16 views

Uploaded by Muhammad Lutfi Maulidi

Attribution Non-Commercial (BY-NC)

- Marcet Boiler lab report
- Introduction to Offshore Petroleum Production System
- Development of a Universal Group Contribution Equation of State
- (484318736) bender.docx
- MSc Thesis AlanNehemy
- Exs
- CHE-707_Ten Num_probs in ChemEng
- Chang General Chemistry Questions and Answers
- IS Methods of Sampling Chemical & Chem Products
- 12-2 Worksheet #3 FAGP
- ie800763x
- Analyzer Sample Systems Ver Happen
- Sci Physics Prelim 09 4E5NA P1
- Perfect Gases
- New Explicit Correlation for the Compressibility Factor
- IIT-JEE 2002 Mains Paper With Answer Key
- Double Retrograde Vaporization
- ICBPT1Intro2Unit(1)(1)
- Three States of Matter
- Chapter 3 Cont'

You are on page 1of 9

9 The Virial EOS: 9 Limited to moderate pressure (~10bar) due to difficulty of getting additional constants beyond the second virial coefficient 9 Virial coefficients at f(T) and unique to each gas. PV = ZnRT 9 The generalized EOS can be written as 9 At the Boyle temperature, PV = nRT

9 Cubic EOS and their merit 9 The van der Waals EOS for high pressure and two phase regions. 9 The ideal gas limit of the van der Waals EOS. 9 The critical point test for the van der Waals EOS. 9 The Virial equivalent of the van der Waals EOS. 9 Saving the van der Waals EOS. 9 The principle (theorem) of corresponding state.

1/28/2008 van der Waals EOS 1

The VEOS is accurate only to moderate pressure and additional constants are needed in the high density region, which is very difficult to obtain. In VEOS, the intermolecular forces are summed in the single constant. The VEOS does not work in two-phase region. We need another EOS which approximates P-V-T behavior at high pressure and accounts phase change. The van der Waals EOS accounts liquefaction,critical point, and unlike the virial equation, it works in high density region.

1/28/2008

The excluded volume is the first concept in the van der Waals Equation of State.

The result of this excluded volume is that pressure in real gases is no longer given by:

P=

RT V

..but must account the excluded volume effect and should be written:

P=

1/28/2008

RT V b

van der Waals EOS 3

Now we have accounted for the repulsive force (excluded volume), what happens to the attractive forces? Within molecules both repulsive and attractive forces are present and the net result is governed by the dominant one. The pair of attracting molecule is proportional to the number density, 1/V.

1 V2

and the pressure must be reduced by this amount. The van der Waals equation then takes the form:

P=

RT a 2 V b V

The ideal gas limit of the van der Waals EOS is readily seen when the volume is very large.

1/28/2008 van der Waals EOS 4

P= RT a V b V 2

RTc 2a P evaluated + 3 at T ,P ,V = 0 = 2 V T (Vc b ) Vc c c c 2 P evaluated 2 RTc 6a =0= 4 2 3 at T ,P ,V V V (Vc b ) c c c c T

V = V c = 3b T = Tc = 8a 27bR a P = Pc = 27b 2

a= b=

27 R 2Tc 2 64 Pc RTc 8 Pc

a and b are positive constants independent of temperature but characteristics of each gas!

1/28/2008 van der Waals EOS 5

The compressibility factor at the critical point and the virial equivalent of the van der Waals EOS

At critical point, the van der Waals EOS tells us that, irrespective of the type of gas: a 2 3b PV 3 c c Zc = = 27b = = 0.375 RTc R(8a / 27bR) 8 What about the compressibility factor anywhere else?

RT a V b V 2 PV V a = Z= RT V b RTV P=

B = B' RT

Z=

PV 1 a = 1+ b RT RT V

van der Waals EOS 6

1/28/2008

The merit of the equation is that it provides the presence of critical point in real gases.

P=

RT a a ab RT 2 V3 + b V 2 + V =0 V b V P P P

Cubic in volume (3 roots) 9At T>Tc one root 9 At the critical point all three roots equals Vc 9Two-phase region (three roots)

1/28/2008

Cubic in Volume (has three roots). Any real root has to be positive and should be greater than the constant b.

It predicts 3 roots, two of which are real and the third has no physical meaning. It also predicts that

P = + ve V T

which violates our common sense.

1/28/2008

Contrary to experimental observations the van der Waals EOS oscillates in the two-phase region with some meaningless behavior. Metastable: subcooled vapor

P = ve V T

P = + ve V T P = ve V T

The Maxwell plot The flat portion has to be an artificial add-on since no cubic equations have flat line with finite length.

1/28/2008 van der Waals EOS 9

9 Cubic EOS: van der Waals 9 The van der Waals EOS for high pressure and two phase regions. 9 The ideal gas limit of the van der Waals EOS. 9 The critical point test for the van der Waals EOS. 9 The Virial equivalent of the van der Waals EOS. 9 Saving the van der Waals EOS. The principle (theorem) of corresponding state.

1/28/2008

10

a P + 2 (V b ) = RT V V = Vc = 3b; T = Tc = a 8a ; P = Pc = 27bR 27b 2 Applying some tricks to (2) and substituting into (1) and some algebraic reduction we get: (1) (2)

(3)

1/28/2008 van der Waals EOS

(4)

11

Z = Z (Pr , Tr )

Examples of simple & spherical molecules are Ar, Xe, Kr, Ne

This principle fails when applied to complex gases, with strong dipolar moments and/or non-spherical force fields.

