A COMPILATION OF RATE PARAMETERS 

OF WATER-MINERAL INTERACTION 

KINETICS FOR APPLICATION TO 

GEOCHEMICAL MODELING 

U.S. GEOLOGICAL SURVEY

PEN FILE REPORT 2004-1068

repared in cooperation with the

atory – United States Department of Energy

O

P

National Energy Technology Labor

U.S. Department of the Interior 

U.S. Geological Survey 
A COMPILATION OF RATE PARAMETERS 

OF WATER-MINERAL INTERACTION 

KINETICS FOR APPLICATION TO 

GEOCHEMICAL MODELING 

James L. Palandri and Yousif K. Kharaka 

U.S. GEOLOGICAL SURVEY 

OPEN FILE REPORT 2004-1068 

Prepared in cooperation with the 

National Energy Technology Laboratory – United States Department of Energy 

Menlo Park, California 

 March 2004 
U.S. DEPARTMENT OF THE INTERIOR 

GALE NORTON, Secretary 

U.S. GEOLOGICAL SURVEY

CHARLES GROAT, Director 

Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the

U.S. Government. 

For Additional Information 

Write to: 

Copies of this report may be 

obtained from the authors or 

James Palandri 

345 Middlefield Road, MS 427 

Menlo Park, CA 94025 

U.S. Geological Survey 

Information Center 

Box 25286, MS 517

Denver Federal Center 

Denver, CO 80225

ii
CONTENTS 

ABSTRACT..................................................................................................................... 1

1. INTRODUCTION........................................................................................................ 1

2. METHODS .................................................................................................................. 2

2.1 Rate Equations...................................................................................................................... 2 

2.2 Data Reduction..................................................................................................................... 6 

2.3 Limitations and Uncertainties............................................................................................. 11 

3. RESULTS.................................................................................................................. 12

3.1 Tectosilicates....................................................................................................................... 12 

3.1.1 SiO2 Polymorphs.......................................................................................................... 12 

3.1.1.1 Quartz.................................................................................................................... 12 

3.1.1.2 Amorphous SiO2, Cristobalite, and SiO2 Polymorph Precipitation...................... 14 

3.1.2 Feldspars...................................................................................................................... 16 

3.1.2.1 Plagioclase Feldspars............................................................................................ 16 

3.1.2.2 K-feldspar ............................................................................................................. 24 

3.1.3 Feldspathoids: Nepheline and Leucite......................................................................... 26 

3.2 Orthosilicates...................................................................................................................... 28 

3.2.1 Olivine Group .............................................................................................................. 28 

3.2.2 Garnet Group ............................................................................................................... 31 

3.2.3 Al2SiO5 Group ............................................................................................................. 32 

3.2.4 Staurolite...................................................................................................................... 33 

3.2.5 Epidote Group.............................................................................................................. 33 

3.3 Cyclosilicates...................................................................................................................... 35 

3.3.1 Cordierite and Tourmaline........................................................................................... 35 

3.4 Inosilicates.......................................................................................................................... 36 

3.4.1 Pyroxene Group / Pyroxenoid Group .......................................................................... 36 

3.4.2 Amphibole Group ........................................................................................................ 37 

3.5 Phyllosilicates..................................................................................................................... 38 

3.5.1 Mica Group .................................................................................................................. 38 

3.5.2 Clay Group................................................................................................................... 38 

3.5.3 Miscellaneous Phyllosilicates...................................................................................... 39 

3.6 Oxides................................................................................................................................. 40 

3.7 Hydroxides.......................................................................................................................... 41 

3.8 Carbonates........................................................................................................................... 41 

3.9 Sulfates................................................................................................................................ 42 

3.10 Sulfides ............................................................................................................................. 43

3.11 Phosphates......................................................................................................................... 44 

3.12 Halides.............................................................................................................................. 45 

4. CONCLUSIONS........................................................................................................ 46

REFERENCES.............................................................................................................. 47

iii
LIST OF FIGURES

Figure 1. Rates of albite dissolution from 25 to 300 °C and pH from 1.3 to 10.3. Data at 100, 

200, and 300 °C (open diamonds, triangles and squares, respectively) from Hellman, 1994, 

and at 25 °C (open circles) from Chou and Wollast, 1985. Dashed curves: results from 

non-linear regression. Straight black lines: results from piecewise linear regression of 100 

°C data. Black curves: sum of results from piecewise linear regression. ............................... 8 

Figure 2. Rates of magnesite dissolution at 25 °C and pH from 0.19 to 10.13. Data 25 °C from

Pokrovsky and Schott, 1999; open triangles, data used in piecewise linear regression; open 

squares, other data. Dashed lines, results from piecewise linear regression of acidic and 

neutral mechanisms. Black curves, sum of results from piecewise linear regression. Gray 

curve, results from non-linear curve fitting. ......................................................................... 10 

LIST OF TABLES 

Table 1. Albite Dissolution Rate Parameters.................................................................................. 8 

Table 2. Dissolution Rate Parameters.......................................................................................... 10 

Table 3. Quartz dissolution Rate Data in Pure H2O...................................................................... 12 

Table 3. Quartz dissolution Rate Data in Pure H2O - continued. ................................................. 12 

Table 4. Quartz Dissolution Rate Parameters............................................................................... 14 

Table 5. Amorphous Silica Dissolution Rate Data in Pure H2O................................................... 14 

Table 5. Amorphous Silica Dissolution Rate Data in Pure H2O - continued. .............................. 15 

Table 6. Amorphous Silica and Cristobalite Dissolution, and Silica Polymorph 

Precipitation Rate Parameters............................................................................................... 15 

Table 7. Albite Dissolution Rate Data. ......................................................................................... 17 

Table 8. Oligoclase Dissolution Rate Data................................................................................... 18 

Table 9. Andesine Dissolution Rate Data..................................................................................... 19 

Table 10. Labradorite Dissolution Rate Data. .............................................................................. 20 

Table 11. Bytownite Dissolution Rate Data. ................................................................................ 21 

Table 12. Anorthite Dissolution Rate Data................................................................................... 22 

Table 12. Anorthite Dissolution Rate Data - continued................................................................ 23 

Table 12. Anorthite Dissolution Rate Data - continued................................................................ 24 

Table 13. Plagioclase Dissolution Rate Parameters...................................................................... 24 

Table 14. K-feldspar Dissolution rate Data. ................................................................................ 25 

Table 14. K-feldspar Dissolution rate Data. ................................................................................ 26 

Table 15. K-Feldspar Dissolution Rate Parameters...................................................................... 26 

Table 16. Nepheline Dissolution Rate Data................................................................................. 27 

Table 17. Leucite Dissolution Rate Constants and Reaction Ordersa........................................... 27 

Table 18. Feldspathoid Dissolution Rate Parameters. .................................................................. 27 

Table 19. Forsterite Dissolution Rate Data.................................................................................. 28 

Table 19. Forsterite Dissolution Rate Data - continued............................................................... 29 

Table 19. Forsterite Dissolution Rate Data - continued............................................................... 30 

Table 19. Forsterite Dissolution Rate Data - continued............................................................... 31 

Table 20. Orthosilicate Dissolution Rate Constants and Reaction Ordersa. ................................. 31 

Table 21. Kyanite Dissolution Rate Data. ................................................................................... 32 

iv
Table 23. Orthosilicate Dissolution Rate Parameters. .................................................................. 35 

Table 24. Cyclosilicate Dissolution Rate Constants and Reaction Ordersa.................................. 35 

Table 25. Cyclosilicate Dissolution Rate Parameters................................................................... 36 

Table 26. Pyroxene and Pyroxenoid Dissolution Rate Parameters............................................... 37 

Table 27. Amphibole Dissolution Rate Parameters...................................................................... 37 

Table 28. Orthosilicate Dissolution Rate Parameters. .................................................................. 38 

Table 29. Clay Group Mineral Dissolution Rate Parameters. ...................................................... 39 

Table 30. Miscellaneous Phyllosilicate Mineral Dissolution Rate Parameters. ........................... 40 

Table 31. Oxide Mineral Dissolution Rate Parameters. ............................................................... 40 

Table 32. Hydroxide Mineral Dissolution Rate Parameters. ........................................................ 41 

Table 33. Carbonate Mineral Dissolution Rate Parameters.......................................................... 42 

Table 34. Sulfate Mineral Dissolution Rate Parameters............................................................... 43 

Table 35. Sulfide Mineral Dissolution Rate Parameters............................................................... 43 

Table 36. Phosphate Mineral Dissolution Rate Parameters.......................................................... 44 

Table 37. Halide Mineral Dissolution Rate Parameters................................................................ 45 

Conversion Factors

Multiply By To obtain

meter (m) 39.37 inch (in.)

meter (m) 3.281 foot (ft)

meter (m) 1.094 yard (yd) 

square meter (m2) 10.76 square foot (ft2)

square meter (m2) 1549.44 square inch (in2)

kilogram (kg) 35.27 ounce, avoirdupois (oz)

kilogram (kg) 2.205 pound avoirdupois (lb)

joule (J) 0.0000002 kilowatt-hour (kWh)

Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows:

°F = (1.8 × °C) + 32 

v 
ABSTRACT 

Geochemical reaction path modeling is useful for rapidly assessing the extent of 

water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of 

some systems, such as those at low temperature with relatively high hydrologic flow rates, or 

those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account 

for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled 

parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including 

phases from all the major classes of silicates, most carbonates, and many other non-silicates. The 

compiled dissolution rate constants range from -0.21 log moles m-2

 s

-1 for halite, to -17.44 log 

moles m-2 s-1 for kyanite, for conditions far from equilibrium, at 25 °C, and pH near neutral. 

These data have been added to a computer code that simulates an infinitely well-stirred batch 

reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates 

are expected to be much slower than those predicted by the selected computer code, primarily 

because actual geochemical processes commonly involve flow through porous or fractured 

media, wherein the development of concentration gradients in the aqueous phase near mineral 

surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further 

differences between observed and computed reaction rates may occur because of variables 

beyond the scope of most geochemical simulators, such as variation in grain size, aquifer 

heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary 

minerals that may lead to decreased porosity and clogged pore throats. 

1. INTRODUCTION 

Equilibrium-based geochemical modeling is a method for predicting the identity and 

extent of chemical reactions in both geological and industrial processes. The method usually 

entails computer-aided simultaneous solution of a system of non-linear equations. Given a 

pressure (P), a temperature (T), and a bulk chemical composition (x), a geochemical modeling 

program or simulator computes the equilibrium distribution of the chemical components among 

gaseous, aqueous, or mineral phases. The variables P, T, or x can be changed incrementally over 

the course of a simulation with equilibrium recomputed at each step, thereby defining a reaction 

path. Some geochemical simulators, such as GAMSPATH (for a description of GAMSPATH, 

and comparison of GAMSPATH to other geochemical simulators, see Perkins et al., 1997), 

require the presence of an aqueous fluid phase and are well suited to simulation of systems at 

shallow to moderate depth in the Earth’s crust, or wherever there is open space that is saturated 

with water, such as pores or fractures. Water is the medium that allows mass transfer by 

diffusion or fluid flow, and redistribution of the components via chemical reaction among the 

gaseous and various mineral phases, and species in the aqueous phase. Considered herein is the 

quantification of the rates at which these reactions occur. 

Local non-redox chemical equilibria among fluids, gases, and alteration minerals is a 

valid assumption in many volcanic-hosted hydrothermal systems (Arnórsson, 1983; Arnórsson et 

al., 1983; Giggenbach, 1980; Giggenbach, 1981; Pang and Reed, 1998; Reed, 1982; Reed, 1997; 

1
Reed, 1998; Reed and Spycher, 1984), and in many sedimentary systems with low fluid flow 

rates at temperatures as low as 75-80 °C (Bazin et al., 1997a; Bazin et al., 1997b; Palandri and 

Reed, 2001). In other systems, equilibrium with an alteration mineral assemblage cannot always 

be assumed, especially in systems where low temperature leads to slow rates of chemical 

reaction, or if there exists a perturbation away from equilibrium, e.g. relatively fast hydrologic 

flow rates from one lithologic regime into another. It is important to recognize that equilibrium

between aqueous fluid and primary minerals is commonly lacking, and in some cases cannot be 

attained, e.g. anorthite or forsterite at T and P of H2O liquid-vapor saturation. Further, 

equilibrium between aqueous fluid and secondary minerals containing redox elements such as Fe 

and S generally requires higher temperatures than for those minerals containing only non-redox 

elements (other than oxygen). 

For many geologic systems it is desirable to know the length of time required for a 

system to equilibrate with respect to alteration minerals, and perhaps more importantly, the rate 

of dissolution of primary minerals. An illustrative example is the geologic sequestration of

carbon dioxide (CO2) from anthropogenic sources, such as fossil fuel-fired electrical power 

plants, is injected into depleted oil or gas reservoirs, coal seams, or deep saline aquifers. As a 

result of CO2 injection, these systems are perturbed far from equilibrium, and will require some

length of time to re-equilibrate with alteration minerals, due to the relatively slow kinetics of

mineral-CO2-water interactions at aquifer temperatures and pressures. While dissolution of 

supercritical CO2 into aquifer fluids is expected to be kinetically rapid, the rate at which 

dissolved CO2 reacts with primary minerals, and the rates at which secondary minerals 

precipitate are much slower (Gunter et al., 1997). 

To model systems where the time dependence of geochemical reactions is of critical 

importance, there is a need to quantify rates of mineral dissolution and precipitation, and to a 

lesser extent, of aqueous speciation. Therefore, we compiled directly or determined using 

regression and curve-fitting, the parameters conforming to a general, Arrhenius-type rate 

equation for over 70 minerals, including most of the rock-forming minerals. For a few minerals, 

we have also compiled more specialized rate equations and parameters, where some workers 

have clearly shown that those equations provide a better fit to experimental data, e.g. quartz 

(Dove, 1994; Dove, 1999; Dove and Nix, 1997) and barite (Dove and Czank, 1995). The rate 

parameters compiled herein are for surface controlled reactions at conditions that are far from

equilibrium, rather than diffusion controlled reactions. This compilation does not contain rate 

parameters for aqueous speciation. 

