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EXERCISE NO.

2
Computation of the Compression Factor and Fugacity Coefficient of Real Gases

Parakikay Rollan Paul P.


Masibag, Riden A.
Taghap, Kem M.
Torrano, Yvegeny Von D.
Lachica, Michael Aaron J.

Date Performed: August 24, 2017


Date Submitted: September 7, 2017

CHEM 111.1
6L

Rhiza Lyne E. Villones


Laboratory Instructor
I. Introduction

Gases do not have definite shape and volume, and assume the shape and volume of
its container. The behaviour of gases is then described by using properties such as pressure
(P), volume (V), temperature (T), and number of molecules (n). The quantitative relationship
between these properties gives rise to an equation of state (EOS) for a gas. The fact that there
are numerous factors that affect the behaviour of gas in various conditions makes it difficult to
explain its behaviour. Scientists have constructed an idea which neglects such factors giving
rise to a reference equation, the ideal gas equation (EQN 2-1). Ideal gas equation describes
the behaviour of an ideal gas having the assumption that molecules are in constant random
motion, do not occupy space (negligible volume), and molecules do not exhibit intermolecular
forces of attraction. Such properties are achieved at high temperature and low pressure.

𝑃𝑉 = 𝑛𝑅𝑇 EQN 2-1

Since assumptions of ideal gas equation do not always hold true, several equations of
state have been constructed in an attempt to describe the behaviour of real gases which do
not conform with the assumptions of the ideal gas. The most commonly used equations of
state for a gas are Van der Waals, Berthelot, Redlich-Kwong, Dieterici, and Virial EOS. For
the exercise, the Van der Waals and Redlich-Kwong EOS are used:
𝑅𝑇 𝑎
Van der Waals: 𝑃 = 𝑉̅−𝑏 − 𝑉̅ 2
EQN 2-2
𝑅𝑇 𝑎
Redlich-Kwong: 𝑃 = 𝑉̅−𝑏 − 1 EQN 2-3
̅ (𝑉
𝑇2 𝑉 ̅ +𝑏)

where 𝑉̅ is the molar volume (V/n), R is the ideal gas constant (8.314 J/mol K), and a and b
are gas constants.

One way to express deviation of a real gas from ideal gas can be through the
compressibility factor, Z. It is the ratio of the observed molar volume of a gas to the molar
volume of an ideal gas at the same temperature and pressure (EQN 2-4). For an ideal gas,
Z=1. If Z>1, it means that the real gas has a larger molar volume than the ideal; repulsive
forces are dominant. If Z<1, the molar volume of the real gas is smaller than that of the ideal;
attractive forces are dominant (Atkins and de Paula, 2006).

̅𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑
𝑉 ̅ 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑
𝑃𝑉
Ideal gas: 𝑍= ̅𝑖𝑑𝑒𝑎𝑙
= EQN 2-4
𝑉 𝑅𝑇

𝑏𝑃 𝑏𝑃 2 𝑏𝑃 3 𝑎𝑃
Van der Waals: 𝑍 = 1 + 𝑅𝑇 + (𝑅𝑇) + (𝑅𝑇
̅̅̅̅
) − (𝑅𝑇)2
EQN 2-5

𝑏𝑃 𝑏𝑃 2 𝑏𝑃 3 𝑎𝑃 EQN 2-6
Redlich-Kwong: 𝑍 = 1 + 𝑅𝑇 + (𝑅𝑇) + (𝑅𝑇
̅̅̅̅
) − (𝑅𝑇+ 𝑏𝑃)𝑅𝑇 3/2

Fugacity is the effective pressure and is the equivalent of activity. It comes from the
Latin for fleetness in the sense of “escaping tendency” (Atkins and de Paula, 2006). Another
way to express a real gas’ deviation from ideal gas is through the fugacity coefficient 𝛷
which is the ratio of the fugacity, f, to pressure. For ideal gas, 𝛷 = 1.

𝑓
𝛷= EQN 2-7
𝑃
The fugacity coefficient 𝛷 pertains to the deviation of a real gas from an ideal gas as a
function of temperature and pressure. Real gases have their standard state at the standard
state pressure 1 bar in which fugacity coefficient value is also equal to 1 (Graetzel and
Infelta, 2000).It could also be expressed as a function of compressibility factor as shown in
EQN 2-8.
𝑃
(𝑍 − 1) EQN 2-8
𝑙𝑛 𝛷 = ∫ 𝑑𝑃
𝑃∗ 𝑃

Using this relationship, 𝛷 for EOS are determined by calculating 𝑒 𝑙𝑛𝛷 .

Various methods can be used to compute for Z and 𝛷 of a gas. This experiment was
designed to (1) measure the degree of deviation from the ideal gas behaviour of hydrogen
gas by determining its compressibility factor and fugacity coefficient; (2) apply mathematical
techniques like Simpson’s method, non-linear curve fitting and Newton-Raphson method; (3)
evaluate the fugacity coefficients using different mathematical methods; (4) compare the
different methods used in terms of accuracy, consistency, and precision; and (5) explain the
effect of changes in temperature and pressure on the behaviour of gases.

II. Materials and Methods

Hydrogen gas was assigned to the class. To solve for the fugacity coefficient of the
gas, EQN 2-8 was evaluated using direct calculation method, Newton—Raphson method,
Simpson’s method, and weighing method.

Using direct calculation method, the values of the fugacity coefficient for Van der
Waals and Redlich-Kwong EOS at various temperature and pressure were obtained through
EQN 2-9 and EQN 2-10, respectively.

