WELCOME

TO NARAYANA GROUP

Topic : S-BLOCK ELEMENTS

 S-BLOCK ELEMENTS

 The elements where differentiating electron enters in to outermost s-orbital are

called s-block elements

 S- orbital can accommodate maximum 2 electrons so s-block contain two groups .

Group –I (IA Alkali metals) and group –II (II A Alkaline Earth metals)
Introduction of Group-1 elements:

 group 1 elements consists of lithium(Li), sodium(Na), potassium(K), rubidium(Rb),

caesium(Cs) and francium(Fr) also known as alkali metals because they forms hydroxides
on reaction with water which are strongly alkaline in nature.

 The word “alkali” is derived from the word al-qalīy meaning the plant ashes, referring to
the original source of alkaline substances.

 Among all the groups in periodic table this group is least complicated because the effect
of increasing atomic size/ atomic radium shows regular change in physical and chemical
properties of elements.
Occurrence of group-I elements:
 All the elements are available in combined state Order of abundance is Na > K > Rb > Li >
Cs

 Na is 7th most abundant element. The largest source of ‘Na’ is Rock salt.

 K is 8th most abundant element. It mainly occurs as KCl, Soluble potassium salts are
collectively called ‘Potash’

 ‘Rb’ & ‘Cs’ are obtained as by-products from ‘Li’ processing.

 Fr’ does not occur appreciably in nature and it’s a radio active element
All the elements are available in combined state, some the important minerals of 1st group
Introduction of Group-II elements:
 Group –II consists of Beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr),
barium (Ba) and radium (Ra)

 These elements (except Be) are commonly known as the alkaline earth metals. because
its oxides and hydroxides are alkaline in nature and these metal oxides found in earth
crust.

Occurrence of group-II elements:

 Order of occurrence is Ca > Mg > Ba > Sr > Be.

 Mg’ is the 6th most abundant element in the earth’s crust (2.76%). ‘Mg’ slats occur about
0.13% in sea water.
 ‘Ca’ is the 5th most abundant element in the earth’s crust (4.66%)

 Sr & Ba are found in the form of carbonates, sulphates.

some the important minerals of 2nd group

Electronic configuration of Ist group elements:

 The general valence shell electronic configuration of alkali metals is [noble gas] ns1
where ‘n’ represents the period number.
Electronic configurationof II group elements:

 The general valence shell electronic configuration of alkaline earth metals is [noble gas]
ns2 where ‘n’ represents the period number.
Atomic and ionic radii of Ist & 2ndgroup elements:

 Being the first element of each period, alkali metals have the largest atomic and ionic
radii in their respective periods.

 Li+ is much smaller than the other ions. For this reason ‘Li’ mixes with only ‘Na’ above
380 ºC , and it is immiscible with the metals K, Rb and Cs even in molten state.

 Na, K, Rb and Cs are miscible with each other in all proportions.

 The atomic and ionic radii of alkaline earth metals are smaller than the corresponding
members of the alkali metals.
 Ionization enthalpies of Ist & 2nd group elements:

 Alkali metals have the lowest ionization enthalpy (IE1) compared to other elements
present in the respective period.

 The second ionization enthalpies (IE2) of alkali metals are very high. The removal of an
electron from the alkali metals gives monovalent cations having stable electronic
configurations similar to the noble gas.

 The first ionization enthalpies of the alkaline earth metals are higher than those of the
corresponding Group 1st metals. This is due to their small size as compared to the
corresponding alkali metals.
 IP2 of alkaline earth metal is nearly double compared to its IP1 this is due to in IP2
electron we are removing from cation where nuclear charge on outermost electron will be
more compare to neutral atom

 It is interesting to note that the second ionization enthalpies of the alkaline earth metals
are smaller than those of the corresponding alkali metals.
Electropositive or Metallic character of I & II group elements:

 As their IE1 values are low, so alkali metals are strongly electropositive or metallic nature

 On moving down the group from Li to Cs electropositive or metallic character increases

 2nd group elements are less electropositive than 1st group elements

Electronegativity and Bond type I & II group elements:

 Electronegativity values for the elements in this group are very small. In fact the smallest
values of any element. Most of the alkali metal compounds are predominantly ionic. (Some
compounds of ‘Li’ are covalent).
 Electronegativity of alkaline earth metals are less but their values are more than alkali
metals
 PHYSICAL PROPERTIES
 All the alkali and alkaline earth metals are silvery white, soft and light
metals.

