Hardness is the sum of the multivalent metal ions in solution, whereas alkalinity is a measure of the solution’s ability to neutralize acids (sum of hydroxide, carbonate and bicarbonate ions). In natural water systems, calcium carbonate is usually present and responsible for different characteristics of the water. Both hardness and alkalinity are expressed as a concentration of CaCO 3 for convenience of reporting a single number to represent multiple chemicals, and for ease in calculating a solution’s carbonate and non-carbonate hardness.
Phenolphthalein alkalinity determination by titration uses a phenolphthalein indicator that changes from pink to colorless at the endpoint. If the sample does not turn pink after adding the indicator, the sample does not have phenolphthalein alkalinity. The sample will not have any phenolphthalein alkalinity if its pH is less than 8.3.
Samples with an acid capacity above 8 mmol/L must be diluted with deionized (DI) water that contains no carbon dioxide (CO 2). One can remove CO 2 from deionized water by boiling. The absence of CO 2 in the water used for dilution can be checked by carrying out a blank measurement. If the samples have high buffering capacity, dilute with DI water. CO 2 in the DI water will interfere when diluting samples or standards for this colorimetric test. The CO 2 free water is not as critical in the titration vs. the colorimetric procedure. The colorimetric test is more sensitive to slight changes in CO 2 concentration due to the colorimetric detection method and small sample volume used.
Some common interferences in alkalinity titration methods include:
- Chlorine – Chlorine at levels above 3.5 mg/L can cause a yellow-brown color when the Bromcresol Green-Methyl Red Powder Pillow is added. To remove the interference, pretreat the sample by adding 1 drop of Sodium Thiosulfate Standard Solution, 0.1 N per 100 mL sample, before adding any other reagents.
- Color or turbidity – Color or turbidity can make it difficult to see the color change at the endpoint. Do not filter or dilute samples with color or turbidity. Use a pH meter and titrate the samples to the specified endpoints:
Sample composition |
Phenolphthalein alkalinity |
Total alkalinity |
Alkalinity approximately 30 mg/L |
pH 8.3 |
pH 4.9 |
Alkalinity approximately 150 mg/L |
pH 8.3 |
pH 4.6 |
Alkalinity approximately 500 mg/L |
pH 8.3 |
pH 4.3 |
Contains silicates or phosphates |
pH 8.3 |
pH 4.5 |
Industrial wastes or complex systems |
pH 8.3 |
pH 4.5 |
Routine or automated analysis |
pH 8.3 |
pH 4.5 |
- Soaps, oily matter, suspended solids and precipitates – Oils or solids can collect on the pH probe and cause a slow response. Clean the probe immediately after use.
Yes, both alkalinity and hardness can be measured together using appropriate testing methods and equipment.
Download our application note on cooling cycle analysis to learn more about measuring alkalinity and hardness in water treatment processes.
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Total Alkalinity
Total alkalinity is a measure in parts per million of all the alkali (all carbonate, bicarbonate and hydroxide ions) present in a sample. Therefore, total alkalinity is a measurement of water's ability to resist changes in pH.
Total alkalinity is determined by titration to a pH of 4.9, 4.6, 4.5, or 4.3, depending on the amount of carbon dioxide present.
Phenolphthalein Alkalinity
Phenolphthalein alkalinity (p-alkalinity) is determined by titration to a pH of 8.3 (the end point when phenolphthalein indicator changes color) and it registers the total hydroxide and one half the carbonate present. Phenolphthalein alkalinity is a subset of total alkalinity.
Typically, hard water is alkaline, while soft water is more acidic. However, exceptions exist in unusual circumstances.
Alkalinity in water is primarily influenced by compounds like bicarbonates, carbonates, and hydroxides of calcium, magnesium, and sodium. These substances act as buffers against pH changes, ensuring water stability. Hach offers comprehensive solutions for accurately measuring and managing alkalinity levels, empowering industries to maintain water quality standards effectively