𝑏 1 𝑏 1 𝑏 𝑎
𝑙𝑛𝛷 = (𝑃 − 𝑃∗ ) + ( )2 (𝑃2 − 𝑃∗2 ) + ( )3 (𝑃3 − 𝑃∗3 ) − (𝑃 − 𝑃∗ ) EQN 2-9
𝑅𝑇 2 𝑅𝑇 3 𝑅𝑇 (𝑅𝑇)2

𝑏 1 𝑏 1 𝑏 𝑎 (𝑅𝑇 + 𝑏𝑃)
𝑙𝑛𝛷 = (𝑃 − 𝑃∗ ) + ( )2 (𝑃2 − 𝑃∗2 ) + ( )3 (𝑃3 − 𝑃∗3 ) − 𝑙𝑛 EQN 2-10
𝑅𝑇 2 𝑅𝑇 3 𝑅𝑇 𝑏𝑅𝑇 3/2 (𝑅𝑇 + 𝑏𝑃∗ )

Using the Newton-Raphson Method, the fugacity coefficient for Vander Waals EOS
was obtained through EQN 2-11. Prior to calculation of 𝛷, 𝑉̅ was calculated in terms of P
using EQN 2-12; from the obtained values, Z was calculated using EQN 2-13.
𝑃 𝑍−1 𝑃
𝑙𝑛Φ = ∫𝑃∗ 𝑃
𝑑𝑃 = (𝑍 − 1) ∙ 𝑙𝑛 𝑃∗
EQN 2-11
𝑃∗ 𝑉 3 − (𝑃∗ 𝑏 + 𝑅𝑇)𝑉̅ 2 + 𝑎𝑉̅ − 𝑎𝑏
𝑉̅𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 = 𝑉̅𝑖𝑑𝑒𝑎𝑙 − EQN 2-12
3𝑃∗ 𝑉̅ 2 − 2(𝑃∗ 𝑏 + 𝑅𝑇) + 𝑎
̅𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑
𝑉
𝑍= EQN 2-13
̅𝑖𝑑𝑒𝑎𝑙
𝑉

where P* is the lowest pressure in the data

For the Simpson’s method, evaluation of EQN 2-8 was done through Microsoft
ExcelTM. First, the values of Z, P, T, (Tc) and (Pc) were tabulated in Part II tab. Using the P
and Z values, a scatter plot with trend line was created. Then, a plot of (Z-1)/P vs P was
made. Next, in the Part III tab on the Excel Worksheet, the value of dZ was minimized using
the Solver feature of Microsoft ExcelTM. Then the value of the fugacity coefficient was
displayed in the Simpson’s Rule Empirical tab. On the other tabs, the corresponding fugacity
for the specific temperatures and pressures for the Van der Waals and Redlich-Kwong
equations were also calculated. Then, the values of the pressure in Part II tab were changed
to get the fugacity for the same temperature but different pressure.
All the graphs produced from Simpson’s method were printed and photocopied three
times for the computation of fugacity coefficient using weighing method. From the printed
graphs, a cut out of a standard rectangle outside the curve was weighed and then its area was
calculated. Next, the curves were cut out and weighed. The areas under the curves were then
calculated using EQN 2-14. From the obtained area under the curve, the fugacity coefficients
were computed using EQN 2-15.

𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑟𝑒𝑐𝑡𝑎𝑛𝑔𝑙𝑒


𝑡𝑜𝑡𝑎𝑙 𝑎𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑡ℎ𝑒 𝑐𝑢𝑟𝑣𝑒 = (𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑟𝑒𝑐𝑡𝑎𝑛𝑔𝑙𝑒) 𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑢𝑟𝑣𝑒 EQN 2-14

𝑙𝑛Φ = 𝑡𝑜𝑡𝑎𝑙 𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑢𝑟𝑣𝑒


EQN 2-15

III. Results and Discussion

Real gas deviates from an ideal gas. Another parameter expressing non-ideal gas
behaviour that was not included in the exercise was the Joule-Thomson coefficient. It is the
extent of the temperature change with pressure change. This can prove useful for relating
the heat capacities at constant pressure and volume and for a discussion of the liquefaction
of gases (Atkins and de Paula, 2006.
As mentioned, gases are generally described using pressure, temperature, volume,
and number of moles. However, experiments have established the sufficiency of using only
three of these variables. That is, one variable can be fixed so that the behaviour of gases
can be described mathematically using an equation of state (Atkins and de Paula, 2006).
With this, using Van der Waals (VdW) and Redlich-Kwong EOS, the deviation of a real gas
from ideal behavior can also be expressed in a different manner as shown in the following
equations:

Evaluating Z using VdW EOS:

𝑅𝑇 𝑎 𝑉
𝑍=( − 2)
𝑉 − 𝑏 𝑉 𝑅𝑇
𝑉 𝑎
𝑍= −
𝑉 − 𝑏 𝑅𝑇𝑉
1 𝑎
𝑍= −
𝑏 𝑅𝑇𝑉
1−𝑉

Using power series expansion and replacing 𝑉̅ by RT/P, Z is finally expressed using EQN 2-
16for VdW EOS:
1 𝑏 𝑏 𝑏
=1+ + ( )2 + ( )3 + ⋯
𝑏 𝑉 𝑉 𝑉
1−𝑉
𝑏 𝑏 𝑏 𝑎
𝑍 =1+ + ( )2 + ( )3 −
𝑉 𝑉 𝑉 𝑅𝑇𝑉

