*

Simplified models used to predict scale

tendencies
1) Write the reaction
𝑁𝑎𝐶𝑙 𝑠, ℎ𝑎𝑙𝑖𝑡𝑒 = 𝑁𝑎+ 𝑎𝑞 + 𝐶𝑙 − (𝑎𝑞)

2) Convert to an Equilibrium equation (shorthand form shown)

𝑎𝑁𝑎+ ∗ 𝑎𝐶𝑙− 𝑦𝑁𝑎+ ∗ 𝑚𝑁𝑎+ ∗ 𝛾𝐶𝑙− ∗ 𝑚𝐶𝑙−
𝐾𝑠𝑝 𝑁𝑎𝐶𝑙, ℎ𝑎𝑙𝑖𝑡𝑒 = =
𝑁𝑎𝐶𝑙 (𝑠) 𝑁𝑎𝐶𝑙 (𝑠)
3) Rearrange to test for solids
𝑦𝑁𝑎+ ∗ 𝑚𝑁𝑎+ ∗ 𝛾𝐶𝑙− ∗ 𝑚𝐶𝑙−
𝑆=
𝑁𝑎𝐶𝑙 𝑠 ∗ 𝐾𝑠𝑝 𝑁𝑎𝐶𝑙, ℎ𝑎𝑙𝑖𝑡𝑒
1.0 by definition
4) Simplify
𝑦𝑁𝑎+ ∗ 𝑚𝑁𝑎+ ∗ 𝛾𝐶𝑙− ∗ 𝑚𝐶𝑙−
𝑆=
𝐾𝑠𝑝 𝑁𝑎𝐶𝑙, ℎ𝑎𝑙𝑖𝑡𝑒

*
 measured calculated

Na,ppm (mol/kg) Cl, ppm (mol/kg) Ksp (@T, C / P, atm) Na Cl

86,000 (3.74) 145,000 (4.09) 38.2 (@25 / 1) 0.84 0.84

(symmetry)

𝑎𝑁𝑎+ ∗ 𝑎𝐶𝑙− 𝑦𝑁𝑎+ ∗ 𝑚𝑁𝑎+ ∗ 𝛾𝐶𝑙− ∗ 𝑚𝐶𝑙−

Step 1) 𝐾𝑠𝑝 𝑁𝑎𝐶𝑙, ℎ𝑎𝑙𝑖𝑡𝑒 = =
𝑁𝑎𝐶𝑙 (𝑠) 𝑁𝑎𝐶𝑙 (𝑠)

2) 𝑚𝑁𝑎+ ∗ 𝑚𝐶𝑙− ∗ 𝑦𝑁𝑎+ ∗ 𝛾𝐶𝑙−

𝑆=
𝐾𝑠𝑝 𝑁𝑎𝐶𝑙, ℎ𝑎𝑙𝑖𝑡𝑒

15.30 ∗ 0.71 = 10.86

Solve) 3.74 ∗ 4.09 ∗ 0.84 ∗ 0.84
𝑆= = 0.28
38.2

*
Na,ppm (mol/kg) Cl, ppm (mol/kg) Ksp Na Cl S S
(@T, C / P, atm) (w/o ) (with )
87,250 (4.30) 134,549 (4.30) 35.8 (@90/70) 0.74 0.74 0.52 0.28
147,250 (6.41) 225,414 (6.36) 36.5 (@125/200) 1.11 1.11 1.12 1.37
10,800 (0.47) 19,850 (0.56) 41.3 (@4/100) 0.69 0.69 0.006 0.003
(symmetry)

*
 Cation Anion
ppm (mol/kg) Act coef (25C, 1atm) ppm (mol/kg) Act coef (25C, 1atm)
Na+ 14,500 (0.63) 0.665 Cl- 22,510 (0.69) 0.681
K+ 1,234 (0.032) 0.612 SO4-2 2,142 (0.022) 0.087
Ca+2 1,420 (0.035) 0.253 HCO3- 158 (4.0e-3) 0.555
Ba+2 2 (1.4e-5) 0.207 CO3-2 (1.18e-5) 0.093

