Abundant supplies of fresh water are essential to the development of industry.

Enormous quantities are

required for the cooling of products and equipment, for process needs, for boiler feed, and for sanitary
and potable water supply.

THE PLANETARY WATER CYCLE

Industry is a small participant in the global water cycle .The finite amount of water on the planet
participates in a very complicated recycling scheme that provides for its reuse. This recycling of water is
termed the "Hydrologic Cycle" (see Figure 1-1).

Evaporation under the influence of sunlight takes water from a liquid to a gaseous phase. The water
may condense in clouds as the temperature drops in the upper atmosphere. Wind transports the water
over great distances before releasing it in some form of precipitation. As the water condenses and falls
to the ground, it absorbs gases from the environment. This is the principal cause of acid rain and acid
snow.

WATER AS A SOLVENT

Pure water (H20) is colorless, tasteless, and odorless. It is composed of hydrogen and oxygen.
Because water becomes contaminated by the substances with which it comes into contact, it is not
available for use in its pure state. To some degree, water can dissolve every naturally occurring
substance on the earth. Because of this property, water has been termed a "universal solvent."
Although beneficial to mankind, the solvency power of water can pose a major threat to industrial
equipment. Corrosion reactions cause the slow dissolution of metals by water. Deposition reactions,
which produce scale on heat transfer surfaces, represent a change in the solvency power of water as its
temperature is varied. The control of corrosion and scale is a major focus of water treatment
technology.

WATER IMPURITIES

Water impurities include dissolved and suspended solids. Calcium bicarbonate is a soluble salt. A
solution of calcium bicarbonate is clear, because the calcium and bicarbonate are present as atomic
sized ions which are not large enough to reflect light. Some soluble minerals impart a color to the
solution. Soluble iron salts produce pale yellow or green solutions; some copper salts form intensely
blue solutions. Although colored, these solutions are clear. Suspended solids are substances that are
not completely soluble in water and are present as particles. These particles usually impart a visible
turbidity to the water. Dissolved and suspended solids are present in most surface waters. Seawater is
very high in soluble sodium chloride; suspended sand and silt make it slightly cloudy. An extensive list
of soluble and suspended impurities found in water is given in Table 1-1.

Table 1-1. Common impurities found in fresh water.

Constituent Chemical Formula Difficulties Caused Means of Treatment

imparts unsightly appearance to
water; deposits in water lines,
non-expressed in analysis coagulation, settling, and
Turbidity process equipment, etc.;
as units filtration
interferes with most process
uses
Hardness calcium and magnesium chief source of scale in heat softening; demineralization;
salts, expressed as exchange equipment, boilers, internal boiler water
CaCO3 pipe lines, etc.; forms curds with treatment; surface active
 soap, interferes with dyeing, etc. agents
lime and lime-soda softening;
bicarbonate(HCO3-), foam and carryover of solids with
acid treatment; hydrogen
2-
carbonate (CO3 ), and steam; embrittlement of boiler
zeolite softening;
Alkalinity -
hydroxide(OH ), steel; bicarbonate and carbonate
demineralization
expressed as CaCO3 produce CO2 in steam, a source
dealkalization by anion
of corrosion in condensate lines
exchange

