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Energy Changes When Kaolin Minerals Are Heated

This document summarizes research into how energy changes occur when kaolin minerals like kaolinite are heated. The key points are: 1) Dehydration of kaolin minerals occurs between 400-700°C, but the temperature varies between different minerals. This dehydration is an endothermic reaction. 2) Between 900-1000°C, a marked exothermic reaction occurs, possibly preceded by a small endothermic reaction. A second exothermic reaction happens around 1200°C. 3) Experiments were conducted to determine the activation energies of dehydration for various kaolin minerals using thermal analysis. Activation energies and frequency factors were calculated to provide insight into the reactions.

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0% found this document useful (0 votes)
177 views10 pages

Energy Changes When Kaolin Minerals Are Heated

This document summarizes research into how energy changes occur when kaolin minerals like kaolinite are heated. The key points are: 1) Dehydration of kaolin minerals occurs between 400-700°C, but the temperature varies between different minerals. This dehydration is an endothermic reaction. 2) Between 900-1000°C, a marked exothermic reaction occurs, possibly preceded by a small endothermic reaction. A second exothermic reaction happens around 1200°C. 3) Experiments were conducted to determine the activation energies of dehydration for various kaolin minerals using thermal analysis. Activation energies and frequency factors were calculated to provide insight into the reactions.

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ENERGY CHANGES W H E N KAOLIN M I N E R A L S

