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Natural Resources Research, Vol. 13, No. 2, June 2004 (

C 2004)

A Review and Evaluation of Specific Heat Capacities

of Rocks, Minerals, and Subsurface Fluids.
Part 1: Minerals and Nonporous Rocks

Douglas W. Waples1 and Jacob S. Waples2

Received 25 July 2003, revised 6 April 2004

Heat capacities of the rocks within a sedimentary basin can significantly influence geother-
mal gradients if sedimentation or erosion is rapid. This paper provides data on specific heat
capacities of minerals and nonporous rocks at 20 C, derives equations for calculating specific
heat capacities of minerals and nonporous rocks at temperatures between 0 C and 1200 C,
and shows that pressure effects on heat capacities of solids can be neglected. It derives an
equation for estimating specific heat capacity of any mineral or nonporous rock as a function
of density. Finally, it shows how to calculate the specific heat capacity of any mixture of solid
materials. A companion paper discusses specific heat capacities of the fluids in pore spaces of
rocks and of fluid-filled porous rocks.
The data for minerals and rocks provided herein can be incorporated directly into existing
modeling software by users. However, the temperature-dependent equations would have to
be incorporated by software developers.

KEY WORDS: Basin modeling, thermal capacity, specific heat capacity.

INTRODUCTION In some situations we refer to the specific heat

The heat capacity of any substance is the amount
of heat required to raise the temperature of that sub-
stance by one degree (usually Celsius or Kelvin, which
are equivalent in this calculation). As the tempera-
ture of a substance increases, this heat is stored in
its molecules in the form of higher translational, ro-
tational, and vibrational energies. The stored heat is
capacity per unit volume of substance, which is ob-
tained by multiplying the specific heat capacity by
the density. This property is termed the thermal
capacity:
Thermal capacity = (Specific heat capacity) (Density)
(1)
Thermal capacity is expressed in units of J/cm /K. 3

released when the substance cools down.
The specific heat capacity (also noted as specific
heat) of a substance is the heat capacity per unit
mass of that substance. Here we discuss specific heat
capacity using SI units (J/kg/K). These units can be
converted to cal/g/ C by dividing by 1000 and then
dividing again by 4.184. Specific heat capacity also
can be expressed in heat units per mole.
1
Consultant, 9299 William Cody Drive, Evergreen, CO 80439
USA; e-mail: dwwaples@cs.com.
2 Golder Associates, 44 Union Boulevard, Suite 300, Lakewood,
CO 80228 USA; e-mail: jwaples@golder.com.
Heat capacity (C) can be expressed at constant
volume (Cv) or constant pressure (Cp); in this pa-
per we use Cp. Heat capacity is isotropic; that is,
it is uniform in all directions. In this respect it con-
trasts strongly with thermal conductivity, which may
be highly anisotropic.
Heat capacities are of significance in modeling
thermal history, because when sediments and rocks
are heating up rapidly, the heat required to raise the
temperature of the rocks can represent a substan-
tial fraction of the total heat flux. The heat reach-
ing the upper sedimentary levels in a rapidly sub-
siding basin thus can be considerably less than the

97
1520-7439/04/0600-0097/1
C 2004 International Association for Mathematical Geology
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98
Figure 1. Temperature profiles calculated using BasinMod for hy-
pothetical section consisting of equal amounts of interbedded sand-
stone and shale deposited at constant rate of 1000 m/my. Radio-
genic contribution: not included. Basal heat flow: constant at 60
mW/m2 . Matrix conductivities: sandstone = 4 W/m/ C, shale = 1.5
W/m C. Porosity: calculated using exponential equation of Sclater
and Christie (1980). Total conductivities of layers: averaged har-
monically. BasinMod conductivity correction factors (for effects of
temperature): sandstone = 244, shale = 75. Matrix specific heat
capacities: 2250 kJ/m3 / C (2250 J/kg/K) for both lithologies. Basin-
Mod does not vary specific heat capacity as function of temperature.
Surface temperature: 20 C. Heavy line: temperature profile consid-
ering heat capacities. Thin line: temperature profile ignoring heat
capacities.
heat available for the deepest layers. Consequently,
geothermal gradients and subsurface temperatures
in areas of rapid sedimentation are lower than they
would be if sedimentation rates were lower. Figure 1
illustrates this point: a section consisting of equal
amounts of interbedded sands and shales 10 km thick
deposited at a rapid rate of 1 km/my, with a constant
basal heat flow of 60 mW/m2 , has a calculated temper-
ature of 325 C at 10 km depth when temperature is
calculated taking heat capacity into consideration, but
a higher temperature (375 C) and geothermal gradi-
ent when heat capacity is ignored.3
3
In reality, this example significantly underestimates the magnitude
of the problem. The temperature profile considering heat capac-
ity in Figure 1 was calculated using BasinModr software, which
does not vary the specific heat capacity of either the mineral mat-
ter or water as a function of temperature. As we see later, because
specific heat capacity is higher at higher temperatures, more heat
is absorbed by rocks at high temperature. The calculated tem-
perature of 325 C at 10 km depth is thus an overestimate, and
the real difference between the two gradients is greater than that
shown.
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Waples and Waples
Similarly, when erosion is fast, the heat released
upon cooling is added to the basal heat flow, resulting
in higher geothermal gradients. When sedimentation
or erosion are slow, however, the effect of heat capac-
ity is small, because the amount of heat taken up or
released by the rocks and sediments represents only
a small fraction of total heat flow, and thus does not
strongly affect the geothermal gradient.
Figure 1 shows that at a depth of 10 km there
can be a temperature difference of as much as 50 C
(>15% of the true temperature) when we consider
the heat capacity of the sedimentary rocks. Errors of
1030% in matrix and pore-fluid heat capacity (a re-
alistic appraisal of the situation in the current default
values and calculation functions in some software pro-
grams: see footnote 3) thus could lead to errors on
the order of 515 C in calculated subsurface temper-
atures. Errors of this magnitude could significantly
affect calculated amounts of hydrocarbon generation
or cracking. Because it is easy to avoid major errors in
heat capacity by selecting reasonable values for each
lithology at all temperatures, it would seem advisable
to do so.
Unfortunately, this area of investigation has been
almost totally ignored by researchers interested in
problems of basin modeling. This paper attempts to
fill that void by providing data and equations on spe-
cific heat capacities of rocks and minerals, and on the
temperature dependence of specific heat capacities of
those materials. Those values and equations then can
be used directly in modeling (both by software devel-
opers and by modelers).
OBJECTIVE
The immediate objectives of this paper are (1) to
provide values of and equations for specific heat ca-
pacities for solid materials (minerals and nonporous
rocks) at temperatures from 0 C to 1200 C, and (2) to
develop equations for calculating specific heat capac-
ities of mixtures of minerals and mixtures of litholo-
gies. A companion paper (Waples and Waples, 2004)
considers the specific heat capacities of fluids occur-
ring in rocks, and of porous rocks containing those
fluids in various combinations. The ultimate purpose
in providing these data is to help modelers describe
the specific heat capacities of real rocks with reason-
able accuracy under subsurface conditions in maturity
modeling and basin modeling, and to help model de-
velopers better define the effects of temperature and
pressure in their software.
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 99

HEAT CAPCITIES OF MINERALS

AND NONPOROUS ROCKS

Measured heat capacities of rocks include the

heat capacities of any pore fluids present in the sam-
ples analyzed. Because the specific heat capacity of
water is higher than that of any mineral, the measured
heat capacities of porous, wet rocks do not give a good
indication of the heat capacities of the solid materials.
Measured data obtained from rocks with significant
porosity therefore are not used in this study. Instead,
we focus on the heat capacities of minerals and non-
porous rocks.

Figure 3. Measured specific heat capacities plotted as function of

Reference Temperature
Specific heat capacities of minerals and non-
porous rocks increase substantially with temperature
(Figs. 2 and 3). Thus it is important to establish a stan-
dard reference temperature for comparing heat ca-
pacities of the various substances. In this study we
arbitrarily use 20 C as the reference temperature.
Unfortunately, specific heat capacity is not al-
ways measured at the same temperature in laboratory
investigations. For most rocks and minerals included
in this study, at least one measurement was available
at a temperature below 100 C, but the actual measure-
ment temperature differed. Table 1 shows the mea-
temperature for four nonporous rocks, showing general increase in
heat capacity with increasing temperature. Compare with Figure
2. Data for slate from Kappelmeyer and Haenel (1971). Data for
quartzite, basalt, marble, and serpentine from Cermak and Rybach
(1982).
sured specific heat capacities for the minerals used in
this study, and the temperature at which each mea-
surement was made.
Because of the strong temperature dependence
of specific heat capacity at low temperature, it was nec-
essary to adjust all measured specific heat capacities
to the value at the reference temperature. The method
for carrying out this adjustment is discussed in a later
section. For the moment let us simply work with the
specific heat capacities adjusted to 20 C, which are
shown in Table 1 and Figure 4.

