SPE 82211

Organic Acids in Carbonate Acidizing

Marten Buijse, SPE, Peter de Boer, SPE, Bert Breukel, SPE, Monique Klos, Shell International Exploration and
Production BV, Gerardo Burgos, Shell Venezuela S.A.
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE European Formation Damage Conference to be held in The Hague, The Netherlands 13-14 May 2003.
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Abstract
This paper discusses the use of organic acid as a stimulation
fluid in carbonate formations. Organic acids such as acetic or
formic acid have been used for many years as alternatives to
HCl, due to the retarded reaction rate, low corrosivity and reduced tendency to form acid-oil sludge in asphaltene rich crudes. In Venezuela, organic acids were pumped in acid fracturing treatments in deep hot limestone formations. Case histories
are discussed in the paper. Although these treatments were
very successful, optimization of the design was hampered by
the fact that models for organic acid-carbonate spending did
not exist.
In this paper a new model for acid spending is proposed
that can be used for strong acids (HCl) and for weak (organic)
acids and also for acid mixtures. Compared to existing (HCl)
models the only new element is the acid dissociation constant,
describing the differences between strong and weak acids. The
model was verified by comparing simulated reaction rates
with rates actually measured in the laboratory with the rotating
disk. Results of acid fracture simulations, comparing etched
length and width of organic acid with HCl acid are also discussed in this paper.
Introduction
In most carbonate stimulation treatments, above and below
fracturing pressure, hydrochloric acid (HCl) is pumped as the
main stimulation fluid. HCl is cheap, it has a high rock dissolving power and the reaction products are usually soluble.
However, the HCl-carbonate reaction is also fast, especially at
the higher temperatures encountered down hole1,2. The rapid
HCl spending prevents deep penetration of acid into the formation. In matrix treatments this results in only short wormholes or even compact dissolution with only marginal skin
decrease3,4. In acid fracturing treatments it results in poor
etched length, often considerably less than the fracture half-

length created with the pad fluid. Other disadvantages of HCl

are excessive tubing corrosion and associated high cost of inhibition5 and the tendency to form acid-oil sludge in asphaltene rich crudes6.
Organic acids such as acetic or formic are good alternatives to HCl and find more and more applications as cleanup
and stimulation fluids, especially in high BHT wells. These
are weak acids that spent slower on carbonate rock, compared
to HCl, providing deeper penetration and improved stimulation. This will be illustrated in the paper with case histories of
organic-acid fracturing treatments in the Maraca limestone
(Lake Maracaibo, Venezuela). Although these treatments were
very successful, optimization of the design was hampered by
the fact that models for organic acid-carbonate spending did
not exist.
In order to effectively apply organic acids in stimulation
treatments, a proper understanding of the acid-rock reactivity
is required. The HCl-carbonate reactivity has been studied
extensively1,2,7,8, and many models are described in literature
to calculate the acid penetration distance in a fracture, wormhole lengths in a matrix treatment, etc.9,10. In contrast, organic
acid-carbonate reactivity has not been studied a lot. In the 70s
some work was done on the thermodynamic limitations that
are responsible for the incomplete spending of organic acids at
high pressure1,11. Even less work has been done on reaction
rate studies of organic acid reactions with carbonate rock. A
paper was published recently by Fredd et. al.12 in which the
kinetics of calcite dissolution in acetic acid was investigated.
However, a comprehensive model of organic acid spending on
carbonate rock does not yet exist. For example, the acid
spending models in commercially available acid fracturing
software packages are all based on HCl acid, and have only
limited use in the design of an organic acid treatment.
The goal of this study was to build a general model of
acid-carbonate spending that can be used for strong acids
(HCl) as well as for weak (organic) acids and also for acid
mixtures. Both the thermodynamic issues (incomplete spending) and the reaction rate are addressed. The model is applicable to those acids that dissolve rock in a reaction that involves
the H+ ion, such as acetic acid or formic acid. The model is not
applicable to other organic acids, such as EDTA, that dissolve
carbonate by complexing the calcium. The intend was to keep
the model simple, and no attempt was made to capture all
physics and chemistry. Compared to existing (HCl) models the
only new element is the acid dissociation constant, describing
the differences between strong and weak acids. The model
was verified by comparing simulated reaction rates, with rates

