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6 Redox (2) (S)
6 Redox (2) (S)
1. Determine the oxidation state of the underlined element in the species below.
(a) N2O5 (b) KClO (c) [PtCl6]2 (d) S2O82 (e) BaCrO4 (f) ICl
(a) +5; (b) +1; (c) +4; (d) +7; (e) +6; (f) 1
B Definitions
[Refer to lecture notes pages 3 4 and 7 – 10]
(b) Cu2+ gains 2 electrons to form Cu, and hence Cu2+ undergoes reduction.
(c) Zn loses 2 electrons to form Zn2+, +, and hence Zn is the reducing agent.
(d) Cu2+ gains 2 electrons to form Cu and hence Cu2+ is the oxidising agent.
3. Using the changes in oxidation number, determine which of the following equations represent
redox reactions. For such reactions, identify the oxidising agent and reducing agent present.
(a) BaCl2(aq) + H2SO4(aq) BaSO4(s) + 2HCl(aq)
(b) 2Cu2+(aq) + 4I−(aq) 2CuI(s) + I2(aq)
(c) Sn(s) + Sn(OH)62−(aq) 2Sn(OH)3−(aq)
(a) Non-redox reaction as the oxidation state of all the atoms remain unchanged.
(b) Redox reaction. I− is the reducing agent and Cu2+ is the oxidising agent. I− loses electrons to
Cu2+ and hence oxidation state of iodine increases from 1 in I− to 0 in I2 i.e. I− is oxidised.
Simultaenously, Cu2+ gains electrons from I− and hence oxidation state of copper decreases
from +2 in Cu2+ to +1 in CuI, i.e. Cu2+ is reduced.
(c) Redox reaction. Sn is the reducing agent and Sn(OH)62− is the oxidising agent. Sn loses electrons
to Sn(OH)62− and hence oxidation state of tin increases from 0 in Sn to +2 in Sn(OH)3− i.e. Sn is
oxidised. Simultaneously, Sn(OH)62− gains electrons from Sn and hence oxidation state of tin in
Sn(OH)62− is reduced from +4 in Sn(OH)62− to +2 in Sn(OH)3− i.e. Sn(OH)62− is reduced.
6. Balance the following redox reactions in acidic medium using the half-equation method.
(a) IO4− + I− I2
(b) MnO4− + ClO− Mn2+ + ClO4−
7. Balance the following redox reactions in alkaline medium using the half-equation method.
(a) N2H4 + ClO3− NO + Cl−
(b) Br2 Br− + BrO3−
D Redox Titrations
D1 Manganate(VII) Titrations
[Refer to lecture notes pages 15 16]
8. 12.50 cm3 of a given solution of hydrogen peroxide were diluted to 500 cm 3 with distilled water.
25.0 cm3 of this diluted solution required 22.50 cm3 of 0.0200 moldm−3 potassium manganate(VII)
solution for titration in acidic medium.
(a) Construct an equation for the reaction between H2O2 and MnO4 ions.
(b) Describe how you would recognise the end-point during this titration.
(c) Use your equation from (a) and the data above to calculate the original concentration, in
mol dm3, of the hydrogen peroxide solution.
(1.80 mol dm3)
(b) The endpoint of the titration is reached when the colour of the solution in the conical flask changes
from colourless to permanent faint pink after one excess drop of the MnO4− is added to the conical
flask.
(c) 22.50
Amount of MnO4– = 0.0200 1000 = 4.500 10−4 mol
9. N16/P3/Q3(c)
Solder is a low-melting alloy used to join metals together, and is used for plumbing and in the
electronics industry. Often solders are alloys of tin and lead. The tin content of a solder can be
determined by the following method.
(a) Write an equation for the oxidation of Sn2+ by acidified MnO4−. Assume that tin(IV) exists
as Sn4+ ions.
(b) A 25.0 cm3 sample of solution X required 22.50 cm3 of 0.0200 mol dm−3 KMnO4 solution for
complete reaction.
