+ All Categories
Home > Documents > Mol. Phys (ginoza)

Mol. Phys (ginoza)

Date post: 06-Apr-2018
Category:
Upload: moshky-lemoto
View: 232 times
Download: 0 times
Share this document with a friend

of 13

Transcript
  • 8/3/2019 Mol. Phys (ginoza)

    1/13

    This article was downloaded by: [University of Guanajuato]On: 18 October 2011, At: 12:10Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

    Molecular PhysicsPublication details, including instructions for authors andsubscription information:

    http://www.tandfonline.com/loi/tmph20

    Simple MSA solution and

    thermodynamic theory in a hard-

    sphere Yukawa system

    Mitsuaki Ginozaa

    aDepartment 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

    PLEASE SCROLL DOWN FOR ARTICLE

    Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions

    This article may be used for research, teaching, and private study purposes. Any

    substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,systematic supply, or distribution in any form to anyone is expressly forbidden.

    The publisher does not give any warranty express or implied or make anyrepresentation that the contents will be complete or accurate or up to date. Theaccuracy of any instructions, formulae, and drug doses should be independentlyverified with primary sources. The publisher shall not be liable for any loss, actions,claims, proceedings, demand, or costs or damages whatsoever or howsoevercaused arising directly or indirectly in connection with or arising out of the use ofthis material.

    http://www.tandfonline.com/page/terms-and-conditionshttp://www.tandfonline.com/page/terms-and-conditionshttp://dx.doi.org/10.1080/00268979000101701http://www.tandfonline.com/loi/tmph20
  • 8/3/2019 Mol. Phys (ginoza)

    2/13

    MOLECULAR PHYSICS, 1990, VO L. 71, N O. 1, 1 45 -15 6

    S i m p l e M S A s o lu t io n a n d th e r m o d y n a m i c th e o r yin a hard-sphere Yukawa sys temB y M I T S U A K I G I N O Z A

    D e p a r t m e n t o f P h y s i c s , C o l l e g e o f S c ie n c e,U n i v e r s i t y o f th e R y u k y u s , N i s h i h a r a - C h o ,

    O k i n a w a 9 0 3 - 0 1 , J a p a n(Received 29 January 1990; accepted 11 April 1990)

    A simple expression for the mean-spherical-approximation (M SA ) solutio nof the Orn stein-Ze rnike (OZ) equation in the Baxter formalism is presented forthe case with n comp onen ts and a s ingle Yu kaw a term with factorizable pre-factor: all coefficients of the MS A solution are given in term s of s imple rationa lfunctions of a parameter that is defined as the acceptable solution of a non-linear equation. The m anifold of solutions of the nonlinear equation an d th echoice o f the acceptable solution are diseussed. A therm ody nam ic theo ry is alsopresented in terms o f simple ration al functions of the above-men tioned par-ameter, and the effec t of the ' charge-non -neutra l i ty ' condi t ion on thermo dyna-mic functions is discussed.1. Introduction

    S t u d ie s o f t h e t h e r m o d y n a m i c a n d s t r u c t u r a l p r o p e r t ie s o f a h a r d - s p h e r eY u k a w a (H S Y ) m i x t u r e , i n c l u d i n g a n e u t r a l h a r d - s p h e r e m i x t u r e a n d a c h a r g e dh a r d - s p h e r e m i x t u r e a s l im i t i n g ca se s, h a v e b e e n m a d e b y m a n y w o r k e r s [ 1, 2] . I nt h e s e s t u d i e s , t h e m e a n - s p h e r i c a l a p p r o x i m a t i o n ( M S A ) h a s o f t e n b e e n e m p l o y e d .T h e f o r m a l M S A s o l u t i o n o f t h e O r n s t e i n - Z e r n i k e ( O Z ) e q u a t i o n f o r t h e n -c o m p o n e n t m - Y u k a w a - t e r m e a s e h a s b e e n g i v e n b y B l u m a n d H o y e [ 3 ] i n t h eB a x t e r f o r m a l i s m a n d b y N i i z e k i [ 4 ] u s i n g t h e L a p l a c e - t r a n s f o r m t e c h n i q u e . I n t h ec a s e o f Y u k a w a t e r m s w i t h f a c t o r i z a b l e c o e ff ic i en t s, t h e p r e s e n t a u t h o r [ 5 ] s h o w e dt h a t t h e s y s t e m o f n o n l i n e a r a l g e b r a i c e q u a t i o n s d e f i n i n g t h e c o e f fi c i en t s o f t h eB l u m - H o y e s o l u t i o n c a n b e s im p l if ie d r e m a r k a b l y , a n d i n t h e s i n g l e - Y u k a w a - t e r mc a se , i n p a r t i c u l a r , t h e s y s t e m c a n b e r e d u c e d t o a s in g l e n o n l i n e a r e q u a t i o n .

    I t is w e l l k n o w n t h a t t h e a b o v e s y s t e m o f n o n l i n e a r e q u a t i o n s h a s a m a n i f o l d o fs o l u t i o n s . R e c e n t l y , P a s t o r e [ 6 ] g a v e a n i n t e r e s t i n g d i s c u s s i o n r e g a r d i n g t h e m a n i -f o l d a n d s h o w e d t h a t t h e b r a n c h o f t h e a c c e p ta b l e M S A s o l u t i o n c a n b e s in g l ed o u tb y t h e c r i t e ri o n o f n o n - s i n g u l a r i t y o f th e B a x t e r m a t r i x i n t h e u p p e r h a l f o f th ec o m p l e x - w a v e n u m b e r p l a n e a s w e l l a s o n t h e r e a l a x i s . I n t h i s c o n t e x t , i t i s i n t e r -e s t in g t o i n v e s t i g a t e in d e t a i l t h e m a n i f o l d o f s o l u t i o n s o f th e s i n g l e n o n l i n e a re q u a t i o n f o r th e n - c o m p o n e n t s in g l e - Y u k a w a - t e r m c a se .