Variation by Mineralogy

Specific Heat Capacity

The great majority of the specific heat capaci-

Figure 2. Measured specific heat capacities plotted as function
of temperature for four typical minerals, showing general in-
crease in heat capacity with increasing temperature. Irregular-
ity in heat capacity trend for quartz represents phase change
from quartz to quartz at about 580 C. Other minerals
also show rapid changes in heat capacity during phase changes.
Data for olivine from Kappelmeyer and Haenel (1974). Data
for quartz from Cermak and Rybach (1982). Data for anhydrite
from Goranson (1942). Data for fayalite from Roy, Beck, and
Touloukian (1981).
ties of minerals at 20 C are between about 600 and
900 J/kg/K, with a strong preference for values be-
tween 700 and 800 J/kg/K (Fig. 4 and Table 1). The
mean value for all the inorganic minerals in our
database is 660 J/kg/K, with a standard deviation of
235 J/kg/K. Specific heat capacities at 20 C of the inor-
ganic minerals in our data set differ from a low of 180
J/kg/K for bromyrite (AgBr) to a high of 1485 J/kg/K
for epsomite. The lowest values generally occur in
compounds that contain one or more heavy-metal
atoms (especially sulfides, silver halides, tungstates,
and some oxides and carbonates), whereas the high-
est values are for minerals such as epsomite, brucite,
and gypsum, which are either hydroxides or contain
significant amounts of water of crystallization. The
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100 Waples and Waples

Table 1. Measured Specific Heat Capacities for Various Classes of Minerals, and the Temperatures at Which the Measurements were Made.
In Some Data Sources the Measurement Temperature was Simply Specified as Room Temperature. In Those Situations the Temperature
was Assumed to be 20 C. Also Shown is the Specific Heat Capacity at the Reference Temperature of 20 C Calculated Using Equations
(18) and (19). When Multiple Values were Available in the Literature, a Typical Value was Selected. In Most Instances the Published Values
were in Good Agreement with Each Other. In a few Situations, However, the Published Values from Different Sources were Different. In
Those Instances a Maximum and Minimum Published Value were Included, Rather Than a Single Typical Value. Discrepancies may Reflect
Variations in Mineral Composition or Measurement Error. The Measured Specific Heat Capacity for Mirabilite Seems Suspiciously Low,
Because it Contains a Large Amount of Water of Hydration.

Cp (J/kg/K) at Thermal capacity

Density Measurement measurement Cp (J/kg/K) (J/cm3 /K) Measured Cp Density
Mineral 3
(g/cm ) temperature ( C) temperature
at 20 C at 20 C reference reference

Sulfides, arsenides, selenides,

stibnides, tellurides
Acanthite 7.254 0 320 335 2.43 M M
Argentite 7.2 150 350 282 2.03 M M
Arsenopyrite 6.05 20 400 400 2.42 M M
Berzelianite 6.749 0 420 440 2.97 G W
Bismuthinite 6.78 25 238 235 1.60 B W
Bournonite 5.83 50 310 292 1.70 G W
Braggite 10 25 190 188 1.88 B W
Chalcocite 5.65 20 510 510 2.88 M M
Chalcopyrite 4.2 20 534 534 2.24 D O
Cinnabar 8.15 20 215 215 1.75 M M
Clausthalite 8.269 20 187 187 1.55 M M
Cleiofan 4 20 500 500 2.00 M M
Cobaltite 6.25 58 410 380 2.37 M M
Covellite 4.7 0 490 513 2.41 G W
Dyscrasite 9.75 25 229 226 2.21 B W
Galena 7.55 20 210 210 1.59 M M
Greenockite 4.826 20 395 395 1.91 M M
Hauerite 3.481 20 660 660 2.30 M M
Marcasite 4.75 20 605 605 2.87 M M
Metacinnabar 7.66 20 205 205 1.57 M M
Millerite 5.374 0 506 530 2.85 M M
Molybdenite 4.65 20 574 574 2.67 D W
Nickeline 7.7 20 246 246 1.89 M M
Oldhamite 2.58 25 658 651 1.68 B W
Orpiment 3.49 20 475 475 1.66 M M
Proustite 5.57 50 340 320 1.78 G W
Pyrargerite 5.85 50 320 301 1.76 G W
Pyrite 5.05 20 510 510 2.58 M M
Pyrrhotite 4.6 0 594 622 2.86 G W
Realgar 3.58 20 435 435 1.56 M M
Sphalerite 4 0 450 471 1.88 G W
Stibnite 4.63 20 343 343 1.59 D W
Tellurobismuthite 7.815 100 203 175 1.37 B W
Troilite 4.74 0 606 634 3.01 G W
Wurtzite 4.04 20 520 520 2.10 M M
Heavy-metal halides
Bromyrite 6.477 20 180 180 1.17 M M
Calomel 7.15 0 214 224 1.60 B W
Cerargerite 5.571 20 395 395 2.20 M M
Cotunnite 5.8 25 276 273 1.58 B W
Iodyrite 5.684 20 205 205 1.17 M M
Marshite 5.68 25 285 282 1.60 B W
Nantokite 4.136 25 491 486 2.01 B W
Other halides
Carobbiite 2.56 20 795 795 2.04 M M
Chloromagnesite 2.32 0 805 843 1.96 G W
Cryolite 2.97 0 909 952 2.83 G W
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 101

Table 1. Continued

Cp (J/kg/K) at Thermal capacity

Density Measurement measurement Cp (J/kg/K) (J/cm3 /K) Measured Cp Density
Mineral (g/cm3 ) temperature ( C) temperature at 20 C at 20 C reference reference

Fluorite 3.185 20 900 900 2.87 M M

Fluorite 3.18 25 892 882 2.81 Y Y
Halite 2.16 25 926 916 1.98 Y Y
Sellaite 3.18 25 860 851 2.71 Y Y
Sylvite 1.987 25 975 965 1.92 Y Y
Villiaumite 2.802 20 1005 1005 2.82 M M
Heavy-metal oxides
Baddeleylite 5.725 20 455 455 2.60 M M
Ba Orthotitanite 5.8 25 900 890 5.16 Y Y
Braunite 4.79 20 660 660 3.16 M M
Bunsenite 6.62 20 595 595 3.94 M M
Cassiterite 6.95 20 375 375 2.61 M M
Cerianite 7.22 20 370 370 2.67 M M
Chromite 4.9 20 690 690 3.38 M M
Cuprite 6.075 20 460 460 2.79 M M
Eskolaite 5.23 20 770 770 4.03 M M
Franklinite 5.25 25 625 619 3.25 B W
Hematite 5.15 20 620 620 3.19 M M
Hercynite 4.258 20 720 720 3.07 M M
Ilmenite 4.75 25 858 849 4.03 Y Y
Limonite 3.65 20 921 921 3.36 D D
Litharge 9.33 20 220 220 2.05 M M
Magnetite 5.175 20 586 586 3.03 D W
Manganite 4.3 20 765 765 3.29 M M
Manganosite 5.365 20 685 685 3.68 M M
Minium 9.05 25 214 212 1.92 B W
Perovskite 4.02 25 833 824 3.31 Y Y
Pseudobrookite 4.7 25 870 861 4.05 Y Y
Pyrolusite 5 20 775 775 3.88 M M
Rutile 4.24 25 816 807 3.42 Y Y
Sr Metatitanite 5.11 25 873 864 4.42 Y Y
Tenorite 6.5 0 520 544 3.54 G E
Thorianite 9.79 20 234 234 2.29 M M
Titanomagnetite 4.37 25 874 865 3.78 Y Y
Uraninite 10.969 20 240 240 2.63 M M
Wuestite 5.745 20 730 730 4.19 M M
Zincite 5.66 0 480 502 2.84 G W
Other oxides
Anatase 3.84 25 820 811 3.12 Y Y
Arsenolite 3.87 25 567 561 2.17 B W
Bromellite 3.008 20 1020 1020 3.07 M M
Chalcedony 2.59 20 700 700 1.81 M M
Chrysoberyl 3.75 50 840 790 2.96 G W
Corundum 4.022 0 720 754 3.03 G W
Cristoballite 2.33 20 735 735 1.71 M M
Diaspore 3.4 20 1060 1060 3.60 M M
Geikielite 3.84 25 817 808 3.10 Y Y
Hydrargillite (Gibbsite) 2.34 25 1193 1180 2.76 B E
Lime 3.45 20 750 750 2.59 M M
Opal 2.1 20 725 725 1.52 M M
Periclase 3.55 20 970 970 3.44 M M
Quartz 2.648 20 740 740 1.96 M M
Spinel 3.6 20 820 820 2.95 M M
Titanite 3.5 25 818 810 2.83 Y Y
Tridymite 2.285 20 745 745 1.70 M M
Hydroxides
Brucite 2.38 35 1300 1260 3.00 G O, X
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102 Waples and Waples

