Answers to end-of-chapter questions

Chapter 20
1 a i pH = log10[H+] ii Kw = [H+][OH] iii K a = [H+ ][A ]  [HA] [1] [1] [1] [1] [1] [1] b methyl orange will change colour at a point corresponding to the maximum pH change at neutralisation; [1] phenolphthalein changes colour between pH 810 which does not correspond to the steepest slope of the graph (it would change colour after neutralisation, and it would change very slowly) [1] c
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0

b [H+] = 0.00400moldm3 pH = log10(0.00400) = 2.40 c Ka = 1.51 105 = [H+ ]2  0.00400

= 2.46 104moldm3 pH = log10(2.46 104) = 3.61 number of moles 0.25 = volume in dm 3 2.00 = 0.125moldm3 Kw = [H+][OH] = 1.00 1014mol2dm6 Kw 1.00 1014 [H+]= = [OH ] 0.125 d [NaOH] = = 8.00 1014moldm3 pH = 13.1  2 a
12 11 10 9 8 7 6 5 4 3 2 1 0 0 10 Volume of NH3(aq) added / cm3

[1] [1]

[1]

pH

so [H+] = (1.51 10 5 ) (0.00400)

50 Volume of ethanoic acid added / cm3

[1] [1] Total = 11

initial pH less than 1 (since strong acid pH of 0.7) vertical line at 10cm3 to show maximum pH change when the volume of ammonia is near the equivalence point; line tails off to pH about 10 since ammonia is a weak base

[1] [1] [1]

initial pH at about 13.3 (since strong base) [1] vertical line at 50cm3 to show maximum pH change when the volume of ethanoic acid is near the equivalence point; [1] (the ethanoic acid is half the concentration of the sodium hydroxide) line tails off to about pH 3 since ethanoic acid is a weak acid [1] d phenolphthalein will change colour at a point corresponding to the maximum pH change at neutralisation; [1] methyl orange changes colour between pH 34.5, which does not correspond to the steepest slope of the graph (it would change colour after neutralisation, and it would change very slowly) [1] e bromocresol green is suitable for the HCl/NH3 titration; [1] since its pKa value is within the range 46 (so its colour will change at the end point); [1] neither indicator is suitable for the ethanoic acid/sodium hydroxide titration; [1] since neither pKa value is within the range 810 where the steepest pH change occurs [1]  Total = 14

PH

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Answers to end-of-chapter questions: Chapter 20

3 a rearrange the equilibrium expression to make [H+] the subject: [CH3COOH] [H+] = Ka  [CH3COO ] 0.100 [H+] = 1.74 105 0.100 = 1.74 105moldm3 so pH = log10[H+] = log10(1.74 105) = 4.76 b here we have to rearrange the equilibrium expression to make the conjugate base (sodium ethanoate) the subject: [H+ ][CH3COO ] [CH3COOH] [CH3COOH] [CH3COO] = Ka [H+ ] K a =

[1]

[1] [1]

convert pH 5.40 to [H+] pH = log10[H+] so [H+] = 3.98 106moldm3 [1] use equilibrium expression: [CH3COOH] [CH3COO] = Ka  [1] [H+ ] calculate [CH3COO] [CH3COO] = 1.74 105 c 0.0100  [1] 3.98 106 [CH3COO] = 0.0437moldm3 [1] number of moles = concentration volume in dm3 = 0.138 2 = 0.0874mol [1] The buffer solution contains a conjugate pair of weak acid and conjugate base. CH3COOH(aq) H+(aq) + CH3COO(aq) [1] The added acid combines with the ethanoate ions to form un-ionised ethanoic acid / the equilibrium shifts to the left on adding more hydrogen ions (from the hydrochloric acid). [1] The changes in the concentrations of un-ionised acid and conjugate base will be small, so the pH will not change significantly. [1] Total = 11 [1] [1]

