EXERCISE 4:

Vapor Pressure of a Liquid

CHEM 111.1 7L
Peter James Q. Dequiña
GROUP 1
Claudine Castillo Bugtong
Jermaine Comprendio
Danica Enguerra
Raphael Angelo Gonzales
Marion Michal Fe G. Hall

EXERCISE PERFORMED ON: March 1, 2019

FULL REPORT SUBMITTED ON: March 11, 2019
I. Introduction
The molecules of an ideal gas have negligible volume and do not exhibit intermolecular
forces of attraction, and the reference equation that describes this in terms of pressure
(P), temperature (T), molar volume (𝑉) and the ideal gas constant (R) can be seen in
equation 2-1 below.

𝑃𝑉 = 𝑅𝑇 (2-1)
While it is possible for some gases to behave approximately as if they were ideal at
ordinary working temperatures and pressures, most especially at high temperature
and low pressure, there is no true ideal gas.
An equation of state (EOS) is a semi-empirical functional relationship between the
pressure, volume and temperature of a pure substance (Ramdharee, Muzenda &
Belaid, 2013). Currently, there are several equations of state for real or non-ideal
gases, two of which were used in this exercise, namely Van der Waals and Redlich-
Kwong (see equations 2-2 and 2-3, respectively).
𝑅𝑇 𝑎
𝑃 = 𝑉−𝑏 − (2-2)
𝑉2
𝑅𝑇 𝑎
𝑃 = 𝑉−𝑏 − 1 (2-3)
𝑇 2 𝑉(𝑉+𝑏)

The Van der Waals equation of state relates the density of gases and liquids to the
pressure, volume, and temperature, and it is viewed as an adjustment to the ideal gas
law that takes into account the non-zero volume of gas molecules, which are subject
to inter-particle attraction (Adewumi & Tuckerman, 2017). It was one of the very first
attempts to try to produce an equation which related P, V, n and T for real gases; Van
der Waals’ quantitative approach proposed the continuity of gases and liquids and
provided the most important contribution to EOS development (Ramdharee, Muzenda
& Belaid, 2013).
The Redlich-Kwong equation of state, on the other hand, is an empirical, algebraic
equation that relates temperature, pressure, and volume of gases, and it is said to be
more accurate than the Van der Waals EOS and the ideal gas equation, at
temperatures above the critical temperature (Adewumi & Tuckerman, 2017). Redlich
& Kwong introduced a temperature dependency to the attraction parameter a of the
Van der Waals EOS (Ramdharee, Muzenda & Belaid, 2013).
The compressibility factor (Z) is used as a correction factor, usually defined as 2-4, it
is a thermodynamic property for modifying the ideal gas law to account for the real
gas behavior (Liley, 2011).
𝑃𝑉
𝑍 = 𝑅𝑇 (2-4)

Fugacity is an effective partial pressure which replaces the mechanical partial

pressure in an accurate computation of the chemical equilibrium constant (Kfugacity),
which is determined by experimental process or estimated from various EOSs, and
the ideal gas pressure and fugacity are related through the dimensionless fugacity
coefficient (ɸ) as seen in equation 2-5 below.
𝑓
ɸ= (2-5)
𝑃
 In this exercise, three mathematical techniques were utilized in order to evaluate the
compression factor and fugacity coefficient: (1) the direct calculation method, which
involved manual calculation done by the researchers using several derived equations,
(2) the Newton-Raphson Method, which uses iterative calculation in order to solve for
volume in terms of temperature before solving for compressibility and fugacity, and (3)
Simpson’s Method, which makes use of numerical calculation of the area under the
curve and can be done using Microsoft Excel. Following this, the thermodynamic
equilibrium constant of a hypothetical gas-phase equilibrium reaction was determined
via direct calculation.
II. Materials and Methods
For this exercise, no physical experimental setup was needed. In order to obtain the
fugacity coefficient (ɸ) of the inert gas argon, three different methods were used to
evaluate the given integral
𝑃 (𝑍−1)
ln ɸ = ∫𝑃∗ 𝑃
𝑑𝑃 (2-6)

