1

Chapter 4

Energy Analysis of Closed Systems

4.1 Boundary Work

Consider the gas enclosed in a piston-cylinder device below. The initial pressure is P, the total
volume is V and the cross-sectional area of the piston is A. When the piston moves a distance
ds in a quasi-equilibrium manner, the differential work done during this process is

Wb Fds PAds PdV

The total boundary work done during the entire process is obtained by adding all the
differential works from the initial to the final state
2
Wb PdV ( kJ )
1

The integral can only be evaluated when P is stated in terms of V , i.e. P = f (V).

F
A gas does Wb work as it forces
the piston to move by ds
ds
P
gas

Consider a quasi-equilibrium expansion process as shown below. On the P-V diagram, the
differential area dA is equal to PdV, which is Wb . The total area under the process curve 12
is obtained by adding the differential areas:

2 2

Area = A = dA
1
PdV
1

That is, the area under the process curve on a P-V diagram is equal, in magnitude, to the work
done during a quasi-equilibrium expansion or compression process of a closed system.

P 1
process path

dA = PdV

2
V
V
V1 dV V2
P
 2

For different paths followed by the gas as it expands from state 1 to state 2, the area underneath
the curve (and the work done) will be different. It is expected since work is a path function it
depends on path and end states.

P is the pressure at the inner surface of the piston. It is only equal to the gas pressure in the
cylinder if the process is quasi-equilibrium.

During an expansion process, Wb is transferred from the system.

During a compression process, Wb is transferred to the system

4.1.1 Boundary Work for Constant Volume Process

For a constant volume process, Wb = 0.

Example.
A rigid tank contains air at 500 kPa and 150 oC. As a result of heat transfer to the surroundings,
the temperature and pressure inside the tank drop to 65 oC and 400 kPa, respectively.
Determine the boundary work done during this process.
0
2

For a rigid tank, its volume is constant. Thus dV = 0, for which Wb PdV = 0.
1
500 kPa 400 kPa P, kPa
150 oC 65 oC
. cooling 500 1
1 V = constant 2

400 2
V
* Note : Wb = area under process curve
For constant volume, area = 0 !

4.1.2 Boundary Work for a Constant-Pressure Process

2 2

For a constant-pressure process, Wb PdV P dV PV2 V1 = mP v 2 v1 .

1 1
(kJ)
where P = P1 = P2.

Example
A frictionless piston-cylinder device contains 5 kg steam at 400 kPa and 200 oC. Heat is
transferred to the steam until the temperature reaches 250 oC. Determine the work done by the
steam during this process.
P, kPa
1 2

5 kg heating 400
400 kPa
200 oC P=C 250 oC

1 2 v
 3

. v1 = 0.53434 v2 = 0.59520

Although not explicitly stated, this is a constant-pressure process since the weight of the piston
and the atmospheric pressure are constant.

Wb P1 V2 V1 mP1 v 2 v1

State 1 is at (400 kPa, 200 oC) superheated v1 = 0.53434 m3/kg

State 2 is at (400 kPa, 250 oC) superheated v2 = 0.59520 m3/kg
Thus,
Wb 5 400 0.59520 0.53434 =121.7 kJ

The +ve sign indicates work is done by the system (steam) on the surroundings.

4.1.3 Boundary Work for Isothermal Compression of an Ideal Gas

Example
A piston-cylinder device contains 0.4 m3 of air at 100 kPa and 80 oC. The air is compressed to
0.1 m3 in such a way that the temperature inside the cylinder remains constant. Determine the
work done during this process.
P, kPa 2
.

0.4 m3 T = 80 oC
100 kPa compression PV = C
80 oC 0.1 m 3
1
air T=C 80 oC 100

1 2 V
. 0.1 0.4 m3
Assume air is an ideal gas and the process is quasi-equilibrium.
C
PV mRT = C P
V
mRT is constant since m, R and T are constants.

