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TECHNIFAX® Alkalinity Relationships

in Water Chemistry

Alkalinity is the presence of In general, the alkalinity of most
alkaline (acid neutralizing) natural water supplies is caused
minerals in water. By definition, by dissolved bicarbonate salts.
total alkalinity — also called The following equations show
“M alkalinity” — is that which how rain, picking up CO2 from
produces a pH above the methyl the atmosphere and from the
orange (M) endpoint of about respiration of soil organisms,
4.2–4.4, and which reacts with dissolves magnesium and calcium
mineral acids to produce a neutral from a common mineral, dolo-
salt at the M endpoint. Also by mite, to produce hardness and
definition, then, alkalinity ceases alkalinity in ground water: Figure 1 — Approximate relationship
to exist at pH 4.2–4.4, and further of carbon dioxide, alkalinity, and pH
reduction of pH produces free H2O + 2CO2 + MgO → Mg (HCO3)2 value
mineral acidity. The concentra- H2O + CO2 + CaCO3 → Ca (HCO3)2
tion of acidity is measured by pH,
partly influenced by the level of There remains a balance between
In the region above pH 8.2–8.4,
total dissolved solids according to excess CO2 and bicarbonate ions,
the “P” endpoint, it is convenient
Table 1. which is measured by pH value,
to use a “shorthand” device to
as shown in Figure 1.
easily calculate the balance
Table 1 — Mineral acidity* vs pH value
Theoretically, a pH of 7.0 repre- between HCO3, CO3, and OH
H+, ppm as CaCO3 pH sents a neutral system, with based on P and M alkalinities.
2–3 4.3 higher pH being alkaline and These expressions are as follows:
4–5 4.0 lower pH acid. Obviously, in
Below pH 9.8–10.0 (where P Alk. is
6–7 3.9 water chemistry the expression
less than 1/2 M Alk.):
8–9 3.8 “neutral pH” has little or no
10–11 3.7 meaning, since even at a pH of 5, CO3 = 2 x P Alk.
12–13 3.6 alkalinity is present. To properly HCO3 = M – CO3 = M – 2P
14–16 3.5 define a water condition, pH OH = Zero
17–20 3.4 should be expressed accurately.
Above pH 9.8–10.0 (where P Alk.
21–25 3.3
When the pH exceeds 8.2–8.4, the exceeds 1/2 M Alk.):
26–30 3.2
free CO2 disappears and the
31–40 3.1 CO3 = 2 (M – P)
bicarbonate begins to convert to
41–50 3.0 OH = 2P – M
the carbonate ion. This progresses
*Mineral acidity is reported as the H+ ion. HCO3 = Zero
to a pH of about 9.8–10, at which
point all of the CO2 - originating
Another significant alkalinity alkalinity is essentially in the form
measure is “P alkalinity,” which of carbonate.
exists at pH's above the phenol-
phthalein end-point range of pH