    T h e H S Y m i x t u r e h a s o f t e n b e e n u s e d as a si m p l e m o d e l t o d e s cr i be c o m p o u n d -f o r m i n g a n d p h a s e - s e p a r a t i n g l i q u i d s d i re c t l y [1 , 2 ] , a n d i t m a y a l s o s e r v e a s ar e f e r e n c e s y s t e m i n p e r t u r b a t i o n a l o r v a r i a t i o n a l m e t h o d s f o r t h e d e t e r m i n a t i o n o ft h e t h e r m o d y n a m i c s a n d s t r u c t u r e o f a l i q ui d s y s te m w i t h m o r e c o m p l e x p o t e n ti a ls .F o r t h e s e p u r p o s e s, i f a s im p l e M S A s o l u t io n a n d t h e r m o d y n a m i c th e o r y c a n b eo b t a i n e d , i t m a y b e u s e fu l .

    T h e a i m o f t h i s p a p e r i s (i) t o p r e s e n t s i m p l e e x p r e ss i o n s f o r th e M S A s o l u t i o na n d t h e t h e r m o d y n a m i c t h e o r y , ( ii ) t o d i sc u s s th e m a n i f o l d o f s o l u t io n s o f t h e

    0026-8976/90 $3.00 9 1990 Taylor & Francis Ltd

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    3/13

    1 46 M . G i n o z an o n l i n e a r e q u a t i o n a n d t h e c h o i c e o f t h e a c c e p t a b l e s o l u t i o n a n d (iii) t o in v e s t i g a t et h e t h e r m o d y n a m i c e f f e c t o f t h e ' c h a r g e - n o n - n e u t r a l i ty ' c o n d i t io n a s a n a p p li c a ti o n .

    I n s e c t i o n 2 , t h e M S A s o l u t i o n i n t h e B a x t e r f o r m a l i s m i s g i v e n f r o m o u rp r e v i o u s w o r k [ 5 ] , a n d i t i s s h o w n i n t h e A p p e n d i x t h a t , u n d e r t h e ' c h a r g e -n e u t r a l i t y ' c o n d i t i o n , t h i s M S A s o l u t i o n a g r e e s w i t h t h a t i n t h e o r i g i n a l f o r m a l i s mo f t h e O Z e q u a t i o n . I n s e c t i o n 3 , t h e m a n i f o l d o f s o l u t io n s o f t h e n o n l i n e a r e q u a t i o na n d t h e c h o i c e o f t h e a c c e p t a b l e s o l u t i o n a r e d i s c u ss e d . I n s e c t io n 4 , a t h e r m o d y n a -m i c t h e o r y is o b t a i n e d o n t h e b a s i s o f t h e a c c e p t a b l e s o l u t i o n a b o v e , a n d t h et h e r m o d y n a m i c e f fe c t o f t h e 'c h a r g e - n o n - n e u t r a l i t y ' c o n d i t io n w i ll b e in v e s t ig a t e d .C o n c l u d i n g r e m a r k s a r e g i v e n i n s e c t io n 5 .

    2. Th e s imp le analyt ic M SA solutionL e t u s c o n s i d e r a n n - c o m p o n e n t H S Y m i x t u r e c o n s i s ti n g o f e q u a l -s i ze h a r d

    s p h e r e s i n te r a c ti n g w i t h e a c h o t h e r v i a Y u k a w a p o t e n t i a ls o u t s i d e s p h e re s . T h et h e r m o d y n a m i c s a n d t h e s ta t ic s t r u c t u r e o f t h e m i x t u r e a r e i n v e s ti g a te d b y m e a n s o ft h e p a r t i a l c o r r e l a t i o n f u n c t i o n s h o & ) o r t h e p a r t i a l d i r e c t c o r r e l a t i o n f u n c t i o n s c o & .T h e l a tt e r a r e d e fi n e d b y t h e O Z e q u a t i o n

    ho ( r ) = c o ( r ) + p ~ c , f d r 1 c , ~ [ r 1 - r I ) h o ( rl ), ( 1)w h e r e p is t h e t o ta l n u m b e r d e n s i t y a n d c , i s t h e c o n c e n t r a t i o n o f / - s p e c i e s s p h e re s .B a x t e r I - 7 ] g a v e a t r a n s f o r m a t i o n o f (1 ) i n a d i s o r d e r e d s y s t e m . I n t h e t r a n s f o r m -a t io n , h e in t r o d u c e d a m a t r ix Q ( k ) t h a t i s a s s u m e d t o b e n o n - s i n g u l a r i n t h e u p p e rh a l f o f t h e c o m p l e x - w a v e n u m b e r (k ) p l a n e a s w e ll a s o n t h e r e a l a x i s a n d w h o s e (i, j )e l e m e n t i s o f t h e f o r m 6 o - p ( c i c j ) l / 2 O o ( k ) , where 0 o ( k ) h a s t h e f o r m

    a n d s a t i s f i e s~ 0~ 1 7 6Q . o (k ) = d r Q o ( r ) e ik " (2)

    ~ o ( k ) = - J d r c o ( r ) e i h " " (3 a )= Q o(k) + ~4 ,~- k ) - p ~ c t Q a ( k )Q j t ( - k ) . ( 3 b )l

