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2.
When ammonium salts are dissolved in water, the following reaction occurs.
NH4+ (aq) + H2O(1)
(a)
Identify the acid/base conjugate pairs in this reaction by writing appropriate symbols
under each of the species in the equation above.
(b)
Write an expression for the dissociation constant, Ka, for NH4+ (aq).
(c)
(Total 5 marks)
3.
There is no suitable indicator for the titration of ethanoic acid with ammonia.
Why is this?
............................................................................................................
............................................................................................................
............................................................................................................
(2)
4.
(a)
NT Exampro
(ii)
(iii)
Explain why this reaction goes almost completely to the right despite the fact that
both hydrochloric and sulphuric acids are strong.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(3)
(b)
When concentrated sulphuric acid reacts with solid sodium iodide, hydrogen sulphide,
sodium hydrogensulphate and water are formed together with one other product.
(i)
Identify this product and state how you would recognise it.
..........................................................................................................................
(2)
(ii)
(iii)
Hence write the full ionic equation for the reaction between concentrated sulphuric
acid and sodium iodide.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
(iv)
NT Exampro
(c)
Explain concisely why the type of reaction occurring in (b) does not occur with
sodium chloride.
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....................................................................................................................................
....................................................................................................................................
(2)
(Total 15 marks)
5.
Acid-base indicators are weak acids, which can be represented as HIn. In aqueous solution the
following equilibrium is set up:
HIn(aq)
H+(aq) + In(aq)
HIn and In have different colours. The dissociation constant for the indicator equilibrium is
called in.
pH is related to pKin by the equation
pH = pKin + log
(a)
(i)
[In ]
[ HIn ]
For bromophenol blue Kin = 1 104 mol dm3. Calculate the pH of a solution in
which [In] = [HIn] for this indicator.
(2)
(ii)
The colour of In is seen when [In] is roughly ten times [Hln], and the colour of
HIn when it is in tenfold excess over In. Use this information to show the
approximate range of pH over which indicator changes can be detected visually.
(2)
(b)
NT Exampro
The selection of a correct indicator for a reaction depends on the nature of the reaction and
the concentrations of the substances used. The neutralisation curves for the addition of
sodium hydroxide solution to 100 cm3 of hydrochloric acid of the same concentration are
shown for two different concentrations of acid and alkali.
(i)
It is often said that the titration of a strong acid with a strong alkali can be
performed with any indicator. In the light of the table and titration curves given,
comment on
this statement.
(2)
pK In
Indicator
Methyl orange
3.7
Bromophenol blue
4.0
Methyl red
5.1
Bromothymol blue
7.0
Phenolphthalein
9.3
Thymolphthalein
9.7
14
1.00 mol dm 3
12
0.01 mol dm 3
10
pH
8
6
4
0.01 mol dm 3
2
1.00 mol dm 3
0
0
50
100
150
volume of alkali added / cm 3
200
From a consideration of the curve below suggest a practical difficulty that could
arise if a titration were to be attempted using dilute solutions of ethanoic acid and
ammonia.
14
12
10
8
pH
6
4
2
0
0
25
volume of alkali added / cm
50
3
NT Exampro
(iii)
(c)
The titration curve for the addition of sodium hydroxide solution to ethanoic acid
is shown.
14
12
10
8
pH
6
4
2
0
0
25
50
volume of 0.1 mol dm3 sodium hydroxide3 solution / cm 3
Explain why the pH of the solution when the acid has been half-neutralised is equal
to pKa for the acid.
(ii)
Explain why at this pH the mixture acts as a buffer and why it is most effective at
this pH
(7)
(d)
Methyl orange is an azo dye, usually used as its sodium salt. It can be made by the series
of reactions shown in the flow-scheme below.
O3 S
NH 2
NaNO2 , HCl
0 5 C
O3 S
CH 3
O3 S
N+
in NaOH(aq)
CH 3
(i)
CH 3
O3 S
N
CH 3
Explain why the temperature for the first step should be above 0 C and below 5 C.
(2)
(ii)
NT Exampro
(iii)
Methyl orange is soluble in hot water, fairly soluble in cold water, and even less so
in cold aqueous sodium chloride. Suggest in outline how a sample of impure
methyl orange could be purified so as to maximize the yield. A detailed
experimental account is not required.
