Book Corrections for Thermodynamic Models

8/8/2019 Book Corrections for Thermodynamic Models

1/18

Book Corrections for Thermodynamic Models

for Industrial Applications: From Classical and

Advanced Mixing Rules to Association Theories

by Georgios Kontogeorgis and Georgios Folas

The Acknowledgments should read as:

Acknowledgments

We wish to thank all our students and colleagues and especially the faculty members

of IVC-SEP Research Center, at the Department of Chemical and Biochemical

Engineering of the Technical University of Denmark (DTU), for their many inspiring

discussions during the past 10 years which have largely contributed to the shaping of

this book. Our very special thanks go to Professor Michael L. Michelsen for the

endless discussions the authors have enjoyed with him on thermodynamics.

In the preparation of this book we have been assisted by many colleagues, friends,

current and former students. Others have read chapters of the book, others providedmaterial prior to publication, while we have had extensive discussions with others.

We would particularly like to thank Professors J. Coutinho, G. Jackson, I. Marrucho,

G. Sadowski, L. Vega, M. E. Vigild, E.C. Voutsas and N. von Solms, Doctors M.

Breil, H. Cheng, Ph. Coutsikos, S. Derawi, C. Eenschooten, J.-C. de Hemptinne, I.

Economou, J. Gabrielsen, A. Grenner, E. Karakatsani, I. Kouskoumvekaki, Th.

Lindvig, E. Solbraa, N. Muro-Su, A. Tihic, I. Tsivintzelis, A. Vrachnos and W.

Yan, as well as the current PhD and MSc students of IVC-SEP, namely A. Avlund, J.

Christensen, L. Faramarzi, F.Leon, B.Maribo-Mogensen, Th. Rove and A. Sattar-Dar.

We are particularly grateful to Professor Nicolas von Solms for his contributions in

the SAFT chapters and to Dr. Martil Breil for proof-reading Chapters 15 and 19.

All contributions have been highly valuable and we are deeply grateful for them.
http://eu.wiley.com/WileyCDA/Section/id-302479.html?query=Georgios+Kontogeorgishttp://eu.wiley.com/WileyCDA/Section/id-302479.html?query=Georgios+Folashttp://eu.wiley.com/WileyCDA/Section/id-302479.html?query=Georgios+Folashttp://eu.wiley.com/WileyCDA/Section/id-302479.html?query=Georgios+Folashttp://eu.wiley.com/WileyCDA/Section/id-302479.html?query=Georgios+Kontogeorgis


2/18

Chapter 1

Table 1.3. The caption should read:

Phase Equilibrium equations in specific cases including basic equations for

equilibrium calculations with equations of state (EoS). The fugacity coefficient of a

compound in a mixture is defined as:

i

i

i

f

x P , where ix can be the concentration

either in the liquid, vapour or solid phase. The vapour pressure Psat

is obtained from

correlations based, for example, on the Antoine equation or the DIPPR correlations.

Table 1.4, lines 2 and 3 should read:

Ideal gas or liquid solution

at any pressure

(Lewis-Randall)

Valid in practice at low

pressure and mole fractions

above 0.9 [it is essentially

representation of : Amolecule feels at home

when it is alone with its

own kind than with

company.]

,

i i i i i i pure i

i

V n V V V f y f

v l

i i i iy f x f

Chapter 2

Page 26, points 2 and 3. The repulsive van der Waals forces and other applications of

van der Waals forces are discussed in Chapter 18 (not in Chapter 16).

Page 19. The correct units of dielectric permittivity in Table 2.1 and the text

following Table 1 are

C2J

-1m

-1.


