Computation of the Compression Factor and Fugacity Coefficient of Real Gases

I. Case

. calculate for Carbon Dioxide factor and fugacity coefficient and consider the carbon
dioxide is a real gas at various temperatures and pressures were determined using several
methods. The first method that was used was by direct calculation. The van der Waals and the
Redlich-Kwong equations of state were both used. The following equations were the one used
for van der Waals and Redlich-Kwong equations of state, respectively

Solution

Real gases are also described by several equations of state. The most common
equation of states are shown below:
RT a (2-1)
Van der Waals: P= − 2
V −b V
RT a (2-2)
Berthelot: P= − 2
V −b TV
RT a (2-3)
P= − 1
Redlich-Kwong: V −b
T 2 V (V +b)

Compression factor, Z, is one measure of deviation. Mathematically, this is the ratio

between the molar volume of the gas to the molar volume of the perfect gas. For a perfect gas,
Z = 1 in all conditions. Therefore, deviation from one shows the deviation of gas from ideality. At
very low pressures, gases behave ideally which means that their Z = 1 or very close to 1. At
very high pressures, Z > 1 which signifies that the molar volume of the gas is greater than that
of the molar volume of the perfect gas (Mortimer, 2008).

V observed (2-4)
Z=
v ideal

Another measure of deviation is the fugacity coefficient. This is a dimensionless quantity

which is dependent on the type of gas, pressure, and temperature. Fugacity coefficient is the
ratio between fugacity or effective pressure and the pressure of the gas. Several books also
refer to fugacity as the activity (Rogers, 2011). Under very low pressures, the effective pressure
and pressure of the gas is equal which gives a fugacity of equal to one (Atkins, 2011).

f (2-5)
ϕ=
P

By using several mathematical integrations and derivations, the compression factor, Z,

and the fugacity coefficient, ø, are related by the following integral:
P
(Z−1)
ln Φ=∫ dP (2-6)
P
¿ P

In this exercise, this integral was evaluated using several methods. These methods
include direct calculation, Simpson’s method, Newton-Raphson method, and weighing method.
These methods vary from each other and it is the goal of this exercise to know which is the most
effective or appropriate method to use for the determination of fugacity coefficient of a Carbon
Dioxide at different temperatures. Each method has its own unique characteristic. Using these
methods, the deviation of Carbon Dioxide from ideality will be measured. Also, these methods
will be compared with each other. This also aims to apply mathematical tools such as the non-
linear curve fitting and the Newton-Raphson method. It also aims to evaluate the fugacity of
Carbon Dioxide at different pressures and temperatures.
II. METHODOLOGY

In this exercise, the fugacity coefficient of Carbon Dioxide at various temperatures and
pressures were determined using several methods. The first method that was used was by
direct calculation. The van der Waals and the Redlich-Kwong equations of state were both
used. The following equations were the one used for van der Waals and Redlich-Kwong
equations of state, respectively.

[ ( ) ( ) P − R aT ] dP
P 2 3
b b b
ln ∅=∫ + P+ 2
(2-7)
P
¿ RT RT RT 2 2

ln φ=
b
RT
( p−p∗)+
1 b 2 2
2 RT
( p − p∗2 )+ ( )
1 b 3 3
3 RT
( p − p∗3 )−
a
( RT )2
( p−p∗) ( ) (2-8)

[ ]
P

( ) ( ) P − R T ( RTa + bP) dP
2 3
b b b
ln ∅=∫ + P+ 2
(2-9)
P
¿ RT RT RT 2
3
2

( ) ( ) ( p − p∗ )−
2 3
b 1 b 1 b a ( RT +bP )
ln φ= ( p−p∗)+ ( p 2− p∗2 )+ 3 3
ln (2-10)
RT 2 RT 3 RT 3 ( RT +bP∗)
2
bRT
Another method that was used was the Newton-Raphson method. The molar volume
was solved in terms of P for the van der Waals equation of state. The fugacity coefficient was
computed using the equation below.
P
(Z−1) (2-11)
ln ∅=∫ dP
P
¿ P

