ISSN 0036 0244, Russian Journal of Physical Chemistry A, 2012, Vol. 86, No. 11, pp. 1732–1735. © Pleiades Publishing, Ltd., 2012.

Original Russian Text © S.A. Nekrasov, 2012, published in Zhurnal Fizicheskoi Khimii, 2012, Vol. 86, No. 11, pp. 1859–1863.

COLLOID CHEMISTRY AND ELECTROCHEMISTRY

Calculating the Electrostatic Field in the Bulk of an Aqueous Solution
S. A. Nekrasov
South Russia State Technical University, Novocherkassk, 346428 Russia e mail: Nekrasoff_Novoch@mail.ru
Received: August 17, 2012

Abstract—The problem of an external electric field penetrating into the bulk of an electrolyte solution is investigated. An exact solution to the problem of calculating the static electric field in a finite electrolyte vol ume between two galvanically isolated flat electrodes is found. Corresponding examples of applying the obtained relations are considered. Keywords: electrolyte, static electric field, calculation. DOI: 10.1134/S0036024412110209

INTRODUCTION Treating solutions with magnetic and electric fields is one promising trend of applied physical chemistry and electrochemistry [1–7]. The considerable number of works in this area deal mostly with studying the effect of an electric current passing through a solution [1–4, 6, 7]. The effect of an external magnetic field on a moving electrolyte solution, resulting in the ener gence of ionic currents circulating in the solution, and of a dense so called ionic electric double layer (EDL), was investigated in [2–4]. The effect of an external static electric field on the properties of a bulk electro lyte has been studied to a lesser degree. This is explained in particular by the existence of the Gouy and Chapman theory [1, 8, 9] of EDLs, according to which an external static electric field penetrates into an electrolyte layer to a distance on the order of the Debye radius. The Gouy and Chapman theory [1, 8, 9] was elab orated for an infinite electrolyte layer. This work dem onstrates conclusively that the DES theory holds almost completely, and thus no statistical electric field is responsible for the substantial effect on bioobjects placed in a treated solution. EQUATION SYSTEM DESCRIBING A STATIC ELECTRIC FIELD AND DIFFUSION IN THE FINITE VOLUME OF AN AQUEOUS SOLUTION The scheme of the setup used in [5] shown in Fig. 1. The bulk solution is in a Plexiglas reservoir of parallelepiped form. Flat aluminum electrodes, embedded in the Plexiglas of the bottom and the cover, are hermetically isolated from the water and air, and are connected to a voltage source. Plexiglas is a famil iar insulating and water resistant material. There are

no other sources of an electromagnetic field that can act on water or aqueous electrolyte solution. The electric field in the bulk solution depends on the value of the voltage applied to voltage electrodes U (which is assumed to be constant and equal to several tens of kilovolts); the concentration, mobility, and space distribution of charged particles in electrolyte volume: the length of the bulk solution (l a ≈ 1 m), the thickness of material of walls (hrw ≈ 5 mm), the thick ness of air gap (hag ≈ 1 mm). Under these conditions, the electric field is plane parallel because of the symmetry of the geometrical shape of the electrolyte volume and the electrodes and can be described by the following unidimensional boundary problem (BP) [1, 3, 4]:

d 2ϕ

= 0, 0 < x < hag + hrw, dx 2 l a < x < l a + hag + hrw,

(1)

Fig. 1. Unit scheme.

