Chapter 3 - Group

Elements and
their compounds
 Groups of Elements in the
Periodic Table
Eight Groups (the 7 groups of representative elements and
the group of noble gases):

I. Alkali metals: (H), Li, Na, K, Rb, Cs

II. Alkali earth metals: Be, Al, Ca, Sr, Ba, Ra
III. Boron family: B, Al, Ga, In, Tl
IV. Carbon family: C, Si, Ge, Sn, Pb
V. Nitrogen family: N, P, As, Sb, Bi
VI. Chalcogens O, S, Se, Te, Po
VII.Halogens F, Cl, Br, I, At
VIII. Noble gases: (He), Ne, Ar, Kr, Xe, Rn

Representative metals (I and II) and non-metals (VI and VII). 2

General Properties of Metals
~lustrous surface (shiny)
~dense
~malleable (can be flattened, deformed)
~ductile (can be pulled into wires)
~ high thermal conductivity
~ high 3D electrical conductivity
~hard
…even though two orders of magnitude difference between
worst (plutonium) and best (silver) metal conductivities under
ambient conditions, plutonium conductivity is 105 higher than
best conducting nonmetallic element

Sodium and potassium have high natural abundances, occurring

widely as salts such as the chlorides.
3
Group I – Alkaline
Metals
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals

Much of the important chemistry of the alkali and alkaline earth metals can
be understood on the basis of their low ionization enthalpies (or
electronegativities) and the favourability of ionic bonding.
5
What Dictates the Chemistry of
Alkali Metals?
• Low ionization energies to make +1 cations

• M+ ions are spherical and hard (low polarizability)

• High 2nd ionization energies prevent the +2 oxidation state

• Most bonding interactions are ionic due to low polarizability (Li+ is

strongest in terms of polarizing ability due to size/charge ratio in
other words it forms the most covalent compounds)

• Li is least reactive, Cs is most reactive

6
The Alkali Metals (Group 1 Except Hydrogen)
What is an alkali metal?
• Any element in Group 1 except hydrogen
• A soft silvery metal that has a relatively low
melting point, boiling point and density (for a
metal)
• Typically stored under oil because it reacts with
air (both oxygen and water vapour)

Melting Boiling Density

Point Point (at 20 °C)
Lithium 180.54 °C 1347 °C 0.534 g/cm3

Sodium 97.81 °C 883.0 °C 0.971 g/cm3

Potassium 63.65 °C 773.9 °C 0.862 g/cm3

Rubidium 39.05 °C 687.9 °C 1.532 g/cm3

Cesium 28.4 °C 678.5 °C 1.873 g/cm3

The Alkali Metals (Group 1 Except Hydrogen)
The Alkali Metals (Group 1 Except Hydrogen)
What is an alkali metal?
• Only forms one cation (+1) and no anions
• Has only one valence electron (electron
configuration [N.G.] ns1) and a low first ionization
energy

• An excellent reducing agent (good at losing

electrons so that other elements can be reduced).
First Ionization Standard Reduction
Energy (kJ/mol) Potential (V = J/C)

Lithium 520.2 -3.040

Sodium 495.8 -2.713
Potassium 418.8 -2.924
Rubidium 403.0 -2.924
Cesium 375.7 -2.923
The Alkali Metals (Group 1 Except Hydrogen)
How can I distinguish between the alkali metals?
• Flame test - All of the alkali metals give
positive flame tests (as shown in the table
below).

• Reactivity with water - All of the alkali metals

react exothermically with water to give the
corresponding hydroxide and hydrogen gas.
Flame Colour Strength of Reaction with Water*

Lithium Red Slow

Sodium Orange Vigorous

Potassium Lilac Flames

Rubidium Bluish red Explodes

Cesium Blue Explodes

The Alkali Metals (Group 1 Except Hydrogen)

Reaction with water

Metals Results Reactivity @

25oC with
water
Li(s) LiOH, ½ H2 Slow
Na(s) NaOH, ½ H2 Vigorous

K(s) KOH, ½ H2 Flames

Rb(s) or Cs (s) MOH, ½ H2 Explodes
The Alkali Metals (Group 1 Except Hydrogen)
Reaction with oxygen

Metals Results Reactivity @

25oC with
oxygen
Li(s) LiO2, trace Li2O2 Slow
Na(s) Na2O2, forced Vigorous
NaO2
K(s), Rb(s) or Cs (s) MOH, ½ H2 Flames
M20 M2O2 MO2
Oxides Peroxides Superoxides
O2- ˉO-Oˉ (O22-) O2-
If we limit the amount of oxygen available, we can force
sodium to stop at sodium oxide. Potassium, rubidium and cesium
cannot be stopped at the oxide – only at the peroxide.
The Alkali Metals (Group 1 Except Hydrogen)
What do we know about the ionic compounds of alkali metals?
• They are all soluble in water - A solution of sodium
chloride in water is often written as NaCl(aq), but that’s a
bit misleading. When table salt is dissolved in water, the
following occurs:

1. All of the ionic Na-Cl bonds have been broken, and the
sodium cation is solvated by water molecules (as is the
chloride anion):
The Alkali Metals (Group 1 Except Hydrogen)

• To indicate this solvation, we can write

Na(OH2)6+(aq) or Na+(aq).

• For an ionic compound to be soluble in

water, the solvated ions must be more
stable (lower energy) than the initial
crystal lattice so that energy is released.
Alkali metals have large hydration
enthalpies. (The beaker gets hot when
NaOH is dissolved in H2O!).
The Alkali Metals (Group 1 Except Hydrogen)

The lithium cation is particularly well stabilized by solvation

with water. In other words, it has an unusually large enthalpy
of hydration - the reason for this, is the lithium cation’s small
size (only 59 pm – remember that the electron configuration of
Li+ is 1s2 2s1) which allows the oxygen atoms of the surrounding
water molecules to approach more closely than they could for a
larger cation.

This unusually large enthalpy of hydration is the reason that

lithium gives up its electron more easily in aqueous solution than
any other alkali metal (hence the most negative standard
reduction potential) despite having the highest first ionization
energy.
The Alkali Metals (Group 1 Except Hydrogen)
• Pure alkali metals don’t exist in nature, so how are they made?
• Pure sodium is obtained by electrolysis of NaCl in a Downs cell.
• Because sodium is so reactive, it is difficult to convert sodium
salts to sodium metal. To do so requires a significant input of
energy. Industrially, this is accomplished by electrolysis
(application of a potential to “force” a reaction to go in the
unfavourable direction).

• Because H+ is more easily reduced than Na+, there can be no

water present in the electrolysis. Instead, the sodium salt is
melted. (NaOH melts at 318 °C; NaCl melts at 808 °C; adding
BaCl2 or CaCl2 lowers the melting point of NaCl to ~600 °C;
Ba2+ and Ca2+ are more difficult to reduce than Na+)

• Pure sodium is insoluble in molten NaCl and less dense than it.
As such, it can be removed from the cell. It must, of course,
be kept separate from the other product of the Downs cell –
chlorine gas!
• Lithium is obtained in a similar fashion (electrolysis of LiCl).
The Alkali Metals (Group 1 Except Hydrogen)
The Alkali Metals (Group 1 Except Hydrogen)
If aqueous NaCl is electrolyzed (instead of molten NaCl), NaOH
is obtained instead of sodium metal. This is the main way in which
sodium hydroxide and chlorine gas are prepared industrially.

As in the Downs cell, the reaction at the anode and cathode are:
2𝐶𝑙 − 𝑎𝑞 → 𝐶𝑙2 𝑔 + 2𝑒 −
𝑁𝑎+ (𝑎𝑞) + 𝑒 − → 𝑁𝑎(𝑙)
𝟐𝑵𝒂+ (𝒂𝒒) + 𝟐𝑪𝒍− (𝒂𝒒) → 𝟐𝑵𝒂(𝒍) + 𝑪𝒍𝟐 (𝒈)

In an aqueous electrolysis of NaCl, the reaction at the anode and

cathode are:
2𝐶𝑙 − (𝑎𝑞) → 𝐶𝑙2 (𝑔) + 2𝑒 −
𝐻2 𝑂(𝑙) → 𝐻 + (𝑎𝑞) + 𝑂𝐻−
2𝑁𝑎+ (𝑎𝑞) + 2𝑂𝐻 − (𝑎𝑞) → 2𝑁𝑎𝑂𝐻(𝑎𝑞)
𝟐𝑵𝒂+ (𝒂𝒒) + 𝟐𝑪𝒍− (𝒂𝒒) + 𝟐𝑯𝟐 𝑶(𝒍) → 𝟐𝑵𝒂𝑶𝑯(𝒂𝒒) + 𝑯𝟐 (𝒈) + 𝑪𝒍𝟐 (𝒈)

It is important to keep the NaOH and chlorine gas separate. If

they are allowed to react, they will make bleach (NaOCl):
The Alkali Metals (Group 1 Except Hydrogen)
The Alkali Metals (Group 1 Except Hydrogen)
Pure potassium is made by reaction of KCl with sodium metal.
• Potassium cannot be made by electrolysis (like sodium is) because
potassium is soluble in molten KCl. As such, it could not easily be
removed from an electrolytic cell.

• Potassium has a lower boiling point than sodium (774 °C vs 883 °C),
so potassium can be distilled (selectively evaporated) out of a
mixture of sodium and potassium.

• When molten KCl is reacted with molten sodium, an equilibrium is

established:

• Industrially, this is done at 850 °C. The removal of potassium

vapour pushes the reaction to continue in the “forward” direction to
try to restore equilibrium.
Rubidium and cesium are obtained in a similar fashion (reduction of a
salt by a reducing agent).
 Clear cut grouping of metals (Groups I and
II) forming binary compounds with non-
metals (Groups VI and VII)
Alkali metals, X: Li, Na, K, Rb, Cs
X2 O Li2O, Na2O, K2O, Rb2O, Cs2O
XCl LiCl, NaCl, KCl, RbCl, CsCl

Alkali earth metals, X: Be, Mg, Ca, Sr, Ba

XO BeO, MgO, CaO, SrO, BaO
XCl2 BeCl2, MgCl2, CaCl2, SrCl2, BaCl2

Chalcogens, X: O, S, Se, Te
Na2X Na2O, Na2S, Na2Se, Na2Te
CaX CaO, CaS, CaSe, CaTe

Halogens, X: F, Cl, Br, I

LiX LiF, LiCl, LiBr, LiI
CaX2 CaF2, CaCl2, CaBr2, CaI2
21
Hydroxides

• NaOH etc., white, very hygroscopic (deliquescent) solids

(means they literally dissolve in the moisture from the air)

• solids also absorb CO2 from the atmosphere (solutions do as

well)

Salts

• MX where X is many types of anions

most give colourless, crystalline ionic compounds

Anomalies arise with lithium compounds –

Why?
Mainly due to its small size and its effect on lattice energies.
 Carbonates
Group 1 carbonates M2CO3: Formed on bubbling carbon
dioxide into excess hydroxide solution

2MOH(aq) + CO2(g) → M2CO3(aq) + H2O(l) (M = Li, Na, K, Rb, Cs)

ionic equation: 2OH–(aq) + CO2(g) → CO32–(aq) + H2O(l)

The carbonates are white solids, quite soluble in water, and,

apart from lithium, thermally stable to red–heat.

Hydrated sodium carbonate, Na2CO3.10H2O, is known as

washing soda and is used to soften water by precipitating
magnesium and calcium salts as their less soluble carbonates.
 Hydrogencarbonates
Group 1 hydrogencarbonates MHCO3: Formed on bubbling excess
carbon dioxide into the hydroxide solution

The reaction above happens first and then:

M2CO3(aq) + H2O(l) + CO2(g) → 2MHCO3(aq) (M = Li, Na, K, Rb,

Cs)

ionic equation: CO32–(aq) + H2O(l) + CO2(g) → 2HCO3–(aq)

They are white solids, slightly soluble in water, weakly alkaline and
readily decompose on heating to form the carbonate and carbon
dioxide gas.

e.g. at 270°C: 2NaHCO3(s) → Na2CO3(s) + H2O(l) + CO2(g)

 Standing in Group 2A(2), Looking Backward
to 1A(1) and Forward to 3A(13)

Fig. 14.6 (P 551)

 CONTENTS
• General properties
• Trends in electronic configuration
• Trends in atomic and ionic radius
• Trends in melting point
• Trends in ionization energy
• Reaction with oxygen and water
• Oxides and hydroxides
• Carbonates
• Sulphates
 GROUP PROPERTIES

GENERAL • metals
• all have the electronic configuration (ns2)

TRENDS • melting point

• electronic configuration
• electronegativity
• atomic size
• ionic size
Important Reactions of the Alkaline Earth Metals - I

1. The metals reduce O2 to form the oxide:

2 M(s) + O2 (g) 2 MO(s)
Barium also forms the peroxide BaO (s).
2. The Metals of higher atomic weight reduce water to form hydrog
gas:
M(s) + 2 H2O(l) M(OH)2 (aq) + H2 (g)
M = Ca, Sr and Ba
Be and Mg form an adherent oxide coating that allows only slig
reaction.
3. The metals reduce halogens to form ionic halides:
M(s) + X2(-) MX2 (s) X = F, Cl, Br, I
4. Most of the metals reduce hydrogen to form ionic hydrides.
M(s) + H2 (g) MH2 (s) all except Be
 THE s-BLOCK ELEMENTS
Elements in Group I (alkali metals) and Group II (alkaline earths) are known as
s-block elements because their valence (bonding) electrons are in s orbitals.

