View Article Online / Journal Homepage / Table of Contents for this issue

DETERMINATION OF VOLATILE MATTER YIELDED BY COALS 1145

Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

CXXV1.-A New Method for Determining the Volatile

Matter yielded by Goals u p to Various Temperatures.
By WILLIAMARTHURBONE and LEONARD
SILVER.
IT has always been considered important, in connexion with the
so-called " proximate analysis " of coals, to determine the amounts
of volatile matter expelled from them under certain prescribed
conditions. Such determinations, if properly carried out, would
be capable of giving results of scientific as well as commercial
value, inasmuch as they are useful in connexion with the classifica-
tion of coals. The value of a particular test depends, however,
largely upon the trustworthiness of the information it affords as
to (a)the precise amount of volatile matter expelled from the
coal under given temperature conditions, and ( b ) the character
of the carbonaceous residue obtained. However, as the amount
of volatile matter yielded by a given coal varies considerably with
the temperature at which it is carbonised, it is obvious that, unless
the temperature conditions of a test are carefully attended to, its
quantitative value may be small. Also, unless the heating opera-
tion is carried out in such a manner as will effectually eliminate,
or a t least render negligible, the influence of air, the results may be
misleading.
Hitherto, it has been customary to employ one or other of the
two following methods. The first was recommended in 1899 by
the American Chemical Society ( J . Amer. Chem. Soc., 1899, 21,
1122), and is known as the " American Method '' ; it was originally
prescribed as follows :
" Place 1 gram of fresh undried powdered coal in a platinum

crucible, weighing 20 to 30 grams, and having a tightly fitting

cover. Heat over the full flame of a Bunsen burner for seven
minutes. The crucible should be supported on a platinum triangle
with the bottom 6 t o 8 cm. above the top of the burner. The
R R 2
 View Article Online

1146 BONE AXD SILVER: A NEW METHOD FOR

flame should be fully 20 cm. high when burning free, and the deter-
mination should be made in a place free from draughts. The upper
surface of the cover should burn clear, but the under surface should
remain covered with carbon. To find the Volatile Combustible
Matter subtract the percentage of moisture from the loss found
here."
A similar test waa adopted by the chemists responsible for the
Canadian Coal Survey, the only difference being that it was carried
Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

out on the dry, instead of the undried,coal (vide " An Investigation

of the Coals of Canada," Vol. II., p. 134, by J. B. Porter, R. J.
Durley, and others, issued in 1912 by the Canadian Department
of Mines). The chief objections which have been urged against
the method are (1) that the temperature conditions are not suffi-
ciently defined, (2) that the influence of air is not sufficiently elimin-
ated, (3) that the employment of a platinum crucible introduces
catalytic influences to a,n unknown extent, and (4) that it does not
enable a trustworthy judgment t o be formed about the coking
properties of a coal.
The second method is known as the "Crucible Test," and is
usually carried out by carbonising 20 grams of the dried coal in a
No. 3 Morgan fireclay crucible fitted with a suitable lid at a tempera-
ture of 900" in a muffle furnace, the heating being continued for
ten minutes after the evolution of inflammable gases has entirely
ceased (for further details vide W. A. Bone, " Coal and its Scientific
Uses," p. 57). This test is capable of giving valuable information
as to the coking properties of the coal, and inasmuch as it can always
be carried out a t a definite temperature (900"being usually selected),
i t is on the whole perhaps preferable to the " American " method.
Neither of the methods is, however, capable of the degree of pre-
cision which is nowadays needed for purposes of scientific classi-
fication.
Some years ago, Lessing ( J . Soc. Chem. I d . , 1912, 31, 465)
described " A New Apparatus for the Coking Test of Coal " which
obviated some of the dimdvantages of the crucible test. One gram
of the powdered coal was electrically heated, under slight pressure,
for between five and seven minutes, in a, long, vertical quartz tube,
of about 10 mm. diameter, open a t the upper end. The heating
arrangements were such that most of the heat was concentrated
at the bottom of the tube and on its walls for a distance of 15 mm.
u p ; the upper part of it, being exposed to the air, was kept rela-
tively cool. " The practical value of the apparatus " was said
by its author " to lie principally in the fact that the coke obtained
in it brings out the peculiarities of a coal in a much more striking
fashion than does the coke in the crucible test " (ibid., p. 466).
 View Article Online

