Society of Petroleum Engineers of AIME PAPER

6200 North Central Expwy. NUMBER SPE 6609

Dallas, Texas 75206

Time Dependent Electrical

Properties of Rock-Solution Systems
by
H. C. Weed, A. J. Piwinskii, and P. R. Keller,
Lawrence Livermore Laboratory

THIS PAPER IS SUBJECT TO CORRECTION

©Copyright 1976
American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc.
This paper was prepared for the 1977 SPE-AI ME International Symposium on Oilfield and Geothermal Chemistry,
held in La Jolla, California, June 27-28, 1977. Permission to copy is restricted to an abstract of not more than 300
words. Illustrations may not be copied. The abstract should contain conspicuous acknowledgement of where
and by whom the paper is presented. Publication elsewhere after publication in the JOURNAL OF PETROLEUM
TECHNOLOGY or the SOCIETY OF PETROLEUM ENGINEERS JOURNAL is usually granted upon request to the
Editor of the appropriate journal, provided agreement to give proper credit is made. Discussion of this paper is
invited.

ABSTRACT porosity, pore solution concentration,

The electrical conductivity of 25.4-mm
diameter cylindrical cores of sedimentary and
igneous rocks was measured at a frequency of
1 kHz under ambient conditions after saturation
in tap water and in 0.1 M NaCl solution.
Between measurements, each rock was stored in
contact with its own separate solution that at
the start of the experiment was either tap
water or 0.1 M NaCl solution. Eighteen rocks
having porosities between 0.07 and 42 percent
were investigated; ten were sedimentary, eight
were igneous. All solution conductivities were
measured employing a dip cell. The time
dependence of the conductivity was investigated
as well as the range of validity of Archie's
law. The formation factor and conductivity of
rock specimens and their reacting solutions
display time-dependent behavior up to 8,000
hours. The formation factor and electrical
conductivity depend on the salinity of the pore
fluid, the rock porosity and permeability, and
the clay minerals present in the rock.
INTROOOCTION
We are currently investigating rock-
solution interaction and its effect on electri-
cal properties of rocks as a function of time,
References and illustrations at end of paper.
frequency, specimen aspect ratio, and Soxhlet
extraction procedures. This work is part of a
program to construct a laboratory data-base as
an aid in the interpretation of field geoelec-
trical data. We 1 previously observed that the
formation factor and the electrical conductivity
of the Pictured Cliffs sandstone (permeability
range, 7 x 10-4 -4 x 10- 1 md; porosity range,
3.8 to 4.9 percent) display time-dependent
behavior when the sandstone is saturated in tap
water. Pretreatment of the rock by Soxhlet
extraction lowers the formation factor, F, but
does not significantly change the time
dependence. Also, Duba et al. 2 reported on the
~ of cylindrical cores of Westerly granite;
Nugget, St. Peter, and Kayenta sandstones; and
Indiana limestone having aspect ratios (length/
diameter) from 2.00 to 0.25. Before measuremen~
the cores were saturated in distilled water,
tap water, and in 0.1 M NaCl solution. Aspect
ratio affects least the conductivity of rocks
saturated in 0.1 M NaCl; for these rocks a
linear relationship exists between log d and
log cp, commonly termed "Archie's law." However,
no simple correlation was found between log d
and log cp for rocks saturated in tap or
distilled water. This paper is a progress
report on the d and F as a function of time up
to 104 hours for 18 rocks saturated in tap water
or in 0.1 M NaCl solution at 100 kPa pressure.
214 TIME-DEPENDENT ELECTRICAL PARAMETERS OF ROCK-SOLUTION SYSTEMS
A paper discussing these results and the
results obtained for rocks saturated in 1.0
and 5.0 M NaCl solution is in preparation.
SAMPLES AND EXPERIMENTAL METHOD
The types of rock employed in this
investigation, their porosity, and other
ancillary information are provided in Table 1.
Details of the experimental procedure have been
