Titrations

Titrations are done often to find out the concentration of one substance by reacting it with another
substance of known concentration.
They are often done with neutralisation reactions, but can be done with redox reactions.

One substance (generally the one we don’t

know the concentration) is put in the conical
flask. It is measured using a volumetric burette
pipette.
The other substance is placed in the burette

However, the standard phrase: titrate solution

A with solution B means that A should be in the conical
conical flask and B should be in the burette. flask

A conical flask is used in preference to a beaker

because it is easier to swirl the mixture in a conical
flask without spilling the contents.

pipette

Method for Titration

Make sure bottom of
Using the pipette meniscus is on line on
neck of pipette

•rinse pipette with substance to go in it (often

alkali).
•pipette 25 cm3 of solution A into conical flask.
The volumetric pipette will have a mark on its neck
to show the level to fill to. The bottom of the
meniscus should sit on this line.
•touch surface of solution with pipette ( to
ensure correct amount is added). A small amount
of solution will be left in the pipette at this stage.
The calibration of the pipette will take into account
this effect. It should not be forced out.

1
Using the burette
The burette should be rinsed out with substance that will
be put in it. If it is not rinsed out the acid or alkali added
may be diluted by residual water in the burette or may
react with substances left from a previous titration. This
would lead to the concentration of the substance being
lowered and a larger titre being delivered.

Don’t leave the funnel in the burette because small drops

of liquid may fall from the funnel during the titration
leading to a false burette reading (would give a lower titre
volume)

make sure the jet space in the burette is filled with the
solution and air bubbles are removed.

If the jet space in the burette is not filled properly prior to commencing
the titration it will lead to errors if it then fills during the titration, leading to
a larger than expected titre reading.

Read the bottom of the meniscus on the burette

This is reading 9.00cm3

Even though a burette has marking reading to 0.1cm3, the burette

readings should always be given to 2dp either ending in 0.00 or
0.05. 0.05cm3 is the volume of 1 drop of solution delivered from a
burette and so this is the smallest difference in readings that can be
measured. If the bottom of the meniscus sits on a line it should end
with a 0.00 as in the above example 9.00cm3. If the meniscus sits
between two lines it should end 0.05. e.g. if the bottom of the
meniscus sits between the lines marked 9.1 and 9.2, you should
record 9.15

Adding indicator Use a white tile underneath the flask to help

Add a few drops of indicator and refer to colour observe the colour change
change at end point
Methyl orange
phenolphthalein Methyl orange is a suitable indicator for
If acid is added from the burette the colour change neutralisation reactions where strong acids are
would be pink (alkali) to colourless (acid): end point used.
pink colour just disappears [use with titrations using It is red in acid and yellow in alkali. It is orange at
strong alkalis e.g. NaOH ] the end point.

Methyl orange
Methyl orange Methyl orange
Alkali colour
end point acid colour
phenolphthalein phenolphthalein acid
Alkali colour colour
2
Add solution from burette whilst swirling the mixture and add dropwise
at end point

Distilled water can be added to the conical flask during a titration to wash
the sides of the flask so that all the acid on the side is washed into the
reaction mixture to react with the alkali.
It does not affect the titration reading as water does not react with the
reagents or change the number of moles of acid added.

note burette reading before and after addition of solution

Only distilled water should be used to
repeats titration until at least 2 concordant results are wash out conical flasks between
obtained- two readings within 0.1 of each other titrations because it does not add any
extra moles of reagents
A single titration could be flawed. Repeating allows
for anomalous titres to be spotted and discounted
lf 2 or 3 values are within 0.10cm3
and therefore concordant or close
Recording results then we can say results are accurate
•Results should be clearly recorded in a table and reproducible and the titration
•Result should be recorded in full (i.e. both initial and final technique is good and consistent
readings)
•Record titre volumes to 2dp (0.05 cm3)
Working out average titre results
Titration number 1 2 3 Only make an average of the
concordant titre results

Initial burette reading (cm3 ) 0.50 2.50 1.55 Average titre = (24.50+ 24.40)/2 =
24.45
Final burette reading (cm3 ) 24.50 27.00 25.95

Titre (cm3 ) 24.00 24.50 24.40

Safety precautions

Acids and alkalis are corrosive

(at low concentrations acids are irritants)
Wear eye protection and gloves
If spilled immediately wash affected parts after spillage

If substance is unknown treat it as potentially toxic and wear

gloves.