SPE 82211

actually measured in the laboratory with the rotating disk. Despite the models simplicity, it proved to be accurate enough
for our purposes and it is now build into our Acid Fracturing
software. The model was used to analyze acid spending and
etching in a fracture. Results of these simulations, comparing
the performance of organic acids with HCl are discussed in
this paper. The mathematical details of the model are described in the Appendix.
Organic Acid Fracturing in Venezuela
The Cogollo group is a tough carbonate play in Lake Maracaibo, consisting of three formations -Maraca, Lisure and
Apon- totaling some 1000 ft. thickness at a depth of 15,000 ft.
The interval of best quality is the vuggy limestone of the Maraca formation, some 25-50 ft thick with porosities ranging
from 4-8% and permeabilitys of about 10-20 md. Well stimulation is required to make the wells economical. Acid fracturing with HCl acid was considered but modeling indicated an
etched length of only 30-40 ft. The reason for the poor etched
length is the very high spending rate of HCl with the limestone
at the downhole temperature of 280F. The goal of these
treatments was to create as much etched length as possible. It
was therefore decided to use a retarded (organic) acid system.
The organic acid spends slower on rock, compared to HCl,
and will penetrate deeper into the formation, providing for
more conductive length13. Additional benefits of organic acids
over HCl are its lower corrosivity and easier inhibition and a
reduced tendency to form acid-oil sludge. A mixture of 13/9%
acetic/formic acid was chosen because it has the same total
acid strength as 15% HCl. (Note, however, that the rock dissolving power of 13/9% acetic/formic is considerably less than
that of 15% HCl; see further below).
Stage
1
2
3
4
5
6
7
8
9
10
11
12
13

Fluid
Organic acid
Gelled water
Crosslinked PAD
Gelled Organic Acid
Crosslinked PAD
Gelled Organic Acid
Crosslinked PAD
Gelled Organic Acid
Gelled water
Organic Acid (CFA)
Organic Acid (CFA)
Water w/methanol
Water

Volume
bbl
5
145
200
220
100
220
100
220
200
170
40
50
161

Rate
bpm
2
2-18
18
18
18
18
18
18
18-20
20-4
4
4
4

Table 1. Typical organic acid fracturing treatment.

Table 1 illustrates a typical treatment procedure, pumping a
total of 880 bbl organic acid in four stages. The last stage was
a closed fracture acidizing stage (CFA), pumped at low rates,
to ensure good conductivity in the near wellbore.
The post-job production increase in a number of wells is illustrated in table 2. Post-job skins were in the range of -3 to
-6. The production gains and the highly negative skin values
were an indication that the etched length was (much) more
than the 30-40 ft that could be expected in an HCl treatment.
Analysis of post treatment well tests indeed indicated an
etched length in excess of 150 ft. Although successful, the
impression was that these treatments could be further opti-

mized. However, a proper model for organic acid spending in

a fracture did not exist. This prompted the research into organic acid-carbonate reactivity and the development of a new
acid spending model.
Net Pay
ft
14
22
17
26
47
22
16
9
45
25
28

Well
A
B
C
D
E
F
G
H
I
J
K
Total

Prod. Before
bopd
0
350
0
1000
1525
0
450
0
0
0
294
3619

Prod. After
bopd
1252
1717
1940
3152
4290
260
2005
350
2485
882
2162
20495

Table 2. Pre- and post job production results.

