Geochimrca n Cosmcchimica Acta Vol. 53, pp. 2649-2651 00167037/89/53.00 + .

lIO
Copyright @ 1989 Ptxgamon Res pk. Printed in U.S.A.

A chemical kinetic model of vitrinite maturation and reflectance

ALAN K. BURNHAMand JERRY 3. SWEENEY
Lawrence Livermore National Laboratory, Livermore, CA 94550, U.S.A.

(Received December 28, 1988; accepted in revisedform July 14, 1989)

Abstract-A chemical kinetic model is presented that uses Arrhenius rate constants to calculate vitrinite
elemental composition as a function of time and temperature. The model uses distributions of activation
energies for each of four reactions: ehmination of water, carbon dioxide, methane, and higher hydrocarbons.
The resulting composition is used to calculate vitrinite reflectance via correlations between elemental
composition and reflectance. The correlations are derived from published measurements. The model is
valid for %Ro values from slightly less than 0.3 to slightly greater than 4. Model calculations are compared
to published vitrinite data from both laboratory experiments and sedimentary columns where adequate
thermal histories are available. Calculated and measured %Ro values generally agree within 0.1 at low
rank and 0.4 at high rank, which is comparable to uncertainties in the experimental values. This confirms
our starting premise that vitrinite reflectance is properly described by standard chemical kinetics with
activation energies that extrapolate from laboratory to geological maturation temperatures. The model
indicates that the relationship between the extent of oil generation and vitrinite reflectance is nearly
independent of heating rate.

