Hydrothermal reaction kinetics.

The decomposition of nickel(I1) hydroxide

THOMAS A N D TONYC. T . WONG
W. SWADDLE'
Depccrctlretrc qf'Cl~o~ri.tery.
711eU t ~ i ~ ~ e or f. Colgcrry,
~i~y Ctrlgorj, Alco.. Co~rtrtltr7 2 N l1V4
Received A L I ~2L, 1977
I~~
THOMAS W. SWADDLE and Tony C. T. WONG.Can. J. Chem. 56, 363 (1978).
The fractional extent a of decomposition of ripened Ni(OH), into green NiO in alkaline
hydrothermal conditions under nitrogen is given by the rate law all3 = k,[OH-If, where
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kc = 2.4 x kg mol-' s-' at 561 K. The Arrhenius activation energy is 220 1 25 kJ

mol-'. The reaction is accelerated moderately by OZ (giving black NiO,+,) and strongly by
added NiO. A reaction mechanism involving dissolution of Ni(OH), as Ni(OH),-(aq) and rate-
determining, surface-controlled reprecipitation of this as NiO is proposed.

THOMAS W. SWADDLE et TONYC. T. WONG. Can. J. Chem. 56, 363 (1978).

A 561 K, on peut exprimer la fraction, a , de la dtcomposition de Ni(OH), vieilli en NiO
vert dans des conditions hydrothermiques alcalines sous atmosphire d'azote par la loi de
vitesse all3 = k,[OH-]I ou k c = 2.4 x lo-' kg mol-' s-I. L'energie d'activation d'ArrhCnius
est de 220 i 25 kJ mol-I. I1 y a une lCgtre acceleration de la reaction par la presence de O2
(conddisant a du NiOl+Bnoir) et une forte acceleration par I'addition de NiO. On propose un
mecanisme de reaction impliquant la dissolution de Ni(OH)2 sous forme de Ni(OH),-(aq) et
une reprecipitation sous forme NiO, contrblee par la surface, determinant la vitesse.
[Traduit par le journal]
For personal use only.

Introduction where x = 0.5-0.7 (12) which grow on standing

The study of the kinetics and thermodynamics of in water ('aging' or 'Ostwald ripening') into hexag-
the conversion of nickel(I1) hydroxide into nickel(I1) onal plates with the brucite structure following loss
oxide under hydrothermal conditions is of tech- of intercalary water, ultimately reaching some 40 nm
in diameter and 7 nm in thickness (25-27). The
poorly crystalline (turbostratic) initial material, often
nological interest in connection with the corrosion designated a-Ni(OH),, is characterized by a reflection
of nickel alloy components (such as heat exchangers in the powder X-ray diffraction pattern correspond-
in water-cooled nuclear power plants) by neutral or ing to a spacing of 0.81-0.85 nm (1 1, 14, 25, 28), and
alkaline water at elevated temperatures (1-3). It may an idealized crystal structure based on an expanded
also be expected to provide an experimentally con- brucite-type lattice corresponding to the forinula
venient model for the mechanisms of hydrothermal 3Ni(OH),.2H20 has been proposed (1 I), but detailed
reactions of transition metal hydroxides and oxides consideration of this poorly reproducible material
in general. has provoked controversy (13, 20, 29). The fully
There is, however, no general agreement regarding 'aged' or P-Ni(OH), form, however, is relatively
the thermodynamics of reaction 1. Data published well-crystallized and reproducible; a similar material
by the U.S. National Bureau of Standards (NBS) of composition Ni(OH),.xH,O (where x = 0.17 +
(4), and calculations based on these (5), indicate that 0.10, decreasing to 0.07 on warming) can be obtained
reaction I should proceed spontaneously at or near by precipitating Ni(OH), in boiling water (16), while
the saturated vapor pressure throughout the entire hydrothermal ripening (7, 10-14, 30) gives essentially
liquid range of water, whereas experimentally it has, stoichiometric P-Ni(OH), in platelets with crystallite
with one exception (6), been found not to occur dimensions around 30 nm thick and 50 nm across
below about 545 K (7-15), although decomposition (30). Hydrothermal ripening is generally favored by
of Ni(OH), can be observed at 470 K or less in the high temperatures (up to 543 K in plain water) (1 1)
'dry' state (14, 16-23). and high hydroxide ion concentrations (up to 4 0 x
This apparent discrepancy arises partly because KOH at 513 K) (12), although other standard
nickel(I1) hydroxide can exist in more than one hydrothermal 'mineralizers' such as KC1 or NH,I
form. When freshly precipitated at or near room seem to be ineffective (10).
temperature, it takes the form of poorly crystalline It is clearly P-Ni(OH), which is relevant to the
particles (21) of size on the order of 3-8 nm (24, 25) present hydrothermal study. The solubility product
and composition best represented by Ni(OH),.xH,O of 6.5 x lo-'' reported by Gayer and Garrett (31)
evidently refers to the P form, since these authors pre-
'Author to whom correspondence should be sent. pared Ni(OH), by precipitation from hot solutions.
 364 C A N . J . C H E M . VOL. 5 6 , 1978

