Reactivity of Solids, 1 (1986) 207-220 207

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

REACTION OF KCr(SO,), 12H,O (CHROME ALUM) WITH

l

AMMONIA: A (GAS-SOLID) REACTION THAT PROCEEDS WITH

THE INTERVENTION OF A VISCOUS LIQUID INTERMEDIATE
PHASE

ANDREW K. GALWEY

Department of Pure and Applied Chemistry, The Queen’s University of Belfast,

Berfast BT9 5AG (U.K.)

and

GIULIO G.T. GUARINI *

Dipartimento di Chimica, Universitb degli Studi di Firenre, Via Gino Capponi 9,

50121 Firenze (Italy)

(Received June lOth, 1985; accepted October 8th, 1985)

ABSTRACT

Exposure of partially dehydrated chrome alum [KCr(SO,),+12H,O] to ammonia gas

initiated reaction with the solid in a viscous liquid product layer across the crystal surfaces.
We identify this as displacement of water coordinated to the Cr3+ ions by ammonia and
some retention at the reactant face of water in the viscous fluid that constitutes the medium
in which chemical changes occur. This water elimination reaction is therefore fundamentally
different from the dehydration of this solid in vacuum which appears to be a nucleation and
growth process.
High-magnification microscopy, using replicas, was successfully applied to investigate the
surface textural changes that occur during the reaction. It is shown that, under appropriate
conditions, a liquid phase intervenes in this reaction, which might otherwise be regarded as a
gas-solid process. Elucidation of the detailed mechanism, however, appears to require
investigation of the homogeneous chemistry of the solutions involved, including consideration
of the solubilities of the various participants, and diffusional properties as the product
appears to constitute a barrier layer to contact between the reactants.

INTRODUCTION

In a recent study [l] of alum dehydrations it was concluded that the

function of the nucleus is to retain, at the reaction interface, a small amount

016%7336/86/$03.50 0 1986 Elsevier Science Publishers B.V.

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of water, which promotes the chemical changes that ultimately result in

deposition of the residual crystalline product. Hence the autocatalytic be-
haviour, characteristic of these rate processes, is a consequence of the
temporary retention of the volatile product within the active reaction zone.
This proposed mechanism directly contrasts with the earlier view [2] that the
solid product comprising the nucleus offers no impedence to volatile product
escape. Recent work, however, has shown that in certain other diverse
reactions of solids there may be involvement of a liquid which is a con-
densed product [3] (e.g., KBr + Cl,), a fluid intermediate [4] (NH,ClO,) or
a melt arising through eutectic formation [5] [(NH,),Cr,O,].
This recognition that a liquid may participate in reactions hitherto re-
garded as proceeding in the solid state is a recent development and a review
[6] of nucleus function has been given. The role of possible fluid inter-
mediates in reactions of solids has not been widely discussed in the recent
literature.
This paper discusses the participation of a thin superficial layer of viscous
liquid, recognized as occurring during the reaction between partially dehy-
drated chrome alum [KCr(SO,), .12H,O] crystal surfaces and ammonia gas.
The surface textural changes that develop during reaction have been ob-
served (through replication [7]) in the scanning electron microscope. These
observations permit the direct characterization of surface behaviour and
(again [6]) demonstrate the value of microscopic methods in the elucidation
of mechanisms of solid-state reactions. This work is entirely consistent with
and extends a previous optical microscopic study [8] of the same rate
process. The principal conclusion from this earlier study was the recognition
that a superficial layer of liquid participated in the reaction.

EXPERIMENTAL

The apparatus and experimental procedure employed were identical with

those previously described [l]; the vacuum equipment is illustrated in Fig. 1
in that paper. This work effectively continues one aspect of the previous
study of the dehydration of alums.
Large crystals of chrome alum of good habit were grown by slow evapora-
tion of aqueous solutions. Reactant specimens studied here were exclusively
{ill} cleavage faces exposed on fracture of the most perfect crystals by a
sharp blow with a knife edge immediately before admission to the vacuum
apparatus. All such specimens were partially dehydrated before contact with
the known pressure of the gaseous reactant, ammonia dry or containing [8] a
known amount of water vapour.
Partial dehydration of the reactant, as applied in this study, refers to
crystals containing growth nuclei, usually up to ca. 0.1 mm in diameter, that
resulted from water loss during evacuation at ca. 10e3 Torr for periods of
 209

60-120 min at 290-305 K. After such dehydration, specimens were exposed

to ammonia for reaction (usually at 290 K) and dried by evacuation for a
further 5 min at the same temperature. Surfaces for examination in the S 180
scanning electron microscope were replicated by the technique already
described [7]. All representative features of interest were photographed and
the illustrations reproduced here were selected as being reproducible and
typical of the textures developed during reaction. Dehydration nuclei that
have not been exposed to ammonia are shown in previous papers [1,7].

