ISSN 0036 0244, Russian Journal of Physical Chemistry A, 2012, Vol. 86, No. 11, pp. 17321735.

Pleiades Publishing, Ltd., 2012. Original Russian Text S.A. Nekrasov, 2012, published in Zhurnal Fizicheskoi Khimii, 2012, Vol. 86, No. 11, pp. 18591863.

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

AbstractThe 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 [17]. The considerable number of works in this area deal mostly with studying the effect of an electric current passing through a solution [14, 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 [24]. 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 2

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

(1)

Fig. 1. Unit scheme.

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d 2 = e (C + C ), 2 s dx

(2)

y, rel. units

2 d D d C2 d C = 0, hag + hrw < x < l a, (3) dx dx dx (0) = U , (x* 0) = (x* + 0),

0.8

d d (4) (x* 0) (x* 0) = (x* + 0) (x* + 0), dx dx x* {hag, hag + hrw, l , l + hag }, (l + hag + hrw ) = 0,
d D dC C = 0, x = 0, dx dx x = l a + hag + hrw,
la

0.6 0.4 E

(5)

0.2

1 C (x)dx = C , i0 la

(6)

0.2

0.4

0.6

0.8 1.0 x, rel. units

where (1) and (2) are unidimensional Laplace and Poisson equations for the electric potential, is the electrostatic potential, x is the abscissa, l a is the length of the bulk solution, hag is the thickness of the air gap separating the electrode and the reservoir with the solution, hrw is the thickness of the reservoir wall, e is the electron charge, s is the dielectric constant of the solution, C is the concentration of positive (+) and negative () free charges in the water, D are diffusion coefficients, is the ion mobility, Ci 0 is the ion con centration in the bulk solution with no field, (3) is the equation of ion diffusion in the solution with an elec tric field, the areas of application of equations (2) and (3) coincide, (4) are the boundary conditions for the electrostatic potential, (5) are those for ion concentra tions, and (6) are equations expressing the law of charge conservation. Due to conditions (5) and (6), the bulk drift and diffusional components balance each other out in solution and there is no summary current. The solution to system (1)(5) can be expressed in quadratures using standard analytic methods. It follows from Eq. (1) that the electric field inten sity in the air gap Eag and inside the Pexiglass Erw is constant. The solution to diffusion equation (3), allowing for boundary conditions (5) and the NernstEinstein relation for the mobility of ions, are the functions

Fig. 2. Normalized graph of potential and field intensity.

Because of symmetry, 0 = (x 0 ) = U /2 , C+(x0) = C (x0) = A, and consequently

e( ) (8) C + C = 2 A sinsh 0 . kBT Inserting (8) into Poisson equation (2), we obtain a quasilinear differential equation after some elemen tary transformations:
d 2 2 1 (9) = d z sinsh ( z( 0 )) , 2 dx where z = e , and d is the Debye radius of water in kBT the middle of the solution:

skBT (10) d = 2 . 2e A The solution to Eqs. (9) can be expressed in quadratures,

z ( A 0 )

1/2

x A x x 0, (11) u z (0 ) + 4sinsh 2 where xA = hag + hrw, A = (x A ), = E 0 zd , and (x) = U (2x 0 x) at x > x0. The electric field intensity is determined using the formula

du

1/ 2

x xA , d

e( 0 ) (7) C = A exp , kBT where kB is the Bolzman constant; T is absolute tem perature; and A are constants that can be determined from law of charge conservation (6), where x 0 = l a /2 + hag + hrw is the abscissa of the aquariums middle.
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z( 0 ) . (12) 2 A qualitative description of the dependences of the potential and electric field intensity is shown in Fig. 2. From boundary conditions (4), we find (13) 0 E ag = rw E rw = s E = s E , E(x) = z 1d 1 2 + 4sinsh 2
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where 0 is a dielectric constant; E A = E(x A ), E K = E(x K ) is the electric field intensity near the aquarium walls around the anode and cathode, respectively; and x K = la + x A . Allowing for (4) and (13),

A = U E ag hag E rw hrw h h = U s E ag + rw = U hE A, 0 rw where h = s ( hag / 0 + hrw / rw ) .

(14)

Let us estimate the values of E A and A at the top of the aquarium. From (12) and (14), 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. We initially calculate the value of the Debye radius for pure water, d 0 , which depends on the ion concentration according to (10). It is known [810] 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 = A + hz d

1 1

+ 4sinsh
2

z( A 0 ) 2

1/2

2H 2O H3O+ + OH . In pure water at 25, the concentration of ions is [8, 9]

Ci0 = [H +] = [OH ]
7 19 3 = 10 mol/L 6.14 10 m . The relative dielectric penetrability of water at room temperature is 81 [11]. After inserting the correspond ing numerical values into (10) we find that the Debye radius of distilled water is ~1 m. Since l a = 1 m, hag = 103 m, hrw = 5 103, = 2.50 (for typical Plexiglas [11]), and U = 50 kV, we found that h h h = s ag + rw 0.24 m. 0 rw According to (19), voltage drops by no more than 0.4 V in water (i.e., by less than 0.01% of the interelec trode voltage). The voltage of the electric field in the middle of the water volume is infinitesimally small: E 0 < 10 200000 V/m. A field with this value can have no impact on bioobjects in a volume of water; for the sake of com parison, a water molecule would have nearly the same effect on an electron if they were 10100 km apart. All of the electric field is concentrated in a very thin micro scopic layer 0.01 mm thick. In ordinary fresh water or in aqueous electrolyte solutions, the concentration of free ions is many orders of magnitude higher than in distilled water, and the Debye radius is less than 0.1 m. Hence, the electric field is many times weaker than in distilled water.