    T h e O Z e q u a t i o n i n th is B a x t e r f o r m a l i s m is t h u s [ 3 , 7 ]

    fo ard | d rn r c o ( r ) = - Q o ( r ) + p ~ c~ Q ~ ( t + r ) Q j t( t) , (4 a )~ d ~ on r h o ( r ) = - Q o { r ) + 2 r i p ~ c t d t h,~ l t - r l ) ( r - t ) Q o { t ) . (4 b )

    E q u a t i o n ( 4 a ) i s t h e r e a l s p a c e r e p r e s e n t a t i o n o f ( 3 b ), w h i l e ( 4 b ) is o b t a i n e d f r o m ( 1)a n d ( 3 ) u s i n g t h e n o n - s i n g u l a r i t y o f t h e B a x t e r m a t r ix , Q ( k ).T h e M S A f o r t h e n - c o m p o n e n t a n d s i n g i e - Y u k a w a - t e r m c a s e is , a s u s u a l, d e f in e db y t h e f o l l o w i n g c l o s u r e r e l a t i o n s f o r (1 ) o r ( 4 a , b ) :

    h o ( r ) = - 1 ( r < a ) , (5 a )c o ( r ) = K _ ~ e - z , / , ( r > a ) , (5 b )r

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    4/13

    S i m p l e M S A s o lu t io n i n a H S Y m i x t u r e 147w h e r e a i s th e h a r d - s p h e r e d i a m e t e r . L e t u s d e f in e t h e f a c t o r i z a b l e ca s e b y

    K i j = K e z Z i Z j , (5 c)a n d , w i t h o u t l o s s o f g e n e r a l i t y , w e a s s u m e ~ l cz Z ~ = 1.

    B l u m a n d H o y e I - 3, 8 ] s o l v e d (4 a , b ) w i t h c l o s u r e r e l a t i o n s o f t h e m o s t g e n e r a lf o r m c o n s i st i n g o f a n a r b i t r a r y n u m b e r o f Y u k a w a t e r m s . F o r t h e c a s e o f (5 b), th e i rs o l u t i o n i s

    ( 8 9 - a ) + t i f f - a ) + C o ( e - z ' / " - e - z )Q o ( r ) = ~ + D o e - z r /" ( r < a ) , ( 6 a )

    / D e -z r/~ ( r > a ) . ( 6 b )k i jT h e c o e f f ic i e n ts i n ( 6 a , b ) a re d e f i n e d b y a n u m b e r o f e q u a t i o n s r e l a t e d t o t h ea c c e p ta b l e s o l u t i o n o f t h e s y s te m o f n o n l i n e a r e q u a t i o n s , a n d w e d o n o t q u o t e t h e mh e r e b e c a u s e o f th e i r l e n g t h .

    T h e p r e s e n t a u t h o r [ 5 ] s h o w e d t h a t i n t h e f a c t o r i z a b l e c a s e s u c h a s (5 c ), t h i ss y s t e m o f n o n l i n e a r e q u a t i o n s c a n b e r e d u c e d t o t h e n o n l i n e a r e q u a t i o n f o r ap a r a m e t e r F , a n d t h e e x p r e s s io n s f o r t h e c o e ff i c ie n t s i n (6 a , b ) c a n b e c o m e e x t r em e l ys im p l e. A f t e r s o m e s t r a i g h t f o r w a r d c a l c u la t i o n a n d n o n - d i m e n s i o n a l i z a t i o n s u si n g o fa , w e o b t a i n t h e f o l l o w i n g f r o m t h e r e s u l t o f [ 5 ] :

    Aj = 1 + + ~ PN a j , (7 a)

    f l j = a - ~ + a A N a j , (7 b)D o = - a Z Z i a j e z , (7 c)

    B i e - Z / 2 " ~ zC i j = ( 7 2 Z i -g J a i e , (7 d)

    w h e r e

    AN = - - ~ Z 2 l + 8 9 D x,

    B i e # 2 = --- 8 9 ~ c j Z j ~ d t [ h o ( r ) + 1] e - Z ( r l r - 1 )) ,J r

    = - - F X i + (O to + o q F ) D 1 ,r ~ F X i

    a i - 3r/D 2 ,Z i - Z Z,X ~ - +C k o (z )F + 1 ~ , F + ~ o '

    J

    ( 8 a )

    ( 8 b )

    ( 8 c )( 8 c ' )( 8 , / )

    ( 8 e )(8 f )

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    5/13

    1 48 M . G i n o z aw i t h

    = E c j Z j ,Jrt = 6inp a 3,

    A = 1 - ~ / ,1 - e - z

    C o ( Z ) - - - ,Z

    1 - - 8 9 + { z ) e - zl ( z) - z 3 ,

    ~Po = 1 + -~- qgo(Z - - 7 ~ l(z ) 1 + 89+ ,12r/

    4 1 = 0 ( Z ) - - ~ I / / I( Z ) '

    12rt tl= + 8 9

    ~ o = ~ l l + 8 9 - ~ .A s c a n b e s e e n f r o m ( 7 a - d ) a n d ( 8 a - f ) , al l coeff ic ien ts in (6 a ,b ) a r e g i v e n b y s i m p l er a t i o n a l f u n c t i o n s o f F , w h i c h s a ti sf ie s t h e f o l l o w i n g n o n l i n e a r e q u a t i o n :

    F 2 + z F = - - 6K t /D2(F ) . (9 )O"

    Since ~o(k) i s ob ta in ed f ro m (2 ) , (3 a ,b ) a n d (6 a,b) , i t is a ls o a r a t i o n a l f u n c t i o n o fF . M o r e o v e r , a s w il l b e d i s c u ss e d i n s e ct io n 4 , t h e r m o d y n a m i c f u n c t io n s c a n b ee x p r e s s e d i n t e r m s o f s i m p l e r a t i o n a l f u n c t i o n s o f F . T h e r e f o r e a l l w e h a v e t o d ob e f o r e in v e s t i g a ti o n o f th e s t a ti c s t r u c t u r e a n d t h e r m o d y n a m i c s o f th e m i x t u r e i s tos o l v e (9 ) . T h i s , h o w e v e r , h a s a m a n i f o l d o f s o l u t i o n s , a n d t h e c h o i c e o f t h e a c c e p t -a b l e s o l u t i o n w i l l b e d i s c u s s e d i n t h e n e x t s e c t io n .

