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By Dan Vanderpool, Laurel Functional Chemicals

Abstract

There are several important pH values for cooling water systems. These pHs are used to understand the potential for scale formation. They are also used to assess a pilot cooling towers ability to a model an actual cooling tower and to design research and laboratory evaluations. This article explains each of these pHs and the calculations used to derive them. Key Words: Ion Equilibrium Model, Langelier Saturation Index, Ryznar Stability Index, Practical Scaling Index, Regression Method, Atmospheric Equilibrium, Temperature effect on pH, pHs.

Introduction

pH has a pivotal role in the chemistry of water. It influences the driving forces for scale and corrosion. Yet, a measured pH value becomes meaningful only when it is put into context with the other important pH values that are characteristic of the water. These characteristic pH values are derived from basic ionic equilibria and from empirically established relationships. The commonly used pH relationships in Table 1 are important benchmarks for cooling water. The example water shown in Table 2 will be used to compute these pH values.

Table 1: Characteristic pH Relationships for Cooling Water Kunz: pH = 1.6 Log (Alk as mg/L CaCO3) + 4.4 Caplan: pH = 1.8 Log (Alk as mg/L CaCO3) + 4.0 LSI = pH pHs LSI = approximate Log(CaCO3 Saturation) RSI = 2 pHs pH PSI = 2 pHs pHe pHe = 1.46 Log (Alk as mg/L CaCO3) + 4.54 Langelier: pHs = -Log [H] = Log (Ksp/K2) + p[Ca] + p(Alk) Larson & Buswell: pHs = Log (Ksp/K2) + p[Ca] + p(Alk) + [2.5(I)1/2]/[1+5.3(I)1/2 + 5.5I] Alk at pHs = -[H] + Kw/[H] + [H](Ksp/K2[Ca]) + 2 Ksp/[Ca] Atmospheric Equilibrium pH = 0.92 Log (Alk as mg/L CaCO3) + 6.6 (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)

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Table 2: Composition of Example Water Used for Calculation Comparisons Calcium as CaCO3 Alkalinity as CaCO3 Chloride as Cl Sulfate as SO4= Conductivity Temperature pHs @ 77 oF pHe Atmospheric Equilibrium (Atm Equil) 375 mg/L 600 mg/L 266 mg/L 14 mg/L 1455 mho 77 oF 6.59 8.60 pH 9.2

The operating pH of a cooling tower unfortunately cannot be accurately forecasted from equilibrium equations. The reason is that typical cooling water has a lower pH than expected due to excess carbon dioxide arising from neutralization of alkalinity and biological respiration. Forecasting the operating pH requires another approach. In the mid-1970s, R. D. Kunz took samples from operating cooling tower waters to determine an empirical relationship for forecasting the operating pH.1 Caplan updated this equation by averaging nine other empirical relationships.2 Equations 1 and 2 show the two relationships. Equations 1 and 2 are used for estimating the alkalinity required achieving a target pH in cycled-up cooling water, and for calculating the acid needed to neutralize excess alkalinity in the make-up. They are also used for comparing the operation of a cooling-tower with typical towers, and in evaluating pilot cooling-towers as mimics of real towers.

The pHs is the pH at which water has a calcium carbonate saturation of one and it is commonly used to quantify calcium carbonate scaling tendency. Langelier defined the scaling tendency for calcium carbonate, the LSI, as the difference between the operating pH and pHs, as shown by equation 3. This value is approximately equal to the Log of CaCO3 saturation as shown by equation 4. An important limitation of the LSI is the non-consideration of the chemical complexes of calcium, and approximation of the carbonate/bicarbonate ratio inherent in the pH difference. The LSI begins to significantly deviate from the true CaCO3 saturation above pH 8.0; and above pH 10, where the CaOH+ complex becomes important. The LSI becomes meaningless with regard to CaCO3 saturation. Table 3 shows the deviation of the LSI saturation from the true saturation. Another measure of scaling tendency based on pHs was developed by Ryznar.3 He recognized that above pH 10 the LSI would falsely predict scaling where, in actuality, the water was corrosive, i.e., the water would

