Practical Guide OCR

This guide includes details about the PAGs for A-level chemistry. It also contains information about other
experiments that often occur in A-level examinations. You may be asked to describe these experiments in details
or be asked about reasons for doing individual steps.
You may be asked about other unfamiliar experiments but these will be using the skills and techniques that are
described in the following experiments.

Safety and hazards

Irritant - dilute acid and alkalis- wear googles Hazardous substances in low
Corrosive- stronger acids and alkalis wear goggles concentrations or amounts will
Flammable – keep away from naked flames not pose the same risks as the
Toxic – wear gloves- avoid skin contact- wash hands after use pure substance.
Oxidising- Keep away from flammable / easily oxidised materials

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 This method could be used for measuring mass loss in various
PAG1 Heating in a crucible
thermal decomposition reactions and also for mass gain when
reacting magnesium in oxygen.

Oxidation reaction. The mass gain by reacting magnesium in

The lid improves the accuracy of the
oxygen can be measured by the following method
experiment as it prevents loss of solid
Mg (s) + O2 (g) → MgO(s)
from the crucible but should be loose
Method.
fitting to allow gas to escape/enter.
•Weigh an empty clean dry crucible and lid .
•Add 2g of coiled magnesium ribbon (that has been cleaned
with emery paper) to the crucible and weigh again
•Heat strongly with a Bunsen for a couple of minutes
•Occasionally lift lid with tongs to allow in some oxygen but
taking care not to let magnesium oxide powder escape
•Allow to cool
•Weigh the crucible and contents again
•Heat crucible again and reweigh until you reach a constant
mass ( do this to ensure reaction is complete).

Decomposition reaction. The water of crystallisation in calcium sulfate crystals can be removed as water
vapour by heating as shown in the following equation.
CaSO4.xH2O(s) → CaSO4(s) + xH2O(g)
Method.
•Weigh an empty clean dry crucible and lid .
•Add 2g of hydrated calcium sulfate to the crucible and weigh again
•Heat strongly with a Bunsen for a couple of minutes
•Allow to cool
•Weigh the crucible and contents again
•Heat crucible again and reweigh until you reach a constant mass ( do this to ensure reaction is complete).

Large amounts of hydrated calcium sulfate, such as 50 g,

should not be used in this experiment as the decomposition is
likely to be incomplete. Small amounts of the solid , such as
0.100 g, should not be used in this
The crucible needs to be dry otherwise a wet crucible would experiment as the percentage
give an inaccurate result. It would cause mass loss to be too uncertainties in weighing will be too
large as the water would be lost when heating. high.

Example 1. 3.51 g of hydrated zinc sulfate were heated and 1.97 g of anhydrous zinc sulfate were obtained.
Calculate the value of the integer x in ZnSO4.xH2O
Calculate the mass of H2O = 3.51 – 1.97 = 1.54g
Calculate moles of Calculate moles of = 1.54
= 1.97 H2O
ZnSO4 161.5 18

= 0.0122 =0.085

Calculate ratio of mole of 0.0122 = 0.085

ZnSO4 to H2O =
0.0122 0.0122
=7
=1
X=7

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Measuring gas volumes
Make sure you don’t leave gaps in
Using a gas syringe your diagram where gas could
Gas syringes can be used for a variety of escape
experiments where the volume of a gas is
measured, possibly to work out moles of
gas or to follow reaction rates.

Potential errors in using a gas syringe

•gas escapes before bung inserted If drawing a gas syringe make sure
•syringe sticks you draw it with some
• some gases like carbon dioxide or sulphur dioxide are measurement markings on the
soluble in water so the true amount of gas is not barrel to show measurements can
measured. be made.

The volume of a gas depends on pressure Alternatively gas volumes can be

and temperature so when recording volume measured ‘over water’ with an up-turned
it is important to note down the measuring cylinder in a trough of water
temperature and pressure of the room.

Moles of gas can be calculated from gas

volume (and temperature and pressure)
using ideal gas equation PV = nRT or using
the molar gas volume (1mol gas =24dm3 at
room temperature and pressure

Method for using a gas syringe to calculate the Mr of propanone

1. Extract 0.20 cm3 of propanone into a hypodermic syringe and then measure the mass of this syringe
2. using hand protection, remove a gas syringe from the oven and note the volume of air already in the
barrel – about 5 cm3.
3. inject the propanone through the self-seal cap into the barrel. The plunger will move straight away.
4. Put the gas syringe back into the oven.
5. Measure the mass of the empty hypodermic syringe immediately.
6. After a few minutes measure the volume of the gas in the gas syringe, record the temperature of the oven
shelf and the pressure of the room.

Example 2 : 0.150g of a volatile liquid was injected into a sealed gas syringe. The gas syringe was placed in an oven at
70oC at a pressure of 100kPa and a volume of 80cm3 was measured. Calculate the Mr of the volatile liquid (R = 8.31)

moles = PV/RT 100 kPa = 100 000 Pa

= 100 000 x 0.00008 / (8.31 x 343) 80 cm3 = 0.00008 m3
= 0.00281 mol

Mr = mass/moles
= 0.15 / 0.00281
= 53.4 g mol-1

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PAG2. Make up a volumetric solution and carry out a simple acid–base titration

Making a solution

• Weigh the sample bottle containing the required mass of solid Alternatively the known mass of solid
on a 2 dp balance in the weighing bottle could be
• Transfer to beaker transferred to beaker, washed and
• Reweigh empty sample bottle washings added to the beaker.
• Record the difference in mass

• Add 100cm3 of distilled water to the beaker. Use a glass rod to

stir to help dissolve the solid.

•Sometimes the substance may not dissolve well in cold water so

the beaker and its contents could be heated gently until all the
solid had dissolved.
Remember to fill so the bottom of the
• Pour solution into a 250cm3 graduated flask via a funnel. meniscus sits on the line on the neck of the
• Rinse beaker and funnel and add washings from the beaker flask. With dark liquids like potassium
and glass rod to the volumetric flask. manganate it can be difficult to see the
• make up to the mark with distilled water using a dropping meniscus.
pipette for last few drops.
• Invert flask several times to ensure uniform solution. Shake the volumetric flask thoroughly to
ensure a uniform concentration

A graduated flask has one mark on the neck which the level to
fill to get the accurate volume. Do not heat or put hot
solutions in the volumetric flask because the heat would cause
the flask to expand and the volume would then be incorrect.

Measuring mass accurately:

In many experiments the best method for measuring mass is
1. Measure mass on 2 or 3d.p. balance of a weighing bottle
with the required quantity of solid in it
2. Empty mass into reaction vessel/flask
3. Reweigh the now empty weighing bottle
4. Subtract the mass of the empty weighing bottle from the
Graduated/volumetric flask first reading to give exact of mass actually added.

Dilutions

Diluting a solution
Using a volumetric pipette is more accurate
than a measuring cylinder because it has a
•Pipette 25.0cm3 of original solution into a 250cm3 smaller uncertainty
volumetric flask
•make up to the mark with distilled water using a dropping Use a teat pipette to make up to the mark in
pipette for last few drops. volumetric flask to ensure volume of solution
• Invert flask several times to ensure uniform solution. accurately measured and one doesn’t go over
the line

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Titrations PAG2. Make up a volumetric solution and carry out a simple acid–base titration
General Method
•rinse equipment (burette with acid, pipette with alkali, conical flask with distilled water)
•pipette 25 cm3 of alkali into conical flask
•touch surface of alkali with pipette ( to ensure correct amount is added)
•adds acid solution from burette
•make sure the jet space in the burette is filled with acid
•add a few drops of indicator and refer to colour change at end point
•phenolphthalein [pink (alkali) to colourless (acid): end point pink colour just disappears] [use if NaOH is used]
•methyl orange [yellow (alkali) to red (acid): end point orange] [use if HCl is used]
•use a white tile underneath the flask to help observe the colour change
•add acid to alkali whilst swirling the mixture and add acid drop wise at end point
•note burette reading before and after addition of acid
•repeats titration until at least 2 concordant results are obtained- two readings within 0.1 of each other

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. burette

One substance (generally the one we don’t know the

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

However, the standard phrase: titrate solution A

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

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

Detailed 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.

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 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 0.1cm 3, 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
Indicators are generally weak acids so only add a few
Add a few drops of indicator and refer to colour change drops of them. If too much is added they will affect
at end point the titration result
phenolphthalein Methyl orange
If acid is added from the burette the colour change would
Methyl orange is a suitable indicator for neutralisation
be pink (alkali) to colourless (acid): end point pink colour
reactions where strong acids are used.
just disappears [use with titrations using strong alkalis e.g.
It is red in acid and yellow in alkali. It is orange at the end
NaOH ]
point.

Methyl orange
Methyl orange Methyl orange
Alkali colour
end point acid colour
phenolphthalein phenolphthalein acid
colour Use a white tile underneath the flask to help
Alkali colour
observe the colour change

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Add solution from burette whilst swirling the mixture and add drop-wise 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 titrations
obtained- two readings within 0.1 of each other 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 then we
Recording results can say results are accurate and
•Results should be clearly recorded in a table repeatable and the titration technique
•Result should be recorded in full (i.e. both initial and final readings) is good and consistent
•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
Common Titration Equations
Acids and alkalis are corrosive CH3CO2H + NaOH  CH3CO2-Na+ + H2O
(at low concentrations acids are irritants)
Wear eye protection and gloves H2SO4 + 2NaOH  Na2SO4 +2H2O
If spilled immediately wash affected parts after spillage HCl + NaOH  NaCl +H2O
NaHCO3 + HCl  NaCl + CO2 + H2O
If substance is unknown treat it as potentially toxic and wear
gloves. Na2CO3 + 2HCl 2NaCl + CO2 + H2O

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

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Manganate Redox Titrations The purple colour of manganate can make it
The redox titration between Fe2+ with MnO4– (purple) is a very common difficult to see the bottom of meniscus in
exercise. This titration is self indicating because of the significant colour the burette.
change from reactant to product.
If the manganate is in the burette then the
MnO4-(aq) + 8H+ (aq) + 5Fe2+ (aq)  Mn2+ (aq) +4H2O (l) + 5Fe3+ (aq) end point of the titration will be the first
Purple colourless permanent pink colour.
Colourless  purple

Detailed Procedure : how much iron in iron tablets

• Weigh accurately two 'ferrous sulfate' tablets.

