Fuel 79 (2000) 1267–1276

www.elsevier.com/locate/fuel

Thermochemical history in the genetic path of coal: derivation of a novel

correlation for heat of combustion
B.K. Mazumdar*
Flat 3B, 3rd Floor, 88, Raja SC, Mullick Road, Calcutta 700 047, India
Received 9 September 1998; received in revised form 26 August 1999; accepted 12 October 1999

Abstract
A plot of the heat of combustion of coal (Q) vs sum-total of the C and H contents (on Parr’s basis), for bright coals, has been found to show
three clear-cut linear phases in the transition from lignite to anthracite, marked by two turning points, one at about 84–85 and the other at
about 92 wt% C. Significantly, analogous curves showing exactly the same pattern of variation of Q vs rank, have also been found to emerge
from the plots of Q vs C or Q vs O. The first long linear step (AB) encompasses the high-volatile (hv) low rank coals (C: 65–84 wt%), the
second (BC), the middle rank coals (C: 84–92 wt%) and the third (CD), the highest rank coals (C: 92–97 wt%), tending to end up linearly at
the point for graphite. Attention is drawn to the one-to-one correspondence of the above thermochemical paths with what had been observed
earlier in the “genetic path” of coal, traced out from a plot of atomic H/C 0 ratio vs rank for the same range and types of coals, showing the
same three linear steps, demarcated by the same two turning points. The Q vs (C 1 H) relationship is considered more significant because of
its direct relevance to the C–H matrix of coal and its progressive structural change as shown by the sequential changes of its atomic H/C 0
ratio. Such interpolation of the thermochemical and genetic paths has led to the development of the following novel correlation, holding good
from lignite to anthracite:

Q…MJ=kg† ˆ 0:512…C 1 H† 2 11:19 1 6:75…H=C 0 2 0:78†

which, in turn, simplifies to Eq. (7): Q ˆ 0:512 …C 1 H† 1 81:07 H=C 2 16:46; with atomic H/C 0 ratio replaced by its weight ratio (H/C).
Parallel correlations have also been developed based on Q vs C or Q vs O relationships but the Q vs (C 1 H) has been found to be the most
accurate, and is recommended for general use.
Allowing for contributions of heat due to S and mineral-matter (MM) transformation to ash, it has also been possible to logically deduce a
derivative (Eq. (8)) giving calorific value on dry basis, directly from dry coal data:

Qd ˆ 0:512 …Cd 1 Hd † 1 …81:07 Hd 1Cd 2 16:46† × …100 2 MM†=100 1 12 Sd 2 0:007 Ashd

The “genetic” correlations have been found to apply excellently well to all coals irrespective of their rank, region and variable petrographic
composition, predicted values seldom deviating from experimental values by more than 0.5%. Its (Eq. (8)) potential accuracy is likely to be
far better as assessed from a special test conducted on US coals.
The success of the newly found correlations, is attributed mainly to the role of its H/C term, significance of which is discussed in full vis a
vis rank and petrographic factors of coal. q 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Thermochemistry; Genetic path: H/C ratio; Heat of combustion

