The Dissolution of Magnesium Oxide in Dilute Sulfuric Acid1

DIGBYD. MACDONALD
AND D. OWEN
Whiteshell Nuclear Research Establishment, Research Chemistry Branch,
Atomic Energy of Canada Limited, Pinawa, Manitoba
Received May 5. 1971

The kinetics of dissolution of sintered magnesium oxide pellets in dilute sulfuric acid at 4.00 and
25.00 "C have been investigated using the rotating disc technique. The rate of depletion of hydrogen
ions in the bulk solution is found to be controlled by both transport through the diffusion layer and
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chemical reaction with the oxide surface. The chemical reaction occurring at the oxide surface has an acti-
vation energy of 13 kcal mol-'. The diffusion coefficients for hydrogen ion in dilute sulfuric acid at the
two temperatures of interest have been calculated. These coefficients yield an activation energy of 3.6
kcal mol-' for the diffusion of hydrogen ions to the oxide surface.

Les cinetiques de dissolution de pastilles d'oxyde de magnesium fritte dans de l'acide sulfurique dilu6,
ont BtC etudiees 4.00 et 25.00 "C,au moyen de la technique du disque tournant. La vitesse de diminution
des ions hydrogene dans le volume de la solution est contrblee a la fois par le phenomene de transport
a travers la couche de diffusion et par la reaction chimique avec la surface de l'oxyde. La r6action chimi-
que se fait a la surface de I'oxyde a une Cnergie d'activation de 13 kcal mol-'. Les coefficients de diffusion
de I'ion hydrogene dans l'acide sulfurique dilue ont etC calcules pour les deux temperatures; ces coeffi-
cients conduisent a une Cnergie d'activation de 3.6 kcal molt1 pour la diffusion des ions hydrogene
vers la surface de Poxyde.
For personal use only.

Canadian Journal of Chemistry, 49, 3375 (1971)

Introduction
The dissolution behavior of metal oxides in
aqueous solution is important to many fields of
chemistry and technology. A great number of
studies have been reported in which the dissolu-
tion experiment is performed upon powdered
samples. In view of the fact that dissolution is
a heterogeneous process this technique suffers
from many drawbacks. Perhaps the two most
serious disadvantages are the lack of a well
defined hydrodynamic or transport regime and
an inherent uncertainty as to the actual (or even
apparent) surface area of the sample. Accord-
ingly, most studies of this type are reduced to
qualitative interpretation.
In the present study the dissolution of mag-
nesium oxide in dilute sulfuric acid was investi-
gated using a rotating disc (1, 2). The rotating
disc technique allows the dissolution reaction to
be studied under
conditions while maintaining a relatively con-
stant surface area. The results of this study clearly
demonstrate that the rates of dissolution oi
magnesium oxide in dilute sulfuric acid are
and permit quantitative
interpretation of the process involved.
'A.E.C.L. No. 4003.
Experimental
Materials
Weighed portions (1.80 g) of British Drug Houses
(B.D.H.) or Anachemia reagent grade magnesium oxide
powder were pressed into pellets at 7500 p.s.i.g. and sin-
tered in air at 800 "C for 15 h. The sintered pellets were
strong, easily polished and showed no tendency to "flake"
when rotated in sulfuric acid. The density of the pellets
was found to be 2.00 g ~ m - This~ . figure is well below the
theoretical density of 3.58 g ~ m and - suggests
~ consider-
able porosity in the sample. However, longer sintering
times (up to 4 h) did not increase the density markedly
so all pellets used in this work were prepared as described
above. The dissolution reaction was limited to a well
defined area by painting the sides and one face of each
pellet with polyurethane varnish. Pellets prepared in this
manner using both the B.D.H. and Anachemia oxides
gave identical results within experimental error.
Dilute sulfuric acid solutions (0.005-0.050 M) were
prepared by diluting reagent grade concentrated sul-
furic acid with deionized distilled water.
Apparatus
The rotating disc used in this study was similar to that
described previously (3) and incorporated features
by Riddiford (2). The disc was machined
from Teflon and contained an inset on the underside of
sufficient size t o accept a magnesium oxide pellet.
Immediately before a run was started the pellet was
pressed into place and the exposed face was ground down
to within 0.5 mm of the surrounding Teflon surface with
No. 600 silicon carbide paper. Any free magnesium oxide
grindings were washed away with distilled water. The
disc was screwed on to a threaded stainless steel shaft
 3376 CANADIAN JOURNAL OF CHEMISTRY. VOL. 49, 1971

