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    Thermodynamics of Surfaces. Thermodynamics and your applications. Tester & Modell

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    Thermodynamics of Surfaces. Thermodynamics and your applications. Tester & Modell

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    © All Rights Reserved
    Download as PDF or read online from Scribd
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    2 views15 pages

    Cap 19 Tester

    Uploaded by

    lizethtairina
    Thermodynamics of Surfaces. Thermodynamics and your applications. Tester & Modell

    Copyright:

    © All Rights Reserved
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    ‘Systems under Stes, in Electomagnaic or Potential Fields Chapler 18 Data: Assume that he ozean temperature = 10°C for wate a 10°C = 1230 Pa “The parti pressure of water over the ocean at the surface, is 1207 Pa (this value assumes a 3.5% NaCl soltion) Density of seawater = 1.0255 giem” The partial oar volume of 0 in seawater i approximately equal tothe pure molar volume of 1,0. Thermodynamics of Surfaces 19 In the absence of gravity or other body forces, free liquids assume a spherical shape Intermolecular attractive forces operate to poll the molecules together; this attraction results in the formation of spheres. A conventent way to characterize this behavior is to assume that the surface isin tension (ie., each element ofthe surface layer experiences tensile forces from neighboring elements); the net result is a surface somewhat similar to that inan elastic balloon, ‘The analogy to the balloon ray be carried further. We know that there exists a pressure difference between the inside and outside of a balloon because ofthese tensile forces. Similarly, in a bubble or drop of liquid, we will show that the internal pressure also exceeds that outside the drop. To demonstrate this, we will again use the concept of surface tension forces. In this chapter we first examine surfaces from the standpoint of work interactions (je., we derive an expression to allow us to determine the work necessary to Vary both the volume and area of a surface layer). Following this, we explore the effects of ccurvature-on small liquid drops and crystal nuclei. In the remainder ofthe chapter we develop the important thermodynamic expressions for surface layers and also apply the criteria of equilibrium to the nucleation of new phases. The extensive subject matter of surfaces i examined only from aclassial thermodynarnic point of views; interesting and very important phenomena such as wetting, surface activity, and adhesion must be left for the reader to enjoy in specialized texts, such as Adamson (1982). 19.1 Surface Tension ‘To illustrate more clearly the mechanical analog of surface forces, consider a plane interface between phases ct and B. The clement shown in Figure 19.1 measures x units wide, y units deep, and has a thickness t such thatthe top and bottom of the element are Jocated in the homogeneous phases cand B, respectively. Each side ofthis parllelpiped is subjected to a normal, compressive pressure P that is equal at all points. “This equality results from the criteria of phase equilibria derived for plane surfaces in Chapter 6. Also, in the two directions perpendicular to the thickness, , there is the tension force 6 per unit length (.e, the tensile force on the front and back faces would be Gr; on each side face, 69). In ST units, ois expressed in Newtons per meter (N/m). 892 Thermodynamics of Surtaces Chapter 19 Phase “ i Le ; Figore 19.1 Element in plane interface. If we choose the parallelpiped as our system, the work done by the system on the: surroundings when the volume is increased by dx dy dt is negative and given as, BW = (Pry) det (Pty oy) d+ (Pu ox)dy OW = Ply drt yy drt dy) — oly det xdy) or with V=xyt and @ = xy bw = -Pdv+oda In this case, the work term given by Bq, (19-1) includes both volume deformation (P dV) and surface deformation (6 da) contributions. (19-1) 19.2 Equiliorium Considerations Consider the equilibrium system shown in Figure 19.2, Itis composed of two distinct parts; abulk phase oc and a small fragment of a different phase B, Pbase is maintained ‘at constant temperature and pressure by contact with the large isobaric and isothermal reservoirs Rp and Rr Except for the presence of the fb phase, the situation is identical to that shown in Figure 6.5 and as described as case (c) in Section 6.3. There, with no B phase, it was shown that the system attained an equilibrium state when the total Gibbs energy was a rinimom. —— Section 182 Equilibrium Considerations oc) “epee ass igure 19.2 System interactions with constant pressure or temperature reservoirs. ‘The present case is, however, somewhat different because the small element of phase B does nat necessarily have the same intensive properties as phase cteven though both phases are in equilibrium. In addition, we must consider energy contributions for the surface phase (6) between and B. Ifthe same nomenclature as in Section 63 is used, the criterion for stable equilibrium states is AvP =au+Au*+au*r>0 ‘where the superscript represents the global system and terms that are not superseripted refer to the cB system. As shown before, for variations in volume or entropy, au% = -Pavir=Pav (192) AU*r= TAS =-TAS (19-3) where the global conservation of total volume and entropy has been employed. The P and T values in Eqs. (19-2) and (19-3) are those that characterize the continuous phase e:but not necessarily phase f or. Also, AU=AU" +AU + aU" (19-4) where B and 6 represent the B and surface phases, respectively. If Eqs. (19-2) (19-3), and (19-4) are substituted into Eq. (6-16) with the expansions (19-5) (19-6) then, 84 ‘Thermodynamics of Surfaces Chapter 19 (AU + PAV? — TASS) + (AUP + P AV — TASP}+ (AU +? AV? - TAS%) > 0 (19-7) In a fashion analogous to that presented in Chapter 14, lets introduce a term called the availability, B, where Us PV-TS (19-8) In this definition, P and T are constants and equal to the pressure and temperature in the extemal reservoirs Rp and Ry. Eqvation (19-7) states that availabilty is the thermodynamic function that attains & maximum or minimum value in the «-B-< system; then, at equilibrium, aB 09-9) and for stability fB>0 (19-10) where dB is the lowest order, nonvanishing