ALKALI METALS 29

CHAPTER-2

ALKALI METALS

2.1 Electronic Structure

Group 1 elements all have one valence electron in their outer orbital – an s electron which occupies a
spherical orbital. Ignoring the filled inner shells the valence shell electronic structures may be written as 2s1,
3s1, 4s1, 5s1, 6s1 and 7s1. The single valence electron is a long distance from the nucleus, is only weakly held
and is readily removed. In contrast the remaining electrons are closer to the nucleus, more tightly held, and
are removed only with great difficulty. Because of similarities in the electronic structures of these elements,
many similarities in chemical behaviour would be expected.
Table : Electronic Structure
Atomic
Element Symbol Electronic Structure
Number
Lithium 3 Li ls2 2s1 or [He] 2s1
Sodium 11 Na ls2 2s22p6 3s1 or [Ne] 3s1
Potassium 19 K ls2 2s22p6 3s23p64s1 or [Ar] 4s1
Rubidium 37 Rb ls2 2s22p6 3s23p63d10 4s2 4p65s1 or [Kr] 5s1
Caesium 55 Cs ls2 2s22p6 3s23p63d10 4s2 4p6 4d105s25p6 6s1 or [Xe] 6s1
Francium 87 Fr [Rn] 7s1

2.2 Size of Atoms and Ions

Group 1 atoms are the largest in their horizontal periods in the periodic table. When the outer electron
is removed to give a unipositive ion, the size decreases considerably. There are two reasons for this
1. The outermost shell of electrons has been completely removed.
2. Having removed an electron, the positive charge on the nucleus is now greater than the charge on
the remaining electrons, so that each of the remaining electrons is attracted more strongly towards
the nucleus. This reduces the size further.
Positive ions are always smaller than the parent atom. Even so, the ions are very large and they
increase in size from Li+ to Fr+ as extra shells of electrons are added.
The Li+ is much smaller than the other ions. For this reason, Li only mixes with Na above 380°C,
and it is immiscible with the metals K, Rb and Cs, even when molten; nor will Li form substitutional
alloys with them. In contrast the other metals Na, K, Rb and Cs are miscible with each other in all
proportions.

Q. Among the molten alkali metals, the examples of an immiscible pair (in all proportions) is
[NET-JRF, Dec-2013]
(a) K and Na (b) K and Cs (c) Li and Cs (d) Rb and Cs
ALKALI METALS 30

2.3 Density
The atoms are large, so Group 1 elements have remarkably low densities. Lithium metal is only about
half as dense as water, whilst sodium and potassium are slightly less dense than water. It is unusual for
metals to have low densities, and in contrast most of the transition metals have densities greater than 5g
cm–3. for example iron 7.9 g cm–3, mercury 13.6 g cm–3, and osmium and iridium (the two most dense ele-
ments) 22.57 and 22.61 g cm–3 respectively.
Table: Size and density
Ionic radius M+ Density
Group-I Elements Metallic radius (Å)
six-coordinate (Å) (gcm–3)
Li 1.52 0.76 0.54
Na 1.86 1.02 0.97
K 2.27 1.38 0.86
Rb 2.48 1.52 1.53
Cs 2.65 1.67 1.90

2.4 Ionization Energy

The first ionization energies for the atoms in this group are appreciably lower than those for any other
group in the periodic table. The atoms are very large so the outer electrons are only held weakly by the
nucleus: hence the amount of energy needed to remove the outer electron is not very large. On descending
the group from Li to Na to K to Rb to Cs, the size of the atoms increases due to increase in number of shells:
the outermost electrons become less strongly held, so the ionization energy decreases.
The second ionization energy — that is the energy to remove a second electron from the atoms — is
extremely high. The second ionization energy is always larger than the first, often by a factor of two,
because it involves removing an electron from a smaller positive ion, rather than from a larger neutral atom.
The difference between first and second ionization energies is much larger in this case since in addition it
corresponds to removing 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.
Table: Ionization energies
First ionization energy Second ionization energy
Group-I Elements
(kJ mol–1) (kJ mol–1)
Li 520.1 7296
Na 495.7 4563
K 418.6 3069
Rb 402.9 2650
Cs 375.6 2420

2.5 Electronegativity and Bond Type

The electronegativity values for the elements in this group are very small, in fact the smallest values of any
element. Thus when these elements react with other elements to form compounds, a large electronegativity
difference between the two atoms is probable, and ionic bonds are formed.
ALKALI METALS 31

Electronegativity of Cl = 3.0
Electronegativity of Na = 0.9
Electronegativity difference  2.1

Table : Electronegativity values

Group-I Elements Pauling’s

electronegativity
Li 1.0
Na 0.9
K 0.8
Rb 0.8
Cs 0.7
An electronegativity difference of approximately 1.7–1.8 corresponds to 50% ionic character. The
electronegativity difference value 2.1 in NaCl indicates that the bonding in NaCl is predominantly ionic.
Similar arguments apply to other compounds: for example, the electronegativity difference in LiF is 3.0, and
in KBr is 2.0, and both the compounds are ionic.

