GROUP 1: Reaction with water:

General electronic configuration: ns1 Li is slowly hydrolysed by water, Na reacts vigorously, while K, Rb, Cs react
Highly reactive, hence don’t occur in free state but widely distributed In explosively to form MOH and liberate H2 gas.
nature as halides, oxides, silicates, borates and nitrates. Dissolve in water to These metals also reacts with alcohol gives alkoxide and H2:
produce hydroxides-basic/alkaline nature. 2Li + 2C2H5OH → 2C2H5O-Li+ + H2
Na is 7th, K is 8th, Rb is 23rd , Cs is 46th and Li is 35th most abundant element by Reaction with oxygen: .
weight on earth’s crust. Fr is rare and radioactive, discovered by Pierre. Li forms monoxide[ Li2O], Na forms peroxide [Na2O2], while K, Rb, Cs for
Isotope of Fr, i.e, Fr233 has the longest half life of 21 minutes. superoxides [ KO2, RbO2, CsO2] due to the fact that comparable sizes of ions
Li mainly occurs in the form of silicates, such as spodumene [LiAl(SiO3)2] and form the strongest lattice.
lepidolite [(Li,Na,K)2 Al2(SiO3)3F(OH)] and amblygonite [LiAl(PO4)F]. Their stability order is: Normal oxide > Peroxide > Superoxide
Minerals of Na are: rock salt (NaCl), borax (Na2B4O7.10H2O), trona (Na2CO3 Oxides are usually colourless, but Rb2O is pale yellow and Cs2O is orange.
NaHCO3.2H2O), Chile salt petre (NaNO3),Mirabilite (Na2SO4). Reactivity towards Dihydrogen:
K mainly occurs as: sylvite/sylvine (KCl), carnalite (KCl.MgCl2.6H2O), felspar 2M + H2 → 2MH (M= Li, Na, K, Rb or Cs)
(K2O.Al2O3 6SiO2)
Properties of hydrides:
Size of atoms: Grp 1 atoms have the largest size in their resp. periods. (M+ <
1. Alkali metal hydrides have NaCl type structure.
M is true for all cations); Li+ is much smaller, so it is miscible only with Na that 2. Ionic in character: LiH<NaH<KH<RbH<CsH
too above 380oC, it is immiscible with K, Rb, Cs.
3. Stability of hydride: LiH>NaH>KH>RbH>CsH
Density: Remarkably low density Li density=1/2 density of water
Solubility in liquid NH3:
Na,K-slightly less dense than water
 They dissolve in liquid NH3 (upto 5M) giving highly conducting blue soln,
Strucuture: At normal temp, grp 1 metals adopt a body centred cubic type of also containing ammoniated electrons and cations.
lattice (coordination number 8). However at low temperatures, Li for  Upto 3M, soln is dark blue and conc greater than 3M soln colour changes to
hexagonal closed packed structure (Coordination no.=12). Very soft,can be cut copper-bronze and soln acquires metallic lustre due to formation of metal
with knife, but Li is harder cluster.
Cohesive enrgy hold the ions to form solids, and it determines hardness  The blue coloured solns are paramagnetic due to large presence of
Cohesive energy of grp 1 is half od group 2 , 1/3 of group 13 unpaired e- but bronze solns are diamagnetic due to formation of e-
Softness: Li>Na>K>Rb>Cs clusters.
Colour of compounds:Typically white, except if anion is coloured. Compounds 2e- (NH3)y →[↑e- (NH3)y][↓e-(NH3)y]
are also mostly diamagnetic. Na2[CrO4] (Yellow), K2[Cr2O7] (orange), K[MnO4]  Soln of alkali metals in Liquid NH3 are good conductors of electricity but
(deep purple) the conductivity decreases as con of NH3 decreases. This sis due to the fact
Properties that decrease down the group: [↓] that the ammoniated metal cations are bound by the free unpaired
 IE1, IE2, EN, MP and BP electrons and this situation is reffered to as expanded metals.
 Hydration enthalpy and Lattice enthalpy Basic strength of Hydroxides of alkali metals:
 Charge density and polarising power Basic strength of alkali metals decreases down the group, due to lower IEs. All
 Reactivity towards hydrogen OHs of alkali metals are highly soluble in water and thermally stable except for
Properties that increase down the group: [↑] LiOH, which decomposes on heating to give Li2O.
