Chapter 9/19 [71 

marks]
1. [1 mark]
Which gives the equation and cell potential of the spontaneous reaction?

Markscheme
D
2. [1 mark]
What would be the electrode potential, E⦵, of the Mn2+ (aq)|Mn (s) half-cell if Fe3+ (aq)|Fe2+ 
(aq) is used as the reference standard?
Mn2+ (aq) + 2e− ⇌ Mn (s)           E⦵ = −1.18 V

Fe3+ (aq) + e− ⇌ Fe2+ (aq)          E⦵ = +0.77 V

A.  −1.95 V
B.  −0.41 V
C.  +0.41 V
D.  +1.95 V

Markscheme
A
3a. [3 marks]
Oxidation and reduction reactions can have a variety of commercial uses.
A student decides to build a voltaic cell consisting of an aluminium electrode, Al (s), a tin
electrode, Sn (s), and solutions of aluminium nitrate, Al(NO 3)3 (aq) and tin(II) nitrate,
Sn(NO3)2 (aq).
Electron flow is represented on the diagram.
Label each line in the diagram using section 25 of the data booklet.

Markscheme
Al/aluminium «electrode» AND aluminium nitrate/Al(NO3)3/Al3+ on left ✓
Sn/tin «electrode» AND tin«(II)» nitrate/Sn(NO3)2/Sn2+ on right ✓
salt bridge AND voltmeter/V/lightbulb ✓

Award [1] if M1 and M2 are reversed.

Award [1] for two correctly labelled solutions OR two correctly labelled electrodes for M1 and
M2.
Accept a specific salt for “salt bridge”.
Accept other circuit components such as ammeter/A, fan, buzzer, resistor/heating
element/R/Ω.
3b. [1 mark]
Write the equation for the expected overall chemical reaction in (a).
Markscheme
3Sn2+ (aq) + 2Al (s) → 3Sn (s) + 2Al3+ (aq)
OR
3Sn(NO3)2 (aq) + 2Al (s) → 3Sn (s) + 2Al(NO3)3 (aq) ✓
If half cells are reversed in part-question (a) then the equation must be reversed to award the
mark.
Do not penalize equilibrium arrows.
3c. [1 mark]
Calculate the cell potential using section 24 of the data booklet.

Markscheme
«1.66 + (−0.14) = +»1.52 «V» ✓
 
Calculation must be consistent with equation given in 3 b.
3d. [2 marks]
Calculate the Gibbs free energy change, ΔG⦵, in kJ, for the cell, using section 1 of the data
booklet.
Markscheme
«ΔG⦵ = −nFE⦵ = −6 × 9.65 × 104 × 1.52 =» −880080 «J mol−1»
OR
6 «electrons» ✓
−880080
« =» −880 «kJ» ✓
1000
 
Award [1] for “«+»880”.
Award [2] for correct final answer.
4a. [1 mark]
A voltaic cell is made up of nickel and magnesium half-cells.
¿
Write the balanced equation for the reaction in this voltaic cell.

Markscheme
¿ ✔
Accept a balanced molecular equation such as “ M g+ N i S O 4 → M g S O4 + N i ”.
4b. [3 marks]
Calculate the cell potential for 0.0100 m o ld m−3 M g2 +¿ (a q ) ¿ and 0.800 m o ld m−3 N i 2 +¿ (a q ) ¿ at
298 K . Use sections 1, 2 and 24 of the data booklet.

Markscheme
O
E =¿<2.37 − 0.26=¿ >¿ ✔

¿<Q= ( 0.0100
0.800 )
=¿>0.0125  AND ¿< n=¿> 2 ✔

¿< E=E − ( ) ln Q=2.11 − (

2× 96 500 )
O RT 8.31× 298
ln 0.0125=¿> ¿ ✔
nF

Award [3] for correct final answer.

4c. [1 mark]
Predict, giving a reason, how an increase in temperature affects the potential of this cell.

