PAPER 2009-015

Application of Citric Acid in

Acid Stimulation Treatments
M.H. ALKHALDI
University of Adelaide

H.A. NASR-EL-DIN
Texas A&M University

H.K. SARMA
University of Adelaide

This  paper  is  accepted  for  the  Proceedings  of  the  Canadian  International  Petroleum  Conference  (CIPC)  2009,  Calgary, 
Alberta,  Canada,  16‐18  June  2009.    This  paper  will  be  considered  for  publication  in  Petroleum  Society  journals. 
Publication rights are reserved. This is a pre‐print and subject to correction.

Abstract
Mass transfer process during the reaction of citric acid with
calcite was investigated using the rotating disk apparatus. The
effects of disk rotational speed, initial citric acid concentration,
and temperature on the effective diffusion coefficient of citric
acid were examined.
Using various citric acid concentrations (1, 2, 5, 7.5 wt%),
the diffusion coefficient of citric acid was calculated at 25, 40,
50°C. The effective diffusion coefficient of citric acid was found
to be a function of the interplay between the calcium citrate
precipitation and the presence of the counter calcium ions. At
high initial acid concentration, (5, 7.5 wt%), the effects of
calcium citrate precipitation and counter calcium ions were
significant and the calculated citric acid diffusion coefficients
were not comparable with its measured effective diffusion
coefficients using the rotating disk. However, the effects of both
the calcium citrate precipitation and the counter calcium ions
on the citric acid diffusivity were minimal at low initial citric
acid concentrations.
The effect of temperature on the diffusion coefficient of
citric acid at a constant citric acid concentration was found to
follow Arrhenius law, and the activation energy is equal to 37.9
kJ/mol.
Introduction
Citric acid (C6H8O7) has historically been used in oil field
treatments as an iron-control agent(1). It is commonly used to
stabilize iron in spent HCl acids and prevent precipitation of
ferric hydroxide(2), and/or iron sulfide(3,4). Besides its iron-
chelating ability, citric acid possesses another important
chemical characteristic. Citric acid is a weak acid and this
makes it less reactive with reservoir rocks than hydrochloric
acid. Because it is weak acid, citric acid is a good alternative to
hydrochloric acid in high temperature formations, where
concentrated HCl solutions can cause severe corrosion problems
and poor etching patterns(5).
Over the last few years, various acid systems, such as gelled
acids, viscoelastic surfactants-based acids (VES), emulsified
acids, and encapsulated citric acid, have been introduced to
address some of the concerns with HCl. Except of citric acid
system; these acids have been extensively studied and
successfully employed in acid fracturing treatments(6-10).

1
 Citric acid has been used in some field treatments as an it will form a layer on the calcite surface and then it will act as a
alternative to other conventional weak acids such as formic acid diffusion barrier, which will slow the overall mass transfer
(HCOOH) and acetic acid (CH3COOH). It was introduced process. Therefore, it is very important to measure the pH value
because it can be used in an encapsulated form, which prevents of the bulk solution and examine the surface of the calcite disk
its reaction with both the production tubulars and the formation at the end of each experiment to determine whether calcium
up to 180ºF(11,12), and hence this will protect well tubulars, citrate precipitated during the citric-calcite reaction or not.
especially those made of corrosion resistant alloys. The use of
encapsulated citric acid in the field has met with mixed results. Mass Transfer into a Rotating Disk in
Blauch et al.(11) reported positive field results and that the
formation damage because of calcium citrate precipitation was Reactive Environments
not a major concern at down-hole conditions. However, Burgos The calcite-citric reaction can be described by the following
et al.(12) reported that there was no improvement in the three steps: (1) the transport of citric acid molecules to the solid
performance of an acid-fractured well after the application of surface, (2) the dissociation of citric acid and the reaction at the
encapsulated citric acid. They explained the unexpected field surface, and (3) the transport of products away from the
results in terms of calcium citrate precipitation. These mixed interface, Figure 2. The overall reaction rate is determined by
field results highlighted the need for better understanding of the the slowest step.
reaction of citric acid with calcite. In the diffusion-limited regime, the mass transfer flux of a
Previous studies have investigated the reaction of citric acid species i, Ji, can be expressed in terms of the concentration of
with calcite. Using the rotating disk apparatus, these studies the transferring species, and the mass transfer coefficient, kmti,
have shown that the reaction is mainly limited by the mass as follows:
transfer process and the calcium citrate precipitation plays an
important role in the reaction of citric acid with calcite. Ji  k mt i (C Bi  CSi ) ……………………………………………....(8)
However, these studies have been conducted over very limited
range of parameters(13,14). The mass transfer coefficient in Newtonian fluids is a function
As stated above, citric acid has been used as an alternative of the effective diffusion coefficient of species i, physical
to hydrochloric acid in acid fracturing treatments because it has properties of the solution, and the square root of the rotational
slower reaction rate and can be inhibited at elevated speed. It can be determined under laminar flow conditions (Re ≤
temperatures. However, to design an effective acid fracturing 3*105 and Sc >100) using Equation 9(16,17):
treatment, it is essential to know the effective diffusivity of the
acid system at different field conditions, which is needed to 
0.62048 Sc 2 / 3    i
determine the geometry of the fracture. Therefore, the
objectives of this study are to: (1) measure the calcite
k mt 
  