for a given pressure (P) and temperature, wherein P* is the lowest pressure given in
the set of Z and P data; as given by the instructor, P* was known to be 1 bar or 1 x
10-5 Pa.
A. Direct Calculation Method
By direct calculation method, all computations were done manually; the fugacity
coefficients of both the Van der Waals (2-2) and Redlich-Kwong (2-3) EOSs were
determined using the following equations,
𝑏 1 𝑏 2 1 𝑏 3
ln ɸ = 𝑅𝑇 (𝑃 − 𝑃∗ ) + 2 (𝑅𝑇) (𝑃2 − 𝑃∗2 ) + 3 (𝑅𝑇) (𝑃3 − 𝑃∗3 ) (2-7)
𝑎
− (𝑃 − 𝑃∗ )
(𝑅𝑇)2
for Van der Waals, and
𝑏 1 𝑏 2 1 𝑏 3
ln ɸ = (𝑃 − 𝑃∗ ) + ( ) (𝑃2 − 𝑃∗2 ) + ( ) (𝑃3 − 𝑃∗3 ) (2-8)
𝑅𝑇 2 𝑅𝑇 3 𝑅𝑇

𝑎 (𝑅𝑇 + 𝑏𝑃)
− 𝑙𝑛
𝑏𝑅𝑇 3/2 (𝑅𝑇 + 𝑏𝑃 ∗ )
for Redlich-Kwong, were the literature values of constants a and b for argon were
obtained from Appendix B in the laboratory manual.
B. Newton-Raphson Method
By Newton-Raphson method, the computations were done manually in order to
solve for 𝑉 in terms of P for the Van der Waals equation of state, using the following
equations based on repeated iteration, wherein 2-9 is plugged into 2-10.
3 2
𝑃𝑉 −(𝑃𝑏+𝑅𝑇)𝑉 +𝑎𝑉−𝑎𝑏
𝑉𝑛 = 3 (2-9)
3𝑃𝑉 −2(𝑃𝑏+𝑅𝑇)𝑉+𝑎
3 2
𝑃𝑉 −(𝑃𝑏+𝑅𝑇)𝑉 +𝑎𝑉−𝑎𝑏
𝑉𝑛 + 1 = 𝑉𝑛 − 3 (2-10)
3𝑃𝑉 −2(𝑃𝑏+𝑅𝑇)𝑉+𝑎
 This process was repeated until the calculated 𝑉 remained unchanged; following
its determination, the fugacity coefficient was calculated by using the
compressibility factor taken from equation 2-4 using the calculated 𝑉, wherein the
obtained Z was then substituted into equation 2-6.
C. Simpson’s Method
By use of Microsoft Excel’s spreadsheets, obtaining the fugacity coefficient by
Simpson’s Method is made easier instead of manual numerical calculation of the
area under the curve. However, for each gas, the data required in the Excel
template are the values for the compression factor and pressure at the different
temperatures, where the compressibility data is taken from Appendix B in the
laboratory manual.
Through use of the Excel program, the researchers obtained: fitted a and b values
for argon for the Van der Waals and Redlich-Kwong equations of state, Z-1/P vs P
graph using the fitted a and b values for each temperature, and values of the
fugacity coefficient for empirical, Van der Waals and Redlich-Kwong for each of
the assigned temperatures and pressures.
III. Results and Discussion
Using the direct calculation method, the gas constants a and b were taken from
Appendix B of the laboratory manual under argon (see Table 2.1.), and these
constants were then used in equations 2-7 and 2-8 in order to solve for the fugacity
coefficients of different temperatures and pressures (see Sample Calculations for
exact method of calculation), resulting in the data seen in Table 2.2. There many other
variations wherein the fugacity coefficient may be solved through direct calculation,
such as using the compressibility factor by computation of 𝑉 ideal and 𝑉 real using a
specified EOS and then using equation 2-6, however this single equation method is
used instead in order to decrease the time needed to solve, as the researchers needed
to solve for the fugacity coefficients of four temperatures and three pressures.
As seen in Table 2.2., it can be observed that there are several instances wherein the
value of the fugacity coefficient appears to increase with increasing temperature or
pressure, however this does not hold true for all computed values.
Between the two equations of state used, it can be noted that the fugacity coefficient
values obtained using the Redlich-Kwong EOS are higher than that of the Van der
Waals EOS; for Redlich-Kwong, it also appears that after 800 K the fugacity coefficient
decreases substantially, in contrast to the continuously increasing trend of Van der
Waals. As it has been said that the Redlich-Kwong EOS is more accurate than the
Van der Waals EOS (Adewumi & Tuckerman, 2017), it may follow that the values
obtained from its equation are closer to the “true value”, as in their derivation of this
EOS, Redlich & Kwong introduced a temperature dependency to the attraction
parameter a of the Van der Waals EOS (Ramdharee, Muzenda & Belaid, 2013).
Using the direct calculation method does create more room for computation errors to
occur, considering the manual derivation, estimation, as well as human input using a
scientific calculator and instrumental error during calculation; despite knowing the
equations to use and the values, there is always a chance of error that may alter the
resulting value by several decimal places which may vastly affect the understanding
of the data, especially in terms of trends among the resulting values.
Table 2.1. Gas constants (a and b) of argon for different equations of states (EOS).

