SM
An index for determining
the amount of calcium
carbonate scale formed
by a water
By John W. Ryznar
The purpose of this investigation was to obtain a
formula that will give a quantitative index of the
amount of calcium carbonate scale that would be
formed by a water at any temperature up to 200°F
and to predict, if possible, the corrosiveness of wa-
ters that are non-scale forming. This information was
also desired for waters in which inhibitors of the
polyphosphate or molecularly dehydrated phosphate
type were present.
Scale formation in distribution mains, domestic hot-
water heaters, and various types of cooling equipment
is well known. Scale is also a problem in boiler
feedwater heaters and feedwater lines. In view of
these and other problems caused by undesirable
deposits and incrustations, a formula having quanti-
tative significance would be of great value in predict-
ing the behavior of a water and in recommending the
necessary corrective treatment.
The molecularly dehydrated phosphates were studied
because of their ability to stabilize a water and thus
prevent deposition of CaCO3. It was thought that this
quantitative index or formula could be best obtained
by using the values and corrections for the different
equilibria affecting calcium carbonate solubility.
The factors affecting CaCO3 solubility equilibria have
been studied by many investigators. Larson and
Buswell, in their paper “Calcium Carbonate Satura-
tion Index and Alkalinity Interpretations,” give a good
bibliography on this phase of the problem. Prof. W. F.
Langelier receives credit for first developing a gen-
eral expression that takes into consideration the
different readily determined variables in a water
affecting CaCO3 solution or precipitation.
For waters in a pH range of 6.5-9.5, Langelier’s for-
mula for the pH at which a water is in equilibrium
with calcium carbonate is:
pHs = (pk'2 – pk's) + pCa + pAlk
K'2 and K's are apparent constants computed from
the true thermodynamic constants K2 and Ks, values
Reprint R-20
of which have been determined. K'2 is the second dis-
sociation constant for carbonic acid, and K's is the
activity product of calcium carbonate. The term (K'2
– K's) varies with ionic strength, dissolved solids, and
temperature. pCa is equal to the negative logarithm
of the calcium ion concentration in moles per liter;
pAlk is the negative logarithm of the total alkalinity
of the water to methyl orange in terms of titratable
equivalents per liter.
Larson and Buswell, using more recent data for evalu-
ation of the constants and their variation with tem-
perature and total dissolved solids, express the
formula for the pH of CaCO3 as:
Ks
pHs = log – log (Ca+2)
K 2
– log (alk) + 9.30
2.5 √ u
+
1 + 5.3 √ u + 5.5
In this equation (Ca+2) and (alk) are expressed in parts
per million as Ca and CaCO3, respectively.
The difference between the actual pH of a sample of
water and its calculated pH is the measure of the
degree of calcium carbonate saturation and has been
called the saturation index or:
Saturation Index = Actual pH – pHs
A plus value for the saturation index indicates a ten-
dency to deposit CaCO3; a minus value indicates a
tendency to dissolve CaCO3.
The saturation index is only qualitative, and, as
Langelier emphasized, “the saturation index is an
indication of directional tendency and of driving
force, but it is in no way a measure of capacity.”
The saturation index, however, is not always
reliable in predicting this because some wa-
ters with a positive index may actually
be quite corrosive.
Reasons for this are that the Langelier index does The effect of a molecularly dehydrated phosphate on
not indicate how much calcium carbonate will deposit, the stability index of a water was studied. The
nor does it indicate whether a state of supersatura- polyphosphates have the ability of stabilizing an oth-
tion will be present that will be great enough to pro- erwise unstable water. In the presence of small
duce a precipitate, or whether it is great enough to amounts of these phosphates, a water that would or-
give a protective film. This can be seen more clearly dinarily form a heavy deposit of CaCO3 remains stable
by assuming that there are two waters with the fol- for extended periods of time.
lowing characteristics:
Water A at 75°C; pHs = 6.0;
actual pH = 6.5; EXPERIMENTAL WORK
Saturation Index = + 0.5
Water B at 75°C; pHs = 10.0; In determining the pHs of a water, the constants and
actual pH = 10.5 corrections for salinity and temperature as given by
Saturation Index = + 0.5 Larson and Buswell were used. At higher dissolved
solids and temperatures, the values were extrapolated
The saturation index would predict both waters to be using the same formulas as for obtaining pHs at the
equally scale forming. Actually, water A would be scale lower dissolved solids and temperatures. No attempt
forming, while water B would be quite corrosive. was made to check experimentally, at the higher tem-
To eliminate misinterpreting a positive saturation peratures and salinity, the values thus obtained of
index as being non-corrosive or scale forming, a new the constants K'2 and K's.
empirical expression, 2pHs – pH, is proposed. Experimental tests to determine the amount of scale
The value obtained by the expression 2pHs – pH is formed by various waters were made on waters
called the stability index to differentiate it from the having different 2pHs – pH values and on different
saturation index. This stability index is not only an waters having similar 2pHs – pH values.
index of CaCO3 saturation, but is also of quantitative The equipment for carrying out these tests is shown
significance. Using this expression, waters are much in Figure 1. In the tests reported, the water was
more accurately typed to determine whether scale passed through the system only once.
formation or corrosion is to be expected.
