SM
TECHNIFAX®
Calcium and magnesium salts
are called water hardness be-
cause they react with soap and
make water hard to wash with.
Softening is the process of
reducing or removing these
hardness minerals. This can be
done with softening chemicals
(lime, soda ash, caustic, phos-
phate, etc.), which react with
dissolved hardness, causing it to
come out of solution. The pre-
cipitated hardness is then settled
out or filtered from the water.
In treating water with chemicals,
the water is also conditioned in
other ways: bicarbonate alkalin-
ity is removed, turbidity is
reduced, and, under proper
conditions, some oxygen, carbon
dioxide, and silica is removed.
The extent of this water condi-
tioning depends on a number of
factors: water temperature, type
and amount of chemicals used,
and equipment used in the
softening process.
Water softening reverses the
conditions under which water
dissolves hardness and holds it
in solution. How hardness gets
into water is, therefore, the key
to how it can be removed.
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Conditioning Water Chemically
HOW WATER DISSOLVES
HARDNESS
Natural waters pick up carbon
dioxide from the air, from micro-
organisms, and from decaying
vegetation. The carbon dioxide
helps water dissolve calcium and
magnesium out of alkaline “rock”
by making the water slightly acid:
H2O + CO2 ↔ H2CO3
water carbon carbonic
dioxide acid
In addition, carbon dioxide helps
keep hardness in solution. It
reacts with dissolved calcium and
magnesium carbonates, making
them more soluble.
CaCO3 + CO2 + H2O → Ca(HCO3)2
calcium calcium
carbonate bicarbonate
MgCO3 + CO2 + H2O → Mg(HCO3)2
magnesium magnesium
carbonate bicarbonate
The bicarbonates formed are more
than a hundred times more
soluble than the carbonates.
SOFTENING PRINCIPLES
For soluble calcium hardness to
be removed, then, the following
two reactions must take place:
1. Conversion of carbon dioxide
to bicarbonate alkalinity
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TF-16
2. Conversion of calcium bicar-
bonate to insoluble calcium
carbonate
Adding enough hydroxide to
raise the pH to a certain level will
force both of these conversions to
take place. For magnesium hard-
ness to be removed, free hydrox-
ide must be present. This free
(1) hydroxide reacts with magnesium
to form insoluble magnesium
hydroxide. Due to economic
considerations, the form of hy-
droxide most often used to raise
the pH in softening is lime
(Ca(OH)2). Figure 1 shows the
relative concentration of the
various carbonate species at
different pH's. As seen in Figure
(2)
1, the reduction of carbon dioxide
continues until the pH reaches
8.2–8.4, at which point the concen-
(3) tration of carbon dioxide drops to
near zero. Above this pH, a
portion of the bicarbonate ion
converts to carbonate. Also, at
pH's above 8.2–8.4, free hydroxide
(OH–) begins to convert bicarbon-
ate alkalinity to carbonate alkalin-
ity. Significant amounts of free
hydroxide do not appear until pH
exceeds 9.8–10.0. Also above this
pH, the relative concentration of
bicarbonate (HCO3–) drops to low
levels with carbonate (CO3–2)
concentration predominating. As

Figure 1 — Alkalinity species as a
function of pH
pH increases in lime softening, the
following interactions between
alkalinity and hardness take place:
1. At typical raw water pH's of
5.5–8.0, carbon dioxide coexists
with bicarbonate alkalinity. The
hydroxide from lime reacts with
carbon dioxide to form bicar-
bonate:
CO2 + OH– ↔ HCO3–
hydroxide bicarbonate
2. When the pH is raised to 8.2, all
of the carbon has reacted to
form bicarbonate alkalinity.
