52 Metallurgical Thermodynamics PV=RT_ for one mole of an ideal gas, Thus, : 7 . dg=C,dinT'+ Rdln os, 3 Int + Rin +S, Afr integrating, S=C,nT+R Bay where, S, is an integration constant, j Darin Therefore, Sa GpIng te Rin 2 Equation 3.36 can be rewritten in the form: S=(Cp-R)InT+ RIV +S, =C,In THRmE+s, (338) =Cp)InT+RInR-RInP+S S=C,InT-RInP+S” 63) q, A AS =(S,-S,)=C, In - R In 649 (8-5) =C, 7, ? ) L, V, B Therefore, AS,=C,In2; AS,=C, ne AS;= Rin = Rin ia ‘ * Restriction of Applicability of the Combined Statement (dU = Tas — Pav) The formulation of the combined statement tacitly implies that, * itis a closed system, that is, there is no exchange of matter with its surroundings, and * only the work done due to volume change has been considered. However, other types of work such as, Sydn (chemical work), G4Z (electrical work), y d4, (surface tension work), J0dM (magnetic work) and others have not been taken into account. Accordingly, the most useful form of the combined statement involving P and T is to be developed with the use of the auxiliary functiong, 3.13 Auxiliary Functions It has already been demonstrated that the combinat; Thermodynamics has led to the following relation: dU = 74s ~ pay (3.29) ion of the First and the Second Law ofee Concept of Entropy and the Second Law of Thermodynamics $3 of state provi , independent variables Sead Yin, ‘ltionship between the dependent variable U and the 7 pores a closed syst iti ‘ich is it ty with een Bs. iphonvenient choivs aires ae combined statement is the fact that Sand V are an eariieaiehts oF coat a lependent variables from the point of view of experimental - Although V of a system can be measured or controlled, the entropy Scan neither be simply measured nor contro! s thus desirable to develop tr n simply mea i ey ay ured nor controlled. It is thus desirable t i : ; (0 Eq. 3.29, which wi independent variables Pearce 13:29: Which will allow the choice of more convenient : erimentalin’a psinretyi Cn a ialepeudent variables poate ‘imentalist’s point of view, the most convenient pair 3 an ich are easi in practice. \d T, which are easily measurable or controllable Therefore, there is ivatic that of Eq. 3.29, eee aeivation of eauation of state ofa similar simple form as establishment of a criterion for attai pendent variables, which subsequently needs Constant ttainment of equilibrium in a constant temperature and Pressure system. Alternatively, from the theoretician’s poi i Vand Tas the independ F an’s point of view, the choice of independent variables would be most convenient, since constant temperature, constant volume Processes are most amenable to the theoretical calculations using the methods of statistical mechanics. The second difficulty with Eq. 3.29 is that it can neither be applied to systems which undergo compositional changes arising from occurrence of chemical reactions within the system, nor can it be applied to systems which do other forms of work besides the simple P-V work. ‘A number of systems, however, undergo compositional changes during the change of state or during the progress of a reaction; for example, the transfer of an impurity from an impure metal being refined to the refining slag or to the atmosphere adjoining the system as in the case of removal of C, P, S, Mn, Si and so-on during the steel making process; precipitation of a second phase in an initially homogeneous alloy, that is, the precipitation of various metal carbides during tempering of steel (precipitation-hardening or age-hardening type of alloys) and others. These phenomena are very common and are of prime importance to metallurgists and material scientists. It is therefore essential to include compositional variables in any equation of state and in establishment of the criterion for attainment of equilibrium. Similarly, it sometimes becomes absolutely necessary to consider forms of work other than the P-V type which a system may perform, such as, electrical work performed by a galvanic cell, surface tension work in liquid-vapour, liquid-liquid, solid-vapour systems, magnetic work as during induction furnace melting of metals and alloys and so on. Thus, it becomes necessary to introduce the concepts ‘of some auxiliary functions of state which as dependent variables are