ADNAN CHOWDHURY

CHEMISTRY TEACHER
UNIT 3B
ALTERNATIVE TO
PRACTICAL
 UNIT 3B NOTES

Experimental method to determine the Enthalpy of Combustion of a liquid:

Measurements:

Volume of water = V cm3

Initial temperature of water = 1 C

Mass of spirit burner + fuel before burning = m1 g

Mass of spirit burner + fuel after burning = m2 g

Final temperature of water = 2 C

Assumptions:

Density of water = 1 gcm-3

Specific heat capacity of water = 4.18 J g-1 C-1

No heat is lost to the surrounding.

No heat is absorbed by the metal container (copper calorimeter).

Calculations:

Mass of water, M = density volume = 1 V = V g

Change in temperature, = (2 - 1)C

Heat produced by the combustion of the fuel in Joules = M c

M = mass of water in the beaker (not the mass of fuel burnt).

c = specific heat capacity of water = 4.18 J g-1 C-1

= change in temperature.

mass of fuel burnt, m = (m1 m2) g

Amount / Number of moles of fuel burnt = m/Mr

m = mass of fuel burnt

Mr = molar mass of fuel

Enthalpy of Combustion = -

The negative sign is due to the fact the reaction is exothermic.

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 UNIT 3B NOTES

Example 1:

Liquid Mass of burner Mass of burner Temperature at Temperature at

at start/g at end /g o o
start/ C end / C
Ethanal, C2H4O 115.78 115.59 21 29

Mass of water = 100g

Calculation:

Energy = m x C x = 100 x 4.2 x 8 = 3360 J Moles = 0.19 / 44 = 0.0043

H = -3360 / 0.0043 = -781,395 J/mol = -781 kJ/mol (3 sig fig).

If the experiment is repeated with a number of alcohols, it can be shown that the values of the enthalpies of
combustion of successive alcohols differ by a similar amount. This is because each member of a homologous
series differs from the next by CH2. The combustion of this unit should result in the same release of energy
(about 650 kJmol-1) whatever the homologous series being investigated.

Example 2:

Example 3:

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 UNIT 3B NOTES

Alternative Accurate Method:

The temperature of the water in the calorimeter is measured every minute for three minutes.

The burner is lit after 3.5 minutes.

The temperature of the water is continued recording every minute.

When the temperature has reached a suitable rise, the flame in the spirit burner is extinguished and
the burner immediately reweighed.

The temperature readings are stopped 5 minutes after the temperature has reached a maximum value.

Sources of Errors:

As the experiment takes a long time, not all the heat lost to the surroundings is compensated for the
extrapolation of the graph.

Some of the heats released in burning heats up the air and not the water.

The beakers absorb some of the heat produced.

Some of the ethanol may not burn completely to carbon dioxide and water. Incomplete combustion
would cause black soot to be deposited on the bottom of the container.

The conditions are not standard. Water vapour, and not liquid water, is produced.

Assuming the volume (and therefore mass) of water used in the calculation is the same as the volume
of the solution used in the reaction.

Improvements:

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 continually.

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.

A bomb calorimeter can be used.

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 UNIT 3B NOTES

An experiment to measure Enthalpy of Neutralisation:

Using a measuring cylinder, 30 cm3, 1.0 moldm-3 of dilute hydrochloric acid is placed into an
expanded polystyrene cup.

A thermometer is placed in the solution and the temp is recorded every minute for 3 minutes.

30cm3, 1.1 moldm-3 of sodium hydroxide solution is measured out. Sodium hydroxide is taken in slight
excess to ensure complete neutralisation of the acid.

At 3.5 minutes the sodium hydroxide solution is added.

The mixture is stirred continuously.

Readings continue to be taken every minute up to ten minutes.

A graph of the readings is plotted and the lines extrapolated as shown in the diagram below.

Assumptions:

Density of solution = 1 gcm-3

Specific heat capacity of water = 4.18 J g-1 C-1

No heat is lost to the surrounding.

No heat is absorbed by the polystyrene cup.

Calculations:

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

Total volume, V = 30 + 30 = 60cm3

Total mass of solution, M = density volume = 1 V = V g

Change in temperature, is recorded from graph.

Heat produced in Joules = M c

M = total mass of water in the beaker (not the mass of fuel burnt).

c = specific heat capacity of solution = 4.18 J g-1 C-1

= change in temperature.

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 UNIT 3B NOTES

Amount / Number of moles of H2O = Amount / Number of moles of HCl = Concentration Volume

Enthalpy of Neutralisation = -

The negative sign is due to the fact the reaction is exothermic.

Example 4:

Example 5:

Example 6:

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 UNIT 3B NOTES

Example 7:

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). For enthalpy of
solution experiments, the water must be in large excess to ensure that all the solid dissolves.

Measuring the temperature for several minutes before the start of the reaction and for several minutes
after the reaction has finished. The measurements are used to plot a graph, which is extrapolated to
find the theoretical temperature rise.

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 UNIT 3B NOTES

Continually stirring the contents of the expanded polystyrene cup.

Placing a lid on the cup to prevent heat loss through evaporation.

Weighing the cup empty and then, before the reaction starts, weighing it containing the solution. This
gives an accurate value of the mass of the solution. The assumption that the density of a solution is 1
gcm-3 is not wholly accurate.

Measuring the volume of solution using a pipette rather than a measuring cylinder, so that the amount
(moles) can be accurately determined. This is not necessary for enthalpy of solution determinations.

Calculation:

Heat produced or lost by the reaction 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-1C-1

T = change in temperature.

Amount / Number of moles of solute reacted = concentration (moldm-3) volume (dm3)

For enthalpy of solution determination,

( )
Amount / Number of moles of solute reacted =

Enthalpy of Reaction, Hr =

If there is a temperature rise, H is negative; if the temperature falls, H is positive.

Example 8:

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 UNIT 3B NOTES

Example 9:

Example 10:

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 UNIT 3B NOTES

Instantaneous Reactions:
Neutralisation and precipitation reactions are neutralisation 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.

Calculation:

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 limiting solution = concentration (moldm-3) volume (dm3)

Enthalpy of Reaction, Hr =

If the temperature rises, H is negative; if the temperature falls, H is positive.

Enthalpy Titration:
The concentration of a solution can be determined by measuring the temperature change when an
alkaline solution of known concentration is added gradually, until it is in excess.

25 cm3 of the acid solution is pipetted into an expanded polystyrene cup.

The temperature of the acid is recorded with a thermometer.

Standard 1 moldm-3 solution of sodium hydroxide is added from a burette in 2cm3 portions, stirring
and measuring the temperature after each addition.

Sodium hydroxide is continued adding after the maximum temperature is reached.

A graph of temperature against volume of sodium hydroxide is plotted.

This method is suitable for a weak acid weak base titration where no indicator is suitable.

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 UNIT 3B NOTES

Example 11:

Solubility of Group 2 Sulfates:

The solubility of the sulfates decreases down the group:

Beryllium and magnesium sulfates are very soluble.

Calcium sulfate is slightly soluble.

Strontium sulfate is very slightly soluble.

Barium sulfate is insoluble.

The solubility of sulfates decreases down the group. Again, calcium sulfate is somewhere in between
soluble and insoluble. Barium sulfate is used in 'barium meal' X-ray investigations because it is
insoluble, and so it is not absorbed from the gut. It is useful to use barium compounds, despite their
poisonous nature, because barium shows up well on X-rays because it has so many electrons.

On adding a solution of any sulfate to a solution of calcium, strontium and barium compounds, a white
precipitate of an insoluble sulfate is produced.

