WEEK 4

TOPIC: HYDROGEN
Hydrogen is the lightest element making up about 1% of the earth crust. It is widely distributed in
combination with other elements in the form of water, acids, organic substances and petroleum products. It
is found uncombined in very small quantity in the atmosphere.
Hydrogen is the first element in the Periodic Table. Its atom consists of one proton and one electron. It
can be placed both in Group I and Group VII of the Periodic Table. In Group I because it has one electron
in its valence shell and in group VII because it is only one electron short of the noble gas structure of
helium. The electronic configuration is 1S1.
Laboratory preparation of hydrogen
Hydrogen can be prepared in the laboratory by 3 different methods
A) Action of dilute acid on zinc: dilute HCl or H2SO4 reacts with granulated zinc to liberate hydrogen gas.
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)
The hydrogen gas is given off in a gas jar over water. If it is required dry, it is passed through fused calcium
chloride or conc. H2SO4 and collected by downward displacement of air (or by upward delivery) since it is
lighter than air.
Note: dilute HNO3 is not used for this reaction because it is a strong oxidizing agent. It will oxidize the
hydrogen formed to water. It will only produce hydrogen gas with magnesium.

(B) Action of cold water on active metal: sodium and potassium metals react vigorously with cold water
to liberate hydrogen gas. Calcium undergoes the same reaction but at a slower rate.
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)

(C) Action of steam on iron: iron at red heat reacts with steam to produce triiron-tetraoxide (a black
residue) and hydrogen gas.
3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

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INDUSTRIAL PREPARATION OF HYDROGEN
(1) FROM WATER GAS (BOSCH PROCESS): water gas is produced when steam is passed over red hot coke at
about 1100 C. When excess steam is mixed with the water gas and the mixture passed over a suitable
0

catalyst (iron (III) oxide or chromium (III) oxide at 4500C, the carbon (II) oxide in the water gas is converted to
carbon (IV) oxide and more hydrogen is produced.
C(s) + H2O(l) CO + H2 endothermic reaction
CO + H2 + H2O(g) CO2(g) 2H2(g) exothermic reaction
The carbon(IV) oxide is separated from the hydrogen by dissolving it in water at 30 atm pressure, or
bypassing the mixture through an alkali solution which absorbs carbon(IV) oxide leaving hydrogen.
H2O(l) + CO2(g) H2CO3(aq)
NaOH(aq) + CO2(g) Na2CO3(aq) + H2O(l)
Any remaining trace of carbon(II) oxide is absorbed under pressure by ammoniacal solution of copper (I)
ethanoate.
(2) FROM HYDROCARBONS (METHANE):when methane is treated with steam at 8000C and 30 atm. in the
presence of nickel catalyst, a mixture of carbon(II) oxide and hydrogen gas is produced. This is known as
synthesis gas
CH4(g) + H2O(g) Ni
CO + 3H2(g)
Synthesis gas;
(note the difference between water gas and synthesis gas)
The synthesis gas is mixed with more steam and passed over iron (III) oxide catalyst at 450 C. carbon (II)oxide
0

is converted to carbon(IV) oxide with further yielding of hydrogen. Carbon (IV) oxide and any unreacted
carbon (II) oxide are removed the same way as in Bosch process.
(3) BY ELECTROLYTIC METHOD: hydrogen is obtained as a by-product in the electrolysis of brine. When a
cheap source of electricity is available, hydrogen is also obtained from the electrolysis of acidified water.
PHYSICAL PROPERTIES OF HYDROGEN
1. Pure hydrogen is a colourless, odourless and tasteless gas.
2. It is neutral to litmus paper
3. It is the lighted substance known; about 14.4 times less dense than air
4. It has a very low boiling point of about -2530C.
5. It is relatively insoluble in water.
6. It burns with a pale blue flame but does not support combustion.
7. It is not poisonous
Chemical properties
The chemical properties of hydrogen can be explained on the basis of its ability to:
- Gain an electron and form a negative hydride ion, H-.
- Forming a covalent bond by sharing its lone electron as it is in hydrogen molecule, H – H.
- Donating its lone electron to form positive hydrogen ion, H+ which enters into dative bonding
with a molecule having lone pairs of electrons, e.g. formation of ammonium ion, NH 4+.
The chemical properties of hydrogen are as follows:
1. Reaction with metals: hydrogen combines directly with the more reactive metals to form ionic
hydrides. 2Na(s) + H2(g) 2NaH(s)
2. Reaction with oxygen: pure hydrogen burns with a pale blue flame in oxygen to form steam.
2H2(g) + O2(g) 2H2O(g)
3. With halogens: hydrogen combines directly with halogens to form halides;
H2(g) + Cl2(g) 2HCl(g)
4. Reaction with nitrogen: hydrogen combines directly with nitrogen to produce ammonia.
N2(g) + 3H2(g) 2NH3(g)
5. Reducing action: hydrogen is a strong reducing agent. it reduces the heated oxides of copper,
lead, iron and zinc to the corresponding metals; CuO(s) + H2(g) Cu(s) + H2O(l)
Uses of hydrogen
- Hydrogen is used in the synthesis of ammonia

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- It is used in the hardening of vegetable and animal oil for the manufacturing of margarine, soap and candle.
- Liquid hydrogen is used as rocket fuel
- It is used in oxy-hydrogen flame to produce high temperature of over 2000 0C that is capable of melting
metals.
- It is used in atomic hydrogen flame
- It is used for filling balloons
- It is a constituent of many gaseous fuels such as water gas and coal gas.
- It is used for the extraction of tungsten from its ore.
Test for hydrogen
When a lighted splinter is inserted into a test-tube containing hydrogen, it burns with a pop sound.

Isotopes of hydrogen
Hydrogen has three isotopes namely
- Protium or hydrogen – 1H
1

- Deuterium or heavy hydrogen – 1H 2

- Tritium – 1H
3

The most abundant is protium, although it is less reactive. Tritium is radioactive with a half life of about12
years.
Hydrides
When reactive metals like sodium, potassium and calcium react with hydrogen, ionic hydrides are
formed. The ionic hydrides share some properties with other ionic compounds e.g.
1. They are crystalline solids with high boiling and melting points
2. They conduct electricity when molten
3. They combine readily with water to form hydroxides and liberate hydrogen gas
CaH(s) + 2H2O(l) Ca(OH)2(aq) + 2H2(g)
- Aluminium and boron form complex covalent hydrides which are important reducing agents
especially in organic chemistry, e.g. lithium tetrahydridoaluminate(III), LiAlH 4 and sodium
tetrahydrido borate (III), NaBH4.
- Non-metals like chlorine and nitrogen form simple covalent hydrides which are gaseous at room
temperature. The hydrides of fluorine and oxygen however are liquid at room temperature
because of the presence of hydrogen bonds.
- The hydrides of the more electronegative elements like chlorine and sulphur form acidic
solutions when dissolved in water.
Assignment
Answer question 4 on page 228 of Essential Chemistry
Tutorial questions
1. State three properties of hydrides
2. What are the isotopes of hydrogen?
3. State the property of hydrogen which makes it suitable for filing balloons
4. Why is helium preferred to hydrogen in filling balloons?
5. State three industrial methods for preparing hydrogen
6. Under what conditions will hydrogen react with (i) oxygen (ii) chlorine (iii) nitrogen (iV) calcium.
Write balance equations for the reactions.
7. state the test for hydrogen

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WEEK 5
TOPIC: OXYGEN
Oxygen is the most abundant element on earth. It belongs to the Group VI of the Periodic Table. The
other elements in the Group are sulphur, selenium, tellurium and polonium. There is an increase in
metallic properties from oxygen to polonium; hence the elements in oxygen family vary widely in their
chemical properties. The following trends are seen in the Group;
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- All the elements have an outer electronic configuration s ,p4
- The atomic radius increases down the Group
- The melting and boiling points increase from oxygen to tellurium
- Electronegativity decreases down the Group
General properties of Group VI elements
1. They are chemically reactive
2. They have high electron affinity and tend to form covalent compound with other non-metals.
Only polonium which is a metal is an exception to this property.
3. The most common oxidation state is -2. However, +2, +4 and +6 oxidation states are possible for
sulphur, selenium, tellurium and polonium.
The bonding capacity of oxygen
The electronic configuration of oxygen is 1s2,2s2,2p4(2,6). It requires two more electrons to completely
fill its valence shell. This is achieved by gaining or sharing electrons. When oxygen gains two electrons
from metals, it form ionic compounds e.g. Na2O, CaO MgO etc. When it shares electrons with other
non-metal, covalent compounds are formed e.g. O2, SO2, CO2 etc. Oxygen can also form coordinate
bonding in molecules e.g in CO
Laboratory preparation of oxygen
1. By the reaction of hydrogen peroxide with acidified potassium tetraoxomanganate (VII) in the
cold. It is a redox reaction in which KMnO4 is the oxidizing agent and H2O2 is the reducing agent.
5H2O2(aq) + 2KMnO4(aq) + 3H2SO4(aq) K2SO4(aq) + 2MnSO4(aq) + 8H2O(l) + 5O2(g)

2. By catalytic decomposition of potassium trioxochlorate (V). KClO3 is heated with the catalyst
MnO2. The KClO3 decomposes to oxygen and potassium chloride;
2KClO3(s) heat 2KCl(s) + 3O2(g)In both cases, oxygen is collected over water.

