The non-redox titration Questions

I've tried to quote the data to the appropriate significant figures and
associated 'trailing zeros'.

Q1 A solution of sodium hydroxide contained 0.250 mol dm-3. Using

phenolphthalein indicator, titration of 25.0 cm3 of this solution required 22.5
cm3 of a hydrochloric acid solution for complete neutralisation.

(a) write the equation for the titration reaction.

(b) what apparatus would you use to measure out (i) the sodium hydroxide
solution? (ii) the hydrochloric acid solution?

(c) what would you rinse your apparatus out with before doing the titration ?

(d) what is the indicator colour change at the end-point?

(e) calculate the moles of sodium hydroxide neutralised.

(f) calculate the moles of hydrochloric acid neutralised.

(g) calculate the concentration of the hydrochloric acid in mol/dm3 (molarity).

 

Q2 A solution made from pure barium hydroxide contained 2.74 g in exactly
100 cm3 of water. Using phenolphthalein indicator, titration of 20.0 cm3 of this
solution required 18.7 cm3 of a hydrochloric acid solution for complete
neutralisation. [atomic masses: Ba = 137, O = 16, H = 1)

(a) write the equation for the titration reaction.

(b) calculate the molarity of the barium hydroxide solution.

(c) calculate the moles of barium hydroxide neutralised.

(d) calculate the moles of hydrochloric acid neutralised.

(e) calculate the molarity of the hydrochloric acid.

 
Q3 4.90g of pure sulphuric acid was dissolved in water, the resulting total
volume was 200 cm3. 20.7 cm3 of this solution was found on titration, to
completely neutralise 10.0 cm3 of a sodium hydroxide solution. [atomic
masses: S = 32, O = 16, H = 1)

(a) write the equation for the titration reaction.

(b) calculate the molarity of the sulphuric acid solution.

(c) calculate the moles of sulphuric acid neutralised.

(d) calculate the moles of sodium hydroxide neutralised.

(e) calculate the concentration of the sodium hydroxide in mol dm-3 (molarity).

 

Q4 100 cm3 of a magnesium hydroxide solution required 4.5 cm3 of sulphuric

acid (of concentration 0.100 mol dm-3) for complete neutralisation. [atomic
masses: Mg = 24.3, O = 16, H = 1)

(a) give the equation for the neutralisation reaction.

(b) calculate the moles of sulphuric acid neutralised.

(c) calculate the moles of magnesium hydroxide neutralised.

(d) calculate the concentration of the magnesium hydroxide in mol dm-

3
 (molarity).

(e) calculate the concentration of the magnesium hydroxide in g cm-3.

 

Q5 Magnesium oxide is not very soluble in water, and is difficult to titrate

directly.

Its purity can be determined by use of a 'back titration' method.

4.06 g of impure magnesium oxide was completely dissolved in 100 cm3 of

hydrochloric acid, of concentration 2.00 mol dm-3 (in excess).
The excess acid required 19.7 cm3 of sodium hydroxide (0.200 mol dm-3) for
neutralisation using phenolphthalein indicator and the end-point is the first
permanent pink colour.

This 2nd titration is called a 'back-titration', and is used to determine the

unreacted acid.

[atomic masses: Mg = 24.3, O = 16)

(a) (i) Why do you have to use excess acid and employ a back titration?

(ii) write equations for the two neutralisation reactions.

(b) calculate the moles of hydrochloric acid added to the magnesium oxide.

(c) calculate the moles of excess hydrochloric acid titrated.

(d) calculate the moles of hydrochloric acid reacting with the magnesium
oxide.

(e) calculate the moles and mass of magnesium oxide that reacted with the
initial hydrochloric acid.

(f) hence the % purity of the magnesium oxide.

(g) what compounds could be present in the magnesium oxide that could lead
to a false value of its purity ? explain.

doc b future note:

(i) for an insoluble carbonate you might need to use methyl orange/screened
methyl orange indicator because of dissolved carbon dioxide?

(ii) work out another problem like this where 25cm3 aliquots are titrated, more
efficient and accurate than a one off titration.
 

Q6 2.00 dm3 of concentrated hydrochloric acid (10.0 M) was spilt onto a

laboratory floor. It can be neutralised with limestone powder. [atomic masses:
Ca = 40, C = 12, O = 16)
(a) give the equation for the reaction between limestone and hydrochloric
acid.

(b) how many moles of hydrochloric acid was spilt?

(c) how many moles of calcium carbonate will neutralise the acid?

(d) what minimum mass of limestone powder is needed to neutralise the acid?

(e) If 1000 dm3 of sulphuric acid, of concentration 2.00 mol dm-3, leaked from a
tank,

calculate the minimum mass of magnesium oxide required to neutralise it.

 

Q7 A 50.0 cm3 sample of sulphuric acid was diluted to 1.00 dm3. A sample of
the diluted sulphuric acid was analysed by titrating with aqueous sodium
hydroxide. In the titration, 25.0 cm3 of 1.00 mol dm-3 aqueous sodium
hydroxide required 20.0 cm3 of the diluted sulphuric acid for neutralisation.

(a) give the equation for the full neutralisation of sulphuric acid by sodium
hydroxide.

(b) calculate how many moles of sodium hydroxide were used in the titration?

(c) calculate the concentration of the diluted acid.

(d) calculate the concentration of the original concentrated sulphuric acid

solution.
 

Q8 A sample of sodium hydrogencarbonate was tested for purity using the
following method. 0.400g of the solid was dissolved in 100 cm3 of water and
titrated with 0.200 mol dm-3 hydrochloric acid using methyl orange indicator.

23.75 cm3 of acid was required for complete neutralisation. [Ar's: Na = 23, H =
1, C = 12, O = 16]

(a) Write the equation for the titration reaction.

(b) Calculate the moles of acid used in the titration and the moles of sodium
hydrogencarbonate titrated.

