Chemistry Unit 3B

Unit 3B Notes
Prepared By Adnan Chowdhury
Civil Engineer, BUET, A Level Chemistry Course

Instructor Maple Leaf International
PREPARED BY ADNAN CHOWDHURY
Flame tests:
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.
MAPLE LEAF INTERNATIONAL SCHOOL Page 1

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.
Action of heating a Solid:

Gas or vapour or other Possible source
carbon dioxide carbonates of metals (including Li2CO3) other
than group 1.
Li2CO3(s) Li2O(s) + CO2(g)
MCO3(s) MO(s) + CO2(g)
M = Group 2 metal
when a hydrated carbonate such as sodium
carbonate is heated.
Na2CO3.10H2O(s) 2NaOH(s) + CO2(g) + 9H2O(l)
oxygen group 1 nitrates (other than LiNO3)
2MNO3(s) 2MNO2(s) + O2(g)
M = Group 1 metal
oxygen and nitrogen nitrates of group 2 (and LiNO3)
dioxide 4LiNO3(s) 2Li2O(s) + 4NO2(g) + O2(g)
2M(NO3)2(s) 2MO(s) + 4NO2(g) + O2(g)
M = Group 2 metal
water hydrated salts or hydrogen carbonate
2MHCO3(s) M2CO3(s) + CO2(g) + H2O(l)M = Group 1 metal
a white solid sublimes on the ammonium salt present
cooler part of the tube e.g. NH4Cl (s) NH3(g) + HCl(g)

Recognition and identification of common gases:

Gas Observations
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)
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
When a hydrated carbonate such as sodium carbonate is heated.
Heating a hydrogen carbonate
2MHCO3(s) M2CO3(s) + CO2(g) + H2O(l)
M = Group 1 metal

Gas Observations
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 a 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)
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)
*nitrogen dioxide, NO2 a brown gas.
Nitrogen dioxide is produced by:
Heating a group-2 nitrate or LiNO3
4LiNO3(s) 2Li2O(s) + 4NO2(g) + O2(g)
2M(NO3)2(s) 2MO(s) + 4NO2(g) + O2(g)
M = Group 2 metal
hydrogen, H2 a colourless, odourless gas which ignites a lighted splint with a pop sound.
Hydrogen is produced by:
The reaction between an acid and a reactive metal.
M(s) + nH+(aq) Mn+(aq) + n/2 H2(g)
The reaction between an alcohol and sodium
ROH(l) + Na(s) RO-Na+(l) + H2O(l)
The reaction between water and either a group-1 metal, or calcium,
strontium, or barium.
M(s) + H2O(l) MOH(aq) + H2(g)
M = Group 1 metal
M(s) + 2H2O(l) M(OH)2(aq) + H2(g)
M = Ca, Sr or Ba

Gas Observations
hydrogen chloride, HCl steamy fumes on exposure to moist air, acidic and forms white smoke with
ammonia.
Hydrogen chloride is produced by:
The reaction between concentrated sulfuric acid 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) ROCl(l) + POCl3(l) + HCl(g)
water vapour, 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)
chlorine, Cl2 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)
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
*bromine, Br2 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 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.

Gas Observations
iodine, I2 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.
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.
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 carbonate or hydrogencarbonate
gas which gives a white precipitate with CO32-(s)/(aq) + 2H+(aq) CO2(g) + H2O(l)
limewater (calcium hydroxide solution)
HCO3-(s)/(aq) + H+(aq) CO2(g) + H2O(l)
i.e. it turns limewater milky.
Carbon dioxide evolved
a colourless, odourless gas evolves which ignites a a metal
lighted splint with a pop sound. M(s) + 2H+(aq) 2M+(aq)/M2+(aq) + H2 (g)
Hydrogen evolved
yellow solution turns orange chromate(VI) to dichromate(VI)
2CrO42-(aq) + 2H+(aq) Cr2O72- (aq) + H2O(l)
sulfur dioxide evolved which is a thiosulfate
colourless, acidic gas and decolourises S2O32-(aq) + 2H+(aq) S(s) + SO2 (g) + H2O(l)
acidified potassium dichromate(VI) paper
or solution from orange [Cr2O72- (aq)] to
green [Cr3+(aq)].
Also pale yellow sulfur precipitate is
formed
sulfur dioxide evolved on warming which sulfite
is a colourless, acidic gas and SO32-(aq)/(s) + 2H+(aq) SO2 (g) + H2O(l)
decolourises acidified potassium
dichromate(VI) paper or solution orange
[Cr2O72- (aq)] to green [Cr3+(aq)].

