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Molecular Physics

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**Simple MSA solution and thermodynamic theory in a hardsphere Yukawa system
**

Mitsuaki Ginoza

a a

Department of Physics, College of Science, University of the Ryukyus, Nishihara-Cho, Okinawa, 903-01, Japan Available online: 11 Aug 2006

To cite this article: Mitsuaki Ginoza (1990): Simple MSA solution and thermodynamic theory in a hard-sphere Yukawa system, Molecular Physics, 71:1, 145-156 To link to this article: http://dx.doi.org/10.1080/00268979000101701

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A thermodynamic theory is also presented in terms of simple rational functions of the above-mentioned parameter. 1. For these purposes. The aim of this paper is (i) to present simple expressions for the MSA solution and the thermodynamic theory. In these studies. 2]. Okinawa 903-01. Japan (Received 29 January 1990. it is interesting to investigate in detail the manifold of solutions of the single nonlinear equation for the n-component single-Yukawa-term case. The HSY mixture has often been used as a simple model to describe compoundforming and phase-separating liquids directly [1. The manifold of solutions of the nonlinear equation and the choice of the acceptable solution are diseussed. and the effect of the 'charge-non-neutrality' condition on thermodynamic functions is discussed. It is well known that the above system of nonlinear equations has a manifold of solutions. the present author [5] showed that the system of nonlinear algebraic equations defining the coefficients of the Blum-Hoye solution can be simplified remarkably. University of the Ryukyus. 1. In the case of Yukawa terms with factorizable coefficients. 2]. VOL. and in the single-Yukawa-term case. in particular. the system can be reduced to a single nonlinear equation. 1990.MOLECULARPHYSICS. it may be useful. (ii) to discuss the manifold of solutions of the 0026-8976/90 $3. accepted 11 April 1990) Downloaded by [University of Guanajuato] at 12:10 18 October 2011 A simple expression for the mean-spherical-approximation (MSA) solution of the Ornstein-Zernike (OZ) equation in the Baxter formalism is presented for the case with n components and a single Yukawa term with factorizable prefactor: all coefficients of the MSA solution are given in terms of simple rational functions of a parameter that is defined as the acceptable solution of a nonlinear equation. The formal MSA solution of the Ornstein-Zernike (OZ) equation for the ncomponent m-Yukawa-term ease has been given by Blum and Hoye [3] in the Baxter formalism and by Niizeki [4] using the Laplace-transform technique. if a simple MSA solution and thermodynamic theory can be obtained. NO. 71. In this context.00 9 1990 Taylor & Francis Ltd . Pastore [6] gave an interesting discussion regarding the manifold and showed that the branch of the acceptable MSA solution can be singled out by the criterion of non-singularity of the Baxter matrix in the upper half of the complex-wavenumber plane as well as on the real axis. Nishihara-Cho. and it may also serve as a reference system in perturbational or variational methods for the determination of the thermodynamics and structure of a liquid system with more complex potentials. have been made by many workers [1. including a neutral hard-sphere mixture and a charged hard-sphere mixture as limiting cases. the mean-spherical approximation (MSA) has often been employed. College of Science. Introduction Studies of the thermodynamic and structural properties of a hard-sphere Yukawa (HSY) mixture. 145-156 Simple MSA solution and thermodynamic theory in a hard-sphere Yukawa system By MITSUAKI GINOZA Department of Physics. Recently.