2 2
C 1 V
Wb PdV = V dV
1
C
V
dV C ln 2
V1
1

where C = mRT1 = mRT2 = P1V1 = P2V2

can use here !
V2 0.1
Wb P1V1 ln 100 0.4 ln = 55.45 kJ
V1 0.4
V2 P
Note : Since P1V1 = P2V2 1
V1 P2

The ve sign indicates that work is done on the system by the surroundings, which is always
true for compression processes.
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4.1.3 Boundary Work for a Polytropic Process

In practice, expansion and compression processes of gases often obey the equation : PVn = C,
where n and C are constants. Such a process is called polytropic process. For such a process
between state 1 and state 2,

PV n C P CV n

V2
2 2
V n 1 V2 n 1 V1 n 1
Thus, Wb PdV CV n
dV C = C
1 1 n 1 V1 1 n
since C = P V 1 1
n
P2V 2
n
then,

P2V2nV2 n 1 P1V1nV1 n 1 P V P1V1

Wb = 2 2 general
1 n 1 n
equation !
-----------------------------------
For an ideal gas, PV = mRT , then the equation can be written as:

P2V2 P1V1 mRT2 mRT1 mR T2 T1

Wb = = ( kJ )
1 n 1 n 1 n
for n 1 .
------------------------------------
For a special case, when n = 1, it follows that PV = C or P = CV 1 for which

2 2
C 1 V
Wb PdV = V dV
1
C
V
dV C ln 2
V1
. general, n = 1
1

where C = P1V1 = P2V2 . This is also the equation for an ideal gas undergoing an isothermal
process !

Example
A piston-cylinder device contains 0.05 m3 of a gas initially at 200 kPa. At this state, a linear spring (k =
150 kN/m) is touching the piston but exerts no force on it. Heat is transferred to the gas causing the
piston to rise and to compress the spring until the volume inside the cylinder doubles. The cross-
sectional area of the piston is 0.25 m2. Determine (a) the final pressure inside the cylinder, (b) the total
work done by the gas, and (c) the fraction of this work done against the spring to compress it.

P, kPa
. x
. 2
. P2
. Heating x=0 II
. 1
200 kPa V2 = 2V1 200
0.05 m3 = 0.1 m3 I
 5

1 2 0.05 0.10 V, m3

(a)
The final volume (state 2) is, V2 = 0.2 V1 = 2(0.05) = 0.10 m3
From the undisturbed position, the spring is compressed a distance of,

V 0.10 0.05
V Ax x = = 0.2 m
A 0.25

At state 2, the force exerted by the spring is, F = k x = 150 (0.2) = 30 kN

At state 1, force balance on the piston (Fspring = 0), gives

mg Patm A P1 A

At state 2, force balance on the piston gives,

Fspring mg Patm A P2 A
Fspring 30
Fspring P1 A P2 A P2 P1 200 200 + 120 = 320 kPa
A 0.25

(b) The work done is the area under the process curve (a trapezoid) from state 1 to state 2,

W area
200 320 0.1 0.05
= 13 kJ
2

The work done is positive because integral of PdV is positive (P and dV are positive).

(c)
The rectangular area (region I) is work done against the piston and the atmosphere, and the
work done against the spring is represented by the triangular area (region II). Thus,

1
Wspring area II 320 200 0.10 0.05 = 3 KJ
2
Note: A similar result could also be obtained from :
k x 22 x12 = 150 0.2 2 0 2 = 3 kJ
1 1
Wspring
2 2
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4.2 Energy Balance for Closed Systems

Energy balance for any system undergoing any kind of process is

E in E out E system .... ( kJ )

Net energy transfer = Change in internal, kinetic,

by heat, work, mass potential, etc energies

or in rate form, it is written as

dE system
E in E out . ( kW )
dt
Rate of et energy transfer = Rate of change in internal, kinetic,
by heat, work, mass potential, etc energies

The energy balance on a per unit mass basis is,

ein eout e system . ( kJ/kg )

and in differential form as,

E in E out dE system or ein eout de system

For a closed system undergoing a cycle, the initial and final states are identical, thus

E system E final E initial 0

Ein E out 0 or E in E out

Since a closed system has no mass flow across its boundaries, the only energy interactions
possible are work and heat transfer only. Therefore, for a cycle:

Wnet ,out Qnet ,in or Wnet ,out Qnet ,in

For a closed system, the general energy balance equation is :

Qnet ,in Wnet ,out E system or

Q W E
where,
Q Qnet ,in Qin Qout is net heat input
W Wnet ,out Wout Win is net work output

Other forms of first-law relation for closed systems are :

q w e per unit mass ( kJ/kg )
q w de per unit mass; differential form ( kJ/kg )
Note : The 1st law cannot be proven mathematically !
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Example
A piston-cylinder device contains 25 g saturated water vapor that is maintained at a constant
pressure of 300 kPa. A resistance heater within the cylinder is turned on and passes a current of
0.2 A for 5 min from a 120 V source. At the same time, a heat loss of 3.7 kJ occurs. Determine
the final temperature of the steam.

