Ind. Eng. Chem. Fundam.

1981, 20, 155-161 155

theory predicts and experiments seem to confirm that
separation rapidly diminishes as operation moves away
from a condition of inifinite recycle (batch operation). The
reduction in separation (expressed as inverse NTU) is
predicted to be linearly related to lean-product production
rate, and this forecast is apparently confirmed by the
particular experiments undertaken. A design relationship
has evolved which can be used for engineering estimates.
Earlier experiments have confirmed that solid (resin)
diffusion is the rate-limiting step for this system, and this
fact is used to show that two key dimensionless groups
determine the extent of separation; these are the Hodgson
number (solid diffusion time constant/cycle-time) and a
new group which represents the ratio of mass exchange per
unit lean product removed.
Acknowledgment
The experimental portion of this work was undertaken
a t the University of Queensland, Australia. The authors
gratefully acknowledge the support of the Australian Re-
search Grants Committee in conducting this research.
Nomenclature
A = fluid displacement (distance travelled per half-cycle)
A, = column cross-sectional area
up = packing mass transfer area per unit volume interstitial
fluid
b = Pigford's separation parameter (k,AT/k)
C* = equilibrium fluid composition
D,= effective solid diffusion coefficient
D = molecular diffusion coefficient
d = particle diameter
If= axial dispersion coefficient
H = dissipation function (stage height or HTU)
k, = particle mass transfer coefficient
Ij(7') = isotherm slope (defined by eq 4)
K = isotherm slope at mean temperature, k ( T )
ko, k l = linear isotherm temperature parameters (defined in
eq 5)
L = column length
LH = hot (desorption) penetration distance
L c = cold (adsorption) penetration distance
NHo = Hodgson number ( d ; / t , c&,)
NT = transfer number (klAT</QB)
q = particle phase composition
4B, QT = product volume per half-cycle
Q, = dimensionless production rate, defined by eq 24 and 25
AT = temperature amplitude ( T H - T c ) / 2
Wp = weight dry solids ( ~ 5 A & ~-( ltb))
Greek Letters
a, = separation factor (C,/CB) at steady-state (t m)
0 = solids hold-up per unit volume void space (pp(l - tb)/tb)
-
€b = bulk bed voidage
tp = particle voidage
q = dispersion pre-coefficient (eq 10)
pp = particle density
w = frequency of operation
In (am)= number of transfer units (NTU)
Literature Cited
Chen, H. T.; Hili, F. 8. Sep.Sci. 1971, 6 , 411.
Dabby, S. S. et ai. Paper IWC-76-20, 37th Int'i. Water Conf., 1976, Pitts-
burgh.
Foo, S. C.; Rice, R. 0. AIChE J. 1075, 21, 1149.
Foo, S.C.; Rice, R. G. AIChE J. 1977, 23, 120.
Foo, S.C. Ph.D. Thesis, University of Queensland, 1977.
Foo, S. C.; Rice, R. G. Ind. Eng. Chem. Fundam. 1979, 78, 68.
Glueckauf, E.; Coates, J. I. J. Chem. Soc. 1057. 1315.
Kiinkenberg, A.; Sjenker, F. Chem. Eng. Sci. 1058, 5, 258.
Perry. J. H., Ed. "Chemical Engineer's Handbook", McGraw-Hill: New York,
1963; Chapter 5.
Pigford, R. L.; Baker, B.; Bium. D. E. Ind. Eng. Chem. Fundam. 1960, 8 ,
RIA
Rice,'-d. G. Ind. Eng. Chem. Fundam. 1075, 14, 202.
Rice, R. 0.; Foo, S. C. Roc. 5th Australian Conf. Chem. Eng. 1977,
179- 183.
Rice, R. G. Sep. Purif. Methods 1078; 5(1), 139-168.
Rice, R. G.; Foo, S. C.; Gough, G. J. Ind. Eng. Chem. Fundam. 1079, 78,
117.
Rice, R. G.; Foo, S. C. Ind. Eng. Chem. Fundam. 1979, 18, 63.
Sweed, N. H.; Gregory,R. A. AIChE J . 1071, 17, 171.
Thompson, D. W.; Bowen, B. D. Ind. Eng. Chem. Fundam. 1972, 7 7 , 415.
Weis, D. E. et ai. 7sfInt. Symp. Wafer Desalination 1065, 2.
Weis, D. E. et ai. J. Wafer Polluf. Control Fed. 1086, 38, 1782.
Wilhelm, R. H.; Rice, A. W.; Rolke, R. W.; Sweed, N. H. Ind. Eng. Chem.
Fundam. 1986. 7, 337.
Wiiheim, R. H.; Rice, A. W.; Bendelius, A. R. Ind. Eng. Chem. Fundam.
1986, 5, 141.
Receiued for review April 1, 1980
Accepted February 19,1981

