The study of relationships

involving heat,
mechanical work, and
other aspects of energy
and energy transfer for
the system.

CHAPTER 15:
Thermodynamics
(4 Hours)
Thermodynamic system is
any collection of objects that is
convenient to regard as a unit,
and that may have the
potential energy to exchange
energy with its surroundings.
surroundings
 SUBTOPIC

15.1 First Law of Thermodynamics

15.2 Thermodynamics Processes
15.3 Thermodynamics Work

2
Learning Outcome:
15.1 First law of thermodynamics (1 hour)
At the end of this chapter, students should be able to:
 Distinguish between work done on the system and work
done by the system.
 State and use first law of thermodynamics,

Q  U  W

3
 15.1 First Law of Thermodynamics
• Thermodynamics is the study of energy relationships that
involve heat, mechanical work, and other aspects of energy
and energy transfer.
• The first law of thermodynamics is the extension of the
principle of conservation of energy to include both heat
and mechanical energy.
• 3 quantities involved in a thermodynamic system :
1. Heat , Q
2. Internal energy , ΔU
3. Work , W

4
 15.1 First law of thermodynamics
15.1.1 Signs for heat, Q and work, W
 Sign convention for heat, Q :
Q = positive value Heat flow into the system
Q = negative value Heat flow out of the system
 Sign convention for work, W:
W = positive value Work done by the system
W = negative value Work done on the system
 Figures 15.1 show a thermodynamic system may exchange
energy with its surroundings (environment).
(a) Surroundings (b) Surroundings
(environment) (environment)

System System
Q0 W 0 Q0 W 5 0
(c) Surroundings (d) Surroundings
(environment) (environment)

System System
Q0 W 0 Q0 W 0

(e) Surroundings (f) Surroundings

(environment) (environment)

System System
Q0 W 0 Q0 W 0
Figure 15.1
6
 Example for work done by the system and work done on the
system are shown in Figure 15.2.
Motion of
Motion of piston
piston

Air
Air
Air
Initially Expansion Compression
Figure 15.2
 When the air is expanded,
expanded the molecule loses kinetic
energy and does positive work on piston.
 When the air is compressed,
compressed the molecule gains kinetic
energy and does negative work on piston. 7
15.1.2 Work done in the thermodynamics system
 Consider the infinitesimal work done by the gas (system) during
the small expansion, dx in a cylinder with a movable piston as
shown in Figure 15.3.

A
Initial Gas

dx
 A
Final F

Figure 15.3
 Suppose that the cylinder has a cross sectional area, A and the
pressure exerted by the gas (system) at the piston face is P.
8
 • The work, dW done by the gas is given by

dW  Fdx cos  where   0  and F  PA

dW  PAdx and Adx  dV
dW  PdV
• In a finite change of volume from V1 to V2,
V2
 dW   V1
PdV
V2 (15.1)
W   PdV
V1
where W : work done
P : gas pressure
V1 : initial volume of the gas
9 V 2 : final volume of the gas
 •the work done is given by
dW  P dV
V2
 dW   V1
PdV
W : work done
W  P V 2  V1  P : gas pressure
V1 : initial volume
V 2 : final volume

W  PV W = - PV
Work done by the system Work done on the system
• Gas expands • Gas is compressed
• Volume increases • Volume decreases
•+W •-W

10
The First Law of Thermodynamics (FLoT)

“ The change in internal energy of a closed

system, ΔU, will be equal to the heat added to
the system minus the work done by the system “

U  Q  W

+ U : increase in internal energy

- U : decrease in internal energy
+ Q : heat is added to the system +Q -Q
system
- Q : heat is removed from the system
-W +W
+ W : work is done by the system
- W : work is done on the system

11
 U  Q  W

Rearrange Q = U + W

Translation :
• When Q is added to a system (gas) , the temperature of the
gas increases, thus causing the internal energy to increase
by an amount of ΔU joule.

• At the same time, when its temperature increases, its

volume increases too.

• When the volume of the gas increases, work is done by the

gas (W).

12
Example 15.1
A 2500 J heat is added to a system and 1800 J work is
done on the system. Calculate the change in internal
energy of the system.

