ZCT 212/2

thermodynamics
Chapter 3
The first law of
thermodynamics

Chapter 3: The first law of
thermodynamics
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
2
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
ds
dF
e
= P
e
dA
dA
V
The figure shows work
done by a system
expanding against an
external force,
given by P
e
dA ds
MKS units for
pressure is Nm
-2
, for
work is Nm or J
dAds P ds dF
e e
=
5
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, P
e
equals the pressure P
exerted against the boundary by the system
(3.2)
dV P dW =
6
- In a finite reversible process in which the volume
changes from V
a
to V
b
, the total work is:

(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
}
=
b
a
V
V
dV P W
7
- In an isobaric process
the pressure is constant
and the work is
represented by the area
of the shaded rectangle
as shown:



(3.4)
( )
}
= =
b
a
V
V
a b
V V P dV P W
P
P
V
V
a
V
b

8
If P is not constant, and if the system is an
ideal gas:


For an isothermal process with T constant;

V
nRT
P =
a
b
V
V
V
V
ln T R n
V
dV
T R n W
b
a
= =
}
(3.5)
9
- The work is represented
by the shaded area in the
figure
If V
b
>V
a
, the process is
an expansion and work
is positive
If V
b
<V
a
, the process is a
compression and work is
negative
P
T
V
V
a
V
b

10
2. Work depends on the path
- Work depends on path and not
simply on its endpoints
- Work is a path function


- The quantity dW is an inexact
differential and work W is not a
property of the system
dV P W d W
b
a
V
V
b
a
} }
=
'
=
11
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 v
1
to a specific
volume v
2
.
12
Solution:
Van der Waals gas
2
v
a
b v
RT
P

=
( )
( )
( )
|
|
.
|

\
|
+

=
(

+ =
1 2 1
2
ln
ln
2
1
v
a
v
a
b v
b v
RT
v
a
b v RT
v
v
}
}
|
.
|

\
|

=
=
2
1
2
1
2
v
v
v
v
dv
v
a
b v
RT
dv P W
13
- If the system in the
figure is taken from
state a to state b
along path I and then
returned from state b
to state a along path
II, the system
performs a cyclic
process
P
V
I
II
a
b
14
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
V
I
II
a
b
15
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:

(3.14)
} }
= = dV P dW W
P
V
I
II
a
b
16
3. Configuration work and
dissipative work
- The configuration of a
system can change
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
P
e
=0
17
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 P
e
on the
diaphragm is zero
In a free expansion of a gas, configuration
work is zero
18
The work in a free expansion is:



The work is zero even though the volume of the
gas increases
}
= = 0 dV P W
e
19
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
20
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
21
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
22
example 3.2
Work done by a
system does not
only depend on
the initial and
final states but
also on the paths
followed.
P
2P
0

V
f
b
a i
P
0

V
0
2V
0

23
Referring to the figure shown,
Work done by following the
path iaf is

Work done by following the
path ibf is

Work done by following the
path if (diagonally) is
P
2P
0

V
f b
a i
P
0

V
0
2V
0

0 0
2 V P
0 0
V P
0 0
2
3
V P
24
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
25
- 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
26
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
27
dU is defined as the negative of the adiabatic
work dW
ad
done by the system or as equal
to the adiabatic work done on the system


ad
dW dU =
ad
b
a
ad a b
U
U
W dW U U dU
b
a
= = =
} }
28

(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 (U
a
- U
b
) in the internal energy of
the system
ad b a
W U U =
ad
b
a
ad a b
U
U
W dW U U dU
b
a
= = =
} }
29
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
30
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:

(3.17)
(unit J, Joule)
ad
W W Q =
31
Depending on the nature of a process, the
work W may be greater or less than the
adiabatic work W
ad
therefore, Q may be positive or negative
If Q is positive there is a heat flow into the
system
If Q is negative there is a heat flow out of
the system
32
If the temperature of the surroundings is
greater than that of the system, there will be a
heat flow into the system and Q is positive
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 is negative
33
If a process is adiabatic, the work W
becomes simply the adiabatic work W
ad

and from equation (3.17) Q is zero;
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
ad
W W Q =
34
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

(3.18)

(3.19)
W Q U U
a b
=
dW dQ dU =
General form of the first law
35
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
36
For a reversible process, the dissipative
work is zero
The only work is configurative work
and for a PVT system, dW = P dV

(3.20)

dV P dQ dU =
37
7. Heat flow depends on path
- Equations (3.18) and (3.19) can be
written :

( ) W U U Q
a b
+ =
dW dU dQ + =
38
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),
W Q=
W Q U U
a b
=
39
In such a process, the net heat flow Q
into the system equals the net work W
done by the system
W Q=
40
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:
J calorie 186 . 4 1 =
41
- In a thermodynamic process, the internal
energy U of the system may
(a) increase (U > 0),
(b) decrease (U < 0) or
(c) not change/remain the same (U = 0)
as shown in the next slides;