Dissolution of Silicate Minerals by Hydrofluoric Acid

Wllllam E. Kline and H. Scott Fogler'
Department of Chemlcal Engineering, The University of Michigan, Ann Arbor, Michigan 48 109

A slurry reactor was used to measure the rates of dissolution of silicates in hydrofluoric acid. Reaction rate laws
are reported for the dissolution of kaolinite, sodium montmorillonite, illite, pyrophyllite, muscovite, talc, and biotite.
The measured rates of dissolution are attributed entirely to attack by the HF molecules, rather than by F- or HF2-
ions. The rate of reaction is proportional to the concentration of HF molecules adsorbed at surface lattice bonds.
For sodium montmorillonite, the magnitude of the HF adsorption constant KA is significant, and the kinetic rate
law is of the Langmuir-Hinshelwood form. However, for each of the other silicates studied, the Langmuir-Hin-
shelwood rate law reduces to a simple first-order rate law with respect to the concentration of molecular HF.

Introduction understanding of the elementary processes of dissolution

Despite widespread applications in the electronics and
petroleum industries, the dissolution of silicates by hy-
drofluoric acid is not well understood. Indeed, the entire
field of solid-liquid heterogeneous chemical reactions is
one that has not been studied extensively outside the field
of electrochemistry. Therefore, in order to gain a better
0196-4313/81/1020-0155$01.25/0
by chemical reaction in general, and of silicate dissolution
in particular, an investigation of the various factors af-
fecting the kinetics of silicate dissolution by hydrofluoric
acid has been undertaken.
This paper addresses the relationships between the
kinetics of dissolution and the chemical species present
0 1981 Amerlcan Chemical Society
156 Ind. Eng. Chem. Fundam., Vol. 20, No. 2, 1981
4. \ii'rTGSTOY ?"lei fer
Figure 1. Distribution of fluorine containing species in aqueous
mixtures of HF, HC1, and NH,Cl as a function of hydrogen ion
concentration at 25 "C.
in aqueous hydrofluoric acid. The rates of dissolution of
a number of silicates are reported as functions of the
concentration of hydrofluoric acid, and kinetic rate laws
are developed. The general forms of these rate laws yield
important insights into the fundamental nature of disso-
lution, thus providing increased understanding of the re-
action mechanism.
HF Equilibria
Hydrofluoric acid is a weak acid that undergoes both
dissociatin and association. The associated species, Hipi,
are strongly acidic. Consequently aqueous HF solutions
are characterized by the following equilibria
Of the equilibrium constants Ki, only K1 and K 2 have
been well documented (Ellis, 1963). The higher order
fluoride species, however, become important only in con-
centrated HF solutions where dissociation is not sup-
pressed by the presence of other strong acids such as HC1
(Hekim and Fogler, 1977). Throughout the range of HF
concentrations used in this work (0.1-3 g-mol/L) the mole
balance of fluorine atoms is well represented by
(HF), = (HF) + 2(HFJ + (F-)
where
(F-) = Ki(HF)/ (H+)
and
(HF2-) = K2(HF)2/(H+)
Figure 1shows the fluorine fractions in the form of HF,
F-, and HF2- as a function of hydrogen ion concentration
for aqueous mixtures of hydrofluoric acid, hydrochloric
acid, and fluoride or bifluoride salts at 25 "C.The vertical
marks indicate the distribution in a solution of 1.0 M
hydrofluoric acid. The pH may be lowered by increasing
the concentration of HC1 in the mixture and raised by
increasing the concentration of fluoride or bifluoride salts.
One observes that at a hydrogen ion concentration greater