INTRODUCIlON then calculates vitrinite reflectance from correlations of re-

VITRINITEREFLECTANCE IS A major indicator of thermal ma-
turity for oil and gas exploration (HUNT, 1979; WAPLES,
1981; TISSOT and WELTE, 1984; TISSOT et al,, 1987). It has
been recognized for many years that vitrinite reflectance cor-
relates with coal rank, which is primarily a function of time
and temperature (VAN KREVELEN, 1961; TSCHAMLERand
DE RUITER, 1963). The first popular kinetic model of vi-
trinite maturation related to petroleum exploration ( WAPLES,
1980) used the Lopatin approach ( LOPATIN, 197 1 ), which
assumes that the rate of maturation doubles every 10C. Al-
though this rule of thumb is stated in some elementary
chemistry texts, it is generally not very accurate. In particular,
it implies that the activation energy for the reaction is a func-
tion of temperature and equal to 20 kcal/mol at 103C.
Some early kinetic models of oil generation in sedimentary
columns also used very low activation energies (TISSOT, 1969;
CONNAN, 1974), but these erroneously low values arise be-
cause they did not account for a dist~bution of reactivity
( HANBABA,1967, quoted in JUNTGENand VANHEEK, 1970;
BRAUNand BURNHAM, 1987). The distribution ofreactivity
is usually treated by using a distribution of activation energies,
and it is now generally accepted that the correct mean acti-
vation energy for oil generation is about 50 kcal/mol (UN-
GERER and PELET, 1987; TISSOT et al., 1987; SWEENEYet
al., 1987; BURNHAM et al., 1987; QUIGLEY et al., 1987;
MACKENZIEand QUIGLEY, 1988 ) .
The correct activation energy for vitrinite maturation is
less well established, but LARTER ( 1989) has shown that vi-
trinite maturation is also consistent with an activation energy
distribution model using chemicaily meaningful parameters.
This paper presents a related but more comp~hensive model
for vitrinite maturation and reflectance. We caJculate vitrinite
composition from a chemical kinetic model that considers
separate reactions for elimination of water, carbon dioxide,
methane, and higher hydrocarbons from the structure, and
2449
flectance with carbon content and with H/C and O/C atomic
ratios. Derivation of the composition-reflectance correlations
is given first, development of the compositional kinetic model
is given next, followed by comparisons of measured vitrinite
reflectance with values calculated from thermal histories.
RELA~ONS~IP BETWEEN VITIUNITE ~OMPOS~ON
AND REPLECIANCE
The underlying assumption of our model is that reflectance
of vitrinite (or any other maceral) is related to its chemical
composition. Reflectance of light at any interface is related
to the refractive and absorption indices by the Fresnel-Beer
equation ( TSCHAMLERand DE RUITER, 1963 ) . Both indices
are a function of the materials density and electronic struc-
ture, both of which are determined by the materials chemical
structure. If the detailed chemical structure of vitrinite were
known as a function of maturity, the refractive index could
be estimated, at least at low rank, from correlations that have
been developed for the refractive index of organic liquids and
polymers f VAN REEVELEN,1976). Estimations at higher rank
would have to take into consideration the fact that the po-
larizability per carbon atom becomes larger as the aromatic
rings become larger due to the higher mobility of the rr elec-
trons (SCHUYERet al., 1953). However, estimating %Ro from
such correlations requires more structural inFo~ation than
is presently available, especially considering that absorption
constants would have to be estimated as well as refractive
indices. Furthermore, to achieve the object of this work, we
would need some way of calculating the detailed vitrinite
structure as a function of time and temperature.
A more tractable approach is to assume that the electronic
properties of vitrinite vary smoothly with elemental com-
position. MCCARTNEYand ERGUN ( 1958) showed that the
logarithm of vitrinite reflectance correlated strongly with the
H/C atomic ratio of vitrinite. NEAVEL( 198 1) later attributed
the relation
2650 A. K. Bumbam and .I. .J.Sweeney
%Ro = 15.64 exp[-3.6(H/C)J
to MCCARTNEYand ERCUN ( 1967 ), where OioRois the per-
cent of reflected tight in oil immersion. This is logical because
the polar&ability densities (molar refractivity divided by
molar volume) of aromatic groups are higher than those of
aliphatic groups (VAN KREVELEN, 1976 1. However, it is ev-
ident in MCCARTNEYand ERGUN ( 1958 ) as well as in a later
figure in MCCARTNEYand TEICHM~LLER( 1972 f that there
is some curvature in the reIationship. An improved corre-
lation can be obtained by recognizing that oxygen content
also tends to reduce the refractive index. The average polar-
izability density of carboxylate groups is about the same as
that of methylene groups, and ethers and hydroxyl groups
are substantially less poiarizable (VAN KREVELEK 1976 ).
We derived by inspection the relation
oRo = 12 exp[-3.3(H/C)] - (O/C!.
which is compared in Fig. 1 with the MCCARTNEY and
TEKHM~LLER ( 1972) results. We have used an average re-
lation between O/C and H/C to derive our curve. It may
look as though this oxygen correction is too huge, but evidence
presented in the next section indicates that it is approximately
correct. Any improvement in this correlation would require
more extensive data at low reflectance, possibly by including
individual O/C ratios in a multiple regression analysis.
Correlations between reflectance and carbon content have
also been presented (VAN KREVFLEN, 196 I ; TKHAMLER and
DE RUIWR, 1963; MCCARTNEY and TEI~HMULLER. 1972:
DAVIS, 1978; HUNT, 1979). We derived by inspection an
equation based on results given by DAVIS ( 1978 ).
%Ro = exp(-1.25 + 4.58 + 3OO.I + 1.6 q 10x~).
where A = (wt% C - 65)/ 100. This equation is compared
with his data in Fig. 2. Again, it is doubtful that the data
warrants more rigorous curve fitting.
...___.
/ 1 / .A
0.2 0.4 0.6 0.8 1 .O 1.2
H/C, atomic ratio
Frc. 1. Comparison of vitrinite reflectance data ( MCCARTNEI
and TEICHMULLER,1972) to that calculated with E&s. ( I ) and (2 )
The syrnboIs retain their original meaning: 0.0 European v&kites:
3 U.S. coals.
(I)
c i-
OIL---
* 70
:
75 80
:-_-I-_~___
85 90
__. _
9s
Carbon, % ~~~~F, Parr)
(2) FIG. 2. Comparison of Eqn. (3) to the vitnnite retlectance data oi
DAVIS ( 1978 ) to which it was calibrated.
It is important to recall that vitrinite reflectance can be
anisotropic. When maturation occurs under hthostattc QreS-
sure, the aromatic rings tend to reorient along the bedding
planes. Since the rings are more polarizable along the ring
than orthogonal to it, the reflectance will be greater along the
bedding plane. This anisotropy is insignificant for PRO less
than 1, but it is about a factor of two when PRO reaches 4
f SHARKEYand MCCARTNEY, 1963 ) ~Our correlations have
been derived for the maximum reflectance orientation
COMFOSITIONAL MODEL OF
(3) VITRINITE MATURATION
To take advantage of the relationship in the preteens
section, we need a chemical kinetic model that can calculate
the carbon content and H/C and O/C atomic ratios of vi.
trinite as a function of time and temperature. The van Krec
, elan diagram (H/C versus O/C) is commonly used to plot
changes in composition with maturation (VAN ~EVELEk.
1961; TSAI, 1982; TISSOT and WELTE, 1984; Mo~T~I~~I~
et al., 1985; SAXBY et al., 1986 j. It is evident from these
plots that coal, which is dominated by vitrinite, and vitrinite.
when analyzed separately, preferentially eliminate water and
carbon dioxide during the early maturation stages and elim-
inate hydrocarbons in the later stages. This can be treated
most simply by considering four independent paraltel reac-
tions:
vitrinite + residual vitrinite + HZ0
vitrinite -c residual vitrinite + CO1
vitrinite --* residual vitrinite T i.H,
vitrinite --) residuat vitrinite t CH,
1.4 The third reaction, generation of higher hydrocarbons iCEi,)_
is not essential for calculation of vitrinite reflectance. How-
ever, we have included it for generality because the same
kinetic model could be used to calculate compositional mat-
uration trends for other mace&i that may generate signifi~n~
amounts of higher hydrocarbons. The material balance
 Kinetics of vitrinite maturation 2651