derivative. We will utilize the stability criterion later ip Section 19.7. ‘At equilibrium, with Eqs. (19-7), (19-8), and (19-9), in differentials dB = dB + dB? + dB" 19-11) To determine the specific equilibrium criteria for this case, U%, UP, and U° are expanded using the Pondamental Equations in energy representation, dU" = Tas Pdv*+ > uf ant (19-12) A P= Bast Pah +S pant 19.13) A dU? = 1 dS°— FP? dV +.6da+ Yu? dno (19-14) mn With Eqs. (19-11) through (19-14) subject to the constraints of V+ P+ = constant end S*+5°+S° = constant, and with the understanding that T= 7° and P= P* are constants and are determined by the reservoir temperatures and pressures. In this situation, we are effectively saying that the bulk continuous phase (a) is kept at constant T and P. With these assomptions, we get PD A$ +1) a8 + Yuh ans Dap ay i A (19-15) + Lup any ~p) apy av? +0.da=0 A Section 182 Equirium Considerations 895, Before examining Eq, (19-15), the conservation of mass restraint must be included Foreach component, this is equivalent to saying that AN, = dNS + dN} + dNf =0 (19-16) If Eq, (19-16) is multiplied by —U% (chosen as a Lagrange rovltiplier) and added to Eq, (19-15), each variation is independent and the coefficients must be zero. Therefore, (19-17) cag-t8) as-19) (19-20) and (PPP) dv + (P°— P) dV aa. (19-21) ‘The first four equalities are as we expected: the teraperatures and chemical potentials of each component are equal throughout the system. In this regard, our results do not differ from what we found earlier for phase equilibrium erteria. Equation (19-21) is, however, a different result. It expresses a condition of mechanical equilibrium where ‘now there is a connection between V®, V7, and @ that depends on the geometry of the B phase. First, let us consider the term (P° — P) dY°. We have some latitude in defining the extent ofthe surface phase and, depending on our choice, we could have different values of P® and dV. If we were to define our surface phase boundary so thatthe surface had properties similar to phase oy then P° = P*= P and (P°— P) dV is essentially zero. ‘Usually, however, the surface layer is associated withthe discontinugus phase (in this, case, B), so the (P° — P) dV® term is incorporated into the (P? — P) dV term. Equation (19-21) then reduces to a PPP Pao (19-22) The final relation expresses the pressure difference across a curved interface in an equilibrium system Example 19.1 ‘What would the pressure difference (PP — P# be forthe following cases? (9) If phase B were a sphere of radius T, () IF phase were assumed to be a solid with the shape of eylinder or pancake disk of radius r and some fixed height hs, (h is some multiple ofthe lati spacing.) This case is often used in two-dimensional nucleation theories involving crystallization on a flat surface, 896 ‘Thermodynamics of Surfaces Chapter 19 (©) The phase boundary between the a and B phases consists of arbitrarily curved surface that is completely charactecized by two radii of curvature C, and C as shown in Figure 193. Solution (6) Let the radius ofthe sphere of phase B be r. Then, from Bq, (19-25 42, =(4/3)R ? and then, da PP ping = ave (©) For ne assumed pancake shane, only he area ofthe curved suctace is ofnterest Thus d=2nrhand P= nr (19-23) Phe pe, (19-24) (© In Figure 19.3 a small clement of the surface is shown, ‘The aca is xy. If we ——Piase ot Figure 19.3, extend the element by 8 and thereby increase C, to Cy + 8t and C, to Cy +64, then the increase in area and volume of phase becomes Ba=(y + 8y)(x+ bx) —ay=y Bx +x By Bu, by similar triangles, ‘Then, ‘Section 19.3 Elects of Pressure Differences across Cuved nteriaces 87 = 2 HGH and HTH Substituting the Ax and By terms into the expression for Bland using Ba (19-22), oops } (ob/C, +981/C)0 xt Papel Lib (19-25) late 5 (19-25)isthe general form ofthe Young Laplace oquaton {se alto Adamson (1982), 6-8), Porasphere, Ci = Cz = r,and Eq. (19-25)reduces to Eq. (19-23); fora plane surface, Cy = Cy=oeand PP = P# ‘The lter ease yields the pressure equality we foundearler when we studied phase equilibrium for planar surfaces (ee Section 65) 19.3 Effects of Pressure Differences across Curved interfaces For our equilibrium system containing a large bulk phase ct and fragments of a different phase 8, we have shown that the pressure in phase 8 excceds that in 0. If Bis spherical, the pressure difference is given by Eq, (19-23). If B has a different curvature, wwe can always revert to the general case as shown by Bg, (19-25). These relations show how the pressure difference depends on the size and shape of the fragroent of phase B, To estimate the pressure inside the small fragments of phase , it is convenient to relate P? to the true equilibrium pressure in the system when a phase with the same composition and temperature as phase cis in equilibrium with a planar surface of phase B. Several examples are given below to illustrate the methodology. Phase B: small spherical liquid drops; Phase cz: vapor Let us begin with the case where a pure component vapor at P® and 7° is in equilibrium with small liquid drops with radii r. The pressure inside the drop is P® but, by Eq, (19-17) the drop temperature 7°= 7". The chernical potential equality between te liga op and vapor phase ie expresed in tes of fg oe Seton 9:7) wih LPT =FPD, (19-26) ‘The fugacity of the vapor (<) phase may be written in terms of its fugacity coefficient ¢”: FPN = 9 DP san For the fugacity of the Liquid drop (B) phase, we can relate the fugacity at P® to the planar equilibrium pressure P,, by the Poynting correction [see Bq, (15:94)] o P PP) =p, Tex { | 4 o| 19-28) 398 Thormodynamics of Surfaces Chapler 19 ‘The fugacity ofthe liquid drop at P,, and Tis equal tothe fugacity ofthe pure vapor at Pj and T, so, in an analogous fashion to Ea, (29-27), PP Daf Pp D=O Pay DPy (19-29) Combining Eqs. (19-26) through (19-29), we obtain \ 8 Pay DP ex (ley. v a =oe* (19-30) Equation (19-30) relates the pressures P* and P® to P,, and other properties of the system. If we further asstime that the pure vapor behaves as an ideal gas at P,, and P4, both fugacity coefficients are unity. Also, assume that the iguid molar volume, , is nota strong function of pressure. Then, Eq (19-30) simplifies to wep.) = VP Po) 19-31) PR=Py | aT a From Example 19.1, using the Young-Laplace equation, P? = P* + 26/r, s0 