Chemical Geology 151 Ž1998.

199–214

An experimental study of calcite and limestone dissolution rates

as a function of pH from y1 to 3 and temperature from 25 to
808C
Marwan Alkattan ) , Eric H. Oelkers, Jean-Louis Dandurand, Jacques Schott
´
Laboratoire de Geochimie, CNRSr UMR 5563-OMP-UniÕersite´ Paul-Sabatier, 38 rue des Trente-Six Ponts, 31400 Toulouse, France

Abstract

Dissolution rates of single calcite crystals, limestones, and compressed calcite powders were determined from sample
weight loss using free-drift rotating disk techniques. Experiments were performed in aqueous HCl solutions over the bulk
solution pH range y1 to 3, and at temperatures of 258, 508, and 808C. Corresponding rates of the three different sample
types are identical within experimental uncertainty. Interpretation of these data using equations reported by Gregory and
Riddiford wGregory, D.P., Riddiford, A.C., 1956. Transport to the surface of a rotating disc. J. Chem. Soc. London 3,
3756–3764x yields apparent rate constants and Hq diffusion coefficients. The logarithms of overall calcite dissolution rates
Ž r . obtained at constant disk rotation speed are inversely proportional to the bulk solution pH, consistent with r s kX2 aHq ,b ,
where kX2 stands for an apparent rate constant and aHq ,b designates the hydrogen ion activity in the bulk solution. This
variation of dissolution rates with pH is consistent with corresponding rates reported in the literature and the calcite
dissolution mechanism reported by Wollast wWollast, R., 1990. Rate and mechanism of dissolution of carbonates in the
system CaCO 3 –MgCO 3. In: Stumm, W. ŽEd.., Aquatic Chemical Kinetics. Wiley, pp. 431–445x. Apparent rate constants for
a disk rotation speed of 340 rpm increase from 0.07 " 0.02 to 0.25 " 0.02 mol my2 sy1 in response to increasing
temperature from 258 to 808C. Hq diffusion coefficients increase from Ž2.9 to 9.2. = 10y9 m2 sy1 over this temperature
range with an apparent activation energy of 19 kJ moly1. q 1998 Elsevier Science B.V. All rights reserved.

Keywords: Calcite; Limestone; Dissolution rates; Diffusion coefficients

1. Introduction 1974; Millero, 1974, 1979; Plummer and MacKen-

The motivation of this study is the improved
understanding of calcite dissolution rates in low-tem-
perature acidic solutions. The dissolution rates of
calcite and other carbonate minerals have received
considerable attention over the past thirty years
ŽLangmuir, 1968, 1971; Pytkowicz, 1967, 1973,
1983; Griffin and Jurinak, 1973; Berner and Morse,
)
Corresponding author. Fax: q33 561 52 0544.
zie, 1974; Lund et al., 1975; Busenberg and
Clemency, 1976; Plummer and Wigley, 1976;
¨
Sjoberg, 1976, 1978, 1983; Garrels and Wollast,
1978; Plummer et al., 1978, 1979; Busenberg and
Plummer, 1982, 1986; Plummer and Busenberg,
¨
1982; Rickard and Sjoberg, 1983; Morse, 1983;
¨
Sjoberg and Rickard, 1983, 1984a,b, 1985; Amrhein
et al., 1985; Guy, 1989; Schott et al., 1989; Chou et
al., 1989; Compton and Pritchard, 1990; Compton
and Unwin, 1990; Wollast, 1990; MacInnis and

0009-2541r98r$ - see front matter q 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 Ž 9 8 . 0 0 0 8 0 - 1
200 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214

Brantley, 1992; Arakaki and Mucci, 1995; Dreybrodt
et al., 1996; Liu and Dreybrodt, 1996.. Some of
these studies have been performed to better under-
stand sedimentary rock evolution ŽLangmuir, 1968;
Dreybrodt, 1981a,b; Buhman and Dreybrodt,
1985a,b., ocean water chemistry ŽPytkowicz, 1967,
1973, 1983; Morse and Berner, 1972, 1979; Berner
and Morse, 1974; Morse et al., 1979; Millero and
Leung, 1976; Berner, 1975, 1978; Mucci, 1986;
Burton and Walter, 1987., and acid fracturation of
oil field reservoirs ŽVan Pollen and Argon, 1968;
Hung et al., 1989; Daccord et al., 1989; Hoefner and
Folger, 1989; Gdanski and Lee, 1989; Cheung and
Van Arsdale, 1989; Tinker, 1989; Van Domelen,
1992; Yan et al., 1993; Wang et al., 1993; Hill et al.,
1994.. Building upon these studies the dissolution
rates of single calcite crystals, limestones, and com-
pressed calcite powders were measured in the pre-
sent study over the pH range y1 to 3 and at
temperatures from 258 to 808C. These data are essen-
tial for evaluating and optimizing acid induced frac-
turing of carbonate rocks leading to enhanced oil and
gas recovery. The purpose of the present communi-
cation is to report the results of this experimental
study and to compare them with corresponding data
available in the literature.
2. Materials and methods
All dissolution rates obtained in the present study
were measured using rotating disk techniques. This
technique is extremely useful in measuring dissolu-
tion rates over a wide range of hydrodynamic condi-
tions. Dissolution rates were determined from the
weight loss of solid samples dissolved in HCl solu-
tions. Three types of samples were considered: single
calcite crystals, limestones, and compressed calcite
powders. Calcite crystal samples were obtained from
cutting and polishing oriented crystals of Pourtalet
´ ´ France. calcite. Sample disks exposing
ŽPyrenees,
faces either parallel to the cleavage plane or perpen-
dicular to the c crystallographic axis were created
from these crystals. Two different limestones were
considered: Saint Maximin and Lavoux limestone.
Sample disks having a diameter of 23 " 0.02 mm
were cut from each of these solid samples. The
chemical composition of both Pourtalet calcite and
the two limestones considered in this study are given
in Table 1. Disks of calcite powder were produced
from approximately 2 g of ground Pourtalet calcite
Ž- 125 mm fraction., which was compressed into
13 " 0.02 mm diameter cylinders at a pressure of
500 MPa. Resulting disks were 8–10 mm thick. All

