Journal of Nuclear Science and Technology

ISSN: 0022-3131 (Print) 1881-1248 (Online) Journal homepage: http://www.tandfonline.com/loi/tnst20

Dissolution Rates of Amorphous Silica in Highly

Alkaline Solution

Yuichi NIIBORI , Masahisa KUNITA , Osamu TOCHIYAMA & Tadashi CHIDA

To cite this article: Yuichi NIIBORI , Masahisa KUNITA , Osamu TOCHIYAMA & Tadashi CHIDA
(2000) Dissolution Rates of Amorphous Silica in Highly Alkaline Solution, Journal of Nuclear
Science and Technology, 37:4, 349-357, DOI: 10.1080/18811248.2000.9714905

To link to this article: http://dx.doi.org/10.1080/18811248.2000.9714905

Published online: 07 Feb 2012.

Submit your article to this journal

Article views: 1667

View related articles

Citing articles: 13 View citing articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=tnst20

Download by: [University of the Philippines Diliman] Date: 24 April 2017, At: 09:26
 Journal of NUCLEAR SCIENCE and TECHNOLOGY, Vol. 37, No. 4, p. 349-357 (April 2000)

Dissolution Rates of Amorphous Silica

in Highly Alkaline Solution
Yuichi NIIBORI*,t, Masahisa KUNITA**, Osamu TOCHIYAMA* and Tadashi CHIDA**

* Department of Quantum Science and Energy Engineering,

Graduate School of Engineering, Tohoku University
** Department of Geoscience and Technology, Graduate School of Engineering, Tohoku University

(Received February 18, 1999)

Cement is an essential materials to construct the subsurface radioactive waste disposal system. However,
cementitious materials alter the groundwater pH to highly alkaline condition about 13. To comprehend the
effect of such a hyperalkaline condition on the repository surroundings, this study focused on the dissolution
rates of amorphous silica at [NaOH]=l0- 1 mol·dm- 3 . The used samples were three kinds of pure commercial
silica and a natural silica scale which was obtained from inside wall of the hot-water pipe of a geothermal power
plant. The observed dissolution rates were interpreted with using the model, which assumed that the particle
sizes decrease with the progress of dissolution. Moreover, due to the particle size distribution anticipated
in the natural silica scale, this analysis assumed it contained particles with various initial diameters. In
the results, (1) all pure silica samples and at least 60 wt% of the silica scale showed good agreement of the
activation energy of the dissolution in the range of 77 through 88 kJ-mol- 1 in the highly alkaline solution, (2)
these rate constants were of the order of 10-s_10- 7 mol·m- 2 -s- 1 at around 310 K and were definitely larger
than those already reported for quartz, (3) the specific surface area based on BET method was revealed to
be an important factor to give the main difference in the dissolution rates between the synthetic silica and
the natural silica.

KEYWORDS: amorphous silica, dissolution rate, highly alkaline solution, radioactive

wastes, repository system, alternation, kinetics, silica scale, silica gel, activation energy,
pH value, solidification, waste processing, temperature dependence, radioactive waste dis-
posal

dissolution rate of silica is considered to be the drastic

I. Introduction
A main concern about the use of cement in the ra-
dioactive waste disposal system is that groundwater con-
tacting with cement may attain pH values as high as
13( 1 )( 2 ). The hyperalkaline plume would cause continu-
ous alterations in the physical and chemical properties
of the fractured layer or of the host rock surrounding the
repository. Among various materials affected by such a
change in pH, silica is one of the most important be-
cause of its abundant and ubiquitous existence and of
its dominant role in the static and dynamic hydrogeo-
chemical phenomena. Thus far, the dissolution rates of
silica have been discussed particularly about the crys-
talline silicaC 3 )-C 12 l. These results have been applied to
the feasibility study of placing the radioactive waste in
man-made repositories situated in natural rock forma-
tion C1 ). However, as for the amorphous silica, the dis-
solution rates have not been discussed sufficientlyC 13 )-C 15 )
in spite of its importance in the understanding of the
radionuclide migration, particularly, through fractured
layers accompanied by groundwater.
In basic solution, the important factor governing the
*,** Ammaki, Aoba-ku, Sendai 980-8579.
t Corresponding author, Tel. & Fax. +81-22-217-6338,
E-mail: niibori@qse.tohoku.ac.jp
increase in the concentration of the negatively charged
surface species, [=Si-o-J. When the silica is in contact
with water, the surface interaction can be described by
=Si-0-S=+H 2 0---+2(=Si-OH), where =Si-0-Si= repre-
sents a part of Si0 2 frameworkC 4 )C 5 ). In basic solution,
=Si-OH changes into =Si-O-, depending on [OH-J.
Brady and WaltherC 16 ) found from the dissolution rates
of quartz that the rates are nearly proportional to
[=Si-O-J. This fact suggested that the surface depro-
tonation (i.e., the formation of =Si-0-) leads to highly
polarized interatomic Si-0 bonds and thus facilitates the
detachment of Si into the solution. This dependency of
the dissolution rate on [=Si-O-J has been also confirmed
for amorphous silica by Niibori et al. C17), where the disso-
lution rates of two types of amorphous silica were shown
to be almost proportional to [OH-jD- 5 in the range of pH
from 10 through 13. However, the study was not suf-
ficient to evalua_te the rate constants, particularly, with
regard to the fraction of [=Si-0-J on the surface and
the difference of specific surface area. Allen et al. C18 )
conducted the pH titration of suspended amorphous sil-
ica, and confirmed that above pH 12, almost all surface
sites are present as =Si-o- sites. Thus in highly alkaline
plume with pH 13, the dissolution rate strongly reflects
on the surface concentration of =Si-O-.