Titrating mixtures
Testing batches If titrating a mixture to work out the concentration
In quality control it will be necessary to do of an active ingredient it is necessary to consider
titrations/testing on several samples as the if the mixture contains other substances that
amount/concentration of the chemical being tested may have acid base properties.
vary between samples. If they don’t have acid base properties we can
titrate with confidence.

3
 Example 1: 23.6cm3 of H2SO4 neutralised 25.0cm3 of 0.150M
Common Titration Equations
NaOH. What is the concentration of the H2SO4? CH3CO2H + NaOH  CH3CO2-Na+ + H2O
H2SO4 + 2NaOH  Na2SO4 +2H2O
H2SO4 + 2NaOH  Na2SO4 +2H2O
Step 1: work out amount, in mol, of sodium hydroxide HCl + NaOH  NaCl +H2O
amount = conc x vol NaHCO3 + HCl  NaCl + CO2 + H2O
= 0.15 x 0.025
= 0. 00375 mol Na2CO3 + 2HCl 2NaCl + CO2 + H2O

Step 2: use balanced equation to give moles of H2SO4 Example 3

2 moles NaOH : 1 moles H2SO4
So 0.00375 NaOH : 0.001875 moles H2SO4
950 mg of impure calcium carbonate tablet was crushed. 50.0
cm3 of 1.00 mol dm–3 hydrochloric acid, an excess, was then
Step 3 work out concentration of H2SO4 added and the mixture was transferred to a volumetric flask.
The volume was made up to exactly 100 cm3 with distilled
conc= amount/Volume
water. 10.0 cm3 of this solution was titrated with 11.1cm3 of
= 0.001875 / 0.0236 0.300 mol dm–3 sodium hydroxide solution.
= 0.0794 mol dm-3 What is the percentage of CaCO3 by mass in the tablet
1. Calculate the number of moles of sodium hydroxide used
amount = conc x vol
Example 2: A 25.0cm3 sample of vinegar was diluted in a = 0.30 x 0.0111
250cm3 volumetric flask. This was then put in a burette and = 0. 00333 mol
23.10cm3 of the diluted vinegar neutralised 25.0 cm3 of 0.100
2. Work out number of moles of hydrochloric acid left in 10.0 cm3
M NaOH. What is the concentration of the vinegar in gdm-3 ?
use balanced equation to give moles of HCl
CH3CO2H + NaOH  CH3CO2-Na+ + H2O
1 mol NaOH : 1 mol HCl
So 0.00333 NaOH : 0.00333 moles HCl
Step 1: work out amount, in mol, of sodium hydroxide
amount = conc x vol 3. Calculate the number of moles of hydrochloric acid left in
= 0.10 x 0.025 100 cm3 of solution
= 0. 00250 mol
Moles in 100cm3 = 0.00333 x10
Step 2: use balanced equation to give moles of CH3CO2H =0.0333
1 moles NaOH : 1 moles CH3CO2H
So 0.00250 NaOH : 0.00250 moles CH3CO2H 4. Calculate the number of moles of HCl that reacted with
the indigestion tablet.
Step 3 work out concentration of diluted CH3CO2H in 23.1
(and 250 cm3)in moldm-3 In original HCl 50.0 cm3 of 1.00 mol dm–3 there is 0.05moles
conc= amount/Volume
moles of HCl that =0.05 -0.0333
= 0.00250 / 0.0231 reacted with the =0.0167
= 0.108 mol dm-3 indigestion tablet.
Step 4 work out concentration of original concentrated
CH3CO2H in 25cm3 in moldm-3 5 Use balanced equation to give moles of CaCO3
CaCO3(s) + 2HCl(aq)  CaCl2(aq) + CO2(g) + H2O(l)
conc = 0.108 x 10 = 1.08 mol dm-3 2 mol HCl : 1 mol CaCO3
So 0.0167 HCl : 0.00835 moles CaCO3
Step 5 work out concentration of CH3CO2H in original
concentrated 25 cm3 in gdm-3
6. work out the mass of CaCO3 in original tablet
conc in gdm-3 = conc in mol dm-3 x Mr
mass= amount x Mr
= 1.08 x 60 = 64.8 g dm-3
= 0.00835 x 100 = 0.835 g
To turn concentration measured in mol dm-3
into
concentration measured in g dm-3 multiply by Mr of the percentage of
CaCO3 by mass in = 0.835/0.950 x100
substance
the tablet
conc in g dm-3 = conc in mol dm-3 x Mr = 87.9 %
The concentration in g dm-3 is the same as the mass of
solute dissolved in 1dm3

