I

1
Principles Thermodynamic Functions The Ideal Gas

It would be inaccurate to say thai the development of thennodynamics is not based on

experimentation. II is from observation thai the concepts of quantity of heal, of temperalure, of energy of II system. and of irreversibility have been c1cveloped. However, there was an importanlluming lXlinl when the statements orlhe first and second laws allowed us not only to "condense" the observations that produced them, but also to establish a priori la....'5 that subsequent observations have verified, to generalize from them and diversify the field of their application. The greatest diversity cKists, however. within the field of thermodynamics. Mechanical engineers, energy specialists.. and chemists apply the Slime principles.. but they have constructed their own conventions renecting lheir practical concerns. Many statemenlS of Ihese principles can be sel forth and il is nOllhe goal of lhis chapter 10 enumerate them or to demonslrale lheir equivalence. For lhe most part. they arc familiar 10 the reader who may. if he 50 wishes. consult lhe general references listed in lhe bibli ography.ln this chapter. we will limit ourselves to a few lopics emphasizing the points lhal seem most imporlanlto us for the rest of this study. First. we must review the lerminology proper to lhermodynamics. We derive our inspiration rrom the teachings of A. Pl!ncloux 119921.

1.1

DEFINITIONS

Thermodynamics applies to a physical entity. lhe "s}"Slem". possibly composed or distinct parts. or "subsyslems-. The system is defined only if its physical limitalions or "bound. aries- are specified. as well as the nalure of lhe exchanges lhat il may maintain with the or "open" accordrest or lhe universe (..the surroullodinp"). The syslem is termed ing 10 whether or nOI exchanges of maller arc possible. For cltample. ils properties may change duc to differences of tcmpeTlllure or pressure belween the syslem and lhe surroundings. Its boundaries on the other hand may reSiSl such IranSfOrmalions. The energy exchanges ,,'Ith the SUTroundinp will therefore havc 10 be specified according 10 the exchanges or mailer. Similarly. certain changes may be excluded by virtue of internal

,
oonslrllints: first and foremost. those changes defining the possible bollndaries of tems lhat may be rued or mobile. adiabatic or diathermic. impermeable or porous. It is also well known thai ccrtllin chemical reactions occur onl)' wilh a calalrst or an iniliator. Ihal olher reactions may be inhibited and. for example. 1hal we may apply Ihe laws of thermodynamics to the solubility of air in hydrocarbons withollt being concerned 300m the possibility of comhustion. As with boundaries. tllese constraints must also be specified in order to describe 11 "system" and lhc changes that we may expect or exclude. The most nalural subsystems thai we can define are made up of the phases into which maHer is organi:red. In panicular. we slllll1 sllIdy Ihe equilibria between the liquid and vapor phases. A "pbllse" forms a "homogeneous" physical entity in thc sense that all the parts of equal volume have the &amc properties (they have the same quantity of malter, the same composition, etc.). With a defined system. in principlc wc may describe its "5111"" by dctermining its crttes. or stille '"II.lucs", meaning the entirety of what is "observable": temperawre. pressure, volumc, quantity of maller, and composition. for example. These properties are not totally independent. and we Itnow very weHthat the volume occupied b)' a system is fixed from the moment we Itno'" the quantities of each component, the pressure. and the temperawre. Within the scope of this these properties can be defined only for "slelld}oSllIlc" sys terns whose slate does not change over the course of time (and whose state does nOt depend on its development), In fact. this steady-state is often due to the of appropriate boundaries or constraints. and insofar as these boundaries are precisely described, we will state that the system is in a state of "equilibrium", This means that the system will return to this state after any infinitesimal disturbance with respect to its bound aries-A state of equilibrium depends on the constraints imposed on the system:eonstraints which we will talte into account when defining and applying the conditions of equilibrium stated in the laws of thermodynamics. Some of these properties are "additive" in the sense that if we nawrally or artificially divide thc syslCm into several parts. such a property of the whole is calculated by using the sum of the values of this property in each of the parts. For a homogeneous system. this value is proportional to the size of the system, namely the quantity of matter. Volume is the simplest cxample of such a property. but it is the same for internal energy. entropy. etc.. which we will define later. Such properties are termed 'c.:tensi"c" and we shall consistently denote them by the capital letter symbols V. U. S. cte. On the other hllfld. other properties in a homogeneous 5ystcm arc independent of the size of the s)stem: density. pressure, temperatuTC. cte. They are termcd "iutensh'c" and on this subject, we recall the definition given by Pc!ncloux [1992]: "phase fcfefli to the entirety of intensive properties". Among these properties arc some that govern the equilibrium among the various parts of a syStem. If twO parts arc separated by a mobile boundary. the pressures must be the same in each part.ll is the &ame with temperatures if the boundary is diathermic. and with the chemical potential (which we shall define in Chapter 5) of each component if the boundary does not resist exchanges of matu::r. Such intensive properties are "potentials" and intervene in conjunction with corresponding extensive properties: volume, entropy, and quantities of mailer. There are other intensive properties defined by

