SPE 164127

Interrelationship of CO
2
, Weak Acids, Bases, and pH in Scale Prediction and
Control
Amy T. Kan, SPE, Nan Zhang, SPE, Wei Shi
1
, Kevin Wang
2
, Lu Wang, Chao Yan, Fei Yan and Mason B. Tomson,
SPE, Rice University and Ross C. Tomson, SPE, Huiguang Zhu, Syed M.A. Razavi, Shale Water Research Center
Copyright 2013, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposiumon Oilfield Chemistry held in The Woodlands, Texas, USA, 810 April 2013.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of PetroleumEngineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of PetroleumEngineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.


Abstract
pH is one of the most important parameters for evaluating the scale and corrosion potential of the water during oil and gas
production. The effectiveness of chemical treatment can also be influenced by pH in the production tubing and reservoir.
Unfortunately, pH is not a conservative parameter that can be determined independently. pH changes from reservoir to surface
facilities due to changes in temperature and pressure of the production system and the corresponding G/O/W phase changes.
Measured pH value of a produced water sample is often unreliable and influenced by temperature and ionic strength of the
solution, degree of degassing and sample preservation. Measuring pH in line or with downhole probe at real field condition
can be expensive and difficult. pH can be predicted theoretically from charge balance equations more economically and
reliably by assuming a good knowledge of thermodynamic equilibrium constants, activity coefficients, G/O/W flow rates,
temperature, pressure, and reliable produced water composition. The authors research group recently developed a new
automatic titration method to simultaneously measure total alkalinity and weak organic acids concentrations of brine. The
carbonate thermodynamics were evaluated with calcite solubility studies at ultra-high temperature and pressure. The newly
developed thermodynamic data and method enable accurate prediction of produced water pH at temperature and pressure
typically encountered in deep water production. In this paper, the influences of water chemistry parameters on pH are
reviewed. The newly developed automatic alkalinity titration method is discussed. pH calculated by the recently validated
thermodynamic constants and activity coefficients are compared with live water pH measurements.


1
This author is currently in Aquateam - Norsk vannteknologisk senter AS
2
This author is currently in Duke university
Introduction
pH is an important variable in problems related to scale formation, corrosion, and inhibitor action. Scale and corrosion control
is a vital part of not only production process but also development planning phase. Corrosion potential of the water is
important for material selection for tubing, pipeline, and process equipment, and scaling potential is critical for the selection of
an optimal scale formation strategy by choice of operation conditions and treatment technologies.

pH is defined as the hydrogen ion activity in Eq. 1. Procedures used to measure pH of a surface sample are often of
questionable reliability. In-situ measurement of live formation temperature and pressure are available (Raghuraman et al.
2008; Mathews et al. 2009), but can be expensive and the colorimetric method has not been calibrated to the temperature and
pressure condition for ultra HTHP deep water wells. The detailed thermodynamic framework and the reason of the
impossibility of measuring pH are discussed in the Appendix A.
(1) ) ( log ) ( log
10 10
+ + +
=
H H H
m a pH
Theoretically, pH of the fluid from formation to wellhead can be estimated if the brine chemistry, CO
2
composition in the gas
phase, and the fluid flow rates are known. Coupling good reservoir sample analysis, equation of state (EOS) calculation,
rigorous thermodynamic data and robust alkalinity measurement are essential for an accurate pH prediction at all operation
conditions. The objective of this paper is to summarize the recent progress made in the authors research group on 1) the
validation of the thermodynamic data at ultra-high temperature and pressure and 2) automation of a robust simultaneous
2 SPE 164127
alkalinity and organic acid titration to improve our knowledge of pH calculation for the production system based on
thermodynamic approach and revised thermodynamic data and methodologies.

The solution pH in production system is controlled by the equilibrium of dissolved weak acids, i.e., carbonates, sulfides,
organic acids, borates, silicates, ammonia and phosphates as defined in the following alkalinity equation (Eq.2).
- 2- - - 2-
3 3
- 2-
4 4 3 4 2 4
Alkalinity=[HCO ]+2[CO ]+[Ac ]+[HS ]+2[S ]
+[NH ]+[B(OH) ]+[H SiO ]+2[H SiO ]
+[HP
+
2- 3- - +
4 4 3 4
O ]+2[PO ]-[H PO ]+[OH ]-[H ] (2)
In natural brine at the normal pH range of 4-9, the contributions of borate, silica, phosphate and ammonia to alkalinity are
negligibly small as can be seen from seawater composition listed in Table 1. The borate, silica, phosphate concentrations are
one to two orders of magnitude lower than the carbonates. Then, the relationship between pH, alkalinity, CO
2
partial pressure
and organic acids can be simplified in Eq. 3, where the activity coefficients are ignored, for clairity. A complete equation
including all species and activity coefficients can be found in Appendix B.
3
2 2 2
- 2- - - - +
3 3
1,H CO CO CO ,gas 2, 1,H CO CO , CO ,gas
2 3 2 2 2 3 2 2
2
, H S,gas
Alkalinity [HCO ]+2[CO ]+[Ac ]+[HS ]+[OH ]-[H ]
2

10 (10 )

10 10
HCO gas
pH pH
H S H S gas
HAc
HAc pH pH
HAc
K K P K K K P
K K P
K
T
K


~
~ + +
+ +
+
10 (3)
10
pH w
pH
K

Typically, the gas phase CO
2
concentration is measured from gas phase analysis with a surface sample or from reservoir fluid
analysis. Then, the CO
2
partial pressure can be calculated with EOS and mass balance relationship at any production condition.
The validity of pH calculated from Eq. 3 will depend on the accuracy of alkalinity and organic acids measurements and the
accuracy of the large number of thermodynamic constants shown in the Appendix C.

Recently, the authors research group conducted calcium carbonate solubilities at ultra-high temperature and pressure and
validated the corresponding temperature, pressure, and Pitzer activity model parameters to a temperature and pressure ranges
of 0-250 C and 14.7-21,000 Pisa at the presence of mixed electrolytes. The dominant reactions are described in Eq. 4 to 7 and
thorough discussion is presented in a companion paper (Shi et al. 2013).
3 3
2 ( )
2 2
2
2 2 3 3
2 2 3 1
( )
2 (4)
, K (
CO aq
H HCO HCO
CO aq
H O
CO H O CaCO Ca HCO
a m a
CO H O HCO H
a m
+
+
+
+ + +
+ + =
2 2
3 3
3 3
2 2 2 2
3
3 3
2
3 3 2
2 2
3 3 ,
5)
, K (6)
, K
H CO CO
HCO HCO
sp CaCO
Ca Ca CO CO
a m a
HCO CO H
m
CaCO Ca CO m m

+

+ +
+
+
+ =
+ = (7)

A set of equilibrium constants was selected based upon experimental measurements, which, together with Pitzer coefficients
for activity coefficients, produce predictions consistent with measured data for the NaCl system and hence, validate the
thermodynamic constants required to calculate pH at ultra-high temperature and pressure ranges via Eq. 3.

