LABORATORY TECHNIQUES REVISION UNIT 3B

Solubility of Sulphates

To a solution of a group 2 metal compound, if a solution of any sulphate is added then a precipitate is
likely.

Group 2 ion in solution

Effect of adding a sulphate solution

Mg2+
Ca2+
Sr2+
Ba2+

No precipitate, MgSO4 is soluble

White precipitate of CaSO4
White precipitate of SrSO4
White precipitate of BaSO4

Solubility of Hydroxides

To a solution of a group 2 compound, if sodium hydroxide is added then a precipitate is likely.

Group 2 ion in solution

Effect of adding a hydroxide solution

Mg2+
Ca2+
Sr2+
Ba2+

white precipitate of Mg(OH)2

Faint white precipitate of Ca(OH)2
Faint white precipitate of Sr(OH)2 on standing
No precipitate, Ba(OH)2 is soluble

Heating carbonates and nitrates

Substance

Effect of heat

Lithium and all group 2 carbonates

Sodium and potassium carbonates

Carbon dioxide detected

No effect (except water of crystallisation may be
given off)
Oxygen only gas evolved
Nitrogen dioxide and oxygen evolved

Sodium and potassium nitrates

Lithium and all group 2 nitrates

Action of heat on compounds

Carbonates - Carbon dioxide is given off.

Hydrogen carbonates - Carbon dioxide and water formed.
Group 1 nitrates - Nitrite and oxygen formed.
Group 2 nitrates - Oxide, brown fumes of nitrogen dioxide and oxygen formed.

Distinguishing between hydrocarbons

Alkanes: Burn /oxidise /combust them. They will burn with a yellow flame and form CO 2 and H2O
(Limited supply of oxygen they produce CO).
Alkanes does not decolourise aqueous bromine water.
Alkenes: A yellow, sootier flame is produced (due to the higher ratio of carbon : hydrogen).
Alkenes decolourise aqueous bromine water from orange to colourless.

Identifying some functional groups

Alkenes - Add to orange bromine water. The alkene will decolourise it.

Halogenoalkanes - Heat with sodium hydroxide solution. Acidify with dilute nitric acid and then test with
silver nitrate solution as with inorganic halides.

Alcohols or carboxylic acids containing C-OH - In a dry test tube (i.e. dry alcohol), add PCl 5.
Misty fumes of HCl are produced, which turns blue litmus paper red.

Distinguishing between different classes of alcohol

Primary - Warm it with aqueous potassium dichromate (K2Cr2O7) and dilute H2SO4. Misty fumes are given
off and the colour changed from orange to green --> aldehyde.

Secondary - changes to green --> ketone.

Tertiary - no colour change.

Performing a Flame Test

Dip nichrome wire in concentrated HCl and into the test sample. Heat wire in centre of the flame. If the
flame colour changes

Flame Colour
Carmine Red

Ion
Li+

Yellow

Na+

Lilac

K+

Brick Red

Ca2+

Crimson Red

Sr2+

Apple Green

Ba2+

Blue

Cu2+

Test For Cations

Ion
NH4+

Test
Add NaOH Solution and heat

Mg2+

Add NaOH

Inference
Pungent smell of Ammonia which turns damp red
litmus blue.
White precipitate of Mg(OH)2 is formed.

Identifying AN IONS:
Ion

Formula

Carbonate

CO32-

Test

Observations

Add dilute HCl to the solid.

Vigorous effervescence of carbon dioxide which turns

lime water milky due to the formation of calcium
carbonate.

Hydrogen
carbonate

HCO3-

Add boiling water

Effervescence of carbon dioxide which turns lime water

milky due to the formation of calcium carbonate.

Sulphate

SO42-

Acidify the solution with dilute HCl and

Add barium chloride solution.

White precipitate of barium sulphate forms.

Sulphite

SO32-

Warm the sulphite with dilute HCl.

Effervescence of sulfur dioxide gas which turns the

paper soaked in acidified potassium dichromate (VI)
from orange to green.

Chloride

Cl-

Test 1
Add concentrated sulphuric acid to the
solid chloride.
Test 2
Acidify the solution with dilute nitric acid.
This eliminates any carbonates or
sulphites.
Add silver nitrate to the solution.