3
lhe value taken by an extensive propcny for Ihe unit of mailer (one mole): molar volume. molar heat capacity. etc. These are sometimes referred to as We shall give them the same symbols. but in lower case: v, molar volume. II, internal molar energy. elc. If ceflain constraints thai assure the equilibrium of a system aTc removed. lhe system generally undergoes a "Innsformlilion", and changes via a series of intermediate states 10 a new state of equilibrium. This ,hangc I;l(1;lITS by variation of its properties. and. in gen eraL by "energy exdlllnKH" with lhe surroufldings. such as the work done by pressure. if ilS volume changes. for example. In some cases. we can imagine thallhe opposite progression might be possible. II would then be a "",vII'Qible" transformation. and in panicular. il might occur via a series of closely related states of equilibrium in wlliclltlle properties of tile system do not cllange from one state to tile next except in a finite manner. We arc lllen speaking about a '"quasistalic:" transformation. To accomplislltllis.tlle motive agenlS of tllis transformation will c:ontinually adapt to tile state of tile system. Sucll is tile case witll a compression process during wllicll tile extemal pressure remains practically equal 10 tllat of tile system, or witll a transfonnation due to an infinitesimal differenlX in temperature.

1.2

THE FIRST LAW

1.2.1 The Energy of a System

The first law is based on attributing an extensive property to any closed material system, namety energy. and on the establishmenl of an exaet balance between the variations of this properly during tile course of a transformation on tile one Iland. and on the other. tile work accumplislled by the surrounding environment due to mechanical. electrical. and magnetic forces. as well as so-called heat exchanges caused by differences in temperature. Certain components of energy are familiar and independent of tile internal structure of the system. In the first place. they involve p<ltenlillJ energy in the gravitational field 1""" which is expressed as a function of mass m. the acceleration of gravity g. and the calculaled elevation compared to an arbitrary reference Z. It is the same for the kineli<: t'neTV of the that is related to ma5S.,to tht' moment of inertia, and to the speed of the entire system. system. Mechanics is a function of these components. In themlodynamics we also take into aceount""intemal energy"", U, which originates from: First and foremost, the kinetic energy tllatll.ccompanies the random movement of the molecules that make up the syslem (translalion, rotation of all or pari of lhe molecule, longitudinal or transversal vibrations of the interatomic bonds), Ii determines the properties of lhe '"ideal gas"". Secondly. the intennolecular cohesive energy related to the forces of altraclion lind repulsion between the molecules. Opposing the disordered kinetic agitation of molecules. they contribute 10 the organization of maHer in different phases. And finally. the interatomic cohesive energy thaI assures the stability of the molecu lar structure and is evidenl during chemical reactions.

p'

Of course. it would be appropriate to quantify the intraatomic cohesive energies that are much mOTC numerous. but they do not occur in the phenomena studied here thai preserve the structure of the Dtom. As with the potential energy in the gravitational field. internal energy can be calculated only in relation to an arbitrary reference.
We therefore write:

'" Epc>< +

+U

(1.1)

In the problems we present here. m05t oftell the variations of potential energy in the gravitational field and in the kinetic energy of the system will be leTO or negligible. The variations of system energy will be reduced to variations of internal energy.

