I.

Introduction
When real gases are considered, the ideal gas law is not applicable because one
assumption of the ideal gas, which is ideal gas should have no interaction with each other, is not
followed by real gases since it either have repulsive or attractive forces. The repulsive forces aid
in the expansion while the attractive forces aid the compression (Atkins and de Paula, 2006).
When real gases deviate from ideality, certain parameter are used to describe these deviations.
These parameters are: compressibility factor (Z), fugacity coefficient (), and Joule-Thomson
coefficient (JT) (Mortimer, 2008).

As stated above, the ideal gas equation is not enough in describing the state of real gases.
Alternatively, the mathematical expressions known as equations of state (EOS) are used in
describing real gases. Some common equations of state used are: van der Waals, Berthelot, and
Redlich-Kwong. Their corresponding equations are given below:

Van der Waals: =

2 (2-1)

Berthelot: =

2

(2-2)

Redlich-Kwong: =
1 (2-3)
(
+)
2
Compressibility factor is mathematically defined as the ratio of observed molar volume,
obs, to the ideal molar volume of the gas, ideal, at constant temperature and pressure (Atkins
and de Paula, 2006).
(2-4)
=

On the other hand, fugacity coefficient is known as the effective pressure of the gas and
is mathematically defined as the ratio of fugacity, f, of the gas to the pressure. It is dimensionless
since fugacity and pressure have the same unit. Also, this ratio is dependent on the identity of
gas, pressure, and temperature.
(2-5)
=

Both the compressibility factor, Z, and fugacity coefficient, , have the value of one (1) when the
gas is ideal. Also, the equation below relates the two quantities:

( 1) (2-6)
=

In this exercise, the values of compressibility factor and fugacity coefficient will be
determined using various techniques such as direct calculation, Newton-Raphson method,
Simpsons Method, and Weighing method. Also, these methods will be compared to each other
to determine which method is the most accurate, precise, and consistent. Lastly, the effect of
temperature and pressure to the value of compressibility factor and fugacity coefficient will also
be investigated.

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II. Materials and Methods

Different methods were employed in determining the values of compressibility factor, Z,

and fugacity coefficient, , of hydrogen gas. These methods are: Direct computation, Newton-
Raphson method, Simpsons method, and Weighing method. Also, these methods used the
equations of state known as Van der Waals EOS, and Redlich-Kwong EOS.

Compressibility factor, Z, determination

The compressibility factor is mathematically defined as:

(2-7)
=

Using the Van der Waals EOS, the derivation of Z as a function a, b, and P is given by:
1 (2-8)
=1+ + ( ) + ( )2 2 +

On the other hand, using the Redlich-Kwong EOS, the derivation of Z as a function of a, b, and P
is given by:

2 3
=1+ +( ) +( ) 3 (2-9)

2 ( + )
Fugacity coefficient, , determination

By Direct calculation
The fugacity coefficient for van der Waals EOS was computed using the formula:

1 2 2 1 3 3
ln = ( ) + ( ) ( ) + ( ) ( 3 )
2 ( ) (2-10)
2 3 ()2

On the other hand, the fugacity coefficient for Redlich-Kwong EOS was computed using the
formula:

1 2 2 1 3 3 ( + )
ln = ( ) + ( ) ( ) + ( ) ( 3 )
2
3 (
2 3 + )
()2

Using the Newton-Raphson Method (2-11)

In this method, the value of molar volume, , in terms of P for van der Waals EOS was
initially determined. The value of was determined using the formula:
3 ( + )
2 +
= (2-12)
3 2 2( + ) +

Next, the value of was determined using the formula:

= (2-13)

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Lastly, the value of fugacity coefficient was determined using the formula:

= ( ) ln( ) (2-14)

