F322: Chains, Energy and Resources 2.2.4 Alcohols



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F322: hains, Energy and Resources 2.2.4 Alcohols 167 marks 1. This question is about the six alcohols below. butan-2-ol 2-methylpentan-3-ol propan-1-ol ethane-1,2-diol 2-methylpropan-2-ol propan-2-ol Which alcohol is an example of a tertiary alcohol?... [Total 1 mark] 2. Ethane-1,2-diol can be dissolved in water to act as an anti-freeze in car radiators. Explain why ethane-1,2-diol is very soluble in water............. [Total 2 marks] 3. Ethane-1,2-diol is heated under reflux with ethanoic acid and a small amount of 2 SO 4 catalyst. ompound A is formed with molecular formula 6 10 O 4. Draw the structure of compound A. [Total 2 marks] Plymstock School 1

4. Butan-2-ol is heated with 2 SO 4 catalyst. A mixture of three alkenes forms, B, and D. The alkenes B and are stereoisomers. Draw the structures of the two stereoisomers B and. What type of stereoisomerism is shown by B and?... (iii) Draw the structure of the other alkene, D, that is formed in this reaction. [Total 4 marks] Plymstock School 2

5. Alcohol E is one of the following alcohols. butan-2-ol 2-methylpentan-3-ol propan-1-ol ethane-1,2-diol 2-methylpropan-2-ol propan-2-ol A student oxidises alcohol E by heating under reflux with excess acidified potassium dichromate(vi). An organic product F is isolated. The mass spectrum of the alcohol E is shown below. 100 80 relative intensity 60 40 20 0 10 15 20 25 30 35 40 45 50 55 60 m/z The infrared spectrum of the organic product F is shown below. 100 transmittance (%) 50 0 4000 3000 2000 1500 1000 500 wavenumber / cm 1 Plymstock School 3

Name or draw the structures of the alcohol E and the organic product F. Write an equation for the reaction of alcohol E with acidified potassium dichromate(vi). Use [O] to represent the oxidising agent, acidified potassium dichromate(vi). In your answer, you should make clear how each structure fits with the information given above. [Total 7 marks] 6. Alcohols A, B, and D are shown below. 3 3 3 2 O O 3 2 2 O 3 O 3 3 A B D (a) ompound A is ethanol, a very useful alcohol. Identify the two main methods used in the industrial production of ethanol. Write an equation for each method. method 1...... equation...... method 2...... equation... [4] Plymstock School 4

(b) A student heated each alcohol, A D, with acidified potassium dichromate(vi) as the oxidising agent. With alcohols A, B and, the colour turned from orange to green. Identify the organic product and write a balanced equation for the reaction of alcohol B with acidified potassium dichromate(vi). Use [O] to represent the oxidising agent, acidified potassium dichromate(vi). organic product: balanced equation: The organic product obtained from was analysed by infrared (IR) spectroscopy. The IR spectrum of the product is shown below. 100 transmittance (%) 50 0 4000 3000 2000 1500 1000 500 wavenumber / cm 1 wavenumber / cm 1 Plymstock School 5

Use your Data Sheet to identify the organic product. Explain your reasoning. organic product: reasoning... [3] (c) The student heated alcohol D with ethanoic acid in the presence of an acid catalyst. An organic product E was formed with a fruity smell. Name alcohol D. Name the functional group in the organic product E. (iii) Draw the structure of the organic product E. [Total 13 marks] Plymstock School 6

7. Ethanol, 2 5 O, is manufactured on a large scale for a wide range of uses such as alcoholic drinks, as an industrial solvent and as a raw material for the synthesis of many organic compounds. Ethanol, 2 5 O, is manufactured on a large scale by two methods: Fermentation, using yeast, of sugars, such as glucose, 6 12 O 6. 6 12 O 6 (aq) 2 2 5 O(aq) + 2O 2 (g) The ethanol is then distilled off. ydration of ethene, 2 4, with steam in the presence of an acid catalyst. 2 4 (g) + 2 O(g) 2 5 O(g) ompare the sustainability of these methods of manufacturing ethanol in terms of: availability of starting materials and energy requirements; atom economy. In your answer, you should make clear how the atom economy of the processes links with chemical theory..................................... [Total 7 marks] Plymstock School 7