ALKALI METALS ALKALINE EARTHS

Gp I Gp II

1s2 2s1 Li Be 1s2 2s2

1s2 2s2 2p6 3s1 Na Mg 1s2 2s2 2p6 3s2

1s2 2s2 2p6 3s23p64s1 K Ca 1s2 2s2 2p6 3s23p64s2

… 5s1 Rb Sr … 5s2

… 6s1 Cs Ba … 6s2

Fr Rn

Francium and radium are both

short-lived radioactive elements
 Group Trends
Electronic Configuration

Be Mg Ca Sr Ba
Atomic Number 4 12 20 38 56
Old e/c 2,2 2,8,2 2,8,8,2 2,8,18,8,2 2,8,18,18,8,2
New e/c 1s2 2s2 …3s2 … 4s2 … 5s2 … 6s2

As the nuclear charge increases, the electrons go into shells further

from the nucleus.

The extra distance of the outer shell from the nucleus affects…

Atomic radius Ionic radius

Ionisation energy Melting point
Chemical reactivity
 Group Trends
Atomic & Ionic Radius
Be Mg Ca Sr Ba
Atomic radius / nm 0.106 0.140 0.174 0.191 0.198
Electronic config. 2,2 2,8,2 2,8,8,2 2,8,18,8,2 2,8,18,18,8,2

ATOMIC RADIUS INCREASES down Group

• the greater the atomic number
the more electrons there are;
these go into shells increasingly
further from the nucleus
1s2 2s2 2p6 3s2 1s2 2s2 2p6 3s23p64s2

• atoms of Group II are smaller than

the equivalent Group I atom

the extra proton exerts a greater

attraction on the electrons 11 protons 12 protons
1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2
 Group Trends
Atomic & Ionic Radius
Be Mg Ca Sr Ba
Atomic radius / nm 0.106 0.140 0.174 0.191 0.198
Electronic config. 2,2 2,8,2 2,8,8,2 2,8,18,8,2 2,8,18,18,8,2

Be2+ Mg2+ Ca2+ Sr2+ Ba2+

Ionic radius / nm 0.030 0.064 0.094 0.110 0.134
Electronic config. 2 2,8 2,8,8 2,8,18,8 2,8,18,18,8

IONIC RADIUS INCREASES down Group

• ions are smaller than atoms – on removing the outer shell
electrons, the remaining electrons are now in fewer shells

1s2 2s2 2p6 3s2 1s2 2s2 2p6 1s2 2s2 2p6 3s23p64s2 1s2 2s2 2p6 3s23p6
 Group Trends
Melting Point
Be Mg Ca Sr Ba
Melting point / ºC 1283 650 850 770 710
Electronic config. 2,2 2,8,2 2,8,8,2 2,8,18,8,2 2,8,18,18,8,2

DECREASES down Group

• each atom contributes two electrons to the delocalised cloud
• metallic bonding gets weaker due to increased size of ion

Larger ions mean

that the electron
cloud doesn’t bind
them as strongly

• Group I metals have lower melting points than the equivalent Group II
metal because each metal only contributes one electron to the cloud

NOTE: Magnesium doesn’t fit the trend because crystalline structure can
also affect the melting point of a metal
 First Ionisation Energy
Be Mg Ca Sr Ba
1st I.E. / kJ mol-1 899 738 590 550 500
2nd I.E. / kJ mol-1 1800 1500 1100 1100 1000
3rd I.E. / kJ mol-1 14849 7733 4912 4120 3390

DECREASES down the Group

Despite the increasing nuclear charge the values decrease due to the
extra shielding provided by additional filled inner energy levels

MAGNESIUM
There are now 12 protons
pulling on the outer shell
4+ electrons. However, the extra
12+
filled inner shell shield the
nucleus from the outer shell
electrons. The effective
nuclear charge is less and the
BERYLLIUM electrons are easier to
There are 4 protons pulling remove.
on the outer shell electrons
1st I.E. = 738 kJ mol-1
1st I.E. = 899 kJ mol-1
 Successive Ionisation Energies
Be Mg Ca Sr Ba
1st I.E. / kJ mol-1 899 738 590 550 500
2nd I.E. / kJ mol-1 1800 1500 1100 1100 1000
3rd I.E. / kJ mol-1 14849 7733 4912 4120 3390

Successive Ionisation Energy values get larger

12+ 12+ 12+

1st I.E. = 738 kJ mol-1 2nd I.E. = 1500 kJ mol-1 3rd I.E. = 7733 kJ mol-1
There are now 12 protons and There is a big jump in IE
only 11 electrons. The because the electron being
increased ratio of protons to removed is from a shell nearer
electrons means that it is the nucleus; there is less
harder to pull an electron out. shielding.
Properties Down Group II

Reactivity increases down the

group.

So Barium is the most reactive, and

is often stored under oil like the
alkali metals, as a result!
Chemical Properties Of The Elements
Reactivity increases down the Group due to the ease of cation formation

OXYGEN react with increasing vigour down the group

Mg burns readily with a bright white flame

0 0 +2 -2
2Mg(s) + O2(g) —> 2MgO(s)

Ba burns readily with an apple-green flame

2Ba(s) + O2(g) —> 2BaO(s)

In both cases…
the metal is oxidised Oxidation No. increases from 0 to +2
oxygen is reduced Oxidation No. decreases from 0 to -2

Mg —> Mg2+ + 2e¯

O + 2e¯ —> O2-
 CHEMICAL PROPERTIES OF THE
ELEMENTS
Reactivity increases down the Group due to the ease of cation formation

WATER react with increasing vigour down the group

Mg reacts very slowly with cold water

Mg(s) + 2H2O(l) —> Mg(OH)2(aq) + H2(g)

but reacts quickly with steam

Mg(s) + H2O(g) —> MgO(s) + H2(g)

Ba reacts vigorously with cold water

Ba(s) + 2H2O(l) —> Ba(OH)2(aq) + H2(g)
 Properties Down Group II
Reactions with Water
Beryllium has no reaction with water or steam even at red heat
– This is due to a thick oxide layer on the surface
Magnesium has a very slight reaction with cold water.

The reaction soon stops because magnesium hydroxide is almost

insoluble in water and forms a barrier preventing further reaction.

Magnesium will react with STEAM to form the metal oxide and
hydrogen gas.

Calcium, strontium and barium all react with cold water with
increasing vigour to give the metal hydroxide and hydrogen.
Reaction with Chlorine
 Oxides Of Group II

Bonding • ionic solids; EXCEPT BeO which has covalent character

• BeO (beryllium oxide) MgO (magnesium oxide)

CaO (calcium oxide) SrO (strontium oxide)
BaO (barium oxide)

Reaction
with water
Be Mg Ca Sr Ba
Reactivity with water NONE reacts reacts reacts reacts
Solubility of hydroxide Insoluble Sparingly Slightly Quite Very
g/100cm3 of water soluble soluble soluble soluble
pH of solution - 9-10

React with water to produce the hydroxide (not Be)

e.g. CaO(s) + H2O(l) —> Ca(OH)2(s)
 Hydroxides of Group II

Properties basic strength also increases down group

• this is because the solubility increases

• the metal ions get larger so charge density decreases
• get a lower attraction between the OH¯ ions and
larger 2+ ions
• the ions will split away from each other more easily
• there will be a greater concentration of OH¯ ions in
water
 Hydroxides of Group II
Properties basic strength also increases down group

• this is because the solubility increases

• the metal ions get larger so charge density decreases
• get a lower attraction between the OH¯ ions and larger 2+ ions
• the ions will split away from each other more easily
• there will be a greater concentration of OH¯ ions in water

BeO MgO CaO SrO BaO

Reactivity with water NONE reacts reacts reacts reacts
Solubility of hydroxide Insoluble Sparingly Slightly Quite Very
in water soluble soluble soluble soluble
pH of solution - 10.4 9-10 13.0 13.1

Lower charge density of the larger Ca2+

ion means that it doesn’t hold onto the
OH¯ ions as strongly. More OH¯ get
released into the water. It is more
soluble and the solution has a larger
pH.
 Hydroxides of Group II

Uses

Ca(OH)2 used in agriculture to neutralise acid soils

Ca(OH)2(s) + 2H+ (aq) —> Ca2+(aq) + 2H2O(l)

Mg(OH)2 used in toothpaste and indigestion tablets as an

antacid
Mg(OH)2(s) + 2H+ (aq) —> Mg2+(aq) + 2H2O(l)

Both the above are weak alkalis and not as caustic as sodium hydroxide

©HOPTON
 Carbonates of Group II
Properties

• insoluble in water
MgCO3 CaCO3 SrCO3 BaCO3
Solubility g/100cm3 of water 1.5 x 10-4 1.3 x 10-5 7.4 x 10-6 9.1 x 10-6
Decomposition temperature / ºC 400 980 1280 1360

• undergo thermal decomposition to oxide and carbon dioxide

e.g. MgCO3(s) → MgO(s) + CO2(g)

• the ease of decomposition decreases down the group

EASIER HARDER

One might think that the greater charge density of the smaller Mg2+ would mean that
it would hold onto the CO32- ion more and the ions would be more difficult to separate.

The driving force must be the formation of the oxide. The smaller ion with its
greater charge density holds onto the O2- ion to make a more stable compound.
 Sulphates
MgSO4 CaSO4 SrSO4 BaSO4
Solubility g/100cm3 of water 3.6 x 10-1 1.1 x 10-3 6.2 x 10-5 9.0 x 10-7

SOLUBILITY DECREASES down the Group

• as the cation gets larger it has a lower charge density
• it becomes less attracted to the polar water molecules

Greater charge density of Mg2+ ion Lower charge density of larger Ca2+ means
means that it is more attracted to that it is less attracted to water so the ionic
water so the ionic lattice breaks up lattice breaks up less easily – IT IS LESS
more easily SOLUBLE

USE: barium sulphate’s insolubility is used as a test for sulphates

©HOPTON
Properties Down Group II
 Properties Down Group II
Reaction of Oxides with Hydrochloric/Nitric Acid
 Properties Down Group II

Reaction of Hydroxides with Hydrochloric/Nitric Acid

Properties Down Group II

SULPHATE HYDROXIDE
solubility solubility
DECREASES INCREASES
down the down the
group group
 Properties Down Group II
Solubility is determined by two factors:
Lattice dissociation enthalpy (energy needed to break up a
crystal lattice)
Hydration enthalpy (energy released when ions are hydrated)

Ionic size has an effect on these factors.

• Solubility of Hydroxides
• There is a decrease in lattice
dissociation enthalpy down the
group.
• This outweighs the change in insoluble
enthalpy of hydration.
• As a result, there is an slightly soluble
INCREASE in SOLUBILITY soluble
down the group.
soluble
 Properties Down Group II
Solubility is determined by two factors:
Lattice dissociation enthalpy (energy needed to break up a
crystal lattice)
Hydration enthalpy (energy released when ions are hydrated)

Ionic size has an effect on these factors.

Solubility of Sulphates
Magnesium and calcium
sulphates are soluble.

Anion >> Cation: so lattice

enthalpy does not vary much
down group as cation size soluble
changes. soluble

However, hydration enthalpy insoluble

decreases down the group.
insoluble
Therefore, solubility decreases
down the group.
Properties Down Group II
 Properties down group II
Thermal Stability of Carbonates

Carbonates of Group 1 are thermally stable:

Exception is lithium carbonate which decomposes to
give the oxide:

All group 2 carbonates decompose to form stable oxides.

E.g.
 Properties Down Group II
Explanation of stability of carbonates
• The positive ion attracts the
Polarising the carbonate ion delocalised electrons in the
carbonate ion towards itself.
• The carbonate ion becomes
polarised.
• If this is heated, the carbon
dioxide breaks free to leave the
metal oxide.

• The smaller the positive ion is, the higher the charge density, and the
greater effect it will have on the carbonate ion.
• As the positive ions get bigger as you go down the Group, they have less
effect on the carbonate ions near them.
• To compensate for that, you have to heat the compound more in order to
persuade the carbon dioxide to break free and leave the metal oxide.
• In other words, as you go down the Group, the carbonates become more
thermally stable.
(A similar explanation can be used for the stability of nitrates.)
Properties Down Group II
• Electrons occupy certain
discrete energy levels.

• When an electron is promoted

from its usual energy level to a
higher one, the atom becomes
excited.

• When the electron drops back

down to its ground state (usual
energy level), the atoms emits a
photon of light in the visible
range
– Meaning a certain amount of
energy that has a wavelength
corresponding to a certain
colour.
 Thermal decomposition
One theory of the thermal instability trend

The lower down the metal in the group the more thermally stable is
its hydroxide, nitrate, carbonate or sulphate etc.

This is because the polarising power of the cation increases up the

group with the smaller ionic radius,

AND, in most cases discussed here, the smaller the cation the
greater the lattice enthalpy of the oxide formed on decomposition
(meaning the oxide is more thermodynamically stable up the group).

Particularly for the tiny Li+ and Be2+ ions, the polarising effect
considerably reduces the stability of their compounds (e.g. BeCO3 is
quite unstable and Li2CO3 decomposes on gentle heating).
The 'polarising power' of a cation is a measure of its electric
field effect to attract and distort electron charge on a
neighbouring anion:

The cation polarising power increases with increase in charge

on the ion or decreasing the radius of the ion, both of which
increase the intensity of the electric field - a high charge
density.

This high charge density effect polarises the O-H in

hydroxides, the N-O bond in nitrates and C-O bond in the
carbonate ion.