Table 1
Chemical and mineralogical composition of the solids dissolved in this study
Major oxides Žwt.%.
Al 2 O 3 SiO 2 Fe 2 O 3 MgO CaO CO 2 Total
Pourtalet calcite 0.32 0.72 0.29 0.07 55.8 43.9 100.4
St. Maximum limestone 0.34 17.50 0.13 0.70 44.34 36.28 99.1
Lavoux limestone t 0.05 0.12 0.50 55.55 43.78 100.0

Trace elements Žppm.

Mn Sr K S Ni Pb Co
Pourtalet calcite 2000 1000 – – 20 5 5
St. Maximum limestone t 700 2000 700 – – –
Lavoux limestone t t t t – – –

Mineralogical composition Žvol%.

Calcite Quartz Clay minerals Mg-carbonates
Pourtalet calcite 99.6 – – 0.1
St. Maximum limestone 79 16 0.9 1.5
Lavoux limestone 99.1 – 0.2 0.4

Dashes and t corresponds to below the detection limit and trace quantities present, respectively.
 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214
sample disks were set in Araldite epoxy resin Žcast
using AY103 and hardener HY219. leaving the de-
sired face free. This face was polished with 220,
800, and 1200 abrasive paper, and ultimately with
Nylon using silicon oil. The silicon oil was removed
by washing the surfaces with methyl alcohol. All
samples were oven-dried at 908C for 72 h before and
after each experiment. Reactive solutions were com-
posed of pure analytical grade HCl and deionized
H 2 O. For experiments conducted at pH ; 3, KCl
was added to these solutions to maintain an approxi-
mately constant 10y2 molal ionic strength. Neither
the pH nor the ionic strength of the reactive solutions
were controlled during the experiments. The differ-
ence between the pH of the reactive solution prior to
and following the experiments was 0.001 pH units
for experiments conducted at pH f y1, increasing
to as much as 0.32 pH units for experiments con-
ducted at pH f 3. The ionic strength of the reactive
solutions increased by a maximum of 15% for the
Fig. 1. Schematic illustration of the rotating disk reactor used to measure dissolution rates.
201
experiments performed at pH f 2, but by less than
5% at all other pH. All experiments were controlled
so that sample dissolution did not change the hydro-
dynamic conditions near the disk surface ŽAlkattan,
1996. and the reactive solutions were highly under-
saturated with respect to all solid phases including
calcite.
Experiments were performed using the double
glass walled rotating disk reactor depicted in Fig. 1
at thermostated bath temperatures of 258, 508, and
80 " 18C. One liter of reactive fluid was placed into
this reactor at the start of each experiment. The
sample disk was placed in a support which was fixed
to a rotator and immersed in the reactive solution.
Both the sample disk and its support were preheated
to the experimental temperature before introduction
into the solution. The sample disk was kept 7 cm
from the reactor walls and 6 cm below the solution
surface and was rotated using a Heidolph motor. The
rotation speed ranged from 0 to 2000 " 4 revolutions
202 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214

per minute Žrpm.. This reactor was kept at an angle
of approximately 308 from horizontal to allow the
departure of CO 2 bubbles, which form as a result of
calcite dissolution, leaving the total mineral surface
in contact with the reactive fluid during the experi-
ments. At pH G 2, the bulk reactive solution pH was
measured in the reactor during the dissolution exper-
iments with a Schott H63 combined electrode cali-
brated using DIN 19266rNIST standards ŽpH s
4.008 and 6.865 at 258C. at the temperature of

