Group-1(Alkali Metals)

ALKALI METALS
(Li, Na, K, Rb, Cs, Fr*)
(Fr-223 is radioactive is a beta emitter having half life period 21.8 minutes and forms Ra-223)
PHYSICAL:
1. EC : ns1
2. Physical State : Silvery White (exception : Cs- golden yellow), lusture tarnishes due to oxide layer- soft
(cut by knife) and light - highly malleable (Fr is radioactive)
3. Atomic and Ionic Radii : Highest in ther respective periods, increases from Li - Cs
4. Density : Increases from Li - Cs (exception : K < Na)
5. MP/BP : low - decreases from Li(1860C) - Cs (290C) - due to decrease in metalling bond strength
6. IE : least their respective periods - decreases from Li - Cs (lowest: hence found in combined state)
7. EN/Bonding/OS : Low EN - strong metals - ionic bond - +1 state (M+ ion)
8. Hardness : Soft metals - softness increases from Li - Cs due to decrease in metallic bond strength
9. Photoelectric Effect : increases from Li - Cs as IE decreases
10. Flame Colouration : Alkali metals and their salts show distinct colour in flame :
Li - Crismson Red, Na- golden yellow K - Lilac/violet Rb - Purple Cs - Blue
Due to low IE, the valence electron is excited to higher level and on deexcitation emits light. In case of ionic
compound, first electron is received back from anion and then excitation-deexcitation occurs.
11. Thermal and Electrical Conductivity : High due to presence of free electrons
12. Hydration of Ions and Electrical conductivity in aq. solution:
Hydration energy is the energy evolved when one mole of gaseous ions are completed hydrated.
M+(g) + aq. -----> M+(aq.) + H.E
H.E ∝ charge density, HE ∝ 1/size; Hence Li + > Na+ > K+ >Rb+ > Cs+ (HE)
Hence Li salts are hydrated : LiCl.2H2O
Electrical conductivity in aq. solution : Li + < Na+ < K+ < Rb+ < Cs+
Hydrodynamic radius of Li+ is the greatest and of Cs+ the least.
13. Electrode Potential(Reducing Power)
The Standard Oxidation Potentials(SOP) of M(s)/M+(aq.) electrodes are high and hence are good
RAs
Li > K ≈ Rb > Cs > Na
SOP of an electrode is higher if the sum of the following three energy terms is lower.
(a) Heat of sublimation (+ve) (b) IE (+ve) (c) HE (-ve)
+ +
Due to highest HE of Li , the sum is lowest for Li(s)/Li (aq.) although its IE is also highest.
Na has a high sublimation energy for which this sum is highest for it.
14. Extraction of Metals: Electrolysis of fused(molten) salts (not by chemical reduction method as they
themselves are strong RAs)
CHEMICAL
1. Reactivity : highly reactive - stored under kerosine -
2. With Water : Li < Na < K < Rb < Cs (due to decrease in mp, spreads quickly and reaction rate increases)
Moreover IE decreases. M + H2O MOH + H2, exothermic and cathces fire
3. With Air : Li + O2 Li2O; Na + O2 Na2O2(major) + Na2O(minor)
K + O2 KO2, Rb + O2 RbO2 Cs + O2 CsO2
Li gives monoxide, Na gives peroxide while K, Rb and Cs give superoxide due to increase size, more number
of O required for stable crystal structure
4. With haogens : M + X2 MX (ionic compounds) (LiCl/LiBr/LiI have appreciable covalent character)
5. With H2 : M + H2 --673K MH ( Li > Na > K > Rb > Cs) due to greater decrease in lattice energy
Dr. S. S. Tripathy
 Group-1(Alkali Metals)
6. With Nonmetals : M + S M2S; 2M + x S M2Sx (polysulphides)
M + P4 P3P etc.
7. With liquid NH3 : Alkali metal dissolves in pure liquid ammonia forming an intense blue solution containing
ammoniated M+ and ammoniated electrons(e).
M(s) + NH3(l) M+(NH3)x + e(NH3)y The solution is
(a) highly conducting due to free electrons (b)paramagnetic (c) Strong RA
On standing, it slowly liberates hydrogen and forms metal amides. In concentrated solution, its colour turns
bronze and becomes diamagnetic.
In presence of a little impurity such as Fe, Fe2O3, Pt etc. it decomposes rapidly to form H2 and metal amide.
M + NH3---impurity MNH2 + H2
8. Formation of Alloys : (i) Na-K alloy is a liquid -used as coolant in NPP.
(ii) Amalgams - Na-Hg, K-Hg etc. used to decrease the reactivity of alkali metals
(iii) Na-Pb used for the preparation of TEL(Tetra Ethyl Lead) used as anti knocking additive in petrol
but now banned for pollution hazards.
9. OXIDES AND HYDROXIDES:
Oxides dissolve in water forming hydroxides exothermically. These are strong bases.MOH are white
crystilline solids and are highly deliquescent(absob water and get dissolved in it).
Na2O2 + H2O NaOH + H2O2; KO2 + H2O KOH + H2O2 + O2
Superoxide ion is paramagnetic and the MO2 is yellow to orange in colour.
10. HALIDES:
(i) Heat of formation of halides is negative.
M(s) + ½ X2(g/l/s) MX(s) + heat (ΔH0f = –ve) ΔH0f = standard heat of formation
(a) For flourides, the numerical value of the heat of formation decreases as we go down the group
while for other halides, the values increases(exception RbBr < KBr).
(b) For a given alkali metal the numerical value decreases from flouride to iodide.
(ii) MP/BP of halides: flouride > chloride > bromide > iodide (for a given alkali metal)
(iii) Solubility : Solube in water. But LiF is sparingly soluble due to its high lattice energy. CsI also has
low solubility in water due to low hydration energy. Other halides of Li are soluble in ethanol, acetone and ethyl
acetate due to appreciable covalent character(Fajan’s rule). LiCl is also soluble in pyridine.
11. CARBONATES AND BICARBONATES:
Alkali metal carbonates(except that of Li) are stable to heat. Stability of carbonates increases
from Li to Cs. Bicarbonates decompose to carbonates, CO2 and water.
Anomalous Behavior of Li:
(i) Formation of nitride : Li + N2 Li3N (others do not)
(ii) Decomposition of Li2CO3( CO2) , LiNO3( NO2 and O2) , LiOH
(iii) F–, CO32-, OH–, PO43- are sparingly soluble
(iv) Li compounds have appreciable covalent character (Fajan’s rule) due to small size and hence
appreciable solubility in organic solvents
(v) LiHCO3 does not exist as a solid.
(vi) much harder than other alkali metals
(vii) Least reactive but strongest RA.
(viii) Forms mainly monoxide with oxygen.
(ix) LiCl chloride forms dihydrate. Others do not form hydrates.
(x) Does not react with ethyne.
DIAGONAL RELATIONSHIP WITH Mg:
(i) Light (ii) hydroxides are less soluble (iii) form nitrides (iv) chlorides soluble in ethanol (v)
chlorides form hydrated salts. (Diagonal relationship is due to similar ionic radii)