3. By catalytic decomposition of hydrogen peroxide: add 10 volume or 3% hydrogen peroxide solution very
slowly to a catalyst such as manganese (IV) oxide (MnO2). Oxygen gas will be liberated;
“H2O2(aq) O2(g) + 2H2O(l)

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Industrial preparation of oxygen
Oxygen is prepared industrially by the fractional distillation of air. The following are the steps involved’
- Cold air is compressed to about 150atm
- The compressed air is cooled by refrigeration to separate out CO2 and water vapour. The two
gases become solids and are removed by filtration.
- Cold air is allowed to expand through a nozzle. The expansion causes air to cool rapidly.
- The compression and expansion cycles are repeated until the temperature reaches about -2000C,
when liquid air is produced.
- The liquid air is warmed up and then fraction ally distilled.

Physical properties of oxygen

1. it is slightly denser than air
2. It is a colourless and odourless gas
3. It has no effect on moist litmus paper
4. It is sparingly soluble in water
5. It does not burn but support combustion
6. It is non-poisonous
Chemical properties of oxygen
A. Reaction with metals: the reaction of oxygen with metals depends on the reactivity of the metals.
- Alkali metals react readily with oxygen; hence they are usually kept under oil e.g. sodium
4Na(s) + O2(g) 2Na2O(s)
- Alkali earth metals like magnesium burn vigorously in oxygen to form oxides
2Mg(s) + O2(g) 2MgO(s)
- Metals such as iron and cupper react with oxygen, only when heated strongly, to form oxides e.g.
2Fe(s) + 2O2(g) heat Fe3O4(s)
B. Reaction with non-metals:
- Hydrogen burns in oxygen with pale blue flame to form water
2H2(g) + O2(g) 2H2O(l)
- Carbon burns in limited supply of oxygen to produce carbon (II) oxide gas;
2C(s) + O2(g) 2CO(g)
- In excess oxygen, carbon burns to produce carbon (IV) oxide;
C(s) + O2(g) CO2(g)
- Sulphur burns with a bluish flame to produce sulphur (IV) oxide;
S(s) + O2(g) SO2(g)
The reactions of oxygen with metals and non-metals are all oxidation reactions. Oxidation reactions
include burning of fuels, rusting o iron and respiration.
Binary compounds of oxygen
An oxide is a compound of oxygen and another element. They are grouped into five;

5
1. Acidic oxide
2. Basic oxide
3. Amphoteric oxide
4. Neutral oxide
5. Higher oxide
Acidic oxides: these are oxides of non-metals. They dissolve in water to form acids e.g. SO2, CO2, SO3,
NO2, P4O10.
SO2(g) + H2O(l) H2SO3(aq)
Acidic oxides do not react with acids but react with alkalis to form a salt and water.
SO2(g) + 2NaOH(aq) Na2SO3(aq) + H2O(l)
Silicon (IV) oxide, SiO2 is a solid at room temperature. It is an acidic oxide. It does not dissolve in water
but react with sodium hydroxide to form sodium trioxosilicate (IV) and water.
SiO2(s) + 2NaOH(aq) Na2SiO3(aq) + H2O(l)
Properties of acidic oxides
- They are usually gases at room temperature (except P4O10 and SiO2)
- If soluble, they dissolve in water to form acidic solution
- They react with alkalis or bases to form a salt and water only.
Basic oxide: they are oxides of metals. Most of them are insoluble in water. A few of them such as Na2O
and K2O dissolve readily in water. These soluble oxides are called alkalis. Calcium oxide (quick lime)
dissolves moderately in water (a vigorous reaction) to form lime water.
Basic oxides are solids at room temperature. They react with acids to form salts and water only, e.g.
CaO(s) + 2HNO3(aq) Ca(NO3)2(aq) + H2O(l)
Amphoteric oxide: these are metallic oxides that react with both acids and bases to form salts and
water only e.g. zinc oxide-ZnO, aluminium-Al2O3 and lead (II) oxide – PbO.
Neutral oxides: some non-metals form oxides that show neither basic nor acidic properties. They are
called neutral oxides. They are insoluble in water (except water itself). Examples are water, carbon (II)
oxide and nitrogen (II) oxide.
Higher oxides: Higher oxides are oxides containing a higher proportion of oxygen than the ordinary oxides.
Example Perioxides (H2O2, K2O2, CaO2, BaO2), Dioxides (PbO2, MnO2) and Mixed oxides (Pb3O4, Fe3O4)
Uses of oxygen
Oxygen is used:
1. In steel making industry to burn off or oxidize impurities such as carbon, sulphur andphosphorus.
2. In the hospital to help patients with breathing difficulties
3. By mountain climbers, pilots of high-flying fighter planes and deep sea divers to help thembreathe at high
altitude and under water.
4. In the oxy-acetylene flame (about 35000C) to cut metals or weld them together.
5. In the manufacture of important chemical compounds like tetraoxosulphate (VI) acids,trioxonitrate (V)
acid and ethanoic acid
6. Liquid oxygen and fuels are used as propellants for space rockets.
Test for oxygen
When a glowing splinter is interted into the jar containing the unkown gas, if the gas is oxygen, the
splinter will be rekindled.
Assignment
Dinitrogen (I) oxide behaves like oxygen when brought close to glowing splinter. Highlight the
differences between oxygen and dinitrogen (I) oxide.
Tutorial questions
1. State the steps involved in the industrial preparation of oxygen
2. Give any three uses of oxygen
3. With two examples each, briefly describe types of oxides
4. Give four physical properties of oxygen
5. with the aid of balanced equation, Show the reaction of oxygen with a metal and a non-metal
6. Describe one way by which oxygen can be produced in the laboratory

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WEEK 6
TOPIC: HALOGENS
The halogens are the group VII elements. The family comprises of fluorine, chlorine, bromine, iodine and
astatine. Each member of the family contains 7 electrons at the valence shell. Halogens are the most
reactive non-metals; hence, they don’t occur freely in nature but combine with metals to form salts.
Fluorine is the most reactive element in the family and is in many ways unique. Bromine and iodine are
chemically very similar to chlorine. Astatine is a radioactive element and has been made artificially. It
does not occur naturally.
Electronic configuration and properties of halogen
The electronic configuration of halogens is one electron short of the noble gas structure. Each atom of
the elements in the group complete its octet structure by either:;
- Gaining one electron usually from group I and II to form a univalent negative ion, e.g. F-, Cl-, Br-.
Or
- Sharing a pair of electrons in a single covalent with another atom having a fairly similarelectronegative
value as in gaseous chlorine; Cl – Cl, and hydrogen chloride; H – Cl.
The electronic configurations of halogens are:
9F – 2,7
17Cl – 2,8,7
35Br – 2,8,18,7
53I – 2,8,18,18,7
85At – 2,8,18,32,18,7
General properties of halogens
1. They are all diatomic molecules; hence they have low melting and boiling points and are soluble
in covalent non-polar liquids.
2. At room temperature, fluorine and chlorine are gases, bromine is liquid and iodine is solid. The
boiling point increases down the group.
3. They are coloured with typical penetrating odours. The colours deepen down the group. Fluorine
is pale yellow, chlorine is greenish-yellow, bromine is reddish-brown and iodine is purple balck.
4. Their reactivity decrease down the group. The reactivity series such as volatility, solubility,
electronegativity, oxidizing ability and tendency to enter into chemical reaction decrease down
the group. This gradation in properties is due to the increasing complexity of the atoms as their
atomic numbers increase from fluorine to iodine.
5. All halogens dissolve to some extent in water. Fluorine reacts vigorously with water to produce
oxygen and hydrogen fluoride.
6. They are all strong oxidizing agents. Fluorine oxidizes water to peroxide. Chlorine reacts slowly
with water to give oxochlorate (I) acid, (HClO). The oxochlorate (I) acid decomposes to give
hydrochloric acid and oxygen.
2HClO(aq) 2HCl(aq) + O2(g)
7. They all combine readily with most metals (except gold, platinum and titanium) and non-metals
(except oxygen, carbon and nitrogen) to form ionic and covalent compounds respectively. These
compounds contain halide ion, X- in which they have oxidation state of -1. E.g.
2Na(s) + X2 2NaX(s)
2P(s) + 3X2 2PX3(s)
Note: under certain conditions, the less reactive halogens react more vigorously than chlorine.
For example, bromine is capable of corroding gold because it is a liquid and has more
concentration than chlorine which is a gas.
1. They combine with hydrogen to form gaseous covalent compounds of formula HX. The halide ionhas an
oxidation state of -1.
2. They react with silver to form silver halide. Only silver fluoride is soluble. Silver chloride is white,

