2400 Pierre Bracconi and Louis-Claude Dufour

N. Mori and T. Mitsui, J. Phys. SOC.Jpn., 26, 1087 (1969).
M. Hansen and P. Anderko, "Constitution of Binary Alloys", 2nd ed,
McGraw-Hill, New York, N.Y., 1958, p 466.
L. N. Larikov and 0. A. Shmatko, Fiz. Met. Metalloved., 30 (6), 1173
11970).
(16) F. S. Stone and R. J. D. Tilley, React. Solid, Proc. lnt. Symp., 7th. 1972,
262 (1972).
(17) H. Jagodzinski, 2.Kristallogr., 109, 368 (1957).
(18) K. P. Sinha and A. P. B. Sinha, J. Phys. Chem., 61, 758 (1957); A. W.
Laubengayer and H. W. Mc Cune, J. Am. Chem. Soc., 74,2362 (1952).
(19) A. Deschanvres and B. Raveau, Rev. Chim. Miner., 5 , 201 (1958).
(20) G. K. Bansal and A. H. Heuer. Phil. Mag., 30, 709 (1974).
(21) R. Sun, J. Chem. Phys., 28, 290 (1958).
(22) T. E. Bradburn and G. R. Rigby, Trans. Brit. Ceram. SOC., 52, 417
11953).
(23) B. Gillot and P. Barret, C.R. Acad. Sci. Paris, Ser. C,278, 57 (1974).
(24) A. L. G. Rees, "Chemistry of the Defect Solid State", Methuen, London,
1954.
(25) M. H. Tikkanen, Genie Chim., 92 (3), 57 (1964).
(26) G. Grube and M. Flad, 2.flektrochem., 42 (7), 377 (1942).
(27) H. Davies and W. W. Meltzer, J. flectrochem. SOC., 121 (4), 543
(1974).

Hydrogen Reduction of Cobalt-Chromium Spinel

Oxides. II. CoCr204-Co304 Solid Solutions

Pierre Bracconi* and Louis-Claude Dufour

Laboratoire de Recherches sur la Reactivite des Solides (associe au Centre National de la Recherche Scientifique),Departement B,
Faculte des Sciences Mirande, 21000-Dijon, France (Received June 10, 1974; Revised Manuscript Received June 5, 1975)
Publication costs assisted by the Universlty of Dijon

The hydrogen reduction of stoichiometric cobalt chromite (Sl)was investigated in the first part of this se-
ries. Here, we are concerned with the reduction of two cobalt chromite-cobalt cobaltite solid solutions,
4 2 - x = 0.06 in specimen S2 and x = 0.45 in specimen S3; S2 contains, in addi-
Co2+ [ c r ~ - ~ 3 + c o ~ 3 + ] B owith
tion, a large amount of vacancies on the octahedral (B) sites and of associated Cr6+ ions. From the results
concerning the reduction of S3 (lattice parameter a = 8.281 A) it is obvious that, below 55OoC,the x COB^+
can be reduced to CO$+, but that, simultaneously, a fraction (x/2) of the tetrahedral C O A ~is+ reduced to
the metallic state, x water molecules are formed and the lattice parameter increases continuously; a spinel
lattice ( a = 8.320 A) with an abnormal cationic distribution is obtained, which can be formally regarded as
an intermediate between CoCr204 and COO.At higher temperatures these COB^+ are reduced to the metal-
lic state and the spinel rearranges into C O ~ + [ C ~ ~ ~ +( a] B =O ~ ~ A)
8.330 - which finally reduces to fcc-Co and
a-CrzO3. These two steps have not been separated thermodynamically, but, as they proceed consecutively,
it is clear that the reactivity of the cobaltous ion is here related to the type of crystallographic site it oc-
cupies. The presence of octahedral vacancies in S2 does not modify the absolute rate of reduction into Co
and Cr203 as compared with that measured for S1. Such an observation is in agreement with the conclusion
that the rate-determining step of these reactions is a diffusion phenomenon of cobaltous ions through the
spinel lattice tetrahedral sites.

