Innovations in Applied and Theoretical Rock Mechanics Editors – Hassani, Hadjigeorgiou, Archibald

©2015 by the Canadian Institute of Mining, Metallurgy & Petroleum and ISRM, ISBN 978-1-926872-25-4
13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP

IN PIERRE SHALE

A., Hayatdavoudi
University of Louisiana-Lafayette, Louisiana
Corresponding Author:asad.hayatdavoudi@gmail.com

K.G., Sawant, F., Boukadi

University of Louisiana-Lafayette, Louisiana

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
A. Hayatdavoudi, K.G. Sawant, F. Boukadi 1
 13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

ABSTRACT

In this work, we found that contact between shale and water results in development of micro fractures.
Based on results of experiments on Pierre shale, we conclude that appearance of micro fractures begin with
saturation of capillaries, ionic and diffusive transport of water into the shale clays and once capillaries are
saturated, the cause of micro fracture propagation is the conversion of ionic activity/exchange to excess
pressure that did not exist before fracking. Based on these findings, the spread of micro fractures appear to
be a time-dependent phenomenon which has not been addressed in the existing macro/micro fracture
models.

KEYWORDS
Free energy, Virial coefficient, Capillary saturation, Pitzer, De-bye Huckel limiting law, Pourbaix, Time-
dependent shale/water interactions.

INTRODUCTION

Shale has often been involved as a hazard in drilling operations. This hazard can be defined as
“destabilization” of shale. When contacted with water-based drilling fluids, some shales readily swell and
sometimes, cause the wellbore to cave-in, slough, wash-out, close, and pack-off, impeding the drilling by
sticking the drill-pipe. However, once drilling reaches the desired depth or length, the casing is set,
cemented, and perforated, and then actually we wish to initiate fractures and destabilize the shale formation,
using hydraulic fracturing.
Clays constitute a major portion of minerals in shale. These clays contain a large amount of free energy
which is the main factor for “slick” water adsorption/absorption. In fact, the reason for using “surfactants”
in hydraulic fracturing fluids is to make the penetration of the fluid into the capillaries much easier, thus
water meets with less resistance to enter the small capillaries. Also, the result of high capillary suction
pressure is due to small Angstrom size capillaries, smaller pores and presence of ions and hydrateable metal
atoms. The free energy is thus, related to all the above mentioned and other affects. Capillary pressure,
osmotic pressure and other pressures are responsible for creating the micro-fractures in shale, thus,
increasing the network of micro-fractures which leads to more gas production.
The objective of this study is to evaluate the pressures of the individual ions which are released by the
diffusing “slick” water into shale. These pressures would be added to the above mentioned capillary
pressure, osmotic pressure, bacterially-induced pressures, chemically-induced reaction pressure, pressure
due to exchangeable ion-transport, pressure due to release of free energy of solvation and eventually to the
pore pressure as suggested by Terzaghi’s equation.

THEORY

Figure 1. Typical Minifrac Injection Test

In a typical Mini-frac injection test, the bottomhole pressure has to reach the fracture or the breakdown
pressure of a particular formation. The fracture closure stress, as shown in Figure.1 is a transition point
between the pre-closure and the after-closure stresses. The authors believe that prolonged shut-in of the well

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
2 A. Hayatdavoudi, K.G. Sawant, F. Boukadi
13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

will help the aforementioned pressures to build-up in Pierre shale, as shown in Figure.1, thus, enhancing
development and propagation of micro-fractures resulting in higher gas production.
The micro-fracture network formed in shale, as shown in Figure.2, is a result of water vapor diffusion and
consequently, swelling of shale (Savage, 2014). But the same micro-fracture network can be developed
around the walls of the main hydraulic fracture with prolonged shut-in time after hydraulic fracturing of
shale gas wells. Often, diffusion of “slick” water occurs as a result of concentration difference of solutes in
water and shale. As a result of diffusion, the concentrations of exchangeable cations/anions increase in
“slick” water, which were earlier, equal to zero, assuming no shale-stabilizer salts were added to the slick
water. The exchange causes the water vapor pressure to fall until an equilibrium value is reached. This
concentration can be related to pressure via the formula

Pion = Po + ∆G/V (1)

where: Pion, is the ionically-induced pressure, Po is the reference pressure, ∆G = RT(ϒionCion); R is the
Universal Gas Constant, T is the temperature, ϒion is the activity coefficient, Cion is the ion concentration
and V is the molar volume.