7
silver bromide is pale yellow and silver iodide is bright yellow. This characteristic can be used totest for
halides.
3. They all react with sodium hydroxide to give a mixture of halide salt and oxochlorate (I) salts e.g.
Cl2(g) + 2NaOH(aq) NaCl(aq) + NaClO(aq) + H2O(l)
4. More reactive halogen displaces (displacement reaction) less reactive halogens from their salts.
This is a typical redox reaction e.g. Br2(aq) + 2KI(aq) 2KBr(aq) + I2(aq)
CHLORINE AND ITS COMPOUNDS
Chlorine is most important halogen. It does not occur freely in nature but in combined state as
chlorides, mostly sodium chloride.
Laboratory preparation of chlorine
Chlorine is usually prepared by the oxidation of concentrated hydrochloric acid with a strong oxidizing
agent such as manganese (IV) oxide – MnO2, potassium tetraoxomanganate (VII)-KMnO4 or lead (IV)
oxide – PbO2.
- Using MnO2: heat a mixture of MnO2 and conc. HCl . the acid is oxidize to liberate chlorine.
MnO2(s) + 4HCl(aq) heat MnCl2(aq) + 2H2O(l) + Cl2(g)
- Using KMnO4 – heat is not required. The conc. HCl is oxidized upon addition of KMnO4.
2KMnO4(aq) + 16HCl(aq) 2MnCl2(aq) + 2KCl(aq) + 8H2O(l) + 5Cl2(g)

Industrial preparation of chlorine

Chlorine is manufactured industrially by the electrolysis of (a) brine (ii) the molten chlorides of sodium,
magnesium or calcium. The chlorine is then liquefied and stored under pressure in steel cylinder.
Physical properties of chlorine
1. It is a greenish – yellow gas with an unpleasant choking smell.
2. It is moderately soluble in water
3. It is about 2.5 times denser than air
4. It can easily be liquefied under a pressure of about 6atm.
5. It is poisonous
Chemical properties of chlorine
- Displacement of other halogens (except fluorine) – chlorine displaces other halogens below it in
the Periodic Table from their respective acids and salts e.g
Cl2(g) + 2NaBr(aq) 2NaCl(aq) + Br2(l)
Cl2(g) + 2HI(aq) 2HCl(aq) + I2(s)
- Direct combination with other elements:
(i) Metals react readily with chlorine especially when heated to form the corresponding chloride e.g.
2Fe(s) + 3Cl2(g) 2FeCl3(s)
Note: where a metals forms more than one chloride, the higher chloride is usually formed due to the
oxidative nature of chlorine. For example, Iron(III) chloride and not iron (II) chloride is formed in the
reaction above.
(ii) All non-metals (except the noble gases, oxygen, nitrogen and carbon) burn in chlorine to produce the
corresponding chlorides e.g. hydrogen and chlorine combine explosively in bright sunlight to produce
hydrogen chloride. The reaction is slower in diffuse light.

8
H2(g) + Cl2(g) 2HCl(g)
- Reaction with hydrogen – chlorine reacts readily with molecular hydrogen as well as compounds
containing hydrogen to form hydrogen chloride e.g.
(i) with hydrocarbons – chlorine removes hydrogen from burning hydrocarbon like wax, candle, petrol or
methane to form hydrogen chloride fumes and soot. Also, a filter paper saturated with turpentine (C 10H16)
will rapidly catch fire in a jet of chlorine to form soot and misty fumes of hydrogen chloride gas.
C10H16(l) + 8Cl2(g) 10C(s) + 16HCl(g)
Under controlled condition, substitution reaction occurs. In this reaction, chlorine reacts with
saturated hydrocarbons to produce chlorinated hydrocarbons and hydrogen chloride e.g.
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)
Chloromethane
CH3Cl(g) + Cl2(g) CH2Cl2(g) + HCl(g)
Dichloromethane
CH2Cl2(g) + Cl2(g) CHCl3(g) + HCl(g)
Trichloromethane
CHCl3(g) + Cl2(g) CCl4(g) + HCl(g)
Tetrachloromethane
(ii) with ammonia – chlorine reacts with ammonia to form nitrogen and hydrogen chloride. The
hydrogen chloride then reacts with excess ammonia to form ammonium chloride.
2NH3(g) + 3Cl2(g) N2(g) + 6HCl(g)
HCl(g) + NH3(g) NH4Cl(s)
(iii) with hydrogen sulphide – when hydrogen sulphide and chlorine are mixed, a yellow deposit
of sulphur is formed as a result of oxidation of sulphide by chlorine.
H2S(g) + Cl2(g) 2HCl(g) + S(l)
(iv) with water – chlorine water (formed by bubbling chlorine through water) gives off oxygen
when exposed to sunlight. This is due to the formation of oxochlorate (I) acid which decomposes
slowly to yield hydrogen chloride and oxygen.
Cl2(g) + H2O(l) HCl(g) + HOCl(aq)
2HOCl(aq)sunlight 2HCl(aq) + O2(g)

- As an oxidizing agent – chlorine is a powerful oxidizing agent because of: (i) its ability to remove
hydrogen (ii) its readiness to accept electron from reducing agents to from chloride ions e.g.
(i) 2FeCl2(aq) + Cl2(g) 2FeCl3(aq)
Green yellow
(ii) when bubbled through a freshly prepared solution of H2SO3, chlorine oxidizes the
trioxosulphate (IV) ion to tetraoxosulphate (VI) ion.
H2SO3(aq) + H2O(l) + Cl2(g) H2SO4(aq) + 2HCl(aq)
- As a bleaching agent – in the presence of water, chlorine bleaches most dyes and inks except
those containing carbon like printer’s ink. The bleaching action of chlorine is due to its ability to
react with water to form oxochlorate (I) acid. The oxochlorate (I) acid is unstable and
decomposes to release oxygen which oxidizes the dye to form a colourless compound.
HOCl(aq) HCl(aq) + [O]
Dye + [O] (dye + O)
Coloured colourless
- Reaction with alkali

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(i) with dilute alkali – when chlorine is bubbled through a cold dilute solution of sodium
hydroxide, a pale – yellowish mixture of the oxochlorate (I) and chloride of the metal is formed
e.g. Cl2(g) + 2NaOH(aq) NaOCl(aq) + NaCl(aq) + H2O(l)
Sodium oxochlorate (I)
Bleaching powder is prepared by bubbling chlorine through a freshly prepared solution of slaked
lime; Cl2(g) + Ca(OH)2(s) CaOCl2. H2O(s)
Slaked lime bleaching powder
(ii) with conc. Alkali solution – if chlorine is bubbled through a hot conc. Solution of sodium
hydroxide, a mixture of trioxochlorate (V) and chloride of the metal is formed.
3Cl2(g) + 6NaOH(aq) NaClO3(aq) + 5NaCl(aq)
Sodium trioxochlorate (V)
Test for chlorine
1. Drop a piece of damp blue litmus paper into the gas jar of the unknown gas. If the litmus paper
turns pink and then becomes bleached, the gas is chlorine.
2. Drop a piece of damp starch-iodide paper into the unknown gas jar. If the paper turns dark blue,
then the gas is chlorine.
Uses of chlorine
- As a powerful germicide, it is used in the sterilization of water
- It is used as a bleaching agent for cotton, linen and wood-pulp. It is too strong for bleaching
animal fibre.
- It is used in the manufacture of;
Important organic solvents like CHCl3, CCl4 etc
Polyvinyl chloride (PVC) a widely used plastic
Hydrochloric acid
KClO3 used for making matches and in fireworks and NaClO3 which is a weed killer.
Bleaching powder and NaClO used in dye works and laundry.
Domestic antiseptic e.g. acidified NaClO
HYDROGEN CHLORIDE
Hydrogen chloride is a hydride of chlorine. It exists as a gas at s.t.p. and dissolves in water to form
hydrochloric acid. It was first prepared by priestly in 1772.
Laboratory preparation of hydrogen chloride
Hydrogen chloride is prepared in the laboratory by the action of concentrated tetraoxosulphate (VI) acid
on sodium chloride. The gas is dried by passing it through concentrated H 2SO4 and is collected bydownward
delivery.
2NaCl(s) + H2SO4(aq) Na2SO4 + 2HCl(g)

Industrial preparation of hydrogen chloride

It is prepared industrially be the direct combination of hydrogen and chlorine gases obtained from the
electrolysis of brine.
H2(g) + Cl2(g) 2HCl(g)
Physical properties of hydrogen chloride
- It is colourless with a sharp irritating smell
- It is slightly denser than air
- It turns moist blue litmus paper red (property of an acidic oxide)