Ba2+(aq) + 2SO42-(aq) BaSO4(s)

Barium sulfate is so insoluble that when dilute sulfuric acid is added to a piece of barium metal, the
reaction stops almost at once. The initial reaction causes a layer of insoluble barium sulfate to form
on the surface of the metal. This layer prevents further acid from reaching the unreacted metal.

Solubility of Group 2 Hydroxides:

The solubility of group 2 hydroxides increases down the group:

Beryllium hydroxide is insoluble.

Magnesium hydroxide is very slightly soluble.

Calcium hydroxide is slightly soluble.

Strontium and barium hydroxides are more soluble.

Thermal stability of Group 1 Nitrates:

All group 1 nitrates decompose on strong heating. However, lithium nitrate decomposes in a different
way from the other nitrates. The products are lithium oxide, nitrogen dioxide and oxygen. The
nitrogen dioxide is visible as a brown gas:

4LiNO3(s) 2Li2O(s) + 4NO2(g) + O2(g)

The small radius of the lithium ion causes it to have a high charge density, which polarises the O-N
bond in the nitrate ion sufficiently to break it and form an O2- ion.

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 UNIT 3B NOTES

The other group 1 cations are too large to polarise to this extent. Therefore, on heating, their nitrates
do not decompose to give an oxide. Very strong heating causes them to melt, giving off oxygen and
leaving a molten nitrite that contains the NO2- ion, for example:

2NaN03 2NaN02 + O2

The temperature at which thermal decomposition occurs is lowest for lithium nitrate and increases
down the group as size of cation increases so charge density increases.

Thermal stability of Group 2 Nitrates:

The nitrate ion in a group 2 nitrate is sufficiently polarised by the 2+ cation to result in thermal
decomposition by the same pathway as lithium nitrate.

On heating, group 2 nitrates decompose to the metal oxide, nitrogen dioxide and oxygen. The
temperature at which thermal decomposition occurs is lowest for beryllium nitrate and highest for
barium nitrate, which requires very strong heating before brown fumes of nitrogen dioxide are seen.
The equation for the decomposition is:

2M(N03)2 2M0 + 4N02 + 02

M = Group 2 metal

Mg(N03)2 6H20(s) MgO(s) + 02(g) + 2N02(g) + 6H20(l)

Observation:

the solid dissolving in the water of crystallization.

the solution boiling, and water condensing at the top of the test tube.

a solid reforming as the water boils away.

the solid melting

and finally a brown gas (nitrogen dioxide) given off, and also a gas that relights a glowing splint.

Thermal stability of Group 1 Carbonates:

Only lithium carbonate decomposes when heated. This is because the Li+ cation is very small and
polarises the O-C bond in the CO32- ion sufficiently for it to break and form an 02- ion:

Li2C03(s) Li2O(s) + C02(g)

The other group 1 cations have larger radii. Therefore, their polarising power is not sufficient to cause
decomposition of the anhydrous carbonates. When a hydrated carbonate, such as hydrated sodium
carbonate (washing soda), Na2CO3.H2O, is heated, i.e. water of crystallisation hydrolyses the
carbonate and carbon dioxide and steam are given off:

Na2C03.10H20(s) 2Na0H(s) + CO2(g) + 9H20(g)

Thermal stability of Group 2 Carbonates:

All the group 2 carbonates decompose on heating:

MC03(s) MO(s) + C02(g)

Beryllium carbonate is so unstable that it does not exist at room temperature.

Barium carbonate requires strong heating before it is decomposed. (It can be said it is thermally
stable).

An experiment to study Thermal Decomposition:

The relative ease of decomposition of group 2 carbonates or nitrates can be studied by the following
experiment:

Same amount of each carbonate (or nitrate) is placed in a series of hard glass test tubes.

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 UNIT 3B NOTES

The Bunsen burner is lit and the time taken for the gas to reach the mark on the test tube in the
water bath is recorded.

The experiment is repeated with the same amount (moles) of metal carbonate, using the same
intensity of flame and also distance between heat source and test tube is kept constant.

The group 2 carbonate that, or heating, fills the test tube the fastest is the one that is the easiest to
decompose.

Flame Test:

Procedure:

First the test sample is converted into a chloride salt by adding concentrated HCl acid. This is because
chloride salts are more volatile than any other compounds and hence some of the unknown goes into
the gas phase readily when heated in the hot flame.

A platinum or nichrome wire or a specially marketed flame test rod is taken. Platinum or nichrome
wire is chosen because they have high heat conductivity. A spatula or a wooden splint cannot be
taken. The wire is cleaned by dipping it in some concentrated HCl acid on a watch glass and then
placing it in the hottest part (blue part) of a Bunsen flame. The flame should not be coloured. If it is,
the treatment will be repeated until the flame is not coloured.

Once again, the clean wire is dipped in concentrated HCl acid and then some of the solid under test.

This is then placed in the hottest part (blue part) of the flame and the colour of the flame is
observed.

Flame colour Inference

yellow sodium ion, Na+

lilac potassium ion, K+

yellow-red / brick red* calcium ion, Ca2+

crimson red* lithium ion, Li+

carmine red* strontium ion, Sr2+

pale / apple green barium ion, Ba2+

blue copper (II) ion, Cu2+

no colour magnesium ion, Mg2+

*Further tests would be needed to distinguish these ions.

The flame test is the only test for a group-1 metal cation in a compound.

The flame test cannot be used on mixtures containing two of these ions because the colour produced
by one of the ions will mask the colour produced by the other metal ion.

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 UNIT 3B NOTES

Origin of Flame Colour:

The heat energy of the flame causes the compound to vaporize and promotes an electron in the metal ion
into a higher energy level or excited state. The electron falls back to its normal shell or ground state and as
it does so, energy in the form of visible light is emitted. The light that is emitted of a characteristic
frequency, and hence colour, is dependent on the energy level difference between the two shells.

A more accurate test is the flame photometer that can be used to measure quantitatively the
wavelengths of light give out of the ions such as potassium, sodium and barium in a sample by
analysing the flame produced.

Action of heating a Solid:

Gas or vapour or other Possible source

carbonates of metals (including Li2CO3) other than group 1.

Li2CO3(s) Li2O(s) + CO2(g)
MCO3(s) MO(s) + CO2(g)
carbon dioxide M = Group 2 metal
when a hydrated carbonate such as sodium carbonate is heated.
Na2CO3.10H2O(s) 2NaOH(s) + CO2(g) + 9H2O(l)

group 1 nitrates (other than LiNO3)

oxygen 2MNO3(s) 2MNO2(s) + O2(g)
M = Group 1 metal
nitrates of group 2 (and LiNO3)
4LiNO3(s) 2Li2O(s) + 4NO2(g) + O2(g)
oxygen and nitrogen dioxide
2M(NO3)2(s) 2MO(s) + 4NO2(g) + O2(g)
M = Group 2 metal
hydrated salts or hydrogen carbonate
water Na2CO3.10H2O(s) 2NaOH(s) + CO2(g) + 9H2O(l)
2MHCO3(s) M2CO3(s) + CO2(g) + H2O(l)M = Group 1 metal

a white solid sublimes on ammonium salt present

the cooler part of the tube e.g. NH4Cl (s) NH3(g) + HCl(g)

Recognition and identification of common gases:

Gas Observations

a colourless, odourless gas which relights a glowing splint.

oxygen, O2

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.
carbon dioxide, CO2
Ca(OH)2(aq) + CO2(g) CaCO3(s) + H2O(l)
CaCO3(s) + H2O(l) + CO2(g) Ca(HCO3)2(aq)