4
Measurements F323 1

MEASUREMENTS AND ERRORS

Accuracy A measure of the closeness of agreement between an individual result and the
accepted value. An accurate result is in close agreement with the accepted value.

Error The difference between an individual measurement and the true value (or
accepted reference value) of the quantity being measured.

Precision The closeness of agreement between independent measurements obtained under

the same conditions. It depends only on the distribution of random errors (i.e. the
spread of measurements) and does not relate to the true value.

Uncertainty An estimate attached to a measurement which characterises the range of values

within which the true value is said to lie. It is written, for example, as 44.0 ± 0.4.

Reliability The opposite of uncertainty; high uncertainty = not very reliable measurement

Accuracy of measurements
Uncertainty is often taken to be half a division on either side of the smallest unit on the
scale. However, the accuracy of measurements also depends on the quality of the apparatus
used (e.g. Grade A or Grade B glassware.)

example If a 100 cm3 measuring cylinder is graduated in 1 cm3 divisions.

• Class A - maximum error of half a division (0.5 cm3 )
• Class B - maximum error of a whole division (1 cm3)

Glassware
When glassware is manufactured there will always be a maximum error. This is usually marked
on the glassware.

Temperature Volumetric equipment must not get warm because expansion of the glass will
alter the volume; the temperature is marked on the apparatus.

In or out? Apparatus either...

holds an accurate measure (IN) or delivers an accurate volume (EX)
volumetric flask burette
measuring cylinder pipette

Ex 20°C Ex 20°C
25cm 3

25 cm3

In 20°C In 20°C
250cm3
250 cm3

© KNOCKHARDY PUBLISHING 2008

2 F323 Measurements

Reading values

Digital • top pan balance or pH meter

• record all the digits shown
67.36 67.356

2-places 3-places

Non-digital • burette, measuring cylinder

• record all the figures that are known for certain
• read to half a division
• for a burette, record values to two decimal places ending in a 5 or a 0

26.0 2.0 2.0

27.0 3.0 3.0

26.50 cm3 3.00 cm3 2.45 cm3

Maximum errors
Burette • graduated in divisions every 0.1 cm3
• maximum error is half a division i.e. ± 0.05 cm3
• burettes are read twice, so the overall maximum error is 2 x 0.05 = ± 0.1 cm3

Pipette • a 25 cm3 pipette has a maximum error of 0.06 cm3

• like all volumetric equipment it must be used properly

Q.1 Calculate the maximum error of a ...

• 50 cm3 measuring cylinder cm3
• 10 cm3 measuring cylinder cm3

Balances a two-decimal place balance may a three-decimal place balance may

have a maximum error of 0.005 g have a maximum error of 0.0005 g

67.32 67.33 67.357 67.356

The significance of the maximum error in a measurement depends upon how large
a quantity is being measured. It is useful to quote this error as a percentage error.

© KNOCKHARDY PUBLISHING 2008

Measurements F323 3

Percentage • based on two factors - maximum error

Error - value of measurement

• percentage error = maximum error x 100%

value of measurement

• the smaller the value measured, the greater the percentage error

Volumetric maximum error = 0.2 cm3

flask (250 cm3)
percentage error = 0.2 cm3 x 100 = 0.08%
250 cm3

Pipette maximum error = 0.06 cm3

(25 cm3)
percentage error = 0.06 cm3 x 100 = 0.24%
25 cm3

Burette maximum error = 0.05 cm3 per reading

0.10 cm3 per titration (you read it twice)

percentage error depends on the volume delivered

(the smaller the volume, the bigger the % error)

for a 25.00 cm3 delivery = 0.10 cm3 x 100 = 0.40%

25.00 cm3

for a 15.00 cm3 delivery = 0.10 cm3 x 100 = 0.67%

15.00 cm3

2-decimal place
top-pan balance mass of beaker + solid = 32.56 g maximum error = 0.005 g
mass of empty beaker = 32.16 g maximum error = 0.005 g
mass of solid = 0.40 g maximum error = 0.01g

percentage error = 0.01 g x 100 = 2.5%

0.40 g

3-decimal place
top-pan balance maximum error over two readings will be 0.001 g (2 x 0.0005)
using the above values, percentage error will be = 0.25%