1  0.2980 Sc 1 / 3  0.1451 Sc  2 / 3  …………….……..(9)
dissolution rate using the rotating disk apparatus over a wide
range of parameters, and (2) determine the effects of the initial Mobility of Citric Acid in Aqueous Solutions
citric acid concentration and temperature on the overall mass The mobility of citric acid molecules plays an essential role
transfer coefficient. in determining the reaction rate of citric acid with calcite. One
of the main steps of the citric acid reaction with calcite is the
transport of the citric acid molecules to the disk surface. The
Theory transport rate is mainly dependent on the mass transfer
coefficient which is, in turn, mainly dependent on the disk
Chemistry of Citric Acid and Precipitation of rotational speed and the effective diffusion coefficient of citric
Calcium Citrate acid, Equation 9.
Citric acid (H3AOH) is a weak organic acid, which ionizes in Previous studies have reported the diffusivity of citric acid in
water stepwise as shown in Equations (1)–(4)(15): water. According to Muller and Stokes(18), the diffusion
coefficient of citric acid molecules in water depends on its ionic
H3AOH H2AOH− + H+............................................................. .(1) and molecular diffusion coefficients as follows:
H2AOH− HAOH2− + H+............................................................... (2)
HAOH2− AOH3− + H+..................................................... ...(3)
2 1    
AOH3− AO4− + H+........................................................................ (4) D  Dm  Di ........................................................(10)
2 2
where A is C6H4O6. The distribution of citric acid species as a
 d ln y   0  0
function of equilibrium pH values is shown in Figure 1. D m  D0m 1  C  , D m  6.57 E  6 cm 2 / s ……(11)
The reaction of citric acid with calcite at pH values of 1.8 to  dC   
5 is as follows:
 0 0 
 0   2RT   H   H 2Cit  
2H+ + CaCO3 Ca2+ + H2O + CO2 ↑, pH = 1.8 – 5.............................(5)
Di  Di0  , Di0   2  0  …………....(12)
    F   H   0H Cit  
H2AOH− + Ca2+ CaH2AOH+, pH = 1.8 – 5.......................................(6)    2 
Ca2+ + 2(CaH2AOH+)(aq) Ca3(AOH)2 (s) ↓ + 4H+...........................(7)
Muller and Stokes(18) measured the overall diffusion coefficient
Based on the above equations and Figure 1, it is clear that of citric acid in water, with no other ions present, using different
citrate ions are present in the reaction solution at pH values citric acid concentrations at 25°C. They reported that the
above 6, so calcium citrate is expected to precipitate at pH overall diffusion coefficient of citric acid decreased as the
values of 6.0 or above. However, according to Alkhaldi et concentration of citric acid increased, Figure 3. This trend can
al.(13), precipitation of calcium citrate occurs at low pH values be explained based on Equations 10-12. From Equations 11
of nearly 3.0. If calcium citrate precipitates during the reaction, and 12, it is clear that the molecular diffusion coefficient of

