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Paper 2 (Short answers and extended-response questions)

Topic 8: Acids and bases

1. Identify the Brønsted-Lowry acids in the following reaction.


H2SO4 + HNO3 ⇄ HSO4− + H2NO3+

2. Identify with an explanation which of the following is not a Brønsted-Lowry acid - conjugate base pair.
(a) CH3COOH / CH3COO–
(b) H3O+ / OH–
(c) H2SO4 / HSO4–
(d) HSO4– / SO42–

3. Determine the pH of an alkaline solution with a hydroxide concentration of 3.00 x 10−3 mol dm−3.

4. The pH of a solution of 0.100 mol dm-3 ethanoic acid, CH3COOH(aq), is about 3 and the pH of a
solution of 0.100 mol dm-3 nitric acid, HNO3(aq), is 1.

(a) Explain why the solution of ethanoic acid has a higher pH value even though both acids have the same
concentration.
(b) Approximately how many times stronger is the nitric acid solution compared to the ethanoic acid
solution?
(c) Approximately how much distilled water would need to be added to 25 cm3 of the nitric acid solution
so that the resulting mixture has the same pH as the ethanoic acid solution?

5. The pH of 0.100 mol dm-3 potassium hydroxide solution, KOH(aq), is 13 and the pH of 0.100 mol dm-3
ammonia solution, NH3(aq), is about 11. Explain why the pH values of the two solutions are different
even though their concentrations are the same.

6. The equilibrium constant for the dissociation of ethanoic acid, CH3COOH, in water is 1.8 x 10-5. The
equilibrium constant for the dissociation of chloroethanoic acid, CH2ClCOOH, in water is 1.4 x 10-3.

(a) Write the equation for the dissociation of ethanoic acid in water.

(b) Write the equilibrium expression for the dissociation of ethanoic acid in water.

(c) Deduce which of the two acids given above is weaker and explain your reasoning.

7. The ethoxide ion, C2H5O−, is a stronger base than the hydroxide ion, OH−. Deduce how the equilibrium
constant for the dissociation of ethanol will differ to the dissociation of water at the same temperature.

8. Sulfuric acid is often assumed to be a strong diprotic acid. In fact the equilibrium constant for the
dissociation of H2SO4(aq) to form HSO4–(aq) and H+(aq) is 2.4 x 106 and the equilibrium constant for the
dissociation of HSO4–(aq) to form SO42–(aq) and H+(aq) is 1.0 x 10-2.
Use this information to properly describe the strength of sulfuric acid.

9. Carbon dioxide is naturally present in rain water as carbonic acid.


(a) Explain why pure rain water containing dissolved carbon dioxide cannot have a pH lower than 5.6
(b) How much more acidic than rain water with a pH of 5.6 is a sample of acid rain with a pH of 4.6 ?

10. (a) Nitrogen oxide, NO, is produced in car engines. Give the equations to show how it eventually
forms nitric acid, HNO3 and nitrous acid, HNO2 in the atmosphere.
(b) Sulfur dioxide, SO2, is formed when S-containing fossils fuels are combusted. Give the equations to
show how it eventually forms sulfuric acid, H2SO4, and sulphurous acid, H2SO3, in the atmosphere.
11. Describe and explain how acid rain affects the growth of trees.

12. The image above shows a statue of a lion in Leeds, U.K. that has been badly affected by acid
deposition.
Give the ionic equation for the reaction of acid with the carbonate ions in the statue.

13. Explain how adding either calcium hydroxide or calcium oxide can counter the effects of acidification
of lakes.

14. The cyanide ion, CN− is a good ligand. It is poisonous as it reacts irreversibly with transition metal
ions in the body.
(a) Draw the Lewis structure of the cyanide ion.
(b) Use the concept of formal charge to suggest why it is the carbon atom of the cyanide ion that bonds to
the transition metal ion and not the nitrogen atom.
(c) Using information from the spectrochemical series suggest why drinking an aqueous solution of
iron(II) sulfate is an effective antidote to cyanide poisoning provided it is taken immediately after the
cyanide has been ingested.