A R E HEA TED
By F. VAUGHAN
British Ceramic Research Association, Stoke on Trent.
[Read 6th November, 1954]
ABSTRACT
The work outlined in this paper was undertaken to show how, by a
consideration of the energy changes involved, some insight may be
gained into the reactions occurring when kaolin minerals are heated.
Activation energies have been determined experimentally for the
dehydration of various kaolin minerals. The fireclay mineral is dis-
tinctive and it is suggested that it does not form part of a halloysite-
kaolinite series. It is further thought possible that there is a series of
fireclay minerals.
From thermochemical and thermodynamic considerations the heat of
formation of kaolinite has been calculated approximately and enthalpy
and free energy changes have been estimated for the exothermic reaction
at 980~ These indicate that, if a compound is produced during de-
hydration, the most probable explanation of the exothermic reaction is
the simultaneous production of mullite, ),A1203 and SiO2. Finally
the lattice energies of kaolinite and its thermal decomposition products
have been calculated.
INTRODUCTION
An extensive literature testifies to the considerable research that
has been carried out on the thermal decomposition of kaolinite and
related minerals. Nevertheless a complete picture has not yet been
obtained of the various changes that occur on heating.
(A) Dehydration. In less well-crystallized kaolin minerals sorbed
water is removed in an initial endothermic reaction at about 100~
All minerals in the kaolin group undergo dehydration within the
temperature range 400-700~ but the dehydration temperatures
differ for the various members, being highest for dickite and nacrite.
The start of dehydration is also determined by other factors. The
precise nature of the dehydration product is still not settled but most
workers consider it to be either a poorly-organized compound,
A12Si20 v, or a mixture of alumina and silica. A minority think it to
be similar to a solid solution, and various other theories, not now
seriously held, have been propounded. The literature has been
reviewed by Pieters (1928), Mellor (1938) and others. The de-
hydrated material is essentially amorphous, but pseudomorphs after
the parent mineral are common; a few may persist to very high
temperatures (1,300-1,400~ although other reactions must have
occurred within them.
The researches of both Nelson and Hendricks (1944) and Brown
and Gregg (1952) suggest that the loss of combined water results in a
smaller increase of surface area than might be expected. In this
connection, it is interesting to note that Slawson and Vaughan (1954),
using the electron microscope, have observed that, in the absence of
deflocculating agents, there is an aggregation of the pseudomorphs
265
266 v. VAUGHAN
after kaolinite and dickite. Suspensions of the dehydrated material
were also found to settle more rapidly than unfired kaolinite and
dickite.
(B) High-temperature reactions. Between 900~ and 1,000~ a
marked exothermic reaction occurs, possibly immediately preceded
by a small endothermic reaction, and a second evolution of heat is
observed at about 1,200~ There is no universal agreement about
these reactions and there exists little information about reactions
above 1,300~ The temperatures at which the reactions begin
vary for the different kaolin minerals; they are functions of time and
temperature (Richardson, 1951), and there are other complicating
factors to consider such as catalysis and grain size.
The work outlined in this paper was undertaken to show how
some insight may be gained into the reactions by a consideration of
the energy changes involved. More accurate data than are at present
available may well yield a final elucidation.
KINETICS
Before 1932 there existed little quantitative data on th~ decom-
position rates of clays. Schwartz and Trageser (1932), Budnikov and
Bobrovnik (1936), and Murray and White (1949), obtained informa-
tion indicating that kaolinite dehydrated according to a first-order
law. The last workers estimated the activation energy by using the
Arrhenius (1889) equation, and applied the data to differential thermal
analysis.
(,4) Determination of clay mineral content. The author has studied
a number of cla'ys; china clay, ball clay,fireclay, dickite and halloysite.
Chemical analyses, petrological, electron-microscope and X-ray
studies, d.t.a, examinations and estimations of organic matter and
carbonate content were made. Halloysite and dickite contained no
impurities capable of interfering in the dehydration studies. The
china clays, ball clays and fireclays all contained some mica but, at
the dehydration temperatures used, its interference is negligible. The
organic matter in the ball clays and fireclays was removed by hydrogen
peroxide treatment; an initial heating (below 400~ of halloysite,
ball clays and fireclays ensured the removal of sorbed water. Re-
producible dehydration curves were best obtained after the ball-,
china and fire-clays had been ground to pass a 120 mesh B.S. sieve,
but the dickite and halloysite were used as received.
For each mineral a weight loss-v-tifne curve was determined by
placing weighed samples in a small laboratory electric furnace main-
tained at a constant temperature. Temperatures from 450 to 550~
proved adequate in studying all the minerals except dickite for which
temperatures between 550~ and 650~ were necessary.
Two methods were used to estimate the amount of clay mineral
initially present, that o f Murray and White (1949) and a method
based on the following equations:
k = l [loge xl - loge (X2 - (1)
ENERGY CHANGES OF HEATED KAOLINS 267
and
X 2 --X 1
a ~- (2)
e - kt 1-e - kt2
where k is the velocity constant at a particular temperature in the
dehydration range ( e . g . , 550~ a is the amount of clay mineral
initially present, and x t , x 2 are the amounts decomposed in times
t 1, t z respectively. The full derivation o f these equations will not
be given here but equation (1) is only valid when t 2 = 2 t r The weight
losses occurring at 10 and 5 minutes, 12 and 6 minutes and so on,
were derived from the loss-time curves and, by substitution in equation
(1), k was calculated. Both methods confirmed that the dehydration
was a first-order reaction, and for such reactions k can be substituted
in equation (2) and the amount of clay mineral (a) calculated.
Values of a obtained by the Murray and White method agreed quite
well with those obtained from equations (1) and (2); they should, of
course, yield identical values since both methods are based on a
first-order equation. The differences between them may be a
measure of the accuracy of the experimental dehydration curve.
(Owing to the small amounts of dickite and halloysite available full
dehydration curves for these minerals were not obtained, and a
was estimated on the basis of the preliminary studies mentioned
earlier). The results are given in Table 1 where the clay contents
obtained using the author's procedure are compared with those
obtained when using the Murray and White method.
TABLE 1--Clay mineral contents of clays using different methods.

Clay Mineral Content (~o)


Experimental
Values
Substance Locality Calculated Value used
Murray from for
Vaughan and ultimate subsequent
method White Analysis calculations
method
China clay 1 Cornwall 86.8 86,1 86.6 87
China clay 2 Cornwall 98'0 95,0 95.0 98
Fireclay 1 Shropshire 43-1 40,2 42.4 43
Fireclay 2 Lincolnshire 22-5 22.9 20"8 23
Fireclay 3 Staffordshire 61 "0 61.4 47.2 61
Fireclay 4 Durham 54-2 52.1 50-0 54
Fireclay 5 Yorkshire 34 '4 34.8 40.4 34
Fireclay 6 Scotland 71 "0 66-0 78"0 71
Ball clay 1 Dorset 38.5 39.5 50.5 39
Ball clay 2 North Devon 43 -0 40.7 50.2 43
Ball clay 3 South Devon 23.1 23-0 20.4 23
Halloysite Djebel-Debar 97
(A12Si207.
2H20)
Dickite Chihuahua, 100
Mexico
268 F. VAUGHAN
(B) Activation Energies. Graphs of log10 ( a - x ) against t showed
the reactions all to be of the first-order at other temperatures and,
knowing velocity constants in the dehydration range, activation
energies and frequency factors were evaluated from the Arrhenius
equation :
k = Ae - E / R T (3)
where k is the velocity constant, R the gas constant, T the absolute
temperature, A the frequency factor and E the activation energy.
Values of E and A are given in Table 2, together with times of half-
reaction at 550~ calculated from:
0.6931.
tt-- k
TABLE2--Values for E, A and half-reaction time for clays.