2
citric acid is a function of (D0m, µ0/µ, 1+C d lny/dC), and the
ionic diffusion coefficient of citric acid is a function of (µ0/µ,
D0i). As a result, the diffusion coefficient of citric acid is
dependent on (µ0/µ, D0m, D0i, α, and 1+C d lny/dC). In other
words, the diffusion coefficient of citric acid is dependent on
the physical and chemical properties of its solution. Based on
the data reported by Muller and Stokes(18), increasing the
concentration of citric acid from 0.097 to 0.24 M at 25°C,
resulted in a decrease of 0.03 (33 %) and 0.05 (5%) in the
values of α and µ0/µ, respectively, while the value of (1+C d
lny/dC) increased from 1.02 to 1.05 (3%). These changes in the
physical and chemical properties of citric acid solutions resulted
in a decrease of 3.3 E-7 (5%) in diffusion coefficient of citric
acid.
The overall diffusion coefficient of citric acid using various
concentrations can be calculated at higher temperatures using
Equations 10-12. At higher temperatures, the values of
solution viscosity (µ), solvent viscosity (µ0), the dissociation
degree (α), and the ionic citric acid diffusion coefficient at
infinite dilution (D0i) have to be corrected for temperature
changes. The values of (µ) and (µ0) at higher temperatures
were measured and then Equation 11 was used to correct the
value of Dm at higher temperatures. Equation 12 was used to
correct the value of (Di) at higher temperatures where the values
of (µ) and (µ0) measured at these values were used. The values
of the mean activity coefficient (y) were reported by Levien(15),
whereas the values of the limiting equivalent conductance (λ0)
were reported by Shamim and Eng(19). Table 1 shows the
calculation of the diffusion coefficient of citric acid using
various concentrations at 40°C.
Experimental Studies
Materials
Citric acid powder was obtained from ADM Ringaskiddy
Company, US Pharmacopeia (USP grade). XRD analysis
showed that it contained 99 wt% anhydrous citric acid and 1
wt% mono-hydrated citric acid. Calcite marble (CaCO3) with a
trade name of “Acqua Bianca” was obtained from Italy. XRD
analysis indicated that it contained 99 wt% calcium carbonate
and trace amounts of albite, quartz, and chlorite. Calcium
carbonate powder (ACS grade) was supplied by Fisher
Scientific Co. Citric acid solutions were prepared using
distilled water with a resistivity greater than 18MΩ/cm at room
temperature. A corrosion inhibitor for organic acids was added
to the citric acid at 0.1 wt% to protect surface-wetted areas.
Measurements calcium concentration in the samples collected
from the rotating disk reactor showed that the addition of the
corrosion inhibitor at 0.1 wt% did not affect the reaction rate of
citric acid with calcite.
Rotating Disk Apparatus (RDA)
The RDA used in this work was RDA-100, manufactured by
CoreLab Instruments Ltd. All acid-wetted surfaces are
manufactured from Hastelloy B-2 or C-276 alloy for corrosion
resistance. Figure 4 shows a schematic diagram of this
apparatus.
Calcite disks with a diameter of 1.5-inch and a thickness of
0.65-inch were soaked in 0.1N HCl for nearly 30 minutes, and
then thoroughly rinsed with distilled water before use.
According to Fredd and Fogler(20), this procedure greatly
improves the reproducibility of results. The calcite disk was
mounted on the rotating assembly using heat-shrinkable Teflon
tubing. The disk was rotated in citric acid solution with a
3
known initial acid concentration. The experiments were run
and 10 cm3 samples of the bulk solution were collected for pH
and calcium analysis. Samples were collected every 2 minutes
for the first 10 minutes; and then every 5 minutes for 25
minutes; and the two final samples after 45 and 50 minutes,
respectively. Corrections were made to account for changes in
the volume of the reactants that occurred due to sample
withdrawal(21,22). The rotating disk experiments were conducted
to determine the effects of initial citric acid concentration (1, 2,
5.0, 7.5 wt%), temperature (25, 40, 50°C), and rotational speed
(100–1,000 rpm) on the calcite dissolution rate. All
experiments were performed at 1,000 psi to ensure that CO2
remained in solution. A new calcite disk was used for each
experiment.
Analytical Techniques
An auto-titrator (Mettler DL70ES) was used to determine
the concentration of citric acid using 0.096M NaOH up to a pH
value of 8.0, with a few drops of phenolphthalein as an
indicator. The concentration of Ca in samples was measured
using inductively coupled plasma (ICP). Density measurements
were made with a Paar digital density meter (DMA 35N). To
measure the pH of the collected samples, an Orion model 250A
meter and Cole Parmer Ag/AgCl single junction pH electrode
were used. The viscosity of initial citric acid solutions
(Newtonian fluids) was measured using a capillary viscometer
at 25, 40, and 50°C.
Results and Discussion
Calcium Citrate Precipitation
Calcium citrate plays an important role in citric acid reaction
with calcite. It has low solubility in water (0.0018 mol/1000 g
water at 22.8 ◦C), which decreases further with temperature(23).
As a result, it will act as a diffusion barrier if it forms during the
reaction. Therefore, it is very important to know if it
precipitated during the citric-calcite reaction or not.
Calcite disks reacted with different initial citric acid
concentrations for 50 minutes at 50C were examined. The
reacted disks were analyzed by scraping the surface with a
spatula and running XRD analysis on the collected solids. The
results showed that the scrapped solids contained a mixture of
calcium citrate tetra-hydrate and calcium carbonate. However,
calcium citrate precipitation at low initial citric acid
concentrations (1, 2 wt%) was relatively minimal when
compared to the precipitation at high initial citric acid
concentrations, (5, 7.5 wt%), which was evident from the
amount of the of calcium citrate found in the solids collected by
scraping the surface of the reacted calcite disk. Due to
calcium citrate precipitation, it was expected that the pH value
of the bulk solution to be above 3.0, based on Equations 5-7.
However, the maximum increase in the pH value of the bulk
solution was measured at 7.5 w% at 50C, where the pH
increased from 1.8 to 2.3 due to the reaction, but no precipitate
was noted in the solution. Calcium citrate precipitated on the
disk surface and not in the bulk solution, which is in agreement
with the observations made by Burgos et al.(12).
The pH at the reaction interface is expected to exceed 3.0
based on the fact that calcium citrate precipitate was noted at
the reacted calcite disk. The pH value at the reaction interface
is expected to be buffered in the range of 4-5 due to the
presence of carbonic acid H2CO3:
CO2 + H2O  H2CO3……………………………………………….(13)
H2CO3 + H2O  H3O+ + HCO3-…………………………………….(14)
HCO3- + H2O  H3O+ + CO32-……………………………………...(15)
According to Buijse et al.(24), during the reaction of weak acids
with calcite, the final equilibrium pH value will be nearly 4.0
provided that the generated CO2 stays in solution by applying
high pressure > 1000, psi. Based on this, it was concluded that
the pH value at surface of the reacted calcite disks is nearly in
the range of 4-5, while it remained at 2.3 in the bulk solution.
The pH at the reaction surface will not be more than 5 because
of the buffer effect of carbon dioxide as stated above.
Species Distribution during Citric-Calcite
Reaction
The average initial and final pH values of citric acid
solutions using different concentrations was nearly 1.8 and 2.3
after the reaction with calcite for 50 minutes at 50C. Based on
Figure 1, it is clear that the present species at these pH values
are citric acid molecules, mono-citrate, and H+ ions. The
concentration of mono-citrate ion will be equal to that of H+ ion.
All the three species will diffuse from the bulk solution to the
reaction surface. However, based on these pH values, the
maximum concentration of each of the mono-citrate and
hydrogen ions is 0.02 M in citric acid solution of an initial
concentration of 7.5 wt%. This maximum concentration of both
hydrogen and citrate ions during the citric-calcite reaction
represents less than 5% of the total citric acid concentration,
where 7.5 wt% is equal to 0.39 M. Therefore, the transport of
these species into the interface was neglected, and in the
following analysis, citric acid molecules are considered to be
the main diffusing species that control the overall mass transfer
process during the citric-calcite reaction.
Calcite Dissolution in Citric Acid Solutions
Figures 6 and 7 show typical plots of the moles of calcium
in solution [Ca2+]Bulk as a function of the reaction time. In these
plots, the calcite disks reacted with citric acid of initial
concentrations of 1.0 and 5.0 wt%, respectively, the rotational
speed was 1,000 rpm, and system pressure was 1,000 psi.
Similarly, several plots were generated at different rotational
speeds using 1.0, 2.0, 5.0, and 7.5 wt% citric acid with 0.1 wt%
corrosion inhibitor. In all plots, the moles of calcium in
solution increased linearly with time, with a correlation
coefficient, R2, greater than 0.99. In all experiments, collected
samples from the bulk solution showed that the average pH
values of the bulk solution increased from an initial value of 1.8
to a final value of 2.3 after a reaction time of 50 minutes The
change of the bulk solution pH value started after a reaction
time of nearly 20-25 minutes. Therefore, only the linear
relationship of the moles of calcium with time during the first
10 minutes of reaction is used in the analysis of the calcite
dissolution rates, although there was no deviation noted in the
linear relationship between the moles of calcium and reaction
time. This approach was also used by Lund and Fogler(25) and
Taylor et al.(21).
The dissolution rate of calcite was calculated from the slope
of the linear relationship of the calcium moles in solution with
time, the initial surface area of the disk, A0, and time, t, as
follows:
dN Ca
calcite dissolution rate  ……………………….....(16)
A 0dt
4
Figure 8 plots the calculated dissolution rates of calcite at
initial citric acid concentrations of 1, 2, 5, and 7.5 wt%, at 50C
and 1,000 psi, as a function of the square root of the disk
rotational speed. In the mass-transfer regime, the calcite
dissolution rate is equal to the citric acid mass flux, J, and based
on Equation 18, it will have a linear relationship with the
square root of the disk rotational speed at a constant citric acid
bulk concentration. From the slope of straight lines in Figure
8, the Schmidt number can be calculated, and hence the
diffusion coefficient of citric acid can be determined at various
initial concentrations using Equation 9. Equations 8 and 9 can
be rewritten as follows:
J
k mt  , CS of citric acid  0, as disscussed earlier …....(17)
CB
 
