1

Chapter 5-Sonntag
ENERGY ANALYSIS OF
CLOSED SYSTEMS
Florio
Sonntag-Cengel-10
2
Chapter Objectives
Examine the moving boundary work or P dV work. Commonly
encountered in reciprocating devices such as automotive engines
and compressors.
Identify the first law of thermodynamics as simply a statement of
the conservation of energy principle for closed (fixed mass)
systems.
Develop the general energy balance applied to closed systems.
Define the specific heat at constant volume and the specific heat at
constant pressure.
Relate the specific heats to the calculation of the changes in
internal energy and enthalpy of ideal gases. Use of tables
Describe incompressible substances and determine the changes in
their internal energy and enthalpy.
Solve energy balance problems for closed (fixed mass) systems
that involve heat and work interactions for general pure
substances, ideal gases, and incompressible substances.
2
3
Adiabatic work
System System
Work Transfer
Surroundings Surroundings
Adiabatic Boundary
4
Equivalence of adiabatic processes
First Law First Law-- All All
adiabatic processes adiabatic processes
between two between two
equilibrium states equilibrium states
require the same require the same
adiabatic work adiabatic work to be to be
done on the system done on the system
regardless of the regardless of the
path path
State 1 State 1
State 2 State 2
3
5
First Law Statement
The adiabatic work done on The adiabatic work done on
a closed system to connect a closed system to connect
two equilibrium states two equilibrium states
is independent of path, therefore is independent of path, therefore
Identifies a change in a thermodynamic Identifies a change in a thermodynamic
property called energy. property called energy.
6
The First Law
,1 2 2 1 adby
W E E

=
Work done Work done by (out of) by (out of) the system the system
is is
positive by convention positive by convention minus minus
work by is work on (in) work by is work on (in)..
4
7
For a non adiabatic process, the Heat
transfer to the system, Q, is defined by
,1 2 ,1 2
,1 2 2
,1 2
,1 2 1
Heat transfer is defined as
the difference between the work by
and the adiabatic work by
for the same change in state
a to b y y
o
db
by t
Q W W
Q W E E
or

=
= +
8
Define Internal energy, U change between two states at
at the same extrinsic state , i.e. the same velocity and
position but different intrinsic properties.
,1 2 2 1 adby
W U U

Work done by the system is positive by Work done by the system is positive by
convention. convention. KE KE
11--22
= 0, and = 0, and PE PE
11--22
= 0 = 0
Which are the adiabatic work on the system at Which are the adiabatic work on the system at
same intrinsic state but different extrinsic state. same intrinsic state but different extrinsic state.
5
9
Energy Balances: change = in - out
Net change of
energy in the
system.
Heat transfer
into system
from
surroundings.
Work done by
system on
surroundings.
(Work transfer
to surrounding)
Path, or process, dependent Path, or process, dependent
quantities between states quantities between states
d(U+KE+PE)
Q W
10
Energy Balances:
Change = transfer in transfer out
==
Change of Energy Change of Energy
in the System in the System
--
Heat Transfer to at Heat Transfer to at
System Boundary System Boundary
Work Done by Work Done by
the System the System
These terms are evaluated at the system
boundary. They represent energetic
interactions between the system and its
surroundings.
Net energy
Transferred into the
system=
=
6
11
Motor
in
W

from
Q

inmass sys out motorsystem

m
W W
PE

=
=

mm
Example 1 Example 1
For steady operation, there For steady operation, there
is no change of the state of is no change of the state of
the system, and for the motor system the system, and for the motor system
0
in out loss
W W Q =

12
Example 2 - unsteady
Mechanical Mechanical
Work to Raise Work to Raise
the Mass, m the Mass, m
Heat Loss from Heat Loss from
from Motor from Motor
Force = mg Force = mg
Battery has stored Battery has stored
energy. It is released energy. It is released
via electrical current. via electrical current.
M
BB
mm
System Boundary System Boundary
7
13
Example 3: Q
5
Q
1
W=E
battery
+ E
motor
QQ
55
To correctly analyze this arrangement, all energy & work transfers To correctly analyze this arrangement, all energy & work transfers
must be counted. Where is the primary energy source? What are must be counted. Where is the primary energy source? What are
the possible systems for analysis? the possible systems for analysis?
B
W
Motor
QQ
11
QQ
22
QQ
33
QQ
44
Fan
Battery
14
Cyclic Processes
P
1
P
2
SS
11
SS
22
2 1 , 2 1 2 1
=
by
W Q dU
1 2 1 1 2 1 1 2 1
0
by
dU Q W