𝑏𝑃 𝑏𝑃 𝑏𝑃 𝑎𝑃
𝑍 =1+ + ( )2 + ( )3 − EQN 2-16
𝑅𝑇 𝑅𝑇 𝑅𝑇 (𝑅𝑇)2

Evaluating Z using Redlich-Kwong EOS:


𝑅𝑇 𝑎 𝑉
𝑍=( − 1 )
𝑉−𝑏 𝑅𝑇
𝑇 2 𝑉(𝑉 + 𝑏)

𝑉 𝑎
𝑍=( − 3 )
𝑉−𝑏
𝑅𝑇 2 (𝑉 + 𝑏)

1 𝑎
𝑍=( − )
𝑏 3
1 − 𝑉 𝑅𝑇 2 (𝑉 + 𝑏)

Using Taylor series expansion and once again replacing 𝑉̅ by RT/P, Z for Redlich-Kwong EOS
is expressed using EQN 2-17:
𝑏 𝑏 𝑏 𝑎
𝑍 =1+ + ( )2 + ( )3 − 3
𝑉 𝑉 𝑉
𝑅𝑇 2 (𝑉 + 𝑏)

𝑏𝑃 𝑏𝑃 𝑏𝑃 𝑎𝑃 EQN 2-17
𝑍 =1+ + ( )2 + ( )3 − 3 𝑅𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑅𝑇 2 ( + 𝑏)
𝑃

Fugacity coefficient can be derived from the chemical potential 𝜇 of a one-component


system given in EQN 2-18. Chemical potential is the energy that can be absorbed or
released during a chemical reaction.

𝑑𝜇 = −𝑆̅𝑑𝑇 + 𝑉̅ 𝑑𝑃 EQN 2-18

At constant temperature, EQN 2-18 becomes

𝑑𝜇 = 𝑉̅ 𝑑𝑃 EQN 2-19

For an ideal gas,


𝑅𝑇 EQN 2-20
𝑑𝜇 = 𝑑𝑃
𝑃

Integrating EQN 2-20 and giving consideration to the standard state of the Gibb’s energy
where the pressure is fixed at P* (1 bar), the equation then becomes

𝑃 EQN 2-21
𝜇 − 𝜇∗ = 𝑅𝑇𝑙𝑛
𝑃∗
The role of fugacity in determining the Gibbs energy of a real gas is the same as the role of
pressure in determining the Gibbs energy of an ideal gas (Mortimer, 2008). Thus, for a real
gas, EQN 2-21 is rewritten as:

𝑓
𝜇 − 𝜇∗ = 𝑅𝑇𝑙𝑛
𝑓∗

Combining EQN 2-19 and the differential equation of EQN 2-21:

𝛿𝑙𝑛 𝑓
𝑑𝜇 = 𝑉𝑑𝑃 = 𝑅𝑇( ) 𝑑𝑃 = 𝑅𝑇𝑑𝑙𝑛𝑓
𝛿𝑃 𝑇
𝑃
𝑅𝑇𝑙𝑛𝑓 = 𝑅𝑇𝑙𝑛𝑓 ∗ + ∫ 𝑉̅ 𝑑𝑃
𝑃∗
Manipulating equations, it is then becomes,
𝑃
𝑃 𝑅𝑇
𝑅𝑇𝑙𝑛 ∗
− ∫ 𝑑𝑃 = 0
𝑃 𝑃∗ 𝑃
Adding and rearranging equations,
𝑃 𝑃
𝑃 𝑅𝑇
𝑅𝑇𝑙𝑛𝑓 = 𝑅𝑇𝑙𝑛𝑓 ∗ + ∫ 𝑉̅ 𝑑𝑃 + 𝑅𝑇𝑙𝑛 ∗
− ∫ 𝑑𝑃
𝑃∗ 𝑃 𝑃∗ 𝑃

𝑓 𝑓∗ 𝑃
𝑅𝑇
𝑅𝑇𝑙𝑛 = 𝑅𝑇𝑙𝑛𝛷 = 𝑅𝑇𝑙𝑛 ∗ + ∫ (𝑉̅ − ) 𝑑𝑃 EQN 2-22
𝑃 𝑃 𝑃∗ 𝑃

As the pressure approaches zero, the real gas and the corresponding ideal gas
become identical (Mortimer, 2008). In this condition, the first term on the right side of EQN 2-
22 becomes negligible. Solving for 𝑉̅ from EQN 2-4 and substituting it to the resulting
equation gives the relation between fugacity coefficient and compressibility factor of a real
gas.
𝑃
𝑅𝑇
𝑅𝑇𝑙𝑛𝛷 = ∫ (𝑉̅ − ) 𝑑𝑃
𝑃∗ 𝑃

𝑃
𝑍𝑅𝑇 𝑅𝑇
𝑅𝑇𝑙𝑛𝛷 = ∫ ( − ) 𝑑𝑃
𝑃∗ 𝑃 𝑃

𝑃
𝑅𝑇 (𝑍 − 1)
𝑅𝑇𝑙𝑛𝛷 = ∫ ( ) 𝑑𝑃
𝑃∗ 𝑃

𝑃
(𝑍 − 1)
𝑅𝑇𝑙𝑛𝛷 = 𝑅𝑇 ∫ ( ) 𝑑𝑃
𝑃∗ 𝑃

Thus, a general equation for the formula of fugacity was obtained (EQN 2-8).