3/18

Chapter 3

Page 48, text prior to eq. 3.7. The reference for methane-alkanes is 27 not 2, i.e. the

text should read:

Methane-alkanes27

Page 48, Table 3.7, next to last line: The mixture is HCl-HJ (not HC-HJ)

Chapter 5

Equation 5.37 should read:

R

TS

RT

AC

CT

dR

UC

T

dT

RT

U

RT

A

EE

T

T

T

ET

T

EE

)(lim

1

0

0

/1

/1

/1

/1

0

00

5.37

Corrected Figure 5.6

Figure 5.6. Vapor-liquid equilibria correlation with UNIQUAC for one mixture with

positive (right/bottom figure, acetonitrile (1)-benzene (2) at 45

o

C) and another onewith negative deviations from Raoults law (left /top figure, acetone (1)-chloroform

(2) at 50oC). Excellent correlation is achieved in both cases.


4/18


5/18

Reference for Table 5.10:

From G.M. Kontogeorgis, 2004. Models for Polymer Solutions. In: G.M. Kontogeorgis, R. Gani,

2004. Computer-Aided Property Estimation for Process and Product Design. Elsevier, 2004.

Chapter 6

Page 164, Table 6.4, lines 5 and 6.

The equation for MHV2 should read:

i i

i

E

i

ii

i

iibbx

RTgxqxq ln

,*

2221

Page 167.

The text prior to equation (6.4) should read:

For PR, the expression for the mixture energy parameter a is similar to that of Huron-Vidal

Equations 6.4 and 6.5 should read:

(6.4)

,*

0.6232

E

ii

i i

aa gx

b b

(6.5)

1

i j

i j ij

E

ii

i i

ax x b

RTb

aAx

RT b RT


6/18

Page 171, Table 6.6.

The PSRK-new and VTPR model equations should read:

,*,

1

1E res

i i

i

gx

A RT

The UMR-PR model (last line) should read:

, ,

1

1E SG E res

i ii

g gx

q RT RT

Page 172. The first line should read:

This is essentially the PSRK-new mixing rule.

Pages 173 and 178. The copyright year is (1994) in the captions of figures 6.9 and 6.13.

Page 173, following equation 6.14:

PR EoS: Av = - 0.623, AM= - 0.52

Page 174. Equation 6.16 should read:

,*,

1

1E res

i i

i

gx

q RT

Page 179, Figure 6.16. The LCVM calculations are at 35oC and 60

oC, as indicated in the figure

caption.

Page 190. Equation 6.26 should read:

, ,1

ln 2 ln 2ln 2

E E

i i i i

i i

x a x ag a ga b

RT RT b RTb b


7/18

Chapter 8

Table 8.2 should read as:

Table 8.2. CPAa special case of SAFT-variants.

Model Reference Main applications

CPA (based on SRK + SAFT)

e-CPA

Kontogeorgis et al.20,21

Kontogeorgis et al.22,23

Ruffine et al.24

Lin et al.25

Water-alcohols(glycols)-

hydrocarbons (V)LLE

Acids, amines, etc

Acid gases (H2S)

Electrolytes (water-salts VLE,

SLE)

ESD Elliott et al.26

Suresh and Elliott27,28

Puhala and Elliott

29

Water-alcohols-gases-

hydrocarbons

PR-CPA (+extra electrolyte

term)

Wu and Prausnitz30

Water-hydrocarbons-salts

PR-CPA Pfohl et al.31

CO2-phenols/cresol

PR-CPA Perakis et al.32,33

Voutsas et al.34

CO2-water-ethanol and acetic

acid VLE

Water-alkanes

CO2-polars

PR-CPA Huang et al.35

CO2/alcoholaspirin,

naproxen SCFE

Page 226, following equation 8.8 should read:

As von Solms discusses124,125

: The temperature dependency of the size parameter does have a

physical significance: it accounts for the fact that real molecules are not hard-spheres, but ratherthere is some degree of interpenetration between molecules, particularly at high temperatures, thus

the effective hard-sphere diameter of a segment is smaller at higher temperatures. This effect

seems, however, to be small in practical applications.

Page 229 (in the SAFT-VR section) should read:

Von Solms124,125

emphasizes that the introduction of this extra term gives SAFT-VR greater

flexibility, since an extra pure pure-component parameter is available. Although it is generally

desirable to describe pure component liquid densities and vapor pressure with the minimum number


8/18

of parameters, the extra variable-range parameter may be necessary for the description of certain

anomalous behaviours in systems containing water124,125

.