= =

8
15
Initial System Initial System
State 1 State 1
Deformed System Deformed System
Boundary Boundary
State 2
xx
yy
zz
P
1
1
2
P
3
P
2
Process Path Process Path
dW=PdAdN
16
MOVING BOUNDARY WORK
Reversible-Moving boundary work
(P dV work): The expansion and
compression work in a piston-cylinder
device. Observer moving with the system
The work associated
with a moving
boundary is called
boundary work.
A gas does a
differential
amount of work
W
b
as it forces
the piston to
move by a
differential
amount ds.
Quasi-equilibrium process:
A process during which the system
remains nearly in equilibrium at all
times.
W
b
is positive for expansion
W
b
is negative for compression
9
17
The area under the process
curve on a P-V diagram
represents the boundary work.
The boundary
work done
during a process
depends on the
path followed as
well as the end
states.
The net work done
during a cycle is the
difference between
the work done by
the system and the
work done on the
system.
18
Polytropic, Isothermal, and Isobaric processes
Polytropic process: C, n (polytropic exponent) constants
N=1
Polytropic
process
Polytropic - for ideal gas
When n = 1
(represents an
isothermal process
for-ig )
Schematic and
P-V diagram for
a polytropic
process.
Constant pressure process
10
19
ENERGY BALANCE FOR CLOSED SYSTEMS
Energy balance for any system
undergoing any process
Energy balance
in the rate form
The total quantities are related to the quantities per unit time is
Energy balance per unit mass basis
where represents an amount of
rather than a change of.
Energy balance in
differential form
Energy balance
for a cycle
in by system
q w de =
20
Equations
In solving thermodynamics problems
Define the problem
Examine data. Is the substance known? Are two intensive properties
identified at the each end state?
Can the work be evaluated or is it known ?
Can heat transfer be evaluated or is it known?
Write the energy equation in form appropriate to the system.
What modeling approximations can be made or need to be made?
Write the conservation of mass equation, and if possible relate to the
given data.
Are there a sufficient number of equations for the # of unknowns?
In some cases additional fundamental laws or particular equations must
be applied- i.e. equation of state ( or equivalent use of tables) and
further modeling assumptions made.
Verify or check validity of assumptions, i.e. iterate.
11
21
Scientific Method- eight step format
1. Define the problem
2. Collect the data.
3. Analyze the data
4. Form an hypothesis
5. Test the hypothesis
6. Analyze the results
7. Accept or reject the hypothesis
8. If necessary, iterate
22
net-in net-out system
Net energy transfer
Change in internal, kinetic,
by heat, work
potential, etc. energies
in ,ou 2 1
in ,ou 2 1
( ) (since KE=PE=0)
( )
b t
b t
Q W E
Q W U m u u
Q W m u u
=
= =
= +

P
v
1
2
300 kPa
75 kPa
45 A saturated water mixture at 75 kPa , 13 % quality with an initial volume of 2 m
3
is contained in a
linear spring-loaded piston-cylinder device It is heated until the pressure is 300 kPa and volume
increases to 5 m
3
. The heat transfer and the work done are to be determined.
Assumptions 1 The cylinder is stationary and thus the kinetic and potential energy changes are
zero. 2 There are no work interactions involved other than the boundary work. 3 The thermal energy
stored in the cylinder itself is negligible. 4 The compression or expansion process is quasi-
equilibrium.
Analysis We take the contents of the cylinder as the system. This is a closed
system since no mass enters or leaves. The energy balance for this stationary
closed system can be expressed as
P
eq
= A + B Vol
12
23
The initial state is saturated mixture at 75 kPa. The specific volume and internal energy at this state are (Table B1.2),
kJ/kg 89 . 658 ) 8 . 2111 )( 13 . 0 ( 36 . 384
/kg m 28914 . 0 ) 001037 . 0 2172 . 2 )( 13 . 0 ( 001037 . 0
1
3
1
= + = + =
= + = + =
fg f
fg f
xu u u
xv v v
The mass of water is
kg 9170 . 6
/kg m 28914 . 0
m 2
3
3
1
1
= = =
v
V
m The final specific volume is
/kg m 72285 . 0
kg 9170 . 6
m 5
3
3
2
2
= = =
m
V
v
The final state is now fixed. v> v
g
The internal energy at this specific volume and 300 kPa pressure is
(Table B1.3)
kJ/kg 2 . 2657
2
= u
1 2 3
,out 2 1
3
With a linear spring, the quasi-equilibrium P varies linearly with the volume, thus
(75 300)kPa 1 kJ
( ) (5 2)m
2 2 1 kPa m
b
P P
W PdVol Vol Vol
+ + | |
= = = =
|
\

