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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.

2

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

3

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.

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.

4

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?

5

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

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

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 )

6

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

He-4 5.2 2.27 C2 H6 305.4 48.9

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

0.04275

B=0.021+T

pr 0.65

4

C=Ppr (E + FPpr + GPpr )

E=0.6222-0.224Tpr

0.0657

F=T 0.037

pr 0.85

(4.)Mahmouds equation

Z=(0.702e2.5Tpr )Ppr

2

-(5.524e2,5Tpr )Ppr + (0.044Tpr

2

0.164Tpr + 1.15)

a

(P + V2 (Vm b) = RT

m

7

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 )

He 0.03457 0.02370 C2 H6 5.562 0.06380

)

NO 1.358 0.02789 C5 H12 (n) 19.26 0.1460

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.

8

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

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

9

(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

10

CO2

R= 0.08315

Tc= 304.2

Pc= 73.8

a= 3.64

b= 0.04267

T= 600

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

11

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.

12

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.

13

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 >

14

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