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 UNIT 3B NOTES

Gas Observation

a colourless gas which is acidic and decolourises acidified potassium

sulfur dioxide, SO2 dichromate(VI) paper or solution from orange, Cr2O72-(aq)] to green [Cr3+(aq)].

a colourless, pungent smelling gas which turns moist red litmus paper blue and
ammonia, NH3 forms a white smoke with hydrogen chloride gas.
NH3(g) + HCl(g) NH4Cl(s)

*nitrogen dioxide, NO2 a brown gas.

a colourless, odourless gas which ignites a lighted splint with a pop sound.
hydrogen, H2

steamy fumes on exposure to moist air, acidic and forms white smoke with
hydrogen chloride, HCl ammonia.

it turns blue cobalt chloride paper pink and white anhydrous copper (II) sulfate
water vapour, H2O to blue hydrated copper (II) sulfate.
CuSO4(s) + 5H2O(l) CuSO4. 5H2O(aq)

a pale green gas which turns moist red litmus paper first blue 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)
chlorine, Cl2 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.
Adding dilute HCl acid to a solution containing chlorate(I) ions
a brown gas which turns moist red litmus paper first blue and then bleaches it
but it does more slowly.
If bromine gas is passed into a solution of excess potassium iodide, the
colourless solution becomes deep red brown. This is because iodine is
liberated, and then reacts with excess I- ions to form the red brown I3-. Excess
*bromine, Br2 bromine would give a grey black precipitate of iodine.
2KI(aq) + Br2(g) 2KBr(aq) + I2(aq)/(s)
I2(aq) + I-(aq) I3-(aq)
*Bromine is a brown fuming liquid at rtp.
*Bromine dissolves in organic solvents to form a brown solution whereas
nitrogen dioxide is insoluble.

a purple vapour which has no effect on moist red litmus paper. It turns starch
solution dark blue or blue black.
Copper (II) ions, Cu2+ in copper (II) sulfate react with iodide ions, I- in
potassium iodide and forms a whitish brown precipitate.
iodine, I2
2Cu2+ (aq) + 4I- (aq) 2CuI (s) + I2 (aq)
white brown
Iodine is grey-black solid at rtp. Solutions in aqueous potassium iodide are red
brown and aqueous solutions are pale brown.

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 UNIT 3B NOTES

Element Physical State at room temperature

Fluorine Pale yellow gas

Chlorine Greenish yellow gas

Bromine Red - brown volatile liquid

Iodine Dark grey lustrous solid; the vapour is purple

Element Colour in water Colour in hexane

Chlorine virtually colourless virtually colourless

Bromine yellow/orange orange/red

Iodine brown pink/violet

Reaction of Halide salts:

Reaction with concentrated Sulfuric acid:

When a few drops of concentrated sulfuric acid (H2SO4) are added to a solid or aqueous halide the
observed reaction products may be used to identify the particular halide ion present. This is a
potentially hazardous reaction.

It must be carried out on a small scale and in a fume cupboard.

The products in brackets will not be observed since they are colourless gases. The halide ion may be
identified without the need to test for these gases. No attempt should ever be made to detect these
gases by smell.

Observations on adding concentrated

Halide Observed reaction products
H2SO4

fluoride steamy fumes (HF), vigorous reaction F-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HF(g)

Cl-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HCl(g)

chloride steamy fumes (HCl), vigorous reaction

steamy fumes (HBr), brown Br-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HBr(g)

bromide
vapour,(Br2) vigorous reaction 2HBr(g) + H2SO4(aq) Br2(g) + SO2 (g) + 2H2O(l)

steamy fumes (HI), black solid I-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HI(g)

[I2(s)], purple vapour [I2(g)], yellow 2HI(g) + H2SO4(aq) I2(s) + SO2 (g) + 2H2O(l)
iodide
solid (S), smell of rotten egg (H2S), 6HI(g) + SO2 (g) H2S(g) + 3I2(s) + 2H2O(l)
vigorous reaction

Reactions with fluoride and chloride are not redox as oxidation number of sulfur does not change.

Silver nitrate solution:

Aqueous silver nitrate is commonly used to test for the presence of halide ions in solution. Anions
which would interfere with the test (e.g. carbonate, sulphite) are removed by adding dilute nitric acid
before the aqueous silver nitrate.

The identity of a halide may be confirmed by the addition of aqueous ammonia, (NH3), both dilute and
concentrated.

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 UNIT 3B NOTES

Silver halides which dissolve in ammonia do so to form a colourless solution of the complex ion,
[Ag(NH3)2]+.

AgX(s) + 2NH3(aq) [Ag(NH3)2]+(aq) + X-(aq)

X = Cl, Br

HCl(aq) or H2SO4(aq) acid cannot be used as these acids react with AgNO3.

Ionic equation:

Ag+(aq) + X-(aq) AgX(s)

Precipitate Addition of aqueous NH3

Anion
colour formula dilute concentrated

chloride white AgCl soluble

soluble in
bromide cream AgBr soluble
excess

iodide yellow AgI insoluble insoluble

Silver halides decompose when light shines on them producing silver and the halogen.

2AgX(s) 2Ag(s) + X2(g)

Silver halides are decomposed by light. Photochromic lenses contain silver chloride, which dissociates to form
silver in the glass. When the light source is removed, the silver recombines with the chlorine. Photographic
emulsions contain silver chloride or bromide. Exposure to light makes it easier to reduce the silver halide to
silver in the developing bath than the unexposed compound.

Action of dilute acids:

When dilute sulfuric or hydrochloric acid is added to a substance a gas may be evolved or there may be
a colour change in the solution.

Action of acid Possible source

effervescence of a colourless, odourless gas which gives a

carbonate or hydrogencarbonate
white precipitate with limewater (calcium hydroxide
solution) i.e. it turns limewater milky. CO32-(s)/(aq) + 2H+(aq) CO2(g) + H2O(l)
Carbon dioxide evolved HCO3-(s)/(aq) + H+(aq) CO2(g) + H2O(l)

a colourless, odourless gas evolves which ignites a lighted

a metal
splint with a pop sound.
M(s) + 2H+(aq) 2M+(aq)/M2+(aq) + H2 (g)
Hydrogen evolved
chromate(VI) to dichromate(VI)
yellow solution turns orange
2CrO4 2-(aq)
+ 2H+(aq) Cr2O72- (aq) + H2O(l)

sulfur dioxide evolved which is a colourless, acidic gas and

decolourises acidified potassium dichromate(VI) paper or thiosulfate
solution from orange Cr2O72- (aq) to green Cr3+(aq). S2O3 2-(aq) + 2H+(aq) S(s) + SO2 (g) + H2O(l)
Also pale yellow sulfur precipitate is formed

sulfur dioxide evolved on warming which is a colourless,

acidic gas and decolourises acidified potassium
dichromate(VI) paper or solution orange Cr2O72- (aq) to
sulfite
green Cr3+(aq). SO32-(aq)/(s) + 2H+(aq) SO2 (g) + H2O(l)

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 UNIT 3B NOTES

Tests for oxidizing and reducing agents:

Reducing agents usually:

decolourise aqueous acidified potassium manganate(VII) from purple to colourless and
may also turn aqueous, acidified potassium dichromate(VI) from orange to green.
Reducing agents include:
iron(II) ions
iodide ions
hydrogen peroxide**

sulfite ions

Oxidizing agents usually:

liberate iodine as a brown solution or black solid from aqueous potassium iodide.
Iodine solution gives a blue-black coloration with starch.
Oxidizing agents include:
acidified manganate(VII) ions
acidified dichromate(VI) ions
hydrogen peroxide** copper(II)ions
aqueous chlorine
aqueous bromine.

