UNIT 5 SPECIFIC HEATS AND THE REVERSIBLE

PROCESS
Unit Structure
5.0 Overview
5.1 Lernin! O"#ective$
5.% Intr&'ucti&n
5.( S)eci*ic Het$
5.(.1 Intern+ Ener!,
5.(.% Ent-+),
5.(.( S)eci*ic Het$ &* I'e+ .$e$
5./ T-e Rever$i"+e Pr&ce$$
5.5 Tut&ri+ S-eet
5.0 Su11r,
5.2 An$wer$ t& Activitie$ n' Tut&ri+ S-eet
5.0OVERVIE3
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 athematics operations of
integration and differentiation.
Unit 5
!
5.1 LEARNIN. OB4ECTIVES
"y the end of this unit, you should be able to do the following#
!. $efine the internal energy, enthalpy and specific heat at constant volume and at
constant pressure.
%. Identify the relationship between internal energy, enthalpy and specific heats.
&. 'olve problems on reversible processes by using specific heats.
5.% 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.( 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. (ll 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
%
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 *.!.
! kg Iron ! kg +ater
%, -C &, -C %, -C &, -C
C
v
. /.* k0 C
v
. /.!1 k0
Fi!. 5.1 C&1)ri$&n &* $)eci*ic -et$.
5.(.1 Intern+ Ener!,
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 intern+ ener!, &* n i'e+ !$ i$ 'e)en'ent &n t-e )r&)ert,
te1)erture &n+,, i.e.,
u . u 2T3 E5uti&n 5.1
In thermodynamics, there are two types of specific heats that will be of interest to us#
- S)eci*ic -et t c&n$tnt v&+u1e C
v
# defined as the energy
required to raise the temperature of unit mass of a substance by ! degree as the
volume is maintained constant
and the
6 S)eci*ic -et t c&n$tnt )re$$ure C
p
# defined as the energy
required to raise the temperature of unit mass of a substance by ! degree as the
pressure is maintained constant.
4or ideal gases, a simplified expression can be obtained for internal energy#
du . C
v
dT E5uti&n 5.%
where C
v
is a function of temperature
Unit 5
&
and u . u
%
) u
!
.
( )dT T C
%
!
v

2k05kg3 E5uti&n 5.(

5.(.% Ent-+),
6nthalpy h has been defined previously as#
h = u + Pv E5uti&n 5./
"ut we know from the ideal 7 gas equation of state that Pv . 8T. 8eplacing in equation
*./#
h = u + RT E5uti&n 5.5
(s u is a function of temperature and R a constant it follows that h wi++ +$& "e
*uncti&n &* te1)erture &n+,#
h = h(T) E5uti&n 5.0
4or ideal gases, a simplified expression can be obtained for the variation of enthalpy#

h = h
2
h
1 .
( )dT T C
%
!
p

2k05kg3 E5uti&n 5.2

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
/
Activit, 1
! kg of water at a pressure of ,.! Pa is compressed from an initial state at &,,
,
C to a
final state at %,,
,
C at constant pressure. +hat is the change in enthalpy9 2:se property
tables3.
5.(.( S)eci*ic Het$ &* I'e+ .$e$
+e 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
#
E7)re$$i&n *&r S)eci*ic Het$8
4rom equations *.% and *.; and using the !
st
law of Thermodynamics, we can write#
q 7 w . u. (t constant volume# w . ,, q . u.
4or C
v
,
C
v
dT . du at constant volume
C
v .
v
T
u

,
_

E5uti&n 5.9
4or C
p
,
q w = u
"ut we know from the definition of work, equation /.! that
w = Pv
8eplacing for w we obtain#
q = u + w = u + Pv
= h
C
p
dT = dh
Unit 5
*
C
p
.
p
T
h

,
_

E5uti&n 5.:
4rom the equations *.1 and *.<, 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
)
is the change in the specific enthalpy of a substance per unit change in temperature at
constant pressure.
:nits for C
v
and C
p
=
K . kg
kJ
or
C . kg
kJ
,