1732

D ± are diffusion coefficients. x = 0. (3) dx dx dx ϕ(0) = U . 2 εs dx (2) y. (5) are those for ion concentra tions. dx dx x* ∈ {hag. ϕ A = ϕ(x A ). ± dϕ −D ± dC ∓ C ±μ ± = 0.4 E (5) 0. The solution to diffusion equation (3). are the functions Fig.0 x. (11) u z (ϕ−ϕ0 ) κ + 4sinsh 2 where xA = hag + hrw. l а. rel.4 0. kBT ⎠ ⎝ where kB is the Bolzman constant. hag is the thickness of the air gap separating the electrode and the reservoir with the solution. ( ) 0. and (6) are equations expressing the law of charge conservation. ⎝ 2e A ⎠ The solution to Eqs. units 2 ± ± ± ± dϕ D d C2 ± d C µ = 0. the areas of application of equations (2) and (3) coincide. where x 0 = l a /2 + hag + hrw is the abscissa of the aquarium’s middle. (4) are the boundary conditions for the electrostatic potential. x is the abscissa. Ci 0 is the ion con centration in the bulk solution with no field.2 1 C ± (x)dx = C . Normalized graph of potential and field intensity. i0 la ∫ 0 (6) 0 0.8 1. hrw is the thickness of the reservoir wall. The electric field intensity is determined using the formula ∫ ( du 2 2 ) 1/ 2 = x − xA . Because of symmetry. rel.2 0. 86 No. (12) 2 A qualitative description of the dependences of the potential and electric field intensity is shown in Fig. T is absolute tem perature. C is the concentration of positive (+) and negative (–) free charges in the water. µ ± is the ion mobility. d ⎛ e(ϕ − ϕ0 )⎞ (7) C ± = A± exp ⎜ ∓ ⎟. The solution to system (1)–(5) can be expressed in quadratures using standard analytic methods. RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A z(ϕ − ϕ0 ) .CALCULATING THE ELECTROSTATIC FIELD 1733 d 2ϕ = − e (C + − C − ). hag + hrw < x < l a. (9) can be expressed in quadratures. ⎝ kBT ⎠ Inserting (8) into Poisson equation (2). and A± are constants that can be determined from law of charge conservation (6). units where (1) and (2) are unidimensional Laplace and Poisson equations for the electric potential. 2. we find (13) ε 0 E ag = ε rw E rw = ε s E А = ε s E К . the bulk drift and diffusional components balance each other out in solution and there is no summary current. hag + hrw. and ϕ(x) = U − ϕ(2x 0 − x) at x > x0. 2 dx where z = e . l а + hag }. allowing for boundary conditions (5) and the Nernst–Einstein relation for the mobility of ions. l a is the length of the bulk solution.6 ϕ 0. and consequently − ⎛ e(ϕ − ϕ) ⎞ (8) C + − C − = 2 A sinsh ⎜ 0 ⎟. 11 2012 ( ) 1/ 2 . From boundary conditions (4). ϕ is the electrostatic potential. la 0. εs is the dielectric constant of the ± solution. It follows from Eq. (1) that the electric field inten sity in the air gap Eag and inside the Pexiglass Erw is constant. z (ϕ A −ϕ0 ) 1/2 x A ≤ x ≤ x 0. Due to conditions (5) and (6).6 0. e is the electron charge. C+(x0) = C (x0) = A.8 dϕ dϕ (4) ε(x* − 0) (x* − 0) = ε(x* + 0) (x* + 0). (3) is the equation of ion diffusion in the solution with an elec tric field. E(x) = z −1d −1 κ 2 + 4sinsh 2 Vol. ϕ(l а + hag + hrw ) = 0. ϕ0 = ϕ(x 0 ) = U /2 . κ = E 0 zd . 2. ϕ(x* − 0) = ϕ(x* + 0). and d is the Debye radius of water in kBT the middle of the solution: ε skBT ⎞ (10) d =⎛ ⎜ 2 ⎟ . dx dx x = l a + hag + hrw. we obtain a quasilinear differential equation after some elemen tary transformations: d 2ϕ −2 −1 (9) = d z sinsh ( z(ϕ − ϕ 0 )) .

