2.

The First Law of Thermodynamics

2.1 Introduction to the First Law of Thermodynamics

q The first law of thermodynamics states that the energy of a system is conserved. It can be transferred
between the system and its surroundings or converted from one form to another.

q The first law of thermodynamics, also known as the law of energy conservation, states that energy
cannot be created or destroyed in an isolated system.

q It can only be transferred or transformed from one form to another. In other words, the total energy
of a closed system remains constant.

q The first law of thermodynamics has several important implications. It implies that energy is a
conserved quantity, and any energy transfer or transformation within a system must be accounted
for. It also establishes a relationship between heat transfer, work done, and the change in internal
energy of a system.

q Overall, the first law of thermodynamics is a foundational principle in thermodynamics and provides a
basis for understanding and analyzing energy interactions in various physical systems.

2.2 The mathematical expression and the equivalent statements of the first
law thermodynamics

q The first law of thermodynamics can be mathematically expressed as:

dU =δ q −δ w

∆ U =q − w

where: ∆U represents the change in internal energy of a system, Q represents the heat transferred to
the system, and W represents the work done by the system.

q Sign conventions: The signs of Q and W determine the direction of energy flow. Positive values
indicate energy being added to the system, while negative values indicate energy being transferred
out of the system.
q This equation states that the change in internal energy of a system is equal to the heat added to the
system minus the work done by the system. It highlights the fundamental principle that energy is
conserved within a closed system. The implications of this expression are:

 Conservation of energy: The equation shows that the change in internal energy (∆U) of a system is
equal to the heat transferred to the system (Q) minus the work done by the system (W). This
implies that energy is conserved in a thermodynamic process.

 Heat and work are interchangeable: The equation demonstrates that heat and work are
interchangeable forms of energy. An increase in internal energy can result from either heat transfer
or work done on the system, or a combination of both.

 Energy transfer and transformation: The equation highlights that energy can be transferred into or
out of a system as heat or work. It also allows for the transformation of energy between different
forms, such as potential energy, kinetic energy, and thermal energy.

 The first law of thermodynamics the internal energy of a system can be changed by doing work on it
or by heating/cooling it. “The change in internal energy of a system is equal to the difference
between heat added to the system and the work done by the system”.

 The internal energy of a system tends to increase if energy is added via heat (Q) and decrease via
work (W) done by the system.

q Overall, the mathematical expression of the first law of thermodynamics quantifies the relationship
between heat, work, and the change in internal energy, providing a framework for analyzing energy
changes in thermodynamic processes.

q Note that: The first law of thermodynamics tells us that in order to change the internal energy of a
system we must add (or remove) heat and do work on (or have work done by) the system.

q The Equivalent alternative statements of the first law of thermodynamics:

q The first law of thermodynamics, also known as the law of conservation of energy, can be expressed
in several alternative equivalent statements. Here are some of them:

 Energy is conserved in an isolated system: In an isolated system where no heat or work is

exchanged with the surroundings, the total energy of the system remains constant.

 The energy added to a system is equal to the work done on the system plus the heat transferred
to the system: If heat (Q) is added to a system and work (W) is done on the system, the change in
internal energy (ΔU) will be the sum of Q and W.

 The change in internal energy of a system is equal to the heat added to the system minus the
work done by the system: If heat (Q) is added to a system and work (W) is done by the system,
the change in internal energy (ΔU) will be Q minus W.
q These alternative statements highlight different aspects of the first law of thermodynamics but
ultimately convey the same fundamental principle of energy conservation within a system.

2.3 Sample practice problems related to the first law thermodynamics and
Evaluation Enthalpies and Free Energies:

1. Problem: A gas is compressed from an initial volume of 5 L to a final volume of 2 L. During the
compression, 500 J of work is done on the gas. If no heat is transferred, calculate the change in internal
energy (∆U) of the gas.

Solution:

∆U = Q - W

Since no heat is transferred (Q = 0),

∆U = 0 - (-500 J) (negative sign because work is done on the gas)

∆U = 500 J

Therefore, the change in internal energy (∆U) of the gas is 500 J.

