Nanoscale Gas Flow in Shale Gas Sediments
F. JAVADPOUR, D. FISHER, M. UNSWORTH
Alberta Research Council
Abstract
Production of gas out of low permeability shale packages is
very recent in the Western Canadian Sedimentary Basin (WCSB).
The process of gas release and production from shale gas sed-
iments is not well understood. Because of adsorptive capacity
of certain shale constituents, including organic carbon content,
coalbed methane models are sometimes being applied to model
and simulate tight shale gas production behaviour. Alternatively,
conventional Darcy flow models are sometimes applied to tight
shale gas. However, neither of these approaches takes into ac-
count the differences in transport mechanisms in shale due to ad-
ditional nanopore networks. Hence, the application of existing
models for shale results in erroneous evaluation and predictions.
Our analysis shows that a combination of a nanopore network
connected to a micrometre pore network controls the gas flow in
shale. Mathematical modelling of gas flow in nanopores is dif-
ficult since the standard assumption of no-slip boundary condi-
tions in the Navier-Stokes equation breaks down at the nanometre
scale, while the computational times of applicable molecular-dy-
namics (MD) codes become exorbitant. We found that the gas
flow in nanopores of the shale can be modelled with a diffu-
sive transport regime with a constant diffusion coefficient and
negligible viscous effects. The obtained diffusion coefficient is
consistent with the Knudsen diffusivity which supports the slip
boundary condition at the nanopore surfaces. This model can be
used for shale gas evaluation and production optimization.
Introduction
Shale gas is a type of reservoir classified under the Unconven-
tional Gas heading. These ‘difficult to produce’ reservoirs will play
an increasingly important role in Canadian gas production because
they are showing the potential to offset declining conventional gas
production.
Quite simply, shale gas is natural gas produced from shale se-
quences. Gas shales are predominantly lithified clays with organic
material and detrital minerals present in varying amounts. Organic
matter is an integral constituent of a productive shale gas reservoir.
In addition, these fine-grained rocks are microporous, causing low
permeabilities.
While shale gas production has had a long history in the United
States, dating back about 80 years, it is still at the very early stages
of commercial production in Canada. Very little public data exists
on shale gas production, yet industry interest is on the rise. A va-
riety of estimates indicate that between 550 and 860 trillion cubic
feet of gas-in-place could exist in potential shale gas formations in
Western Canada(1, 2).
Peer Reviewed Paper (“Review and Publication Process” can be found on our Web site)
October 2007, Volume 46, No. 10 55
But shales can be difficult to evaluate using conventional labora-
tory techniques. Much of this has to do with resident clays that can
have bound water either as part of their matrix or loosely bound in
the interlayers in amounts of 75 to 80%. Another challenge can be
the accurate measurement of in situ permeabilities, which are on
the nanoscale. Core samples have often been subjected to coring-
induced or stress release fractures, resulting in greatly overstated
permeability measurements.
While some shales in Western Canada are, at this early stage,
showing the proper geochemical and reservoir properties to sup-
port gas production, new techniques need to be developed to more
accurately understand shale properties and their productive poten-
tial. Modelling shale gas data to better understand storage mech-
anisms and diffusive flow would benefit the nascent shale gas
industry in Canada.
The use of desorption curves through canister desorption testing
is a standard laboratory procedure, which is an important step in
the analysis of coalbed methane production. The same technique is
currently used for shale gas. The need to establish an estimate of
gas volume in representative samples is the primary goal of reserve
estimation since the value of a reservoir is related to the amount of
recoverable gas-in-place.
Many of the models used for coal assume gas production is
being controlled by a constant diffusivity coefficient from per-
fectly spherical objects connected by a relatively large fracture
network(3). Application of this general model to shale may result in
the introduction of large errors in the production model, although
in the current shale gas testing environment, the same desorption
tests developed for coal may be used as at least partial indicators of
reserves potential for shales. However, gas production from shale
is the outcome of several different types of gas release processes,
including, but not limited to, desorption. In fact, the data sets are
incorrectly referred to as ‘desorption graphs’ and should in fact
be referred to as ‘gas evolution graphs’ in order to encompass all
forms of gas transport mechanisms.
We have developed a new descriptive model of flow dynamics
in structures which have complex pore networks. The idea that the
nanopore networks of shale behave differently than Darcy flow has
shaped our preliminary observations.
Physics of Gas Evolution and Production
Understanding the physical aspects of gas production from
shale gas sediments is important for reservoir evaluation and pro-
duction optimization. Figure 1 shows the spider diagram of the
shale gas research study. The research is divided into experimental
and theoretical studies. From the experiments, pore size distribu-
tion and characteristic coefficients such as permeability and dis-
persion coefficient can be determined. From theoretical modelling,