Within a group of cations e.g. groups 1 or 2, the effect of the

charge density increases up the group as the atomic/ionic
radius gets smaller (for the same positive charge). So the
hydroxide, carbonate or nitrate tend to get less thermally
stable up the group.
The trend down Groups I & II of increasing thermal stability of the
MCO3 carbonate is also paralled by an increase in ionic character of
the carbonate (also nitrates and hydroxides).

As you go up Groups I & II the radius of the Group I & II ions, (M+
& M2+), decreases, therefore the ion's electric field effect is much
stronger, i.e. increase in polarising power of the metal ion.

Therefore the polarising effect of the increasingly smaller Mn+ ion

on the outer electron clouds of the carbonate ion (or any other ion)
increases, distorting the electron clouds of the carbonate ion
towards the metal ion.

This increases the potential for orbital overlap i.e. increase in

covalent character of the metal ion - carbonate ion bond up the
group.

Therefore down the group, there is a decrease in covalent

character as the polarising metal ion gets larger.
The p-block
Elements
Position of p-block in periodic table
 What are p-block elements?

• p-block elements are the elements in which the last

electron enters ‘np’ orbital which include six groups of
elements i.e. group 13 to 18, boron family, carbon family,
pnicogens, chalcogens, halogens and noble gases.
 General Electronic Configuration &
Oxidation State

Group 13 14 15 16 17 18
G. E. C ns2 np1 ns2 np2 ns2 np3 ns2 np4 ns2 np5 ns2 np6
First B C N O Cl He
Group
G. O. S. +3 +4 +5 +6 +7 +8
Other +1 +2 +3 +4 +5 +6
O. S.
-4 -3 +2 +3 +4
-2 +1 +2
• As metals,non-metals and
metalloids exist only in p-
block of periodic table.

• The heaviest element in

each p-block group is
mostly metallic in nature.

• Non-metallic character of
elements decreases down
the group.
• Non metals have higher ionization enthalpy and electronegetivity
than the metals.

Hence metals form cations, and non metals form anions.

• Compounds formed between non metals are largely covalent in

nature, while the compounds formed by highly reactive non-metal
and metal have large difference in electronegativities.

p-block elements differ…

• Size and all the properties of size
because of this the lightest p-block elements show the same kind
of differences as the lightest s-block element i.e. lithium and
beryllium.

• Elements starting from boron are restricted to maximum

covalence of four (using 2s and three 2p orbitals).
 Introduction

1. Group 13 elements and their uses

2. Boron – Electronic structure, Chemical properties

3. Aluminium - Structure and properties

4. Equations

5. Conclusion
Group 13 elements: The boron
family
Gallium melts in the hand
 All of the elements form hydrides, oxides, and halides in the +3
oxidation state. The +1 oxidation state becomes more stable down the
group and is the most stable oxidation state for compounds of thallium

The most useful compound of boron is borax; the most

commercially important element is aluminium.
Important Reactions of Boron Group

1. The elements react sluggishly, if at all, with water:

2Ga(s) + 6H2O(hot) → 2Ga3+(aq) + 6OH−(aq) +3H2(g)

2Tl(s) + 2H2O(steam) → 2Tl+(aq) + 2OH− + H2(g)

2. When strongly heated in pure O2, all members form oxides:

4 M(s) + 3O2(g) → 2M2O3(s) (M = B, Al, Ga, In)

4Tl(s) + O2(g) → 2Tl2O(s)

Oxide acidity decreases down the group:

B2O3 (weakly acidic) > Al2O3 > Ga2O3 > In2O3 > Tl2O (strongly
basic) for Tl, the +1 oxide is more basic than the +3 oxide.
3. All members reduce halogens (X2):

2M(s) + 3X2(g) → 2MX3(l) (M = B, Al, Ga, In)

2Tl(s) + X2(g) → 2TlX(s)

BX3 are volatile covalent molecules. Trihalides of Al, Ga, and In are
(mostly) ionic solids but occur as covalent dimers in the gas phase;
in this way, the 3A atoms attains a filled outer level.

Reaction of boron chloride with water to form boric acid and hydrochloric
acid.

BCl3(l) + 3H2O(l) → B(OH)3(aq)* + 3HCl(aq)

* can also be, but less accurately, written as H3BO3.

Reaction of Aluminium chloride with a little water it rapidly, and

exothermically hydrolyses to form aluminium hydroxide and nasty fumes of
hydrogen chloride gas.

AlCl3(s) + 3H2O(l) → Al(OH)3(s) + 3HCl(g)

• However, if a large excess of water is rapidly added, a
weakly acidic solution of aluminium chloride is formed, with
the minimum of nasty fumes!

AlCl3(s) + aq → Al3+(aq) + 3Cl–(aq)

or more correctly:

AlCl3(s) + 6H2O(l) → [Al(H2O)6]3+(aq) + 3Cl–(aq)

The solution is slightly acidic, because the hexa–aqua

aluminium ion can donate a proton to a water molecule forming
the oxonium ion.

[Al(H2O)6]3+(aq) + H2O(l) ⇌ [Al(H2O)5OH]2+(aq) + H3O+(aq)

5. The overall reaction in the production of aluminum metal is
a redox process:

2 Al2O3 (s) + 3 C(s) 4 Al(s) + 3 CO2 (g)

This electrochemical process is carried out in the presence
of cryolite (Na3AlF6), which lowers the melting point of the
reactant mixture and takes part in the change.

6. A displacement reaction produces gallium arsenide, GaAs:

(CH3)3Ga(g) + AsH3 (g) _________________

 Important Compounds of Boron
Group Elements - I
1. Boron oxide, B2O3. Used in the production of borosilicate glass.
.
2. Borax, Na2[B4O5(OH)4] 8H2O. Major mineral source of boron
compounds and B2O3. Used as a fireproof insulation material
and as a washing powder (20-Mule Team Borax).

3. Boric acid, H3BO3 [ or B(OH)3]. Used as external disinfectant,

eyewash, and insecticide.

4. Diborane, B2H6. A powerful reductant for possible use as a

rocket fuel. Used to synthesize higher boranes, compounds that
.
led to new theories of chemical bonding.

5. Aluminum sulfate (alum), Al2(SO4)3 18H2O. Used in water

purification, tanning leather, and as an antiperspirant.
 Important Compounds of Boron
Group Elements - II
6. Aluminum oxide, Al2O3. Major compound in natural source
(bauxite) of Al metal. Used as abrasive in sandpaper, sanding
and cutting tools, and toothpaste. Large crystals with metal ion
impurities often of gemstone quality. Inert support for
chromatography. In fibrous forms, woven into heat-resistant
fabrics; also used to strengthen ceramics and metals.

7. Tl2Ba2Ca2Cu3O10. Becomes a high-temperature superconductor

at 125 K, which is readily attained with liquid Nitrogen. (77K)
 C-C : ethane(C2H6), benzene (C6H6), graphite, diamond
B-N : amine-borane(BNH6), borazine (B3N3H6), boron nitride,
borazon
Graphite & Boron Nitride
Influence of Transition Elements on
Group 3A(13)
Zeff increases for the larger 3A elements due to poor
shielding by d and f electrons.

The larger 3A elements have smaller atomic radii and larger

ionization energies than electronegativities than expected.

These properties influence the physical and chemical

behavior of these elements.
Features of Group 3A(13) Elements

Larger Group 3A elements exhibit multiple oxidation states.

They may lose either the np electron only, or both the np
and ns electrons.

The lower oxidation state becomes increasingly prominent

down the group, since the ns2 electrons form an inert pair.

Oxides of the element in the lower oxidation state are more

basic than oxides in the higher oxidation state.
In2O is more basic than In2O3.
• Boron – glasses, ceramics and
agriculture
• Aluminum – electrical devices and
construction materials
• Gallium – amplifiers, solar cells and
satellites
• Indium – coatings and alloys
• Thallium – photo electric cell, and toxics
 Boron
• Electronic structure – 1s2 2s2 2p1 Atomic radius – 90 pm.

• Due to this relatively small size of boron, the sum of its first three
ionization enthalpies is very high.

• This prevents it to form 3+ ions and forces it to form only covalent

compounds.

• In the trivalent state, boron can be called as electron deficient as

it will have only 6 electrons in its outer most orbit. Thus, Boron has
a tendency to accept a lone pair of electrons from another
compound to become stable.

• This property also makes the compound a Lewis acid.

• It is unreactive in crystalline form

• However, amorphous boron on heating in air forms B203.It reacts

with di nitrogen at high temperatures to form nitrides.

• B2O3 is acidic and reacts with basic oxides forming metal borates

• It does not react with acids and alkanes.

 1. Borax
It is the most important compound of boron. It is a white crystalline
solid of formula Na2B4O7⋅10H2O. Borax dissolves in water to give an
alkaline solution.

𝑁𝑎2 𝐵4 𝑂7 + 7𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 + 4𝐻3 𝐵𝑂3

Orthoboric acid

On heating, borax first loses water molecules and swells up. On

further heating it turns into a transparent liquid, which solidifies into
glass like material known as borax bead.

Δ Δ
𝑁𝑎2 𝐵4 𝑂7 ∙ 10𝐻2 𝑂 → 𝑁𝑎2 𝐵4 𝑂7 → 2𝑁𝑎𝐵𝑂2 + 𝐵2 𝑂3
sodium metaborate
 2. Orthoboric acid

Orthoboric acid, H3BO3 is a white crystalline solid, with soapy touch.

It is sparingly soluble in water but highly soluble in hot water.

It can be prepared by acidifying an aqueous solution of borax.

𝑁𝑎2 𝐵4 𝑂7 + 2𝐻𝐶𝑙 + 5𝐻2 𝑂 → 2𝑁𝑎𝐶𝑙 + 4𝐵 𝑂𝐻 3

It has a layer structure in which planar BO3 units are joined by

hydrogen bonds.

Boric acid is a weak monobasic acid. It is not a protonic acid but acts
as a Lewis acid by accepting electrons from a hydroxyl ion:

𝐵 𝑂𝐻 3 (𝑎𝑞) + 2𝐻𝑂𝐻(𝑙) → 𝐵 𝑂𝐻 − (𝑎𝑞) + 𝐻3 𝑂+ (𝑎𝑞)

4
pka = 9.2
• On heating, orthoboric acid above 370K forms metaboric acid, HBO2
which on further heating yields boric oxide, B2O3.

Δ Δ
𝐻3 𝐵𝑂3 → 𝐻𝐵𝑂2 → 𝐵2 𝑂3

3. Diborane, B2H6
• The simplest boron hydride known, is diborane. It is prepared by
treating boron trifluoride with LiAlH4 in diethyl ether.

4𝐵𝐹3 + 3𝐿𝑖𝐴𝑙𝐻4 → 2𝐵2 𝐻6 + 3𝐿𝑖𝐹 + 3𝐴𝑙𝐹3

• A convenient laboratory method for the preparation of diborane

involves the oxidation of sodium boron hydride with iodine

2𝑁𝑎𝐵𝐻4 + 𝐼2 → 𝐵2 𝐻6 + 2𝑁𝑎𝐼 + 𝐻2

Diborane is produced on an industrial scale by the reaction of BF3 with

sodium hydride.
450𝑘
2𝐵𝐹3 + 6𝑁𝑎𝑎𝑂𝐻 𝐵2 𝐻6 + 6𝑁𝑎𝐹
 Properties of diborane
1. Diborane is a colourless, highly toxic gas with a b.p. of
180 K.

2. Diborane catches fire spontaneously upon exposure to

air. It burns in oxygen releasing an enormous amount of
energy.

3. Reaction of ammonia with diborane gives initially

B2H6.2NH3, further heating gives borazine, B3N3H6
known as “inorganic benzene” .
The structure of diborane is shown below . The four terminal
hydrogen atoms and the two boron atoms lie in one plane. Above
and below this plane, there are two bridging hydrogen atoms. The
four terminal B-H bonds are regular two centre-two electron
bonds while the two bridge (B-H-B) bonds are different and can be
described in terms of three centre two Electron bond.
 Boron
Boron has low density and very low electrical conductivity, finds many
applications.

1. Boron fibres are used in making bullet-proof vest and light material
for aircraft.

2. The boron-10 isotope has high ability to absorb neutrons and there f
metal borides are used in nuclear industry as protective shields and
control rods.

3. The main industrial application of borax and boric acid is in the

manufacture of heat resistant glasses like glass-wool and fibreglass.

4. Borax is used as a constituent of medicinal soaps. An aqueous

solution of orthoboric acid is generally used as a mild antiseptic.
 Aluminum and other group 13
elements
• Sum of the first three ionization enthalpies is less, as
compared to Boron. Thus, it due to the easy tendency to lose
electrons It is able to form Al 3+.

• In the other elements, due to poor shielding effect of d and

f orbitals, the nucleus holds the outer most s electrons
tightly. Thus, only p bonding may be available for bonding.

• In all 3 elements, both +1 and +3 oxidation states are seen.

• The compounds in +1 state are more ionic than those in +3

state.
 Aluminum
1. Aluminium is the most abundant metal in the Earth’s crust
(8.3 % by mass). It is found in a mineral called bauxite.

2. Al is a bright silvery-white metal. It has a high electrical

and thermal conductivity.

3. It forms alloys with Cu, Mn, Mg, Si and Zn. Aluminium and
its alloys can be given shapes of pipe, tubes, rods, wires,
plates or foils and, therefore, find uses in packing, utensil
making, construction, aeroplane and transportation
industry.

4. The use of aluminium and its compounds for domestic

purposes is now reduced considerably because of their
toxic nature.
• Aluminum forms a very thin oxide layer. With di nitrogen
at high temperatures they form nitrides.

• It dissolves in mineral acids and aqueous alkalies and thus

show amphoteric character.

