Not es

NON- I S OT HE RMAL KI NETI CS

P. D. GARN
The University of Akron, Akron, Ohio, USA
(Received December 14, 1972)
The fl urry of cont r over sy over MacCal l um and Tanner ' s [1] suggestion t hat
onl y i sot hermal met hods can be used to eval uat e the order of react i on, the pre-
exponent i al f act or and t he act i vat i on energy has br ought out several deficiencies
in our view of bot h i sot hermal and non- i sot her mal kinetics as appl i ed to decom-
posi t i ons of solids.
Hill [2], in his criticism of MacCal l um and Tanner ' s concl usi on, appeal s to
aut hor i t y (Ki ssi nger [3]) which has been under criticism f r om several quart ers.
The st at ement t hat " The onl y effect of an i nst ant aneous change of t emper at ur e
is in the vel oci t y of t her mal mot i on of the part i cl es", is t oo specific. Assumi ng
we could per f or m t hat i nst ant aneous change, we know onl y t hat we have changed
the t ot al energy. Whet her or not the i ncr ement in energy leads t o instability and
change in di rect i on and/ or vel oci t y will depend upon the t emper at ur e and, in some
cases, ot her variables.
In citing the aut hori t y, Hill failed to not e t hat the expression
d x Ox -OT t dt
dt = ?:t T +
was al ready shown to be i ncompl et e by Ki ssi nger' s own dat a. Both the di l ut i on
and the radi us of the sampl e hol der influence t he rate, so t he rat e is a funct i on
of at l east t hree variables. Ot her wor k [4] suggests t hat Primo, r at her t han r, is the
appr opr i at e vari abl e.
Ki ssi nger' s DTA curve also displays a clear lag in t emper at ur e duri ng the decom-
posi t i on of kaolinite, so dT/ dt is varyi ng quite mar kedl y duri ng the event. But
dT/ dt , rat her t han T, is used in his cal cul at i ons of t he act i vat i on energy. The act ual
value used, appar ent l y, was the nomi nal heat i ng rate. By measur i ng outside t he
sampl e, this very real gradi ent coul d be shoved under the carpet , but this conceal -
ment woul d not change its reality.
The anal ogy suggested by Hill is i ndeed i nfi rm; referri ng to an ar r ow in flight
he states ( Zeno' s hypot hesi s) "al t hough the ar r ow is in mot i on, at any mome nt
it is at rest ". Mor e accurat el y, for some pur poses it may be consi dered at rest.
MacCal l um' s [5] reply is pert i nent ; i f the ar r ow were aflame, its condi t i on woul d
depend upon the i nst ant of t i me chosen. But t here are ot her variables. A par t i cul ar
16" J. The r mal Anal . 6, 1974
238 G A R N : N O N - I S O T H E R MA L K I N E T I C S
poi nt in space may be occupi ed by a poi nt in t he ar r ow at a given instant, but this
does not define t he ori ent at i on of t he arrow. It may occupy t hat poi nt in space
f r om a number of directions or have t he same or i ent at i on with a number of velo-
cities. The anal ogy now is more descriptive. The condi t i on of virtually any of t he
materials under consi derat i on will differ dependi ng upon the pat h by which it
reached t hat poi nt in time - or even level of decomposi t i on. In any real case,
t he condi t i ons of t he sample at, say, 50 % decomposi t i on will depend upon t he
geomet r y and/ or at mosphere as well as t he heat i ng rat e [6]. The react i on is by
no means homogeneous. Even t he at mospher e sur r oudi ng a given particle will
var y with t emper at ur e or time and differently f or a surface t han for a cen-
t ral l y l ocat ed particle.
MacCal l um and Tanner [1 ] refer t o homogeneous kinetics - but t o pol ymer
samples. Except in t he case of successive losses of monomer , it is hardl y likely
t hat this is a homogeneous decomposi t i on or even t he same t hr ough the course
of t he react i on. The argument s of homogeneous kinetics do not apply. For i nor-
ganic systems it is well known to solid state kineticists t hat a single descri pt i on will
not fit the whol e course of react i on [6]. Hul ber t [7] and Young [8] have shown
t hat at least five distinct regions can be identified in some i sot hermal decomposi t i ons.