349
350 Y. NIIBORI et al.

Although the natural sample of amorphous silica pro-

duced in underground are not easily available, it is crucial
to examine the dissolution rates of natural silica besides
the man-made samples to estimate the role of silica in un-
derground transport-phenomena. This paper discusses
the dissolution rates of amorphous silica in high pH (13)
solutions, using three kinds of commercial silica gel and
a silica scale, where the latter is collected from Onuma
geothermal field as a natural sample of amorphous silica.
While highly alkaline plume mainly results from the
dissolution of Ca(OH)2 in cement, this study used
10- 1 mol-dm- 3 NaOH solution to avoid side reactions
caused by Ca 2+ and to keep [=Si-O-J constant at the
surface. In this solution, [OH-J was considered to be
constant, since sufficiently small amounts of the sam-
ples were used in the experiments so that the amount of
proton released by the dissolution could be neglected as
compared with that of OH- in the solution. On the other
hand, we could not ignore the change of the surface area
accompanying the dissolution process. ·In order to con-
sider its dependency in the course of time, the shrinking
spherical particle model was applied to the rate estima-
tion in this study.
II. Experimental
1. Samples
Table 1 gives three kinds of pure amorphous sil-
ica used in this study, as well as some of their physi-
cal/ chemical properties. They were obtained from Wako
Pure Chemical Industries, Ltd., and from Mallinckrodt
Co., and which will be respectively referred to as Wako-
gel C-200, Wako-gel LC-50H and Mallinckrodt silica in
this paper. All of their X-ray diffraction patterns showed
amorphous feature. Since Mallinckrodt silica was pur-
chased as powder of 100 mesh under and contained
small granules or coherent aggregates of submicron par-
ticlesC19l, a size fraction of 74-149 µm particle diameters
was separated by sieving. While, the particle sizes of
the Wako-gel C-200 and LC-50H are in the given diam-
eter ranges without sieving. Specific surface areas were
estimated through BET method using N 2 gas.
Photograph 1 shows the photomicrograph of Wako-
gel C-200 before dissolution. The Wako-gel C-200
grains exhibit surface morphology characteristic of an-
gular grains with conchoidal mechanical fracturing pat-
Photo. 1 The photomicrograph of pure silica sample
(Wako-gel C-200)
The similar morphology was observed also for
Wako-gel LC-50H and Mallinckrodt silica.
terns. The similar morphology was observed also for
Wako-gel LC-50H and Mallinckrodt silica.
As an amorphous natural silica, this study examined
the silica scale collected from the inside wall of the hot-
water pipe at Onuma geothermal power plant located
in Akita prefecture, Japan. Ito et al.C 20 l have reported
its chemical composition, which indicated that Si0 2 was
rich, and the weight ratios of Ab0 3 /Si0 2 and CaO /Si0 2
were in the ranges from 0.03 to 0.15 and from 0.01 to
0.05, respectively. The X-ray diffraction pattern showed
only the amorphous feature. This natural sample is re-
ferred to as Onuma silica scale.
Onuma silica scale was crushed in agate mortar. Since
the crushed silica contained very fine particles sticking
to relatively larger ones, it was impossible to sieve the
crushed sample. Photograph 2 shows the scanning
electromicrographs (SEM) of Onuma silica scale before
(f=O) and after (!=0.7) dissolution, where f denotes
the fraction dissolved, that is, !=(amount of soluble sil-
ica)/ (amount of silica sample introduced into the alkaline
solution). As shown in Photo. 2(a), they clearly indi-
cate that the diameters of the particles are smaller than
100 µm and not uniform. As for the specific surface area,
BET method by N2 gas and the air permeability method
indicated l.2m 2 ·g- 1 and 0.95m 2 ·g- 1 , respectively, for
Onuma silica scale. The latter method is based on

