J.

Bevan OH,
J. Rex Goates, Comparisons of Equations of State in
and H. Tracy Hall Jr.
Brighom Young University
Provo, Utah 84601
Effectively Describing PVT Relations

una proximacion bastante buena

I t is difficult to find quantitative infor- gases-to a fairly good approximation-show similar
mation, especially in a textbook, that shows how well PVT relations when compared in the same reduced
an equation of state will describe the PVT relations state. This generalization enormemente
greatly simplifies the
of any given gas. Generally the student's only in- problem of presenting the evaluation information.
formation on the subject has come from one or two The alcance
extent to which the Law of Corresponding States is
comparative calculations. This small sampling of the valid can be seen from the graph in Figure 1, originally
data can, of course, lead to some had misconceptions. presented by Goug-Jen Su.' The compressibility
trazada
For example, the molar volume of Cot gas a t 70 atm factor z = PVIRT is plotted
varios
versus the reduced pres-
and 31C calculated from the van der Waals equation is sure (?r = PIP,) for several values of the reduced
very close to the experimental value. The calculated temperatures ( 7 = T/Tc). P, and T, are the critical
sin embargo
volume, however, a t only 5 atm higher and the same state pressure and temperature, respectively. From
temperature is in error by more than 40%. Since the this graph, it is evident that, to a good approximation,
above change takes one through the critical point, one all gases follow the same reduced isotherm when z is
comportamiento
might expect somemuchas ratherdeunusual behavior in this plotted versus the reduced pressure. This behavior
las grandes
region. However, many large deviations may be provides a convenient method for comparing the pre-
found under circumstances which are more difficult to dictions of an equation of state with the experimental
predict. For example, for methane gas at OC (con-
siderably above the critical temperature) the van der
Waals equation predicts a value for the molar volume
which is 7.5y0 high a t 100 atm pressure, within 1%at
165 atm and 17% low at 400 atm. Under the same
conditions, the Dieterici equation predicts very low
values a t moderate pressures (38% low at 150 atm) hut
agrees well with the experimental data a t higher pres-
sures (less than 5y0 low a t 600 atm).
ausencia
The reason for the lack of comprehensive information
rendimiento
in the literature ahout the performance of an equation
of state is understandable. The degree of success of
an equation in describing P V T relationships depends
not only on the temperature and pressure, butpor onlothe
tanto
physical and chemical properties of the gas. Hence,
at first, it appears that a large body of information is
necessary for an evaluation to he made. Fortunately,
as implied in the Law of Corresponding States, all Figure 1 . Groph of the compressibility factor for a number of gases
como se deduce versus their reduced pressure at several reduced temperotvrer. The
d a t a taken from Goug-Jen Su (see foomoto 1) illustrate the vdidity of the
SU,Ind. Eng. C h . ,38,803 (1946).
G~UG-JEN principleof corresponding stater

Equations of State (1 Mole) Examined in this Study

Compressibility factor
Equation of state Equation of state (reduced form) (reduced form)

van der Waals p = - - RT

-
V-b
a
Va
T = 87 -
3p - 1
-
3
pn
z = a/. (T)
Berthelat
RT
p = ---
V -b
--
a
TV2
T = - - -87
3 - 1
3
rpP
z = a/, (7)
Modified
+&1 -) ]
. = - [ RT
I+ 9 PT.
Berthelot V 1 8 p ( -) ] 9 =
a = rp/R'r

where or

RTe-dVRT
R' = RT,/P.V,
re(z - Z/?d
z=l+--
1;8 :( - 3
1

Dieterici P = = z = 2sp/re1
21p - 1
T
V- b
a and b are constants different for each equation of state.