Combining this result with thermodynamic d a t a for
N i O a n d H 2 0 (4), we obtain AG: = -458.1 k J
mol-' for P-Ni(OH),(c), which is 10.9 k J mol-'
more negative t h a n the N B S value (4) (which evi-
dently refers t o t h e ill-defined a-Ni(OH),(c)) b u t
which agrees well with t h e value a d o p t e d b y N a u m o v
et al. (32). This leads t o AGO = +9.25 k J mol-' for in a nitrogen-filled glovebox, when oxygen was to be excluded;
reaction 1 a t 298 K , i.e., NiO(c) is actually utwtable
with respect t o P-Ni(OH),(c) in liquid water a t 298 K ,
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compared with over 200 m2 g-I for the dry, unripened
Ni(OH), .
Kit~eticsof the Hydrorl~erninlRenctiot~
Weighed amounts of P-Ni(OH)2 were placed in capped
35 cm3 PTFE liners with (usually) 20 cm3 NaOH solution, and
-
sealed into titanium/0.2% palladium alloy autoclaves (35)
leaving 25 crn3gas space. These operations were carried out
measurements using a Rexnord oxygen meter showed the O2
content of solutions handled in this way to be less than 0.1

a s pointed o u t b y Baes a n d Mesmer (33), although it pg/g (cf. 8 pg/g for water in equilibrium with air at 294 K and
90 kPa). The sealed vessels were thermostatted ( t 0 . 2 K) in a
is stable relative t o a-Ni(OH),(c). Knowledge of t h e preheated forced-convection oven as described previously (37),
temperature dependence o f AG: o f P-Ni(OH),(c) is and quenched in cold water after chosen intervals r,. The solid
needed t o determine t h e minimum temperature at reaction products were filtered, washed with water, and dried
which reaction 1 becomes thermodynamically fa- under reduced pressure at 110°C for I h. Therrnogravimetric
analysis of 5-10 mg portions over the range 300-800 K with a
vored in water a t its saturated v a p o r pressure; s ~ ~ c hPerkin-Elmer TGS-I thermobalance gave the relative amounts
d a t a seem t o be lacking, although M u k a i b o et al. (3) of Ni(OH)2 and NiO. These analyses were confirmed semi-
have estimated this temperature t o be a b o u t 440 K , quantitatively by powder X-ray diffraction measurements,
whereas others (7, 9, 10) have published purported which also showed that NiO and p-Ni(OH), were the only
phase relationships which suggest transition tem- detectable solid phases present.
peratures o f a b o u t 560 K. Kitletics of Decon~positionof Ni(OH), it1 Dry Etlvirotlt11etirs
A major factor contributing to t h e confusion over Isothermal thermogravimetric analyses were carried out
t h e occurrence o f reaction 1 is its slowness, even a t with the Ni(OH)2 in a shallow layer in an open dish in atmo-
For personal use only.