110 100 90 80 70 60 50 40 30 20 10 0 10 8. In the laboratory, ethanol can be oxidised with acidified potassium dichromate(vi). (a) The ethanol can be oxidised to form either ethanal, 3 O (Fig. 1), or ethanoic acid, 3 OO (Fig. 2). water out ethanol and acidified potassium dichromate(vi) water out ethanol and acidified potassium dichromate(vi) water in water in water bath at 60º distillate ice-water mixture heat Fig. 1 Fig. 2 The boiling points of ethanol, ethanal and ethanoic acid are given in the table below. 3 2 O 3 O 3 OO boiling point / 8 21 118 Use this table of boiling points to explain: why the organic product is likely to be ethanal if the apparatus shown in Fig. 1 is used, Plymstock School 8

why the organic product is likely to be ethanoic acid if the apparatus shown in Fig. 2 is used. (b) Write a balanced equation for the oxidation of ethanol to ethanoic acid. Use [O] to represent the oxidising agent.... [Total 6 marks] 9. Ethanol can be formed by fermentation of glucose, 6 12 O 6. Write a balanced equation, including state symbols, for the formation of ethanol by fermentation.... Fermentation only occurs in the presence of yeast. State two other essential conditions....... (iii) ow would you know when fermentation of glucose is complete?...... [Total 5 marks] Plymstock School 9

10. Propan-2-ol is flammable and readily burns. Write a balanced equation for the complete combustion of propan-2-ol.... [Total 2 marks] 11. Four possible structural isomers of 4 10 O are alcohols. Two are shown below. O O butan-1-ol butan-2-ol Draw the other two structural isomers of 4 10 O that are alcohols isomer 1 isomer 2 Name isomer 1.... [Total 3 marks] Plymstock School 10

12. Butan-2-ol can be dehydrated to produce a mixture of three alkenes each with a molecular formula 4 8. Draw the displayed formula for each of the three alkenes. [Total 3 marks] 13. (a) Butan-1-ol can be oxidised to form butanal. State a suitable oxidising mixture for this reaction. State the colour change you would see during this oxidation. from... to... (b) A sample of the butanal from (a) was analysed using infra-red spectroscopy. The infra-red spectrum contained an absorption in the region 1680 1750 cm 1 but did not contain a broad absorption in the region 2500 3300 cm 1. Refer to the Data Sheet for hemistry provided. What does the absorption in the region 1680 1750 cm 1 indicate? What does the absence of a broad absorption in the region 2500 3300 cm 1 indicate? Plymstock School 11

(iii) The reaction in (a) was carried out using distillation and not reflux. Explain why. [Total 7 marks] 14. (a) yclohexane can be converted into cyclohexene via a three-stage synthesis. O stage 1 l 2 compound A stage 2 stage 3 cyclohexane cyclohexanol cyclohexene In stage 1, cyclohexane reacts with chlorine to form the organic product, compound A. Show the structure of compound A. Stage 3 involves the dehydration of an alcohol. State a suitable reagent for dehydrating an alcohol. Plymstock School 12

(iii) Write a balanced equation for the dehydration of cyclohexanol, 6 11 O. (b) The reaction in stage 1 is difficult to control. One other possible chlorinated product is 1,4-dichlorocyclohexane.This is shown below. l stage 1 l 2 stage 2 stage 3 compound B compound and D l cyclohexane 1,4-dichlorocyclohexane 1,4-Dichlorocyclohexane reacts in the same way as compound A in stages 2 and 3. Suggest the structure of compound B. Plymstock School 13

Two cyclic alkenes, and D are formed in stage 3. and D are structural isomers. Suggest the structures of and D. [Total 6 marks] 15. Ethanol and glycerol (propane-1,2,3-triol) are both produced industrially on a large scale. Ethanol is manufactured by both fermentation and the hydration of ethene. Glycerol is produced as a by-product of soap manufacture. O ethanol O O O glycerol The relatively low volatility of alcohols such as ethanol can be explained by the existence of intermolecular bonds. Plymstock School 14

Explain what is meant by the terms: low volatility,...... intermolecular bonds...... On the ethanol molecules below, label any relevant dipoles, show the intermolecular bond formed and state the type of intermolecular bond. O O type of intermolecular bond... [3] (iii) Glycerol forms the same type of intermolecular bonds as ethanol. Predict, with a reason, whether the boiling point of glycerol will be higher or lower than that of ethanol. The boiling point of glycerol will be... than that of ethanol because...... [Total 6 marks] Plymstock School 15