Time of half Activation Log~0


Substance dehydration Energy, E (Frequency
at 550~ (rain.) (cal./g.mol.) Factor)
China clay 1 6-3 40,610 9"83
China clay 2 5.0 38,100 9"26
Fireclay 1 4.7 25,750 6"01
Fireclay 2 3.7 26,300 6"26
Fireclay 3 5-0 23,740 5"44
Fireclay 4 4.8 22,870 5'24
Fireclay 5 3-7 25,980 6"18
Fireclay 6 3.2 29,270 7"11
Ball clay 1 3-1 34,300 8 "47
Ball clay 2 2-0 29,730 7"44
Ball clay 3 1.9 26,300 6"55
Halloysite 4.6 34,900 8 "45
Dickite 34-7 48,020 10"94

The exact significance of the frequency factor is not known, but it


may be related to the vibration frequencies of the hydroxyl groups in
the middle layer of the lattice. The activation energy of dehydration
is associated with ease of decomposition, and thus indirectly with
mineral structure. A high activation energy does not necessarily
indicate a slow reaction or vice-versa, because the driving force
is not the activation energy but the free energy of activation.
For this reason presumably the ball clays in this study dehydrated
faster than some of the fireclays, although their dehydration activa-
tion energies were somewhat higher.
These results do not support the view that fireclays and ball clays
occupy an intermediate position in a halloysite-kaolinite series but
emphasise the distinctive natures of their minerals. The name
livesite has been proposed for the fireclay mineral (Carr, Grimshaw
and Roberts, 1952), but Table 2 suggests the possibility of a series of
fireclay minerals. No evidence was obtained that the appreciable
amounts of impurities present in some of the fireclays and ball clays
inhibited dehydration, and the determined activation energies prob-
ENERGY CHANGES OF HEATED KAOLINS 269

ably represent those obtaining in free dehydration. The water


vapour pressure above the sample did not reach a level sufficient to
cause any appreciable retardation of dehydration.
(C) Differential Thermal Analysis. D . G . Beech (1954) has derived
several equations relating kinetic behaviour to d.t.a., assuming that
the main endotherm i~ largely dependent upon the values for E and A
and the heating rate, and neglecting other thermal factors such as
conductivity, etc. These equations are thus only approximate. The
main endotherm may be obtained from the equation:
dXl00 I{ AE.e-Y 2 6 24 120 720 }1
dt -=100Ae-Y exp 1 - f +~-~-T "~ y4
B.---.-.-.-.-.-.-.-.~T yS ~ (4)
The series may be terminated where desired, the error being of the
order of the last term retained. In equation (4) B is the heating rate
(~ y = E / R T , and the other symbols have the significances
mentioned earlier.
At the endothermic peak temperature
y 2=~.-~
AE "e-Y (5)
AE y
or 2 loglo y=loglo ~-~ 2.303 (6)

Values of T = ~may be inserted until the left-hand expression


..I

becomes equal to the right-hand expression; T is then the endo-


thermic peak temperature. Beech's equations have been used in
conjunction with the data from Table 2 and reasonable agreement
(within 8~ was obtained between calculated and determined peak
temperatures for seven of the kaolin minerals. Agreement in the
other six instances was not so good. This work leads to the belief
that kaolin minerals are not as simply inter-related as has sometimes
been assumed and further research is desirable.
T~RMOCHEMISTRY AND THERMODYNAMICS
If, as suggested by Maier and Kelley (1932), the molar heat
capacity (Cp) varies with the absolute temperature according to the
equation
C p = a + bT - cT -2 (7)
the heat of reaction (AH) and free energy (AF) vary with temper-
ature as follows :--
A H = A H o + A a T + 2 Tz + A c T -~ (8)

