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THE CALCINATION OF DOLOMITE

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PART 11.-THE THERMAL DECOMPOSITION OF DOLOMITE

BY H. T. S. BRITTON,S. J. GREGGAND G. W. WINSOR

University College, Exeter
Received 27th April, 1951 ; in final form 8th August, 1951

The kinetics of the isothermal decomposition in vucuo of four specimens of dolomite

(H, J, K, L) has been studied at a series of temperatures, covering the range 640"to 720" C,
with the automatically recording sorption balance referred to in part I ; in all cases the
course of the decomposition can be represented by an equation of the same type as that
found to hold for the decomposition of calcite and magnesite (cf. part I), viz.
+
(w/wo)" = - kt u (where w/wo = portion decomposed at time t; k, n and u are con-
stants). The mean value of (1 - n) is : series H, 0.67 ; J, 0.70 ; K, 0 7 7 ; L, 0.73. The
decomposition probably occurs at an interface advancing from the exterior of the sample
or of each lump to the interior. The initial product is a solid solution of (Ca, Mg)O
which quickly breaks up into crystallites of CaO and of MgO, so that if the escape of
C02 is hindered, considerable quantities of CaCO3 will be formed behind the interface.
This occurs if the dolomite is decomposed in air or in the presence of C02. When
vacuum-decomposed dolomite is exposed to C02 at 800" C the gas i s rapidly taken up
to an extent rather less than that corresponding to the total Ca content of the original
dolomite.
The energy of activation of the decomposition is (cal mole-1) : H, 55,600 ; J, 53,800 ;
K, 49,400 ; L, 52,300 ; it is therefore higher than the energy of decomposition of calcite
and of magnesite.

The thermal decomposition of dolomite has been studied by a number of

workers 1 and on the whole their results support the view that the substance de-
composes in a different manner from a mixture of calcite and magnesite. This
is only to be expected, for dolomite is a specific substance having a distinct crystal
lattice of its own,2 different from that of calcite and of magnesite.
The kinetics of the decomposition, particularly under conditions where the
carbon dioxide is continuously pumped off, appears to have been largely neglected,
however. The present paper describes measurements of the rate of isothermal
decomposition in a vacuum (maintained by continuous pumping), together with
experiments on the extent of recombination of the decomposed dolomite with
carbon dioxide. The results permit some conclusions to be drawn as to the
mechanism of decomposition.
EXPERIMENTAL
MATERZALS.-In all, four different specimens of dolomite were used (H, J, K, L),
and one series of experiments was performed on each. Details of these specimens are
+
given below. The material was sieved to - 10 20 mesh in each case.
Specimen H-Dolomite from Steetley Quarries.-Pale straw-coloured,marked crystalline
appearance, and relatively free from impurities. Analysis : CaO, 30.49 % (30.4) ; MgO,
21.53 % (21-8); CaO : MgO, 1.42 (1.39) ; Fe2O3, Al2O3, 0-28 %. (Figures in brackets
.
are theoretical for dolomite CaC03 MgC03.)
J-Dolomite from Suther1und.-Kindly provided by the Geological Museum, London :
CaO, 29.6 %; MgO, 21-1 %; CaO: MgO, 1.40 (traces of Si02, Al2O3, TiO2); Fe203,
0.1 % ; loss on ignition 46.4 % ; insoluble residue, 3.0 %. Hard grey-black rock.
K-Dolomite from Grifln and Tatlock Ltd.-Of unknown origin. Very pale buff
coloured.
L-A selectedspecimen of true dolomitefrom St. Gothard.-Pearly white crystalline solid.
70
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H . T. S . B R I T T O N , S . J . G R E G G A N D G . W . WINSOR 71
PROCEDURE.-The automatically recording sorption balance, already described in
part I, was again used ; the same procedure was adopted, except that the temperatures
studied fell within the approximate range 640" to 720" C. The '' end-point " of the
decompositionwas again obtained by raising the temperature of the furnace to ca. 900" C.
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The weight of the sample in each experiment was ca. 0.40 g, and some 10 to 15 separate
isothermal decompositions were carried out with each specimen, giving experimental
series H, J, K and L.
RESULTS
In all the experiments the curve of weight against time was continuous throughout
its course (cf. fig. l), no break being detectable. The data fitted an equation of the type
already referred to in part I, viz.
(w/wo)= +
~ - kt a (1)
though the experimental points tended to lie rather more irregularly than with magnesite
and calcite. On plotting as (w/wo)"against t, for example,- they showed some scatter
(fig. 2).