Markscheme
cell potential/ E increases AND increasing temperature favours forward reaction
OR
cell potential/ E increases AND G becomes more negative
OR
cell potential/ E increases AND R T /n F ln Q becomes more negative ✔

Accept any correct mathematical explanation using the Nernst equation.

5. [1 mark]
Which is not a requirement of the standard hydrogen electrode (SHE)?
A. V = 1 dm3
B. p(H2) = 100 kPa
C. use of platinum as the electrode material
D. [H3O+] = 1 mol dm−3

Markscheme
A
6. [1 mark]
Consider the following table of standard electrode potentials.

Which is the strongest oxidizing agent?

A. Pb2+
B. Pb
C. Al3+
D. Al

Markscheme
A
7a. [2 marks]
A proton-exchange membrane (PEM) fuel cell uses pure hydrogen gas as the fuel and a
proton exchange membrane as the electrolyte.
 
Deduce the half-equations for the reactions occurring at the electrodes.

Anode (negative electrode):

Cathode (positive electrode):

Markscheme
Anode (negative electrode):
H2 (g) → 2H+ (aq) + 2e− ✔
Cathode (positive electrode):
O2 (g) + 4H+ (aq) + 4e− → 2H2O (l) ✔
NOTE: Accept any correct integer or fractional coefficients. Award [1 max] for M1 and M2 if
correct half-equations are given at the wrong electrodes OR if incorrect reversed half-
equations are given at the correct electrodes.
7b. [1 mark]
Calculate the cell potential, Eθ, in V, using section 24 of the data booklet.

Markscheme
(+)1.23 «V» ✔
NOTE: Do not accept “-1.23 «V»”.
7c. [1 mark]
Suggest how PEM fuel cells can be used to produce a larger voltage than that calculated in
(b)(i).

Markscheme
connect several fuel cells in series
OR
increase pressure/concentration of reactant/hydrogen/oxygen ✔
NOTE: Do not accept changes in [H+]/pH as they do not affect cell potential in this case.
Do not accept reference to quantity for “concentration”.
7d. [1 mark]
Suggest an advantage of the PEM fuel cell over the lead-acid battery for use in cars.

Markscheme
liquid in cell is less/not corrosive
OR
does not contain lead/toxic chemicals
OR
larger energy density/charge capacity/current per unit mass
OR
does not have to be charged prior to use / is always ready for use «as long as fuel is
available» ✔
7e. [3 marks]
A dye-sensitized solar cell (DSSC) uses light energy to produce electricity.
Outline the functions of the dye, TiO2 and the electrolyte in the operation of the DSSC.
Dye: 
TiO2:
Electrolyte:
Markscheme
Dye:
absorbs photons/light
OR
releases electrons ✔
TiO2:
conducts current/electricity
OR
semiconductor ✔
Electrolyte:
reduces/regenerates «the oxidized» dye ✔
7f. [1 mark]
Suggest an advantage of the DSSC over silicon-based photovoltaic cells.
Markscheme
Any one of:
cheaper/ease of manufacture
OR
plentiful and renewable resources «to construct DSSC cells» ✔
use light of lower energy/lower frequency/longer wavelength
OR
use of nanoparticles provides large surface area for exposure to sunlight/sun/light
OR
can absorb better under cloudy conditions ✔
operate at lower «internal» temperatures
OR
better at radiating heat away «since constructed with thin front layer of conductive plastic
compared to glass box in photovoltaic cells» ✔
better conductivity ✔
more flexible/durable ✔
NOTE: Accept “lower mass/lighter «so greater flexibility to integrate into windows etc.»” OR
“greater power-conversion efficiency «with latest DSSC models»”.
8. [1 mark]
Which is correct for a redox reaction where the standard electrode potential is negative?
ΔGΘ = −nFEΘ and ΔGΘ = −RT ln K
 
A.   ΔGΘ is negative and K is less than 1.
B.   ΔGΘ is negative and K is greater than 1.
C.   ΔGΘ is positive and K is less than 1.
D.   ΔGΘ is positive and K is greater than 1.

