The s-block elements:

Alkali and alkaline earth metals

 The s-block elements:alkali and alkaline earth metals

Alkali metals
oThe alkali family is found in the first column of
the periodic table include; Li, Na, K, Rb, Cs, Fr.
o Metallic elements.
o Among the alkali metals;
 sodium and potassium are abundant and
 lithium, rubidium and caesium have much
lower abundances.
 Francium is highly radioactive; its longest-
lived isotope 223Fr has a half-life of only 21
minutes.
 The s-block elements:alkali and alkaline earth metals

Alkali metals

oAtoms of the alkali metals have a single

electron in valence shell (1 valence
electron) and electron configuration of 1s1.
oSoft metals (easily cut with a knife).
oThey are the most reactive metals.
oThey react violently with water.
oAlkali metals are never found as free
elements in nature. They are always
bonded with another element.
 The s-block elements:alkali and alkaline earth metals
Alkali metals
The metals are all very reactive* when pure.
– strongly reducing (very powerful reducing agents)
 In nature, these elements only ever appear as their +1 cations.
 Their cations (with the exception of lithium) have low charge densities.
– often leads to good solubility and an ability to stabilize anions that can not
be formed along with any other cation.
Cations occur in wide variety of important chemicals.
 Form ionic compounds with highly electronegative (nonmetals) found in
Groups 6 (O, S, Se and 7 (F, Cl, Br, I, At) , as well as P and N from Group 5.

*Most alkali metals are stored under oil. But lithium is so light that it floats on oil. So
a coat of petroleum jelly is applied to lithium before it is stored.
 The s-block elements:alkali and alkaline earth metals

Physical Properties
• Lowest ionization energies and electronegativities in periodic table
- easily ionized to form ions with +1 charge/+1 oxidation state.
 The s-block elements:alkali and alkaline earth metals

Physical Properties
• They are good conductors of electricity.
Their ability to conduct electricity is due to the availability of their outer electrons.
• Low densities.
• Low melting points and boiling points.
Due to the presence of a single valence electron.
 The s-block elements:alkali and alkaline earth metals
Flame tests
o Alkali metal ions are identied by flame tests.
o In flame ions in excited states return to their ground states  emit light.
o The emission spectrum depends
on a number of factors;
- the flame temperature;
- but is most strongly is the
energy levels of the emitter, leading
to characteristic colours.

Element Li Na K Rb Cs
Flame colour crimson yellow lilac purple blue
 The s-block elements:alkali and alkaline earth metals

Production of alkali metals

o Lithium sodium and potassium metal are produced by electrolysis of
the molten chlorides.

o Overall reactions:
LiCl(l)  Li(l) + ½ Cl2(g)
NaCl(l)  Na(l) + ½ Cl2(g)
 The s-block elements:alkali and alkaline earth metals

Chemical reactions

Reactivity towards Bronsted acids

The alkali metals react even with weak Bronsted acids such as water
– The rate of reaction depends upon the acidity of the medium
2Na + 2H2O  2NaOH + H2
2Na + 2EtOH  2NaOEt +H2
2Na + 2NH3  2NaNH2 +H2
– very slow reaction in absence of catalyst
 The s-block elements:alkali and alkaline earth metals
Oxides of the alkali metals
oAlkali metal on combustion in Oxygen
M + O2 → depends on the alkali metal
Li2O (oxide) The oxidation state of O?
Na2O2 (peroxide)
KO2, RbO2, CsO2 (superoxide)

o On combustion in excess of air, lithium forms mainly the oxide, Li2O (plus
some peroxide Li2O2), sodium forms the peroxide, Na2O2 (and some
superoxide NaO2) whilst potassium, rubidium and caesium form the
superoxides, MO2.
oThe increasing stability of the peroxide or superoxide, as the size of the
metal ion increases, is due to the stabilisation of large anions by larger
cations through lattice energy effects.
 The s-block elements:alkali and alkaline earth metals

Oxides of the alkali metals

o These oxides and peroxides are colourless when pure, but the superoxides
are yellow or orange in colour. The superoxides are also paramagnetic.
Sodium peroxide is widely used as an oxidising agent in inorganic chemistry.

oAll oxides compounds react violently with H2O (hydrolysis) under

formation of hydroxide
Li2O(s) + H2O(l)  2 LiOH(s)
Na2O2(s) + 2 H2O(l)  2 NaOH(s) + H2O2(l)
2 KO2(s) + 2 H2O(l)  2 KOH(s) + H2O2(l) + O2(g)
 The s-block elements:alkali and alkaline earth metals