which passed through a roller bearing assembly at the

top of the reaction vessel. This bearing was designed to
ensure minimum eccentricity of the disc (< 1% of the
pellet radius). The shaft was rotated by an adjustable The material balance equations for hydrogen and
speed electric motor via a pulley-belt arrangement. sulfate are therefore given by eqs. 4 and 5,
Rotational velocities were measured using a General
Radio Type 1531-AB stroboscope. The temperature of
the reaction vessel was maintained to within 1 0 . 0 5 "C
of the desired value using a water bath thermostat.
Method where a denotes the number of moles of H,S04
The reaction vessel was assembled and thermostated per liter of solution at zero time assuming no
for 1 h to ensure thermal equilibrium with the water
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bath. The reaction was initiated by pipetting 300 ml of

dissociation and c is the concentration of mag-
prethermostated dilute sulfuric acid into the reaction nesium ion at the time of interest. Since the con-
vessel and starting the electric motor which had been centration of sulfate ion is determined by eq. 6
preset at the desired rotational velocity. The underside
of the disc was viewed with a mirror to ensure that no gas
bubbles were trapped on the magnesium oxide surface.
Alicluots (10 ml) of reaction solution were removed at
regilar time intervals and analyzed for magnesium ion it is possible to eliminate and [HS04-]
by titration with standard disodium EDTA solution
using Erichrome Black T as indicator. The duration of using eqs. 4, 5, and 6 and to express [ H ' ] as a
each run was such that more than 50% of the available function of the known parameters c, K2, and a.
hydrogen ions were consumed.
Rotational velocities were restricted to the range
10.47-104.72 rad s-' (100-1000 r.p.m.). The upper limit
For personal use only.

was chosen so that the maximum Reynolds number

(eq. 11,
[11 Re,,, = r2w/v
where v and w represent the kinematic viscosity and
angular velocity, respectively, did not exceed the critical In all subsequent calculations K2 was taken as
value (2 x lo5) for transition to turbulent flow (2). 1 x lo-' and 2 x l o w 2 M at 25 and 4 "C,
Substituting r and v equal to 0.952 cm and 8.9 x
cm2 s-' (4), respectively, into eq. 1 yields a maximum
respectively (5'
Reynolds number of 1.07 x lo4, i.e. well below the The kinetir xder of the reaction between
critical value given above. The lower limit (10.47 rad magnesium c de and hydrogen ion was deter-
s-') is sufficiently high to ensure negligible contribution mined by c a l ~dating In (d [H lldt),,, graph-
+

to mass transport to or from the oxide surface by natural
convection (2).
Results
The stoichiometry of the reaction between
magnesium oxide and hydrogen ion in solution is
represented by eq. 2
121 MgO + 2H+ -t Mg2+ + H20
In order to determine the kinetic order of the
dissolution process with respect to hydrogen ion
and to formulate a rate expression for the reac-
tion, it is necessary to determine the actual con-
centration of hydrogen ion in solution at any
given time This can be assuming
that the first dissociation of sulfuric acid is com-
plete and that the concentration of hydrogen ion
at anv given time is determined bv reaction 2 and
the secGnd dissociation representkd by eq. 3
ically from plots of [ H i ] vs. time for runs
differing only in the initial concentration of sul-
furic acid and plotting this quantity against
In [ H + I,=, as shown in Fig. 1. The solid line is
drawn with a gradient equal to one. This plot
clearly establishes that the dissolution reaction is
first order with respect to hydrogen ion. Accord-
ingly, the rate equation can be written as eq. 9,
where A is the projected surface area of the
exposed oxide and vt is the volume of the solu-
tion. Since the concentration of magnesium ion,
c, (and therefore [ H +1) is determined by removing
aliquots of solution, Vt musf be regarded as time
dependent when integrating eq. This integra-
tion yields eq. (6),
1101 - Cvt In ( [ H ' l t / [ H + It-,,) = kAt
 MACDONALD AND OWEN: DISSOLUTION OF MAGNESIUM OXIDE IN DILUTE SULFURIC ACID 3377

I I I

14 -

---'i
+
u
\

L.3 -
a 13
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-c
I

I I I
3.0 4.0 5.0
-In [~+l+.~
FIG. 1. Dependence of the initial rate on hydrogen
+
For personal use only.