2. METHODS 

2.1 Rate Equations 

Any rate equation that is to be used in geochemical computer modeling must contain only 

parameters that are available during program execution as variables or constants. The general 

rate equation and rate parameters compiled herein are compiled specifically for the program

GAMSPATH (Perkins et al., 1997), which uses a general, semi-empirical rate equation to which 

experimental rate data for many minerals can be reasonably well fit. A general form of the 

2 
equation for a single reaction mechanism modified from Lasaga and co-workers (1984; 1995; 

1998) is given by 

= −SA⋅ Ae f (a ) ( G ) RT

E

∆ r g dt

d

i

 (1) 

 and for multiple mechanisms

m −

[ ( ) ( G )] , ∆ r = − ⋅∑ j j i j j

j

SA A e f a g dt (2)

−

RT

E dm j

The rat

The dimensionless terms f (a ) are functions of the activity of the ith aqueous species 

p is commonly 

xpressed as the product of species activities 

i i

 (3a)

i represen

o

atic when ai is 

ero and n is positive, because the rate becomes zero, which cannot occur for some mechanisms, 

o ical singularity occurs. These problems can be 

voided by defining f with adsorption isotherms (Blum and Lasaga, 1991; Brady, 1992; Casey 

e, dm/dt, is in units of mol s-1. The surface area is represented by SA (m

2

), A is the 

Arrhenius pre-exponential factor (mol m-2 s-1), E is the activation energy (J mol

-1), T is the 

temperature (K), and R is the gas constant. 

j i,j

articipating in the jth reaction mechanism. The function for a single mechanism

e

= ∏ ni f (a ) a

i

where the exponents n t the reaction order with respect to species ai (Lasaga, 1995; 

Lasaga, 1998; Lasaga et al., 1994; Oelkers et al., 1994). For example, the expression 

0.5 0.5 ( ) + 3+− =

H Fe f ai a a

 (3b)

is for one of the reaction mechanisms for pyrite (McKibben and Barnes, 1986), discussed further, 

below. Positive and negative exponents denote catalysts and inhibitors respectively, except in 

the case of hydroxide-catalyzed mechanisms (as above in eqn. (3b)), which are quantified in 

terms of aH+ raised to a negative exponent (recall that for aqueous fluids, aH+aOH- = 10-14) t

simplify calculations. It is important to recognize that eqn. (3b) becomes problem

z i

r if ai is zero and ni is negative, because a numer

a

and Sposito, 1992; Furrer and Stumm, 1986; Gautier et al., 1994; Kline and Fogler, 1981; 

Pokrovsky and Schott, 1999; Stillings and Brantley, 1995), which have the form

3
⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

+

= + + +

+ +

Na Na

Na Na

i ad K a

K a

f a k

1 ( ) 1

This ex ,

95;

(3c)

pression is an example is an isotherm of the Langmuir type for quartz (Dove, 1994; Dove

1999; Dove and Nix, 1997), where KNa+ is the adsorption coefficient for Na+

, and kad is a 

constant factor by which the overall rate constant in adjusted. The sign of kad is positive for

catalysts and negative for inhibitors. GAMSPATH currently does not implement adsorption 

isotherms, and uses the form as in eqns. (3a) and (3b). 

The dimensionless term g(∆Gr) is a function of the chemical affinity to account for 

slowing of reaction rates as equilibrium is approached, and may be expressed as (Lasaga, 19

Lasaga, 1998; Lasaga et al., 1994; Oelkers et al., 1994): 

i

i

i i q

p

p q

r

Q

g( G ) (1 ) (1 ) ⎡ ⎤ ∆ = − Ω = −

⎣K ⎦ (4) 

⎢ ⎥

aturation index where Q is the activity product, and K 

the equilibrium constant. The parameters p and q are empirical and dimensionless, although 

ave been quantified for only a few minerals 

iscussed below), and for those minerals only for a single mechanism; in all other cases, the 

default values for pi and qi are to a first approximation, unity. Uncertainties in values for pi and 

qi are currently the source of much uncertainty in the length of time

computed in models of water-rock interaction. It has been observed here

an apparent significant slowing of the dissolution rate at low degrees of undersaturation 

emented in GAMSPATH is a sum of multiple mechanisms

Omega (Ω = Q/K) is the mineral s

is i i

pi can be predicted from transition state theory if the details of the reaction mechanism are 

known (Lasaga, 1995; Lasaga, 1998); pi and qi h

(d

to system equilibration 

for some minerals that t

is

(Lasaga, 1995; Lasaga, 1998; Lasaga et al., 1994). For example gibbsite (Nagy and Lasaga, 

1992) and albite (Burch et al., 1993), show a stepped shape in a plot of dissolution rate versus 

chemical affinity. 

The overall equation impl

[ (1 ) ] ,

, i i i j

j

i j

RT

i

i

SA Ae a

dt = − ∑ ∏ − Ω

 (5) 

but recast in terms of rate constants at 298.15 K (25 °C) and pH = 0 to facilitate comparison of 

various rates among minerals at near-surface T 

dm i n p q −E

[ (1 ) ] ,

,

298.15

1 1

298.15 i i i j

i

n p q

i j

R T K

E

K SA ki e a

dt

dm = − ∑ ∏ − Ω

⎟

⎠

⎞ ⎜

⎝

⎛ − −

 (6) 

i j

4 
In general, the most well-studied mechanisms are those in pure H2O (neutral pH), and those 

catalyzed by H+

 (acid) and OH- (base). For many minerals, the full equation includes a term for 

each of these three mechanisms: 

⎥

⎥

⎥

⎥

⎦ ⎢

⎢

⎢

⎢

⎣

+ −Ω

= − + −Ω

+

⎟

⎠

⎞ ⎜

⎝

⎛ − −

3 3 3 (1 )

(1 )

298.15

1 1

298.15 n p q

H

R T K

E

K

base

neutral

k e a

SA k e

dt

base (7) 

The OH

⎥ ⎟

⎞ − 1 1 ⎥

⎥

⎤

⎢

⎢

⎢

⎡

+ −Ω

⎠ ⎜

⎝

− ⎛

⎟

⎠

⎞ ⎜

⎝

⎛ − −

2 2

1 1 1 (1 )

298.15 298.15

298.15

1 1

298.15

R T K p q

E

K

n p q

H

R T K

E

K kacid e a

dm neut

acid

se

rite, pyrrhotite), and O (pyrite). In the case of pyrite and pyrrhotite, the 

OH-

-ca r

ica from fluids that are grossly supersaturated with 

spect to quartz. Further, quartz precipitation is prohibitively slow at low degrees of superturation. Therefore, we use the principle of microscopic reversibility (Lasaga, 1998): 

-

-catalyzed mechanism in eqn. (7) uses the activity of H+ raised to a reaction order with

negative sign, to simplify data reduction. Additional terms are added to or removed from eqn. 

(7) to account for other mechanisms or the absence of data. Other mechanisms include tho

catalyzed by HCO3

-

, (especially the carbonate minerals, which are quantified in terms of either 

HCO3

-

 or PCO2), Fe3+ (py 2

talyzed mechanism is apparently slowed by presence of Fe3+. This effect is accounted fo

by substituting a term in the form of eqn. (3b) for the H+

 activity and reaction order in the third

term in eqn. (7). It should be recognized that although the pyrite dissolution rates were measured 

at low pH, the reaction order with respect to H+

 is negative, i.e. the reaction is OH--catalyzed. 

Precipitation rate data do not exist for most minerals, because in mineral precipitation 

experiments, undesired metastable reaction products usually precipitate instead of the desired

mineral, especially far from equilibrium at high degrees of super-saturation. One example of this

behavior is the precipitation of amorphous sil

re

sa

− k k precipitation

librium

 (8)

where the precipitation rate constant can be calculated from the dissolution rate constant

equilibrium constant. However, it must be recognized that this relation requires that both the 

forward and backward reactions must both proceed by a single reversible mechanism. Related i

the phenomenon of nucleation, where some degree of super-saturation is required fo

+ = = k K dissolution

equi

and the

s

r

precipi

k

tation to proceed (Lebrón and Suárez, 1996; Nordeng and Sibley, 1994; Normand et al., 

2002; Reddy, 1986; Schoonen and Barnes, 1991b; Shiraki and Brantley, 1995; Sibley et al., 

1987; Steefel and Van Cappellen, 1990); in some cases this can be substantial, as for siderite 

(Greenberg and Tomson, 1992; Jensen et al., 2002). Nucleation may be either homogeneous, 

5
where nucleation occurs spontaneously in a liquid phase, or heterogeneous, where nucleation of 

a new phase occurs on the surface of a pre-existing solid phase (Lasaga, 1998). For most 

minerals, the degree of super-saturation required for homogeneous or heterogeneous nucleation 

has not

70),

, Lasaga

et al. (1994), Oelkers et al. (1994), Petrovich (1981a), Petrovich (1981b), Schoonen et al. (1998), 

S l and Van Cappellen (1990), Sverdrup (1990), Talman and 

esbitt (1988), Tuncay et al. (2002), Wieland et al. (1988), Wood and Walther (1983), Xiao and 

an example because it’s rate data clearly conform to eqn. (6) in one 

of its simplified forms, eqn. (7), where rates are controlled by H+

 and OH- catalysis and 

temperature. The magnesite example illustrates some problems that may arise if the ability to 

account for adsorption isotherms is absent: saturation of a m +

and the affects of Na+

, which may catalyze or i

The variables that have the greatest effect on reaction rates are temperature and pH, and 

ys reported in by experimentalists. Many minerals 

plots) between dissolution rates and pH, roughly in 

p a given temperature, rates are generally slowest at and near 

as a net charge of zero, usually within one or two pH units of 

ed by H+

, and at high pH, rates 

An example of this behavior is shown in Figure 1 for the mineral albite; the data points at 

100 to 300 °C are from Hellman (1994a), and at 25 °C, fr

curves in Figure 1 are obtained from the data (open symb e

itting (gray curves) and unweighted piecewise linear regression (black curves). Non-linear 

curve f

been quantified.

For further general discussions of mineral dissolution and precipitation, the reader may 

wish to consult Anbeek (1993), Bertrand et al. (1994), Brady and Walther (1989), Casey and 

Sposito (1992), Fleer and Johnston (1986), Gallup (1998), Gérard et al. (1998), Helgeson (19

Jeschke and Dreybrodt (2002a), Kline and Fogler (1981), Lasaga (1984), Lasaga (1995)

teefel and Lasaga (1992), Steefe

N

Lasaga (1994), and Xiao and Lasaga (1996). 

2.2 Data Reduction

In this section, we outline a general strategy for the determination of rate parameters 

conforming to eqn. (6) from experimental data, using the minerals albite and magnesite as 

examples. Albite is used as

ineral surface with a (H ) catalyst, 

nhibit dissolution depending on pH. 

fortunately, these variables are almost alwa

show a U-shaped relation (V-shaped on log

arallel with their solubilities. For

the pH where the mineral surface h

neutral. At low pH, rates increase with decreasing pH catalyz

ncrease with increasing pH, catalyzed by OH- i . 

om Chou and Wollast (1985). The 

ols) using unweighted non-linear curv

f

itting is accomplished by fitting all of the data to a modified version of eqn. (7): 

( ) 1 3 RT n

E

RT

E

RT n

E

A e a A e A e a acid H neut base H dt

dm − acid − neut − base

= − + + + + (9) 

The chemical affinity term has been omitted, because we have selected data that is obtained from

experiments performed under conditions that are far from equilibrium where Ω approaches zero

and the chemical affinity term approaches unity. The data have been normalized to 1.0 m

the surface area term is omitted as well. 

, 2

, and 

6 
Piecewise linear regression is accomplished by first segregating the data into acid, 

neutral, and basic regions, and fitting the groups of data separately to each of the terms in eqn. 

(9). For albite the acidic, neutral, and basic regions were selected by Hellman (1994a) to be in

the ranges of pH 1.3 to 4.0, 5.6 to 8.2, and 8.6 to 10.3 respectively. For the acidic and basic 

mechanisms, the equation 

+

+

⎟

⎠

⎞ ⎜

⎝

⎛ −

= = H

acid

n

H

RT

E

acid A e a

dt

dm

rate (10)

can be transformed into the linear relation 

n pH RT

E rate A

H

acid = acid − − + (2.3025 ) log( ) log( ) (11) 

and for the neutral mechanism, the following relation is used 

(2.3025 ) log( ) log( ) E rate A neutral = neutral − RT (12) 

The black d li in igu lt for

anism C t a rv s t u I c e i

r curve fitting provides a slightly better fit to the data, but for most minerals, lack of 

t i a e o k s i n e b

e res ts for p cew se linear re ression and non-linear regression for albite are shown 

in Table 1 both in term f th Arrh ius re-e onenti facto A and term the rate 

at 25 and p = 0. Our r sult for p ewise near eg ss re i ee ent with 

ecommend application of these 

he

 25 to 300 °C, and pH25°C from 1.3 to 10.3. Albite is one of 

lly determined, but only in alkaline 

fluids (

,

y

ashed straight nes F re 1 show the resu s each of the three

mech s at 100° , and he bl ck cu e represen their s m. t an be se n in F gure 1 that

non-linea

agreemen n the dat among diff rent w r ers make this d ffere c negligi le.

Th ul ie

s o

i

e

g

en p xp al r , in s of

constant °C H e s iec li r re ion a n agr m

those of Hellman (1994a) and Chou and Wollast (1985). We r

parameters only to modeling of systems within the range of conditions under which t

parameters were obtained, i.e. from

the few minerals for which p and q have been experimenta

Alekseyev et al., 1997) at pH = 9; these parameters are also shown in Table 1. 

A second illustrative example is for magnesite dissolution at 25 °C (Pokrovsky and 

Schott, 1999). In this case, magnesite dissolution rates are catalyzed by H+

, and at low pH the

mineral surfaces become saturated with H+

 so that further decrease in pH does not cause further 

increase in dissolution rate. Further, dissolution rates are apparently catalyzed or inhibited by 

Na+

 depending on pH. Finally, magnesite dissolution rates are independent of OH-. These 

experiments were conducted at pH between 0.19 to 10.13 with pH controlled using HCl, NaOH

NaHCO3, and Na2CO3, and ionic strength controlled by NaCl. The results are shown graphicall

in Figure 2. 

7
-4

Albite Dissolution

-7

-6

-5

dis s olution, 1 m 2

) -13

-12

0

g-11

k + -10

dis s olu

-9

-8

Lo ( tion) = Log rate (

2 4 6 8 10 12 14 pH

25°C

100°C

t

black lines: results from piecewise 

linear

Acid Mechanism Neutral Mechanism Base Mechanism 

200°C

300°C

Figure 1. Rates of albite dissolution from 25 to 300 °C and pH from 1.3 to 10.3. Data a

100, 200, and 300 °C (open diamonds, triangles and squares, respectively) from 

Hellman, 1994, and at 25 °C (open circles) from Chou and Wollast, 1985. Dashed 

curves: results from non-linear regression. Straight

regression of 100 °C data. Black curves: sum of results from piecewise linear 

regression. 

Table 1. Albite Dissolution Rate Parameters. 

a

A blog k cE dn aA blog k cE aA blog k cE dn 

Linear 

Regression

3.23E+01 -9.87 65.0 0.457 1.52E+00 -12.04 69.8 2.96E-05 -16.98 71.0 -0.572 

Non-Linear 

Regression

1.66E+01 -10.16 65.0 0.317 6.66E-02 -12.56 65.0 1.11E-04 -15.60 66.5 -0.471

p q p q p q 

e

Chemical

Affinity

-- -- -- -- 0.76 90.0 

a. Arrhenius pre-exponential factor A, mole m-2 s-1 for use with equation (5). 

b. Log rate constant k computed from A and E, 25°C, pH=0, log moles m-2 s-1 for use with equation (6). 

c. Arrhenius activation energy E, kJ mole-1. 

d. Reaction order n with respect to H+

. 

e. Chemical affinity parameters p and q default to unity if not specified. 

8 
In the pH range of 0 to ~3, there is only a minimal dependence of rates on pH, the 

reaction order with respect to activity of H+

 is small, and increased H+ activity leads to only a 

small increase in rates (Figure 2, open squares). This behavior results from the saturation of

reactive surface sites with H+

, and can be described using adsorption isotherms (Pokrovsky and 

Schott, 1999). In the pH range of 3 to 5, faster rates (Fig. 2, open diamonds) apparently result 

from catalysis by Na+

 at ionic strength 0.1 to 0.5, as compared with slower rates in experiments 

with low Na+

 concentration (Fig. 2, open triangles) at ionic strength ≤0.1; this behavior can be 

described using adsorption isotherms for Na+

. Between pH values of 5 and 8, there is minimal 

dependence on the activity of H+ or Na+ (Fig. 2, open triangles) over the entire range of ionic 

strength from 0.01 to 0.5. At pH greater than 8, Na+

 apparently inhibits reaction rates (Fig. 2, 

open circles) at ionic strength from 0.004 to 0.20); again, this behavior can be described using 

adsorption isotherms for Na+

; the fastest rates in this pH range are slightly slower than the rates 

in the near-neutral pH range because alkaline pH values require a finite amount of Na+

 from

NaOH. 