than lo-' M virtually all of the fluorine is in the form of
free H F while at any hydrogen ion concentration less than
5X M the fraction of H F molecules is very small.
The stoichiometry and equilibrium of the reaction
products have been duscussed by Labrid (1971) and by
Hekim and Fogler (1977). The reaction products consist
of highly stable fluosilicate and fluoaluminate complexes
SiFm4-"and AlFn3-". The distribution of these products
is a function of temperature, HF concentration, and pH.
Lowering the pH shifts the equilibrium distribution toward
those complexes coordinated by fewer fluorine atoms, thus
reducing the consumption of hydrofluoric acid.
Previous Work
Most of the previous studies of the acid dissolution of
silicates have investigated the attack by strong acids such
as HC1. These reactions are in fact leaching processes, in
which the preferential removal of aluminum, magnesium,
and iron from the lattice leaves a silica structure saturated
with protons. The dissolution of silicate minerals by hy-
drofluoric acid, on the other hand, is entirely stoichio-
metric. In contrast to the leaching reactions characterizing
the attack by strong acids, we have shown (Kline, 1980)
that hydrofluoric acid removes silicon, aluminum, mag-
nesium, and any other components at rates proportional
to their concentrations in the lattice.
The attack by hydrofluoric acid is also orders of mag-
nitude more rapid than dissolution by strong acids. Tumer
(1964) reported that in 30% HC1 at 65 "C,half of the
aluminum is leached from kaolinite after a period of 16
days. At the same temperature an equivalent concentra-
tion of hydrofluoric acid will dissolve an identical sample
of kaolinite in a matter of minutes. It is evident that it
is attack by fluorine containing species, rather than simply
the action of the H30+ ion, that determines the rates at
which silicates dissolve in hydrofluoric acid.
The previous kinetic studies describing the dissolution
of silicate minerals by hydrofluoric acid are sparse and for
the most part inconsistent. Blumberg (1959,1960) mea-
sured the rates of dissolution of vitreous silica in HF
concentrationsranging from 0.1 to 2.0 rn. A first-order rate
law was reported
-r = Izo exp(-E/RT) (HF)
where
ko = 2.0 X (g-mol of Si)/(cm2 s HF molality)
and
E = 9.0 kcal/g-mol
Dissolution rates at specific HF concentrations and tem-
peratures have also been published for various other forms
of silica, including quartz cristobalite, tridymite, and
coesite. These results are summarized by Iler (1979).
Gatewood et al. (1970) attempted some rough estimates
of the rates of dissolution of feldspars, kaolinite, and
montmorillonite. Residual HF was measured at 5-min
intervals for dissolution in solutions containing 3% to 9%
HF and 9% to 12% HC1. Unfortunately, in each exper-
iment the reaction reached completion before the end of
the first 5-min interval, so that calculation of the rate of
dissolution as a function of concentration is not possible.
The first detailed kinetic data describing the dissolution
of aluminosilicates in hydrofluoric acid was reported by
Fogler et al. (1975), who used a rotating disk to study the
HF dissolution of sodium and potassium feldspar. The
dissolution of these minerals was shown to follow first-
order kinetics with respect to the concentration of HF.
There is a lack of consensus as to which of the fluoride
species present in hydrofluoric acid solutions dissolves the
silicate lattice. Significant dissolution cannot be attributed
to independent attack by the F- ion, even when it is
present in appreciable quantities. Semmens and Meggy
(1966) showed that while some dissolution of kaolinite does