© KNOCKHARDY PUBLISHING 2008

4 F323 Measurements

Thermometers
Scale • maximum error depends on the scale and how many degrees per division
• maximum error when measuring a temperature change is one division

Temperature • the greater the temperature change, the lower the percentage error
change

°C
Q.2 What is the reading on each thermometer? °C

A B 21 22

What is the maximum error involved? 20 20

A B
A B

Calculate the percentage error measuring a temperature change of 20°C using

A B

Calculate the percentage error measuring a temperature change of 2°C using

A B

Significant
figures When quoting a result, it should contain the same number of significant
figures as the measurement that has the smallest number of significant figures.

Rounding off • if the last figure is between 5 and 9 inclusive round up

• if the last figure is between 0 and 4 inclusive round down

• should only be done at the end of a calculation

• should not be done after each step of a calculation (it causes rounding errors)

example 50.67 rounded to 3 sig figs is 50.7

2 sig figs is 51
1 sig figs is 100

• for larger numbers, use standard form

example 371 rounded to 2 sig figs is 3.7 x 102
3 sig figs is 3.71 x 102

© KNOCKHARDY PUBLISHING 2008

Measurements F323 5

Recording volumes during titrations

Burette measurements should be recorded to 2 decimal places with the last figure either 0 or 5.

During a titration, initial and final burette readings should be taken; the titre (actual volume
delivered) is calculated by difference. Record titration results in a table as shown below.

Approx 1 2 3

final volume / cm3 26.00 26.75 30.85 24.60

initial volume / cm3 1.00 2.30 6.00 0.25
titre / cm3 25.00 24.45 24.85 24.35
tick if used to calculate mean ✓ ✓

Mean titres • repeat the titrations until there are two concordant titres (within 0.10 cm3)
• take an average of the concordant titres
• if this is not possible, use the two titres that have the closest agreement

example the two concordant titres are the 1st and 3rd (within 0.1 cm3 of each other)

mean (average) titre value = 24.45 cm3 + 24.35 cm3 = 25.40 cm3
2

overall maximum error = 2 x 0.05 = 0.10 cm3

overall percentage error = 0.10 cm3 x 100 = 0.39%
25.40 cm3

There is a case for arguing that the accumulated errors indicate that one decimal
place is more appropriate but this should not be used. The maximum error is the
worst-case scenario and it is likely that the actual titre will in reality be more
accurate than one decimal place.

If concordant titres within 0.05 cm3 of one another are found there is a problem
when calculating the mean titre. For example, a student may obtain three recorded
titres of 24.45 cm3, 24.85 cm3 and 24.40 cm3.

mean titre value = 24.45 cm3 + 24.40 cm3 = 24.425 cm3

2

This mean titre has a value that is more accurate than the burette can measure.
The value of 24.425 cm3 should more correctly be ‘rounded’ to 24.43 cm3. It would
seem very unfair not to credit a mean titre of 24.425 cm3 in this case, especially as
the results showed a better concordancy.

In assessed A level practical tasks, the mean of two titres of 25.25 cm3 and
25.20 cm3 will be allowed as 25.2, 25.20, 25.25 or 25.225 cm3.

© KNOCKHARDY PUBLISHING 2008

6 F323 Measurements

Errors in
procedure The accuracy of a final result also depends on the procedure used.

For example, in an enthalpy experiment, the measurement of a temperature

change may be precise but there may be large heat losses to the surroundings
which affect the accuracy of overall result.

Anomalous
readings Where an experiment uses repeated measurements of the same quantity, (e.g.
titrations) anomalous readings should be identified. If a titre is clearly outside the
range of all other readings, it can be judged as being anomalous and should be
ignored when the mean titre is calculated.