ion concentration. T = 25.00 0.05 "C, o = 31,42 rad

s-'. The numbers in parentheses represent the initial
concentrations of sulfuric acid. 0 30 60 90 120 150
t (rnin)
here V , is the volume of solution in the time FIG.2. Rate plot for the dissolution of magnesium
interval t - 6 t to t. A typical plot of eq. 10 is oxide in dilute sulfuric acid. a = 0.050 M, T = 4.00 +
shown in Fig. 2. These plots were quite linear 0.05 ' C , and = 52.40 rad s-l. cc = ZV. In {[H+],-6./
over most of the reaction studied. In some cases, [H+I,).
however, and especially so for high rotational
velocities, the rate plots deviated slightly from TABLE1. Rate constants for the dissolution
of magnesium oxide in dilute sulfuric acid
linearity near the end of the run. This phenom-
enon is illustrated in Fig. 2 by the plot of { C V , In k x lo3 (cm s-')
( [ H ' ] t / [ H ' ] t - s , ) ) / tus. t. A strictly linear rate 0
plot would yield a horizontal line. In practice, (rad s-') 4 "C 25 "C
however, the plot "curls" upwards near the end 10.48 4.03+0.07 7.20+0.10
of the run with an apparent increase in k A (see
eq. 10) of 2-3%. Consequently, all rate constants
were calculated from (kA),,, and the projected
area of the exposed oxide surface. The time
dependence of k A most likely arises from the
influence of a steadily roughening surface on the
hydrodynamics of the system and possibly from the high reproducibility that can be obtained by
the concomitant increase in surface area. careful control of the hydrodynamics of the
Rate constants for the dissolution of mag- system.
nesium oxide in sulfuric acid are listed in Table 1.
Each value represents the mean of at least three Discussion
determinations. The uncertainties quoted are the The reaction between hydrogen ion and mag-
average deviations from the means. These average nesium oxide takes place in the following
deviations are seldom more than +2% of the sequence: (a) transport of hydrogen ion to the
corresponding rate constants and demonstrate oxide surface, (6)chemical reaction at the surface,
 3378 CANADIAN JOURNAL OF (:HEMISTRY. VOL. 49, 1971

and (c) transport of the products from the surface

to the bulk liquid. The transport processes, (a)
and (c), are determined by the hydrodynamics
of the system whereas the rate of the chemical
process reflects the difference in free energy
between the initial state and the transition state
for the kinetic path involved. Of the three pro-
cesses identified above only the first two involve
the rate of depletion of hydrogen ions in the bulk
solution. The role played by both of these
processes in the dissolution of magnesium oxide
Can. J. Chem. Downloaded from cdnsciencepub.com by 106.66.62.199 on 09/03/22

in sulfuric acid is examined in detail in the

following discussion.
According to the Nernst theory (7) for diffusion
controlled reactions the rate constant for trans-
port of hydrogen ions to the oxide surface can be
expressed by eq. 11

1/2 (rod 112 s - ' / 2 )

where D is the diffusion coefficient of the reactant FIG.3. The dependence of rate on rotational velocity.
(hydrogen ion) and 6 is the thickness of the
"ideal" Nernst diffusion layer. Solution of the where A' is the true surface area of the oxide.
For personal use only.

Navier-Stokes equations for nonturbulent trans- Similarly, the rate of transport of hydrogen ions
port to the surface of a rotating disc yields eq. 12 to the surface is given by eq. 14,
for the transport rate constant (1, 2)

where [Hf 1, represents the hydrogen ion con-

where v and o have been defined previously
(see eq. 1). Equation 12 predicts that if the rate of
depletion of hydrogen ions in the bulk solution is
purely transport controlled then a plot of kT us.
w1l2 will be linear. Plots of this type for the
dissolution of magnesium oxide in sulfuric acid
at 4.00 and 25.00 "C are shown in Fig. 3. These
plots are not linear and exhibit greatest curvature
at the lowest temperature. The direction of curva-
ture suggests that the observed rate constant
approaches a limiting value at high rotational
velocities. This indicates that over the range of
rotational velocities employed in the present
study both the transport and chemical processes
exert some control of the overall rate of depletion
of hydrogen ions in the bulk solution. Accord-
ingly, the concentration of hydrogen ion at the
oxide surface is neither effectively zero (transport
control) nor equal to the concentration in the
bulk solution (chemical controll. Since the
chemical reaction at the oxide surface is first
order with respect to hydrogen ion then the rate
of reaction can be written as eq. 13.
centration at the oxide surface. At steady-state
d[H+],/dt is identical to d[Hf ]/dt and hence
[H'], can be expressed in terms of the bulk
hydrogen ion concentration and the two rate
constants k , and kc.
Substitution of eq. 15 into eq. 14 yields the
following expression for the rate of depletion of
hydrogen ions in the bulk solution.
where a is the roughness factor for the oxide
surface, i.e. (A'IA). Comparison of eqs. 16 and 9
reveals that the observed rate constant is related
to k , and kc by eq. 17.
or, by substituting eq. 12 for k , and rearranging
Plots of k-I us. o-'l2 for the dissolution of
magnesium oxide in sulfuric acid at 4.00 and
 MACDONALD AND OWEN: DISSOLUTION OF MAGNESIUM OXIDE IN DILUTE SULFURIC ACID 3379

for reaction 19 is sufficiently negative to support

this view. In the present study, therefore, it seems
reasonable to associate the chemical process
occurring at the surface with the rapid hydration
of MgO to produce Mg(OH), which in turn
reacts with protons in the rate determining step
(eq. 20).
slow
+ H+ + Hz0
-
[201 Mg(OHb, , Mg(OH),,+
fast
+ H+ + Hz0
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[21I Mg(OH),,+ Mg,,Z+