Vp"-P,+20/r)] - VRE Pag t 26/1) : In most cases (P*— Py) << 20/r, 0 Eq, (19-32) becomes 208 Po ryen(t ‘Thisis the Kelvin equation, to illustrate its use, suppose that our & phase were pure water vapor at P* and 313 K. At ths emperature, the vapor pressure of water is 7370 Pa, That is ifthe water vapor were in equilibrivr with aplanar liguid water surface, the pressure would be 7370 Pa, However, ifthe water vapor were in equilibrium with small spherical water droplets, the pressure wovld exceed 7370 a, For instance, ifthe droplet radii were 10 nm, then P* = 8070 Pa. If droplet radii could be made as small as 1 2m, P™ = 20,000 Pa. Inusing Eq, (19-33) tomake suchestimates, we have assumed thatthe srface tension ‘of water is independent of drop size. This assumption is questionable for very small drops 9-33) Example 19.2 If spherical drops of water (ofthe same size) were in equilibrium with water vapor at 1.1 bar and 373 K, estimate the droplet radii and the pressure within the drops. At 373 K, the surface tension of water is 0,0589 Nim and the molar volume is 1.87 x 10-° m°/mol. The ‘vapor pressure of water at 373 K is 1.013 bar. Solution With Bq. (19-33), 2) (0.0589)(1.87 x 1 8314)373)r Seaton 19.3 Effects ct Pressure Differences across Curved Intrtaces 299 with r=8.6% 107 m=8.6.nm, PB p28 = ONO.0589) _ 1 37 107 Pa 7 36x10 and PR 11x 10° 41.37% 107= 1.38 x 107 Pa Within such drops, the calculated pressure is very large. It is this high pressure thet increases the fugacity of the Liquid water so that a higher vapor phase Fugacity results at ‘equilibrium. [A similar treatment is possible forthe case where We have a vapor-phase mixture at 7* and P% in equilibrium with small liquid drops. Let x? represent liquid mole fractions within the droplet and ybe the vapor mole fractions in phase c. The analogs for Eqs. (19-26) through (19-30) with 7= 7° = 7? are: BP Th) =f. 9) (19-34), FPP T= HP% TPF (19:35) POO TH HO Mash Vf ye] co39 In Bq, (19-35), 6 isthe fugacity coeticient of component j inthe vapor. isthe activity coefficient of jin the liquid drop phase and depends on P® and 2°. 9f(Pyys 7) is the fugacity coefficient of pore vapor j at Tand Py Substituting Eqs. (19-35) aod (19-36) into Eq, (19-34) leads to a rigorous but unwieldy expression, To simplify matters, assume the vapor phase is an ideal-gas euixture (6)’= 1.0), the liquid drop is an ideal solution (f= 1.0), tbe pure vapor of j at Py is ideal (Q} = 1.0), and that VP #fP). Then ve-P,,)] =P, a exp| UP Pad . POS =P yal on | (aa) ‘This equation may be compared to Ba. (19-31) for a pure component under similar conditions. ‘There are n relations of the form of Eq. (19-37) and, as shown in Example 19.1, one ‘equation showing how P* and P* depend on drop size (r). These are sufficient t0 solve for the (n= }) unknown mofe fractions in the B phase ag well as for P* and PP. Note that the exponential term in Bq, (19-37) can be considered asa factor that enhances the vapor pressure of each component in the liquid. Since molar volumes and vapor pressures differ from one component to another, the equilibrium liquid drop composition will differ from that of a planar liquid surface in equilibrium with the same vapor. 200 Themodynamics of Surfaces Chapter 19 Phase 6: spherical vapor bubble; Phase o: liquid Lets again start witha pure-component case. The «pase is now liquid at P®, while the B phase consists of vapor bubbles of radi. (The temperatures in both phases are eqhal) Following the same technique illstrated above, PP) =f (19-38) PP” =4(P)Pop on|(z7) , ve «| (19:39) Assuming ideal gases ond V"2f(P), Marygexp eral] (19-40) Equation (19-40) is identical to Ba, (19-31) withthe cB superseripts interchanged, “The interpretation is, however, different, a illustrated in Example 19:3 Example 193 ‘We have a bulk liquid phase of pure ethane at I bar pressure and at a temperature of 270 K. This liquid is in equilibrium with small vapor bubbles of radii. Calculate r and, alto, the pressure within the bubbles, ‘At 710 K the vapor pressure of ethane is 22.1 bar, the liquid molar volume is 738 x 10°8 m'/mol, andthe surface tension is 3.5 x 10" Nin. Solution In this case we have liquid ethane, which is highly superheated, (From Problem 7.3 we see thatthe ethane is ina state very Close tothe limit of stability from a thermodynaraic point of view) Ifthe fiquid ethane were in equilibrium with planar vapor interface, the pressure ‘would be 22.1 bat With Bq (1940), - 4108 exp) (23821075) 108 22.4 x 109] _ s P= (92.1 x 105) | 6314270) = 20.6x 10° Pa with = 206 108 105 = ABSIT 7=3.6x 10° m=36 nm As we noted inthe liquid drop-vapor case, the pressure inside the vapor bubble of the By ‘phase is significantly bigher than the bulk liquid phase, 20.6 bar versus I bar. In contrast to the liquid droplet ase, howerer, the vapor pressure was slightly reduced over its planar value oF 22.) bar Section 19. Effects of Pressure Diflorences across Curved Interfaces oor ‘As we shall see fter, calculation of the equilibrium bubble (or drop) size is an important step in formulating a theory of nucleation of phase B from a bulk ct phase. The equilibrium ‘bubble pressure and size fora superheated liquid mixture can be determined by a similar approach, Phase 8: solid spherical particles; Phase o: liquid For this situation, consider a pure liquid in equilibrium with finely divided solid of the same material. If the solid phase were large and planar, the temperature would correspond tothe freezing point ofthe liquid. The fact that the solid is composed of small fragments leads to a prediction that the freezing point will be depressed, If we assume thatthe solid fragments are spherical in shape with radii r, -26r,, I” A (9.4i) 7 BB py where T, = freezing point of the liquid in equilibrium with the finely divided solid (K) normal freezing point ofthe liquld in equilibrium with a planar solid (K) molar volume of the solid T,, and at the liquid pressure (m"/mol) solid-liquid interfacial tension (Nim) enthalpy of fusion (I/mol) Ad, Ine ‘The derivation of Eq, (19-41) is left as a problem at the end of the chapter. Actual calculations of AT are difficult as few values of c are known, In fact, the measurement of AT for a known value of r has been used to infer values of 0. Phase 8: solid spherical particles; Phase a: liquid solution Inthis case one is interested in exploring whether