You are on page 1of 5

1152

J . Phys. Chem. 1984,88, 1152-1156

A Theory for the Apparent “Negative Second Wien Effect” Observed in
Electric-Field-Jump Studies of Suspensions‘
Z. A. Schelly* and R. D. Astumian
Department of Chemistry, University of Texas at Arlington, Arlington, Texas 76019-0065
(Received: June 27, 1983; In Final Form: August 15, 1983)

Transient conductance decrease has recently been observed during E-jump relaxation kinetic studies of adsorption-desorption
processes in several colloidal suspensions. A theoretical analysis of these observations is given and an interpretation is described,
where electric-field-induced increased adsorption of ions is shown to be responsible for the apparent negative second Wien
effect. A dipole model system is discussed, which exhibits a true negative second Wien effect. It is suggested that such
a dipole mechanism may provide an interpretation for the hitherto unexplained negative second Wien effects in homogeneous
solutions, which had been observed previously.

Introduction
In relaxation kinetic studies2 of fast rate processes, an equilibrium system is perturbed by a small, rapid, stepwise (transient
or jump methods) or periodic (stationary methods) variation of
a thermodynamic variable, followed by the measurement of the
rate and amplitude of the subsequent reequilibration, by monitoring a physical parameter that is proportional to the concentrations. During the perturbation, energy is introduced into the
system. For a reversible exchange of energy between a system
and its surrounding, the total differential of the Gibbs free enthalpy
G, in general, is given by3
dG = COj dFj - A dC;
J

(1)

where Oj and Fj are conjugate extensive (generalized displacements)
and intensive (generalized forces) variables, respectively. A is
the affinity, and C; is the extent of the reaction. Clearly, depending
on the nature of the system, the change of any of the conjugate
variables in (l), i.e.
SdT

fidg

ni dpi

? dl?

can affect the shift of the equilibrium. In addition ot the familiar
thermodynamic symkols (S, T, V, P , ni) in <2), pi stands for the
chemical potential, is the electric field, P is the polarization
of dielectric media, D* is related to_the “electric displacement”,2
M denotes the magnetization, and H is the magnetic field. It was
found theoreticall? that the rate 7 of reequilibration is faster (and
therefore possibly less easily measurable) if the perturbation is
accomplished by the change of an intensive variable Fj while the
extensive variables 0, are kept constant. Nevertheless, experimentally it is much easier to suddenly change an Fj, which led
to the development2 of the T-jump, P-jump, E-jump, and solvent(pi)-jump5 methods, as well as the sound absorption and
dispersion and different dielectric6 relaxation methods.
In the present paper we shall focus on some aspects of the
electric field (E)-jump method. This method is based on the
sensitivity of chemical equilibria involving ions, dipolar, or po( I ) Abstracted in part from R.D.A.’s Dissertation, University of Texas at
Arlington, 1983.
(2) Eigen, M.; DeMaeyer, L. In “Technique of Organic Chemistry”, Part
2; Friess, S. L.; Lewis, E. S.; Weisberger, A,, Eds.; Interscience: New York,
1963; Vol. 8.
(3) Schelly, Z. A. J . Chem. Educ. 1980, 57, 247.
(4) Schlogel, R. Z . Phys. Chem. (Wiesbnden) 1956, 9 , 259.
( 5 ) Chao, D. Y.; Schelly, Z. A. J . Phys. Chem. 1975, 79, 2734.
(6) DeMaeyer, L.; Persoons, A. In “Techniques in Chemistry”, Part 2;
Hammes, G. G., Ed.; Wiley: New York, 1973; Vol. 6.

0022-3654/84/2088-1152$01.50/0

larizable species to the electric field strength, according to the
relation

(a In Ka/ait)p,T= A ~ * / R T

(3)

where K, is t_he thermodynamic equilibrium constant of the reaction and AD* is the change in the macroscopic electric moment
of the system per mole equivalent transformation of reaction
partners