EOS a b
Van der Waals 0.1342 3.167 x 10-5
Redlich-Kwong 1.671 2.195 x 10-5

Table 2.2. Fugacity coefficient (ɸ) of argon at different temperature and pressure
obtained by direct calculation method.

Paramete Fugacity coefficient (ɸ)

rs
Van der Waals Redlich-Kwong
Temperat 400 600 800 1000 400 600 800 1000
ure (K)
Pres 1 0.97919 1.0116 1.0184 1.0194 0.99522 1.0181 1.0204 1.0192
sure 0 11232 29287 4602 20863 7 67238 28425 04917
(bar) 0
2 0.96897 1.0281 1.0394 1.0410 0.99966 1.0401 1.0431 1.0399
0 03084 51545 88008 3748 40415 74736 19647 35554
0
3 0.97093 1.0502 1.0648 1.0648 1.01360 1.0661 1.0680 1.0620
0 99236 38385 5736 91614 8458 67116 44915 99321
0

Using the Newton-Raphson method, similar to the direct calculation method, also
requires manual computation, however the equations to be used are significantly
shorter than that of direct calculation. It is a method for approximating x* such that its
function is equal to zero or simply f(x*) = 0, which involves the iterative calculation of
xn based on the slope of f(x) at xn,
𝑓(𝑥𝑛 )−0
𝑓 ′ (𝑥𝑛 ) = (𝑥 (2-11)
𝑛 −𝑥𝑛+1 )

where solving for xn+1 gives:

𝑓(𝑥 )
𝑥𝑛+1 = 𝑥𝑛 − 𝑓′ (𝑥𝑛 ) (2-12)
𝑛

The aforementioned equations can be modified so that they may be applied to the Van
der Waals and Redlich-Kwong equations, which are cubic equations, in order to solve
for 𝑉 in terms of P, which will be followed by integration of the following equation that
yields the fugacity coefficient, as seen in equations 2-9 and 2-10; use of equation is
repeated until only a single, unchanging result is determined (see Table 2.3.), and this
result will then be used by calculation of the compressibility factor to find the fugacity
coefficient (see Table 2.4.).
From the computed volume data in Table 2.3., it can be observed that the value of
volume increases with increasing temperature, and the computed compressibility
factor also follows this trend; this observed relationship is due to the increased
movement of the gas molecules which causes increased collision, thus resulting in a
brief increased pressure that causes the hypothetical container to push outward in a
volume increase, by the discovery of Gay-Lussac (ChemTeam, 2011). It can also be
noted that the values of the fugacity coefficient appear much closer to 1 when using
the Newton-Raphson method as opposed to the direct calculation method, which may
be indicative of the former’s accuracy.
The Newton-Raphson method is advantageous due to its simple implementation and
relative efficiency due to the lack of many equations and complicated derivation,
however there are several disadvantages, such as: (1) requiring derivatives of f(x),
which, if complicated, may cause the method to fail, (2) requiring a very accurate initial
value, and (3) if the method does not converge, the computed values may result in a
loop instead of a single result. As the Newton-Raphson method is also calculated
manually, there is also the chance of human error in the computation process, as well
as instrumental error considering the use of a scientific calculator.