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- It is very soluble in water forming an aqueous solution of hydrochloric acid
- It fumes strongly in moist air forming droplets of hydrochloric acid
- It does not burn or support combustion
- Dry hydrogen chloride dissolves readily in non-polar solvent like chloroform and toluene, but
does not ionize as it does in polar solvent.
Chemical properties of hydrogen chloride
1. Reaction with ammonia – hydrogen chloride gas reacts with ammonia gas to form a dense white
fumes of solid ammonium chloride.
HCl(g) + NH3(g) NH4Cl(s)
2. Reaction with metals – hydrogen chloride gas on heating reacts with many metals, forming the
corresponding chlorides and hydrogen. If the metal can form two chlorides, the lower chloride is
formed.
Zn(s) + 2HCl(g) ZnCl2(s) + H2(g)
Fe(s) + 2HCl(g) FeCl2(s) + H2(g)
Assignment
Describe an experiment to show that hydrogen chloride gas in readily soluble in water. Name another
gas which shows this property.
Tutorial question
- Name any five gases that are collected by downward delivery
- Name any three gases that are collected by upward delivery
- Draw and label the laboratory set up for the preparation of chlorine gas
- Show the reaction of chlorine with saturated hydrocarbon to produce chlorinated hydrocarbon.
What condition is required for the reaction to take place? What type of reaction is it?
- With the aid of balanced equations, show the reaction of chlorine with (i) dilute alkali (ii) conc.
Alkali solution
- State five physical properties of hydrogen chloride
- State what happens when chlorine reacts with iron (II) chloride
- State five general properties of halogens
- How do we test for chlorine
- State three uses of chlorine

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WEEK 7
TOPIC: NITROGEN AND ITS COMPOUNDS
Nitrogen forms about 78% by volume of the atmosphere. It can be found in combined form in trioxonitrate
(V) of sodium and calcium. It can also be found in organic matters like proteins, urea and the vitamin B
compounds.
Laboratory preparation of nitrogen
- From air: nitrogen can be obtained from air by removing the other constituents. The CO2 and O2
can be removed by passing the air through caustic soda and heated copper turning respectively.
The nitrogen obtained by this method contains about 1% by volume of rare gases as impurities
and is denser than pure nitrogen.

- From ammonium dioxonitrate (III) – NH4NO2: thermal decomposition of NH4NO2 yields pure nitrogen. The
NH4NO2 should not be heated directly because it is unstable and decomposes exothermically. Hence, a
mixture of NaNO2 and NH4Cl in a ratio of 7:5 is heated to yield NH4NO2which in turn decomposes to form
nitrogen and steam.
NaNO2(aq) + NH4Cl(aq) NH4NO2(aq) + NaCl(aq)
NH4NO2(aq) N2(g) + 2H2O(l)

- From ammonium heptaoxodichromate (VI): when (NH4)2Cr2O7 is heated, it decomposes to yield

nitrogen. (NH4)2Cr2O7(s) N2(g) + Cr2O3(s) + 4H2O(l)
- From ammonia: when ammonia is oxidized by hot copper (II) oxide, nitrogen is liberated.
2NH3(g) + 3CuO(s) 3Cu(s) + 3H2O(g) + N2(g)
- From dinitrogen (I) oxide: when N2O is paased over red hot copper, the gas is reduced to
nitrogen. N2O(g) + Cu(s) CuO(s) + N2(g)
Industrial preparation
In the industries, nitrogen is prepared by the fractional distillation of liquid air. Carbon (IV) oxide is first
12
removed from air, by passing the air through caustic soda, before liquefaction. The liquid air (without
CO2) is subjected to successive compression and cooling processes. During distillation, nitrogen gas first
evolves at -1960C (at s.t.p) and is separated from oxygen which distils at -1830C (at s.t.p). the nitrogen is
stored in steel cylinders and sold as liquid nitrogen or as the compressed gas.
Physical properties of nitrogen
1. It is a colourless, odourless and tasteless gas
2. Pure nitrogen is slightly lighter than air
3. It is only slightly soluble in water
4. It has a boiling point of -1960C and melting point of -2100C.
Chemical properties of nitrogen
Nitrogen is a Group V element which forms covalent bonds in it compounds. It can also form ionic bonds
with Group I and II elements by accepting 3 electrons to form nitride ion; N3-. The oxidation states vary
from -3 to +5 in its various compounds. Nitrogen gas is unreactive under ordinary conditions because of
the high bond energy of the triple bond (N≡N) in its atoms. However, at high temperature and pressure
nitrogen combines directly with hydrogen, oxygen and certain metals.
1. Reaction with metals: Nitrogen combines directly with very electropositive metals to form
nitrides e.g
3Mg(s) + N2(g) Mg3N2(s)
Mg3N2(s) + 6H2O(l)warm 3Mg(OH)2(aq) + 2NH3(g)
2. Reaction with non-metals: nitrogen combines reversibly with hydrogen to form ammonia. With
oxygen, it combines directly at very high temperature of about 20000C or in the presence of a
high voltage electric spark to form small amount of nitrogen (II) oxide. This reaction occurs in the
atmosphere during lightning flashes.
N2(g) + O2(g) 2NO(g)
Uses of nitrogen
- It is used in the manufacturing of ammonia, cyanide, cyanomide, and carbamide (an importantfertilizer)
- Liquid nitrogen is used as cooling agent
- Because of its inert nature, it is used as a carrier gas in gas chromatography, provision of inertcondition for
certain industrial processes that involve easily oxidizable chemicals e.g. themanufacturing of transistors and
annealing of metals.
- It is used as preservative to prevent rancidity in packaged foods

COMPOUNDS OF NITROGEN
AMMONIA
Ammonia is a very important chemical. It is a hydride of nitrogen.
Laboratory preparation of ammonia
Ammonia is prepared in the laboratory by heating any ammonium salt with a non-volatile base.
Ammonium chloride and calcium hydroxide are usually employed because calcium hydroxide is cheap
and not deliquescent like sodium hydroxide and potassium hydroxide. The two reactants must be
properly grounded to provide maximum surface area for the reaction.
Ca(OH)2(s) + 2NH4Cl(s) CaCl2(s) + 2H2O(l) + 2NH3(g)
The suitable drying agent for ammonia is quicklime (CaO). Silica gel may also be used.
Laboratory preparation of ammonia

13
Industrial preparation of ammonia
The industrial process for the production of ammonia is called Haber process. It involves mixing nitrogen
and hydrogen in the volume ration 1:3 and passing the mixture:
- Over finely divided iron as catalyst
- At a temperature of about 4500C and
- A pressure of about 200 atm.
The yield of ammonia is about 15%. The Ammonia is liquefied by cooling while the unused gases are
recirculated
for further production.
N2(g) + 3H2(g) 2NH3(g)
An ammonia molecule has pyramidal shape. The presence of lone pair of electron and the different
electronegativity values of nitrogen and hydrogen makes ammonia molecule polar. Because of this,
hydrogen bonds occur readily between ammonia molecules and between ammonia and water
molecules.
Physical properties of ammonia
1. It is a colourless gas with choking smell
2. It is poisonous when in large quantity because of its effects on respiratory muscles.
3. It is an alkaline gas
4. It is about 1.7 times less dense than air
5. It is a very soluble gas. About 1200 volumes of ammonia dissolves in 1 volume of water at s.t.p.
This is due to the readiness with which it forms hydrogen bonds with water to give aqueous ammonia –
NH3.H2O. The aqueous ammonia ionizes slightly to give ammonium ion and hydroxylion. The hydroxyl ion
gives aqueous ammonia its weak alkaline property.
Chemical properties of ammonia
- Ammonia burns readily in oxygen, but not in air, with a greenish yellow flame to form watervapour and
nitrogen;
4NH3(g) + 3O2(g) 6H2O(g) + 2N2(g)
In the presence of heated platinum catalyst however, ammonia reacts with air to produce
nitrogen (II) oxide;
4NH3(g) + 5O2(g)platinum n4NO(g) + 6H2O(l)
- As a reducing agent
(i) It reduces heated copper (II) oxdie to metallic copper
2CuO(s) + 2NH3(g) 3Cu(s) + 3H2O(l) + N2(g)
(ii) It reduces chlorine to hydrogen chloride and nitrogen. The hydrogen chloride then reacts withexcess
ammonia to produce dense white fume of ammonium chloride.
2NH3(g) + 3Cl2(g) 6HCl(g) + N2(g)
6NH3(g) + 6HCl(g) 6NH4Cl(s)
Overall reaction ; 8NH3(g) + 3Cl2(g) 6NH4Cl(s) + N2(g)
The ammonia must be supplied in excess. If however, chlorine is in excess, nitrogen (II) chloride – NCl 3, an
explosive and oily liquid will be formed.
NH3(g) + 3Cl2(g) NCl3(l) + 3HCl(g)
- Reaction with carbon(IV) oxide: at about 1500C and 150 atm, ammonia reacts with carbon (IV)
oxide to produce urea, an important organic compound.
2NH3(g) + CO2(g) (NH2)2CO(s) + H2O(l)
- Thermal decomposition; at temperature above 5000C or during prolong sparkling, ammoniadecomposes to
form nitrogen and hydrogen
- As a base: ammonia is a weak base because it can accept proton to form ammonium ion. It
reacts with acids to form ammonium salt.
NH3(g) + H+ (aq) NH4+(aq)
2NH3(g) + H2SO4(aq) (NH4)2SO4(s)
- As a precipitating agent: aqueous ammonia precipitates the insoluble hydroxides of metals fromthe
solution of their salts. The following are the common insoluble hydroxides.
Pb2+(aq) + 2OH-(aq) Pb(OH)2(s) – white ppt
14
Zn2+(aq) + 2OH-(aq) Zn(OH)2(s) – white gelatinous ppt
Fe3+(aq) + 3OH-(aq) Fe(OH)3(s) - reddish brown ppt
Cu2+(aq) + 2OH-(aq) Cu(OH)2(s) – blue ppt
Some of these hydroxide like Cu(OH)2 and Zn(OH)2 dissolve in excess ammonia to form complex ions.
The complex ion formation is used as confirmatory test for copper and zinc in qualitative analysis.
Cu(OH)2(s) + 4NH3(aq) Cu(NH3)42+(aq) + 2OH-(aq)
Deep blue solution
Zn(OH)2(s) + 4NH3(aq) Zn(NH3)2+ + 2OH-(aq)
Colourless solution
Test for ammonia
1. Action of litmus paper – hold a damp red litmus paper into the jar containing the unknown gas
with choking smell. If the litmus paper turns blue, then the gas is ammonia.
2. Action with hydrochloric acid – dip a glass rod in con. HCl and then insert it in the gas jar
containing the unknown gas, white fumes are formed if the gas is ammonia.
Uses of ammonia
- It is used for softening temporary hard water
- Aqueous ammonia is used in laundry as solvent for removing grease and oil stains
- Aqueous ammonia is used as a refrigerant, although it is being replaced by less toxic compounds
- It is used in the manufacture of HNO3 and Na2CO3.
- It is used in the manufacturing nitrogenous fertilizers like (NH4)2SO4, NH4NO3, (NH4)3PO4 and
carbamide.
Assignment
Briefly discuss the nitrogen cycle
Tutorial questions
1. State the test for ammonia
2. Describe the preparation of nitrogen from air
3. State three uses of ammonia
4. Describe any three chemical properties of ammonia
5. Explain what happens when aqueous ammonia is added in excess to a solution of copper(II) salt.

