Representation of Equilibrium

Constant Data
EDWARD G. SCHEIBEL
Hydrocarbon Research.
A nomograph is presented which gives the equilibrium
constant data for hydrocarbon mixtures. It covers a
wider range of temperatures and pressures with much
greater accuracy than previous ones. The construction of
the nomograph is completely empirical, with the calibration
of the temperature scale based on the liquid fugacity
of a reference substance and the pressure scale based on
the vapor fugacity of the reference substance. The nomograph
is useful in the calculation of bubble points, dew
points, and equilibrium flashes on hydrocarbon mixtures
in that a single setting gives the value of the equilibrium
constants for all the components.
N AN IDEAL multicomponent mixture the partial pressure of
any component is proportional to its concentration. This ie
known as Raoult s law and, when combined with Dalton s and
Avogadro s laws, can be expressed in the familiar form (6,8):
y = KX
where y = mole fraction of component in vapor
z = mole fraction of component in liquid
K = equilibrium constant
The value of K is a function of the temperature and pressure,
and also varies with the different components. In ideal solutions it
can be readily shown to be equal to the ratio of the vapor pressure
of the pure liquid to the total pressure on the system. A more
general expression is the ratio of the fug%city of the liquid to the
fugacity of the vapor. This takes into account the deviations of
the vapor and liquid from ideality.
The K values are usually represented by a set of graphs showing
either the effect of temperature and pressure on the equilibrium
constant of a given compound or the effect of temperature on the
equilibrium constants for the different compounds at a given
pressure, The first set requires the use of all the necessary charts
to carry out the usual bubble point, dew point, and equilibrium
flssh calculations. The second set is generally more convenient to
use but is difficult to interpolate at pressures not given by the
charts.
Several attempts have been made to represent all the data on a
single plot. Shiah (9) developed a chart baaed on the assumption
that the relation, between the temperatures at which any two
compounds have the same K value is independent of pressure.
This is not strictly true. However, Shiah was able to equalize the
errors by choosing as the reference substance a compound occurring
at the center of the series of compounds covered by thechart,
namely, +pentane.
A better chart was developed by Othmer (5) who found that the
logarithm of the K values of any compound at a given pressure
waa a linear function when plotted against the logarithm of the
vapor pressure of water at the same temperature. A more convenient
and precise chart was also developed by Othmer, based
on the fact that at a constant K value the logarithm of the pressure
was a linear function of the logarithm of the vapor pressure
of water at the same temperature. The nomograph was limited
by the fact that deviations occurred which made it inadvisable to
AND FRANK J. JENNY
Inc., New York, N. Y.
construct the scales over the complete range of temperatures and

pressures usually encountered in design calculations.

Recently Miller and Barley (4) presented a nomograph based
on the principle that the liquid fugacity is a function of temperature
alone and the vapor fugacity is a function of pressure alone.
This latter effect does not hold at high pressures since temperature
then becomes an appreciable factor. Thus their nomograph was
also somewhat limited in the range over which accurate results
could be obtained. Also the construction of the nomograph was
such that two separate operations were required to obtain the K
value of any particular compound.
CONSTRUCTION OF NOMOGRAPH
Figure 1 is based on the principles used by Miller and Barley
and applied to the type of nomograph presented by Othmer to
combine both the convenience and the precision of application.
The temperature scale is baaed on the logarithm of the fugacity
of liquid pentane. The pressure scale is based on the logarithm
of the fugacity of the vapor of pentane. For this calibration
a curve passing approximately through the center of the range
of fugacity variation waa chosen. If the vapor fugacity were
independent of temperature, all the component scales in the
nomograph would be straight lines parallel to the pressure and
temperature scales and logarithmically calibrated. The major
deviations are compensated by the curved lines which result from
the empirical construction of various compound scales. All ot
these scales were found by the intersection of lines connecting the
various temperature and pressure conditions which give the particular
K value to be located.
The scales of methane through octane were based on the K
values reported by Sherwood (8) and by Robinson and Gilliland
(6). The scales of decane and tetradecane were based on values
given by Brown (I), and the remaining scales were located by interpolation
and extrapolation of the data of Brown (I). The gap
between the scales of octane and nonane corresponds to the
change in the source of the data. However, the values for heptane
and lighter components given by Brown are for all practical
purposes in sufficient agreement with those of Sherwood and
Robinson and Gilliland.
USE OF THE NOMOGRAPH
A line connecting the given temperature and pressure intersects
all the component scales at the values of the respective equilibrium
constants. Over the greatest range of conditions the nomograph
gives values which agree with published data with an accuracy
of about 2%. This is within the reliability of the basic
data. However, at pressures greater than 300 and less than 10
pounds per square inch, the deviation of the values given by the
nomograph from the published data increases to about 10% or
more at certain temperatures.
At high pressures the K values for the different components
have been found to vary with the composition of the mixture.
This variation is greatest as the critical point of the mixture is
approached. At the critical point the K values of all components