I. Introduction Speculation about the reduction behavior of such com-

The authors studying the reduction of ternary metallic
oxides (ref 1-3, see also ref 1-3 and 23 in part I, preceding
article in this issue) did not consider the possible relation-
ships between the kinetics and mechanism of such reac-
tions and the particular structure of the initial oxides stud-
ied. Dobrovinskii and Balakirev4 observed that some of the
successive equilibrium states occurring in the reduction of
the spinel CoFe1.75Cr0.2504a t 1000°C and decreasing oxy-
gen partial pressure corresponded to different successive
compositions of the spinel phase. On the contrary, the re-
duction of Co304 by HZ5and by CHd6 is known to yield
COOas an intermediate phase.
The purpose of this paper is to investigate, in compari-
son with CoCi-204, the reduction kinetics and mechanism of
other cobalt-chromium spinel oxides with different compo-
sitions, S2 and S3, in which cobaltic ions replace part of the
Cr3+ on the octahedral (B) sites. In addition, one of them,
S2, contains octahedral vacancies and associated Cr6+ ions.
pounds gives rise to interesting questions. For instance, if
the CoB3+can be reduced to Co2+,these ions might either
migrate on tetrahedral (A) sites (their normal location in
the spinel structure) or be expelled in a separate phase
such as COO. Concerning S2, the reduction kinetics and
mechanism can be, a priori, expected to depend upon the
vacancies existence.
11. Experimental Section
Techniques. This work was carried out with the same ex-
perimental techniques as those already described in part I.
Materials. Preparation and Characterization. Specimen
2 (S2) was obtained by decomposition of CoCrz07-4C5H5N
in air at 120OOC for 24 hre7Similar to specimen S1 (see part
I, section 11) it is crystallized in octahedral grains (see Fig-
ure 1 (top)) of average edge size a = 1.5 f 0.5 wm. Its com-
position is Co~.0~Cr1.~104.00 and its structure of spinel type
with a parameter equal to 8.305 f 0.003 A. It is obvious,