Using the Simpsons Method

The computation of fugacity coefficient using the Simpsons method used an Excel
worksheet. In this worksheet, the compressibility factors of a specific temperature for various
pressures, ranging from 1 bar to 1000 bar from Appendix C of the lab manual, were inputted.
The critical parameters, namely critical temperature, Tc, and critical pressure, Pc, were also
included in the first tab of the worksheet. Then, a graph was created from the inputted data
range. The equation of the line from the generated graph was copied and the calculation for
proceeded by clicking the second tab of the worksheet. In this tab, the values from the equation
copied from the first graph was inputted. Also, the gas constants, a and b, of the hydrogen gas
were entered in this tab. Then, the plot of (Z 1)/P vs P was completed and another graph was
created in this tab. Then, the calculation proceeded in the third tab of the worksheet. In this tab,
the value of dZ was minimized using the solver feature of Microsoft Excel. Finally, the values of
fugacity coefficient for Simpsons Rule Empirical, van der Waals EOS, and Redlich-Kwong EOS
was determined after clicking the succeeding tabs in the worksheet.
Using the Weighing Method
The graphs of (Z 1)/P vs P, for each temperature and pressure range, generated from
the Simpsons method were used in the weighing method. Ideally, each graph should contain
three curves derived from Simpsons Empirical data, van der Waals EOS, and Redlich-Kwong EOS.
Unfortunately, only two graphs, one for Simpsons Empirical and another from Redlich-Kwong
EOS, were generated. Nevertheless, the weighing method was still performed.

In this method, each graph was printed out using similar type of paper. Then, a standard
rectangle was drawn and cut out from each graph. Then, the areas of these standard rectangles
were calculated by multiplying the length and width of the rectangle using the dimension and
scale of each graph as the basis. Next, each standard rectangle was then weighed. The curves,
for empirical and Redlich-Kwong EOS, in each graph were also cut out from the paper and
weighed. Lastly, the fugacity coefficient for empirical, and Redlich-Kwong EOS were calculated
using the formula:

= = ( )

(2-15)

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III. Results and Discussion

In this exercise, the compressibility factor and fugacity coefficient of Hydrogen gas at varying
temperature and pressure were determined using various methods. The table 2.1. below tabulate
the values of P* (initial pressure), P (pressure), T (temperature), gas constant a of H2, and gas
constant b of H2 used in determining Z and in all methods.

Table 2.1. Values of the different parameters used in determining Z and of all methods.

Parameter Values
Gas constant, a of H2 gas in VDW EOS, 2.479x10-2 (Pa m6)/mol2
Gas constant, b of H2 gas in VDW EOS 26.6x10-6 m3/mol
Gas constant, a of H2 gas in Redlich-Kwong 14.47x10-2 (Pa m6 K1/2)/mol2
EOS
Gas constant, b of H2 gas in Redlich-Kwong 18.44x10-6 m3/mol
EOS
Initial pressure, P* 1 bar
Pressure, bar Temperature, K
100 400
200 600
400 800
--- 1000

By direct calculation
As stated above, the mathematical expression of Z is equal to:
(2-7)
=

Also, recall that the equation for the van der Waals equation of state is equal to:

= 2 (2-1)

Substituting the equation (2-1) to equation (2-7) lead to:

=( 2)


Distributing will simplify the equation to:

=


1
Dividing the first term with

will yield:

1
=


1

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Recall that using the Taylors series expansion, the first term can be simplified into:

1 2 3
=1+ +( ) +( ) +

1

With the assumption that the third-degree equation of the Taylor series is sufficient, Z then
become:

2 3
=1+ +( ) +( )



Also, since there is an assumption that
, Z then becomes:

2 3
=1+ +( ) +( )

()2

Recall equation (2-6) which relates Z to ln , the equation then become:

2 3
= [ + ( ) + ( ) 2 ]

()2
After integrating the equation above, it yields:

= ( ) + ( ) ( ) + ( ) ( )
( )
()

(expression of fugacity coefficient for van der Waals EOS) (2-10)

On the other hand, the equation of Redlich-Kwong equation of state:

(2-3)
=
1
2 ( + )

Also, substituting the equation (2-2) to equation (2-7) then lead to:

=( )
1
2 ( + )

Distributing
will simplify the equation to:

=
3
2 ( + )
1
Dividing the first term with
will yield:

1
= 3

1 2 ( + )

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After performing the simplification of the first term using again the Taylors series expansion,

assuming that the third-degree of the Taylor series is sufficient, and substituting , Z then
becomes:

2 3
=1+ +( ) +( ) 3

2 ( + )
Again, recall equation (2-6) which relates Z to ln , the equation then become:

2 3
= [ + ( ) + ( ) 2 3 ]

2 ( + )
After integrating the equation above, it yields:

( + )
= ( ) + ( ) ( ) + ( ) ( )

(
+ )
()

(expression of fugacity coefficient for Redlich-Kwong EOS) (2-11)

After simply substituting each and every value of pressure and temperature in table 2.1. to
equations (2-10) and (2-11), the fugacity coefficient, for van der Waals EOS and Redlich-Kwong
EOS, for various temperature and pressure are determined. Table 2.2 below tabulates the
experimental values obtained using direct calculation method.
Table 2.2. Values of fugacity coefficient computed using the Direct Calculation Method.

Temperature, Pressure,
Phi, vdw Phi, rk
K bar

100 1.062223205 1.051467297

400 200 1.213386409 1.110270915
400 1.338841897 1.253456382
100 1.055761789 1.03560803
600 200 1.09678205 1.074518431
400 1.220007116 1.162613301
100 1.035481074 1.027069214
800 200 1.075687538 1.056039922
400 1.163429669 1.119462314
100 1.021519648 1.021793183
1000 200 1.060421166 1.04483734
400 1.12996753 1.094320711
vdw = van der Waals EOS, rk = Redlich-Kwong EOS

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As stated above, an ideal gas has a value of one (1) for both compressibility factor, and fugacity
coefficient. Also, recall that gas ideality happens under conditions of high temperature and low
pressure (Atkins and de Paula, 2006). The data for direct calculation supports this claim since the
phi value under 1000 K and 100 bar is the nearest value to one (1) which is 1.021793183. On the
other hand, the phi value under 400 K and 400 bar is the farthest value to one (1) which is
1.253456382. Hence, increasing the temperature and decreasing the pressure leads to ideality of
the gas which in this case is hydrogen gas.

In order to further illustrate the dependence of ideality of the gas with temperature and pressure,
refer to the following graphs below:

Graph of fugacity coefficient vs Temperature at

constant pressure of 100 bar
1.06
Fugacity coefficient

1.05
1.04
1.03
1.02
1.01
1
400 600 800 1000
Temperature, K

van der Waals Redlich-Kwong Ideal

Figure 2.1. Graph of fugacity coefficient vs Temperature at constant pressure of 100 bar

As observed from the graph, the value of reaches ideality or equates to 1 as the temperature
increases.

Graph of fugacity coefficient vs Pressure at

constant temperature of 1000 K
1.15

1.1
Fugacity coefficient

1.05

0.95

0.9
100 200 400
Pressure, bar

Figure 2.2. Graph of fugacity coefficient vs Pressure at constant temperature of 1000K

7|Page
As observed from the graph, the value of reaches ideality or equates to 1 as the pressure
decreases.

Atkins and de Paula (2006) explained that the effect of high pressure is that gas molecules are
very near to each other that they exhibit interactions of attraction and repulsion with one another.
Also, they also explained that the effect of low temperature, on the other hand, is that gas
molecules have low kinetic energy which leads to low speed thus each molecule can capture one
another. Hence, both conditions are undesirable since it deviate the behavior of gas from ideality.

Using Newton-Raphson Method

In this method, only the van der Waals EOS was used to determine the fugacity coefficient.
First, this equation of state was transformed into a simple function as followed below:

= 2

Combining the two terms into one then yield:

( 2 ) ( )
=
( 2 )

After performing cross-multiplication then yield:

2 ( ) = ( 2 ) ( )

Then, transposing the right side into left lead to:

2 ( ) ( 2 ) + ( ) = 0

After further simplification, the equation finally becomes:

(): 3 ( + ) 2 + = 0

Next, the first derivative, in terms of , of the function was determined and was given by the
equation:
(): 3 2 2( + ) + = 0

Then, the ratio of F(x)/F(x) was determined. It was then subtracted to Vo which is equal to RT/P.
When the answer displayed by the calculator became constant, it was then divided by RT/P to
obtain the (Vobs/Videal) expression. This expression was then used to obtain the fugacity coefficient
using the the equation:

= ( ) ln( )

The process of continuously pressing the ANS key in the calculator until a constant answer is
displayed is also be referred as standard approximation. Table 2.3 below tabulates the data
obtained from this method alongside the corresponding percent error.