Markscheme
C
9. [1 mark]
Consider the standard electrode potentials:
Cr3+ (aq) + 3e− ⇌ Cr (s)       EΘ = −0.74 V
Hg2+ (aq) + 2e− ⇌ Hg (l)      EΘ = +0.85 V
What is the cell potential, in V, for the voltaic cell?
2Cr (s) + 3Hg2+ (aq) → 3Hg (l) + 2Cr3+ (aq)
 
A.   −1.59
B.   +0.11
C.   +1.07
D.   +1.59

Markscheme
D
10a. [2 marks]
The diagram shows an incomplete voltaic cell with a light bulb in the circuit.

Identify the missing component of the cell and its function.

Markscheme
salt bridge
 
movement of ions
OR
balance charge
 
Do not accept “to complete circuit” unless ion movement is mentioned for M2.
[2 marks]
10b. [2 marks]
Deduce the half-equations for the reaction at each electrode when current flows.

Markscheme
Positive electrode (cathode):
Ag+(aq) + e– → Ag(s)
 
Negative electrode (anode):
Mg(s) → Mg2+(aq) + 2e–
 
Award [1 max] if correct equations given at wrong electrodes.
[2 marks]
10c. [1 mark]
Annotate the diagram with the location and direction of electron movement when current
flows.

Markscheme
in external wire from left to right
[1 mark]
10d. [1 mark]
Calculate the cell potential, in V, using section 24 of the data booklet.

Markscheme
«E = +0.80 V – (–2.37 V) = +» 3.17 «V»
[1 mark]

10e. [2 marks]
Determine the loss in mass of one electrode if the mass of the other electrode increases by
0.10 g.

Markscheme
0.10 g
«moles of silver »
107.87 g mo l −1
 0.5× 0.10 ≪ g ≫
moles of magnesium ¿ −1
107.87≪ g mol ≫
24.31 g mol × 0.5× 0.10 g
«loss in mass of magnesium ¿ −1
=¿» 0.011 «g»
107.87 g mol
 
Award [2] for correct final answer.
[2 marks]
11. [1 mark]
What is the standard half-cell potential of copper if the “zero potential reference electrode”
is changed from the standard hydrogen electrode to a standard zinc electrode?

A.     –1.1
B.     –0.34
C.     +0.34
D.     +1.1

Markscheme
D
12a. [2 marks]
Vanadium has a number of different oxidation states.
Determine the oxidation state of vanadium in each of the following species.
Markscheme
V 2 O5 :+5
2+¿:+ 4 ¿
VO
 
Do not penalize incorrect notation twice.
[2 marks]
12b. [1 mark]
Electrode potentials for the reactions of vanadium and other species are shown below.

Identify, from the table, a non-vanadium species that can reduce VO 2+(aq) to V3+(aq) but no
further.
Markscheme
H2SO3(aq)
OR
Pb(s)
[1 mark]
12c. [1 mark]
+¿(aq)¿
Identify, from the table, a non-vanadium species that could convert VO2  to V2+(aq).

Markscheme
Zn(s)
[1 mark]
12d. [1 mark]
Formulate an equation for the reaction between VO2+(aq) and V2+(aq) in acidic solution to
form V3+(aq).

Markscheme
3+ ¿( aq)+ H O( l)¿
2
+¿ (aq )→ 2V ¿
2+ ¿(aq)+ 2H ¿
2+¿(aq)+V ¿
VO
 
Accept equilibrium sign.
[1 mark]
12e. [3 marks]
Comment on the spontaneity of this reaction by calculating a value for Δ Gθ  using the data
given in (b) and in section 1 of the data booklet.