DETERMINING VOLATILBI MATTHR YIBLDED BY COALS, ETC. 1147

But, as regards the accurate determination of the volatile matter
in a coal, it seems to us to be open to criticism in that (a) air is not
excluded, (b) there is nothing to indicate with certainty the precise
moment when the expulsion of volatile matter ceases, and (c) the
temperature to which the coal is heated during the test can scarcely
be regulated with sufficient accuracy.
In the course of an investigation which one of us was asked to
carry out upon a certain seam of anthracitic coal, it was desired
Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

to obtain accurate information concerning a suspected gradual

transition in the character of the coal in both vertical and hori-
zontal directions in the seam. The extent and direction of the sus-
pected change would be shown by corresponding variations in the
yields of volatile matter obtained from samples taken at different
parts of the seam. Since, however, the total variation in such
yields throughout the whole of the seam was not expected to amount
to more than two or three per cent., it will be seen that the degree of
accuracy required in the determinations was considerably more
than could be ensured from the employment of any of the methods
already referred to. Moreover, on trying the first two methods,
they utterly failed to give results of any value for the purpose in
view.
Accordingly, a new method had to be devised and, after extended
trials, the following was ultimately adopted. As subsequent
experience with it has shown its applicability to all types of coal,
we propose now to describe it in the hope that other workers may
find it useful.
E x P E R I M E N T A L.
The New Method.-The new method consists essentially in car-
bonising a weighed quantity of the finely divided coal a t a definite
temperature in a silica tube from which air is excluded during the
operation, The tube is heated in an electric resistance-furnace
which can easily be maintained within a few degrees of the desired
experimental temperature, which is read by means of a suitable
thermo-couple device. The general arrangement of the apparatus
is shown in the accompanying diagram.
The coal, having previously been dried and ground so as to pass
a sieve having 30 meshes to the linear inch, is quickly weighed out
into a small silica tube, A (12 cm. x 1.5 cm.), which is closed at one
end. The quantity of coal taken (usually 6 grams) should about
half-fill this tube, which is then pushed, open end fist, to the far
end of the larger silica tube, B (30 cm. x 2% cm.). Throughout
the ensuing test this " retort " part of the apparatus is kept in an
inclined position so aa to retain the coal in the smaller tube, which
 View Article Online

1148 BONE AND SILVER: A NEW METHOD FOR

is held towards the closed end of the larger one by means of the
silica rod, C, as shown in the diagram. Into the mouth of B is
fitted a rubber stopper carrying a glass delivery tube, D , communi-
cating with the upper part of the flask, E,which is three-quarters
filled with water. A second glass tube, F , passes from near the
bottom of E to near that of a second flask, G , which is open to the
outside atmosphere and, a t the outset of the experiment, contains
nothing but air.
Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

All these preparations having been completed, the retort system

is thereupon gradually introduced into a nichrome-wound and elec-
trically heated tube furnace, H H , of suitable dimensions, which
has previously been raised throughout a length of at least 30 cm.
to a ,uniformly constant temperature of goo", as indicated by any

FIG. 1.

suitable form of thermo-junction pyrometer. The furnace is so

mounted that the axis of the tube coincides with that of the retort
system. If experiments are to be made in duplicate, a small
electrically heated muffle furnace may be advantageously employed,
the two retort systems being simultaneously heated side by side
in it. I n either case, it is preferable that the furnace body be
suitably mounted on small wheels, so that it may be gradually
slid over the retort system; but, for the sake of simplicity, this
adjunct is not shown in the diagram.
As soon as the retort system has attained the temperature of
the furnace, the volatile constituents of the coal are rapidly expelled,
driving the air out of the tube before them. The water in the flask
E is soon displaced into flask G by the issuing gas, which then
bubbles through the water-seal in G into the open air. The rate
of evolution of the gas can thus be gauged, and the end of the
carbonisation is indicated by its cessation. The time taken for
 View Article Online

