Unit 3. Water 1.A most important Chemical Although hydrogen makes up only 0.14% of the earth’s crust, atmosphere and oceans, its compound water is the most significant chemical in the biosphere. Water circulates in gaseous and liquid form in the atmosphere and forms an earth layer of its own - the hydrosphere. It is found on comets, some moons, gas giants and in space itself. Water is an excellent solvent because of the : bent and polar nature of its molecules. The Water is a polar solvent oxygen has two lone pairs of firee electrons with positive and negative sides which repel the hydrogen branches forming a bent molecule. oe “4 = Two electron lone pairs are unbonded ‘and repel the covalent bonds down ‘The oxygen end is negative and the hydrogen ends are positive. When a chemical drops into water, these positive and negative ends attract and carry off ions and molecules causing the chemical to break up and dissolve, When a chemical dissolves in water, itis called the Water is a bent molecule solute and the mixture is called the solution, Life appeared in the hydrosphere. The oceans experience less extremes of temperature than the land, at least at the surface. Even when plants, bacteria and animals finally conquered the land, the life forms carried their water with them in salty form, trapped inside the living cells. All land animals and plants have a continuous requirement for water. When they invaded the land in quantity 500 million years ago, Water was available, ‘Water has the peculiar property of being able to expand when it freezes. By freezing in the cracks of rocks in winter, it breaks rocks down into smaller fragments. ‘Water, dissolved acids, and oxygen combine to attack miner- als that would normally survive for millions of years. The rock minerals are quickly broken down into the simple salts required by plants and animals for their metabolic reactions. So quartz crumbles to form the coarser soil particles. Feld- spars form clays and salts of calcium, potassium and sodium, Black ferromagnesian minerals, such as biotite, yield the iron needed for our blood and the magnesium needed for plants. ‘Add life and we have a truly living soil all courtesy of the Most solids have higher densities power of water. than their gases. Ice does not because its crystal structure is ; very open. The water molecules Water has its own cycles. The major ice-age cycles and their form the comers of hexagons which thawings had a significant effect on the evolution of man. are arranged like honeycomb. Chem 3.1During an ice age, much of the earth’s water is locked up into solid form and the ice reflects much energy back into space. ‘The earth dries out and the winds blow strongly. Australia was transformed from a rainforest country with a rich marsupial fauna into the dry continent that it is now. We need to understand the triggers for these major water events. Much Antarctic research focuses on the recovery and study of ancient ice cores. ‘The main water cycle involves the evaporation of water from sea and lakes, the formation of clouds and the precipitation of the water as liquid on sea and land. © Set 3.1 Learning to love water 1. Define the terms: a) solvent b) solute : ©) solution 2. Outline the significance of water oS a) to living cells b)as a less extreme habitat for the genesis of life ©) as an agent of physical and chemical No answers are provided for this set. 3. Account for the fact that ice has a lower density than water. Mandatory Prac 11 Density of Water Compared to Ice ‘The density formula has been known long since cobwebs were found in the first science laboratory, which was probably used to work out what was wrong with eating snake-ridden apples. Density (in g/mL) ~ mass (in grams) volume (in mL) Procedure for water 1, Weigh a measuring cylinder. Carefully add 100mL water and re- weigh. Work out the mass of water only and use the density formula above. As you measured 100mL water, this has three figures and should dictate the number of significant figures in your answer. Analternative procedute is to use a hydrometer similar to the one they use to measure the acid density in car batteries. Procedure for Ice 2. The ice calculation is more difficult because it is an irregular solid. How do you measure the volume of an irregular solid? A crude way is to find the largest measuring cylider that you can find and ice to fit. Put water in the cylinder and measure it, Dry and weigh some ice. Push it just under the water in the cylinder using the tip of a pencil and measure the volume of ice by difference. Then use the density for- mula again, Chem 3.2Mandatory Prac 12 Effect of antifreeze and salt on the freezing point and/or Boiling point of water Safety Audit 1) Ethylene glycol (antifreeze) is used to depress the freezing point of ‘water in car radiators in cold countries. It is very dangerous if drunk, ‘They say that itis a very painful experience as your brain solidifies. 2) Do not attempt to freeze glass containers of water. They will ex- plode. 3) Do not attempt to freeze water containing thermometers, particularly the mercury ones. They will crack. You can see that I am not keen on this choice of prac. Procedure 1, Pour an equal quantity of ethylene glycol and water on identical ice cubes in a beaker, Record observations. 2. Place a small amount of ethylene glycol and water in a tin can (not sealed) in a freezer overnight. Attempt to freeze, Use an identical can with water as a control. Record observations. 