8|Page
 Table 2.2. Values of fugacity coefficient computed using Newton-Raphson Method.

Temperature, Pressure, Phi, vdw from direct Phi, vdw from Newton-
Percent Error, %
K bar calculation Raphson method
100 1.062223205
400 200 1.213386409
400 1.338841897
100 1.055761789
600 200 1.09678205
400 1.220007116
100 1.035481074
800 200 1.075687538
400 1.163429669
100 1.021519648
1000 200 1.060421166
400 1.12996753
vdw = van der Waals EOS

Using Simpsons Method

In this method, the program Microsoft Excel was used to calculate the fugacity coefficient of
hydrogen gas using again both van der Waals and Redlich-Kwong as equations of states. After
plugging in the necessary values in the worksheet, the program generated various graphs of (Z
1)/P vs P, which was also used in the weighing method, and phi values for Simpsons rule
empirical, van der Waals EOS, and Redlich-Kwong EOS. Table 2.4 below tabulates phi values
generated by Microsoft Excel after performing the Simpsons method. Also, the percent error
for phi values of each equation of state was determined using the Simpsons rule empirical data
as the true value.
Table 2.4. Values of fugacity coefficient computed using the Simpsons Method.

Temperature, Pressure, Percent Error, %

Phi, emp Phi, vdw Phi, rk
K bar VDW RK
100 1.048701307 1.045920757 1.045910264 0.2651422 0.2661427
400 200 1.101124158 1.096778625 1.096779248 0.3946452 0.3945886
400 1.214587078 1.214645326 1.214646906 0.0047956 0.0049257
100 1.034194747 1.032538105 1.032538113 0.1601866 0.1601858
600 200 1.070037929 1.067419469 1.067419469 0.2447071 0.2447071
400 1.144439019 1.144930667 1.144930667 0.0429597 0.0429597
100 1.025964270 1.024497611 1.024497609 0.1429541 0.1429543
800 200 1.052648522 1.050490803 1.050490801 0.2049800 0.2049802
400 1.107164717 1.106624277 1.106624817 0.0488129 0.0487642

9|Page
 100 1.020968681 1.019214265 1.019214265 0.1718384 0.1718384
1000 200 1.042298315 1.040126216 1.040126215 0.2083951 0.2083951
400 1.085376643 1.083825835 1.083825834 0.1428820 0.1428821
emp = Simpsons Rule Empirical, vdw = van der Waals EOS, rk = Redlich-Kwong EOS

Using Weighing Method

As stated, various (Z 1)/P vs P graphs are generated in the previous method was used in this
method. However, only the empirical and Redlich-Kwong EOS curves appeared on all the graphs
thus the phi value of van der Waals EOS using weighing method was not determined.

In this method, all graphs to be were printed on the same type of paper with uniform thickness
and density. Then, a standard rectangle was drawn in each graph and cut out of the paper. Each
of these standard rectangles were then weighed and their area were also determined using the
dimension and scale of each graph, from where it was cut out, as the basis. Then, the curves of
each graph were also weighed thus each graph had two masses since each graph had two
curvesone for empirical, and one for Redlich-Kwong EOS. Then, the total area under each curve
was determined using the formula below which was also equal to the natural logarithm of phi:

= = ( )

Table 2.5 below tabulates the data obtained using this method. Also, included below are the
percent errors for Redlich-Kwong phi values using Simpsons rule empirical as the true value.
Table 2.5. Values of fugacity coefficient computed using the Weighing Method.