1. Introduction 33.5 MJ/kg or so, at the meta-anthracitic level, is well-

The variation of the heat of combustion of coal, from as
low as 24.4 for brown coal to as high as 37.2 MJ/kg up to the
end of the bituminous range (C , 92 wt%), followed by the
almost linear reversal from the peak value down to about
* Tel.: 191-33-413-1987.
E-mail address: bengali@cal2.vsnl.net.in (B.K. Mazumdar).
0016-2361/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0016-236 1(99)00229-X
known. Yet such classical knowledge [1–3], if closely
re-examined in the context of latest knowledge about coal
chemistry and its structure [4–11], especially in the light of
sequential structural changes across the genetic path
[12–13] of coal, may be quite rewarding in the way of either
consolidation of old knowledge an/or generation of new
knowledge. In fact, such a fresh look appears to have put
the subject in its proper perspective and in turn, seems to
have led to the deduction of a strange but true correlation
1268 B.K. Mazumdar / Fuel 79 (2000) 1267–1276
Fig. 1. The variation of the heat of combustion of coal with increasing
carbon content (on Parr’s basis) for vitrinites and/or vitrain-rich coals.
relating heat of combustion of coal with its elementary
composition.
2. Thermochemical history of coal
2.1. A new concept
As early as the fifties, studies on the systematics of coals
[14,15], especially the high-volatile coals (hv), led to the
recognition that such coals (C: 70–84 wt%) are unique in
character and “a class by themselves”, “essentially due to
their similar structural pattern in contradistinction to that of
Fig. 2. The variation of the heat of combustion of coal from lignite to
anthracite, i.e. with decreasing oxygen content (Parr’s basis), for vitrinites
and/or vitrain-rich coals.
the high rank coals”. Such a tentative conclusion about hv
coals having some structural commonalities [15], later
received strong and independent support from a plot of
atomic H/C ratio of coals vs rank [12], as designated by
the carbon content. The hv coals (largely bright coals)
were all found to line up in the horizontal part of the
diagram, registering almost a near-constant H/C ratio of
0:80 ^ 0:03; up to 84 wt% C-level.
The distinctive status of hv coals as cited above,
prompted a search for the existence, if any, of a similar
pattern in the thermochemical path of coal.
2.2. Thermochemical changes: basis of study
Many such studies have been reported in the past [16], but
the true variation of the heat of combustion of coal with
rank, especially its pattern, has been missed and/or masked
over, due to two factors, e.g. (a) plot of coals of non-descript
character and (b) lack of proper basis for such plots.
Keeping the above factors in view, only vitrinites of high
purity and/or vitrain-rich coals were chosen for an initial
study. For the proper datum line, Parr’s basis [17] (i.e. dry
mineral-matter and sulphur-free basis) was adopted. The
series of high purity vitrinites of van Krevelen et al. [7,8]
were used. Sulphur contents of these samples were quite
small (wt% S: 0.4–0.6), but even so, their elementary
analyses and calorific values, were all suitably converted
to Parr’s basis. As for the vitrainous coals, a set of British
bright coals [18], varying in rank from sub-bituminous to
anthracite, was chosen. These were available directly on
Parr’s basis.
2.3. Heat of combustion (Q) of coal with rank: a new
evaluation
Three sets of such relationships were studied, e.g. (a) Q vs
carbon content (C); (b) Q vs oxygen content (O) and (c) Q vs
(C 1 H) content—all on Parr’s basis. Such depictions
covering a long range of bright coals from lignite to
anthracite, are presented in Figs. 1–3, respectively. It can
be seen that virtually an identical pattern emerges in all
three plots, showing up three clear-out linear steps, AB,
BC and CD, (Figs. 1–3), demarcating coals into three
distinct groups, e.g. (i) the low rank hv coals (C: 70–
84 wt%); (ii) the medium rank coals (C: 84–92 wt%) and
(iii) the highest rank coals (C . 92 wt%) encompassing
semi-anthracites and anthracites. It is also significant that
the last phase (C . 92 wt%) in all the three thermochemical
paths, proceeds linearly and tends to end up at a point,
virtually coinciding with that for graphite.
In essence, all the three figures present the same thing,