Table 2
Dissolution rates of single calcite crystals, compressed calcite powder, and limestones at 258C and pH s 1 as a function of disk rotation
speed
Sample Sample Weight Elapsed Rotation Dissolution
number loss Žg. time Žmin. speed Žrpm. rate = 10 3
Žmol my2 sy1 .
Single calcite crystalsa 524 0.43490 10 2000 17.4
512 0.56730 12 2000 19.4
527 0.49180 10 2000 19.7
534 0.32410 10 1000 13.0
556 0.32970 10 1000 13.2
531 0.23535 10 500 9.43
562 0.22670 10 500 9.09
535 0.36775 20 340 7.37
560 0.34525 20 340 6.92
522 0.73170 90 100 3.26
547 0.52100 60 100 3.48
552 0.56685 60 100 3.79
513 1.12400 210 50 2.41
544 0.53880 90 50 2.40
559 0.65780 90 50 2.93
528 0.51070 120 20 1.71
521 0.79950 240 10 1.33
536 0.35445 90 10 1.58
Compressed calcite powder 457 0.14185 10 2000 18.7
458 0.12705 10 2000 18.7
474 0.08550 10 1000 12.6
476 0.08785 10 1000 12.9
470 0.05560 10 1000 8.19
472 0.04970 10 500 7.32
461 0.08785 20 340 6.47
464 0.08730 20 340 6.43
585 0.16680 60 100 4.09
593 0.17980 60 100 4.41
463 0.18500 90 50 3.03
471 0.19070 90 50 3.12
St. Maximin limestone 491 0.06435 6 100 4.41
493 0.58165 60 100 3.99
501 0.05340 6 100 3.66
506 0.51100 60 100 3.50
504 0.73370 90 50 3.35
507 0.67570 90 50 3.09
486 0.06015 15 20 3.99
481 0.71950 120 20 2.47
494 0.23575 120 20 2.09
603 0.23575 90 10 1.08
604 0.24715 90 10 1.13
a
Cross section oriented perpendicular to the c-crystallographic axis.
 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214 203

Table 3
Dissolution rates of single calcite crystals with cross section oriented perpendicular to the c-crystallographic axis at 508 and 808C and
pH s 1 as a function of disk rotation speed
Temperature Sample Weight Elapsed Rotation Dissolution
Ž8C. number loss Žg. time Žmin. speed Žrpm. rate = 10 3
Žmol my2 sy1 .
50 613 0.90305 10 2000 36.2
616 0.85080 10 2000 34.1
622 0.39810 10 1000 16.0
619 0.39110 10 1000 15.9
626 0.27790 10 500 11.1
629 0.24450 10 500 10.2
540 0.74870 30 340 10.0
554 0.86865 30 340 11.6
566 0.69810 40 100 6.99
546 0.52050 40 100 5.22
565 0.65355 60 50 4.37
563 0.75015 60 50 5.01
80 681 0.34495 3 2000 46.1
669 0.36520 3 2000 48.8
680 0.38625 6 1000 25.8
683 0.44790 6 1000 29.9
670 0.54145 10 500 21.7
675 0.54850 10 500 22.0
685 0.63185 15 340 16.9
684 0.59610 15 340 16.0
630 0.87110 30 340 11.7
615 0.80740 30 340 10.8
676 0.78810 30 100 10.5
665 0.86885 30 100 11.6
664 1.12685 60 50 7.53
682 1.09845 60 50 7.34

interest. pH values at more acidic conditions were surface Ž rc . with the composition of the fluid imme-
computed using equations reported by Pitzer Ž1991, diately adjacent to the mineral surface can be quanti-
see Appendix A. because of the low accuracy of fied in terms of transition state theory. According to
standard glass electrodes at these conditions ŽBates, Wollast Ž1990. calcite dissolution can proceed via a
1973.. variety of mechanisms including the hydration of the
calcite surface consistent with
CaCO 3 Ž s . ™ Ca2qq CO 32y , Ž 1.
3. Theoretical background
the protonation by one or two hydrogen ions accord-
The overall reaction rate of a rapidly dissolving ing to
mineral, such as calcite under acidic conditions stems CaCO 3 Ž s . q Hq™ Ca2qq HCOy
3 , Ž 2.
from two distinct effects: detachment from the min-
or
eral surface Ž‘surface reaction’ effect., and diffu-
sional transport of dissolved aqueous species from CaCO 3 Ž s . q 2Hq™ Ca2qq H 2 CO 30 , Ž 3.
this surface through an interfacial layer into the bulk and the carbonation of the calcite surface by the
solution Ž‘transport’ effect. ŽDibble and Tiller, 1981; reaction
Guy and Schott, 1989; Murphy et al., 1989.. The
variation of CaCO 3 detachment rate from the calcite CaCO 3 Ž s . q H 2 CO 30 ™ Ca2qq 2HCOy
3 . Ž 4.
204 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214

The chemical reaction rate at these pH’s and at far

from equilibrium conditions is thus given by
rc s k 2 aH q ,s s k 2 g H q ,s c H q ,s Ž 7.
where g H q ,s and c H q ,s represent the activity coeffi-
cient and concentration of hydrogen ions in the
solution adjacent to the calcite surface.

Fig. 2. Reciprocal of calcite and limestone dissolution rates as a

function of the inverse square root of the disk rotation speed at a
temperature of 258C and pH s1. The symbols represent experi-
mental data and the solid lines represent a fit of these data to Eq.
Ž15. Žsee text..