Page 230 (in the PC-SAFT section) should read:

There is, however, a fundamental difference between PC-SAFT and the previous versions of SAFT.

As von Solms presents it124,125

the dispersion term attempts to account for dispersion attraction

between whole chains. Referring to figure 8.1 should make this clear. Instead of adding the

dispersion to hard-spheres and then forming chains, we first form hard-sphere chains and then add a

chain dispersion term, so the route in figure 8.1 would be (b)-(d)-(c)-(e)124,125

.

Figure 8.11. Revised figure caption.

Figure 8.11. VLE for CO2-methyl oleate with sPC-SAFT using EoS parameters estimated from the

group-contribution method ofTihic et al.66

. From Tihic126

.

Additional references in Chapter 8:

124. Nicolas von Solms. 2003. SEP 0343. Short Course on PC-SAFT. IVC-SEP, Department of

Chemical and Biochemical Engineering (internal report). June 2003

125. Georgios M. Kontogeorgis and Nicolas von Solms, 2009. Chapter 11: Thermodynamics ofpolymer solutions (pages 499-537). In Handbook of Surface and Colloid Chemistry, Editor K.S.

Birdi, 3rd

ed., CRC Press, Taylor and Francis

126. A. Tihic, Group contribution sPC-SAFT equation of state. PhD Thesis, The Technical

University of Denmark, 2008.


9/18

Chapter 9

Figure 9.20 (left) should be replaced by the following one:

Chapter 10

Figure caption 10.7. The correct reference is ref. 3 of Chapter 10.

Figure captions 10.2110.24 and Table 10.4. The correct reference is Yan et al., 2009 (ref. 42 of

Chapter 10).

Chapter 11

The first lines in the caption of figure 11.20 should read:

Figure 11.20. (Left): VLLE with CPA for the system DiPE-water at 101.32kPa. VLE data are from

Hunsmann et al., Chem.-Ing.-Tech., 1966, 38, 1053 ().

Table 11.5. It should be added: From N. Muro-Su (private communication).

Moreover, the A21 parameter of set 2 should read:

-157.6-1.8972T

0.0001

0.001

0.01

0 20 40 60 80 100 120 140

m

olefraction

P / bar

273.15K

298.15K

313.15K


10/18

Chapter 12

Figure 12.13 (page 382). The aniline mole fraction is depicted in the x-axis.

Chapter 13

In the figure caption 13.15 (b), the first line should read: VLE and LLE for

The following reference should be added in Table 13.6 is:

Modified from A. Grenner, A. Tihic and E. Karakatsani (private communication).

Chapter 14

The correct spelling in the captions of figures 14.9, 14.12, 14.16, 14.17 and 14.29 is: Nicolas von

Solms.

Tables 14.3 and 14.6. It should be added. From Kouskoumvekaki et al.32

.

Table 14.4. It should be added. From Tihic et al.48.

Table 14.5 as well as figure 14.16b. It should be added: From Tihic49.

The text prior to eq. 14.9 should read:

Since diethylene glycol has one ether group, triethylene glycol has two ether groups and

tetraethylene glycol has four ether groups, the number of additional association sites in the molecule

attributed to the ether groups can be approximated by (A. Grenner, personnal coomunication):

Figure 14.6. A reference should be added: A. Grenner (private communication).


11/18

The permission line in the caption of figures 14.2, 14.22 and 14.23 should read as:

Reprinted with permission from Molecular Simulation, Solubility of gases and solvents in silicon

polymers: molecular simulation and equation of state modeling by Ioannis G. Economou, Zoi A.

Makrodimitri, Georgios M. Kontogeorgis and Amra Tihic, 33, 9, 851-860 Copyright (2007) Taylorand Francis.

Additional reference in Chapter 14

49. A. Tihic, Group contribution sPC-SAFT equation of state. PhD Thesis, The Technical

University of Denmark, 2008.