In section 2. 7] 2nrco(r ) = . In section 4. is the concentration of/-species spheres. The simple analytic MSA solution Let us consider an n-component HSY mixture consisting of equal-size hard spheres interacting with each other via Yukawa potentials outside spheres. a ct ~o dt h. the MSA solution in the Baxter formalism is given from our previous work [5]. while (4 b) is obtained from (1) and (3) using the non-singularity of the Baxter matrix. (1) where p is the total number density and c. defined by the following closure relations for (1) or (4 a. the manifold of solutions of the nonlinear equation and the choice of the acceptable solution are discussed. he introduced a matrix Q(k) that is assumed to be non-singular in the upper half of the complex-wavenumber (k) plane as well as on the real axis and whose (i. where 0o(k) has the form Q. The latter are defined by the OZ equation ho(r) = co(r ) + p ~ c. In section 3.~. as usual.1 co(r) = K_~ e-z. and it is shown in the Appendix that. (r < a).~l t .~[r 1 . a thermodynamic theory is obtained on the basis of the acceptable solution above.p(c i cj)l/2Oo(k). (5 a) (5 b) r .k) . The MSA for the n-component and singie-Yukawa-term case is.p ~ ct Qa(k)Qjt(. Ginoza nonlinear equation and the choice of the acceptable solution and (iii) to investigate the thermodynamic effect of t h e ' charge-non-neutrality' condition as an application. Downloaded by [University of Guanajuato] at 12:10 18 October 2011 2.r l)(r .b): ho(r ) = . Concluding remarks are given in section 5. j) element is of the form 6 o .drd Qo(r) + p ~ c~ | 2nrho(r ) = - ~dQo{r) + 2rip ~ fo dr Q~(t + r)Qjt(t). In the transformation. under the 'chargeneutrality' condition. The thermodynamics and the static structure of the mixture are investigated by means of the partial correlation functions ho& ) or the partial direct correlation functions co& ).k). Baxter I-7] gave a transformation of (1) in a disordered system. f dr 1 c. and the thermodynamic effect of the 'charge-non-neutrality' condition will be investigated.o(k) = and satisfies ~0~176 dr Qo(r)e ik" (2) ~o(k) =. Q(k)./. (r > a).146 M. this MSA solution agrees with that in the original formalism of the OZ equation. | (4 a) (4 b) Equation (4 a) is the real space representation of (3 b). (3 a) l (3 b) The OZ equation in this Baxter formalism is thus [3.t)Qo{t).J dr co(r)e ih" " = Qo(k) + ~4.r I)ho(rl).

Let us define the factorizable case by Kij = K e z Z i Z j.J r Dx.~ Z 2 l + 8 9 B i e #2 =---89 ~ c j Z j ~ d t [ h o ( r ) + 1] ) ./) (8 e) (8 f ) = . After some straightforward calculation and non-dimensionalizations using of a. D o = . we obtain the following from the result of [5] : Aj = 1+ + ~ PN a j.Simple M S A solution in a H S Y mixture 147 where a is the hard-sphere diameter. without loss of generality. X~- Zi . b) are defined by a number of equations related to the acceptable solution of the system of nonlinear equations.a) + t i f f . this system of nonlinear equations can be reduced to the nonlinear equation for a parameter F. (6a) (6b) The coefficients in (6a. and we do not quote them here because of their length.. (7 a) (7 b) (7 c) (7 d) flj = a -~ + aA N aj.1 ) (8 b) (8 c) (8 c') (8. where (8 a) AN = .Z Z. The present author [5] showed that in the factorizable case such as (5 c). and the expressions for the coefficients in (6 a. their solution is ( 89 .F X i + (Oto + oqF)D1. C i j = (7 2 Z i Bie-Z/2"~ z -g Ja ie .b) with closure relations of the most general form consisting of an arbitrary number of Yukawa terms. (5 c) and. For the case of (5 b). F + ~o' J . / k Downloaded by [University of Guanajuato] at 12:10 18 October 2011 D ij e-zr/~ (r>a). e .aZZi aje z.b) can become extremely simple. Blum and Hoye I-3. 8] solved (4 a..Z(rflr . + Cko(z)F + 1 ~ .3r/D2 . we assume ~l cz Z~ = 1.e -z) Qo(r) = ~ + D o e -zr/" (r < a). r~FX i a i .a) + Co(e -z'/" .

It may be of interest to prove directly the equality of the MSA solution obtained above with that of (1) and (5). This. = 12rt tl + 89 ~o=~l l+ 89 -~. 3. which satisfies the following nonlinear equation: F 2 + zF = -. the explicit expression of the latter has not been given except for the two-component case under the 'charge-neutrality' condition. q. however. As can be seen from (7 a-d) and (8 a-f). as will be discussed in section 4. As far as the author is aware.. A = 1 -~/. 1-. We discuss this problem in the Appendix.0 with x = F/z.89 l(z) z3 + { z ) e -z .b).. Moreover. (3 a. J M. Ginoza rt = 6inpa 3.7 ~l(z) 1 + 89+ ) 12r/ 4 1 = •0(Z) -.qgo(Z . and the choice of the acceptable solution will be discussed in the next section.b) are given by simple rational functions of F. our MSA solution in the Baxter formalism contains the quantity F determined by (9). (10a) .e -z Co(Z) - . thermodynamic functions can be expressed in terms of simple rational functions of F. O" (9) Since ~o(k) is obtained from (2). 1 . all coefficients in (6 a.b) and (6 a. has a manifold of solutions.~ I//I(Z)' . Therefore all we have to do before investigation of the static structure and thermodynamics of the mixture is to solve (9).148 with = E cjZj. Downloaded by [University of Guanajuato] at 12:10 18 October 2011 ~Po = 1 + -~.f) as follows: f(x.Z .6Kt/D2(F). however. This equation can be written explicitly with the use of (8 e. The manifold of solutions and the choice of acceptable solution As has been shown in section 2. it is also a rational function of F. z. 6) = .