e.g. the nature of variation of Q with increasing rank of coal,
as designated by C, O or (C 1 H), all showing unmistakably
the same trend.
Before an attempt is made to interpret the relationships
the significance of the plot of Q vs (C 1 H), needs to be
considered. Prima facie, this appears to be irrational,
 B.K. Mazumdar / Fuel 79 (2000) 1267–1276
Fig. 3. Variation of the heat of combustion of coal with sum of carbon and hydrogen contents (Parr’s basis). [The line AB, if extended downwards would
passthrough brown coals having (C 1 H) values ranging from 66 to 70 corresponding to heat of combustion varying from about 23–25 MJ/kg 21 not shown in
the figure.)]
considering the fact that the heat of combustion of H is more
than 4 times that of C. Thus, this raises the question as to
how these two added together, and plotted against Q, give a
good relationship and moreover the same pattern of relation-
ships found against carbon (Fig. 1) or oxygen (Fig. 2)?
There must be a common explanation for such a common
feature, which obviously is linked to the changing structural
features of coal from lignite to anthracite [11]. The idea of
plotting (C 1 H) vs Q, is not really so much intended to
represent the summation of the elements as it is to denote
the proportion of C–H matrix in the total coal substance,
essentially made up of carbon, hydrogen, nitrogen and
oxygen. Of the four elements, C and H constitute the
combustible entities (polycondensed aromatic–hydro-
aromatic complex [4,5,11]), which bereft of O, N and S,
essentially contribute to the heat of combustion of coal. If
viewed in this perspective, the plot (Fig. 3) becomes as
meaningful as the other two analogous plots.
2.4. Interpretation of the relationships
In the first instance it is remarkable to see that the trends
in all the three thermochemical paths (Figs. 1–3), appear to
be a complete replica of what had earlier emerged in the
genetic path [12] from a plot of atomic H/C ratio vs rank,
showing up the same three linear steps AB, BC and CD,
demarcated by the same two turning points at about 84 and
92 wt% carbon (cf. Fig. 1 of Ref. [12]).
The previous interpretation was that the geochemical
evolution [12,13] of the long range of hv coals (C: 62–
84 wt%) mainly entailed a process of de-oxygenation (dehy-
droxylation and decarboxylation), without any significant
change in the C–H matrix and keeping the atomic H/C
ratio virtually constant at the level of 0:80 ^ 0:03: It is not
surprising that such a matrix maintaining more or less the
same chemical status throughout, would be well defined by
1269
its (C 1 H) content in the total coal substance and in turn,
show up a perfectly rectilinear relationship with its heat of
combustion (Q) as is now actually observed in Fig. 3.
The same interpretation, would also hold good for the
allied relationships as in Figs. 1 and 2. A rough and ready
parallelism to Q vs (C 1 H) relationship (in so far as hv
coals are concerned), was previously illustrated [5] in
terms of an organic series, such as phloroglucinol !
resorcinol ! phenol ! benzene. Here, with progressive
“dehydroxylation,” carbon weight percent increases as
oxygen decreases, keeping the H/C ratio constant (at
1.00), a near simulation of what has been broadly found
for hv coals [12,13]. Thus, heat of combustion of such a
series would naturally bear a perfectly rectilinear relation-
ship with either its carbon or oxygen or (C 1 H) contents.
And this is what was actually observed [5].
3. A novel correlation
3.1. Mathematical treatment of the graphical relations
It will now be seen that the Q vs (C 1 H) relationship
(Fig. 3) is not only novel but also perhaps more significant
(than the other two in Figs. 1 and 2), because of its direct
relevance to structural features of coal.
The linearity of the first phase over a long range of hv
coals as defined by their (C 1 H) values, e.g. from as low as
74 to as high as 90–91 wt% is impressive (Fig. 3) the upper
limit of which seems to be mutually consistent with 84–
85 wt% carbon or 7.5–8.00 wt% oxygen, as registered in
Figs. 1 and 2. The ‘break’ in the relationship at or immedi-
ately after 84–85 wt% C, may be ascribed to the commence-
ment at this stage of a profound change, [12] (e.g.
progressive aromatisation) shown to occur in coal structure
due to the onset of dehydrogenation-cum-demethylation
1270 B.K. Mazumdar / Fuel 79 (2000) 1267–1276

