The acid-base titration involves a neutralisation reaction.

Here an acid or base of known

concentration is used to determine the concentration of a given base or acid by neutralisation. In
this type of titration, a drop of an indicator is used at the start, which changes its colour to
indicate the endpoint. The indicator changes the colour with the change in the pH of the solution.
A suitable indicator should be used to determine the equivalence point and reduce indicator
error.

1. What is the molarity of the solution of barium hydroxide, if 35 ml of 0.1 M HCl is used in
the titration of 25 ml of the barium hydroxide solution?

(a) 0.35

(b) 0.07

(c) 0.28

(d) 0.14

Answer: (b)

2. Which of the following titrations will have the equivalence point at a pH more than 8?

(a) HCl and NH3

(b) CH3COOH and NH3

(c) HCl and NaOH

(d) CH3COOH and NaOH

Answer: (d)

3. Which of the following is used as an indicator in the titration of a strong acid and a weak
base?

(a) Phenolphthalein

(b) Thymol blue

(c) Fluorescein

(d) Methyl orange

Answer: (d)
4. Which of the following is used as an indicator in the titration of a weak acid and a strong
base?

(a) Bromothymol blue (6 to 7.5)

(b) Methyl orange (3 to 4)

(c) Methyl red (5 to 6)

(d) Phenolphthalein (8 to 9.6)

Answer: (d)

5. The ideal indicator for the titration of strong acid and weak base should have pH range
between

(a) 5-8

(b) 4-6

(c) 8-10

(d) 7-8

Answer: (b)

6. A difference between strong and weak acid is

(a) presence and absence of halogen ions

(b) negative and positive pH

(c) complete and partial ionisation

(d) proton donation and electron acceptance

Answer: (c)

7. Find the concentration of HCl, if 10 ml of 0.5 M Ca(OH)2 is required to titrate 50 ml of

HCl.

(a) 5 M

(b) 1/10 M

(c) 10 M
(d) 1/5 M

Answer: (d)

8. Which of the following is a buffer solution?

(a) H2SO4 + CuSO4

(b) CH3COOH + CH3COONH4

(c) NaCl + NaOH

(d) CH3COONa + CH3COOH

Answer: (d)

9. If 30 ml of acid is neutralised by 15 ml of 0.2 N alkali, then the concentration of acid is

(a) 0.4 N

(b) 0.1 N

(c) 0.3 N

(d) 0.15 N

Answer: (b)

10. What is the concentration of the sulphuric acid solution, if 100 ml of the solution is
neutralised by 50 ml of 0.5 M Ba(OH)2 solution?

(a) 0.25 M

(b) 50 M

(c) 0.5 M

(d) 100 M

Answer: (a)
Unit 12 Quiz--Acid and Base Titrations

Multiple Choice (Choose the best answer.)

1. In the laboratory experiment, Heat of Acid / Base Reactions, you saw that a 2.0 M
solution of HNO3 was a great counductor of electrcity. What explains this?

HNO3 is a strong acid.

HNO3 ionizes completely in water.

HNO3 neutralizes bases.

Both A and B are correct.

 A, B, and C are correct.

 The ionic reaction for the neutralization of HCl (a strong acid) with NaOH (a strong base) is:

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

H + (aq) + Cl - (aq) + Na + (aq) + OH - (aq) H + (aq) + OH - (aq) + Na + (aq) + Cl - (aq)

H + (aq) + Cl - (aq) + Na + (aq) + OH - (aq) H2O (l) + Na + (aq) + Cl - (aq)

H + (aq) + Cl - (aq) + Na + (aq) + OH - (aq) H2O (l) + NaCl (s)

 None of the above are correct.

 The end point ( or equivalence point ) your acid / base titration between HCl and NaOH
occurred when:

the acid and the base neutralized each other.

the phenolphthalein indicator turned a faint pink color.

the moles of H += the moles of OH -.

Both A and B are correct.

 A, B, and C are correct.

The information given at Concentration HCl -- 0.35 M

right will be used in
Volume HCl -- 24.35 mL
questions
4, 5, and 6. Volume NaOH -- 36.44 mL
 The data above refers to a titration of NaOH with a known concentration of HCl. Calculate
the moles of HCl at the end point.

8.5 moles HCl

0.14 moles HCl

0.0096 moles HCl

0.0085 moles HCl

 None of the above are correct.

 Calculate the moles of NaOH present at the end point of the titration.

12.8 moles NaOH

0.013 M NaOH

0.0096 moles NaOH

0.0085 moles NaOH

 None of the above are correct.

 Calculate the molarity of NaOH.