Acid-Carbonate Spending Equilibrium
The difference between a strong acid and a weak acid is the
degree of dissociation in solution. For acid HA the dissociation reaction is:
HA H+ + A-

(1)

This is an equilibrium reaction, with the equilibrium (dissociation) constant given by:
KA =

[ H + ] [ A ]
[ HA]

(2)

Strong acids such as HCl are nearly 100% dissociated and KA

has a value >>1. Weak acids are much less dissociated and the
corresponding value of KA is <<1. In table 3 the value of KA
and the strength of a 1 mol/l solution is listed for HCl, acetic
and formic acid. Note that the % dissociation of formic acid,
which is one of the stronger organic acids, is still only 1.6%.

acid type
HCl
Formic
Acetic

diss. constant KA
(mol/l)
>>1
1.8E-4
1.8E-5

strength of 1 mol/l
+
[H ]
pH
mol/l
0
1.0
1.8
0.016
2.3
0.005

Table 3. Dissociation constant and strength of HCl,

acetic and formic acid.
The acid is consumed in the acid-carbonate reaction:
2H+ + CaCO3 Ca2+ + H2O + CO2

(3)

The depletion of H+ results in a pH increase and this will drive

the acid dissociation reaction to the right, and more acid will
dissociate. The final acid-carbonate equilibrium state depends
on the amount of CO2 in solution. The CO2 generated in the
reaction will stay in solution at pressures >1000 psi2. Part of
the CO2 will be present as carbonic acid, H2CO3. Due to buffering action of the carbonic acid, the final acid-carbonate equilibrium pH will be in the range 4.0-6.0. At these pH values, a
weak acid is not yet completely dissociated. For example,

SPE 82211

when 10% acetic acid spends on carbonate rock at 200F, the

final pH is about 5, but 46% of the acid is still undissociated
and will not spent. The conclusion is that under downhole
conditions weak acids do not spend 100%. This is further illustrated in fig. 1, were the equilibrium pH and % spending
are plotted as function of pKA=-log(KA). HCl has a negative
pKA value and will spend 100%. Formic and acetic acid have
pKA values of 3.7 and 4.7 respectively and will not spend
to completion.

Acetic

% spending

% spending

80

acid
strength
mol/l

6.5
6

0.5
1
2
4

60

5.5
5

40

4.5

pH

20
0
0

0.5
1
2
4

equiv.
HCl %
3.4
6.8
8.5
14.1
16.5

Table 4. Spending of acid components in acid mixtures, and equivalent HCl concentration.
In an acid mixture the spending of the weakest component
is suppressed even more. For example, when 10% acetic
spends on carbonate rock about 54% of the acetic spends.
However, in the mixture 15/10% HCl/Acetic, only 24% of the
acetic acid will spend. From a rock dissolving point of view,
the 10% acetic acid does not add much in this mixture.

pH

Formic
100

% of acid component spend

HCl
Acetic
Formic
54
85
31
82
100
78
100
24
-

acid mix
10% Acetic
10% Formic
13/9% Ac/Fo
7/11% HCl/Fo
15/10% HCl/Ac

3.5
3
8

pKA = -log(KA)

Figure 1. Equilibrium pH and % spending as a function of KA.

The incomplete spending of organic acids under downhole
conditions is by no means a new finding, and is actually extensively discussed in literature1,2,11. However, this knowledge
is often forgotten in the design of organic acid treatments.
For example, the mixture 13/9% acetic/formic is quite popular
because it has the same strength (4.4 mol/l) as 15% HCl. This
suggests that the dissolving power of 13/9% acetic/formic is
equal to that of 15% HCl 5. In reality, however, the dissolving
power under downhole conditions is equivalent to that of
about 8% HCl.
The curves in fig. 1 are calculated with the newly derived
model described in the Appendix. Three pieces of data enter
the model: the solubility product of CaCO3, the equilibrium
constants of the carbonic acid reactions and the acid dissociation constant KA. The result is a simple quadratic equation that
must be solved to calculate the equilibrium pH (eq. A-14).
Once the equilibrium pH is known, the amount of undissociated acid and the % spending can be easily calculated from eq.
(2). The % spending calculated with the model for acetic and
formic acid compares well with the empirical results discussed
elsewhere in literature1,2. The model can also be used to calculate the % spending in acid mixtures. In table 4 the % spending of acid components in several mixtures is calculated.