• All the group 13 elements except thallium show reactivity

towards halogens.

• Acid treatment of Al2O3 is important in water

purification:

2 Al2O3 (s) + 3 H2SO4 (l) → Al2(SO4)3 (s) + 4 H2O(l)

• In water, Al2(SO4)3 and CaO form a colloid that aids in

removing suspended particles.
 Aluminium oxide – Amphoteric
Nature
Reaction of aluminium oxide with acids:

It behaves as a basic oxide dissolving to form the chloride,

sulphate and nitrate salt in the relevant dilute acid.

Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O(l)

Al2O3(s) + 3H2SO4(aq) → Al2(SO4)3(aq) + 3H2O(l)

Al2O3(s) + 6HNO3(aq) → 2Al(NO3)3(aq) + 3H2O(l)

ionic equation: Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(l)

Reaction of aluminium oxide with strong
bases/alkalis:

The oxide also behaves as an acidic oxide by dissolving

in strong soluble bases to form aluminate(III) salts.

e.g.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2Na[Al(OH)4](aq)

forming sodium aluminate(III) with sodium hydroxide.

ionic equation:
Al2O3(s) + 2OH–(aq) + 3H2O(l) → 2[Al(OH)4]–(aq)

Therefore aluminium oxide is an amphoteric oxide,

because of this dual acid–base behaviour.
 Amphoteric nature of aluminium
hydroxide
The addition of limited amounts of the bases sodium
hydroxide or ammonia solution to an aluminium salt
solution.

[Al(H2O)6]3+(aq) + 3OH–(aq) → [Al(H2O)3(OH)3](s) +

3H2O(aq)

A white gelatinous precipitate of aluminium hydroxide

is formed.

Simplified equation: Al3+(aq) + 3OH–(aq) →

Al(OH)3(s)
The further addition of excess sodium hydroxide or ammonia
solution.

With excess ammonia there is no effect, but with excess

sodium hydroxide the aluminium hydroxide dissolves to form a
soluble aluminate complex anion – therefore exhibiting
amphoteric behaviour. since the hydroxide will also dissolve in
acids (paragraph below NaOH equation).

[Al(H2O)3(OH)3](s) + 3OH–(aq) → *[Al(OH)6]3–(aq) + 3H2O(aq)

Simplified equation: Al(OH)3(s) + 3OH–(aq) → *[Al(OH)6]3–(aq)

*The products will be an equilibrium mixture including

[Al(H2O)2(OH)4]–(aq) and [Al(H2O)(OH)5]2–(aq) too.

You could write the equation in terms of forming these species

too and any of the three possibilities should get you the
• The addition of sodium carbonate solution to an
aluminium salt solution.

Bubbles of carbon dioxide and a white gelatinous

precipitate of aluminium hydroxide are formed.

2[Al(H2O)6]3+(aq) + 3CO32–(aq) → 2[Al(H2O)3(OH)3](s) +

3CO2(g) + 3H2O(aq)

[Al(H2O)6]3+(aq) + CO32–(aq) → 2[Al(H2O)4(OH)2]+(aq) +

CO2(g) + 3H2O(aq)

This equation shows the hexaaquaaluminium ion acting

as a Bronsted–Lowry acid donating two protons to the
carbonate ion (B–L base) to form carbon dioxide and
water.
This reaction shows why 'aluminium carbonate' 'Al2(CO3)3' cannot
exist. The hydrated highly charged central metal ion is too acidic to
co–exist with a carbonate ion. The same situation applies to the
chromium(III) Cr3+ and iron(III) Fe3+ ions i.e. no chromium(III)
carbonate or iron(III) carbonate exists. However with a lesser
charged, lesser acidic ion, carbonates can exist, so there is an iron(II)
carbonate FeCO3.

The addition of excess sodium carbonate solution has no further

effect. Sodium carbonate is too weak a base to effect the amphoteric
nature of aluminium hydroxide and dissolve the aluminium hydroxide
precipitate.

All are, for simplicity, treated as octahedral complexes of 6 ligands –

either water H2O or hydroxide ion OH–.

[Al(H2O)6]3+ => [Al(OH)(H2O)5]2+ => [Al(OH)2(H2O)4]+ => [Al(OH)3(H2O)3](s)

precipitate
dissolving => [Al(OH)4(H2O)3]– => [Al(OH)5(H2O)]2– => [Al(OH)6]3–
 Extraction of Aluminum
• Hall found that mixing aluminum oxide (2045°C) with
cryolite (Na3AlF6) produced a mixture that melted at a
much lower temperature of 1012°C.

• The aluminum oxide is dissolved in molten cryolite and

contained in a graphite-lined iron tank. The graphite rods
used as an anode are consumed during the process.

Anode: C(s) + 2O2-(l) → CO2(g) +4e-

Cathode: 3e- +Al3+(l) → Al(l)

• The products are carbon dioxide and molten aluminum metal.

Because the aluminum is more dense than the aluminum
oxide-cryolite mixture, it collects at the bottom of the tank
and is drawn off periodically.
Raw materials for the electrolysis process:

Bauxite ore, made of impure aluminium oxide [Al2O3 made

up of Al3+ and O2– ions]

• Carbon (graphite) for the electrodes.

• Cryolite reduces the melting point of the ore and saves

energy, because the ions must be free to move to carry
the current

• Electrolysis means using d.c. electrical energy to bring

about chemical changes e.g. decomposition of a compound
to form metal deposits or release gases. The electrical
energy splits the compound!
• At the electrolyte connections called the anode
electrode (+, attracts – ions) and the cathode
electrode (–, attracts + ions). An electrolyte is a
conducting melt or solution of freely moving ions
which carry the charge of the electric current.

• At the positive anode, oxygen gas is formed (non–

metal*). This is quite a problem. At the high
temperature of the electrolysis cell it burns and
oxidises away the carbon electrodes to form toxic
carbon monoxide or carbon dioxide. So the electrode
is regularly replaced and the waste gases dealt with!
Aluminum Oxide
Anode:
6𝑂2− (𝑎𝑞) → 3𝑂2 (𝑔) + 12𝑒 −
3𝐶(𝑠) + 3𝑂2 (𝑔) → 3𝐶𝑂2 (𝑔)
Overall Anode reaction:
6𝑂2− 𝑎𝑞 + 3𝐶(𝑠) → 3𝐶𝑂2 𝑔 + 12𝑒 −

Cathode:
4𝐴𝑙 3+ (𝑎𝑞) + 12𝑒 − → 4𝐴𝑙(𝑙)

Overall cell reaction:

4𝐴𝑙 3+ (𝑎𝑞) + 6𝑂2− (𝑎𝑞) + 3𝐶(𝑠) → 4𝐴𝑙(𝑙) + 3𝐶𝑂2 (𝑔)
Gallium, Indium and Thallium

➢ The elements Gallium, Indium and Thallium are only

found in the form of miner components of various
minerals and the elements are produced or
extracted by electrolytic reduction in aqueous
solution

➢ Gallium, Indium and Thallium are relatively soft and

reactive, which readily dissolve in acids.
 Gallium, Ga
Gallium has the chemical symbol Ga and atomic number 31. It has
the electron configuration [Ar] 2s2 2p1 and +3 oxidation state.
The melting point is 29.8º C and therefore melts by increasing
room temperature by a little.

• Gallium is important because it forms gallium arsenide (GaAs),

which can convert light directly into electricity. Also due to
thermite reaction, aluminum can extract oxygen from water and
hydrogen is released.

• By combining gallium and aluminum, this protective layer does not

form and aluminum will reduce water to hydrogen. This alloy can
provide a great hydrogen source
 Gallium, Ga
• Gallium is one of three elements that naturally occur
as a liquid at or close to room temperature, the other
two being mercury and Cesium. Ga has a melting point
of 29.76°C and a boiling point of 2204°C.

• Gallium easily forms alloys with most metals, and is

used to create low melting alloys and used in low
temperature solders.

• Gallium has a liquid range of 2174°C, one of the

largest liquid ranges of any metal, so it has found use
in high temperature thermometers.
 Gallium, Ga
• Gallium is an important element in the electronics
industry and has applications as doping material in
semiconductors. One of the most important of these
materials is gallium arsenide, GaAs, which can produce
laser light directly from electricity and is used in
diode lasers and Light Emitting Diodes (LEDs).

• The fluorescent compound MgGa2O4 is used in

photocopiers.

• Due to it's melting point, gallium melts in our hands.

 Indium, In
Indium has the chemical symbol In and atomic number
49. It has the electron configuration [Kr] 2s22p1 and
may have +1 or +3 oxidation state. However the +3
oxidation state is more common. It is a soft malleable
metal and similar to gallium, indium can form InAs
which is found in photoconductors in optical
instruments.

Indium is also extracted by electrolytic process and like

gallium is also an important element in the electronics
industry.
 Indium, In

Many indium compounds find applications in semi

conducting materials for transistors,
thermistors and photo-active devices, e.g. A
thin layer of indium tin oxide can be found on
LCD displays, such as through the monitor in
which you are reading.
 Thallium, Tl
Thallium has the chemical symbol Tl and atomic number 81.
It has the electron configuration [Xe] 2s22p1 and has
the +3 or +1 oxidation state. Since thallium is heavier, it
has a greater stability in the +1 oxidation state (inert
pair effect). Hence, it is found more commonly in its +1
oxidation state.

Thallium is soft and malleable. It is very poisonous but

nevertheless it is still used, such as for high
temperature superconductors. For its toxicity, thallium
was widely used in insecticide and rat poison but in 1975,
its uses was prohibited. Currently its usage is limited
and must be handled with care.
• Thallium is extracted from the fine dusts
from the sulphide ores of other elements by
dissolution in warm dilute acids. It is then
separated from impurities and purified by
electrolysis and deposition.

• Thallium and all its compounds are extremely

toxic. The element itself has no major uses;
however the thallium (I) compound Tl2SO4 was
once used as rodenticide and ants killer. Its
use for these purposes has since been banned
in most countries due to its odourless and
tasteless nature making the risk of accidental
poisoning unacceptably high.
• The electrical conductivity of thallium sulphide
changes with exposure to infrared light, and so
this compound is used in photocells.

• Thallium oxide has been used to produce glasses

with a high refractive index, and is also used in
the manufacture of photocells.

• At one time, thallium sulphate was used in

medicine as a depilatory agent, and thallium
carbonate was used to treat mildew in textiles.
• Thallium bromide-iodide crystals have been used as
infrared optical materials. Thallium has been used in
treating ringworm and other skin infections; however,
its use has been limited because of the narrow margin
between toxicity and therapeutic benefits.

• Thallium also has two stable states, Tl (I) and Tl (III),

and Tl (II) is a mixed valence compound of monovalent
and trivalent Tl.

• Since the element is very poisonous the metal and its

compounds should be handled carefully.
• Thallium is a little more reactive and is
oxidized by air to get a tinge oxide.

• Thallium changes color when exposed to air

(metallic gray color to Bluish-grey tint).

• Thallium has no taste or odor warning its

presence.
• The influence of the non-metallic character in this Group is
reflected by the softness of the metals.

• The melting points of all the elements are high, but the melting
point of boron is much higher than that of beryllium in Group 2,
whereas the melting point of aluminium is similar to that of
magnesium in Group 2 (diagonal relationship).

• The densities of all the Group 13 elements are higher than those of
Group 2 elements.

• The ionic radii are much smaller than the atomic radii.
– This is because the atom contains three electrons in a quantum level
relatively far from the nucleus, and when they are removed to form
the ion the remaining electrons are in levels closer to the nucleus.

– In addition, the increased effective nuclear charge attracts the

electrons towards the nucleus and decreases the size of the ion.
Standing in Group 4A(14), Looking Backward
to 3A(13) and Forward to 5A(15)
 Introduction

❖ Group 14 Elements: The Carbon Family

❖ Carbon & Its Uses
❖ Silicon & Its Uses
❖ Germinium & Uses
❖ Tin & Its Uses
❖ Lead & Its Uses
❖ Atomic & Physical Properties
❖ Chemical Properties
 Atomic and physical properties: group 14 elements
Property Elements
Carbon Silicon Germanium Tin Lead
Atomic number 6 14 32 50 82
Atomic mass(g/mol) 12.01 28.09 72.60 118.71 207.2
Electronic configuration [He]2s22 [Ne]3s23p [Ar]3d104s24p2 [Kr]4d105s25 [Xe]4f145d10
2
p2 p2 6s26p2
Covalent radius/pm 77 118 122 140 146
Ionic radiusM4+/pm _ 40 53 69 78
Ionic radius M2+/pm _ _ 73 118 119
Ionization 1086 786 761 708 715
enthalpy/Kjmol-1
(∆iH)
Electronegativity 2.5 1.8 1.8 1.8 1.9
Density/g cm-3 3.51 2.34 5.32 7.26 11.34
Melting point/K 4373 1693 1218 505 600
Boiling point/K _ 3550 3123 2896 2024
Electrical resistivity/ohm 1014-1016 50 50 10-5 2 X 10-5
cm
 Chemical properties
Oxidation state:-
• Carbon and silicon have +4 oxidation state.
• C & Si have very rare +2 compounds.
• Ge, Sn & Pb show both +2 and +4 oxidation states.
• The +2 state is more stable than +4 state as we go down the group.
• Fajan’s rule:- “smaller is the cation, the greater is the covalent
character in its compounds”. Eg Sn4+ compounds are covalent and Sn2+
compounds are ionic in nature.
• Generally speaking down a p block group the element becomes more
metallic in chemical character.
• Carbon and silicon are essentially non–metals, germanium is a metalloid.
• Tin is basically metallic with a little non–metallic chemical character,
lead is a metal.
 Chemical properties (CONT----)
Catenation:-
• The property of self linkage leading to the formation of
long chains and rings is termed catenation.