spheres of helium or, as desired, oxygen. Sample temperature

temperatures o n t h e o r d e r of 500 K . A primary measurements were calibrated against the magnetic transition
objective of this study was to demonstrate t h a t temperatures of alumel, nickel, perkalloy, and iron.
failure t o observe reaction 1 a t elevated temperatures
(7-15) may result f r o m a combination of t h e f o r m Results
of t h e rate law a n d a high activation energy, rather Despite t h e availability o f m u c h d a t a in t h e
t h a n from unfavorable thermodynamic factors. literature (14, 16-23), t h e isothermal decomposition
kinetics of d r y Ni(OH), in helium were investigated
Experimental Section
again in t h e present study for purposes o f direct
Nickel(I1) lrydroxide was prepared using only polyethylene comparison with the hydrothermal measurements o n
or polytetrafluoroethylene laboratory ware. Contact between
the solutions and glassware led to the appearance of one well- similarly prepared material, since t h e mode of
defined and one diffuse extraneous reflection, corresponding preparation of Ni(OH), is k n o w n t o affect t h e
to spacings at 0.725 and 0.95 nm respectively, in the powder decomposition rate (10, 14, 18, 19). T h e rate in
X-ray diffraction pattern of the final product, indicating the helium decreased progressively, a n d could be
hydrothermal formation of nickel antigorite (Ni3Si20,(OH),)
and a trace of nickel montmorillonite (Ni3Si40,0(OH)2)(34). represented by t h e equation
Typically, 1 mol nickel(I1) nitrate or chloride in 400 cm3 water
was added dropwise with stirring to 4 mol NaOH in 600 cm3
water at room temperature. The mixture was stirred overnight where cr is t h e mole fraction of NiO formed by time
and filtered under suction, and the solid was washed with
1000 cm3 NaOH (1.0 111; t t ~= mol kg-') followed by several t , No is the molar a m o u n t of Ni(OH), originally
dm3 water until the filtrate was neutral. Then, the wet solid was present, k,, is a rate coefficient, a n d the index n is 2
either dried under reduced pressure at 110°C for 1-3 h and the for a 'contracting area' a n d 3 f o r a 'contracting
resulting cake ground to a fine powder for future use, or else volume' process (18). Hazel1 a n d Irving (19) inter-
dispersed in 1.0 ttl NaOH (about 0.1 mol Ni(OH)2 to 25 cm3),
preted their rate d a t a for t h e decomposition of d r y
sealed under nitrogen in PTFE-lined autoclaves of 35 cm3
capacity (33, and heated at 200°C for 24 h. The resulting Ni(OH), o n the basis o f t h e contracting a r e a
'ripened' solid p-Ni(OH), was filtered, washed with water formula, arguing t h a t t h e brucite-type layer structure
until the filtrate was neutral, and dried under reduced pressure would favor inward progress of decomposition a l o n g
at 110°C. t h e planes o f t h e lamellae f r o m t h e edges. Marcellini
The ripened solid was seen under the transmission electron
microscope to consist of hexagonal lamellae, 70-160 nm in a n d Teichner (IS), however, found empirically t h a t n
diameter. Powder X-ray diffraction patterns detected no was close to 3 for samples in a n o p e n dish, a n d
crystalline compounds other than P-Ni(OH),, and indicated this is supported by t h e correlation coefficients r listed
the lamellae to be about 20-40 nm thick according to the in T a b l e 1. T h e distinction is, however, a fine one,
Scherrer formula (36) (which, however, was at the limit of its
especially since t h e effective zero o f the reaction time
applicability). The BET(N2) surface area of the ripened
material was determined using a Micromeritics Model 2200 scale had t o be treated as a parameter t o be calcu-
High-Speed Surface Area Analyzer to be - 16 m2 g-l, as lated (in practice, t h e calculated zero time followed
 SWADDLE A N D WONG

TABLE1. Isothermal decomposition of nickel(I1) hydroxide" in dry gaseous environments

Correlation coefficient r.
T Flow rate 105k3'
(K) Gasb (cm% - ') 12 = 3 12 =2 s-')
508 He 25 0.9998 0.9986 3.9
513 He 25 0.9992 0.9971 5.0
He 25 0.9908 0.9882 14.0d
He 0 0.9971 0.9952 3.5
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0 2 30 0.9991 0.9978 4.8

02 0 0.9997 0.9995 2.5
518 He 25 0.9981 0.9945 7.2
523 He 25 0.9992 0.9969 9.3
nHydrothermally ripened (specific surface -16 m2 g - ' ) e xcepl as indicated; initial quantity No
bPressure 90 kPa.
- 0.08-0.10 mmol.
<Standard error ?2%.
dunripenedNi(OH), (specific surface 2 200 m' g-I).
the beginning of the formal reaction time scale t, by TABLE2. Decomposition of Ni(OH), in aqueous NaOH under
as little as 35-70 s). The reaction was not followed nitrogen
-
beyond ci 0.8 because of the retention of some
water by the NiO product (18, 19, 22); indeed Initial Volume Ni (OH), remaining
mass Ni(OH), 0.474 m NaOH after 10 h at 573 K
Erkelens and Egginck-DuBurck (22) took ci = 0.8 to
represent complete reaction, which gave n 1.
The rate coefficients k, listed in Table 1 are
- (g) (cm3 at 294 K) (%I
For personal use only.