Production
optimization
Reserve
Rock
estimation Simulation
Kerogen & Clays
fluid
Deliverability
Fluid flow
Characterization
Desorption
Desorption in coefficient
nanopores
Dispersion
Theoretical coefficient
modeling Experiment
* (Nanopores
Pore size
* distribution
Flow in nanopores
FIGURE 1: Spider digram of the shale gas research study. The
materials presented in this paper are marked by *.
(a) Conventional (b) Shale gas
FIGURE 2: Comparison between pores in conventional (a) and
unconventional shale gas (b) reservoirs.
the flow and desorption in nanopores can be studied. Combining
experiments with the theoretical model results in shale gas sed-
iment characterization for reserve estimation and deliverability
analysis. Furthermore, the obtained knowledge will be used to de-
velop/modify reservoir simulators for production optimization. In
this paper, we present the experimentally obtained permeabilities
(pulse decay method) of 152 samples from nine reservoirs with
pore-size distribution of several shale samples at 415 MPa (60,000
psi) mercury injection pressure, as well as desorption data for a
representative shale sample. For the theoretical part, we present
gas flow in nanopores and describe gas evolution curves using
probability density functions.
The phenomena of gas storage and flow in shale gas sediments
are a combination of different controlling processes. Gas is stored
as compressed gas in pores, as adsorbed gas to the pore walls and as
soluble gas in solid organic materials, i.e., kerogen and clays. Gas
flows through a network of pores with different diameters ranging
from nanometres (nm = 10-9m) to micrometres (μm = 10-6m)(4).
Figure 2 compares the pore distribution in conventional and un-
conventional (shale) reservoirs. As shown in this schematic figure,
the number of nanopores is higher in unconventional shale gas sed-
iments. Diameter of pores in shale gas sediments range from a few
nanometres to a few micrometres.
In shale gas systems, nanopores play two important roles. First,
for the same pore volume, the exposed surface area in nanopores
is larger than in micropores. This is because surface area is propor-
tional to 4/d, where d is the pore diameter. This large exposed area
permits large volumes of gas desorption from the surface of the
kerogen in nanopores. Consequently, higher mass transfer of gas
molecules occurs inside the bulk kerogen. Secondly, gas flow in
nanopores is different from the Darcy flow. This issue will be dis-
cussed in detail in the following section.
Figure 3(a-e) illustrates the sequence of gas production at dif-
ferent length scales. Production from a new drilled wellbore (a) is
happening through the large pores (b), and then the smaller pores
56 Journal of Canadian Petroleum Technology
Wellbore
(a) Macroscale
(Reservoir)
Mesoscale
(b) (micro-fractures
network)
Adsorption
coefficient
Microscale
(c)
network)
Nanoscale
(d) (gas desorption
from nanopore
walls)
Molecular scale
(e) (mass transfer from
kerogen/clay bulk to
pore surface
FIGURE 3: Gas evolution and production in shale gas sediments
at different length scales. (a) Macroscale: gas flow from the
reservoir to the wellbore, (b) Mesoscale: gas flow in large pores,
(c) Microscale: gas flow in nanopores, (d) Nanoscale: gas desoption
from the nanopore walls, and (e) Molecular scale: diffusion of gas
molecules in the kerogen/clay.
(c). During reservoir depletion the thermodynamic equilibrium be-
tween kerogen/clays and the gas phase in the pore spaces changes.
Hence, gas desorbs from the surface of the kerogen/clays (d). This
non-equilibrium process further drives the gas molecules to dif-
fuse from the bulk of the kerogen to the surface of the kerogen ex-
posed to the pore network (e). It is well documented that quantities
of gas can be stored either as a dissolved phase in liquid hydrocar-
bons, or as an adsorbed phase on other materials within the shales
of the kerogen, i.e., certain forms of illite. However for the sake
of simplicity, liberation of gas by these mechanisms is neglected
in this study.
Flow in Micropores
This aspect of the flow in shale gas is similar to conventional
gas reservoirs. The Darcy equation is a suitable equation for these
types of pores, i.e., laminar flow.
Flow in Nanopores
In general, fluid flow through nanopores is modelled using ei-
ther the continuum or the molecular approach(5, 6). The continuum
approach solves for macroscopic fluid properties as a function of
the spatial coordinate and is used widely for fluid flow applica-
tions. As the length scale of a physical system decreases, the va-
lidity of the standard continuum approach with no-slip boundary
conditions diminishes. Figure 4 illustrates the no-slip and slip
boundary conditions on the inner surface of a pore. Figure 4a illus-
trates the Poisseuille parabolic velocity profile in a pore with zero
velocity (no-slip) on the walls. Figure 4b illustrates the slip con-
dition, where gas molecules can freely slip on the surface of the
pores and collide with the wall or other gas molecules. A widely-
recognized dimensionless parameter that determines the degree of
appropriateness of the continuum model is the Knudsen number(5,
 Table 2: Flow regime condition based on Knudsen
(a) number.
U=0
Navier-Stokes Equation
No-slip (Kn < 0.001) Slip (0.001 < Kn < 0.1)

