The initial mission of researchers to develop a general model or

theory of adsorption that would reproduce with precision

 (i) Shape of the adsorption isotherm

 (ii) Surface area of the solid

 (iii) Effect of temperature on adsorption

Classification of Ion Exchange Equations
Most of the equations which are important in soil chemistry

 i. Double Layer theory: Gouy-Chapman theory and Stern

Layer theory.

 ii. Donnon Equilibria.

 iii. Statistical Thermodynamics: Davis Equation

 iv. Based on Mass Action: Gapon Equation, Vanselow

Equation, Kerr Equation.

 v. Kinetic Approach: Freundlich and Langmuir Equations

 Diffuse Double Layer or Double Layer Theory
Commonly it is referred as Gouy-Chapman theory
(Gouy, 1910; Chapman, 1913)
Assumptions
 Ions interact electro-statistically like charged particles of zero size but in reality
ions and their associated water molecules have appreciable physical size.
 Exchangeable cations exist as point charges but in fact ions have definite size.

 Colloidal surfaces are planner and essentially infinite in extent.

 Surface charge is distributed uniformly over the entire surface of a colloid.

Correct to the extent of permanent charge but invalid for variable charge which
concentrates on edges.
The structure of the DDL is determined by the

 Surface charge density

 Kind of counter ions

 Temperature

 Concentration of electrolytes in soil solution

The exchangeable ions are surrounded by water molecules and

may thus be considered forming a solution − the micellar
solution or inner solution. Bulk solution, beyond the thickness
of DDL, is known as outer or inter-micellar solution.
DDL theory

 The concentration of counter ions is the highest in the

immediate vicinity of a surface and decreases at first rapidly
and then asymptotically to the inter-micellar solution of
uniform ionic concentration.

 The potential at the surface is ψ0 which decreases with

distance from the surface.
Boltzman equation
 ni = nio exp (˗zi e ψx / kT)----------------- (8.1)

 n+ = n+o exp (˗ z+ e ψx / kT) for cations ----- (8.2)

 n- = n-o exp (˗ z- e ψx / kT) for anions ------( 8.3)

ni is Conc. of ion 'i' at point x as ions cm-3, T is Absolute

temperature, nio is Conc. of ion i in the bulk solution as ions cm-3,
e = Electron charge, x is Distance from the charged surface, is exp
= 2.7183 and is constant, zi is Valency of ion ‘i’, ψx is Electric
potential at distance x, and k is Boltzman (1884) constant = R/NA
, i.e. 8.31 j mol-1 Kalvin-1/6.023 × 1023 = 1.3799 × 10-23 j K-1.
 No specificity of the adsorbed or repulsed ions is assumed

 The distribution of ions in the DDL is a function of the ratio of

electrostatic potential energy and thermal energy

i.e. zieψx / kT. This ratio is dimensionless.

 The charge density 'p' at any point in the DDL is the difference
between the concentration of positive and negative charge at
point in question:

 p = izieni or p = +z+en+ or p = - z-en- -------------- (8.4)

 The relation between the local charge density (p) and the electrical
potential (ψ) is given by the Poisson equation:
d2ψ / dX2 = 4πp /D ----------------- (8.5)
D is Dielectric constant,
x is = Distance from the surface,
d2ψ / dX2 = Variation in the field strength (˗ dψ / dX) with distance
from the surface.
This treatment assumes an infinite flat surface and that charge varies
only in the direction normal to the surface.
 Substituting values of ni from the Boltzman equation into equation
8.4, and substituting the product in the Poisson equation 8.5 gives:
(˗zi e ψx )
p = izi e nio exp ------------- --------- (8.6)
kT
d2ψ [4π ∑i zi e nio exp(˗ zi e ψx / kT) ] [4π] [∑izienioexp (˗ zieψx)]
--- = ---------------------------- = ------ × --------------------(8.7)
dX2 D D (kT)
 For simplicity, assume that the suspension contains a single
symmetrical electrolyte, i.e. z+ = z-, accordingly in the bulk
solution it could be assumed n+o = n-o = nio.

d2ψ 4π zi e nio exp (˗ zi e ψx) exp (zi e ψx)