The data used in calculation of magnesite rate parameters are for low ionic strength only 

(≤0.1) in the acidic pH range of 3 to 5, and in the circum-neutral pH range of 5-8 all data are 

used; these data are denoted with open triangles in Figure 2. For non-linear regression, these 

data are simultaneously fit to a form of eqn. (9) from which the term for the basic mechanism has 

been omitted; the data were obtained from experiments at 25 °C only, so the activation energy is 

omitted as well 

( ) 298.15 1 298.15K

neutral

n

H

K Kacid a K

dt

dm

= − + + (13)

For linear regression, the data are fit to a modified form of eqn. (11) for the acidic mechanism

298.15

 (14)

and for the neutral mechanism, a s alculated, yi ding

25 °C and an acidic mechanism (posit ctio der. The gray cur in F show the 

resu e non-linear , the da tr ine

the r th the ac , and the black cu .

ta are la he t tur en of a

activation energies for calcite (discussed below) are used as a first approximation, allowing for 

the c lculation of the pre-ex ential fa rs. The hemical affinity factors p and

direc okrovsky an om experiments in which the 

initial solutions contai 2+ 2- ate parameters 

deri

data cause of the inability of the selected rate equations 

to ac ous rate catalyzing and inhibiting species. However, the 

non rs that are accurate to a

first approximation over a wide range of circum-neutral pH. 

rate K n pH acid H ) = log − +

K log(

imple average is c el the rate constants at

ive) rea n or ves igure 2

lts of th regression

idic and neutral m

black

echanism

shed s

s

aight l s in Figure 2 show separately 

esults for bo rve represents their sum

Since da cking for t empera e dep dence m gnesite dissolution rates, the 

a pon cto c q are taken 

tly from P d Schott (1999), and were derived fr

ned varying amounts of Mg and CO3 . Data for the r

ved from the regression are summarized in Table 2. 

Neither piecewise linear regression nor non-linear curve fitting provide a good fit to the 

under acidic and basic pH conditions, be

count for surface adsorption of vari

-linear curve fitting method allows the calculation of rate paramete

9
Magnesite Dissolution

-7.0

-11.5

-11.0

-10.5

-10.0

-9.5

-9.0

-8.5

-8.0

-7.5

Log 

Rate (

mol m-2 s-1

)

0 1 234 5 6 789 10 11

pH

Figure 2. Rates of magnesite dissolution at 25 °C and pH from 0.19 to 10.13. Data 

25 °C from Pokrovsky and Schott, 1999; open triangles, data used in piecewise lin

regression; open squares, other data. Dashed lines, results from piecewise linear 

regression of acidic and neutral mechanisms. Black curves, sum of results from 

piecewise linear regression. Gray curve, results from non-linear curve fitting. 

Table 2. Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism 

ear

a

A blog k cE dn aA blog k cE 

Linear 

Regression

1.40E-04 -6.38 14.5 0.589 6.05E-06 -9.34 23.5

Non-Linear 

Regression

1.62E+32 32.21 14.5 0.448 4.27E-10 -9.37 23.5 

p q p q e

Chemical 

Affinity 

4.00 1.00 -- -- 

a. Arrhenius pre-exponential factor A, mole m-2 s-1 for use with equation (5). 

b. Log rate constant k computed from A and E, 25°C, pH=0, log mole m-2 s-1 for use with 

equation (6). 

c. Arrhenius activation energy E, kJ mole-1.

d. Reaction order n with respect to H+.

e. Chemical affinity parameters p and q default to unity if not specified. 

10 
2.3 Limitations and Uncertainties

etics to geochemical modeling is subject to a number of limitations 

es in the experimental methods and materials from which the rate 

parameters are derived, and from the modeling software used for the simulations. Ideally, 

available over wide ranges of temperature and pressure for 

dissolution of perfectly crystalline minerals under conditions far from equilibrium i.e. where the 

is large, so that further increases in chemical affinity lead to no observed 

on rates. Additional data would be available to quantify slowing of reaction 

rates as the chemical affinity decreases, as equilibrium is approached with increasing 

concen

minerals 

ite.

ilable

lcite

(Alkattan et al., 1998); 2) in some experimental reactor designs, particle abrasion may lead to 

surface fines which can be removed 

with solvents, but also may produce particles which may chemically re-bind to mineral surfaces

(P ch, 1981b), and/or produce crystal defects at or near mineral surfaces (Bloom, 1983; 

Furrer et al., 1993; Nagy, 1995; Nagy et al., 1991; Petro , 198 eland and Stumm, 1992), 

which may lead to faste l ap rates; d 4) there is also a degree of uncertainty as to 

whether the reactive su rea equate with th omet ET e area

(Aa rd an son ; Ga t al., 2 1; Hel et al., 1984; Lasaga, 1998). At 

leas e stu utie 200 uartz ssolutio s shown that an increase in BET 

surface area during dis n co rimarily of un- tive e wal con

that geometr ce ovid more accurate calculation of dissolution rates.

The rate equation we have selected, eqn. (7), is also subject to furthe atio oes

not account for temperature dependence of the pre-expo ial factor resulting from variation in 

the velocity ion solv ies, no oes it not t for rent pH

dependence of the activation ener ich ca be desc usin rptio herms (Lasaga, 

1995). The selected equation applies only to bulk dissolution rates, and does not account for 

cry ograp tro inera lution e. variation of dissolution rates on different 

crystallographic surface planes. 

Application of kin

resulting from uncertainti

experimental data would be

chemical affinity

increase in reacti

tration of dissolved components that are contained in the mineral structure. Further data 

would be available for dissolved components not contained in the mineral structure that might 

catalyze or inhibit the reactions. Further, data would also be available to account for varying 

mineral compositions in each solid solutions series. Finally, data would be available for

that are not perfectly crystalline, i.e. minerals with crystal defects, cation disordering, or igneous 

exsolution features — for which the required number of experiments would be nearly infin

Most of these data do not yet exist, and for those minerals for which data exist, data are ava

mostly for experiments conducted only under conditions that are far from equilibrium, and 

values for p and q are assumed to be equal to unity, which is likely incorrect. 

Additional limitations include various factors of experimental design and solid phase 

preparation: 1) stirring rates may be insufficient to ensure that there are not concentration 

gradients near mineral surfaces, which may slow dissolution reactions(Alkattan et al., 1998; 

Metz and Ganor, 2001), especially for minerals that have fast overall rates such as ca

faster apparent rates; 3) grinding of samples may produce

etrovi

vich 1b; Wi

r initia parent an

rface a can be d e ge ric or B surfac s

gaa d Helge , 1982 utier e 00 geson

t on dy (Ga r et al., 1) of q di n ha

solutio nsists p reac tch pit ls, and cludes

ic surfa area pr es for

r limit ns. It d

nent

in solut of dis ed spec r d does accoun appa

gy, wh n ribed g adso n isot

stall hic con l of m l disso , i.

11
3. SU

3.1 Tecto tes

3.1.1 SiO2 orp

3.1 Qua

ate d pa ters for quartz from several sources were evaluated (Bennett, 1991; 

Bennett et al., 1988; Bird et al., 1986; Blake and Walter, 1999; Brady, 1992; Dove, 1994; Dove, 

1999; Dove and Crerar, 1990; Dove and Elston, 1992; Dove and 97; r et 01;

Knauss and Copenhaver, 1995; Knauss and W ry, 1988; Rimstidt and Barnes, 1980; 

Schwartzentruber et al., 1987; Tester et al., 1994; Welch d Ullm 92) from er et

al. were sele r the al pH m ecause utho ab orrel

con ntly per al resu with the esults o ny w incl Ben

(1991), Berger et al. (1994), Blum et al. (1990), Brady and Walther (1990), Dove and Crerar 

(19 Kita 960) stidt a Barnes ( 980), Sie ert et al. (1963), Van Lier et al. (1960), 

In the acidic region, dissolution 

tes are apparently independent of pH (Dove, 1994; Knauss and Wolery, 1988; Rimstidt and 

arnes, 1980), and can be equated with rates in the neutral region at identical T and P. The data 

sed to

RE LTS

silica

Polym hs

.1.1 rtz

R data an rame

Nix, 19 Gautie al., 20

ole

an an, 19 . Data Test

cted fo neutr mechanis b the a rs were le to c ate

siste their ex iment lts r f ma orkers, uding nett

90), hara (1 , Rim nd 1 b

and Weill and Fyfe (1964) at temperatures from 25 to 625 °C.

ra

B

u regress rate parameters using eqn. (11) for neutral pH are shown in Table 3. 

Table 3. Quartz dissolution Rate Data in Pure H2O. 

T, °C T, K alog k blog k T, °C T, K alog k blog k

23 296.15 -13.41 -14.24 400 673.15 -4.45 --

23 296.15 -13.38 -14.21 400 673.15 -4.35 --

50 323.15 -12.22 -13.05 440 713.15 -4.16 -- 

323.15 -12.21 -13.04 440 713.15 -4.35 --

50 323.15 -12.19 -13.02 440 713.15 -4.51 --

70 343.15 -11.33 -12.18 480 753.15 -4.41 --

100 373.15 -10.19 -11.03 480 753.15 -4.19 --

100 373.15 -10.22 -11.06 70 343.15 -12.16 -12.22

100 373.15 -10.20 -11.04 80 353.15 -11.46 -11.52

100 373.15 -10

125 398.15 -9.32 

50

.45 -11.3 90 363.15 -11.16 -11.22 

-10.17 248 521.15 -6.08 -- 

125 398.15 -9.20 -10.05 250 523.15 -5.98 -- 

125 398.15 -9.08 -9.93 269 542.15 -5.84 -- 

125 398.15 -9.17 -10.02 291 564.15 -5.55 -- 

125 398.15 -9.19 -10.03 315 588.15 -5.22 -- 

125 398.15 -9.55 -10.4 332 605.15 -5.02 -- 

125 398.15 -9.75 -10.6 400 673.15 -3.95 -- 

125 398.15 -9.58 -10.43 625 898.15 -2.97 -- 

125 398.15 -9.82 -10.67 105 378.15 -10.27 -11.5 

125 398.15 -9.59 -10.44 145 418.15 -8.36 -9.59 

150 423.15 -8.42 -9.26 170 443.15 -8.43 -9.66 

150 423.15 -8.48 -9.33 265 538.15 -6.56 -7.79 

Table 3. Quartz dissolution Rate Data in Pure H2O - continued. 

12 
T, °C T, K a

log k blog k T, °C T, K alog k blog k

175 448.15 -8.38 -9.23 305 578.15 -6.14 -7.37 

175 448.15 -8.34 5 -10.75 -11.18 

175 448.15 -8.38 353.15 -10.89 -11.25 

175 448.15 80 353. 1.52

175 448. -8.32 -9.16 200 473 -7.63 -7.93 

473 -7.88 -8.72 200 473. -7.35 -7.65 

473 -7.82 -8.67 200 473.1 -7.28 -7.58 

473 -7.05 -- 200 473.1 -7.38 -7.68 

473 -7.21 -- 200 473.1 -7.26 -7.56 

473. -7.30 -- 201 474.1 -7.43 -7.73 

523.1 -6.67 -- 250 523 -6.74 .04

-5.97 

-6.01 -6.31 

-- 300 573.15 -6.15 -6.45 

-- 40 313.15 -13.13 -12.7 

50 323.15 -11.73 -12.3 

60 333.15 -11.33 -11.9 

70 343.15 -10.83 -11.4 

221 494.15 -6.96 -- 200 473.15 -6.84 -7.92 

221 494.15 -7.12 -- 300 573.15 -5.38 -6.46 

253 526.15 -6.38 -- 300 573.15 -5.63 -6.71 

a. Log mole m s , calculated by Tester et al. (1994) using geometric surface area 

b. Log mole m-2 s-1, calculated by Tester et al. (1994) using BET surface area 

-9.19 80 353.1

-9.23 80

-8.28 -9.12 15 -10.99 -1

15 .15

200 15

200

.15

.15 5

200 .15 5

200 .15 5

200 15 5

250 5 .15

5

-7

184 457.15 -7.96 -- 300 573.1 -6.27 

184 457.15 -8.10 -- 300 573.15

184.5 457.65 -8.32

202 475.15 -7.31

202.5 475.65 -7.49 -- 

203 476.15 -7.29 -- 

215 488.15 -7.05 -- 

221 494.15 -6.89 -- 70 343.15 -10.93 -11.5

255 528.15 -6.50 -- 

-2 -1

ism

for rates under alkaline conditions, which are given terms of reaction order with respect 

to OH .

ic

re summarized in Table 4. The source

f the small difference between our results and those of Tester et al. (1994) is uncertain. The 

hemical affinity parameters were not determined, and the chemical affinity parameters p and q

Another series of studies from Dove and co-workers (Dove, 1994; Dove, 1999; Dove and 

Crerar, 1990; Dove and Elston, 1992; Dove and Nix, 1997) demonstrate an important 

phenomenon, that sodium ion catalyzes the OH-

-catalyzed (base) dissolution reaction mechan

(as do Li, K, Mg, Ca, and Ba). These data were not used because adsorption isotherms must be 

used to implement their results; therefore, we use the results from Knauss and Wolery (1988) 

directly

-

Results from the regression calculations for the neutral mechanism using both geometr

and BET surface area performed herein and those performed by Tester et al. (1994), and results 

from Knauss and Wolery (1988) for the base mechanism a

o

c

are assumed to be unity. 

13
Table 4. Quartz Dissolution Rate Parameters. 

Linear Regression Parameters

Neutral Mechanism Base Mechanism a b

log k blog c A E cE aA k dn e

quart 3 .9 -- -- f

quart 2 .1 -- -- g

quart 2 .6 -- -- h

quart 2 .7 -- -- i

quart -- -16.29 66 .5

a. Arrhenius pre-expone r A, mole with equation (5). 

b. log rate constant k co m A and pH=0, log mo m-2 s-1 for use quation (6

c. Arrh activation e J mole-1

d. Reaction order n with respect to H+.

a.

ace area. 

From Knauss and Wolery (1988), A adjusted here from 491 to 10 to be consistent with the results of Tester et al. (1994).

z 33 -13.40 90 -- -- 

z 76 -13.34 90 -- -- 

z 3.3 -13.99 87 -- -- 

z 4 -13.99 87 -- -- 

z -- -- -2 -110 1083 -0

ntial facto

mputed fro

m s for use 

E, 25°C, le with e ).

enius nergy E, k .

e. Calculated using geometric surface area. 

f. Calculated by Tester et al. (1994)using geometric surface area. 

g. Calculated using BET surface are

h. Calculated by Tester et al. (1994)using BET surf

i.

3.1.1.2 Amorphous SiO2, Cristobalite, and SiO2 Polymorph Precipitation 

culated rate equation p for am us silica d tion from

Icenhower and Dove (2000), and Rimstidt and 80) w luated. D rom

Icenho 00) were selected beca onduc ny individual experimental 

runs, and they were able to correlate their data with data from o rkers. Th parameters 

are sum able 6. The presence of sm ts of solution ficantly

enhances dissolution rates (21x at 0.05m Incenhower and Dove, 2000), this can be accounted for 

by using adsorption isotherms, but cannot be de ith ou ted rate eq ns (eqns. 5

and 6) 

iled directly from Rimstidt 

and Ba under the assumption 

that th 1980),

nd eq

Table 5. Amorphous Silica Dissolution Rate Data in Pure H2O. 