    I t m a y b e o f i n t er e s t t o p r o v e d i r ec t ly th e e q u a l i t y o f t h e M S A s o l u t i o n o b t a i n e da b o v e w i t h t h a t o f (1 ) a n d ( 5 ). A s f a r a s t h e a u t h o r i s a w a r e , h o w e v e r , t h e e x p l ic i te x p r e ss i o n o f th e l a t t e r h a s n o t b e e n g i v e n e x c e p t f o r t h e t w o - c o m p o n e n t c a s e u n d e rt h e ' c h a r g e - n e u t r a l i t y ' c o n d i t io n . W e d i sc u s s t h is p r o b l e m i n t h e A p p e n d i x .

    3 . T h e m a n i f o l d o f s o l u t i o n s a n d t h e c h o i c e o f a c c e p t a b l e s o lu t i o nA s h a s b e e n s h o w n i n s e c t i o n 2 , o u r M S A s o l u t i o n i n t h e B a x t e r f o r m a l i s m

    c o n t a i n s t h e q u a n t i t y F d e t e r m i n e d b y ( 9 ). T h i s e q u a t i o n c a n b e w r i t t e n e x p li c it lyw i t h t h e u s e o f (8 e , f ) a s f o l l o w s :

    f ( x ; z , q , 6 ) = - 0 wi th x = F / z , ( 1 0 a )

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    6/13

    S im p le M S A s o lu tio n i n a H S Y m i x t u r e 149w h e r e

    , I F ( 6 / : X I - ~ ) + (6/z2)6 7f(x; z, r/, 6)= (x 2 -[- x ) / L ( ~ o ZX - . ~ i~- (~l~iz -]- (~o)2J (10b)0 = kr/, ~b~ = ~bo(Z) (11 )(7t ~ ~ 2 .

    I n o r d e r t o d e m o n s t r a t e t h e m a n i f o l d o f s o l u t io n s o f ( 10 a) , f ( x ; z , r l, 6 ) i s s h o w ni n f i gu re 1 a s a f un c t i o n o f x w i t h z = 1 , ~ / = 0 . 125 a nd 6 = 0 . 5 . I n t h i s f i gu re , t hes o l u t i o n s o f ( 1 0 a ) c o r r e s p o n d t o t h e i n t e r s e c ti o n s o f t h e c u r v e a n d t h e h o r i z o n t a ll in e g i v e n b y t h e o r d i n a t e v a l u e o f - 0 . I t c a n b e s e e n f r o m t h e f ig u r e t h a t t h e r e a r es ix d if f e r e n t b r a n c h e s o f s o l u t io n s f o r x : A B , B C , C D , D E , E F a n d F G . T h i s i s t h egen e ra l c ha rac t e r i s t i c o f ( 10 a ) w i t h 0 < 6 < 1 . I n t h e spec i a l ca ses o f 6 = 0 and 1 , a sw i ll b e d i s c u s s e d i n s e c t i o n 5 , t h e r e a r e o n l y f o u r b r a n c h e s .

    T h e a s y m p t o t i c s o l u t i o n s o f ( 1 0 a ) o n t h e se s ix b r a n c h e s i n 101 ~ 1 c a n e a s i ly b eo b t a i n e d , a n d t h e y a r e a s fo l lo w s :

    6 ( 6 ) 0X A B = - - ~ 1 - - 6 + ~ ,6 I 1 - 6 6 ]x ~,~ = - 1 + ~ ( , / ,o Z - - l Y + ( r - ~ o ) ~ o ,

    l [ ( 6 / z ~ X l _ - 6 ) l o l ] 1/2,xco ~oZ -~

    2X D E ~ ~ 0 Z X C D ~

    r F" (6/Z2)~"~10] 71/2XEF = - - @IZ + L'~o(@o - ' ~ : ) J '

    2@0X F G : r X E F "

    0.03

    CF b ~ /0 x-0,03B

    Figu re 1. Plo t o ff (x ; z, ~/, 6) as a funct ion of x, where z = 1, ~/= 0.125 and 6 = 0.5 . Fo r agiven value o f 0, the solut ions of (10 a) corr esp ond to the intersections of the curve an dthe hor izo nta l line g iven by the ordinate va lue of - 0 . Th e point s B , C , D, E and F arethe po ints w here two different solut ions merge, and A a nd G are infinite points on thecurve.

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    7/13

    1 50 M . G i n o z aW e n o w d i s c u s s th e c h o i c e o f t h e a c c e p t a b l e b r a n c h f o r s o l u t i o n s o f (1 0 a ).