A F = A H o - AaTlnT - -~-T 2 + 2 T - ' + IT (9)


In equation (7) a, b and c are constants and, if data are available both
for reactants and products then da, Ab and Ae can be evaluated.
Knowing AH and AF at one temperature the constants AH o and I
respectively can be calculated.
270 F. VAUGHAN
(A) Dehydration. Published values for the heat of dehydration of
kaolinite range from about 10,000 to 60,000 cal/g.mol. (AlzSizO 7.
2I-I20), but a value of the order of 30,000 to 40,000 cal/g.mol, is now
gaining more general acceptance. For dehydration at 550~ AH
may be taken as 35,000 cal/g.mol, since the activation energy (Table
2) of an endothermic reaction cannot be less than the heat absorbed
in that reaction. Table 2 also suggests that AH should be highest
for dickite dehydration and lowest for the dehydration of certain
fireclays. It therefore seems likely that AH ranges from about
20,000-45,000 cal/g.mol, f o r the kaolin minerals. Stone (1952)
found that the dehydration heat of dickite was 140 cal/g. (c. 36,000
cal/g, mol.).
Only approximate heat capacity data are available for kaolinite
and its decomposition products and the validity of some of the data
is questionable. They are insufficiently accurate to justify inclusion
of the Y-2 terms. However, if the following values are substituted,
Kaolinite . . . . . a=39-53 b-----55-75• 10 -3
Dehydrated kaolinite a = 5 0 . 9 7 b=22-75 x 10-3
W a t e r v a p o u r . . . a = 7.33 b = 2.48• -3
AH298 is found to be about 29,000 cal/g, tool. The kaolinite
constants were calculated from an equation for kaolin in the Hand-
book of Physical Constants (1942) but for dehydrated kaolinite
and water the a and b values were derived from published specific
heat data.
Suggested "best" values for heats and free energies of formation
are given in Table 3.
T A B L E 3--Heats and free energies of formation of clay minerals.

Heat of formation at Free energy of formation


Substance 298~ (cal/g. mol.) at 298~ (cal/g. mol.)
Kaolinite c . - 945,000 n.d,
Metakaolin (A128i207) - 803,700 - 719,410
Water vapour - 57,798 - 54,636
Amorphous silica c . - 202,000 c . - 191,000
Amorphous alumina - 389,490 c . - 367,000
e-alumina -- 395,100 c . - 373,000
Mullite -1,804,000 -1,711,530