2.6 Structures of the Metals, Hardness and Cohesive Energy

At normal temperatures all the Group l metals adopt a body-centred cubic type of lattice with a
coordination number of 8. However, at very low temperatures lithium forms hexagonal close-packed
structure with a coordination number of 12.
The metals are all very soft, and can be cut quite easily with a knife. Lithium is harder than the others,
but is softer than lead.
The cohesive energy is the force holding the atoms or ions together in the solid. (This is the same in
magnitude, but the opposite in sign, to the enthalpy of atomization, which is the energy required to break the
solid up into gaseous atoms.) The cohesive energies of Group l- metals are about half of those for Group 2,
and one third of those for Group 13 elements. The magnitude of the cohesive energy determines the
hardness, and it depends on the number of electrons that can participate in bonding and on the strength of the
bonds formed. The softness, low cohesive energy and weak bonding in Group l elements are consequences
of these metals having only one valency electron which can participate in bonding (compared with two or
more electrons in most other metals), and of the large size and diffuse nature of the outer bonding electron.
The atoms become larger on descending the group from lithium to caesium, so the bonds are weaker, the
cohesive energy decreases and the softness of the metals increases.
Table: Cohesive energy.

Group-I Elements Cohesive energy

(enthalpy of atomization) (kJ mol–1)
Li 161
Na 108
K 90
Rb 82
Cs 78

2.7 Melting and Boiling Point

ALKALI METALS 32

Low values for cohesive energy are reflected in the very low values of melting and boiling points in
the group. The cohesive energy decreases down the group, and the corresponding melting points
decreases also.
The melting point of elements ranges from lithium 181°C to caesium 28.5°C. These are extremely low
for metals, contrast with the melting points of the transition metals, most of which are above 1000°C.
The melting point of lithium is nearly twice as high (in °C) as that for sodium.
Table : Melting and Boiling points

Group-I Elements Melting point (°C) Boiling point (°C)

Li 181 1347
Na 98 881
K 63 766
Rb 39 688
Cs 28.5 705

(a) Characteristic Flame Coloration : All the alkali metals give characteristic colours in bunsen flame.
The reason is that when an alkali metal or any of its compounds is heated in a bunsen flame, the
electrons get excited to higher energy levels. When these electrons return to their original (ground)
level, the excitation energy which had been absorbed by them, is released in the form of light in the
visible region of the spectrum. Now for the same excitation energy, the energy level to which the
electron in Li rises is lower than that to which the electron in Na rises and this, in turn, is lower than
the level to which the electron in K rises and so on. These differences are on account of differences
in the forces of attraction between the nucleus and the outermost electron. Consequently, when the
electron returns to the ground state, energy released is lowest in Li and increases in the order LiCs.
As a result of this, the frequency of the light emitted when the compound is placed in the bunsen
flame will be minimum in the case of lithium. It increases in the order LiCs. Thus, the colour of
the flame is crimson red in the case of Li, golden yellow in the case of Na, violet in the case of K and
almost the same in the case of Rb and Cs.
2.8 Lattice Energies :
Salts of alkali metals consist of cations and anions only and are, therefore, called ionic solids. The
lattice energy of an ionic solid is defined as the energy released when cations and anions in gaseous
state are brought from infinity to their respective crystal sites to form one mole of the ionic crystal.
Thus, we have.
Li  g   Cl –  g  
 Li+ Cl –  s  ; H  Lattice energy of Li  Cl –
Cs  g   Cl –  g  
 Cs+ C1–  s  ; H  Lattice energy of Cs Cl –

Lattice energies of ionic solids are quite high : This is to be expected in view of strong
electrostatic attraction between oppositely charged ions. When such ions come close together, the
system acquires minimum energy and, therefore, a large amount of energy is released to the
surroundings. Since coulombic forces of attraction vary directly as the product of the charges, it
follows that the higher the charge on the ions (i.e., the higher the valency of the ions), the greater
should be the lattice energy of the ionic solid. Thus, lattice energy increases as we move from uni-
univalent ionic solids like lithium flouride (Li+F– ) to uni-bivalent solids like calcium* fluoride
(Ca2+2F–) and to bi-bivalent solids like magnesium sulphide (Mg2+S2–).
For cation of the same valency, lattice energy of ionic solids having the same anion, decreases with
increase in the size of the cation. Thus, lattice energy of Li+ F– is 1034 kJ mol–1 while that of Cs+ F– is
ALKALI METALS 33

