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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.
2
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
3
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
P1 V1 T2
P2 =
T1 V2
P1 V T2 25 T2
= =
T1 2V 2 325
T2
=
26
4
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
5
Since the system is isothermal dT = 0,
V
dV = dP
P T
V
But , = 1
V P
T
dV = V dP (5)
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.
6
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
W = A = 4(r22 r12 )
= 0.02239 4((1.1 106 )2 (1 106 )2 )
= 5.909 1014 J
1
A. W. Adamson, A. P. Gast.; Physical chemistry of surfaces; 6Ed, Wiley, 1997
2
Langes Handbook of Chemistry 10th ed.