Higher 2 = Paper 2 Structured Questions _ a GENERAL PAPER ‘Answer all the questions. Planning (P) The reaction between a carboxylic acid and an alcohol to form an ester and water is reversible. Usually the rate of reaction is slow and so a strong acid catalyst is used. Even with a catalyst the reaction mixture must be left for one week to reach equilibrium. To determine the equilibrium constant, K,, it is necessary to determine the amounts of carboxylic acid, alcohol, ester and water present in the equilibrium mixture. One way of doing this is described below. Known amounts of a carboxylic acid, an alcohol and a dilute strong acid are mixed and stored in a sealed container. After sufficient time, the whole mixture is titrated against a standard solution of sodium hydroxide. This allows the total amount of acid in the mixture to be found. This total amount of acid is made up of the strong acid and the carboxylic acid present in the equilibrium mixture. The change in the amount of carboxylic acid present in the ivitial mixture and the equilibrium mixture can then’be calculated. This can be used to deduce the amounts of each of the other components in an equilibrium mixture, Using these data, a value for K, may then be determined. Amore reliable average value for K, is obtained if the experiment is repeated several times using different initial ratios of reactants each time. Using the information given above, you are required to write a plan for determining a value for the ‘equilibrium constant, K,, for the reaction between propanoic acid and methanol, to form methyl propanoate and water. Data name M, propanoic acid 74.0 methanol 32.0 water 18.0 - (a) Write a balanced equation to represent the reversible reaction between propanoic acid and methanol. Show the displayed formula of the ester. (11 (2015)16 H2 Chemistry(b) You may assume that you are provided with 1.00moldm sodium hydroxide, approximately 3moldm® hydrochloric acid, 10g propanoic acid, 10g methanol, the equipment and materials normally found in a school or college laboratory. Your plan should include the following. « anoutline of how the accurate concentration of the hydrochloric acid may be determined an outline of how results would be obtained for two different initial reaction mixtures: brief, but specific, details of how the results would then be used to obtain the amounts in moles of 4. _allthe components in one of your initial reaction mixtures 2. propanoic acid present in this mixture at equilibrium 3. all the other components in this mixture at equilibrium (For the purposes of this calculation, you may assume that 1.00cm* of hydrochloric acid contains 1.00.cm? of water and that the density of water is 1 genr®.) «any relevant safety precaution you consider important These data could then be used in the following expression to determine K.: ester] [water = Tearboxylic acid] [alcohol] You do not need to show how a K, value is calculated. m1 [Total: 12] (2015)17 H2 Chemistry2 Methane, methanol and hydrogen have all been investigated as possible alternative fuels for motor vehicles that currently use petrol. The table below compares the energy released on combustion of these fuels. . tet | |aseGand (otkPa amie} Orn ee See (gdm) (MJdm~*) petrol 740-770 = 473 33.6-36.4 methane 0.645 891 55.5 0.0358 methanol 792 726 22.7 18.0 hydrogen 0.0884 -286 143 0.0126 (a) (i) Define the term standard enthalpy change of combustion, AH’. - 2 (ii) Suggest why no value is quoted for the standard enthalpy change of combustion of petrol in the table above. (1 (b) Although methane and hydrogen release large amounts of energy per gram on combustion, the large volume needed to store these gases limits their use in vehicles. One solution is to store the gas in a pressurised cylinder operating at 24.8MPa. [1MPa = 10°Pa] wo Es ke data above to calculate the eneray released per dm® of methane at 25°C and .8MPa. 1] (ii) Although hydrogen releases less than half the energy per dm? than methane, many people believe that hydrogen is a better alternative fuel compared to methane. Suggest why. (201518 H2 Chemistry(c) Methanol has the advantage of being a liquid at 25°C, so it can be stored in conventional fuel tanks. Explain in terms of the intermolecular forces involved, two reasons why methanol has a significantly higher boiling point than methane. (d) One alternative fuel technology involves the conversion of liquid methanol into hydrogen gas, as shown by the equation below. CH,OH(!) > 2H,(g) + CO) (1) Calculate the standard enthalpy change, AH®, for this reaction using appropriate data from the table on page 6. ‘You will also need to use the standard enthalpy change of combustion of carbon monoxide, which is -263kJmoh" (2) (ii) If the standard entropy change, AS®, for this reaction is +332JK"'mol", calculate the minimum temperature above which this reaction is spontaneous. 