562.5 kJ
Substituting into energy balance equation gives
kJ 14,385 = + = + = kJ/kg ) 89 . 658 kg)(2657.2 9170 . 6 ( kJ 5 . 562 ) (
1 2 out , in
u u m W Q
b
24
Energy balance when sign convention is used (i.e., heat input and work
output are positive; heat output and work input are negative).
Various forms of the first-law relation
for closed systems when sign
convention is used.
For a cycle E = 0, thus Q = W.
The first law cannot be proven mathematically, but no process in nature is known
to have violated the first law, and thus until a violation of the law is observed, it
should be taken as valid.
Energy EQ Using Sign General Convention
of 1st Law
General finite -period-
: /



Forms
Q W E
Rate form Eq Q W DE Dt
NeglectingKE PE Q W U
mass base q w e
Differentialmassbase q w de
=
=
=
=
=

13
25
TANK A
2 kg
1 MPa
300C
TANK B
3 kg
150C
x=0.5
Q
42 Two tanks initially separated by a partition contain steam at different states. Now the partition is
removed and they are allowed to mix until equilibrium is established. If the final pressure is 300 kPa ,
the temperature and quality of the steam at the final state and the amount of heat lost from the tanks
are to be determined.
Assumptions 1 The tank is stationary and thus the kinetic and potential energy changes are
zero. 2 There are no work interactions.
Analysis (a) We take the contents of both tanks as the system. This is a closed system since no
mass enters or leaves. Noting that the volume of the system is constant and thus there is no
boundary work, the energy balance for this stationary closed system can be expressed as
The properties of steam in both tanks at the initial state are (Tables B1.1 through B1.3)
kJ/kg 7 . 2793
/kg m 25799 . 0
C 300
kPa 1000
, 1
3
, 1
, 1
, 1
=
=

=
=
A
A
A
A
u T
P
v
( ) [ ]
( ) kJ/kg 4 . 1595 4 . 1927 0.50 .66 631
/kg m 0.19679 0.001091 0.39248 0.50 0.001091
kJ/kg 4 . 1927 , 66 . 631
/kg m .39248 0 , 001091 . 0
50 . 0
C 150
1 , 1
3
1 , 1
3
1
, 1
= + = + =
= + = + =
= =
= =
)
`

=
=
fg f B
fg f B
fg f
g f B
u x u u
x
u u x
T
v v v
v v
[ ] [ ]
in out system system
Net energy transfer Change in internal, kinetic,
by heat, work potential, etc. energies
2
out 2 1 2 1
[ ) ) ]
( ) ( )
(with
A B
A B
A B
A B
Q W E U
m m m
U mu mu mu
Q U U U m u u m u u
W
= =
= +
= +
= = + = +

KE=PE=0) =
26
Two intensive properties are required to define final state. Assume the final state is an equilibrium state.
The total volume and total mass of the system are
kg 5 2 3
m 106 . 1 /kg) m 19679 . 0 kg)( 3 ( /kg) m 25799 . 0 kg)( 2 (
3 3 3
, 1 , 1
= + = + =
= + = + = + =
B A
B B A A B A
m m m
m m v v V V V
Now, the specific volume at the final state may be determined
/kg m 22127 . 0
kg 5
m 106 . 1
3
3
2
= = =
m
V
v
which fixes the final state and we can determine other properties. Table B1.2 Since
V
f
<v<v
g
at 300 kPa- mixture
( ) kJ/kg 8 . 1282 1 . 1982 0.3641 .11 561
001073 . 0 60582 . 0
001073 . 0 22127 . 0
/kg m 22127 . 0
kPa 00 3
2 2
2
2
kPa 300 @ sat 2
3
2
2
= + = + =
=