• Grind up the tablets with a little 1M sulphuric acid, using a pestle and mortar.
• Through a funnel, transfer the resulting paste into a 100cm3 volumetric flask. Use further small volumes of 1 M
sulfuric acid to rinse the ground-up tablets into the flask.
• Then add sufficient 1M sulfuric acid to make up the solution to exactly 100cm3. Stopper the flask and shake it to
make sure that all the contents are thoroughly mixed. They will not all be in solution although the Fe 2+ ions which
were present in the tablets will be dissolved.
• Titrate 10.0 cm3 portions of the solution with 0.0050 M potassium manganate(VII). The end-point is marked by the
first permanent purple colour.

Choosing correct acid for manganate titrations.

The acid is needed to supply the 8H+ ions. Some acids are not suitable as they set up alternative redox reactions and
hence make the titration readings inaccurate.
Only use dilute sulfuric acid for manganate titrations.
Insufficient volumes of sulfuric acid will mean the solution is not acidic enough and MnO 2 will be produced instead of
Mn2+.
MnO4-(aq) + 4H+(aq) + 3e-  MnO2 (s) + 2H2O
The brown MnO2 will mask the colour change and lead to a greater (inaccurate) volume of manganate being used in
the titration.
Using a weak acid like ethanoic acid would have the same effect as it cannot supply the large amount of hydrogen
ions needed (8H+).

It cannot be conc HCl as the Cl- ions would be oxidised to Cl2 by MnO4- as the Eo MnO4-/Mn2+ > Eo Cl2/Cl-
MnO4-(aq) + 8H+(aq) + 5e–  Mn2+ (aq) + 4H2O(l) E+1.51V
Cl2(aq) +2e–  2Cl–(aq) E +1.36V
This would lead to a greater volume of manganate being used and poisonous Cl 2 being produced.

It cannot be nitric acid as it is an oxidising agent. It oxidises Fe 2+ to Fe3+ as Eo NO3-/HNO2> Eo Fe3+/Fe2+

NO3- (aq) + 3H+(aq) + 2e–  HNO2(aq) + H2O(l) Eo +0.94V
Fe3+ (aq)+e–  Fe2+ (aq) Eo +0.77 V
This would lead to a smaller volume of manganate being used.

Example 3 Manganate titration Step1 : find moles of KMnO4

A 2.41g nail made from an alloy containing iron is moles = conc x vol
dissolved in 100cm3 acid. The solution formed contains 0.02 x 9.8/1000
Fe(II) ions. = 1.96x10-4 mol
10cm3 portions of this solution are titrated with Step 2 : using balanced equation find moles Fe2+ in 10cm3
potassium manganate (VII) solution of 0.02M. 9.80cm3
= moles of KMnO4 x 5
of KMnO4 were needed to react with the solution
= 9.8x10-4 mol
containing the iron.
Step 3 : find moles Fe2+ in 100cm3
Calculate the percentage of iron by mass in the nail
= 9.8x10-4 mol x 10
MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+(aq) + 4H2O + 5Fe3+ = 9.8x10-3 mol
Step 4 : find mass of Fe in 9.8x10-3 mol
mass= moles x RAM = 9.8x10-3 x 55.8 = 0.547 g
Step 5 : find % mass
% mass = 0.547/2.41 x100
= 22.6%

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Other useful manganate titrations
With hydrogen peroxide
Ox H2O2  O2 + 2H+ + 2e-
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O The reaction between MnO4- and
Overall 2MnO4-(aq) + 6H+(aq) + 5H2O2  5O2 + 2Mn2+ (aq) + 8H2O C2O42- is slow to begin with (as the
With ethanedioate reaction is between two negative
ions). To do as a titration the conical
Ox C2O42-  2CO2 + 2e-
flask can be heated to 60o C to
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O
speed up the initial reaction.
Overall 2MnO4-(aq) + 16H+(aq) + 5C2O42-(aq)  10CO2(g) + 2Mn2+(aq) + 8H2O(l)

With Iron (II) ethanedioate both the Fe2+ and the C2O42- react with the MnO4-
1MnO4- reacts with 5Fe2+ and 2 MnO4- reacts with 5C2O42-

MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+ (aq) + 4H2O + 5Fe3+

2MnO4-(aq) + 16H+(aq) + 5C2O42-  10CO2 + 2Mn2+ (aq) + 8H2O
So overall
3MnO4-(aq) + 24H+(aq) + 5FeC2O4  10CO2 + 3Mn2+ (aq) + 5Fe3+ + 12H2O

So overall the ratio is 3 MnO4- to 5 FeC2O4

Example 4 Step1 : find moles of KMnO4

A 1.412 g sample of impure FeC2O4.2H2O was moles = conc x vol
dissolved in an excess of dilute sulfuric acid 0.0189 x 23.45/1000
and made up to 250 cm3 of solution. 25.0 cm3 = 4.43x10-4 mol
of this solution decolourised 23.45 cm3 of a
Step 2 : using balanced equation find moles FeC2O4.2H2O in 25cm3
0.0189 mol dm–3 solution of potassium
manganate(VII). = moles of KMnO4 x 5/3 (see above for ratio)
Calculate the percentage by mass of = 7.39x10-4 mol
FeC2O4.2H2O in the original sample. Step 3 : find moles FeC2O4.2H2O in 250 cm3
= 7.39x10-4 mol x 10
= 7.39x10-3 mol
Step 4 : find mass of FeC2O4.2H2O in 7.39x10-3 mol
mass= moles x Mr = 7.39x10-3 x 179.8 = 1.33g
Step 5 ; find % mass
%mass = 1.33/1.412 x100
= 94.1 %

EDTA titrations
The formation of the stable EDTA complex with metal ions can with the choice of suitable indicator be done in a
quantitative titration.
[Cu(H2O)6]2+ + EDTA4-  [Cu(EDTA)]2- + 6H2O Always the same 1:1 ratio with any metal ion

Example 5 Step1 : find moles of EDTA4-

A river was polluted with copper(II) moles = conc x vol = 0.0150 x 6.45/1000
ions. 25.0 cm3 sample of the river = 9.68x10-5 mol
water was titrated with a 0.0150 Step 2 : using balanced equation find moles Cu2+
mol dm–3 solution of EDTA4– , 6.45
1:1 ratio
cm3 were required for complete
reaction. = 9.68x10-5 mol
Calculate the concentration, in mol Step 3 : find conc Cu2+ in 25cm3
dm–3, of copper(II) ions in the river = 9.68x10-5 /0.025
water. = 0.00387 moldm-3

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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 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)  0.10 cm3 apparatus in each measurement

Calculate the percentage error for each piece of equipment used by

% uncertainty =  uncertainty x 100

Measurement made on apparatus Uncertainty of a measurement using a
burette. If the burette used in the
e.g. for burette titration had an uncertainty for each
% uncertainty = 0.10/average titre result x100 reading of +/– 0.05 cm3 then during a
titration two readings would be taken so
To calculate the maximum total percentage apparatus uncertainty in the the uncertainty on the titre volume would
final result add all the individual equipment uncertainties together. be +/– 0.10 cm3 .

To decrease the apparatus uncertainties

Reducing uncertainties in a titration
you can either decrease the sensitivity
uncertainty by using apparatus with a
Replacing measuring cylinders with pipettes or burettes which have
greater resolution (finer scale divisions ) or
lower apparatus uncertainty will lower the % uncertainty
you can increase the size of the
measurement made.
To reduce the % uncertainty in a burette reading it is necessary to make
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 If looking at a series of measurements in
the concentration of the substance in the burette. an investigation, the experiments with
the smallest readings will have the
highest experimental 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 < percentage
Calculating the percentage difference between the actual difference between the actual value and the calculated
value and the calculated value 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 > percentage
Calculate difference 214-203 = 11 difference between the actual value and the calculated
% = 11/214 x100 value then there is no discrepancy and all errors in the
=5.41% results can be explained by the sensitivity of the
equipment.

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PAG3. Measurement of an enthalpy change
Measuring the Enthalpy Change for a Reaction Experimentally
Calorimetric method This equation will only give the
energy for the actual quantities
For a reaction in solution we use the following equation used. Normally this value is
converted into the energy
energy change = mass of solution x heat capacity x temperature change
change per mole of one of the
Q (J) = m (g) x cp (J g-1K-1) x T ( K) reactants. (The enthalpy change
of reaction, H)

Calorimetric method
One type of experiment is one in which substances are mixed This could be a solid dissolving or reacting in a
in an insulated container and the temperature rise measured. solution or it could be two solutions reacting
together

General method
 washes the equipment (cup and pipettes etc) with the solutions to be used
 dry the cup after washing
 put polystyrene cup in a beaker for insulation and support
 Measure out desired volumes of solutions with volumetric pipettes and transfer to
insulated cup
 clamp thermometer into place making sure the thermometer bulb is immersed in
solution
 measure the initial temperatures of the solution or both solutions if 2 are used. Do this
every minute for 2-3 minutes
 At minute 3 transfer second reagent to cup. If a solid reagent is used then add the
solution to the cup first and then add the solid weighed out on a balance.
 If using a solid reagent then use ‘before and after’ weighing method
 stirs mixture (ensures that all of the solution is at the same temperature)
 Record temperature every minute after addition for several minutes

If the reaction is slow then the exact temperature rise can be

difficult to obtain as cooling occurs simultaneously with the
reaction

To counteract this we take readings at regular time intervals and

extrapolate the temperature curve/line back to the time the
reactants were added together.

We also take the temperature of the reactants for a few minutes

before they are added together to get a better average
temperature. If the two reactants are solutions then the
temperature of both solutions need to be measured before
addition and an average temperature is used.

Errors in this method Read question carefully. It

may be necessary to
• energy transfer from surroundings (usually loss) describe:
• approximation in specific heat capacity of solution. The method assumes all • Method
solutions have the heat capacity of water. • Drawing of graph with
• neglecting the specific heat capacity of the calorimeter- we ignore any energy extrapolation
absorbed by the apparatus. • Description of the
• reaction or dissolving may be incomplete or slow. calculation
• Density of solution is taken to be the same as water.