DETERMINING VOLATILE MATTER YIELDED BY COALS, ETC. 1149

the completion of the test is usually about forty minutes, being
rather longer for anthracitic than for most bituminous coals. If,
however, the coal contains a high percentage of volatile matter,
care must be taken to draw the furnace very gradually over the
retort system.
As soon as the expulsion of gas from the coal has ceased, the retort
system is carefully withdrawn from the furnace and allowed to
cool while still connected with the flasks E and G . The ensuing
Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

contraction of the gases in the apparatus causes water to be sucked

back from G into E , but no air can be drawn into the system.
When the retort is cool enough t o be handled, the inner tube is
carefully removed, contact with any remains of tarry matter in
the lower part of the outer tube being avoided; it is then cooled
in a vacuum desiccator, and finally weighed as rapidly as possible.
The loss in weight gives the yield of volatile matter a t 900".
General Applicability of the Method.-How entirely satisfactory
the method proved to be when applied to the particular class of
anthracitic coals for which it was originally devised may be judged
from the following tabulated results, in which the Roman numerals
indicate the actual sequence of the various samples in the seam
under investigation; attention is directed both to the close agree-
ment between duplicate determinations and t o the unmistakable
way in which the continuous and gradual change in the character
of the coal along the seam is brought out.

TABLEI.
Results showing the gradual Change in the Character of an

-
Anthracitic Coal along a particular Seam.
Coal Percentage of volatiles at 900"
Sample No. found in different experiments. Mean.
I 11.90 11.91 11.96 12-00 11.94
I1 11.59 11-69 11.65
I11 11-54 11-67 11.60
IV 11.38 11.30 11.34
V 11.01 11.08 11.05
VI 10.79 10.86 10.83
VII 10.70 10-74 10.72
VIII 10-60 10.62 10.61
IX 10.01 10.03 10.02
X 9.88 9.91 9.90
At a later stage of the investigation it was found that satisfactory
results, showing a high degree of concordance, could be obtained
with almost every class of coal. The method of heating, however,
required to be modified in certain cases. For example, one type
of coal was found to decompose a t red heat with considerable
violence; so much SO that when it was carbonised in a fireclay
 View Article Online

1160 BONE AND SILVER: A NEW METHOD E'OR

crucible by the ordinary " crucible method " there resulted an

explosion powerful enough to fracture the crucible. The difficulty
was overcome by putting the retort system in the furnace when its
temperature was 500", and then gradually raising the temperature
until 900" was attained in about an hour and a half. This method
of slow heating also proved successful in the case of coals with a
very high percentage of volatiles, where there was a risk of loss
through the rapid evolution of gas blowing some of the finer coal
Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

out of the tube.

Comparison of the New with Former Methods.-In order to ascer-
tain how results obtained by our new method compare with those
yielded by the " American " and " Crucible " tests, respectively,
a series of trials was made in which samples representative of different
classes of coal were carbonised by each of the three methods. The
results obtained are tabulated below, together with the differences
observed in the results of duplicate tests by each method :

TABLE11.
Comparison of Results obtained by the diflerent Methods.
Percentage of volatiles a t
900" aa determined by Differences between
duplicate determina-
(a) (b) (c) ' tions in
Silica American Crucible
Coal. tube. method. 1method. (a) (b) (c)
1. Welsh anthracitic 11-96 12-82 13.59 0.10 0.20 1.12
2. Welsh steam ...... 17.76 18.11 18.66 0.11 0.02 0.28
3. Welsh coking ... 19.93 21-19 20.34 0.07 0.06 0-04
4. Durham coking ... 26-29 26.71 24.62 0.22 0.37 0.04
6. Brodsworth soft 37.43 40.24 36.64 0.06 0.48 0.16
6. Bullcroft soft ...... 39.86 41-35 39.52 0.02 1.36 0.16
7. Peruvian ............ 37.60 36.68 35.64 0-36 0.44 1.64
8. Nigyrian sub-bitu-
mmow ......... 41.32 43.23 38-94 0.05 0.06 0-04
9. Camel (S. Wales) 54-05. 56-42 52.92 0.02 0.68 0.88