(c) Calculate the mass of sodium hydrogen carbonate titrated and hence the
purity of the sample.

(d) If 0.400g of another group 1 hydrogencarbonate in its pure state, was

titrated with the same acid and it took 20.00 cm3 to neutralise it, calculate ...

(i) moles of acid needed for neutralisation and moles of hydrogen carbonate
titrated

(ii) the formula mass of the hydrogencarbonate

(iii) by working out the atomic mass of M, suggest the identity of M in the
group 1 hydrogencarbonate formula MHCO3
 

Q9 This question involves theoretical calculations to do with 'how much to

weigh out' for titrations and a common requirement to show development in
coursework projects. They involve reagents such as pure anhydrous sodium
carbonate, standardised hydrochloric acid and EDTA titrations (theory).

Atomic masses: O = 16, H = 1, Na = 23, C = 12, Ca = 40, P = 31.0

9(a)(i) Write out the equation, complete with state symbols for the reaction
between hydrochloric acid and sodium carbonate.

(ii) A pipetted 25.0 cm3 aliquot of a solution of sodium carbonate is to be

titrated with an approximately 1.0 mol dm-3 hydrochloric acid to be
standardised.

What mass of dried anhydrous sodium carbonate must be dissolved in 250

cm3 of deionised water, so that a 25.0 cm3 aliquot of the carbonate solution
will give a 20.0 cm3 titration with the hydrochloric acid?

What is the molarity of the sodium carbonate solution, assuming 100% purity.

9(b)(i) The simplified molecular structure of 2-ethanoylhydroxybenzoic acid

('Aspirin') is CH3COOC6H4COOH.

Give the equation of its reaction with sodium hydroxide.

(ii) A sample of aspirin was to be analysed for purity by titrating it with
standardised 0.100 mol dm-3 sodium hydroxide using phenolphthalein
indicator. Assuming 100% purity and access to a 4 decimal place electronic
balance, calculate the mass of Aspirin that should be weighed out to give a
titration of 23.0 cm3 of the alkali.

(iii) The main contaminant is likely to be unreacted 2-hydroxybenzoic acid.

Why is this likely to be an impurity? and how will this affect the % purity you
calculate i.e. why and how will the % purity be in error?

9(c) Pure calcium carbonate can be used to make a standard calcium ion

solution to practice a complexometric titration of calcium ions with EDTA or
determine the molarity of the EDTA reagent.

See Appendix 1. for theoretical information on EDTA structure and function in

titrations (advisable to read).

(i) Give a simple equation to show the chelation reaction between hydrated
calcium ions and the EDTA anion at pH10 and what sort of reaction is it?

(ii) To make a standard calcium ion solution 0.250 g of A.R. calcium carbonate
was dissolved in a little dilute hydrochloric acid and made up to 250 cm3 in a
calibrated volumetric flask.

Calculate the molarity of the calcium ion in this solution.

(iii) Approximately 1.0g of the solid disodium dihydrate salt of EDTA was
dissolved in 250 cm3 of water in a volumetric flask. 25.0 cm3 of this was
pipetted into a conical flask and ~1 cm3 of a conc. ammonia/ammonium
chloride pH10 buffer was added. After adding a few drops of Eriochrome
Black T indicator, the EDTA solution was titrated with the standard calcium ion
solution (from part ii) until the reddish tinge turns to blue at the endpoint. If
25.7 cm3 of the EDTA solution was required to reach the equivalence point,
what was the molarity of the EDTA?

(iv) In human teeth, approximately 96% of the outer enamel and 70% of the
inner dentine are composed of the apatite mineral, calcium hydroxy
phosphate.

If the simplest empirical formula is Ca5(PO4)3OH

calculate the % calcium in the apatite mineral.

(v) A dried 1.40g human tooth was dissolved in a small quantity of hot conc.
nitric acid. A drop of methyl orange indicator was added followed by drops of
6M sodium hydroxide until the indicator turned orange to neutralise the
solution. The solution was then made up to 250 cm3 in a volumetric flask. 10.0
cm3 of this solution was pipetted into a conical flask and ~1 cm3 of a conc.
ammonia/ammonium chloride pH10 buffer was added.

This solution was then titrated with 0.0200 mol dm-3 EDTA using Eriochrome
Black T indicator. The indicator turned blue after 22.5 cm3 of EDTA was
added. Calculate the average % by mass of calcium throughout the tooth.

Q10 25.0 cm3 of seawater was diluted to 250 cm3 in a graduated volumetric

flask.

A 25.0 cm3 aliquot of the diluted seawater was pipetted into a conical flask
and a few drops of potassium chromate(VI) indicator solution was added.

 On titration with 0.100 mol dm-3 silver nitrate solution, 13.8 cm3 was required
to precipitate all the chloride ion.

[Atomic masses: Na = 23, Cl = 35.5]

(a) Give the ionic equation for the reaction of silver nitrate and chloride ion.

(b) Calculate the moles of chloride ion in the titrated 25.0 cm3 aliquot.

(c) Calculate the molarity of chloride ion in the diluted seawater.

(d) Calculate the molarity of chloride ion in the original seawater.

(e) Assuming that for every chloride ion there is a sodium ion, what is the
theoretical concentration of sodium chloride salt in g dm-3 in seawater?

Q11 0.12 g of rock salt was dissolved in water and titrated with 0.100 mol dm-
3
 silver nitrate until the first permanent brown precipitate of silver chromate is
seen.

19.7 cm3 was required to titrate all the chloride ion.

[Atomic masses: Na = 23, Cl = 35.5]

(a) How many moles of chloride ion was titrated?

(b) What mass of sodium chloride was titrated?

(b) What was the % purity of the rock salt in terms of sodium chloride?