 Atomic number, Atomic mass Reaction with nitrides:
 Metallic radius, Ionic radius Only Li combines with N2 directly to form Li3N. Li3N is hydrolysed by water to
 Density (exception: K<Na) form ammonia.
 Reactivity towards water and oxygen 6Li + N2 → 2Li3N
 Thermal & electrical conductivity Li3N + 3H2O → 2LiOH + NH3
Flame colouration: Similar rxn is applicable to Na, but its is difficult and only at high temperature.
Li Na K Rb Cs Nitrates: MNO3
Crimson Yellow Pale violet/Lilac Red-Violet Blue These are colourless, soluble in water and covalent in nature.
Nitrates of Li and Na are delinquesent in nature.
CHEMICAL PROPERTIES: On heating all alkali metals (except Li), give:
Li is the strongest reducing agent in aqueous solution, because Li has the 2MNO3 ∆→2MNO2 + O2
most negative standard reduction potential [E- = -3.04 V]. 2LiNO3 ∆→ Li2O + 2NO2 + O2
1
2
Oder of reducing chr in aqueous soln:
Carbides:
Li> Cs> Rb> K>Na
Only Li reacts with carbon to form an ionic carbide, Li2C2.
Other metals form carbon compounds when heated with acetylene (Na) or
graphite (K, Rb, Cs).
Reactivity towards halogens:
For any given alkali metal, their reactivity decreases as:
Fluoride> Chloride> Bromide>Iodide
Thus fluorides are most stable while Iodides are least stable.
Lattice & Hydration enthalpies:
Both lattice and hydration enthalpies decrease down the group:
1. Greater/more –ve the lattice enthalpy, higher the MP and lower the
solubility in water
2. Greater/more –ve the hydration energy, greater is solubility of the
compound in water
3. Ionic mobilites of alkali metal ions in aq soln should be : Li+>
Na+>K+>Rb+>Cs+
Due to decreasing order of charge densities, but observed order is
reverse as above, i.e, : Li+><Na+<K+<Rb+<Cs+due to decreasing order of
extent of hydration
4. Similarly, order of hydration radius is:
Li+> Na+>K+>Rb+>Cs+
5. Solubility of LiF in H2O is low due to high lattice enthalpy where as low 3. LiNO3 decomposes on heating to give Li2O+NO2+O2, while others give
solubility of CsI is due to less/-ve values of hydration enthalpies of the 2 MNO2+O2
ions. 4. LiCl is deliquescent and forms hydrate [LiCl.2H2O] while others do not
6. Solubilites of most alkali metal halides except that of Fluorides, decreases form hydrates
down the group 5. LiOH is a weaker base than others
7. The solubility of alkali metal fluorides increases from LiF to CsF because 6. Halides of Li are covalent
the increase in lattice enthalpy more than compensates the decrease in 7. Li does not react with acetylene while others react to form metal
hydration energy acetylide. But Li, on heating with C, forms lithium acetylide while others
Ionic, Covalent chrs of Alkali metal halides: do not react with C directly.