1.2.2 Energy Exchanges during a Transformation

When the system in question changes from one Slale of equilibrium to a new stale of equilibrium due to the removal of certain constraints that insured the stability of the initial state. this transformation is accompanied b), energ), exchanges with the surrounding environment. We shall now attempt to specif)' the nature of these exchanges- For the most part, the)' are altributable to external forces acting on the system. and in particular, to Ihe forces of pressure.lrthe pressure acting on the s)'stem is designated p...,. the work supplied to the system Clln be expressed by the equation:

DlV

dV

(1.2)

For this tmnsformatioll to be reversible. it is necessary that the pressure acting on the system p., be equal to the prevailing pressure within the system P. and the work dW_ will then be cqual to: (1.3) SW... =-PdV If we take into account the sign of the variation of volume dV that is related to the vIIIues of p... and P respectivel)'. we can easil)' convince ourselves that:

DlV ... 8IV...

or

OW"'-PdV

(1.4)

It is similarl), appropriate to point out. for example. the work due to the presence of electrical and magnetic fields surrounding the S)'l'lem.ln general the)' will be absent from the transformations that we will stud)', and as a reminder we shall designate them here as W'. We also know Ihat. due to the difference in temperature between the surrounding environment and the S)'l'tem.the state of the system rna)' change. It is customary to state that the surrounding environment "provides heat" to the system. Certainly this statement is incorrect as neither the surroundings nor the system possesses heat. Nevertheless. we retain this term as it has passed into practice and is unambiguous. These heat exchanges Shall be designated h)' Q. or for an infinitesimal transformation. b)' OQ.

1. f'r;"dples. ThonKJdynamic Func:,iorn. """ kiNl Gas

1.2.3 Statement of the First Law Applied to a Closed System

1.2.3.1 General
TIle ftrJI ....., applied 10. dosed syslem,est.bUsMs ... eltJld balance boetWft.. lbe \'aliItio" 01 the 10taJ eDe1JY 01 the system dari"a'''Y tramlormation. 01" lrn"ersible. and lhe total_rk. and lbe Glhe.t Ib$orbed by thl! system:
<1E_I1(E,..+Eklo +U)_W+W'+Q (1.5)

lite symbol 11 daip.les e"Mrgy nn.Uon: E_ - E_, Very often. when retaining only the internal energy ...ariation!!.. tbe work done by pressure and the thennal uehanges. wc shall write the equation in the fonn:
(1.6a)

or. for an infinitesimal change. as:

dU",(jQ+5W'

(1.6b)

At this point. it is appropriate to consider a few particular cases that colTcspond to this simplified ...ersion of the firsllaw.

1.2,3,2 lsochoric Transformations

If the transfonnation in question takes place at constant YOlume and the work done by

pressure is equal to zero. the preceding equation is redlll;:ed to:

/J,Uv"'Q ..
or. ror an infinitesimal change. 10:

(l.7a) (l.7b)

The thennal e:o;changes accompanying an isochoric transfonnation therefore correspond to the ...ariat;on of the internal energy of the system. If this transfonnation has as its only dfe<:t a ...ariation in the temperalure of the system (Ihere is neither a change in phase nor a chemicallransfonnation). the heat exchanges may thcn be e:o;prcssed as a [unction of the heal capacity al conslant YOlume. CO', and of Ihe temperature ...ariation:
( 1.8)

1.2.3.3 Adiabatic Compression

In Ihis case. thermal exchanges equal zero. and the work done by adiabalic compTC5Sion is upressed as:
(1.9)


1.2.3.4 Transformations at Constant Pressure
Ir the eKlernal pressure is constant. and the system is in pressure equilibrium with the surroundings at bmh the onset and allhe end of this lransfonnalion.lhe work done by pre$sure is expressed by lhe equation;
lY,.=_P. L\V (1.10)

and. if we tate into account the pressure equilibrium conditions at both the beginning and allhe cnd of Ihe transformation. we can write:
POl' lI.V=L\(PV),.

where P stands for the s)"llcm pressure. such lhal Ihe first law 3110....11 us to caleulate the quantity of heal exchanged:
(1.11) TIle sum U.;. PV is the "enlhldpy" of the system. [\ is an extensive property just like internal energy and volume. It is more commonly used in practical calculations because the prcvioWi equation relales thc!;!: variations to isobaric hcal Cllehanges. II is also used in thc cllpression of the first law applied to open systcms. as we shall see subsequenlly.ll is designated by the symbol H: H=U+PV (1.12)

such that we can write:

(1.13)

Thcreforc thc quantities of heat nccessary for fusion. for lhe vaporization of a pure substance. or for a chemical reaction performcd at constant pressure will oflen be called "enthalpy of fusion" (negative of lhe enlhalpy of melting), "cnthalpy of vaporization" or enthalpy of reaction". If lhc only cffcct of the transformation is 10 ellUse a varialion in systcm temperature, it would seem lhat the elementary enthalpy variation is expressed as a function of heat capacity at constant pressure. and may then be written as:
(1.14)