WEEK 8
TOPIC: NITROGEN AND ITS COMPOUNDS
Oxides of Nitrogen
Oxides are known for every oxidation state of nitrogen from +1 to +5. These are Dinitrogen(i)oxide, N 2O,
nitrogen(ii)oxide NO, nitrogen(iii)oxide, N2O3, nitrogen(iv)oxide, NO2 and nitrogen(v)oxide, N2O5.
Assignment
Give the preparation (Laboratory and industry), properties (physical and chemical), uses and test of all the
five oxides of nitrogen.
Trioxonitrate (V) acid – HNO3
It is an important acid used in the laboratory and in the industries. It was previously known as aquafortis;
meaning strong water.
Laboratory preparation of HNO3
HNO3 can be prepared from any trioxonitrate(V) salt. KNO3 and NaNO3 are usually used because theyare
cheap. When these trioxonitarte (V) salts are reacted with conc. H2SO4, HNO3( a more volatile acid)is
displaced.
KNO3(aq) + H2SO4(aq) KHSO4(aq) + HNO3(g)
NaNO3(aq) + H2SO4(aq) NaHSO4(aq) + HNO3(g)

15
Laboratory preparation of HNO3

Physical properties of HNO3

- It is a fuming liquid with a sharp choking smell. The pure HNO3 is colourless but turns yellowish after
sometimes due to the decomposition of some of the acid to yield NO2 which then dissolves in it.
- Pure HNO3 is miscible with water in all proportions and forms a constant boiling mixture with it at 121 0C.
this mixture consisting of about 68% HNO3 is the ordinary conc. HNO3 found in the laboratory. Pure HNO3
containing 98% acid is known as fuming HNO3.
- Pure and ordinary conc. HNO3 are corrosive and must be handled with care.
Chemical properties of HNO3.
1. As an acid
(i) it neutralizes bases and alkalis to form metallic trioxonitrate (V) and water
NaOH(aq) + HNO3(aq) NaNO3(aq) + H2O(l)
CaO(s) + 2HNO3(aq) Ca(NO3)2(aq) + H2O(l)
(ii) it reacts with metallic trioxocarboantes(IV) to liberate carbon(IV) oxide.
CaCO3(s) + 2HNO3(aq) Ca(NO3)2(aq) + H2O(l) + CO2(g)
(iii) very dilute HNO3 (about 1%) react with calcium, magnesium or manganese to liberate hydrogen. Conc.
HNO3 does not liberate hydrogen gas when reacted with metals, unlike other acids, because the hydrogen
gas formed is immediately oxidized to water by the HNO3.
Mg(s) + 2HNO3(aq) Mg(NO3)2 + H2(g)

2. As an oxidizing agent:
HNO3 is a strong oxidizing agent. it can undergo reduction in many ways to form various products like NO 2,
HNO2, NO, N2O, N2, N2OH, N2H4 and NH4+, depending on the concentration of the acid, the strength of the
reducing agent and the temperature.
When dilute HNO3 acts as the oxidizing agent, the trioxonitrate (V) ion, NO 3-
- is reduced to NO
e.g. NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l)
When conc. HNO3 is the oxidizing agent, the NO3
- is reduced to NO2
NO3-(aq) + 2H+(aq) + e- NO2(g) + H2O(l)
With non-metals: Hot conc. HNO3 oxidizes non-metals to their highest oxides which may thenreact with
water to form the corresponding acids. At the same time, the acid itself is reduce tonitrogen (IV) oxide;
e.g C(s) + 4HNO3(aq)heat CO2(g) + H2O(l) + 4NO2(g)
S(s) + 6HNO3(aq)heat H2SO4(aq) + 2H2O(l) + 6NO2(g)
With metals:
(i) metals which are mild reducing agents like Cu, Pb, Hg and Ag when reacted with pure HNO 3are oxidized
ton their trioxonitrates (V) while the HNO3 itself is reduced to NO2. However, with moderately conc. HNO3
(about 50%) these metals still react the same way but the HNO3 isreduced to NO e.g.
Cu(s) + 4HNO3(aq) Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g)
Pure
3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 4H2O(l) + 2NO(g)

16
(ii) Aluminium and iron do not react with the conc. HNO3. This may be due to the formation of a surface
coating of oxide which is passive and stops any further reaction by the acid. Conc. HNO 3 is thus usually
transported in containers lined with aluminium or iron.
(iii) magnesium, zinc and iron reacts with dilute HNO3 to form the corresponding metallic trioxonitrates(V)
and ammonium trioxonitrate (V) or nitrogen (I) oxide.
4Zn(s) + 10HNO(aq) 4Zn(NO3)2(aq) + 3H2O(l) + NH4NO3(aq)
(iv) Tin reacts with conc. HNO3 to form a hydrated oxide instead of a trioxonitrate (V)
Sn(s) + 4HNO3(aq) SnO2.H2O(s) + H2O(l) + 4NO3(g)
(v) Gold and platinum are not attacked by HNO3 at all.
With reducing agents
(i) HNO3 oxidizes H2S to sulphur, some of which may be further oxidized to H2SO4. The HNO3 is itself reduced
to NO2.
H2S(g) + 2HNO3(aq) S(s) + 2H2O(l) + 2NO2(g)
(ii) iron (II) salts are oxidized to iron (III) salts by HNO3. The acid is then reduced to NO, which on
exposure to air is converted to NO2.
6Fe2+(aq) + 8H+(aq) + 2NO3-(aq) 6Fe3+(aq) + 4H2O(l) + 2NO(g)
3. Decomposition
HNO3 decomposes slowly at room temperature (especially in the presence of sunlight) and rapidly when
heated to yield NO2 and O2.
4. Nitration reactions
HNO3 dissociates in the presence of conc. H2SO4 to form the nitryl cation (nitronium ion), NO2+.The nitronium
ion can replace the hydrogen ion from many compounds like benzene, methylbenzene and phenol. The
process is called nitration and is very important in the industries.
C6H6(l) + HNO3(aq) C6H5NO2(l) + H2O(l)
Nitrobenzene
Uses of HNO3.
- It is used as an acid, oxidizing agent and nitrating agent in the laboratory.
- It is used as a rocket fuel
- It is used as an oxidizing agent in the production of important polymers like nylon and terylene.
- A mixture of hydrochloric acid and HNO3 in ratio 3:1 (known as aqua regia) is used as a solvent for gold and
platinum.
- It is used as an important starting material in the production of many trioxonitrates (V) and organic nitro-
compounds which are used for the production of fertilizers, dyes, drugs and explosives e.g. methyl-2,4,6-
trinitrobenzene – TNT)
TRIOXONITRATES (V)
Trioxonitrates (V) can be prepared by any of the general methods used for preparation of salts e.g.
- Neutralization of HNO3 with appropriate alkali
- Action of HNO3 on metals, a metal oxide or a trioxocarbonate (IV) Precipitation method cannot be used for
the preparation of trioxonitrates(V) because they are allsoluble. Crystallization is the only suitable method
for recovering the trioxonitrate (V) salt from theaqueous solution because they decompose easily on
heating.
Action of heat on trioxonitrates(V)
All trioxonitrate(V) salts decompose on heating but the product depend on the position of the metal in
the electrochemical series. Below are the products of the decomposition of trioxonitrates(V).
Metal Decomposition of trioxonitrate (V)
K
Na
The Trioxonitrates (V) decompose to dioxonitrate (III) and oxygen
2KNO3(s) 2KNO2(s) + O2(g)
Ca
Mg
Zn
Pb