take place in solutions of F- salts, the rate of dissolution
is negligible when compared to the reaction in equivalent
concentrations of HF. Therefore it can be concluded that
the kinetic contribution of the F ions originating from the
dissociation of HF is also negligible. Assessing the degree
to which the dissolution of silicates by hydrofluoric acid
is a function of the concentration of the bifluoride (HF,)
ion is more difficult, since rate experiments where HF,
is the only fluorine-containing species are not possible.
Solutions of bifluoride salts contain significant equilibrium
fractions of F and HF. At 25 “C, for instance, an aqueous
solution prepared by adding 1.0 g-mol of ammonium bi-
fluoride to a liter of water contains 0.4 g-mol/L of HF, 0.44
g-mol/L of F-, and 0.58 g-mol/L of HF;.
Born (1979) reported a rate law of the form
-r = k(H+)(HF2-)
for the dissolution of “silica” in mixtures of hydrofluoric
acid and hydrochloric acid. It should be noted that the
experiments upon which this conclusion is based employed
solutions containing only very small concentrations of HF,
(0.00098-0.0043 g-mol/L), where the concentrations of
molecular HF (1.12-2.4 g-mol/L) were two to three orders
of magnitude greater than the corresponding concentra-
tions of HF2-. Moreover, plots of the reported dissolution
rates as a function of the concentration of free HF are also
linear, a result that contradicts the conclusion of a first-
order functionality with respect to the concentration of
HF2-. The product (H+) (HF2-)varies with the square of
the concentration of molecular HF. From eq 2 one can
write
-r = k(H+) (HF2-) = kK2(HF)2
Judge (1971) studied the ratesof dissolution of oxidized
single crystal silicon wafers in aqueous mixtures of HC1
and NH&l and concluded that attack by bifluoride ion
is dominant. A rate law of the form
-r = A(HF) + B(HF2-) C + All of the rate experiments were carried out in a slurry
was reported, where C is a finite negative constant and B
is four to five times the magnitude of A. Judge, however,
reported no experiments at the extremes (i.e., in solutions
where either the HF concentration or the HF2- concen-
tration is suppressed to negligible fractions of the total
fluoride concentration). Consequently the kinetic effects
of the two species were never actually isolated. Experi-
ments in solutions of HF and HC1, where the concentra-
tions of HF2- were very small, were performed by Blum-
berg (1960) and by Fogler et al. (1975). First-order func-
tionalities with respect to the concentration of molecular
HF were reported for the dissolution of vitreous silica and
feldspar, respectively.
The strongest conclusion that can be drawn from these
previous studies is that silicate dissolution in hydrofluoric
acid is a function of the concentration of molecular HF,
and that the bifluoride ion may or may not be important
in determining the rate of reaction. This uncertainty,
however, has remained only because previous workers did
not undertake experiments to study the attacking species
independently. In this investigation the kinetics of dis-
solution with respect to the individual concentrations of
HF2- and molecular HF are separated and characterized.
Rate laws are then developed, and the nature of the in-
teractions between the silicate surface and the attacking
species are discussed.
Experimental Section
Initial rate experiments were used to determine the
dissolution rates for a number of different silicate minerals.
Ind. Eng. Chem. Fundam., Vol. 20, No. 2, 1981 157
@Sampling Syringe
Submicron Filter
Sampling
Figure 2. Slurry reactor.
Knolinite (3-5pn)
05N HF, 25-C
8
u 70;
d 60
Y,,,,,,,,
‘ 0 I 2 4 5 7 8
3 6
TIME 1Minulerl
Figure 3. Raw data for typical slurry reactor experiment.
The initial rate tecnnique was employed because the solid
phase surface areas and bulk phase acid concentrations are
complex functions of the extent of reaction. Consequently,
only at time t = 0 can the reaction rates be related to actual
measured surface areas and acid concentrations.
reactor, shown in Figure 2. The specific advantage of a
slurry reactor, as opposed to a rotating disk apparatus, is
the fact that the slurry reactor enables dissolution rates
to be measured for naturally fine grained minerals such
as clays. The reactor used in these experiments was fa-
bricated from acid-resistant Hastelloy B. Agitation is
provided by a Teflon-coated magnetic stirring bar, and
temperature is maintained by a surrounding water bath.
The dissolving slurry is placed under nitrogen pressure,
allowing samples to be withdrawn at short time intervals
through submicron filters. Filtration of the mineral par-
ticles stops the dissolution reaction in the sample aliquots
so that they are representative of dissolved mineral as a
function of time. The progress of the reaction is monitored
by analyzing the filtrate samples for dissolved lattice
components by atomic absorption spectroscopy, and the
initial rate is calculated from the slope of a plot of dissolved
aluminum or silicon as a function of time at time t = 0
(Figure 3). As mentioned previously, the dissolution rates
with respect to aluminum and silicon correspond to their
relative stoichiometric ratios within the mineral lattice.
Another important advantage of the slurry reactor is
that mass transfer effects can be eliminated. Very small
particles (less than 5 pm for clays, less than 20 pm for
feldspar, quartz, and mica) were dissolved at high agitation
rates. It can be shown (Kline, 1980) that the mass transfer
rates to the surfaces of these small particles are two to five
orders of magnitude larger than the observed dissolution
rates. It can also be shown that the shear stresses resulting
from the agitation of particles of this size are negligible.
158 Ind. Eng. Chern. Fundarn., Vol. 20, No. 2, 1981