Density:
 Order of densities of alkalimetals is Li < K < Na < Rb < Cs

Density = Mass / volume

 On moving down both atomic mass and atomic volume increases but increase in the
atomic volume can not compensate increase in atomic mass. Exceptionally lower density
of K than Na is due to abnormal increase in size of K

 Li, Na & K are less denser than water. Hence they float in water. Rb & Cs are more
denser than water.
 Densities of alkaline earth metals decreases slightly from Be to Ca after again
increases.

 The decrease in densities from Be to Ca might be due to less closed packing of atoms in
solid lattice of Mg and Ca. These metals are denser, heavier, and harder than alkali
metals due to smaller atomic size and strong metallic bond

 All are denser than water and density order is Ra > Ba > Sr > Be > Mg > Ca
Cohesive energy:
 The cohesive energy determines the most physical properties like softness, melting points
and boiling points in metals.

 The energy which holds the atoms together in metals is called cohesive energy.

 The energy which holds the two atoms in covalent compounds is known as bond energy

 The energy which holds two atoms in ionic compounds is known as lattice energy

 It is same in magnitude but the opposite in sign to the enthalpy of atomization.

 It depends on the number of electrons that can participate in bonding and on the
strength of the bonding.
 Li to Cs the cohesive energy decreases and the softness of the metals increases.

 In alkaline earth metals valance electrons are 2 so two electrons involved in metallic
bonding so cohesive energy is more compare to alkali metals; due to this alkaline earth
metals are stronger than alkali metals

Melting and Boiling points:

 Melting and Boiling points of the alkali metals are low indicating weak metallic bonding
due to the presence of only a single valence electron in them.

 The cohesive energy decreases down the group and M.P. & B.P. decrease correspondingly.

 M.P -----> Li > Na > K > Rb > Cs

 B.P -----> Li > Na > K > Rb > Cs

 The melting and boiling points of these metals are higher than the corresponding alkali
metals due to smaller sizes. With in the group M.P and B.P do not show any regular
trend because different crystel structure adopted by different metals (Be, Mg = hcp,
Cs, Sr = ccp, Ba = bcc)

Flame Colors:
 Each of the alkali metals produces a characteristic flame color when a sample of an alkali
metal salt is placed in a flame
 The colour actually arises from electronic transitions in short-lived species which are
formed momentarily in the fame. The fame is rich in electrons, and in the case of sodium
the ions are temporarily reduced to atoms

 The electrons in Be & Mg are too strongly bound to get excited by flame hence these
elements do not impart any colour. Remaining 4 metals show different colours to
bunsen flame.

 Different colours due to different energies required to electronic excitation – de-

excitation.
Ion Hydration:
 Hydration enthalpy is a measure of the energy released when attractions are set up between
positive or negative ions and water molecules ( ion-dipole attraction).

 A major factor contributing to the strength of the ion-dipole attraction is the charge density of
the ions.
 The alkali metals have very low charge densities compared to those of other metals.

 Smaller the ion (more charge density) stronger the attraction with water so as we go down the
group size of the ion increases so hydration enthalpy also decrease.
 In this ionic tug-of-war, we find that high charge density usually favors retention of all
or part of the hydration sphere in the solid phase, while salts of low-charge density ions
tend to be anhydrous.

 The charge densities of lithium and sodium ions are high enough to favor the formation of
a few hydrated salts.

 An extreme example is lithium hydroxide, which forms an octahydrate, LiOH·8H2O.

One more example is LiCl.2H2O.

 Order of conductivity of anhydrous ion is Li+ > Na+ > K+ > Rb+ > Cs+

 Order of conductivity of hydrated ion is Cs+ > Rb+ > K+ > Na+ > Li+
 The hydration energies of group-2 ions are four or five times greater than for group-1
ions. It is largely due to their smaller size and increased charge.

 Enthalpy of hydration decreases down the group as the size of the ions increases.

 The crystalline compounds of group-2 contain more water of crystallisation than the
corresponding group-1 compounds. Thus NaCl, KCl are anhydrous but MgCl2·6H2O,
CaCl2·6H2O and BaCl2·2H2O are have water of crystallization.

 In the case of Be a further factor is the very strong complex [Be(H2O)4]2+ that is formed.