----- = ------------- × ------------------ − ----------------- --(8.9),
dX2 D kT kT
 zi is the absolute valence of either ion. If y = zi e ψx / kT,
equation 8.9 reduces to

d2ψ / dX2 = 4π zi e nio / D[exp(˗ y) ˗ exp(y) ------------- (8.10)

 By definition, the hyperbolic sin of 'y' is:

sinhy = [exp (y) ˗ exp (˗ y)] / 2 or 2sinhy = [exp (y) ˗ exp (˗ y)] ---- (8.11)

 Hence equation 8.10 4.22 becomes:

d2 ψ/ [8π zi e nio] [8π zi e nio] (zi e ψx)

------- = ------------ × sinhy = ---------------- sinh ------------ ------ (8.12)
d X2 D D kT

 This equation 8.12 is the fundamental differential equation of

the DDL theory.
 For small surface potentials, ψo< 25 mV or zie ψ0 / kT < 1.0.
The solution of equation 8.12 is:

 ψx = ψoexp (˗ Kx) or lnψx /ψo = ˗ KX ------------- (8.13), where

 ψx is electrical potential at distance 'X' from the surface which

has a total potential of ψo and

 K = [8πzi2 e2nio / DkT]1/2 cm-1 -------------- (8.14)

 The dielectric constant 'D' is also called relative permittivity .

 The ratio of the capacitance of a capacitor with a specified medium

(dielectric) between the plates to the capacitance of the same
capacitor with free space between the plates, i.e. ϵr = ϵ / ϵ0 or
D=Ds/D0.

 The equation 8.13 shows the decay or decrease in potential with

distance from the surface to be exponential and dependant on the
parameter K.
 A unique feature of the 'K' is that it has the dimensions of
reciprocal length, cm-1, i.e.
K = 1/cm or cm = 1/K ------------------ (8.15)

 Equation 8.13 indicates that when distance 'X' equals to 1/K, the
potential Ψx has dropped to a fraction 1/e of the value Ψ0 at the
surface, i.e. If X = 1/K, then KX = 1 and Ψx = 1/2.73 × Ψ0 = 0.37
× Ψ0.

 The distance 1/K coincides closely with the center of gravity of

the space charge of the DDL, i.e. as many counter ions are on one
side of a hypothetical plane at distance 1/K from the surface as
are on the other side.
 For this reason, 1/K is taken as the effective thickness of the
DDL. A graphic presentation of Ψ= Ψ0 exp (˗ KX) is given
assuming Ψ0 = 10 mV (Fig. 8.1).
12

Effective thickness,
8

X=1/K,
, mv

 = 0.37 0
4 00

00 0.5 1.0 1.5 2.0 2.5 3.0

Relative distance, KX
Fig. 8.1. Schematic diagram of Ψ= Ψ0 exp (˗
KX) is given assuming Ψ0 = 10 mV .
Factors Affecting DDL Thickness

 Major factors include

 (i) Electrolyte concentration

 (ii) Surface charge density

 (iii) Valence of counter ions

 (iv) Temperature.

 Effect of the first two factors (i and ii) on the DDL thickness in
aqueous solution at room temperature is combined equation
8.16: K = 3 × 107z(c)1/2 ---------------------- (8.16)
  where K is reciprocal of DDL thickness, ‘z’ is the valency of
counter ion and ‘c’ is electrolyte concentration in the bulk
solution as mol L-1. The DDL thickness is thus:
1/K = 3 × 10-7 / z (c)1/2 cm -------------------- (8.17)

Table 8.2. Concentration and valence effect on the 1/K of DDL for surface with small Ψ0
values
Conc. (mol L-1) 1/K for monovalent 1/K for divalent
10-5 10-5 = 100 nm 0.5 × 10-5 = 50 nm
10-3 10-6 = 10 nm 0.5 × 10-6 = 5 nm
10-1 10-7 = 1 nm 0.5 × 10-7 = 0.5 nm
 Ψ0
100
80
, mv
60

c=10-5 (mol L-1), 1/K=100nm

40

c=10-3 (mol L-1), 1/K=10nm

20

c=10-1 (mol L-1), 1/K=1nm

0

00 50 100 150 200 250 300 350

Distance from charged surface (x), nm

Fig. 8.2. Effect of monovalent electrolyte concentration,

NaCl, on DDL (Schematic diagram).
 The effect of increased salt concentration (salinity) arises
from reduced cation diffusion from the surface towards the
bulk solution and increased anion diffusion in the opposite
direction.

