Chapter 24 Water and Solution

Purification plants in swimming baths use chlorine to keep the water comparatively free from bacteria which cause infectious disease. Purification A sample of fairly pure water can be made from rain water , tap water, or river water b the process of distillation. The pure water being placed in the distillation flask and heated to boiling. The steam comes off whilst the solid impurities are left behind. The steam is condensed to water in the condenser. A pure liquid distils at a constant temperature which is its boiling point at the prevailing pressure ( 1atm, for water 100 degrees Celsius at 760mmhg) This behavior is recognized test for purity of a liquid. Properties Water is a clear colourless liquid with an insipid taste. It is usually recognized in the laboratory by its capacity to turn anhydrous copper(II) sulphate to a blue color. CuSO4 (S) + 5H2O (l) CuSO4 .5H2O (s) This test of course merely denotes the presence of water and not the absence of everything else except water, e.g. a dilute solution of sulphuric acid would turn anhydrous copper sulphate from white to blue. Pure water has the following properties: 1. It freezes at 0 2.It boils at 100 at a pressure of 760 mmhg, and pure water will boil away completely with no change in temperature 3. Its maximum density is 1g/cm3 4.It is neutral to litmus. ***It also turns cobalt chloride paper from blue to pink. There are a few substances which do not dissolve in water to some extent. Experiment to show that tap water contains dissolved gases As the water is heated, bubbles of gas are seen to rise and these will collect and be carried over into the burette. Boil the water until no more gas is given off. The gas can be shown to differ from air in that its oxygen content is much higher , and the gas boiled out will rekindle a glowing splint.

The oxygen of the air dissolves in water to the extent of only 4 volumes of oxygen in 100 volumes of water ( i.e. 1 dm3 of water contains only a maximum of 40 cm3 of oxygen) Although this amount is very small, it is of utmost importance of fish life. The fish rely on this oxygen for breathing , in just the same way as we rely on the air around us. CHEMICAL VALUE OF THE SOLVENT PROPERTIES OF WATER When the particles dissolve in water they have an opportunity for movement which place which do not take place if the reactants are solids ( ionization) AgNO3 (aq) + NaCl (aq) AgCl(s) + NaNO3(aq) The above reaction will not take place if sodium chloride and silver nitrate are ground together in a mortar. Reaction of water with metals K Na React with cold water Ca Mg Al( does not react with steam because Al is usually covered with a thin layer of aluminium oxide ) Zn React with steam Fe Pb Cu Hg Do not react with water or steam Ag Au Experiment-Reaction of potassium with water The potassium melts to a silvery ball and darts about the water. A gas is given off (hydrogen) which burns spontaneously wit lilac flame. 2K(s) + 2H2O(l) 2KOH(aq) + H2(g) If a few drops of phenolphthalein indicator are placed in the solution it will turn red because of the presence of potassium hydroxide , which is an alkali.

Experiment- Reaction of sodium with water The sodium melts to a silvery ball, but does not burn unless it is restricted in movement. Effervescence occurs, a gas is liberated , and if a light is applied , it burns with a yellow flame. 2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) Experiment-Reaction of calcium with water Drop a piece of calcium ( a grey metal) into a dish of water. The calcium sinks, unlike the potassium and sodium ; there is effervescence , and a gas (hydrogen) us given off which explodes if mixed with air and a flame is applied The calcium gradually disappears and a white milky suspension is produced. The calcium hydroxide formed is only slightly soluble. If the suspension is carefully filtered to give a clear solution, carbon dioxide can then be blown through to give usual suspension of calcium carbonate. Ca(s) + 2H2O (l) Ca(OH)2 (aq) +H2(g) Experiment-Reaction of magnesium with steam Put a 15 cm magnesium ribbon in the tube, and 2 or 3 cm3 of water , insert the cork and clamp the apparatus by the cork. Heat gently at first, with a Bunsen burner , keeping the latter moving to maintain an atmosphere of steam . Continue to pass the steam until all the air has been expelled from the tube. Finally, heat strongly. The magnesium will burn, as will the liberated hydrogen as it meets the outside air. Mg (s) + H2O(g) MgO(s) + H2(g) Zinc Zn (s) + H2O(g) ZnO(s) + H2(g) Iron 3Fe(s) + 4H2O(g) Fe3O4(S) + 4H2(g) REACTION OF WATER WITH NON-METALS Carbon Carbon reacts with steam at a white heat, forming carbon monoxide and hydrogen. C(s) + H2O(g) CO(g) + H2(g) Chlorine Cl2(g) + H2O(l)HOCL(aq) + HCL(aq) (disproportionation) how to test Cl2? -It turns damp blue litmus paper red , then bleaches it.