The above results show that, in general (1)the silica tube method
gives values intermediate between those given by the other two,
the American method usually giving a higher, and the crucible
assay method a lower figure, and (2) the degree of concordance
is greater for the silica tube method than in either of the others.
The figures obtained by the American method are probably as
a rule too high for the following reasons : (1) the temperature
attained may rise beyond 900", and (2) the evolution of the gas
is so rapid that small particles of the coal are apt to be carried out
of the crucible. Also, the results may be affected by the catalytic
action of the platinum.
.Judging from our experiments, the crucible method gives results
 View Article Online

DETERMINING VOLATILE MATTER YIELDED BY COALS, ETC. 1151

which, whilst usually too high for coals yielding less than about
20 per Cent. of " volatiles," are almost invariably too low in the case
of their yielding more than that percentage. The reason for this
rather curious circumstance became apparent during our investiga-
tion of the silica tube method. It was then found that whilst the
evolution of gas was fairly rapid during the early stages, it became
very slow towards the end of the carbonisation, and continued to
be so for a considerable time before finally ceasing; the whole
Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

process required about forty minutes for its completion. NOW

in the crucible method, as ordinarily carried out, the period of heating
usually extends over about thirty minutes for a 20 gram charge;
and in the cases of coals containing more than about 20 per cent.
of volatiles, it seems that the evolution of gas would usually con-
tinue for longer than ten minutes after the disappearance of visible
flame, when the crucibles are withdrawn from the furnace. To
leave them in long enough to complete the carbonisation would
entail the risk of appreciable loss by oxidation through air coming
in contact with the topmost layer of the carbonaceous residue (coke);
hence the practice of withdrawing them (as it now seems) somewhat
prematurely, with consequent low results, in such cases. On the
other hand, when coals yielding less than about 20 per cent. of
" volatile " a t 900" are tested, the usual time allowed in the furnace

is sufficient both to complete the carbonisation, and also to allow

of some oxidation of the carbonaceous residue, so giving results
which are too high.
It would appear, therefore, that the determination of the yield
of " volatiles " at goo", or any other selected temperature, can be
carried out with greater accuracy by the new method described
in this paper than by either of the other two in common use. The
chief advantages to be gained by using the new method may be
summarised as follows :
(1) The temperature conditions are more accurately known,
and can be regulated to a nicety. This applies also to any tem-
perature that may be selected as the desired uppermost limit.
(2) The rate of heating of the charge is under perfect control.
(3) The carbonisation is carried out in an inert atmosphere, and
there is no risk of oxidation.
(4) Completeness of carbonisation at any selected temperature
is assured, since the heating is always continued until no more
bubbles of gas are evolved.
(5) The volatile products, more especially the gas, can be collected
for examination, if desired, by attaching to the retort system any
suitable arrangement of collecting and measuring vessels.
(6) If the carbonaceous residue is sufficiently coherent to form a
R R*
 View Article Online

1152 COFFEY : THE MECHANISM O F THE

coke, the latter is obtained in a cylindrical form which is very

convenient for subsequent examination.

I n conclusion, we desire to state that this investigation has

formed part of the work carried out by one of us during his tenure
of a Salters’ Fellowship a t the Imperial College of Science and
Technology, South Kensington.
FUELLABORATORIES,
Published on 01 January 1921. Downloaded on 10/27/2018 15:12:37.

COLLEGE OF SCIENCE
IMPERIAL AND TECHNOLOGY,
SOUTHKENSINGTON. [Received, May 26th, 1921.1