3. Make a saturated solution of salt and water. Boil the mixture whilst stirring and using a thermometer. The normal boiling point of water is what? Record your observations and make an inference, 2. Water's Special Molecular Structure and Properties ‘Water is our special chemical of life. Our existence on this planet has depended on the fact that water has some anomolous properties, when compared to its related chemicals. ° a) Water crystals are held together by hydrogen bonding b °), By now you should have realised that water forms molecular crystals. The units A molecular crystals are water molecules HO held together by intermolecular forces. So when you Consist of molecules melt ice, it does not break up into atoms as covalent network solids do, or ions held by intermolecular as ionic lattice solids do, it breaks up into molecules of water. forces (i) The weakest intermolecular bonds are found in non-polar compounds Xap mayo such as H, or CH,. These chemicals have perfect symmetry in the way the xN=No electrons are arranged. There is little reason for these molecules to attract unless the electron clouds are made to wobble. So they are normally gases. NyS7onpolar forces (ii) Some molecular crystals such as CO have polar molecules. When you oo draw their Lewis dot structures, one side of the molecule has more valence ° electrons than the other. These molecules are polar. The electron side is more H-cl¢ negative than the other side which is positive. The intermolecular bonds ba holding these cuties together are called dipole-dipole forces. These ee gasis a te lecul: str a with strong dipole- intermolecular bonds are stronger. dipole 3 These are also hydrogen bonds Chem 3.3(iii) The smallest atom is hydrogen. It only has one electron and even if sharing, has only two electrons around it. Ifyou bond hydrogen with other non metals, the other non metal is very negative and the hydrogen very positive. ‘There are four lots of hydregen bonding Molecules of hydrogen atoms bonded to some ion metal atoms between two water experience hydrogen bonding. Hydrogen bonding is a super i di 7 Hydrogen bonding is a dipole-dipole force. Hydrogen bonding i between hydrogen and a ‘The atoms that exhibit hydrogen bonding with hydrogen are ‘ron metal such as C or © ‘fluorine F, nitrogen N and oxygen O. © Set 3.2 Looking at Molecules 1, This is revision from topic 1. You may also like to use data page 13. I quote a dot point: “Construct Lewis electron dot structures for water, ammonia and hydrogen sulphide to identify the distribution of electrons.” Identify the molecules as polar or non polar. 2. Clarify the terms polar and non polar with respect to molecules. 3. Explain why polar molecules have higher melting points than non polar molecules. 4. Compare hydrogen bonds with dipole-dipole forces. 5. Account for the differences in melting and boiling points: Chemical Formula Melting point Water H,0 orc Hydrogen sulphide | HS -83°C Ammonia NH, -78°C 6, Explain why ethane CH, is a gas and ethanol CyH,OH is a liquid at room temperature. a) Some effects of strong hydrogen bonding (i) Surface tension Molecules deep within water tend to stick to each other by hydrogen bonding. The surface ofa liquid exhibits surface tension. They cohere more strongly to the molecules to the sides of them. This forms a surface film held by bonds which prevent objects from breaking the film, Surface tension is what holds water into droplets and water bubbles together. They are important to insects such as water striders which walk on the water layer. Detergents are chemicals that substantially reduce surface tension, Surface tension also decreases in hot water Chem 3.4(ii) Cohesive Forces ‘This diagram shows both the cohesive Surface tension forces and adhesive forces found between forces water molecules in a beaker of water. Both N\ are reasonably strong in water because they are both caused by hydrogen bonding, (iii) Adhesive forces ‘The adhesive forces are not shown. These are the forces between the glass container and the water. The hydrogens of the water are attracted to the oxygens in the glass by hydrogen bonding. So water sticks to and “wets” the glass. The top of the water forms a concave meniscus, curving down. Cohesive forces in liquid When you put mercury in a beaker, this does not happen. Mercury does not stick to the glass and forms an upwardly curving convex meniscus. Capillary glass tubes are very narrow as are straws, Place a capillary tube in water and the water will rise up the tube. The height is a measure of the adhesive forces between the water and the glass. These effects are important in the way more complex plants are structured. The vascular bundles are structured to be narrow to encourage water to flow up them by capillary action. (iv) Viscosity Viscosity or “glugginess” is the ability of a liquid to resist flowing. Water is reasonably viscous compared to some liquids because of the strength of the hydrogen bonding between molecules. (v) Boiling and Melting Points Again the strength of the hydrogen bonds causes water to have anomolously high melting and boiling points, So liquid is allowed to cover the planet. Liquids are necessary for our form of life. (vi) Hardness and Brittleness Ice is not as hard as covalent lattice structures such as minerals because the hydrogen bonds are one order of magnitude less in strength than covalent bonds. You cannot move water molecules easily through the ice crystals so water is brittle. ‘The following table on the next page deals with some of these anomolous properties for water and provides a brief explanation for those properties. Chem 3.5Weirdness Compared with Explanation HighM.P.0°C Chloroform CHCl; -63°C_ | To melt water, we need to break 4 strong hydrogen bonds between each pair of molecules. HighB.P. 100°C | Chloroform CHCl; 61°C |The hydrogen bonds are strong, These prevent water molecules escaping at the surface. So water has a low vapour pressure above its surface, Boiling cannot occur until the vapour pressure equals the external pressure. This factor has allowed a liquid to exist on the surface of our planet, High surface tension | Carbon tetrachloride CCl, | Water molecules on the surface are pulled 73 mi/m? 27 mJ/m? at 20°C sideways by strong hydrogen bonds. Energy is needed to increase the surface area, This is the source of the surface tension. High viscosity Pentane 0.22cP at 25°C | Viscosity is “liquid gluggynesss”. Viscous 0.89¢P (relatively, liquids do not flow easily because the molecules butnot enough to are restricted by each other. Water has strong, prevent water from hydrogen bonding between the molecules. moving within living cells). Shrinkson melting | Ice volume=1,09x water | Ice has an open crystal structure where all the water molecules have 4 tetrahedrally oriented hydrogen bonds Freezing ice weathers rocks to soil High specific heat | Pentane 1.661/g As water is heated, much energy is needed to 4.180/g, bend and break the H-bonds. This energy is not used to increase water temperature. So oceans are not easily heated allowing life to survive. © Set 3.3 The Unusual Properties of Water 1, Explain the following anomolous properties for water a) surface tension b) adhesion ©) cohesion 4d) viscosity ¢) boiling and melting points £ hardness and brittleness 2. Analyse the implications of 2 of these water properties for plants or animals on earth. (No solutions will be provided.) Chem 3.6nee Water H* os H “93 /o - H H Polar BENT H H is xo | N Ammonia ¢N 3H oN—H / | \ xo | Polar H H H H H PYRAMIDAL Hydrogen sulphide Hiss H-s? ree 7 py Polar H pent H 2. Non polar means that the electrons are symmetrically distributed within the molecule, Polar molecules have electrons concentrated at one side, so that one side is slightly positive and one side slightly negative, 3. Polar molecules have stronger intermolecular bonds called dipole-dipole forces. These forces are anattraction between the slightly positive end of one molecule with the slightly negative end of an- other. 