by less than 0. The drop in voltage in water can be estimated at the top from the value ϕ A − ϕ K = 2(ϕ A − ϕ0 ) < Ud / ( h + d ) < Ud / h. The equation Vol. and there is virtually no transfer of mass from the bulk solution to the EDL. 13]. From (12) and (14). hrw = 5 × 10–3. and bioobjects therefore lie beyond the action of the electric field. 1 + h/ d According to (11). (14) Let us estimate the values of E A and ϕ A at the top of the aquarium. 2d (20) ESTIMATING THE EFFECT OF OTHER FACTORS EDLs are so thin that their convection processes are negligibly small.1 μm. and thus E 0 < U / hsinsh la .14 × 10 m . 86 No. 9] Ci0 = [H +] = [OH −] −7 19 −3 = 10 mol/L ≈ 6. ϕA < U x − xA < d z(ϕ A −ϕ0 ) ϕ A − ϕ0 < U . The voltage of the electric field in the middle of the water volume is infinitesimally small: E 0 < 10 −200000 V/m. ⎜ E 0h ⎣ ⎝ E 0h ⎠⎦ ⎟ κ2 + u2 ⎝ ⎠ whence U /E 0h > sh (l a /2d ) . Hence. It is known [8–10] that conductivity in pure water is a result of the − hydrogen H + and hydroxyl OH ions formed as a con sequence of dissociation reactions H 2O ↔ H ++OH − and self ionization U = ϕ A + hz d −1 −1 ( κ + 4sinsh 2 2 z(ϕ A − ϕ0 ) 2 ) 1/2 2H 2O ↔ H3O+ + OH −. ( x − xA . (17) E(x) < z −1d −1 × × ⎡κ + 4sinsh ⎢ ⎣ 2 2 ( z(ϕ A − ϕ0 ) x − xA ⎤ exp − ⎥ ⎦ 2 d ( ⎡ ⎛ x − x A ⎞⎤ zU ≤ z −1d −1 ⎢κ 2 + 4sinsh 2 ⎜ exp − ⎟⎥ . the concentration of free ions is many orders of magnitude higher than in distilled water. E K = E(x K ) is the electric field intensity near the aquarium walls around the anode and cathode. and the Debye radius is less than 0. a water molecule would have nearly the same effect on an electron if they were 10100 km apart. and x K = la + x A . (19) Let us now estimate the value for field intensity E 0 at the middle of the aquarium. hag = 10–3 m.4 V in water (i. d ) x ≤ x0. which depends on the ion concentration according to (10).01 mm thick.e. d whence 1 + h/(2d) . ε = 2. ⎝ ε 0 ε rw ⎠ According to (19). > ϕ A + h (ϕ A − ϕ0 ). and the theory of boundary layer thus applies. the concentration of ions is [8. and U = 50 kV. we find CALCULATING THE ELECTROSTATIC FIELD IN VOLUMES OF DISTILLED AND ORDINARY WATER Our numerical estimates for the value of an electric field in the bulk of an aqueous solution are based on the above relations. In ordinary fresh water or in aqueous electrolyte solutions. ε ε ⎝ 0 rw ⎠ where h = ε s ( hag / ε 0 + hrw / ε rw ) . After inserting the correspond ing numerical values into (10) we find that the Debye radius of distilled water is ~1 μm. In pure water at 25°С. respectively.01% of the interelec trode voltage). for the sake of com parison. At the boundary of a solution (near the reservoir walls).1734 NEKRASOV where ε 0 is a dielectric constant.. Allowing for (4) and (13). the so called conditions of adherence and impermeability hold [12. voltage drops by no more than 0. All of the electric field is concentrated in a very thin micro scopic layer 0. We initially calculate the value of the Debye radius for pure water. Since l a = 1 m. The relative dielectric penetrability of water at room temperature is 81 [11]. ϕ A = U − E ag hag − E rw hrw ⎛h h ⎞ = U − ε s E А ⎜ ag + rw ⎟ = U − hE A. d 0 . ϕ − ϕ0 u (16) whence ϕ0 ≤ ϕ ≤ ϕ0 + (ϕ A − ϕ0 )exp − In view of (12). the electric field is many times weaker than in distilled water. d ⎠⎦ ⎣ ⎝ 4(1 + h/ d) x ≤ x 0. Allowing for (19) and inserting x = x 0. we found that ⎛h h ⎞ h = ε s ⎜ ag + rw ⎟ ≈ 0. 2(1 + h/ d ) (15) z(ϕ−ϕ0 ) ∫ du = ln ϕ A − ϕ 0 . E A = E(x A ). 11 2012 RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A . A field with this value can have no impact on bioobjects in a volume of water. Fish eggs and plant seeds are many times larger than the thickness of a EDL. we use (11) to obtain la < 2d z(ϕ A −ϕ0 ) ( )) 1/2 ) (18) 1/2 ∫ 0 1/ 2 ⎛U ⎡ ⎛ U ⎞⎤ ⎞ du < ln ⎜ + ⎢1 + ⎜ ⎟⎥ ⎟ .24 m.5ε0 (for typical Plexiglas [11]).