15. Aluminium chloride. AlCl3 readily dimerises to form Al2Cl6. Explain this dimerisation reaction in
terms of Lewis acid and base theory clearly identifying the Lewis acid and the Lewis base.

16. The graph below shows how the ionic product of water changes with temperature. Use the graph to
determine:
(a) the value of Kw at 80 oC.
(b) the hydrogen ion concentration at 70 oC.
(c) the hydroxide concentration at 70 oC.
(d) the pH at 50oC.
(e) the pOH at 80 oC.

17. Calculate the pH of the resulting solution at 25 oC when 50.1 cm3 of 0.100 mol dm-3 sodium hydroxide
solution has been added to 50.0 cm3 of (a) 0.100 mol dm-3 hydrochloric acid solution and (b) 0.100 mol
dm-3 ethanoic acid solution. pKa of ethanoic acid = 4.76 at 25 oC.

18. Deduce the pH of the resulting solution obtained at 25 oC when 25.0 cm3 of 0.100 mol dm-3 potassium
hydroxide solution has been added to 50.0 cm3 of 0.100 mol dm-3 methanoic acid solution, HCOOH(aq).
pKa of methanoic acid = 3.75 at 25 oC.
19. (a) (i) State an equation for the reaction of ethanoic acid with water.
(1)
(ii) Calculate the pH of 0.200 mol dm–3 ethanoic acid (pKa = 4.76).
(3)
(b) Determine the pH of a solution formed from adding 50.0 cm3 of 1.00 mol dm–3
ethanoic acid, CH3COOH(aq), to 50.0 cm3 of 0.600 mol dm–3 sodium hydroxide,
NaOH(aq).
(4)
(c) Explain how the solution formed in part (b) can act as a buffer. Use equations to support
your answer.
(2)
20. Water is an important substance that is abundant on the Earth’s surface.
(i) State the expression for the ionic product constant of water, Kw.
(1)
(ii) Explain why even a very acidic aqueous solution still has some OH– ions present in it.
(1)
(iii) State and explain the effect of increasing temperature on the value of Kw given that the
ionization of water is an endothermic process.
(3)
(iv) State and explain the effect of increasing temperature on the pH of water.
(2)
21. (Paper 3 only) Buffer solutions resist small changes in pH. A phosphate buffer can be made by
dissolving NaH2PO4 and Na2HPO4 in water, in which NaH2PO4 produces the acidic ion and
Na2HPO4 produces the conjugate base ion.
(i) Deduce the acid and conjugate base ions that make up the phosphate buffer and state the
ionic equation that represents the phosphate buffer.
(3)
(ii) Describe how the phosphate buffer minimizes the effect of the addition of a strong base,
OH–(aq), to the buffer. Illustrate your answer with an ionic equation.
(2)
(iii) Describe how the phosphate buffer minimizes the effect of the addition of a strong acid,
H+(aq), to the buffer. Illustrate your answer with an ionic equation.
(2)
22. A 0.10 mol dm–3 ammonia solution is placed in a flask and titrated with a 0.10 mol dm–3
hydrochloric acid solution.
(i) Explain why the pH of the ammonia solution is less than 13.
(2)
(ii) Estimate the pH at the equivalence point for the titration of hydrochloric acid with
ammonia and explain your reasoning.
(2)
(iii) State the equation for the reaction of ammonia with water and write the Kb expression
for NH3(aq).
(2)
(iv) When half the ammonia has been neutralized (the half-equivalence point), the pH of the
solution is 9.25. Deduce the relationship between [NH3] and [NH4+] at the half-
equivalence point.
(1)
(v) Determine pKb and Kb for ammonia based on the pH at the half-equivalence point.
(3)
(vi) Describe the significance of the half-equivalence point in terms of its effectiveness as a
buffer. (1)
23.
(a) Predict and explain, using equations where appropriate, whether the following solutions
are acidic, alkaline or neutral.
(i) 0.1 mol dm–3 FeCl3(aq) – not in the syllabus
(1)
(ii) 0.1 mol dm–3 NaNO3(aq)
(1)
(iii) 0.1 mol dm–3 Na2CO3(aq)
(1)
(b) Acidic gases can be released into the atmosphere that have an environmental impact
when they are deposited as acid rain. State two elements that form the acidic gases and
describe two impacts they have on the natural environment.
(3)