• Carbon has a greater tendency of self linking than other

elements.

• Catenation tendency follows the order,

C >> Si > Ge ≈ Sn >> Pb
Bond C─C Si─Si Ge─Ge Sn─Sn
Bond enthalpy (Kjmol-1) 348 222 167 155

• Since, the M─M bond enthalpy decreases steadily from C to

Sn. Therefore, the catenation tendency also decreases down
the group.
Chemical properties (CONT----)
Formation of multiple bonds :- pi bonding

• Carbon forms stable multiple bonds with itself and with other
elements.

• >C=C< ─C≡C─ >C=O >C=N

─C≡N >C=S

• Other elements of this group show no tendency to form pi bonds.

• However a few compounds containing multiple bonds have been

isolated.

• Effect of pi bonding on the structure may be seen in graphite.

 Chemical properties (CONT---)

Hydride formation:-

• Covalent hydrides of the type MH4 are known for all group
14 elements except lead.

• Tendency of hydride formation decreases in going from C to

Pb.

• Carbon forms a large number of cyclic and acyclic hydrides

known as hydrocarbons.

• Silicon and germanium form fewer hydrides of the general

formula SinH2n+2 & GenH2n+2 known as silanes and germanes
respectively..
 Chemical properties (CONT---)
Oxide formation:-
• Group 14 elements form three types of oxides:-
MO(monoxide) MO2(Dioxide)
M2O3(MO+MO2)(Mixed oxide)

• All elements of group14 expect silicon form monoxides of the

formula MO.

• While CO is neutral, all other oxides are basic in character.

• Carbon monoxide(CO) is the most important monoxide.

• All group 14 elements form dioxides having the formula MO2.

• These oxides differ in their properties and structures.

 Chemical properties (CONT---)
Halide formation:-

• Elements of group 14 form the following types of halides,

MX4 type eg., CCl4 (carbon tetrachloride)
MHX3 type eg., CHCl3 (Chloroform)
MX2 type eg., SiCl2 (Silicon dichloride)

• Dihalides of Ge, Sn & Pb are more ionic in nature.

• The stability of dihalides increases in going down the group

• Tetrahalides of the type MX4 are known for all the elements of group14.

• Tetrahalides are tetradedral and covalent.

• The tetrahalides of all elements except of carbon undergo hydrolysis.

 Important Reactions of the Carbon Family - I
1. The elements are oxidized by halogens:

M(s) + 2X2(g) → MX4(l) (M = C, Si, Ge)

The +2 halides are more stable for tin and lead, SnX2
and PbX2.

• Reaction of chlorides with water:

SiX4(l) + 2H2O(l) → SiO2(s) + 4HCl(l)

2. The elements are oxidized by O2:

M(s) + O2(g) → MO2(g) (M = C, Si, Ge, Sn)

Pb forms the +2 oxide, PbO. Oxides become more basic down the group.
The reaction of CO2 and water provides the weak acidity of natural
unpolluted waters:

CO2(g) + H2O(l) ⇌ [H2CO3(aq)] ⇌ H+(aq) + HCO3−(aq)

 Important Reactions of the Carbon Family - II
3. Reaction of oxide with bases/alkalis:

It is a weakly acidic oxide dissolving very slowly in hot concentrated sodium

hydroxide solution to form sodium silicate.

SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)

or simplified ionic equation: SiO2(s) + 2OH–(aq) → SiO32–(aq) + H2O(l)

It is a weakly acidic oxide dissolving sodium hydroxide solution to form

sodium carbonate.

CO2(g) + 2NaOH(aq) → Na2CO3(aq) + H2O(l)

ionic equation: CO2(g) + 2OH–(aq) → CO32–(aq) + H2O(l)

With excess of carbon dioxide, sodium hydrogencarbonate is formed.

CO2(g) + Na2CO3(aq) + H2O(l) → 2NaHCO3(aq

Important Reactions of the Carbon Family - II

4. Air and steam passed over hot coke produce gaseous fuel
mixtures (producer gas and water gas):

C(s) + air(g) + H2O(g) → CO(g) + CO2(g) + N2(g) + H2(g)

(not balanced)
5. Hydrocarbons react with O2 to form CO2 and H2O. the
reaction for methane can be adopted to yield heat or
electricity:
CH4(g) + 2 O2(g) → __________________

The gas is used to make other organic compounds and as a

fuel in welding.
Important Reactions of the Carbon Family- III

6. Freons (chlorofluorocarbons) are formed by fluorinating

carbon tetrachloride:
CCl4(l) + HF(g) → CFCl3 (g) + HCl(g)

Production of trichlorofluoromethane (Freon-11), the

major refrigerant in the world, is being eliminated
because of its severe effects on the environment, the
ozone destruction in the stratosphere.

7. Silica is reduced to form elemental silicon:

SiO2(s) + 2 C(s) → Si(s) + 2 CO(g)
This crude silicon is made ultrapure through zone refining
for the manufacture of computer chips.
Important Compounds of the Carbon Family - I

1. Carbon monoxide, CO. Used as a gaseous fuel as a precursor for

one-carbon organic compounds, and as a reactant in the purification
of nickel. Formed in internal combustion engines and released as a
toxic air pollutant.

2. Carbon dioxide, CO2. Atmospheric component used by

photosynthetic plants to make carbohydrates and O2. The final
oxidation product of all C - based fuels; its increase in the
atmosphere is leading to global warming. Used industrially as a
refrigerant gas, blanketing gas in fire extinguishers, and
effervescent gas in beverages. Combined with NH3 to form urea for
fertilizers and plastics manufacture.

3. Methane, CH4. Used as a fuel and in the production of many organic

compounds. Major component of natural gas. Formed by anaerobic
decomposition of plants (swamp gas) and by microbes in termites
and certain mammals. May contribute to global warming.
Important Compounds of the Carbon Family - II

4. Silicon dioxide, SiO2. Occurs in many amorphous (glassy) and

crystalline forms, quartz being the most common. Used to make
glass and as an inert chromatography support material.

5. Silicon carbide, SiC. Known as carborundum, a major industrial

abrasive and a highly refractory ceramic for tough, high-temperature
uses. Can be doped to form a high-temperature semiconductor.

6. Organotin compounds, R4Sn. Used to stabilize PVC (polyvinyl

chloride) plastics and to cure silicone rubbers. Agricultural biocide
for insects, fungi, and weeds.

7. Tetraethyl lead, (C2H5)4Pb. Once used as a gasoline additive to

improve fuel efficiency, but now removed because of its inactivation
of auto catalytic converters. Major source of lead as a toxic air
pollutant.
 Roman baths such as these in
Bath, England, used lead pipes for water

Source: Getty Images

Lead (II) oxide
 Carbon
Introduction
• Symbol :-C.
• Latin word:- "carbo" meaning"charcoal"
• Atomic Number = 6, Atomic Mass = 12.01
• Most common element: graphite, diamonds and coal.
• Most common compounds:- Hydrocarbons and Carbon
dioxide.

Physical Properties
• Carbon is a soft, dull gray or black non-metal that can
be scratched with a fingernail.

• The density of carbon as graphite is 2.267 g/mL, which

means it will sink in water.
 Carbon

• Carbon and silicon are two elements which form giant covalent structures i.e.
they are high melting and insoluble solids.

• Carbon (diamond) and silicon form networks based on tetrahedral arrangements

of C–C or Si–Si bonds around each atom. Both are very hard substances because
of the strong bonding, diamond is harder because the smaller C atoms give
shorter stronger bonds. Both are poor conductors of electricity because the
outer electrons are strongly held and localised between the two atoms of any
bond.
 Carbon
• Carbon in the form of graphite, forms hexagonal ring layers
in which the three C–C single bonds are supplemented by
delocalised electron bonding from the 4th out electron of
carbon. This makes graphite a moderately good electrical
conductor as the electrons can move freely through a layer.
The layers are held together by weak inter–molecular
forces and easily slip over each other making graphite a
'slippery' brittle solid. But as a giant covalent structure it is
still high melting and insoluble.

• mpt 3547°C; bpt 4827°C; very hard colourless/light

coloured diamond (poor conductor) or dark softish/slippery
crystals of graphite (moderate conductor of
heat/electricity).

• Graphite is used as a lubricant.

 Carbon-uses
Diamond
• Jewellery
• Manufacturing tools
• In making dies

Graphite
• Lubricant at high temperature
• Manufacturing lead pencils

Coal
• Fuel
• Manufacturing coal tar, coke and coal gas
• Manufacturing synthetic petrol
 SILICON
Introduction
• Symbol :-Si.
• Latin word:- “Silicium”
• Atomic Number = 14, Atomic Mass = 28.09
• Most common compounds:-Silicon dioxide (SiO2),Silicon
carbide (SiC),Sodium silicate (Na2SiO3) and Silicon
tetrachloride (SiCl4)

Physical Properties
• Crystalline silicon has a metallic grayish color
• Silicon is relatively inert, but it is attacked by dilute
alkali and by halogens
• Silicon transmits over 95% of all infrared wavelengths
(1.3 - 6.7 mm)
 Silicon-uses

• Electronic devices such as transistors, diodes

and chips

• For producing ferrosilicon

• As a deoxidiser in steal industry

• Important to plant and animal life

 Germanium
Introduction
• Symbol :-Ge
• Latin word:- “Germania”
• Atomic Number = 32, Atomic Mass = 72.60
• Most common compounds:- Oxide(s): GeO, GeO2 Chloride(s):
GeCl2, GeCl4 , Hydride(s): GeH4, Ge2H6

Physical Properties
• Germanium is a lustrous, hard, gray-white semi-metallic
element
• Germanium expands as it freezes
• It is a semiconductor
• Germanium and the oxide are transparent to infrared
radiation
 Germanium-uses

• Semiconductor devices

• Making prisms, lenses and windows in instruments

based on IR

• As catalyst
 Tin
Introduction
• Symbol :-Sn
• Latin word:- “Stannum”
• Atomic Number = 50, Atomic Mass = 118.69
• Most common compounds:-SnF4, Sncl4, Snbr4 and SnCl2

Physical Properties
• Tin is a malleable silvery-white metal which takes a high
polish
• It possesses a highly crystalline structure and is
moderately ductile.
• When a bar of tin is bent, the crystals break, producing a
characteristic 'tin cry‘.
• Tin has a cubic structure.
• Upon warming, at 13.2°C gray tin changes to white
 Tin-uses
• For tinning of copper and brass utensils

• For making tin foils for wrapping cigarettes

• For making alloy:- solder, bronze and gun metal

• Sno2 coated glass is scratch resistant i.e. aircraft

windows

• Used in agriculture to control fungi such as potato

blight
 Lead
Introduction
• Symbol :-Pb
• Latin word:- “plumbum”
• Atomic Number = 82, Atomic Mass = 207.19
• Most common compounds:- PbCl2 ,PbO2 ,Pb(NO2)2
,Pb3O4 ,Pb(CH3)4

Physical Properties
• Lead is a soft, malleable and poor metal
• It is also counted as one of the heavy metals
• Metallic lead has a bluish-white color after being
freshly cut, but it soon tarnishes to a dull grayish color
when exposed to air
• Lead has a shiny chrome-silver luster when it is melted
into a liquid
 Lead-uses

• For making water pipes

• Lead storage battery

• For making bullets, shots, etc

• Alloys:- solder

• Used for preparing high refractive index glasses

Group 15 - Pnictogens
 Group 15 elements - sometimes called
“Pnictogens”

Much of the important chemistry of the group 15 elements can be

understood on the basis of their electronic structure. Since the elements
have a [core] ns2 np3 electron configuration, neutral group 13 compounds can
form up to five bonds. This provides for two common oxidation states (+3
and +5) electrons (with a complete octet) around the group 15 atom so such
compounds are called “electron-rich”.
 Group 15
General characteristics:-

Electronic confgn: ns2 np3

▪ Extra stable due to half-filled p-confgn.
Because of the same reason, they have higher
ionization enthalpies than gr-14 elements
(Carbon family).

▪ They are very small in size from As to Bi

due to completely filled d- and f- orbitals in
heavier members (they have poor shielding
effect).
 Group 15
Physical properties:
❖ Metallic character increase down the group
❖ Bi is a strong metal due to higher I.E. because of its
small size
❖ Except nitrogen, all show allotropy

Chemical properties
❖ Oxidation states: -3, +3, and +5
❖ The tendency to show -3 state decreases as we go down
the group due to an increase in size and metallic
character
❖ The stability of +3 increases down the group whereas
that of +5 decreases due to INERT- PAIR effect
❖ Bi shows +5 only with fluorine (BiF5) due to the high
polarizing power of fluorine.
 Group 15
Consequences of inert-pair effect
✓ Nitrogen compounds disproportionate in acid
solutions.
3HNO2 HNO3 + H2O + 2NO

✓ Similarly, in case of phosphorus nearly all

intermediate oxidation states
disproportionate into +5 and –3 both in alkali
and acid.

✓ But the +3 oxidation state in case of arsenic,

antimony and bismuth becomes increasingly
stable and do not undergo disproportionation.
Anomalous properties of
Nitrogen
➢ It can show a maximum covalency of four only whereas
others show 5 and 6. E.g.:- PCl5 and PF6. This is due to
the absence of vacant d-orbitals in N-atom.