obviously influenced not only by the particle size but

also by the nature and flow rate of the gas, as
suggested by the results of Marcellini and Teichner
(18), and furthermore the omission of the factor
TABLE3. Decomposition of Ni(OH), in aqueous NaOH a t
No1'"by other authors makes direct comparison of 561.2 K under nitrogena
our k,, values with their data difficult. Our isothermal
measurements give an Arrhenius activation energy Experiment Time t r in furnace 105ko,s,b
Ea of 132 i 8 kJ mol-I in helium (flowing or still) No. (h) a 6-I1
for the decomposition of dry, hydrothermally
ripened Ni(OH),, and this value was confirmed by 1 3.9 0.02 2.4
4.9 0.03 2.1
thermal volatilization measurements i r ~ vncuo; un- 6.0 0.11 2.6
ripened Ni(OH)2 gave Ea = 114 kJ mol-I in iso- 6.9 0.16 2.5
thermal thermogravimetry. These values are similar 8.0 0.26 2.5
to, or slightly higher than, those reported by other 9.0 0.42 2.5
10.0 0.54 2.5
authors (14, 18, 19, 22). 2 9.2 0.40 2.4
For the hydrothermal decomposition reaction, 10.1 0.51 2.4
Table 2 shows that the fractional extent of decom- 11.3 0.76 2.4
position of P-Ni(OH), per given time is independent 12.1 0.84 2.3
3 9.9 0.64 2.6
of the quantities both of the aqueous phase and of 1 1 .O 0.75 2.5
Ni(OH),, so that the mole fraction ci of NiO product 12.0 0.94 2.4
is again a useful quantity for expressing reaction 4 9.0 0.39 2.5
rate. It is seen that a is reproducible to i 0 . 0 2 . 9.5 0.53 2.6
Table 3 presents values of a,determined in four "Ni(OHh (0.8g) initially in 20 cm3 aqueous NaOH (0.474mol kg-').
*Calculated from kObld= aY/i with y = 113, and t = i r - 0.8 h (to
independent series of hydrothermal experiments, correct for warm-up time).
which are to be correlated with the effective reaction
time t, where t is the time tf spent by the vessels in dependence of ci upon t is typical of topotactic dry
the furnace less the warm-up time (shown previously decomposition reactions of certain other ionic
(37) to be about 0.8 h for reaction temperatures near solids, and can be represented by the Erofeyev
570 K). In contrast with the dry decomposition equation (38)
reaction, the hydrothermal reaction is seen to be very
slow initially but to accelerate progressively, and one
is faced with the problem of choosing an appropriate or similar generalized equations (39); the data of
mathematical function to represent the data. Such a Table 3 fit eq. 3 satisfactorily, with n, = 3.76 $- 0.15,
 366 C A N . J . CHEM.
k , = (2.9 f 0.3) x s-', and correlation
coefficient r = 0.9894, using all 16 data points.
Equations such as [3] were originally developed
for solid state reactions on the basis of assumed rate
control by propagation of reaction product growth
from nuclei within crystals of the starting material,
and, even though more detailed theoretical con-
siderations (40) indicate that the empirical usefulness
of eq. 3 beyond the stage where cr is small is some-
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what fortuitous, the choice of eq. 3 implies the
assignment of a solid-state, internal nucleation
mechanism to reaction 1. There are, however,
several reasons for rejecting this assignment in favor
of a dissolution mechanism.
Firstly, the rate law for the decomposition of
Ni(OH), in the dry state (eq. 2) bears no resemblance
t o eq. 3, and suggests surface rather than internal
nucleation. It could, however, be argued that the
surface nucleation process involves reversible dehy-
dration and that this is suppressed in liquid water;
indeed, the hydrothermal reaction is much slower
than dry decomposition, the rate of which is sensitive
For personal use only.
to the gaseous environment.
Secondly, the rate of hydrothermal decomposition
of Ni(OH), is essentially proportional to [OH-] at
high p H (see below). This suggests a dissolution
mechanism, but could still be accommodated by an
intracrystalline nucleation mechanism of the type
proposed by Ball and Taylor (41) for the decom-
position of dry brucite (Mg(OH),, isomorphous with
P-Ni(OH),), which depends on chain transfers of
protons from internal nuclei to surfaces and which
could be facilitated by surface adsorption of O H - .
Thirdly, transmission electron microscopy showed
that, even after only 4% reaction in 0.474 m NaOH
under N, at 573 K, the newly formed cubes of NiO
were typically of 1 pm edge, whereas the diameters
of the hexagonal Ni(OH), crystals had increased
only slightly and were on the order of 100-200 nm
(BET measurements confirmed that the Ni(OH), had
undergone some further hydrothermal ripening at
this high temperature, reducing the surface area by a
factor of about 3, but it was established that neither
NiO nor Ni(OH), could have reached dimensions on
the order of 1 pm by hydrothermal ripening under
these conditions). Towards the end of the reaction,
the well-crystallized NiO cubes had reached sizes of
3-6 pm side, i.e., their masses had increased in pro-
portion t o the extent of reaction cr. These observa-
tions rule out all topotactic mechanisms, and indicate
growth of NiO by crystallization from solution on
to a fixed number of nuclei in the s a m ~ l e .
[4a] Ni(OH),(c) + xOH-(aq) =2Ni(OH)2+,'-(aq)
[4b] Ni(OH),+,"-(aq) -+ NiO(c) + xOH-(aq) t H 2 0
VOL. 56. 1978
The importance and relatively rapid establishment
of the equilibrium 4a at 540-575 K is demonstrated
by the effectiveness of alkali in promoting hydro-
thermal growth of P-Ni(OH), even at 470 K,
although the absence of massive dissolution of
Ni(OH), indicates that the equilibrium 4a still lies
far to the left. Thus, step 4b must be rate controlling,
involving deposition of fresh NiO on pre-existing
NiO crystals or nuclei, and the rate of the overall
reaction 4 will be proportional to the xth power of
the hydroxide ion activity a,, and to the available
surface area of NiO.
If this mechanism is correct, added NiO should
accelerate the reaction greatly; this was found to be
true (see below), and so we can write, for a single
NiO crystal and hydroxide activity a,,,
where k is the rate coefficient, m is the mass (in mol)
of NiO in the given NiO crystal, V is the molar
volume of NiO, and o is a shape factor (6, for a
perfect cube). The total mass M of NiO in a Ni(OH),
sample containing N growth centers (i.e., NiO
crystals) is N m , and, if p is the number of such
centers per mol of original Ni(OH),, then
where Mo is eitlzer the molar amount of Ni(OH),
originally present in the decomposing sample or the
molar amount of NiO seeds deliberately added at the
start of the reaction (in the latter case, all NiO
growth would occur on the seeds, to the exclusion
of latent nuclei in the Ni(OH),). Then,
Integration then gives
1101 = k'aOFIXt
[Ill = kob,,t at a given [OH -1
where M, = NiO in mol present a t time t , and M , =
NiO present at t = 0. When M , = 0, M, ranges
from 0 at t = 0 to Mo at the end of the reaction, so
The validity of eq. 12 was tested by carrying out a
linear regression analysis of In t on In cr, using the
data of Table 3 (which are unedited experimental
 SWADDLE A N D WONG

