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SCHOOL OF CHEMICAL ENGINEERING

EKC 108
ANALYTICAL & PHYSICAL CHEMISTRY
SEMESTER 2 2015/2016
ASSIGNMENT : CONSTRUCT CURVES Z VERSUS PRESSURE FOR CO2
USING PAPAY,
BEGGS, KUMAR, MAHMOUD AND VAN DER WAAL.

PREPARED BY:
MUHAMMAD HAZIM BIN MOHD FAUZI (129097)
YEW KEAT YEN (131172)
NURIN DIANAH BINTI D.M.PREMNAJEEB (129119)
JOAN MARY A/P PATRICK GEORGE (129073)

PREPARED FOR:
ASSOCIATE PROFESSOR DR. MOHD ROSLEE BIN OTHMAN

SUBMISSION DATE:
23 MAY 2016
ACKNOWLEDGEMENT
This project consumed huge amount of dedication,work,research and understanding
among team members. Still, implementation would not have been possible if we did not have a
support of many individuals. Therefore we would like to extend our sincere gratitude to all of
them.
Firstly, we would like to thank our lecturer, Associate Professor Dr Mohd Roslee Bin
Othman and our seniors for giving us guidelines and willing to spend their valuable time to
discuss and explain about this project to us.
In addition, we also would like to expand our gratitude to our friends and coursemates
who willing to help us to correct our mistakes and also willing to share information with
us.Without their help,our project would not have been completed successfully.

We thank to all those who have helped us directly and indirectly in writing this project.

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TABLE OF CONTENT
No CONTENT Page
1 ACKNOWLEDGEMENT 2

2 TABLE OF CONTENT 3

3 ABSTRACT 4

4 INTRODUCTION 5

5 METHODOLOGY 6-8

6 RESULT 9-11

7 DISCUSSION 12

8 CONCLUSION 13

9 REFERENCE 14

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Title: Thermodynamics
1.0 ABSTRACT
Based on the thermodynamics topic, it contains two type of gases which are ideal and real gases.
For ideal, PV = nRT.

P = pressure, V = volume, n = number of moles, R = ideal gas constant, T = temperature

To understand the behaviour of real gases, the following must be taken into account :-

1) Compressibility effects
2) Variable specific heat capacity
3) Van der Waals forces
4) Non-equilibrium thermodynamics effects
5) Issues with molecular dissociation and elementary reactions with variable composition

The compressibility factor increases with increase of pressure at constant temperature and
it decreases with increase of temperature at constant pressure. For an ideal gas, Z always has a
value of 1. For real gases, the value may deviate positively or negatively, depending on the effect
of the intermolecular forces of the gas. The closer a real gas is to its critical point or to its
saturation point, the larger are the deviations of the gas from ideal behavior.

In this work, discussion about real gases will be dominant because it is variable. Many
researches such as Papay, Beggs, Kumar, Mahmood and Van der Waals have found the
correlation of gas compressibility and the pressure of the gas. Thus, the curves z (compressibility)
versus pressure is difference from each other.

Keywords:
Ideal gases, real gases, gas compressibility.

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2.0 INTRODUCTION
In thermodynamics itself, it consists of two type of gases which are ideal and real gases.
For ideal gas, the equation is easy to remember and use, PV=nRT. The ideal gas obeys the Ideal
Gas Law thus its very useful to use. Generally, at higher temperature and lower pressure the gas
will behave ideally. This is because the potential energy and the size of particles become less
significant. The volume will be higher than ideal when the pressure is higher and the pressure
will be lower than ideal when the temperature is lower. The compressibility, z is the deviation
value form the ideal gas behavior.
z = PV/nRT
Gas compressibility or deviation factor (Z-factor) is defined as the ratio of the actual
volume to the ideal volume and is an indication of the gas deviation from ideal behaviour. Some
thermodynamic properties such as density, isothermal compressibility and viscosity can be
calculated by means of Z-factor. [2] The compressibility factor (Z) is a useful thermodynamic
property for modifying the ideal gas law to account for behavior of real gases. It is a measure of
how much the thermodynamic properties of a real gas deviate from those expected of an ideal
gas. It may be thought of as the ratio of the actual volume of a real gas to the volume predicted
by the ideal gas at the same temperature and pressure as the actual volume.
Compressibility factor, z can also be calculated by considering the ratio of molar volume at real
gas to ideal gas.
Z=Vreal/Videal
It is also important parameter for gas engineering calculations. It can be stated that
compressibility factor values of natural gases are required in gas engineering calculations such as
gas metering, gas compression, and design of pipelines.

