaneous reaction is possible at any temperature?

(A) ∆H=−ve, ∆S=+ve

 (B) ∆H=−ve, ∆S=−ve

(C) ∆H=+ve, ∆S=+ve

(D) None of the above

Solution: Correct option is (A). For a spontaneous process ΔG=−ve (i.e.

ΔG<0). Also, ΔG=ΔH−TΔS but ΔH=−ve and ΔS=+ve. Thus, the given
condition reveals ΔG=−ve.

11. The Gibbs free energy change for the reaction for which ΔH=−393.4kJ
and ΔS=−2.9JK −1mol−1 at 298K is:

(A) − 352 KJ

(B) − 392 KJ

(C) + 352 KJ

(D) + 392 KJ

Solution: Correct option is (B). ΔG=ΔH−TΔS. We are given that :

ΔH=−393.4 kJ/mol and ΔS=−2.9 JK −1 mol −1. So, we can calculate the
change in Gibb’s free energy as:

ΔG=−393400−298×2.9=−392535.8 J≈−392 kJ

Hence, option B is correct.

12. Which one of the following has ΔSo positive?

(A) CaO (S) + CO2 ⇌ CaCO3 (S)

(B) NaCl (aq) ⇌ NaCl (S)

 (C) NaNO3 (S) + H2O ⇌ Na+(aq) + −¿3NO ¿(aq)

(D) N2(g) + 3H2(g) ⇌ 2NH3(g)

Solution: Correct option is (C). Dissolution of compound in solvent

increases entropy. In other option, no. of gas molecules in reactant is
greater than no. of molecule in product. Hence there will be more
randomness in the reactant than product so △So is –ve. △So is +ve only in
option c.

13. The standard entropies of N2(g), H2(g) and NH3(g) are 191.5, 130.5, and
192.6 JK-1mole-1. The value of the standard entropy formation (∆S°) of
1
ammonia, if the formation chemical reaction of ammonia is given by: 2
3
N2(g) + 2 H2(g) ⇌ NH3(g)

(A) - 98.9 JK-1mole-1

(B) + 98.9 JK-1mole-1

(C) ____ JK-1mole-1

(D) ____ JK-1mole-1

Solution: The standard entropy formation of ammonia at standard state

condition (at T= 298 & P=1atm) can be calculated as:
❑
0 =∑ ¿ ¿
298
∆S
❑

Where n & m are stoichiometric constant coefficients of the chemical

reaction.
 ∆ S = ( 1mol × Δ 0S
0298 298, NH 3 (g)
)− ( 12 mol × Δ 0
298, N 2(g)
S
3
+ mol × Δ 0298,
2 S
H 2 (g)
)
0298
[
∆ S = 1 mol ×(192.6 k
J
m ][
1 J 3 J
ol . K) − mol ×(191.5 k ol . K )+ mol ×(130.5 k ol . K)
2 m 2 m ]
298 kJ kJ
0 ∆ S =192.6 −291.5
K K

kJ
∴ 0298
∆ S =−98.9
K

kJ
Hence, the standard entropy formation of ammonia is −98.9 K .

1. Which of the following statements best describes the Second Law of Thermodynamics?

a) Energy cannot be created or destroyed.

b) The total entropy of an isolated system always increases.

c) Heat flows from a high temperature to a low temperature.

d) The internal energy of a system remains constant.

Answer: b) The total entropy of an isolated system always increases.

2. The Second Law of Thermodynamics is based on which fundamental principle?

a) Conservation of energy

b) Conservation of mass

c) Conservation of momentum

d) Conservation of entropy

Answer: d) Conservation of entropy

3. The Second Law of Thermodynamics states that:

a) Energy is conserved in all processes.

b) Heat always flows from a cold object to a hot object.

 c) It is impossible to convert heat completely into work.

d) The entropy of an isolated system remains constant.

Answer: c) It is impossible to convert heat completely into work.

4. Entropy is a measure of:

a) The amount of energy in a system.

b) The disorder or randomness in a system.

c) The temperature of a system.

d) The pressure of a system.

Answer: b) The disorder or randomness in a system.

