The first law of thermodynamics states that when a system undergoes a change from one

state to another, the change in its internal energy is

𝛥𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊

where Q is the energy transferred into the system by heat and W is the work done on the
system. Although Q and W both depend on the path taken from the initial state to the final
state, the quantity 𝛥𝐸𝑖𝑛𝑡 does not depend on the path. First law of thermodynamics is nothing
but the conservation of energy. It was first discovered or originated by the great scientist
Joule.

Problem:
60 J of work is done on a gas, and the gas loses 150 J of heat in its surrounding. What is the
change in its internal energy? Does the temperature of the gas remain constant?
Solution:
Internal Energy, 𝛥𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊
= −150𝐽 + (+60𝐽)
= − 90𝐽

Minus sign indicates that the internal energy is decreased. Roughly, we can say temperature
of the gas is decreased.

Some idealized thermodynamic processes:

In a cyclic process (one that originates and terminates at the same state), 𝛥𝐸𝑖𝑛𝑡 = 0
and therefore 𝑄 = −𝑊. That is, the energy transferred into the system by heat equals the
negative of the work done on the system during the process.

In an adiabatic process, no energy is transferred by heat between the system and its
surroundings (𝑄 = 0). In this case, the first law gives 𝛥𝐸𝑖𝑛𝑡 = 𝑊.

In the adiabatic free expansion of a gas, 𝑄 = 0 and 𝑊 = 0, so 𝛥𝐸𝑖𝑛𝑡 = 0 . That is, the
internal energy of the gas does not change in such a process.

An isobaric process is one that occurs at constant pressure. The work done on a gas in such
a process is
𝑊 = −𝑃(𝑉𝑓 − 𝑉𝑖 )
An isovolumetric process is one that occurs at constant volume. No work is done in such a
process, so
𝛥𝐸𝑖𝑛𝑡 = 𝑄

An isothermal process is one that occurs at constant temperature. The work done on an
ideal gas during an isothermal process is
𝑣𝑓
𝑊 = 𝑛𝑅𝑇 𝑙 𝑛 ( )
𝑣𝑖

Application of the First Law

The heat engine is the most common practical application of the First Law. The first law of
thermodynamics finds application in several special cases:

Adiabatic processes: 𝑄 = 0, 𝛥𝐸𝑖𝑛𝑡 = −𝑊

constant-volume processes: 𝑊 = 0, 𝛥𝐸𝑖𝑛𝑡 = 𝑄

cyclical processes: 𝛥𝐸𝑖𝑛𝑡 = 0, 𝑄 = 𝑊

free expansions: 𝑄 = 𝑊 = 𝛥𝐸𝑖𝑛𝑡 = 0

Heat Engine:
A heat engine is a system which converts heat into work by taking heat from the reservoir (hot body)
to carry out some work. A schematic diagram of heat engine is given below.

Hot Reservoir at temperature T1

𝑄1 heat is entered into the system.

Work done by the engine is

Heat Engine
𝑊 = 𝑄1 − 𝑄2

𝑄2 heat leaves the system.

Cold Reservoir at temperature T2

Carnot Engine
A Carnot engine is an ideal engine that can operate in a reversible closed thermodynamic cycle where
the working substance goes through four successive operations such as isothermal expansion,
adiabatic expansion, isothermal compression, and adiabatic compression. Carnot engine basically
draws heat (𝑄1) from the source and rejects heat (𝑄2) to the sink while performing an amount of work,
𝑊 = 𝑄1 – 𝑄2.

The complete cycle incorporates:

Isothermal Expansion:
During the isothermal expansion of an ideal gas, we use the temperature of source T1 which will draw
Q1 amount of heat. Since the expansion is isothermal the total change in internal energy is zero and
the heat absorbed by the gas will be equal to the work done by the gas on the environment.

Adiabatic Expansion:
During the adiabatic expansion of an ideal gas, the temperature of an ideal gas falls from source
temperature T1 to sink temperature T2. Here, the pressure falls and volume increases because no heat
energy is being supplied to gas as it expands. The work is less, and the pressure must be lower.

Isothermal Compression:
During the process of isothermal compression of an ideal gas sink temperature T2 further goes down
as it rejects heat Q2 to the sink.

Adiabatic Compression:
During adiabatic compression of an ideal gas temperature naturally raises from T2 to T1 and hence
working substance returns to its original state by completing one cycle.
 𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒
The efficiency of the Carnot engine is given as, 𝜂 =
𝐻𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡
We know that,

Work done, 𝑊 = 𝑄1 − 𝑄2,

𝐻𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 = 𝑄1

𝑊 𝑄1 −𝑄2 𝑄
Then, Efficiency, 𝜂 = = = 1 − (𝑄2)
𝑄1 𝑄1 1

which is the efficiency of the heat engine.