FIG. l.--Curve of weight against time for a typical example of dolomite decomposition
(St. Gothard dolomite at 720" C).
Ordinates : drum reading in cm (1 cm = 0.0134 g).
Abscissae : time in minutes.

FIG.2.-Plot of (w/w0)0.25against time for Griffin and Tatlock dolomite at 657"C.

Ordinates : ( w / w o ) O . ~ S
Abscissae : time in minutes.
The best value of (1 - n) was found in the same manner as in part I and it varied from
one experiment to another of the same series somewhat more widely than for. calcite
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72 C A L C I N A T I O N OF DOLOMITE

and magnesite. The mean value of (I - n) is, series H, 0.67 ; J, 0.70 ; K, 0.77 ; L, 0.73.
The value of (1 - n) is again sufficiently close to 0.67 to suggest that the decomposition
OCCUTS at an interface advancing from the outside towards the centre, the deviations from
0.67 being ascribable to disturbing factors. Some direct evidence for the presence of
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an interface was obtained in a separate experiment: two lump samples of (Steetley)

dolomite were partially decomposed in vacuu on the sorption balance and were then broken
open. A definite interface could be seen by the naked eye ; the core in the centre was
grey and hard, was similar in appearance to the original dolomite apart from a change
in colour (due to iron?) and different from the outside layer. The two portions were
separated by hand and analyzed ; as will be seen from the following table, the decomposi-
tion in the centre portion was much less than in the outer layer. The rate of dissolution
of the centre sample in HCl also supported the contention that it was largely undecomposed
dolomite and did not contain much calcite ; it dissolved rather slowly, whereas calcite
dissolves rapidly, the relative rates of dissolution of calcite, dolomite and magnesite
being 100,OOO : 650 : 9 according to Ferrari.3

TABLEAN ANALYSIS OF STEETLEY DOLOMITE AFTER HEATING IN VACUUM

loss of weight
sample in preparation position % con % free CaO
L 28 % centre 41.3 6.9
outer layer 11.0 -
M 25 % centre 43.7 0.7
outer layer 12.0 -
original dolomite - - 46-4 -

It would seem that, in vacuum, the loss of C02 occurs at an advancing interface.
This could come about in either of two ways : (a)by the direct decomposition of the dolo-
mite,4 leading to the formation of a solid solution (Ca, Mg)O, which subsequently breaks
up into crystallites of CaO and of MgO ; or (6) by the break-up of the dolomite into crystal-
lites of CaC03 and MgCO3, which then decompose to oxides. Alternative (b) does not
fit the facts of table 1, however ; for, as is clear from the data of part I, the MgC03 would
decompose extremely rapidly (" instantaneously "), and the CaC03 very slowly, at the
temperature of experiment, so that there would be a high C02 content, nearly 50 % of
the original, behind the advancing interface, i.e. in the outer layer.
Loss AND UPTAKE OF C02.-1t is of interest to know whether all of the decomposed
dolomite will recombine with C02, or only that part of it corresponding to the CaO
content. It was shown in part I that CaO obtained by decomposition of calcite in vacuu
will recombine rapidly at temperatures above 400" C or so, and that MgO from the de-
composition of magnesite shows no tendency to recombine with carbon dioxide at such
temperatures. Accordingly, a sample of dolomite was decomposed on the sorption
balance in vacuu, and C02 was then admitted up to a pressure of 74 cm, with the sample
at 800" to 810" C. With each of the four varieties of dolomite, an almost instantaneous
uptake of C02 occurred which ended abruptly. In table 2 the quantity of C02 so taken
up is given as a percentage of the C02 content of the original sample.
TABLE
2.-uPTAKE OF C02 BY DOLOMITIC LIME

sample % reformed
Sutherland 39.6
Sutherland 45-0
Griffin and Tatlock 40-2
Steetley 39.6
Steetley 41.7
St. Gothard 28.3