~. ~oZ -~ 2 ~0 Z XCD ~ r 2@0 r F" (6/Z2)~"~10] 71/2 '~:)J ' XEF = -. CD.6 + ~ 6 ) 0 . C.5. ~/= 0.~ = . where z = 1.~) + (~l~iz -].125 and 6 = 0. as will be discussed in section 5.~o) ~ o. z. E and F are the points where two different solutions merge.oZ--lY +(r 1-6 . ~/= 0. For a given value of 0. 6) as a function of x.0 . and they are as follows: X A B = . Plot off(x. x~. (7 t~ ~ 2 . The asymptotic solutions of (10a) on these six branches in 101 ~ 1 can easily be obtained.~6 ( 1 . BC. It can be seen from the figure that there are six different branches of solutions for x: AB.Simple MSA solution in a HSY mixture where 149 f(x. .@IZ + L'~o(@o - XFG : XEF" 0.x)/L(~oZX-.125 and 6 = 0. DE. the solutions of (10 a) correspond to the intersections of the curve and the horizontal line given by the ordinate value of . rl. In the special cases of 6 = 0 and 1. ~/. 6) is shown in figure 1 as a function of x with z = 1./.. In this figure. the solutions of (10 a) correspond to the intersections of the curve and the horizontal line given by the ordinate value of . z. The points B.03 Figure 1. x (6/z2)6 7 (10b) (11) ~b = ~bo(Z) ~ ' Downloaded by [University of Guanajuato] at 12:10 18 October 2011 In order to demonstrate the manifold of solutions of (10 a). r/. there are only four branches. 6) = (x 2 -[. f(x. EF and FG.0 . This is the general characteristic of (10 a) with 0 < 6 < 1..i~-~ 0 = kr/. z.(~o)2J.1 + ~ 6I (.5. D. and A and G are infinite points on the curve.03 C F b ~ B /0 x -0. . IF(6/:XI . 6 ] l xco XDE ~ [(6/z~Xl_-6)lol] 1/2.

since this discussion is based on the non-singularity of the Baxter matrix 0(k). (7 c) and (11). as B = Q(iz/~)A. In order to investigate the relation between solutions of (10 a) and the non-singularity of O(k). it is necessary to investigate the non-singularity of 0(k) for the solutions on the branch AB. ktq/ IOl << 1. Equation (12) is a direct consequence of the non-singularity of Q(k) in the upper half of the complex k plane. E is expressed as fiE = ~2 . With the use of the definition of B i given by (8 c). This exception may also be confirmed by using the result from the previous section: in the case of 6 = 1 in figure 4. for example. with kB Boltzmann's constant and T temperature. where the /-components of the vectors A and B are az c~/2 and -27r0Ztc~/e/z~l respectively. namely equation (16) of [5]. we can easily show that. = - z?] . 4.0375 for the solution at the point B. using (5 c). This equation and the non-singularity of ~(k) lead to the following: 2~0 /. However. it may be concluded that the acceptable solutions of (10a) are on the branch AB except in the vicinity of the point B.-0. As will be shown in section 5. in order to complete the choice of the acceptable solution. it is convenient to start with the original form of (10 a). det [O(k)] = 0 at Re (ktr) = 0 and Im (ka) = 0. and all the solutions of (10 a) that do not satisfy (12) must be rejected. the branches here can be related to those discussed by Pastore [6]. Ginoza We now discuss the choice of the acceptable branch for solutions of (10 a).B. Therefore only the solution on the branch AB is acceptable. among the solutions obtained above. As a result. (12) J where Qns(iz/a) is the Baxter matrix corresponding to the hard-sphere system (0 = 0). According to this relation and Pastore's result. Now. The simple thermodynamic theory Let us derive simple and analytic expressions for the internal energy E. In fact. Q(k) is non-singular in the upper half of the complex-k plane and on the real axis for the solutions on the branch AB except in the vicinity of the point B.150 M.1.360 and 0 = 0. J .~ . by calculating the asymptotic behaviour of ai in [ 0 [ << 1 with the use of (8 d . In the present case the latter can be written. where x -. Pastore [6] investigated this problem in detail in a more general HSY system.0537 (or K* = 0/~/= 0-430). Pastore [6] related this problem to the non-singularity of O(k) on the real axis and in the upper half of the complex-k plane... and B = Z c j Z j B j e z]2. K a (13) where fl = (ka T). the Helmholtz free energy F and the entropy S per particle on the basis of the conclusions of the preceding section.\ 1/2 Z Downloaded by [University of Guanajuato] at 12:10 18 October 2011 a.f ) . only XAn is compatible with (12).