The Journal of Physical Chemistry, Vol. 79, No. 22, 1975

tiydr-n Reduction of Cobait-Chromium Spinel Oxides
Figure 1. SEM micrographs of (top)S2 initial grains, X 20,000 (bot-
tom) S2 reduction products (at 712% far 42 hr. a = 1.16 gatom).
X19.500.
from the above formula, that the number of normally occu-
pied sites defined hy the fcc oxygen lattice exceeds the
number of available Cr and Co cations, hut, as S1
(CoCrz04) was prepared from S2 by solid state reaction
with chromium oxide, the observed nonstoichiometry must
then he due to cationic vacancies, and not to impurities, ac-
cording to Col.osCrl.sloo.l3Or.oo.The density calculated on
that basis, d = 5.11 f 0.01 glcm?, agrees well with the ex-
perimental value of d = 5.08 g/cm3.
Moreaus prepared specimen 3 (S3) through a method
originally used by Adkins and Conofl for copper chromite
preparation. The solid obtained a t 45OoC is finely divided;
its BET-surface area, after outgassing a t 450°C, reaches
the maximum value S = 20 m2/g. Comparison with the re-
sults of SEM observations and of X-ray diffraction line
broadening measurement suggests that these grains are, as
a first approximation, nonporous, monocrystalline, and
spherical in shape, with an average diameter d , = 500 A.
However that value can be modified substantially above
600OC as shown by the surface area decrease of samples an-
nealed under vacuum (Figure 2a). The duration of thermal
equilibration and outgassing of the samples prior to kinetic
experiments were then shortened to the minimum. Under
vacuum, gases desorb from its surface, up to 450%. in an
amount representing 0.65 +
0.10 wt %, and between 800
2401
I I
0 0.5 1 1.5 O(gA1)
Figure 2. (a) Accumulated variation of ihs relative BET-surfacs area
(rep&+ to ihs maximum value S-0 = 20 m2/g) of an S3 sample
successweiy annealed at maximum 0 temperatures reached with a
linear temperature rise of 125”CIhr. (b. c, d) Variation with a of the
relative BET-surfacearea of S3 samples at different temperatures.
and 9OooC, a very small weight loss is still observed, which
may he due to the decomposition of remaining precursor or
c0304 traces. Then the spinel phase composition in S3, cal-
culated from the corrected concentrations of the elements,
is C01.45Cr1.5504.00.
If only Cr3+ ions are assumed in S2, the ionic formula ac-
counting for the lattice electroneutrality involves C O ~ ions
+
on A sites, hut the following results, which have been col-
lected with the aim of establishing, experimentally, the S2
and S3 ionic structures, show that the nonstoichiometry in
S2 is more probably due to the presence of C$+ ions.
(a) As shown in Figure 3, the lattice parameter of our
specimens decreases proportionally with chromium to co-
halt ratio as expected for CoCrzO4-CosO4 solid solutions
from the works of Makkonen’O and of Hanck and Lai-
tinen.” The vacancies in S2 may explain why its parameter
is slightly smaller than that of the normal solid solution
having the same CrICo ratio. But Makkonen’s conclusions
on the ionic structures of these compounds may he consid-
ered as erroneous; it is clear now that CoaO4 is, as CoCrzO4,
a normal spinel, and according to the sites “preference”
rules in the spinel s t r u c t ~ r e it
~ ~may
- ~ ~be predicted that
the Cr3+ will only locate on the B sites, while the Co2+and
the Co3+ will respectively prefer the A and the B sites.
Concerning the cation vacancies, in the spinels y-Fep03, y-
AI&, yCr203, and y-Mnz0316 as well as in other nonstoi-
chiometric spinel oxides’? they are distributed (orderly or
randomly) on B sites. Hence a similar location can he rea-
sonably assumed for S2. More simply, S3 is likely to have
the following structure:
Col.~2+~Crl.s53+C~.453+lB~4.00z-
i
(b) Experimental evidence supporting these conclusions
was initially sought by means of X-ray diffractometry. Un-
fortunately, the atomic scattering factors of the various
cations are nearly equal and the problem is further compli-
cated for S3 by the diffraction line broadening due to the
grain size. The presence of vacancies in S2 either on A or B
sites was hoped to modify sufficiently the relative intensi-
ties of certain diffraction lines compared to the stoichio-
metric chromite S1 of same grain size. These were calculat-
ed with the formula
1+cos228
I = , PJ-
sin2 8 cos e
2402
2 1.5 1.0 cr/cO 0.5
u
0 0.5 1
Figure 3. Experimental lattice parameter vs. CrKo ratios for S1, S2.
and S3 (0)compared to the results of Makkonen (0)and of Hanck
and Laitinen (A)for Co1+,Cr2-,04 solid solutions.
where the structure factors are given by Bertaut.18 How-
ever the differences so calculated and experimentally ob-
served for the reflections (ill), (220), (311), (222), and
(400) are very weak, and we will only conclude that octahe-
dral location of the vacancies is more probable.
(c) On the other hand, the atomic magnetic moments of
C?+, Co3+, and Co2+ have fairly different values. In partic-
ular, octahedral Co3+ are almost always in a low spin state,
as in c0304,~' and have a zero moment instead of 5.4 pug in
the high spin state. The moment of tetrahedral Co2+ in
c0304 is ~ ( C O A ~ =+4.75
) Le., slightly higher than the
value we measured in S1: 4.58 f 0.11 p ~ The . Cr3+ have a
spin only magnetic moment p(Cr3+) = 3.87 pug. Each speci-