T, °C T, K alog k T, °C T, K alog k 

Rate data and cal arameters orpho issolu

Barnes (19 ere eva ata f

wer and Dove (20 use they c ted ma

ther wo e rate

marized in T all amoun NaCl in signi

scribed w r selec uatio

Rate parameters for α-cristobalite and β-cristobalite are comp

rnes (1980). The rate parameters were calculated by the authors

e precipitation rates for all of the SiO2 polymorphs are equal (Rimstidt and Barnes,

a n. (8). These data are also summarized in Table 6. 

40 313.15 -11.36 80 353.15 -10.47 

40 313.15 -11.17 80 353.15 -10.47 

60 333.15 -10.75 250 523.15 -6.59 

60 333.15 -10.84 225 498.15 -6.86 

60 333.15 -10.63 225 498.15 -6.96 

60 333.15 -10.57 200 473.15 -7.4 

60 333.15 -10.65 200 473.15 -7.34 

60 333.15 -10.99 175 448.15 -7.89 

60 333.15 -10.97 175 448.15 -7.74 

14 
Table 5. Amorphous Silica Dissolution Rate Data in Pure H2O - continued. 

T, °C T, K alog k T, °C T, K alog k 

60 333.15 -10.92 150 423.15 -8.41 

60 333.15 -10.98 150 423.15 -8.53 

60 333.15 -10.93 225 498.15 -6.86 

60 333.15 -10.97 225 498.15 -7.05

60 333.15 -10.93 200 473.15 -7.24

60 333.15 -11.05 200 473.15 -7.27

60 333.15 -11.22 175 448.15 -7.97

60 333.15 -11.2 175 448.15 -8.1

60 333.15 -11.15 150 423.15 -8.24

60 333.15 -11.18 125 398.15 -8.75

60 333.15 -11.09 100 373.15 -9.36

80 353.15 -10.28 100 373.15 -9.54

a. Log mole m-2 s-1 for use with equation (6); data for experiments in de-ionized water only, from 

Icenhower and Dove, 2000.

Table 6. Amorphous Silica and Cristobalite Dissolution, and Silica Polymorph 

Precipitation Rate Parameters. 

Neutral Mechanism

Dissolution aA blog c k E 

d

Amorphous Silica 6.65E+00 -12.23 74.5 e

Amorphous Silica 1.01E+01 -12.31 76.0 

f

Amorphous Silica 1.85E-01 -12.77 68.7 

f

α-cristobalite 1.20E-01 -12.31 65.0

f

β-cristobalite 7.60E-02 -12.14 62.9

Precipitation f

All SiO2 polymorphs 2.02E-01 -9.42 49.8 

a. Arrhenius pre-exponential factor A, mole m-2 s-1 for use with equation (5). 

b. log rate constant k at 25°C and pH = 0, log mole m-2 s-1 for use with equation (6).

c. Arrhenius activation energy E, kJ mole-1. 

d. Reported values for k and E from Incenhower and Dove (2000), A calculated herein. 

e. A and E regressed using data from Incenhower and Dove (2000), Table 5; k calculated from A and E herein. 

f. Reported values for k and E from Rimstidt and Barnes (1980); A calculated from k.

15
3.1.2 Feldspars 

3.1.2.1 Plagioclase Feldspars

re evaluated from Alekseyev et al. (1997), Amrhein 

and Suarez (1988), Amrhein and Suarez (1992), Berg and Banwart (2000), Bevan and Savage 

(198 ter (199 ), Blak Blum d Stilli

a lther (1989), Brantley and Sti (199 Bur l. (19 3), B erg Cle

(1976), Carroll and Knauss (2001), Casey et al 91) and posito 92), a

Brantley (1997), Chen et al. (2000), Chou and Wollast (1984), Ch and W last ),

et al. (2003), Fleer and Johnston (1986),Gautier et al. (1994), Haja et al. 98), es

al. 84) H en rner 979), dren and Speyer (1987), Hellma 994 ell

(1994a), Hellman ( Kna s and lery ), and openh r (19 La

(19 , Lag (1 üttg et al. ( 9), M y a ns (1 86), M kam (1

Mu y an lge 87; 1 89), O ers e 19 lkers nd Sc (19 el

and Gislason (2001), Oelkers (2001b), Oxburgh et al. (1994), Rafal'skiy e 199 afa

an syag (199 illing et al. ), S gs 996 Swoboda-Colberg and 

D (19 Talm d Ne itt (1 Tay t al 0a), T uzuki Suzu 198

Teng et al. (2001), Utsunomiy et al. ), W an an (1 92), W an lma

(1993), We nd n (19 6), an lch llm 000).

Unlike the plagioclase endmem albi cus ove, issolu ates the

re der o pl ase so lution seri strain os he

available data are b owar low t u d n utral acid (B nd

Stillings, 1995). One important but poorly qua ed o tion that di olution rates 

in e co ous h inc effect is more pronounced for 

m nort com ons; 25°C and pH = 5, rates increase by approximately one order of 

m ude albite (log k ≈ 12 lo -2 to l rite ( g k ≈ -11 log mo

-2

 s

-1), 

and by alm ree s of m gnitu twe bra and anorthite (log k ≈ -8 log mo

m inishes with decreasing pH, and the 

difference in the logarithm of rate approaches a linear relation with respect to composition at pH 

= 2. A secon observ tion tha as no n w uan s tha issolut n activ ion ene y

decreases with increa g anorthite content. 

Our general strategy is to identify data from various workers that are consistent with one 

sible rate data are selected from experiments in 

ow-through reactors, where dissolution rates were measured using the concentration of 

issolved silica in the reactor output fluid, and where silica concentrations were allowed to reach 

eady-state, thus indicating steady-state thickness of any possible leached layer. One issue not 

ddressed in the cited works is the extent to which cation disorder in the minerals may affect the 

iven rates. Data were selected for the plagioclase solid solution series, and are summarized in 

bles as follows: albite, Table 7; oligoclase, Table 8; andesine, Table 9; labradorite, Table 10; 

ytownite, Table 11; anorthite, Table 12. Primary constraints are the data and results for albite 

= 25 to 300 °C, pH = 1.3 to 10.3) and anorthite (T = 8 to 95 °C, pH = 2.43 to 10.2), with 

interpolation obtained graphically for the components of the solid solution. The derived 

parameters are summarized in Table 13. Chemical affinity parameters p and q for albite are 

Plagioclase dissolution rate data we

9), Blake and Wal 6 e and Walter (1999), an ngs (1995), Brady

nd Wa llings 4), ch et a 9 usenb and mency

. (19 , Casey S (19 Chen nd

ou ol (1985 Fenter

sh (19 Helg on et

(19 oldr and Be (1 Hol n (1 b), H man 

1995), us Wo (1986 Knauss C ave 95), gache

65) ache 976), L e 199 anle nd Eva 9 ura i et al. 998),

rph d He son (19 9 elk t al. ( 94), Oe a hott 95), O kers

t al. ( 0), R l'skiy 

d Pri ina 1), St s (1995 tillin et al. (1 ),

rever 93), an an sb 988),

(1999

lor e

elch

. (200

d Ullm

s and

elch

ki (

d Ul

0),

a 9 n

lch a Ullma 9 d We and U an (2

ber te dis sed ab d tion r for

main f the agiocl lid so es are not as well con ed. M t of t

iased t d emperat re an ear-ne to ic pH lum a

ntifi bserva is ss

creas ntinu ly wit reasing anorthite content. This

ore a hitic positi at

agnit from - g mol m s

-1) abrado lo l m

ost th order a de be en la dorite l

-2

 s

-1) (Blum and Stillings, 1995). This effect dim

d a t h t bee ell q tified i t d io at rg

sin

another as primary constraints, and to interpolate pre-exponential factors and activation energies 

that are consistent with the data. Wherever pos

fl

d

st

a

g

ta

b

(T

16 
0.760 and 90.0 respectively (Alekseyev et al., 1997), but their use in modeling should be limited 

to conditions near the experimental conditions under which they were obtained, 300 °C and pH = 

9. 

Table 7. Albite Dissolution Rate Data. 

Acid Mechanism Neutral Mechanism Base Mechanism 

T, °C a log k a pH log k T, °C pH T, °C pH log k 

25 1.1 -10.25 25 5.1 -11.82 25 9.95 -10.97 

25 2 -1 5 -11. 95 -11.05 

2 -1 2 -11. 95 -11.13 

-1 5 -11. 5

- 1 -11. 1.2 -10.55 

- 4 -11. .55 -10.6 

1 -11.47 25 7.73 -11.83 25 12.3 -10.38 

7.95 -11.67 100 10.3 -8.92 

100 2.0 -9.07 100 5.7 -9.47 200 9.3 -7.15 

100 4.0 -9.00 100 5.7 -9.62 300 8.6 -6.25 

100 4.0 -9.50 100 7.7 -9.35 300 8.6 -6.01 

100 4.0 -9.38 100 8.2 -9.77 300 9.2 -5.97 

200 2.0 -6.72 172 5.7 -8.09 300 9.2 -5.46 

200 2.0 -6.63 191 5.6 -7.61 300 10.0 -5.29 

200 2.0 -6.80 200 5.6 -7.79 

200 4.0 -7.54 200 7.5 -7.79 

300 1.3 -5.13 222 5.6 -7.27 

300 2.2 -5.17 300 5.7 -6.35 

300 2.2 -5.57 300 5.7 -6.44 

300 3.4 -6.06 300 5.7 -6.30 

300 4.0 -6.36 300 6.8 -6.13 

 300 7.4 -6.30 

 300 7.7 -5.92 

 300 7.7 -6.03 

a. Log mole m-2 s-1. Data at 25 °C from Chou and Wollast (1985), for Amelia albite, composition not specified. Data from 100 to 300 

°C from Hellman (1984), for Amelia Albite, Ab100An0Or0 (1984). 

.05 0.5 25 5.35 75 25 9.

25 .45 0.8 25 5.47 65 25 9.

25 2.9 1.2 25 5.63 83 25 10.6 -10.9

25 3 11. 25 5.63 92 25 1

25 3.5 11. 25 5.73 92 25 11

25 4.

100 2.0 -9.05 25

17
Table 8. Oligoclase Dissolution Rate Data.

a

Composition

an ab or T, °C bpH clog k Source 

20 -- -- 25 2 -10.85 Casey et al., 1991

20 -- -- 25 2 -10.44 Casey et al., 1991

21 -- -- 25 2 -10.69 Casey et al., 1991 

13 -- -- 25 3 -11.47 Oxburgh et al., 1994 

20 -- -- 25 3 -10.94 Holdren and Speyer, 1987

-

7 cy, 1976 

a. -- = Not given

b. Acid mechanism, pH 2-4. tral mechanism, pH 5.1-7. 

c. Log mole m-2

13 -- -- 25 3.6 -11.70 Oxburgh et al., 1994 

13 -- - 25 4 -11.92 Oxburgh et al., 1994

13 -- -- 25 4.6 -12.22 Oxburgh et al., 1994 

13 -- -- 25 5.1 -12.10 Oxburgh et al., 1994 

24 0 6 25 5.3 -11.59 Busenberg and Clemen

22 73 

-- 

5 25 5.4 -11.63 Stillings et al., 1996

13 -- 25 7 -11.96 Oxburgh et al., 1994 

.

6; neu

s

-1.

18 
Table 9. Andesine Dissolution Rate Data.

a

Composition

an ab or T, °C bpH clog k Source 

46 -- -- 25 2 -10.16 Casey et al., 1991 

46 -- -- 25 2 -10.01 Casey et al., 1991 

46 -- -- 25 3 -10.64 Holdren and Speyer, 1987

49 -- -- 22 3.1 -9.78 Welch & Ullman., 1993 

49 -- -- 22 3.1 -9.27 Welch & Ullman., 1993 

46 -- -- 25 3.1 -10.65

-1

Oxburgh et al., 1994 

47 51 2 25 3.13 0.62 Stillings et al., 1996 

49 

49 

-- 

-- 

-- 

-- 

22 

22 

3.8 

4.1 

-10.12

-9.81 

Welch & Ullman., 1993 

Welch & Ullman., 1993 

46 -- -- 25 4.1 -11.15 Oxburgh et al., 1994 

47 51 2 25 4.11 -11.15 Stillings et al., 1996 

47 51 2 25 5.08 

4

993

mency, 1976 

993

993

991

991

a. -- = Not given

b. Acid mechanism, pH 2-4. utral nis .1-7. echanis , pH

c. Log mole m-2 s

-11.24 Stillings et al., 1996 

46 -- -- 25 5.1 -11.24 Oxburgh et al., 199

49 -- -- 22 5.3 -10.47 Welch & Ullman., 1

43 50 8 25 5.3 -11.86 Busenberg and Cle

49 -- -- 22 5.6 -10.51 Welch & Ullman., 1

43 50 7 25 5.61 -11.52 Stillings et al., 1996

49 -- -- 22 5.7 -10.78 Welch & Ullman., 1

49 -- -- 22 5.8 -10.74 Welch & Ullman., 1993 

35 65 0 250 6.83 -8.48 Rafal'skiy and Prisyagina, 1

47 51 2 25 7.22 -11.21 Stillings et al., 1996 

46 -- -- 25 7.3 -11.29 Oxburgh et al 1994 

35 65 0 150 7.46 -9.39 Rafal'skiy and Prisyagina, 1

49 -- -- 22 7.7 -10.7 Welch & Ullman., 1993 

49 -- 

.

-- 22 9 -10.31 Welch & Ullman., 1993 

11; Ne mecha m, pH 5 7; base m m 9. -1.

19
Table 10. Labradorite Dissolution Rate Data.

a

Composition

an ab or T, °C bpH clog k Source 

51 -- -- 230 0.41 -6.44 Tsuzuki and Suzuki, 1980

51 -- -- 245 0.45 980

980

980

0.98 

980

, 1980

1.69 980

1976

-- 31 3.2 -9.45 Carroll and Knauss, 2001 

.02 Carroll and Knauss, 2001 

60 -- -- 61 3.2 -8.37 Carroll and Knauss, 2001 

60 -- -- 100 3.2 -8.34 Carroll and Knauss, 2001 

60 -- -- 30 3.21 -9.53 Carroll and Knauss, 2001 

60 -- -- 130 3.22 -7.67 Carroll and Knauss, 2001 

60 -- -- 100 3.24 -8.11 Carroll and Knauss, 2001 

60 -- -- 130 3.24 -7.66 Carroll and Knauss, 2001 

60 -- -- 100 3.25 -8.09 Carroll and Knauss, 2001 

60 -- -- 60 3.29 -8.83 Carroll and Knauss, 2001 

60 -- -- 100 3.29 -8.31 Carroll and Knauss, 2001 

60 -- -- 130 3.3 -7.72 Carroll and Knauss, 2001 

60 -- -- 100 3.37 -8.52 Carroll and Knauss, 2001 

60 -- -- 150 3.5 -7.18 Carroll and Knauss, 2001 

57 43 0 200 4.88 -8.48 Lagache, 1965 

53 44 3 25 5.3 -11.9 Taylor et al., 2000 

70 -- -- 80 6 -9.01 Blake and Walter, 1999 

a. -- = Not given. 

b. Acid mechanism, pH 0.84-6. 

c. Log mole m-2 s-1.

