A Level Chemistry 9701 Paper 22, Oct/Nov 2023

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9701/22 · Oct/Nov 2023

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1

The elements silicon, phosphorus and sulfur are in Period 3 of the Periodic Table.

a(i)

Describe the variation in atomic radius from silicon to sulfur.

[1]
a(ii)

The melting point of silicon is 1410°C. The melting point of sulfur is 113°C. Explain this difference.

[3]
b(i)

Table 1.1 shows some properties of the elements Si to S. The first ionisation energy of P is not shown. Table 1.1 Complete Table 1.1 to show the total number of s and p electrons in an atom of Si, P and S.

[2]
b(ii)

Construct an equation to represent the first ionisation energy of Si.

[1]
b(iii)

Three possible values for the first ionisation energy of P are given. 619 kJ mol–1 893 kJ mol–1 1060 kJ mol–1 Circle the correct value. Explain your choice, including a comparison of your chosen value to those of Si and S.

[4]
b(iv)

SiCl4 and PCl5 each react with water, forming misty fumes. Identify the chemical responsible for the misty fumes.

[1]
b(v)

Predict the shape of the SCl2 molecule.

[1]
2

NO and NO2 react at 25 ∘C to give N2O3 as shown in the equation. NO(g)+NO2(g)⇌N2O3(g)ΔH=−7.2 kJ mol−1 The reaction is reversible and reaches equilibrium in a closed system.

Figure 1 of 1 for question 2
a

Fig. 2.1 shows how the rate of the forward reaction changes with time. Initially, the rate of the reverse reaction is zero. Complete Fig. 2.1 to sketch how the rate of the reverse reaction changes with time.

[1]
b

State how the position of equilibrium changes, if at all, when the reaction takes place at 100°C. Explain your answer. Assume the pressure remains constant.

[2]
c

Table 2.1 shows the composition of an equilibrium mixture of NO(g), NO2(g) and N2O3(g) at 101 kPa. Table 2.1 Calculate Kp, the equilibrium constant with respect to partial pressures. Deduce the units of Kp. $K_p = $ ..................................... units .......................................

[3]
d

Identify one natural process and one man-made process that cause the formation of atmospheric NO and NO2. natural process ......................................................................................................................... man-made process ....................................................................................................................

[2]
e(i)

NO2 is a brown gas that can be used to form nitric acid. NO2 is a free radical. Define free radical.

[1]
e(ii)

NO2 has a catalytic role in the oxidation of atmospheric sulfur dioxide. Write equations to show the catalytic role of NO2 in this oxidation.

[2]
e(iii)

State one environmental consequence of the oxidation of atmospheric sulfur dioxide.

[1]
f(i)

A student titrates nitric acid with a base to form a solution containing aqueous magnesium nitrate. Identify a base that the student could use.

[1]
f(ii)

The student evaporates the water to obtain magnesium nitrate solid. When this solid is heated it decomposes. Write an equation for the decomposition of magnesium nitrate.

[1]
f(iii)

State how the thermal stability of Group 2 nitrates changes down the group.

[1]
3

Phosphoric(V) acid, H3PO4, is used in both inorganic and organic reactions.

Figure 1 of 2 for question 3
Figure 2 of 2 for question 3
a(i)

H3PO4 is made in a two-step process from phosphorus. step 1 Phosphorus reacts with an excess of oxygen to form a white solid. step 2 The white solid then reacts with water to form H3PO4. Write an equation for each step. step 1 ................................................................................................................................ step 2 ................................................................................................................................

[2]
a(ii)

H3PO4 is a weak Brønsted–Lowry acid. Define weak Brønsted–Lowry acid.

[2]
b(i)

H3PO4 is also formed in the process shown in reaction 1. reaction 1 4H3PO3→3H3PO4+PH3 Table 3.1 shows some relevant thermodynamic data. Table 3.1 Define enthalpy change of formation.

[2]
b(ii)

Use the data in Table 3.1 to calculate the enthalpy change, ΔHr, of reaction 1. ΔHr= ................................................. kJ mol−1

[2]
b(iii)

Explain why reaction 1 is a disproportionation reaction. Explain your reasoning with reference to relevant oxidation numbers.

[2]
c(i)

Fig. 3.1 shows a reaction scheme that involves H3PO4 in several reactions. Fig. 3.1 Identify A, which reacts with propene in the presence of H3PO4 in reaction 2.