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Calculating the enthalpy change of reaction, Hr from experimental data
The heat capacity of water is 4.18
General method J g-1K-1. In any reaction where the
reactants are dissolved in water
1. Using q= m x cp x T calculate energy change for quantities used we assume that the heat capacity
is the same as pure water.
2. Work out the moles of the reactants used
3. Divide q by the number of moles of the reactant not in excess to give H Also assume that the solutions
have the density of water, which is
4. Add a sign and unit (divide by a thousand to convert Jmol -1 to kJmol-1
1g cm-3. Eg 25cm3 will weigh 25 g

Example 6. Calculate the enthalpy change of reaction for the reaction where 25.0cm3 of 0.20M
copper sulfate was reacted with 0.01mol (excess of zinc). The temperature increased 7.0oC .

Step 1: Calculate the energy change for the amount of reactants in the test tube.
Q = m x cp x T Note the mass is the mass of the copper sulfate
Q = 25 x 4.18 x 7 solution only. Do not include mass of zinc powder.
Q = 731.5 J

Step 2 : calculate the number of moles of the reactant not in excess.

moles of CuSO4 = conc x vol If you are not told what is in excess, then you need to work
= 0.2 x 25/1000 out the moles of both reactants and work out using the
= 0.005 mol balanced equation which one is in excess.

Step 3 : calculate the enthalpy change per mole, H (the enthalpy change of reaction)
H = Q/ no of moles
= 731.5/0.005
= 146300 J mol-1
= 146 kJ mol-1 to 3 sf
Remember in these
Finally add in the sign to represent the energy change: if temp increases the questions: sign, unit
reaction is exothermic and is given a minus sign e.g. –146 kJ mol-1

Example 7. 25.0 cm3 of 2.0 mol dm-3 HCl was neutralised by 25.0 cm3 of 2.0 mol dm-3 NaOH. The temperature
increased 13.5 oC. Calculate the enthalpy change per mole of HCl.

Step 1: Calculate the energy change for the amount of reactants in the test tube.
Q = m x cp x T
Note the mass equals the mass of acid + the
Q = 50 x 4.18 x13.5 mass of alkali, as they are both solutions.
Q = 2821.5 J

Step 2 : calculate the number of moles of the HCl.

moles of HCl = conc x vol
= 2 x 25/1000
= 0. 05 mol

Step 3 : calculate H the enthalpy change per mole which can be called the enthalpy change of neutralisation
H = Q/ no of moles
= 2821.5/0.05 Remember in these
= 56430 J mol-1 Exothermic and so is given a minus sign questions: sign, unit,
= -56.4 kJ mol-1 to 3 sf

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12
Often Hess’s law cycles are used to measure the enthalpy change for a reaction that cannot be measured directly by
experiments. Instead alternative reactions are carried out that can be measured experimentally.

H reaction This Hess’s law is used to work out the

enthalpy change to form a hydrated salt from
CuSO4 (s) + 5H2O (l) CuSO4.5H2O (s)
an anhydrous salt.

-66.1 kJ mol-1 + aq + aq +11kJ mol-1

This cannot be done experimentally because it
is impossible to add the exact amount of water
CuSO4 (aq) without the solid dissolving and it is not easy to
measure the temperature change of a solid.

H reaction + 11kJmol-1 = -66.1 kJ mol-1 Instead both salts are dissolved in excess water
H reaction= -66.1 - 11 to form a solution of copper sulfate. The
temperature changes can be measured for
= -77.1 kJ mol-1
these reactions.

Detailed method for measuring enthalpy change of solution of anhydrous copper(II) sulfate
1. Weigh out between 3.90 g and 4.10 g of anhydrous copper(II) sulfate in a dry weighing bottle. The precise mass
should be recorded.
2. Using a volumetric pipette, place 25 cm3 of deionised water into a polystyrene cup and record its temperature at the
beginning (t=0), start the timer and then record the temperature again every minute, stirring the liquid continuously.
3. At the fourth minute, add the powdered anhydrous copper(II) sulfate rapidly to the water in the polystyrene cup and
continue to stir, but do not record the temperature.
4. Reweigh the empty weighing bottle
5. At the fifth minute and for every minute up to 15 minutes, stir and record the temperature of the solution in the
polystyrene cup.
6. Plot a graph of temperature (on the y-axis) against time. Draw two separate best fit lines; one, which joins the points
before the addition, and one, which joins the points after the addition, extrapolating both lines to the fourth minute.
7. Use your graph to determine the temperature change at the fourth minute, which theoretically should have
occurred immediately on addition of the solid.
8. Using q= m x cp x T calculate energy change
= 20 x 4.18 x T
9. Calculate Hsolution by dividing q by number of moles of anhydrous copper(II) sulfate in mass added

The above method is then repeated using hydrated copper sulfate. The two Hsolution can then be used to calculate
the H for the enthalpy change of forming a hydrated salt as in the example above

N Goalby chemrevise.org 13
Measuring Enthalpies of Combustion using Flame Calorimetry

Enthalpies of combustion can be calculated by using calorimetry.

Generally the fuel is burnt and the flame is used to heat up water in a
metal cup.
Need to measure
• mass of spirit burner before and after
• Temperature change of water
• Volume of water in cup

Errors in this method

• energy losses from calorimeter
• Incomplete combustion of fuel
• Incomplete transfer of energy
• Evaporation of fuel after weighing
• Heat capacity of calorimeter not included
• Measurements not carried out under standard conditions as H2O is
gas, not liquid, in this experiment

Example 8. Calculate the enthalpy change of combustion for the reaction where 0.65 g of propan-1-ol was
completely combusted and used to heat up 150g of water from 20.1 to 45.5 oC

Step 1: Calculate the energy change used to heat up the water.

Q = m x cp x T
Note the mass is the mass of water in
Q = 150 x 4.18 x 25.4
the calorimeter and not the alcohol
Q = 15925.8 J

Step 2 : calculate the number of moles of alcohol combusted.

moles of propan-1-ol = mass/ Mr

= 0.65 / 60
= 0.01083 mol

Step 3 : calculate the enthalpy change per mole which is called cH (the enthalpy change of combustion)
H = Q/ no of moles
= 15925.8/0.01083
= 1470073 J mol-1
= 1470 kJ mol-1 to 3 sf
Remember in these
Finally add in the sign to represent the energy change: if temp increases the
questions: sign, unit
reaction is exothermic and is given a minus sign eg –1470 kJ mol-1

N Goalby chemrevise.org 14
PAG4: Testing for cations: Group 2, NH4+
Method: adding dilute sodium hydroxide This test can be used
a) Place about 10 drops of 0.1 mol dm–3 metal ion solution in a test tube. on group 2 metal
b) Add about 10 drops of 0.6 mol dm–3 sodium hydroxide solution, mixing well. ions and transition
c) Continue to add sodium hydroxide solution, dropwise with gentle shaking, until in excess metal ions.

Results for Group 2

The results in this test are an application of the trend that group II hydroxides become more soluble down the group.

Magnesium hydroxide is classed as insoluble in water and

will appear as a white precipitate. A suspension of magnesium hydroxide in water
will appear slightly alkaline (pH 9) so some
Simplest Ionic Equation for formation of Mg(OH)2 (s) hydroxide ions must therefore have been
Mg2+ (aq) + 2OH-(aq)  Mg(OH)2 (s). produced by a very slight dissolving.

Calcium hydroxide is classed as partially soluble in water and

will appear as a white precipitate (it may need more sodium A suspension of calcium hydroxide in water will
hydroxide to be added before it appears compared to a appear more alkaline (pH 11) than magnesium
magnesium solution.) hydroxide as it is more soluble so there will be
more hydroxide ions present in solution.
Simplest Ionic Equation for formation of Ca(OH)2 (s)
Ca2+ (aq) + 2OH-(aq)  Ca(OH)2 (s).
Strontium and barium salts will not form a hydroxide precipitate on addition of
sodium hydroxide due to their high solubility. The solutions will be highly alkaline

Results for transition metals

Copper solutions form a blue ppt, [Cu(H2O)6]2+ (aq) + 2OH- (aq)  Cu(H2O)4(OH)2 (s) + 2H2O (l)
iron (II) solutions form a green ppt [Fe(H2O)6]2+ (aq) + 2OH- (aq)  Fe(H2O)4(OH)2 (s) + 2H2O (l)
iron (III) solutions form a brown ppt
[Fe(H2O)6]3+ (aq) + 3OH- (aq)  Fe(H2O)3(OH)3 (s) + 3H2O (l)
Manganese (II) forms a pale brown ppt
Chromium (III) forms a green ppt [Mn(H2O)6]2+ (aq) + 2OH- (aq)  Mn(H2O)4(OH)2 (s) + 2H2O (l)

[Cr(H2O)6]3+ (aq) + 3OH- (aq)  Cr(H2O)3(OH)3 (s) + 3H2O (l)

Testing for Ammonium ions (NH4+)

a) Place about 10 drops of 0.1 mol dm–3 ammonium chloride in a test tube. Results: alkaline
b) Add about 10 drops of 0.4 mol dm–3 sodium hydroxide solution. Shake the mixture. ammonia gas is released
c) Warm the mixture in the test tube gently using a water bath. which turns the red
d) Test the fumes released from the mixture by holding a piece of damp red litmus litmus paper blue
paper in the mouth of the test tube.

Method: adding sulfate ions The results in this test are an

a) Place about 10 drops of 0.1 mol dm–3 metal ion solution in a test tube. application of the trend that
b) Add about 10 drops of 1.0 mol dm–3 sulfuric acid ( or other soluble sulfate solution. Group II sulfates become less
c) Continue to add sulfuric acid solution, dropwise with gentle shaking, until in excess soluble down the group

magnesium and calcium salts will not form a sulfate precipitate on addition of sulfate
ions due to their high solubility.

Strontium and barium solutions will form white precipitates with addition of sulfate ions

Full equation : SrCl2(aq) + Na2SO4 (aq)  2NaCl (aq) + SrSO4 (s)

Ionic equation: Sr2+ (aq) + SO42-(aq)  SrSO4 (s).
Ionic equation: Ba2+ (aq) + SO42-(aq)  BaSO4 (s).