 
2 / 3

 0.62048    
 D  0.5
J 1 / 3 2 / 3
* C B* ….(18)
   
1  0.2980  D   0.1451   
   D 
The citric acid effective diffusion coefficient can be
determined from the slope of the straight lines shown in Figure
8 using Equation 18. The appendix gives the procedure used to
solve this equation.
Besides the disk rotational speed, it is interesting to note
that the calcite dissolution in citric acid solutions is also
dependent on the initial citric acid concentration. It is clear that
the dissolution rate of calcite in citric acid solutions of low
initial concentrations, 1 and 2 wt%, is proportional to the square
root of the rotational speed up to 1,000 rpm. This indicates that
the calcite dissolution at initial citric acid concentrations of 1
and 2 wt%, is mass-transfer limited. A different trend was
noted at high citric acid concentrations. At rotational speeds
below 500 rpm, the calcite dissolution is proportional to the
square root of the disk rotational speed, indicating that the
reaction was also mass-transfer limited, while the plateau
portion, above 500 rpm, indicates that the dissolution rate is
limited by the surface reaction. At the beginning, the plateau
portion was thought to be a result of calcium citrate
precipitation. As stated earlier, calcium citrate precipitated
during the reaction of citric acid with calcite even when low
concentrations of citric acid were used. Therefore, it was
thought that the calcium citrate precipitation covered the surface
of the calcite disk and then it stopped the citric-calcite reaction
as reported by Alkhaldi et al.(14) when the citric-calcite reaction
was carried for two hours. . However, this hypothesis was ruled
out because it is evident from the calcium concentration shown
in Figure 7 that the reaction of 5 wt% citric acid with calcite at
50C was continuous and it did not stop throughout the
experiment, showing that not all calcium carbonate cites were
blocked by calcium citrate precipitation. In other words,
although calcium citrate precipitation did not stop the
dissolution of calcite disk, however, it limited their dissolution
rate in citric acid solutions by blocking some of calcite sites.
Therefore, the plateau portion in Figure 8 shows the effect of
the mass-transfer limitation of the calcite dissolution in citric
acid solutions.
As it can be seen from Figure 8, there is a difference
between the profile of the calcite dissolution in high initial citric
acid concentrations and its dissolution in low initial citric acid
concentrations. This difference can be explained when one
considers the mass transfer and reaction rate equations:

J  k mt (C B  CS )  k mt * C B , CS  0 ……..……………....(19)
J  k rxn * CSR ……………………………………………....(20)
The dissolution rate is determined by the slowest step. The
dissolution rate is mass-transfer limited when the value of
Equation 19 is higher than that of Equation 20. In citric acid
solutions of high initial concentrations, the high driving force,
(CB-0), combined with the high kmt value at high rotational
speeds (based on Equation 9), result in mass transfer rates
higher than the reaction rates. Hence, the overall dissolution
rate is limited by the surface reaction rate at these high initial
citric acid concentrations and high disk rotational speeds.
However, in citric acid solutions of low initial concentrations,
because of the relatively low driving force, (CB-0), the mass
transfer rates never exceeded the reaction rate even at high
rotational speeds, 1,000 rpm. Therefore, the overall dissolution
rate of calcite in low concentration citric acid solutions is mass-
transfer limited even at high rotational speeds.
The dissolution rate of calcite is dependent on the initial
citric acid concentrations. Figure 8 shows the effect of
increasing the initial citric acid concentration on the calcite
dissolution rate. In low initial citric acid concentrations, the
effect of increasing citric acid concentration is significant,
where doubling the citric acid concentration from 1 to 2 wt%
increased the calcite dissolution rate from 2.8E -7 to 6.0E -7,
respectively, at 500 rpm. However, at high initial citric acid
concentrations, the effect of increasing citric acid concentration
is not significant. For example, increasing the initial citric acid
from 5 to 7.5 wt% increased the calcite dissolution from 9E -7
to 1E -6, at 700 rpm. Even at higher rotational speeds, 1,000
rpm, the effect of initial citric acid concentration on the calcite
dissolution becomes less pronounced, where citric acid
solutions of 2, 5, and 7.5 wt% have nearly identical calcite
dissolution rates. This finding is of interest in designing citric
acid treatments. In matrix acidizing treatments, which are
usually conducted at high pumping rates, low and high citric
acid concentrations will have almost identical calcite dissolution
rates, but high citric acid concentrations will be favored due to
their high dissolving power. However, the high citric acid
concentrations of citric acid will result in significant calcium
citrate precipitation. Therefore, there is no more added value of
using high citric acid concentrations.
Calculation of the Diffusion Coefficient of
Citric Acid
Effect of Initial Citric Acid Concentration on its Diffusion
Coefficient
Under a constant temperature, the diffusion of citric acid is
controlled by its mobility, its initial concentration, and its
degree of dissociation. According to Muller and Stokes(18), the
diffusion of citric acid molecules in water can be determined
using Equations 10-12, provided that no counter ions are
present. In order to calculate the diffusion coefficient of citric
acid, at 50°C, using Equations 10-12, the viscosity values of
various citric acid solutions at 50°C were measured, Figure 9.
It is clear that the viscosity of citric acid solution increased as
its initial concentration increased, while the viscosity value
decreased as the solution temperature increased. The viscosity
value of 7.5 wt% citric acid at 25ºC is in good agreement with
that reported by Levien(15).
5
Figure 10 shows the calculated diffusion coefficients of
different citric acid solutions at 50°C, using Equations 9-11.
The calculated diffusion coefficients of different citric acid
solutions (Figure 10) showed the same trend noted by Muller
and Stokes(18). The diffusion coefficient of citric acid decreased
as its initial concentration increased. This behavior is due to the
changes in the physical and chemical properties of the citric
acid solutions as discussed earlier. It is useful to compare these
calculated diffusion coefficients of citric acid with its effective
diffusion coefficients measured using the rotating disk.
According to Conway et al.(26), the diffusivity of HCl is affected
by the presence of other ions, which act as counter ions. In the
presence of counter ions (Ca2+, Mg2+), the diffusivity of
hydrogen ion increases if the ratio of H+ to counter ion is high,
[H+]/[counter ion]. In other words, the diffusivity of HCl is
lower than its effective diffusivity in the presence of counter
ions. They reported that this trend occurred during the reaction
of hydrochloric acid with both dolomite and calcite rocks, using
acid concentrations of 4 to 28 wt%. Based on this, it is
expected that the diffusivity of citric acid will be lower than its
effective diffusivity in the presence of counter ions and calcium
citrate precipitation. Therefore, it is useful to compare the
calculated citric acid diffusion coefficients with its effective
diffusion coefficients measured using the rotating disk
apparatus. This is comparison will assess the effect of both the
calcium citrate precipitation and the presence of counter
calcium ions.
Compared to HCl and other organic acids such as acetic and
formic, citric acid has a lower diffusion coefficient at 25ºC. For
example, the diffusion coefficient of 0.25 M citric acid is 6.4E -
6 cm2/s, while the diffusion coefficients of 0.5M HCl, 0.5 M
acetic acid, and 0.5 M formic acid are 3.6E -5(27), 1.1E -5, and
3.0E -5 cm2/s(28), respectively.
Effect of Initial Citric Acid Concentration on its Effective
Diffusion Coefficient
The data presented in Figure 11 show the comparison of the
obtained effective diffusion coefficients of citric acid from
rotating disk experiments with the calculated diffusion
coefficients determined using Equations 10-12. The profile of
the effective diffusion coefficients of citric acid as a function of
initial citric acid concentration can be divided into two main
trends: 1) an initial linear decrease, which was followed by 2) a
gradual increase.
The first trend shows that the effective diffusion coefficients
of citric acid decreased when the initial citric acid concentration
increased. This behavior occurred in low acid concentrations, 1
and 2 wt%, and it is identical to the trend of the profile of the
calculated diffusion coefficients shown in Figure 10. In
addition, the effective diffusion coefficients of low initial acid
concentrations show a good agreement with the calculated
diffusion coefficients. For example, the effective diffusion
coefficient and the calculated diffusion coefficients of citric
acid at 1 wt %are 6.6E -6 and 6.8E -6 cm2/s, respectively. The
effective diffusion coefficient of 1 wt% citric acid is 3% lower
than the calculated diffusion coefficient calculated using
Equations 10-12. This small error indicates that the effects of
both the counter calcium ions and the calcium citrate
precipitation on the diffusion coefficient of citric acid are not
significant at low citric acid concentrations. This is also evident
from the concentration of calcium ions in 1 wt% citric acid
shown in Figure 6. The maximum concentration of calcium
ions in 1 wt% initial citric acid concentration is 320 mg/l.
However, in solutions of high initial citric acid concentrations
(5 and 7.5 wt%), calcium ion has significant effect on the
diffusivity of citric acid. This is evident from the comparison
between the effective diffusion coefficients of citric acid and the
calculated ones as shown in Figure 11. For example, the
effective and calculated diffusion coefficients of citric acid at 5
wt% are 2.1E -6 and 6.2E -6 cm2/s, respectively. This
difference indicates that the effect of both the counter calcium
ions and the calcium citrate precipitation are significant at high
initial citric acid concentrations. The maximum concentration
of calcium ions in 5 wt% citric acid solution is 1,350 mg/l.
It is clear that calcium ions affect the diffusivity of citric
acid. Calcium ions have significant effect on citric acid
diffusivity when they are present at high concentrations.
Therefore, Equations 10-12 are applicable to predict the
effective diffusion of citric acid at low initial acid
concentrations because the effect of counter calcium ion and the
amount of calcium citrate are not significant, Table 2.
Besides its effect on the value of the diffusion coefficient of
citric acid, calcium ion also controls the behavior of the
effective citric acid diffusivity as the initial citric acid
concentration increases. As shown in Figure 11, the effective
diffusion coefficients of citric acid decreased as the initial citric
acid increased and then suddenly the diffusivity of citric acid
increased as the initial citric acid increased. This behavior was
first thought to be a result of the calcium citrate precipitation at
the disk surface. However, if that was the case, then the
effective diffusion coefficient should have decreased as the
initial acid concentration increased. However, the effective
diffusion coefficient of citric acid increased as its concentration
was increased from 5 to 7.5 wt%. Therefore, the effective
diffusivity of citric acid is affected by the calcium citrate alone.
According to Conway et al.(26), the diffusivity of HCl increases
if the ratio of H+ to counter ion is high, [H+]/[counter ion].
Therefore, the citric acid molar ratio to calcium ion, citric
acid/counter ion, was calculated at various citric acid
concentrations. It was interesting to find out that the molar ratio
for 1, 2, 5, and 7.5 wt% are 1.78, 1.92, 2.2, and 4.6,
respectively. Based on this, it was concluded that the trend
shown in Figure 11 is mainly due to the interplay between the
counter calcium ions and the precipitation of calcium citrate. At
the beginning, when the initial citric acid increased, this resulted
in an increase in the amount of the calcium citrate precipitation
as was noted from the collected solids from the surface of the
reacted calcite disks. As a result, the effective diffusivity of
citric acid decreased. However, further increase in the initial
citric acid concentration resulted in a relatively higher citric
acid/calcium molar ratio, when 7.5 wt% citric acid solution was
used. This high citric acid\calcium molar ratio resulted in a
relatively higher effective diffusivity of citric acid when it is
compared to its effective diffusivity at different concentrations.
It is evident that the diffusion coefficient of citric acid
measured using the rotating disk is more representative for field
applications than the one measured using Equations 10-12.
Rotating disk data give the effective diffusion coefficient of
citric acid in its reaction solutions where the effects of both
counter calcium ions and calcium citrate precipitation on the
diffusivity of citric acid are significant.
Effect of Temperature on the Effective Diffusion Coefficient
of Citric Acid
Figure 12 shows the dissolution rate of calcite in citric acid
solutions of initial concentrations of 7.5 wt% as a function of
the temperature at rotational speeds of 100 to 1,000 rpm and
1,000 psi. It was found that the increase in temperature resulted
6
in higher dissolution rate, as expected. However, it is evident
from the data that temperature has a significant effect on the
calcite dissolution in the reaction-limited regime when it is
compared to its effect in the mass-transfer-limited regime. This
is mainly due to the strong dependence of the reaction rate
constant on temperature(29). In general, log of the rate constant
of any chemical reaction has a linear relationship with the
inverse value of the reaction temperature.
Figure 13 and Table 3 show the effect of temperature on the
effective diffusion coefficients of citric acid in its reaction
solutions of initial concentration of 7.5 wt% at 1,000 psi. The
temperature dependence of diffusion coefficients is usually
quantified using the Arrhenius equation:
E 
D  D0 exp a  …………………………………….…..(21)
 R gT 
 