Assuming that precipitation occurs by the single

reaction ŽPlummer et al., 1978; Busenberg and Plum-
mer, 1986.
Ca2qq CO 32y ™ CaCO 3 Ž s . , Ž 5.
a general equation for calcite dissolution rates can be
expressed as ŽWollast, 1990.
rc s k 1 q k 2 a H q ,s q k 3 aH2 q ,s q k 4 aH 2 CO 3 ,s
y k 5 aCa2q ,s aCO 32y ,s Ž 6.
where k 1 , k 2 , k 3 , k 4 , and k 5 stand for the chemical
rate constants of reactions Ž1. to Ž5. and ai,s refers to
the activity of the ith aqueous species adjacent to the
calcite surface. At acidic conditions ŽpH - 5., the
k 2 a H q ,s term dominates the right side of Eq. Ž6.
ŽBusenberg and Plummer, 1986; Chou et al., 1989. 1.

1
Van Cappellen et al. Ž1993. argued that the linear dependence
of calcite dissolution rates on hydrogen ion activity at acidic
conditions was due to the fact that these rates are proportional to
the second power of the surface concentration of protonated
carbonate sites.
Fig. 3. Reciprocal of calcite and limestone dissolution rates as a
function of the inverse square root of the disk rotation speed at
pH s1 and temperatures of Ža. 508 and Žb. 808C. The symbols
represent experimental data and the solid lines represent a fit of
these data to Eq. Ž15. Žsee text..
 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214 205

Table 4
Physical and chemical parameters used or obtained in the present study
X
Temperature n D Hq k2
Ž8C. Ž=10 7 m2 sy1 . a Ž=10 9 m2 sy1 . Ž=10 2 mol my2 sy1 .
25 9.0 2.9 " 0.4 7"2
50 5.6 4.0 " 0.4 16 " 2
80 3.7 9.4 " 0.4 25 " 2
a
Viscosity of 0.1 molal HCl solutions computed from equations and parameters reported by Zaytser and Aseyer Ž1992..

Proton consumption by calcite dissolution, in ac- hydrogen ion activity in the bulk solution consistent
cord with reaction Ž2., provokes a dramatic hydrogen with
ion concentration decrease in the fluid adjacent to r s kX2 g H q ,s c H q ,b f kX2 a H q ,b Ž 12 .
the mineral surface relative to the bulk solution. This
leads to the diffusional transport of hydrogen ions where kX2 designates an apparent rate constant de-
which can be described using fined by
kt k2
rt s k t Ž c H q ,b y c H q ,s . , Ž 8. kX2 ' Ž 13 .
k t q k 2 g H q ,s
where rt signifies the transport rate, c H q ,b refers to
This apparent rate constant has two limits, when
the hydrogen ion concentration in the bulk solution,
k t 4 k 2 g H q ,s then kX2 f k 2 , but when k t < k 2 g H q ,s
and k t denotes a transport rate constant. At station-
then kX2 f k trg H q ,s .
ary state, the quantity of hydrogen ions transported
Experimental studies of calcite dissolution at
to the surface equals that consumed by reaction Ž2.
acidic conditions are typically interpreted to generate
such that
kX2 , which is a function of both the chemical and
r s rc s rt . Ž 9.
Eqs. Ž7. – Ž9. can be combined to yield
k t c H q ,b
c H q ,s s , Ž 10 .
k 2 g H q ,s q k t

and
k t k 2 g H q ,s
rs c H q ,b . Ž 11 .
k t q k 2 g H q ,s

To the extent that g H q ,s and k t are independent of

solution composition and g H q ,b f g H q ,s , 2 the over-
all calcite dissolution rate is a linear function of the

2
These assumptions are only approximately correct. Aqueous
HCl diffusion coefficients and activity coefficients at 258C vary
over the range Ž3.05 to 3.43.=10y9 m2 sy1 ŽRobinson and
Stokes, 1959. and 0.8 to 1 ŽHelgeson et al., 1981., respectively,
with HCl concentration from 0 to 1 molal.
Fig. 4. Logarithm of measured Hq diffusion coefficients as a
function of reciprocal temperature. The symbols correspond to the
experimentally determined values generated in the present study
and the curve is consistent with an apparent activation energy of
19 kJ moly1 .
206 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214