Table 1 Pure amorphous silica samples examined in this study

Samples Wako-gel C-200 Wako-gel LC-50H Mallinckrodt silica

Particle diameter (µm) 74-150 50 74-149
Specific surface area (m 2/g) 450 450 350
Apparent specific gravity (g/cm 3 ) 2.2 2.2 2.0
-H20 (TG, up to 378K) Si02·0.41H20 Si02·0.51H20 Si02·0.86H20
+H20 (TG, from 378 to 1,073K) Si02·0.23H20 Si02 ·0. l8H20 Si02·0.38H20

-H20 and +H20 indicate the water contents obtained by thermogravimetry (TG), where -H20 refers to the
molar amount of H20 per Si02 lost by heating from room temperature to 378K (sorbed water), while +H20 by
heating from 378 to 1,073K (essential water).

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Dissolution Rates of Amorphous Silica in Highly Alkaline Solution
Photo. 2 The SEM micrographs of the Onuma silica scale
((a) the fraction dissolved, f=O, i.e., the state
before dissolution and (b) f =0. 7, temperature:
330 K, stirring rate: 8.3 s- 1 )
Kozeny-Carman equation relating the surface area with
the residence of air-flow through the bed packed with
the particles. These estimated values around 1 m 2 -g- 1
are very small as compared with the other pure samples
shown in Table 1. The agreement of the specific surface
area by the BET method with that by the air perme-
ability method suggests that Onuma silica scale has little
inner pores in the particle. For the water contents, TG
showed that -H 2 0 was 6.3wt% and +H 2 0 was 8.6wt%,
where wt% was adopted because the sample was not
pure. (If pure, 8.6 wt% corresponds to Si0 2 ·0.31H 2 0 for
+H 2 0. This value is almost similar to those for the other
pure samples.) The specific gravity was 2.lg·cm- 3 .
2. Procedure
Figure 1 illustrates the apparatus used for the dis-
solution experiment. Purified nitrogen was continuously
passed through the vessel to avoid contact with air. The
gas had been saturated beforehand by water vapor at
each temperature. The polyethylene vessel with the
cover has a fluid volume of 500 cm3 . The alkaline so-
VOL. 37, NO. 4, APRIL 2000
351
Ribbon heater
~ Polypropylene stirrer
Flow me--;-e; - - f~
N2gas
Overflow
Thermostat
Fig. 1 Illustration of experimental apparatus
lutions were prepared by dissolving analytical reagent-
grade sodium hydroxide in distilled water. The con-
centration, i.e., the initial [NaOH], was always set at
10- 1 mol-dm- 3 in each experiment. This alkaline so-
lution was put into the vessel and mechanically stirred
with a polypropylene stirrer. The vessel was submerged
into the thermostat. The temperature was kept con-
stant within ±0.5 K of sufficient precision. Weighed
amount of the pure silica gel (100 mg) or the crushed
silica scale (200 mg) was then introduced into the vessel,
and aliquots (less than 9 cm 3 ) were periodically taken for
analysis. After the samples had been filtered through the
membrane filter of pore size 0.45 µm, the amount of sol-
uble silica was determined photometrically by the yellow
silicomolybdate method. The values of initial and final
pH were measured to confirm its constancy.
To estimate the dissolution rates, the dissolution ex-
periment should be carried out under such condition that
the concentrations of dissolved silica are always well be-
low the solubility limit. Since the solubility of the amor-
phous silica at pH>9 could not be determined with suf-
ficient precision due to its strong dependence on [OH-J
( e.g., Ref. (19)), the rates of dissolution into the solutions
containing various initial concentrations of soluble silica
were compared. Figure 2 shows an example of the frac-
tion dissolved, f, against time. The results agree with
each other within the experimental error, indicating that
the dissolution rate, df / dt, does not depend on the ini-
tial concentration of soluble silica. This means that the
experiments were carried out under the condition suffi-
ciently lower than the solubility limit. Also, we can rec-
ognize that the amount of proton liberated through the
dissolution of Si0 2 does not give any appreciable change
in the dissolution rate. This can be confirmed from
the estimation that, e.g., 100mg of Si0 2 -l.24H 2 0 (for
Mallinckrodt silica in Table 1) in 500 cm3 corresponds
to [Si0 2 ]=2.4x 10- 3 mol·dm- 3 , which will consume less
than 5x 10- 3 mol-dm- 3 of [OH-] when converted into
H 3 Si0 4 and/ or H 2 Si0~-c 21 Jc22J.
The stirring rate 8.3 s- 1 (500 rpm) was selected by
judging from the preliminary experiments. As shown in
Fig. 3, the dissolution is not affected by increased stir-
ring from 1. 7 s- 1 (100 rpm) to 16. 7 s- 1 (1,000 rpm) over
the whole range of the fraction dissolved. This means
352 Y. NIIBORI et al.