743.9 kJ mol–1. Similarly, lattice energy of Li+ I– is 718.4 kJ mol–1, while that of Cs+ I– is 584.5 kJ
mol–1. Since the fluoride ion in the first case and the iodide ion in the second case is common the
higher values for lithium salts are due to the smaller size of Li+ ion as compared to that of Cs+ ion in
the respective ionic solids. We may thus conclude that, as a general rule, lattice energies of salts of
alkali metals having a given anion decrease with increase in atomic number of the alkali metal.

Born-Haber Cycle : Energy changes in the formation of Ionic Compounds

Hess’s law states that the energy change occurring during a reaction depends only on the energy of the
initial reactants and the energy of the final products, and not on the reaction mechanism, or the route taken.
Thus, by Hess’s law, the energy change for the reaction of solid sodium and chlorine gas to form a sodium
chloride crystal by the direct route (measured as the enthalpy of formation) must be the same as the sum of
all the energy changes going round the cycle by the long route, i.e. by producing first gaseous atoms of the
elements, then gaseous ions, and finally packing these to give the crystalline solid

Figure : Born-Haber cycle for the formation of NaCl.

This may be expressed as.
ΔH f = + H s + I + 12 H d + E + U

Where, H f  Enthalpy of formation

H s  Enthalpy of sublimation
H d  Enthalpy of dissociation
ALKALI METALS 34

All the halides MCl have negative enthalpies of formation, which indicates that thermodynamically
(that is in terms of energy) it is feasible to form the compounds MCl from the elements.
1. The most negative enthalpies of formation occur with the fluorides. For any given metal, the values
decrease in the sequence fluoride > chloride > bromide > iodide. Thus the fluorides are the most
stable, and the iodides are the least stable.
2. The enthalpies of formation for the chlorides, bromides and iodides become more negative on
descending the group. This trend is observed with most salts, but the opposite trend is found in the
fluorides.
Ionic compounds may also be formed in solution, when a similar cycle of energy changes must be
considered, but the hydration energies of the positive and negative ions must be substituted for the
lattice energy.

2.9 Colour of Compounds

Colour arises because the energy absorbed or emitted in electronic transitions corresponds to a
wavelength in the visible region. The all Group l metal ions have noble gas configurations in which
all the electrons are paired. Thus promoting an electron requires some energy to unpair an electron,
some to break a full shell of electrons and some to promote the electron to a higher level. The total
energy is large : hence there are no suitable transitions and the compounds are typically white. Any
transitions, which do occur will be of high energy, will appear in the ultraviolet region rather than in
the visible region and will be invisible to the human eye. Compounds of Group l metals are typically
white, except those where the anion is coloured, for example sodium chromate Na2[CrO4] (yellow),
potassium dichromate K2[Cr2O7] (orange), and potassium permanganate K[MnO4] (deep purple). In
these cases the colour comes from the anions [CrO4]–, [Cr2O7]2– or [MnO4]– and not from the Group-I
metal ion.
When Group-I elements form compounds (usually ionic, but there are a few covalent compounds),
all the electrons are paired. Because of this Group l compounds are diamagnetic. There is one notable
exception-the superoxides.

2.10 Oxides, Hydroxides, peroxides and superoxides.

(a) Reaction with O2
The metals all burn in air to form oxides, though the product varies depending on the metal. Lithium
forms the monoxide Li2O (and some peroxide Li2 O2), sodium forms the peroxide Na2O2 (and some
monoxide Na2O), and the others form superoxides of the type MO2.
All five metals can be induced to form the normal oxide, peroxide or superoxide by dissolving the
metal in liquid ammonia and bubbling in the, appropriate amount of dioxygen.

Note: Reaction with dinitrogen

Lithium is the only element in the group that reacts with dinitrogen to form a nitride. Lithium nitride, Li3N, is ionic (3Li+
and N3–), and is ruby red. Two reactions of the nitride are of interest. First, on heating to a high temperature it
decomposes to the elements, and second, it reacts with water, giving ammonia.

heat
2Li3 N 
 6Li  N 2
Li 3 N  3H 2 O 
 3LiOH  NH3
ALKALI METALS 35

(b) Normal oxides - monoxides

The monoxides are ionic, for example 2Li+ and O2–.Li2O and Na2O are pure white solids as expected,
but surprisingly K2O is pale yellow, Rb2O is bright yellow and Cs2O is orange. Metallic oxides are usually
basic. The typical oxides M2O are strongly basic oxides, and they react with water, forming strong bases.
Li2 O  H 2 O 
 2LiOH
Na 2 O  H 2 O 
 2NaOH
K 2 O  H 2 O 
 2KOH
The crystal structures of Li2O, Na2O. K2O and Rb2O are anti-fluorite structures. The anti-fluorite
structure is like that for fluorite CaF2, except that the positions of the positive and negative ions are
interchanged. Thus Li+ fill the sites occupied by F–. and O2– fill sites occupied by Ca2+. Cs2O has an anti-
CdCl2 layer structure.

