Redox Questions

1. 300 cm3 of a mixture of dinitrogen monoxide and nitrogen dioxide, at r.t.p. conditions is bubbled through 75 cm3 of 0.10 mol/dm3 acidified hydrogen peroxide solution. The nitrogen dioxide is oxidized to nitrate(V) ions, while the inert dinitrogen monoxide does not react. The remaining hydrogen peroxide in 50.0 cm3 of the resulting solution is then titrated with a 0.050 mol/dm3 acidified potassium manganate(VII) solution, of which 22.0 cm3 was required. Calculate the % by volume of dinitrogen monoxide in the gas mixture. 2. Titanium(IV) oxide is heated in H2(g) to give H2O(l) and a new oxide of titanium, TixOy(s). If 1.598g of titanium(IV) oxide produced 1.438g of TixOy, what is the formula of the new oxide (ie. what are the values of x and y)? 3. 10cm3 of a solution of iodate(V) ions of unknown molarity, was mixed with excess iodide ions. Both iodate(V) ions and iodide ions reacted with each other (in a redox reaction) to generate molecular iodine. The iodine generated required 30cm3 of 0.1 mol/dm3 of thiosulfate ions for complete redox reaction. a) Write all half-equations and balanced redox equations relevant to the problem above. b) Calculate the molarity of the iodate(V) solution used. 4. On heating, Group I metal nitrate(V) compounds decompose giving the metal nitrate(III) and oxygen gas, while Group II metal nitrate(V) compounds decompose giving the metal oxide, nitrogen dioxide and oxygen gas. 15.35g of a mixture of sodium nitrate(V) and magnesium nitrate(V) was heated in a fume cupboard until no more gases were evolved. The water soluble part of the residue was dissolved in 1dm3 of water to give solution A. 10cm3 of solution A was mixed with 20cm3 of 0.02mol/dm3 acidified potassium manganate(VII) solution, giving solution B. The excess potassium manganate(VII) in 15cm3 of solution B required 6cm3 of 0.05mol/dm3 of sodium ethandioate (Na2C2O4) solution for complete reaction. (a) Write all half-equations and balanced redox equations relevant to the problem above. (b) Calculate the sample masses of sodium nitrate(V) and magnesium nitrate(V) in the mixture. 5. MnO4-(aq) + 8H+(aq) + 5e-==> Mn2+(aq) + 4H2O(l) and Fe3+(aq) + e- ==> Fe2+(aq) (a) Calculate the percentage of iron in a sample of steel wire if 1.51 g of the wire was dissolved in excess of dilute sulphuric acid and the solution made up to 250 cm3 in a standard graduated flask. A 25.0 cm3 aliquot of this solution was pipetted into a conical flask and needed 25.45 cm3 of 0.0200 mol dm-3 KMnO4 for complete oxidation. (b) Suggest reasons why the presence of dil. sulfuric acid is essential for an accurate titration and why dil. hydrochloric and nitric acids are unsuitable to be used in this context.

(c) 8.25g of an iron(II) salt was dissolved in 250 cm3 of pure water. 25.0 cm3 aliquots were pipetted from this stock solution and titrated with 0.0200 mol dm-3 potassium manganate(VII) solution. The titration values obtained were 23.95 cm3, 23.80 cm3 and 23.85 cm3. (d) What titration value should be used in the calculation and why? (e) Calculate the % iron in the salt. 6. 2.83 g of a sample of haematite iron ore [iron (III) oxide, Fe203] were dissolved in concentrated hydrochloric acid and the solution diluted to 250 cm3. 7. 25.0 cm3 of this solution was reduced with tin(II) chloride (which is oxidised to Sn4+ in the process) to form a solution of iron(II) ions. This solution required 26.4 cm3 of 0.0200 mol dm-3 potassium dichromate(VI) for oxidation. (a) Deduce the fully balanced redox equations for the reactions (i) the reduction of iron(III) ions by tin(II) ions and (ii) the oxidation of iron(II) ions by the dichromate(VI) ion. (b) Calculate the percentage of iron(III) oxide in the ore. (c) Why isn't potassium manganate(VII) used for this titration? 8. An approximately 0.02 mol dm-3 potassium manganate(VII) solution was standardized against precisely 0.100 mol dm-3 iron(II) ammonium sulphate solution. 25.0 cm3of the solution of the iron(II) salt were oxidized by 24.15 cm3 of the manganate(VII) solution. (a) What is the molarity of the potassium manganate(VII) solution? 9. Calculate x in the formula FeSO4.xH2O from the following data: 12.18 g of iron(II) sulphate crystals were made up to 500 cm3 acidified with sulphuric acid. 25.0 cm3 of this solution required 43.85 cm3 of 0.0100 mol dm-3 KMnO4 for complete oxidation. 10. A piece of rusted iron was analysed to find out how much of the iron had been oxidised to rust [hydrated iron(III) oxide]. A small sample of the iron was dissolved in excess dilute sulphuric acid to give 250 cm3 of solution. The solution contains Fe2+ ions from the unrusted iron dissolving in the acid, and, Fe3+ ions from the rusted iron. (a) 25.0 cm3 of this solution required 16.9 cm3 of 0.0200 mol dm-3 KMnO4 for complete oxidation of the Fe2+ ions. Calculate the moles of Fe2+ ions in the sample titrated. (b) To a second 25.00 cm3 of the rusted iron solution an oxidising agent was added to convert all the Fe2+ ions present to Fe3+ ions. The Fe3+ ions were titrated with a solution of EDTA4-(aq) ions and 17.6 cm3 of 0.100 mol dm-3 EDTA were required. Assuming 1 mole of EDTA reacts with 1 mole of Fe3+ ions, calculate the moles of Fe3+ ions in the sample. Calculate the ratio of rusted iron to unrusted iron and hence the percentage of iron that had rusted. 11. 1.01g of an impure sample of potassium dichromate(VI), K2Cr2O7, was dissolved in dil. sulphuric acid and made up to 250 cm3 in a calibrated volumetric flask. A 25.0 cm3 aliquot of this solution pipetted