Next method that was used was the Simpson’s method. In this method, Microsoft Excel
and what was done was data was just plugged in to the prepared spreadsheet in Microsoft
Excel. The parameters that were needed to compute for the fugacity coefficient were values of
compression factor, and pressure. The value of temperature was also varied. In this method, the
fitted a and b values for the Carbon Dioxide gas for the van der Waals and Redlich-Kwong
equation of states were determined. Also, the values of fugacity coefficient for Empirical, van
der Waals, and Redlich-Kwong for different temperatures and pressures were obtained. The
graph of Z-1/P vs. P was printed and was used for the next method to be utilized for the
determination of fugacity coefficient.
Lastly, the weighing method was used. The graphs obtained from the previous method
were photocopied using similar papers. First, a standard rectangle outside the resulting curve
was weighed first. The standard rectangle was obtained by simply cutting out from the graph the
largest area possible. The considered dimensions were that of the graph. The rectangle under

(2-12)
the curve was cut out and was weighed. This was done for each of the graph of van der Waals,
Redlich-Kwong and Empirical. After weighing, the fugacity coefficient was computed using the
following equation.

ln ∅= A=
( )
A standard
M standard
(MT)

III. RESULTS AND DISCUSSIONS

In this exercise, the fugacity coefficient of Carbon Dioxide at various temperatures and
pressures was determined using several methods. The first method used was direct calculation.
Direct calculation is simply substitution to equation 2-6. Two equations of state, the van der
Waals and the Redlich-Kwong, were used. The temperature values used were 400K, 600K,
800K and the 1000K. For the pressure values, 100 bar, 200 bar and 300 bar were used. The
initial pressure or the lower limit of the integral in equation 2-7 and 2-9 was set to 1 bar or 1x10 5
Pa. These values were substituted one by one to equations 2-8 and 2-10. The constants, a and
b, are also dependent to the equation of state and the identity of the gas. For Carbon Dioxide,
the following constants were used.
Table 2.1. Literature values used in the experiment.

van der Waals Redlich-Kwong

6 2
a, Pa-m /mol 36.490 x 10-2 644.80 x 10-2
b, m3/mol 42.74 x 10-6 29.63 x 10-6
R, J/mol-K 8.314

Shown below are the values of fugacity coefficient of Carbon Dioxide using van der Waals and
Redlich-Kwong equations of state.
Table 2.2. Values of compression factor using direct calculation method.
Temperature, K
EOS P, bar
400 600 800 1000
van der Waals 0.8172186623 0.9470089639 0.9861688656 1.0013955630
100
Redlich-Kwong 0.8300790579 0.9632809280 0.9972867323 1.0084703410
van der Waals 0.6802075043 0.9124733364 0.9821882332 1.0088916670
200
Redlich-Kwong 0.7207676037 0.9454781450 1.0031089860 1.0216376680
van der Waals 0.6017028697 0.9001669322 0.9896501457 1.0233034350
300
Redlich-Kwong 0.6677491584 0.9462454323 1.0175214160 1.0396205190

Table 2.2. Values of fugacity using direct calculation method.

Temperature, K
EOS P, bar
400 600 800 1000
van der Waals 0.8265940602 0.9450933960 0.9842349971 0.9999973382
100
Redlich-Kwong 0.8319990908 0.9597638842 0.9952336135 1.0072682420
van der Waals 0.6461889728 0.9003663639 0.9730660419 1.0028995900
200
Redlich-Kwong 0.7128052977 0.9295592684 0.9946564694 1.0170302310
van der Waals 300 0.6012052377 0.8662524874 0.9670302851 1.0090200120
 Redlich-Kwong 0.6289908316 0.9088019354 0.9983386014 1.0293211120

As seen from the table, all the values of the fugacity coefficient are near a value of one.
This only implies that the effective pressure of the gas is greater than or less than its actual
pressure. Also, from the table, it is seen that for both the equations of state and for all
pressures, the value of fugacity coefficient approaches one as the temperature rises. This
implies that the greater the temperature, the lesser is its deviation from one, and therefore, the
closer it is to ideal behavior. This result is expected since the idealizing conditions include high
temperatures and low pressures. The graph below further shows this relationship. The graph is
only a representative graph which made use of the pressure 300 bar.