24. An experiment was carried out to determine the concentration of aqueous ammonia by
titrating it with a 0.150 mol dm–3 sulfuric acid solution. It was found that 25.0 cm3 of the
aqueous ammonia required 20.1 cm3 of the sulfuric acid solution for neutralization.
(a) Write the equation for the reaction and calculate the concentration, in mol dm–3, of the
aqueous ammonia.
(4)
(b) Several acid-base indicators are listed in Table 16 of the Data Booklet. Identify one
indicator that could be used for this experiment. Explain your answer.
(3)
(c) (i) Determine the pOH of 0.121 mol dm–3 aqueous ammonia (pKb = 4.75).
(4)
(ii) State what is meant by the term buffer solution, and describe the composition of an
acid buffer solution in general terms.
(3)

(iii) Calculate the pH of a mixture of 50.0 cm3 of 0.100 mol dm–3 aqueous ammonia
and 50.0 cm3 of 0.0500 mol dm–3 hydrochloric acid solution.
(4)

25. (a) The pKa value for propanoic acid is given in Table 15 of the Data Booklet.
(i) State the equation for the reaction of propanoic acid with water.
(1)
(ii) Calculate the hydrogen ion concentration (in mol dm–3) of an aqueous solution of
0.100 mol dm–3 propanoic acid.
(2)
(b) The graph below shows a computer simulation of a titration of 25.0 cm3 of
0.100 mol dm–3 hydrochloric acid with 0.100 mol dm–3 sodium hydroxide and the pH
range of phenol red indicator.
Sketch the graph that would be obtained for the titration of 25.0 cm3 of 0.100 mol dm–3
propanoic acid with 0.100 mol dm–3 potassium hydroxide using bromophenol blue as
an indicator. (The pH range of bromophenol blue can be found in Table 16 of the Data
Booklet).

(3)

Answers:

1. H2SO4 and H2NO3+

2. (b) H3O+ / OH– . (a), (c) and (d) all show the acid and the conjugate base formed by losing one
proton. The conjugate base of H3O+ is H2O not OH–.

3. [H+] x [OH﹣] = 1.00 x 10﹣14


[H+] = 1.00 x 10﹣14 ÷ 3.00 x 10−3 = 3.33 x 10−12 mol dm-3
pH = ﹣log10[H+] = ﹣log10 3.33 x 10−12 = 11.5

4. (a) Ethanoic acid is a weak acid so is only slightly dissociated into its ions so the concentration of
hydrogen ions will be lower than for nitric acid which being a strong acid is fully dissociated.
(b) As the difference in pH is two units, nitric acid is approximately one hundred times stronger.
(c) It needs to be diluted 100 times so 2475 cm3 of distilled water needs to be added to bring the total
volume to 2500 cm3.
5. Potassium hydroxide is a strong alkali so is completely dissociated into potassium ions and hydroxide
ions in aqueous solution. Ammonia is a weak base and only slightly reacts with water to form ammonium
ions and hydroxide ions.
NH3(aq) + H2O(l) ⇄ NH4+(aq) + OH–(aq)
As the concentration of hydroxide ions in ammonia solution is lower than the concentration of hydroxide
ions in potassium hydroxide solution the concentration of hydrogen ions will be higher so the pH will be
lower.

6. (a) CH3COOH(aq) + H2O(l) ⇄ CH3COO–(aq) + H+(aq)


(b)

(c) Although both are weak acids, ethanoic acid is weaker as the value for its equilibrium constant is
lower so it is even less dissociated than chloroethanoic acid.

7. Ethanol, the conjugate acid of the ethoxide ion, will be less dissociated than water as it will be a weaker
acid than water, the conjugate base of the hydroxide ion so the equilibrium constant will be smaller. This
is because the ethoxide ion is the stronger base so will have the weaker conjugate acid.