16. This question is about the halogenoalkane 2-chlorobutane. 2-hlorobutane reacts with NaO, but the products are dependent on the solvent used. l O (aq) O (ethanolic) alcohol A a mixture of three alkenes B, and D 2-hlorobutane reacts with O in aqueous conditions to produce alcohol A. Identify alcohol A. Describe, with the aid of curly arrows, the movement of the electrons in the mechanism. Show any relevant dipoles, lone pairs of electrons and the products. [4] [Total 5 marks] 17. ompound E can be oxidised to form a carboxylic acid. State a suitable oxidising mixture for this reaction.... Plymstock School 16

Write a balanced equation for this oxidation of compound E. Use [O] to represent the oxidising mixture. 3 3 2 2 compound E O 2 [3] (iii) Explain how compound E and the carboxylic acid could be distinguished by infra-red spectroscopy....... [Total 6 marks] 18. (a) In the presence of a suitable catalyst, cyclohexanol reacts with compound Y. The organic product is shown in the equation below. O O + compound Y O + 2 O organic product State a suitable catalyst.... Identify compound Y. Plymstock School 17

(b) yclohexanol can also be oxidised to form cyclohexanone. State a suitable oxidising agent for this reaction. Write a balanced equation for the oxidation of cyclohexanol to cyclohexanone. Use [O] to represent the oxidising agent. [Total 4 marks] 19. Ethanol, 2 5 O, can be produced by the fermentation of glucose, 6 12 O 6. Write a balanced equation for the fermentation of glucose.... [Total 2 marks] 20. Ethanol has a relatively high boiling point. This can be explained in terms of intermolecular hydrogen bonds. Draw a second molecule of ethanol alongside the one drawn below and show how a hydrogen bond could be formed. learly show any relevant dipoles and lone pairs of electrons. O 2 3 [Total 3 marks] Plymstock School 18

21. (a) When ethanol is heated with acidified potassium dichromate(vi) solution, it can be oxidised to form either ethanal, 3 O (Fig. 1), or ethanoic acid, 3 OO (Fig. 2). water out ethanol and acidified potassium dichromate(vi) water out water in water bath at 60 water in distillate ice-water mixture ethanol and acidified potassium dichromate(vi) heat Fig. 1 Fig. 2 The boiling points of ethanol, ethanal and ethanoic acid are given in the table below. 3 2 O 3 O 3 OO boiling point/ 78 21 118 Use this table of boiling points to explain why the organic product is likely to be ethanal if the apparatus shown in Fig. 1 is used, Plymstock School 19

why the organic product is likely to be ethanoic acid if the apparatus shown in Fig. 2 is used. (b) Write a balanced equation for the oxidation of ethanol to ethanoic acid. Use (O) to represent the oxidising agent.... (c) The ethanal collected using the apparatus shown in Fig. 1 was analysed by infra-red spectroscopy. Use your Data Sheet to justify which of the three spectra shown below is most likely to be that of ethanal. Plymstock School 20

spectrum A spectrum B spectrum Plymstock School 21

The organic product collected when using the apparatus shown in Fig. 1 is most likely to be that shown by spectrum... because......... [3] [Total 9 marks] 22. Acrolein, 2 ==O, and acrylic acid, 2 ==OO, are both used in industry for the manufacture of plastic resins and polymers. Both acrolein and acrylic acid can be made from prop-2-en-1-ol, 2 == 2 O. (a) Draw the structures of prop-2-en-1-ol and acrolein. learly display the functional groups in each compound. prop-2-en-1-ol acrolein Name the functional group common to both prop-2-en-1-ol and acrolein. (b) Prop-2-en-1-ol can be oxidised to form either acrolein or acrylic acid. Identify a suitable oxidising mixture. Write a balanced equation for the oxidation of prop-2-en-1-ol into acrolein. Use (O) to represent the oxidising agent. [Total 6 marks] Plymstock School 22

23. Acrylic acid reacts with prop-2-en-1-ol to produce an ester. omplete the balanced equation for this reaction. 2 ==OO + 2 == 2 O... +... Draw the structure of the ester. learly display all of the functional groups. [Total 4 marks] 24. (a) There are four structural isomers of 4 10 O that are alcohols. One of the isomers has been drawn for you. omplete the table below to show the other structural isomers. O butan-1-ol isomer 1 isomer 2 isomer 3 [3] (b) Butan-1-ol is oxidised by an acidified solution of potassium dichromate(vi) to Plymstock School 23