Le. the difference of partial molar_“polarization” of products and
reactants. The quantity D = tO5Eis usually called electric displacement, which differs from D* by the volume V of the field
space between the electrodes. The symbols to and t in (4) are the
permittivity of vacuum (rational system of units) and the macroscopic dielectric constant of the homogeneous medium, respectively. The implication of eq 3 is that, if a reaction in question
involves a net change in the dipole moments or the number of ions,
an electric field can be used to perturb the system. Generally,
field strengths of the order of 5C-100 kV/cm must be used to cause
observable effects in homogeneous solutions.
In the first E-jump experiment,’ perturbation was caused by
a single, strongly damped sinusoidal pulse of the field that also
drove the Wheatstone bridge for conductivity detection. The
application of a square pulse8 instead of the sinusoidal pulse has
the advantage that the relaxation time can be determined in a
single experiment. Subsequent instrumental developments included
the replacement of the several hundred meters of coaxial delay
cables by a low-inductance plastic capacitorg and the introduction
of photometric detection,I0 where the use of a pulsed” or synchronized flashI2 light source significantly improved the signalto-noise ratio. In spite of the advanced instrumentation, however,
only a relatively small number of chemical systems have been
studied by the E-jump method.13 The majority of these systems
involved weak electrolytes (in water as well as o r g a n i ~ ’ ~solvents)
J~
Eigen, M.; Schoen, J. 2.Elektrochem. 1955, 59, 483.
Eigen, M.; DeMaeyer, L. Z . Elektrochem. 1955, 59, 986.
. . Olsen, S. L.; Silver, R.L.; Holmes, L. P.; Auborn, J. J.; Warrick, P.,
Jr .; Eyring, E. M. Rev. Sci. Znstrum. 1971, 42, 1247.
(10) Ilgenfritz, G. Dissertation, George August University, Goettingen,
West Germany, 1966.
(11) Olsen, S . L.; Holmes, L. P.; Eyring, E. M. Rev. Sri. Instrum. 1974,
45, 859.
(12) Savage, C. R.; Herrmann, U.; Sumdani, G.; Schelly, Z. A. Rev. Sci.
Instrum. 1980, 51, 1190.
(13) For recent reviews, see: Eyring, E. M. In “Chemical and Biological
Applications of Relaxation Spectrometry”; Wyn-Jones, E., Ed.; Reidel:
Dordrecht, Holland, 1975. Purdie, N.; Eyring, E. M.; Rodriquez, L. In
“Techniques of Chemistry”; Weissberger, A.; Rossiter, B., Eds.; Wiley: New
York, 1980; Vol. 9.
(14) Massey, M. W.; Schelly, Z. A. J . Phys. Chem. 1974, 78, 2450.
0 1984 American Chemical Societv

