Why Scale Forms and

How To Predict It
".E. Oddo, SPE, Water Research Inst. Inc. and M.B. Tomson, SPE, Rice U.

Summary. Predicting potential scaling problems can be difficult, and numerous saturation indices and computer algorithms have
been developed to determine if, when, and where scaling will occur. The Langelier, Stiff-Davis, and the Oddo-Tomson saturation in-
dices, all widely used in the oil field, are compared and contrasted relative to calcium carbonate scale. New saturation indices for bari-
um, strontium, and calcium sulfate scale formation are introduced and discussed, along with an updated version of the Oddo-Tomson
calcium carbonate index. An updated version of the CaC0 3 saturation index is presented that includes correction terms for fugacity
effects and changes in the solubility of COz in oil and gas wells as functions of temperature, pressure, water cut, and hydrocarbons
present. The CaC0 3 saturation index does not require a measured pH and can accommodate the presence of weak acids, such as HzS,
and weak organic acids in the system. The sulfate scale prediction methods (for gypsum, hemihydrate, and anhydrite) are easy to use,
reliable, and designed for field use by an operator who may be untrained in chemistry. The prediction methods can be applied to any
production well where calcium carbonate, calcium sulfate, strontium sulfate, or barium sulfate scale occurs.

Introduction and Need for Improvements

As the petroleum industry produces more water to recover hydrocar-
bons more efficiently from existing fields, scale formation and cor-
rosion will become increasingly difficult problems. Calcium
carbonate and sulfate scale problems are incipient to some fields
but also occur where incompatible waters are introduced to the pro-
duction scheme during waterfloods or workovers. A general dis-
cussion of saturation indices and sulfate and carbonate predictive
equations are given later.
The sulfate scales of Ca, Sr, and Ba are well described. 1-6 How-
ever, the chemistry of the individual scale formers is described brief-
ly, along with supporting field application to lend credibility to the
predictive equations developed here. Predictive equations were de-
veloped for celestite (SrS04), gypsum (CaS04 . 2H zO), hemihy-
drate (CaS04 '1/2H zO), anhydrate (CaS04), and barite (BaS04)'
BaS04 is a growing problem in the industry owing to the regula-
tion of naturally occurring radioactive materials in the scale.
Calcium carbonate scale is generally predicted with saturation
indexes 3,? that compare the amount of the scaling constituents in
solution to the solubility. The original Langelier 8 saturation index
was proposed for corrosion control in municipal water distribution
systems. Numerous corrections for temperature, pressure, and ionic
strength have been proposed for the Langelier index, and most of
these corrections have been in the form of either data tables or plots
and figures. In addition to the standard difficulties with sample col-
lection and analyses, all the above indices require measurement of
the brine pH. In municipal water plants, pH measurement is not
a problem; but in gas and oil wells, realistic pH measurement is
rarely feasible. In the original version of the CaC0 3 saturation in-
dex published by the authors, the pH could be calculated; however,
the effects of the changes in the fugacity of COz and the partition-
ing of COz were ignored as were the effects of weak acids on the
alkalinity. All these effects have been included in the updated
version.
Saturation Index Method
The saturation ratio, Fs, is usually defined as the ratio of the ion
activity product to the solubility product:
Fs=[MeHAn]IKsp ' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)
where Me=Mg2+ , Ca2+ , Sr2+ , or Ba2+ , An=CO~- or SOi- ,
and Ksp = solubility product.
Activity is defined as the product of the activity coefficient and
the concentration. The activity coefficient is a function of temper-
ature, T, pressure, p, and ionic strength, Si' It has been useful to
include the activity coefficients in the solubility constant term so
that the measured or free (discussed later) concentrations of the metal
and anion are used in the equations. The solubility product term
is then a function of T, p, and Si' 9 The resulting conditional solu-
Copyright 1994 Society of Petroleum Engineers
bility product term, K c ' is then used in the predictive equations.
The general saturation index, Is (Eq. 29) can then be expressed
as the log of the Fs:
[MeHAn]
Is=log(Fs)=log " ...................... (2a)
Kc(T,p,Si)
or Is=log[MeHAn]+pKc(T,p,Si) ..................... (2b)
where the brackets represent concentration in molar units and
pKc = -log Kc'
When Is=O, the solution is at equilibrium with the solid scale;
an Is >0.0 indicates a supersaturated or scaling condition; an
Is < 0.0 is a subsaturated or nonscaling condition of the solution
with respect to the scale in question. Development of saturation
indices for the various salts depends on finding Kc values that are
a function of ionic strengths, temperatures, and pressures common
in the petroleum industry. The derivation of the sulfate and calci-
um carbonate Is equations is analogous to that used by the authors
to develop the original Is for CaC0 3 . 9
The conditional constants needed to solve the Is equations for
the salts of interest were derived from literature data as a function
oftemperature, pressure, and ionic strength [total dissolved solids
(TDS)]. The advantage of using experimental solubility data is that
the activities of the respective metal ions and the anion of interest
need not be determined directly but are included implicitly in the
conditional constants. Solubility data for the scales were obtained
from the literature for gypsum,IO-14 hemihydrate,IZ,13 anhy-
drite,IZ-15 celestite,16-19 and barite. 20,21 Pressure data for the
CaS04 systems can be found in or calculated from data in the liter-
ature. ll ,13-15,22 Pressure data for the BaS04 system also can be
found in or calculated from literature data. 20 ,23 The approach and
results for calcium carbonate are similar to those reported previ-
ously,9 so the specifics are not repeated here.
Once data sets were located for the solubilities of the salts of in-
terest, a nonlinear least-squares fit 24 of the data sets was performed
on each to find a conditional constant with the NONLlN module
of SYSTAT. 25 The derived conditional constants and associated
errors can be obtained from the authors.
The derived equations are of the functional form
pKc=a+bT+cTZ +dp+eS?.5 +jSigS?·5, .............. (3)
where pKc = the negative log of the conditional solubility product.
Most published equilibrium constants are in molality units; how-
ever, we have converted to molarity units for convenience. The
functional form for temperature dependence is similar to that used
by Blount and Dickson. 15. The form of the ionic strength depend-
ence is similar to that used by Millero. 26 The cross-product term
(S?·5 T) was introduced to allow the conditional solubility constants
to vary as functions of ionic strength in conjunction with tempera-

