CHM 101 Dr.

ONIPEDE’s Part

Recommended texts: 1. Concise Inorganic Chemistry by J.D. Lee, 2. Inorganic Chemistry

by Catherine E. Housecroft and Alan G. Sharpe, Modern Inorganic Chemistry by C.
Chamber and A.K. Holliday

Comparative chemistry of group IA, group IIA and group 14.

Group IA (Hydrogen [H] (1s1) Lithium [Li] (1s22s1) Sodium [Na] (1s22s22p63s1), Potassium
[K] (1s22s22p63s23p64s1), Rubidium [Rb] (1s22s22p63s23p63d104s24p65s1) Cesium [Cs]
(1s22s22p63s23p63d104s24p64d105s25p66s1), Francium [Fr] ([Rn] 7s1),

Rn: 1s22s22p63s23p63d104s24p64d105s25p64f145d106s26p6

Group IA are called the alkali metals; they are all silvery-white metals but Cs is golden yellow
metal and excellent conductors of electricity, they are soft and highly reactive metals, (the
softness and low melting point is as a result of the elements contributing only one electron to the
molecular orbital). they have one electron in their outer valence electron and thus form univalent
ionic and colourless compounds the oxides and hydroxides are strong bases and the oxosalts are
very stable. Because of the one valence electron in their outmost shell, they have the largest
atomic size in their period. Nonetheless on losing the single valence electron, the outermost shell
is completely lost in ionization; hence they have the smallest ionic size in their period. They also
have the lowest ionization energy in their respective period.

They are very reactive and form simple ionic compound which are soluble in water, they are
reactive with air and water, and thus they are stored under inert solvent (hydrocarbon solvent).
They are found combined in nature as a result of their reactivity. They readily form alloy among
themselves (e.g. Na/K) and with other metals (e.g. Na/Hg), they tarnish rapidly in air giving a
layer of oxide, peroxide and dioxide. At ambient temperature all group IA, adopt a body centre-
cubic structure but at low temperature lithium forms hexagonal close-packed structure.

Lithium is the first member of the group and show marked difference from other members of the
group. But the head element usually has the diagonal relationship with the diagonally next
element to it. Sodium and potassium make about 4% of the earth crust. Despite their close
chemical similarities the elements do not occur together primarily because their ions are of
different sizes.

The ores of group IA include tourmaline (Na 3Li3Al6(BO3)3(SiO3)6F4) spodumene LiAl(SiO3)2

petalite (LiAl(Si2O5)2, borax (Na2B4O7.10H2O), mirabilite (Na2SO4), sylvite (KCl) carnallite
(KCl.MgCl2.6H2O), lepidolite K(Li,Al)3(Al,Si,Rb)4O10(F,OH)2 avogadrite (K,Cs)BF4), londonite
((Cs,K)Al4B4(B,Be)12O28 while francium is found in trace amount in ores of uranium and
thorium. The metals are all reactive and hence cannot be extracted by the furnace, but could only
be extracted by electrolysis.

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In flame lithium gives crimson, sodium gives yellow colour, potassium gives lilac, rubidium
gives red-violet and caesium gives blue colour.

Some selected properties of group IA metal are as tabulated below

Lithium Sodium Potassium Rubidium Cesium Francium

atomic symbol Li Na K Rb Cs Fr
atomic number 3 11 19 37 55 87
atomic mass 6.94 22.99 39.10 85.47 132.91 223
valence electron
2s1 3s1 4s1 5s1 6s1 7s1
configuration
melting point/boiling point
180.5/1342 97.8/883 63.5/759 39.3/688 28.5/671 27/—
(°C)
density (g/cm3) at 25°C 0.534 0.97 0.89 1.53 1.93 —
atomic radius (pm) 167 190 243 265 298 —
first ionization energy
520 496 419 403 376 393
(kJ/mol)
most common oxidation
+1 +1 +1 +1 +1 +1
state
ionic radius (pm)* 76 102 138 152 167 —
electron affinity (kJ/mol) −60 −53 −48 −47 −46 —
electronegativity 1.0 0.9 0.8 0.8 0.8 0.7
standard electrode potential
−3.04 −2.71 −2.93 −2.98 −3.03 —
(E°, V)
product of reaction with O2 Li2O Na2O2 KO2 RbO2 CsO2 —
type of oxide basic basic basic basic basic —
product of reaction with N2 Li3N none none none none —
product of reaction with X2 LiX NaX KX RbX CsX —
product of reaction with H2 LiH NaH KH RbH CsH —
*The values cited are for four-coordinate ions except for Rb+ and Cs+, whose values are given for the
six-coordinate ion.