42
environment
system
Q = 150 J W = 100 J
U = Q W = + 50 J
a) The internal energy of the system will increase
when there is more heat supplied into the
system than work done by the system
43
b) The internal energy will decrease when there
is more heat leaving the system than work
done on the system
environment
system
Q = -150 J W = -100 J
U = Q W = -50 J
44
c) There is no change in internal energy when
heat supplied into the system is equivalent to
the work done by the system
environment
system
Q = 150 J W = 150 J
U = Q W = 0 J
45
Example 3.3
1 g of water (1 cm
3
) becomes 1671 cm
3
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 10
6
Jkg
-1
, calculate its
increase in internal energy.
46
Solution:
1 atm = 1.01310
5
Pa
( )
( ) ( ) ( )
J .
.
V V P dV P W
V
V
2 169
10 1 1671 10 013 1
6 5
1 2
2
1
=
=
= =

}
( )( ) J
W L m
W Q U
2087 169 10 256 . 2 10
6 3
= =
=
= A

Work done by the system

against the surroundings while
expanding from liquid to vapor
47
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.
a) Why is work
negative?
b) Find the change in
internal energy and
the heat added during
this process.
c) If the cyclic process
occurs in a clockwise
direction, what would
be the total work?
p
p
a

p
b

V
a
V
b

V
a
b
48
Solution:
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
p
p
a

p
b

V
a
V
b

V
a
b
49
b) For this or any cyclic process where the
initial and final states coincide,
U = 0,
so that Q = W = -500 J.
Here, 500 J of heat is dissipated out
of the system (leave the system)
50
c) The total work would be positive
showing work done by the system
51
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
a) the change in
internal energy in
the process ab,
b) the change in
internal energy in
the process abd, and
c) the total heat added
in process acd.
p
8.0 10
4
Pa
V
c
b
a
d
3.0 10
4
Pa
2.010
-3
m
3
5.010
-3
m
3

52
Solution:
In each process we will use U = Q W
Given Q
ab
= +150 J and Q
bd
= +600 J (both values
are +ive because heat is added to the system)
a) no volume change occurs during process ab,
so W
ab
= 0 and U
ab
= Q
ab
= 150 J
b) process bd occurs at constant pressure, so
the work done by the system during this
expansion,
p
8.0 10
4
Pa
V
c
b
a
d
3.0 10
4
Pa
2.010
-3
m
3

5.010
-3
m
3

53
( )
( )( )
J
. . .
V V p W
bd
240
10 0 2 10 0 5 10 0 8
3 3 4
1 2
=
=
=

J W W W
bd ab abd
240 240 0 = + = + =
J Q Q Q
bd ab abd
750 600 150 = + = + =
J W Q U
abd abd abd
510 240 750 = = = A
54
c) because U is independent of path, the
internal energy change is the same for path
acd as for path abd,
J U U
abd acd
510 = A = A
( )
( )( ) J . . .
V V p W W W
cd ac acd
90 10 0 2 10 0 5 10 0 3
0
3 3 4
1 2
= =
+ = + =

J W U Q
acd acd acd
600 90 510 = + = + A =
55
9. Heat capacity
The mean heat capacity of a system, is
defined as the ratio of the heat flow Q into
the system to the corresponding change in
temperature, T:
(3.27)

The true heat capacity:

(3.28)
(unit J K
-1
)
C
T
Q
C
A
=
dT
dQ
T
Q
lim C
T
=
A
=
A 0
56
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, C
P
C
P
depends on the pressure and temperature
57
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, C
V
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
58
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 c
P
or c
v
Unit of specific heat capacity is J kg
-1
K
-1
or
J kilomol
-1
K
-1

59
At low temperatures (< 300 K), values of c
P

and c
v
are almost equal
At high temperatures (>300 K), c
P
values
continue increasing while c
v
values become
constant (2510
3
J kilomol
-1
K
-1
known
as Dulong and Petit value for many solids)
The specific heat capacity at constant volume,
c
v
at high temperatures is nearly equal to 3R
where R is the gas constant
60
For a monatomic gases,

and

For diatomic gases,

and

2
5
~
R
c
P
2
3
~
R
c
v
2
7
~
R
c
P
2
5
~
R
c
v
61
- The total quantity of heat flowing into a
system in any process is;





where C is the heat capacity
} } }
= = =
2
1
2
1
T
T
T
T
dT c n dT C dQ Q
( ) ( )
1 2 1 2
T T c n T T C Q = =
dT
dQ
C =
62
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
Conservation of energy allows us to write
the mathematical representation of the
energy statement as

