INORGANIC CHEMISTRY

PERIOD 03 ELEMENTS
1.

ELEMENT SYMBOL
Sodium Na
Magnesium Mg
Aluminium Al
Silicon Si
Phosphorus P
Sulfur S
Chlorine Cl
Argon Ar

2. Physical Properties

(a) Atomic & Ionic Radius

(i) Atomic Radius

 Sodium, magnesium and aluminium have a metallic radius

 Silicon, phosphorus, sulfur and chlorine have a covalent radius
 Argon has a Van der Waal’s radius
 Across the period, atomic radius decreases
 This is because the proton number increases so electrons enter the same shell, but
as the nuclear charge is increasing and the distance from the nucleus is about the
same, the outer electrons are held more tightly by the positively charged nucleus
 The electron cloud shrinks and contracts
(ii) Ionic Radius

 Sodium, magnesium, aluminium and silicon have a cation radius which is smaller than
the corresponding atomic radius
 This is because the cation has one less shell of electrons
 The remaining electrons in the cation experience a greater effective nuclear
charge as there are more protons than electrons
 Phosphorus, sulfur and chlorine have an anion radius which is larger than the
corresponding atomic radius as the anion has more electrons than protons
 The nuclear attraction on the valence electrons is less than in the neutral atom
 Therefore, the outer electrons are held less tightly and the electron cloud expands
(b) Melting Point

 Melting point increases from sodium to aluminium as the metallic bonds become
stronger; therefore more energy is required to weaken the metallic bonds
 The strength of these metallic bonds depends on:
 number of electrons available to the sea of delocalized electrons[more
electrons means stronger bond]
 atomic radius[as atomic radius decreases, metallic bonds become shorter as
the electrostatic force of attraction between the cation nucleus and the
sea of delocalized electrons is stronger]
 The melting point of aluminium is only slightly higher than that of magnesium as the
metallic bond in aluminium is only slightly stronger as the Al3+ cation has a high
charge density[so smaller radius]
 Hence, it tends to attract the delocalized electrons back to itself and this reduces
the number of valence electrons contributed to the delocalized electron cloud
 Silicon, due it being a metalloid, has a giant covalent structure and hence has a very
high melting point as strong covalent bonds have to be broken and a lot of energy is
required to break these bonds
 Phosphorus, sulfur, chlorine and argon are simple molecular compounds with ID-ID
forces of attraction with sulfur having the highest melting point as it has the
largest Mr, therefore more polarizable electrons so ID-ID forces in sulfur are the
strongest
 (c) Electrical Conductivity

 Electrical conductivity increases from sodium to aluminium[good conductors] due

to their mobile, delocalized electrons to conduct
 Silicon is a semi-conductor[electrical conductivity is moderate] as it is a
metalloid
 Phosphorus, sulfur, chlorine and argon are non-conductors as they are simple
molecular, hence no free electrons

(d) 1st Ionization Energy

 Generally increases across the period

 Electrons enter the same shell so shielding stays almost the same
 Effective nuclear charge increases so first ionization energy increases
 There are few exceptions too due to the different sub shells from where electrons
are removed
 3. Chemical Properties

(a) Reaction with Oxygen

(i) Sodium [Na]

 4Na + O2 --------> 2Na2O [white residue]

 Burns with a yellow flame
 Ionic oxide, soluble in water

(ii) Magnesium [Mg]

 2Mg + O2 --------> 2MgO [white ash]

 Requires heat
 Burns with an intense white flame
 Superficial oxidation at room temperature
 Ionic oxide, partially soluble in water

(iii) Aluminium [Al]

 4Al + 3O2 --------> 2Al2O3 [white solid]

 Requires heat
 Burns with a white flame
 Superficial oxidation at room temperature
 Ionic oxide, insoluble in water

(iv) Silicon [Si]

 Si + O2 --------> SiO2 [white solid]

 Requires heat
 Covalent oxide, insoluble in water
 Does not oxidise at room temperature

(v) Phosphorus [P]

 P4 + 5O2[excess] --------> P4O10 [white residue]

 Requires heat
 Covalent oxide, soluble in water (reacts)
 Burns with a white flame
 Dense white fumes of P4O10, which sublime to give white residue
 P4 + 3O2 --------> P4O6
 Covalent oxide, reacts with water
(vi) Sulfur [S]

 S + O2 --------> SO2
 Requires heat
 Burns with a blue flame
 Covalent oxide (gas), reacts with water
 Stays as SO2 as very high activation energy is required to convert it to SO3