Figure 2. Process of Micro-fracture propagation with respect to time in Pierre shale (Savage 2014)

In order to estimate the concentration trend of various ions specific to the Pitzer (Plummer, 1988 et.al.)
model, we evaluated their activities and Gibbs free energy by solving the following second-order
differential diffusivity equation. The second order one-dimensional differential diffusivity equation is given
by

∂C/∂t = D.(∂2C/∂x2) (2)

For which the solution is approximated by

Cion = Co.erf(x/2√ (Dt)) (3)

Where: Co is the initial ion concentration, D is the diffusion coefficient, t is time and x is the space co-
ordinate.
GIBBS FREE ENERGY
A portion of the total energy includes Gibbs free energy of the system of clays. This energy is available to
do work and is defined by the equation
∆G = ∆H – T∆S (4)
Where: ∆G is the Gibbs free energy, ∆H is the Enthalpy, ∆S is the entropy.
According to Figure.3, as suggested by one of the authors, different types of clays have different Gibbs free
energy, the highest being in Smectite and the lowest, in Kaolinite. Smectite is the main clay constituent in
Pierre shale and its free energy is available to do work, for example, potential work such as Eh (Redox
Potential). The shale fracturing water, i. e. the “slick” water, uses this available free energy to activate the

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
A. Hayatdavoudi, K.G. Sawant, F. Boukadi 3
 13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

capillaries and other macro, meso and micro pores thus, creating a micro-fracture networks along the main
faces of hydraulic fractures.

Figure 3. Suggested scale for relationship between Hydration Index and Gibbs free energy at standard
isentropic conditions for a family of basic clays found in shale (Adapted from SPE 50729)

To get a better appreciation of relationship between concentration of ions and Gibbs free energy, for high
concentration ions, we use the Pitzer model. However, for low concentration ions, we use the Extended
Debye-Huckel Limiting Law.
PITZER MODEL
The Pitzer model allows one to make geochemical calculations in brines and other electrolyte solutions of
high concentrations. In this method, we used the Pitzer virial-coefficient approach for activity coefficient
corrections. These coefficients characterize the interactions between solute molecules as well as between the
solute and solvent. “This model can be used in reaction modeling which include calculation of (1) aqueous
speciation and mineral-saturation index (2) mineral solubility (3) irreversible reactions and mineral-water
mass transfer etc. The computed results for each aqueous solution include the osmotic coefficient, water
activity, mineral saturation indices, mean activity coefficients, total activity coefficients and scale-
dependent values of pH, individual-ion activities and individual-ion activity coefficients”(Plummer, L.N. et.
al).
The osmotic co-efficient, φ, and the activity coefficients of the cations, and anions are given by
Harvie and Weare, 1980, as follows:

(5)

(6)

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
4 A. Hayatdavoudi, K.G. Sawant, F. Boukadi
13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

(7)
Where: ϕ is the osmotic coefficient, I is the ionic strength, m is the molality of ion, c and M are cation
subscripts, a and X are anion subscripts, z is the ionic charge, Bϕ, C, ψ are virial coefficients.
The activity coefficients calculated in our work are based on the above mentioned model, and its corollaries
are used in order to estimate the Gibbs free energy and the equivalent pressure for each ion which enters the
diffusing slick water from the shale. It is this pressure that the authors believe is responsible for creating
micro-fractures which liberate more gas from the shale.