When the 'charge neutrality' condition is imposed (Z = 0 or 6 = 0).cq)r . (14) and (17).F) yields s = sHs .6)F q~oF + 1 6[(1 -. 2 d o O" (15 a) where F' is the acceptable solution of (9) with K' in place of K and Downloaded by [University of Guanajuato] at 12:10 18 October 2011 Srls 5 + ~ { ' ~ 3 /~_/~: o gt 2 1 1 rj -~ j = l Cj __ k2~flh2 ] j -- Cj log } Cj r/(4 -. let us first regard K in (5 c) and (9) as a 'coupling parameter'.1. Transforming the integration variable from K' to F' in (15 a) and using the equations above. (16) and (17) that thermodynamic quantities are given in terms of simple rational functions of F. 11]. The result is as follows: /~F = ~ .6)F +~o--T--+ 6[(1 .' 1 (~r3 + 89 where EHS and SHS are E and S in the hard-sphere mixture (K = 0) and we have used (13). -0. using (8 c'. these expressions reduce to the corresponding expressions of Hafner et al.e.SHS --g.2. where the lack of the curve in the case of 0 = 0. we show the cases 0 = -0-3. 0.2.~to]} ~?T~o . On the other hand.ao] 4~1F + 4~o (14) Substitution of (14) into (13) gives the desired expression for E in terms of F. we can obtain from (9) and (14) K a I "2 + z f &ID2(F) d dF B(F) = -.1. This effect may be embodied in the dependences of these quantities on 6.3r/) (1 .SHS _ "':[--dK' B(F'). In each figure.?])2 ' (15 b) mj and h being the mass of the ith species of sphere and Planck's constant divided by 2n respectively [10. e.D2(F) respectively. we can easily perform the integration in (15 a).s)= ~ { AS = SSHS = -- 0 (1 . This parameter is in the range of 0 ~< 6 ~< 1. and 6 = 0 means the 'charge neutrality'.Simple M S A solution in a H S Y mixture 151 which can be written. as B= (1 .B(r) + 1 ( ~r 3 + 89 (16) The substitution of (13) and (16) into S = fl (E ..f).a l ) r -. Feynman's theorem [9] reads flF = ~ -. let us investigate the effect of t h e ' charge-non-neutrality' condition (6 ~ 0) on the following quantifies: AE = ~(E. As an application of our simple thermodynamic theory. -0.~ ( ~ r ~ + 89 1 (17) We can see from (13). 0. Figures 2 and 3 are the results for AE and AS respectively. [12] (see the Appendix).15 and 0. For the system under consideration. which should be done on the acceptable branch AB discussed in the preceding section. In order to obtain the expression for F.2 is due to the fact that there is no solution of (10 a)--which has been .

The numbers by the six curves give the values of 0. where z = 3 and ~/= 0. The acceptable branch for solutions of the nonlinear equation has been determined. rl.4. this trend cannot be maintained for 6 = 0 and 1 : figure 4 shows f ( x . The numbers by the six curves give the values of 0. the equivalence of this to the MSA solution in the original formalism of the OZ equation has been proved. In section 3.2. Ginoza -2 -1 -0. and. 011 Figure 3. however. Equation (10 a) has no solution at low ~ for 0 = 0.152 M. and it has been shown that the effect of the 'charge-non-neutrality' condition on these functions is significant.4. Concludingremarks The results in the present paper can be summarized as follows.2. 5.3~~ -0. interpreted by Waisman [13] as phase separation of the system. where z = 3 and ~/= 0. (ii) Simple expressions for thermodynamic functions have been presented. i ~ 11 Plot of AE as a function of 6.1 Downloaded by [University of Guanajuato] at 12:10 18 October 2011 --2 0. Plot of AS as a function of 6. 3) as a function of x with . (i) A simple expression for the MSA solution in the Baxter formalism has been presented. z. As can be seen from the denominator of (10 b). under the 'charge-neutrality' condition. These results obviously show that the effect of t h e ' charge-non-neutrality' condition on the thermodynamic functions is significant. we have investigated the manifold of solutions of the nonlinear equation (10a) in the range 0 < ~ < 1 where the trend shown in figure 1 was general.5 Figure 2. Equation (10 a) has no solution at low ~ for 0 = 0.