=
= =

=
=
fg f
f g
f
u x u u
x
T T
P
0.3641
C 133.5
v v
v v
v
(b) Substituting,
[ ] [ ]
out 2 1, 1
2 1 2 1
[ ] [ , ]
( ) ( )
(2 kg)(1282.8 2793.7)kJ/kg (3 kg)(1282.8 1595.4)kJ/kg 3959 kJ
A A B B
A B
Q U m u m u m u
m u u m u u
= = + =
+
= + =
or
kJ 3959 =
out
Q
14
27
Energy balance for a constant-pressure
expansion or compression process
H W U
b
= +
For a constant-pressure expansion
or compression process:
An example of constant-pressure, P
equ
,
bdy condition-not reversible-no piston-
friction
General analysis for a closed system
undergoing a quasi-equilibrium
constant-pressure process. Q is to the
system and Wis from the system.
Wb
W
e e e
0.3A
Since frictional effects neg
28
Net out system
Net energy transfer Change in internal, kinetic,
by heat, work potential, etc. energies
e,in pw,in
e,in pw,in 2 1
(since =KE=PE=0)
( )
(
Netout
Q W E
W W PAdh U Q
W W m h h
I t
=
+ =
+ =

Volt
pw,in 2 1
) ( ) W m h h + =
H
2
O
P
equil
.
W
pw
W
e
v
P
1 2
- -- -39 39 39 39An insulated cylinder is initially filled with 5 L of saturated liquid water at a pressure of 175 kPa. The water is heated electrically with a
current of 8A for 45 min through a resistor as it is stirred by a paddle-wheel with constant pressureboundary condition. If one half of the
liquid is evaporated during this process and the paddle wheel work is 400 kJ, determine the voltage of the current source . Show the
process on a P-v diagram.
Assumptions Assumptions Assumptions Assumptions 1 1 1 1 The cylinder is stationary and thus the kinetic and potential energy changes are zero. 2 2 2 2 The cylinder is well-insulated and
thus heat transfer is negligible. 3 3 3 3 The thermal energy stored in the cylinder itself is negligible. 4 4 4 4 The piston moves with no friction and
negligible acceleration.
Analysis Analysis Analysis Analysis We take the contents of the cylinder as the system. This is a closed system since no mass enters or leaves. The energy balance
for this stationary closed system can be expressed as
U+ W
b
= H Since the initial and final P is the same and the end
states are-equilibrium states. The properties of water are (Tables
B1.1through B1.3)
( )
kg 4.731
/kg m 0.001057
m 0.005
kJ/kg 1593.6 1 . 2213 5 . 0 01 . 487
5 . 0
kPa 175
/kg m 0.001057
kJ/kg 487.01
liquid sat.
kPa 175
3
3
1
1
2 2
2
2
3
kPa 175 @ 1
kPa 175 @ 1 1
= = =
= + = + =
)
`

=
=
= =
= =
)
`
=
v
V
v v
m
h x h h
x
P
h h P
fg f
f
f
Substituting,
(400 kJ) (4.731 kg)(1593.6 487.01)kJ/kg
4835 kJ
4835 kJ 1000 VA
(8 A)(45 60 s) 1 kJ/s
elect
elect
W
I t
+ =
=
| |
= =
|

\
W = V
V 223.9 V
15
29
Steam
0.15 kg
3.5 MPa
Q
154 A piston-cylinder device contains 0.15 kg steam at 3.5 MPa , superheated by 5 C in a cylinder with a set of stops.
As Heat is lost from the steam, the piston moves down and hit the stops at which point the state is saturated liquid. It is
cooled further until a temperature of 200 C is reached. The final pressure and quality (if mixture), the boundary work,
and the heat transfer until the piston first hits the stops and the total heat transfer are to be determined.
Assumptions 1 The kinetic and potential energy changes are negligible,
. 2 The friction between the piston and the cylinder is negligible.
Analysis (a) We take the steam in the cylinder to be the system. This is a closed system since no mass
crosses the system boundary. The energy balance for this stationary closed system can be expressed as
net-in net-out system system
Net energy transfer
Change in internal, kinetic,
by heat, work
potential, etc. energies
b,in out
(since KE PE 0)
Q W E U
W Q U
= =
= = =