Volume 48, Number 8, August 1971 / 515


behavior of a gas. The equations of state we will be
considering can be written in a reduced form; that is,
an equation relating T , s, and the reduced volume,
q = V/V,. When written in the reduced form, the
equations become completely general. All constants
identifying a particular gas (such as the van der Waals
a and b ) cancel out. A graph of z calculated from the
reduced equation as a function of a at various T values
then applies to any gas. We will consider the solid lime
in Figure 1 to he a good representation of the experi-
mental PVT properties of any gas. A comparison of
this curve with the one obtained from the reduced
equation of state will show how well the calculation
represents the data.
We have chosen to consider the four commonly en-
countered, two-parameter equations of state listed in
Ayuda
the table. With the aid of a Hewlett-Packard calcn-
lator (2-y plotter system), we have plotted z versus a
a t various reduced temperatures for each of the four
equations. The smoothed experimental data from
Figure 1 are included for comparison. Figures 2-5
cubre the reduced pressure range a = 0-5.
cover Since
varian
critical pressures of most substances vary from 50 to
100 atm,extienden
the pressures considered in these graphs
generally extend from 0 up to 250-500 atm, a range in
which an equation ofpermiten
state might be expected to have
a simple vista
utility. The graphs allow one to see a t a glance the
magnitud
extent to which the equation of state describes the
P V T relations of the real gas under a given set of T
and a conditions. A few general observations that can
he made are
Re6YI.d Pre..YIe, 7
7
Figure 2. Comparison of the oxperimentolr (dotted lines) with the z valuer
calsulated from the van dor W a a h oquotion of state (solid lined.
R.d"C.d P
.,".
, *
Figure 3. Comparimn of tho experimental r valuer (dotted liner) with
the r values cdculoted from the Berthelot equation of state (solid lines).
516 / Journol of Chemical Education
llamativas
1 ) The rather striking limitations of a11 four equations are
evident. I t is interesting that a t 7 = 2, for example, the van der
Wads equation predicts no better z values than the ideal gas
equation ( z = I), the z values from the van der Wadsencima equation
being about ss much below as those of the ideal gas are above the
experimentalvalue. sin embargo ajsute
2) In some regions of the graph, however, the fit of the experi-
mental dsts. becomes very good; far exemple, the van der Waals
equation st r < 1 far 7 values in the range 1.0-1.2, the Berthelot
and the Dieterici equation for r < 1 a t T = 1, and the modified
Berthelot equation for r values up to 3 a t r = 2.
3) The desviarse
modified Berthelot equation, being linear in pressure,
beeins to deviate widelv from the emenmental data a t r > 3.
4 ) In general, thr van der Waali eq.mtion is suprrior exito 10 rite
varia
other three iu pr~dictiuyco~nplr~silrility factors, Iwt its success
widely a ~ t T
vsrie. ampliamnete h and P conditions 8s already noted.
como ya se han nombrado
Important applications of equations of state have
to do with corrections of exnerimental thermodvnamic
data to standard state ionrkons. Since these" calcu-
implican
lations involve relatively low pressures, it is instructive
to expand the a < 0.6 regions of Figures 2 3 . This is
done in Figures 6-9. A few general observations are
1) The performance of all the equations is, of course, much
better in this low reduced pressure region. In some regions, the
fit of the experimental data is excellent; for example, the van der
Wads equation a t r = 1.2.
2) The Berthelot and Dieterici equation are very inadequate
far quantitative calculations.
3) The Modified Berthelot equation, which was designed speoif-
ically for the low pressure region, gives z values that are con-
sistently high.
Since the predictions of compressibility factors by
the Modified Berthelot equation all differ in the same
direction, it seems reasonable to modify the semi-em-
Figure 4. Comparison of the experimental r volues (dotted lined with
the r volues calculated fmm the Modified Berthelot equation of state
(solid lined.
 R.d"C.0 Pr*..urr, n
Figure 6. Compori=on of the experimental z valuer (dolled lines) in the Figure 8. Compmison of the experimental r valuer (dotted liner) in ths
low pressure region wilh the z voluer calculated from the v m der Wmolr low preaure region with the z vduer colcvloted from the Modified Borthelot
equation of stole frolid lined. equation of rtote (solid liner).

\ 8'. I
0 01 0.2 as 0.. 05 06

W6ue.d Pr.1.ur.. "

Figure 7. Comporiron of the experiment01 z voluer (dotted lines) in the
low preswro region wilh the z valuer colcvlotod from the Berthelot equo-
lion of itate (solid lines). Figure 9. Comporimn of the oxporimsntal z values (dotted lines) in the
low pressure region with the r values calculated from tho Dieterici equation
of state ( d i d lines).
pirical constants of this equation to improve the agree-
ment with the experimental data. This we have done
by obtaining a least squares fit of the experimental
obteniedno un ajuste de minimos cuadrados
data (in the form of the Modified Berthelot equation)
for values of ?r from 0 to 0.6, and for the six r values of
1.0,1.1,1.2,1.3,1.5,and2.0. Theresultis

A comparison of this equation with the experimental

data is shown in Figure 10. The new constants are
seen to produce a better over-all fit of the experimental
desordenada
data, and a t the same time make for a less cluttered
equation. We have used the Modified Berthelot
equation with the new constants in fugacity coefficient
calculations, standard state entropy corrections, and
capacidad
with calculatious of the effect of pressure on heat ca- caloifica
ligeramnete
pacity (requires a h2P/bT2derivative) with slightly
Figure 10. Comparison of the experiment01 r values (dolled lines) in lho
better results than are obtained with the old set of low pressure region wilh the r values solsulated from e q n (1) (solid
constants. lines).

Volume 48, Number 8, August 1971 / 517