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Anda di halaman 1dari 17

2

Computation of the Compression Factor and Fugacity Coefficient of Real Gases

Masibag, Riden A.

Taghap, Kem M.

Torrano, Yvegeny Von D.

Lachica, Michael Aaron J.

Date Submitted: September 7, 2017

CHEM 111.1

6L

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.

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

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.

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

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.

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

EQN 2-15

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:

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

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

system given in EQN 2-18. Chemical potential is the energy that can be absorbed or

released during a chemical reaction.

𝑑𝜇 = 𝑉̅ 𝑑𝑃 EQN 2-19

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∗

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.

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

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

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 )

𝑅𝑇 𝑎

𝑃= − 2

̅

𝑉−𝑏 𝑉 ̅

𝑎 𝑎𝑏

𝑃(𝑉̅ − 𝑏) = 𝑅𝑇 − +

𝑉̅ 𝑉̅ 2

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.

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

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

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.

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.

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.

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.

the accuracy of the Newton-Raphson method, Simpson’s method, and weighing method can

be determined using 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.

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

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

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.

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

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

( 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

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

𝑅𝑇

𝑉𝑂 =

𝑃∗

8.314𝑘𝐽

( ) (400𝐾)

𝑉𝑂 = 𝑚𝑜𝑙

1𝑥105 𝑃𝑎

𝑉𝑂 = 0.033256

𝑉1 = 𝑉𝑂 −

3𝑃∗ 𝑉 2 − 2(𝑏𝑃 − 𝑅𝑇)𝑉 + 𝑎

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

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

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

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