168 Colloid ond lnt<Jfoce Scknce

Solving Eq. (5.42), we obtain

(
dlf)' (2/cT) . ( Z;<')
-;!; = l'o 7"' exp -kT +I,
I= constant (5.43)
The COnSiant Of inlegnlliOn (f) Cjln be delennined from !he boundary eondilion: OS X-> \"= 0 and
d vJd.t = 0. Therefore,
r'COm Eqs. (5.43) and (5.44), we obtain
2kT"' -
/:-- uni
a'o i
(5.44)
(5.45)
We= proceed to solve Eq. (5.45) funher for lhc systems in which the elwrolyte is symmetric (i.e.
z : z type, such as NaCI or MgSO.). In that case, we have
(5.46)
Therefore, Eq. (5.45) becomes
(Zr

(5.47)
Solution of F.q. (5.47) with the boundary condition: ' = l"d at .< = d give.< the variation of 'I' with
x. The details of integration are presented in Appendix 58. The solution is
(5.48)
This equation is known as the Gouy-Chupmtm equation which describes the variation of poc:ential
in the diffuse pan of the electrostatic double layer with distance starting from the OHP. A comparison
with the appro.x.imation !Eq. (5.39)] shows that !"varies with x in a more complicaltd
manner. The computation of the potential profile (similar to the variation of potential with distance
shown in Figun: 5.8) is left as an cxcr<:isc for the reader. If the potential at the OHP (i.e. '1'
4
) is large
then. tanh I. When the potential is small, i1 can be shown easily that the Debye-HUckel
4kT
approximation given by Eq. (5.39) is ob1ained (see Problem 5.11). AI a distance far away from the
inlerface whue 1he polential (I') is low, The po1ential in that ease can be
c-alculated from the equation
If= (
4
*T)tanh(Z<I(I d )exp[ -K(X -d)]
u 4kT
(5.49)
Jntcrmol.ulor and Surfar:e ForCe$ 169
The Grahame Equation
The Grahamc equation gives the relationship between the interfacial charge density and the
potential at the interface. The charge dcnshy dcpem.ls on the numbe.r of charged group.." on the
imcrfacc. We will dcri\'C thts relationship the Gouy-Chapman model. At the charged interface.
the O\'erall electroneutrality condition be satisfied. The total charge in a volume clement of the
solution of unit of the diffuse layer from the OHP (i.e. x =: d) to x = oo mus-t equal the
charge of opposite nature that the unit area of the interface contains. Jr ad is t.his churgc density (in
C/m
1
). lhen
where Zl" is the potential gradient at x = d. The potential gradient is zero as x oo, From
Eq. (58.3) in Appendix 58, we get
dl" = (2kfn- )
112
[p(-Z<\"4 )-exp( Zel/'4 ) ]
tit
4
cc
0
2kT 2kT
(5.51)
From Eqs. (5.50) and (5.51), we gel
u
4
= -cc
0
dl"l = (2kTr.c
0
n"J' " [exp(Zf\11 )-exp(-

) ]
dr d 2kT 2kT
(5.52)
Equation (5.52) can be: wriucn in renns of hyperbolic sine function
ad = (8kT
0
n-)
1
/ 'l sinh ( U\1'" )
2kT
(5.53)
Equation (5.53) is kn0\\'11 as Grahame cquotion. Jn lcmt."i of the concentration (,_... (in mul/m:J),
Eq. (5.53) can be wriuen a<
u, =

<inb(
where R = kNA is the gas constant
(5.54)
BXA.MI'LH S.l2 lf the ch;.rge density of surf;.c:c- iJ' ....0. 1 Clm
1
, cnlc:ulale the sur13ee rutenti ::.l at
298 K in I moVm
3
and I 0 moVm
3
aqueous NaCI solutions using the Grahame equation.
Solution Rearranging Eq. (5.54), the surface potential can be calculaced from lhe oqualion,
Therefore.
1kT = 2xl.381xi0-
21
x298 = 0.0
514
v
e 1.602 X 10-
19
I
!J
J
''
*
-I
L.
170 Colloid cr.nd Scienct
For c .. = I moVml:
" 0.1 0.1
=- --
(8RTeeoc-)11' (8x8.314x298x78.5x8.8S4x!O-a xtJ'" 3.712 x 10
3
- 26.94
sinh" ' [ a,

(8RToc-)
Thcn:fore. \'{( X 3.987 -{1.2049 Y = - 204.9 mY
For c"" = I 0 moVm
3
:
" - - 0.1 =- 0.1 =-8.55
(8RT&eoc")l/> - (8x8.314x298x78.5x8.854xlO"" xtOJ'" 0.0117
sinh'[ a,

