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M ASDAR I NSTITUTE OF S CIENCE AND T ECHNOLOGY

CHE501 - Chemical Engineering


Thermodynamics
Assignment 1

Author: Supervisor:
Aravind Muthiah Dr. Simo Pehkonen

February 9, 2012
Problem 1
For a pure substance:
(a) Show by the Gibbs Phase rule that the molar volume can be completely described as a function
of T, P i.e.
 V=V(T, P).
(b) Find P T
in terms of , the coefficient of thermal expansion, and , the compressibility
V
coefficient.
(c) Show that the expression you derived above is identical to direct differentiation of the equation
of state if the substance is an ideal gas.

Solution:
a. Gibbs Phase Rule: F = C - P + 2
For a single phase pure substance: C = 1, P = 1
F =11+2=2
This means that 2 independent properties are sufficient to describe the properties of the substance.
Since T and P are independent properties, they can be used to define the molar volume.

b. ! !
V V
dV = dT + dP
T P
P T

Dividing throughout by V;
! !
1 1 V 1 V
dV = dT + dP
V V T V P
P T

But , the coefficient of thermal expansion, and , the compressibility coefficient are given by;
!
1 V
=
V T P
!
1 V
=
V P
T
by substituting we get
1
dV = dT dP
V
Now at constant V;
0 = T P
P = T

1
Hence  
P
=
T V
c. Ideal Gas law;
P V = RT
Differentiating ideal gas equation with V being constant

V dP = R dT
 
P R P
= = (1)
T V V T
Differentiating ideal gas equation with P being constant

P dV = R dT
!
V R
=
T P
P
R
V = (2)
P
Rewriting ideal gas equation
RT
V =
P
Differentiating with T being constant
RT
dV = dP
P2
!
V RT
=
P P2
T
RT
V = (3)
P2
Now dividing 2 by 3 we get
P
=
T
or
P
= (4)
T
Comparing 1 and 4  
P
=
T V
which is the same as the equation obtained before.

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Problem 2
A cylinder is fitted with a heavy piston (mass of 74 kg). The cylinder contains a gas at a pressure of
25 bar and a temperature of 325 K. The cylinder has an inside radius of 0.15 m and a height to the
piston of 0.35 m. Assume that the gas is ideal with Cv = 5/2R. The piston is allowed to move, with
considerable friction, until the internal volume is doubled and then the piston is stopped. Estimate
the final temperature and pressure of the gas in the cylinder. State any assumptions you make.
Consider three cases:
(1) the cylinder is pointed vertically upward,
(2) the cylinder is horizontal and
(3) the cylinder is pointed vertically downward.

Solution:
m = 74 kg
Pint = P1 = 25 bar
T1 = 325K
r = 0.15m
h = 0.35m
Cv = 5/2R
Assume Frictional heat loss = 10 N
Assume Pext = 1.01325 bar

V1 = V = r2 h
= 0.152 0.35
= 0.0247m3

Change in volume,

V = V2 V1
= 2V V
=V

Number of moles,
P1 V1
n=
RT1

E = W + Q and U = E KE P E

U = W + Q KE P E

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Where,
U = nCv T is the Internal Energy of the system
W = Pext V is the work done on the piston by external force
Q = Ff x = 10 0.35 = 3.5J it is the heat dissipated through friction (here frictional forceFf
is assumed to be 10N)
KE = 0 piston starts from rest and loses its velocity to stop at a later point
P E = mgy where y is height to which piston is raised with reference to start point

nCv T = Pext V + 3.5 + mgy + 0


P1 V1
(5/2)R (T2 T1 ) = 1.01325 105 0.0247 + 3.5 + 74 9.8 y
RT1
25 105 0.0247
(5/2) (T2 325) = 2502.73 + 3.5 + 725.2 y
325
2506.23 + 725.2 y
T2 = 325
475
P 1 V1
Since the no. of moles in the cylinder is constant, T1 = PT2 V2 2

