ZCT214/3

Thermodynamics
Chapter 3: The first law of
thermodynamics
1
DR. SAIFUL NAJMEE BIN MOHAMAD
SCHOOL OF PHYSICS
UNIVERSITI SAINS MALAYSIA
2

1. Work in a volume change

2. Work depends on the path
3. Configuration work and dissipative work
4. The first law of thermodynamics
5. Internal Energy
6. Heat flow
7. Heat flow depends on path
8. The mechanical equivalent of heat
9. Heat capacity
10. Heats of Transformation and Enthalpy
3 1. Work in a volume change

When a system expands against an

external pressure, dV is positive,
the work is positive and we say that
work is done by the system
When a system is compressed, dV is
negative, the work is negative; and
we say that work is done on the
system
4

dFe = Pe dA
 The figure shows
work done by a
ds dA system expanding
against an external
V force, given by Pe dA
ds
 MKS units for
pressure is Nm-2, for
work is Nm or J
5

 Moving boundary work

(P dV work): The expansion
and compression work in a
piston-cylinder device.

′W F=
d= ds PA=
ds P dV

 A gas does a differential

amount of work d′W as it
forces the piston to move by a
differential amount ds.
6

The work of the external forces exerted on

the boundary of a system is known as
external work
If a process is reversible, the system is in
mechanical equilibrium at all times and the
external pressure, Pe equals the pressure P
exerted against the boundary by the system
(3.2)
d ′W = P dV
7
• In a finite reversible process in which the
volume changes from Va to Vb, the total work
is:
Vb
W= ∫Va
P dV (3.3)

• The relation between pressure and volume of

a system, in any reversible process, can be
represented by a curve in the P-V plane
• The work in an isochoric process is zero as
V = constant
 8

P
• In an isobaric process the
pressure is constant and the
work is represented by the
area of the shaded rectangle as
shown: P

dV = P (Vb − Va )
Vb
W =P ∫
Va

Va Vb V
(3.4)
9

 If P is not constant, and if the system is an

ideal gas:
nRT
P=
V
 For an isothermal process with T constant;

Vb dV Vb
W = n RT ∫Va V
= n RT ln
Va
(3.5)
10

 The work is represented P

by the shaded area in
the figure
 If Vb>Va, the process is
an expansion and work
is positive
T
 If Vb<Va, the process is a
compression and work
is negative V
Va Vb
11 2. Work depends on the path

• Work depends on path and not simply on

its endpoints
• Work is a path function
b Vb
W = ∫ d ′W = ∫ P dV
a Va

• The quantity d’W is an inexact differential

and work W is not a property of the system
12 Example 3.1

 Derive the general expression for the work per

kilomole of a van der Waals gas in expanding
reversibly and at a constant T from a specific
volume v1 to a specific volume v2.
13 Solution: RT a
Van der Waals gas P= − 2
v −b v
v2
W =∫ P dv
v1

v2  RT a
=∫  − 2  dv
v1
 v−b v 
v2
 a
=  RT ln (v − b ) + 
 v  v1

= RT ln
(v2 − b )  a a 
+  − 
(v1 − b )  v2 v1 
14

P
• If the system in the
figure is taken from b
state a to state b
I
along path I and
then returned from
state b to state a II
a
along path II, the
system performs a
cyclic process
V
 P

I b
15
a II

 The positive work along path I is greater

than the negative work along path II
 The net work in the cycle is positive, or
work is done by the system
 Net work is represented by the area bounded
by the closed path
 P

I b
16
a II

V
 If the cycle is traversed in the opposite sense,
from a to b along path II and returned from b
to a along path I, the net work is negative and
work is done on the system
 In either case, the magnitude of net work is:

∫
W = dW = P dV ∫ (3.14)
17 3. Configuration work and
dissipative work

• The configuration of a
system can change
Pe=0 without the
performance of work
• In the figure, a vessel is
divided into two parts
by a diaphragm
• The space above the
diaphragm is evacuated
and that below contains
a gas
18