/ ........
,/
p
"
/ ' Initial [SiOz]Jmol dm-3
0.5
.," -o-o_ ....o .... 303K

ii
'Pl
...../lo .....

---c---
0.6xl0-3
1.8xl.0-3
.... +..... 294K
.....,!!...... 289K

Wako-gel C-200
0 50 100 150 200
200 400 600
time (min)
time (min)
Fig. 2 Effects of initial [Si02] on the dissolution rate
The initial solutions were prepared by dissolving

·l:
1 ~ ~ ~ - . . - { ' : 1 - T - , R - - ~ ~......-~~~-
Mallinckrodt silica (0 mol·dm- 3 , 0.6x 10- 3 mol·dm- 3
and l.8x 10- 3 mol·dm- 3 in [Si0 2], respectively) into ,./;!';"'°...+" .. .A......... Ls··"(b).
[NaOH]=l0- 1 mol·dm- 3 at 293 K. After filtering the
each solution through the membrane filter of pore
f . . . i. . 11. ../
size 0.45 µm, 100 mg of the Mallinckrodt silica was
added to the solution (stirring rate: 8.3s- 1 ).
r l ,/
0.5 O.i ! ...i./
.... -0-- 303K
. . +.... 293K
0
~
..._, .,.=i • .f ,./ .....,!!...... 288K
'+-<
"O~
.i ,...-IS.
CL) ,i.(,.t{ Wako-gel LC-508
.e0
~ 0.5 200 400 600
;,a ..... a..... 1.7 s-1 time (min)
.§ -o- 8.3 s-1
u
,a ---A--- 16.7 s-1

(c)
0 50

time (min)
100 150 200
-
~
"'"'
·,::J
CL)

Fig. 3 Effect of the stirring rate on the dissolution rate ~

0
rJl 0.5
(sample: the Mallinckrodt silica, sample amount: :.a
.... o .... 304K
100 mg, and temperature: 293 K)
..
d
......
u
0
. .. +.... 292K
e:
'1;
.....,!!...... 288 K
that in the range of from to l.7s- 1the disso- 16.7s- 1 .....IJ.. •·· 283 K
lution rate is not limited by the rate at which dissolved
Mallinckrodt
silica or orr- is transported through the film existing be-
tween bulk and solid surface under these conditions. The 0 200 400 600
importance of diffusion processes through such a film is time (min)
frequently pointed out in some water-rock interactions.
However in this case, since the reaction at the surface Fig. 4 Experimental results of dissolution behaviors for the
silica is slow in comparison with the diffusion, the whole pure silica gels
dissolution process is controlled by the reaction at the ((a) the Wako-gel C-200, (b) the Wako-gel LC-50H
surface. Under such a condition, the concentrations of and (c) the Mallinckrodt silica, (stirring rate:. 8.3s- 1
solutes adjacent to the surface can be considered to be and sample amount: 100 mg))
the same as the bulk solution.