men Curie constant is the average of four values calculated
by least-squares analysis from the susceptibilities mea-
sured between room temperature and 400°C under argon
pressure and with four different magnetic field values. We
calculated that the diamagnetic contribution of the oxygen
ions is negligible. The Curie constant is related to the
atomic moments by
where ni is the number of gram atoms of i-type cation, and
pi its magnetic moment (in Bohr magneton, p ~ ) N , is Avo-
gadro's number, and k the Boltzmann constant. For S3,
Cexpt = 0.0247 f 0.0003 "K cm3/g; the same value can be
calculated from the above relation with p(cOB3+) = 0 and
~ ( C O A ~=+4.75
) confirming the expected ionic structure
(i). For S2, Cexpt = 0.0277 f 0.0004 "K cm3/g; with
~ ( C O A ~=+4.58
) and p ( C o ~ ~=+ 0,) a satisfactory value can
be calculated for the tetrahedral Co3+ moment with the as-
sumption of tetrahedral vacancies; p(CoA3+)= 5.45 instead
of 4.83 with the assumption of octahedral vacancies. How-
ever, the hypothesis of Cr6+ also gives a C value, C =
0.0275 "K cm3/g, consistent with the experimental one.
Therefore, the presence in our specimens of octahedral co-
baltic ions in a low spin state is clearly demonstrated; but
the existence of either tetrahedral Co3+ or Cr6+, in S2, is
not definitively established; although the first possibility is
the least convenient since it requires the vacancies to be on
A sites (in opposition to many examples of nonstoichiomet-
ric spinels) in order to fit the above magnetic data.
(d) An attempt to detect the species CoA3+in S2 by EPlZ
was unsuccessful, but this also cannot be regarded as a de-
finitive conclusion. On one hand, at 77"K, S2 (as Sl) is an-
tiferromagnetic and the method is not valid; on the other
hand, at 150°K and above (temperatures at which no anti-
The Journal of Physical Chemistry, Vol. 79, No. 22, 1975
Pierre Bracconi and Louis-Claude Dufour
ferromagnetic interactions between C O A ~and + CrB3+ ions
occur any longer), no characteristic EPR spectra of either
C O A ~or+ CoA3+ions could be observed.
However, Cr6+ assumption has been finally selected, as
no example of a cobaltic compound in the structure of
which Co3+ is normally tetrahedrally coordinated with oxy-
gen is known yet.
As a conclusion, the ionic structure of S2 will be
111. Results
As expected from part I, fcc-Co and a-CrzO3 are the final
reaction products obtained below 750°C. Owing to its high
surface area, S3 is very reactive; its reduction is investi-
gated in a temperature range (500-700°C) where the reduc-
tion of a-CrzO3 does not interfere.
Kinetics. In Figures 4 and 5, a represents the weight loss
by reduction, at P H =~ 50 Torr, of S3 and S2 samples as a
number of oxygen gram atoms per formula i and ii. The hy-
drogen pressure has a very weak effect on the reaction
rates; for instance, for S3 and in the range 10 Torr < PH%<
60 Torr, they vary within experimental error limits.
For S2 (Figure 4), the a ( t ) curves are very similar to that
observed for S1.They differ, however, on the two following
points. (a) The limit corresponding to complete reduction
into fcc-Co and a-Cr2O3 ( a = 1.281) is hardly attainable
below 750°C. The reaction rate becomes generally very low
for a values (poorly reproducible) between this upper limit
and that corresponding to the reduction alone of the cobalt
ions ( a = 1.095). (b) An initial deformation of the curves up
to approximately a = 0.05 g-atom can be observed especial-
ly a t the lowest temperatures.
The activation energy over the whole temperature range
and for 0.1 < a < 1.0 is 40 kcal/mol. The maximum reac-
tion rates at given temperatures are equal to those mea-
sured, with the same conditions for S1 reduction (see Fig-
ure 3 in part I). All the experimental observations that
were explained in part I a5 due to the reduction of a-Cr203
were observed here again and will not be given any further
attention.
For S3, the curves daldt vs. a , derived from a ( t ) curves
recorded at PH*= 50 Torr, are shown in Figure 5. In the
first part of the reaction up to a = x (where x represents
the number of cobaltic ions on B sites) the rate is constant-
ly decreasing and can even become zero at T < 550°C and
a = J C .Up to this limit, a is proportional to a fractional
power o f t : CUT= (kTt)l/n with n E 3. The activation ener-
gy calculated from the constants kT is found to be E = 30
kcal/mol. A t higher a values and for T > 550"C, this energy
increases; it is 35 kcal/mol at a = 0.6 and 0.7 and finally
reaches the characteristic value for the CoCrzO4 reduction
E = 40 kcal/mol.
Structural and Magnetic Analysis. S3 lattice parameter
increases during the reduction. This is revealed by X-ray
diffractograms of partially reduced samples and Debye and
Scherrer photographs on which all the diffraction lines can
be indexed in the lattices of a spinel matrix (of variable pa-
rameter) and of fcc-Co. It is clear from Figure 6 that the
lattice parameter initially increases continuously from a =
8.281 A at a = 0 to 8.320 A at a = x (the corresponding
solid phase will be called +), and then slowly reaches the
CoCrz04 characteristic value a = 8.330 A.
Similar observations are made with S2, the lattice pa-
Hydrogen Reduction of Cobalt-Chromium Spinel Oxides 2403