Solution

13
Example 15.3
A gas in a cylinder expands from a volume of 0.400 m3 to
0.700 m3. Heat is added just rapidly enough to keep the
pressure constant at 2.00 x 105 Pa during the expansion.
The total heat added is 1.40 x 105 J.
Calculate the work done by the gas and the change in
internal energy of the gas.
Solution

14
Exercise
1. A system absorbs 200 J of heat as the internal energy
increases by 150 J. What work is done by the gas ?
50 J

2. In a chemical laboratory, a technician applies 340 J of

energy to a gas while the system surrounding the gas
does 140 J of work on the gas. What is the change in
internal energy ?
480 J

3. 8000 J of heat is removed from a refrigerator by a

compressor which has done 5000 J of work. What is the
change in internal energy of the gas in the system?
-3000 J
15
Learning Outcome:
15.2 Thermodynamics processes (1 hour)
At the end of this chapter, students should be able to:
 Define the following thermodynamics processes:
 Isothermal, ΔU= 0
 Isovolumetric, W = 0
 Isobaric, ΔP = 0
 Adiabatic, Q = 0
 Sketch PV graph for all the thermodynamic processes.

16
17
REVISIT! – Kinetic Theory of Gases
Ideal gas equations
Boyle’s Law
 states : “The pressure of a fixed mass of gas at constant
temperature is inversely proportional to its volume.”
volume
1
P or P1V1  P2V2
V
o Charles’ Law
states : The volume of a fixed mass of gas at constant
pressure is directly proportional to its absolute
temperature.”
temperature
V1 V2
V T

or T1 T2
o Pressure Law
states : The volume of a fixed mass of gas at constant
pressure is directly proportional to its absolute
temperature.”
temperature
PT or P P
1 2

T1 T2 18
Equation of state for an ideal gas

 An ideal gas is defined as a perfect gas which obeys the

three gas laws (Boyle’s, Charles’s and Gay-Lussac’s)
exactly.
exactly

 For n mole of an ideal gas,

gas the equation of state is written as

PV  nRT
 where n : the number of mole gas
R : molar gas constant, R  8 .31 J K 1 mol 1
15.2 Thermodynamics processes

• There are 4 common processes of thermodynamics:

1) Isothermal process
2) Isochoric (isovolumetric) process
3) Isobaric process
4) Adiabatic process

(“iso” = same)
T V,P

20
 1) Isothermal process

• Isothermal process is defined as a process that occurs

at constant temperature.

•  U  0 U  U2 - U1 T1 = T2
f f
U  nRT2 - nRT1  0
2 2
From FLoT, U  Q  W
If U = 0 then Q =W

• From the Boyle’s law :

PV = constant
P1V1  P2V 2
21
2) Isochoric (isovolumetric) process

• Isochoric (isovolumetric) process is defined as a

process that occurs at constant volume.

• W =0 W = P (V 2 - V1 ) = 0 V1 = V2

From FLoT, U  Q  W

If W = 0 then
U = Q

22
3) Isobaric process
• Isobaric process is defined as a process that occurs
at constant pressure.

From FLoT, U  Q  W
 U  Q  P V 2  V1  W  PV
4) Adiabatic process
• Adiabatic process is defined as a process that occurs
without the transfer of heat (into or out of the system).

• Q=0 From FLoT, U  Q  W

If Q = 0 then
23
U = - W
 Pressure-Volume Diagram (graph) for
Thermodynamic Processes
P
T4 > T3 > T2 > T1
A E
PA
T4
D B T3
C T2
T1
0 VA V
Path AB Isothermal process (TB=TA)
Path AC Adiabatic process (TC<TA)
Path AD Isochoric process (TD<TA)
Path AE Isobaric process (TE>TA) 24
Exercise
1. A gas system which undergoes an adiabatic process
does 5.0kJ of work against an external force. What is
the change in its internal energy?
5000 J
2. A gas is compressed under constant pressure,
i) Sketch the pressure –volume graph.
ii) How is the work done in compressing the gas
calculated?
iii) Explain what will happen to the final temperature
of the gas.
3. A gas undergoes the following thermodynamics
processes: isobaric expansion, heated at constant
volume, compressed isothermally, and finally expands
adiabatically back its initial pressure and volume. Sketch
all the processes given on the same P-V graph. 25
Learning Outcome:
15.3 Thermodynamics work (2 hours)
At the end of this chapter, students should be able to:

 Derive expression for work , W   PdV

 Determine work from the area under the p-V graph

 Derive the equation of work done in isothermal,
isovolumetric, and isobaric processes.
 Calculate work done in
 isothermal process and use
V2 p1
W  nRT ln  nRT ln
V1 p2
 isobaric process, use
W   PdV  p (V2  V1 )
 isovolumetric process, use
W   PdV  0
26
15.3 Thermodynamics work
Work done in the thermodynamics system
 Consider the infinitesimal work done by the gas (system) during
the small expansion, dx in a cylinder with a movable piston as
shown in Figure 15.3.