0.23 M NaOH

0.35 M NaOH

0.53 M NaOH

1.9 M NaOH

 None of the above are correct.

 It required 42.35 mL of H2SO4 to neutralize 21.17 mL of 0.5000 M NaOH. Calculate the

concentration of H2SO4. (Hint: Write a balanced reaction to help you perform the calculation.)

0.2499 M H2SO4

0.1250 M H2SO4

0.4998 M H2SO4

1.000 M H2SO4

 None of the above are correct.

 In your acid / base titration lab, you found the molecular weight of a solid acid. Perform the
same calculation given that 0.50 g of acid required 20.00 mL of 0.25 M NaOH to titrate it.
(Assume that the acid and base react on a one-to-one molar basis.)

0.0025 g/mol
0.010 g/mol

0.10 g/mol

4.0 x 102 g/mol

 None of these answers are correct.

 A 20.0 mL of 0.500 M HCl are mixed with 15.0 mL of 0.500 M NaOH. What is true about
the resulting solution?

The solution will be acidic with a pH > 7.

The solution will be acidic with a pH < 7.

The solution will be basic with a pH > 7.

The solution will be basic with a pH < 7.

 None of the above are true.

 Calculate the pH of the mixture in problem 9. You may have to refer to questions 10 and 11
in your supplemental problems.

pH = 0.3010

pH = 0.9031

pH = 1.146

pH = 2.602

None of these are correct.

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/dm 3 (molarity).

Q2 A solution made from pure barium hydroxide contained 2.74 g in exactly 100 cm 3 of
water. Using phenolphthalein indicator, titration of 20.0 cm 3 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 cm 3 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 cm 3 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 25cm 3 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 dm 3. 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 cm 3 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 cm 3 of

deionised water, so that a 25.0 cm3 aliquot of the carbonate solution will give a 20.0 cm 3
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 cm 3 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 cm 3 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 cm 3 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 cm 3 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(CaCl 2) 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 cm 3 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 cm 3 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 cm 3 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 cm 3 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 cm 3 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 (C 6H5COOH) was titrated with a
solution of sodium hydroxide of unknown molarity. If 22.5 cm 3 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 cm 3 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 cm 3 of
deionised water, and then filtered. 50.0 cm 3 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 cm 3, 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 cm 3 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

Appendix 1. Information on EDTA structure and function

EDTA is an acronym abbreviation for the old name EthyleneDiamineTetraAcetic acid
and is used in equations.

It is a hexadentate ligand i.e. it can donate 6 electron pairs to form 6 dative-covalent

bonds and binds strongly with many metal cations Mn+ where n is usually 2 or 3.

Multi-dentate ligands are called chelating* agents, because the two ligand bonds
become part of a five membered ring system. (*The chelate is from the Greek word
meaning a crab's claw)

The solid EDTA 'off the shelf' used in analysis is usually the disodium dihydrate salt,
which has the structure

(Na+-OOCCH2)(HOOCCH2)NCH2CH2N(CH2COOH)(CH2COO-Na+).2H2O (Mr = 372.2)

The full unionised structure is (HOOCCH2)2NCH2CH2N(CH2COOH)2 which we could

abbreviate to H4EDTA since theoretically four hydrogens from the four carboxylic acid
groups are ionisable.

With increasing pH (L ==> R) the following structures becoming more likely,

H4EDTA(1) ==> H3EDTA-(2) ==> H2EDTA2-(3) ==> HEDTA3-(4) ==> EDTA4-

( for those interested pKa(1) = 2.0, pKa(2) = 2.66, pKa(3) = 6.16, pKa(4) = 10.24 )

of which H2EDTA2- is the most prominent chelating species in solutions of pH10 in

titrating calcium ions though the complex is actually formed by the combination of a
metal ion and the EDTA4- ion.

The theory behind the titration of calcium ions with EDTA reagent is a bit complicated
and the titration should be carried out in the presence of magnesium ions, usually
included in the EDTA volumetric reagent, but if not, they must be in the mixture being
titrated. This may seem to prelude an incorrect titration for calcium since magnesium
ions reacting with EDTA, but it doesn't (see explanation later).

Hydrated/hexa-aqua metal ions like aqueous calcium and magnesium ions (M 2+) give
the following reaction with EDTA reagent,

(eq 1) [M(H2O)6]2+(aq) + H2EDTA2-(aq) ==> [MEDTA]2-(aq, colourless) + 2H+(aq) + 6H2O(l)

which, for theoretical explanation of the titration and subsequent calculations, is best
simplified to

(eq 2) M2+(aq) + H2EDTA2-(aq) ==> [MEDTA]2-(aq, colourless) + 2H+(aq) (M = Mg, Ca)

and sometimes just shown as (eq 3) M2+(aq) + EDTA4-(aq) ==> [MEDTA]2-(aq)

Both calcium and magnesium EDTA complexes are strongly formed i.e. virtually 100%
to the right BUT the Kstab for the formation of the EDTA-calcium ion complex is greater
than that for the EDTA-magnesium ion complex i.e. the calcium ion complex is more
stable and calcium ions will displace magnesium ions from their EDTA complex.