-6.48 Tsuzuki and Suzuki, 1

51 -- -- 230 0.81 -6.35 Tsuzuki and Suzuki, 1

51 -- -- 245 0.84 -6.71 Tsuzuki and Suzuki, 1980

51 -- -- 230 0.96 -6.71 Tsuzuki and Suzuki, 1

51 -- -- 245 -6.71 Tsuzuki and Suzuki, 1980

51 -- -- 230 1.21 -7.6 Tsuzuki and Suzuki, 1

51 -- -- 245 1.23 -7.48 Tsuzuki and Suzuki

51 -- -- 230 1.67 -7.48 Tsuzuki and Suzuki, 1980

51 -- -- 245 -7.44 Tsuzuki and Suzuki, 1

60 -- -- 25 2 -9.85 Busenberg and Clemency,

61 -- -- 25 3.2 -10.6 Casey et al., 1991 

61 -- -- 25 3.2 -10.5 Taylor et al., 2000 

61 -- -- 25 3.2 -10.5 Taylor et al., 2000 

61 -- -- 25 3.2 -10.6 Taylor et al., 2000 

61 -- -- 25 3.2 -10.5 Taylor et al., 2000 

61 -- -- 25 3.2 -10.6 Taylor et al., 2000 

60 --

60 -- -- 60 3.2 -9

20 
Table 11. Bytownite Dissolution Rate Data.

a

Composition

an ab or T, °C pH blog k Source 

76 -- -- 25 2 -9.74 Oxburgh et al., 1994

76 -- -- 25 3 -9.7 Oxburgh et al., 1994

3.1 

4.4 ., 1994

5.3 

5.65 

976

a. -- = Not given. 

b. Acid mechanism, pH 2-5. tral mechanism, pH 5.65-7.

c. Log mole m-2 s

76 -- -- 25 -10.31 Oxburgh et al., 1994

77 -- -- 35 3.2 Welch and Ullman, 2000 

3.8 

-11.13

76 -- -- 25 -10.91 Oxburgh et al., 1994 

77 -- -- 22 4 -8.69 Welch and Ullman, 1993 

76 -- -- 25 -10.91 Oxburgh et al

76 -- -- 25 4.75 -8.67 Casey et al., 1991 

77 -- -- 22 4.9 -8.89 Welch and Ullman, 1993 

76 -- -- 25 5 -10.97 Oxburgh et al., 1994 

76 -- -- 25 -9.91 Holdren and Speyer, 1987

77 -- -- 5 -11.86 Welch and Ullman, 2000 

77 -- -- 20 5.65 -11.4 Welch and Ullman, 2000 

76 24 0 25 5.65 -10.76 Stillings et al., 1996 

77 22 -- 25 5.65 -11.97 Busenberg and Clemency, 1

77 -- -- 22 5.7 -10.2 Welch and Ullman, 1993 

77 -- -- 22 7.2 -10.12 Welch and Ullman, 1993 

3; Neu 2. -1.

21
Table 12. Anorthite Dissolution Rate Data.

a

Composition

an ab or T, °C pH blog k Source 

100 0 0 25 2 -10.32 Fleer, 1982 

100 0 0 50 2 -9.72 Fleer, 1982 

100 0 0 70 2 -9.59 Fleer, 1982 

92 -- -- 25 3 -9.77 Holdren and Speyer, 1987

93 -- -- 25 3.6 -10.24 Amrhein and Suarez, 1992

97 -- -- 60 2.53 -6.78 Oelkers and Schott, 1995 

unk -- -- 25 4 -10.65 Bailey, 1974 

unk -- -- 45 4 -10.35 Bailey, 1974 

unk -- -- 65 4 -10.35 Bailey, 1974 

93 -- -- 25 4.45 -10.83 Amrhein and Suarez, 1992

93 -- -- 25 4.65 -11.33 Amrhein and Suarez, 1992

93 -- -- 25 4.7 -11.27 Amrhein and Suarez, 1992

93 -- -- 25 6 -10.14 Amrhein and Suarez, 1992

93 -- -- 25 6 -10.69 Amrhein and Suarez, 1992

100 0 0 25 6.7 -10.83 Berg and Banwart, 2000 

100 0 0 25 7.4 -11.15 Berg and Banwart, 2000 

93 -- -- 25 7.65 -11.37 Amrhein and Suarez, 1992

100 0 0 25 8.1 -11.11 Berg and Banwart, 2000 

100 0 0 25 8.4 -10.82 Berg and Banwart, 2000 

100 0 0 70 10.2 -11.41 Fleer, 1982 

97 -- -- 45 2.46 -6.79 Oelkers and Schott, 1995 

97 -- -- 45 2.47 -6.86 Oelkers and Schott, 1995 

97 -- -- 45 2.65 -7.09 Oelkers and Schott, 1995 

97 -- -- 45 2.56 -7.01 Oelkers and Schott, 1995 

97 -- -- 45 2.56 -7.06 Oelkers and Schott, 1995 

97 -- -- 45 2.58 -6.97 Oelkers and Schott, 1995 

97 -- -- 45 2.48 -6.94 Oelkers and Schott, 1995 

97 -- -- 60 2.53 -6.65 Oelkers and Schott, 1995 

97 -- -- 60 2.78 -7.09 Oelkers and Schott, 1995 

97 -- -- 60 2.54 -6.75 Oelkers and Schott, 1995 

97 -- -- 60 2.65 -6.94 Oelkers and Schott, 1995 

97 -- -- 60 2.56 -6.82 Oelkers and Schott, 1995 

97 -- -- 60 2.52 -6.76 Oelkers and Schott, 1995 

97 -- -- 60 2.52 -6.74 Oelkers and Schott, 1995 

97 -- -- 60 2.51 -6.58 Oelkers and Schott, 1995 

97 -- -- 60 2.72 -6.92 Oelkers and Schott, 1995 

97 -- -- 60 2.54 -6.77 Oelkers and Schott, 1995 

97 -- -- 60 2.77 -7.04 Oelkers and Schott, 1995 

97 -- -- 60 2.52 -6.70 Oelkers and Schott, 1995 

97 -- -- 60 2.62 -6.87 Oelkers and Schott, 1995 

97 -- -- 60 2.50 -6.68 Oelkers and Schott, 1995 

97 -- -- 60 2.65 -6.96 Oelkers and Schott, 1995 

97 -- -- 60 2.78 -7.16 Oelkers and Schott, 1995 

22 
Table 12. Anorthite Dissolution Rate Data - continued. 

a

Composition

an ab or T, °C pH blog k Source 

97 -- -- 60 2.74 -7.13 Oelkers and Schott, 1995 

97 -- -- 60 2.68 -7.00 Oelkers and Schott, 1995 

97 -- -- 60 2.63 -6.94 Oelkers and Schott, 1995 

97 -- -- 60 2.81 -7.21 Oelkers and Schott, 1995 

97 -- -- 60 2.59 -6.93 Oelkers and Schott, 1995 

97 -- -- 60 2.56 -6.89 Oelkers and Schott, 1995 

97 -- -- 60 2.71 -7.14 Oelkers and Schott, 1995 

97 -- -- 60 2.54 -6.90 Oelkers and Schott, 1995 

97 -- -- 60 2.56 -6.64 Oelkers and Schott, 1995 

97 -- -- 60 2.60 -6.77 Oelkers and Schott, 1995 

97 -- -- 60 2.75 -7.06 Oelkers and Schott, 1995 

97 -- -- 60 2.66 -6.92 Oelkers and Schott, 1995 

Oelkers and Schott, 1995 

97 -- -- 60 2.55 -6.85 Oelkers and Schott, 1995 

97 -- 2.70 O lkers an

97 - 2.61 O lkers

- -- 60 2.72 O lkers hott,

- 2.58 O lkers hott,

- - 2.77 O lkers a Schott, 1995 

- - 2.65 O lkers a Schott, 1995 

- - 2.63 O lkers a Schott, 1995 

- - 2.46 O lkers a Schott, 1995 

- - 2.41 O lkers a Schott, 1995 

Oelkers and Schott, 1995 

2.51 -6.61 Oelkers and Schott, 1995 

60 2.55 -6.72 Oelkers and Schott, 1995 

97 -- -- 60 2.61 -6.88 Oelkers and Schott, 1995 

97 -- -- 60 2.53 -6.74 Oelkers and Schott, 1995 

-- 60 2.58 -6.94 Oelkers and Schott, 1995 

97 -- -- 60 2.67 -6.77 Oelkers and Schott, 1995 

97 

5

75 2.61 -6.78 Oelkers and Schott, 1995 

97 -- -- 75 2.67 -6.86 Oelkers and Schott, 1995 

97 -- -- 60 2.51 -6.70 

-- 60 

-- 60

-7.13 e d Schott, 1995 

- -7.02 hott,

-6.96

e

e

and Sc

and Sc

1995

97 995

97 

-

-- and Sc

1

- 60 -6.72 e 1995

97 - - 60 -7.10 e nd

97 - - 60 -6.89 e nd

97 - - 60 -6.85 e nd

97 - - 60 -6.70 e nd

97 - - 60 -6.55 e nd

97 -- -- 60 2.62 -6.81 

97 -- -- 

97 -- -- 

60 

97 -- 

-- -- 60 3.08 -7.52 Oelkers and Schott, 1995 

97 -- -- 60 2.90 -7.22 Oelkers and Schott, 1995 

97 -- -- 60 2.87 -7.16 Oelkers and Schott, 1995 

97 -- -- 60 3.00 -7.40 Oelkers and Schott, 1995 

97 -- -- 60 2.91 -7.28 Oelkers and Schott, 1995 

97 -- -- 60 2.94 -7.38 Oelkers and Schott, 1995 

97 -- -- 75 2.52 -6.53 Oelkers and Schott, 1995 

97 -- -- 75 2.54 -6.63 Oelkers and Schott, 1995

97 -- -- 75 2.71 -6.94 Oelkers and Schott, 1995 

97 -- -- 75 2.56 -6.69 Oelkers and Schott, 199

97 -- -- 

23
Table 12. Anorthite Dissolution Rate Data - continued.

a

Composition

an ab or T, °C pH blog k Source 

97 -- -- 75 2.51 -6.63 Oelkers and Schott, 1995

97 -- -- 75 2.50 95

2.65 95

2.60 95

2.53 95

2.73 95

2.58 95

2.55 95

2.68 95

2.58 95

-6.61 Oelkers and Schott, 19

97 -- -- 95 -6.71 Oelkers and Schott, 19

97 -- -- 95 -6.61 Oelkers and Schott, 19

97 -- -- 95 -6.48 Oelkers and Schott, 19

97 -- -- 95 -6.91 Oelkers and Schott, 19

97 -- -- 95 -6.59 Oelkers and Schott, 19

97 -- -- 95 -6.54 Oelkers and Schott, 19

97 -- -- 95 -6.80 Oelkers and Schott, 19

97 -- -- 95 -6.64 Oelkers and Schott, 19

Tab 13. P iocla Dis ion te Pa ters.

Acid chan Neu echani anism 

le lag se solut Ra rame

Me ism tral M sm Base Mech

g k a b E cn alo bE cn log k E alog k b

Albite -10.16 65.0 0.457 -12.56 69.8 -15.60 71.0 -0.572 

Olig lase .67 .0 7 -11.84 69 8 -- 

Andesine .88 .5 1 -11.47 57 4 -- 

Labradorite .87 .1 6 -10.91 45.2 -- 

Byt nite .85 .3 8 -9.82 31.5 -- 

Ano ite .50 .6 1 -9.12 17.8 -- 

a. R constan mpute A and E, 25°C, , mol

b. A nius act n ener kJ mo

c. R tion orde ith respect to H+

oc -9 65 0.45 . -- -- 

-8 53 0.54 . -- -- 

-7 42 0.62 -- -- 

ow -5 29 1.01 -- -- 

rth -3 16 1.41 -- -- 

ate t k co d from pH = 0 e m-2 s-1

rrhe ivatio gy E, le-1. 

eac r n w

3.1.2.2 K-feldspar 

Diss ion r data eva ted f leksey et Savage

(19 ), Bla nd W r (19 Bl d (1999 Blu ),

Busenberg and Clem y (1 Fe t a ), Gau er e n et al.

(19 ), Hol and yer ( 7), ss enhav r (1 ), Manley

and Evans (1986), Rafal'skiy l. (1 , an et al. 001 re taken

directly from Blum a Stilli ec anis herein for

the utral hanis rom data (Table 14) in Helgeson et al. ( ic

mechanism data (Table 14) in Bevan an ge (19 9), B (1995),

Gautier et al. (1994), Knauss & Copenhaver ( . The d rive re

summarized in Table 15. 

olut ate were lua rom A ev al. (1997), Bevan and

89 ke a alte 96), ake an Walter

l 3

), m and Stillings (1995

enc 976), nter e . (200 ti t al. (1994), Helgeso

84 dren Spe 198 Knau and Cop e 995), Lagache (1976

et a 990) d Teng (2 ). Rate parameters a

nd ngs (1995) for the acidic m h m, and are regressed

ne mec m f 1984) and for the bas

 from d Sava 8 lum and Stillings

1995) e d rate parameters a

24 
Table 14. K-feldspar Dissolution rate Data.

a

Composition

an ab or T, °C bpH clog k Source 

0 16 84 25 4 -8.65 Helgeson et al. 1984 

0 16 84 50 4 -7.54 Helgeson et al. 1984 

0 16 84 100 4 -5.76 Helgeson et al. 1984 

0 16 84 150 4 -4.39 Helgeson et al. 1984 

0 16 84 200 4 -3.3 Helgeson et al. 1984 

eson et al. 1984 

0 16 84 300 4 -1.69 Helgeson et al. 1984 

0 16 84 350 4 -1.07 Helgeson et al. 1984 

Helgeson et al. 1984 

Helgeson et al. 1984 

0 200 Helg

0 200 H

0 84 00 -3 H n et a 4

0 H et 4

0 Helgeson et al. 1984 

0 5.64 -9.03 Helgeson et al. 1984 

0 16 84 200 5.64 -3.3 Helgeson et al. 1984 

0 16 84 300 5.65 -8.26 Helgeson et al. 1984 

Helgeson et al. 1984 

Helgeson et al. 1984 

0 16 84 150 5.82 -4.39 Helgeson et al. 1984 

0 

et al. 1984

0 16 84 100 6.13 -10.18 Helgeson et al. 1984 

0 16 84 100 6.13 -5.76 Helgeson et al. 1984 

0 16 84 50 6.64 -11.01 Helgeson et al. 1984 

0 16 84 50 6.64 -7.54 Helgeson et al. 1984 

0 16 84 25 7 -11.52 Helgeson et al. 1984 

0 16 84 25 7 -8.65 Helgeson et al. 1984 

0 16 84 150 8.94 -7.79 Gautier et al. 1994 

0 16 84 150 8.94 -7.6 Gautier et al. 1994 

-- -- 97 300 9 -6.3 Alekseyev et al. 1997 

-- -- 97 300 9 -6.3 Alekseyev et al. 1997 

0 16 84 250 4 -2.42 Helg

0 16 84 100 4 -6.2 

0 16 84 150 4 -4.38 

16 84 

84 

4 -3.52 

-3.27 

eson et al. 1984 

16 n et a 84

16

4 

4

elgeso

elgeso

l. 19

2 19

2

l. 8

16 84 50 5 -8.61 al. 198

58 -2.42 

.58 elgeson

16 84 250 5.

16 84 200 

0 16 84 300 5.65 -1.69 

0 16 84 150 5.82 -9.54 

16 84 350 5.91 -7.97 Helgeson et al. 1984 

0 16 84 350 5.91 -1.07 Helgeson et al. 1984 

0 16 84 25 6 -8.65 Helgeson et al. 1984 

0 16 84 50 6 -7.54 Helgeson et al. 1984 

0 16 84 100 6 -5.76 Helgeson et al. 1984 

0 16 84 150 6 -4.39 Helgeson et al. 1984 

0 16 84 200 6 -3.3 Helgeson et al. 1984 

0 16 84 250 6 -2.42 Helgeson et al. 1984 

0 16 84 300 6 -1.69 Helgeson et al. 1984 

0 16 84 350 6 -1.07 Helgeson

25
Table 14. K-feldspar Dissolution rate Data. 

a

Composition

an ab or T, °C pH clo Source b g k

0 7 93 70 9 -12.03 Bevan and Savage 1989 

0 7 93 95 9 -1 Bevan and Savage 1989 

0 7 93 95 9 -1 Bevan and Savage 1989 

0 6 95 70 -1 Knauss and Copenhaver 1995 

a. -- = Not given. 

b. Acid mechanism, pH 4-5.91; tral me , pH 6- bas 4-13.

c. Log mole m-2 s-1.

