Name ……………………………. Set ……..

A2 – Scheme B

CHEMISTRY

HomeworkHomeworkBookletBooklet2009-10

6

2009-10

Homework page

Independent Study - Optical isomerism 3

Isomerism 4Carbonyl Chemistry 5-6Carboxylic Acids 7-8Independent StudyReaction Summaries and Biodiesel

10

Esters and Carboxylic Acid Derivatives 11-12New Mass Spec and IR 13-14NMR and Chromatography 15-16

Introductory Ideas About Benzene, C6H6 18Alkenes vs Arenes 19-20Phenols 21Amines 22Amides, Azo Dyes and Aromatic amines 23-24Polymers and Amino Acids 25-26Synthetic Reaction Schemes 27-28Organic Synthesis 29-30More Organic Synthesis 31-32

As well as completing your set homework task you should also work on the Independent Study tasks on the next page.

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A–level Chemistry Independent Study (second year)

As with last year you are responsible for your own learning and going beyond the restraints of the syllabus.

It is important that you know how Chemistry is relevant to contemporary issues and how it influences the world around us.

The topics we would like you to focus on this year are;

Supramolecular chemistry.The importance of Organic Synthesis in the Pharmaceutical industry.The importance of understanding reaction mechanisms in drug synthesis.The use of Combinatorial chemistry in drug research.Chemical Analysis using Gas Chromatography (GC).Chemical Analysis using Nuclear Magnetic Resonance (NMR) Spectroscopy.

We would like you to continue your notebook to record your independent study.

In it you should record;

Explanatory notes regarding each of the above topics.

Any articles in the news or in journals such as; New Scientist, Scientific American and Chemistry Review, that relate to the above topics.

A list of useful websites you have found and use.

The A2 Chemistry pages on the RGS infonet contain context studies written by the exam board for each topic. They are an ideal place to start your independent study.

You will continue to be graded on Independent study throughout the year and your notebook will be assessed by your teacher.

We will be looking for evidence of interest, knowledge and reading around these areas of Chemistry.

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Independent Study – Optical Isomerism

Research the following in your scrapbook.

Optical isomerism – Chirality.Enantiomers.Issues with chirality in drug design.Stereospecific drugs - Thalidomide.

Remember to record;

Explanatory notes regarding each of the above topics.

Any articles in the news or in journals such as; New Scientist, Scientific American and Chemistry Review, that relate to the above topics.

A list of useful websites you have found and use.

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IsomerismChemistry for A2 Chapter 6 pg 79-85 Total /35

1. Define: (a) Isomerism (b) Structural isomerism (c) Stereoisomerism [3]

2. Explain clearly, but in words only, how (a) geometric and (b) optical isomerism occur.[2]

3. Use diagrams to clearly explain how (a) geometric and (b) optical isomerism occur. [4]

4. Discuss the various types of isomerism using the following as examples. In each case state the form(s) of isomerism present and draw structures of all possible isomers:

(a) C2H6O [3](b) C2H2Cl2 [5](c) (CH3)(CH3CH2)(H)SiCl [3]

5. (a) Why do enantiomers have identical physical properties? [2](b) How can one distinguish between two enantiomers? [2](c) Draw and give the name of the smallest alkane that exhibits optical isomerism. [2]

6. Look at the sequence below.

(a) Draw a diagram of ethanal (A) which shows the 3D shape about the C=O bond. [1](b) Draw an isomer of (A) [1](c) Draw both enantiomers of B. [2](d) Hydrolysis of B results in a 50:50 mixture of the two enantiomers of lactic acid.

What name is given to such mixtures? [1](e) From a stereochemical point of view, how does the natural synthesis of lactic acid in

muscles differ? [1]

7. Explain why it is very important in drug research to account for chirality in compounds having potential therapeutic activities? [3]

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Carbonyl ChemistryChemistry for A2 Chapter 7 pg 86-95 Total /62

1) Use systematic nomenclature to name the following carbonyl compounds:a) H—CHOb) CH3COCH2CH3

c) d) e)

[5]

2) Draw the full structural and skeletal formulae of the following compounds:a) butanal b) pentan-2-one c) 3-methylbutan-2-one [6]

3) Which of the following alcohols can be oxidised to an aldehyde or a ketone? In each case, state which type of carbonyl compound would be formed and draw its skeletal formula.

a) CH3CH2CH(OH)CH(CH3)CH3

b) CH3C(CH3)2CH2OHc) CH3CH2CH(CH3)CH(OH)CH3 [3]

4) Use the [O] notation to write balanced equations for the oxidations in 3a), 3b) and 3c). [6]

5) The following carbonyl compounds can be reduced to alcohols. In each case draw the

structural formula of the alcohol formed and state whether it is a primary or secondary alcohol.

a) CH3-CH2-CH2-CHOb) CH3-CO-CH2-CH3

c) CH3-C(CH3)2-CO-CH3 [3]d) Name the reagent and conditions needed to reduce the carbonyl groups in a) to c) to alcohols. [2]

6) Aldehydes and ketones undergo nucleophilic addition reactions with hydrogen cyanide in the presence of alkali. Draw the structural formula for the products (include any isomers) of the reaction between HCN and each of the following compounds.

a) CH3-CH2-CHO [3]b) CH3-CH2-CO-CH3 [3]c) Using the compound in part a) as an example explain how the reaction is a nucleophilic addition. [1]

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7) This question is about the 'Lily of the Valley' molecule used in perfumery:

a) Suggest why 'Lily' is dissolved in propanol rather than water when sold as a perfume. [3]b) Classify the two functional groups present in 'Lily of the Valley'. [2]c) Draw the structure of the product formed when 'Lily' reacts with:

(i) warm acidified potassium dichromate [2](ii) warm acidified potassium cyanide [2](iii) lithium aluminium hydride in dry ether [2]

d) Give the observation (from what, to what) when 'Lily' is reacted with:(i) aqueous silver nitrate and excess ammonia [2](ii) Fehling's or Benedict’s solution [2](iii) acidified 2,4-dinitrophenolhydrazine[2](iv)acidified potassium dichromate [2]

