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    Tutorial 20: Electrochemistry - Suggested Solutions 1 (A) (1) (I)

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    The document provides solutions to tutorial questions on electrochemistry. It includes: 1) Summaries of half-reactions and standard reduction potentials for various redox couples. 2) Calculations of standard cell potentials and determining spontaneity of reactions. 3) Explanations of how changing conditions affects equilibrium and cell potential. 4) Examples of galvanic and electrolytic cells, including calculations for amounts of substance deposited.

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    Tutorial 20: Electrochemistry - Suggested Solutions 1 (A) (1) (I)

    Uploaded by

    Dom
    151 views7 pages
    The document provides solutions to tutorial questions on electrochemistry. It includes: 1) Summaries of half-reactions and standard reduction potentials for various redox couples. 2) Calculations of standard cell potentials and determining spontaneity of reactions. 3) Explanations of how changing conditions affects equilibrium and cell potential. 4) Examples of galvanic and electrolytic cells, including calculations for amounts of substance deposited.

    Original Description:

    A level chemistry

    Original Title

    Electrochemistry [Ans]

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    The document provides solutions to tutorial questions on electrochemistry. It includes: 1) Summaries of half-reactions and standard reduction potentials for various redox couples. 2) Calculations of standard cell potentials and determining spontaneity of reactions. 3) Explanations of how changing conditions affects equilibrium and cell potential. 4) Examples of galvanic and electrolytic cells, including calculations for amounts of substance deposited.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    151 views7 pages

    Tutorial 20: Electrochemistry - Suggested Solutions 1 (A) (1) (I)

    Uploaded by

    Dom
    The document provides solutions to tutorial questions on electrochemistry. It includes: 1) Summaries of half-reactions and standard reduction potentials for various redox couples. 2) Calculations of standard cell potentials and determining spontaneity of reactions. 3) Explanations of how changing conditions affects equilibrium and cell potential. 4) Examples of galvanic and electrolytic cells, including calculations for amounts of substance deposited.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 7
    At a glance
    Powered by AI
    The document discusses electrochemistry concepts including standard electrode potentials, galvanic/voltaic cells, and factors that affect cell potential.

    The two half-reactions are: H2O2 (aq) + 2H+ (aq) + 2e- ⇌ 2H2O (l) and O2 (g) + 2H+ (aq) + 2e- ⇌ H2O2 (aq)

    The cell potential can be decreased by either decreasing the reduction potential or increasing the oxidation potential. The reduction potential can be decreased by using reactants of lower concentrations in the reduction half-cell. The oxidation potential can be increased by using reactants of higher concentrations or pressures in the oxidation half-cell.

    Tutorial 20: Electrochemistry Suggested Solutions

    1(a)(1)
    (i)

    Cr2O72 (aq) + 14H+ (aq) + 6e 2Cr3+ (aq) + 7H2O (l)

    E = +1.33 V

    Cu2+(aq) + 2e- Cu (s)

    E = +0.34 V

    Cathode: Pt electrode in Cr2O72 (aq) / Cr3+ (aq) halfcell


    Red:
    Cr2O72 (aq) + 14H+ (aq) + 6e 2Cr3+ (aq) + 7H2O (l)
    Anode:

    Copper electrode in Cu2+ (aq) / Cu (s) halfcell

    Oxid:

    Cu (s) Cu2+ (aq) + 2e

    [1]

    (ii)

    Cr2O72 (aq) + 14H+(aq) + 3Cu(s) 2Cr3+ (aq) + 7H2O(l) + 3Cu2+(aq)

    (iii)

    Ecell

    =
    =

    +1.33 (+0.34)
    +0.99 V

    (iv)

    [1]

    [1]

    [1]
    Correct drawing & labeling
    Correct conditions
    Correct e direction

    e
    V
    T = 298 K

    [1]
    [1]
    [1]

    Cu
    salt bridge
    Pt
    [Cr2O72 (aq)]
    = [Cr3+(aq)]
    = [H+(aq)]
    = 1 mol dm3

    2+

    [Cu (aq)]
    = 1 mol dm3

    1(a)(2)
    (i)

    H2O2 (aq) + 2H+ (aq) + 2e 2H2O (l)

    E = +1.77 V

    O2 (g) + 2H+ (aq) + 2e H2O2 (aq)

    E = +0.68 V

    Cathode: Pt electrode in H2O2 (aq) / H2O (l) halfcell


    Red:
    H2O2 (aq) + 2H+ (aq) + 2e 2H2O (l)

    [1]

    Anode:
    Oxid:

    [1]

