Table Of ContentVolume Properties
Liquids, Solutions and Vapours
Volume Properties
Liquids, Solutions and Vapours
Edited by
Emmerich Wilhelm
Institute of Physical Chemistry, University of Vienna, Vienna, Austria
Email: [email protected]
Trevor M. Letcher
University of KwaZulu-Natal, Durban, South Africa
Email: [email protected]
PrintISBN:978-1-84973-899-6
PDFeISBN:978-1-78262-704-3
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
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Preface
Themajorityofchemicalprocessesofinterestoccurinthefluidstate.Thus,
gases or vapours, pure liquids and liquid solutions are of prime scientific
and engineering importance, and many of the most significant develop-
mentsinphysicalchemistryandchemicalphysics(iftheyare,indeed,fields
apart), biophysical chemistry and chemical engineering are based on con-
tributions originating from chemical thermodynamics as applied to fluid
systems.1–3Themostprofitableapproachforpracticalapplicationsaswellas
theoretical advances is based on a combination of chemical thermo-
dynamicswithmolecular theoryand statisticalmechanics,therebycreating
the field of molecular thermodynamics (this term was coined by Prausnitz
more than four decades ago). The continuously increasing number of
articles reporting experimental data on thermodynamic properties of
fluids (pure and mixed) and on fluid phase equilibria, as well as on novel
experimental techniques, improved data reduction methods, advances in
molecular theory and computer simulation, demonstrate the unabated
growthofthisfield.Ofparticularnoteareactivitiesinbiophysicalchemistry
aimed to broaden our understanding of the thermodynamic basis of
physico–chemical phenomena associated with biological processes.
Volume properties belong to the most important thermodynamic/ther-
mophysicalproperties,andplayacentralroleinthepuresciencesaswellas
in chemical engineering and industrial applications. For instance, virial
coefficients and their temperature derivatives allow the description of
many thermophysical properties of real gases, an approach thoroughly
grounded in statistical mechanics. For gases/vapours as well as dense
liquids,PVTxdataorPr Txdataprovidethebasicinputforthedevelopment
n
of equations of state (EOS) valid for both pure fluids and fluid mixtures
which are based on the pioneering ideas of van der Waals.4 Here, P is
the pressure, V is the molar volume, T is the temperature, r ¼1/V is the
n
VolumeProperties:Liquids,SolutionsandVapours
EditedbyEmmerichWilhelmandTrevorM.Letcher
rTheRoyalSocietyofChemistry2015
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
vi Preface
amount-of-substance density and x is the mole fraction. There can be little
doubtthatthemostpopularclassofEOSistheonecomprisingtheso-called
cubic EOS, which evolved from the famous equation proposed by van der
Waals in his PhD dissertation at the University of Leiden in 1873:
RT a
P¼ (cid:2) :
V (cid:2)b V2
Here, R denotes the (molar) gas constant, and a and b are positive
parameters characterising attraction and repulsion, respectively, in a
particular fluid. Over the past five decades, numerous improved modifi-
cations were developed (including extensions to multicomponent mixtures
via semiempirical mixing rules and combination rules), and these general-
isedvanderWaalsequationsremainindispensableforappliedresearchand
development in chemical engineering. In contradistinction, modern
thermodynamic property formulations for fluids are based on fundamental
equations that are usually explicit in the Helmholtz energy as a function of
temperature and density.5 These semiempirical fundamental ‘‘equations of
state’’ allow the calculation of any thermodynamic fluid property via
differentiation only. For developing such an accurate multi-parameter
Helmholtz energy-based EOS, besides extensive density data, perfect-gas
state heat capacities as a function of temperature are essential, and vapour
pressures. In addition, high-precision data of the thermodynamic speed of
ultrasound (that is sound speeds at sufficiently low frequencies, well below
the dispersive region) are becoming increasingly important. However, the
required amount of experimental input data and state-of-the-art data treat-
ment is considerable, and the equations available for selected pure liquids
still have benchmark character.6,7
Liquid mixtures are usually more easily dealt with via properties that
measure their deviation from ideal-solution behaviour, that is to say, via
excess properties as a function of temperature, pressure and composition.8
Excess molar volumes VE(T,P,{x})¼(@GE(T,P,{x})/@P) are of particular
i i T,{x}
i
importance,andChapter7isdevotedtothistopic;here,{x}denotestheset
i
ofcompositionalvariables(molefractions)andGEistheexcessmolarGibbs
energy.Finally,wewouldliketopointoutthat,duringthelasttwodecades,
research activities have been rapidly extended to include volumetric
properties of multicomponent systems of increased complexity, including
systemsandprocessesofbiochemicalinterest,9suchasproteinsinaqueous
solutions,10,11 and the protein folding problem in vitro and in the cellular
environment.12,13
In this monograph the reader will find 22 contributions dealing with
volume properties and related thermodynamic properties of liquid systems
and gases/vapours, both pure and mixed. The topics are approached from
different angles representing the varying research background of the re-
spective authors. This book has its origin in committee meetings of the
International Association of Chemical Thermodynamics (IACT) which is an
Preface vii
associate organisation of the International Union of Pure and Applied Chem-
istry (IUPAC). The IACT developed from the IUPAC Commission on Thermo-
dynamics and has continued to play an active role in the definition and
maintenance of standards in all aspects of thermodynamics and in the de-
velopmentofthesubjectandtheencouragementofyoungscientiststotake
up research careers in chemical thermodynamics (further information can
be found at www.IACTweb.org).