Table 1. Continued

Cp (J/kg/K) at Thermal capacity

Density Measurement measurement Cp (J/kg/K) (J/cm3 /K) Measured Cp Density
Mineral (g/cm3 ) temperature ( C) temperature at 20 C at 20 C reference reference

Heavy-metal carbonates
Cerussite 6.55 20 330 330 2.16 M M
Malachite 4.05 57 740 687 2.78 G W
Rhodochrosite 3.7 0 700 733 2.71 G W
Siderite 3.944 20 740 740 2.92 M M
Smithsonite 4.434 20 660 660 2.93 M M
Strontianite 3.785 20 570 570 2.16 M M
Witherite 4.25 20 437 437 1.86 M M
Other carbonates
Aragonite 2.93 20 785 785 2.30 M M
Calcite 2.745 20 815 815 2.24 M M
Dolomite 2.84 20 870 870 2.47 M W
Magnesite 2.975 20 880 880 2.62 M M
Nitrates
Nitratine 2.215 20 1150 1150 2.55 M M
Nitre 2.109 0 1190 1246 2.63 G W
Heavy-metal sulfates
Anglesite 6.324 20 344 344 2.18 M M
Barite 4.25 20 540 540 2.30 M M
Celestite 3.95 20 590 590 2.33 M M
Other non-hydrated sulfates
Anhydrite 2.9 20 585 585 1.70 M M
Arcanite 2.66 20 715 715 1.90 M M
Thenardite 2.664 25 971 960 2.56 B W
Hydrated sulfates
Epsomite 1.677 32 1510 1472 2.47 G W
Gypsum 2.32 20 1070 1070 2.48 M M
Kieserite 2.571 9 1000 1025 2.64 G W
Phosphates
Apatite 3.225 20 700 700 2.26 M M
Berlinite 2.618 20 770 770 2.02 M M
Tungstates
Huebnerite 7.12 25 409 405 2.88 B W
Scheelite 6.12 20 440 440 2.69 M M
Tungstite 7.16 0 330 345 2.47 G W
Plagioclases
Albite 2.62 20 730 730 1.91 M M
Analcime 2.25 20 730 730 1.64 M M
Andesine 2.67 20 711 711 1.90 D W
Anorthite 2.76 20 711 711 1.96 D W
Labradorite 2.71 60 820 757 2.05 G O, X, D
Oligoclase 2.64 20 837 837 2.21 D W
Na-K Feldspars
Adularia 2.59 20 685 685 1.77 M M
Cancrinite 2.45 20 750 750 1.84 M M
Leucite 2.485 20 749 749 1.86 D W
Microcline 2.58 20 700 700 1.81 M M
Nepheline 2.6 20 800 800 2.08 M M
Orthoclase 2.6 20 628 628 1.63 D W
Sanidine 2.575 20 690 690 1.78 M M
Olivines
Fayalite 4.24 20 840 840 3.56 M M
Forsterite 3.222 27 820 808 2.60 R W
Monticellite 3.8 20 770 770 2.93 M M
Olivine 3.4 0 550 576 1.96 C D
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 103

Table 1. Continued

Cp (J/kg/ K) at Thermal capacity

Density Measurement measurement Cp (J/kg/ K) (J/cm3 / K) Measured Cp Density
Mineral (g/cm3 ) temperature ( C) temperature at 20 C at 20 C reference reference

Pyroxenes
Aegirine 3.25 20 780 780 2.54 M M
Augite 3.38 20 670 670 2.26 S W
Bronzite 3.38 20 810 810 2.74 M M
Diopside 3.3 20 711 711 2.35 D W
Hypersthene 3.34 20 796 796 2.66 D D
Jadeite 3.4 20 670 670 2.28 M M
Petalite 2.417 58 850 788 1.90 G W
Pyroxene 3.3 0 752 787 2.60 G W
Spodumene 3.1 60 900 831 2.58 G W
Micas
Biotite 3 20 770 770 2.31 S W
Muscovite 2.85 20 760 760 2.17 S W
Phlogopite 2.8 20 780 780 2.18 M M
Vermiculite 2.78 20 770 770 2.14 M M
Zeolites
Natrolite 2.35 20 760 760 1.79 M M
Amphiboles
Actinolite 3.2 20 705 705 2.26 M M
Amphibole 3.2 20 749 749 2.40 D W
Andalusite 3.15 0 770 806 2.54 G W
Asbestos 3.08 20 710 710 2.19 M M
Chlorite 2.8 20 600 600 1.68 M M
Clinoenstatite 3.4 25 787 779 2.65 B E
Kaolinite 2.65 0 930 974 2.58 G W
Kyanite 3.6 0 700 733 2.64 G W, D
Mullite 3.19 0 770 806 2.57 M M
Serpentine 2.55 20 650 650 1.66 M M
Sillimanite 3.25 0 743 778 2.53 G W
Topaz 3.525 50 840 790 2.79 M M
Tourmaline 3.08 20 540 540 1.66 M M
Tremolite 3 27 803 791 2.37 R W, D
Zircon 4.65 20 669 669 3.11 D W
Garnets
Almandine 3.8 20 750 750 2.85 M M
Andradite 3.86 0 750 785 3.03 M M
Beryl 2.77 55 840 783 2.17 M M
Dioptase 3.5 34 770 748 2.62 G W
Epidote 3.4 20 780 780 2.65 M M
Grossularite 3.594 127 713 593 2.13 R W
Pseudowollasonite 2.912 0 730 764 2.23 G X
Rhodonite 3.575 0 660 691 2.47 M M
Talc 2.8 20 750 750 2.10 M M
Wollastonite 2.845 0 695 728 2.07 M M
Miscellaneous
Boracite 2.94 0 796 833 2.45 G W
Gehlenite 3.038 0 750 785 2.39 G W
Hornblende 3.08 20 710 710 2.19 S O
Kerogen 1.2 1500 1.80
Moissanite 3.218 25 664 657 2.11 B W
Prehnite 2.92 50 840 790 2.31 G W
Willemite 4 25 546 541 2.16 B W

References: B = Blanke, 1989; C = Cermak and Rybach, 1982; D = Dortman, 1976; E = Geological Survey of Canada; G = Goranson, 1942;
M = Melnikova and others, 1975; O = Olhoeft and Johnson, 1989; R = Roy and others, 1981; S = Schon, 1996; W = Weast and Selby, 1967;
X = Roberts and others, 1990; Y = Rossini and others, 1956, Z = Robie and Stout, 1963.
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104
Figure 4. Histogram showing distribution of measured specific heat capacities of minerals
corrected to 20 C. Values on x-axis refer to maximum value in group. Data are taken from
Table 1. Mean (excluding kerogen) = 660 J/kg/K.
various types of silicates have specific heat capacities
that cluster near the middle of the range.
The specific heat capacity of kerogen has not
been published, but it can be estimated from that of
coal. As we shall see later, the specific heat capacity
of coal decreases with increasing maturity, as a di-
rect result of the increasing amount of polycyclic aro-
matic structures (van Krevelen, 1961). Because most
kerogens have less polycyclic aromatic character than
coals, their specific heat capacities should be higher.
This assumption is supported by data on oils, which
are dominated by aliphatic structures and generally
have only minor amounts of polycyclic aromatic ma-
terial. The specific heat capacity of oil near room tem-
perature is about 1850 J/kg/K (Gambill, 1957; see also
Waples and Waples, 2004). If we assume that a typ-
ical kerogen is intermediate in specific heat capac-
ity between an oil and a coal (specific heat capacity
1300 J/kg/K at room temperature: see next section),
we estimate the specific heat capacity for kerogen at
20 C to be about 1500 J/kg/K.
Thermal Capacity
Figure 5 shows that the variation in thermal ca-
pacity [specific heat capacity per unit volume: see
Eq. (1)] is similar to the variation observed in spe-
cific heat capacity per unit mass (Fig. 4). The mean
thermal capacity of the inorganic minerals in Table 1
and Figure 5 is 2.46 J/cm3 /K, with a standard devi-
Style file version Nov. 07, 2000
Waples and Waples
ation of 0.65 J/cm3 /K. The results in Figure 5 thus
are consistent with those obtained by Roy, Beck, and
Touloukian (1981), who noted that for most minerals
and impervious rocks the thermal capacity is equal
to 2.3 J/cm3 /K 20%. The data of Robertson (1988)
also show a similar distribution.
Minimum thermal capacities occur mainly in the
least-dense minerals, including kerogen, evaporite
salts, feldspars, and the various forms of SiO2 , as
well as in the dense sulfides (Table 1). The highest
thermal capacities occur in dense nonsulfide miner-
als, including heavy-metal oxides, pyroxenes, olivines,
and amphiboles. Figure 6 shows the relationships be-
tween thermal capacity and mineral density. Among
the low- and medium-density minerals ( < 4 g/cm3 :
Kobranova, 1989) that make up by far the dominant
portion of sedimentary rocks, there is a gradual in-
crease in thermal capacity with increasing density.
Among high-density minerals ( > 4 g/cm3 ), in con-
trast, thermal capacity declines with increasing den-
sity. This decrease is more pronounced if the precious
metals are included (Kobranova, 1989).
A regression line through the data for all low- and
medium-density inorganic minerals gives a predic-
tive relationship between mineral density and thermal
capacity at 20 C, where is mineral density in g/cm3
(Fig. 6):
Thermal capacity (J/cm3 /K) = 1.0263 exp(0.2697)
(2)
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 105

Figure 5. Histogram of thermal capacities for minerals at 20 C, derived from data in Table 1. Values on x-axis refer
to maximum value in group. Mean = 2.46 J/cm3 /K.