    Pt electrode in O2 (g) / H2O2 (aq) halfcell


    H2O2 (aq) O2 (g) + 2H+ (aq) + 2e

    (ii)

    2H2O2 (aq) 2H2O (l) + O2 (g)

    (iii)

    Ecell

    =
    =

    [1]

    +1.77 (+0.68)
    +1.09 V
    e

    (iv)

    [1]
    Correct drawing & labeling
    Correct conditions
    Correct e direction

    V
    T = 298 K

    O2
    (1 atm)

    [H2O2(aq)]
    = [H+(aq)]
    = 1 mol dm3

    salt bridge
    Pt

    Pt

    [H2O2(aq)]
    = [H+(aq)]
    = 1 mol dm3

    [1]
    [1]
    [1]

    1(b)(i)

    CO32- precipitates out Cu2+ so that [Cu2+(aq)] decreases.

    [1]

    This shifts the position of equilibrium in Cu2+(aq) + 2e Cu(s) to the left so that EL
    decreases. Hence Ecell = ER EL increases (i.e. Ecell > Ecell).
    [1]
    (ii)

    Br reduces Cr2O72 to Cr3+.


    This decreases [Cr2O72 (aq)] but increases [Cr3+ (aq)] [1] so that the position of
    equilibrium in Cr2O72(aq) + 14H+(aq) + 6e 2Cr3+(aq) + 7H2O(l) shifts to the left and so
    ER decreases.
    Hence Ecell = ER EL decreases (i.e. Ecell < Ecell).
    [1]

    1(c)(i)

    To decrease Ecell, either decrease ER or increase EL.


    (1) ER can be decreased by using H2O2 or H+ of a lower concentration in the H2O2/H2O
    halfcell.
    [1]
    +
    (2) EL can be increased by using O2 of a higher pressure, H of a higher concentration
    or H2O2 of a lower concentration in the O2 / H2O2 halfcell.
    [1]

    (ii)

    Hydrogen peroxide can spontaneously undergo oxidation and reduction under standard
    conditions:
    2H2O2 (aq) 2H2O(l) + O2 (g),
    Ecell = +1.77 (+0.68)V = +1.09V > O
    [1]
    reaction is energetically feasible and spontaneous under standard conditions.
    Hence bubbles of oxygen are given off by a solution of hydrogen peroxide on standing.
    Disproportionation. [1] (In general, substances disproportionate if their ER > EL.)

    2(a)

    I2 (aq) + 2e 2I (aq)

    E = +0.54 V

    Fe2+ (aq) + 2e Fe (s)

    E = 0.44 V

    Ecell = 0.44 (+0.54)


    = 0.98 V < 0
    reaction is not likely to occur.
    (b)

    [1]

    H2O2 (aq) + 2H+ (aq) + 2e 2H2O (l)

    E = +1.77 V

    I2 (aq) + 2e 2I (aq)

    E = +0.54 V

    Ecell =
    =

    +1.77 (+0.54)
    +1.23 V > 0

    [1]

    reaction is energetically feasible and spontaneous under standard conditions.

    H2O2 (aq) + 2H+ (aq) + 2I (aq) 2H2O (l) + I2 (aq)


    A brown solution is formed.
    (c)

    [1]
    [1]

    Cr2O72 (aq) + 14H+ (aq) + 6e 2Cr3+ (aq) + 7H2O (l)

    E = +1.33 V

    SO42 (aq) + 4H+ (aq) + 2e- SO2 (aq) + 2H2O (l)

    E = +0.17 V

    Ecell = +1.33 (+0.17)


    = +1.16 V > 0
    [1]
    reaction is energetically feasible and spontaneous under standard conditions.
    Cr2O72(aq) + 2H+ (aq) + 3SO2 (aq) 2Cr3+ (aq) + H2O (l) + 3SO42 (aq)
    Orange solution turns green.
    2

    [1]
    [1]

    2(d)

    O2 (g) + 2H2O (l) + 4e 4OH (aq)

    E = +0.40 V

    Cr3+ (aq) + e Cr2+ (aq)

    E = 0.41 V

    Ecell = +0.40 (0.41)


    = +0.81 V > 0
    [1]
    reaction is energetically feasible and spontaneous under standard conditions.
    O2 (g) + 2H2O (l) + 4Cr2+ (aq) 4Cr3+(aq) + 4OH (aq)

    [1]

    and Cr (aq) + 3OH (aq) Cr(OH)3 (s)


    Blue solution decolourises and a greyishgreen ppt is formed in a green solution.
    3+

    [1]
    [1]

    3(a)

    O2 (g) + 4H+ (aq) + 4e 2H2O (l)

    [1]

    (b)

    CH4 (g) + 2H2O (l) CO2 (g) + 8H+ (aq) + 8e

    [1]

    (c)

    CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l)

    [1]

    (d)

    So long as the two reactants i.e. O2(g) and CH4(g) are not in direct contact [1], there is
    no need to have two separate fuel cells. (These two reactants are in fact, separated by a
    common electrolyte i.e. aqueous dilute H2SO4.)