2. Problem: A system undergoes a cyclic process where 300 J of heat is absorbed and 200 J of work is
done by the system. Calculate the net change in internal energy (∆U) of the system.

Solution:

∆U = Q - W

∆U = 300 J - 200 J

∆U = 100 J

Therefore, the net change in internal energy (∆U) of the system is 100 J.

7. Problem: A piston-cylinder device contains 0.2 kg of air at an initial pressure of 3 bar. The air is
compressed adiabatically to a final pressure of 6 bar. If the work done by the system during the
compression is 200 J, calculate the change in internal energy (∆U) of the air.

Solution:

∆U = Q - W

Since the process is adiabatic, Q = 0 (no heat transfer)

∆U = 0 - (-200 J) (negative sign because work is done by the system)

∆U = 200 J
 Therefore, the change in internal energy (∆U) of the air is 200 J.

8. Problem: A system absorbs 400 J of heat and does 200 J of work on the surroundings. Calculate the
heat transfer (Q) if the change in internal energy (∆U) of the system is -100 J.

Solution:

∆U = Q - W

-100 J = Q - 200 J (negative sign because work is done on the surroundings)

Q = -100 J + 200 J

Q = 100 J

Therefore, the heat transfer (Q) is 100 J.

9. Problem: A gas expands from an initial volume of 2 L to a final volume of 6 L while absorbing 500 J of
heat. Calculate the work done by the gas during the expansion.

Solution:

∆U = Q - W

Since ∆U = 0 (no change in internal energy),

0 = 500 J - W

W = 500 J

Therefore, the work done by the gas during the expansion is 500 J.

10. Problem: A system undergoes a reversible isothermal expansion from an initial pressure of 2 atm to
a final pressure of 1 atm. If the initial volume is 5 L, calculate the final volume of the system.

Solution: For a reversible isothermal process, the relationship between pressure and volume is given by:

P1V1 = P2V2

(2 atm)(5 L) = (1 atm)(V2)

V2 = 10 L

Therefore, the final volume of the system is 10 L.

3. Problem: A container initially contains 1 mole of an ideal gas at a pressure of 2 atm and a volume of
10 L. The gas expands isothermally to a final volume of 20 L. Calculate the work done by the gas during
the expansion.
Solution: For an isothermal process, the work done can be calculated as:

W = nRT ln(Vf/Vi)

W = (1 mole)(0.0821 L.atm/mol.K)(273 K) ln(20/10)

W = 5.72 atm.L

Therefore, the work done by the gas during the expansion is 5.72 atm.L.

4. Problem: A system undergoes an adiabatic expansion where the pressure decreases from 5 atm to 2
atm. If the initial volume is 10 L, calculate the final volume of the system.

Solution: For an adiabatic process, the relationship between pressure and volume is given by:

P1V1^γ = P2V2^γ

(5 atm)(10 L)^γ = (2 atm)(V2)^γ

V2^γ = (5/2)(10^γ)

V2 = (5/2)^(1/γ) * 10

V2 = 8.66 L

Therefore, the final volume of the system is 8.66 L.

2.4 Review Multiple Choice Questions on the first law thermodynamics

Here are some multiple-choice questions on the first law of thermodynamics along with their answers:

1. ________________ is the total energy of all the microscopic particles (atoms or molecules)
that makeup the body of a particular TDs system.
(A)Kinetic Energy (B) Internal Energy (C) Potential Energy (d) Heat

