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Non-linear regression analysis to determine Antoine equation constants W.R.

Wilcox, Clarkson University, spring 2004


Use Solver to find the best values for A, B and C in the Antoine equation (ln(p) = A - B/(T + C)),
i.e., those giving the maximum value of R
2
. Use the template at the tab below.
As initial guesses start with A=10, C=-10, B=100 and with the negative of those values.
How do the new values of A, B, C and R
2
compare with those from the previous exercise?
Using 10, -10 and 10, almost the same, assuming you did previous exercise correctly.
Do the values of A, B, C and R
2
found by Solver depend on the initial guesses?
Sometimes.
Why is it better to base the calculations on ln(p) rather than p?
ln(p) because p varies over orders of magnitude and one would not expect the
magnitude of the error to be the same for all of these. The percent error,
on the other hand, is more likely to be about the same (although surely not
identical). Consequently, the error in ln(p) will be less dependent on p.
In using least squares on ln(p) we are assuming the percent error is
independent of p. While probably not true, it's much better than assuming
the absolute error is independent of p.
W.R. Wilcox, Clarkson University, spring 2004
Analysis of data on vapor pressure of Oxygen
Fit to Antoine equation (ln(p) = A - B/(T + C)). Where T is absolute temperature and A, B, C are constants to be determined.
Solution: Use solver to maximize R
2
starting with A = 13.68 13.68
A=10, C=-10, B=100 and with the negative of those values C = -4.18 -4.18
Click on cells to see formulas used. B = 780 780
from solver Values from previous exercise
Correlated Deviation squared
p (torr) T (C) p (Pa) T (K) ln(p) (ln(p)-ln(p
avg
))
2
ln(p) (ln(p
exp
)-ln(p
cor
))
2
1 -222.0 133 51.2 4.89 29.44 -2.93 61.138551
5 -217.2 667 56.0 6.50 14.57 -1.39 62.233936
10 -215.0 1333 58.2 7.20 9.75 -0.77 63.486294
20 -212.8 2666 60.4 7.89 5.91 -0.21 65.527706
40 -210.0 5333 63.2 8.58 3.02 0.45 66.075993
60 -208.1 7999 65.1 8.99 1.77 0.87 65.955656
100 -205.7 13332 67.5 9.50 0.67 1.35 66.358258
200 -201.3 26664 71.9 10.19 0.02 2.15 64.603225
400 -196.3 53329 76.9 10.88 0.32 2.95 63.006877
760 -191.3 101325 81.9 11.53 1.46 3.64 62.229630
202650 89.7 12.22 3.61 4.55 58.755977
T (C) p (atm) 506625 102.5 13.14 7.93 5.74 54.654112
-191.3 1 1013250 112.2 13.83 12.32 6.46 54.359691
-183.5 2 2026500 123.5 14.52 17.67 7.14 54.488084
-170.7 5 3039750 131.3 14.93 21.24 7.54 54.547601
-161.0 10 10.32 129.70 917.4216
-149.7 20 -6.073563383 R
2
using solver to maximize by varying A, B, C
-141.9 30 0.999082699 R
2
using A, B, C from previous exercise
The solution (values of A, B, C) depends on the initial values. Some combinations may not give a solution.
It is better here to do regression on ln(p) because p varies over 3 orders of magnitude.
Using ln(p) gives equal emphasis to minimizing the percent error for both large and small p.
If p is used, regression strongly emphasizes large values, so the result will be a poor fit
for small values of p.
Original Data Modified units Experimental
4.00
8.00
12.00
16.00
50 60 70 80 90 100 110 120 130 140
V
a
p
o
r

p
r
e
s
s
u
r
e
,

P
a

Temperature, K
Antoine correlation for CO
Experimental
Correlation

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