Topic 1

The s-block elements

(Group 1 and 2)
Part 1
• Occurrences and extraction of the elements.
• Physical and chemical properties of the metals.
• Uses of metals and their compounds.

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ELEMENTS OF S-BLOCK
Elements of Group I – Alkali Metals
Li : [He] 2s1
Na : [Ne] 3s1
K : [Ar] 4s1
Rb : [Kr] 5s1
Cs : [Xe] 6s1
Fr : [Rn] 7s1

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Existence and abundance

Li – 35th most abundant obtained as silicates “Spodumene”, LiAl(SiO3)2 and

“Lepidolite”, Li2Al2(SiO3)3(FOH)2.

Na and K – 7 and 8th most abundant obtained as NaCl and KCl in sea water.
- Other sources are “Saltpetre”, NaNO3 and “Borax”, Na2B4O7.10 H2O.
- K mainly as deposits of KCl “Sylvite” and “Carnallite”, KCl.MgCl2.6H2O.

No convenient source of Rb and Cs.

– obtained as by-products from Li processing.

Fr - lowest known electronegativity of all known elements. A highly radioactive

metal that decays into astatine, radium, and radon.

Eg.
223 t1/2 = 21 min 223
0
Fr e + As
89 -1 88
6
Extraction of Alkali metal
A– Graphite anode where Cl- ions are
Li and Na – isolated using electrolysis of its oxidized to Cl2 gas which rises up
chloride melt via Down cell. and collected via an inverted trough.

Construction of a Down cell

B– At the cathode where Na+ ions is
reduced to form Na atoms. The molten
Na rises to the top of the cell to be
collected.
C – The steel cathode encircles the graphite
anode.
D – A cylinder of steel gauge surrounds the
anode to prevent the Na and Cl2 from
A C E recombining to form NaCl again.
D
B E - Molten or fused NaCl placed in a firebrick
lined container, mixed with CaCl2 to lower its
m.pt. to 600oC (from 801oC).

Potassium metal is obtained from reduction of fused KCl from molten sodium.
850oC
eg. KCl (l) + Na (l)  NaCl (l) + K (g) 
Rb and Cs can be obtained with Ca as reducing agent.
Advantages of Down's process
Sodium metal obtained has high degree of purity (99.5%).
The starting material, sodium chloride is very cheap. 7
Chlorine is obtained as a useful by-product
Physical and Chemical Properties Of The Metals

Electronic structure
-All have one valence electron in their outer orbital.

-The single valence electron is long distance from the nucleus, weakly held and is readily
removed.

- The remaining electrons are closer to the nucleus and more tightly held.

- Similarities in the electronic structures gave similar chemical behaviour.

Size of Atoms And Ions

-Group 1 elements are the largest in their horizontal periods in the periodic table.

-When the outer electron is removed to give M+ , the size decreases due to:
i. The outermost shell of electrons has been completely removed.
ii. The positive charge on the nucleus become greater. Thus, each of the remaining
electrons is attracted more strongly towards the nucleus.
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Ionization Energy
-Low ionization energy.

• The outer electrons are only held weakly by the nucleus.

• When going down the group, the atomic size increases, the outer most electrons become
less strongly held, so the ionization energy decreases.

• The second ionization is extremely high because:

i. Involves removing an electron from a smaller positive ion rather than from a larger neutral
atom.
ii. Much higher energy is required to remove an electron from a closed shell.

• A second electron is never removed under normal conditions, as the energy required is
greater than that needed to ionize the noble gases. The elements commonly form M+ ions.

Element First ionization Second ionization Table 1. Ionization

energy (kJ mol-1) energy (kJ mol-1) energies of group
Li 520.1 7296 1 elements.
Na 495.7 4563
K 418.6 3069
Rb 402.9 2650
Cs 375.6 2420 9
Electronegativity

- Low electronegativity.