equations presented in this section are general and could
therefore be applied to other macerals or mixtures.
By the application of simple conservation relations, it is
possible to derive equations giving the composition of the
residual vitrinite as a function of the initial vitrinite com-
position and the extent of each of the four reactions above.
We start by writing the reaction
U-LO, - C,-&-dH*-za_nr_4dOp2ti+ a Hz0
+bC02+cCH,+dCH4.
The compositional properties of the residual solid can be
calculated easily from its empirical formula. Time depen-
dence is added by merely replacing the factors u-d with the
product of the maximum possible yield and the fraction re-
acted for each species. We define (Yand @as the fraction of
initial oxygen that is removed as H20 and C02, respectively,
and y and 6 as the fraction of initial carbon removed as CH,
and CH4, respectively. A concern is to choose the maximum
yields so that the hydrogen and oxygen contents do not be-
come negative. There is ordinarily enough hydrogen for all
the water to be removed without depleting hydrogen, and
the yield of CH, is usually small enough that it does not
exceed hydrogen availability. In contrast, methane is a major
fate of hydrogen and the last product to be evolved in this
model. Therefore, we derive an equation to calculate the
maximum possible methane yield assuming values for the
other products and the desired end state. If we define x as
the desired residual H/C atomic ratio after all of the above
reactions are complete, it can be shown that
6 = [x - 2Ycu - 2y - X( 1 - yp/2 - y)]/(4 - X). (4)
If we defined as the fraction of the jth species evolved, then
the composition of the remaining material as a function of
conversion is given by
H/C = (x - 2ycvL - nrf - 4%)l
(1 - YPf/2 - Yf, - %), (5)
O/C = Y( 1 - 4 - PXdl( 1 - yPfs/2 - rf, - G), (6)
a maximum carbon content of 93.3%, which results in a
maximum reflectance of 4.62%.
We need chemical kinetic expressions to calculate the ex-
tent of the above reactions. In general, maturation reactions
can be a function of time, temperature, and pressure. High
pressure is required in laboratory experiments to simulate
geological maturation of low rank coals ( MONTHIOUXet al.,
1985 ). In low-pressure laboratory experiments, oxygen-con-
taining tars are evolved during the early stages of reaction,
the ratio of water to CO2 increases, and other oxygen is con-
verted to refractory cross-linking bonds, thereby causing the
coal to follow a more direct path to the origin of the van
Krevelen diagram. For simplicity, we chose not to include
pressure explicitly in our model. However, our model does
assume that the pressure is high enough so that time and
temperature are the only important variables. We further
assume that this dependence is described adequately by the
Arrhenius equation
k = A exp(-EIRT) (8)
where k is the rate constant, A is the frequency factor, and
E is the activation energy. We assume that each of the four
reactions above is really a complex set of reactions that can
be described by a set of parallel first-order reactions:
dCiJdt = -kiCi, (9)
where C represents the precursor of H20, C02, CH, , or CH., ,
and i represents the ith component of that precursor. We
also assume that the kis for a given precursor have different
Es but share a common A.
There is insufficient information in the literature to
uniquely define the required rate parameters for vitrinite.
The kinetic parameters are given in Table 1 from trial-and-
error matching of the model to results from both geological
maturation ( TSAI, 1982; POLASTROand BARKER, 1986 ) and
laboratory pyrolysis ( DURAND-SOURONet al., 1982; MON-
THIOUXet al., 1985; SAXBYet al., 1986). The methane kinetic
parameters are taken with minor modification from a mass
spectrometric investigation of coal pyrolysis ( BURNHAM et