(vii) Chlorine & Argon

 No reaction

(b) Oxidation States of Oxides

 Oxidation state corresponds to the number of electrons used for bonding

 The oxidation state of the element in the oxide is always positive as oxygen always
has an oxidation state of -2
 Maximum oxidation number increases across the period [sodium has +1 while
magnesium has +2]

(c) Oxides with Water

 Forms acids
 SO2 + H2O --------> H2SO3[sulfurous acid: PH 1-2]
 SO3 + H2O --------> H2SO4[sulfuric acid: PH 1-2 (highly exothermic)
 Cl2O + H2O --------> 2HOCl[hypochlorous acid] (reversible)
 Cl2O7 + H2O --------> 2HClO4[chloric (VII) acid]

(d) Reaction of Oxides with Acids & Alkalis

(i) Basic Oxides

 React with acids to form salts and water

 Na2O + HCl --------> 2NaCl + H2O
 Na2O + H2SO4 --------> Na2SO4 + H2O
 MgO + 2HCl --------> MgCl2 + H2O
 MgO + 2HNO3 --------> Mg(NO3)2 + H2O
 Na2O + 2CH3COOH --------> 2CH3COONa + H2O

(ii) Amphoteric Oxides

 React with both acids and bases

 Al2O3 + 6HCl --------> 2AlCl3 + 3H2O
  AL2O3 + H2O +2NaOH[hot & concentrated] --------> 2NaAl(OH)4 [tetra hydroxi
sodium aluminate]

(iii) Acidic Oxides

 React with alkalis to form salts and water

 SiO2 + 2NaOH[hot & concentrated] --------> Na2SiO3 [sodium silicate] + H2O
 SiO2 + CaO --------> CaSiO3 [calcium silicate]
 Blast furnace reaction
 Slag, silicon impurities; used in extraction of iron
 P4O6 +12NaOH --------> 4Na3PO3 [soft sodium phosphite] + H2O
 P4O10 + 12NaOH --------> 4Na3PO4 [sodium phosphate] + H2O
 SO2 + 2NaOH --------> Na2SO3 [sodium sulfite] + H2O
 SO3 + 2NaOH --------> Na2SO4 [sodium sulfate] + H2O
 CL2O7 + 2NaOH --------> 2NaClO4 [sodium chlorate (VII)] + H2O

(e) Reaction with Chlorine

 Forms chlorides
 Si + 2Cl2 --------> SiCl4(l)
 Requires heat
 Covalent chloride, colourless liquid
 P4 + 6Cl2 --------> 4PCl3(l)
 Requires heat
 Covalent chloride, colourless fuming liquid
 Further reacts with excess Cl2
 PCl3 + Cl2 --------> PCl5(s) [off white solid]
 P4 + 10Cl2 --------> 4PCl5
 Direct reaction
 Fuming, reacts with moisture in air (HCl)
 2S + Cl2 --------> S2Cl2(l)
 Covalent orange liquid
 Foul odour
(f) Chlorides

NaCl MgCl2 AlCl3 SiCl4 PCl3/PCl5 S2Cl2

Structure Giant ionic Ionic with Covalent Covalent Covalent Covalent

some chloride chloride chloride chloride
covalent [simple [simple [simple [simple
character molecular] molecular] molecular] molecular]
Melting High High Sublimes Low Low Low
Point
Effect of Dissolves Dissolves Reacts Reacts Reacts Reacts
water
PH of Neutral Slightly ≈3 2 2 2
solution [7] acidic
[6.5]

(g) Reaction of Chlorides with Water

(i) Sodium Chloride

 NaCl(s) + aq. H2O --------> Na+ (aq) + Cl− (aq)

 Dissolves
 PH of 7

(ii) Magnesium Chloride

 MgCl2(s) + aq. H2O --------> Mg 2+ (aq) + 2Cl− (aq)

 These ions form hexaaqua magnesium (II) chloride [𝑀𝑔(𝐻2𝑂)6]2+ + 2𝐶𝑙 −
 Magnesium ion, 𝑀𝑔2+ , has a small ionic radius and a high charge density, hence more
polarizing power so it can polarize the water molecules surrounding it, causing the
water to dissolve to give up hydrogen ions
 [Mg(H2O)6]2+ ⇌ [Mg(H20)5 (OH − )]+ + H +
 PH of 6.5