Fig. 4. Variation of heat of combustion with sum of carbon and hydrogen contents (C 1 H) for high-purity vitrinites, showing the break between AB and BC.
[The cut-out point between the phases AB and BC is more clearly evident in the inset diagram. This appears to be at a (C 1 H) value of about 90.6 wt%.]

reactions. Such a process is reflected [12] in the correspond-
ing change in atomic H/C ratio throughout this phase (BC).
Remaining virtually constant at the peak value of about 0.80
throughout the hv coals up to 84–85 wt% C, H/C then
decreases almost linearly down to about 0.55–0.56 in this
phase, [12] marked by the 92 wt% C level. Again, beyond
this crucial point, another sharp break in the genetic path
(H/C vs C content [12]), was found to occur leading to very
fast rate of decrease in the H/C ratio but perfectly linear till
the end of the coal series (CD), tending to become almost nil
(apparently merging with the point for graphite).
It is now clear that the progressive structural changes in
C–H matrix of coal as earlier identified in its genetic path
[12,13] and the same phase-wise changes now observed in
the thermochemical path (Fig. 3), are concomitant events,
one being the cause and the other its effect.
A simple linear equation of the type, y ˆ mx 1 c; relating
Q with (C 1 H), can be easily deduced from Fig. 3, exclu-
sively for the hv coals (AB). But before this is done, it is
important to ascertain its upper limit more precisely than
possible from Fig. 3. Impact of petrographic variability on
such a relationship also needs to be more clearly defined.
With a view to precisely defining the above uncertainties,
especially the upper limit of the linearity of AB, a magnified
version of Fig. 3 is presented in Fig. 4 using only the high
purity vitrinite samples of van Krevelen et al. [7,8] (also to
preclude the adverse effect of petrographic impurity). An
inset diagram is also set out therein to indicate more clearly
the corresponding change in atomic H/C values with
increasing (C 1 H) values of the samples plotted. The cut-
off point for hv coals from the high rank coals is at a
(C 1 H) value of about 90.6% (on Parr’s basis), with almost
a constant atomic H/C ratio around 0:78 ^ 0:01: (Fig. 4).
From Fig. 4, the following correlation, exclusively valid
for all hv bright coals of (C 1 H) value # 90.6 wt% has
been derived:
Q ˆ 0:512…C 1 H† 2 11:19 …1†
where, Q denotes calorific value of coal in MJ/kg and C and
H are carbon and hydrogen weight percent on Parr’s basis.
Similarly, and with the same reservations, the following
two parallel correlations could also be deduced from Figs. 1
and 2 for the same range and types of hv coals (vitrains), in
terms of their carbon and oxygen contents, respectively
Q ˆ 0:54 C 2 10:7 …2†
and
Q ˆ 38:66 2 0:465 × O: …3†
3.2. Correlation coefficients (r) of the relationships
Based on 12 samples of vitrinites and vitrain-rich coals
ranging in rank from sub-bituminous to bituminous coals
…C # 84:5 wt%†; used in the present work for the relation-
ships (Eqs. (1)–(3)), have been found to be 1.00, 0.80 and
0.99, respectively, indicating strong correlations for all the
three, the highest and the best being for Q vs (C 1 H)
relationship (Eq. (1)). The relation with oxygen (Eq. (3))
appears to be almost equally strong but as oxygen is
generally obtained “by difference” (therefore involving
cummulative errors), Eq. (1) involving (C 1 H) is obviously
preferred for more reasons than one.
3.3. Extension of Eq. (1) to high rank coals (C . 84–85 wt%)
The reason for the discontinuity of the linear relationship
beyond 84–85 wt% C (Fig. 4), as already discussed, is
mainly due to the onset of dehydrogenation leading to
Table 1
Illustrating the remarkable features and function of the ‘correction factor’ of Eq. (4)1 in correct placement of coal in its metamorphic path (Fig. 3) leading to correct estimate of its calorific value, irrespective of
its petrographic character

Some relevant particulars of coal chosen for the study Position in Fig. Magnitude and sign of the Calorific value MJ/kg, dmf (Parr)
3, (located by “correction factor” MJ/kg
(C 1 H) value)
Expl. Calculated by Eq. (4) a Dev.

% (C 1 H), Parr’s basis Atomic (H/C) 0 ratio

B.K. Mazumdar / Fuel 79 (2000) 1267–1276

Source and Rank %C amf
petrographic
character

1. Vitrinites [7,8] (of high purity van Krevelen)

76.4 81.4 0.79 1st phase, AB 10.07 30.41 30.55 10.14
80.4 85.6 0.77 1st phase, AB 20.07 32.69 32.57 20.12
90.5 95.5 0.67 2nd phase, BC 20.74 36.83 36.96 10.13
95.0 97.5 0.32 3rd phrase, CD 23.11 35.34 35.62 10.28
96.0 97.8 0.225 3rd phrase, CD 23.75 34.97 35.13 10.16
2. British bright coals [18] (Vitrain-rich coals vitrinite content being 75–85%)
81.8 87.1 0.78 1st phase, AB Nil 33.41 33.41 0.00
84.1 89.6 0.78 1st phase, AB Nil 34.83 34.69 20.14
90.2 95.0 0.64 2nd phase, BC 20.94 36.53 36.51 20.02
94.2 97.3 0.38 3rd phase, CD 22.70 35.92 35.93 10.01
3. Indian coals [25] (some dull coals chosen) b
Kotma 83.4 88.3 0.70 AB 20.54 33.32 33.48 10.16
Ramagundam 82.7 87.3 0.65 AB 20.88 32.71 32.63 20.08
Kothagudium 82.0 86.3 0.63 AB 21.01 31.95 31.99 10.04
Bisrampur 81.5 86.0 0.65 AB 20.88 31.90 31.96 10.06

a
Eq. (4): Q ˆ 0:512 …C 1 H† 2 11:19 1 6:75 …H=C 0 2 0:78†; where the last term is the “correction factor”. The latter corrects for both the rank and petrographic character of a coal.
b
These coals are from MP and Godavari Valley coalfields [25], most of which are usually highly sub-hydrous in nature, vitrinte content being as low as 30–50%.