1.3

APPLICATION Of THE fiRST LAW TO AN OPEN SYSTEM

1.3.1 General
We have made il clear lhat lhc preceding equations relme to a closed system that does not ellchange matter with the surroundings. In practice. however. such exchanges are the rule and it is appropriate to accounl for lhe energy conlained within the flows of matter that enter into or exit from lhe syslem in question, just as we will have 10 include their mass in establishing a balance of mass. Examples of open systems are varieu: a b"lIoon that .....e blow up. a reservoir that we fiJI, a section of a pipeline. or a turbine. Seyeral of these examples can be combined to make up a less elementary open syslem. A distillation column, a chemical rcactor. or a moving car

7 are other cases. In such systems. neilher the pressure nor the temperature arc uniform:
they change in splice and time.

During a shorl interval of time, ell. the kinctic energy, the pQtential energy in the gravitational field. the internal energy of the system. and the mass of the sysu:m will vary. They vary according to the type of content. mechanical work. and Ihe heal and modifications of the system properties (pressure. temperature. nature of components). The system can be defined initially by the position of its boundaries (certain of which are real. other.; imaginary). For example. a unit of pipeline will be marked between two dearly indicated sections. We will denote flows of maIler dm j where III is mass. and assign them a positive value if mailer enters into tile system. and a negative one if flows are lea... ing the system. We can also account for outflows; dm;" D/ck Each flow characterized by a certain number of properties: potential energy E"",J' kinetic energy Ek .... , temperature T;, pressure P,. and, gi...en here per unit of mass: ...olume v;. internal energy II;. and enthalpy II;. Heat transfers emanating from sources with temperature T, will. however. be denoted by l'JQj' Other energy transfers., OW. will also be excluded. for ellOample, the work done by pres sure accompanying the possible variation in ...olume of the system (a balloon being blown up). the energy supplied by the motor of a pump, etc. Howe...er. at this le ...el we shall not exclude the work aCl:ompanying tile transfer of mailer. The lOtal energy of the system 0 is:

(1.1)
Transfer of maller is broken down into two steps. Mass dm; occupies a ...olume II/ dm/. and possesses an internal energy ,,;dm/. First. we shall unite the system ilSelf with the mass dm" This step therefore increases the mass of the system by dm/. and its energy by: dEo '" 1'1"".1 dm,
+ ckin,i dm; + u/ dm l

This step is not accompanied by work done by pressure: the ...olume of the system has. howe...er, ...aried by + "I dm/" In the second step. we will reduce the new system formed in this way to its initial boundaries. The variation in ...olume will therdore be -IIi dill; and the work that we must supply P/II/ dmi' The of maller therefore is accompanied by a total amount of energy equi...alent 10: e 1"".'dm+e, '''''''+'''''''',+ P,"."'".=(h.+c .+c,.....,)dm, , ".' " "" pol.' In the total balancc that describes the energy ...ariation of the system, we will sum these elementary transfers., as ....ell as those corresponding to the work performed on the system and the quantities of heat: dEo =

L
,

(h/+cpol./+Clio,/)dt,,/+

J'

6Q;+

OW.

(1.IS)

This ...ery general expression of tile first law ob...iously must be adapted to each particular case.

I. Principles.

FunaioM.

n,., 1d&J/ Cd>-

1.3.2 SteadyState Systems

We say lhal an open system is in a steady-stale when there is no variation on any point in the quantity of mailer or energy. over lime. Temperature, pre$Sure. and composition may vary from one point to the neXI within the system. but remain on all points invariable over lime. The previous equation therefore may be integrated oyer any time pcriod 61 wilh dEo '" O. We denote by Q the quantity of total /leat supplied to the system during this time span. by W the sum of work (other than that corresponding to Ihe transfer of matter), by 112 the enthalpy of the nows of mailer leaving the system, and by HI the enthalpy of llle

nOWl; of matter entering into the system:

If l

H 1 =-L.Il;D1trJ
"

if
if

Dj

'"

0 (dlll i

'"

0)

+ L.h j D i 6J

0;

0 (d",." 0)