Mm
U = Umax
Continuum flow Slip flow
Darcy flow Knudsen Diffusion
U=0

10
(b)

Transition
flow
1

0.1

Slip flow
10 nm
0.01
50 nm

Kn
0.001
300 nm

No-slip
nm

flow
1 Mm
0.0001
10 Mm
0.00001
50 Mm
FIGURE 4: Comparison of gas flow (a) in micropores where the
0.000001
flow is no-slip and (b) in nanopores where the flow is slip. 100 1,000 10,000 100,000
P (kpa)
Table 1: Mole fraction, molar mass, and collision
diameter δ for each component in typical shale gas FIGURE 6: Knudsen number for the gas mixture as a function of
sediment gas sample. pressure for different pore sizes at 350 K.

Gas Mole Collision Diameter Molar Mass
Components (%) (δ, nm) (kg/kmol)
CH4 87.4 0.4 16.0
C2H6 0.12 0.52 30.0
CO2 12.48 0.45 44.0
average 0.41 19.5
80
60
350 K
(nm)
Equation (2) is not very accurate at very high pressures. That is
why it is predicting a mean-free-path smaller than the collision di-
ameter at very high pressures.
The Knudsen number is a measure of the degree of rarefaction
of gases encountered in gas flow through small pores. Table 2 de-
scribes different regimes of fluid flow depending on the Knudsen
number(7). At a low Knudsen number (Kn < 0.001) the no-slip
boundary condition in the continuum flow regime is valid. At a
high Knudsen number regime (0.001 < Kn < 0.1), the rarefaction ef-
fects become more pronounced and eventually the continuum ap-
proach breaks down. Figure 6 presents the Knudsen number as a
function of pressure for different pore sizes ranging from 10 nm to
50 μm. The Knudsen number decreases by increasing the pressure,
and also it is smaller at larger pores.