I
l 6 C Kaolinite 2 5 O C
H F = 0 5 g m mole/l
Nri:=3Cgmmoe/P

A Quartz 25OC
HF = I O gm mole/P
\b:-3Ogmmoie/~

I
06C I

01 01 IO 15
id?;) gm mole/P

Figure 4. Initial rates of dissolution as a function of the concen-

tration of HF2-.

Electron micrographs of undissolved particles withdrawn

1
0.5

from the slurry reactor showed no evidence of mechanical " o i 2 3 4 5 -

breakage (Kline, 1980). HF CONCENTRATION (rnoles/P)
The surface area important in particle dissolution is that
Figure 5. Sodium montmorillonite dissolution rates at 25 "C.
wetted by the acid solution. This wetted surface area can
be considerably larger than the surface area measured by
nitrogen BET, because water molecules can penetrate
between the unit layers of certain expandable clays such
as montmorillonite. Nitrogen molecules, on the other
1
2 1
$ 51
n
1 Dissolulion of Sodium Montmorillonite
a t 25°C
!
hand, are adsorbed only on the exterior particle surface.
In this work the wetted surface areas were conveniently
measured by a nuclear magnetic resonance (NMR) tech-
nique. The basic concept of the NMR method is derived -

from the fact that the proton spin polarization relaxation Least Squares
time of a liquid in contact with a solid surface, T I , is x
different from the relaxation time of the bulk, TB. The
surface to volume ratio of a water-saturated pack of par- I 2 3 4 5 6 7 8 9 IO
1 / ( HF ) ( g mmoles / I).'
ticles is given by
Figure 6. Test for Langmuir-Hinshelwood kinetics,

Dissolution Rates as a Function of the

Where 4 is the fractional void volume and A is a constant
determined by calibration with known surface areas.
Further details of the theory have been discussed by
Korringa et al. (1962).
Dissolution Rates as Function of the HF2-Ion
The possibility that the measured rates of dissolution
result in part from attack by the HF, ion was investigated
by initial rate experiments in which the HF; concentration
was varied at constant concentrations of molecular HF.
The desired concentrations were obtained by adjusting the
proportions of hydrofluoric acid, NH4HF2,and NH4Cl
according to eq 1 through 3. (NH4C1was added to the
solutions in order to maintain a constant concentration of
NH4+,since it has been shown (Kline and Fogler, 1981)
that the presence of salt cations can affect the kinetics of
silicate dissolution.)
Figure 4 compares the rates of dissolution of kaolinite
and quartz in mixtures of hydrofluoric acid and ammonium
bifluoride (-r(HF, HF2-)) with the corresponding rates in
solutions containing only hydrofluoric acid and NH4Cl
(-r(HF)). The dimensionless ratio of these corresponding
rates, -r(HF, HF2-)/-r(HF), is plotted as a function of the
concentration of HF2- so that the effect of the bifluoride
ion on the dissolution rates of both silicates can be shown.
One notes that HF; concentrations as high as 2.0 g-mol/L
do not increase the rates of dissolution in solutions of 0.5
N and 1.0 N molecular HF. Even in a solution of 48%
hydrofluoric acid the concentration of HF, is less than 1.0
g-mol/L. Hence it can be concluded that the rapid dis-
solution of silicates by hydrofluoric acid cannot be solely
or even partially attributed to attack by the HF, ion.
Concentration of Molecular HF
With the exception of sodium montmorillonite,all of the
minerals studied followed first-order kinetics with respect
to the concentration of molecular HF.
-r = ko(HF) (4)
The rate constants ko are tabulated as a function of tem-
perature in Table I. It is emphasized that the concen-
tration (HF) in eq 4 refers to the associated hydrogen
fluoride molecule. The total hydrofluoric acid concen-
tration is always greater than the concentration of mo-
lecular HF because of dissociation.
As can be seen from Figure 5, sodium montmorillonite
follows first-order kinetics at low HF concentrations, but
the reaction order decreases as the concentration of HF
is increased, suggesting Langmuir-Hinshelwood kinetics.
-r = ki (HF)
1 + k,(HF)
This form of the rate law was confirmed by plots such as
Figure 6, which shows that the reciprocal reaction rate is
a linear function of the reciprocal HF concentration over
the entire concentration range. Montmorillonite dissolu-
tion therefore can be modeled by assuming a first-order
reaction with respect to the concentration of HF molecules
adsorbed on the surface
-r = kKA(HF) (5)
1 + KA(HF)
where k is a rate constant and KAis the equilibrium con-
stant for the adsorption of HF at reactive sites. In Table
 Ind. Eng. Chem. Fundam., Vol. 20,No. 2, 1981 159

Table I. Experimental Values of the Rate Constant k,

--t = k ,f( HF)
~~

dry (BET) wetted (NMR) k , mol mineral

surface area, surface area, dissolved/wetted
mineral m2/g m2/g temp, "C cm2/(sHF molarity)
kaolinite 15 16 0 6.6 X
A14Si4010( OH), 25 4.9 x 10-'2
37.6 1.3 x
49.2 2.7 x lo+
32 22 25 2.3 x 10-13
37.6 6.2 x 10-13
49.2 1.4 x
60 3.8 x
70 5.4 x 10-'2
muscovite 11 30 37.6 3.2 x 10-13
KA13Si4010(0H)2 49.2 7.5 x 10-13
60 1.4 x
70 2.4 x le-1z
7 34 25 1.7 x
60 1.0 x lo-"
4 41 25 9.5 x 10-13
37.6 1.6 x
49.2 2.8 X
60 5.3 x 10-'2
biotite" 6 30 25 7.4 x lO"2
illite b 31 79 25 2.1 x
35 4.3 x 10-'2
45 7.7 x
sodiumc montmorillonite 32 520 0 8.7 x 1044
25 4.3 x 10-13
a Formula KMgl~,Feo~3AlSi30,,(
OH), determined by AAS analysis. Formula K1,Al,,Fe0~,Mg0~,Si,,Al,,0,,(OH), deter-
mined by AAS analysis. Formula Nao~,All,Mg,,Fe,,Si3~,Alo~3010(
OH), determined by AAS analysls.