Denoting when piston first hits the stops as state (2) and the final state as (3), the energy balance relations may be written as
30
) u - (
) u - (
1 3 3 - out,1 in b,
1 2 2 - out,1 in b,
u m Q W
u m Q W
=
=
The properties of steam at various states are (Tables B1.1 through B 1.3)
sat@3.5 MPa
1
242.56 C
242.56 5 247.56 C
sat
T
T T dSH
=
= + = + =
kJ/kg 3 . 2617
/kg m 05821 . 0
C 56 . 247
MPa 5 . 3
1
3
1
1
1
=
=
)
`

=
=
u T
P v
kJ/kg 4 . 1045
/kg m 001235 . 0
0
MPa 5 . 3
2
3
2
2
1 2
=
=
)
`

=
= =
u x
P P v
kJ/kg 55 . 851
C 200
/kg m 001235 . 0
3
3
3
3
3
2 3
=
=
=

=
= =
u
P
x
T
kPa 1555
0.00062
v v
(b) Noting that the pressure is constant until the piston hits the stops during which the boundary work is done, it can be determined from
its definition as
kJ 29.91 = = =
3
2 1 1 in b,
0.001235)m 21 kPa)(0.058 kg)(3500 15 . 0 ( ) ( v v mP W
(c) Substituting into energy balance relations, yields Q
out 1-2
= m (h
1
h
2
) or
kJ 265.7 = = kJ/kg ) 3 . 2617 4 . 1045 ( kg) 15 . 0 ( kJ 91 . 29
2 - out,1
Q
(d) kJ 294.8 = = kJ/kg ) 3 . 2617 55 . 851 ( kg) 15 . 0 ( kJ 91 . 29
3 - out,1
Q
Specific volume comparison
out,1-2 2 1 b,in,1-3
out,1-3 3 1 b,in,1-3 out,1-2 out,2-3
( -u )+
( -u )+
Q m u W
Q m u W Q Q
=
= = +
16
31
SPECIFIC HEATS- properties of a substance
Specific heat at constant volume, c
v
: Informal definition-The energy
required to raise the temperature of the unit mass of a substance by
one degree as the volume is maintained constant.
Specific heat at constant pressure, c
p
: Informal definition-The energy
required to raise the temperature of the unit mass of a substance by
one degree as the pressure is maintained constant.
Specific heat is a property
that can be q
rev
/dT as the
energy required to raise the
temperature of a unit mass
of a substance by one
degree in a specified way.
Constant-
volume and
constant-
pressure specific
heats c
v
and c
p
(values are for
helium gas).
32
The equations in the figure are valid for any substance undergoing any
process.
c
v
and c
p
are properties.
c
v
is related to the changes in internal energy and c
p
to the changes in
enthalpy.
A common unit for specific heats is kJ/kg C or k J/kg K. Are these units
identical?
The specific heat of a substance
changes with temperature.
c
p
is always greater or
equal to c
v
.
Formal definitions of c
v
and c
p
.
17
If the heat transfer results in changes of the translational ke of the molecule, the
specific heat will remain constant; but if some of the input energy is diverted to the
rotational or viberational modes than the specific heat will increase, pjf
33
v
1
v
2
U(T,v)
T
T
u
34
INTERNAL ENERGY, ENTHALPY,
AND SPECIFIC HEATS OF IDEAL GASES
For ideal gases, u,
h, c
v
, and c
p
vary
with temperature
only(Tables--.
Internal energy and
enthalpy change of
an ideal gas
General internal energy relation for a
pure , simple compressible substance
( , )
/ [ / ]
v v
u T v
du u T dT T P T P dv
=
= +
Molecular-kinetic + potential
18
35
Specific heats
Quantities are defined that are related to the variables applicable to
reversible work.
The specific heat at constant volume for a simple compressible sub is
defined to be cv = u/T)v at constant displacement (volume).
For a reversible constant volume process this is equivalent to cv = q
rev
/dT)v
Another specific heat is defined in terms of the Thermodynamic Force
36
Specific heat at const force
The specific heat at constant pressure for a scs is defined as c
P
= h/T)
P
,at const
Thermo force. [h=u +p v>u]
For a reversible process,
this is equivalent to c
P
= qrev /T)
P
.
For an ideal gas u and h are functions only of temperature. Thus, so to are the specific
heats.
For an ideal gas, c
p
= c
v
+ R. (important)
For a gas, at any T the energy is distributed between the translational ke, rotational
ke and vibrational energy and electronic. Only the first is directly proportional to
the temperature,T.
For an ideal gas undergoing a polytropic process the equivalent specific heat is
C
n
= C
v
+ 1/(1-N)
For a given substance rotation of the molecule begins at a critical velocity of impact . As
more molecules collide at or above the critical speed the more will be put into rotation.
When the velocities become high enough to cause the molecules to vibration and result in