(4)
(Total 25 marks)
6.
(a)
pH .....................................................................................................................
(1)
(ii)
Kw ......................................................................................................................
(1)
(b)
(c)
(1)
(ii)
NaOH (aq) of concentration 0.800 mol dm3 (Kw = 1.00 1014 mol2 dm6).
(2)
(d)
(1)
NT Exampro
(ii)
(3)
(e)
A buffer solution contains HA(aq) at a concentration of 0.300 mol dm3, and its sodium
salt, NaA, at a concentration of 0.600 mol dm3. Calculate the pH of this buffer solution.
(3)
(Total 13 marks)
7.
(a)
(i)
CH3CH2COO(aq) + H3O+(aq)
Indicate, in the space provided below the equation, the two acid/base conjugate
pairs.
(2)
(ii)
Write the expression for the acid dissociation constant, Ka, for propanoic acid.
(1)
NT Exampro
(iii)
Calculate the pH of a 0.100 mol dm3 solution of propanoic acid, for which
Ka = 1.3 105 mol dm3.
(3)
(iv)
(3)
(b)
If sodium propanoate is dissolved in water, the pH of the resulting solution is not 7, but is
near to 8. By writing the equation for the reaction occurring suggest why this is so.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(c)
NT Exampro
(ii)
(3)
(Total 16 marks)
8.
(a)
(i)
(1)
(ii)
(4)
(b)
(1)
NT Exampro
(ii)
Write equations to show the two successive ionisations of sulphuric acid, H2SO4, in
water.
......................................................................................................................
......................................................................................................................
(2)
(iii)
Suggest why the concentration of hydrogen ions is not 0.20 mol dm3 in 0.100 mol
dm3 sulphuric acid.
......................................................................................................................
......................................................................................................................
(1)
(c)
2Cl2(g) + 2H2O(g)
H = 115 kJ mol1.
0.800 mol of hydrogen chloride was mixed with 0.200 mol of oxygen in a vessel of
volume 10.0 dm3 in the presence of a copper(I) chloride catalyst at 400 C. At
equilibrium it was found that the mixture contained 0.200 mol of hydrogen chloride.
(i)
(1)
(ii)
(4)
NT Exampro
10
(d)
State and explain the effect, if any, on the position of equilibrium in (c) of:
(i)
(ii)
(iii)
9.
The values of Ka for a series of organic acids at 25 C are shown in the table below:
Acid
NT Exampro
Formula
Ka/mol dm3
ethanoic acid
CH3COOH
1.75 105
chloroethanoic acid
CH2(Cl)COOH
1.38 103
bromoethanoic acid
CH2(Br)COOH
1.26 103
iodoethanoic acid
CH2(I)COOH
6.76 104
11
(a)
(i)
(1)
(ii)
(3)
(iii)
Calculate the pH of a mixture which is 0.100 mol dm3 with respect to ethanoic
acid and 0.125 mol dm3 with respect to sodium ethanoate.
(iv)
(b)
(i)
(ii)
Suggest a reason for the trend Ka values shown in the table above.
....
....
(1)
NT Exampro
12
(iii)
(c)
Ethanoyl chloride, CH3COCl, reacts violently with water, whereas chloroethanoic acid
reacts much more slowly in order to substitute the chlorine atom. Suggest why this is so.
.....
.....
.....
(2)
(Total 15 marks)
10.
(a)
Define
(i)
pH :
(1)
(ii)
Kw :
(1)
(b)
Calculate the pH of 0.100 mol dm3 sodium hydroxide solution at 25 C. The value of Kw
at this temperature is 1.0 1014 mol2 dm6.
(2)
(c)
100 cm3 of 0.100 mol dm3 sodium hydroxide solution was added to 100 cm3 of 0.200 mol
dm3 ethanoic acid.
(i)
(ii)
(iii)
(iv)
State and explain what happens if a small amount of hydrochloric acid is added to
this mixture.
(3)
(d)
NT Exampro
When the solutions in part (c) are mixed, 560 J of heat energy is evolved. If hydrochloric
acid of the same concentration is used instead of ethanoic acid, 580 J of heat energy is
13
11.
