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Mineral Surfaces

Minerals which are precipitated can also


interact with other molecules and ions at
the surface
Attraction between a particular mineral
surface and an ion or molecule due to:
Electrostatic interaction (unlike charges attract)
Hydrophobic/hydrophilic interactions
Specific bonding reactions at the surface

Charged Surfaces
OH
OH
OH2

H+

OH
OH
OH
OH

H+

Mineral surface has exposed


ions that have an unsatisfied
bond in water, they bond to
H2O, many of which rearrange
and shed a H+
S- + H2O SH2O SOH + H+

GOUY-CHAPMAN
DOUBLE-LAYER
MODEL

STERN-GRAHAME
TRIPLE-LAYER
MODEL

Surface reaction vs. transport


control vs. diffusion control
3 possibilities for controlling overall rate of
mineral dissolution:
Surface reaction chemical process at the
mineral surface with a reactant
Diffusion control physical process of
dissolved component(s) diffusing into the bulk
solution
Transport control physical process of
dissolved component(s) being advectively
carried from the mineral surface

General mineral dissolution rates


(surface reaction)
General rate law for minerals:
d [mineral ]
kA[reactant ]
dt

Where k is in something similar to units of mol -1


sec-1 to give a rate, R, in terms of mol cm -3 sec-1
Many ways to write the rate constant units
depending on the rate law (which is almost never
an elementary rxn for minerals), but dissolution
rate for minerals is normalized to surface area as
the primary control on overall rates!

Diffusion Rates
Diffusion, Fickian:
First law (steady state):

C
J D
x

Second Law (change w/time):

C
C
D 2
t
x
2

Where J is the flux (concentration area-1 time-1), D is the


diffusion coefficient (area-1 time-1), C is concentration
and t is time.

Mineral diffusion rates


For diffusion controlled rates:
Rd=DA(Cs-C)/r
Where Rd is the diffusion rate (mass volume-1 time-1), D is the
diffusion coefficient (cm2/sec), is porosity, A is the surface
area of the dissolving crystals per volume solution, Cs is the
equilibrium concentration of ion in question, C is
concentration, and r is spherical radius of dissolving
crystals

Diffusion rates are generally the slowest rate


that controls overall dissolution

Transport controlled rates


For systems where water is flowing:

dC
RkfC
dt

Where R is the surface-controlled rate of


dissolution (R=k+[Cs-C]), kf is the flushing
frequency (rate of flow/volume), Cs is the
saturation concentration, and C is conc.
SO at high flow rate dissolution is surface
reaction controlled, at low flow rate it is diffusion
controlled

Zero-order mineral dissolution kinetics


Most silicate minerals (feldspars, quartz
polymorphs, pyroxenes, amphiboles) are
observed to follow zero-order kinetics:
R=Ak+

Log dissolution rate

where A is the surface area and k is the rate constant (mol


cm-3 sec-1) for rate, R, of an ion dissolving from a mineral

pH

Rate and equilibrium


pH dependence of silicate mineral dissolution,
suggests activated surface complex for dissolution:
Q
R k [ H ] [1
]
K eq
n

where n is a constant, p is the average


stoichiometric coefficient, Q is the activity quotient,
and Q/Keq is the saturation index (how far from
equilibrium the mineral is)
Far from equilibrium, Q/Keq < 0.05, simplifies to
R=k+[H+]n

Ligand-assisted dissolution
Thought to be minor for many
aluminosilicates, but key for many other
minerals (ex.: FeOOH minerals)
Similar to surface-complex control, ligands
strongly binding with surface groups on
the mineral surface can greatly increase
rate (and solubility of the ion in solution,
changing the SI)

Mineral precipitation kinetics


How do minerals form?
Ion-ion interaction cluster aggregation
nanocrystal formation crystal growth
(ionic aggregation, ostwald ripening,
topotactic alignment)
What controls the overall rate?

Nuclei formation
Classical view of precipitation start with the
formation of a critical nuclei, which requires
a large degree of supersaturation
Energy to form a nuclei: Gj=Gbulk-Gsurf
Rate of nuclei formation is then related to
the energy to form the particle, the size of
the critical nuclei, collisional efficiency of
ions involved, the degree of supersaturation,
and temperature

Nucleation rate
B 2 2
J exp 3 3
2
k T (ln S )
Where B is a shape factor equal to 16/3 for a sphere and
32 for a cube, is the interfacial free energy, is the
molecular volume, k is Boltzmanns constant (1.38x10-23
J/K), T is temperature (K), S is the supersaturation ratio
(C/Cs), and is a pre-exponential factor (around 10333
cm-3 sec-1 and approximated by ( = D/(^5/3) )