Equation (2) is moderately successful in predict-
ing the thermal capacity of the low- and medium-
density inorganic minerals in our data set. The
standard deviation of the error in prediction result-
ing from Equation (2) [that is, the difference be-
tween measured thermal capacity and that calcu-
lated using Eq. (2)] is 0.38 J/cm3 /K, which is 16%
of the mean measured value of 2.31 J/cm3 /K for this
data set. The median error in the calculated spe-
cific heat capacity [calculated by dividing the ther-
mal capacity obtained using Eq. (2) by density]
is 11%.

Figure 6. Thermal capacity at 20 C plotted against mineral density for all low-density
minerals in Table 1 except kerogen. Regression line establishes Equation (2) for estimating
thermal capacity of low- and medium-density rocks or minerals.
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106
Figure 7. Thermal capacity at 20 C plotted against mineral density for all minerals in Table 1.
Regression line establishes Equation (3) for estimating thermal capacity of high-density rocks or
minerals, shown as open diamonds. Solid diamonds are the low- and medium density minerals
shown in Figure 6 (not included in regression line). The large open circle on the left is kerogen.
A polynomial regression curve through the data
for all high-density minerals also yields a predictive
relationship between mineral density and thermal ca-
pacity at 20 C, where is mineral density in g/cm3
(Fig. 7):
Thermal capacity (J/cm /K) = 0.0123
3 4
+ 0.399 4.64 + 22.66 36.42
3 2
(3)
However, Equation (3) is less successful in pre-
dicting the thermal capacity of the high-density min-
erals in our data set than Equation (2) was for the
low-density minerals. Fortunately, these minerals nor-
mally make up only a tiny fraction of all minerals in a
given section, and therefore can be neglected for most
purposes.
Variation by Lithology
Table 2 shows a compilation of measured values
of specific heat capacity for nonporous rocks at a va-
riety of temperatures, as well as the calculated values
at our reference temperature of 20 C. Figure 8 shows
the same data in histogram form.
Coals behave somewhat differently from other
rocks. According to van Krevelen (1961), the spe-
cific heat capacity of coal depends strongly on car-
bon content, which in turn depends on coal rank.
Heat capacity of a coal changes during thermal evo-
lution as a result of chemical changes in the coal
structure.
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Waples and Waples
Using van Krevelens (1961) data, we have
derived Equation (4), which calculates specific heat
capacity as a function of the percent of carbon in the
coal.
Cp = 0.0000828C4 + 0.00955C3 + 0.505C2
105C + 4845 (4)
In Equation (4) Cp is in J/kg/K and C is the %
carbon in the coal. Figure 9 shows graphically the re-
lationship between specific heat capacity and carbon
content for coals.
Gambill (1957), citing Clendenin and others
(1949), expressed the specific heat capacity of coal as
a function of the volatile-matter content of the coal,
which, similar to carbon content, is a function of coal
rank. For bituminous and anthracite coals the specific
heat capacity (J/kg/K) is given by Equation (5),
where T is in C and V is the percent volatile matter
in the coal:
Cp = 4184 (0.2 + 0.00088T + 0.0015V) (5)
At our reference temperature of 20 C, Equa-
tion (5) reduces to
Cp = 910.4 + 6.276V (6)
Richardson (1992), in analyzing 25 coals and
related materials over a wide range of ranks (matu-
rity levels), derived a more complex empirical rela-
tionship for heat capacity as a function of volatile-
matter content (%) and temperature. He proposed
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 107

Table 2. Measured Specific Heat Capacities for Rocks, and the Temperatures at Which the Measurements were Made. In Data Sources
Where the Measurement Temperature was Simply Specified as Room Temperature the Temperature was Assumed to be 20 C. Also
Shown is the Specific Heat Capacity at the Reference Temperature of 20 C Calculated Using Equations (18) and (19). When Multiple Values
were Available in the Literature, a Typical Value was Selected. In Most Situations the Published Values were in Good Agreement with
Each Other. In a few Instances, However, the Published Values from Different Sources were Different. In Those Situations a Maximum and
Minimum Published Value were Included, Rather Than a Single Typical Value. Discrepancies may Reflect Variations in Mineral Composition
or Measurement Error.

Cp (J/kg/K) at Thermal capacity

Density Measurement measurement Cp (J/kg/K) (J/cm3 /K) Measured Cp Density
Rock type (g/cm3 ) temperature ( C) temperature at 20 C at 20 C reference reference

Amphibolite 3.01 20 700 700 2.11 Y G

Amphibolite 3.01 20 1134 1134 3.41 S, D G
Andesite 2.66 20* 815 815 2.17 S O
Anhydrite 2.95 20 590 590 1.74 Y Y
Anhydrite 2.96 20 940 940 2.78 C D
Apatite 2.95 20 700 700 2.07 Y Y
Argillite 2.69 20 850 850 2.29 Y Y
Basalt 2.87 0 858 898 2.58 K O
Clay 2.68 20 860 860 2.30 B D
Coal 1.35 1300 1.76 V V
Diabase 2.79 0 699 731 2.04 K D
Diabase 2.79 20 860 860 2.40 D D
Diorite 2.87 20 1140 1140 3.27 C O
Dolerite 2.9 20 900 900 2.61 C O
Dolomite 2.8 20 900 900 2.52 Y Y
Dunite 2.55 20 720 720 1.84 Y Y
Epidosite 3.27 20 540 540 1.77 Y Y
Gabbro 3 20 650 650 1.95 Y Y
Gabbro 2.97 20 1000 1000 2.97 C O
Gneiss 2.7 20 770 770 2.08 C O
Gneiss 2.7 20 979 979 2.64 S, D O
Granite 2.65 20 600 600 1.59 Y Y
Granite 2.62 20 1172 1172 3.07 M M
Granodiorite 2.84 20 650 650 1.85 Y Y
Granodiorite 2.73 20 1046 1046 2.86 M M
Gypsum 2.37 20 1010 1010 2.39 R D
Gypsum-Anhydrite 2.68 20 710 710 1.90 Y Y
Harzburgite 3.20 27 771 759 2.43 T T
Homblendite 3.1 56 530 493 1.53 Y Y
Homfels 20 1470 1470 C
Ijolite 2.93 20 900 900 2.64 Y Y
Lherzolite 3.20 27 790 778 2.49 T T
Limestone 2.77 20 680 680 1.88 Y Y
Limestone 2.76 20 880 880 2.43 C W
Marble 2.76 20 883 883 2.44 R W
Marl 2.72 20 950 950 2.58 Y Y
Metapyroxenite 20 921 921 D
Microquartzite 2.625 20 950 950 2.49 Y Y
Migmatite 2.75 20 849 849 2.34 L L
Monchiquite 2.96 20 800 800 2.37 Y Y
Norite 2.99 20 670 670 2.00 Y Y
Orthogneiss 2.70 20 1347 1347 3.64 L L
Pegmatite 2.7 20 710 710 1.92 Y Y
Peridotite 3.19 20 1005 1005 3.21 D D
Peridotite, serpentinized 2.74 20 705 705 1.93 Y Y
Phyllite 2.72 20 1090 1090 2.96 C G
Plagiogranite 2.70 20 874 874 2.36 L L
Pyroxenite 3.24 20 660 660 2.14 Y Y
Pyroxenite 3.19 20 1000 1000 3.19 C D
Pyroxenite, serpentinized 2.53 20 1243 1243 3.14 Z Z
Quartz monzonite 2.64 27 892 879 2.32 R O
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108 Waples and Waples

