The effect of direct interactions on Brownian diffusion

C. Van den Broeck, F. Lostak, and H. N. W. Lekkerkerker

Citation: The Journal of Chemical Physics 74, 2006 (1981); doi: 10.1063/1.441244
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N.24 has shown that the diffusion coefficient D starts from a Smoluchowski equation for the N-particle in Eq. (1) can be written probability distribution in configuration space. W. Brussels. 23. (1) problem can be distinguished. Consider a cylindrical vessel filled with a suspension dence of the mobility and the osmotic compressibility.24 relating mobility and diffusion. Specific examples of such potentials are considered in some detail. This tendency that even for the simple case of hard spheres a number can be described by a current density j which is pro- of different theoretical results have been given.O.225. mental importance in the further discussion we briefly to the case of interacting particles. The effect of direct interactions on Brownian diffusion C. We first give a simple derivation of this where A is the area of the cross section of the vessel. The first approach l . 1. Belgium. 2006 J. (2) is of funda- Einstein argument. Phys. Lostak. Fakulteit Wetenschappen. Belgium (Received 14 November 1979. I.00 © 1981 American Institute of Physics This article is copyrighted as indicated in the article. Lekkerkerker Vrije Universiteit Brussel. Van den Broeck. sion process is the osmotic pressure gradient along Felderhof also indicated why previous authors failed the Z axis. Reuse of AIP content is subject to the terms at: http://scitation.44 On: Sun. to a force in the Z direction given by actions between the suspended particles on their diffu- sion coefficient starting from the generalized Einstein [II(z) . Local differences of this denSity will be of the experimental data has be~n confused by the fact smoothed out by the process of diffusion. Basically two different theoretical approaches to the j= -Dgradn. are in complete agreement with the ones obtained by 1). Felderhof l4 has shown by explicit calculation sion of particles takes place as the result of a concen- that the results obtained from the Smoluchowski equation tration gradient along the (horizontal) Z axis (see Fig. W. 13 much where b is the mobility of the suspended particles and simpler. 1981 0021·9606/81/032006·05$01. Diffusion of Brownian particles in a cylindrical vessel under influence of an osmotic pressure gradient along the hori- alAspirant N. 21 Dec 2014 22:46:24 . FIG. This description must then be reduced to a closed equation for the one-body distribution function which displays D=b(aII) an T. whereas a repulsive term has the opposite effect. portional to gradn. 74(3).P . in which diffu- Recently. These pended particle measured along the Z axis results then allow us to consider the denSity dependence of the diffusion coefficient for a given interaction poten- tial between the particles. then remains is the..r instance. Thus. The thermodynamic driving force for this diffu- Batchelor from the generalized Einstein approach. The problem that sketch its derivation following Einstein's argument.14 and ex. General conclusions are f=-~ :~=-~(:~)T'P :. It is shown that an attractive potential added to the hard core repulsion leads to a decrease of the diffusion coefficient. we discuss the possibility to obtain information on the interaction potential between suspended particles from the density dependence of their diffusion coef- ficient.22 work.. we obtain for the thermodynamic force per sus- of the mobility and the osmotic compressibility. relation. calculation of the denSity +dz)] A. Simple examples of attractive and repulsive potentials are considered in some detail. zontal Z axis. INTRODUCTION II. approach is based upon an extension of the II is their osmotic pressure. fo. ticles enclosed between the vertical sections Sand S' of the vessel at the positions z and z + dz are subject In this paper we discuss the influence of static inter. Using these results the possibility to obtain information on the interaction potential between suspended particles from their diffusion coefficient is discussed. F. The quantitative interpretation density n. accepted 31 January 1980) The effect of direct interactions between suspended particles on their diffusion coefficient is investigated starting from the generalized Einstein relation. and H. Chem. Downloaded to IP: 128.240. (2) the diffusion coefficient explicitly.1 Feb. (3) drawn for the case that the potential comprises in addi- tion to a hard core part a (purely) attractive or (purely) repulsive part.12 23 Einstein . fundamental relation and present the density dependence Thus.aip. The second. Since Eq. DIFFUSION MOBILITY AND OSMOTIC The study of the diffusion of interacting particles has COMPR ESSI BI L1TY recently been the object of much theoretical l .a) F. Consider a system of suspended particles with number perimental 15. the suspended par- to find this agreement. in thermal and mechanical equilibrium. Based upon these re- sults.

