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s-BLOCK ELEMENTS - ALKALI METALS

ELEMENTS OF GROUP 1

Li  - Lithium   Na - Sodium K  - Potassium
Rb - Rubidium Cs - Caesium Fr - Francium
These elements are known as alkali metals.
Lithium is known as a bridge element and was discovered by Arfwedson.
Sodium and potassium were discovered by Davy, rubidium and caesium by Bunsen and Kirchhoff while francium by Perey.
These do not occur in the  native state (i.e.,do not occur free in nature).

GENERAL CHARACTERISTICS

Physical properties of alkali metals are:-

ELECTRONIC CONFIGURATION

These are s-block elements and have one electron in the valence shell in
s-orbital. In general  their electronic configuration may be represented as [noble gas ] ns1  where ‘n’ represents the valence shell.
Element     
Atomic no.
Electronic configuration
Valence shell configuration
Li
3
[He] 2 s1
2 s1
Na
11
[Ne] 3 s1
3 s1
K
19
[Ar] 4 s1
4 s1
Rb
37
[Kr] 5 s1
5 s1
Cs
55
[Xe] 6 s1
6 s1
Fr
87
[Rn] 7 s1
7 s1

SIZE OF THE ATOMS - ATOMIC RADII

  • The alkali metals atoms have the largest atomic radii in their respective periods.
  • Atomic radii increases as we move down the group from Li to  Cs due to the addition of a new shell at each step.

SIZE OF THE ION - IONIC RADII

  • The ions of the alkali metals are much smaller than their corresponding atomic radii due to lesser number of shells and contractive effect of the increased nuclear charge.
  • The ionic radii like atomic radii of all these alkali metal ions goes on increasing on moving down the group because of the same reason.

DENSITY

  • These are light metals having low densities. Lithium is the lightest known metal.
  • On moving down the group, both the atomic size and atomic mass increases and since the increase in latter is not compensated by increase in former,consequently density increases from Li to Cs.
  • The density of potassium is lesser than that of sodium because of the abnormal  increase in size on moving from Na to K.

MELTING AND BOILING POINTS

  • The melting and boiling points of alkali metals are quite low and decreases down the group due to weakening of metallic bond.
  • Fr is a liquid at room temperature.

SOFTNESS

These are soft,malleable and ductile solids which can be cut with  knife. They possess metallic lustre when freshly cut due to oscillation of electrons.

ATOMIC VOLUME

Atomic volume of alkali metals is the highest in each period and goes  on increasing down the group
Element
Li
Na
K
Rb
Cs
Gram atomic volume in cm3
13
24
46
56
71

IONISATION ENERGY

  • The first ionisation energy of alkali metals is the lowest amongst the elements in their respective periods and decreases on moving down the group.
Element
Li
Na
K
Rb
Cs
Fr
IE, (kJ mol–1)
520
496
419
403
376
----
  • The second ionisation energies of all the alkali  metals are very large because on releasing an electron from the elements, the resulting ions acquire noble gas (stable) configurations.

ELECTROPOSITIVE CHARACTER

Because of their low ionisation energies, alkali metals are strongly electropositive or metallic in nature and this character increases from Li to Cs.

CRYSTAL STRUCTURE

All alkali metals possess body centred cubic structures with coordination number 8

OXIDATION STATE

  • The alkali metal atoms show only +1 oxidation state, because their unipositive ions have the stable gas electronic configuration in the valence shell.
  • Since the alkali metal ions have noble gas configuration with no unpaired electrons, they are diamagnetic and colourless but their permanganates and dichromates compounds are coloured.

HYDRATION OF IONS

  • All alkali  metal salts are ionic (except Lithium) and soluble  in water due to the fact that cations get hydrated by water molecules. The  degree of hydration depends upon the size of the cation. Smaller the size of a cation, greater is its hydration energy.

Relative ionic radii :

Relative ionic radii in water or relative degree of hydration :
  • The alkali metal ions exist as hydrated ions    in the aqueous solution.
  • Since the degree of hydration of decreases as we go down the group, the hydration  energy of alkali metal ions decreases from

FLAME COLOURATION

  • All alkali metals and their salts impart characteristic colours to the flame  because of the bonding of the outermost electron.The outer electrons of these atoms are excited to higher energy levels. On returning to the original state they give out visible light of characteristic wavelength. This gives a characteristic colour to the flame.
  • On moving down the group, the ionisation energy goes on decreasing and hence the energy or the frequency of emitted light goes on increasing in the order Li  < Na < K < Rb < Cs. As a result, the colour shows following trend-
Li
Na
K
Rb
Cs
crimson
golden
pale  
purple
sky blue
red
yellow
violet
(violet)

PHOTOELECTRIC EFFECT

Due to low I.E., alkali metals especially K and Cs show photoelectric effect (i.e.  eject electrons when exposed to light) and hence are used in photoelectric cells.