4, Hydrogen bonds are a very strong dipole-dipole bond. Hydrogen is small, has few electrons and has avery positive end. With N,O of F it forms an intermolecular bond ten times as strong as normal dipole-dipole forces. 5. The water and ammonia have hydrogen bonding and so have higher melting and boiling points than the rotten egg gas which has only normal dipole-dipole forces. Water obviously has stronger hydrogen bonding than ammonia. This is probably caused by the fact that the oxygen in the water molecule is more electronegative than nitrogen, 6. Ethanol molecules have a polar -OH end, This causes hydrogen bonding between the O of one molecule and the H's of another. So ethanol molecules are harder to wrench apart. Mandatory Prac 13 Some properties of water Problem “Perform a first hand investigation to demonstrate the following properties of water: a) surface tension b) adhesion ©) cohesion ¢) viscosity” Procedure a) You will need a pneumatic trough or larger tray of water, eyedropper, detergent, alfoil, scissors. Cut small alfoil boat similar to the above. Smooth and curve it with your fingernail until you have some- thing that floats. Place it on the left side of your tray. Add a smalll drop of detergent to the cavity. This destroys surface tension behind the boat but not in front. It should be pulled forward. Chem 3.7b) Demonstrate capillary action by placing a number of tubes including a capillary tube in coloured water, Measure the height rise in each case. Make an inference. It is the same capillary action that draws water up wicks, soils and filter papers. Capillary action is caused by adhesive forces. Compare the action of water with other liquids such as alcohol. c) Compare viscosities by rolling 1mL of various liquids down a board of gentle slope. Time the passage to the bottom using a stopwatch. Tabulate your results and make an inference. 3. Water as a solvent a) Some solubilities The following table shows the solubilities in g/100mL water for a range of solute chemicals: NOTE FOR SOME CHEMICALS, WATERS OF CRYSTALLISATION ARE NOT SHOWN. Chemical Formula Classification Solubility in g/100mL water aluminium chloride AICI; Tonic 45g aluminiumoxide 1,0; Covalentnetwork insoluble ammonia NH, Polar molecular 48g ammonium chloride NH,Cl Ionic 39g barium sulphate BaSO, Tonic 0,00025g bromine Br, Non polar molecular 3.5 hydrogen bromide HBr Polar molecular acid 193g hydrogen chloride HCl Polar molecular acid 70g calcium carbonate CaCO; Ionic 0.013g calcium chloride CaCl, Tonic 83g carbon tetrachloride CCl, Non polar molecular 0.08g methane CH, Non polarmotecular 0,0021g carbon c Covalentnetwork insoluble carbon dioxide CO, Non polar molecular 0.145g chlorine cl, Non polarmolecular 0.63g coppersulphate CuSO4 Tonic 22g iodine L Non polarmolecular 0.034g silicon carbide sic Covalentnetwork insoluble silicon dioxide SiO, Covalent network insoluble Some trends become evident: (@ Ionic solids show variable solubility. Some are quite insoluble in water and some are very soluble. The polar water molecules attempt to carry off the ions in the ionic crystal. The hydrogen ends attract the negative anions and the oxygen ends attract the positive anions. A soluble ionic erystal, such as NaCl will rapidy break up into its units and disappear in water. Some ionic solids are strongly bound and resist the attractions of the polar water molecules, (ii) Non Polar Molecular chemicals are slightly soluble at best . Polar molecular compounds such as HCI and NH; are often quite soluble. They mix quite readily with their polar relation water. Often these are acidic or basic chemicals and react with the water as well as dissolve. Chem 3.8,(iii) Covalent network solids are mostly insoluble. Their strong covalent bonds resist the attentions of the polar water molecules. © Set 3.4 Water as a Solvent 1, Summarise what you have learned in this section. 2. Predict solubilities for these chemicals after classifying the types of crystals that they form 2) potassium chloride ») silicon sulphide c) iron oxide yo 4) fluorine gas e) lead sulphate & covalent network solids oe & such as diamond resist a Reena VO ‘SB the polar water molecules ¢ h) nitrogen gas & oO i) phosphorus {) silicon hydride Mandatory Prac 14 Solubilities of Chemicals in water Procedure Use test tube racks with large test tubes. Wear goggles, Attempt to dissolve small quantities of a range of liquid and solid ‘chemicals in water. Shake in the approved manner, Include ‘examples of all chemical groups. In your results (data) table include formula, classification (non polar molecular, polar molecular, ionic and covalent network solids), prediction and observations. Active at an overall inference from your results. b) Diffusion and Osmosis Like the flight of the bumblebee, the syllabus now visits diffusion and osmosis, These have great relevance to how living cells pump themselves up with water, Itis vital for living things that water be able to penetrate living cells. Other wise the cell would have no cytoplasm (cell watery fluid). Two different processes are at work. They are called diffusion and osmosis. Ifyou sit a potato in water, both processes will work to force water into the potato cells. Chem 3.9(® Diffusion When given energy, molecules will begin é P o- moving randomly. Q Ifa chemical is more concentrated at one point in a fluid, it will gradually move into the ao g o point of low concentration until the concentra- fe aoe High Concentration tion is uniform everywhere. This