TABLE
4. Rate coefficients" for the decomposition of Ni(OH), to NiO in aqueous NaOH

T [NaOH] 105k,b,dc NO. of Range lo5k,

(K) Atmosphereb (mol kg-') (s-') data ofci (kg mol-Is-')
542.2 N2 1.026 0.64k0.09 11 0.13-1 .OO 0.62
552.5 Nz 1.027 0.9720.05 11 0.13-0.93 0.95
561.2 N2 1.026 2.5k0.1 16 0.02-0.94 2.4
5614 Air 1 .026 4.520.5 4 0.10-0.97 4.4
561.2 0 2 1 ,026 6.0k0.9 8 0.06-0.92 5.9
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572.5 N2 1.027 6.6k0.8 7 0.08-0.94 6.4

570.7 N2 0.474 2.520.3 11 0.24-0.86 5.3
572.2 N2 0.098 0.47k0.07 5 0.22-0.93 4.8
'k.,,d = a113/l;k, = k,b,dl[NaOHl.
bO~iginally90 kPa at 294 K.
CUncertaintiesare standard deviations.

results); the correlation coefficient r was 0.9915 for
all 16 data points, giving a slope (index of a) of
0.32 i 0.01 and k,,,, = (2.49 f 0.05) x l o p 5 s-'.
Similarly, the constancy of the calculated values of
+
k,,,, in Table 3 (mean k,,,, = (2.45 0.12) x l o p 5
s-') is remarkably good (fortuitously so, for a <
0.10), and vindicates the use of eq. 12. Table 3 refers
only to hydrothermally ripened Ni(OH), as the
For personal use only.
decomposition relative to the small ( 1 0 . 2 m' g-',
BET) specific surface of the hydrothermal NiO.
In principle, eq. 1 1 permits the calculation of the
time-dependence of reaction 1 catalyzed by added
NiO (hydrothermally prepared, to ensure the appro-
priate value of o). In practice, the separate hydro-
thermal preparations of NiO tend to yield agglom-
erates of crystals which must be completely broken

