JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 108, NO. B3, 2139, doi:10.

1029/2002JB001783, 2003

Compensation effect for electrical conductivity and its applications

to estimate oxygen diffusivity in minerals
Xiaoping Wu and Yong-Fei Zheng
Department of Earth and Space Science, University of Science and Technology of China, Hefei, China

Received 23 January 2002; revised 5 November 2002; accepted 3 December 2002; published 7 March 2003.
[1] The compensation effect for electrical conductivity is observed for minerals such as
calcite, corundum, enstatite, ferrosilite, olivine, leucite, and periclase, which is referred to a
linear correlation between the natural logarithm of preexponential factor and activation
energy for the electrical conductivity in each mineral. It is shown that the electrical
conductivity due to different conducting species tends to converge to a constant at a
characteristic temperature in each mineral. On this basis, the preexponential factor for the
oxygen diffusion coefficient is calculated from the electrical conductivity by the Nernst-
Einstein equation, while the activation energy for oxygen diffusion is determined by
anion porosity. The estimated oxygen diffusion coefficients from the electrical conductivity
in minerals obey the compensation law well, and the linear compensation equation is in
good agreement with that from the experimentally determined oxygen diffusion data.
Experimentally determined cation diffusion coefficients also test the validity of our method.
Comparison between the estimated oxygen diffusion coefficients and the determinations by
the ionic porosity method shows that the present method provides useful constraints on
the other empirical model to predict diffusion coefficient. INDEX TERMS: 3914 Mineral
Physics: Electrical properties; 3630 Mineralogy and Petrology: Experimental mineralogy and petrology; 5109
Physical Properties of Rocks: Magnetic and electrical properties; 5120 Physical Properties of Rocks: Plasticity,
diffusion, and creep; 5139 Physical Properties of Rocks: Transport properties; KEYWORDS: electrical
conductivity, compensation effect, diffusivity, anion porosity
Citation: Wu, X., and Y.-F. Zheng, Compensation effect for electrical conductivity and its applications to estimate oxygen diffusivity
in minerals, J. Geophys. Res., 108(B3), 2139, doi:10.1029/2002JB001783, 2003.

1. Introduction ionic species in minerals. Thus empirical predicting methods

are highly desirable. Fortier and Giletti [1989] presented a
[2] Oxygen is the most abundant element in the Earth.
simple relationship for estimating hydrothermal oxygen
Study of the rates of oxygen isotope exchange by self-
diffusivity from total ionic porosity. Muehlenbachs and
diffusion in rock-forming minerals can provide important
Connolly [1991] proposed a similar relationship for predict-
data for interpretation of thermal histories in geological
ing anhydrous oxygen diffusivity from anion porosity.
processes [Giletti, 1985, 1986]. Experimentally determined
Zheng and Fu [1998] established an empirical model for
oxygen diffusion data for rock-forming minerals have been
predicting oxygen diffusivity from anion porosity under both
growing recently [Freer, 1981; Giletti and Yund, 1984; Cole
anhydrous and hydrothermal conditions. The empirical
and Ohmoto, 1986; Farver and Giletti, 1989; Sharp, 1991;
models can provide useful extrapolation of existing exper-
Farver, 1994; Ryerson and McKeegan, 1994]. However,
imental diffusion data. However, they were originally estab-
they are still considerably less abundant than what is
lished in terms of the compensation effect of diffusion from
required in geochemical applications because of difficulties
existing experimental diffusion data. It is well known that
in laboratory investigations. Recently atomistic simulation
errors in the experimental diffusion data and their resultant
methods have been proven a very promising theoretical
compensation relationship may be large (particularly in
method to predict diffusional properties. By defining an
preexponential factor), which will result in considerable
interatomic potential function to describe the total energy
uncertainties in predicted diffusion coefficients. On the other
of a system in term of atomic positions, Wright et al. [1995,
hand, the empirical models are usually evaluated by a
1996] employed the atomistic approach to investigate the
comparison between the predicted diffusivities and the
diffusion of oxygen in grossular garnet and albite. However,
known experimental diffusion data, which is not to test the
the methodology used does not allow the calculation of validity of the empirical models independently. Therefore
absolute diffusion rates. In this regard, there is no established investigations on the empirical model incorporating the other
model to theoretically predict the diffusion coefficients of properties of mineral or experimental measurements are high
desirable.
Copyright 2003 by the American Geophysical Union. [3] Electrical conductivity in minerals is used in studies
0148-0227/03/2002JB001783$09.00 of mineral structure, electronic and ionic transport pro-