The indicators used e.g. Eriochrome Black T (represented in a 'free' anionic form as
HIn2-) weakly complexes with ions such as the magnesium ion.

(eq 4) Mg2+(aq, colourless) + HIn2-(aq, blue) [MgIn]-(aq, red) + H+(aq) (M = Mg, Ca)

Both metal ions form a weak complex with the indicator at the start of the titration, but
the indicator is displaced by the stronger binding EDTA (ligand displacement reactions),
but much more slowly from the calcium complex than the magnesium complex i.e.

(eq 5) [MgIn]-(aq, red) + H2EDTA2-(aq) = fast => [MgEDTA]2-(aq, colourless) + HIn2-(aq, blue) + H+(aq)

(eq 6) [CaIn]-(aq, red) + H2EDTA2-(aq) = slow => [CaEDTA]2-(aq, colourless) + HIn2-(aq, blue) + H+(aq)

and this means without the presence of magnesium ions, the end-point is sluggish
giving an inaccurate with just the calcium ions present, because (eq 6) is too slow.

Therefore the order of complex ion stability is [CaEDTA] 2-(aq) > [MgEDTA]2-(aq) > [MgIn]-(aq)
and this order of stability is crucial to the success of the titration as the ensuing
argument will show.

In the EDTA solution are the Mg-EDTA complex ion plus excess uncomplexed EDTA
ions. As the EDTA reagent is run into the calcium ion solution the calcium ion-EDTA
complex is formed by reactions (eq 7) or (eq 8).

(eq 7) Ca2+(aq) + H2EDTA2-(aq) ==> [CaEDTA]2-(aq) + 2H+(aq)

(eq 8) Ca2+(aq) + [MgEDTA]2-(aq) ==> [CaEDTA]2-(aq) + Mg2+(aq)

In (eq 8)  the magnesium ion is displaced from its EDTA complex on a 1 : 1 molar basis
by the calcium ion and then the free magnesium ions form a red complex with the blue
indicator (eq 4) below. This continues as long as there are still Ca 2+ ions to titrate and
magnesium ions to be displaced i.e. no blue colour is seen yet.

(eq 4) Mg2+(aq, colourless) + HIn2-(aq, blue) [MgIn]-(aq, red) + 2H+(aq)

Continued addition of EDTA eventually converts all the 'free' calcium ions into their
EDTA complex ion via (eq 7 or 8), BUT, the 1st drop of excess EDTA after the calcium
ions are all complexed then releases the blue form of the indicator via the fast reaction
(eq 5),

(eq 5) [MgIn]-(aq, red) + H2EDTA2-(aq) ==> [MgEDTA]2-(aq, colourless) + HIn2-(aq, blue) + H+(aq)
so giving the sharp end point from red to blue at pH10.

In the case of analysing a mixture of calcium and magnesium ions in the same mixture,
one method is to analyse for Ca2+ as above (VCa). Obviously, you do NOT add
magnesium ions to the EDTA or the mixture being titrated if you wish to estimate the
total (Mg2+ + Ca2+). You add a known excess of standardised EDTA solution (V excess) and
then back titrate with another standardized M2+ ion solution (Vback) and the end point is
blue to red.

Therefore: (Vexcess) - (Vback) = (VCa+Mg) and (VMg) = (VCa+Mg) - (VCa)

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MCQ MOLARITY - MOLALITY - MOLE

FRACTION - PERCENT COMPOSITION
IIT JEE - AIEEE
1) Two solutions of a substance (non electrolyte) are mixed
in the following manner. 480 mL of 1.5 M first solution + 520
mL of 1.2 M second solution. What is the molarity of the
final mixture? 
(AIEEE 2005 - equivalent to IIT JEE MAIN)

1) 1.20 M 

2) 1.344 M 

3) 1.50 M

4) 2.70 M

Logic & Solution:

Molarity of a mixture, Mmix can be calculated by:

Mmix = (M1V1 + M2V2) / (V1 + V2) = (1.5 x 480) + (1.2 x 520)/(480 + 520) = 720+624/1000 =
1.344 M

Conclusion:

The correct option is '2'.

