Physical Chemistry from a Different Angle: Introducing Chemical Equilibrium, Kinetics and Electrochemistry by Numerous Experiments

654 Pages·2016·13.4 MB·English

by  Georg Job

Georg Job
Regina Rüffl er
Physical Chemistry
from a Diff erent
Angle
Introducing Chemical Equilibrium,
Kinetics and Electrochemistry by
Numerous Experiments
Physical Chemistry from a Different Angle
ThiSisaFMBlankPage
Georg Job • Regina Ru¨ffler
Physical Chemistry from
a Different Angle
Introducing Chemical Equilibrium, Kinetics
and Electrochemistry by Numerous
Experiments
GeorgJob ReginaRu¨ffler
JobFoundation JobFoundation
Hamburg Hamburg
Germany Germany
TranslatedbyRobinFuchs,GETS,Winterthur,Switzerland
HansU.Fuchs,ZurichUniversityofAppliedSciencesatWinterthur,Switzerland
ReginaRu¨ffler,JobFoundation,Hamburg,Germany
BasedonGermanedition“PhysikalischeChemie”,ISBN978-3-8351-0040-4,publishedby
SpringerVieweg,2011.
Exercisesaremadeavailableonthepublisher’swebsite:
http://extras.springer.com/2015/978-3-319-15665-1
BycourtesyoftheEduard-Job-FoundationforThermo-andMatterdynamics
ISBN978-3-319-15665-1 ISBN978-3-319-15666-8 (eBook)
DOI10.1007/978-3-319-15666-8
LibraryofCongressControlNumber:2015959701
SpringerChamHeidelbergNewYorkDordrechtLondon
©SpringerInternationalPublishingSwitzerland2016
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this
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arebelievedtobetrueandaccurateatthedateofpublication.Neitherthepublishernortheauthorsorthe
editorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinorforanyerrors
oromissionsthatmayhavebeenmade.
Printedonacid-freepaper
Springer International Publishing AG Switzerland is part of Springer Science+Business Media
(www.springer.com)
Preface
Experience has shown that two fundamental thermodynamic quantities are espe-
cially difficult to grasp: entropy and chemical potential—entropy S as quantity
associatedwithtemperatureTandchemicalpotentialμasquantityassociatedwith
the amount of substance n. The pair S and T is responsible for all kinds of heat
effects, whereas the pair μ and n controls all the processes involving substances
suchaschemicalreactions,phasetransitions,orspreadinginspace.Itturnsoutthat
Sandμarecompatiblewithalayperson’sconception.
In this book, a simpler approach to these central quantities—in addition to
energy—is proposed for the first-year students. The quantities are characterized
bytheirtypicalandeasilyobservableproperties,i.e.,bycreatingakindof“wanted
poster” for them. This phenomenological description is supported by a direct
measuringprocedure,amethodwhichhasbeencommonpracticeforthequantifi-
cationofbasicconceptssuchaslength,time,ormassforalongtime.
The proposed approach leads directly to practical results such as the predic-
tion—baseduponthechemicalpotential—ofwhetherornotareaction runsspon-
taneously.Moreover,thechemicalpotentialiskeyindealingwithphysicochemical
problems. Based upon this central concept, it is possible to explore many other
fields. The dependence of the chemical potential upon temperature, pressure, and
concentration is the “gateway” to the deduction of the mass action law, the
calculation of equilibrium constants, solubilities, and many other data, the con-
struction of phase diagrams, and so on. It is simple to expand the concept to
colligative phenomena, diffusion processes, surface effects, electrochemical pro-
cesses, etc. Furthermore, the same tools allow us to solve problems even at the
atomic and molecular level, which are usually treated by quantum statistical
methods. This approach allows us to eliminate many thermodynamic quantities
thataretraditionallyusedsuchasenthalpyH,GibbsenergyG,activitya,etc.The
usage of these quantities is not excluded but superfluous in most cases. An opti-
mized calculus results in short calculations, which are intuitively predictable and
canbeeasilyverified.
v
vi Preface
Because we choose in this book an approach to matter dynamics directly by
usingthechemicalpotential,applicationoftheconceptofentropyislimitedtothe