ECV 1-1
ECV 1-2 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION
cesses. Ionic motion dominates electrical transport in
many kinds of silicate glasses. Therefore studying elec-
trical transport is an important alternative approach to
understanding diffusion behavior. The increased sensitivity
of electrical measurements in comparison to concentration
measurements and the opportunities to change polarities
and frequencies allow access to properties and phenomena
which are beyond the reach of normal diffusion measure-
ments. The electrical conductivity can be measured at
very low temperature where conventional diffusion meas-
urements are not feasible anymore, and the electrical
conductivity can be measured in situ in high temperature
melts where classical diffusion measurements invariably
study quenched products. In this study, we present the
compensation effect for electrical conductivities in calcite,
corundum, enstatite, ferrosilite, olivine, leucite and peri-
clase, and calculate the preexponential factors D0 for
diffusion coefficient from electrical conductivity in these
minerals. This provides a relatively independent method
to investigate oxygen diffusivity as well as cation diffu-
sivity through measurements of electrical conductivity in
minerals.
2. Theoretical Background
[4] The relationship between electrical conductivity and
diffusion coefficient is given by the Nernst-Einstein
equation
s ¼ Dz2 e2 n=ðkT Þ; ð1Þ
where D is the diffusion coefficient, z is the valence of the
conducting species, e is the charge of the electron, n is the
number per unit volume of the conducting species, k is
Boltzmann’s constant, and T is the absolute temperature.
[5] Diffusion is a thermally activated process, Arrhenius
diffusion relation is written as:
D ¼ D0 expðQ=RT Þ; ð2Þ
where D0 is preexponential factor (in cm2 s1), Q is
activation energy (in KJ mol1), and R is gas constant.
Therefore the temperature dependence of the conductivity
will be of the common form
s ¼ s0 expðE=kT Þ; ð3Þ
in which s0 (in S m1) and E (in eV) are preexponential
factor and activation energy of electrical conductivity,
respectively. It is noticed that the activation energy E for
electrical conductivity and the activation energy Q for
diffusion coefficient have different units; the equivalent
value of 1 eV is 96.485 KJ mol1 (1 eV = 96.485 KJ
mol1).
[6] Electrical conductivity in a material is the sum of the
conduction of each charge carrier (or defect) type acting in
parallel. In general, all defects are present in some amount
in every crystal and each contributes to the total conductiv-
ity. Usually only one or two types of defects dominate under
a given set of thermodynamic conditions. Plots of the
logarithm of electrical conductivity versus 1/T that cover
an extended range of temperature frequently show one or
two linear regions. The variations in slope can be caused
either by transition from one dominant conducting species
to another or by a transition from extrinsic to intrinsic
conductivity. Each linear region is then described by an
expression of the form of equation (3). Thus more precise
and mechanistically more meaningful form is
s ¼ s01 expðE1 =kT Þ þ s02 expðE2 =kT Þ; ð4Þ
where the subscripts 1 and 2 refer to the two different lines.
[7] Gautason and Muehlenbachs [1993] calculated ionic
conductivity for the lower mantle from oxygen diffusivity in
(Mg, Fe)SiO3 perovskite by Nernst-Einstein equation (1).
However, there are few calculations of oxygen diffusion
coefficient from electrical conductivity by the Nernst-Ein-
stein relation for the purpose of geosciences application.
The problem is that many minerals are mixed conductors
with electrical and ionic conductivities. If equation (1) is
used to estimate diffusion coefficient from conductivity
measurements, one has to separate partial conductivities
due to individual ions from total conductivity, which is very
difficult because of complicated conductivity mechanism in
silicate minerals. In fact, the activation energy for oxygen
diffusion is completely different from the activation energy
for electrical conductivity in most minerals, which shows
oxygen ion is not dominant conducting species. It is there-
fore difficult to determine the activation energy Q in
Arrhenius oxygen diffusion equation (2) from electrical
conductivity in those minerals.
[8] The activation energy Q for oxygen diffusion can be
determined by the atomistic simulation methods [Wright et
al., 1995, 1996]. However, a more feasible method we use
in this study is to empirically determine Q for oxygen
diffusion by anion porosity (f) in minerals. Actually, the
rate of oxygen diffusion in minerals is principally controlled
by the void space in the crystal, and its activation energy is
the obstacle which must be overcome by oxygen diffusion.
Obviously, the activation energy for oxygen diffusion is
related to anion porosity. Connolly and Muehlenbachs
[1988] observed that anion porosity is proportional to the
activation energy of oxygen diffusion. Zheng and Fu [1998]
illustrated a high degree of negative correlation between
anion porosity and activation energy for oxygen diffusion
experimentally determined under anhydrous and hydrother-
mal conditions, respectively. The anion porosity can be
accurately calculated from crystal-chemical parameters.
Thus the activation energy Q in Arrhenius oxygen diffusion
equation (2) can be determined.
[9] Many et al. [1955] were the first to note a linear
correlation between preexponential factor and activation
energy for electrical conductivity in a mineral, which is
generally referred to as the compensation effect. We will
show that if the compensation effect exists in a mineral,
electrical conductivities due to the different conducting
species approach a constant in the mineral at a given
temperature which is called the characteristic temperature.
Thus the electrical conductivity conducting by oxygen ion
as well as cation is assumed to be the constant at the
characteristic temperature even though we do not under-
stand the conduction mechanism in the mineral, and it can
be used to determine another parameter D0 in Arrhenius
oxygen diffusion relation by the Nernst-Einstein equation.
 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION ECV 1-3