REACTION OF WATER WITH OXIDES Potassium oxide K2O(s) + H2O(l) 2KOH(aq) Sodium oxide Na2O(s) + H2O(l) 2NaOH(aq) Calcium oxide Place a piece of calcium oxide in a dish and add water a few drops at a time. For a little while nothing is observed and then water-vapour is seen to come off, whilst a hissing sound as the water drops on indicates that the mass is becoming hot. It begins to expand and crack , and finally crumbles to a powder, calcium hydroxide known as slaked lime. CaO(s) + H2O(l) Ca(OH)2 (s) The above three hydroxides are soluble in water( calcium hydroxide onl slightly) and together with ammonia from common alkalis. Sulphur dioxide SO2(g) +H2O(l) H2SO3(aq) SO3(g) +H2O(l)H2SO4(aq) 2NO2(g)+H2O(l) HNO2(aq)+ HNO3(aq) CO2(g)+H2O(l)H2CO3(aq) HARDNESS OF WATER Calcium sulphate is present because many rocks and soils contain gypsum ( CaSO4,2H2O) which is slightly soluble in water ( 1: 500) and hence some of it dissolves in any water with which it comes into contact. Calcium hydrogencarbonate is present in temporary water because water which contains carbon dioxide is capable of very slowly dissolving limestone or chalk. CaCO3(s) + H2O(l) +CO2(g)Ca(HCO3)2(aq) Hard water can be denied as follows: Hard water is water which will not readily form a lather with soap. CAUSE OF HARDNESS If there is a calcium compound dissolved in water, soap is precipitated in the form of calcium sulphate ( which appears as a curd) 2NaSt(aq) + CaSO4 (aq) Na2SO4 (aq) + CaSt2(s) Until the whole of the calcium compound has been acted upon by the soap, none of the latter can form a lather. Thus, with a hard water, a large amount of soap is used to precipitate and remove the calcium, and only a small extra amount to cause a lather. In this way the valuable stearate group, which loosens the dirt.

REMOVAL OF HARDNESS Removal of calcium as calcium carbonate (chalk). Many of the methods of rendering a hard water soft have as their object the conversion of a soluble calcium salt into the insoluble carbonate . In this way the calcium is removed , since the calcium carbonate being insoluble, takes no further part in the reaction with NaSt. An insoluble calcium salt cannot cause hardness. TEMPORARY HARDNESS Hardness which is due to the presence of calcium hydrogencarbonate can be removed by heating the water to boiling for a few minutes. Heat decomposes the calcium hydrogencarbonate into calcium carbonate (chalk) and carbon dioxide is expelled. Ca(HCO3)2(aq) CaCO3 (s) + H2O(l) + CO2(g) Because it can be removed only by boiling , the name temporary is given to this type of hardness. This method of removal would be expensive on the large scale. REMOVAL OF TEMPORARY HARDNESS BT ADDITION OF CALCIUM HYDROXIDE Temporary hardness can be removed by the addition of the calculated quantity of calcium hydroxide(excess would cause hardness on its own account). Ca(OH)2 (s) + Ca(HCO3)2 (aq) 2CaCO3( s) + 2H2O(l) A third method of removal of temporary hardness is to add sodium carbonate. (Permanent hardness is also removed at the same time). Na2CO3(aq) + Ca(HCO3)2 (aq) 2NaHCO3(aq) + CaCO3(s) Permanent Hardness This is due mainly to the presence of dissolved calcium sulphate, which cannot be decomposed by boiling, and hence the name 'permanent' is given to this type of hardness. It is most easily removed by adding washing soda crystals to the water. This causes a precipitate of insoluble calcium carbonate to be thrown down and thus prevents the calcium from interfering. CaSO4(aq) + Na2CO3(aq) CaCO3(s) + Na2SO4(aq) ION EXCHANGE METHOD OF SOFTENING WATER The above methods of softening water(i.e. boiling and adding soda)are used mainly in the house for solving small amounts of water .In the treatment of larger supplies of water the ion exchange process is used. The ion exchange substance is complex but we can regard it as Na2Y. When a dissolved calcium salt runs over it, ion-exchange occurs. The sodium substance Na2Y will finally become a calcium substance, CaY, and it can be made fresh again by running concentrated common salts solution over it and washing away the soluble calcium chloride formed.