S)eci*ic -et$ re &* 1uc- i1)&rtnce $ t-e, cn -e+) in 'eter1inin! t-e vriti&n
in intern+ ener!, n' ent-+),.
In fact there are three ways by which the changes in internal energy and enthalpy can be
determined#
2i3 by using the values of u and h from the property tables
2ii3 by integrating the expressions of C
v
and C
p
as a function of
temperature.
2iii3 by using the average of C
p
and C
v
at two different
temperatures.
Unit 5
=
C
)
&r
C
v
C
) v
&r
C
v v
Actu+
A))r&7.
T
T
1
T
v
T
%
Fi!ure 5.%
Activit, %
(ir at &,, > and %,, kPa is heated at constant pressure to =,,>. $etermine the change
in internal energy of air per unit mass using
2i3 data from the air table
2ii3 the functional form of specific heat
2C
p
. a ? bT ? cT
%
? dT
&
3
the values of a,b,c and d are given in annex 2in table ()%3.
C
p
. C
v
) 8
N&te$8 Re+ti&n "etween C
)
n' 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.
( relationship can be derived for C
p
and C
v
by differentiating equation *./#
h . u + Pv
= u + RT 2from ideal)gas equation of state@ equation &.%3
$ifferentiating# dh . du + RdT
8eplacing dh by equation *.; and du by equation *.%#
C
p
dT . C
v
dT ? 8dT
Unit 5
;
$ividing by dT#
C
p
= C
v
+ R E5uti&n 5.10
The specific heat ratio is defined as#
v
p
C
C

E5uti&n 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.
Activit, (
2a3 ! kg of an ideal gas is heated from &,
,
C to ;,
,
C at 2i3 constant
pressure and 2ii3 constant volume.
+hich process will require more energy9 (nd why9
2b3 'how that for an ideal gas C
p
7 C
v
. 8
5./ THE REVERSIBLE PROCESS
( reversible process is one, which can be reversed without leaving any trace on the
surroundings. 2i.e., the net heat and net work done between system and surroundings . ,3.
The conditions for a reversible process to occur are#
!) the process must be frictionless i.e. the fluid must have no internal friction.
%) the difference in pressure between system and surroundings during process
must be infinitely small, i.e. the process must take place infinitely slowly.
&) the difference in temperature between the fluid and its surroundings during the
process must be infinitely small.
4or 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
Unit 5
1
which it strikes, thus illustrating the reversilibity of a process. In real life, the above
example does not occur and is only an idealised situation i.e., the ball never bounces back
to its original starting point.
'imilarly, 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. Aowever, 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#
;< C&n$tnt V&+u1e Pr&ce$$
In a constant volume process, the work done 2which is equal to Pv3 . , and the first
law of thermodynamics 2q ) w . u3 simplifies to
q . u
%
) u
!
E5uti&n 5.1%
In other words, we can say that all the heat supplied in a constant volume process
increases the internal energy.
In case of i'e+ !$e$ &n+,, we can write@
( ) ( )
! %
T T C m T mC Q
v v

E5uti&n 5.1(
Fi!ure 5.( C&n$tnt V&+u1e Pr&ce$$
Unit 5
<
v ;1
(
=>!<
v
1
?v
%
P=>P
P
%
P
1
;"< C&n$tnt Pre$$ure )r&ce$$
In the case of a constant pressure process, the work done will be equal to the product of
pressure and change in volume.
( )


%
!
v
v
! %
v v P dv P Pdv w
(pplying the first law of Thermodynamics to closed systems#
u w q
( )
( ) ( )
! ! %
! % !
! %
!
Pv u Pv u
Pv Pv u u
Pv Pv u
v v P u
w u q
2
+ +
+
+
+
+
2
2




q . h
%
7 h
!
E5uti&n 5.1/
In other words, all the heat supplied in a constant pressure process increases the enthalpy.
In the case of i'e+ !$e$, we will also write#
( )
! %
T T mC T mC Q
p p