8) Cinnamaldehyde is present in the spice cinnamon. It is used as a flavouring in biscuits, cakes and mulled wine. The structure of cinnamaldehyde is :-

a) A sample of cinnamadehyde was refluxed with dilute sulphuric acid and potassium dichromate (VI). Draw a displayed formula to show the structure of the product. [2]

b) 2,4 Dinitrophenyl hydrazine is used as the test to show the presence of the carbonyl group in cinnamaldehyde. Draw the structure of the organic compound formed from the test and give the observations that you would expect. [2]

c) Give the name and formula of the reagent which will reduce cinnamaldehyde to cinnamyl alcohol. [2]

d) Describe a chemical test to show that cinnamaldehyde is an aldehyde and not a ketone. Give the observations expected. [3]

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Carboxylic AcidsChemistry for A2 Chapter 8 pg 96-100 Total / 73

1. Explain the following:(a) Butanoic acid has a higher boiling point than butan-1-ol. [2](b) Ethanoic acid is more acidic than ethanol. [2](c) Carboxylic acids of short hydrocarbon chain are soluble in water but the solubility in water rapidly decreases with increased chain length. [2]

2. Write balanced symbol equations for the following reactions:(a) propanoic acid + pentan-1-ol [3](b) butanoic acid + phosphorous pentachloride [3](c) methanoic acid + sodium hydrogen carbonate [3](d) propanoic acid + lithium aluminium hydride [3]

3. Give the reagents and conditions required for the following transformations: a)

b)

c)

d)

e)

f)

[12]

4. Acid chorides can be made using either PCl5 or SCl2O. Explain which method is best. [2]

5. Describe how you would purify an impure sample of solid octanoic acid by recystallisation. [5]

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6. Consider the following reaction scheme:

a) Identify the intermediate B. (Hint – B is made from the aldehyde A). [2]b) Give the reagents and essential reaction conditions required for:

i) step 1ii) step 2 [4]

c) Name the final product C. [1]d) Name and draw the reaction mechanism that takes place in step 1. [4]e) The final product C is chiral. Label the chiral atom with an asterisk *. [1]f) Explain why the final product doesn’t rotate plane polarised light, even though it is chiral.[2]

7. Citric acid is a natural carboxylic acid present in citrus fruits. It is used as a flavouring and a food additive and is the acid component of many soft drinks.

a) Write down the molecular formula for citric acid. [1] b) i) How would you show that citric acid was an acid? [1] ii) How would you show that citric acid was a weak acid? [1]

c) Draw the skeletal formulae of the organic product formed when citric acid is treated with an excess of the following reagents: i) aqueous sodium hydroxide solution.ii) phosphorus pentachloride.iii) ethanol and a trace of concentrated sulfuric acid. iv) lithium tetrahydridoaluminate(III).

[8]d) Describe how you would determine the exact citric acid content in fruit, assuming that the only

acid present is citric acid. [3]e) In a typical experiment to find the citric acid content in a sample of fruit it was found that 25cm3

of a fruit solution reacted with exactly 14.3 cm3 of 0.01M sodium hydroxide solution. Calculate the concentration of citric acid in the sample of fruit tested. [3]

f) Many effervescent tablets (such as Alka-Seltzer) contain citric acid. i) Explain why there is fizzing when Alka-Seltzer is put in water, given that the tablets also contain sodium hydrogencarbonate (NaHCO3) (in addition to the painkiller aspirin). [1] ii) Write a balanced equation for the reaction that takes place. [2] iii) Why is water necessary for the reaction to start? [2]

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Independent StudyReaction Summaries and Biodiesel

1) Make a summary flow diagrams for the reactions of; Aldehydes

Ketones and Carboxylic Acids.

Remember to record;

Reaction conditions and reagents.

Any mechanisms that you need to know.

2) Research the following in your scrapbook.

The formation of Biodiesel.

The ‘greenness’ and carbon footprint of Biodiesel.

Remember to record the sources you have found and used.

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Esters and Carboxylic Acid DerivativesChemistry for A2 Chapter 8 pg 101-108 Total / 70

1. Esters have characteristic floral or fruity smells. Two examples are given below;

Fragrance = Pears Fragrance = Apples

a) Give the skeletal formulae and names of the carboxylic acid and alcohol required to make;i) Ester A.ii) Ester B. [4]

b) Draw a labelled diagram of the apparatus that might be used to prepare one of the esters on a small scale in the lab. [3]

c) Since esterifications are equilibria reactions, what is the practical way of pulling the equilibrium to the right hand side to increase the yield of the ester? [2]

d) Describe two factors that would need to be considered if the technique to make the esters needed to be scaled up to be made on a larger scale. [2]

e) What is the relationship between the two esters A and B? [1]f) Apart form their use in food flavourings, give one other use of esters. [1]g) Give reagents and conditions used to make propylpentanoate. [2]h) Give the structure of 2,2-dimethylpropylmethanoate. [1]i) Glycerol (propan-1,2,3-triol) is a by-product in soap manufacture.

Explain why and include a balanced equation for the formation of soap. [4]

2. Write balanced symbol equations for the following reactions:(a) ethyl ethanoate + sodium hydroxide (heated under reflux) [3](b) propanoic acid + phosphorous(V) chloride [3](c) butanoyl chloride + concentrated ammonia [3](d) methanoic acid + ethanol [3](e) propyl ethanoate + hydrochloric acid (under reflux) [3]

3. Positive Tollens and Fehlings tests result in the salts of carboxylic acids as by-products.a) What type of compound do these two reagents test for? [1]b) What is the observation with Tollens reagent? [1]c) What sort of chemical change occurs to the organic sample when the test is positive?[1]d) Why is the salt if the carboxylic acid formed? [1]

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4. Describe how you could use simple chemical tests to distinguish between the six unlabeled bottles following compounds. Your plan must be logical and involve a minimal number of tests.