the solubility of solute ina solution is modified ifthe solution isin equilibrium with small soli fragments rather than with large (planar) solute crystals, To formulate the problem, suppose that we bave a binary solution of 1 and 2 at some pressure and temperature P#, 7%. This solution is in ‘equilibrium with small fragments of a pure solute phase (component 1) at 7 and P®. Then 19-42) FP) = FO8 A) woe Next, assume that a liquid solution of I and 2 atthe sare temperature and pressure (P% were in equilibrium with a planar solute surface. In this case the solute concentration in the liquid is the “equilibrinm" solubility 2f ¢, 19-43) FEY =HKO Ey) » we Themodynarics of Surtaces Chapter 18 ‘Note that in the planar case, the solid pressure is P®. Taking logarithms of Eqs. (19-42) and (19-43) and subtracting, then, with Bq, (8-158), we obtain a ye a ee) (19-44) ‘where ay is the activity of the solute in the solution that is in contact with the small solid solute particles and a, eis the Solute activity ina solution in contact with large planar surface (the normal equilibrium solubility case). Approximating the ratio of activities by the ratio of concentrations and using P®— P= 26/r yields «0 ?) (a9-4s) Since the exponential terms greater than unity, the solubility C, exceeds the equilibrium solubility C), IF the solid ionizes during dissolution, the exponential argument sbould be divided by i, the increase in the number of particles during dissolution and electrolytic dissociation Equation (19-45) may be criticized from many points of view. Small particles are probably not spherical, and a departure from this simple shape can considerably affect CiCyq values (see, for example, Jones (1913)]. Also, the correspondence between ‘concentration and activity may not be acceptable for highly soluble compounds. Finally, and most important, itis probably not reasonable to associate 6 with a solid-liquid interfacial tension, since, for small aggregates of only a few molecules, this interfacial tension loses any meaning. Harbury (1946) suggests that a fcitious interfacial tension, ©, be used where, from the few data available, 6” is much less than 0. "A modification of Bq. (19-45) has been used in tbe developrnent of two-dimensional nucleation and growth theories, {see Ohara and Reid (1973) for further discussion}, ‘where itis assumed that crystal growth is controled by the rate of formation of small pancake-shaped nuclei on a large planar crystallite surface. For such a solid shape, as ‘shown in Example 19.1, P® — P® 0/7, so, when Eq (19-45) is derived, the factor of 2 has been dropped from the expovential term. Then, if the solution supersaturation for ‘Solute | is defined as Ge (19-46) ¢he equilibrium pancake radius is ov ra _ 19-4 AT In (1+S) (oe A definite size of a two-dimensional nucleus is then associated with a given supersaturation of the solution. ‘Section 18.4 Pure-Componant Relations 908 19.4 Pure-Component Relations The Fundamental Equations for any two phases & and B, separated by a surface phase «G, have already been given in Eqs. (19-12) through (19-14). Let us assume that the interface between and B is not highly curved so that P*= P* = P® and begin our evelopment by considering a closed system in which there is but a single nooreacting component j present. We have algo showm that, at equilibrium, T= Tand uf =pP = uf = py. The total Legendre transform of Eqs. 29-12) through (19-14) yields ‘Gibbs-Dubem equations (see Eq, (5-105) forte ce and i phases, Sar + VP aP dy = 19-48) -S ar+ dP ay= (19-49) and for the surface phase, in extensive form, = ar+V aP—ado-N? dy =0 (19-50) ‘We divide Bq, (19-50) by @ to obtain the intensive form: ~S dT +d? ~ do-T dyy=0 a9-st) In Bq, (19-51), S° = $°/4 is the entropy per unit area, Similarly, t= V°/aL is the thickness of the surface and T = Nf/d is the surface concentration, moles of j per unit area Eliminating dP and du, from Eqs. (19-48), (19-49), and (19-51), do TH yst- sy -S = 9-1) -&— (19-52) Oe ‘Equation (19-52) is symmetrical in o. and B and terms containing these superscripts ray be intochanged, ‘Tbe Euler form of Eq. (19-14) may be written a5 o=I-1S'-Ty 029-53) [If Eq, (19-52) is nmaltiplied by 7 and the result added to Eq, (19-53) and then the Euler form of Eq, (19-13), as multiplied by Fis used to eliminate the Ty term, we get: 0-78 i rab) = Eva) to) vi where H° = H?/a = (U° + Pa. Equations (19-52) and (19-54) relate the surface tension and surface tension-temperature gradient to thermodynamic properties such as entropy, enthalpy, and volume. Iti oot immediately obvious, however, that these relations are invariant, ‘with respect tothe variations in thickness, of the surface. Suppose fr instance, that Tis extended by a slight arnount into phase B, then aso ae 904 ‘Thermodynamics of Surfaces Chapter 19 at ae Differentiating Eq. (19-52) with respect oa variation in into phase B, the right-hand side becomes zero. Thus, te relation is not dependeat on ths particular variation in Similar results are obtained if tis increased into phase 0. ‘This invariance leads, of course, to an indefiniteness about terms such as $°, H®, 2, and As noted above, fora given 1, there is a given S°. If tis increased in phase B, per ‘unit area, the entropy will increase by S*(dt/V¥). This new S° will depend on the value of S? to a degree proportionate to the increase in t. We are accustomed to visualizing the properties of the surface layer to be more representative of aless mobile phase or of 1 discontinuous phase in a two-liquid system. For example, in 2 liquid-gas system, we ‘often imagine the surface phase to possess nearly liquid-like properties. (Note that this is always possible by choosing the position of the surface layer in a manner to exclude any appreciable gas phase.) By choices of this nature, we may simplify Eqs. (19-52) and (19-54) to more common forms. For example, in a gas-liquid system, if phase B were Tiguid and phase ot gas, then 1/T is comparable to = V-, which is much less than (V— V4) =(W" - ). Equations (19-52) and (19-54) then become ‘Se -1st (19-55) “at do - - 19-56) oT opa HT (19-56) ore ass Even in these simplified forms, $°, H°, and I" are still indefinite and depend on <, although neither (5° — TS) nor (HTH) depend on © Surface tension decreases with increasing temperate anda convenient estimation ‘equation for nonpolar