Equation 21 differs from Equation 12 in that Equation 21
shows the temperature dependence of the citric acid diffusion
coefficient, while Equation 12 shows the temperature
dependence of the citric acid ionic diffusion coefficient. Citric
acid diffusion coefficient is dependent on both the ionic and
molecular diffusion coefficients as shown in Equation 10.
From Figure 13, it is evident that the effect of temperature
on the effective diffusion coefficient of citric acid follows
Arrhenius law. The activation energy was found to be 37.9
kJ/mol. From Table 4, it is evident that the calculated value of
the apparent activation energy for calcite dissolution rate in
citric acid solutions is in good agreement with the activation
energy values for calcite dissolution in various reactive systems
when the reaction is controlled by mass-transfer rates. This
confirms our analysis that the reaction of citric acid with calcite
is mass-transfer limited at the conditions shown in Figures 8
and 12.
Conclusions
The calcite dissolution rate was measured in different citric
acid solutions using the rotating disk apparatus. The effects of
initial citric acid concentration on the diffusion coefficient in its
reaction solutions with calcite were investigated. The following
conclusions were obtained:
1. The dissolution rate was found to be dependent on the
initial citric acid concentration, temperature, and disk
rotational speed.
2. At low initial citric acid concentrations, the effective
diffusion coefficients of citric acid decreased as the
initial concentration increased. However, at high
initial citric acid concentrations, the effective
diffusion coefficients increased as the initial
concentration increased.
3. The presence of counter calcium ions and the calcium
citrate precipitation had significant effect on the
effective diffusion coefficient of citric acid, especially
at high initial citric acid concentrations.
4. The effect of temperature on the effective diffusion
coefficient of citric acid was found to follow
Arrhenius law.
Acknowledgements Separation Plant Disposal Water into Tight Carbonate
Reservoirs; SPEJ, Vol. 10, No. 4, pp. 374–384,
The authors would like to thank the Operation and Services December 2005.
Division of Saudi Aramco EXPEC ARC for lending their 5. Crowe, C.W., McGowan, G.R. and Baranet, S.E.,
Rotating Disk Apparatus for conducting this study. Ali Al- Investigation of Retarded Acids Provides Better
Aamri is acknowledged for his help in conducting the Rotating Understanding of Their Effectiveness and Potential
Disk experiments. In addition, thanks go to M. Al-Fahad, of Benefits; paper SPE 18222 presented at the SPE
Saudi Aramco R&D Center for measuring the concentration of Annual Technical Conference and Exhibition,
calcium ions. Houston, TX, 2–5 October 1988.
6. Al-Mohammad, A.M., Nasr-El-Din H.A., Al-Aamri,
A.M. and Al-Fuwaires, O., Reaction of Calcite with
NOMENCLATURE Surfactant-Based Acids; paper SPE 102838 presented
A0 = disk initial surface area, cm2 at the SPE Annual Technical Conference and
C = citric acid concentration, mol/cm3 Exhibition, San Antonio, TX, 24-27 September 2006.
CB = citric acid concentration in the bulk solution, mol/cm3 7. Nasr-El-Din H.A., Al-Mohammad, A.M., Al-Aamri,
CS = citric acid concentration at the disk surface, mol/cm3 A.D. and Al-Fahad, M.A., Quantitative Analysis of
CSR = reactants surface concentration, mol/l
Reaction Rate Retardation in Surfactant-Based Acids;
D = citric acid diffusion coefficient, cm2/s
D0 = diffusion coefficient at infinite temperature, cm2/s SPEPO, Vol. 24, No. 1, pp. 107-116, February 2009.
Di = citric acid ionic diffusion coefficient, cm2/s 8. Al-Mutairi, S.H., Hill, A.D. and Nasr-El-Din, H.A.,
D0i = citric acid ionic diffusion coefficient at infinite Effect of Droplet Size and Acid Volume Fraction on
dilution, cm2/s the Rheological Properties and Stability of Emulsified
Dm = citric acid molecular diffusion coefficient, cm2/s Acid; SPE Production and Operations, Vol. 23, No. 4,
D0m = citric acid molecular diffusion coefficient at infinite
pp. 484-497, November 2008.
dilution = 6.57 E-6 cm2/s at 25°C
Ea = diffusion activation energy, kJ/mol 9. Nasr-El-Din H.A., Al-Mohammad, A.M., Al-Aamri,
F = Faraday constant = 96,485 coulomb (C)/mol A.M. and Al-Fuwaires, O., Reaction of Gelled Acids
J = citric acid mass transfer flux, mol/cm2/s with Calcite; SPE Production and Operations, Vol.
kmt = reaction rate constant, mol1-n. cm3n-2/s 23, No. 3, pp. 353-361, August 2008.
NCa = calcium moles in solution, moles 10. Al-Mutairi, S.H., Nasr-El-Din, H.A., Hill, A.D. and
R = Calcite disk radius, cm Al-Aamri, A., Effect of Droplet Size on the Reaction
Re = Reynolds number = (ω*R2)/ν Kinetics of Emulsified Acid with Calcite; accepted
Rg = universal gas constant = 8.314 J/mol/K for publication in SPEJ, 2009.
Sc = Schmidt number = (ν/D) 11. Blauch, M.E., Cheng, A. and Rispler, K., Novel
t = time, s Carbonate Well Production Enhancement Application
T = Temperature, K for Encapsulated Acid Technology: First-Use Case
y = mean activity coefficient History; paper SPE 84131 presented at the SPE
Annual Technical Conference and Exhibition,
Greek letters Denver, CO, 5–8 October 2003.
α = dissociation degree 12. Burgos, G., Birch, G. and Buijse, M., Acid Fracturing
λ0 = limiting equivalent conductance of ions at infinite with Encapsulated Citric Acid; paper SPE 86484
dilution at 25°C, cm2/(ohm.mol) presented at the SPE International Symposium and
µ = solution viscosity, cP Exhibition on Formation Damage Control, Lafayette,
µ0 = solvent viscosity, cP
LA, 18–20 February 2004.
ν = citric acid kinematic viscosity, cm2/s
13. Akhaldi, M.H., Nasr-El-Din, H.A., Blauch, M.E. and
ω = disk rotational speed, rpm
Funkhouser, G.P., New Findings on Damage
Potential, Geochemical Reaction Mechanisms, and
Production Enhancement Applications for Citric
REFERENCES Acid; SPEJ, Vol. 10, No. 3, pp. 267–275, September
1. Hall, B.E. and Dill, W.R, Iron Control Additives for 2005.
Limestone and Sandstone Acidizing of Sweet and 14. Alkhaldi, M., Nasr-El-Din, H., Mehta, S. and
Alaamri, A., Reaction of Citric Acid with Calcite;
Sour Wells; paper SPE 17157 presented at the SPE
Chemical Engineering Science, Vol. 62, pp. 5880-
Formation Damage Control Symposium, Bakersfield, 5896, November 2007.
CA, 8–9 February 1988. 15. Levien, B.J., A Physicochemical Study of Aqueous
2. Taylor, K.C., Nasr-El-Din, H.A., and Al-Alawi, M., Citric Acid Solutions; J. Physical Chemistry, Vol. 59,
Systematic Study of Iron Control Chemicals Used No. 7, pp. 640–644, July 1955
During Well Stimulation; SPEJ, Vol. 4, No. 1, pp. 19- 16. Levich,V., Physicochemical Hydro-Dynamics;
24, March 1999. Prentice-Hall, Englewood, NJ, pp.100-130, 1962.
17. Newman, J., Schmidt Number Correction for the
3. Stanley, C. and Martell, A., Organic Sequestering
Rotating Disk; J. Physical Chemistry, Vol. 70, No. 4,
Agents; Wiley, New York, 1959. pp. 1327-1328, April 1966.
4. Raju, K.U., Nasr-El-Din, H.A., Hilab, V., Siddiqui, S. 18. Muller, G.T. and Stokes, R.H., The Mobility of the
and Mehta, S., Injection of Aquifer Water and Gas/Oil Undissociated Citric Acid Molecule in Aqueous

