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CHAPTER 14: THERMODYNAMICS

14.1 FIRST LAW OF THERMODYNAMICS

LO 14.1(a) State the first law of thermodynamics.

LO 14.1(b) Solve problems related to first law of thermodynamics.

1) A closed system is a system whose mass remain constant but the energy is allowed to
increase/decrease.
2) Two ways of energy transfer:
Energy
Heat (Chapter 13)

Energy transfer due to temperature difference

System Surroundings
Work (Chapter 5)

Energy transfer as a result of force

Energy
3) Therefore, any system can exchange energy with its surroundings in two general ways, as
heat or work.
4) In Chapter 14, we defined internal energy of a system as the total of kinetic energy and
potential energy of all particles in the system.
5) We would expect that the internal energy of a system would be increase if work was done on
the system, or if heat were added to it. Similarly the internal energy would be decreased if
heat flowed out of the system or if work were done by the system on something to the
surroundings. Therefore, it is reasonable to extend conservation energy and propose an
important law:

The first law of thermodynamics

The change in internal energy of a closed system, ∆𝑈, will be equal to the energy added by
the system by heat, minus the work done by the system on the surroundings.

Or
∆𝑈 = 𝑄 − 𝑊

∆𝑈: The change in internal energy

𝑄: Heat added into the system
𝑊: Work done by the system

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** We must be careful and consistent in following the sign conventions for Q and W. Because W
in equation 15-1 is the work done by the system, then if work done on the system, W will be
negative and ∆𝑈 will increase. Similarly Q is positive for heat added into the system, so if heat
leaves the system, Q is negative.

Heat into the system Heat out of the system

Q (+ve) Surroundings Q (-ve)

System

∆𝑈 = 𝑄 − 𝑊

Work done on the system Work done by the system

W (-ve) W (+ve)
Figure 14.1 Sign convention

Example 1

2500 J of heat is added to a system, and 1800 J of work is done on the system What is the change
in internal energy of the system? [4300 J]

Example 2

A gas expands under constant temperature condition and does work of 30 J against the
surrounding.
a) What is the change in the internal energy of the gas? [0 J]
b) Find the amount of heat absorbed or lost by the gas. [30 J]

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14.2 Thermodynamic Process

LO 14.2(a) Define the following thermodynamics processes:

i. Isothermal
ii. Isochoric
iii. Isobaric
iv. Adiabatic
LO 14.2(b) Discuss p-V graph for all the thermodynamics processes. ∆𝑈 = 𝑄 − 𝑊
 A thermodynamic process is process where the parameters of a system such as pressure, volume
& temperature undergo changes.
Isothermal Isovolumetric Isobaric Adiabatic
(Isochoric)
Is defined as a process Is defined as a process Is defined as a process Is defined as a process
that occurs at constant that occurs at constant that occurs at constant that occurs without
temperature volume pressure heat transfer into or
out of a system
T constant, At constant V, P is constant 𝑸=𝟎
𝑾=𝟎
Since 𝑈 ∝ 𝑇 Thus, Thus,

U constant Thus, ∆𝑈 = 𝑄 − 𝑊 ∆𝑈 = 𝑄 − 𝑊
Therefore ∆𝑈 = 0 − 𝑊
∆𝑼 = 𝟎 ∆𝑈 = 𝑄 − 𝑊 In an isobaric ∆𝑈 = −𝑊
𝑄 = ∆𝑈 expansion, heat added
Thus, to the gas as it is heated In an adiabatic
and increasing ∆𝑈 and expansion work done by
∆𝑈 = 𝑄 − 𝑊 If the heat added to a work done by the gas. the gas on the
0 = 𝑄−𝑊 gas kept at constant (Figure 14.2 c) surrounding leads to
𝑄=𝑊 volume, all the heat corresponding decrease
goes into increasing the in its internal energy
All heat transfer into the internal energy of the (∆𝑈 negative)
system is converted into gas which is (figure 14.2 d)
work done by the accompanied by
system to the increase in temperature Conversely, in an
surroundings. (figure 14.2 b) adiabatic compression,
the work done on the
Or Conversely, if heat is gas results in a
lost in an isochoric corresponding increase
All work done on the process, the internal in internal energy (∆𝑈
system is converted into energy of the gas positive)
heat lost to decrease so does the
surroundings. temperature Decrease in internal
energy indicates by
decrease in temperature
and vice versa.

