Examzone

Examzone

Examzone: Unit 4 Test 1 (chapters 1.1 to 1.5)

1 The kinetics of reactions can be followed in various ways. The techniques usually involve either sampling the reaction mixture at various times together with a means of slowing or stopping the reaction in the sample, or making use of some physical method for following the reaction continuously. The iodination of propanone occurs in aqueous solution, and is catalysed by acid: H+ CH3COCH3(aq) + I2(aq) CH3COCH2I(aq) + HI(aq) The rate is followed by finding the iodine concentration at various times. a i What continuous method would you use to determine the iodine concentration? (2) c A suitable quenching solution for the method described in part a(ii) is sodium hydrogencarbonate (sodium bicarbonate) solution. It neutralises the acid catalyst without making the solution so alkaline that other reactions occur. i If sodium hydroxide solution, a strong alkali, were used, propanone and iodine would give another product. Name it, and write an equation for the reaction occurring. (3)

ii At 25C, Ka for propanoic acid is 1.30 105 mol dm3. Find the pH of a solution of propanoic acid of concentration 0.0100 mol dm3. State any assumptions you make. (3) iii Increasing the temperature of the propanoic acid solution causes the pH to decrease. What does this tell you about the enthalpy of dissociation? Justify your answer. (3) (Total 9 marks) 4 a i Define pH. (1) (1)

6 Hydrogen and iodine react together to give an equilibrium: H2(g) + I2(g) 2HI(g) a Write an expression for Kp for this equilibrium, giving consideration to its units. (2) b When 0.50 mol of I2 and 0.50 mol of H2 were mixed in a closed container at 723 K and 2 atm pressure, 0.11 mol of I2 were found to be present when equilibrium was established. i Calculate the partial pressures of I2, H2 and HI in the equilibrium mixture. (3) (2)

ii Define Kw, the ionic product of water.

ii Hence calculate the value of Kp at 723 K. c

ii This reaction is used to detect the presence of either of two possible structures in organic molecules. Give these structures. (2) iii Describe briefly a test you could use to distinguish between these two structures. (1) (Total 15 marks) 2 In an experiment designed to find the mechanism of the reaction between a halogenoalkane, RX, and hydroxide ions, the following data were obtained at constant temperature.
Initial concentration of RX/mol dm3 0.01 0.01 Initial concentration of OH/mol dm3 0.04 0.02 0.04 Initial rate/ mol dm3 s1

b Calculate the pH of the following solutions. (The ionic product of water, Kw, should be taken to be 1.00 1014 mol2 dm6) i A solution of sulfuric acid having a concentration of 0.100 mol dm3. (1)

ii If you withdrew samples at various times and stopped the reaction with a suitable reagent, how might you then determine the iodine concentration? (2) iii Suggest a reason why the continuous method might be preferable. (1) b The variation of iodine concentration with time in such an experiment is shown below.

ii A solution of sodium hydroxide having a concentration of 0.0500 mol dm3. c i What is the principal property of a buffer solution?

In an experiment to establish the equilibrium concentrations in part b, the reaction was allowed to reach equilibrium at 723 K and was then quenched by addition to a known, large volume of water. The concentration of iodine in this solution was then determined by titration with standard sodium thiosulfate solution. i Write an equation for the reaction between sodium thiosulfate and iodine. (2)

(2)

(1)

8 106 4 106 4 106

ii The dissociation constant for ethanoic acid is 1.80 105 mol dm3. Calculate the pH of a buffer solution which has a concentration of 0.0150 mol dm3 with respect to ethanoic acid and 0.0550 mol dm3 with respect to sodium ethanoate. (3) (Total 9 marks) 5 Ammonia is manufactured from hydrogen and nitrogen in the Haber Process: N2(g) + 3H2(g) 2NH3(g) H = 92 kJ mol1

ii What indicator would you use? Give the colour change at the end point. (2) iii In this titration and in titrations involving potassium manganate(VII), a colour change occurs during the reaction. Why is an indicator usually added in iodine/thiosulfate titrations but not in titrations involving potassium manganate(VII)? (2) (Total 13 marks)

iodine concentration/ mol dm 3

0.005

time/s

a Deduce the order with respect to RX and OH, and hence write the rate equation for the reaction. (3) b Calculate a value for the rate constant for the reaction. (2) (Total 5 marks) 3 a Propanoic acid is a weak acid. Explain the term weak. (1) b i (1) Give an equation for the dissociation of propanoic acid, and hence an expression for its dissociation constant, Ka. (2)

a What is meant by the term dynamic equilibrium? (2) b State the conditions employed industrially in the manufacture of ammonia, and justify them on physico-chemical grounds. (5) c What effect does a catalyst have on the rate of achievement of the equilibrium and the composition of the equilibrium mixture?