into a conical flask and excess potassium iodide solution and starch indicator were added. The liberated iodine was titrated with 0.100 mol dm-3 sodium thiosulphate and the starch turned colourless after 20.0 cm3 was added. Calculate the total mass of potassium dichromate(VI) in the original sample and hence its % purity.

Acid-Base Titrations
1. 50cm3 of aqueous sulfuric(VI) acid of unknown molarity was mixed with 75cm3 of 0.45mol/dm3 of aqueous potassium hydroxide. 55cm3 of the resulting alkaline solution A was mixed with 80cm3 of 0.35mol/dm3 of phosphoric(V) acid. 90cm3 of the new resulting acidic solution B required 39.97cm3 of aqueous sodium carbonate of unknown molarity, for complete neutralization. In a separate experiment, 625cm3 of the same aqueous sulfuric(VI) acid solution required 192.3cm3 of the same aqueous sodium carbonate solution for complete neutralization. Calculate the molarities of the sulfuric(VI) acid solution and the sodium carbonate solution. 2. 125cm3 of a solution of phosphoric(V) acid were mixed with 75cm3 of 0.25mol/dm3 of barium hydroxide. A 50cm3 aliquot of the resultant mixture required 7.5g of sodium carbonate for exact neutralization, in which a gas was produced. (a) Calculate the volume of the gas produced, at (i) r.t.p, and at (ii) s.t.p. (b) By calculating the molarity of phosphoric(V) acid used, calculate the sample mass of solid phosphoric(V) acid that needs to be dissolved in 125cm3 of pure water to prepare this molarity. 3. The monoprotic (monobasic) hydroxycarboxylic acid Z, derived from an alarm pheromone used by the African ant, has the molecular formula CH3RC(OH)COOH (where R refers to an alkyl group). It is known that Z contains 2 chiral carbons (where a chiral carbon refers to a carbon atom bonded to 4 different groups). A solution formed by dissolving 1.0g of Z in 250cm3 of water, had a pH of 2.73; a 25.0cm3 aliquot of this solution required 6.85cm3 of 0.10 mol/dm3 NaOH(aq) for neutralization. Draw the full displayed structural formula of compound Z. 4. 100 cm3 of a magnesium hydroxide solution required 4.5 cm3 of sulphuric acid (of concentration 0.100 mol dm-3) for complete neutralisation. (a) give the equation for the neutralisation reaction. (b) calculate the moles of sulphuric acid neutralised. (c) calculate the moles of magnesium hydroxide neutralised. (d) calculate the concentration of the magnesium hydroxide in mol dm-3 (molarity). (e) calculate the concentration of the magnesium hydroxide in g cm-3. 5. A 50.0 cm3 sample of sulphuric acid was diluted to 1.00 dm3. A sample of the diluted sulphuric acid was analysed by titrating with aqueous sodium hydroxide. In the titration, 25.0 cm3 of 1.00 mol dm3 aqueous sodium hydroxide required 20.0 cm3 of the diluted sulphuric acid for neutralisation. (a) give the equation for the full neutralisation of sulphuric acid by sodium hydroxide. (b) calculate how many moles of sodium hydroxide were used in the titration?