Step 1) 𝑪𝒂𝑪𝑶𝟑 = 𝑪𝒂+𝟐 + 𝑪𝑶𝟑 −𝟐

…
𝛾𝐶𝑎+2 ∗ 𝑚𝐶𝑎+2 ∗ 𝛾𝐶𝑂3−2 ∗ 𝑚𝐶𝑂3−2
Step 4) 𝑆=
𝐾𝑠𝑝,𝐶𝑎𝐶𝑂3 (𝑐𝑎𝑙𝑐𝑖𝑡𝑒),(𝑇,𝑃)

Assemble necessary variables (from software or literature)

𝐾𝑠𝑝,𝐶𝑎𝐶𝑂3,(25 𝐶,1 𝑏𝑎𝑟) = 2.43𝑒 −9
Plug in data and calculate
Answer: ST=3.99

*
T P CaSO4 BaSO4 CaCO3 Na Ca Ba Cl SO4 CO3
C Bar Ksp Ksp Ksp      
50 30 2.78E-05 1.99E-10 2.41E-09 0.647 0.216 0.185 0.664 0.135 0.083
80 150 1.30E-05 2.61E-10 1.63E-09 0.624 0.178 0.164 0.636 0.113 0.068
120 300 3.28E-06 2.37E-10 4.65E-10 0.589 0.134 0.137 0.596 0.082 0.049
140 460 1.61E-06 1.96E-10 2.35E-10 0.568 0.115 0.124 0.575 0.066 0.040
170 600 4.46E-07 1.37E-10 6.06E-11 0.535 0.088 0.104 0.538 0.045 0.028

T P, bar CaSO4 BaSO4 CaCO3

C Bar S S S
50 30
80 150
120 300
140 460
170 600

*
*
Hand calculations that include methods to predict
K and 
 CaCO3 BaSO4, Halid Unique K 
CaSO4, es scales
SrSO4
semi-empirical Langlier Saturation Index 
Ryznar Stability index  
Pukoris Scale Index  
Stiff Davis   
Oddo-Tomson    
Theoretical Computer Models (like OLI)      

*
 Cation Anion
Ion ppm (mol/kg)  ion ppm (mol/kg) 
Na+ 14,500 (0.63) 0.665 Cl- 22,510 (0.69) 0.681
K+ 1,234 (0.032) 0.612 SO4-2 2,142 (0.022) 0.087
Ca+2 1,420 (0.035) 0.253 HCO3- 158 (4.0e-3) 0.555
Ba+2 2 (1.4e-5) 0.207 CO3-2 (1.18e-5) 0.093

Step 1) 𝑪𝒂𝑺𝑶𝟒 = 𝑪𝒂+𝟐 + 𝑺𝑶𝟒 −𝟐

…
𝛾𝐶𝑎+2 ∗ 𝑚𝐶𝑎+2 ∗ 𝛾𝑆𝑂4−2 ∗ 𝑚𝑆𝑂4−2
Step 4) 𝑆=
𝐾𝑠𝑝,𝐶𝑎𝑆𝑂4 (𝑎𝑛ℎ𝑦𝑑𝑟𝑖𝑡𝑒),(𝑇,𝑃)
Assemble necessary variables (from software or literature)

𝐾𝑠𝑝,𝐶𝑎𝑆𝑂4,(25 𝐶,1 𝑏𝑎𝑟) = 4.40𝑒 −5

Plug in data and calculate

Answer: ST=0.385

*
* Well known, pre-computer method
𝐿𝑆𝐼 = 𝑝𝐻𝑚𝑒𝑎𝑠 − 𝑝𝐻𝑠
* Developed in 1936 to predict pHmeas = measured pH
corrosion and CaCO3 scale in
pHs = pH at saturated CaCO3
municipal water

* Results (next slide)

* LSI>0 Scale forms 𝑝𝐻𝑠 = 𝑝𝐾𝐴2 − 𝑝𝐾𝑠𝑝 − log 𝐶𝑎+2 − log 𝐴𝑙𝑘
* LSI<0 Scale dissolves
pK2 =HCO3  CO3 equilibrium const.
* Limits
pKsp = Calcite solubility product const.
* 6.5 – 9.0 pH
Ca+2 = Calcium conc. (mol/l)
* 4000 mg/l TDS
Alk = Alkalinity conc. (mol/l as HCO3-)
* 95o C