40 An accurate approach to describe a high Kn flow regime is the

400 K molecular model(5), which recognizes the fluid as a swarm of dis-
crete particles. In this model, the position, inertia and state of all
20 individual particles are calculated either deterministically(7) or
probabilistically(9) at all times. The molecular approach considers
300 K individual particle dynamics based on a Boltzmann distribution at
0 the temperature of interest. The interaction between two particles
100 1,000 10,000 100,000 is given by the two-body potential energy and transient evaluation
P (kpa) of particle positions which are determined by numerical integra-
FIGURE 5: Average mean-free-path λ for the gas mixture as
tion of Newton’s equation of motion. In spite of the theoretical ap-
function of pressure and temperature. propriateness of molecular-dynamics (MD) models for the purpose
of capturing the small-scale interactions, it is unrealistic to simu-
late a reasonably practical nanoscale network in shale gas sediment
7).It is defined as the ratio of the gas mean-free-path λ and the pore
using present-day supercomputers. Most MD calculations are re-
diameter d.
stricted to femtoseconds (10-15 s) time steps limiting the results to a
short time-scale such as picoseconds (10-12 s) to nanoseconds (10-9
λ
Kn = s) phenomena(5, 10).
d ................................................................................................... (1)

Where λ is defined as(8):

Alternative Approach
An alternative approach for gas flow in nanopores is to describe
k BT the flow consistent with a diffusive transport regime with a con-
λ=
2 πδ2 P ........................................................................................... (2) stant diffusion coefficient and negligible viscous effects. Mathe-
matically, this is expressed as(10):
in which kB is the Boltzmann constant (1.3805 × 10-23J/K), T is
qρM ∆P
temperature (K), P is pressure (Pa) and δ is the collision diameter = Dk
of the gas molecule. Table 1 presents the gas properties of a typ- φA RTL
...................................................................................... (3)
ical shale gas sediment. In Figure 5, the average mean-free-path of
the gas presented in Table 1 is plotted versus pressure at three dif- where q is the flow rate, φ is porosity, A is the exposed area, ∆P
ferent temperatures. The average mean-free-path of the gas mix- is the pressure drop across the porous bed, L is the thickness, R is
ture decreases by increasing pressure or decreasing temperature. the universal gas constant, ρ is density, M is molar mass and T is
October 2007, Volume 46, No. 10 57
 (a) (a)
50
106
N = 152 samples from 9 reservoirs
1 2
40 105
Frequency

3
30 104 5 4

Pc (kPa)
103
20 1: Shale I (~50 nD)
2: Shale II (~300 nD)
102 3: Shale III (~700 nD)
10 4: Crossfield Cardium Sand (230 µD)
Mode = 54 nD 101 5: Indiana Limestone (4,000 µD)

0
0 50 100 150 200 250 300 350 400 100
100 90 80 70 60 50 40 30 20 10 0
Permeability (nd) SHg (%)
(b)
(b)
100
100
Cumulative Frequency (%)

90
80 90 2
80
70
70
60 3
uSHg 60
50 1
u(lnPc) 50
40 5
40
30
30
20 20 4
10 10
0 0
0 50 100 150 200 250 300 350 400
10-3 2 10-2 2 10-1 2 100 2 101 2 102
Permeability (nd) Pore Throat Diameter ( m)

FIGURE 7: Frequency versus permeability of 152 shale gas samples FIGURE 8: (a) capillary pressure versus mercury saturation for
from nine reservoirs. (a) permeability distribution, (b) cumulative 3 shale samples, one sand sample and one limestone sample. (b)
frequency distribution. the pseudo-flow determined from the capillary pressure plots to
demonstrate dominant pore sizes to flow.
temperature. The expression Dk is the Knudsen diffusion coeffi-
cient given as: permeabilities are in nanoDarcies. Figure 7(b) presents the cu-
mulative frequency of the permeability data. From this figure, we
d 8 RT observed that 90% of the measured permeabilities are less than
Dk = 150 nD.
3 πM ........................................................................................ (4)