Dr. S. S. Tripathy
 Group-1(Alkali Metals)

USES: 1. Li-Pb alloy(white metal) used bearing for motor engines; Li-Al alloy used for making aircraft parts,
Li-Mg alloy used to make armour plates. LiD used in thermonuclear reaction(hydrogen bomb).
3. KCl as fertiliser and KOH used for manufacturing soap and absorb CO2
4. Cs as photolectric material

SODIUM
Ores: Chile Salt Peter( NaNO3), Salt cake (Na2SO4), Rock salt (NaCl), Borax or Tincal(Na2B4O7.10H2O),
Trona (Na2CO3.NaHCO3.2H2O)

Electrolytic Extraction: (Down’s Process):

Electrolyte : Molten mixture : NaCl(40%) + CaCl2(60%) : mp = 6000C
Why CaCl2 is mixed ? (i) mp is lowered from 800 to 6000C. (ii) prevent the vaporization and condensation
of Na as colloidal particles in molten NaCl whose isolation would have been very difficult. Morever further
electrolysis stops due Na colloidal particles.
(iii)prevents catching of fire by Na vapours as VP at 6000C is low
(iv) reduces cost
Na+ needs smaller voltage to discharge than Ca2+
At cathode : Na+ + e Na At anode : 2Cl– Cl2
Reactions of Na:
Na + O2 Na2O2 Na + H2O NaOH + H2
Na + O3 ----liquid NH3 NaO3 Na + SiO2 Na2O + Si
Na + CO2 Na2CO3 + C Na + H2 NaH
Na + Cl2 NaCl Na + NH2 ---Pt NaNH2 + H2
Na + H2SO4(dil.) Na2SO4 + H2 Na + HNO2(dil) NaNO3 + N2O + H2O
Na + CO Na2C2 + Na2CO3
USES: (i) Preparation of TEL using Na-Pb alloy : (4 Na-Pb + 4 C2H5Cl (C2H5)4Pb + 3Pb + 4NaCl)
(ii) Redn. of Zr, Ti from theri oxides (iii) Prepn. of NaNH2, NaH, NaCN etc.