What does this tell you about: i the rate of reaction over a period of time (1)

ii the order of reaction with respect to iodine (1) iii the rate-determining step of the reaction iv the least number of steps in the reaction mechanism? (1)

(2)

(Total 9 marks)

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Examzone

Examzone: Unit 4 Test 2 (chapters 1.6 and 1.7)

1 a What is meant by a chiral compound? (1) Consider the following series of reactions and answer the questions which follow.

2 The steps in the process of recrystallisation are detailed below: A B C D E Add a little solvent to the sample. Dry the product. Allow the solution to cool. Filter cold. Wash the residue with a small amount of cold solvent. F Warm until the sample dissolves. G Filter while the solution is still hot. a Put these steps for recrystallisation in the correct order. (2)

Draw the structure of the ester formed from the reaction of propan-2-ol with propanoic acid in the presence of concentrated sulfuric acid. (1)

d State the name of the organic product if propan2-ol is heated with concentrated sulfuric acid and classify the type of reaction occurring. (2) (Total 7 marks) 4 Propanone can be prepared in the laboratory by oxidising propan-2-ol. A student was given the following instructions and data. Dissolve 10 g of potassium dichromate(VI) in 30 cm3 of water. Add 12 cm3 of propan-2-ol followed by 6 cm3 of concentrated sulfuric acid. Boil the mixture for 15 minutes. The boiling temperatures of the volatile substances are:
Substance Boiling temperature/C 82 100 56

C6H12O2 A

NaOH (aq)

C4H10O B

CH3CO2Na+ C

NaOH(aq) C4H8 F H2/Pt C4H10 G

b Compound E displays optical isomerism. i State what this means.

HCl(aq) CH3CO2H D

ethanolic KOH HBr

b Give the reasons for the words in bold type in step A and in step E. (2) (Total 4 marks) 3 An alcohol, C3H8O, was analysed by low-resolution NMR spectroscopy. The spectrum is given below.

C4H9Br E

propan-2-ol water propanone

(1) (2) a What safety precaution, in addition to wearing eye protection, must be taken when adding the concentrated sulfuric acid? (1)
7 6 5 4 3 2 1 0

ii Sketch the optical isomers of E. c The reaction of E to give B is a nucleophilic substitution. i What is meant by the term nucleophile?

(1) b i (1)
ppm

ii Give the structural formula for B.

iii Give a simple chemical test for the functional group in B, and say what you would see. (2) d The type of reaction exemplified by A B + C is important in the manufacture of soap. i What type of reaction is this? (1)

The chemical shifts of some hydrogen nuclei are given in the following table (where R represents an alkyl group).
Group CH3R RCH2R CHR3 /ppm 0.81.2 1.11.5 1.5 Group ROH RCH2OH R2CHOH /ppm 1.06.0 3.34.0 3.24.1

Draw a diagram of the apparatus that you would use to boil the mixture for 15 minutes. (2)

ii Outline how you would obtain propanone from this aqueous mixture after it had been boiled for 15 minutes. (2) c The sample of propanone was dried. Describe a test that you would do to show that your final sample of propanone did not contain any propan-2-ol. (2) (Total 7 marks)

ii A could be reacted with aqueous acid to give B and D. If the same quantity of A was treated with aqueous acid, instead of aqueous alkali, how would the yield of B differ? Explain your answer. (1) e Consider the reaction C D. i Name D. (1) (1) (2) (Total 14 marks)

a Show that the alcohol must be propan-2-ol.