- When react with other elements to form compounds, a large electronegativity difference
between the two atoms is probable, and ionic bonds are formed.
eg.
Na electronegativity 0.9
Cl electronegativity 3.0

Electronegativity difference 2.1 (ionic bonding)

-An electronegativity difference of ~ 1.7-1.8 corresponds to 50% ionic character.

-eg. electronegativity difference of LiF = 3.0 ; KBr = 2.0

Table 2. Electronegativity values

Element Pauling’s electronegativity
Li 1.0
Na 0.9
K 0.8
Rb 0.8
10
Cs 0.7
Solubility
If a salt is insoluble its lattice energy > hydration energy.

For a substance to dissolve, the energy evolved when the ions are hydrated
(hydration energy) must be larger than the energy required to break the
lattice (lattice energy).

Solubility of most Gp I metals decreases on descending the group is because

the lattice energy only changes slightly but the free energy of hydration
changes more.

But Gp I fluorides and carbonates are exceptional in that their solubilities

increases rapidly on descending the group because their lattice energies
change more than the hydration energies.

eg. Lattice energy for a salt MX refers to the process :

M+(g) + X-(g)  MX(g)
And is proportional to z+z -/ r, where z+ and z - = charge on cation and anion,
respectively, and r = sum of ionic radii of cation and anion.
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Hydration refers to the process :

M+(g) + nH2O(l)  [M(H2O)n]+(aq)

Li+ is very small and has a large hydration energy

 always heavily hydrated eg. LiCO3·3H2O.
Hence it moves only slowly in solution.
Therefore, its ionic mobility in aqueous
solution is in the order Cs+ > Rb+ > K+ > Na+ > Li+.

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Other physical properties:

-Group 1 metal ions are colorless because all have the noble gas configurations.

-Group 1 metals are all very soft and with low melting point due to low cohesive energy
because only 1 valence electron per atom results in weak bonds.

-Cohesive energy is the force holding the atoms or ions together in the solid.

-The softness, low cohesive energy and weak bonding in Group 1 elements are
consequences of these metals having only one valency electron can participate in bonding.

Group I metals are different from the other Groups in their weak tendency to form
complexes. This is predictable because the factors favoring complex formation are small
size, high charge and empty orbitals of low energy for bond formation and Group I metal
ions are very large and have a low charge of +1.

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Anomalous behavior of Lithium

Lithium differs from characteristic properties of the metals of Group 1, due to the
following reasons:
(1) The size of lithium atom and ion is very small.
(2) The polarizing power of Li+ ion is quite high and results in the covalent
character of its compounds.
(3) It has high ionization energy and least electropositive character.

Important distinctions between lithium and other family members

(1) Lithium is the hardest of all the alkali metals.
(2) The melting and boiling points of lithium are much higher than those of other
elements of Group 1.
(3) Lithium is less reactive as compared to other metals and it does not get
tarnished readily in air.

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(4) It forms only monoxide, Li2O with oxygen while sodium forms peroxide-
Na2O2; other elements form superoxide, MO2.
(5) Because of high polarizing power of Li+ ion, the salts of lithium have
lower ionic character than salts of other alkali metals.
(6) While other alkali metals do not react with nitrogen, lithium does, forming
nitride.
(7) Lithium hydroxide and carbonate are less basic than the other metals,
therefore unstable and decompose on heating while the corresponding
compounds of the rest of the family members are stable and do not
decompose:

Heat
2LiOH  Li2O + H2O

Heat
2Li2CO3  Li2O + CO2

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(8) When lithium nitrate is heated it gives nitrogen dioxide and oxygen
4LiNO3  2Li2O + 4NO2 + O2

When sodium nitrate and potassium nitrate upon strong heating form
corresponding nitrites and evolve oxygen.
2NaNO3  2NaNO2 + O2

(9) Lithium chloride and nitrate are soluble in alcohol, while the salts of sodium
are insoluble in alcohol.