1981. the time scale for the period between t = 0 and t l has been expanded by about a factor of 10 in this figure. M. H.z2uz)/(ui + u2)k71 I ... F. K. Two opposite charges of equal magnitude zeo must be separated to a distance of 1/2p to form a dipole that acquiresJhe energy -kT if aligned in the direction of the applied field E . Eyring. Fuoss. Kim. 198. Dashed line: Expected signal for a system where only the sorption of ions on the induced dipoles occurs. that is triggered at time t = 0 and terminated at t l . Thus. (19) Wien. 1449. R. J . Inoue.zzeo2/8mq. T. (22) Onsager.2 R. Sasaki. the expected exponential increase of the conductance during the application of the high electric field was preceded by a transient decrease of conductance.. 1928. 1957. 1957. T. J. Z. before the application of the perturbation square pulse. Chem. the E-jump method was also used to study heterogeneous systems.. It was found that the major effect of the field on strong electrolytes21is the acceleration of ions to such an extent that they are able to break away from their surrounding ion atmosphere. Chem. electrolysis. Eyring. the ratio 209 of the two characteristic distances q and 1/2P describes the probability of two ions escaping from an ion pair under the influence of an external field. The energy of Coulombic interaction between two ions bearing charges of zleOand zzeOin a medium with dielectric constant e becomes equal to kT when they approach each other to a distance of 29. (b). -t Figure 2. 85. 1983.= R2 = 50 0. R. K. 61. Moriya. 88.1984 1153 for which the field-induced equilibrium shift is typically much larger than for dipolar equilibria. Phys.. L..... Z . K. Kan.= 104-10s a. For the balanced bridge. submitted for publication. Strohbusch. (20) Wien. 2. In contrast to (a). upon the application of the external field.. Vol.. Narl. which produces ions. T. the approximate values of the circuit components are as follows for the sample (s) and reference (r) cells: C. D. 32. Ibid. Sasaki.S. and (c). 1866. 6. Vol.16i8 Interestingly. Schematic representation of the several different transient (7) where uiare the mechanical mobilities (reciprocal of the friction constants) of the ions. The relative increase of the equilibrium constant K2 = k2/k-2due to this ”dissociation field effect” is given byZZ l o where Kz(E) and Kz(E=O) are the dissociation constants at a field E and E = 0. Ashida. Phys.83. in the absence of the second Wien effect. 545. D. Discussion Wien’s experimental observations of conductivity increases upon the application of high electric fields to both strongig and weak20 electrolytes are now referred to as the first and second Wien effects. 2 25 p F R. L. (23) DeMaeyer. which leads to increased mobilities. Phys. Phys. The last is due to the buildup of double layers at the electrodes in less than 1 ps at the high fields Another effect. (21) Onsager. The relaxation time and the amplitude of the decrease are dependent on E . Onsager.A. However. (18) Hachiya. in a first approximation. namely the adsorption-desorption equilibria of ions at the solid-liquid interface in aqueous suspensions of colloidal metal oxide particles. Astumian. and the effect is more amenable to detection.23 ~ I ~~~ (15) Marshall. Chem. J . Chem. OSC = oscilloscope. Z . 29. U. (5) k-2 field is the asymmetric perturbation of the ionic Brownian motion. T. (d) Expected signal for a system where polarization is the only effect.. For weak where the dissociation is described by eq 5. No. The quantity q = -z. leading only to an increase of the rate constant kz. M.) ion pair =A + + Bk2A Figure 1. R. (c) Solid line: Typical signal observed in the suspensions discussed (ref 16-18). In an actual E-jump experiment. Moriya. 1969. J . 14. M. In “Methods of Enzymology”. (b) Typical conductance increase caused by the second Wien effect for a weak electrolyte. 1978.Apparent Negative Second Wien Effect The Journal of Physical Chemistry. 1979.61.. Yasunaga. Kustin. Lundy-Douglas. respectively. and Fuoss have provided theoretical interpretations for both types of deviation from Ohm’s law. M. Academic Press: New York.. M. 1934. Onsager. Chem. signals observed or expected for the models discussed in the text and their temporal relationship to the perturbation square pulse (a). (16) Sasaki. L. 2549. Yasunaga. The quantity 2@ represents a reciprocal distance and is defined as 20 = IEeo(ziu1 . with relaxation times ranging from 5 to 50 ps. Acad. J. Joule heating. respectively. Phys. H. Phys.. Kim.. Phys. 1931.. M. The subsequent conductance increase is caused by the simultaneous second Wien effect on the surface of the particles. The initial conductance decrease is due to the sorption of ions on the colloidal particle dipoles induced by the external field 8. (24) Schelly. (17) Astumian. R. Schematic representation of the conductometric detection (Wheatstone) bridge in E-jump experiments. electrode polarization. M. Yasunaga. L. 599. and space charge effects are also present. of course. A. one usually wishes to establish the time dependence of the major (second Wien) effect. = C.87. M. 668.. D. Proc. E. B. 751. M. In the present paper we propose a field-induced increased adsorption of ions on the particles as an explanation for the apparent “negative second Wien effect”. 2270. S.. Recently.kT is known as the “Bjerrum radius”. several secondary effects such as the first Wien effect. t=O t. Ed. . 75.. Sci. the major effect of the electric k AB k-l (A+-B. K. M. This results in an overall shift to the right of eq 5. which. in contrast to the ionic electrical mobilities which are given by zieoui.