starting material; experiments using unripened up and dispersed in the fresh reaction medium with-
Ni(OH), gave somewhat faster but poorly repro- out crushing the individual crystals, and this is
ducible rates. difficult to achieve. Nevertheless, the experimental
Activity coefficients for aqueous hydroxide ion are fractional extents of reaction (M, - M I ) listed in
not available for the conditions of this study, but, by Table 5 approach the calculated values sufficiently
analogy with values for 298 K, it may be assumed closely to indicate that eqs. 9-1 1 and the underlying
that they remain tolerably constant from 0.1 to 1.0 theory describe the hydrothermal decomposition of
mol kg-' NaOH. Thus, the data ofTable 4 show that Ni(OH), accurately.
x in eqs. 4, 5, and 8-10 may be taken to be unity, and The large catalytic effect of NiO illustrated by
we can write Table 5 was considerably reduced when undispersed
NiO agglomerates were used, as expected for a
surface-controlled reaction.
This confirms that the main nickel(I1) species
present in strongly alkaline water is indeed Discussion
Ni(OH),-(aq) (or, more generally, [HNiOy In practical terms, k,,,, represents the reciprocal
yH,O]-), as has been assumed by Gayer and Garrett of the time required for reaction 1 to reach 100%
(3 1). Attempts to follow reaction 1 at p H values near completion. More significantly, eq. 13 and the kc
neutral led to poorly reproducible, very slow values of Table 4 permit extrapolations to be made
reaction rates.
The activation energy E, from Table 4 is 220 25 + TABLE
5. Decomposition of Ni(OH)2 in aqueous NaOH in the
presence of added NiOa
kJ mol-', i.e., roughly twice that of the dry decom-
position reaction. Table 4 also shows that the
presence of 0, causes a marked acceleration of the (M2 - MI), calculated (%)
Time tf M2* M2 - M I b
hydrothermal decomposition, the product being (h) (mmol) ( NiO catalysisc No catalysisd
black NiO,,, rather than the leaf green, stoichio-
metric (42-44) NiO that was obtained in the reactions 0 4.28 0 0 0
under nitrogen. Green NiO prepared hydrothermally 2.0 4.87 17 19 0.007
3.75 5.50 35 52 0.1
was not visibly affected by subsequent exposure to 5.0 5.92 48 78 0.3
air, whereas green NiO prepared by decomposition 9.0 7.17 84 Complete 2.4
of dry Ni(OH), in vacuo turned black immediately ONaOH (1.026 m),553.2 K, under N 2 ; added NiO prepared hydrotherm-
on contact with air; this difference may be attributed ally under these same conditions.
bMl = total NiO present at time I ; M, = NiO present initially = 4.28
to the much larger specific surface of the small, mmol; Ma = (M1),,. = NiO present at end of reaction = 7.73 mmol.
CCalculated from (M,IMo)Il' = (MI/Mo)113= kobldt.
porous (30) NiO particles formed by the vacuum dCalculated from (MI - M1)/(Mo- MI) = a = (kt)'.
 368 CAN. J . CHEM. VOL. 56. 1978
to calculate the times needed for an experimentally
significant extent of reaction to occur in the absence
of pre-existing NiO; thus, the first 1% reaction
requires about 80 days at 523 K, or over 2 years at
473 K, in 1.0 m NaOH, and proportionately longer
times at lower [OH-].
This initial slowness of reaction 1 raises doubts
concerning the thermodynamic validity of the
experimental pressure-temperature phase relations
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reported for the Ni(OH),-NiO-H,O system (7, 9,
10). The calculations of Mukaibo et al. (3), on the
other hand, seem realistic; a thermodynamic
threshold of about 440 K is predicted for reaction
1 at the saturated vapor pressure of water, which
accommodates the considerable thermodynamic
stability of p-Ni(OH), at 298 K noted in the Intro-
duction and also its apparent catalytic conversion
to NiO in some ferrite syntheses at 473 K (6). This
explains why all attempts to demonstrate the
hydration of NiO to Ni(OH), have failed (1, 7, 9,
10); the reaction is probably thermodynamically
possible only below about 440 K , and even at this
For personal use only.
-
temperature 1% conversion would require over 200
years in 1.0 m NaOH (since kc 3 x lo-'' kg mol-'
s-l, and the forward and back reactions would have
the same rates).
The slightly faster and rather poorly reproducible
rates observed for reaction 1 when unripened
Ni(OH), was used in place of the hydrothermally
prepared hydroxide are unlikely to originate in the
relatively rapid pre-equilibrium
but may reflect a greater (and variable) number of
growth centers p per mol of unripened Ni(OH),,
which would facilitate the rate determining step
Similarly, the accelerating effect of 0, may
originate in the creation of Ni3+ defects in NiO, so
assisting the formation of growth spirals; certainly,
NiOl+, is the product when 0, is present. Alterna-
tively, the normal mechanism of reactions 14 and 15
may be supplemented by a sequence of the type
Under hydrothermal conditions, reaction 17
evidently proceeds at about 513 K, and reaction 18
near 563 K (10, 12,45). Reaction 16 may be expected
to occur to a small extent on the surface of a
p-Ni(OH), crystal, as the electrochemical analogue
of this reaction proceeds smoothly with 26 ranging
from 0 to 1 without changing the main structural
features of the crystal (reaction 18 similarly involves
minimal structural changes) (12, 46).
To conclude, the alkaline hydrothermal decom-
position of Ni(OH), in the absence of oxygen con-
sists of a rate-determining, autocatalytic precipita-
tion reaction followil~grelatively rapid dissolution
of the metastable p-Ni(OH), as Ni(OH),-(aq). This
is in accordance with the general observation (47)
that dissolution and ripening reactions (reaction 14)
occur by relatively rapid diffusion-controlled pro-
cesses, whereas precipitation of new phases (reaction
15) occurs by slower, interfacial processes. For this
reason, the dissolved nickel(I1) species of eqs. 4, 14,
and 15 is more appropriately written as Ni(OH),-
than as NiO(0H)-, etc., implying readier repre-
cipitation as Ni(OH), than as NiO. The practical
significance of this reaction mechanism and the
large E, (-220 kJ mol-') associated with it is that
Ni(OH), can exist metastably in water at tempera-
tures on the order of 570 K for remarkably long
periods, especially if the p H is not high and there is
little 0, or solid NiO in the system. It follows that
p-Ni(OH), will often be an important product of the
hydrothermal corrosion of nickel alloys, and that its
thermodynamic properties should be used in place
of those of NiO in calculations relating to the courses
of chemical reactions in high-temperature aqueous
systems. The same is probably true of cobalt(I1)
hydroxide, the pink p-form of which is isostructural
with p-Ni(OH), and forms hydrothermally from the
blue a-Co(OH), (6).
Finally, this study serves to emphasize the im-
portance of reaction mechanism, as well as thermo-
dynamics, in determining the outcome of hydro-
thermal reactions.
Acknowledgments
We thank Miss Margaret Sisley for some pre-
liminary experiments, Dr. P. Bayliss for X-ray
diffraction measurements, Alberta Sulphur Research,
Ltd., for assistance with thermogravimetry, Drs. D.
W. Shoesmith, T. E. Rummery, and A. G. Wikjord
for discussions, and Atomic Energy of Canada, Ltd.,
for financial support.
1 . N. S . McIN-I-YRE, T . E. R U M M E R Y M., G. COOK,and D.
O W E NJ. . Electl.ochem. Soc. 123, 1164 (1976).
2. R. GASPARINI and E. I O A N I L LProc.
I . Am. PowerConf. 33,
776(1971).
3. T . M U K A I B OS, . MASUKAWA, M . MAEDA, and M.
HOSHIDO. Denki Kagaku, 34,388 (1966).
4. D. D. WAGMAN, W. H. EVANS, V . B. PARKER, 1. HALOW,
S. M. B A I L E Yand, R. H. S C H U M MSelected
. values of
chemical thermodynamic properties. NBS Technical Notes
270-3 (1968) and 270-4 (1969). U.S. Department of Com-
merce, Washington, DC.
 SWADDLE A N D WONG 369

