M Alkalinity and P Alkalinity

Three Types of Alkalinity

Alkalinities are classified according to the endpoint of titration with strong

acid:1

(1a) M alkalinity = Alk = total alkalinity (endpoint: CO2 EP)

(1b) P alkalinity = carbonate alkalinity (endpoint: HCO3- EP)
(1c) caustic alkalinity (endpoint: CO3-2 EP)

Here, “M” refers to the pH indicator methylorange (endpoint 4.2 to 4.5); “P” refers to the pH
indicator phenolphthalein (endpoint 8.2 to 8.3).2 “M alkalinity” is what we usually call
“alkalinity” or “general alkalinity” or “total alkalinity”.

The type of alkalinity found in water depends on the pH, such as P-alkalinity (phenolphthalein)
and M-alkalinity (methyl orange).

The P and M alkalinity values are determined by measuring the acid

neutralizing ability of a water supply to a set pH value.

P-alkalinity is measured down to a pH of 8.3.

The M-alkalinity is measured down to a pH of 4.3.

The M-alkalinity is also called the total alkalinity.

Alkalinity is normally measured in parts per million (ppm) as calcium carbonate.

The different types of alkalinity present can be calculated from the P and M values reported.
Testing Alkalinity In Boiler Water
Alkalinity is a key control parameter for boilers (outside of the prescribed operating range, it can
lead to corrosion, caustic metal embrittlement, and carryover) and cooling water systems (where
it has a significant effect on chemical treatments for scale and corrosion inhibition).

P, M, and T

Depending upon the pH of the water, alkalinity can exist in water in three basic forms: carbonate
(CO3), bicarbonate (HCO3), or hydroxide (OH). Total alkalinity is the sum of these three forms.
Alkalinity is measured by titrating a water sample with a standard acid to a designated pH and is
recorded as P, M, or T alkalinity. P alkalinity is titrated with phenolphthalein to pH 8.3, M
alkalinity with methyl orange indicator to pH 4.6, and T alkalinity with total alkalinity indicator
to pH 4.5. Once you know the values for P, M, or T alkalinity you can use the table of
relationships below to determine treatment control and effectiveness.

Alkalinity Relationships

In boiler water, treatment specialists must maintain M (or T) alkalinity below a maximum level
prescribed by the boiler's manufacturer to help prevent foaming and carryover. Typically, as
boiler operating pressure increases so does the need for higher purity water. At the same time,
water treaters need to maintain a minimum level of OH alkalinity (generally, over 150 ppm as
CaCO3) to prevent scaling tendencies while ensuring excess alkalinity doesn't interfere with
other chemical treatment components. In cooling water, treatment professionals aim to control
alkalinity (and pH) to prevent corrosion and scaling. Below acceptable levels, these parameters
can contribute to corrosion. The higher the pH, the more alkalinity is present in the carbonate
species, which can react with calcium in the water to form scale.