SPE Production & Facilities, February 1994 47

 TABLE 1-RECOMMENDED SATURATION INDEX EQUATIONS FOR COMMON SULFATE SCALE MINERALS

Calculate: log Kst = + 1.86 + 4.5 x 10 -3 T -1.2 x 10 -6 T2 + 10.7 x 10 -Sp -2.38S;' + 0.58S j -1.3 x 10 -3S;' T

2 - {1 + Kst(EC M -C .)} + ([1 + Kst(EC M -C so .)]2 +4K St C so • }o.s

Calculate free sulfate: [SO 4-) = - - - - - - - - - - ' -so
---------.:-'--'------'----
2K st

Calculate the free metals: [Mg 2+)=C Mg /(1 +Kst[SO~-));

[Ca 2+) = C ca /(1 + KsdSO~-))
[Sr 2 +) =C Sr /(1 + Kst[SO~-))
[Ba 2+)=C /(1 +KstlSO~-)) Ba
Calculate the Saturation Indices:
For CaS04 = log10 ([Ca 2+ )[SO~-)} +3.47 + 1.8 x 10 -3T + 2.5x 10 -6T2 -5.9 x 10 -sp -1.13S;' +0.37S j -2.0 x 10 -3S;' T
For CaS04 = log 10 {[Ca 2+ )[SO~-)} + 4.04 -1.9 x 10 -3T + 11.9 x10 -6 T2 - 6.9 x 10 -sp -1.66S;' + 0.49S j - 0.66 x 10 -3SY' T
For CaS0 4 = log 10 ([Ca 2+ )[SO~-)} + 2.52 + 9.98 x 10 -3 T - 0.97 x 10 -6 T2 - 3.07 x 10 -sp -1.09SY' + 0.50S j - 3.3 x 10 -3SY' T
For SrS04 = log 10 ([Sr 2+ )[SO~-)} + 6.11 + 2.0 x 10 -3 T + 6.4 x 10 -6 T2 -4.6 x 10 -sp -1.89SY' + 0.67S j -1.9 x 10 -3SY' T
For BaS04 = log 10 ([Ba 2+ )[SO~-)} + 10.03 - 4.8 x 10 -3 T + 11.4 x 10 -6 T2 - 4.8 x 10 -sp - 2.62SY' + 0.89S j - 2.0 x 10 -3SY' T
T = Temperature (OF); p = total absolute pressure (psia); S; = ionic strength (M),,'mg/L TDS + 53,470'" mg/L CI - + 32.460'; C so. = total sulfate concentration = mg/L
SO~ - + 96.060; C Mg = total magnesium concentration (M) = mg/L Mg + 24,305; C Ca = total calcium concentration (M) = mg/L Ca + 40,080; C s, = total strontium concentration
(M)=mg/L Sr+87,620; CBa =total barium concentration (M)=mg/L Ba+137,330 and ECM =CCa +CMg +Cs, +CBa .

• Average conversion factor for 20 oilfield brines.

mass-balance equations for the total dissolved calcium, magnesi-

TABLE 2-TYPICAL WATER COMPOSITION FROM
THE NINAN FIELD IN THE NORTHERN SEA um, strontium, barium, and sulfate are
AND SEAWATER COMPOSITION C S04 = [CaSO~] + [MgSO~] + [SrSO~] + [BaSO~] + [SO~-],
Formation ................................... (6a)
Water" Seawater
CCa=[Ca2+]+[CaSO~], .......................... (6b)
Component mg/L mM mg/L mM
--- CMg=[Mg2+]+[MgSO~], ......................... (6c)
Na 8,440 367 10,680 464
K 159 4.1 396 10.1 CSr = [Sr2+] + [SrSO~], ............................ (6d)
Mg 25 1.03 1,279 52.6
Ca 150 3.75 409 10.2 and CBa=[Ba2+]+[BaSO~], ......................... (6e)
Sr 44 0.5 7.9 0.09
Ba 20 0.15 0.022 0.00016 where Cx = total molar concentration of Species x in solution (typi-
CI 12,555 354 19,193 541 cally, the measured amount in solution in milligrams per liter).
S04 14 0.15 2,689 28.0
HC0 3 1,418 23.2 141 2.31 Saturation Index Equations. The numerical values of the stabil-
Calculated Sj 396 692 ity constants for the four sulfate/metal ion complexes are nearly
Original molal values converted to molarity. equal at room temperature. 27 Assuming them to be equal greatly
"Personal communication with P.J. Schuler, Chevron Petroleum Technology Co. simplifies the calculation procedures and causes an error of ±0.1
log units or less in any practical calculation of Is values. With these
assumptions, Eqs. 5 and 6 can be solved as a quadratic equation
ture and was found to be significant for all salts except calcium
for the free metal and sulfate concentrations in solution. Numeri-
carbonate. The cross-product terms between temperature and pres-
cal values for K st and pKc from the literature can then be obtained
sure and the second-order ionic strength/temperature (S;T2) were as functions of T, p, and Si' Table 1 shows the final saturation in-
found to be insignificant. dex equations. The least-squares-curve-fitted equations for pKst
and pKc were then used to calculate the Is values for published
Sulfate Saturation Indices equlibrium solubility data. Because these experiments are assumed
Calculation of Is for the five sulfate salts under consideration re- to be at equilibrium, the calculated Is values should be zero. The
quires the concentrations of the free metal and free sulfate ions be- average calculated Is for 65 sulfates was 0.011 Is units. Details
cause of the complexing or ion pairing of the metals with sulfate of the derivation and data analysis are available from the authors.
in solution. The extent of complexation depends on the solution
temperature, pressure, ionic strength, and total concentrations of Calcium Sulfate Phases. CaS04 poses a unique problem for the
the metal and sulfate ions. salts under consideration because it occurs with various regularity
Complex formation between calcium and sulfate is used as an as one of three different phases. Gypsum, the most common scale
example: former,3 occurs at relatively low temperatures. At higher temper-
atures [above about 100°C (212°F)], the stable phase predicted is
Ca2+ +SO~- .... CaSO~ ............................. (4)
anhydrite (CaS04)' However, hemihydrate has been known to
The mass-action stability constant, Ksl' is given by form at about 212 to 250°F, especially in nonturbulent systems and
in high-ionic-strength brines. 2,6,22 Whether anhydrite, hemihy-
[CaSO~] drate, or gypsum is the actual phase that forms in any particular
K st = ............................... (5)
[Ca 2 + ][SO~-] production system in this transition temperature range is beyond
the scope of these and any other predictive equations. Field or lab-
CaSO~ refers to the neutral ion pair, or complex in solution, not oratory simulations should be conducted to gain insight into the ki-
to the solid. Similar chemical equilibria and stability constants can netically preferred phase, although some guidelines can be offered.
be written for magnesium, strontium, and barium sulfates. The Under 176 of, the most likely phase will be gypsum in brine solu-