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Comparative relationship between lithium and magnesium

1. Salt of lithium and magnesium exhibit high level covalent character in their bonding.
2. Carbonates of lithium and magnesium decompose to give the metal oxide and carbon-
dioxide, down the group IA the carbonates becomes increasingly stable to thermal
decomposition.
3. Lithium and magnesium form normal oxides with oxygen (group IA metals form
peroxide and dioxides), the peroxides of both metals can be formed by reacting LiOH or
Mg(OH)2 with H2O2
4. Lithium forms organometallic compounds similar to those of magnesium.
5. Lithium readily combines with nitrogen to give the nitride Li 3N, while Mg reacts with
nitrogen to give Mg3N2
6. LiF and MgF2 are sparingly soluble in water; the latter group IA fluorides are soluble.
7. LiOH is much less soluble in water than other alkali metal hydroxides Mg(OH) 2 is
sparingly soluble.
8. LiClO4 is much more soluble in water than the other alkali metal perchlorates, Mg(ClO 4)2
and the latter group IIA metal perchlorates are soluble.
9. Lithium and magnesium nitrates decompose on heating to give oxide, nitrogen oxide and
oxygen
4LiNO3 2Li2O + 2N2O4 + O2
2Mg(NO3)2 2MgO + 2N2O4 + O2
While sodium nitrate and the later alkali metal nitrates decompose to the give oxide

2MNO3 2MNO2 + O2 (M = Na, K, Rb, Cs)

Chemical properties of group IA metals

1. All group IA metals react with water to liberate hydrogen and forming hydroxides.
2Li +2H2O 2LiOH + H2
2. All group IA metals tarnish rapidly in dry air, Na, K, Rb and Cs form oxides of various
types, but lithium forms mixture of oxides and the nitride.
M+O Li2O, Li2O2, Na2O2, Na2O, KO2, RbO2
6Li +N2 2Li3N
Ozonides of K, Rb, and Cs can be prepared by heating the peroxide or dioxide with ozone
3KO2 +O3 3KO3
3. All group IA metals form azide by the reaction
2NaNH2 + N2O NaN3 + NaOH + NH3
But lithium reacts directly with nitrogen to give nitride
6Li +N2 2Li3N
4. All group IA metals react with hydrogen to form hydride.

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 2Na + H2 2NaH
Finely divided sodium hydride can ignite if left exposed to humid air and are difficult to
extinguish because carbon dioxide is reduced when it comes in contact with hot metal
hydride, the hydrides react with water liberating hydrogen.
5. All group IA metals react with halogen to form halides
2M + X2 2MX
All group IA metals react with interhalogen compounds forming ionic polyhalide
compounds
KBr + ICl K[BrICl]
6. In the presence of catalyst such as Fe, group IA metals react with liquid ammonia to form
a metal amide and hydrogen
M + NH3 MNH2 + ½H2
7. Lithium reacts on heating with carbon to form carbide.
2Li + 2C Li2C2
However other group IA members do not react directly but form similar carbide when
heated with ethyne or when ethyne is passed through a solution of the metal in liquid
ammonia.
Na + C2H2 NaHC2 Na2C2
8. All group IA metals form soluble carbonate with the exception of Li 2CO3 which is only
sparingly soluble in water
2NaHCO3 Na2CO3 + H2O + CO2
The bicarbonate are formed by bubbling carbon dioxide through saturated solution of the
carbonate.
Na2CO3(aq) + CO2 + H2O 2NaHCO3
9. All group IA metals form sulphate
2NaCl + H2SO4 Na2SO4 + 2HCl
10. All group IA metals form phosphides arsenides and stibnides
3M + P M3P
3M + As M3As
3M + Sb M3Sb
11. All group IA metals form sulphides, selenides and tellurides
2M + S M2S
2M + Se M2Se
2M + Te M2Te

Differences between lithium and other group IA metals

1. The melting and boiling point of Li are much higher than other group IA elements.
2. Lithium is much harder than other group IA metals.