P, kPa
.
.
.
. Heating 1 2
. 300
300 kPa P=C
25 g
. heater

1 2

Let Wother = work done on the system other than boundary work.
For the process, 0 0
Qin Wother Wb U KE PE
Qin Wother Wb U
Qin Wother P V2 V1 U 2 U 1
= P2V2 P1V1 U 2 U 1
= U 2 P2V2 U 1 P1V1
= H 2 H 1 = m h2 h1

where enthalpy is defined as H = U + PV

Conclusion:
For constant-pressure process, we can use :
Qin Wother Wb U or
Qin Wother H 2 H 1

The electrical work done by the surroundings is (the heater is inside the system),

We VIt = 120 (0.2) 300 = 7200 J = 7.2 kJ

At state 1 (300 kPa, sat. vapor) h1 hg ,300 kPa = 2724.9 kJ/kg

Qin Wother H 2 H 1 = m h2 h1

Qin = 3.7 kJ (heat loss)

Wother = We = 7.2 kJ

3.7 ( 7.2) = 0.025 h2 2724.9 h2 = 2864.9 kJ/kg

At state 2 (300 kPa, h = 2864.9) superheated steam T2 = 200 oC

Example
 8

A rigid tank is divided into two equal parts by a partition. Initially, one side of the tank contains
5 kg of water at 200 kPa and 25 oC, and the other side is evacuated. The partition is then
removed, and the water expands into the entire tank. The water is allowed to exchange heat
with the surroundings until the temperature in the tank returns to the initial value of 25 oC.
Determine (a) the volume of the tank, (b) the final pressure, and (c) the heat transfer for this
process.
P, kPa

Evacuated partition 1
. 200
.
. partition
200 kPa removed 5 kg
25 oC 25 oC
5 kg 2

1 2 v
(a)
State 1 (200 kPa, 25 oC) is compressed liquid v1 v f , 25 C = 0.001003 0.001
m3/kg
At state 1, volume occupied by water is : V1 mv1 = 5 (0.001) = 0.005 m3
Total volume of tank = 2 V1 = 2 (0.005) = 0.01 m3

V 0.01
(b) At state 2, v 2 = 0.002 m3/kg
m 5
At 25 oC, vf = 0.00103 m3/kg, vg = 43.340 m3/kg.
Since vf < v2 < vg state 2 is mixture. Thus P2 = Psat, 25C = 3.1698 kPa

(c) At state 1, u u f , 25C = 104.83 kJ/kg

v2 v f 0.002 0.001
At state 2, x 2 = 2.3 x 10-5
v fg 43.34 0.001
u 2 u f x 2 u fg = 104.83 + (2.3 x 10-5)(2304.3) = 104.88 kJ/kg

The work term is zero, Wb and other forms of work are not present.
0
Q W m u 2 u1 = 5 (104.88 104.83) = 0.25 kJ

The +ve sign indicates heat is transferred to the water during the process.

4.3 Specific Heats

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cv = specific heat at constant volume is the energy required to raise the temperature of a unit
mass of a substance by one degree as the volume is maintained constant.

cp = specific heat at constant pressure is the energy required to raise the temperature of a unit
mass of a substance by one degree as the pressure is maintained constant

cp > cv because for the expansion process, work must be supplied to the system.
u
cv (kJ/kg.K or kJ/kg.oC)
T v

h
cp . (kJ/kg.K or kJ/kg.oC)
T P

cp and cv are properties, since they are expressed in terms of other properties.

4.3.1 Internal Energy, Enthalpy, and Specific Heats of Ideal Gases

It has been demonstrated experimentally that for an ideal gas, u = u(T).

For an ideal gas, Pv = RT

Definition of enthalpy, h = u + Pv
Thus, h = u + RT

Since R is constant and u = u(T) h = h(T)

Since u and h depend only on temperature for an ideal gas, cp and cv also depend on
temperature only. Thus, for ideal gases :

du dh
cv and cp
dT v dT P

or
du cv dT
dh c p dT

The change in internal energy or enthalpy for an ideal gas during a process from state 1 to state
2 is obtained by integrating these equations, to give :
2
u u 2 u1 c v dT .. ( kJ/kg )
1
2
h h2 h1 c p dT ( kJ/kg )
1

Although cv and cp are temperature dependent, using average specific heats simplifies the
calculations :
u 2 u1 cv ,avg T2 T1
h2 h1 c p ,avg T2 T1
For an ideal gas, h = u + RT can be differentiated to give
dh = du + RdT
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Using the specific heats, c p dT c v dT RdT

c p dT cv dT RdT
Dividing by dT,
dT dT dT
gives cp cv = R

Note : cp and cv can be used for any process and any system !