48 SPE Production & Facilities, February 1994

 TABLE 3-RECOMMENDED EQUATIONS TO CALCULATE CALCITE SATURATION INDEX AND pH FOR OIL AND GAS WELLS
C Ca = Ca 2 + = total calcium

Gas phase present

(Ca2+ )(HCO; )2l -3 -6 2 -s '/2

Is=log [ py~02f~02 J+5.85+15.19X10 T-1.64x10 T -5.27x10 p-3.334(S,) +1.431(S,) ........... . (T3-1)

pH = IOg[ p~~~~~L J + 8.60+5.31 x 10 -3T -2.253 x 10 -6T2 -2.237x 10 -sp-0.990(S,)'/2 + 0.658(S,) .............. (T3-2)

f~02 =exp p(2.84 x 10- 4

0.255
- ---
J co co /[ pf~02
(5.0 BWPO + 10.0 BOPO) x 10 -s
and Yg 2 =Yt 2 1.0+ .:........:'--......:....--------'-----
J
[ T+ 460 MMscf(T + 460)

Gas phase absent

Is = log [
(Ca2+ )(HCO -)2
C02 3
J
+ 3.63 + 8.68 x 10 -3T + 8.55 x 10 -6 T2 - 6.56 x 10 -sp - 3.42(S,) v, + 1.373(S,) . . . . . . . . . . . . . . (T3-3)
C aq

PH=I09[ (H~~2;) l +6.39-1.198x 10 -3T +7.94x 10 -6T2 -3.53x 10 -sp-1.067(S,)'/2 +0.599(S,) .................. ("T3-4)
C aq J
Measured pH with gas phase present or absent

Is = log[(Ca 2 + )(HCO; I + pH - 2.76 +9.88 x 10 -3 T + 0.61 x 10 -6T2 - 3.03 x 10 -sp - 2.348(S,) '/2 + 0.770(S,) ............ (T3-5)

Ca 2+ stotal calcium (M = mglL +40,000); (HCO; sbicarbonate alkalinity (M= mg1L+61 ,000); pstotal absolute pressure (psia); Tstemperature (oF); S, sionic strength
(M)=mgIL TDS +53,470' HmglL CI - + 32,460'); f~o, sfugacity coefficient of C02 gas as a minor species in CH. + C02 gas; y~o, . mole or volume fraction of C02 in
the gas phase at the specified T and p; yyO, s mole or volume fraction of CO 2 considering gas plus oil plus brine-this is essentially the fraction CO 2 in the gas at the
surface; MMscfstotal number of MMscfID gas produced at standard temperature and pressure; BWPDsbarrels of brine produced per day; BOPDsbarrels of oil produced
per day; C~c?2 =7,289.3xnf0 2 1(V aq +3.04Vo); nf o , =MMscf of C02 per day at STP=(MMscf)(Yfo,).

'Average conversion factors fo 20 oilfield brines.

tions. Between 176 and 250 o P, any of the three phases may form, pKst = 1.86+4.5 x 10 -3(220 P) -1.2 x 1O-6(220 P)2
0 0

with gypsum being more likely at the low end and anhydrite at the
high end. However, in this temperature range, hemihydrate is com-
monly found in a nonturbulent system with high ionic strength,
+ 10.7 x 10 -5 (4,300 psi) -2.38(0.42M) v, +0.58(0.42M)
-1.3 x 10- 3(0.42M) v, (220 P) ....................... (7)
0

which means that a scaling problem may not be as severe as one 0

might think if the prediction equations for the less soluble anhy-
drite were used. Above 250 o P, the produced scale will almost cer-
tainly be anhydrite.
Example of Use of the BaS04 's in the North Sea
Table 2 shows an example of a typical brine composition from the
Ninian field in the North Sea and the seawater composition. The
logarithm of the conditional equilibrium constant for the MgSO~
and CaSO~ solution complexes is calculated with the first equa-
tion in Table I as follows:
Using the downhole temperature of 220 P and a pressure of 4,300
psi, we find log K st = I. 79. The free [SO~-] and [Ba2+] concen-
trations are found to be 11.0 and 20 mg/L, respectively, or 0.00015
and O.ooOIIM.
The pKc can then be calculated from the equations in Table 1
similarly to the log K st calculation (Eq. 7) and has a value of7.71.
The necessary values have now been determined for substitution
into Eq. 2b to determine the Is for the Ninian field formation
waters at downhole conditions by use of the water composition in
Table 2:
I s =log[(0.00015M)(0.0001lM)] + 7.71. ............... (8)

TABLE 4-EQUATIONS TO CALCULATE 4pH AND .lIs FOR OIL AND GAS WELLS

Gas phase present

Ll/S = log [ Pdy~02)1(f~02)1 J

0
P2(Y~ 2)2(f g 2)2
co +15.19x10
-3
LlT-1.64x10
-6 ( 2
Ll T )-5.27x1
O-S Llp .............................. (T4-1 )

LlpH = log[ (PY~:2 f~:2 )1 l + 5.31 x 10 -3 LlT _ 2.253 x 10 -6 Ll(T2) _ 2.237 x 10 -s Llp ............................... : (T4-2)
(PY g 2 fg 2 h J
0.255
f~02 = exp p(2.84 x 10 -4 - - - -
J co [ pf~O 2 (5.0 BWPO + 10.0 BOPO) x 10- S
and Y g 2 = 1.0 + - - ' ' - - - - - - - - - - - - - -
J
[ T +460 MMscf(T +460)