Table 1. High-Temperature Electrical Conductivity of Minerals Given in the Format s = A1 exp (E1/kT )
Temperature T, Pressure log A1,
Mineral K P, GPa S m1 E1, eV Comments References
Caclite, CaCO3(Cc) Mirwald [1979]
573 – 773 6.15 0.1
773 – 998 1.15 0.9
998 – 1073 4.22 0.2
1073 – 1258 1.00 1.5
1258 – 1473 3.48 2.0
Corundum, Al2O3 (Coru) Pappis and Kingery [1961]
Single crystal 1573 – 1998 5.60 2.97 fO2 = 105Pa
1573 – 1873 3.96 2.62 fO2 = 1Pa
1898 – 1998 11.71 5.50 fO2 = 1Pa
1573 – 1873 5.01 2.84 fO2 = 105Pa
1898 – 1998 13.01 5.80 fO2 = 105Pa
Leucite (Lu) Maury [1968a, 1968b]
Rocca Monfina, 673 – 898 3.81 0.91
K0.96Na0.04AlSi2O6 698 – 1173 0.80 0.37
Synthetic, KAlSi2O6 673 – 898 3.40 0.84
898 – 1173 1.32 0.48
Synthetic, RbAlSi2O6 673 – 1173 3.64 0.89
Polycrystalline, (Mg,Fe)SiO3 Seifert et al. [1982]
En100 (Enstatite) 550 – 1000 2.0 3.25 1.59
En90Fs10 550 – 1050 2.0 3.00 1.40
En80Fs20 500 – 1020 2.0 2.80 1.18
En50Fs50 510 – 1020 2.0 2.15 0.80
En20Fs80 510 – 1010 2.0 2.10 0.55
Fs100 (Ferrosilite) 520 – 950 2.0 2.05 0.42
Temperature T, Pressure P, s = A1exp(E1/kT)
Mineral K GPa + A2exp (E2/kT)a Comments References
Olivine, polycrystalline  
1:99 1:45
San Carlos Olivine, 1063 – 1673 Roberts and Tyburczy [1991]
12:65 4:87
(Fo91) (Mg0.91, Fe0.09)SiO4
 
2:40 1:60
Model (SO2), 998 – 1773 Constable et al. [1992]
9:17 4:25
(Fo91) (Mg0.91, Fe0.09)SiO4
 
1:67 1:38
Model (SO1), 1373 – 1773 Shankland and Duba [1990]
8:70 3:90
(Fo90) (Mg0.91, Fe0.09)SiO4

Periclase (Pc) Sempolinski and Kingery

[1980a, 1980b]
 
