Introductory Chemistry 2013/14 J11ICH

Titrations

Background
Chemists study a wide variety of chemical reactions by titration. Titrations are a simple
means by which knowledge of a particular reaction can be used to obtain quantitative
information. Titrimetry is used for an extensive range of environmental analyses, such as
carbonate, chloride and bicarbonate. The text below will summarise, using an example,
the procedure required for this type of quantitative analysis and will illustrate the
information required to allow quantification of an analyte to be undertaken. How the
results are used to calculate the final answer will also be discussed.


Introduction
The experiment which follows was undertaken to determine the concentration of sodium
hydroxide in an unknown solution. If an acid of known concentration had been
available then this could have been used directly to determine the concentration of sodium
hydroxide. However as an acid of only approximate concentration was available, it was
necessary to standardise this using a standard base. Once the exact concentration of the
acid had been found the acid was used to quantitatively determine the concentration of
sodium hydroxide in the unknown solution.

The reactions employed are illustrated below:

Na
2
CO
3(aq)
+ 2 HNO
3(aq)
2NaNO
3(aq)
+ CO
2 (g)
+ H
2
O
(l)

sodium carbonate nitric acid sodium nitrate carbon dioxide water
(standard base) (acid to be standardised)

NaOH
(aq)
+ HNO
3(aq)
NaNO
3(aq)
+

H
2
O
(l)

sodium hydroxide nitric acid sodium nitrate water

(unknown base) (standardised acid)

Methodology
Standardising the acid was achieved by first preparing a standard base, sodium carbonate.
This was done by weighing a known amount of the base on an electronic balance,
dissolving the base with distilled water in a beaker, transferring the solution to a volumetric
flask and making up to volume (diagram 1). When preparing standard solutions and
undertaking titrations the laboratory procedures are straightforward but require careful
technique (see diagrams). Great care has to be taken when preparing the standard as it is
assumed that the calculated concentration is correct and that no errors have occurred
during the preparation! It is essential that standard solutions, indeed any quantitative
determinations, are undertaken in a meticulous manner in an attempt to avoid erroneous
results. Once the standard base had been prepared a known volume (20 mL) was
transferred to a conical flask to which a few drops of indicator were added. The unknown
acid solution was loaded into the burette and the acid was slowly added to the base in the
flask (diagram 2). As the titration neared its end, indicator molecules changed colour
near a drop of added acid due to a temporary excess of H
+
ions. As soon as the solution
was swirled, however the indictors basic colour returns. The end point in the titration
occurs when a tiny excess of H
+
ions, too small to measure as a volume, is added to change
the colour of the indicator from the basic colour to the acid colour. Thus the end point
occurs when the basic ions (OH
-
) are exactly neutralised by the acidic ions (H
+
) added.
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Diagrams




Diagram 1



Diagram 2


Apparatus

Electronic balance ( 4 decimal places ) Spatula
Weighing boat Funnel
Wash bottle Glass rod
2 x 500 mL Volumetric flasks 4 x 250 mL beakers
1 x 100 mL beaker 4 x 250 mL conical flasks
1 x 25 mL graduated pipette Pipette filler
1 x 25 mL burette (0.1 mL graduations) Retort stand and burette clamp
White tile Pasteur pipette and bulb


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3
Once the acid concentration had been determined a known volume of unknown sodium
hydroxide (20 mL) was transferred to a clean conical flask to which a few drops of
indicator were added. The unknown acid solution was loaded into the burette and the acid
was slowly added to the base in the flask (diagram 2). The end point was determined in a
similar manner to that employed previously.

The main results obtained are shown below.

Mass of sodium carbonate taken was 2.6370 grams.



Standardisation of nitric acid

Rough 1 2

Final burette reading 19.5 19.2 19.4

Initial burette reading 0.1 0.0 0.2

Total volume of acid used 19.4 19.2 19.2




Determination of unknown sodium hydroxide solution

Rough 1 2

Final burette reading 15.5 14.7 14.6

Initial burette reading 0.2 0.3 0.1

Total volume of acid used 15.3 14.4 14.5



Calculations (see also the moles route after summary)
The results can be used to calculate the concentration of sodium hydroxide in solution. In
this example this is achieved in three distinct steps.
Firstly the concentration of the primary standard is calculated. Secondly the concentration
of nitric acid is determined and thirdly the concentration of unknown sodium hydroxide is
calculated. What follows is details of these calculations together with explanation.


Firstly calculate the concentration of the prepared sodium carbonate standard.