rameter also increasing during the reaction. However, as

the specimens are reduced in the temperature range 700-
85OoC,the fractional reaction (up to a = x = 0.063) expect-
ed by analogy with S3 cannot be clearly distinguished.
The amount of ferromagnetic cobalt present in S3 sam-
ples partially reduced to the a values a = 0.28, 0.40, and
0.45 was calculated from the ratio of these samples satura-
tion magnetization to that of a totally reduced one. This
amount expressed in gram atoms of cobalt is proportional
to a: n(Co g-atom) = (0.54 f 0.05) a , Le., n N a/2. Unfor-
tunately the presence of the ferromagnetic phase does not
allow the magnetic susceptibility and Curie constant of the
spinel matrix to be measured and, hence, its ionic structure
to be interpreted.
Morphology. From this view-point S1 and S2 reductions
are shown to be perfectly similar by SEM (see Figure 1)
which allows the same conclusions to be drawn in both
0 5 n ) o
t ( h l 1 cases (see part I, section 111).
The reduction of S3 was investigated by measurement of
Figure 4. Isothermal thermogravimetric curves for the reduction (at the BET-surface area of initial and partially reduced sam-
PHz= 50 Torr) of S2. a represents the weight loss in oxygen gram
atoms per mole of C O ~ . O ~ C ~ ~ . ~ I O ~ . ples (Figure 2). A t low temperatures (curve b) the area re-
mains practically constant up to a = x , indicating (provid-
ed that the influence of the metallic phase already present
is negligible) that each grain of S3 yields one grain of the
intermediate spinel phase (6).At higher temperatures a
process of heterogeneous sintering of Co with Cr2O3 rather
than an independent sintering of Co alone can explain both
the observed decrease of surface area (curves c and d) and
the abnormally easy reducibility of Cr2O3 above 750'C (see
part I, section IVb). Moreover, we observed that, first, the
reoxidation of the cobalt (in reduced samples) was very
easy; under oxygen pressure Po2 = 10 Torr and at increas-
ing temperature (150°C/hr) it is completely oxidized into
Cos04 at 550OC; second, S3 spinel synthesis from the Co304-
Cr2O3 mixture so obtained is completed within 5 hr only at
63OoC, indicating that C0304-Cr203 interface and hence
Co-Cr203 interface in the reduced samples is very large.

IV. Discussion
A correct interpretation of the intermediate reduction of
I
0.5 1 L5 S3, C02+[Cr2-,3+C0,3+]B042- where x = 0.45, must ac-
a(gA') count for the three fundamental observations: (a) continu-
Flgure 5. Variation with a of the reaction rate daldt derived from ous variation of the spinel matrix lattice parameter up to a
the isothermal and isobaric a(t)curves for the reduction of S3. a is = 8.320 A; (b) production of x/2 gram atoms of metallic co-
the weight loss in oxygen gram atoms per mole of C O ~ . ~ ~ C ~ ~ .balt;
~ ~ and
O ~ (c)
. formation of x water molecules. Then, the two
following assumptions which do not satisfy all these condi-
tions, have to be discarded.
(1) As occurs in the reduction of c 0 3 0 4 , ~cobaltous
~~
oxide would form according to

S3 -,xC00 +
(1 - -3CoCrzO4 + 2 Co + xH2O
condition (a) would not be satisfied and no cobaltous oxide
was experimentally observed.