where d is the diameter of the nanopore. The derivation of Equa-

Extremely High Pressure Mercury (Hg)
tion (4) is presented in Appendix A. Injection
To obtain pore-size distribution of the core samples, traditional
Desorption mercury injections to obtain capillary pressure measurements were
made. The apparatus operates at extremely high pressures (up to
Gas molecules desorb from the surface of the kerogen to the
415 MPa or 60,000 psi). The results are plotted in Figure 8 for
pore space and then carry on due to pressure depletion. Desorption
three shale samples. The data of sandstone and limestone samples
in shale gas will be addressed in detail in a subsequent work.
are also plotted for comparison. As shown in Figure 8(a), capil-
lary pressure of the three shale samples (marked by 1, 2 and 3)
Diffusion in Kerogen increases rapidly by injecting mercury into the samples. For sand-
Once the gas molecules from the surface of the kerogen desorb stone (4) and limestone (5), the capillary pressure is lower. The de-
to the pore space, the gas concentration difference between the rivative of the mercury saturation SHg with respect to the natural
bulk of the kerogen and the surface of the kerogen controls gas dif- log of capillary pressure ln(Pc) is plotted versus pore throat diam-
fusion in solid kerogen. eters obtained from the Laplace equation in Figure 8(b). This de-
scribes the flow of mercury in the pores. As shown in Figure 8(b),
for the shale samples (1, 2 and 3), pore diameters in the range of 4
nm to 200 nm are the dominant flow passages, while for the sand-
Experiments stone and limestone, much larger pores contribute to flow.
The results of three sets of experiments are presented in this
section: pulse decay experiments used to measure permeability, Gas Evolution and Desorption Tests
extremely high pressure mercury injection to find pore-size dis-
tribution and gas evolution experiments from selected shale The general method of measuring the evolution of gas is based
samples. on the work of the Gas Research Institute(3) in their study of
coalbed methane. It can be summarized as follows: as soon as the
Pulse Decay Permeability core starts its trip up the wellbore, the start time is recorded; once
the core has been removed from the core barrel, it is examined and
Pulse decay is a technique used to measure permeability of cut into sections. Those sections where the on site geologist de-
tight rocks and synthetic materials(11, 12). Figure 7 presents per- cides good prospects lie, are then weighed and placed in plastic
meability data for 152 shale samples from nine reservoirs. Figure bags, and then placed in a standard core desorption canister. These
7(a) is the frequency versus permeability plot, where the measured canisters have a pressure gage and a valve on the top lid, and are
58 Journal of Canadian Petroleum Technology
closed with an o-ring seal. Once the canister is sealed, it is placed deviation (σ) is determined for each curve and converted to diffu-
in a water bath at reservoir temperature. At this point, gas volume sion coefficient (D):
measurements can begin. A schematic diagram of the set up is il-
lustrated in Figure 9.
(σVi )
2

