Water and solutions

All life depends on water. Water is by far the commonest natural compound on Earth. Water is used to generate electricity, in cooling, transporting things, cleaning and as a medium for reactions. Water is needed to irrigate crops. Most of all it is needed for the correct functioning of our bodies (humans cannot live for more than 7 days without water). Water can be considered as being the oxide of hydrogen - it is a neutral oxide.

Physical properties of pure water

1. Pure water has no smell, no taste and no colour. 2. Pure water boils at 100oC (at a pressure of 760mm mercury) and freezes at 0oC. 3. The solid form of water (ice) is unusual because unlike other substances, it is less dense than the liquid form. This is why ice floats on water. The reason for this is that water expands upon freezing unlike other liquids. This causes pipes to burst in winter. In fact its maximum density is 1gcm-3 at 4oC. 4. The intermolecular forces holding water molecules together are called hydrogen bonds. The water molecule consists of O-H bonds. Now, although this is a covalent bond, where electrons from the atoms are shared, oxygen has a greater affinity for electrons than hydrogen. We say that oxygen is more electronegative than hydrogen. This causes electrons shared between O and H in an O-H bond to be shifted towards the oxygen atom. This leaves a partial positive charge on the hydrogen atom and a partial negative charge on the oxygen atom. 5. This causes intermolecular forces to exist between the O-H bonds of one water molecule and the O-H bond of another molecule. These are called hydrogen bonds. 6. These hydrogen bonds cause water to have a high latent heat of vaporization, i.e. a high amount of heat energy must be applied to convert water to a vapour. Also a part of this energy at first, is not used to increase the temperature of the water but to break the hydrogen bonds between the water molecules. 7. Water is a very good solvent, especially for ionically bonded substances. 8. It is neutral to litmus.

Water and solutions

Solvent action of water

Water has often been described as the universal solvent because it dissolves most common substances, even if for some, it only dissolves them slightly. It is wrong to think that all ionically bonded substances are soluble in water. Calcium carbonate which is ionically bonded, is in fact insoluble in water. Other ionic compounds which are insoluble in water include barium sulfate and silver chloride. It is also wrong to think that all covalently bonded substances are insoluble or barely soluble in water. Chlorine, bromine, and sugars such as glucose are all covalently bonded but they all dissolve in water.

What happens during the dissolving process ?

Lets take the case of copper(II) sulfate. The latter exists as an ordered crystal lattice made up of the positively charged copper ions and the negatively charged sulfate ions. This lattice must be first broken down, and then the particles diffuse in between the solvent molecules. Energy must be used to break down the lattice and this is usually taken from the solvent; in fact the temperature of the solvent usually falls when a solid is dissolved in it. Water is so good a solvent that it does not exist as pure water in nature. It has many dissolved substances, mostly solids and gases, in it. In fact if some tap water is heated using the apparata shown:

In the first case large concentric rings of solid matter were left as the water evaporated. In the second case, bubbles of water were seen to form as the water is boiled. This is not steam but dissolved gases, mostly oxygen, that were

Water and solutions

in the water. It is important that the delivery tube is filled with water to remove any air present before the experiment.

Dissolved gases in water are of most importance especially to marine and freshwater life. Note that: 1. Air is soluble in water and it is what gives water its taste - remember that pure water has no taste. 2. Carbon dioxide is not very soluble in water, but its solubility increases with pressure. As we said water does not exist in the pure form in nature. Sea water and ground water are to very important aqueous solutions. Ground water: when rain water falls onto the ground, it seeps into the ground forming underground reservoirs of water. It contains solid impurities which would have dissolved into it whilst it is going down. If the rocks through which it falls contain limestone (calcium carbonate) as in Malta, rain water will dissolve these rocks and ground water would contain a relatively high percentage of calcium hydrogencarbonate. Such water is called hard water (see Topic 12). Sea water: the main solid dissolved in sea water is sodium chloride. But, since sea water is the reservoir into which all impurities, (because rain water eventually flows back to the sea), it contains a relatively high level of solid impurities (3.6%). It would also contain calcium hydrogencarbonate because ground water eventually also makes its way to the sea. Other solids found in naturally occurring water include calcium sulfate, magnesium hydrogencarbonate, magnesium sulfate, silicates, nitrates and

Water and solutions

ammonium salts. Gases such as oxygen, nitrogen and carbon dioxide will also be found.