2. Which one of the following statement is not correct?

(A)For an ideal gases, the heat capacity of at constant pressure is always greater than at
constant volume.
(B)The heat capacity of liquids or solids at constant pressure and volume is
approximately the same.
(C) The change in internal energy of any TDs system only depends on temperature.
(D)The heat capacity can be affected by the change in temperature , amount and nature
of the substance
(E)None of the above
3. Which one of the following statement is not correct?
 (A)For an ideal gases, the heat capacity of at constant pressure is always greater than at
constant volume.
(B)The heat capacity of liquids or solids at constant pressure and volume is
approximately the same.
(C) The change in internal energy of any TDs system only depends on temperature.
(D)The heat capacity can be affected by the change in temperature , amount and nature
of the substance
(E)None of the above
4. The change in Enthalpy (∆ H) is much greater than the change in internal energy (∆ U)
for an ideal gaseous TDs system.
(A)True
(B) False
5. if the pressure acted on an ideal gas is doubled and the temperature is also halved, then
we can say that the volume of the gas is:
(A)Quartered
(B)Halved
(C) Constant
(D)Doubled
(E)None of the above
6. Which of the following is not a state TD function?
(A)Change in Internal energy (∆ U )
(B)Change in Enthalpy(∆ H ¿
(C) Change in Gibbs free energy (∆ G ¿
(D)Change in Entropy ( ∆ S )
(E)None of the above
7. Which of the following statements will always apply when a reversible chemical
reaction has attained equilibrium?
(A) All reactants will convert to products

(B) The reaction proceeds alternately in the forward and reverse directions

(C) The Gibbs free energy of the system reaches a minimum

(D)The forward reaction will dominate over the reverse reaction

8. A drug used to treat hypertension undergoes a decomposition reaction to give an

insoluble product. Calculate the temperature at which this reaction becomes
spontaneous if the enthalpy of the reaction at 298 K is 51 kJ mol and the entropy of the
reaction at this temperature is 118.74 J K mol .
(A)430 K

(B)2300 K
 (C) 0.5 K

(D)430 C

9. Which one of the following equations defines the enthalpy of reaction, ΔH, for a reaction
occurring at constant pressure that does expansion work? All terms have their usual
meanings.
(A) ΔH = ΔU

(B) ΔH = ΔU + p ΔV

(C) ΔH = ΔG - T ΔS

(D)ΔH = q + w

10. The combustion of methanol is described by the following equation: CH OH + O → CO +

2H O Use Hess's Law to calculate the enthalpy of combustion (ΔH ) of methanol given
the following standard enthalpies of formation (ΔH ).
(A) ΔH methanol = - 238.0 kJ mol
(B) ΔH H O = - 285.5 kJ mol
(C) ΔH CO = - 393.51 kJ mol
(D) ΔH O = 0 kJ mol
Ans :

a) -1203.2 kJ mol

b) -441.35 kJ mol

c) 727.2 kJ mol

d) -727.2 kJ mol

11. Which one of the following definitions best describes the concept of work?
(A)the flow of energy from one object or substance to another due to a difference in
temperature.

(B)the flow of energy from one body to another through uniform molecular motion.

(C) the force associated with molecular motion.

(D)the random motion of molecules in a gas at low pressure

12. A change in the state of gas during which the pressure of the gas remains constant is
called …………….change.

(A)Adiabatic
 (B)Isothermal

(C) Isobaric

(D)isochoric

13. A change in the state of gas during which the pressure of gas remain constant is
called…………..change.

(A)Adiabatic

(B)isothermal

(C) isobaric

(D)isochoric

14. A change in the state of gas during which the volume of gas remains constant is called
……….change.

(A) Adiabatic

(B) isothermal

(C) isobaric

(D) isochoric

15. The energy store in the substance or system is known as it's ………….energy

(A) internal

(B) potential

(C) kinetic

(D) pressure

16. All natural processes are………..

A) reversible

B) isothermal

C) irreversible

D) none of the above

17. Isothermal change for a perfect gas takes place at

A) constant pressure

B) constant volume

C) none of these

D) constant temperature

18. A system which neither exchange energy nor matter with its surrounding is known
as………….

A) open system

B) isolated system

C) closed system

D) none of the above

19. The adiabatic relation between pressure and temperature of gas is

A) Pγ-1 Tγ = CONST

B) P Vγ = CONST

C) Pγ T γ-1 = CONST

D) T𝛄/ P γ-1 = CONST

20. The adiabatic relation between Volume and temperature of gas is

A) T ᵞ-1 Vᵞ = CONST

B) T Vᵞ = CONST

C) T Vᵞ-1 = CONST

D) Tᵞ / V ᵞ-1 = CONST