However. we will exclude the variations in kinetic and potential energy of these flows of maLter. Undcr Lhcse conditions. the energy balance is wrillen as: (1.16) Applit'4 to /In 0lH'n Iystem in 5teadY1tllte. Illtd, inasmodJ ItS the "Ilrilltiom; of polenl..1 energy in tlte gnvitlltiOnal field Ilnd Ihe kinetic enere of lhe flow of mlltt" lIUIy be esdudt'4.lhe Rnllaw eslablishes lID e:oct ba!aDee belween the """lI.tlon of entlullpy from lite enlry Into. 10 Ihe e:Q1 from the Iplem Oft tlte one haneI. Ilnd on tlte olher band lite q..... tltift of hut and the work absorbed by tbe 5}"l1fem elldudi"l Ihose IK:almpllnying exdJllnga of mlltler. This equation is closely related to the equation expressing the first law for a closed system. Enthalpy has been substituted for internal energy (to include the work of transfer). Moreover. the operator <l. here corresponds to the difference produced between ellit from and entry into the system. while in a closed system. it CQrresponds to the difference between the final state and ttle initial state. We must also recognize the importance of the fundion of enthalpy. The energy balances of open systems in steady-state arc enthalpic balances. In this way. for example. the variation in enthalp}' will correspond to the work of adiabatic compression. or even to the heat balance of an item in the absence of work other Lhan transfer work. finally, flow that takes place without eschange of heat or work is called

1.4

THE SECOND LAW

The first law in no way permits us to specify how the energy exchanges arc distributed (work done by pressure. heat. etc.) during the course of a transformation. It expresses only Ihe total energy exchange. However. we have seen Ihat the work done by pressure is at least equal to an attained limit in eases of reversible change. Are heat transfers also limited?

9
We know that the 5lcadY-!ilale of a system is assured only by the cllistence of appropriate boundaries. If some are removed, the system will evolve toward a new state and the revcl"!iC change will nOi be possible. Given two Siales, it is therefore important [0 know which one is favored. It is equally importantlo specify the conditions that the properties of the system must satisfy in order for its state 10 be favored in relation to ailiransformations respecting cerlain conditions (transformations at constant temperalUre or prc5Sure. for example), and that it is in a SIMe of equilibrium. II is to such qucSiions thaI the second law of thermodynamics responds. Its statement varieli considerably from one author to another, and an 'n-depth analysis sho...."S that it is in facl inseparable from the fil1il law.

1.4.1 Entropy
The statement of the seCQnd principle. the definition of the function of entropy lind that of the absolute temperature scale. are inseparable: Given a s)'!Ilem described by ih yolume. internal encorgy, and the " ....tity of maner for eadl of ih oomponents. there emil a property of the 5)'!1lem.lI'ntropy S: II is an ulCO,w", fllllClion a .... broken dOlm Inlo 11'1'0 lenns: During a lnlnsl'onn.tion Its ...

(1.11)
The term cIS. is relaled 10 heal ellmange by thi!' "'IlUltion:

cIS. , T

6Q
"II'

(1.18)
deslg

wbll're T is a property of the syllem th.I dcopends 5Olll'ly on lis IlI'mpenotare, and natll' tbis property as "ab50lute lempenotu.......

IiSj is tconn reblted to Inlernal moditicatioM of lhe Iyllem. II is " ... ays po5illve for spontlncoltS tl'1lJ\ljfonnaliollS, ....d u:ro for reversible tl'1lrulfornutions.

clSj;oo 0
COfl!lCquenlly:

(1.19)
(1.20)

dS.T

6Q

The previous definitions leave the signs undetermined (which are related) for absolute temperature and for entropy. As a convention. we state T> O. We see later on that the properties of low density nuid allow us to determine the rela tionship of two absolutll' temperatures. The absolute scale willthercfore be filled by adoptIng a filled point: by convention we state:

T= 213.16

at the triple point of water

II that for lUI Isoblled system. and tberefore In lhe abllellCe of hut umanse with the lunoundinp. entropy can InCTeISll' only duri... ine1lenible procases and stabi_

10

,. Principles. rI>tYmodrfldlllic FmlClioits.

the Ide<II G.>s

iliielf al II maximum l'lIl1te ,,-hen juilibrium is 1I1tliined. or oourw. in the caR .fhut ndunge. enlropy mllY

Moreover. the Equation (1.20) may be wnllcn as:

(1.21)

and thus corresponds 10 the limit mentioned earlier (Eq. 1.4) for the work done by presSUfe:

SWia'-PdV

(1.4)

1.4.2 Relationship between Internal Energy and Entropy

The variation or internal energy between two stalcs may be arrived al by observing any transformation connecting the 11'0'0 states. We may do this using a ql,lOSiSt3tic transronnalion during which. if the work done to the system is limited 10 the work done by pre5Sure. we will always have:
o'tV,=-PdV
and

lKl,= TdS

(1.22)

We therefore obtain the fundamental expressions thai tie the first and second law together: dU",TdS-PdV (1.230)
and:

I f> dS= -dU+ -dV

(1.24a)

1111:$1: equalions generally perlain 10 one mole: dll=Tds-Pd"

(l.23b) (l.24b)

w ..