This book, entitled Volume Properties: Liquids, Solutions and Vapours, is
publishedundertheauspicesofbothIACTandIUPAC.Ontheonehand,it
continuesthetopic-orientedapproachrepresentedbytherecentmonograph
entitledHeatCapacities:Liquids,SolutionsandVapours,editedbyE.Wilhelm
and T. M. Letcher, and published in 2010 (Royal Society of Chemistry,
Cambridge),andontheotherhanditmaybeconsideredasanothervolume
in the tradition of the long line of books that started in 1956 with Experi-
mental Thermochemistry, Volume I (Interscience Publishers, Inc., New York)
editedbyF.D.Rossini,andExperimentalThermochemistry,VolumeII,edited
by H. A. Skinner, and published in 1962 (Interscience-Wiley, New York).
Followingthesetwomonographs,overtheyearsaseriesofbooksonvarious
aspectsofexperimentalthermodynamics(inabroadsense)havebeenadded.
Sofar,eightvolumeshavebeenpublished:(a)VolumeI,CalorimetryofNon-
Reacting Systems, edited by J. P. McCullough and D. W. Scott (Butterworths,
London, 1968); (b) Volume II, Experimental Thermodynamics of Non-Reacting
Systems,editedbyB.LeNeindreandB.Vodar(Butterworths,London,1975);
(c) Volume III, Measurement of the Transport Properties of Fluids, edited by
W. A. Wakeham, N. Nagashima and J. V. Sengers (Blackwell Science Publi-
cations, Oxford, 1991); (d) Volume IV, Solution Calorimetry, edited by K. N.
Marsh and P. A. G. O’Hare (Blackwell Science Publications, Oxford, 1994);
(e) Volume V, Equations of State for Fluids and Fluid Mixtures, edited by J. V.
Sengers, R. F. Kayser, C. J. Peters and H. J. White, Jr. (Elsevier, Amsterdam,
2000); (f) Volume VI, Measurement of the Thermodynamic Properties of Single
Phases, edited by A. R. H. Goodwin, K. N. Marsh and W. A. Wakeham
(Elsevier, Amsterdam, 2003); (g) Volume VII, Measurement of the Thermo-
dynamicPropertiesofMultiplePhases,editedbyR.D.WeirandT.W.deLoos
(Elsevier, Amsterdam, 2005); and (h) Volume VIII, Applied Thermodynamics
of Fluids, edited by A. R. H. Goodwin, J. V. Sengers and C. J. Peters (Royal
Society of Chemistry, Cambridge, 2010).
In true IUPAC spirit, the authors represent some of the most important
names in their respective fields and come from many countries around the
world, including: Australia, Austria, Belarus, Canada, Czech Republic,
France, Germany, Israel, Japan, Poland, Russia, South Africa, Spain, United
Kingdom and the United States of America.
One of the objectives of the book is to bring together research from
disparate disciplines which have a bearing on volume properties of fluids.
Cross-links between these chapters, we believe, will lead to new ways of
looking at volume property-related issues, and thus to new ways of solving
associatedproblemsinphysics,chemistryandengineering.Underlyingthis
viii Preface
philosophyisourinherentbeliefthatabookisstillanimportantvehiclefor
the dissemination of knowledge.