    P a s t o r e [ 6 ] r e l a t e d t h i s p r o b l e m t o t h e n o n - s i n g u l a r i t y o f O ( k ) o n t h e r e a l a x i s a n di n t h e u p p e r h a l f o f th e c o m p l e x - k p l a n e . I n o r d e r t o i n v e s t i g a t e th e r e l a t i o n b e t w e e ns o l u t i o n s o f ( 10 a ) a n d t h e n o n - s i n g u l a r i t y o f O (k ), i t i s c o n v e n i e n t t o s t a r t w i t h t h eo r i g i n a l f o r m o f ( 10 a ), n a m e l y e q u a t i o n ( 1 6 ) o f [ 5 ] . I n t h e p r e s e n t c a s e t h e l a t t e r c a nbe w ri t ten , u s ing (5 c), (7 c) and (11) , as

    B = Q( iz /~)A,w h e r e t h e / - c o m p o n e n t s o f t h e v e c to r s A a n d B a r e a z c ~ / 2 a n d - 2 7 r 0 Z t c ~ / e / z ~ lr e s p e ct i v el y . T h i s e q u a t i o n a n d t h e n o n - s i n g u l a r i t y o f ~ ( k ) l e a d t o t h e f o l l o w i n g :

    2~ 0 /,~ .\ 1/2a , = - Z , I O l < < 1 . ( 1 2 )

    z?] J k t q /w h e r e Q n s ( i z / a ) i s t h e B a x t e r m a t r i x c o r r e s p o n d i n g t o t h e h a r d - s p h e r e s y s t e m( 0 = 0 ). E q u a t i o n ( 12 ) i s a d i r e c t c o n s e q u e n c e o f t h e n o n - s i n g u l a r i t y o f Q (k ) i n t h eu p p e r h a l f o f th e c o m p l e x k p l a n e , a n d a ll t h e s o l u t i o n s o f ( 10 a ) t h a t d o n o t s a t is f y(12) m us t b e re jec ted .

    N o w , b y c a l c u l a t i n g t h e a s y m p t o t i c b e h a v i o u r o f ai i n [ 0 [

  • 8/3/2019 Mol. Phys (ginoza)

    8/13

    S im p l e M S A s o lu t io n in a H S Y m i x t u r e 15 1w h i c h c a n b e w r i t t e n , u s i n g (8 c ', e , f ) , a s

    B = (1 - 6 )F 6[(1 - - a l ) r - - ao ] (14)q~oF + 1 4~1F + 4~oS u b s t i t u t i o n o f (1 4) i n t o ( 1 3 ) g i v es th e d e s i r e d e x p r e s s i o n f o r E i n t e r m s o f F .

    I n o r d e r t o o b t a i n t h e e x p r e s s i o n f o r F , l e t u s f ir s t r e g a r d K i n (5 c ) a n d ( 9) a s a' c o u p l i n g p a r a m e t e r ' . F o r t h e s ys te m u n d e r c o n s i d e ra t io n , F e y n m a n ' s th e o r e m [ 9 ]r e a d s

    f lF = 2 -- SHS _ "':[-- d K ' B(F' ) , (15 a)d o O"w h e r e F ' i s t h e a c c e p t a b l e s o l u t i o n o f (9 ) w i t h K ' i n p l a c e o f K a n d

    5 + ~ { ~_/~ : rr~ 3 / 2 1 1 o g - - l o g } r/(4 - - 3 r/) (1 5 b )Srls -~ __ Cj k2 ~f lh2 ] j Cj Cj ( 1 - - ? ] ) 2 'j = lm j a n d h b e i n g t h e m a s s o f t h e i th s p e ci e s o f s p h e r e a n d P l a n c k ' s c o n s t a n t d i v i d e db y 2 n r e s p e c t i v e l y [ 1 0, 1 1]. O n t h e o t h e r h a n d , w e c a n o b t a i n f r o m (9 ) a n d (1 4)

    K I "2 + z f da &ID2(F ) d F B(F) = - - D2(Fr e sp e c ti v el y . T r a n s f o r m i n g t h e i n t e g r a t i o n v a r i ab l e f r o m K ' t o F ' in (15 a ) and us ingt h e e q u a t i o n s a b o v e , w e c a n e a s il y p e r f o r m t h e i n t e g r a t i o n i n ( 1 5 a ), w h i c h s h o u l d b ed o n e o n t h e a c c e p t a b l e b r a n c h A B d i s c u s s e d i n t h e p r e c e d i n g s e c t i o n . T h e r e s u l t i sa s f o l l o w s :

    1/ ~F = ~ - S HS --g - B ( r ) + ( ~ r 3 + 8 9 ( 1 6 )T h e s u b s t i t u t i o n o f ( 13 ) a n d ( 1 6) i n t o S = f l ( E - F ) y i e l d s

    1s = s H s - ~ ( ~ r ~ + 89 (17)W e c a n s e e f r o m ( 13 ) , (1 6) a n d ( 1 7 ) t h a t t h e r m o d y n a m i c q u a n t i t i e s a r e g i v e n in

    t e r m s o f s i m p l e r a t io n a l f u n c t i o n s o f F . W h e n t h e ' c h a r g e n e u t r a l i t y ' c o n d i t i o n i si m p o s e d ( Z = 0 o r 6 = 0 ), t h e s e e x p r e s s i o n s r e d u c e t o t h e c o r r e s p o n d i n g e x p r e s s i o n so f H a f n e r et a l . [12] ( see the A ppend ix ) .