Q12 5.00 g of a solid mixture of anhydrous calcium chloride(CaCl2) and

sodium nitrate (NaNO3) was dissolved in 250 cm3 of deionised water in a
graduated volumetric flask. A 25.0 cm3 aliquot of the solution was pipetted into
a conical flask and a few drops of potassium chromate(VI) indicator solution
was added.

On titration with 0.1 mol dm-3 silver nitrate solution, until the first permanent
brown precipitate of silver chromate was formed, 21.2 cm3 was required to
precipitate all the chloride ion. [Atomic masses: Ca = 40, Cl = 35.5]

(a) Calculate the moles of chloride ion titrated.

(b) Calculate the equivalent moles of calcium chloride titrated.

(c) Calculate the equivalent mass of calcium chloride titrated.

(d) Calculate the total mass of calcium chloride in the original 5.0 g of the
mixture.

(e) The % of calcium chloride and sodium nitrate in the original mixture.

Q13 A bulk solution of hydrochloric acid was standardised using pure

anhydrous sodium carbonate (Na2CO3, a primary standard).

13.25 g of sodium carbonate was dissolved in about 150.0 cm3 of deionised

water in a beaker.

The solution was then transferred, with appropriate washings, into a

graduated flask, and the volume of water made up to 250 cm3, and thoroughly
shaken (with stopper on!) to ensure complete mixing.
25.0 cm3 of the sodium carbonate solution was pipetted into a conical flask
and screened methyl orange indicator added. The aliquot required 24.65
cm3 of a hydrochloric acid solution, of unknown molarity, to completely
neutralise it. [atomic masses: Na = 23, C = 12, O = 16]

(a) Calculate the molarity of the prepared sodium carbonate solution.

(b) Write out the equation between sodium carbonate and hydrochloric acid,
including state symbols.

(c) How many moles of sodium carbonate were titrated?

(d) How many moles of hydrochloric acid were used in the titration?

(e) What is the molarity of the hydrochloric acid?

Q14 For this question, the relevant formula mass and equation are in the
answers to Q13.

A 1.35g sample of impure sodium carbonate was titrated with standardised

1.00 mol dm-3 hydrochloric acid with methyl orange indicator.

If 25.3 cm3 of acid was required for complete neutralisation calculate the
following:

(a) the moles of acid used in the titration,

(b) the moles of sodium carbonate titrated,

(c) the mass of sodium carbonate titrated and hence its % purity.

Q15 (a) Describe a procedure that can used to determine the molecular mass
of an organic acid by titration with standardised sodium hydroxide solution.
Indicate any points of the procedure that help obtain an accurate result and
explain your choice of indicator.

0.279g of an organic monobasic aromatic carboxylic acid, containing only the

elements C, H and O, was dissolved in aqueous ethanol. A few drops of
phenolphthalein indicator were added and the mixture titrated with 0.100 mol
dm-3 sodium hydroxide solution.

It took 20.5 cm3 of the alkali to obtain the first permanent pink. [at. masses: C
= 12, H = 1 and O = 16]

(b) How many moles of sodium hydroxide were used in the titration?

(c) How many moles of the organic acid were titrated? and explain your
reasoning.

(d) Calculate the molecular mass of the acid.

(e) Suggest possible structures of the acid with your reasoning.

Q16 Using the method outlined in the answer to Q15(a), 0.103g of a

dibasic/diprotic non-aromatic carboxylic acid required 19.85 cm3 of a
standardised sodium hydroxide solution for complete neutralisation. If the
concentration of the alkali was 0.0995 mol dm-3. [at. masses: C = 12, H = 1
and O = 16]

Calculate ...

(a) moles of sodium hydroxide used in the titration,

(b) moles of dibasic/diprotic acid titrated giving your reasoning,

(c) the molecular mass of the acid,

(d) a possible structure of the acid.

Q17 The % purity of an organic acid can be determined by the procedure

outlined in the answer to Q15(a).

0.236g of benzoic acid required 19.25 cm3 of 0.100 mol dm-3 sodium

hydroxide for complete neutralisation.

Calculate ...
(a) moles of sodium hydroxide used in titration,

(b) moles and mass of benzoic acid titrated [at. masses: C = 12, H = 1 and O
= 16]

(c) % purity of benzoic acid from this assay titration.

Q18 Using the method described in the answer to Q15(a), sodium hydroxide

solution can be standardised. 0.250 g of very pure benzoic acid (C6H5COOH)
was titrated with a solution of sodium hydroxide of unknown molarity. If 22.5
cm3 of the alkali was required for neutralisation, calculate ...

(a) moles of acid titrated [at. masses: C = 12, H = 1 and O = 16],

(b) mol alkali used in titration,

(c) the molarity of the alkali.

Q19 The solubility of calcium hydroxide in water can be measured reasonably

accurately to 3sf by titrating the saturated solution with standard hydrochloric
acid.

(a) If the standard hydrochloric acid is made by diluting '2M' bench acid, what
volume of the '2M' acid is required to make up 250 or 500 cm3 of
approximately 0.1 mol dm-3 hydrochloric acid and how might you do it?

(b) Why must the 2M acid be diluted and why must the diluted acid be
standardised?

In the calculation below assume the molarity of the standardised hydrochloric

acid is 0.1005 mol dm-3.

(for standardisation method see Q13)

At 25oC, a few grams of solid calcium hydroxide was shaken with about 400
cm3 of deionised water, and then filtered. 50.0 cm3 samples of the 'limewater'
gave an average titration of 15.22 cm3 of 0.1005 mol dm-3 hydrochloric acid
using phenolphthalein indicator.
(c) If the acid is in the burette, how would you measure out the calcium
hydroxide solution? and why is phenolphthalein indicator used?

(d) Give the equation for calcium hydroxide reacting with hydrochloric acid.

(e) What is the reacting mole ratio of Ca(OH)2 : HCl and hence calculate the
moles of them involved in the titration.