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**
sulphite 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

brown precipitate manganate(VII), brown precipitate is
MnO2
purple solution is decolourised manganate(VII) in acid solution
pale green solution turns yellow iron(II) to iron(III) in acid solution

Observation on adding H2O2 Inference

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.)
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.
Likely ion Observation on adding small Observation on Observation on adding

amount of dilute NaOH or adding excess excess dilute aqueous NH3
dilute aqueous NH3 dilute NaOH
zinc(II), [Zn(H20)6]2+ a white precipitate of precipitate dissolves precipitate dissolves to
[Zn(OH)2(H2O)4] to a colourless give a colourless solution
solution of of [Zn(H2O)2(NH3)4]2+
[Zn(OH)4(H2O)2]2-
magnesium, [Mg(H20)6]2+ a white precipitate of precipitate is insoluble precipitate is insoluble
[Mg(OH)2(H2O)4]
silver, [Ag(H20)6]+ a white precipitate of precipitate is insoluble precipitate dissolves to give
[Ag(OH)(H2O)5]+ which is a colourless solution of
dehydrated to form a brown [Ag(NH3)2]+.
precipitate of Ag2O
The brown precipitate of
Ag2O is often not seen
because the ammonia
complex forms very easily.
lead(II), Pb2+ a white precipitate of precipitate dissolves to precipitate is insoluble
Pb(OH)2 a colourless solution of
[Pb(OH)4(H2O)2]2-

Likely ion Observation on adding small Observation on Observation on adding

amount of dilute NaOH or adding excess excess dilute aqueous NH3
dilute aqueous NH3 dilute NaOH
barium, Ba2+ a white precipitate of precipitate is insoluble precipitate is insoluble
Ba(OH)2
strontium, Sr2+ a white precipitate of precipitate is insoluble precipitate is insoluble
Sr(OH)2
calcium, Ca2+ a white precipitate of precipitate is insoluble precipitate is insoluble
Ca(OH)2
aluminium, Al3+ a white precipitate of precipitate is insoluble precipitate is insoluble
Al(OH)3
lithium, Li+ a white precipitate of precipitate is insoluble precipitate is insoluble
LiOH
sodium, Na+ no precipitate
potassium, K+ no precipitate
ammonium, NH4+ no precipitate.
On heating, a colourless,
pungent smelling gas evolves
that turns a damp or moist
red litmus paper blue. The
gas is ammonia, 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
carbonate, CO32-/ a white precipitate forms which dissolves on
hydrogencarbonate, HCO3- 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.
Pb2+(aq) + CO32-(aq) PbCO3(s)
PbCO3(s)+ 2H+(aq) CO2(g) + H2O(l) + Pb2+(aq)
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)
sulfite, SO32- 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 [Cr3+(aq)].
Pb2+(aq) + SO32-(aq) PbSO3(s)
PbSO3(s) + 2H+(aq) SO2 (g) + H2O(l) + Pb2+(aq)
sulphate, SO42- a white precipitate forms which does not dissolve on

addition of an acid.
Pb2+(aq) + SO42-(aq) PbSO4(s)
chloride, Cl- a white precipitate forms which dissolves on heating
and reappears on cooling.
Pb2+(aq) + 2Cl-(aq) PbCl2(s)
bromide, Br- a white precipitate forms which dissolves on heating
and reappears on cooling.
Pb2+(aq) + 2Br-(aq) PbBr2(s)

Anion Inference
iodide, I- a yellow precipitate forms which has no effect on
heating.
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
sulfate, SO42- a white precipitate forms which does not dissolve

on addition of HCl acid.
Ba2+(aq) + SO42-(aq) BaSO4(s)
sulfite, SO32- 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)].
BaSO3(s)+ 2H+(aq) SO2(g) + H2O(l) + Ba2+(aq)
carbonate, CO32-/ a white precipitate forms which dissolves on
hydrogencarbonate, H CO3- 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.
Ba2+(aq) + CO32-(aq) BaCO3(s)
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)