*
Start with this 𝑝𝐻𝑠 = 𝑝𝐾2 − 𝑝𝐾𝑠𝑝 − log 𝐶𝑎+2 − log 𝐴𝑙𝑘

Rearrange 𝑝𝐾𝑠𝑝 = 𝑝𝐾2 − 𝑝𝐻𝑠 − log 𝐶𝑎+2 − log 𝐴𝑙𝑘

Convert p to -log −log 𝐾𝑠𝑝 = −log 𝐾2 + log 𝐻𝑠 − log 𝐶𝑎+2 − log 𝐴𝑙𝑘

Multiply by -1 log 𝐾𝑠𝑝 = log 𝐾2 − log 𝐻𝑠 + log 𝐶𝑎+2 + log 𝐴𝑙𝑘

𝐾2 ∗ 𝐶𝑎+2 ∗ 𝐻𝐶𝑂3 −
Take the exponent 𝐾𝑠𝑝 =
𝐻+

−2 𝐾2 ∗ 𝐻𝐶𝑂3 −
Insert CO3 equation 𝐶𝑂3 =
𝐻+

End with Solubility 𝐾𝑠𝑝 = 𝐶𝑎+2 ∗ 𝐶𝑂3 −2

*
LSI Scaling and Corrosion Tendency Treatment

+4 Severe Scale Forming Required

+3 Significant Scale Forming Recommended

+2.0 Moderate Scale-forming Suggested

+0.5 Slightly scaling and noncorrosive

0 Balanced but corrosion possible No Treatment

-0.5 Slightly corrosive and non-scaling

-1 Mild Corrosion Suggested

-2.0 Moderate Corrosion Recommended

-3 Severe Corrosion Required

*
Measured data Constants and pH
Ion mg/l mol/l 25C 100C
Na+ 23,000 1.0 pK2 10.33 10.09
Ca+2 400 0.01 pKsp 8.62 9.28
Cl- 35,500 1.0 pH 7.54 7.47
Alk 610 0.01

Results 𝐿𝑆𝐼 = 𝑝𝐻 − 𝑝𝐾2 − 𝑝𝐾𝑠𝑝 − log 𝐶𝑎+2 − log 𝐴𝑙𝑘

25C 100C
LSI
OLI(ScaleTend) 6.8 35

𝐿𝑆𝐼25𝐶 = 7.54 − 10.33 − 8.62 − log 0.01 − log 0.01 = 1.83

𝐿𝑆𝐼100𝐶 = 7.47 − 10.09 − 9.25 − log 0.01 − log 0.01 = 2.63

* Calculate LSI for the following

water
http://www.lenntech.com/calculators/langelier/index/langelier.htm

http://www.csgnetwork.com/langeliersicalc.html

http://www.cleanwaterstore.com/technical/water-treatment-
calculations/langlier.html

*
These website contain an LSI calculator
 Ryznar (1942) refined LSI to 𝑅𝑆𝐼 = 2𝑝𝐻𝑠 − 𝑝𝐻𝑚𝑒𝑎𝑠
distinguish waters with same
LSI but different Ca/Alk Where:
ratios 𝑝𝐻𝑠
 A ionic strength term is = 𝑝𝐾2 − 𝑝𝐾𝑠𝑝
added to include salinity +2 − log 𝐴𝑙𝑘 + 𝐼′
effects and:− log 𝐶𝑎
2.5 𝐼
 Primarily for corrosion, semi- 𝐼′ =
1 + 5.3 𝐼 + 5.5𝐼
quantitative for scale
and:
1
 RSI is inverted: low values 𝐼 = ෍ 𝑚𝑖 𝑧𝑖2
indicate scaling. High values 2
𝑖
indicate corrosion pK2 and pKs are same as Langelier constants
I=ionic strength
M=concentration (mol/kg)
z=ion charge