➢ It forms strong pπ-pπ multiple bonds due to its small

size. This is why it exists as a diatomic molecule with a
triple bond between two N-atoms. Others do not form
such bonds b’coz their atomic orbitals are so large and
diffused that they can not have effective overlapping.

➢ N does not catenate. This is because N-N bond is weaker

than the P-P bond due to the high interelectronic
repulsions of the non-bonding in the N-N due to the
small size of N atom.
 Group 15

Except nitrogen and bismuth, all other

elements of this group show allotropy.
e.g.
Phosphorus exists as - white, black or red
phosphorus

Arsenic exists as - yellow or grey arsenic

Antimony exists as - yellow or silvery

grey allotropic forms.
 14.0
N Nitrogen [He] 2s22p3
7
31.0
Phosphoru
P s [Ne] 3s23p3
15
74.9
As Arsenic [Ar] 3d104s24p3
33
121.8
Sb Antimony [Kr] 4d105s25p3
51
209.0
Bi Bismuth [Xe] 4f145d106s26p3
83
 Group 15
• Group 5 elements can form 3 covalent
bonds
– Sharing the 3 unpaired electrons
– Gives compounds with oxidation state of
+3 or –3 for group 5 element

• Each atom has a lone pair of electrons

– Enables atoms to form dative covalent
bonds
– When they do this Group 5 elements can
form some compounds with oxidation state
of +5 for the Group 5 element
Reaction of nitrogen with oxygen
At high temperatures e.g. in car engines, nitrogen(II) oxide
(nitrogen monoxide) is formed.

N2(g) + O2(g) → 2NO(g)

and the nitrogen(II) oxide rapidly reacts in air to form

nitrogen(IV) oxide (nitrogen dioxide).

2NO(g) + O2(g) → 2NO2(g)

The theoretical highest oxide is N2O5 nitrogen(V) oxide

(nitrogen pentoxide) and does exist.
 Reaction of nitrogen oxides with
water
• Nitrogen(IV) oxide dissolves to form an acidic solution of
weak nitrous acid and strong nitric acid.

2NO2(g) + H2O(l) → HNO2(aq) + HNO3(aq)

or 2NO2(g) + 2H2O(l) → HNO2(aq) + H3O+(aq) + NO3–(aq)

• NO and N2O are neutral oxides but nitrogen(V) oxide is

strongly acidic and dissolves to form nitric acid.

N2O5(s) + H2O(l) → 2HNO3(aq)

or N2O5(s) + 3H2O(l) → 2H3O+(aq) + 2NO3–(aq)

• Reaction of nitrogen oxides with acids:

None, only acidic (N2O3 (very unstable), NO2 and N2O5) or neutral
(N2O and NO), in nature.

• Reaction of nitrogen oxides with bases/alkalis:

Nitrogen(IV) oxide or nitrogen dioxide forms sodium nitrite and

sodium nitrate with sodium hydroxide solution.

2NO2(g) + 2NaOH(aq) → NaNO2(aq) + NaNO3(aq) + H2O(l)

ionic equation: 2NO2(g) + 2OH–(aq) → NO2–(aq) + NO3–(aq) + H2O(l)

As well as being a neutralisation reaction, it is also a redox reaction,

the oxidation states of oxygen (–2) and hydrogen (+1) do not change
BUT the oxidation state of nitrogen changes from two at (+4) to one
at (+3) and one at (+5). The simultaneous change of an element into
an lower and upper oxidation sate is sometimes called
disproportionation.
• Reaction of nitrogen with chlorine:
None, but the unstable yellow oily liquid chloride can be made
indirectly.

• Reaction of chloride with water:

Slowly hydrolyses to form weak nitrous acid and strong

hydrochloric acid.

NCl3(l) + 2H2O(l) → HNO2(aq) + 3HCl(aq)

or NCl3(l) + 2H2O(l) → HNO2(aq) + 3H+(aq) + 3Cl–(aq)

or NCl3(l) + 5H2O(l) → HNO2(aq) + 3H3O+(aq) + 3Cl–(aq)

• Reaction of nitrogen with water:

Slightly soluble but NO reaction.

 Nitrogen
• Very abundant element (76% by mass)

• Very unreactive

• N2 unreactive because of strong triple

bond holding N’s together
– Bond enthalpy of N Ξ N is +945 kJ mol-1
(Bond enthalpy of N-N is +158 kJ mol-1)
– Hence most reaction of N2 have high EA and
require high T and catalysts to make them
occur
• Haber process- high T + Fe catalyst….
• Lightning or >2000ºC to make N2 react with O2
 Nitrogen

• Nitrogen is used in medicines, fertilizers,

explosives, and plastics
• The biggest commercial use for elemental
nitrogen gas is in the formation of ammonia in
the Haber process
• N is very electronegative and it is the only group
15 element that can form hydrides capable of
hydrogen bonding
• N has a wide range of oxidation numbers.
Nitrogen compounds are known to have every
whole number oxidation number from -3 to +5.
In addition, some fractional oxidation numbers
are known to exists.
• N can only form up to four bonds
Reactivity towards Hydrogen
• All the elements of Group 15 form hydrides of
the type EH3 where E = N, P, As, Sb or Bi.

• The stability of hydrides decreases from NH3 to

BiH3 due to decrease in their bond dissociation
enthalpy.

• Consequently, the reducing character of the

hydrides increases.

• Ammonia is only a mild reducing agent while BiH3

is the strongest reducing agent amongst all the
hydrides.
• Basicity also decreases in this order:
NH3 > PH3 > AsH3 > SbH3 > BiH3.
Reactivity towards Hydrogen
• Stability decreases b’coz bde
decreases

• Basicity decreases b’coz electron

density around the central atom
decreases due to increase in size

• Reducing nature increases b’coz bde

decreases

• BDE decreases b’coz size of E

increases
 Ammonia

• Ammonia is nitrogen
hydride, NH3

• Lone pair not involved

in bonding
– Dative covalent
bonds (dcb’s)
possible
 Ammonia
• NH3 is a base and
forms dcb’s to H+
ions to give
ammonium ions
(NH4+)
– Remember once dcb’s
formed no different
from cb’s!

• NH3 also forms dcb’s

(dichlorobenzenes)
with TM ions and is a
good ligand in
complexes
 Ammonia
• On a small scale ammonia is obtained from ammonium salts
which decompose when treated with caustic soda or lime.
2NH4Cl + Ca(OH)2 → 2NH3 + 2H2O + CaCl2
(NH4)2SO4 + 2NaOH → 2NH3 + 2H2O + Na2SO4

• On a large scale, ammonia is manufactured by Haber’s

process.
N2(g) + 3H2(g) → 2NH3(g)
• Enthalpy change = – 46.1 kJ mol–1
• Conditions for better yield are:-
• In accordance with Le Chatelier’s principle, high pressure
would favour the formation of ammonia.

• The optimum conditions for the production of ammonia are

a pressure of 200 atm, a temperature of ~ 700 K and the
use of a catalyst such as iron oxide with small amounts of
K2O and Al2O3 to increase the rate of attainment of
equilibrium.
Properties of Ammonia
• Ammonia gas is highly soluble in water as it
forms intermolecular H-bonds with water
molecules.
• It is a Lewis base as it can donate the lone pair
present on the N-atom.
• It donates the electron pair forming linkages
with metal ions and therefore form complex
compounds. This finds applications in detection
of metal ions such as Cu2+, Ag+:

Cu2+(aq) + 4NH3(aq) → [Cu(NH3)4]2+(aq) Deep blue

AgCl(s) + 2NH3(aq) → [Ag(NH3)2]Cl(aq)

White ppt Excess Soluble
Reactivity towards Oxygen
• All these elements form two types of oxides:
E2O3 and E2O5.

• The oxide in the higher oxidation state of

the element is more acidic than that of lower
oxidation state.

• Their acidic character decreases down the

group.

• The oxides of the type E2O3 of nitrogen and

phosphorus are purely acidic, that of arsenic
and antimony amphoteric and those of
bismuth(Bi2O3))is predominantly basic.
 Nitrogen Oxides

Name / Appearance Where it comes from

Formula
• Nitrogen • Colourless • Combustion
monoxide gas, turns processes
• NO to brown • Thunderstorms
NO2 in air • Formed in the soil
by denitrifying
bacteria
 Nitrogen Oxides

Name / Appearance Where it comes from

Formula
• Nitrogen • Brown gas • From oxidation of
dioxide (toxic) NO in the
• NO2 atmosphere
• Dinitrogen • Colourless • Formed in the soil
oxide gas by denitrifying
• N2O bacteria
 Nitrates
• 2 Kinds of nitrate ions involved in
the nitrogen cycle:
– Nitrate(III), NO2-
– Nitrate(V), NO3-

• Both are called nitrates, but

distinguished by showing OS of N
 Bonding in Nitrates
Nitrate(III) Nitrate(V)
The charge is delocalised By using its lone pair to a
over the two N-O bonds, dative covalent bond to an
which are equivalent oxygen atom, the nitrogen
increases its oxidation
state to +5
 Nitrates
Name and Commonly Properties
Formula called

•Nitrate(V) ion •Nitrate • Oxidising agent

•NO3- • Metal nitrate(V)
compounds are very
soluble in water
•Nitrate(III) ion •Nitrite • Can be reducing or
•NO2- oxidising agent
• Metal nitrate(III)
compounds are soluble
in water
 Nitric Acid
Large Scale Manufacture:- Ostwald process.
Based on catalytic oxidation of ammonia: Pt/Rh
4NH3 (g) + 5O2 (g) → 4NO(g) + 6H2O(g)
(from air) 500K; 9 bar

Nitric oxide thus formed combines with oxygen giving NO2.

2NO(g) + O2 (g) → 2NO2 (g)

Nitrogen dioxide so formed, dissolves in water to give HNO3.

3NO2(g) + H2O → 2HNO3(aq) + NO(g)

NO thus formed is recycled and the aqueous HNO3 can be

concentrated by distillation upto ~ 68% by mass. Further concentration
to 98% can be achieved by dehydration with concentrated H2SO4.
 Nitric Acid
• Lab. Preparation of Nitric acid:-

In lab, nitric acid is prepared by heating potassium nitrate or sodium

nitrate with conc. sulphuric acid in a glass resort.

NaNO3 + H2SO4 → NaHSO4 + HNO3

Properties of Nitric acid

In aqueous solution, nitric acid behaves as a strong acid giving
hydronium and nitrate ions.
HNO3(aq) + H2O(l) H3O+(aq) + NO3-(aq)
Concentrated nitric acid is a strong oxidising agent and attacks most
metals except noble metals such as gold and platinum. The products of
oxidation depend upon the concentration of the acid, temperature and
the nature of the material undergoing oxidation.
 3Cu + 8 HNO3(dilute) 3Cu(NO3)2 + 2NO + 4H2O

Cu + 4HNO3(conc.) Cu(NO3)2 + 2NO2 + 2H2O

Zinc reacts with dilute nitric acid to give N2O and with concentrated
acid to give NO2.

4Zn + 10HNO3(dilute) •→ 4 Zn (NO3)2 + 5H2O + N2O

Zn + 4HNO3(conc.) → Zn (NO3)2 + 2H2O + 2NO2

Some metals (e.g., Cr, Al) do not dissolve in concentrated nitric acid
because of the formation of a passive film of oxide on the surface.

Concentrated nitric acid also oxidises non–metals and their compounds.

Iodine is oxidised to iodic acid, carbon to carbon dioxide, sulphur to
H2SO4, and phosphorus to phosphoric acid.
 Uses of Nitric Acid
• In the mfr. of ammonium nitrate for fertilizer.

• In the mfr. of nitrates required for making explosives

and pyrotechnics.

• In making TNT, nitroglycerin

• In pickling of stainless steel, etching of glass

• As oxidizer in rocket fuels.

Group 16 - Chalcogens
Physical Properties
 Physical Properties
1. They have ns2 np4 general electronic configuration.

2. The elements of this group have lower ionisation enthalpy

values compared to those of Group 15 in the corresponding
periods - This is due to the fact that Group 15 elements have
extra stable half-filled p orbital electronic configurations.

3. Because of the compact nature of oxygen atom, it has less

negative electron gain enthalpy than sulphur.

4. Next to fluorine, oxygen has the highest electronegativity value

amongst the elements.

5. Oxygen and sulphur are non-metals, selenium and tellurium

metalloids, whereas polonium is a metal. Polonium is radioactive
and is short lived (Half-life 13.8 days).

6. The large difference between the melting and boiling points of

oxygen and sulphur may be explained on the basis of their
atomicity; oxygen exists as diatomic molecule (O2) whereas
sulphur exists as polyatomic molecule (S8).
 Oxidation states

1. Since electronegativity of oxygen is very

high, it shows only negative oxidation
state as –2 except in the case of OF2
where its oxidation state is +2.

2. The stability of +6 oxidation state

decreases down the group and stability
of +4 oxidation state increase (inert pair
effect).
Anomalous behaviour of Oxygen
1. The anomalous behaviour of oxygen, like other
members of p-block present in second period is
due to its small size and high electronegativity.
One typical example of effects of small size
and high electronegativity is the presence of
strong hydrogen bonding in H2O which is not
found in H2S.

2. The absence of d orbitals in oxygen limits its

covalency to four and in practice, rarely
exceeds two. On the other hand, in case of
other elements of the group, the valence shells
can be expanded and covalence exceeds four.
Reactivity with Hydrogen

1. All the elements of Group 16 form hydrides of

the type H2E (E = O, S, Se, Te, Po).
2. H2O H2S H2Se H2Te

BDE Decreases

Stability decreases

Acidity increases

Reducing nature increases

Reactivity towards Halogens

• The stability of the halides decreases in the

order F– > Cl– > Br– > I–.
• Amongst hexahalides, hexafluorides are the
only stable halides.
• They have octahedral structure.
• Sulphurhexafluoride, SF6 is exceptionally stable
for steric reasons.