 Excess of cations near the colloid surface (due to attraction

by the –vely charged surface) and the corresponding deficit
of anions (due to repulsion by the surface –ve charge)
 Ψ0
100
40 60 80
, mv

z=1
2
z=1
20

3
z=1
0

00 50 100 150 200 250 300 350

Distance
Distance from
from charged
charged surface
surface (x), nm
(x, nm)
Fig.Effect
8.3. Effect of monovalent
of valence of electrolyteselectrolyte
on the DDLconcentration,
(Schematic
NaCl, on the DDL (Schematic diagram)diagram).
Ion Distribution in DDL
 Both positive and negative adsorption occurs at the
liquidsolid interface.
 For any given situation, the distribution of cations and anions
can be described by equations 8.2 and 8.3.
 The total charge density (equation 8.2) of the DDL is the sum
of a+ and a- (also see equation 8.4).
 with an increase in salinity of soil solution, there will be a
decreases in the apparent CEC.
 Correspondingly, the CEC increases on dilution and
approaches the amount of isomorphic substitution as an upper
limit.
 Dilution increases CEC due to ion pairing like CaCO3,
CaCO3+, CaCO3- negative charge contribution to CEC.

 Dilution Increases pH which ultimately increases CEC.

 It can be noted (Fig. 8.4) that the negative adsorption of an ion
is limited to zero concentration whereas positive adsorption of
counter ions has less constraints.

n+ = n+oexp (˗ z+eψx / kT) ---- 8.2(4.15)

A+
n-=n-oexp(˗z-eψx / kT) ----- 8.3(4.16)
Cations
(4.16)
p=∑izieni or p=∑+z+e n+=∑-z-en----- 8.4(4.17)

n+ = n+o exp (˗ z+ e ψx / kT) ---- (4.15)

Conc. of ion ni

n0 Bulk Soln
n+ = nn++oo exp
= exp(˗(˗z+z+e eψn+xψ=/xnkT)
-/ kT)
--------
Anions (4.15)
a- Distance from surface

Fig. 8.4. Cation and anion distribution in the DDL and bulk soil
solution (Schematic diagram).
 The DDL theory predicts that a certain volume of water close
to the surface of a clay mineral is not available to anions.

 Thus an increase in relative concentration of anions in the

solution external of the DDL is natural.

 This explains why anion concentration (e.g. Cl) in soil extract

is often higher than the calculated amount.

 This is particularly true if soils are extracted at water levels

below field capacity.
 A formula derived from the DDL theory which can be used to
estimate the number of cations per unit volume at a distance ‘x’
from the surface is:

n+ = no[cot h × X × K/2]2 = no[cot h × X/2[8π e2 z2 no / DKT]1/2 ---- (8.18)

 where cot h is hyperbolic cotangent and is equal to
ex + e-x
cot h = ---------- (8.19), where ‘e’ is a constant and has value of 2.7183.
ex - e-x
0.001[cot h (0.16 × 1× 0.0316 × 50]2 = 0.001[cot h(0.2528)2]
2.71830.2528 + 2.7183-0.2528 1.2876 + 0.7766
n+ = 0.001[ ---------------------------------- ]2 = 0.001 [ ---------------------]2
2.71830.2528 ˗ 2.7183-0.2528 1.2876 ˗ 0.7766
2.0642
n+ = 0.001 [----------]2 = 0.001 (4.0395)2 = 0.0163178 = 0.16
0.5110
 And at room temperature
 n+ = no [0.16 × X × z (no)1/2]2 ----------------------------- (8.20)

 where n+ is concentration of cations at a distance 'x' as Å from

a negatively charged surface.

 no is concentration of ions in the bulk solution.

 z is valence of the cation.