According to Eq. 3, the alkalinity, not bicarbonate concentration, is a "conservative" property of the brine. The pH will
increase as CO
2
and H
2
S gas are released from solution while the brine flows up a well. As the pH changes the relative amount
of various weak acids on the right hand side of Eq. 3 will change, but the total alkalinity does not change at all. Therefore, with
the partial pressure of CO
2
, alkalinity is a robust tool to calculate the pH, bicarbonate concentration, corrosion and carbonate
scaling tendencies at different conditions from downhole to wellhead. Alkalinity is often incorrectly assumed to be equal to the
bicarbonate concentration. But this relation no longer holds in the presence of weak organic acid. Oilfield water may contain
significant amount of organic acids (Carothers and Kharaka 1978; Lundegard and Kharaka 1990). Carother and Kharaka
(Carothers and Kharaka 1978) reported the concentrations of short chair aliphatic acid anions (acetate, propionate, butyrate
and valerate) in 95 formation water samples from 15 oil and gas fields in California and Texas. The water samples at reservoir
temperatures between 80 and 160 C contain aliphatic acid anions up to 4,900 mg/L. The aliphatic acids often contribute more
than 50% and sometimes up to 100% of the measured alkalinity.

There is no easy method to measure alkalinity when organic acid concentration contributes to a significant fraction of total
alkalinity. As shown in Figure 1, the alkalinity can be determined when bicarbonate is the predominant contributor to total
SPE 164127 3
alkalinity by acid titration (American Public Health Association. et al. 1998). Numerous efforts have been made to accurately
determine the ending point when the bicarbonate alkalinity was titrated (Thomas and Lynch 1960; Survey 2012). However, in
the presence of high fraction of organic acids, the titration end point is smeared and it is difficult to determine the ending point
and hence the total alkalinity. Furthermore, the total alkalinity often deteriorates rapidly during the shipment and storage of
samples, especially when proper sampling procedure is not followed. Therefore, sampling procedure and alkalinity
measurement remains the most difficult brine chemistry problems and there is, as yet, no automated instrumental method to
measure alkalinity. Previously, we developed a rigorous theoretical solution of this problem and proposed a corresponding
experimental method to accurately measure both bicarbonate and weak acids simultaneously with minimal experimental
difficulty (Tomson et al. 2005; Tomson et al. 2006). In this paper, this method has been automated with continuous addition of
acids and the curve fitting procedure has been updates with the addition of silicates, ammonia, borate, and phosphate species.
With the addition of this method, the pH, scaling and corrosion tendencies of a production system can be properly predicted.
In the following, the new automated titration method and testing results will be discussed.

Materials and Method

In short, the method involves the automated titration of a filtered solution at a fixed PCO
2
, to pH of 3.0. The procedure uses
the solution as its own reference and is not highly sensitive to either temperature or PCO
2
. Typically solutions should be
titrated at room temperature and PCO
2
greater than .01 atm or greater than existing natural conditions. A schematic
representation of the experimental apparatus is shown in Figure 2. Note that adding or removing neutral CO
2
or H
2
S from
solution has no effect on the alkalinity. By sparging the original brine with CO
2, gas
, sulfides in solution are removed as H
2
S
, gas

and each moles of sulfide is substituted by bicarbonate (Eq. 8). Thus, sulfides will not be included in the curve fitting equation
for determining the alkalinity and organic acid discussed below.
, gas
2,gas 3 2
HS CO HCO H S 8

+ +
Samples Preparation and Particulates Alkalinity.
All chemical were analytical grade. Synthetic brines with a total alkalinity from 200-2000 mg/L were prepared for the
accuracy test. Produced water from a northwest Texas shale basin were collected by using screw-cap sample bottles, stored at
4 C and analyzed until solutions reach back to room temperature. The composition of the synthetic brines and the field sample
are listed in Table 2 and 3, respectively.
Sample alkalinity may transfer from solutes to particulates because of the following oxidation and precipitation reactions
(Eq. 9-12)
(9) 2H ) ( 5 . 2 25 . 0 Fe Oxidation
, 3 2
2
2
+ +
+ + +
solid
OH Fe O H O
(10) 2 ion Precipitat
, 3 2 , 3 3
2
aq solid
CO H CaCO HCO Ca + +
+
(11) 2 ion Precipitat
, 3 2 , 3 3
2
aq solid
CO H FeCO HCO Fe + +
+
(12) 2 ion Precipitat
2
2
aq
S H FeS HS Fe + +
+

Each moles of Fe or Ca precipitated consumes two equivalent of alkalinity. Hence, the loss of alkalinity due to oxidation and
precipitation can be quantitatively corrected after the titration measurement. In this method, the water sample was filtered by a
0.45 m filter, , which was then put in 50 mL 1% nitric acid to dissolve Ca and Fe precipitates. Ca
2+
and Fe
2+
concentrations
from the acid extract were analyzed by inductively coupled plasma-optical emission spectrometry (ICP-OES, Perkin Elmer
Optima 4000 DV, Atlanta, GA, USA), thus the alkalinity from the particulates was determined. Then, the errors due to such
sampling problems is automatically accounted for in the Rice Simultaneous Alkalinity and Organic Acid Titration Method

Excel program.
Automated Titration with acid.
Sample pH was measured and Phenolphthalein pH indicator was added before titration. If the initial sample pH is greater
than 8.3, 1N HCl was added to lower the solution pH to 8.3 pH. A N
2
gas containing 1% CO
2
was sparged into approximately
100 ml filtered sample vigorously for about 20-30 min until the pH reached equilibrium, indicating the sample is saturated
with CO
2
. CO
2
was equilibrated with water vapor before introduced into samples to avoid the water evaporation from samples
during vigorous sparging. HCl standard solution (1.000 N) was delivered into the sample with a flow rate of 2 ml/hr by a
syringe pump (NE300 Just Infusion
TM
Syringe Pump), so the pH can re-equilibrium after each acid addition. A lower flow rate
of 0.5 ml/hr may be used for samples with alkalinity as low as 100 mg/L. pH was measured by a pH electrode Ross electrode
by Orion) and recorded automatically by a data logger (Fisher Scientific Datalog Assist Software) until the end point of about
pH 3 was reached.
Simultaneous Alkalinity and Organic Acids Method and Curve Fitting Equation.
The automated titration method can simultaneously measure the organic acids and total alkalinity in one titration. A
theoretical equation derived from the general alkalinity equation is used to calculate HCl needed at each titration point.
Detailed derivation of the curve fitting equation is discussed in Appendix D. In order to accommodate a wide variety of
water samples, in this study the alkalinity equation used in curve fitting includes all weak anion species (carbonate,
organic acid, borate, silica, phosphate, ammonia) in Eq. 2. The silica, boron and phosphorus concentrations can be
measured by ICP. Note that this method can accommodate all possible weak acid species in the system, as long as the
4 SPE 164127
TotAcid concentration is know along with ionization constants; this would include such materials as H
3
AsO
4
, H
3
AsO
3
,
naphthenic acids, HOCl, humic acids etc., as well as the metals such as TotFe(III), Cu(II), Mo(VI), Al(III), etc. The
alkalinity equation could be expanded as below:
2 3
2
3 3
1,H CO CO CO ,gas , 2,
2 3 2 2
HCO CO
2
1
Alkalinity ( )
(All additional deprotonated weak acid species for which TotAcid concentrations are kno
g CO HCO
HAc HAc w H
HAc
HAc HAc H
H H H AC OH H
K K P K
K K a
T
a a a K a