 Alkaline earth metals readily form divalent ions in aq. Solution, because hydration energy
is greater than sum of IP1 & IP2
Additional information: Solubility and Hydration:
Standard reduction potential:
 Since the alkali metals have a great tendency to lose their s-electrons they act as
powerful reducing agents.

 these elements have very low values of SRP

 Higher the –ve SRP value stronger the reducing agent.

 from the above values it is clear that though Li has a higher IE value it is the strong
reducing agent.
 This could be explained if we understand the fact that the ionization energy is the
property of isolated atoms in the gaseous state while the reduction potential is concerned
itself with the metal when it goes into solution.

 The ionization energy involves only the following change.

The ionization energy involves only the following change:

 On the other hand, the reduction potential involves the process.

 The process is thought to take place in three consecutive steps.

 The energy required in step (i) is known as sublimation energy. This energy is about the
same for all alkali metals.

 The energy required for step (ii) is the ionization energy. This is the highest for lithium.

 The energy liberated in step (iii) is known as hydration energy. Lithium ion has the
highest heat of hydration as explained in previous section. The net result of energy
liberated in all the three steps is larger for lithium. This explains the lowest reduction
potential of lithium.
 The reduction potential of ‘Be’ is much less negative than those for the rest of the group.
It indicates that ‘Be’ is much less electropositive than the others and ‘Be’ doesn’t react
with water. It may react with steam to form the oxide BeO or fails to react at all.

 Order of SRP Be > Mg > Ca > Sr > Ba ≈ Ra

 Alkaline metals are strong reducing agents than alkaline earth metals
 Solutions of alkali metals in liquid ammonia:
 The alkali metals dissolve in liquid ammonia giving bright blue, metastable solutions with
unusual properties.

 Such solutions have been extensively studied and it is now known that similar solutions
are formed by the heavier alkaline earth metals (Ca, Sr and Ba) and the divalent
lanthanoids europium and ytterbium in liquid ammonia. Many amines share with
ammonia this ability though to a much lesser extent.

 The solubility of alkali metals in liquid ammonia is favoured by low metal lattice energy,
low ionization energies and high cation solvation energy.
 The properties like colour, electrical conductivity and paramagnetism of these solutions
have been interpreted in terms of ionization of alkali metals to form alkali metal cations
and electrons which are solvated by ammonia.

 Ammoniated electrons are responsible for the blue colour while the electrical
conductance's are due to the both ammoniated cations as well as ammoniated electrons.

 The conductivity of the dilute solutions is an order of magnitude higher than that of
completely ionized salts in water

 When ammonia is pure and if there are no impurities evaporation of ammonia from these
solution results in the recovery of unchanged alkali metals.
 In the presence of impurities or catalysis such as Fe, the alkali metals react with Liq. NH3
to form a metal amide & H2

 The metals Ca, Sr and Ba dissolve in liquid ammonia as do the Group 1 metals.

 These solutions decompose very slowly, forming amides and evolving hydrogen, but the
reaction is accelerated by many transition metals and their compounds.

2NH3 + 2e- → 2NH2− + H2

 Evaporation of the ammonia from solutions of Group 1 metals yields the metal, but with
Group 2 metals evaporation of ammonia gives hexammoniates of the metals. These slowly
decompose to give amides

M(NH3)6 → M(NH2)2 + 4NH3 + H2

 Concentrated solutions of the metals in ammonia are bronze coloured due to the
formation of metal clusters.
 CHEMICAL PROPERTIES OF ALKALIMETALS
Alkali metals exhibits high chemical reactivity because of low ionization energy and large
size, reactivity increases if we go down the group.

 Reaction with air: air contain oxygen, nitrogen and moisture and so on so we can
discuss separately how these alkali metals are reacting.

 These elements tarnish rapidly in dry air

 Reaction with Oxygen: All these metals reacts with oxygen forms different products.

 Lithium forms monoxide Li2O

4Li + O2 ------> 2 Li2O (Oxide)

 Na forms peroxide Na2O2 2Na + O2 ------> Na2O2 (peroxide)

 Other metals (K, Rb, Cs) forms superoxide

 M + O2 --------> MO2 (superoxide) (M = K , Rb, Cs)

 All five metals can be induced to form the normal oxide, peroxide or superoxide by
dissolving the metal in liquid NH3 and bubbling in the appropriate amount of dioxygen.

