2.

In moths a pheromone, P, acts as an attractant for the opposite sex. P has the molecular formula C7H12O. What can be deduced about the structure of P from the following information? (a) (i) 1 mole of P reacts with 1 mole of Br2 molecules to form a compound with the formula C7H12OBr2.
(1)

(ii)

When lithium tetrahydridoaluminate is reacted with P a compound with the formula C7H14O is formed.
(1)

(iii) P forms an orange precipitate with 2,4-dinitrophenylhydrazine.

(1)

(iv) When P is heated with Fehlings or Benedicts solution, the solution remains blue.
(1)

(v) (b)

P is a Z-isomer.
(1)

What does the following physical data tell you about the structure of P? Use your Data booklet where necessary. (i) The infrared spectrum of P has the following absorptions at wavenumbers above 1600 cm1. 3060 cm1 2920 cm1 1690 cm1 1660 cm1
(3)

(ii)

The nmr spectrum does not have a peak corresponding to a chemical shift, H, of between 9 and 10.
(1)

(iii)

The mass spectrum showed the presence of peaks at mass/charge ratios of 15 and 29, but no peak at 43.
(3)

(c)

Given that P has a straight chain of carbon atoms in its formula, use the information you have deduced above to suggest a displayed formula for the pheromone P.
(2)

(d)

How could you use a purified sample of the orange precipitate in (a)(iii) to confirm the formula of P?
(2) (Total 16 marks)

3.

Compound V, the structure of which is shown below, is found in human sweat. CH3 C CH3 CH2 CH2 C C H O

OH Compound V

(a)

Compound V contains two functional groups. Identify both functional groups and state a chemical test for each. The result of each test should also be included in your answer.
(4)

(b)

Compound V can be converted into two carbonyl compounds W and X, shown below.

H C C O W

O CH3CH2CH2 C OH X

CH3 O

(i)

Which of the compounds W or X would react when warmed with Fehlings solution to give a red precipitate? Justify your answer.
(1)

(ii)

Compound W can be reduced in two steps to compound Y of molecular formula C2H6O2. Identify Y.
(1)

(iii) Compound W can be oxidised to compound Z of molecular formula C2H2O4. Identify Z.

(1)

(c)

The compounds Y and Z react together under suitable conditions to form a polymer. (i) (ii) Draw the structural formula of the repeating unit for the polymer formed.
(2)

What type of polymerisation reaction occurs between compounds Y and Z?

(1) (Total 10 marks)

4.

Cyanide ions react with 2-bromo-2-methylpropane in the following way: (CH3)3CBr + CN The rate equation for this reaction is 2 (CH3)3CCN + Br

rate = k[(CH3)3CBr] (i) (ii) What information does this rate equation give about the mechanism of this reaction?
(2)

Give the mechanism for this reaction consistent with the rate equation.
(3) (Total 5 marks)

5.

One of the alarm pheromones for ants, compound Q, has the molecular formula C6H10O. (a) State what can be deduced about compound Q from each of the following pieces of information. (i) Q, C6H10O, is a non-cyclic organic compound. When saturated it would contain 14 hydrogen atoms.
(1)

(ii)

Compound Q does not react with sodium.

(1)

(iii) One mole of compound Q reacts with one mole of bromine molecules, Br2, in the absence of sunlight.
(1)

(iv) Compound Q gives a yellow precipitate with Bradys reagent, 2,4dinitrophenylhydrazine.

(1)

(v)

When compound Q is warmed with Benedicts solution, a red precipitate is formed.

(1)

(vi)

Compound Q exists in the trans form.

(1)

(vii) Given that compound Q is a straight chain molecule with the two functional groups next to one another, give the displayed formula of Q.
(2)

(b)

(i)

Compound Q, C6H10O, can be converted into C6H14O in two steps. Give the reagent and any catalyst needed for each step.
(2)

(ii)

Name the functional group which would now be present? ...........................................................................................................................

(1) (Total 11 marks)

7.

Consider the following compounds.

H H H Compound X HCCCC H H H

O H OCH H

H C Compound Y H C

H H H

CCH OH H

H Compound Z

HCCCC OH H H O

(a)

Name the functional groups present in the three compounds X, Y and Z. Compound Functional groups present

Z
(3)

(b)

Compounds X, Y and Z are heated separately with alkaline ammoniacal silver nitrate solution. Draw the full structural formula, showing all bonds, of any organic product formed. If a reaction does not occur, write no reaction. 4

(c)

Draw the formulae of the organic products formed by the reaction of (i) X, CH3CH2CH2COOCH3, with aqueous sodium hydroxide solution.
(2)

(ii)

Z, CH2(OH)CH2CH2CHO, with hydrogen cyanide.

(1) (Total 9 marks)

8.

(a)

Draw the displayed formula of a branched chain ketone containing five carbon atoms.
(2)

(b)

Give the systematic name for this ketone.

(1)

(c)

What is the molecular formula of the alcohol this ketone could be made from?
(1)

(d)

An alcohol can be converted into a ketone by oxidation with sodium dichromate(VI) and sulphuric acid. Explain why refluxing the mixture first, rather than immediately distilling the product over from the beginning, results in a higher yield of the ketone.
(1) (Total 5 marks)

9.