Table 11. Values of the Rate Law Parameter K A for Table IV. Adsorption Constants K A Characterizing the
Sodium Montmorillonite Dissolution of Sodium Montmorillonite in Mixtures of
HF and HCI at 25 "C
T,"C KA
0 0.58 HF adsorption
25 0.39 HCl, g-mol/L constant, K A
0.0 0.39
Table 111. Experimental Heats of Wetting 0.1 0.31
heat of cation- 1.0 0.44
wetting, exchange 3.0 0.33
kcal/gmol capacity,
mineral of H,O meauiv/100 e stant to the hydrogen ion concentration is consistent with
kaolinite 0.67 3-15 a model in which the HF molecule itself is the attacking
illite 1.4 10-40 species, as opposed to a mechanism involving simultaneous
Na 4.3 80-150 attack by the dissociated H+ and F- ions. Furthermore,
montmorillonite it can be concluded that the surface adsorption of HF and
H+ takes place independently.
I1 the values of KA are shown at 0 and 25 O C . The first-order kinetics characterizing the dissolution
The variation of any equilibirum constant with tem- of kaolinite, pyrophyllite, muscovite, illite, talc, and
perature is given by the Van't Hoff equation phlogopite can also be related to the surface concentration
d(1n KA) = -rn of molecular HF by noting that the Langmuir-Hinshel-
wood rate law reduces to a firsborder proportionality with
dT RP respect to the bulk concentration of the adsorbed species
and the fact that KAdecreases with temperature is con- at small values of the adsorption constant KA.
sistent with an exothermic adsorption process. Although -r = kKA(HF)
AH cannot be precisely established with just two tem-
peratures, it can nevertheless be noted that the value of Moreover, the fact that the constants KAobtained from
AH calculated from these data, -2.5 kcal/g-mol of HF, is the rate laws describing the dissolution of sodium mont-
comparable to the heats of wetting for the adsorption of morillonite are larger than the adsorption constants for
water at clay surfaces. The following heats of wetting for each of the other minerals studied is analogous to the
kaolinite, illite, and sodium montmorillonite are given by strong adsorption of water by montmorillonite particles.
Grim (1968) (Table 111). In Table 111the heat of wetting of sodium montmorillonite
Significantly, neither the form of the montmorillonite is three times the heat of wetting of illite and more than
rate law nor the magnitude of the parameter KAchanges six times that of kaolinite. In general, silicates charac-
when an independent source of hydrogen ions is added to terized by large cation-exchange capacities are hydrated
the hydrofluoric acik Table IV presents values of the more strongly than silicates for which the cation exchange
adsorption constant KA obtained from the initial rates of capacity is low (Grim, 1968). This trend is attributed to
sodium montmorillonite dissolution in mixtures of HF and the strong adsorption of the polar water molecules at
HC1. This insensitivity of the apparent adsorption con- negative lattice sites as well as the hydration of the ex-
160 Ind. Eng. Chem. Fundam., Vol. 20, No. 2, 1981
changeable cations themselves. The hydrogen fluoride
molecule is also highly polar, and an analogy can be drawn
in which the adsorption constants KA are largest for sili-
cates characterized by substantial cation-exchange ca-
pacities. Conversely, where the cation exchange capacity
is low, either because of a lack of isomorphous lattice
substitution (e.g., kaolinite) or because the compensating
cations are fixed within the lattice (e.g., muscovite), it can
be expected that the magnitude of the adsorption con-
stants KAwill be considerably smaller. When the product
KA(HF) is small compared to unity, the Langmuir-Hin-
shelwood rate law reduces to a simple first-order rela-
tionship.
Comments on the Nature of Surface Interaction
There are three different ways by which HF molecules
can interact with silicate surfaces. The kinetic results
provide insight in distinguishing the particular interaction
that leads to dissolution.
(1) Chemical replacement of surface hydroxyls (Iler,
1979)
-X-
I
+ HF - I
X- + H20
where X represents a lattice atom such as silicon or alu-
minum.
(2) Hydrogen bonding at lattice hydroxyls (Dickman and
Bray, 1941)
I
I
I,
0 0
I I
-i-O-i- + HF C i-0-i-
(3) Nucleophyllic chemisorption at the lattice bonds
(Iler, 1979; Samson, 1952)
The possibility that the rate of dissolution is primarily
determined by the replacement of surface hydroxyls can
be discounted by noting that silicate surfaces are also