1 P -d"+-d,,

Of COUI"SC. if Olhcr forms of energy transfer inlervene (for example. due 10 Ihe existence
of an elcclromotive force). il is appropriate 10 take them into accounl and we would wrile:
(1.25)

Wilhin lhC$I: expressions appear the intensive values. or polentials. p. 1: Fl' and lhe eXlensive values with whieh they are associated S. V. and 1/. These equations in no way allow for the calculation of work done 011 the system or the heat transfen during the course of any process. We can stllte ollly: (1.26)

p'

1. Principles. Jhermodyn.lmic F!Jf>CIiom. The

II

1.4.3 Application of the Equilibrium Condition

This equilibrium condilion shall be ilIuslTated using an isolaled systcm, namely one that e:llchanges neither heat nor work (of any kind) with the surroundings: dW=O.dQ"'O The inlcrnal energy and Ihe volume are therefore oonstanl: dU",O.dV=O and. according 10 the seoond law. entrop)' can only increase or be al ma:llimum:

We will splillhis system into Iwo subsystems A and B, using a panition that will be fi:lled initially. adiabatic, and impervious to all flow of mailer such thai each of Ihese two subsystems is also isolated. On either side of the partition temperature, pressure. and composition may be differenl. Let us now suppose that the panition is diathermic. that is to 58y that it allows for heat flow. As internal energy and the entropy are e:lltensive functions and the system is isolated. we have: We shall express the entropy varialions of each pan A and B by applying Equation 1.24a. Since the volumes V A and V II are unchanged and the tOlal internal energy is oonstanl, we obtaio:

entropy can only increase. the result is thai dUA and T,4 - "f/j are opposite in sign. If we now suppose that the partition is at the same lime diathermic and mobile, we must take into account the variations in volume dV,4 and dV/j' which are related:
AJ;,

dVA + dVIl = 0

and would write: dS" dS,4 + dS/j and thus:

and, finally:

dS. - - - dUA + - - - dV,.

The maximum condition imposed on tile system by the second law thus yields the equality of temperatures and pressures.

' Til ') (T,4

(P, Po) TA T,

J2

1. Principles. 11>cm>ody""mi<; function. The Ideal

Finally. if we had considered thaI the partition separating the two subsystems WIIS not impermeable. we would have had [0 use the derivatives of entropy as related 10 quantities of maner.and would have established the condition of equality of chemical potentials. This condition will be examined later (Chapter 5).

1.4.4 Statistical Significance of Entropy

In statistical thermodynamics I'"e can calculate the number of configurations 'Wlhat II system cin assume, given the energy and volume. It is possible to show thaI this number is related to entropy by the equation; (1.27) .( being the Boltzmann conslant.
In this way entropy is II measure of the disorder of the system. of its indetermination. This equation must be retained in order 10 interpret the sign of the variations of entropy .....ith vohime, the entropy of mixing (Chapter S). and to establish the expression of combinatorial entropy (Chapter 7).

1.5

HELMHOLTZ ENERGY AND GIBBS ENERGY

We have examined the condition of equilibrium and change in an isolated system. Any possible change may be characterized as internal rearrangement. and is possible only with an increase in entropy. In prnctice. we will deal with transformations during which the system exchanges heat and work with the surroundings.. In order to take these exchanges into aCCOllnt. we relate the t.....o equations:

dU=liQ+c5W+oW'
in which t5W' represents the work done by pressure and c5W' the other work (electrical, etc.). and; l5Q TdS (1.21) Substituting liQ we obtain:

OW+ oW' .. dU-TdS

l)uring the course of a change at constant temperature. this equation may be wrinen lIS;

O\v +.5\\1' .. d(U - TSh

or

w + W' .. tJJ.U -

TSh

(1.28)

Furthermore. if the system changes at constant volume. then the work of pressure force is zero and this equation becomes:

bl'''d(U-TS)rv
The function:

or W'''A(U-TS) at constant temperature and volume

A=U-TS
is called the Helmholtz energy.

