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# CHEMISTRY OLYMPIAD 2007 UK Round One

1. This question is about launching the space shuttle
To launch the space shuttle, two propulsion systems are used. Most of the thrust for the first two minutes of flight comes from the two reusable solid rocket boosters. The socalled ‘external tank’ provides the remainder of the thrust needed to get the shuttle into orbit. The external tank is filled with li uid hydrogen and li uid oxygen which react to form water. The solid rocket boosters use a mixture of aluminium powder and ammonium perchlorate, !"#\$l%#, together with an iron oxide catalyst and an organic binder. (a) &rite the e uation for the reaction between hydrogen and oxygen. (b) The external tank has a mass of '( tonnes )'(,*** kg+ when empty and (#, tonnes when full. -ssuming these are present in the correct stoichiometric proportions, calculate the masses of hydrogen and oxygen in the external tank. (c) .n practice, the actual masses of hydrogen and oxygen used are /*# and 0/# tonnes respectively. 1iven that the densities of li uid hydrogen and oxygen are *.*(*2 and /./#/ g cm34, calculate the volumes of these li uids needed and hence the total capacity of the external tank in m4. The reaction that takes place during the combustion of the solid rocket booster fuel has been summari5ed as6 /*-l)s+ 7 0!"#\$l%#)s+ #-l'%4)s+ 7 '-l\$l4)s+ 7 /'"'%)l+ 7 4!')g+ (d) 1iven the following standard enthalpies of formation, calculate the standard enthalpy change at '82 9 for this reaction as given. !"#\$l%#)s+ ΔfH : k; mol3/ 3'8,.4 -l'%4)s+ 3/0(,.( -l\$l4)s+ 3(*#.' "'%)l+ 3'2,.2

(e) 1iven that #,* tonnes of solid propellant are used in the solid rocket boosters in total, and that aluminium is the limiting reagent present at /0< in the mixture, calculate the energy released when this is reacted according to the above e uation. 2. This question is about geometric shapes in chemistry =hosphorus exists as a number of allotropes, the most reactive being white phosphorus. This was first prepared in the /(th century from the reduction of the phosphate present in urine. >olid white phosphorus contains =# molecules, with each = atom at the vertex of a regular tetrahedron. cuboctahedron (a) ?raw the structure of a molecule of =#, showing all the chemical bonds. (b) "ow many edges are there in total in a regular tetrahedron@ &hite phosphorus spontaneously ignites in air to form a mixture of phosphorus)...+ oxide and phosphorus)A+ oxide. (c) &rite an e uation for the formation of i) phosphorus)...+ oxide and ii) phosphorus)A+ oxide from the elements. The structure of each oxide is also based on a regular tetrahedron. The phosphorus atoms remain at the vertices but are no longer bonded to each other. .nstead the = atoms are Boined by bridging oxygens. (d) ?raw the structure of phosphorus)...+ oxide. =hosphorus)A+ oxide has a further oxygen atom bonded to each phosphorus atom at the vertex of the tetrahedron. (e) ?raw the structure of phosphorus)A+ oxide.