N Goalby chemrevise.org 15
 Precipitation Reactions with sodium hydroxide and ammonia
The bases OH- and ammonia when in limited These reactions are classed as precipitation
amounts form the same hydroxide precipitates. reactions

[Cu(H2O)6]2+ (aq) + 2OH- (aq)  Cu(H2O)4(OH)2 (s) + 2H2O (l) Cu2+ (aq) + 2OH- (aq)  Cu(OH)2 (s)
Blue solution blue ppt Blue solution blue ppt
[Mn(H2O)6]2+ (aq) + 2OH- (aq)  Mn(H2O)4(OH)2 (s) + 2H2O (l) Mn2+ (aq) + 2OH- (aq)  Mn(OH)2 (s)
Very pale pink solution Pale brown ppt Very pale pink solution Pale brown ppt
[Fe(H2O)6]2+ (aq) + 2OH- (aq)  Fe(H2O)4(OH)2 (s) + 2H2O (l) Fe2+ (aq) + 2OH- (aq)  Fe(OH)2 (s)
green ppt green solution green ppt
green solution

[Fe(H2O)6]3+ (aq) + 3OH- (aq)  Fe(H2O)3(OH)3 (s) + 3H2O (l) Fe3+ (aq) + 3OH- (aq)  Fe(OH)3 (s)
brown ppt brown ppt
Yellow/brown solution Yellow/brown solution

[Cr(H2O)6]3+ (aq) + 3OH- (aq)  Cr(H2O)3(OH)3 (s) + 3H2O (l) Cr3+ (aq) + 3OH- (aq)  Cr(OH)3 (s)
green solution green ppt green solution green ppt

With ammonia when added in limited amounts the same hydroxide precipitates form. The ammonia acts as
a base, removes a proton from the aqueous complex and becomes the ammonium ion
[Mn(H2O)6]2+ (aq) + 2NH3 (aq)  Mn(H2O)4(OH)2 (s) + 2NH4+ (aq)

[Fe(H2O)6]3+ (aq) + 3NH3 (aq)  Fe(H2O)3(OH)3 (s) + 3NH4+ (aq)

Reaction with excess OH-

•This hydroxide is classed as amphoteric because it
With excess NaOH, the Cr hydroxide dissolves. can react with alkali to give a solution and react with
Cr becomes [Cr(OH)6]3- (aq) green solution acid to form the aqueous salt

Cr(H2O)3(OH)3 (s) + 3OH- (aq ) [Cr(OH)6]3- (aq) + 3H2O(l) Cr(H2O)3(OH)3 (s) + 3H+ (aq ) [Cr(H2O)6]3+(aq)

Reaction with excess NH3

With excess NH3 ligand exchange reactions occur with Cu and Cr, and their hydroxide precipitates dissolve in excess
ammonia

The ligands NH3 and H2O are similar in size and are
uncharged. Ligand exchange occurs without change of co- Cr becomes [Cr(NH3)6]3+ purple solution
ordination number for Cr

This substitution may, however, be incomplete as in Cu becomes [Cu(NH3)4(H2O)2]2+ deep blue solution
the case with Cu

Cr(OH)3(H2O)3(s) + 6NH3 (aq)  [Cr(NH3)6]3+(aq) + 3H2O(l) + 3OH- (aq)

Cu(OH)2(H2O)4(s) + 4NH3 (aq)  [Cu(NH3)4(H2O)2]2+ (aq) + 2H2O (l) + 2OH- (aq)

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PAG4: Testing for anions: – Group 7 (halide ions), OH– , CO32– , SO42–

Testing for presence of a sulfate ion

BaCl2 solution acidified with hydrochloric acid is used as a reagent to test for
sulphate ions.
If acidified barium chloride is added to a solution that contains sulfate ions a white
precipitate of barium sulfate forms.

Simplest ionic equation Other anions should give a negative

result which is no precipitate
Ba2+ (aq) + SO42-(aq)  BaSO4 (s).
forming.

The hydrochloric acid is needed to react with carbonate impurities that are often found in salts which
would form a white barium carbonate precipitate and so give a false result. You could not use sulfuric
acid because it contains sulfate ions and so would give a false positive result.

2HCl + Na2CO3  2NaCl + H2O + CO2 Fizzing due to CO2 would be observed if a carbonate was present.

Testing for presence of halide ions with silver nitrate. The role of nitric acid is to react with any
carbonates present to prevent formation of the
This reaction is used as a test to identify which halide ion is precipitate Ag2CO3. This would mask the desired
present. The test solution is made acidic with nitric acid, and observations
then silver nitrate solution is added dropwise.
2 HNO3 + Na2CO3  2 NaNO3 + H2O + CO2

Fluorides produce no precipitate

Chlorides produce a white precipitate
Ag+(aq) + Cl- (aq)  AgCl(s)
Bromides produce a cream precipitate
Ag+(aq) + Br- (aq)  AgBr(s)
Iodides produce a pale yellow precipitate
Ag+(aq) + I- (aq)  AgI(s)

The silver halide precipitates can be treated with ammonia solution to help differentiate between them
if the colours look similar:

Silver chloride dissolves in dilute ammonia to form a complex ion

AgCl(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Cl- (aq)
Colourless solution
Silver bromide dissolves in concentrated ammonia to form a complex ion
AgBr(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Br - (aq)
Colourless solution
Silver iodide does not react with ammonia – it is too insoluble.

Testing for presence of carbonate ions

Add any dilute acid and observe effervescence.
Bubble gas through limewater to test for CO2 – will turn limewater cloudy Fizzing due to CO2 would be
observed if a carbonate was
2HCl + Na2CO3  2NaCl + H2O + CO2 present

Testing for presence of a hydroxide ions

Alkaline hydroxide ions will turn red litmus paper blue.

N Goalby chemrevise.org 17
 More on Insoluble salts and Precipitation reactions

Insoluble salts can be made by mixing appropriate solutions of ions so that a precipitate is formed
barium nitrate (aq) + sodium sulfate (aq)  barium sulfate (s) + sodium nitrate (aq)
These are called precipitation reactions. A precipitate is a solid

There are some common rules for solubility of salts. No syllabus requires these to be learnt but a good
chemist does know them.
Soluble salts Insoluble salts
All sodium, potassium and ammonium salts
All nitrates
Most chlorides, bromides, iodides Silver, lead chlorides, bromides iodides
Most sulfates Lead, strontium and barium sulfates
Sodium, potassium and ammonium Most other carbonates
carbonates
Sodium, potassium and ammonium Most other hydroxides
hydroxides

When making an insoluble salt, normally the salt would be removed by filtration, washed with distilled
water to remove soluble impurities and then dried on filter paper

Filtration
Filter
paper Buchner
residue
funnel
Filter Filter paper
funnel
Buchner flask (has
Air outlet to
thicker glass walls than
water pump
a normal flask to cope
filtrate with the vacuum )

This is gravitational filtration. Use This is vacuum filtration. The apparatus is connected
if small amounts of solid are to a water pump which will produce a vacuum. Use
formed. if larger amounts of solid are formed.

For both types of filtration apparatus OCR expect filter paper to be drawn on the diagram

Writing ionic equations for precipitation reactions

We usually write ionic equations to show precipitation Spectator ions are ions that are
reactions. Ionic equations only show the ions that are • Not changing state
reacting and leave out spectator ions. • Not changing oxidation number

Take full equation Ba(NO3)2 (aq) + Na2SO4 (aq)  BaSO4 (s) + 2 NaNO3 (aq)

Separate (aq) solutions into Ba2+(aq) + 2NO3-(aq) + 2Na+ (aq)+ SO42-(aq)  BaSO4(s) + 2 Na+(aq)+ 2NO3- (aq)
ions

Cancel out spectator ions leaving

Ba2+ (aq) + SO42-(aq)  BaSO4 (s).
the simplest ionic equation

N Goalby chemrevise.org 18
PAG5. Preparation of a pure organic liquid

Purifying an organic liquid

General method
• Put the distillate of impure product into a separating funnel
Sodium hydrogencarbonate will neutralise
• wash product by adding either
any remaining reactant acid.
• sodium hydrogencarbonate solution , shaking and
releasing the pressure from CO2 produced.
Sodium chloride will help separate the
• Saturated sodium chloride solution
organic layer from the aqueous layer
•Allow the layers to separate in the funnel, and then run and
discard the aqueous layer. The layer with lower density will be the
upper layer. This is usually the organic layer
•Run the organic layer into a clean, dry conical flask and add three
spatula loads of drying agent (e.g. anhydrous sodium sulfate, The drying agent should
calcium chloride) to dry the organic liquid. When dry the organic •be insoluble in the organic liquid
liquid should appear clear. • not react with the organic liquid

• Carefully decant the liquid into the distillation flask Decant means carefully pour off organic
liquid leaving the drying agent in the
•Distill to collect pure product conical flask

Separating funnel

Distillation It’s important to be able to

draw and label this apparatus
In general used as separation technique to separate an accurately. Don’t draw lines
thermometer between flask, adaptor and
organic product from its reacting mixture. Need to
condenser.
collect the distillate of the approximate boiling point
range of the desired liquid.

Note the bulb of the thermometer should be Liebig condenser

at the T junction connecting to the
condenser to measure the correct boiling
point

Note the water goes in the bottom of the Water

condenser to go against gravity. This allows more out
efficient cooling and prevents back flow of water.
Round Water in
bottomed
flask
Electric heaters are often used to heat organic Heat
chemicals. This is because organic chemicals are
normally highly flammable and could set on fire The collection flask can be
with a naked flame. cooled in ice to help improve
yield of distillate

N Goalby chemrevise.org 19
 Detailed method for preparing and purifying a haloalkane from an alcohol
1. Measure 8 cm3 of 2-methylpropan-2-ol in a measuring cylinder and measure its mass.
2. Pour the 2-methylpropan-2-ol into a separating funnel, and reweigh the measuring cylinder to find the
mass of the 2-methylpropan-2-ol used.
3. In a fume cupboard, add 20 cm3 of concentrated hydrochloric acid to the separating funnel, in portions
of 3cm3. After each portion, stopper the flask and invert it several times . Open the tap when doing this
to release the pressure.
4. Allow the separating funnel to stand in the fume cupboard for about 20 minutes. Gently shake it at
intervals.
5. After 20 minutes, allow the layers to separate in the funnel. Open the tap and remove the lower
aqueous layer. Dispose of this layer.
6. Add sodium hydrogencarbonate solution in 2 cm3 portions to the separating funnel. This neutralises any
remaining acid. Shake the funnel after each addition, and release the pressure. Continue until no more
bubbles of CO2 are seen.
7. Allow the layers to separate in the funnel. Again remove and pour away the lower aqueous layer. Run
off the organic layer into a clean conical flask and add two spatulas of anhydrous sodium sulfate.
Stopper the flask, shake the contents and allow this to stand until the liquid becomes clear. This step
dries the organic liquid.
8. Decant the liquid into a weighed clean distillation flask.
9. Distil the liquid by holding a 250ml beaker half-full of boiled water around the flask using standard
distillation set up. Collect the liquid that distils in the range 47-53oC.
10. Measure the mass of the 2-chloro-2-methylpropane collected.