[12]

5. Methyl benzoate (C6H5CO2CH3) can be prepared from methanol and benzoic acid as shown in the equilibrium equation:

C6H5CO2H + CH3OH C6H5CO2CH3 + H2O

An incomplete experimental procedure for the preparation of methyl benzoate is outlined below:

Put 10.0 g of benzoic acid and 20 cm3 of methanol into a 100 cm3 round-bottomed flask. Add 2 cm3 of concentrated sulfuric acid and then fit a reflux condenser. Heat the mixture under reflux, with an electrical heater, for 45 min. After allowing the reaction vessel to cool to room temperature, pour the reaction mixture into a

separating funnel containing 40 cm3 of cold water. Rinse the reaction flask with 20 cm3 hydrocarbon solvent and add the solvent to the contents of the

separating funnel. After shaking and leaving to settle to form two layers, the aqueous layer is run off and the

hydrocarbon layer washed successively with water and sodium carbonate solution. The hydrocarbon layer is then dried over a suitable compound and then filtered.

a) What is the purpose of the concentrated sulfuric acid in point 2? [1] b) Draw a labelled diagram of the apparatus used for heating the reaction mixture to reflux. [3] c) Why is the reaction mixture not simply heated in a beaker? [1] d) Why is an electrical heater used to heat the mixture, rather than a Bunsen? [1] e) After refluxing, why is the reaction mixture washed with water in the separating funnel (point 4)? [1] f) Why is the reaction flask rinsed with hydrocarbon solvent (point 5) and not water? [1] g) Why is the hydrocarbon layer washed with sodium carbonate in the separating funnel (point 7)? [1] h) Name a suitable compound for drying the hydrocarbon layer (point 7). [1]

i) Having filtered the hydrocarbon layer to remove the drying agent, describe how you could obtain a pure sample of methyl benzoate, given that it is a liquid at room temperature. [2]

j) How might you test and verify the purity of the sample of methyl benzoate that you obtained? [2]

k) 4.6 g of pure methyl benzoate is produced in the reaction. Given that the methanol is present in excess at the start of the reaction, calculate the percentage yield of the reaction. [3]

l) Calculate and comment on the atom economy of the reaction. [2]

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IR and Mass SpecChemistry for A2 Chapter 9 pg 116-120 Total / 41

Answer Qu 1-4 on the activity on Jasmine on page 119 and 120 of Chemistry for A2. [11]

1) a) In infrared spectroscopy, what is the region below 1500cm-1 called? [1]b) Explain how this region could be used to show that an unknown ketone was cyclohexanone

and not hexan-3-one. [2]c) Assign the peaks labelled in the infrared spectra below and identify the function groups

present in each compound. [9]

III

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2) The infrared and mass spectra of an unidentified organic compound Y are shown below; Y decolourises bromine, but only in the presence of an iron catalyst.

a) Name the functional groups present in Y. [2]b i) What is the RFM of compound Y? [1] ii) Identify the fragments that are responsible for the mass spectrum peaks at;

m/e 122m/e 105m/e 77m/e 51 [4]

3) The mass spectrum of methyl benzoate (C6H5COOCH3) is shown below:

a) What is the m/e value of;i) The M+, molecular (parent), ion? [1]ii) The (M+1) peak? [1]

b) Explain why this (M+1) peak occurs and why it is so small. [2]c) Suggest skeletal formulae for the fragments responsible for the peaks at:

i) m/e 136ii) m/e 105iii) m/e 15 [3]

d) Describe two practical uses of mass spectroscopy. [4]

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NMR and ChromatographyChemistry for A2 Chapter 9 pg 111-115 and 121-129 Total / 54

1) For each of the following compounds indicate the number of signals, and relative intensity and multiplicity of each signal (using the n+1 rule) in its NMR spectrum. a) CH3COCH3

b) CH3CH=CH2 c) CH2BrCHBrCH3

d) CH3CH2COOCH2CH3 [12]

2) Use the molecular formula and high resolution NMR spectra to identify the molecules below; (Explain your answers fully).a) C5H10O [4]

b) C2H4O [4]

c) C4H8O2 [4]

3. Quantitative analysis of compound B shows it to contain 22.2% C, 4.6% H and 73.2% Br by

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mass. The mass spectrum and NMR spectrum are given below:

(a) Calculate the empirical formula of B. [2](b) Explain which peak on the mass spectrum represents the molecular ion of B and write the ion’s formula. [2](c) Use the mass spectrum to deduce the relative molecular mass and hence give the molecular formula of B. [2](d) Determine the ratio of hydrogen atoms in each environment from the NMR data. [1](e) Give the structure and hence name of B. [4]

4 a) Briefly explain how Column chromatography is used to separate mixtures of organic compounds. [3]

b) What is meant by the retention time in gas chromatography and how can it be used to identify the composition of a mixture of organic compounds? [3]

c) Why is gas chromatography often combined with mass spectrometry? [2]

5. Read the activity on pg 128-129 of Chemistry for A2 and answer questions 1-5. [11]

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Introductory Ideas About Benzene, C6H6Chemistry for A2 Chapter 12 pg 180-188 Total / 55

1. Draw out all the structural isomers of C6H6 (think laterally here: anything goes as long as carbon has four bonds and hydrogen has one). [6]

2. For each of the following pieces of information, state the likely implication for the actual structure of benzene:a) all six carbon-carbon bonds are of identical length.b) all bond angles are 120C. [4]

3 a) The benzene molecule is said to contain delocalised -electrons.Use a suitable diagram to show what this means. [3]

b) Comment upon the following enthalpies of reaction; [3]

4. Draw and name all the isomers of formula C6H3Cl3. (Only consider compounds which

contain a benzene ring; use the hexagon notation to represent the ring on each case.) [6]