ELECTRICAL CONDUCTIVITY

Due to the presence of loosely held valence electrons which are free to move throughout the metal structure, the alkali metals are good conductors of heat and electricity. Electrical conductivity increases from top to bottom in the order

REDUCING CHARACTER

  • All the alkali metals are good reducing agents
    and it is due to their low ionisation energies.
    Their reducing character, follows the order
  • Among the alkali metals Li has the highest negative electrode potential, which depends upon its (i) heat of vaporisation (ii) ionisation energy and (iii) heat of hydration and hence Li is the strongest reducing agent.
Elements
 Li
  Na
K
 Rb
Cs
Fr
(V)at at 298 K
–3.05
–2.71
–2.93
–2.99
–2.99
 —

CHEMICAL PROPERTIES

ALKALI METALS FORM IONIC COMPOUNDS

(Lithium can form covalent compounds because of its high ionisation energy) and others form ionic compounds because of their large atomic size and low I.E. 

ALKALI METALS ARE VERY REACTIVE

Due to low I.E. and high electropositive character the alkali metals are chemically very reactive.

ACTION OF AIR

On exposure to moist air, their surface is tarnished due to the formation of  their oxides, hydroxides and carbonates at the surface.
Hence they are kept under inert liquid kerosene oil but lithium is kept wrapped in paraffin wax because it floats on the surface of kerosene oil due to its very low density.

ACTION OF OXYGEN

  • All the alkali metals when  heated with oxygen form different types of oxides for example, lithium forms lithium oxide, sodium forms sodium peroxide , while K, Rb and Cs form their respective superoxides ( where M=K, Rb or Cs). The increasing stability of peroxides and superoxides of alkali metals from Li to Cs  is due to stabilisation of larger anions by larger cations through lattice energy.
  • Superoxides are coloured and paramagnetic as these possess three electron bond where one unpaired electron is present.Sodium peroxide acquires yellow colour due to the presence of traces of superoxide as an impurity.is orange, is brown and   is orange in colour.
  • All oxides, peroxides and superoxides are basic in nature.
  • The solubility and basic strength of oxides increase in the order  
  • The stability of peroxides and superoxides increases in the order
     

ACTION WITH WATER AND OTHER COMPOUNDS CONTAINING ACIDIC HYDROGEN

  • All the alkali metals readily react with water  evolving hydrogen.
(where M=Li, Na, K, Rb or Cs)
The reactivity with water increases on descending the  group from Li to as
Li < Na < K < Rb < Cs  due to increase in electropositive character in the same  order.
  • Alkali metals also react with alcohols and acetylene and liberate

ACTION OF HYDROGEN  

Alkali metals combine with hydrogen to form ionic hydrides M+H-
The reactivity of alkali metals towards hydrogen decreases as we move down the group i.e. Li  > Na > K > Rb > Cs, due to the decreasing lattice energy of these hydrides with the increasing size of the metal cation. Thus the stability of  hydrides follows the order
LiH > NaH > KH > RbH > CsH

REACTION WITH HALOGENS

  • Alkali metals combine readily with halogens to form ionic halides
[where M= Li,Na, K etc. and X = F,Cl, Br,I]
  • The reactivity of alkali metals towards a particular halogen increases in the order  :
Li < Na  < K < Rb < Cs
while that of halogen  towards a particular alkali metal decreases in the order :
  • All alkali halides except LiF are freely soluble in water (LiF is soluble in non-polar solvents. Since it has strong covalent bond.)
  • The power of the cation to polarise the anion  is known as the polarising power while the tendency of the anion to get polarised is known as its polarisability. The polarising power of cation and polarisability of anion depends on the following factors (which are collectively referred to as Fajan’s rules)
    • Size of the cation - Smaller the size of cation greater is its polarising power. So LiCl is more covalent than KCl.
    • Size of the anion - Bigger the anion, larger is its polarisability. Hence the covalent character of lithium halides  is in the order -
LiI > LiBr > LiCl > LiF
    • Charge of the ion and electronic configuration - Larger the charge on the cation, greater is its polarising power
Thus the covalent character of various halides is in the order
when two cations have same charge and size, the one having 18 electrons in their outermost shell will have larger polarising power than a cation having 8 electrons in the outermost shell. For example CuCl is more covalent than NaCl.
Above rules help to predict the ionic /covalent character of metal halides.