17
H Cu
The trioxonitrates (V) decompose to give the metallic oxide, oxygen and brown fumes of
nitrogen (IV) oxide e.g.
2Zn(NO3)2(s) 2ZnO(s) + O2(g) + NO2(g)
Hg
Ag
Au
The trioxonitrate(V) decompose to give the metal, oxygen and brown fumes of nitrogen (IV)oxide e.g.
2AgNO3(s) 2Ag(s) + O2(g) + 2NO2(g)
Unlike the metallic trioxonitrate (V), ammonium trioxonitrate (V) decomposes on heating to
producenitrogen (I) oxide and water.
NH4NO3(s) N2O(g) + 2H2O(l)
Action of H2SO4
All trioxonitrate (V) salts liberate HNO3 when heated with conc. H2SO4.
NO3-(aq) + H2SO4(aq) HSO4-(aq) + HNO3(aq)
Formation of brown ring
When conc. H2SO4 is added slowly down the side of a test tube containing an aqueous solution of a
trioxonitrate(V) and FeSO4, the acid sinks to the bottom and two layers are formed. A brown ring is formed
at the junction of the two layers. This formation of brown ring can be used as a test for trioxonitrates (V) but
it is unreliable because iodide and bromides too give coloured rings. Metallic radicals which form insoluble
tetraoxosulphate (VI) also interfere with the test.
Test for trioxonitrate (V)
- With H2SO4: warm the unknown solid with a little conc. H2SO4 in a test tube. If trioxonitrate (V) is present,
some HNO3 will be condensed as oily drops on the upper part of the tube. On further heating, the acid
decomposes to yield brown fumes of NO2.
H2SO4(aq) + NO3-(aq) HNO3(l) + HSO4-(aq)
4HNO3(l) 4NO2(g) + O2(g) + 2H2O(l)
- With copper turnings: warm the mixture of the unknown solid and copper turnings with some
conc. H2SO4. If a trioxonitrate (V) is present, reddish brown fumes of NO2 will be formed.
H2SO4(aq) + NO3-(aq) HNO3(aq) + HSO4-(aq)
Cu(s) + 4HNO3(aq) Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
Tutorial questions
1. How do we test for trioxonitrates (V) in the laboratory?
2. With the aid of balanced chemical reactions show the thermal decomposition of;
(i) sodium trioxonitrate (V)
(ii) copper (II) trioxonitrate (V) and
(iii) Silver trioxonitrate (V)
3. State three uses of trioxonitrate (V) acid
4. Briefly describe the acidic properties of trioxonitrate (V) acid
5. How is HNO3 produced in the laboratory?

18
WEEK: 9
TOPIC: SULPHUR AND ITS COMOUNDS
Sulphur is a non-metal in the same family (Group VI) with oxygen in the Periodic Table. Sulphur is
different from oxygen in that:
- it is a solid at room temperature
- it shows the valencies of -2, +4 and +6
The electronic configuration of sulphur is 1S2,2S2,2P6, 3S2,3P4 (2,8,6). It gains two electrons from a metallic
element to form an ionic bond or shares two pairs of electrons with other non-metallic element to form
covalent bond.
Allotropes of sulphur
Allotropy is a phenomenon whereby an element occurs in two or more free forms in the same physical
state. The different forms are called isotopes. The main allotropes of sulphur are:
- Rhombic sulphur(α sulphur)
- Monoclinic or prismatic sulphur (β sulphur)
- Amorphous sulphur (δ sulphur) and
- Plastic sulphur
Rhombic sulphur
It is the only stable allotrope of sulphur at temperature below 960C. They are bright yellow and
octahedral crystals. They are made up of S8 molecules. Each S8 molecule consists of a ring of 8 atoms.
Rhombic sulphur is prepared by allowing a saturated solution of sulphur in carbon (IV) sulphide to
evaporate slowly. The octahedral structure will gradually be deposited. The preparation is done in the
fume cupboard because of the poisonous and highly inflammable nature of carbon (IV) sulphide.
Monoclinic sulphur
It is the only stable allotrope at temperature between 960C and 1190C. The crystals are long, thin and
needle-shaped. They consist of S8 molecules. At room temperature, they slowly revert to rhombic
sulphur crystals. The S8 molecules in monoclinic sulphur are more tightly packed; hence, monoclinic
sulphur is less dense than rhombic sulphur.
To prepare monoclinic sulphur, some powdered sulphur is heated in a crucible till it melts. Add more;
continue heating and stirring at the same time. Repeat the process until the crucible is almost filled with
molten sulphur. Allow the molten sulphur to cool. After sometime, a hard crust will be formed at the
top. Pierce two holes through the crust and pour off the remaining molten sulphur from inside before
removing the crust. Needle-shaped crystals of monoclinic sulphur can be found as deposit on the sides
of the crucible. The relationship between rhombic and monoclinic sulphur is shown below.
Between 960C and 1190C
Rhombic sulphur monoclinic sulphur
Below 960C
Comparison between the two allotropes
Property Rhombic Monoclinic
Colour Bright yellow Amber
Shape Octahedral Needle-shaped
Density (g/cm3) 2.08 1.98
Melting point (0C) 113 119
Stability Below 960C Between 960C and 1190C
Note: 960C is the transition temperature between the two allotropes.

Amorphous sulphur
It has no regular crystalline shape. It is pale yellow in colour and can be prepared in two ways;
- By bubbling hydrogen sulphide through water for a long time and the saturated solution
exposed to the air; 2H2S(g) + O2(g) 2H2O(l) + 3S(s)
- By chemical reaction e.g action of dilute hydrochloric acid on a trioxothiosulphate (VI) solution;
S2O32-(aq) + 2H+(aq) H2O(l) + SO2(g) + S(S)
Plastic sulphur
It is generally not considered to be a true allotrope of sulphur because it is unstable and reverts to
19
rhombic sulphur on standing. It is regarded as a super-cooled form of sulphur. It is prepared by heating
yellow sulphur and pouring it in cold water. It rolls up into yellow ribbons which look like plastic
material. It is soft and elastic and does not dissolve in carbon (IV) sulphide.
Physical properties of sulphur
1. It is a yellow solid which exists in two forms; amorphous and crystalline
2. It is insoluble in water but soluble in carbon (IV) sulphide and methyl benzene (toluene)
3. It is a bad conductor of heat and electricity
4. The density depends on the allotropic form
[Link] melting point is 1190C and the boiling point is 4440C
Chemical properties of sulphur
Sulphur is a Group VI element. It gains two electrons from Group I or II elements to form sulphide ion; S 2-. It
also shares electrons with other non-metals to obtain its octet structure. The oxidation state ranges from -2
to +6. The chemical properties include;
Direct combination with other elements.
- With metals: sulphur combines directly with many metals to form sulphides when heated in the
absence of air. Reactive metals may not require heat if the metals and the sulphur are finely
divided; Fe(s) + S(s) FeS(s)
- With oxygen: when heated in a plentiful supply of air, sulphur burns with a bright blue flame to form SO 2
and a small amount of SO3; O2(g) + S(s) SO2(g)
- With carbon: sulphur combines with coke in an electric furnace to form a colourless liquid known as carbon
(IV) sulphide ( CS2) which vaporizes to form poisonous and highly inflammable fumes;
C(s) + 2S(s) CS2(l)
- With other non-metals: sulphur combines with other non-metals to form various sulphides e.g. disulphide
dichloride; S2Cl2, sulphur hexafluoride SF6.
Reaction with oxidizing acids
When warmed with conc. H2SO4, sulphur is oxidized to form sulphur (IV) oxide; SO2.
2H2SO4(aq) + S(s) 2H2O(l) + 3SO2(g)
With conc. HNO3 when warmed and using bromine as catalyst, sulphur is oxidized to H2SO4.
6HNO3(aq) + S(s) H2SO4(aq) + 6NO2(g) + 2H2O(l)
Action of hot conc. Alkalis:
When sulphur is reacted with hot. Conc. Alkaline solutions, a mixture of sulphides and trioxosulphate
(IV) are formed. In the presence of excess sulphur, a polysulphide and a trioxothiosulphate (VI) are
formed respectively.
3S(s) + 6OH-(aq) 2S2- + SO32- + 3H2O
S2- + nS Sn+1
2- (where n = 1 – 8)
SO32- + S S2O32-

