(ii) Group 1 Elements

•Allaki Metals
(Alkali – Arabic word “ al kalya for soda Na2CO3)
• electron configuration:ns1
Li •Conduct electricity and heat, soft, have low m.p. that decreases
down the group

Na •Electropositive, reducing.

•Common Oxidation states: 0, +1 (Li+, Na+, K+)

K
•Na-1 is observed

Rb •Metals are prepard from electrolysis of molten salts

They form a wide range of salts which exhibit typical ionic
properties – high mp and are water soluble
Cs
The thermal stability of the carbonates, nitrates and suflates,
peroxides and superoxides increases down the group.
Fr
The solubilities of the hydroxides in water increases down the
group
LiOH < NAOH < KOH < RbOH < CsOH
 •The reactivity of the metals towards O2 and water
increases down the group
4 Li + O2 → 2Li2O (oxide)
2Na + O2 → Na2O2 (peroxide)
K+ O2 → KO2 (superoxide)

•React vigorously with water: reactivity increases

down the group

2 M(s) + 2 H2O (l) → 2 MOH + H2

Na metal + water
280
520

260
500

-1
First ionization energy/ kJmol
240 480
Atomic radius/pm

220 460

440
200
420
180
400

160
380

140 360
Li Na K Rb Cs Li Na K Rb Cs
(a) Lithium

Preparation of Metallic Lithium : electrolysis of molten LiCl

2 LiCl (l) 2Li(s) + Cl2(g)

The melting point of LiCl (610 oC) is reduced by adding KCl

LiCl is obtained mainly from spodumene LiAlSi2O6

LiCl

spodumene Lithium metal

Lithium in compounds :
present in all its compounds in +1 oxidation state
Lithium citrate
•Most important coordination number + 4
(e.g. Li(H2O)4+, Li(NH3)4+ and six (octahedral in LiH, LiCl)
•The lithium cation is the most polarizing of the alkali metal cations – significant
covalent character in bonding.
•Unique in reacting with N2 to form purple Li3N (lithium nitride) and only Li and Na
can react with carbon to form Li2C2 and Na2C2 (carbides)

Applications of Li compounds:
Li2CO3, Li citrate are drugs for manic depression and bipolar disorder
Organolithium compounds are commonly used in organic synthesis, e.g.
methyllithium 2 Li + MeBr → LiMe + LiBr
O-Li+ OH
O +
+ H
+ MeLi + Li+

CH3 CH3
CH3Li – methyllithium
Structure of CH3Li : a distorted cube

Li
H3 C
68o CH3

Li
C
H3
Li 268 pm
Li

231 pm
C
H3

♦ 4 Li+ ions occupying the corners of a tetrahedron whose 4 faces

are capped by CH3-groups
♦As two lone-pair electrons are shared by three Li+ ions, the bonding
between CH3- and Li+ is “two-electron-four-center bond”
♦ Li-Li distance (263 pm) is very close to the Li-Li distance (267.3
pm) in gaseous Li2 molecule : strong Li-Li bond
 The bonding between Li+ and CH3- ions is highly covalent
The covalent character is due to the high polarizing power
Li Be associated with high charge density.

Mg2+ also form highly covalent compounds.

Na Mg
Similarity between Li+ and Mg2+ - diagonal relationship due to
similar ionic radii (Li+ = 76 pm, Mg2+ = 72 pm)
K Ca
e.g. Li and Mg form normal oxide, whereas other group 1 metals
form peroxide and superoxide
Rb Rb
Li is the only group 1 metal that form Li3N. All gp 2 metals can form
nitrides.
Cs Cs
They form similar organometallic compounds: MeLi, Me2Mg

Fr Fr Carbonates of Li and Mg decompose upon heating to metal oxides

whereas carbonates of other gp 1 metals are thermally stable
 Lithium Nitride as a Potential H2 storage Material
synthesis

6 Li (s) + N2 (g) 2 Li3N (s)

BMW Hydrogen 7 Luxury Automobile

elevated temp,
high pressure
Li3N (s) + 2 H2 (g) LiNH2 (s) + 2 LiH (s)
1700 oC
(b) Crown Ethers

Charles J. Pedersen
Du Point
1909 – 1989
Nobel prize in chemistry 1987

Cyclic Polyethers
O

O O

O O

15-crown-5
What are the names of these crown ethers?

O O O

O O O O

O O
O O
O O
 Some Complexes
+

OH2
+ + O
OH2
O O O
O Li O O Na O K

O O O O
O O
O

O O O
O

O K+
O
[K(dibenzo-30-crown-10]+
O O
O
O
 Selective Binding of Alkali Ions

The stability of the complex of crown ethers and alkali ions

depends critically on the fit between the hole in the crown
ether and the cation
 Different Structures: relative sizes of ions and
the interior space of the donor

Encircled with the crown

encircled Partially embedded ether shaped like seam on
a tenis ball

e.g. [K(18-crown-6]+ e.g. [Na(H2O)18-crown-6]+

e.g. [K(dibenzo-
outside 30-crown-10]+
Sandwiched

e.g. [Rb(SCN)(18-crown-6)]+

e.g. [K(benzo-15-crown-5)2]+
 Ionic Nature of the Interactions

12-Crown-4 Electric Potential

Surface: The electric potential surface
is a measure of charge
distribution. Red indicates regions of
negative charge, green corresponds to
neutral areas, and blue indicates
regions of positive charge.
K+ Ion Transporters in Nature: Ionophore
Valinomycin : isolated from cultures of Streptomyces fulvissimus

•It is a circular molecule, made up of 3 repeats

of the sequence shown above

• Very selective for binding K+: bind K+ more strongly

than Na+ by a factor of 104 at room temp
 O
O

O K+

O O
O

•Puckering of the ring, stabilized by H-bonds, allows

valinomycin to closely surround a single unhydrated K+ ion.
Six oxygen atoms of the ionophore interact with the bound
K+, replacing O atoms
of waters of hydration.
•Whereas the interior of the valinomycin-K+ complex is polar, the
surface of the complex is hydrophobic. This allows valinomycin to
enter the lipid core of the bilayer, to solubilize K+ within this
hydrophobic environment
Valinomycin is a passive carrier for K+. It can bind or
release K+ when it encounters the membrane surface.
Valinomycin can catalyze net K+ transport because it
can translocate either in the complexed or uncomplexed
state. The direction of net flux depends on the
electrochemical K+ gradient
 An Interesting Application of Crown Ether –
Isolation of Allkalides

When the alkali metals (except Li) are dissolved in aliphatic

amines or polyethers, they disproportionate to a small
extent into solvated cation M+ and solvated anion (alkalide)
with a helium shell. H2C CH2 Me O Me
O O
H2N NH2

Solvent
2M M+(solv) + M-(solv)
Addition of crown ether can drastically increase the
solubility of the alkali cations in the solvent and thus
increases the concentration of the alkalide M-.
e.g. [Na(18-crown-6)]+Na-