(iii) Aluminium Chloride

 Hydrolysis in water
 Forms hexaaqua aluminium (III) chloride [Al(H2O)6]3+ + 3Cl−
 PH ≈ 3
  Acidic nature of the solution is due to the small but highly charged aluminium ions
which polarize the water molecules to a greater extent, causing them to give up
hydrogen ions, making the solution slightly acidic
 [Al(H2O)6]3+ ⇌ [Al(H2O)5 (OH − )]2+ + H +

(iv) Silicon (IV) Chloride, Phosphorus (III) Chloride & Phosphorus (V) Chloride

 Hydrolyze in water to form strongly acidic solutions

 SiCl4 + 2H2O --------> SiO2 + 4HCl
 White fumes of HCl
 White precipitate
 PH 2
  PCl3 + 3H2O --------> H3PO4 + 3HCl
 PH of 1-2
 PCl5 + 4H2O --------> H3PO4 + 5HCl
 Vigorous reaction

(v) Sulfur Chloride

 S2Cl2 + H2O --------> HCl + S + H2S

 Mixture of products
 Very slow reaction
 White fumes of HCl

(h) Reaction of Elements with Water

(i) Sodium

 2Na + 2H2O --------> 2NaOH + H2

 Vigorous reaction at room temperature
 Sodium metal darts about the surface of water
 It dissolves
  Sodium metal melts
 Colourless gas produced which extinguishes a burning splinter with a ‘pop’ sound

(ii) Magnesium

 With cold water:

 Mg + 2H2O(l) ------> Mg(OH)2 + H2
 Partially soluble
 Forms a thin layer on the magnesium ribbon and stops it from reacting
further
 With steam:
 Mg + H2O(g) --------> MgO(s) + H2
 Slow reaction
 Bubbles of colourless gas

(iii) Aluminium

 2Al + 3H2O(g) --------> Al2O3 + 3H2

 No reaction with cold water
 Reacts with steam using heat

(iv) Phophorus & Sulfur

 No reaction

(v) Chlorine

 Dissolves to some extent

 Cl2 + H2O ⇌ HCl(aq) + HOCl(aq) [hydrochlorous acid]
 Disproportionational reaction as chlorine getting both oxidized [to HCl] and
reduced [to HOCl]
 GROUP 02 ELEMENTS

1. They are the alkaline earth metals

2.

NAME SYMBOL ATOMIC NUMBER ELECTRONIC

CONFIGURATION
Beryllium Be 4 1𝑠 2 2𝑠 2
Magnesium Mg 12 1𝑠 2𝑠 2 2𝑝6 3𝑠 2
2

Calcium Ca 20 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 4𝑠 2

Strontium Sr 38 [Ar] 4𝑠 2 3𝑑10 4𝑝6 5𝑠 2
Barium Ba 56 [Xe] 6𝑠 2
Radium Ra [radioactive] ---

3. General Properties

 Very reactive elements

 Show only one oxidation state (+2) as they lose 2 electrons to form stable ions
 Occur in nature in combination with other elements as metal deposits or ores such
as CaCO3, MgS and Mg(SO3)2
 4. Physical Properties

(a) Atomic Radii

 Increases down the group

 This is because each successive element has one more shell of electrons
 The outermost electrons are progressively further away from the nucleus

(b) 1st Ionization Energy

 Decreases down the group

 This is because as the atomic radius increases, the outer electrons are further
shielded from the nucleus and less tightly held
 Therefore less energy is required to remove an electron

(c) Electronegativity

 Decreases down the group

 Elements lose electrons more readily as atomic radius increases as the shielding
effect increases, and the outer electrons are held less tightly
 They are electropositive

(d) Melting Point

 Decreases down the group

 As atomic radius increases, the delocalized valence electrons are more diffused
 There is weaker attractive force between the ‘sea of electrons’ and the cations
 Metallic bond becomes longer and weaker
 Less energy required to break the metallic bonds for melting

5. Reactions

(a) Burning in Oxygen

 Form oxides
 2M + O2 --------> 2MO
 Beryllium usually does not follow the chemical properties as the other metals
 All reactions require heat
 2Mg + O2 --------> 2MgO
 Intense white flame
 2Ca + O2 --------> 2CaO
 Brick red flame
  2Sr + O2 --------> 2SrO
 White or crimson red flame
 2Ba + O2 --------> 2BaO
 Apple green flame