Bromide

Iodide

Br-

I-

Test 1
Add concentrated sulphuric acid to the
solid bromide.
Test 2
Acidify the solution with dilute nitric acid.
This eliminates any carbonates or
sulphites.
Add silver nitrate to the solution.
Test 1
Add concentrated sulphuric acid to the
solid Iodide.
Test 2
Acidify the solution with dilute nitric acid.
This eliminates any carbonates or
sulphites.
Add silver nitrate to the solution.

Nitrate

NO3Test 1
Heat solid nitrate.

White steamy acidic fumes of HCl are seen.

White precipitate of AgCl forms which dissolves in

dilute ammonia.

Steamy brownish acidic fumes are seen.

Cream precipitate of AgBr forms which dissolves in

concentrated ammonia.

Purple acidic fumes are seen. The mixture turns to a

brown slurry

Pale yellow precipitate of AgI forms which is insoluble

in concentrated ammonia.
If group 1 solid (not Li) then will decompose to give the
nitrite and oxygen.
All other solid nitrates decompose to give the metal
oxide, brown fumes of nitrogen dioxide and oxygen.

Test 2
Make the solution alkaline with NaOH
and add aluminum foil/ Devardas alloy
and heat gently.

Pungent smell of ammonia gas is evolved which turns

red litmus blue.

Recognition and identification of common gases:

1 hydrogen (H2):
A colour less, odourless gas which ignites a lighted splint with a pop sound.
Hydrogen is produced by:
The reaction between an acid and a reactive metal.
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
The reaction between an alcohol and sodium
ROH(l) + Na(s) RO-Na+(l) + H2(g)
The reaction between water and either a group-1 metal, or calcium, strontium, or barium.
M(s) + H2O(l) MOH(aq) + H2(g)
2 Oxygen (O2):
A colourless, odourless gas which relights a glowing splint.
Oxygen can be produced by:
Heating a group-1 nitrate (apart from LiNO3)
2MNO3(s) 2MNO2(s) + O2(g)
M = Group 1 metal
Heating other nitrate, but NO2 is also present.
4LiNO3(s) 2Li2O(s) + 4NO2(g) + O2(g)
2M(NO3)2(s) 2MO(s) + 4NO2(g) + O2(g)
M = Group 2 metal
The catalytic decomposition of H2O2.
H2O2(aq) 2H2O(l) + O2(g)

3 carbon dioxide (CO2):

A colourless, odourless gas which gives a white precipitate with limewater (calcium hydroxide solution)
i.e. it turns limewater milky. If excess CO2 is passed, the precipitates dissolves giving a colourless
solution.
Ca(OH)2(aq) + CO2(g) CaCO3(s) + H2O(l)
CaCO3(s) + H2O(l) + CO2(g) Ca(HCO3)2(aq)
Carbon dioxide is produced by:
A reaction between an acid and a carbonate or hydrogen carbonate.
CO32-(s)/(aq) + 2H+(aq) CO2(g) + H2O(l)
HCO3-(s)/(aq) + H+(aq) CO2(g) + H2O(l)

 Heating a carbonate (apart from sodium, potassium or barium carbonates).