The Stern Modification of the DDL Model

 Stern (1924) introduced two major corrections to the

Gouy−Chapman model.
 (i) Finite dimensions of counter ions in the region adjacent
to the charged surface were corrected.
 (ii) Possibility of the specific adsorption of counter ions by
the surface was included.
 According to Stern, the counter ions can be considered as
divided between diffuse layer of point charges and an immobile
surface layer of some thickness, which can contain a certain
maximum number of counter ions cm-2 of the interface.
 The layer of adsorbed counter ions immediately adjacent to the
surface is referred as the Stern layer.

 The Langmuir type adsorption equilibrium is assumed to exist

between the ions in solution and those in the Stern layer.

 Stern described this region as a ‘molecular condenser’ formed

between the surface charge and the charge in the plane of the
center of the closest counter ions (Fig. 8.5).
 Stern layer
ΨZ
Ψ Stern potential
Electrical Potential

Plane of shear
Diffuse or Gouy-Chapman
layer
Only the specifically
adsorbed ions and not
potential determining
ions

Distance from charged surface ‘x’

Fig. 8.5. Schematic diagram of the plane of shear and zeta potential.
 The surface potential drops linearly with distance across the
Stern layer.

 When distance from surface ‘x’ is equal to the thickness of the

DDL, then Ψ0 has dropped to some potential ‘Ψ’ and is called
as the Stern potential.

 The Stern layer thickness ‘’ is in the order of 5 × 10-8 cm.

 Total charge of counter ions is divided between the stern layer

and the diffuse layer, i.e.
a+ = a1 + a2 (assuming a negatively charged surface)---(8.22),
 where ‘a1’ is charge of counter ion in the Stern layer and a2 is
the charge of counter ion in the DDL.

 At small electrical potential of the colloid surface, the DDL

outside the Stern layer is treated in the same way as the DDL of
Gouy−Chapman except Ψ is substituted for Ψ0, i.e.

Ψx = Ψ exp {˗ K (x ˗)}------------------------- (8.23)

 It can be seen that when

x- = 1/K, then ΨDL = 0.37  ------------------- (8.24)

 The greater the energy of adsorption (specificity) for a given
ion in the Stern layer, greater is the drop in potential across the
layer and thus smaller the value of Ψ.

 Increasing concentration of electrolytes in bulk solution

decreases the thickness of DL and forces the counter ions into
the Stern layer but within limits, thus decreasing the value of
Ψ.

 The Stern modification of the DDL theory has generally proved

satisfactory in explaining experimental data.
Electro-kinetic Phenomenon or Zeta Potential
(Ψz)

 It may be defined as the relative motion of a charged particle

with respect to the bulk solution.

 Although the ion atmosphere of the DDL is bound to the

charged surface by electric forces which prevent its escape into
bulk solution, a portion of DDL is within the free solvent and
hence not held with great tenacity.

 Indeed, a certain portion of the DDL can be made to move

along the surface if an appropriate force is applied.
 An outside electric force applied to a colloid system can cause a
separation of the DDL with a certain amount of solvent and
counter ions fixed to the charge surface and the remaining portion
of the DDL moving as free solvent (water).

 The plane of separation of the DDL into its ‘bound’ and ‘free’
components is called the plane of shear (Fig. 8.5). The electric
surface potential which exists in the DDL at the plane of shear is
called the Ψz.

 Ψz is the potential difference between the dispersion medium and

the stationary layer of fluid attached to the dispersed particle.
 The distance of the plane of shear from the colloid surface is
indeterminate and may or may be associated with the Stern
layer.

 Although Ψz < Ψ, it is generally considered that Ψz is a

reasonable estimate of Ψ.

 The zeta potential is not a phase boundary potential, it is

developed totally within the liquid region.
 Factors Affecting Zeta Potential

 Assume a particle in suspension with a negative zeta potential,

then following changes could occur:

 If more alkali is added to this suspension, particles tend to

acquire more negative charge.

 If an acid is added to this suspension, point will reach where

the charge will be neutralized. Further addition of acid will
cause a build up of positive charge.
 In general, a zeta potential versus pH curve will be positive at
low pH and lower or negative at high pH.