** Hydrogen peroxide acts both as an oxidizing agent and reducing agent.

Hydrogen peroxide:

Aqueous hydrogen peroxide (H2O2) can act as both an oxidizing and a reducing agent often with the evolution
of oxygen, although this may be unreliable.

Observation on adding H2O2 Inference

manganate(VII), brown precipitate is

brown precipitate
MnO2
purple solution is decolourised manganate(VII) in acid solution

pale green solution turns yellow iron(II) to iron(III) in acid solution

green precipitate turns brown iron(II) hydroxide to iron(III) hydroxide

green alkaline solution goes yellow chromium(III) to chromate(VI)

brown solution or black precipitate iodine from iodide in acid solution

brown precipitate in alkaline lead (II); brown precipitate is PbO2
solution
Solubility:

Soluble ionic compounds include:

All group-1 salts.

All ammonium salts.

All nitrates.

All chlorides, apart from silver chloride and lead(II) chloride. (The solubility of bromides and iodides is
similar to that of chlorides.)

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 UNIT 3B NOTES

All sulfates, apart from barium sulfate, strontium sulfate and lead(II) sulfate. Calcium sulfate and
silver sulfate are slightly soluble.

Insoluble ionic compounds include:

All carbonates apart from group-1 carbonates and ammonium carbonates.

All hydroxides, apart from group-1 hydroxides, barium hydroxide and ammonium hydroxide. Calcium
and strontium hydroxides are slightly soluble.

PRECIPITATION REACTIONS:

When two aqueous solutions are mixed together and an insoluble compound is formed this is known as a
precipitate not a suspension. The observation that a precipitate is formed should always be accompanied by
the colour of the precipitate, even if this is white. Some reagents should be added until they are in excess.
This may result in a precipitate forming then dissolving in excess reagent.

SODIUM HYDROXIDE AND AMMONIA SOLUTION:

When small amount of dilute sodium hydroxide (NaOH) solution is added to a solution containing a
metal ion a precipitate of the insoluble hydroxide is usually formed. Precipitates which are
amphoteric hydroxides will dissolve in excess sodium hydroxide to give a solution containing a
complex ion.

Small amount of dilute aqueous ammonia (NH3), when added to a solution containing a cation, will
form the same hydroxide precipitate as dilute sodium hydroxide solution. Excess aqueous ammonia
may dissolve the precipitate to form a complex ion.

Aqueous sodium hydroxide or aqueous ammonia should be added until it is in excess even if this is not
explicitly stated in the instructions.

Observation on adding
Observation on Observation on adding
small amount of dilute
Likely ion adding excess dilute excess dilute aqueous
NaOH or dilute aqueous
NaOH NH3
NH3
a white precipitate of
calcium, Ca2+ precipitate is insoluble precipitate is insoluble
Ca(OH)2

precipitate dissolves
3+ a white precipitate of
aluminium, Al to give a colourless precipitate is insoluble
Al(OH)3
solution of [Al(OH)6]-

precipitate dissolves to precipitate dissolves to

a white precipitate of give a colourless solution
Zn(OH)2 a colourless solution of
zinc(II), Zn2+ [Zn(OH)4]2- of
[Zn(NH3)4]2+

sodium, Na+ no precipitate

a white precipitate of
Magnesium, Mg2+ Mg(OH)2 precipitate is insoluble precipitate is insoluble

potassium, K+ no precipitate

precipitate dissolves to
give a colourless solution
a white precipitate of AgOH of [Ag(NH3)2]+.
silver, Ag+ which is dehydrated to form The brown precipitate of
a brown precipitate of Ag2O precipitate is insoluble
Ag2O is often not seen
because the ammonia
complex forms very
easily.

ADNAN CHOWDHURY 18
 UNIT 3B NOTES

Observation on adding
Observation on Observation on adding
small amount of dilute
Likely ion adding excess dilute excess dilute aqueous
NaOH or dilute aqueous
NaOH NH3
NH3

a white precipitate of precipitate dissolves

lead(II), Pb2+ Pb(OH)2 to a colourless solution precipitate is insoluble
of [Pb(OH)4]2+

a white precipitate of
barium, Ba2+ precipitate is insoluble precipitate is insoluble
Ba(OH)2

no precipitate.
On heating, a colourless,
pungent smelling gas
evolves that turns a damp
or moist red litmus paper
blue. The gas is ammonia,
ammonia, NH4+ NH3.
NH4+(aq)+ OH-(aq)
NH3 (g) + H2O(l)
The test for NH4 + ion is
carried out with dilute
NaOH only.

Lead (II) Nitrate or Lead (II) Ethanoate Solution:

Most lead(II) compounds are insoluble. When aqueous lead ions (either lead (II) nitrate or lead (II)
ethanoate) are added to a solution containing the appropriate anion a precipitate will form.

Anion Inference
a white precipitate forms which dissolves on addition of an acid with
effervescence of 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.
Carbon dioxide evolved
Pb (aq) + CO32-(aq) PbCO3(s)
2+

PbCO3(s)+ 2H+(aq) CO2(g) + H2O(l) + Pb2+(aq)

carbonate, CO32-/
hydrogencarbonate, HCO3-
Pb2+(aq) + 2HCO3-(aq) Pb(HCO3)2(s)
Pb(HCO3)2 (s)+ 2H+(aq) 2CO2(g) + 2H2O(l) + Pb2+(aq)

Ca(OH)2(aq) + CO2(g) CaCO3(s) + H2O(l)

CaCO3(s) + H2O(l) + CO2(g) Ca(HCO3)2(aq)

a white precipitate forms which dissolves on addition of an acid with

effervescence of a colourless, acidic gas which decolourises acidified
potassium dichromate (VI) solution or paper from orange Cr2O72- (aq)] to green
sulfite, SO32- Cr3+(aq).
Pb2+(aq) + SO32-(aq) PbSO3(s)
PbSO3(s) + 2H+(aq) SO2 (g) + H2O(l) + Pb2+(aq)

a white precipitate forms which does not dissolve on addition of an acid.

sulfate, SO42- Pb2+(aq) + SO42-(aq) PbSO4(s)

a white precipitate forms which dissolves on heating and reappears on

chloride, Cl- cooling.
Pb (aq) + 2Cl-(aq) PbCl2(s)
2+

ADNAN CHOWDHURY 19
 UNIT 3B NOTES

Anion Inference

a white precipitate forms which dissolves on heating and reappears on

bromide, Br- cooling.
Pb (aq) + 2Br-(aq) PbBr2(s)
2+

a yellow precipitate forms which has no effect on heating.

iodide, I-
Pb2+(aq) + 2I-(aq) PbI2(s)

nitrate, NO3- no precipitate

ethanoate, CH3COO- no precipitate

Barium chloride solution:

Aqueous barium chloride forms precipitates of insoluble barium salts with a number of anions but is usually
used as the test for the sulfate, SO42, ion. Aqueous barium chloride is usually used with dilute hydrochloric
acid.

Test-1:

To a small portion of the aqueous test sample, a few drops of Barium chloride, BaCl2 solution is added
followed by addition of few drops of dilute hydrochloric acid, HCl.