If a plotted graph reveals that a value is anomalous, then it too should be ignored.

Introducing rounding errors in multi-step calculations

Example When 6.074 g of a carbonate is reacted with 50.0 cm3 of 2.0 mol dm-3 HCl(aq)
(which is an excess), a temperature rise of 5.5 °C is obtained.
[The specific heat capacity of the solution is 4.18 J g-1 K-1 ]

Heat produced = 50.0 x 4.18 x 5.5 = 1149.5 J = 1.1495 kJ (by calculator)

Since the least certain measurement (the temperature rise) is only to 2

significant figures the answer should also be quoted to 2 significant figures.

Therefore, the heat produced should be quoted as 1.1 kJ

If this figure is to be used subsequently to calculate the enthalpy change per mole
then a ‘rounding’ error will be produced. The 1.1495 kJ value must be used.

For example, if the carbonate has a molar mass of 84.3 g mol-1, the enthalpy
change per mole of carbonate can be calculated from the value above.

Using the calculator value of 1.1495 kJ for the heat produced

enthalpy per mole = 15.95371255 kJ mol-1 = 16 kJ mol-1 (to 2 sig figs)

Using the rounded value of 1.1 kJ for the heat produced,

enthalpy per mole = 15.26671057 kJ mol-1 = 15 kJ mol-1 (to 2 sig figs)

Rounding to 2 sig figs too early produces a ‘rounding error’.

References The Royal Society of Chemistry has produced several very helpful documents
on measurements and errors;
www.rsc.org/education/teachers/learnnet/pdf/learnnet/RSCmeasurements_teacher.pdf
www.rsc.org/pdf/amc/brief13.pdf

© KNOCKHARDY PUBLISHING 2008

Uncertainty
Readings and Measurements
Readings Measurements In general, if uncertainty is not indicated
the values found from a single the values taken as the on apparatus, the following assumptions
judgement when using a piece difference between the are made:
of equipment judgements of two values For an analogue scale-
(e.g. using a burette in a The uncertainty of a reading (one
titration)
judgement) is at least ±0.5 of the smallest
scale reading.
Calculating Apparatus Uncertainties
The uncertainty of a measurement (two
Each type of apparatus has a sensitivity uncertainty
judgements) is at least ±1 of the smallest
•balance  0.001 g (if using a 3 d.p. balance) scale reading.
•volumetric flask  0.1 cm3 - If the apparatus has a digital scale, the
•25 cm3 pipette  0.1 cm3 uncertainty is  the resolution of the
•burette (start & end readings and end point )  0.15 cm3 apparatus in each measurement

Calculate the percentage error for each piece of equipment used by

Uncertainty of a measurement using a
burette. If the burette used in the
% uncertainty =  uncertainty x 100
titration had an uncertainty for each
Measurement made on apparatus
reading of +/– 0.05 cm3 then during a
titration two readings would be taken so
e.g. for burette
the uncertainty on the titre volume would
% uncertainty = 0.15/average titre result x100
be +/– 0.10 cm3 . Then often another 0.05
is added on because of uncertainty
To calculate the maximum total percentage apparatus uncertainty in the
identifying the end point colour change
final result add all the individual equipment uncertainties together.

Reducing uncertainties in a titration To decrease the apparatus uncertainties

you can either decrease the sensitivity
Replacing measuring cylinders with pipettes or burettes which have uncertainty by using apparatus with a
lower apparatus uncertainty will lower the % uncertainty. greater resolution (finer scale divisions ) or
you can increase the size of the
To reduce the % uncertainty in a burette reading it is necessary to make measurement made.
the titre a larger volume. This could be done by: increasing the volume
and concentration of the substance in the conical flask or by decreasing
the concentration of the substance in the burette. If looking at a series of measurements in
an investigation, the experiments with
the smallest readings will have the
highest measurement uncertainties.
Reducing uncertainties in measuring mass
Using a balance that measures to more decimal places or using
a larger mass will reduce the % uncertainty in weighing a solid.

Weighing sample before and after addition and then calculating

difference will ensure a more accurate measurement of the
mass added.