 If the diaphragm is punctured, the gas

expands into the evacuated region and fills
the entire vessel
 The process is known as a free expansion
 Since the space above the diaphragm is
evacuated, the external pressure Pe on the
diaphragm is zero
 In a free expansion of a gas, configuration
work is zero
19

 The work in a free expansion is:

∫
W = Pe dV = 0

 The work is zero even though the volume of

the gas increases
20

Examples of dissipative work

 a stirrer immersed in fluid and doing stirring
work (mechanical)
 the work (electrical) needed to maintain an
electric current I in a resistor of resistance R
Dissipative work has close connection
with a flow of heat
21

Any process in which dissipative

work is done is necessarily
irreversible
 Work is done on a system when a stirrer in a fluid
is rotated, but a small change in the external
torque rotating the stirrer will not result in work
being done by the system
 A small change in the terminal voltage of a source
sending a current through a resistor will not
result in work being done by the resistor
22

If a process is to be reversible, the

dissipative work must be zero
A process is reversible implies that
(i) the process is quasistatic
(ii) the dissipative work is zero
In a reversible process, the total work
equals the configuration work
23 example 3.2
Work done by a system does not only depend on the
initial and final states but also on the paths followed.

i a
2P0

P0 b f

V
V0 2V0
24

Referring to the figure shown,

P
 Work done by following the
path iaf is 2 P0V0
2P0 i a

 Work done by following the

path ibf is P0V0 P0 b f

V0 2V0 V
 Work done by following the
path if (diagonally) is 3
P0V0
2
25 4. The first law of
thermodynamics
 An adiabatic process means that there is no
energy that enters or leaves a system by heat; Q
=0
 This can be achieved either by thermally
insulating the walls of a system, or by
performing the process rapidly, so that there is
negligible time for energy to transfer by heat
26

 Consider an adiabatic process between two

given states of which a system is enclosed by
an adiabatic boundary and its temperature is
independent of the surroundings
 The boundary need not be rigid, so that
configuration work can be done on or by the
system
 Assume that dissipative work can be done on
the system, and there is no change in KE and
PE
27

 a-c adiabatic free expansion (no net work done and

assume there is no dissipative work)
 c-b reversible adiabatic expansion ( work=shaded area
under cb curve)
Wa −c −b = area shaded under cb curve
28

 a-d reversible adiabatic expansion (work=shaded area

under ad curve)
 d-b adiabatic free expansion (no net work done and
assume there is no dissipative work)

Wa − d −b = area shaded under ad curve

29

 a-e reversible adiabatic expansion (work=shaded area

under ae curve)
 e-b dissipative process (work = dissipative work)
 From experiment
Wa −=
e −b Wa −e − We −b Wd −e = We −b
30

 From experiment
=
Wa − c −b W=
a − d −b Wa −e −b

 it can be concluded that the entire structure of

thermodynamics is consistent with the statement of the
first law of thermodynamics
31

• First law of thermodynamics

the total work is the same in all adiabatic

processes between any two equilibrium
states having the same kinetic and
potential energy
32 5. Internal Energy

 A property of a system, U such that the difference

between its values in states a and b is equal to the
total work done by the system along any adiabatic
path from a to b; is known as the internal energy
of the system
 The value of the internal energy depends only on the
state of the system, hence dU is an exact differential
33

dU is defined as the negative of the adiabatic

work d′Wad done by the system or as equal
to the adiabatic work done on the system

dU = −d 'Wad
Ub b
∫Ua
dU =Ub − U a =− ∫ d ′Wad =
a
− Wad
34
Ub b
∫Ua
dU = U b − U a = − ∫a
dWad = − Wad

U a − U b = Wad (3.16)

 The total work W ad done by a system in any

adiabatic process between two states a and b having
the same KE and PE is equal to the decrease ( Ua -
Ub) in the internal energy of the system
35 6. Heat flow