Acid-carbonate reaction rate

The rate of the HCl-carbonate reaction has been studied extensively1,2,7,8. The dissolution reaction is:
H+ + CaCO3 Ca2+ + HCO3-

(4)

The kinetic rate equation is generally expressed as:

Rkin = k [ H + ]ns ,

(5)

with [H+]s the concentration of H+ at the reacting surface and

k and n the reaction rate constant and reaction order respectively. When H+ is consumed at the surface, a concentration
gradient [H+]b-[H+]s develops between bulk and surface. This
gradient generates a diffusion flux of H+ from bulk to surface.
The rate of the diffusion process can be expressed conveniently in terms of a mass transport coefficient KMT:

RMT = K MT [ H + ]b [ H + ] s

(6)

KMT will generally depend on the diffusion coefficient, fluid

viscosity and properties of fluid flow close to the surface. In
an equilibrium situation, the rate of consumption of H+ at surface is equal to the rate of transport of H+ from bulk
to surface:
equilibrium: Rkin = RMT

(7)

For reaction order n=1 this equation can be solved analytically

for [H+]s. Back substitution into eq. (5) or (6) gives the following expression for the rate:
R=

k K MT
[ H + ]b
k + K MT

(8)

HCl-carbonate reactions are usually very fast and k>>KMT.

Under these conditions the overall spending rate is limited by
the mass transport rate and the rate constant k drops out of the
rate equation:
R K MT [ H + ]b

(9)

SPE 82211

The rate in eq. (9) is proportional to the bulk acid concentration [H+]b. This is also illustrated in fig. 2, where the dissolution rate measured in a rotating disk test is plotted as a function of bulk acid strength. For HCl the measured rate is indeed
proportional to the bulk acid concentration.

are not transported by diffusion from bulk to surface, but are

generated in-situ at the surface through the dissociation reaction. It is the undissociated acid that diffuses from bulk to solution. This process is visualized in fig. 3.
Figure 3. Reaction of weak acid with CaCO3.

7.0E-06

Rotating Disk
Rock: Calcite
Sample size: 5.1 cm
Rotational speed: 300 RPM
Temperature: 30 deg C
Pressure: 100 bar
order n: 0.49
rate constant k: 2.9E-3

6.0E-06

H+ Rate (mol/cm2/s)

HCl
5.0E-06

4.0E-06

CO2
diffusion

3.0E-06

Formic

2.0E-06

Ca2+

HA

dissociation
HA H+ + A-

boundary
layer

1.0E-06

Acetic
0.0E+00
0.0

0.5

1.0

1.5

2.0

2H+ + CaCO3 Ca2+ + H20 + CO2

Acid concentration C0 (mol/l)

Figure 2. Results of rotating disk tests for HCl, Formic and Acetic acid. Curves are rates predicted with
new model.
This relatively simple model nicely explains the HClcarbonate spending process, but fails when applied to organic
acid-carbonate spending. For example, it was shown in ref.
[12] that acetic-carbonate spending is diffusion limited
(straight line when rate is plotted as function of square root of
RPM). If the HCl-model were applicable, the rate would be
described by eq. (9). However, in an 1 mol/l acetic acid solution, the H+ concentration is only 0.005 mol/l (see table 3).
This would imply a rate that is about 200 times slower than
that of a 1 mol/l HCl solution. The measured rates, however,
are much higher (see fig. 2) and only a factor of about 7 lower
than the HCl-rate. Furthermore, the rate for acetic and formic
acid in fig. 3 is not proportional to the bulk acid concentration.
In fact, for acetic acid the strength increase with a factor of 4,
but the rate increases only with a factor of about 1.3. This effect was also noted by Fredd12. In his tests the acetic acid concentration was increased with a factor of 30, but the increase
in rate was only a factor of 2.
The HCl model fails when applied to organic acids because the acid dissociation constant KA is not included in the
model. Schechter tried to correct this and derived a rate equation for organic acids that includes KA 2. However, in his derivations he assumed the equality [H+]=[A-], which is true in
unspent acid, but certainly not true when the acid is partially
spent. Also, at the reacting surface the equality [H+]=[A-]
does not hold.
In the derivation of a new model to describe organic acidcarbonate spending we make the reasonable assumption that
reaction (4) and rate eq. (5) are independent of the type of
acid. This means that k and n have the same value for strong
and weak acids. The difference in observed dissolution rate
between a strong and a weak acid depends solely on the magnitude of the H+ concentration at the surface. When a weakly
dissociated acid spends on carbonate rock, H+ is consumed at
the surface. This drives the dissociation reaction (1) to the
right , generating more H+. So in contrast to HCl, the H+ ions