Two features are of paramount importance in monographs like this one:
the timeliness of the topic and the coverage and critical evaluation of the
pertinent publications. In fact, important features of this book include the
underlying theory, some of the most important experimental techniques,
modelling and computer simulation, as well as significant and new results
related to volume properties. The authors have endeavoured to cover the
relevantliteratureupto2013.Thisbookismeantforresearchersinchemical
thermodynamics, either from academia or from chemical industry, and
providesanoverviewoftheprogressrecentlyachieved.Itssuccessultimately
restswiththe32authorsandwe,theeditors,wouldliketothankallofthem
for their cooperation and enthusiastic contributions which are highly
valued.WewouldalsoliketothankProfessorRonWeirwho,onbehalfofthe
IUPAC subcommittee, the Interdivisional Committee on Terminology, Nomen-
clature and Symbols (ICTNS), checked each chapter for the correct usage of
thermodynamic quantities, units and symbols, always exercising the liberal
spirit invoked in the Green Book of IUPAC.14 Finally we wish to thank the
Royal Society of Chemistry, whose representatives were helpful and patient
in producing this monograph on Volume Properties.
Emmerich Wilhelm
Institute of Physical Chemistry,
University of Wien (Vienna),
Wien (Vienna), Austria
Trevor M. Letcher
University of KwaZulu-Natal,
Durban,
South Africa
References
1. J. H. Hildebrand, J. M. Prausnitz and R. L. Scott, Regular and Related
Solutions. The Solubility of Gases, Liquids, and Solids, Van Nostrand
Reinhold Company, New York, USA, 1970.
2. J. S. Rowlinson and F. L. Swinton, Liquids and Liquid Mixtures,
Butterworth Scientific, London, UK, 3rd edn, 1982.
3. J. M. Prausnitz, R. N. Lichtenthaler and E. G. de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, Prentice Hall PTR, Upper
Saddle River, NJ, USA, 3rd edn, 1999.
4. J. D. van der Waals, On the Continuity of the Gaseous and Liquid States,
ed. (and with an Introduction by) J. S. Rowlinson, Dover Publications,
Inc., Mineola, NY, USA, 2004.
5. (a) R. T. Jacobsen, S. G. Penoncello, E. W. Lemmon and R. Span,
Multiparameter Equations of State, in Equations of State for Fluids and
Preface ix
Fluid Mixtures: Experimental Thermodynamics, Vol. V, ed. J. V. Sengers,
R.F.Kayser,C.J.PetersandH.J.WhiteJr.,Elsevier/IUPAC,Amsterdam,
The Netherlands, 2000, ch. 18, pp. 849–881; (b) E. W. Lemmon and
R. Span, Multi-parameter Equations of State for Pure Fluids and
Mixtures, in Applied Thermodynamics of Fluids, ed. A. R. H. Goodwin,
J. V. Sengers and C. J. Peters, Royal Society of Chemistry/IUPAC,
Cambridge, UK, 2010, ch. 12, pp. 394–432.
6. International Thermodynamic Tables of the Fluid State, IUPAC: Vol. 1,
Argon, ed. S. Angus, B. Armstrong and K. M. de Reuck, Butterworths,
London, UK, 1972 through Vol. 13, Methane, ed. W. Wagner and K. M.
de Reuck, Blackwell Scientific, Oxford, UK, 1996.
7. W. Wagner and A. Pruß, The IAPWS Formulation 1995 for the
Thermodynamic Properties of Ordinary Water Substance for General
and Scientific Use, J. Phys. Chem. Ref. Data, 2002, 31, 387–535.
8. J. P. O’Connell and J. M. Haile, Thermodynamics: Fundamentals for
Applications, Cambridge University Press, New York, NY, USA, 2005.
9. M. Gruebele and D. Thirumalai, Perspective: Reaches of chemical
physics in biology, J. Chem. Phys., 2013, 139, 121701–1–121701-9.
10. Frontiers in High Pressure Biochemistry and Biophysics, ed. C. Balny,
P. Masson and K. Heremans, Elsevier Science B. V., Amsterdam, The
Netherlands, 2002.
11. T. V. Chalikian, Volumetric Properties of Proteins, Annu. Rev. Biophys.
Biomol. Struct., 2003, 32, 207–235.
12. K. A. Dill, S. B. Ozkan, M. S. Shell and T. R. Weikl, The Protein Folding
Problem, Annu. Rev. Biophys, 2008, 37, 289–316.
13. D. Thirumalai, E. P. O’Brien, G. Morrison and C. Hyeon, Theoretical
Perspectives on Protein Folding, Annu. Rev. Biophys, 2010, 39, 159–183.
14. International Union of Pure and Applied Chemistry: Quantities, Units and
Symbols in Physical Chemistry, RSC Publishing/IUPAC, Cambridge, UK,
3rd edn, 2007.