(2)

ii Identify the acidbase conjugate pair in this reaction. iii Explain why the reaction occurs.

b What would the observation be if propan-2-ol is reacted with aqueous iodine in the presence of alkali? (2)

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Examzone

Examzone: Unit 5 Test 1 (chapters 2.1 and 2.2)

1 The following data concern the redox chemistry of halogen elements and sodium thiosulfate. E/V Cl2(g) + 2e

25.0 cm3 portions of this solution were pipetted into a titration flask and an excess of potassium iodide solution added. The liberated iodine was then titrated against sodium thiosulfate solution of concentration 0.100 mol dm3. 18.7 cm3 of the sodium thiosulfate solution was required for complete reaction. O E /V Ni2+(aq) + 2e Ni(s) Zn2+(aq) + 2e Zn(s) S4O62(aq) + e S2O32 Cu2+(aq) + e 2.71 0.76 +0.09 +0.15 +0.34 +0.54

4 State three properties which distinguish transition metals from main group metals. (3) (Total 3 marks) 5 Look at this reaction scheme: [Cu(H2O)6]2+(aq) blue precipitate deep blue solution A B C a Name the types of reaction involved in the conversion of: i A to B (1) (1) (1)

2Cl(aq)

+1.36 +1.07 +0.57 +0.54 +0.09

Br2(l) + 2e 2Br(aq) 2SO42(aq) + 10H+(aq) + 8e S2O32(aq) + 5H2O(l) I2(s) + 2e 2I(aq) S4O62(aq) + 2e

Cu+(aq)

ii B to C b Give the formula of compound B. c

Cu2+(aq) + 2e Cu(s) I2(aq) + e I(aq) a i

2S2O32(aq)

a What is the maximum change in oxidation number of sulfur which can be brought about by the action of sodium thiosulfate with: i iodine (2) (3)

NO3(aq) + 2H+(aq) + e NO2(g) + H2O(1) +0.81 Using the appropriate half-equations, write an equation for the reaction of any one of the metals in nickelbrass with concentrated nitric acid. (2) (1)

Draw the structure of the ion responsible for the colour in solution C and show its shape. (2) (Total 5 marks)

ii chlorine? Write full ionic equations for each reaction.

ii What type of reaction is taking place? b Identify by giving full formulae: i the complex cations present in A

6 a Suggest why the hydrated ion [V(H2O)6]2+ is coloured. (1) b Name the types of bonding within ions of this type. (2) (Total 3 marks)

b Suggest a reason why bromine cannot be estimated by direct titration with sodium thiosulfate in the same way that iodine can. ) 2 ( (Total 7 marks) 2 a What do you understand by the term standard electrode potential? (2)

(2) (2) (1)

ii the precipitates in B iii any metal-containing anion in C. c i

b If a metal is immersed in a solution of its ions, the potential set up between the metal and the solution cannot be measured without using a reference electrode. Explain why this is so. (2) c i What is meant by disproportionation? (1)

Write an equation for the precipitation of any one of the metal ions in A with sodium hydroxide. (2)

ii What type of reaction is occurring in c(i)? (1) d Suggest an explanation why it is necessary to add sodium hydroxide, followed by dilute sulfuric acid, before performing the titration. (3) e On addition of the potassium iodide solution, the only reaction which occurs is: 2Cu2+(aq) + 4I(aq) 2CuI(s) + I2(aq)

ii Use the following data to deduce whether MnO2 will disproportionate in acidic solution.
O MnO4(aq) + 4H+(aq) + 3e MnO2 + 2H2O(l) E = +1.70 V O MnO2(s) + 4H+(aq) + 2e Mn2+(aq) + 2H2O(l) E = +1.23 V (2) (Total 7 marks)

3 Some modern British coins are made from an alloy, nickelbrass, which consists essentially of the metals copper, nickel and zinc. A one pound coin weighing 9.50 g was completely dissolved in concentrated nitric acid, in which all three metals dissolve, to give solution A. Dilute sodium hydroxide solution was then added carefully with stirring, until present in excess. Zinc hydroxide is amphoteric. The precipitate formed, B, was filtered off from the supernatant liquid, C. The precipitate, B, was quantitatively transferred to a graduated flask of 500 cm3 capacity. Dilute sulfuric acid was then added to dissolve the whole of the precipitate, B, and the solution made up to 500 cm3 with distilled water.