Gas phase absent

Llls =8.68x 10- 3LlT -1.64x 10- 6Ll(T 2)-6.56x 10- s Llp ..................................................... (T4-3)
LlpH = -1.198 x 10 -3 LlT -7.94 x 10 -6 Ll(T 2) - 3.53 x 10 -s Llp .................................................. (T4-4)

pstotal absolute pressure (psia); Tstemperature (oF); fgco, sfugacity coefficient of CO 2 gas as a minor species in CH. +C02 gas; y~O, smole or volume fraction of
C02 in the gas phase at the specified T and p; MMscf~total number of MMscflD gas produced at standard temperature and pressure; BWPDsbarrels of brine produced
per day; BOPDsbarrels of oil produced per day.

SPE Production & Facilities, February 1994 49

 Is= -0.07 ........................................ (9)
Note that the formation is at equilibrium with barite.
A similar calculation for the seawater composition in Table 2
determines Is = -1.45 for barite under the same conditions. How-
ever, a 50/50 mixture of the two waters would generate Is=1.12
at downhole conditions, and serious scaling with barium sulfate is
predicted. This is indeed the case in the wells, and scale treatment
programs have been initiated to combat the problem. Z8
Calcium Carbonate Saturation Indices
Improvements to the original saturation index 9 for CaC0 3 include
algorithms to calculate the partitioning or changing mole fraction
of CO 2 with varying temperature and pressure conditions, the in-
clusion of both oil and CH 4 phases in the system, and an algorithm
to calculate the fugacities of COz and CH 4 . Tables 3 and 4 give
the equations needed to calculate Is for a calcium carbonate sys-
tem. The Is similar to Eq. 2 for CaC0 3 is 9
(Ca2+)(HCo3 )Zl ( Kz )
Is = log [ +log (T,p,S;)
pyfOzffO z KspKJKr;;J;z
................................. (10)
where p=total pressure and (T,p,Sj) are shown to emphasize the
temperature, pressure, and ionic strength dependence of the four
conditional equilibrium constants. Table 3 summarizes these vari-
ables.
Similarly, the value of pH = -log[H +] can be represented by
(HC03) l
pH = log [ -log(K[Kr;;J;z )(T,p,Sj) . ........ (11)
pyfozffOz
Three issues need to be addressed to use these equations in oil-
and gasfield situations: (1) the T, p, and Sj dependence of the
equlibrium constants; (2) the thermodynamic nonideality of the gas-
phase COz at high pressure; and (3) the variation of the mole frac-
tion of CO 2 in the gas phase with pressure and with gas/oil/water
volumetric ratios. Remember that activity coefficients are included
in the conditional constants.
Temperature, Pressure, and Ionic Strength Effects. The explicit
temperature, pressure, and ionic strength functional dependencies
of the equilibrium constants (K 10 K2 , Ks?, and Kr;;J;Z) were ob-
tained by nonlinear least-squares curve fittmg of the respective data
and revised from the previous work 9 :
pK] =6.39-1.l98x 1O- 3 T+7.94x 1O- 6 T2 -3.53 x 1O- 5 p
-1.067(Sj) y, +0.599(Sj), .......................... (12)
pK2 = 1O.70-5.19x 1O- 3 T+ 11.29x 1O- 6 T2 -3.57x 1O- 5 p
-1.332(S;) Ih +0.496(Sj), .......................... (13)
pKsp =7.94-4.69x 10- 3 T+ 11.90x 10- 6 TZ -6.60x 1O- 5 p
-3.68(Sj) y, + 1. 270(Sj), ........................... (14)
and pKfoz =2.212+6.51 x 1O- 3 T-IO.19x 1O- 6 T2
-1.290 x 1O- 5 p+0.077(Si) Ih +0.059(Sj)' ............ (15)
Nonideality or Fugacity of CO 2 Gas. The thermodynamic
nonidealities of aqueous solution components in the above discus-
sion were included by curve fitting the Sj and p dependence of the
equilibrium constants (Eqs. 12 through 15), but the corresponding
gas-phase nonideality corrections were not made. The gas-phase
nonideality can be considered in the saturation index derivation by
including a dimensionless fugacity coefficient, ffoz, in the
denominator of the logarithmic term of Eqs. 10 and 11:
Cr;;J;z =Kr;;J;zPcozffoz, .......................... (16)
where Cr;;J;z = aqueous-phase concentration of COz (M) and Peoz
ff Oz =fugacity of COz at a given temperature and pressure. The
fugacity coefficient varies with pressure and gas-phase composi-
50
tion and generally is calculated from compressibility data or from
some thermodynamic equation of state (EOS), such as the van der
Waals or Peng-Robinson EOS.Z9 When the gas phase is a mixture
of gases, the theoretical problem of calculating fugacity coefficients
is more difficult than for a pure gas. Refs. 29 and 30 provide com-
plete discussions of the background thermodynamics of fugacity.
Two calculation procedures were used, Curl and Pitzer's3] "ta-
ble look-up" accentric theory and an 18-term extended Redlich-
Kwong EOS.32 With the extended Redlich-Kwong EOS, includ-
ing the effect of water vapor was possible. Reid et al. Z9 discussed
both calculation procedures. For gas-phase CO 2 and methane, a
series of fugacity coefficients, f fO z and f f H 4, were calculated
at various reduced temperatures, reduced pressures, and mole frac-
tions. Theseffoz andff H4 values were plotted vs. pressure, and
the shape of the curves suggested the use of an exponential func-
tion to represent the fugacity coefficients empirically. Least-squares