Reason behind the formation of different oxides:

 Li+ is the smallest and has a strong positive field around it which attracts negative
charge so strongly that it does not permit oxide ion to reacts with O2 further.

 Na+ is larger then Li+ and its positive field is weaker then Li+ so it cannot prevent
conversion of oxide into peroxide.

 The large K+, Rb+ and Cs+ ions have weak positive field then Na+ so peroxide ion
reacts with O2 further forming super oxide ion.
Oxides:

 Li2O and Na2O are pure white solids

 K2O is pale yellow

 Rb2O is bright yellow

 Cs2O is orange

 Li2O, Na2O, K2O and Rb2O are anti-fluorite structures

 Cs2O has an anti-CdCl2 layer structure

 These oxides are strongly basic and soluble in water.

Ionic character: Li2O < Na2O < K2O < Rb2O < Cs2O (Fajan’s rule)

Basic nature: Li2O < Na2O < K2O < Rb2O < Cs2O (due to increasing ionic character)

Thermal stability: Li2O > Na2O > K2O > Rb2O > Cs2O (Lattice enthalpy)

Solubility in water: Li2O < Na2O < K2O < Rb2O < Cs2O

Reason: solubility of ionic compounds depends on the lattice enthalpy and hydration enthalpy. While
moving from top to bottom size of cation increases so hydration enthalpy decreases so solubility can
decrease BUT WHY SOLUBILITY INCREASES?

Lattice enthalpy is α size of the cation and anion; here size of the cation increases so lattice enthalpy
decreases but here decrease in lattice enthalpy is more than hydration enthalpy so solubility increases
Peroxides and superoxides:

 The peroxides all contain the [—O—O—]2- ion. They are diamagnetic (all the electrons
are paired), and are oxidizing agents

 They may be regarded as salts of the dibasic acid H2O2, and they react with water and
acid, giving hydrogen peroxide H2O2.

 Na2O2 + 2H2O ----> 2NaOH + H2O2

 Na2O2 is pale yellow in colour.

 It is used industrially for bleaching wood pulp

paper and fabrics such as cotton and linen.
 Na2O2 is a powerful oxidant, and many of its reactions are dangerously violent,
particularly with materials that are reducing agents such as aluminium powder, charcoal,
sulphur and many organic liquid
Na2O2 + Al → Al2O3

 Because it reacts with CO2 in the air it has been used to purify the air in submarines and
confined spaces, as it both removes CO2 and produces O2.

Na2O2 + CO → Na2CO3
2Na2O2 + 2CO2 → Na2CO3 + O2

 The superoxides contain the ion [O2]- , which has an unpaired electron, and hence they
are paramagnetic and are all coloured (LiO2 and NaO2 yellow, KO2 orange, RbO2 brown
and CsO2 orange).
 Superoxides are even stronger oxidizing agents than peroxides, and give both H 2O2 and
O2 with water.
KO2 + 2H2O → KOH + H2O2 + 1/2O2

 KO2 is used in space capsules, submarines, and breathing masks, because it both produces
dioxygen and removes carbon dioxide. Both functions are important in life support
systems.
4KO2 +2CO2 → 2K2CO3 + 3O2

Different oxides reaction with same substrate:

Reaction with nitrogen (present in air):
 Li is the only alkali metal which reacts with N2 (present in air) produce lithium nitride (ionic
compound ruby red solid)
6Li + N2 -----> 2Li3N
 at high temperature it decomposes back to elemental form.

 It reacts with water giving ammonia

Li3N + 3H2O → 3LiOH + NH3
Reaction with water:
 All alkali metals gives metal hydroxides in presence of water and liberates H2.
reaction is highly exothermic. Some times evolved H2 catches fire.

 The reaction becomes increasingly violent on descending the group. Thus lithium reacts
gently, sodium melts on the surface of the water and the molten metal skates about
vigorously and may catch fire and potassium melts and always catches fire.

 The standard electrode potentials E° (in volts) are Li+|Li = -3.05 Na+|Na = -2.71, K+|K =
-2.93, Rb+|Rb = -2.92, Cs+|Cs = -2.92.
 Standard electrode potentials E° and Gibbs free energy ΔG are related by the equation
ΔG = −nFE°
 where n is the number of electrons removed from the metal to produce the ion, and F is
the Faraday constant.