Citric acid is used in foodstuffs as an antioxidant and, together with its sodium salt, as an acidity
regulator. It occurs naturally in fruit juices.
A formula of citric acid is
CH 2 CO 2 H
HO
CO 2 H
CH 2 CO 2 H
(a)
(i)
RCO 2 + H3O+
(ii)
(b)
The use of citric acid together with its salt, sodium citrate, as an acidity regulator depends
on the ability of this mixture to act as a buffer.
(i)
(2)
NT Exampro
14
(ii)
Describe how the mixture of citric acid and sodium citrate achieves this buffering
action. Give equations for the TWO reactions you describe.
(3)
(iii)
Calculate the pH of a buffer solution containing 0.200 mol dm3 of citric acid and
0.400 mol dm3 of sodium citrate.
(2)
(c)
Citric acid forms a liquid ester which has the structural formula
CH 2 COOC 2 H 5
HO
COOC 2 H 5
CH 2 COOC 2 H 5
(i)
Describe a test you could use to show that the ester contains an OH group.
(2)
(ii)
(1)
(iii)
Treatment of the products of the reaction in (c)(ii) leads to the production of a pure
sample of citric acid. How would you show the presence of the CO2H group in
the citric acid other than by the use of an indicator?
(2)
(Total 16 marks)
NT Exampro
15
12.
Acids differ in the number of hydrogen ions that can be liberated from one molecule of the
undissociated acid. Hydrochloric acid is a strong monobasic, or monoprotic acid, liberating one
hydrogen ion per molecule. Sulphuric acid is a dibasic, or diprotic acid, its ionisation in aqueous
solution being:
H2SO4(1) + H2O(1)
Ka = very large
II
(i)
State the hydrogen ion concentration in 0.01 mol dm3 hydrochloric acid, which is a
strong acid, and hence find the pH of this solution.
(1)
(ii)
State the hydrogen ion concentration of 0.1 mol dm3 sulphuric acid arising from the
first stage of ionisation, I.
(1)
(iii)
(iv)
In fact the pH of 0.1 mol dm3 sulphuric acid is about 0.98. This indicates a
hydrogen ion concentration of 0.15 mol dm3. By considering the reactions I and II
in the presence of one anotherexplain why this is so. You are not expected to
perform any further calculations.
...
...
...
(2)
(v)
If Ka for ionisation II has a value of 0.02 mol dm3 at 80 C, state with reasons,
whether the ionisation is endothermic or exothermic.
...
...
(2)
(vi)
NT Exampro
16
(b)
Pure sulphuric acid is a liquid, with a boiling temperature of 338 C, which mixes with
water in all proportions. Hydrogen chloride is a gas with a boiling temperature of 85 C
and is extremely soluble in water.
(i)
Suggest reasons, in terms of the structure and bonding of H2SO4 and HCl for the
large difference between their boiling temperatures.
...
...
(2)
(ii)
(iii)
1.83
1920
BaSO4
9.43 106
1360
...
...
...
...
(3)
(Total 15 marks)
13.
A buffer solution of pH =3.87 contains 7.40 g dm3 of propanoic acid together with a quantity of
sodium propanoate. Ka for propanoic acid = 1.35 105 mol dm3 at 298 K.
(i)
Explain what a buffer solution is and how this particular solution achieves its buffer
function.
(8)
(ii)
(iii)
14.
NT Exampro
17
H2SO4
(i)
Cl
HCl
HSO4
Identify the conjugate acid/base pairs in this reaction by writing suitable identifying
symbols under the equation.
(2)
(ii)
(iii)
Explain why this reaction goes almost completely to the right despite the fact that both
hydrochloric and sulphuric acids are strong.
........................................................................................................................
........................................................................................................................
........................................................................................................................
(3)
(Total 6 marks)
15.
(a)
CH3CH2CO2(aq) + H3O+(aq)
(1)
(ii)
Given that Ka for this reaction is 1.35 105 mol dm3 at 298 K, calculate the pH of
a 0.100 mol dm3 solution of propanoic acid at this temperature.