Chapter 15

The text prior to equations 15.6 and 15.7 should read:

The rational asymmetric activity coefficients ( 10 * iix ): Normalized so that the activity

coefficients are one at infinite dilution:

The molal-based activity coefficients (hypothetical ideal solution at unit molality, m0:

10 miim ):

The text after eq. 15.7 should read as:

As discussed by Thomsen, all three standard states are related to each other as119

:

io

ii RT ln* 15.8a

00

*lnln mMRTmMRT wi

o

iwi

m

i

15.8b

Page 478, Figure 15.1. The first line should read:

Nitric acid-water calculations with the e-NRTL model.


12/18

Page 471, Table 15.1 (Continued)

The Born term, mid in page 471 should read:

ions iiiA Zn

DkTeN

2

0

2

114

Page 501, Table 15.7. Correction needed in the Absorption Capacity column. The correct is:

Highest absorption capacity for MDEA and lowest for MEA.

Table 15.11. It should be added: From Gabrielsen95a.

Reference for Figure 15.22. A. Vrachnos (private communication).

Additional reference in Chapter 15:

119. K. Thomsen, "Electrolyte Solutions: Thermodynamics, Crystallization, Separation methods",

Lecture notes, DTU Chemical Engineering,Technical University of Denmark, 2009. Available at:

http://orbit.dtu.dk/AdvancedSearchPublications,resultSetTable.recordLink.sdirect?sp=192574

Chapter 16

Figure 16.4caption. The temperatures are 318.15 K and 328.15 K, as shown in the figure.

Figure 16.14caption. At the end it should read The best results are obtained with COSMO-RS.

Chapter 17

Table 17.3, under 1973.

It should read:

Many lakes, rivers etc. are now cleaned, see e.g. figure 17.3.
https://owa.kt.dtu.dk/exchweb/bin/redir.asp?URL=http://orbit.dtu.dk/AdvancedSearchPublications,resultSetTable.recordLink.sdirect?sp=192574https://owa.kt.dtu.dk/exchweb/bin/redir.asp?URL=http://orbit.dtu.dk/AdvancedSearchPublications,resultSetTable.recordLink.sdirect?sp=192574https://owa.kt.dtu.dk/exchweb/bin/redir.asp?URL=http://orbit.dtu.dk/AdvancedSearchPublications,resultSetTable.recordLink.sdirect?sp=192574


13/18

Table 17.6.

The following reference should be added: From H. Cheng. Thermodynamic Modelling of

Surfactants Solutions. PhD Thesis. Technical University of Denmark, Lyngby, Denmark, 2003.

Chapter 18

Figure 18.13.

The following reference should be added: From H. Cheng. Thermodynamic Modelling of SurfactantsSolutions. PhD Thesis. Technical University of Denmark, Lyngby, Denmark, 2003.

Chapter 19

The caption of figure 19.23 should read:

Figure 19.23. CH4 MEG vapor liquid equilibrium. Experimental data (points) and NRHB

calculations with kij= 0.05482.

Page 652, last line under 1st

point should read:

Figure 19.23 below shows a typical result with NRHB for MEG-methane.


14/18

Corrections in the web-site material

Problem 6.1 (1 in chapter 6)

In the first and 4th

line of the problem, it should read excess Gibbs energy (and not excess Gibbs

free energy)

Problem 6.3 (3 in chapter 6)

In the 4th

line of the problem, it should read excess Gibbs energy (and not excess Gibbs free

energy)

Problem 4 in Chapter 17

The correct symbols in the units (line 2) are lg/ and l/kg

Answers to selected problems

Problem 4.2.

The correct answer is:

Jx 2312 1038.10 = 62.509 J/mol or 0.06 KJ/mol.

Problem 6.3.i

i.

bRT

a

u

x

ub

bx

RT

g

i

ii

i

i

P

E

,1

1ln1

1lnln

0


15/18

Additions in Appendix A

Following Tables A.1 and A.2 the following text (references) should be added:

References for the parameters presented in Tables A.1 and A.2

G.M. Kontogeorgis, I.V. Yakoumis, H. Meijer, E. Hendriks, and T. Moorwood,

Fluid Phase Equilib., 158-160:201, 1999.