1.63

1.72

9.51 0.7

Neu chanism 7; e mechanism, pH 8.9

Table 15. K-F spar issol ate ar

Acid Mechanism Base Mechanism 

eld D ution R P ameters.

Neutral Mechanism a

log k n alog alog k bE cn bE c k bE

-10.06 51.7 0.500 -12.41 38.0 -21.20 94.1 -0.823 

a. Rate constant k computed from , 25°C, H =

b. Arrhenius activation energy E, . 

c. Reaction order n with respect to

A and E p 0, mole m-2 s-1. 

kJ mole-1

+ H .

3.1.3 Feldsp

Dissolution rate data for nepheline were evaluated from Brady and Walther (1989), 

ole et al. (1986),

and for leucite, from Sverdrup (1990). Data for nepheline were selected from Tole et al. (1993) 

for the acidic and ms b au d rom ex er

range f tem ot refe enc da o e 3

summarized in Table 16, and the rate parame ermi lin ar on h us

eters for the basic mechanism for 

and basic mechanisms for leucite were compiled from Sverdrup 

990) and are summarized in Table 17, with activation energies calculated herein from reported 

athoids: Nepheline and Leucite

Hamilton et al. (2001), Murphy and Helgeson (1989), Sverdrup (1990), and T

neutral mechanis ec se they were obtaine f periments at a wid

o peratures than the her r es. The ta from T le t al. (199 ) are

ters det ned by e regressi erein ing

eqns. (11) and (12) are given in Table 18. Rate param

nepheline and acidic, neutral,

(1

rate constants at 8 and 25 °C; the results are also tabulated in Table 18. 

26 
Table 16. Nepheline Dissolution Rate Data.

a b T, °C pH log k Source 

25 3 -6.30 Tole et al. 1986 

25 3 -6.30 Tole et al. 1986 

-8.24 Tole et al. 1986 

60 11 -7.14 Tole et al. 1986 

a. Acid mechanism, pH 3-5; Neutral mechanism, pH 7-11. 

b. Log mole m-2 s-1. 

60 3 -4.89 Tole et al. 1986 

60 3 -4.89 Tole et al. 1986 

80 3 -4.33 Tole et al. 1986 

80 3 -4.33 Tole et al. 1986 

25 5 -8.24 Tole et al. 1986 

25 5

60 5 -7.30 Tole et al. 1986 

60 5 -7.30 Tole et al. 1986 

80 5 -6.78 Tole et al. 1986 

80 5 -6.78 Tole et al. 1986 

25 7 -8.62 Tole et al. 1986 

25 7 -8.62 Tole et al. 1986 

60 7 -7.41 Tole et al. 1986 

60 7 -7.41 Tole et al. 1986 

80 7 -6.89 Tole et al. 1986 

25 11 -8.56 Tole et al. 1986 

Table 17. Leucite Diss te Constants and Reac a

. 

Acid han utral c hanism 

olution Ra tion Orders

Mec ism Ne Me hanism Base Mec

log k8°C 25°C g k8°C l k25°C

b log k n b

n lo og k25°C log k8°C log

Leucite -10.40 -9.0 0.700 -13.00 -12.2 -11.40 -10.8 -0.200 

a. Data fr rdrup, 1990; units, lo le m-2 s

b. Reacti r n with respe +

.

om Sve

on orde

log k

ct to H

g mo -1. 

Table 18. Feldspath Disso ion R aram te

Acid hanis utral ec Base Mechanism 

oid lut ate P e rs.

Mec m Ne M hanism a

log k alog k bE cn bE cn alog k bE

Nepheline -2.73 62.9 1.130 -8.56 65.4 -10.76 37.8 -0.200 

Leucite -6.00 .2 00 .20 -10.66 56.6 -0.200 

a. Rate constant k computed pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy mole-1. 

c. Reaction order n with respe +

.

132 0.7 -9 75.5

from A and E, 25°C,

 E, kJ

ct to H

27
3.2 Orthosilicates

3. rou

lution ra ta fo ivine valua d . (2000), Bailey (1974), 

Blum a saga (198 Chen Bran 000) r ), Jonckbloedt (1998), 

Luce (1972), Murphy and Helgeson (1987; 1989), Oelkers (2001a), Pokrovsky and Schott 

(2000b), Pokrovsky and Schott (2000a), Rosso and Rim erdrup (1990), Van Herk

et al. (1989), Westrich al. (19 , Wo and W lth ogelius and Walther 

(1992) and Xiao et al. (1999). 

lution ra ta we electe forste te Brantley (2000), Oelkers

(2001a rovsky an chott 00b), vsky d , and Wogelius and 

Walthe 2); these a are s mariz able 9. anism for forsterite 

apparently operates at pH up to ~9, and there appare tly . Rate parameters 

for the acidic and neutral mecha ms w

summarized in Table 20. Rate parameters for the ac ic r fayalite is compiled from

Sverdr 90; Tabl ), wi ivati rgies alc rate

constan 8 and 25 for th tral nism, a “cut-off” rate constant at 25 °C was 

calcula that rate not ase w incr si on energy is

set equal to the acidic hani The rame rs ized in Table

20. 

Table orsterite ssolu Rate .

Com ion T, 

2.1 Olivine G p

Disso te da r ol were e te from Awad et al

nd La 6), and tley (2 , G andstaff (1986

stidt (2000), Sv

et 93) gelius a er, (1991), W

Disso te da re s d for ri from Chen and

), Pok d S (20 Pokro an Schott (2000a)

r (199 dat um ed in T 1 The acidic mech

n is no basic mechanism

nis ere regressed using eqn. (11), and the results are 

id mechanism fo

up (19 e 20 th act on ene c ulated herein from reported

ts at °C; e neu mecha

ted so s do decre ith pH ea ng above 9, and the activati

mec sm. rate pa te for fayalite are also summar

19. F Di tion Data

posit °C apH blog k Source 

fo91 25 1.03 -7.23 Pokrovsky and Schott, 2000

fo91 25 1.11 -7.33 Pokrovsky and Schott, 2000

fo91 25 1.12 -7.28 Pokrovsky and Schott, 2000

fo91 65 1.8 -6.29 Wogelius and Walther, 1992 

fo91 25 2 -7.80 Oelkers, 2001 

fo91 25 2 -7.75 Oelkers, 2001 

fo91 25 2 -7.92 Oelkers, 2001 

fo91 25 2 -7.91 Oelkers, 2001 

fo91 25 2 -7.85 Oelkers, 2001 

fo91 25 2 -7.81 Oelkers, 2001 

fo91 25 2 -7.98 Oelkers, 2001 

fo91 25 2 -7.88 Oelkers, 2001 

fo91 25 2 -7.88 Oelkers, 2001 

fo91 25 2 -7.90 Oelkers, 2001 

fo91 25 2 -7.89 Oelkers, 2001 

fo91 25 2 -7.92 Oelkers, 2001 

fo91 25 2 -7.90 Oelkers, 2001 

fo91 25 2 -7.91 Oelkers, 2001 

28 
Table 19. Forsterite Dissolution Rate Data - continued. 

Composition T, °C apH blog k Source 

fo91 25 2 -7.87 Oelkers, 2001 

fo91 25 2 -7.93 Oelkers, 2001 

fo91 25 2 -7.91 Oelkers, 2001 

fo91 25 2 -7.93 Oelkers, 2001 

fo91 25 2 -7.89 Oelkers, 2001 

fo91 25 2 -7.99 Oelkers, 2001 

fo91 25 2 -7.89 Oelkers, 2001 

fo91 25 2 -7.92 Oelkers, 2001 

fo91 35 2 -7.58 Oelkers, 2001 

fo91 45 2 -7.03 Oelkers, 2001 

fo91 55 2 -6.97 Oelkers, 2001

fo91 65 2 -6.09 Chen and Brantley, 2000 

fo91 65 2 -6.57 Oelkers, 2001 

fo91 25 2.13 -7.70 Pokrovsky and Schott, 2000 

fo91 25 2.18 -7.71 Pokrovsky and Schott, 2000 

fo91 25 2.21 -7.72 Pokrovsky and Schott, 2000 

fo91 25 2.7 -7.73 Pokrovsky and Schott, 2000 

fo91 25 2.74 -7.83 Pokrovsky and Schott, 2000 

fo91 25 2.81 -7.82 Pokrovsky and Schott, 2000 

fo91 25 2.82 -7.89 Pokrovsky and Schott, 2000 

fo91 25 2.85 -8.30 Pokrovsky and Schott, 2000 

f091 65 2.95 -6.76 Chen and Brantley, 2000 

f091 65 2.95 -6.83 Chen and Brantley, 2000 

f091 65 2.95 -6.85 Chen and Brantley, 2000 

f091 65 2.95 -6.82 Chen and Brantley, 2000 

fo91 65 2.95 -6.68 Chen and Brantley, 2000 

fo91 25 2.99 -7.93 Pokrovsky and Schott, 2000 

fo91 25 3.03 -7.97 Pokrovsky and Schott, 2000 

fo91 25 3.05 -8.18 Pokrovsky and Schott, 2000 

fo91 25 3.05 -8.28 Pokrovsky and Schott, 2000 

fo91 25 3.08 -8.14 Pokrovsky and Schott, 2000 

fo91 25 3.16 -8.25 Pokrovsky and Schott, 2000 

fo91 25 3.26 -8.34 Pokrovsky and Schott, 2000 

fo91 25 3.34 -8.55 Pokrovsky and Schott, 2000 

fo91 25 3.6 -8.80 Pokrovsky and Schott, 2000 

f091 65 4 -7.60 Chen and Brantley, 2000 

fo91 25 4.15 -9.03 Pokrovsky and Schott, 2000 

fo91 25 4.2 -8.69 Pokrovsky and Schott, 2000 

fo91 25 4.22 -8.78 Pokrovsky and Schott, 2000 

fo91 25 4.41 -8.80 Pokrovsky and Schott, 2000 

fo91 25 4.49 -8.98 Pokrovsky and Schott, 2000 

29
Table 19. Forsterite Dissolution Rate Data - continued. 

Composition T, °C apH blog k Source 

fo91 25 4.55 -9.03 Pokrovsky and Schott, 2000 

fo91 25 4.77 -8.98 Pokrovsky and Schott, 2000 

fo91 25 4.85 -9.02 Pokrovsky and Schott, 2000 

fo91 25 4.95 -9.15 Pokrovsky and Schott, 2000 

f091 65 5 -7.92 Chen and Brantley, 2000 

fo91 25 5.4 -9.31 Pokrovsky and Schott, 2000 

fo91 25 5.44 -9.47 Pokrovsky and Schott, 2000 

fo91 25 5.44 -9.47 Pokrovsky and Schott, 2000 

fo91 25 5.47 -9.57 Pokrovsky and Schott, 2000 

fo91 25 5.61 -9.79 Pokrovsky and Schott, 2000 

fo91 25 5.7 -9.49 Pokrovsky and Schott, 2000 

65 6 -8.13 Wogelius/Walther, 1992 

fo91 25 6.13 -9.92 Pokrovsky and Schott, 2000 

fo91 -10.04 

fo91 .9 y nd

fo91 7.1 0.1 ky nd 00

2 7. 0.04 Pokrovsky and Schott, 2000 

2 7. .88 Pokrovsky and Schott, 2000 

1 2 7. .93 Pokrovsky and Schott, 2000 

1 2 7 0.47 Pokrovsky and Schott, 2000 

1 2 7 0.57 P sky nd S 2000

fo91 2 7. 0.39 Pokrovsky and Schott, 2000 

.13 Pokrovsky and Schott, 2000 

fo91 25 8.13 -10.33 Pokrovsky and Schott, 2000 

fo91 25 8.38 -10.18 Pokrovsky and Schott, 2000 

8.5 -10.33 Pokrovsky and Schott, 2000 

8.53 -10.17 Pokrovsky and Schott, 2000 

fo91 25 8.55 -10.42 Pokrovsky and Schott, 2000 

9.3 -10.49 Pokrovsky and Schott, 2000 

fo91 25 9.58 -10.54 Pokrovsky and Schott, 2000 

fo91 25 10.08 -10.79 Pokrovsky and Schott, 2000 

fo91 25 10.24 -10.72 Pokrovsky and Schott, 2000 

fo91 25 10.76 -10.38 Pokrovsky and Schott, 2000 

fo91 25 10.78 -10.95 Pokrovsky and Schott, 2000 

fo91 25 10.85 -10.31 Pokrovsky and Schott, 2000 

fo91

fo91 25 6.18 -9.60 Pokrovsky and Schott, 2000

fo91 25 6.28 -9.72 Pokrovsky and Schott, 2000

25 6.39 

25 6.6 

Pokrovsky and Schott, 2000 

-9 7 Pokrovsk a Sch

Schott, 2

ott, 2000

25 9 -1 1 Pokrovs a 0

fo91

fo91

5 21 -1

5 25 -9

fo9 5 33 -9

fo9 5 .6 -1

fo9 5 .9 -1 okrov a chott,

5 98 -1

fo91 25 8.02 -10

fo91 25 

fo91 25

fo91 25 8.55 -10.40 Pokrovsky and Schott, 2000 

fo91 25 8.63 -10.44 Pokrovsky and Schott, 2000 

fo91 25 8.68 -10.46 Pokrovsky and Schott, 2000 

fo91 25 8.71 -10.60 Pokrovsky and Schott, 2000 

fo91 25 

30 
Table 19. Forsterite Dissolution Rate Data - continued. 

Composi a b tion T, °C pH log k Source 

fo91 25 10.9 -10.44 Pokrovsky and Schott, 2000 

fo91 25 10.9 -10.69 Pokrovsky and Schott, 2000 

fo91 25 10.95 -10.60 Pokrovsky and Schott, 2000 

fo91 25 11.01 -10.57 Pokrovsky and Schott, 2000 

fo91 25 11.1 -10.65 Pokrovsky and Schott, 2000 

91 25 11.11 -10.56 Pokrovsky and Schott, 2000 

Pokrovsky and Schott, 2000 

fo91 25 11.13 -10.71 Pokrovsky and Schott, 2000 

fo91 25 11.15 0.57 sky a chott,

fo91 25 0.85 P vsky a hott,

a. Acid mechanism, pH 1.03-8.71; mech H 9.3-12 . 

b. Log mole m-2 s-1.

fo

fo91 25 11.12 -10.52 

-1 Pokrov nd S 2000

12.06 -1 okro nd Sc 2000

Neutral anism, p .06

Table 20. Orth cate lutio te Con tants a eac rde

 Acid Mechanism Neutral Mech Bas hanism 

osili Disso n Ra s nd R tion O rs . 

a

anism e Mec

 log log bn log 8°C lo °C log k8°C k25°C

b k8 n °C k25°C k g k25 log

Fayalite -5.8 -4.8 1.0 -- -- -- -- -- 

Almandine -6.2 -5.2 1. -11.8 9.1 -0.3 

Grossular -6 -5.1 1.0 -11.8 -- -- -- 

Andradite -6.2 -5.2 1. -11.8 -- -- -- 

Staurolite -7.1 -6.9 1. -12.8 1.1 0.6 -0.3 

Zoisite -7 0.5 - -- -- -- 

a. Data from Sverdru 0; log k og mo

b. Reaction order n w pect to

0 -10.7 - -8.7 

-10.7

0 -10.7

0 -12.2 -1 -1

-8.2 .5 -2 -1- --

p, 199

ith res

units, l

 H

le m s . +

.