+ + + +
~ + + + +
+
wn)

(13)
Acetic acid is used as a model species for all carboxylic acids, which share a similar pKa value, around 4.7 at STP. The
experimental titration data (pH versus volume of acid added) can be curve fitted using rigorous non-linear least square curve
fitting procedure. Curve fitted parameters are alkalinity (Alk), total organic acids concentrations (TAc), and two correction
parameters (f1 and f2) that correct uncertainties in electrode response, errors in the equilibrium, various organic acid species
and PCO
2
. Therefore, the procedure is not sensitive to the exact purge gas CO
2
concentration or the organic acid compositions.
For synthetic solutions of known composition or well characterized field samples, the f1 and f2 are generally close to 1.00.
Rice Simultaneous Alkalinity and Organic Acid Titration Method

, an excel based program, was used to processes the

titration data from the pH log file by automatically selecting 20 evenly spaced points for the curve fitting. Then, the program
computes the sum of squared errors of the calculated and observed HCl (M) vs. pH and minimizes the error by changing the
Alk, TAc, f1 and f2 values using a Newton-Raphson procedure in Excel Solver. Standard deviations of the curve-fitted
parameters and correlation coefficients of the fit and are calculated according to a procedure modified from Billo (Billo 2001).

Results and discussion

Accuracy of the Method and Comparison with Conventional alkalinity titration method..
Excellent agreement between the ture and calculated alkalinity and carboxylic acid concentration was observed in three
sythetic brines. Bicarbonate was added into brine 1 and 3 as the only source of alkalinity and 0.9 M and 0.01 M NaCl were
added respectively as background electrolytes. Brine 2 were prepared with the same bicarbonate concentration as brine 1 but
different total alkalinity by adding sodium acetate into the solution. The titration curves were used to calculate total alkalinity
for all three brines (Table 2) with an error less than 3%. As mentioned in our previous papers the carboxylic acid concetrations
can not be easily determined independently through GC and ion chromatography A measurement of this degree of accuracy is
especially useful in the prediction of the change in alkalinity, as discussed earlier, due to the strong dependent relationship
between HCO
3
-
and carboxylate anions. Furthermore, all the experimental titration data fit the theoretic equeation well with a
correlation coefficient (r) of 0.999 or better. In this method, the alkalinity is determined by analyzing the shape of the titration
curve instead of the titration end point as is conducted in traditional titration. Therefore, the goodness of the curve fitting is
critial for the accuracy of the calculated alkalinity value. In Figure 3, the theoretical pH values are calculated based on the
alkalinity equation with 0.01 molal total alkalinity and then the pH values were generated by random error generator using
Microsoft Excel program. The calculated total alkalinity was maintain in the 6102 mg/L for a theoretically generated ideal
titration curve with up to 6% random errors, indicating that this method is quite robust.
Four produced water from a northwest Texas shale basin have been tested by this automated titration procedure. In Figure 4
is shown the titration results from our program. Alkalinity was also determined by the conventional alkalinity method
recommanded by U.S. EPA and U.S.G.S., which underestimates the total alkalinity when organic acids are present. The results
from two methods were compared in Table 4. With the conventional method, no carboxylic acid is theorecitally considered,
not to mention that the titration end point becomes extremely difficult to identify as shown in the titration data (Figure 4).
However, significant concentrations of organic acid can be found in the oilfield brines (Table 4), for which cases this method
is theoretically correct and shall be more accurate in determining the total alkalinity and carboxylic acid concentration
simultaneously.

Prediction of pH under Various Temperature, Pressure and TDS.
When a producer plans a deepwater project, it is important to evaluate the reservoir fluid systems and thus to gauge the future
impact of fluids on wellbore corrosion. pH is a critical evaluation parameter, but it can vary significantly with the change of
temperature, pressure and TDS in the reservoir. A lower solution pH can be observed at higher temperature by further
dissociation of water. Solving the equilibrium constant and the charge balance equation at a given temperature, the pH of water
can be expressed by Eq. 14.
( )
1/ 2
1/ 2
10 10
- log log (14)
H
w
H
OH
pH a K

+
+

| |
| |
|
= = |
|
|
\ .
\ .


Since the water dissociation constant (K
w
) varied from 10
-14
to 10
-12.26
, the pure water pH changes from 7 pH to 6.13 pH when
temperature changes from 25 to 100 C.
Dissolved ions also yield solutions of lower pH. As described in the above equation, the pH differs from the pure water
value only by the square root of the ratio of activity coefficients of the hydrogen and the hydroxide ions. The activity
SPE 164127 5
coefficient of the hydroxide ion is always less that of hydrogen. In addition, the value read on a pH meter, when calibrated by
the standard method, differs from the true pH (pH -log
10
(a
H+
)), by the junction potential of a standard electrode (Eq.15 and
Appendix A2). For example, at 1.0 M NaCl, or 23,000 mg/L Na
+
and 35,450 mg/L Cl
-
, and 25 C:
H+
= 0.876 and
OH-
= 0.609
and pH = - log
10
(10
-14
0.876/0.609) -0.13 = 6.79.
1/ 2

-0.13 ( , ) (15)
meter reading true junction potential true
pH pH pH pH IS M = A =

Introduction of CO
2
in the system will furthermore complicate the matter. With the present of CO
2
, The pH will decrease
and the effects of temperature and pressure can become very large and hence, cause the steel to corrode (deWaard and
Williams 1975). For example, in the presence of 1% CO
2
in the gas and at room temperature and one atm pressure, the pH
meter
reading
= 4.68. First, increasing the T to 93C (200 F), but still at 1 atm pressure, raises the pH from 4.68 to 4.96. This is due to
the fact that at the same P
CO2
= 0.01 atm, the amount of CO
2
that is pushed into solution is less than it is at 25 C (77 F).
There is a secondary impact of the change in the ionization constants of carbonic acid and of water, but the primary effect is
due to the decreased solubility of CO
2
in water at the higher temperature. Next, raising the pressure to 10,000 psi at the same
temperature of 100C (212 F) would lower the pH to 3.68. This is of course because the increased pressure greatly increases
the P
CO2
and the amount of CO
2
that is correspondingly pushed into the salt water. A lower pH will occur when the
temperature and pressure further increase to the ultra-temperature and pressure regimes, for example, the pH is reduced to 3.61
pH at 200C (392 F) and 20,000 psia.