Table 2. Continued

Cp (J/kg/K) at Thermal capacity

Density Measurement measurement Cp (J/kg/K) (J/cm3 /K) Measured Cp Density
Rock type (g/cm3 ) temperature ( C) temperature at 20 C at 20 C reference reference

Quartzite 2.64 0 699 731 1.93 K D

Quartzite 2.64 20 1013 1013 2.67 C, D D
Rischorrite 2.74 20 650 650 1.78 Y Y
Rischorrite 2.72 20 900 900 2.45 Y Y
Salt 2.16 20 880 880 1.90 C D
Sandstone 2.64 20 775 775 2.05 Y Y
Schist 2.77 20 790 790 2.19 Y Y
Schist 2.9 20 1096 1096 3.18 S, D O
Serpentinite 2.27 20 730 730 1.66 Y Y
Serpentinite 2.54 20 1005 1005 2.55 D D
Siderite 3.18 20 715 715 2.27 Y Y
Siltstone 2.68 20 910 910 2.44 Y Y
Slate 2.77 20 1113 1113 3.08 Z Z
Slate 2.78 0 707 740 2.06 K O
Syenite 2.82 20 460 460 1.30 Y Y
Sylvinite 2 20 560 565 1.13 Y Y
Talc 2.78 20 1000 1000 2.78 C W
Tuff 2.69 20 795 795 2.14 M M
Tuff 2.75 20 1090 1090 3.00 C G

Assumed; not specified in reference.

Note. References: B = Buntebarth, 1984; C = Cermak and Rybach, 1982; D = Dortman, 1976; G = Geological Survey of Canada; K =
Kappelmeyer and Haenel, 1974; L = Lyubimova et al., 1975; M = Moiseenko et al., 1970; R = Roy et al., 1981; S = Schon, 1996; T = Tkach
and Yurchak, 1972; V = van Krevelen, 1961; W = Weast and Selby, 1967; Y = Melnikova et al., 1975; Z = Dudarev and Tychinskiy, 1972.

Equation (7), where Cp is in J/g/K: K). For example,

Cp = 0.01((A + B(V) + C(V) + D/(V + 0.1)) (7)
2 A = PA0 + PA1 T + PA2 T2 (8)

In Equation (7) each of the values A, B, C, and Table 3 shows the values for the twelve constants
D is itself a quadratic function of temperature T (in required in Richardsons equations. He comments

Figure 8. Histogram showing distribution of measured specific heat capacities of

nonporous rocks corrected to 20 C. Values on x-axis refer to mean value in group.
Data are taken from Table 2. Mean = 938 J/kg/K.
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock
Figure 9. Specific heat capacity of coal plotted as a function of %
carbon in the coal. Symbols: measured values from van Krevelen
(1961). Line: Best-fit polynomial through the data (see Equation
(4)). Correlation coefficient r2 = 0.98.
that the average error in predicting heat capacity
within his calibration set was about 2% to 3% for
the calibrated temperature range from 300K to 600K.
Merrick (1983) developed a theoretical ap-
proach based on the Einstein model, and Coimbra
and Queiroz (1995) subsequently substantiated the
validity of his approach using measured data on
50 coals. However, their equations require knowl-
edge of calorific value in addition to volatile mat-
ter, and thus are applied less easily than those of
Richardson (1992). In any situation, direct applica-
tion of the model of Coimbra and Queiroz (1995) to
Richardsons (1992) data set showed only minor dif-
ferences in the predicted heat capacities.
The density of coal depends in a complex way
on coal rank (van Krevelen, 1961) as well as on coal
composition (Stach and other, 1975), but an average
density of 1.35 g/cm3 seems to be appropriate for ash-
free coal. Although the specific heat capacity of coal
is the highest of any mineral, coals low density re-
sults in thermal capacity that is lower than most other
lithologies. The Cp at 20 C calculated using equation
(1) is 1.755 J/cm3 /K.
Table 3. Constants for Equations (7) and (8). From Richardson
(1992)
A B C D
P0 0.5943 1.791 2.07 0.02985
P1 9.092E-03 1.507E-02 1.744E-02 5.248E-04
P2 7.340E-06 1.960E-05 2.209E-05 5.537E-07
19:56 Style file version Nov. 07, 2000
109
Mineralogy vs. Lithology
In comparing Figures 4 and 8 and the data in
Tables 1 and 2, it is evident that the measured spe-
cific heat capacities of nonporous rocks are on the
average considerably higher (mean excluding coal =
938 J/kg/K) than those of inorganic minerals (mean =
660 J/kg/K). The difference between the two data sets
cannot be the result our selection of an equation for
temperature correction, because all measurements
were made at relatively low temperatures, where cor-
rections are small and all correction functions yield
similar results (see next section). It also is difficult
to believe that the difference is caused by the pres-
ence of pore water, because the nonporous rocks
are mainly igneous, and thus have little intergranular
porosity. Fracture porosity would not be great enough
to affect measured heat capacities. A simple calcula-
tion shows that the nonporous rocks would have to
have an impossibly high average water-filled porosity
of more than 15% in order to account for the differ-
ence between the mean specific heat capacities of the
two groups.
Another possible explanation is that the mineral
database (Table 1 and Fig. 4) contains many unusual
ore minerals with lower specific heat capacities than
those of the minerals dominant in most rocks. How-
ever, removing all ore-forming minerals from the data
set only raises the mean specific heat capacity for the
main rock-forming minerals to 748 J/kg/K, a value
considerably below that for the nonporous rocks.
We suspect that the difference between the two
data sets is the result data quality. Robertson (1988)
has commented that heat capacities measured on
rocks using traditional methods are not particularly
reliable unless extreme care is taken. He therefore
prefers to calculate heat capacities of rocks from
their mineral contents, rather than measuring them
directly. Goranson (1942) had earlier made a similar
recommendation. This preference implies a greater
confidence on their part in measurements made on
minerals than on rocks.
Heat capacities measured as part of a series
of measurements at different temperatures support
Robertsons and Goransons idea. Series data are
probably more reliable than data in which only a
single measurement was made for each sample. The
mean of the specific heat capacities for nonore-
forming minerals measured at temperatures between
0 C and 27 C is 768 J/kg/K, whereas that for non-
porous rocks measured in the same temperature
range is actually slightly lower: 752 J/kg/K. That both
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110
these values are considerably closer to the average
value for minerals in Table 1 than to the average for
nonporous rocks in Table 2 suggests that the mea-
sured data for minerals measured at a single temper-
ature are in fact more reliable than those for rocks
measured at a single temperature.
We therefore conclude that measured specific
heat capacities for rocks are on the average about
15% higher than those for the dominant rock-forming
minerals. It seems that measured specific heat capac-
ities for rocks are frequently in error unless multiple
measurements at different temperatures were made.4
In a later section we will see how to overcome this
weakness in the rock database by calculating specific
heat capacities for rocks from data on their mineral
compositions or densities.
Temperature Dependence
Inorganic Minerals and Nonporous Rocks
Because Figures 2 and 3 show that the specific
heat capacities of individual minerals and nonporous
rocks increase with increasing temperature, it is useful
to have equations to calculate specific heat capacity
as a function of temperature. A number of workers
have developed empirical equations describing the
temperature dependence of specific heat capacity for
rocks and minerals. The original standard equation
was a polynomial function, usually terminated after
the quadratic term, in which the constants A, B, and
C were determined empirically for each substance:
Cp = A + BT + CT2 (9)
For example, according to Somerton (1992),
Gomaa (1973) used a quadratic equation to describe
the temperature dependence of thermal capacity of
sandstones:
Thermal capacity = 2.05 + 0.00381T + 3.35T2 (10)
where thermal capacity is in J/cm3 /K and T is in C.
Maier and Kelley (1932) eventually rejected th-
ese quadratic equations, claiming that Equation (11)
yielded a better overall fit:
Cp = A + BT + CT2 (11)
4 Scharli and Rybach (2001) recently have proposed what they
claim to be a reliable and simplified method for obtaining heat
capacities of rocks using rock fragments. The heat capacities they
obtained for rocks are consistent with those for most rock-forming
minerals.
Style file version Nov. 07, 2000
Waples and Waples
The form of Equation (11) is derived from
standard methods of working up calorimetric data
(Goranson, 1942). It has been applied by Kelley (1934,
1949, 1960), Goranson (1942), and England (1978),
and cited by others (e.g., Schon, 1996).
Equation (11) may be satisfactory in principle, es-
pecially at relatively low temperatures, but Englands
(1978) oft-cited version [Eq. (12), where T is in K and
Cp is in J/kg/K)] is not particularly good.
Cp = 754 (1 + 0.000614T 19280 T2 ) (12)
One problem is that Equation (12) is based on
limited data, and does not provide a good fit to those
data. Second, it uses the same constants and assigns
the same specific heat capacity to all rocks. Goranson
(1942), in contrast, used distinct constants A, B, and
C in Equation (11) for each mineral. His approach is
more scientifically reasonable, because Figures 2, 3,
10, and 11 clearly show that not all nonporous rocks
and minerals have the same specific heat capacity.
Haas and Fisher (1976) developed a more com-
plex polynomial to calculate the specific heat capacity
as a function of temperature:
Cp = a + 2bT + cT2 + gT0.5 + fT2 (13)
They characterized it as an extension of the
Maier-Kelley equation (11). Robie, Hemingway, and
Fisher (1978) used the same equation.
Holland (1981), however, pointed out that at
temperatures above 700-800K Equation (13) greatly
Figure 10. All available measured specific heat capacities of min-
erals plotted as function of temperature, showing general increase
in heat capacity with increasing temperature. Data from Roth and
Bertram (1929), Goranson (1942), Rossini and others (1956), Kap-
pelmeyer and Haenel (1971), Roy, Beck, and Touloukian (1981),
Cermak and Rybach (1982), and Blanke (1989).
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 111

