Linear regression analysis to determine Antoine equation constants

W.R. Wilcox, Clarkson University, s

Correlations of data have great utility for comparison with theory and for summarizing
the data in a more convenient form for engineering calculations. One parameter highly
useful for chemical engineers is the vapor pressure of a liquid versus temperature. For
pure liquids, the Antoine equation is often used to correlate vapor pressure data. This
equation is given by ln(p) = A - B/(T + C), where p is the vapor pressure, T is absolute
temperature, and A, B & C are constants to be determined. If linear regression analysis is
to be used to find these constants, we must put this equation into a linear form. This may
be done by multiplying the Antoine equation by (T + C)/T and rearranging to obtain
ln(p) = A + (AC - B)/T - C ln(p)/T. In this linear form, ln(p) is the dependent variable, 1/T and
ln(p)/T are the independent variables, A is the intercept, (AC - B) is the coefficient for 1/T
and -C is the coefficient for ln(p)/T. Use the Regression tool in Data Analysis to find A, B & C
for the carbon monoxide vapor pressure data via the tab below. Plot the experimental
and predicted values of p versus T. Convert to a log scale for p in order to show the
smaller values. Show the experimental values as points and the predicted values
as a curve. Change the scales to reduce wasted space on the graph.
As is customary, put the dependent variable on the vertical (y) axis
and the independent variable on the horizontal (x) axis.

ox, Clarkson University, spring 2004

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A
B
C
D
E
F
G
H
I
Solution to Laboratory Assignment 27
Analysis of data on vapor pressure of carbon monoxide from Perry's Chemical Engineers Handbook
Fit to Antoine equation (ln(p) = A - B/(T + C)).
Where T is absolute temperature and A, B, C
Solution: One linear form is ln(p) = A + (AC-B)/T - C ln(p)/T
are constants to be determined.
Click on cells to see the formulas used.
Original Data
p (torr)
T (C)
1
5
10
20
40
60
100
200
400
760
T (C)
-191.3
-183.5
-170.7
-161.0
-149.7
-141.9

-222.0
-217.2
-215.0
-212.8
-210.0
-208.1
-205.7
-201.3
-196.3
-191.3

p (atm)
1
2
5
10
20
30

Modified units
p (Pa)
T (K)
133
51.2
667
56.0
1333
58.2
2666
60.4
5333
63.2
7999
65.1
13332
67.5
26664
71.9
53329
76.9
101325
81.9
202650
89.7
506625
102.5
1013250
112.2
2026500
123.5
3039750
131.3

Parameters for regression p (Pa) from

ln(p)
1/T
ln(p)/T
correlation
4.89 0.0196
0.096
132
6.50 0.0179
0.116
734
7.20 0.0172
0.124
1412
7.89 0.0166
0.131
2544
8.58 0.0158
0.136
4971
8.99 0.0154
0.138
7497
9.50 0.0148
0.141
12062
10.19 0.0139
0.142
25931
10.88 0.0130
0.142
54084
11.53 0.0122
0.141
100861
12.22 0.0112
0.136
225131
13.14 0.0098
0.128
613903
13.83 0.0089
0.123
1098707
14.52 0.0081
0.118
1895541
14.93 0.0076
0.114
2594755

Using Analysis Tools, Regression we get the output below.

SUMMARY OUTPUT
Regression Statistics
Multiple R
2
R = R Square
Adjusted R Square
Standard Error
Observations

0.999691
0.999382
0.999279
0.081747
15

ANOVA
df
Regression
Residual
Total
Parameter
Intercept
1/T
ln(p)/T

SS
MS
F
Significance F
2 129.617 64.8085 9698.15 5.59E-020
12 0.080191 0.00668
14 129.6972

Coefficient Standard Et Stat

P-value Lower 95% Upper 95%
19.08881 0.234994 81.2311 8E-018 18.576807
19.600822
-805.3223 5.877155 -137.03 2E-020 -818.12752 -792.517075
16.13833 1.650594 9.77728 5E-007 12.54199 19.7346626

From this we see:

A = 19.08881
C = -16.13833
B = 497.2608
Interpretation of results produced by Regression

K
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Antoine correlation for CO

10000000

Vapor pressure, Pa

1000000

100000

Experimental
Correlation
10000
To get a smooth line for the correlation, right
click on a correlation point, select Format
Data Series, Patterns, Line Custom
Smoothed, Marker None. Do not try to use
Trendline as none of the equations built into
this tool is the Antoine equation.

1000

100
50.0

60.0

70.0

80.0

90.0

100.0

Temperature, K

110.0

120.0

130.0

140.0