Anion Inference

a white precipitate forms which does not dissolve on addition of HCl acid.
sulfate, SO42-
Ba2+(aq) + SO42-(aq) BaSO4(s)

a white precipitate forms which dissolves on addition of HCl acid with

effervescence of a colourless, acidic gas which decolourises acidified potassium
dichromate (VI) solution or paper from orange [Cr2O72- (aq)] to green [Cr3+(aq)].
sulfite, SO32-
Ba2+(aq) + SO32-(aq) BaSO3(s)
BaSO3(s)+ 2H+(aq) SO2(g) + H2O(l) + Ba2+(aq)

a white precipitate forms which dissolves on addition of HCl acid with

effervescence of a colourless, odourless gas which gives a white
precipitate with limewater (calcium hydroxide solution) i.e. it turns
limewater milky.
Carbon dioxide evolved
carbonate, CO32-/
Ba (aq) + CO32-(aq) BaCO3(s)
2+
hydrogencarbonate, HCO3-
BaCO3(s)+ 2H+(aq) CO2(g) + H2O(l) + Ba2+(aq)

Ba2+(aq) + 2HCO3-(aq) Ba(HCO3)2(s)

Ba(HCO3)2 (s)+ 2H+(aq) 2CO2(g) + 2H2O(l) + Ba2+(aq)

Test-2:

To a small portion of the aqueous test sample, a few drops of dilute hydrochloric acid, HCl is added followed
by addition of few drops of Barium chloride, BaCl2 solution

Anion Inference

a white precipitate forms

sulfate, SO42-
Ba2+(aq)+ SO42-(aq) BaSO4(s)

effervescence of a colourless, acidic gas which decolourises acidified

sulfite, SO32- potassium manganate(VII) paper or solution from orange to green.
SO32-(aq) + 2H+(aq) SO2 (g) + H2O(l)

ADNAN CHOWDHURY 20
 UNIT 3B NOTES

Anion Inference
effervescence of a colourless, odourless gas which gives a white
precipitate with limewater (calcium hydroxide solution) i.e. it turns
limewater milky.
carbonate, CO32-/ Carbon dioxide evolved
hydrogencarbonate, HCO3- CO3 (aq) + 2H+(aq) CO2(g) + H2O(l)
2-

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

Test for the nitrate ion:

Since all nitrates are soluble no precipitation test is possible for the nitrate ion. A solid which is suspected of
being a nitrate then the following tests should be carried out:

warmed with aqueous sodium hydroxide and aluminium or zinc powder or Devadras alloy

if the solid is a nitrate then ammonia gas will be evolved. This will turn damp red litmus blue and a
white smoke HCl gas

3NO3-(aq) + 8Al(s) + 5OH-(aq) + 18H2O(l) 3NH3(g) + 8[Al(OH)4]-(aq)

NH3(g) + HCl(g) NH4Cl(s)

Acid Base Titration:

Preparation of a Standard Solution:

In any titration, the concentration of one of the solutions must be accurately known. The method is as
follows:

The mass of the solid needed to make a solution of the required concentration is calculated.

A weighing bottle is placed on a toppan balance. The tare button is pressed, so that the scale reads
zero.

The solid is added to the weighing bottle until the required mass is reached.

The best way to do this is to remove the bottle from the pan and then the solid is added, checking the
mass until the correct amount has been added. This prevents errors caused by spilling solid onto the
pan of the balance.

The contents of the weighing bottle is transferred into a beaker. Any remaining solid is washed from
the bottle into the beaker.

Some distilled water is added to the beaker containing the solid. Using a glass rod, the solution is
stirred until all the solid has dissolved. In order to dissolve the solid completely, it may be necessary
to heat the beaker.

The solution is transferred through a funnel into a volumetric flask (250 cm3 or 100 cm3). The stirring
rod and the beaker is washed, making sure that all the washings go through the funnel into the
volumetric flask.

More distilled water is added to the solution until the bottom of the meniscus is level with the mark
on the standard flask.

The stopper is placed on the flask and mixed thoroughly by inverting and shaking several times.

Performing a Titration:

Apparatus required:

Burette

Pipette (25cm3 or 10cm3)

Conical Flask

ADNAN CHOWDHURY 21
 UNIT 3B NOTES

Chemicals required:

Standard solution

The solution of unknown concentration

Suitable indicator

Procedure:

A small amount of one of solution (normally acid) is drawn into a pipette using a pipette filler and it is
rinsed with the solution. The rinsings are then discarded.

Using a pipette filler, the pipette is filled so that the bottom of the meniscus is on the mark.

The pipette is allowed to discharge into a washed conical flask. When the pipette has emptied, the
surface of the liquid is touched in the flask with the tip of the pipette.

Making sure that the tap is shut, a burette is rinsed out with a small amount of the other solution
(normally alkali) and the rinsings are discarded.

Using a funnel, the burette is filled to above the zero mark and the liquid is run out until the meniscus
is on the scale. It is checked that the burette below the tap is filled with liquid and that there are no
air bubbles. The funnel is then removed.

The initial volume is recorded by looking at where the bottom of the meniscus is on the burette scale.

The liquid is run slowly from the burette into the conical flask, continually mixing the solutions by
swirling the liquid in the flask. The liquid is added dropwise as the end point is neared and stopped
when the indicator shows the end point colour. The burette reading is recorded to the nearest
0.05cm3.

The titration is repeated until three concordant (it means that the difference between the highest and
the lowest titre is not more than 0.2 cm3) are obtained.

Any non-concordant titres are ignored and average of the concordant values is calculated, to get the
mean titre.

Example 12:

ADNAN CHOWDHURY 22
 UNIT 3B NOTES

23.67cm3 is incorrect because the burette cannot be read to that level of accuracy.

23.62cm3 should not have been used to calculate the mean titre because it is not in the range of
accuracy of the other two values. Two titres are required that are the same or 0.20cm3 of each
other.

Too many significant figures in the mean titre answer.

Example 13:

Example 14:

Example 15:

Example 16:

ADNAN CHOWDHURY 23
 UNIT 3B NOTES

Example 17:

Example 18:

ADNAN CHOWDHURY 24
 UNIT 3B NOTES

Example 19:

Example 20:

Example 21:

Redox Titrations:

A substance which is found at a high state of purity is known as a primary standard substance.

The crystals of a primary standard substance are neither deliquescent (it does not become a liquid by
absorbing moisture from air) nor efflorescent (it does not loose water of crystallisation, if any, to
atmosphere).

The water of crystallisation in a primary standard substance is fixed.

The molarity (concentration) of a primary standard substance can be calculated accurately if the mass
or number of moles and the volume of the solution is known.

Substances which are not primary standard are usually standardised by titrating them against a
primary standard substance. These titrations are normally redox titrations.

ADNAN CHOWDHURY 25
 UNIT 3B NOTES

Iodometric Titration:

Sodium thiosulfate, Na2S2O3.nH2O is not a primary standard substance as the water of crystallisation is
variable (maximum value of n = 5).

So it is standardised against a solution of iodine, I2 or potassium iodate(V), KIO3 or potassium

dichromate(VI), K2Cr2O7.

Thiosulfate reduces iodine to iodide ions, I- and forms tetrathionate, S4O62-.

2S2O32-(aq) S4O62-(aq) + 2e-

I2(aq) + 2e- 2I-(aq)

2S2O32-(aq) + I2(aq) S4O62-(aq) + 2I-(aq)

The standardised sodium thiosulfate solution can then be used to determine the percentage purity of
copper in a substance, the percentage purity or concentration of KIO3, H2O2, K2Cr2O7, etc.

The substance to be analysed must be an oxidising agent and will produces iodine in another reaction
by oxidation of iodide ions.