related ina simple form to a more convenient choice of independent variables such as P, T, composition and so on. = j Now, some thermodynamic functions will be introduced and their importance in the thermodynamic treatments of various simple and complex reaction systems will be discussed. These functions are: F = Helmholtz free energy or work function (H von Helmholtz, 1821-1894), G = Gibbs free energy (JW Gibbs, 1839-1903) and #4,= the chemical potential of the species ‘i’ ina solution or mixture. Their particular characteristics and interrelationshipsBee ¥y mics thermody” 5 gst the many ther jonships amongs y thermodynang _ The relation t only th or OF Gand ea ‘innumerable, but only the more usofiy, form will be dissed i eo “tee : os ergy (U), the concept of enthalpy (17) 4, when the system undergoes a change ree q thalpy has already been defined as =U4 pet Unde, ein 5 sone can Wile A = de crane Property thi Shoat cio, examined in detail Tater on in relation to varius of the eta ees the total heat content of any system, systems. Entha “ etaltureica! ral en cept of interna’ « once namics be discussed: ; ilar to the concel ST of Thermody from the Firs conditions. Ent AIOUS tea react ‘Oy 3.14 Concept of Free Energy? Gibbs and Helmholtz Free Energies stem is said to be in thermodynamic equilibrium when its entropy is ap algal problems, we are mainly concerned with examining the eae” within a system which is not isolated from its surroundings. For example, heat treatmeny 7 alloys, thermal analysis of various substances, steel making Processes and so on. ft isa distinct drawback to rely solely upon the entropy concept, since, in such cases not only the entropy change of the system but that of its surroundings are also to be assessed ig establishment of the equilibrium criterion. The requirement is to define some thermodynamig function ofa system, which can be used to define the conditions of equilibrium of te sym under all conditions in the same way as the entropy can be used to define equilibrium foran isolated system. Such a function (for systems only) that is used quite frequently is referred to as free energy function. Let us consider a system which can exchange energy with its surroundings. For sucha (system + surrounding) combination, the already established relation is, Ss tm + ESssrounting 2 O Gal) An isolated sys maximum. Inm ice the greater-than sign signifies spontaneous processes and the equality sign stands for than le process or the attainment of equilibrium. If it is assumed that the system absorbs mount of heat Ag from its surroundings (very big) at temperature T and pressure P, We can write: ~ US ssnateg = Wey Woche = “AS, em == (%) i ca at constant pressure G-) Combining Eqs 3.41 and 3,49, mi ir ASS em 20Concept of Entropy and the Second Law of Thermodynamics 55 or, (IT = TAS) gym $0 (3.43) Now, differentiating the expression d(/1 — TS). ; : dH ~ TAS — SAT = dH - TAS. Therefore, for an isothermal process, (d/ ~ TS)ey4em <0 3; . S) system S G44) Under isothermal and isobari an irreversible reaction, d(/ — TS) < 0. This ex i je reaction, d(H ~ TS) = 0. For energy, the free enthalpy, the thermodynamic potential is 79) is called he oe a and temperature. It is denoted by the symbol G. ct fie eee ee The tendency for the entropy to be at a maximum value can therefore be replaced by the more useful tendency of the Gibbs free energy of the system, to have a minimum value (4@)syam $ 0). In a reversible reaction, such as an allotropic transformation, the change of Gibbs fe energy for the transformation is 20 (4G =0). This means that ‘oth the allotropes coexist at equilibrium, While for an irreversible or spontaneous reaction, the change in Gibbs free energy is always negative (dG < 0), that is, such a process is accompanied by 2 decrease in free energy and the system moves spontaneously to a lower free energy stale. If instead ofisothermal or isobaric conditions, we choose isothermal and constant volume conditions, then we can write, 54 au os as, --(%) --(# 3.45) onsen (HF) (FLO Then from Eq. 3.41, s(2)_» 0 be = au -TaS <0 Ge) au- TS)y.750 (3.48) The expression, (U ~ TS) is called the Helmholtz free energy or free enerey at constant temperature and constant volume, or work function. Wt is denoted by the symbol