to form a precipitate of ammonium molybdophosphate.molybdenum atom lies at each vertex of the cuboctahedron and these are Boined by oxygen atoms with every edge of the cuboctahedron being bridged by an oxygen atom.further oxygen atom is Boined to every vertex. Ioth Ga=%# and -l=%# are essentially insoluble in water and are therefore removed as precipitates.single phosphate unit lies at the centre of the structure with each of its four oxygen atoms coordinating to three molybdenum atoms.'.2 mmol dm34. (i) "ow many i) vertices and ii) edges are there in a cuboctahedron@ (j) \$alculate the number of i) molybdenum atoms and ii) oxygen atoms in the molybdophosphate ion. (a) &hich two of the following statements explain why so many moles of hydroxide are needed per mole of ammonium molybdophosphate@ \$ircle the correct options in the answer booklet. . To determine the concentration of phosphate ions in solution.# Ganthanum carbonate )marketed as FosrenolTM+ is currently being used to treat hyperphosphataemiaH aluminium sulfate has been used to control phosphate levels in ponds.uantitative method for determining phosphate levels in a ueous solution involves adding ammonium molybdate.safe level of phosphate in blood serum is D/. . caused by an inability of the kidneys to filter out excess phosphate from food. to phosphate ions+ is titrated with !a%" using a phenolphthalein indicator. ammonium molybdophosphate )formed by the addition of ammonium molybdate. This question is about phosphate levels in our environment Cxcess phosphate is undesirable in our water supply since it promotes the growth of algae. . \$alculate the concentration of phosphate in the blood serum in mol:dm4. (f) ?raw the molecular structure of phosphoric)A+ acid. (k) 1iven that no atom changes its oxidation state during the formation of ammonium molybdophosphate. )!"#+'Mo%#.* cm4 of treated blood serum was reacted with excess ammonium molybdate and the precipitated ammonium molybdophosphate re uired /(. "igh phosphate levels in the blood )hyperphosphataemia+. The structure of this solid is based on a cuboctahedron ) shown above+.Cach oxide reacts with water to form an acid 3 phosphorus)A+ oxide forms phosphoric)A+ acid.*/** mol:dm4 !a%". )!"#+'Mo%#. showing all of the bonds. (c) The degree to which a phosphate ion is protonated in a ueous solution depends on the p". %ne mole of ammonium molybdophosphate contains one phosphate unit and re uires '4 moles of !a%" in the titration before the end point is reached. . calculate the overall charge of the molybdophosphate ion and hence the formula of ammonium molybdophosphate. (h) \$alculate the oxidation state of molybdenum in ammonium molybdate. (g) &rite the e uation for the reaction forming phosphoric)A+ acid. . . Ese the following data to calculate which form of phosphate is prevalent in blood serum at p" F (. "4=%#. cause a range of bone diseases. ! >odium hydroxide is a weak alkali " -mmonium molybdophosphate has a very high molecular mass # The molybdenum-containing species is acidic \$ =hosphate ions are acidic % The molybdophosphate ion contains many molybdenums (b) /*. . cm4 of *.

using sulfuric acid for acidification )there is only one other product+.+ with chlorine gas. sulfur dioxide. was the first oxide of chlorine to be discovered.f an e uimolar solution of aluminium and lanthanum ions is added slowly to a solution containing phosphate ions. The company Sabre produce their \$l%' by oxidising sodium chlorate). (d) &rite a balanced e uation for the formation of \$l%' by this reaction. \$l%'. it has been used to remove mould from houses flooded following "urricane 9atrina in !ew %rleans.n the laboratory. \$hlorine dioxide was first obtained by "umphry ?avy by the very ha5ardous disproportionation of chloric acid. ii+ Esing these oxidation states. (b) i) 1ive the oxidation states of chlorine in \$l%'. write a balanced e uation for the formation of \$l% ' from "\$l%4. The saturated concentrations of these phosphates can be worked out from their solubility products )Ksp+6 Ksp)Ga=%#+ F JGa47)a +KsatJ=%#43)a +Ksat F (. ii+ &rite a balanced e uation for the formation of \$l%' from chlorine and sodium chlorate). \$l%' is made by the partial reduction of !a\$l% 4 under acidic conditions using a variety of reducing agents. \$l%' is produced by the reaction between !a\$l%4 and oxalic acid. The other products of this disproportionation reaction are water and perchloric acid. (c) &rite a balanced e uation for the formation of \$l% ' by this reaction. or otherwise. which phosphate would precipitate first@ &. for example. Mor pulp bleaching. (a) ?raw a ‘dot L cross’ diagram of a \$l% ' molecule showing the outershell electrons. More recently.. -lthough unstable as a li uid or gas.. . it is now produced on a very large scale for the bleaching of wood pulp and for water treatment. )\$%%"+'. formed by adding concentrated sulfuric acid to a solid chlorate such as 9\$l% 4. "\$l%4 and "\$l%#. This question is about chlorine dio'ide \$hlorine dioxide.+. chlorine dioxide is usually generated where it is to be used.*2×/*3'( mol' dm30 Ksp)-l=%#+ F J-l47)a +KsatJ=%#43)a +Ksat F 8. . again in the presence of sulfuric acid. iii+ 1ive the structure of a molecule of perchloric acid.+. "\$l%#.. This also generates \$%'... "\$l%4. which dilutes the \$l%'. &hat is the bond angle in the perchlorate ion@ Mor safety reasons.(d) &rite the e uation for the reaction between lanthanum carbonate and the hydrochloric acid present in the stomach. (e) i) >uggest the formula for sodium chlorate).2#×/*3'/ mol' dm30 (e) \$alculate the concentration of a saturated solution of lanthanum phosphate. (f) .. 1ive an estimate of the %-\$l-% bond angle.