(b) With Water

(i) Beryllium

 No reaction

(ii) Magnesium

 Magnesium reacts with water at room temperature to form magnesium hydroxide

 Mg + 2H2O(l) --------> Mg(OH)2 + H2(g)
 Very slow reaction
 Bubbles of colourless gas produced
 Not very soluble
 PH ≈ 9
 Magnesium reacts with steam to form magnesium oxide
 Mg + H2O(g) --------> MgO +H2(g)
 Bubbles of colourless gas
 White solid produced
 Requires heat

(iii) Calcium

 Reacts with water at room temperature to form calcium hydroxide

 Ca + 2H2O(l) --------> Ca(OH)2 + H2(g)
 Faster reaction
 Partially soluble
 Bubbles of colourless gas

(iv) Strontium

 Sr + 2H2O(l) --------> Sr(OH)2 + H2(g)

 Very vigorous reaction

(v) Barium

 Ba + 2H2O(l) --------> Ba(OH)2 + H2(g)

 Very vigorous reaction
 Very soluble

(c) With Acids

 Reactivity increases down the group
 Form salt and hydrogen
 The general ionic equation is:
 M + 2H + --------> M 2+ + H2(g)
 All chlorides are soluble
 Sulfates become less soluble down the group
 Except beryllium, metals of this group undergo a redox reaction
 Metal is oxidized from 0 to +2
 Hydrogen’s oxidation state changes from +1 to 0
 Strontium and barium react more vigorously
 Solubility of oxides and hydroxides increases and forms an alkaline solution
 Carbonates are water insoluble
 All nitrates are soluble

6. Thermal Decomposition of Group 02 Nitrates

 The general equation is:

1
 M(NO3)2 --------> MO [white solid] + 2NO2(g) [brown gas] + 2O2(g)
 On heating, a group 02 nitrate decomposes to give a white residue, a brown gas and
a colourless gas that relights a glowing splinter
 The reaction and products are same for all elements
 Going down the group, from Mg(NO3)2 to Ba(NO3)2, thermal stability increases,
that is the nitrates become more stable to heat so more energy is required to
decompose them, hence they decompose at higher temperatures
 This is because as the cation radius increases, the charge density decreases and
the polarizing power of the cations decreases
 Magnesium ion has a higher charge density and therefore it can polarize the
‘electron cloud’ of the nitrate ion more effectively i.e. it distorts the electron
density of the nitrate ion, therefore lower temperature is needed to decompose
Mg(NO3)2
 Barium has a larger ionic radius than the magnesium ion and a lower charge density,
therefore it polarizes the nitrate ion less effectively than the magnesium ion,
hence a higher temperature is needed to decompose Ba(NO3)2

7. Thermal Decomposition of Carbonates

 The general equation is:

 MCO3 --------> MO(s) [white solid] + CO2(g)
 On heating, group 02 carbonates decompose to form a white solid and a colourless
gas that turns limewater milky
 From MgCO3 to BaCO3, thermal stability increases
  Reaction and products are same for all elements

8. Uses of Group 02 Compounds

(a) MgO

 Giant ionic compound

 Made up of 𝑀𝑔2+ and 𝑂2− ions held together by strong electrostatic forces of
attraction
 Has a very melting point
 Used as a refractory material to line furnaces as it can withstand high
temperatures and is resistant to chemical attack
 Good insulator

(b) Calcium

(i) Types of Compounds

 CaO: quicklime
 Ca(OH)2(aq): lime water
 CaCO3: limewater
 Ca(OH)2(s): slaked lime

(ii) Uses

 Calcium oxide, CaO, is used to neutralize acidic soils by farmers

 Calcium oxide, CaO, reacts with water to form calcium hydroxide [lime water]
 CaO(s) + H2O(l) --------> Ca(OH)2(aq)
 Calcium hydroxide is used to test for carbon dioxide gas by bubbling the gas
through it, forming a white solid which starts to precipitate out
 Ca(OH)2(aq) + CO2(g) --------> CaCO3(s) + H2O(l)
 Calcium carbonate, limestone, is used in flue gas desulfurization in which SO2
[acidic oxide] is the main pollutant, thus forming calcium sulfite which further
oxidises to form calcium sulfate
 SO2 + CaCO3 --------> CaSO3 + CO2
1
 CaSO3 + 2O2 --------> CaSO4
GROUP 17 ELEMENTS: THE HALOGENS
1. Group 17 elements have 7 valence electrons.