is diffusion, ‘9 b aA Diffusion is fastest in gases and mighty slow 8 ehty Ina game of random movement, particles Low concentration in solids. will tend to move to from a region of high ee concentration with respect to that le: Gi) Osmosis This isa special type of diffusion through semi-permiable membranes ofthe sort that surround living cells. Nature has designed membranes to protect themselves. The structure is as shown. They need to be semi-permiable, to let some things in selectively. So they have pores, The outside of the cell is ‘more concentrated with respect to water than the inside, So water will naturally diffuse through the pore openings. This diffusion through membranes is called osmosis. The water actually exerts an ‘osmotic pressure on the cell to pump it up with water. Water diffuses from high to low water concentration Outside is fresh water Cell membrane + 2 lipid layers Protein layer © Set 3.5 Diffusion and Osmosis 1. Distinguish between diffusion and osmosis 2. Explain why people who sit in freshwater baths for too long develop wrinkly fingers. No solutions provided to this set, Solutions 3.4 2a) soluble ionic b) insoluble covalent network c) insoluble covalent network d) reacts with water, non polar molecular e) insoluble ionic f) soluble ionic g) very soluble polar molecular h) slightly soluble non polar molecular i) insoluble non polar molecular j) insoluble non polar molecular Chem 3.10¢) Acidic and alkaline solutions Water is a curious chemical. It is supposed to be molecular, but actually breaks up into ions ever so slightly as follows:- HO) > Hag + OR ag, water hydrogen ions hydroxide ions Itis a very slight effect with only one molecule in 10'¢ being broken into ions at any one time in pure water. The genius who discovered it used platinum apparatus to measure the tiny electrical ‘conductivity caused by the presence of the ions. ‘The two ions are significant. Normally there is a balance between the two ions in water. The pH is 7. But if you add chemicals to the water to upset the balance, you change the pH and cause one ion to dominate in the watery solution. Acids have mostly hydrogen ions and pH less than 7 Alkalis have mostly hydroxide ions and pH greater than 7 (i) Acids are species that form hydrogen ions with water These tables introduce some acids which form hydrogen ions with water. The pKa is a measure of acid strength. We use it for weak acids. With strong acids, just about every molecule breaks up into hydrogen ions. Strong Acids Hydrochloric acid HClgy Sulphuric acid H,S0y0) Nittie acid HNO, Chromic acid 1,10, Weak Acids are those acids where only a few molecules of acid react with water by losing their protons. The larger the pKa, the weaker the acid, Acid species, Formula pKa Bisulphate ion HSO; 1.99 Boric acid HBO, 9.24 Butanoie acid CH,CH,CH,COOH 4.82 Carbonic acid 1,0, 6.35 Ethanoic acid CH,COOH 4.76 Hydrogen sulphide HS 7.02 Hydrofluoric acid HF 3.17 Methanoic acid HCOOH 3.74 Nitrous acid HNO, 3.14 Phosphoric acid HPO, 2.13 Sulphurous acid HyS0, 1.90 (Chem 3.11© Set 3.6 Acids dissociate in water ‘These are worked examples showing how boric acid (borax), a solid acid, and hydrogen fluoride gas form hydrogen ions in water. Write similar equations for the addition of the acid chemicals below to water. Note (S) = SOLID (L)=LIQUID (G)=GAS (AQ) = ions in water solution eg Boric acid with water H3BO;q Hug + HZBOs(aqy eg2 Hydrogen fluoride gas with water HE) Hog * Frag First you subtract the hydrogen, then you subtract the single positive charge making the other ion particle one more negative. y ‘Acids make 7 eae a hydrogen ions iter. 1) hydrogen chloride gas inwater 2) concentrated sulphuric acid (an oily liquid) 3) nitric acid (a liquid) 4) bisulphate ion (in sodium bisulphate, an acid salt much used in old chemistry sets) 5) carbonnic acid (in soft drink) 6) ethanoic acid (in vinegar) 7) hydrogen sulphide (rotten egg gas, a volcanic gas of the sea floor and acid-sulphate soils) 8) methanoic acid (= formic acid, ant sting and citrus stink bugs) 9) phosphoric acid (cheap soft drink preservative) 10) sulphurous acid (should be banned as a meat preservative as some people are sulphur allergic). (ii) Bases are species that form hydroxide ions with water ‘There are two ways of doing this. First you can dissolve a soluble metal hydroxide in water: NaOH s)-> Na“ aq + OH'(ag) Ifyou are wondering why we would want to do this the answer is that the hydroxide ion is a very usefl little nasty critter, Its caustic and will bum your skin and eyes. Its especially useful in making soap with fats. The second way is to take a base species and react it with water. Reactions with water are called hydrolysis reactions. The base takes an H* from the water and combines with it, The other product is the hydroxide ion. Metal oxides contain the base oxide ion. 2- : 7 OF (nq) +H20qy > OH aq) + OH'aq Thaye not added up the two similar products so that you could see what was happening. We have added an H* to the O* and then taken it off the water. ‘Chem 3.12© Set 3.7 Bases dissociate in water ‘Write similar equations to the worked examples before for the addition of the base chemicals below to water: 1) potassium hydroxide powder = 2) calcium hydroxide powder 3) magnesium hydroxide powder 4)asolution containing carbonate ions 2 5)a solution containing sulphide ions Wi Alkalis make 6) ammonia gas NH3,¢) 2 Ze hone 7) phosphine gas PH.) tons in water. 