5. Draw the structural formulae of the following arenes:a) 3-nitrochlorobenzene,b) 1,4-dihydroxybenzene. [2]

6. Draw the skeletal formulae of the following arenes:a) 2,4,6-triethylmethylbenzene,b) 1,2,5-tribromobenzene,c) Phenylethene. (Note phenyl means a substituted benzene ring). [3]

7. Give the name(s) and structural formula(e) of the product(s), if any, obtained when benzene is reacted with:a) Bromine water,b) Bromine in the presence of an iron catalyst,c) Hydrogen gas and a Nickel catalyst at 200oC.d) Concentrated (fuming) sulphuric acid. [8]

8. Read the activity on g 190-191 of Chemistry for A2.Draw a labelled diagram of the apparatus used to chlorinate benzene and answer questions 1-6 on pg 191. [20]

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Alkenes vs ArenesChemistry for A2 Chapter 12 pg 185-192 Total / 60

1. Explain why:a) both alkenes and benzenes undergo electrophilic reactions.b) alkenes tend to undergo addition reactions.c) arenes tend to undergo substitution reactions. [6]

2. Draw the mechanism for the electrophilic addition reaction between propene and bromine.[3]

3. Draw the mechanism for the electrophilic substitution reaction between methyl benzene and bromine with an iron catalyst. [4]

4. Consider the molecule below:

a) There are three different types of carbon-carbon bonds present. List them in order of increasing bond length. [1]

b) Draw the likely product when the molecule is reacted with:(i) one mole equivalent of hydrogen on nickel. [2](ii) a mixture of conc sulphuric and conc nitric acids. [2](iii) bromine water. [2](iv) itself, under pressure in the presence of a catalyst. [2](v) fuming sulphuric acid. [2](vi) propanoyl chloride and aluminium trichloride. [2](vii) 2-chloropropane and aluminium trichloride. [2](viii) Acidified potassium manganate(VI). [2]

c) The molecule exhibits stereoisomerism.(i) What type? [2](ii) How does it arise? [2](iii) Draw the other isomer. [2]

5. The enthalpy of combustion of ethyne (C2H2) is –1300 kJ/mol and that for benzene (C6H6)is –3300 kJ/mol. Does this make benzene more, or less, stable than predicted? Explain your answer. [3]

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6. Two reactions of benzene are summarised in the diagram;

a) What is the meaning of the circle in the diagram of both benzene and substance E? [2]

b) Name the substances A to E: [5]

c) Name the type of reaction involved in the formation of A. [1]

d) Name the type of reaction involved in the formation of E [2]

e) Draw the mechanism for reaction involved in the formation of E from benzene. [4]

7. TNT can be made from benzene in the three step synthesis below.

a) Suggest suitable reagents and conditions for Step 1. [2]

b) Suggest suitable reagents and conditions for Step 2. [3]

c) Explain why careful temperature control is needed in Step 2. [2]

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PhenolsChemistry for A2 Chapter 12 pg 193-196 Total / 50

1. Look at the molecules below: Thymol (oil of thyme) Eugenol (oil of cloves)

a) In general terms, suggest why these compounds have not entirely dissimilar smells. [2] b) Explain why Thymol and Eugenol are slightly soluble in water. [2] c) Draw the structure of the product formed when Thymol reacts with:

(i) sodium metal. [2](ii) sodium hydroxide. [2]

d) Draw a possible product when Eugenol is reacted with:(i) a mixture of conc sulphuric and conc nitric acids. [2](ii) excess liquid bromine (in the absence of bright light). [3]

2. When phenol is reacted with dilute nitric acid, a mixture of 2- and 2, 4-dinitrophenol is formed. a) Explain why 2- and 2,4-dinitrophenol are formed. [2] b) Suggest why the nitration of phenol requires miler conditions than the nitration of benzene.

[3] c) Draw and name the mechanism for the conversion of phenol into 4-nitrophenol. [4]

3. Read the activity on pg 194-195 of Chemistry for A2.Draw the equations present in the cumene process and answer questions 1-5 on pg 195.

[18]4. An alternative two step method of making phenol is shown below.

o Benzene is heated under reflux with concentrated sulphuric acid for several hours.

o The product is then heated with molten sodium hydroxide, phenol is produced.