> A + h ( A 0 ), d
whence
1 + h/(2d) , 1 + h/ d According to (11), A < U
x xA < d
z( A 0 )

A 0 <

U . 2(1 + h/ d )

(15)

z(0 )

du = ln A 0 , 0 u

(16)

whence

0 0 + ( A 0 )exp
In view of (12),

x xA , d

x x0. (17)

E(x) < z 1d 1 + 4sinsh

2 2

z( A 0 ) x xA exp 2 d

x x A zU z 1d 1 2 + 4sinsh 2 exp . d 4(1 + h/ d) x x 0. The drop in voltage in water can be estimated at the top from the value A K = 2( A 0 ) < Ud / ( h + d ) < Ud / h. (19)
Let us now estimate the value for field intensity E 0 at the middle of the aquarium. Allowing for (19) and inserting x = x 0, we use (11) to obtain
la < 2d
z( A 0 )

))

1/2

(18)
1/2

1/ 2 U U du < ln + 1 + , E 0h E 0h 2 + u2

whence U /E 0h > sh (l a /2d ) , and thus

E 0 < U / hsinsh

la . 2d

(20)

ESTIMATING THE EFFECT OF OTHER FACTORS EDLs are so thin that their convection processes are negligibly small, and the theory of boundary layer thus applies. At the boundary of a solution (near the reservoir walls), the so called conditions of adherence and impermeability hold [12, 13], and there is virtually no transfer of mass from the bulk solution to the EDL. Fish eggs and plant seeds are many times larger than the thickness of a EDL, and bioobjects therefore lie beyond the action of the electric field. The equation
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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. However, computa tional experiments show that this factor produces no new qualitative results and has virtually no effect on the order of EDL thickness. The degree of ion hydra tion is normally not considered when calculating the processes of electron and mass transfer in weak elec trolytes. There is thus virtually no electrostatic field in a vol ume of water, 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. It is con sequently assumed that the sensational discovery reported by the CIBAGEIGY 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. 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, relative to the Debye radius. The above relations obtained above can also be used in particular to calculate the electric field in microscopic capillaries filled with electrolyte solution, and in dielectric liquids with very low concentrations of free charges. Similar conditions hold for so called capacitors with electric double layers [14]. A model of an electric double layer was first created by Helmholtz, 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). Gouy, Stern and Frumkin then formulated the classic theory on the structure and properties of electric double layers in aqueous electrolytes [1, 8, 9]. It was established that the specific capacity of a EDL was very high (~0.2 F/m2), and the potential differ ence in a EDL can be 1 V or even higher. The charge of a capacitor with a electric double layer is deter mined from the formula = Q/, where is the change in the interphase potential difference, and Q is the accumulated charge on interphase boundary. The above properties are used in energy accumu lating capacitors of a relatively new kind: electric dou ble layer capacitors, known in the Russian literature as ionistors and as supercapacitors or electrochemical capacitors in the foreign literature. Some types of these capacitors are able to accumulate more than 10 kJ/kg of energy, and to discharge it into a load with

specific power of between 1 and 10 kW/kg [14]. In ion istors, the energy is accumulated via charging by means of electric double layer polarization at the boundaries of the anodeelectrolyte and cathode electrolyte interfaces. One feature of the above electrolytic systems is the interaction (overlapping) of electric double layers. The results from calculations for one such system are pre sented in Fig. 2. 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). The Debye radius of the solution was d = 106 m; the value of the potential at the solu tion boundary was (0) 0.19 V; (la) 0.19 V; the field intensity in the middle of the solution was E0 = 104 V/m; and the field intensity at the solution bound ary (in a dense ionic layer) was E(0) = E(la) 106 V/m. REFERENCES
1. B. B. Damaskin and O. A. Petrii, Electrochemical Kinet ics: an Introduction (Vyssh. Shkola, Moscow, 1987). 2. A. Ya. Tretyak and S. A. Nekrasov, Building of Petro leum and Gas Wells on Earth and Sea (VNIIOENG, Moscow, 1995), No. 12, p. 28 [in Russian]. 3. S. A. Nekrasov, Izv. Vyssh. Uchebn. Zaved., Elek tromekh., No. 2, 22 (2003). 4. S. A. Nekrasov, Ionic Transfer in Flow of Electrolyte at the Action of Magnetic Field, Izv. Ross. Akad. Nauk Elektrokhim. 2013 (in press). 5. Dr. G. Ebner and H. Schuerch, AT Patent No. 86066 (1993). 6. Chem. Abstr. 95 (165987b), 453 (1981); M. Vosyliene et al., Reaction of Aquatic Animals to Electric Fields. 9. Sensitivity of Trout and Carp to an Electric Current and Content of Biogenic Monoamines in Their Tissues during Various Seasons of the Year, Liet. TSR Mokslu Akad. Darb., Ser. C, No. 3, 109118 (1981). 7. R. Goodman and A. S. Henderson. Bioelectromagnet ics 7, 23 (1986). 8. N. L. Glinka, General Chemistry (Khimiya, Leningrad, 1986) [in Russian]. 9. L. A. Sleta, Chemistry: Manual (Folio, Kharkov, 1997) [in Russian]. FS Information, Report Sendung 10. Suedwestfunk (Baden Baden, 1992). 11. N. P. Bogoroditskii, V. V. Pasynkov, and B. M. Tareev, Electrotechnical Materials (Energoatomizdat, Lenin grad, 1985) [in Russian]. 12. G. Korn and T. Korn, Guide on Mathematics (Nauka, Moscow, 1978) [in Russian]. 13. A. V. Lykov, Heat and Mass Transfer (Energy, Moscow, 1978) [in Russian]. 14. V. P. Kuznetsov, Elektron. Tekh., Ser. 5, No. 4, 85 (1991).

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