fluorinated by F salts (Dickman and Bray, 1941; Samson,
1952). While slow compared to the dissolution reaction
- I -
-x- I
+ F -X- 4- OH
in HF, this replacement of surface hydroxyls by fluorine
ions is still much faster than any dissolution of the silicate
lattice in solutions of F- salts. Therefore the surface
fluorination is by itself not the rate-determining step.
Furthermore, decreasing the concentration of H+ to nearly
zero at a constant concentration of molecular HF does not
decrease the rate of dissolution. One observes from Figure
4 that increasing the concentration of the bifluoride ion
from 0.1 M to 2.0 M decreases the hydrogen ion concen-
tration by a factor of 20, yet the rate of dissolution at
constant concentrations of the HF molecule remains the
same. Hence the replacement of surface hydroxyls by the
attacking HF molecules, followed by reaction with H+ ions,
can also be ruled out as the primary mechanism.
It can also be argued that the rates of dissolution in
hydrofluoric acid are not determined by the HF molecules
adsorbed on the surface hydroxyls. One would expect that
the adsorption equilibrium of the attacking HF molecules
would change as the hydroxyls are protonated by H+ ions.
As discussed previously, no such change was observed in
the rate law adsorption parameters.
The observed characteristics of the dissolution of sili-
cates in hydrofluoric acid are best explained by a mecha-
nism whereby the rate-determining HF molecules are ad-
sorbed at the surface lattice bonds. Adsorption at these
sites is a function of the structure and composition of the
silicate lattice, but is not affected appreciably by the
dissociation or protonation of the surface hydroxyls.
Furthermore, adsorption at the lattice bonds is consistent
with a surface reaction mechanism discussed by ller (1979)
and by Strelko (1973). Both concluded that the dissolution
of silicates by any nucleophyllic agent including phosphoric
acid, OH- and F ions as well as hydrofluoric acid, can be
attributed to the fact that adsorption of the attacking
species increases the coordination of the surface silicon,
aluminum, and magnesium atoms, thus weakening the
lattice bonds. When HF molecules are adsorbed at the
silicate surface, the surface bonds are further weakened
by the association of the HF protons with the adjacent
lattice oxygens. Consequently the reactive intermediate
is a surface site at which the lattice atoms are partially
bonded to one another and partially to hydrogen and
fluorine. Since the rates at which silicates dissolve in HCl
F
OH,/)',\', OH OH OH
lg i) \\I
---X-O-X-
I
X-F + OH-X-
I
or NH4F solutions are negligibly slow compared to the
rates of dissolution in hydrofluoric acid, the dissolution
by HF cannot be attributed solely to either the protonation
of the lattice bonds or the nucleophyllic fluoride attack.
Rather, it can be concluded that both steps must take place
simultaneously,and that the lattice bonds must be readily
accessible to both the proton and the fluorine of the HF
molecule. This important condition is best satisfied by
adsorption of HF at the lattice bonds, rather than by ad-
sorption at the surface hydroxyls or by a hydroxyl re-
placement mechanism whereby only fluorine is present at
the surface.
Summary
A slurry reactor was used to measure the rates of dis-
solution of a number of silicates in hydrofluoric acid.
Kinetic data was obtained for the dissolution kaolinite,
sodium montmorillonite, illite, pyrophyllite, muscovite,
phlogopite, talc, and biotite, and rate laws were deter-
mined. The results show that the rates of dissolution can
be wholly attributed to attack by the associated HF
molecules, rather than F- and HF2- ions also present in
hydrofluoric acid solutions. All of the silicates studied
except sodium montmorillonite follow first-order kinetics
with respect to the concentration of molecular HF. The
dissolution of sodium montmorillonite is described by a
Langmuir-Hinshelwood rate law. The Langmuir-Hin-
shelwood rate law reduces to first-order proportionality
with respect to the attacking HF molecules at small values
of the adsorption constant Kk It is concluded that the
rate of silicate dissolution in hydrofluoric acid is deter-
mined by HF molecules adsorbed at the surface lattice
bonds.
Acknowledgment
All surface area measurements used in this work were
provided by the Chevron Oil Field Research Company.
 Ind. Eng. Chem. Fundam. 1981, 20, 161-164 181