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These approximations are very Table 3 — Approximate relationships of and then filtered was analyzed for
useful, but they may be subject to P, M, and pH (not corrected for TDS or hardness and alkalinity before and
interferences especially in con- after limestone treatment. If it had
taminated waters where ammo- P Alk., % of total a deposit-forming tendency, the
nia may be high, for example. In alkalinity Approx. pH hardness and alkalinity would
some cases, the carbonate is 10 8.2–8.4* drop; if it were an aggressive
precipitated first by addition of 15 8.7–8.9* (corrosive) water, these values
BaCl2, and subsequent titration to 10 9.0–9.2* would increase.
the P endpoint gives hydrate 15 9.3–9.4*
alkalinity alone more accurately Langelier developed an index
20 9.5–9.6* based on solubility products and
than can be calculated from usual 25 9.6–9.7*
P and M relationships. dissociation constants which very
30 9.7–9.8* ingeniously related alkalinity, pH,
Waste waters may contain ions in 35 9.8–9.9* and calcium hardness and deter-
addition to HCO3 and CO3 which 50 9.9–10.0 mined the pH at which saturation
are alkaline, such as bisulfides, *Assuming zero CO2. For pH values below 8.2 should occur at various tempera-
sulfides, and phosphates. When *in presence of CO2 , see Table 2. tures. The Langelier Index in a
dealing with such waters, M and simplified form (uncorrected for
P titrations are inadequate to When free hydroxyl ion appears, concentrations of total dissolved
determine HCO3 – CO3 relation- above pH 9.8–10.0, the concentra- solids) is shown by Figure 2.
ships, and acid evolution of CO2 tion can be approximated from
must be resorted to. Table 2, subject to some variation
caused by the level of total
dissolved solids. Below pH 10,
Table 2 — Caustic alkalinity vs pH the pH may be approximated by
the ratio of P alkalinity to M
OH, ppm as CaCO3 pH
alkalinity, as shown by Table 3.
2–3 9.7
4–5 10.0 These alkalinity relationships are
6–7 10.1 extremely important in water
8–9 10.2 chemistry, since the most promi-
10–11 10.3 nent water problems are deposits
12–13 10.4 and corrosion, and these are
14–16 10.5 closely related to the instability of
17–20 10.6 each specific water caused by the
21–25 10.7 tendency of CaCO3 to dissolve in Figure 2 — Simplified Langelier Index
26–30 10.8 or precipitate from it.
31–40 10.9
In the early days of water chemis-
41–50 11.0
try, the “marble test” was used as
a measure of a water supply's
stability. A sample of water
shaken with finely ground marble
Using this graph, assume a water In titrating a mixture of OH and
supply with a calcium hardness CO3, the following would apply:
of 240 ppm, an alkalinity of 190
1. At the P endpoint, all OH and
ppm, and pH 6.8. The saturation
1/2CO3 would be reacted.
pH (pHs) is found to be 7.3. The
Langelier Index is — 2. At the M endpoint, all OH and
all CO3 would be reacted, or,
pH – pHs = 6.8 – 7.3 = –0.5
P = 1/2CO3 + OH; 2P = CO3 + 2OH
The Langelier Index assumes that
M = CO3 + OH; M = CO3 + OH
a positive value shows the water
to be scale forming (CaCO3 will Figure 3 — Neutralization of alkaline Subtracting, 2P – M = OH
water with H2SO4 (assume 50 ppm
probably drop out), and a nega- M alkalinity)
tive value indicates corrosive Since M is total alkalinity,
tendencies. (This is an over- CO3 = (M – OH) = [M – (2P – M)]
simplification, since the concen- tion of Na2CO3, as shown in = 2 (M – P)
tration of dissolved oxygen has Figure 3. It is obvious that it is
a pronounced effect.) virtually impossible to control the In summary, the relationships of
pH of the NaOH neutralization at the various forms of alkalinity in
Working from these data, Ryznar water are fundamental to any
evaluated the Langelier Index pH 7, since there is a vertical drop
between pH 9 and 4.3. As a evaluation of problems in water
against actual field experiences systems. These basic relation-
with corrosive and scale-forming corollary to this, it is considerably
easier to control the pH of an ships can be used to control such
waters in municipal systems. He diverse operations as corrosion
developed his Stability Index, acidic waste with Na2CO3 than
with NaOH, provided the CO2 control, lime softening, and pH
whereby correction.
generation can be controlled
SI = 2 pHs – pH without excessive foaming.
and in this framework an index Figure 3 provides the basis for the
over 6 was found to be corrosive P–M rules of thumb for calculat-
and below 6, scaling. ing HCO3– CO3– OH relationships
expressed earlier. On the NaOH
A final consideration is the
neutralization curve —
importance of buffer effect in
alkaline waters. This can be a P = M = OH
critical factor where careful
control of pH may be necessary in while on the Na2CO3 curve
treating either a raw water supply P = 1/2 M = 1/2 CO3
or a wastewater. As an example
of this, compare the neutraliza-
tion of NaOH to the neutraliza-


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