Detailed method for preparing and purifying Cyclohexene from cyclohexanol

OH
Conc
H3PO4
+H2O

a) Pour about 20 cm3 of cyclohexanol into a weighed 50 cm3 pear-shaped flask. Reweigh the flask and record
the mass of cyclohexanol.
b) Using a plastic graduated dropping pipette, carefully and with frequent shaking, add to the flask
approximately 8 cm3 of concentrated phosphoric acid.
c ) Add a few anti-bumping granules to the flask and assemble the distillation apparatus, so that the contents
of the flask may be distilled. Heat the flask gently, distilling over any liquid which boils below 100 °C.
d) Pour the distillate into a separating funnel and add 50 cm 3 of saturated sodium chloride solution. Shake
the mixture and allow the two layers to separate.
e) run off the lower layer into a beaker and then transfer the upper layer, which contains the crude
cyclohexene, into a small conical flask.
f) Add a few lumps of anhydrous calcium chloride or anhydrous sodium sulfate(VI) or anhydrous magnesium
sulfate to the crude cyclohexene to remove water. Stopper the flask, shake the contents and allow this to
stand until the liquid becomes clear.
g) Decant the liquid into a clean, dry, weighed sample container.
h) Reweigh the container, calculate the mass of dry cyclohexene produced

N Goalby chemrevise.org 20
Detailed Method for Preparing and Purifying an Ester
Propyl ethanoate can be made in the laboratory from propan-
1-ol and ethanoic acid.
The equation for the reaction is
CH3COOH + CH3CH2CH2OH  CH3COOCH2CH2CH3 + H2O
Procedure
1. Propan-1-ol (50 cm3) and ethanoic acid (50 cm3) are mixed
thoroughly in a 250 cm3 round-bottomed flask.
2. Concentrated sulfuric acid (10 cm3) is added drop by drop Sulfuric acid is a catalyst
Adding conc H2SO4 is an exothermic reaction- to
to the mixture, keeping the contents of the flask well-shaken
prevent uncontrolled boiling over add drop by drop
and cooled in an ice-water bath. and cool

3. When the acid has all been added, a reflux condenser is In reflux the reactant vapours of volatile compound
fitted to the flask and the mixture gently boiled over an are condensed and returned to the reaction mixture.
electric heating mantle for about 30 minutes. The reaction is slow so it is heated for 30 minutes
The electric heating mantle allows for controlled
heating and stops flammable vapour igniting
4. The mixture is cooled, and the apparatus rearranged for
distillation. The crude ester (about 60 cm3) is distilled off. Sodium carbonate reacts with unreacted acid and
5. The distillate is placed in a separating funnel and shaken remaining catalyst still present after distillation.
with about half its volume of 30% sodium carbonate solution, The reaction produces CO2 so the pressure of gas
with the pressure being released at intervals. The lower needs to be released.
The upper layer is organic because it has a lower
aqueous layer is then discarded.
density than water

6. The crude ester is shaken in a separating funnel with about

half its volume of 50% calcium chloride solution, which
removes unreacted alcohol. The lower layer is discarded.
Calcium chloride is a drying agent. The liquid will
7. The ester is run into a clean, dry flask containing some appear clear when dry.
anhydrous calcium chloride and swirled.

8. The ester is filtered into a clean, dry flask, with a few anti- Anti-bumping granules are added to the prevent
bumping granules, and distilled. The fraction boiling between vigorous, uneven boiling by making small bubbles
100°C and 103°C is collected. form instead of large bubbles

Measuring boiling point

Purity of liquid can be determined by measuring a boiling point. This can be done
in a distillation set up or by simply boiling a tube of the sample in an heating oil To get a correct measure of
bath. If the liquid is pure it will have the boiling point referred to in data books. If boiling point the
impure the boiling point tends to be higher than the pure liquid thermometer should be
above the level of the surface
of the boiling liquid and be
Pressure should be noted as changing pressure can change the boiling point of
measuring the temperature
a liquid
of the saturated vapour.

Measuring boiling point is not the most accurate method of identifying a

substance as several substances may have the same boiling point.

N Goalby chemrevise.org 21
PAG6. Preparation of a pure organic solid and test of its purity

Purifying an organic solid: Recrystallisation Used for purifying aspirin

Step Reason

1. Dissolve the impure compound in a minimum volume An appropriate solvent is one which will dissolve both
of hot (near boiling) solvent. compound and impurities when hot and one in which the
compound itself does not dissolve well when cold.
The minimum volume is used to obtain saturated
solution and to enable crystallisation on cooling
2. Hot filter solution through (fluted) filter paper quickly. This step will remove any insoluble impurities and heat
will prevent crystals reforming during filtration
3. Cool the filtered solution by inserting beaker in ice Crystals will reform but soluble impurities will remain in
solution form because they are present in small quantities
so solution is not saturated. Ice will increase the yield of
crystals
4. Suction filtrate with a Buchner flask to separate out The water pump connected to the Buchner flask reduces
crystals the pressure and speeds up the filtration.
5 Wash the crystals with distilled water To remove soluble impurities

6. Dry the crystals between absorbent paper

Loss of yield in this process

• Crystals lost when filtering or washing
• Some product stays in solution after recrystallisation
• other side reactions occurring

If the crystals are not dried properly the mass will be larger
than expected which can lead to a percentage yield >100%

Buchner flask

The crystals formed through

recrystallisation may appear as
larger, needle-like crystals, that
are lighter in colour.

N Goalby chemrevise.org 22
PAG6. Preparation of a pure organic solid and test of its purity
Detailed method for Preparation of Aspirin Aspirin is made from 2-hydroxybenzoic
O acid which contains a phenol group. In the
CO2H
CO2H CH3 C O
reaction the phenol group is turned into an
ester by reacting it with the reactive
OH
+ O  O C CH3 + CH CO H
3 2
ethanoic anhydride
CH3 C
O Aspirin Ethanoic anhydride is used instead of
Add to a 50 cm3 pear-shaped flask 2.0 g of 2-hydroxybenzoic acid and acid chlorides because it is cheaper, less
4 cm3 of ethanoic anhydride. corrosive, less vulnerable to hydrolysis,
To this mixture add 5 drops of 85% phosphoric(v) acid and swirl to and less dangerous to use.
mix, Fit the flask with a reflux condenser and heat the mixture on a
The excess ethanoic anhydride will
boiling water bath for about 5 minutes. Without cooling the mixture,
hydrolyse and the contents of the flask
carefully add 2 cm3 of water in one portion down the condenser.
will boil.
When the vigorous reaction has ended, pour the mixture into 40 cm 3
of cold water in a 100 cm3 beaker, stir and rub the sides of the beaker
with a stirring rod necessary to induce crystallisation and, finally,
allow the mixture to stand in ice bath to complete crystallisation.
Collect the product by suction filtration and wash it with a little water.

Purification stage: recrystallisation

Using a measuring cylinder, measure out 15 cm3 of ethanol into a
boiling tube.
Prepare a beaker half-filled with hot water from a kettle at a Avoid naked flames due to
temperature of approximately 75 °C. flammability of ethanol
Use a spatula to add the crude aspirin to the boiling tube with ethanol
and place the tube in the beaker of hot water.
Stir the contents of the boiling tube until all of the aspirin dissolves
into the ethanol.
Pour the hot solution containing dissolved aspirin through a warmed This step will remove any insoluble
filter funnel and fluted filter paper to hot filter impurities and heat will prevent crystals
Then pour filtrate into 40 cm3 of water in a conical flask. reforming during filtration
Allow the conical flask to cool slowly and white needles of aspirin
should separate. Soluble impurities will remain in solution form
Cool the whole mixture in an ice bath. because they are present in small quantities
Filter off the purified solid under reduced pressure and allow it to dry so solution is not saturated. Ice will increase
on filter paper. the yield of crystals
Record the mass of the dry purified solid

Detailed method for Nitration Procedure

Conc acids are corrosive- wear
Measure 2.5 cm3 of methyl benzoate into a small conical flask and then gloves
dissolve it in 5 cm3 of concentrated sulfuric acid. When the liquid has The acids react together to make
dissolved, cool the mixture in ice. the NO2+ ion
Prepare the nitrating mixture by adding drop by drop 2 cm3 of This reaction is exothermic so acids
concentrated sulfuric acid to 2 cm3 of concentrated nitric acid. Cool this are kept cool and acid is added
mixture in ice as well. dropwise

Now add the nitrating mixture drop by drop from a dropping pipette to
the solution of methyl benzoate. Stir the mixture with a thermometer and The temperature is kept low at this
keep the temperature below 10 °C. When the addition is complete, allow stage to prevent multiple
the mixture to stand at room temperature for another 15 minutes. substitution of nitro groups on the
After this time, pour the reaction mixture on to about 25 g of crushed ice benzene ring
and stir until all the ice has melted and crystalline methyl 3-nitrobenzoate
has formed.
Then use same purification method as in aspirin above

N Goalby chemrevise.org 23
 Reflux
Reflux is used when heating organic reaction mixtures for long periods. The
condenser prevents organic vapours from escaping by condensing them back Water out
to liquids. The reactant vapours of volatile compound are condensed and
returned to the reaction mixture.
condenser
Never seal the end of the condenser as the build up of gas
pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated including the
distillation set up

Anti-bumping granules are added to the flask in both distillation Water in

and reflux to prevent vigorous, uneven boiling by making small
bubbles form instead of large bubbles

Round
It’s important to be able to draw and label this apparatus bottomed
flask
accurately.
• Don’t draw lines between flask and condenser.
• Don’t have top of condenser sealed
• Condenser must have outer tube for water that is sealed
Heat
at top and bottom
• Condenser must have two openings for water in and out
that are open

Measuring melting point

One way of testing for the degree of purity is to determine the melting
“point”, or melting range, of the sample.
Thermometer with
If the sample is very pure then the melting point will be a capillary tube
sharp one, at the same value as quoted in data books. strapped to it
containing sample
If impurities are present (and this can include solvent from the
recrystallisation process) the melting point will be lowered and the Heating oil- needs to
sample will melt over a range of several degrees Celsius have boiling point
higher than samples
melting point and low
Melting point can be measured in an electronic melting point machine or flammability
by using a practical set up where the capillary tube is strapped to a
thermometer immersed in some heating oil.
In both cases a small amount of the sample is put into a capillary tube. The
tube is heated up and is heated slowly near the melting point

Heat
Comparing an experimentally determined melting point value
with one quoted in a data source will verify the degree of
purity.