Related questions
2) The density (in g mL–1) of a 3.60 M sulphuric acid solution that is 29% H2SO4
(Molar mass = 98 g mol–1) by mass will be:

(AIEEE 2007) 

1) 1.45 

2) 1.64 

3) 1.88 

4) 1.22

Solution: 

The relation between Molarity, M and mass percent (%) is given by:

M = (% x 10 x d) / MW

Where:

MW = molecular weight of solute

d = density of solution

Therefore:

d = M x MW / (% x 10) = 3.60 x 98 / 29 x 10 = 1.216 g mL-1

Conclusion:

The correct option is '4'.

3) 25 mL of a solution of barium hydroxide on titration with 0.1 molar solution of

hydrochloric acid gave titer value of 35 mL. The molarity of barium hydroxide
solution was :
 (AIEEE 2003) 

1) 0.07 

2) 0.14 

3) 0.28 

4) 0.35

Solution: 

The reaction involved in the titration is:

Ba(OH)2 + 2HCl -------> BaCl2 + 2H2O

The equation that is used to find the molarity of unknown solutions in titrations is:

M1V1/n1 = M2V2/n2

Where

M1 and M2 are, respectively, the molarities of Ba(OH)2 & HCl solutions.

V1 and V2 are, respectively, the volumes of Ba(OH)2 & HCl solutions.

n1 = Stoichiometric coefficient of Ba(OH)2 = 1

n2 = Stoichiometric coefficient of HCl = 2

Therefore:

molarity of barium hydroxide solution, M1 = (M2V2/n2) x (n1/V1) = (0.1 x 35 / 2) x (1/25) = 0.07

M

Conclusion:

The correct option is '1'.

4) The density of a solution prepared by dissolving 120 g of urea (mol.mass = 60

u) in 1000 g of water is 1.15 g/mL. The molarity of this solution is: 

(AIEEE 2012) 

1) 1.02 M 
2) 2.05 M 

3) 0.50 M 

4) 1.78 M

Solution: 

Molarity of a solution (M) = n/V

Where:

n = number of moles of urea = 120/60 = 2 mol

V = volume of the solution = mass of solution / density of solution  =  (120 + 1000) g / 1.15 g
mL-1 = 974 mL = 0.974 L

Therefore:

M = 2 mol / 0.974 L = 2.05 mol L-1

Note: Volume of solution should be expressed in litres.

Conclusion:

The correct option is '2'.

5) Density of a 2.05 M solution of acetic acid in water is 1.02 g/mL. The molality
of the solution is: 

(AIEEE 2006) 

1) 1.14 mol kg-1 

2) 3.28 mol kg-1 

3) 2.28 mol kg-1 

4) 0.44 mol kg-1

Solution: 

Molarity of acetic acid solution = 2.05 M

Therefore the number of moles of acetic acid in 1 L solution  = 2.05 mol

mass of acetic acid in 1 L solution  = no. of moles x molar mass = 2.05 mol x 60 g mol-1 = 123 g

Note: molar mass of acetic acid is 60 g mol-1

Density, d = mass of solution / volume of solution

Hence:

mass of solution = density x volume of solution = 1.02 g mL-1 x 1000 mL = 1020 g

mass of solvent = mass of solution - mass of solute = 1020 - 123 = 897 g = 0.897 kg

molality, m = no. of moles / mass of solvent (in Kg) = 2.05 mol / 0.897 kg = 2.285 mol kg-1

Conclusion:

The correct option is '3'.

6) With increase in temperature, which of these changes? 

(AIEEE 2002) 

1) molality 

2) fraction of solute present in water 

3) weight fraction of solute 

4) mole fraction

Logic: 

Temperature will affect the volume of solution. Hence the expression for concentration that
contain volume will change with temperature.

Conclusion:

The weight fraction of solute present in water will change with temperature.

7) A 5.2 molal aqueous solution of methyl alcohol, CH 3OH is supplied. What is

the mole fraction of methyl alcohol in the solution? 

(AIEEE 2011) 
(1) 0.050 

(2) 1.100 

(3) 0.190 

(4) 0.086 

Logic & solution: 

molality of aqueous solution = 5.2 mol kg-1

Therefore, the number of moles of methyl alcohol in 1 kg of solvent (water) = 5.2 mol

And the number of moles of solvent (water)  = weight / molar mass = 1000 g / 18 g mol-1 = 55.55
mol

Hence:

Mole fraction of methyl alcohol = nMeOH /nMeOH + nwater = 5.2 / 55.55 + 5.2 = 0.08559

Conclusion:

The correct option is '4'.

Homework

1) Define molarity.

2) Define molality.

3) What is mole fraction?

4) Which concentration term has no units?