INTERACTION OF MINERAL SURFACES WITH SOLUTIONS.

GEOCHEMISTRY
Yetzabbel Flores1
1
Institute of Environmental Management

INTRODUCTION
It involves the interface between solution and solids, where the properties of the surface as particle size
less of 1µm, play a main role with three significant consequences (Langmuir, 1997):
 Increase in the solubilities of small particles
 Stability on suspension and transport availability.
 Unsatisfied surface charge making them a potential sorbent
The surface area to volume ratio on sedimentary particle is high, in fact the concentration of many trace
elements dissolved in flowing water is controlled by adsorption on and desorption from the solid media
of transition. It plays a role in soil fertility, seawater unsaturation and dispersion of pollutants.

ADSORPTION
Adsorption is the attachment of an ion in solution to a pre/existing solid surface (White, 2013). It affects
the surface of suspended particles and colloids which influence their aggregation and transport, and for
its full understanding is required the physical and chemical property characterization of the solute, the
sorbent and the solvent (Stumm, 1992; Langmuir, 1997).
 Surface complex formation: Coordinate bond between metals and ligands at the surface.
 Electrostatic interactions: The electrical charge of the surface, called electrostatic force, affects the
surface complex formation and loosely binds other ions.
 Hydrophobic adsorption: Non polar substances are insoluble in water, and they tend to be adsorbed
on the surface because they are repelled by water.
The adsorption is described in terms of adsorption isotherms, where initially the measurements were
done at constant temperature (Merkel et al., 2002).

Linear regression isotherm:

The simplest form of adsorption isotherm with advantage of simplicity, but with a serious disadvantage
of no upper limit because the relation is linear.

θ M =K ad [ M ]

Where: θ M _ fraction of surface sites occupied by species M

[ M ]_ dissolved concentration of M
K ad _ adsorption equilibrium constant
Using this relation, a transport equation (Merkel et al., 2002) can be writing as:
 Bd
∗θM
q Bd
Rf =1+ =1+ ∗K ad
[M] q
Where: Bd _ bulk density
q _ water content
Langmuir isotherms:
It reflects saturation of the surface. It is derivate from kinetic fundamentals or from thermodynamic
principles, under the assumptions (1) the free energy of adsorption is independent of the number of sites
available, (2) the law of mass action applies, and (3) only a monolayer of adsorbate can form.

K ad [ M ]
θM=
1+ K ad [ M ]
Using this relation, a transport equation (Merkel et al., 2002) can be writing as:

Rf =1+
Bd
q
∗
[ K ad
( 1+ K ad [ M ] )
2
]
Freundlich isotherms:
It is a merely empirical exponential relation between sorbet and dissolved molecules, and it doesn't
show saturation (White, 2013). It is based on a model of a multi-lamellar coating of the solid surface
assuming a priori that all sites with the largest binding energy are occupied (steep section of the curve)
and with increasing grade, sites with lower binding energy (flattening of the curve) are occupied. (Merkel
et al., 2002).
n
θ M =K ad [ M ]
Where: n _ an empirical constant
Transformation on a retardation factor for transport equation (Merkel et al., 2002) can be writing as:
Bd n−1
Rf =1+ ∗n∗K ad∗[ M ]
q

Surface complexation model:

It is a generalization of Langmuir isotherm; it incorporates chemical bounding of solute species to surface
atoms and electrostatic interactions between the surface and solute ions (White, 2013). The free energy
of adsorption is the sum of a complexation (intrinsic) and electrostatic term (coulombic).
∆ G ad=∆ Gintr +∆ Gcoul
The equilibrium constant:
K ad =K intr K coul
The complexation constant, K, gives information about the complex stability. Large complex constants
indicate a strong tendency for complexation, or high complex stability (Merkel et al., 2002).
The adsorption reaction:
≡ S+ M ↔ ≡ SM
An additional possibility is multidentate adsorption, where x sites are involved.
x ≡ S + M ↔ ≡ Sx M
And the corresponding equilibrium equation:

[ ≡ Sx M ]
K ad = x
[≡ S ] [ M ]
Where: x_ number of sites involved
M_ species being adsorbed

A better approach is to assume that the reaction occurs with a multidentate surface species. In this case
the equilibrium constant will be expressed as:

[ ≡ Sx M ]
K ad =
[≡S]
[M ]
x
Because H+ and OH- are involved in the phenomena, the adsorption of metal (positive charge part) and
ligands (negative charge part) for the functional groups will be pH-dependent. Adsorption of cations
increase with increasing pH, while adsorption of anions decreases.
The positively charged part is usually a metal ion or hydrogen, but may also be another positively
charged complex. Ligands are molecules, which have at least one free pair of electrons (bases) (Merkel
et al., 2002).

Figure 1. Scheme of a surface complex. (White, 2013)

Surface complexes (Figure 1) may be divided into inner sphere which involve some degree of covalent
bonding between the adsorbed species and atoms on the surface, and outer sphere where one or more
water molecules separate the adsorbed ion and the surface, in it the adsorption involves electrostatic
forces. A third possibility involves an ion held within the diffuse layer by long range electrostatic forces.
On this basis, three models will be discussed (Figure 2), which enable a calculation of the electrical
potential (Merkel et al., 2002):
 Constant-capacitance: The constant-capacitance model assumes that the double layer on the solid-
liquid phase boundary can be regarded as a parallel-plate capacitor.
 Diffuse-double-layer: In the area of the boundary layer between solid and aqueous phase,
independently of the surface charge, increased concentrations of cations and anions within a diffuse
layer exists because of electrostatic forces.
 Triple-layer model: the protons and hydroxide ions are bound at the layer (o-plane) close to the
phase boundary, whereas inner-sphere complexes are bound in a β-plane somewhat dislodged. Both
planes are assumed as constant- capacity layers. The range outside the β -plane containing the
outer-sphere complexes is modeled as a diffuse layer.