 The reaction Li+ + e- → Li has the largest negative E° value, and hence the largest positive
ΔG value thus the reaction does not occur.

 However, the reverse reaction Li → Li+ + e- has a large negative value of ΔG, so lithium
liberates more energy than the other metals when it reacts with water.

 Surprisingly Li reacts with water gently where as Na or K which liberate less energy react
vigorously even may catch fire
 No doubt, maxium energy is evolved with Li but its melting point is high compare to Na
and K

 Potassium has a low melting point, and the heat of reaction is suffcient to make it melt,
or even vaporize.

 The molten metal spreads out, and exposes a larger surface to the water, so it reacts even
faster, gets even hotter and catches fire.

Reaction with moist air: A mixture of several products obtained with moist air
Hydroxides properties:
All hydroxides are colourless crystalline solids, deliquiscent in nature.
deliquiscent: the process by which a substance absorbs moisture from the atmosphere until it dissolves
in the absorbed water and forms a solution
Hygroscopic: A hygroscopic substance tends to absorb moisture from the air.

Deliquescence Substances Hygroscopic Substances

When exposed to atomspheric air When exposed to atomspheric air
at ordinary temperature, they at ordinary temperature, they
absorb moisture and dissolve absorb moisture and donot
dissolve

Deliquescent substances change Hygroscopic substances donot

their physical state on exposure change their physical state on
to air exposure to air

Deliquescent substances are Hygroscopic substances may be

crystalline solids. amorphous solids or liquids
crystalline solids.
 All these hydroxides are highly soluble in water and solubility increases from LiOH to CsOH, due to
increase in ionic character (Fajan’s rule)

 Their dissolution in water is exothermic due to hydration enthalpy

 Of all the hydroxides known, the alkali metal hydroxides are strongest bases.

 The basic strength of the hydroxide increases regularly from lithium to cesium hydroxide. Due to
more ionic character (fajan’s rule). LiOH is more covalent character due to small size of the Li+

 Thermal stability of these hydroxides is LiOH < NaOH < KOH < RbOH < CsOH

 Thermal stability of oxides is Li2O > Na2O > K2O > Rb2O > Cs2O
Explanation: for binary compounds thermal stability decreases with increase of cation size. (lattice
energy) where as for ionic compounds having the multi atomic anions more the ionic nature more the
thermal stability
 Lithium hydroxide less stable compare to other hydroxides tends to lose water on heating.
2LiOH ----> Li2O + H2O

 Other alkali metal hydroxides do not decompose on heating. However, they sublime at about 673K.

 All these hydroxides reacts with acids to form salts; these hydroxides reacts with CO2 so they are
used to remove CO2 from air (astronauts use LiOH to absorb CO2).
 Salts of Oxo-acids: Carbonates, Bicarbonates, Nitrates, Nitrites and Sulphates

 The acids in which the acidic proton is on a hydroxyl group with an Oxo group attached to the
same atom are called Oxo-acids. E.g.: H2CO3 [OC(OH)2], sulphuric acid H2SO4 [O2S(OH)2]; nitric
acid [O2N (OH)], etc. The alkali metals form salts with all the oxo-acids.

Carbonates: All the alkali metals form carbonates and have the general formula M2CO3

The thermal stabilities of the alkali metal carbonates increases with increase in the size of the cation.

Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3

 Lithium carbonate decomposes on heating, to lithium oxide and carbon dioxide, whereas the
carbonates of the other alkali metals are highly stable to heat.

 The small Li+ ion exerts a strong polarising action and distarts the electron cloud of nearby oxygen
atom of the large CO32- ion. This results in the weakening of C-O bond and strengthing of Li-O
bond favouring the formation of Li2O and CO2.

 High lattice energy of Li2O than Li2CO3 also favours the decomposition of Li2CO3

 Except lithium carbonate the other alkali metal carbonates are stable upto 1273 K, above which
they melt and then are converted into oxides.
 All the carbonates (except Li2CO3 which is less soluble in water, solubility increase from Na2CO3 to
Cs2CO3 because their lattice energy decreases more rapidly than hydration energy

 Aqueous solution of these carbonates are alkaline due to hydrolysis

Bicarbonates: All the alkali metals (except Li) form solid bicarbonates with general formula MHCO3.