Figure 11. Measured specific heat capacities plotted as function of temperature for
all nonporous rock samples in Table 2, showing general increase in heat capacity with
increasing temperature. Data from Kappelmeyer and Haenel (1971), Tkach and Yurchak
(1972), Roy, Beck, and Touloukian (1981), Cermak and Rybach (1982), and Robertson
and Hemingway (1995).

overpredicts heat capacity. He therefore simplified
Equation (13) to Equation (14) and recalibrated it
using some fabricated high-temperature data:
Cp = A + BT + CT2 + DT0.5
Robertson and Hemingway (1995) also have
used Equation (14).
Berman and Brown (1985) offered Equation (15)
and Fei and Saxena (1987) proposed Equation (16) in
an effort to provide functions that would work for
a large range of temperatures. They took particular
care that their equations would yield values that do
not exceed those predicted by the Petit-Dulong law
or the Einstein limit at high temperatures.
Cp = k0 + k1 T0.5 + k2 T2 + k3 T3 (15)
Cp = 3Rn 1 + k1 T1 + k2 T2 + k3 T3
+ (A + BT) + Cp0
In Equation (16) R is the gas constant, n is the
number of atoms per unit formula, the (A + BT) term
focuses on thermal expansion, and the Cp0 term takes
into consideration empirically a variation of factors,
including cation disordering, anharmonicity, and elec-
tronic contributions.
In his extensive compilation Blanke (1989) has
used Equation (17), which probably is not valid at
high temperatures.
(14) Cp = A + BT + CT2 + DT2 (17)
Equations (11)(17) all share an important lim-
itation: a different set of constants must be derived
for each mineral. Moreover, published data are for
minerals rather than for real rocks. Thus it is difficult
or impossible to develop general rules for predicting
values for materials that have not been directly mea-
sured.
We have taken a different approach in this study.
Whereas earlier workers have derived unique equa-
tions for the relationship between specific heat ca-
pacity (or thermal capacity) and temperature for each
mineral or each lithology they studied, we seek a more
(16) general solution. Our goal here is to develop a math-
ematical function that describes the general temper-
ature dependence of all rocks and minerals, and that
can be personalized easily for individual rocks and
minerals. To this end we have normalized the plots
of specific heat capacity vs. temperature by divid-
ing all measured specific heat capacities for a given
mineral or nonporous rock by the measured specific
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112
Figure 12. Normalized specific heat capacities plotted as function of
temperature for same minerals shown in Figure 10. Normalization
was carried out by dividing all reported specific heat capacities by
the value for same mineral at 200 C. Line represents best-fit third-
order polynomial. Correlation coefficient r2 = 0.62.
heat capacity for that mineral or nonporous rock at
200 C. (200 C was selected for convenience because
data were available at or near that temperature for
all samples.) Figures 12 and 13 show plots of nor-
malized heat capacities as a function of temperature
for minerals and nonporous rocks.
For both groups there is a high degree of con-
sistency in the trends of normalized specific heat ca-
pacities. A single third-order polynomial gives a rea-
sonable fit to each data trend in Figures 12 and 13
Figure 13. Normalized specific heat capacities plotted as function
of temperature for same nonporous rocks shown in Figure 11. Nor-
malization was carried out by dividing all reported specific heat
capacities by value for same rock at 200 C. Line represents best-fit
third-order polynomial. Correlation coefficient r2 = 0.93.
Style file version Nov. 07, 2000
Waples and Waples
Figure 14. Normalized specific heat capacities plotted as function
of temperature for all minerals and nonporous rocks shown in Fig-
ures 12 and 13. Line represents best-fit third-order polynomial.
Correlation coefficient r2 = 0.65.
(r 2 = 0.62 for minerals, 0.93 for nonporous rocks).
The trends for minerals and nonporous rocks are
similar, although not identical. The differences be-
tween nonporous rocks and minerals actually are
smallusually less than 1% at temperatures below
500 C, which are the temperatures of greatest inter-
est for most thermal-history modeling. (In contrast,
as we saw earlier, the nonnormalized values for rocks
were considerably higher than those for minerals.) We
therefore have combined the mineral and rock data
sets (Fig. 14) to obtain a single regression Equation
(18) for the normalized heat capacity (Cpn) of a min-
eral or a nonporous rock at any temperature T ( C):
CpnT = 8.95 1010 T3 2.13 106 T2
+ 0.00172T + 0.716 (18)
The correlation coefficient r2 for the combined
data set is 0.65. Because CpnT is unitless and valid for
any mineral or nonporous rock, it can be adapted to
calculate the specific heat capacity of any mineral or
nonporous rock in any units at any temperature T2 ,
provided a measured value (CpT1 in those same units
at any temperature T1 ) is available for that rock or
mineral:
CpT2 = CpT1 CpnT2 /CpnT1 (19)
For example, if the measured value of CpT1 =
0.200 cal/g/ C at a temperature of 66 C, the sam-
ples calculated specific heat capacity at our reference
temperature of 20 C (T2 ) is obtained in two steps.
First, Equation (18) is applied at both temperatures.
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 113

Figure 15. Specific heat capacity calculated using Equations (18) and (19) in this study,
plotted against specific heat capacity calculated using Equation (12), taken from England
(1978). See text for discussion. Solid diagonal line represents perfect agreement. Tempera-
ture increases as heat capacity increases. Temperatures used in calculations range from 0 C
to 1200 C. Point at which the two methods yield the same specific heat capacity is about
750 C.

This calculation yields CpnT2 = 0.750 and CpnT1 =
0.820. Next, applying Equation (19), we obtain
CpT2 = 0.183 cal/g/ C at 20 C, which is equivalent to
766 J/kg/K. Similarly, the value of Cp at 500 C for
the same sample is calculated to be 0.281 cal/g/ C =
1179 J/kg/K.
Figure 15 compares specific heat capacities calcu-
lated using Englands function [Eq. (12)] with those
calculated using Equations (18) and (19) at tempera-
tures ranging from 0 C to 1200 C. For Equations (18)
and (19) we used a typical specific heat capacity
of 770 J/kg/K at 0 C. Equation (12) yields lower spe-
cific heat capacities at temperatures up to 750 C. At
higher temperatures, however, Equation (12) yields
higher specific heat capacities than those calculated
using Equations (18) and (19) from this study.
Figure 16 compares specific heat capacities cal-
culated for granite and basalt using Equations (18)
and (19) with those calculated using Equation (11).
The constants in Equation (14) are those derived by
Robertson and Hemingway (1995) for those same
lithologies. For purposes of comparison, we have as-
sumed that our granite and basalt have the same
specific heat capacity as the granite and basalt of
Robertson and Hemingway (1995) at their low-
est measured temperature (0.8118 J/g/K for granite,
0.7973 J/g/K for basalt, both at 65.5 C). Agreement
between values calculated using our generalized func-
tions and that of Robertson and Hemingway (1995)
is equally good for both lithologies over the entire
range of temperatures (0 C750 C), with a maximum
difference of less than 4%.
The advantage of our equations to Equation (14)
of Robertson and Hemingway (1995) is that Equa-
tion (14) requires that different constants be devel-
oped for each lithology (see Fig. 16 caption). Because
those constants are only available for a few specific
samples of igneous rocks, Equation (4) is of little im-
mediate value in modeling sedimentary basins. Our
Equations (18) and (19), in contrast, can be used for
any type of rock.
Figure 17 shows calculated specific heat capaci-
ties of four abundant minerals calculated as a func-
tion of temperature using Equation (19). Together
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114 Waples and Waples