Markscheme
θ
E ≪=+0.34 V −(− 0.26V ) ≫=+0.60 ≪ V ≫
θ θ 4 −1 −1 −1 −1
Δ G =≪− n F E =− 9.65 ×10 C mol ×0.60 J C =≫− 57 900 ≪ J mo l ≫ /− 57.9≪ kJ mol ≫
spontaneous as Δ Gθ  is negative
 
Do not award M3 as a stand-alone answer.
Accept “spontaneous” for M3 if answer given for M2 is negative.
Accept “spontaneous as Eθ  is positive” for M3.
[3 marks]
13a. [1 mark]
An acidic sample of a waste solution containing Sn2+(aq) reacted completely with
K2Cr2O7 solution to form Sn4+(aq).
Identify one organic functional group that can react with acidified K 2Cr2O7(aq).
Markscheme
hydroxyl/OH
OR
aldehyde/CHO
 
Accept “hydroxy/alcohol” for “hydroxyl”.
Accept amino/amine/NH2.
[1 mark]
13b. [1 mark]
Corrosion of iron is similar to the processes that occur in a voltaic cell. The initial steps
involve the following half-equations:
Fe2+(aq) + 2e– ⇌ Fe(s)
1
O (g) + H2O(l) + 2e– ⇌ 2OH–(aq)
2 2
Calculate E θ, in V, for the spontaneous reaction using section 24 of the data booklet.

Markscheme
«E θ =» +0.85 «V»
 
Accept 0.85 V.
[1 mark]
13c. [2 marks]
Calculate the Gibbs free energy, ΔG θ, in kJ, which is released by the corrosion of 1 mole of
iron. Use section 1 of the data booklet.

Markscheme
ΔG θ «= –nFE θ» = –2 «mol e–» x 96500 «C mol–1» x 0.85 «V»
«ΔG θ =» –164 «kJ»
 
Accept “«+»164 «kJ»” as question states energy released.
Award [1 max] for “+” or “–” 82 «kJ».
Do not accept answer in J.
[2 marks]
13d. [3 marks]
Explain why iron forms many different coloured complex ions.

Markscheme
incompletely filled d-orbitals
colour depends upon the energy difference between the split d-orbitals
variable/multiple/different oxidation states
different «nature/identity of» ligands
different number of ligands
[3 marks]
13e. [1 mark]
Zinc is used to galvanize iron pipes, forming a protective coating. Outline how this process
prevents corrosion of the iron pipes.

Markscheme
Zn/zinc is a stronger reducing agent than Fe/iron
OR
Zn/zinc is oxidized instead of Fe/iron
OR
Zn/zinc is the sacrificial anode
 
Accept “Zn is more reactive than Fe”.
Accept “Zn oxide layer limits further corrosion”.
Do not accept “Zn layer limits further corrosion”.
[1 mark]
14. [1 mark]
Which signs for both Eθcell and ΔGθ result in a spontaneous redox reaction occurring under
standard conditions?
Markscheme
D
15a. [4 marks]
Tin(II) chloride is a white solid that is commonly used as a reducing agent.
(i) State why you would expect tin(II) chloride to have a similar lattice enthalpy to
strontium chloride, using section 9 of the data booklet.
(ii) Calculate the molar enthalpy change when strontium chloride is dissolved in water,
using sections 18 and 20 of the data booklet.
(iii) Tin(II) chloride reacts with water to precipitate the insoluble basic chloride, Sn(OH)Cl.

Suggest why tin(II) chloride is usually dissolved in dilute hydrochloric acid.

Markscheme
(i)
same charge AND same/similar ionic radius
(ii)
enthalpy of hydration «= −1483 + 2 (−359)» = −2201 «kJmol −1»
enthalpy of solution «= 2170 − 2201» = −31 «kJmol−1»
Award [2] for correct final answer.
Award [1 max] for +31 «kJmol−1».
Award [1 max] for ±4371.
(iii)
hydrochloric acid shifts equilibrium to left
OR
hydrochloric acid prevents the basic chloride forming/precipitating
Accept “hydrochloric acid reacts with «basic» chloride” OR “hydrochloric acid suppresses salt
hydrolysis”.
 
15b. [3 marks]
Tin can also exist in the +4 oxidation state.