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dissolve cement rather than deposit CaCO3. Ryznar apparently, however, did not recognize that the failure of the LSI at high pH is due to the neglect of the complexes of calcium with alkalinity and hydroxide. Ryznar developed an empirical index, known as the Ryznar Stability Index (RSI), as shown by equation 5. Although this index has no physical meaning, it is frequently used to quantify calcium carbonate scaling and corrosivity to concrete. Puckorius & Brooke introduced a modification of the Ryznar Stability Index, known as the Practical Scaling Index (PSI), as shown by equation 6. Rather than using the measured pH as in the Ryznar Stability Index, Puckorius & Brooke used a formula to calculate a practical pH based on their experience of treating CaCO3 scaling, they called their pH, pHe, as shown by equation 7. How do the Scaling Indexes compare? Table 4 compares the True CaCO3 Saturation, LSI, RSI, and PSI for the example water, whose pHs is 6.59.

Table 3: Comparison of the Saturation Calculated from the LSI with the True Calcium Carbonate Saturation pH of the Water: Scaling Index LSI (= pH pHs; pHs = 6.59) Approx CaCO3 Saturation = 10LSI True CaCO3Saturation 7.5 0.91 8 8 8.0 1.14 26 23 8.5 1.91 82 66 9.0 2.41 257 159 9.2 2.61 407 210

Table 4: Variation of Scaling Indexes with pH pH of the Water: Saturation Index True CaCO3 Saturation Log (True CaCO3 Saturation) LSI = pH pHs; pHs = 6.59 RSI = 2 pHs pH PSI = 2 pHs pHe; pHe = 8.60 7.5 8 0.88 0.91 5.68 4.58 8.0 23 1.36 1.41 5.18 4.58 8.5 66 1.82 1.91 4.68 4.58 9.0 159 2.20 2.41 4.18 4.58 9.2 210 2.32 2.61 3.98 4.58

Notice that the PSI scaling tendency remains the same, indicating no change in scaling tendency even though the pH and True CaCO3 saturation change: this results from the use of pHe rather than the actual pH.

Calculation of pHs

There are several formulas used to calculate pHs. They differ by the approximations used in the calculations. They share the common definition of alkalinity, defined by Langelier as consisting only of hydrogen, hydroxide, bicarbonate and carbonate ions. (ionic charges are not shown for clarity): Alk = -[H] + [OH]+ [HCO3]+ 2[CO3]. They also share the definition of unit

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saturation for calcium carbonate according to the equation CaCO3 solid + H+ = Ca++ + HCO3-, namely, ([Ca][HCO3]/[H])/(Ksp/K2) = 1; where, Ksp = [Ca][CO3] for calcite, and K2 = [H][CO3]/[HCO3] for the second dissociation constant of carbonic acid. Langelier derived his formula for pHs by rearranging this equation to give [H] = (K2/Ksp)[Ca][HCO3]. And thus, pHs = -Log [H] = Log (Ksp/K2) + p [Ca] + p[HCO3]. All the terms on the right side are known except [HCO3], so Langelier used the definition of Alkalinity to calculate [HCO3] as follows: Alk = -[H] + Kw/[H] + [HCO3] + 2K2[HCO3]/[H], where, [OH] = Kw/[H]; and [CO3] = K2[HCO3]/[H]. Upon rearrangement one obtains [HCO3] = (Alk + [H] Kw/[H])/(1 + 2K2/[H]); or, p[HCO3] = p(Alk + [H] Kw/[H]) - p(1 + 2K2/[H]). Since Alk >> [H] and Kw/[H]; and 1 > 2K2/[H], where K2 is approximately 10-10.3 and [H] is approximately 10-7, then p[HCO3] = approximately p(Alk). Thus, pHs is given by Langelier as pHs = -Log [H] = Log (Ksp/K2) + p[Ca] + p(Alk), as shown by equation 8. Langelier therefore used an approximate value of [HCO3]; moreover, he did not correct the values of Ksp, K2, and [H] for dissolved salts, although the values of Ksp and K2 were corrected for temperature. To improve the accuracy for cooling water, Larson & Buswell added a new term to approximately correct for dissolved salts to give: pHs = Log (Ksp/K2) + p[Ca] + p(Alk) + [2.5(I)1/2 ]/[1+ 5.3(I)1/2 + 5.5I], as shown by equation 9. In contrast to these approximate approaches a precise way to calculate pHs is the regression method, which rigorously calculates the bicarbonate concentration and incorporates dissolved salts corrections. It starts by combining the equation for unit saturation and the definition of alkalinity to give an equation for the unknown [H] (where [Ca] is equal to the calcium hardness): Alk = -[H] + Kw/[H] + [H](Ksp/K2[Ca]) + 2Ksp/[Ca], as shown by equation 10. The solution to this equation using the Newton-Ralphson method is given in Appendix 1. Then, [H] is corrected by its activity coefficient to yield pHs, i.e., pHs = -Log ([H]fh). A Comparison of these three ways of calculating pHs is shown in Table 5 for the example water at 77 oF.