(f) Calculate the molarity of the solution in terms of mol Ca(OH)2 dm-3.

(g) What is the approximate solubility of calcium hydroxide in g Ca(OH)2 per

100g water?

Q20 ASPIRIN ASSAY ANALYSIS This question follows on in some respects

from Q9b which I'd forgotten I'd already written, apologies for some repetition!

2-ethanoylhydroxybenzoic acid (acetylsalicylic acid), known commercially as

aspirin, can be analysed by titration with standard sodium hydroxide solution
when a sample of it is dissolved aqueous alcohol (a mixture of ethanol and
water) and using phenolphthalein indicator (pKind = 9.3, useful range pH 8.3-
10). In the pharmaceutical industry, aspirin is manufactured by reacting 2-
hydroxybenzoic acid (salicylic acid) with ethanoic anhydride. Prior to this
reaction, 2-hydroxybenzoic acid is manufactured by reacting carbon dioxide
with phenol, the mixture is heated under pressure sodium hydroxide in the so
called Kolbe Reaction. Aspirin, therefore, always contains a small percentage
of 2-hydroxybenzoic acid as an impurity!

(a) Give the equation for the Kolbe synthesis of 2-hydroxybenzoic acid.

(b) Give the equation for the formation of aspirin from 2-hydroxybenzoic acid.

(c) Give the molecular formulae and calculate the molecular masses of 2-
hydroxybenzoic acid and aspirin.

Accurate relative atomic masses: Ar(C) = 12.01, Ar(H) = 1.01, Ar(O) = 16.00

(d) Why must ethanol be added to the water prior to doing the titration?
(e) Five samples of aspirin were titrated with commercially purchased
precisely 0.1000 mol dm-3 (0.1000M) sodium hydroxide solution and the
results are given below.

The titration values were recorded to the nearest 0.05 cm3, which is
reasonable of a burette calibrated in 0.1 cm3 increments.

mass of aspirin (g) titration/cm3 of 0.1M NaOH titre/mass

0.3591 20.05 ?
0.3532 19.65 ?
0.3686 20.60 ?
0.3583 19.90 ?
0.3635 20.25 ?
av titre/mass = ?  cm3/g

In each case calculate the titre/mass and work out its average value for the
five titrations.

(f) Assuming that only aspirin was titrated (though not true), from the average
titre/mass figure calculate the 'theoretical' % purity of the aspirin by the
following sequence:

(i) What volume of 0.1000 M NaOH is equivalent to 1.000 g of aspirin?

(ii) Give the reaction equation for the titration.

(iii) How many moles of aspirin can be titrated by your answer to (i)

(iv) from (iii) calculate the theoretical mass of aspirin titrated.

(v) From (iv) calculate the theoretical % purity of the aspirin!

(g) Why is the theoretical % purity based on this titration method always likely
to be over 100%?, ignoring any titration errors - which does not necessarily
explain why via this method of analysis you will always tend to get >100%,
especially if you do the titration very accurately!

(h) Assuming that 2-hydroxybenzoic acid is titrated with NaOH on a 1 : 1

molar basis, calculate the % of this impurity in the aspirin by the follow
sequence:

(i) From your answer to (f)(iii) calculate an average molecular mass

(ii) From the average molecular mass, and a little bit of algebra, using x as the
% of the 2-hydroxybenzoic acid impurity, calculate the value of x.

(i) Suppose for the sake of argument, there was an error of 0.1 cm3 on the
titration value which is likely to be the biggest source of error. Obviously there
are errors associated with the NaOH molarity, the weighing, burette reading.

(i) What is the approximate % error on the titration value?

(ii) What error range of values for Mr(av) would this give?

(iii) Using the minimum and maximum values from (ii), recalculate the % of 2-
hydroxybenzoic acid in the aspirin using the method indicated in (h) and quote
the range of possible values.

(iv) Comment on the results of your calculations, a bit worrying for some
coursework projects! yes?

(v) In principle, what must an alternative method be capable of doing? Can

you suggest an appropriate method - and forget acid-alkali titrations!
ANSWERS
Most of the answers have been rounded up or rounded down to three
significant figures (3sf)

Q1 ANSWERS (a) NaOH(aq) + HCl(aq) ==> NaCl(aq) + H2O(l)

(b) (i) pipette (ii) burette

(c) everything with distilled water, then pipette with a little of the NaOH(aq)
and the burette with a little of the HCl(aq)

(d) pink to colourless, the first drop of excess acid removes the pink alkaline
colour of phenolphthalein

(e) moles sodium hydroxide neutralised: 0.250 x 25.0/1000 = 0.00625 mol

NaOH

(remember: moles = molarity x volume in dm3 and its two rearrangements and

1 dm3 = 1000 cm3)

(f) moles HCl = moles NaOH (equation) = 0.00625 mol HCl (in 22.5 cm3)

(g) concentration hydrochloric acid = 0.00625 x 1000 ÷ 22.5 = 0.278 mol

dm-3 (3sf)

(scaling up to 1 dm3 = 1000 cm3 to get the molarity)

Another way to work it out is 22.5 cm3 = 22.5 ÷ 1000 = 0.0225 dm3

Therefore molarity = 0.00625 ÷ 0.0225 =  0.278 mol dm-3

 

Q2 ANSWERS (a) Ba(OH)2(aq) + 2HCl(aq) ==> BaCl2(aq) + 2H2O(l)

(b) formula mass of Ba(OH)2 = 171, moles = 2.74 ÷ 171 = 0.016 mol in 100
cm3, (scaling up x 10)

therefore 0.16 mol in 1000 cm3, so molarity of Ba(OH)2 = 0.16 mol dm-3
(c) moles Ba(OH)2 used in titration = 0.16 x 20/1000 = 0.0032 mol

(d) moles HCl titrated = 2 x moles of Ba(OH)2 used (2 : 1 in equation) 2 x .