Vanadium can be reduced from an oxidation state of +4 to +3 according to the equation:

(i) Calculate the cell potential, EΘ, and the standard free energy, ΔGΘ, change for the reaction
between the VO2+ and Sn2+ ions, using sections 1 and 2 of the data booklet.
EΘ:
ΔGΘ:
(ii) Deduce, giving your reason, whether a reaction between Sn2+(aq) and VO2+(aq) would
be spontaneous.

Markscheme
(i)
EΘ «= 0.34 − 0.15» = 0.19«V»
∆GOΘ«= − nFEΘ = −2 × 96500 × 0.19» = −36670 / −37000«J» / − 37«kJ»
Accept −18335 «J» or −18 «kJ» as equation not specified.
(ii) 
yes AND ∆GΘ is negative
OR
yes AND EΘ for the cell is positive
OR
yes AND Sn2+ (aq) is a stronger reducing agent than V3+(aq)
OR
yes AND EΘ SN4+ (aq) is more negative that  EΘ or VO2+ (aq)
OR
yes AND VO2+ (aq) is a stronger oxidizing agent than Sn4+ (aq)
OR
yes AND EΘ for  VO2+  (aq) is more positive than EΘ for SN4+ (aq)
Do not accept reference to anti-clockwise rule.
15c. [2 marks]
Outline, giving the full electron configuration of the vanadium atom, what is meant by the
term transition metal.
Markscheme
1s22s22p63s23p63d34s2
OR
1s22s22p63s23p64s23d3 
incomplete d «sub-» level/orbital/shell «in its compounds/ions»
15d. [3 marks]
In an aqueous solution of vanadium(III) chloride, the vanadium exists as [V (H 2O)6]3+, [VCl
(H2O)5]2+ or [VCl2(H2O)4]+ depending on the concentration of chloride ions in the solution.
(i) Describe how Cl− and H2O bond to the vanadium ion.
(ii) Outline what would happen to the wavelength at which the vanadium complex ions
would absorb light as the water molecules are gradually replaced by chloride ions, using
section 15 of the data booklet.

Markscheme
(i)
give/donate a lone/non-bonding electron pair
Accept “through the formation of a dative/ coordinate bond”.
Accept “by acting as Lewis bases”.
Do not accept “act as ligands”.
(ii)
«more chlorido ligands» smaller energy gap between split d-orbitals
OR
Cl− is lower than H2O in spectrochemical series
OR
Cl− is a weaker ligand/has lower charge density
the absorption will move to longer wavelengths
OR
the absorption wavelength will increase
Do not accept answers in terms of change of frequency.
15e. [6 marks]
Eight successive ionisation energies of vanadium are shown in the graph below:

(i) State the sub-levels from which each of the first four electrons are lost.
First:    Second:    Third:    Fourth:    
(ii) Outline why there is an increase in ionization energy from electron 3 to electron 5.
(iii) Explain why there is a large increase in the ionization energy between electrons 5 and
6.
(iv) Vanadium is comprised almost entirely of 51V. State the number of neutrons an atom
of 51V has in its nucleus.
Markscheme
(i)
First: 4s AND Second: 4s AND Third: 3d AND Fourth: 3d
Do not apply ECF from (c).
(ii)
«in the same sub-shell and a» decrease in electron-electron repulsion
OR
«in the same sub-shell and» as more electrons removed, the pull of of the nucleus/positive
ions holds the remaining electrons more tightly
Do not accept “greater nuclear charge/ effective nuclear charge”.
(iii)
electron 5 is lost from the 3d orbital
OR
electron 5 is lost from the valence shell
electron 6 is lost from a 3p orbital
OR
electron 6 is lost from a «complete» inner shell
3p orbital/complete inner shell experiences a much larger effective nuclear charge
OR
3p orbital/complete inner shell is less well shielded
OR
3p orbital/complete inner shell is nearer the nucleus
Award [1 max] (for M1/M2) (ECF) if candidate recognises electrons 5 and 6 are from
different levels.
(iv)
28
 

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