Unit 5

1
UNIT 5 SPECIFIC HEATS AND THE REVERSIBLE
PROCESS

Unit Structure

5.0 Overview
5.1 Learning Objectives
5.2 Introduction
5.3 Specific Heats
5.3.1 Internal Energy
5.3.2 Enthalpy
5.3.3 Specific Heats of Ideal Gases
5.4 The Reversible Process
5.5 Tutorial Sheet
5.6 Summary
5.7 Answers to Activities and Tutorial Sheet


5.0 OVERVIEW

In this unit, specific heats are defined together with internal energy and enthalpy. The
concept of reversibility is also introduced and expressions are derived for the most
frequently encountered processes in thermodynamics.

In order to be successful in this unit, it is recommended that you have a good knowledge
of Physical Chemistry and are very familiar with simple Mathematics operations of
integration and differentiation.

Unit 5
2

5.1 LEARNING OBJECTIVES

By the end of this unit, you should be able to do the following:

1. Define the internal energy, enthalpy and specific heat at constant volume and at
constant pressure.
2. Identify the relationship between internal energy, enthalpy and specific heats.
3. Solve problems on reversible processes by using specific heats.


5.2 INTRODUCTION

The first part of this unit is devoted to the treatment of properties like internal energy and
enthalpy. The definitions of these two properties eventually lead to the concept of
specific heats. The two types of specific heats are developed and we will try to derive the
relationship between them. The different methods of calculating the changes in internal
energy and enthalpy are then explained.

In the second part of the unit, you will learn about the concept of reversibility and you
will be shown how to derive expressions for the cases when we have constant volume,
constant pressure and constant temperature processes and also adiabatic processes.


5.3 SPECIFIC HEATS

The heat required by a homogeneous system undergoing some specified process depends
upon the mass and type of material studied, its state and the path followed. All the
above-required information is usually given as the specific heat. The specific heat is a
property that enables us to compare the energy storage capacities of different substances.
Unit 5
3
Thus the specific heat is defined as the energy required to raise the temperature of a unit
mass of a substance by one degree.
It takes different amounts of energy to raise the temperature of different substances by the
same amount as illustrated in figure 5.1.
1 kg Iron 1 kg Water
20 C 30 C 20 C 30 C
C
v
= 4.5 kJ C
v
= 4.18 kJ
Fig. 5.1 Comparison of specific heats.

5.3.1 Internal Energy

It has been shown before that the energy stored by a system, which is not in motion, is
usually in the form of internal energy. It has been proved both mathematically and
experimentally that the internal energy of an ideal gas is dependent on the property
temperature only, i.e.,

u = u (T) Equation 5.1

In thermodynamics, there are two types of specific heats that will be of interest to us:

- Specific heat at constant volume C
v
: defined as the energy
required to raise the temperature of unit mass of a substance by 1 degree as the
volume is maintained constant
and the
- Specific heat at constant pressure C
p
: defined as the energy
required to raise the temperature of unit mass of a substance by 1 degree as the
pressure is maintained constant.

For ideal gases, a simplified expression can be obtained for internal energy:
du = C
v
dT Equation 5.2
where C
v
is a function of temperature
Unit 5
4
and u = u
2
- u
1
= ( )dT T C
2
1
v

(kJ/kg) Equation 5.3

5.3.2 Enthalpy

Enthalpy h has been defined previously as:

h = u + Pv Equation 5.4

But we know from the ideal gas equation of state that Pv = RT. Replacing in equation
5.4:

h = u + RT Equation 5.5


As u is a function of temperature and R a constant it follows that h will also be a
function of temperature only:

h = h(T) Equation 5.6

For ideal gases, a simplified expression can be obtained for the variation of enthalpy:

h = h
2
h
1 = ( )dT T C
2
1
p

(kJ/kg) Equation 5.7
where C
p
is a function of temperature only.
In order to be able to carry out the integration, the expression for the variation of C
p
as a
function of temperature has to be known.





Unit 5
5
Activity 1

1 kg of water at a pressure of 0.1 MPa is compressed from an initial state at 300
0
C to a
final state at 200
0
C at constant pressure. What is the change in enthalpy? (Use property
tables).

5.3.3 Specific Heats of Ideal Gases

We have already previously stated that in thermodynamics there are two types of specific
heats that will be of interest to us, namely C
v
and C
p
:

Expression for Specific Heats:

From equations 5.2 and 5.7 and using the 1
st
law of Thermodynamics, we can write:

q w = u. At constant volume: w = 0, q = u.

