Example Problems

A gas undergoes a thermodynamic cycle consisting of three processes:

Process 1 - 2:

Compression with pV = constant from p1 = 105 Pa,

V1 = 1.6 m3, V2 = 0.2 m3, (U2 U1) = 0.

Process 2 3:

Constant pressure expansion from V2 to V3.

Process 3 1:

Constant volume, (U3 U1) = -3549 kJ.

(a) Sketch the cycle.

(b) Determine the heat transfer and the work for process 2 3.
p

(a)
2

Notes:
For 1 - 2: Since U12 = 0, Q12 = W12

1
V

For 3 1: Since dV31 = 0, W31 = 0.

Ucycle = 0.

Example Problems

(b)

U cycle U12 U 23 U 31

0 U 23 - 3549 0
U 23 3549 J
The work in the process 2 3 is given by,

dW23 VV3 pdV p2 (V3 V2 )

2

In order to determine this work, we need V2 since we know that V3 = V1.

We can get V2 from the relation, pV = constant .

p1V1 constant p2V2 ; p2 p1V1 / V2 8 x105 Pa.

W23 p2 (V3 V2 ) 8 x105 (1.6 0.2) 1120 kJ
Q23 U 23 W23 3549 1120 4669 kJ.
Also note that since UQ12W and,

W12 pdV

V2

V1

V2 dV
constant
dV
p1V1
1.6 x105 ln 0.2 /1.6 332.7 kJ
V1 V
V

Example Problems
Summary in kJ, note that U for the cycle = 0.

U12 = 0

W12 = -332.7

Q12 = -332.7

U23 = 3549

W23 = 1120

Q23 = 4669

U31 = -3549

W31 = 0

Q31 = -3549

Wcycle = Qcycle = 787.3 kJ

A gas in a piston-cylinder assembly undergoes an expansion process

for which the relationship between pressure and volume is given by

PVn = constant = A
The initial pressure is 3 bars, the initial volume is 0.1m3
and the final volume is 0.2 m3. Determine the work for the process in kJ if
(a) n = 1.5, (b) n = 1.0 and (c) n = 0.

In each case the work is given by,

pdV

A
Vn
V2

V21 n V11 n
dV
W A n A

n
V

V1
n
n
The constant A can be evaluated at either end state p2V2 p1V1 A

V2

V21 n V11 n p2V2 p1V 1

dV
W A n A

n
1

n
V

V1
This expression is valid for all n except n =1.

(a) To evaluate W, the pressure at state 2 is required.

n

V1
0.1
p2 p1 3bar

V
0.2

1.5

1.06bar

1.06bar 0.2m3 3bar 0.1m3 105 N / m

2
1kJ
W

3
1

1.5
1
bar
10
N
/
m

17.6kJ
(b) For n = 1 we need to consider this special case, pV A

V2
W p1V1 ln
V1
W 20.79kJ

(c) For n = 0, the pressure volume relation is just p = A

W pdV p V2 V1
W 30kJ

Example Problems
A gas is enclosed in a cylinder with a movable
piston. Under conditions that the walls are
Adiabatic, a quasi-static increase in volume
results in a decrease in pressure according to,

PA, VA

PV 5 / 3 constant for Q = 0.

WAB

105

P (Pa)

Find the quasi-static work done on the

system and the net heat transfer to the
system in each of the three processes,
ADB, ACB and the linear AB. In the
process ADB the gas is heated at
constant pressure (P = 105 Pa) until its
volume increases from 10-3 to 8 x 10-3
m3. The gas is then cooled at constant
volume until its pressure decreases to
105/32 Pa. The other processes (ACB
and AB) can be similarly interpreted
according to the figure.

105/32

C
10-3

V (m3)

8 x 10-3

Example Problems
U = Q W

From the first Law:

U = W

For the adiabatic process:

VA
V

5/3

dV
dP

WAB P V dV= 3, where
P
(
V
)

(
V

V
)
A
A

P V V
V

VA
2
dV
linearABprocess

VB

U U B U A WAB PA

VB

VA

2 / 3

5/3

2 / 3

3
= 25 100 112.5 J
2

Following
integration,

For the process ADB: W

WAB 360.9 J

ADB

but, U B U A QADB WADB

PdV P V
A

VA 700 J

and from the result of the adiabatic process

QADB U B U A WADB 112.5 700 587.5 J

and from the first law, Q = 248.4 J

Example Problems
Similarly for the process ACB: we find that WACB = -21.9 J and QACB = -90.6 J

For the process AB: W can also calculated from the area:

WAB 360.9 J and from the first law, Q AB = 248.4 J

Note that while we can calculate QADB and QACB , we can not calculate QAD , QDB , QAC
and QCB , separately for we do not know (UD UA) or (UC UA).

Given the standard enthalpies of formation, H f ,find the enthalpy for the
following reaction at 298K and 1 atmosphere pressure.
o

H of kJ / mol
MnSiO3
-246
MnO
-384
SiO2
-910

MnSiO3 ( s, 298) MnO(s,298) + SiO 2 (quartz,298)

H o

products

H of

H of

reac tan ts

910 384 (246) 1048 KJ

Given the specific heat functionality find the heat of reaction at 800K.
Heat capacity Constants (J/mol-K)
a

c x 10-5

b x 103

MnSiO3
110 16.2
-25.8
MnO
46.0 8.2
-3.7
SiO2
46.934.2
-11.3

Temp range (K)

298-1500
298-900
298-1000

First bring each of the components in the reaction from 298K to 800K

dH C p dT

800

298

dH

800

298

C p dT

H (800) H (298)

800

298

H (800) H

800

H (800) H

800

o
f
o
f

298

298

C p dT

C p dT

a bT cT dT
2

Then evaluate H for the reaction at 800K

H (800) H
o
f

800

298

a bT cT dT

b 2 c

H of aT
T
2
T

800

298

a =-17.1
b = 26.2 x 10-3
c = 10.8 x 105

26.2 x 10-3
2
2
H (800) H 17.1 800 298
800

298

o
f

1
1
10.8 x 10

800
298

H (800) 1048kJ 1.0kJ 1049kJ

P,V, T Relations and Thermodynamic Properties

Graphical equation of state

P, v, T surface projected
on the P-T plane.