materials is given by Brock and Bird (1955): o= Fr a -1)" (19-58) where P, is in bar, T, in K, and o in N/m, (15-59) and T),=TYT- ‘Other estimation techniques bave been suggested (Reid, Prausnitz, and Poling (1987), and Scriven and Davis with their colleagues Carey and Boniomo (1976, 1978) have employed mean field theory to calculate surface tensions Since da/dTis negative, (S? ~ Sis positive. This quantity represents the difference ‘between the entropy (per unit area) in the surface film and the entropy the same surface would have if it had the properties of the buik liquid phase. In a similar anner, 6 ~ T(do/dT) may be visualized as the enthalpy difference between the surface film and Section 195 Multicomponent Relations 908 bulk liquid. With Bq, (19-57), the surface tension itself may be considered to be the difference in Gibbs surface energy and the bulk liquid Gibbs energy expressed on a unit area basis, This isothermal Gibbs energy cbange is often defined to be the reversible ‘work required to bring material from the bulk liquid to form a unit area of surface. ‘Before leaving this section on pure component surface thermodynamics, let's review the developments presented thus far. In the initial sections of this chapter, from mechanical considerations only, the concept of surface tension was developed. These same arguments led to some interesting conclusions such as the pressure difference existing actoss curved interfaces, the euhanced vapor pressure over small convex liquid or solid surfaces, ete. The application of thermodynamics in this development as ‘minimal although it was proved that in any equilibrium multiphase system, regardless cf curvature, the temperature and chemical potentials were equal in all phases. Fromn these concepts, the surface tension and its temperature gradient were related to fundamental thermodynamic properties of the surface, The utility of this latter development may be questioned. The surface layer emphasized in the foregoing paragraphs is held by some to be completely fictitious and devoid of true physical significance; its depth is indefinite, i is @ composite of the properties ofthe bounding phases, and the absolute values of S°, H°, et. are dictated solely by the exact position and thickness of the layer~as defined by the user--not by nature. 19.5 Multicomponent Relations The thermodynamics of surface layers in multicomponent systems is straight-forward extension from those developed in Section 19.4 for single components, although the algebra is considerably more complex. The relations employed are shown below; as before, the surface-layer equations are expressed in terms of a unit area of surface (ie,, S° ¥/a; T)=Nj/G). The Gibbs-Duhem relation, Eq. (19-51), becomes 7 nds = Sar-tdP+Y. Td, (19.60) a For both phases cand 8 one may express the chemical potential of any component as, for example, in phase Bi, a aero ened ag (9-61) me (OF waa) At constant composition, inthe Band «phases, with Eqs. (19-60) and (19-61), -Sret lar — and from equations ofthe fokm of Eq (19°61) for any composentk, with all de = 0, de Love ar 9.62) a 908 Thermodynamics of Surfaces Chapter 19 (all constant) (19-63) Equation (19-62) may be substituted into Eq, (19-63) to eliminate all pressure ferms. Applying Bq, (19-62) to a vapor-liqud system where the vapor phase is Land the liquid phase is B, «/20 is comparable to the liquid-phase volume VE = Ef, x£Vf. Assuming ideal solutions where VA = Vk. “Ser P+ Sy(-¥= . eEMbev Ene En (sow ase “Thus, inthis case, & =S°- 1,5; (constant composition in L phase) (19-65) a Equation (19-64) is a good approximation to eliminate the “AP* term since the smal residue £1; 0 must still be divided [as from Eq, (19-63)} by a large number, (Hi -F)= AVeoponaason t0 Teduce further the magnitude of the multiplier of the "dP" term. The forme of Bq. (19-65) i identical to Eq. (19-55) andthe discussion following ‘the latter equation is also applicable to Eq. (19-65). Thats, the equation is invariant with respect tothe position or thickness of the surface layeras long as each bounding surface of the interfacial layer isin a different phase. ‘There is, however, a limitation to either Bq, (19-61) or (19-62), That is, the composition of all components inthe liquid phase must be held constant. This restriction originates from the elimination of the di, terms in Eq. (19-60) with Bq. (19-61) as simplified by forcing the terms containing (@u,/axp)dy to be zero. There is no thermodynamic inconsistency here since frot the phase rule there are n independent variables and if ( ~ 1) compositions in the liquid phase are fixed, theo o can be expressed as a function of temperature only. Similar statements may be made if the derivation of Eq. (19-62) were made by using a relation ofthe form of Eq. (19-61) but for the a phase. The final resulting equation (19-62) or (19-65) does have this composition restriction, and as such, the genera? applicability is reduced. As in the case of many other multicomponent zhermodynamic relations, other composition restrictions may be imposed and different results obtained. 19.6 Surface Tension—Composition Relationships Euler integration of Eq. (19-14) allows one to define a Gibbs energy for the surface phase. Section 19.6 Surface Tension—Composton Relationships 07 P= -18 +P 0a Lup «1966) z Lets restrict our presentation toa binary systemn of 1 and 2. Then, if Bq. (19-66) is divided by the tral moles inthe surface layer, M*= NP +N, oe 19.67) where G* is the Gibbs energy per mole in the surface layer, 6 is the surface tension of the mixture, and x9, xf are the mole fractions of 1 and 2 in this layer. Qis the area per mole and is often written Q= 20, +299, (19-68) , and O, are partial molar areas for components 1 and 2. Substituting Eq. (19-68) into Eq, (19-67), we obtai =H, + 0) + 394, + 02) (19-69) Next, we can express the swaface Gibbs energies for pure components 1 and 2 at the ‘same temperature as Gaw+oQ, and Gl=uh+0,0, (19-70) In Bq, (19-70), pf and uf refer to chemical potentials of pure J and 2, and 6, are the ppure-component surface tensions, and ©, and ( are the pure-component surface areas per mole of material. ‘With Eqs. (19-69) and (19-70), we can form a mixing fanetion, AG? = 6 —1GF — BGP xFL(U + 2,)— GY +.9,9,)] (19-71) + 5llty +00) ~ (H3 +.6,0)] If we then write the analogous equation for the Gibbs energy mixing function for the bulk liquid phase, AG = xh, — 12) + (hy — WS) = RT In ay +4 RT In ay (9-72) Comparing Eqs. (19-71) and (19-72) suggests that it might be convenient to define "surface chemical potentials" as follows: Gant, and Gantoh, and for pure component reference states, (19-73) Gewi+o,Q, and Ganj +o,0, Thus, G.