RESULTS AND DISCUSSION

Investigation of reaction stoichiometry

Prolonged exposure of a chrome alum crystal to dry ammonia gas (72 h at

285 K) yielded a highly viscous (glue-like) liquid product. This smelled
strongly of ammonia and the composition corresponded to KCr(SO,), .
2.5NH,. xH,O (the water content varied). Ammonia also reacted with the
residual product of chrome alum dehydration [l] [KCr(SO,), - 6H,O], yield-
ing a viscous product of approximate composition KCr(SO,), - 1.5NH, .
4.5H,O.
The overall compositions of the residual products of these reactions do
not permit characterization of the constituents present as the liquid may be
inhomogeneous; double salts, solid solutions or mixtures may result from
water removal. Moreover, various complex ions may be present in which the
Cr3+ ion is coordinated with H,O, NH, and SO:-. We conclude from the
available evidence that ammonia displaces some water from the crystalline
reactant, presumably by coordinating with the Cr3+ ion in its place. Re-
leased water then provides a solution medium in the form of a viscous liquid
and this, if dried by evacuation, is converted into a mixture of crystalline
residual sulphate products.

Reaction of chrome alum with dry ammonia

Exposure of pristine (i.e., undehydrated) chrome alum surfaces, following

brief (5 min) initial evacuation, to 50 Torr of dry ammonia for 20 min at 290
K resulted in no appreciable reaction. At higher pressures of ammonia a
slow surface process was detected, but the reactivity was always significantly
below that observed for comparable reactions in air. This difference is
attributed to the absence of water in the surface layer under conditions
favouring its rapid removal by evaporation.
Several crystals were partially dehydrated (under conditions specified in
the Experimental section above) and subsequently exposed to 70 Torr of dry
ammonia for 7 min at 290 K before being dried by evacuation (5 min),
210

replicated and the surface textures examined in the scanning ek :ctron mic:ro-
scope. Typical photographs illustrating the modifications of nu cleus text Lure
which result from the exposure to ammonia are shown in Fig. 1. There 1was
no evidence on the surface of angular structures, such as step e dges that are

Fig. 1.
 211

Fig. 1. Chrome alum [KCr(SO,),. 12H,O] crystal surfaces, for examination using the scan-
ning electron microscope, were freshly cleaved and dehydrated as described in the text. The
three examples show typical textures developed following exposure to 70 Torr of dry
ammonia for 7 min at 290 K. Some variations in texture were evident across each surface
examined, and these were selected as being representative. (a) A growth nucleus shows
modification at the periphery adjoining the original crystal surface attributable to solution-
promoted product recrystallization. (b) Recrystallization of the surface is more advanced and
there is wrinkling of the surface beyond the zone previously dehydrated, again consistent with
the generation of a superficial liquid layer. (c) Surface liquefaction has proceeded to the point
where replication of the intranuclear crack structure is not possible but the viscous fluid
retains the rounded remnants of the dehydration nuclei.

present on unreacted cleavage faces. Ammonia-treated surfaces, however,

included rounded features, attributed to control by surface tension forces
after reaction of the outer layer of the reactant crystal had produced a
superficial liquid layer. Modifications around the periphery of the nucleus
surface suggest the gradual movement of Iiquid into the intranucIear cracks.
Such product modification, probably accompanied by recryst~lization, has
commenced in Fig. la and is further advanced in Fig. lb (note the wrinkling
of crystal surface beyond the nucleus). In Fig. lc these changes have filled
the outer zones of the product crack structure and thus their inner portions
cannot be replicated. The extent of such changes varied appreciably across
the individual surfaces examined here. These textural modifications are
(again [S]) explained by the formation of a superficial layer of highly viscous
liquid that becomes rounded at angular features and flows into surface
cracks, including those within the nuclei.
212

Reaction of partially dehydrated crystals in 100 Torr of an lmonia for 5

min at 290 K resulted in the retexturing of internuclear surfa ices (Fig. 2a)
and separation of the reactant-product contact at the nucle us boundary

Fig. 2.
 213

Fig. 2. Surface structures observed after exposure of a dehydrated crystal to 100 Torr of
ammonia for 5 min (a) and (b) or 120 min (c) at 290 K. (a) Internuclear surface that has
undergone retexturing attributable to reaction in a surface fluid followed by recrystallization
on dehydration. (b) A nucleus on the same surface as (a); separation of the reactant-product
contact has occurred and this zone is now penetrated by the replicating material. (c) This
surface was exposed to ammonia (100 Torr) for a longer time (120 mm), treatment which
resulted in much more extensive reaction, cracking during later dehydration and separation of
a loosely adherent superficial product layer (thickness ca. 1 pm).