reported previously,1,2 and will not be
detailed here. Essentially, right circular
cylinders (25.4-mm diameter x 25.4-mm length)
of rock were simultaneously and reproducibly
saturated with the solution in question so that
as the solution began to enter the pore struc-
ture of the rock it would do so under a con-
stant pressure differential between the vapor
pressure of the solution advancing inside the
rock and the laboratory atmospheric pressure
on the surface of the saturating fluid exterior
to the rock. The r:f measurements at 1 kHz were
conducted as a function of time for both rock
and solution. Rocks were measured using the
two-electrode technique without a guard ring
at approximately 25.5 °C. Duba et al. 2
°
previously reported that measurements of
water-saturated and 0.1 M NaCl-saturated
samples using a guard ring were not appreciably
different from those obtained without a guard
ring. Solutions were measured at 25.0 oC
utilizing a dip cell. An important aspect of
the procedure is that during the experiment,
each rock was stored in contact with its own
separate solution, which at the start of the
experiment was either tap water or 0.1 M NaCl
solution. Thus, the solution and the rock
constituted a pair of coupled SUbsystems.
EXPERIMENTAL RESULTS
The experimental results are treated in
terms of the Keller and Frischknecht modifica-
tion of Archie's law4 :
= °s/0 R = a¢ -m • • • • • • • • ( 1)
F stone (E), Buggy basalt (F), in Figs. 2a and
From the definition of F, and differentiating
with respect to log t, we obtain:
d log Os d log OR
d log F
d log t
::
d log t d log t
. . (2)
We consider the experimental data in the order
os' dR' and F.
Solution Conductivity, Os
The Os for tap water solutions is either
constant with time [Diamond Dust tuff (R),
Jorum rhyolite (p), and Box Car rhyolite (C)J,
or is monotonically increasing with time as in
the case of Pictured CUffs sandstone (K) 1 and
SPE 6609
all other rocks. Since rock and solution are
coupled subsystems, increase in Os occurs by
transport of soluble material from the rock.
When the Os remains constant, this is evidence
that the corresponding rock is either devoid
of appreciable clay minerals or that it has
little water-soluble material on its pore
surface. In the case of the 0.1 M NaCl solu-
tions, the conductivities remain constant with
time except for Pictured Cliffs sandstone,
which shows a slight increase at long times.
Evidently the NaCl conductivity dominates the
conductivity for the entire solution; contribu-
tions by rock or material lining the pores are
negligible by comparison. This can be
summarized by
d log Os
d log t ~ 0 for tap water, •• (3)
d log Os
:: 0 for 0.1 M NaCl . • • (4)
d log t
Thus, in 0.1 M NaCl, log F behaves oppositely
to log d ~Qth respect to time; but in tap
water, t~e situation is more complicated.
Rock Conductivity, OR
Log OR is plotted as a function of log t
and log ¢ for rocks saturated in tap water and
0.1 M NaCl solution in Figs. la and lb,
respectively. For rocks saturated in tap water,
there is no simple relation between log OR and
log ¢ (Fig. la). Rocks in 0.1 M NaCl increase
in log OR with increasing log ¢, especially at
time > 100 hours. Figs. 2a and 2b are projec-
tions of Figs. la and lb on the log dR-log t
plane for all the rocks. Rocks saturated both
in water and 0.1 M NaCl show essentially four
types of behavior. For one group of rocks, log
OR increases constantly until a steady state is
attained at approximately 4,000 to 5,000 hours
[i.e., Hard Hat granite (A), Rio Blanco sand-
2bJ. This corresponds to entry of solution
into the interconnected pores of the rock, but
without measurable transport of material from
rock to solution. For Hoggar granite (D) and
Simpson sandstone (J), log OR decreases
significantly in 3,000 to 8,000 hours. This
corresponds to transport of material from low-
porosity rock to solution. Log OR of high
porosity, extrusive igneous rocks like Mt.
Helen tuff (Q), Diamond Dust tuff (R), and