oa li r . z. the acceptable branch is again the branch AB except in the vicinity of the point B. t/. Plot o f f ( x .125: : I I I I I I I if ~ ! : :" ~ .125.. .125: .~176 . . .Simple MSA solution in a HSY mixture 153 i ~ \ \:/. . z...0a \i' ql I Figure 5. . \ o. As is easily s h o w n from a similar discussion to that in section 2. J drr[ho(r ) + 1]e -~'/r = + 1 + ' where w e have used (8 c) and (14). It can be seen that there are only four branches of solutions of (10 a) for these values of 6. \ f li tJ xx~j.. ~7..1 and r/= 0.. . "I \ .-0.125: .. t/.'~. P a s t o r e [6] investigated solutions of (10a) by c o n s i d e r i n g f ( x .03 Downloaded by [University of Guanajuato] at 12:10 18 October 2011 Figure 4. z. . Plot o f f ( x .. however. . . . . .c'22 -"" "' . 6) as a function of G* with z = 1 and tl = 0. . 6 = 0. ..--.. .. z = 1 and ~ / = 0. . . . we s h o w f ( x . .. . The points A and B have the same meanings as in figure 1. 6 = 1. where z --.. 6) as a function of x. .. .: 9"" I i I I g G" ~:ZB II . .. The relation of the branches of solutions in section 3 to those in the w o r k of P a s t o r e [6] can be established by introducing G* defined as follows: G* = ~ c~ZicjZ J Z. .. 6) as a function of G*...-0. . ~1. 6 = 0. 9 . . where z = 1 and ~/= 0. 6) as a function of G*..~ . . . . ~ ~:-1 ~". z.03 II I I =:.I. In figure 5.I '\ t / . . 6 = 1.. The points A and B have the same meanings as in figure 1.~176 ~176176 // ] // J / 1 I I -0... . . . This gives a transformation from x ( = F/z) to G*. 0 x ~ ".

1. Cs(r) = Ao+A. h.r])h.I ) r (r < ~). [12. (r > ~).).(r). The extension of this solution to the case of an ncomponent mixture can be obtained using the similar method to that in our previous work [18]. It can be shown by direct substitution that ( A l a ._1+ 2--711-cosh (zr)]} -. Figure 2 of [6] is for 6 = 1.(r)=-ff- ooo{o-. Hafner et al. The M S A solution Waisman [13] and Copestake et al. ho(r ) = h~(r) + Z. [17] obtained an explicit solution of (1) and (5a. . -r A + O" 3 ( r ) a. (A 1 a) (A 1 b) where hs(r) = cs(r) + p J dt . The result on the effect of the 'charge-non-neutrality' condition in section 4 prompts us to use the simple theory in section 4 as a model. (A 4) c. 14-16] investigated thermodynamic and structural properties of liquid alloys with strong chemical short-range order using a simple model corresponding to the special case of 6 = 0 in section 4. Equation (A 2 a) was solved by Wertheim [19] and Thiele [20]. (A2a) (A 2 b) (A2c) (A3a) (A 3 b) (A 3 c) h~(r)=-I cs(r) = 0 (r<a).t I)h~(r. Zj h. Ginoza the branch AB in figure 4 is transformed to the branch AB in figure 5. h.(r) = c. for a twocomponent HSY mixture. Appendix The result under the "charge-neutrality' condition ( 2 = O) Downloaded by [University of Guanajuato] at 12:10 18 October 2011 A.' ( ' / ' .(rl). (A 5) . while (A 3 a) was solved by Waisman [13] : for r < a.154 M.(r).b) with (5c) by using the 'charge-neutrality' condition.(r) = 0 Ca(r) = K e .cs(I cx . b) with (A2a-c) and (A 3 a-c) satisfies (1) and (5 a-c). (r > a). 2 = 0. We give the result here without the derivation: co(r ) = c~(r) + Z i Z s c.(r) + p f d r l c.(I rx .