Limitations of Pitzer model

“The Pitzer interaction parameters are defined for a system of Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-
CO2-H2O extended to Fe (II), Mn (II), Sr, Ba, Li and Br”. However, the authors believe that the lack of
Pitzer interaction parameters for aqueous aluminum and silicon species is one of the main deficiencies in
the Pitzer approach for measurements of Eh.
To account for the effect of Si+4 ions, the activity and consequently, the Gibbs free energy have been
calculated with the help of Extended Debye-Huckel activity model. This was the best that the authors could
attempt to perform calculations on Si+4 ion, as given by:

log ϒ = (-Az2√I)/(1+Bao√I) (8)

where:A = 1.82x106(ϵT)-3/2, B = 50.3(ϵT)-1/2, ϵ is the dielectric constant, I is the ionic strength of the solution
and ao is the ion-size parameter ranging from 3 to 9, depending on the type of ion. For silicon ion, the
authors assumed a value of 10.

EXPERIMENTAL PROCEDURE
Two dry shale samples, each of about 1cubic inch, in volume were weighed and the masses were recorded.
We used 100 mL deionized water, and we immersed the pH/Eh and temperature electrode into this
deionized water in such a manner that the bulb and the reference junction of the electrode were covered with
water. The data was recorded every 3 seconds for 1 hour. Simultaneously, a microscope was installed right
above the sample in order to video capture the top view of the shale and the surrounding water activity.
Thus, we generated a time-series data for pH, Eh and temperature along with the recording of events
observed under microscope. These events included release of gas bubbles and dispersion of shale. To
differentiate the effect of input energy on the liberation of ions, one sample was subjected to agitation and
the other was not. The two samples were stored in a cold environment for about two days and then tested for
ion concentration using ICP-MS (Inductively Coupled Plasma with Mass Spectroscopy).

RESULTS

Figures 4 and 5 show the electric potential or more precisely, the redox potential (Eh). The profile for
samples 1 and 2 follow the same trend since we used the same species of Pierre shale; the only difference
being sample 1 looks smoother than sample 2. This could be the effect of the number of fussility planes
being less in sample 1. In Figure 5, due to instrument error, as a result of dispersed shale particles
contacting the electrode, there is an abnormal dip in the redox potential near the end of experiment. These
redox potentials are the best guide in judging the concentration profiles for the shale samples and have been
used in ionic diffusion coefficient calculations. The authors interpret the significance of initial horizontal
profiles, as recorded in sections (1) of the Figures 4 and 5 for both samples, as an indication of surface
saturation by water during the immersion of shale under water and the subsequent release of the first,
observed gas bubble from the shale. The driving force in section (1) is the constant hydraulic potential
exerted by the head of water on the surfaces of shale specimens. The first sharp slope change in section (2)
of Figures 4 and 5 are indicative of diffusion of water during post surface saturation time. In this section
water diffuses into the largest pores of shale specimen, i.e. the macro-pores. The evidence suggests that in
one hand, the diffusive invasion of largest pores by water molecules appears to be associated with the

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
A. Hayatdavoudi, K.G. Sawant, F. Boukadi 5
 13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

largest slope change, the highest amount of cation concentration, and the release of larger gas bubbles.
However, on the other hand, the smaller change of slope in section (3) and after is attributed to further
diffusion of water into smaller pores, i.e. meso-pores and micro-pores so on and so forth. Thus, after the
saturation period, he diffusive processes of water into the shale mass begin with ionization of various
adsorbed or structural cations immediately followed by displacement of gas bubbles of various sizes from
the host shale. The end result of saturation and diffusion processes is development of micro-fracture
networks through which gas bubbles flow. We have used the changes of slope in these figures to estimate
the diffusion coefficient of water into various sizes of shale pores and activation of capillaries which release
various sizes of gas bubbles from the shale mass (Hayatdavoudi, et.al)

Figure 4. Electric Potential as a function of time for sample 1

Figure 5. Electric Potential as a function of time in sample 2.

Figures 6 and 7 show the concentration trends for the ions with respect to time for samples 1 and 2. The
concentration profile for sodium ion is the strongest for both the samples. This is obvious since sodium is
the exchangeable cation in Smectite and is the most affected by diffusing water, followed by bicarbonate,
sulfate and chlorine ions. The remaining ions are at very low concentrations in water, hence their
concentration profiles are not strong enough to stand out as sodium. The average diffusivity coefficients for
samples 1 and 2 are 38.82 x 10-8 m2/s and 35.72 x 10-8 m2/s. These values of D are used in Equation 3 to
estimate the concentration profiles.