2. They gain an electron to complete their octet to form a halide ion which has a stable
electronic configuration [𝑋 − ion]

3. As they readily gain electrons, the halohgens are good oxidizing agents.
4.

ELEMENT SYMBOL + PROTON ELECTRONIC

NUMBER CONFIGURATION
Fluorine F [19] 1𝑠 2 2𝑠 2 2𝑝5
Chlorine Cl [17] 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝5
Bromine Br [35] 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑10 4𝑠 2 4𝑝5
Iodine I [53] [Kr] 4𝑑10 5𝑠 2 5𝑝5
Astatine At [85] [Xe] 4𝑓 14 5𝑑10 6𝑠 2 6𝑝5

5. General electronic configuration is 𝑛𝑠 2 𝑛𝑝5 , where ‘n’= quantum number.

6.

ELEMENT COLOUR AT RTP STATE AT RTP BOILING

POINT/°∁
F2 pale yellow gas -188
Cl2 pale green gas -35
Br2 Red-brown liquid 58
I2 Black solid 183
At2 Black solid - [Radioactive]

7.

ELEMENT SOLUBILITY IN WATER SOLUBILITY IN

ORGANIC SOLVENT
F2 very soluble No
Cl2 moderately soluble yellow solution
Br2 slightly soluble orange-brown solution
I2 Insoluble purple solution
At2 - -

8. Iodine is insoluble in water but is dissolved in aqueous potassium iodide solution to form
a solution known as aqueous iodine:

 I2(s) + KI(aq) --------> KI3(aq) [red-brown solution]

 Ionic equation: I2 + I − → I3− (aq)

9. Physical Properties
(a) Atomic Radius

 Increases down the group as there are more complete shells of electrons

(b) 1st Ionization Energy

 Decreases down the group as the outer shell electrons are increasingly further
away from the nucleus
 Outer shell electrons are less tightly held by the positively charged nucleus and are
more shielded by inner electrons
 Therefore shielding effect increases

(c) Volatility

 Decreases down the group

 Since the boiling point increases, the Mr also increases [high]
 There are more polarizable electrons, hence stronger ID-ID forces so more energy
required to overcome these forces

10. Reactions of Group 17 Elements

(a) Halogens as Oxidizing Agents

 Oxidizing power decreases down the group

 This is because they become less reactive down the group and their electron
affinity decreases
 Their reducing power increases down the group
 Fluorine is the strongest oxidizing agent
 General reduction equation is:
 X2 + 2e− --------> 2X −

(b) With Sodium thiosulfate

 Both chlorine and bromine oxidize sodium thiosulfate [Na2SO3] to sodium sulfate
[Na2SO4]
 4Cl0 + S2+2 O32− + 5H2O --------> 2S 6+ O42− + 10H + + 8Cl−
 4Br 0 + S2+2 O32− + 5H2O --------> 2S 6+ O42− + 10H + + 8Br −
 In both reactions, sulfur is oxidized as its oxidation number increases of +2
to +6 and both chlorine and bromine are reduced as they go from 0 to -1
 Iodine oxidizes Na2SO3 to a lesser extent than chlorine
 I20 + 2S +2 O32− --------> S4+2.5 O62− [tetra thionate ion] + 2I −
 Iodine oxidizes sulfur from +2 to 2.5 and gets reduced from 0 to -1
(c) With Hydrogen

 Form hydrides
 F2 + H2 --------> 2HF(g)
 Very rapid reaction, explodes
 White fumes of HF
 Cl2 + H2 --------> 2HCl(g)
 Condition for this reaction is UV light
 Very rapid, explodes in sunlight
 Br2 + H2 --------> 2HBr
 Very slow reaction, heat at 200℃ with a platinum catalyst
 I2 + H2 --------> 2HI
 No reaction until heated strongly

(d) Thermal Stability of Hydrides

 As the atomic radius of the halogens increases down the group, the H-X bond
becomes longer and weaker and is easily broken
 Hydrogen fluoride is most stable
 Hydrogen fluoride and hydrogen chloride do not decompose
 2HBr [white fumes] --------> H2 + Br2 [red brown vapour]
 2HI [white fumes] --------> H2 + I2 [purple iodine]
 Requires hot glass rod as it provides the activation energy to decompose HI