Free Mineral H2SO4 , HCI. etc.,

corrosion neutralization with alkalies
Acid expressed as CaCO3

corrosion in water lines,

Carbon aeration, deaeration,
CO2 particularly steam and
Dioxide neutralization with alkalies
condensate lines
hydrogen ion
concentration defined as: pH varies according to acidic or pH can be increased by
alkaline solids in water; most
PH 1 alkalies and decreased by
natural waters have a pH of 6.0-
pH = log acids
+ 8.0
[H ]
adds to solids content of water,
but in itself is not usually demineralization, reverse
Sulfate SO42- significant, combines with osmosis, electrodialysis,
calcium to form calcium sulfate evaporation
scale
adds to solids content and demineralization, reverse
Chloride Cl - increases corrosive character of osmosis, electrodialysis,
water evaporation
adds to solids content, but is not
usually significant industrially:
demineralization, reverse
- high concentrations cause
Nitrate NO3 osmosis, electrodialysis,
methemoglobinemia in infants;
evaporation
useful for control of boiler metal
embrittlement
cause of mottled enamel in teeth; adsorption with magnesium
also used for control of dental hydroxide, calcium
Fluoride F-
decay: not usually significant phosphate, or bone black;
industrially alum coagulation
adds to solids content of water:
demineralization, reverse
when combined with OH-, causes
Sodium Na+ osmosis, electrodialysis,
corrosion in boilers under certain
evaporation
conditions
hot and warm process
removal by magnesium salts;
scale in boilers and cooling water
adsorption by highly basic
systems; insoluble turbine blade
Silica SiO2 anion exchange resins, in
deposits due to silica
conjunction with
vaporization
demineralization, reverse
osmosis, evaporation
discolors water on precipitation; aeration; coagulation and
source of deposits in water lines, filtration; lime softening;
Fe2+ (ferrous)
Iron 3+ boilers. etc.; interferes with cation exchange; contact
Fe (ferric)
dyeing, tanning, papermaking, filtration; surface active
etc. agents for iron retention
Manganese Mn2+ same as iron same as iron
 usually present as a result of floc
carryover from clarifier; can
improved clarifier and filter
Aluminum AI3+ cause deposits in cooling
operation
systems and contribute to
complex boiler scales
corrosion of water lines, heat
deaeration; sodium sulfite;
Oxygen O2 exchange equipment, boilers,
corrosion inhibitors
return lines, etc.
Hydrogen cause of "rotten egg" odor; aeration; chlorination; highly
H2S
Sulfide corrosion basic anion exchange
corrosion of copper and zinc cation exchange with
Ammonia NH3 alloys by formation of complex hydrogen zeolite;
soluble ion chlorination; deaeration
refers to total amount of
lime softening and cation
dissolved matter, determined by
exchange by hydrogen
Dissolved evaporation; high concentrations
none zeolite; demineralization,
Solids are objectionable because of
reverse osmosis,
process interference and as a
electrodialysis, evaporation
cause of foaming in boilers
refers to the measure of
undissolved matter, determined subsidence; filtration, usually
Suspended
none gravimetrically; deposits in heat preceded by coagulation and
Solids
exchange equipment, boilers, settling
water lines, etc.
refers to the sum of dissolved
see "Dissolved Solids" and
Total Solids none and suspended solids,
"Suspended Solids"
determined gravimetrically

Surface Water

The ultimate course of rain or melting snow depends on the nature of the terrain over which it flows. In
areas consisting of hard packed clay, very little water penetrates the ground. In these cases, the water
generates "runoff". The runoff collects in streams and rivers. The rivers empty into bays and estuaries,
and the water ultimately returns to the sea, completing one major phase of the hydrologic cycle shown
in Figure 1-1.

As water runs off along the surface, it stirs up and suspends particles of sand and soil, creating silt in
the surface water. In addition, the streaming action erodes rocky surfaces, producing more sand. As the
surface water cascades over rocks, it is aerated. The combination of oxygen, inorganic nutrients
leached from the terrain, and sunlight supports a wide variety of life forms in the water, including algae,
fungi, bacteria, small crustaceans, and fish.

Often, river beds are lined with trees, and drainage areas feeding the rivers are forested. Leaves and
pine needles constitute a large percentage of the biological content of the water. After it dissolves in the
water, this material becomes a major cause of fouling of ion exchange resin used in water treatment.

The physical and chemical characteristics of surface water contamination vary considerably over time.
A sudden storm can cause a dramatic short term change in the composition of a water supply. Over a
longer time period, surface water chemistry varies with the seasons. During periods of high rainfall, high
runoff occurs. This can have a favorable or unfavorable impact on the characteristics of the water,
depending on the geochemistry and biology of the terrain.

Surface water chemistry also varies over multi year or multidecade cycles of drought and rainfall.
 Extended periods of drought severely affect the availability of water for industrial use. Where rivers
discharge into the ocean, the incursion of salt water up the river during periods of drought presents
additional problems. Industrial users must take surface water variability into account when designing
water treatment plants and programs.

Groundwater

Water that falls on porous terrains, such as sand or sandy loam, drains or percolates into the ground. In
these cases, the water encounters a wide variety of mineral species arranged in complex layers, or
strata. The minerals may include granite, gneiss, basalt, and shale. In some cases, there may be a
layer of very permeable sand beneath impermeable clay. Water often follows a complex three
dimensional path in the ground. The science of groundwater hydrology involves the tracking of these
water movements.

Table 1-2. A comparison of surface water and groundwater characteristics.