curve fit of the calculated coefficients yielded the following for
CO 2 :
ffoz=exP[p(2.84XIO-4- 0.255 )l,r=1.00 ....... (17)
T+460
and similar results were obtained for methane:
ff H 4 =exp[p(1.35 x 10- 4 - 0.107 )l,r=1.oo . ...... (18)
T+460
For a detailed discussion and derivation of the curves, contact the
authors.
Note that, as the fraction of CO 2 in the gas phase approaches
zero,ffo z does not approach unity, as might be expected by anal-
ogy with aqueous species. For example, at 5,000 psia and 212°F,
yfOz -+0, ff oz -+a constant, ff oz =0.62. The fugacity coeffi-
cients calculated compare favorably with the Chevron Peng-
Robinson code. TheffOz values varied from 0.45 to 0.97. Agree-
ment between the more elaborate Chevron code and Eq. 17 is gener-
ally within about 5 %. Completely neglecting f f Oz could cause a
systematic error as high as 0.3 in Is, but an error of 5% inffOz
would change the calculated Is by only 0.02, which is well within
the expected error of the various pK values in Eqs. 12 through 15.
The final Is and pH equations will be expressed in terms off fO z
so that, in the future, any other algorithm can be used in place of
Eq. 17. A more formal derivation and explanation of the assump-
tions is available from the authors.
The yf0 2 Variation With Pressure and Gas/Oil/Water Volu-
metric Ratios. The fraction of CO 2 in the gas phase of a well can
change as the pressure changes if there is a significant amount of
brine, oil, or both because different gases at the same partial pres-
'sure have different solubilities in water or oil. Detailed calcula-
tions are again available from the authors. The result for methane
and CO 2 in contact with water and oil is
yCOz =yfOz I[ 1.0+
g
ffOZ(5.0 BWPD+1O.0 BOPD)XIO- 5P
MMscf(T+460)
l,
................................... (19)
where yfOz =mole fraction of CO 2 measured at standard condi-
tions and BWPD, BOPD, and MMscf=production per day (see Ta-
ble 3).
The validity of Eq. 17 has been tested directly with IGT reser-
voir recombination data for the Riddle-Saldana Well No. 2.33 Gas
containing the naturally occurring percent of CO z , methane,
ethane, through heptanes at 300°F was pressurized to the bub-
b1epoint, 6,632 psia. The system was flashed in four steps to ap-
proximately atmospheric pressure (plus the vapor pressure of water).
The BOPD was negligible and the ratio of MMscf to BWPD was
1.40 x 10- 4 MMft 3 /bbl. When these values were used in Eq. 17,
the calculated fraction of COz was calculated to change from
14.2% to 1.77% vs. the measured 14.2% to 1.80%. On commer-
SPE Production & Facilities, February 1994
cial gas wells with higher gas/water ratios, the CO 2 fraction rare-
ly changes over such a wide range.
Absence of Gas Phase (p~Bubblepoint). So far, the derivation
has assumed that a gas phase was present. A gas phase might be
absent for two reasons: the system pressure may be greater than
the bubblepoint down the production hole and the gas phase might
be removed in a separator before brine disposal. (Note that the sys-
tem pressure still exceeds the bubblepoint.) To evaluate the Is with
Eq. T3-3 in Table 3, a value for cJiq°z, the molar concentration
of aqueous CO 2 , must be obtained. If the gas phase is absent be-
cause the pressure is greater than the bubblepoint, C~oz can be
set equal to the total CO 2 produced per day in the equivalent
volume of brine and oil. The relative partitioning of CO 2 between
oil and brine, C{;02 / CS:qoz , can be expressed by a ratio of the re-
spective Henry's law constants:
K{;Oz /KS:!?2 = C{;02 / Cs:!?z. .. ...................... (20)
By noting that all the CO 2 is in either the oil or the water and
assuming that K[;o2/KS:!?2 =3.04, we can show that
nF02
- - - - - .......................... (21)
Vaq +3.04BOPD
This value of CS:!?z can be used in the denominator of Eq. T3-3
when the system pressure exceeds the bubblepoint. The pH can be
calculated similarly, and the result is presented in T3-4.
Often, gas and oil are separated on the surface by a three-phase
separator, and the remaining brine is injected down a disposal well.
Eqs. T3-3 and T3-4 can be used to calculate the saturation index
and pH of the brine, at least down to the receiving formation. Once
the brine enters the new formation, it can either dissolve or precipi-
tate minerals, which will change the parameters in the Is and pH
equations. Additionally, the terms needed to calculate 0i,p2 should
be corrected for the CO 2 removed in the sales gas and oil. The
CS:!?z can be obtained by sampling the disposal brine, measuring
the residual Cs:pz directly by standard methods, and using this
measured value in Eqs. T3-3 and T3-4. If it is not feasible to measure
CS:!?z in the disposal brine, a reasonable estimate can be calculat-
ed from the partial pressure of CO 2 in the separator gas:
10g(0i!?z )=log Peo2 -2.212-6.51 x 10 -3 T+ 10.19 X 1O- 6 T2
-1.290 x 10 -5 p -0.077(S,.} v, -0.059(S,.}, ............ (22)
where the units are as defined in Table 3 and fa~02 = 1 has been