Single crystal 40 ppm Al 1473 – 1773 1:23 1:92 f o2 103  104 Pa
7:14 3:81

 
1:23 1:92
1473 – 1773 f o2  1 MPa
5:87 3:66
 
2:68 2:11
320 ppm Fe 1473 – 1773 f o2 103  104 Pa
7:48 3:68
 
2:68 2:11
1473 – 1773 f o2  101 Pa
6:57 3:49
 
2:68 2:11
1473 – 1773 Fo2  1 MPa
5:94 3:08
 
2:97 2:16
400 ppm Al 1473 – 1773 f o2 103  104 Pa
8:40 4:07
 
2:97 2:16
1473 – 1773 f o2  1 MPa
5:16 3:24
a
Values in braces are fits to the two-term expression s = A1 exp (E1/kT ) + A2 exp (E2/kT ), where the top line is A1 and E1 and the bottom line is A2
and E2. Pressures are 1 bar total unless otherwise stated and fO2 is the oxygen fugacity.
ECV 1-4 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION
We also show that the method in this study is valid for the
determinations of cation diffusivities.
3. Compensation Effect for Electrical
Conductivity
[10] The relation of the natural logarithm of preexponen-
tial factor ln s0 (s0 in S m1) and activation energy E (in
eV) for the electrical conductivity takes the general linear
form approximately [Gutmann and Lyons, 1967]:
Ln s0 ¼ a þ b E; ð5Þ
where a and b are the constants. Equation (5) is generally
referred to as the compensation effect which were
observed in many organic crystals [Eley, 1967; Eley et
al., 1968; Rosenberg et al., 1968; Johnston and Lyons,
1970] and many inorganic semiconductors, such as TiO2,
Fe2O3 , BaTiO 3 [Mooser and Pearson, 1960]. The
compensation effect for electrical conductivity has been
also observed in certain ionically conducting glasses by
Hughes and Isard [1972] and in silicate melts by Tyburczy
and Waff [1983].
[11] We examine published experimental data for electrical
conductivity in minerals. Table 1 lists the electrical conduc-
tivity data and relevant references, which also can be found in
the compilation of Tyburczy and Fisler [1995]. The param-
eters s0 and E are different in each of the experimental
investigations for each mineral under different temperature
range, impurity content or oxygen fugacity etc. However, we
observe positive correlation between ln s0 and E in each
mineral. Figure 1 illustrates compensation trends between ln
s0 (s0 in S m1) and E (in eV) in calcite, corundum, enstatite,
ferrosilite, olivine, leucite, and periclase, respectively. The
coefficients a and b of fitted regression line for compensation
trends, as well as linear correlation coefficients R, are listed in
Table 2. The high degrees of correlation between ln s0 and E
show significant compensation effect for the electrical con-
ductivity in calcite, corundum, enstatite, ferrosilite, olivine,
leucite, and periclase.
[12] It is necessary to explain the compensation plot
(Figure 1) for the conductivity in olivine. The conductivity
of olivine is described by the sum s0i exp (Ei/kT ) as the
form of equation (4), s0i and Ei are the preexponential
factor and activation energy particular to conduction mech-
anism i. The low-temperature term s1 = s01 exp (Ei/kT )
and high-temperature term s2 = s02 exp (Ei/kT ) are
similar to the single mechanism form of equation (3).
Therefore the parameters (s01, E1) and (s02, E2) in equation
(4) represent two points in the compensation plot for
olivine. The conductivity data for olivine in Table 1 are
three different fits with the form of equation (4), each of
which has low-temperature parameters and high-temper-
ature parameters. Thus there should be six points fitting a
line in the compensation plot (Figure 1) for the conductiv-
ity in olivine. Similarly, the conductivity data for periclase
in Table 1 are seven different fits with two terms, there are
Figure 1. (opposite) Compensation plots of activation energy E (in eV) versus the natural logarithm of preexponential
factor ln s0 (s0 in S m1) for electrical conductivity in calcite, corundum, enstatite, ferrosilite, forsterite, leucite, periclase,
respectively. The data and relevant references are given in Table 1.
10 points fitting a line in the compensation plot for
periclase (Figure 1) except for four overlapping points.
The correlation between ln s0i and Ei for olivine, as well as
periclase, just shows that the compensation effect for
electrical conductivity is due to different conduction mech-
anisms in each mineral, which will be discussed below.
4. Investigation of the Compensation Effect for
Electrical Conductivity
[13] If the electrical conductivity due to a conducting
species or conduction mechanism in a substance is
expressed as the form of equation (3), its preexponential
factor s0 and activation energy E satisfies the compensation
equation (5) for this substance, then the electrical conduc-
tivity can be written as the form
ln s ¼ ln s0  E=kT ¼ a þ ðb  1=kT ÞE: ð6Þ
Suppose we write
b  1=kT0 ¼ 0;
then
T0 ¼ ðbk Þ1 ;
where T0 is called the ‘‘characteristic temperature’’ of the
substance. This implies that if the compensation effect
exists in the substance, the electrical conductivity due to
each conducting species or conduction mechanism tends to
converge to a constant sC = exp(a) at the characteristic
temperature T0. The calculated values of T0 and sC for
calcite, corundum, enstatite, ferrosilite, olivine, leucite, and
periclase are also listed in Table 2.
[14] In order to further investigate the problem, Arrhenius
plots of the electrical conductivity due to the different
mechanisms or species in olivine are shown in Figure 2.
First, we consider the parameters of the preexponential
factor and activation energy for olivine conductivity in
Table 1. Shankland and Duba [1990] used equation (4) to
fit the experimental conductivity data because of indications
that two conduction mechanisms operate in the temperature
range 1200– 1500C; Roberts and Tyburczy [1991] showed
the grain interior conductivity of San Carlos olivine displays
a change in slope and is fit with two straight lines, which
may be relate to the change in charge carrier observed by
Schock et al. [1989]; Constable et al. [1992] suggested that
the low-temperature parameters (s01, E1) and high-temper-
ature parameters (s02, E2) are to be electronic (polarons) and
ionic (Mg vacancies) conduction mechanisms, respectively.
As discussed above, although the mechanisms according to
these parameters are different, however, six straight lines of
Arrhenius plot for olivine approximately intersect at the
point A (T0, sC) in Figure 2, the values of T0 and sC in
olivine are listed in Table 2. Furthermore, Roberts and
WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION ECV 1-5
ECV 1-6 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION

Table 2. Coefficients a and b for Linear Compensation Trends in studies also showed that the solubility of hydrogen at 300
Mineralsa MPa is 20– 80 ppm H/Si. Then the conductivity due to H
Mineral a b R T0, K sC, S m1 diffusion is calculated by the Nernst-Einstein equation (1) as
Calcite(Cc) 13.35954 10.76330 0.989 1078 1.58  106
Karato [1990] did, the average solubility of 50 ppm H/Si is
(±1.11434) (±0.93448) used in the calculation. Similarly, the conductivities in olivine
Corundum(Coru) 6.10165 6.13162 0.997 1892 2.24  103 due to Fe-Mg interdiffusion and Co-Mg interdiffusion are
(±1.10894) (±0.58864) calculated by the Nernst-Einstein equation (1) using the
Enstatite(En) 3.41619 2.49779 0.979 4644 3.04  101 diffusion coefficients listed in Table 3. Figure 2 shows that
(±0.27953) (±0.25881)
Ferrosilite(Fs) 3.41619 2.49779 0.979 4644 3.04  101 the Arrhenius plots of the ionic conductivities due to H
(±0.27953) (±0.25881) diffusion, Fe-Mg interdiffusion, and Co-Mg interdiffusion
Olivine(Ol) 5.38972 6.68005 0.993 1736 4.56  103 also intersect approximately at the point A(T0, sC).
(±1.28858) (±0.39592) [15] Previously, we have shown that if the compensation
Leucite(Lu) 3.02489 12.89082 0.999 900 4.86  102
(±0.15466) (±0.21074)
effect exists in the mineral, electrical conductivities due to
Periclase(Pc) 8.63542 6.72729 0.971 1724 1.78  104 the different conducting species approach a constant at
(±1.88904) (±0.58864) the characteristic temperature T0. Therefore the electrical
a
Values in parentheses denote the statistical errors. The linear correlation conductivity conducting by oxygen ion is assumed to be
coefficient R, characteristic temperature T0 and the conductivity constant sC the constant sC at T0 even without knowing anything
in minerals are also listed. about the dominate conduction mechanism in the mineral.
On this basis, we determine D0 in Arrhenius oxygen
diffusion relation (2) by the Nernst-Einstein equation
Tyburczy [1991] presented the grain boundary conductivity from the electrical conductivity, while the activation
of olivine which has an activation of 2.47 eV and a preexpo- energy Q for oxygen diffusion is determined by anion
nential factor of 4.36  105 S m1. Figure 2 shows that the porosity.
Arrhenius plot of the grain boundary conductivity also
intersects the other lines at the same point A(T0, sC) approx-
imately, it gives another evidence to support the opinion
5. Relation of Activation Energies for Oxygen
above. Second, we discuss the ionic conductivity due to
cation diffusion. The values of hydrogen diffusivity in olivine Diffusion to Anion Porosity
experimentally determined by Mackwell and Kohlstedt [16] Dowty [1980] suggested that anion porosity gives a
[1990] at 300 MPa are listed in Table 3. Their experimental direct measure of atomic packing density in the structure of

Figure 2. Arrhenius plots of the electrical conductivity due to the different mechanisms or species in
olivine: 1 – 3, conductivities according to the low-temperature parameters (s01, E1) from Roberts and
Tyburczy [1991], Constable et al. [1992], Shankland and Duba [1990], respectively; 4 – 6, conductivities
according to the high-temperature parameters (s02, E2) from Roberts and Tyburczy [1991], Constable et
al. [1992], Shankland and Duba [1990], respectively; 7, the grain boundary conductivity from Roberts
and Tyburczy [1991]; 8, conductivity due to Fe-Mg interdiffusion; 9, conductivity due to Co-Mg
interdiffusion; and 10, conductivity due to H diffusion.
 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION ECV 1-7

Table 3. Experimental Diffusion Data in Olivine and Corresponding Referencesa

Diffusing P, f O2 , Q, ln D0
Mineral Component T, C MPa MPa kJ mol1 cm2 s1 References
Olivine (Fo91Fa9) H 800 – 1000 300 ‘‘wet’’ IW 130 0.51 Mackwell and Kohlstedt [1990]
Olivine (Fo92Fa8) -fayalite powder Fe-Mg interdiffusion 1125 – 1200 0.1 1013 243 4.05 Buening and Buseck [1973]
Olivine (Mg2SiO4) – (Co2SiO4) Co-Mg interdiffusion 1300 – 1400 0.1 air 526 14.48 Morioka [1980]
a
Q is activation energy, ln D0 is the natural logarithm of the preexponential factor. Conditions of the experiment including temperature T, pressure P, and
oxygen fugacity fo2 are also listed.