(10) The hydride of lithium (LiH) is more stable as compared to the hydrides of
other members of the family.

(11) The Li+ ion and its compounds are more heavily hydrated than those of
sodium.

(12) Lithium fluoride, carbonate, hydroxide, oxalate are sparingly soluble in water.
The corresponding salts of sodium and potassium are readily soluble.

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Diagonal relationship
Lithium has a diagonal relationship with magnesium
and both have similarities in some of their characteristics.
The atomic radius of both elements is close; lithium (152 pm) and magnesium (160 pm).
Both have almost similar electronegativities (Li = 1.0, Mg = 1.2)
Both Li and Mg are quite hard.
Both LiOH and Mg(OH)2 are weak bases.
Lithium reacts with N2 to form lithium nitride, while magnesium also reacts in a similar
way. Other members of the group do not display this characteristic.
6Li + N2  2Li3N
3Mg + N2  Mg3N2

Both lithium and magnesium combine with oxygen to form mainly monoxides. Other
member form peroxides and superoxides.
Heat
2Mg + O2  MgO
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On strong heating, the hydroxides of both metals decompose to form respective oxides
Heat
2LiOH  Li2O + H2O
Heat
Mg(OH)2  MgO + H2O

When heated, the carbonates of both these metals evolve CO2.

The nitrates of both lithium and magnesium evolve nitrogen dioxide and oxygen
on heating

Heat
4LiNO3  2Li2O + 4NO2 + O2

Heat
2Mg(NO3)2  2MgO + 4NO2 + O2

Lithium hydroxide, fluoride, phosphate, oxalate and carbonate are comparable to

those of the corresponding magnesium compounds. However, the solubilities are
much less soluble than the corresponding sodium and potassium salts.
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Chemical properties
1. Reaction with water

-Group 1 metals all react with water, liberating hydrogen and forming hydroxides.

2 Li + 2 H2O 2 LiOH + H2

2 Na + 2 H2O 2 NaOH + H2

2 K + 2 H2O 2 KOH + H2
- The reaction becomes increasingly violent on descending the group.
eg. -Lithium reacts gently;
-Sodium melts on the surface of the water and the molten metal skates
about vigorously and may catch fire;
-Potassium melts and always catches fire.

Li Na K 19
Chemical properties

2. Reaction with Nitrogen

Only Li reacts with nitrogen  lithium nitride, Li3N.
Li3N is termed as an inorganic superbase which is a typical salt with a highly
charged, small negative ions, which has extreme negative charge density, N3-
and so is highly attracted to acids.

eg. 2Li3N  6Li + N2


Li3N + 3H2O  3LiOH + NH3
Li3N + 3HCl  3LiCl3 + NH3

3. Reaction with Oxygen

- alkali metal reacts with O2 to give a variety of oxide ions.

- oxide ions which can obtained are M2O (simple oxide), M2O2 (peroxide) and
MO2 (superoxide).
i) Simple oxides, X2O
In limited supply of O2,
O2
Li  Li2O + some Li2O2
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
Reaction of simple oxide, M2O

Reaction with water

These are simple basic oxides, reacting with water to give the metal hydroxide.
eg. M2O + H2O  2MOH

Reaction with dilute acids

These simple oxides all react with an acid to give a salt and water.
eg. M2O + 2HCl  2XCl + H2O

ii) Peroxides, X2O2

Peroxide is anion O22−. It is highly basic and ionic in nature.

Pure peroxides (containing only cations and the peroxide anions) are usually
formed by burning alkali metals or alkaline earth metals in air or oxygen.

Sodium peroxide Na2O2 is a typical example.

The peroxide ion contains two electrons more
than the oxygen molecule.
Sodium peroxide
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These two electrons, according to the molecular orbital theory, complete the two
π* antibonding orbitals.
This has as result a weakening of the bond strength of the peroxide ion and a
greater length for the bond O-O : Li2O2 130 pm to BaO2 147 pm.
Furthermore, the peroxide ion is diamagnetic.