Table 5: Comparison of Three Methods of Calculating pHs Method Langelier original Larson & Buswell Regression pHs 6.29 6.49 6.59 Comment No ionic strength; approximate [HCO3] Uses approximate ionic strength; approximate [HCO3] Uses exact ionic strength; exact [HCO3]

Notice that pHs varies by up to 0.3 units between the calculations. This translates to a two fold variation in terms of CaCO3 saturation according to the relation (CaCO3 saturation) = approximately 10LSI.

pH decreases when temperature is raised in a confined space where CO2

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cannot escape. Langelier believed it was important to account for this effect.4 The true scaling tendency in the heat exchanger, where scaling is usually most problematic, requires the use of this lower pH. The conversion of the pH of the basin water to the pH in the heat exchanger requires two separate calculations. Here is how Langelier approached the two calculations. First, the dissolved carbon dioxide concentration is determined from the conditions at the measured pH using the Langelier definition of alkalinity: Alk = -[H] + Kw/ [H] + K1[CO2*]/[H] + 2K2K1[CO2*]/[H]2, where, [OH ] = Kw/[H]; [HCO3] = K1 [CO2*]/[H]; [CO3] = K2[HCO3]/[H]; and, the equilibrium constants are for the temperature of pH measurement. Since [H] is known from the measured pH, this equation is now a function of [CO2*]. [CO2*] can be found by the regression equations given in Appendix 2. The results yield the total carbon dioxide at the measured pH as: Tco2 = [CO2*] + [HCO3] + [CO3]. Since Tco2 stays the same while the water is inside the heat exchanger, it is used along with the alkalinity equation, to calculate the redistribution of carbonate species and pH at the second temperature. The calculation uses the equilibrium constants for the second temperature, Kw, K1, and K2. See the spreadsheet on the AWT website www.awt.org\members\publications\analyst\2004 \spring\Langelier_SatCalc1.htm for a working layout of the calculations. Table 6 shows the effect of temperature adjustment for the example water in Table 2, with measured pH of 8.0 at 77 oF, and heat exchanger temperature of 112 oF.

Table 6: Effect of Temperature Correction of pH on Calcium Carbonate Saturation Value Uncorrected for Temp pH pHs for 112 oF LSI = pH pHs for 112 oF Approx CaCO3 Saturation = 10LSI 8.0 (measured at 77 oF) 6.44 1.56 36 Corrected for Temp 7.93 (at 112 oF) 6.44 1.49 31

In this example, the temperature adjustment of the pH has a relatively small effect of only 0.07 LSI units, which arises from the lower pH in the heat exchanger; this results in a 15 % difference in the CaCO3 saturation values.

The atmospheric equilibrium pH is the pH achievable when pH-control is not practiced and provided that no calcium carbonate precipitation occurs. Knowledge of the atmospheric equilibrium pH will define how closely a cooling system is operating to its natural pH limit and may help to obtain more cycles from a given make-up water. For example, typical municipal potable water used as makeup has a higher pH than expected because it contains too little carbon dioxide. The pH can be lowered to the atmospheric equilibrium pH by adding a small amount of

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scale becomes limiting.