Consider processes between a given pair

of equilibrium states that are not adiabatic
The system is not thermally insulated
from its surrounding with one or more
systems whose temperature differs
36

 Under these circumstances, there is a heat flow

Q between the system and its surroundings
 heat flow Q into a system in any process is the
difference between the total work and adiabatic
work:
Q = W − Wad (3.17)
 (unit J, Joule)
37

 Depending on the nature of a process, the work W

may be greater or less than the adiabatic work Wad

 therefore, Q may be positive or negative

 If Q is positive there is a heat flow into the

system

 IfQ is negative there is a heat flow out of the

system
38

 If the temperature of the surroundings is

greater than that of the system, there will be a
heat flow into the system and Q > 0
 If the temperature of the surroundings is lower
than that of the system, there will be a heat
flow out of the system and Q < 0
39
Q = W − Wad

If a process is adiabatic, the total work W

becomes simply the adiabatic work Wad and
from equation above Q =0; this means that
there is no flow of heat even if there is a
temperature difference between the surfaces of
the boundary
An adiabatic boundary is an ideal heat
insulator
40

 The increase in internal energy of a system

(in any process in which there is no change
in the KE and PE of the system) equals the
net heat flow Q into the system minus the
total work W done by the system

Ub −Ua = Q −W (3.18)

dU = dQ − dW (3.19)

General form of the first law

41

 Equations (3.18) and (3.19) is also known as

the analytical formulation of the first law of
thermodynamics
 Equations (3.18) and (3.19) can be used in
processes that are reversible and
irreversible
42

For a reversible process, the

dissipative work is zero
The only work is configurative work
and for a PVT system, dW = P dV

dU = dQ − P dV (3.20)
43 7. Heat flow depends on path

• Equations (3.18) and (3.19) can be

written :

Q = (U b − U a ) + W

dQ = dU + dW
44
Ub −Ua = Q −W

 dQ, like dW is an inexact differential and

Q is not a property of a system
 Heat, like work is a path function
 If the process is cyclic (its end states
coincide); there is no change in internal
energy and from eqn. (3.18),

Q =W
45

In such a process, the net heat flow Q

into the system equals the net work W
done by the system

Q =W
46 8. The mechanical equivalent
of heat

The change in internal energy of a

system, in a dissipative process, is the
same as if there had been a heat flow Q
into the system, equal in magnitude to
the dissipative work
Heat can be measured in unit calorie:

1 calorie = 4.186 J
47

• In a thermodynamic process, the internal

energy U of the system may

ΔU > 0),
(a) increase (

(b) decrease (ΔU < 0) or

(c) not change/remain the same (ΔU = 0)

as shown in the next slides;
48 a) The internal energy of the system will
increase when there is more heat
supplied into the system than work done
by the system

environment

Q = 150 J W = 100 J
system

ΔU = Q – W = + 50 J
49 b) The internal energy will decrease when
there is more heat leaving the system
than work done on the system

environment

Q = -150 J W = -100 J
system

ΔU = Q – W = -50 J
50 c) There is no change in internal energy
when heat supplied into the system is
equivalent to the work done by the system

environment

Q = 150 J W = 150 J
system

ΔU = Q – W = 0 J
51 Example 3.4 The figure below shows a pV
diagram for a cyclic process, where the initial and
final states coincide. It starts at point a and goes in a
counter clockwise direction to point b, and then it
returns to point a with total work W = -500 J.
p
a) Why is work negative?
b) Find the change in internal a path 2
energy and the heat added pa
during this process.
c) If the cyclic process occurs pb b
in a clockwise direction,
what would be the total path 1
work?
V
Va Vb
 p
a
52 Solution: pa

pb b

V
Va Vb
a) Work done is equivalent to the area under the
curve, where the area is considered positive if the
volume of the system increases and negative if the
volume decreases.
The area under the curve from a to b is positive but
of a lesser magnitude than the area under the curve
from b to a that has a negative area
Therefore, the shaded area in the figure shows a
negative work, which is work done of 500 J on the
system
53

