First Law of Thermodynamics – Review

❖ The first law is a statement of Conservation of Energy.

❖ The first law states that a change in internal energy in a system can occur
as a result of energy transfer by heat, by work, or by both.

The limitation of the first law of thermodynamics is that

➢ It does not say anything about the direction of flow of heat.

➢ It does not say anything whether the process is a spontaneous process or
not.
➢ In actual practice, the heat doesn't convert completely into work.

The Second Law of Thermodynamic

➢ Mixtures of chemically reactive species can evolve toward reactants or

toward products, How do we know which of these reactions is
spontaneous?

Entropy, designated by S, is the state function that predicts the direction

of natural, or spontaneous, change.

➢ Spontaneous does not mean that the process occurs immediately, but
rather that it will occur with high probability if any barrier to the change is
overcome. For example, the transformation of a piece of wood to CO 2 and
H2O in the presence of oxygen is spontaneous, but it only occurs at elevated
temperatures because an activation energy barrier must be overcome for the
reaction to proceed.
 ‫تعاريف حفظ‬
A reversible process is one in which both the system and its environment can
return to exactly the states they were in by following the
reverse path.

• Phase change like freezing or boiling of water

• slow isothermal compression or expansion of gases
An irreversible process is one in which the system and its environment cannot
return together to exactly the states that they were in.

The irreversibility of any natural process results from the second law of
thermodynamics.
• Death.
• Heat transfer through a finite temperature difference.
• Friction.
• Plastic deformation.
• Flow of electric current through a resistance.

• all natural spontaneous processes are irreversible.

Spontaneous reactions are those chemical or biological reactions that take

place without the influence of external factors.

Non- Spontaneous reactions are those chemical reactions that require an energy
input or the influence of external factors to proceed
 Major players in developing the Second Law

Nicolas Léonard Sadi Carnot was a French

physicist, who is considered to be the "father of
thermodynamics," for he is responsible for the
origins of the Second Law of Thermodynamics, as
well as various other concepts.

The current form of the second law uses entropy

rather than caloric, which is what Sadi Carnot used
to describe the law.

Rudolf Clausius was a German physicist, and he

developed

the Clausius statement,

"Heat generally cannot flow spontaneously from a

material at a lower temperature to a material at a
higher temperature." ‫حفظ‬

William Thompson, also known as Lord Kelvin,

formulated the

Kelvin statement

"It is impossible to convert heat completely in a

cyclic process." ‫حفظ‬

This means that there is no way for one to convert

all the energy of a system into work, without losing
energy.
 Heat Engine

A heat engine is a device that takes in energy by heat and, operating in a cyclic
process, expels a fraction of that energy by means of work.
Example – Internal Combustion engine of an automobile

Repeatedly undergoes a acyclic

process ∆𝑈 = 0
➢ Draws heat from a hot reservoir
; 𝑄ℎ
➢ Convert heat to work ; 𝑊𝑜𝑢𝑡
➢ Wastes some of the heat input
out to a cold reservoir, 𝑄𝑐

➢ Efficiency 𝑒 = 𝑊𝑜𝑢𝑡 /𝑄ℎ

Heat Pumps and Refrigerators

➢ Energy is extracted from the cold
reservoir, |QC|
➢ |Energy is transferred to the hot reservoir
|Qh|,
➢ Work must be done on the engine, W

the Clausius statement,

"Heat generally cannot flow

spontaneously from a material at
a lower temperature to a
material at a higher temperature
 The Carnot Cycle

Heat engine that operates most efficiently between high temperature reservoir
and low temperature reservoir, it is an ideal engine that uses reversible processes
to form its cycle of operation.

The Carnot cycle consists of the following four processes:

I. A reversible isothermal gas expansion process. In this process, the ideal

gas in the system absorbs qin amount heat from a heat source at a high
temperature Thigh, expands and does work on surroundings.

II. A reversible adiabatic gas expansion process. In this process, the system is
thermally insulated. The gas continues to expand and do work on
surroundings, which causes the system to cool to a lower temperature, Tlow.

III. A reversible isothermal gas compression process. In this process,

surroundings do work to the gas at Tlow, and causes a loss of heat, qout

IV. A reversible adiabatic gas compression process. In this process, the system
is thermally insulated. Surroundings continue to do work to the gas, which
causes the temperature to rise back to Thigh.
P-V Diagram

The P-V diagram of the Carnot cycle is shown in a Figure .