Percent
Temperature, K Pressure, bar Phi, emp Phi, rk
Error, %
100 1.624615116 1.765829744 8.692189702
400 200 1.648805606 1.801544768 9.263624586
400 1.460159176 1.390378146 4.779001589
100 1.455677058 1.388686953 4.601989496
600 200 1.221479699 1.237316451 1.296521873
400 1.221902962 1.238135104 1.328431314
100 1.276936078 1.312975765 2.822356393
800 200 1.276169051 1.312215248 2.824562905
400 1.280585758 1.316445922 2.800293877
100 1.225641729 1.241943095 1.33002705
1000 200 1.280805501 1.314907385 2.662534207
400 1.284192184 1.322528526 2.98524962
emp = Simpsons Rule Empirical, rk = Redlich-Kwong EOS

10 | P a g e
Analyzing the behavior of hydrogen gas
Since there is an expression that relates the fugacity coefficient and compressibility factor which
is given by equation (2-6):

( 1)
= = ( 1) ln( )

The value of Z can be calculated by manipulating the equation above to become:

+1=

ln( )

Using representative values of phi from representative values of temperature and pressure, Z is
equal to:

Phi value from direct calculation using 100 bar, 1000 K from van der Waals EOS
ln(1.021519648)
+1=
100105
ln ( )
1105
= 1.004623362
This calculation also proved that gas ideally behave when under low pressure and high
temperature conditions.

On the other hand, the highest pressure and lowest temperature was also used to calculate Z in
order investigate whether the hydrogen gas favors attraction or repulsion:
Phi value from direct calculation using 400 bar, 400 K from van der Waals EOS
ln(1.338841897)
+1=
400105
ln ( )
1105
= 1.048703448

Since both the fugacity coefficient and compressibility factor are greater than 1, it can be stated
that obs > ideal and that repulsive forces of the hydrogen gas are more dominant than its
attractive forces. Also, it can be said that hydrogen gas is more difficult to compress in this
condition. On the other hand, when either phi or Z is/are less than 1, obs < ideal and attractive
forces of the hydrogen gas are more dominant than its repulsive forces and it is easier to compress
(Atkins and de Paula, 2006).

Analyzing the percent errors

In the Simpsons method, it can be observed that there are only little deviations of phi values
obtained from the two EOS with respect to the phi values obtained from the empirical. Also, the
experimental values also describe that either of the two EOS can be used when the Simpsons
method is the method to be used in determining the fugacity coefficient since the phi values from
the two EOS are relatively similar to each other based from their percent errors.

On the other hand, table 2.6 below tabulates the percent errors obtained from all methods with
the phi values from direct calculation as the true value.

Insert table here

11 | P a g e
As observed from the table above, the most accurate equation of state and method to use in
determining the fugacity coefficient of a real gas is the Redlich-Kwong equation of state via
Simpsons Method since it yielded the phi values with the lowest percent errors. On the other
hand, the method which is the most vulnerable to errors is the weighing method since it reported
the phi values with the highest percent errors.

IV. Summary and Conclusion

In this exercise, the parameters used to describe the deviations of real gases from ideality known
as compressibility factor and fugacity coefficient were investigated using four different methods
namely: by direct calculation, Newton-Raphson method, Simpsons method, and Weighing
method. The gas used was hydrogen gas and it was subjected under varying temperatures (400
K, 600 K, 800 K, and 1000 K) and pressures (100 bar, 200 bar, and 400 bar). Two of the most
common equations of state was used in this experiment namely: van der Waals EOS, and Redlich-
Kwong EOS.

Compressibility factor demonstrates the extent at which the behavior of real gases is affected by
the distance of molecules from each other. It is mathematically defined as the ratio of observed
molar volume and the ideal molar volume of the gas. On the other hand, the fugacity coefficient
is another parameter used to describe deviations from ideality of real gases which is
mathematically defined as the ratio of fugacity and pressure. Since fugacity and pressure have
the same dimensions, this parameter is unitless. Both parameters have a value of one when the
gas behaves ideally. However, when the gas to be considered is subjected to high pressure and
low temperature, the gas deviates from ideality yielding to a value of higher than one or less than
one. When these parameters have a value greater than one, the gas favors repulsion. On the
other hand, when the value is lower than one, then the gas favors attraction. In this experiment,
it was found out that the hydrogen gas favored the repulsive forces because the experimental
values of , and Z are greater than one.

