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Alkalinity is the presence of
alkaline (acid neutralizing)
minerals in water. By definition,
total alkalinity — also called
“M alkalinity” — is that which
produces a pH above the methyl
orange (M) endpoint of about
4.2–4.4, and which reacts with
mineral acids to produce a neutral
salt at the M endpoint. Also by
definition, then, alkalinity ceases
to exist at pH 4.2–4.4, and further
reduction of pH produces free
mineral acidity. The concentra-
tion of acidity is measured by pH,
partly influenced by the level of
total dissolved solids according to
Table 1.
Table 1 — Mineral acidity* vs pH value
H+, ppm as CaCO3
2–3
4–5
6–7
8–9
10–11
12–13
14–16
17–20
21–25
26–30
31–40
41–50
*Mineral acidity is reported as the H+ ion.
Another significant alkalinity
measure is “P alkalinity,” which
exists at pH's above the phenol-
phthalein end-point range of pH
8.2–8.4.
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Alkalinity Relationships
in Water Chemistry
TF-84
In general, the alkalinity of most
natural water supplies is caused
by dissolved bicarbonate salts.
The following equations show
how rain, picking up CO2 from
the atmosphere and from the
respiration of soil organisms,
dissolves magnesium and calcium
from a common mineral, dolo-
mite, to produce hardness and
alkalinity in ground water: Figure 1 — Approximate relationship
of carbon dioxide, alkalinity, and pH
H2O + 2CO2 + MgO → Mg (HCO3)2 value
H2O + CO2 + CaCO3 → Ca (HCO3)2
There remains a balance between
In the region above pH 8.2–8.4,
excess CO2 and bicarbonate ions,
the “P” endpoint, it is convenient
which is measured by pH value,
to use a “shorthand” device to
as shown in Figure 1.
easily calculate the balance
Theoretically, a pH of 7.0 repre- between HCO3, CO3, and OH
pH sents a neutral system, with based on P and M alkalinities.
4.3 higher pH being alkaline and These expressions are as follows:
4.0 lower pH acid. Obviously, in
Below pH 9.8–10.0 (where P Alk. is
3.9 water chemistry the expression
less than 1/2 M Alk.):
3.8 “neutral pH” has little or no
3.7 meaning, since even at a pH of 5, CO3 = 2 x P Alk.
3.6 alkalinity is present. To properly HCO3 = M – CO3 = M – 2P
3.5 define a water condition, pH OH = Zero
3.4 should be expressed accurately.
Above pH 9.8–10.0 (where P Alk.
3.3
When the pH exceeds 8.2–8.4, the exceeds 1/2 M Alk.):
3.2
free CO2 disappears and the
3.1 CO3 = 2 (M – P)
bicarbonate begins to convert to
3.0 OH = 2P – M
the carbonate ion. This progresses
HCO3 = Zero
to a pH of about 9.8–10, at which
point all of the CO2 - originating
alkalinity is essentially in the form
of carbonate.
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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
temperature)
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
supply with a calcium hardness
of 240 ppm, an alkalinity of 190
ppm, and pH 6.8. The saturation
pH (pHs) is found to be 7.3. The
Langelier Index is —
pH – pHs = 6.8 – 7.3 = –0.5
The Langelier Index assumes that
a positive value shows the water
to be scale forming (CaCO3 will
probably drop out), and a nega-
tive value indicates corrosive
tendencies. (This is an over-
simplification, since the concen-
tration of dissolved oxygen has
a pronounced effect.)
Working from these data, Ryznar
evaluated the Langelier Index
against actual field experiences
with corrosive and scale-forming
waters in municipal systems. He
developed his Stability Index,
whereby
SI = 2 pHs – pH
and in this framework an index
over 6 was found to be corrosive
and below 6, scaling.
A final consideration is the
importance of buffer effect in
alkaline waters. This can be a
critical factor where careful
control of pH may be necessary in
treating either a raw water supply
or a wastewater. As an example
of this, compare the neutraliza-
tion of NaOH to the neutraliza-
In titrating a mixture of OH and
CO3, the following would apply:
1. At the P endpoint, all OH and
1/2CO3 would be reacted.
2. At the M endpoint, all OH and
all CO3 would be reacted, or,
P = 1/2CO3 + OH; 2P = CO3 + 2OH
M = CO3 + OH; M = CO3 + OH
Figure 3 — Neutralization of alkaline Subtracting, 2P – M = OH
water with H2SO4 (assume 50 ppm
M alkalinity)
Since M is total alkalinity,
CO3 = (M – OH) = [M – (2P – M)]
tion of Na2CO3, as shown in = 2 (M – P)
Figure 3. It is obvious that it is
virtually impossible to control the In summary, the relationships of
pH of the NaOH neutralization at the various forms of alkalinity in
water are fundamental to any
pH 7, since there is a vertical drop
between pH 9 and 4.3. As a evaluation of problems in water
systems. These basic relation-
corollary to this, it is considerably
easier to control the pH of an ships can be used to control such
diverse operations as corrosion
acidic waste with Na2CO3 than
with NaOH, provided the CO2 control, lime softening, and pH
correction.
generation can be controlled
without excessive foaming.
Figure 3 provides the basis for the
P–M rules of thumb for calculat-
ing HCO3– CO3– OH relationships
expressed earlier. On the NaOH
neutralization curve —
P = M = OH
while on the Na2CO3 curve
P = 1/2 M = 1/2 CO3
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