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Some of the characteristics of halides are :

(i) Beryllium halides are covalent while halides of other alkaline earth metals are ionic.
The ionic character of halides increases down the group due to gradual increase in ionic size.
(ii) Beryllium halides being covalent are soluble in organic solvents.
(iii) Fluorides of other elements are generally insoluble in water due to high magnitude of lattice enthalpy but bromides,
chlorides and iodides are soluble in water.
(iv) The anhydrous halides are hygroscopic and form hydrates such as MgCl2.6H2O, CaCl2.6H2O, SrCl2.6H2O and
BaCl2.2H2O. The tendency to form halide hydrates decreases down the group. Because of this property anhydrous
calcium chloride is used as dehydrating agent. Beryllium chloride fumes in moist air due to its hydrolysis.
BeCl2 + 2H2O Be(OH)2 + 2HC1
(Moisture) (Fumes)
8. Nitrides
The alkaline earth elements burn in nitrogen to form ionic nitrides with formula M3N2.
3Ca + N2 Ca3N2 3Mg + N2 Mg3N2
The nitrides are, in general, crystalline solids and are decomposed by water to produce ammonia and metal hydroxide
Ca3N2 + 6H2O 3Ca(OH)2 + 2NH3
9. Solubility in Liguid Ammonia
Like alkali metals, the alkaline earth metals dissolve in liquid ammonia to give deep blue black solution. These
solutions contain ammoniated cations and ammoniated electrons.
M + (x + y) NH3 [M (NH3)x]2+ + 2 [e(NH3)y]
10. Complex Compounds
Group 2 elements have a tendency to form stable complexes.Their ability to form complexes is more as compared to
alkali metals. This is because of the smaller size and higher charge ot the alkaline earth metal ions as compared to
alkali metal ions. Among the elements of group 2, beryllium and magnesium, have greater tendency of complexation,
For example, magnesium is present in green colouring material of plants, i,e., chlorophyll.
ANOMALOUS BEHAVIOUR OF BERYLLIUM AND ITS DIAGONAL RELATIONSHIP WITH ALUMINIUM
Anomalous Behaviour of Beryllium.
The properties of beryllium, the first member of the alkaline earth metals, differ from rest of the members. It is mainly
because of
1. Its small size and high polarizing power;
2. Relatively high electronegativity and ionization enthalpy as compared to other members ;
3. Absence of vacant d-orbitals in its valence shell.
Some important points of difference between beryllium and magnesium are given below :
1. Be is lighter than Mg.
2. Melting point and boiling point of Be are higher than those of Mg.
3. Be does not react with water even at high temperature while Mg decomposes boiling water.
4. The oxide and hydroxide of beryllium are amphoteric while those of other alkaline earth metals are basic in nature. For
example BeO is amphoteric while MgO is weakly basic.
5. Beryllium carbide reacts with water to give methane while magnesium carbide produces acetylene,
Be2C + 4H2O 2Be(OH)2+ CH4 MgC2 + 2H2O Mg(OH)2 + C2H2
Methane Acetylene
6. Beryllium does not exhibit co-ordination number more than four as it has only four orbitals in the valence shell. The
other members of this group can have a co-ordination number 6.
Resemblance of Beryllium with Aluminium
Beryllium resembles aluminium to some extent due to nearly the same value of charge to radius ratio. The
following points illustrate the anomalous behaviour of beryllium and its resemblance with aluminium :
1. Unlike group-2 elements but like aluminium, beryllium forms covalent compounds.
2. The hydroxides of beryllium, (Be(OH)2) and aluminium, (A1(OH)3) are amphoteric in nature, whereas those of other
elements of group-2 are basic in nature.
3. Like aluminium, beryllium is not readily attacked by acids because of the presence of an oxide film.
4. Beryllium and aluminium form fluoro-complex ions, [BeF]2 and [AlFg]3 in solution, whereas the other elements of
group-2 do not form stable fluoro-complexes in solution.
5. The oxides of both Be and Al, i.e., BeO and A12O3 are high melting insoluble solids.
6. Carbides of both Al and Be give methane on hydrolysis.
7. BeCl2 like A12C16 has a bridged polymeric structure. Both these compounds are strong Lewis acids and are soluble
in organic solvents.
8. The salts of beryllium as well as aluminium are extensively hydrolysed.

