PHY-107 Module 13: Thermodynamics

MODULE 13: THERMODYNAMICS

(Dr. Rubaiyet I. Haque)

LECTURE 26
OUTLINE:
▪ 1st law of thermodynamics
▪ Energy conservation law

FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics states that for a closed thermodynamic system, the change in internal
energy of a system is equal to the work done by the system due to the heat flows into the system.
In a closed system (i.e., there is no transfer of matter into or out of the system), the first law states
that the change in internal energy of the system (𝛥𝑈𝑠𝑦𝑠𝑡𝑒𝑚 ) is equal to the difference between the heat
supplied to the system (𝑄) and the work (𝑊) done by the system on its surroundings.
∆𝑈𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑄 − 𝑊

Important facts:
- The heat (𝑄) is positive when heat is transferred into the system. When the heat (𝑄) is transferred
out of the system, then 𝑄 is negative (e.g., −𝑄).
- When the work is done by the system, 𝑊 is positive. If the work is done on the system, 𝑊 is
negative (e.g., −𝑊).
- Change of internal (∆𝑈 or ∆𝐸𝑖𝑛𝑡 ) energy is path independent. It only depends on the internal energy
of the initial (𝑈𝑖 ) and final (𝑈𝑓 ) states.

Total Internal Energy: When two initially isolated systems (i.e., there is no transfer of matter and
energy into or out of the system) are combined into a new system, then the total internal energy of
the new system, 𝑈𝑠𝑦𝑠𝑡𝑒𝑚 , will be equal to the sum of the internal energies of the two initial systems,
𝑈1 and 𝑈2 ,
𝑈𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑈1 + 𝑈2
This equation states that any change in the internal energy of a system is equal to the heat added to
the system minus the work done by the system.

Key Points About the First Law of Thermodynamics:

- Conservation of Energy: The law asserts that energy is conserved in a closed system, and the total
energy remains constant.
- Energy Transfer: Energy can be transferred into or out of the system in the form of heat (thermal
energy) or work (mechanical energy).
- Internal Energy: The internal energy of a system is a measure of its total energy content, including
both kinetic and potential energy.

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 PHY-107 Module 13: Thermodynamics

- Sign Convention: The convention for the signs of heat and work is that heat transferred into the
system and work done by the system are positive, while heat transferred out of the system and
work done on the system are negative.

CHECKPOINT: The figure here shows four paths on a 𝑝 − 𝑉

diagram along which a gas can be taken from state 𝑖 to state 𝑓. Rank
the paths according to (a) the change ∆𝐸𝑖𝑛𝑡 in the internal energy of
the gas, (b) the work 𝑊 done by the gas, and (c) the magnitude of the
energy transferred as heat 𝑄 between the gas and its environment,
greatest first.
ANSWER: (a) all tie ∆𝐸𝑖𝑛𝑡 depends on 𝑖 and 𝑓, not on path);
(b) 4, 3, 2, 1 (Compare areas under curves);
(c) 4, 3, 2, 1 (Eq. ∆𝐸𝑖𝑛𝑡 = 𝐸𝑖𝑛𝑡,𝑓 − 𝐸𝑖𝑛𝑡,𝑖 = 𝑄 − 𝑊)

PROBLEM (EXTRA): A gas within a closed chamber

undergoes the cycle from 𝑠𝑡𝑎𝑡𝑒 𝐴 to 𝑠𝑡𝑎𝑡𝑒 𝐵 to 𝑠𝑡𝑎𝑡𝑒 𝐶, and
then back to 𝐴, as shown in the 𝑝 − 𝑉 diagram of Figure. The
vertical scale is set by 𝑝𝑠 = 40 𝑃𝑎, and the horizontal scale is
set by 𝑉𝑠 = 4.0 𝑚3 . Calculate the net energy added to the
system as heat during one complete cycle.

ANSWER: Over a complete cycle, the internal energy is the

same at the beginning and end, so the heat 𝑄 absorbed equals
the work done: 𝑄 = 𝑊.
The 𝐴𝐵 portion of the cycle is at constant pressure and the work done by the gas is,
𝑊𝐴𝐵 = 𝑝𝐴 ∆𝑉𝐴𝐵 = 𝑝𝐴 (𝑉𝐵 − 𝑉𝐴 )
Since, 𝑝𝐴 = 𝑝𝐵 = 20 𝑃𝑎, 𝑉𝐴 = 1.0 𝑚3 and 𝑉𝐵 = 3.0 𝑚3 we have
𝑊𝐴𝐵 = 𝑝𝐴 (𝑉𝐵 − 𝑉𝐴 ) = (20 𝑃𝑎)(3.0 𝑚3 − 1.0 𝑚3 ) = 40 𝐽