The correct mass transport rate equation therefore is:

RMT = K MT (Cb C s )

(10)

with Cb and Cs the bulk and surface concentration of the undissociated acid [HA]. The diffusion coefficient that goes into
KMT will obviously depend on the type of acid used. As is
shown in the Appendix (eq. A-3), it is actually more convenient to take for concentration C the sum of [H+] and [HA]
because it makes the model applicable to both weak and
strong acids.
The acid dissociation constant KA enters the model through
the relation between Cs and [H+]s (see eq. A-4):
Cs = [ H + ]s +

[ H + ] s C0

[ H + ]s + K A

(11)

Similar to the HCl acid model (eq. 8), we can set n=1 and
solve eqs. (7), (10) and (11) for [H+]s. Back substitution into
eq. (10), and assuming unspent acid (i.e. Cb=C0) results in the
following equation for the rate R:

R k K MT
=
C0
R 1 +
k K A k + K MT

(12)

Compare rate eq. (12) with rate eq. (8) for strong acids. The
additional term (1+R/kKA) in eq. (12) is responsible for the
lower spending rate of weak acids, compared to strong acids.
For large values of KA the additional term is approximately
equal to 1, and eq. (12) reduces to the strong acid eq. (8). Interestingly, when the rate is diffusion limited, i.e. for k>>KMT,
the rate constant k drops out of the RHS of eq. (12) but the
LHS still depends on k. This means that even in the diffusion
limited regime, the spending rate of the acid depends on the
kinetic rate of the surface reaction. Only for extremely high
values of k the term (1+R/kKA) reduces to 1 and the rate is no
longer dependent on k.

SPE 82211

(C C s )2n
Rkin = k [ H + ]ns X n 0

[ H + ]ns

(13)

The backward reaction term in eq. (13) is only important for

pH>4. At lower pH values this term has negligible contribution. X is a constant -defined in eq. A-13- that depends on the
solubility product for CaCO3 and on the equilibrium constants
of the carbonic acid reactions. Although the value of X depends on temperature and pressure, it was found that setting X
to a value of 2.E-10 produced satisfactory results for a wide
range of conditions. Alternatively, X can be used as a fitting
parameter (in addition to k and n) to optimize the
rate equation.
In fig. 2 the results of simulations with the new model are
shown. The new model successfully predicts the rate of HCl,
acetic and formic acid reactions with calcite rock. Note that
the model can also be used to calculate the rate of
acid mixtures.

The HCl concentration decreases rapidly, due to the rapid

spending. As expected, the concentration of the organic acid
decreases much more slowly and the acid penetrates deeper
into the fracture. Note that the organic acid does not spent to
completion, due to the thermodynamic limitations. Fig. 5 gives
an indication what to expect for the etched length and width
along the fracture. 15% HCl will mainly spent close to the
wellbore and the etched length will be limited to about 30 m.
The organic acid will create less etched width close to the
wellbore, but the etched length is more than twice that of
15% HCl.
10
9
13/9% Acetic/Formic
increased volume to match
dissolving power of 15% HCl

8
etched width (mm)

To complete the model the incomplete spending of weak

acids, as discussed in the previous section, must be added.
This requires modeling of the backward reaction in eq. (4).
The necessary equations are derived in the Appendix. The
final kinetic rate equation is:

7
6
5

15% HCl

4
3

13/9% Acetic/Formic

2
1
0

Acid Fracturing with Organic Acids

Updating existing acid fracturing models (based on HCl), to
include the new acid spending model, is relatively simple. It
requires replacing the kinetic rate eq. (5) with eq. (13), and
adding the relation between Cs and [H+]s, eq. (11). (Or eq. A-6
when acid mixtures are used.) To test the model we implemented it in the acid fracturing model developed by Settari in
ref [9], in which acid spending is calculated in a fracture with
pre-defined geometry. Results for a mixture of 13/9% acetic/formic and for 15% HCl are shown in fig. 4.