can become a major factor.Schelly and Astumian 1154 The Journal of Physical Chemistry. the Coulombic interaction between the particle and the ions will be balanced by their thermal motions after the formation of an electrical double layer around the particle. K. (29) 0 Konski. 66.26 Le.U ( € 2 - €1) + 2a1 . In both cases a charged interface results.~~~~~ by surface cond~ctivity. No. 153. S. very rapid electronic and atomic polarization of the particle. 69.64. Upon the application of a homogeneous.v(a2 .S. they involve the movement of ions over one or more molecular distances or lattice sites. (a) A positively charged particle at equilibrium with the electrolyte solution in the absence of an external field. For the systems under investigation a1 > az is the case. Ado. the relevant polarization mechanisms are all migratory in nature.. (2)). The relaxation time of the polarization process is given by3’ 2q 7Mw = 2a1 + €2 . is the polarization of the particles of the system under investigation. Robertson. S. the particle undergoes rapid polarization.charges arrive from the solution at the interface faster than they can be transported through the solid. 13. (c) Illustration of the quantities relevant for surface. the bridge is balanced to UDB= 0 with a small alternating potential applied across AC (see Figure 1). Charges in the double layer represent excess local charges. J. V. “Dielectrophoresis”. 66. J . and the final effective induced dipole moment pMwbyz5 Surface conductivity is a frequency-independent mechanism by which charge is transferred from one side of the sphere to the other.Cambridge University Press: Cam- bridge. the sample cell contains the weak electrolyte studied. the surface potential of the particle. the relaxation time for the surface-conductance modified interfacial polarization is given by33 €2 rMws = a2 + 2A. H. which essentially determines Zl/ZZ (25) Dukhin. (b) Maxwell-Wagner polarization of an uncharged particle for the case u1 > u2. and references therein. Schematic representation of the models discussed. Shilov. 271.d is the effective surface conductance of the shell. (28) y g n e r . J* = 0. A. . Electrotech. along the surface. 2636. If u1> u2. In a typical E-jump experiment. Physical Model. Vol. Arch. Progr. Maczuk. and the reference cell is fitted with a solution of strong electrolyte that has the same specific conductivity as the weak electrolyte. Prior to the application of the high-voltage perturbation square pulse. C. Chem. (32) Miles. G. C. 1 . Colloid Sci. Surface conductivity can be treatedz9as a part of the total conductance u2/ of the particle ai = a2 + 2u. 3. let us consider one of the spherical particles of colloidal size (radius r > 100 A) carrying a free charge Q. 1970. = a. 2626./r + 2tl . J . 7.v(t2 + a2 . (Berlin) 1914. The most important polarization mechanisms are the Maxwell-Wagner (interfacial) p o l a r i z a t i ~ npolarization .32within a thin shell of thickness d and conductivity a.u(u2 + 2AJr . (Figure 3c).al) (13) where A. P. and the overall system is electrically neutral. Maxwell-Wagner polarization occurs if the conductivity of the medium is different from that of the particle (cf. the double layer may be broken down into two portions... 83. (34) Dukhin.. The particle itself has a conductance of u2 and a dielectric constant c2. J.. conductance us. “A Treatise on Electricity and Magnetism”. Pauly. All the secondary influences can be reduced to a negligible minumum by suitable difference measurements. UK. Phys. H. If ul < a2. W.a1) €1) (10) (where u denotes the volume fraction of the spheres).25 The dense part at the sphere surface is the layer of tightly bound (chemisorbed) ions.. The outside diffuse part is made up of the supporting counterions. The medium is a dilute electrolyte. 1973. 88. Colloid Znterface Sci. Phys. (27) Maxwell. To interpret the transient conductivity decrease (Figure 2c) observed in colloidal systems. (31) van Beek. Schwarz. J . B. N. P. 1932. Details are given in ref 2 and 23. 1960. Polarization results only if a. and the choice of the experimental conditions. UK. 2nd ed. = qr3E . between the plates of the capacitor. Clarendon Press: Oxford. Chem. suspended in a medium of conductance ul and dielectric constant t l between the plates of a capacitor (Figure 3a). H. :7) p = po + p . Phys. Dielectr. 583. the essential part of the experimental setup is the Wheatstone bridge (Figure 1) that was used also in the studies of the colloidal syswhich we wish to analyze. The anticipated effective induced dipole moment p of a charged sphere with a surface conductance is found34to be ( . 1978. 6. for small volume fraction v. constant electric field ?!. H. > ul. 1962. (30) Schwarz.+ . For conductivity detection. Under this condition the impedances of the arms of the bridge fulfill the relationship WZr = (8) During the perturbation. In the absence of an electric field. which are held by Coulombic attraction.2~ and bound layer30 and diffuse layerz5 polarization. the dissociation field effect increases the conductivity of the sample cell.1984 I Figure 3. 1962. Phys.- -1 (14) where po and ps are the induced dipole moment components of (26) Pohl. Chem.. Vol. 2. the net fluxes of both positive and negative ions toward the sphere are zero.charges arrive from the particle interior faster than they can be carried away toward the electrodes through the solution. Besides the negligibly small. with charge accumulation at the two polar regions of the sphere facing the electrodes.d/r (12) If it is assumed that the outer surface of the conducting shell provides still another surface upon which charge accumulation can occur in the Maxwell-Wagner sense. L. 1881. S. 40. during which process work w is done on the system (cf. J. If the charge Q of the particle is due to chemisorbed ions. resulting in a situation depicted in Figure 3b. Surf. (d) Bound and diffuse layer polarization of a positively charged particle at steady state in an external field. 1980. resulting in a typical relaxation signal given in Figure 2b. the proper design of the instrument. At equilibrium. G. as we shall show. 605. Figure 3b). Rev. (33) Schwan. T. The dielectric constant e and conductance u of the medium (1) and the particles (2) are valid for all pictures.