G.K. Folas, S.O. Derawi, M.L. Michelsen, E.H. Stenby, and G.M. Kontogeorgis,


G.K. Folas, J. Gabrielsen, M.L. Michelsen, E.H. Stenby, G.M. Kontogeorgis, Ind. Eng. Chem. Res.

2005, 44, 3823.

I.V. Yakoumis, G.M. Kontogeorgis, E.C. Voutsas, and D.P. Tassios, Fluid Phase Equilib., 130:31

47, 1997.

S.O. Derawi, J. Zeuthen, M.L. Michelsen, E.H. Stenby G.M. Kontogeorgis, Fluid Phase Equilibria,

2004, 225, 107.

S.O. Derawi, G.M. Kontogeorgis, M.L. Michelsen, and Stenby E.H.,Ind. Eng. Chem. Res.,42:14701477, 2003.

S.O. Derawi, G.M. Kontogeorgis, M.L. Michelsen, and Stenby E.H., Fluid Phase Equilib.,

209:163184, 2003.

M. Kaarsholm, S.O. Derawi, M.L. Michelsen, G.M. Kontogeorgis, Ind. Eng. Chem. Res., 2005,

44(12), 4406.

E.C. Voutsas, G.M. Kontogeorgis, I.V. Yakoumis, and D.P. Tassios, Fluid Phase Equilib., 132:61

75, 1997.

G.K. Folas.Modeling of Complex Mixtures Containing Hydrogen Bonding Molecules. PhD thesis,

Technical University of Denmark, DTU, 2007.

N.M.F. Garrido, G.K. Folas, G.M. Kontogeorgis, Fluid Phase Equilibria, 2008, 273, 11.

A.S. Avlund, G.M. Kontogeorgis, M.L. Michelsen,Ind. Eng. Chem. Res., 2008, 47, 7441.

G.M. Kontogeorgis, G.K. Folas, N.Muro-Su, F. Roca Leon, M.L. Michelsen, OGST - Revue de

IIFP, 2008, 63, 305.


16/18

G.K. Folas, G.M. Kontogeorgis, M.L. Michelsen, E.H. Stenby, Ind. Eng. Chem. Res., 2006, 45(4),

1516.

Muro-Su, N., Kontogeorgis, G.M., von Solms, N., and Michelsen, M.L., Ind. Eng. Chem. Res.,

2008, 47, 5660.

G.K. Folas, S.O. Derawi, M.L. Michelsen, E.H. Stenby G.M. Kontogeorgis, Fluid Phase Equilibria,

2005, 228-229, 121.

G.M. Kontogeorgis, M.L. Michelsen, G. Folas, S. Derawi, N. von Solms, E.H.Stenby, Ind. Eng.

Chem. Res., 2006, 45(14), 4869.

G.K. Folas, G.M. Kontogeorgis, M.L. Michelsen, E.H. Stenby, Ind. Eng. Chem. Res., 2006,45,

1527.

G.K. Folas, G.M. Kontogeorgis, M.L. Michelsen, E.H. Stenby, Fluid Phase Equilibria, 2006, 249,

67-74.

Caption of Table A.5.

The following sentence should be added:

The parameters are taken from a broad collection of publications which is presented at the

end of table A.6

The list of publications at the end of Table A.6, part Collection of parameters should be

updated, as follows:

Collection of parameters from the Lyngby group (Kemiteknik-DTU) based on the following

publications:Kouskoumvekaki et al, Fluid Phase Equilibria,2004, 215,71-78

Kouskoumvekaki et al,Ind. Eng. Chem. Res.,2004, 43, 2830-2838

Kouskoumvekaki et al,Ind. Eng. Chem. Res.,2004, 43, 826-834

von Solms et al.,Ind. Eng. Chem. Res., 2003, 42, 1098-1105

von Solms et al, Fluid Phase Equilibria,2004, 222, 87-93



17/18

von Solms et al.,Ind. Eng. Chem. Res.,2004, 43, 1803-1806



Grenner et al.,Ind. Eng. Chem. Res., 2006, 45, 8170-8179

Grenner et al.,Ind. Eng. Chem. Res., 2008, 47, 5636-5650

Tsivintzelis et al.,Ind. Eng. Chem. Res., 2008, 47, 5651-5659

Grenner et al., Fluid Phase Equilibria,2007, 258, 83-94

Grenner et al., Fluid Phase Equilibria,2007, 261, 248-257

Grenner et al.,Mol. Physics,2007, 13-14, 1797-1801

Tihic et al., Fluid Phase Equilibria, 2006, 248, 2943

Tihic A., Group Contribution sPC-SAFT Equation of State. Ph.D. Thesis, Technical University of

Denmark, 2008.

At the end of Appendix B the following text should be added

References for the CPA interaction parameters

Alcohol-hydrocarbons, alcohol-water (tables B.1-B.4)

G.K. Folas, J. Gabrielsen, M.L. Michelsen, E.H. Stenby, and G.M. Kontogeorgis.

Ind. Eng. Chem. Res., 44:38233833, 2005

G.K. Folas, S.O. Derawi, M.L. Michelsen, E.H. Stenby, and G.M. Kontogeorgis,


Acid-containing mixtures (tables B.5-B.7, B13-should read B.13b, B.14, etc)

S.O. Derawi, J. Zeuten,M.L.Michelsen, E.H. Stenby, and G.M. Kontogeorgis, Fluid Phase Equilib.,

225:107113, 2004.

Muro-Su, N., Kontogeorgis, G.M., von Solms, N., and Michelsen, M.L., Ind. Eng. Chem. Res.,

2008, 47, 5660.


18/18

G.M. Kontogeorgis, G.K. Folas, N. Muro-Sun, N. von Solms, M.L. Michelsen, E.H. Stenby, Fluid

Phase Equilibria, 2007, 261, 205.

G.M. Kontogeorgis, G.K. Folas, N.Muro-Su, F. Roca Leon, M.L. Michelsen, OGST - Revue de

IIFP, 2008, 63, 305.

Glycol-containing mixtures (tables B.8, B.9)

(In B.9 ECR should be written instead of Elliott)

S.O. Derawi, G.M. Kontogeorgis, M.L. Michelsen, and Stenby E.H, Fluid Phase Equilib., 209:163

184, 2003.

G.K. Folas, G.M. Kontogeorgis, M.L. Michelsen, and E.H. Stenby, Ind. Eng. Chem. Res., 45:1527

1538, 2006.

S.O. Derawi, G.M. Kontogeorgis, M.L. Michelsen, and Stenby E.H. ,Ind. Eng. Chem. Res.,

42:14701477, 2003.

Amines (Tables B.10-B.12)

(In B.11 ECR should be written instead of Elliott)

M. Kaarsholm, S.O. Derawi, M.L. Michelsen, and G.M. Kontogeorgis,Ind. Eng. Chem. Res.,

44:44064413, 2005.

Water-hydrocarbons (Table B.13should read B.13a)

G.K. Folas, G.M. Kontogeorgis, M.L. Michelsen, and E.H. Stenby, Ind. Eng. Chem. Res., 45:1527

1538, 2006.

Chemicals (acetone, etc)

G.K. Folas, G.M. Kontogeorgis, M.L.Michelsen, and E.H. Stenby, Ind. Eng. Chem. Res., 45:1516

1526, 2006.

G.K. Folas et al., 2009. The Cubic-Plus-Association EoS. Parameters for pure compounds and

interaction parameters. Technical Report (Editor: Martin P. Breil), IVC-SEP, DTU Chemical

Engineering.

Book Corrections for Thermodynamic Models

Documents

Transcript of Book Corrections for Thermodynamic Models