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(6)
where F* is the shaly sand formation resistivity
factor. We can then write
where Cs is the specific surface conductance of
the clay (ohm-I) and Qs is the number of equivalents
(4)
of exchange cation per unit of surface area. Further,
COMPARISON WITH EARLIER WORK Conductivity data for about 315 shaly sand cores
have been published by Hill and Milburn.3 These
Similar assumptions as to the equivalence of the data include independent cation-exchange capacity
cell factors for surface and bulk solution conductivity and Qv determinations on 36 samples. Additional
were made by Cremers and Laudelout l3 - 15 in their unpublished measurements including Qv and
work on clay mineral suspensions and gels. Their conductivity data on some 54 cores, together with
data indicate that isoconductivity points exist for conductivity data on 167 other samples, were made
different clay mineral gel-salt systems. By extrap- available to us by H. J. Hill. The conductivity data
olating the straight-line portions of the Co vs C w generally include three to four experimental points
plots for a series of gels consisting of varying in the straight-line portion of the curve (C w > 0.05
percentages of the identical clay species, a common mho em-I) and one to two points in the curved
isoconductivity point is found. Cremers and region, but these usually were obtained at
Laudelout observed that the conductivity at an equilibrating solution conductivities greater than 7
isoconductivity point is independent of gel m mho cm- 1 (solution resistivities less than about
porosity. By comparison, they found that their form 1.4 ohm m). Group 1 refers to all the above samples.
of the P-¢ function is in formal agreement with that While a large variety of rock types is represented
derived from theories by Burger 16 and Fricke,17 in Group 1, the distribution of Qv values is weighted
relating electrical conductance of stationary heavily in the range 0 ~ Qv ~ 1 equiv/liter; this
particles in dilute suspensions to particle shape group contains about 94 percent of the total number
factors and porosity. The Cremers-Laudelout P-¢ of samples. Another set of shaly sands (Group 2)
relation clearly is not applicable to shaly sands; was selected on the basis of a wider distribution of
moreover, the accuracy of the Cremers-Laudelout Qv values; with these samples, conductivity
data does not permit calculation of reliable values measurements at low equilibrating solution conduc-
of exchange - cation mobilities for clay plugs tivities (down to about 2.1 m mho em-I) were
equilibrated at any salt concentration. IS emphasized. Conductivity data for Group 2 cores
The proposed mechanism differs from that are probably the most accurate and complete with
sugges ted by Wyllie and his co-workers. 1,10,12 respect to range of Qv and C w values examined.
They represented the conduction process by an
equivalent resistor model containing three resistance GROUP 1
components in parallel instead of two as suggested Independent Qv determinations, together with
here. Two resistor elements are common to both Co·Cw measurements, were described for a selected
models; the third consists of conductive solid and set of sands by Hill and Milburn. 3 Petrophysical
electrolyte solution elements in series. Contribu- and conductivity data for this set are presented in
tions from this component can account for the sharp Table I. Similar measurements were carried out on
increase in the conductivity curves at low C w 54 additional cores. A description of these samples
values, rather than an increase in exchange-ion is given in Table 2; petrophysical characteristics
mobility. The Wyllie model requires four geometric and conductivity data are summarized in Table 3.
parameters, three of which are independent. These Table 4 gives general characteristics and petro-
can be obtained by appropriate manipulation of the physical data for the remaining samples used in
conductivity equation under various limiting the conductivity studies.
conditions. Experimental procedures employed in these
Some comparison should be made with the work conductivity measurements were described by Hill
of de Witte.19 He concluded from empirical consid- and Milburn. 3
erations that the conductivity behavior of water-
Qv Determinations
bearing shaly sands could adequately be represented
by the equation Cation-exchange capacities (CEC) as determined
by Hill and Milburn (Table 1) were measured
. . . . (12) chromatographically using ammonium acetate
solutions. Further CEC determinations (Table 3)
where AD and BD are constants. Eq. 12 is similar were made using a procedure suggested by Mortland
to that originally proposed by Patnode and Wyllie 20 and Mellor .21 This method requires repeated
and neglects the curved portion of the conductivity equilibration of the crushed rock sample with
plots at low Cw's. However, de Witte defined a concentrated BaCl 2 solution and washing to remove
"maximum formation factor", the limiting value of excess barium ions, followed by conductometric
TABLE 1 - PETROPHYSICAL AND CONDUCTIVITY DATA, SHAL Y SANDS (HILL AND MILBURN3)
Sample Porosity Air Q'I l
Suite Number (%) Permeability Exp. F* Co (Conductivity Units, m mho cm- )
(md) (equiv./liter)
4, Group 2 19 20.3 0.1 0.293 33.0 0.340 1.80 2.92 4.61 6.79
Sample Porosity
Air Brine
. Q" Co (Conductivity Units, m mho cm- 1 )
Sui te Permeability Permeabi lity Exp. F*
Number (%)
(md) (md) (equiv,/liter) 21.3 37.3 81.9 228. -C,
0.14
0.012
Qy. meq / ml
'-~ 0.12
E
0.052
...." ~ 0.10
o
~ 0.008 -: 0.08
E 26
o
o
~
o
o
1.47 12 Q 0.06
.....