1.2000000000

1.0000000000 Ideal

0.8000000000
Fugacity coefficient

0.6000000000 van der Waals

Redlich-Kwong
0.4000000000

0.2000000000

0.0000000000
300 400 500 600 700 800 900 1000 1100
Temperature, K

Figure 1. Fugacity coefficient of Carbon Dioxide at 300 bar and at varying temperature
using the VDW and RK equations of state.

Aside from the effect of temperature, the effect of pressure was also observed. At a
certain temperature, it was observed that as the pressure rises, the fugacity coefficient
decreases. In other words, the higher the pressure, the greater is the deviation of the gas from
ideal behavior. This result is also expected because a gas behaves ideally at very low
pressures. So at high pressures, it becomes less and less ideal and this is proven by the results
using the direct calculation method. To further illustrate this trend, a graph is shown below.
 1.1000000000
1.0000000000 ideal
0.9000000000
Fugacity coeffeicient 0.8000000000
0.7000000000
0.6000000000
0.5000000000 van der Waals
0.4000000000 Redlich-Kwong
0.3000000000
0.2000000000
0.1000000000
0.0000000000
0 100 200 300 400
Pressure, bar

Figure 2. Fugacity coefficient of Carbon Dioxide at 400K and at varying pressures using
the VDW and RK equations of state.

The results of effect of temperature and pressure are supported by Atkins (2008),
deviations from the law (ideal gas) are particularly important at high pressures and low
temperatures. He also stated that, 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.

Next method that was employed was the Simpson’s method. In this method, Microsoft
Excel was used. This method made use of the following parameters: compression factor, Z, and
pressure P at different temperatures. The evaluation of the integral for the computation of the
fugacity coefficient is done by Microsoft Excel. The values of the temperatures and pressures
were just placed in the respective cells. Shown below are the values and graphs acquired using
the Simpson’s method.
Table 2.3. Fugacity coefficient for Empirical, van der Waals and Redlich-Kwong using
Simpson’s method.

Temperature, K Pressure, bar Empirical van der Waals Redlich-Kwong

100 0.907357 0.849463 0.846596
423.15 200 0.822168 0.742604 0.742706
300 0.744960 0.673592 0.675181
100 0.980654 0.972041 0.980486
623.15 200 0.961492 0.958909 0.974952
300 0.942704 0.962997 0.983426
100 1.215189 1.201635 1.198142
873.15 200 1.481700 1.557166 1.527861
300 1.802975 2.223292 2.099683
100 1.337414 1.271261 1.267417
973.15 200 1.797430 1.793143 1.755658
300 2.415960 2.899789 2.719119
 0.00000003
Empirical
Values
0.000000025
vdw fitted
0.00000002
RK fitted
(Z-1)/P

0.000000015

0.00000001

0.000000005
P
0
0.00E+00 1.00E+06 2.00E+06 3.00E+06 4.00E+06 5.00E+06 6.00E+06
Figure 3a. Curves for empirical, vdW, RK using fitted a,b at 873.15K

0.000000035
Empirical
Values
0.00000003
vdw fitted
RK fitted
0.000000025

0.00000002
(Z-1)/P

0.000000015

0.00000001

0.000000005
P
0
0.00E+00 1.00E+06 2.00E+06 3.00E+06 4.00E+06 5.00E+06 6.00E+06

Figure 3b. Curves for empirical, vdW, RK using fitted a,b at 973.15K
0.000000008
Empirical
Values
0.000000006
vdw fitted

0.000000004 RK fitted
(Z-1)/P

0.000000002

0
0.00E+00 1.00E+07 2.00E+07 3.00E+07 4.00E+07 5.00E+07 6.00E+07
-0.000000002
P
-0.000000004

Figure 3c. Curves for empirical, vdW, RK using fitted a,b at 423.15.