For C
v
,
C
v
dT = du at constant volume

C
v =
v
T
u
|

\
|

Equation 5.8
For C
p
,
q w = u
But we know from the definition of work, equation 4.1 that
w = Pv
Replacing for w we obtain:
q = u + w = u + Pv
= h
C
p
dT = dh

Unit 5
6
C
p
=
p
T
h
|

\
|

Equation 5.9

From the equations 5.8 and 5.9, it can also be said that C
v
is the change in the specific
internal energy of a substance per unit change in temperature at constant volume and C
p

is the change in the specific enthalpy of a substance per unit change in temperature at
constant pressure.

Units for C
v
and C
p
=
K . kg
kJ
or
C . kg
kJ
0



Specific heats are of much importance as they can help in determining the variation
in internal energy and enthalpy.

In fact there are three ways by which the changes in internal energy and enthalpy can be
determined:

(i) by using the values of u and h from the property tables
(ii) by integrating the expressions of C
v
and C
p
as a function of temperature.
(iii) by using the average of C
p
and C
v
at two different temperatures.








Figure 5.2

C
p
or
C
v
C
p av
or
C
v av
Actual
Approx.
T
T
1
T
av
T
2
Unit 5
7


Activity 2

Air at 300 K and 200 kPa is heated at constant pressure to 600K. Determine the change
in internal energy of air per unit mass using

(i) data from the air table
(ii) the functional form of specific heat

(C
p
= a + bT + cT
2
+ dT
3
)

the values of a,b,c and d are given in annex (in table A-2).
C
p
= C
v
- R

Notes: Relation between C
p
and C
v


C
p
is always greater than C
v
because at constant pressure, the system is allowed to expand
and energy for expansion work must also be supplied.

A relationship can be derived for C
p
and C
v
by differentiating equation 5.4:

h = u + Pv


= u + RT (from ideal-gas equation of state; equation 3.2)

Differentiating: dh = du + RdT

Replacing dh by equation 5.7 and du by equation 5.2:
C
p
dT = C
v
dT + RdT
Dividing by dT:
Unit 5
8
C
p
= C
v
+ R Equation 5.10

The specific heat ratio is defined as:


v
p
C
C
= Equation 5.11

The specific heat ratio is also an ideal-gas property. The above relations are necessary
for solving a number of problems encountered in Thermodynamics.

Activity 3

(a) 1 kg of an ideal gas is heated from 30
0
C to 70
0
C at (i) constant pressure and (ii)
constant volume.
Which process will require more energy? And why?
(b) Show that for an ideal gas C
p
C
v
= R


5.4 THE REVERSIBLE PROCESS

A reversible process is one, which can be reversed without leaving any trace on the
surroundings. (i.e., the net heat and net work done between system and surroundings = 0).
The conditions for a reversible process to occur are:
1- the process must be frictionless i.e. the fluid must have no internal friction.
2- the difference in pressure between system and surroundings during process
must be infinitely small, i.e. the process must take place infinitely slowly.
3- the difference in temperature between the fluid and its surroundings during the
process must be infinitely small.
For example, if a tennis ball is dropped in an evacuated space, it will bounce back
isothermally to its exact initial point without in any way changing itself or the surface on
which it strikes, thus illustrating the reversilibity of a process. In real life, the above
Unit 5
9
example does not occur and is only an idealised situation i.e., the ball never bounces back
to its original starting point.

Similarly, if a gas in a cylinder fitted with a piston is compressed adiabatically and then
expanded adiabatically to its original state, the surroundings should also be back to their
initial state if the process were reversible. However, in real situations, the expanding gas
does not yield the work required for its recompression due to some sort of friction.

There are a number of processes that you are going to encounter and the most common
ones are:

(a) Constant Volume Process

In a constant volume process, the work done (which is equal to Pv) = 0 and the first
law of thermodynamics (q - w = u) simplifies to

q = u
2
- u
1
Equation 5.12

In other words, we can say that all the heat supplied in a constant volume process
increases the internal energy.
In case of ideal gases only, we can write;
( ) ( )
1 2
T T C m T mC Q
v v
= = Equation 5.13








Figure 5.3 Constant Volume Process
v (m
3
/kg)
v
1
=v
2

P/kPa
P
2

P
1

Unit 5
10
(b) Constant Pressure process

In the case of a constant pressure process, the work done will be equal to the product of
pressure and change in volume.