crystal minerals and thus it has a strong influence on ionic
diffusion through given structure. The anion porosity is
defined as the percentage of unit cell volume not occupied
by anion according to
f ¼ ð1  VA =VC Þ  100;
where VC is the volume of unit cell and VA is the volume of
anions in the unit cell which is calculated by use of anion
radii and assumption of spherical geometry.
[17] Obviously, the activation energy is the obstacle
which must be overcome by oxygen diffusion. Therefore
activation energy for oxygen diffusion is related to the anion
porosity. The higher the anion porosity of a mineral, the
lower the activation energy of oxygen diffusion and the
greater the rates of oxygen diffusion in the mineral. Zheng
and Fu [1998] illustrated high degree of correlation between
anion porosity f and activation energy Q (in kJ mol1) for
oxygen diffusivity experimentally determined under anhy-
drous and hydrothermal conditions, respectively. These
were written as
Qdry ¼ 20:78ð1:88Þf þ 1513:4ð22:9Þ
Qwet ¼ 11:89ð2:62Þf þ 894:9ð13:9Þ
where the superscripts dry and wet denote the anhydrous
and hydrothermal conditions, respectively. The anion
porosity in minerals can be calculated from crystal-chemical
parameters, and then activation energy for oxygen diffusion
can be calculated from equations (8) and (9). Table 4 lists
anion porosity and calculated activation energy for oxygen
diffusion in calcite, corundum, enstatite, ferrosilite, olivine,
leucite, and periclase under anhydrous and hydrothermal
conditions, respectively. The activation energy Q for
oxygen diffusion can be determined from anion porosity
in these minerals. Then the preexponential factor D0 in
equation (2) can be calculated to solve for oxygen diffusion
coefficient, which will be discussed in section 6.
6. Estimate of Oxygen Diffusivity in Minerals by
ð7Þ
Electrical Conductivity
[18] The basic relationship between electrical conductiv-
ity and diffusion coefficient is given by the Nernst-Einstein
equation (1). Considering the correlation factor of the
diffusion process which is a measure of the correlation
between successive atomic jumps, we express the diffusion
coefficient as [Chakraborty, 1995]


D ¼ HR s kT = z2 e2 n ; ð10Þ
if the electrical conductivity s in equation (10) is due to the
motion of one kind of ion. If D is the self-diffusion
coefficient, then HR is the Haven ratio related to the
correlation factor. The Haven ratio HR usually has a value
between 0.1 and 1, so that even without knowing anything
about its magnitude, it is possible to get a reasonable (within
ð8Þ an order of magnitude) estimate of diffusion rates if
conductivity is measured. Because the experimental values
ð9Þ of HR are not available for the minerals discussed in this
study, we simply let the natural logarithm of Haven ratio be
the average of ln 1.0 and ln 0.1 in next calculations, i.e., ln
HR = 1.15.
[19] Now the problem is that many minerals are mixed
conductors with electrical and ionic conductivities. Second,
there may be more than one kind of ion responsible for
electrical conduction. Therefore, if equation (10) is used to
estimate diffusion coefficient from conductivity measure-
ments, one has to separate partial conductivities due to
individual ions from total conductivity. Although these can
be obtained through the measurement of electrical trans-

Table 4. Density r, Anion Porosity f, Activation Energy Q, and the Natural Logarithm of Preexponential Factor ln D0 for Oxygen
Diffusion in Mineralsa
r, Qdry, ln Ddry
0 , Qwet,
Mineral g cm3 f, % kJ mol1 kJ mol1 ln Ddry-s
0 kJ mol1 lnDwet
0 lnDwet-s
0

Calcite (Cc) 2.71 62.80 208 11.04 8.64 148 13.92 15.33
Corundum (Coru) 3.98 43.61 607 10.26 14.19 376 1.83 0.50
Enstatite (En) 3.22 55.44 361 2.87 4.43 236 9.28 7.67
Ferrosilite (Fs) 3.99 57.64 316 5.31 5.54 210 10.67 8.28
Olivine (Ol) 3.22 55.90 352 3.38 0.82 230 9.85 7.63
Leucite (Lu) 2.50 69.78 63 18.79 13.36 65 18.32 13.10
Periclase (Pc) 3.56 55.14 368 2.54 1.08 239 9.10 10.08
a
Here D0 is in cm2 s1, and ln D0dry and ln D0drys are determined by ionic porosity method [Zheng and Fu, 1998] and electrical conductivity (this study),
respectively.
ECV 1-8 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION

Figure 3. Compensation plot from Zheng and Fu [1998] on the basis of the experimental data for
oxygen diffusion under anhydrous and hydrothermal conditions. The estimated oxygen diffusions in
leucite from the electrical conductivity and the ionic porosity method, which is denoted as Lus and Luf,
respectively, are joined.

ference number (the fraction of current carried by a
particular kind of ion), there is almost no measurement
of electrical transference number in minerals which we
concern.
[20] As pointed out above, electrical conductivity tends to
converge to the constant sC at the characteristic temperature
T0 regardless of different conducting species because of the
compensation effect. The ionic conductivity due to oxygen
diffusion is also equal to sC at the characteristic temperature
T0, then equation (10) at the characteristic temperature T0 is
written as


