CHAPTER 1 WATER SOURCES, IMPURITIES, AND CHEMISTRY

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 (H2O) 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.
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.
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.
Table 1-2. A comparison of surface water and groundwater characteristics.
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 break-down 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 be 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 under-standing 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, H3O+) and the hydroxyl radical, OH¯. In neutral water the acid concentration equals the
¯7
hydroxyl concentration and at room temperature they both are present at 10 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
¯7
expressed. Water that has 10 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.
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).
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 1 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
2¯
forces a second transformation–into carbonate, CO3 . 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
½CO3²¯ ; 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.
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Figure 1-1. Global water cycle. (Source: U.S. Geological Survey.)

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Figure 1-2. Carbonic acid, bicarbonate, and carbonate distribution as a function of pH.