[1]
c(ii)

Draw the structure of B.

[1]
c(iii)

Name the type of reaction that occurs in reaction 3.

[1]
c(iv)

Reaction 3 is monitored using infrared spectroscopy. It is not possible to use the O—H absorption frequency to monitor the reaction. Use Table 3.2 to identify a suitable bond whose absorption frequency can be used to monitor the progress of reaction 3. State the change you would see in the infrared spectrum during reaction 3. bond .................................................................................................................. change in infrared spectrum .............................................................................................. ...........................................................................................................................................

[2]
d(i)

H3PO4 also reacts with alcohols to form organophosphates. Organophosphates are compounds similar to esters. They have the general structure shown in Fig. 3.2. Fig. 3.2 Complete the equation to suggest the products of the reaction of H3PO4 with methanol, CH3OH. H3PO4+3CH3OH→ ..................................................................................................

[1]
d(ii)

Compound T is a simple organophosphate. The mass spectrum of T shows a molecular ion peak at m/e=182. This peak has a relative intensity of 12.7. The relative intensity of the M+1 peak is 0.84. Deduce the number of carbon atoms in T. Hence suggest the molecular formula of T. Assume that phosphorus and oxygen exist as single isotopes. Show your working. number of carbon atoms in T = ............................................. molecular formula of T = .......................................................

[3]
4

Lactic acid, CH3CH(OH)COOH, and pyruvic acid, CH3COCOOH, both contain two functional groups. Fig. 4.1

Figure 1 of 4 for question 4
Figure 2 of 4 for question 4
Figure 3 of 4 for question 4
Figure 4 of 4 for question 4
a(i)

Explain why lactic acid exists as optical isomers.

[1]
a(ii)

Give the systematic name of lactic acid.

[1]
a(iii)

Lactic acid forms hydrogen bonds with water. Complete Fig. 4.2 to show the formation of a hydrogen bond between one molecule of lactic acid and one molecule of water. Label the hydrogen bond. Show any relevant dipoles and lone pairs of electrons.

[3]
b(i)

Two possible syntheses of pyruvic acid are shown in Fig. 4.3 and Fig. 4.4. Each synthesis has a total of three steps. Fig. 4.3 Fig. 4.4 Complete the diagram in Fig. 4.5 to show the mechanism for the reaction of propene with Br2. Include charges, dipoles, lone pairs of electrons and curly arrows, as appropriate.

[3]
b(ii)

Write an equation for the oxidation of lactic acid to pyruvic acid, the third step of Fig. 4.4. Use [O] to represent one atom of oxygen from an oxidising agent. CH3CH(OH)COOH+ ...................................................................................................

[1]
b(iii)

Complete Table 4.1 to give details of the reagents and conditions used in each of the two syntheses shown in Fig. 4.3 and Fig. 4.4. Table 4.1

[4]

Mark scheme

9701/22 · Oct/Nov 2023

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1a(i) · 1 mark

  • 1 mark

    decreases (from Si to S)

1a(ii) · 3 marks

  • M1

    Si giant covalent AND S is simple molecular OR Si giant covalent AND S has IMFs

  • M2

    Si involves breaking covalent bonds AND S involves breaking IMFs

  • M3

    more energy needed to break covalent bonds than IMFs OR covalent bonds are strong AND IMFs are weak

1b(i) · 2 marks

  • 1 mark

    total e– in s subshell 6 6 6

  • 1 mark

    total e– in p subshell 8 9 10

1b(ii) · 1 mark

  • 1 mark

    Si(g) → Si+(g) + e–

1b(iii) · 4 marks

  • 1 mark

    1060 (is circled)

  • 1 mark

    P / it has greater attraction of nucleus for outer electrons compared to Si ORA

  • 1 mark

    P / it has greater nuclear charge than Si ORA

  • 1 mark

    S has two electrons in a (3)p orbital AND resulting in spin-pair repulsion

1b(iv) · 1 mark

  • 1 mark

    hydrogen chloride / HCl

1b(v) · 1 mark

  • 1 mark

    non-linear

2a · 1 mark

  • 1 mark

    curved line from (0,0) to reach same horizontal line

2b · 2 marks

  • 1 mark

    equilibrium position would / it moves to left / reactants

  • 1 mark

    forward reaction is exothermic (so disfavoured by increase in T)