0.20 y
I / I (2) The amount of CoB3+ would decrease up to a new
value corresponding to an equilibrium concentration in the
thermodynamical conditions of the reaction
8.26 /
05
1.0
Ci IgAt)
S3 - C o ~ - ~ ~ ~ z + [ C r ~ - x 3 + C o ~+~-
4
3x
+
+ ] ~xH2O
~ 3Co O~-xz~

Figure 6. Variation with a of the lattice parameter of the spinel ma-
trix in S2 and S3 samples partially reduced at the temperatures indi-
cated on the figure and PH? = 50 Torr; (0H) values from photo-
graphs by the powder method; (0)values from diffractograms; (A)
value calculated from the (311) reflection line only on a diffracto-
gram. The open signs refer to S3,the black squares to 52.
conditions (a) and (b) would not be satisfied. The parame-
ter of this solid solution (x = 0.253) would be 8.305 8, (see
Figure 3).
We rather think that all the CoB3+is reduced to COB^+ in
the matrix; this requires (in accordance with condition (b))

The Journal of Physical Chemistry, Vol. 79, No. 22, 1975

 2404
the fraction x/2 of the C O A ~to+ be simultaneously reduced
to the metallic state so as to respect the electroneutrality
condition in it, according to
S3 - +X
C 0 1 + + / 2 ~ + C r 2 - ~ ~ + 0 4 --Co +
~ ~ - xH2O
2 can be discarded. This would yield a solid solution of same
Then, the number of normally occupied sites available in
the spinel becomes smaller than the number of cations, and
the structure must be regarded as abnormal. The following
ionic arrangement
4 = [C01-x/22+]A[Cr2-r3+cOx2+]B04-x2-
with excess Co2+on normally unoccupied B sites and a lack
of Co2+ on the A sites, has the formal advantage of being
valid for any x value. Indeed, when x = 0, S3 and 4 =
CoCrzO4, i.e., no such intermediate phase forms in the re-
duction of CoCr204. When x = 2, i.e., when the reduction of
co2+[co23+]Bo42-is concerned, 4 = [co2+]Bo2-. This last
ionic structure is equivalent to cobaltous oxide in which the
Co2+ ions occupy all the octahedral sites of the fcc oxygen
sublattice.
The second step of S3 reduction involves a further in-
crease of the lattice parameter up to the CoCr204 charac-
teristic value a = 8.330 A, and may be interpreted by
co1-x/22+[c~2-~3+cox
2+]Bo4-x 2- --*
+ + xH2O
i.e., 4 - C 0 1 - ~ / 2 ~ + [ C r 2 - ~ ~ + ] ~ 0 4 - XCO
+ +
(1 - x/2)CoCr204 xCo xH2O. The CoCrzO4 so
obtained is finally reduced into Co and Cr2O3 as described
2~~-
in part I, section IVa. This means that the octahedral co-
baltous ions are more readily reduced to the metallic state
than the tetrahedral ones. However, that reactivity differ-
ence related to the site location is very weak.
I t is probable that the above three successive reaction
steps, whose simpler formulation reduces to
xcoB3+ 4 xCOB~+ and X/2coA2+ - x/2 Coometal (l)
x COB'+ x Coometal
-
+
(1 - x/2)coA2+ (1- X/2)CO0metal
proceed according to the same elementary processes, i.e., a
Co2+ outward diffusion and a rearrangement of the other
unreduced cations in the spinel matrix; however the cation-
ic rearrangements involved in these three steps differ as
follows. In step 1, the rearranged structure (4) extends to
the whole bulk of each grain without causing it to split, and
there exists temperature conditions (2' < 55OOC) where
this reaction can be isolated (from the kinetic viewpoint).
In step 2 the rearranged structure (CoCr204) can still ex-
tend to a sufficiently large volume of the grains so as to be
experimentally in evidence, but reactions 2 and 3 are no
longer separable. Step 3 corresponds to CoCrzOs reduction
and thus may be accounted for by the reaction model de-
veloped in part I for S1. In this case the transient cationic
