Chapter 2 - Porosity

2.39
2.5 Pore Structure Measurement
Application of the Carmen-Kozeny model requires precise measurements of pore
level parameters; e.g., specific surface area and tortuosity. Numerous methods have been
developed to measure the specific surface area of a sample from early statistical methods to
current day imaging techniques. The advanced technology has improved the estimation of
specific surface area. Tortuosity measurements have been confined to electrical resistivity
measurements on samples with the underlying assumption that the electrical path and fluid
flow path are the same. In most measurement techniques, a physical sample must be
extracted from the reservoir; i.e., core for the analysis. Recent advances in NMR logging;
however, have provided an alternative to this requirement.
This section will explain the various measurement techniques for these parameters
and discuss the relevant advantages and limitations.
Methods for Specific Surface Area
Accurate specific surface area measurements of porous media are required when
predicting permeability using the Kozeny or Kozeny-Carman equations. The three common
techniques for estimating specific surface area per unit volume are: Petrographic Image
Analysis (PIA), gas adsorption method and Nuclear Magnetic Resonance (NMR). Each
method measures at a different scale: NMR at sub-electron level, BET at the electron level,
and PIA at the pore level. Figure 2.25 illustrates the result of these different levels of
measurement on a hypothetical pore body.
NMR
PIA
BET

Figure 2.25. Hypothetical example of specific surface area measurements
Due to the additional surface area measured, the resulting relationship is valid: A
s
(NMR) >
A
s
(BET) > A
s
(PIA). However, the extra surface area measured by the NMR is not relative,
Chapter 2 - Porosity
2.40
because it does not affect flow. The preferred method is the PIA because it is a pore-level
measurement, which is directly related to flow.
Statistical Methods
One of the earliest techniques, but not very accurate, was to repeatedly drop a needle
on a thin section and count the times a pore surface is intersected by the needle and the
number of times the end of the needle falls within the pore space. The probability of
selecting a pore or pore perimeter is given by [Perez-Rosales,1967]:
m
nL
c
bv
S
| 4
= (2.32)
where
c = the number of perimeter intersections
n = number of points in pores
L = needle length
M = magnification
The lack of scientific background and reliance on probability made this method unpopular.
Adsorption method
These methods rely on the measurement of the volume of physical adsorption of an
inert gas (Argon or Nitrogen) on the solid surface at reduced pressure and temperature, near
the normal liquefaction temperature of the gas. Isothermal adsorption theory developed by
Brunauer-Emmett-Teller (BET) allows for the determination of the amount of gas to cover
the solid surface with a single layer of gas molecules. The total surface area (A
s
) is given by:
o * n
s
A = (2.33)
where o is the effective surface area covered by a molecule of gas (15.2
2
for nitrogen and
13.6 for Argon), and n is the number of molecules in the volume of gas to form a mono-
molecular layer.
M
N
m
V
n

= (2.34)
where,
V
m
= volume of gas to form a mono-molecular layer, cc.
= density, gm/cc
N = avagadros number, 6.023x10
23
molecules/gm-mole
Chapter 2 - Porosity
2.41
M = molecular weight, gm/gm-mole
A literature survey reveals that there are few reported measurements on specific
surface area of geological porous material. Brooks and Purcell [1952] and Tignot et al.
[1952] reported surface areas of a few sandstones and also compared the direct measurement
method developed by Brunauer Emmett Teller (BET) against predicted value of specific
surface area calculated using the Kozeny equation. Brooks and Purcell first investigated
specific surface area for an unconsolidated pack of uniform, spherical glass beads. Using
mercury capillary pressure curves, the effective zoning factor was determined,
}
=
=

=
1
0
2 12
10 87 . 9
2
) cos (
S
S
c
p
dS
k x
T
k
u o |
(2.35)
where,
p
c
= capillary pressure, dynes/cm
2

o = interfacial tension, dynes/cm
k = permeability, md
Substitution of k
T
into Carman-Kozeny equation results in determination of specific surface
area. The results by this method are slightly greater (1.05 to 1.35) than geometrically
computed values. The difference is attributed to minor imperfections of the spherical beads;
therefore the true surface area is greater than the computed value; and to an assumed contact
angle of 140. The second step was to analyze specific surface area for consolidated porous
solids. Using the same procedure as above, k
T
was determined to be 8 to 40. In comparison,
Kozeny = 2
Carman = 5
Glass beads = 3 to 4
The increased tortuosity is considered the reason for the discrepancy in values. A further
step was to compare the specific surface from gas adsorption with the CK equation.
Brooks and Purcell reported that observed surface areas as determined by gas
adsorption are from 5 to 100 times larger than the areas calculated from the Kozeny
equation for consolidated sand and heterogeneous rocks. The discrepancy was attributed to
variations in pore structure when glass beads were replaced with a naturally occurring porous
media. Furthermore, the Kozeny equation only applies to external surface area of the solid
Chapter 2 - Porosity
2.42
particles that would be contacted by a moving fluid. Thus any surfaces that are exposed but
not in contact with a moving fluid (i.e. dead-end pores) would not be counted using the
Kozeny relationship, but would be measured using a gas adsorption method.
It was postulated from these findings that "the lack of uniform pore size in naturally
occurring rocks may limit the applicability of Kozeny equation to such porous solids and may
contribute, in part to the observed differences between the Kozeny and gas adsorption
surface areas". Donaldson et al. [1975] using an apparatus modified from Nelson and
Eggertsen for porous media, found excellent agreement between the surface areas obtained
from Kozeny-Carman equation and nitrogen adsorption on glass beads, and good agreement
for crushed sand. Donaldson et al. attributed this agreement of crushed sand to the grinding
process, which rounded the grains.
It should be noted that no author has attributed any discrepancy to the assumptions
made when using the Kozeny relationship. The constant in the Kozeny or Kozeny-Carman
equations, which supposedly compensates for tortuosity, shape factor, sizing and in turn
generalizing the equation for non-ideal systems has to date not been considered as a source
for these inconsistencies.
The gas adsorption method is widely used in the determination of specific surface
areas of porous solids. However, it should be limited to porous media, which do not have
large specific surface, and the grains of the matrix are singularly smooth and regular.
Consequently, it can be safely assumed that the adsorption method, as currently practiced,
does not measure the same surface area as that involved in fluid flow experiments of most
porous rocks; especially when the rock samples are crushed. However, for unconsolidated
porous systems, the specific surface area obtained by the gas adsorption method is adequate.
Fig. 2.26 shows a log-log plot of S
gv
, versus d
g
data obtained experimentally. The equation of
the straight line is,
g
d
gv
S
27 . 4
= (2.36)
where
S
gv
= specific surface area per unit grain volume; cm
-1