Characteristic Surface Water Ground Water

Turbidity high low
Dissolved minerals low-moderate high
Biological content high low
Temporal variability very high low

In contrast to surface supplies, groundwaters are relatively free from suspended contaminants, because
they are filtered as they move through the strata. The filtration also removes most of the biological
contamination. Some groundwaters with a high iron content contain sulfate reducing bacteria. These
are a source of fouling and corrosion in industrial water systems.

Groundwater chemistry tends to be very stable over time. A groundwater may contain an undesirable
level of scale forming solids, but due to its fairly consistent chemistry it may be treated effectively.

Mineral Reactions: As groundwater encounters different minerals, it dissolves them according to their
solubility characteristics. In some cases chemical reactions occur, enhancing mineral solubility.

A good example is the reaction of groundwater with limestone. Water percolating from the surface
contains atmospheric gases. One of these gases is carbon dioxide, which forms carbonic acid when
dissolved in water. The decomposition of organic matter beneath the surface is another source of
carbon dioxide. Limestone is a mixture of calcium and magnesium carbonate. The mineral, which is
basic, is only slightly soluble in neutral water. The slightly acidic groundwater reacts with basic
limestone in a neutralization reaction that forms a salt and a water of neutralization. The salt formed by
the reaction is a mixture of calcium and magnesium bicarbonate. Both bicarbonates are quite soluble.
This reaction is the source of the most common deposition and corrosion problems faced by industrial
users. The calcium and magnesium (hardness) form scale on heat transfer surfaces if the groundwater
is not treated before use in industrial cooling and boiler systems. In boiler feedwater applications, the
thermal breakdown of the bicarbonate in the boiler leads to high levels of carbon dioxide in condensate
return systems. This can cause severe system corrosion.

Structurally, limestone is porous. That is, it contains small holes and channels called "interstices". A
large formation of limestone can hold vast quantities of groundwater in its structure. Limestone
formations that contain these large quantities of water are called aquifers, a term derived from Latin
roots meaning water bearing.
 If a well is drilled into a limestone aquifer, the water can he withdrawn continuously for decades and
used for domestic and industrial applications. Unfortunately, the water is very hard, due to the
neutralization/dissolution reactions described above. This necessitates extensive water treatment for
most uses.

CHEMICAL REACTIONS

Numerous chemical tests must be conducted to ensure effective control of a water treatment program.
Most of these tests are addressed in detail in Chapters 39-71. Because of their significance in many
systems, three tests, pH, alkalinity, and silica, are discussed here as well.

pH Control

Good pH control is essential for effective control of deposition and corrosion in many water systems.
Therefore, it is important to have a good understanding of the meaning of pH and the factors that affect
it.

Pure H2O exists as an equilibrium between the acid species, H+ (more correctly expressed as a
protonated water molecule, the hydronium ion, H30+) and the hydroxyl radical, OH -. In neutral water
the acid concentration equals the hydroxyl concentration and at room temperature they both are
present at 10-7 gram equivalents (or moles) per liter.

The "p" function is used in chemistry to handle very small numbers. It is the negative logarithm of the
number being expressed. Water that has 10-7 gram equivalents per liter of hydrogen ions is said to
have a pH of 7. Thus, a neutral solution exhibits a pH of 7. Table 1-3 lists the concentration of H+ over
14 orders of magnitude. As it varies, the concentration of OH - must also vary, but in the opposite
direction, such that the product of the two remains constant.

Table 1-3. pH relationships.

OH - Concentration,
H+ Concentration
pH H+ Concentration, -
OH Concentration, Exponential
a Exponential Notation, pOH -
Normality Normality Notation, gram
gram moles/L
moles/L
0 100 1 0.00000000000001 10-14 14
1 10-1 0.1 0.0000000000001 10--13 13
2 10-2 0.01 0.000000000001 10--12 12
3 10-3 0.001 0.00000000001 10-11 11
4 10-4 0.0001 0.0000000001 10 -10
10
5 10-5 0.00001 0.000000001 10-9 9
-6 -8
6 10 0.000001 0.00000001 10 8
7 10-7 0.0000001 0.0000001 10-7 7
8 10-8 0.00000001 0.000001 10-6 6
9 10-9 0.000000001 0.00001 10-5 5
10 10-10 0.0000000001 0.0001 10-4 4
11 10-11 0.00000000001 0.001 10-3 3
12 10-12 0.000000000001 0.01 10-2 2
13 10-13 0.0000000000001 0.1 10-1 1
14 10-14 0.00000000000001 1 100 0

a
pH+pOH=14.
 Confusion regarding pH arises from two sources:

 the inverse nature of the function

 the pH meter scale

It is important to remember that as the acid concentration increases, the pH value decreases (see Table
1-4).