Li2CO3(s) Li2O(s) + CO2(g)
MCO3(s) MO(s) + CO2(g)
M = Group 2 metal
Heating a group-1 hydrogen carbonate.
2MHCO3(s) M2O(s) + CO2(g) + H2O(l)
M = Group 1 metal
4 sulfur dioxide (SO2):
A colourless gas which is acidic and decolourises acidified potassium dichromate (VI) paper or solution
from orange [Cr2O72- (aq)] to green [Cr3+(aq)].
Sulfur dioxide is produced by:
Warming an acid with a sulfite.
SO32-(aq)/(s) + 2H+(aq) SO2(g) + H2O(l)
Burning sulfur.
S(s) + O2(g) SO2(g)
Reducing concentrated sulfuric acid.
Br-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HBr(g)
2HBr(g) + H2SO4(aq) Br2(g) + SO2 (g) + 2H2O(l)
I-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HI(g)
2HI(g) + H2SO4(aq) I2(s) + SO2(g) + 2H2O(l)
6HI(g) + SO2(g) H2S(g) + 3I2(s) + 2H2O(l)
5 chlorine (Cl2):
A pale green gas which turns moist blue litmus paper first red and then bleaches it rapidly.
If chlorine gas is passed into a solution of potassium bromide, the colourless solution becomes brown.
2KBr(aq) + Cl2(g) 2KCl(aq) + Br2(aq)
The brown colour is due to Br2(aq).
A solution of chlorine can be tested in the same way.
Chlorine is produced by:
Electrolysis of a solution of chloride.
6 hydrogen chloride (HCl):
Steamy fumes on exposure to moist air, acidic and forms white smoke with ammonia,
Ammonium chloride is produced.
NH3(g) + HCl(g) NH4Cl(s)
Hydrogen chloride is produced by:
The reaction between concentrated sulfuric acid with a chloride.
Cl-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HCl(g)
The reaction between phosphorus pentachloride and either an alcohol or carboxylic acid.
ROH(l) + PCl5(s) RCl(l) + POCl3(l) + HCl(g)
RCOOH(l) + PCl5(s) RCOCl(l) + POCl3(l) + HCl(g)
7 nitrogen dioxide (NO2):
A brown gas.
Nitrogen dioxide is produced by:
Heating Group 2 nitrate or heating lithium nitrate.
4LiNO3(s) " 2Li2O(s) + 4NO2(g) + O2(g)

2M(NO3)2(s) " 2MO(s) + 4NO2(g) + O2(g)

M = Group 2 metal
8 Ammonia (NH3):
A colourless, pungent smelling gas which turns moist red litmus paper blue and forms a
white smoke with hydrogen chloride gas.
NH3(g) + HCl(g) NH4Cl(s)
Ammonia is produced by:
Heating sodium hydroxide with an ammonium salt.
NH4+(aq) + OH-(aq) NH3(g) + H2O(l)
Adding sodium hydroxide and aluminium powder to a nitrate.
3NO3-(aq) + 8Al(s) + 5OH-(aq) + 18H2O(l) 3NH3(g) + 8[Al(OH)4 ]-(aq)
9 Watervapour (H2O):
It turns blue cobalt chloride paper pink and white anhydrous copper (II) sulfate to blue hydrated copper (II)
sulfate.
CuSO4(s) + 5H2O(l) CuSO4. 5H2O(aq)

Heating under reflux:

It is used when the reaction is slow and one of the reactants is volatile.
The organic vapours that boil off as the reaction mixture is heated are condensed and flow back into
the reaction vessel.
As most organic compounds are flammable, it is safer to heat the mixture using an electric heater or a
water bath rather than direct heating.

Distillation:

This is used to remove a volatile substance from a mixture containing non-volatile inorganic species,
such as acid or alkali.
This can also be carried out to separate two volatile organic substances present in a homogeneous
mixture only when there is a large enough difference in the boiling temperature of the organic substances.
The product must not decompose at the boiling temperature
The mixture is carefully heated and the vapour that comes over at 2C of the boiling temperature
(obtained from a data booklet) of the particular substance is condensed and collected.

Safety Precautions:

 Distillation (simple or steam) and heating under reflux must be carried out in a fume cupboard if the
vapour of one of the reactants or products is harmful, poisonous (toxic) or irritant.
The thermometer bulb must be placed adjacent to the mouth of the joint at the neck of round bottom
flask.
If the mixture is being heated under reflux or distilled, there must be some outlet to the air. If there is
not, pressure will build up in the apparatus, which will then fly apart, spraying hot, flammable, and often
corrosive, liquid around.
Gloves must be worn when corrosive substances are used. Such substances are must always be
handled with care.
The flask should never be heated with a naked flame. This is because almost all organic substances
are flammable and if the liquid being heated were to spill over or the flask to crack, a fire would result.

Solvent Extraction:

An organic product can often be separated from inorganic substances by solvent extraction.
This is useful when the components of a mixture have similar boiling temperatures and
fractional distillation is not possible.
The organic compound is separated by adding a suitable organic solvent which dissolves the organic
compound but not the inorganic one. The organic compound and the solvent should have a large enough
difference in boiling temperature so that they can be later separated by distillation.