Table 2.3. Determination of the actual molar volume (𝑉actual) and compression factor
(Z) of argon at different temperatures using the Newton-Raphson Method.
Parameters Value
Van der Waals
Temperature (K) 400 600 800 1000
𝑽ideal 0.033256 0.049884 0.066512 0.08314

𝑽2 0.03324734883 0.0498878816 0.06652351027 0.08315554352

𝑽3 0.03324734432 0.04988878724 0.06652350628 0.08315553771

𝑽actual 0.03324734432 0.04988878724 0.06652350628 0.08315553771

Z 0.9997397259 1.000095968 1.000172996 1.000186886

Table 2.4. Fugacity coefficient (ɸ) of argon at different temperature and pressure
obtained using Newton-Raphson method.
Parameters Fugacity coefficient (ɸ)

Van der Waals

Temperature (K) 400 600 800 1000

Pressure (bar) 100 0.9988021113 1.000442044 1.000796993 1.000861013

200 0.9986219354 1.000508596 1.000917008 1.000990673

300 0.9985165543 1.000547528 1.000987219 1.001066526

Simpson’s Method involves the numerical calculation of the area under the curve of
𝑏
the function f(x), which is a solid line, from a to b in ∫𝑎 𝑓(𝑥)𝑑𝑥 , wherein f(x) is
approximated with quadratic polynomials instead of a linear polynomial; this process
is made simpler by use of the spreadsheets in Microsoft Excel.
As seen in Table 2.5., upon using Excel’s calculations, it can be observed that the
fugacity coefficients between Van der Waals and Redlich-Kwong barely differ from one
another; they are mostly similar up to at least the fifth decimal place and at most the
seventh, in a stark contrast to the fluctuating values obtained by the direct calculation
method. It can also be noted that these values vary from the previously obtained
fugacity coefficients using the other two methods, and they also vary substantially from
the empirical fugacity coefficient obtained with the same method (see Table 2.6.).
While Simpson’s method cannot also be said to be accurate, there is likely a margin
wherein it is considerably more accurate that the direct calculation method as well as
the Newton-Raphson method in this exercise, as the very use of a computation
program over manual calculation lessens the instances of human error by a substantial
amount, though there still may be the presence of instrumental or systematic error
brought about by Excel’s programmable coding. There are also several disadvantages
to the method, such as the fact that integrals themselves allow exact answers in terms
of fundamental constants, which is not possible with this method, and the fact that it is
often necessary to use a large number of ordinates to gain a good approximation to
the true integral (such as the use of a large amount of compressibility data).
Table 2.5. Fugacity coefficient (ɸ) of argon at different temperature and pressure
obtained using Simpson’s method.
Paramet Fugacity coefficient (ɸ)
ers
Van der Waals Redlich-Kwong
Tempera 400 600 800 1000 400 600 800 1000
ture (K)
Pres 1 1.00389 1.02310 1.02084 1.02375 1.00389 1.02310 1.02084 1.02381
sure 0 21329 20395 77582 52780 21341 20353 77562 27245
(bar) 0
2 1.00785 1.04754 1.04280 1.04892 1.00785 1.04754 1.04280 1.04904
0 44585 59316 68736 33132 44612 59236 68698 45306
0
3 1.01184 1.07318 1.06572 1.07535 1.01184 1.07318 106572 1.07554
0 81832 26100 89378 57185 81876 25986 89325 71104
0

Table 2.6. Empirical fugacity coefficients (ɸ) of argon at different pressure and
temperature as obtained by Simpson’s method.

Parameters Empirical fugacity coefficient (ɸ)

Temperature (K) 400 600 800 1000

Pressure (bar) 100 1.0017156430 1.0217395753 1.0203926837 1.0240129620

 200 1.00115498418 1.1142479408 1.0437864991 1.0489079237

300 1.0299525153 0.9527566492 1.0700245978 1.0748134452

Following the computation of the compressibility factors and fugacity coefficients, the
thermodynamic equilibrium constant of a hypothetical gas-phase equilibrium reaction
was determined by direct calculation, using the reversible reaction between ethene
and propene,
3C2H4 (g) ⇌ 2C3H6 (g)
where the reaction took place at 500 K in a 10.00-L container with a 1.00 mol initial
amount of ethene, and follows the Van der Waals EOS.
From Table 2.7., the calculated constants originated from given literature data of
critical values as well as standard enthalpy of formation and standard chemical
potential of formation, to assist in calculation of the excess potential, which would then
help determine the thermodynamic equilibrium constant (see Sample Calculations).
From the values of the standard enthalpy and standard free energies, the free energy
value of the reaction was calculated at each temperature using the Gibbs-Helmholtz
equation seen in 2-13 below.
µ𝑇2 µ𝑇1 −Δ𝑟𝑥𝑛 H 1 1
𝑇2
− 𝑇1
= 𝑅
(𝑇 −𝑇) (2-13)
2 1