    A s a n a p p l i c a t i o n o f o u r s i m p l e t h e r m o d y n a m i c t h e o r y , le t u s i n v e st i g at e t h ee f fe c t o f t h e ' c h a r g e - n o n - n e u t r a l i t y ' c o n d i t i o n (6 ~ 0 ) o n t h e f o l lo w i n g q u a n ti f ie s :

    0 (1 - 6 )F 6[(1 - cq )r - ~to]}A E = ~ ( E - e . s ) = ~ { +~o--T--- ~ ? T ~ o . '1 ( ~ r 3 + 89A S = S - S H S = - -

    w h e r e E HS a n d SHS a r e E a n d S i n t h e h a r d - s p h e r e m i x t u r e ( K = 0 ) a n d w e h a v euse d (13), (14) an d (17) .T h i s e f f e ct m a y b e e m b o d i e d i n t h e d e p e n d e n c e s o f th e se q u a n t i t i e s o n 6 . T h i s

    p a r a m e t e r i s i n t h e r a n g e o f 0 ~< 6 ~< 1 , a n d 6 = 0 m e a n s t h e ' c h a r g e n e u t r a l i t y ' .F i g u r e s 2 a n d 3 a r e t h e r e s u lt s fo r A E a n d A S r e sp e c t iv e l y . I n e a c h f i gu r e , w e s h o wt h e c a s e s 0 = - 0 - 3 , - 0 . 2 , - 0 . 1 , 0 . 1 , 0 .1 5 a n d 0 .2 , w h e r e t h e l a c k o f t h e c u r v e i n t h ec a s e o f 0 = 0 . 2 is d u e t o t h e f a c t t h a t t h e r e i s n o s o l u t i o n o f ( 10 a ) - - w h i c h h a s b e e n

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    9/13

    1 5 2 M . G i n o z a

    -2 -0 .3~~ --1 -0.1

    --2 i0;5 ~ 11

    F i g u r e 2. P l o t o f A E a s a f u n c t i o n o f 6 , w h e r e z = 3 a n d ~ / = 0 .4 . T h e n u m b e r s b y t h e s ixcurves give the values of 0. Eq uat io n (10 a) has no solut ion at low ~ for 0 = 0.2.

    011Figure 3. Plo t of AS as a funct ion of 6 , where z = 3 and ~/= 0 .4 . The num bers by the s ixcurves give the values o f 0. Eq uat io n (10 a) has no solut ion at low ~ for 0 = 0.2.i n t e r p r e t e d b y W a i s m a n [ 1 3 ] a s p h a s e s e p a r a t i o n o f t h e s y st e m . T h e s e r e s u lt s o b v i -o u s l y s h o w t h a t t h e e ff ec t o f t h e ' c h a r g e - n o n - n e u t r a l i t y ' c o n d i t i o n o n t h e t h e r m o d y -n a m i c f u n c t i o n s i s s i g n if ic a n t .

    5. Con cluding emarksT h e r e s u l ts i n t h e p r e s e n t p a p e r c a n b e s u m m a r i z e d a s fo l lo w s .

    ( i ) A s i m p l e e x p r e s s i o n f o r t h e M S A s o l u t i o n i n t h e B a x t e r f o r m a l i s m h a s b e e np r e s e n t e d , a n d , u n d e r t h e ' c h a r g e - n e u t r a l i t y ' c o n d i t i o n , t h e e q u i v a l e n c e o ft h is t o t h e M S A s o l u t i o n i n th e o r i g i n a l f o r m a l i s m o f t h e O Z e q u a t i o n h a sb e e n p r o v e d . T h e a c c e p ta b l e b r a n c h f o r so l u ti o n s o f t h e n o n l i n e a r e q u a t i o nh a s b e e n d e t e r m i n e d .

    (ii) S i m p l e e x p r e s s io n s f o r t h e r m o d y n a m i c f u n c t io n s h a v e b e e n p r e s e n t e d , a n d i th a s b e e n s h o w n t h a t t h e e ff ec t o f t h e ' c h a r g e - n o n - n e u t r a l i t y ' c o n d i ti o n o nt hese func t i ons i s s i gn i f i can t .

    I n s e c t i o n 3 , w e h a v e i n v e s ti g a te d t h e m a n i f o l d o f s o l u t i o n s o f th e n o n l i n e a re q u a t i o n ( 1 0 a ) i n t h e r a n g e 0 < ~ < 1 w h e r e t h e t r e n d s h o w n i n f ig u r e 1 w a sg e n e ra l . A s c a n b e s e e n f r o m t h e d e n o m i n a t o r o f ( 10 b ), h o w e v e r , th i s t r e n d c a n n o tb e m a i n t a i n e d f o r 6 = 0 a n d 1 : f i g u r e 4 s h o w s f ( x ; z , rl, 3 ) a s a f u n c t i o n o f x w i t h

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    10/13

    Simple MSA so lu t i on in a HSY mix ture 1 5 3

    \ f l ii ~ o . o a l ir\ - , . - - , t J

    \ : / , , \xx~ . . . . . . . . ~ ~ : - 1~ " . . 0 x

    ~ " . . . " I\ . .. . , . . I' t / . , - 0 . 0 3

    F i g u r e 4 . P l o t o f f ( x ; z , t/ , 6 ) a s a fu n c t i o n o f x , w h e r e z = 1 a n d ~ / = 0 . 1 2 5 : . . . . , 6 = 0 ;- - - , 6 = 1 . T h e p o i n t s A a n d B h a v e th e s a m e m e a n i n g s a s i n f ig u r e 1 .z = 1 a n d ~ / = 0 . 1 2 5 . I t c a n b e s e e n t h a t t h e r e a re o n l y f o u r b r a n c h e s o f s o l u t i o n s o f( 1 0 a ) f o r t h e s e v a l u e s o f 6 . A s i s e a s il y s h o w n f r o m a s i m i l a r d i s c u s s i o n t o t h a t i ns e c t i o n 2 , h o w e v e r , t h e a c c e p t a b l e b r a n c h i s a g a i n t h e b r a n ch A B e x c e p t i n th ev i c i n i ty o f t h e p o i n t B .