MELTING POINTS OF ALKALI METAL HALIDES

  • For the same alkali metal, the melting points decrease in the order with the     increase in the size of halides ion. Fluorides > chlorides > bromides > iodides
  • For the same halide ion, melting points decreases with the increasing size of the  metal but lithium halides being covalent have lower melting point than corresponding sodium halides.

REACTION WITH NITROGEN

Only lithium reacts  with nitrogen and forms lithium nitride ()

REACTION WITH SULPHUR AND PHOSPHORUS

Alkali metals  react with sulphur and phosphorus on heating and form respective sulphides and phosphides.

SOLUBILITY  IN LIQUID AMMONIA

All alkali metals dissolve in liquid ammonia giving deep blue solution, which has some characteristic properties given below due to formation of ammoniated metal cations and ammoniated electrons in the solution.
            
  • Colour - The blue colour is due to the excitation of ammoniated electron to higher energy levels and the absorption of photons occurs in the red region of the spectrum.Thus the solution appears blue.But at very high concentration  the solution attains the colour like that of metallic copper.
  • Conductivity - It is highly conducting because of the presence of ammoniated electrons and ammoniated cations.However, on cooling,the conductivity increases further.
  • Paramagnetism - It is paramagnetic due to the presence of an unpaired electrons and ammoniated  cations.However the paramagnetism decreases with increasing concentration due to the  association of ammoniated electrons to yield diamagnetic species containing electron pairs.
  • Reducing property - Due  to the presence of ammoniated electrons, solution is a very powerful reducing agent and used in organic chemistry under the name Birch reduction.

COMPLEX FORMATION

Alkali metals have a weak tendency to form complexes but polydentate ligands such as crown ethers and cryptands form highly stable complexes collectively called as Wrap Around Complexes. Cryptands are macrocyclic molecules with N and O  atoms and their complexes are called cryptates. The name cryptate came from the  fact that metal ion is hidden in the structure.

NATURE OF HYDROXIDES

Alkali metals hydroxides are very strong bases, highly soluble in water and are not decomposed on heating.However, LiOH decomposes on heating to give  because latter is more stable than former.
Their  basic strength increases from LiOH to CsOH due to a corresponding decresae in the I.E., of the metal in a group,i.e., the order:-  
LiOH < NaOH < KOH < RbOH < CsOH

NATURE OF CARBONATES AND BICARBONATES

  • is unstable towards heat and decomposes to give
The thermal stability of carbonates increases with  the increasing basic strength of metal hydroxides on moving down the group.Thus the order is
  • The bicarbonates of all the alkali metals are known. All the bicarbonates (except which exits in solution) exist as solids and on heating form carbonates.
  • The solubility of the carbonates and bicarbonates increases  on moving down the group due to lower lattice energies. Thus, order is

NATURE OF NITRATES  

On heating decomposes to give   while the nitrates of the other alkali metals decompose on  heating to form nitrites and.
All nitrates are soluble in water.

NATURE OF SULPHATES

  • Li2SO4 is insoluble in water whereas other sulphates i.e, Na2SO4, K2SO4 are soluble in water.
  • Lithium sulphate does not form alums and is also not amorphous with other sulphates.

ANOMALOUS BEHAVIOUR OF LITHIUM

Lithium, the first member of the  alkali metal family shows an anomalous behaviour because of the following main reasons:-
  • It has the smallest size in the group
  • It has very high ionization energy and highest electronegativity  in the group.
  • It has no vacant d-orbital in the valence shell.