Peroxide is a compound containing an oxygen-oxygen single bond.

Peroxide is the anion O22−. It is highly basic, and ionic in nature.
O2
eg. Na  Na2O2 + some Na2O


Reaction of peroxide, M2O2

Reaction with water

If the reaction is done ice cold because it is strongly exothermic, a solution of the
metal hydroxide and hydrogen peroxide is formed.
eg. M2O2 + 2H2O  2MOH + H2O2
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Reaction with dilute acids
These reactions are even more exothermic than the ones with water.
eg. M2O2 + 2HCl  2MCl + H2O2

Uses of peroxides
Peroxides are powerful oxidizers, and usually fairly unstable.
Ionic peroxides react with water and diluted acids to form hydrogen peroxide.
Sodium peroxide is used as a carbon dioxide absorber and oxygen regenerator
(e.g. in some submarines), through the reaction:

eg. 2Na2O2 + 2CO2 → 2Na2CO3 + O2

Applications of inorganic peroxides and peroxo compounds include:

i) household detergents, polymerization catalysts
ii) effluent treatment
iii) organic synthesis as well as uses in pyrotechnics
iv) to crosslink rubber compositions containing high vinyl styrene-butadiene rubber
v) dough conditioning
vi) hydrometallurgy
vii) medicine eg. mild antiseptic. 23
iii) Superoxides, XO2
Superoxide is the anion O2−. It is important as the product of the one-electron
reduction of dioxygen, which occurs widely in nature.
With one unpaired electron, the superoxide ion is a free radical, and, like
dioxygen, it is paramagnetic.
O
eg. M 
2
MO2 . . . . . .(M= K, Rb and Cs)


Reaction of superoxide, MO2

Reaction with water

These are strongly exothermic reactions and the heat produced will inevitably
decompose the hydrogen peroxide to water and more oxygen.
eg. MO2 + 2H2O  2MOH + H2O2 + O2

Reaction with dilute acids

Again, these reactions are even more exothermic than the ones with water.
eg. 2MO2 + 2HCl  2MCl + H2O2 + O2
Salts also decompose in the solid state, but this process requires heating:
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eg. 2NaO2 → Na2O2 + O2
Uses:

a) The above reaction is the basis of the use of potassium superoxide as an

oxygen source in chemical oxygen generators, such as those used on the
space shuttle and on submarines.
eg. 4KO2 + 2CO2 → 2K2CO3 + 3O2
a) Inorganic superoxides are used as solid rocket propellents.

4. Halogen
All the Gp I elements react directly with the halogen elements.
eg. 2M + X2  2MX (X = F2, Cl2, Br2, I2)

Li+ being the smallest in the group would be expected to form hydrated salts
eg. LiX.3H2O but the other alkali metal halides are anhydrous.

Alkali metal halides react with halogens and interhalogen compounds

forming ionic polyhalide compounds:
eg. KI + I2 → K[I3]
KBr + ICl → K[BrICl]
KF + BrF3 → K[BrF4] 25
5. Sulfur
All the metals react with sulfur, forming sulfides such as Na2S and
polysulfides, Na2Sn where n = 2, 3, 4, 5 or 6. The polysulfide ions
are made from zig-zag chains of sulfur atoms.

S S Na S S S Na
Na S S S S Na S S

Na2S can be made by heating NaSO4 with carbon or by passing H2S into
NaOH solution.
eg. Na2SO4 + 4C  Na2S + 4CO
NaOH + H2S  NaHS + H2O
NaOH + NaHS  Na2S + H2O

Gp I sulfides hydrolyse in water to give strong alkaline solution

eg. Na2S + H2O  NaSH + NaOH
sodium mercaptan
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6. Alkali Hydrides

Group I metals – ALL react with H2  ionic hydrides, M+H-.