form a carboxylic acid. State the colour change that you would see. olour changes from... to... Write a balanced equation for this oxidation of butan-1-ol to form a carboxylic acid. Use [O] to represent the oxidising agent. (iii) Identify which of the isomers, 1, 2 or 3, in (a) could also be oxidised to form a carboxylic acid. isomer... (c) Butan-1-ol reacts with hot concentrated sulphuric acid to form compound B. (iii) ompound B has an empirical formula of 2 and a relative molecular mass of 56. Use this information to deduce the molecular formula of compound B. Show your working. Write a balanced equation to show the conversion of butan-1-ol into compound B. One of the isomers, 1, 2 or 3, in (a) also reacts with hot concentrated sulphuric acid to form compound B. Identify which isomer. isomer... (d) The ester, 3 OO 2 2 2 3, was formed by reacting ethanoic acid with butan-1-ol. O O catalyst 3 + 3 2 2 2 O + 2 O 3 O O 2 2 2 3 butan-1-ol ester M r = 116 Plymstock School 24

State a catalyst for this reaction. In an experiment, 6.96 g of the ester was produced from 0.100 mol of butan-1-ol. alculate the number of moles of ester produced. (iii) alculate the percentage yield. [Total 14 marks] 25. itronellol, 10 20 O, occurs naturally in both rose and geranium oils. The structural and skeletal formulae of citronellol are shown below. 3 3 2 3 2 2 2 O O structural formula skeletal formula (a) Name the two functional groups present in citronellol....... and... (b) The functional groups in citronellol can be identified either by chemical tests or by infrared spectroscopy. State which of the two functional groups you named in (a) is: 1 identified when bromine is added to citronellol,... 2 more easily identified from the infra-red spectrum.... State what you would see when bromine is added to citronellol. Plymstock School 25

(iii) Draw the skeletal formula of the organic product formed when bromine is added to citronellol. (iv) The infra-red spectrum of citronellol is shown below. Mark on this spectrum, with the letter X, the absorption that confirms the presence of the functional group that is most easily identified from this spectrum. transmittance wave number / cm 1 (c) Reaction of a sample of citronellol, 10 20 O, with hydrogen in the presence of a catalyst results in the formation of a saturated compound. Suggest a catalyst for this reaction. Determine the molecular formula of the saturated compound. (iii) onstruct a balanced equation for this reaction. [Total 9 marks] Plymstock School 26

26. (a) Write an equation for the combustion of ethanol.... (b) In this question, one mark is available for the quality of written communication. Describe, with the aid of equations, the industrial manufacture of ethanol from glucose, 6 12 O 6, and from ethene, 2 4. Name each type of reaction and state all essential conditions. Future supplies of ethanol are likely to come from glucose rather than from ethene. Explain why. [9] Quality of Written ommunication [Total 12 marks] 27. This question is about the compounds A-F below. (a) Answer the following questions by referring to the compounds A-F. Plymstock School 27

What is the molecular formula of compound D? What is the empirical formula of compound? (iii) Which two compounds are structural isomers of each other?... and... (iv) Which two compounds are cis-trans isomers of each other?... and... (b) ompound E can be dehydrated to form compound A. omplete a balanced equation for this reaction. O (c) ompound can be dehydrated to form a new compound, G, with the molecular formula, 4 6. Suggest a structural formula and a name for G. name... [Total 7 marks] Plymstock School 28

28. Lavandulol, 10 18 O, is a fragrant oil which is found in lavender. The structural and the skeletal formulae of lavandulol are shown below. 3 3 3 2 2 O O structural formula skeletal formula (a) Identify two different functional groups in lavandulol.... and... Why does lavandulol not have cis-trans isomerism? (b) Lavandulol, 10 18 O, also reacts with bromine to form a saturated organic product. State what you would see in this reaction and deduce the molecular formula of the organic product. observation... molecular formula... Plymstock School 29

(c) Lavandulol could be converted into an ester X, which is also found in lavender oil. O O 3 ester X State a reagent and a catalyst that could be used to form ester X from lavandulol. reagent... catalyst... (d) Lavanduloi can be oxidised to produce either compound Y or compound Z. O O lavandulol O 10 18 compound Y O 10 16 OO compound Z O 10 16 2 Plymstock School 30

Write a balanced equation for the oxidation of lavandulol to produce compound Z. Use the molecular formulae given above and use [O] to represent the oxidising agent. An infra-red spectrum of either compound Y or compound Z was obtained and was found to contain an absorption between 1680 1750 cm 1. owever, there was no broad absorption between 2500 3300 cm 1. By referring to your Data Sheet, use this information to deduce whether the infra-red spectrum was of compound Y or of compound Z. Show your reasoning. The infra-red spectrum was of compound... because... [Total 12 marks] Plymstock School 31