Figure 2. Idealized distribution of electrical potential. (Merkel et al., 2002)

DEVELOPMENT OF SURFACE CHARGE AND THE ELECTRIC

DOUBLE LAYER
The surface charge result from the sorption reaction itself, by three main ways (Stumm, 1992; White,
2013):
 Complexation reactions between the surface and dissolved species
 Lattice imperfections at the solid surface
 Hydrophobic adsorption or surfactant ionization.
The above type of surface charge contributes to the net total particle charge. The net density of electrical
charge on the solid surface is denoted by σ net :

σ net=σ 0 +σ H +σ SC

Where: σ 0_ permanent structural charge

σ H _ net proton charge

 σ SC _ complexation charge
σ H =F ( Γ H −Γ OH ¿
σ SC =F ( Z M Γ M +Z A Γ A ¿
σ SC =σ IS + σ OS

Where: F _ Faraday constant (96,490 C mol-1)

Γ ❑_ Adsorption densities of H+ and OH- (mol/m2)
M and A_ Metal and anions
σ _ Charge of the ion
It is broken into inner sphere (IS) and outer sphere (OS)
The net charge (White, 2013) on the mineral surface can be rewriting as:
σ net=σ 0 + F ( Γ H −Γ OH + Z M Γ M + Z A Γ A ¿
The isoelectric point or zero point of charge (ZPC) is the pH value where the surface charge of the solid
caused by binding of all ions is 0.

Surface potential and the double layer

The charge on a surface exerts a force on ions in the adjacent solution and gives rise to an electrical
potential, which will depend upon the nature and distribution of ions in solution as well as intervening
water molecules. The distribution is usually idealized as an electric double layer (Stumm, 1992).
The charge and potential at the surface can be related by Gouy-Chapman theory:
σ =¿ ¿
Where: z_ a symmetrical background electrolyte
Ψ ¿ potential at the surface
T _ Temperature
F _ Faraday constant
R _ Gas constant (8.314 J mol-1 K-1)
I _ Ionic strength of the solution in contact with the surface
ε r_ Dielectric constant of water (78.5 at 25° C)
ε 0_ Permittivity of a vacuum (8.854 x 10-12 C V-1 m-1 or 8.854 x 10-12 C2 J-1 m-1)

At 25 °C, the equation can be defined by:

0.5
σ =α I sinh(βz Ψ 0 )
Where: α= 0.1174
β=19.5
Where the potential is small, the potential is expressed as a function of distance from the surface:

Ψ (x)=Ψ 0 ⅇ− Kx
Where the double layer thickness or Debye parameter or Debye length is defined by:

K=
√ 2 F2 I
ε r ε 0 RT
An excess concentration of oppositely charged ions develops adjacent to the surface will generated and
electric double layer (Figure 3). The inner layer, Stern layer, consist of charges fixed to the surface; the
outer layer, Gouy layer, consists of dissolved ions that retain some freedom of thermal movement.

Figure 3. Charge and potential in the double layer complexation over a clay mineral. (White, 2013)

The Gouy layer is consider to be the Debye length (1/k), it will collapse in high ionic strength solution
and expand in low ionic strength ones.
In compacted clays retardation of diffusion of ions can occurs, and clay act as semi-permeable
membranes where a chemical fractionation of the diffusing fluid can result.
 At low ionic strength, the charged layer surrounding a particle can be strong enough to repel similar
particles with their associated Gouy layers, it will prevent coagulation forming a relatively stable colloidal
suspension. But if the ionic strength of the solution increase, the Gouy layer is compressed and the
repulsion between particles decreases allowing the particles bound together by van der Waals forces
between them and settle out of the solution.

Effect of the surface potential on adsorption

The importance of the surface properties of given material exposed to solution increase in proportion to
the surface area of the material and its surface charge, because the sportive abilities of minerals are
proportional to their surface areas and surface-site densities (Langmuir, 1997).
An ion must overcome the electrostatic forces associated with the electric double layer before it can
participate in surface reaction. It can be taken in account by applying a correction factor derivate from
the electric double layer theory of the mass law constants for surface reactions (Stumm, 1992).
∆ G ads=∆ Gintr + ∆G coul

Where: ∆ G ads_ Total free energy of adsorption reaction

∆ Gintr _ Intrinsic free energy of the reaction

∆ G coul_ Free energy due to the electrostatic forces
∆ G coul =F∆Z Ψ 0
∆Z is the change in molar charge of the surface species due to the adsorption reaction.
The effect of surface potential (Figure 4Error: Reference source not found) on a given adsorbate will be
to shift the adsorption curves to higher pH for cations and lower pH for anions.

Figure 4. Effect of the surface potential in the adsorption curves of Pb on hydrous ferric oxide. (White, 2013)

Surface charge may be permanent and independent of the solution composition, or variable changing
with solution composition (Langmuir, 1997).
BIBLIOGRAPHY
Langmuir, D. (1997) AQUEOUS ENVIRONMENTAL GEOCHEMISTRY. Upper Saddle River: Prentice Hall.
Merkel, B. J. et al. (2002) Groundwater Chemistry. A practical guide to modeling of natural and
contaminated aquatic systems. Springer.
Stumm, W. (1992) Chemistry of the solid-water interface: processes at the mineral-water and particle-
water interface in natural systems. John Wiley & Sons Inc.
White, W. M. (2013) ‘Mineral surfaces and their nteraction with solutions’, in. Wiley & Sons, pp. 253–
265.