Literature Cited
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Dickman, S. R.; Bray, R. H. So/iScl. 1841, 52. 283.
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1870. 22. 693.
Grim, R.’E.; ;‘Clay Mineralogy”, 2nd ed.; McGraw Hili: New York.
Heklm. Y.; Fogler, H. S. Chem. Eng. Sci. 1977, 32, 1.
Iler, R. K. “The Chemistry of Silica”, Wiley: New York, 1979.
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Kline, W. E. Ph.D. Thesis, The Unhrerslty of Michigan, Ann Arbor, 1980.
Kline, W. E.; Fcgler, H. S. J. Golbhl Interface. S d . 1961, in press.
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Samson, H. R. Clay Mineral. Bull. 1952, 1 , 266.
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Received for review July 21,1980
Accepted February 23,1981

Components in Chemical Stoichiometry

Pehr Bjornbom
Department of Chemical Technology, Royal InstnUre of Technology, S-100 44 Stockholm, Sweden

Jouguet’s and Brinkiey’s definitions of components are compared. In restricted chemical stoichiometry, when all
chemical changes permitted within the framework of the atomic material balances cannot take place, these
definitions give different results. In such cases only Jouguet’s definition Is compatible with Gibbs’ phase rule. If
Jouguet’s definition is adopted, rather than Brinkley’s, the constraints placed upon the composition changes in
restricted chemical stoichiometry cases can be interpreted as material balances over components. A proposed
definition of chemical stoichiometry is based on this resuit.

Introduction Of course, neither of these definitions can be wrong since

In chemical stoichiometry the concepts of components
and independent reactions are very important. These
concepts were introduced by Gibbs (1876) in the theory
of chemical equilibrium and have subsequently been dis-
cussed by several authors. Literature references are given
elsewhere (BjBrnbom, 1975,1977;Smith and Missen, 1979).
As Smith and Missen (1979) recently have pointed out,
the results of research in chemical stoichiometry have not
been given due attention as a separate field. The reason
for this is probably that chemical stoichiometry has not
been discussed separately but in the context of chemical
equilibrium and chemical kinetics.
In a previous paper (Bjornbom, 1975)) the concept of
independent reactions was discussed. It was found that
in order to avoid difficulties in treating restricted chemical
equilibrium problems the definition of this concept by
previous authors should be extended with the requirement
of independently variable reaction extents.
Definition 1. A set of chemical reactions are inde-
pendent if and only if (1)the reactions are linearly inde-
pendent; (2) they can describe all composition changes in
the system; and (3) the corresponding reaction extents can
vary independently. Basically it is not the equilibrium
which is restricted, but the stoichiometric behavior of the
system is restricted due to the absence of certain ele-
mentary reactions (Bjornbom, 1977). Therefore it is more
correct to say restricted chemical stoichiometry than re-
stricted equilibrium.
In the literature after Gibbs, two different types of
mathematical definitions of components exist. The first
method due to Jouguet (1921) starts from the independent
reactions. The second method due to Brinkley (1946) and
recently used by Smith and Missen (1979) starts from the
elemental balances.
In many cases these definitions are equivalent. However,
in restricted chemical stoichiometry problems they produce
different results.
0196-4313/81/1020-0161$01.25/0
neither of them contains inherent contradictions. How-
ever, according to the criterion chosen it is possible that
one of the definitions is better than the other. The aim
of the present paper is to investigate this and to elaborate
on the component concept.
Although the concept of components is a tool for de-
scribing the chemical stoichiometry this concept cannot
be completely isolated from chemical equilibrium, for
components play a very important role in the theory of
chemical equilibrium and especially in Gibbs’ phase rule.
Therefore the criterion used to compare Jouguet’s and
Brinkley’s definitions of components will be compatibility
with Gibbs’ phase rule.
Remarks on Terminology
There is some variation in the terminology in this field
motivating some clarifications. We will consider a system
composed by molecular species which are compounds of
atomic species, the elements. Occasionally there are free
atoms in the system.
The molecular species and the free atomic species are
components of the system. However, due to chemical
reactions all these components are not independent, since
some of them can be formed out of others. Thus only a
subset of the Components are needed to form an arbitrary
mixture of all the components.
Such a subset occasionallyis called a set of independent
components. However, since a set of independent com-
ponents consequently can be considered ultimate compo-
nents of the system, independent is often dropped, so
components will mean the same as independent compo-
nents. This terminology will be adopted in this paper. The
term substance will be used in this paper for those com-
ponents which are not independent.
Definition of Components
Definition 2. A component is one of a set of C species
of the chemical system, the number of which is the least
0 1981 American Chemical Society