8. Sulfuric acid a strong monoprotic acid as it is almost completely dissociated to form the HSO4– ion and
H+ but not a strong diprotic acid as HSO4– behaves as a weak acid when it forms the SO42– ion.

9. (a) Carbonic acid is a weak acid so is only very slightly dissociated


H2CO3(aq) ⇄ H+(aq) + HCO3–(aq)
so that, even in a saturated solution, the concentration of hydrogen ions can never give a pH lower than
5.6.

(b) Ten times more acidic (as the pH has decreased by one unit)

10. (a) 2NO(g) + O2(g) → 2NO2


2NO2(g) + H2O(l) → HNO3(aq) + HNO2(aq)
(nitric acid can also be formed from: 4NO2(g) + O2(g) + 2H2O(l) → 4HNO3(aq) )
(b) SO2(g) + H2O(l) → H2SO3(aq)
2SO2(g) + O2(g) → 2SO3(g) then SO3(g) + H2O(l) → H2SO4(aq)

11. Tree growth is stunted with thinning of the tops and loss and yellowing of leaves. This is due to the
leaching of important nutrients, such as Ca2+, Mg2+ and K+ from the soil. The loss of Mg2+ causes a
reduction of chlorophyll which lowers the ability of the tree to photosynthesise. The leaching of Al3+ from
rocks into the soil affects the ability of the roots of the tree to take up sufficient water and nutrients to
survive.

12. CO32–(s) + 2H+(aq) → CO2(g) + H2O(l)

13. Calcium hydroxide and calcium oxide are both strong bases and can neutralise the acid.
Ca(OH)2(aq) + 2H+(aq) → Ca2+(aq) + 2H2O(l)
CaO(s) + 2H+(aq) → Ca2+(aq) + H2O(l)
This increases the amount of calcium ions in the lake water and also helps to precipitate aluminium ions
from the water.
14. (a)

(b) Both the carbon and the nitrogen atoms in the cyanide ion possess a non-bonding pair of electrons.
The formal charge on the carbon atom = 4 − 2 − (1/2 x 6) = −1; the formal charge on the nitrogen atom =
5 − 2 − (1/2 x 6) = 0. Since the carbon atom has a more negative formal charge it is more likely to donate
its non-bonding pair of electrons to the transition metal ion.
(c) From the spectrochemical series it can be seen that cyanide ion ligands are more electron dense than
water ligands as they causes greater splitting of the d orbitals. Because the cyanide ion is more electron
dense it is a stronger ligand than water. If aqueous iron(II) ions, [Fe(H2O)6]2+, are added to cyanide ions
the cyanide ions replace the six water ligands irreversibly to form [Fe(CN)6]4−. This means the cyanide are
no longer free to form coordinate bonds with other transition metal ions in the body.

15. The aluminium atom in AlCl3 is electron deficient as it only has six electrons in its outer shell. It can
therefore act as a Lewis acid accepting a non-bonding pair of electrons from one of the chlorine atoms
from another molecule of aluminium chloride. At the same time one of its own chlorine molecules also
donates a pair of electrons to the other aluminium atom. AlCl3 is therefore acting as both a Lewis acid and
a Lewis base.

16. (a) 2.2 x 10-13 (note that equilibrium constants do not have units)
(b) Kw = 1.6 x 10-13; so [H+(aq)] = (1.6 x 10-13)1/2 = 4.0 x 10-7 mol dm-3
(c) [OH−(aq)] = (1.6 x 10-13)1/2 = 4.0 x 10-7 mol dm-3
(d) Kw = 7.0 x 10-14 so [H+(aq)] = (7.0 x 10-14)1/2 = 2.65 x 10-7 mol dm-3 so pH = 6.6
(e) [OH−(aq)] = (2.2 x 10-13)1/2 = 4.69 x 10-7 mol dm-3 so pOH = 6.3