Anion Inference
chromate(VI), CrO42- a yellow precipitate forms which dissolves to

give a orange solution
Ba2+(aq) + CrO42-(aq) BaCrO4(s)
2BaCrO4(s) + 2H+(aq) Cr2O72-(aq) + 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
sulfate, SO42- a white precipitate forms

sulfite, SO32- effervescence of a colourless, acidic gas which
decolourises acidified potassium manganate(VII) paper or
solution from orange to green.
SO32-(aq) + 2H+(aq) SO2 (g) + H2O(l)
carbonate, CO32-/ effervescence of a colourless, odourless gas

hydrogencarbonate, H CO3- which gives a white precipitate with limewater
(calcium hydroxide solution) i.e. it turns
limewater milky.
CO32-(aq) + 2H+(aq) CO2(g) + H2O(l)
HCO3-(aq) + H+(aq) CO2(g) + H2O(l)
chromate(VI), CrO42- yellow solution turns orange.
2CrO42-(aq) + 2H+(aq) Cr2O72- (aq) + H2O(l)
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 (eg 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.
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)

Anion Precipitate Addition of aqueous NH3

colour formula dilute concentrated
chloride white AgCl soluble
bromide cream AgBr soluble in excess soluble
iodide yellow AgI insoluble insoluble
fluoride no precipitate
Silver halides decompose when light shines on them producing silver and
the halogen.
2AgX(s) 2Ag(s) + X2(g)
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.
Halide Observations on adding Observed reaction products

concentrated H2SO4
fluoride steamy fumes (HF), vigorous reaction F-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HF(g)
chloride steamy fumes (HCl), vigorous reaction Cl-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HCl(g)
bromide steamy fumes (HBr), brown Br-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HBr(g)

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

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)
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 Possible identity pH of Possible Inference
compound solution identity
dissolve in water simple alcohols, simple above 7 amines It forms hydrogen
carboxylic acids, bonds with water
propanone, simple -OH group is present
aldehydes, simple below 7 carboxylic (for alcohol or
amines and their salts acids, carboxylic acid)
phenols
dissolve in dilute acid amines
but may not dissolve in
water
two layers are formed It does not form
hydrogen bonds with
water.
No OH group or an
acid or alcohol or
carbonyl compound
with at least four
carbon atoms

Test and solubility of Possible identity pH of Possible Inference

compound solution identity
dissolve in aqueous carboxylic acids, phenols
alkali but may not
dissolve in water
a small amount of It is a neutral substance.
universal indicator is
added and solution
turns green
blue litmus paper or carboxylic acids It is an acid.
solution is added and
it turns red
Ignition:
Igniting an organic unknown on a crucible lid may help in identifying it.
Observation Possible inferences

burns with a smoky flame high carbon to hydrogen ratio.
aromatic eg benzene, unsaturated eg alkene.
burns with a clear non-smoky flame saturated low molar mass compound
low carbon to hydrogen ratio.
no residue most lower molar mass compounds
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
bromine water is red brown or yellow alkene (C=C) electrophilic addition

added and shaken colour is decolourised
i.e it turns colourless
two layers are formed

potassium purple solution turns alkene (C=C) oxidation

manganate (VII) colourless
solution and a dilute two layers are formed
acid (eg sulfuric
acid) or a dilute
alkali (eg sodium
hydroxide) are
added and warmed
neutral potassium purple solution turns to a alkene (C=C) or oxidation
manganate (VII) brown precipitate aldehyde (CHO)
solution
is added
dilute sodium White precipitate, soluble in C-Cl present. RCl(l) + OH-(aq) ROH(l) + Cl-(aq)
hydroxide solution or dilute ammonia solution Cl-(aq) + Ag+(aq) AgCl(s)
ethanol (it acts as a
solvent) is added AgCl(s) + 2NH3(aq)
and warmed. Then [Ag(NH3)2]+(aq) + Cl-(aq)
excess nitric acid is Cream precipitate, insoluble in C-Br present. RBr(l) + OH-(aq) ROH(l) + Br-(aq)
added to neutralise dilute but soluble in
Br-(aq) + Ag+(aq) AgBr(s)
the sodium concentrated ammonia
hydroxide.Then solution. AgBr(s) + 2NH3(aq)
silver nitrate [Ag(NH3)2]+(aq) + Br-(aq)
solution is added. A Yellow precipitate, insoluble in C-I present. RI(l) + OH-(aq) ROH(l) + I-(aq)
precipitate is formed concentrated ammonia
whose solubility is I-(aq) + Ag+(aq) AgCl(s)
solution.
tested with diute or AgI(s) + 2NH3(aq) no reaction
concentrated Note:
ammonia
All are precipitation reactions.
Nitric acid is added because sodium hydroxide will react with silver nitrate to give a
black precipitate of silver oxide.
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