E5uti&n 5.15
Fi!ure 5./ C&n$tnt Pre$$ure Pr&ce$$
;c < C&n$tnt Te1)erture Pr&ce$$
Unit 5
!,
v;1
(
=>!<
v
1
v
%
P
1
? P
%
P=>P
C&n$tnt Pre$$ure
If we start with the defining equation 2*./3 of enthalpy#
Pv u h +
$ifferentiating# vdP Pdv du dh + +
"ut we have seen in sections *.&.! and *.&.% that h and u are functions of temperature.
Aence, 4B8 I$6(C D('6', if we are at constant temperature, dh . du . ,
cst Pv ln
cst v ln P ln
cst P ln cst v ln
dP
P
!
dv
v
!
dP
P
!
dv
v
!
vdP Pdv

+
+ +




cst Pv E5uti&n 5.10
'o for a constant temperature process 2Isothermal3, the relation Pv = cs will apply.
;'< Rever$i"+e A'i"tic Pr&ce$$
( fourth case which, can be encountered is the reversible adiabatic process#
2i.e., q 7 w . u3. +e will now try to find a relationship to characterise reversible
adiabatic process by applying the first law of thermodynamics#

, Pdv du
, v P u
, w u
u u u )w
# that implies This
, q process adiabatic an with dealing are we 'ince
u w q
! %
+
+
+

&r




"ut we know from section &.& that#
h . u ? Pv
Unit 5
!!
$ifferentiating dh . du ? Pdv ? vdP
8e)arranging the above dh 7 vdP . du ? Pdv
'ince du ? Pdv . ,, it follows that dh 7 vdP . ,
In the case of i'e+ !$e$ we can derive an expression starting with du ? Pdv .,
>nowing that
( ) ( ) % & % * . . !q
v
RT
P h" "#d . . !q dT C du
v

> v ln
C
8
T ln
# C by $ividing
k v ln 8 T ln C
# g Integratin
,
v
dv
8
T
dT
C
# T by $ividing
, dv
v
8T
dT C
v
v
v
v
v
+
+
+
+
( )
k
v
v
8
Pv
ln
k v ln !
8
Pv
ln
k v ln
C
8
8
Pv
ln
,
8
Pv
T placing 8e
v

+
+

",
!
C
8
"ut
C
8
!
C
C
8 C C
v
v v
p
v p




v
)
C
C

cs Pv

E5uti&n 5.12
Unit 5
!%
Aence, for a rever$i"+e 'i"tic )r&ce$$@ cs Pv

will apply.
In the general case, when we have Pv
n
. cst, the processes governed by such laws will be
called polytropic processes.
+ith Pv
n
. cst . >, we will now derive an expression for the heat transferred and work
done.
n !
v P v P
n !
v
>v
v
>v
n !
>v
dv >v Pdv w
! ! % %
n
!
!
n
%
%
v
v
! n %
!
%
!
n
%
!

1
]
1

w.
n !
v P v P
! ! % %

"ut for an i'e+ !$

P
!
v
!
. 8T
!
and P
%
v
%
. 8T
%
w .
( )
#
T T R
#
RT RT

! !
! % ! %
(pplying the first law of Thermodynamics 2q)w . u3 to closed systems#
Unit 5
!&
( )
( )
( )
( ) ( )
( )( ) ( )( )
( )( )
( )
! !
T 8

! !
! !

! !