2 (e) Carbon monoxide produced by the above process is toxic to humans because it reduces the capacity of haemoglobin to transport oxygen around the body. In terms of the bonding involved, explain how carbon monoxide prevents oxygen from being transported around the body. (21 [Total: 13] (2015)19 H2 Chemistry3 Whenbriefly exposed to a bright light, a mixture of hydrogen gas and chlorine gas reacts explosively to give hydrogen chloride gas. H,(g) + Cl,(g) -» 2HCI(g) (a) (i) Use relevant bond energy values given in the Data Booklet to calculate the enthalpy change for this reaction, AH. t) (li) Draw arrows on the energy diagram below to show each of the bond breaking and bond making steps you have used in your calculation above. Label each level with the appropriate formulae. energy Tks H,(9) + Clg) sn ep (3) (b) (i) Explain why the reaction only starts when it is exposed to bright light. ~ (t] (ii) Suggestthe type of mechanism occurring in this reaction and write an equation to represent the first step in the mechanism. (2) (iii) Suggest why the reaction continues with increasing rate after the brief exposure to the bright light has stopped. (2015)20 . H2 Chemistry{c) Gaseous bromine reacts with hydrogen in a similar way to chlorine but is less reactive. Explain this difference in reactivity by referring to relevant bond energies from the Data Booklet. (d) Hydrogen chloride gas can also be made by the addition of concentrated sulfuric acid to sodium chloride. (i) Write an equation for this reaction. (1) (ii) Explain with the aid of an equation why this method would not be suitable to prepare hydrogen bromide from sodium bromide. (e) Both hydrogen chloride and hydrogen bromide dissolve readily in water. Describe a chemical test, which does not involve silver nitrate, that could distinguish between aqueous solutions of these two gases. [Total: 18] (2015)21 H2 Chemistry4 Noradrenaline and adrenaline are hormones that are produced by the body during times of stress. OH OH i Ho. NH, Ho. N. oe 2 aes “CH, HO" HO’ noradrenaline adrenaline (a) These hormones act by binding to protein receptors in the body. This involves hydrogen ‘bonding between the hormone molecule and amino acid side chains, such as the CH,OH side chain in serine, Draw a displayed formula to show a possible hydrogen bond between an adrenaline molecule and a serine side chain. Show any relevant dipoles. 2) (b) Adrenaline is formed from noradrenaline in the body by an S,2 reaction between the amine group of noradrenaline and a suitable methyl compound. (i) Draw a mechanism for the reaction between an amine, R-NH,, and methyl iodide to form R-NHCH, and any other products. Show relevant lone pairs and dipoles, and use curly arrows to indicate the movement of electron pairs. (4) (ii) Explain why this reaction proceeds mainly via an S,2 mechanism rather than an S,1 mechanism. (2015)22 H2 Chemistry(c). These hormones are used widely for clinical treatment and are synthesised by drug companies from simpler compounds. (i) Complete the reaction scheme to show how noradrenaline could be synthesised from 3,4-dihydroxybenzaldehyde in two steps using inorganic. reagents. Show the structure of the intermediate compound and state the reagents and conditions for each step. ° OH ao 4 step 4 step2 4 NH, = = HO" H 3.4-dihydroxybenzaldehyde noradrenaline Intermediate compound step 1 . step 2 7 3 (li) Explain why 50% of the drug synthesised by the method above is unlikely to be active in the human body. (2015)23 H2 Chemistry(d) ‘The concentration of a solution of adrenaline can be determined by oxidation with silver(I) ‘oxide to form a pink coloured compound with formula C,HjNO;. The half equation for the oxidation of adrenaline is shown below. CH,,NO, > °C,H,NO,)+ 4H" + den (i) Construct a half equation for the reduction of silver(1) oxide. se Et] (ii) Adrenaline solution for medical use typically has a concentration of 3.0 x 10*moldnr*. Use your answer in (i) to calculate the mass of silver(I) oxide that would be required for the complete oxidation of a 50cm? sample of adrenaline solution - (2) Total: 16] (2015)24 H2.Chemistry5. Two unknown organic compounds X and Y were found to contain carbon, hydrogen and chlorine only. The following investigations were carried out. (a) Both X and Y were heated separately under reflux with dilute aqueous sodium hydroxide for 30 minutes. No reaction occurred in either case. State what information this result gives about the compounds, and explain why they do not react with aqueous sodium hydroxide under these conditions. (b) (1) Compound X contains 49.0% carbon, 2.7% hydrogen and 48.3% chlorine by mass. Determine the empirical formula, showing all your working. empirical formula . (ii) A sample of compound X weighing 0.344g was vaporised at 181°C and 101kPa, and found to occupy a volume of 87.4cm?. Use this data and your answer from (i) to determine the molecular formula of this compound. molecular formula ....... . 4 (2015)25 H2 Chemistry{c) Compound ¥ has a molecular formula of C,H,Cl. ‘Suggest three possible structures for Y. State the name of each structure you have drawn. (3) (d) Mononitration of compound Y produces just one compound rather than a mixture of isomers. Use this additional information to identify which structure in (c) is that of Y, and write an equation for the mononitration of Y with a suitable reagent. (2) [Total: 13] (2015)26 H2 Chemistry