No other metal form solid bicarbonate except alkali metals excluding Li, whose bicarbonate is known
only in solution state due to the fact is observed due to unbalanced Hydration enthalpy as well as
lattice energy (in aq medium Li is in hydrated form lattice energy is not dominated the hydration
energy).

** NH4HCO3 (ammonium bicarbonate exist in solid state)

 Stability increases from LiHCO3 to CsHCO3 and even on gentle heating they decompose in to
carbonates.

 Bicarbonates of alkali metals are soluble in water and solubility increases from Li to Cs carbonate

 Aqueous solution of bicarbonate is alkaline due to anionic hydrolysis, and this is less basic than
carbonates

 The crystal structures of NaHCO3 and KHCO3 both show hydrogen bonding, but are different. In
NaHCO3 the HCO3− ions are linked into an infnite chain, whilst in KHCO3 a dimeric anion is formed.
 Nitrates: Alkali metals form nitrates of the general formula MNO3

 These can be prepared by the action of HNO3 on carbonates or hydroxide

M2CO3 + 2HNO3 -----> 2MNO3 + H2O + CO2

MOH + HNO3 -----> MNO3 + H2O

 All these nitrates are soluble in water

 Solid LiNO3 and NaNO3 are deliquescent, and because of this KNO3 is used in preference to NaNO3
in gunpowder (gunpowder is a mixture of KNO3, sulphur and charcoal)

 On strong heating they undergo decomposition

Reaction with halogens:
 The alkali metals readily react with halogens to form ionic halides, M+ X–.

2M + X2 -----> 2MX

 Li’ halides are some what covalent. It is due to high polarization capability of Li ion (The distortion
of electron cloud of the anion by the cation is called polarisation). The Li+ ion is very small in size
and has high tendency to distort electron cloud around the negative halide ion. Since anion with
large size can be easily distorted, among halides, lithium iodide is the most covalent in nature.

 These halides also can be prepared by the reaction of metal oxide, hydroxide or carbonate with aq.
HX
properties:
 All the halides of alkali metals are colorless solids with high melting points and boiling
points

 On heating colourless halides become coloured and color of the alkali metal halides
resembles with color of flame imparted by the alkali metal

 Stability: the stability of these metal halides can be compared by comparing their
standard enthalphy of formation.

 standard enthalpies of formation ΔfHº of these halides are high negative

 For fluorides ΔfHº become less –ve as we go down the group; which means
 LiF formation is more exothermic
 CsF formation is less exothermic
 Thus LiF is most stable while CsF is least. However the trend is opposite to as may be
predicted by Fajan’s rule but high lattice enthalpy of LiF accounts for the observed order.

LiF > NaF > KF > RbF > CsF (Order of stability also)
 For other halides (Cl, Br & I) ΔfHº become more –ve as we go down the group; which
means

 LiX (X = Cl, Br & I) formation is less exothermic

 CsX (X = Cl, Br & I) formation is more exothermic

 LiX < NaX < KX < RbX < CsX ( X = Cl, Br & I)

 This order is according to fajan’s rule as from Li+ and Cs+, size of cation increases and so
anion is less polarized, resulting in the more ionic character
For a given metal ΔH0f value vary in the order

Ionic Nature: With the exception of some lithium halides all are ionic compounds.
For a given halide

lithium halides acquire some covalent character because of Li+ is smallest and polarize anion
to maximum extent.

For a given alkali metal

Solubility:
 The solubility of a salt in water depends on its lattice energy and hydration energy. For a
substance to dissolve, the hydration energy must be larger than the lattice energy.
Conversely, if the hydration energy is less than the lattice energy the solid is insoluble.

 Among fluorides, the order of solubility is LiF < NaF < KF < RbF < CsF

 The low solubility of LiF is due to its very high lattice energy (due to small sizes of both
cation and anion).
 In the case of lithium halides except LiF other halides are highly soluble in water because
of the large hydration energy of small Li+ ion.

 Except fluorides, for the other halides the solubility decreases from NaX to KX and then
increases to CsX.

 The solubility of potassium salts is less than sodium salts. This is because the difference in
hydration and lattice energies of potassium salts is positive, whereas in the case of other
metal halides is negative

 Lithium halides (except LIF) have significant covalent character and hence soluble in
organic solvents like pyridine, alcohol, acetone, etc.
Melting point:
 The melting points of the alkali metal halides can be explained basing on their lattice
enthalpies.
 The greater the lattice enthalpy, the higher is the melting point. The m.pts and b.pts, are
given in Table

 For a given alkali metal, the melting points and boiling points are in the order.
 Fluoride > Chloride > Bromide > Iodide
For a given halogen the melting and boiling points are in the order
Lithium < Sodium > Potassium > Rubidium > Caesium

 For any particular halide ion (X−), NaX has the highest melting and boiling point but not
LiX.