A
Initial Gas

dx
 A
Final F

Figure 15.3
 Suppose that the cylinder has a cross sectional area, A and the
pressure exerted by the gas (system) at the piston face is P.
27
 The work, dW done by the gas is given by
dW  F dx cos  where   0  and F  P A
dW  PAdx and Adx  dV
dW  PdV
 In a finite change of volume from V1 to V2,
V2
 dW   V1
PdV
V2
W   PdV (16.1)
V1
where W : work done
P : gas pressure
V1 : initial volume of the gas
V 2 : final volume of the gas
28
PV diagram Work done = area under the P-V graph
P P
isothermal isothermal
P1 1 expansion P2 2 compression

P2 2 P1 1
W 0 W 0
0 V1 V2 V 0 V2 V1 V
P P
isobaric expansion 2
1 P2
P1 2 isochoric

W 0
W  P1 V 2  V 1   0
P1 1
0 V1 V2 V 0 V1 V 29
Equation of work done in thermodynamic processes
1) Isothermal
U  0
Q =W U = Q - W = 0
V2 nRT
V2
Q = W = ∫V1 PdV = ∫V1 dV
V
V2
W = nRT ln From Boyle’s law : P1V1  P2V 2
V1
 V2   P1 
P1     
W = nRT ln  V1   P2 
P2

30
2) Isochoric (isovolumetric)
 Since the volume of the system in isovolumetric process
remains unchanged, thus
dV  0
 Therefore the work done in the isovolumetric process is
Work done at constant
W   PdV  0 volume

3) Isobaric
The work done during the isobaric process which change of
volume from V1 to V2 is given by
V2
W   PdV and P  constant
V1

V2 Work done at
W  P  dV W = P  V = P (V 2 - V1 ) constant
V1 pressure
31
Example 15.4
How much work is done by an ideal gas in expanding
isothermally from an initial volume of 3.00 liters at 20.0
atm to a final volume of 24.0 liters?
Solution
V1 = 3.00 liters, V2 = 24.0 liters ,
P = 20.0 atm

32
Example 15.5
Two liters of an ideal gas have a temperature of 300 K
and a pressure of 20.0 atm. The gas undergoes an
isobaric expansion while its temperature is increased to
500 K. What work is done by the gas ?
Solution T1 = 300 K, T2 = 500 K , P = 20.0 atm, V1 =2 liters

33
 Example 15.8
A gas in the cylinder of a diesel engine can undergo cyclic
processes. Figure below shows one cycle ABCDA that is
executed by an ideal gas in the engine mentioned.
a. If the temperature of the gas in states A and B are 300 K
and 660 K, respectively. Calculate the temperature in
states C and D.
b. Determine the work done by the gas in process BC.
P / x 10 5 P a
B C
16.0
D
7.8

1.0 A

0 1.40 6.00 10.00 V / x 10  4 m 3 34

 Example 15.10
(a) State i. the isobaric process.
ii. the isothermal process.
iii. the adiabatic process. [3 marks]

(b) State the 1st law of thermodynamics. [2 marks]

35
Solution 15.10

b. 1st law of thermodynamics :

36
Exercise
Two moles of ideal gas are at a temperature of 300K and
pressure 2.5 x 105 Pa. The gas expands isothermally to
twice its initial volume, and then undergoes isobaric
compression to its initial volume.

i) Calculate the initial volume of the gas.

ii) What is the pressure of the gas after the gas
expands isothermally to twice its initial volume?
iii) What is the final temperature of the gas after
being compressed isobarically?
iv) Calculate the work done in the isothermal
expansion.
v) Draw the P-V graph for the processes above.
0.02 m3,1.3 x 105 Pa, 150 K, 3.5 x 103 J
37