The proposed rate determining step is consistent
with the observed activation energy.
The gradients of the k-' us. o-' i2 plots pre-
sented in Fig. 4 permit determination of the
diffusion coefficients for hydrogen ipn in dilute
sulfuric acid at the two temperatures of interest.
The viscosity and density of dilute sulfuric acid
solutions (<0.1 M ) differ little from the corre-
FIG. 4. Plot of reciprocal rate constant us.
sponding quantities for pure water (10). Accord-
ingly, the kinematic viscosities for pure water
For personal use only.

(4) at 4 "C (1.57 x l o p 2 cm2 s- ') and at 25 "C

25.00 "C are presented in Fig. 4. 1he plots are
(8.91 x cm2 s- I) are used here to calculate
linear as predicted by eq. 18 for consecutive first
the hydrogen ion diffusion coefficients. These
order rate processes. If the dissolution process
calculations result in values of 4.5, x and
were completely transport controlled over the
range of rotational velocities and temperatures
7.1, x cm2 s- 'at 4 and 25 "C, respectively.
Riddiford (2) has recently summarized previous
studied then the lines drawn in Fig. 4 should pass
determinations of DH+ at 18-25 "C and found
through the origin. However, this is not the case
and the finite intercepts at = 0 demon-
that the most reliable values fall in the range
2.8 x lo-' to 1 x cm2 s-I depending
strate the existence of joint transport/chemical
upon the solution employed. While no specific
control.
values are quoted for 0.050 M sulfuric acid, the
The intercepts at o-Ii2 = 0 yield numerical
diffusion coefficients reported in the present
values for (ctk,) of 1.92 x l o p 2 cm s-' and
study seem very reasonable. The temperature
10.0 x cm s-' at 4.00 and 25.00°C,
dependence of DH+ can be represented by eq. 22
respectively. If it is assumed that cl is independent
of temperature then the (ctk,) values listed above
correspond to an activation energy of 13 kcal [221
DH+ = Z Dexp (- ED/RT)
mol-' for the reaction of hydrogen ions with where 2, is the pre-exponential factor and ED
the magnesium oxide surface. is the activation energy for the diffusion process.
Vermilyea (8) has shown in a recent study that The diffusion coefficients calculated in this study
'
the dissolution behavior of powdered magnesium yield a value of 3.6 kcal mol- for ED.This value
oxide is quite similar to that for the magnesium lies within the range 2-6 kcal mol-I normally
hydroxide. This led him to conclude that the associated with diffusion of ions in aqueous
magnesium oxide surface is rapidly converted to solution.
the hydroxide (eq. 19) and that this later species
reacts with hydrogen ion in the dissolution The authors wish to thank Dr. S. Banerjee for his
reaction. interest in this work.

[I91 MgO + H 2 0 & Mg(0H)z 1. V. G. LEVICH. Physicochemical hydrodynamics.

AGO = - 6.45 kcal mol-I Prentice-Hall, Inc., Englewood Cliffs, New Jersey.
1962.
The calculated standard free energy change (9) 2. A. C. RIDDIFORD.Advances in electrochemistry
 3380 CANADIAN JOURNAL O F CHEMISTRY. VOL. 49, 1971

and electrochemical engineering. Edited by P. 7. L. L. BIRCUMSHAW and A. C. RIDDIFORD.Q. Rev.

Delahay. Interscience Publ. Inc., New York. 4, 47 6, 157 (1952).
(1966). 8. D. A. VERMILYEA. J. Electrochem. Soc. 116, 1179
3. D. D. MACDONALD and G. A. WRIGHT. Can. J. (1969).
Chem. 48,2847 (1970). 9. Selected values of chemical thermodynamic prop-
4. Handbook of chemistry and physics. The Chemical erties N.B.S. Circular 500. Part 1. 1961.
Rubber Co., Cleveland Ohio. 50th ed. 1969. 10. M. R. SAVINO and V. VITAGLTANO. Ric. Sci. Ser. 11,
5. D. D. PERRIN.Pure Appl. Chem. 20(2), 133 (1969). 2 341 (1962).
6. R. S. BRADLEY.Trans. Faraday Soc. 34,278 (1938).
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For personal use only.