If the %uncertainty due to the apparatus <

Calculating the percentage difference between the actual percentage difference between the actual value and
value and the calculated value the calculated value then there is a discrepancy in
the result due to other errors.
If we calculated an Mr of 203 and the real value is 214, then
the calculation is as follows: If the %uncertainty due to the apparatus >
Calculate difference 214-203 = 11 percentage difference between the actual value and
% = 11/214 x100 the calculated value then there is no discrepancy and
=5.41% all the difference between values can be explained
by the sensitivity of the equipment.

5
Errors in Titrations

1) A student carried out an experiment to determine the concentration of ethanoic acid in a solution of
vinegar.
• The student used a measuring cylinder to measure out 25.0 cm3 of the vinegar solution.
• This solution was then transferred to a 250 cm3 volumetric flask and the liquid level
was carefully made up to the mark with distilled water.
• A pipette was used to transfer 25.0 cm3 portions of the acidic solution to conical flasks.
• The solution was then titrated with sodium hydroxide solution, concentration
0.100 mol dm–3, using phenolphthalein as the indicator.
The average titre was 26.5cm3

a) Suggest, with reasons, how the student’s method of preparing the diluted solution could be improved.
b) The maximum total errors for the pipette and the burette in the titration are
pipette ±0.05 cm3
burette ±0.15 cm3
These errors take into account multiple measurements.
Estimate the combined maximum percentage error in using both of these pieces of apparatus.
c) Give two changes you could make to reduce the percentage error in using the burette.
d) State why it is important to fill the space below the tap in the burette with sodium hydroxide before
beginning an accurate titration.
e) Give a reason why a 250 cm3 conical flask is preferred to a 250 cm3 beaker for a titration.
f) During a titration, a chemist rinsed the inside of the conical flask with deionised water. The water used
for rinsing remained in the conical flask.
(i) Give a reason why this rinsing can improve the accuracy of the end-point.
(ii) Explain why the water used for rinsing has no effect on the accuracy of the titre.
g) Give a reason why repeating a titration makes the value of the average titre more reliable.
h) Phenolphthalein is an acid. State how the average titre would change if a few cm3, rather than a few
drops, of the indicator were used by mistake in this titration.
i)Vinegar contains other substances which improve flavour. Suggest one reason why these substances
could affect the titration with sodium hydroxide.
j) Suggest why the student checks the concentration of the ethanoic acid in several batches of vinegar.

k) Calculate the concentration of the vinegar in the 250 cm3 flask.

Errors in the method will lead to an inaccurate value of the concentration of acid
being calculated. How would the following situations affect the magnitude of the concentration of
vinegar calculated? Explain why
i. air lock below tap in burette
ii. air bubble in pipette of vinegar
iii. too much water is added so the meniscus of the diluted acid is above the line on the neck of the
volumetric flask
iv. the concentration of the alkali has been incorrectly given. It is actually 0.095mol dm-3
v. The conical flask contains some distilled water before the vinegar is added.
vi. The burette is not rinsed with sodium hydroxide
vii. The pipette was washed with water between titres

6
2) In a series of titrations a student obtained the following titres (all in cm3).

State what this student must do in order to obtain an accurate average titre in this experiment.

3) A student wanted to test the acidity of a 100cm3 sample of shampoo. She suggested
that the 100 cm3 shampoo should be divided into four portions before the titration.
Explain how this change increases the reliability and decreases the accuracy of the
experiment.

4) A student carried out an experiment to calculate the value of x in Na2CO3.xH2O The

correct value of x is 10, making the Mr of Na2CO3.10H2O is 286.0

a) The maximum percentage error in the experiment that can be due to the apparatus
is ±1.0%. If the only error is apparatus error, calculate the minimum value of the Mr of
Na2CO3.10H2O that could be obtained from an experiment.
Use this minimum value of the Mr to calculate a minimum experimental value
for x

b) A titration was carried out with a sample of pure washing soda that had been stored
for some time. A student obtained a value of 8.6 for the value of x. The container from
which the hydrated sodium carbonate was taken was labelled Na2CO3.10H2O.
Assume that the student carried out the titration and the calculation accurately. State a
reason why the number of moles of water of crystallisation is less than 10.