Sometimes an error may occur if the temperature on the thermometer is not the same as the temperature in the
actual sample tube.

N Goalby chemrevise.org 24
Separation of species by thin-layer chromatography

Method: Thin-layer chromatography

Wear plastic gloves to prevent contamination
a) Wearing gloves, draw a pencil line 1 cm above the bottom of a from the hands to the plate
TLC plate and mark spots for each sample, equally spaced along
line. pencil line –will not dissolve in the solvent
b) Use a capillary tube to add a tiny drop of each solution to a tiny drop – too big a drop will cause different
different spot and allow the plate to air dry. spots to merge
c) Add solvent to a chamber or large beaker with a lid so that is no
more than 1cm in depth Depth of solvent– if the solvent is too deep it will
d) Place the TLC plate into the chamber, making sure that the level dissolve the sample spots from the plate
of the solvent is below the pencil line. Replace the lid to get a
lid– to prevent evaporation of toxic solvent
tight seal.
e) When the level of the solvent reaches about 1 cm from the top Will get more accurate results if the solvent is
of the plate, remove the plate and mark the solvent level with a allowed to rise to near the top of the plate but the
pencil. Allow the plate to dry in the fume cupboard. Rf value can be calculated if the solvent front does
f) Place the plate under a UV lamp in order to see the spots. Draw not reach the top of the plate
around them lightly in pencil.
g) Calculate the Rf values of the observed spots. dry in a fume cupboard as the solvent is toxic

UV lamp used if the spots are colourless and not

visible

Rf value = distance moved by amino acid

distance moved by the solvent

If the stationary phase was polar and the moving

Separation by chromatography depends on the
phase was non- polar e.g. Hexane. Then non-polar
balance between solubility in the moving phase and
compounds would pass through the plate more quickly
retention in the stationary phase.
than polar compounds as they would have a greater
solubility in the non-polar moving phase.
A solid stationary phase separates by adsorption, (Think about intermolecular forces)
A liquid stationary phase separates by relative solubility

Rf values are used to identify different substances.

N Goalby chemrevise.org 25
PAG7. Tests for alcohol, aldehyde, alkene and carboxylic acid

Functional group test for an Alkene

To 0.5 cm3 of bromine water in a test tube add a few drops of the unknown and shake.
Observation: alkenes should decolourise bromine water

Reaction with 2,4-dinitro phenylhydrazine

2,4-DNP reacts with both aldehydes and ketones. The product Use 2,4-DNP to identify if the compound is a
is an orange precipitate, It can be used as a test for a carbonyl carbonyl. Then to differentiate an aldehyde
group in a compound. from a ketone use Tollens’ reagent.

The melting point of the crystal formed can be used to help

identify which carbonyl was used. Take the melting point of
orange crystals product from 2,4-DNP. Compare melting point
with known values in database

Functional group tests for an Aldehyde

Tollens’ Reagent
Reagent: Tollens’ reagent formed by mixing aqueous ammonia and silver
nitrate. The active substance is the complex ion of [Ag(NH 3)2]+ .
Conditions: heat gently
Reaction: aldehydes only are oxidised by Tollens’ reagent into a carboxylic
acid and the silver(I) ions are reduced to silver atoms
Observation: with aldehydes, a silver mirror forms coating the inside of the
test tube. Ketones result in no change.

CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+

Tollens’ reagent method

Place 1 cm3 of silver nitrate solution in each of two clean boiling tubes.
Then add one drop of sodium hydroxide solution to form a precipitate of
silver oxide. Add ammonia solution dropwise until a clear, colourless
solution is formed. Add a few drops of the unknown and leave in the
water bath for a few minutes.

Fehling’s solution
Reagent: Fehling’s solution containing blue Cu 2+ ions. Fehling's solution method
Conditions: heat gently Place 1 cm3 of Fehling's A into each of
two boiling tubes, and then add Fehling's
Reaction: aldehydes only are oxidised by Fehling’s Solution
into a carboxylic acid and the copper (II) ions are B until the blue precipitate redissolves.
reduced to copper(I) oxide . Add a few drops of the unknown and
Observation: Aldehydes :Blue Cu 2+ ions in solution change leave in the water bath for a few
to a red precipitate of Cu2O. Ketones do not react minutes.

CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+

N Goalby chemrevise.org 26
Partial Oxidation of Primary Alcohols H
O

Reaction: primary alcohol  aldehyde

Reagent: potassium dichromate (VI) solution and dilute sulfuric acid. H C C

Conditions: (use a limited amount of dichromate) warm gently and distil out
the aldehyde as it forms: H
H

Ethanal

Observation: the orange

O + H2O
OH + [O] dichromate ion (Cr2O72-) reduces
to the green Cr 3+ ion
CH3CH2CH2OH + [O]  CH3CH2CHO + H2O
propan-1-ol propanal

Detailed Method: The partial oxidation of propan-1-ol

This experiment uses a limited quantity of oxidising agent (0.01 mol) and the product is distilled from the reaction
mixture immediately it is formed. In this way we hope to achieve a partial oxidation of propan-1-ol.

 Place about 10 cm3 of dilute sulfuric acid in a flask and add about 3g of potassium dichromate(VI) and 2 or 3 anti-
bumping granules. Shake the contents of the flask until solution is complete (do not warm).
 Add 1.5 cm3 of propan-1-ol in drops from a dropping pipette, shaking the flask so as to mix the contents, and
then assemble distillation apparatus as shown below
 Gently heat and slowly distil 2 cm3 of liquid into a test tube, taking care that none of the reaction mixture
splashes over.

SAFETY
You must wear gloves when handling solid potassium dichromate(Vl) since it is highly toxic and a category 2 carcinogen;
it is also an irritant. Avoid inhaling any dust. Concentrated sulfuric acid is corrosive.
Reflux: Full Oxidation of Primary Alcohols
H H
Reaction: primary alcohol  carboxylic acid
O

Reagent: potassium/sodium dichromate(VI) solution and H C C C

sulfuric acid
Conditions: use an excess of dichromate, and heat under O H
reflux: (distil off product after the reaction has
H H

finished) Propanoic acid

Observation: the
OH OH orange dichromate
+ 2[O] + H2O ion (Cr2O72-)
O reduces to the
green Cr 3+ ion
propan-1-ol Propanoic acid

Detailed method
 Measure 5 cm3 of water into a boiling tube. Add 6 g of sodium dichromate(VI), shake and set aside to dissolve.
 Put about 1.5 cm3 propan-1-ol into a 50 cm3 round bottomed flask and add about 5 cm3 of water and two or
three anti-bumping granules. Put a condenser on the flask for reflux, as shown in figure below.
 Add 2 cm3 of concentrated sulfuric acid down the condenser in drops from a dropping pipette. While the
mixture is still warm, start to add your sodium dichromate(VI) solution down the condenser in drops from a
dropping pipette. The energy released from the reaction should make the mixture boil. Add the solution a drop
at a time so that the mixture continues to boil without any external heating.
 When all the sodium dichromate(VI) solution has been added, use a low Bunsen burner flame to keep the
mixture boiling for 10 minutes, not allowing any vapour to escape.
 At the end of that time remove the Bunsen burner and arrange the apparatus for distillation. Gently distil 2-3
cm3 of liquid into a test tube.

N Goalby chemrevise.org 27
 Functional group test for a Carboxylic acid The presence of a carboxylic acid can be tested by
To 0.5 cm3 of your unknown solution in a test tube add a addition of sodium carbonate. It will fizz and produce
small amount of sodium carbonate solid and observe. carbon dioxide
Result carboxylic acids will fizz with sodium carbonate 2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2

Testing for haloalkanes method

• Arrange three test tubes in a row and add three drops of halalkane in the sequence 1-chlorobutane, 1-
bromobutane, 1-iodobutane.
• Add 4 cm3 of 0.02 M silver nitrate to each haloalkane.
• Without delay, put all three test tubes simultaneously in a hot water bath.
• Note the order in which precipitates appear

Comparing the rate of hydrolysis of haloalkanes reaction

Hydrolysis is defined as the splitting of a molecule ( in this case a Water is a poor nucleophile but it can react
haloalkane) by a reaction with water slowly with haloalkanes in a substitution
reaction
CH3CH2X + H2O  CH3CH2OH + X- + H+

Aqueous silver nitrate is added to a haloalkane and the halide CH3CH2I + H2O  CH3CH2OH + I- + H+
leaving group combines with a silver ion to form a silver halide
Ag+ (aq) + I-(aq)  AgI (s) - yellow precipitate
precipitate.
The precipitate only forms when the halide ion has left the The iodoalkane forms a precipitate with the
haloalkane and so the rate of formation of the precipitate can be silver nitrate first as the C-I bond is weakest
used to compare the reactivity of the different haloalkanes. and so it hydrolyses the quickest

The quicker the precipitate is formed, the faster the substitution

reaction and the more reactive the haloalkane AgI (s) - yellow precipitate
AgBr(s) – cream precipitate forms faster
The rate of these substitution reactions depends on the strength of the AgCl(s) – white precipitate
C-X bond . The weaker the bond, the easier it is to break and the faster
the reaction.

Phenols

Phenols are very weakly acidic. They are weaker acids than carboxylic acids.
Both phenols and carboxylic acids will react with sodium metal and sodium
hydroxide. Only carboxylic acids will react with sodium carbonate as a phenol is not
strong enough an acid to react.