These measurements are done in small time increments as long D=

as the gas production volumes are large, but these increments are
lengthened as the produced volume decreases. The first set of high
rate measurements are done in the field but once the rate slows
down, the canisters are placed in an ice bath and returned to the
laboratory where the samples are transferred to the water baths
again. The gas volume readings are continued for several months
until the gas volume change becomes too small to measure. At
each measurement of the gas volume in the manometre, the atmo-
spheric pressure and ambient temperature are recorded so that the
final gas volumes can be converted to standard temperature and
pressure (STP).
In Figure 10, we show plots for coalbed methane and the shale
gas sample. In Figure 10(a), the gas evolution of coalbed methane
is presented. The solid line is the model prediction based on the
spherical diffusion model. Figure 10(b) presents our shale sample
measurements for a typical cumulative gas volume versus time.
The gas evolution is clearly different from the coalbed methane
evolution curve. Hence, the spherical diffusion model might not be
accurate for the shale gas samples.
Different gas production rates are evident in Figure 10(b). These
different gas production rates are the basis of our analysis. Each
section of the curve represents a specified type of gas flow with
overlaps of each other. The next section explains how these sec-
tions are determined.
2t ............................................................................................. (6)
where Vi is the interstitial velocity and t is the time at the mean.
In Figure 10(b), data points are labeled as ‘data.’ Using Equation
(5), four different gas transport processes can be extracted from the
overall gas evolution curve. Process A, as shown in Figure 10(b),
corresponds to the gas flow in micropores which happens at the
early times of gas flow from the sample. This can be described by
Fickian diffusion or sometimes by a Darcy equation depending on
the original pressure in the system. Process B, in Figure 10(b), is
the gas flow in nanopores where a Knudsen diffusion is valid. Pro-
cess C describes gas desorption from the surface of the kerogen/
clays to the pore networks. Finally, Process D describes the gas
molecule diffusion from the kerogen bulk or clays to the exposed
surfaces. This process is very slow. Note that all these processes
overlap each other.
The extracted data from Figure 10(b), suggests that diffusion
coefficient in Process B (gas flow in the nanopore) is 4 × 10-7 m2/s,
which is consistent with the value of 3.8 × 10-7 m2/s (35 nm pore
at 375 K) obtained from the analysis of the theoretical model as
presented in Equation (4). Also, the determined diffusion coeffi-
cient for the gas molecule transport in the kerogen bulk is 2 × 10-10
m2/s which is consistent with the measurement of the gas diffusion
in bitumen(14). Assuming that kerogen and bitumen are alike, this
finding supports our preliminary approach of analysis.

Mathematical Modelling Conclusions

Assuming that gas flow behaviour in shale gas sediment is a The gas flow behaviour in shale gas sediments is studied with an
combination of all the above mentioned processes, i.e., gas diffu- emphasis on nanopore flow.
sion in kerogen/clays, desorption and flow in nanopores and mi-
cropores, then a group of Gaussian distribution curves can be used
to cover all these events(13) (see Appendix B for details): (a)

 2 m −x 1,200
n
( )  + C
∑ Fx = ∑ 0.5 ⋅ 2 ⋅ π ⋅hi ⋅ σ i ⋅ erf 

t
2σ i  1,000
Spherical model
i=1  
Gas Volume (cc)

............................... (5)
800

where, σ is Gaussian standard deviation, m is Gaussian mean, x is

600
an independent variable and h is a scaling factor.
The results of the analysis are presented in Figure 10(b). Each 400
process takes a Gaussian distribution function. Gaussian standard
200
Coalbed methane

Valve 0
100 2 101 2 102 2 103 2 104 2 105 2 106 2
Time (hrs)

Manometer (b)
7,000
Canister
6,000 data
5,000
Gas Volume (cc)

4,000 D
Sample
3,000

2,000
C
1,000 B
0

-1,000 A Shale gas

-2,000
0 10 20 30 40 50 60

Time (hrs)
Water Bath
FIGURE 10: (a) Gas evolution for a coalbed methane sample with
FIGURE 9: Schematic diagram of the setup for gas evolution the spherical model fit, (b) Gas evolution and production from a
measurement. shale gas sample with the Gaussian standard deviation plots.