CaY (s) + 2NaCl(aq) Na2Y (s) + CaCl2(aq) Water of Crystallisation When a few crystals of copper(II) sulphate are heated gently in a test-tube, a copious evolution of water-vapour takes place. The colour and shape of the crystals disappears and in place of blue crystals of hydrated copper sulphate, a white powdery mass of anhydrous copper sulphate forms. CuSO4,5H2O(s) CuSO4(s) + 5H2O(g) hissing is heard and steam is evolved, showing that heat is generated. A blue solid is left. This liberation of heat energy occurs because the anhydrous copper sulphate is hydrated by the water. The heat generated is called heat of hydration. Water of crystallization is necessary to create the crystalline shape of some crystals and is that definite amount of water with which the substance is associated on crystallizing out from an aqueous solution. Substances which contain water of crystallization -sodium carbonate crystals ( Na2CO3,10H2O) -sodium sulphate crystals (Na2SO4,10H2O) -Copper(II) sulphate crystals ( CuSO4,5H2O) -Iron (II) sulphate crystals ( FeSO4,7H2O) SOLUTION In general, to produce such a solution, the ordered crystal lattice of the solid(the solute) built up from positive and negative ions or form molecules, must first be broken down so that its particles can diffuse between the molecules of the liquid (the solvent) and move among them. Since the particles in the solid lattice are electrically attracted to each other, energy must be supplied to separate them. This energy is taken from the heat energy of the liquid, consequently, there is usually a fall of temperature as a solid dissolves in water. If, however, some form of chemical action occurs at the same time, e.g. hydration of ions, this action may liberate enough heat to cause an overall rise in temperature. Suspension A solid is said to be in suspension in a liquid when small particles of it are contained in the liquid, but are not dissolved in it. If the mixture is left undisturbed the solid particles will slowly settle to the bottom of the containing vessel, leaving the pure liquid above them. Muddy water is a typical suspension. The mud would settle after a time if left undisturbed, leaving a brown residue on the bottom of the containing vessel and clear water above. The particles of mud would be retained by a filter

paper whilst the water would pass through. Saturated Solution a saturated solution of a solute at a particular temperature is one which contains as much solute as it can dissolve at that temperature, in the presence of the crystals of the solute. The concentration of a saturated solution varies with the solute , the solvent, and also with the temperature. A rise in temperature will cause more to dissolve times more soluble in water at 80 than it is in water at 10. DETERMINATION OF SOLUBILITY The solubility of a solute in a solvent at a given temperature is the number of moles of the solute necessary to saturate 1 kg of the solvent at that temperature. It denotes a limit, that is , the maximum amount which can normally be held in solution. Solubility is also sometimes in moles of solute per dm3 of solution at a given temperature. Experiment- To determine the solubility of potassium nitrate in water at the temperature of the laboratory This determination must be carried out in two stages. It is first necessary to prepare a saturated potassium nitrate solution at laboratory temperature and then to find the proportions of potassium nitrate and water in it. To make the saturated solution. The rate of solution of a solid in cold water is generally so slow that it is almost impossible to obtain a saturated solution of it in a reasonable time by merely shaking the solid with the water. The quicker and more certain way is to crystallize from a warm solution by cooling. Half fill a boiling tube with and dissolve in it some potassium nitrate. Warm and shake well. Pour off a small sample into a test tube and cool it under the tap . If no crystals appear, return the sample to the boiling tube and add more solute. Test another sample and continue in this way till a sample gives crystals. Then cool the whole solution. When the crystals have separated and the solution is quite cold, take the temperature of it . Then filter it through a dry filter paper and funnel into a dry receiver to avoid diluting it. The filtrate is a saturated solution of potassium nitrate at the observed temperature. To obtain the solubility of potassium nitrate using this solution .Weigh a clean dry

dish and add some of the saturated solution to it. Weigh again. Once having weighed be careful not to lose any portion of the solution. Place the dish on a steam bath, and evaporate until the potassium nitrate is left quite dry. (The dish on a gauze may be warmed very gently over the Bunsen flame for a few minutes to complete the removal of water ) Allow the dish to cool and weigh it . Calculate the number of moles of the potassium nitrate which would have dissolved in 1 kg of water as in the following calculation. Specimen results Mass of dish=14.32g Mass of dish and solution=35.7g Mass of dish and potassium nitrate=18.6g Temperature of saturated solution = 15 17.1g of water dissolved 4.28g of potassium nitrate Therefore, 1000g of water dissolved 4.28 x 1000g of KNO3= 250g of KNO3 17.1 Molar mass of KNO3= (39+14+16x3)g =101g thus, 250g of KNO3= 250 mol=2.48 mol 101 Solubility of KNO3 in water at 288K is 2048 mol/kg Generally, any increase in temperature will increase the solubility of a solute in water. This is because most solutes dissolve in water with absorption of heat. FRACTIONAL DISTILLATION If two liquids have reasonable different boiling points , e.g. water 100 , ethanol 78 at standard pressure, they can be separated ( though not always completely) by fractional distillation. Various forms of fractionating column can be used. Their general purpose is to provide surfaces, e.g. flat discs, on which ascending vapour can condense. This produces a succession of liquid films in which, as the column is ascended , there is an increasing concentration of the more volatile liquid . Example: liquefied air to obtain N2 and O2