0.000000008
Empirical
0.000000006 Values
vdw fitted

0.000000004 RK fitted
(Z-1)/P

0.000000002

0
0.00E+00 1.00E+07 2.00E+07 3.00E+07 4.00E+07 5.00E+07 6.00E+07
P
-0.000000002

-0.000000004
 Figure 3d. Curves for empirical, vdW, RK using fitted a,b at 623.15.

The graphs obtained using the Simpson’s method were reproduced using the same
quality of paper and was used for the next method, the weighing method. In this method, a
standard rectangle was cut. A standard rectangle is the biggest possible rectangle outside the
curve. The value of ln ø using this method is determined by using equation 2-12.
Table 2.4. Fugacity coefficients for Empirical, van der Waals and Redlich-Kwong using
Weighing method.

EOS P (bar) 400 K 600 K 800 K 1000 K

100 1.031999 1.020006 1.031778 1.033685
Empirical 200 1.067068 1.044052 1.068132 1.070968
300 1.102423 1.074793 1.111645 1.108023
100 1.027859 1.00913 1.029194 1.028936
Van der Waals 200 1.065183 1.030917 1.068057 1.06693
300 1.114419 1.0679 1.119372 1.109294
100 1.029266 1.014194 1.030182 1.031281
Redlich-Kwong 200 1.065655 1.038503 1.068398 1.069202
300 1.110044 1.07023 1.114535 1.112563

Lastly, the Newton-Raphson method was used. In this method, only the van der Waals
equation of state was utilized. The molar volume of the perfect gas was solved for using the
following equation.
RT (2-13)
V O= ¿
P
From here, the molar volume of the real gas was solved for using standard
approximation. This method was continued until the solved for V n ≈ V n+1 . The following equation
was used for standard approximation.
¿ 3 2
P V −( bP−RT ) V O + aV O−ab (2-14)
V 2=V 1 − ¿ 2
3 P V −2 ( bP−RT ) V + a
¿ 3 2
P V O −( bP−RT ) V O +a V O −ab (2-15)
V 1=V O − ¿ 2
3 P V −2 ( bP−RT ) V + a
After this, the compression factor of the gas was solved for by getting the ratio between
the molar volume of the actual gas and the molar volume of the ideal gas. Then, the fugacity
coefficient was solved for by evaluating the integral in equation 2.10 or by simply substituting
values in the following equation.
P (2-16)
ln ∅= ( z −1 ) ln ¿
P
 The succeeding tables summarize the obtained fugacity coefficient using the different
Newton-Raphson method.
Table 2.5. Fugacity coefficients using van der Waals and Newton-Raphson method.

Temperature, K P, bar Videal Vobs Z Φ

100 0.9991627768
400 200 0.0665120000 0.0664999030 0.9998181232 0.9990368228
300 0.9989631519
100 0.999937529
600 200 0.0831400000 0.083138872 0.999986434 0.999928127
300 0.999922627
100 0.9991627768
800 200 0.0665120000 0.0664999030 0.9998181232 0.9990368228
300 0.9989631519
100 0.9999375294
1000 200 0.0831400000 0.0831388721 0.9999864342 0.9999281269
300 0.9999226269

For easier comparisons, values of fugacity coefficient per Equation of State will be
grouped in one table.
Table 2.6. The fugacity coefficient of the van der Waals gas at certain temperatures and
pressures using different methods.

ø
Pressure (bar) Temperature (K)
Simpson’s Weighing Newton-Raphson
400 0.849463 1.027859 0.9991627768
600 0.742604 1.00913 0.999937529
100
800 0.673592 1.029194 0.9991627768
1000 0.972041 1.028936 0.9999375294
400 0.958909 1.065183 0.9990368228
600 0.962997 1.030917 0.999928127
200
800 1.201635 1.068057 0.9990368228
1000 1.557166 1.06693 0.9999281269
300 400 2.223292 1.114419 0.9989631519
 600 1.271261 1.0679 0.999922627
800 1.793143 1.119372 0.9989631519
1000 2.899789 1.109294 0.9999226269

Table 2.7. The fugacity coefficient of the Redlich-KWong gas at certain temperatures and
pressures using different methods.

