2/10/2011

1
PhysicalChemistryIforBiochemists
Chem340 Chem340
Lecture13(2/11/11)
YoshitakaIshii os ta a s
-LastMinuteUpdate
Correction for answer
P3.30) Use the relation
and the cyclic rule, and the van der Waals
i f d i i f
P V
V P
T
V
T
P
T C C |
.
|

\
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c
c
|
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\
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c
c
+ =
equation of state to derive an equation for
C
P,m
C
V,m
in terms of V
m
, T, and the gas
constants R, a, and b.
Using the van der Waals equation:
W t t b l ti
( )
2
m m
V
a
b V
T R
p

=
V | | c
We start by evaluating:
Applying the cyclic rule:
( )
( )
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|
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|

\
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=
2
m
3
m
2
m
2
m V, m p,
b V
T R
V
a 2
b V
T R
C C ( )
( )
)

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c
c
(
(

|
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c
c
= |
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\
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c
c
2
m
3
m
m
T m V
p
m
b V
T R
V
a 2
b V
R
V
p
T
p
/ 1
1 -
T
V
m
p
m
T
V
|
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\
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c
c

2/10/2011
2
Q11. AnidealgasofNmolecules(massm)isenclosed
inacubicboxoflengthL. Assumingthateachgas
moleculeistravelingalongthexaxisatavelocityofv
x
,
andhitawallandboundsbackatavelocityofv
x
,the
force that the molecule applies on one side of the wall forcethatthemoleculeappliesononesideofthewall
isgivenbyF=Ap/At=2mv
x
/(2L/v
x
)=mv
x
2
/L.Obtaina
pressurePappliedonthewallbytheNmolecules
using<v
x
2
>istheaverageofv
x
2
andtheareaofone
sideofwallisgivenbyL
2
.Choosethemost
appropriateformula.
(a)mv
x
2
/L(b)m<v
x
2
>/L (c)Nm<v
x
2
>/L (d)Nmv
x
2
/L
(e)Nm<v
x
2
>/L
3
(f)Nmv
x
2
/L
3
(g)Nm<v
x
2
>L(h)Nmv
x
2
L
F(x)=x
n
J(x)=(x b)
n
K(x)=A(x)
m
+B(x b)
n
CalculatedF(x)/dx,dJ(x)/dx,dK(x)/dx?
Foranidealgas,V(P,T)=nRT/P
Whatis(cV(P,T)/cT)
P
?
P
Whatisasuitableexpressionfor
dV =(Q1)dP +(Q2)dT?
2/10/2011
3
2.10ReversibleAdiabaticExpansion(foran
idealgas)
Adiabatic process q=0
AU=wC
V
dT =P
ext
dV
ForareversibleprocessP
ext
=P
int
C
V
dT =P
int
dV
C
V
dT =nRT/VdV
C
V
(1/T)dT =nR(1/V)dV
) / ln( ) / ln(
) / ( ) / (
ini fin ini fin V
V
V
T
T
V
V V nR T T C
dT V nR dT T C
in f
ini
in f
ini
=
=
} }
1 1
Understandtheprocessof
thefollowingderivation
) / ln( ) / ln(
ini fin ini fin V
V V nR T T C =

ini
fin
ini
fin
V
V p
ini
fin
V
ini
fin
V
V
V
V
C
C C
V
V
C nR
T
T
ln ) ( ln ) ln( ) / ( ) ln( =

= = 1
ini ini V ini ini
) (
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\
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=
1
ini
fin
ini
fin
V
V
T
T

|
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|

\
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|
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\
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=
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=
1
f
i
1
i
f
1
i
f
i
f
p
p
T
T
V
V
T
T

|
|
.
|

\
|
=
|
|
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|

\
|
1
f
i
i
f
p
p
T
T

1
i
f
1
f
i
i
f
p
p
p
p
T
T

|
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\
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=
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=
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(VT:1 )
(PT:(1)/ )
. \ . \ . \ f i i i
p
. \ . \ f i
p
) 1 (
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\
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=
ini
fin
ini ini
fin fin
V
V
V P
V P
) (
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|

\
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=
ini
fin
ini
fin
V
V
P
P

(VP:)
A=B
X
A
(1/x)
=B
) / 1 (
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\
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=
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|

\
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ini
fin
ini
fin
P
P
V
V
Memorizetheseequationsifyoucannotderivethem.
2/10/2011
4
3.4HasafunctionofP &T
HvariesbychangingPandTas
dT
H
dP
H
T P dH
|
|

| c
+
|
|

| c
= ) (
[Q1]
WhendP=0(&P=P
ext
)
dT
T
dP
P
T P dH
P T
|
.

\
c
+
|
.

\
c
= ) , (
dT
T
H
dH Dq
P
p p
|
.
|

\
|
c
c
= =
About Derivation See Sec. 3.6
P
P
P
C
dT
Dq
T
H
=
|
.
|

\
|
c
c
P T
T
V
T V
P
H
|
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|

\
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c
c
=
|
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\
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c
c
AboutDerivationSeeSec.3.6
WhenV=kTThistermiszero
Q. Canyouwritetheformula?
[Q2]
[Q3]

Q. Whatisthesignofthetotalworkforthecycle?
Q2.Whatisthesignoftheworkforeachprocess?
Q3.Whatisthesignoftheworkifthereversedcycle?
6
8
10
p [bar]
p
1
V
i
6
8
10
p [bar]
p
1
V
i
0
2
4
10 20 30 40 50 60 70 80 90 100 110 120 130
p
i
V
2
p
i
V
i
0
2
4
10 20 30 40 50 60 70 80 90 100 110 120 130
p
i
V
2
p
i
V
i
2/10/2011
5
Derivation 3.7JouleThompsonExp
ImprovedversionofJoulesexptofind(cU/cV)
T
P
L
ext
=P
1
P
R
ext
=P
2
Workapplied
w=w
left
+w
right
P
1
>P
2
ext 1
ext 2
g
2 2 1 1
2
0
2
0
1
1
V P V P dV P dV P
V
R
V
L
= =
} }
Adiabatic:q=0
AU=U
2
U
1
=w=P
2
V
2
+P
1
V
1
[1]
Eq [1] can be rearranged to Eq.[1]canberearrangedto
U
2
+P
2
V
2
=U
1
+P
1
V
1
H
2
=H
1
:Isenthalpicexpansion
ATandAPinJTexperimentyieldsJouleThompsonCoefficient
H H
P
T J
P
T
P
T
|
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\
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c
c
= |
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|

\
|
A
A
=
A

0
lim
Howis
JT
relatedto(cH/cP)
T
and(cU/cV)
T
?
dT C dP
P
H
dH
p
T
+ |
.
|

\
|
c
c
=
I J l Th i dH 0
[C
p
=(cH/cT)
P
]
Usingeq.[3.43]inCh3.6
InJouleThompsonexperimentdH=0.

dT C dP
P
H
p
T
= |
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c
c
T J p
H
p
T
C
P
T
C
P
H

= |
.
|

\
|
c
c
= |
.
|

\
|
c
c

Foranidealgas,(cH/cP)
T
=0
JT
=0
g q [ ]

V
dP
dV
P
V
U
P
H
T T T
+ |
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|

\
|
)
`

+ |
.
|

\
|
c
c
= |
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|

\
|
c
c
V
dP
dV
P
V
U
C
T T
T J p
+ |
.
|

\
|
)
`

+ |
.
|

\
|
c
c
=