Comparison of calculated versus measured pHs.
The validity of pH calculations were done by comparing the pHs calculated by ScaleSoftPitzer (SSP) to both laboratory and
field observed pHs. It should be noted that pH is only defined by the National Institute of Standards and Technology (NIST,
formerly NBS) to 0.01 pH. Kassa (Kaasa 1998) reported the pHs of two solutions containing 16.53 mM NaHCO
3
and 8.53
and 35.18 mM acetic acid at equilibrium with 0 600 psi CO
2
partial pressure at 60 C. In Figure 5 is the comparison of the
pH values calculated by SSP versus that measured by Kassa (Kaasa 1998). The agreement between calculated and measured
pH values is excellent, indicating that the equilibrium constants and activity coefficients used in the above equation agree with
measurements (Figure 5).
Raghuraman et al.(Raghuraman et al. 2008) described a technique to measure in-situ pH using a downhole InSitu probe.
Rhe pH measurement is done based on the color of a colorimetric dye injected directly into the flow stream where the optical
spectrometer detects the color change. The measurement not only reflects the condition of the water at formation temperature
and pressure, but also includes the effects of hydrogen sulfide and CO
2
. Note that the pH measurement technique is calibrated
for temperature up to 302 F and pressure to 10,000 psi and ionic strength to 3 gmol/kg. Its applicability outside the specified
range has not been known. They reported a downhole pH of 6.260.2 for a well located in the Norwegian Sea at ~54 C and
90 bar. Using the condition given in that paper, we are able to calculate a downhole pH of 6.28 with SSP.
Mathews et al. (Mathews et al. 2009) compared the calculated and measured reservoir pHs of three Gulf of Mexico wells
using modified technique than that of Raghuraman et al. The temperature and pressure range of the three wells are 137.0-242.0
F and 9,766-19,543 psi (See Table 5). The new technique involves adding pH sensitive dyes to pressurized single phase water
samples collected using a formation tester and spectroscopically determining pH in the laboratory after the formation water
sample was reheated to reservoir condition. pH measured by this technique was named Live sample pH and the results were
comparable to pH measured with the downhole InSitu probe for two of these wells. Using the measured pH of the same
reservoir water sample immediately after flashing to atmosphere enable us to calculate the corresponding reservoir pH and
calcite saturation index (SI) with our model in Table 5. Similarly, the corresponding calcite SI at reservoir condition is
calculated using the reported reservoir pHs. Note that the calculated reservoir pH by SSP are 0.14 and 0.23 pH units higher
than the in-situ probe pH for wells A-1 and A-2 and it is about 0.3 pH unit below the live pH measurement for well B-l. Note
that the live pH value for well B-1 is of uncertain quality since the pressure is beyond the calibrated range for the pH
measurements. Interestingly, the reservoir calcite SIs calculated based on SSP method are closer to zero than that based on the
measured in-situ pH or live pH. Since it is reasonable to expect that the pore water is at equilibrium with calcite in the
reservoir (i.e., calcite 0 at reservoir condition), the results in Table 5 may indicate that the calculated reservoir pH by SSP is
more representative of the true reservoir pH. Equations used in the calculation are illustrated in Appendix E. We have checked
quite a few of our pH calculations with published data, both directly and indirectly. In all cases tested, to date, the agreement is
excellent, typically about 0.05 pH, or better. For more moderate conditions this agreement is likely as close as 0.02 pH. At
the minimum, SSP is able to provide a reasonable pH at the ultra-high temperature and pressure where no direct measurement
is possible.
The significance of organic acid in scale, corrosion and pH measurements can be illustrated in Figure 6. Brine composition
of a South Texas gas well (Table 1, Demo brine) with 281 mg/L alkalinity was used in the calculation to demonstrate what the
downhole pH, calcite, siderite and iron sulfide scaling indices will be if the brine also contains a significant concentrations
(140 or 281 mg/L) of organic acids. In the presence of increasing amount of organic acids, the scaling indices of all three
mineral phases at downhole to wellhead temperature and pressures were significantly reduced due to the lower pH caused by
the presence of organic anions in brine. Therefore, corrosion could be the main problem for this South Texas well if the brine
containing a significant fraction of organic anions as total alkalinity. Otherwise, scale is the main problem as expected. In
Table 6 is shown the same calculation for four brines from Texas shale basin (Brine A, B, C and D). Disagreement between
6 SPE 164127
the prediction of pH, calcite and iron carbonate scaling indices based on alkalinity from this method and conventional method
become more significant with more organic acids in the solution, such as Brine C. Note that based on the total alkalinity and
organic acid measured from our updated method the calcite saturation indices calculated are much closer to zero at downhole
conditions, indicating the prediction of pH, scaling and corrosion potential is more reliable. On the other hand, for Brine A the
pH, SI, etc. are quite similar, whether this method or the conventional method is used; this is because when the true carboxylic
acid (305 mg/L) is subtracted from the true total alkalinity (619 mg/L) the difference is similar to the measurement by the
conventional method (340 mg/L).

Conclusions
Formation water analysis plays a role in dynamic modeling of reservoirs, quantifying reserves and calculating completion
costs. Water analysis helps operators to estimate operating expenditures and assists development planner to determine whether
new discoveries can be tied into existing infrastructure. pH is an important parameter to monitor under the various phases of
development and production. However, it is also a parameter that cannot be easily measured. In this paper, the relation
between pH, PCO
2
, and alkalinity and the validity of pH calculation are illustrated. Two primary factors that contribute to the
validity of pH calculation at system temperature and pressure are the improvement on the calcite solubility validation at ultra-
high temperature and pressure as well as the development of a rigorous alkalinity and organic acids simultaneous titration
methodology. When organic acids is more than 25% of the total alkalinity, ignoring the organic acid contribution to brine
chemistry can yield significant error in scale and corrosion prediction. The simultaneous alkalinity and organic acid titration at
constant CO
2
partial pressure method has been automated using a syringe pump to deliver acids during the titration and this
method was improved to include the contribution of borate, phosphate, ammonia, and/or silicates contribution to total
alkalinity as discussed. The method has been tested with a wide variety of produced water, natural water, and wastewater and
with commercially available autotitrator (e.g. Mettler Toledo). Implications of the importance to pH, scaling and corrosion
tendencies are also discussed.