Oxides of the alkali metals

oThe oxides are all basic. They react readily with acids (even weak acids)
– Na2O + H2O  2NaOH (the water acts as an acid)
– Na2O + HCl  2NaCl
The alkali metal hydroxides are the strongest of all bases.

oThey react with CO2 to form carbonates:

Li2O(s) + CO2(g)  2 Li2CO3(s)
2 Na2O2(s) + 2 CO2(g)  2 Na2CO3(s) + O2(g)
4 KO2(s) + 2 CO2(g)  2 K2CO3(s) + 3 O2(g)

KO2 is used as CO2 and H2O absorber in diving gear.

 The s-block elements:alkali and alkaline earth metals

Reactivity of Alkali Metals with Group 5, Elements (N, P)

o With Phosphorus
12 M + P4 → 4 M3P (phosphides)

o With Nitrogen
6 Li + N2 → 2 Li3N (nitride)
Only Li forms a nitride.
The lattice energy for nitrides with larger alkali metal cations is not
sufficient to make ΔGrxn<0.
 The s-block elements:alkali and alkaline earth metals

Reactivity of Alkali Metals with Group 7 Elements “Halogens”

o The reactivity of alkali metals increases as the ionization energy decreases

Cs > Rb > K> Na > Li
o Reactivity increases moving down the group.

oExample:

o The resulting compounds are colorless, crystalline ionic salts called halides.
 The s-block elements:alkali and alkaline earth metals

Reactivity of Alkali Metals with Group 7 Elements “Halogens”

o The melting and boiling points always follow the trend:

ofluoride > chloride > bromide > iodide.

oAll these halides are soluble in water.

oThe low solubility of LiF in water is due to its high lattice enthalpy.
oThe low solubility of CsI is due to smaller hydration enthalpy of its two
ions. Other halides of lithium are soluble in ethanol and acetone; LiCl is
soluble in pyridine also.
 The s-block elements:alkali and alkaline earth metals

Some typical reactions

Reaction with water:
All alkali metals react with water to produce hydrogen and the metal
hydroxide.
M(s) + H2O(l)  M+ (aq) + OH- (aq) + ½ H2(g)

The metals are called alkali metals because the resulting solution is alkaline
owing to the presence of the hydroxide ion.

Reaction of lithium with oxygen:

2Li(s) + ½ O2(g)  Li2O(s)
 Alkali metal compounds are almost ionic.
 The s-block elements:alkali and alkaline earth metals

Some typical reactions

Reaction with halogens (group 17: F2, Cl2, Br2, I2)
• All alkali metals react with halogens to form ionic halides.
M(s) + 1/2 X2  MX(s)
Ex. 2Na(s) + Cl2(g)  2NaCl(s)

• The most vigorous reaction occurs between the elements which are furthest
apart on the Periodic Table:
- the most reactive alkali metal, francium (Fr), at the bottom of Group 1,
with the most reactive halogen, fluorine, at the top of Group 7.
 The s-block elements:alkali and alkaline earth metals

Activity Series for Alkali Metals

The most active metals are the most easily oxidized. Consequently, they are the
best reducing agents.
Activity decreases going down the group; ease of oxidation.
 The s-block elements:alkali and alkaline earth metals

Basicity of oxides, sulfides nitrides

Salts containing high charge density anions
like O2-, S2-, N3-, P3- with low charge
density cations (alkali metal and most
alkaline earth metals) are basic
– S2- + H2O  HS- + OH-
– N3- + 3H2O  NH3 + 3 OH-
 The s-block elements:alkali and alkaline earth metals

Hydration

o An ion in solution is surrounded by water molecules.

o Hydration enthalpy ( hydrH): Enthalpy change

for the transfer of an ion from the gas phase to
solution
M+(g)  M+ (aq)
 The s-block elements:alkali and alkaline earth metals

Solubility of alkali metal compounds

o Alkali metals have relatively large, negative enthalpies of hydration.

o Because they carry a single charge, the forces holding their crystals
together, are less strong than those holding together crystals of more highly
charged ions.
o As a consequence, almost all alkali metal compounds are extremely soluble
in water.
(solubilities often reaching several hundred grams per litre).
o Exception: some lithium compounds with highly charged anions,
example, Lithium phosphate: 0.39 g L-1
 The s-block elements:alkali and alkaline earth metals

Chemical reactions
Summery of the general reactions of alkali metals
 The s-block elements:alkali and alkaline earth metals

Lithium

Lithium is the most reducing of all the alkali metals

– but not the most reactive.