The heats of formation of metakaolin, y-alumina and mullite were


given by KrtSger (1953). Avgustinik and Mchedlov-Petrosyan (1952)
gave the same mullite value, but gave -767,500 cal/g, mol. and
-391,290 cal/g, mol. for the heats of formation of metakaolin and
y-alumina respectively. This value for metakaolin is also quoted in
the H a n d b o o k of Chemistry and Physics (1950), and in the same
compilation the heat of formation of amorphous alumina is given.
The free energies of formation of metakaolin and mullite were given
by Avgustinik and Mchedlov-Petrosyan (1952) and the value of
- 369,060 cal/g, tool. was given for the free energy of formation of
y-alumina. The data for water vapour are taken from Rossini et. al.
ENERGY CHANGES OF H E A T E D KAOLINS 271
(1952). The remaining values in Table 3 were estimated by the author
by comparison with data from a number of sources, but they require
experimental confirmation.
From these results an estimate of the heat of formation of kaolinite
has been made. Two possibilities exist, however; if dehydration
results in a compound the value is c-950,000 cal/g, mol., if a
mixture c-940,000 cal/g, mol. The probable order of the true
value for the heat of formation is therefore about - 945,000 cal/g, mol.
Available information is not sufficient to decide the exact nature of
the dehydration product from kaolinite but for dickite, Vaughan and
Wilde (1954) found that all the original lines of the X-ray pattern
persisted for about 45 minutes after complete dehydration at 550"~C.
The lattice then collapsed, only one line remaining (at about 4.35 ~,)
possibly due to an impurity.
(B) HL~h-temperature endothermic reaction. Grim and Bradley
(1948) noted a small endothermie reaction immediately preceding the
first exothermic reaction in certain well-crystallized clays. This may
be due to the release of a small amount of water retained in the
lattice (see also Roberts, 1951). In this connection it is interesting to
note that De Boer and Houben (1954) suggest that water is involved
in the structure of ~,-alumina. A thermodynamic explanation is
possible if the effect is caused by collapse of a c o m p o u n d into amor-
phous products, since this would result in an increase of entropy and
an absorption of heat.
(C) Exothermic reaction at 980~ ~,-alumina and mullite forma-
tion have both been suggested to account for the first kaolinite
exothermic reaction (980~ Published values for the heat evolved
range from 8 - 4 0 cal/g, of kaolinite but most are between 1 6 - 2 5
cal/g. There are several possible explanations of this reaction. If
the dehydration product is a mixture of silica and alumina, then, after
the conversion of amorphous alumina to ~,-alumina (Reaction 1)
mullite formation might proceed as follows:--
3)'-AlzO3 + 2SIO2 ~A16SizOl 3 (Reaction 2)
If the dehydration product is a compound then possible modes of
breakdown are :--
AlzSi_,OT--amorphous A1203 +2SIO2 (Reaction 3)
or A12Si207-~-A120 3 + 2SiO 2 (Reaction 4)
or 3(AI/Si,_O7)--AI6Si2013 -~ 4SIO2 (Reaction 5)
or 4(Al/SizOT)--A16SizO~3 +y-AlzO 3 + 6SiO z (Reaction 6)
AHz98 and AF298 calculated from the data in Table 3, are given in
Table 4. Values calculated from data given by Avgustinik and
Mchedlov-Petrosyan (1952) are given in brackets. Combining heat
capacity equations from various sources with the results in Table 4 it
was found that, at 980~ the greatest free energy change accompanied
reaction 6. These approximate calculations need confirmation but,
if correct, imply that the most probable mode of decomposition, if a
compound is produced in dehydration, is into mullite, ~,-alumina
and silica. If the dehydration product is a mixture this conclusion is
invalid. Glass (1954) suggested from X-ray studies that the exo-
272 F. VAUGHAN

thermic reaction is due to formation of mullite nuclei, y-alumina and


amorphous silica from an amorphous compound.
TABLE4--AH and AF calculated from the data of table 3.

Reaction AH298 (cal./g. tool.) AIF298(cal./g. mol.)


5,610 6,000
- 214,700 ( - 213,530) - 210,500 ( - 213,690)
+ 10,200 - 29,600
+ 4,600 ( - 40,390) - 35,600 ( - 40,310)
-- 200,900 ( - 334,700) 317,300 ( -- 334,620)
-- 196,300 t - 375,090) - 352,900 ( - 374,930)