𝑃
(𝑍 − 1)
𝑙𝑛𝛷 = ∫ 𝑑𝑃
𝑃∗ 𝑃
Now, for a Van der Waals gas,

𝑏𝑃 𝑏𝑃 2 𝑏𝑃 3 2 𝑎
𝑙𝑛𝛷 = ∫[ + ( ) 𝑃 + ( ) 𝑃 − ]𝑑𝑃
𝑅𝑇 𝑅𝑇 𝑅𝑇 (𝑅𝑇)2
Finally obtaining

𝑏𝑃 1 𝑏𝑃 2 1 𝑏𝑃 3 𝑎
𝑙𝑛𝛷 = + ( ) + ( ) −
𝑅𝑇 2 𝑅𝑇 3 𝑅𝑇 (𝑅𝑇)2
For a Redlich-Kwong gas,

𝑏 𝑏 2 𝑏 3 2 𝑎
𝑙𝑛𝛷 = ∫[ + ( ) 𝑃 + ( ) 𝑃 − 3 𝑅𝑇 ]𝑑𝑃
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑃𝑅𝑇 2 ( 𝑃 + 𝑏)
Obtaining a final equation of

𝑏𝑃 1 𝑏𝑃 2 1 𝑏𝑃 3 𝑎
𝑙𝑛𝛷 = + ( ) + ( ) − 3 ln(𝑅𝑇 + 𝑏𝑃)
𝑅𝑇 2 𝑅𝑇 3 𝑅𝑇
𝑏𝑅𝑇 2

Z and 𝛷 represent the deviation of a real gas from the ideal behaviour. As already
mentioned, these variables both take a value of 1 for an ideal gas. For real gases, the values
of Z and 𝛷 could take values greater than or less than one. For Z and 𝛷 values greater than
1, repulsive forces acting on the gas are dominant; for For Z and 𝛷 values smaller than 1,
attractive forces acting on the gas are dominant. The farther the value is from 1, the larger is
the deviation from ideal behaviour.
In the exercise, EQN 2-9 and EQN 2-10 were used to directly calculate the value of
the fugacity coefficient of the hydrogen gas at different temperature and pressure shown in
Table 2.1. For the temperature values given, the equation was evaluated from P*= 1x105 Pa
to the corresponding pressures. The gas constants for the hydrogen gas for the VdW EOS
𝑃𝑎∙𝑚6 𝑚3
are 𝑎 = 2.479 × 10−2 and 𝑏 = 26.60 × 10−6 , while for Redlich-Kwong EOS, 𝑎 =
𝑚𝑜𝑙 2 𝑚𝑜𝑙
𝑃𝑎∙𝑚6 𝑚3
14.47 × 10−2 𝑚𝑜𝑙2 and 26.74 𝑏 = 18.44 × 10−6 𝑚𝑜𝑙.

Table 2.1. Data on the fugacity coefficient of hydrogen gas at different temperature
and pressure for Vander Waals and Redlich-Kwong EOS using direct computation
method.

Temperature Pressure Fugacity coefficient, 𝛷


K 105 Pa VdW RK
100 1.062223205 1.051467297
400 200 1.137377659 1.110270915
300 1.228177219 1.177121744
100 1.045400465 1.035608030
600 200 1.096782050 1.074518431
300 1.154665670 1.116725909
100 1.035481074 1.027069214
800 200 1.074444274 1.056039922
300 1.116943913 1.086786661
100 1.029060703 1.021793183
1000 200 1.060421166 1.044837340
300 1.093999772 1.068987956

Since a low pressure is an idealizing condition, it is expected that with increasing


temperature, the gas deviates from the ideal behaviour. The results of the computation show
that at constant temperature with increasing pressure, the value of 𝛷 increases and deviates
from 1 consequently implying a deviation from ideal behaviour. Also, at higher
temperatures, a gas is expected to behave more ideally. The data show that 𝛷 values
approaches 1 as temperature is increased.
At high pressures, the gas molecules are near to one another that attraction and
repulsion among them affects the ideality of the gas. As well as at low temperatures, the gas
molecules have relatively low mean speeds that they can be captured by one another resulting
to deviation from ideality again (Atkins and de Paula, 2006).
Another method used for computing for the fugacity coefficient of a gas is the
Newton-Raphson method. This method is a way of evaluating roots of a function (or the zero
of a function) which employs iterative process to approach one specific root. It involves the
use of tangent lines to replace the graph of y=f(x) near the point where f is zero. The iterative
calculation is based on the slope of f(x) at xn.

𝑓(𝑋𝑛 ) − 0
𝑓 ′ (𝑥𝑛 ) =
𝑋𝑛 − 𝑋𝑛+1

𝑓(𝑋𝑛 ) EQN 2-23


𝑋𝑛+1 = 𝑋𝑛 −
𝑓′(𝑋𝑛 )

In EQN 2-23, 𝑋𝑛 represents the current known value, 𝑓(𝑋𝑛 )the value of the function
at 𝑋𝑛 , 𝑓′(𝑋𝑛 ) the slope at 𝑋𝑛 , and 𝑋𝑛+1 the value we are trying to find out.
In Newton-Raphson method, Z can be expressed as the ratio of the observed molar
volume 𝑉̅𝑜𝑏𝑠 to the ideal molar volume 𝑉̅𝑖𝑑𝑒𝑎𝑙 . While 𝑉̅𝑖𝑑𝑒𝑎𝑙 is solved using ideal gas equation,
𝑉̅𝑜𝑏𝑠 can be solved by applying EQN 2-23 to volume computations:

𝑓(𝑉̅0 )
𝑉̅𝑜𝑏𝑠 = 𝑉̅𝑖𝑑𝑒𝑎𝑙 −
𝑓′(𝑉̅0 )

Solving for 𝑓(𝑉̅0 )and 𝑓′(𝑉̅0 ),


𝑅𝑇 𝑎
𝑃= − 2
̅
𝑉−𝑏 𝑉 ̅

Multiplying both sides of the equation by (𝑉̅ − 𝑏),

𝑎 𝑎𝑏
𝑃(𝑉̅ − 𝑏) = 𝑅𝑇 − +
𝑉̅ 𝑉̅ 2

Multiplying both sides of the equation by 𝑉̅ 2 ,

𝑃𝑉̅ 3 − 𝑃𝑏𝑉̅ 2 = 𝑅𝑇𝑉̅ 2 − 𝑎𝑉̅ + 𝑎𝑏


EQN 2-24
𝑃𝑉̅ 3 − (𝑃𝑏 + 𝑅𝑇)𝑉̅ 2 + 𝑎𝑉̅ − 𝑎𝑏 = 0= 𝑓(𝑉̅0 )
EQN 2-25
3𝑃𝑉̅ 2 − 2(𝑃𝑏 + 𝑅𝑇)𝑉̅ − 𝑎 = 0 = 𝑓′(𝑉̅0 )
Substituting equations EQN 2-24 and EQN 2-25 to EQN 2-23 and replacing P by 𝑃∗ gives the
final equation EQN 2-12for the observed molar volume.

𝑃∗ 𝑉 3 − (𝑃∗ 𝑏 + 𝑅𝑇)𝑉̅ 2 + 𝑎𝑉̅ − 𝑎𝑏


𝑉̅𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 = 𝑉̅𝑖𝑑𝑒𝑎𝑙 −
3𝑃∗ 𝑉̅ 2 − 2(𝑃∗ 𝑏 + 𝑅𝑇) + 𝑎

On the other hand, integration of EQN 2-8 gives the formula for the fugacity coefficient for the
Newton-Raphson method as shown in EQN 2-11:

𝑃
𝑙𝑛∅ = (𝑍 − 1)𝑙𝑛
𝑃∗
̅𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑
𝑉
where 𝑍 = ̅𝑖𝑑𝑒𝑎𝑙
𝑉

In solving for the fugacity coefficient of hydrogen gas using Newton-Raphson


method, the observed molar volume was determined first by repeated iteration until the root
is achieved. This value was then substituted to EQN 2-11 and the resulting value was finally
used to solve for the fugacity coefficient (for Van der Waals EOS). The calculated values
(Table 2.2) show that at constant temperature and increasing pressure, the value of fugacity
coefficient slightly increases and deviates farther from 1. At same pressure condition but
increasing temperature, the fugacity coefficient moves closer to ideal behaviour where ф is
equal to 1. The data for this method were in agreement with the theoretical; low pressure
and high temperature are idealizing conditions.

Table 2.2. Compression factor and fugacity coefficient of hydrogen gas for Van der
Waals EOS using Newton-Raphson method

Pressure Compression Factor, Z Fugacity coefficient, ф


Temperature, K (VdW)
105 Pa (VdW)
100 1.000576015 1.002656168
400 200 1.003056572
300 1.003290867
100 1.000433712 1.001999312
600 200 1.002300584
300 1.002476859
100 1.000343932 1.001585122
800 200 1.001823924
300 1.001963640
100 1.000284100 1.001309186
1000 200 1.001506386
300 1.001621759

For the Simpson’s method, Microsoft Excel was used to obtain the integral for the
computation of fugacity coefficient. This method involves the use of quadratic polynomials
instead of linear polynomial to approximate the value of an integral by adding the areas of
the parabolic arcs of the graph of a function f(x). Simpson’s rule states that “if a function f is
continuous on the closed interval [a, b], n is an even integer, and the numbers 𝑎 =
𝑥𝑜 , 𝑥1 , 𝑥2 , … , 𝑥𝑛−1, 𝑥𝑛 = 𝑏 form a regular partition of [a, b], then:
𝑏
𝑏−𝑎
∫ 𝑓(𝑥)𝑑𝑥 ≈ [𝑓(𝑥𝑜 ) + 4𝑓(𝑥1 ) + 2(𝑥2 ) + 4𝑓(𝑥3 ) + 2𝑓(𝑥4 ) + ⋯ + 2(𝑥𝑛−2 ) + EQN 2-26
𝑎 3𝑛
4𝑓(𝑥𝑛−1 ) + 𝑓(𝑥𝑛 )”

Thus, this method solves for the area under the curve of the function under a certain interval
and uses equal parts of the curve to approximate the integral.

In this exercise, to obtain the fugacity coefficients of the said equations of state
above, first, the areas under the curves were obtained using the general equation EQN 2-50
𝑍 −1
above where𝑓(𝑥𝑖 ) = 𝑖𝑃 . Then, using EQN 2-51, fugacity coefficients were computed from
𝑖
these areas.

𝐴𝑛 = 𝑙𝑛𝛷 EQN 2-27

It was observed that as usual, with increasing pressure, the computed fugacity
coefficients deviated away from Φ=1. All of these were greater than 1 which means that
repusilve forces ruled the molecules and so expansion occurred.

Table 2.3. Fugacity coefficient of nitrogen gas for Van der Waals and Redlich-Kwong EOS
using Simpson’s method.