and
Table 1. Kinetic constams used in the compositional
model of vitrinite maturati0n.a
wt% C = 1200/[12 + (H/C) + 16(0/C)] - 1.5. (7)
Energy % of soecies characterized bv eiven E
The constant of 1.5 in Eqn. (7) accounts for nitrogen and kcal/mol H20 Co;? CH, CH4
other elements, which we assume are eliminated from the
38
vitrinite structure at a rate such that their ratio to carbon 40 1:
does not change. This approximation is supported by analyses 42 15 5
44 20 15
of both naturally (SENFTLE et al., 1986) and artificially 46 20 5
( MONTHIOUX et al., 1985 ) matured samples. Most calcula- 48 15 ;:
50 10 15 :: 7
tions in the next section used an initial atomic H/C(x) of 52 5 10 12
0.9, an initial atomic O/C(Y) of 0.35, and a residual atomic S 2: 14
:: 10 13
H/C(X) of 0.28. The fractions of oxygen evolved as H20( (Y) 5 12
and CO,(p) were 0.25 and 0.7, respectively, and 1% of the 2 11
62 9
carbon was evolved as CH,(7), with n = 1.7. Using these 7
parameters in Eqns. (4) and (5) gives a methane yield of :
68 :
12.5% of the initial carbon and a residual atomic O/C of 70
0.024. Substituting the residual H/C and O/C atomic ratios 72 ;
74 1
into Eqn. (2) reveals a maximum calculated reflectance of
4.74%. Similarly, substituting them into Eqn. (7), one obtains aA is 2~013 s-1 for cH, and 1~1013s-1 for others
2652 A. K. Bumham and J. J. Sweeney

al., 1989). At atmospheric pressure, molecular hydrogen

continues to evolve after methane evolution is complete
( BURNHAMet al., 1989). Extension of the present model to
higher reflectance would require kinetics for elimination of
0.61 4
this additional residual hydrogen.
The kinetic parameters in Table 1 were used in a spread-
sheet implementation of our maturation model. Integration
of the kinetic equations, which is required in order to calculate
the jj in Eqns. (5) and (6), is done by using the algorithms
given by BRAUN and BURNHAM ( 1987) for a series of se-
quential time segments with constant but independent heatin
rates. The results from Eqns. ( 5 )-( 7 f were then used in Eqns.
[ 2 f and (3) to calculate vitrinite reflectance. Calculation of 4 i(!,i -,_.-------
.
all parameters including vitrinite reflectance took about 0.5 - WC correlation
second per segment on a ~-MHZ IBM AT with a math co- cj I- -- - - C correlation
processor. ; 4

VERIFICATION OF THE MATURATION- 3

REFLECTANCE MQDEL =tz 2 I-
/
?!
The kinetic and stoichiometric parameters were initially
verified by comparing crossplots of various compositional
variables with published data ( TSAI, 1982; SENFTLE et al..
1986). These calculations assumed a constant heating rate
of 1OC/ Ma. A few examples of these comparisons are given t / / /
.I-. --- _-_-_-___.,_i

in Figs. 3 and 4 for vitrinite com~sitions published by 62 70 78 86 94

SENFTLE et al. ( 1986). The calculated maturation curve in
Fig. 3 ends at H/C = 0.32 because not all methane has been
generated by 280C at lOC/Ma.
While these plots verify that both the relative rates of reiease
of the four species at geological conditions and the compo-
sitional relationships to reflectance are adequate, they do not
address the absolute rates of release. The extent of the four
reactions as a function of temperature at typical geologic and
laboratory heating rates is given in Eig. 5. We compare these
results to published data and models, keeping in mind that
all published kinetic data are for coal, not vitrinite, and that
our model does not correspond exactly to other matumtion
models.
We first consider geologic maturation. TLSSOTet al. ( 1987 )
presented a kinetic model for hydrocarbon generation from
Type III kerogen, which they seem to imply is mostly for oil
generation. They used the same discrete activation energy
Carbon content, wt%
FIG. 4. Further comparison of calculated maturation trends wtth
data given by SENRLE (1986). The H/C and O/C atomic ratios
and vitrinite reflectance are c&dated at lOF/Ma.
formalism used in this paper. They attributed 20% of the
reaction to an activation energy of 52 kcalimol, 40% to 54
kcal/mol, 20% to 56 kcal/mol, plusother minor components.
They gave a generation midpoint of 150C at a heating rate
of 3.3*C/Ma, which corresponds to a frequency factor of
1.1. lOI s-. QUIGLEYet al. ( 1987) presented rate constants
for gas generation from refractory kerogen derived from
wood. Their parameters are A = 1.8 - 10 s s _ and a Gaussian
distribution of energies with a mean of 66.7 kcalimol and a
dis~bution width of 3 kcal/mol. We calculate a gas gener-