Apart from the St. Gothard dolomite, these values range from 39.6 to 45 %, and
they therefore approach the value (50 % for " ideal " dolomite) to be expected if the C02
combines with the CaO content only, of the undecomposed material. They show that
a large proportion of the solid solution (Mg, Ca)O has broken up into MgO and CaO
even before the admission of the C02. Indeed, some break-up will be able to occur during
the decomposition run itself, thereby explaining the fact that the C02 content behind the
interface in the experiment of table 1, though small, was not zero.
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H . T . S . B R I T T O N , S. J . G R E G G A N D G . W . WINSOR 73
By hindering the escape of C02 the extent of the overall rate of decomposition will
be decreased, so that there will be more time for formation of CaO and MgO by recrystal-
lization ; the content of C02 (due to formation of CaC03 by recombination of CaO C02) +
behind the interface should be correspondingly greater. This was tested by partially
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decomposing(to 65 %) a piece of Steetley dolomite in air, on the ordinary thermal balance *

TABLE3.-sTEETLEY DOLOMITE, AFTER HEATING IN AIR TILL IT HAS LOST 30 %

OF ITS ORIGINAL WEIGHT (I.E. 65 % DECOMPOSITION)
i ii iii
% co2 % CaO (free) % CaO (free)
expt. calc.
centre 31.4 1.9 0.7
outer layers 27.6 7.7 7.7
surface powder t 5.1 - -
original dolomite 46.4 - -
t This material was not included in the " outer layers " sample ; it was very small
in quantity and confined to the surface.

where the removal of C02 is much slower than in vczcuo. On breaking open the lump,
no interface could be detected, and analytical data confirmed its absence: samples of

FIG. 3.-Plot of loglo s where s = rate of decomposition when fraction decomposed

is 0.30 against 1/T for different batches of dolomite.
curve I : GriflGn and Tatlock dolomite (use abscissa scale A)
curve I1 : Sutherland dolomite (use scale B)
curve I11 : St. Gothard dolomite (use scale C)
curve IV : Steetley dolomite (use scale C).
Ordinates : loglo s
Abscissae: (1/7') x 103 (Tin OK).

material from the centre, from the outer layer and from the powdery surface coating
gave the results of table 3, columns (i) and (ii). (The CaO was determined by extraction
with water and titrating with acid. The values in column (iii) were calculated on the
assumption that all the residual COz in the part of the specimen analyzed was present as
CaC03.) As will be seen, there is a very considerable content of CaC03 in the outer
layers, i.e. behind the interface.
If the decomposition be carried out in an atmosphere of C02 one would expect no CaO
* See Gregg and Winsor, Analyst, 1945, 70,336, for references,
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74 C A L C I N A T I O N OF DOLOMITE