(13). 1 February 1981 This article is copyrighted as indicated in the article.... The coefficient C can be obtained from the MacMillan- age velocity with respect to a volume fixed frame of Mayer 26 .. (13) scopic time and length scales. III. Vol. Therefore.27 virial expansion for the osmotic pressure reference (12) (U)= bj. and Lekkerkerker: Brownian diffusion 2007 As a result of this force the particles acquire an aver.). ). ). the direct nonhydrodynamical Stokes expression interactions have been accounted for in a statistical sense in that they affect the pair correlation function. The results given in Eqs. 74. EFFECTS OF DIRECT INTERACTIONS ing the osmotic pressure and the mobility. coefficient in this same frame of reference.)]r2dr. (4) is to be understood as a thermodynamic result valid on macro. A. { 0 for r>2a.225. Phys. The denSity dependence of the mo- bility was first considered by Burgers 28 and further j=n(0=_b(all) an. (10) with CHS =8 (16) C = 2B2/ j-lTa3 (11) and (13). Eq.240. since b represents sideration. (2) sidered here. Substituting the above expressions in Eq.. Downloaded to IP: 128.3. b = bo= 1/6lT1)a. (14) in (12).44 On: Sun. and Goldman. The resulting current density where W12 (r) is the potential of mean force between the j thus reads suspended particles. (4) where b is the mobility. Reuse of AIP content is subject to the terms at: http://scitation. General considerations At low concentrations these effects can be taken into account by expanding II and b in a power series of the In the discussion of the effect of direct interactions concentration it is convenient to distinguish the contribution of the II = kT (n+B 2n2+ . hard core from the remaining interactions. mobility reduces to the In deriving Eq. and for spherical particles the. On such scales On- sager's assumption25 is valid and states that a system The first three terms represent the effect of the motion cannot distinguish between external and thermodynamic of the surrounding particles on the particle under con- forces.~[exp( -k~12)-1] Note that in the derivation the thermodynamic force is treated as if it were an external force acting on the 1 1 ~ xrdr+"2+as 52. This is (7) achieved by writing b = {l/6lT1)a) (1 + A¢ + . 21 Dec 2014 22:46:24 . (8) (14) Here B2 is the second osmotic virial coefficient and ¢ is the volume fraction where ¢= j-lTa 3n. Lostak. whereas it is clear that its origin is of a statistical nature. (6) ficient for a given potential. one obtains D=Do{l + kD ¢ +". Cox. however. In Eq. (12) and (13) allow one to the diffusion coefficient calculate the density dependence of the diffusion coef- Do = kT/6lT1)a. there will be both static and hydrodynamic interactions between the particles affect. (2) is an expression for the diffusion duced in itself by the presence of the other particles. (5) refined by Batchelor. (6) to (8) together with Eq. It should also be noted that. x [A(r)+2B(r)-3(1+. 12 . 31 respectively. case of one particle moving in a thermal ensemble of t icles and 1) is the shear viscosity of the suspending surrounding particles by Phillies. (15) Here where kD =C +A. Chern. and Brenner. WHS _ 00 for Os rS 2a. The effect on the dynamics itself. calculated for the Here a is the hydrodynamic radius of the suspended par. (2) allow one to write the diffusion coefficient as Substituting Eq. No. Van den Broeck. Eq. In general. 32 will not be con- medium. The last term takes into account the effect the mobility with respect to a volume fixed frame of of the motion of the particle under consideration in- reference. (9) C=C HS +C INT .P az tains Comparing this result with expression (1) for the cur- rent density one is led to the Einstein relation (2). exp -kT (W) 12 suspended particles. respectively. A=~ f [exp(-k~12 )-1] r2dr+~ 5. one obtains the famous Stokes-Einstein expression for The results given in Eqs. boA(r) is the mobility of a pair of sus- pended particles separated by a distance r along the At infinite dilution where all interactions between the line connecting their centers and boB(r) is the mobility particles can be neglected the osmotic pressure is given perpendicular to this line. Exact expressions for A(r) by the Van't Hoff equation and B(r) have been obtained by Stimson and Jeffery 30 ll=llo=nkT. 29 From the latter work one ob- an T.