OH + Na
-
O Na+ + ½ H2

The sodium phenoxide

-
Na+ + H2O compound is more soluble than
OH + NaOH O
the original phenol. So the solid
phenol dissolves on addition of
sodium phenoxide NaOH

N Goalby chemrevise.org 28
Summary of Identification of Functional Groups by test-tube reactions

Functional group Reagent Result

Alkene Bromine water Orange colour

decolourises
carbonyl 2,4-DNP Orange precipitate
formed
Aldehyde Tollens’ Reagent Silver mirror formed

Carboxylic acid Carbonate ions CO32- Effervescence of CO2

e.g. Sodium carbonate evolved
1o 2o alcohol and Sodium dichromate and Orange to green colour
aldehyde sulfuric acid change
haloalkane Warm with aqueous Slow formation of white
silver nitrate in ethanol precipitate
phenols Will react with sodium Fizzing with sodium but
and sodium hydroxide- no reaction with sodium
won’t react with carbonate
Carbonate ions CO32-

N Goalby chemrevise.org 29
PAG8. Measuring the EMF of an electrochemical cell
Electron
flow
Method
• Clean the zinc and copper foils with emery before use. Salt bridge
Degrease the metal using some cotton wool and copper
propanone. electrode
Zinc
• Place the copper strip into a 100 cm3 beaker with
electrode
about 50 cm3 of 1 mol dm–3 CuSO4 solution.
• Place the zinc strip into a 100 cm3 beaker with about
50 cm3 of 1 mol dm–3 ZnSO4 solution. 1 mol dm–3
1 mol dm–3
• Use a strip of filter paper soaked in saturated zinc sulfate copper
potassium nitrate solution for the salt bridge solution sulfate
• Connect the Cu(s)|Cu2+ (aq) and Zn(s)|Zn2+ (aq) half- solution
cells by connecting the metals using the crocodile clips
and leads provided to the voltmeter

Salt Bridge
The salt bridge is used to connect up the circuit. The free moving ions conduct the charge.

A salt bridge is usually made from a piece of filter paper (or material) soaked in a salt solution, usually Potassium Nitrate.
It can also be a glass U tube containing a salt solution plugged with cotton wool

The salt should be unreactive with the electrodes and electrode solutions.. E.g. potassium chloride would not be suitable
for copper systems because chloride ions can form complexes with copper ions.

A wire is not used because the metal wire would set up its own electrode system with the solutions.

Pt electrode
Salt bridge
Method copper KNO3 (aq)
If one or both of the half cells do not contain a electrode
conducting metal, we must use an inert platinum
electrode.
Set up a copper half cell using a similar
arrangement to the previous one. Combine it
with a Fe2+/Fe3+ half-cell with a platinum 1 mol dm–3
electrode. copper
The half cell should have a mixture of acidified sulfate
solution
1.0 mol dm–3 iron(II) sulfate solution and an equal
volume of 0.5 mol dm–3 iron(III) sulfate solution 1 mol dm–3 FeSO4 and
as the electrolyte. Use a fresh salt bridge. 0.5 mol dm–3 Fe2(SO4)3

Note: in the electrode system containing two solutions it is

A platinum electrode is used because it is necessary to use a platinum electrode and both ion solutions must
unreactive and can conduct electricity be of a 1 mol dm–3 concentration so [Fe2+] = 1 mol dm–3 and
[Fe3+] = 1 mol dm–3 .

N Goalby chemrevise.org 30
 PAG9 measuring the rate of reaction: by an continuous monitoring method

When we follow one experiment over time recording the change in

concentration it is the continuous rate method.

concentration
The gradient represents the rate of reaction. The reaction is
fastest at the start where the gradient is steepest. The rate
drops as the reactants start to get used up and their
concentration drops. The graph will eventual become
horizontal and the gradient becomes zero which represents
the reaction having stopped.
time

Measurement of the change in volume of a gas

This works if there is a change in the number of moles of gas
in the reaction. Using a gas syringe is a common way of
following this. It works quite well for measuring continuous
rate but a typical gas syringe only measures 100ml of gas so gas syringe
you don’t want at reaction to produce more than this volume.
Quantities of reactants need to be calculated carefully.

Mg + HCl  MgCl2 +H2

Typical Method
The initial rate is the rate at the start of the • Measure 50 cm3 of the 1.0 mol dm–3 hydrochloric acid
reaction, where it is fastest. It is obtained by taking and add to conical flask.
the gradient of a continuous monitoring conc vs • Set up the gas syringe in the stand
time graph at time = zero. A measure of initial rate • Weigh 0.20 g of magnesium.
is preferable as we know the concentrations at the • Add the magnesium ribbon to the conical flask, place the
start of the reaction. bung firmly into the top of the flask and start the timer.
• Record the volume of hydrogen gas collected every 15
seconds for 3 minutes.
concentration

Large excess of reactants

rate = gradient of In reactions where there are several reactants, if the
tangent to curve concentration of one of the reactant is kept in a large excess
then that reactant will appear not to affect rate and will be
pseudo-zero order . This is because its concentration stays
virtually constant and does not affect rate.
time

Continuous rate experiments

Continuous rate data
0.060 This is data from one experiment where the concentration of a
substance is followed throughout the experiment.
If half-lives are constant
[A]

then the order is 1st order

This data is processed by plotting the data and calculating
0.030 successive half-lives.

0.015 The half-life of a first-order reaction

0.0075 is independent of the concentration and is constant

If half-lives rapidly increase then the order is

t½ t½ t½ 2nd order
Time (min)

N Goalby chemrevise.org 31
PAG10 measuring the rate of reaction: by an initial rate method
The initial rate can be calculated from taking the Initial rate can also be calculated from clock reactions
gradient of a continuous monitoring conc vs time where the time taken to reach a fixed concentration is
graph at time = zero measured.

A Common Clock Reaction (no need to learn details)

In clock reactions there are often two
Hydrogen peroxide reacts with iodide ions to form iodine. The thiosulfate
successive reactions and an end point is
ion then immediately reacts with iodine formed in the second reaction as
achieved when one limited reactant runs
shown below.
out, resulting in a sudden colour change

H2O2(aq) + 2H+(aq) + 2I–(aq) → I2(aq) + 2H2O(l)

By repeating the experiment several times,
2S2O32–(aq) + I2(aq) → 2I–(aq) + S4O62–(aq) varying the concentration of a reactant e.g.
I–, ( keeping the other reactants at constant
When the I2 produced has reacted with all of the limited amount of concentration )you can determine the
thiosulfate ions present, excess I2 remains in solution. Reaction with the order of reaction with respect to that
starch then suddenly forms a dark blue-black colour. reactant
A series of experiments is carried out, in which the concentration of iodide
ions is varied, while keeping the concentrations of all of the other reagents
the same. In each experiment the time taken (t) for the reaction mixture to The initial rate of the reaction can be
turn blue is measured. represented as (1/t )

Detailed method
• Put each of the chemicals in the table in separate burettes.
• In each experiment, measure out required volumes of the potassium iodide, sodium thiosulfate, starch and
water into a small conical flask from the burettes
• Measure the hydrogen peroxide into a test tube
• Pour the hydrogen peroxide from the test tube into the conical flaks and immediately start the timer. Stir the
mixture.
• Time until the first hint of blue/ black colour appears

Sulfuric Potassium Sodium Hydrogen

Experiment peroxide ml
acid (H+) ml Starch ml Water ml iodide(I-) ml Thiosulfate S2O32- ml

1 25 1 20 5 5 10
10
2 25 1 15 10 5
3 25 1 10 15 5 10

4 25 1 5 20 5 10

5 25 1 0 25 5 10

Normally to work out the rate equation we do a series of experiments where the initial concentrations of reactants are
changed (one at a time) and measure the initial rate each time.
Working out rate order graphically
In an experiment where the concentration of one of
log (rate)

the reagents is changed and the reaction rate measured

it is possible to calculate the order graphically
gradient = n
Taking rate equation
Rate = k [I- ]n = change in y
y intercept = log K
change in x
Log both sides of equation
Log rate = log k + n log [Y]
log [I- ]
Y= c + mx
In this experiment high concentrations with quick
A graph of log rate vs log [I- ] will yield a straight line where the
times will have the biggest percentage errors.
gradient is equal to the order n
N Goalby chemrevise.org 32
Investigation of how the rate of a reaction changes with temperature
Experiment: sodium thiosulfate and hydrochloric acid
In the experiment between sodium thiosulfate and hydrochloric acid we usually measure
reaction rate as 1/time where the time is the time taken for a cross placed underneath the
reaction mixture to disappear due to the cloudiness of the sulfur .
Na2S2O3 + 2HCl  2NaCl + SO2 + S + H2O
This is an approximation for initial rate of reaction as it does not include the change in
concentration term. We can use this because we can assume the amount of sulfur
produced to block out the cross in each experiment is the same and constant so each time
we do the experiment the same amount of sulphur is produced. The change in
concentration of sulfur is therefore the same for each experiment so only the time taken to
reach this concentration is relevant.

Typical Method
•Measure 10 cm3 of 0.2 mol dm-3 hydrochloric acid and 10 cm3 of sodium thiosulfate in separate clean
measuring cylinders. Put the solutions in separate boiling tubes
•Choose a temperature to investigate use water bath to get the two solutions to that temperature by
placing the boiling tubes in the water bath.
•Place the flask on the centre of the large cross; first add the sodium thiosulfate to the flask. Then add the
hydrochloric acid and start the stopwatch and swirl to mix the solutions.
•Stop the clock when the cross disappears and note the time.
•Repeat the experiment for four more different temperatures (maximum temperature should be 70 oC).