0032

= 2 x 0.0032 = 0.0064 mol HCl in 18.7 cm3 of the acid solution, 18.7 cm3 =
0.0187 dm3

(e) therefore molarity of HCl(aq) = 0.0064/0.0187 = 0.342 mol dm-3

 

Q3 ANSWERS (a) 2NaOH(aq) + H2SO4(aq) ==> Na2SO4(aq) + 2H2O(l)

(b) moles H2SO4 = 4.90 ÷ 98 = 0.050 mol in 200cm3

scaling up to get molarity of the sulphuric acid solution, 0.050 x 1000 ÷

200 = 0.25 mol dm-3

(c) moles of sulphuric acid neutralised = 0.250 x 20.7/1000 = 0.005175 mol

(d) moles of sodium hydroxide neutralised = 2 x 0.005175 = 0.01035 mol (2 :

1 in equation)

(e) concentration of the sodium hydroxide = 0.01035 x 1000 ÷ 10 = 1.035 mol

dm-3 (molarity 1.04, 3sf)
 

Q4 ANSWERS (a) Mg(OH)2(aq) + H2SO4(aq) ==> MgSO4(aq) + 2H2O(l)

(b) moles of sulphuric acid neutralised = 0.100 x 4.5/1000 = 0.00045 mol

(c) moles of magnesium hydroxide neutralised also = 0.00045 (1:1 in

equation) in 100 cm3

(d) concentration of the magnesium hydroxide = 0.00045 x 1000 ÷

100 = 0.0045 mol dm-3

(scaling up to 1000cm3 = 1dm3,  to get molarity)

(e) molar mass of Mg(OH)2 = 58.3

so concentration of the magnesium hydroxide = 0.0045 x 58.3 = 0.26 g dm-
3
 (= g per 1000 cm3),

so concentration = 0.26 ÷ 1000 = 0.00026 g cm-3

 

Q5 ANSWERS (a)(i) The magnesium oxide is insoluble in water and so

cannot be titrated directly by a volumetric analysis method. By dissolving
in excess acid you are sure to get all the MgO into solution, and then
determine the excess acid, from which you can derive the amount of MgO that
dissolved.

(a)(ii) MgO(s) + 2HCl(aq) ==> MgCl2(aq) + H2O(l)

NaOH(aq) + HCl(aq) ==> NaCl(aq) + H2O(l)

(b) moles of hydrochloric acid added to the magnesium oxide = 2 x

100/1000 = 0.20 mol HCl

(c) moles of excess hydrochloric acid titrated = 19.7 ÷ 1000 x 0.200 = 0.00394

mol HCl

{mole ratio NaOH : HCl is 1 : 1 from equation (ii)}

(d) moles of hydrochloric acid reacting with the magnesium oxide = 0.20 -

0.00394 = 0.196 mol HCl

(e) mole MgO reacted = 0.196 ÷ 2 = 0.098 {1: 2 in equation (i)}

the formula mass of MgO = 40.3

therefore mass of MgO reacting with acid = 0.098 x 40.3 = 3.95 g

(f) % purity = 3.95 ÷ 4.06 x 100 = 97.3% MgO

(g) Mg(OH)2 from MgO + H2O, MgCO3 from the original mineral source, both

of these compounds react with acid and would lead to a false titration value.
 

Q6 ANSWERS (a) CaCO3(s) + 2HCl(aq) ==> CaCl2(aq) + H2O(l) + CO2(g)

(b) moles of hydrochloric acid was spilt = 2.00 x 10.0 = 20 mol HCl

(c) moles of calcium carbonate to neutralise the acid = 20 ÷ 2 = 10.0 mol

CaCO3 (1:2 in equation)

(d) formula mass of CaCO3 = 100,

so mass of limestone powder needed to neutralise the acid = 100 x

10 = 1000g CaCO3

(e) the neutralisation reaction is MgO + H2SO4 ==> MgSO4 + H2O,

moles H2SO4 = 1000 x 2 = 2000 mol acid, 2000 mol MgO needed (1:1 in

equation),

mass MgO needed = 2000 x 40.3 = 80600 g or 80.6 kg

 

Q7 ANSWERS (a) 2NaOH(aq) + H2SO4(aq) ==> Na2SO4(aq) + 2H2O(l)

(b) moles of sodium hydroxide used in the titration = 25.0 x 1/1000 = 0.025

mol NaOH

(c) mol H2SO4 = mol NaOH ÷ 2 = 0.0125 mol in 20.0 cm3,

so scaling up to 1000 cm3 to get molarity of diluted acid = 0.0125 x 1000 ÷

20 = 0.625 mol dm-3

(or molarity = 0.0125 mol/0.02 dm3 = 0.625 mol dm-3)

(d) scaling up from 50 to 1000 cm3, gives the concentration of the original

concentrated sulphuric acid solution,

 = 0.625 x 1000 ÷ 50 = 12.5 mol dm-3

 

Q8 ANSWERS (a) NaHCO3(s) + HCl(aq) ==> NaCl(aq) + H2O(l) + CO2(g)

(b) mol = molarity x volume in dm3, mol acid = 0.200 x 23.75/1000 = 4.75 x 10-
3 
mol HCl
from equation HCl:NaHCO3 is 1:1 by ratio

so mol HCl = mol NaHCO3 = 4.75 x 10-3

(c) mass = mol x formula mass, f. mass NaHCO3 = 23 + 1 + 12 + (3 x 16) =

84

mass NaHCO3 = 4.75 x 10-3 x 84 =  0.399 g

% purity of NaHCO3 = 0.399 x 100/0.40 =  99.75% (99.8%, 3sf)