    T h e r e l a t io n o f t h e b r a n c h e s o f s o l u t i o n s i n s e c t i o n 3 t o t h o s e in t h e w o r k o fP a s t o r e [ 6 ] c a n b e e s t a b l i s h e d b y i n t r o d u c i n g G * d ef i n ed a s fo l l o w s :

    G * = ~ c ~ Z i c j Z J d r r [ h o ( r ) + 1 ] e - ~ ' / rZ, J

    = + 1 + '

    w h e r e w e h a v e u s e d ( 8 c ) a n d ( 1 4) . T h i s g i v e s a t r a n s f o r m a t i o n f r o m x ( = F/z ) t o G * .P a s t o r e [ 6 ] i n v e s t i g a te d s o l u t i o n s o f ( 1 0 a ) b y c o n s i d e r i n g f ( x ; z , ~7, 6 ) a s a f u n c t i o no f G * . I n fi g u r e 5 , w e s h o w f ( x ; z , t /, 6 ) a s a f u n c t i o n o f G * w i t h z = 1 a n d tl = 0 . 1 2 5 :

    : II Ii f ~ II! /

    : 1/:" /~ ].~ /.~176 /~ 1 7 6 1 7 6 J

    = : . c ' 2 2 - " "

    IIII

    - 0 . 0 3 IIII

    , ~ 1 7 6 . . . . . . . . . . . . . . . . . . . . . . . . 9 ' ~ . :9 " I i g G "" ' I I

    ~ : Z B I I\ i '- 0 . 0 a IqlF i g u r e 5 . P l o t o f f ( x ; z , ~1, 6 ) a s a f u n c t i o n o f G * , w h e r e z --- 1 a n d r / = 0 . 1 2 5 : . . . . . 6 = 0 ;, 6 = 1 . T h e p o i n t s A a n d B h a v e t h e s a m e m e a n i n g s a s in fi g ur e 1 .

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    11/13

    1 54 M. G i n o z athe b ranch AB in f igure 4 i s t r ansfo rmed to the b ranch AB in f igure 5 . F igure 2 o f[6] is for 6 = 1.

    H a f n e r e t a l . [12 , 14-16] inves t iga t ed the rmodynamic and s t ruc tu ra l p rope r t i e sof l i qu id a l loys wi th s t rong chemica l shor t - range o rde r us ing a s imple mode l cor re -spo nd in g to the spec ia l ca se o f 6 = 0 in sec t ion 4. The re su l t on the e f fect o f the' c h a r g e - n o n - n e u t r a l i t y ' c o n d i t io n i n s e c t io n 4 p r o m p t s u s to u se t h e si m p le t h e o r yin sec t ion 4 a s a mode l .

    A p p e n d i xT h e r e s u l t u n d e r th e " c h a r g e - n e u t r a l i t y ' c o n d i t io n ( 2 = O )

    A.1 . T h e M S A s o lu t i o nW a i s m a n [ 1 3 ] a n d C o p e s t a k e e t a l . [17] ob ta ined an exp l ic i t so lu t ion o f (1) and

    (5a ,b ) w i th (5c ) by us ing the ' cha rge -n eu t ra l i t y ' cond i t ion , 2 = 0 , fo r a two-c o m p o n e n t HS Y m i x tu r e. T h e e x t en s i o n o f th is so l u t i o n t o t h e c ase o f a n n -c o m p o n e n t m i x t u r e c a n b e o b t a i n e d u s i n g t h e s i m i l a r m e t h o d t o t h a t i n o u rprev ious work [18] . We g ive the re su l t he re wi thou t t he de r iva t ion :

    c o ( r ) = c ~ ( r ) + Z i Z s c , ( r ) , (A 1 a)h o ( r ) = h ~ (r ) + Z , Z j h . ( r ) , (A 1 b)

    w h e r e

    h s ( r = c s ( r) + p J dt ,cs(I cx - t I)h~(r,),h ~ ( r ) = - I ( r < a ) ,c s ( r ) = 0 ( r > ~ ) ,h . ( r ) = c . ( r ) + p f d r l c . (I rx - r ] )h .( r l) ,h . ( r ) = 0 ( r < ~ ) ,C a(r = K e - ' ( ' / ' - I ) ( r > a ) .

    r

    ( A 2 a )(A 2 b)( A 2 c )( A 3 a )(A 3 b)(A 3 c)

    I t c a n b e sh o wn b y d i r e c t su b s t i t u t i o n t h a t ( A l a , b ) w i th ( A 2 a - c ) a n d (A 3 a - c )sat isfies (1) and (5 a - c ) .

    Eq ua t io n (A 2 a ) was so lved by W er the im [19] and Th ie le [20] , whi l e (A 3 a ) wasso l v e d b y W a i sm a n [ 1 3 ] : f o r r < a ,

    Cs(r A o + A , r ( r ) a-+A 3 ,O"o o o { o - ; _ 1 ( z r ) ]c . ( r ) = - f f - + 2 - - 7 1 1 - c o s h - ; , (A 4)( A 5 )

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    12/13

    S i m p le M S A s o lu t io n in a H S Y m i x t u r e 155w h e r e

    (1 + 2 q ) 2 _ 2A 3 6 t /(1 + 89 2A o = - - , A 1 -(1 - ~/)4 q (1 - ~/)4a n d co i s t h e a c c e p t a b l e s o l u t io n o f t h e n o n l i n e a r e q u a t i o n a s

    t20[89 + 13" = co(z - 89 (A 6)O n t h e o t h e r h a n d , t h e M S A s o l u t i o n i n se c t io n 2 b e c o m e s v e ry s i m p l e w h e n

    2 = 0 . S i nc e (8 e , f ) a n d 2 = 0 g i v e D a = 0 , w e g e t AN = 0 a n d P N = 0 f r o m ( 8 a,b).T h e r e f o r e ( 7 a - d ) , ( 8 a - f ) a n d 2 = 0 g i v e t h e f o l l o w i n g c o e f f ic i e n t s o f ( 6 a,b):