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
6 A. Hayatdavoudi, K.G. Sawant, F. Boukadi
13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

Figure 6. Ionic Concentration Profile as calculated by Pitzer and extended Debye-Huckel Model for
sample1

Figure 7. Ionic Concentration Profile as calculated by Pitzer and extended Debye-Huckel Model for
sample2

Figures 8, 9, 10 and 11 provide proof for the presence of the ions in water which eventually results in a
change in (P/P0) for water due to ionic diffusion, using Equation 1. In sample 1, for ions like sodium,
bicarbonate, chlorine and sulfate, which have stronger concentration profiles as shown in Figure 6, the
pressure trends are likely to have less curvature. This means, the pressure required in order to remove these
ions from shale depends on the strength of the concentration profile of these ions. For example, the pressure
for sodium ion increases from 14.7 psi to 16.4 psi per gram of sample, which is an indication that sodium
initially had a hidden pressure of at least 2 psi locked in the shale. On the contrary, our examination of
pressure trends as contributed by calcium or potassium, the final pressures being 39 psi and 34 psi per gram
of sample, respectively, the curvature signifies that an ample amount of energy needs to be spent for
displacing these ions from the shale. Regarding the pressure for magnesium ion, in sample 1, the curve is
less “bow” than sample 2. The reason for this is only the final concentrations of magnesium in samples 1
and 2 (2.7 ppm and 1.7 ppm per gram of sample, respectively). The same reason can be explained for the
iron ion. In Figures 9 and 11, barium, strontium, iron, manganese show negative pressures which
consequently takes us to the obvious result that these ions were present in negligible quantities in shale (the

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
A. Hayatdavoudi, K.G. Sawant, F. Boukadi 7
 13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

pressure to be established to remove barium at that minute concentration in samples 1and 2, i.e., 1,000,000
psi is impossible).

At this point it is important to mention that all pressures in terms of ionic concentration of each species in
the shale and the adsorbed-absorbed water will add up to lead to pressure build up in post fracturing shut-in
period. Obviously this will depend on each species’ ionic concentration within a given molar volume of the
fracturing fluid and its own partial pressure. Consequently, these ionically dependent pressures will add up
to create an excess pressure that was not there prior to hydraulic fracturing. These pressures simply appear
after interaction and reaction of water with the shale mass. The consequence of the pressure build up is
creation of more and more number of micro fractures in the shale mass (Hayatdavoudi, Chitila et. al. 2015)

Figure 8. Change in water vapor pressure due to change in ionic concentration profiles as a function of time
for sample 1

Figure 9. Change in water vapor pressure due to change in ionic concentration profiles as a function of time
for sample 1

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
8 A. Hayatdavoudi, K.G. Sawant, F. Boukadi
13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

Figure 10. Change in water vapor pressure due to change in ionic concentration profiles as a function of
time for sample 2

Figure 11. Change in water vapor pressure due to change in ionic concentration profiles as a function of
time for sample 2

Using Pitzer model, we evaluated the activity coefficients which are listed in Table 1. These coefficients are
used in calculating the activities from the concentration profiles in Figures 6 and 7. The results for the
activity coefficients had zero electrical imbalance error for both samples 1and 2. Since the Pitzer model is
not yet compatible with aluminum and silicates, the authors have estimated the activity coefficient for
silicon ion with the help of Extended Debye-Huckel Law. This assumption leads to a discrepancy in the
pressure profiles of silicon having less curvature as seen in Figures 8 and 10.
The authors measured the pH of samples 1 and 2. The pH ranged from 8 to 9. At the same time, we
measured the redox potential (Eh). Placing the range of pH and the corresponding Eh values for the two
samples, as shown in Figure 12, justifies the absence of aluminum ion (Al+3) in the aqueous solution.
However, according to Figure 12, we observe that aluminum complexes such as AlO2- are likely to be
present in the solution.