*
 RSI Scaling and Corrosion Tendency

4.0-5.0 Heavy Scale

5.0-6.0 Light Scale

6.0-7.0 Little Scale or Corrosion

7.0-7.5 Some Corrosion

7.5-9.0 Heavy Corrosion

9.0+ Corrosion Intolerable

*
http://www.lenntech.com/calculators/ryznar/index/ryzn
ar.htm

*
Based on water buffering capacity and the maximum
quantity of precipitate that can form
𝑃𝑆𝐼 = 2 𝑝𝐻𝑆 − 𝑝𝐻𝑒𝑞
Where:
𝑝𝐻𝑠 = 9.3 + 𝐴 + 𝐵 − 𝐶 − 𝐷 & 𝑝𝐻𝑒𝑞 = 1.465 ∗ log10 𝐴𝑙𝑘 + 4.54

and:
log 𝑇𝐷𝑆 − 1
𝐴=
10
𝐵 = −13.12 ∗ log 𝑇𝐾 + 34.55 𝐷 = log 𝐴𝑙𝑘 𝑎𝑠 𝐶𝑎𝐶𝑂3
𝐶 = log 𝐶𝑎+2 𝑎𝑠𝐶𝑎𝐶𝑂3 − 0.4 𝐴𝑙𝑘 = 𝐻𝐶𝑂3 + 2 ∗ 𝐶𝑂3 + 𝑂𝐻

*
http://corrosion-doctors.org/Corrosion-by-Water/Scaling-indices.htm
 Stiff and Davis (1952) refined
LSI to correct for high salinity
of oilfield waters 𝑆𝑆𝐼 = 𝑝𝐻 + log 𝐶𝑎+2 + log 𝐴𝑙𝑘 − 𝐾

 All the corrections are

contained within a
Temperature / Salinity plot

*
 4

3.5
0oC
3 30oC

2.5 50oC
60oC
70oC
K

2
80oC
1.5 90oC

100oC
1

0.5

0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4
Molar Ionic Strength

*
Measured data Constants and pH
Ion mg/l mol/l mz2
25C 100C
Na+ 23,000 1.0 1
pK2 10.33 10.09
Ca+2 400 0.01 0.04
pKsp 8.62 9.28
Cl- 35,500 1.0 1
pH 7.54 7.47
Alk 610 0.01 0.01
1
𝜇= 1 + 0.04 + 1 + 0.01 = 1.025
2

Results 𝑆𝑆𝐼 = 𝑝𝐻 + log 𝐶𝑎+2 + log 𝐴𝑙𝑘 − 𝐾

𝑆𝑆𝐼25𝐶 = 7.54 − 2 − 2 − 3.3 = 0.24
𝑆𝑆𝐼100𝐶 = 7.47 − 2 − 2 − 1.4 = 2.07

25C 100C
Stiff Davis
OLI(ScaleTend) 6.8 35

*
Initially developed in 1980’s
Available for CaCO3, CaSO4, BaSO4, and SrSO4
Includes gas phase for calcite scale
based on English units; F and psia

Oddo-Tomson was a significant advancement over previous

indices. Operators and service companies created spreadsheets
with this model. Many are still in use.

*
Equations for Calculating CaCO3 scaling with a gas phase present.
 𝐶𝑎+2 𝐻𝐶𝑂3 − 2
𝑆𝐼 = log + 5.85 + 𝐴 − 𝐵 + 𝐶
𝑃 𝑦𝑔𝐶𝑂2 ∅𝑔𝐶𝑂2

𝐴 = 0.001519 ∗ 𝑇 − 1.64 ∗ 10−6 ∗ 𝑇 2

𝐵 = 5.27𝑥10−5 ∗ 𝑃
𝐶 = 1.431 ∗ 𝐼𝑆 − 3.334 ∗ 𝐼𝑆

  4 0.255  
 P  2.84 x10  
T  460  
 CO
g
2
 exp  

1

CO 2 
P CO 2
(5 * V  10V ) x10 5

y gCO 2  ytot 1 
g brine oil

 ntot (T  460) 
 

*
T in Fahrenheit, P in psia, I in mg/l TDS/58400
J.E. Oddo, J.P. Smith, and M.B. Tomson. 1991. Analysis of and solutions to the CaCO3 and CaSO4 problems in West Indonesia. SPE22782.
 2 1/2
𝑝𝐾 ′ 𝑝𝐾 ′ 𝑝𝐾 ′
𝐶𝑆𝑂4 − 𝐶𝑀𝑔 − 10 + 𝐶𝑆𝑂4 − 𝐶𝑀𝑔 − 10 + 4 ∗ 10 𝐶𝑆𝑂4
−2
𝑆𝑂4 =
2