5. R. E. V O N MASSOW,G . R. S U L L I V A N and, G . N. W A U G H . 27. V. P. K o ~ o vZavod.

. Lab. 10,503 (1941).
Solubility of nickel and cobalt ferrite in water up to 300°C. 28. S . L E B I H A Nand M. FIGLARZ. J. Cryst. Growth, 13114,458
Report No. AECL-4582, Atomic Energy of Canada, Ltd.. (1972).
Ottawa, Ont.. Canada. 1975. 29. W. DENNSTEDT. Electrochim. Acta, 19,535 (1974).
6. A. R. GAINSFORD, M. J . SISLEY.T . W. S W A D D L Eand , P. 30. F. FIEVETand M. FIGLARZ. J. Cata!. 39,350 (1975).
BAYLISS. Can. J . Chem. 53, 12 (1975). 31. K. H . G A Y E Rand A. B. GARRETT. J . Am. Chem. Soc. 71,
7. L . A. ROMO.J . Phys. Chem. 60, 1021 (1956). 2973 (1949).
8. C. KLINGSBERG and R. ROY.Am. Mineral. 44,819 (1959). 32. G . B. N A U M O VB. , N. R Y Z H E N K O
and
, J. L. KHODAKOV-
9. C. W. F . T . P l s . r o ~ l u s Z.
. Phys. Chem. Frankfurt am Main, S K I . Handbook of thermodynamic data. Atomizdat, Mos-
34,287 (1962). cow. Russia. 1971.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 112.133.233.140 on 08/28/20