ø
Pressure (bar) Temperature (K)
Simpson’s Weighing
400 0.846596 1.029266
600 0.980486 1.014194
100
800 1.198142 1.030182
1000 1.267417 1.031281
400 0.742706 1.065655
600 0.974952 1.038503
200
800 1.527861 1.068398
1000 1.755658 1.069202
400 0.675181 1.110044
600 0.983426 1.07023
300
800 2.099683 1.114535
1000 2.719119 1.112563

Table 2.8. The fugacity coefficient of the gas obeying empirical formula at certain temperatures
and pressures using different methods.

ø
Pressure (bar) Temperature (K)
Simpson’s Weighing
400 0.907357 1.031999
600 0.980654 1.020006
100
800 1.215189 1.031778
1000 1.337414 1.033685
400 0.822168 1.067068
600 0.961492 1.044052
200
800 1.481700 1.068132
1000 1.797430 1.070968
400 0.744960 1.102423
600 0.942704 1.074793
300
800 1.802975 1.111645
1000 2.415960 1.108023
 By considering the data, almost the same trend was observed for every method. For
Simpson’s method, as the pressure is held constant, and the temperature is increased, the
fugacity coefficient increases which means that it is closer to 1 for low pressures. For high
pressures, the fugacity deviated from unity largely, which is explainable by the increase of
pressure that leads to increase in deviation. Slight deviation on the 800K and 100bar for van der
Waals data can be accounted for errors in encoding the values in the excel file.

1.2

1
Fugacity Coefficient

0.8

0.6
Simpson's Method
Weighing
0.4 Newton-Raphson

0.2

0
300 400 500 600 700 800 900 1000 1100
Temperature, K

Figure 3. Fugacity coefficient of van der Waals gas at 100 bar and varying temperatures
using different methods.

For the weighing method, a consistent trend was observed. As the temperature
increases and the pressure held constant, the value of the fugacity coefficient increases but are
still close to unity which means that the van der Waals and the Redlich-Kwong gases behave
almost ideally. On the other hand, when the temperature is held constant and the pressure is
increased, the deviation of the fugacity coefficient from 1 becomes greater as shown in Figure 4.
Among all the methods, this is the one method prone to a number of possible sources of error.
First is the cutting of rectangles needed. This error affects the entire calculation of the fugacity
coefficient using the weighing method. Another possible source of error here is instrumental
error.
 2.5

Fugacity Coefficient 1.5

Simpson’s
1 Weighing
Newton-Raphson

0.5

0
50 100 150 200 250 300 350
Pressure, bar

Figure 4. Fugacity coefficient of van der Waals gas at 400K and varying pressures using
different methods.

Lastly, the Newton-Raphson method which was employed on the van der Waals gas
only. In the table above, the trend is seen to be the same with the previous methods discussed.
That is, as the pressure is held constant and the temperature is increased, the value of the
fugacity coefficient is increasing and approaching unity more. As for when the temperature is
held constant and the pressure is increased, the value of the fugacity coefficient is also
increased or approaches an ideal gas. Among the methods used, the amount of decrease in the
fugacity coefficient as the temperature is increases is very minimal.
The following graphs are only included for comparison of trends of Simpson’s and
Weighing method.
 1.4

1.2

Fugacity Coefficient 0.8

0.6 Simpson’s
Weighing
0.4

0.2

0
300 400 500 600 700 800 900 1000 1100
Temperature, K

Figure 5. Fugacity coefficient of Redlich-Kwong gas at 100 bar and varying temperatures
using different methods.

1.2

1
Fugacity Coefficient

0.8

0.6
Simpson’s
0.4 Weighing

0.2

0
50 100 150 200 250 300 350
Pressure, bar

Figure 6. Fugacity coefficient of Redlich-Kwong gas at 400K and varying pressures using
different methods.