( )

= = =
2
1
v
v
1 2
v v P dv P Pdv w

Applying the first law of Thermodynamics to closed systems:
u w q =

( )
( ) ( )
1 1 2
1 2 1
1 2
1
Pv u Pv u
Pv Pv u u
Pv Pv u
v v P u
w u q
2
+ + =
+ =
+ =
+ =
+ =
2
2





q = h
2
h
1

Equation 5.14
In other words, all the heat supplied in a constant pressure process increases the enthalpy.
In the case of ideal gases, we will also write:

( )
1 2
T T mC T mC Q
p p
= = Equation 5.15









Figure 5.4 Constant Pressure Process
v(m
3
/kg)
v
1
v
2

P
1
= P
2

P/kPa
Constant Pressure
Unit 5
11
(c ) Constant Temperature Process

If we start with the defining equation (5.4) of enthalpy:

Pv u h + =
Differentiating: vdP Pdv du dh + + =

But we have seen in sections 5.3.1 and 5.3.2 that h and u are functions of temperature.
Hence, FOR IDEAL GASES, if we are at constant temperature, dh = du = 0


cst Pv ln
cst v ln P ln
cst P ln cst v ln
dP
P
1
dv
v
1
dP
P
1
dv
v
1
vdP Pdv
=
= +
+ = +
=
=
=


cst Pv = Equation 5.16

So for a constant temperature process (Isothermal), the relation Pv = cst will apply.

(d) Reversible Adiabatic Process

A fourth case which, can be encountered is the reversible adiabatic process:
(i.e., q w = u). We will now try to find a relationship to characterise reversible
adiabatic process by applying the first law of thermodynamics:

Unit 5
12

0 Pdv du
0 v P u
0 w u
u u u -w
: that implies This
0 q process adiabatic an with dealing are we Since
u w q
1 2
= +
= +
= +
= =
=
=
or





But we know from section 3.3 that:
h = u + Pv

Differentiating dh = du + Pdv + vdP

Re-arranging the above dh vdP = du + Pdv

Since du + Pdv = 0, it follows that dh vdP = 0

In the case of ideal gases we can derive an expression starting with du + Pdv =0

Knowing that ( ) ( ) 2 3 2 5 . . eq
v
RT
P that and . . eq dT C du
v
= =

K v ln
C
R
T ln
: C by Dividing
k v ln R T ln C
: g Integratin
0
v
dv
R
T
dT
C
: T by Dividing
0 dv
v
RT
dT C
v
v
v
v
v
= +
= +
= +
= +

Unit 5
13
( )
k
v
v
R
Pv
ln
k v ln 1
R
Pv
ln
k v ln
C
R
R
Pv
ln
,
R
Pv
T placing Re
v
=
= +
= +

by


1
C
R
But
C
R
1
C
C
R C C
v
v v
p
v p
=
=
=
=
v
p
C
C



cst Pv =

Equation 5.17

Hence, for a reversible adiabatic process, cst Pv =

will apply.

In the general case, when we have Pv
n
= cst, the processes governed by such laws will be
called polytropic processes.

With Pv
n
= cst = K, we will now derive an expression for the heat transferred and work
done.


n 1
v P v P
n 1
v
Kv
v
Kv
n 1
Kv
dv Kv Pdv w
1 1 2 2
n
1
1
n
2
2
v
v
1 n 2
1
2
1
n
2
1

=
(

= = =
+

w=
n 1
v P v P
1 1 2 2

But for an ideal gas

P
1
v
1
= RT
1
and P
2
v
2
= RT
2


Unit 5
14
w =
( )
n
T T R
n
RT RT

1 1
1 2 1 2

Applying the first law of Thermodynamics (q-w = u) to closed systems:


( )
( )
( )
( ) ( )
( )( ) ( )( )
( )( )
( )
1 1
T R

1 1
1 1

1 1

1
1
1 2
1 2 1 2
1 2 1 2
1 2
1 2
1 2
1 2

=

+
=

+

=
|

\
|

+ =
=

n
n
T
n
T T R T T n R
T T
n
R
T T
R
n
T T
R T T C q
T T C
n
T T R
q
v
v



1
=
R
C
v


|
|

\
|


=
1
n
w q


5.5 TUTORIAL SHEET

1) 0.05 kg of a certain fluid is heated at constant pressure of 2 bars until the volume
occupied is 0.0658 m
3
. Calculate the heat supplied and the work done:

(a) When the fluid is steam, initially dry and saturated.
(b) When the fluid is air, initially at 130
0
C.
(C
p
=1.005kJ/kg.K)

2) Steam at 7 bar and dryness fraction 0.9 expands in a cylinder behind a piston
isothermally and reversibly to a pressure of 1.5 bars. Calculate the change in
Unit 5
15
internal energy and the change in enthalpy per kg of steam. The heat supplied
during the process is found to be 547 kJ/kg. Calculate the work done per kg of
steam.