10. M. A. AIA.J . Electrochem. Soc. 113, 1045 (1966). 33. C. F. BAES,J R . and R. E. MESMER.The hydrolysis of
11. H. BODE,K . DEHMELT,and J . W1-r.r~.Electrochim. Acta, cations. J. Wiley and Sons, New York, NY. 1976. pp.
11, 1079(1966). 245-246.
12. R. S . MCEWEN.J . Phys. Chem. 75, 1782 (1971). 34. J . J . B. V A N EIJKV A N VOORTHUIJSEN and P. F R A N Z E N .
13. S . LE B I H A Nand M. FIGLARZ.Electrochim. Acta, 18, 123 Rec. Trav. Chim. Pays-Bas, 70,793(1951).
( 1973). 35. T . W. S W A D D L EJ., H. LIPTON,G . GUASTALLA, and P.
14. S . L>E B I H A Nand M. FIGLARZ.Therniochim. Acta, 6 , 319 BAYLISS.Can. J. Chem.49,2433(1971).
(1973). 36. E. S U O N I N E NT ,. J U N T U N E NH.
, JUSTEN,and M. PESSA.
15. V . CHERTOVand R. S . T Y U - I - Y U N NKolloidn. IK. Zh. 37.323 Acta Chem. Scand. 27,2013 (1973).
(1975). 37. M. H E N D E R S O N I., ~MIASEK,
. and T. W. S W A D D L ECan.
.
16. A. MERLINand S . T E I C H N E RC.. R. Acad. Sci. 236, 1892 J . Chem. 49, 317(1971).
(1953). 38. B. V. EROFEYEV.C. R. Dokl. Acad. Sci. URSS, 52, 511
17. S . J . T E I C H N E RR. , P. M A R C E L L I Nand I , P. RUE. Adv. (1946).
Catal. 9,458 (1957). 39. J . H. T A M P L I NAust.
. J. Chem. 29,27 (1976).
18. R. P. M A R C E L L I N andI S. J. TEICHNER J .. Chim. Phys. 58, 40. A. R. ALLNATTand P. W. M. JACOBS.Can. J. Chem. 46,
625 (1961). 11 1 (1968).
19. 1. F. H A Z E L L ~ J. ~ ~I RRV.I N GJ.. Chern. Soc. A,669(1966). 41. M. C . B A L Land H. F. W. TAYLOR.Mineral. Mag. - 32. 754
For personal use only.

20. W. DENNSTEDT and W. LOSER.Electrochim. Acta, 16,429 (1961).

(1971). 42. S . P. MITOFF.J. Chem. Phys. 35,882 (1961).
21. M. SAKASHITA and N. SATO. Bull. Chern. Soc. Jpn. 46, 43. R. N E W M A Nand R. M. CHRENKO.Phys. Rev. 114, 1507
1983 (1973). (1959).
22. J. E R K E L E NandS S . H . EGGINCK-DUBURCK. Rec. Trav. 44. F. J. M O R I NPhys.
. Rev. 93, 1199(1954).
Chim. Pays-Bas, 92,658 (1973). 45. R. W. C A I R N Sand E. OTT. J . Am. Chem. Soc. 55, 527
23. M. TOPIC,F. J. MICALE,C. L. C R O N A NH. , LEIDHEISER, (1933); 55,534 (1933).
J R . , and A. C. ZETTLEMOYER. Adsorption at interfaces. 46. H . BODE, K . DEHMELT,and J . WI.I-I-E.Z. Anorg. Allg.
A.C.S. Symposium Series No. 8,225 (1975). Chem. 366, l(1969).
24. A. O B E R L I NBull.
. SOC.Fr. Mineral. 77,833 (1954). 47. A. G . WALTON.The formation of precipitates. Intersci-
25. S. L E B I H A NJ, . GUENOT,and M. F I G L A R ZC. . R. Acad. ence, New York, NY. 1967. Chapt. 2.
Sci. Ser. C , 270.2131 (1970).
26. D. L O U E R ,D. WEIGEL.and J. I. LANGFORD.J. Appl.
Crystallogr. 5,353 (1972).
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