Write an equation for the reaction between sodium thiosulfate and the liberated iodine. What indicator would you use in this titration? At what stage would you add it? Give a reason for your answer. (3)

ii Calculate the percentage of copper in the alloy. (5) iii Suggest why this reaction occurs in the light of O the E values given. (3) (Total 25 marks)

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Examzone

Examzone: Unit 5 Test 2 (chapters 2.3 to 2.5)

1 a The enthalpy change for the reaction CH2=CH2 + H2 CH3CH3 is 120 kJ mol1, whereas that for the reduction of benzene, C6H6, to cyclohexane, C6H12, is 208 kJ mol1. What may be deduced from the fact that this value is not three times the first one? (2) b i State the conditions under which benzene may be nitrated to form mononitrobenzene. (2)

Why should the reaction mixture be kept between 0 C and 5 C?

(2)

ii Is the diazotisation reaction exothermic or endothermic? How do you know? (2) d Give the equation, using structural formulae, for the diazo coupling reaction between benzene diazonium chloride and 2-naphthol. (2) (Total 9 marks) 3 Outline how the following conversions could be carried out in the laboratory, giving reagents, conditions and equations. a i

b Suppose that you have to purify a sample of A by recrystallisation from trichloromethane. This solvent is toxic by inhalation and skin absorption but is not flammable. i What safety precautions would you take using this solvent? (2)

ii Describe in detail how you would recrystallise a sample of about 5 g of A. (5) iii What simple test would you use to determine the purity of your recrystallised material? (2) (Total 15 marks) 5 This question relates to the following reaction scheme: C2H5Br C2H5CN C2H5CH2NH2 step 1 step 2 C2H5CH2NHCOCH3 step 3 a Give the reagents, the conditions required and the equation for: i Step 2 (3) (3)

CH3 to

CH2Cl

ii Both of the reagents that are used to nitrate benzene are usually regarded as acids. However, in this instance, one of them behaves as a base. Show how this is so. (2) iii Give the mechanism for the nitration of benzene. (2)

(3) ii Given that the boiling temperatures of these two compounds are 111C and 179C, respectively, how would you isolate a pure sample of the chlorohydrocarbon? (2) b CH3CH2CH2NH2 to CH3CH2CH2NH3+Cl (3) (Total 8 marks) 4 Consider the compound A.

iv Explain why benzene tends to undergo substitution rather than addition reactions. (1) (Total 9 marks) 2 The following is adapted from a textbook of practical chemistry which gives details for the preparation of the azo dye phenylazo-2-naphthol. Dissolve 2.5 g of phenylamine in a mixture of 8 cm3 of concentrated hydrochloric acid and 8 cm3 of water in a small beaker. Place in an ice bath; ignore any crystals that may appear. When the temperature is between 0 C and 5 C, add drop by drop a solution of 2 g of sodium nitrite dissolved in 10 cm3 of water, not allowing the temperature to rise above 5 C. Addition of the sodium nitrite solution should continue until, after a wait of 3-4 minutes, a drop of the reaction mixture gives an immediate blue coloration with starchiodide paper. Prepare a solution of 3.9 g of 2-naphthol in 10% aqueous sodium hydroxide solution in a 250 cm3 beaker, and cool in ice bath to below 5 C; add 1015 g of crushed ice to this solution. Stir the mixture, and add the diazonium salt prepared as above very slowly; red crystals of the azo compound will separate. When addition is complete, allow the mixture to stand in ice for 10 minutes and then filter the product, using gentle suction on a Buchner funnel. Wash with water. The product may be recrystallised from glacial ethanoic acid. It has a melting temperature of 131 C. a Phenylamine is toxic by inhalation and skin absorption; concentrated hydrochloric acid is corrosive and gives harmful fumes. What specific precautions would you therefore take when doing this experiment? (2) b Write the equation for the reaction between phenylamine and hydrochloric acid.

ii Step 3

b What drug is based on the compound formed in step 3? (1) (Total 7 marks)

H A C OH

CH3 C H NH2

It is related to the hormone adrenaline. a Draw the structures of the organic product(s) which you expect from the reaction of A with: i phosphorus pentachloride (1) (1) (2) (1) (1)

ii dilute hydrochloric acid iii ethanoyl chloride iv hot alkaline potassium manganate(VII) v hot concentrated sulfuric acid

(1)

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