SODIUM HYDROXIDE(NaOH) OR CAUSTIC SODA

Castner-Kellner Cell :
Cathode : Hg; Anode : Graphite
+
At cathode : Na + Hg + e Na/Hg ( the reduction potential of this reaction is greater than that of the
+
reduction of H )
Sodium amalgam is siphoned to another chamber where it reacts with water to form NaOH + H2 and
Hg. Mercury is recycled to the electrolytic bath.
PROPERTIES: It highly deliquescent and corrosive. Melts at 591K.
(The reactions below are not balanced. The learners are required to balance them and study the logic)
NaOH + CO2 NaHCO3(Na2CO3 + H2O)
NaOH + SO2 NaHSO3(Na2SO3 + H2O)
NaOH(cold and dil.) + Cl2 NaCl + NaOCl + H2O
NaOH(hot and conc.) + Cl2 NaCl + NaClO3 + H2O
NaOH + Zn Na2ZnO2 + H2 NaOH + Al + H2O NaAlO2 + H2
NaOH + Sn Na2SnO3 + H2 NaOH + ZnO Na2ZnO2 + H2O
AlCl3 + NaOH Al(OH)3(gelatinous white ppt.) + NaCl
Al(OH)3 + NaOH(excess) NaAlO2(soluble) + H2O
NaOH + SnO2 Na2SnO3 + H2O NaOH + Cr(OH)3 NaCrO2 + H2O
NaOH + PbO Na2PbO2 NaOH + NH4Cl NH3 + NaCl + H2O
Dr. S. S. Tripathy
 Group-1(Alkali Metals)
NaOH + P4 NaH2PO2 + PH3 NaOH + Si Na2SiO3 + H2
NaOH + S Na2S + Na2SO3 + H2O NaOH + B NaBO2 + H2
NaOH + CO HCOONa NaOH + NO2 NaNO2 + NaNO3 + H2O
NaOH + H3PO4 Na3PO4 + H2O (Depending on mole ratio, NaH2PO4/ Na2HPO4/Na3PO4 formed)
ZnCl2 + NaOH Zn(OH)2(white ppt.) + NaCl
Zn(OH)2 + NaOH(excess) Na2ZnO2(soluble) + H2O
Preparation of Na from NaOH: Magnesium metal powder reacts with NaOH powder(solid) to form sodium
metal and hydrogen gas
2Mg(s) + 2NaOH(s) 2MgO + 2Na + H2
Although magesium does not react with dilute or conc. NaOH solution,, the two solids when mixed in powdered
state, reaction does occur. The reaction is highly exothermic to ignite hydrogen produced. Sodium metal can
be seprated with the help of any mineral oil(kerosine) in which sodiium does not dissolve.
USES: (1) Preparation of soap, dyes, paper, artificial silk (2) purification of bauxite
(3) mercerizing cotton in textile industries (4) in petroleum refining

Na2CO3.10H2O(Washing Soda)
Preparation:
I. LE BLANC PROCESS :
NaCl + NaHSO4 Na2SO4 + 2HCl
Na2SO4 + CaCO3 + 4C [Na2CO3 + CaS] + 4CO
Black Ash
Black Ash is dissovled in water in which Na2CO3 becomes soluble and CaS does not. The filtrate is crystallized
to form Na2CO3.10H2O.
II. SOLVAY AMMONIA SODA PROCESS:
Step I : NH3 + CO2 + H2O NH4HCO3
Step II: NH4HCO3 + NaCl(brine) NaHCO3 ↓ + NH4Cl
Step III: 2NaHCO3 ----heat----> Na2CO3 + H2O + CO2
Raw Materials : Lime Stone(CaCO3) and NaCl(brine):
Recycling of CO2 and NH3 :
CaCO3 CaO + CO2, NH4Cl + CaO ---heat--> NH3 + CaCl2 + H2O
NH4Cl formed in step II reacts with CaO to form the NH3. So CaCl2 is the byeproduct in the process.
PROPERTIES: It is a white crystalline solid.
standing
Na2CO3. 10 H 2O Na2CO3.H2O + 9H 2O
efflorescence
373K
(2)
Na2CO3 + H 2O
soda ash
(3) Its aq. solution is basic due to hydrolysis. CO32– + H2O HCO3– + OH–
(4) Chemical Reactions: Na2CO3 + HCl NaCl + CO2 + H2O
Na2CO3 + CO2 + H2O 2NaHCO3
Na2CO3 + SO2 Na2SO3 + CO2 Na2CO3 + CaCl2 CaCO3 ↓+ NaCl
Na2CO3 + BaCl2 BaCO3 ↓ + NaCl
USES: (1) Softening hard water (2) laundering and cleaning (3) manufacture of glass, soap, borax,
caustic soda, paper, paints, textile (4)Fusion mixture (K2CO3 + Na2CO3) in qualitative analysis