all the mechanisms discussed above predict a relaxation time of polarization T~~ < 2 ps. this approximation cannot be used.21r cos 0)-1/2 . When y >> 1. with the that the major effect is the polarization of the double layer. to a good approximation. clearly. Since both p and I . respectively. the system would reach a steady state (in contrast to an equilibrium state in the absence of an external field) with respect to the thermal motions and fluxes. The concerted effect of the fields is the preferred motion of the ions toward the oppositely charged ends of the dipoles where they adhere to the particles (Figurg 4). Thus. Charges in the double layer represent excess local charges. . we shall investigate only the equilibrium case. we are interested only in the outside region.+~/ZkT)+ 3m exp(eo{/2kT)]/~r (18) with the dimensionless parameter m being m = el(kT)2/6~qDeo2 (19) In eq 18 and 19. z I Figure 5. opposite to the field. in the bulk solution. characterized by div J* = 0 for both positive and negative ions.(r2 I2 21r cos ~ ) ] . the charge component dominates and the particle polarizes in the direction of the field. & represents the surface charge equilibrium density of the bound ions. where r >> I. linearly increase with the field E. The two surfaces re are not spherical. which would result in a pulse-shaped response (Figure 2d) of the Wheatstone bridge. free ions is drastically reduced. K is the Debye-Hiickel reciprocal distance. these mechanisms predict a sizeable polarization with little or no direct contribution to the dc conductivity. and for r = 500 nm.26 The more successful treatment^^^. 88. The net result of the sudden (in less than 0. and co is the ion concentration in the bulk solution.r. uncharged particle with a spherical permanent-dipole particle. where the contribution of the bound layer is muted by that of the diffuse portion (Figure 3d). The “Binding” Constant of Free Ions to a Dipole. It is instructive to investigate how the number of ions associated with a dielectric spherical particle changes upon its polarization. the following expression was derived:34 where 3 = [e~p(e. qd represents the potential at the outer Stern plane. each suspended in a dilute electrolyte solution. close to the surface. the surface conductance component of the dipole is small and the particle polarizes by the Maxwell-Wagner mechanism.l /(21) ~ Although. Schematic representation of the sorption of ions on an induced-dipole particle (positively charged). under associated we mean that the potential energy of interaction between the two moieties is greater than 2kT. even in the surface-conductance modified version. {the zeta potential. how a permanent dipole (without an external field) binds ions.are the ionic charges. but diffusion away from the surface requires overcoming a considerable activation barrier. no ions are associated with the particle. If the polarization of our model system was the only effect. in contrast to the simplified drawing given. eq 21 reduces to + = 2Q1 cos 0 / h r 2 e o q (22) in our case. if the polarization is very fast. The charges within the equipotential surface re represent excess local charges. For particles of r < 80 nm. 7 the viscosity of the medium. At some value of y the induced dipole moment is zero. the strength of the dipoles is decreasing because of partial charge neutralization at the poles. During the formation of the giant particle dipoles.^^ involve the consideration of the electrically flexible parts of the ionic double layer. They found the expression for the relaxation time of polarization as TBDL = r2/2DJ4 (15) where D. one expects both the amplitude and the rate of the conductance decrease to do so too. where the potential of the dipole is + = ( Q / 4 i ~ e ~ q ) ( r-~r2-l) -~ (20) which according to the law of cosines can be written as + + + +(r. The amount of ions adsorbed should be proportional to the induced dipole moment p of the particles and the rate 7-l of their adsorption to the average bulk ion current I in the solution. its dipole moment is p = 21Q. and y = u. Thus./u. In the first system. Comparison of the several theories shows that simple bulk factors such as considered in the Maxwell-Wagner approach. it would only increase the capacitance of the sample cell (Figure l ) . with the rise time of the first pulse approximately equal to the relaxation time of polarization T ~ ~ . with reference to Figure 5 . Bound and diffuse layer polarization both represent mechanisms where ionic motion tangent to the surface is relatively unhindered. Dukhin et ale’sanalysis34suggests that both must be present and that the latter is more important. Illustration of a permanent-dipole particle oriented by an external field. is the production of giant dipoles aligned in the direction of the field. to a good approximation. however. In the second system. Vol. which is called the isopolarization state. The details of the sorption process with respect to the depth of penetration of the double layer by the ions is less important than the fact that the mobility of a significant number of originally Figure 4. 1984 1155 Apparent Negative Second Wien Effect the sphere uncharged and that due to charge flow on the surface. 6. No. When y is very small and u1 > u2. the free ions in the solution are exposed not only to the external field but also to the local fields of the dipoles.The Journal of Physical Chemistry.( Z + + Z-)Kpb/co (16) where z+ and z. For the induced dipole moment due to doublelayer polarization. During the “binding” of ions. Following Onsager. The expected signal for this situation is depicted by the dashed line in Figure 2c. Either because they actually adsorb at the bound layer or because they become incorporated in the diffuse layer. Le. we are comparing two systems: a spherical.O) = (Q/4iT€o€l)[(r2 Iz . with the systems and experimental conditions of ref 18-18. there is a decrease of free charge carriers. as was borne out by experiments (see Figures 2 and 3 of ref 16). if the dipole particle consists of two point charges *Q that are located at the surface. For illustration. Several authors considered the possibility of each of the bound and diffuse layer polarizations occurring alone. Since the ions cannot penetrate the sphere. at this point. but they increase the surface capacitance. are inadequate to account for the experimental facts of the anomalous ”giant” polarization of suspensions in polar solvents. If no other processes (second Wien effect) occurred simultaneously. and D the mean diffusion coefficient of the counterions. is the coefficient of bound ion diffusion and M denotes hf = 1 + Z + z . We propose this field-induced increased adsorption of ions to be the source of the transient conductivity decrease observed (Figure 2c).1 ps) application of the external dc field. in essence. T~~ < 50 fis.