ii the common ion effect is the decrease in the solubility of a dissolved salt [1] by adding a solution of a compound which has an ion in common with the dissolved salt [1] b i Ksp = [Cu+][Br] Since the concentrations of Cu+ and Br ions are the same, we can write the equilibrium expression: Ksp = [Cu+]2 3.2 108 = [Cu+]2 [1] + 8 so [Cu ] = 3.2 10 = 1.8 104moldm3 [1] (This is also the solubility of copper(I) bromide since one formula unit of CuBr contains one Cu+ ion.) ii Ksp = [Cu+][Br] the bromide ion concentration is 0.0100moldm3 (neglecting the Br from the CuBr) so 3.2 108 = [Cu+] (0.0100) [Cu+] = 3.2 106moldm3 [1] iii The addition of the common ion Br; [1] has shifted the equilibrium to the left (so copper(I) bromide precipitates). [1]  Total = 9 moles volume (in dm3 ) 6.00 6.00g of ethanoic acid = = 0.100mol 60.0 0.100 concentration = = 0.500moldm3 0.200 12.3 b 6.00g of sodium ethanoate = 82.0 = 0.150mol 5 a concentration = concentration = c [H+] = Ka 0.150 = 0.750moldm3 0.200

[1] [1]

[1] [1]

4 a i product of the ionic concentrations in a saturated solution; with each concentration raised to the power of the relative concentrations of the ions (Ksp = [Cy+]x[Ax]y for 2 marks)
2
Answers to end-of-chapter questions: Chapter 20

[CH3COOH] [CH3COO ] 0.500 [H+] = 1.74 105 0.750 5 = 1.16 10 moldm3 so pH = log10[H ] = log10(1.16 10 ) = 4.94
+ 5

[1] [1]

AS and A Level Chemistry Cambridge University Press

d in the equilibrium CH3COOH(aq) H+(aq) + CH3COO(aq) + added H ions are removed because they react with ethanoate ions to form un-ionised ethanoic acid molecules; [1] added OH ions are removed because they react with H+ ions to form water molecules and the equilibrium shifts to the right to form more ethanoate ions; [1] there are still relatively high amounts of un-ionised ethanoic acid and ethanoate ions in the solution, so the pH does not change very much [1] e the equilibrium is CO2(g) + H2O(l) HCO3(aq) + H+(aq) [1] + excess H ions combine with HCO3 ions and the position of equilibrium moves to the left; [1] excess OH ions are neutralised by H+ ions and the equilibrium moves to the right to restore [H+] and minimise change in pH [1]  Total = 12 6 a Ksp = [Cu ] [S ] [1] b Mr (Cu2S) = (2 63.5) + 32.1 = 159.1 1.91 10 12 concentration in moldm3 = 159.1 = 1.20 1014moldm3 [1] for every formula unit of Cu2S that dissolves, two Cu+ ions and one S2 ion are formed; [S2] = 1.20 1014moldm3 [Cu+] = 2 (1.20 1014)moldm3 = 2.40 1014moldm3 [1] + 2 2 Ksp = [Cu ] [S ] [1]
+ 2 2

inserting the values: Ksp = (2.40 1014)2 (1.20 1014) = 6.91 1042mol3dm9


c copper(II) chromate will be precipitated / a precipitate will be observed; [1] the product of the ions in solution exceeds the solubility product of copper(II) chromate / [Cu2+][CrO42] > Ksp [1] because of the common ion effect / copper(II) ions are present in both compounds [1]  Total = 9 7 a hydrochloric acid is a strong acid so [HCl] = [H+] pH = log10(0.25) = 0.56 b Kw = [H+][OH] = 1.00 1014mol2dm6 (since [H+] = [OH], Kw (1.00 1014) = [H+]2) so [H+] = 2.00 1013moldm3 pH= 12.7 c i methyl orange changes colour between pH 3 and 4.5 which does not correspond to the steepest slope of the graph ii phenolphthalein will change colour at a point corresponding to the maximum pH change at neutralisation d first convert pH to [H+] [H+] = 103.1 = 7.94 104moldm3 since [H+] = [C2H5COO] [H+ ]2 [H+ ]2 or K a =  [HA] [C 2 H5COOH] entering the values: (7.94 104 )2 K a =  (0.0500) K a = = 1.26 105moldm3 

[1 mark for value; 1 mark for correct units]

[2]

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

[1] [1] Total = 9

AS and A Level Chemistry Cambridge University Press

Answers to end-of-chapter questions: Chapter 20