Knowing that there is a relationship between the fugacity coefficient and the
compression factor, certain information can be deduced from the data observations for fugacity
coefficient. As seen in the tables above, almost every value of the fugacity coefficient is greater
than 1. Using the relationship in equation 2.11, in order for the value of fugacity coefficient to be
greater than 1, Z should be greater than 1. If Z is less than 1, the value of lnø will b negative
giving a fugacity coefficient of less than 1. When Z > 1, it means that the molar volume of the
gas is greater than the molar volume of the perfect gas at the same pressure and temperature.
This is usually observed at high pressures. In this case, the repulsive forces are dominant which
means that the gas is not easily compressed. The other case is when Z < 1 and this is the exact
opposite. Attractive forces are dominant in this case and compression is favored (Atkins, 2006)
As stated in the introduction, this exercise aimed to determine the most efficient method
of determining the fugacity coefficient. To do this, the percent error of the methods was
calculated. The value of fugacity coefficient obtained using direct calculation was considered to
be the true value. Also, it aimed to determine the accuracy of the equations of states. This was
done by getting the percent error of the calculated fugacity coefficients used in the Simpson’s
method. The value of the fugacity coefficient using the empirical data was the one considered
as the true value. The table below summarizes all these information.

Table 2.5. Percent error of the different methods and of the equations of state.

% error
Pressur Temp
Equation Direct Calculation Empirical Data
e .
of State Newton-
(bar) (K) Simpson’s Weighing Simpson’s Weighing
Raphson
400 20.8770816 2.766647 24.348737 -6.38051 13.28058
600 5.70773503 -21.42533 6.7757131 -9.677341 22.740147
100
800 1.49640633 -31.56187 4.5679552 -9.580112 38.154318
1000 -0.0059809 -2.795641 2.8939008 -0.878291 4.9234765
400 54.7423693 48.394516 64.840778 -0.268645 10.784378
Van der 600 11.0573059 6.9561279 14.499778 2.152638 9.3574961
200
Waals 800 2.68190788 23.489563 9.7619817 -1.115382 -12.10778
1000 -0.38515991 55.266391 6.3845062 5.093204 -27.99286
400 66.160088 269.80583 85.36418 23.31241 -38.18998
600 15.4325724 46.754095 23.278187 -4.946337 -20.15185
300
800 3.40194535 85.427802 15.753567 -0.238507 -37.72375
1000 -0.90160601 187.38667 9.9377416 20.02637 -54.08476
400 1.7544381 23.710019 -6.696482 13.435642
600 -22.61576 5.6711723 -9.664935 23.356023
100
800 -32.15854 3.5115966 -9.366812 38.286915
1000 -2.658899 2.383929 -0.017131 5.162555
400 36.776761 49.501571 1.399908 10.833488
Redlich- 600 5.7948679 11.719941 4.319702 10.162158
200 N/A
Kwong 800 20.45787 7.41381 -1.402827 -12.07965
1000 50.227688 5.1297913 3.115408 -27.83952
400 233.81774 76.480217 16.45658 -38.43262
600 39.4602 17.762701 -5.233757 -19.97768
300
800 75.85797 11.639002 -2.323985 -37.99284
1000 164.16625 8.0870998 12.54818 -53.94943
IV. SUMMARY AND CONCLUSIONS

In this exercise, the deviation of real gases from ideal behavior was studied using
parameters which include compression factor, Z, and fugacity coefficient, ø. Carbon Dioxide gas
was used and its behavior 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 favored. On the other hand, 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. Another measure of deviation is
the fugacity coefficient. This 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 a computer program made in Microsoft Excel 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
which means it is further from one which also means it behaves further from ideality. Such
results were expected since it is known that gas behaves ideally in high temperatures and
extremely low pressures.
Using percent error analysis, it was concluded that among all the methods used, the
Simpson’s method is the most inaccurate. As for the performance of the equations of state, the
Redlich-Kwong is more accurate to use to describe the behavior of Carbon Dioxide when using
the Simpson’s method and as well as in the weighing method.
V. SAMPLE CALCULATION

A. DIRECT CALCULATION
Van der Waals
Given: P = 100x105, P* = 1x105, T = 800K

ln φ=
b
RT
( p−p∗)+
1 b 2 2
2 RT ( )
( p − p∗2 )+
1 b 3 3
3 RT
( p − p∗3 )−( ) a
( RT )2
( p−p∗)

