Date | November 2019 | Marks available | 1 | Reference code | 19N.2.hl.TZ0.6 |
Level | HL | Paper | 2 | Time zone | TZ0 |
Command term | Comment | Question number | 6 | Adapted from | N/A |
Question
Copper forms two chlorides, copper(I) chloride and copper(II) chloride.
Two electrolysis cells were assembled using graphite electrodes and connected in series as shown.
Copper(I) chloride undergoes a disproportionation reaction, producing copper(II) chloride and copper.
2Cu+ (aq) → Cu (s) + Cu2+ (aq)
Dilute copper(II) chloride solution is light blue, while copper(I) chloride solution is colourless.
State the electron configuration of the Cu+ ion.
Copper(II) chloride is used as a catalyst in the production of chlorine from hydrogen chloride.
4HCl (g) + O2 (g) → 2Cl2 (g) + 2H2O (g)
Calculate the standard enthalpy change, ΔHθ, in kJ, for this reaction, using section 12 of the data booklet.
The diagram shows the Maxwell–Boltzmann distribution and potential energy profile for the reaction without a catalyst.
Annotate both charts to show the activation energy for the catalysed reaction, using the label Ea (cat).
Explain how the catalyst increases the rate of the reaction.
Solid copper(II) chloride absorbs moisture from the atmosphere to form a hydrate of formula CuCl2•H2O.
A student heated a sample of hydrated copper(II) chloride, in order to determine the value of . The following results were obtained:
Mass of crucible = 16.221 g
Initial mass of crucible and hydrated copper(II) chloride = 18.360 g
Final mass of crucible and anhydrous copper(II) chloride = 17.917 g
Determine the value of .
State how current is conducted through the wires and through the electrolyte.
Wires:
Electrolyte:
Write the half-equation for the formation of gas bubbles at electrode 1.
Bubbles of gas were also observed at another electrode. Identify the electrode and the gas.
Electrode number (on diagram):
Name of gas:
Deduce the half-equation for the formation of the gas identified in (c)(iii).
Determine the enthalpy of solution of copper(II) chloride, using data from sections 18 and 20 of the data booklet.
The enthalpy of hydration of the copper(II) ion is −2161 kJ mol−1.
Calculate the cell potential at 298 K for the disproportionation reaction, in V, using section 24 of the data booklet.
Comment on the spontaneity of the disproportionation reaction at 298 K.
Calculate the standard Gibbs free energy change, ΔGθ, to two significant figures, for the disproportionation at 298 K. Use your answer from (e)(i) and sections 1 and 2 of the data booklet.
Suggest, giving a reason, whether the entropy of the system increases or decreases during the disproportionation.
Deduce, giving a reason, the sign of the standard enthalpy change, ΔHθ, for the disproportionation reaction at 298 K.
Predict, giving a reason, the effect of increasing temperature on the stability of copper(I) chloride solution.
Describe how the blue colour is produced in the Cu(II) solution. Refer to section 17 of the data booklet.
Deduce why the Cu(I) solution is colourless.
When excess ammonia is added to copper(II) chloride solution, the dark blue complex ion, [Cu(NH3)4(H2O)2]2+, forms.
State the molecular geometry of this complex ion, and the bond angles within it.
Molecular geometry:
Bond angles:
Examine the relationship between the Brønsted–Lowry and Lewis definitions of a base, referring to the ligands in the complex ion [CuCl4]2−.
Markscheme
[Ar] 3d10
OR
1s2 2s2 2p6 3s2 3p6 3d10 ✔
ΔHθ = ΣΔHθf (products) − ΣΔHθf (reactants) ✔
ΔHθ = 2(−241.8 «kJ mol−1») − 4(−92.3 «kJ mol−1») = −114.4 «kJ» ✔
NOTE: Award [2] for correct final answer.
Ea (cat) to the left of Ea ✔
peak lower AND Ea (cat) smaller ✔
«catalyst provides an» alternative pathway ✔
«with» lower Ea
OR
higher proportion of/more particles with «kinetic» E ≥ Ea(cat) «than Ea» ✔
mass of H2O = «18.360 g – 17.917 g =» 0.443 «g» AND mass of CuCl2 = «17.917 g – 16.221 g =» 1.696 «g» ✔
moles of H2O = «=» 0.0246 «mol»
OR
moles of CuCl2 =«= » 0.0126 «mol» ✔
«water : copper(II) chloride = 1.95 : 1»
« =» 2 ✔
NOTE: Accept « =» 1.95.
NOTE: Award [3] for correct final answer.
Wires:
«delocalized» electrons «flow» ✔
Electrolyte:
«mobile» ions «flow» ✔
2Cl− → Cl2 (g) + 2e−
OR
Cl− → Cl2 (g) + e− ✔
NOTE: Accept e for e−.
«electrode» 3 AND oxygen/O2 ✔
NOTE: Accept chlorine/Cl2.
2H2O (l) → 4H+ (aq) + O2 (g) + 4e– ✔
NOTE: Accept 2Cl– (aq) → Cl2 (g) + 2e–.
Accept 4OH− → 2H2O + O2 + 4e−
enthalpy of solution = lattice enthalpy + enthalpies of hydration «of Cu2+ and Cl−» ✔
«+2824 kJ mol–1 − 2161 kJ mol–1 − 2(359 kJ mol–1) =» −55 «kJ mol–1» ✔
NOTE: Accept enthalpy cycle.
Award [2] for correct final answer.
Eθ = «+0.52 – 0.15 = +» 0.37 «V» ✔
spontaneous AND Eθ positive ✔
ΔGθ = «−nFE = −1 mol × 96 500 C Mol–1 × 0.37 V=» −36 000 J/−36 kJ ✔
NOTE: Accept “−18 kJ mol–1 «per mole of Cu+»”.
Do not accept values of n other than 1.
Apply SF in this question.
Accept J/kJ or J mol−1/kJ mol−1 for units.
2 mol (aq) → 1 mol (aq) AND decreases ✔
NOTE: Accept “solid formed from aqueous solution AND decreases”.
Do not accept 2 mol → 1 mol without (aq).
ΔGθ < 0 AND ΔSθ < 0 AND ΔHθ < 0
OR
ΔGθ + TΔSθ < 0 AND ΔHθ < 0 ✔
TΔS more negative «reducing spontaneity» AND stability increases ✔
NOTE: Accept calculation showing non-spontaneity at 433 K.
«ligands cause» d-orbitals «to» split ✔
light absorbed as electrons transit to higher energy level «in d–d transitions»
OR
light absorbed as electrons promoted ✔
energy gap corresponds to «orange» light in visible region of spectrum ✔
colour observed is complementary ✔
full «3»d sub-level/orbitals
OR
no d–d transition possible «and therefore no colour» ✔
octahedral AND 90° «180° for axial» ✔
NOTE: Accept square-based bi-pyramid.
Any two of:
ligand/chloride ion Lewis base AND donates e-pair ✔
not Brønsted–Lowry base AND does not accept proton/H+ ✔
Lewis definition extends/broader than Brønsted–Lowry definition ✔