Phase diagram

P,v, T surface projected

on the P- v plane.
P,v, T surface for a substance
that expands on freezing.

v = V/m, specific volume

P,V, T Relations and Thermodynamic Properties

Graphical equation of state

P,v, T surface for a substance

that contracts on freezing.

Phase diagram and P-v surface

for a substance that contracts on
freezing.

P,V, T Relations and Thermodynamic Properties

Phase change: consider a container of liquid water heated at constant
pressure (1 Atm ~ 105 Pa)

(a) The temperature of the water

rises to 100 C.
(b) At 100 C the heat energy goes
into converting the liquid water to
water vapor. The volume of the
system increases. The temperature
of the two phase, liquid/vapor
system stays constant (100 C) until
the last drop of liquid disappears.
(c) After all the fluid is converted to vapor, the temperature and volume rise as
heat is added to the vapor.

P,V, T Relations and Thermodynamic Properties

Saturated liquid

Saturated vapor
x

1-x

f
vf

vg

P,v, T surface projected on

the T- v plane for water.

Lever rule:

x(vg v) (1 x)(v v f )
v (1 x)v f xvg rule of mixtures
x

v vf
vg v f

vg-v

v-vf

vf

vg

x is the mass fraction of the

vapor called the quality.

mvap
mliq mvap

P,V, T Relations and Thermodynamic Properties

Specific internal energy and enthalpy

u = U/unit mass(J/kg)
h = H/unit mass
(J/kg)

u = Q/mass W/mass
h = u + pv
The simple rule of mixtures can always be used for any of the specific
quantities (v, u, h):

h = (1-x)hf + xhg
u = (1-x)uf + xug
v = (1-x)vf + xvg
h, u, v are the specific enthalpy, internal energy, and volume in the two-phase
fluid/gas region.

Example
Water in a piston cylinder assembly undergoes two processes from an initial state
where the pressure is 106 Pa and the temperature is 400 C.
Process 1-2:
The water is cooled as it compressed at constant pressure to the
saturated vapor state at 106 Pa.
Process 2-3: The water is cooled at constant volume to 150 C.
Sketch the processes on p-v and T-v diagrams.
For the overall process determine the work and heat transfer in kJ/kg.
Water

1
10

400 C

179.9 C
4.758

v (m3/kg)

150 C

T (C)

P (105 Pa)

Boundary

106 Pa
400 C

179.9 C 2
4.758 x 105 Pa

150 C
3

v (m3/kg)

The only work done in this process is the constant pressure compression,
process 1-2, since process 2-3 is constant volume.
V2

W pdV p V2 V1
V1

W
V V
p 2 1 p v2 v1
m
m m
Since for state 1 we know P and T, we can get the specific volume from a data Table,

(properties of superheated water vapor) v1 = 0.3066 m3/kg. The specific volume

at state 2 is the saturated value at 10 bar v2 = 0.1944 m3/kg.
W/m = 106 (0.1944 0.3066) = -112.2 kJ/kg

The minus sign indicates

work done ON the system

From the 1st Law, Q = U + W, and dividing through by the mass,

Q U W
W

u3 u1
m
m
m
m

P (105 Pa)

u1 is the specific internal energy in state 1, which we can get also get
from a Table as 2957.3 kJ/kg.
To get u3 note that we are in a 2-phase fluid/vapor region, so u3 will be a linear
combination of uf and ug determined from the quantity of fluid and vapor present
at v3 = v2. The mass fraction of vapor present or quality is given by,
Table
2

10

400 C

179.9 C
4.758

v (m3/kg)
vf

v3 v
g

150 C

v3 v f

0.1994 1.0905 x103

x3

0.494
3
vg v f 0.3928 1.0905 x10
Then using the rule of mixtures we can evaluate

u3.
u3 1 x u f xu g 1583.9 kJ/kg
631.68

2559.5

Finally,

Q U W
W

u3 u1 1583.9 2957.3 112.2 1485.6 kJ/kg

m
m
m
m
The minus sign indicates that heat is
transferred OUT of the system

A two-phase liquid-vapor mixture is initially at 5 bar in a closed container of

volume 0.2 m3 and quality, x = 0.10. The system is heated until only saturated
water remains. Determine the mass of the water in the tank and the final pressure.
Given Data
V = 0.2 m3
P1= 5 bar
x1 = 0.10
x2 = 1.0 (saturated water)

H2O

Using the Table:

State 1:
vf1= 1.0296 x 10-3 m3/kg
vg1= 0.3749 m3/kg

The water is in a closed system and the total volume and mass are constant.

P (bar)

v1 xvg1 (1 x)v f 1 0.03842m3 / kg

1 m

v V
V
0.2m3
m
5.21kg
v 0.03842m3 / kg

P2 =?

5.0

P1

v2 v1
P2 Psat @ v2 51.45bar linearly extrapolated between

vf1

v v
g1

50 and 60 bar.