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sc 2.25 SA OA}{1 -1 sc 1.5 SA OA}{1 -1 sc 1 SA OA}{270 CA OA}{180 CA OA}{120 CA OA}{90 CA OA}{1 -1 sc 270 CA OA}{1-1 sc 180 CA OA}{1 -1 sc 120 CA OA}{1 -1 sc 90 CA OA}{1 -1 sc 270 AA}{1 -1 sc 180 AA}{1 -1 sc 120 AA}{1 -1 sc 90 AA}]e g exec gr}b/ac{arcto 4{pp}repeat}b/pA 32 d/rO{4 lW m}b/Ac{0 0 px dp m py dp m a sqrt 0 360 arc cm sm gs sg fill grst}b/OrA{py px at ro px dp m py dp m a sqrt dp rev{neg}if sc}b/Ov{OrA 1 0.4 sc 0 0 1 0 360 arc cm sm gs sg fill gr st}b/Asc{OrA 1 27 dv dp sc}b/LB{9 -6 mv 21 -10 27 -8 27 0 cv 27 8 21 10 9 6 cv -3 2 -3 -2 9 -6 cv cp}b/DLB{0 0 mv -4.8 4.8 l-8 8 -9.6 12 -9.6 16.8 cv -9.6 21.6 -8 24.6 -4.8 25.8 cv -1.6 27 1.6 27 4.8 25.8 cv 8 24.6 9.6 21.6 9.6 16.8 cv 9.6 12 8 8 4.8 4.8 cv cp}b/ZLB{LB}b/Ar{dp 39 lt{Ar1}{gs 5 1 r o o xl 3 -1 r e s 3 1 r s e o 0 lt o 0 lt ne/rev xdp 0 lt{1 -1 sc neg}if/py x dp 0 lt{-1 1 sc neg}if/px x np[{py 16 div dup 2 S lt{pp 2 S}if/lp x lp 0 p mv 0 0 p l 0 py p l lp py p l px lp s 0 p mv px 0 p l px py p l px lp s py p l cm sm st}{py 16 div dup 2 S lt{pp 2 S}if/lp x lp 0 p mv 0 0 0 py lp ac0 py 2 dv lp neg o lp ac 0 py 2 dv 0 py lp ac 0 py lp py lp ac px lp s 0 p mv px 0 px py lp ac px py 2 dv px lp a o lp ac px py 2 dv px py lp ac px py px lp s py lp ac cm sm st}{py dp 2 dv py 180 pA s 180 pA a arc st np px py s py 2 dvpy pA dp neg arcn st}{0 0 p mv 0 py p l px py p l px 0 p l cp cm sm st}{px lW 2 dv a lW -2 dv p mv rO dp rlineto px lW 2 dv a rO a py lW 2 dv a rO a p l rO lW -2 dv a py lW 2 dv a rO a p l lW -2 dv py lW 2 dv a p l 0 py p l px py p l px 0 p l cp fill0 0 p mv 0 py p l px py p l px 0 p l cp cm sm st}{0 rO p mv 0 py px py rO ac px py px 0 rO ac px 0 0 0 rO ac 0 0 0 py rO ac cp cm sm st}{rO py p mv rO rO xl 0 py px py rO ac px py px 0 rO ac px 0 0 0 rO ac rO neg dp xl px py 0 py rO accp fill 0 rO p mv 0 py px py rO ac px py px 0 rO ac px 0 0 0 rO ac 0 0 0 py rO ac cp st}{1.0 Ac}{0.5 Ac}{1.0 Ov}{0.5 Ov}{Asc LB gs 1 sg fill gr cm sm st}{Asc LB gs 0.5 sg fill gr cm sm st}{Asc LB gs 0.5 sg fill gr gs cm sm st grnp -1 -1 sc LB gs 1 sg fill gr cm sm st}{Asc LB gs 0.5 sg fill gr gs cm sm st gr np -0.4 -0.4 sc LB gs 1 sg fill gr cm sm st}{Asc LB gs 1 sg fill gr gs cm sm st gr np -0.4 -0.4 dp sc LB gs 0.5 sg fill gr cm sm st}{Asc DLB -1 -1 sc DLB gs 1 sg fill grgs cm sm st gr np 90 ro DLB -1 -1 sc DLB gs 0.5 sg fill gr cm sm st}{Asc gs -1 -1 sc ZLB gs 1 sg fill gr cm sm st gr gs 0.3 1 sc 0 0 12 0 360 arc gs 0.5 sg fill gr cm sm st gr ZLB gs 1 sg fill gr cm sm st}{Asc gs -1 -1 sc ZLB gs 0.5 sgfill gr cm sm st gr gs 0.3 1 sc 0 0 12 0 360 arc gs 1 sg fill gr cm sm st gr ZLB gs 0.5 sg fill gr cm sm st}{0 0 p mv px py p l cm sm st}{gs bW 0 ne{bW}{5 lW m}ie sl 0 0 p mv px py p l cm sm st gr}{gs dL 0 0 p mv px py p l cm sm st gr}{OrA 1 16 dv dp sc0 1 p mv 0 0 1 0 1 ac 8 0 8 -1 1 ac 8 0 16 0 1 ac 16 0 16 1 1 ac cm sm st}]e 39 s g exec gr}ie}b/Cr{0 360 np arc st}b/DS{np p mv p l st}b/DD{gs dL DS gr}b/DB{gs 12 OB bW 0 ne{bW}{2 bd m}ie sl np 0 0 p mv 0 p l st gr}b/ap{e 3 ix ae 2 ix a}b/PT{8 OB 1 sc 0 bd p 0 0 p 3 -1 r s 3 1 r e s e 0 0 p mv 1 0 p l 0 0 p ap mv 1 0 p ap l e n e n 0 0 p ap mv 1 0 p ap l pp pp}b/DT{gs np PT cm sm st gr}b/Bd{[{pp}{[{DS}{DD}{gs 12 OB np bW 0 ne{bW 2 dv/bd x}if dp nH dv dp 3 -1 ro 2 dv s{dp bd p mv bd n p l}for st gr}{gs 12 OB 1 sc np bW 0 ne{bW 2 dv/bd x}if 1 1 nH 1 s{nH dv dp bd m wF m o o p mv n p l}for cm sm st gr}{pp}{DB}{gs 12 OB np 0 lW 2 dv o o n p mv p l bW 0 ne{bW 2 dv}{bd}ie wF m o o p l n p lcp fill gr}{pp}{gs 12 OB/bL x bW 0 ne{bW 2 dv/bd x}if np 0 0 p mv bL bd 4 m dv round 2 o o lt{e}if pp cvi/nSq x bL nSq 2 m dv dp sc nSq{.135 .667 .865 .667 1 0 rcurveto .135 -.667 .865 -.667 1 0 rcurveto}repeat cm sm st gr}]o 1 g 1 s g e 2 4 gi al pp5 -1 r exec}{al pp 8 ix 1 eq{DD}{DS}ie 5 -1 r 2 eq{DB}{DS}ie pp}{2 4 gi al pp DT}]o 0 g g exec}b/CS{p mv p l cw lW cW 2 m a sl sp sl}b/cB{12 OB 0 0 p mv 0 p l cm sm cw bW 0 ne{bW}{bd 2 m}ie cW 2 m a sl sp sl}b/CW{12 OB 1 sc cW lW 2 dva 0 o p mv 0 e n p l bW 0 ne{bW 2 dv}{bd}ie wF m cW a 1 o n p l 1 e p l cp cm sm}b/CB{np[{[{CS}{CS}{cB}{CW}{pp}{cB}{CW}{pp}{cB}]o 1 g 1 s g e 2 4 gi al pp 5 -1 r exec}{al pp p mv p l CS pp pp}{2 4 gi al pp PT cm sm cw cW 2 m sl sp sl}]o0 g 1 s g exec clip}b/Ct{bs rot g bs rot g gs o CB CB 1 setgray clippath fill 0 setgray Bd gr}b/wD 18 dict d/WI{wx dx ne{wy dy s wx dx s dv/m1 x wy m1 wx m s/b1 x}if lx ex ne{ly ey s lx ex s dv/m2 x ly m2 lx m s/b2 x wx dx ne{b2 b1 s m1 m2 s dv}{wx}iedp m2 m b2 a}{ex n dp m1 m b1 a}ie}b/WW{gs wD begin bs e g 2 4 gi al pp o o xl 4 -1 r 3 -1 r s/wx x s/wy x bs e g 2 4 gi al pp 4 -1 r 3 -1 r s/lx x s/ly x 0 bW 2 dv wF m o o wy wx at mt ro tr/dy x/dx x ly lx at mt ro tr n/ey x n/ex x np wxwy p mv WI p l ex n/ex x ey n/ey x dx n/dx x dy n/dy x lx ly p l WI p l cp fill end gr}b/In{px dx ne{py dy s px dx s dv/m1 x py m1 px m s/b1 x}if lx 0 ne{ly lx dv/m2 x ly ey s m2 lx ex s m s/b2 x px dx ne{b2 b1 s m1 m2 s dv}{px}iedp m2 m b2 a}{ex n dp m1 m b1 a}ie}b/BW{wD begin bs e g/wb x bs e g/bb x wb 4 g/cX x wb 5 g/cY x bb 4 g cX eq bb 5 g cY eq and{bb 2 g bb 3 g}{bb 4 g bb 5 g}ie cY s/ly x cX s/lx x/wx wb 2 g cX s d/wy wb 3 g cY s d 0 bW 2 dv ly lx at mt ro tr/ey x/ex x0 bW 2 dv wF m wy wx at mt ro tr/dy x/dx x 0 lW 2 dv wy wx at mt ro tr wy a/py x wx a/px x gs cX cY xl np px py p mv In p l lx ex s ly ey s p l ex n/ex x ey n/ey x dx n/dx x dy n/dy x wx 2 m px s/px x wy 2 m py s/py x lx ex s ly ey s p lIn p l px py p l cp fill gr end}b/Db{bs{dp type[]type eq{dp 0 g 2 eq{gs dp 1 g 1 eq{dL}if 6 4 gi al pp DS gr}{dp 0 g 3 eq{2 4 gi al pp DT}{pp}ie}ie}{pp}ie}forall}b/I{counttomark dp 1 gt{2 1 rot{-1 r}for}{pp}ie}b/DSt{o/iX x dp/iY x o/cXx dp/cY x np p mv counttomark{bs e g 2 4 gi al pp o cX ne o cY ne or{4 1 r 4 1 r}if pp pp o/cX x dp/cY x o iX eq o iY eq and{pp pp cp}{p l}ie}repeat pp st}b/SP{gs/sf x/lW x/bW x/cW x count 9 ge 7 ix 192837465 eq and{ 7 -1 r pp6 -2 r o o xl 7 -1 r s e 7 -1 r s e 5 -1 r dv neg e 5 -1 r dv neg e sc neg e neg e xl}{xl pp pp}ifelse 1 1 S dv dp sc cm currentmatrix pp lW sl 4.0 setmiterlimit np}b end