Problem statement:
How does the theories of the researches differ from each other and how the curve of
compressibility versus pressure will form if different theories applied?

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3.0 METHODOLOGY
5 different compressibility factor,z versus pressure,P curves by using Papay, Beggs, Kumar,
Mahmoud and Van der Waals equation respectively are plotted ,A few steps are done in order to
calculate the compressibility factor of CO2 at varies pressure but at constant temperature ,600K.
The compressibility factor,z is calculated by using Papay, Beggs, Kumar,Mahmoud and Van Der
Waals equation as shown below:

1.Papays equation
Ppr Ppr
Z=1-Tpr [0.3648758 0.04188423( Tpr )]

Where,
P
Ppr=Ppc

T
T=Tpc

Ppc= yi Pci
Tpc= yi Tci

Ppc= pseudocritical pressure of the gas mixture


Tpc= pseudocritical temperature of the gas mixture
Pci=critical pressure of component i in the gas mixture
Tci = critical temperature of component i in the gas mixture
yi = mole fraction of component i in the gas mixture.

(2.)Beggs equation
(1A) D
Z=A+ + CPpr
eB

A=1.39(Tpr 0.92)0.5 0.36Tpr 0.101


0.066 2 0.32 6
B=(0.62-0.23Tpr) Ppr + [(T ) 0.037]Ppr +(109 (T )Ppr
pr 0.86 pr 1)

C=0.132-0.32 log(Tpr )
2
D=10(0.30160.49Tpr +0.1824Tpr )

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Gas Tc (K) Pc (bar) Gas Tc (K) Pc (bar)

H2 33.2 13.0 CH4 190.6 46.0


He-4 5.2 2.27 C2 H6 305.4 48.9

N2 126.2 34.0 C3 H8 369.8 42.5

O2 154.6 50.5 C4 H10 (n) 425.2 38.0

Cl2 417 77.0 C4 H10 (iso) 408.1 36.5


Bromin 584 103.0 Ethylena 282.4 50.4
Ammonia 405.6 113.0 Propylena 365.0 46.3
H2 O 647.1 220.5 CO2 304.2 73.8

(3.)Kumars equation
Ppr
Z=A+BPpr + (1 A) exp(C) D( 10 )4

Where A= -0.101-0.36Tpr + 1.3868Tpr 0.919


0.04275
B=0.021+T
pr 0.65

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C=Ppr (E + FPpr + GPpr )

D=0.122 exp (-11.3(Tpr 1))

E=0.6222-0.224Tpr
0.0657
F=T 0.037
pr 0.85

G=0.32 exp (-19.53(Tpr 1))

(4.)Mahmouds equation

Z=(0.702e2.5Tpr )Ppr
2
-(5.524e2,5Tpr )Ppr + (0.044Tpr
2
0.164Tpr + 1.15)

(5.)Van der Waals equation


a
(P + V2 (Vm b) = RT
m

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Van der Waals constants:
27R2 T2c
a= 64Pc

RT
b= 8P c
c

Gas a(L2 bar. mol2 ) b(L. mol1 ) Gas a(L2 bar. mol2 ) b(L. mol1 )

H2 0.2476 0.02661 CH4 2.283 0.04278


He 0.03457 0.02370 C2 H6 5.562 0.06380

N2 1.408 0.03913 C3 H8 8.779 0.08445

O2 1.378 0.03183 C4 H10 (n) 14.66 0.1226

Cl2 6.579 0.05622 C4 H10 (iso 13.04 0.1142


)
NO 1.358 0.02789 C5 H12 (n) 19.26 0.1460

NO2 5.354 0.04424 CO 1.505 0.03985

H2 O 5.536 0.03049 CO2 3.640 0.04267

The compressibility factor, z values calculated by using different equation as stated are then
tabulated into tabled form.Graphs of z versus pressure,p are plotted.