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 3. Li react the least readily with oxygen, forming the normal oxide, it forms peroxide only
with great difficulty and higher oxides are unstable.
4. Lithium hydroxide is less basic than other hydroxide in the group hence many of its salts
are less stable.
5. Only Lithium form nitride Li3N in group IA no other member of the group forms nitride
but alkaline earth metals form nitride.
6. Only Lithium reacts directly with carbon to form carbide no other member of the group
react directly form carbide but group IIA metals react directly with carbon to form
carbide.
7. Lithium forms more complexes than other group IA metals and ammoniated salts such as
[Li(NH3)4]I exist as solids.
8. Li2CO3, Li3PO4 and LiF are insoluble in water and LiOH is only sparingly soluble. But
other group IA metals form soluble compounds. Magnesium salt show similar trends.
9. Halides and alkyls of lithium are far more covalent than their sodium counterparts.
10. Lithium ion itself and also its compounds are heavily hydrated than those of the rest of
the group.

Group IIA (Beryllium [Be] (1s22s2), Magnesium [Mg] (1s22s22p63s2), Calcium [Ca]
(1s22s22p63s23p64s2), Strontium [Sr] (1s22s22p63s23p63d104s24p65s2) Barium [Ba]
(1s22s22p63s23p63d104s24p64d105s25p66s2), Radium [Ra] ([Rn]7s2)

Rn: 1s22s22p63s23p63d104s24p64d105s25p64f145d106s26p6

They are called alkaline earth metals; they are all silvery in colour but Be and Mg are greyish
metal they are highly reactive metals; but are less reactive than group IA counterparts. They are
divalent and form colourless ionic compound, the oxides and hydroxides are less basic than their
group IA counterpart. Thus their oxosalts such as carbonates, sulphates, and nitrates are less
stable to heat. Their atomic and ionic sizes are smaller than their group IA counterpart but they
have higher densities than group IA metals. The group IIA metals have two valence electrons
which participate in bonding, hence are harder, have higher cohesive energy as well as higher
melting and boiling point than their group IA counterpart. Beryllium is the head element in the
group and hence shows marked difference from other members of the group.

They all dissolve in liquid ammonia like their group IA counterpart to give a blue solution. The
solutions decompose very slowly forming amide and hydrogen. Evaporation of the ammonia
from group IA metals yields the metals, but with group IIA metals evaporation of ammonia gives
hexammoniates of the metals; they slowly decompose to give amides.

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M(NH3)6 M(NH2)2 + 4NH3 + H2

They are highly reactive metals and hence cannot be extracted by oxidation or reduction in the
furnace, but can only be purified by electrolysis. The ores of alkaline earth metals include beryl;
Be3Al2Si6O18, phenacite ; Be2SiO4, kieserite: MgSO4.H2O, carnallite; KCl.MgCl2.6H2O,
Limestone; CaCO3, Gypsum; CaSO4.2H2O, celestite; SrSO4 and strontianite SrCO3, Baryte
BaSO4, radium is radioactive and found in uranium ore pitch blende.

The flame test of beryllium is white, magnesium is brilliant white, calcium; brick red, strontium
crimson, barium apple-green, radium; crimson red.

Some selected properties of alkaline earth metals are as tabulated below

Beryllium Magnesium Calcium Strontium Barium Radium

atomic symbol Be Mg Ca Sr Ba Ra
atomic number 4 12 20 38 56 88
atomic mass 9.10 24.31 40.08 87.62 137.34 226
valence electron configuration 2s2 3s2 4s2 5s2 6s2 7s2
839/149
melting point/boiling point (°C) 1287/2500 649/1105 768/1381 727/1850 700/1700
4
density (g/cm3) at 25°C 1.85 1.74 1.55 2.62 3.62 5.5
atomic radius (pm) 112 160 197 215 222 —
first ionization energy (kJ/mol) 899 737 590 549 503 509
most common oxidation state +2 +2 +2 +2 +2 +2
ionic radius (pm)* 31 72 100 118 135 148
electron affinity (kJ/mol) ≥0 ≥0 –2 –5 – 14 –
electronegativity 1.5 1.2 1.0 1.0 0.9
standard electrode potential
– 1.85 – 2.38 – 2.87 – 2.89 – 2.90 – 2.92
(E°, V)