Purification of a liquid that is insoluble in water:

The product is distilled out of the reaction mixture and the following processes are carried out:
The distillate is washed with sodium carbonate or sodium hydrogen carbonate solution in a
separating funnel. This removes any acidic impurities. The pressure must be released from time to time to
get out the carbon dioxide. This washing is repeated until no more fizzing is seen.

CO32-(aq) + 2H+(aq) CO2(g) + H2O(l)

HCO3-(aq) + H+(aq) CO2 (g) + H2O(l)

 The aqueous layer is discarded and the organic layer is washed with water. This removes any
unreacted sodium salts and any soluble organic substances, such as ethanol.
The aqueous layer is discarded and the organic layer is dried, usually with lumps of anhydrous
calcium chloride or calcium oxide or silica gel.

Hazards and Risks:

Hazard is the potential of a substance or activity to do harm.

Risk is the chance that a substance or activity will cause harm.

Types of Hazards And General Safety:

Toxic/carcinogenic use gloves, fume cupboard

Flammable Water baths, no naked fumes.
Harmful gases Use fume cupboard
Corrosive wear goggles/gloves
Spillage of concentrated acid wash with plenty of water.

Risks can be reduced by:

Using less material the reaction is easier to contain and to control, and the risk of spillage is reduced.
Using lower concentrations of solutions diluted corrosive solutions can become irritants, still a hazard
but a much reduced one.
Using specific protective clothing e.g. gloves when handling corrosive liquids.
Doing a reaction in a fume cupboard thus removing harmful vapours from the work area.
Reducing the temperature at which the procedure is carried out thus slowing the reaction and
reducing the risk of overheating and too many fumes being produced.
Changing the materials used less hazardous material may not react as quickly or give as much as
product, but they will allow the same reaction to be studied.

Yield:

Yields are less than 100 percent because of:

Competing / side reactions.
Handling losses during transfer and purification.

Volumetric analysis

Volumetric analysis (titration) involves the reaction between two solutions. For one solution, both the
volume and the concentration are known; for the
other, the volume only is known. Apparatus used includes a burette, a pipette and a volumetric flask.

What is a standard solution?

A solution for which concentration is accurately known. The concentration may have been found by a
previous titration or by weighing the solute and making
a solution of known volume. Such a solution is a primary standard solution.

How is a 250cm3 standard solution prepared?

Make sure that the balance is clean and dry. Wipe it with a damp cloth.
Place the weighing bottle on the pan and take the balance (i.e. re-zero it)
Take the bottle off the balance and add solid to it. This ensures that no spillages fall on the pan.
Take the balance of the weighing bottle + solid and find the balance of solid by subtraction.
Replace on balance, and if the required amount is added, withdraw the mass.
When you have the required amount, write its value down immediately.
Wash out a 250cm3 volumetric flask three times using pure water.
Transfer the solid to a 250cm3 volumetric flask using a funnel, and wash out the weighing bottle into the
flask through the funnel using distilled water.
Add about 100cm3 of distilled water to the flask.
Stir the solution using a glass rod until all the solid visibly dissolves into a solution.
Wash all remaining apparatus including the glass rod, funnel and transfer the rest of this to the flask.
Make up to 250cm3 with distilled water so that the bottom of the meniscus just touches the 250cm3
mark.
Attach a stopper to the flask.
Shake the flask vigorously and/or invert the flask 5 or 6 times to create a solution with uniform
concentration.

Concentration of solution = mass of solid used/molar mass of solid x 1000/250 (units moldm-3)

Using the pipette

A glass bulb pipette will deliver the volume stated on it within acceptable limits only.
Using a pipette filler, draw a little of the solution to be used into the pipette and use this to rinse the
pipette.
Fill the pipette to about 2-3cm3 above the mark. Pipette fillers are difficult to adjust accurately, so quickly
remove the filler and close the pipette
with your forefinger (not thumb). Release the solution until the bottom of the meniscus is on the mark.
Immediately transfer the pipette to the conical flask in which you will do the titration, and allow the
solution to dispense under gravity.