Analysis of results to calculate Activation Energy 1/T

The Arrhenius equation can be rearranged

ln k = constant – EA/(RT)
ln (Rate)

Gradient = - EA/ R
k is proportional to the rate of reaction so ln k can be
replaced by ln(rate)
EA = - gradient x R
From plotting a graph of ln(rate) or ln k against 1/T the
activation energy can be calculated from measuring the
gradient of the line

Example 8 1/T
0.0029 0.003 0.0031 0.0032 0.0033 0.0034
Temperature time t -1.6
T (K) 1/T (s) 1/t Ln (1/t) x1,y1
297.3 0.003364 53 0.018868 -3.9703 -2.1
310.6 0.00322 24 0.041667 -3.1781
ln (Rate)

317.2 0.003153 16 0.0625 -2.7726 -2.6

323.9 0.003087 12 0.083333 -2.4849

-3.1
335.6 0.00298 6 0.166667 -1.7918

-3.6
x2,y2
gradient = y2-y1 The gradient should
x2-x1 always be -ve -4.1

In above example gradient =-5680 use a line of best fit

EA = - gradient x R (8.31) use all graph paper
= - -5680 x8.31 choose points far apart on the graph to
= 47200 J mol-1 calculate the gradient

The unit of EA using this equation will be J mol-1 . Convert

into kJ mol-1 by dividing 1000
EA = +47.2 kJ mol-1

N Goalby chemrevise.org 33
Techniques to investigate rates of reaction

There are several different methods for measuring reactions rates. Some reactions can be measured
in several ways
measurement of the change in volume of a gas
This works if there is a change in the number of moles of
gas in the reaction. Using a gas syringe is a common
way of following this.

(CH3)2C=CH2(g) + HI(g) (CH3)3CI(g)

HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)

Measurement of change of mass

This works if there is a gas produced which is allowed to

escape. Works better with heavy gases such as CO2
HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)

Titrating samples of reaction mixture with acid, alkali, sodium thiosulfate etc
1. Small samples are removed from the reaction mixture
2. quench (which stops the reaction)- can be done by
• by dilution with water
• by cooling
• by adding a reagent that reacts with one of the reactants
3. then titrate with a suitable reagent.

HCOOCH3(aq) + NaOH(aq)  HCOONa(aq) + CH3OH(aq) The NaOH could be titrated with an acid

BrO3 –(aq) + 5Br –(aq) + 6H+(aq)  3Br2(aq) + 3H2O(l) The H+ could be titrated with an alkali

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq) The I2 could be titrated with sodium
thiosulfate

Colorimetry.

If one of the reactants or products is coloured H2O2(aq) + 2I- (aq) + 2H+(aq)  2H2O(l) + I2(aq)
then colorimetry can be used to measure the
change in colour of the reacting mixtures The I2 produced is a brown solution

Measuring change in electrical conductivity

Can be used if there is a change in the number HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)
of ions in the reaction mixture

Measurement of optical activity.

If there is a change in the optical activity through
the reaction this could be followed in a CH3CHBrCH3 (l) + OH−(aq)  CH3CH(OH)CH3 (l) + Br−(aq)
polarimeter

N Goalby chemrevise.org 34
 PAG11 Titration curves
Constructing a pH curve
1. Transfer 25cm3 of acid to a conical flask with a volumetric Calibrate meter first by measuring known pH of a
pipette buffer solution. This is necessary because pH meters
2. Measure initial pH of the acid with a pH meter can lose accuracy on storage.
3. Add alkali in small amounts (2cm3) noting the volume Most pH probes are calibrated by putting probe in a
added set buffer (often pH 4) and pressing a calibration
4. Stir mixture to equalise the pH button/setting for that pH. Sometimes this is
5. Measure and record the pH to 1 d.p. repeated with a second buffer at a different pH
6. Repeat steps 3-5 but when approaching endpoint add in
Can also improve accuracy by maintaining
smaller volumes of alkali
constant temperature
7. Add until alkali in excess

Strong acid – Strong base e.g. HCl and NaOH

pH

13

Long steep part from

The equivalence point lies
around 3 to 9
at the mid point of the
7 extrapolated vertical
pH at equivalence
portion of the curve.
point = 7

25 cm3 of base

Weak acid – Strong base e.g. CH3CO2H and NaOH Half neutralisation volume

At the start the pH rises quickly and then levels off. The For weak acids
flattened part is called the buffer region and is formed because [H+ (aq)][A- (aq)]
a buffer solution is made Ka=
[HA (aq)]
pH
At ½ the neutralisation volume
13 the [HA] = [A-]

Equivalence point >7 So Ka= [H+] and pKa = pH

7 If we know the Ka we can then work out the pH

at ½ V or vice versa.
pH starts Steep part of curve >7 (around
near 3 7 to 9) If a pH curve is plotted then the pH of a weak
acid at half neutralisation (½ V) will equal the pKa
1

½V V cm3 of base

Weak acid – Weak base

pH Strong acid – Weak base
e.g. HCl and NH3 pH
e.g. CH3CO2H and NH3
13
13
No Steep part of the curve

Steep part of curve <7

7
(around 4 to 7)
7

Equivalence point < 7

1
1
25 cm3 of base
3
25 cm of base

N Goalby chemrevise.org 35
Practical: Working out equilibrium constant Kc
A common experiment is working out the equilibrium constant for an esterification reaction. Ethanol and
ethanoic acid are mixed together with a sulphuric acid catalyst.

CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O

Ethanoic acid Ethanol Ethyl Ethanoate

Method
Part 1 Preparing the equilibrium mixture
1 Use burettes to prepare a mixture in boiling tube of carboxylic acid, alcohol, and dilute sulfuric acid.
2 Swirl and bung tube. Leave the mixture to reach equilibrium for one week

Part 2 Titrating the equilibrium mixture

1 Rinse a 250 cm3 volumetric flask with distilled water.
Use a funnel to transfer the contents of the boiling tube into the flask. Rinse the boiling tube with water and add
the washings to the volumetric flask.
2 Use distilled water to make up the solution in the volumetric flask to exactly 250 cm 3.
Stopper the flask, then invert and shake the contents thoroughly.
3 Use the pipette to transfer 25.0 cm3 of the diluted equilibrium mixture to a 250 cm3 conical flask.
4 Add 3 or 4 drops of phenolphthalein indicator to the conical flask.
5 Set up the burette with sodium hydroxide solution..
6 Add the sodium hydroxide solution from the burette until the mixture in the conical flask just turns pink. Record
this burette reading in your table.
7 Repeat the titration until you obtain a minimum of two concordant titres.

The sodium hydroxide will react with the sulfuric acid catalyst and any unreacted carboxylic acid in the
equilibrium mixture

There are many different calculations that can be based on this experiment. Let’s
look at general stages. Not all calculations will use all the stages.

Working out initial amount of moles of reactants

The amount of moles of alcohol and carboxylic acid can be calculated from the densities
and volumes of liquids added
Mass = density x volume
then
Moles = mass / Mr
The initial amount of moles of acid catalyst used is usually determined by titrating a
separate sample of catalyst with sodium hydroxide

Working out equilibrium amount of moles of acid present from the titre results
39.0 cm3 of 0.400 mol dm-3 sodium hydroxide was used in the above titration. The initial moles of sulfuric acid
was 5x10-4 mol. Calculate the moles of ethanoic acid present at equilibrium

Amount of NaOH = vol X conc

= 0.039 x 0.400
= 0.0156 mol
So total amount of H+ present in 25cm3 = 0.0156 mol
So total amount of H+ present in 250cm3 = 0.156 mol

Total mol acid present = moles of carboxylic acid + moles of acid catalyst
So X 2 because H2SO4
Amount of carboxylic acid at equilibrium = 0.156 – (5x10-4 x 2) has 2 H+
= 0.155 mol

The pink colour of the phenolphthalein in the titration can fade after the end-point of the titration has been reached
because the addition of sodium hydroxide may make the equilibrium shift towards the reactants

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Working out equilibrium amount of moles of other substances
Calculate the equilibrium amount of ethanol, ethyl ethanoate and water if there were initially 0.400 mol of
ethanol and 0.500 mol of ethanoic acid and at equilibrium there were 0.155 mol of ethanoic acid.

Amount of ethanoic acid that reacted = initial amount – equilibrium amount

= 0.5 – 0.155
= 0.344mol
Amount of ethanol at equilibrium = initial amount - amount that reacted
= 0.400 – 0.344
= 0.056 mol
Amount of ethyl ethanoate at equilibrium = initial amount + amount that formed
= 0 + 0.344
= 0.344 mol
Amount of water at equilibrium = initial amount + amount that formed The amount of water at
= 0 + 0.344 equilibrium would not really be
= 0.344 mol 0 as there would be water
present in the acid catalyst

Calculating the equilibrium constant

Finally calculate the equilibrium constant.
To work out equilibrium concentrations divide the equilibrium amounts by the total volume. Then put in Kc
expression

Kc = [CH3CO2CH2CH3 ] [H2O]
[CH3CO2H] [CH3CH2OH]

In order to confirm that one week was sufficient time for equilibrium to be established in the mixture
from Part 1, several mixtures could be made and left for different amount of time. If the resulting Kc is
the same value then it can be concluded the time is sufficient

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Spectrophotometry
If visible light of increasing frequency is passed through a Absorption of visible light is used in spectrometry to
sample of a coloured complex ion, some of the light is determine the concentration of coloured ions.
absorbed.
The amount of light absorbed is proportional to the method
concentration of the absorbing species (and to the distance •Add an appropriate ligand to intensify colour
travelled through the solution). •Make up solutions of known concentration
Some complexes have only pale colours and do not absorb •Measure absorption or transmission
light strongly. In these cases a suitable ligand is added to •Plot graph of absorption vs concentration
intensify the colour. •Measure absorption of unknown and compare

Spectrometers contain a coloured filter. The colour of the filter is chosen to only allow the wavelengths of light
through that would be most strongly absorbed by the coloured solution.

Detailed method- measuring absorption of copper solutions

• Take nine 100cm3 graduated flasks and pipette 20cm3 of 2 mol dm-3 ammonia solution into each one.
Use the 0.05M solution of aqueous copper sulfate to make up solutions which are concentrations of 0.005 to 0.04
mol dm-3 of [Cu(NH3)4(H2O)2 ]2+
• Mix each solution thoroughly.
• Insert the red filter into the colorimeter.
• Use a cuvette with distilled water to zero the colorimeter
• Then put each prepared solution in cuvette and measure the absorbance of each solution.
• Plot graph of absorption vs concentration
• Measure absorption of unknown solution and determine its concentration from the calibration curve

0.005 to 0.04 mol dm-3 solutions of [Cu(NH3)4(H2O)2 ]2+

Calibration curve
1.8
1.6
1.4
1.2
absorption

1
0.8
0.6
0.4
0.2
0
0 0.01 0.02 0.03 0.04 0.05
concentration in mol dm-3

colorimeter
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