300 62 37 61 40 80 20 20 chemdict begin SP 5420 2080 5710 1890 35 Ar 5979 1701 5689 1890 35 Ar 4720 1840 3600 1840 2 Ar 940 2100 1230 1910 35 Ar 1499 1721 1209 1910 35 Ar /bs[[1 1 5240 1600 5240 2140][1 1 5240 2140 5708 2410][1 1 5708 2410 6176 2140][1 1 6176 2140 6176 1600][1 1 6176 1600 5708 1330][1 1 5240 1600 5708 1330][1 1 6176 1600 6500 1330][1 1 760 1620 760 2160][1 1 760 2160 1228 2430][1 1 1228 2430 1696 2160][1 1 1696 2160 1696 1620][1 1 1696 1620 1228 1350][1 1 760 1620 1228 1350][1 1 1696 1620 2020 1380]]d [0 5 4 3 2 1 I 5240 2140 DSt [6 I 6500 1330 DSt [7 12 11 10 9 8 I 760 2160 DSt [13 I 2020 1380 DSt Db gr end

OHSO3H

+ NaOH

a) Discuss why the cumene process is the preferred manufacturing process for the production of phenol.

[7]b) Predict all the possible final products when methylbenzene is heated under reflux with conc sulphuric acid and then heated with molten sodium hydroxide. [3]

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AminesA2 Chemistry Chapter 13 pg 198-203 Total / 60

1) Draw the full structural and skeletal formulae of the following compounds:a) pentylamine b) 2-methylbutyl methylamine c) dimethyl ethylamine [6]

2) Classify the three amines above as either tertiary, secondary or primary [3]

3) Explain why tertiary amines are not very soluble in water and are limited in their reactivity.

[3]

4) Give an explanation of the relative basicities of ammonia, ethylamine and phenylamine. [3]

5) . Explain the following:(a) Ethylamine has a higher boiling point than ethane. [2](b) Propylamine has a lower boiling point than propan-1-ol. [2](c) Amines of short hydrocarbon chain are soluble in water but the solubility in water rapidly decreases with increased chain length. [2]

6) Write balanced equations for the following reactions:(a)

[2](b)

[2](c)

[2]

7) a) Describe what happens when ethylamine is added to copper(II) ions in CuSO4. [2]b) What is observed during the reaction in part a). [1]

8) Adrenaline has the structure shown below.

a) What is the molecular formula of adrenaline. [1] b) Name the functional groups in adrenaline. [3] c) Identify the chiral carbon in adrenaline and hence draw both optical isomers. [3] d) How can the two optical isomers be differentiated between in the lab? [1] e) Explain why only one isomer is biochemically active. [2]

9) Read the activity on Paracetamol pg 202 of Chemistry for A2.