acid concentration (mol/l)

5
4.5
4
3.5
3

15% HCl

2.5
2

Fracture height: 20 m.
Fracture width: 0.5 cm
Fracture length: 100 m.
Pump rate: 15 bpm
Volume: 100 m3
Acid viscosity: 10 cp
Reaction order n: 0.49
Rate constant k: 2.9E-3

13/9% Acetic/Formic

1.5
1
0.5
0
0

20
40
60
80
distance from wellbore (m)

100

Figure 4. Acid concentration as a function of penetration depth in the fracture. 13/9% acetic/formic is
compared with 15% HCl (equal strength in mol/l).

20
40
60
80
distance from wellbore (m)

100

Figure 5. Etched width for 13/9% acetic/formic and

for 15% HCl.
In calculating the etched width in fig 5, the same volume
was used for HCl and organic acid. However, the incomplete
spending of organic acids will make them less efficient in dissolving rock, compared to HCl. Furthermore, the slower
spending rate will increase the amount of unspent acid that is
lost from the fracture due to leak off. To compensate for the
reduced efficiency, the volume of organic acid must be increased. In the example calculations in fig. 5, the volume of
13/9% acetic/formic must be about doubled to match the total
dissolving power of 15% HCl. This increase in volume obviously has a positive effect on etched width.
In fig. 6 the performance of the 13/9% acetic/formic mixture is compared to that of 9% formic. It is clear that the 13%
acetic acid does not contrinute much to the etched width. This
agrees with the results in table 4 that show that only 31% of
the acetic acid will actually spend. The remaining 69% will be
returned to surface unspent. The acetic component, being
weaker than formic, will penetrate deeper and create slightly
more etched length but it is doubtful if this will have any effect on final production.

SPE 82211

5
4.5
etched width (mm)

4
3.5
3

13/9% Acetic/Formic

2.5
2
1.5

9% Formic

1
0.5
0
0

20

40
60
80
distance from wellbore (m)

100

Figure 6. Etched width for 13/9% acetic/formic and

for 9% formic.
Conclusions
Organic acids are good alternatives to HCl, especially in
high temperature formations. The retarded nature of organic acids results in deeper penetration into the formation
and improved stimulation.
The organic acid-carbonate chemistry is different from
HCl-carbonate chemistry. Models developed for HClcarbonate
spending
fail
to
describe
organic
acid-carbonate spending.
A new model was developed to describe acid-carbonate
spending. The model is applicable to strong and weak acids and also to acid mixtures. The main differences with
the existing HCl model are:
o Weak acid dissociation constant KA is build in
o Thermodynamic limitations of weak acid spending
o A new (kinetic) rate equation is introduced
The new model explains the increased etched lengths observed in acid farcturing treatments with organic acid and
can be used to further optimize these treatments
Nomenclature
C = acid concentration mol/l
C0 = initial total acid concentration mol/l
KA = acid dissociation constant mol/l
KMT = mass transport coefficient cm/s
Ksp = solubility product (mol/l)2
K1,2,3 = equilibrim constants carbonic acid
R = dissolution rate (flux) mol/cm2/s
subscripts
s = surface
b = bulk
eq = equilibrium
kin = kinetic
MT= mass transport
References
1 Williams, B.B., Gidley, J.L., Schechter, R.R.: Acidizing Fundamentals , Monograph Volume 6, SPE