Temperature, Pressure, Fugacity coefficient, ф


K bar Van der Waals Redlich-Kwong Empirical
100 1.0459204634 1.0459207604 1.0487013067
400 200 1.0967786245 1.1522746693 1.1011241583
300 1.1527736176 1.0967794780 1.1564634366
100 1.0324431201 1.0324431160 1.0341947472
600 200 1.0674194832 1.0674194695 1.0700379290
300 1.1048336634 1.1048336390 1.1068205423
100 0.9997579602 0.9997579602 1.0003026441
800 200 1.0506678757 1.0506678750 1.0526485226
300 1.0781124991 1.0781124980 1.0796995624
100 1.0195679793 1.0195679791 1.0209686313
1000 200 1.0401262161 1.0401262157 1.0422983151
300 1.0615286135 1.0615286128 1.0637553929

At varying temperature, fugacity coefficients were observed to first increase and then,
reached a value farthest from the ideal value 1. However, as the temperature continued to
rise, the fugacity coefficients returned to approach 1 which shows, somehow, the theoretical
observation.
Comparing the obtained fugacity coefficients from the Van der Waals and Redlich-
Kwong equations of state using the direct calculation and Simpson’s method, basically, the
values obtained did not differ largely from each other. Slight differences could be noticed but
the same trend is observed.
Finally, the fugacity coefficient at different temperature and pressure were calculated
using weighing method. This method involves cutting out of the closed figure on the paper
where the graph obtained from Simpson’s method was printed. The area of this cut-out is
determined together with the total mass. The total mass of the curve is also obtained by
cutting the entire graph through the borders and then weighing. From these data, the total
area under the curve is obtained using EQN 2-14. From the calculated total area under the
curve, the fugacity coefficient can be determined using equation EQN 2-15.
Negative area was not observed in the graphs. In the presence of negative area, the
total area under the curve is calculated by subtracting the negative area from the positive
area.
After plotting the values for Simpson’s method, only Redlich-Kwong and Empirical
show graph. An error may have been committed when the values were inputted.

Table 2.4. Data on the fugacity coefficients for the Redlich-Kwong and Empirical equations
of state at specific temperatures and pressures using the weighing method.

Equation of Temperature, Pressure, Mass of std Area of std Mass of Fugacity


State K bar rectangle, g rectangle curve, g coefficient, ф
100 0.0923 1.047967728
400 200 0.0394 0.02 0.1846 1.098236360
300 0.2408 1.153196984
Redlich-Kwong
100 0.1030 1.034233043
600 200 0.0306 0.01 0.2038 1.068869243
300 0.3168 1.108860468
100 0.0933 1.048499827
400 200 0.0394 0.02 0.1898 1.011340870
300 0.2837 1.154895833
Empirical
100 0.1080 1.035924348
600 200 0.0306 0.01 0.2141 1.072413133
300 0.3209 1.110565429

From the obtained results, the same can be said about the fugacity coefficient: as the
pressure increases, its value deviates further from 1. The fact that all the values obtained are
greater than one implies that the repulsive forces are dominant. As the temperature increases,
fugacity coefficient became closer to 1, and the gas became closer to ideality.

Considering the values of fugacity coefficient obtained by direct calculation method,


the accuracy of the Newton-Raphson method, Simpson’s method, and weighing method can
be determined using EQN 2-28.

𝑎𝑐𝑡𝑢𝑎𝑙 𝑣𝑎𝑙𝑢𝑒 − 𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑣𝑎𝑙𝑢𝑒 EQN 2-28


𝑝𝑒𝑟𝑐𝑒𝑛𝑡 𝑒𝑟𝑟𝑜𝑟 = 𝑋100
𝑎𝑐𝑡𝑢𝑎𝑙 𝑣𝑎𝑙𝑢𝑒

The following tables show that in general, of all the methods used, Newton Raphson
has the largest percent error. Weighing method had the lowest percent errow, which is
unusual because possible errors may be made during weighing. Between Newton-Raphson
and Simpson’s method, the latter generally gives more accurate results.

Table 2.5. Percent error of Newton-Raphson method.

Temperature, K vdW
Pressure, bar
100 200 300
400 -5.607770244 -11.809717390 -18.310578366
600 -4.151629400 -8.598352844 -13.180335637
800 -3.273449736 -6.758875446 -10.294184963
1000 -2.696781394 -5.544910749 -8.444061454

Table 2.6. Percent error of Simpson’s method.

Temperature, K vdW
Pressure, bar
100 200 300
400 -1.534775511 -3.569529798 -6.139472413
600 -1.239462329 -2.677156026 -4.315708700
800 -3.449905059 -2.212901944 -3.476576856
1000 -0.922464906 -1.913857494 -2.968113815
RK
100 200 300
400 -0.527504436 3.783198615 -6.825314879
600 -0.305609234 -0.660664470 -1.064922868
800 -2.659144454 -0.508697328 -0.798147688
1000 -0.217774388 -0.450895479 -0.697794860

Table 2.7. Percent error of Weighing method.

T, K RK
Pressure, bar
100 200 300
400 -0.332827188 -1.083929628 -2.032479617
600 -0.132770964 -0.525741377 -0.704330446
800 -0.143801823 -0.285523852 -0.416258293
1000 -0.094680310 -0.457728763 -0.695574798

On the other hand, the accuracy of the Van der Waals and Redlich-Kwong EOS in
determining the fugacity coefficient of hydrogen gas can be evaluated using the empirical
values obtained from Simpson’s method. Table 2.8 shows that the Redlich-Kwong EOS gives
higher percent errors consequently giving less accurate results compared to Van der Waals
EOS.
Table 2.7. Percent error of Van der Waals and Redlich-Kwong EOS with respect to empirical
on Simpon’s method.

