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H
dP
P T
H
dT +
T P
dH =
P T
T
+
P H
H
T P
H
=
P
[2]
H P
H
P T
T
=
P H
JT =
Because
[1]
[3]
T P
H
=V T
P P
[4]
V TC
V
= T where ; =40.6
T V
V T
V
=
T p
RT 1
P=
[6]
][ ( ) ] ( )
c
b
V +B 0 1
6
V
VT
V
A0 1
a
V
[7]
( ){
]}
2 A 0 4 c 2 B0 b 3 A 0 a 5 B 0 c
1
= ~ B0 +
+ +
+
p
RT T 3
RT
Cp
( RT )2 R T 4
[8]
After experimentally determining the JT coefficient this
value was compared against van der Waals equation of state
predicted values. Van der Waals, Beattie-Bridgeman and
Leonnard-Jones using constants from given the data in table 1.
2a
b
(
[
RT ) ]
=
~
Cp
(vdW)
[5]
The Beattie-Bridgeman equation of state comes
from taking equation four and using the triple
product rule of partial volume partial temperature
and substituting to make equation six. Using
equation seven and taking partials with respect to
temperature and then with respect to volume and
substituting back into the JT coefficient. Finally
substitute the coefficients for BB and this results in
equation eight.
V T
1
=
Cp
B (T )
P~
V
=1+ 2~
RT
V
[9]
T
1
=
Cp
[10]
B2 2 PV V
V
=
T
RT T
T
( )
] r dr
B (T )=2 N [ 1e
U (r )
kT
[11]
[( ) ( ) ]
r
U ( r )=4
12
[12]
r<
( r )= < r <
0 r>
B 2 (T )=2 N 0 [ 01 ] r dr 2 N 0 [ e
2
/kT
1 ] r dr2 N 0 [ e 01 ] r 2 dr
2
[13]
U(r) vs r
U(r)
Linear ()
f(x) = 0x - 0
R = 0.99
3. Results and Data Analysis:
Thus having B2 solved for; next equation nine can be rearranged
and taken a derivative to solve for Bs/T. Finally the JouleThomson coefficient can be solved for using equation 10. This
creates three different methods to solve for the jewel Thomson
coefficient. Comparing each of the four solving methods allowed
for a gauge to what assumptions and conditions match best of the
four different models.
2. Methods
There were several alterations to the procedure for this lab found
on page 103 of Experiments in Physical Chemistry. The pressure
was increased throughout the majority of the lab unlike the
procedure where the majority of data was collected as pressure
decreased. Pressure never exceeded two bars unlike the procedure
3J.O.Hirschfelder,C.F.Curtiss,andR.B.
Bird,MolecularTheoryofGasesandLiquids,
chap.3andtableIA,Wiley,NewYork(1964).