0.004
_ 0.28
d' 0.04
" . : ,e.. :.
-c "~0.02 ..._ e.
- 4'"
FIG. 3_ELECTRICALCONDUCTIVITY (Co) OF THREE FIG. 4 - PLOT OF [ANae Qvl OBTAINED FROM
SHALY CORES VS EQUILIBRATING BRINE CONDUC- CONDUCTIVITY CURVES VS Qv DETERMINED BY
TIVITY (Cw )' DIRECT MEASUREMENT FOR GROUP 1 CORES.
Eocene 12859 ft 23.9 0.017 19.1 13.2 7.85 4.43 2.44 1. 282 0.680 0.3625 0.1929 Co
I
2 Eocene 12486 ft 21.2 0.052 16.6 11.41 6.84 3.87 2.14 1.169 0.6435 0.3609 0.2049
Eocene 12665 ft 23.1 0.052 14.35 8.59 4.86 2.68 1.451 0.7877 0.4345 0.2408
4 Eocene 12552 ft 8.0 0.26 2.01 1.14 0.64~ 0.3674 0.206 0.1198 0.0700
Eocene 12737 ft 15.4 0.20 11. 01 6.61 3.80 2.16 1.219 0.7105 0.4296 0.2677
6 Eocene 12687 ft 21.5 0.095 13.6 12.7 8.75 5.27 3.03 1. 712 0.971 0.568 0.330 0.2073
Eocene 12692 ft 17.1 0.053 8.84 6.14 3.73 2.14 1. 212 0.7005 0.4135 0.2524 0.1599
8 Eocene 12692 ft 17.1 0.053 9.22 6.41 3.89 2.23 1.258 0.7154 0.414 0.2473 0.1515
9 Eocene 12883 ft 19.9 0.085 13 .1 9.03 5.44 3.14 1.79 1.025 0.602 0.3698 -0.2342
10 Eocene 12697 ft 12.5 0.253 1.62 1. 06 0.671 0.402 0.239 0.1459 0.0924 0.0598 0.0391
11 Eocene 12697 ft 12.5 0.253 0.967 0.592 0.350 0.211 0.1265 0.0798 0.0490 0.0323
12 Eocene 12884 ft 11.0 0.28 5.89 5.53 3.85 2.404 1.46 0.895 0.5737 0.3616 0.2461 0.1993
13 Eocene 12884 ft 11.0 0.28 3.80 2.39 1.48 0.926 0.6022 0.4155 0.2888 0.2246
14 Eocene 12884 ft 11. 0 0.28 7.52 5.29 3.32 2.00 1.233 0.7965 0.5455 0.3800 0.2940
'f.
15 Eocene 12698 ft 9.2 0.41 1.73 1. 16 0.755 0.479 0.311 0.2052 0.1416 0.0948 0.0687
o
-
~
/"l
>-l
><!
16
17
Eocene
Eocene
12955 ft
12720 ft
10.3
14.0
0.67
0.33
3.01
4.19
1.956
2.72
1.30
1.82
0.895
1.25
0.6576
0.9227
0.505
0.6824
0.3788
0.553
0.3225
o 4730
o 18 Albian 152{.5 m 25.9 0.59 13.9 9.86 6.39 4.11 2.734 1. 924' 1. 353 1. 070 0.9409
"'l
"ll
/"l 19 Albian 1521.5 m 25.9 0.59 14.7 10.44 6.61 4.13 2.626 1.746 1.238 0.8949 0.7140
>-l
:=
o 20 Albian 1521.5 m 25.9 0.59 20.1 18.8 13.2 8.28 5.09 3.171 2.062 1.405 1.016 0.7641
t"'
/"l
~ 21 Lower Tertiary 1045.5 m 23.8 0.29 13 .62 9.98 6.96 4.17 2.55 1.571 0.957 0.7039 0.5585
il:
t'l 22 Lower Tertiary 1044.3 m 22.5 0.72 7.58 6.43 4.95 3.69 2.52 1. 79 1. 351 1.092 0.9523 0.8956
2
-
<;"J
2
/"l
/"l
23
24
Lower Tertiary
Lower Tertiary
981.6 m
1040.4 m
24.2
21.6
1.04
0.81
10.36
6.36
8.83
5.46
6.88
4.28
5.21
3.27
3.63
2.34
2.61
1.77
1.960
1.380
1. 576
1.102
1. 356
0.9952
1.2720
0.9707
:=
ff>
...o 25 Lower Tertiary 1021.1 m 18.7 1. 27 5.46 4.72 3.76 2.97 2.24 1.77 1.481
~ 26 Lower Tertiary 981.9 m 22.9 1.47 7.50 6.49 5.21 4.13 3.14 2.48 2.046 1.826 1. 597 1. 503
:=
2
...
t"'
27 Lower Tertiary 983.4 m 20.9 1.48 7.04 6.10 4.90 3.88 2.97 2.41 2.039
...