rearrangement (of y-Cr2O3 type) is limited to very small
superficial domains of the grains. Thus the different kinet-
ics observed for steps 1 and 3 are explained; they are both
regulated by cobaltous ions diffusion (along similar diffu-
sion paths, within different spinel structures) in the first
case, through the entire bulk of the grains, and in the sec-
ond one, through a discontinuous "interfacial layer" of lim-
ited thickness.
Concerning the reduction of S2, we first emphasize that
The Journal of Physical Chemistry, Vol. 79, No. 22, 1975
Pierre Bracconi and Louis-Claude Dufour
the assumption from which the Cr6+ would be first reduced
into Cr3+ (with vacancies destruction) according to
s 2 -I-0.17H2 - -!- 0.17H20
0.96C0~+[Crl.~~~+Coo.ii~+]~O4~-
nature as S3 which would be reduced with the same mecha-
nism. The corresponding overall kinetics would be com-
pletely different from the experimental one and the lattice
parameter would also increase more slightly than observed.
S2 reduction can be understood on the same basis as s3,
the few (0.06) CoB3+ions being first reduced to COB^+ (for
a < 0.06) and then to the metallic state (for 0.06 < a <
0.12) according to
S2 + 0.12H2 - +
0.97C0~+[Crl.~4~+Cr0.13~+00.~3]~04~-
O.09Co 0.12H20 +
The first step explains the initial deformation of the a ( t )
curves and the associated lattice parameter increase. At
this point of the reaction ( a N 0.12) vacancies and the Cr6+
ions are still present in the spinel matrix, the lattice param-
eter is consequently smaller than that of CoCr204. It may
seem a priori to be surprising that the reduction rates of
this nonstoichiometric structure and of stoichiometric
CoCr204 (Sl) are equal (cf. Figure 3, part I). This is ex-
plained a5 follows. First, S1 and S2 have similar initial sur-
face areas, and the first 52 intermediate reaction step does
not modify this situation since it does not cause any split-
ting of the initial octahedral grains. Hence the reaction
rates can directly be compared. Second, in the spinel struc-
ture, the normally occupied octahedral sites, and thus the
vacancies in S2 do not lie on the energetically most favor-
able diffusion path for C O ~ +Therefore,
.~~ they do not mi-
grate and are not involved in the rate-determining step of
the reaction.
I t seems from the slight inadequacy between the expect-
ed and observed gravimetric results below 750°C (see sec-
tion 111,kinetics (a)) that either not all the Cr6+ ions are re-
(2) duced into Cr3+ during the spinel lattice destruction or
that all of them are reduced to intermediate oxidation
(3) states, Cr5+ or Cr4+. In both cases these Cr5+, Cr4+, or re-
maining Cr6+ would have to be incorporated as excess
point defects into the a-CrzO3 lattice. Unfortunately the
presence of ferromagnetic cobalt in the reduced samples
does not allow this to be checked, by measurement of the
a-Cr2O3 magnetic constants, so that no definitive conclu-
sion can be drawn on this particular point.
References and Notes
(1) J. Guerassimov, Congr. h t . Chim. Pure Appl., 16th 1957, 227 (1958).
(2) F. Colin and J. Thery, Rev. Chim. Miner., 3, 121 (1966).
(3) K. Shimakage, T. Ejima, and S. Morioka, Trans. Jpn. lnst. Met., 11, 335
(1970).
(4) R. Yu. Dobrovlnskii, V. F. Balakirev, V. I. Dvinin, B. 2 . Kudinov, and G. I.
Chufarov. Dokl. Akad. Nauk. SSSR, 176 (5), 1067 (1967).
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Structure of Chemisorbed Ammonia on Silica 2405

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Infrared Studies of Reactions on Oxide Surfaces. IV.