assumed. In the disposal well in the absence of a gas phase, only
temperature and pressure change. Therefore, once CJiq0 2 has been
calculated or measured, it can be used in Eqs. T3-3 and T3-4 to
calculate Is and pH down the disposal well to the formation face.
Cautions for Using Measured pH. It may be possible to measure
the pH, or [H +], directly in surface facilities by use of a high-
temperature, high-pressure pH electrode. If the pH can be meas-
ured, the Is can be calculated directly with Eq. T3-5. The pH value
should be measured in the flowing brine stream, not in a collected
sample. As the collected sample degases, the dissolved CO 2
evolves and various brine components react with atmospheric oxy-
gen. Degasing, reacting with oxygen, etc., change the solution pH.
Until a reliable in-line pH electrode is commercially available, we
would suggest caution in using equations like Eq. T3-5.
Effect of Carboxylic Acids on the Calcite Is Calculations.
Generally, alkalinity titrated to pH 4.5 to 4.7 can be assumed to
be equal to the HCO; and used in Is calculations. However, when
weak organic acids are important with respect to the total alkalin-
ity, they should be taken into consideration. Most calcite and car-
bonate calculation algorithms use the dissolved bicarbonate-ion
concentration (HCO;) and assume that the bicarbonate concentra-
tion equals the total alkalinity. Furthermore, it is generally assumed
that the bicarbonate concentration and the total alkalinity are in-
dependent of Peoz' In produced waters, a substantial concentra-
tion of carboxylic acids often is present, normally represented as
SPE Production & Facilities, February 1994
equivalent concentration of acetic acid (CAe)' The presence of car-
boxylic acids often causes the brine acid titration endpoint to be
smeared and ill-defined. Hence, the concentration of carboxylic
acids in brine is generally measured by gas chromatography. When
the concentration of carboxylic acids is substantial relative to the
bicarbonate concentration, brine alkalinity can be assumed equal
to the sum of the concentration of free acetate (Ac -) plus bicar-
bonate (HCO;):
Alk=(Ac-)+(HCO;), ........................... (23)
where the units are moles per liter. This is an excellent assumption
from about pH 3.5 to 9. As long as neither a strong acid nor a strong
base is added to the brine, alkalinity will be constant, but the
(Ac - )/(HCO;) ratio will depend on pH, which in turn depends
on Peoz and hence the total pressure. When K 1 and KH for car-
bonic acid and K Ae for acetic acid are substituted into Eq. 23, the
following quadratic equation in terms of readily measurable quan-
tities can be obtained to calculate the (HCO;) needed in the cal-
cite saturation index equations:
(HCO;)2 + {K'Peo 2 +CAe-Alk}(HCO;)-K'Peo2Alk=0,
................................... (24)
where (HCO;), CAe' and Alk are in mollL(M); Peo2 is in psia;
and K' = K 1KH / K Ae' Al ways use the positive root of the quadrat-
ic equation. The general solution of Eq. 24 using the quadratic equa-
tion is
a=l.O,
b=K'Peoz +TAe-Alk,
c = - K'Peoz Alk,
-b+(b 2 -4c) Yz
and (HCO;)= - - - - - ..................... (25)
2
The T, P, and Si dependence of K', or pK' = -loglO(K'), can
be calculated:
pK' =3.79+6.80x 1O- 3 T-13.2 x 1O- 6 T2 -3.66x 1O- 5p
-0.097Si Yz +0.221Si .............................. (26)
For completeness, the equation for KAe is included:
pKAc =4.81-1.49x 10- 3 T+ 1.095 x 10- 5 T2 -1.16x 10- 5 p
-0.893S/' +0.437Si , ............................. (27)
where the units are as defined before. Peo2 =Ptyf02ff02 as de-
fined in Table 3. The final unknown is the "true" alkalinity, Alk.
Measuring Alk is more difficult than it appears. Several methods
are possible; the following three-step procedure is suggested for
use with oilfield brines. For illustration purposes, assume that
CAe =9.0 mM from gas chromatographic analysis.
1. Acidify the brine to about pH 2 with an excess of HCl and
remove all the dissolved carbonic acid by either boiling the solu-
tion or sparging it with nitrogen. In the present example, assume
that 20.0 mM of HCl was added, although different amounts could
have been used.
2. Titrate the solution to a phenolphthalein-red endpoint with
NaOH. In this case, assume that 19.0 mM of NaOH was required.
3. Calculate the alkalinity with
Alk=HCI Added to about 2 pH - NaOH To phenolphthalien endpOint
+CAe ·
In this example, that equation becomes
10.0 mM=20.0 mM-19.0 mM+9.0 mM.
To illustrate the effect of acetic acid on the calculated IS for cal-
cite with the present example, further assume that a well produces
2,000 BWPD with si=0.8 M, 100 BOPD and 3 MMscflD total
gas with yfOz =0.05 mole fraction. Calculate the (HCO;) in the
separator at 200°F and 160 psia and downhole at 240°F and 5,000
psia. In the separator, pK'=4.33 (K' = 1O-4.33),ffo2 =0.98, and
51
 TABLE 5-SURFACE AND DOWNHOLE WELL DATA TABLE 6-CHEMICAL AND TEMPERATURE/PRESSURE
FOR THE PRETS WELL IN THE HITCHCOCK FIELD, DATA FOR WELLS FAA-7 AND THE ZEB-8 OPERATED
NEAR GALVESTON, TX BY MAXUS SOUTHEAST SUMATRA, INC., INDONESIA