(Fig. 2b). Longer exposure of similarly pretreated surfaces to 100 Torr of

ammonia for 120 mm at 290 K resulted in extensive cracking of a distinct
product layer (thickness ca. 1 pm). These results are evidence of slow
reaction across all surfaces of the reactant crystal. The texture of the
internuclear zones after the short reaction period (5 min, Fig. 2a) suggests
modification as a result of water evaporation from droplets of saturated
solution. The texture developed after dehydration following longer reaction
(120 mm, Fig. 2c) suggests water removal from a coherent product layer that
undergoes extensive cracking during shrinkage. Penetration of the reaction
interface by replicating fluid (Fig. 2b and c) shows separation of the
reactant-product contact, but there is no marked enhancement of reaction
within the nucleus.
A crystal dehydrated for a longer period (evacuation for 350 min at 293
K) was exposed to 75 Torr of dry ammonia for 5 mm and characteristic
features are shown in Fig. 3. Two significant structures are of interest. The
mosaic texture of the internuclear surface areas are different from those seen
214

Fig. 3. Textures developed after a considerably extended period of initial evacuation to 10P3
Torr for 350 min at 293 K, followed by exposure to 75 Torr of ammonia for 5 min and 5 min
evacuation. The internuclear zones developed a mosaic texture and this difference from the
other samples indicates time-dependent changes of the surface during evacuation. There is
also evidence that ammonia has resulted in separation of reactant-product contact at the
former reaction interface.

before, giving evidence that such zones change during extended times of
dehydration. The separation of the reactant-product contact at the nucleus
periphery may result from some retention of water at the reaction interface
in this large nucleus (the replica here, Fig. 3, has extended partially into the
hemispherical outer boundary of the nucleus).

Reaction of chrome alum with ammonia and water vapour

Previous work [8] showed that in the presence of water vapour the amount
of superficial liquid present increased. Admission of relatively small propor-
tions of water under the present reaction conditions resulted in appreciable
modifications of behaviour.
The sequence of reaction conditions experienced by the nucleus shown in
Fig. 4a only differed from those in Fig. 1 by the inclusion of 3 Torr of water
vapour in the ammonia gas admitted. The internal structure of these nuclei
was different from those observed following the other reactions by the
presence of an additional, concentric intranuclear crack system. This pre-
sumably results from product phase recrystallization. Elsewhere on the
 215

Fig. 4. Changes following exposure of dehydrated surfaces to ammonia containing a small

proportion of water vapour. (a) After 7 mm exposure to 70 Torr of amm lonia and 3 T err of
water the crack structure within the nucleus had been modified by th le appearance : of a
second, concentric crack pattern. This is ascribed to product recrystalliza tion and was never
observed for replicas of untreated dehydration nuclei. (b) Exposure to a higher press ure of
ammonia, for 5 min in 100 Torr of ammonia and 3 Torr of water, resultec d in more extl ensive
reaction and cracking of the internuclear zones following subsequent dehydration . The
nucleus structure has evidently not been modified here.
216

internuclear surfaces the rounded features were the same as those found after
exposure to dry nitrogen.
As shown in Fig. 4b, inclusion of 3 Torr of water vapour in 100 Torr of
ammonia and reaction for 5 mm resulted in much more extensive surface
modification than after similar treatment with dry ammonia as can be seen
on comparison with Fig. 2a and b. Longer exposure to ammonia-water
vapour mixtures increased the thickness of the layer retextured. Optical
microscopic observations, using the reflection mode [l], also revealed the
occurrence of surface retexturing [8] on the exposure of dehydrated crystal
faces to ammonia-water vapour mixtures contained in a nitrogen flow. Two

Fig. 5. Optical micrographs (Reichert Zetopan in the reflection mode) of the cleaved (111)
surface of a chrome alum crystal. Magnification X 140. (a) Before admitting the nitrogen-am-
monia-water mixture; (b) after ca. 1 mm of treatment at 296.2 K with a 28.6 cm3 min-’ flow
of nitrogen containing 1.75.10-* mol crne3 of ammonia and ca. 4.10-” mol cmW3 of water.
 217

successive stages in such a reaction are shown in Fig. 5a and b (details of the
reaction conditions are given in the caption). The appearance of the inter-
nuclear zones is strongly indicative of the development of a fluid layer.
Under prolonged action of the gaseous mixture, dendritic growth of the
“nuclei” took place, followed by the disappearance of the fluid and the
beginning of dehydration [9].