 This can be largely rationalized in terms of the very small size of the Li+ ion–a fact that
leads to appreciable covalent character of lithium halides because of more polarizing
power of small Li+ ion with more charge density.
 Further due to small size of Li+ ion there exists anion–anion repulsion resulting in the
considerable increase of Li−X distance in the lithium salts than the expected from the sum
of ionic radii. This results in appreciable lowering of the energy of the crystal, which, in
turn, leads to lower the melting and boiling points.

Reaction with Hydrogen (hydrides):

 All the alkali metals reacts with hydrogen at 673 K (1073 for Li) to form colourless
crystalline ionic hydrides.
 Order of reactivity is explained on the basis of lattice energy, which decreases from LiH
to CsH due to increase in size of cation.

 Also, due to this trend of lattice energy the stability order of these hydrides is
LiH > NaH > KH > RbH > CsH

 On electrolysis of these molten liquids, H2 is formed at anode.

 These hydrides accepts proton from proton donar and liberates hydrogen

 MH + H2O --------> MOH + H2

 Alkali metals also forms complex hydrides like LiAlH4 and NaBH4 . Which are good
reducing agents
Anomalous Properties of Lithium:

 Although lithium shows most of the characteristic properties of Group IA, it also shows
some differences in many respects. This is mainly due to

 (i) small size

 (ii) high electronegativity

 Lithium is the hardest metal among the alkali metals. Its melting and boiling points are
higher than those of the other alkali metals.

 Unlike the other alkali metals, lithium reacts with nitrogen directly forming nitride Li3N

 When burnt in air or oxygen lithium forms only monoxide while other alkali metals form
peroxides and superoxides.
 Lithium hydroxide decomposes on heating to form Li2O while other alkali metal
hydroxides do not decompose on heating but melts on heating.

 Li2O and LiOH are weakest bases among the oxides and hydroxides of alkali metals.

 Lithium carbonate decomposes on heating but other alkali metal carbonates do not
decompose on heating.

 Lithium nitrate, on heating, decomposes giving Li2O, NO2 and O2 while other alkali metal
nitrates on heating converts into nitrites evolving oxygen.
 CHEMICAL PROPERTIES OF ALKALINE EARTH METALS

 The alkaline earth metals are highly reactive like alkali metals . (less reactive than the
alkali metals). The reactivity of these elements increases on going down the group.

 Reactivity towards air: Air contain O2, N2 and water we will discuss reactivity
separately

Reaction with oxygen:

 Under suitable conditions, all the alkaline earth metals burn in air to form oxides (MO),
which are crystalline solide 2M + O2 ----> 2MO

 Ba, Sr and Ra forms peroxides

 The order of reactivity towards oxygen increases from Be to Ra

 Beryllium and magnesium are kinetically inert to oxygen because of the formation of an
oxide film on their surface.

 Beryllium oxide is made by ignition of the metal or its compounds in oxygen because this
does not react with oxygen at the same conditions where Ba Sr & Ra reacts

 Alkaline earth metal oxides are also formed by heating their oxosalts such as M(NO3)2 and
MSO4 and also by heating M(OH)2.

 The oxosalts are less stable to heat than the corresponding Group-IA salts because the
metals and their hydroxides are less basic than those of Group-IA.

 The oxides of alkaline earth metals except beryllium are ionic and BeO is covalent
 BeO is insoluble in water. MgO is not very reactive CaO, SrO and BaO react
exothermically with water forming hydroxides. Solubility in water increase from BeO to
BaO,

 Due to high reactivity Ca, Sr, Ba are stored in kerosene oil or paraffins.

 Be Mg can be stored as such because they form protected layer of oxide on their surface.

 Beryllium oxide is amphoteric and reacts slowly with strong acids. It also react with
strong bases.
 CaO, SrO and BaO are basic in nature and form hydroxides with water and forms salt
with Acid
Reaction with water:
 Beryllium do not react with water or steam even at high temperature.