1271
1272 B.K. Mazumdar / Fuel 79 (2000) 1267–1276

Table 2
New correlation vs the Exxon formula in the prediction of calorific value of coal on dmf basis (Parr’s basis): (assessment made reference to a suite of British
coals a)

Correlation No. of Rank range, Assessment results

coal samples a %C, dmf (Parr)
Average absolute Standard deviation Average bias Average absolute
deviation, MJ/kg MJ/kg MJ/kg deviation percent

Author’s (Eq. (4)) 23 77–94 0.12 0.165 1 0.02 0.35

(sub-bituminous to anthracite)
Exxon b 23 0.13 0.174 1 0.07 0.37

a
This is a well-known and well-standardised series of typical British bright coals [18] (vitrinite content ranging from 75 to 85%), code-numbered as D0 to
D22, elementary analysis and calorific value of which were available on Parr’s basis and therefore, could be readily used for the above comparative study.
b
The Exxon formula [22], as given for dmf calorific value (Parr’s basis) is: Btu=lb ˆ 145:6 C 1 568:6 H 2 51:44 × O; where C, H and O are the usual
notations for the elements on percentage weight basis. Values thus obtained were multiplied by 0.0023267 to get corresponding values in MJ/kg unit.

progressive aromatisation up to 92 wt% C. From this point
a drastic process of “dehydrogenation” due to aromatic
ring coalescence was shown to the major reaction
(anthracitisation/graphitisation) [12,13,18] in the geo-
chemical evolution of semi-anthracites/anthracites. These
stepwise structural changes in the genetic path can be
quantified [13] in terms of consequent changes in atomic
H/C 0 ratio for the evaluation of the structural parameters of
coal. In view of this, it occurred to the author that perhaps
the concomitant thermal changes of the C–H matrix of coal
beyond the 84–85 wt% C (Fig. 3), could also be measured
in terms of changes in atomic hydrogen to carbon (H/C 0 )
ratio. 1 Such a concept has enabled the development of a
suitable ‘correction’ factor involving atomic H/C, which
in turn, makes it possible to extend Eq. (1) to all ranks of
coal, from lignite to anthracite
calculated calorific values on dmf basis (Parr), will be
found to be materially the same as their experimental
values, seldom deviating by more than 0.50%.
3.5. Analogous extension of Eqs. (2) and (3)
Q vs C and Q vs O correlation (Eqs. (2) and (3)) can also
be extended to apply to coals in general from lignite to
anthracite
Q ˆ 0:54 C 2 10:7 1 10:7…H=C 0 2 0:78† …5†
Q ˆ 38:66 2 0:465 × O 1 4:89…H=C 0 2 0:78† …6†
All the correlations (Eqs. (4)–(6)) are equally valid for all
types of coals and their accuracy has/also been found to be
of a similar order.

Q ˆ 0:512…C 1 H† 2 11:19 1 6:75…H=C 0 2 0:78† …4† 3.6. Simplification of Eq. (4)

3.4. Applicability to overall coals of varying petrographic
composition
Another remarkable feature of the extended correlation
(Eq. (4)) is that due to the ‘correction’ factor, it has also
been found to apply equally well to all types of coals includ-
ing highly sub-hydrous and/or perhydrous coals. This is less
surprising in view of the proliferation of the primordial
organic mass of coal into various petrological species
being reflected [7,8] in their atomic H/C 0 ratios vis a vis
the vitrainous component. Moreover, it is believed that
abnormal dehydrogenation in early stages of coal formation
[19], might have been the cause of fusinisation in the normal
path of coalification and hence the resemblance found [20]
between fusinites and vitrinites in some structural aspects.
Such universal applicability of Eq. (4), is demonstrated in
Table 1 by applying it to three groups of coals of varying
rank and types, e.g. (a) vitrinites of high purity, (b) some
bright coals and (c) some highly sub-hydrous coals. The
1
To avoid confusion between atomic and weight ratio of hydrogen to
carbon (both of which has been used in the present work) H/C 0 is adopted to
indicate atomic ratio as against H/C, the simple weight ratio.
Compared to the general run of ultimate formulae [16]
such as, the Dulong, Mott-Spooner, IGT [21], Exxon [22]
and the like, the newly found correlation involving atomic
H/C 0 ratio, may be found inconvenient for routine use. This
factor can simply be eliminated and the entire equation
recast in terms of carbon and hydrogen percentages only,
as shown below:
As atomic H/C 0 ratio is 12.01 times its weight ratio (H/C),
Eq. (4) may be rewritten as follows:
Q ˆ 0:512…C 1 H† 2 11:19 1 6:75…12:01H=C 0 2 0:78†
i.e.
Q ˆ 0:512…C 1 H† 2 16:46 1 81:07H=C …7†
Eq. (7) is the final form of Eq. (4). It requires only C and H
data on weight percent Parr basis.
3.7. Comparative accuracy of Eq. (7)
Eq. (7) is possibly the first of its own kind being radically
different both in nature and form, from the general run of
ultimate formulae. Amongst the latter, the formula
advanced by Neaval et al. [22], is claimed to be one of the
 B.K. Mazumdar / Fuel 79 (2000) 1267–1276 1273