(d)(i) mol = molarity x volume in dm3, mol acid = 0.200 x 20.00/1000 = 4.00 x

10-3 mol HCl

from equation above HCl : MHCO3 is 1 : 1 by ratio

so mol HCl = mol MHCO3 = 4.00 x 10-3

(ii) to get to the relative formula mass

moles = mass / Mr,  Mr = mass / mol = 0.400 / 4.00 x 10-3 = 100

(iii) for MHCO3, Mr(HCO3) = 1 + 12 + 48 = 61, Ar (M) = 100 - 61 = 39,

which, from the periodic table relative atomic mass values, corresponds to
potassium

So the formula of the group 1 hydrogencarbonate titrated was KHCO3

Q9 ANSWERS (a)(i)  Na2CO3(aq) + 2HCl(aq) ==> 2NaCl(aq) + H2O(l) + CO2(g)

9a(ii) 20.0 cm3 of 1.0 mol dm-3 hydrochloric acid contains 1.0 x 20.0/1000 =

0.02 mol HCl

From the equation, 0.020 mol HCl reacts with 0.010 mol Na2CO3, Mr(Na2CO3)
= 106

therefore mass Na2CO3 titrated = 0.01 x 106 = 1.06 g per aliquot,

since 250 cm3 is 1/10th of the aliquot, 10 x 1.06 = 10.6 g of Na2CO3 would be

used to make up the solution.
Molarity of Na2CO3(aq) = (10.6 g/106 g mol-1)/0.25 dm3 = 0.40 mol dm-3

9(b)(i) CH3COOC6H4COOH + NaOH ==> CH3COOC6H4COO-Na+ + H2O

9b(ii) 23.0 cm3 of 0.100 mol dm-3 NaOH contains 0.100 x 23.0/1000 = 0.0023

mol NaOH

From the equation, mol Aspirin = mol NaOH, Mr(CH3COOC6H4COOH) = 180

so need Aspirin mass of 0.0023 x 180 = 0.414 g

9b(iii) The last stage in the synthesis of 2-ethanoylhydroxybenzoic acid

('Aspirin') is made by esterifying 2-hydroxybenzoic acid with ethanoic
anhydride.

Mr(HOC6H4COOH) = 138, is 42 units less than aspirin. In terms of this

particular impurity the % aspirin will be overestimated for the following
reason. The 2-hydroxybenzoic acid will also be titrated with the aspirin, and,
with its smaller molecular mass, it will need more alkali to neutralise than
aspirin per equivalent mass of material. This can result in >100% purity!!!!

9(c)(i) It is a ligand substitution/replacement reaction.

[Ca(H2O)6]2+(aq) + EDTA4-(aq) ==> [CaEDTA]2-(aq) + 6H2O(l)

more simply Ca2+(aq) + EDTA4-(aq) ==> [CaEDTA]2-(aq)

or [Ca(H2O)6]2+(aq) + H2EDTA2-(aq) ==> [CaEDTA]2-(aq) + 2H+(aq) + 6H2O(l)

more simply Ca2+(aq) + H2EDTA2-(aq) ==> [CaEDTA]2-(aq) + 2H+(aq)

9(c)(ii) Mr(CaCO3) = 100, mol CaCO3 = mol Ca2+ in solution = 0.250/100 =

0.00250 mol

since 250 cm3 = 0.25 dm3, molarity Ca2+ = 0.0025/0.25 = 0.010 mol dm-3

9(c)(iii) mole CaCO3 = mol Ca2+ = mol EDTA used in titration.

Therefore from c(ii) mol Ca2+ = mol EDTA = 0.01 x 25.0/1000 = 0.00025 mol in
25.70 cm3 (0.0257 dm3) EDTA solution,

so molarity EDTA = 0.00025/0.0257 = 0.00973 mol dm-3 (3 sf)

9(c)(iv) Mr(apatite) = (5 x 40) + 3 x (31 + 4 x 16) + (16 + 1) = 502

% Ca in apatite = 200 x 100/502 = 39.8%

9(c)(v) In the titration mol Ca2+ = mol EDTA,

therefore mol Ca2+ = 22.5 x 0.0200/1000 = 0.00045,

since 10/250 of the original solution was used in the titration,

the total mol of calcium in the tooth solution = 0.00045 x 250/10 = 0.01125
mol Ca

total mass of Ca in tooth = 0.01125 x 40 =  0.45 g

% by mass Ca in the tooth = 0.45 x 100/1.40 = 32.1 %

Q10 ANSWERS (a) Ag+(aq) + Cl-(aq) ==> AgCl(s) (sodium ions and nitrate ions
etc. are spectator ions)

(b) from equation: moles silver nitrate (AgNO3) = moles chloride ion (Cl-)

moles = molarity AgNO3 x volume of AgNO3 in dm3

= 0.100 x 13.8/1000 = 1.38 x 10-3 mol Cl- (in 25.0 cm3 aliquot)

(c) moles in 1 dm3 of diluted seawater = 1.38 x 10-3 x 1000/25 = 0.0552

(scaling up to 1000 cm3)

So molarity of chloride in diluted seawater is 0.0552 mol dm -3

(d) Now in the titration 25.0 cm3 of the 250 cm3 was used,

so the molarity of chloride ion in the original seawater must be scaled up

accordingly.

molarity of chloride ion in seawater = 0.0552 x 250/25.0 = 0.552 mol dm-3

(e) Mr(NaCl) = 23 + 35.5 = 58.5

concentration of NaCl in g dm-3 = molarity x formula mass = 0.552 x
58.5 =  32.3 g dm-3

Q11 ANSWERS (a) moles = molarity AgNO3 x volume in dm3 = 0.100 x

19.7/1000 = 1.97 x 10-3 mol Cl- ion

[AgNO3:NaCl or Ag+ : Cl- is 1 : 1, see Q10(a)/(b)] f. mass NaCl = 23 + 35.5 =

58.5

(b) mass = mol x formula mass = 1.97 x 10-3 x 58.5 = 0.1152 g NaCl

(c) % purity = 0.1152 x 100/0.12 = 96.0 % in terms of NaCl (3sf)