Acknowledgments
This work was financially supported by Brine Chemistry Consortium companies of Rice University, including Baker Hughes,
BP, Champion Technologies, Chevron, Clariant, ConocoPhillips, Dow, Halliburton, Hess, Kemira, Kinder Morgan, Marathon
Oil, Multi-Chem, Nalco, Occidental, Petrobras, Saudia Aramco, Schlumberger, Shell, Shengli Engineering & Consulting Co.,
Statoil, Southwestern Energy and Total, China-U.S. Center for Environmental Remediation and Sustainable Development.
Funding for Nan Zhang was provided by the China Scholarship Council [Grant 2008102375].

Appendix A.

A1. The Thermodynamic Definition of pH in Water.
The negative of the Briggsian (common) logarithm (base ten) of the hydrogen ion activity on a molality scale (moles per
1.000 kg of water) with the activity coefficient equal to 1.000 at infinite dilution in water:
) ( log ) ( log
10 10
+ + +
=
H H H
m a pH

From half cells of the following type an attempt can be made to measure pH:

-(H
+
+ 1e
-
H
2
) E
o
0.000 V assumed to be zero at all temperatures
Ag
+
+ 1e
-
Ag
0
E
o
= +0.799 V at 25 C and 1 atm (bar)
H
2
+ Ag
+
H
+
+ Ag
0
E
o
= +0.799 V

AgCl
solid
Ag
+
+ Cl
-
E
o
= - 0.576 V (logKsp = -9.52 (x0.0591 V/log10))
H
2
+ AgCl
s
H
+
+ Cl
-
E
o
= +0.223 V


) (m . ) (m . E
) m (m . E
) a (a . E
Bar) atm ( . P ) at a (a
F
RT
E E(V)
Cl Cl H H
o
Cl Cl H H
o
Cl H
o
H
Cl H
o
+ +
+ +
+
+
=
=
=
~ = =
10 10
10
10
log 0591 0 log 0591 0
log 0591 0
log 0591 0
00 1 ln
2

We can measure the absolute value of
+
H
m
,

Cl
m
, the cell voltages E(V) and E
o
, but there is no way to determine the
individual ion activity coefficients product,
) (
Cl H
+

! Therefore, it is not possible to measure the thermodynamic
) ( log
10
+

H
a pH
.
A2. Junction Potential for pH Measurement and Operational Definition of the pH value
For any real solution and pH measurement there will always be a junction potential, E
j
, due to the difference in the salt
content of the measured solution and the reference electrode filling solution, generally KCl:

j
Cl H Cl H
o
E ) m (m
F
RT
E E(V) + =
+ +
ln

The junction potential, E
j
, is a result of two processes. First, there is generally a concentration gradient from the measured
solution to the reference electrode filling solution at the liquid junction, which causes a voltage difference. Second, the cations
and anions typically diffuse at different rates, given by their transference numbers or essentially their mobility (
o
/F). KCl is
used as a filling solution because the mobility of the ions are very similar {73.52(K
+
) vs. 76.34(Cl
-
) Scm
2
/eq.}. Values of E
j

can be estimated by use of the Henderson equation (Bates, Bard and Faulkner, and other texts on electrochemistry). Also, E
j
,
can be measured using HCl and the values generally vary from 0.02 to 0.5 pH units. For dilute aqueous solutions (potable
waters) E
j
is approximately constant at 1 mV relative to the standard buffer solutions.
A3. Impossibility of thermodynamical pH measurement and the Operational definition of the pH value
There are at least three fundamental and one practical problems with the concept of pH and all four can only be
approximately addressed. Fundamentally (Bates),
1. It is impossible to separate the activity coefficient product,
) (
Cl H
+

;
2. There will always be a junction potential, E
j
(V) between the measured solution and the reference electrode;
3. There is no theoretical way to measure nor to calculate the transfer free energy of the proton from pure water to a mixed
water-alcohol (etc.) solvent; and
Practically, the measurement of pH is quite problematic in gas and oil wells at very high T, P, and TDS. A few quotes from
Roger G. Bates book to illustrate these ideas. Note that Roger Bates, while working at NBS [now NIST] established our NBS
standards for pH buffers in America.
The concentration of hydrogen ion is, of course, a well-defined concept, and the conventional activity of hydrogen ion is
usually made to approach concentration of this ion is solution of low ionic strength at all temperatures. Yet it may be that the
increased rate of an acid-catalyzed reaction at elevated temperatures and rapid dissolution of a metal, for example, indicate
an increase in absolute hydrogen ion activity that the conventional scale cannot reflect. Page 30
The impossibility of determining experimentally a pH value with exact fundamental definition and of defining simply the
quantity measured with the pH meter necessitates a compromise. Inasmuch as the pH cannot in every instance, or even in a
majority of instances, be an exact numerical expression of a single quantity, the fundamental meaning of the practical scale of
pH is limited. Page 31
Is there any possible means, still awaiting discovery, of determining loga
H
exactly and thus endowing the pH with the
full significance of a true physical constant? Thermodynamics leads us to believe there can be none. A consideration of cell
with a hydrogen ion electrode and a liquid junction underscores the fundamental difficulties of such a determination. Page
32
8 SPE 164127
With the awareness of those fundamental and one practical problems, operational definition of the pH value (page 60,
RGB) is represented as
10 ln RT
)F E (E
pH(S) pH
S X

+

where pH is the value read on a pH-meter, pH(S) is the value assigned to as standard reference buffer (e.g., pH(S) = 4.008 for
0.05 m KH phthalate buffer at 25
o
C,) E
S
is the voltage in pH(S) buffer, E
X
is voltage in unknown solution, T is temperature in
Kelvin, F = 96,484.6 coulombs/equivalent, R = 8.31441 J(mol
o
K)
-1
, and ln10 = 2.3026. Then, (RTln10)/F = 0.05916 V/log10
at 298.15
o
K. In short, pH is the value read on a pH-meter, when calibrated as above. How consistent are the NBS standards
within themselves and how closely do they correspond the thermodynamic concept of pH? Bates, page 85/86: an
inconsistency slightly greater than 0.01 unit is apparent for the carbonate standard and for the borax standard at elevated
temperatures The uncertainty of pH(S) appears then to be about 0.006 at 25 C and somewhat larger at other
temperatures. The uncertainty relative to the thermodynamic standard appears to be 0.003 pH units.

Appendix B.