dg = grain diameter, cm
Chapter 2 - Porosity
2.43

Figure 2.26 Relationship between specific surface area and grain size from gas adsorption
method.

It is obvious from Fig. 2.26 that the specific surface area of the rock material increases as the
size of the constituent grains decreases, with the result in a loss in permeability.
Furthermore, for porous media composed of clay minerals, which have large specific surface
areas, a reduction in permeability will also occur. The following list [Lake, 1998] contains
measured S
gv
for various media illustrating two orders of magnitude in difference for clays in
comparison to sandstones. It is therefore a common observation that permeability will be
inversely proportional to clay content.

Chapter 2 - Porosity
2.44
Material S
gv
, cm
-1

Berea 20
Torpedo 80
Kaolinite 500
Illite 2800
Smectite 1300

From mathematical principles the specific surface area of a spherical glass bead is:
g
d
gv
S
6
= (2.37)
The difference between the compute value of 6 and the empirical value of 4.27 is due to the
roughness and irregular shape of the grains; consequently the total surface area exposed to
fluid is appreciably reduced by contacts between grains. A general equation can be derived
for S
gv
in the form of,
g
d
sg
K
gv
S = (2.38)

where K
sg
is the effective grain shape factor. A similar analysis can be applied to pores for
uniform pore-sized media, i.e.:
p
d
sp
K
pv
S = (2.39)
where K
sp
is the effective pore shape factor and d
p
is the mean pore diameter.
Petrographic Image Analysis
The Petrographic Image Analysis method relies on sophisticated imaging techniques
of thin sections to determine surface area [Clelland & Fens, 1991]. X-ray, back-scattered
electrons, and SEM are imaging methods currently used. Equipment consists of an image-
processing system, petrographic microscope and a camera. It has the advantages of requiring
a small sample, 5 to 10 mm
2
and fast measurement time, 20 to 30 minutes. PIA method may
be used to characterize the porous rock if samples are prepared with good optical contrast
Chapter 2 - Porosity
2.45
between the pores and grains, and the thin sections are obtained at overburden conditions.
The specific pore surface can be determined as:
p
A
p
L
pv
S
t
4
= (2.40)
where L
p
and A
p
are the pore perimeter and the pore cross-section, respectively. Using PIA a
pore shape factor can be determined as [Tiab, 1994], [Bekri, et al. 2000]:
p
A
p
L
sp
f
t 4
2
= (2.41)
The factor f
sp
indicates what the perimeter L
p
would be if the planar feature was a given
shape. For example, if the 2D pore shape is a circle, then substituting for L
p
= 2tr and A
p
=
tr
2
results in f
sp
= 1. To convert to 3D space, K
sp
= 6*f
sp
. The table below shows f
sp
and K
sp
values for a variety of pore shapes.
Pore Shape f
sp
(2D) K
sp
(3D)
1.00 6.00

1.27 7.62

1.65 9.90

3.75 22.5

5.84 35.0
Nuclear Magnetic Resonance
The NMR (Nuclear Magnetic Resonance) method can also be used to estimate the specific
surface area from:
ma nmr
A
gv
S * = (2.42)
where
A
NMR
= NMR surface area of dry material, m
2
/gm

ma
= grain-matrix density, gm/cc
Chapter 2 - Porosity
2.46
S
pv
and S
gv
values obtained from NMR are considerably higher than values obtained by PIA,
or the gas adsorption technique. Several studies have found that the specific surface area,
measured with any of the three methods, i.e., the adsorption method, PIA and NMR, is
related to the irreducible water saturation or simply water saturation by a relationship of the
general form:
b
w
aS
pv
S = (2.43)
where a and b are constants of correlations. Zemanek investigated low-resistivity sandstone
reservoirs and found surface areas measured with the NMR technique were quantitatively
consistent with the irreducible water saturations from the capillary pressure curve data. Figs.
2.27 and 2.28 demonstrate an excellent correlation between S
pv
and S
wi
and S
w
.
Figure 2.27 Relationship between surface area and S
wi
for a sandstone formation
Figure 2.28 Relationship between surface area and S
w
for a sandstone formation