Avgustinik and Mchedlov-Petrosyan (1952) studied the thermo-


dynamics of mullite formation and evaluated free energy changes at
various temperatures using for metakaolin the equation.
C p = 2 1 . 6 7 + 6.41 • 10-3T
which is very different from that used by the author for the de-
hydration product.
(D) Exothermic Reaction at 1200~ F r o m heat of solution
measurements Shvetsov and Gevorkyan (1942) found that the second
exothermic reaction at about 1200~ involves the evolution of
7.2 • 1.7kcal/g. tool. This may arise from conversion of amorphous
silica to cdstobalite, although others believe that this second heat
evolution is connected with formation and/or growth of mullite
crystals.
LATTICE ENERGY
Kapustinsky (1943) has derived the following general equation:
0.345 1
U=287.2L'n~l~Z~rl+r2(. 1 ~t ~r2 )
in which U is the lattice energy, Zn is the number of ions in the
molecule, ~a, n2 are the valencies of cation and anion respectively,
and r 1 and r 2 their ionic radii. An alternative method of calculating
lattice energies is afforded by the Born-Haber (1919) thermodynamic
cyclical process which may be summarised in the expression
U=AHf + S S + Z I +27D - E a
where U is the lattice energy, A H f i s the heat of formation of the
substance, SS is the total heat of sublimation of metal atoms, 271 is
the total heat Of ionization, XD is tbe total dissociation energy
involved in the cycle, and E is the electron affinity. It follows that,
by comparing the results of the Born-Haber method with those
obtained by the Kapustinsky and other methods, some insight may be
obtained into hitherto incompletely known structures.
To apply the Kapustinsky method to a complex lattice like that of
kaolinite, it is necessary to split the structure into simpler units.
For kaolinite these were 2SIO2 and A12(OH)6, the whole corres-
ponding to a formula AlaSi2H6OI0, which is one H 2 0 group more
than the accepted kaolinite formula. Hence, the lattice energies of
ENERGY CHANGES OF HEATED KAOLINS 273
silica and A12(OH)6 are evaluated and the energy contribution of one
molecule of water is subtracted. The general method of splitting
complex structures into simpler neutral ionic units when applying
Kapustinsky's equation has been shown to hold for complex sub-
stances by Gruchvitski (1941). Values for heats of sublimation,
dissociation and ionization at absolute zero, have been obtained from
data given by Rossini et. al. (1952). The electron affinity of oxygen
has been taken as 71 kcal (Vier and Mayer 1944). From these
values the lattice energies given in Table 5 have been calculated.
TABLE 5--Lattice energies of compounds.
Lattice energy (cal/g. mol.)
Substance
Born-Haber Cycle Kapustinsky's Equation
Silica 2,640,000 3,060,000
Alumina 3,600,000
Amorphous alumina 2,957,000
y-alumina 2,963,000
Metakaolin (A12Si207) 8,250,000
Mullite 14,380,000
Kaolinite 9,820,000 8,290,000
Previously published values for the lattice energy of silica range
from 2,660,000 to 3,350,000 cal/g.mol, and for alumina are of the
order of 3,600,000 ~al/g.mol. Lattice energies for various forms of
alumina could be deduced because their heats of formation were
known, but the Kapustinsky method did not permit differentiation
between the various modifications, and only an overall estimate could
be made. Because the structures of mullite and metakaolin (if it
exists) are not clearly known only the Born-Haber values are given.
In using Kapustinsky's method for kaolinite the weak interlayer
forces have been neglected so that a lower value than that given by
the Born-Haber cycle might be expected. Other methods of cal-
culating lattice energies are of course available, but as lattice energies
can also be calculated without knowing structural details it becomes
possible to work back and elucidate structures.
Acknowledgements. The author wishes to thank Dr R. C. Mackenzie for
providing the sample of dickite used in this investigation, and Dr A. T. Green,
O.B.E., Director of Research, British Ceramic Research Association, for per-
mission to publish this paper.
DISCUSSION
Dr P. Murray wished to point out that the sample sizes and packing
densities could influence the results obtained.
M r R. W. Nurse added to these factors the variation which would
be caused by particle size and particle size distribution.
Dr R. C. Mackenzie wished to make known that the fireclay mineral
(the b/3 disordered form of kaolinite) was not fitting into a kaolinit~-
halloysite series and the reason was perhaps that it was not the fire-
clay mineral which was in error but the halloysite. He added that
some fireclay' mineral specimens had a lower peak temperature than
those normally encountered.
274 F. VAUGHAN
D r G. Nagelschmidt suggested that such variation between kaolin-
ite, fireclay mineral, halloysite could well be due merely to grain size
differences.
M r F. Vaughan (written c o m m u n i c a t i o n ) : stated that in some early
trials he had found that d o u b l i n g the a m o u n t of sample h a d b r o u g h t
a b o u t a n increase in the value of the velocity constants of dehy-
dration of a china clay, b u t the values of E and A were n o t greatly
altered. He did n o t pursue the matter further but decided to work
with a c o n s t a n t sample weight. I n c o n n e c t i o n with Dr R. C.
Mackenzie's remarks, d.t.a, curves for m a n y fireclays obtained at the
B.C.R.A. indicated that in general, the fireclay mineral had a lower
endothermic peak temperature than either halloysite or kaolinite.
Possibly a fireclay-kaolinite series existed, but as Dr Mackenzie had
indicated the position of halloysite was somewhat anomalous. The
influence of the fineness of a clay mineral upon its kinetic behaviour
requires further investigation but observed kinetic differences could
not be fully explained in terms of particle size variation.
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