(*)
63
hot cold
Q Q =
Suppose m
x
is the mass of a sample of some
substance whose specific heat we wish to
determine. Let us call its specific heat c
x
and
its initial temperature T
x
. Likewise, let m
w
,
c
w
and T
w
represent corresponding values for
the water. If T
f
is the final equilibrium
temperature after everything is mixed, from
64
T mc Q A =
we find that the energy transfer for the water is
positive because T
f
> T
w
, and that the energy transfer
for the sample of unknown specific heat is , which is
negative.
Substituting this expression into eqn (*) gives;


65
( ) ( )
( )
( )
f x x
w f w w
x
x f x x w f w w
T T m
T T c m
c
T T c m T T c m

=
=
Example 3.6
A 0.05 kg ingot of metal is heated to 200C
and then dropped into a beaker containing
0.4 kg of water initially at 20C. If the final
equilibrium temperature of the mixed system
is 22.4C, find the specific heat of the metal.

66
Solution:
67
( ) ( )
( ) ( )
( ) ( ) C c kg
C
C kg
J
kg
T T c m T T c m
x
x f x x w f w w

=
|
|
.
|

\
|

=
200 4 . 22 05 . 0
20 4 . 22 4186 4 . 0
C kg
J
c
x

= 453
The ingot is most
likely iron, from the
Table shown

68
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.
69
End example
70
Example 3.7
The heat capacity for a metal at low
temperature changes with temperature as
follows;


where a, b and are constants.
How much heat per mole is transferred into a
process if its temperature changes from 0.01
to 0.02?
bT
aT
C +
u
=
3
3
71
Solution:
u
u
(

+
u
=
02 0
01 0
2
3
4
2 4
.
.
bT aT
dT bT
aT
dT C Q
.
.
|
|
.
|

\
|
+
u
= =
} }
u
u
3
3
02 0
01 0
( ) ( )
2 4 8
2 2
2
4 4
3
4
10 5 1 10 75 3
01 0 02 0
2
01 0 02 0
4
u + u =

u
+
u
u
=

b . a .
. .
b
. .
a
End example
72
10. Heats of Transformation
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

73
The system is said to absorb heat, and the
heat of transformation l 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
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.
74
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.
75
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.
76
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.
77
The energy required to change the phase of a
given mass m of a pure substance is


Latent heat of fusion L
f
is the term used
when the phase change is from solid to liquid
and the latent heat of vaporization L
v
is
the term used when the phase change is from
liquid to gas.
78
mL Q =
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
79

80
Example 3.8
What mass of steam initially at 130C is
needed to warm 200 g of water in a 100 g
glass container from 20C to 50C?
81
Solution:
The steam loses energy in three stages. In the
first stage, the steam is cooled to 100C. The
energy transfer in the process is





where m
s
is the unknown mass of steam.

82
( )
|
|
.
|

\
|
=

|
|
.
|

\
|

=
A =
kg
J
m
C
C kg
J
m
T c m Q
s
s
s s
4
3
1
10 03 . 6
130 100 10 01 . 2
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:

83
|
|
.
|

\
|
=
kg
J
m Q
s
6
2
10 26 . 2
In the third stage, the temperature of water
created from the steam is reduced to 50C.
This change requires an energy transfer of
84
( )
|
|
.
|

\
|
=

|
|
.
|

\
|

=
A =
kg
J
m
C
C kg
J
m
T c m Q
s
s
w s
5
3
3
10 09 . 2
100 50 10 19 . 4
Adding the energy transfers in these three
stages,
85
|
|
.
|

\
|
=
+ + =
kg
J
m
Q Q Q Q
s
hot
6
3 2 1
10 53 . 2
Now, turning to the temperature increase of
the water and the glass, we have

86
( ) ( )
( ) ( )
J
C
C kg
J
kg
C
C kg
J
kg Q
cold
4
3
10 77 . 2
20 50 837 1 . 0
20 50 10 19 . 4 2 . 0
=

|
|
.
|

\
|

+

|
|
.
|

\
|

=
T mc Q A =
Using eqn (*) and solving for the unknown
mass;
87
g kg m
Q Q
s
hot cold
9 . 10 10 09 . 1
2
= =
=

End example
88
- If a phase change takes place at constant
temperature, the pressure is constant too and
the specific work done by the system is



- Changes of phase are always associated with
changes in volume, so that work is always
done on or by a system
( )
1 2
v v P w =
89
From the first law, the change in specific
internal energy is;
( )
1 2 1 2
v v P l u u =
( ) ( )
1 1 2 2
Pv u Pv u l + + =
dW dQ dU =
90
specific enthalpy is;

(J kg
-1
or J kilomole
-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;
Pv u h + =
1 2
h h l =
( ) ( )
1 1 2 2
Pv u Pv u l + + =
91
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