Parameter Surface Bottomhole Well FAA-7 Well ZEB-8

T, of 196 214
p, psig 150 3,561 Parameter Surface Bottomhole Surface Bottomhole
Ca,M 0.0112 0.0112 T, OF 210 220 180 190
Total alkalinity, M 0.0198 0.0198 p, psig 340 1,558 360 1,114
Total acetic acid, M 0.0125 0.0125
0.00734 0.00762 Ca, mg/L 200 200 152 152
HC0 3 , M
0.68 0.68 HC0 3 , mg/L 766 766 897 897
5" M
CO 2 , % 0.65 0.30' S"M 0.22 0.22 0.24 0.24
MMscfID STP 0.76 0.76 CO 2 , % 4.38 2.40 1.94 1.80
Brine, BWPO 5,423 5,423 MMscf/O, STP 0.217 0.217 0.440 0.440
Oil, BOPO 27.6 27.6 Brine, BWPO 380 380 294 294
'Calculated with the mole fraction equation in Table 3.
Oil, BOPO 750 750 132 132

yfOz =0.0496. Therefore, Pcoz =160 psiaxO.98xO.0496=7.77 ration can be estimated. Henry's law constant, K~JS, and the first
psia. With CAe =0.009 M and Alk=O.OlO M, (HC0 3 )=0.00176 ionization constant, KF2S, are defined as for CO 2 , For H 2 S be-
M from Eq. 25. For downhole conditions, ff oz =0.67 and low pH 9, the bisulfide, (HS-), species contributes to alkalinity.
yfOz =0.043 at 5,000 psia and 240°F; therefore, Pcoz = 144 psia l\t a given pH, the bisulfide concentration is given by the counter-
and (HC0 3 )=0.005 M. part to the bicarbonate equation:
The solution concentration (HC0 3 ) increases from 0.00176 M
in the separator to 0.005 M at the bottom of the well. Because the _ _
(HS )-K J
H2S H2 PHzS
Kaq S .......................... (28)
Is for calcite is related to the square of the (H C0 3 ) concentration (H+)
(Table 3), this increase in actual (HC0 3 ) with depth would cause
the Is to be 0.91 Is units higher at the formation face than if the Coincidentally, the product Kr 2S KU 2S is approximately equal
bicarbonate at the separator were used. Put another way, the actu- to the carbona~e pro~u~t, K JK~?2. Therefore,. at a given pH, ~he
al change in Is from the bottom of the well to the surface would (HS - )/(HC0 3 ) ratIo IS approxImately the ratIo of the respectIve
be 0.91 Is units lower than calculated without correcting for the partial pressures:
presence of acetic acid. This large difference in the calculated Is
could easily change the interpretation of what scale formation is ............................... (29)
expected. (HC0 3 ) PC02
Effects of H 2 S on Is Calculations. Some wells contain a signifi- Eq. 29 or one like it should be used to subtract the HS - effect
cant amount of H 2 S in the produced gas. The effect on calcite satu- from the total alkalinity. Crolet and Bonis' 34 thorough discussion
of the effect ofH 2 S on pH, alkalinity, and related solution chemis-
try should be studied if PH2S is similar to or greater than Pcoz'
0.007 1.00

."
M
. 1 a.
0.95
Concept of Change in the Saturation Index. In practical appli-
cations of the Is and pH equations, it is often sufficient to know
0
Q 0.006 only the change in the Is or pH. For example, when a field is
c 0.90
0 known to be completed in a calcite-cemented reservoir, the forma-
i!
tion Is can be assumed to be 0.0 in the reservoir under shut-in con-
l3
'0
0.005 0.85 .
~
u
co ditions of pressure and temperature. The quantity, Ills, can be
ti
c
0
0.80
...
:>
defined as
...I! 0.004
0.75
Ms=IS2 -lSI' ................................... (30)
~ Mole Fraction
where the subscripts refer to brine Conditions 1 and 2; generally,
::E
0.003 0.70 it is assumed that the reference condition is downhole at the pro-
0 2000 4000 6000 8000 10000 duction zone, although this is not necessary. If it is assumed that
Depth (Feet) a gas phase is present, as is generally the situation, then Ms is
1.0 7.20 given by subtracting the two Is equations for the different condi-
0.9 1 b. tions of interest. In many production wells, the chemical parame-
0.8
7.00 ters, (Ca 2 +) and (HC0 3 ), and Si do not change more than a few
0.7 percent from bottomhole to the surface, and the ratio of (y~02) 1/
=
."
.5 0.6
6.80
:z:a.
(y~?2 h eliminates the need to measure the fraction of CO 2 ,
c
0 0.5 6.60
ypoz. With these simplifications, the Ms equation can be writ-
~:> ten as Eq. T4-1 in Table 4.
0.4
6.40 Eq. T4-1 is a function of only the physical variables of produc-
~ 0.3
tion, T, P, BWPD, BOPD, and MMscf/D gas produced-i.e., all
0.2 the chemical parameters have been eliminated.
6.20
0.1 In addition to the above measurement advantages of using M s
6.00 equations, systematic errors associated with the thermodynamic
2000 4000 6000 8000 10000 equilibrium constants vs. temperature and other conditions will tend
Depth (Feet) to be reduced. Table 4 gives corresponding Ills equations for the
absence of a gas phase and IlpH. Some large-volume gas-producing
wells also produce a few barrels of brine per day. A significant
Fig. 1_(a)f;02 and y;02 vs. depth for the Prets well using
fraction of this brine volume often comes from condensation owing
the data in Table 5; (b) plot of saturation index and pH vs.
depth for the Prets well. to gas expansion and cooling. 35 When this is true, Eq. T4-1 should
be used with the appropriate dilution ratios.