Reactivity decreases from Li Cs
eg. LiH + H2O  LiOH + H2
H− has stable electron configuration of helium with a filled 1s -orbital.
These hydrides are called binary if they only involve two elements including
hydrogen eg. binary ionic hydrides typically MH (as in LiH).
Ionic hydrides are strongly nucleophilic, reducing, or basic properties
As the charge on the metal increases, the M-H bonding becomes more covalent
as in MgH2 and AlH3.
Ionic hydrides are commonly encountered as basic reagents in organic
synthesis:
C6H5C(O)CH3 + KH → C6H5C(O)CH2K + H2
Such reactions are heterogeneous because the KH does not dissolve.
Typical solvents for such reactions are ethers. . . . . (refer to crown and crypts
ethers) 27
 Water and other protic solvents cannot serve as a medium for ionic hydrides
because the hydride ion is a stronger base than hydroxide and most hydroxyl
anions. Hydrogen gas is liberated in a typical acid-base reaction.
Hydrogen gas is liberated in a typical acid-base reaction.
NaH + H2O → H2 (gas) + NaOH . . . . . .ΔH = −83.6 kJ/mol
ΔG = −109.0 kJ/mol
Alkali metal hydrides react with metal halides. Lithium aluminium hydride (often
abbreviated as LAH) arises from reactions with aluminium chloride.
4 LiH + AlCl3 → LiAlH4 + 3 LiCl

Uses
i) Hydrides such as, sodium borohydride and lithium aluminium hydride are
commonly used as reducing agents in organic synthesis, reduces carbonyl
compounds to alcohol.
eg. Li[AlH4] + RCOH  RCH2O-Li+  RCH2OH
H3O+

ii) Hydrides are important in rechargeable battery technologies such as Li-metal

hydride battery.
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7. Alkali Hydroxide

All alkali hydroxides are very corrosive, being strongly alkaline.

- ALL Group I elements react with water to give MOH.
- A strong base completely ionizes in aqueous solution to give OH- and a cation.
eg. LiOH + H2O  Li+ + 2 OH-
- Crystalline white solid and deliquescence.
- High m.pt. eg. NaOH (318oC), KOH (360oC).
- Absorb CO2 from atmosphere.
eg. 2NaOH + CO2  Na2CO3 + H2O
- Dissolve in water and alcohol to give strong alkali.
eg. NaOH + EtOH  NaOEt + H2O
Uses

i) Sodium hydroxide solutions, also known as lye and caustic soda, are used in the
manufacture of paper, textiles, drinking water, soaps and detergents.

ii) Used in breathing gas purification systems for eg. Spacecraft, submarine to remove
carbon dioxide from exhaled gas.
eg. 2 LiOH + CO2 → Li2CO3 + H2O 29
8. Alkali Carbonate
- carbonates are extremely stable (melting pt. >1000oC) except for Li2CO3 which is less
stable and decomposes readily.
Group I metal also forms solid bicarbonates, MHCO3 , which evolve CO2 upon warming.
2NaHCO3  Na2CO3 + H2O + CO2 ↑

Sodium bicarbonate is an amphoteric compound.
It has a pKa of 6.3 in water which causes aqueous solutions to be mildly alkaline:
HCO3- + H2O → H2CO3 + OH-
Sodium bicarbonate can be used as a wash to Uses :
remove any acidic impurities from a "crude“ liquid, 1. Fire extinguishers
1000°C
producing a more pure sample. Reaction of sodium eg. Na2CO3  Na2O + CO2
bicarbonate and an acid to give a salt and carbonic
2. Anti-acid medication
acid, which readily decomposes to carbon dioxide
and water: 3. Baking powder such as baking soda,
bread soda, cooking soda or
NaHCO3 + HCl → NaCl + H2CO3
bicarbonate of soda which consists
H2CO3 → H2O + CO2 of 30% NaHCO3 and 10% Ca(H2PO4)2.
Reaction of sodium bicarbonate and acetic acid:
4. Dehydrogenation of alcohols using
NaHCO3 + CH3COOH → CH3COONa + H2O + CO2 alkali catalyst
Sodium bicarbonate reacts with bases:
NaHCO3 + NaOH → Na2CO3 + H2O 30
Organic Compounds
i) Alkali metals can replace H in organic acids forming salts
eg. 2CH3COOH + 2Na → 2CH3COONa + H2
2C6H5COOH + 2K → 2C6H5COOK + H2
Soap is a mixture of sodium salts of palmitic, oleic and stearic acids by saponification.
eg. C15H31 COOH + NaOH → C15H31 COONa + H2O
palmitic acid soap