to be formed at all (" half burning "). This was tested in a number of experiments in
+
which 0.5 g of - 10 20 mesh dolomite was heated at ca. 775" C on the sorption
balance in the presence of C02 at appraximately 75 cm pressure ; this temperature was
chosen as being above the dissociation temperature of MgC03 and below that of CaCO3.
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Decomposition occurred fairly rapidly for 20 to 25 min and then further change in weight
became negligible. The experimental loss in weight was quite close to the weight of the
C02 (given in brackets) which corresponds to the Mg content of the sample : Steetley,
23.1 % loss (22-3 %); Sutherland, 1st expt., 22.5 % (23.1 %); Sutherland, 2nd expt.,
21.8 % (23.1 %) ; St. Gothard, 22.4 %.
ENERGYOF AmAmON.--The variation of the index (1 - n) was, as in part I, some-
what too wide to permit the calculation of the energy of activation E from the temperature-
dependence of k ; and accordingly the rate of decomposition for W / W O = 0.30 was again
estimated from the weight-time curve and its logarithm plotted against 1/T (cf. fig. 3).
The slope of the best straight line was calculated by the method of least squares, and
the value of E was obtained thence as 2.303 x 1-98 x s. The results are given in
table 4, along with the corresponding standard deviations.
TABLE4.-ENERGY OF ACTIVATION E FOR THE THERMAL DECOMPOSITION
OF VARIOUS DOLOMITES

series source of E
dolomite kcal mole-1
H Steetley 55,600 & 5,600
J Sutherland 53,800 rt 4,000
K Griffin and Tatlock 49,400 rt 6,300
L St. Gothard 52,300 A 3,400

It is of interest that these values are definitely higher than the energy of decomposition
of calcium carbonate at these temperatures, viz. 40,000 cal mole-1 (see part I, note A)
and also of magnesite, ca. 27,000 cal mole-1 (see part I, note B).

DISCUSSION

The results obtained in this paper are consistent with a mechanism in which
the initial decomposition OCCLU-s at an interface, giving a solid solution (Mg, Ca)O,
which soon breaks up into separate crystallites of magnesium oxide and of calcium
oxide.
The solid solution would probably have the pseudo-lattice of dolomite, and
so long as this persists the carbon dioxide molecules would move to the exterior
by a lattice migration, each molecule jumping from a lattice hole left by a pre-
vious molecule, to an adjacent one. If then the reaction is carried out rapidly
so that the solid solution breaks up slightly or not at all whilst the experiment is
in progress, a definite interface will be present.
If, however, the rate of escape of the carbon dioxide is slowed down (by allowing
a " back pressure " of carbon dioxide to build up) extensive recrystallization of
the solid solution into the two oxides will occur during the experiment ; and lattice
migration of the carbon dioxide will now be confined to the region adjoining
the interface (where the solid solution has not yet had time to break up) and the
carbon dioxide molecules will move largely through the gaps left between the
crystallites. Some recombination of the calcium oxide, but not of the magnesium
oxide, to carbonate will occur on each crystallite, presumably at an interface
advancing towards its centre.
The reason for the absence of an obvious interface in the " air " experiments
is now fairly clear: the original interface between the dolomite and the solid
solution of (Mg, Ca)O has indeed moved through the lump or sample, but the
recombination to CaC03 has occurred at an interface which is located on the
separate crystallites of CaO/CaC03 ; these are distributed throughout the lump or
sample, and so the recombination interface is no longer parallel to the original,
decomposition interface.
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H. T . S. B R I T T O N , S . J . GREGG A N D G . W . WINSOR 75
This work was part of an investigation carried out for the Ministry of Supply
at University College, Exeter, during the years 1944 to 1948. This paper is pub-
lished by permission of the Chief Scientist of the Ministry.
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1 E.g. Gill, Can. J . Res., 1934, 10, 703. Conley, Industrid Minerals (Non-Metallics),
1942, 148, 330. Nutting, GeoIogicaE Survey ProfessionaE Paper (U.S. Dept. of the
Interior, 1943). Budnikov, J. AppE. Chem., U.R.S.S., 1937, 10, 797. Clarke, Bradley
and Azbe, Ind. Eng. Chem., 1940, 32, 972. Esin, Gel'd and Popal, Zhur. Priklad. Khim.,
1949, 22, 240, 354.
2 Miers, Mineralogy (Macmillan, 1929), p. 296. Wyckoff, Crystar Structures, 1948,
chap. 7, p. 7. 3 Ferrari, Gazz. Chem. Ital., 1937, 67, 501.
4 Cf. Hedvall, Reaktiomfahigkeit fester Stofe, p. 196.