DIFFUSE DOUBLE-LAYER EQUATIONS IN SI UNITS

By Albert T. Yeung,1 Associate Member, ASCE

INTRODUCTION
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The interaction of the short range repulsion force and the long range
attraction between clay particles may have a profound influence on the
engineering properties of the soil (Mitchell 1976). The energy of repulsion
depends on electrolyte concentration, cation valence, pH, temperature and
permittivity of the pore fluid. All these effects are accounted for by the
Gouy-Chapman theory of diffuse double layer (Gouy 1910; Chapman 1913).
In most textbooks, the derivations of the equations describing the diffuse
double layer are presented in electrostatic units (Mitchell 1976; van Olphen
1977). As the applications of the diffuse double-layer equations are not
limited to clay mineralologists, the equations and units used should be
unified to enhance multidisciplinary communications. Two recent applica-
tions of diffuse double-layer computations in hazardous waste management
are discussed here as examples.
Available experimental data on the hydraulic conductivity of compacted
clay exposed to chemicals indicated that the effects of chemicals on hydraulic
conductivity are consistent with their effects on the diffuse double layer and
interparticle forces that control flocculation, dispersion, shrinkage, and swelling
(Sridharan and Jayadeva 1982; Acar et al. 1985; Alther et al. 1985; Mitchell
and Madsen 1987). Hence, the thickness of diffuse double layer may give
a quantitative assessment of the possible change in hydraulic conductivity
of a compacted clay landfill liner, in response to permeation with different
chemicals.
Recently, the potential uses of electrokinetics in hazardous waste re-
mediation are being investigated. All conceivable mechanisms involve cou-
pled flows of water, electricity, and contaminants under the combined in-
fluence of hydraulic, electrical, and chemical gradients (Yeung 1990, Hamed
et al. 1991, Mitchell and Yeung 1991, Yeung and Mitchell, in press, 1992).
Coupled flow occurs when one type of flow is induced by a force of another
type. In these cases, the consistency of units is extremely important in the
theoretical formulation and subsequent computations.
As the amount of research in hazardous waste management and site
remediation is growing and the number of involved researchers from dif-
ferent disciplines is increasing, the problem of inconsistent fundamental
relationship and units becomes apparent. Hence it is worthwhile to rede-
velop the Stern-Gouy-Chapman equations to eliminate these ambiguities
and redundant conversion factors, and to enable researchers of hazardous
waste management from different disciplines to communicate on a unified
platform. Moreover, this technical note intends to clarify some of the com-
mon typographical errors existing in a number of widely used textbooks.

'Asst. Prof., Dept. of Civ. Engrg., Texas A&M Univ., College Station, TX 77843-
3136.
Note. Discussion open until June 1, 1993. To extend the closing date one month,
a written request must be filed with the ASCE Manager of Journals. The manuscript
for this paper was submitted for review and possible publication on February 27,
1991. This paper is part of the Journal of Geotechnical Engineering, Vol. 118, No.
12, December, 1992. ©ASCE, ISSN 0733-9410/92/0012-2000/$1.00 + $.15 per page.
Paper No. 1451.
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J. Geotech. Engrg. 1992.118:2000-2005.

 The mathematical description of the Gouy-Chapman theory of diffuse
double layer is treated here. The Stern correction for finite ion size is
included and other corrections are also discussed. However, it should be
noted that the SI equations can be obtained very conveniently by replacing
the dielectric constant term in esu equations by the product of 4-rr and the
permittivity of the medium. The permittivity of a medium is related to the
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permittivity of free space e0 by (4) presented later in the technical note.

The permittivity of free space is given by (Mills et al. 1988)

e0 = - ^ — kg-im-iC 2 « 8.854188 X 10~12 C ^ - ^ - 1 (1)

4irC0
where C0 = speed of light in free space. The numerical constants 4TT are
introduced into the definition of e0 to avoid their appearance in equations
relating to systems with rectangular symmetry. When factors of 4ir are
introduced this way, the equations are described as rationalized.

DERIVATION OF GOUY-CHAPMAN THEORY

The following idealizing assumptions are made in the derivation: (1) Ions
in the diffuse double layer can be considered to be point charges, and there
is no interaction between them; (2) charges on the particle surface are
uniformly distributed; (3) the particle surface is a plate that is large relative
to the thickness of the diffuse double layer (one-dimensional condition);
and (4) the permittivity e of the medium is independent of position.
The concentration of ions of type i, nt, in an electric field is given by the
Boltzmann equation,

/-v,e®\ .„.
n, = ni0 exp [ kT J (2)
where ni0 = concentration of the reference state (ions/m3); v, = ionic
valence; e = unit electronic charge (1.602 x 10~19 C); $ = electrical
potential at the position (V); k = Boltzmann constant (1.381 x 10~ 23 JK _1 );
and T = absolute temperature (K).
The Poisson equation in one dimension relating potential, charge and
distance is given by,