 There may be a point where the curve passes through zero zeta
potential which is called the isoelectric point (Fig. 8.6).

 It is normally the point where the colloidal system is least

stable.
 40 60
Stable
Zeta Potential
-60 -40 -20 00 20

Isoelectric point Stable

2 4 6 8 10 12
pH
Fig. 8.6. Schematic diagram showing isoelectric point and
stability of colloidal system.
 Significance of Zeta Potential

 The significance of Ψz is that its value can be related to the stability of

colloidal dispersions.

 It indicates the degree of repulsion between adjacent similarly charged

particles, i.e. degree of dispersion.

 For molecules and particles that are small enough, a high Ψz will
confer stability, i.e. the solution or dispersion will resist aggregation.

 When the potential is low, attraction exceeds repulsion and the

dispersion will break and flocculate.
 Colloids with high Ψz (negative or positive) are electrically
stabilized while colloids with low zeta potentials tend to
coagulate or flocculate.

 The magnitude of the Ψz gives an indication of the potential

stability of the colloidal system.

 A dividing line between stable and unstable aqueous

dispersions is generally taken at either +30 or -30 mV.

 Particles with Ψz > +30 mV are normally considered stable

and those with > -30 mV are normally considered stable
Table 8.2. Relationship between Ψz and stability of colloids

Zeta potential [mV] Stability of soil colloids

from 0 to ±5 Rapid flocculation
from ±10 to ±30 Incipient instability
from ±30 to ±40 Moderate stability
from ±40 to ±60 Good stability
more than ±61 Excellent stability
 The Ψz is widely used for quantification of the magnitude of
the electrical charge at the DDL.

 Zeta potential is not equal to the Stern potential or electric

surface potential in the double layer (Kirby, 2010).

 Zeta potential is often the only available path for

characterization of DDL properties.

 The Ψz should not be confused with electrode potential or

electrochemical potential because electrochemical reactions are
generally not involved in the development of Ψz.
 The most important factor that affects Ψz is pH.

 A Ψz versus pH curve will be positive at low pH and lower or

negative at high pH.

 There may be a point where the curve passes through zero Ψz.

 This point is called the iso-electric point (Fig. 8.6) and is very
important from a practical consideration.

 It is normally the point where the colloidal system is least

stable
Determination of Zeta Potential (Ψz)

 The Ψz is not measurable directly .

 It can be calculated using theoretical models and an
experimentally determined electrophoretic mobility or dynamic
electrophoretic mobility.
 i. Electrophoresis
 Consists of setting up a potential gradient in a suspension of
charged particles .
 Determining their velocity of motion across the potential
gradient as viewed through calibrated microscope lens.
 . The determination of particle velocity in an electric field is
called electrophoresis (Fig. 8.7)

Microscope with
calibrated lense
Clay suspension

Anode + -
Cathode
Clay suspension Clay particle
movement
Fig. 8.7. Sketch of electro-phonetic cell for the determination of zeta
potential.
 The relation between electrophoretic velocity (W) and Ψz is:

W = DΨzV / 4 ηπ ------------------- (8.25)

D is Dielectric constant.
 V is Field strength gradient, i.e. voltage applied.

 η is Viscosity.

 W is Electrophoretic velocity.

 Dielectric constant (D) is the ratio of the capacitance of a capacitor

with a specific medium (Ds) between the plates to the same capacitance
of the same capacitor with free space (D0) between the plates, i.e. ϵr =
ϵ / ϵ0 or D = (Ds)/ (D0).
 It is also known as relative permitivity.
 ii. Electro-osmosis:
 When applied potential is placed across the capillary plug
(porous), the counter ions in the DDL move toward the
appropriate electrode.
 Since the ions move along solvent, a flow is created (Fig.
8.8)

Porous plug (Clay) Clay suspension

Cathode  + Anode

Water movement
Fig. 8.8. Apparatus for electro-osmosis for the determination of zeta
 When a field is established, electro-osmotic flow will occur
toward cathode (in the above example, the solid is negatively
charged).

 As a hydrostatic head develops in the stand pipe, counter flow

sets in and a steady-state electro-osmotic pressure is reached
such that the counter flow balances the electro-osmotic flow.