2c · 3 marks

  • 1 mark

    mole fraction: NO = 0.605/1.60 (= 0.378125), NO2 = 0.605/1.60 (= 0.378125), N2O3 = 0.390/1.60 (= 0.24375)

  • 1 mark

    (partial pressure / kPa 38.19 38.19 24.62) Kp = 24.62 ÷ 38.19² = 0.0169

  • 1 mark

    kPa–1

2d · 2 marks

  • 1 mark

    natural process: lightning

  • 1 mark

    man-made process: internal combustion engines

2e(i) · 1 mark

  • 1 mark

    species with 1 or more unpaired electrons

2e(ii) · 2 marks

  • 1 mark

    NO2 + SO2 → SO3 + NO

  • 1 mark

    NO + ½ O2 → NO2

2e(iii) · 1 mark

  • 1 mark

    (formation of) acid rain

2f(i) · 1 mark

  • 1 mark

    magnesium hydroxide / Mg(OH)2

2f(ii) · 1 mark

  • 1 mark

    Mg(NO3)2 → MgO + 2NO2 + ½O2

2f(iii) · 1 mark

  • 1 mark

    increases

3a(i) · 2 marks

  • 1 mark

    4P / P4 + 5O2 → P4O10

  • 1 mark

    P4O10 + 6H2O → 4H3PO4

3a(ii) · 2 marks

  • 1 mark

    proton / H+ donor

  • 1 mark

    partially dissociates (in solution / in water / when aqueous)

3b(i) · 2 marks

  • 1 mark

    enthalpy change when one mole of a compound / substance is formed

  • 1 mark

    from its constituent elements in their standard states

3b(ii) · 2 marks

  • 1 mark

    ΔHf = +9 + 3(–1281) – 4(–972) = (+)54 (kJ mol–1)

  • 1 mark

    Any two from: use correct stoichiometry for all three values; use correct expression regardless of stoichiometry for all three values; calculated correctly

3b(iii) · 2 marks

  • 1 mark

    P (in H3PO3) is (both) oxidised and reduced (simultaneously)

  • 1 mark

    P (is oxidised) from (+)3 / (+)III → (+)5 / (+)V AND (reduced to) –3 / –III

3c(i) · 1 mark

  • 1 mark

    H2O / steam

3c(ii) · 1 mark

  • 1 mark

    2-bromopropane skeletal formula

3c(iii) · 1 mark

  • 1 mark

    condensation

3c(iv) · 2 marks

  • 1 mark

    C=O

  • 1 mark

    absorption changes to frequency / wavenumber / from 1670–1740 to 1710–1750 cm–1

3d(i) · 1 mark

  • 1 mark

    H3PO4 + 3CH3OH → (CH3O)3PO + 3H2O

3d(ii) · 3 marks

  • 1 mark

    (0.84 / 12.7) × (100 / 1.1) (= 6.013)

  • 1 mark

    no. of carbon atoms = 6

  • 1 mark

    molecular formula = C6H15O4P

4a(i) · 1 mark

  • 1 mark

    (it has molecules that) contain a chiral carbon / centre OR are non-superimposable mirror images

4a(ii) · 1 mark

  • 1 mark

    2-hydroxypropanoic acid

4a(iii) · 3 marks

  • 1 mark

    dashed (or distinctly labelled) bond between O and H in different molecules of H-O-H and propanoic acid

  • 1 mark

    correct sequence of three partial charges over the H-bond Hδ+ Oδ–—Hδ+ OR Oδ– Hδ+—Oδ–

  • 1 mark

    lone pair on O in line with H-bond

4b(i) · 3 marks

  • 1 mark

    curly arrow from C=C bond to Brδ+ AND curly arrow from Brδ+—Brδ– bond to Brδ– AND Br δ+ closest to the double bond

  • 1 mark

    correct intermediate

  • 1 mark

    curly arrow from lone pair on Br– to C(+) of the intermediate

4b(ii) · 1 mark

  • 1 mark

    CH3CH(OH)COOH + [O] → CH3COCOOH + H2O

4b(iii) · 4 marks

  • 1 mark

    HCN&KCN OR NaCN with H2SO4

  • 1 mark

    NaOH(aq)

  • 1 mark

    dilute / aq(ueous)HCl / H2SO4

  • 1 mark

    acidified K2Cr2O7

Questions

  1. 1
    Question 113 marks
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  2. 2
    Question 215 marks
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  3. 3
    Question 319 marks
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  4. 4
    Question 413 marks
    Mark scheme ›

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