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Dissolution Rates of Amorphous Silica in Highly Alkaline Solution
Ill. Results
Figure 4 shows the relation of fraction dissolved,
f, to time for the pure samples, i.e., Wako-gel C-200
(Fig. 4(a)), Waka-gel LC-50H (Fig. 4(b)) and Mallinck-
rodt silica (Fig. 4( c)). In all cases, the dissolution rates,
df / dt, increase as the temperature of solution is set to
higher value. However, the dependency on tempera-
ture is different between the samples. That is, Wako-
gel C-200 and LC-50H have the similar tendency against
temperature, even if these geometric particle sizes are
different. On the contrary, Mallinckrodt silica indicated
relatively larger dissolution rates than that for Waka-gel
C-200 or LC-50H.
Photograph 3 shows the SEM micrographs of
Mallinckrodt silica at (a) f=O and (b) /=0.7. It clearly
indicates that the conchoidal fracturing patterns such as
those indicated by the arrows in Photo. 3(b) are retained
through the dissolution process. If the rate determining
step is the diffusion process through the film, the shape of
the grains would become round, because the film thick-
ness between the surface and bulk depends on the irreg-
Photo. 3 The SEM micrographs of the Mallinckrodt silica
((a) f=O and (b) f=0.7, temperature: 293 K, stir-
ring rate: 8.3 s- 1 and arrows in (b) examples of
the surface of the conchoidal fracturing patterns)
VOL. 37, NO. 4, APRIL 2000
353
ularities of particle-surface. Namely, the thickness will
be relatively thick on the concave surface and thin, in
reverse, on the convex surface. If the dissolution rate of
particle is controlled by diffusion through the film, the
concave surface lags behind in dissolution, as compared
with the convex surface. Such a local gap in dissolution
rate will make the particle surface round gradually.
Figure 5 shows the dissolution behaviors of Onuma
silica scale. While the initial dissolution rate at each
temperature was relatively larger than the pure silica
gels, the fraction dissolved at 400 min was smaller than
those of the pure silica gels even if the temperature was
set to 323K.
IV. Discussion
Considering the tendencies shown in Chap. III. Re-
sults, we have tried to interprets the observed dissolu-
tion rates with using the shrinking spherical modelC 23 l,
which assumed that the particle is sphere with the ini-
tial radius r 0 and its sizes decrease with the progress of
dissolution. Moreover, this analysis assumed that the
silica scale contained particles with various initial diam-
eters due to its particle size distribution. To estimate
the dissolution rate, first, we assume
dC
Vai = akS, (1)
where V is the bulk volume (dm3 ), C the concentra-
tion of the soluble silica (mol·dm- 3 ), k the rate constant
(mol·m- 2 -s- 1 ), S the total surface area of silica particles
(m2 ), t the time (s) and a the fraction defined by
[===Sio-1
a = ---'----'--- at the surface, (2)
[= SiOH] + [= SiO-] '
where the introduction of a to the rate equation is based
on the approach by Brady and WaltherC 16l. In this
work, we will assume a=l because [OH-J»(H4Si04]t0 ta1,
1 ---------------
0 200 400
time(min)
Fig. 5 Experimental results of dissolution rate for Onuma
silica scale (stirring rate: 8.3 s- 1 and sample amount:
200mg)
354 Y. NIIBORI et al.

where [H4Si04]t 0 tal is the total concentration of the sol-

uble silica. Applying the shrinking spherical particle
model to the dissolution processes, the relation of C to
f is

8
(3) 6:
~0.5
I
where n is the number of particles, r 0 the initial ra- y
,-<
dius (m) of particles, M the gram-molecular amount
of Si0 2-xH 20 (kg·mol- 1 ), where x indicates the molar
amount of the essential water per one mole of Si02, and
Ps is the particle density (kg·m- 3). Also, the relation of
Wako-gel C-200
Sand f is
S = n47fr5(l - !) 213 . (4) 200 400 600
time (min)
Since silica particles are not spherical in geometry, the
actual surface area is not equal to S. Moreover, BET
data suggest the existence of inner surface, to which not
only nitrogen gas but also solution may be accessibleC 24 ).
However, if the particles and their inner pores at vari-
ous dissolution stage retain their initial morphology and
are similar in shape as shown in Photo. 3, the effective
surface area is considered to be proportional to S. There-
fore, kin Eq. (1) is the apparent rate constant including
the proportionality constant of the true surface area to
\o.s,-<
y
s. ,-<

Substituting Eqs. (3) and (4) into Eq. (1), we obtain

dt = k* (1 - !)2/3' (5)
Wako-gel LC-SOH
where k* is 3Mk/(rop 8 ). Further, Eq. (5) yields 01(¥0........--'----''--.J...--'--'---'-'---...,___.____,_~
0 200 400 600
1 - (1 - f)l/3 = !k*t (6) time (min)
3 .
Figure 6 shows the application of Eq. (6) to the
experimental results for the pure silica gels, shown in
Fig. 4. Each line in Fig. 6 was drawn by selecting the
data so that they would give the correlation coefficient
of 1-(l-!) 1 13 against t larger than 0.99. In all cases,
Eq. (6) cannot describe the initial dissolution stage be-
havior at 1-(1-1) 113<0.1 (or f<0.27). The deviation 8
6:
from Eq. (6) is more remarkable at lower temperature. ~0.5
I
Probably, this delay in dissolution is caused by the extra C 1
time that is necessary for the solution to diffuse into the ,-<