7
 Solutions; J. Trans. Faraday Soc., Vol. 53, pp. 642, 1 and 62ºC at pH 2.7 to 8.4 in Aqueous Solutions;
1957. Geochemica et Cosmochemica Acta, Vol. 48, No. 3,
19. Shamim, M., and Eng, S., Transference Numbers of pp. 485-493, March 1984.
Aqueous Citrate Acid and the Limiting Molar
33. AlKattan, M., Oelkers, E., Dandurand, J. And Schott,
Conductance of the Dihydrogen Citrate Ion at 25˚C; J.
Solution Chemistry, Vol. 11, No. 5, pp. 309-314, May J., An Experimental Study of Calcite and Limestone
1982. Dissolution Rates as a Function of pH from −1 to 3
20. Fredd, C.N. and Fogler, H.S., The Kinetics of Calcite and Temperature from 25 to 80ºC; Chemical Geology,
Dissolution in Acetic Acid Solutions; Chemical Vol. 151, No.(1-4), pp. 199-214, October 1998.
Engineering Science, Vol. 53, No. 22, pp. 3863–3874, 34. Maryadele, J.O., Heckelman, P. and Smith, A., Merck
November 1998. Index 9th edition; Merck & Co, Rahway, 1976.
21. Taylor, K.C., Al-Ghamdi, A. And Nasr-El-Din, H.A.,
Effect of Additives on the Acid Dissolution Rates of
Calcium and Magnesium Carbonates; SPEJ, Vol. 19,
No. 3, pp. 122–127, August 2004.
22. Taylor, K.C. and Nasr-El-Din, H.A., Measurement of
Appendix
Acid Reaction Rates with the Rotating Disk Solving Eq. 18 for the value of the citric
apparatus; paper 2007-015 presented at the 8th
Canadian International Petroleum Conference, acid diffusion coefficient
Calgary, Alberta, 12-14 June 2007. Based on Eq. 18, it is known that the calcite dissolution rate
23. Apelblat, A., Solubilities of Organic Salts of will have a linear relationship with the square root of the disk
Magnesium, Calcium, and Iron in Water; Journal of rotational speed and the slope of this relationship is equal to:
Chemical Thermodynamics, Vol. 25, No. 12, pp.
1443-1445, 1993. 2 / 3