1 February 1981 This article is copyrighted as indicated in the (20a)) kD = /lri B + kbNT . one obtains pare with Eq.WI2 /kT) in Eqs.. for a"" 3. the effect of attractive forces is simu- x [ A (r) + 2B (r) . (25) For this model potential the attractive contribution to which follows again from the values tabulated by Batche. One notes that no similar general conclusions can be obtained for po- . (24). ?1 range potentials. (20a). (20b). (29) This inequality is based upon the fact that for 2a(1+x)<r. No. Thus an attractive W~fT leads to an increase k1NT = .kT W12) -1I r .0.3] is always XINT = O.1] rdr. (10) and (15). Note that the frame of reference the effect of the backflow hinders latter contribution is small so that one may generally the motion of particles far away from one another.O. (27b) we have written explicitly the contribution posite effect. A(r)+2B(r)-3~ 3a/r (r2: 2a). the osmotic compressibility is of the form lor. Attractive and repulsive potentials + ai ~: [ex p (-k~12 )-1J A very simple model to take into account the effect of attractive forces has been proposed by Batchelor. (27c) note x [A(r) + 2B(r) . Thus we find that the diffusion coefficient follows the behavior of the osmotic A more detailed model for attractive interactions compressibility. (21) where AINT = ~ ~: [ exp ( -k~12) . 2008 Van den Broeck. the diffusion coefficient decreases for From the values for A and B compiled by Batchelor it increasing a.. Lostak.lHS = _ 6. such as the one considered here. we clearly have to decrease of the osmotic compressibility whereas a repulsive W IfT has the opposite effect.O. (23) that in agreement with the general conclusions reached in Sec. Phys.6] r2 dr. In particular. 13 and (23) yields The result (19) was first obtained by Batchelor using numerical values for A(r) and B(r) derived from the C INT = _ a. approximate XINT by only its direct contribution [com- Combining Eqs.dr 2a obtains for the mobility INT (18) =t IC I. IXINT I~ t ICINTI· (24) for 2a<r~2a(1+x). (28) (22) This approximate expression of AINT allows consider- and able Simplification in analytic calculations and we will henceforth use it. whereas in a volume fixed and the induction contribution .(20). Substituting Eq. W ~rT has the opposite effect. (25) in Eq. and Lekkerkerker: Brownian diffusion (17) From Eq. (27b) positive. (26) x [A(r) + 2B(r) . it immediately follows that C INT = _ 8(e Y -1) [(1 +x)3 -1]. (17) it is clear that an attractive W ~fT leads Thus. The error is maximal for short + kINT _ D .240. )] r2 dr (20a) lated by an excess number act> of nearly touching par- ticles.!.225.55 (19) tentials with both attractive and repulsive contributions and in wlfT.6] is always negative. 5a arising from the direct hydrodynamic effect of sur- the fact that a pair of particles moving close to each rounding particles on the particles under consideration. (20b) Substitution of g(O) = exp(. (30) J. 06a = O. 44a. . it can even be shown that in that still can be handled easily is the square well model these cases: for O~ r~ 2a. (7). the effect of follows that [A(r) + 2B(r) . other drag one another. Vol. From Eq.3. where which completes the proof of Eq. From these values it also follows that [A(r) + 2B(r) . In fact. 21 Dec 2014 22:46:24 .3 ( 1 +.1] 2a g(O)(r)=g~OB) (r)+~aao(r-2a). 5a . and is then of the order of 10%. (27a) exact expressions for these quantities. 56a.44 On: Sun. Physically this can be understood from O. AINT=~~: (-:r12 )-1]rdr [exp B.3] r2 dr.aip. This means that the pair correlation function to lowest order in the denSity g(O)(r) is given by 1 = (? J(= [ exp (-~ W 12) . This the attractive interactions cancels the effect of the implies that a purely attractive W~rT leads to a decrease hard core and the Stokes-Einstein value Do for the dif- of the diffusion coefficient whereas a purely repulsive fusion coefficient is recovered. (27c) of the mobility whereas a repulsive W ~fT has the op- In Eq. III. Downloaded to IP: 128. 29 In this model. Chern. A. 74. Similarly one IAINT I ~ -A a f=2a I exp (.. Reuse of AIP content is subject to the terms at: http://scitation.