Table 5
Dissolution rates of single calcite crystals, compressed calcite powder, and limestones at 258C and a disk rotation speed of 340 rpm as a
function of average bulk solution pH
Sample Sample pH Weight Elapsed Dissolution rate
number loss Žg. time Žmin. Žmol my2 sy1 .
Single calcite crystalsa 614 3.19 0.04510 240 7.53 = 10y5
623 3.16 0.04420 240 7.38 = 10y5
509 2.10 0.36970 240 7.60 = 10y4
510 1.04 1.04090 60 6.95 = 10y3
535 1.00 0.36775 20 7.37 = 10y3
560 1.00 0.34525 20 6.92 = 10y3
511 0.51 0.43290 10 1.73 = 10y2
564 0.09 0.33465 2 6.71 = 10y2
538 0.09 0.29825 2 5.98 = 10y2
679 y0.96 0.82355 1 3.30 = 10y1
687 y0.96 0.80170 1 3.21 = 10y1
674 y0.96 0.6197 1 2.48 = 10y1
Single calcite crystalsb 693 3.15 0.05155 240 8.61 = 10y5
709 3.15 0.04270 240 7.13 = 10y5
689 1.97 0.16675 60 1.11 = 10y3
711 2.03 0.10830 60 0.72 = 10y3
699 1.00 0.31240 30 4.17 = 10y3
712 1.00 0.29440 30 3.93 = 10y3
703 0.50 0.14525 5 1.16 = 10y2
707 0.50 0.14542 5 1.17 = 10y2
710 y0.96 0.62620 1 2.51 = 10y1
Compressed calcite powder 473 2.96 0.00250 60 6.13 = 10y5
466 3.03 0.01100 240 6.75 = 10y5
465 1.97 0.04440 120 5.45 = 10y4
475 2.04 0.09235 240 5.67 = 10y3
469 1.00 0.15380 45 5.03 = 10y3
393 0.99 0.12630 45 4.13 = 10y3
462 0.50 0.17140 10 2.52 = 10y2
460 0.48 0.15240 10 2.24 = 10y2
591 0.09 0.08280 2 6.10 = 10y2
594 0.09 0.07470 2 5.50 = 10y1
590 y0.96 0.27970 1 4.12 = 10y1
St. Maximin limestone 482 3.03 0.05595 240 9.59 = 10y5
499 2.02 0.16290 60 1.12 = 10y3
505 2.02 0.15450 60 1.06 = 10y3
497 1.00 0.16070 5 1.32 = 10y2
502 1.00 1.15800 45 1.06 = 10y2
490 1.00 1.05600 45 9.66 = 10y3
503 0.46 0.89360 10 3.68 = 10y2
488 0.47 0.89700 10 3.69 = 10y2
496 0.50 0.18900 2 3.89 = 10y2
597 0.09 0.85690 2 1.76 = 10y1
598 0.09 0.87830 2 1.81 = 10y1
850 0.09 0.42355 1 1.71 = 10y1
851 0.09 0.46068 1 1.86 = 10y1
802 y0.96 1.78470 1 7.22 = 10y1
803 y0.96 1.60915 1 6.51 = 10y1
804 y0.96 1.22875 1 4.97 = 10y1
805 y0.96 1.4117 1 5.71 = 10y1
Lavoux limestone c 635 3.20 0.03060 240 5.15 = 10y5
636 3.20 0.03225 240 5.43 = 10y5
 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214 207

Table 5 Žcontinued.
Sample Sample pH Weight Elapsed Dissolution rate
number loss Žg. time Žmin. Žmol my2 sy1 .
Lavoux limestone c 637 2.04 0.09245 60 6.23 = 10y4
638 2.04 0.08525 60 5.74 = 10y4
639 1.01 0.31070 30 4.19 = 10y3
640 1.02 0.26560 30 3.58 = 10y3
641 0.50 0.11245 5 9.09 = 10y3
642 0.50 0.11680 5 9.44 = 10y3
844 y0.96 0.83810 1 3.36 = 10y1
845 y0.96 0.91735 1 3.71 = 10y1
Lavoux limestoned 846 0.99 0.43840 20 8.86 = 10y3
847 0.97 0.49770 20 1.01 = 10y2
848 0.50 0.28620 20 2.31 = 10y2
849 0.50 0.33025 5 2.67 = 10y2
788 0.09 0.26500 1 1.07 = 10y1
791 0.09 0.27990 1 1.13 = 10y1
794 0.09 0.27075 1 1.09 = 10y1
800 0.09 0.24955 1 1.01 = 10y1
789 y0.96 1.77975 1 7.20 = 10y1
790 y0.96 1.30860 1 5.29 = 10y1
792 y0.96 1.26940 1 5.13 = 10y1
799 y0.96 2.07225 1 8.38 = 10y1
a
Cross section orientated perpendicular to the c-crystallographic axis.
b
Cross section orientated parallel to the cleavage.
c
Group 1.
d
Group 2.