-22-

Draw the skeletal formulae of aspirin and paracetamol and answer questions 1-6. [20]

-23-

Amides, Azo Dyes and Aromatic aminesChemistry for A2 Chapter 13 pg 199-205 Total / 45

1. . Explain the following:a) Ethanamide is soluble in water. Draw a diagram to explain your answer. [2]b) Hexanamide is insoluble in water. [2]

2. Explain why amides are unreactive. [2]

3. Sunset Yellow is used as a food colourant (E110) in sweets, orange squash and jams. It is produced by the following reactions:

a) What type of compound is Sunset Yellow? [1]b) What reagent must compound B be treated with and under what conditions in order to

make compound C, before C is added to D to produce Sunset Yellow? [3]c) The sodium sulphonate (SO3

-Na+) groups have little effect on the colour of Sunset Yellow. Suggest a reason why these groups are needed in the molecule. [2]

4. Phenylazobenzene has the structure shown below.

a) What is the molecular formula of Phenylazobenzene? [1] b) Phenylazobenzene exhibits stereoisomerism. Explain why? [3] c) Draw the cis isomer of Phenylazobenzene. [2] d) Phenylazobenzene is an orange dye.

What feature of the molecule makes it absorb certain frequencies of visible light? [2]

e) Suggest why this dye interacts better with non-ionic fibres such as polyester rather than ionic fibres such as acrylic. Hint: intermolecular forces? [2]

f) The wash-fastness of dyed fabrics can be likened to a tug-of-war between fibre and water. Explain this statement using phenylazobenzene as the example. [3]

g) Give details of how you would synthesise this azo-dye in the lab from benzene. [5]Mechanisms are not required but you should give any particular experimental conditions.

-24-

5. An active ingredient in many sunscreen creams is 4-aminobenzoic acid.C O O H

N H 2

It can be prepared as described below.

o To 15 g of 4-nitrobenzoic acid, in a flask fitted with a reflux condenser, add 35 g of powdered tin and 75 cm3 of concentrated hydrochloric acid.

o Heat the mixture until the reaction commences, remove the flame and shake the flask gently from time to time. After about 20 minutes cool and decant the liquid into a beaker, wash the residual tin with 15 cm3 of water and add the washings to the beaker.

o Add concentrated ammonia solution until the solution is just alkaline, filter off the precipitate of hydrated tin oxide, wash it well with water and add these washings to the filtrate.

o Acidify the filtrate with concentrated ethanoic acid and evaporate on a water bath until crystals commence to separate.

o Cool in ice, filter the crystals at the pump and dry in a steam oven.

o The yield of 4-aminobenzoic acid, melting temperature 192 °C, is 12 g.

(After ‘A Textbook of Practical Organic Chemistry’ by A. E. Vogel)

(a) Suggest reasons for each of the following: (i) the use of a mixture of tin and hydrochloric acid; (1) (ii) heating the mixture but then taking the flame away; (2) (iii) the use of a reflux condenser; (1) (iv) adding ammonia; (1) (v) adding ethanoic acid. (2)

(b) Calculate the percentage yield of 4-aminobenzoic acid from 4-nitrobenzoic acid, (NO2)C6H4COOH. (3)

(c) 4-aminobenzoic acid can be converted into benzocaine, a local anaesthetic which is used to relieve the pain of sunburn.

2

2 3

C

O O C H C H

N H

(i) Suggest reagents and conditions for carrying out this conversion. (2) (ii) Name the type of reaction involved in this step. (1) (d) A better local anaesthetic than benzocaine is novocaine,

2

2 2

2 3

2 3

C

O O C H C H N C H C H

N H

+

–

H

C H C H

C l

which can be injected into tissues.State with a reason what feature of novocaine, absent in benzocaine, might be responsible for itssolubility in non-fatty tissue. (2)

(Total 15 marks)

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Polymers and Amino AcidsChemistry for A2 Chapter 14 pg 207-221 Total / 70

1 a) Explain the differences between addition and condensation polymerisation. [4] b) Draw the structure of polypropene making the repeat unit clear. [2] c) Draw the mechanism for the formation of polypropene from propene. [4]

2. Read the activity on ‘Covering the O2’ pg 218 of Chemistry for A2. Answer questions 1-8. [15]

3. Terylene is the UK trademark for the polyester formed between ethane-1,2-diol and terephthalic acid.

a) Use the structures of the monomers above to draw the structure of the polyester formed by the elimination of three water molecules. [4]

b) Suggest why polyesters such as this have a high tensile strength and give a consequential use for such polymers. [4]

4. Read the activity on ‘Monitoring and synthesising polyamides’ pg 222 of Chemistry for A2. Answer questions 1 and 3. [16]

5 a) Draw the structure of the repeat unit of nylon 6,6 (formed from 1,6-diaminohexane and hexan-1,6-dioic acid). [4]

b) Suggest why this sort of polyamide lends itself, like Terylene, to being drawn into thin fibres. [2] c) Nylon has a greater tensile strength than polyesters, however. Explain what further intermolecular

force is responsible for this with a suitable diagram and give a consequential use of nylon. [4]d) Explain why polyester fibres are better at absorbing sweat and water than polyamide fibres.[3]

6. Three amino acids are shown below.

a) Explain why glycine is the only amino acid that isn’t chiral. [2] b) Draw the two enantiomeric forms of valine [2] c) Explain why L-serine is over 100 times cheaper than D- serine. [2] d) Draw the structural formula of the dipeptide Val-Ser [2] e) Draw the structural formula of another dipeptide formed between Val and Ser. [2] f) Draw the structure of glycine in an acidic solution. [2] g) Draw the structure of glycine in an alkaline solution. [2] h) Draw the zwitterionic form of glycine. [2] i) Explain why amino acids are solids at room temperature. [2]

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Synthetic Reaction SchemesChemistry for A2 Chapter 15 pg 232-233 Total / 50

1. Read the activity on ‘Converting one functional group to another’ pg 233 of Chemistry for A2. Answer questions 1 and 2. [15]

2. a) Use the information in the scheme below to deduce the structures of A to I. [18]

b) Identify the two compounds that have chiral carbons. [2]

A is C5H10O and has an absorption at 1700 cm-1 in the infra red.C has pH 3 in aqueous solution.I does not react with acidified potassium dichromate.