Thermochemical measurements

We have also obtained evidence from thermochemical measurements

(Mettler TA 2000 apparatus) that reaction proceeds through two distinct
steps (Fig. 6). An initial endothermic process occurs very rapidly after
admission of the nitrogen-ammonia-water mixture and is ascribed to the
surface process. Immediately following and sometimes overlapping with this
process (the separation being dependent on ageing, the shape of the crystal
and on the rate of gas flow) there follows the slower but very much more
extensive endothermic transformation that is ascribed to continuation of the
chemical change into the bulk of the reactant. The separation of the total
heat of transformation into two (surface plus bulk) contributions appears to
be a general property of the rehydration reactions of dehydrated crystal
surfaces [lO,ll]. Further, a partial separation for the dehydration of sodium
thiosulphate pentahydrate has been reported [12].

Fig. 6. Diagrammatic representation of the separation of the surface and bulk contributions
of the heat of transformation obtained by treating crystals of chrome alum cleaved parallel to
(111) with a flow of nitrogen-ammonia. Typical isothermal recording conditions were
temperature, 295-303 K; nitrogen-ammonia-water flow-rate, 20 cm3 min-‘, containing ca.
8.10-’ mol cme3 of ammonia and ca. 1.5.10V9 mol cmm3 of water; recorder chart speed, 2
cm mitt-’ up to the asterisk and then 4 cm hh’; sample mass, lo-30 mg; and mean duration
of an experiment, 10 h.
218

At the end of the complete (surface-bulk) endothermic process the change

in weight of the cleaved crystals corresponded to the loss of six water
molecules as in the vacuum dehydrations and the total enthalpic change was
almost identical (306.3 rt 5.0 kJ/mol compared with 296.3 f 6.3 kJ/mol)
with that determined using dry nitrogen as a dehydrating agent (in the latter
instance however, the thermal peak was unique). The mean value + standard
de~ation for eighteen deter~nations of the ratio between the heat corre-
sponding to the first peak and the total heat was 2.4 +10e3 f 1.1 . 10S3, i.e.,
lower than but comparable to the corresponding value found for rehydra-
tions [ll]. This is taken as an indication that the surface layers involved in
the two processes have almost the same thickness. It is also thought that the
bulk reaction is delayed in the presence of ammonia because of the forma-
tion of the liquid layer on the crystal surfaces.
All the above results are entirely consistent with the explanation that the
accumulation of water on the reactant surface provides the medium in which
the initial chemical changes occur.

CONCLUSIONS

The above observations, considered in the context of our previous work

[8,9], lead us to conclude that chrome alum reacts with ammonia to yield
water, which is retained in a superficial layer of viscous liquid on the crystal
surface. Within this layer the chemical changes proceed. The initial stage in
this process is identified as ligand replacement, II,0 by NH,, at the Cr3+
ions which may be regarded as dehydration of the solid. Formation of the
fluid phase necessitates water retention at the crystal surface, and this is
determined by (among other factors) the prevailing pressure of gas which
controls its rate of diffusive removal. The retained fluid constitutes the
medium within which chemical changes occur and also represents a barrier
to contact between reactants.
The reaction geometry [6] of the overall chemical change studied here
differs markedly from the nucleation and growth process characteristic of
dehydration in a vacuum [l]. The present reaction was initiated across a/i
boundary surfaces of the crystal, indicative of the zones wherein the sub-
surface release of water can lead to the generation of the fluid reaction
medium. The overall extent of this interface reaction increased with time of
exposure to ammonia and with the availability of water in the gas admitted.
There was no evidence that reaction occurred preferentially within estab-
lished nuclei, zones from which water had already been withdrawn. Indeed,
after exposure to ammonia, the surface fluid tended to enter the surface
cracks of grown nuclei (Fig. 1) and there was separation of reactant product
contact at the active reaction interface (Figs. 2b and c, and 3). There was
some inconclusive evidence from replicas that, after ammonia pretreatment,
 219