Chemical properties of group IIA metals

1. Be reacts with steam but Ca, Sr, and Ba react with cold water to give hydroxide and
hydrogen, but Mg reacts with hot water to give oxide or hydroxide and hydrogen.
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 Ca+ 2H2O Ca(OH)2 + H2
Mg + 2H2O Mg(OH)2 + H2
Mg + H2O MgO + H2
2. Be(OH)2 is amphoteric but hydroxides of Mg, Ca, Sr and Ba are basic and the strength of
the bases increases from Mg to Ba.
The bicarbonates are produced by bubbling excess CO2 into the solution of the carbonate
CaCO3 + H2O + CO2 Ca(HCO3)2
3. All group IIA metals react with acids and liberates hydrogen, Be, reacts slowly, Be is
passivated by concentrated HNO3 forming thin layer of the oxide on the metal. Be being
amphoteric react with NaOH to liberate H2 and sodium berrylate. But others do not.
Mg + 2HCl MgCl2 + H2
Be + 2NaOH + 2H2O Na2[Be(OH)4] + H2
Or NaBeO2.2H2O + H2
4. All group IIA metals burn in oxygen to form the oxide
M+ ½O2 MO
All burn in dry air to give oxide and nitride
Mg + air MgO + Mg3N2
The thermal decomposition of the oxosalts (CO3, NO3, OH and SO4) also gives oxide.
5. All group IIA metals form sulphate, the solubility of the sulphate decreases down the
group. Be > Mg >> Ca > Sr > Ba.
CaCl2 + Na2SO4 CaSO4 + 2NaCl
6. All group IIA metals form nitrate by reaction of the nitric acid with carbonate, oxides or
hydroxides. But beryllium form both normal nitrate salt as well as basic nitrate salt.
BeCl2 + 2HNO3 + 2N2O4 Be(NO3)2.2N2O4 (50oC, vacuum) Be(NO3)2
o
(125 C) [Be4O(NO3)6].
7. All group IIA metals react with hydrogen to form hydride except beryllium. Beryllium
does not react directly with hydrogen and the hydride is made through lithium aluminum
hydride route.
M + H2 MH2 (M = Mg. Ca, Ba,Sr)
BeCl2 + LiAlH4 2BeH2 + LiCl + AlCl3
8. All group IIA metals react with halogens to form halide,
M + F2 MF2
M + Cl2 MCl2
M + Br2 MBr2
M + I2 MI2
9. All group IIA metals burn in dinitrogen and form ionic nitride M 3N2. But nitride of
beryllium is very volatile because covalence tendency of Be but other members of the
group form nonvolatile nitrides.
3Ca + N2 Ca3N2

7
 10. All group IIA metals and their oxides react at high temperature with carbon to give
carbide, the carbide of beryllium react with water to form methane while carbide of other
group IIA metals give ethyne on reaction with water.
BeO + 2C Be2C + CO
Ca + 2C CaC2
CaO + 3C CaC2 + CO

Comparative relationship between beryllium and aluminum

1. Beryllium and aluminum form carbide which forms methane on reaction with water
while other groups IIA carbides liberates ethyne on reaction with water.
2. Be and aluminum form covalent hydrides, halides and oxides other group IIA analogues
are predominantly ionic.
3. BeCl2 and AlCl3 fume in moist air, reacting to give HCl.
4. Beryllium oxide (BeO) and aluminum oxide (Al2O3) are amphoteric but magnesium
oxide is basic.
5. Beryllium and aluminum form [Be(OH)4]2 – and [Al(OH)4] – respectively in the presence
of excess OH – ions but Mg does not react with OH – ions.
6. Beryllium hydride is electron deficient and polymeric with multicenter bonding like
aluminum hydride.
7. Beryllium form many complexes not typical of group IA and group IIA.
8. Be and aluminum alike are rendered passive by nitric acid.
9. The standard electrode potential of Be and Al are – 1.85V and – 1.66V respectively
which are much closer than for Ca, Sr and Ba (– 2.87V, – 2.89V, – 2.90V) respectively.
10. Be salts are extensively hydrolysed.
11. Be salts are among the most soluble salts known.