transport rate constant. In general, the transport con-
stant depends on the hydrodynamics and geometry of
the experimental system. Consequently, kX2 values
generated from experimental data available in the
literature depend to a large extent on the experimen-
tal design. Owing to the complexities of both natural
systems and most experiments designed to measure
calcite dissolution rates, the transport constant cannot
be directly quantified, and thus measured rates can-
not be used to directly deduce the chemical rate
constant k 2 . An experimental design that allows
identification of the transport constant is the rotating
disk reactor. The transport rate constant for the
rotating disk reactor at disk rotation speeds 4 0, is
given by ŽGregory and Riddiford, 1956; Pleskov and
Filinovski, 1976; Alkattan et al., 1997a,b.
k t s Drd s 0.6 D 2r3ny1 r6v 1r2 ,
where d signifies the thickness of the diffusion
layer, n corresponds to the kinematic solution vis-
cosity, v represents the disk rotation speed, and for
the case of calcite dissolution at acidic conditions, D
stands for the Hq diffusion coefficient. It follows
from Eqs. Ž11. and Ž14. that for a rotating disk
reactor
1 1 1
s q 2r3 y1r6
vy1 r2 .
r k 2 c H q ,b g H q ,s 0.62 D n c H q ,b
Ž 15 .
At constant bulk solution pH, the reciprocal overall
dissolution rate Ž1rr . is a linear function of the
reciprocal square root of the rotating disk speed
Ž vy1 r2 .. The intercept of this straight line can be
used to deduce k 2 , the chemical rate constant, while
its slope allows determination of the diffusion coeffi-
cient Ž D .. Note, however, that when the chemical
rate constant Ž k 2 . is large compared to the transport
rate constant Ž k t ., the first term on the right side of
Ž 14 .
the Eq. Ž15. becomes small. Therefore, plots of 1rr
vs. vy1 r2 will yield a linear function that appears to
pass through the origin. At such conditions it is not
possible to determine the chemical rate constant
208 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214

directly from dissolution rate data obtained from a linear function of vy1 r2 . The solid line in these
rotating disk reactors. figures represents the regression of these data using
Eq. Ž15.. Because, within the uncertainty of the data,
these regression curves pass through the origin it is
4. Experimental results and discussion not possible to determine the chemical rate constant
Ž k 2 . from these data. The distribution of data points
Disk weight loss, elapsed times, rotation speeds, in Figs. 2 and 3 suggest that the intercepts of the
average bulk solution pH, and computed dissolution linear regression curves, corresponding to 1rr at
rates for all experiments are presented in Tables 2, 3, vy1 r2 s 0, do not exceed 25, 15, and 10 m2 s moly1
5–7. pH values reported in these tables are the
average of the initial and final pH of the bulk
reactive solution. Dissolution rates listed in these
tables were computed from
Dm
rs Ž 16 .
stW
where D m represents the weight loss of the solid, s
designates the geometric surface area of the disk, t
represents elapsed time, and W signifies the molecu-
lar weight of calcite Ž100.1 grmol.. As the pH and
ionic strength were allowed to drift, computed r
values represent an integrated average of the dissolu-
tion rates during each experiment. The uncertainties
of each individual dissolution rate reported in Tables
2, 3, 5–7 stem from corresponding uncertainties in
sample weighting, experiment duration, disk rotation
speeds, and temperature. Slight irregularities in sam-
ple surface morphology, variations in crystal orienta-
tion, and the evolution of CO 2 bubbles at the calcite
surface also add to the scatter apparent in the experi-
mental data. Taking into account these factors, the
overall uncertainty in the individual dissolution rates
given in these tables is ; 15%.
Single calcite crystal, limestone, and compressed
calcite powder dissolution rates measured at a bulk
solution pH of 1 as a function of disk rotation speed
at 258C are given in Table 2. Corresponding data
obtained for the dissolution of single calcite crystals,
orientated perpendicular to the c-crystallographic axis
performed at 508 and 808C are listed in Table 3. The
reciprocal of these measured dissolution rates are
depicted as a function of the inverse square root of
the disk rotation speed in Figs. 2 and 3, respectively.
It can be seen in Fig. 2 that the measured dissolution
rates of each of the three different sample types are Fig. 5. Measured Ža. calcite and Žb. limestone dissolution rates at
258C and a disk rotation speed of 340 rpm as a function of
identical within experimental uncertainty. According average bulk solution pH. The symbols represent experimental
to Eq. Ž15., for a series of experiments performed at data obtained in the present study and the linear curve represents a
constant bulk solution pH, 1rr can be considered as fit of these data to Eq. Ž12. Žsee text..
 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214 209

at 258, 508, and 808C, respectively. These 1rr upper
bounds limit k 2 to be greater than 0.4, 0.7, and 1.0
mol my2 sy1 at 258, 508, and 808C. The slopes of
the regression curves depicted in Figs. 2 and 3 are
used together with solution viscosities Ž n . listed in
Table 4, to generate the diffusion coefficients Ž D .
values given in Table 4. The Hq diffusion coeffi-
cient Ž D . resulting from this analysis at 258C is
Ž2.9 " 0.4. = 10y9 m2 sy1. This value is similar to
that of Robinson and Stokes Ž1959., who reported a
diffusion coefficient of 3.05 = 10y9 m2 sy1 for 0.1
molal HCl solutions at 258C.
The variation of Hq diffusion coefficients as a
function of temperature can be described with an
Arrhenius equation of the form
D s A exp Ž yEA rRT .
where EA represents an apparent activation energy
and A a pre-exponential factor. The logarithms of
diffusion coefficients obtained in the present study
are plotted as a function of 1000rT in Fig. 4. It
follows from Eq. Ž17. that the slope of the straight
line in Fig. 4 is equal to yEA r2303R and its
intercept to log A. The slope of the linear curve
depicted in Fig. 4 is consistent with an apparent
activation energy EA s 19 " 4 kJ moly1 ; this value
is somewhat higher than the 13.2 kJ moly1 obtained
for the apparent activation energy of HCl diffusion
by Oelkers and Helgeson Ž1988..
Single calcite crystal, limestone, and compressed
calcite powder dissolution rates measured at 258C, a
constant disk rotation speed of 340 rpm, and various
average bulk solution pH are given in Table 5 and
illustrated by symbols in Fig. 5. It can be seen in this
figure that the dissolution rates of the various solid
Ž 17 .
materials are identical within experimental uncer-
tainty. Moreover the logarithms of these rates exhibit
a linear dependence on average bulk solution pH.