Relation of CO
2
pressure, alkalinity and pH
The acid dissociation reactions that govern the alkalinity of water (Eq. 2) in oil and gas production are expressed as below:
2,
1, 2
2, 3
2 ,
2
2, 2,
2, 3
2
3 3
for n=0-4
3 2 3 2
2 2
2
( ) ( )
Naphthenic acid
H
CO g
CO
HCO
AC
AC
H S gas
H S
K
gas aq
K
aq
K
K
n n
K
K
gas aq
K
aq
CO CO
CO HCO H
HCO CO H
CH CH COOH CH CH COO
Naphthenate
S H S
H S HS H
+
+

+
+

+

3 3
1, 4 4
2, 3 4
4
1, 3 4
2, 2 4
3, 2 4
3 3 3
4 4 3 4
2
3 4 2 4
4 3
3 4 2 4
2
2 4 4
3
4 4
H BO
H SiO
H SiO
NH
H PO
H PO
H PO
K
K
K
K
K
K
K
H BO HBO H
H SiO H SiO H
H SiO H SiO H
NH NH H
H PO H PO H
H PO H PO H
HPO PO H
+
+
+
+ +
+
+
+
+
+
+
+
+
+
+


Substituting these equilibrium constants into Eq. 2, the following governing equation to relate alkalinity, CO
2
partial pressure
and the brine compositions are illustrated. Typically, ammonia is an added chemical to control pH and it is not present in
natural brine. The organic acids represent the summation of C2-C6 aliphatic acids and naphthenic acids. Since these carboxylic
acids share a similar pKa values, the overall weak acid concentration is represented by a single acid value in the following
equation.

2
3
2
3 3
3 3 3 3 4 4
3 3
4
3 3 3 3
4 4 2 3
1,H CO CO CO ,gas ,
2,
2 3 2 2
HCO CO
2
1
Alkalinity ( )

g CO
HCO
HAc HAc w
HAc
HAc HAc H
H H H AC OH
H BO H BO NH NH
H BO
NH
NH H BO H B
H NH NH H H BO
K K P
K
K K
T
a a a K a
K
K
T T
a K a K

+ + +
+ +
+
+ + + +
~ + + +
+
+ +
+ +
2
2 4
2
3 4 3 4
2 2
3
2 4 2 4
4 3 4 3 4 3 4
3 3
4 4
2 2 2
4 4 3 4 2 4 4 3
4
2,
2
1, 4 2, 2,
3
3, 1, 2, 3,
(2 )
( 1)
2
(
H H SiO
SiO
H SiO H SiO
O
H SiO H H SiO H
H SiO H SiO H SiO H SiO
H PO H PO
HPO HPO H PO H PO HPO H P
PO
a
T
K
a a
K K K
a a
K K K K
T

+

+ +

+ +

+
+
+ +
+
+
4
3 3 3
4 4 4
2 2 2 2
3 4 2 4 4 3 4 2 4 4 2 4 4 4
3 2
1, 2, 3, 2, 3, 3,
)
1
O
H
H PO H PO H PO H
H PO H PO HPO H PO H PO HPO H PO HPO HPO
a
a a a
K K K K K K


+ + + +

+ + +


where Alk is total alkalinity (equiv./L), T
HAC
, T
NH4
, T
H3BO3
, T
SiO2,
and T
PO4
represent the equivalent sum of molal
concentrations of organic acids, ammonia, borate, silica, and phosphate in solution. The silica, boron and phosphorus
concentrations can be measured by ICP. PCO
2
, is the CO
2
partial pressure (atm), ks are equilibrium constants and s are the
activity coefficients. The values of the activity coefficients and equilibrium constants are calculated from temperature and
ionic strength. Acetic acids are used as a model species for all organic acids.



SPE 164127 9
Appendix C.

C1. Thermodynamic variables
Thermodynamic variables are state functions, they depend upon and only upon of temperature, pressure, and composition.
Most thermodynamic models to predict activity coefficients are based upon the following excess function approach:

) (
n
/RT G

+ =
) (T,P,n ) + G (T,P,n ) = G G(T,P,n
i
i
E
E
i
Excess Ideal
i
Excess
i
Ideal
i
ln
or
=
|
|
.
|

\
|
c
c
=

For example, the Redlich-Kister and the Margules theories for non-electrolytes are based upon the Guggenheim general
function for non-electrolytes and non-polymers:

possible. heory simplest t the represent ln
: equation suffix" two Margules " Then
12 4 4 5 3 ln
or
2
2 1
4
2
3
2
2
2
1
1
2
2 1 2 1 2 1
2
Ax ) (
... C...)x ( ...)x C (B C...)x B (A
n
G
) (
+...]} ) -x ) + C(x -x [A + B(x x = RT{x G
T,P,n
E
E
=
+ + + + + =
|
|
.
|

\
|
c
c
=

C2. Pitzers specific ion interaction theory
Pitzer theory is based on the same general approach, the excess free energy is assumed to be a Virial (power series)
expansion of binary and ternary interactions with a leading term of a Debye-Huckel (Meyer/Meyer) type. Essentially:

j
n P T
i
Excess
Pitzer
ijk ij
i,j ijk
k j i ijk w j i ij w

w
Excess
Pitzer
n
RT G
Pitzer
at I
I
I
A
kg
} n n n w n (I)n w f {w RT G
, ,
i
2 / 1
2 / 1
2 / 1
w
2 1
/
) ln(
ent rearrangem le considerab after ts coefficien activity Then
for water. atm 1 and C 25 3915 . 0 A with ) 2 . 1 1 ln(
2 . 1
2
2 . 1 1
f
and constants ternary and binary are and
moles, is n
(m), molal strength, ionic I
water, of w where

|
|
.
|

\
|
c
c
=
=
|
|
.
|

\
|
+ +
+
=
=
=
+ + =

|
|

For example for a metal (M) and cations ions (c), anions (a), and neutral molecules (n):

n. compositio and I P, T, of functions are and , , , , , , constant where
2
2 2
ln
'
2
nM ca Maa Mca Mc Ma Ma
c a n
nM n ca a c
a a'
M Maa' a' a
c
Mca
a
a Mc c
a
Ma Ma a m
T,P,n
M
Excess
Pitzer
M
C C B
m C m m z m m
) m ( m ) ZC B ( m F(I) z
n
/RT G
) (
j
+ + u
+ +
+ + + + + =
|
|
.
|

\
|
c
c
=


<


Appendix D.

Detailed derivation of the curve fitting equation for simultaneous alkalinity and organic acids titration method
From the general expression of alkalinity in Appendix B, , the following relationship can be derived for the amount of acid
added and the pH. The experimental titration data (pH versus volume of acid added) was fitted to this equation using Newton-
Raphson procedure in Microsoft Excel Solver. Curve fitted parameters are alkalinity (Alk), total organic acids concentrations
(TAc), and two correction parameters (f
1
and f
2
) to correct for uncertainties in the equilibrium constants and activity
coefficients. For each titration data point i, the amount of acid added into the brine can be described as:
10 SPE 164127


2
2
3 3
3 3 3 4 4
3 3
4
3
4 4
1 1,H CO CO CO ,gas , 2,HCO
2 2 3 2 2 3
2
HCO CO
v =Alk
2
1
( )
brine brine acid
acid
acid acid
g CO
HAc HAc w
HAc
HAc HAc
H H H AC H OH
H BO H NH NH
H
H BO
NH
NH
H H NH NH
V V V
M M
f K K P K
f K K
T
a a a f K a
K
K
a
T T
a K