The relative molecular mass (RMM) of sodium carbonate is 105.9888
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4

As 2.6370 grams were actually weighed the concentration of the prepared solution is given
by
mass weighed/RMM * 1000/ volume prepared in mL

As a 500 mL standard was prepared the concentration of the standard is given by

2.6370/105.9888 * 1000 / 500

Therefore the prepared sodium carbonate standard was 0.0498 M to 4 d.p.
It must be reiterated that it is essential that quantitative analysis is undertaken diligently.
Should the actual concentration of the standard be different than that calculated, due for
instance, to careless loss of material during preparation, then this will have a knock on
effect on the reliability of any subsequent results.
Now that the concentration of the base is known the results from the first titration between
the standard base and the prepared nitric acid solution can be used to find the concentration
of the acid. In order to calculate the Molarity of the nitric acid it is necessary to write an
overall balanced equation for the reaction between the acid and the standard base.

Na
2
CO
3
(aq)
+ 2 HNO
3
(aq)
2NaNO
3
(aq)
+ CO
2
(g)
+ H
2
O
(l)
Sodium carbonate Nitric acid Sodium nitrate Carbon dioxide Water

The equation that allows the Molarity to be calculated is;

M
a
* V
a
= M
b
* V
b

a b
Where;
M
a
= Molarity of nitric acid ( to be found )
V
a
= volume of nitric acid
a = number of molecules of nitric acid in the balanced equation
M
b
= Molarity of sodium carbonate
V
b
= Volume of sodium carbonate
b = number of molecules of sodium carbonate in the balanced equation

By rearranging the equation to make M
a
the subject of the equation. Then:

M
a
= M
b
* V
b
* a
b * V
a


as M
b
is 0.0498 M ; V
b
is 20 mL; a is 2; b is 1 and V
a
is 19.2 mL then, by substitution;

M
a
= 0.0498 * 20 * 2
1 * 19.2

The Molarity of the nitric acid was found to be 0.1037M to 4.d.p

Note: It must be pointed out that whilst Molarities have been quoted to 4 decimal places,
the actual Molarity (to many decimal places) is used in the calculations. This prevents
any bias from being be carried forward to further calculations which, if included, would
impair the final answer.
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5

Now that the concentration of the acid is known, the Molarity of the unknown sodium
hydroxide solution can be calculated using the second of the titration results.
Again an overall balanced equation of the reaction is required.

NaOH
(aq)
+ HNO
3(aq)
NaNO
3(aq)
+

H
2
O
(l)

Sodium hydroxide Nitric acid Sodium nitrate Water


The equation that allows the Molarity to be calculated is;

M
a
* V
a
= M
c
* V
c

a c

Where
M
a
= Molarity of nitric acid
V
a
= volume of nitric acid
a = number of molecules of nitric acid in the balanced equation
M
c
= Molarity of sodium hydroxide (to be found)
V
c
= Volume of sodium hydroxide
c = number of molecules of sodium hydroxide in the balanced equation



By rearranging the equation to make M
c
the subject of the equation. Then;

M
c
= M
a
* V
a
* c
a * V
c


by substituting the appropriate values into the above equation the following results

M
c
= 0.1037 * 14.45 * 1
1 * 20

The Molarity of the unknown sodium hydroxide solution was found to be 0.0749 M to 4
decimal places.

In the above equation the average of the 2 accurate titrations are used in the calculation.
Commonly when undertaking titrations, especially when the end point is unknown a rough
titration is undertaken to give an idea of the end point volume. This end point result is not
fit for quantitative analysis due to the non-quantitative manner in which the result is
determined. After the rough titration, two accurate titrations are undertaken and the
average of the two accurate results are used in the calculation. Sometimes there is a
discrepancy between the two end-point volumes but commonly the two titrant volumes
should be within 0.1 mL of each other. Should the two volumes be outside this range
then a third accurate titration may be undertaken an the appropriate erroneous data
removed.

Note
Some of you will be used to using moles as a means of calculation. Please feel free to
use whichever method of calculation you are comfortable with.
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6
Summary
Whilst titrations are simple to execute they are nevertheless a powerful analytical tool. In
a modern analytical laboratory using state of the art equipment such as autotitrators
around a hundred determinations could be carried out per Man day. You should appreciate
that this method of analysis is still used extensively for analytical purposes. You should
further realise that a knowledge of many of the topics being studied in introductory
chemistry (periodic table, formula of compounds, Molarity, acids; bases and equation
balancing, redox and solubility and equilibria) is essential when undertaking quantitative
analysis by titration.