Calculate the percentage by mass of tin in the solder.
(44.5%)
(b) 22.50
Amount of MnO4– added = 0.0200 1000 = 4.500 10−4 mol
Mole ratio of MnO4– : Sn2+ = 2 : 5
5
Amount of Sn2+ in 25.0 cm3 of solution = (4.500 10−4) 2 = 1.125 10−3 mol
Amount of Sn2+ in 250 cm3 of solution = 0.001125 10 = 0.01125 mol
Sn + 2H+ Sn2+ + H2
Amount of Sn = Amount of Sn2+ in 250 cm3 of solution = 0.01125 mol
Mass of Sn = 0.01125 118.7 = 1.3353 g
1.3353
Percentage by mass of Sn = 3.00
100% = 44.5 %
D2 Dichromate(VI) Titrations
[Refer to lecture notes pages 17 18]
10. N13/P2/Q2(c)
Iron ore from different mines will contain different percentage by mass of iron. The percentage of
iron in a sample of ore can be estimated by converting all of the iron present into Fe 2+(aq) ions
and then using a redox titration.
The sample of ore is crushed, weighed and then the iron( III) oxide is dissolved in aqueous acid.
The Fe3+(aq) ions are then reduced to Fe2+(aq) ions by reaction with an excess of aqueous tin(II)
chloride, SnCl2.
A sample of iron ore weighing 11.15 g was converted to Fe2+(aq) ions using the method describe
above. The solution was mixed with dilute sulfuric acid and made up to a volume of exactly
250.0 cm3 in a volumetric flask. 25.0 cm3 portions of this solution were then titrated with
0.100 mol dm−3 aqueous potassium dichromate(VI) using a suitable indicator. The results are
shown below.
titration number 1 2 3
3
initial burette reading / cm 0.00 21.85 0.00
final burette reading / cm3 21.85 43.25 21.50
3
titre / cm
(a) Complete the table and use the results to calculate the number of moles of potassium
dichromate(VI) required to react with the Fe2+ ions in 25.0 cm3 of the solution.
(0.00215)
(b) Construct an ionic equation for the reaction of Fe2+ ions with acidified Cr2O72− ions.
(c) Calculate the total number of moles of Fe2+ ions in the original solution made up from the
iron ore, and hence calculate the percentage by mass of iron in the sample of iron ore.
(64.4%)
Amount of K2Cr2O7 required = 0.02145 × 0.100 = 2.145 × 10−3 = 2.15 × 10−3 mol
11. "Chromium oxide" cassette tapes contain CrO2, an unusual oxide of chromium. It is both highly
conductive and ferromagnetic, and provides a good audio frequency response.
When the oxide from a length of such tape is dissolved in dilute acid, CrO2 disproportionates to
Cr3+ and Cr2O72‒. The resultant solution needed 10.0 cm3 of 0.0200 mol dm‒3 Fe2+(aq) to
completely reduce the Cr2O72‒ to Cr3+.
(a) CrO2 disproportionates to Cr3+ and Cr2O72‒. Explain the term in italics with respect to this
reaction.
(b) Construct balanced equations for the disproportionation reaction of CrO2, and that between
Cr2O72− and Fe2+. You may assume an acidic medium for both reactions.
(c) Use the given data to calculate the mass of CrO2 in the length of tape.
(0.0168 g)
(a) CrO2 is simultaneously oxidised, as the oxidation state of chromium increases from +4 in CrO2 to
+6 in Cr2O72−, and reduced, as its oxidation state decreases from +4 in CrO2 to +3 in Cr3+.
(c) 10.0
Amount of Fe2+ = 0.02000 × 1000 = 2.000 10−4 mol
Mole ratio of Cr2O72− : Fe2+ = 1 : 6
1
Amount of Cr2O72− = (2.000 10−4) × 6 = 3.3333 × 10−5 mol
D3 Iodine-Thiosulfate Titrations
[Refer to lecture notes pages 19 20]
12. The carbon monoxide in a sample of polluted air can be readily determined by passing the gas
over solid iodine(V) oxide, I2O5, to produce carbon dioxide and iodine.