* * * * *

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(ii) These hydroxides are less soluble in water as compared to the alkali metal hydroxides. However, they give strongly
alkaline solutions due to their ready ionizability to form OH(aq). All these bases neutralize acids to give salts &
water.
M(OH)2 + 2HCl MCl2 + 2H2O
(M = Mg, Ca, Sr, Ba)
(iii) The solubility of the hydroxides in water increases with the increase in atomic number. Be(OH)2 and Mg(OH)2 are
almost insoluble, Ca(OH)2 is sparingly soluble while Sr(OH)2 and Ba(OH)2 are increasingly more soluble.

Reason. Among the hydroxides of this group it is observed that the magnitude of hydration enthalpy decreases but
less significantly whereas the magnitude of lattice enthalpy also decreases but more significantly down the group
due to increase in size. Thus, the overall net effect of the two factors, (Hlattice - HHydration = Solution) HSolution
becomes more negative from Be to Ba accounting for increase in solubility.
Aqueous solutions of calcium hydroxide (lime water) and barium hydroxide (baryta) are used to detect and estimate
carbon dioxide because they give precipitates of corresponding carbonates with CO2.
Ca(OH)2 + CO2 CaCO3 + H2O Ba(OH)2 + CO2 BaCO3 + H2O
White ppt. White ppt
However, if excess CO2 is passed, the precipitates dissolve due to the formation of soluble bicarbonates.

CaCO3 + H2O Ca(HCO3)2

4. Reaction with Water:


All these metals react with water to give the hydroxides and hydrogen. The reactivity increases with increasing
atomic number. Beryllium is hardly affected by water at room temperature. It does not react readily even with boiling
water. Magnesium, on the other hand, reacts only with boiling water, whereas calcium, strontium and barium react
vigorously with water even at room temperature.
M(s) + 2H2O(l) M2+(aq) + 2OH(aq) + H2(g)
The reaction of alkaline earth metals with water is less vigorous as compared with that of alkali metals.
5. Carbonates:
Carbonates of alkaline earth metals are insoluble in water. These can be precipitated by addition of sodium or
ammonium carbonate solution to the solution of salts of these metals. For example,
CaCl2 + Na2CO3 CaCO3 + 2NaCl
ppt.
All the carbonates decompose on heating to give carbon dioxide and metal oxide.
MCO3 MO + CO2


However, as the atomic number increases, the stability of the carbonates towards heat increases. Beryllium carbonate
is unstable and can be kept only in an atmosphere of CO2.
Reason: The stability of carbonate towards heat depends upon the relative stability of the resulting metal oxide.
More is the stability of the resulting metal oxide lesser is the stability of the carbonate towards heat and vice
versa. Now the stability of resulting metal oxides decreases down the group due to decrease in lattice enthalpy,
(because of bigger size) therefore the stability of carbonates towards heat increases.
6. Sulphates:
Sulphates of alkaline earth metals can be prepared by the reaction of H2SO4.with the metals, their oxides, hydroxides
or carbonates.
Ca + H2SO4 CaSO4 + H2 CaO + H2SO4 CaSO4 + H2O
Ca(OH)2 + H2SO4 CaSO4 + 2H2O CaCO3 + H2SO4 CaSO4 + CO2 + H2O
The sulphates of alkaline earth metals are less soluble than the corresponding salts of alkali metals. Their solubilities
decrease on going down the group.
Reason. It is because in going down the group from Be to Ra, the magnitude of hydration enthalpy decreases
significantly, due to increase in the atomic size of alkaline earth metals, bringing about a decrease in solubility of
their sulphates.
Unlike carbonates, sulphates of alkaline earth metals are stable to heat.
7. Halides:
Alkaline earth metals react with halogens directly, on heating, to form halides having general formula,
M + X2 MX2 (X = F, Cl, Br, I)
Alkaline earth metal halides can also be obtained by the action of halogen acids on metals, their oxides, carbonates
and hydroxides.
M + 2HXMX2 + H2 MO + 2HXMX2 + H2O
MCO3 + 2HX MX2 + H2O + CO2 M(OH)2 + 2HX MX2 + 2H2O