Geologic temperature, Z_:

1 : 8 __..__._ ___^._:_-.
-._
I
100 180

calcutation
c:
0 0.6 c
1

0.4 i
[I / I 1 /
o.30 .-i_i
0.1 0.2 0.3 0.4
O/C, atomic ratio 300 400 !iOo 600
Laboratory temperature, 62
FIG. 3. Calculated van Kreveten maturation path of vitrinite com-
pared to data given by SE-E et al. ( 1986). The calculation was FIG. 5. Cumulative amount of&O, COz, CH.. and CH4 evolveu
from 20 to 28OC at IOC/Ma. from coal for reaction at 3.3C/Ma and 4C/min
 Kinetics of vitrinite maturation 2653

ation midpoint of 180 at 3.3C/Ma from these parameters. . I

For comparison, our generation midpoints at 3.3CjMa are

143C for higher hydrocarbons and 192C for methane.
We noted earlier that our methane generation kinetics were
derived from laboratory experiments on coal ( BURNHAMet
al., 1989). The parameters were calibrated by comparison
to experiments at a single heating rate of 4C/min, so they
agree by design at that heating rate. Because of an assumed
mean activation energy, however, they do not necessarily
extrapolate to geologic conditions. Therefore, the agreement
with Quigleys refractory kerogen kinetics at 3.3C/Ma is
important because it indicates that our methane parameters
are good. The comparison of our hi8her hydrocarbon kinetics
to laboratory experiments is complicated by the pressure ef-
fects mentioned above. We chose our mean kinetic param-
eters to be close to those for Green River (lacustrine) kerogen
(SWEENEYet al., 1987; BURNHAMet al., 1987). The gener-
ation of dkanes from coal occurs at roughly the same tem-
perature as from Green River shale f BURNHAMet al., 1989 ) .
The water and carbon dioxide generation kinetics are also
not well-constrained. DURAND-SOURONet al. ( 1982 ) report
that when very immature terrestrial kerogen is pyrolyzed at
SC/min in a vacuum, both are evolved over a wide tem-
perature range with a maximum rate at about 300C which
is slightly lower than for our calculated evolution rates. For
all species, the temperature of maximum evolution rate for
laboratory pyrolysis increases with coal rank, which is con-
sistent with the predictions of an activation energy distri-
bution model. Finally, an overall test of the kinetics is pro-
vided in Fig. 6, where we compare our calculated H/C and
O/C atomic ratios to the measured values from hi&r-pressure
sealed-tube experiments of MONTHIOUXet al. ( I985 ) . Their
results indicate slightly faster hydrocarbon generation kinetics
and slightly broader distributions for the oxygen species, but
the overall agreement is very good.
The preceding paragraphs indicate that our calculated rates
of product release and our correlations between composition
and reflectance are inde~ndently valid. A more stringent
, I I found that vitrinite reflectance in coal increased much faster
jr-55 I ,
me Calculated
ii q 0 Measured
6.8 -
0.9 1 p I;Og:
f 0.8 D---m
250 C 200 C
u 0.7 =----a
E 300%
2 0.6 i _
0 0.1 0.2 0.3 0.4
O/C, atomic tatlo
FIG. 7. van Krevelen diagram comparing data of SAXBY et al.
( 1986) for brown coal heated at IT/week with our model calcu-
lations for the same thermal history. The initial H/C and O/C atomic
ratios for the calculations are equal to those of the brown coal.
test is whether the model can accurately calculate the reflec-
tances of a series of samples heated for different, known times.
We now present such a comparison for both laboratory and
geolog_ical series.
SAXBY et al. ( 1986) heated samples of a brown coal and
a torbanite in sealed glass tubes from 100 to 400C at a heating
rate of 1C/week. At 50C intervals, a tube of each material
was removed and analyzed. The measured compositions of
the brown coal are compared with our model calculations in
Fig. 7. The agreement is good, except that hydrogen is elim-
inated in Saxbys experiments a little fmter relative to oxygen.
The vitrinite reflectance from both samples is compared with
our model calculation in Fig. 8. The agreement is generally
excellent. However, the reflectance of vitrinite in their tor-
banite sample seems to start at an anomalously high value,
possibly because the vitrinite in the torbanite is recycled or-
ganic matter from a more mature coal.
LEWAN ( 1985) reported vi~nite-re~e~n~ data for two
source rocks and two coals pyrolyzed under subcritical water
at various temperatures for 72 hours. Unlike Saxby, Lewan
I
with initial heating than vitrinite mixed with a larger amount
i of hydrogen-rich kerogen. Our calculated values are compared