Unlike the other alkali metals; it reacts with nitrogen to form a nitride.
 The s-block elements:alkali and alkaline earth metals

ANOMALOUS PROPERTIES OF LITHIUM

The anomalous behaviour of lithium is due to the:

(i) exceptionally small size of its atom and ion, and

(ii) high polarising power (i.e., charge/ radius ratio).

As a result,

i. there is increased covalent character of lithium compounds which is

responsible for their solubility in organic solvents.

ii. Further, lithium shows diagonal relationship to magnesium which has

been discussed later.

 The s-block elements:alkali and alkaline earth metals

Points of Difference between Lithium and other Alkali Metals

(i) Lithium is much harder. Its m.p. and b.p. are higher than the other alkali

metals.

(ii) Lithium is least reactive but the strongest reducing agent among all the

alkali metals.

On combustion in air it forms mainly monoxide, Li2O and the nitride, Li3N

unlike other alkali metals.

(iii) LiCl is deliquescent and crystallises as a hydrate, LiCl.2H2O whereas

other alkali metal chlorides do not form hydrates.

 The s-block elements:alkali and alkaline earth metals

(iv) Lithium hydrogencarbonate (LiHCO3) is not obtained in the solid form

while all other elements form solid hydrogencarbonates.

(v) Lithium nitrate when heated gives lithium oxide, Li2O, whereas other

alkali metal nitrates decompose to give the corresponding nitrite.

4LiNO3 → 2Li2O + 4 NO2 + O2

2 NaNO3 → 2NaNO2 + O2

(vi) LiF and Li2O are comparatively much less soluble in water than the

corresponding compounds of other alkali metals.

 The s-block elements:alkali and alkaline earth metals

Points of Similarities between Li and Mg

o The similarity between Li and Mg arises

because of their similar sizes:

atomic radii, Li = 152 pm, Mg = 160 pm;

ionic radii : Li+ = 60 pm, Mg2+= 65 pm.

 The s-block elements:alkali and alkaline earth metals

Points of Similarities between Lithium and Magnesium

oThe main points of similarity are:

(i) Both lithium and magnesium are harder and lighter than other elements in
the respective groups.
(ii) Lithium and magnesium react slowly with water.
-Their oxides and hydroxides are much less soluble and their hydroxides
decompose on heating.
-Both form a nitride, Li3N and Mg3N2, by direct combination with
nitrogen.
(iii) The oxides, Li2O and MgO do not combine with excess oxygen to give
any superoxide.
 The s-block elements:alkali and alkaline earth metals

Points of Similarities between Lithium and Magnesium

(iv) The carbonates of Li and Mg decompose easily on heating to form the

oxides and CO2.

-Solid hydrogencarbonates are not formed by Li and Mg.

(v) Both LiCl and MgCl2 are soluble in ethanol.

(vi) Both LiCl and MgCl2 are deliquescent and crystallise from aqueous

solution as hydrates, LiCl·2H2O and MgCl2·8H2O.

 The s-block elements:alkali and alkaline earth metals

Uses
• The most important use of lithium is in rechargeable batteries for mobile
phones, laptops, digital cameras and electric vehicles.
• Lithium metal is used to make useful alloys,
for example with lead to make ‘white metal’ bearings for motor engines,
with aluminium to make aircraft parts.
• Used in anti-depression medication.

• Organometallics of lithium are important.

 The s-block elements:alkali and alkaline earth metals

Li- bipolar disorder

About two million people in the US experience the extreme mood swings of
bipolar disorder.
During a manic phase, they think they can conquer the world. During a
depression, they may feel hopeless.
The ionic compound lithium carbonate often is used to control these
symptoms.
Lithium ions probably have an effect on the transmission of messages
between brain cells.
 The s-block elements:alkali and alkaline earth metals

In 1991, Sony Corporation released the first commercial lithium ion

battery with a carbon anode. Nowadays, many devices use rechargeable
lithium ion batteries and several cathode chemistries have been
developed.

Why Li ??
Lithium is the lightest of all metals;
has the greatest electrochemical potential and
provides the largest specific energy per weight.
 The s-block elements:alkali and alkaline earth metals

Li- ion battery

Charge

Anode Electrolyte Cathode

(Carbon / graphite) (LiPF6 in EC:DMC) LiCoO2
Anode: Cathode:
Li  Li+ + e- Co4+ + e-  Co3+
The cathode reactions are solid state redox reactions.