Using the burette

Making sure that the tap is shut, add about 10-15cm3 of the appropriate solution to the burette and rinse
it out, not forgetting to open the tap and rinse
the jet.
Close the tap and fill the burette. A small funnel should be used to add the solution but be careful not to
overfill the funnel.
Remove the funnel, because titrating with a funnel in the burette can lead to serious error if a drop of
liquid in the funnel stem falls into the burette
during the titration.
Bring the meniscus on to the scale by opening the tap to allow solution to pass through the burette.
There is no particular reason to bring the meniscus
exactly to the zero mark.
Make sure that the burette is full to the tip of the jet.
After a suitable indicator has been added to the solution in the conical flask, swirl the flask under the
burette with one hand whilst adjusting the burette
tap with your other hand.
Add the solution in the burette to the conical flask slowly, swirling the flask all the time.

As the endpoint is approached, the indicator will change colour more slowly. The titrant should be added
drop by drop near to the endpoint.
Repeat the titration until you have three concordant titres, i.e. volumes that are similar. This means within
0.2cm3 or better if you have been careful.
Taking the mean of three titres that differ by 1cm3 or more is no guarantee of an accurate answer.

Common indicators

Indicator
Phenolphthalein
Methyl Orange

Acid
Colourless
Red

Neutral
Colourless
Orange

Alkali
Pink
Yellow

Litmus

Red

Purple

Blue

Enthalpy of Combustion:
Ways to increase the accuracy of the experiment include the following:

The copper calorimeter should be first weighed empty and then when containing water. Alternatively,
water could be added to the calorimeter using a pipette, not a measuring cylinder. If the volume of water
is measured, the mass is calculated using the density of water, which is 1 gcm -3.
A screen should be placed around the calorimeter to maximize the transfer of heat from the
hot combustion gases to the beaker of water.
To ensure an even temperature throughout, the water in the calorimeter must be stirred continuously.
The temperature of the water should be measured for several minutes before lighting the fuel and for
several minutes after putting out the burner flame.
The temperature-time measurements are used to plot a graph from which the theoretical temperature
rise is estimated by extrapolation. This reduces the error caused by heat loss from the beaker to the
surroundings.
The burner and its contents should be weighed before and immediately after the experiment, using a
balance that reads to an accuracy of 0.01 g or better.

The calculation is carried out in three steps:

 Heat produced by the combustion of the fuel in Joules = m c T

m = mass of solution in the cup (not the mass of solute reacted).
c = specific heat capacity of water, 4.18 J g-1 C-1
T = change in temperature.
Amount / Number of moles of fuel burnt = (mass before mass after) molar mass of Fuel
Enthalpy of Combustion, Hc = - heat produced in kilo Joules moles of fuel burnt
The negative sign is due to the fact the reaction is exothermic.

Displacement Reactions and Enthalpies of Solution:

In both displacement reactions and experiments to determine the enthalpy of solution, a solid is added
to a liquid or solution and temperature change is measured.
Temperature time graphs are necessary because the reactions are not instantaneous.

Errors can be reduced by:

Using powdered solids rather than lumps. This speeds up the reaction, so there is less time for cooling.
Making sure that, for displacement reactions, enough metal is taken to ensure that the solution of the
salt of the less reactive metal is the limiting reagent (so that it reacts completely).

Instantaneous Reactions:
Neutralisation and precipitation reactions are instantaneous reactions.

Errors can be reduced by:

Using pipettes, rather measuring cylinders, to measure out the volume of the two liquids.
Making sure that one of the reactants is in excess. The value of H can then be worked out using the
amount in moles of the limiting reagent.

 For neutralisation reactions only, weighing the expanded polystyrene cup empty and after the reaction.
This is a more accurate way of obtaining the mass of solution than using a pipette and assuming that the
solution has a density of 1 gcm-3.
Measuring the temperature of both liquids before mixing and averaging the two values.
Stirring immediately on mixing the two solutions.
Reading the maximum temperature reached.
The calculation is carried out in three steps:
Heat produced or lost by the reaction in Joules = m c T
m = total mass of the two solutions in the cup (not the mass of solute reacted).
c = specific heat capacity of water, 4.18 J g-1 C-1
T = change in temperature.
Amount / Number of moles of solute reacted = concentration (moldm -3) volume (dm3)