Dr. S. S. Tripathy
 Group-1(Alkali Metals)

SODIUM HYDROGEN CARBONATE/ BICARBONATE(Baking Soda):

Preparation : (1) Solvay’s Process (2) Na2CO3 + CO2 + H2O 2NaHCO3
PROPERTIES: Low solobility in water. Decomposes to give sodium carbonate/CO2 and water.
USE: Mild antiseptic for skin infections, used in cakes and pastries, used in fire extinguishers

SODIUM THIOSULPHATE (Na2S2O3.5H2O)/ HYPO:

Preparation:
Na2SO3 + S Na2S2O3 Na2SO3 + Na2S + I2 Na2S2O3 + NaI
0
Na2S2O3. 5H2O 215 C Na2S2O3 + 5 H 2O

heat
Properties:
Na2SO4 + Na2S5

Na2S2O3 + HCl NaCl + S + SO2 + H2O Na2S2O3 + I2 NaI + Na2S4O6

Na2S2O3 + AgNO3 Ag2S2O3(white ppt.) + NaNO3 (sliver thiosulphate further reacts with water)
Ag2S2O3 + H2O Ag2S(black) + H2SO4
AgBr + Na2S2O3 Na[Ag(S2O3)] and Na3[Ag(S2O3)2] (soluble complexes)
Na2S2O3 + Cl2 + H2O Na2SO4 + HCl + S
USES: As antichlor, extraction of Ag and Au, Fixing agent in photography, qualitative analysis (iodimetry)
POTASSIUM:
Ores: Carnalite (KCl. MgCl2.6H2O), Indian Salt Petre(NItre) : KNO3 Sylvite: KCl
Extraction : Electrolysis of fused KCl + CaCl2 (same as Na)
PROPERTIES: Similar to Na (except K gives KO2 with oxygen)
Na2SO4.10H2O (Glauber salt):
Mined as Glauber salt. Can also be prepared by the reaction of NaCl and H2SO4 followed by crystallisation.
Anhydrous salt dissolves in water below 32.3840C and its solubility decreases with further increase in
temperature. Anhydrous salt is used as drying agent and in the preparation of glass and paper.

NaCN:
Preparation : NaNH2 + C NaCN + H2 CaNCN + Na2CO3 + C NaCN + CaCO3
Properties : Forms complexes with Cu, Ag, Au, Cd, Zn and Fe
Au + NaCN + H2O + O2 Na[Au(CN)2] + NaOH (Ag gives similar complex)
CuSO4 with excess of NaCN gives Na3[Cu(CN)4] , CdSO4 gives Na2[Cd(CN)4]
USES : (1) extraction of Ag and Au (2) Electroplating of Au and Ag
POTASSIUM CARBONATE(K2CO3)/ Pearl Ash or Potash
SAQ: Why K2CO3 cannot be prepared by Solvay’s process ?
Answer : KHCO3 is highly soluble in water and cannot be isolated.
It is prepared by Le Blanc Process like for Na2CO3.
BIOLOGICAL IMPORTANCE OF Na and K:
(1) In a 70 Kg man there are 90 g of Na+ and 170 g of K+ (only 5 g of Fe and 0.06 g of Cu)
(2) Na+ exist outside the cells in blood plasma. They participate in the transmission of nerve signals, in regulating
the flow of water across cell membranes and in the transport of sugars and amino acids into cells.
(2) K+ ions exist inside cells and activate many enzymes, participate in the oxidation of glucose to produce ATP
also participate in the transmission of nerve signals alongiwth Na+.
(3) Outside the cell : Na+ = 143 mmol/L and K+ = 5 mmol/L while inside cell : Na+ = 10 mmol/L and K+=105
mmol/L. In order to keep appropriate concentrations of Na+ and K+ inside and outside cells, Na-K pump(an
enzyme present in the cell membrane) pumps more Na+ out and less K+ in(3 : 2). For this process ATP is used.

Dr. S. S. Tripathy