Procedure:

A known volume of the solution of the oxidising agent is transferred into a conical flask using a
pipette.

Dilute sulfuric acid is then added to the conical flask using a measuring cylinder (as it is in excess).

Iodine is liberated and the solution becomes brown. It must be ensured that if any solid particles
produced must be completely dissolved.

The liberated iodine is then titrated against standardised sodium thiosulfate solution added from a
beaker.

The brown colour fades to a pale yellow or pale straw colour.

At this point, freshly prepared starch solution is added and the solution becomes blue black. If the
starch solution is not freshly prepared, then blue black colour may not appear. Starch solution should
not be added too early because enough iodine may not be liberated nor too late because at that
event, the end point will be missing. Without starch solution, the colour would gradually fade away
and no sharp end point will be obtained. The blue black complex is formed because the remaining
unreacted iodine will react with the starch reversibly.

The thiosulfate solution is continued adding drop by drop until the blue black colour disappears and
the solution becomes colourless.

The procedure is repeated until at least two concordant titres are obtained.

Determination of Copper:

Points 1, 2 and 3 are as before.

Iodine is liberated and solution becomes milky brown.

2Cu2+ (aq) + 4I- (aq) 2CuI (s) + I2(aq)

white brown

Point 5 as before.

The milky brown or white brown fades to a whitish yellow colour.

Point 6 as before (except for the fact that the solution now becomes whitish or milky blue black).

Point 7 as before (except for the fact that the solution changes colour from milky blue black to
colourless.)

Point 8 as before.

ADNAN CHOWDHURY 26
 UNIT 3B NOTES

Example 22:

3.22g of iodine and 7g of potassium iodide are dissolved in distilled water and made up to 250 cm3. A 25 cm3
portion of this solution required 19.0cm3 of sodium thiosulfate solution in a titration. What is the
concentration of the sodium thiosulfate solution?

Example 23:

5.65g of a copper (II) salt is dissolved in water and made-up to 250 cm3. A 25.0 cm3 sample of solution is
added to an excess of potassium iodide, KI. The iodine formed by the reaction required 21.0cm3 of a 0.10
mol dm-3 solution of sodium thiosulfate for its reduction. What is the percentage by mass of copper in the
salt?

Example 24:

ADNAN CHOWDHURY 27
 UNIT 3B NOTES

Example 25:

Example 26:

Example 27:

ADNAN CHOWDHURY 28
 UNIT 3B NOTES

Example 28:

Example 29:

ADNAN CHOWDHURY 29
 UNIT 3B NOTES

Example 30:

Example 31:

ADNAN CHOWDHURY 30
 UNIT 3B NOTES

Example 32:

Experimental Methods:

The rate of a reaction can be estimated in a number of ways. A common method is to measure the time, t,
for a certain amount of the mixture to react or the time for a certain amount of product to be formed. The
assumption is then made that 1/t is a measure of the rate. This is not strictly accurate because the rate will
have been decreasing from the moment that the reactants were mixed. It is only a fair assumption if the
concentrations of the reactants do not change significantly during the time of the experiment.

Measurable physical changes:

There are a number of physical changes that can be used to estimate the rate of a chemical reaction.

Production of a gas:

If a gas is given off in a reaction, then the volume of the gas can be recorded at regular intervals of time
either by using a gas syringe or measuring cylinder.

ADNAN CHOWDHURY 31
 UNIT 3B NOTES

Gas syringe can be used for collecting acidic, alkaline as well as neutral gases.

Measuring cylinder can only be used for collecting neutral gases as acidic or alkaline gases will react
with water and the yield of the gas will be low.

The advantage of using measuring cylinder over gas syringe is that it is user friendly, as volume of gas
is recorded from the downward displacement of water, and removes any impurities present in the gas.

Example 33:

CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

CO2 is only slightly soluble in water so it can be collected using measuring cylinder.

This is also a suitable method for measuring the decomposition of hydrogen peroxide using, for example,
either different catalysts or different concentrations of hydrogen peroxide:

This method is also suitable for studying the effect of temperature on the rate of reaction between
magnesium and hydrochloric acid:

Change in mass:

If a gas is given off in a reaction, the system will lose mass. The change in mass can be recorded at regular
intervals of time using a mass balance.

ADNAN CHOWDHURY 32
 UNIT 3B NOTES

Colour Change:

The change in colour of either a reactant or a product is measured using a colorimeter.

The rate of the reaction between acidified potassium dichromate(VI) solution and an alcohol can be studied
by measuring the intensity of the colour of the solution, which changes from orange to green as the
dichromate(VI) is reduced by the alcohol.

Production of a Solid:

The time taken to produce enough solid to hide a cross on a piece of paper under the reaction apparatus or
on the side of the apparatus can be measured.

This method is used to measure the decomposition of sodium thiosulfate by acid. The solutions are mixed and
placed in a boiling tube that has a felt-pen cross marked on the side. The time taken for enough sulfur to be
produced to hide the cross, when viewed from the other side of the boiling tube, is measured. The
experiment can then be repeated, for example, with either different concentrations or at different
temperatures.

Catalysts are not used up during a reaction. It can be proved by weighing the catalyst with the help of
a mass balance at the start of reaction. When the reaction is complete, the catalyst is filtered, dried
and re-weighed. It will be seen there will be no change in mass.

ADNAN CHOWDHURY 33
 UNIT 3B NOTES

Example 34:

Example 35:

Iodine chloride is placed in a U tube and chlorine passed over it.

As chlorine is passed into the system its concentration is increased. The system acts to reduce the chlorine
level again by shifting to the right.

As the chlorine concentration is decreased. The system acts to increase it again by shifting to the left.

Example 36:

If the sealed syringe is placed in a beaker of hot water, the gas becomes darker as the equilibrium shifts to
the right (the endothermic direction) more NO2 is produced.

ADNAN CHOWDHURY 34
 UNIT 3B NOTES

If the gas in the syringe is compressed, its get darker at first as concentration has increased. But then the
mixture gets paler as some brown NO2 is converted into colourless N2O4. As pressure is increased, the
equilibrium has moved towards the side with fewer moles of gas to reduce the pressure again.

Organic compounds:

It will always be told if a compound, or mixture of compounds, to be identified is organic. Often the
molecular formula, or the number of carbon atoms in a molecule, of a compound will be given. Chemical tests
may be followed by spectroscopic information.

Appearance:

Simple organic compounds are usually colourless liquids or white solids. It is unlikely that appearance alone
will provide firm evidence for identification.

Solubility:

Test and solubility of pH of Possible

Possible identity Inference
compound solution identity

simple alcohols, simple above 7 amines It forms hydrogen

carboxylic acids, bonds with water
dissolve in water propanone, simple carboxylic -OH group is present
aldehydes, simple below 7 acids, (for alcohol or
amines and their salts phenols carboxylic acid)

dissolve in dilute acid

but may not dissolve in amines
water

It does not form

hydrogen bonds with
water.
No OH group or an
two layers are formed
acid or alcohol or
carbonyl compound
with at least four
carbon atoms

dissolve in aqueous
alkali but may not carboxylic acids, phenols
dissolve in water
a small amount of
universal indicator is It is a neutral substance.
added and solution
turns green
blue litmus paper or
solution is added and carboxylic acids It is an acid.
it turns red

Ignition:
Igniting an organic unknown on a crucible lid may help in identifying it.

Observation Possible inferences

high carbon to hydrogen ratio.
burns with a smoky flame aromatic e.g. benzene, unsaturated e.g.
alkene.
saturated low molar mass compound
burns with a clear non-smoky flame low carbon to hydrogen ratio.

no residue most lower molar mass compounds

ADNAN CHOWDHURY 35
 UNIT 3B NOTES

Chemical tests:
The details of how these tests are to be carried out will be included in the instructions to students in the
assessment activities.