Temperature, K vdW
Pressure, bar
100 200 300
400 -0.265170195 -0.394645215 -0.319060584
600 -0.169371108 -0.244705886 -0.179512290
800 -0.054451910 -0.188158427 -0.146991196
1000 -0.137188544 -0.208395137 -0.209331902
RK
100 200 300
400 -0.265141874 4.645299135 -5.160903208
600 -0.169371504 -0.244707167 -0.179514494
800 -0.054451910 -0.188158493 -0.146991298
1000 -0.137188564 -0.208395175 -0.209331968

For the errors in weighing method, incorrect reading of mass would affect the fugacity
coefficient calculated. Another would be the paper used is not uniform or the size of the cut
outs is not uniform. Also, when the paper being weighed is marked by pencil, or the paper
absorbs moist in the environment, its mass would increase and fugacity coefficient would also
be affected.

IV. Summary and Conclusion

In this exercise, the deviation of real gases from ideal behaviour was studied using
parameters which include compression factor, Z, and fugacity coefficient, ø. Hydrogen gas
was used as a model and its behaviour at pressures 100 bar, 200 bar, and 300 bar and
temperatures 400K, 600K, 800K and 1000K was evaluated. Two equations of state were used
– van der Waals and Redlich-Kwong equation of state.
Compression factor is the measure of the molecular interactions of the gas. When Z >
1, it means that repulsive forces are dominant and expansion is favoured; when Z < 1,
attractive forces are dominant and compression is favored. It is also described as the ratio
between the molar volume of the real gas with the molar volume of the perfect gas. As Z
approaches 1, it means that the gas is close to ideal behavior.
Fugacity coefficient is the ratio between the effective pressure and the pressure of the gas.
Also, when the value of the fugacity coefficient is close to 1, it means that the gas behaves
almost ideally. Four different methods were employed to describe the deviation of the gas.
These methods include direct calculation, Simpson’s method, weighing method and Newton-
Raphson method.
For the direct calculation, mere substitution of the values of pressure and temperature,
as well as the constants a and b, was done. The equations used to evaluate the fugacity
coefficient were derived from the two equations of state used. The Simpson’s method made
use of Microsoft Excel spreadsheet wherein parameters such as compression factor,
pressure, and temperature were used to compute for the fugacity coefficient. Weighing method
was done by weighing analytically the mass of the curve generated in the previous method.
Lastly, the Newton-Raphson method, a mathematical method, was used to evaluate the
fugacity coefficient first by solving the molar volume of the gas. From this, compression factor
was determined and after determining the compression factor, this was substituted to the
integral for the determination of the fugacity coefficient.
In all these methods, as well as for both equations of state, the general trend is as the
pressure is kept constant and the temperature is increased, the fugacity coefficient becomes
closer to 1 which means it approaches ideality. On the other hand, when temperature is kept
constant and the pressure is increased, the value of the fugacity coefficient also increases;
the gas deviates from ideal behavior. Such results were expected since it is known that gas
behaves ideally in high temperatures and extremely low pressures.
Based on percent errors computed, it was concluded that among all the methods used,
the Newton Raphson method is the most inaccurate. Weighing method gave the lowest
percent error. As for the performance of the equations of state, the Van der Waals is more
accurate to use to describe the behavior of hydrogen when using the Simpson’s method and
as well as in the weighing method.

V. Sample Calculation

DIRECT CALCULATION

Van der Waals

Given: P = 100x105, P* = 1x105, T = 400K

2 3
b 1 b  1 b  3 a
ln   ( p  p*)    (p  p* )  
2 2
 (p  p* ) 
3
( p  p*)
RT 2  RT  3  RT  ( RT ) 2

26.60 x 10−6 𝑚3
𝑙𝑛∅ = 𝑚𝑜𝑙 (100𝑥105 − 1𝑥105 )𝑃𝑎
8.314𝑘𝐽
( ) (400𝐾)
𝑚𝑜𝑙
2
26.60 x 10−6 𝑚3
1 𝑚𝑜𝑙 2 2
+ ( ) (100𝑥105 − 1𝑥105 )𝑃𝑎
2 (8.314𝑘𝐽) (400𝐾)
𝑚𝑜𝑙
3
26.60 x 10−6 𝑚3
1 𝑚𝑜𝑙 3 3
+ ( ) (100𝑥105 − 1𝑥105 )𝑃𝑎
3 ( 8.314𝑘𝐽
) (400𝐾)
𝑚𝑜𝑙
26.60 x 102 𝑃𝑎𝑚6
− 𝑚𝑜𝑙 2 (100𝑥105 − 1𝑥105 )𝑃𝑎
8.314𝑘𝐽 2
[( ) (400𝐾)]
𝑚𝑜𝑙

𝑙𝑛∅ = 0.06036407494

∅ =1.062223205
Redlich-Kwong

Given: P = 100x105, P* = 1x105, T = 400K

( RT  bP)
2 3
b 1 b  2 1 b  3 a
ln   ( p  p*)    (p  p* )  
2
 (p  p* ) 
3
ln
2  RT  3  RT  bRT 2 ( RT  bP*)
3
RT