Table 1-4. Comparative pH levels of common solutions.

12 OH - alkalinity 500 ppm as CaCO3

OH - alkalinity 50 ppm as CaCO3
11
Columbus. OH, drinking water, a
10 OH - alkalinity 5 ppm as CaCO3
9 strong base anion exchanger effluents
8 phenolphthalein end point
7 neutral point at 25 °C
6 Weymouth, NIA, drinking water, a
5 methyl orange end point
4 FMA 4 ppm as CaCO3
FMA 40 ppm as CaCO3
3
strong acid cation exchanger effluent
2 FMA 400 ppm as CaCO3

a
Extremes of drinking water pH

The pH meter can be a source of confusion, because the pH scale on the meter is linear, extending
from 0 to 14 in even increments. Because pH is a logarithmic function, a change of I pH unit
corresponds to a 10 fold change in acid concentration. A decrease of 2 pH units represents a 100 fold
change in acid concentration.

Alkalinity

Alkalinity tests are used to control lime-soda softening processes and boiler blowdown and to predict
the potential for calcium scaling in cooling water systems. For most water systems, it is important to
recognize the sources of alkalinity and maintain proper alkalinity control.

Carbon dioxide dissolves in water as a gas. The dissolved carbon dioxide reacts with solvent water
molecules and forms carbonic acid according to the following reaction:

CO2 + H2O = H2CO3

Only a trace amount of carbonic acid is formed, but it is acidic enough to lower pH from the neutral point
of 7. Carbonic acid is a weak acid, so it does not lower pH below 4.3. However, this level is low enough
to cause significant corrosion of system metals.

If the initial loading of CO2 is held constant and the pH is raised, a gradual transformation into the
bicarbonate ion HCO3- occurs. This is shown in Figure 1-2.
 The transformation is complete at pH 8.3. Further elevation of the pH forces a second transformation
into carbonate, CO32-. The three species carbonic acid, bicarbonate, and carbonate can be converted
from one to another by means of changing the pH of the water.

Variations in pH can be reduced through "buffering" the addition of acid (or caustic). When acid (or
caustic) is added to a water containing carbonate/bicarbonate species, the pH of the system does not
change as quickly as it does in pure water. Much of the added acid (or caustic) is consumed as the
carbonate/bicarbonate (or bicarbonate/carbonic acid) ratio is shifted.

Alkalinity is the ability of a natural water to neutralize acid (i.e., to reduce the pH depression expected
from a strong acid by the buffering mechanism mentioned above). Confusion arises in that alkaline pH
conditions exist at a pH above 7, whereas alkalinity in a natural water exists at a pH above 4.4.

Alkalinity is measured by a double titration; acid is added to a sample to the Phenolphthalein end point
(pH 8.3) and the Methyl Orange end point (pH 4.4). Titration to the Phenolphthalein end point (the P-
alkalinity) measures OH - and 1/2 CO32-; titration to the Methyl Orange end point (the M-alkalinity)
measures OH -, CO32- and HCO3 .

Silica

When not properly controlled, silica forms highly insulating, difficult to remove deposits in cooling
systems, boilers, and turbines. An understanding of some of the possible variations in silica testing is
valuable.

Most salts, although present as complicated crystalline structures in the solid phase, assume fairly
simple ionic forms in solution. Silica exhibits complicated structures even in solution.

Silica exists in a wide range of structures, from a simple silicate to a complicated polymeric material.
The polymeric structure can persist when the material is dissolved in surface waters.

The size of the silica polymer can be substantial, ranging up to the colloidal state. Colloidal silica is
rarely present in groundwaters. It is most commonly present in surface waters during periods of high
runoff.

The polymeric form of silica does not produce color in the standard molybdate based colorimetric test
for silica. This form of silica is termed "nonreactive". The polymeric form of silica is not thermally stable
and when heated in a boiler reverts to the basic silicate monomer, which is reactive with molybdate.

As a result, molybdate testing of a boiler feedwater may reveal little or no silica, while boiler blowdown
measurements show a level of silica that is above control limits. High boiler water silica and low
feedwater values are often a first sign that colloidal silica is present in the makeup.

One method of identifying colloidal silica problems is the use of atomic emission or absorption to
measure feedwater silica. This method, unlike the molybdate chemistry, measures total silica
irrespective of the degree of polymerization