As stated above, four methods were used in determining the fugacity coefficient of the hydrogen
gas. Direct calculation method involved direct substitution of necessary values in the derived
equations for each equation of state. This method also served as the true value of the experiment
which was used to determine the percent error of the other methods. Newton-Raphson method
involved the use of standard approximation technique using a scientific calculator. This method
also only involved direct substitution of necessary values to the derived equations for each
equation of state. On the other hand, Simpsons method involved the use of Microsoft Excel in
determining the value of fugacity coefficient. After plugging the necessary values in the pre-made
worksheet, the fugacity coefficient was determined from this method. The generated graphs in
this method were also used in the Weighing method. Lastly, the weighing method involved using
standard rectangles with measured mass and area, and weighed curves in determining the area
under the curve of each graph. This area under the curve corresponds to the fugacity coefficient
of hydrogen gas.

Each equation of state was compared to another under the same method to determine their
accuracy, precision, and consistency. After analysis, it was found out that either van der Waals
EOS or Redlich-Kwong EOS can be used in determining an accurate phi value since the
experimental values obtained from the two EOS were similar to each other. Also, the accuracy of

12 | P a g e
Newton-Raphson, Simpsons method, and Weighing method were compared using the Direct
calculation as the true value. After determining the percent errors of the phi values obtained from
each method, it was found out that using the Redlich-Kwong EOS via Simpsons method in this
exercise yielded the most accurate phi value of hydrogen gas with respect to the direct calculation.

V. Sample Calculation

By direct calculation (van der Waals EOS)

400 K, 100 bar

Conversion of 100 bar, and 1 bar to Pa

100000
= 100 ( ) = 10000000
1
100000
= 1 ( ) = 100000
1
Then, substitute the values of P, P*, a, b, R, and T to the formula:

1 2 2 1 3 3
ln = ( ) + ( ) ( ) + ( ) ( 3 )
2 ( )
2 3 ()2

26.60106 3
( )
2
ln = (10000000 100000)

(8.314 ) (400)

2
26.60106 3
1 ( )
+ ( 2 ) (100000002 1000002 )
2 (8.314
)(400)

3
26.60106 3
1 ( )
+ ( 2 ) (100000003 1000003 )
3 (8.314
)(400)

2.479102 6
( )
2
2
(10000000 100000)

((8.314 ) (400))

=
= .

By direct calculation (Redlich-Kwong EOS)

400 K, 100 bar

Conversion of 100 bar, and 1 bar to Pa

100000
= 100 ( ) = 10000000
1

13 | P a g e
 100000
= 1 ( ) = 100000
1
Then, substitute the values of P, P*, a, b, R, and T to the formula:

)
1 2 2 1 3 3 ( + )
ln = ( + ( ) ( + ( ) ( 3 )
2 )
3 (
2 3 + )
()2
2
3 6
3
(18.44106 ) (18.4410 )
ln = (10000000 100000) + 1 ( ) (100000002
2 (8.314 )(400)
(8.314 )(400)

3
3
1 (18.44106 )
1000002 ) + ( ) (100000003 1000003 )
3 (8.314
)(400)

1
6 2
2 3
(14.4710 2 ) ((8.314 )(400) + (18.44106 )(10000000)

3 3 3
((18.44106 )(8.314 )(400))2 ((8.314 )(400) + (18.44106 )(100000)

=
= .

Using the Newton-Raphson Method

Using the Simpsons Method

All calculations using this method was performed by Microsoft Excel

Using the Weighing Method

Simpsons Rule Empirical
1000 K, 200 bar

= = ( )

0.01
= = ( ) 1.1434
0.0462
= =
= .

14 | P a g e
Redlich-Kwong EOS
1000K, 200 bar

= = ( )

0.01
= = ( ) 1.2648
0.0462
= =
= .

VI. LITERATURE CITED

Atkins, P. and de Paula, J. Physical Chemistry, 8th edition. Great Britain: Oxford University Press,
2006. 14-15.

Mortimer, R.G. Physical Chemistry, 3rd edition. Californina: Elsevier Academic Press, 2008. 24-25.

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