Figure 16. Specific heat capacity of granite (solid circles) and basalt (open squares)
calculated using Equations (18) and (19) in this study, plotted against specific heat ca-
pacity calculated using Equation (14), taken from Robertson and Hemingway (1995).
Values of constants in Equation (14) for granite: A = 2.29354; B = 1.9986 104 ;
C = 2.0526 104 ; D = 29.3049. For basalt: = 1.65291; B = 0.9541 104 ; C =
0.89296 104 ; D = 13.5666 (Robertson and Hemingway, 1995). See text for dis-
cussion. Diagonal line represents perfect agreement. Temperature increases as heat
capacity increases. Temperatures used in calculations range from 0 C to 750 C.

with kerogen (Fig. 18), the minerals shown in Fig-
ure 17 approximately define the maximum range
of variation in specific heat capacities of the major
minerals.
Figure 19 shows calculated specific heat capac-
ities for seven representative types of igneous and
metamorphic lithologies plotted as a function of tem-
perature. High-temperature values were calculated
using Equation (19) from knowledge of a single mea-
sured value at a low temperature. The high specific
heat capacity of serpentinite reflects its high water
content.
Figure 20 shows calculated specific heat capac-
ities of six sedimentary lithologies as a function of
temperature. For all lithologies except shale the cal-
culation was carried out as described for the igneous
and metamorphic lithologies. Because no measured
specific heat capacity data were available for shale,
the specific heat capacity at 20 C was calculated as a
function of matrix shale density using Equation (2).
Specific heat capacities of all lithologies as a func-
tion of temperature were then calculated using Equa-
tion (19).
The error associated with application of
Equations (18) and (19) to nonporous rocks is small.
Figure 21 shows the error (absolute value of the dif-
ference between the measured specific heat capacity
of nonporous rocks and that calculated using those
two equations) plotted as a function of measurement
temperature. The median error (see figure caption
for explanation) increases with increasing tempera-
ture. Except at high temperatures, the error is less
than 5%, and at the temperatures generally used in
basin modeling (<300 C) the error usually will be
less than 3%. For temperatures reached at the base
of the lithospheric upper mantle (1200 C) the typ-
ical error is only 10%, and is random rather than
systematic.
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock
Figure 17. Specific heat capacities of four abundant minerals calculated using Equation
(19), plotted as a function of temperature. Values for Cp at 20 C taken from Table 1.
Coal
As we have seen, Equations (5) and (7) calcu-
late the specific heat capacity of coal as a function
of temperature and coal rank (maturity), the latter
expressed as the volatile-matter content. Using the
equivalency charts of Hood, Gutjahr, and Heacock
(1975) and McCartney and Teichmuller (1972) (the
latter cited in Barker, 1989), we can convert the
volatile-matter content into vitrinite reflectance (Ro)
equivalents. Using a typical thermal history (geother-
mal gradient = 3 C/100 m; sediments heated at a rate
of 3 C/million years), we then can calculate the ap-
proximate temperature at which any given Ro value is
reached. Figure 22 shows the resulting plot of volatile-
matter content (V in %) as a function of temperature
T ( C). The relationship derived from Figure 22 is
V = 6.566 1012 T6 + 5.686 109 T5
1.831 106 T4 + 2.735 104 T3 0.01967T2
+ 0.4117T + 60.15 (20)
where T 270 C. At higher temperatures (T >
270 C), V is assumed to be 4%. Substituting V
from Equation (20) into Equation (5) yields, after
19:56 Style file version Nov. 07, 2000
115
simplification,
Cp = 4.1208 1011 T6 + 3.5686 108 T5
1.1491 105 T4 + 0.0017165T3
0.12345T2 + 6.2657T + 1214.3 (21)
Equation (20) can be substituted into Equation (7), if
that equation is preferred to Equation (5).
Equation (21) takes into account temperature
effects as well as maturity-related changes in coal
structure through the temperature variable, and thus
could be applied easily in existing modeling soft-
ware. Table 4 shows specific heat capacities of coals
of various ranks at 20 C calculated using Equations
(4)(7). Results obtained using the three different
sets of equations are consistent. Richardsons Equa-
tion (7) yields the lowest heat capacities, whereas van
Krevelens Equation (4) gives the highest. Using all
these equations, specific heat capacity at 20 C de-
creases as maturity (coal rank) increases (Fig. 23).
In contrast, Figure 22 shows the relationship be-
tween specific heat capacity and in-situ temperature
calculated using Equation (21). As with inorganic
minerals, specific heat capacity of coal increases with
increasing temperature.
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116
Figure 18. Specific heat capacity of coal as function of temperature from 0 C to 300 C,
calculated using Equation (21).
Merrick (1993) predicted that the heat capacity
of coal should reach a maximum at about 500 C and
then decrease somewhat. No experimental data are
available to test directly this hypothesis, and Equa-
tions (20) and (21) do not make that prediction. Thus
the application of Equations (20) and (21) at ex-
tremely high temperatures may not be valid.
Pressure Effects
Schon (1996) offered data showing that ther-
mal conductivity of igneous rocks increases by about
0.05% to 0.15% for every increase in pressure of
10 MPa (equivalent to about 600 m of rock col-
umn). The increase in thermal diffusivity () (thermal
conductivity () divided by thermal capacity (Cp):
Equation (22)) is even smaller: about 0.03% for ev-
ery 10 MPa (Schon, 1996).
= /(Cp) (22)
Cermak and Rybach (1973) noted that pres-
sure effects on thermal diffusivity are negligible com-
pared to temperature effects, because the increase
Style file version Nov. 07, 2000
Waples and Waples
in thermal diffusivity with increasing pressure par-
tially cancels the increase in thermal conductivity
in Equation (22). Substituting those increases into
Equation (22), and assuming that changes in density
with increasing pressure also are minor, we see that
the specific heat capacity at 10 MPa pressure is only
about 1.0007 times the specific heat capacity at atmo-
spheric pressure. This corresponds to an increase of
about 0.1% per km of rock column, an amount that
can be safely neglected.
Mixtures
Because rocks are composed of minerals, and be-
cause the thermal capacity of a mineral mixture is
simply the sum of the thermal capacities of its com-
ponents (Gambill, 1957; Holland, 1981; Robertson,
1988), the thermal capacity of a real rock can be cal-
culated as the weighted average of the thermal ca-
pacities of its mineral components. If the specific heat
capacity at 20 C of the mineral in question is avail-
able (for example, from Table 1), that value can be
used directly. Alternatively, if the themal capacity of
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock
Figure 19. Specific heat capacities of six abundant metamorphic and igneous rocks calculated
as function of temperature using Equation (19) and single measured value at low temperature
taken from Table 2.
the mineral is not known, it can be estimated using
Equations (2) or (3). Table 1 shows typical densities
at room temperature for a wide variety of minerals.
We then can calculate the specific heat capacity of in-
Figure 20. Specific heat capacities of solid material in four abun-
dant sedimentary rocks calculated as function of temperature us-
ing Equation (19). See text for discussion. Data at 20 C are from
Table 2.
19:56 Style file version Nov. 07, 2000
117
organic minerals as a function of temperature using
Equation (19), where CpT1 is the specific heat capac-
ity at 20 C. For kerogen we can use a specific heat
capacity of about 1500 J/kg/K at 20 C, as discussed
under Variation by Mineralogy. The heat capacity
of kerogen at other temperatures is calculated using
Equation (21). Finally, dividing the calculated thermal
capacity of the mixture by its density yields its specific
heat capacity.
Similarly, the thermal capacity of a mixture of
lithologies can be calculated as the weighted average
of the thermal capacities of its component lithologies.
One can use either measured values for specific heat
capacity of individual lithologies, or those calculated
from densities of the lithologies. As an example, let
us take a rock unit that is 100 m thick, consisting of
various thin beds. Let us assume that the sum of the
thicknesses of shale beds is 30 m, that of the sand-
stones is 3 m, and that of the limestones is 67 m.
Let us further assume that the shales have an aver-
age TOC content of 2% (by weight), and that the
inorganic portion of the shales is estimated to con-
sist of 90% clay and 10% quartz. Let us also suppose
that the sandstone is fairly typical (60% quartz, 20%
feldspars (mainly orthoclase), 20% granitic lithic frag-
ments), and that the limestone is slightly dolomitic
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118 Waples and Waples

Figure 21. Median error in specific heat capacity plotted as function of measurement tem-
perature ranges for nonporous rocks. Error was calculated as absolute value of difference
between the measured specific heat capacity and that calculated using Equations (18) and
(19). Values at high temperatures show considerable scatter because data are sparse.