Example
Air at 300 K and 200 kPa is heated at constant pressure to 600 K. Determine the change in
internal energy per unit mass using the average specific heat value (Table A-2b).

Average temperature = (300 + 900)/2 = 450 K

At this temperature from table, cv = 0.733 kJ/kg.K
Thus,
u 2 u1 cv T2 T1 = 0.733 (600 300) = 220 kJ/kg

Example
An insulated rigid tank initially contains 0.7 kg of helium at 27 oC and 350 kPa. A paddle
wheel with a power rating of 0.015 kW is operated within the tank for 30 min. Determine (a)
the final temperature and (b) the final pressure of the helium gas. Take cv as 3.1156 kJ/kg.oC.

P, kPa T2
He
0.7 kg Wsh 0.7 kg P2
27 oC
350 kPa paddle 27 o
C

1 2 350
V
(a)
The amount of paddle-wheel work done on the system is

Wsh Wsh t = 0.015 (30 x 60) = 27 kJ

The system is insulated Q=0

Qin Wout m u 2 u1 mc v T2 T1
0 ( 27) = 0.7 (3.1156) (T2 27) T2 = 39.4 oC

P1V P2V
(b) At state 1, m and at state 2, m
RT1 RT2
P1 P P1 350
Thus, 2 P2 T2 39.4 273 = 364.5 kPa
T1 T2 T1 27 273

Note : In an ideal gas equation, P and T are absolute quantities !

Example
A piston-cylinder device initially contains 0.5 m3 of nitrogen at 400 kPa and 27 oC. An electric
heater within the device is turned on an allowed to pass a current of 2 A for 5 min from a 120 V
 11

source. Nitrogen expands at constant pressure, and a heat loss of 2800 J occurs during the
process. Determine the final temperature of nitrogen. Take R = 0.297 kJ/kg.K and cp = 1.039
kJ/kg.K, for nitrogen gas.

Electrical work done on nitrogen, We = VI t = 120 (2) (5 x 60) = 72 000 J = 72 kJ

P1V1 400 0.5
At state 1, m = 2.245 kg
RT1 0.297 300
Qin = 2800 J = 2.8 kJ
For constant-pressure process, Qin Wother ,out H 2 H 1 m h2 h1 = mc p T2 T1
2.8 ( 72) = 2.245 (1.039) (T2 27 )
T2 = 56.7 oC
Example
A piston-cylinder device initially contains air at 150 kPa and 27 oC. At this state, the piston is resting on
a pair of stops, and the enclosed volume is 400 L. The mass of the piston is such that a pressure of 350
kPa is required to move it. The air heated until its volume doubles. Determine (a) the final temperature,
(b) the work done by the air, and (c) the total heat transferred to the air. For air, R = 0.287 kJ/kg.K and
cv = 0.823 kJ/kg.K.
.
.
.
. Heating Heating
.
150 kPa V=C 350 kPa P=C 350 kPa
400 L 400 L 800 L
27 oC

1 2 3
P1V1 PV PV 350 800
(a) m 3 3 T3 T1 3 3 300 = 1400 K
RT1 RT3 P1V1 150 400

(b) From 1 to 2, Wb = 0. From 2 to 3, W23 is boundary work for a constant-pressure process.

Thus total boundary work done by the system is

Wtotal ,out W12 W23 0 P2 V3 V2

= 350 kPa (0.8 m3 0.4 m3) = 140 kJ +ve sign indicates work done by system
(c)
P1V1 150 0.4
m = 0.697 kg
RT1 0.287 300
Process 12 Q12 W12 U 2 U 1 . W12 = 0 for constant volume process
Process 23 Q23 W23 U 3 U 2
Adding, gives Q12 Q23 W12 W23 U 3 U 1 or
Qtotal ,in Wtotal ,out m u 3 u1 mcv T3 T1
Qtotal ,in 140 0.697(0.823)(1400 300)
Qtotal ,in = 771 kJ .. +ve sign indicates heat is transferred to system.