    A j = A , f l j = a f t , D i j = Z i Z j t 7 2 D o , C i j = Z i Z j a 2 C o ,w h e r e (= --~ 1 + f l = - ~ , D o = - 2 r [ c k o ( z ) r + 13 e'---~n C O = 2 r 1 +' 6 q ' ~ -~ "W i t h 2 = 0 , (9 ) b e c o m e s

    6 0F 2 + z F + = O .[ ~ o ( ~ ) r + 13 5S u b s t i t u t i o n o f th e s e c o e f f i c ie n t s i n t o ( 6 a ,b ) y i e l d s

    Q d r ) = Q o (r ) + Z ~ Z j Q , ( r ) ,w h e r e

    ( A 7 )

    (A8a)

    c , j r ) = _ O a 2 F { e - Z ' / ~ - 1 e - " 2 F [ 1 - c ~ ( rz /a )] ~ ( A 9 b ). r O o ( z ) r + 1 2 z + T j '

    a n d es(r a n d ca(r) a r e g i v e n b y ( A 4 ) a n d ( A 3 e ) re s p e c t iv e l y .N o w c o m p a r i s o n o f ( A 9 b ) w i t h ( A 5 ) s u g g e s ts t h a t co a n d F a r e r e l a t e d a sf o l l o w s :

    2 Fco = dpo(z)F + 1" (A 10)U s i n g t h i s r e la t i o n , i t i s e a s y t o s h o w t h e e q u a l i t y o f t h e s o l u t i o n g i v e n b y ( A 9 a ,b )a n d ( A 7 ) w i t h t h a t g i v e n b y ( A 1 a ) , ( A 4 ) , ( A 5 ) a n d ( A 6 ) .

    w h e r e

    Q o ( r )= { ~ A r ( r - a ) + p a ( r - a ) ( r < ~ ) ,( r > ~) , (A 8 b)) ' a 2 C o ( e - z r / r _ e - Z ) 4- a 2 D o e - z ' /a ( r < a ) , (A 8 c )

    Q l ( r ) = [ a 2 D ~ e - Z ' / a ( r > a ).I t i s s t r a i g h t f o r w a r d t o o b t a i n t h e f o ll o w i n g w i t h th e s u b s t i t u t i o n o f ( A 8 a-c ) i n t o( 4 a ) a n d t h e u s e o f ( A 7 ) :

    ~c~(r) + Z~ Z j c '~(r) (r < a) ,c i j( r ) = ~ Z i Z j Ca(r ( r > a ) , (A 9 a )Do

    wnloa

    dedby[UniversityofGuanajuato]at12:1018October2011

  • 8/3/2019 Mol. Phys (ginoza)

    13/13

    1 56 M . G i n o z aA . 2 . T h e t h e r m o d y n a m i c t h e o ry

    I t i s e a s y t o s h o w t h a t t h e u s e o f c o d e f i n e d b y ( A 1 0 ) i n p l a c e o f F i n ( 1 3) , ( 14 ),( 16 ) a n d ( 17 ) y i e ld s th e c o r r e s p o n d i n g e x p r e s s i o n s f o r th e r m o d y n a m i c f u n c t io n sg i v e n b y H a f n e r e t a l . [ 1 2 ] .

    References[ 1 ] M A R C H ,N. H . , and TosI , M . P . , 1984, C o u l o m b L i q u i d s (Academic Press) .[2 ] Y O U N G ,W . H. , 1987, Can. J . Phys . , 65, 241.[3 ] B L U M ,L. , and H o w , J . S., 1978, J . s t a t i s t. P h ys . , 19, 317.[4] NnZEK I, K . , 1984, M o l e c . P h y s ., 43, 251.I-5] GINO ZA, M . , 1985, J . p h ys . S o c . Ja p a n , 5 4 , 2783; 1986a , Ib id . , 55, 95 ; 1986b, Ib id . , 55,1782.[6] PASTOP.E,G. , 1988, M o l e c . P h y s . , 63, 371.I-7] .BAXT ER, R. J., 197 0, J . ch em. P h ys . , 52, 4559.[8 ]. BLUM, L. , 1 980, J . s ta t i s t . Phys . , 22, 661.[9] FEVNMAN,R. P., 197 2, S t a t is t i c a l M e c h a n i c s (Benjamin).[10] CARNArlAN,N. F. , and STARLING,K. E. , 1969, J . ch em. Ph ys . , 51, 635.[11] CARNAnAN,N. F. , and STARLING,K. E. , 1970, J . ch em. Ph ys . , 53, 600.[12] HAFNER, . , PASTUREL,A., an d HICTER, P. , 1984 , J . P h y s . F, 14, 1137.1-13] W~dSMAN,E., 1973, J . ch em. Ph ys . , 59, 495.[14 ] HAFN~R, . , PAS ~RE L, A. , an d HICTER,P. , 1984, J . P h y s . F, 14, 2279.[15] PASa'UPa.ZL,A. , HAF r~R, J . , and HICT~R, P. , 1985, P h y s . R e v . B, 32, 5009.[16 ] HA t,mR , J . , and JANK, W . , 1988, J . P h y s . F, 18, 333.[17] COPESTAK~,A. P., EVANS, R., RUPPERSBERG,H . , an d SCrlmMACrmR, W . , 1983, J . Ph ys . ,

    13, 1993.[18 ] G IN O Z A ,M., 1987, J . p h ys . S o c . Ja p a n , 5 6 , 5 .[19] WERTHEIM,M . S., 1963, Ph ys . Rev . Le t t . , 10, 321.[20] TmELE, E . , 1963, J . ch em. Ph ys . , 39, 474.

    Downloa

    dedby[UniversityofGuanajuato]at12:1018October2011


Recommended