Q12 ANSWERS (a) mole Cl- = moles Ag+ [=AgNO3, see Q10(a)/(b)]

mole Cl- = molarity AgNO3 x vol AgNO3 = 0.100 x 21.2/1000 = 2.12 x 10-3 mol

Cl-

(b) Since calcium chloride is CaCl2, mol CaCl2 = mole Cl-/2  = 2.12 x 10-
3
/2 = 1.06 x 10-3 mol CaCl2

(c) Mr(CaCl2) = 40 + (2 x 35.5) = 111

mass = mol x f. mass = 1.06 x 10-3 x 111 = 0.1177 g CaCl2

(d) Since 1/10th of original solution titrated, original mass of CaCl2 in mixture

= 10 x 0.1177 g = 1.177g CaCl2 (1.78g 3sf)

(e) Therefore % = 1.177 x 100/5.0 =  23.5% CaCl2 (3 sf)

and % NaNO3 = 100 - 23.5  = 76.5% (3 sf)

Q13 ANSWERS (a) moles = mass/f. mass, f. mass Na2CO3 = 106, mol

Na2CO3 = 13.25/106 = 0.125

molarity = mol/vol. in dm3, 250 cm3 = 0.250 dm3,

molarity Na2CO3 = 0.125/0.250 = 0.50 mol dm-3

(b) Na2CO3(aq) + 2HCl(aq) ==> 2NaCl(aq) + H2O(l) + CO2(g)

(c) mol = molarity x volume

mol Na2CO3 titrated = 0.5 x 25.0/1000 = 0.0125 mol Na2CO3 (in the 25

cm3 aliquot pipetted)

(d) from equation, mole ratio Na2CO3:HCl is 1:2,

so mol HCl = 2 x mol Na2CO3  = 2 x 0.0125 = 0.025 mol HCl (in the 24.65

cm3 titre)

(e) molarity = mol/vol. in dm3, dm3 = cm3/1000, 24.65/1000 = 0.02465 dm3

therefore molarity HCl = 0.025/0.02465 = 1.014 mol dm-3 (1.01 3sf)

Q14 ANSWERS (a) mol HCl = 1.00 x 25.3/1000 = 0.0253 mol

(b) reacting mole ratio, Na2CO3:HCl is 1:2

so mol Na2CO3 titrated = mol HCl/2 = 0.0253/2 = 0.01265 mol

(c) mass = mol x f. mass, so mass Na2CO3 = 0.01275 x 106 = 1.34 g

therefore % purity of Na2CO3 =  1.34 x 100/1.35 =  99.3% (3sf)

Q15 ANSWERS (a) An appropriate quantity of the acid is weighed out,

preferably on a 4 sf electronic balance. It can be weighed into a conical flask
by difference i.e. weight acid added to flask = (weight of boat + acid) - (weight
of boat).  The acid is dissolved in water, or aqueous-ethanol if not very soluble
in water. The solution is titrated with standard sodium hydroxide solution using
phenolphthalein indicator until the first permanent pink.

The burette should be rinsed with the sodium hydroxide solution first. During
the titration the flask should be rinsed around the inside to ensure all the acid
and alkali react, and drop-wise addition close to the end-point to get it to the
nearest drop - the first permanent pink colour.
The pKind for phenolphthalein is 9.3, and its effective pH range is 8.3 to 10.0.
The pH of a solution of the sodium salt of the acid (from strong base + weak
acid) is in this region and so the equivalence point can be detected with this
indicator.

(b) moles = molarity x volume in dm3 (dm3 = cm3/1000)

mol NaOH = 0.100 x 20.5/1000 = 0.00205 mol

(c) mol NaOH = mol RCOOH = 0.00205

because 1:1 mole ratio for a monobasic acid: RCOOH + Na+OH- ==> RCOO-
Na+ + H2O

(d) moles = mass (g)/Mr, so Mr = mass/mol = 0.279/0.00205 = 136.1

(e) The simplest aromatic carboxylic acid is benzoic acid C6H5COOH, Mr =

122

136-122 = 14, which suggests an 'extra' CH2 (i.e. -CH3 attached to the

benzene ring instead of a H), so, since the COOH is attached to the ring,
there are three possible positional/chain isomers of CH3C6H4COOH (Mr = 136)

2-, 3- or 4-methylbenzoic acid.

Q16 ANSWERS (a) moles = molarity x volume in dm3 (dm3 = cm3/1000)

mol NaOH = 0.0995 x 19.85/1000 = 0.001975 mol

(b) The titration reaction for complete neutralisation is:

R(COOH)2 + 2Na+OH- ==> R(COO-Na+)2 + 2H2O

this 1 : 2 reaction mole ratio means that mol dibasic acid = mol NaOH/2 =
0.001975/2 = 0.0009875
(c) moles = mass (g)/Mr, so Mr = mass/mol =
0.103/0.0009875 = 104.3 (approx. 104 3sf)

(d) Since a dibasic acid, and 2 x COOH = 2 x 45 = 90 mass units, the

remaining 14 units could be CH2,

and so the structure is likely to be HOOC-CH2-COOH,

propanedioic acid (malonic acid), Mr = 144

Q17 ANSWERS (a) mol NaOH = 0.100 x 19.25/1000 = 0.001925

(b) mol NaOH = mol acid = 0.001925, mol ratio 1:1, C6H5COOH + Na+OH- ==>
C6H5COO-Na+ + H2O

Mr (C6H5COOH) =122, mol = mass (g)/Mr or mass = mol x Mr

so mass acid = 0.001925 x 122 = 0.2349 g

(c) % purity = actual mass of acid titrated x 100 / mass of original sample

% purity = 0.2349 x 100/0.236 = 99.5% (3 sf)

Q18 ANSWERS (a) Mr (C6H5COOH) =122, mol acid = mass (g)/Mr =

0.250/122 = 0.002049 mol

(b) mol alkali = 0.002049 mol, since mol acid, 1:1 mole ratio in reaction (see
Q17(b)).