(a) Write a balanced equation for the reaction between carbon monoxide and iodine(V) oxide.
(b) The iodine produced is removed and titrated with aqueous sodium thiosulfate according to
the equation.
2Na2S2O3 + I2 Na2S4O6 + 2NaI
A 1.0 dm3 sample of air produced iodine that required 20.0 cm3 of 0.10 mol dm‒3 sodium
thiosulfate for complete reaction. Determine the mass of carbon monoxide in the sample.
(0140 g)
(b) 20.0
Amount of S2O32‒ = 0.10 = 2.000 10−3 mol
1000
Mole ratio of I2 : S2O32 = 1 : 2
Amount of I2 liberated = (2.000 10−3 ) ÷ 2 = 1.000 10−3 mol
Mole ratio of I2 : CO = 1 : 5
Amount of CO = (1.000 10−3)5 = 5.000 10−3 mol
Mass of CO = (5.000 10−3) 28.0 = 0.140 g
13. N11/P3/Q1(c)
N-chlorosuccinimide, C4H4O2NCl, is used in some water purification tablets. It dissolves in water
to give a solution of chloric(I) acid, HClO, which kills waterborne bacteria.
O O
N Cl + H2O N H + HClO
O O
N-chlorosuccinimide
(a) Construct a balanced equation for the reaction between HClO and acidified KI(aq).
When one tablet was subjected to the above procedure, 6.0 cm3 of 0.0050 mol dm−3 sodium
thiosulfate were required to discharge the colour of I2.
(b) 6.0
Amount of S2O32‒ = 0.0050 1000 = 3.000 × 10−5 mol
Mole ratio of I2 : S2O32 = 1 : 2
Amount of I2 liberated = (3.000 × 10−5) ÷ 2 = 1.500 × 10−5 mol
Mole ratio of I2 : HClO = 1 : 1
Amount of HClO = 1.500 × 10−51 = 1.500 × 10−5 mol
Mole ratio of C4H4O2NCl : HClO = 1 : 1
Amount of C4H4O2NCl = 1.500 × 10−51 = 1.500 × 10−5 mol
Mass of C4H4O2NCl = (1.500 × 10−5) 133.5 = 2.00 × 10−3 g
14. N00/P1/Q3(c)
In a titration experiment, 20.0 cm3 of 0.0200 mol dm‒3 BrO3− was found to react completely with
80.0 cm3 of 0.0100 mol dm−3 NH2OH to give aqueous Br− as one of the products.
(b) Calculate the amount of BrO3− and NH2OH used in the titration.
(4.00 × 10−4 mol and 8.00 × 10−4 mol)
(c) Using your answers to (a) and (b) as well as the list of possible product below, determine
the other nitrogen-containing product of the reaction.
Possible products: N2O, NH3, NO, NO2−.
(d) Hence, construct an overall equation for the reaction between NH2OH and BrO3−.
(b) 20.0
Amount of BrO3‒ = 0.0200 = 4.00 × 10−4 mol
1000
80.0
Amount of NH2OH = 0.0100 1000 = 8.00 × 10−4 mol
(c) Amount of electrons gained by BrO3‒ = (4.00 × 10−4) 6= 0.002400 mol
Amount of electrons lost by NH2OH = 0.002400 mol
Amount of electrons lost by 1 mol of NH2OH = 0.002400 ÷ (8.00 × 10−4) = 3 mol
Since 1 mol of NH2OH loses 3 mol of electrons, its oxidation state will increase by 3 units (from
1 in NH2OH) to +2.
Product is NO.