an increase in the specific heat. Molecules shake , rotate while they move. Rotational
energy mostly transform to translational energy on cooling, while vibration converts to
thermal radiation.
19
37
Diatomic molecule lower level Energy
Translation, rotation,vibration
At higher T the heat in part goes to increase the translational ke, resulting in T increase,
part to rotation, then part to vibration; thus for a given amount of Q the more that goes
into other than translation results in a smaller increase in T,
the ratio of dQ/dT increases due to smaller increase in T.
Translation - T
rotation not proportional to T
vibration
not prop
to T
Q (same
amount)
38
Specific heats for ideal gases. ~(f+2)/2
(Ideal gas tables)
tri
di
mon
rotation
vibration
translation
20
39
Real gas Pressure effect on cp, low P ~ig as P increase deviation from ig
40
Ideal-gas constant-
pressure specific
heats for some
gases (see Table
A6 for c
p
equations).
At low pressures, all real gases approach
ideal-gas behavior, and therefore their
specific heats depend on temperature only.
The specific heats of real gases at low
pressures are called ideal-gas specific
heats, or zero-pressure specific heats, and
are often denoted c
p0
and c
v0
.
u and h data for a number of
gases have been tabulated, A-7.
These tables are obtained by
choosing an arbitrary reference
point and performing the
integrations by treating state 1
as the reference state.
In the preparation of ideal-gas
tables, 0 K is chosen as the
reference temperature.
21
41
(kJ/kg)
For small temperature intervals, the
specific heats may be assumed to vary
linearly with temperature, for such a
case the average value is at the
average T.
Internal energy and enthalpy change and
use the mean value theorem for specific
heat average value
The relation u = c
v
T
is valid for any kind of
process, constant-
volume or not.
Area=
h
2
h
1
42
1. By using the tabulated u and h, A7 -
8 data. This is the easiest and most
accurate way when tables are
readily available.
2. By using the c
v
or c
p
relations (Table
A-6) as a function of temperature
and performing the integrations. This
is very inconvenient for hand
calculations but quite desirable for
computerized calculations. The
results obtained are accurate.
3. By using average specific heats.
This is very simple and certainly very
convenient when property tables are
not available. The results obtained
are reasonably accurate if the
temperature interval is not very
large. A.5 at 25 C
Three ways of calculating u and h
Three ways of calculating u
With varying accuracy.
For a linear variation, c
p,avg
=
(c
p
(T
2
) + c
p
(T
1
))/2
cp
22
43
Specific Heat Relations of Ideal Gases
The c
p
of an ideal gas can be
determined from a knowledge of
c
v
and R.
On a molar basis
The relationship between c
p
, c
v
and R
Specific
heat ratio
The specific ratio varies with
temperature, but this variation is
very mild.
For monatomic gases (helium,
argon, etc.), its value is essentially
constant at 1.667.
Many diatomic gases, including air,
have a specific heat ratio of about
1.4 at room temperature.
dh = c
p
dT and du = c
v
dT
44
0 pe ke
Q
O
2
T
1
= 25C
T
2
= 300C
Q
O
2
T
1
= 25C
T
2
= 300C
71 1-kg of Oxygen is heated from 25 to 300 C to experience a specified temperature change. The heat transfer
is to be determined for two cases., a) a constant volume process and b) a constant pressure process for both
cases assume the initial volume is 1 unit of volume.
Assumptions 1 Oxygen is an ideal gas since it is at a high temperature and low pressure relative to its critical
point values of 154.8 K and 5.08 MPa. 2 The kinetic and potential energy changes are negligible,
. 3 a. Constant specific heats can be used for oxygen, b. Variable specific heats..
Properties The specific heats of oxygen at the average temperature of (25+300)/2=162.5C=436 K are c
p
=
0.952 kJ/kgK (Table A-6).
Analysis We take the oxygen as the system. This is a closed systemsince no mass crosses the boundaries of
the system. The energy balance for a constant-volume process can be expressed as
net-in net-out system 2 1
Net energy transfer
Change in internal, kinetic,
by heat, work
potential, etc. energies
in 2 1
( )
( )
v
Q W E m u u
Q U m u mc T T
= =
= = =