- Gearing? =RTin yet G-GQeRTing=RTin fat 9-74) 908 ‘Thermodynamics of Surfaces Chapter 19 Equation (19-74) then allows us to introduce surface activities and activity coefficients in terms of surface chemical potentials. Using Eqs. (19-73) and (19-74) for component =RT In a, =RT nym, we get UD 6, - 3,0) = Rn fs? (19-75) = RT In Yyx, + (6D, - 6,2) (19-76) ‘InBq, (19-16), the surface composition of component 1 is elated othe bulk composition (x,) and activity coefficient (¥;). The surface properties involved are ¥f, 6, 6), Q), and 2), Writing the cornparable equation For component 2 and adding, Hh [Mo] a [O~G%] 1g a9 sof Sams Ee er (9-77) Before discussing the use of Eq. (19-77), let us simplify it to illustrate an important point. Assume ideal solutions in both the bulk and surface layers and fet 2, 2, =2)=0; ther, afer rearrangement and expansion, we get 6 16 Poa (6,-09" 097 ‘With an estiraate of ©, the mixture surface tension may then be determined. Also, one should note that Eq, (19-78) predicts that o is smaller than the mole fraction (bulke liquid) average of the pure-component surface tensions. Returning to Eq, (19-76) or (19-77), these wese used by Sprow and Prausnitz (1966) toestimate surtace compositions and mixture surface tensions for simple liquid mixtures. In this case the surface was modeled as a regular solution to obtain surface activity coefficients. Also, surface areas were correlated with liquid volumes raised to the two-thirds power. A different approach to estimate surface compositions uses the Gibbs-Duhem equation for the surface layer (Eq. (19-50)] (see also Shih and Chen (1968) and Goggenbeim (1967). Fora binary of | and 2 at constant temperature and pressure, .do+NF di, + ME dy =O (19-79) Dividing by N°, the moles in the surface layer, we obtain do +29 dh, +28 ahi, =0 (19-80) where = a/N® and xf = N/M. From the Gibbs-Duhem equation written for the bulk liquid, at constant temperature and pressure, Seaton 186 Surface Tension—Compostion Relationships 908 xy dh +5 dhiy =0 (19-81) Eliminating dj, between Eqs. (19-80) and (19-81) and making use of Bq. (19-68) yields yee TDi do/t) 1144 -B)(dora,) As in Eg. (19-76), partial areas ©, and Q, are necessary to estimate surface com- positions when employing Ea, (19-82). The derivative (d6/,) could be written as ds _ do/dx, do/dx, Gy G7, ~ REA OY 7AR, and evaluated from data showing how the mixture surface tension and bulk-liquid activity coefficients vary with composition. (19-82) (19-83) Example 19.4 [Bstimate the ethanol surface mole fraction in » 20 mole % ethanol-water solution at 298 K Some mixcare data are given below for T= 298 K Mole Surface Ehanol—Ligald molar fraction tension activity "volume ethanol (N/mm x1@2)_coefBident _ (emo 10 20 10 387 09 26 10 543. os 232 1.02 99 07 2385 1.06 454 06 246 133 410 os 234 325 307 oa 2638 Las Bi 903 n6 176 231 02 Br 22 254 01 366 302 216 0.04 09 342 195 ° a2 = 1805 Solution Equation (19-82) is used. To estimate the panial molar areas for ethanol and water, the relation given by Sprow and Prausnitz (1966) is used: ~ [Ww Ll x, 3, ff [om ‘where V7 is the partial molar volume of compoventj inthe surface layer. We will assume 310 ‘Thenodynamics of Surfaces Chapter 19 about 04, the molar volume daa show that Tgy = 587 cml and Tho = 15:8 cem'/mol. Thus, sa7_Y* =(— 875} (6.020% 10° Qe H (coast | (6.022 107) = 1.28 x 10° em?/mol = 1.28 x 10° m°/mol y= 5.3 X 108 cm*imol = $.3 x 104 m?/mol “To determine dae), this derivative is writen as (UR do/A In (2) oe and © ploted versus In C}pox The slope when poy = 0.2 18—1.6% 10"? Nim’, Therefore, do _-1.6«107 2 Berg PG -— 64010 mat With Bq, 19-82), ___0.2~ (0.85.3 x 10°)(-6.4 x 10°) =o EONS Ty (0.8)(1.28 x 1085.3 x 10) 6.4 x 10°) Tein teresting to note that if Ba 19-76) i used to estimste Sioy, and Yon i equated {0 Yeon i the data table at xpog ~ 0.77, ten Yagn = 1.08 o y = y3)(1.28% 105)] _ oe OBE | Oe «00 “The agreement between the two methods 0 esinate Boys not particularly good. In Eq (19-76), due to the exponential term, the ealeulated value of 22 i uit sensitive to the surface tensions and areas used inthe computation 19.7 Nucleation "Nucleation refers to the birth process of a new phase. Jt obviously has many important ramifications in science and engineering. Ifa homogeneous, particle-free, pare vapor is cooled until the pressure is equal o the vapor pressure, thermodynamics would indicate that a liquid (or solid) phase should form. The actual facts show that this frequently does not occur. In such a case, tbe temperature must be decreased below the normal dew-point or saturation temperature before the second phase appears. Such undercooling is, however, not found ifthe gas contains many “dust-like” particles o if the gas were “seeded” with a small quantity of the liquid (or solid) phase when the dew point was reached. Similar statements apply to he precipitation of solids from liquids or the supetheating of liquids. “The reason for these phenomena lies inthe fact, developed in Section 19.3, that srnall "nuclei" of the new phase have higher vapor pressures (or more accurately, higher chemical potentials) than tbose of a bulk, planar phase. ‘These nuclei will only be stable ‘when present in a supersaturated mother phase. ‘Section 19.7 Nucleation out ‘The equilibrium and stability criteria that are applicable to the formation of a new phase have already been giver in Egs. (19-9) and (19-10); that is, at equilibrium, the availability fonction, B, is either a minimum for stable equilibrium or a maximum for unstable equilibrium, Let us assume that we have initially a B-free phase, ot, which is always at T and P as dictated by isothermal and isobaric reservoirs (see Figure 19.2). We shall allow the formation of a B phase but at the same time insist that phase ot remain at T and P, The moles in the O-B systerp are constant, We wish to determine the change in availability during this process. From the definition of B in Eq. (19-8), 4B=B-Byy (19-84) where Bq is the initial total availability before the B