January 2014 (IAL) QP - Unit 4 Edexcel Chemistry A-Level PDF
January 2014 (IAL) QP - Unit 4 Edexcel Chemistry A-Level PDF
January 2014 (IAL) QP - Unit 4 Edexcel Chemistry A-Level PDF
Chemistry
Advanced
Unit 4: General Principles of Chemistry I – Rates, Equilibria
and Further Organic Chemistry (including synoptic
assessment)
Monday 13 January 2014 – Afternoon Paper Reference
Instructions
t Use black ink or ball-point pen.
t Fill in the boxes at the top of this page with your name,
centre number and candidate number.
t Answer all questions.
t Answer the questions in the spaces provided
– there may be more space than you need.
Information
t The total mark for this paper is 90.
t – use this asfora guide
The marks each question are shown in brackets
as to how much time to spend on each question.
t written
Questions labelled with an asterisk (*) are ones where the quality of your
communication will be assessed
– you should take particular care with your spelling, punctuation and grammar, as
well as the clarity of expression, on these questions.
t A Periodic Table is printed on the back cover of this paper.
Advice
t Read each question carefully before you start to answer it.
t Keep an eye on the time.
t Try to answer every question.
t Check your answers if you have time at the end.
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P44451A
©2014 Pearson Education Ltd.
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SECTION A
Answer ALL the questions in this section. You should aim to spend no more than 20 minutes on
this section. For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .
1 Select the correct states for the stationary and mobile phases in HPLC.
A liquid gas
B gas liquid
C solid liquid
D solid gas
(b) Which of the following has two peaks in its low resolution NMR spectrum?
(1)
A Dichloromethane, CH2Cl2
B Ethane, CH3CH3
C Methanal, HCHO
D Methanol, CH3OH
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(1)
A Seven
B Six
C Five
D Four
3 Energy is given out when one mole of gaseous strontium ions is hydrated.
Sr2+(g) + aq o Sr2+(aq)
This reaction is less exothermic than the corresponding reaction for magnesium ions,
Mg2+(g), because
A the sum of the first two ionization energies of magnesium is more than that of
strontium.
B the lattice energies of magnesium compounds are more exothermic than the
lattice energies of corresponding strontium compounds.
C the solubility of magnesium hydroxide is less than the solubility of
strontium hydroxide.
D the ionic radius of Mg2+ is less than the ionic radius of Sr2+.
Use this space for any rough working. Anything you write in this space will gain no credit.
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4 Use the data below to calculate the enthalpy change of solution of magnesium
chloride.
Which method would be most suitable to investigate the rates of the following
reactions?
(a) CH3CH2Br(l) + OH−(aq) o CH3CH2OH(l) + Br−(aq)
(1)
A
B
C
D
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7 The rate equation for the oxidation of bromide ions by bromate(V) ions in acid
solution is shown below.
Rate = k[BrO3−(aq)][Br−(aq)][H+(aq)]2
If the concentrations of all three reactants double, the rate will increase by a factor of
A 2
B 4
C 8
D 16
8 The gaseous first order reaction, A o B + C, was found to have a half-life of 20 s
when the initial pressure of A was 2 atm.
When the initial pressure of A is increased to 4 atm, the half-life is
A 10 s
B 20 s
C 40 s
D 400 s
Use this space for any rough working. Anything you write in this space will gain no credit.
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9 The equation for the equilibrium between nitrogen and oxygen may be written in
two ways.
N2(g) + O2(g) U 2NO(g) Equilibrium constant K1
½N2(g) + ½O2(g) U NO(g) Equilibrium constant K2
The standard enthalpy change, ǻH 9 , for the reaction as shown in the first equation is
+180 kJ mol–1.
(a) What is the standard enthalpy change for the reaction as shown in the second
equation?
(1)
–1
A +45 kJ mol
B +90 kJ mol–1
C +180 kJ mol–1
D +360 kJ mol–1
Use this space for any rough working. Anything you write in this space will gain no credit.
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10 Which of the following solutions, when mixed, would make a buffer with pH greater
than 7?
A Ethanoic acid and sodium ethanoate.
B Sodium hydroxide and sodium chloride.
C Ammonia and sodium chloride.
D Ammonia and ammonium chloride.
11 In acid solution, methyl orange is red. When an alkali is added, the solution turns
yellow because the indicator
A gains OH− ions to form cations.
B loses H+ ions to form cations.
C gains OH− ions to form anions.
D loses H+ ions to form anions.
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14 Which of the following compounds has both optical and E-Z isomers?
A CH3CH CHCH2CH3
B CH3CHBrCH C(CH3)2
C CHBr CHCHBrCH3
D CH2 CHCHBrCH3
15 At which of the following m/e values would you not expect to find a peak in the mass
spectrum of ethanoyl chloride?
A 35.5
B 37
C 43
D 78
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SECTION B
Answer ALL the questions. Write your answers in the spaces provided.
16 This question is about the reaction scheme below which may be used to convert
propanoic acid to ethyl butanoate in five steps.
CH3CH2COOH
Step 1
CH3CH2CH2OH
Step 2
CH3CH2CH2Cl
Step 3
Butanenitrile
Step 4
CH3CH2CH2COOH
Step 5
CH3CH2CH2COOCH2CH3
(a) Give the structural formula for butanenitrile, showing any multiple bonds.