b) For this or any cyclic process where the initial

and final states coincide,
ΔU = 0,
so that Q = W = -500 J.
Here, 500 J of heat is dissipated out of the
system (leave the system)
54

c) The total work would be positive

showing work done by the
system
55 Example 3.5 A series of thermodynamic
processes is shown in the pV diagram below. In
process ab, 150 J of heat is added to the system,
and in process bd, 600 J of heat is added. Find
p
a) the change in internal
b
energy in the process 8.0 ×104 Pa d
ab,
b) the change in internal
energy in the process
abd, and
c) the total heat added in 3.0 ×104 a c
process acd. Pa

2.0×10-3 m3 5.0×10-3
m3
 p

Solution:
b
56 8.0 ×104 Pa d

3.0 ×104 Pa a c

V
2.0×10-3 m3 5.0×10-3 m3

In each process we will use ΔU = Q – W

Given Qab = +150 J and Qbd = +600 J (both values are
+ive because heat is added to the system)
a) no volume change occurs during process ab, so
Wab = 0 and ΔUab = Qab = 150 J
b) process bd occurs at constant pressure, so the
work done by the system during this expansion,
57

Wbd = p(V2 − V1 )
(
= 8.0 × 10 4
)(5.0 × 10 −3
− 2.0 × 10 −3
)
= 240 J
Wabd = Wab + Wbd = 0 + 240 = 240 J

Qabd = Qab + Qbd = 150 + 600 = 750 J

∆U abd = Qabd − Wabd = 750 − 240 = 510 J
58

c) because ΔU is independent of path, the

internal energy change is the same for path
acd as for path abd,

∆U acd = ∆U abd = 510 J

Wacd = Wac + Wcd = p(V2 − V1 ) + 0
= (3.0 × 10 )(5.0 × 10
4 −3
− 2.0 × 10 −3
) = 90 J
Qacd = ∆U acd + Wacd = 510 + 90 = 600 J
59 9. Heat capacity
 The mean heat capacity C of a system, is defined
as the ratio of the heat flow Q into the system to the
corresponding change in temperature, ΔT:

Q
C= ( 3.27 )
∆T
 The true heat capacity:
Q dQ
= =
C lim
∆T →0 ∆T
( 3.28)
dT
(unit J K-1)
60

 The heat capacity of a system depends both on

the nature of the system and the particular
process the system may undergo
 The heat capacity in a process in which a system is
subjected to a constant external pressure is called
the heat capacity at constant pressure, CP
 CP depends on the pressure and temperature
61

 If a system is kept at constant volume while heat

is supplied to it, the corresponding heat capacity
is called the heat capacity at constant volume, CV
 To measure the heat capacity of a system
experimentally, we must measure the heat flowing
into the system in a process, and measure the
corresponding change in temperature
62

 The specific heat capacity or the heat capacity

per unit mass or per mole, is the characteristic of
the material of which the system is composed of,
known as cP or cv
 Unit of specific heat capacity is J kg-1K-1 or
J kilomol-1K-1
Q
c=
m∆T
63

c c
 At low temperatures (< 300 K), values of P and v are
almost equal

c
 At high temperatures (>300 K), P values continue
c
increasing while v values become constant
(25×10 J kilomol K – known as Dulong
3 -1 -1
and Petit value for many solids)

c
 The specific heat capacity at constant volume, v at high
temperatures is nearly equal to 3R where R is the gas
constant
64

 For a monatomic gases,

cP 5 cv 3
≈ and ≈
R 2 R 2
 For diatomic gases,

cP 7 cv 5
≈ and ≈
R 2 R 2
 dQ
65 C=
dT

• The total quantity of heat flowing into a

system in any process is;
T2 T2
Q = ∫ dQ = ∫T1
C dT = n ∫
T1
c dT

where C is the heat capacity

Q = C (T2 − T1 ) = n c (T2 − T1 )
66

 The larger the heat capacity of a system, the

smaller its change in temperature for a given heat
flow
 A system of very large heat capacity is called a
heat reservoir
 Any reversible process carried out by a system in
contact with a heat reservoir is isothermal
67