Jorum rhyolite (p), is virtually independent
of time in low-salinity solutions (see Figs. 2a
and 2b). Evidently these rocks do not contrib-
ute measurable amounts of conductive material
to the solution, even at long times. The
Rulison (H), Pictured Cliffs (K), and Wagon
Wheel (L) sandstones show a maximum in log dR
at ~20 hours. The existence of a maximum in
SPE 6609 H. C. WEED, A. J. PIWINSKII, and P. KELLER
log dR as a function of log t for Rulison and
Wagon Wheel sandstones suggests that the solu-
tion fills the interconnected pore space of the
rock within 20 to 40 hours, similarly to the
Pictured Cliffs sandstone. 1
Formation Factor, F
Log F is plotted as a function of log t
and log ¢ for rocks saturated in tap water and
0.1 M NaCl solution in Figs. 3a and 3b
respec t ~vely. There is no simple relation
o '
between log F and log ¢ in tap water but for
me d ~um-porosity rocks, log F appears to
o '
increase with lo~ t in an essentially monotonic
fashion (Fig. 3a). However, for rocks
saturated in 0.1 M NaCl, log F decreases with
increasing log ¢ as one would expect for a
system that was behaving somewhat in agreement
with Archie's law (Fig. 3b). Projection down
the porosity axis on to the log F-log t plane
in Figs. 3a and 3b provides clearer information
on the time dependence of log F for all the
rocks investigated (Figs. 4a and 4b). In tap
water, the following rocks display a minimum
in log F vs log t: Hard Hat granite (A)
Solnhofen limestone (B)t Box Car rhyolit~ (C)
Rio Blanco sandstone (E), and Buggy basalt (F)
(see Fig. 4a). The formation factor of high
porosity, extrusive igneous rocks [Diamond Dust
tuff (R), Mt. Helen tuff (Q), and Jorum
rhyolite (p)] is virtually independent of time.
Formation factors of the other rocks increase
with time to 8,000 hours. In the case of
Kayenta (0), Nugget (I), Rulison (H), and
Simpson (J) sandstones, Indiana limestone (N)
and Westerly granite (G), log F increases ' variance--a time-dependent part and a solution-
approximately in a linear fashion with respect
to log t from 10-2 hours to 1 hour. However
the linear behavior may be an artifact of th~
graphical interpolation method used in the
calculation of formation factor.
For rocks saturated in 0.1 M NaCl (Fig.
4b), the time variation appears smaller and the
rocks behave in a more orderly fashion than in
Fig. 4a. In particular, relatively small
changes in log F occur for Nugget (I)
Simpson (J), Kayenta (0), and St. Pet~r (M)
sand~tonest Indiana limestone (N), and Westerly
gran~te (G) from 10-2 to 104 hours. Formation
factors of Hard Hat granite (A), Solnhofen
limestone (B), Rio Blanco sandstone (E), and
Buggy basalt (F) decrease with time. Again
the formation factors of high porosity
o
ext rus~ve 'time- ,
igneous rocks are virtually
independent.
On the basis of an approximate correlation
between rock type and formation factor in 0.1
M NaCl for times from 103 to 104 hours, the
rocks can be divided into three groups. Group
I includes Hard Hat, Hoggar, and Westerly
granites, and Solnhofen limestone, with F
215
Nl,OOO. These rocks have low porosity and
little or no clay minerals. Therefore, con-
ductivity contributions from rock to solution
are small, so that solution conductivities
change little with time. Group II includes Mt.
Helen and Diamond Dust tuffs with F ",,10. These
are high porosity, extrusive igneous rocks
containing only traces of clay minerals'
zeolites are present,3 however. Group III
includes the rest of the rocks, with F between
15 and 220. Most of them are sandstones, some
containing appreciable amounts of clay
minerals, but Indiana limestone and Buggy
basalt are also included.
The correlation between log F and log ¢ in
Figs. 3a and 3b is analyzed by the method of
least squares using the logarithmic form of Eq.
1:
log F = C1 + C2 log ¢
Results are shown in Figs. 5a, 5b, 6a, and 6b,
which are projections of Figs. 3a and 3b on
the log F-log ¢ plane. The straight lines are
the calculated values of log F using the least-
