CHM 104: Introductory Inorganic

Chemistry

Course Lecturer:- Akeem A. Bamigbade

Group IA: - Alkaline metal

Element Symbol Atomic number Electronic configuration

Lithium Li 3 He2s1
Sodium Na 11 Ne3s1
Potassium K 19 Ar4s1
Rubidium Rb 37 Kr5s1
Caesium Cs 55 Xe6s1
Francium Fr 87 Rn 7s1

The electronic structure: - The element of group one, all have one electron in their outermost
orbital, so without considering the inner filled orbitals, the electronic structure are just written as
2s1 ,3s1 ,4s1 ,5s1 ,6s1 & 7s1 . Based on these similarities of the electronic structure, they will have
similar chemical properties. The group one A or alkaline metals are typically soft, they are
highly reactive, univalent metal and they form colourless ionic compound.

General properties of alkaline metal

1. The atoms are largest in their corresponding period in the periodic table.
2. Their ions are very large and increases in size
3. The elements have low density
4. They have low ionization energy
5. The element emits electron when irradiated with light, hence their use in photoelectric
cell.
6. The electronegativity values for the element are very small
7. Ionic compound because their heat of formation is negative
8. The metal ions all have inert gas configuration thus they have no unpaired electrons and
are therefore diamagnetic and odourless.
9. In fact all compound formed by group one metals are white except those where the acid
radical is coloured e.g. chromate and permanganate.

Chemical properties

1. Chemically these elements are very reactive and tarnish rapidly in air to form an oxide.
2. Lithium nitrite is ruby red in colour and is ionized on heating to high temperature. It
decomposes to the element and react with water given out ammonia i.e.
Li 3 N  3H 2 O  3LiOH  NH3
3. Lithium liberates more energy than other element when it reacts with water because of its
high hydration energy and standard electrode potential.
Metal Standard electrode potential
 Li  3.05V
Na  2.71V
K  2.93V
Rb  2.92V
Cs  2.92V

4. When the metals are burnt in air oxide are formed, lithium formed lithium oxide ( Li 2 O ),
sodium formed peroxide ( Na 2 O 2 ) and other forms super oxide ( MO2 ). The typical
oxide MO2 is strongly basic oxide which reacts with water to form strong bases. Thus
caustic alkaline ( NaOH & KOH ) are strongest basic known except the lithium hydroxide
( LiOH ). These basic oxides are very soluble in water and they are thermally stable.
5. The peroxide and super oxide are oxidizing agent and they react with water and acid
given hydrogen peroxide ( H 2 O 2 ) and oxygen gas ( O 2 ).
6. Lithium aluminium hydride is useful reducing agent in organic chemistry and is made
from lithium hydride in ether solution i.e. 4LiH  AlCl3  LiAlH4   3LiCl . LiAlH 4  ,
will reduce carbonyl group or atom to alcohol but it react violently with water. It will also
reduce a number of inorganic compounds in this way i.e.
BCl 3  LiAlH 4   B 2 H 6
PCl 3  LiAlH 4   PH 3
SiCl 4  LiAlH 4   SiH 4
The aluminium hydride ion is tetrahedral AlH 4  sodium borohydride NaBH 4  is
another complex hydride.it is also ionic and is tetrahedral.

Solubility and hydration

All the simple salt is soluble in water. The conductivity measurement is of the following order
Cs   Rb   K   Na   Li  in aqueous solution.

Stability of oxylsalt (carbonate and bicarbonate and nitrate)

1. Due to high electropositive or basic nature of these metal, their oxylsalt are quite stable
2. The carbonate are remarkably stable and melt before they will eventually decomposed
into oxide at temperature over 100 o C
3. Lithium carbonate Li 2 CO 3  is considerably less stable and decomposed more readily
4. Since group one metal is so strongly basic, they also form solid bicarbonate. Apart from
NaHCO3 , ammonia bicarbonate these are the only solid bicarbonate known and
decompose to carbonate on gentle heating liberates CO 2 i.e.
2NaHCO3  Na 2 CO 3  H 2 O  CO 2 .
 5. The nitrate are very soluble in water and solid lithium nitrate LiNO 3  and NaNO3 are
deliquescent while KNO3 is used in gun powder.