For the 𝐵𝐶 portion of the cycle, volume remain constant, so no work is done. Thus,
𝑊𝐵𝐶 = 0
Over the portion of the cycle from 𝐶 to 𝐴 the pressure 𝑝 is a linear function of the volume 𝑉 and
we may write 𝑝 = 𝑎 − 𝑏𝑉 . The work done over this portion of the cycle is,
𝑉𝐴 𝑉𝐴
𝑉 𝑉 1
𝑊𝐶𝐴 = ∫ 𝑝 𝑑𝑉 = ∫ (𝑎 − 𝑏𝑉)𝑑𝑉 = 𝑎𝑉|𝑉𝐴𝐶 − 𝑏𝑉 2 |𝑉𝐴𝐶 = 𝑎(𝑉𝐴 − 𝑉𝐶 ) − 𝑏(𝑉𝐴2 − 𝑉𝐶2 )
𝑉𝐶 𝑉𝐶 2
From graph we get, 𝑝 = 40 𝑃𝑎 when 𝑉 = 3.0 𝑚3 . Therefore, 40 𝑃𝑎 = 𝑎 − 3𝑏 𝑚3 .
Similarly, 𝑝 = 20 𝑃𝑎 when 𝑉 = 1.0 𝑚3 . Thus, 20 𝑃𝑎 = 𝑎 − 𝑏 𝑚3 .
Solving these two equations, we get, 𝑎 = 10 𝑃𝑎 and 𝑏 = −10 𝑃𝑎/𝑚3 .
Thus, the pressure function can be written as,

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PHY-107 Module 13: Thermodynamics

𝑃𝑎
𝑝 = 10 𝑃𝑎 − (−10 3
) 𝑉 = 10 𝑃𝑎 + (10 𝑃𝑎/𝑚3 )𝑉
𝑚

Therefore, the work done going from 𝐶 to 𝐴 is, Since, 𝑉𝐴 = 1.0 𝑚3 and 𝑉𝐶 = 3.0 𝑚3 , we get,
1
𝑊𝐶𝐴 = 𝑎(𝑉𝐴 − 𝑉𝐶 ) − 𝑏(𝑉𝐴2 − 𝑉𝐶2 )
2
1 𝑃𝑎
𝑊𝐶𝐴 = (10 𝑃𝑎)(1.0 𝑚3 − 3.0 𝑚3 ) − (−10 3 ) [(1.0 𝑚3 )2 − (3.0 𝑚3 )2 ]
2 𝑚
𝑊𝐶𝐴 = −20 𝐽 − 40𝐽 = −60 𝐽

The total work done by the gas is, 𝑊 = 𝑊𝐴𝐵 + 𝑊𝐵𝐶 + 𝑊𝐶𝐴
𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒, 𝑊 = 40 𝐽 + 0 − 60𝐽 = −20 𝐽
Thus, the total heat absorbed is 𝑄 = 𝑊 =– 20 𝐽. This means the gas loses 20 𝐽 of energy in the
form of heat.

ALTERNATIVE METHOD: BY CALCULATING AREA UNDER THE CURVES:

The 𝐴𝐵 portion of the cycle is at constant pressure and the work done by the gas is,
𝑊𝐴𝐵 = 𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑐𝑢𝑟𝑣𝑒 𝐴𝐵 = (20 𝑃𝑎)(2 𝑚3 ) = 40𝐽
The volume increases during this portion of the cycle, so the work done WAB is positive. Thus,
𝑊𝐴𝐵 = +40𝐽.

For the 𝐵𝐶 portion of the cycle, volume remain constant, and the work done by the gas is,
𝑊𝐵𝐶 = 𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑐𝑢𝑟𝑣𝑒 𝐵𝐶 = (20 𝑃𝑎)(0 𝑚3 ) = 0𝐽
Over the portion of the cycle from 𝐶 to 𝐴 the pressure 𝑝 is a linear function of the volume 𝑉 and
the work done by the gas is,
1
𝑊𝐶𝐴 = 𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑐𝑢𝑟𝑣𝑒 𝐶𝐴 = (20 𝑃𝑎)(2 𝑚3 ) + (20 𝑃𝑎)(2 𝑚3 ) = 40𝐽 + 20𝐽 = 60𝐽
2
Since, the volume decreases during this portion of the cycle, so the work done WCA is negative.
Thus, 𝑊𝐶𝐴 = −60𝐽.