F, So, the condition can be written as: (dy Dsysien 0 3.49) Then the following conclusions can be made under equilibrium conditions: =H-TS, isata minimum () Atagiven temperature and pressure, the Gibbs free energy, ‘under equilibrium conditions and the change in free energy, Gp p= MH - T9)y2=0 eei dynamics 56 Metallurgical Thermodyn mholtz free energy (F = U~ 75) the Hel ¢ is (ii) Ata given temperature and vol ovine change in fee ener fs minimum under equilibrium conditio rf OF p= (U- T)n7= &s, Both G and F are state functions. For irreversible or spontaneous processes, 4 < Gp 7 =A(H ~ T5)p,r = AH ~ T85)p,7 | 2 OF, p= d(U ~TS)y,7= (AU ~ T85)y,7 <0 52) v= , These quantities can be divided into two separate functions: dH,,<0 or dUyr0 or dS,7>0 (3.54) The energy and entropy functions can be thought of as mathematical formulations of two ‘opposing tendencies in a system. On the one hand, there is a striving fora minimum free energy for stabilization, and on the other hand, a striving for maximum entropy to attain a stable state. At absolute zero, the entropy term tends to zero (consequence of the Third Law, which will be discussed later on) and the stable state of the system is that with lowest values of energy functions (H or U). This state generally corresponds to the degree of order in the system. A pure metal at absolute zero is a solid rather than a liquid—ordered or disordered. When the temperature is increased, ordering in the solid decreases due to increased vibrations of atoms. The entropy function becomes more predominant with a rise in temperature, since this favours the disordered state. The temperature at which the entropy begins to predominate will depend on the magnitude of the attractive forces between the atoms. At the melting point, the two opposing tendencies cancel each other, since AH=TAS or AU=TAS Thus, AG=0 and AF=0 3.15 Expressions Derived from the First and Second Laws of Thermodynamics for a Closed System of Fixed Composition We have already deduced: () dU = TAS - Pav thatis, U=/(S, Y) (3.55) Further, F has been defined as F = U~ 73 we get, ' Then differentiating the above expression. dF = dU - Tas - sar (3.56) Combining with Eq. 3.55,Concept of Entropy and the Second Law of Thermodynamics 57 (i) dF=S4T-PaV thatis, F=s(v, 7) (3.57) Now, differentiating the expression, G = 1 -TS, / dG = dH - Tas- SdT (3.58) It is also known that H = U+ PV. Differentiating this expression, : dH = dU + PdV + VaP (3.59) Combining Eqs 3.55, 3.59 and 3.58, (iii) dG=VdP-SdT thatis, G=/(P,7) (3.60) Further, combining Eqs 3.55 and 3.59, (iv) dH=TdS4VdP thatis, H=/(S,P) (3.61) The above four combined statements (Eqs 3.55, 3.57, 3.60 and 3.61) are applicable to systems of fixed composition, that is, there is no exchange of matter with the surroundings and no reaction within the system leading to compositional variation. However, in practice, one has to contend with variable composition systems; the system may be composed of multi- components. If the composition of a system is variable, that is, the number of moles of various species present within the system varies due to a chemical reaction, the minimization of the G value at constant T and P occurs only when the system has a unique composition. If we consider a system consisting of CO,(g), CO(g) and O,(g) at constant 7 and P, minimization of the G function would occur when the equilibrium of the following reaction is established: €O,(g) = CO(8) +3 0408) 6.2) That is, as soon as 7’and P are fixed, a particular ratio of a will be established within the system and that ratio will generate a specific oxygen partial pressure or oxygen potential in the gas phase. Therefore, the composition variable should be included along with 7 and P for the G function. Thus, GHf(P Tims My ler) (3.63) where 1,11), Myer = number of moles of the respective species. Then, from the theorem of partial derivatives, OG «-(%] ar+(Z) av (22 } dn, OF Jp any A Jon .nym MD) ptm. 6.64) (Z] dn, (2) dn, + OM; Jo.rmim BAP Toman ) If the number of moles is fixed, it has already been shown that‘Thermodynamics 58. Metallurgical dG=VaP- SAT aG 2 2) =V and [57 =-8 a Jrmanym pease . ions for variable compositi i lowing expressions ON syste Therefore, we ean write the fo tif 3g ™ — dn, IG =VaP - SAT + [ | i, a > on, PT. (45 al 5 ical potential of species ‘i’ in The term (2) is called the chemical pot pi he system anit, WD prnyen designated by the symbol /i,. oG _ oh, = This is defined as the increase in Gibbs free energy of the system for an infinitesimal addition of the species ‘i’ at constant P and 7, such that the number of moles of other. Species Virtually does not change in the system. Now, Eq, 3.65 can be represented by, k 4G =VaP - SaT + ¥° 4, dn, 6.46) a The last term represents the summation of k terms, each of which is obtained by differentiating G with respect to the number of moles of ‘i’th species at constant T and P and nny where n Tepresents the number of moles of every species other than the ‘th species. The above equation can thus be applied to open systems which exchange matter as well as energy with the surroundings and also to closed systems which undergo compositional changes due to any reaction within the system, Similarly, other expressions involving dU, dH, and dF can be made applicable to open Systems by including the terms describing the composition dependencies of the values of U Hand F. Thus, the following expressions can be written: L dU =TdS - Pay “3(2) dn, (3.67) TINO sven L dH =Tas+vaP + ( ) dn, 6.68) INTs, payer, t dF =~sar pay +3(2] dn, oe) WV rmen ta on,: Concept of Entropy and the Second Law of Thermodynamics 59 Comparing Eqs 3.65, 3.67, 3.68 and 3,69, a-(¥) (2 (au au ‘Toten AO), ah, =| (3.70) sayemy S.Pimjen SV.njen J an, Thus, the chemical potential of species ¢'j * in a mixture or it i e defined a shown in Eq. 3.70. Hence, the complete set ripe canbe Sennc = of equations is: ‘ dU = TAS - Pav + Yn, dn, a G.11) 1 dH =TdS + VAP +", dn, (3.72) a t 4G =VaP ~ Sar +9" ,dn, (3.73) a ‘ dF =-SdT ~ PAV + 4,dn, (3.74) Inthe above expressions, work only due to the chemical potential term has been included and other forms of work, such as €dZ (electrical), IdM (magnetic) and dA (surface tension), have not been considered. From the above four expressions, the following relations can be obtained, which provide definitions of 7, P, V, S. #1) (%) r=|= |] =| (3.75) au (=) P= == (3.76) (Ft... oH (¥) v=|— =| (3.77) (32) -{2| (3.78) Us 'P, Comp or ¥ Comp 3.16 Maxwell’s Relations Let Z be a state function while x and y are the chosen independent variables for a closed system of fixed composition, that is, Z=/(x, y).60 Metallurgical Thermodynamics ‘| a a eee edi Then, wz=(¥) oe(Z) ly WA (az It is then assumed that, M -(3) and N= (), These partial derivatives are functions of x and y. Ory Therefore, dZ= Max + Ndy om where M,N, Zare all functions of x and y. Differentiating M partially with espe.) N with respect to x, Y and oM) _| 2 (2) oz ay), [ay \ae),|~ acay G1) (*)-[2(4)]-2 a), Lardy), | Ardy (3.82) It is also known that Z is a state function, the change in Z is independent of the order of differentiation. ; 3-2) ae ay), ar), (383) This is known as the condition for exact differential. Application of Eq. 3.83 to Eqs 3.71, 3.72, 3.73 and 3.74 under fixed composition condition results in the following set of relations which are known as Maxwell’s relations (J.C Maxwell, 1831-1879). . ( oT oP “BL DV) comp — \ BSI comp @ (2) (2) OP }s,com \ OS Jp, comp (iii) () -{2) OF Jp cmp OP Jrcomp » (FA _-] gy [25)~ 2f ov ‘T,.Comp or V Comp ic (Sytudies’ If one remembers the sentence ‘(P)rofessor (Verifies through (7)hermodynamic OF a and use the square with different state functions such as P, V, T, S at the come! 6.84)Coneept of Ent : iropy and the Seca above sequence (Fig. 3.10) and no eee vertical lines like PS and 17. then ong correct form. ” en ts considered for the di: aa e ‘als by for the © can easily wtite all the Is but only for the well’s relations in their (ve (ve _ s T Fig. 3.10 P-V/—7-S square for correct writing of Maxwell's relations, If one considers work due to composition variables besides the P-V type, then the following expressions can be written: dG=VAP—SAT + .dn + ,dm+mdnte| (85) dU = TAS — PAV + dn, + 14, dn, + fady + nn write Maxwell’s relations in terms of chemical potentials and changes in We can the! composition: ee) Ah J,r.m mre Ott Jp rmomon 86) : My )s,y.nsmom AM, )s,y,.m0 many experimentally determinable quantities can be ns, With the help of these relatio! obtained: (3.87)