internuclear cracks became wider at their innermost extremities, correspond-

ing to the active reaction zone. This may be evidence of water retention here,
but the observations were not regarded as sufficiently reliable to be accepted
as a final proof, confirming this important feature of our proposed mecha-
nism for the dehydration reaction. The present results do show, however,
that the amount of water retained within such nuclei is not large.
The contributory chemical changes that together constitute the present
reaction are not envisaged as occurring at an interface [6], but within the
liquid layer. These are, therefore, subject to controls determined by solubil-
ities and concentrations of the several possible participants, both reactants
and products, together with inhomogeneities resulting from diffusion of
reactants across the barrier layer, water evaporation, reactant dissolution,
product precipitation [6], etc. The present examination has demonstrated the
complexity of overall behaviour but it would undoubtedly be very difficult,
probably impossible, to elucidate the reaction mechanism in detail from
these kinetic and observational data alone. Identification of the factors
controlling the reactions in the fluid phase would be more directly achieved
by studies of the homogeneous concentrated solution chemistry of the ionic
entities involved [5] and interpreted in the context of the present observa-
tions.
This present study, therefore, draws attention to the possible role of fluids
in reactions of solids and indicated the necessity for complementary studies
of the properties of the solutions postulated in formulating reaction mecha-
nisms in detail. Kinetic data alone are unlikely to result in the identification
of the factors that control the present reaction. The use of microscopy has
been most valuable in elucidating the general pattern of behaviour.
The observation that the reaction is initiated on the whole of the crystal
faces is a further manifestation of a more generally observed phenomenon.
In fact, there are a growing number of examples of reactions of solids in
which reactivity appears to be a property of, or at least to be dominated by,
the boundary (interphasal) layer. Behaviour of this kind has been described
in several of the papers already cited here, as in the dehydration of alums [l],
the KBr + Cl, reaction [3] and the decomposition of (NH,)&r,O, [5].
Similar enhanced reactivity within mobile interphasal layers has been ob-
served by Dei et al. [12] and Warble [13] and the relatively facile migration
_
of surface species by Haber [14]. Moreover, most recently the formation of a
two-dimensional surface layer having mobile properties has been considered
to explain the catalytic oxidation of carbon monoxide on platinum wires
v51.

ACKNOWLEDGEMENTS

We thank Mr. R. Reed for his help and advice in obtaining the electron
micrographs, and Dr. A. Fallavollita and Mr. M. Rustici for the collection
220

and critical revision of thermal data; G.G.T.G. also acknowledges financial

support from the Italian Minister0 della Pubblica Istruzione.

REFERENCES

1 A.K. Galwey, R. Spinicci and G.G.T. Guarini, Proc. Roy. Sot. London, Ser. A, 378 (1981)
477.
2 G.P. Acock, W.E. Garner, J. Milsted and H.J. Willavoys, Proc. Roy. Sot. London, Ser. A,
189 (1947) 508.
3 A.K. Galwey and L. Poppl, Philos. Trans. Roy. Sot. London, Ser. A, 311 (1984) 159.
4 A.K. Galwey and M.A. Mohamed, Proc. Roy. Sot. London, Ser. A, 396 (1984) 425.
5 A.K. Galwey, L. Pbppl and S. Rajam, J. Chem. Sot., Faraday Trans. I, 79 (1983) 2143.
6 A.K. Galwey, Thermal Analysis, Proc. 7th Int. Conf., Kingston, August 23-28, 1982,
Wiley, New York, 1982, p. 38.
7 A.K. Galwey, R. Reed and G.G.T. Guarini, Nature (London), 283 (1980) 52.
8 A.K. Galwey, G.G.T. Guarini and R. Spinicci, Reactivity of Solids 9, Proc. 9th Int. Symp.
Reactivity of Solids, Cracow, 1980, Elsevier, Amsterdam and P.W.N., Warszawa, 1982, p.
397.
9 G.G.T. Guarini, R. Spinicci and A.K. Galwey, in W. Hemminger (Editor), Thermal
Analysis, Proc. I.C.T.A. 80, Vol. 2, Birkhaeuser Verlag, Basel, 1980, p. 217.
10 G.G.T. Guarini and L. Dei, J. Chem. Sot., Faraday Trans. I, 79 (1983) 1599.
11 L. Dei, G.G.T. Guarini and S. Piccini, J. Therm. Anal., 29 (1984) 755.
12 L. Dei, G.G.T. Guarini and S. Piccini, in P. Barret and L.-C. Dufour (Editors), Reactivity
of Solids 10, Proc. 10th Int. Symp. Reactivity of Solids, Dijon, August 27-31, 1984,
Elsevier, Amsterdam, 1985, p. 691.
13 C.E. Warble, in P. Barret and L.-C. Dufour (Editors), Reactivity of Solids 10, Proc. 10th
Int. Symp. Reactivity of Solids, Dijon, August 27-31, 1984, Elsevier, Amsterdam, 1985, p.
893.
14 J. Haber, Pure Appl. Chem., 56 (1984) 1663.
15 A.K. Galwey, P. Gray, J.F. Griffiths and SM. Hasko, Nature (London), 313 (1985) 668.