Table 6
Dissolution rates of single calcite crystals, compressed calcite powder, and limestones at 508C and a disk rotation speed of 340 rpm as
function of average bulk solution pH
Sample Sample pH Weight Elapsed Dissolution rate
number loss Žg. time Žmin. Žmol my2 sy1 .
Single calcite crystalsa 553 3.23 0.06805 240 1.14 = 10y4
550 3.22 0.05895 240 9.85 = 10y5
539 2.00 0.21640 60 1.45 = 10y3
557 2.00 0.21780 60 1.45 = 10y3
540 1.01 0.74870 30 1.00 = 10y2
554 1.04 0.86865 30 1.16 = 10y2
533 0.50 0.42795 5 3.43 = 10y2
545 0.50 0.31455 5 2.60 = 10y2
Compressed calcite powder 742 3.02 0.02835 250 1.67 = 10y4
743 3.03 0.02155 250 1.27 = 10y4
751 2.03 0.03815 60 9.36 = 10y4
747 2.02 0.04755 60 1.17 = 10y3
749 1.00 0.22655 30 1.11 = 10y2
744 1.01 0.25365 30 1.24 = 10y2
746 0.50 0.08605 5 2.53 = 10y2
741 0.50 0.09010 5 2.65 = 10y2
Lavoux limestone 730 3.24 0.05350 240 9.01 = 10y5
732 3.24 0.04950 240 8.34 = 10y5
733 2.10 0.14480 60 9.76 = 10y4
731 2.10 0.11190 60 7.54 = 10y4
734 1.05 0.65470 30 8.82 = 10y3
735 1.05 0.55360 30 7.46 = 10y3
736 0.50 0.23975 5 1.94 = 10y2
737 0.50 0.31630 5 2.56 = 10y2
a
Cross section oriented perpendicular to the c-crystallographic axis.
210 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214

The slope of the linear curves drawn through these
data is equal to y1, which is consistent with Eqs.
Ž11. and Ž12. and the concept that reaction Ž2. is the
dominant calcite dissolution mechanism over the pH
range y1 to 3. The slight decrease in rates relative
to the regression curve at pH s y1 may be due to
uncertainties in calculating pH at these extreme con-
ditions. Corresponding dissolution rates as a function
of pH at 508 and 808C are given in Tables 6 and 7,
and illustrated in Fig. 6. Again corresponding rates