17. (a) After 50.1 cm3 of NaOH(aq) has been added there will be 0.1 cm3 of 0.100 mol dm-3 NaOH(aq)
present in 100.1 cm3 (say 100 cm3) of solution.
Amount of NaOH(aq) = 0.1 x 0.100 x 1.0/1000 = 1 x 10-5 mol
NaOH(aq)] = [OH–(aq)] = 1 x 10-5 x 1000/100 = 1 x 10-4 mol dm-3
pOH = – log10 1 x 10-4 = 4.00 so pH = 10.0

(b) The same answer as part (a), i.e. pH = 10.0

18. Since this is the half-equivalence point (when [HCOOH(aq)] = [HCOO–(aq)]) then pH = pKa = 3.75.

19. (a) (i) CH3COOH(aq) + H2O(l) CH3COO–(aq) + H3O+(aq);


OR
CH3COOH(l) + H2O(l) CH3COO–(aq) + H3O+(aq);
OR
CH3COOH(aq) CH3COO–(aq) + H+(aq);
Must include .
Ignore state symbols. 1

(ii) Ka =10–4.76 / 1.74 × 10–5


[H + ] 2
1.74 × 10–5 = / [H+] = 0.00187;
0.200
pH = 2.73;
Award [3] for correct final answer, allow mark for correct
conversion of [H+] to pH even if [H+] incorrect. 3

(b) (initial)[CH3COOH] = 0.500 mol dm–3 and) eqm [CH3COOH] = 0.200 mol dm–3;
(initial)[CH3COO–] = 0.300 mol dm–3 and) eqm [CH3COO–] = 0.300 mol dm–3;
Allow 0.02 moles and 0.03 moles instead of 0.200 and 0.300 mol dm–3.
[CH 3 COOH] [SALT]
[H+] = Ka –
= 1.16 × 10–5 mol dm–3 / pH = pKa + log ;
[CH 3 COO ] [ACID]
pH = 4.94;
Award [3 max] for correct final answer if no working shown. 4

(c) (if acid added) CH3COO– + H+ → CH3COOH;


(if alkali added) CH3COOH + OH– → CH3COO– + H2O;
Explanation marks cannot be awarded without equations.
Accept H+ + OH– → H2O as OH– reacts with H+ in the buffer to form water. 2

20. (i) (Kw) = [H+][OH–] / (Kw) = [H3O+][OH–];


Do not award mark if [ ] omitted or other brackets are used. 1

(ii) [H+] increases, [OH–] decreases but still some present (Kw constant) /
Kw
[OH–] cannot go to zero as equilibrium present / [OH–] = ,
[H + ]
thus [OH–] cannot be zero / OWTTE; 1
(iii) (changing T disturbs equilibrium) endothermic reaction / forward reaction
favoured / equilibrium shifts to the right;
to use up (some of the) heat supplied;
Kw increases (as both [H+] and [OH–] increase); 3

(iv) (as [H+] increases) pH decreases / pH < 7;


No mark for more acidic.
1
inverse relationship between pH and [H+]/pH = –log[H+]/pH = log10 + ;
[H ]
Accept [H3O+] in place of [H+]. 2

21. Paper 3 only (i) Acid: H2PO4–;


(Conjugate) base: HPO42–;
No mark for NaH2PO4 or Na2HPO4.
H2PO4–(aq) H+(aq) + HPO42–(aq);
Accept reverse equation or reaction with water.
Ignore state symbols, but equilibrium sign is required.
Accept OH– (ions) react with H+ (ions) to form H2O. 3

(ii) strong base/OH– replaced by weak base (H2PO42–, and effect minimized) /
strong base reacts with acid of buffer / equilibrium in (i) shifts in forward
direction;
OH–(aq) + H2PO4–(aq) → H2O(l) + HPO42–(aq);
Ignore state symbols, accept equilibrium sign.
Accept OH– added reacts with H+ to form H2O. 2
(iii) strong acid/H+ replaced by weak acid (H2PO4–, and effect minimized) /
strong acid reacts with base of buffer / equilibrium in (i) shifts in
reverse direction;
H+(aq) + HPO42–(aq) → H2PO4–(aq);
Accept reaction with H3O+.
Ignore state symbols. 2