3) 1 kg of nitrogen is compressed reversibly and isothermally from 1.01 bars, 20
0
C.
to 4.2 bars. Calculate the work done and the heat flow during the process.
Assume nitrogen to be a perfect gas.

4) 1 kg of steam at 100 bars and 375
0
C expands reversibly in a perfectly thermally
insulated cylinder behind a piston until the pressure is 38 bars and steam is dry
saturated. Calculated the work done by the steam.

5) Air at 1.02 bars, 22
0
C initially occupying a cylinder volume of 0.015 m
3
is
compressed reversibly and adiabatically by a piston to a pressure of 6.8 bars.
Calculate the temperature, the final volume, and the work done on the mass of air
in the cylinder. ( for Air = 1.4).

6) In a steam engine, the steam at the beginning of the expansion process is at 7 bars,
dryness fraction 0.95 and the expansion follows the law PV
1.1
= constant. down to
a pressure of 0.34 bars. Calculate the work done per kg of steam during the
expansion and the heat flow per kg of steam.

7) 1 kg of a perfect gas is compressed from 1.1 bars, 27
0
C according to a law PV
1.3
=
constant until the pressure is 6.6 bars. Calculate the net heat flow to or from the
cylinder walls.

(a) when the gas is ethane (Molar mass 30 kg/kmol) which has a C
p
= 2.10
kJ/kg.K
(b) when the gas is argon (Molar mass 40 kg/kmol) which has C
p
=0.520
kJ/kg.K.

Unit 5
16
8) In the cylinder of a steam engine, the steam expands from 5.5 bars to 0.75 bar
according to a hyperbolic law PV = constant. If the steam is initially dry
saturated, calculate the work done per kg of steam and the heat flow to or from
the cylinder walls.

5.6 SUMMARY

The concepts of specific heats C
p
and C
v
have been defined and it has been shown how
they are directly related to the properties internal energy and enthalpy

v
v
P
p
u
C
T
h
C |

\
|

= |

\
|

=
T
and
It has also been shown how C
p
and C
v
are related to each other:

R C C
C
C
v p
v
p
=
=

You have also been taught how to calculate the changes in internal energy u and
enthalpy h :

Firstly by using property tables
Secondly by integrating the expression of C
p
and C
v
in terms of T.
Thirdly by averaging C
p
or C
v
between two temperatures.

The concept of reversibility and its use in deriving expressions for the following
processes have also been demonstrated:

(a) constant volume process :
1 2
u u q = q = C
v
T
(b) constant pressure process :
1 2
h h q = q = C
p
T
Unit 5
17
(c ) constant temperature process : cst Pv =
(d) adiabatic process : cst Pv =

(e) polytropic process :
n 1
v P v P
w
cst Pv
1 1 2 2
n

=
=

q =
1
n
w



So far, you have seen how the first law of Thermodynamics is applied to Closed Systems.
In the next unit, you will see how the 1
st
law is applied to Open Systems i.e., system in
which there is both mass interaction and energy interaction.


5.7 ANSWERS TO ACTIVITIES AND TUTORIAL SHEET

Activity 1

kJ h h h 199
1 2
= =

Activity 2
(i) 220.71 kJ/kg
(ii) 222.3 kJ/kg

Activity 3
(a) The first one. Because at constant pressure, there is expansion and energy for
expansion must also be supplied.
(b) Using h = u + Pv
= u + RT (from the ideal gas equation of state Pv = RT)
Unit 5
18

R C C
R C C dT by
RdT dT C dT C
dT C du and dT C dh
RdT du dh
RT u h
v p
v p
v p
v p
=
+ =
+ =
= =
+ =
+ =



ating Differenti


Tutorial Sheet
1) (a) W = 86.1 kJ/kg Q = 365.1 kJ/kg
(b) W = 7.4 kJ Q = 25.9 kJ
2) u = 217.9 kJ/kg h = 245.8kJ/kg W = 329.1 kJ/kg
3) W = -124 kJ
4) W = 162.9 kJ/kg
5) T = 507 K V = 0.00387 m
3
W = -2754J
6) W = 436 kJ/kg Q = 125.2 kJ/kg
7) (a) Q = 137.2 kJ (b) Q = -58.8 kJ
8) W = 375.5 kJ/kg Q = 320 kJ/kg