JVi/V.83. A. micelles. 1967. the corresponding stoichiometric equations can be obtained by simply replacing S by R in (26) and (28). governed by the rate constants. Eyring. if the bulk number density of the i-type ions in the solution is oni = .A.' i CiNo.l of the bound i-type ions per dipole can be obtained from iN. A. within which ions are considered bound. Furthermore. Jr.**A-) k-1 ion pair kz S2-C' + A- (28) k-2 + It is important to remember that the and . Patterson. Yasunaga. The angle runs around the axis of the dipole. E. In case of a field-induced dipole of the same magnitude p (instead of starting with a permanent dipole). in this case slower. Spinnler. To find re. as for a strong electrolyte. While oppositely charged ions are deposited at the poles by the field (Figure 4). In the case of a homogeneous system. which can be contrasted to the situation depicted in Figure 3d. involving ionic groups permanently attached to the surface. etc. polyelectrolytes. A. the ionic atmospheres are somewhat distorted. local charge density. Generalization to Homogeneous Systems. the integration is carried out only for the first octant. in an electric field.. Patterson.eoJ/(r.eo. Then. and the resulting increase of conductance ultimately may become dominant.in (28)) produces ions at the slower rates of the chemical relaxation(s) of (28).J . coupled with the reaction CA&C+ k-3 + A- If K3 is large. In this final steady state. at rates of the ion currents in the solution. until the overall process reaches a steady state.. K. F.NdciNb) i K3 4 (25) 1 Thus. Jr. With respect to the ion binding. 500. if all the possibly different types of cations and anions present are denoted by C+ and A-. Vol.. administered by the American Chemical Society. E. Phys. eq 5 can be rewritten for the colloidal systems as S-C-A k 2 (S-C+-A-) k-l ion pair S-C+ + A- (26) k-2 $=O Since the problem has cylindrical symmetry with respect to the y axis and planar symmetry with respect to the xz plane. Rampton. It seems that the role of the particle S can also be assumed by a molecular moiety R of large polarizability a. chemical reactions (eq 5) take place because of the second Wien effect. Acknowledgment. M. Chern. 69.D. A detailed analysis of dipolar systems will be published in a forthcoming paper. J . however. F.^' Chemical-Physical Model. ki S?-C-A + (Sf-C+. the fluxes are maintained by the continuous input of energy. rapidly transforms the particles to large dipoles S+ (Figure 3d). R. after setting J/ = 2kT/z. J . J. (37) Cole. This work was partially supported by the R. 1761. but possibly also chemically. with an even larger expected true negative second Wien effect. respectively. (36) Spinnler. simultaneously with the polarization and ion-sorption processes also. The field. We are grateful for stimulating discussions with Professors H. Systems involving biological macromolecules with many adsorption sites.l = 8 s " s r e ~ r ' 2 0 nexp(-z. 1961. the "binding constant* can be written as the fraction Kb = [bound ions] [free ions] - in which the reaction is. Acknowledgment is made to the donors of the Petroleum Research Fund. F. however. If the permanent dipole in equilibrium with its two different ionic atmospheres at the poles is exposed to an external dc field. simultaneously the second Wien effect (. until the termination of the perturbing square pulse.symbols on S? represent a large number of elementary charges and that the two polar regions of the particle are not equivalent. which would correspond to a true negative second Wien effect. They differ in polarity. the. 71. No. At this point we only would like to mention that the dipolar mechanisms we have outlined may provide an interpretation for the hitherto unexplained negative second Wien effects in homogeneous systems. 