Halides

Since lithium ion is the smallest ion, it will be expected to form hydrated salt more readily than
the other metals. Lithium chloride, lithium bromide and lithium iodide form trihydrate
LiX.3H 2 O but the other alkaline metal halides form anhydrous crystal. All the halides adopt
the sodium chloride type of structure except CsCl, CsBr & CsI . The alkaline metal halide reacts
with halogen and inter-halogen compound forming ionic polyhalide compound i.e.
KI  I 2  KI 3  .

Extraction of metal

The metals of this group are the strongest chemical reducing agent known. So they are not
prepared by reducing oxide. Since the metal is so electropositive they react with water.
Attempted displacement of one element from solution by another higher in the electrochemical
series will be unsuccessful. Sodium is made by down process (electrolytic of NaCl with CaCl 2
added). Higher temperature is needed to electrolyse KCl and these result in the vaporization of
the liberated potassium. Recently the modern method for extraction of potassium is to pass
through sodium vapour in a large fractionating tows i.e. Na  KCl  NaCl  K .

Chemical properties

1. Reaction with carbon: - If lithium is heated with carbon and ionic carbide is formed
Li 2 C 2  . The other metal form similar carbide when heated with acetylene i.e.
Na  C 2 H 2  NaHC2  Na 2 C 2 & Na 2 C 2  H 2 O  NaOH  C 2 H 2 .
2. The alkaline metal replace hydrogen in organic acid forming salt such as sodium acetate
i.e. CH 3 COOH  Na  CH 3 COONa and CH 3 COOH  K  CH 3 COOK .
3. Alkaline metal form a number of alkyl and halide 2K  HgR 2  Hg  2KR

Group 2A: Alkaline earth metal

Element Symbol Atomic number Electronic configuration

Beryllium Be 4 He2s 2
Magnesium Mg 12 Ne3s 2
Calcium Ca 20 Ar4s 2
Strontium Sr 38 Kr5s 2
Barium Ba 56 Xe6s 2
Radium Ra 88 Rn 7s 2

Electronic structure: - All group two elements have s 2 electron in the outermost shell. They are
typically divalent and forms are well graded series of highly reactive metals. Generally forming
colourless ionic compounds and being less basic than group one. Beryllium show considerably
difference from the rest of group and diagonal relationship similar with aluminium in group 3.

General properties

Beryllium is unfamiliar partly because it is not very abundant and partly because it is very
difficult to extract. It is found in small quantity as the silicate minerals Be 2SiO 4 , Be3 Al2Si 6 O18 
. Magnesium and calcium are abundant among the 8 most common elements in the earth crust.
Magnesium salt occurs in some quantities in sea water and as deposit as magnetite MgCO3  and
dolomite MgCaCO 3 2  .

Calcium carbonate is found extensively as calcite and limestone in many mountain ranges.
Strontium and barium are much less abundant but are well known because they occur as
concentrated ores and are easy to extract. Radium is extremely scares and its radioactivity is very
important. The atom of group two are large but smaller than group one and their ion is also larger
but smaller than group ion.

Group two elements are denser than group one elements. The compounds are divalent and ionic
since the atoms are smaller than those in group one, the electrons are more tightly held so that
they needed to remove the first electron (first ionization energy) is greater than that needed for
group four times greater than the amount needed to ionise the group one elements. The hydrated
energy of the ions is four or five times greater than for group one elements because of their
smaller sizes and increase charge. Enthalpy change H decreases down the group as the size of
the hydrated ion increases. The solid compounds are also more heavily hydrated than those in
group one e.g. MgCl 2 .6H 2 O, CaCl 2 .6H 2 O & BaCl 2 .6H 2 O . Since the divalent ion have an inert
gas structure with no unpaired electron their compound are diamagnetism and colourless.