1 1
′ −3 −6 2 −5 −3 2
𝑝𝐾 = 1.86 + 4.5𝑒 𝑇 − 1.2𝑒 𝑇 + 10.7𝑒 𝑃− 2.38𝐼 2 + 0.58𝐼 − 1.3𝑒 𝐼 𝑇

1 1
𝑆𝐼𝐶𝑎𝑆𝑂4,𝑔𝑦𝑝𝑠𝑢𝑚 = log10 𝐶𝐶𝑎 𝑆𝑂4 −2 + 3.47 + 1.8𝑒 −3 𝑇 + 2.5𝑒 −6 𝑇 2 − 5.9𝑒 −5 𝑃 − 1.13𝐼2 + 0.37𝐼 − 2𝑒 −3 𝐼 2 𝑇
1 1
−2 −3 −6 2 −5 −3 2
𝑆𝐼𝐶𝑎𝑆𝑂4,𝑎𝑛ℎ𝑦𝑑𝑟𝑖𝑡𝑒 = log10 𝐶𝐶𝑎 𝑆𝑂4 + 2.52 + 9.98𝑒 𝑇 + 0.97𝑒 𝑇 − 3.07𝑒 𝑃− 1.09𝐼2 + 0.5𝐼 − 3.3𝑒 𝐼 𝑇

*
T in Fahrenheit, P in psia, I in mg/l TDS/58400
J.E. Oddo, J.P. Smith, and M.B. Tomson. 1991. Analysis of and solutions to the CaCO3 and CaSO4 problems in West Indonesia. SPE22782.
 2 1/2
𝑝𝐾 ′ 𝑝𝐾 ′ 𝑝𝐾 ′
𝐶𝑆𝑂4 − 𝐶𝑀𝑔 − 𝐶𝐶𝑎 − 10 + 𝐶𝑆𝑂4 − 𝐶𝑀𝑔 − 𝐶𝐶𝑎 − 10 + 4 ∗ 10 𝐶𝑆𝑂4
−2
𝑆𝑂4 =
2

1 1
𝑆𝐼𝑆𝑟𝑆𝑂4,𝑐𝑒𝑙𝑒𝑠𝑡𝑖𝑡𝑒 = log10 𝐶𝑆𝑟 𝑆𝑂4 −2 + 6.11 + 2.0𝑒 −3 𝑇 + 6.4𝑒 −6 𝑇 2 − 4.6𝑒 −5 𝑃 − 1.89𝐼 2 + 0.67𝐼 − 1.9𝑒 −3 𝐼 2 𝑇

1 1
𝑆𝐼𝑆𝑟𝑆𝑂4,𝑏𝑎𝑟𝑖𝑡𝑒 = log10 𝐶𝐵𝑎 𝑆𝑂4 −2 + 10.03 + 4.8𝑒 −3 𝑇 + 11.4𝑒 −6 𝑇 2 − 4.8𝑒 −5 𝑃 − 2.62𝐼2 + 0.89𝐼 − 2.0𝑒 −3 𝐼 2 𝑇

*
T in Fahrenheit, P in psia, I in mg/l TDS/58400
J.E. Oddo, J.P. Smith, and M.B. Tomson. 1991. Analysis of and solutions to the CaCO3 and CaSO4 problems in West Indonesia. SPE22782.
*
*
*
 Multi Scale (Expro Petrotech)
 ScaleSoftPitz (Rice University)
 Downhole SAT (French Creek Software)
 ScaleChem (OLI Systems)

*
  Equilibrium and steady-
state
 Equation of state *
 Chemical Speciation*
 Activity coefficient *
 Phase equilibrium
 Mass balance
 Charge balance
 Energy balance
 Process simulation
 non-Equilibrium and
transient
 Mass transfer
 Phase velocity
 Nucleation kinetics
 Precipitation kinetics
 Scale inhibition
 Scale adhesion

*
Contain some-many of the following
equations/models
* - minimum required for accurate oilfield scale prediction
 Many scale prediction tools available
 All based on fundamental equilibrium equations
 Each have adjustments for temperature and salinity
 All have some value
 Low cost
 Easy to use
 Can calculate complex systems
 Can model mixing and inhibition