(c) calculate the concentration of the diluted acid. (d) calculate the concentration of the original concentrated sulphuric acid solution. 6. (a) A pipetted 25.0 cm3 aliquot of a solution of sodium carbonate is to be titrated with an approximately 1.0 mol dm-3 hydrochloric acid to be standardised. What mass of dried anhydrous sodium carbonate must be dissolved in 250 cm3 of deionised water, so that a 25.0 cm3 aliquot of the carbonate solution will give a 20.0 cm3 titration with the hydrochloric acid? (b) What is the molarity of the sodium carbonate solution, assuming 100% purity of sodium carbonate? (c) The simplified molecular structure of 2-ethanoylhydroxybenzoic acid ('Aspirin') is CH3COOC6H4COOH. Give the equation of its reaction with sodium hydroxide. (d) A sample of aspirin was to be analysed for purity by titrating it with standardised 0.100 mol dm3 sodium hydroxide using phenolphthalein indicator. Assuming 100% purity and access to a 4 decimal place electronic balance, calculate the mass of Aspirin that should be weighed out to give a titration of 23.0 cm3 of the alkali. (e) The main contaminant is likely to be unreacted 2-hydroxybenzoic acid. Why is this likely to be an impurity? How will this affect the % purity you calculate? (f) In human teeth, approximately 96% of the outer enamel and 70% of the inner dentine are composed of the apatite mineral, calcium hydroxy phosphate. If the simplest empirical formula is Ca5(PO4)3OH, calculate the % calcium in the apatite mineral. (g) A dried 1.40g human tooth was dissolved in a small quantity of hot conc. nitric acid. A drop of methyl orange indicator was added followed by drops of 6M sodium hydroxide until the indicator turned orange to neutralise the solution. The solution was then made up to 250 cm3 in a volumetric flask. 10.0 cm3 of this solution was pipetted into a conical flask and ~1 cm3 of a conc. ammonia/ammonium chloride pH10 buffer was added. This solution was then titrated with 0.0200 mol dm-3 EDTA using Eriochrome Black T indicator. The indicator turned blue after 22.5 cm3 of EDTA was added. Calculate the average % by mass of calcium throughout the tooth. 7. 25.0 cm3 of seawater was diluted to 250 cm3 in a graduated volumetric flask. A 25.0 cm3 aliquot of the diluted seawater was pipetted into a conical flask and a few drops of potassium dichromate(VI) indicator solution was added. On titration with 0.100 mol dm-3 silver nitrate solution, 13.8 cm3 was required to precipitate all the chloride ion. (a) Give the ionic equation for the reaction of silver nitrate and chloride ion. (b) Calculate the moles of chloride ion in the titrated 25.0 cm3 aliquot. (c) Calculate the molarity of chloride ion in the diluted seawater. (d) Calculate the molarity of chloride ion in the original seawater.

(e) Assuming that for every chloride ion there is a sodium ion, what is the theoretical concentration of sodium chloride salt in g dm-3 in seawater? 8. 5.00 g of a solid mixture of anhydrous calcium chloride(CaCl2) and sodium nitrate (NaNO3) was dissolved in 250 cm3 of deionised water in a graduated volumetric flask. A 25.0 cm3 aliquot of the solution was pipetted into a conical flask and a few drops of potassium dichromate(VI) indicator solution was added. On titration with 0.1 mol dm-3 silver nitrate solution, 21.2 cm3 was required to precipitate all the chloride ion. [Atomic masses: Ca = 40, Cl = 35.5] (a) Calculate the moles of chloride ion titrated. (b) Calculate the equivalent moles of calcium chloride titrated. (c) Calculate the equivalent mass of calcium chloride titrated. (d) Calculate the total mass of calcium chloride in the original 5.0 g of the mixture. (e) The % of calcium chloride and sodium nitrate in the original mixture. 9. A bulk solution of hydrochloric acid was standardised using pure anhydrous sodium carbonate (Na2CO3, a primary standard). 13.25 g of sodium carbonate was dissolved in about 150.0 cm3 of deionised water in a beaker. The solution was then transferred, with appropriate washings, into a graduated flask, and the volume of water made up to 250 cm3, and thoroughly shaken (with stopper on!) to ensure complete mixing. 25.0 cm3 of the sodium carbonate solution was pipetted into a conical flask and screened methyl orange indicator added. The aliquot required 24.65 cm3of a hydrochloric acid solution, of unknown molarity, to completely neutralise it. (a) Calculate the molarity of the prepared sodium carbonate solution. (e) What is the molarity of the hydrochloric acid? 10. 0.279g of an organic monobasic aromatic carboxylic acid, containing only the elements C, H and O, was dissolved in aqueous ethanol. A few drops of phenolphthalein indicator were added and the mixture titrated with 0.100 mol dm-3 sodium hydroxide solution. It took 20.5 cm3 of the alkali to obtain the first permanent pink. (a) Calculate the molecular mass of the acid. (e) Suggest possible structures of the acid with your reasoning. 11. The solubility of calcium hydroxide in water can be measured reasonably accurately to 3sf by titrating the saturated solution with standard hydrochloric acid. (a) If the standard hydrochloric acid is made by diluting '2M' bench acid, what volume of the '2M' acid is required to make up 250 or 500 cm3 of approximately 0.1 mol dm-3 hydrochloric acid and how might you do it? (b) Why must the 2M acid be diluted and why must the diluted acid be standardised? In the calculation below assume the molarity of the standardised hydrochloric acid is 0.1005 mol dm-3. At 25oC, a few grams of solid calcium hydroxide was shaken with about 400 cm3 of deionised