1. The covalent character decreases as the size of cation increases: 8. LiHCO3 does not form a solid
LiCl>NaCl>KCl>RbCl>CsCl 9. Li ion is the largest hydrated ion
2. The covalent character decreases as size of anion decreases: 10. Li is harder and has higher MP and BP
LiI>LiBr>LiCl>LiF 11. Alkyl and aryls of Li are more stable
3. Covalent chr of some halides decreases in the order as the charge on 12. Li shows greater tendency to form complexes
cation decreases: 13. Li forms Li2O while others form Na2O2,or MO2
AlBr3>MgBr2>NaBr Diagonal relationship of Li & Mg:
4. Similarly, K3PO4>K2SO4>KCl Due to similar charge densities, Li and Mg resemble in properties:
5. CuBr is more covalent than NaBr, because Vu is a pseudo noble gas have 1. Both form Nitrides with N2 (Li3N and Mg3N2)
18e- in outer most shell 2. Hydroxides decompose to give Li2O and MgO resp
Melting point: 3. Compounds of both are deliquescent and form hydrates (LiCl2. H2O and
1. Mp decreases as: Fluoride > Chloride > Bromide> Iodide MgCl2.6H2O)
This is due to decrease in lattice enthalpies as size of halide ion increases 4. Both do not form solid bicarbonates
2. For the same halide ion, Mp decreases down the group, due to decrease 5. Both form oxides with O2 (Li2O and MgO)
in lattice enthalpies as size on cation increases. 6. Nitrates of both decompose to give (Li2O or MgO) + NO2+ O2
NaCl>KCl>RbCl>CsCl 7. The hydroxides, carbonates and fluorides are all sparing soluble in H2O
3. LiCl MP is lower than that of other alkali metal halides, due to small size 8. Both lithium perchlorate[LiClO4] and magnesium perchlorate [Mg(ClO4)2]
of Li are highly soluble in ethanol
Salt of Oxoacids: Extraction of Alkali metals:
Alkali metal hydroxides being stong, form salts with all oxoacids (HNO3, 1. They are strong reducing agents and hence cannot be extracted by
HNO2,H2SO4, H2CO3, H3PO4),and are generally soluble in water and stable reduction of their oxides and chlorides.
towards heat. 2. They cannot be obtained by electrolysis of aq solns of their salts
Carbonates & Bicarbonates: 3. Cannot be displaced from their aq soln by other metals due to high
1. All soluble in H2O, and their solubilities increase down the group because electropositive character
lattice enthalpies decrease more rapidly than hydration enthalpies down 4. Melting points are usually very high
the group Extraction of Li: Obtained by electrolysis of a fused mixture of dry LiCl(55%)
2. M2CO3 are stable upto 1275K above which they decompose to form and KCl (45%). Alternatively, electrolysis of LiCl soln in pyridine, ethanol or
oxides. acetone can be done.
3. Li2CO3 is less stable and decomposes readily to give [ Li2O + CO2] It cannot be stored in kerosene oil,as it floats on the surface, it is therefore
4. No other metals form solid bicarbonates except alkali metals, though stored in paraffin wax. It is the lightest metal known.
NH4HCO3 exists as a solid. Uses:
Exception: Li does not form bicarbonate but exists as solution 1. In the preparation of alloys:
5. On heating, decomposition: 2MHCO3 ∆→M2CO3 + CO2+ H2O a. White metal (or lI-Pb) alloy (0.005% Li)
6. Thermal stability of carbonates ∝ 1/ (Ionic potential) b. Li-Al alloys
Order of stability is – c. Li-Mg alloys (14%)
Cs2CO3> Rb2CO3> K2CO3> Na2CO3> Li2CO3 2. To make electrochemical cells.
Sulphides: Extraction of Na: Obtained by electrolysis of NaCl(40%) + CaCl2 (60%) in a
Alkali metals react with sulpur to form sulphides of formulae, M2Sx where Down’s cell at 873K using graphite anode and iron cathode.
x=1,2,3,4,5 or 6. Monosulpihdes are prepared by burning metals in sulphur Uses:
vapour or by high temp reduction of their sulphates with carbon. 1. To make tetraethyl lead pg(C2H5)4, which is used as a anti-knocking agent
2Na + S →Na2S for gasoline
Na2SO4 + 4C → Na2S + 4CO 2. Used in sodium vapour lamps
Polysulphides are formed by action of sulphur on metal solution in liquid 3. Used as a reducing agent in the extraction of B and Si
ammonia. The polysulphide ions form a crystal lattice with zig-zag chain of 4. Used as a reagent in Wurtz reaction
sulphur atoms. Extraction of K: Cannot be obtained by electrolysis of KCl. Therefore KOH is
Sodium sulphite can be made by reacting with sulphur or, heating sodium hydrolysed to obtain K at cathode and O2 at anode.
sulphate with carbon, or passing H2S into NaOH soln. Compounds of Na:
Na2SO4 + 4C → Na2S + 4CO 1. Washing soda [ Na2CO3.10H2O]: It is prepared by solvay-ammonia procress.