The criticism by Gilles and Tompa [9] assumes arbi t rari l y t hat T is an explicit
funct i on of t, which it is not. While a measureabl e react i on is t aki ng place, larger
t emper at ur e gradients will exist in the sample (and possibly the sample hol der)
compar ed to the steady state. Furt her, these gradients will depend upon the heat i ng
rate, t he nat ure and condi t i on of the sample, etc.
Fel der and Stahel [10] not ed t hat the pr oposed correct i on was impossible to cal-
culate because, " cont r ar y to l ogi c", "i t i mp l i e s . . , t hat t he i nst ant aneous react i on
rat e depends not onl y on the present state of the s y s t e m. . , but also . . . on pre-
v i o u s . . , states". As poi nt ed out above, the "pr esent st at e" in a real react i on
is very much a result of t he path. The "far-reachi ng i mpl i cat i on t h a t . . , the non-
i sot hermal r eact or mo d e l l i n g . . , has been f undament al l y uns ound" is hardl y
new. The suggestion has been made quite explicitly f or solid state kinetics by solid
state kineticists several times. This aut hor [6] has discussed the reasons for the
success of calculated "act i vat i on energies". Fel der and Stahel also not e t hat the
Arrheni us expression is a frequent l y erroneous, semi-empirical expression, and
cite some of t he condi t i ons under which it is not valid. These conditions, plus
varyi ng composi t i ons of gaseous pr oduct s at the react i on interface, are common
in solid state decomposi t i ons.
The at t empt by Simmons and Wendl andt [11 ] to j ust i fy Hill' s criticism by an
"exercise in f undament al calculus" fails f or several of the reasons al ready advanc-
ed. The assumpt i on t hat T is an explicit funct i on of t fails j ust when it is needed
most ; the uni f or m addi t i on of even an infinitesimal quant i t y of heat in the absence
of a t emper at ur e gradi ent (within the sample) is clearly an impossibility. Mor e
i mport ant , setting down the claim t hat a result will necessarily fol l ow " i f an
expression (the Arrheni us equat i on) is assumed valid onl y f or i sot hermal react i ons"
has no meani ng when t hat expression is not valid even f or i sot hermal reactions.
J. The r mal Anal . 6, 1974
GARN: NON-ISOTHERMAL KINETICS 239
MacCal l um' s [5] defense against Felder and Stahel' s [10] emphasis on t hermal
equi l i bri um, t hat "t hi s woul d seem t o be more of a pract i cal t han a t heoret i cal
pr obl em" is quite intriguing, consi deri ng t hat this cont roversy arose because of
the failure of t heor y t o describe practice.
Suppor t by t he U. S. Na t i ona l Sci ence Fo u n d a t i o n is gr at ef ul l y acknowl edged.
References
1. J. R. MACCALLUM a nd J. TANNER, Nat ur e, 225 (1970) 1127.
2. R. A. W. HILL, Nat ur e, 227 (1970) 703.
3. H. E. KISSINGER, J. Res. Nat . Bur. St d. , 57 (1956) 217.
4. P. D. GARN, Ther moanal yt i cal me t hods of i nvest i gat i on, Academi c Press, New Yor k,
1965.
5. J. R. MACCAELUM, Nat ur e, 232 (1971) 41.
6. P. D. GARN, Ki net i c i nvest i gat i ons by t echni ques of t her mal anal ysi s, Cr i t i cal Revi ews
i n Anal yt i cal Chemi st r y, 3 (1972) 65.
7. S. F. HUEaERT, Ther mal Anal ysi s, p. 1013, Academi c Press, New Yor k, 1969. Edi t ed by
R. F. Schwenker , Jr. , a nd P. D. Ga r n.
8. D. A. YOUNG, De c ompos i t i on of Sol i ds, Per gamon Press, New Yor k, 1966.
9. J. M. GIEEES a nd H. TOMPA, Na t ur e 229 (1971) 57.
10. R. M. FEEDER a n d E. P. STAHEE, Nat ur e, 228 (1970) 1085.
l l . E. L. SIMMONS a nd W. W. WENDEANDT, Ther mochi m. Act a 3 (1972) 498.
J . Thermal Anal, 6, 1974