ii) Reactivity of metals in liquid ammonia

eg. M + NH3 → MNH2 + ½H2 . . . . . . in the presence of impurity or catalyst eg. Fe.

In absence of impurity, dilute soln of alkali metals in liq. NH3  dark blue
higher conc. ………………………….  lustre copper-bronze because
metal clusters are formed.
Very high conductivity due to
solvated electrons.

Acts as powerful reducing agents esp. towards elements of Gp IV, V and VI.

eg. Bi + Na/NH3  Na3Bi

S + Na/NH3  Na2S
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Organometallic Compounds

Carbides
When Li is heated with C or other alkali metals heated with acetylene, ionic carbides are formed
eg. 2Li + 2C  Li2C2 …………. contains [CC]2-
Na + C2H2  NaHC2  Na2C2 . …………. contains [CC-H] -

Reacts with water

eg. Na2C2 + 2H2O  2NaOH + C2H2

Li and Mg showed covalent character and form a number of alkyl and aryl compounds called
Grignard Compounds.
Uses
(i) Synthesis of aromatic derivatives
eg. RCl + Li → LiR + LiCl

(ii) Synthesis of organometallic and organic compounds

eg. LiBu + ArI → LiAr + BuI

eg. 3LiR + BCl3 → BR3 + 3LiCl (Organoboron compounds)

4LiR + SnCl4 → SnR4 + 4LiCl (Organotin compounds)
3LiR + P(OEt)3 → PR3 + 3LiOEt (Organophosphorus compounds)
LiR + 3CO → R2CO + 2LiCO (Ketone) 32
 Crowns and Cryptates
Group I metals have a weak in forming complexes eg. large size, low charge and lack of
empty orbitals of low energy to form bonds.
Crown ethers are multidentate macrocyclic complexing agents with nitrogen and oxygen.
Their characteristic properties are their ability to solubilize inorganic compounds in organic
solvents, and thus increase the range of their reactivities.
The bonding of the metal ion to these molecules is largely electrostatic and a close fit between
the size of the metal ion and the hole in the ring is essential  selective for alkali metal ion.
eg. benzo-12-crown-4 is selective for Li+, crown-5 for Na+ and crown-6 for K+ (refer to
diagram).

Applications of Crowns and Cryptates

i) There are added to organic solvents to dissolve
inorganic salts as in preparative organic synthesis.
ii) Crown ethers strongly bind certain cations, forming a
variety of new complexes.
iii) The oxygen atoms are well situated to coordinate
with a cation located at the interior of the ring,
whereas the exterior of the ring is hydrophobic. The
resulting cations often form salts that are soluble in
nonpolar solvents, and for this reason crown ethers
are useful in phase transfer catalysis. 33
Cryptates

Cryptates are even more selective and even stronger complexing agents than the
crown ethers. There differ by having N as well as O atoms to bond to the metal ion.
Since they are polycyclic they can bond to the metal ion completely.
For example, elemental Na or K dissolves very little in ethyl amine to form very
dilute solutions.
When Crypt-222 is added, the solubility increases by a factor of 103-104 !!!

-15oC
Eg. 2Na + Crypt-222  [Na(Crypt-222)]+Na- . . . . . . Sodium sodide
“golden complex”

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