(e) Displacement Reactions

 Each halide ion can be oxidized by the halogen above it

 A more reactive halogen displaces a less reactive halogen from its compound

COMPOUND Cl2 Br2 I2

 NaCl No reaction No reaction No reaction
NaBr 2NaBr + Cl2 -----> No reaction No reaction
2NaCl + Br2
Red brown vapour
NaI 2NaI + Cl2 -----> 2NaI + Br2 -----> No reaction
2NaCl + I2 2NaBr + I2
Black solid (s) Red brown liquid
Purple vapour (g) disappears
Purple vapour
appears
Black solid is seen

(f) Chlorine with NaOH

 With cold aqueous NaOH at 15℃:

 Cl2(aq) +2NaOH(aq) --------> NaCl + NaClO + H2O
 Forms sodium chloride and sodium chlorate (I)
 Chlorine is reduced from Cl2 to NaCl as the oxidation state of chlorine
reduces from 0 to -1
 Chlorine is oxidized too from Cl2 to NaClO as the oxidation state of chlorine
increases from 0 to +1
 Disproportional reaction as chlorine is getting both oxidized and reduced
 With hot aqueous NaOH at 70℃:
 3Cl2 + 6NaOH(aq) --------> 5NaCl(aq) + NaClO3 + 3H2O
 Forms sodium chloride and sodium chlorate (V)
 Chlorine is oxidized from Cl2 to NaClO3 as its oxidation state increases
from 0 to +5
 Chlorine is reduced from Cl2 to NaCl as its oxidation state reduces from 0
to -5
 Disproportional reaction as chlorine gets both oxidized and reduced

(g) Halides with Concentrated H2SO4

 NaCl:
 NaCl + conc. H2SO4 --------> HCl(g) + NaHSO4
 Forms hydrogen chloride and sodium hydrogen sulfate
  White fumes of HCl are seen
 NaBr:
 HBr + conc. H2SO4 --------> Br2 + SO2 + 2H2O
 Bromine and sulfur dioxide are formed
 Orange vapour of Br2/ red brown liquid of Br2 and a pungent gas are
observed
 Concentrated H2SO4 is a stronger oxidizing agent than bromine so it
oxidizes HBr to Br2
 NaI:
 NaI + conc. H2SO4 --------> HI(g) + NaHSO4
 Forms hydrogen iodide and sodium hydrogen sulfate
 White fumes seen
 HI + H2SO4 --------> 4I2 + H2S + 4H2O
 Purple vapour in gaseous state or black solid in solid state
 HI is oxidized by concentrated H2SO4 to iodine (I2)

11. Test for Halide Ions

 The reagent used is colourless aqueous silver nitrate [Ag(NO3)] (aq)

 The silver halide, AgX, is precipitated out as the product with aqueous silver
nitrate
 The general ionic equation is:
 Ag + (aq) + X − (aq) --------> AgX(s)
 The general equation is:
 AgNO3(aq) + NaX(aq) --------> AgX(s) + NaNO3
 Test for chloride ion:
 NaCl(aq) + AgNO3(aq) --------> NaNO3(aq) + AgCl(s) [white precipitate]
 To the white precipitate of AgCl, excess of cold aqueous NH3 is added
 White precipitate dissolves in aqueous ammonia
 2AgCl(s) + 2NH3(aq) --------> [𝐴𝑔(𝑁𝐻3)2]+ 𝐶𝑙 − [diamine silver (i) chloride]

 Precipitate is soluble in concentrated aqueous ammonia

 Test for bromide ion:
 NaBr(aq) + AgNO3(aq) --------> NaNO3(aq) + AgBr(s) [cream precipitate]
  To the cream precipitate of AgBr, excess of cold aqueous NH3 is added
 Cream precipitate is partially soluble in aqueous ammonia
 AgBr(s) + 2NH3(aq) --------> [𝐴𝑔(𝑁𝐻3)2]+ 𝐵𝑟 −[diamine silver (i) bromide]
 Precipitate is soluble in concentrated aqueous ammonia
 Test for iodide ion:
 NaI(aq) + AgNO3(aq) --------> NaNO3(aq) + AgI(s) [yellow precipitate]
 To the yellow precipitate of AgI, excess of cold aqueous NH3 is added
 Yellow precipitate is insoluble in aqueous ammonia
 AgI(s) + 2NH3(aq) --------> [𝐴𝑔(𝑁𝐻3)2]+ 𝐼 − [diamine silver (i) iodide]
 Precipitate is insoluble in concentrated aqueous ammonia

12. Uses of Halogens

(a) Fluorine

 Used in manufacture of CFCs

 To make polymers like PTFE [poly tetra fluoro ethane] which is used for non-stick
coating in fry pans
 Added to toothpaste to prevent cavities