ϕ(la) ≈ 0.. S.. P. Korn.2 F/m2). P.” Liet. 13. A. Zaved. Uchebn. “Ionic Transfer in Flow of Electrolyte at the Action of Magnetic Field. Nekrasov. Tekh. Nauk Elektrokhim. 2. 1995). Report Sendung 10. Tareev. p. The normalized plots of the potential and the intensity of the electric field were obtained for a microscopic flat capillary with a width of several Debye radii (la = 6d). Ross. Ya. 5. No. 1978) [in Russian]. and the potential differ ence in a EDL can be 1 V or even higher. S. Izv. V. V.. 12. TSR Mokslu Akad. 8. One feature of the above electrolytic systems is the interaction (overlapping) of electric double layers. Ser. and to discharge it into a load with specific power of between 1 and 10 kW/kg [14]. A. The Debye radius of the solution was d = 10–6 m.. where Δϕ is the change in the interphase potential difference. computa tional experiments show that this factor produces no new qualitative results and has virtually no effect on the order of EDL thickness. Akad. and B. No. 86066 (1993). 1997) [in Russian]. 2. Some types of these capacitors are able to accumulate more than 10 kJ/kg of energy. Glinka. Nekrasov. 12. Similar conditions hold for so called capacitors with electric double layers [14]. 4. M. Heat and Mass Transfer (Energy. 23 (1986). Vosyliene et al. The results from calculations for one such system are pre sented in Fig. 7. 9. However. Gouy. No. Chem. Abstr. 11 2012 . 11. 28 [in Russian]. 3. relative to the Debye radius. V. Schuerch. Moscow. 9]. Moscow.” Izv. Chemistry: Manual (Folio. Guide on Mathematics (Nauka. 14. In ion istors. S. Elektron. Pasynkov. FS Information. and in dielectric liquids with very low concentrations of free charges. The degree of ion hydra tion is normally not considered when calculating the processes of electron and mass transfer in weak elec trolytes. Darb. A. Dr. 2013 (in press). 3. Ebner and H. Korn and T. the value of the potential at the solu tion boundary was ϕ(0) ≈ –0. Bogoroditskii. N.19 V. the energy is accumulated via charging by means of electric double layer polarization at the boundaries of the anode–electrolyte and cathode— electrolyte interfaces. the field intensity in the middle of the solution was E0 = 104 V/m. B. The above properties are used in energy accumu lating capacitors of a relatively new kind: electric dou ble layer capacitors. Moscow. Tret’yak and S. Sensitivity of Trout and Carp to an Electric Current and Content of Biogenic Monoamines in Their Tissues during Various Seasons of the Year. Stern and Frumkin then formulated the classic theory on the structure and properties of electric double layers in aqueous electrolytes [1. 1978) [in Russian]. A. The above relations obtained above can also be used in particular to calculate the electric field in microscopic capillaries filled with electrolyte solution. The charge of a capacitor with a electric double layer is deter mined from the formula С = ΔQ/Δϕ. C. 1986) [in Russian]. B. and ΔQ is the accumulated charge on interphase boundary. There is thus virtually no electrostatic field in a vol ume of water.. Goodman and A. Vyssh. Elek tromekh. R. who demonstrated that a EDL is essen tially a capacitor with one plate being the charged electrode surface and the other being the layer of ions with opposite charge in the electrolyte (an ionic con ductor). Sleta. It is con sequently assumed that the sensational discovery reported by the CIBA–GEIGY laboratory in [5] is explained not by the influence of an external electro static field but by factors of a different nature not yet explained. Lykov. 109–118 (1981). RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 95 (165987b). Damaskin and O. 1992). OTHER POSSIBLE APPLICATIONS OF RELATIONS OBTAINED Note that there are cases of practical importance where the final electrolyte sizes must be considered due to the low density of free charges or by the rela tively small size of their area. Electrotechnical Materials (Energoatomizdat. Ser. General Chemistry (Khimiya. 86 No. Electrochemical Kinet ics: an Introduction (Vyssh. 9. It was established that the specific capacity of a EDL was very high (~0. “Reaction of Aquatic Animals to Electric Fields. known in the Russian literature as ionistors and as supercapacitors or electrochemical capacitors in the foreign literature. 6. 5. 1987). Leningrad. A. Moscow. 2. since it is screened by the microscopi cally thin layer of ions in the electric double layer and cannot affect the vital activity of organisms. Lenin grad. A model of an electric double layer was first created by Helmholtz. 22 (2003). Building of Petro leum and Gas Wells on Earth and Sea (VNIIOENG. Nekrasov. L. 85 (1991). M. A. REFERENCES 1. N. G. L. G. A. Petrii.19 V. Kharkov. No. Kuznetsov.CALCULATING THE ELECTROSTATIC FIELD 1735 for the state of an electrolyte with allowance for the displacement of water molecules by ions and the final size of ions is generally nonlinear. and the field intensity at the solution bound ary (in a dense ionic layer) was E(0) = E(la) ≈ 106 V/m. Suedwestfunk (Baden Baden. 453 (1981). 4. 8. Bioelectromagnet ics 7. AT Patent No. Henderson. Shkola. V. 1985) [in Russian].

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