5. Which of the following is an example of an irreversible process?

a) Boiling water

b) Mixing two gases

c) Melting ice

d) Expansion of a gas against a vacuum

Answer: d) Expansion of a gas against a vacuum

6. The efficiency of a heat engine is given by:

a) Work input / Work output

b) Work output / Heat input

c) Heat input / Work output

d) Heat output / Heat input

Answer: b) Work output / Heat input

7. The Carnot efficiency of a heat engine depends on:

a) The temperature of the hot reservoir only

b) The temperature of the cold reservoir only

c) Both the temperature of the hot and cold reservoirs

 d) The pressure of the working fluid

Answer: c) Both the temperature of the hot and cold reservoirs

8. Which of the following statements is true for a reversible process?

a) The entropy change is zero.

b) The heat transfer is zero.

c) The work done is zero.

d) The temperature change is zero.

Answer: a) The entropy change is zero.

9. The Clausius statement of the Second Law of Thermodynamics states that:

a) It is impossible to reach absolute zero temperature.

b) Heat cannot be transferred from a cold object to a hot object without external work being done.

c) The entropy of a system always increases in a spontaneous process.

d) Energy is conserved in all processes.

Answer: b) Heat cannot be transferred from a cold object to a hot object without external work being
done.

10. The Kelvin-Planck statement of the Second Law of Thermodynamics states that:

a) It is impossible to reach absolute zero temperature.

b) Heat cannot be transferred from a cold object to a hot object without external work being done.

c) The entropy of a system always increases in a spontaneous process.

d) Energy is conserved in all processes.

Answer: b) Heat cannot be transferred from a cold object to a hot object without external work being
done.

11. The direction of natural processes is determined by:

a) The First Law of Thermodynamics

b) The Second Law of Thermodynamics

c) The Third Law of Thermodynamics

 d) The Zeroth Law of Thermodynamics

Answer: b) The Second Law of Thermodynamics

12. Which of the following is an example of a reversible process?

a) Combustion of fuel in an engine

b) Melting of ice

c) Mixing of two gases

d) Expansion of a gas against a piston

Answer: b) Melting of ice

13. The entropy of a system is a measure of:

a) The energy content of the system

b) The temperature of the system

c) The disorder or randomness of the system

d) The pressure of the system

Answer: c) The disorder or randomness of the system

14. The Carnot cycle is an idealized cycle that:

a) Represents the most efficient heat engine possible

b) Represents the least efficient heat engine possible

c) Represents a reversible heat engine

d) Represents an irreversible heat engine

Answer: c) Represents a reversible heat engine

15. Which of the following statements is true regarding the entropy change of the universe in a
spontaneous process?

a) The entropy of the universe always decreases.

b) The entropy of the universe always increases.

c) The entropy of the universe remains constant.

d) The entropy of the universe depends on the specific process.

 Answer: b) The entropy of the universe always increases.

16. The concept of entropy is closely related to which other thermodynamic property?

a) Enthalpy

b) Temperature

c) Gibbs free energy

d) Internal energy

Answer: c) Gibbs free energy

17. Which of the following is an example of a process that violates the Second Law of Thermodynamics?

a) A refrigerator cooling down a room

b) A heat engine converting heat into work

c) A cup of hot coffee spontaneously cooling down

d) A person gaining energy without any external input

Answer: d) A person gaining energy without any external input

18. The Second Law of Thermodynamics implies that:

a) Energy is conserved in all processes.

b) Heat always flows from a cold object to a hot object.

c) It is impossible to convert work completely into heat.

d) The internal energy of a system remains constant.

Answer: c) It is impossible to convert work completely into heat.

19. The direction of heat flow is determined by:

a) The First Law of Thermodynamics

b) The Second Law of Thermodynamics

c) The Third Law of Thermodynamics

d) The Zeroth Law of Thermodynamics

Answer: b) The Second Law of Thermodynamics

20. Which of the following processes is most likely to have a negative entropy change?

a) Combustion of fuel

b) Freezing of water

c) Evaporation of liquid

d) Expansion of a gas

Answer: b) Freezing of water