inner pores of the sample. In general, silica gel is pro-

duced in a liquid medium, in which case the pores are
filled with the liquid. In the case of commercial (synthe-
sized) silica gels, the liquid is removed by heating the wet
gel in an autoclave to the temperature above the boiling 200 400 600
point of the liquidC 18 l. These processes may give the in- time (min)
ner pores that require a kind of induction period before
the continuous dissolution stage described by Eq. (6). As Fig. 6 Application of the shrinking particle model to the
shown in Fig. 6, Mallinckrodt silica indicated the induc- experiment data for (a) the Wako-gel C-200, (b) the
tion period shorter than Wako-gel C-200 and LC-50H. Wako-gel LC-50H and (c) the Mallinckrodt silica
This seems to correspond with the fact that Mallinck-
rodt silica has smaller specific surface area (less inner
pores) than Wako-gel C-200 and LC-50H, as shown in
Table 1. After such a period, the dissolution behavior

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Dissolution Rates of Amorphous Silica in Highly Alkaline Solution 355

follows Eq. (6). In this study, the rate constants are Table 2 Apparent rate constants evaluated for Onuma sil-
evaluated from the linear part, as shown in Fig. 6. ica scale
On the other hand, for Onuma silica scale, the dis-
Apparent rate constant, kl,
tribution of particle-size should be taken into considera-
defined by Eq. (8) (s- 1 )
tion for the analysis, as shown in Photo. 2. We divided Temperature
the sample into several groups according to their par- (K) Small sized Intermediate Large sized
ticle size, and introduced each initial value of particle particles sized particles particles
radius of i-th group as Toi, and its fraction dissolved as i=l i=2 i=3
fi. When the initial weight fraction of particle with Toi 343 00 2.69x 10- 4 2.42x10- 5
is described by Woi, the over-all fraction dissolved, f m, 333 00 1.21xl0- 4 9.18x10- 7
is 323 00 4.48x10- 5 5.00xl0- 7

(7)
constants estimated for each-sized particles. In contrast
In the same way as in Eq. (6), fi can be expressed in to the case of the commercial silica gels, Onuma silica
terms of the rate constant of i-th group, k7, as

fi = 1 _ ( 1 _ ~k;t r
Substituting Eq. (8) into Eq. (7), we finally obtain
3
fm=l-L(l-~k;t) woi·
i
The curves in Fig. 7 show the result of fitting of the
experiment data for silica scale to Eq. (9). In apply-
ing Eq. (9) to the data, this study assumed three kinds
of particle sizes, i.e., small (i=l), medium (i=2) and
large (i=3), having different k7 (i=l, 2, 3), respectively.
Least-squares fitting of the data to Eq. (9) was done
by the simplex method. If we divide the sample into
the fractions of w01 =0.05, w 02 =0.60, and w 03 =0.35, the
calculated curve agrees fairly well with the experimen-
tal data for each temperature, as shown in Fig. 7. All
three curves intercept f-axis at 0.05, indicating that the
small sized particles dissolve immediately after the con-
tact (i.e., ki is very large). Table 2 shows the rate
1 ,----,--,.--.--........-..---..---,-~-,
(8)
scale does not show any induction period in its dissolu-
tion behavior. Probably this is because the silica scale
has not experienced such heating treatment as done for
commercial silica gel or powder to remove pore-waters.
Since the over-all dissolution rates of the silica scale were
found to be small compared with those of the pure sam-
(9) ples, the temperatures examined for the silica scale were
set at relatively higher values than those for the pure sil-
ica samples. In Fig. 7, the rates remarkably decrease as
f exceeds 0.65, and it takes 400 min until f reaches 0.8
even at 343 K.
Figure 8 shows that the contribution of large-sized
particles to each !-curve shown in Fig. 7 is very small.
In Fig. 8, the solid line indicates !-curves in Fig. 7 at
each temperature, and the dotted line indicates the con-
tribution of the particles other than large-sized ones. As
shown in Fig. 8, the rate constants of large particles were
negligibly small as compared to those for the medium-
sized particles. Thus, Fig. 7 mainly reflects the dis-
solution behavior of the medium-sized particles, whose
weight fraction is 0.6.
Figure 9 shows the dependencies of k* on the temper-
ature for all samples, where for Onuma silica scale, the

I
:.a"' 0.5

j
o~_....___._ __,__ _,__....__.....__....___._.
0 200 400
time (min) 'O .____._ __,__ _.__....__...__.____._ _._....
0 200 400
Fig. 7 Dissolution behavior of Onuma silica scale time(min)
Curves indicate the result of fitting by the shrink-
ing particle model considering the particle size dis- Fig. 8 Contribution of large-sized particles to each f-curve
tribution. shown in Fig. 7