squares results for Cl and C2 from Table 2. ThE
total length of the vertical bars is 2 S.D.
Figs. 5a and 5b include data from 10-2 to 104
hours, whereas Figs. 6a and 6b include data for
only long periods (i.e., 770 < time < 1,100
h~u:s) where time effects on F have been sig-
n~f~cantly reduced or possibly eliminated. In
the subsequent discussion, we assume that there
are at least two contributions to the total
dependent part. Therefore, we compare the
variance for two solutions and two times in
order to estimate their relative contribution.
In Table 2, the variance is greater in tap
water than it is in 0.1 M NaCl and ~cv = 0.20
to 0.23. The time-dependent part of the
variance is also greater in tap water than in
0.1 M NaCl; ~tV = 0.034 to 0.013, or about an
order of magnitude less than ~cv. Thus, in
spite of the definite time dependence shown in
Figs. "4a and 4b, time-dependent effects are less
important than solution-dependent effects.
Porosity-dependent effects are treated
explicitly in Eqs. 1 and 5, where C2 corre-
sponds to the Archie's law exponent, -m. C2
ranges between -0.35 and -0.99 for all data and
is significantly greater in tap water than in
0.1 M NaCl solution.
SUMMARY AND CONCLUSIONS
We have measured the 1-kHz d and F of 18
rocks saturated in tap water and 0.1 M NaCl
solution as a function of time up to approxi-
mately 104 hours. The d and F of most rock
specimens and their reacting solutions display
time-dependent behavior to 8,000 hours. F and
216 TIME-DEPENDENT ELECTRICAL PARAMETERS OF ROCK-80LUTION SYSTEMS
cr depend on the pore fluid, porosity, perme-
ability, and clay minerals present in the rock.
The Archie's law exponent, m, ranges from 0.35
to 0.50 for rocks saturated in tap water and
from 0.85 to 0.99 for rocks saturated in 0.1
M NaCI solution. This concentration dependence
precludes the use of Archie's'law for rocks
saturated in low-salinity solutions.
NOMENCLA TURE
a = coefficient in the Keller and
Frischknecht4 modification of Archie's
law
first coefficient in the least-squares
analysis; C1 = log a
second coefficient in the least-squares
analysis; C2 = -m
F formation factor; F = as/OR
f number of degrees of freedom in the
least-squares analysis
m parameter in Archie's law
r residual; the difference between
observed and calculated value
S.D. standard deviation; (S.D.) = vO.5
t time, hours 2 England (1966) 519 pp.
variance; v = lr /f
concentration-dependent change in vari-
ance
time-dependent change in variance
electrical conductivity of rock,
Siemens/meter
electrical conductivity of solution,
S/m
sum of the squares of the residuals,
taken over all the data
¢ = porosity; ¢ = pv/(total volume);
O~¢ <:1
SPE 6609
ACKNOWLEmMENTS
We thank A. Duba and H. Heard for review
and B. Hornady for typing the manuscript. The
work was performed under the auspices of the
U. S. Energy Research & Development Administra-
tion under contract No. W-7405-Eng. 48.
REFERENCES
1. Piwinskii, A. J. and Weed, H. C.: "A
Study of Rock-8olution Interaction and Its
Effect on Archie's Law," IEEE Trans.
Geosci. Electronics (1976) GE-14, No.4,
221-223.
2. Duba, A., Piwinskii, A. J., Santor, M.,
and Weed, H. C.: "The Electrical
Conductivity of Sandstone, Limestone and
Grani te," Geophys. J. Roy. Astron. Soc.
(1977) in press.
3. McKague, H.: personal communication
( 1977).
4. Keller, G. and Frischknecht, F.:
Electrical Methods in Geophysical
Prospecting, Pergamon Press, Oxford,
NOTICE
"This report was prepared as an account
of work sponsored by the United States Govern-
ment. Neither the United States nor the United
States Atomic Energy Commission, nor any of
their employees, nor any of their contractors,
subcontractors, or their employees, makes any
warranty, express or implied, or assumes any
legal liability or responsibility for the
accuracy, completeness or usefulness of any
information, apparatus, product or process
disclosed, or represents that its use would not
infringe privately-owned rights."
 Table 1. Data on Rock Specimens Used in Experiments