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P-V graph for thermodynamic processes

Isothermal Isovolumetric
P
P

𝑃2 A
A
A’

B
𝑇2
𝑃1 B
𝑇1
B’
0 V
0 V
𝑉
Figure 14.2 (a) Ideal gas undergoing isothermal Figure 14.2 (b) Isovolumetric processes. 𝑇𝐴 > 𝑇𝐵
processes at two different temperatures. T2 > T1

Isobaric Adiabatic

P
P
A
A B
𝑃

𝑇2

0 V 𝑇1
𝑉1 𝑉2 B V
0

Figure 14.2 (c) Isobaric processes (expansion). 𝑇𝐵 > Figure 14.2(d) Adiabatic processes (expansion).
𝑇𝐴 𝑇2 > 𝑇1

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Example 3

Sketch a PV diagram of the following process: 2.0 L of ideal gas at atmospheric pressure are
cooled at constant pressure to a volume of 1.0 L, and then expanded isothermally back to 2.0 L,
whereupon the pressure is increased at constant volume until the original pressure is reached.

Example 4

A 1.0 L volume of air initially at 3.5 atm of pressure is allowed to expand isothermally until the
pressure is 1.0 atm. It is then compressed at constant pressure to its initial volume, and lastly
brought back to its original pressure by heating at constant volume. Draw the process on PV
diagram, including numbers and label for the axes.

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Example 5
A vessel contains an ideal gas in condition A as shown in
figure. When the condition of the gas changes from that
of A to B, there is a change in internal energy of 2.49 kJ.
When the condition of the gas changes from B to C,
there is a change in internal energy of 3.74 kJ.
Determine the total amount of heat transfer in the
process ABC. State whether heat has been transferred
into or out of the gas at the end of the process ABC.
[2.75 kJ]

Example 6

When the gas expands from state A directly to state C,

the total quantity of heat absorbed by the gas is 10.0 kJ.
Determine :
a) the change in the internal energy of the gas [-0.13 kJ]
b) the total quantity of heat transferred to the gas if the
following path are taken : (i) ABC (ii) ADC
[15.928 kJ ; 3.925 kJ]

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14.3 Thermodynamic Work

LO 14.3 (a) Discuss the work done in isothermal, isochoric and isobaric processes.
LO 14.3 (b) Solve problems related to work done in
V  P 
i. Isothermal process, W  nRT ln 2   nRT ln 1 
 V1   P2 
ii. Isobaric process, W   PdV  PV 2  V1 
iii. Isochoric process, W   PdV  0
Work done in volume changes

Derivation

𝑑𝑥
P V

(a) (b)
Figure 15.4 (a) A gas in a cylinder occupying a volume V at a pressure P. (b) Pushing the piston
down compresses the gas

a) Consider a gas contained in a cylinder fitted with a movable piston (Figure 15.4).
b) At equilibrium, the gas occupies a volume V and exerts a uniform pressure P on the
cylinder’s wall and on the piston.
c) If the piston has a cross-sectional area A, the magnitude of the force exerted by the gas
on the piston is:
𝐹 = 𝑃𝐴
d) By Newton’s third law, the magnitude of the force exerted by the piston is also .
e) Now let’s assume we push the piston inward and compress the gas quasi-statically
(Volume of a system changes at a rate slow enough to allow pressure to remain
constant throughout the system)
f) As the piston is pushed downward by an external force F, through small displacement
𝑑𝑥, the work done on the gas is, according to our definition of work in chapter 5,
𝑑𝑊 = 𝐹𝑑𝑥
𝑑𝑊 = 𝑃𝐴 𝑑𝑥
Since 𝐴 𝑑𝑥 = 𝑑𝑉, we can express work done on the gas as,

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𝑑𝑊 = 𝑃 𝑑𝑉
For a finite change in volume from 𝑉𝑖 to 𝑉𝑓
∫ 𝑑𝑊 = ∫ 𝑃 𝑑𝑉

𝑊 = ∫ 𝑃 𝑑𝑉
𝑉𝑓
𝑊 = ∫ 𝑃 𝑑𝑉
𝑉𝑖

Work done in isobaric process

In the isobaric process, the pressure remain

P
constant, so
𝑉𝑓 A B
𝑊 = ∫ 𝑃 𝑑𝑉 𝑃
𝑉𝑖
𝑉2
𝑊 = 𝑃 ∫ 𝑑𝑉
𝑉1
𝑉
𝑊 = 𝑃[𝑉]𝑉21
0 V
𝑉1 𝑉2
Figure Isobaric processes.
𝑊 = 𝑃(𝑉2 − 𝑉1 )

 Work done is represented on the PV diagram by the area under the graph.