Above pH 8.2, additional
hydroxide reacts with bicarbon-
ate to form carbonate:
HCO3– + OH– → CO3–2 + H2O
carbonate
It is this carbonate that reacts with Lime is not effective in precipitat-
calcium to produce calcium ing hardness that is not associated
carbonate precipitate. According with alkalinity (noncarbonate
to Figure 1, the conversion of hardness). While it does precipi-
bicarbonate to carbonate contin- tate magnesium sulfate, for
ues until pH 10.2 when all the example, the reaction adds
bicarbonate is converted. As more calcium hardness to the solution:
carbonate is produced and the pH
Ca(OH)2 + MgSO4 →
approaches 10.2, more calcium lime magnesium
can precipitate. Above pH 10.2, sulfate
free hydroxide persists, and can Mg(OH)2↓ + CaSO4 (9)
magnesium calcium
precipitate with magnesium. It is hydroxide sulfate
significant that precipitation
occurs only when the required Additional chemicals are needed
alkalinity species is present. to supplement lime in removing
Calcium does not precipitate as both carbonate and noncarbonate
calcium carbonate below pH 8.2, hardness.
and magnesium is not removed in
appreciable amounts below pH
10.2. However, in practice, a small Soda Ash Reactions
percentage of the magnesium will
precipitate during any lime Soda ash (sodium carbonate)
softening operation because of converts hardness salts to the
localized high pH in the vicinity carbonate form, making them less
of the lime feed point. soluble, as shown in the following
reactions:
Na2CO3 + CaSO4 →
soda ash calcium
Lime Reactions sulfate
Lime reacts with CO2, calcium CaCO3↓ + Na2SO4 (10)
calcium sodium
bicarbonate, and magnesium carbonate sulfate
bicarbonate, as shown in the
following reactions: Soda ash is therefore used for
Ca(OH)2 + 2CO2 ↔ Ca(HCO3)2 (6)
precipitation and removal of
noncarbonate hardness.
Ca(OH)2 + Ca(HCO3)2 ↔
2CaCO3↓ + 2H2O (7)
Mg(HCO3)2 + Ca(OH)2 ↔ Lime-Soda Reactions
(4) Mg(OH)2↓ + CaCO3 (8)
When lime and soda ash are added
to the water, they react to form
Remember that for these reactions caustic soda.
to take place, the pH requirements
explained earlier must be met. Na2CO3 + Ca(OH)2 →
soda ash lime
2NaOH + CaCO3↓ (11)
caustic
soda
(5)
(Caustic, as such, is not usually
added to the water alone because
it is difficult to handle and usually
too expensive for softening
reactions.) The caustic produced is
an effective softening chemical:
2NaOH + MgSO4 →
caustic magnesium
sulfate
Mg(OH)2↓ + Na2SO4 (12)
magnesium sodium
hydroxide sulfate
In general, lime and soda ash
produce hardness compounds in
their least soluble form. While
dissolved hardness can be re-
duced to low levels, it is not
completely eliminated by this
process. Good control of softening
chemical dosages is needed for
best results since excess lime can
actually increase hardness by
contributing calcium to the water.
CALCULATING LIME-SODA
DOSAGES
Since lime reacts with carbon
dioxide, calcium bicarbonate, and
magnesium, lime dosages are
based on the amounts of each of
these. A slight excess is usually
figured in the dosage to give a
hydroxide residual. Lime dosages
for hot process softening can be
determined as shown in Figure 2.
For cold process softening, the
diagonal lines represent “P”
alkalinity plus the magnesium
to be removed.
Soda ash reacts with calcium
noncarbonate hardness (calcium
hardness minus the alkalinity) as
shown in Reaction 10. Soda ash
requirements are therefore based
simply on the amount of
noncarbonate hardness in the
water (Figure 3).
Figure 2 — Hot process lime softening
(based on OH excess of 10 ppm)
Figure 3 — Soda ash requirements for
complete softening
Once initial dosages are estab-
lished, some adjustment must be
made routinely (based on control
tests) to take care of variations in
water composition.
SOFTENING AIDS
After the softening chemicals have
reacted, the precipitated hardness
must be effectively removed.
