Technical Bulletin

Alkalinity and Water Chemistry

Acid neutralizing minerals in water are known as alkalinity. Alkalinity is either bicarbonate (HCO3)
carbonate (CO3) and/or hydroxide (OH). The alkalinity in most water supplies is caused by dissolved
bicarbonate salts.

The process is dependent on rain water picking up CO2 from the atmosphere and from the respiration
of organisms in the ground. Water and carbon dioxide act to dissolve calcium and magnesium from
minerals in the soil. From this natural occurrence, both hardness (calcium and magnesium) and
alkalinity are dissolved into water. This process is represented by the following two equations:

H2O + CO2 + MgO = Mg(HCO3)2

H2O + CO2 + CaCO3 = Ca(HCO3)2

ALKALINITY IS TYPICALLY CLASSIFIED IN THREE FORMS: M, P AND/OR O.

M ALKALINITY is also known as Total Alkalinity. M Alkalinity is actually methyl orange alkalinity.
This titration endpoint coincides with a pH of 4.2 4.4. M alkalinity is the bicarbonate and carbonate
or carbonate and hydroxide. The laws of chemistry dictate that bicarbonate and hydroxide cannot co-
exist.

P ALKALINITY is phenolphthalein alkalinity. This titration endpoint occurs at a pH of 8.2 8.4. P

alkalinity is the carbonate and all of the hydroxide alkalinity.

O ALKALINITY is a calculation of hydroxide alkalinity. O alkalinity exists only above a pH of 9.8

10.0 and is calculated according to the following formula:

O = 2P M

When the calculation (2P M) result is zero or a negative number, O alkalinity is zero. This will
occur below the 9.8 10.0 pH level.

NO ALKALINITY IS PRESENT IN WATER WITH A PH <4.2

Alkalinity is present in water from a pH of 4.2 4.4 and above. Below 4.2, the methyl orange end-
point, free mineral acidity (FMA) is present. FMA is hydrogen acidity.

Publication Date: 09/16/02 Print Date: 4/14/14 1

A DEFINITION OF pH

Since pH has been referenced frequently in this explanation of alkalinity and is a very important factor
in water chemistry, a definition of pH is necessary.

pH is an indicator of the relative acidity or basicity of water. pH values range from 0 (maximum
acidity) to 14 (maximum basicity). The scientific definition of pH is that ph is the negative logarithm
of the concentration of the hydrogen ion in a solution. A ph value of 7.0 is considered neutral, as
the number of hydrogen and hydroxide ions are equal in numbers.

ALKALINITY AND BUFFERING pH

The reaction of bicarbonate and carbonate alkalinity to buffer (stabilize) pH is critically important in
water chemistry. Without the buffering influence of bicarbonate and carbonate alkalinity, maintaining
pH values between 4.2 and 10.0 would be nearly impossible.

It is useful to recognize the relationship between CO2 and alkalinity. In particular, the relationships
associated with the P endpoint are important. When the pH exceeds 8.2 8.4, the free CO2
disappears and the bicarbonate begins to convert to the carbonate ion. This progresses to a pH of
9.8 10.0 where all of the CO2 is essentially in the form of CO3.

Above the P endpoint the balance between the HCO3, CO3 and OH can be calculated with the
following equation:

Below pH 9.8 10.0

CO3 = 2 x P
HCO3 = M CO3 = M- 2P
OH = Zero

Above pH 9.8 10>0

CO3 = 2(P M)
HCO3 = Zero
OH = 2P - M

SUMMARY

The understanding of the alkalinity relationships in water chemistry is fundamental. Water problems
are frequently the result of scale deposition or corrosion. In their simplest definitions, scale and
corrosion are driven by the instability of calcium carbonate in water. This instability is the tendency
for calcium carbonate to dissolve in water or precipitate from water.

Publication Date: 09/16/02 Print Date: 4/14/14 2