(b) Chlorine

 To make polymers like PVC [poly vinyl chloride]

 Manufacture of HCl
 Disinfectant in purification of water:
 Cl2(g) + H2O --------> HCl + HOCl
 Chlorine is oxidized to HOCl and reduced to HCl
 HOCl is used as a disinfectant due to its antibacterial properties
 To manufacture organic solvents such as CCl4, CH2Cl2 for dry cleaning and CHCl3
for chloroform fluid

(c) Bromine

 NaBr is used to produce AgBr which is used in photography as the film is coated in
AgBr
 Dyes and pharmaceutical industry
 To make flame retardants such as CH2BrCl and CBrF3

(d) Iodine

 As AgI in photographic film

 Aqueous iodine is used as a mild antiseptic
NITROGEN AND SULFUR
 1. Nitrogen

 Has the formula of N2

 N2 gas makes up 78% of the atmosphere
 Unreactive as the activation energy required to break the N≡N triple covalent bond
is very hard
 Electronic configuration is 1𝑠 2 2𝑠 2 2𝑝3
 5 valence electrons and has a valency of -3 as it is easier for it to gain 3 electrons
to complete its octet rather than lose 5 electrons:
 N(g) + 3𝑒 − --------> N 3−(g) [nitride ion]

2. Ammonia as an Abundant Nitrogen Compound

(a) Structure

 Has a trigonal pyramidal shape

 Has an angle of 107°
 Has the formula NH3
(b) Formation of Ammonium ion

 An ammonium ion forms due to dative bonding between a nitrogen of ammonia and a
hydrogen of water
 NH3 + H2O --------> NH4++ OH −

(c) Properties

 NH3 is a weak base i.e. it dissociates partially in water to form hydroxide ion:
 NH3 + HNO3 --------> NH4NO3
 2NH3 + H2SO4 --------> (NH4)2SO4
 NH3 is very soluble in water, as it can form hydrogen bonds with water

(d) Test for Ammonium NH4+ Ion

 Ammonium ion is acidic so it will react with a base to release ammonia (only alkaline
gas)
 React an ammonium salt with sodium hydroxide and place a damp red litmus at the
mouth of the test tube
 Observations:
 Damp red litmus turns blue
 Colourless pungent gas is formed
 Reaction Examples:
 NH4Cl + NaOH(aq) --------> NaCl + NH3
 (NH4)2SO4 + 2NaOH --------> Na2SO4 + 2NH3 + 2H2O
 2NH4Cl + CaO --------> CaCl2 + 2NH3 + H2O
(e) Uses of Ammonia

 Used in the manufacture of fertilizers:

 H4)2SO4
 NH3 + HNO3 --------> NH4NO3
 Higher the composition of nitrogen in the fertilizer, the better the fertilizer as
plants need nitrogen to form proteins
 Manufacture of explosives such as Trinitrotoluene (TNT)

3. Problems of Fertilizers

(a) Eutrophication

 Excessive fertilizers leach into the soil

 This reaches rivers and streams and collects in them
 This leads to excessive growth of algae which block sunlight coming from the
water’s surface
 Algae consume the oxygen in water
 Aquatic life dies
 Dead plants and animals decompose by activity of bacteria
 Dissolved O2 in water decreases
 Everything dies

(b) Health

 Nitrates from these fertilizers can contaminate the groundwater that is fed into
the supply of towns
 Nitrate ions (NO3−) are poisonous as they can oxidize the 𝐹𝑒 2+ ions in haemoglobin
 This reduces the oxygen carrying capacity of blood
 4. Oxides of Nitrogen (NOx)

(a) Production

(i) Natural Causes

 Lightning storms have energy which break the N≡N in the atmosphere

(ii) Man-Made Causes

 In car engines, high temperatures are needed for fuel to undergo combustion
 At high temperatures, nitrogen in the air breaks and it combines with oxygen to
form NOx in an endothermic reaction:
 N2 + O2 --------> 2NO(g) [colourless gas]
 2NO + O2 --------> 2NO2(g) [brown gas]

(iii) Fossil Fuels

 Burning of these fossil fuels in power stations releases NOx

(b) NOx Effects on Atmosphere

 NOx causes problems in the lower atmosphere as it combines with other air
pollutants to form ozone
 Ozone O3(g), is an eye irritant and causes headaches as well as respiratory
problems