Test Observation Inferences Type of Reaction & Equation

red brown or yellow
colour is
decolourised i.e. it
alkene (C=C) electrophilic addition
turns colourless
two layers are
bromine water is added formed
and shaken
red brown or yellow colour
is decolourised i.e. it turns
colourless and a white phenol electrophilic substitution
precipitate is also formed

potassium manganate
(VII) solution and a purple solution turns
dilute acid (e.g. colourless
sulfuric acid) or a alkene (C=C) oxidation
two layers are
dilute alkali (e.g.
formed
sodium hydroxide) are
added and warmed
neutral potassium alkene (C=C) or
manganate (VII) purple solution turns to a
solution aldehyde (CHO) oxidation
brown precipitate
is added
RCl(l) + OH-(aq) ROH(l) + Cl-(aq)
White precipitate, soluble in Cl-(aq) + Ag+(aq) AgCl(s)
C-Cl present.
dilute ammonia solution AgCl(s) + 2NH3(aq)
[Ag(NH3)2]+(aq) + Cl-(aq)

Cream precipitate, insoluble RBr(l) + OH-(aq) ROH(l) + Br-(aq)

in dilute but soluble in Br-(aq) + Ag+(aq) AgBr(s)
C-Br present.
concentrated ammonia AgBr(s) + 2NH3(aq)
solution.
[Ag(NH3)2]+(aq) + Br-(aq)

dilute sodium hydroxide RI(l) + OH-(aq) ROH(l) + I-(aq)

Yellow precipitate, insoluble
solution or ethanol (it
in concentrated ammonia C-I present. I-(aq) + Ag+(aq) AgCl(s)
acts as a solvent) is
solution. AgI(s) + 2NH3(aq) no reaction
added and warmed.
Then excess nitric acid
is added to neutralise
the sodium hydroxide.
Then silver nitrate
solution is added. A Note:
precipitate is formed All are precipitation reactions.
whose solubility is Nitric acid is added because sodium hydroxide will react with silver nitrate to give a
tested with dilute or black precipitate of silver oxide.
concentrated ammonia AgNO3(aq) + NaOH(aq) AgOH(s) + NaNO3(aq)
2AgOH(s) Ag2O(s)+H2O(l)
To compare the reactivities, three test tubes are set up each containing a different
halogenoalkane (RCl, RBr, RI), ethanol (as a solvent), nitric acid and silver nitrate
solution in a beaker of hot water.
It will be observed that yellow precipitate appears first, then creamy and finally
white. So rate of hydrolysis is I->Br->Cl-
If the experiment is repeated with three different chloro or bromo or iodoalkanes
(1, 2, 3) then rate of hydrolysis is 3>2>1

ADNAN CHOWDHURY 36
 UNIT 3B NOTES

Test Observation Inferences Type of Reaction & Equation

1 alcohol
orange to green solution 2 alcohol
aldehyde

to distinguish between 1 and 2 alcohol, the

potassium dichromate oxidation
final product will be treated with a small
(VI) solution and dilute amount of any alcohol, concentrated sulfuric
sulfuric acid are added acid and warmed. Then the solution is poured
and heated under reflux into a beaker containing some sodium
carbonate solution and cautiously the product
is smell. If a fruity smell is formed with fizzing
then the product is a carboxylic acid and the
reactant is a 1 alcohol.

3 alcohol
no change no reaction
ketone

1 alcohol
orange to green solution 2 alcohol

potassium dichromate
(VI) solution and dilute oxidation
sulfuric acid are added to distinguish between 1 and 2 alcohol, the
and the product is final product will be treated with Tollens
immediately distilled reagent. If a silver mirror is formed then the
final product is an aldehyde and the reactant
is a 1 alcohol.

3 alcohol
no change no reaction
ketone
bubbles evolved -OH group in
a small piece of sodium ROH(l) + Na(s) RO-Na+(l) + H2(g)
sodium disappears or alcohol or
is added
carboxylic acid RCOOH(l) + Na(s) RCOO Na (l) + H2(g)
- +
a white solid forms

solid phosphorous (V)

chloride is added and steamy fumes
ROH(l) + PCl5(s) RCl(l) + POCl3(l) +
any gas evolved is evolved -OH group in HCl(g)
tested with a glass rod white smoke formed alcohol or
dipped in concentrated carboxylic acid RCOOH(l) + PCl5(s) RCOCl(l) +
NH3(g) + HCl(g) NH4Cl(s)
ammonia or damp blue litmus goes red POCl3(l) + HCl(g)
litmus paper

Note:
Alternative reagent: SOCl2(s)
ROH(l) + SOCl2(s) RCl(l) + SO2(g) + HCl(g)
RCOOH(l) + SOCl2(s) RCOCl(l) + SO2(g) + HCl(g)
This is better because two inorganic gases are produced which remove themselves so no
separation technique is required

ADNAN CHOWDHURY 37
 UNIT 3B NOTES

Test Observation Inferences Type of Reaction & Equation

a colourless, odourless gas
which gives a white
precipitate with limewater
(calcium hydroxide
solution) i.e. it turns
limewater milky. If excess
solid sodium carbonate 2RCOOH(l) + Na2CO3(s)/(aq)
CO2 is passed, the
or sodium hydrogen 2RCOO-Na+(l) + CO2(g) + H2O(l)
precipitates dissolves
carbonate (or solution) Carboxylic acid
giving a colourless RCOOH(l) + NaHCO3(s)/(aq)
is added and any gas (COOH)
solution. RCOO-Na+(l) + CO2(g) + H2O(l)
evolved is tested with
limewater Ca(OH)2(aq) + CO2(g)
CaCO3(s) + H2O(l)
CaCO3(s) + H2O(l) + CO2(g)

Ca(HCO3)2(aq)

blue litmus solution or Carboxylic acid

litmus goes red
paper (COOH)
a small amount of any
alcohol, concentrated
sulfuric acid are added
and warmed. Then the fizzing Carboxylic acid
solution is poured into a
smell of fruity smell (COOH)
beaker containing some
sodium carbonate
solution and cautiously
the product is smelled
a small amount of any
carboxylic acid,
concentrated sulfuric
acid are added and
warmed. Then the fizzing
alcohol
solution is poured into smell of fruity smell
a beaker containing
some sodium carbonate
solution and cautiously
the product is smelled
bubbles evolved
a small magnesium magnesium disappears or Carboxylic acid 2RCOOH(l) + Mg(s)
ribbon is added a (COOH) (RCOO-)2Mg2+(l) + H2(g)
white solid forms

blue solution gives red

aldehyde oxidation
precipitate
a small amount of
Fehlings (or Benedicts) blue solution remains ketone no reaction
solution is added and
warmed Note:
Fehling solution consists of Fehling A (Cu2+ e.g. CuSO4 complexed with an alkali) and
Fehling B (sodium potassium tartrate)

silver mirror formed aldehyde oxidation

solution stays colourless ketone no reaction

Note:
a small amount of
Tollens reagent is Tollens reagent is prepared by mixing small amount of sodium hydroxide with small
added and warmed amount of silver nitrate. A black precipitate forms.
AgNO3(aq) + NaOH(aq) AgOH(s) + NaNO3(aq)
2AgOH(s) Ag2O(s)+H2O(l)
The precipitate is dissolved in minimum volume of dilute ammonia which gives colourless
[Ag(NH3)2]+

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Test Observation Inferences Type of Reaction & Equation

a small amount of purple solution turns

potassium dichromate colourless aldehyde oxidation
(VII) solution and dilute
sulfuric acid is added
and warmed solution stays purple ketone no reaction
methyl ketone
or ethanol,
a small amount iodine Oxidation
in an alkaline solution methyl
pale yellow precipitate RCOCH3 + 3I2 + 4NaOH CHI3(s) +
(sodium hydroxide) are secondary
added and warmed RCOO-Na+ + 3NaI + 3H2O
alcohol or
ethanol

If all the above tests are negative, the unknown is probably an alkane.