As a result, it differs from the other member of the alkali metal family  in following respects:
  • Lithium is harder than other alkali metals, due to strong metallic bond.
  • Lithium combines with to form lithium monoxide, , whereas other alkali metals form Peroxides, and superoxides.
  • Lithium, unlike the other alkali metals, reacts with nitrogen to form the nitride.
  • LiOH  is a weak base and decomposes to give the corresponding oxide while the hydroxides of alkali metals are stable to heat and sublime as such.
  • , LiF and lithium phosphate are insoluble in water while the corresponding salts of other alkali metals are soluble in water.
  • LiH is the stablest among all the alkali metal hydrides.
  • decomposes on heating to evolve whereas other alkali metal carbonates do not.
  • Lithium nitrate on heating  evolves O2 and NO2 and forms Li2O while other alkali metal nitrates on heating evolve and form their respective nitrites.
  • Lithium when heated with ammonia forms lithium imide  while other alkali metals form amides of the general formula ( where M=Na,K, Rb and S).
  • Only lithium combines directly with carbon to form lithium carbide, , while other alkali metals  react with ethyne to form the corresponding metal carbides.

DIAGONAL RELATIONSHIP

Lithium shows diagonal relationship with magnesium, the element of group 2 and this resemblance is due to polarising power, i.e,  is similar for both of these elements.

Lithium resembles magnesium in the following respects:
  • The atomic radius of Lithium is  while that of magnesium is
  • The ionic radius of which is very close to that of Mg2+ ion (0.65Å).
  • Lithium (1.0) and magnesium (1.2) have almost similar electronegativities.
  • Both Li and Mg are hard metals.
  • LiF is partially soluble in water like .
  • Both decompose water only  on heating.
  • Alkyls of lithium and magnesium are soluble in organic solvents.
  • Both combine with to form  monoxides,e.g., and MgO.
  • Both LiOH and are weak bases.
  • Both LiCl and are predominantly covalent.
  • Both Li and Mg  combine with to form their respective  nitrides, and.
  • The hydroxides and carbonates of both Li and Mg  decompose on heating and form their respective oxides.
  • Both lithium and magnesium nitrates on heating  evolve and leaving behind their oxides.
Fire caused by burning of alkali metals is extinguished by sprinkling .
A mixture of and dil.HCl is commercially called Oxone and is used for bleaching delicate fibres.

METALLURGY OF SODIUM

OCCURRENCE AND MINERALS

  • Sodium does not occur in the  free state because of its high reactivity.
  • Important  minerals of sodium are -
    • Common salt or rock salt,NaCl
    • Chile saltpetre,
    • Sodium carbonate,
    • Sodium sulphate or Glauber’s salt  Na2SO4. 10 H2O
    • Cryolite,
    • Borax,

EXTRACTION  OF SODIUM

  • Sodium metal is extracted by electrolysis of fused NaCl containing a little and KF at 873 K. This process is known as Down process.
  • Reactions during electrolysis
  • Difficulties during the process
    • Sodium cannot be extracted from  aqueous NaCl because the metal liberated at the cathode reacts with to form metal hydroxide and.
    • NaCl melts at 800º C and it is difficult to attain and maintain this high temperature.
    • Molten Na forms a metallic fog (colloidal solution ) with fused NaCl.
Above difficulties were removed by adding and KF  to fused NaCl which themselves do not undergo decomposition at the voltage employed and lower the melting point of NaCl to about. The electrodes are separated by a wire gauze to prevent the reaction between Na and

METALLURGY OF POTASSIUM

OCCURRENCE AND MINERALS

  • Potassium also does not occur in free state.
  • Important minerals of potassium are
    • Sylvine, KCl
    • Carnallite,
    • Feldspar,
    • Kainite,

EXTRACTION OF POTASSIUM

Potassium is not obtained by the electrolysis of fused KCl because K has lower boiling point (1039 K)  than the melting point of KCl (1063K) and hence it get vaporises. Therefore, K metal is extracted by the following methods :-
  • By the electrolysis of fused KOH - The reaction involved are
  • Modern method - By the  reduction of molten KCl with metallic sodium in stainless steel vessel  at 1120-1150 K.

COMPOUNDS OF SODIUM

SODIUM CHLORIDE, COMMON SALT OR TABLE SALT, NaCl

  • It is obtained by evaporation of sea water in sun but due to presence of impurities like  it is deliquescent It is purified by passing HCl gas through the impure saturated solution of NaCl and  due to common ion effect, pure NaCl gets precipitated.
  • 28% NaCl solution is called Brine.

SODIUM HYDROXIDE, CAUSTIC SODA, NaOH

PREPARATION
  • Causticizing process ( Gossage process) - A 10% solution of  is treated with milk of lime, .
  • Electrolytic process - In this process a concentrated solution of sodium chloride is electrolysed where is evolved at the anode and at the cathode. However gas reacts with  NaOH forming NaCl and  sodium hypochlorite.