22. (i) NH3 weak(er) base/partial dissociation;


[OH–] < 0.1(0) /pOH > 1 (thus pH < 13 / pH + pOH = 14); 2
(ii) around pH = 5;
Accept a value between 4 and 6.
strong acid–weak base titration, (thus acidic) / at equivalence point, NH4+
present is acidic / NH4+ NH3 + H+; 2

(iii) NH3(aq) + H2O(l) NH4+(aq) + OH–(aq);


Ignore state symbols, but equilibrium sign required.
+
[ NH 4 ][OH - ]
Kb = ; 2
[ NH 3 ]

(iv) [NH3] = [NH4+]; 1

(v) pOH = 14.00 – 9.25 = 4.75;


pKb (= pOH) = 4.75;
Kb = 1.78 × 10–5;
Ignore units.
Award [3] for correct final answer. 3

(vi) optimum/most effective/highest buffer capacity/50 %–50 % buffer/equally


effective as an acidic buffer and a basic buffer / OWTTE; 1

23.
(a) (i) acidic and [Fe(H2O)6]3+ is a weak acid
[Fe(H2O)6]3+(aq) [Fe(OH)(H2O)5]2+(aq) + H+(aq); 1
“FeCl3 is acidic” is not acceptable.

(ii) neutral and NaNO3 / sodium nitrate is formed from strong base
and strong acid / ions do not hydrolyse; 1
(iii) alkaline and CO32– is a weak base /
CO32–(aq) + H2O(l) HCO3–(aq) + OH–(aq); 1
Award [1] only for correct identification of solutions as acidic,
neutral and alkaline only, without explanation.

(b) nitrogen and sulfur;


kills/harms fish/aquatic life in lakes/rivers;
leaching of soils damages plant life/trees; 3

24. (a) 2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq); 4


Accept correct equation with NH4OH instead of NH3
n(H2SO4) = 0.0201×0.150 (mol);
n(NH3) = 6.03×10–3 (mol);
[NH3] = 0.241 (mol dm–3);
Award [3] for the correct final answer for the concentration
calculation.

(b) bromocresol green;


reaction of weak base and strong acid;
pH range of bromocresol green is 3.8 to 5.4/occurs at pH < 7; 3

(c) (i) Kb = 10–4.75 = 1.78×10–5;


[ NH 4+ ][OH - ]
Kb = /[OH - ] = K b [ NH 3 ];
[ NH 3 ]

[OH–] = 1.78 ´ 10 -5 ´ 0.121;


pOH = 2.83; 4
Award [4] for the correct final answer.
Allow ECF, for example any correct conversion of [OH–] to
pOH.

(ii) a solution which resists change in pH / changes pH very slightly;


when small amounts of acid or base are added;
weak acid and its salt / weak acid and its conjugate base; 3
(iii) n(NH3) = 0.00500 (mol) and n(HCl) = 0.00250 (mol);
[ NH 4+ ] = [ NH 3 ];
[OH–] = Kb = 1.78×10–5;
(pOH = 4.75 so) pH = 9.25 (allow 9.2 to 9.3); 4
Award [4] for correct final answer.
Accept other valid methods.

25. (a) (i) CH3CH2COOH + H2O CH3CH2COO– + H3O+


/ CH3CH2COOH CH3CH2COO– + H+;
required for mark. 1

(ii) (pKa for propanoic acid = 4.87)


[H+]2 = 0.100 × Ka;
[H+] = 1.16 × 10–3 (mol dm–3); 2

(b) sketch to show:


indicator range between pH 3.0 and pH 4.6 (with “yellow” at
pH 3.0 and “blue” at pH 4.6);
initial pH of acid at 2.9 ± 1.0 (when no KOH has been added);
half-equivalence point (does not need to be named) at pH 4.9
when 12.5 cm3 of KOH have been added;
equivalence point at approx pH 8.5–9.0 when 25.0 cm3 of KOH(aq)
added;
upper part of curve from 25.0–50.0 cm3 added identical to original
curve;
Award [1] each for any three points. 3 max

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