best and hence this was chosen for assessing the relative

Taken as given in USBM RI No. 5085, 1955; 57: [24]. The value for calorific value in MJ/kg within parenthesis as above, has been calculated by the present author using the factor: 1 Btu/lb ˆ 0.0023267 MJ/kg.
performance of Eq. (7). Such assessment is presented in
Table 2 in respect of a suite of 23 British coals [18], ranging
in rank from sub-bituminous coals to anthracite (C: 77–
94 wt%). A comparative statistical assessment of the two
formulae (Table 2), indicates a distinct superiority of the
new correlation (Eq. (4)), respective standard deviations
(SD) found being 0.165 and 0.174 MJ/kg and average abso-
lute deviation being 0.35 and 0.37%. Interestingly, Eqs. (5)
and (6) (e.g. Q vs C and Q vs O), were found to apply to the
same set of British coals with standard deviations of 0.168
and 0.170 MJ/kg, respectively.

13,960 ( ; 32.48 MJ/kg) a

Calorific value, Btu/lb
4. Calorific value on commercial basis

The new formula (Eq. (7)) is of academic interest because

this gives calorific values on pure coal basis. Secondly, such

[Qd(MJ/kg) bˆ 0:512…76:6 1 5:2† 1 0:889…81:07 × 5:2=76:6 2 16:46† 1 0:12 × 3:1 2 0:007 × 8:7 ˆ 41:88 2 9:74 1 0:37 2 0:06 ˆ 32:45 MJ=kg
values (as per design of the correlation) exclude heat due to
sulphur, which may be substantial in case of high S
(organic) coals. For commercial evaluation, values are

% Ash (dry)
required either on as-received, air-dry or dry basis, contain-
ing all the minerals including those containing sulphur.

8.7
Such values can be calculated back from pure coal values
obtained by Eq. (7), and then suitably corrected for heat due
to sulphur as well as for endothermic and/or exothermic
changes [22,23] which occur during coal combustion. To
circumvent such cumbersome procedures, it has been

4.9
possible to convert the pure coal formula (Eq. (4) or its
O

Calculated from Eq. (8): Qd ˆ 0:512…Cd 1Hd † 1 f …81:07Hd =Cd 2 16:46† 1 0:12Sd 2 0:007 Ashd :
equivalent, Eq. (7)) to its logical derivative, which directly
yields calorific value on any basis desired, without detract-
An example showing the working of Eq. (8) for the computation of calorific value on dry basis

ing from the fundamental principles behind the original

correlation. The calorific value on dry basis, Qd, is given by
1.5

Qd ˆ 0:512…Cd 1 Hd † 1 f …81:07 Hd =Cd 2 16:46†

N

1 0:116 Sd 2 0:007 Ashd …8†

where Cd, Hd, Sd, and Ashd denote carbon, hydrogen, sulphur
3.1

and ash percentages of coal—all on dry basis, and f is the

S

mineral matter (MM) factor which equals to …100 2

MM†=100:
Compared to any typical ‘ultimate’ formula the new
correlation on dry basis, (Eq. (8)) may look formidable
Basic data, % dry basis a

Hence, MM factor …f † ˆ …100 2 11:1†=100 ˆ 0:889

Calculation: MM ˆ 1:08 Ash 1 0:55 × S ˆ 11:1
5.2

with so may terms in it. In practice, however, its operation

H

may be found quite simple, being essentially based on two

simple terms, e.g. (i) sum-total of carbon and hydrogen
percentages on dry basis, and (ii) their weight ratio, (Hd/
Cd). In Table 3, for a high-sulphur US coal the calculated
76.6

value agrees closely with the experimental value.