 Then steady - state pressure (P) is:

P = 2 Ψz DV / π R2 ----------------------- (8.26)
 Where
 P is Counter flow pressure,
 Ψz is Zeta potential.
 D is Dielectric constant.
 V is Total applied voltage.
 π = 22/7, and R2 is Radius of capillaries in the porous plug.

 At 250 C, when potentials are in volts and R is in cm.

P = 4.2 × 10-8 V Ψz / R2 as cm of mercury -------- (8.27)

 The process involves deriving a solid anode and a perforated
cathode in the ground at a given distance apart.
 When voltage is applied, water collects inside the cathode and
is pumped out.
iii. Streaming Potential:

 It is the reverse of electro-osmosis.

 The streaming potential, Vs, is the voltage difference

developed between the ends of a capillary tube or porous
plug through which liquid is forced to flow by an applied
pressure difference, P (Fig. 8.9)
Applied pressure (P)
Cathode 
Porous plug (Clay)

Potential meter
Fig. 8.9. Apparatus streaming potential to determine zeta
potential.
 An electric potential difference in the direction of flow is
established.

 A reverse flow of electricity (i.e. counter flow of counter ions)

through the liquid will occur.

 At steady - state, the charge transported by the displaced DDL

per unit time will be balanced by the current conducted through
the liquid.

 The general equation is:

Vs = P ψz D / 4 π ηλ --------------- (8.28)
  Vs is Streaming potential,
 P is Counter flow pressure.
 ψz is Zeta potential.
 η is Viscosity.
 D is Dielectric constant.
 λ is Specific conductance as ohm-1 cm-1 = mho cm-1.

 In water at 250 C, the Vs is:

Vs = 10-5 P ψz / λ ------------------ (8.29)
 The electrokinetic data have shown that increasing the salt
concentration in the bulk solution decreases the values of ψz
because of the shift of the ions toward the Stern layer
iv. Laser Doppler Velocimetry:
 Laser beams are aligned at the stationary layer in the cell.

 At the crossing point of beams, Young's interference fringes of

known spacing are formed.

 Particles moving through these fringes under the influence of the

applied electric field scatter light whose intensity fluctuates with a
frequency that is related to the particles velocity.
 Photons detected are input to a digital correlator and a
frequency spectrum is produced from which the mobility and
hence zeta potential are calculated.

 However, particles with no charge will not move in an applied

electric field and thus these could not be detected.

 This problem is overcome by making the interference fringes to

move which is done by using a device called as modulator.
Forces in the DDL and Suspension Stability

Repulsive Forces
 When two like-charged particles approach each other in a
suspension, their DDL (ion atmosphere) overlap (Fig.
8.10a).
 The two DDLs, bearing the same sign, can not develop fully
when they overlap.
 Hence the potential drop between the two surfaces can not
be as large as between the surfaces and the solution where
ψx = 0 (Fig. 8.10b).
 Interaction between the two DDLs of the two particles of
the same sign of charge is the source of repulsion
 The repulsive potential energy (VR) between the opposite
square centimeters of parallel plates from the interaction of

VR = 2(Gd ˗ G%) ----------------- (8.30)

their DDLs is:

 Where

 VR is Repulsive potential energy,

 Gd is Gibbs free energy of the DDL cm-2 when plate

distance is 2d.
 a. Interacting particles b. Non interacting particles

0 0 0

,
mv
mv

0 d 2d 0 1/K 2/K
Distance from surface Distance from surface
Fig 8.10. Schematic diagram of repulsive potential energy (VR) according to Verwey
and Overbeek (1948 ).
The Free Energy of Repulsion (VR)
 The VR is the amount of work that has to be performed to
bring two particles from infinity to some distance, 2d, apart.
 The solution for Gd and G% for the DDL at constant
potential is estimated by Verwey and Overbeek (1948) and
their calculations show:
VR = {64 n kT / K}{y2 exp (˗ 2 K d) --------------------- (8.31)
 where d is distance midway between the plates, n is ion
concentration in the bulk solution, and K is Boltzman constant.
k = (8 π z2 e2 n)1/2 / DKT ------------------------------------ (8.32)

y = [{e(z e ψ0 / 2 KT)} ˗ 1] / [{e(z e ψ0 / 2 KT)} + 1)] ------------- (8.33)

 The equation 8.31 shows that the repulsion potential decays
exponentially with distance (d) and is essentially independent
of the surface potential (ψ0) but strongly dependent on K.