+ + + +
+ +
+
+ + + +
+
+
+ + +
+
+ +
+
2
2 4
2
3 3 4 3 4
2 2
3 3 3 3 2 4 2 4 2 3
4 3 4 3 4 3 4
3 3
4 4
2 2
4 4 3 4 2 4
4
2,
2
1, 4 2, 2,
3
3, 1, 2, 3,
[H ]
( 2)
( 1)
2
(
H SiO
SiO
BO H SiO H SiO
H BO H BO H SiO H H SiO H H H BO
H SiO H SiO H SiO H SiO
H PO H PO
HPO HPO H PO H PO HP
PO
T
K
a a a K
K K K
a a
K K K K
T

+ + +

+ +

+
+
+
+
+ +
+
+
2
4 3 4
3 3 3
4 4 4
2 2 2 2
3 4 2 4 4 3 4 2 4 4 2 4 4 4
3 2
1, 2, 3, 2, 3, 3,
)
1
O H PO
H PO H PO H PO
H PO H PO HPO H PO H PO HPO H PO HPO HPO
a a a
K K K K K K

+ + +

(
(
(
(
(
(
(
(
(
(
` (
(
(
(
(
(
(
(
(
+ + +
(
)





Appendix E.

Relationship of calcite solubility to carbonate equilibrium and reservoir pH prediction
The reservoir fluid is typically saturated with respect to calcite, i.e., the calcium carbonate saturation index (SI) equals zero
at reservoir condition.

2 2
3 3
2 3, . 2 3, .
2
3
2,
2
3, 2 3, 3
2 2
2, 3 2
10 10 10
1 1, 2
2
2,
10 10
2
log log log ( , )
log log
aq aq
gas
solid aq
Ca HCO Ca HCO HCO
H CO sp H CO sp CO aq
Ca HCO HCO
CO
CaCO H CO Ca HCO
a a a a
K K
SI T P
a K K a K K
a a
K
a
+ +
+
+
+ +
| | | |
| |
= | = | +
|
|
| |
\ .
\ . \ .
| |
= | +
|
\ . 2 2,
3
1,
( , )
aq gas
sp CO CO
T P
K K K
| |
|
|
\ .

where
2 2 2
3 3 3
2, 2, .
2 2 2
10 10
2
log log

gas gas
Ca HCO Ca HCO Ca HCO
CO CO
a a m m
a PCO f

+ + +
| | | |
| = |
| |
\ . \ .

The above equation is not a function of pH. The reservoir pH can be calculated by assuming the SI =0 with the bicarbonate
concentration and CO
2
partial pressure.

Reference

American Public Health Association., American Water Works Association., Water Pollution Control Federation. and Water Environment
Federation. 1998. Standard methods for the examination of water and wastewater. New York, American Public Health Association: v.

Billo, J. 2001. Excel for Chemists. New York, John Wiley and Sons.

Carothers, W. W. and Kharaka, Y. K. 1978. Aliphatic acid anions in oil-field waters-Implications for origin of natural gas. Am. Assoc. Pet.
Geol. Bull. 62(12): 2441-2453.

deWaard, C. and Williams, D. E. 1975. Prediction of Carbonic Acid Corrosion in Natural Gas Pipelines. First International Conference on
the Internal and External Protection of Pipes, Univ. of Durham, UK.

SPE 164127 11
Kaasa, B. 1998. Prediction of pH, mineral precipitation and multiphase equilibria during oil recovery. Institutt For Uorganisk Kjemi.
Trondhein, Norge Teknisk-Naturvitenskapelige Universitet: 267.

Lundegard, P. D. and Kharaka, Y. K. 1990. Geochemistry of organic acids in subsurface waters. Field data, experimental data, and models.
ACS Symposium Series (Chem. Model. Aqueous Syst. 2) 416: 169-89.

Mathews, S. G., Raghuraman, B., Rosiere, D. W., Wei, W., Colacelli, S. and Rehman, H. A. 2009. Laboratory Measurement of pH of Live
Waters at High Temperatures and Pressures. SPE International Symposium on Oilfield Chemistry. The Woodlands. Texas, Society of
Petroleum Engineers.

Raghuraman, B., O'Keefe, M., Eriksen, K. O., Tau, L. A., Vikane, O., Gustavson, G. and Indo, K. 2008. Real-Time Downhole pH
Measurement Using Optical Spectroscopy. SPE Reservoir Evaluation & Engineering 10(3): 302-311. SPE-93057-PA. doi:10.2118/93057-
PA.

Shi, W., Zhang, N., Wang, W., Kan, A. T. and Tomson, M. B. 2013. SPE 1640454 Dissolution of Calcite at High Temperature and Pressure
in Complex Solution. 2013 SPE International Symposium on Oilfield Chemistry, Woodlands, TX, USA.
, 8 - 10 April, 2013


Survey, U. S. G. 2012. Techniques of Water-Resources Investigations Book 6 Chapter 6.6 Alkalinity. S. A. Rounds.

Thomas, J. F. J. and Lynch, J. J. 1960. Determination of Carbonate Alkalinity in Natural Waters. Journal (American Water Works
Association) 52(2): 259-268. 0003150X.

Tomson, M. B., Kan, A. T., Fu, G. and Cong, L. 2006. Measurement of total alkalinity and carboxylic acid and their relation to scaling and
corrosion. SPE J. 11(1): 103-110. SPE-87449-PA. doi: 10.2118/87449-PA.

Tomson, M. B., Kan, A. T., Fu, G., Wu, X., Al-Thubaiti, M., Kirk, J., Martin, R., Prukop, G., Inan, E. E. and Davis, S. T. 2005. SPE 93266
Simultaneous analysis of total alkalinity and organic acid in oilfield brine. . SPE International Symposium on Oilfield Chemistry Houston,
Texas, U.S.A., SPE.



Table 1. Composition of a South Texas produced water (Demo brine) and seawater

Ions Demo Brine
(mg/L)
Seawater
(mg/L)
Na
+
19,872 11,020
K
+
500 408
Mg
2+
54 1322
Ca
2+
6,500 422
Sr
2+
700 6.89
Ba
2+
550 0.02
Fe
2+
12 0
Cl
-
43,000 19,805
SO
4
2-
5 2,775
F
-
NA* 1.4
Br
-
NA 67
Silicone 1 4.6
Alkalinity 281 145
Organic acids 0 0
Boron NA 4.2
H
2
S,aq 4.3 0
TDS 70,000 35,968
*NA= Not analyzed





Table 2. Composition of three synthetic brines for alkalinity titration

Brine 1 Brine 2 Brine 3
Synthetic
(mg/L)
Measured
(mg/L)
Synthetic
(mg/L)
Measured
(mg/L)
Synthetic
(mg/L)
Measured
(mg/L)
Na
+
+
(mg/L)
19,595 19,608 230
K
+
+
(mg/L)
116 116 0
Mg
2+
(mg/L) 226 228 0
Ca
2+
(mg/L) 0
Sr
2+
(mg/L) 94 97 0
Ba
2+
(mg/L) 42 42 0
Cl
-
(mg/L) 30,957 29,978 0
CH
3
COOH (mg/L) 0 0
(2)*
1,697 1654
(4)*
0 0
(0)*
Total Alkalinity (mg/L) 207 201 (1)* 1,909 1956 (3)* 610 593 (8)*
TDS (mg/L) 51,236 51,981 840
Goodness of fit (r) 1.000 1.000 0.999
*Values in parentheses are the standard deviation of the calculated values.