3.2.2 Garnet Group 

Rate pa ters for the acidic, neutral, and basic mechanisms for almandine, and acidic 

and neutral mechanisms (data are absent for the basic mechanism) for grossular and andradite are 

compiled from Sverdrup (1990; Table 20), with activation energies calculated herein from

reported rate constants at 8 and 25 °C. The rate parameters for the garnet group minerals are 

summarized in Table 22. 

rame

31
3.2.3 Al2SiO5 Group 

Dissolution rate data for kyanite were obtained from Oelkers and Schott (1999; Table 21) 

for the acidic mechanism only. The rate parameters are regressed herein using eqn. (11), and are 

summarized in Table 23. For the neutral mechanism, a “cut-off” rate constant at 25 °C was 

calculated so that rates do not decrease with pH increasing above 7, and the activation energy is 

set equal to that for the acidic mechanism.

Table 21. Kyanite Dissolution Rate Data. 

T, °C pH alog k T, °C pH alog k 

150 1.65 -9.63 150 2.04 -9.87 

150 1.65 -9.55 150 2.04 -9.87 

150 1.65 -9.42 150 2.04 -9.86 

150 1.85 -9.84 150 2.04 -9.79 

150 1.85 -9.66 150 2.04 -9.88 

150 1.85 -9.65 150 2.04 -9.79 

108 2.03 -10.96 150 2.04 -9.82 

108 2.03 -10.96 131 2.04 -9.98 

111 2.03 -10.54 174 2.06 -9.89 

113 2.03 -10.28 175 2.06 -9.67 

121 2.03 -10.48 175 2.06 -9.69 

121 2.03 -10.48 175 2.06 -9.62 

121 2.03 -10.66 175 2.06 -9.69 

122 2.03 -10.48 175 2.06 -9.61 

125 2.03 -10.40 175 2.06 -9.56 

125 2.03 -10.34 175 2.06 -9.77 

125 2.03 -10.28 194 2.07 -9.46 

126 2.03 -10.40 194 2.07 -9.27 

126 2.03 -10.29 150 2.24 -10.40 

150 2.04 -9.86 150 2.24 -10.24 

150 2.04 -9.92 150 2.24 -10.21 

150 2.04 -9.84 150 2.24 -10.37 

a. Log mole m-2 s-1.

32 
3.2.4 Staurolite 

Rate parameters for the acidic, neutral, and basic mechanisms for staurolite were 

compiled from Sverdrup (1990; Table 20), with activation energies calculated herein from

reported rate constants at 8 and 25 °C. The rate parameters for the staurolite are summarized in 

Table 23. 

3.2.5 Epidote Group 

Dissolution rate data for epidote and zoisite were evaluated from Rose (1991), 

Kalinowski et al. (1998), and Sverdrup (1990). Data for the acidic, neutral, and basic 

mechanisms for epidote from Rose (1991), and Kalinowski et al. (1998) were selected, and are 

tabulated in Table 22. The rate parameters for epidote are regressed herein using eqn. (11), and 

are summarized in Table 23. Rate parameters for the acidic mechanism for zoisite was compiled 

from Sverdrup (1990; Table 20), with the activation energy calculated herein from reported rate 

constants at 8 and 25 °C; for the neutral mechanism, a “cut-off” rate constant at 25 °C was 

calculated so that rates do not decrease with pH increasing above 7, and the activation energy is 

set equal to the acidic mechanism. The rate parameters for zoisite are summarized in Table 23. 

33
Table 22. Epidote Dissolution Rate Data. 

T, °C apH blog k Source

25 0.2 -10.23 Kalinowski et al. 1998 

25 1.08 -10.49 Kalinowski et al. 1998 

25 1.29 -11.31 Kalinowski et al. 1998 

90 1.29 -8.715 Rose 1991

25 1.4 -11.53 Kalinowski et al. 1998 

25 1.4 -11.528 Rose 1991

50 1.4 -10.322 Rose 1991

70 1.4 -9.268 Rose 1991

70 1.4 -9.63 Rose 1991

70 1.4 -9.677 Rose 1991

90 1.4 -8.9 Rose 1991

25 1.99 -11.19 Kalinowski et al. 1998 

25 2.01 -10.73 Kalinowski et al. 1998 

25 2.5 -11.8 Kalinowski et al. 1998 

90 2.5 -9.2 Rose 1991

90 2.5 -9.269 Rose 1991

25 2.98 -11.36 Kalinowski et al. 1998 

25 2.99 -11.63 Kalinowski et al. 1998 

25 3 -11.64 Kalinowski et al. 1998 

25 3.03 -11.42 Kalinowski et al. 1998 

25 3.47 -12.02 Kalinowski et al. 1998 

90 3.47 -9.424 Rose 1991

90 3.47 -9.424 Rose 1991

90 3.47 -9.528 Rose 1991

25 4.02 -12.19 Kalinowski et al. 1998 

25 4.05 -11.72 Kalinowski et al. 1998 

25 4.05 -12 Kalinowski et al. 1998 

25 4.12 -11.65 Kalinowski et al. 1998 

25 4.38 -12.17 Kalinowski et al. 1998 

90 4.38 -9.578 Rose 1991

25 5.5 -12.15 Kalinowski et al. 1998 

90 5.5 -9.55 Rose 1991

25 5.6 -11.8 Kalinowski et al. 1998 

25 6.48 -12.29 Kalinowski et al. 1998 

25 6.5 -11.93 Kalinowski et al. 1998 

90 6.62 -9.795 Rose 1991

90 7.75 -9.892 Rose 1991

90 8.64 -10.048 Rose 1991

90 10.83 -8.831 Rose 1991

25 10.6 -11.44 Kalinowski et al. 1998 

a. Acid mechanism, pH 1.2 – 4.38; Neutral mechanism, pH 5.5-7.75; basic 

mechanism, 8.64-10.8. 

b. Log mole m-2 s-1.

34 
Table 23. Orthosilicate Dissolution Rate Parameters. 

 Acid Mechanism Neutral Mechanism Base Mechanism a

log k bE cn alog k bE alog k bE cn 

Forsterite -6.85 67.2 0.470 -10.64 79.0 -- -- -- 

Fayalite -4.80 94.4 -12.80 94.4 -- -- -- 

Almandine -5.20 94.4 1.000 -10.70 103.8 -13.71 37.8 -0.350 

Grossular -5.10 85.0 1.000 -10.70 103.8 -- -- -- 

Andradite -5.20 94.4 1.000 -10.70 103.8 -- -- -- 

Kyanite -10.17 -53.9 1.268 -17.44 53.9 -- -- -- 

Staurolite -6.90 18.9 1.000 -12.20 56.6 -14.90 47.2 -0.300 

Epidote -10.60 71.1 0.338 -11.99 70.7 -17.33 79.1 -0.556 

Zoisite -7.50 66.1 0.500 -11.20 66.1 -- -- -- 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

3.3 Cyclosilicates 

3.3.1 Cordierite and Tourmaline 

Rate parameters for the acidic and neutral mechanisms (data are absent for the basic 

mechanism) for cordierite and tourmaline were compiled from Sverdrup (1990; Table 24), with 

activation energies calculated herein from reported rate constants at 8 and 25 °C. The rate 

parameters for the garnet group minerals are summarized in Table 22. 

Table 24. Cyclosilicate Dissolution Rate Constants and Reaction Ordersa

. 

 Acid Mechanism Neutral Mechanism 

 log k8°C log k25°C

b

n log k8°C log k25°C

Cordierite -5.0 -3.8 1.000 -11.5 -11.2 

Tourmaline -7.3 -6.5 1.000 -12.1 -11.2 

a. Data from Sverdrup, 1990; log k units, log mole m-2 s-1. 

b. Reaction order n with respect to H+

.

35
Table 25. Cyclosilicate Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism a

log k bE cn alog k bE 

Cordierite -3.80 113.3 1.000 -11.20 28.3 

Tourmaline -6.50 75.5 1.000 -11.20 85.0 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+.

3.4 Inosilicates 

3.4.1 Pyroxene Group / Pyroxenoid Group 

Dissolution rate data for pyroxenes and pyroxenoids were evaluated from Bailey (1974), 

Brantley and Chen (1995), Chen and Brantley (1998), Knauss et al. (1993), Murphy and 

Helgeson (1987; 1989), Rimstidt and Dove (1986), Schott and Berner (1985), Schott et al. 

(1981), Siegel and Pfannkuch (1984), Sverdrup (1990), and Weissbart (2000). 

Dissolution rate data for the acidic and neutral mechanisms (data are absent for the basic 

mechanism) were selected as follows: augite, from Schott et al. (1981) and Sverdrup (1990); 

bronzite, from Sverdrup (1990); diopside, from Brantley and Chen (1995), Chen and Brantley 

(1998), Knauss et al. (1993), and Schott and Berner (1985); enstatite, from Schott and Berner 

(1985); jadeite, from Sverdrup (1990); spodumene, from Sverdrup (1990); wollastonite, from

Murphy and Helgeson (1987; 1989) and Rimstidt and Dove (1986). The rate parameters were 

regressed using eqn. (11), except for the bronzite data from Sverdrup (1990), for which rate 

constants at 8 and 25 °C for single mechanisms are used herein to calculate the activation energy. 

The resulting rate parameters are summarized in Table 26. 

For enstatite and augite, the available data are limited to pH less than ~7. Although rates 

may decrease further with further pH increase above 7, a “cut-off” rate constant at 25 °C was 

calculated for the neutral mechanism so that rates do not decrease with pH increasing above 7, 

and the activation energy is set equal to the acidic mechanism.

36 
Table 26. Pyroxene and Pyroxenoid Dissolution Rate Parameters. 

 Acid Mechanism Neutral Mechanism a

log k bE cn alog k bE 

augite -6.82 78.0 0.700 -11.97 78.0 

bronzite -8.30 47.2 0.650 -11.70 66.1 

diopside -6.36 96.1 0.710 -11.11 40.6 

enstatite -9.02 80.0 0.600 -12.72 80.0 

jadeite -6.00 132.2 0.700 -9.50 94.4 

spodumene -4.60 94.4 0.700 -9.30 66.1 

wollastonite -5.37 54.7 0.400 -8.88 54.7 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

3.4.2 Amphibole Group 

Dissolution rate data for amphiboles were evaluated from Brantley and Chen (1995), 

Chen and Brantley (1998), Sverdrup (1990), and Zhang and Bloom (1999). Data for the acidic 

and neutral mechanisms (data are absent for the basic mechanism) were selected as follows: 

anthophyllite, from Chen and Brantley (1998); glaucophane, hornblende, riebeckite and 

tremolite, from Sverdrup (1990). The rate parameters were regressed using eqn. (11), except for 

the data from Sverdrup (1990), for which rate constants at 8 and 25 °C for single mechanisms are 

used herein to calculate the activation energy. The resulting rate parameters are summarized in 

Table 27. 

Table 27. Amphibole Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism a

log k bE cn alog k bE 

anthophyllite -11.94 51.0 0.440 -14.24 51.0 

glaucophane -5.60 85.0 0.700 -10.10 94.4 

hornblende -7.00 75.5 0.600 -10.30 94.4 

riebeckite -7.70 56.6 0.700 -12.20 47.2 

tremolite -8.40 18.9 0.700 -10.60 94.4 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

37
3.5 Phyllosilicates 

3.5.1 Mica Group 

Dissolution rate data for the micas were evaluated from Acker and Bricker (1992), 

Clemency and Lin (1981), Kalinowski and Schweda (1996), Knauss and Wolery (1989), 

Kuwahara and Aoke (1999), Lin and Clemency (1981a; 1981b), Malmstrom and Banwart 

(1997), Nagy (1995), Robie (1976), Sverdrup (1990), Swoboda-Colberg and Drever (1993), 

Taylor et al. (2000b), and Trotignon and Turpault (1992). 

Data were selected as follows: biotite, from Acker and Bricker (1992) and Nagy (1995); 

glauconite, from Sverdrup (1990); muscovite, paragonite, phlogopite and pyrophyllite, from

Nagy (1995). The rate parameters were regressed using eqn. (11), except for the data from

Sverdrup (1990), for which rate constants at 8 and 25 °C for single mechanisms are used herein 

to calculate the activation energy. The compiled rate parameters are summarized in Table 28. 

Table 28. Orthosilicate Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism Base Mechanism a

log k bE cn alog k bE alog k bE cn 

biotite -9.84 22.0 0.525 -12.55 22.0 -- -- -- 

glauconite -4.80 85.0 0.700 -9.10 85.0 -- -- -- 

muscovite -11.85 22.0 0.370 -13.55 22.0 -14.55 22.0 -0.220 

muscovite -- -- -- -13.00 22.0 -- -- -- 

paragonite -- -- -- -13.00 22.0 -- -- -- 

phlogopite -- -- -- -12.40 29.0 -- -- -- 

pyrophyllite -- -- -- -12.40 29.0 -- -- -- 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

3.5.2 Clay Group 

Dissolution rate data for three additional clay group minerals were evaluated: kaolinite 

(Bauer and Berger, 1998; Cama et al., 2002; Carroll and Walther, 1990; Carroll-Webb and 

Walther, 1988; Devidal et al., 1997; Ganor et al., 1995; Hayashi and Yamada, 1990; Huertas et 

al., 1999a; Huertas et al., 2001b; Huertas et al., 1999b; Metz and Ganor, 2001; Nagy, 1995; Nagy 

et al., 1991; Nagy and Lasaga, 1990; Nagy and Lasaga, 1993; Oelkers et al., 2001; Polzer and 

Hem, 1965; Soong, 1993; Soong and Barnes, 1991; Sutheimer et al., 1999; Wieland and Stumm, 

1992); montmorillonite (Furrer et al., 1993; Hayashi and Yamada, 1990; Huertas et al., 2001a; 

Nagy, 1995; Zysset and Schindler, 1996); and smectite (Altaner, 1986; Bauer and Berger, 1998; 

Cama et al., 2000; Cama et al., 1994; Novák and Cícel, 1978). 

Data for the clay group minerals were selected as follows: kaolinite, from Carroll and 

Walther (1990), Ganor et al. (1995), Huertas et al. (1999a), Huertas et al. (1999b), Nagy et al. 

(1991), Soong (1993); montmorillonite, from Nagy (1995); smectite, from Bauer and Berger 

38 
(1998), Huertas et al. (2001a), Sverdrup (1990), and Zysset and Schindler (1996). The rate 

parameters were regressed using eqn. (11), except for the data from Sverdrup (1990), for which 

rate constants at 8 and 25 °C for single mechanisms are used herein to calculate the activation 

energy. The compiled rate parameters are summarized in Table 29. Nagy et al. (1991) have 

quantified the chemical affinity parameters for kaolinite at 80 °C and pH = 3; with the 

experimental uncertainty, the experimental data can be fit to eqn. (4) with either p = 1.000 and q

= 0.897, or p = 0.850 and q = 1.000. 