In order to solve for the equilibrium constant, it was important to first solve for the
separate equilibrium pressure, ideal volume, real volume, compression factor, and
fugacity coefficient manually for both ethene and propene, following this is solving for
µ0excess, which is found by solving for the ideal chemical potentials of the equilibrium
reaction using equations 2-14 and 2-15, and getting the difference of the two.
µ0ideal = -RTln(KP) (2-14)
µ0real = -RTln(Kfugacity) (2-15)
Afterwards, ln K ɸ and K ɸ were calculated from the fugacity coefficients of the
component gases, and the thermodynamic equilibrium constant (KP) was determined
using the real chemical potential (see Table 2.8.).
It can be observed from the gathered data that the equilibrium pressure of propene is
smaller than that of ethene, likely due to a greater amount of propene molecules
present at equilibrium causing the lesser volume that ethene took up to have a greater
pressure in contrast to propene’s lower pressure. As seen from the calculated
equilibrium constant, the value is much less by several decimal places, indicating a
greater amount of ethene over propene at equilibrium.
As the calculation of the equilibrium constant used direct calculation, there is also room
for human error in derivation and calculation, as well as possible instrumental error in
use of a scientific calculator.
 Table 2.7. Calculated Van der Waals constants of the gases.

Compound a (atm L2 mol-2) b (L mol-1)

C2H4 2.599221768 0.0437
C3H6 5.0976 0.06666666667

Table 2.8. Determination of the thermodynamic equilibrium constant of the

equilibrium reaction.

Parameters C2H4 C3H6

Equilibrium Pressure (atm) 2.462282209 1.093678527
Ideal Volume (L/mol) 16.66259044 37.51376568
Real Volume (L/mol) 16.64303014 37.45621541
Compression Factor (Z) 0.9988260948 0.9984658894
ln ɸ -1.057792675 x 10-3 -1.373747127 x 10-4
ln K ɸ 2.8986286 x 10-3
µ0excess (J/mol) -12.04959909
Kɸ 1.002902834
Kfugacity 0.0803571911

IV. Summary and Conclusions

In determination of the fugacity coefficient and compressibility factor, out of the three
methods used in the exercise, the Simpson’s Method proved to have room for the least
amount of error, due to most of the calculation having been done by formulation on
the prepared Microsoft Excel template, which minimizes the probability of human error
that comes with manual derivation and computation; however, the margin for
instrumental and systematic error increases slightly due to a large portion of the
Simpson’s method relying on Excel’s computation.
Generally, use of these three methods were useful in determining both the
compression factor and fugacity coefficient at varying levels of difficulty and tedium,
though with a variation of different results and differing accuracies, while there only
appeared to be a single method, which was by direct calculation, for the computation
of the thermodynamic equilibrium constant.
V. Sample Calculations
 Direct Calculation of the Fugacity Coefficient for the Van der Waals EOS
  Direct Calculation of the Compressibility Factor for the Van der Waals EOS

VI. Literature Cited

Adewumi, M. & Tuckerman, M. (2017). Van der Waals and Redlich-Kwong Equations
of State. Retrieved February 20, 2019, from:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Te
xtbook_Maps/Map%3A_Physical_Chemistry_(McQuarrie_and_Simon)/16%3A_
 The_Properties_of_Gases/16.2%3A_van_der_Waals_and_Redlich-
Kwong_Equations_of_State

ChemTeam. (2011). Charles’ Law. Retrieved February 20, 2019, from:

https://www.chemteam.info/GasLaw/Gas-Charles.html
Liley, P.E. (2011). Compressibility Factor. Retrieved February 20, 2019, from:
http://www.thermopedia.com/content/645/

Ramdharee, S., Muzenda, E. & Belaid, M. (2013). Review of the Equations of State
and their Applicability in Phase Equilibrium Modeling. Retrieved February 20,
2019, from: http://psrcentre.org/images/extraimages/13%20413142.pdf