potassium orange to green solution 1 alcohol oxidation

dichromate (VI) 2 alcohol
solution and dilute aldehyde
sulfuric acid are
added and heated
under reflux
to distinguish between 1 and 2 alcohol, the final

product will be treated with a small amount of any
alcohol, concentrated sulfuric acid and warmed. Then the
solution is poured 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.
no change 3 alcohol no reaction

ketone
potassium orange to green solution 1 alcohol oxidation
dichromate (VI) 2 alcohol
solution and dilute
sulfuric acid are
added and the
product is
immediately distilled
to distinguish between 1 and 2 alcohol, the final
product will be treated with Tollens reagent. If a
silver mirror is formed then the final product is an
aldehyde and the reactant is a 1 alcohol.
no change 3 alcohol no reaction

ketone
a small piece of bubbles evolved -OH group in ROH(l) + Na(s) RO-Na+(l) + H2(g)
sodium is added sodium disappears or a alcohol or RCOOH(l) + Na(s) RCOO-Na+(l) +
white solid forms carboxylic acid H2(g)
solid phosphorous steamy fumes evolved -OH group in ROH(l) + PCl5(s) RCl(l) + POCl3(l) +
(V) chloride is added white smoke formed alcohol or HCl(g)
and any gas evolved NH3(g) + HCl(g) NH4Cl(s) carboxylic acid RCOOH(l) + PCl5(s) RCOCl(l) +
is tested with a glass
litmus goes red POCl3(l) + HCl(g)
rod dipped in
concentrated
ammonia or damp
blue 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
solid sodium a colourless, odourless gas Carboxylic acid 2RCOOH(l) + Na2CO3(s)/(aq)
carbonate or sodium which gives a white (COOH) 2RCOO-Na+(l) + CO2(g) + H2O(l)
hydrogen carbonate precipitate with limewater RCOOH(l) + NaHCO3(s)/(aq)
(or solution) is (calcium hydroxide solution)
added and any gas i.e. it turns limewater milky. RCOO-Na+(l) + CO2(g) + H2O(l)
evolved is tested If excess CO2 is passed, the
with limewater 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)
blue litmus solution litmus goes red Carboxylic acid

or paper (COOH)
a small amount of fizzing Carboxylic acid
any alcohol, smell of fruity smell (COOH)
concentrated
sulfuric acid are
added and warmed.
Then the solution is
poured into a beaker
containing some
sodium carbonate
solution and
cautiously the
product is smelled
a small amount of any fizzing alcohol
carboxylic acid, smell of fruity smell
concentrated sulfuric
acid are added and
warmed. Then the
solution is poured into
a beaker containing
some sodium
carbonate solution and
cautiously the product
is smelled

a small magnesium bubbles evolved Carboxylic acid 2RCOOH(l) + Mg(s)

ribbon is added magnesium disappears or a (COOH) (RCOO-)2Mg2+(l) + H2(g)
white solid forms
a small amount of blue solution gives red aldehyde oxidation
Fehlings (or precipitate
Benedicts) solution
is added and
warmed
blue solution remains ketone no reaction
Note:
Fehling solution consists of Fehling A (Cu2+ eg CuSO4 complexed with an alkali) and Fehling B
(sodium potassium tartrate)
a small amount of silver mirror formed aldehyde oxidation
Tollens reagent is
added and warmed
solution stays colourless ketone no reaction

Note:
Tollens reagent is prepared by mixing small amount of sodium hydroxide with small 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]+
a small amount of purple solution turns aldehyde oxidation

potassium manganate colourless
(VII) solution and
dilute sulfuric acid is
added and warmed
solution stays purple ketone no reaction

a small amount pale yellow precipitate methyl Oxidation

iodine in an alkaline ketone or RCOCH3 + 3I2 + 4NaOH CHI3(s) +
solution (sodium 21thanol, RCOO-Na+ + 3NaI + 3H2O
hydroxide) are
added and warmed C CH3
O
methyl
secondary
alcohol or
ethanol
CH CH3
OH
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.
Steam Distillation:
It is used to extract a volatile substance that is insoluble in water from a reaction

mixture that contains an immiscible liquid as well as a solution.
it is particularly useful for obtaining a substance that would decompose at its boiling
point.

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 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.

Less dense liquid
More dense liquid
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 forms 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.
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 compounds
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.
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 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.
The calculation is carried out in three steps:
Heat produced by the combustion of the fuel in Joules = m c T

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
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). 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.
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.