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9. Characteristic Flame Colouration :
Except Be and Mg, the alkaline earth metals impart characteristic colour when introduced into the flame of a bunsen
burner. Calcium imparts brick red, strohtium crimson and barium grassy green colour. This property is due to the
ease of excitation of their valence electrons
Beryllium and magnesium do not impart colour to the flame.
Reason. Be and Mg have very high ionization enthalpies and therefore, large amount of energy is required to
excite their electrons. This energy is not available from the flame and hence their electrons are not excited.
10. The alkaline earth metals are denser and harder than the corresponding alkali metals:
Reason. The atoms of alkaline earth elements have smaller size and are hence held by stronger metallic bonds, as
compared to alkali metals. Therefore, they are more closely packed in their crystal lattices which accounts for
high density and increased hardness of these elements.
11. Melting Point and Boiling Point
The alkaline earth metals because of their smaller size and a more close packed structure have higher melting and
boiling points than the alkali metals.
The reactivity of these elements increases on going down the group. As compared to alkali metals, these elements
are less reactive because they have relatively higher ionization enthalpies.
1. Hydrides
All the members of the group, except beryllium, combine with hydrogen on heating to , form metal hydrides, MH2.
M + H2 MH2
BeH2 can, however, be produced by reduction of BeCl2 with LiAlH4.
BeCl2 + LiAlH4 2BeH2+LiCI + A1C13
Some of the characteristics of hydrides are :
(i) MgH2 is covalent in nature, while CaH2, SrH2 and BaH2 are ionic in nature. CaH2 is also known as hydrolith.
(ii) These hydrides have high reactivity with water. They react in water producing hydrogen gas
MH2(s) + 2H2O(l) M2+(aq) + 2OH(aq) + 2H2(g)
CaH2(s) + 2H2O(l) Ca2+(aq) + 2OH(aq) + 2H2(g)
2. Oxides
Beryllium and magnesium are kinetically inert towards oxygen due to formation of a film of oxide on their surface.
However, all the alkaline earth metals burn in oxygen forming oxides. Beryllium, magnesium and calcium form monoxides
while strontium and barium form peroxides.
2M + O2 2MO (M = Be, Mg or Ca)
(Monoxide)
M + O2 MO2 (M = Ba or Sr)
(Peroxide)
The monoxides can also be prepared by decomposition of their respective carbonates.
MCO3MO + CO2 (M = Be, Mg, Ca, Sr or Ba)
The reactivity of these metals towards oxygen increases as we move down the group.
Alkaline earth mgtals burn in air forming oxides and nitrides.
2Mg + O2 2MgO 3Mg + N2 Mg3N2
Some of the characterstics of oxides are:
(i) They are very stable due to large enthalpies of formation.
(ii) The monoxides of all the alkaline earth metals, except BeO, have rock salt structure.
(iii) BeO is amphoteric while oxide of another elements are basic in nature.The amphoteric nature of BeO is illustrated by
its reaction with acids as well as alkalies.
BeO + 2HC1 BeCl2 + H2O BeO + 2NaOH + H2O Na2[Be(OH)4]
Sodium beryllate
(iv) All these oxides, except BeO, react with water with evolution of heat to form corresponding hydroxides which are
sparingly soluble.
MO(s) + H2O(l) M2+(aq) + 2OH(aq) + heat
3. Hydroxides:
The hydroxides of these elements can be formed either by dissolving.metal oxides in water or by reaction of these
elements with water. All the alkaline earth metal hydroxides are base except Be(OH)2 which is amphoteric.
Some of the characteristics of hydroxides are :

(i) The hydroxides of magnesium, calcium, strontium and barium are bases and
their basic strength increases from magnesium to barium. It is becuase of decrease
in ionization enthalpy down the group due to which the strength of MO bond
in MOH decrease and hence causes an increase in basic character.

