SS 115 – Soil Chemistry

DIFFUSE DOUBLE LAYER

THEORY & ADSORPTION
ISOTHERMS
Group 3
Diffuse Double Layer (DDL)

• It is the result of clay-water-electrolyte interaction.

• Cations are held strongly on the negatively charged surface of

dry fine-grained soil or clays.

• Those cations in excess of those needed to neutralize

electronegativity of clay particles and associated anions are
present as salt precipitates.
Diffuse Double Layer (DDL)

•Theory:
“ As the distance from the exchange site
increases, the layering of the ions decreases
because it is a function of the surface area
exposed having the exchange charge
reachable”.
Diffuse Double Layer (cont’d)

• When dry clays come in contact with water, the precipitates

can go into solution.

• The adsorbed cations would try to diffuse away from the clay
surface and tries to equalize the concentration throughout
pore water. However, this movement of adsorbed cations are
restricted/ minimized by the negative surface charge of clays.
Diffuse Double Layer (cont’d)

Fig. 2.8 Distribution of ions adjacent to clay surface

(modified from Mitchell and Soga 2005)
Assumptions in the DDL Theory:
• Ions in the double layer are point charges and there are no
interactions among them.

• Charge on particle surface is uniformly distributed.

• Platy particle surface is large relative to the thickness of double

layer (to maintain one dimensional condition).

• Permittivity of medium adjacent to particle surface is independent

of position. Permittivity is the measure of the ease with which a
molecule can be polarized and oriented in an electric field.
Concentration of ions in force field at equilibrium is given by
Boltzmann equation as follows:

ni = Concentration of ions of type (no of ions/m3)

E = the potential energy
T = the temperature in Kelvin,
k = the Boltzmann constant (1.38 x 10M-23 J/K)

subscript 0 represents reference state which is at a

large distance from the surface.
Adsorption Isotherms

• Describe the adsorption of solutes by solids at

constant temperature and pressure
• Shows the amount of adsorbate (solute) adsorbed by
an adsorbent as a function of the equilibrium
concentration of the solute.
• Isotherm shapes may vary depending on the affinity
of the adsorbate for the adsorbent
Adsorption Isotherms
• Describe the adsorption of solutes by solids at
constant temperature and pressure
• Shows the amount of adsorbate (solute) adsorbed by
an adsorbent as a function of the equilibrium
concentration of the solute.
• Isotherm shapes may vary depending on the affinity
of the adsorbate for the adsorbent
• There must be a known amount of adsorbate added
to the system containing a known amount of
adsorbent
Adsorption Isotherms
• The amount of adsorbate removed from the solution at
equilibrium is assumed to be adsorbed.
• Equilibrium conditions must prevail and secondary reactions
must be eliminated / corrected
• Precipitation is indicated by rapid increase in apparent adsorption
with small change in equilibrium solution concentration

• Some Adsorption equations:

• Langmuir
• Freundlunch
Langmuir Equation
• Initially derived for adsorption of gasses by solids.

• Assumptions:
• Constant energy of adsorption is independent of the
extent of surface coverage
• Adsorption on specific sites, with no interaction
between adsorbate molecultes
• Maximum adsorption equal to a complete
monomolecular layer on all reactive adsorbent
surfaces.
Common form of Langmuir Equation
• Where:
C = Equilibrium concentration of
adsorbate in question

x/m = weight of adsorbate per unit

weight of adsorbent

K = constant related to binding

strength

b = maximum amount of
adsorbate that can be adsorbed
Langmuir equation (cont.)
• The equation was derived by assuming constant free energy
adsorption
• The net effect: 2 phenomena tend to compensate for each
other  relative constant adsorption energy
• Langmuir equation is limited to the range for which
experimental data are available.
• In systems where energy adsorption is not strictly constant,
Langmuir equation may still describe adsorption over a
portion of adsorption range due to the variation in energy of
adsorption (depending on bonding site or dominant
mechanism).
Advantages of Langmuir Equation

• Defines a finite limit of adsorption on a given array of

sites which meet the Langmuir model criteria
• Enables one to estimate the total adsorption capacity
of soils for various adsorbates
• Comparing such capacities may also suggest
adsorption mechanisms