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Homework 1 Solution

CBE 60553
September 2, 2014

Problem 1
AB
U = 2.5P V + C,

UAB = UB UA = 2.5[(P V )B (P V )A ] = 10000 J


Z VB
dV = 4000 J
WAB = P
VA

UAB = QAB + WAB


QAB = 14000 J

BC
Need pressure as a function of volume along this path. From the figure, the relationship is linear and
given by
P (V ) = 15 106 V + 0.65 106
Integrate to find the work
Z

VC

WBC =


P dV =

VB

15 106 V 2
+ 0.65 106 V
2

From our expression for U


UBC = 2500 J
QBC = 9500 J

CA
UCA = UC UA = 7500 J
Since volume is constant
WCA = 0
Which means
QCA = 7500 J

VC
= 7000 J
VB

Total change ABCA


Qcycle = 14000 7500 9500 = 3000 J
Wcycle = 4000 + 0 + 7000 = 3000 J
Ucycle = Qcycle + Wcycle = 0 J

Problem 2
Along the Parabola
P = 105 + 109 (V 0.02)2
the work can be found by integration
Z

VB

WAB =
VA


.03
P dV = 500000V + 2 107 V 2 3.333 108 V 3 .01 = 2666.67 J

Since
UAB = 10000
then
QAB = 12666.67 J

Problem 3
For an adiabat we know that
dU = P dV
and we can also write



U
U
dU =
dV +
dP
V P
P V

and we have the expression for U


U = 2.5P V + C
taking the partial derivatives
dU = 2.5P dV + 2.5V dP = P dV,
Z
5V dP = 7P dV,

3.5P dV = 2.5V dP
P

5
1

5 ln P = 7 ln V + C,

dP
=7
P

Z
1

dV
V

5 ln P + 7 ln V = C

P 5V 7 = C

Problem 4
There are three postulates we are testing for

II
S
>0
U
III
S(U, V, N ) = S(U, V, N )
IV
U
= 0, as S 0
S
Use Mathematica script to test all three postulates for each function given
For example, for equation a,

1/3
Sa[u , v , n ]:= R2 ( )
(n v u)1/3
(*II*)Sa[, , ]
(*III*)D[Sa[U, 1, 1], U ]
(*IV*)D[Solve[Sa[U, 1, 1] == s, U ], s]
R = 2, v = 1, = 1
(a)
P ostulateII
22/3

P ostulateIII

22/3
3U 2/3
1/3
3

P ostulateIV

3s2
4

(b)
2 21/3
3U 1/3
1/3
2 2/3


3 s
0
2 2

P ostulateII
P ostulateIII
P ostulateIV
(c)

P ostulateIII

1
p
2(2 + U )

6 2

P ostulateIV

{{0 s}}

P ostulateII

(d)
4
U2
4


P ostulateII
P ostulateIII


4
0 2
s

P ostulateIV

(e)
2 23/5 U

P ostulateII

5 (U 2 )4/5
1/5
23/5 5
((
) (
))
5s3/2
5s3/2
0
, 0
4 2
4 2

P ostulateIII
P ostulateIV
(f)

2
U
2Log[2]
nn
oo
0 es/2

P ostulateII
P ostulateIII
P ostulateIV
(g)

2 eU
r
22
e
{{0 es}}

P ostulateII
P ostulateIII
P ostulateIV
(h)
P ostulateII
P ostulateIII
P ostulateIV

eU/2 eU/2 U

2
2U

2
e
h 2i

2Log s2
i
h
0 
2

s 1 + Log s2

(i)

P ostulateII

P ostulateIII
P ostulateIV

h i

2Log 2U2
h i
0 

U 1 + Log 2U2

2
2
s
s/2
s/2
e
e
(1 + )
2

(j)
((

))
 U
2Log 2e
 U 
0
U 1 + Log 2e

P ostulateII
32

P ostulateIII
P ostulateIV

es/2 s + 1/4es/2 s2

a
b
c
d
4
e
f
g
h

10

-2

Figure 1: S vs. U, given relations A through H

14

12
j

10

0.5

1.0

Figure 2: U vs. S, given relations I and J

1.5

2.0

Function
A
B
C
D
E
F
G
H
I
J

Postulate II

!
!
!
X
!
!
!
X
!

Postulate III

!
X
!
!
!
!
!
X
!

Postulate IV

!
!
!
X
!
X
!
X
!
!

Plots
Results
B, D, F, H, J are not physically permissible

Problem 5
Call
X=

UA
UA + UB

we know UA + UB = 80, therefore


UB = 80 (1 X)

UA = 80X,
Then setting R, 0 , = 1 and plugging in VA , NA

SA = (NA VA UA )1/3 = 0.129X 1/3


Similarly
SB = (NB VB UB )1/3 = 0.086(1 X)1/3
Summing to get S
S = 0.129X 1/3 + 0.086(1 X)1/3
Entropy is maximized when X = .65, which is where we would expect the system to go to at
equilibrium once the internal wall is made diathermal. When that happens
X = 0.65, UA = 80X = 52 J
UB = 28 J
An alternative non-graphical method is to solve for where
S
=0
U
Since
S
0.043
0.029
= 2/3
=0
U
x
(1 x)2/3
X = 0.6475,

UA = 51.8,

UB = 28.2

which is just a higher precision calculation than my first estimate from the plot.

Entropy vs. Ua/(Ua+ub)


0.18
0.17
0.16
0.15

0.14
0.13
0.12
0.11
0.1
0.09
0.08

0.1

0.2

0.3

0.4

0.5
0.6
Ua/(Ua+Ub)

0.7

A
Figure 3: S(X), X = U U+U
A
B

Problem 6

A=
T V

(P ) =
T


A
V T

(S)
V

Problem 7
a)
3
b)
1/2
c)
1
d)
0
e) not homogenous

0.8

0.9

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