NaOH + H2S → NaHS + H2O Raw materials used: Brine (NaCl) soln saturated with NH3 and CaCO3. It is
NaOH + NaHS → Na2S + H2O used for softening hard water.
Grp 1 sulphides hydrolyse appreciably in water, giving strong alkaline solns.
Na2S is used to make organic sulphur dyestuffs. Na2S is readilyoxidised by air
to form sodium thiosulphae (used in photography, to dissolve silver halides,
and in labs for iodine titrations).
2Na2S + 2O2 + H2O → Na2S2O3 + 2NaOH
2 Na2S2O3 + I2 →Na2S4O6 + 2NaI
Abnormalities of Lithium:
Due to its small size, high charge density, high IE, strong intermediate Note: K2CO3 cannot be prepared by Solvay process. NaHCO3 is sparing
bonding, Li differs on some properties: soluble in H2O,while KHCO3 is fairly soluble in H2O.
1. Forms nitrides with N2
2. LiOH (thermally unstable) and Li2CO3 decompose to give Li2O
2. NaCl: It is produced by the vapourization of sea water. Crude NaCl is
obtained by crystallization of brine solution and contains impurities of
Na2SO4, CaSO4,CaCl2, MgCl2.

3. Caustic soda [NaOH]: It is prepared by the electrolysis of an aqueous soln of

NaCl using mercury cathode and graphite anode in a vessel called Castner
and Kellners’s cell or mercury cathode cell.

Biological importance of Na and K: Na+ ions are found outside the cell in
blood plasma, other interstitial fluids, K+ ions are present inside the cell. These
ions help in regulating the flow of water across the cell membrane, in
transmission of nerve signals. K+ ions activate many enzymes, and participate
in oxidation of glucose to ATP. Due to diff concentrations of Na+ and K+ ions on
the opposite sides of cell membrane, Na-K pump operates and consumes
more than 1/3rd of ATP of resting human being.
Additional notes:
1. Li is not used in photo electric cell because of highest IE among alkali metals.
2. Peroxides (O2 2-) of 1st group are colourless and diamagnetic, while
superoxides (O2-) are coloured and paramagnetic.
3. 1st group metals can be induced to form normal oxides, i.e, monoxides,
peroxides and superoxides by dissolving metals in liquid NH3, and passing
4. Baking soda [NaHCO3]: Prepared by saturating a soln of Na2CO3 appropriate amount of O2.
with CO2. 4. Except Cs2O, all other monoxides, eg. Li2O, Na2O, K2O, Rb2O have
Na2CO3+H2O+CO2 → 2NaHCO3 antifluoritestructures. Cs2O has anti CdCl2 layer structure.
5. Potassium superoxide [KO2] combines directly with CO2 forming K2CO3, and
with CO2 and moisture forming KHCO3.
4KO2 + 2CO2 → 2K2CO3 + 3O2
4KO2 + 4CO2 + 2H2O → 4KHCO3 + 3O2
6. Both KO2 and Na2O2 are used as a source of oxygen in confined space such as
submarines, space shuttles and in emergency breathing instrument such as
Compounds of K: oxygen masks. The moisture o the breath reacts with KO2 and Na2O2 to
literate O2 and simultaneously KOH and NaOH remove CP2 as it is exhaled,
thereby allowing the atmosphere in mask to be continuosly regenerated.
4KO2(s) + 2H2O(g) → 4KOH(aq) + 3O2 (g)
2Na2O2(s) + 2H2O(g) → 4NaOH(aq) + O2(g)
KOH or NaOH + CO2 → KHCO3 or NaHCO3
7. LiOH is also used to remove CO2 from exhaled air inn confined spaces such as
submarines and space shuttles.
8. Potassium Ozonide (KO3) is an orange coloured solid and contains
paramagnetic O3- ion and is prepared by passing O3 through KOH soln.
9. Li does not form alums due to tiny size.
10. Grp 1 metals form amalgams with Hg with release of energy.
11. Alkali metals react with halogens and interhalogens to form polyionic
compounds.
NaI + I2 → NaI3
NaBr + ICl → Na [BrICl]
NaF + BrF3 → Na [BrF4]
12. Lithia water is an aqueous solution of LiHCO3 and is used for the treatment of
gout.