Mean
Sym- Mean Length Mean Radius Volume
Rock bol Depth and Identification (mm) (mm)

Blan~
Poros itv
Rio 1970.3 m interval. CER Geo-
sandstone E nuclear Hole RB-E-Ol, S14T- 25.471 12.660 0.66%
- ,35R9811 RiQ 61on~0 Ct~, Colo.
Mt. Hel en Surface outcrop, Mt. Helen,
tuff Q Nevada. 25.048 12.676 41.65%

Diamond Dust 47.6-47.9 m interval; Area

tuff R 16, Nevada Test Site 25.557 12.641 40.78%

Rulison 2564.5-2564.8 m interval.

sandstone H S25T75R95W, Garfield Cty, 25.808 12.719 1.96%
Colo.
Solnhofen
11 imestone B Solnhofen, Bavaria. 25.952 12.687 0.47%

[BUggy 70.1-70.5 m interval. Hole 25.980 12.675 I 1.57%

basa It F #1, Area 30, Nevada Test Site

IHard Hat 236.3 m 1eve 1, U 15a ho 1e, 26.022 12.718 0.07%

granite A Climax Stock, Nevada.
;
iHoggar Taourirt Tan Afella massif, 26.062 12.757 0.73%

I:::~"
D Algeria. 24°03'N, 5°02'E.
--.~-

140.2 m level. U 20e #1, 25.843 12.665 22.54%

rhyo 1ite P Nevada Test Site.

Iwagon Wheel 3103.3 m interval, S5T30N-

sandstone L R108W, Sublette Cty, Wyo. 25.869 12.662 9.04%

Ipictured Cliffs 1248.3 m level. San Juan

!sandstone K basin ~45 km east of Farm- 25.809 12.656 4.97%
inqton N.M.
ISimpson 3943.2 m level. Sunray,
sand stone J Cullen, S34T10NR7W, Okla. 25.803 12.670 3.98%
Southeast Anadarko basin.
St. Peter 30 m depth, S4T16NR8E, Doug-
sandstone M las Cty, Ill. 26.223 12.q56 14.57%

Kayenta 0.5 m level. t·1ixed Co. Site, I

sandstone 0 t~esaCty, Co 10., P. I. Core 26.245 12.617 23.05%
11- 1 I
Nugget I 26.100 12.652
sandstone I Utah. I 2.50%
I

Indiana I 26.222
limestone N Quarry, Bedford, Ind. 12.605 14.89%

Westerly I
granite G Westerly, R. I. 26.264 12.671 1.28%
I
Box Car
C Paiute Mesa, Area 20, 26.052 12.757 2.91%
rhyo 1ite Nevada Test Site, U 20i i

Table 2. Least Squares Analysis Results for Tap Water and 0.1 M NaCl Solution: log F Cl + C2 log ~.

Variance analysis
Figs. 5a, 5b Figs. 6a, 6b v = (S.0.)2
All data: 10- 2_10 4 hrs Data at long times: 770-1064 hrs All data Long time
I 2 4 data
Cl C2 S.D. Cl C2 S.D. 10 _10 770-1064 lit
I hrs hrs I
i
Tap Water 0.620±0.089 -0.353±0.056 I 0.601 O. 589±0. 250 -0.504±0.167 0.572 0.361 0.327 0.034
I

• !
0.1 M NaCl 0.687 to. 046 ! -0.993±0.028 I 0.369 0.807±0.014 -0.84S±0.090 0.351 0.136 0.123 I 0.012

II
c
--- I,, --- --- --- --- --- 0.225 0.204 0.021
I
 0.0 0.0
Tap water 0.1 M NaCI
E -1.5
c;, E-1.5
c;,
0;-
0;-
F-3.0 F-3.0
log ¢
-3 -2 ! -1 0 -3 -2
-4.5
ii' -4.5 L-~'----------4r-t-r--r--llf.---i!t--"-+
4.0 I
\
4.0

,..- f/1' III ,..- \

~I/'/
--;;; 2.0 Iii
i i:! ' \ 2.0\'
""~ 0
\ ,',I
','; ~
::.. ::.. \
'",.-
0 o.
j
~ 0_\
\
\
-2.0
A 01 C,F! I ! M/ IQ -2.0 'I
O.P I R
I
8 E,G I J
K
l N
P,O