Conservation of energy allows us to

write the mathematical representation of
the energy statement as

Qcold = −Qhot (*)

68

 Suppose mx is the mass of a sample of some substance

whose specific heat we wish to determine. Let us call
its specific heat cx and its initial temperature Tx.
Likewise, let mw, cw and Tw represent corresponding
values for the water. If Tf is the final equilibrium
temperature after everything is mixed, from

Q = mc∆T
69

 we find that the energy transfer for the water is ,

which is positive because Tf > Tw, and that the
energy transfer for the sample of unknown specific
heat is , which is negative.
 Substituting this expression into eqn (*) gives;

m w c w (T f − Tw ) = −m x c x (T f − Tx )
m w c w (T f − Tw )
cx =
m x (Tx − T f )
70 Example 3.6

 A 0.05 kg ingot of metal is heated to 200°C and

then dropped into a beaker containing 0.4 kg of
water initially at 20°C. If the final equilibrium
temperature of the mixed system is 22.4°C, find
the specific heat of the metal.
71 Solution:

mwcw (T f − Tw ) = − mx c x (T f − Tx )
 J 
(0.4 kg ) 4186 (22.4 − 20 )°C =
 kg ⋅ °C 
− (0.05 kg ) c x (22.4 − 200 )°C

J
c x = 453
kg ⋅ °C
72

 The ingot is most likely

iron, from the Table
shown
73

 Note that the temperature of the ingot is initially

above the steam point. Thus, some of the water
may vaporize when we drop the ingot into the
water. We assume that we have a sealed system
and that this steam cannot escape. Because the
final equilibrium temperature is lower than the
steam point, any steam that does result
recondenses back into water.
74 Example 3.7

The heat capacity for a metal at low temperature

changes with temperature as follows;

aT 3
C = 3 + bT
θ
where a, b and θ are constants.
How much heat per mole is transferred into a process
if its temperature changes from 0.01θ to 0.02θ?
75 Solution:
Q = ∫ C dT
0.02θ
 aT 3 
= ∫θ
0.01
 3 + bT  dT
 θ 
0.02θ
 aT bT  4 2
=  3 + 
 4θ 2  0.01θ
aθ 4 θ 2
=
4θ 3
(
0.02 4
− 0.014
+
b
2
) (
0.02 2
− 0.012
)
= 3.75 ×10−8 aθ + 1.5 ×10−4 bθ 2
 10. Heats of Transformation
76 and Enthalpy

Consider a portion of an
isothermal process in either
the solid-liquid, liquid-
vapor or solid-vapor region,
and let the process proceed
in such a direction that a
mass m is converted from
solid to liquid, liquid to
vapor or solid to vapor
77

 The system is said to absorb heat, and the

l
heat of transformation is defined as
the ratio of the heat absorbed to the mass
m undergoing the change of phase
 Unit of l is J kg-1 or J kilomole-1
78

 A substance often undergoes a change in

temperature when energy is transferred between
it and its surroundings.
 There are situations, however, in which the
transfer of energy does not result in a change in
temperature.
 This is the case whenever the pysical
characteristics of the substance change from one
form to another; such a change is commonly
referred to as a phase change.
79

 Two common phase changes are from solid to liquid

(melting) and from liquid to gas (boiling);
another is a change in the crystalline structure of a
solid.
 All such phase changes involve a change in internal
energy but no change in temperature.
80

 The amount of energy transferred during a phase

change depends on the amount of substance
involved.
 If a quantity Q of energy transfer is required to
change the phase of a mass m of a substance, the
ratio characterizes an important thermal property
of that substance.
81

 Because this added or removed energy does not result

in a temperature change, the quantity L is called the
latent heat (literally, the “hidden” heat) of the
substance.
 The value of L for a substance depends on the nature
of the phase change, as well as the properties of the
substance.
82