VOL. 37, NO. 4, APRIL 2000

356
10-2 .------.--..--.---,---.------.--..-...........
a Onuma 0 Wako C-200
+ Wako LC-50H
A Mallinckrodt
10-S ..___._ ___.__ _.__..,__.____._ ___.__ _.__.
2.8 3 3.2 3.4 3.6
l03(f (K1)
Fig. 9 Arrhenius plots for Wako-gel C-200, Wako-gel
LC-50H, Mallinckrodt silica and Onuma silica scale
rate constants for the medium-sized particles are plotted.
From the slopes, the activation energies were obtained
to be 85 kJ·mo1- 1 for Mallinckrodt silica, 88 kJ·mo1- 1
and 77kJ·mo1- 1 for Wako-gel C-200 and LC-50H, respec-
tively, and 84 kJ ·mo1- 1 for the medium-sized particle of
the Onuma silica scale. This rough agreement in the acti-
vation energy suggests the same dissolution mechanism.
Further, Wako-gel C-200 and LC-50H agreed in rate con-
stants, even if the particle diameters were different. This
suggests that Wako-gel C-200 and LC-50H have the sim-
ilar value of inner surface area per unit weight. (The
inner surface is a kind of the effective surface directly
contributes to the dissolution.) As for Onuma silica scale
in Fig. 9, the apparent rate constant for the temperature
range from 300 to 310 K is predicted around at 10- 5 s- 1 .
This value is two orders of magnitude smaller than the
rate constants for the pure silica samples, and is at least
one order larger than the rate constant for quartz already
evaluated in the solution of [NaOH]=l0- 1 mol·dm- 3 (6).
We can translate k* into k through the relation of
k*=3Mk/(rops), if the effective surface area, 3/(rops),
for each sample is reliably estimated. Onuma silica
scale showed no induction period for the dissolution,
indicating negligible contribution of inner pores. By
using the surface area obtained by the BET and the
air-permeability methods (i.e., 3/(r0 p 8 )=1m2 ·g- 1 ), the
rate constants for the medium-sized particles of Onu-
ma silica scale can be estimated to be of the order
of 10- 7 mol·m- 2 ·s- 1 at 310K. On the other hand,
as mentioned above, synthesized silica gels are con-
sidered to have inner pores. The BET surface ar-
eas were estimated to be in the range of from 350 to
450rn 2 ·g- 1 , as shown in Table 1, which are two or-
ders larger than that of Onuma silica scale (1 m 2 ·g- 1 ).
While, the apparent rate constant, k*, for the pure sam-
ples were two orders larger than that of Onuma sil-
ica scale. At 310 K, the each rate-constant, k, was
Y. NIIBORI et al.
computed to be 9.4x 10- 8 mol·m- 2 ·s- 1 for Mallinckrodt
silica, 3.5x 10- 8 mol·m- 2 ·s- 1 for Wako-gel C-200 and
2.8x10-s mol·m- 2 ·s- 1 for Wako-gel LC-50H. These val-
ues of k are in roughly same order of Onuma silica scale.
If the rate-constant is exactly equal to each other, it
can be inferred that the synthesized pure silica gels have
the effective surface area slightly smaller than those es-
timated from their BET data.
V. Conclusions
This paper discussed the dissolution rates of the amor-
phous silica in 10- 1 mol·dm- 3 NaOH solution. As the
pure samples, we took up some commercially available
pure silica gels, i.e., Wako-gel C-200, Wako-gel LC-50H
and Mallinckrodt silica. Applying the shrinking spheri-
cal particle model to the experiment data of each silica
sample, these dissolution behaviors were compared with
Onuma silica scale as one of natural amorphous silica
sample. The moderate size of Onuma silica scale and
the pure silica samples showed good agreements in the
activation energy ranging from 77 to 88 kJ·mo1- 1 . This
suggests the same dissolution mechanism for the pure
silica gels and Onuma silica scale. Moreover, the rate
constants were definitely larger than those already re-
ported for quartz.
While the pure silica gels required a kind of induction
period before the continuous dissolution stage described
by the shrinking spherical particle model, Onuma silica
scale did not need such induced time. In addition to this
result, the BET method and the air-permeability method
showed that Onuma silica scale has little inner pores.