(5%), with the remainder calcite. Table 5 shows these
data, together with the estimation of the specific heat
capacity and the thermal capacity of each layer, and
of the entire rock unit.
We obtain the results in Table 5 by first calcu-
lating the volume of organic matter in the shales, af-
ter converting weight percent to volume percent. We
then estimate the specific heat or thermal capacity of
each component from data in Tables 1 and 2. Using
a specific heat capacity of 1500 J/kg/K for kerogen
and assuming a typical density5 of 1.2 g/cm3 , we cal-
culate the thermal capacity of kerogen to be about
1.8 J/cm3 /K. The thermal capacity of quartz given in
Table 1 is 1.96 J/cm3 /K. Table 1 also gives 2.24 J/cm3 /K
as the thermal capacity of calcite, 2.47 J/cm3 /K as that
for dolomite, and 1.63 J/cm3 /K as that for orthoclase.
From Table 2 we can obtain the specific heat capacity
for granite as an average of the two different samples
listed: 886 J/kg/K. Multiplying this value by a typical
density for granite (2.635 g/cm3 ), we obtain a thermal
capacity for granite of 2.33 J/cm3 /K.

5 Smith (1961) measured a density of 1.07 g/cm3 for highly aliphatic

Figure 22. Volatile-matter content of coals as function of subsurface
temperature. Volatile-matter/Ro relationship taken from Hood,
Gutjahr, and Heacock (1975). and McCartney and Teichmuller
(1972), cited in Barker (1989). Volatile-matter contents at low ma-
turities are estimated. Ro-temperature relationship estimated by
modeling at typical heating rate. Equation for regression line: V =
6.566 1012 T6 + 5.686 109 T5 1.831 106 T4 + 2.735
104 T3 0.01967T2 + 0.4117T + 60.15.
kerogen from the Green River Shale. Humic coal, which has a
highly aromatic structure, has a density of about 1.35 g/cm3 (van
Krevelen, 1961). We therefore estimate the density of a typi-
cal kerogen to be intermediate between those two extremes. It
should be noted that this value is somewhat lower than most of
the kerogen densities reported by Kinghorn and Rahman (1980)
and Nwachukwu and Barker (1985).
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock 119

Table 4. Specific Heat Capacity of Coal at Various Maturity Levels (Ro, % Volatile Matter, and % Carbon are Cross-Correlated as Shown in
the Footnotes. Specific Heat Capacity was Calculated Using Equations (4)(7). Temperatures Required to Reach the Various Ro Levels were
Calculated Using the Ro Kinetics of Burnham and Sweeney (1989) Applied to a Typical Burial History. They do not Apply in all Situations,
but are Generally Valid, and are Required for Calculations Using Equations (5) and (7)

In-situ % Cp at in-situ Cp at in-situ

Ro temperature Volatile % Cp at 20 C Cp at 20 C Cp at 20 C temperature temperature
Coal rank (%)2 ( C)1 Matter2,3 Carbon3 (Equation (4)) (Equation (6)) (Equation (7)) (Equation (5)) (Equation (7))

Surface 0.2 20 62 60 1353 1300 1189 1300 1189

Begin HV Bituminous C 0.5 90 47 70 1257 1205 1115 1463 1368
Begin HV Bituminous B 0.65 112 41.5 76 1212 1171 1097 1510 1420
Begin HV Bituminous A 0.75 126 39 78 1195 1155 1090 1545 1457
Begin MV bituminous 1.2 163 29 85 1111 1092 1067 1619 1541
Begin LV bituminous 1.5 179 22 88 1058 1048 1049 1634 1561
Begin Semianthracite 1.9 195 14.5 91 991 1001 1015 1646 1553
Begin Anthractie 2.5 217 8 95 871 961 947 1686 1511

1 Calculated
using modeling.
2 From Hood and others (1975).
3 From McCartney and Teichmuller (1972), cited in Barker (1989).

Clay is a bit more difficult, because we do not
have data on smectite and illite. The only clays listed
in Table 1 are chlorite and kaolinite, which are not typ-
ical of most clays. Let us therefore estimate the ther-
mal capacity of typical clays from their density using
Equation (2). The result using a density of 2.7 g/cm3 ,
is 2.16 J/cm3 /K.
We then multiply each of the thermal capacities
by the thickness of each component, and sum the con-
tributions. As Table 5 shows, the thermal capacity of
a column of this rock 100 m thick is 22.06 kJ/cm2 /K.
The average thermal capacity of the entire rock unit
is thus 2.206 J/cm3 /K.
Alternatively, we can estimate the thermal ca-
pacity from the average grain density of the rock unit,
which is calculated in Table 5 to be 2.713 g/cm3 . Us-
ing Equation (2), we then can estimate the average
thermal capacity of the rock unit as 2.167 J/cm3 /K.

Figure 23. Specific heat capacity of coals of different ranks (maturity levels) as measured by
vitrinite reflectance, calculated using Equations (4) (solid diamonds), (6) (open squares),
and (7) (solid triangles). See Table 4 for data.
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120 Waples and Waples

Table 5. Sample Calculation of Thermal Capacity of an Inhomogeneous Rock Unit. See Text for Description and Discussion

Mineral Mineral Thermal Thermal

Mineral Mineral component component volume capacity capacity
Lithology Thickness (m) components density weight % % within layer (J/cm3 / K) (kJ/cm2 / K)

Shale 30
25.9 Clay 2.7 86.3 2.16 5.59
2.9 Quartz 2.648 9.7 1.96 0.57
1.2 TOC (kerogen) 1.2 2 4.0 1.8 0.22
Limestone 67
63.6 Calcite 2.745 95.0 2.24 14.25
3.4 Dolomite 2.84 5.0 2.47 0.84
Sandstone 3
1.8 Quartz 2.648 60.0 1.96 0.35
0.6 Feldspar 2.6 20.0 1.63 0.10
0.6 Granite 2.635 20.0 2.33 0.14
Rock Unit 100 2.712 2.167a 22.06
2.206b

a Calculated using Equation (2).

b Calculated as the weighted average of the thermal capacities of the various components.

This estimated value differs by less than 2% from CONCLUSIONS

the value of 2.206 J/cm3 /K calculated by the more-
detailed method outlined.
That the thermal capacity of the rock unit is
slightly lower than the mean for all the minerals in
this study (2.45 J/cm3 /K) is consistent with the absence
of ore-forming minerals in these lithologies. It also is
clear from Figure 6 that sedimentary rocks will on
the whole have lower matrix thermal capacities than
igneous rocks, because they are on the average less
dense. In contrast, ultramafic rocks and other high-
density rocks (or any sedimentary rocks with large
proportions of minerals from such source areas) will
have high thermal capacities. Conversely, evaporites
and coals will tend to have abnormally low thermal
capacities.
This example shows that the concept of thermal
capacity (specific heat capacity expressed per unit vol-
ume) and the values of thermal capacity are useful
for modeling. Modeling software (or modelers) need
only multiply the thermal capacity by the thickness of
the rock unit in question to calculate the specific heat
capacity of that rock unit.
The process outlined here is obviously too
tedious to be carried out by hand for each model-
ing project. However, it would be easy to construct a
software program to perform such calculations au-
tomatically. Individual modelers could construct a
spreadsheet outside their basin-modeling software
and simply import the resulting values. Alterna-
tively, software developers, could build the calculation
scheme into their software.
Specific heat capacity data are available for many
minerals. Where unavailable, specific heat capacity
can be estimated with reasonable confidence from
mineral density. For low- and medium-density min-
erals specific heat capacity increases with increasing
density, whereas for the rarer high-density minerals it
tends to decrease. Specific heat capacities of mixtures
of minerals (e.g., nonporous rocks) can be estimated
either from the density of the mixture or as a weighted
average of the specific heat capacities of the compo-
nent minerals. Specific heat capacities of sedimentary
rocks tend to be lower than those of ultramafic ig-
neous rocks, but similar to those of felsic and mafic
rocks. Coal is exceptional in having an unusually high
specific heat capacity that decreases with increasing
coal rank.
The thermal capacity of any material is the spe-
cific heat capacity calculated per unit volume, by mul-
tiplying the specific heat capacity by the density of the
material. The thermal capacity of a mixture of solid
materials can be calculated as the weighted average
of the thermal capacities of all its components.
The specific heat capacity of any mineral or
nonporous rock (including kerogen and coal) at
any temperature can be calculated using generalized
equations developed in this paper. Uncertainty is on
the order of 5%. Specific heat capacity of all solids
increases substantially with increasing temperature
from 0 C to about 400 C, and then increases more
slowly at higher temperatures.
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Specific Heat Capacities of Rocks, Minerals, and Subsurface Fluids: Minerals and Nonporous Rock
Specific heat capacity of rocks plays an impor-
tant role in controlling heat flow and geothermal
gradient whenever rocks are heating up or cooling
down quickly (that is, during rapid burial or rapid ero-
sion). Errors of the magnitude introduced by uncer-
tainties and errors in specific heat capacities of rocks
within modeling software programs could affect deep
temperatures by as much as 5 to 15 C when erosion or
burial is rapid. Use of the data and equations provided
in this paper could eliminate much of this potential
error.
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