Table 29. Clay Group Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism Base Mechanism a

log k bE cn alog k bE alog k bE cn 

kaolinite -11.31 65.9 0.777 -13.18 22.2 -17.05 17.9 -0.472 

d

montmorillonite -12.71 48.0 0.220 -14.41 48.0 -14.41 48. -0.130 e

smecite -10.98 23.6 0.340 -12.78 35.0 -16.52 58.9 -0.400 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

. 

d. Montmorillonite, K0.318(Si3.975Al0.025)(Al1.509Fe0.205Mg0.283)(OH)2. 

e. Smectite, K0.04Ca0.5(Al2.8Fe0.53Mg0.7)(Si7.65Al0.35)O20(OH)4.

3.5.3 Miscellaneous Phyllosilicates 

Dissolution rate data for several miscellaneous phyllosilicate minerals were evaluated: 

serpentine (Bales and Morgan, 1985; Cetisli and Gedikbey, 1990; Gronow, 1987; Hume and 

Rimstidt, 1992; Lin and Clemency, 1981b; Nagy, 1995; Sverdrup, 1990; Thomassin et al., 1977), 

chlorite (Hayashi and Yamada, 1990; Johnson et al., 2001; Nagy, 1995; Sverdrup, 1990), talc 

(Lin and Clemency, 1981b; Nagy, 1995), and prehnite (Rose, 1991). 

Data for these phyllosilicate minerals were selected as follows: lizardite serpentine, from

Sverdrup (1990); chrysotile serpentine, from Nagy (1995); chlorite, from Nagy (1995); talc, from

Nagy (1995); and prehnite, from Rose (1991). The compiled parameters are summarized in 

Table 30. 

39
Table 30. Miscellaneous Phyllosilicate Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism Base Mechanism a

log k bE cn alog k bE alog k bE cn 

lizardite -5.70 75.5 0.800 -12.40 56.6 -- -- -- 

chrysotile -- -- -- -12.00 73.5 -13.58 73.5 -0.230 

d

chlorite -11.11 88.0 0.500 -12.52 88.0 -- -- -- 

talc -- -- -- -12.00 42.0 -- -- -- 

prehnite -10.66 80.5 0.256 -13.16 93.4 -14.86 93.4 -0.200 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

. 

d. Clinochlore 14 Å.

3.6 Oxides 

Dissolution rate data for several oxide minerals were evaluated: goethite (Ruan and 

Gilkes, 1995), hematite (Bruno and Duro, 2000; Bruno et al., 1992; Hummel, 2000; Petrie, 1995; 

Ruan and Gilkes, 1995), ilmenite (White et al., 1994), magnetite (White et al., 1994), manganite 

(Petrie, 1995), pyrolusite (Petrie, 1995), and uraninite (Grandstaff, 1976). Data for the oxide 

minerals were selected as follows: goethite, from Ruan and Gilkes (1995); hematite, Ruan and 

Gilkes (1995); ilmenite, White et al. (1994); magnetite, White et al. (1994); pyrolusite, Petrie 

(1995); and uraninite Grandstaff (1976). The compiled parameters are summarized in Table 31. 

Table 31. Oxide Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism a

log k bE cn alog k bE 

goethite -- -- -- -7.94 86.5 

hematite -9.39 66.2 1.000 -14.60 66.2 

magnetite -8.59 18.6 0.279 -10.78 18.6 

ilmenite -8.35 37.9 0.421 -11.16 37.9 

uraninite -- -- -- -7.98 32.0 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

40 
3.7 Hydroxides 

Dissolution rate data for brucite (Jordan and Rammensee, 1996; Lin and Clemency, 

1981b; Nagy, 1995; Sverdrup, 1990), gibbsite (Bloom, 1983; Bloom and Erich, 1987; Chang et 

al., 1979; Ganor et al., 1999; Mogollón et al., 1996; Mogollón et al., 2000; Nagy, 1995; Nagy 

and Lasaga, 1990; Nagy and Lasaga, 1992; Nagy and Lasaga, 1993; Packter and Dhillon, 1974; 

Scotford and Glastonbury, 1972a; Scotford and Glastonbury, 1972b), and diaspore (Chang et al., 

1979) were evaluated. Data for brucite were selected from Nagy (1995) and Jordan and 

Rammensee (1996). Data for gibbsite were selected from Nagy and Lasaga (1992) and Packter 

and Dhillon (1974). The compiled parameters are summarized in Table 32. 

Table 32. Hydroxide Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism Base Mechanism a

log k bE cn alog k bE alog k bE cn 

brucite -4.73 59.0 0.500 -8.24 42.0 -- -- -- 

gibbsite -7.65 47.5 0.992 -11.50 61.2 -16.65 80.1 -0.784 

diaspore -- -- -- -13.33 47.5 -23.60 47.5 -1.503 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

3.8 Carbonates 

Dissolution rate data for four carbonate minerals were evaluated: calcite (Alkattan et al., 

1998; Alkattan et al., 2002; Berner and Morse, 1974; Brown et al., 1993; Busenberg and 

Plummer, 1986; Chou et al., 1989; Deleuze and Brantley, 1997; House, 1981; Inskeep and 

Bloom, 1985; Jeschke and Dreybrodt, 2002b; Jiménez-López et al., 2001; Jordan and 

Rammensee, 1998; Lebrón and Suárez, 1996; Lebrón and Suárez, 1998; MacInnis and Brantley, 

1992; Maldonado et al., 1992; Morse, 1978; Mucci, 1986; Mucci and Morse, 1983; Plummer and 

Wigley, 1976; Plummer et al., 1978; Plummer et al., 1979; Reddy, 1986; Reddy and Gaillard, 

1981; Reddy et al., 1981; Schott et al., 1989; Shiraki and Brantley, 1995; Sjöberg, 1976; Sjöberg 

and Rickard, 1983; Sjöberg and Rickard, 1984a; Sjöberg and Rickard, 1984b; Sjöberg and 

Rickard, 1985; Talman et al., 1990; Teng et al., 2000; Zhang and Dawe, 1998; Zhang and Dawe, 

2000; Zhong and Mucci, 1989; Zhong and Mucci, 1993; Zuddas and Mucci, 1994; Zuddas and 

Mucci, 1998); dawsonite (Johnson et al., 2001); dolomite (Arvidson and Mackenzie, 1999; Baker 

and Kastner, 1981a; Baker and Kastner, 1981b; Busenberg and Plummer, 1982; Busenberg and 

Plummer, 1986; Chou et al., 1989; Gaines, 1980; Gautelier et al., 1999; Katz and Matthews, 

1977; Lüttge et al., 2003; Nordeng and Sibley, 1994; Sibley et al., 1987); magnesite (Chou et al., 

1989; Higgins et al., 2002; Johnson et al., 2001; Jordan et al., 2001; Pokrovsky and Schott, 

1999); and siderite (Greenberg and Tomson, 1992; Jensen et al., 2002). 

Data for the carbonate minerals were selected as follows: calcite, from Plummer et al. 

(1978) and Talman et al. (1990); dawsonite, Johnson et al. (2001); dolomite, Busenberg and 

41
Plummer (1982); and magnesite, Chou et al. (1989) and Pokrovsky and Schott (1999). The rate 

parameters were regressed using eqn. (11), and are summarized in Table 33. In the absence of 

data for the activation energy for magnesite dissolution, the activation energy of calcite is 

assigned to magnesite. Pokrovsky and Schott (1999) have quantified the chemical affinity 

parameters for magnesite at 25 °C with pH ranging from 0.2 to 12, with p = 4.00 and q = 1.00. 

Table 33. Carbonate Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism Carbonate Mechanism a

log k bE cn alog k bE alog k bE dn 

calcite -0.30 14.4 1.000 -5.81 23.5 -3.48 35.4 1.000 

dawsonite -- -- -- -7.00 62.8 -- -- -- e

dolomite -3.19 36.1 0.500 -7.53 52.2 -5.11 34.8 0.500 

f

dolomite -3.76 56.7 0.500 -8.60 95.3 -5.37 45.7 0.500 

magnesite -6.38 14.4 1.000 -9.34 23.5 -5.22 62.8 1.000 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

. 

d. Reaction order n with respect to P(CO2). 

e. Sedimentary (disordered) dolomite. 

f. Hydrothermal (ordered) dolomite.

3.9 Sulfates 

Dissolution rate data for several sulfate minerals were evaluated: anhydrite (Barton and 

Wilde, 1971; Bildstein et al., 2001; Dove and Czank, 1995; Jeschke and Dreybrodt, 2002b); 

anglesite (Dove and Czank, 1995); barite (Christy and Putnis, 1993; Dove and Czank, 1995; 

Kornicker et al., 1991); celestite (Dove and Czank, 1995); and gypsum (Jeschke et al., 2001; 

Raines and Dewers, 1997). Data for the sulfate minerals were selected as follows: anhydrite, 

from Barton and Wilde (1971) and Dove and Czank (1995); anglesite, barite and celestite, from

Dove and Czank (1995); and gypsum, from Raines and Dewers (1997). The rate parameters 

were regressed using eqn. (11), and are summarized in Table 34. Date were insufficient to 

calculate activation energies for the neutral mechanism for gypsum, and the acidic mechanisms

for anglesite and barite; activation energies for the neutral mechanisms for anglesite and barite 

are assigned to the respective acidic mechanisms. The acidic mechanism for celestite apparently 

extends to alkaline pH, and there is no evident neutral mechanism.

42 
Table 34. Sulfate Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism a

log k bE cn alog k bE 

anglesite -5.58 31.3 0.298 -6.50 31.3 

anhydrite -- -- -- -3.19 14.3 

gypsum -- -- -- -2.79 0 

barite -6.90 30.8 0.220 -7.90 30.8 

celestite -5.66 23.8 0.109 -- -- 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

3.10 Sulfides 

Dissolution rate data for several sulfide minerals were evaluated: AsS, amorphous 

(Lengke and Tempel, 2003); As2S3, amorphous (Lengke and Tempel, 2001); Orpiment and 

As2S3, amorphous (Lengke and Tempel, 2002); pyrite (Gibbs et al., 1997a; Gibbs et al., 1997b; 

Holmes and Crundwell, 2000; Kamei and Ohmoto, 2000; Lennie and Vaughan, 1992; McKibben 

and Barnes, 1986; Moses and Herman, 1991; Moses et al., 1987; Nicholson et al., 1988; 

Nicholson et al., 1990; Rickard, 1997; Rickard and Luther, 1997; Rickard, 1975; Rimstidt and 

Vaughan, 2003; Schoonen and Barnes, 1991a; Schoonen and Barnes, 1991b; Schoonen and 

Barnes, 1991c; Wiersma and Rimstidt, 1984; Williamson and Rimstidt, 1994); pyrrhotite 

(Dekkers and Schoonen, 1994; Janzen et al., 2000; Thomas et al., 2001); Realgar (Lengke and 

Tempel, 2003); and Sphalerite (Weisener et al., 2003). 

Data for the sulfide minerals were selected as follows: As2S3, amorphous, from Lengke 

and Tempel (2001); pyrite, from McKibben and Barnes (1986); and pyrrhotite, from Janzen et al. 

(2000). The rate parameters were regressed using eqn. (11) or compiled directly from the 

references, and are summarized in Table 35. 

Table 35. Sulfide Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism Base Mechanism a

log k bE cn dn alog k bE en alog k bE cn 

pyrite -7.52 56.9 -0.500 0.500 -4.55 56.9 0.500 -- -- -- f

pyrrhotite -8.04 50.8 -0.597 0.355 -- -- -- -- -- -- g

pyrrhotite -6.79 63.0 -0.090 0.356 -- -- -- -- -- -- h

As2S3 -- -- -- -- -9.83 8.7 0.180 -17.39 8.7 -1.208 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

. 

d. Reaction order n with respect to Fe+++. 

e. Reaction order n with respect to O2. 

f. Monoclinic pyrrhotite. 

g. Hexagonal pyrrhotite. 

h. Amorphous As2S3. 

43
3.11 Phosphates 

Dissolution rate data for apatite from several references were evaluated (Chien, 1977; 

Chien et al., 1980; Christoffersen et al., 1978; Fawzi et al., 1978; Fox et al., 1978; Guidry and 

Mackenzie, 2003; Hull and Hull, 1987; Valsami-Jones et al., 1998). Data for hydroxyapatite and 

fluorapaite were selected from Fawzi et al. (1978) and Valsami-Jones et al. (1998). The rate 

parameters were regressed using eqn. (11), and are summarized in Table 36. For the neutral 

mechanism, a “cut-off” rate constant at 25 °C was calculated so that rates do not decrease with 

pH increasing above 7, and the activation energy is set equal to the acidic mechanism. The 

uncertainty in activation energy may be quite large because it was computed from dissolution 

rates obtained from experiments with minimal temperature difference, 25 and 28 °C (Fawzi et 

al., 1978); these data were for experiments with hydroxyapatite, and the tabulated activation 

energy for fluorapatite dissolution is taken equal to that of hydroxyapatite. 

Table 36. Phosphate Mineral Dissolution Rate Parameters. 

 Acid Mechanism Neutral Mechanism a

log k bE cn alog k bE 

hydroxyapatite -4.29 250.0 0.171 -6.00 250.0 

fluorapatite -3.73 250.0 0.613 -8.00 250.0 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

44 
3.12 Halides 

Dissolution rate data for halite (Alkattan et al., 1997a; Alkattan et al., 1997b) and fluorite 

(Bosbach et al., 1995; Christoffersen et al., 1988; Gardner and Nancollas, 1976; Hamza et al., 

1987; Hamza and Hamdona, 1991; Zhang and Nancollas, 1990) were evaluated. Data for halite 

were selected from Alkattan (1997a), and the rate parameters were regressed using eqn. (11); the 

far from equilibrium rate constant was calculated from data at Ω = 0.90 to 0.94 and the apparent 

rate constant. For fluorite, the rate constant at 25 °C in pure water was selected from Zhang and 

Nancollas (1990), where the far from equilibrium rate constant was calculated from data at Ω = 

0.40 and the apparent rate constant, and the activation energy was selected from Hamza and 

Hamdone (1991). The rate parameters for halite and fluorite are summarized in Table 37. 

Table 37. Halide Mineral Dissolution Rate Parameters. 

Acid Mechanism Neutral Mechanism a

log k bE cn alog k bE 

halite -- -- -- -0.21 7.4 

fluorite -7.14 73.0 1.000 -13.79 73.0 

a. Rate constant k computed from A and E, 25°C, pH = 0, mole m-2 s-1. 

b. Arrhenius activation energy E, kJ mole-1. 

c. Reaction order n with respect to H+

.

45
4. CONCLUSIONS 

This work is intended as a preliminary starting point for the implementation of the 

kinetics of mineral dissolution and precipitation in aqueous fluids in reaction path modeling of 

water-rock-gas systems. The list of cited references may be as useful as, or perhaps more useful 

than, the rate parameters compiled herein, as the references commonly provide information to 

further refine rate equations that have been implemented, particularly with regard to the use of 

adsorption isotherms to quantify the effects of dissolved constituents upon reaction rates. The 

general rate equation and rate parameters were compiled specifically for the program

GAMSPATH (Perkins et al., 1997), which simulates an infinitely well stirred batch reactor. For 

the program GAMSPATH, the rate parameters compiled provide the ability to compute, to a first 

approximation, the minimum length of time required for a system to equilibrate. 

For most minerals, there is currently a high degree of uncertainty in experimentally 

determined dissolution and precipitation rates. For many minerals, variation in composition, 

degree of cation disorder, degree of crystallinity, as well as the frequency and distribution of 

crystal defects, contribute to these uncertainties. In many cases, the lack of data over a wide 

range of temperatures results in a large degree of uncertainty in the Arrhenius activation energy. 

Furthermore, the possible effects of many common dissolved species have not been quantified. 

It is clear that much experimental work remains to be done to determine the kinetics of mineral 

dissolution and precipitation under conditions that are encountered in natural systems. 

46 
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