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Date May 2014 Marks available 6 Reference code 14M.2.hl.TZ2.5
Level HL Paper 2 Time zone TZ2
Command term Deduce and State Question number 5 Adapted from N/A

Question

Bleaches in which chlorine is the active ingredient are the most common, although some environmental groups have concerns about their use.

In aqueous chlorine the equilibrium below produces chloric(I) acid (hypochlorous acid), HOCl, the active bleach.

\[{\text{C}}{{\text{l}}_2}{\text{(aq)}} + {{\text{H}}_2}{\text{O(l)}} \rightleftharpoons {\text{HOCl(aq)}} + {{\text{H}}^ + }{\text{(aq)}} + {\text{C}}{{\text{l}}^ - }{\text{(aq)}}\]

Aqueous sodium chlorate(I), NaOCl, the most common active ingredient in chlorine based bleaches, oxidizes coloured materials to colourless products while being reduced to the chloride ion. It will also oxidize sulfur dioxide to the sulfate ion.

The standard electrode potential for the reduction of the chlorate(V) ion to the chloride ion is \( + 1.49{\text{ V}}\).

(i)     Describe the colour change that occurs when aqueous chlorine is added to aqueous sodium bromide.

(ii)     Outline, with the help of a chemical equation, why this reaction occurs.

[3]
a.

Chloric(I) acid is a weak acid, but hydrochloric acid is a strong acid. Outline how this is indicated in the equation above.

[1]
b.i.

State a balanced equation for the reaction of chloric(I) acid with water.

[1]
b.ii.

Outline, in terms of the equilibrium in aqueous chlorine, why it is dangerous to use an acidic toilet cleaner in combination with this kind of bleach.

[2]
b.iii.

Suggest why a covalent molecule, such as chloric(I) acid, is readily soluble in water.

[2]
b.iv.

Partial neutralization of chloric(I) acid creates a buffer solution. Given that the \({\text{p}}{K_{\text{a}}}\) of chloric(I) acid is 7.53, determine the pH of a solution that has \({\text{[HOCl]}} = 0.100{\text{ mol}}\,{\text{d}}{{\text{m}}^{ - 3}}\) and \({\text{[Cl}}{{\text{O}}^ - }{\text{]}} = 0.0500{\text{ mol}}\,{\text{d}}{{\text{m}}^{ - 3}}\).

[4]
b.v.

Describe, using HIn to represent the indicator in its acid form, why an indicator changes colour when excess alkali is added.

[3]
b.vi.

(i)     Deduce a balanced equation for the reaction between the chlorate(I) ion and sulfur dioxide from the appropriate half-equations.

 

 

 

 

 

(ii)     State the initial and final oxidation numbers of both chlorine and sulfur in the final equation.

M14/4/CHEMI/HP2/ENG/TZ2/05.c.ii

[6]
c.

(i)     Define the term standard electrode potential.

 

 

(ii)     Referring to Table 14 of the Data Booklet, deduce, giving a reason, whether the oxidation of the chromium(III) ion to the dichromate(VI) ion by the chlorate(V) ion is energetically feasible.

[3]
d.

Markscheme

(i)     from (pale) green/colourless to yellow/orange/brown;

Initial colour must be stated.

Do not accept “clear/transparent” instead of “colourless”.

(ii)     chlorine more reactive/more powerful oxidizing agent (than bromine);

Accept opposite statements for bromine.

Accept “chloride ion a weaker reducing agent” / “bromide ion a stronger reducing agent”.

Accept “chlorine more electronegative than bromine”.

\({\text{C}}{{\text{l}}_2}{\text{(aq)}} + {\text{2NaBr(aq)}} \to {\text{B}}{{\text{r}}_2}{\text{(aq)}} + {\text{2NaCl(aq)}}/{\text{C}}{{\text{l}}_2}{\text{(aq)}} + {\text{2B}}{{\text{r}}^ - }{\text{(aq)}} \to {\text{B}}{{\text{r}}_2}{\text{(aq)}} + {\text{2C}}{{\text{l}}^ - }{\text{(aq)}}\);

Ignore state symbols.

Do not accept with equilibrium sign.

a.

chloric(I) acid (shown as) a molecule/molecular, but hydrochloric acid (shown as being) split into ions / OWTTE;

Accept “chloric(I) acid is partially dissociated and hydrochloric acid is fully dissociated”.

Reference needed to both acids for mark.

b.i.

\({\text{HOCl(aq)}} \rightleftharpoons {{\text{H}}^ + }{\text{(aq)}} + {\text{Cl}}{{\text{O}}^ - }{\text{(aq)}}/{\text{HOCl(aq)}} + {{\text{H}}_2}{\text{O(l)}} \rightleftharpoons {{\text{H}}_3}{{\text{O}}^ + }{\text{(aq)}} + {\text{Cl}}{{\text{O}}^ - }{\text{(aq)}}\);

Equilibrium sign required for the mark.

Ignore state symbols.

b.ii.

acid displaces the equilibrium to the left (to form chlorine);

chlorine is toxic/poisonous/harmful/lung irritant;

Accept answers that refer to the (b) (ii) equilibrium.

b.iii.

chloric(I) acid has –OH group / hydrogen attached to a very electronegative atom;

Accept polar molecule.

can form hydrogen bonds to water;

hydrogen bonding to water increases its solubility;

(as a weak acid it is) in equilibrium with ions;

b.iv.