supported by the Interuniversitair Instituut voor Kern- SubstitutingEq. one obtains for . 21 Dec 2014 22:46:24 . 1 February 1981 This article is copyrighted as indicated in the article. decreased to the value e. (39) For large values of A. can be effectively interpreted as an increase of the hard cient k1NT . Finally.225. Phys. No. (17) and (28). (40) Results (30)-(32) are in agreement with those obtained by Altenberger. and Ii = ~ LO [( 1 + ~ ) -A _ 1] ~u (A2) AINT~+ ~ ~: [ex p ( -k~12 ) -1 ] dr. Note that C INT and AINT . Diffusion is a convenient alternative to obtain informa- tion about the mobility given the value of the osmotic As a more realistic example for a repulsive potential compressibility. have the same dependence on the well depth ykT. action (36). the integrand on the right-hand side of Eq. (41) x«l. Downloaded to IP: 128. A similar interpretation has been given by Onsager 34 for the osmotic pressure As the counterpart of the simple a model for attrac- for the case of Coulomb interaction between two plane tive interactions. (A2) can be approximated by (e. which both are influenced by the direct interac- tions between these particles. For increasing range Thus the effective diameter equals the actual diameter of the potential this ratio decreases and it thus gives increased by the distance Ii for which the potential has an indication of the range of the potential. (30) and (31). (36) We thank Dr. This allows us to approximate Eqs. However. Van den Broeck.!. (24)]. Reuse of AIP content is subject to the terms at: http://scitation. one finds for the coeffi. and Lekkerkerker: Brownian diffusion 2009 From Eqs. 561kT. (36)inEqs. Vol. Thus the Expression (40) can be given a simple physical meaning ratio of any two of these quantities depends only on the by noting that range of the potential 2ax.240. principle the dependence of the diffusion coefficient on A and~. (31) Combining Eqs. for the square well potential. is much smaller than the radius of the particle. (32) Ii "" ~ (InA + C). conclude from Eq.--~- ]}-A -1 (37) (A1) is only appreciably different from zero for r close to 2a. Lostak. For short range potentials W12 (2a + Ii) ~ kT e. AINT = 6(eY -1)[ (1 +x)2 -1]. the Debye length ~ of the individual quantities separately. (28) and (29). (34) The diffusion coefficient depends on a combination of the static and dynamic properties of the suspended par- and thus ticles. 74. DISCUSSION AINT = _ 6 [ (1 + {3)2 .. (33) IV. (36) we find explicitly for Ii.44 On: Sun. More spe- bility and the osmotic compressibility allows a more cifically we study the case of charged particles sur- detailed knowledge of the interaction potential than each rounded by a thin double layer. and consequently K1NT .2a)/~]. (40) that interactions by introducing an effective hard sphere Ii may be Significantly larger than ~. i. This work has been surface charge or surface potential of the we simulate the effect of repulsive double layers.3. (A1).c = O. Veretennicoff for several illuminat- where A> 0 is a strength factor which is related to the ing discussions on this problem.2a) exp(-WI2 /kT)-1= {l+exp [ .(r . where C denotes Euler's constant tion in the latter paper is accounted 'for incompletely. it is possible to obtain conve- APPENDIX nient approximate analytic expressions by suitably ex- plOiting the short range character of the repulsive inter.c kT. Chern. c= 0. diameter 2a(1 + {3) with {3 > O. e. the ratio IAINT/CINTI is close to its maximal value t [compare with Eq. The dependence on dy- (35) namic properties stems from the dependence on the Note that the ratio I AINT / C INT I is the same here as mobility which is difficult to evaluate experimentally. one obtains in wetenschappen (uKW). From Eq.5772'" . The combined knowledge of the mo- we consider a shielded Coulomb potential. (17) and (28) Introducing the new variable by u=A exp[ . core diameter from 2a to 2a + Ii. the hard sphere contribu. Indeed the quantity (r.1] . (38) one finds from Eq.\INT. One then obtains C INT = 8[ (1 + {3)3 -1]. 4 However.2(eY -1)[ (1 +x)2(1 + 4x) -1].U -l}/u and The remaining quantity one obtains J.. The shielded Coulomb potential can then be written33 ACKNOWLEDGMENTS WI2(r)=AkTln{1+exp[-(r-2a)/~]} (r~ 2a). When A is large the value of Ii can be approximately written (see Appendix) kbNT = .aip.