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2. Ionization Enthalpy and Electropositive Character:
The alkaline earth metals owing to their large size of atoms have fairly low values of ionization enthalpies as compared
to the pblock elements. However, within the group, the ionisation enthalpy decreases as the atomic number increases.
Although the first ionization enthalpies alkaline earth metals are higher than those of alkali metals while the second
ionization enthalpies values are much lower than those of alkali metals.
Reason : The second electron in the case of alkali metals is to be removed from a cation which has already acquired
a noble gas configuration while in alkaline earth metals, the second electron is to be reamoved from a monovalent
cation which is yet to acquire the stable noble gas configuration. Therefore, the second electron can be removed
more easily in the case of group 2 elements than in group 1 elements.
3. Hydration Enthalpies:
The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metals ions. Therefore, compounds
of alkaline earth metals are more extensively hydrated. For example, magnesium chloride and calcium chloride exist as
hexahydrates (MgCl2 6H2O and CaCl2 6H2O) whereas sodium chloride and potassium chloride do not form such
hydrates.
Among alkaline earth metal ions the hydration enthalpies decreases on moving from top to bottom in the group
Be2+ > Mg2+ > Ca2+ > Sr2+> Ba2+
This trend can be explained in terms of increase in ionic size down the group.

4. Oxidation states:
Alkaline earth metals exhibit +2 oxidation state in their compounds.
Although the second ionization enthalpies of these elements are high as compared to the first, yet they exist as
divalent ions in most of their compounds because of the following reasons:
(i) Divalent ions have the stable noble gas configuration.
(ii) The divalent cations result in stronger lattices than monovalent cations and hence a lot of energy called lattice enthalpy
is released which easily compensates for the high second ionization enthalpy. This accounts for the existence of divalent
ions in solid state.
(iii) The divalent cation due to smaller size gets hydrated in water to a greater extent and thus the hydration enthalpy
released compensates for the second ionization enthalpy. This accounts for the existence of divalent ions in aqueous
state.
5. Reducing Properties:
All the members of group 2, owing to their low ionisation energies have a tendency to lose their valence electrons and
thus act as strong reducing agents. As the reduction potential values decreases down the group it indicates the
increase in strength as a reducing agent. However, the members of this group are weaker reducing agents than the
alkali metals. It is because of higher ionization enthalpy of earth metlas as compared to alkali metals.
6. Nature of Bonds Formed:
The elements of this group form ionic compounds. The tendency for forming ionic compounds increases down the
group. The first member, Be forms covalent compounds. Mg also shows some tendency for covalency.
Reason. Due to low ionization enthalpies these form ionic compounds. As the ionization enthalpy decreases down
the group, therefore, tendency to form ionic compounds increases. Beryllium on the contrary because of its small
size and high ionization enthalpy forms covalent compounds.
7. Electropositive Character or Metallic Character:
Strong electropositive character or metallic character. However, they are less electropositive than the alkali
metals.
8. Nature of Metallic Bonding in Alkaline Earth Metals:
In contrast to the single electron per atom contributed to metallic bonding in alkali metals; two electrons of the
alkaline earth metals are involved in the metallic bonding. Moreover, sizes of alkaline earth metal ions are smaller than
those of alkali metal ions. Consequently, strong metallic bonds are formed which result in the close packing of the
atoms. Due to the presence of stronger metallic bonds alkaline earth metals have (i) higher melting points ; (ii)
higher boiling points ; (iii) higher densities and (iv) are harder than the corresponding alkali metals.

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12Na + P4 4Na3P


Sodium phosphide
7. Complex Compounds :
The group 1 metal ions form fewer complex compounds than any other group of metal ions. The complex forming
ability decreases in the order.
Li > Na > K > Rb > Cs.
ANOMALOUS PROPERTIES OF LITHIUM AND ITS DIAGONALRELATIONSHIPWITH MAGNESIUM
The main reasons for the amomalous behaviour of lithium as compared to other alkali metals are:
(i) The extremely small size of lithium atom and its ion.
(ii) Greater polarizing power of lithium ion (Li+), due to its small size which results in the covalent character in its
compounds.
(iii) Least electropositive character and highest ionization enthalpy as compared to other alkali metals.
The reason for resemblance of properties of lithium with magnesium is, that these two elements have almost same atomic
radii (Li = 152 pm, Mg = 160 pm) and ionic radii (Li+ = 76 pm, Mg2+=72 pm).
The following points illustrate the amomalous properties of lithium and its diagonal relationship with magnesium :
(1) The melting point and boiling point of lithium are comparatively high as compared to that of other alkali metals.
(2) Lithium is much harder than the other alkali metals. Magnesium is also a hard metal.
(3) Lithium reacts with oxygen least readily to form normal oxide whereas other alkali metals form peroxides and superoxides.
Magnesium also forms normal oxide.
(4) LiOH like Mg(OH)2 is a weak base. Hydroxides of other alkali metals are strong bases.
(5) Due to their appreciable covalent nature, the halides and alkyls of lithium and magnesium are soluble in organic
solvents.
(6) Unlike elements of group 1 but like magnesium, lithium forms nitride with nitrogen.
6Li + N2 2Li3N;
3Mg + N2 Mg3N2