If 𝑄2 = 0, then efficiency = 100%. This is known as the Carnot engine. It is an ideal case
here the efficiency is 100%. However, there will be some loss of energy in the system and
hence, for every engine, there will be a limit of efficiency. Meanwhile, it is also known that
𝑄 𝑇
thermodynamically, (𝑄2) = (𝑇2)
1 1
Therefore,
𝑇2
𝜂 = 1– ( )
𝑇1

Work done in each step:

Isothermal expansion:
𝑉2
𝑊1 = 𝑄1 = 𝑛𝑅𝑇1 𝑙𝑛 ( )
𝑉1
Adiabatic expansion:
𝑛𝑅
𝑊2 = (𝑇 − 𝑇2 )
𝛾−1 1
Isothermal compression:
𝑉4
𝑊3 = 𝑄2 = 𝑛𝑅𝑇2 𝑙𝑛 ( )
𝑉3
Adiabatic compression:
𝑛𝑅
𝑊4 = (𝑇 − 𝑇1 )
𝛾−1 2

Hence, the total work done by the gas on the environment in one complete cycle is given by,
𝑊 = 𝑊1 + 𝑊2 + 𝑊3 + 𝑊4
Problem:
A Carnot heat engine receives 500 𝑘𝐽 of heat per cycle from a high-temperature source at 652°C and
rejects heat to a low-temperature sink at 30°C. Determine (a) the thermal efficiency of this Carnot
engine and (b) the amount of heat rejected to the sink per cycle.

Solution:
(a) The thermal efficiency of this Carnot engine,
𝑇
𝜂 = 1 − 𝑇2
1
(30 + 273)𝐾
= 1 − (652 + 273)𝐾 = 0.672
(b) The amount of heat rejected to the sink per cycle
𝑄2 𝑇2
=
𝑄1 𝑇1

𝑇2
𝑄2 = 𝑄
𝑇1 1

(30 + 273)𝐾
𝑄2 = 500 𝐾𝐽
(652 + 273)𝐾

303 𝐾
𝑄2 = × 500 𝐾𝐽
925 𝐾

𝑄2 = 164 𝐾𝐽

Problem:
An engine following Carnot’s cycle produces power of 90,000 𝐾𝑊. Find the rate at which heat is
absorbed into the system from hot reservoir and leaves out of the system to the cold reservoir
for an engine operating between the reservoirs 750 𝐾 and 300 𝐾.

Solution:
We have,
𝑇2
𝜂 =1−
𝑇1

300𝐾
=1−
750 𝐾

= 0.6
We also have,
𝑊
𝜂=
𝑄1
 𝑊
𝑄1 =
𝜂
90,000 𝐾𝑊
𝑄1 = = 150,000 𝐾𝑊
0.6

Thermodynamically,
𝑄1 𝑇1
=
𝑄2 𝑇2

𝑇2
𝑄2 = 𝑄1
𝑇1

300 𝐾
𝑄2 = 150,000 𝐾𝑊
750 𝐾

𝑄2 = 60,000 𝐾𝑊

Reversible process: A process in which it is possible to return both the system and surroundings to
their original states.

Irreversible process: A process in which it is impossible to return both the system and surroundings
to their original states.

The second law of thermodynamics

The Kelvin–Planck statement of the second law of thermodynamics, which is expressed as follows:
“It is impossible for any device that operates on a cycle to receive heat from a single reservoir and
produce a net amount of work.”

The Kelvin–Planck statement can also be expressed as no heat engine can have a thermal efficiency
of 100 percent, or as for a power plant to operate, the working fluid must exchange heat with the
environment as well as the furnace.

The Clausius Statement is expressed as:

It is impossible to construct a device that operates in a cycle and produces no effect other than the
transfer of heat from a lower- temperature body to a higher-temperature body.
It is common knowledge that heat does not, of its own volition, transfer from a cold medium to a
warmer one.

Entropy is a measure of disorder or randomness of a system. An ordered system has low entropy.
A disordered system has high entropy.
Total entropy may be conserved during a reversible process.

If a total amount of heat 𝑄 is added during a reversible isothermal process at absolute

temperature T, the total entropy change,

Δ𝑆 = 𝑆2 − 𝑆1 is given by
𝑄
Δ𝑆 = 𝑆2 − 𝑆1 =
𝑇

We define the infinitesimal entropy change 𝑑𝑆 during an infinitesimal reversible process at

absolute temperature T as

𝑑𝑄
𝑑𝑆 =
𝑇

Total entropy changes of a system having final temperature 𝑇2 and initial temperature 𝑇1 is

𝑇2
𝑑𝑄
𝑑𝑠 = ∫
𝑇1 𝑇

𝑇2
𝑚𝑠 𝑑𝑇
=∫
𝑇1 𝑇

𝑇2
𝑑𝑇
= 𝑚𝑠 ∫
𝑇1 𝑇

𝑇2
= 𝑚𝑠 ln ( )
𝑇1

Problem: What is the change of entropy of 1 kg of ice that is melted reversibly at 0° C and
converted to water at 0° C. The heat of fusion of water is 𝐿𝑓 = 3.34 × 105 𝐽/𝑘𝑔.

Solution:
The melting occurs at a constant temperature 0°C or 273 K, so this is an isothermal
reversible process.

The heat needed to melt the ice is

𝑄 = 𝑚𝐿𝑓 = 1 × 3.34 × 105 = 3.34 × 105 𝐽.
 𝑄 3.34 × 105
𝑑𝑠 = = 𝐽/𝐾
𝑇 273

= 1.22 × 103 𝐽/𝐾

Problem:
One kilogram of water at 0°C is heated to 100°C. Compute its change in entropy. Assume
that the specific heat of water is constant at 4190 J/kg·K over this temperature range.

Solution:
Change in entropy,
𝑇2
𝑑𝑆 = 𝑚𝑠 ln ( )
𝑇1

373
= 1 × 4190 × ln ( )
273

= 1.31 × 103 𝐽/𝐾