phase forms. Thus, AB = (US + PY*— 3) + (UP + Pye_ 3) ++ PTS) -U4 PTS), (19-85) Now NE, = N+ NBs Ne 19-86) Ut TS PVE + ut (19-87) Pars! — Pe +P s woa Ua TS - P4054 0 ne” ye Oye so that substitution of Eqs. (19-86) and (19-87) into Eq. (19-85) yields AB= Muh) +P- P| +00 + A((UP— U9) + (P- PV) (19-88) Equation (19-88) is, of course, very similar to Eq. (19-15); the principal difference is that inthe former we assumed thatthe temperatures were everywhere equal inthe final system. A finite, rather than infinitesimal change was also proposed. If we proceed one step further and assume that the final state is an equilibrium state, AB equals the change in availability when a homogeneous phase ot changes to an 8. system with small fragmeats of the B phase in equilibrium with the residual ot phase. Also, at this terminal state, as we have shown in Eqs. (19-19) and (19-20), there is equality of chemical potentials throughout the system, so that Bg (79-88) sropifies to AB=MP- PY? 40a (19-89) ‘where we have also neglected the very small contibution due to N°(P - P®)V®.1f phase Bisa apher, then fom Bq (19-23) with @= 47 and = (398, ove Tremocjnemics of Surfaces Chal 18 16 Soe ap= 19-90) BaF pe Expressions for (P? — P) that were derived in Section 19.3 may be used to determine AB in terms of P* and other system variables. Relative to the question of stability, we note from Eq, (19-88) that B= fF, 9) since VP and @ depend on r. If we expand the availability in a Taylor series around the state of equilibrium, we get B-B,,=B, 8r + By BN +B,, 8? + 2B, Br 5 (19-91) By ON + where we have adopted a shorthand notation for partial derivatives [eg., B, = (QB/2r)y2, Buy = (B/N), etc.]. The first-order terms are zero at equilibrium; that is, from Bq, (19-88), neglecting the surface phase since it contributes negligibly, and noting that u%, P, and 6 are constants, we obtain 6) > ()-s(2], += Phan) +enor (19-92) ‘The first two terms cancel since 4 fat), Se 99 3 or we \ or Thus, B,=(P— Pan) + Bor (19-94) and, as expected, at equilibrium, using Eq. (19-23), we have B,=0 Next, we will show that By is also 2ero at equilibrium. Beginning again with Ea. (19-88) with a spherical nucleus assumed (N° = 4/3 xr°), we get By - 3] 19-95) but Say. a (a (1996 » (ant ‘Therefore, ‘Section 19.7 Nucleation ong oO 9.97) by Bq, (19-19). Next, considering the second-order terms, they may be rearranged by forming a sum of auaes B, (B, BA Y(8r) Bt Ze)» Ma ae We need to develop expressions for Byyy Bry, and By Burt Beginning with Eg (19-97) and difereniaig with respect to NP, with wa (19-98) conttant, fay?) fn=(B »(l (19.99) ‘To obtain amore convenient expression for By since phase B is a constant 7, Pof0h Applying Euler's theorem yields 4a] ™ (oe (19-100) Let a “Fe 9-101) w ‘Theo, with Eg. (19-100, (19-101) and Y= $07, (19-102) (19-103) But (19-104) So 24K 128 _ ge 19-108) _ B,y: Beginning with Eq, (19-94) and differentiating with respect to N®, we have 914 Thermodynamics of Surfaces Chapter 19 ap?) _ 4m? By= ~4nr| 22 | = - 19-106 y= 4 lav} a (19-106) ‘where Egs. (19-100) and (19-101) have also boon used. Clearly, Byyy is positive since K> 0. Thus, the stability of our system is determined solely by the coefficient (Byyy B,,~ B) in Eq, (19-98), 3-H Sn? ony eno) 164 (Bro) GRP) - IR _ oe {8010 mB Biv OB eM” ea (19-107) By ~tn0 <0 (19-108) ‘The interpretation of this results that a phase B erabryo, in equlibriom witha mother phase o, is ina state of unstable equilitriam, 1a his examination, the formation of a new phase B from a mother phase cr actually procesds by increasing the availability of a system—a progression thats counter to our intuition and to usual tends in therroodynamaics. Normally, systems seek astate of lowest availability In a molecular sense, by fluctuations in density, sroll fragments of a new phase aze formed from a mother phase 0: which is in a metastable condition, All these new feagments are unstable and disappear until a fragment ofa critical size is formed. Then, and only then, can the fragment grow to form & bulk new phase B. ‘The change in availability to form an equilibrium-sized sphere of phase B (Eq. (29-90)1 is often employed in nacleation theory, wherein itis assurned that che rate of nucleation is proportional to exp( - AB/R7). An interesting study of the supecheating of liquids which demonstrates the utility ofthe availabilty concepts summarized in the work of Apfel (1970). References and Suggested Readings Adamson, A.W. (1982), Pico! Chemistry of Surfaces, st e, Wiley Interscience, NY. [Chapters {and I provide complementary material from a Physical Chemist's perspective) Apfel, RE. (1970), "Vapor cavity formation in liquids,” Tech. Memo. 62, Acoustics Research Laboratory, Harvard University, Cambridge, MA.; see also Apfel, RE. (1971), J. Chem. Phys. $4, 62. Brock, LR. and Bird, RB (195), “Surface teasion and the principle of corresponding states,” AICHE J. 1, p 174-977. Carey, BS., Scriven, LE., and Davis, H.7, (1978), "Semiempiricl theary of surface tensions ‘of pure and normal alkanes and alcohols,” AICAE J.,24, p, 1076-1080; and Bongiomo, V., Scriven, LE,, and Davis, H.7, (1976), "Molecular theory of fuid interfaces,” J. Coll In Set, 57, p 462-475 Problems 318 Guggenbeim, E.A. (1967), Thermadynamics, 8h ed, North Holland, Amsterdam, p 159-169, 213-217, 237-238. [excellent review of surface thermodynamics} Harbury, L, (1946), "Solubility and melting poiat as functions of particle size," J Phys. Chem, 80, 190 Jones, WJ. (1913), "Uber die Beaichung zwischen geometischer Form und Damptdeuck, sliheit, und Formenstailiit," Arn Phys, 41,9 441 (Ohara, M, and Reid, R.C. (1973), Modeling Crystal Growth Rates from Solution, Prentice-Hall, Englewood Cli, NJ, Chap. 2 Reid, RC. Prauoitz,1M., and Poling, BE, (1987), Properties of Gases and Liquids, te. ‘MeGraw-Hil, NY., Chapter 12, p 632-65. Shih, ¥-P. and Chen, S-A. (1968), A note on the thermodynamics of surface tensions of binary solution,” AICHE, 14, p 973, Sprow, FB. and Prausnitz, IM, (1966), "Surface tensions of simple liquid mixtures," Trans. Faraday Soc., 62, 1105, Problems 19.1. In a distillation tray there is considerable spray of very fine liquid droplets. Since small droplets have higher vapor pressures than plane liquid-vapor interfaces, we would lke to know whether or not the small spray mists have significantly different relative volaiites than those of plane interfaces. Take, for exearple,ethanol-water at 298 K. Using the data given below, estimate the relative volatility of alcohol-to-water for 0.1-ym-diametee drops and compare this tothe volatility for plane surfaces. x(tmole ethanol) Pasent Pa) 0 00 10 2310 Py 3570 20 4160 ry 4560 30 4920 0 5350 7 5850 80 6440 90 710 100 7870 (© Liquid composition, 50 mote % water. (©) Planar vapor-liqud equilibrium at 298 K. (©) Surface tension of $0 mole % ethanol-water solution at 298 K = 0.0254 Nin @) Densities ofiqud at 298 Kare given in Example 19.4 (@) Assume thatthe surface tension is independent of drop size. 918 92. 