Tetrafluorides, have sp3d hybridisation and thus,

have trigonal bipyramidal structures in
which one of the equatorial positions is occupied
by a lone pair of electrons. This
geometry is also regarded as see-saw geometry.
Reactivity with halogens

Dihalides have sp3 hybridisation and thus,

have tetrahedral structure.

The well known monohalides are dimeric in

nature. Examples are S2F2, S2Cl2, S2Br2,
Se2Cl2 and Se2Br2.

These dimeric halides undergo

disproportionation as given below:
2Se2Cl2 →SeCl4 + 3Se
 Dioxygen
1. Molecular oxygen, O2 is unique in being
paramagnetic inspite of having even number of
electrons.

2. Its combination with other elements is often

strongly exothermic which helps in sustaining
the reaction. However, to initiate the reaction,
some external heating is required as bond
dissociation enthalpy of oxgyen-oxygen double
bond is high (493.4 kJ mol–1).

Some compounds are catalytically oxidised, e.g,

2SO2 + O2 → 2SO3

5HCl + O2 → 2Cl2 + 2H2O

 Ozone
1. Ozone is an allotropic form of oxygen. It is too reactive
to remain for long in the atmosphere at sea level. At a
height of about 20 kilometres, it is formed from
atmospheric oxygen in the presence of sunlight. This
ozone layer protects the earth’s surface from an
excessive concentration of ultraviolet (UV) radiations.

2. Preparation:-When a slow dry stream of oxygen is

passed through a silent electrical discharge, conversion
of oxygen to ozone (10%) occurs. The product is known
as ozonised oxygen.

3O2 → 2O3 ∆H = +ve

Since the formation of ozone from oxygen is an endothermic

process, it is necessary to use a silent electrical discharge
in its preparation to prevent its decomposition.
 Ozone properties

Ozone is thermodynamically unstable with respect

to oxygen since its decomposition into oxygen
results in the liberation of heat (∆H is negative)
and an increase in entropy (∆S is positive). These
two effects reinforce each other, resulting in
large negative Gibbs energy change (∆G) for its
conversion into oxygen.
 Sulphur

Yellow rhombic sulphur = Monoclinic sulphur

Transition temp = 369 K

Both rhombic and monoclinic sulphur have S8

molecules.

At elevated temperatures (~1000 K), S2 is the

dominant species and is paramagnetic like O2
 Sulphur dioxide

Sulphur dioxide is formed together with a little

(6-8%) sulphur trioxide when sulphur is burnt
in air or oxygen:
S(s) + O2(g) →SO2 (g)

In the laboratory it is readily generated by

treating a sulphite with dilute sulphuric acid.
SO32- + 2H+(aq) → H2O(l) + SO2 (g)
Sulphur dioxide Uses

Sulphur dioxide is used

(i) in refining of petroleum and sugar
(ii) in bleaching wool and silk and
(iii) as an anti-chlor, disinfectant and preservative.

Sulphuric acid, sodium hydrogen sulphite and

calcium hydrogen sulphite (industrial chemicals)
are manufactured from sulphur dioxide.

Liquid SO2 is used as a solvent to dissolve a

number of organic and inorganic chemicals.
Oxoacids of Sulphur
 Sulphuric Acid
Sulphuric acid is manufactured by the Contact Process
which involves three steps:

burning of sulphur or sulphide ores in air to generate

SO2. S+ O2 → SO2

conversion of SO2 to SO3 by the reaction with oxygen in the

presence of a catalyst (V2O5)
2SO2 + O2 → 2SO3
absorption of SO3 in H2SO4 to give Oleum (H2S2O7).
SO3 + H2SO4 → H2S2O7

H2S2O7 + H2O → 2H2SO4

The favourable conditions for maximum yield are a pressure

of 2 bar and a temperature of 720K.
Properties of Sulphuric Acid
1. It dissolves in water with the evolution of a large
quantity of heat. Hence, care must be taken while
preparing sulphuric acid solution from concentrated
sulphuric acid. The concentrated acid must be added
slowly into water with constant stirring.

2. The chemical reactions of sulphuric acid are as a result

of the following characteristics: (a) low volatility (b)
strong acidic character (c) strong affinity for water and
(d) ability to act as an oxidising agent.

3. In aqueous solution, sulphuric acid ionises in two steps.

H2SO4 + H2O → H3O+ + HSO4- ( Ka1 = very large )
HSO4- + H2O → H3O+ + SO42- ( Ka2 = very low)
The larger value of Ka1 means that H2SO4 is largely
dissociated into H+ and HSO4- ions–.
Greater the value of dissociation constant (Ka), the stronger
is the acid.
Properties of Sulphuric Acid
4. 2MX + H2SO4 → 2HX + M2SO4 (X = F, Cl, NO3)
(M = Metal)

5. Concentrated sulphuric acid is a strong

dehydrating agent.
C12H22O11 → 12C + 11H2O
c-H2SO4

6. Hot concentrated sulphuric acid is a moderately

strong oxidizing agent.

Cu + 2H2SO4(conc.) → CuSO4 + SO2 + 2H2O

3S + 2H2SO4(conc.) → 3SO2 + 2H2O
C + 2H2SO4(conc.) → CO2 + 2SO2 + 2H2
Uses of Sulphuric Acid
• In the manufacture of fertilizers (e.g.,
ammonium sulphate, superphosphate).
• petroleum refining,
• manufacture of pigments, paints and dyestuff
intermediates,
• detergent industry,
• Metallurgical applications (e.g, cleansing metals
before enameling, electroplating and galvanising,
storage batteries,
• in the manufacture of nitrocellulose products
and,
• as a laboratory reagent.
 Acid Rain
Natural rain water has a pH of 5.6.

Naturally slightly acidic due mainly to CO2

Rain water with a pH lower than 5.6 is called

acid rain.

Acid rain is linked to damage in ecosystems and

structures.
 The Current Limits
• US Standard (Atmospheric
Concentration)
– SO2 1.2 mol/m3
– NO2 2.1 mol/m3
• Deposition limits (suggested)
– SO2 20-40 mol/m2 yr (wet and dry
deposition)
– NO2 40-80 mol/m2 yr (wet and dry
deposition)
http://www.epa.gov/ord/htm/CAAA-2002-report-2col-rev-4.pdf

http://www.epa.gov/airmarkets/arp/index.html
 Emissions
• Newton’s law of air pollution - What goes up must come
down!

• From emission rates we can define a deposition rate, but

not a distribution!

• OHIO river valley

– SO2 360 mmol/m2 yr.
– NO2 210 mmol/m2 yr.
• Northeast
– SO2 130 mmol/m2 yr.
– NO2 120 mmol/m2 yr.
• These levels are 2-10 times lower than emission levels!

• Where do the acidic emissions go?

 Causes of Acid Rain
• Natural Sources
– Emissions from volcanoes and from
biological processes that occur on the land,
in wetlands, and in the oceans contribute
acid-producing gases to the atmosphere

– Effects of acidic deposits have been

detected in glacial ice thousands of years
old in remote parts of the globe
 Causes of Acid Rain
• The principal cause of acid rain is from
human sources
– Industrial factories, power-generating
plants and vehicles
– Sulphur dioxide and oxides of nitrogen are
released during the fuel burning process
(i.e. combustion)
 Deposition of NOx and SO2
• Wet deposition
– Rain, snow, fog
– SO2 and NOx form HNO3 and H2SO4
– Soluble gasses that dissolve in raindrops
– The H cation goes into solution, causing acid rain

• Dry deposition
– Particulates and aerosols absorbed by plants or
deposited on surfaces
– Ammonia and sulfuric acid form ammonium sulfate,
a particle that water condenses around to form
clouds and thus aerosols. Land directly on
surfaces.
– If Nitric Acid doesn’t go into solution, it can
directly deposit on the ground
Formation of Acid Rain
 Formation of Acid Rain
• When water vapour condenses, or as the
rain falls, they dissolve in the water to
form sulphuric acid (H2SO4) and nitric
acid (HNO3).

• While the air is cleaned of the

pollutants in this way, it also causes
precipitation to become acidic, forming
acid rain
Formation of Acid Rain
 SO2 Chemistry
• Combustion processes produce SO2.
• SO2 can be dry deposited to the earth or
can be oxidized in the atmosphere
• Gas phase reactions: (1-5% hr)

SO2 + ·OH Þ M Þ HOSO2

HOSO2 + O2 Þ SO3 + HO2
SO3 + H2 O Þ M Þ H 2 SO4
__ __ __ __ __ __ __ __ __ __ __ __ __ __ _
net · OH + SO2 + O2 + H 2O Þ H2 SO4 + HO2
 NO2 Chemistry

• Combustion processes produce NOx.

• NOx can be dry deposited to the earth or
can be oxidized in the atmosphere
NOx + O3 Þ NO2 + O2
• Gas phase reactions: (hours)
NO + HO2 Þ NO2 + OH
NO2 + OH Þ M Þ HNO3
 NO2 Chemistry
• Gas/Liquid (cloud based reactions):
 Summary
Many natural and pollutant gases dissolved in the
air are non-metal oxides.
CO2, SO2, NO2

Non-metal oxides are acidic

𝐶𝑂2 𝑔 + 𝐻2 𝑂(𝑙) ⇌ 𝐻2 𝐶𝑂3 (𝑎𝑞)
2𝑆𝑂2 𝑔 + 𝑂2 𝑔 + 2𝐻2 𝑂(𝑙) ⇌ 2𝐻2 𝑆𝑂4 (𝑎𝑞)
4𝑁𝑂2 𝑔 + 𝑂2 𝑔 + 2𝐻2 𝑂(𝑙) ⇌ 4𝐻𝑁𝑂3

Processes that produce non-metal oxide gases as

waste increase the acidity of the rain.
Natural – volcanoes and some bacterial action
Man made – combustion of fuel
 Affected Areas
• Canada
– Acid rain is a problem in Canada

– Water and soil systems lack natural alkalinity

such as lime base
• Cannot neutralize acid

– Canada consists of susceptible hard rock such

as granite
• Do not have the capacity to effectively neutralize
acid rain
 Affected Areas
• Industrial acid rain is a substantial problem in
China, Eastern Europe and Russia and areas
down-wind from them.

• Acid rain from power plants in the Midwest

United States has also harmed the forests of
upstate New York and New England.

• This shows that the effects of acid rain can

spread over a large area, far from the source of
the pollution
 Effects of Acid Rain

• Harmful to aquatic life

– Increased acidity in water bodies

– Stops eggs of certain organisms (e.g. fish) to

stop hatching
• Changes population ratios
• Affects the ecosystem
 Effects of Acid Rain
• Harmful to vegetation
– Increased acidity in soil

– Leeches nutrients from soil, slowing plant growth

– Leeches toxins from soil, poisoning plants

– Creates brown spots in leaves of trees, impeding

photosynthesis

– Allows organisms to infect through broken leaves

 Geochemical Effects of Acid Rain
The ability of soils to neutralize some or all of the acidity of acid rainwater is called “buffering capacity.” High buffering capacities
lead to soils that do not become acidified. Differences in soils are an important reason why some areas that receive acid rain show
more damage than other areas that receive the same amount. “The ability of forest soils to resist acidity depends on the thickness
and composition of the soil, as well as the type of bedrock beneath the forest floor. Midwestern states like Nebraska and Indiana have
soils that are well buffered. Places like New York's Adirondack and Catskill Mountains, have thin soils with low buffering capacity.”
Alkaline Soils neutralize the acid directly and have the highest buffering capacity.
H+ +CaCO3 →Ca2+ + HCO3-
Granite soils and volcanic rocks are not good at neutralizing acid.
Thicker soils are better than thin ones because they have a larger ion exchange. Soils with negative and positively charged particles
will have hydrogen replace the positively charged particles. This is bad because the Na, NH4, Ca etc. are important as nutrients and
when they are leached away it buffers the acid but leaves the plants with little nutrients. Thin soils have smaller buffering capacities
because all nutrients are leached easily.
The ecological effects of acid rain can also be seen in the water environments. Acid rain flows to water sources after falling on land,
buildings, and roads. Most lakes and streams have a pH between 6 and 8, although some lakes are naturally acidic even without the
effects of acid rain. Acid rain primarily affects sensitive bodies of water, which are located in watersheds whose soils have a limited
ability to neutralize acidic compounds. Lakes and streams become acidic when the water itself and its surrounding soil cannot buffer
the acid rain enough to neutralize it. In areas where buffering capacity is low, acid rain also releases aluminum from soils into lakes and
streams; aluminum is highly toxic to many species of aquatic organisms.

Natalie Maida
Source: EPA,
geocities
Effects of Acid Rain
 Effects of Acid Rain

• Accelerates weathering in
metal and stone structures
– Eg. Parthenon in Athens,
Greece; Taj Mahal in Agra,
India

MSN Encarta http://www.lauraknauth.com/photos/france/thinker.jpg

 Effects of Acid Rain
• Affects human health
– Respiratory problems, asthma, dry coughs, headaches
and throat irritations

– Leeching of toxins from the soil by acid rain can be

absorbed by plants and animals. When consumed, these
toxins affect humans severely.