SPE 164127 13
Table 3. Composition of four produced waters from a northwest Texas shale basin

Ions Brine A
(mg/L)
Brine B
(mg/L)
Brine C
(mg/L)
Brine D
(mg/L)
Na
+
70,575 11,020 18,946 64,807
K
+
259 408 185 320
Mg
2+
674 1,322 100 295
Ca
2+
4,526 422 520 1926
Sr
2+
438 6.89 169 347
Ba
2+
2.3 0.02 1.1 1.6
Fe
2+
4.0 0 19.6 0.2
Cl
-
70,575 19,805 19,460 66,302
Silicone 5.7 4.6 36.2 7.7
Boron 24.5 4.2 54.1 22.8
TDS 144,000 35,968 39,400 134,000
pH* 6.9 7.2 7.0
*pH refers to the measured value after sampling.








Table 4. Comparison of alkalinity and organic acids concentrations of four produced water from a
northwest Texas shale basin measured by the automatic alkalinity and organic acids titration method and
by the conventional alkalinity measurements

This Method
HACH
Colorimetric
Method

Total
Alkalinity
(mg/L)
Std. dev.
Organic
Acids
(mg/L)
Std. dev.
Alkalinity
(mg/L)
Brine A 619 7 305 26 340
Brine B 395 4 236 10 283
Brine C 1459 35 918 37 1179
Brine D 699 47 196 49 648



















14 SPE 164127
Table5. Comparison of literature reported and ScaleSoftPitzer (SSP) calculated reservoir water pH and
calcite saturation indices. The literature data were that of Mathews et al. 2009.

Well A-1 Well A-2 Well B-1
Reservoir T (F) 137.8 137.0 242.0
Reservoir P (psi) 9868.5 9766 19,543
GWR (scf/stb) 0.3 0.2 8.0
pH after flush at T
1
6.49 6.43 6.21
Temp for pH
measurement (F)
2
101 90 75.2
pH @
Reservoir
T & P
Live
sample
6.06 5.83 6.05

In-situ 6.14 5.91
SSP Calc 6.28 6.14 5.75
Reservoir
Calcite SI
calc from
in-situ pH
-0.30 -0.14 0.21
4

calc from
pH after
flush at T
-0.17 0.09 -0.07
1
The pH is measured immediately after the reservoir water sample was flashed to 1 atm.
2
While the water sample is flashed to 1 tam, the temperature is not controlled and is recorded as the flash temperature
3
In situ pH is measured with the InSitu formation tester.
4
Calcite SI calculated using the live sample pH value.
5
The reservoir pH is extrapolated from the live sample pH measured at reservoir temperature and 8, 000 psi to the reservoir pressure of 19,543 psi.








Table 6. The impact of the presence of organic acids on brine pHs, calcite and iron carbonate scaling
indices and at downhole (DH) and wellhead (WH) temperatures and pressures

Brine A Brine B Brine C Brine D

This
Method
HACH
Conventional
Method
This
Method
HACH
Conventional
Method
This
Method
HACH
Conventional
Method
This
Method
HACH
Conventional
Method
Alkalinity mg/L 619 340 395 283 1459 1179 699 648
Organic
acid
mg/L 305 NA 236 NA 918 NA 196 NA
Calcite SI
DH -0.02 -0.07 0.01 0.13 0.00 0.26 0.02 0.06
WH 0.94 0.99 0.26 0.54 0.47 0.85 0.86 0.97
Iron
Carbonate
SI
DH -1.39 -1.44 -1.73 -1.61 0.33 0.61 -2.36 -2.28
WH -0.51 -0.47 -1.26 -0.98 0.75 1.17 -1.53 -1.40
pH
DH 5.30 5.25 5.59 5.51 5.75 5.69 5.42 5.40
WH 6.90 6.90 6.90 6.90 7.20 7.20 7.00 7.00

SPE 164127 15
3.0
4.5
6.0
7.5
0.000 0.001 0.002 0.003
p
H
HCl added (M, Exp)
Well #22
3.5
4.0
4.5
5.0
5.5
6.0
6.5
p
H
Well #6-6


Figure 1. Alkalinity titration of two field brines from well #22 and well #6-6. Well #22 contains 560 mg/L alkalinity and organic acids
concentration is below detection limit. Well #6-6 contains 139 mg/L alkalinity and 96 mg/L organic acids.















Figure 2. Schematic diagram of the autotitration apparatus (1. CO2/N2 gas cylinder 2. Gas regulator 3. HPLC 10m solvent filter 4.
Magnetic sitter 5. pH electrode 6. pH meter 7. Syringe pump 8. Syringe)
16 SPE 164127



Perfect data 2% Error 4% Error 6% Error
r
2
1.00
Std.
Err.
0.996
Std.
Err.
0.931
Std.
Err.
0.849
Std.
Err.
Alk.(mg/L) 610 0 612 3 610 20 608 15
Carboxylic
acid
(mg/L)
0 0 0 0 4 36 0 0


Figure 3. Calculated pH versus acid concentrations of brine 3 with the random error in titration data following the simultaneous
titration of alkalinity and organic acid titration at 0.01 atm CO2 partial pressure.







































Figure 4. pH versus acid concentrations of four brines following the simultaneous titration of alkalinity and organic acid titration at
0.01 atm CO2 partial pressure. The red symbols are fitted titration curve.

3.0
4.0
5.0
6.0
7.0
8.0
0.0000 0.0010 0.0020 0.0030
p
H
HCladded (M,Exp)
Exp Calc
3.0
4.0
5.0
6.0
7.0
8.0
0.0000 0.0100 0.0200 0.0300
p
H
HCladded (M,Exp)
Exp Calc
Brine A Brine B
Brine C Brine D
SPE 164127 17

Figure 5. SSP calculated versus measured pHs. The pH of two solutions at equilibrium with different CO2 partial pressure in the gas
phase. The experimental data were from Kaasa(Kaasa 1998). The two solutions containing 16.53 mM sodium bicarbonate and either
8.53 or 35.18 mM acetic acid. The pHs were measured at 60 C and the solution is at equilibrium with 0 500 psi CO2 partial pressure
(0-40 bar).






Figure 6. Illustration of the impact of the presence of organic acids on a demo brine to brine pHs at downhole (DH) and wellhead
(WH) temperatures and pressures of 340 F, 7000 psia and 140F, 400 psia.