A Torbanite
:
ae V Brown coal
- 3
$
5
5 2
5L

Ia /
C&i
/
366
00
l*. 0 g
460
Q
$
500
d 07 i I I I I J
100 150 200 250 300 350 400
sample Temperature,%
Final temperature,C
FIG. 6. Comparison of measured atomic ratios of residual coal
from high-pressure pyrolysis (MONTHIOLJXet al., 1985) with those FIG. 8. Vitrinite reflectsnce data Of SAXBY et al. ( 1986) compared
calculated for 24.hour exposure at the indicated temperature. to that calculated with our kinetic model and Eqns. (2) and ( 3 ).
2654 4. K. Bumham and J. J. Sweeney

with his data in Fig. 9. Initially, our calculated values are Vltrlnlte reflectance, Y&o
intermediate between his coal and marine source-rock values.
but our calculations agree very well with his marine source-
rock values at higher temperatures. The difference in Lewans
results for his two samples may be due to different types of
vitrinite ( TISSOT et al., 1987 ) or to the hydrogen-rich envi-
ronment of the Phosphoria shale (PRICEand BARKER,1985 )
Larter
In any event, it appears that the difference between Saxbys
and Lewans results is more significant than the difference
between our calculations and either data set. ; *
C corr.
We next compare our model with vitrinite reflectance data \ . \ \ JI H/C corr. j
from sedimentary columns where the thermal histories are
known fairly well. LARTER( 1989) demonstrated that his ki-
netic model was consistent with vitrinite reflectance for the
COST #1 well in the Gulf of Mexico. Thermal history and
vitrinite reflectance data for the COST #1 well is given by
WAPLES( 198 1). Our model calculations using Wapfes ther-
mal history model are compared in Fig. 10 with both the
experimental data and with Larters model. Our H/C cor-
relation, Eqn. (2), works somewhat better than our carbon __-..__a-_--. ._i_ _.i i_..._ . . . . _ -..

correfation, Eqn. (3). Our H/C correlation agrees with Lar-

ters method over the range that his is valid, but our calcu-
tation works over a larger range. The disagreement between
our calculations and the measured data at depths above 2000
m could be due to the thermal model used, as well as to the
limitations of our model. A similar comparison IS shown in
Fig. 1I for the Wagon Wheel well in Wyoming. The thermal
history for this calculation was derived from the burial history
of POLLASTROand BARKER ( 1986) by assuming that all
stratigraphic levels follow parallel burial histories and by using
a geothermal gradient of 23.7C/km (SPENCER, 1987). Here
the correspondence is good over the entire range of data.
QWGLEY et al. ( l987) presented vitrinite data for three basins
FIG. f 0. A comparison of vitrinite reflectance data fmm WAPLES
( 198 I ) for theCOST #I welt, Gutfcoast, U.S.A.. with that calculated
by various kinetic equations. All calculations used Waples thermal
history.
with different but roughly constant heating rates. Our model
calculations using our H/C correiation at the extreme healing
rates bracket the data, as shown in Fig. 12. The calculated
curves are not quite linear, and there is too much scatter XI
the data to test whether they should be linear. The curves
from the carbon correlation are similar but tend to be more
nonlinear.