(( ) ((
−6 3 −6 3 2 −
42.74 x 10 m 42.74 x 10 m 42.74 x 10
mol ( 100 x 105−1 x 105 ) Pa+ 1 mol ( 100 x 105 −1 x 105 ) Pa+ 1
2 2
mol
ln ∅=
(
8.314 kJ
mol )
( 800 K )
2 8.314 kJ
mol )
( 800 K )
3 8.314 kJ
mol )(8

ln ∅=−0.013927675576
∅=0.9861688656
Redlich-Kwong
Given: P = 100x105, P* = 1x105, T = 800K

( ) ( ) ( p − p∗ )−
2 3
b 1 b 1 b a ( RT +bP )
ln φ= ( p−p∗)+ ( p 2− p∗2 )+ 3 3
ln
RT 2 RT 3 RT 3 ( RT +bP∗)
2
bRT

29.63 x 10−6 m3 29.63 x 10−6 m3 2 29.63 x 10−

mol ( 100 x 105−1 x 105 ) Pa+ 1 ( mol 1 mol
) ( 100 x 10 −1 x 10 ) Pa+ (
2 2
5 5
ln ∅=
(
8.314 kJ
mol )
( 800 K )
2 8.314 kJ
mol (
( 800 K ) ) 3 8.314 kJ
mol
(8 ( )
−3
ln ∅=−2.716955283× 10
∅=0.9972867323

B. WEIGHING METHOD
Van der Waals
P = 100x105, P* = 1x105, T = 800K
ln φ=A=
( )
A std
M std
( MT )

ln φ= ( 0.0. 01237 g )(0 . 0682 g )

ln φ=0 . 02877637131
φ=1. 029194411

C. NEWTON-RHAPSON METHOD
Van der Waals
Given: P = 100x105, P* = 1x105, T = 800K
RT
V O= ¿
P

V =
( mol )
8.314 kJ
(800 K )
O
1 x 105 Pa
V O =0.066512

P ¿ V O3−( bP−RT ) V O2 +a V O −ab

V 1=V O −
3 P¿ V 2−2 ( bP−RT ) V + a

P¿ V 3 −( bP−RT ) V O 2+ aV O−ab
V 2=V 1 −
3 P¿ V 2−2 ( bP−RT ) V + a
V final =V actual

[( ) ( ) ]
−6 3
( 1 x 10 5 Pa ) ( 0.066512 m3 ) − 42.74 x 10 m ( 1 x 105 Pa ) + 8.314 kj ( 500 K )
3

mol mol

V 1=0.066512m − 3
(0.066512 m3)2 +
( 36.490 x 10−2 Pa m 6
mol 2
()0.066512m 3
) − ( mol
( )
42.74 x 10−6 m3 36.490 x 10−2 Pa m6
mol 2
)

[( ) ( ) ]
−6 3
( ) ( 3 2
) 42.74 x 10 m ( 8.314 kj
1 x 10 Pa ) +
5 5
( 3 ) 1 x 10 Pa 0.066512 m −2 ( 500 K )
mol mol
−2 6
( 0.066512 m 3 ) +( 36.490 x 102 Pam )
mol
3
V 1=0.06649990741m
 3
V 2=0.06649990301m
3
V 3=0.06649990301m
V actual
Z=
V idea ;
3
0.06649990301m
Z=
0.066512m 3
Z=0.9998181232
P
ln ∅= ( Z−1 ) ln ⁡( ¿)
P

100 x 105 Pa
ln ∅= ( 0.9998181232−1 ) ln ⁡( )
1 x 105 Pa
ln ∅=−8.3757368671
∅=0.9991627768

D. PERCENT ERROR

at 8 73 .15 k , 100 bar

φ empirical=1 .215189
φVDW =1 .201635
φ −φ
% errorVDW −EMP = EMP VDW x 100 %
φ EMP
1. 215189−1. 201635
% errorVDW −EMP = x100 %
1. 215189
% errorVDW −EMP =1. 115382
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.
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.