Water of crystallisation
Crystals of many salts contain chemically combined water molecules integrated in them. This kind of water is called water of crystallisation. Salts that contain water of crystallisation are called hydrated salts. If they do not possess the water of crystallisation, they are called anhydrous salts. The hydrated salt and its corresponding anhydrous salt are often different in appearance. For example, hydrated copper (II) sulfate consists of blue crystals, whereas anhydrous copper (II) sulfate appears as a white powder. In fact the anhydrous salts differs from the hydrated one in colour, size and shape of crystals. This is because the water of crystallisation forms an integral part of the structure of the hydrated salt, and if it is removed, it will bring about a change in structure. Usually, the hydrated salt can be changed into its anhydrous counterpart by heating. The process is usually reversed by adding water to the anhydrous salt. CuSO4.5H2O(s) CuSO4(s) + 5H2O(g)

A hydrated salt with 5 water of crystallisation molecules per unit formula, as hydrated copper(II) sulfate above, is called a pentahydrate. Similarly there are monohydrates (1 water of crystallisation molecule), dihydrates (2), hexahydrates (6), heptahydrates (7) and decahydrates (10). Some salts have more than one type of hydrated salt, e.g. it would have the monohydrate and the heptahydrate. Also, some metals form chlorides which are hexahydrates and sulfates which are heptahydrates (e.g. MgCl2.6H2O and MgSO4.7H2O). Some common hydrated salts and their anhydrous counterparts are given in the following table.

Some hydrated salts and their anhydrous forms

Hydrated Salts Anhydrous Salts Na2CO3.10H2O FeSO4.7H2O Na2CO3 FeSO4

Water and solutions

CaCl2.6H2O

CaCl2

Note that water of crystallisation is chemically combined to the salt. A hydrated salt may be perfectly dry even though it contains water. In fact water of crystallisation may be removed by dehydration, which is a chemical reaction. This is different from drying, which removes uncombined water BUT not water of crystallisation.

Deliquescent, efflorescent & hygroscopic substances

Certain substances absorb or give out water. Hygroscopic substances are those which absorb water from the atmosphere (moisture) but do not dissolve in it. Deliquescent substances absorb water vapour from the air and dissolve in it to form a saturated solution. Efflorescent substances are those that lose some or all of their water of crystallisation when exposed to the air. The following table gives some examples of each type:

Some common deliquescent, hygroscopic and efflorescent substances

Deliquescent Calcium chloride Sodium hydroxide Potassium hydroxide Sodium nitrate Phosphorus(V) oxide Iron(III) chloride Hygroscopic Copper(II) oxide Anhydrous copper(II) sulfate Calcium oxide Concentrated sulphuric acid Ethanol Efflorescent Sodium carbonate decahydrate Sodium sulfate decahydrate Copper(II) sulfate pentahydrate

Water and solutions

Chemical tests for water

Anhydrous copper(II) sulfate: water changes white anhydrous copper(II) sulfate
to blue. Cobalt(II) chloride: water changes blue cobalt(II) chloride paper pink.

Hardness in water
Rain water collects various substances as it falls from the atmosphere and eventually reaches the reservoirs. Likewise sea water contains much suspended and dissolved substances. Since both rain water and sea water is used to produce drinking water, it is important to consider what substances are found in rain and sea water. Many suspended substances are removed by filtration and harmful bacteria are destroyed by sterilising agents, e.g. chlorine. The remaining substances dissolved in water are mostly beneficial or harmless, but some of them may be also of a nuisance. As rain water falls down, it dissolves in it some CO2 from the air. Water then combines with the CO2 to form carbonic acid. CO2(g) + H2O(l) H2CO3(aq)

Many rocks in the different parts of the country contain limestone (calcium carbonate) or dolomite (magnesium carbonate). The weak carbonic acid in the rain water attacks these rocks, very slowly dissolving them as it passes through and over these rocks. The dissolved substances are calcium and magnesium hydrogen carbonates.