4. Precipitation Reactions a) Dissolving Equations On data sheet page 8, there is a “solublity rules” table which crudely helps you to work out if some ionic compounds are soluble or not in water. Thinking people would know that most ionic compounds are soluble in water to some extent. It is just a matter of degree. Good chemists know how to interpret. and use solubility product constants to calculate exact solubilities. The skill is advanced and these quantities are listed in chemical data books. Our first worksheet will practise the skills of writing equations for the solution of ionic crystals and polar covalent liquids in water. Look at these examples first: Polar covalent chemicals ‘These equations are simple. We start with the chemical and mix it with water. The molecules survive. (AQ means surrounded by water. eg 1) Write an equation for the solution of methanol CH,OH,) (drink it and you will go blind !) CHOHg) ~> CH,OH 4g) Tonic crystals ‘These may be salts, acids or bases. Some hydrolyse (react with water). Data books will tell you this with the letters “hyd”, We will assume they don’t. eg 2) Write an ionic equation for the solution of barium sulphate with water. We check the solubility table as itis a salt. It does not dissolve, so no equation. eg 3) Write an ionic equation for the solution of sodium sulphate with water. We check the solubility table, It does dissolve, so we do it, NaSOys) > 2Na* aqy +80," (aqy ‘We use valence rules to write the formulae. The ion charges are as on the valence data sheet 5. Chem 3.13© Set 3.8 Dissolving equations Write similar equations to the worked examples for the solution of these chemicals in water: 1) Ethanol C,H,OHy) 2) Nitric acid (liquid) 3) Sodium hydroxide solid 4) Copper hydroxide solid 5) Magnesium carbonate solid 6) Ammonium carbonate solid 7) Sulphuric acid liquid 8) Silver nitrate solid 9) Potassium phosphate solid 10) Zine bromide solid Solutions3.6 1. HClgy > Hag? Crag) 2 HS0q) > Mag t 80a) 3. HNOs4q > Hag t — NOs‘aq : 4 HSOx(4q) Hat — 80,7(agy CDANGER » 5. H,CO, > Hagt — HCO; ¢9) peeteleel 6 CH;COOH a, > H"aqy+ — CH3COO%mg) | CORROSIVE MATERIALS, 1. HSey > Hagt BSag WEAR REQUIRED 8. HCOOHy, > H%qqyt — HCOO‘agy 9. HPO) > Hat — H,POyaq 10. HSO%q > HYaqt —_ HS0s (ag b) Precipitation Equations “Some enchanted evening, You may see a stranger + : ‘You may see a stranger ag (og if Cl log yg G) ** Across a crowded room And somehow you know ‘You know even them .../ ‘With apologies to the movie “South Pacific” Precipitation reactions are all about ions meeting each other in a crowded test tube. They forget about the water molecules milling around each other and their previous partners who they broke up with when water dissolved them. Their new bonding is strong and they attract forming a crystal precipitate which falls to the bottom of the test tube under gravity. ‘So how do they know who their true loves are ? Simple Virginia ! They check the data sheet 8 to see which ion combinations are insoluble. Chem 3.14The Ag CE ,, » precipitate shows what happens when two soluble solutions of silver nitrate and sodium chloride are mixed. We need to check the swapped ion combinations of sodium nitrate (soluble) and silver chloride (insoluble) Le voila! Silver chloride has a match! Once you have found what precipitates, itis a simple matter to w: an equation. ¢g2) Silver nitrate solution is added to sodium sulphate solution. Write an ionic equation for any reaction. F We check silver sulphate and sodium nitrate in the solublity table. Silver sulphate is insoluble. We have a word equation :- Silver ions + sulphate ions ---> silver sulphate F Use valencies to write the right hand side formula first Silver ions + sulphate ions ---> Ag,SO, FF Count ions in formula 2 Silver ions +1 sulphate ion —-> Ag,SO, r Write the ion formulae The first ion is positive. The second is negative The number of the ion charges is the valence number 2AB!(agy + SO¥* (aqy > AB SOx) Set 3.9 Writing Precipitation Reactions ‘Write equations for the precipitation of these chemicals :- 1, Silver iodide 2, Calcium carbonate 3.Lead sulphate 4. Copper hydroxide 5. Silver carbonate Write equations for these additions. The chemicals listed are in solution. 6. Copper sulphate + sodium carbonate 7. Lead nitrate + sodium chloride 8. Calcium nitrate + potassium hydroxide 9. Iron (2) sulphate + sodium carbonate 10. Magnesium sulphate + sodium hydroxide Chem 3.15,Solutions 3.7 KOH (g)-> K*aq + OH(aQ) Ca(OH) p¢g)--> Ca™"(aq) + 20H (gy Mg(OH)pqs)--> Mk?" (4q) + 20H'(4Q) COs" (aq *H20qy > HCOs¢4q) + OM ag) Sq THA) > HS aq + Hag NH3@¢) * Hq.) > NH4*(aqy + OF aqy PH) +H,0q) --> PHy"(aq) * Otay Solutions 3.8 DAYAL e CAUSTIC 1) GHOHg) -> — CHjOH 4g) 2) HINO, > Hagt — NOs‘) 3) NaOH) => NaY FOR QQ) 4) insoluble 5) _—_—insoluble 9) (NH),COss)-> — 2NH,*faqy + S04" (aa) 7) WSO) > tay + $0,7*aq) 8) AgNOys) Agag NO s(aqy 9) KsPOq) 3Kaq + POG aq 10) ZnBrygy > Ei aq + Brag Solutions 3.9 LAgiag + Tag “? Ashe) 2. Ca¥ aq) + C03" (AQ) CaCOy¢g) 3. PL ag) + — SO4(aQy PLSOxs) 4. Cag) + 20H iagy Cu(OH)x¢s) 5. 2Ag* ag) + CO;* (AQ) Ag,COxs) 6 OP ag + CO% aq CuCOss) 7. PO ag) + — 2Cl rq PbClys) 8. Ca¥ nq) + 20H AQ Ca(OH) xis) 9. Fe* (ag) + CO5*‘aQ) FeCOxg) 1O.Me™ag + 20H ag) => MeOH) Mandatory Prac 15 Precipitation Reactions Safety Audit Dropper bottles should never be used as water pistols. Most lab chemicals are murder to eyes Procedure Use glass slides with wells on top of a black tile. This is semi-micro analysis, Chemicals should be in dropper bottles. Wear goggles. It is suggested that sodium chloride, sodium carbonate, sodium sulphate and sodium hydroxide solutions be added to solutions contain- ing these cations: K*, Ca?* , Mg”*, Pb?", Fe*, Cu?*, Ba”. Predict precipitates, tabulate results and write ionic equations for the successful reactions. Chem 3.16¢) Solution Molarities ‘The term" molarity" is not to be confused with the term "mole". Molarity is a measure of the concentration of a chemical which is dissolved in solution. It is measured in moles dissolved per litre of solution, ‘The following situations are equivalent in terms of the molarities of the solutions produced :- 4 moles per 1000 mL. 2 moles per 500 mL 1 mole per 250 mL = 4 molL* = mol L* = 4molL* ‘We remember this formula: moles = grams n=g molecular weight M ‘The molarity ofa solution can be calculated using this new formula: molarity= moles dissolved c litres <2 Ifyou are weighing out chemicals to make up a solution then: grams = molarity x litres x molecular weight | g=Vne _g’day Vince! nis moles in mol cis molarity in mol L Vis volume in L (litres where 1L = 1000mL) gis mass of solute in grams Examples 1. Calculate the mass of common salt required to make 200 mL of 0.02 mol L"! saline solution. grams = molarity x litres x molecular weight. 0.02 x 0.200 x 58.5 234g. Chem 3.172. What is the molarity of a sulphuric acid solution if 16g of concentrated acid is dissolved in an exothermic reaction in 200mls of water ? molarity moles dissolved litres = 16 98x 0.2 = 0.82 mol L"! © Set 3.10 Preparing Solutions A laboratory assistant is required to weigh solute to prepare the following solutions. Calculate the mass of solute required in each cas 1)50 mL4 mol L"! sodium chloride solution BG 2)20 mL 0.1mol L”! copper sulphate using copper sulphate pentahydrate 3) 10 litres 2mol L! sulphuric acid 4) 100 mL 0.02mol L”! potassium permanganate solution 5) 400 mL 3mol L ferrous sulphate using ferrous sulphate heptahydrate 6) 40 mL 0.1mol L! vinegar using pure glacial acetic (ethanoic) acid CHyCOOH. 