 The VR is an exponential function with a Range in order of the

thickness of the DDL.

 Its value remains finite for all the distances of plate separation.

 The more compressed the DDL, closer the particles can

approach each other before the VR becomes operative.
 The effect of electrolyte concentration on VR is shown below in
Fig. 8.11.

Ψ0
VR

Low concentration

Medium concentration
High concentration

00 50 100 150 200 250 300

Distance from charged surface (d), nm
Fig. 8.11. Schematic diagram showing effect of
electrolyte concentration on V R.
Attractive Forces
 This attraction is the most suitable and of a very general kind
and is called London − Van der Waals forces (London, 1932).
 These forces are universally attractive one acting between all
the atoms, molecules and ions. London (1932) originally
explained these forces on the basis of quantum-wave
mechanics.
 At any given instant, the charge (electrons) distribution will be
distorted (i.e. more electrons on one side than those on the
other side of a molecule) producing an instantaneous
fluctuating dipole (Fig. 8.12).
 This temporary dipole nature induces a resonant dipole in an
adjacent second atom resulting in attraction. The fluctuating field
has a frequency of 1015 − 1016 per second.

 When considering the interaction of solid particles, all of the

attractive potential for all the atomic pairs belonging to the
surfaces of the two interacting particles are summed.

 By this method, an expression for the attractive potential (VA) is

derived, i.e.

VA = − A / 48 π d2 --------------------- (8.34)
 A = π2 q2 β, and q = No. of atoms cm-2 of a substance and β is a
system parameter.

a. Hydrogen b. Water
H

+ H ˗ ˗ O 105 o
+
-
e
-
H
Fig. 8.12. Electron distribution in dipole.
Total Particle Interaction
 The net potential energy curve for plate like particle
interaction is determined by adding the contribution of VA
and VR at each inter-particle distance (Fig. 8.13).

 At intermediate electrolyte concentration, repulsion tends to

dominate the interaction; coagulation is slow because of the
existence of barrier.

 Particles must possess sufficient energy (KT energy, and

might be accomplished by heating the suspension) to pass
over the energy barrier before floccules are formed.

 The height of the barrier is a function of the degree of

compression (thickness) of the DDL.
 Fig. 8.14 represents a system with no energy barrier to
flocculation. The VA dominates over the total distance of
separation.

 At low valence and electrolyte concentration (Fig. 8.15), the

VR dominates over much of the distance and a high energy
barrier is the result.

 The system is stable.

 Note value of interaction depends how VR varies with

treatment since VA is insensitive to particle environment.
 VR
+

Energy barrier to flocculation

Interaction

1/K 2/K 4/K

Distance between particles
-

VA
Minimum energy of interaction
Fig. 8.13. Schematic diagram of potential energy curve for plate
like particle where Vinteraction = VA + VR at each inter-particle
distance.
 VR
+
Interaction

1/K 2/K 4/K

Distance between particles
-

VA

Fig. 8.14. Schematic diagram of a system with no energy barrier

to flocculation.
 VR
+

Energy barrier to flocculation

Interaction

1/K 2/K 4/K

distance between particles
-

VA

Fig. 8.15. At low valence and electrolyte concentration, VR

dominates
over much of the distance and a high energy barrier is the result
(Schematic diagram).
Donnon Ion Exchange Equation or Donnon
Equilibria

 A system in which a solution and suspension were separated by a

membrane that was permeable to ions but impermeable to the
exchanger (Donnan, 1911, Bear, 1964).

 An example is the filter paper separating a soil suspension and its

extract.

 Each soil colloid particle with its ion swarm (DDL) is regarded as
being separated by an imaginary membrane from the bulk solution.
 Basic Donnon equilibria apply to homovalent exchange in soils
and can also be used to explain dilution effects during
exchange between ions of different valence.