    (e)

    Direction of e flow
    Labelling of electrodes
    Labelling of electrolyte and gases

    V
    CH4 (g)

    O2 (g)

    (anode)

    (cathode)

    Pt

    Pt

    [1]
    [1]
    [1]

    dilute
    sulphuric
    acid

    (f)

    CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

    [1]

    (g)

    They are the same except for the state of water.

    [1]

    (h)

    More efficient conversion of chemical energy into electrical energy.


    Also the products formed are much less polluting.

    [1]

    4(a)

    MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O (l)

    E = +1.52 V

    Cl2(g) + 2e 2Cl (aq)

    E = +1.36 V

    Cr2O7(aq) + 14 H+(aq) + 6e 2Cr3+(aq) + 7H2O(l)

    E = +1.33 V

    From the E values,


    it can be seen that, under standard conditions, MnO4 can oxidise Cl to Cl
    i.e. Ecell
    = +1.52 (+1.36)
    = +0.16 V > 0

    [1]

    In the titration determination of iron(II) ions (e.g. using aqueous FeCl2), the amount of
    Fe2+ present is determined by the amount of oxidant it reacts with.
    3

    If MnO4 were used, some MnO4 will be consumed by Cl instead of reacting solely with
    Fe2+. [1] This would result in a larger amt of MnO4 used than required i.e. the results
    would be inaccurate.
    On the other hand, under standard conditions, Cr2O72 cannot oxidise Cl to Cl2
    i.e. Ecell
    = +1.33 (+1.36)
    = -0.03 V < 0

    [1]

    Hence all Cr2O72 will be used to react with Fe2+ and thus K2Cr2O7 (aq) can be used for
    the titration determination of iron(II) ions in the presence of chloride ions

    4(b)

    Al3+ + 3e Al

    E = 1.66 V

    Pb2+ + 2e Pb

    E = 0.13 V

    Aluminium has a very low reduction potential and so its ion is not easily reduced to the
    metal.
    [1]
    Its ore (e.g. Al2O3) cannot be reduced by C and requires electrolysis.
    [1]
    (Note: the Al2O3 ore is not soluble in water and even if it were dissolved in acid to make up an
    aqueous solution, the latter would generate H2 (from water) at the cathode. Hence molten ore is
    needed.)

    Lead has a less negative reduction potential and so it is relatively easier for its ion to
    be reduced to the metal.
    [1]
    Hence its oxide can be reduced by C.
    (Note: carbon is a much cheaper raw material compared to the expensive electrical power needed
    for electrolysis.)

    (c)

    At the cathode:
    2H2O(l) + 2e H2(g) + 2OH(aq)
    [1]
    +

    H2 (E = 0.83 V) is preferentially discharged [1] since Na (E = 2.71 V) is less


    readily reduced.
    At the anode,
    gas B contains 80% C by mass high C content; other element present could be H.
    Assuming B is CxHy, then for 1.0 g of B,
    mole ratio of C:H

    0.80 0.20
    = 1:3 i.e. empirical formula = CH3
    :
    12.0 1.0

    B is likely C2H6.

    [1]

    The oxidation of CH3CO2(aq) could likely produce CO2 as the other gas A.
    Hence at anode, the balanced halfequation is:
    2CH3CO2(aq) CH3CH3(g) + 2CO2(g) + 2e

    [1]
    [1]

    From the halfequation, it can be seen that the amt of CO2 is twice that of CH3CH3.
    At the same temperature and pressure, the volume ratio of CO2: CH3CH3 is 2:1.
    [1]

    5(a)(i) amt of Ag deposited

    (ii)

    Ag+(aq) + e Ag
    amt of e
    quantity of charge passed
    current passed

    (iii)

    Cr3+(aq) + 3e Cr (s)
    amt of Cr deposited
    mass of Cr deposited

    (b)

    = 0.100 / 108
    = 9.26 x 104 mol

    = amt of Ag deposited
    = 9.26 x 104 mol
    = 96 500 x 9.26 x 104
    = 89.35 C
    = 89.35 / (30 x 60)
    = 0.0496 A
    0.05 A