38. 69. Langevin. Z. Letamendia. W. and J. R. Phys. Lachaise. Chabrat. 276 2A . Graciaa. 2010 Van den Broeck. J. K. J. 9S. 5G. 34L.eO") -du . N. J. 323 (1978). Hess and R. Benedek. Onsager. Phys. 110 (1926). A 9. 242 (1976). 33 E . L. W. J. D. 11B. Colloid is small so that Eq. 8W. 15J. Klein. J. (1973). Soc.aip. J. Sci. Chern. and A. Mazer. 29 (1979). Phys. 1 February 1981 This article is copyrighted as indicated in the article. Taupin. 14. and C. 405 (1931).org/termsconditions. Stimson and G. C. P. J. Chern. 894 (1973). Chem. (1945). Wesley. Proc. Ann. R. and H. 19B . 5772· ••.240. N. Lachaise. 25 (1978). 70. 111. J. Batchelor. 21. 1895 (1976). Goodwin. Chern. D. Fluid Mech. 269 (1976). Onsager. (Paris) Lett.3. Harris. Chern. Chern. 32G . 29 G . Chern. J. 64. defined by Phys. Chern. Fair. Eng. M. J. R. 74. L. Sci. Downloaded to IP: 128. J. A. 15. 16G. Lett. 664 (1975). Jeffery. 24A . E. E. A 8. 509 (1976). U. J. 19. 351 (1978). M. Chem. Phys. J. Vrij. C. Phys. R. 627 (1949). Langevin. P. E. 253 (1977). 245 (1972). Vaucarnps. Phys. and N. lOB. Sci. A 11.S~ e" -du = O. and R. the integral Interface Sci. B. B 287. Phys. A. Phillies. 62. and Lekkerkerker: Brownian diffusion {j ""~ r A Jo (1 _ eO") du . G. Chang. Phys. 21A . No. G. A. Wet. L. Ser. Fijnaut. Y. 4690 (1977). 66. Phys. Acad. Brown. 74.1177(1941). IJ. J. J. L. 13.1045. Graciaa. 51. K. M. (A3) reduces to Eq. 27'1'. Vol. 45. Schurr. Jamieson. 59. C. R. 67. B. Acad.225. Ned. 976 (1974). 4A. Brenner. G. Reading. Phillies. where we introduced Euler's constant C. A. Vaucarnps. and A. Fluid Mech. J. and C. 1833 25 L . Goldman. J. Reed. 37. An Introduction to Statistical Mechanics (Addison- 3A. Stability of LyophobiC Colloids (Elsevier. 1948). Altenberger and J. Allison. D. Chern. Deutch. Charnbu. J. Felderhof. 21 Dec 2014 22:46:24 . Rouch. Y. R. 59. Altenberger. McMillan and J. (Paris) Lett. 929 (1978). p. Theory of the 12S. J. Amsterdam. J. Phys. Chap. J. Akad. Rouch. C. J. {j""~ ( lnA+C+ J ~ e-" A duU)' (A3) Chern. Anderson and C. Lagues. J. u 13G. J. Batchelor. J. (to be published). Mayer. Ann. 1994 (1979). Letamendia. Ackerson. D. J. 26W. J. Pusey. Phillies. 38. 14B . J. D. 28J. J. Phys. Murphy. D. Lostak. (Leipzig) 17. J. Verwey and J. D.. Chern. u (A4) 18A. Phys. Nieuwenhuis. L. Phys. J. Burgers. 1 (1976). Phys. Mass. This leads immediately to Ottewil. Chern. A (1975) . f A ~ -" e -du U 2oA. "G. 23A . Rev. and A. 1883 (1976). Chabrat. Phys. London Ser. Ackerson. 1960). Phillies. D. 3925 (1975). C. Th. 689 (1978). Cazabat. 44. Bourrel. Chern. 39. Chao. pathrnananoharan. Ober. J. J. C= fo l u 1 - (1 . R. 126 (1941).44 On: Sun. 3240 30M . and C. M. Hill. 59. 7J. Einstein. M. Chern. Electrochern. 9. Phys. Reuse of AIP content is subject to the terms at: http://scitation. J. Phys. G. Phys. 549 (1905). M. status Solidi A 85. 60. L. Cox. Overbeek. 1151 (1966). Einstein. (40). A. 17A. Aguirre and T. Cazabat. 22H. 65. Phys. M. 235 (1908). Proc. M. M. Phys. Chern. 52. Phys.. 64. 235 (1978) . J. Altenberger. Colloid For large values of A. Pouchelon. Interface Sci. Phys. 31A . K. M.