WATER CHEMISTRY

Water is one of the most essential and abundant resources in nature. Three quarters of the
earth's surface is covered with water. The chemical formula for water is H2O. Pure water
is colorless, odorless, and tasteless. Pure water is actually a rarity in nature. Oceans,
rivers, lakes and underground water contain varying amounts of impurities picked up
from the earth as well as dissolved gases picked up from the atmosphere. The impurities
present in a water supply can cause many problems when that water is used in industrial
or commercial heating and cooling systems.

IMPURITIES IN WATER

Most dissolved mineral impurities found in water are present in the form of irons. An ion
is an electrically charged particle. This electrical charge can be either positive or negative.
Ions with a positive (+) electrical charge are called cations. Ions with a negative (-)
electrical charge are called anions. When chemical compound such as calcium carbonate
(CaCO3 ) is dissolved in water, it breaks apart to form the cation calcium (Ca++ ) and the
anion carbonate (CO3-2 ). Under certain circumstances, these ions present in water can
combine again to form the compound.

Ca++ + CO3- - ! CaCO3

Ions have different degrees of electrical charges. The degree of electrical charge of an ion
is termed its valence state and is a measure of its ability to combine with other ions.
Cations may have electrical charges of +1(+), +2(++), +3(+++) or +4(++++). Conversely,
anions may have electrical charges of -1(-), -2(- -), -3(- - -) or -4(- - - -). When anions
combine, the resulting valence of the chemical compound must equal zero. A calcium ion
(Ca-2 ) can combine with one carbonate ion (CO3-2 ) or two chloride ions (Cl ).

Ca++ + CO3 - - ! CaCO3

Ca++ + 2Cl - - ! CaCl2

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This table lists many of the common ions found in water supplies and their valence state.

Positive Ions Symbol Valence Negative Ions Symbol Valence

( Cations ) ( Anions )
Hydrogen H+ + Chloride Cl-
Sodium Na+ + Bicarbonate HCO3--
Calcium Ca++ ++ Hydroxide OH-
Magnesium Mg++ ++ Nitrate NO3--
Ferrous Iron Fe++ ++ Carbonate CO3- -
Aluminum Al+++ +++ Sulfate SO4- -
Ferric Iron Fe+++ +++ Phosphate PO4- - -

Impurities found in water depends greatly upon the source of the water. The two main
sources of water are surface water and ground water. Surface water is water that comes
from lakes, rivers, and oceans. Approximately 80% of all the water used by man is drawn
from surface water supplies. In general, surface water contains the mineral matter that is
dissolved as the water that comes in contact with the earth's crust. Ground water is water
that is stored deep beneath the earth's surface in huge underground reservoirs. It contains
the mineral matter that is dissolved as water filters through the earth's crust. It contains a
higher content of dissolved carbon dioxide as a result of the decay of organic matter
within the earth. The types of impurities in and levels of concentration in a water supply
is a function of the geographic makeup of the area as well as whether it is surface water or
ground water. The following table shows how the composition of water differs depending
upon its source.

CONCENTRATION IN PPM
Miss. Great Well Pacific
River Lakes Water Ocean
Silica as SiO2 13 2.1 12 10
Iron as Fe .1 .01 3.5 trace
Manganese as Mn -- .00 2.5 .01
Calcium as Ca 50 38.0 113.8 400
Magnesium as Mg 14 8.3 19.3 1252
Carbonate as CO3 1.2 .0 .0 0
Bicarbonate as HCO3 158 117 170 140
Sulfate as SO4 97 26 29.0 2650
Chloride as Cl 16 18 76 18980
Nitrate as NO3 4.6 1.8 -- 1.5
Dissolved Solids 326 167 700 34450
Total Hardness as CaCO3 183 130 450 6250
pH (in pH units) 7.9 7.9 6.8 7.5-8.4

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The following is a discussion of several major impurities found in industrial and
commercial water supplies.

HARDNESS

In water treatment terminology, hardness is defined as the calcium (Ca++) and

magnesium (Mg++) ions present in water. Total hardness refers to the sum of the calcium
and magnesium concentrations. Calcium and magnesium ions present in water can
combine with other ions to produce compounds which can precipitate out as scale. The
most common compounds are salts of carbonate and bicarbonate.

Compounds Formula
Calcium Carbonate CaCO3
Calcium Bicarbonate Ca(HCO3)2
Magnesium Carbonate MgCO3
Magnesium Bicarbonate Mg(HCO3)2

Calcium and magnesium ions can combine with a variety of other ions in water to form
other chemical compounds. some of the common ones are listed below.

