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 H
+ + -

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 12 11 10 9 pH 8 7 6 5 4 3 2 1 3 Free Mineral Acidity Carbon Dioxide escapes T alkalinity endpoint Neutral P alkalinity endpoint Bicarbonate alkalinity (HCO3) Carbonate alkalinity (CO3) Hydroxide alkalinity (OH)

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
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