(7) LiCl is deliquescent and crystallizes as a hydrate, LiCl . 2H2O. Other alkali metals do not form hydrates. MgCl2 also
forms hydrate, MgCl2 . 8H2O.
(8) Unlike other alkali metals lithium reacts directly with carbon to form an ionic carbide. Magnesium also forms a similar
carbide.
(9) The carbonates, hydroxides and nitrates of lithium as well as magnesium decompose on heating.
Li2CO3 Li2O + CO2
MgCO3 MgO + CO2

2LiOH Li2O + H2O
Mg(OH)2 MgO + H2O

4LiNO3 2Li2O + 4NO2 + O2
2Mg(NO3)2 2Mg + 4NO2 + O2

The corresponding salts of other alkali metals are stable towards heat.
(10) Lithium nitrate, on heating, decomposes to give lithium oxide, Li2O whereas other alkali metal nitrates decompose to
give the corresponding nitrite.
4LiNO3 2Li2O + 4NO2 + O2
2NaNO3 2NaNO2 + O2

2KNO3 2KNO2 + O2

(11) Li2CO3, LiOH LiF and Li3PO4 are the only alkali metal salts which are insoluble in water. The corresponding magnesium
compounds are also insoluble in water.
(12) Hydrogen carbonates of both lithium and magnesium cannot be isolated in solid state. Hydrogen carbonates of other
alkali metals can be isolated in solid state.

GGGGG 2 GGGGGGGG GG GGGGGGGG GGGGG GGGGGG:


The elements of group 2 are beryllium(Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium
(Ra). All these elements are metallic in nature known as alkaline earth metals. Their general electronic configuration
may be represented as
[Noble gas] ns2 ; n = 2 to 7
GENERALTRENDS INATOMIC AND PHYSICAL PROPERTIES
Like alkali metals, the compounds of these elements are also predominantly ionic. The first member beryllium differs
from the rest of the members. The last element of the group, radium is a radioactive element.
1. Atomic and Ionic Radii:
The atomic radii as well as ionic radii of the members of the family are smaller than the corresponding to members of
alkali metals.
Within the group, the atomic as well as ionic radii increase with increase in atomic number.

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4Li + O2 2Li2O

Lithium oxide
2Na + O2 Na2O2

Sodium peroxide
K + O2 KO2

Potassium superoxide
The stability of peroxide or superoxide increases as the size of the alkali metal increases. This is due to stabilization of
large anions by large cations through lattice energy affects.
The peroxides of alkali metals are colourless and diamagnetic while superoxides are paramagnetic and yellow or
orange coloured.
The normal oxides of alkali metals dissolve readily in water to form hydroxides and a large amount of heat is produced.
M2O(s) + H2O(l) 2MOH(aq) + Heat

The peroxides and superoxides are also readily hydrolysed by water as shown below :
Na2O2(s) + 2H2O(l) 2NaOH(aq) + H2O2(aq)

2KO2(s) + 2H2O(l) 2KOH(aq) + H2O2(aq) + O2(g)

The higher oxides generally act as good oxidising agents. Sodium peroxide is widely used as an oxidizing agent in
inorganic chemistry.
The hydroxides of alkali metals are strong bases.
The basic character of alkali metal hydroxides increases in going down the group.
Alkali metal hydroxides are freely soluble in water and their dissolution in water is accompanied by evolution of much
heat due to intense hydration.
3. Reaction with Water :
Alkali metals react with water and other compounds containing acidic hydrogen atoms such as hydrogen halides
(HX) and acetylene (C2H2) and liberate hydrogen gas.