2 Schechter, R.S.: Oil Well Stimulation, Prentice Hall Inc, Englewood Cliffs, New Jersey, (1992)
3 Buijse, M.A.: "Understanding Wormholing Mechanisms Can
Improve Acid Treatments in Carbonate Formations", paper SPE
38166, presented at the SPE European Formation Damage Conference, 2-3 June, 1997, The Hague, The Netherlands.
4 Daccord, G., Lenormand, R., and Touboul, E.: "Carbonate
Acidizing: Toward a Quantative Study of the Wormholing Phenomenon", SPEPE (Feb. 1989) 63-68
5 van Domelen, M.S., Jennings, A.R.: Alternate Acid Blends for
HPHT Applications, paper SPE 30419, presented at the Offshore European Conference, Sep. 5-8, 1995, Aberdeen
6 Rietjens
7 Lund, K., Fogler, H.S., McCune, C.C., and Ault, J.W.: "Acidization II - The Dissolution of Dolomite in Hydrochloric Acid",
Chem. Eng. Sci., (1975) 30 825-835.
8 Alkattan, M., Oelkers, E.H., Dandurand, JL., Schott, J.: An
experimental study of calcite and limestone dissolution rates as
a function of pH from 1 to 3 and temperature from 25 to
80C, Chemical Geology, (1998), 151, 199-214
9 Settari, A.: Modelling of Acid Fracturing Treatment, paper
SPE 21870, presented at the Rocky Mountain Regional meeting,
Denver, Colorado, April 15-17, 1991
10 Fredd, C.N., Miller, M.J.: Validation of Carbonate Stimulation
Matrix Models, paper SPE 58713, presented at the 2000 SPE
International Symposium on Formation Damage Control, Lafayette, Louisiana, 23-24 February 2000
11 Chatelain, J.C., Silberberg, I.H., Schechter, R.S.: Thermodynamic Limitations in Organic Acid-Carbonate Systems, Soc.
Pet. Eng. J., August 1976, 189-195
12 Fredd, C.N., Fogler, H.S.: The kinetics of calcite dissolution in
acetic acid solutions, Chem. Eng. Science, 53, No 22, (1998),
3863-3874
13 Al-Qahtani, M.Y., Rahim, Z: Optimization of Acid Fracturing
Program in the Khuff Gas Condensate Reservoir of South Ghawar Field Saudi Arabia by Managing Uncertainties Using Stateof-the-Art Technoloy, paper SPE 71688, presented at the Annual Technical Conference and Exhibition, Sep. 30- Oct. 3,
2001, New Orleans, Louisiana

Appendix
Acid strength and dissociation
The dissociation reaction of acid HA in water is:
HA H+ + A-

(A-1)

with the dissociation constant KA given by:

KA =

[ H + ] [ A ] [ H + ] (C 0 [ HA])
=
[ HA]
[ HA]

(A-2)

The acid is present as either H+ or undissociated HA. The total

acid strength C is defined as the sum of these two species:
C = [ H + ] + [ HA]

(A-3)

This definition of total acid strength is convenient because it

can be used for both strong acids and for weak acids. For a
strong acid such as HCl, C [ H + ] , while for a weak acid
such as acetic C [HA] . Eq. A-3, can be rewritten (using eq.
A-2) as:

SPE 82211

[ H + ] C0

C = [H + ] +

(A-4)

[H ] + K A

Eq. A-4 allows calculation of [H+] from the total acid concentration C. For example, for unspent acid, C=C0, eq. A-4 can be
rewritten as:
[H + ]2 + K A [ H + ] C0 K A = 0

(A-5)

For strong acids (KA>>C0) the approximate solution of eq. A-

[CO2 aq ]eq [Ca 2+ ] eq

(A-12)

Eq. A-12 approximately holds because of the large value of

K1. It is further assumed that all CO2 generated in the acidcarbonate reaction stays in solution, which is generally the
case under downhole conditions (high pressure). Combining
eqs. A-7 to A-12 results in a relation between the H+ concentration and acid concentration C at equilibrium:

[ H + ]eq = X C 0 C eq

with X =

5 is: [ H ] C 0 , while for a weak acid (KA<<C0) the approximate solution is: [ H + ] C 0 K A .
The relation between total acid strength C and [H+] in eq. A-4
can easily be extended to a mixture of acids:
N

i =1
N

= [H ] +

(A-6)