The atmospheric equilibrium pH is calculated from Henrys Constant, Kg,

and the partial pressure of carbon dioxide in the atmosphere, Pco2, which is

typically between 10(-3.39)and 10(-3.61) atmospheres. In order to calculate the

atmospheric equilibrium pH, Langelier used the following equilibria to define

the species:

CO2 gas = CO2 aq, where [CO2 aq] = Kg Pco2;

CO2 aq + H2O = H2CO3, where Kh = [H2CO3]/[CO2 aq];

CO2* = [CO2 aq] + [H2CO3], so

[CO2*] = [CO2 aq](1 + Kh) = approximately [CO2 aq] since Kh =

approximately 10(-2.8), also [CO2*] is used to define the first dissociation

constant for carbonic acid, thus [HCO3-] = K1[CO2*]/[H].

The Langelier definition of alkalinity then becomes on expansion: Alk = H + Kw/[H] + K1(KgPco2)/[H] + 2K2K1(KgPco2)/[H]2. The Langelier Alk equation can be solved for [H] by the regression method as in Appendix 3. See the spreadsheet on the AWT website www.awt.org\members\publications\analyst\2004\spring\ AtmEquil_pH_Langelier.htm for working spreadsheet. The calculation can be made more precise by adding the chemical species for hardness and its complexes with carbonates, hydroxide and sulfate. This requires adding the mass balance equations for hardness ([M] = sum of hardness ions) and Total Sulfate: Alk = -[H] + [OH] + [HCO3] + 2[CO3] + [MHCO3] + 2[MCO3] + [MOH]; Total Hardness = [M] + [MHCO3] + [MCO3] + [MOH] + [MSO4]; and Total SO4 = [SO4] +[MSO4]. The solution of this expanded model can be achieved with the regression method for simultaneous equations as demonstrated in the spreadsheet, AtmEquil_pH_Expanded. Alternatively, a much easier way to calculate of the atmospheric equilibrium pH is the alkalinity/pH relation equation 11.5 How do these calculations of atmospheric equilibrium pH compare? Table 7 shows the results for the example water.

Table 7: Three Methods of Calculating Atmospheric Equilibrium pH Calculated Atmospheric Equilibrium pH: Log Pco2 * Langelier model Expanded model Quick Formula** -3.5 9.14 9.19 9.16 -3.61 9.23 9.27 9.16 -3.39 9.05 9.10 9.16

*Pco2 is the carbon dioxide partial pressure in units of atmospheres. **Atmospheric Equilibrium pH = 0.92 Log (Alk as mg/L CaCO3) + 6.6, for Pco2 = 10-3.5; 77 oF. The simple Langelier model and the Quick Formula give the equilibrium pH within 0.05 of a pH unit of the more rigorous Expanded model. In contrast, variation in the normal

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atmospheric carbon dioxide partial pressure of between 10-3.39 and 10-3.61 atmospheres causes greater uncertainty of 0.17 pH units.

Conclusions

The various pH values used to characterize the calcium carbonate scale potential and tower operation have been described, along with their method of calculation. The pH of unit saturation, pHs, is important as it is used in several scaling indexes; the most widely used being the LSI. The LSI is important because it is approximately equal to the logarithm of the true calcium carbonate saturation. Depending on the level of approximation in the calculation of the pHs, pHs can vary by several tenths of a pH unit, or up to two-fold variation in terms of CaCO3 saturation values. The influence of temperature on pH is described: the pH decreases as the temperature is raised (in a confined space where CO2 cannot escape). The temperature affect typically changes the LSI by about a tenth of a pH unit, or approximately 15 % variation in terms of CaCO3 saturation values. Three ways of calculating the atmospheric equilibrium pH are compared. The atmospheric equilibrium pH is the pH attainable when acid is not fed to the cooling water and provided no CaCO3 precipitation occurs. The rudimentary Langelier model and the Quick Formula give values of atmospheric equilibrium pH within a few hundredth pH units of the more rigorous Expanded model. In contrast, the choice of atmospheric carbon dioxide partial pressure causes a greater uncertainty of almost 0.2 pH units. The various pH values can be calculated using the regression formulas in this article with common spreadsheet computer programs like Microsoft Excel, Lotus 123, etc. In setting up even the simplest ionic equilibrium model, one sees the paradoxical nature of dissolved carbon dioxide; namely, its concentration can affect the pH but not the alkalinity.