(3)
(iii)
If the solution referred to in (ii) were to be diluted tenfold, it might be expected that
the pH would rise by one unit. In fact it rises by less than this. Explain.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(3)
NT Exampro
18
(b)
During a titration NaOH solution of concentration 0.100 mol dm3 was added to 30.0 cm3
of 0.100 mol dm3 propanoic acid.
(i)
What property is shown by the reaction mixture when 15.0cm3 of NaOH has been
added to the propanoic acid?
..........................................................................................................................
(1)
(ii)
(3)
(iii)
What criteria must be considered in the selection of an indicator for this titration?
..........................................................................................................................
..........................................................................................................................
(2)
(c)
When hydrochloric or nitric acid is reacted with sodium hydroxide solution, the enthalpy
change is 57.1 kJ mol1. If propanoic acid is used instead of the other acids, the
enthalpy change is less negative.
(i)
(ii)
What would be the effect on the value of H for the reaction of using ammonia
solution instead of sodium hydroxide with propanoic acid?
..........................................................................................................................
(1)
(Total 16 marks)
16.
(a)
CH3CO2 + H3O+
When hydrogen chloride dissolves in ethanoic acid, the equilibrium established is:
CH3CO2H +HCI
NT Exampro
CH3CO2H2+ + Cl
II
19
equilibrium I; .................................................................................................
..........................................................................................................................
(1)
(ii)
(b)
(c)
The value of Ka for ethanoic acid at 298 K is 1.74 105 mol dm3 and for methanoic
acid, HCO2H, it is 1.60 104 mol dm3 at the same temperature.
(i)
(1)
(ii)
(2)
(d)
(ii)
(e)
NT Exampro
(i)
Sketch with reasonable accuracy, on the axes below, how the pH changes during
the titration of 20.0 cm3 of a 0.100 mol dm3 solution of methanoic acid with 0.050
mol dm3 sodium hydroxide solution.
20
12
10
8
pH
6
4
2
0
0
10
15
20
25
30
35 40
45
3
Volume of NaOH solution/cm
50
55
60
(3)
(ii)
Select using the data below a suitable indicator for this titration. Give a brief
reason for your choice based on the curve drawn in (e)(i).
Indicator
pH Range
Bromocresol green
3.5 5.4
Bromothymol blue
6.0 7.6
Phenol red
6.8 8.4
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..........................................................................................................................
(2)
(Total 15 marks)
NT Exampro
21
17.
(a)
Sketch on the axes below the pH curve for the titration of 25 cm3 of 0.1 mol dm3 HCl
with 0.1 mol dm3 ammonia.
pH
14
0
0
(b)
10
20
30
40
50
18.
CH3CH2CO2(aq) + H3O+(aq)
(1)
(b)
Given that Ka for this reaction is 1.35 105 mol dm3 at 298 K, calculate the pH of a
0.100 mol dm3 solution of propanoic acid at this temperature.
(3)
NT Exampro
22
(c)
If the solution referred to in (ii) were to be diluted tenfold, it might be expected that the
pH would rise by one unit. In fact it rises by less than this. Explain.
........................................................................................................................
........................................................................................................................
........................................................................................................................
(3)
(Total 7 marks)
19.
(i)
Give an equation for the dissociation of propanoic acid and hence an expression for its
dissociation constant, Ka.
..........................................................................................................................
(ii)
At 25C Ka for propanoic acid is 1.30 105 mol dm3. Find the pH of a solution of
propanoic acid of concentration 0.0100 mol dm3. State any assumptions you make.
(iii)
Increasing the temperature of the propanoic acid solution causes the pH to decrease.
What does this tell you about the enthalpy of dissociation?
Justify your answer.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(9)
20.
(a)
(b)
NT Exampro
23
(c)
Given that Kb =
[OH ][ NH 4 + ]
calculate the pH of a 0.100 mol dm3 solution
[ NH 3 ]
of ammonia.
The values of Kb and Kw are 1.80 105 mol dm3 and 1.00 1014 mol2 dm6
respectively.
(Total 5 marks)
21.
(a)
(i)
(ii)
(iii)
Given that Kb =
[OH ][ NH 4 + ]
calculate the pH of a 0.100 mol dm3 solution
[ NH 3 ]
of ammonia.