(c) NOx as a Secondary Pollutant

 Nitrogen oxides are examples of primary pollutants because they are given off
directly into the air from the source of pollution such as car exhausts and power
plants
 NOx react with substances in air to form secondary pollutants
 Exhaust fumes contain another primary pollutant called volatile organic compound
(VOCs)
 VOCs are unburnt hydrocarbons from fuel and their oxidized products
 VOCs react with NOx in a photochemical reaction in the presence of sunlight (as a
source of energy) to form preoxyacetyl nitrate (PANs CH3CO2NO2)
 PAN is one of the harmful pollutants found in photochemical smog and causes eye
irritation and discomfort to lungs
 Photochemical smog is a mixture of smoke and fog
 5. Uses of Sulfur Compounds

 Manufacture of fertilizers e.g. (NH4)2SO4

 Manufacture of paint, dyes and used in pharmaceutical industry
 Used for rust removal from steel objects before it can be panted
 Manufacture of explosives
 H2SO4 is used in car batteries
 H2SO4 is used in tanning of leather

6. Sulfur Dioxide SO2

(a) Test for Identification

 React it with an oxidizing agent

 Filter paper is in KMnO4 (aq)
 Colour changes from purple to colourless
 Another way is dipping a filter paper in K2Cr2O2(aq)
 Colour change is from orange to green

(b) Properties

 Acidic gas
 Is a reducing agent
 Has a bent shape with an angle of 119°

(c) Uses

 As a food preservative as it inhibits the growth of bacteria and fungi

 Good reducing agent so it prevents the oxidation of fats and over ripening of fruits
 Used to preserve wines as it prevents wine from getting oxidized to carboxylic acid
(vinegar) at PH<4

7. Acid Rain

(a) Production

 NO2 reacts with water (rain, moisture in air) to form a mixture of nitric acid and
nitrous acid
 2NO2 + H2O --------> HNO2[nitrous acid] + HNO3[nitric acid]
 1
 HNO2 + 2O2 --------> HNO3
 Final equation is:
1
 2NO2 + H2O[rain] + 2O2[atmospheric oxygen] --------> 2HNO3[acid rain]
 SO2 is formed from volcanic eruptions(natural cause) or by burning coal as fuel in
power stations(human cause) and this SO2 is oxidized to acid rain in a reaction
catalyzed by NOx
 Nitrogen oxide, NO, reacts with atmospheric oxygen to form nitrogen dioxide,
NO2:
1
 NO + 2O2 --------> NO2
 SO2 reacts with NO2 to form sulfur trioxide, SO3 and nitrogen oxide, NO
(catalyst is regenerated):
 SO2 + NO2 --------> SO3 + NO
 SO3 reacts with water, rain, to form acid rain:
 SO3 + H2O --------> H2SO4[acid rain]

(b) Effects

 Corrosion of buildings and limestone structures(marble):

 CaCO3 + H2SO4 --------> CaSO4 + H2O + CO2
 Corrosion of steel structures, bridges, buildings and iron in vehicles:
 Fe + H2SO4 --------> FeSO4 + H2
 Acidification of lakes, rivers and ponds, resulting in loss of aquatic life
 Lowers the PH of soil so crop yield is reduced hence farmers have to neutralize the
soil by spreading lime:
 Ca(OH)2 + H2SO4 --------> CaSO4 + H2O
 CaO + H2SO4 --------> CaSO4 +H2O

(c) Prevention

 Burn less sulfur containing fuels e.g. coal

 Treat exhaust gases (flue gas) from industries and power stations with SO2
absorbing chemicals to neutralize SO2 such as calcium oxide, CaO:
 CaO + SO2 --------> CaSO3[calcium sulfite]
1
 CaSO3 + 2O2 --------> CaSO4[calcium sulfate]
 Prevent NOx pollution from vehicles:
 By fitting the exhaust system of cars with catalytic converters
 It converts the harmful gases to less harmful gases
 The catalytic converter is a steel structure coated with a ceramic surface(it
can withstand high temperatures)
  The honeycombed ceramic surface is coated with the catalyst such as
platinum(Pt), palladium(Pd) and rhondium(Rn) which catalyze the reaction:
 It works at a high temperature of 200℃
 2NO + 2CO --------> 2CO2
 2CO + O2 --------> 2CO2
 C8H18[octane pollutant] + 2SO2 --------> 8CO2 + 9H2O
 Operate power stations that burn fossil fuels at a lower temperature