Work done in isovolumetric process P

In the isovolumetric process, volume is
constant. Therefore, 𝑃2 A

𝑑𝑉 = 0

𝑊 = ∫ 𝑃 𝑑𝑉 = 0 𝑃1 B

0 V
𝑉
Figure Isovolumetric processes.

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Work done in isothermal process

In the isothermal process, temperature, T is constant. P

For an ideal gas,

𝑛𝑅𝑇 𝑃1
𝑃=
𝑉
Work done is
𝑉𝑓
𝑊 = ∫ 𝑃 𝑑𝑉 𝑃2
𝑉𝑖 𝑇
𝑉2
𝑛𝑅𝑇
𝑊=∫ 𝑑𝑉
𝑉1 𝑉 0 V
𝑉2
1 𝑉1 𝑉2
𝑊 = 𝑛𝑅𝑇 ∫ 𝑑𝑉
𝑉1 𝑉 Figure Isothermal processes.
𝑊 = 𝑛𝑅𝑇 [ln 𝑉]𝑉𝑉21
𝑊 = 𝑛𝑅𝑇(ln 𝑉2 − ln 𝑉1 )

𝑉2
𝑊 = 𝑛𝑅𝑇 ൬ln ൰
𝑉1

Since temperature is constant, (T constant)

𝑃1 𝑉1 = 𝑃2 𝑉2
𝑃1 𝑉2
=
𝑃2 𝑉1

Therefore,

𝑃1
𝑊 = 𝑛𝑅𝑇 ൬ln ൰
𝑃2

 Work done is represented on the PV diagram by the area under the graph.

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EXAMPLE 8

Figure 15.8 Example 5

Find the numeric value of the work done on the gas in

(a) Figure 15.8 (a) and

(b) Figure 15.8 (b)

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EXAMPLE 9
P P

A 𝑃1 A
𝑃1

B B
𝑃2 𝑃2
𝑇 C 𝑇

0 V 0 V
𝑉1 𝑉2 𝑉1 𝑉2
(a) (b)
Figure 15.9 (a) Isothermal expansion from point A to point B. (b) Expansion from
point A to point B through Isovolumetric process (AC) and Isobaric process (CB)

Is the work done by the gas in process ACB of figure 15.9 (b) is greater than, less than, or equal
to the work done in the isothermal process AB? Explain.

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EXAMPLE 10

First law in isobaric and isovolumetric

P
processes. An ideal gas is slowly compressed at
𝑃1 A constant pressure of 2.0 atm from 10.0 L to
2.0 L. This process is represented in figure 15.10
as the path B to C. (In this process, some heat
flows out of the gas and the temperature drops.)
B
𝑃2 Heat is then added to the gas, holding volume
C 𝑇 constant, and the pressure and temperature is
allowed to rise (line CA) until temperature
0 V (L)
2 10 reaches its original value (𝑇𝐴 = 𝑇𝐵 ). Calculate:
Figure 15.10 Example
6
a) The total work done by the gas in the process BCA.
b) The change internal energy of the gas in the process.
c) The total heat flow into the gas.

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EXAMPLE 11

Suppose 2.60 mol of an ideal gas of volume 𝑉1 = 3.50 𝑚3 at 𝑇1 = 290 𝐾 is allowed to expand
isothermally to 𝑉2 = 7.00 𝑚3 at 𝑇2 = 290 𝐾. Determine:

a) The work done by the gas.

b) Heat added to the gas.
c) The change in internal energy of the gas.

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EXAMPLE 12

Characterize the path in figure 15.11 as isobaric,

isovolumetric, isothermal, or adiabatic. For path B,
𝑄 = 0. The curves are isotherms.

Figure 15.11 Identify the nature

of paths A,B, C and D

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EXAMPLE 13

A 1.0-mol sample of an ideal gas is kept at 0.0 ℃ during expansion from 3.0 L to 10.0 L.

a) How much work is done on the gas during expansion?

b) How much energy transfer by heat occurs between the gas and its surroundings in this
process?
c) If the gas returned to the original volume by means of an isobaric process, how much
work is done on the gas?

EXAMPLE 14

Gas in a cylinder similar to figure 15.4 moves a piston with are 0.200 𝑚2 as energy is slowly
added to the system. If 2.00 × 103 𝐽 of work is done on the environment and the pressure of the
gas in the cylinder remains constant at 1.01 × 105 𝑃𝑎, find the displacement of the piston.

Answer: 9.90 × 10−2 𝑚

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