 The energy required to change the phase of a

given mass m of a pure substance is

Q = ± mL
 Latent heat of fusion Lf is the term used
when the phase change is from solid to liquid
and the latent heat of vaporization Lv is
the term used when the phase change is
from liquid to gas.
83

 The positive sign is used when energy

enters the system, causing melting or
vaporization.
 The negative sign corresponds to energy
leaving a system, such that system
freezes or condenses
84
85 Example 3.8

 What mass of steam initially at 130°C is needed

to warm 200 g of water in a 100 g glass
container from 20°C to 50°C?
86 Solution:
 The steam loses energy in three stages. In
the first stage, the steam is cooled to 100°C.
The energy transfer in the process is

Q1 = m s c s ∆T
 J 
= m s  2.01 × 10 3
(100 − 130 )°C
 kg ⋅ °C 
 4 J 
= −m s  6.03 × 10 
 kg 
 where ms is the unknown mass of steam.
87

 In the second stage, the steam is converted

to water. To find the energy transfer during
this phase change, we use , indicating energy
leaving the steam:

 6 J 
Q2 = −m s  2.26 × 10 
 kg 
88

 In the third stage, the temperature of water

created from the steam is reduced to 50°C.
This change requires an energy transfer of

Q3 = m s c w ∆T
 J 
= m s  4.19 × 10 3
(50 − 100 )°C
 kg ⋅ °C 
 5 J 
= −m s  2.09 × 10 
 kg 
89

 Adding the energy transfers in these three stages,

Qhot = Q1 + Q2 + Q3
 6 J 
= −m s  2.53 × 10 
 kg 
90

 Now, turning to the temperature increase of

the water and the glass, we have

 J 
Qcold = (0.2kg ) 4.19 × 10 3
(50 − 20 )°C
 kg ⋅ °C 
 J 
+ (0.1kg ) 837 (50 − 20 )°C
 kg ⋅ °C 
= 2.77 × 10 J
4
91

 Using eqn (*) and solving for the unknown

mass;

Qcold = −Qhot
m s = 1.09 × 10 − 2 kg = 10.9 g

End example
92 Example 3.9

1 g of water (1 cm3) becomes 1671 cm3 of

steam when boiled at pressure 1 atm.
Calculate the work done by the water when
it vaporizes. If the latent heat of
vaporization at this pressure is 2.256 x 106
Jkg-1, calculate its increase in internal
energy.
93 Solution:
1 atm = 1.013×105 Pa

∫ P dV = P (V − V )
V2
W= 2 1
V1

= (1.013 × 10 ) ((1671 − 1) × 10 )
5 −6

= 169.2 J Work done by the system

against the surroundings while
∆U = Q − W expanding from liquid to vapor

= m L −W
(
= 10 −3
)(2.256 ×10 ) − 169 = 2087 J
6
94

• If a phase change takes place at

constant temperature, the pressure is
constant too and the specific work done
by the system is

=w P ( v2 − v1 )
• Changes of phase are always associated
with changes in volume, so that work is
always done on or by a system
95

 From the first law, the change in specific

internal energy is;

u 2 − u1 = l − P(v 2 − v1 )

l = (u 2 + Pv 2 ) − (u1 + Pv1 )
96

 specific enthalpy is;

h= u + Pv (J kg or J kilomole )
-1 -1

 The heat of transformation in any change of

phase is equal to the difference between the
enthalpies of the system in the two phases;

l = (u 2 + Pv 2 ) − (u1 + Pv1 ) l = h2 − h1
97

 Since enthalpy is a state function, its value

depends only on the state of the system
 If a system performs a cyclic process, the
initial and final enthalpies are equal and the
net enthalpy change in the process is zero
 At the triple point, the heat of sublimation
equals the sum of the heat of vaporization
and the heat of fusion
98

 Read example on pg. 84 of Sears and Salinger