Water that contains mineral salts of calcium and magnesium, principally as bicarbonates, chlorides, and sulfates, and sometimes iron. Hardness caused by calcium bicarbonate is known as temporary, because boiling converts the bicarbonate to the insoluble carbonate; hardness from the other salts is called permanent. The calcium and magnesium in hard waters form a hard, adherent scale on boiler plates, increasing fuel consumption and leading to deterioration through overheating. Home water softeners consist of tanks containing zeolite minerals or ion-exchange resins, which contain sodium ions that change places with the calcium and magnesium.
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Hard water is the type of water that has high mineral content (in contrast with soft water). Hard water minerals primarily consist of calcium (Ca2+), and magnesium (Mg2+) metal cations, and sometimes other dissolved compounds such as bicarbonates and sulfates. Calcium usually enters the water as either calcium carbonate (CaCO3), in the form of limestone and chalk, or calcium sulfate (CaSO4), in the form of other mineral deposits. The predominant source of magnesium is dolomite (CaMg(CO3)2). Hard water is generally not harmful.
The simplest way to determine the hardness of water is the lather/froth test: soap or toothpaste, when agitated, lathers easily in soft water but not in hard water. More exact measurements of hardness can be obtained through a wet titration. The total water 'hardness' (including both Ca2+ and Mg2+ ions) is read as parts per million or weight/volume (mg/L) of calcium carbonate (CaCO3) in the water. Although water hardness usually only measures the total concentrations of calcium and magnesium (the two most prevalent, divalent metal ions), iron, aluminium, and manganese may also be present at elevated levels in some geographical locations.
Temporary hardness is caused by a combination of calcium ions and bicarbonate ions in the water. It can be removed by boiling the water or by the addition of lime (calcium hydroxide). Boiling promotes the formation of carbonate from the bicarbonate and precipitates calcium carbonate out of solution, leaving water that is softer upon cooling.
The following is the equilibrium reaction when calcium carbonate (CaCO3) is dissolved in water:
CaCO3(s) + H2CO3(aq) ⇋ Ca2+(aq) + 2HCO3-(aq)
Upon heating, less CO2 is able to dissolve into the water (see Solubility). Since there is not enough CO2 around, the reaction cannot proceed from left to right, and therefore the CaCO3 will not dissolve as rapidly. Instead, the reaction is forced to the left (i.e. products to reactants) to re-establish equilibrium, and solid CaCO3 is formed. Boiling the water will remove hardness as long as the solid CaCO3 that precipitates out is removed. After cooling, if enough time passes the water will pick up CO2 from the air and the reaction will again proceed from left to right, allowing the CaCO3 to "re-dissolve" into the water.
For more information on the solubility of calcium carbonate in water and how it is affected by atmospheric carbon dioxide, see calcium carbonate.
Permanent hardness is hardness (mineral content) that cannot be removed by boiling. It is usually caused by the presence of calcium and magnesium sulfates and/or chlorides in the water, which become more soluble as the temperature rises. Despite the name, permanent hardness can be removed using a water softener or ion exchange column, where the calcium and magnesium ions are exchanged with the sodium ions in the column.
Hard water causes scaling, which is the left over mineral deposits that are formed after the hard water had evaporated. This is also known as limescale. The scale can clog pipes, ruin water heaters, coat the insides of tea and coffee pots, and decrease the life of toilet flushing units.
Similarly, insoluble salt residues that remain in hair after shampooing with hard water tend to leave hair rougher and harder to untangle.
In industrial settings, water hardness must be constantly monitored to avoid costly breakdowns in boilers, cooling towers, and other equipment that comes in contact with water. Hardness is controlled by the addition of chemicals and by large-scale softening with zeolite and ion exchange resins.
Because it is the precise mixture of minerals dissolved in the water, together with the water's pH and temperature, that determines the behaviour of the hardness, a single-number scale does not adequately describe hardness. Descriptions of hardness correspond roughly with ranges of mineral concentrations:
LSI = pH - pHs
If the actual pH of the water is below the calculated saturation pH, the LSI is negative and the water has a very limited scaling potential. If the actual pH exceeds pHs, the LSI is positive, and being supersaturated with CaCO3, the water has a tendency to form scale. At increasing positive index values, the scaling potential increases.