Experimental data have been correlated with this ex-
pression so that a semi-quantitative value can be
derived for the amount of calcium carbonate scale that
will be formed, and a qualitative estimate can be made
to indicate whether serious corrosion may be expected.
Using waters A and B, the following values would be
obtained for the stability index:
Water A Water B
Saturation Index +0.5 +0.5
Stability Index +5.5 +9.5
Unlike the saturation indexes for these two waters,
the stability indexes are quite different. The stabil-
ity index will be positive for all waters. Experimen-
tal results obtained on various waters indicate that
the behavior of natural and treated waters having a
stability index of 5.5 will be similar and will give an
appreciable amount of calcium carbonate scale.
Waters having a stability index of 9.5 will form only
a limited amount of calcium carbonate scale and may be
severely corrosive, especially at higher temperatures. Figure 1 — Apparatus for incrustation tests
Two tests were made simultaneously. The coils were
carefully cleaned, dried, and weighed before and
after each test to determine the amount of scale de-
posited from the water.
The constant temperature baths could be adjusted to
give an effluent temperature of the water from room
temperature to the boiling point at any desired flow
rate. The tests reported here were made at effluent
temperatures of 120, 160, and 200°F. All tests were
of two hours’ duration with a flow rate of 1 gallon.
This apparatus has been used in the laboratory for
several years and gives results that can be easily
reproduced.
The incrustation obtained in these glass coils has been
checked with field results. Good correlation has been
obtained in all cases, so that a water giving a certain
number of milligrams deposit can be predicted either
as giving trouble-free conditions or an objectionable
scale in a certain length of time. This permits rapid
Figure 2 — Laboratory results showing relationship
recommendation of the proper stabilizing or correc- between stability index and incrustation
tive treatment where necessary.
The results on incrustation on various waters are plot-
ted against the stability index (Figure 2). Without
stabilizing treatment, a water having a stability in- plete and the history of the behavior of the water was
dex of approximately 6.0 or less is definitely scale known. The values for pHs were calculated, using the
forming, while an index above 7.0 may not give a pro- formula of Larson and Buswell.
tective coating of calcium carbonate scale. Corrosion
In most of the cases very little information was given
would become an increasingly greater problem as the
in the literature regarding the condition of the cold-
stability index increased to above 7.5 or 8.0.
water mains. The stability index, in most cases, indi-
With polyphosphate, a water with a stability index cated a corrosive tendency was present. The reactions
as low as 4.0 can be used at temperatures up to 200°F in the cold may have been slow and escaped notice,
with little danger of scale formation. Inasmuch as but it is felt that tuberculation due to corrosion had
these phosphates also have definite corrosion inhibit- in too many cases been taken in a matter-of-fact way
ing powers, a water with a stability index around 7.0 – as something to be expected.
8.5 may be profitably treated with these phosphates.
A New England Water Works Association (NEWWA)
Although the points in the curves lie fairly close along report shows that, based on tests of 473 pipelines in
the plotted lines, it is not claimed that any and all 19 different systems, the average loss in capacity of
waters will fit the curves as well. It is quite possible tar-coated cast iron pipe, after 30 years of service,
in some cases that the stability index may be low, was 52%. Small mains carrying active water may lose
indicating a scaling tendency. Yet if the alkalinity is over 60% of their capacity in this length of time. This
due mainly to hydroxyl ion, there would be very little represents a serious economic loss. Although tuber-
CO3 present to give CaCO3. This would be especially culation due to corrosion is the most frequent cause
true of some lime-soda softened waters. However, it of loss of flow due to increased friction, in certain cases
is felt that a water having a stability index of 7.5 or this could be due to incrustation formed by an un-
more will not form a protective layer of CaCO3. stable water.
To determine how the laboratory results compare with The data obtained by NEWWA indicated that there
field results, a number of cases were taken at ran- was a marked correlation between the pH value of
dom, in which the analyses of the waters were com- water carried and the rate of capacity loss in the
 mains. Waters with a pH value of 6.5 gave twice the
loss in capacity in a given length of time as those
having a pH value of 8.0.
Apparently, a water having a stability index of ap-
proximately 6.0 at about 60°F, to which a stabilizing
treatment of polyphosphate has been added, should
give the best results in terms of minimum corrosion
and/or scale in the whole system. Under these condi-
tions, corrosiveness due to aggressive carbon dioxide
would be near the minimum in most cases.
On the whole, the field data correlate very well with
the laboratory results for the different stability in-
dexes (Figure 3). Only those values are plotted where
definite information is given for a particular tempera-
ture range. With a stability index of 7.5 or higher at
140°F, corrosion is marked. At indexes of 9.0 or higher,
corrosion is serious.
The stability index should implement the usefulness
of the saturation index, and should help to predict
more accurately how badly scaling or corrosive a par-
ticular water supply may be.

Figure 3 — Field results superimposed on curve A

of Figure 2

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