24. Buijse, M., Boer, P., Breukel, B., Klos, M. and 0.62048  * CB
slope  D …………...(A-1)
Burgos, G., Organic Acids in Carbonate Acidizing; 1 / 3 2 / 3
SPE Production and Facilities, Vol. 19, No. 3, pp.  
1  0.2980   0.1451 
128-134, August 2004. D D
25. Lund, K., Fogler, H.S., McCune, C.C and Ault, J.W.,
Kinetic Rate Expressions for Reactions of Selected  -1/3 
With x = ( ) and x2 = ( )-2/3, Eq. (A-1) can be rewritten
Minerals with HCl and HF Mixtures; paper SPE 4348 D D
presented at the Oilfield Chemistry Symposium of the as follows:
Society of Petroleum Engineers of AIME, Denver,
Colo., 24-25 May 1973. 0.62048 * CB  X 2  slope  0 …………………(A-2)
26. Conway, M.W., Asadi, M., Penny, G. And Chang, F., 1  0.2980 X 2  0.1451 x
A Comparative Study of Straight/Gelled/Emulsified
Hydrochloric Acid Diffusivity Coefficient Using Eq. (A-2) can be simplified to a quadratic equation as follows:
Diaphram Cell and Rotating Disk; paper SPE 56532
presented at the SPE Annual Technical Conference
and Exhibition, Houston, TX, 3–6 October 1999. 0.62048 * CB  X 2  slope  0
27. Lund, K., Fogler, H.S., McCune, C.C and Ault, J.W.: 1  0.2980 X 2  0.1451 x
“Acidization II. The Dissolution of Calcite in
0.62048 * CB  X 2  slope * 1  0.2980 X 2  0.1451 x   0
Hydrochloric acid; Chemical Engineering Science,
Vol. 30, No. 8, pp. 825–835, August 1975. 1  0.2980 X 2  0.1451 x
28. Kung, M. S., Flow and Reaction of Weak acids in 0.62048 * CB  X 2  slope * 1  0.2980 X 2  0.1451 x   0
Carbonate Porous Media; MS Dissertation, U of
0.62048 * CB  0.2980 * slope X 2  0.1451* slope X  slope  0 ……...(A-3)
Mich, 1998.
29. Schmidt, L., The Engineering of Chemical Reactions; Eq. (A-3) is a quadratic equation and can be solved for the
Oxford University Press, Oxford, 1998. value of x, and hence the value of the citric acid diffusion
30. Barton, P., and Vatanatham, T., Kinetics of coefficient can be determined from the value of x, where
Limestone Neutralization of Acid Waters; 
Environmental Science and Technology, Vol. 131, No. x = ( )-1/3.
11, pp. 262-266, November 1976. D
31. Plummer, L.N., Wigley, T.M., and Parkhurst, D.L.,
The Kinetics of Calcite Dissolution in CO2 Water
Systems at 5°C to 60°C and 0.0 to 1.0 atm. CO2; J.
American Science, Vol. 278, No. 2, pp. 179-216,
February 1978.
32. Sjöberg, E.L., and Rickard, D., Temperature
Dependence of Calcite Dissolution Kinetics between

8
 Table 1: Calculation of Citric Acid Diffusion Coefficient Using Various Citric Acid
Concentrations at 40°C, Based on Eqs. 10-12.
0 6 2 5 2 6 2
C, M Α µ /µ 1+C(d lny/dC) 10 Dm, cm /s 10 Di, cm /s 10 D, cm /s
0.052 0.116 1.00 1.01 6.63 1.53 7.16
0.104 0.084 0.97 1.02 6.50 1.49 6.86
0.260 0.053 0.95 1.050 6.57 1.46 6.80
0.390 0.044 0.93 1.076 6.61 1.43 6.78

Table 2: The maximum Concentration of Calcium Ions in Reaction Solutions of Citric Acid with
Calcite after 50 minutes at 1,000 rpm, 50°C, and 1,000 psi.
a
Initial Citric Acid Concentration, wt% Concentration of Calcium , mg/l
1 320
2 760
5 1,350
7.5 2,100
a: The calcium concentration is not corrected for volume change due to sample withdrawal.

Table 3: Effect of Temperature on the Diffusion Coefficient of Citric Acid at Initial Acid
Concentration of 7.5 wt% and 1,000 psi.
2 -1
D, cm /s ln (D) T, K 1/T, K
1.3634E -6 -13.505 298 0.003356
2.68E -6 -12.830 313 0.003195
4.5E -6 -12.311 323 0.003096

Table 4: Apparent Activation Energy for Calcite Dissolution Rate in Various Acid Systems.
Reference Rock Type Reactive System Activation Energy, kJ/mol
Mass-transfer limited
(30)
Barton and Vatanatham Limestone Sulfuric Acid 14
(31) Saturated CO2
Plummer et al. Calcite 40
water
(32) a
Sjöberg and Rickard Calcite HCl +KCl 16
(33)
Alkattan et al. Calcite HCl 19
Surface reaction limited
(32) Calcite (Iceland a
Sjöberg and Rickard HCl + KCl 45
Spar)

(32) a
Sjöberg and Rickard Calcite (Marble) HCl + KCl 54
(27)
Lund et al. Calcite HCl 63
a. HCl was added to control the pH value from 2.7 to 8.

9
 Figure 1: Distribution of Citric Acid Species at 25C and 1 atm.
pKa Values Were Obtained from Levien(15), and Maryadele et al.(34).

Figure 2: Mechanism of Calcite Dissolution in Citric Acid Solutions.

10
Figure 3: Diffusion Coefficient of Citric Acid as a Function of Its Concentration at 25°C,
Muller and Stokes(18).

Figure 4: A Schematic Diagram of the Rotating Disk Apparatus.

11
 pH
Calcite Disk 2.3 5.0
-
Boundary Layer

Diffusion of Ca2+ + CO2

Diffusion of H3AOH

Bulk Concentration, CB
Figure 5: Change of pH Value from 2.3 in the bulk solution to 5.0 at the Reacted Calcite Disk
after the Reaction of 7.5 wt% Citric Acid with Calcite for 50 minutes at 50C.

Figure 6: Moles of Calcium in Solution as a Function of Reaction Time. Initial Citric Acid
Concentration of 1 wt% at 1,000 rpm, 50°C, and 1,000 psi.

12
 Figure 7: Moles of Calcium in Solution as a Function of Reaction Time. Initial Citric Acid
Concentration of 5 wt% at 1,000 rpm, 50°C, and 1,000 psi.

Figure 8: Calcite Dissolution in Citric Acid Solutions of Initial Concentrations of 1, 2, 5, and

7.5 wt% as a Function of the Square Root of Disk Rotational Speed at 50°C and 1,000 psi.

13
Figure 9: Viscosity Values of Different Citric Acid Solutions as a Function of Temperature.

Figure 10: Theoretical Diffusion Coefficient of Citric Acid as a Function of Its Concentration
at 50°C.

14
 Figure 11: Experimental Diffusion Coefficient as a Function of Citric Acid Initial
Concentration at 50°C.

Figure 12: Dissolution Rate of Calcite in Citric Acid Solutions of Initial Concentration of 7.5
wt% as a Function of Reaction Temperature, Rotational Speeds of 100 to 1,000 rpm at 1,000 psi.

15
Figure 13: Diffusion Coefficient of 7.5 wt% Citric Acid as a Function of Temperature at 1,000
psi.

16