15. N99/P1/Q3(c)
The oxidation number of vanadium in a complex ion was determined as follows. A sample
containing 0.0130 mol of the complex was dissolved in water and the solution made up to
100 cm3 with distilled water. A 10.0 cm3 portion of this solution required 20.80 cm3 of 0.0250
moldm3 KMnO4 to oxidise all the vanadium to the +5 oxidation state. Use these data to calculate
the original oxidation number of the vanadium.
(+3)
Step 1:
construct the oxidation/reduction half-equation for the MnO4− + 8H+ + 5e− Mn2+ + 4H2O
species of known oxidation state
Step 2: 20.80
calculate the amount of the reducing agent and
Amount of MnO4‒ = 0.0250 1000 = 5.200 10−4
oxidising agent used
Amount of Vn+ in 10.0 cm3 = 0.0130 ÷10
= 1.300 10−3 mol
Step 3:
Amount of electrons gained by MnO4
calculate the amount of electrons transferred by the
species of known oxidation state = (5.200 10−4) 5= 2.600 10−2 mol
Step 4: Amount of electrons lost by Vn = 2.600 10−2 mol
calculate the amount of electrons transferred by per
mole of the species of unknown oxidation state
Amount of electrons lost by 1 mol of V2+
= (2.600 10−2) ÷ (1.300 10−3) = 2 mol
Step 5: Since 1 mol of Vn+ loses 2 mol of electrons, its
determine the oxidation state of the element of the oxidation state will increase by 2 units to +5.
species
F Additional Questions
16. N13/P3/Q3(c)
25.0 cm3 of a solution formed by dissolving SO2 in water was titrated with 0.0200 mol dm3 KMnO4.
20.5 cm3 KMnO4 of this solution were required for the end point.
(a) Construct an equation for the reaction between SO2 and MnO4 ions.
(b) Describe how you would recognise the end-point during this titration.
(c) Use your equation from (a) and the data above to calculate the concentration of SO2 in
mol dm3 in the solution.
(0.0410 mol dm3)
(b) The endpoint of the titration is reached when the colour of the solution in the conical flask changes
from colourless to permanent faint pink after one excess drop of the MnO4− is added to the conical
flask.
(c) 20.5
Amount of MnO4– = 0.0200 1000 = 4.100 10−4 mol
Since the number of moles of NH4+ in the first portion of the solution is the same as the number of moles
of Fe3+ in the other portion of the solution,
in the salt, for every Fe3+ ion, there would be one NH4+ ion.
a=1
formula becomes: (NH4)Fe(SO4)bxH2O
In order for the salt to be neutral and since SO42− is the only anion present,
total charge of compound = charge on NH4+ + charge on Fe3+ + b(charge on SO42−)
0 = + 1 + 3 + b(−2)
b=2
formula becomes: (NH4)Fe(SO4)2xH2O
Amount of the salt, (NH4)Fe(SO4)2xH2O, in 50 cm3 = Amount of Fe3+ in 50 cm3 = 1.040 10−3 mol
Amount of the salt, (NH4)Fe(SO4)2xH2O, in 100 cm3 = (1.040 10−3) 2 = 2.080 10−3 mol
Molar mass of (NH4)Fe(SO4)2xH2O = 1.00 ÷ (2.080 10−3) = 480.8 g mol1
18. Burning sodium in air produces a mixture of sodium oxide, Na2O, and sodium peroxide,
Na2O2.The proportion of sodium peroxide in the mixture can be determined by the following
method.
The mixture is dissolved in water.