Langelier saturation index is defined as:
LSI = pH (measured) - pHs
In practice, water with an LSI between -0.5 and +0.5 will not display enhanced mineral dissolving or scale forming properties. Water with an LSI below -0.5 tends to exhibit noticeably increased dissolving abilities while water with an LSI above +0.5 tends to exhibit noticeably increased scale forming properties.
It is also worth noting that the LSI is temperature sensitive. The LSI becomes more positive as the water temperature increases. This has particular implications in situations where well water is used. The temperature of the water when it first exits the well is often significantly lower than the temperature inside the building served by the well or at the laboratory where the LSI measurement is made.
Ryznar saturation index (RSI) was developed from empirical observations of corrosion rates and film formation in steel mains.
Ryznar saturation index is defined as:
RSI = 2 pHs – pH (measured)
Some studies have shown a weak inverse relationship between water hardness and cardiovascular disease in men, up to a level of 170 mg calcium carbonate per litre of water. The World Health Organization has reviewed the evidence and concluded the data were inadequate to allow for a recommendation for a level of hardness.
In a review by František Kožíšek, M.D., Ph.D. National Institute of Public Health, Czech Republic there is a good overview of the topic, and unlike the WHO, sets some recommendations for the maximum and minimum levels of calcium (40-80 mg/L) and magnesium (20-30 mg/L) in drinking water, and a total hardness expressed as the sum of the calcium and magnesium concentrations of 2-4 mmol/L.
Other studies have shown weak correlations between cardiovascular health and water hardness.
The most economical way to soften household water is with an ion exchange water softener. This unit uses sodium chloride (table salt) to recharge beads made of the ion exchange resins that exchange hardness mineral ions for sodium ions. Artificial or natural zeolites can also be used. As the hard water passes through and around the beads, the hardness mineral ions are preferentially absorbed, displacing the sodium ions. This process is called ion exchange. When the bead or sodium zeolite has a low concentration of sodium ions left, it is exhausted, and can no longer soften water. The resin is recharged by flushing (often back-flushing) with saltwater. The high excess concentration of sodium ions alter the equilibrium between the ions in solution and the ions held on the surface of the resin, resulting in replacement of the hardness mineral ions on the resin or zeolite with sodium ions. The resulting saltwater and mineral ion solution is then rinsed away, and the resin is ready to start the process all over again. This cycle can be repeated many times.
The discharge of brine water during this regeneration process has been banned in some jurisdictions (notably California, USA) due to concerns about the environmental impact of the discharged sodium.
Some softening processes in industry use the same method, but on a much larger scale. These methods create an enormous amount of salty water that is costly to treat and dispose of.
Temporary hardness, caused by hydrogen carbonate (or bicarbonate) ions, can be removed by boiling. For example, calcium hydrogen carbonate, often present in temporary hard water, is boiled in a kettle to remove the hardness. In the process, a scale forms on the inside of the kettle in a process known as "furring". This scale is composed of calcium carbonate.
Ca(HCO3)2 → CaCO3 + CO2 + H2O
Hardness can also be reduced with a lime-soda ash treatment. This process, developed by Thomas Clark in 1841, involves the addition of slaked lime (calcium hydroxide — Ca(OH)2) to a hard water supply to convert the hydrogen carbonate hardness to carbonate, which precipitates and can be removed by filtration:
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
The addition of sodium carbonate also softens permanently hard water containing calcium sulfate, as the calcium ions form calcium carbonate which precipitates out and sodium sulfate is formed which is soluble. The calcium carbonate that is formed sinks to the bottom. Sodium sulfate has no effect on the hardness of water.
Na2CO3 + CaSO4 → Na2SO4 + CaCO3
However, the chemical explanation is that softened water, due to its sodium content, has a much reduced ability to combine with the soap film on your body and therefore, it is much more difficult to rinse off. Solutions are to use less soap or a synthetic liquid body wash.