2Na + 2H2O
2NaOH + H2
2Na + 2HX
2NaX + H2 ; where X = halogen

2Na + 2HC CH
2NaC CH + H2
Sodium acetylide
On descending the group from lithium to caesium, the vigour of the above reaction increases and in the case of heavier
alkali metals, the liberated hydrogen catches fire.
Since all alkali metals react with oxygen and moisture to form oxides and hydroxides, their surface gets tarnished on
exposure to atmosphere. In order to protect from atmospheric oxygen and water, these metals are stored under
kerosene oil.
4. Reaction with Halogens :
2M + X2 2MX; 2Na + Cl2 2NaCl
Reactivity of alkali metals with particular halogen increases from Li to Cs. On the other hand, reactivity of halogens with
particular alkali metal M decreases from F2 to I2.
All the halides of alkali metals except lithium fluoride are freely soluble is water. The low solubility of lithium fluoride is
attributed to greater force of attraction between lithium ions and fluoride ions in the crystal lattice.
5. Solubility in Liquid Ammonia :
All alkali metals dissolve in liquid ammonia giving deep blue solutions which are conducting in nature. These solutions
contain ammoniated cations and ammoniated electrons as shown below:
M + (x + y)NH3 M+(NH3)x + e1 (NH3)y
The blue colour of the solution is considered to be due to ammoniated electrons which abosorb energy corresponding to
red region of visible light for their excitation to higher energy levels. The transmitted light thus, imparts blue colour to the
solution. The electrical conductivity of the solution is due to both ammoniated cations and ammoniated electrons. The
blue solution on standing slowly liberates hydrogen resulting in the formation of amide :
2M + 2NH3 2MNH2 + H2

(Metal amide)
6. Reaction with Sulphur and Phosphorus :
Alkali metals react with sulphur and phosphorus on heating to form sulphides and phosphides respectively.
16Na + S8 8Na2S


Sodium sulphide

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As a result the overall tandency to oxidise itself depends on net effect of these three steps. Now since Li+ ion is the
smallest in size, therefore, the large amount of energy released in step III (enthalpy of hydration) compensates for the
higher ionization enthalpy needed in step II and hence explains the high value of oxidation potential of lithium and its
strongest reducing character.
7. Flame Colouration :
When alkali metals or their salts are heated in the flame of a Bunsen burner, they impart characteristic colours to the
flame as given below :
Reason. When energy is supplied to these elements in their salts, the electron in their valence shells get excited to
higher energy states. When these electrons jump back to their ground states the emit energy in the form of radiations
which fall in the visible region, imparting a characteristic colouration to the flame.
8. Density :
Potassium, however, is lighter than sodium. Lithium is the lightest metal having a density of 0.534 g/cm3. It cannot be
stored in kerosene oil because it floats on the surface. It is kept wrapped in paraffin wax.
Reason. The low density of alkali metals is attributed to their large atomic size and weak metallic bond. However, in
going down the group atomic size as well as atomic mass increases but the corresponding increases in atomic mass is
not compensated by the increase in atomic volume. Thus, the ratio, mass/volume, i.e., density gradually increases.
9. Melting Points and Boiling Points :
Alkali metals have low melting points. The melting points decrease on descending the group as lattice energy
decreases down the group generally.
Reason. The low melting point are attributed to their larger atomic size, due to which the binding energies of their
atoms in the crystal lattice are low. Further, in moving down the group, their atomic size increases and the strength of
metallic bond decreases which causes decrease in melting points. The boiling points of the members of this group also
follow the same order due to same reasons.
10. Soft Metals :
All the alkali metals are soft and can be cut with the help of a knife. Softness of alkali metals is due to weak metallic
bonding. Potassium is softer than sodium.

CHEMICAL PROPERTIES, AND GENERAL CHARACTERISTICS OF ALKALI METAL COMPOUNDS


The alkali metals are highly reactive elements. The cause for their high chemical reactivity is:
(a) low value of first ionization enthalpy; (b) large size; (c) low heat of atomisation.
As the value of ionization enthalpy decreases down the group from lithium to caesium, therefore, the reactivity of
alkali metals increases from Li to Cs.
1. Reaction with Dihydrogen :
Alkali metals react with dry dihydrogen at about 673 K to form crystalline hydrides which are ionic in nature and have
high melting points.