~
2
...."" TABLE 8 - FRACTION (8) OF MAXIMUM EQUIVALENT CONDUCTANCE (ANa) AS A FUNCTION OF WATER CONDUCTIVITY
IQ
0-
00
Values between parentheses considered not reliable because of extreme deviation from the rest of the assembly,
probably due to Qv determination. They were not used in calculating the average.
For Cw > 0.060 mho/em, 6 = 1 .
......
..
Winsauer et al., 23 can be used to relate F* to Values of 8, together with their average values and
porosity. standard deviations, are given as a function of C w
The two maj or tests of the proposed conductivity in Table 8.
model, as discussed previously, are met. Values of B as a function of Cw were calculated
Conductivity data obtained for Group 2 cores are according to Eq. 16 using average values of 8 and
quite detailed in the curved portion of the Co -C w A&a (Fig. 6). The empirical equation representing
plots (2.085 < C w < 52.49 m mho cm- I ) and permit. B as a function of Cw at 25C is found to be
calculation of the increase in counterion mobility
with increasing equilibrating electrolyte concentra- B = [1 - 0.6 exp (-Cw /0.013)]O.046
tions within this concentration range. The increase 2 -1
h
moe m me q , . . . . . . . . . (19)
in flfla has been represented by a simple empirical
relation (Eq. 10) for B as a function of C w and two
and, as shown in Fig. 6, provides a reasonable fit
constants a and y. for these data. Eqs. 9, 10 and 19 describe available
6 [1 - a exp (-Cw/'y)] . . . . (15) shaly sand data about as well as does the Hill-
Milburn equation.
Extrapolation to C w = 0 using Eq. 19 results in
B = 6A~a/l000 . (16)
a calculated value for the equivalent conductance
The equivalent conductance of the clay counterions of the sodium exchange ion (A'f.)' of 18.4 sq cm
is denoted by B, with Afla/1,000 representing B at equiv-Iohm- I . This is substantially equal to the
its maximum value (0 = 1) in the straight-line por- value of equivalent conductance of sodium exchange
tions of the Co' Cw curves. ions of about 18 sq cm equiv- I ohm- I which can be
Values of 8, at each value of C wand for each deduced from conductivity measurements of sodium
core, were calculated from the ratio of the measured montmorillonite-distilled water ge Is at 25.0C reported
Co values to the hypothetical values (C;) of Co' by Van Olphen and Waxman. 24 While this agreement
calculated from the straight-line extrapolation at is quite comforting, some caution should be observed
the same C w (Fig. 1). Since the same formation since the calculated value of (A},a)' is obtained by
factor F* applies throughout the entire electrolyte extrapolating an empirical relation beyond observed
concentration range, data.
The assumption in the model of an exponential
. (17) increase of counterion mobility with increase in
r = solution conductivity is justified by comparison
with shaly sand conductivity data and by the
apparent agreement of extrapolated conductivity at
thus,
Cw = 0 with clay gel conductivities.
( 1000)Cw
. . . . (18) A further general criterion for the model follows
(r - 1) + r from the thermodynamic relation between electrical
A~a Qv transport numbers calculated for conditions of
nonzero electric current flux and zero concentration
1000,--------------------,
gradient, and diffusion potentials measured under
conditions of nonzero concentration gradient and
zero electric current flux. It should be possible to
0.05 r - - - - - - - - - - - - - - - - ,
• I
100
~ 0.04
E
"-
N
E - CALCULATED FROM EQUATION
u
0 0.03
.£: • AVERAGE FROM CONDUCTIVITY
10 E EXPERIMENTS. GROUP ] I
EOCENE SANDS II)
o LOWER TERTIARY
SANDS 0.02
UT.
0 0.08
1L-_-'-------'----'---l---L.l....LLL-_-'-------'---.L...l---L.l~ C w • mho/em
0.01 0.1
4> FIG. 6 - EQUIVALENT CONDUCTIVITY (B) OF THE
COUNTERIONS ASSOCIATED WITH CLAY AS A
FIG. 5 - SHALY SANDS FORMATION RESISTIVITY FUNCTION OF EQUILIBRATING ELECTROLYTE CON-
FACTOR (F*) VS POROSITY (¢). DUCTIVITY (C w )'
j '":::>
n*=2.0
Rw=O.5 ohm m
i
VI
~ o
>
'"ao: "'a:
Q. 0.1 a'
u. u.
o o
z 0.1
z o
o
t=
~
a:
u.
Rw'2 I. 0.5 0.1 0.05 ohm m
.
t=
u
0:
U. 0"'1.2 1.4 1.6 1.8 2.0
VI
i en •
0.01~1_-'---'-1.....L..LL.L-'-;;;-_--'----'-----'--...L.l..L.L':;!;;;-_---'-------'-----'-.L.L~