9.3. 194. ws. 19.6. ‘Themodynamics of Surfaces Chapter 19 (9) Assume that the partial siolar volumes of both components in the Tiguid are independent of pressure. [Estimate the composition of the vapor in small vapor bubbles in equilibrium with » superheated liquid mixture of 95 mole % ethane and 5 mole 8.n-butane at 270 K and | bar pressure. Also, what is the pressure inside the vapor bubble and equilibrium bubble radius? Assume that the liquid mixture forms an ideal solution aad thatthe vapor in the bubble isan idesl-gas mixture, Other data ate shown below at 7= 270 K and Pruuis)™ Var Butane hem, ones oas PyPa anxit saat Vapin hood — 73810 68x 10 Tne surface enson ofthe mize ie etraaed tobe 3.Sdrp + 15.3xq ~ 5.02 xprg) (10°) Sia? where xpi the mole fraction ethane and xg the mole fraction n-butane, In theexpresson for surface work, Eq, (19-1) the pressure-volume tm is given as P dV. one were dealing with a curved surface, the intral pressure difers from th external pressure, Which presture should one use in Eq (19-1)~-ot does itmake any difference? Why? Derive Bq, (19-41) and state any assumptions made ‘Whats the general equation showing the approximate slope of a plot of In P (equilibrium) eps 1/7 er sal ropes of iu? Fr wat 98 K where = 007275 Nn, 24.19% 10" Yimol, Vex 18 cm mol forr= 10" em, what isthe slope in K? How Sect est vaputeion vary wit drop sac? [APh.D. thesis at Syracuse University cariedoutby Dr. Femandex ba studied the growth rats of waterie thin platelets in a subcooled wera slution It was postulated that the platelets grewby extension of scalloped edges ofthe crystal perpendicular tothe basal plane, His physical modal studied two-dimensional rowrh ofa single sallp as showa ‘(Gee Figure P19.6). Seaton exe ee gown rection Flow oF Basal plone — water Cress section of 1 Schlop Figure P96 Problems 917 192. “The geomattc shape af sao is believed to be nearly parabolic, bute curvature near the pis almost constant; ths, tis psd that Ba (19-41) tay be used to eae the tip surface temperature In his cas, the temperature athe ie tp Ts given by peor 2a Tm a vere isthe inertial tension betwen slation and pre water ce, Teh esing Point of pre water, 273.2 K, Wis hemor vole of ie Agee hea of ion fee, and isthe ip curvaie. Asm no het conduction twoagh he oe (a) Detive hit relationship fr salt solution conn weight percent el What appronialions ae necesay? Assuming that the equation given above is applicable, let the growth process be cootrlled by the rate of heat transfer away fram the tip; thats, RAH, (T,-T) and q ro) ‘whore qs the heat ux the heat transfer coefficient, 7,, she bulk temperature inthe salt bath, and R the linear growth rate of the tip. ‘The heat transfer coefficient for flow normal toa parabolic cylinder may be approximated as ‘where ris the tip radius, kand n the thermal conductivity and kinematic viscosity of liquid ‘water, respectively, v the impinging liquid velocity, and A isa constant (©) From these relations and the concept of a steady-state value of R during growth, determine bos 2 depends on the experimental variable AT'= 7, ~T., For example, does R double if ATs doubled? ‘The surface tension of very dilute aqueous solutions of butane! has becn measured at 298 K and reported by Harkins and Wampler (J. Am Chem. Soe., 53 (1931), 850). These authors also report the activities of diluce solutions at «Function of molality as follows: ore 19, Thermodynamics of Sulaces Chapter 19 Surface tension Metality (m) Actety* (Wim x 10) ‘0.00329 0.00328 72.80 ‘0.00658 0.00654 72.26 001320 0.01304 082 0.0264 0.02581 68.00 0.0836 0.05184 als 2.1050) 0.09892 3631 oan 019277 48.08 0.4330 037961 aa87 0.8540 71189 287 “sunt se, Estimate the mole fraction butanol in the interface at a bulk molality o£ 0.1050. If you wish, you may assume that, on the average, one molecule of butanol occupies abo 0.27 ram? and one molecule of water, 0.07 ni: {A spherical bubble is enclosed by a thin ethano! film; the bubble is 1 mm in diameter and the film is 1 10 mm thick. The bubble is in equilibrium with surrounding air, which fs at 1 bar and 298 K. Data: mem->0. For ethanol, the surface tension is believed (o be insensitive to pressure variations but is related to temperature as onoont K.oin Nim) ‘The surface heat cay ‘The density ofeshanol is assumed independent of temperature or pressure and equals 0.79 fem’ and AFap, cas = 930 Ug at 298 K. (@) Evaluate the surface energy ofthe ethanol film, (2U°/8A)p,» Yim? (b) A small tube is inserted into the bubble snd air (at 298 K) blown in so that itis ‘expanded rapidly to a diameter of 3 mm. Neglect any heat or mass transfer from the sir to the liquid film and assume thatthe temperature of the film is uniform throughout, What isthe temperature inthis film after the expansion? Appendixes A Summary of the Postulates 1. For closed simple systems with given internal restraints, there exist stable equilibrium states that can be characterized completely by two independently variable properties in adltion to the ‘masses of the particular chemical species initially charged. IL. In procestes for which there is no net effect on the environment, all systems (simple and composite) with given internal restraints will change in such a way that they approach one and only one stable equilibrium state for each simple subsystem. Io the limiting condition, the entire system is said to be at equilibrium, I, For any tates, (1) and 2), in which a closed syste sat equilibrium, the change of sate represented by (1) -> (2) andor te reverse change (2)» (1) ean occur by at east one adiabatic process, and the adiabatic work interaction between this system and ts suroundings is

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