 The equilibrium condition of a Donnon system is characterized

by the fact that the chemical potential (μ) of every deffusable
electrolyte, and the electrochemical potential of every
deffusable ion species, are constant through out a system.
 For a clay colloid in equilibrium with the intermicellar solution
containing a strong electrolyte (MA), temperature and pressure
being constant, the state of equilibrium is:
μMAi = μMAo --------------------- (8.35)
 where i and o are the inner and outer solution.
 The relation between chemical potential and activity is:
μMA = μoMA + RT ln (MA) ---------- (8.36)
 where μo is standard state chemical potential.
 Now equation 8.35 can be rewritten by putting the value from
equation 8.36:
μoMA + RT ln (MA)i = μoMA + RT ln (MA)o ------------- (8.37) or
(MA)i = (MA)o -------------- (8.38), where ( ) denote activity.
 The equation 8.38 is the general Donnon equilibrium.
According to definition, (MA) = (M) + (A), the equation 8.36
can be written as the well known ion product formula:
(M)i (A)i = (M)o (A)o -------------- (8.39)
 The equations 8.38 and 8.39 help to infer that the activity of
cations and anions varies in opposite directions so that the
activity of electrolyte remains constant at any point of the
liquid phase.
 If the electrolyte is of the type MnAm, the ion product formula
reads:
(M)ni (A)mi = (M)no (A)mo ----------------------------- (8.40)
or
[(M)i / (M)o]1/m = [(A)o / (A)i]1/n ---------------------- (8.41)
 If distinction is made between ions originating from the colloid
and the free salt, the corresponding equation becomes:
[ZM + YM]n [YAm] = [XMn × XAm] ------------------- (8.42)
and
[ZM + YM / XM]1/m = [XA / YA]1/n ----------------------- (8.43)
 Where
 Z is activity of M ionized from the exchanger.
 Y is activity of ions of the free salts in the micellar solution.
 X is corresponding activity in the intermicellar solution.
 For example if an aqueous system containing K, Ca, La, Cl,
OH, and SO4 ions, the equilibrium will be expressed as:
(K+)i / (K+)o = (H+)i / (H+)o = [(Ca2+)i / (Ca2+)o]1/2 = [(La3+)i / (La3+)o]1/3
= (Cl+)o / (Cl+)i = (OH-)o / (OH-)i = [(SO42-)o / (SO42-)i1/2 ----- (8.44)

 Because they are always present in aqueous systems, H+ and

OH- are included here and should be included even if not
mentioned.

 In equation 8.44, corresponding Z + Y may be substituted for

(M)i and X for (M)o.
 i. For Na and K

 The equation 8.44 may be regarded as equivalent to the mass

action formula, the equilibrium constant being equal to:

[(Na+)i (K+)o] / [(K+)i (Na+)o] = 1 ---------------------- (8.45)

 or by introducing concentration term (f), signifying the activity

coefficient:

[(Na+)i (K+)o] / [(K+)i (Na+)o] = [fKi × fNao] / [fNa)i × fKo] = dK,Na

---- (8.46)

 The equilibrium quotient (d) is a measure of the relative

adsorption energy or replacing power of the two ions.
 The Fig. 8.16 gives a schematic picture of ion distribution
around a negatively charged particle according to the Donnon
equilibria.
Activity of cation or anion

ZM + YM

ZM XA XM

YA YM

Distance between particles

Fig. 8.16. Schematic presentation of ion activity distribution
according to the Donnon equilibria around negatively
charged particle, saturated with ion M and in equilibrium
with salt MA. The Z refers to the activity of counter ions,
Y is the activity of free salt in inner solution and X is the
activity of salt in the outer solution.
 The London force or dispersion force is the weakest of the
imtermolecular forces.

 The dispersion force which in fact is an induced dipole - induced

dipole interaction depends on the polarisability of the interacting
molecules and is inversely proportional to the sixth power of
separation.

 The van der Waals force is the sum of attractive or repulsive forces
between molecules (or between parts of the same molecule) other than
those due to covalent bonds or to the electrostatic interaction of ions
with one another or with neutral molecule
Any Question