Table 7
Dissolution rates of single calcite crystals, compressed calcite powder, and limestones at 808C and a disk rotation speed of 340 rpm as a
function of average bulk solution pH
Sample Sample pH Weight Elapsed Dissolution rate
number loss Žg. time Žmin. Žmol my2 sy1 .
Single calcite crystalsa 627 3.25 0.05575 240 9.31 = 10y5
628 3.25 0.06190 240 1.03 = 10y4
673 3.24 0.04845 240 8.09 = 10y5
678 3.25 0.08805 240 1.47 = 10y4
686 3.24 0.05940 240 9.92 = 10y5
661 3.16 0.03855 120 1.29 = 10y4
667 3.19 0.03310 120 1.11 = 10y4
662 2.09 0.15990 60 1.07 = 10y3
671 2.12 0.14440 60 9.65 = 10y4
620 2.10 0.19545 60 1.31 = 10y3
618 2.10 0.19215 60 1.28 = 10y3
668 2.08 0.14010 30 1.87 = 10y3
688 2.06 0.13400 30 1.79 = 10y3
684 1.02 0.59610 15 1.59 = 10y2
685 1.01 0.63185 15 1.69 = 10y2
663 1.03 1.23845 30 1.65 = 10y2
666 1.03 1.17425 30 1.57 = 10y2
672 0.51 0.50495 3 6.75 = 10y2
677 0.51 0.47965 3 6.41 = 10y2
Compressed calcite powders 745 3.02 0.02110 120 2.59 = 10y4
748 3.05 0.01940 120 2.38 = 10y4
567 2.00 0.04600 30 2.26 = 10y3
584 2.00 0.03220 30 1.58 = 10y3
774 1.00 0.18025 15 1.77 = 10y2
768 1.00 0.15565 15 1.53 = 10y2
767 0.50 0.22020 5 6.48 = 10y2
781 0.50 0.17875 5 5.26 = 10y2
765 0.50 0.11650 3 5.72 = 10y2
775 0.50 0.11480 3 5.63 = 10y2
Lavoux limestone 725 3.22 0.07520 240 1.27 = 10y4
726 3.17 0.05165 240 8.70 = 10y5
738 3.17 0.03625 130 1.13 = 10y4
729 3.08 0.05335 120 1.80 = 10y4
739 3.07 0.04180 120 1.41 = 10y4
760 2.09 0.12065 30 1.63 = 10y3
752 2.08 0.12585 30 1.70 = 10y3
756 1.07 1.55655 30 2.10 = 10y2
759 1.05 1.52300 30 2.05 = 10y2
753 1.02 0.63490 15 1.71 = 10y2
757 1.01 0.79620 15 2.15 = 10y2
754 0.50 0.56660 3 7.64 = 10y2
755 0.50 0.57270 3 7.72 = 10y2
a
Cross section oriented perpendicular to the c-crystallographic axis.
 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214
Fig. 6. Measured calcite and limestone dissolution rates at 50 and
808C and a disk rotation speed of 340 rpm as a function of
average bulk solution pH. The symbols represent experimental
data obtained in the present study and the linear curve represents a
fit of these data to Eq. Ž12. Žsee text..
for each solid are identical within uncertainty and
consistent with log r A aH q ,b . The intercepts of the
linear curves shown in Figs. 5 and 6 were used to
generate the kX2 values given in Table 4.
The kX2 value obtained in the present study for
experiments performed at a disk rotation speed of
340 rpm and 258C is Ž7 " 2. = 10y2 mol my2 sy1.
Corresponding values reported in the literature in-
211
clude 8.6 = 10y2 mol my2 sy1 reported by Busen-
berg and Plummer Ž1986. from the dissolution of
calcite crystals in a stirred solutions, 0.51 mol my2
sy1 obtained by Plummer et al. Ž1978. from rotating
disk experiments performed with disk rotation speeds
ranging from 800 to 1300 rpm, and 0.89 mol my2
sy1 deduced by Chou et al. Ž1989. from the interpre-
tation of fluidized bed reactor experiments. Differ-
ences between these results likely stem from the
hydrodynamics of the different experimental designs
used to obtain the rates. According to Eq. Ž13., kX2
will vary from a maximum equal to k 2 to a mini-
mum equal to k trg H q ,s depending on the relative
values of these parameters; the larger k t is relative to
k 2 , the more kX2 tends towards its upper limit, k 2 . As
the kX2 deduced by Chou et al. Ž1989. is the highest
among the reported kX2 values, above the 0.4 mol
my2 sy1 lower bound for k 2 obtained from Fig. 2,
and the geometry of fluidized bed reactors likely
results in a relatively high k t , it seems probable that
this kX2 value most closely approaches k 2 .
5. Conclusions
The experiments described above indicate that the
dissolution rates of single calcite crystals, lime-
stones, and compressed calcite powders at acidic
conditions are identical within experimental uncer-
tainty. These rates are linear functions of bulk solu-
tion pH over the range y1 to 3 at temperatures from
258 to at least 808C. Apparent rate constants and Hq
diffusion coefficients increase substantially with in-
creasing temperature and are consistent with corre-
sponding values reported in the literature. The results
presented in this study will be used together with
calcite dissolution rates in the presence of aqueous
phosphoric acid and magnesium chloride to assess
the effect of these species on calcite dissolution
kinetics at acidic conditions ŽAlkattan et al., 1998..
Acknowledgements
We would like to thank Jean-Luc Bouchez,
Christophe Monnin, Gilles Berger, Gleb Pokrovski,
Oleg Pokrovsky, Jean-Marie Gautier, Maud Gaute-
212 M. Alkattan et al.r Chemical Geology 151 (1998) 199–214

lier, Patrica Fournier, Delphine Yeghicheyan, Carlos

Jove, and Stacey Callahan for helpful discussions
during the course of this study. We are indebted to
Patrick Brady, Alfonso Mucci, and Birgitta Kali-
nowski for providing insightful reviews. Jocelyne
Escalier, Jean Claude Harrichoury, Claude Lurde,
and Christian Saccareau generously aided us with
their technical expertise. Support from Agence Na-
´
tionale pour la gestion des Dechets Radioactifs
ŽANDRA. and the Centre National de la Recherche
Scientifique ŽCNRS. is gratefully acknowledged.

Fig. 7. Variation of pH in aqueous HCl solutions at 258C. The

Appendix A solid curve was computed using the Pitzer equations as a function
of the logarithm of total aqueous HCl concentration and the
dashed line corresponds to pH sylog c HC l Žsee text..
Bulk solution pH for all solutions in the present
study having pH - 2 were computed using the Pitzer
Ž1991. model. Within this model the activity coeffi-
molrkg, but significant differences are apparent at
cient of an aqueous hydrogen ion Žg H q . in the higher concentrations.
system HCl–H 2 O can be computed from
ln g H qs fg q m Cl Ž 2 B HCl q EC HCl .
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