Now, the total work done by the gas is, 𝑊 = 𝑊𝐴𝐵 + 𝑊𝐵𝐶 + 𝑊𝐶𝐴
𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒, 𝑊 = 40 𝐽 + 0 − 60𝐽 = −20 𝐽
Thus, the total heat absorbed is 𝑄 = 𝑊 =– 20 𝐽. This means the gas loses 20 𝐽 of energy in the
form of heat.

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PHY-107 Module 13: Thermodynamics

PROBLEM 18-43: In Fig., a gas sample expands from 𝑉0 to

𝑝
4.0 𝑉0 while its pressure decreases from 𝑝0 to 0 . If 𝑉0 =
4.0
1.0 𝑚3 and 𝑝0 = 40 𝑃𝑎, how much work is done by the gas if
its pressure changes with volume via (a) path A, (b) path B,
and (c) path C?

PROBLEM 18-44: A thermodynamic

system is taken from 𝑠𝑡𝑎𝑡𝑒 𝐴 to 𝑠𝑡𝑎𝑡𝑒 𝐵 to
𝑠𝑡𝑎𝑡𝑒 𝐶, and then back to 𝐴, as shown in the
𝑝 − 𝑉 diagram of Fig. a. The vertical scale is
set by 𝑝𝑠 = 40 𝑃𝑎, and the horizontal scale is
set by 𝑉𝑠 = 4.0 𝑚3 . (a)–(g) Complete the
table in Fig. b by inserting a plus sign, a minus
sign, or a zero in each indicated cell. (h) What
is the net work done by the system as it moves
once through the cycle 𝐴𝐵𝐶𝐴?

PROBLEM 18-45: A gas within a closed chamber undergoes

the cycle shown in the 𝑝 − 𝑉 diagram of Figure. The
horizontal scale is set by 𝑉𝑠 = 4.0 𝑚3 . Calculate the net
energy added to the system as heat during one complete cycle.

PROBLEM 18-46: Suppose 200 𝐽 of work is done on a system and 70.0 𝑐𝑎𝑙 is extracted from the
system as heat. In the sense of the first law of thermodynamics, what are the values (including
algebraic signs) of (a) 𝑊, (b) 𝑄, and (c) ∆𝐸𝑖𝑛𝑡 ?

PROBLEM 18-47: When a system is taken from state

𝑖 to state 𝑓 along path 𝑖𝑎𝑓 in Figure, 𝑄 = 50 𝑐𝑎𝑙 and
𝑊 = 20 𝑐𝑎𝑙. Along path 𝑖𝑏𝑓, 𝑄 = 36 𝑐𝑎𝑙. (a) What is
𝑊 along path 𝑖𝑏𝑓? (b) If 𝑊 = −13 𝑐𝑎𝑙 for the return
path 𝑓𝑖, what is 𝑄 for this path? (c) If 𝐸𝑖𝑛𝑡,𝑖 = 10 𝑐𝑎𝑙,
what is 𝐸𝑖𝑛𝑡,𝑓 ? If 𝐸𝑖𝑛𝑡,𝑏 = 22 𝑐𝑎𝑙, what is 𝑄 for (d) path
𝑖𝑏 and (e) path 𝑏𝑓?

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PROBLEM 18-48: As a gas is held within a closed chamber,

it passes through the cycle shown in Figure. Determine the
energy transferred by the system as heat during constant-
pressure process 𝐶𝐴 if the energy added as heat 𝑄𝐴𝐵 during
constant-volume process 𝐴𝐵 is 20.0 𝐽, no energy is
transferred as heat during adiabatic process 𝐵𝐶, and the net
work done during the cycle is 15.0 𝐽.

SOME SPECIAL CASES OF THE FIRST LAW OF THERMODYNAMICS

Here are four thermodynamic processes, namely, Adiabatic processes, Constant-volume processes,
Cyclical processes, and Free expansions.

Adiabatic Processes: An adiabatic process is a thermodynamic process in which there is no heat

transfer take place into or out of a system. While no heat is transferred, work can still be done on or
by the system.
An adiabatic process is one that occurs so rapidly or occurs in a system that is so well insulated that
no transfer of energy as heat occurs between the system and its environment. Putting 𝑄 = 0 we get,
∆𝑈 = −𝑊 (𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠)
Therefore, if work is done by the system (𝑊 > 0), the internal energy of the system decreases by the
amount of work. Conversely, if work is done on the system (𝑊 < 0), the internal energy of the system
increases by that amount.
Figure shows an ideal adiabatic process. Heat cannot enter
or leave the system because of the insulation. Thus, the
only way energy can be transferred between the system and
its environment is by work.
- If we remove shot from the piston and allow the gas to
expand, the work done by the system (the gas) is
positive and the internal energy of the gas decreases.
- If, instead, we add shot and compress the gas, the work
done by the system is negative and the internal energy
of the gas increases.