(8RT&eoc")
Therefore, V'd = - 0.0514 x 2.84 = -0.1460 Y = -146 mY
The results from Example 5.12 iUustrate how lhe po<ential of a charged surface can be reduced
by the increase in concentration of the electrolyte in the bulk solution. The effects of divalent aDd
J
trivalent ions ore stronger .wbich can be anticipated from Eq. (5.54). The surface charge density is
reduced very effectively by the binding of counterions on lite surface groups. This reduces lhe 1
surface potential strongly. Wbeo a surface contains sites where both anions and cations c.an bind (i.e.
amphoteric surfaces such as the protein surfaces). the charge density can be negathe or positive
depending on the type of electrolyleS in the solution and their concen1111tion. The condition where
lhe mean surface charge density is zero is known as the isoelectric point. Sometimes counterion

binding leads to the reversal of charge of the surface. Binding o countcrions has important
consequences in the adsorption of ionic surfactants at air-water or water-hydrocarbon interfaces
(Kalirtin and Radke, 1996). Countuionbinding is also imponant in mice11isation. Ulus!r.ltivo promes
of concentrations or coions and countcrions near a charged surface are shown in Figure 5.9. The
0
X
Agurt s.t The prollles ollhe colons and the -ns near a <Nf90d sutfal:e.
lnttrrnolecular and Surfocr: Foret$ 171
concentration of the countcrions is high ncar the surface whereas the concentration of the coions is
less. as expected. These profiles show how the concentrations of the ions reach their bulk values.
A comparison of the prediction by Grabame equation with experimental data is shown in
Figure 5.10 for lite surface potential of egg leeithindicetyl phosphate in aqueous NaCl solution at
295 K The mean molecular area of the lipid was taken to be 0.72 nm
2
to estimate the surface charge
density.
- n, (Cim')
0 0.005 O.OOt O.Ot5 0.02 0.025 0.03
0
0
-20
>
0
. -40
0
l>

o NaCI 100 movm,
0
0 NaCI10
- Prediction from Gral\ame equation

0 2 4 6 8 10 12
Dicetyl Phosphate (mol %)
flgu10 5.10 of Grahams equation. Variation of SIJiface poeontial ol ogg leci11tirHicetyl
phosplla!e liposomos 1\th ltle of dice1yl phosphate 8l two c:onc:oroalions of NACI
(F.-z, 1961) (ac!apCed by pem;$$1on from ElseY!er Ltd., II) t!lat).
EXAMPLE 5.13 Consider an aqueous solution of NaCI of I mollm
3
concentration. The surface
potential is 300 m V 31ld the temperatwe is 298 K. Calculate the concentration of counterions ncar
the surface assuming lhe absence of lhc Slem layer. Explo.in your result.
Solulion From Eq. (5.26). we have
- (<"') [t.602xto 9xo.3] 18 10' v '
,:.:c exp -- -= l xexp
13
;::J. x mom
kT t.38lxto x298
Since the ions have finite dimensions, the concentration at lhe surface found by the above caJculation
is too high! Such a IUgh was or the uswnption that lhc ions point charge
and they can approach the surface without any limit. furthennore. Lhe value of surface potential 1;t1
can be several hundreds of millivolts but the value of 'd is much lower than this value as a
consequence of the Stern layer.
5.3.3 The Stem Layer
lbis part of the elecuostatic double layer is concerned with tbe layer of adsorbed ions ori the surface
(Stem, 1924). It is known as lite compact part of tlu! double layer. The Oouy-Chapman
predicts lltat the ions can approach the surface without lintit The result of Example 5.13 shows tlutt
this theory becomes inadequate when a considerable pan of the space charge should be present very
I
"
l
''
*
172 Cotloid and Jnterfo &it nee
close (e.g. O.S nm) to the interface. Stem did not distinguish between the inner :1Jld outer Helmholtz
pl3llcs, but he mentioned the possibility thai such a distinction mi&Jtt be necessary. Let the the
number of odso<hcd ions per unit area of the surface. t;, be the number of ions per unit >'Oiume of
solution. p be the nwtimum number ions thai can be on unit :uu of the surface. and Po be the
maximum number of ions for wbich then: is space in the unit volume of solution. If the cowse of
a single ion is followed for some time. it will be found for fr:tetion of time 8 at the surface and
(or a fmcdon of time lht solution. tf no wodc were required 10 move 11n ion from 1M interior
of the solution to place 01 the inner Helmholtt plane. would he the ratio of the number of free
places on tbe surfilCC to those in the solution. i.e.
8 P-r
-=
0., Po - 'o
(5.55)
If we cons.ider not one ion but all the ions. it is evident that
8 r
-=-
0., '
(5.56)
If the amount or work needed to move an ion from the interior of the solution to a free place at the
surfi!Ce is not zero but nn amount equal to II>. then the right side or Eq. (5.55) needs to be
by the Boll%mann (actor. Therc!oce. we have
r P-r (
to= Po-to cxp- kT
(5.57)
E.'ccpc in very conccntntted solutioos. To << ft. With this simplifoeation. Eq. (5.57) bc:comes
te P-r
Po/t
0
kT
(5.58)
Equation (5.58) con be solved for t to obtain
(5.59)
Experimental evidence suggesos that <Po I r
0
)exp(;) :>:>I (Grohame. 1947). Therefore. Eq. (5.59)
simplifies to
(5.60)
where r..,. is the radius of the non-solwted ion. The worlc II> is composed of the electrical potential
at the inner Hclmholt plane and the adsorption potential of the ions. Stem considered the possibility
of simultaneous adsorption of both cations and anions. Howe\'er. there is hardly any general
cperimcntallyunambiguous procedure Cor dividing up II> in this manner [see Hunter (2005)).
lntt'rmolecular and Surface Fort'eS 173
The potentials at the inner and outer Helmholtz pl!lnr.s can be \\'Iitten in tenns of the charge
density hosed on Eq. (5.50). The tOOll thickncs.s of the compoct lay<r is. d = dt + d
1