7) 5L 0.01 mol L"! sodium carbonate solution using sodium carbonate decahydrate © Set 3.11 Determining Molarities Calculate the molarity of the following solutions :~ 1) 5.3g anhydrous sodium carbonate in 200mL water 2) 5.85g sodium chloride in 500mL water 3) 3.1g copper carbonate in 10 L water 4) 1.01g potassium nitrate in SOmL water 5) 1.05g sodium bicarbonate in 200mL water 6) 27g copper chloride in 400mL water 7) 4.9g concentrated sulphuric acid in 2L water 8) 7.3g HCI gas in 10 L water d) Diluting Solutions Acids are usually available from manufacturers only in concentrated form. For many uses, they need diluting. The problem is to calcuate how much water to add. During dilution, the number of moles of solute remains constant so :- Moles before dilution Moles after dilution Molarity x Litres before Molarity x Litres after Note that V, is the total new volume, It is not the amount of water added. Chem 3.18Problem Iwish to prepare 200mL of 2mol L"! HClusing 10mol L"! acid. How much concentrated acid do T use and how much water to Tadd ? eV =e2¥2 Vi= 22 cr =2x0,200 10 = 004 = — 40mL(add 160mL) © Set 3.12 Diluting Solutions How much concentrated solution do you measure out and how much water do you add to make 1) 500mL 0.1mol L! HCI from 2mol L"! HCL 2)2.L 2mol L'! HSO, from 18mol L"! acid 3) 200mL 0, 1mol L! NaOH from 2mol L"! NaOH 4) 250mL 0.2mol L'! formalin from Smol L"! formalin What is the new molarity when you add :- 5) 50mL water to 200mls Imol L“! NaQH 6) 800mL water to 200 mls 2mol L"! CuSO, 7) 10L water to 10mls 10mol L*! HCl How much water do I add to convert :- 8) 20mL Smol L! NaOH to 2mol L*! NaOH 9) LL 10mol L*! HCI to 0.1mol L7 HCL 10) 50 mL 18mol L"! H,SO, to 0.Imol L! H,SO, Solutions 3.10 1. 11.7g 2. 0.5g 3. 1960g 4. 0,316g 5. 333.6g 6. 0.24g 7. 14.38 Solutions 3.11 1. 0.25mol L"! 2. 0.2mol L 3. 2.5 x 10%mol L*! 4. 0.2mol L*! 5. 0.0625mol L*! 6. 0.Smol L! 7. 0,025mol L! 8, 0.02mol L Solutions 3.13 (to assignment on next page) 1, [Na*] = Smol L"! [CO,? 2. [K*] = [NO,"] = 0.5mol Lt 3. [Na*] = [HCO,"] = 6.25 x 10°mol L*! 4, [H*] = [Cr] = Smol L*! 5. [APY] =3mol L*! [NO,]=9mol Lt 2.5mol Lt Chem 3.19e) Working With Ions We introduce a new convention that is used particularly when dealing with equilibria [GRONK] means molarity of GRONK. For example for !mol L-! HCI, {HC1] = Imol L*! Inproblems when you are asked to work out the molarity of a particular ion, the ion molarity is a simple multiple of the molarity of the parent compound. For example, with 2 mol L"! Al,(SO,),, there are 2 aluminium ions and 3 sulphate ions in the formula so [APY] x 2mol L'! = 4mol'Lt [so,*] Worked Example Calculate the molarity of each ion present when 5.85g NaCl and 14.9g KCl are dissolved in 200 mL, water? For each salt, molarity = moles Litres [Nac] = 1000.x 0.1 200 =0.5molL! (Kcl] = 1000x 0.2 200 =1.0mol L! 0.5mol L*! same molarity as NaCl 1.0mol L*! same molarity as KCL 0.5 + 1.0 one in each L.Smol L*! (Na*] (k'] {cr} © Set 3.13 Ion Molarities Calculate the molarity of each ion present in :- 1. 53g sodium carbonate in 200mL water 2. $.05g potassium nitrate in 100mL water 3. 2.1g sodium bicarbonate in 4L water 4. Smol L! HCI 5. 3mol L"! aluminium nitrate Solutions 3.12 1, 25mL add 475mL 2, 222mL add 1778mL 3. 10mL add 190mL 4, 10mL add 240mL_ 5.0.8mol L’! 6. 0.4mol Lt 7, 9.99 x 103 mol L"! 8. 30mL 9. 99L 10. 8950mL. Chem 3.20Mandatory Prac 16 Diluting Solutions Safety Audit Acid and alkaline solutions are dangerous. Use goggles, Procedure ‘You will be given a number of solutions to dilute. Diluting solutions is an art. You usually use pipettes, measuring solutions and volumetric flasks. When using beakers and stirring rods, you stir thoroughly. When using volumetric flasks, you grease the stopper thoroughly with silicone grease and shake all solutions thoroughly. 1. You are given 0.05M HCI and are asked to dilute it down in steps to - a) 0.001M HCI b) 0.00001M HCI Test its pH. It should be 5. 2. You are provided with 100 mL of a 1% solution of NaCl. This means you have 1g/100mL in the solution. You are asked to convert it to 0.1 mol L"' NaCl,,@). Show all calculation steps and do it 3. You are asked to prepare 100mL 0.01 mol L"! solution of copper sulphate using copper sulphate pentahydrate. Show all steps. What molarities of each ion does it contain ? e) Solubility Product Constants K ‘These constants are listed in chemical data books for insoluble salts and bases. They can be used to calculate the threshold molarities needed to produce precipitation. This table provides a selection: Chemical K Chemical = K AgCl 2x 1010 Ca(OH), 4x 106 Agi 8x 1017 CaSO, 9x 10% AgOH 2x 108 CuOH), 1x 10° Ag,S 6x 10°50 Cus, 6x 1036 AgSO, 2x 10° Fe(OH), 4x 10-40 AI(OH)3, 1x 10°33 FeS 5x 10°'8 BaCO, 5x10 PbCl, 2x 105 Ba(OH), 5x 103 Pb(OH),, 6x 10°16 BaSO, 1x 1010 PbS 1x 1078 CaCO, 5x 109 PbSO, 2x 10% The solubity product constant is a product of the ion molarities in the compound, We will work you through how it works. As before, [ x ] means molarity of x in mol L*! ‘These are two examples of K: for barium carbonate K = [Ba?*][CO,7"] for barium hydroxide K = [Ba*][OH"}? Chem 3.21© Set 3.14 Writing Solubility Product Expressions Write solubility product expressions for these : 1) silver chloride 2) silver sulphide 3) calcium carbonate 4) copper hydroxide 5) lead chloride ‘The solubility product equation allows you to ‘work out the threshold molarity of chemical above which a precipitate will form in a solution and sink to the bottom of the test tube. If the product of the ion ‘molarities exceeds the K value, a precipitate forms. eg. Find the threshold molarity of barium hydroxide for precipitation to begin occurring, for barium hydroxide Ba(OH), 4 K =[Ba*[oH? Letx be the threshold molarity Then [Ba?*] = x [or] = 2x as there are 2 ions present [Ba2*[OHP = 5x 103 [xl2xP = 5x 103 5x 103 1.1.x 10! mol Lt 43 x © Set 3.15 Calculating precipitation threshold molarities eg, Find the threshold molarity of the following, ‘chemicals for precipitation to begin occurring. 