P1 V1 T2
P2 =
T1 V2
P1 V T2 25 T2
= =
T1 2V 2 325
T2
=
26

1. Piston moves upward:


y = h = 0.35
T2 = 319.19K, P2 = 12.28bar

2. Piston moves horizontal:


y = 0
T2 = 319.72K, P2 = 12.30bar

3. Piston moves downward:


y = h = 0.35
T2 = 320.26K, P2 = 12.32bar

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Problem 3
Imagine that 0.1 m3 of a fluid is compressed by a piston in a cylinder from a pressure of 1 bar to a
pressure of 100 bar at 300 K and that the process occurs reversibly at constant temperature.
(a) Determine the work if the fluid is an ideal gas.
(b) Determine the work if the system is liquid H2 O with = 4.46x1010 m2 N1
(c) Determine the volume change of the fluid in each case. The density of H2 O(l) at 300 K is 996
kg m3 .

Solution:
V1 = 0.1 m3
P1 = 1 bar
P2 = 100 bar
a. For an Ideal Gas
P1 V1 = P2 V2

P1 V1 1 0.1
V2 = =
P2 100
3
= 0.001m

V = V2 V1 = 0.001 0.1
= 0.099m3

ZV2
W = P dV
V1
ZV2
dV
= nRT = nRT lnV |VV21 = nRT lnV |0.001
0.1
V
V1
P1 V1
= nRT ln(0.001/0.1) = RT ln0.01
RT1
= 1 105 0.1 ln0.01 = 46, 052J

- sign Indicates work done ON the system.

b. For liquid Water    


V V
dV = dT + dP
T P P T

5
Since the system is isothermal dT = 0,
 
V
dV = dP
P T
 
V
But , = 1
V P
T

dV = V dP (5)

On integrating and solving, we get

lnV |VV21 = P |PP21

lnV |V0.12 = P |100


1
 
V2
ln = 4.46 1010 (100 1) 105
0.1
V2 = 0.099559
V = V2 V1 = 0.099559 0.1 = 4.41 104 m3
Work Done,
ZV2
W = P dV
V1

Now using 5,
ZP2 Z100
W = P V1 () dP = P V1 dP
P1 1
Z100 100
2
P
= V1 P dP = V1
2

1 1

100 12
2
= 0.1 4.46 10 10
1010
2
= 2, 230J

Problem 4
In class we went over an example of water vapor bubble increasing from 1 micron to 1.1 micron
and we calculated the amounts of PV work and surface tension work to accomplish the expansion,
do the same calculation for ethanol vapor/liquid system. How does the result for ethanol differ
from the one obtained for water (in your class notes) and why? For the answer to why, think about
the molecular level differences between ethanol and water.

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Solution:
Ethanol surface tension = 0.02239 N/m 1
Ethanol vapour pressure = 0.058 bar 2
PV Work:

W = P V = P 4/3(r23 r13 )
= 0.058 105 4/3((1.1 106 )3 (1 106 )3 )
= 8.042 1015 J

- sign because work is done by the system.


Surface tension Work:

W = A = 4(r22 r12 )
= 0.02239 4((1.1 106 )2 (1 106 )2 )
= 5.909 1014 J

Now comparing with values of that for water from class-notes;

Entity Water Ethanol


Vapour Pressure (bar) 0.0234 0.058
PV Work (J) 3.24 1015 8.042 1015
Surface Tension (N/m) 0.0728 0.02239
Surface Tension Work (J) 1.92 1013 5.909 1014
Higher Vapour Pressure of Ethanol over Water causes it to have higher PV work and lower Surface
Tension of Ethanol causes it to have lower Surface Tension work. The reason for this high vapour
pressure and low surface tension is the inadequate Hydrogen bonding between Ethanol molecules.
Even though it does have significant H-bond strength, it is low when compared to the H-bond of
water molecules borne out of high charge localisation in the Oxygen atom.

1
A. W. Adamson, A. P. Gast.; Physical chemistry of surfaces; 6Ed, Wiley, 1997
2
Langes Handbook of Chemistry 10th ed.

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