52 SPE Production & Facilities, February 1994

Calibration of the Calcite Is. Scale does not form in well sys-
tems even though predicted at small positive Is values. Feitler 36 •37
discussed the difficulties associated with assuming immediate scale
formation as the saturation index becomes positive and developed
the concept of a critical pH for scale control. This critical pH was
determined to be about 1.7 to 2.0 pH units above where scale is
strictly predicted by a saturation index. The critical pH was deter-
mined by titrating NaOH into a saturated calcium carbonate solu-
tion and noting the pH at which precipitation actually took place.
This range, however, is highly dependent on a number of varia-
bles, such as temperature, impurities, flow rate, seed material avail-
able, and the presence of threshold inhibitors. 3 ,38-41
In our experience, the Ms value or Is value assuming Is=O at
bottomhole conditions for scale formation to occur in systems
producing natural brines is about 0.40, assuming no turbulence in
the system. Turbulence can cause scale to form at small positive
Is values.
Examples of Use of Calcite Is Equations
The Hitchcock Gas Field, South Texas. Several wells in the Hitch-
cock field produce between 5,000 and 8,000 BID brine. Scale has
been a continuous problem since the beginning of coproduction.
Note that scale has been prevented by use of 0.5 to 1.0 mg/L of
various inhibitors. 42 Reliable scale prediction has been of consider-
able assistance in this field. For example, accurate prediction of
scale-forming potential vs. depth permitted optimal scale-inhibitor
injection through treat strings, thereby saving tens of thousands of
dollars per well in wasted materials.
Table 5 lists the well data needed to predict the scale potential,
or Is. vs. depth for the Prets No.1 well in the Hitchcock field.
Although most systems may not require the inclusion of weak or-
ganic acids in the calculation to account for alkalinity corrections
as discussed above, an example was chosen to illustrate the weak
acid correction. The well alkalinity was measured by many differ-
ent techniques. The value shown in Table 5 was measured by titrat-
ing and determining the inflection point at about pH 3.5. Alkalinity
determined by titrating to pH 4.5 or 4.7 would be significantly
smaller in numerical value, and care must be taken to include total
alkalinity when correcting for weak organic acids. If the alkalinity
value used in the calculation has an uncertain history, it is proba-
bly better not to make a weak acid correction, at least initially.
Fig. 1a plots the variation of the fugacity and mole fraction of
CO 2 with depth as determined from Eq. T3-1, and Fig. 1b plots
the calculated saturation index and pH vs. depth. The CO 2 gas-
phase fugacity coefficient drops from 0.98 down to 0.72, a factor
of 1.36. The CO 2 fraction drops from 0.65% to 0.30%, a factor
of 2 .17. The two effects multiply in the denominator of the logarithm
term of Eq. T3-1 to lower the calculated Is by 0.47 units at down-
hole conditions. Consequently, the calculated Is at the perforations
is -0.002, which is extremely close to the expected value ofO.OO.
Note the change in bicarbonate concentration in Table 5 resulting
only from the organic acid effect. When the well was not treated
with a scale inhibitor for 2 weeks, scale formed from 600 ft to the
surface. At 600 ft, the Is=0.40 but drops to <0.2 at 2,000 ft.
Therefore, scale inhibitors have been injected at 1 mg/L through
a 316 L SS treat string at 2,000 ft and scale has not been observed.
Oil Wells in Offshore Indonesia. Scale analyses were performed
for Pertamina and Maxus Southeast Sumatra Inc. to determine the
cause of scale buildup in and around the submersible pumps. A
typical well for which CO 2 analyses were available was Well Far-
ida A-7 (FAA -7). Another producing well , Well Zelda B-8 (ZEB-
8), was included to demonstrate the calculated CO 2 mole fraction.
Table 6 shows chemical analyses for these wells and relevant pres-
sure/temperature data.
When the CO 2 in the gas phase is not known for a particular
well, which is often the case, the mole fraction of CO 2 can be cal-
culated as follows. The measured CO 2 in the produced fluids from
Well FAA-7 was 4.38 mol % of the gas phase, or a mol fraction
of 0.0438. By solving Eq. T3-1 for the mole percent of CO 2 at
bottornhole conditions, assuming an Is=O.O or a brine at equilib-
SPE Production & Facilities, February 1994
rium with calcium carbonate, we obtained 4.84% CO 2 , which is
in good agreement with the measured value. A downhole Is of
0.041 was calculated from Eq. T3-1 with the measured value of
mole percent of CO 2 , The fugacity and mole fraction of the CO 2
at bottornhole conditions were 0.868 and 0.024, respectively.
Is=0.39 was obtained at wellhead conditions. At the near-pump
conditions of approximately 220°F and 500 psi, Is =0.40 was cal-
culated.
Scale formed intermittently in the well near the submersible pump.
The temperature near the pump and pump motor can be signifi-
cantly (up to 100°F) higher than the formation temperature. A 20°F
increase in temperature at 500 psig would raise the Is to 0.68 and
would indicate scaling conditions. The production parameters of
the field in terms of pump type, downhole gas separator, wellhead
pressure, etc., all determine temperature/pressure differences that
contribute to the well's potential to produce scale. It is not surpris-
ing from the scale analysis that some wells produce scale continu-
ously, some intermittently, and some not at all, based on the Is
regions calculated for the wells and the differences in Is values cal-
culated from small differences in production temperatures and
pressures.
The calculated CO 2 in Well ZEB-8 is 1.94%, assuming a bot-
tornhole Is=O.O. The fugacity coefficient and mole fraction of the
CO 2 at bottornhole conditions were 0.886 and 0.018, respectively.
The Is at the wellhead was calculated to be 0.32. The calculated
Is near the submersible pump at 190°F and 500 psig is 0.39. How-
ever, at 210°F and 500 psig, Is=0.62, indicating scale formation.
It is difficult to know the actual temperatures and pressures near
the pumps and hence the true scaling potential of each individual
well. Nevertheless, the estimated scaling potential is found to be
in a region where the sale can be controlled by chemical inhibition.
Nomenclature
An = anion
C = total amount of ionic species in solution, M
f fO z = fugacity of CO 2
Fs = saturation ratio, dimensionless
Is = saturation index, dimensionless
K~,?z = Henry's law constant (M -psi - 1)
Kc = conditional solubility product, M2
Ksp = solubility product, M2
K st = complex stability constant, M-I
KI = first ionization constant of carbonic acid, M
K2 = second ionization constant of carbonic acid, M
Me = metal, { } denotes molar activity, [ 1 denotes molar
concentration, M
p = pressure, m/Lt 2 , psi
Si = ionic strength, M
T = temperature, T, OF
yfOz = mole fraction of CO 2 in the gas phase
EM = CCa + C Mg + C Sr +CBa , M
t:..ls = change in the Is for two temperature/pressure
conditions
Acknowledgments
This work was supported by the Gas Research Inst. (GRI) under
Contract No. 5088-212-1717, but in no way does this constitute
an endorsement by GRI of any products or views contained here.
This work also was supported by a consortium of companies in-
cluding Exxon Chemical Co., Chevron Petroleum Technology Co.,
Arco Oil and Gas Co., Texaco Inc., Conoco Inc., Welchem, Cham-
pion Technologies Inc., FMC Corp.-Product Additives Div., and
Zapata Inc.
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53

Authors
John E. Oddo
earned a BS degree
from the U. of
Akron, an MS
degree from the U.
of Toledo, and a
PhD degree from
Rice U. He con-
tinued working at
Rice U. on prob-
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Oddo Tomson corrosion before
. taking a position
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41. Kossel, W.: "Theory of Crystal Growth," Ann. Phys. (1934) 21.
42. Street, E.H., Oddo, J.E. , and Tomson, M.B .: "Scale Control Aids
Gas Recovery," fPT(Oct. 1989) 1080.
SI MetriC Conversion Factors
bbl x 1.589 873 E-Ol
ft x 3.048* E-Ol
ft3 x 2.831 685 E-02
OF (OF-32)/1.8
psi x 6.894 757 E+OO
·Conversion factor is exact. SPEPF
Original SPE manuscript received for review April 7, 1991. Revised manuscript received
Aug. 13, 1993. Paper accepted for publication Nov. 7, 1993. Paper (SPE 21710) first present·
ed at the 1991 SPE Production Operations Symposium held in Oklahoma C~y, April 7-9.
SPE Production & Facilities, February 1994