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).
Amount / Number of moles of solute reacted = concentration (moldm-3) volume
(dm3)
For enthalpy of solution determination,
Amount / Number of moles of solute reacted = (mass before mass after) molar
mass of fuel
Enthalpy of Reaction, Hr = heat produced or lost in kilo Joules moles of solute
reacted
If there is a temperature rise, H is negative; if the temperature falls, H is positive.
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.
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).
Amount / Number of moles of solute reacted = concentration (moldm-3) volume
(dm3)
Enthalpy of Reaction, Hr = heat produced or lost in kilo Joules moles of solute
reacted
If there is a temperature rise, H is negative; if the temperature falls, H is positive.

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 (25 cm3 or 10 cm3)
Conical Flask
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 ran 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 ran 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 0.05 cm3.
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.
Worked example
A student produced the following results from a titration:
burette reading 1 2 3
final cm3 23.40 23.67 23.40

start cm3 0.00 0.05 0.05
volume used cm3 23.40 23.62 23.35

Mean titre = 1/3 (23.40 + 23.62 + 23.35) = 23.4566 cm3
What are the three errors in the students work?
Answers
(a) 23.67cm3 is incorrect because the burette cannot be read to that

level of accuracy.
(b) 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.
(c) Too many significant figures in the mean titre answer.
Worked Example:
A sample of 2.65g of pure sodium carbonate, Na2CO3, was weighed out, dissolved in water and
made up to 250cm3 in a standard flask. Some of this was placed in a burette and used to
titrate 25cm3 portions of a solution of hydrochloric acid. The equation for the reaction is:
2HCl(aq) + Na2CO3(aq) 2NaCl(aq) + H2O(l) + CO2(g)
The titres obtained are shown in the table.
Experiment Titre / cm3
1 22.35
2 22.40
3 21.85
4 22.50
a) Calculate the concentration of the sodium carbonate solution.

b) Calculate the mean titre.
c) Calculate the amount (in moles) of sodium carbonate solution in the mean titre.
d) Calculate the amount (in moles) of hydrochloric acid that reacted.
e) Calculate the concentration of the hydrochloric acid solution.
Worked Example
25 ibuprofen tablets were reacted with 50cm3 of 1 moldm-3 NaOH solution.

C12H17COOH + NaOH C12H17COO-Na+ + H2O
When the reaction was over, the solution containing excess sodium hydroxide, was made up
to 250cm3 with distilled water. 25cm3 samples were titrated against 0.110 moldm-3
hydrochloric acid solution:
NaOH + HCl NaCl + H2O
Calculate the mass, in mg, of ibuprofen in one tablet.

Worked Example
A fertiliser contains ammonium sulphate and potassium sulphate. When0.50g of the fertiliser
was warmed with sodium hydroxide solution, ammonia gas was evolved. The ammonia
required 15.0cm3 of 0.2 M hydrochloric acid to neutralise it. What is the percentage by mass
of ammonium sulphate in the fertiliser?
Worked Example
A marble chip of mass 5.0g required 40cm3 of 1.5 moldm-3 hydrochloric acid to react with all
the calcium carbonate it contained. What is the percentage of calcium carbonate in the
marble chip?
Worked Example
13.73g of sodium carbonate crystals were dissolved in 1 dm of water. 25cm3 of the solution
were neutralised by 24cm3 of 0.10 mol dm-3 hydrochloric acid. What is the value of n in the
formula Na2CO3.nH2O for sodium carbonate crystals?

Indicators:
pKin acid pH range alkaline neutral

(at 298 K) colour colour colour
1 Methyl violet 0.8 yellow 0.01.6 blue
2 Malachite green 1.0 yellow 0.21.8 blue/green
3 Thymol blue (acid) 1.7 red 1.22.8 yellow
4 Methyl yellow (in ethanol) 3.5 red 2.94.0 yellow
5 Methyl orangexylene 3.7 purple 3.24.2 green orange
cyanole solution
6
7 Methyl orangeblue
Bromophenol 3.7
4.0 yellow re 3.24.4
2.84.6 yellow
blue green
8 Congo red 4.0 violet d 3.05.0 red
9 Bromocresol green 4.7 yellow 3.85.4 blue green
10 Methyl red 5.1 red 4.26.3 yellow orange
11 Azolitmin (litmus) red 5.08.0 blue