R
I
A Q

FIG. lA - lOG dvs. LOG T AND LOG $ FOR ROCKS SATURATED IN TAP FIG. lB - LOG 6 VS. LOG T AND LOG rjJ FOR ROCKS SATURATED IN 0.1
WATER. LETTERS REPRESENT THE FOLLOWING ROCKS: (A) HARD HAT GRA- MNACI SOLUTION; LETTERS REPRESENT ROCKS INDICATED IN FIG. lAo
NITE, (B) SOLNHOFEN LIMESTONE, (C) Box CAR RHYOLITE, (D) HOG GAR
GRANITE, (El RIO BLANCO SANDSTONE, (F) BUGGY BASALT, (G) WESTERLY
GRANITE, (H) RULISON SANDSTONE, (I) NUGGET SANDSTONE, (J) SIMP-
SON SANDSTONE, (K) PICTURED CLIFFS SANDSTONE, (l) WAGON WHEEL
SANDSTONE, (M) ST. PETER SANDSTONE, (N) INDIANA LIMESTONE,
(0) KAYENTA SANDSTONE, (P) JORUM RHYOLITE, (0) Mr. HELEN TUFF,
AND (R) DIAMOND DUST TUFF.

Tap water
-1 0.1 M NaCI

-2 ~

-2

-3

-4

-4

-2 -1 o 2 3 4 -2 -1 o 2 3 4
log (t(hours)) log (t(hours))

FIG. 2A - LOG 6 VS. LOG T FOR ROCKS SATURATED IN TAP WATER; FIG. 2B - lOG 6 VS. LOG T FOR ROCKS SATURATED IN 0.1 M NACl.
LETTERS REPRESENT ROCKS INDICATED IN FIG. lAo LETTERS REPRESENT ROCKS INDICATED IN FIG. lAo
 4.5
Tap water

2.9

1.4
-3
-0.2+-~~---'----··-···-------~-r4-J11t-~----h~~t---t---

4.0 ~\
\

\
-2.0"
A o C,FII
E,G I

FIG, 3A - LOG F YS, LOG T AND LOG ¢ FOR ROCKS SATURATED IN TAP FIG. 3B - LOG F YS. LOG T AND LOG ~ FOR ROCKS SATURATED IN 0.1
WATER; LETTERS REPRESENT ROCKS INDICATED IN FIG, lA, MNACI SOLUTION; LETTERS REPRESENT ROCKS INDICATED IN FIG. lAo

Tap water
4

u.
'"
.!2

-2 -1 o 2 3 4
log Itlhoursll log Itlhoursll

FIG. 4A - LOG F YS. LOG T FOR ROCKS SATURATED IN TAP WATER; FIG. 4B - LOG F YS. LOG T FOR ROCKS SATURATED IN 0.1 MNACI
LETTERS REPRESENT ROCKS LISTED IN FIG. lAo SOLUTION; LETTERS REPRESENT ROCKS LISTED IN FIG. lAo
 Tap water 0.1 M NaCI
~
G
2.5 B G
4

B I I IB
~ i
S
~
,
2.0 8 A
A
II oJ
B G oJ A
A
G
oJ A
D

1.5
A
8
I g
G
3 t
A
A J
A H

I
H
H
H
'"
.£ t1 '"
.£
H
1.0 H F H
H

I
I :II
~ H

~ I
H
H 2

0.5 F

Il
H
H

11
~
N i ~
•I 0

I
~

N
~
~ e
0
• N M
I

-3 -2 -1 -3 -2 -1
log 4) log 4)

FIG. 5A - LOG F VS. LOG ¢ FOR ROCKS SATURATED IN TAP WATER; FIG. 5B - LOG F VS. LOG ¢ FOR ROCKS SATURATED IN 0.1 M NACl
LETTERS REPRESENT ROCKS LISTED IN FIG. 1A. TIMES ARE FROM 10- 2 SOLUTI ON± LETTERS REPRESENT ROCKS LISTED IN FIG. 1A. TIMES ARE
TO 10 4 HOURS. FROM 10- TO 104 HOURS.

0.1 M NaCI
Tap water
3 G
A
B A

H J

K
p
2 " H

~
G
G

~
o R

-3 -2 -1 -3 -2 -1
log 4) log 4)

FIG. 6A - LOG F VS. LOG ~ FOR ROCKS SATURATED IN TAP WATER; FIG. 6B - LOG F VS. LOG ~ FOR ROCKS SATURATED IN 0.1 MNAC1
LETTERS REPRESENT ROCKS LISTED IN FIG. 1A. TIMES ARE BETWEEN SOLUTION; LETTERS INDICATE ROCKS LISTED IN FIG. 1A. TIMES ARE
770 AND 1064 HOURS. BETWEEN 770 AND 1064 HOURS.