Original
sample
1 , 1.1 0.2
Vitrinite reflectance, O/of30
3.0 4.0
-r d I-__r -T--
weti
l Measured

2000
C C
E

360
t
0.2 1.0 1.8

Vltrinite reflectance, %Ro

FOG. 9. Vitrinite reflectance data of LEWAN( 1985) for hydrous FIG. 1I. Similar comparison as in Fig. IO for the Wagon Wheel
pyrolysis of Phosphoria ( 0) and Woodford ( 0) shales and Wilcox well, Wyoming. Also shown is a calculation using Ihe TTI formalism
Fairfield (A) and Blackhawk coals (m) compared to our model cal- and the correlation between TTI and reflectance given by WAPI.ES
culations ( 72 h at indicated temperature 1. (19811.
 Kinetics of vitrinite maturation 2655

$ 2.0-

E
s l.O-
g
=
s 0.5 -
.Z
C
& 0.3 -
>
c.
I 4 I /

0 50 loo 150 200 250

maximum T, C
Oka 100 150 200 250 300 350
FIG.12. Effect of geological heating rate on vitrinite reflectance. Present-day temperature,%
The lines represent calculations of our kinetic model and Eqn. (3),
and the data comes from QUIGLEYet al. ( 1987) for the Scotian Shelf FIG. 13. Comparison of measured and calculated vitrinite reflec-
(A,0.5C/Ma),North!Sea(O, lC/Ma),andPannonianBasin(+, tance values for the Cerro Prieto geothermal field.
30-50C/Ma).

of oil generation. We do not know why the carbon correlation

We present one final comparison that tests the upper range
of our present model parameters. Figure 13 compares mea-
sured and calculated vitrinite reflectance values from the
Cerro Prieto geothermal field. The measured values come
from BARKER and ELDERS (198 1) and were obtained by
comparing vitrinite vs. depth data in their Fig. 2 with the T-
25 profile of present-day temperature vs. depth in their Fig.
3. The solid line is their correlation for vitrinite versus tem-
perature. The broken lines were calculated with our model
by using a heating rate of lOOC/Ma, which corresponds to
reaching 3OOC in 3 Ma. Even though we assumed a constant
heating rate, our model calculations agree with the measured
values at least as well as the correlation of BARKER and EL-
DERS (198 1 ), and our model was developed completely in-
dependent of their data. Any rigorous statistical comparison
is hindered by scatter in the data. Part of the scatter, in fact,
may be due to differences in the exact thermal history paths
for each depth.
does not work quite as well. Second, the calculations for Fig.
14 used a constant heating rate of 3.3C/Ma, but calculations
at heating rates from 0.1 to SOC/Ma yielded curves that
were nearly identical. This disagrees with the suggestion of
YUKLER and KOKESH ( 1984) that the ~lation~ip between
vi&mite reflectance and oil generation depends on heating
rate. Their arguments were based on differing, but obviously
erroneous, effective activation energies for the two processes.
Our calculations agree with the result of LARTER( 1989) that
the effective mean activation energy for vitrinite maturation
near the oil window is close to the approximately 50 kcal/
mol for oil generation.
DISCUSSION
While there is no rigorous argument that the Arrhenius
equation should extrapolate well from laboratory to geological
conditions, the results in this paper provide ad~tion~ con-

RELATIONSHIP BETWEEN VITRINITE REFLECTANCE 1- 1 I .