 Magnesium reacts only with boiling water, whereas other metals react even with cold water.
M + 2H2O --------> M(OH)2 + H2 ( M = Ca, Sr, Ba)

 Mg forms a protective layer of oxide, it does not react readily unless the oxide layer is removed by amalgamating
with mercury.

 Be(OH)2 is amphoteric remaining are basic.

 Basic nature of hydroxides increases from top to bottom

 Solubility, thermal stability increase from top to bottom

 Though both lattice and hydration energies are decreasing down the group the decrease in lattice energy is more
rapid than the hydration energy and so their solubility increases on descending the group.

 On heating they undergo decomposition

 Be(OH)2 is amphoteric reacts with acids & alkali both

Reaction with N2:
 These elements on burning in nitrogen form the nitrides of the type M3N2.

 Be3N2 is volatile due to covalent nature, while others are nonvolatile crystalline solids.

 The ease of formation of nitrides decreases down the group.

 All the alkali earth metals form nitrides where as in alkali metals only Li forms nitrides

 Thermally all the nitrides are unstable and on heating they liberate N2

 They react with water liberating ammonia and form metal hydroxide.
Reaction with halogen:
 Alkaline earth metals form halides of the type MX2. They can be made directly by heating the metals with halogens or by the
action of halogen acid on either of the metal or carbonate.

 Thermal decomposition of (NH4)2BeF4 is the best route for the preparation of BeF2 (additional)

 BeCl2 is conveniently made from the oxide. (additional)

 Beryllium halides are covalent in nature due to small size and soluble in organic solvent. So they do not conduct
electricity in molten state. The ionic character of halides increases from Be to Ra

 The tendency to form halides hydrates gradually decreases.

 Ca, Sr, Ba hydrated chlorides, bromides and iodides on heating undergo dehydration. Be & Mg hydrated halides
suffer hydrolysis.
 Fluorides are relatively less soluble than the chlorides owing to their high lattice energies.

 Solubility order is BeF2 > MgF2 < CaF2 < SrF2 < BaF2

 Chlorides, bromides and iodides of Mg, Ca, Sr and Ba are ionic have much lower melting points than fluorides
and are readily soluble in water. Solubility decreases some what with increasing atomic number.
Additional:
Carbonates and Bicarbonates :
The carbonates of the alkaline earth metals are salts of the weak carbonic acid H2CO3 and strong hydroxides
M(OH)2. The carbonates occur in nature as solid rock materials. These can be prepared by passing carbon dioxide
into the aqueous solutions of alkaline earth metal hydroxides or by adding sodium or ammonium carbonate solution to
the solution of a soluble salt of these metals. The carbonates are precipitated out.

 The thermal stability of carbonates increases from beryllium to barium.

 Since BeCO3 decomposes at low temperatures, it should be stored in an atmosphere of carbon dioxide.
 The solubility of alkaline earth metal carbonates decreases as the atomic number of cation increases.

 All these carbonates are much more soluble in a solution of carbon dioxide than in water due to the formation of
the bicarbonate.

 The bicarbonates of alkaline earth metals cannot be prepared in solid state. They exist only in solution.

 All the carbonates of alkaline earth metals are ionic, but BeCO3 is unusual because it contains the hydrated ion
[Be (H2O)4]2+ rather than Be2+.
Bicarbonates:
Alkaline earth metals form bicarbonates of M(HCO3)2

These bicarbonates can be obtained by treating the aq metal hydroxide with excess of CO2

M(OH)2 + CO2 -----> MCO3 + H2O

MCO3 + H2O + CO2 ------> M(HCO3)2

All the bicarbonates of IIA are stable only in the solution and decompose on heating even in the dissolved state.

M(HCO3)2 + Heat ------> MCO3 + H2O + CO2

These can not be isolated in the solid state and differ in this respect from the bicarbonates of alkali metals
Sulphates:
Sulphates of alkaline earth metals can be obtained by the action of dilute sulphuric acid on metals, oxides, hydroxides
or carbonates.
Nitrates:
Nitrates of general formula M(NO3)2
Carbides (additional):
When BeO is heated with ‘C’ at 1900 – 2000 °C a brick red coloured carbide of formula Be2C is formed.
On hydrolysis it forms methane gas hence it is called as methanide.

Mg, Ca, Sr, Ba form carbides of formula MC2

IMPORTANT ORDERS