^ * = - P .. .. (3)

where x = distance from the surface (m); p = charge density (C/m 3 ); e =

permittivity of the medium ( C 2 J _ 1 m - 1 or Fm _ 1 ).
The permittivity of the medium e is given by
e = er X e0 (4)
where er = relative permittivity or dielectric constant of the medium (di-
mensionless); e0 is the permittivity of free space (8.854 x 10~12 Fm^ 1 ).
The charge density in the diffuse double layer is contributed by the ions,
so that
P = « E VfHi '. (5)
Substituting (2) into (5) gives
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J. Geotech. Engrg. 1992.118:2000-2005.

 p = e X v,-«;0 exp \—^f-j (6)

Substituting (6) into (3) yields

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— = - - 2 v,«„ exp ( - ^ j (7)

Eq. (7) is the general differential equation for the diffuse double layer
adjacent to a planar surface. Its solution provides a basis for computation
of electrical potential and ion concentrations as a function of distance from
the surface.
For the case of a single cation and anion species of equal valence, that
is, i = 2; v+ = - v_ = v; «0+ = «o~ = "o- Eq. (7) simplifies to the Poisson-
Boltzmann equation

d2$ 2n0ev . , / v e $
— 2-2 = . sinh
^ h (—^—) (8)
dx e V kT
Detailed step by step integration of (8) are presented elsewhere (Hunter
1981, Sposito 1984).
The boundary conditions for the first integration are that for x -» c°;
d<£/dx = 0; and $ = 0, so

^=-^vjsmhy (9)
The boundary conditions for the second integration are that for x = 0, $
= $ 0 , so

= e-"* (10a)
tanh [ —-? '
2kT i
where

" - ^ <™»
For small $ and 4>0, the hyperbolic tangents can be approximated by tanh
x = x. Hence (10a) can be approximated by
$ = $ 0 e- KX (11)
as is the case in the Debye-Hiickel approximation for low surface potentials.
The total diffuse double layer charge can be computed from the potential
function as follows:

a=
-L*dx =
*Li£dx = - 8 (fL 0 (i2)
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 Hence, the total surface charge is determined by the initial slope of the
potential function. Substituting $ = $ 0 into (9), (12) becomes

'=-(£L-* s * TC *- h ($) <13)

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For small surface" potential, the hyperbolic sine can be approximated by

sinh x = x. Hence (13) becomes

a = V&07¥ fe|) = K 'e* 0 (14)

Thus the capacity per unit area of the diffuse double layer is equivalent to
that of a parallel plate condenser with plate distance (1/K). This quantity is
referred to as the thickness of the diffuse double layer or the Debye length.
Since the long range interparticle repulsive forces depend on the amount
of overlapping or interaction between adjacent diffuse double layer, the
thickness of the layer can give an approximate quantitative indication of
the effects of the involved factors on the development of soil fabric and
structure, which in turn exert a significant influence on the properties of
clays.
With the relationship between concentration and potential defined by (2),
that between potential and distance by (10) or (11), and charge and surface
potential related by (13) or (14), the diffuse double layer is completely
described, provided the solution concentration n0, cation valence v, and
either the surface chargeCTor surface potential <]?n is known.

STERN LAYER

As indicated by (13), the surface density cr increases linearly with the

square root of the electrolyte concentration in the solution n0 and hyper-
bolically with the surface potential <J>0- As a result, the Gouy-Chapman
theory may predict very high surface density that is physically impossible
as ions are of finite dimensions determined by the forces of repulsion instead
of the assumed point charges. One of the ways to correct this situation was
proposed by Stern in 1924. The mobile portion of the diffuse double layer
is divided into adsorption and diffusion components separated by a hypo-
thetical boundary known as the Stern surface situated at a distance 8 from
the surface. Stern further considered the possibility of specific adsorption
of ions and assumed that these adsorbed ions were also located in the Stern
surface. This layer of adsorbed ions is known as the Stern layer. The po-
tential at the stern surface is denoted by <J>6.
The population of adsorbed ions in the Stern layer is given by the Lang-
muir adsorption isotherm,

(15)
Ns n
* 1 + K N,„
where ns = number of ions of a given type adsorbed per unit area on the
surfaces of particles (ions/m2); Ns = maximum number of adsorption sites
per unit area on the surfaces of particles (ions/m2); nm = number of ions
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J. Geotech. Engrg. 1992.118:2000-2005.