!
!
! %
! % ! %
! % ! %
! %
! %
! %
! %

,
_

#
#
T
#
T T R T T # R
T T
#
R
T T
R
#
T T
R T T C q
T T C
#
T T R
q
v
v
!

R
C
v

,
_

!
#
w q
5.5 TUTORIAL SHEET
!3 ,.,* kg of a certain fluid is heated at constant pressure of % bars until the
volume occupied is ,.,=*1 m
&
. Calculate the heat supplied and the work done#
2a3 +hen the fluid is steam, initially dry and saturated.
2b3 +hen the fluid is air, initially at !&,
,
C.
2C
p
.!.,,*k05kg.>3
%3 'team at ; bar and dryness fraction ,.< expands in a cylinder behind a
piston isothermally and reversibly to a pressure of !.* bars. Calculate the change
in internal energy and the change in enthalpy per kg of steam. The heat supplied
during the process is found to be */; k05kg. Calculate the work done per kg of
steam.
Unit 5
!/
&3 ! kg of nitrogen is compressed reversibly and isothermally from !.,! bars,
%,
,
C. to /.% bars. Calculate the work done and the heat flow during the process.
(ssume nitrogen to be a perfect gas.
/3 ! kg of steam at !,, bars and &;*
,
C expands reversibly in a perfectly
thermally insulated cylinder behind a piston until the pressure is &1 bars and
steam is dry saturated. Calculated the work done by the steam.
*3 (ir at !.,% bars, %%
,
C initially occupying a cylinder volume of ,.,!* m
&
is
compressed reversibly and adiabatically by a piston to a pressure of =.1 bars.
Calculate the temperature, the final volume, and the work done on the mass of air
in the cylinder. 2 for (ir . !./3.
=3 In a steam engine, the steam at the beginning of the expansion process is
at ; bars, dryness fraction ,.<* and the expansion follows the law PE
!.!
. constant.
down to a pressure of ,.&/ bars. Calculate the work done per kg of steam during
the expansion and the heat flow per kg of steam.
;3 ! kg of a perfect gas is compressed from !.! bars, %;
,
C according to a law
PE
!.&
. constant until the pressure is =.= bars. Calculate the net heat flow to or
from the cylinder walls.
2a3 when the gas is ethane 2olar mass &, kg5kmol3 which has a
C
p
. %.!, k05kg.>
2b3 when the gas is argon 2olar mass /, kg5kmol3 which has
C
p
.,.*%, k05kg.>.
13 In the cylinder of a steam engine, the steam expands from *.* bars to ,.;*
bar according to a hyperbolic law PE . 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.
Unit 5
!*
5.0SUAAARB
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


Fou have also been taught how to calculate the changes in internal energy u and
enthalpy h #
4irstly by using property tables
'econdly 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#
2a3 constant volume process #
! %
u u q q = C
v
T
2b3 constant pressure process #
! %
h h q q = C
p
T
2c 3 constant temperature process # cs Pv
2d3 adiabatic process # cs Pv

Unit 5
!=
2e3 polytropic process #
n !
v P v P
w
cst Pv
! ! % %
n

q .
!
n
w

'o far, you have seen how the first law of Thermodynamics is applied to Closed 'ystems.
In the next unit, you will see how the !
st
law is applied to Bpen 'ystems i.e., system in
which there is both mass interaction and energy interaction.
5.2 ANS3ERS TO ACTIVITIES AND TUTORIAL SHEET
Activit, 1
kJ h h h !<<
! %

Activit, %
2i3 %%,.;! k05kg
2ii3 %%%.& k05kg
Activit, (
2a3 The first one. "ecause at constant pressure, there is expansion and energy for
expansion must also be supplied.
2b3 :sing h = u + Pv
. u + RT 2from the ideal gas equation of state Pv = RT3
Unit 5
!;
R C C
R C C dT $%
RdT dT C dT C
dT C du "#d dT C dh
RdT du dh
RT u h
v p
v p
v p
v p

+
+

+
+



ating $ifferenti
Tut&ri+ S-eet
!3 2a3 + . 1=.! k05kg G . &=*.! k05kg
2b3 + . ;./ k0 G . %*.< k0
%3 u . %!;.< k05kg h . %/*.1k05kg + . &%<.! k05kg
&3 + . )!%/ k0
/3 + . !=%.< k05kg
*3 T . *,; > E . ,.,,&1; m
&
+ . )%;*/0
=3 + . /&= k05kg G . !%*.% k05kg
;3 2a3 G . !&;.% k0 2b3 G . )*1.1 k0
13 + . &;*.* k05kg G . &%, k05kg
Unit 5
!1