The energy balance during a constant-pressure process (such as in a piston-cylinder device) can be expressed as
in out system
Net energy transfer
Change in internal, kinetic,
by heat, work, potential, etc. energies
in ,out
in ,out
in , 2 1
( )
( )
b
b
p avg
Q W E
Q W U
Q W P Vol U
Q H m h mc T T
=
=
= = +
= = =

since U + W
b
= H during a constant pressure quasi-equilibrium process. Substituting for both cases,
23
45
in, const , 2 1
( ) (1 kg)(0.952 kJ/kg K)(300 25)K
P p avg
Q mc T T
=
= = = 261.8 kJ
in, const 2 1
( ) (1 kg)(0.692 kJ/kg K)(300 25)K Q mc T T
=
= = = 190.3 kJ
V v,avg
46
INTERNAL ENERGY, ENTHALPY, AND
SPECIFIC HEATS OF SOLIDS AND LIQUIDS
The specific volumes of
incompressible substances
remain constant during a
process.
The c
v
and c
p
values of
incompressible substances are
identical and are denoted by c.
Incompressible substance: A substance whose specific volume
(or density) is constant. Solids and liquids are approximately
incompressible substances ; (T). dh
p
= du(T)
24
47
Internal Energy Changes for an incompressible
substance u(T,v) ; du=
Enthalpy Changes; c
v
=c
p
=c
The enthalpy of a
compressed liquid
Which is more accurate relation than
/ ) / )
v T
u T dT u v dv +
cv=cp=c
dh
p
= du
p
or c
p
= c
v
=c
48
in out system in
Net energy transfer Change in internal, kinetic,
by heat, work, and mass potential, etc. energies

water
E E E Q U = =

Food
Reaction
chamber
Water
T = 3.2C
141 A 2 g sample of a food is burned in a bomb calorimeter, that contains 3 kg of water. The
water temperature rises by 3.2C when equilibrium is established in a reaction chamber that
contains and 100 g of air.. The energy content of the food is to be determined in kJ/kg by
neglecting the energy supplied to the mixer and the thermal storage in the reaction chamber.
Assumptions 1 Water is an incompressible substance with constant specific heats. 2 Air is an ideal gas with constant
specific heats. 3 The energy stored in the reaction chamber is negligible relative to the energy stored in water. 4 The
energy supplied by the mixer is negligible.
Properties The specific heat of water at room temperature is c = 4.18 kJ/kgC (Table A-4). The constant volume specific
heat of air at room temperature is c
v
= 0.718 kJ/kgC (Table A-5).
Analysis The chemical energy released during the combustion of the sample is transferred to the water as heat.
Therefore, disregarding the change in the sensible energy of the reaction chamber, the energy content of the food is
simply the heat transferred to the water. Taking the water as our system, the energy balance can be written as
( )
( ) ( )
food
2 1
water water
[
outofreaction ChemicalE in water
in Water
Q E Q
Q U mc T T

= =
= = (

Substituting,
Q
in
= (3 kg)(4.18 kJ/kgC)(3.2C) = 40.13 kJ
for a 2-g sample. Then the energy content of the food per unit
mass is
40.13 kJ 1000 g
2 g 1 kg
| |
=
|
\
20, 060 kJ/kg - food
To make a rough estimate of the error involved in neglecting the thermal energy stored in the contents of the reaction
chamber, we treat the entire mass within the chamber as air and determine the change in sensible internal energy:
( ) ( ) [ ] ( )( )( ) kJ 0.23 C 3.2 C kJ/kg 0.718 kg 0.102
chamber 1 2 chamber
= = =

T T mc U
v
which is less than 1% of the internal energy change of water. Therefore, it is
reasonable to disregard the change in the sensible energy content of the reaction
chamber in the analysis.
&
Water
sys
For reaction chamber
25
49
Summary
Moving boundary work
W
b
for an isothermal process
W
b
for a constant-pressure process
W
b
for a polytropic process
Energy balance for closed systems
Energy balance for a constant-pressure expansion or
compression process
Specific heats
Constant-pressure specific heat, c
p
Constant-volume specific heat, c
v
Internal energy, enthalpy, and specific heats of ideal gases
Specific heat relations of ideal gases
Internal energy, enthalpy, and specific heats of
incompressible substances (solids and liquids)
50