(1.29)

13
l'he preceding equations are therefore wrilh:n as: OW';;lo dAr,l' or W ... llA al constant lemperature and volume (1.30)

A cbaD,e at collS'anl .nd l'olume is themore posslbIe oilly if the Helmholn. ellC'''IY dKreale$. In Ihill caw, the s)"!Ilem may off II quantity of encrz:y l-W') to lite sunvundinl' lhal is at mOllI e,UII' to lhe the Helmholn. eMrgy.1f the Helmhohz energy inCftllSeS, ror the (:hante to be possible. It ...o.kI be nettSUry to ",pply 10 11M: .JY$lem (in the form of eledrial energy. for enmple) II qaantity of eMflY lhal is III ie_I e(j .... 10 the illa't:ase in the Helmholtz enere- 5il1ft are presumlnllhat tbere are no such ndla:np hen', ...e sh.1l retain lbe cortdltlon of dumge:

dAT.V"O and the rolldilton of equilibrium:

(1.31)
( 1.32)

If the system changes al con$lllni tcmpenture ...... pn'SSure. and In pressure equilibrium with the surroundings. the work done by pressure is then cltpressed by the equations:

OW=-PdV

or

such Ihal we would write Equation 1.28 as:

SW'o-d(U+PV-TSh.p or W'o-d(U+PV-TS) at constant temperature and pressure

The function:
G", U+ PV- TS", H- TS",A + PV

(1.33)

is called the Gibbs energy. The previous equations therefore may be wrinen as:
liW' 0- dG T.P or W' 0- tJ.G at constanttcmpcralUrc and prcssurc

(1.34)

ThWl, I mlnge lit oollStanl lempt'n1lure lind pre5!iure is pofiSible only if 1M Gibb!i ene'1Y decnasa. In Ihis CMe. 1M I)'stem mllY i"e orr. quantity of e_'IJ (-HI') to lite surrollDdiap thIIl Is at IIIO$t equll 10 this decrelSof. If Ihe Gibbs eM'1Y lnCftucs, for the duutge to be possible,it wouW be necnsary 10 supply 10 tlte (ill the fonn of elKtriall enelJY. for eumple) a quanllty of tlle'1Y that is II ItItSI tq.... to tlte increase in lite Gibbs tntrgy. Since we presume that there are no such exchanges. we shall retain the condition of change: (1.35)
.nd tbe oondilion of equilibrium:

dGTJ''''

( 1.36)

or more precisely. minimum G at constant temperature and pressure.

EXAMPLE 1.1

Condensation by dclidbiJIic expansion

To illustmte the use of thermodynamic properties in the calculation of compression work and heat exchanges. we will examine an ethylene condensation process that functions according to the sleps lhat follow. Ethylene. available at atmospheric pressure and at lorrF (37.8"C). is compressed in an isothermal fashion to 50 bar. The fluid then undergoes adiabatic expansion to return to atmospheric pressure. During this expansion. there is partial condensation: the vapor phasc is recycled. It is necessary to calculate the proportion of liquefied ethylene, the work and heat ellchanges accomp.1nying the compression step. and the work that may be collected during clI"pansion. To do this. we make lISC of a diagram (Fig. 1.1) that provides the prcssure variation. shown on the ordinate. as a funclion of enthalpy. shown on the abscissa. along the isothermal or isentropic curves. These calculations will force us to makc certain hypothcses relative to the revcrsibility of each step. Most often. the laws of thermodynamics do nOI allow us to estimate the exchanges of heat and work except in the case of reversibility.

, <orr ',,7...., ' .l.!.' ,

'
,

. .'i'

...f /

'1:""
- roo

""" "" '"

000 000

.
T-

--

-. . -

'
,'.1
\.

" . - " .,

J .,
100

.. .. ..
'" '"
,,

Le", ., i/
.
J
":-1

I .'
I I ; I

7%
.
,,

;';'-ii:

' (','/,\ ' ,J: .... , ",.,/1' ','

" ,
9

,J' I, "

120-

-><.;j

... '

f'-

__ 140 I

I ,.

-,

1"'," , , .r., ,,,

'"

. , , .

I I

I II ,.

'"

...

, "

, , ,' , V ,, , ,

'.

"""

'''''' """

[C.njar and Manning. 19611.