Chemical properties

The group two metals are less electropositive than group one counterpart. They react with water
to give metal hydroxide and hydrogen. Magnesium especially decomposes hot water and other
metals react with cold water. Beryllium hydroxide is amphoteric BeOH2  . The order of
increases in basic strength is from magnesium to barium i.e. increases down the group. Solution
of calcium hydroxide and barium hydroxide are used as lime and barite water to detect CO 2 in
the laboratory. The effect of CO 2 on this is to produce soluble bicarbonate thus removing the
turbidity i.e. Ca OH2  CO 2  CaCO 3  H 2 O Excess, 2  Ca 2 HCO3 2 . This bicarbonate is

CO
only stable in solution and their decomposition to carbonate is the reason for stalactite and
stalagmite formation.

All the elements in this group burn in oxygen to form the oxide MO, where M is the metal and
O is oxygen. This can also be formed by thermal decomposition of their sulphate, carbonate,
hydroxide and nitrate to give their oxides e.g. MCO3  MO  CO 2 , based on this we have
BeO, MgO, CaO etc. As the atom get larger the ionization energy decreases and the element
become more basic, thus beryllium oxide is insoluble in water but dissolve in acid to give salt
and in alkaline to give berylates which on standing form precipitate. It will precipitate to
hydroxide.

Magnesium oxide ( MgO ) react with water to form MgOH2 which is weakly basic, then CaO
react very readily with water to form Ca OH2 and is a moderately strong base while strontium
and barium hydroxide are stronger bases. CaO is prepared on a large scale by heating CaCO 3 in
lime kilns and is used in manufacture of calcium carbide CaC 2  , bleaching powder, glass and
also in cement. The solubility of the sulphate in water decreases down the group i.e.
Be  Mg  Ca  Sr  Ba . Sometimes calcium sulphate is always insoluble, the nitrate of group
two metals can be prepared in solution as a hydrated salt by the reaction of HNO3 on
carbonates, oxide or hydroxide.

All the elements except beryllium formed the hydride MH2  by direct combination of the metal
and hydrogen but impure BeH 2 has been formed or made by reducing BeCl 2 with lithium
aluminium hydride LiAlH 4  . All the metals combine with halogen to form the halide MX2 . The
fluorides MF2 are almost all insoluble. The halides of some of elements are hygroscopic and
form hydrates e.g. CaCl 2 is a good drying agent while anhydrous MgCl 2 is important in the
electrolytic extraction of magnesium.

Organometallic compound

They are compound formed from organic compound and metal and they mostly formed from
group two element particularly magnesium. They are known as Grignard reagent RMgX .
Magnesium formed Grignard reagent which are the most versatile reagent in organic compound.
When magnesium is heated with an alkyl halide or aryl halide agent a Grignard reagent is formed
in an absolutely dry organic solvent such as diethyl ether. Example of Grignard reagent is
CH 3 MgBr .

Extraction of metal

The metals of group two are not easy to produce by chemical reduction because they are strong
reducing agent. They form the carbide, they are also strongly electropositive and so aqueous
solution cannot be used to replace one metal by another or by electrolysis because of the reaction
of metal with water.

Anomalous behaviour of beryllium to other group two elements

It shows a diagonal relationship with aluminium in group 3. Beryllium is very small and has a
high charge density and strong tendency to covalency. The melting point of beryllium is lower
than the rest of the group. Beryllium forms many complexes that are typical of group 1 and 2.
Beryllium like aluminium is rendered passive by nitric acid. Beryllium is amphoteric liberation
H 2 with sodium hydroxide forming berylates while aluminium forms aluminates. The salt of
aluminium and beryllium are extensively hydrolysed, their hydride and alkyl are polymeric.
Beryllium salts are among the most soluble known salt.