1
12 Azolitmin (litmus)
Bromocresol purple 6.3 yellow re 5.08.0
5.26.8 blue
purple
1
13 Bromothymol blue 7.0 yellow d 6.07.6 blue green
1
14 Phenol red 7.9 yellow 6.88.4 red
15 Thymol blue (base) 8.9 yellow 8.09.6 blue
16 Phenolphthalein (in ethanol) 9.3 colourless 8.210.0 red pale pink

1
17 Phenolphthalein (in ethanol)
Thymolphthalein 9.3
9.7 colourless
colourless 8.210.0
8.310.6 red
blue
6
18 Alizarin yellow R 12.5 yellow 10.113.0 orange/red
Thymol blue also changes from red to yellow around a pH of 2

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.
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.
Worked Example
3.22g of iodine and 7g of potassium iodide are dissolved in distilled water and made up to
250cm3. A 25.0cm3 portion of this solution required 19.0cm3 of sodium thiosulfate solution in
a titration. What is the concentration of the sodium thiosulfate solution?
Worked Example
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?
Worked Example
A commercial medication contains potassium iodate. 1.20 g of the medication were dissolved
in water and made up to 250 cm3. A 25 cm3 sample was added to an excess of potassium
iodide, KI. The iodine formed by the reaction required 19.6 cm3 of a 0.05 mol dm-3 solution of
sodium thiosulfate for its reduction.
What is the percentage by mass of potassium iodate in the medication?
(K = 39, I = 127, O = 16)
IO3- + 5I- + 6H+ 3I2 + 3H2O

Worked Example
25 cm3 of liquid bleach, in which the active ingredient is NaClO, are made up to 250 cm3 with
distilled water. 25 cm3 of this solution were added to an excess of potassium iodide. The
iodine formed by this reaction required 20.30 cm3 of a 0.02 moldm-3 solution of sodium
thiosulfate for its reduction. Find the concentration of ClO- ions in the bleach.
2I- + 2H+ + ClO- I2 + H2O + Cl-

Chemistry Unit 3B

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Chemistry Unit 3B

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Unit 3B Notes

Prepared By Adnan Chowdhury

Civil Engineer, BUET, A Level Chemistry Course

A platinum or nichrome wire or a specially marketed flame test rod is taken.

Flame colour Inference

* Further tests would be needed to distinguish these ions.

MAPLE LEAF INTERNATIONAL SCHOOL Page 1

Origin of Flame Colour:

Action of heating a Solid:

MAPLE LEAF INTERNATIONAL SCHOOL Page 2

Recognition and identification of common gases:

MAPLE LEAF INTERNATIONAL SCHOOL Page 3

I-(aq)/(s) + H2SO4(aq) HSO4-(aq) + HI(g)

MAPLE LEAF INTERNATIONAL SCHOOL Page 4

MAPLE LEAF INTERNATIONAL SCHOOL Page 5

Action of dilute acids:

Action of acid Possible source

MAPLE LEAF INTERNATIONAL SCHOOL Page 6

Tests for oxidizing and reducing agents:

Oxidizing agents usually:

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

Observation on adding H2O2 Inference

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

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Observation on adding H2O2 Inference

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

All group-1 salts.

All ammonium salts.

Insoluble ionic compounds include:

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

All hydroxides, apart from group-1 hydroxides, barium hydroxide and

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SODIUM HYDROXIDE AND AMMONIA SOLUTION:

Small amount of dilute aqueous ammonia (NH3), when added to a solution

Aqueous sodium hydroxide or aqueous ammonia should be added until it is in

Likely ion Observation on adding small Observation on Observation on adding

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Likely ion Observation on adding small Observation on Observation on adding

The test for NH4+ ion is

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

Pb2+(aq) + 2HCO3-(aq) Pb(HCO3)2(s)

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

sulphate, SO42- a white precipitate forms which does not dissolve on

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nitrate, NO3- no precipitate

Barium chloride solution:

sulfate, SO42- a white precipitate forms which does not dissolve

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

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chromate(VI), CrO42- a yellow precipitate forms which dissolves to

sulfate, SO42- a white precipitate forms

carbonate, CO32-/ effervescence of a colourless, odourless gas

Silver nitrate solution:

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Anion Precipitate Addition of aqueous NH3

Concentrated sulfuric acid:

Halide Observations on adding Observed reaction products

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

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Test for the nitrate ion:

warmed with aqueous sodium hydroxide and aluminium or zinc powder or