water, and then filtered. 50.0 cm3 samples of the 'limewater' gave an average titration of 15.22 cm3 of 0.1005 mol dm-3 hydrochloric acid using phenolphthalein indicator. (c) If the acid is in the burette, how would you measure out the calcium hydroxide solution? and why is phenolphthalein indicator used? (f) Calculate the molarity of the solution in terms of mol Ca(OH)2 dm-3. (g) What is the approximate solubility of calcium hydroxide in g Ca(OH)2 per 100g water? 12. Analysis of limewater. 25.0 cm3 aliquots of a calcium hydroxide solution were titrated with 0.100 mol dm-3 (0.100M) hydrochloric acid using phenolphthalein indicator. On average it took 10.50 cm3 of the acid to neutralise the limewater. Calculate (a) the molarity of the calcium hydroxide solution (b) the concentration of calcium hydroxide in (i) g dm-3 and (ii) g/100 cm3 13. The purity of anhydrous sodium carbonate can be determined by titration with standard hydrochloric solution. The following results were obtained on titrating accurately weighed amounts of sodium carbonate with 1.00 mol dm-3 hydrochloric acid (1.00 M HCl) to complete neutralisation given by the equation below. Na2CO3 + 2HCl ==> 2NaCl + H2O + CO2 14. Analysis Result 17. (i) 20. (ii) 23. (iii) 15. Mass of Na2CO3 18. 1.113 g 21. 1.092 g 24. 1.166 g 16. titration 19. 20.95 cm3 22. 20.55 cm3 25. 22.00 cm3

The titration values were recorded to the nearest 0.05 cm3 for a burette calibrated in 0.1 cm3 increments. In each case calculate (a) the moles of HCl used in each titration, (b) the moles of Na2CO3 titrated based on the moles of HCl used, (c) the mass of Na2CO3 titrated based on (b), and finally, (d) from your (b) and (c) calculations, calculate the % purity of the anhydrous sodium carbonate, quoting what you think is the most accurate analytical result.

Hydrated Salts/Water of Crystallization

1. A mixture of MgSO4.7H2O and CuSO4.5H2O is heated until a mixture of the anhydrous salts, is obtained. If 5.0g of the hydrated mixture when heated gives 3.0g of the anhydrous salts, calculate the % by mass of CuSO4.5H2O in the initial hydrated mixture. 2. 4.28 g of a hydrated form of the salt sodium sulphate, Na2SO4.xH2O, was heated at 180oC until the remaining mass became constant at 1.89 g. Calculate x, the number of molecules of 'water of crystallisation'.

3. Blue hydrated copper(II) sulfate crystals have the formula CuSO4.xH2O, where x is the number of molecules of 'water of crystallization'. If 3.33g of copper sulphate crystals where heated at 150oC until the residue of anhydrous copper sulphate remained constant at 2.12g. (a) Calculate the % water of crystallisation in the blue copper sulphate. (b) From your answer to (a) calculate the value of x in the formula of the blue crystals. 4. 10.0 g of iron(II) ammonium sulphate crystals were made up to 250 cm3 of acidified aqueous solution. 25.0 cm3 of this solution required 21.25 cm3 of 0.0200 mol dm-3potassium dichromate(VI) for oxidation. Calculate x in the formula FeSO4.(NH4)2S04.xH2O