(1)
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(b) Give the formula of the reagent needed for each of the Steps 1, 2, 4 and 5. The
reagent for Step 3 has been given.
Conditions and solvents are not required.
(4)
KCN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................. . . . . . . . . . . . . . . . .. . . .
Step 3 .............................
(c) Write the equation for the neutralization of sodium carbonate by butanoic acid.
State symbols are not required.
(2)
(d) State two differences between the low resolution proton nuclear magnetic
resonance spectra of butan-1-ol and butanoic acid.
(2)
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(e) Give two differences between the infrared spectra of butan-1-ol and butanoic
acid, mentioning any bonds involved with their wavenumber ranges.
(2)
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(g) Suggest the reagents required for a different, two-step method which could be
used instead of the single step method you have given for Step 5 in part (b), to
obtain ethyl butanoate from butanoic acid.
What is the advantage of using this alternative method?
(3)
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(ii) The table shows the measurements of the rate constant, k, at different
temperatures. Some of the corresponding values for reciprocal of
temperature and ln k are also shown.
Complete the table by calculating the missing values.
(2)
1
T/K k / K −1 ln k
T
280 3.80 × 10−6 3.57 × 10−3 −12.5
290 1.65 × 10−5 3.45 × 10−3 −11.0
300 6.87 × 10−5 3.33 × 10−3 −9.6
310 2.48 × 10−4 3.23 × 10−3 −8.3
320 8.65 × 10−4
*(iii) Plot a graph of ln k on the vertical axis against 1/T on the horizontal axis.
Calculate the gradient of your graph and use this to calculate the activation
energy, Ea. Remember to include units with your answer, which should be
given to three significant figures.
The Arrhenius equation can be expressed as
Ea 1
ln k = − × + a constant
R T
[Gas constant , R = 8.31 J K–1 mol–1]
(7)
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18 (a) Ammonia is a weak alkali. Consider the following equilibrium that exists in an
aqueous solution of ammonia.
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(b) (i) Calculate the pH of 4.0 mol dm–3 hydrochloric acid, assuming it is fully ionized.
(1)
(ii) Draw the titration curve, showing the change in pH when 4.0 mol dm–3
hydrochloric acid is added to 25 cm3 of 4.0 mol dm–3 ammonia solution, until
30 cm3 of the acid have been added.
(4)
12 –
11 –
10 –
9–
8–
7–
pH 6–
5–
4–
3–
2–
1–
0–
–1 –
–
0 5 10 15 20 25 30
Volume of HCl(aq)/cm3
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*(iii) Select a suitable indicator for this titration, giving the colour change you
would expect to see.
Justify your selection.
(3)
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(c) The titration above can be used to determine the concentration of ammonia
solution when ammonia is distributed between the two immiscible solvents,
trichloromethane and water.
An experiment is carried out to find the equilibrium constant for the reaction:
NH3(CHCl3) U NH3(aq)
75 cm3 of 4.0 mol dm–3 aqueous ammonia solution and 75 cm3 of the
trichloromethane are shaken together. The two liquids are allowed to separate
and 25.0 cm3 of the aqueous layer is taken and titrated with 4.0 mol dm–3
hydrochloric acid. The whole procedure is repeated.
The average titre is 24.0 cm3.
(i) Calculate the number of moles of ammonia, and hence the concentration of
ammonia, in mol dm–3, in the aqueous layer.
(3)
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(ii) The initial volumes of the two solvents are the same.
Hence deduce the concentration of ammonia in the trichloromethane layer in
mol dm–3.
(1)
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(iii) Write the expression for the equilibrium constant, Kc , for this reaction and
calculate its value.
(1)
(iv) Suggest why ammonia is much more soluble in water than in trichloromethane.
(1)
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SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
19 This question is about sucrose, the chemical commonly known as sugar. Some
thermochemical data for sucrose and oxygen are given in the table below.
9
(ii) Calculate the standard entropy change of the surroundings, ǻS surroundings , for
this combustion at 298 K. Include a sign and units in your answer.
(2)
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(iii) Calculate the total standard entropy change for the combustion, ǻS total, at
298 K.
State the significance of your answer.
(2)
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(iv) State and explain the effect, if any, of increasing the temperature on
9 9
ǻS surroundings, ǻS total and the extent of the reaction.
(3)
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(v) Icing sugar can be hazardous when it is being finely powdered in a factory.
Explain why sucrose is stable at room temperature, in spite of your answer to
part (iii), but its manufacture is hazardous.
(2)
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(vi) Suggest two risks associated with high levels of sucrose in the diet.
(2)
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. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .
22
*P44451A02224*
PMT
(b) Sucrose can be hydrolysed by warming with dilute hydrochloric acid to form
glucose and fructose.
In aqueous solution, a structure of glucose is
CHO
H C OH
HO C H
H C OH
H C OH
CH2OH
(i) Circle or mark with an asterisk (*) all the chiral centres on the structure of
glucose.
(2)
(ii) State the physical property associated with molecules which have chiral
centres.
(1)
. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .
(iii) State what change you would expect to see when glucose is boiled with
Benedict’s or Fehling’s solutions.
Explain the chemistry involved in this reaction.
(3)
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. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .
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23
*P44451A02324*
PMT
24
*P44451A02424*