(c) Since 0.002049 mol NaOH in 22.5 cm3, so scaling up

molarity NaOH = 0.002049 x 1000/22.5 =  0.0911 mol dm-3 (3 sf)

Q19 ANSWERS (a) The ratio of 2M/0.1M is 20, so need to do 20 fold dilution.

So 25.0 cm3 of 2M diluted to 500 cm3 gives an approximately 0.1 mol dm-

3
 solution. You can do this with a measuring cylinder and beaker.
In practice you could make up 12.5 cm3 of the 2M acid up to 250 cm3. You
could do this with a burette and a 250 cm3 standard volumetric flask, but
standardisation of the acid is still required.

(b) The solubility of calcium hydroxide is low, so it would give a very

inaccurate tiny titration value with relatively concentrated acid. For any
accurate work e.g. to 3sf, standardisation of reagents is required.

(c) 1 x 50.0 cm3 pipette or 2 x 25.0 cm3 pipette would be the most convenient

(or accurate burette?). Phenolphthalein is used for strong base-strong acid
titrations.

(d) Ca(OH)2(aq) + 2HCl(aq) ==> CaCl2(aq) + 2H2O(l)

(e) from equation, mole ratio Ca(OH)2 : HCl is 1:2

and since moles solute = molarity x volume in dm3

mol HCl used in titration = 0.1005 x 15.22/1000 = 0.001530 mol HCl

therefore mol Ca(OH)2 = 0.001558/2 = 0.000765 mol Ca(OH)2

(f) Scaling up from mol Ca(OH)2 in 50 cm3 to 1 dm3 (1000 cm3)

molarity Ca(OH)2 = 0.00765 x 1000/50 = 0.1558 = 0.153 mol dm-3 (to 3sf)

(g) Mr[Ca(OH)2] =74, so solubility in g dm-3 = 0.153 x 74 = 1.13 g dm-3 (3 sf)

Since density of water is ~1.0 g cm-3, the solubility of Ca(OH)2 is about

0.113 g/100 cm3 H2O

Q20 ANSWERS (a)   + CO2 === heat/pressure/NaOH ==> 

(sodium salts status ignored)

(b)   +   == reflux ==>   + 

(c) 2-hydroxybenzoic acid Mr(C7H6O3) = 138.1, aspirin Mr(C9H8O4) = 180.3

(d) Aspirin is not very soluble in pure water and is much more soluble in
ethanol solvent.

(e) The titre/mass data: Note: If you use average mass/average titre you get
55.73 cm3 0.1000M NaOH/g

Note that Q9b explains why 0.35-0.40g is a convenient mass to weigh out for
an individual titration.

mass of aspirin (g) titration/cm3 of 0.1M NaOH titre/mass

0.3591 20.05 55.83
0.3532 19.65 55.63
0.3686 20.60 55.89
0.3583 19.90 55.54
0.3635 20.25 55.71
av titre/mass =  55.72 cm3/g

(f) (i) 55.72 cm3

(ii)   + NaOH ==>   + H2O

(iii) From the titration equation, 1 mole of aspirin = 1 mole of NaOH

therefore mol aspirin = mol NaOH = 55.72 x 0.1000 / 1000 = 0.005572

mol (mol = molarity x volume in dm3)

(iv) mass = Mr(aspirin) x 0.005572 = 180.3 x 0.005572 = 1.00463g

(v) % purity = 100 x g mass titrated/ 1g = 100.5% (1dp, 4sf)

(g) You need to re-read the opening paragraph of the question, particularly
the last line. The problem with this titration is that you also titrate the 2-
hydroxybenzoic acid impurity. This has a smaller molecular mass than aspirin,
therefore for equivalent masses, the 2-hydroxybenzoic acid will give more
moles to react with the NaOH and so give a false, and over estimated value of
moles of aspirin, hence a % purity of >100.

(h) (i) The moles of acid = 0.005572 for 1g, since Mr = mol/mass, Mr(av) =
1/0.005572 = 179.5

(ii) Mr(av) = 179.5 = {x X 138.1(C7H6O3) + (100-x) X 180.3(C9H8O4)} / 100

where x = the % of 2-hydroxybenzoic acid, and multiplying through by 100

gives ...

17950 = 138.1x + 18030 - 180.3x

which on rearranging gives ...

42.2x = 80, x = 80/42.2 = 1.9

therefore the aspirin contained 1.9% impurity of 2-hydroxybenzoic acid.

(i) (i) % error = ~ 0.1 x 100 /20 = 0.5% (this would be good for any
student!)

(Other sources of error are ignored for the purpose of this calculation)

(ii) The error range would be 179.5 ±0.5% of 179.5, 179.5±0.9, giving a range
of 178.6 to 180.4.

(iii) Using an Mr(av) of 178.6 gives 4.0% of 2-hydroxybenzoic acid, 180.4

gives -0.24% !

(iv) This means, for a not unreasonable error range based on the titration, that
a wide range of values of the % impurity in the aspirin, including the possibility
of a -ve percentage. One must conclude that this is not a very accurate
method for small percentages of this particular acidic impurity. It seems at first
that the 0.5% error seems ok, but it isn't in reality, the error in the method is
comparable to the actual % of the impurity!
(v) For low % impurity you need, if possible, a method that directly, as well as
accurately measures the impurity. In this case you can use colorimetry, e.g.
measure the absorbance of the colour produced by reacting the 2-
hydroxybenzoic acid with iron(III) chloride solution. This gives a purple colour
and is a test for the phenol group. (I haven't written this up yet!, but I have
described the use of colorimetry in determining the formula of a transition
metal complex which outlines the essential principles.)