October 2007, Volume 46, No. 10 59

 • A considerably large number of pulse decay permeability
measurements suggest an average of 54 nD permeability for
152 samples from nine selected reservoirs.
• Extremely high pressure mercury injection tests revealed the
dominance of the nanopores in shale samples.
• A method based on Gaussian distribution curves is proposed
to determine different flow behaviour in the shale gas flow.
• Our analysis showed that nanopores in shale gas sediments
contribute to the gas evolution processes. Gas flow in nano-
pores deviates from the traditional flow models, i.e., Fick’s
law or Darcy’s equation. An appropriate theoretical model of
gas flow in nanopores is presented.
Acknowledgements
We would like to thank Ms. B. Jeary, Conventional Oil and
Natural Gas (CONG) business unit manager, for her support and
encouragement.
Nomenclature
A = surface area, m2
c = mean molecular velocity, m/s
d = pore diameter, m
D = diffusion coefficient, m2/s
Dk = Knudsen diffusion coefficient, m2/s
Jk = free molecule flux, molecules/m3
kB = Boltzmann’s constant, J/K
Kn = Knudsen number, dimensionless
L = thickness, m
m = Gaussian mean, hr
M = molar mass, mol/g
P = pressure, Pa
q = flow rate, m3/s
R = universal gas constant, J/molK
t = time, hr
T = temperature, K
Vi = interstitial velocity, m/s
Greek Letters
ρ = density, kg/m3
ρN = number density, molecule/m3
α = dimensionless probability factor
σ = Gaussian standard Deviation, hr
δ = collision diameter of gas molecules, nm
λ = mean-free-path, nm
φ = porosity, fraction
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APPENDIX A: Derivation of Knudsen
Diffusion Coefficient in a Nanopore
Consider a gas with a molecular density of ρN (molecules/m3) at
one side of a pore and a vacuum at the other side. The free-mole-
cule flux Jk (molecules/m2) through the pore is given by(5, 7):
J k = αc ρ N
.......................................................................................... (A.1)
where, α is a dimensionless probability factor and c is the mean
molecular speed (m/s).
If there is gas on both sides of the pore, the net flux is propor-
tional to the difference in gas number densities at the two sides:
(
J k = αc ρ N 1 − ρ N 2 ) ............................................................................ (A.2)
where one represents the side of the tube with denser gas. In order
to use this equation, expressions are required for the mean molec-
ular speed and the dimensionless probability factor. The mean mo-
lecular speed is readily calculated using kinetic theory(8) as:
c=
8 RT
πM .......................................................................................... (A.3)
where R is the universal gas constant (J/kmol K), T the tempera-
ture (K) and M is the molar mass of the gas (kg/kmol). Calculation
of the probability factor α is considerably complicated, requiring
knowledge of the pore geometry. For a long straight circular tube of
diameter d and length L (L>>d) α is given by (d/3L). The method
of derivation of this expression is presented elsewhere(7).
The widely used parallel pore model of porous media uses the
latter of the above simple geometry. Development of this model
is as follows. Substituting α = (d/3L) and c as given by Equation
(A.3) in Equation (A.2) gives:
Jk =
d 8 RT
ρ −ρ ( )
3L πM N 1 N 2 ................................................................ (A.4)
which can be re-written in differential form (applied along the axis
of the cylindrical pore, z) and applying the convention that flux
moves from high to low concentration as:
– d 8 RT  dρ 
Jk =  N 
3 πM  dz  ....................................................................... (A.5)
 Considering the flux Jk to be in mole, not molecules, and con- This function is most valuable in the summation form where we
sidering the rate of change of gas concentration C (mol/m3) rather can convolute multiple distribution functions.
than molecular concentration, gives:
 2 m −x
n
( )  + C
−d 8 RT  dC  ∑ Fx = ∑ 0.5 ⋅ 2 ⋅ π ⋅hi ⋅ σ i ⋅ erf 

i
2σ i 
Jk =   i=1  
3 πM  dz  ............................(B.4)
.......................................................................... (A.6)
where the subscript i represents the parameters described above
Hence, by analogy to continuum gas diffusion, Knudsen diffu- needed to define each dispersion curve and C is the constant of
sion coefficient Dk for flow in a long straight pore is obtained as: integration.

d 8 RT
Dk =
3 πM .................................................................................... (A.7)
Provenance—Original unsolicited manuscript, Nano-Scale Gas Flow in
Shale Gas Sediments (2007-10-14). Abstract submitted for review June
Therefore, the Knudsen diffusion coefficient is propor- 5, 2007; editorial comments sent to the author(s) August 2, 2007; revised
tional to the pore diameter and the mean molecular velocity or manuscript received August 17, 2007; paper approved for pre-press August
temperature. 17, 2007; final approval September 7, 2007.