\({K_{\text{a}}} = {10^{ - 7.53}} = 2.95 \times {10^{ - 8}}{\text{ (mol}}\,{\text{d}}{{\text{m}}^{ - 3}})\);

\({K_{\text{a}}} = \frac{{{\text{[}}{{\text{H}}^ + }{\text{][Cl}}{{\text{O}}^ - }{\text{]}}}}{{{\text{[HOCl]}}}} = \frac{{{\text{[}}{{\text{H}}^ + }{\text{](0.05)}}}}{{{\text{(0.1)}}}} \approx \frac{{{\text{[}}{{\text{H}}^ + }{\text{]}}}}{2} = {\text{2.95}} \times {\text{1}}{{\text{0}}^{ - 8}}{\text{ (mol}}\,{\text{d}}{{\text{m}}^{ - 3}}{\text{)}}\);

\({\text{[}}{{\text{H}}^ + }{\text{]}} = 2 \times 2.95 \times {10^{ - 8}} = 5.9 \times {10^{ - 8}}{\text{ (mol}}\,{\text{d}}{{\text{m}}^{ - 3}}{\text{)}}\);

\({\text{pH}} =  - \log (5.9 \times {10^{ - 8}}) = 7.23\);

Accept other methods of carrying out the calculation.

Award [4] for correct final answer.

b.v.

\({\text{HIn}} \rightleftharpoons {{\text{H}}^ + } + {\text{I}}{{\text{n}}^ - }\);

Do not accept equation without equilibrium arrow.

(weak acid in which the) acid/HIn and conjugate base/In– have different colours / OWTTE;

excess alkali shifts the equilibrium to the RHS/towards the conjugate base;

b.vi.

(i)     \({\text{Cl}}{{\text{O}}^ - }{\text{(aq)}} + {\text{2}}{{\text{H}}^ + }{\text{(aq)}} + {\text{2}}{{\text{e}}^ - } \rightleftharpoons {{\text{H}}_2}{\text{O(l)}} + {\text{C}}{{\text{l}}^ - }{\text{(aq)}}\);

\({\text{SO}}_4^{2 - }{\text{(aq)}} + {\text{4}}{{\text{H}}^ + }{\text{(aq)}} + {\text{2}}{{\text{e}}^ - } \rightleftharpoons {\text{S}}{{\text{O}}_2}{\text{(aq)}} + {\text{2}}{{\text{H}}_2}{\text{O(l)}}\);

Accept SO42–(aq) + 4H+(aq) + 2e\( \rightleftharpoons \) H2SO3(aq) + H2O(l).

For final equation:

\({\text{Cl}}{{\text{O}}^ - }{\text{(aq)}} + {\text{S}}{{\text{O}}_2}{\text{(aq)}} + {{\text{H}}_2}{\text{O(l)}} \rightleftharpoons {\text{SO}}_4^{2 - }{\text{(aq)}} + {\text{2}}{{\text{H}}^ + }{\text{(aq)}} + {\text{C}}{{\text{l}}^ - }{\text{(aq)}}\)

Accept ClO(aq) + H2SO3(aq) \( \rightleftharpoons \) SO42–(aq) + 2H+(aq) + Cl(aq).

correct reactants and products;

balancing and cancelling \({{\text{e}}^ - }\), \({{\text{H}}^ + }\) and \({{\text{H}}_2}{\text{O}}\);

Apply ECF if incorrect half-equations written.

Ignore state symbols and absence of equilibrium arrow for all equations and accept inclusion of Na+ in any equation.

(ii)     Award [2] for all correct, [1] for 2 or 3 correct.

M14/4/CHEMI/HP2/ENG/TZ2/05.c.ii/M

Remember to apply ECF from final (c) (i) equation.

Penalise incorrect notation (eg, 4 or 4+ rather than +4) once only, so award [1] for a fully correct answer in an incorrect format.

c.

(i)     potential (of reduction half-reaction) under standard conditions measured

relative to standard hydrogen electrode/SHE / OWTTE;

Allow “solute concentration of 1 mol dm–3” or “1 bar/1 atm (pressure) for gases” instead of “standard conditions”.

(ii)     yes / energetically feasible;

would have a positive \({E_{{\text{cell}}}}\) / chlorate(V) ion stronger oxidizing agent than dichromate(VI) ion / OWTTE;

d.

Examiners report

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

a.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

b.i.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

b.ii.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

b.iii.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

b.iv.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

b.v.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

b.vi.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

c.

Though it was the least popular question on the paper, it was still answered, though not very well, by a significant number of students. Correct responses to the colour change required in the first part were rare, though more students could write an appropriate equation and outline why the reaction occurred, even though this was often phrased in terms of electronegativity, rather than reactivity or electrode potential. In part (b) many students seemed to be aware of the difference between strong and weak acids, but few could use this to answer the question asked and frequently, even having displayed this knowledge, were unable to write an equation for the required reaction in water. Unfortunately changes in pagination meant that the phrase “the equilibrium above” in part (b) (iii) may have confused candidates with regard to which particular equilibrium the question referred to. Fortunately both of the equilibria that it could have referred to change in the same direction and students scored well on this, and both would eventually result in the release of chlorine, that a number recognized as a toxic gas. In contrast to Question 1, many students could correctly identify the hydrogen bonding, resulting from the –OH group, as being the reason for the solubility of HOCl in water. An encouraging number of students gained full marks for calculating the pH of the buffer, usually by memorizing the Henderson-Hasselbalch equation and substituting in this. An even greater number of students could accurately explain the mode of action of acid-base indicators. In part (c) very few students could write, much less combine, appropriate half equations, even though the reactants and products were given, but far more could correctly deduce the oxidation numbers of the species involved. In the final part most students had some general idea of what a standard electrode potential was, but in many cases the definitions lacked the detail required. Quite a few students correctly deduced that the oxidation of chromium(III) to dichromate(VI) was energetically feasible and give valid reasons to support this.

d.

Syllabus sections

Core » Topic 9: Redox processes » 9.1 Oxidation and reduction
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