Group 14 (Carbon [C] (1s22s22p2), Silicon [Si] (1s22s22p63s23p2), Germanium [Ge]

(1s22s22p63s23p64s23d104p2), Tin [Sn] (1s22s22p63s23p63d104s24p65s24d105p2) Lead [Pb]
(1s22s22p63s23p63d104s24p64d105s25p64f145d106s26p2) Flerovium [Fl]
2 2 6 2 6 10 2 6 10 2 14 10 2 6 14 10 2 2
(1s 2s 2p 3s 3p 3d 4s 4p 4d 5s 4f 5d 6s 6p 5f 6d 7s 7p )

Rn: 1s22s22p63s23p63d104s24p64d105s25p64f145d106s26p6

The group members varies from non-metal (C), to metalloid (Si, Ge) to metal (Sn, Pb) , they are
the most abundant element found on earth as they constitute the earth structure as well as
biological system (such as proteins, carbohydrates, and fats), all except lead exhibit allotropy.

8
Silicon is the second most abundant element by weight in the earth crust and it constitute 24% of
the earth crust.

The ores of group 14 elements include diamond, graphite, fullerene, charcoal, peat, Quartz; SiO 2,
zeolite;, Na2(Al2Si3O10)2H2O, Cassiterite; SnO2, teallite; PbSnS2, Galena; PbS, Anglesite;
PbSO4, boulangerite; Pb5Sb4S11, Winklers’ ore (75% Ag, 15% S 7% Ge)

Some selected properties of group 14 elements

Fleroviu
Carbon Silicon Germanium Tin Lead
m
atomic symbol C Si Ge Sn Pb Fl
atomic number 6 14 32 50 82 114
aomic mass 12.01 28.09 72.64 118.71 207.2 289.19
valence electron configuration 2s22p2 3s23p2 4s24p2 5s25p2 6s26p2 7s27p2
1420/328 327/17 61/150
melting point/boiling point (°C) 4100/5100 945/2850 232/2623
0 51
2.2 (Graphite) 11.7
density (g/cm3) at 25°C 2.33 5.32 7.27(White) 11.30
3.5 (diamond)
atomic radius (pm) 77 117 122 162 175 180
first ionization energy (kJ/mol) 1086 786 760 707 715 832.2
most common oxidation state +4 +4 +4 +4 +4 +4
ionic radius (pm)* 29 40 53 69 77.5
electron affinity (kJ/mol) – 122 – 134 – 119 – 107 – 35
electronegativity 2.6 1.9 2.0 2.0 1.8
standard electrode potential (E°,
0.21 – 0.86 – 0.18 – 0.12 0.79
V)

Differences between carbon silicon and other elements

1. The first element differ from the rest of the elements because of its smaller size and
higher electronegativity, hence have higher ionization energy, being more covalent and
being less metallic than the other members of the group.

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 2. Carbon form π – π multiple bonds such C=C, C≡C C=O, but other member of the group
do not.
3. Carbon has great ability to form chain (catenation) but other member form less chain and
their chains decreases in strength.
4. Carbon and silicon contain only s and p orbital electron hence differ from other members
of the group with d electrons hence other members show graded series.

Comparative relationship between B and Si

1. Boron and silicon form acidic oxides B2O3 and SiO2

2. Boron and silicon form many polymeric oxide structure
3. Boron and silicon form flammable gaseous hydride.

Reactions of group 14 elements

1. All group 14 elements form tetravalent hydride and carbon and silicon form series of
catenated molecule hydride.
CH3COONa + NaOH Na2CO3 + CH4
Al4C3 +12H2O 4Al(OH)3 + 3CH4
C2H5OH C2H4 + H2O
MX4 + LiAlH4 MH4 + LiAlX4
2. All group 14 elements form tetrahalides with halogens but lead form dihalides which are
stable.
Si + 2Cl2 SiCl4
C + 2Cl2 CCl4
Silicon and germanium can form pentahalide with fluorine
SiF4 + 2F – Si F 26 –
Only dihalide of lead is stable and no lead tetrabromide and tetraiodides are known.
Tin tetrahalide can form pentahalides and hexahalides in acidic solution
¿
SnCl4 + 2Cl SnCl 2−¿ 6