Uses of sulphur
- It is used to produced SO2 for the manufacturing of H2SO4
- It is used in the vulcanization of rubber
- Sulphur and some of its products are used as fungicides and insecticides for spraying crops.
- It is used to manufacture the bleaching agent used in the pulp and paper industry
- It is used for the production of CS2, skin ointments, dyes and as sulphides in the manufacture ofmatches,
fireworks and gunpowder.
HYDROGEN SULPHIDE
It occurs naturally in volcanic gases, sulphur springs, coal gas and gases formed during the decay of
organic matter containing sulphur.
Preparation
Both in the laboratory and commercially, H2S is produced by the action of a dilute acid on a metallicsulphide
e.g.
2HCl(aq) + FeS(s) FeCl2(aq) + H2S(g)

20
Ionically; 2H+(aq) + FeS(s) Fe2+(aq) + H2S(g)
The gas is easily liquefied and stored in steel cylinder for sale.

Physical properties of H2S

- It is a colourless gas with a repulsive smell like that of a rotten egg.
- It is very poisonous
- It is about 1.18 times denser than air
- It is moderately soluble in water to form a very weak acidic solution
- It burns with a pale blue flame.
Chemical properties
As an acid:
When H2S dissolves in water, it ionizes slightly to form a weak, dibasic acid;
H2S(g) + H2O(l) H3O+(aq) + HS-(aq)
-
HS (aq) + H2O(l) H3O+(aq) + S2-(aq)
It reacts with alkali to produce normal salt and water but when H2S is in excess, an acidic salt will
beproduced.
2NaOH(aq) + H2S(g) Na2S(aq) + 2H2O(l)
NaOH(aq) + H2S(g) NaHS (aq)+ H2O(l)
Excess acid salt
As a precipitating agent
When H2S is bubbled through the solution of the salts of some metals, coloured sulphides are precipitated
e.g.
ZnSO4(aq) + H2S(g) ZnS(s) + H2SO4(aq)
White
Pb(CH3COO)2(aq) + H2S(g) PbS(s) + 2CH3COOH(aq)
Black
Reaction with oxygen
Although it doesn’t support combustion, H2S burns in a plentiful supply of air with a bright blue flame to
produce SO2. With limited supply of oxygen, a deposit of sulphur may be formed.
2H2S(g) + 3O2(g) 2H2O(l) + 2SO2(g)
Excess supply
2H2S(g) + O2(g) 2H2O(l) + 2S(s)
Limited supply
As a reducing agent
H2S releases 2 electrons to oxidizing agents in a redox reaction. The H2S is itself oxidized to sulphur.
H 2S 2H+ + S2-
S2- S + 2e-
- With acidified KMnO4
2KMnO4(aq) + 3H2SO4(aq) + 5H2S(g) K2SO4(aq) + 2MnSO4(aq) + 8H2O(l) + 5S(s)
Ionically; 2MnO4 (aq) + 6H (aq) + 5H2S(g) 2Mn2+(aq) + 8H2O(l) + 5S(s)
- +

Purple pale pink

- With acidified K2Cr2O7

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K2Cr2O7(aq) + 4H2SO4(aq) + 3H2S(g) K2SO4(aq) + Cr2(SO4)3 (aq) + 7H2O(l) + 3S(s)
Ionically: Cr2O72-(aq) + 8H+(aq) + 3H2S(g) 2Cr3+(aq) + 7H2O(l) + 3S(s)
Orange green
- With halogens:
In the presence of moisture, H2S is oxidized by halogens to sulphur.
Cl2(g) + H2S(g) 2HCl(g) + S(s)
- With FeCl3:
2FeCl3(aq) + H2S(g) 2FeCl2(aq) + 2HCl(aq) + S(s)
Brownish yellow green
- With SO2;
H2S is a stronger reducing agent than SO2. It reduces SO2 to sulphur in the presence of moisture.
SO2(g) + 2H2S(g) 2H2O(l) + 3S(s)
- With oxidizing agents
Oxidizing acids convert hydrogen sulphide to sulphur. Meanwhile, conc. HNO 3 being a verystrong oxidizing
acid converts H2S to H2SO4
H2SO4(aq) + H2S(g) 2H2O(l) + SO2(g) + S(s)
2HNO3(aq) + H2S(g) 2H2O(l) + 2NO2(g) + S(s)
8HNO3(aq) + H2S(g) 4H2O(l) + 8NO2(g) + H2SO4(aq)
Test for H2S
The gas can be suspected by its odour. It smells like rotten egg. To confirm the gas, moisten a piece of filter
paper with Pb(NO3)2 solution and drop it in a gas jar containing the unknown gas. If the gas is H 2S,the paper
will turn black due to the formation of PbS.
Pb(NO3)2(aq) + H2S(g) PbS(s) + 2HNO3(aq)
Note: lead (II) ethanoate also gives the same reaction with H2S.
Uses of H2S
It is used in the analysis of ores and metals. The presence of certain metals is often indicated by its
colour. Also the sulphides of metals have different solubility in acids and alkalis.
SULPHIDES
Almost all sulphides except Na, K and NH4 – sulphides are insoluble in water. Some of the insoluble
sulphides are however soluble in dilute HCl while others are not.
Preparation of sulphides
- Neutralization: the three soluble sulphides are prepared by bubbling H2S through the
corresponding alkalis e.g. 2NaOH(aq) + H2S(g) Na2S(aq) + 2H2O(l)
- By direct combination: FeS and ZnS can be prepared by heating a mixture of the metal and
sulphur e.g. Fe(s) + S(s) FeS(s)
- By precipitation: insoluble sulphides are prepared by bubbling H2S through a solution of the
corresponding salts e.g. SnCl2(aq) + H2S(g) SnS(s) + 2HCl(aq)
Dark brown

Properties of sulphides
Reaction with oxygen
Except mercury (II) sulphide which yields the metallic mercury, most metallic sulphides when heated in
air or oxygen produce the corresponding metallic oxides and sulphur (IV) oxide. This reaction is used for
the extraction of metals from their naturally occurring sulphides.
2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)
HgS(s) + O2(g) Hg(l) + SO2(g)
Reaction with dilute hydrochloric acid
When heated with HCl(aq), most sulphides yield H2S. This reaction is used to test for sulphide. However,
sulphides which are insoluble in dilute hydrochloric acid must first be fused with sodium
trioxocarbonate (IV) before the test is carried out.
PbS(S) + 2HCl(aq) PbCl2(s) + H2S(g)
Uses of sulphides
- FeS is reacted with dilute hydrochloric acid in the kipp’s apparatus to obtain an immediate

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supply of H2S in the lab.
- ZnS is used to coat the inside of television screen as it fluoresces when exposed to light
- Tin (IV) sulphide is used in paints
Tutorial questions
- What is allotropy? List four allotropes of sulphur
- State four physical properties of hydrogen sulphide
- With two balanced chemical equations, show the reducing action of hydrogen sulphide
- State five physical properties of sulphur
- Describe the laboratory test for S2-.

WEEK: 10
TOPIC: SULPHUR AND ITS COMPOUNDS
TRIOXOSULPHATE (IV) ACID – H2SO3
It is an unstable acid formed when SO2 dissolves in water. It is dibasic and decomposes readily to yield SO2
and water.
SO2(g) + H2O(l) H2SO3(aq)
Preparation of H2SO3
It is prepared by adding conc. HCl to Na2SO4 and heating the mixture gently. The SO2 liberated is then
dissolved in water to form H2SO3.
Physical properties
- It is a colourless and unstable acid
- It smells strongly of SO2, which is a product of its decomposition.
- It turn blue litmus paper red.
Chemical properties
1. Action on air: when exposed to air for sometimes, H2SO3 becomes oxidized by the atmospheric oxygen to
H2SO4:
2H2SO3(aq) + O2(g) 2H2SO4(aq)
2. As a reducing agent and bleaching agent: H2SO3 is responsible for all the bleaching and reducing action
of SO2.
3. As an acid: H2SO3 as a weak dibasic acid forms both acid and normal salts with alkalis.
NaOH(aq) + H2SO3(aq) NaHSO3(aq) + H2O(l)
2NaOH(aq) + H2SO3(aq) Na2SO3(aq) + 2H2O(l)
Uses of H2SO3
- It is used for bleaching straw and other fabrics.
- It is used as a germicide

TRIOXOSULPHATES (IV)
These are normal salts formed when SO2 or H2SO3 reacts with excess alkalis e.g.
H2SO3(aq) + 2KOH(aq) K2SO3(aq) + 2H2O(l)
SO2(g) + 2NaOH(aq) Na2SO3(aq) + H2O(l)
Preparation of trioxosulphates (IV)
1. By neutralization: SO2 dissolves in excess KOH and NaOH to produce K2SO3 and Na2SO3 respectively.
H2SO3 also reacts with excess of these alkalis to produce the corresponding salt.
2. By precipitation: when SO2 is bubbled through a solution of metallic salt, the corresponding insoluble
trioxosulphate (IV) are precipitated out e.g.
SO2(g) + H2O(l) + Zn(NO3)2(aq) ZnSO3(aq) + 2HNO3(aq)
Properties of trioxosulphates (IV)
1. Solubility: only the trioxosulphates (IV) of NH4, K, Na and Ca are soluble in water. All other trioxosulphates
(IV) are insoluble.
2. Reaction with acids: they liberate SO2 when heated with conc. Or dilute acids e.g.