 per unit volume in the aqueous medium (ions/m3); N,„ = maximum number
of ions per unit volume in the aqueous medium (ions/m3); and K = a
constant (dimensionless)
The dimensionless constant K in (15) can be shown to be a Boltzmann
factor which takes into account both the electrical energy associated with
the ions in the Stern layer veOs, and the specific adsorption energy for the
given type of ion in the chemical system <)>
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= eXP (
I If / ^
Substituting (16) into (15) and rearranging
N,
(17)
ve4>8 + §
1 + I^ I exp
kT
The Stern layer resembles the parallel plate condenser, therefore
$0 - $5 vens
(18)
0 8c

where es = permittivity of the medium in the Stern layer which is consid-

erably less than that of the bulk medium.
Eqs. (2), (10), (11), (13), and (14) are combined to describe the diffuse
double layer outside the Stern surface. The only modifications of the Gouy-
Chapman analysis are that x is measured from 8 rather than from the surface
and $5 is used in lieu of <J>0 as the potential at the inner boundary of the
diffuse double layer. The charges in the diffusion component is thus given
by substituting $ s for <&0 in (14). The lower ion concentration outside the
Stern surface warrants the approximation of ions as point charges. The lower
inner boundary potential $ B improves the accuracy of (11) and (14).
The condition for electrical neutrality of the system is given by

CT = - — — + V8n0kTe sinh \j£f) (19)

Using Eqs. (17), (18), and (19), $ 8 and * 0 or 8 can be solved. Thus the
diffuse double layer is completely described provided all other quantities
are known.

OTHER CORRECTIONS

Four corrections were attempted to improve the Gouy-Chapman theory

by taking into account the dielectric saturation, polarization of the ion,
Coulombic interaction of the ions, and short-range repulsion between the
ions (Bolt 1955). It was concluded that these effects have a tendency to
balance each other. The required corrections are very small for clay particles
of surface-charge densities of less than 2 x 10~7 meq/cm2. Including the
Stern layer, the Gouy-Chapman theory will give fairly reliable results.

CONCLUSIONS

The Stern-Gouy-Chapman diffuse double theory is redeveloped using

fundamental relationships consistent with other disciplines of science and
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J. Geotech. Engrg. 1992.118:2000-2005.

 engineering and the SI system. Ambiguities and redundant conversion fac-
tors are thus eliminated. Theoretical formulations and computations in cou-
pled flows can be proceeded consistently. Researchers of different back-
grounds working on multidisciplinary projects may communicate on a unified
platform.
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APPENDIX. REFERENCES
Acar, Y. B., Hamidon, A., Field, S. D., and Scott, L. (1985). "The effect of organic
fluids on hydraulic conductivity of compacted kaolinite." Hydraulic Barriers in
Soil and Rock, ASTM STP 874, ASTM, Philadelphia, Pa., 171-187.
Alther, G., Evans, J. C , Fang, H.-Y., and Witmer, K. (1985). "Influence of in-
organic permeants upon the permeability of bentonite." Hydraulic Barriers in Soil
and Rock, ASTM STP 874, ASTM, Philadelphia, Pa., 64-73.
Bolt, G. H. (1955). "Analysis of the validity of the Gouy-Chapman theory of the
electric double layer." /. Colloid Sci., 10(2), 206-218.
Chapman, L. (1913). "A contribution to the theory of electrocapillarity." Philo-
sophical Magazine, Ser. 6, 25(148), 475-481.
Gouy, G. (1910). "Sur la constitution de la charge electrique a la surface d'un
electrolyte." Journal de Physique Theorique et Appliquee, Ser. 4, 9, 457-468 (in
French).
Hamed, J., Acar, Y. B., and Gale, R. J. (1991). "Pb(II) removal from kaolinite by
electrokinetics." /. Geotech. Engrg., ASCE, 117(2), 241-271.
Hunter, R. J. (1981). Zeta potential in colloid science. Academic Press, New York,
N.Y.
Mills, I., Cvitas, T., Homann, K., Kallay, N., and Kuchitsu, K. (1988). Quantities,
unit and symbols in physical chemistry. Blackwell Scientific Publications, Oxford,
England.
Mitchell, J. K. (1976). Fundamentals of soil behavior. John Wiley & Sons, New
York, N.Y.
Mitchell, J. K., and Madsen, F. T. (1987). "Chemical effects on clay hydraulic
conductivity." Geotech. Practice for Waste Disposal 1987: Geotech. Special Publ.
13, ASCE, New York, N.Y. 87-116.
Mitchell, J. K., and Yeung, A. T. (1991). "Electro-osmotic flow barriers in com-
pacted clay." Geotechnical Engineering 1990; Transp. Res. Record 1288, Transp.
Res. Board, Washington, D.C., 1-9.
Sposito, G. (1984). The surface chemistry of soils. Oxford University Press, New
York, N.Y.
Sridharan, A., and Jayadeva,M. S. (1982). "Double layer theory and compressibility
of clays." Geotechnique, London, England, 32(2), 133-144.
van Olphen, H. (1977). An introduction to clay colloid chemistry, 2nd ed., John
Wiley & Sons, New York, N.Y.
Verwey, E. J. W., and Overbeek, J. T. (1948). Theory of the stability of lyophobic
colloids. Elsevier, Amsterdam, The Netherlands.
Yeung, A. T. (1990). "Electro-kinetic barrier to contaminant transport through
compacted clay," PhD dissertation, Univ. of California, at Berkeley.

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J. Geotech. Engrg. 1992.118:2000-2005.