The values of Kb and Kw are 1.80 105 mol dm3 and 1.00 1014 mol2 dm6
respectively.
(5)
NT Exampro
24
(b)
(i)
Sketch on the axes below the pH curve for the titration of 25 cm3 of 0.1 mol dm3
HCl with 0.1 mol dm3 ammonia.
pH
14
0
0
(ii)
10
20
30
40
50
(c)
There is no suitable indicator for the titration of ethanoic acid with ammonia.
Why is this?
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
(d)
Suggest the conditions under which ammonia could be used to convert CH3CHClCO2H to
CH3CH(NH2)CO2H.
....................................................................................................................................
(2)
(e)
NT Exampro
25
22.
(a)
(i)
(ii)
(b)
(ii)
(3)
(c)
(i)
(ii)
The dissociation constant for ethanoic acid is 1.80 105 mol dm3. Calculate the
pH of a buffer solution which has a concentration of 0.0150 mol dm3 with respect
to ethanoic acid and 0.0550 mol dm3 with respect to sodium ethanoate.
(5)
(d)
................................
...................................
(1)
(e)
25.0 cm3 of a solution of phosphoric(V) acid of concentration 0.0590 mol dm3 required
28.1 cm3 of 0.105 mol dm3 sodium hydroxide for reaction in a titration, using
phenolphthalein indicator.
(i)
NT Exampro
26
(ii)
(iii)
Write a balanced equation for the reaction of phosphoric(V) acid with sodium
hydroxide under these conditions.
..........................................................................................................................
(4)
(Total 15 marks)
23.
(i)
(ii)
24.
(i)
(ii)
The dissociation constant for ethanoic acid is 1.80 105 mol dm3. Calculate the pH of
a buffer solution which has a concentration of 0.0150 mol dm3 with respect to ethanoic
acid and 0.0550 mol dm3 with respect to sodium ethanoate.
(Total 5 marks)
25.
Hard water contains dissolved calcium or magnesium ions, which come from the rocks over
which the water has flowed. The concentration of these ions can be found in several ways.
(a)
One method is to titrate a known volume of the water with a standard solution of the
compound edta.
Edta complexes with Ca2+ ions, as well as many transition metal ions, in a 1:1 ratio. To
ensure that the edta complexes satisfactorily with the Ca2+ ions, the solution must be
buffered at about pH 10. At this pH any indicator used will change colour when all the
Ca2+ ions have been complexed. Some other divalent ions, notably Fe2+, will also
complex with edta at this pH, but this can be eliminated if a solution of potassium cyanide
is added first.
(i)
NT Exampro
27
(ii)
The buffer which is usually used in this titration is a mixture of aqueous ammonia
and ammonium chloride solution. Explain how this mixture behaves as a
buffer solution.
(iii)
A given water sample contains Ca2+ and Fe2+ as the only divalent ions. Suggest
why the addition of cyanide ions, CN, prevents the reaction of edta with Fe2+ ions.
(iv)
A 50.0 cm3 sample of tap water was titrated with edta solution of concentration
0.0100 mol dm3; 31.2 cm3 was needed before the indicator changed colour. What
is the Ca2+ ion concentration in the water in mol dm3?
(13)
(b)
A second method for the determination of Ca2+ ion concentration uses the precipitation of
the salt calcium ethanedioate; this is filtered off, dissolved in warm dilute nitric acid, and
the ethanedioate now in solution as ethanedioic acid is determined by titration with
standard potassium manganate(VII) solution.
(i)
25.0 cm3 of a solution of Ca2+ ions containing 0.0500 mol dm3 of Ca2+ ions was
treated with excess ammonium ethanedioate solution, and the precipitate of calcium
ethanedioate was filtered off. Find the mass of the salt which would be
precipitated.
(ii)
The precipitate was washed with warm dilute nitric acid until completely dissolved,
and the washings made up to 250 cm3 with pure water. 25.0 cm3 portions of this
solution were added to about 25 cm3 of dilute sulphuric acid, and the mixture was
titrated at 60C with 0.0200 mol dm3 potassium manganate(VII) solution. Write
equations for the reactions occurring, and calculate the volume of potassium
manganate(VII) solution which would be required.
(iii)
26.
NT Exampro
.................................
.................................
28