The Structure of Chemisorbed Ammonia on Silica

B. A. Morrow,* 1. A. Cody, and,Lydia S. M. Lee

Department of Chemistry, University of Ottawa, Ottawa, Canada, KIN 6N5 (Received May IS, 1975)

Publication costs assisted by the National Research Council of Canada

When gaseous ammonia is allowed to react with silica a t 650°C, the same high wave number spectral fea-
tures (bands a t 3540, 3452, and 1550 cm-l) are produced as when ammonia reacts at 2OoC with a silica
which had been previously degassed at 80OoC prior to reaction. With thin samples (4 mg/cm2), an addition-
al band has been observed a t 932 cm-l. Isotopic shift data .have been used in a force constant refinement
calculation to show that the chemisorbed species is a surface SiNHz group and that the 932-cm-l band can
be assigned to the Si-N stretching mode.

The formation of surface SiNHz groups when ammonia
has been allowed to react with highly dehydroxylated silica
has been postulated by several workers who have used in-
frared spectroscopy as a means of detection.1,2 The assign-
ment was based solely on the observation of two bands near
3500 cm-l which were assigned to the symmetric and an-
tisymmetric NH stretching modes, and of a band a t 1550
cm-', which was assigned to the deformation mode. This
assignment must be considered tentative since SiONH2 or
coordinatively bonded NH3 would give rise to identical
spectral features. Low wave number spectral data have
been lacking in previous studies because the silica was to-
tally absorbing below about 1300 cm-l. In the earlier
work1B2 ammonia was presumed to react with a strained si-
loxane bridge site as follows
cm-') adsorbent-adsorbate stretching modes have been
observed with respect to chemisorbed species on silica.
Experimental Section
The silica samples used in this work (Cab-0-Si1 HS-5,
BET NP surface area 320 m2/g) were compressed into
25-mm diameter disk using pressures of about 1000 lb/in.2
for 2 sec. Sample thicknesses ranged from 40 to 4 mg/cm2,
details are given in the Results section. All samples had
been heated to about 700°C in air prior to disk pressing, in
order to oxidize any hydrocarbon impurities; such silicas
only contain noninteracting SiOH groups as characterized
by the presence of a sharp band a t 3748 cm-l. The disks
were evacuated at 25OoC in order to remove physically ad-
sorbed water prior to use (see Results). The quartz cell4
and the method for preparing oxygen-18 exchanged silicas5

-I
NH2 OH

+ siI
+ NH, si
Si
where the reactive bridge site was formed during the dehy-
droxylation process. In a brief communication3 we reported
that a new type of SiOH group (with v(OH) at 3741 cm-l)
is produced in this reaction (or after reaction with HzO or
CH30H) thus corroborating the above apparent stoichiom-
etry.
In the present paper, we have carried out a detailed spec-
troscopic investigation of all H/D, 15N/14N, and l6O/lSO
isotopic variations, and, combined with the observation of
the SiN stretching mode, we have been able to prove that
the infrared bands observed by others1,2 near 3540, 3450,
and 1550 cm-l can be assigned to SiNH2. (Further details
of the mechanistic aspects of this work will be published as
part IV, but the present spectroscopic proof of the assign-
ment is a necessary precursor to that work.) To the authors
belief, this is the first time that low-frequency (<1300
have been described previously. Nitrogen-15 ammonia
(95.4%15N) was obtained from Merck Sharp and Dohme of
Canada.
All of the spectra obtained in this work were recorded on
a modified Perkin-Elmer Model 13G filter-grating spec-
trometer, employing spectral slit widths of about 2.5 cm-l
and all spectra were accurately calibrated with reference to
known bands of various gaseous species. Force constant
calculations were carried out using the standard computer
programs developed by Schachtschneider.6
Results
Although ammonia does not react with hydroxylated sili-
ca, it is known that chemisorption does occur a t 2OoC if the
silica had been subjected to a prior vacuum degassing a t
temperatures in excess of 400°C.1-3 Infrared bands which
have been attributed to this new surface species are ob-
served near 3540, 3450, and 1550 cm-l. The nature of this
reaction is quite complex and will be discussed in part V.

The Journal of Physical Chemistry, Vol. 79, No. 22, 1975