The principal reaction occurring when 2-bromo-2-methylpropane reacts with aqueous sodium hydroxide is as follows:

CH 3C(CH3)CH3 + NaOH Br

CH3C(CH3)CH3 + NaBr OH

Several experiments were carried out in order to follow the kinetics of this alkaline hydrolysis. A few drops of phenolphthalein were added to a sample of sodium hydroxide, and, after the addition of a measured amount of 2-bromo-2-methylpropane, the mixture was vigorously shaken and a clock was immediately started. The time was taken when the pink colour due to the indicator disappeared. This experiment was repeated twice using different concentrations of the two reactants. All experiments were carried out at the same temperature. The results are shown in the table below. 5

Experiment A B C

2-bromo-2-methylpropane / mol dm3 0.011 0.022 0.022

Sodium hydroxide / mol dm3 8.0 104 8.0 104 1.2 103

Time /s 33 16 24

(a)

(i) (ii)

Identify the attacking species responsible for this alkaline hydrolysis.

(1)

Assuming that the final concentration of sodium hydroxide is zero, calculate the average rates of reaction in mol dm3 s1 for experiments A and B. A ................. mol dm3 s1 B ................. mol dm3 s1
(2)

(iii)

Deduce the order of reaction with respect to 2-bromo-2-methylpropane. Justify your answer.
(1)

(iv) By comparing the average rates of reaction between experiments B and C, deduce the order of reaction with respect to sodium hydroxide.
(2)

(v)

Write the rate equation for the reaction. Rate =

(1)

(vi)

From your rate equation, suggest how this reaction proceeds by giving a possible mechanism.
(3)

(b)

Explain briefly why 1-bromobutane, an isomer of 2-bromo-2-methylpropane, reacts by a different mechanism when it is hydrolysed.
(2) (Total 12 marks)

10.

Methanoic acid and ethanol react together to form ethyl methanoate, HCOOC2H5, and water. This reaction is reversible and can be allowed to reach equilibrium. HCOOH(l) + C2H5OH(l) (a) HCOOC2H5 (l) + H2O(l) H = +45 kJ mol1

Draw the full structural formula of ethyl methanoate, showing all bonds.
(1)

(b) (c)

What type of organic compound is ethyl methanoate?

(1)

In an experiment, 3.00 mol methanoic acid, HCOOH, and 6.25 mol ethanol, C2H5OH, were mixed together. A small quantity of catalyst was added. The mixture was left for several days in a water bath to reach equilibrium at constant temperature. (i) Complete the table. Number of moles in the reaction mixture HCOOH at start of experiment at equilibrium 3.00 0.50
(2)

C2H5OH 6.25

HCOOC2H5 0.00

H2O 0.00

(ii)

Write an expression for the equilibrium constant, K c, for the reaction.

1)

(iii)

Calculate Kc for the reaction at the temperature of the experiment. The total volume of the equilibrium mixture was 485 cm3.
(2)

(iv)

State and explain whether Kc for this reaction has units.

(1)

(d)

(i)

The temperature of this equilibrium mixture is lowered. Explain the effect of this on the value of the equilibrium constant and hence on the yield of ethyl methanoate.
(4)

(ii)

A student added more catalyst to the mixture. State, giving a reason, what would happen to the composition of the equilibrium mixture.
(1) (Total 13 marks)

11.

A chemist has synthesised a compound W believed to be Cl HO CH CH CH C OH O

(a)

State and explain what you would see if W is reacted with: (i) sodium carbonate solution
2)

(ii) (b)

bromine water.
(3)

W shows both types of stereoisomerism. (i) (ii) How many stereoisomers of W are there? Briefly explain your answer.
(2)

Explain why W shows optical isomerism.

(2)

(c)

Describe how you would show that W contains chlorine.

(5) (Total 14 marks)

12.

This question concerns the reactions of some compounds of nitrogen. (a) The ammonium ion reacts with water and behaves as an acid. NH4+(aq) + H2O(l) (i) NH3(aq) + H3O+(aq)

Identify the TWO conjugate acid-base pairs in the spaces provided. acid 1 ................................... base 1 ................................... acid 2 ................................... base 2 ...................................
(1)

(ii)

Write the expression for the acid dissociation constant, Ka, of the ammonium ion.
(1)

(iii)

A solution of ammonium chloride has a pH of 5.00 at 25C. Ka for the ammonium ion is 5.62 1010 mol dm3 at 25C. Calculate the concentration of this solution. State any assumptions you have made.
(4)

iv)

Use the following table and your answer from part (iii) to suggest a suitable indicator for the titration of ammonia solution with hydrochloric acid. Justify your answer. Indicator thymol blue methyl red phenolphthalein pKIn 1.7 5.1 9.3
(2)

(b)

Hydrogen cyanide is a weak acid in aqueous solution. Write an equation to show why aqueous solutions of cyanide ions are alkaline.
(1)

(c)

Hydrogen cyanide reacts with propanal as follows: CH3CH2CHO + HCN CH3CH2CH(OH)CN

Propanal is reacted with a solution of potassium cyanide, KCN, containing a little dilute sulphuric acid. (i) What type of reaction is this?
(1)

(ii)

Give the mechanism for the reaction.