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4.0 RESULT
APPENDIX:
Result calculated by using:
1.Papays CO2
equation Pc (bar) 73.8
pressure Ppr Tpr z Tc (K) 304.2
0 0 1.972387 1 T(K) 600
100 1.355014 1.972387 0.769100882
200 2.710027 1.972387 0.577736945
300 4.065041 1.972387 0.425908188
400 5.420054 1.972387 0.313614612
500 6.775068 1.972387 0.240856216
600 8.130081 1.972387 0.207633001
700 9.485095 1.972387 0.213944967
800 10.84011 1.972387 0.259792113
900 12.19512 1.972387 0.345174439

2. Beggs equation

pressure Ppr Tpr A B C D Z


0 0 1.972387 0.614884771 0 0.037603 1.108467 1
100 1.355014 1.972387 0.614884771 0.266411 0.037603 1.108467 0.96258999
200 2.710027 1.972387 0.614884771 0.614827 0.037603 1.108467 0.93667136
300 4.065041 1.972387 0.614884771 1.04525 0.037603 1.108467 0.92826248
400 5.420054 1.972387 0.614884771 1.557684 0.037603 1.108467 0.94081315
500 6.775068 1.972387 0.614884771 2.15214 0.037603 1.108467 0.97316346
600 8.130081 1.972387 0.614884771 2.828641 0.037603 1.108467 1.02137422
700 9.485095 1.972387 0.614884771 3.587229 0.037603 1.108467 1.08077826
800 10.84011 1.972387 0.614884771 4.427973 0.037603 1.108467 1.14734193
900 12.19512 1.972387 0.614884771 5.350975 0.037603 1.108467 1.21818875

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(3.)Kumar's equation
Tpr=1.972387
A=0.612277783
B=0.053328
D=2.06227E-06

pressure Ppr C E F G z
0 0 0 0.1803854 0.021535981 1.80963E-09 1
100 1.355014 0.283966 0.1803854 0.021535981 1.80963E-09 0.976412
200 2.710027 0.647015 0.1803854 0.021535981 1.80963E-09 0.959811
300 4.065041 1.089149 0.1803854 0.021535981 1.80963E-09 0.959527
400 5.420054 1.610369 0.1803854 0.021535981 1.80963E-09 0.978789
500 6.775068 2.210684 0.1803854 0.021535981 1.80963E-09 1.016081
600 8.130081 2.890102 0.1803854 0.021535981 1.80963E-09 1.067382
700 9.485095 3.64864 0.1803854 0.021535981 1.80963E-09 1.128187
800 10.84011 4.486317 0.1803854 0.021535981 1.80963E-09 1.194722
900 12.19512 5.403163 0.1803854 0.021535981 1.80963E-09 1.264361

(4.)Mahmouds equation

CO2
Pressure Ppr Tpr Z Pc(bar) 73.8
0 0 1.972387 0.997702189 Tc(bar) 304.2
100 1.355014 1.972387 0.952968732 T(K) 600
200 2.710027 1.972387 0.926845981
300 4.065041 1.972387 0.919333936
400 5.420054 1.972387 0.930432598
500 6.775068 1.972387 0.960141966
600 8.130081 1.972387 1.008462041
700 9.485095 1.972387 1.075392821
800 10.84011 1.972387 1.160934308
900 12.19512 1.972387 1.265086502

(5.)Van der Waals equation

Derive Vm from : Solve Vm by deriving it into form:

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CO2
R= 0.08315
Tc= 304.2
Pc= 73.8
a= 3.64
b= 0.04267
T= 600

Pressure,P Vm(real Vm(ideal)


0 Infinite Infinite Infinite Infinite Infinite Infinite
100 -0.682925 0.0364 -0.00155 0.471317 0.640255 0.736139853
200 -0.3627975 0.000213 -0.00078 0.300073 0.3201275 0.937353532
300 -0.256088333 0.012133 -0.00052 0.151552 0.21341833 0.710116191
400 -0.20273375 0.0091 -0.00039 0.118354 0.16006375 0.739417208
500 -0.170721 0.00728 -0.00031 0.10073 0.128051 0.786638792
600 -0.149379167 0.006067 -0.00026 0.090527 0.10670917 0.848356998
700 -0.134135 0.0052 -0.00022 0.083221 0.091465 0.90987098
800 -0.122701875 0.00455 -0.00019 0.07793 0.08003188 0.973735271
900 -0.113809444 0.004044 -0.00017 0.074452 0.07113944 1.046562749

Compressibility factor,Z
1.6
Z versus p Van der Waals'
1.4
Kumar's
1.2
Beggs's
1
Mahmoud's
0.8

0.6

0.4 Papay's
0.2

0 Pressure,P
0 2 4 6 8 10 12

Graph 1: graph of compressibility factor,z versus pressure,p.