C
W.Va, Pittsburgh seam

4.1. A formal assessment of Eq. (8) vis a vis the Exxon

[dev ˆ 0:03 MJ=kg

formula
coal a Rank: Hvab

The Exxon formula was derived [22] by rigorous

regression analysis “of a carefully selected set of 66 US
Table 3

coal samples”, ranging in rank from lignite to low-volatile

b
a

bituminous coal. Its standard deviation was found to be of

1274 B.K. Mazumdar / Fuel 79 (2000) 1267–1276

the order of 0.2 MJ/kg and was superior to all other ultimate

Compiled from USBM Report of Investigations No. 5058, Jan. 1955 and No. 5332, April 1959 [21], in such a manner as to cover most of the major coal-producing states, ranging in rank from lignite to low

It is noteworthy that Neavel et al [22] claimed a standard deviation of about 86 Btu i.e. 0.20 MJ on the basis of studies on 66 US coals, virtually of the same order as obtained in the present work on only 31
Atomic H/C ratio
formulae. Performance of the newly found correlation (Eq.

^ 0.35 MJ
(8)) was therefore compared with that of the Exxon formula

0.59–0.88
on a suite of 31 US coals chosen at random from two USBM

100
100
reports [24]. The selection of data was made so as to cover a
wide range of coals from lignite to lvb coals (C: 73–
91.5 wt% dmf) and having a wide variation of mineral-

Applicability and accuracy of the new correlation (Eq. (8)) for the prediction of calorific value on dry basis, shown in respect of a suite of US coals as against that of Exxon formula

% of Predictions within
matter (2–20 wt%) and S-contents (0.5–4.4 wt%). The

Calorific value, MJ/kg

On dry basis this is: Btu=lb ˆ 145:9 C 1 569:6 H 1 43:08 S 2 53:89 × O 2 6:3Ash: Value thus obtained were converted to MJ/kg by multiplying with the factor 0.0023267.
calculated values (by both the formulae) and their respective
deviations were statistically processed to work out their

24.90–35.27
comparative assessment and this is presented in Table 4.

^ 0.20 MJ
Range of properties of the samples on dry basis
The standard deviation using Eq. (8) was about 0.183
compared to 0.195 MJ for the Exxon formulae. It can also

81
74
be observed that on all other counts too, the new correlation
appears to be superior. The comparative assessment may
be deemed fair, considering that the standard deviation

Av. absolute deviation percent

of about 0.195 MJ as found for Exxon on the basis of
31 samples, is virtually the same as that was originally
obtained for 66 US coals. This rules out any inadvertent
bias in the selection of samples and hence in the assess-
ment.

%S content

0.4–4.4

coals (Table 4B) covering the same rank range. Thus, the above comparative assessment may be deemed to be fair enough.
0.48
0.52
4.2. Potential accuracy

The above accuracy of Eq. (8) has also been corroborated

Av. bias, MJ/kg

by similar studies of coals of other regions, especially those
of India [25] and Canada [26]. This would suggest high
1.7–17
flexibility and tolerance of the correlation to wide variations
% Ash

20.03
20.11
of coal properties. Even so, it is believed that the potential
dry

accuracy of the new correlation could be still better. In the

light of the author’s own experience, sometimes unusual Standard deviation, MJ/kg
errors may occur in routine analytical work which not too
Commercial samples of

infrequently, creates a mismatch between one set of deter-

composite character

minations and the other. In view of this, a special test was

designed for assessing the potential accuracy of the new
B. Results of the statistical assessment vis a vis the 31 US coals as above

correlation, e.g. by bunching of several sets of coal data

^ 0.195 d
A. Some particulars of coals chosen for the comparative assessment a

^ 0.18

(elementary analysis and calorific value on dry basis) at a

Nature

given rank level (say, Hvcb, Hvab, Mvb, Lvb and the like),
and applying the correlation to the mean of such data, treat-
See Eq. (8) and the model calculation given in Table 3.