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
A. Hayatdavoudi, K.G. Sawant, F. Boukadi 9
 13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

Figure 12. Pourbaix Diagram for the presence of aluminum ions and its complexes

Table 1. Activity coefficients for the ions specific to Pitzer system

SAMPLE 1 SAMPLE 2
Ion Activity coefficient Ion Activity coefficient
Na 0.980199 Na 0.983144
Ca 0.914846 Ca 0.928672
Mg 0.916677 Mg 0.930531
K 0.980199 K 0.983144
Si 0.123000 Si 0.142
HCO3 0.980199 HCO3 0.983144
Cl 0.980199 Cl 0.983144
SO4 0.922194 SO4 0.934260
Ba 0.922194 Ba 0.933327
Fe 0.915761 Fe 0.929601
Li 0.980199 Li 0.983144
Mn 0.915761 Mn 0.929601
Sr 0.913018 Sr 0.927743

CONCLUSION

Based on the results, we may conclude that:

1. The Eh profile clearly indicates the capillary saturation and release of the first bubble in the
horizontal section of the graphs.
2. Breaks in the graph indicate penetration of water into the macro, meso and micro pores,
respectively.
3. Concentration profile for sodium is the highest, indicating that it is the most abundant
exchangeable cation, typical of presence of highest Smectite concentration in Pierre shale.
4. The major contributors to the change in vapor pressure of water are sodium, bicarbonates, sulfates
and chlorine.
5. The shape of the curvature related to pressure profiles indicate the differences in the amount of
energy required to displace the respective ions, (Na,Ca,Mg,K,Si,HCO3,Cl,SO4)from the shale in
samples 1 and 2.
6. The discrepancies in the pressure profiles due to silicon ion are a result of lack of Pitzer interaction
parameters for silicon and the use of the alternate extended Debye-Huckel Limiting Law.
7. The non-existence of aluminium ions can be attributed to existence of AlO2- and its complexes, but
not Al+3 itself.

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
IN PIERRE SHALE
10 A. Hayatdavoudi, K.G. Sawant, F. Boukadi
13th International Congress of Rock Mechanics ISRM13
10-13 May 2015, Montreal, Canada

8. Transport of the ions out of shale to water coincides with the initiation and propagation of micro-
fracture networks. This could lead to more gas production upon prolonged post hydraulic
fracturing shut-in time.

REFERENCES

Crank, J., “The Mathematics of Diffusion”, Brunel University, Uxbridge, 2nd edition 1971

Hayatdavoudi, A., “Changing Chemophysical Properties of Formation and Drilling Fluid Enhances
Penetration Rate and Bit Life”, SPE 50729, University of Southwestern Louisiana

Hayatdavoudi, A., Boamah, M. A., Tavanaei, A., Sawant, K.G., Boukadi, F., “Post Frac Gas Production
Through Shale Capillary Activation”, SPE-173606-MS, University of Louisiana at Lafayette

Hayatdavoudi, A., Chitila, D., “Effect of Variable Temperature, Water Vapor and Exposure Time on
Microfracture Propagation in Shale”, 837, ISRM 2015

Plummer, L.N., Parkhurst, D.L., Fleming, G.W., Dunkle, S.A., “A Computer Program Incorporating
Pitzer’s Equations for Calculations of Geochemical Reactions in Brines”

Roberge, P.R., “Corrosion Engineering: Principles and Practice”, McGraw-Hill, 3rd edition

Savage, F., “Effect of Dry-Wet Cycles on Fracture Propagation in Shale and Gas Production Mechanism”,
MS Thesis, University of Louisiana at Lafayette, Spring 2014.

Zhang, G., Spycher, N., Xu, T., Sonnenthal, E., Steefel, C., “Reactive Geochemical Transport Modeling of
Concentrated Aqueous Solutions: Supplement to TOUGHREACT User’s Guide for the Pitzer Ion-
Interaction Model”, Earth Sciences Division, December 2006 Revision 00

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A CHEMO-PHYSICAL MODEL FOR PREDICTING POST-FRACKING PRESSURE BUILD-UP
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A. Hayatdavoudi, K.G. Sawant, F. Boukadi 11