SCALING INDICES

Calculating, Plotting and Understanding

     In this article we consider the calcium-scaling tendencies present in cooling water
systems, indices for their characterization and ways in which these indices are
influenced by the presence of various chemicals.

     The Langelier Saturation Index (LSI), Ryznar Stability Index (RSI), and
Practical/Puckorius Scale Index (PSI) were created so that the several factors which
influence scaling could be reported in a single number. This number can be determined
from charts, tables, and graphs, but slide rules and computer programs are also
extensively utilized. We will suggest here a novel method for arriving at the PSI and
attempt to detail the impact on PSI values of the treatments which might be added.

     Table I lists the most commonly used indices and the scaling tendencies associated
with them. Readers of this article need not be reminded that a water which is "strong
dissolving" for scale is also "corrosive" to other metals.

     The main objective of using these indices is to adjust the cooling water to a
nonscaling condition"', traditionally by the addition of sulfuric acid. The acid lowers the
alkalinity and also converts a portion of the calcium to calcium sulfate, with its higher
solubility. Additional interpretation and use of these indices is now being made and will
be described below.

     The Ryznar Stability Index provides a closer correspondence between calculated
predictions and results obtained in the field, and consequently has replaced the
Langelier in many applications. Knowledge of the values for five system variables is
necessary for the calculation of either the Langelier or Ryznar index.

     The Practical Scale Index consistently gives better indications of actual scaling
conditions than do the other two indicators, especially at pH values above 8.0.
Conveniently for us, the PSI uses the same numbering system and set of descriptions as
does the RSI. The difference between them is that the pH value used in determining the
RSI is replaced by a total alkalinity value in the PSI, thereby providing an indicator of
equilibrium pH not as easily buffered as the measured pH.

     Since total alkalinity is already used for the calculation of these indices, we are able
in determining the PSI to reduce the number of variables to four. Of these, the value for
dissolved solids is usually of minor impact, temperature levels are often relatively
stable, and both factors need be considered only when they present substantial
variations from median values.

     We are cautioned that these numbers and their interpretation are not exact and should
serve only as an indication of directional tendencies. They do, however, provide one of
the few methods for quantifying the scaling tendencies of a system. Our approach
should be to always protect from both scale and corrosion even when we think that they
will not occur.
Formula Development and Calculation

     The formulas for the PSI are as follows,: PSI = 2pH. - pH eq, where pH.=
9.30+A+C-D, and pH = 1.465 loglo (M Alk) + 4.54 with the letters A, B, C, and D used
in the same manner as in the LSI and RSI determinations to indicate respectively: total
dissolved solids (TDS in ppm), temperaFahrenheit), calcium hardness (CaH in ppm
CaCO.), and total alkalinity (M Alk in ppin CaCo.).

     By fitting curves to the published tables, we have obtained: A = 0.1(log TDS - 1).
Perfect fit for TDS of 50 - 1000. B = 1.32 + 0.0084 (150-T). Perfect fit for 100-150,
close for 70-90 and 160-170, and moderately close for 50-60. C = log CaH - 0.4. Perfect
fit for 50-700, very close for 800-900. D = log M Alk. Perfect fit for 10-800.

We combine all of this information to obtain Formula A:

PSI= 19.82-2loglo(CaH)- 3.465loglo(MAlk)+0.2loglo(TDS)-0.0168T, and have verified

it by comparison to five results from Puckorius.

To simplify our calculations, we isolate three terms from this formula to establish
Formula B:

K = 19.82 + 0.2 loglo (TDS) - 0.0168 T, and we then calculate Table II.

For the calculation in this and other tables, we used the Microsoft Excel spreadsheet
program.

We now replace Formula A with Formula C:

PSI = K - 2log,() (CaH) - 3.465 loglo (M Alk).

     For each value of K found in Table II, calculations of the PSI may be made as in
Table III for 18.38. In most cases, we can use one K to represent a range, such as 18.38
for values from 18.26 to 18.49. This introduces an error in the PSI of no more than 0.12.

     Table II also allows us to see the influence of these variables. A change in TDS from
50 to 1000 results in an increase in PSI of 0.26, while a rise in temperature from 50* F
to 160 results in a close to the midpoint reduction in PSI of 1.85.

     These changes are often of small significance for the application we herein consider,
especially changes in TDS. The impact of these variations is further minimized when
we encounter values close to the midpoint of their respective ranges.

     For comparison to TDS and temperature, we return to Table III and find that an
increase in calcium hardness from 100 to 900 reduces the PSI by about 2.9. An increase
in M alkalinity from 100 to 1000 reduces the PSI by about 3.46.

Plotting Curves

To allow us to draw lines between points with the same

PSI values, we adjust formula C to get Formula D:
Call = antilog U18.38 - (PSI) - 3.465loglo(M Alk))/21, or

CaH = J0{18.W-(PSI)~3.4651og(M A&))/2

     Calculations of this formula result in Table IV. Again we must emphasize that the
precision of the mathematical development must not obscure the acknowledged
weaknesses of these indicators and the necessity for caution in their use. Continuing to
use the Excel program, we plot Graph A from Table IV, covering PSI values form 3 to
6. Values from 6 to 9 can also be easily calculated and plotted fi-oin Table IV. Table III
may be used for manual plotting if specific ranges are to be examined in closer focus.
Recall that Tables III and IV and Graph A result from a K value of 18.38.