– Brain damage, kidney problems, and Alzheimer's

disease has been linked to people eating "toxic"
animals/plants.
 Acid Deposition - Biology
Freshwater Lakes

Since only about 10% of the water in lakes and streams comes from rainfall, the acidity of water of freshwater lakes and streams is mostly determined by the soil
and rock types of an area. An area that is most vulnerable to acidification is one that has granite or peat-based soil. Acidification of a lake occurs over a period of
time, but initially acidification of freshwater, causes it to be clear blue. This is due to the settling of decaying organic matter.

Wildlife

Even though the total amount of living organisms remains constant, the diversity of an acidified body of freshwater drops significantly. Soft bodied animals like
leeches, snails, and crayfish die with a very little change in acidity, which is often an indicator of acidification. Acidification of freshwater greatly affects fish
populations. A decrease in pH is often paired with an increase in toxic metals like aluminum and mercury. A decrease in pH and elevated aluminum concentration
will increase fish mortality, decrease fish growth, decrease egg production and embryo survival, and result in physiological impairment of adult fish. Aluminum in
the water can precipitate onto fish gills, which would inhibit diffusion and result in respiratory stress. Acid rain is extremely detrimental to amphibian populations.
Most amphibians lay their eggs in small, shallow ponds which receive most of their water from rainfall. A very small amount of acidic rainfall would kill any
embryos in these small ponds.

Trees

Acid rain does not directly kill trees. Acidic water dissolves the nutrients and minerals in the soil and washes them away before trees and plants can absorb them
out of the ground for use. Acid rain also releases toxic substances such as aluminum into the soil which in very small amounts are very harmful to trees. Trees
high up in the mountains are more at risk to receive acid, from acidic clouds and fog. The trees are often bathed in these clouds, which eats away at the waxy
protective coating on the leaves. After this occurs, the leaves cannot perform photosynthesis and the trees are left unhealthy, weak, and usually die from disease
or from insect attacks.

Matt Aschaffenburg,
http://www.doc.mmu.ac.uk/aric/eae/Acid_Rain/acid_rain.html
 Preventive Measures
• Reduce amount of sulphur dioxide and
oxides of nitrogen released into the
atomosphere
– Use less energy (hence less fuel burnt)

– Use cleaner fuels

– Remove oxides of sulphur and oxides of

nitrogen before releasing
• Flue gas desulphurization
• Catalytic Converters
 Preventive Measures

• Use cleaner fuels

– Coal that contains less sulphur

– "Washing" the coal to reduce sulphur content

– Natural Gas
 Preventive Measures

• Flue Gas Desulphurisation (FGD)

– Removes sulphur dioxide from flue gas (waste gases)

– Consists of a wet scrubber and a reaction tower

equipped with a fan that extracts hot smoky stack
gases from a power plant into the tower

– Lime or limestone (calcium carbonate) in slurry form

is injected into the tower to mix with the stack gases
and reacts with the sulphur dioxide present
 Preventive Measures
• (continued)
– Produces pH-neutral
calcium sulphate that
is physically removed
from the scrubber

– Sulphates can be used

for industrial
purposes

Scrubber at work
MSN Encarta
 Preventive Measures
• Use other sources of electricity (i.e.
nuclear power, hydro-electricity, wind
energy, geothermal energy, and solar
energy)
– Issue of cost

http://upload.wikimedia.org/wikipedia/commons/4/4e/Nuclear_Power_Plant_Cattenom.jpg
Reducing the effects of Acid Rain

• Liming
– Powdered limestone/limewater added to
water and soil to neutralize acid

– Used extensively in Norway and Sweden

– Expensive, short-term remedy

 Costs
• Total structural, ecological, and environmental
costs are estimated at 5 billion dollars per year
• Forests $1.75 B
• Agriculture $1.00 B
• Corrosion of Buildings $2.00 B
• Tourism and fishing $0.25 B

• Reduce SO2 Emissions by 40% $1-2 B

• Reduce SO2 Emissions by 50% $2-4 B
• Reduce SO2 Emissions by 70% $5-6 B

• 1990 Clean Air Act -0ver 50% reduction in

emissions by the year 2000
 Clean Air Act
Phases and Reductions
Title IV of the Clean Air Act set a goal of reducing annual SO2 emissions by 10 million tons below
1980 levels. To achieve these reductions, the law required a two-phase tightening of the restrictions
placed on fossil fuel-fired power plants.

Phase I began in 1995 and affected 263 units at 110 mostly coal-burning electric utility plants located
in 21 eastern and midwestern states. An additional 182 units joined Phase I of the program as
substitution or compensating units, bringing the total of Phase I affected units to 445. Emissions data
indicate that 1995 SO2 emissions at these units nationwide were reduced by almost 40% below their
required level.

Phase II, which began in the year 2000, tightened the annual emissions limits imposed on these large,
higher emitting plants and also set restrictions on smaller, cleaner plants fired by coal, oil, and gas,
encompassing over 2,000 units in all. The program affects existing utility units serving generators
with an output capacity of greater than 25 megawatts and all new utility units.

The Act also called for a 2 million ton reduction in NOx emissions by the year 2000. A significant
portion of this reduction has been achieved by coal-fired utility boilers that will be required to install
low NOx burner technologies and to meet new emissions standards.

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Group 17 - Halogens
 What are the halogens?

The name halogen comes from the Greek

words for salt-making.
 What is the electron structure of
the halogens?
All halogens have seven
fluorine
electrons in their outer shell. 2,7
This means that:

• They can easily obtain a full

outer shell by gaining one
chlorine
electron. 2,8,7

•They all gain an electron in

reactions to form negative ions
with a -1 charge.

•They have similar chemical bromine

properties. 2,8,8,7
 How do halogen molecules
exist?
All halogen atoms require one more electron to obtain a full outer shell
and become stable.

Each atom can achieve this by sharing one electron with another atom
to form a single covalent bond.

F + F F F

This means that all halogens exist as diatomic molecules:

F2, Cl2, Br2 and I2.
What are the general properties of
the halogens?
All the halogens are: They become darker in
colour down the group:
❑ non-metals and so do not
conduct electricity ❖ Fluorine is pale yellow

❑ Brittle and crumbly when ❖ Chlorine is green-

solid yellow

❑ Poisonous and smelly ❖ Bromine is red-brown

❖ Iodine is blue-black
 Trends in boiling point
Halogen molecules increase in size down the group. This leads to greater van
der Waals forces between molecules, increasing the energy needed to
separate the molecules and therefore higher melting and boiling points.

van der Waals

forces

fluorine iodine
atomic radius = 42 × 10-12 m atomic radius = 115 × 10-12 m
boiling point = -118 °C boiling point = 184 °C
 Trends in electronegativity
Electronegativity of the halogens decreases down the group due to an
increase in atomic radius.

Increased nuclear charge has no significant effect because there are more
electron shells and more shielding. Iodine atoms therefore attract electron
density in a covalent bond less strongly than fluorine.

fluorine iodine
atomic radius = 42 × 10-12 m atomic radius = 115 × 10-12 m
electronegativity = 4.0 electronegativity = 2.5
 Astatine

The name astatine comes from the Greek word for

unstable.
Astatine exists in nature in only very tiny amounts. It is
estimated that only 30 grams of astatine exist on Earth
at any one time. This is because it is radioactive, and its
most stable isotope (210At) has a half-life of only 8 hours.

It was first made artificially in 1940, by bombarding 209Bi with a-radiation.

What do you predict for these properties of astatine?

⚫ colour

⚫ state at room temperature

⚫ electronegativity.
 Reactions of the halogens
Halogens react with metals such as sodium and iron:

halogen + sodium → sodium halide

They also react with non-metals such as hydrogen:

halogen + hydrogen → hydrogen halide

They also take part in displacement reactions with halide ions, such as
the reaction that is used to make bromine from potassium bromide in
seawater:

potassium potassium
chlorine + bromide → bromine + chloride
 Reactions with hydrogen
The halogens react with hydrogen gas to product hydrogen halides.
For example:

Cl2(g) + H2(g) → 2HCl(g)

⚫ Chlorine and hydrogen explode in bright sunlight but react slowly in

the dark.

⚫ Bromine and hydrogen react slowly on heating with a platinum

catalyst.

⚫ Iodine combines partially and very slowly with hydrogen, even on

heating.
 Halogen displacement
reactions
Halogen displacement reactions are redox reactions.

Cl2 + 2KBr → 2KCl + Br2

To look at the transfer of electrons in this reaction, the following

two half equations can be written:

Cl2 + 2e- → 2Cl- 2Br- → Br2 + 2e-

What has been oxidized and what has been reduced?

❑ Chlorine has gained electrons, so it is reduced to Cl- ions.

❑ Bromide ions have lost electrons, so they have been oxidized to

bromine.
 Oxidizing ability of halogens
In displacement reactions between

increasing oxidizing ability

fluorine
halogens and halides, the halogen
acts as an oxidizing agent.
This means that the halogen: chlorine

➢ oxidizes the halide ion to the

halogen
➢ gains electrons bromine
➢ is reduced to form the halide
ion.
➢ What is the order of oxidizing
ability of the halogens
iodine
Oxidizing ability of halogens
 Halides as reducing agents
A substance that donates electrons in

increasing reducing ability

a reaction (i.e. is oxidized) is a
reducing agent because it reduces the fluoride

other reactant.

The larger the halide ion, the easier it

is for it to donate electrons and chloride
therefore the more reactive it is.

This is because its outermost electrons

are further from the attraction of the bromide
nucleus and more shielded from it by
other electrons. The attraction for the
outermost electrons is therefore
weaker.
iodide
 Chlorine and
disproportionation
 How does electron structure affect
reactivity?
The reactivity of alkali metals decreases going down the group. What is the
reason for this?

⚫ The atoms of each element get larger going F

down the group.

⚫ This means that the outer shell gets further

away from the nucleus and is shielded by more

decrease in reactivity
electron shells. Cl

⚫ The further the outer shell is from the

positive attraction of the nucleus, the harder
it is to attract another electron to complete
the outer shell.
Br

⚫ This is why the reactivity of the halogens

decreases going down group 7.
 How do the halogens react with
non-metals?
Halogens also react with non-metals. For example, halogens react with
hydrogen to create hydrogen halides

H + Cl H Cl

hydrogen chlorine hydrogen chloride

Unlike their reactions with metals, halogens share electrons with non-metals,
and so react to form covalent compounds.

All hydrogen halides are gases. They dissolve easily in water and become
strong acids.
 Hydrogen halides
Hydrogen halide Boiling point (°C)

HF 20
The hydrogen halides
are colourless gases HCl -85
at room temperature.
HBr -67

HI -35

Hydrogen fluoride has an unexpectedly

high boiling point compared to the other
hydrogen halides. This is due to
hydrogen bonding between the H–F
molecules.
Sodium halides and sulphuric
acid
 Identifying halide ions
Halides can be identified by their reaction with acidified silver nitrate
solution to form silver halide precipitates.

potassium silver potassium silver

chloride + nitrate → nitrate + chloride

KCl(aq) + AgNO3(aq) → KNO3(aq)

+ AgCl(s)

Silver chloride has a low solubility in water,

so it forms a white precipitate: the positive
result in the test for chloride ions.
What are the uses of halogens?
 Reaction of chlorine with
water
Chlorine is used to purify water supplies
because it is toxic to bacteria, some of
which can cause disease. Adding it to
water supplies is therefore beneficial for
the population.
However, chlorine is also toxic to humans,
so there are risks associated with gas leaks
during the chlorination process. There is
also a risk of the formation of chlorinated
hydrocarbons, which are also toxic.
Chlorination of drinking water raises questions about
individual freedom because it makes it difficult for
individuals to opt out.
 Bleach and the chlorate(I) ion
Household bleach commonly contains the chlorate(I) ion, ClO-, in
the form of sodium chlorate(I), NaOCl.

The chlorate(I) ion behaves as an oxidizing agent. It oxidizes the

organic compounds in food stains, bacteria and dyes.

ClO- + H2O + 2e- → Cl- + 2OH-

How many electrons are needed to balance this equation?

Has the chlorine been oxidized or reduced in the reaction?

The chlorine has been reduced because it has gained electrons. Its
oxidation state has decreased from +1 in ClO- to –1 in Cl-
 Halides
When halogens react with metals, they form compounds called halides. Many
naturally-occurring halides have industrial, household and medical applications.

Halide Formula Uses

caesium chloride CsCl Extraction and separation of

DNA

sodium NaAlF6 Electrolysis of aluminium

hexafluoroaluminate oxide

titanium(IV) chloride TiCl4 Extraction of titanium

lithium iodide LiI Electrolyte in batteries

potassium bromide KBr Epilepsy treatment in animals

 Uses of halides in
photography
Silver halides are used in photography.
Photographic film coated with a silver halide is exposed to light, causing the
halide to decompose to form silver. This appears as a black precipitate on the
photographic film.

Ag+ + e- → Ag
light

silver
mask precipitate

paper coated in
silver halide white paper
under mask
 Chapter 4 -
Introduction to
Transition Metals
I. Introduction to Transition Metal Complexes.
Classical complexes (Jorgenson and Werner)
Survey of ligand coordination numbers, geometries and types of ligands
Nomenclature
Isomerism
II. Bonding in Transition Metal Complexes.
Electron configuration of transition metals
Crystal field theory
Valence bond theory
Simple Molecular Orbital Theory
Electronic Spectra and Magnetism
III. Kinetics and Mechanisms of Inorganic Reactions.
Stability and lability
Substitution reactions
Electron transfer reactions
IV. Descriptive Chemistry of TMs.
V. Organometallic Chemistry
18 e- rule, , and  bonding ligands (synergistic bonding)
Metal carbonyls, synthesis, structure, reactions
Compounds with delocalized -conjugated organic ligands.
Reactions and catalysis