descriptionofheateffects.Still,entropyretainsitsfundamentalimportanceforthis
subjectandiscorrespondinglydiscussedindetail.
Thebookdiscussestheprinciplesofmatterdynamicsinthreeparts,
• Basicconceptsandchemicalequilibria(statics),
• Progressionoftransformationsofsubstancesintime(kinetics),
• Interactionofchemicalphenomenaandelectricfields(electrochemistry)
and gives at the same time an overview of important areas of physical chemistry.
Becausestudentsoftenregardphysicalchemistryasveryabstractandnotusefulfor
everyday life, theoretical considerations are linked to everyday experience and
numerousdemonstrationexperiments.
We addressthisbooktoundergraduatestudentsincourseswherephysicalchem-
istryisrequiredinsupportbutalsotobeginnersinmainstreamcourses.Wehaveaimed
tokeeptheneedsofthisaudiencealwaysinmindwithregardtoboththeselectionand
the representation of the materials. Only elementary mathematical knowledge is
necessary for understanding the basic ideas. If more sophisticated mathematical
tools are needed, detailed explanations are incorporated asbackground information
(characterizedbyasmallerfontsizeandindentation).Thebookalsopresentsallthe
materialrequiredforintroductorylaboratorycoursesinphysicalchemistry.
Exercisesaremadeavailableonthepublisher’swebsite.Astudentmanualwith
commentedsolutionsisinpreparation.Detaileddescriptionsofaselectionofdem-
onstrationexperiments(partlywithcorrespondingvideosclips)canbefoundonour
web site (www.job-foundation.org; see teaching materials); the collection will be
continuouslyextended.Furtherinformationtothetopicsofquantumstatisticsandthe
statisticalapproachtoentropy,which wouldgobeyondthescopeofthisbook, can
alsobecalleduponthefoundation’shomepage.
Preface vii
{
We would particularly like to thank Eduard J. Job , the founder of the Job
Foundation, who always supported the goals of the foundation and the writing of
thecurrentbook,withgreatpersonalcommitment.Becauseefficientapplicationof
thermodynamics played an important role in his work as an internationally suc-
cessful entrepreneur in the field of fire prevention and protection, he was particu-
larlyinterestedinasimplifiedapproachtothermodynamicsallowingforfasterand
moresuccessfullearning.
Wegratefullyacknowledgetheconstantsupportandpatienceoftheboardofthe
Job foundation. Additionally, we would like to thank the translators of the book,
Robin Fuchs and Prof. Hans U. Fuchs, for their excellent collaboration, and
Dr.SteffenPaulyandBeateSiekatSpringerfortheiradviceandassistance.Finally,
wewouldliketoexpressourgratitudetocolleagueswhogavetheiradviceonthe
GermaneditionandrevieweddraftchaptersoftheEnglishedition:Prof.Friedrich
Herrmann,Prof.Gu¨nterJakobLauth,Prof.FriedhelmRadandt,andDr.Uzodinma
Okoroanyanwu.
Wewouldbeverygratefulforanycontributionsorsuggestionforcorrectionsby
thereaders.
Hamburg,Germany GeorgJob
November2014 ReginaRu¨ffler
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List of Used Symbols
In the following, the more important of the used symbols are listed. The number
added in parentheses refers to the page where the quantity or term if necessary is
described indetail. Special characters as prefix (j, Δ, Δ , Δ , ...) were omitted
R s!l
whenorderingthesymbolsalphabetically.
Greeklettersinalphabeticalorder:
ΑαΒβΓγΔδΕεΖζΗηΘθϑIιKκΛλMμΝvΞξΟoΠπΡρΣσςΤτΥυΦφΧχ
ΨψΩω.
Roman
A,B,C,... SubstanceA,B,C,...
jA,jB,... DissolvedinA,inB,...(240)
Ad Acid(188)
a,ja Amorphous(19)(alsosubscriptedorsuperscripted)
Bs Base(188)
C Catalyst(462)
c,jc Crystalline(19)(alsosubscriptedorsuperscripted)
d,jd Dissolved(19)(alsosubscriptedorsuperscripted)
E Enzyme(466)
e,e(cid:2) Electron(s)(7,553)(alsosubscripted)
e Eutectic(367)(alsosubscriptedorsuperscripted)
F Foreignsubstance(320)
g,jg Gaseous(19)(alsosubscriptedorsuperscripted)
J Ion,unspecific(533)
l,jl Liquid(19)(alsosubscriptedorsuperscripted)
M Mixture(homogeneous)(346)
M Mixture(heterogeneous)(348)
Me Metal,unspecific(533)
m,jm Metallic(conductingelectrons)(553)(alsosubscriptedor
superscripted)
Ox Oxidizingagent(537)
ix