1) silver chloride 2) silver sulphide 3) calcium carbonate 4) copper hydroxide 5) lead chloride Chem 3.22, Another type of calculation is where we find the threshold molarity ofa particular ion in a solution eg find the molarity of copper ions necessary to begin precipitation in an alkaline solution where (OH-] = 10 mol L* For Cu(OH), [Cu?* J[OH-? = 1x 10°20 [Cu?* J[10? 2 = 1x 1020 [Cu2*} = 1x 10!6mol Lt © Set 3.16 More 1. Find the molarity of calcium ions necessary to begin precipitation in an alkaline solution where [OH] = 10? mol Lt. 2. Find the molarity of lead ions necessary to begin precipitation in an alkaline solution where [OH"] = 10° mol L! 3, Near a smoker vent on the sea floor, the molarity of sulphide ion in the sea water is 10 mol L"!. Find the molarity of copper ions from the volcanic emissions necessary to begin precipitation of copper sulphide on the sea floor. 4, Salt water has a molarity of 10 mol L"!. Find the minimum molarity of silver ions necessary to commence precipitation of silver chloride in salt water. Solutions 3.14 1) K=[Ag*][Cl] 2) K=[Ag*P{S*] 3) K=[Ca?*[CO,2] 4) K=[Cu** on? 5) K=([Pb*ycrP Solutions 3.15 1)For AgCl_ K=[Ag*][CI} Letx be the threshold molarity Then [Ag*][Cr] = 2x 10°10 [x][x] =2 x 10° w=2x 1010 x =14x 10% mol Lt2)For Ag,S K=[Ag*}[S*] Let x be the threshold molarity Then [Ag*?[S*] =6 x 10° [2xP[x] = 6 x 10°50 4x3 = 6 x 10°50 x =2.5x10'7 mol Lt 3) For CaCO, K =[Ca?*][CO,7] Let x be the threshold molarity Then [Ca?*][CO.*] = 5 x 10° [xx] =5 x 10° 2 =5x 10% x =7.1x 105 mol Lt 4) For Cu(OH), K = [Cu?*[OH}? Letx be the threshold molarity ‘Then [Cu?*][OH-} = 1 x 10°20 [x][2x]? = 1 x 10°20 4x3 =1x 100 x =14x 107 mol Lt 5) For PbCl, K=([Pb?*[Cr? Let x be the threshold molarity ‘Then [Pb?*[Cr}? = 2x 10° [x][2x]?= 2x 10°5 4x3 =2x 105 x =17x 10% mol Lt Solutions 3.16 1) ForCa(OH), [Ca®* [oH]? x 106 4x 106 4x 10? mol Lt [Ca¥ y[10? P [ca?*] 2) For Pb(OH), [Pb?* OH? = 6 x 1016 [Pb?* ][105 2 = 6x 1016 [Pb?*] = 6x 10% mol L 3) ForCus [Cu?* [Ss] = 6 x 1036 [Cu* [102] = 6x 1036 [Cu?*] = 6x 1034mol Lt 4) For AgCl [Ag*]ICr] = 2 x 10710 [Ag*][10?] =2 x 10°19 [Ag*]=2x 10% mol L! Chem 3.23 ) Equilibrium Considerations When we write the equation for a precipitation reaction such as our old silver silliness: AB agit Cl (aqy PABCIs) ‘The equation seems to imply that reactants react completely to form a product. This is usually not the case, particularly with closed systems where all the chemicals are enclosed and none are allowed to escape, Ina test tube containing the above reaction, all the chemicals are present in some concentration, ‘There is solid silver chloride on the bottom of the tube and ions of Ag* and Cl” remaining in solution. When you make the precipitate, a state of equilibrium is attained. You can tell that you are at equilibrium when no more changes appear to be occurring. However reactions continue. Both the forward and the reverse reactions are occurring. Some crystal is dissolving: AgClis) —. Ag ag cl “(aq And some crystal is being reformed continually: AB aqyt Cl aq PABCls) Chemical equilibrium is attained when a state of balance is present between the rate of forward and reverse reactions. The condition for equilibrium is : The rate of forward reaction = rate of reverse reaction. An equilibrium, once established, is easy to upset. You can dump in more chemical, or remove a product gas, or heat it, or cool it, or compress it, Chemists are meddling creatures.g) Toxic heavy metal pollutants Those involved in the chemical industry and who use chemicals should be concerned because most cancers have a chemical trigger and many chemicals are toxic. Gone are the days when chemical plants should be allowed to dump their waste into the Cook’s river, where I grew up, and Duck’s Creek Parramatta, where my parents roamed. Heavy metals seem to be a problem. The human body is composed mostly of lighter elements. When we are invaded by heavy metals and semi metals such as lead, mereury, cadmium, arsenic, selenium and copper, there can be quite nasty physiological effects. They retard growth and mental development in children. They can cause abdominal problems, hair loss, cancers and can kill in high concentrations, ‘The toxicity of lead has been known for some time. It was the first paint chemical and is a serious pollutant in old homes. Children would die after chewing their toys, Tetraethy! lead was a petrol additive, This is still being phased out. All car exhausts used to eject lead oxide all over the cities. ‘This inevitably concentrated in soils and waterways, Even ancient water pipes were made of lead. Lead dioxide and lead are still the vital ingredients of car batteries. I once looked down into the water where fishing trawlers were moored and was horrified to see the number of car batteries that they had dumped overboard. Mereury is another chemical of note. Itis still used by the gold mining industry in countries that do not care about the environment, in older style paper and chlorine bleaching plants. I worry about cheap paper recyclers. The Japanese experience in the town of Minimatta was a wake up call. Fish concentrate mercury up the food chain with sharks and rays (boneless fish that you give to babies) the prime culprits. First the cats went crazy, then the villagers. Mercury starved the brain in “mad hatters syndrome.” The hospitals filled with folk with their eyes turned up in their heads aware of little but their own suffering. Mercury cells are still used in flat batteries in clever appliances, They should be banned. ‘The production of heavy metals increases around the world. Rubbish dumps in Sydney have traditionally been sited in filled mangrove swamps near the waterways, To see the danger, one has to understand the nature of chemical equilibrium. Groundwater will continually leach through a rubbish dump with mercury and car batteries. Even though insoluble, some chemical will dissolve. If the product chemical moves down to the waterway, the equilibrium is driven forward, so more solution occurs. So what solutions do we need GOVERNMENT to introduce by regulation ? Old technology involving heavy metal production needs to be made uneconomic by taxation, Clay barriers need to be built around dumps to prevent leaching, Reoycling should be made mandatory. © Set 3.17 Issues 1.a) Outline how a