Linear regression analysis to determine Antoine equation constants W.R.

Wilcox, Clarkson University, spring 2004

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.
W.R. Wilcox, Clarkson University, spring 2004
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A B C D E F G H I J
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.
p (Pa) from
p (torr) T (C) p (Pa) T (K) ln(p) 1/T ln(p)/T correlation
1 -222.0 133 51.2 4.89 0.0196 0.096 132
5 -217.2 667 56.0 6.50 0.0179 0.116 734
10 -215.0 1333 58.2 7.20 0.0172 0.124 1412
20 -212.8 2666 60.4 7.89 0.0166 0.131 2544
40 -210.0 5333 63.2 8.58 0.0158 0.136 4971
60 -208.1 7999 65.1 8.99 0.0154 0.138 7497
100 -205.7 13332 67.5 9.50 0.0148 0.141 12062
200 -201.3 26664 71.9 10.19 0.0139 0.142 25931
400 -196.3 53329 76.9 10.88 0.0130 0.142 54084
760 -191.3 101325 81.9 11.53 0.0122 0.141 100861
202650 89.7 12.22 0.0112 0.136 225131
T (C) p (atm) 506625 102.5 13.14 0.0098 0.128 613903
-191.3 1 1013250 112.2 13.83 0.0089 0.123 1098707
-183.5 2 2026500 123.5 14.52 0.0081 0.118 1895541
-170.7 5 3039750 131.3 14.93 0.0076 0.114 2594755
-161.0 10
-149.7 20
-141.9 30
Using Analysis Tools, Regression we get the output below.
SUMMARY OUTPUT
Regression Statistics
Multiple R 0.999691
R
2
= R Square 0.999382
Adjusted R Square 0.999279
Standard Error 0.081747
Observations 15
ANOVA
df SS MS F Significance F
Regression 2 129.617 64.809 9698.15 5.587E-20
Residual 12 0.08019 0.0067
Total 14 129.697
Parameter CoefficientsStandard Error t Stat P-value Lower 95% Upper 95%
Intercept 19.08881 0.23499 81.231 8.1E-18 18.576807 19.600822
1/T -805.322 5.87716 -137.03 1.5E-20 -818.1275 -792.517075
ln(p)/T 16.13833 1.65059 9.7773 4.6E-07 12.54199 19.7346626
From this we see:
A = 19.08881
C = -16.1383
B = 497.2608
Original Data Modified units Parameters for regression
Interpretation of results produced by Regression
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K L M N O
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Temperature, K
Antoine correlation for CO
Experimental
Correlation
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.