The moles route

Using
Eq 1. moles = mass (grams) / RMM

Eq 2. concentration = moles / volume (litres)

Eq 3. moles = No of atoms / Avogadros No

Firstly calculate the concentration of the prepared sodium carbonate standard.

The relative molecular mass (RMM) of sodium carbonate is 105.9888

As 2.6370 grams were actually weighed the concentration of the prepared solution is given
by

Eq1 . moles = mass (grams) / RMM

moles = 2.6370/105.9888

= 0.024789. moles

Eq 2 concentration = moles / volume (litres)

= 0.024789 / (500/1000

= 0.0497599.. molL
-1


Therefore the prepared sodium carbonate standard was 0.0498 M to 4 d.p.

Secondly calculate the concentration of the nitric acid
Using
Na
2
CO
3
(aq)
+ 2 HNO
3
(aq)
2NaNO
3
(aq)
+ CO
2
(g)
+ H
2
O
(l)
Sodium carbonate Nitric acid Sodium nitrate Carbon dioxide Water

And 19.2 mL of nitric acid neutralises 20 mL of sodium carbonate standard



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7

Calculate number of moles of sodium carbonate in 25mL

Use Eq 2

concentration = moles / volume (litres)

moles = concentration x volume

= 0.0497599.. * (20/1000)

= 0.000995198. moles sodium carbonate

Finding the concentration of nitric acid

as
Na
2
CO
3
(aq)
+ 2 HNO
3
(aq)
2NaNO
3
(aq)
+ CO
2
(g)
+ H
2
O
(l)
Sodium carbonate Nitric acid Sodium nitrate Carbon dioxide Water

Then as 1 mole Na
2
CO
3
(aq)
reacts with 2 moles HNO
3
(aq)
there must be

2 * 0.000995198 moles HNO
3
(aq)
present in 19.2 mL of the acid

= 0.001990396 moles HNO
3
(aq)
present in 19.2 mL of the acid


Using Eq 2
concentration = moles / volume (litres)

concentration = 0.001990396 / (19.2/1000)

= 0.1037M to 4 decimal places


Note.

Whichever calculation method you use, you should get the same answer !!

It is advisable to have a rough answer obtained logically so you can check that your
final answer is likely to be correct.

In this example the volume of acid and base is roughly the same 19.2 mL and 20 mL
respectively. As 2 moles of acid react with 1 mole of base it is logical to assume that the
concentration of the acid is roughly double the concentration of the base. That is what is
found therefore the calculations seem correct !!


Introductory Chemistry 2013/14 J11ICH

8
Questions
An experiment is undertaken to determine the concentration of a calcium chloride solution.
The analysis can be achieved using standard silver nitrate. However only a silver nitrate
solution of unknown concentration is available and it therefore requires standardisation
first.

An experiment is conducted as follows.
(Part 1) 5.0582 g of sodium chloride (primary standard) are weighed and a 250 mL
standard solution is prepared.
(Part 2) silver nitrate solution (to be standardised) is added from a burette and titrated
against 20 mL pipetted aliquots of the standard sodium chloride solution.
(Part 3) silver nitrate solution is added from a burette is titrated against 20 mL pipetted
aliquots of the calcium chloride solution of unknown concentration.

Experimental Results: ( You will need to work out Total Volume Used)
Experiment to standardise silver nitrate ( See part 2 above)

Rough 1 2

Final burette reading (mL) 21.6 20.9 20.8

Initial burette reading (mL) 0.1 0.5 0.4

Total volume used (mL) 21.5

Experiment to determine calcium chloride solution concentration (See part 3 above)

Rough 1 2

Final burette reading (mL) 16.9 16.5 16.7

Initial burette reading (mL) 0.2 0.1 0.2

Total volume used (mL)
Equations :
NaCl
(aq)
+ AgNO
3(aq)
AgCl
(ppt)
+ NaNO
3(aq)

sodium chloride silver nitrate silver chloride sodium nitrate

CaCl
2(aq)
+ 2AgNO
3(aq)
2AgCl
(ppt)
+ Ca(NO
3
)
2(aq)

calcium chloride silver nitrate silver chloride calcium nitrate
Questions
1. Using information from part 1. Calculate the molarity of the standard sodium
chloride solution. [ans 0.3462 M]

2. Using information from part 1 and part 2 and the experimental results for part 2.
Calculate the concentration of the silver nitrate solution. [ans 0.3394 M]

3. Using information from part 2 and part 3 and the experimental results for part 3.
Calculate the concentration of the calcium chloride solution. [ans 0.1396 M]