)lpre 1.1 Diagram of ethylene enthalpy pressure

c,

.(f

h'

Th,_
!l!i,"1IiC'CS' OLI, '.

, 'h ,
,

JU

au

16

and thence derive:

h""'-h

1020-990

hV.tJ_h L " = 1020-815 =0.146

(1.39)

To determine energy exchanges during the isothermal compression. we apply the first law considering thallhc system is llJl open system in steady-slate:
MI"-Q+W

and the second law:

Q ...

(1.16)

T dS

(1.40)

As compression is reversible and isothermal, we have:

Q=Ta5
W r = aH - Q = lJ,C T

(1.41) (1.42)

Calculations will be performed using the units provided in the diagram. In particular. we nOle thai the h:mpcralures are expressed in degrees Rankine (OR).To COIlven 10 Kelvin:

T(R) = 1.8 T(K) = 9("F) + 460

As the unit of energy is Btu/lb. we have:

llb",453.6g.
So. we arrive al:

I BIU",252'cal=10S4J

and

I 8tul1b:Z.J24J.g- 1

T= 560"R Q = 560 (1.55 _ 1.89) = -190.4 Blullb = -442.5 J. g'l

W = (1060 - I 100) - 560 (1.55 _ 1.89) '" 150.4 Blullb., 350 J. g_l

In order for the expansion \0 be reversible. it is appropriate to recover the work of We will apply the previous Equation (1.16) to calculale this work. while laking into account Ihat there is no exchange of heaL. and therefore: W", lJ,H (J.4J) for an adiabatic transformation or:
W = 990 _ 1060 = -70 Btullb = -163 J 'g-'

III reality. compreMion and expansion are irrcversible to a certain degree. and the val ues above represent the limits. Furthermore. compression is accomplished in 1'110 (or more) adiabalic sleps. and therefore is accomrmnied by all increase in temperature. Each increase is followed by cooling 10 restore the initial temperature. Thus the first step can be substituled wilh two isentropic compressions going from atmospheric pressure to 7 bar. and then from 7 to 50 bar. The calculation shows that in this ease the work lhat must be provided is in the neighborhood of 400 J . g-I and lhe heat to be released approximately -500 J . Expansion may also take place wilhout recovering work. We would have Q = 0 and W = 0 al the same lime. Expansion would therefore be isenlhalpie. With the help of the diagram. we may verify thai it would nOi allow for ethylene condensation if Ihe compression slep were not modified. and thatlhe compression should reach malely 120 bar 10 achieve Ihe same rate of condensation.

17

EXAMPLE 1.2

Methanol

battery

The eltromotive force of a methanol battery operating in an alkaline environment al atmospheric pressure and under reversible conditions is theoretically equal to 1.33 V at 2.'i c c. In practice. the following results were observed in the laboratory under the same oondilions of temperature and pressure: a pOlcmial difference of 0.2 V and a heat release of721 kllmal from oxidized methanol. The reaction is described by the slOichiometry:
eliJOH +80W-6e
--t
--t

COJ-+6H 10
60H-

3 "T0z+3Hp+6e

The rcactanlS and the products are in an aqueous liquid solution with the exception of

oxygen. which is gaseous.

These data allow us to determine the variations of the thermodynamic functions

accompanying the oxidation reaction. as well as the exchanges of heal in the case of reversibility or free combustion, we note that the variations of the thennodynamic functions will be the SlIme regardless of the degree of irreversibility of the process. Indeed. the initial and Iinal states are the same. The work done by preso>ure can be easily calculated since the pressure of the surroundings is constant
The variation in volume results from the consumption of OII:ygen. We apply the equation for the ideal gas state: A(PV) '" RT Av where Av denotes the variation ill the number of moles (-1.5 mol) and R (8.3145 J'mol- I . K-l) denotes the ideal gas constalll. We lind that for a mole of methanol oxidi7.ed: IV... '" 3.7 kJ. Furthermore, we can calculate the elcctrical ellergy involved: If designah:s the electromotive force. ?l Avogadro's lIumber (6.022 )( laD). e the electron charge (e'" 1.6(2)( C). and An the number of clcdrons transferred. on the basis of the preceding stoichiometry (All = 6). then: IV' "'?l AntE" 964nAf,E We thus rind thai IV' '" -no kJ in the case of reversibility (E '" 1.33 V) and IV' '" -115.7 kJ from the rcsults observed (E =: 0.2 V). This energy is considered negative as the setup produces energy (electromotive force).