Drew Marine

Relationship between pH and Alkalinity

Introduction
Alkalinity and pH are used in water treatment as an indication of the scaling or corrosion potential of water and
they are often confused as to their relationship and interpretation. This paper will help to distinguish the
difference between them and why the difference is important in water treatment.
Simply stated, the measurement of pH broadly indicates acidity, alkalinity or neutrality of a water solution and
controlling a water treatment program on pH alone can be problematic. For example, an alkalinity titration
defines the form of alkalinity as being bicarbonate, carbonate or hydrate alkalinity. In boiler water treatment, It
is the hydrate alkalinity form that is important for proper sludge conditioning. Measuring pH in boiler water will
not define the hydrate alkalinity.

pH
+

Pure water dissociates to form hydrogen ions, H , and hydroxide ions, OH as seen in the following equation:
H2O

OH

At equilibrium, the concentration of the hydrogen ion times the concentration of the hydroxide ion is a constant
-14
value, known as the dissociation constant. For water, the dissociation constant is 10 or 0.00000000000001.
It is cumbersome to refer to hydrogen and hydroxide ion concentrations in this way, so to simplify matters the
hydrogen ion concentration is expressed as the negative logarithm. As an example, the negative logarithm of
-7
10 becomes 7. The abbreviation for the negative logarithm of the hydrogen ion concentration is pH. The
abbreviation for the negative logarithm of the hydroxyl ion concentration is pOH. The simplified equilibrium
reaction equation becomes:
pH

pOH

14

The relationships between H+, OH-, pH and pOH are shown below.
H+
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
-8
10
-9
10
-10
10
-11
10
-12
10
-13
10

OH-13
10
-12
10
-11
10
-10
10
-9
10
-8
10
-7
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
10

pH
1
2
3
4
5
6
7
8
9
10
11
12
13

pOH
13
12
11
10
9
8
7
6
5
4
3
2
1

The pH scale of 0 to 14 indicates the acidity or alkalinity of a water sample, with 7 being the midpoint noting
neutrality. As the hydrogen ion concentration increases, the solution becomes more acidic and the pH
decreases. As the hydrogen ion concentration decreases, the solution becomes more alkaline and the pH
increases.
Since pH is a logarithmic function, as the hydrogen ion concentration increases by a factor of 10, the pH
decreases by one unit. Conversely, as the hydroxide ion concentration increases by a factor of 10, the pH
increases by one unit.
Changes in pH are caused by the addition of acids (substances that contribute hydrogen ions) and bases
(substances that contribute hydroxide ions) to the water. Theoretically pure water, such as distilled or
deionized water has a pH of 7.0. However, carbon dioxide gas dissolved in the water can cause the pH to be
6.5 or lower. Other impurities may have an effect on the pH.
Measuring pH in buffered waters (waters containing alkalinity that is released when titrated with acid) is fairly
straightforward. Measuring pH in high-purity waters can be problematic since these waters are unbuffered and
can exhibit wide fluctuations in pH as a result of even a slight amount of contamination.

Alkalinity
In natural water, the carbon dioxide, carbonate, and bicarbonate alkalinity equilibrium determine and controls
the pH of the water. In water chemistry, the alkalinity equilibrium is measured and reported as ppm P alkalinity
and ppm T alkalinity using color indicators such as phenolphthalein and bromcresol green methyl red that show
a distinct color change with changes in pH.
P alkalinity exists when the pH is greater than 8.3. A good example of water having a P alkalinity is boiler
water. When boiler water is titrated with acid, the pH steadily decreases as more and more acid is added.
When phenolphthalein is used as the titration indicator, the color of the boiler water sample will change from
pink to colorless when the pH of the sample has decreased to 8.3. This is the P alkalinity or Phenolphthalein
alkalinity and represents all of the hydroxide alkalinity, of the carbonate alkalinity, and 1/3 of the phosphate
and any other alkali producing material present in the sample above a pH of 8.3.
T alkalinity exists when the pH is greater than 4.3. When bromcresol green methyl red indicator is then added
to the boiler water sample above, it will turn a blue green color. As more acid is added, the sample will change
to a form a pinkish purple color when a pH of 4.3 is reached. This is the T alkalinity and represents all of the
hydroxide, all of the carbonate, and 2/3 of the phosphate and other alkali producing material present in the
sample above a pH of 4.3.
Although the P and T alkalinity do not bear any direct relationship to pH, the readings can be used to determine
the carbonate and bicarbonate concentrations in a water sample. The alkalinity determinations represent the
following:
If P alkalinity = 0, all of the alkalinity is bicarbonate
T alkalinity 2P alkalinity = carbonate alkalinity
2P T alkalinity = hydroxide alkalinity
The pH of natural waters is normally less than 8.3 so there is no P alkalinity. They also do not normally have a
pH below 4.3 so they do not contain strong mineral acids.
A graphic representation of the approximate relationship between pH and alkalinity is shown in Figure 1.

Approximate pH and Alkalinity Relationship

Figure 1
14
13

Hydroxide alkalinity
(OH)

12
Carbonate alkalinity
(CO3)

11
10
9
pH

P alkalinity endpoint

8
7

Neutral

Bicarbonate alkalinity
(HCO3)

6
5

T alkalinity endpoint

4
3

Free Mineral Acidity

Carbon Dioxide escapes

2
1
3

Although a pH of 7 is neutral, in water chemistry it is not this pH that separates alkalinity from acidity. In water
chemistry, the pH that separates alkalinity from acidity is approximately 4.3. Waters having a pH below 4.3
are considered to have strong mineral acidity. Waters within the approximate pH range of 4.3 to 8.3
(T alkalinity to P alkalinity) contain bicarbonate alkalinity and weak acids such as carbonic acid (carbon dioxide
in solution) may also exist. In the pH range of approximately 8.3 to 9.6 bicarbonate and carbonate alkalinity
can coexist in the absence of carbon dioxide or hydroxide alkalinity. Above a pH of approximately 9.6,
hydroxide alkalinity becomes measurable.

Summary
It is important to understand the relationship between pH and alkalinity in water treatment to properly interpret
the condition of the water system and the effect of the water treatment program. This ultimately reflects on the
efficiency and life of heat transfer equipment.

WW-3 (11/03)

Drew Marine
One Drew Plaza, Boonton, NJ 07005 USA
Tel: (973) 263-7600 FAX: (973) 263-4491/7463
Drew Marine Web Site: www.drew-marine.com
E-mail: drewmarine@ashland.com

2003 Ashland Inc.

Registered trademark of Ashland Inc. TMTrademark of Ashland Inc.
*Responsible Care and the Responsible Care logo are registered service marks of the American Chemistry Council in the U.S., of the
Canadian Chemical Producers' Association in Canada and of different entities in other countries.