(b) Hydroxides
Group l metals all react with water, liberating hydrogen and forming the hydroxides. 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.

2Li  2H 2 O 
 2LiOH  H 2
2Na  2H 2 O 
 2NaOH  H 2
2K  2H 2 O 
 2KOH  H 2

The standard electrode potentials E° are Li+ | Li = –3.05 volts, Na+ | Na = –2.71, K+ | K = –2.93, Rb+ |
Rb = –2.92, Cs+ | Cs = –2.92. Lithium has the most negative standard electrode potential of any element in
the periodic table, largely because of its high hydration energy. Standard electrode potentials E° and Gibbs
free energy G are related by the equation.
     G = –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 G value.
Thus the reaction does not occur. However, the reverse reaction Li  Li+ + e– has a large negative value of
G, so lithium liberates more energy than the other metals when it reacts with water. In view of this it is at
first sight rather surprising that lithium reacts gently with water, whereas potassium, which liberates less
energy, reacts violently and catches fire. The explanation lies in the kinetics (that is the rate at which the
reaction proceeds), rather than in the thermodynamics (that is the total amount of energy liberated).
Potassium has a low melting point, and the heat of reaction is sufficient 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.
Sodium hydroxide NaOH is often called caustic soda, and potassium hydroxide is called caustic
potash, because of their corrosive properties (for example on glass or on skin). These caustic alkalis are the
strongest bases known in aqueous solution. The hydroxides of Na. K, Rb and Cs are very soluble in water,
but LiOH is much less soluble due to covalent character.
ALKALI METALS 36

Table : Solubility of Group l hydroxides.

Group-I Element Solubility (g /100g H O)

Li 13.0(25°C)
Na 108.3(25°C)
K 112.8(25°C)
Rb 197.6(30°C)
Cs 385.6(15°C)
At 25°C a saturated solution of NaOH is about 27 molar, whilst saturated LiOH is only about 5 molar.
The bases react with acids to form salts and water, and are used for many neutralizations.
NaOH  HCl 
 NaCl  H 2 O
The bases also react with CO2, even traces in the air, forming the carbonate. LiOH is used to absorb
carbon dioxide in closed environments such as space capsules (where its light weight is an advantage in
reducing the launching weight).
2NaOH  CO 2 
 Na 2 CO3 + H 2 O
They also react with the amphoteric oxides, Al2O3 forming aluminates, SiO2 (or glass) forming
silicates, SnO2 forming stannates, PbO2 forming plumbates and ZnO forming zincates.
The bases liberate ammonia from both ammonium salts and coordination complexes where ammonia
is attached to a transition metal ion (ammine complexes).
NaOH.  NH 4 Cl 
 NH 3  NaCl  H 2 O
6 NaOH  2 Co  NH 3 6  Cl3 
 12NH3  Co 2 O3  3NaCl  3H 2O
hexammine
cobalt  III  chloride

NaOH reacts with H2S to form sulphides S2–, and hydrogen sulphides SH–, and it is used to remove
mercaptans from petroleum products.
NaOH  H 2S 
 NaSH 
 Na 2S

The hydroxides react with alcohols, forming alkoxides.

NaOH  EtOH 
 NaOEt  H2O
sodium ethoxide

KOH resembles NaOH in all its reactions, but as KOH is much more expensive it is seldom used.
However, KOH is much more soluble in alcohol. thus producing OC2 H5– ions by the equilibrium.