(3)

(iii)

It is important that the pH is neither too acidic nor too alkaline if a good yield of the product is to be obtained. Explain why this is so.
(2)

(d)

In an investigation of the kinetics of the nucleophilic substitution reaction between 1chloropropane and potassium cyanide in aqueous ethanolic solution, the reaction was found to be first order with respect to 1-chloropropane and first order with respect to cyanide ions. (i) Give the rate equation for the reaction. (1) 9

(ii)

Write a mechanism for the reaction that is consistent with this rate equation.
(3) (Total 19 marks)

13.

(a)

The table below shows the acid dissociation constants, K a, of three carboxylic acids. Acid Chloroethanoic Dichloroethanoic Trichloroethanoic Structural formula CH2ClCO2H CHCl2CO2H CCl3CO2H Ka/ mol dm3 1.3 103 5.0 102 2.3 101

(i)

Write an expression for the acid dissociation constant, Ka, of chloroethanoic acid.
(1)

(ii)

Calculate the pH of a 0.0010 mol dm3 solution of chloroethanoic acid, making the usual assumptions.
(3)

(iii)

Which acid would have the lowest pH at a concentration of 0.0010 mol dm3? Use both the data and the structure of the acids to justify your answer. No further calculation is required.
(2)

(b)

Chloroethanoic acid, CH2ClCO2H, reacts with methanol, CH3OH, in the presence of a sulphuric acid catalyst. (i) Draw the displayed formula and give the name of the organic product formed. **Displayed Formula **Name
(3)

(ii)

What name is given to the functional group formed in this organic product?
(1)

(iii)

What type of reagent is methanol in this reaction? Explain why it is able to behave in this way and describe how it attacks the chloroethanoic acid. You may find it helpful to draw a diagram.
(3)

(iv)

How would you convert the organic product of the reaction between chloroethanoic acid and methanol back into the original compounds?
(2) (Total 15 marks)

10

30.

This question concerns the three isomers A, B and C, each of which has a relative molecular mass of 134. O C CH 2 A CH 3 CH 2 CH 2 B C H O

CH C (a)

CH

CH 2 OH

The mass spectrum of substance A is shown below. Identify the species responsible for the peaks labelled 1, 2 and 3. Peak 1 ......................................................................................................................... Peak 2 ......................................................................................................................... Peak 3 .........................................................................................................................
(3)

(b)

The infra-red spectra of two of these substances were also measured. (i) Use the table and the spectra below to identify which spectrum is that of substance C. Wavenumber / cm1 3000-3100 2850-3000 Wavenumber / cm1 3200-3570 3580-3650

Bond CH (arenes) CH (alkanes)

Bond OH (hydrogen bonded) OH (not hydrogen bonded) C==C (arenes)

C==O

1680-1750

1450-1600

The spectrum of substance C is spectrum number ..........................................

(1)

(ii)

Give one reason for your choice.

(1)

(iii)

Give one other reason why the other spectrum could not be that of substance C.
(1)

11

100 80 Relative intensity 60 40 20 0 25 50 m/e 75 100 1

125

100

Transmittance

50

0 4000

3000

2000 1500 Wavenumber/cm1

1000

100

Transmittance

50

0 4000

3000

2000 1500 Wavenumber/cm1

1000

12

(c)

State which of the substances A, B and C will react with the following reagents and state what would be observed. (i) Bromine dissolved in hexane. Substance(s) ..................................................................................................... Observation ......................................................................................................(2) (ii) A warm ammoniacal solution of silver nitrate. Substance(s) ..................................................................................................... Observation ......................................................................................................(2) (iii) 2,4-dinitrophenylhydrazine solution. Substance(s) ..................................................................................................... Observation ...................................................................................................... (3) (iv) Give the structural formula of the organic product(s) obtained in (c)(i). (1) (v) Give the structural formula of the organic product(s) obtained in (c)(ii). (1)
(Total 18 marks)

31.

The kinetics of the hydrolysis of the halogenoalkane RCH2Cl with aqueous sodium hydroxide (where R is an alkyl group) was studied at 50 C. The following results were obtained: Experiment 1 2 3 (i) [RCH2Cl] 0.050 0.15 0.10 [OH] 0.10 0.10 0.20 Initial rate/mol dm3 s1 4.0 104 1.2 103 1.6 103

Deduce the order of reaction with respect to the halogenoalkane, RCH2Cl, and with respect to the hydroxide ion, OH, giving reasons for your answers.
(4)

(ii)

Hence write the rate equation for the reaction. ................................................................................................................................

(1)

(iii)

Calculate the value of the rate constant with its units for this reaction at 50 C.
(2)

(iv) Using your answer to part (ii), write the mechanism for this reaction.
(3) (Total 10 marks)

13