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CaSO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + SO2(g)
3. Reaction with air: when exposed to the air, trioxosulphates (IV) are slowly oxidized totetraoxosulphates
(VI). The reaction is more rapid when some other oxidizing agents are used.
4. As a reducing agent: they are good reducing agents when in dilute acidified solution.

Test for trioxosulphates(IV)

- Warm the unknown substance with a dilute acid. If it is trioxosulphate(IV), SO 2 will be evolved.
2H+(aq) + SO32-(aq) SO2(g) + H2O(l)
- Add some Ba(NO3)2 to a solution of the unknown substance. A white precipitate of BaSO3 will be formed. If
the unknown solution is trioxosulphate (IV), the precipitate will dissolve in dilute HNO 3 with the evolution of
SO2.
Ba2+(aq) + SO32- BaSO3(s)
BaSO3(s) + 2HNO3(aq) SO2(g) + Ba(NO3)2(aq)
TETRAOXOSULPHATE (VI) ACID – H2SO4
It is a heavy chemical. Almost all manufacturing processes make use of it directly or indirectly.
Industrial preparation of H2SO4 (contact process)
The steps involved can be summarised as follows;
- SO2 which is obtained by burning sulphur in dry air or by roasting sulphide ore is catalytically combined with
oxygen to form SO3.
S(s) + O2(g) SO2(g)
2SO2(g) + O2(g) 2SO3(g) + heat
Note: SO2 is usually mixed with excess air and passed through an electric chamber to remove the impurities
and dusts that could kill the catalyst. The gaseous mixture is then passed through conc. H 2SO4 to remove
moisture before the gases are delivered into the reaction chamber or contact chamber. TheSO 2 and O2
combine in the contact chamber in the presence of vanadium (V) oxide catalyst at a temperature of 450 0C –
5000C and atmospheric pressure to yield SO3.
- The SO3 is cooled and passed into an absorption chamber where it dissolves in conc. H 2SO4 to produce a
very thick liquid called oleum;
SO3(g) + H2SO4(aq) H2S2O7
Oleum
- The oleum is diluted with calculated amount of water to produce the 98% H 2SO4 used in the labs. Other
desired concentration can also be obtained depending on the amount of water added.
Note: SO3 is not dissolved directly in water because the process would evolve enough heat to cause the acid
solution to boil, thereby producing a mist of acid droplets which would spread throughout the factory.
Contact process at a glance
O2 conc. H2SO4 H2O
S + O2 SO2 SO3 H2S2O7 H2SO4

Physical properties of H2SO4

- Conc. H2SO4 (oil of vitriol) is a colourless, viscous liquid with a density of 1.84gcm-3
- It is very corrosive
- It turn blue litmus paper red
- Conc. H2SO4 has a great affinity for water. Hence, it dissolves readily in water.
- Conc. H2SO4 is hygroscopic
Chemical properties of H2SO4
1. As an acid: the acid properties of dilute H2SO4 is shown in its reaction with metals, bases
andtrioxocarbonates (IV) e.g.
H2SO4(aq) + Zn(s) ZnSO4(aq) + H2(g)
H2SO4(aq) + MgO(s) MgSO4(aq) + H2O(l)
H2SO4(aq) + CuCO3(aq) MgSO4(aq) + H2O(l) + CO2(g)
Note: H2SO4 is a dibasic acid. It can form both acid and normal salts.

24
2. As an oxidizing agent: Hot conc. H2SO4 accept electrons from reducing agents. The oxidation number
of sulphur hence changes from +6 to +4 e.g.
Zn(s) + 2H2SO4(aq) ZnSO4(aq) + 2H2O(l) + SO2(g)
C(s) + 2H2SO4(aq) CO2(g) + 2H2O(l) + 2SO2(g)
H2S(s) + H2SO4(aq) SO2(g) + 2H2O(l) + S(s)
3. As a dehydrating agent: Conc. H2SO4 removes water molecules from compounds like sugar, ethanol,
methanoic acid and ethanedioic acid. This removal of water from compounds is called dehydration
reaction.
C12H22O11(s) - 11H2O(l) 12C
Sucrose conc. H2SO4 sugar charcoal
CH2OH-H2O(l) C2H2(g) CH2OH (l) conc. H2SO4
The dehydration reaction of H2SO4 accounts for:
- The corrosive action of the acid on cloth, paper, wood, skin etc
- Removal of water of crystallization from hydrated salts to produce anhydrous salts e.g.
CuSO4.5H2O 5H2O(l) + CuSO4
conc.H2SO4
Blue white
4. Displacement of other acids from their salts: conc. H2SO4 displaces volatile acids from their salts e.g.
KCl(s) + H2SO4(aq) KHSO4(aq) + HCl(g)
NaNO3(s) + H2SO4(aq) NaHSO4(aq) + HNO3(aq)
The reactions depend solely on the boiling point of the acids. HCl and HNO 3 distil over as gases.
Uses of H2SO4
1. Production of fertilizer; Ca(HSO4)2 and (NH4)2SO4
2. Production of pigments e.g titanium (IV) oxide used in paint and dyes
3. For making cellulose film, natural and artificial fabrics and plastics.
4. Purification of crude oil and manufacturing of artificial silk
5. To clean or pickle metals before electroplating or enamelling
6. Used as drying agent for many gases except alkaline gas (NH3) and reducing gases like H2S
7. Used in the preparation of many important chemical compounds like HCl, HNO 3 etc
TETRAOXOSULPHATES (VI)
They are the normal salts formed when all the H+ in H2SO4 are replaced by metallic metallic or
ammonium ion. Most of them are crystalline and soluble in water. The insoluble ones are CaSO 4, PbSO4,
BaSO4 and Hg2SO4
Laboratory preparation
They are prepared in the laboratory by any of the standard methods used for the preparation of salts
depending on the position of the metallic radical in the electrochemical series and the nature of the
tetraoxosulphate (VI). The table below shows the methods:

Metal Method of preparation of SO4

K
Na
By the action of dil. H2SO4 on the oxides, hydroxides or the trioxocarbonates(IV) of the metale.g.
H2SO4(aq) + CaO(s) CaSO4(aq) + H2O(l)
Ca H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)
Mg
Al
Zn
Fe
By the action of dil. H2SO4 on the metals, their oxides or their trioxocarbonates (IV) aluminium requires the
action of conc. H2SO4 e.g.
H2SO4(aq) + Mg(s) MgSO4(aq) + H2(g)
H2SO4(aq) + ZnO(s) ZnSO4(aq) + H2O(l)

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H2SO4(aq) + FeCO3(s) FeSO4(aq) + CO2(g) + H2O(l)
Pb. By double decomposition e.g.
Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(s) + 2NaNO3(aq)
Cu
Hg
Ag
By the action of hot. Conc. H2SO4 on the metals e.g.
Hg(l) + 2H2SO4(aq) HgSO4(aq) + 2H2O(l) + SO2(g)
2Ag(s) + 2H2SO4(aq) Ag2SO4(aq) + 2H2O(l) + SO2(g)
Properties of tetraoxosulphates(VI)
- Most of them are colourless and crystalline
- The soluble ones form hydrated salts/crystals
- The tetraoxosulphates (VI) of Na, K and Ca are very stable to heat while those of metals lower in
the electrochemical series tend to decompose on heating.
- When the hydrated tetraoxosulphate (VI) of Zn2+, Cu2+ and Fe2+ are heated, they lose their water of
crystallization in stages. Further heating of the anhydrous salts brings about their decomposition into
metallic oxides, sulphur (IV) oxides and trioxosulphates (IV).
Uses of tetraoxosulphates (VI)
- Na2SO4 and MgSO4 are used as laxatives
- (NH4)2SO4 is used as fertilizer
- For the production of SO2
- BaSO4 is used in the production of paints
- For the production of plaster of paris PoP
Test for tetraoxosulphate (VI)
Put some of the unknown solution in a test tube and acidify it with dilute HCl. Then add a few drops of
BaCl2 solution. A white precipitate of BaSO4 is formed if the unknown solution contains SO 42-
Theprecipitate remains insoluble in an excess of the dilute acid.
Ba2+(aq) + SO42-(aq) BaSO4(s)
Note: the acidification process is important to prevent the precipitation of other insoluble barium
compounds like BaSO3 or BaCO3 which are soluble in the acidic solution.
Dilute HNO3 and BaNO3 can also be used instead of HCl and BaCl2.
Assignment
Tutorial questions
- Briefly describe the contact process
- State three physical properties of H2SO4
- Describe any two chemical properties of H2SO4. Balance chemical equations important
- State three uses of H2SO4.
- State a laboratory test to distinguish between SO32- and SO42-.
- State the method of preparation of the tetraoxosulphates (VI) of (i) lead (ii) zinc

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