(A 8 b) (A 8 c) )'a2Co(e-zr/r _ e-Z) 4. Cij = Z i Z j a 2 C o .~/)4 _ 2A 3 . [~o(~)r + 135 (A 7) Substitution of these coefficients into (6 a. (r > a). the MSA solution in section 2 becomes very simple when 2 = 0. Therefore (7 a-d). (9) becomes F 2 + zF + 60 = O.-q.c ~ (rz/a)]~ (A9b) . (A 5) and (A 6). (A 9 a) where c. (8 a-f) and 2 = 0 give the following coefficients of (6 a.2 r [ c k o ( z ) r + 13 e'---~n 6q ' C O = 2r ' ( 1+ ~-~" With 2 = 0.a ) + pa(r-a) (r<~). (A 4).a2Do e -z'/a Ql(r) = [a2D ~ e-Z'/a It is straightforward to obtain the following with the substitution of (A 8 a-c) into (4 a) and the use of (A 7): ~c~(r) + Z~ Zj c'~(r) (r < a).~/)4 and co is the acceptable solution of the nonlinear equation as t20[89 + 13" = co(z . Now comparison of (A9 b) with (A 5) suggests that co and F are related as follows: co = 2F dpo(z)F + 1" (A 10) Using this relation.(r). A1 - 6t/(1 + 89 2 (1 . Do = . we get AN = 0 and PN = 0 from (8 a.b) yields Qdr) = Qo(r) + Z~ZjQ. (A8a) where Qo(r)= { ~ A r ( r .89 (A 6) On the other hand.b): Downloaded by [University of Guanajuato] at 12:10 18 October 2011 A j = A. (r < a).jr) = _ Oa 2F {e-Z'/~ . Since (8 e. (r > ~). it is easy to show the equality of the solution given by (A 9 a.b) and (A 7) with that given by (A 1 a). Dij = Z i Z j t 7 2 D o . . flj = aft.b). where A = --~ 1+ fl = -~. cij(r) = ~Z i Z j Ca(r) (r > a).Simple M S A solution in a H S Y mixture 155 where Ao = (1 + 2 q ) 2 (1 .f) and 2 = 0 give D a = 0.r Oo(z)r + 1 2z + T j' and es(r) and ca(r) are given by (A 4) and (A 3 e) respectively.1 e-" 2 F [ 1 .

B. chem. [12] HAFNER. 53. and HICTER. [14] HAFN~R. 661. Phys. 22. 2783. F. chem. 51. chem. J. J.. J. Phys.. PAS~REL. and SCrlmMACrmR. 1987.G.. statist.. [6] PASTOP. Ibid. 1-13] W~dSMAN. BLUM... Phys. Japan. 371.W.. NnZEKI.. 14.. 1986a.. and JANK. J.. and HICT~R.. J. J. 321.N..N.BAXTER. Phys. statist..M. Soc.. Lett. [8]. J. Can. 1983. [17] COPESTAK~. F. 1970. S. Molec. Coulomb Liquids (Academic Press). 474. 1969... [19] WERTHEIM.. 32.R. HAFr~R. H. 5. EVANS. and STARLING..L. Phys. M. 19. 1986b. Phys.. 1987.. F. Phys. 55.H.A.W. 39. 1984. Statistical Mechanics (Benjamin).2.. 1988. E. (16) and (17) yields the corresponding expressions for thermodynamic functions given by Hafner et al... 251. 1970.. J. GINOZA.P. J. Phys. (14). [1] [2] [3] [4] I-5] Downloaded by [University of Guanajuato] at 12:10 18 October 2011 ... 95. 1985.K. Ginoza A. Phys. BLUM. J. 635. 4559. 2279. 59. 1963.. F. M. 1980. Phys. 1963. PASTUREL. Phys.W. 14. 18. 333.. Rev. S. Phys. 1978. J. P. J.E..L. K. [20] TmELE.P. 56.. J.156 M. [16] HAt... YOUNG.J.mR. J.A. 241. 1782.. [18] GINOZA. J. Phys.. H. 1972... E. Japan. phys. A. P. 495. Phys... 1137...M. phys.K. 52. 43. J. F. Ibid. 13. A. Phys. 54. Phys.N. J. [10] CARNArlAN.. and How. [11] CARNAnAN. References MARCH.. 1993. Soc. 600. [12]. 1984. 63.. 65. Rev. RUPPERSBERG. chem. 10. 1984.J. and HICTER.R. J.R. 1984. 5009. Molec.. 55.ZL.. and TosI. [15] PASa'UPa.. and STARLING. 1985. I-7] . [9] FEVNMAN.E. chem. E. The thermodynamic theory It is easy to show that the use of co defined by (A 10) in place of F in (13). P. 317. 1973. 1988.P..