Water and solutions

CaCO3(s) + H2CO3(aq)

Ca(HCO3)2(aq)

Now, rocks may also contain gypsum (calcium sulfate - CaSO4.2H2O) or anhydrite (CaSO4) which are only sparingly soluble in water. All of the salts mentioned, i.e. calcium hydrogen carbonate, magnesium hydrogen carbonate, calcium sulfate and magnesium sulfate may all be present in drinking water. It is these salts that cause HARDNESS in water. The difference between hard water and soft water is shown when it is treated with soap. Soft water readily forms a lather with soap, whereas hard water does not readily form a lather with soap. There are two kinds of hardness in water: Temporary hardness: caused by the presence of dissolved calcium (or magnesium) hydrogen carbonate; Permanent hardness: caused by the presence of dissolved calcium (or magnesium) sulfate (and sometimes chloride) in water.

Effect of heat on hard water

When hard water is boiled or evaporated, a white solid deposit is usually left behind (have a look at your kettle at home !). This deposit consists of those salts (e.g. calcium carbonate or calcium sulfate) that were dissolved in the hard water, and which now have been precipitated. This phenomenon causes furring in kettles and also blockages in water pipes. Stalagmites and stalactites

Water and solutions

Caves are frequently found in limestone areas and as water trickles down through the ground to the roof of a cave, a chemical reaction produces a dilute solution of calcium hydrogen carbonate. As drops of water containing calcium hydrogen carbonate hang from the cave roof, the water evaporates slowly, and the calcium hydrogen carbonate is decomposed to give calcium carbonate which is deposited on the roof and over hundreds of years, these deposits form stalactites. Sometimes the drops of water fall to the ground before they evaporate. They then evaporate later and again form calcium carbonate deposits on the ground just under the deposits on the roof. These form stalagmites.

Action of soap on hard water

Soap is a kind of detergent. Soaps consist of the soluble sodium (or potassium) salts of a few organic acids, e.g. stearic acid (octadecanoic acid), palmitic acid (hexadecanoic acid) . Ordinary soap is a mixture of sodium stearate, sodium palmitate and sodium oleate; soft soaps have potassium salts instead of sodium salts. Since the formulae of these salts are so complicated, e.g. C17H35COONa (sodium stearate), we use St for the stearate (palmitate or oleate) radical. Soaps readily dissolve in water, and the acid anions and sodium (or potassium) cations separate and spread out: NaSt(s) --> Na+(aq) + St-(aq) Solid soap Soap solution If soap is used on soft water, almost immediately a good lather is formed. If on the otherhand, the water is hard, the lather does not form immediately. In fact a larger amount of soap has to be used if any lather is to form. One way how to determine how hard water is, is to titrate soap into the water. When soap is added to hard water, the water becomes very cloudy and a layer of solid material (a precipitate) has formed on the surface of the water. This precipitate forms because of the reaction of the dissolved substances in the hard water with the soap. 2NaSt(aq) + Ca(HCO3)2(aq) --> Ca(St)2(s) + 2NaHCO3(aq)

Water and solutions

The calcium stearate (Ca(St)2) is the white precipitate commonly known as scum. This reaction is an example of double decomposition (i.e. two salts decompose to form two new salts).

There exist also soapless detergents. These do not form scum with hard water, but since they are not made from animal or vegetable fats, they are not biodegradable and hence are not easily broken down. This causes them to be harmful to the environment.