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5.0 DISCUSSION
Graph 1 shows the changes in the compressibility factor , Z with the varies of pressure , P
at constant temperature, which is 600 Kelvin for real gas carbon dioxide(CO2).
From the line graph plotted by using Papays equation,, the curve shows that the compressibility
factor, Z decreases with the increase of pressure at constant temperature. The Papays curve
show a descending slope of curve. This is due to the gas behave ideally at high temperature,600K
and at low pressure.However,there is a minimum value of compressibility factor ,z at particular
pressure and fluctuate to a higher value of compressibility factor as the pressure increase.

By using Beggs equation with constant temperature 600K, at low pressure the
compressibility factor value is closer to 1. This indicates a more ideal behaviour in the gas.
Furthermore, the Beggs curve experiences little deviation. The gas behave ideally at high
temperature which is 600K and low pressure. The graph of compressibility factor of carbon
dioxide against pressure shows little deviation from the ideal gass compressibility factor which
is 1.
Besides of that, by using Kumars equation, the carbon dioxide behaves almost similar
what we obtain from Beggs equation.At constant temperature 600K, CO2 behave almost like an
ideal gas and experience less deviation from ideal gas compressibility factor with value 1, as
compared to Papays, Van Der Waals and Mahmouds equation. CO2 behave ideally at high
temperature which is 600K and low pressure.
At constant temperature 600K, Mahmouds equation show CO2 at low pressure, the
compressibility factor value is closer to 1. The Mahmouds curve of compressibility factor of
carbon dioxide against pressure shows little deviation from the ideal gass compressibility factor
which is 1.This indicates a more ideal behaviour in the gas. Furthermore, the Beggs curve
experiences little deviation. The gas behave ideally at high temperature which is 600K and low
pressure.
Based on graph, the Van Der Waals curve show the compressibility factor of carbon
dioxide at varies pressure but at constant temperature, 600K. The graph from Figure 4.1 shows
that the compressibility factor, Z at first surged up to 1.2, then it decreases with the increase of
pressure at constant temperature. However, it fluctuated and increase with the increade of the
pressure.. As the pressure increase, the pV isotherm deviates more and more from perfect
behavior. It show bigger deviation from compressibility factor 1 as the pressure increase.

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6.0 CONCLUSION
Based on the Papay, Beggs, Kumar, Mahmoud & Van Der Waals equation obtained for real
gas, the closer a real gas is to its critical point or to its saturation point, the larger are the
deviations of the gas from ideal behavior. Compressibility factor of natural gases approach ideal
gas behavior at low pressure and high temperature. At low pressures, It can be seen from the
curves plotted, CO2 almost behave ideally at low pressure at constant temperature 600K.
Hence,the compressibilty factor, Z approaches 1 at low pressure which means that the real
gas behaves much like a perfect gas. Therefore, the compressibility factor of the real gas is
dependence on temperature and pressure.

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7.0 REFERENCE
1. http://opentextbc.ca/introductorychemistry/chapter/6-8-real-gases/
2. http://www.tau.ac.il/~tsirel/dump/Static/knowino.org/wiki/File_Compressibility_Factors.
html
3. http://www.researchgate.net/profile/Ali_Mohebbi/publication/23660194_A_New_Piecew
ise_EOS_for_Compressibility_Factor_Prediction_Based_on_the_M-
factor_Theory/links/00b495329b11ae4713000000.pdf
4. http://www.sciencedirect.com/cache/MiamiImageURL/1-s2.0-S0378381298002441-
gr5.gif/0?wchp=dGLzVBA-zSkzV&pii=S0378381298002441
5. http://en.citizendium.org/wiki/Compressibility_factor_%28gases%29
6. http://www.chemguide.co.uk/physical/kt/realgases.html
7. Levine, I. N. (1988). REAL GAS. In Physical chemistry, third edition (3rd ed.). New York: McGraw-
Hill Book Co
8. Fluid Phase Equilibrium, 25 May 2005, pages 74-89 <
http://www.sciencedirect.com/science/article/pii/S0378381205000828#fig2>
9. Viewed on 24 May 2015 < http://en.wikipedia.org/wiki/Compressibility_factor >
10. Journal of the Taiwan Institute of Chemical Engineers, 16 January 2015, <
http://www.sciencedirect.com/science/article/pii/S1876107014004088 >

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