Thermal Efficiency of a Heat Engine
Thermal efficiency ‫ حفظ‬is defined as the ratio of the net work done by the
engine during one cycle to the energy input at the
higher temperature
𝑊𝑜𝑢𝑡
𝑒=
𝑊𝑜𝑢𝑡 |𝑄ℎ |−| 𝑄𝑐| 𝑄𝑐 𝑄ℎ
𝑒= = =1− 𝑄𝑐
𝑄ℎ |𝑄ℎ | 𝑄ℎ
𝑒 =1−
𝑄ℎ
𝑄𝑐 𝑇𝑐 𝑇𝑐
Since = Then , 𝑒 =1− 𝑊𝑜𝑢𝑡 = Qh – Qc
𝑄ℎ 𝑇ℎ 𝑇ℎ

𝑄𝑐 𝑇𝑐
𝑊𝑜𝑢𝑡 = net work transfer from the engine =
𝑄ℎ = heat transfer to engine at high temperature 𝑇ℎ 𝑄ℎ 𝑇ℎ
𝑄𝑐 = heat expel at low temperature 𝑇𝑐
𝑇𝑐
𝑒 =1−
𝑇ℎ
‫القوانين حفظ جميعها مهمة في حل األسئلة‬
Notes About Carnot Efficiency ‫حفظ‬
▪ Temperatures must be in Kelvins
▪ Efficiency is 0 if Th = Tc
▪ Efficiency is 100% ) only if Tc = 0 K
▪ Efficiency is always less than 100% (all heat engines expel only a
fraction of the input energy by mechanical work. Therefore, their
efficiency is always less than 100%.)
▪ The efficiency increases as Tc is lowered and as Th is raised.

Example 1

An engine transfers 2.00 × 103 J of energy from a hot reservoir during a cycle
and transfers 1.50 × 103 J as exhaust to a cold reservoir.
(A) Find the efficiency of the engine.
𝑄𝑐 1.50 × 103
𝑒 =1− =1- =0.25 or 25%
𝑄ℎ 2.00 × 103

(B) How much work does this engine do in one cycle?

𝑊𝑜𝑢𝑡 = Qh – Qc = 2.00 × 103 – 1.50 × 103= 0.5× 103J
Example 2

An ideal gas is taken through a Carnot cycle. The

isothermal expansion occurs at 250°C, and the isothermal
compression takes place at 50.0°C. The gas takes in 1200 J
of energy from the hot reservoir during the isothermal
expansion. Find (a) the energy expelled to the cold
reservoir in each cycle and (b) the net work done by the gas
in each cycle.
➢ Isothermal expansion at Th = 523 K
➢ Isothermal compression at Tc = 323 K

𝑄𝑐 𝑇𝑐 𝑄𝑐 323𝐾
(a) Since = → = → 𝑄𝑐 = 741𝐽
𝑄ℎ 𝑇ℎ 1200𝐽 523𝐾

(b) 𝑊𝑜𝑢𝑡 = Qh – Qc = 1200- 741= 459J

Example 3

A heat engine performs 200 J of work in each cycle and has an efficiency of
30%. For each cycle, how much thermal energy is
(a) absorbed and (b) expelled?

𝑊𝑜𝑢𝑡 𝑊𝑜𝑢𝑡 200𝐽

)a) 𝑒 = → 𝑄ℎ = = = 667𝐽
𝑄ℎ 𝑒 0.3

𝑄𝑐 𝑄𝑐
(c) 𝑒 = 1 − → 0.3 = 1 −
𝑄ℎ 667

𝑄𝑐
= 0.7
667
𝑄𝑐 = 467𝐽

What is the work output of a cyclical heat engine having a 22.0% efficiency and
6.00 × 109 J of heat transfer into the engine? (b) How much heat transfer occurs
to the environment?
Answer (a) 1.32 × 109 J; (b) 4.68 × 109
This set of Thermodynamics Multiple Choice Questions & Answers (MCQs)
focuses on “Carnot Theorem, Carnot Cycle and Reversed Heat Engine”.

1. Carnot cycle is a reversible cycle.

a) true
b) false
2. A reversible cycle has following processes.
a) 4 isothermal processes
b) 4 adiabatic processes
c) 2 isothermal and 2 adiabatic processes
d) none of the mentioned

3. 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
4. Example of reversed heat engine is
a) heat pump
b) refrigerator
c) both of the mentioned
d) none of the mentioned
5. According to Carnot’s theorem, all heat engines operating between a given
constant temperature source and sink, none has a higher efficiency than a
reversible engine.
a) true
b) false
6. The efficiency of all reversible heat engines operating between the same heat
reservoirs is
a) same
b) independent of the nature of working substance
c) independent of the amount of working substance
d) all of the mentioned

7. Efficiency of a reversible heat engine is given by

a) 1-(T1/T2)
b) 1-(T2/T1)
c) (T1/T2)-1
d) (T2/T1)-1

8. A heat engine has to exchange heat with ___ energy reservoir at ___ different
temperatures to produce net work in a complete cycle.
a) one, one
b) one, two
c) two, two
d) none of the mentioned
9- Clausius statement say that
a) it is impossible to construct a device than can transfer heat from a cooler
body to a hotter body without any effect
b) it is impossible to construct a device than can transfer heat from a hotter body
to a cooler body without any effect
c) it is possible to construct a device than can transfer heat from a cooler body
to a hotter body without any effect
d) none of the mentioned