3. All group 14 elements react with oxygen to produce oxide, dioxide

2C + O2 2CO
2CO + O2 2CO2
Si + O2 SiO2
4. Group 14 elements react with nitrogen to form stable compounds
3Si + 2N2 Si3N4
But carbon produce cyanide ion which is very unstable compound but form stable
compound when complex with other metals or hydrogen

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 2C + N2 (CN)2
5. Carbon form stable sulphide with sulphur
CH4 + 4S CS2 + 2H2S

Atoms, molecules and structures

To predict structures of atoms in a molecule a law must be obeyed which depicts the orientation
of the atoms in the molecule. One of such rules is the Lewis octet rule.

The Lewis octet rule state that elements tend to bond in such a way that each atom has eight
electrons in its valence shell giving it the same configuration as a noble gas. The law could be
obeyed in the following steps

1. For compounds of molecular formula ABn place the atom with lower group number in the
centre because it needs more electrons to attain an octet; usually this is also the atom with
the lower electronegativity. NF3, the N has five electrons and so needs three electrons
whereas each F has seven and needs one electron, thus N goes to the centre with three F
around it.

If the atoms have the same group number, as in SO 3 or ClF3, place the atom with the
higher period number in the center, H can form only one bond, so it is never a central
atom.
2. Determine the total number of valence electrons available; for all molecules, add up the
valence electrons of all atoms.
(1 x 5) + (3 x 7) = 26 valence e –
For polyatomic ions add one e – for each negative charge of the ion or subtract one e – for
positive charge.

3. Draw a single bond from each surrounding atom to the central atom and subtract two
valence electrons for each bond. There must be at least a single bond between the bonded
atom.

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 Subtract 2 e – for each single bond from the total number of valence electrons available to
find the number remaining;
3 N – F bonds x 2 e – = 6 e – therefore 26 e – – 6 e – = 20 e – remaining.

4. Distribute the remaining electrons pairs so that each atom ends up with eight electrons (or
two for H). First place lone pairs on the surrounding (more electronegative) atoms to give
each an octet. If any electrons remain place them around the central atom. Then check
that each atom has 8 e –

Then the proposed structure is trigonal planar

Note: Hydrogen atoms form one bond, carbon atoms form four bonds, nitrogen atoms
form three bonds, oxygen atoms form two bonds and halogens form one bond when they
are surrounding atoms, fluorine is always a surrounding atom.
Examples find the structures of the following CCl2F2, H2S, OF2,

Another law that determines the shape of molecules is the Valence Shell Electron-Pair Repulsion
(VSEPR) theory the principle is that each group of valence electrons around a central atom is
located as far away as possible from the others in order to minimize repulsions.

Rule 1; Regions of high electron concentration (bonds and no lone pairs on the central atom)
repel one another and to minimize their repulsions, these regions move as far apart as possible
while maintaining the same distance from the central atom.

e.g. A molecule with two atoms attached to the central atom BeCl 2, there is no lone pair on the
central atom. To be as far as possible, the two bonding pair lie on the opposite sides of the Be
atom and so the electron arrangement is linear and hence VSEPR model predicts a linear shape
with angle 180o

Boron trifluoride molecule BF3; there are three bonding pairs attached to the central atom and no
lone pairs, to be as far as possible, the three bonding pair must lie at the corners of an equilateral
triangle. Because a F atom is attached to each bonding pair, the BF 3 molecule predicted by
VSEPR to be trigonal planar with angle 120o

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Methane CH4; there are four bonding pairs on the central atom, to be far apart as possible, the
four pairs the molecule must take up a tetrahedral arrangement around the C atom. Because the
electron arrangement is tetrahedral and an H atom is attached to each bonding pair, the molecule
is predicted by VSEPR to be tetrahedral with angle 109.5o

Phosphorus pentachloride PCl5: there are five bonding pairs and no lone pairs on the central
atom. VSEPR predicts they be far apart as possible hence three atoms lie in the corners of
equilateral triangle and two lie above and below the plane of the triangle; bond on the equatorial
plane are 120o the angle between axial and equatorial atoms is 90 o , the axial ClPCl bond angle is
180o and the shape is trigonal bipyramidal.