1/28/2008

12

Z= Z (Pr, Tr), for spherical molecules!

1/28/2008

13

Since the time of van der Waals hundreds of cubic EOS have been developed but most of them were abandoned. Those which found widespread use have the general form

P=

RT attractive term V b

P=

( V- ) RT V b (V b ) V 2 + V +

1/28/2008

=b =a = =0

14

Attractive term

a V2

a T V (V + b )

V (V + b )

a (T )

1976 1899

V (V + b ) + b (V b )

a (T )

a TV 2

15

1/28/2008

1/28/2008

16

Concluding remarks

The van der Waals EOS accounts the presence of critical point, works at higher pressure (density) regions and unlike the virial EOS the attractive and repulsive terms are incorporated separately. It can be reduced to the ideal gas EOS when volume is very large. It suggests Zc= 0.375 which generally is higher than experimentally observed values (0.24-0.3) It has a virial expansion form that gives the second virial coefficient in terms of the van der Waals Constants a & b. It provides the principle of two-parameter corresponding state.

1/28/2008

17

- Marcet Boiler lab reportUploaded byAnna Kay
- Introduction to Offshore Petroleum Production SystemUploaded byJoaoCOS
- Development of a Universal Group Contribution Equation of StateUploaded bymappemaq
- (484318736) bender.docxUploaded bySantiago Alejandro
- MSc Thesis AlanNehemyUploaded byRiccardo Cozza
- ExsUploaded byalphamale173
- CHE-707_Ten Num_probs in ChemEngUploaded byDauda Baba
- Chang General Chemistry Questions and AnswersUploaded byHan Tsu
- 12-2 Worksheet #3 FAGPUploaded byFFF
- IS Methods of Sampling Chemical & Chem ProductsUploaded byshashi1192
- ie800763xUploaded byJuan Palacios
- Analyzer Sample Systems Ver HappenUploaded byIñaki Eseberri
- Sci Physics Prelim 09 4E5NA P1Uploaded bytopcat
- Perfect GasesUploaded byellayusliana
- New Explicit Correlation for the Compressibility FactorUploaded byjudarangoca
- IIT-JEE 2002 Mains Paper With Answer KeyUploaded byNarmadha Ramesh
- Double Retrograde VaporizationUploaded bychemsac2
- ICBPT1Intro2Unit(1)(1)Uploaded bySo Cho Wing
- Three States of MatterUploaded byBajwa Qasim
- Chapter 3 Cont'Uploaded byshruthi venkataraman
- CERN Basic Vacuum 2012 LectureUploaded bychipulino
- Brochure 2010Uploaded byshankarsreekumar
- Chem termo modUploaded byAda Topan
- 3bc412bb-2364-4818-a475-6316b467fba3Uploaded byNihar Ranjan
- Chapter 12 SolutionsUploaded byFikri Azim
- energies-08-08516Uploaded byNhat Cao
- _001Uploaded byplayer wite
- aaUploaded byluis900000
- ch 13 14 states of matter gas laws ppt pdfUploaded byapi-239855791
- Exam 1 Solution Chapter 1 of thremodynamicsUploaded byjay1191

- Massive Japan Earthquake (8.9 Richter Scale!!!) Makes It # 5 Ever Recorded - Magnitude 8 and Greater Earthquakes Since 1900 Sorted by MagnitudeUploaded byZim Vicom
- WIPRO Latest IT Fresher Placement Sample Question PaperUploaded byfreedalionel
- Final 2015.docxUploaded byRayyan Salman
- Pump Technical Information from March Pumps Series MDX-MT3Uploaded byMarch Pumps
- main group chemistryUploaded bySurender Malik
- Victorian EraUploaded byAru Saberfang D'crestfallen
- Instrumentation, Electronics & Control Sensing Devices _ Engineers Edge _ Www.engineersedge.comUploaded byEngEdge
- Bacteriological and Physio Chemical Quality Assessment of Drinking WaterUploaded byEditor IJTSRD
- Silver MealUploaded byMang Adul
- SikaGrout -114 AEUploaded byJacksonSamuel
- Non Metallic Materials Used for Machine Elements2Uploaded byRajanikantJadhav
- The World Conference On Laser, Optic Science & Photonics (LSP 2020) - SponUploaded byHazel Group
- lesson plan dos word finalUploaded byapi-249460707
- sdaie lessonUploaded byapi-290598707
- Cebu City PresentationUploaded bya313
- Essay - Ways of Seeing by John BergerUploaded byKarin Lobo
- ABO Blood Group System.pdfUploaded byPerry Sin
- D1348Uploaded byНенад Кнежевић
- Scenario Mgr - Goal Seek- ExampleUploaded bykaliprasa
- DDSS Unit 1Uploaded byratnakar
- Distributed Database IUploaded byUsmanAhmed
- The Practice of Construction Management Third EditionUploaded byRene
- Upper and lowercase Volume 5—Issue 3Uploaded byaBlaqSerif
- Sparking-Student-Creativity-Book-Study-Guide.docxUploaded byJose Gregorio Vargas
- Villager High Efficiency Multifuel Wood StovesUploaded byOptima Bioenergy
- CITS SlidesUploaded byTay Joo Fang
- Roi Econometric ModelingUploaded byAser A. Abdullah
- ap5tcUploaded byAlberto Leal Cruz
- Buy Gold Bullion RbcUploaded byEd Rees
- Apps DBAUploaded byjagatheeshr@gmail.com