Sodium aluminate aids in the
removal process, reacting with the
precipitated hardness to form
larger particles that can be re-
moved more effectively. It is
especially effective in magnesium
removal. In addition to helping
remove hardness precipitation,
sodium aluminate, which is
alkaline, releases caustic soda as
it dissolves in water:
Na2Al2O4 + 4H2O →
sodium water
aluminate
2Al(OH)3 + 2NaOH (13)
aluminum caustic
hydroxide soda
As illustrated in Reaction 12,
caustic is an effective softening
chemical. Using sodium alumi-
nate, then, will result in a reduc-
tion of lime and/or soda ash
required for softening. Along with
sodium aluminate, two other
types of chemicals can be used to
improve softening: organic coagu-
lants and flocculants. Coagulants
function to neutralize any surface
charge or suspended particles that
may be present in a softener.
Flocculants, which consist of long
molecular chains and branches,
are then added to bridge these
neutralized particles into larger
floc that is more easily filtered.
As a result, settling rates are
improved, and filter run length
is maximized. Unlike sodium
aluminate, coagulants and
flocculants do not release caustic
soda. Jar tests are the best way to
choose the initial dosage and
combination of coagulants, floc-
culants, and sodium aluminate.
HOT VERSUS COLD
PROCESS SOFTENING
Most hardness salts are less
soluble in hot water than in cold.
In addition, the softening reactions
are speeded up as water is heated.
Figure 4 shows the relative effec-
tiveness of hot and cold softening
processes and how sodium alumi-
nate aids softening.
 As the silica content of water gets
lower, it becomes progressively
harder to reduce. In cold process
softening, silica is rarely reduced
below 5 ppm. Hot process soften-
ing, however, can reduce silica to
as low as 1 ppm when chemical
conditions and control are good.

Figure 4 — How sodium aluminate
improves softening
Hot process softening also pro-
vides side benefits. Heating the
water drives off the dissolved
gases, reducing the oxygen and
carbon dioxide in the water. This
reduces lime requirements. Better
silica removal is also accom-
plished in hot process softening.
SILICA REMOVAL
Silica is removed in softening
processes by being adsorbed on
floc that is present in the water. In
cold process softening, sodium
aluminate is most effective in
reducing silica. Sodium aluminate
neutralizes the magnesium
hydroxide precipitates, which in
turn flocculate to form larger floc
that more readily adsorbs or
entraps silica particles in the
water. For reduction of silica in
hot process softeners, the addition
of magnesium oxide is most often
the best method. In colder water,
adding magnesium oxide only
increases total hardness without
significantly reducing silica.
SOFTENING EQUIPMENT
The cold softening process is
either a batch or a continuous
operation. Batch-type softening
simply involves adding chemicals
to water in a tank, allowing the
sludge to settle, and drawing
softened water off the top. Con-
tinuous softening of unheated
water is done in equipment very
similar to that used for clarifica-
tion. Flow rates through the
equipment are usually higher in
softening than in clarifying,
however, since the hardness
precipitates are heavier and settle
faster than natural turbidity.
These are two basic designs of hot
process, lime-soda softeners: the
upflow (sludge blanket) type and
the downflow (up-take funnel)
type. These designs are illustrated
in Figure 5.
In both types, raw water enters
the top and is sprayed with steam
to heat it to within 5–10° of steam
temperature. The hot water
releases most of its “free” carbon
dioxide, and dissolved oxygen is
reduced to about 0.3–0.5 ppm.
These gases are discharged
through vents. Chemicals are
injected into the softener above
the water level to get good distri-
bution. As the chemical reactions
occur, the precipitates accumulate
as sludge.
Figure 5 — Equipment used in hot
process softening
In an upflow softener, the treated
water goes down through a
funnel, or “downcomer.” The
discharge of the lower end of the
funnel is in a blanket of sludge.
The treated water must pass up
through this sludge, which
coagulates and filters the precipi-
tated hardness. In the downflow
softener, the water flows down-
ward and is drawn off through an
inverted funnel. This design is
somewhat less sensitive to rapid
changes in flow rates.
CONCLUSION
The main advantage of lime-soda
softening is that in reducing
hardness, alkalinity, turbidity,
and silica can also be reduced. In
hot process softening, oxygen and
carbon dioxide are also reduced.
The main limitation of lime-soda
softening is that while hardness is
reduced it is not completely
removed. For complete hardness
removal, phosphate or ion ex-
change softening “polishes” the
lime treated water.