Effect of soaps and detergents on water

A question we did not look into then is But why do we use soaps and detergents? Outer molecules on a drop of water are attracted inwards and this, results in a high surface tension for water. This means that water molecules tend to group together in groups and form small drops of water. Because of this water does not spread out evenly and hence it is not a very good cleaning agent. When detergent is added to water, the intermolecular forces between the water molecules are decreased and water spreads out more.

Water and solutions

Detergent molecules can reduce the intermolecular forces between water molecules because the detergent molecules have a part of their molecule which attracts water - it is hydrophilic (meaning water loving, as opposed to hydrophobic meaning water hating). Water molecules are attracted to this part of the detergent molecules and so the forces holding the water molecules together are reduced.

Disadvantages of hard water

1. Soap wastage increases because all the dissolved calcium and magnesium salts have to be precipitated before soap can really start to function (by producing a lather). 2. The scum produced is difficult to remove from fabrics. 3. The dissolved calcium and magnesium salts interfere with dyeing processes. 4. Calcium carbonate deposits are harmful to home appliances, e.g. furring in kettles, deposits on washing machines, dryers etc., blockages in water pipes, and heating pipes (e.g. in steam engines, laundries, central heating systems, etc.). 5. In the lab the calcium and magnesium salts may interfere with any reaction that is going to take place in water. 6. Because of these and other disadvantages it would be advantageous if hard water could be softened in some way. These ways exist as can be seen in the next section.

Advantages of hard water

Besides having several disadvantages, hard water also offers some advantages: 1. The calcium salts in the water help form healthy teeth and bones.

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2. If soft water passes through lead pipes, some lead which is poisonous would dissolve and enter humans. Hard water forms a layer of lead(II) carbonate and sulfate on the pipes which prevents this from happening. 3. Calcium carbonate is important for shell and egg formation in many animals.

Softening of hard water

The basic principle involved in softening hard water is the removal of the calcium or magnesium ions from the water.

Boiling (and distilling)

Temporary hardness is removed by boiling. When heated, the calcium hydrogen carbonate decomposes producing calcium carbonate which is insoluble. Ca(HCO3)2(aq) --> CaCO3(s) + H2O(l) + CO2(g)

Washing soda (Na2CO3)

Both temporary and permanent hardness is removed by adding washing soda to the hard water. Permanent hardness is caused by calcium or magnesium sulfates (or sometimes chlorides). These substances cannot be decomposed by heating so boiling cannot remove permanent hardness. But the addition of sodium carbonate would remove such hardness. CaSO4(aq) + Na2CO3(aq) --> CaCO3(s) + Na2SO4(aq) For temporary hardness, Ca(HCO3)2(aq) + Na2CO3(aq) --> CaCO3(s) + 2 NaHCO3(aq) In both instances the dissolved calcium ion (which is the cause for hardness) is removed as a precipitate (i.e. an insoluble calcium salt).

Ion-exchange
This method can be used to remove both types of hardness. Water is passed through a container filled with a suitable resin in the form of small granules. This resin would contain the sodium ion, and when hard water is passed through the container the calcium (or magnesium ions) are exchanged with the sodium ion. For temporary hardness,

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Ca(HCO3)2(aq) + Na2-resin --> Ca-resin + 2 NaHCO3(aq) For permanent hardness, CaSO4(aq) + Na2-resin --> Ca-resin + Na2SO4(aq) When all the Na ions have been removed from the resin, the resin has to be recharged. Reverse osmosis Availability of freshwater can be a problem in countries that do not have mountains, rivers and lakes, and where rain falls only in some short periods of the year. Countries like this, which include Malta, need to obtain freshwater in other ways. Such a way is reverse osmosis of brackish water (water with a low level of salt content - usually found in small lakes near the sea) and of sea water.

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Osmosis is the passage of water from a solution with a LOW concentration of solute to a solution with a HIGH concentration of solute through a semipermeable membrane. Reverse osmosis is the reverse process where water from a solution with a high solute concentration (i.e. the brackish or sea water) passes to a solution with a lower solute concentration. Energy and pressure is needed for this to occur.

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