Knudsen Diffusion Coefficient in Porous

Media
Authors’ Biographies
Due to the complexity of the geometry of most porous media,
Knudsen diffusion coefficients are typically calculated from ex- Farzam Javadpour received his B.Sc. with
perimental data. If experimental data is not available, a model distinction in petroleum engineering from
must be selected. The approach is to consider porous media as con- the Petroleum University of Technology
sisting of a certain percentage of open pores (porosity) of the mean (Iran), and M.Sc. and Ph.D. degrees in
pore diameter and having a degree of interconnection resulting in chemical and petroleum engineering from
paths longer than a direct path (tortuosity). Hence, Knudsen flow the University of Calgary. He served on the
through porous media can be modelled using a modified form of Technical Committee of the Canadian Inter-
Equation (A.7). national Petroleum Conference (CIPC) in
2004 and 2005. He serves as a member of
φ the Editorial Review Board for the Journal
Dk , pm = D of Canadian Petroleum Technology (JCPT) and is Issue Coordi-
τ k ...................................................................................... (A.8)
nator of the August issue. He is currently working as Research Sci-
entist/Engineer at the Alberta Research Council on projects related
where, φ/τ is the porosity-tortuosity factor. to enhanced oil and gas recovery, shale gas, coalbed methane and
CO2 sequestration. He is also an instructor at the University of Cal-
gary. He worked as a Reservoir Engineer for the National Iranian
APPENDIX B: Determination of Diffusion Oil Company for six years. He has presented and published over 30
technical papers on topics related to reservoir engineering. Farzam
Coefficient from Gas Evolution Data is an invited speaker on the subjects related to transport in porous
The modelling of the gas evolution curves uses a class of mathe- media in Europe and the United States.
matical models based on the characteristics of the probability den-
sity function described by the Gaussian equation(13). Douglas Fisher started his career at the Pe-
troleum Recovery Institute (PRI) in 1976
 2
and joined the Alberta Research Council
(
− x − m ) 
() 1 (ARC) in 2000. It was at PRI that he, along
f x = ⋅ exp   with Selim Sayegh, developed one of the
2π ⋅ σ  2σ
2
 early high-pressure micromodel systems.
.........................................................(B.1)
Over this period, he has acquired expertise
where, σ is Gaussian standard deviation, m is Gaussian mean and x in image analysis and data mining methods
is the independent variable. In a general form, Equation (B.1) can as applied to general research problems. At
be written as: ARC, he focuses on the development of
new methods of image analysis to extract
 2 information from experimental systems such as the new Micro
− x − m( ) 
()
Slim Tube and other related high-pressure micromodels.
f x = h ⋅ exp  
2σ 2
 
Michelle Unsworth received her B.Sc. in
..................................................................(B.2)
geology, as well as a Masters in business
The term h allows this function to represent the distribution administration from the University of Al-
without it being normalized to have an area of one. This is impor- berta. She is currently working at the Al-
tant in physical modelling since, in general, we do not have data berta Research Council as Team Lead of the
sets where the integral is unity. Unconventional Gas Research Group. Her
If we assume that the flow properties of the sample are repre- activities are commercially focused on pro-
sented by pore structures and diffusion mechanisms that can be de- viding oil and gas exploration and devel-
scribed as a group of Gaussian distributions, then we can convert opment companies with accurate, reliable
this form of the equation into its cumulative form. data on natural gas contents of both coalbed
methane, as well as shale gas samples. The
Alberta Research Council has been concentrating its efforts on de-
 2 m −x
( )  + C
∫ f ( x ) dx = 0.5 ⋅
veloping better methods to measure gas evolution, evaluate gas
Fx = 2 ⋅ π ⋅hi ⋅ σ i ⋅ erf  i
 2σ i  composition, determine maturity profiles and delineate between
  different types of gas transport out of highly microporous shales.
.................(B.3)
October 2007, Volume 46, No. 10 61