Compounds Formula
Calcium Sulfate CaSO4
Calcium Chloride CaCl2
Magnesium Nitrate Mg(NO3)2
Magnesium Bicarbonate Mg(OH)2

ALKALINITY

Alkalinity is the measure of those dissolved solids which are alkaline in nature. In
general, alkalinity is expressed as a combination of one or more of the following anions.

ANION SYMBOL
Carbonate CO3- -
Bicarbonate HCO3-
Hydroxide OH-

Hydroxide alkalinity is rarely found in natural water supplies. All forms of alkalinity can
be determined through testing. The presence of bicarbonate alkalinity in boiler water
indicates the probability of carbon dioxide in the boiler. This indicates a need for steam
and condensate treatment. The absence of hydroxide alkalinity and relatively low
amounts of carbonate and bicarbonate alkalinity’s indicates that treatment must provide
for additional alkalinity to raise the alkalinity level of boiler water to recommended level.

CHLORIDES

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Chloride compounds are extremely soluble and generally represent very few problems
with respect to water treatment. When chloride concentrations are abnormally high, they
tend to increase the natural corrosivity of water. Chlorides play an important role in the
control of water characteristics. A chloride test is used to indicate the cycles of
concentration in a boiler or cooling system. By comparing the level of chlorides in the
make-up water the level of chlorides in the recirculation water, the degree to which the
water has concentrated can be determined.

TOTAL DISSOLVED SOLIDS

A measure of all impurities or solids dissolved in water is called the total dissolved solids
(TDS). Control of dissolved solids is vital for a sound water treatment program.
Dissolved solids are generally controlled through mechanical means or precipitation will
occur with or without proper water treatment. The flow of an electrical current through
water is directly related to the level of total dissolved solids present and to the
composition of the dissolved solids. A conductivity meter is often used to measure the
conductance of a water and thus the approximate level of dissolved solids.

pH

The pH value of water provides a value indicating the acidity or alkalinity of a water. The
chart below shows the relationship of acidity and alkalinity expressed a pH.

0 1 2 3 4 5 6 _7 8 9 10 11 12 13 14
Acidic Neutral Alkaline

In water where the level of acid ions equal the number of alkaline ions the water is said to
be neutral. If there are more acidic ions, the water is said to be acidic. If there are more
alkaline ions, the water is said to be alkaline. A change of one pH value represents a
change of 10 times the relative acidity or alkalinity. For example, a pH of 4.0 is ten times
more acidic than a pH of 5.0

CHALLENGES ASSOCIATED WITH IMPURITIES IN WATER

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 SCALE

Water temperature changes have a direct impact upon the solubility’s of chemical
compounds. Some compounds become more soluble as the temperature increases. Others
become more soluble as the temperature decreases. In water treatment systems where
water is being heated or cooled, the solubility of chemical compounds and the ability of
water treatment products to control that solubility become very important. Scale occurs
when the solubility of a particular chemical compound is exceeded either because of
temperature or concentration. Calcium carbonate has a low solubility. The accumulation
of scale on metal heat transfer surfaces greatly reduces the efficiency of heat transfer. The
following list contains some of the most common types of scale.

Calcium Carbonate
Magnesium Hydroxide
Magnesium Silicate
Iron Oxide
Calcium Phosphate
Calcium Sulfate

CORROSION

Corrosion can be defined as metal returning to its original state. Corrosion is an

electrochemical reaction caused by a difference in the electric potential of various
elements. The natural corrosivity of a water will vary with the impurities found in the
water. One common indicator of corrosivity is pH. The lower the pH, the more corrosive
the water. There many other factors that can effect the corrosion. The type and quantity of
dissolved minerals and gases. As well as temperature and velocity of the water has a
direct impact on corrosion. There are many different types of corrosion. Each type can be
identified by the type of reaction and the resulting appearance of the metal surface. The
following list contains some of the major types of corrosion.

Localized Corrosion
Impingement
General Corrosion
Microbiologically Induced Corrosion

MICROBIOLOGICAL CORROSION

Cooling systems experience a number of problems associated with the growth of

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microorganisms (microbes). The organisms can cause fouling of heat exchanger,
microbiological induced corrosion, wood rot, and odor problems. Control of
microorganisms is accomplished through chemical means and mechanical cleaning.

SUMMARY

Water is our most important resource. When water is used in industrial and commercial
heating and cooling systems, there are a number of problems that can arise. These
problems are related to many of factors. The level and type of impurities in the water, the
temperature and velocity of the water, and the degree of microbiological activity in the
water all have a direct impact upon the type and degree of problems. The function of a
water treatment program is to monitor control all of these factors through mechanical and
chemical means.