Appendixes

Appendix 1. Equations used in the Regression Method for pHs. (See Langelier_SatCalc for a working example). The regression equation for Alkalinity, Alk = -[H] + Kw/[H] + [H](Ksp/K2 [Ca]) + 2Ksp/[Ca], is solved using an initial guess value for [H]. The difference between the calculated value of Alk and the true Alk is used to find an improvement to the initial guess of [H]. The improvement is found with the formulas below: Alk = (Alk true Alk calc) [H] = [H guess] Alk/(-[H guess] Kw/[H guess] + [H guess] Ksp/(K2[Ca]) + 2 Ksp/[Ca]) [H] better = [H] guess + [H] Alk is repeatedly calculated with [H] + [H] so that Alk is very small. Generally, 4 repetitions give the correct value of [H] so that Alk < 10-20. pHs is calculated as Log ([H]fh), where fh is the activity coefficient for [H].

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(See Langelier_SatCalc for a working example).

When the pH is given, the unknown in the alkalinity equation, Alk = -[H] +

Kw/[H] + K1[CO2*]/[H] + 2 K2K1[CO2]/[H]2, is the dissolved carbon

dioxide since [H] = 10-pH/fh. These are the equations used in the Newton-

Ralphson method:

Alk = Alk true Alk calc

CO2*=[CO2*] Alk/(-[H] + Kw/[H] + K1[CO2*]/[H] + 2K2K1[CO2*]/

[H]2)

[CO2*] better = [CO2*] guess + CO2*

Appendix 3. Regression equations to calculate the Langelier Atmospheric Equilibrium pH. (See AtmEquil_pH_Langelier for a working example). Solve the Alk equation for atmospheric equilibrium, Alk = -H + Kw/[H] + K1 (KgPco2)/[H] + 2K2K1(KgPco2)/[H]2, by making a guess value of [H]6,7 then calculate improvements with the formula: [H] = [H]( Alk)/(-[H] Kw/[H] - K1KgPco2/[H] - 4K2K1KgPco2/[H]2). The correct concentration of [H] is converted into activity to give pH, i.e., Atmospheric Equilibrium pH = -Log ([H]fh). Web links to spreadsheets for doing the calculations described in this article: True CaCO3 Saturation (See Expanded_SatCalc2.htm) pHs Regression method Dissolved Carbon Dioxide, [CO2*] Temperature Correction of pH (See Langelier_SatCalc1.htm) Atmospheric Equilibrium pH,Langelier Model (See AtmEquil_pH_Langelier.htm) Atmospheric Equilibrium pH, Expanded Model (See AtmEquil_pH_Expanded.htm)

References:

1. R.D. Kunz, A.F. Yen, and T.C. Hess, Cooling Water Calculations, Chemical Engineering, (August 1977) pp 62-71. 2. Gary Caplan, Cooling Water Computer Calculations: Do They Compare? Corrosion /90, NACE International Corrosion Forum, Las Vegas, NV (April 1990) 3. John W. Ryznar, A New Index for Determining Amount of Calcium Carbonate Scale Formed by a Water, J Amer Water Works Assoc (April 1977, vol 36) pp 472-486 4. W.F. Langelier, Effect of Temperature on the pH of Natural Waters,

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J Amer Water Works Association, vol 38 (1946) pp 179-185 5. Dan Vanderpool, Hidden Assumptions in Saturation Calculations, The Analyst, vol IX, No. 3, 2002, p. 25. 6. H. Margenau and R. M. Murphy, Mathematics of Physics and Chemistry, (Van Nostrand Co., NY 1943) p. 476 7. The Atmospheric Equilibrium pH equation is a quadratic with respect to the variable [H]; there are mathematically two correct solutions. To avoid obtaining the inappropriate solution, the initial guess of [H] must be higher than the correct value, while not being too high. The author uses the formula pH = 0.9log(Alk as mg/L CaCO3) + 7.2. [H] is approximately equal to 10-pH. If a low initial guess is used, the convergence finds a physically meaningless solution (equal to the alkalinity.) If too high a guess is used, the first iteration over corrects and jumps to the convergence of the physically meaningless solution. About the Author: Dr. Dan Vanderpool is president of Laurel Functional Chemicals, 2925 32nd Street, Northport, AL 35476, Phone:(205)-339-5718.

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