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3. Use the information in the scheme below to answer the questions that follow.

SCHEME B

a) Give the reagents and an explanatory mechanism for step a). [4]

b) Write equations to show how this azo-dye in step b) could be formed from ethylbenzene and nitrobenzene. [3]

c i) What sort of reaction is Step c? [1]

ii) Explain carefully how aqueous bromine reacts with phenylethene. [3]

d i) Draw the structural formula of poly(phenylethene). [2]

ii) Give two reasons why addition polymers like poly(phenylethene) are difficult to dispose of.

[2]

-28-

Organic SynthesisChemistry for A2 Chapter 15 pg 225-244 Total / 57

1. Design synthetic routes for the following conversions, giving the reagents and conditions needed for each step.

[16]

2. Read the activity on ‘Thalidomide’ pg 241 of Chemistry for A2. Answer questions 1 to 9 on pg 241-242.For question 3 just draw the skeletal formula of thalidomide rather than using a model kit.

[25]

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3. Adrenalin is a hormone which raises blood pressure, increases the depth of breathing and delays fatigue in muscles, thus allowing people to show great strength under stress.Benzedrine is a pharmaceutical which stimulates the central nervous system in asimilar manner to adrenalin.

C H C H (C H ) N H2 2 2 33

H O

H O C H (O H ) C H N

H

C H

B e n zed rin e A d ren a lin

a i) Draw the skeletal formula of Benzedrine and mark with a (*) any asymmetric

carbon atom that causes chirality. [2] ii) Draw the skeletal formulae of the two enantiomeric forms of Benzedrine. [2]

b) Suggest why adrenalin is more soluble in water than is benzedrine. [2]

c) Give the structural formulae of the organic products obtained when benzedrine reacts with:

i) an aqueous acid such as dilute hydrochloric acid; ii) ethanoyl chloride in the absence of a catalyst; iii) excess ethanoyl chloride in the presence of the catalyst anhydrous AlCl3. [4]

d) Comment on any issues that may arise if a drug company wanted to scale up a synthetic scheme to make Benzedrine form benzene by the tonne. [5]

Challenge of the week – You’ve gotta be good to do this one! e) Design a synthetic pathway to make Benzedrine from benzene. Include all the reagents and conditions needed. (Hint it may take over 5 steps!). [10]

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More Organic SynthesisA2 Chemistry Chapter 15 pg 299-305 Total / 42

1. The reaction sequence below shows a method that could be used to convert benzene into benzoic acid.

a i) Name the reagent and catalyst that could be used to convert benzene into A in Step 1. [2] ii) Name the type of reaction in Step 1 and its mechanism. [2] iii) Write an equation to show how the catalyst interacts with the reagent in Step 1 and explain how this helps the reaction to take place. [2] b i) B has several isomers. Draw the structural formula of ONE of these isomers, and give its systematic name. [2]

ii) Name the reagent and catalyst you would use to try to make your isomer from A. [2] c i) Name the type and mechanism of the reaction in Step 3. [2]

ii) By considering halogenoalkane B, suggest whether the reaction in Step 3 is first or second order. Justify your answer. Draw the mechanism that you suggest. [2]

d) What type of reaction is Step 4? [1] e) Suggest TWO reactions in which you would observe the same results when carried out with either compound C or benzoic acid. Describe what you would see in each of the two reactions. [4]

2. Vanillin, the main ingredient of vanilla essence, is one of the commonest flavouring ingredients found in foods. Synthetic vanillin, which is identical to natural vanillin, can be manufactured from methoxybenzene. One synthetic route is shown below:

m e th o x y b en zen e 2 -m e th o x y b en zen e 2 -m e th o x y p h en o l v an illin su lp h o n ic ac id

S O H O H O H

O C H O C H O C H O C H

C H O

3 3 3

3

3

a i) Name the reagent which converts methoxybenzene to 2-methoxybenzene sulphonic acid. ii) Name the type of reaction which occurs and its mechanism. [3] b) After the final stage, in which 2-methoxyphenol is converted to vanillin, the impure product can be purified by recrystallisation. In this process the solid is dissolved in the minimum volume of hot water. The mixture is then filtered whilst still hot. The filtrate is cooled in an ice bath to produce crystals of vanillin. These can be removed by filtration and dried. i) Why is the “minimum volume of hot water” used? [1] ii) The impure vanillin may contain soluble and insoluble impurities. Describe how each of these is removed during recrystallisation. [2] iii) How would you check the purity of the vanillin after recrystallisation, other than by using an infrared spectrometer. [2]

-31-

c) In order to establish whether or not vanillin had been formed, two infrared spectra were obtained: a sample of pure 2-methoxyphenol and a sample of the product. Study the spectra and data below.

In fra red S p ectru m o f 2 -M eth o x y p h en o l

In fra red S p ectru m o f P ro d u ct

1 0 0

8 0

6 0

4 0

2 0

3 0 0 0 2 0 0 0 1 0 0 0

Wa v e n u m b e r / c m –1

Tra n sm itta n c e/ %

1 0 0

8 0

6 0

4 0

3 0 0 0 2 0 0 0 1 0 0 0

Wa v e n u m b er / c m – 1

Tra n sm itta n c e/ %

Comment as to whether any vanillin is likely to have been formed during the process. Support your answer with relevant evidence. [2]

3. Thiols are organic sulphur compounds that undergo similar reactions to alcohols.Phosphines are organic nitrogen compounds that undergo similar reactions to amines.

Design synthetic routes for the following conversions, giving the reagents and conditions needed for each step.

i)

[3]ii)

[5]iii)

[5]

-32-