chemist might identify whether chemical equilibrium has been attained ) Jdentify what is equal in an equilibrium 2. Summarise issues associated with heavy metal pollution. ‘No solutions will be given for this assignment. Chem 3.245. Water has a High Specific Heat C Once again the flight of the bumblebee returns to familiar territory. On page 3.6, we discussed how water with a specific heat of 4.18 J/g is much slower to heat than the hydrocarbon with much larger molecules, pentane, at 1.66J/g. ‘This unusual property of resisting temperature rises has some consequences: a) The oceans resist temperature changes allowing life to stabilise and flourish, 'b) Water is an ideal medium to absorb the heat allowing the accurate measurement of heat changes during chemical reactions. c) Bven given this remarkable property of water, man contiues to meddle with life. Power stations draw water from lakes and return it in heated form. This thermal pollution upsets the biological processes in the lake, a) Specific Heat (C) defined ‘The specific heat of a chemical is the number of Joules of energy needed to raise the temperature of ‘one gram of the substance by one celsius degree. You can see from this table that water does not like being pushed around by heat compared to some other chemicals: Chemical_| Symbol Specific heat (C) at room temp in J/g/"K Water 10 4) 4.18 Pentane CHa) 1.66 Copper Cugy 0.39 Iron Fes) 0.45 Nitrogen | Nyigy 1.04 Oxygen On6) 0.92 b) Types of Enthalpy Changes ‘All changes in the universe are associated with changes in energy. It follows from Einstein’s famous equation AE = Amc?. Changes in the nucleus of atoms involve the most violent energy changes. ‘Chemical and physical changes involve rearranging electrons and the breaking and formation of chemical bonds. The energy changes in chemical reactions can usually be survived. (i) Exothermic reactions Aw = -ve The enthalpy (heat) change AH is negative. ‘The chemicals lose heat to the surroundings. The surroundings get hot and the temperature rises. ‘You feel quite negative as you are being burned. I experienced an exothermic reaction for the first time asa child when I put my hands ona fuel stove in the kitchen. (ii) Endothermic reactions An = +ve ‘The enthalpy (heat) change AH is positive. The chemicals gain heat from the surroundings. The surroundings get cold and the temperature drops. You are a cool dude and feel positive. Chem 3.25iii) So what is this enthalpy stuff eh? Tell me that! Enthalpy is a theoretical thing called the “total energy content” of a system of chemicals. We do not attempt to measure it although some texts imagine that they can graph a chemical change as follows: { Enthalpy Enthalpy | a AH © A a Time Time Reaction 1 Reaction 2 The first graph is for a endothemic process as the enthalpy ends up higher. The second process is the ‘more natural exothermic reaction. Note ‘The enthalpy change AH=c-b ‘There is always an energy barrier to the reaction otherwise it would have been over and done with long ago. This is the hump of the reaction, the activation energy a. Using bunsens to overcome this barrier has been a source of great joy to young chemists. c) Using Calorimeters to Measure Enthalpy Changes Calorimeters are fun things. It looks like you are making coffee, but don’t drink the chemicals! You carefully measure out the chemicals that you are going to react and put $0 - 100ml of water in the cup. You measure the temperature (wait | minute) of the water before you react the chemicals. After adding the chemicals, you record the highest temperature reached for an exothemic reaction or the lowest temperature reached for an endothermic reaction. A typical School Calorimeter ‘The enthalpy change AH is computed using this formula: Stireing rod or straw AH = mCAT Where: Glad weop Allis the enthalpy change injoules. | so with two mis the mass of water in grams. Water : punched holes Cis the specific heat of water with ae (4.185 g1K-}) chemical fee AT is the temperature drop in °K. feta aoe ctystyrene cup Chem 3.26© set 3.18 Calculating Enthalpy Changes in Calorimeter Experiments Let us imagine that Charlie Bloggs has sacrificed his canteen coffee cup and a piece of lunch gladwrap to allow his impoverished class to do an experiment. In each case 100mL of water is used and C = 4.18 gobbledegook units. Use the data to answer the questions: 1, Neddie Evilnerd suggested that we attempt to measure Charlie Bloggs the enthalpy of solution of concentrated sulphuric acid. Perino ete Neddy Evilnerd Charlie is in hospital and Neddie has been taken away by 10 years ard —_the police for questioning - for pinching Charlie’s goggles and for premeditated labour assault. 2. Sodium thiosulphate (Hypo used in photography) Na,$,03.5H,0. We dissolved 2g in the water. The temperature dropped from 23°C to 21.5°C. Calculate a) the enthalpy change in the cup. b) the enthalpy change per gram of solute ) the enthalpy change per mole of solute (equals the enthalpy of solution of the chemical). 3. Potassium hydroxide KOH. We dissolved 3g in the water. The temperature rose from 23°C to 27.5°C. Calculate a) the enthalpy change in the cup. ») the enthalpy change per gram of solute ©) the enthalpy change per mole of solute (equals the enthalpy of solution of the chemical). 4. Calcium Ca. This hydrolyses with water as follows Cais) + H,Oq.)-> Ca* (ag) + 2011 (4qy + Hyg) We dissolved 2.5g in the water. The temperature rose from 23°C to 38°C, Calculate a) the enthalpy change in the cup. b) the enthalpy change per gram of reacting caleium \ ) the enthalpy change per mole of reacting calcium Mandatory Prac 17 Enthalpies of Solution Safety Audit Goggles. Try to avoid using mercury thermometers. The polystyrene cup can be quite “tippy” with the thermometer. You might like to wedge it in a small wooden box with some rock wool Procedure ‘The procedure mirrors the above, so you should know what to do. The temperature change is often quite small, $0 the more solute and the less water the better. The suggested chemicals in the syllabus are ammonium chloride and sodium hydroxide (caustic watch eyes. It is also deliquescent and hard to dissolve). Another suggestion is potassium nitrate. Solutions Set 3.18 2a) 627) b) 313.51/g c) 77748J/mol 3a) -1881J b) -6271/g c) -35,1125/mol 4a)-62705 b)-2508I/g c) -1003203/mol Chem 3.27