Sulfur hexafluoride SF6; there are six atoms attached to the central S atom and no lone pairs on
the central atom; VSEPR predicts that four pair of the atom be at the corner of a square on the
equator and the two pairs above and below the plane of the square, All its bond angles are either
90o or 180o and all the F atoms are equivalent. The shape is predicted to be octahedral.

Rule 2: there is no distinction between single and multiple bonds; a multiple bond it treated as a
single region of high electron concentration.

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Two electron pairs in a double bond stay together and they repel other bond or lone pair as a unit.
The three electron pairs in a triple bond also stay together and act like a single region of high
electron concentration. e.g. CO2 has similar structure to BeCl 2 even though CO2 has double
bonds, also CO2−¿¿
3 , the two pairs of electron in the double bond are treated as a unit and hence
the shape is as given by VSEPR is given as trigonal planar.

When there is more than one central atom, we consider the bonding about each atom
independently, e.g. ethylene CH2=CH2 each carbon has three atoms attached but no lone pairs,
the angle around each carbon is trigonal planar with angle 120o for HCH and HCC

Nitrate ion has nitrogen as the central atom and all oxygen attached to the central atom and it has
a trigonal planar structure.

Molecule with lone pairs on the central atom

VSEPR use AXnEm to identify different combinations of atoms and lone pairs attached to the
central atom. We let A represent a central atom, X an attached atom and E a lone pair. The sulfite
ion SO2−¿¿
3 is an example of AX3E. If there are no lone pairs on the central atom (an AX n
molecule), each region of high electron concentration corresponds to an atom and so the
molecular shape is the same as electron arrangement. However if lone pairs are present, the
molecular shape differs from the electron arrangement because only positions of the atoms are
considered when naming the shape. Example is the four regions of high electron concentration in
SO2−¿¿
3 are farthest apart if they adopt a tetrahedral arrangement. However the shape of the ion is
described by the location of the atoms, not the lone pair. Because only three of the tetrahedral
location are occupied by atoms, the shape of an S O2−¿¿ 3 ion is trigonal pyramidal. This gives the
rule;

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Rule 3: All regions of high electron density, lone pairs and bonds are included in a description of
the electronic arrangement, but only the position of atoms are considered when reporting the
shape of a molecule.

A single unpaired electron on the central atom also is a region of high electron density and is
treated like a lone pair when determining molecular shape. e.g. NO 2 has a single nonbonding
electron, a “lone half-pair.” Thus NO2 has a trigonal planar electron arrangement (including the
unpaired electron on N), but its shape is angular (V shaped).

(V shape)

Because bond angles in molecule with lone pairs are typically smaller than expected, lone pairs
are treated in the VSEPR model as having a strong repelling effect than do electrons in bonds.
i.e. the lone pairs push the atoms bonded to the central atom closer together. We rationalize that
the electron cloud of a lone pair can spread over a larger volume than a bonding pair, because a
bonding pair (or several bonding pairs in a multiple bond) is pinned down by two atoms not one.
This leads to the rule;

Rule 4: The strengths of repulsions are in the order lone pair-lone > lone pair-atom > atom-atom.

The lowest energy is achieved when lone pairs are as far from each other as possible. The energy
is also lowest if the atoms bonded to the central atom are from lone pairs, even though that might
bring the atoms closer to other atoms.
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We can predict electron arrangement in an AX 4E molecule or ion, such as I F 4 is trigonal
bipyramidal, but there are two different possible locations for the lone pair. An axial lone pair
lies on the axis of the molecule, where it repels three electron pairs strongly, an equatorial lone
pair lies on the molecule’s equator on the plane perpendicular to the molecular axis, where it
repels only two electron pair strongly. Therefore the lowest energy is achieved when a lone pair
is equatorial, producing a seesaw-shaped molecule

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An AX3E2 molecule such as ClF3, also has a trigonal bipyramidal arrangement of electron pairs,
but two of the electron pairs are lone pair. These two pairs are farthest apart if they occupy two
of the three equitorial positions but move away from each other slightly. This gives a T-shaped
molecule.

An AX4E2 molecule such as ICl−¿,4

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which has an octahedral arrangement of electron pairs, two of
which are lone pairs, the two lone pairs are farthest apart when they lie opposite each other and
so the molecule is square planar.

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