    = 1/3 x amt of e passed


    = 3.086 x 104 mol
    = 3.086 x 104 x 52.0
    = 0.0160 g

    volume of Al2O3 to be deposited


    mass of Al2O3
    amt of Al2O3

    = 500 x 1 x 103
    = 0.5 cm3
    = 4.0 x 0.5
    = 2.0 g
    = 2.0 / (27.0 x 2 + 16.0 x 3)
    = 0.0196 mol

    At the anode: 2H2O(l) O2(g) + 4H+(aq) + 4e


    then
    4Al(s) + 3O2(g) 2Al2O3 (s)
    amt of e

    [1]

    [1]

    [1]

    [1]
    [1]

    [1]

    [1]

    = 4 x amt of O2 produced
    =4x(

    3
    x amt of Al2O3)
    2

    = 0.1176 mol
    quantity of charge needed

    (c)

    = 96 500 x 0.1176
    = 11 348 C

    Ni2+ (aq) + 2e Ni (s)


    2Ag+ (aq) + 2e 2Ag (s)
    For the same current passed,
    amt of Ag: amt of Ni deposited
    hence mass of Ag: mass of Ni deposited

    =2:1
    = 2 x 108 : 1 x 58.7
    = 3.68 : 1

    [1]

    [1]
    [1]

    5(d)

    2Cu2+ (aq) + 4e 2Cu (s)


    2H2O(l) O2(g) + 4H+(aq) + 4e

    cathode:
    anode:

    amt of O2 produced

    = x amt of Cu deposited
    = x (0.635 / 63.5)
    = 0.005 mol

    vol. of O2 produced at r.t.p.

    = 0.005 x 24.0
    = 0.12 dm3

    [1]
    [1]

    [1]

    Addtional Questions (Optional)

    A1(i)

    Ecell

    (ii)

    Fe3+ (aq) + e Fe2+ (aq)


    Cu (s) Cu2+ (aq) + 2e
    2Fe3+ (aq) + Cu (s) 2Fe2+ (aq) + Cu2+ (aq)

    (iii)

    Ecell of the reaction is +0.43V >>0. Hence even though the conditions in a testtube may
    not be under standard conditions, Ecell is still > 0 such that reaction can proceed in a test
    tube.
    [1]

    (iv)

    (Any suitable halfcell with E > +0.77 V) e.g.


    Cl2 / Cl halfcell: E = + 1.36V
    Electrode: Pt, with chlorine gas and sodium chloride solution.

    A2(i)

    = +0.77(+0.34)

    = +0.43 V

    O2 (g) + 2H2O (l) + 4e 4OH (aq)

    [1]
    [1]
    [1]
    [1]

    [1]
    [1]

    E = +0.40 V

    Zn2+ (aq) + 2e Zn (s)


    E = 0.76 V
    O2(g) + 2H2O (l) + 2Zn (s) 2Zn(OH)2 (s)

    [1]

    Ecell

    [1]

    = +0.40(+0.76)

    (ii)

    = +1.16 V

    O2 (g)

    Zn

    ()

    (+)

    electrolyte (aq)

    (iii)

    aqueous KCl. [1]


    (Note: choice of electrolyte requires careful consideration i.e. it must not oxidise Zn or C.
    e.g.
    dilute acids cannot be used since H+ reacts with Zn.
    solutions containing ions of metals less reactive than Zn (e.g. CuSO4) cannot be
    used as it undergoes displacement reaction with Zn.)

    SelfCheck
    1(i) The standard electrode potential of a halfcell is the electromotive force, measured at 298K
    and 1 atm, between the halfcell and the standard hydrogen electrode, in which the reacting
    species in solution are at molar concentrations.
    (ii) Ecell is the potential difference between two halfcells under standard conditions. It gives a
    measure of the e.m.f. (electromotive force) which pumps the electrons around the circuit.
    2(i)

    V
    T = 298 K
    H2
    (1 atm)

    Cu
    salt bridge
    Pt
    Cu2+
    H+

    [H+(aq)] = 1 mol dm3

    [Cu2+(aq)] = 1 mol dm3

    (ii)

    V
    T = 298 K
    H2
    (1 atm)
    salt bridge
    Pt

    Pt
    2+

    Fe

    Fe3+

    [H+(aq)] = 1 mol dm3

    [Fe2+(aq)] = [Fe3+(aq)]
    = 1 mol dm3

    3(i)
    E of Co2+ / Co = - 0.28V (oxid) Co is negative electrode
    E of Cl2 / Cl = + 1.36V (red) Pt is positive electrode
    (ii) Cl2 (g) + Co(s) 2Cl(aq) + Co2+(aq)
    (iii) Ecell = 1.36 (-0.28) = +1.64V

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