1965. Sasaki. the number of bound i-type ions is ii?b= NdiN<and the total number of bound ions is N d c i i N { . Am. and the two polar regions are separated by a large distance on the molecular scale. In the colloidal systems studied. for partial support of this work and to the Japanese Ministry of Education for a visiting research scholarship to R.. and also additional induced polarization may occur.. which had been observed in ~ t a t i c as ~ ~well 9 ~as kinetic context^.. Chem. 2771. Chem. . 88. P. and C. in this hypothetical model.0)/kT)r2 i sin 0 d r d0 d 4 (24) 8=0 r=l Schelly and Astumian signal (solid line in Figure 2c). the deposited ions can ultimately reach the opposite sides of the particle through surface conductance. A.. etc. as we have shown. which is responsible for the conductance-increase part of the observed (35) Bailey. ions are produced during the chemical relaxation. Welch Foundation and the Organized Research Fund of UTA. eq 26 should be written as Ndcrly. Berg and T. L. It is important to note that this relaxation takes place between two steady states. Naturally. as well as Dr. Hence.. Thus..the number iN. As mentioned before. = (23) Z$O* by setting E. J. ionic concentrations. however.l6-l8 reaction 5 occurs on the surface of the suspended particles. the dipole will orient in the direction of the field. = 2kT we can obtain an equipotential surface re(O. The integration limit Be corresponds to the point where the equipotential surface intersects the particle. R. surface potential. the applied field has negligible effect on equilibrium 27 and thus on its contribution to the conductance change. $ = constant). During the rotation. Hachiya. the two ionic atmospheres face the likecharged electrodes.1156 The Journal of Physical Chemistry. eq 21 must be expanded as a polynomial in r a n d solved. the electric field will shift the equilibrium toward increased association. Savage. the final steady state reached will be the same. Silzars. Let us now turn back to the relaxation signal in Figure 2c. note that in the final aligned position. the conductance does not change any more (Figure 2c). Phys. M. Jensen. SOC. D. increasing the dipole moment from zero t o p increases the binding constant from zero to Kb. at least physically (in case sometof the free ions in the solution are different from those in (26)). D. If the total number of dipoles in the solution is Nd. and so..1984 Since the potential energy of an i-type ion with charge zpo is just E. Thus. the particles S themselves are part of the weak-electrolyte equilibrium shifted by the second Wien effect. seem to be possible prime candidates for the observation of apparent negative second Wien effects in homogeneous solutions. During the application of the external field. T. where a fraction of them may desorb because of the favorable direction of the field. 6.