When such inner pores are ignored, the effective surface
area for dissolution is equivalent to that obtained from
the BET or the air-permeability method. By using the
data, the net rate constant for the medium-sized particle
of Onuma silica scale was estimated to be of the order of
10- 7 mol·m- 2 ·s- 1 at around 310 K. Further, by applying
the BET data to the apparent rate constant for the pure
silica gels, the net rate constants were found to be of
the order of 10- 8 -10- 7 mol·m- 2 -s-1, as well as Onuma
silica scale. This suggests that the specific surface area
is an important parameter giving the difference in the
rate constants between the pure silica gels and the silica
scale.
In this study, it was showed that we need not only
the initial dissolution processes, but also the whole be-
haviors, in order to estimate the dissolution rate with
higher accuracy. Further, this study indicated the im-
portance of the distribution of geometric particle diame-
ter in determining the whole dissolution rates, when the
inner pores can be ignored. To predict the effect of the
hyperalkaline plume (caused by cement) on the reposi-
tory surroundings, as a subject for the future study, we
need to link this understanding for the dissolution rates
of amorphous silica to various bulk conditions, which are
locally changing.
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
Dissolution Rates of Amorphous Silica in Highly Alkaline Solution
ACKNOWLEDGMENTS
The authors express their appreciation to Mr.
Yasuhiro Kubota (Mitsubishi Materials Corp.) for his
providing the silica scale samples. This work was
partly supported by "Research for the Future" Program
(Project No. JSPS-RFTF 97P00901) in the Japan Soci-
ety for the Promotion of Science.
-REFERENCES-
( 1) Steefel, C. I., Lichtner, P. C.: Geochim. Cosmochim.
Acta, 58, 3595 (1994).
( 2) Tanaka, S., et al.: Nihon-Genshiryoku-Gakkai Shi (J.
At. Energy Soc. Jpn.), 39, 1008 (1997), [in Japanese].
( 3) Brady, P. V., Walther, J. V.: Chem. Geol., 82, 253
(1990).
( 4) Dove, P. M., Crerar, D. A.: Geochim. Cosmochim.
Acta, 54, 955 (1990).
( 5) Stumm, W., Morgan, J. J.: "Aquatic Chemistry", (3rd
ed.), John Wiley & Sons, New York, 760 (1996).
( 6) Bergman, I., Paterson, M. S.: J. Appl. Chem., 11, 369
(1961).
( 7) Wirth, G. S., Gieskes, J. M.: J. Colloid Interface Sci.,
68, 492 (1979).
( 8) Rimstidt, J. D., Barnes, H. L.: Geochim. Cosmochim.
Acta, 44, 1683 (1980).
( 9) O'Connor, T. L., Greenberg, S. A.: J. Phys. Chem.,
62, 1195 (1958).
(10) Berger, G., Cadore, E., Schott, J., Dove, P. M.:
Geochim. Cosmochim. Acta, 58, 541 (1994).
VOL. 37, NO. 4, APRIL 2000
357
(11) Knauss, K., Wolery, T. J.: Geochim. Cosmochim. Acta,
52, 43 (1988).
(12) Schwartzentruber, J., Furst, W., Renon, H.: Geochim.
Cosmochim. Acta, 51, 1867 (1987).
(13) Thornton, S. D., Radke, C. J.: SPE (Soc. Pet. Eng.)
Reserv. Eng., 3, 743 (1988).
(14) Shikazono, N.: "Earth System Chemistry, Analysis and
Prediction of Environment and Resources", Univ. of
Tokyo Press, Tokyo, 95 (1997), [in Japanese].
(15) Legrand, P. A.: "The Surface Properties of Silicas",
John Wiley & Sons, New York, 278 (1998).
(16) Brady, P. V., Walther, J. V.: Geochim. Cosmochim.
Acta, 53, 2823 (1989).
(17) Niibori, Y., Kunita, M., Tochiyama, 0., Chida, T.:
Proc. 33rd Conf of SITH (Societe Internationale des
Techniques Hydrothermales), p. 122 (1997).
(18) Allen, L. H., Matijevic, E., Meites, L.: J. Inorg. Nucl.
Chem., 33, 1293 (1971).
(19) Iler, R. K.: "The Chemistry of Silica-Solubility, Poly-
merization, Colloid and Surface Properties, and Bio-
chemistry/', John Wiley & Sons, New York, 462 (1979).
(20) Ito, J., Kubota, Y., Kurosawa, M.: Chinetsu, 14, 173
(1977), [in Japanese].
(21) Fleming, B. A., Crerar, D. A.: Geothermics, 11, 15
(1982).
(22) Southwick, J. G.: Soc. Pet. Eng. J., 25, 857 (1985).
(23) Levenspiel, 0.: "Chemical Reaction Engineering", (2nd
ed.), John Wiley & Sons, New York, 368 (1979).
(24) Tochiyama, 0., et al.: J. Nucl. Fuel Cycle Environ., 5,
3 (1998), [in Japanese].