Gases
1. At r.t.p, 10cm3 of a hydrocarbon, 85.7% CARBON by mass, undergoes complete combustion to produce an acidic oxide, which requires 16.65cm3 of 0.2mol/dm3 of NaOH(aq) for complete neutralization (ie. no acidic protons present in the salt produced). What is the density of the hydrocarbon at r.t.p? 2. When methane was burnt in an incorrectly adjusted burner, it was converted into a mixture of carbon dioxide and carbon monoxide in the ratio of 99:1, together with water vapour. What is the volume of oxygen consumed if xdm3 of methane was burnt? 3. On reaction with dilute hydrochloric acid, 0.428 g of a group 2 metal (M) formed 75.0 cm 3 of hydrogen gas at 298K/1 atm pressure. If the molar volume of gas is 24.0 dm3 at 298K/1 atm, deduce the atomic mass of the metal and identify it from the periodic table.

Extra Aspirin Question (needs organic chem)

2-ethanoylhydroxybenzoic acid (acetylsalicylic acid), known commercially as aspirin, can be analysed by titration with standard sodium hydroxide solution when a sample of it is dissolved aqueous alcohol (a mixture of ethanol and water) and using phenolphthalein indicator (pKind = 9.3, useful range pH 8.3-10). In the pharmaceutical industry, aspirin is manufactured by reacting 2-hydroxybenzoic acid (salicylic acid) with ethanoic anhydride. Prior to this reaction, 2-hydroxybenzoic acid is manufactured by reacting carbon dioxide with phenol, the mixture is heated under pressure sodium hydroxide in the so called Kolbe Reaction. Aspirin, therefore, always contains a small percentage of 2-hydroxybenzoic acid as an impurity! (a) Give the equation for the Kolbe synthesis of 2-hydroxybenzoic acid. (b) Give the equation for the formation of aspirin from 2-hydroxybenzoic acid. (c) Give the molecular formulae and calculate the molecular masses of 2-hydroxybenzoic acid and aspirin.

Accurate relative atomic masses: Ar(C) = 12.01, Ar(H) = 1.01, Ar(O) = 16.00 (d) Why must ethanol be added to the water prior to doing the titration? (e) Five samples of aspirin were titrated with commercially purchased precisely 0.1000 mol dm 3 (0.1000M) sodium hydroxide solution and the results are given below. The titration values were recorded to the nearest 0.05 cm3, which is reasonable of a burette calibrated in 0.1 cm3 increments. mass of aspirin (g) 0.3591 0.3532 0.3686 0.3583 0.3635 av titre/mass = ? cm3/g In each case calculate the titre/mass and work out its average value for the five titrations. (f) Assuming that only aspirin was titrated (though not true), from the average titre/mass figure calculate the 'theoretical' % purity of the aspirin by the following sequence: (i) What volume of 0.1000 M NaOH is equivalent to 1.000 g of aspirin? (ii) Give the reaction equation for the titration. (iii) How many moles of aspirin can be titrated by your answer to (i) (iv) from (iii) calculate the theoretical mass of aspirin titrated. (v) From (iv) calculate the theoretical % purity of the aspirin! (g) Why is the theoretical % purity based on this titration method always likely to be over 100%?, ignoring any titration errors - which does not necessarily explain why via this method of analysis you will always tend to get >100%, especially if you do the titration very accurately! (h) Assuming that 2-hydroxybenzoic acid is titrated with NaOH on a 1 : 1 molar basis, calculate the % of this impurity in the aspirin by the follow sequence: titration/cm3 of 0.1M NaOH 20.05 19.65 20.60 19.90 20.25 titre/mass ? ? ? ? ?

(i) From your answer to (f)(iii) calculate an average molecular mass (ii) From the average molecular mass, and a little bit of algebra, using x as the % of the 2-hydroxybenzoic acid impurity, calculate the value of x. (i) Suppose for the sake of argument, there was an error of 0.1 cm3 on the titration value which is likely to be the biggest source of error. Obviously there are errors associated with the NaOH molarity, the weighing, burette reading. (i) What is the approximate % error on the titration value? (ii) What error range of values for Mr(av) would this give? (iii) Using the minimum and maximum values from (ii), recalculate the % of 2-hydroxybenzoic acid in the aspirin using the method indicated in (h) and quote the range of possible values. (iv) Comment on the results of your calculations, a bit worrying for some coursework projects! yes? (v) In principle, what must an alternative method be capable of doing? Can you suggest an appropriate method - and forget acid-alkali titrations!