𝑙𝑛∅
18.44𝑥10−6 𝑚3 18.44𝑥10−6 𝑚3
𝑚𝑜𝑙 1 𝑚𝑜𝑙 2 2
= (100𝑥105 − 1𝑥105 )𝑃𝑎 + ( )2 (100𝑥105 − 1𝑥105 )𝑃𝑎
8.314𝑘𝐽 2 (8.314𝑘𝐽) (400𝐾)
( ) (400𝐾)
𝑚𝑜𝑙 𝑚𝑜𝑙
18.44𝑥10−6 𝑚3
1 𝑚𝑜𝑙 3 3
+ ( )3 (100𝑥105 − 1𝑥105 )𝑃𝑎
3 (8.314𝑘𝐽) (400𝐾)
𝑚𝑜𝑙
14.47 𝑥10−2 𝑃𝑎𝑚6 8.314𝑘𝑗 18.44𝑥10−6 𝑚3
[( ) (400𝐾) + ( ) (100𝑥105 𝑃𝑎)]
𝑚𝑜𝑙 2 𝑚𝑜𝑙 𝑚𝑜𝑙
− 3 𝑙𝑛
18.44𝑥10−6 𝑚3 8.314𝑘𝐽 8.314𝑘𝑗 18.44𝑥10−6 𝑚3
( ) (400𝐾)2 [( ) (400𝐾) + ( ) (1𝑥105 𝑃𝑎)]
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙

𝑙𝑛∅ = 0.05018661439

∅ =1.051467297

WEIGHING METHOD

Redlich-Kwong

P = 100x105, P* = 1x105, T = 400K

 A 
ln   A   std ( M T )
 M std 
 0.02 
ln    (0.0923 g )
 0.0394 g 
ln   0.04685279153
  1.047967728

NEWTON-RHAPSON METHOD

Van der Waals

Given: P = 100x105, P* = 1x105, T = 400K

𝑅𝑇
𝑉𝑂 =
𝑃∗
8.314𝑘𝐽
( ) (400𝐾)
𝑉𝑂 = 𝑚𝑜𝑙
1𝑥105 𝑃𝑎

𝑉𝑂 = 0.033256

𝑃∗ 𝑉𝑂 3 − (𝑏𝑃 − 𝑅𝑇)𝑉𝑂 2 + 𝑎𝑉𝑂 − 𝑎𝑏


𝑉1 = 𝑉𝑂 −
3𝑃∗ 𝑉 2 − 2(𝑏𝑃 − 𝑅𝑇)𝑉 + 𝑎

𝑃∗ 𝑉 3 − (𝑏𝑃 − 𝑅𝑇)𝑉𝑂 2 + 𝑎𝑉𝑂 − 𝑎𝑏


𝑉2 = 𝑉1 −
3𝑃∗ 𝑉 2 − 2(𝑏𝑃 − 𝑅𝑇)𝑉 + 𝑎

𝑉𝑓𝑖𝑛𝑎𝑙 = 𝑉𝑎𝑐𝑡𝑢𝑎𝑙

𝑉1
= 0.033256𝑚3
26.60𝑥10−6 𝑚3 8.314𝑘𝑗
(1𝑥105 𝑃𝑎)(0.033256𝑚3 )3 − [( ) (1𝑥105 𝑃𝑎) + ( ) (400𝐾)]
𝑚𝑜𝑙 𝑚𝑜𝑙
36.490𝑥10−2 𝑃𝑎𝑚6 2.479𝑥10−6 𝑚3 26.60𝑥10−2 𝑃𝑎𝑚6
(0.033256𝑚3 )2 + ( ) (0.033256𝑚 3)
− ( )( )
𝑚𝑜𝑙 2 𝑚𝑜𝑙 𝑚𝑜𝑙 2

26.60𝑥10−6 𝑚3 8.314𝑘𝑗
(3)(1𝑥105 𝑃𝑎)(0.033256𝑚3 )2 − 2 [( ) (1𝑥105 𝑃𝑎) + ( ) (500𝐾)]
𝑚𝑜𝑙 𝑚𝑜𝑙
2.479𝑥10−2 𝑃𝑎𝑚6
(0.033256𝑚3 ) + ( )
𝑚𝑜𝑙 2

𝑉1 =3.327515595x10^-02 𝑚3
𝑉2 =3.327515595x10^-02 𝑚3
𝑉3 =3.327515595x10^-02𝑚3
𝑉𝑎𝑐𝑡𝑢𝑎𝑙
𝑍=
𝑉𝑖𝑑𝑒𝑎;

3.327515595x10−02 𝑚3
𝑍=
0.033256𝑚3

𝑍 =1.000576015

𝑃
𝑙𝑛∅ = (𝑍 − 1)ln( ∗ )
𝑃

100𝑥105 𝑃𝑎
𝑙𝑛∅ = (1.000576015 − 1)ln( )
1𝑥105 𝑃𝑎

𝑙𝑛∅ = 2.652646829x10^-03

∅ =1.002656168
D. PERCENT ERROR

at 400 K , 100 bar


 empirical  1.0487013067
VDW  1.0459204634
   EMP
%errorVDW  EMP  VDW x100%
 EMP
1.0459204634  1.0487013067
%errorVDW  EMP  x100%
1.0487013067
%errorVDW  EMP  -0.265170195

VI. Literature Cited

Atkins, P. (2006). Physical Chemistry. Great Britain: Oxford University Press. p.19.

Leithold, L. (1996). The Calculus 7. USA: HarperCollins College Publishers. p. 628.

Mortimer, R. (2008). Physical Chemistry. USA: Elsevier Academic Press. P. 176