AND OIL GENERATION
It is normally assumed that intense oil generation from
typical marine source rocks starts at a vitrinite reflectance of 0.8 -
0.5-0.65% and oil generation is completed (oil concentrations B
X
at their maximum) at 0.85-l. 1% ( WAPLES, 1981; TISSOT 8
5 0.6 -
and WELTE, 1984). If we calculate reflectance and the extent 01
of oil generation as a function of time for the same thermal %
history, we can construct the relationships shown in Fig. 14. = 0.4 - WC eorr. (Eq. 2) -
For these calcuiations, we used a frequency factor of 5 - 10 I2 $
ZZ
s- and an activation energy dist~bution of 5, 20, 50, 20, 8
and 5% of the reaction, respectively, at energies of 47-51 g 0.2-
kcal / mol. These kinetic parameters predict a maximum rate
of oil generation of 128C at a heating rate of 3.3C/Ma,
which is near the average of temperatures predicted by several
kinetic models for marine kerogens ( BURNHAMet al., 1987; Vitrinite reflectance, %Ro
TISSOT et al., 1987; YOKLER, 1987; MACKENZIE and QUIG-
LEY, 1988). RG. 14. Relationship between vitrinite reflectance and oil gcuer-
ation cakulated by our model. The temperatures indicated are for a
There are two points of interest concerning Fig. 14. First,
heating rate of 3.3C/Ma, but the retkctanceconvemion relationship
the reflectance calculated from the H/C correlation seems is essentially independent of heating rate for heating rates from 0.1
to agree better with prevailing wisdom concerning the onset to SOC/Ma.
2656 A. K. Bumham and J. J. Sweeney
firmation that it works quite well as long asgood, appropriate
data are properly analyzed. Earlier pessimism (SNOWDON,
1979) was a result of poor data or poor data analysis. The
word appropriate is particularly important for vitrinite.
While pressure does not appear to be particularly important
for Type I and II kerogens, the higher oxygen content of
Type III kerogens (e.g., vitrinite) appears to require data at
high pressures to derive correct, effective rate constants. Al-
ternatively, a detailed chemical kinetic model that includes
both transport processes and secondary reactions might
be able to predict the pressure effects from more basic
phenomena.
A key eiement in deriving kinetic expressions that extrap-
olate over wide temperature ranges is the use of activation
energy distribution models. The very low effective activation
energy that corresponds to the Lopatin method is an artifact
of neglecting the diversity of reactions involved. In a similar
vein, it is possible to derive chemically realistic activation
energies for biomarker generation if an activation energy dis-
tribution model is used ( BURNHAM, 1989). The use of a
single frequency f&or with the activation energy ~~bution
is an obvious simplification of reality, but there is usually
not enough data available over a wide enough temperature
range to determine distributions in both A and E. Altema-
lively, a conve~ionde~ndent A and E is easily derived
(FRIEDMAN, 1963), but it is more difficult to apply in complex
kinetic models.
The compositional model presented here is obviously more
complex than the kinetic model presented previously by
LARTER ( 1989 1. If one is interested only in geological mat-
uration within the range of0.5 to 1.4 %Ro, his model is more
convenient. However, our model, especially with the H/C
correlation, appears to be valid from 0.3 to about 4 %Ro.
Moreover, ours is based on correlating reflectance with com-
positional properties that are more directly related to those
causing reflectance. Latters is based on phenol yield upon
pyrolysis, which correlates directly with vitrinite rank only
over a narrow range. Methoxy- and dioxy-aromatics are
formed instead of phenols at very low ranks (WATCHERet
al., 1988), and there is an insufficient amount of the right
kind of oxygen left in high-rank coal to form significant
amounts of phenols.
It is important not to confuse the model presented in this
paper with the model input parameters. Adjustments in the
input parameters could certainly improve agreement between
the model calculations and experiments for any given limited
set of conditions, and perhaps for all vitrinite reflectance data
as a whole. However, the principal objective of this work is
to show that a relatively simple kinetic model with reasonable
reaction parameters can achieve semi-quantitative agreement
with much data over a very wide range of conditions. A major
impediment to improving the model for more global appli-
cation is the inconsistency among various data sets. There
are issues in addition to inaccurate me~uremen~ and ther-
mal histories. First, there are two different types of organic
matter that are commonly identified as vitrinite, but they
differ in hydrogen content and reflectance ( TIZ+OTet al., 1987,
pp. 1447-1449). Second,it has been proposed that increases
in vitrinite reflectance can be inhibited by reaction with bi-
tumen from other hydrogen-rich macerals (PRICEand BAR.,
KER, 1985). Third, the dependence of reflectance on particte
orientation, which becomes important for reflectances greatei
than l%, is not always taken into account. Kinetic expen-
ments on isolated vitrinites also would aid in model devel.
opment.
We believe that other vitrinite reflectance models not ba.5e.d
on the Arrhenius equation have significantly less merit be
cause they are valid only over relatively narrow heating rate
ranges. The weaknesses of the Lopatin method have been
discussed previously ( QUIGLEY et al., 1987; WOOD. 1988 1:
The time-temperature relationship used by LERCXE et a:
( t984), k = A exp[( T - r,),/rp], also has little theoreticai
basis. Combining previous results for oil ( BURNHAMet al.
1987; UNGEBER and PELET, 1987) and biomarker (BURIZ.
HAM, 1989) generation with the vitrinite results discussed in
this paper, it becomes obvious that the Arrhenius equation
with an activation energy distribution is a superior approach
Acknowledgments-This work was perfom~ed under the auspices 01
the U.S. Department of Energy by the Lawrence Livermore National
Lahoratorv under Contract W-7~5-~n~~8. Financial sunnort came
from the &I& of Basic Energy Sciences and a group of;ndustrial
sponsors (Exxon, Arco, Norsk Hydro, IKU, Chevron, Stat&l, and
JNOC).
Editorial hu~df~~g:R. P. Philp
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