[ H + ] C 0,i

i =1 [ H

] + K A,i

Acid-Carbonate equilibrium
In this section an expression for [H+]eq is derived for the equilibrium state of the acid-carbonate reaction. For clarity we
consider acid spending on calcite, CaCO3. The equations can
be easily modified to describe acid spending on other carbonates, e.g. dolomite, CaMg(CO3)2.
When acid spends on carbonate rock the equilibrium state
is reached when product of the Ca2+ and CO32- concentration
exceeds the solubility product Ksp:
K sp = [Ca 2+ ]eq [CO32 ]eq

(A-7)

The concentrations of the carbonic acid species in solution are

related through the following three equilibria:
H2CO3 CO2aq + H2O
+

H2CO3 H +

HCO3-

HCO3- H+ + CO32-

K1 =

[CO2 aq]
600
[ H 2 CO3 ]

[ H + ] [ HCO3 ]
K2 =
2.5 E 4
[ H 2CO3 ]

K3 =

[ H + ] [CO32 ]
[ HCO3 ]

5.6 E 11

(A-8)

(A-9)

(A-10)

The numerical values for the equilibrium constants K1, K2 and

K3 are valid at 25C. Two additional equations relate the
amount of Ca2+ and CO2 in solution to the amount of acid
spent. If the initial acid concentration is C0, and the acid concentration after spending is Ceq, then:

[Ca 2+ ] eq = 12 C 0 C eq

(A-11)

(A-13)

Solving this equation simultaneously with the general relation

between [H+] and C in eq. A-4 gives the following expressions for [H+]eq:
2
[ H + ] eq
+ K A [ H + ]eq

C = [ H + ] + [ HAi ]

K2 K3
4 K1 K sp

X
1+ X

C 0 K A = 0 (A-14)

For a mixture of acids, [H+]eq can be calculated by (numerically) solving simultaneously eqs. A-13 and A-6. After calculation of [H+]eq it is straightforward to calculate the concentration of undissociated acid [HA]eq and Ceq from the eqs. A-2
and A-3. The fraction of acid that has spent is equal to:
1-Ceq/C0.
Using the numerical values for K1, K2 and K3 in eqs. A-8 to
A-10 and setting Ksp=3.E-8, the constant X is calculated as:
X=2.E-10. Obviously X, being a thermodynamic constant, will
depend on temperature, pressure, etc. We found, however, that
the value X=2.E-10 will produce satisfactory results for a wide
range of conditions.
An alternative equation can be derived from eqs. A-2 and
A-11 to A-13, using the approximation for weak acids,
Ceq [HA]:
KA
4 X

[Ca 2+ ] [CO2 aq ]
[ HA]

(A-15)

Eq. A-15 is written in this form to compare it with the empirically derived equation (3.12) in ref [1]. To produce the constant 1.6E4 in the referenced equation, X must be set to a value
of 2.4E-10, close to the value of 2.E-10 we found above.
Acid-Carbonate reaction rate
The kinetic rate of HCl-carbonate reactions is generally expressed as:
R = k [ H + ] ns ,

(A-16)

with [H+]s the H+ concentration at the reaction surface and k

and n the reaction rate constant and order respectively. Note
that eq. A-16 depends on [H+] and not on the type of acid. So
the rate equation is valid for both weak and strong acids. Rate
equation A-16 only describes the forward reaction. For HCl
this suffices because HCl spends to completion and the back-

SPE 82211

ward reaction rate is negligible. A weak acid, however, does

not spent to completion. We model the backward reaction as:
R = k f [ H + ] ns k b [Ca 2+ ] ns [ HCO3 ] ns

(A-17)

The backward reaction rate constant kb is fixed by the equilibrium condition R=0:
n
2+ n
n
k f [ H + ]eq
, s = k b [Ca ] eq , s [ HCO3 ] eq , s

(A-18)

After some math, using eqs. A-7 to A-13, A-17 and A-18, the
final rate equation is expressed as:

(C C s )2n
R = k f [ H + ] ns X n 0

[ H + ] ns

(A-19)

Note that the two concentrations [H+]s and Cs are related

through eq. A-4 (or A-6 in case of a mixture of multiple acids). When implemented in acid fracturing software eq. A-19
will replace the more familiar eq. A-16. Eq. A-19 must be
solved simultaneously with eq. A-4 (or eq. A-6 for
acid mixtures).