D0 expðQ=RT0 Þ ¼ HR sc kT0 = z2 e2 n : ð11Þ
Therefore the preexponential factor D0 for oxygen diffusion
is expressed as

the linear equations (Table 2), however, the statistical errors
D0 ¼ H R sC expðQ=RT0 ÞkT0 = z2 e2 n ; ð12Þ
where sC = exp(a), T0 = (bk)1, and the activation energy
(Q) for oxygen diffusion is determined by equations (8) and
(9) under anhydrous and hydrothermal conditions. For
oxygen diffusion, z = 2 and e is charge of the electron; n is
the number per unit volume of oxygen ion is expressed as
NA rL
n¼ ; changes in anion radii and the volume of unit cell have
M
where NA is the Avogadro’s number, M is the molecular
weight, r (in g cm3) is the density given by Smyth and Bish
[1988], and L is the number of oxygen atoms in a molecular.
Thus the preexponential factor D0 can be calculated through
measurements of electrical conductivity from equation (12).
The natural logarithms of preexponential factors ln D0
determined by electrical conductivity from equation (12) for
oxygen diffusion in calcite, corundum, enstatite, ferrosilite,
olivine, leucite, and periclase under anhydrous and hydro-
thermal conditions are listed in Table 4.
[21] Uncertainties in the Arrhenius parameters for oxygen
diffusion determined from electrical conductivity can arise
from several sources. First, the Haven ratio HR, which
usually varies between 0.1 and 1, results in a calculation
error in estimates of diffusion rates within an order of
magnitude. It cannot be resolved in this study. Second,
errors in the experimental data of electrical conductivity
result in uncertainties in the compensation trends (Figure 1).
Usually, errors associated with the slopes (b) are much
smaller than errors associated with the intercepts (a) of
in the intercepts (a) are still less than 1.3 except for that in
the intercept of the compensation trends in periclase because
of large scatter. Because ln sC = a in equation (12), the
uncertainty of ln D0 derived from errors in the compensa-
tion trends is not very large. The third is the calculation of
activation energy (Q) from anion porosity. Although com-
pression and thermal expansion of the unit cell of the
minerals may affect the size of anion porosities to some
extent under the mantle conditions, errors due to the
minimal effect on the empirically estimated results. On the
other hand, the empirical equations (8) and (9) are derived
from a thorough examination of the experimental data for
oxygen diffusion, therefore, the uncertainties in the empiri-
 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION ECV 1-9

Figure 4. Compensation plot of activation energies Q versus the natural logarithm of preexponential
factor ln D0 for the oxygen diffusion estimated from the electrical conductivity under anhydrous and
hydrothermal conditions. Solid line denotes the best fit to the calculated oxygen diffusion coefficients
(listed in Table 4), Abbreviations are also given in Table 4.

cal activation energies are not worse than those from the
experimental determinations.
7. Discussion
[22] Winchell [1969] suggested that diffusion in silicate
glasses obeys the compensation law in the Arrhenius
relation, i.e., diffusion of different species shows a positive
correlation between ln D0 and Q. A similar effect was noted
by Hofmann [1980] for cation diffusion in basalt. Hart
[1981] demonstrated that different diffusion species in
silicate minerals exhibit a well-defined compensation effect.
On the basis of a thorough examination of the experimental
data for oxygen diffusion, Zheng and Fu [1998] illustrated a
common compensation trend (in Figure 3) between ln D0 (in
cm2 s1) and Q (in KJ mol1) for oxygen diffusion in
minerals under both anhydrous and hydrothermal condi-
tions, represented by the linear equation:
ln D0 ¼ 0:0534ð0:0062ÞQ  22:15ð3:96Þ; ð13Þ
where the linear correlation coefficient is R = 0.887.
[23] According to the compensation law for diffusivity,
the oxygen diffusion coefficients, which are calculated
through experimentally determined electrical conductivities
in minerals (listed in Table 4), should obey the compensa-
tion equation similar to equation (13). We examine the
compensation effect based on the oxygen diffusion coef-
ficients from conductivity in Table 4, the compensation
trend is illustrated in Figure 4 with higher correlation
coefficient R = 0.954. The linear equation is expressed as
ln D0 ¼ 0:0505ð0:0046ÞQ  19:40ð1:39Þ: ð14Þ
Certainly, equation (14) is very close to equation (13). The
slopes only have 5% of error, and the intercepts of two
linear equations are also close to each other if the scatter
degree SD = 3.96 is considered in equation (13). Therefore
equations (14) and (13) are in good agreement within the
experimental error band.
[24] The experimental data for oxygen diffusivity in
calcite are available under both anhydrous and hydrother-
mal conditions. As shown in Figure 5, the good match exists
between the calculated oxygen diffusivity and the exper-
imental determination of Labotka et al. [2000] under the
anhydrous condition. The estimate for hydrothemal oxygen
diffusion is also in fair agreement with the known exper-
imental data of Farver [1994], there is only about an order
of magnitude difference between them.
[25] Zheng and Fu [1998] presented an ionic porosity
method to predict oxygen diffusion coefficient in minerals.
They determined the activation energy Q for oxygen dif-
fusion from equations (8) and (9) under anhydrous and
hydrothermal conditions, and then estimated the preexpo-
nential factor D0 from equation (13).The preexponential
factors D0 estimated from the ionic porosity method by
Zheng and Fu [1998] are also listed in Table 4. About or
less than an order of magnitude differences exist between
the estimates from the electrical conductivity and those from
the ionic porosity method except for a few results such as the
oxygen diffusion coefficients in leucite. Zheng and Fu
[1998] indicated that errors associated with experimental
diffusion data are the most fundamental to the uncertainties
in the empirical Arrhenius parameters for oxygen diffusion.
Because there are often a wide range of reported values for
oxygen diffusion coefficient for a given diffusion property
of a mineral, usually the error in activation energy is
ECV 1 - 10 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION

Figure 5. Comparison of the estimates from conductivity with the experimental determinations for
oxygen diffusion in calcite under anhydrous and hydrothemal conditions. Sources are 1, this study; 2,
Labotka et al. [2000]; and 3, Farver [1994].

relatively small, but sometimes the preexponential factor D0
differs by as much as several orders of magnitude. This
results in large scatter in actual correlation (see Figure 3). For
instance, the significant calculation error of oxygen diffusion
in leucite may be due to the very large scatter degree of its
experimental data in Figure 3. However, we add the oxygen
diffusion coefficients in leucite estimated from the electrical
conductivity and the ionic porosity method under anhydrous
condition to the compensation plot in Figure 3; it can be seen
that they are in agreement within the experimental error band
though a relatively great difference exists between them, and
both have large errors as compared to the experimental
diffusion coefficient in leucite.
[26] Although the activation energy Q (in kJ mol1) for
cation diffusivity cannot be calculated by the empirical
correlation like equation (8) or (9), we use the experimen-
tally determined activation energy Q to estimate the pre-
exponential factor D 0s for cation diffusivity through
measurements of electrical conductivity by equation (12)
and then compare it with the experimentally determined
preexponential factor to test the validity of the method in
this study for the determinations of cation diffusivities.
Table 5 shows the results of Ca diffusion in calcite, H
diffusion, Fe-Mg interdiffusion, and Co-Mg interdiffusion
in olivine. The experimentally determined cation diffusion
coefficients and those calculated from electrical conductiv-
ity are well matched with about an order of magnitude
differences.
[27] We give a brief summary of this section as follows:
1. The electrical conductivity and its compensation effect
can be used to estimate the oxygen diffusivity as well as the
cation diffusivities. The uncertainties are no worse than the
experimental determinations.
2. The compensation trend equation (13) comes directly
from experimental oxygen diffusion coefficients, and
equation (14) comes indirectly from the experimental
electrical conductivities. They are obtained by the different
methods, but there is a good match between them. It shows
that the method is very valid and the equation (14)
calculated from the electrical conductivity would place
useful constraints on the common compensation trend for
the oxygen diffusion.
3. We have suggested that electrical conductivities in
each mineral due to different conducting species obey the

Table 5. Comparison Between the Experimentally Determined Cation Diffusion Coefficients (Q, ln D0) and Those Calculated From the
Electrical Conductivity (lnD0s)
Q, ln D0, ln Ds0 ,
Mineral Species kJ mol1 cm2 s1 References cm2 s1
Calcite Ca 271 2.99 Fisler and Cygan [1999] 0.52
Olivine (Fo91Fa9) H 130 0.51 Mackwell and Kohlstedt [1990] 1.84
Olivine (Fo92Fa8) -fayalite powder Fe-Mg interdiffusion 243 4.05 Buening and Buseck [1973] 6.00
Olivine(Mg2SiO4) -(Co2SiO4) Co-Mg interdiffusion 196 10.80 Morioka [1980] 9.26
526 14.48 13.59
 WU AND ZHENG: ELECTRICAL CONDUCTIVITY AND DIFFUSION
compensation trend, on this basis, the diffusion coefficients
are calculated by the electrical conductivity. Our results test
the validity of the method. From this aspect, the suggestion
is also proven to be appropriate.
8. Conclusions
[28] It is not a simple process to calculate oxygen diffusion
coefficient through measurements of electrical conductivity
by the Nernst-Einstein equation. Because the compensation
effect for electrical conductivity in minerals exists, the
electrical conductivity conducting by oxygen ion or cation
is equal to a constant at the characteristic temperature T0
without understanding the dominate conduction mechanism.
On this basis, the preexponential factor of oxygen diffusion
coefficients is calculated through the measurement of the
electrical conductivity. The results match the experimen-
tally determined oxygen diffusion coefficients as well as
those determined by the ionic porosity method within error
band. Experimentally determined cation diffusion data also
test the validity of the method. With an increase in the
measurements of electrical conductivity, it is necessary to
further develop the method in order to place more accurate
constraint on the other empirical model to predict diffusion
coefficient.
[29] Acknowledgments. This work was supported by funds from the
Natural Sciences Foundation of China (40033010). Thanks are due to
Stephen Park and two anonymous reviewers for their constructive com-
ments. The authors also thank J. A. Tyburczy, Arizona State University, and
K. Spitzer, TU-Freiberg Germany, for their help.
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X. Wu and Y.-F. Zheng, Department of Earth and Space Science,
University of Science and Technology of China, Hefei 230026, China.
(wxp@ustc.edu.cn)