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.
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Safety Precautions:

Distillation 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.

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 let
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. Solid potassium hydroxide is used to dry amines and alcohols as
they form complex ions with calcium chloride

Purification of a solid by Recrystallisation:

The solid is filtered off from the reaction mixture and purified by recrystallisation.

A suitable solvent is chosen in which the solid is soluble when hot and almost insoluble at room
temperature.

The solid is dissolved in minimum amount of hot solvent. Minimum volume is used to get a saturated
solution.

The solution is filtered through a pre-heated glass filter funnel fitted with a fluted paper. This
removes any insoluble impurities.

The filtrate is allowed to cool and the crystals of the pure solid appears.

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Then filtration is carried out again using a Buchner funnel under reduced pressure. This removes any
soluble impurities.

The solid is washed with a little cold solvent in order to remove any remaining insoluble impurities.

The solid is then dried either between packs of filter paper or else a vacuum desiccator or an electric
oven. Using filter papers will reduce the yield as some of the solids will get stick to the papers.

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:

Toxicity

Absorption through the skin

Irritation if inhaled

Corrosive compounds

High flammability

Carcinogenic compound

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.

Example 37:

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Example 38:

Example 39:

Example 40:

Yield:

Yields are less than 100 percent because of:

Competing / side reactions.

Handling losses during transfer and purification.

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Example 41:

Example 42:

Mass Spectrometer:

The mass spectrometer can be used to determine relative atomic mass, relative molecular mass, relative
isotopic abundance, molecular structure, etc.

There are 5 things that happen when a sample is injected into a mass spectrometer:

1. Vaporisation:

If the sample is a solid or liquid, it is vaporised (turned into a gas) using an electric heater.

2. Ionisation:

The gas particles are bombarded with high energy electrons from a filament wire (by
thermionic emission) to ionise them. Electrons are knocked out and positive ions are formed.
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A(g) + e- A+(g) + 2e- A = an atom

M(g) + e- M+(g) + 2e- M = a molecule.

3. Acceleration:

The positive ions are accelerated by an electric field

4. Deflection:

The positive ions are deflected using a magnetic field. Lighter ions with greater charge have
less momentum and are deflected more compared to heavier ones with less charge. For a given
magnetic field, only ions with a particular mass/charge (m/z) ratio can make it to the
detector. Ions with greater mass/charge ratio will deflect more.

5. Detection:

The magnetic field strength is slowly increased. This changes the mass/charge ratio of ions
that can reach the detector. A mass spectrum is produced.

Bombarding with electrons makes some molecules break up into fragments. These all show up in the
mass spectrum making a fragmentation pattern.

The fragment with the greatest relative abundance is called the base peak.

The fragment with the highest m/z value is called the molecular ion (M+) peak.

For organic compounds, the M+ peak has the second highest m/z value and the highest m/z value is for
the (M+1)+ peak. This happens due to Carbon-13 isotope. The mass spectrum of Ethanol is shown:

Common Fragments lost:

Example 43:

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Example 44:

Example 45:

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Example 46:

Example 47:

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Uses of Mass Spectrum:

Carbon dating is a method of working out the age of carbon-based things. About 1 part in a billion of
the carbon in living things is carbon-14. Carbon-14 is radioactive so it decays, but living things are
constantly taking in fresh carbon, so the amount stays constant. As soon as something dies and stop
taking up new CO2, the proportion of Carbon -14 in the thing starts going down. Scientists can use
mass spectrometry to measure how much Carbon-14 an ancient material contains and then works out
its age.

The pharmaceutical industries use mass spectrometry to identify the compounds in the possible new
drugs, and to tell how long drugs stay in the bod by finding molecules of the drug in blood and urine
samples.

Athletes urine is tested for drugs with mass spectrometry. It shows up the presence of banned
substances such as anabolic steroids by their distinctive spectra.

Probes to Mars have carried small mass spectrometers to study the composition of the surface of Mars
and to look for molecules that might suggest life existed on the planet.

Estimating the age of rocks by analysing the ratio of a radioactive element, e.g. 40K, to its daughter
product, 40Ca.

Infrared (IR) Spectroscopy:

Some molecules absorb energy from infrared radiation.

The extra energy makes their covalent bonds vibrate more.

Only molecules made of different atoms can absorb infrared radiation. This is because the polarities
of their bonds change as they vibrate.

So for example, oxygen (O2) and nitrogen (N2) don't absorb infrared radiation, but carbon dioxide
(CO2), water (H2O), nitric oxide (NO) and methane (CH4) do.

Cases that do absorb infrared radiation are called greenhouse gases because they stop some of the
radiation emitted by the Earth from escaping into space.

Gas molecules bonds have certain fixed energy levels. These are called quantised levels. So a bonds
energy can only jump from one level to another.

This means that only frequencies of radiations corresponding to particular amounts of energy are
absorbed. Different molecules absorb different frequencies of radiation.

In infrared (lR) spectroscopy, a beam of lR radiation goes through a sample of a chemical.

The lR energy is absorbed by the covalent bonds in the molecules, increasing their vibrational energy.

The bending or stretching vibrations of different bonds result in absorption at different frequencies.

Bonds between different atoms absorb different frequencies of lR radiation. Bonds in different places
in a molecule absorb different frequencies too - so the O-H group in an alcohol and the O-H in a
carboxylic acid absorb different frequencies.

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Aldehyde

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Ketone

Example 48:

A chemical was suspected to be a pure sample of an unknown compound. When the chemical was tested
using infrared spectroscopy, the spectrum below was obtained:

Is the chemical an aldehyde? Explain your answer.

If the chemical was an aldehyde, it would contain a carbonyl group (a C=O functional group).

In infrared spectroscopy, a carbonyl group would show a strong, sharp peak at about 16801750cm-1.

The spectrum on the right doesn't have a strong peak at this frequency, and so is not an aldehyde (or
a ketone or a carboxylic acid).

Example 49:

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Example 50:

Example 51:

Example 52:

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Uses of IR spectroscopy:

IR spectroscopy has many commercial uses:

One important use of infrared spectroscopy is in the chemical industry, where a reaction can be
followed so that the point where one functional group changes to another can be measured. E.g. in
the oxidation of a secondary alcohol to a ketone, the point at which all the OH groups in the alcohol
have gone can be seen as well as the point when the first C=O groups in the ketone appear.

The degree of polymerisation that has occurred in polymer manufacture can also be measured with IR
spectroscopy. Modern instruments can take readings up to 32 times a second. The machine is set up so
that the absorption at the frequency of the double bond in the monomer can be recorded. The
number of double bonds change as the polymerisation takes place can be observed.

Polymers can be attacked by oxygen during the processes used to make them into useful objects. This
is invisible to the eye but can be identified using IR spectroscopy. Absorption at about 1700 cm-1 is
seen corresponding to a carbonyl group where the polymer has been oxidised. This is the first step in
the formation of cracks in the polymer.

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