ing it as one ‘sample’ at that particular rank level. The idea

Average deviation, MJ/kg

of bunching or averaging is to minimise and/or smooth out

undue errors of determinations, if any, in any of the coals
Rank range, %C, dmf

selected for a set. In this manner, ten ‘samples’ were

73–92 (Lig–Lvb)

prepared varying in rank from lignite to lvb coals. Relevant

data are presented in Table 5 wherein the results of appli-
cation of Eq. (8) as well as that of the Exxon formula, are
0.15
0.16

also set out, along with the statistical assessment of their

volatile bituminous coal (Lvb).

respective performance. There has been a distinct improve-

ment in both the relative performances, standard deviation,
No. of coal samples a

being as low as 0.102 MJ. The superior performance of the

genetic formula is emphasised in Eq. (8). It appears to be
uniformly accurate for all ranks of coal, average deviation in
Correlation

Author’s b

any group (Table 5) seldom exceeding 0.4–0.5% (which is

Table 4

Exxon c

well within permissible experimental error, ASTM repro-

b

d
a

c
31

ducibility being about 0.21 MJ/kg).

Table 5
A special test designed to adjudge the potential accuracy of the new correlation (Eq. (8)), by bunching several sets of data at a given rank level

A. Source, rank, elementary analysis and calorific value of such bunched coal samples at different rank level

Sl no. Source Rank ASTM Mean of %C, dmf Analytical data, %dry basis (mean of the samples) Calorific value, dry
(mean value) MJ/kg
C H N S Ash O (by diff.)

1. Alberta a Lig 2 Samples 72.8 66.40 4.44 1.40 0.52 7.84 19.40 26.08

B.K. Mazumdar / Fuel 79 (2000) 1267–1276

2. SD Subc 3 Samples 74.5 63.30 4.33 1.07 1.47 13.20 16.63 25.22
3. Alberta a Subb 3 Samples 76.8 67.31 3.98 1.34 0.23 11.37 15.77 26.23
4. WY Suba 5 Samples 78.3 73.83 4.98 1.57 0.72 4.90 14.00 30.13
5. NM Hvcb 5 Samples 80.1 73.38 5.20 1.40 0.62 7.44 11.96 30.39
6. UT Hvbb 5 Samples 80.4 72.31 5.31 1.41 1.28 8.65 11.04 30.33
7. Pa Hvab 5 Samples 85.4 74.33 4.85 1.40 3.30 10.35 5.77 31.25
8. W.Va Hvab 5 Samples 85.3 78.63 5.25 1.50 1.68 6.40 6.54 32.92
9. Pa Mvb 5 Samples 90.0 79.10 4.50 1.43 1.18 10.60 3.19 32.38
10. W.Va Lvb 5 Samples 90.6 85.88 4.45 1.35 0.73 4.48 3.11 34.59
B. Deviation (in MJ/kg) of the predicted values, calculated by the correlations in respect of the “samples” as in A
Sample no b 1 2 3 4 5 6 7 8 9 10
New correlation (Eq. (8)) 10.12 10.22 0.00 20.09 10.05 10.05 20.10 0.00 10.08 10.10
Exxon 20.17 20.13 20.22 20.22 20.12 20.13 20.02 20.14 Nil 10.08
C. Comparative assessment c
Av.dev. in MJ/kg SD in MJ/kg Av. bias in MJ/kg Av. absolute dev.%
New correlation (Eq. (8)) 0.08 ^ 0.10 2 0.004 0.26
Exxon [22] 0.12 ^ 0.15 2 0.11 0.41

a
Taken from E. Sherlock [26], and the rest from USBM Report of Investigations [24].
b
This corresponds to serial number as in Table 5A.
c
Although such assessment may appear to be somewhat hypothetical, this surely indicates the potential accuracy of both the correlations as against their respective normal accuracies in routine work (cf. Table 4).

1275
1276 B.K. Mazumdar / Fuel 79 (2000) 1267–1276
5. Conclusion
The importance of the present work perhaps lies not so
much in the successful development of a novel and accurate
correlation (either Eq. (7) or its derivative, Eq. (8)) for the
computation of the calorific value of coal, as it is in its
highlighting the genetic path, especially in strengthening
the earlier interpretations of the sequence of chemical reac-
tions identified [12,13] in the geochemical evolution of coal
from lignite to anthracite.
Acknowledgements
The author is thankful to his former colleague, Mr N.C.
Sinha, for helpful discussions in matters relating to statis-
tical assessment of the correlations presented herein.
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