The pol<ntial drop in the IHP is
(5.61)
and the potential drop in the OHP is
(5.(>2)
where c; nnd arc the average values of the diclec1ric constanl in the rcspectjve regions. Therefore,
the potential changes linearly wilh diswnce us shown in Pi gun: 5.6. The charge balance requires that
C1o +a, + O'J a 0 (5.63)
A comrtcte solution of potential distribution in the: double layer can the valui;!S of 'KI \1'
1
'I'd
u
1
und In a simpler situation where u
1
= 0. we have
(1Jt/
l'lo - li'J -:--- (5.6-1)
t.o
wbne ,. is the average dielectric consta.nl or the medium in the compacr region. lllcn:fon:. we howe
four unknowns: 114> "'"' G\, and O',r and three equation< lllqs. (5.54). (5.63) nnd (5.64)]. Another
equotion can he derived rom the imposed c"cmal c.m.f. (Hunter. 2005).
l"o s 69'-d.l- (5.65)
where ll9 is the: Galvani potential difference bel ween the: surface: and he: of the solution. :md
b.fdipolc is the potential difference due 10 the oricnlation or the polar molecules at the surface.
The Stem lheory may be considered U$ an improvement over the Gouy-Ot.apman theory. It
distinguishe. between the total double layer potential (I'll) and the potential at the OHP ( yr,). The
experimental daltl show dut r.vcan be of the order of se\crnl hundreds of millivolts where the Gouy-
Chapman theory will be inapplicable. Howc\cr. the \'Aiuc of IJI.J rarely exceeds 100-150 mV. which
has been >crified experimentally (Verwey and Ovctteck. 1948).
It hn!t been suggested th:1t the adsutbed ions in the Stem layer cnn impart repulsion two
llJ)pmaching surfaces. This provides stability to lhc colloids at high concentration of salt As the
thid:nCl.fi of the Stem layer increMeS (by 1he or the adsorbed ions on the surface).
two appi'Oo'LChing surfaces repel each other at a rather l:ttJe scp:u01tion. The between 1hc
two PP"""'hing surfaces can be as large as 2 nm (Ciaesson ct ol 1984). The stability of some
colloidal at high salt concentrations. 5'-"tllin: anti repepcisation c:tn be explained b)' the
Stem lyer stabilisotioo (Freas and Overbeck. 19n).
5.3.4 Double layer around Spherical Particles
The clcctrostotic double l3yer aroond spherical poniclcs has o gre:n impoltllnce in the subility of
colloidaJ panicles. In this section. we will dcrhc the expression of potential distribution with the
Dcbye-HOckel approximation (i.e. low potcotia.l). The difftrenti:ll equation go\ocmiog the vuiation
of tv with r is c;ivcn by
I J ( ' J) ,
-- r -Z. A-f/1
r
1
tlr tlr
(5.66)