Estimation of pH

    At times systems are described to us with measured pH rather than by total alkalinity.
Conversion fi-om one system to the other is often nlecessary and several researchers
have made estimates for that purpose. We list seven sets of these figures in Table V and
then recommend a rounded off version for more convenient use. It is anticipated that
90% of the time these pH estimates will be within 0.5 units of the measured pH. We
have attached these values to Graph A.

    C-10 and C-15 were developed by Caplan. The first was calculated from nine
responses to a survey' the second from data on 43 water samples with no acid added. K-
1 was derived by Kunz, Yeng, and Hess from systems which had received acid
treatment. Iona C4 provides 1-2, Carrier' reprints a Betz graph for B-5, and Puckorius'
lists the formula for P4. Goldstein, et. al.' provide B-3 for equilibrium at 40 degrees C.
and an ionic strength of 5 X 10-3.

Chemical Treatment

     Studies performed in many cooling tower system waters by Puckorius and Brooke 7
have led them to recommend the use of the PSI to quantify the amount of specific
inhibitors to be used under various scaling conditions. The remainder of this section is
based upon their paper, as well as earlier articles by Strauss and Puckorius and by
Brooke.

A. Solubilizing Inhibitors

1. The phosphonates HEDP and AMP perform by increasing the solubility of calcium
scale components and are frequently referred to as "solubilizing inhibitors." They
impact the PSI by shifting the value "at which the water is stable to the deposition or
dissolving of calcium carbonate 9 down to about 4.

2. Another type of scale control involves the use of polyacrylates. These products also
solubilize scale and allow an index down to 4.4 with a "stable water.

B. Crystal Modifiers

     Since the scale forming ingredients are being effectively removed from the cooling
water by these additives at all levels of concentration, the indices are not helpful to us.
The PSI value is seldom less than 6.0 because the water is in a precipitation mode, and
the suspended solids are being converted to sludge or scale. Efficient dosage for crystal
modifiers must be determined under actual or simulated field conditions.

C. Combinations of Solubilizers and Crystal Modifiers

     There are many treatment programs which utilize the solubilizing inhibitors such as
phosphonate or polyacrylate along with crystal modifiers. This means that the system is
in a solubilizing mode until it exceeds the capacity of the solubilizing inhibitors and
then passes into a precipitation mode. The index can be utilized to predict scale (and
treat to prevent it) down to about PSI 4, but not as effectively as in the absence of
crystal modifiers.

D. Phosphates

     With the phosphate programs now being used, the indices are not useful as guides
because calcium phosphate becomes the controlling species rather than calcium
carbonate. If phosphate appears in a system from the degradation of phosphonates, the
index becomes inaccurate to the extent of the phosphate present.

E. Additives Which Do Not Affect PSI

     If the treatment programs contain only zinc or molybdate, the predominant deposits
in a scaling environment will most likely be calcium carbonate, and the indices then
become accurate indicators.

Corrosion

     It is generally recognized that, in addition to their scale prevention properties,

phosphonates and other additives can provide or assist in providing corrosion
prevention. We should also try to determine to what extent PSI values can predict
corrosion.

Bohnsack sought to provide insights which should be considered when discussing the
usefulness of stability indices as corrosion predictors. They found the connections
between a stability index and corrosion to be tenuous and sought "a more scientifically
founded mechanism." They concluded that "the solubility of corrosion products is a
better descriptor of the corrosion behavior of iron in water" than are the stability or
saturation indices.

Paul Puckorius suggests that: "...these indices have also been used to indicate the
corrosivity of cooling water"...an approach that according to Stern..." is in error and has
led to serious problems."' "It should be remembered that cooling water ... is always
corrosive, mainly because of the esence of dissolved oxygen and dissolved solids. This
is true even when the water is scale-forming, and particularly true if it is not
scaleforming.

References
1. Puckorius, Paul. "Get a Better Reading on Scaling Tendency of Cooling Water",
POWER, September, 1983.

2. Caplan, Gary. "Cooling Water Computer Calculation: Do They Compare?",

Corrosion 90, Paper No. 100.

3. Kunz, R.G., Yeng, A.F. and Hess, T.C., "Cooling Water Calculations" Chemical
Engineering, August 1, 1977.

4. Ionac Chemical Company. "Cooling Water Treatment, Practice and Principles",

1962.

5. Carrier System Design Manual: Part 5-Water Conditioning, 1972.

6. Goldstein, D.J., Hicks, R.E., and Liang, L., Prepared Discussion to Boroughs, R.D.,
McKee, J.E., and Moss, R.D. "The Effect of Carbon Dioxide Transfer on Cooling Water
pH and Calcium Carbonate Deposition", IWC 81-27.

7. Puckorius, Paul R., and Brooke, J. Maxey, "A New Practical Index for Calcium
Carbonate Scale Prediction in Cooling Water Systems", Corrosion 90, Paper No. 99.

8. Strauss, Sheldon D. and Puckorius, Paul R., "Cooling-Water Treatment for Control of
Scaling, Fouling, Corrosion," POWER, June, 1984.

9. Brooke, Maxey, "The Calcium Carbonate Story," Corrosion 83, Paper No. 284.

10. Bohnsack, G., Johnson, D.A., and Buss E., "Corrosion in Fresh Water and its
Relationship to Water Quality as Described by Stability Indices," Corrosion 90, Paper
No. 101