Mercury cathode process (Castner - Kellner cell)
This process is  used to avoid reaction between NaOH and .NaOH is obtained by the electrolysis of (aqueous) solution of brine. The cell has three compartments and  involves following reactions :-

In outer compartment -
Anode - Graphite rods
Cathode - Mercury
Electrolyte -Brine solution  
Reaction - At  Anode :
      
At Cathode :

In central compartment -
Anode - Mercury
Cathode - Iron rods
Electrolyte - dil. solution of  NaOH
Reaction - At  Anode :
At Cathode :
  • Lowing's Process
  • Pure Sodium Hydroxide
        
The filtration on evaporation give pure NaOH

PROPERTIES
  • It is a hygroscopic, deliquescent white solid, absorbs CO2 and moisture from the atmosphere.
  • Reaction with salts:- It reacts with metallic salts to form hydroxides out of which some are unstable and decompose to insoluble oxides,
    • Formation of  insoluble hydroxides, e.g.
    • Formation of unstable hydroxides, e.g.
    • Formation of insoluble hydroxides which dissolve in excess of NaOH e.g. Zn, Al, Sb, Pb, Sn and As.
    • Formation of ammonia from ammonium salts :-
  • Reaction with halogens:-
(where X= Cl,Br or I)
  • Reaction with metals :- Less electropositive metals like Zn, Al and Sn etc. give H2 gas with NaOH.
  • Reaction with sand:-
  • Reaction with CO :-
  • Reaction with non-metals e.g.with P, Si, S, F, etc.
  • It breaks down the proteins of the skin flesh to a pasty mass and hence it is commonly known as caustic soda.

SODIUM CARBONATE OR WASHING SODA :

PREPARATION
  • Solvay or ammonia - soda process :- In this process,NaCl (brine), ammonia and are taken as raw materials. The involving reactions are
  • Electrolytic Process :- In this Nelson cell is used for the manufacture of NaOH, CO2 under pressure is blown with steam
  • Leblance Process :-This is now an absolute method.
PROPERTIES
  • Sodium Carbonate crystallizes from water as decahydrate which efflorescence on exposure to dry air forming monohydrate which on heating change to anhydrous salt (soda-ash).
  • On hydrolysis it forms an alkaline solution
  • Aqueous sodium carbonate solution react with CO2 gas and forms sodium bicarbonate.
  • It is used as fusion mixture

SODIUM BICARBONATE, BAKING SODA, NaHCO3

PREPARATION
It is obtained as an intermediate product in Solvay ammonia process.

PROPERTIES
  • Heating effect :- It gives
  • In aqueous medium it is alkaline due to hydrolysis:
  • It is used as a constituent of baking powder and in medicine to remove acidity of the stomach (as antacid).
  • It is present in Selidlitz powder.
  • Baking powder is a mixture of starch, sodium bicarbonate and potassium hydrogen tartarate.
  • Fire extinguishers contain
  • is called Glauber’s salt, anhydrous is called salt cake, is called chile salt-petre, is called nitre cake, mixture   of and dil. HCl is called oxone.
  • When common salt is fused with a little, 5% to 10%and some sugar, it acquires a dark purple colour and has a characteristic saline taste. It is used in medicine and is useful for digestion.It is called kala namak or black salt or sulemani namak.

COMPOUNDS OF POTASSIUM

POTASSIUM HYDROXIDE,CAUSTIC POTASH, KOH

PREPARATION
  • It is prepared in a cell similar to that used for NaOH. In this cell electrolysis of an aqueous solution of KCl takes place.
  • It is also prepared by the action of soda lime on potassium carbonate.

POTASSIUM CARBONATE, POTASH, PEARL ASH, K2CO3

PREPARATION
It is prepared by following two methods-
  • By Leblanc process
  • By Precht process (magnesia process)

POTASSIUM CYANIDE, KCN:

PREPARATION
  • By heating potassium ferrocyanide with metallic potassium
  • It is used  in electroplating and due to the formation of soluble  complexes with gold and silver, it is used in extraction of these metals.

POTASSIUM CHLORATE, KCLO

PREPARATION
  • By passing through boiling concentrated KOH solution.
  • By the action  of KCl on (obtained by electrolysis of NaCl at 345-350K).

PROPERTIES
It used as an oxidising agent and in the laboratory and preparation of .

is called Indian salt petre or nitre.

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