16.7
Amount of S2O32‒ = 0.200 1000 = 3.340 10−3 mol
Mole ratio of I2 : S2O32 = 1 : 2
Amount of I2 liberated = (3.340 10−3) ÷ 2 = 1.670 10−3 mol
Mole ratio of I2 : H2O2 = 1 : 1
Amount of H2O2 = (1.670 10−3)1 = 1.670 10−3 mol
Mole ratio of Na2O2 : H2O2 = 1 : 1
Amount of Na2O2 = (1.670 10−3)1 = 1.670 10−3 mol
Mass of Na2O2 = (1.670 10−3) 78.0 = 0.13026 g
Mass of Na2O = 0.500 – 0.13026 = 0.36974 g
Amount of Na2O = 0.3697462.0 = 5.9635 10−3 mol
moles of Na2 O 0.0059635
= = 3.57
moles of Na2 O2 0.001670
19. 2.00 g of hydrated sodium sulfite, Na2SO3∙ xH2O was dissolved in an aqueous solution of iodine
containing 6.00 g of I2. The resultant solution was made up to 1 dm3 with distilled water. The
sulfite ions were oxidised to sulfate ions according to the equation:
SO32− + I2 + H2O SO42− + 2H+ + 2I−
Subsequently, when 25.0 cm3 of this solution was titrated with sodium thiosulfate solution
containing 2.80 g of thiosulfate ions per dm3, the titre required to react with the excess iodine was
31.50 cm3. Determine,
(a) the mass of iodine remaining in 1 dm3 of the solution after the reaction of iodine with sulfite
ions,
(4.00 g)
(b) the mass of iodine that had reacted with 2.00 g of the sulfite ions, and hence,
(2.00 g)
20. 25.0 cm3 of a solution of X2O5 of concentration 0.100 mol dm‒3 is reduced by sulfur dioxide to a
lower oxidation state. To oxidise X back to its original oxidation state, 50.0 cm 3 of
0.0200 mol dm‒3 potassium manganate(VII) solution was required.
(b) Suggest a formula of the product formed when X2O5 was reduced by sulfur dioxide.
(a) Let the product of the reduction of X2O5 by sulfur dioxide be Xred
Step 1:
construct the oxidation/reduction half-
MnO4− + 8H+ + 5e− Mn2+ + 4H2O
equation for the species of known
oxidation state
Step 2: 50.0
Amount of MnO4‒ = 0.0200 1000
calculate the amount of the reducing
agent and oxidising agent used = 1.000 10−3 mol
25.0
Amount of X2O5 = 0.100 = 2.500 10−3 mol
1000
21. N11/P3/Q5(f)(ii)
An acidified solution of the salt KClOx (x = 1, 2 or 3) will oxidise Fe2+(aq) to Fe3+(aq) quantitatively,
the chlorine being reduced to Cl(aq).
When 0.150 g of the KClOx salt was reacted with 0.500 mol dm‒3 Fe2+(aq) in the presence of
H+(aq), 11.3 cm3 of Fe2+(aq) was needed for complete reaction.
Calculate the value of x and construct an equation for the reaction between Fe2+(aq) and acidified
KClOx(aq).
Step 1:
construct the oxidation/reduction half-
Fe2+ Fe3+ + e−
equation for the species of known oxidation
state
Step 2: 11.3
Amount of Fe2+ = 0.500 = 5.650 10−3 mol
calculate the amount of the reducing agent 1000
Step 3:
Amount of electrons lost by Fe2+
calculate the amount of electrons transferred
= (5.650 10−3) 1= 5.650 10−3 mol
by the species of known oxidation state
Step 4: Amount of electrons gained by ClOx−
calculate the amount of electrons transferred = 5.650 10−3mol
by per mole of the species of unknown
Amount of electrons gained by 1 mol of ClOx−
oxidation state
0.150 0.00565(74.6 + 16.0x)
= 0.00565 ÷ 74.6 + 16.0x = 0.150
mol
Step 5: ClOx− + 2xH+ + 2xe− Cl− + xH2O
determine the oxidation state of the element 0.00565(74.6 + 16.0x)
of the species 0.150
= 2x
0.4215
x = 0.2096 =2
Alternative Method
11.3
Amount of Fe2+ = 0.500 1000 = 5.650 10−3 mol
Amount of electron lost = 5.650 10−3 mol
Therefore, x = 2
CHEM~IS~TRY