2M H 2 Heat
2 M H
Some important characteristics of hydride are given below :
(i) The stability of hydrides decreases from Li to Cs. It is because of the fact that MH bond becomes weaker due to the
increase in the size of alkali metal down the group.
(ii) These hydrides react with waterto form corresponding hydroxides and hydrogen gas.
LiH + H2O
LiOH + H2; NaH + H2O NaOH + H2.

(iii) These hydrides are strong reducing agents and their reducing nature increases down the group.
Alkali metals also form complex hydrides such as LiAlH4 and NaBH4, which are good reducing agents.
2. Oxides and Hydroxides :
Alkali metals when burnt in air form different kinds of oxides. For example, the alkali metals on reaction with limited
quantity of oxygen form normal oxides of the formula, M2O.
4M + O2 2M2O
(where M = Li, Na, K, Rb, Cs)
However, when heated with excess of air, lithium forms normal oxide, Li2O, sodium forms peroxide, Na2O2, whereas
potassium, rubidium and caesium form superoxides having general formula MO2.

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I
ALKALI METALS

The elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb),
caesium (Cs) and francium (Fr), constitute group 1 of the periodic table.
All these elements are metallic in nature and are called alkali metals. It is
because their hydroxides are strong bases or alkalies. Their general
electronic configuration may be represented as
[Noble gas] ns1 ; where n = 2 to 7.
GENERAL TRENDS IN ATOMIC AND PHYSICAL PROPERTIES :
The trends observed in the variation of different physical properties are explained below :
1. Atomic and Ionic Radii :
atomic radii of alkali metals increase on going down the group from top to bottom.
Table : Physical Properties of Group 1 Elements (Alkali Metals)
Elements Atomic Ionic Radius Hydration Ionisation enthalpy Electron Density Melting Boiling E
Radius (pm) (pm) enthalpy (kJ mol1) egativity (g cm3) Point Point (volts)
(kJ mol1) (K) (K) Oxi-
potential

I II
Lithium 152 76 506 520 7298 0.98 0.53 454 1620 3.03
Sodium 186 102 406 496 3562 0.93 0.97 371 1154.4 2.71
Potassium 227 138 330 419 3051 0.82 0.86 336 1038.5 2.93
Rubidium 248 152 310 403 2633 0.82 1.53 312 961 2.93
Caesium 265 167 376 376 2230 0.79 1.90 302 978.0 2.92
2. Hydration Enthalpies :
The hydration enthalpies of alkali metal ions decrease with increase in ionic size.
Li+ > Na+ > K+ > Rb+ > Cs+ ..... Hydration enthalpies
+
Li has maximum degree of hydration and for this reason many lithium salts exist as hydrated salts. For example, LiCl
. 2H2O.
3. Ionization Enthalpy :
The first ionization enthalpies of alkali metals are quite low as compared with the elements of the other groups
belonging to the same period. However, within the group, the ionization enthalpies of the alkali metals decrease down
the group.
Low ionization enthalpies, these metals have a strong tandency to lose their valence electrons and are strongly
electropositive or metallic in character. As this tendency for losing electrons increases down the group, the
electropositive character increases. Caesium is the most electropositive element.
4. Oxidation State :
The alkali metals have a strong tendency to lose their valence electron and change into unipositive ions. Thus, alkali
metals exhibit +1 oxidation state in their compounds.
Reason. Alkali metals have low ionization enthalpies and by losing solitary valence electron, these metals acquire the
stable configuration of nearest noble gas, therefore, these elements have strong tendency to form the M+ ions in their
compounds. The magnitudes of second ionization enthalpies are very high and are not available under the conditions
of formation of chemical bonds. Hence, alkali metals do not form M2+ ions.
5. Metallic Character :
Metallic character increases down the group.
Reason. Due to low ionization enthalpy these elements have a strong tendency to lose electrons and hence are metals.
Since the size increases down the group, and the metallic character increases.
6. Reducing Properties :
The tendency of an element to lose electron is compared by the values of reduction potential.
Reason. Due to low ionization enthalpy the alkali metals have a strong tendency to lose their valency electron easily
and thus, act as good reducing agents. The reducing character increases from Na to Cs because the ionisation energy
decreases in that order. However, Li exhibits an anomolous value. This is because the formation of M+(aq) ion from
M(s) involves three steps as illustrated on the next page.