Thermochimica Acta 404 (2003) 289–290
Short communication
Note on the use of the term “crystolysis”
Tong B. Tang
a,*
, Marek Maciejewski
b
a
NanoTech Institute, Universityof Texas at Dallas, Richardson, TX 75083-0688, USA
b
Institute of Chemical and Bioengineering, Swiss Federal Institute of Technology, ETH Hönggerberg, CH-8093 Zurich, Switzerland
Received 24 February 2003; received in revised form 24 February 2003; accepted 24 March 2003
Recently, Galwey and Vyazovkin have been en-
gaged in a debate over the significance, for the ki-
netics of a solid state reaction, of apparent activation
energy that varies continuously with α, the degree of
reactant conversion [1–3]. Such discussions will, in
our belief, contribute greatly to a healthy development
of solid-state kinetic analysis away from the emphasis
on empirical or numerical data fitting.
This development will surely take years. Here, we
wish to raise a minor point that may, however, be
non-trivial, namely the word “crystolysis” that made
to the title of Galwey’s paper [2], from its origin as
one possibility for the index reference for the decom-
position of solids [4].
We suggest that such terminology is inappropriate,
based on two reasons.
Our first object is philological. The expressions py-
rolysis or thermolysis, photolysis, radiolysis and hy-
drolysis have always denoted decompositions by heat,
light, ionizing radiation and water, respectively. Per-
haps we may also talk of electrolysis of a solid elec-
trolyte by current and “dielectrolysis” of an insulator
by electric field. Such nice convention would be bro-
ken if then “crystolysis” referred to a decomposition
in which the reactant or one or more of the reactants
belong to crystalline phases. Well, frontolysis does in-
*
Present address: Physics Department, H.K. Baptist University,
Kowloon, Hong Kong SAR, China. Tel.: +852-34117036;
fax: +852-34115813.
E-mail address: tbtang@hkbu.edu.hk (T.B. Tang).
deed stand for the dissolution of a weather front, but
that is in the less precise science of meteorology!
The other objection is scientific, and therefore more
fundamental. Although a reactant starts as a single
crystal or as a polycrystalline sample, its decomposi-
tion may not, on the atomic level, proceed in an or-
dered lattice. At active sites on a free surface, or on an
interface between the reactant and an reaction prod-
uct, the atoms may suffer so severe a disorder that
the theoretical description of their rearrangement be-
comes easier if they are treated as amorphous. A crys-
tal may not decompose as a crystal! The peculiarities
in the kinetics of such reactions, f(α), may derive sim-
ply from the geometrical constraints on the surface or
interface, an example being the melting of ice, as Gal-
wey et al. have themselves shown [5]. Prior to a con-
clusive study on a particular solid-state decomposition
we cannot tell how “crystalline” is its decomposition
mechanism, so we should not apply to it any a priori
label “crystolysis”.
We note that, besides Galwey in several of his pub-
lications, L’vov has also employed the title term [6].
On the other hand, the same term has also invoked
for “an early sign of hypoxia in the mitochondria” [of
a cell] by biologists, in a paper [7] entitled “Diagno-
sis of myocardial ischaemia by epicardial detection of
potassium ion activity,” or whatever that means. For-
tunately, a fight over the right to definite this term
seems unnecessary.
In summary, “crystolysis” is inappropriate because
all the other “-olysis” characterize atomic rearrange-
ment phenomena occurring under various influences,
0040-6031/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0040-6031(03)00187-4