Constant-volume Processes: A constant-volume process, also known as an isochoric process, is a

thermodynamic process in which the volume of a system remains constant while other
thermodynamic properties may change. This means that the system does not undergo any change in
its volume during the process.
If the volume of a system (such as a gas) is held constant, that system can do no work. Putting 𝑊 = 0
in the first law yields,

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 PHY-107 Module 13: Thermodynamics

∆𝑈 = 𝑄 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 − 𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠).

- Thus, if heat is absorbed by a system (that is, if 𝑄 is positive), the internal energy of the system
increases.
- Conversely, if heat is lost during the process (that is, if Q is negative), the internal energy of the
system must decrease.

Cyclical Processes: Cyclical processes, also known as thermodynamic cycles, are sequences of
thermodynamic processes that return a system to its initial state after a series of operations.
There are processes in which, after certain interchanges of heat and work, the system is restored to its
initial state. In that case, no intrinsic property of the system including its internal energy can possibly
change. Putting ∆𝑈 = 0 we get,
𝑄 = 𝑊 (𝑐𝑦𝑐𝑙𝑖𝑐𝑎𝑙 𝑝𝑟𝑜𝑐𝑒𝑠𝑠).
Thus, the net work done during the process must exactly equal the net amount of energy transferred
as heat; the store of internal energy of the system remains unchanged. Cyclical processes form a
closed loop on a 𝑝 − 𝑉 plot.

Free Expansions: Free expansion, also known as free adiabatic expansion, is a thermodynamic
process in which no transfer of heat occurs between the system and its environment, and no work is
done on or by the system. Thus, 𝑄 = 𝑊 = 0, and the first law requires that,
∆𝑈 = 0 (𝑓𝑟𝑒𝑒 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛)
Figure shows how such an expansion can be
carried out. A gas, which is in thermal
equilibrium within itself, is initially confined
by a closed stopcock to one half of an
insulated double chamber; the other half is
evacuated. The stopcock is opened, and the
gas expands freely to fill both halves of the
chamber. No heat is transferred to or from the
gas because of the insulation. No work is done
by the gas because it rushes into a vacuum and
thus does not meet any pressure.

- Free expansion differs from all other processes we have considered because it cannot be done
slowly and in a controlled way.
- As a result, at any given instant during the sudden expansion, the gas is not in thermal equilibrium
and its pressure is not uniform.
- Thus, although we can plot the initial and final states on a 𝑝 − 𝑉 diagram, we cannot plot the
expansion itself.

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Table: The First Law of Thermodynamics: Four Special Cases

The first law, ∆𝐸𝑖𝑛𝑡 = 𝑄 − 𝑊
Process Restriction Consequence
Adiabatic 𝑄=0 ∆𝐸𝑖𝑛𝑡 = −𝑊
Constant volume 𝑊=0 ∆𝐸𝑖𝑛𝑡 = 𝑄
Closed cycle ∆𝐸𝑖𝑛𝑡 = 0 𝑄=𝑊
Free expansion 𝑄=𝑊=0 ∆𝐸𝑖𝑛𝑡 = 0

ENERGY CONSERVATION LAW

The energy conservation law, also known as the principle of conservation of energy or the first law
of thermodynamics, is a fundamental principle in physics.
- It states that the total amount of energy in an isolated system remains constant over time. Energy
can neither be created nor destroyed; it can only be transferred or transformed from one form to
another.

The principle of energy conservation is based on the observation that, in all known physical processes,
the total energy of a closed system remains constant. This principle is derived from extensive
experimental evidence and is one of the most fundamental and well-established principles in physics.
Mathematically, the energy conservation law can be expressed as follows:
𝛥𝑈 = 𝑈𝑓𝑖𝑛𝑎𝑙 − 𝑈𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑄 − 𝑊
where 𝛥𝐸 is the change in the total energy of the system, 𝐸𝑓𝑖𝑛𝑎𝑙 is the final energy, 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 is the
initial energy, 𝑄 represents the heat transferred into the system, and 𝑊 represents the work done on
the system.
- This equation states that any change in the total energy of a system is equal to the sum of the heat
added to the system and the work done on the system. If no heat transfer or work is involved, and
the system is isolated, then the total energy remains constant.
- It is important to note that while the total energy of an isolated system is conserved, energy can be
converted from one form to another within the system.
- For example, mechanical energy can be converted into thermal energy, or electrical energy can be
converted into kinetic energy. The conservation of energy provides a fundamental framework for
understanding and analyzing various physical processes in nature.