 OC2 H5–  H 2 O

C2 H5OH  OH  

(d) 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.
Na 2 O 2 + 2H 2 O 
 2NaOH + H 2 O 2
ALKALI METALS 37

Na2O2 is pale yellow in colour : It is used industry for bleaching wood pulp, paper and fabrics such
as cotton and linen. It 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
liquids. 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. Potassium superoxide KO2 is even better for this purpose.
Some typical reactions are.
3Na 2 O 2 + 2Al +2H 2O 
 2NaAlO 2  4NaOH
3O 22 + 2Cr 3+  4OH  
 2CrO 2–
4  2H 2 O

Na 2 O 2 + CO 
 Na 2 CO3
2Na 2 O 2 + 2CO 2 
 2Na 2 CO3 + O 2

The industrial process for forming sodium peroxide is a two-stage reaction in the presence of excess air.
1
2Na + O 2 
 Na 2 O
2  sodium peroxide 
1
Na 2 O + O 2  Na 2 O 2
2  sodium superoxide 

The superoxides contain the ion [O 2 ] , which has a unpaired electron and hence they are paramagnetic
and are all coloured (LiO2 and NaO2 yellow, KO2 orange, RbO2 brown and CsO2 orange.
The normal oxides contain O2– ion, the peroxides contain O2– –
2 ion and superoxides contain O 2 ion. The
peroxides and superoxides become more stable with increase in atomic number of the alkali metal. The
formation and stability of these oxides can be explained on the basis of their lattice energy Li+ ion being a
small ion has a strong positive field around it and can stabilize only a small anion, O2–, whereas Na+ ion
being a large cation can stabilize a large anion and so on. Thus, smaller cation can stabilize smaller anion
and larger cation can stabilize larger anion.
The higher oxides, viz., peroxides and superoxides are important oxidising agents. They react with
dilute acids forming hydrogen peroxide and oxygen, respectively.
Na 2 O 2 + H 2SO4 
 Na 2SO 4 + H 2O 2
4KO 2 + 2H 2SO 4 
 2K 2SO 4 + 2H 2O + 3O 2
Superoxides are even stronger oxidizing agents than peroxides, and give both H2O2 and O2 on reaction
with either water or acids.
1
KO2 + 2 H 2 O 
 KOH + H 2O 2 + O2
2
KO2 is used in space capsules, submarines, for breathing masks, because it both produces dioxygen
and removes carbon dioxide. Both functions are important in life support systems.
4KO 2 + 2CO 2 
 2K 2 CO3 + 3O 2
more CO
2  4KHCO + 3O
4KO 2 + 4CO 2 + 2H 2O  3 2

Sodium superoxide cannot be prepared by burning the metal in dioxygen at atmospheric pressure, but
it is made commercially in good yields by reacting sodium peroxide with dioxygen at a high temperature
and. pressure (450°C and 300 atmospheres) in a stainless steel bomb.
Na 2 O 2  O 2 
 2NaO 2
The peroxide ion [—O—O—]2– has 18 electrons, which occupy the molecular orbitals as shown.
ALKALI METALS 38

 p 2y ,  * 2 p 2y

2 * 2 2 * 2
 1s ,  1s ,  2 s ,  2s ,  2 p x2 ,  
 2 pz2 ,  * 2 p z2
increasing energy

Thus the bond order of O–O is one, corresponding to a single bond.
The superoxide ion [O2]– has only 17 electrons, which give a bond order of 1.5.
 p 2y ,  * 2 p 2y
 
 1s 2 ,  *1s 2 ,  2 s 2 ,  * 2s 2 ,  2 p x2 ,  
 2 pz2 ,  * 2 p1z
increasing energy
 
Generally, large atoms or ions form weaker bonds than smaller ones. The peroxide and superoxide ions are
large, and it is noteworthy that the stability of the peroxides and superoxides increases as the metal ions
become larger. This shows that large cations can be stabilized by large anions, since if both ions are similar
in size the coordination number will be high, and this gives a high lattice energy.

(e) Sodium Bicarbonate, NaHCO3

NaHCO3 can be used on its own to make cakes or bread ‘rise’ since it decomposes between 50°C and 100°C,
giving bubbles of CO2.
gentle heat
2NaHCO3 
 Na 2 CO3  H 2 O  CO 2
Baking powder is more commonly used, and contains NaHCO3, Ca(H2PO4)2 and starch. The
Ca(H2PO4)2 is acidic and when moistened it reacts with NaHCO3, giving CO2. The starch is a filler. An im-
proved ‘combination baking powder’ contains about 40% starch, 30% NaHCO3, 20% NaAl(SO4)2 and 10%
Ca(H2PO4)2. The NaAl(SO4)2 slows the reaction down so the CO2 is given off more slowly.

2.11 Oxosalts-Carbonates,Bicarbonates, Nitrates and Nitrites

Group 1 metals are highly electropositive and thus form very strong bases, and have quite stable
oxosalts.
The carbonates are remarkably stable, and will melt before they eventually decompose into oxides at
temperatures above 1000°C. Li2CO3 is considerably less stable and decomposes more readily.
Because Group l metals are so strongly basic, they also form solid bicarbonates (also called
hydrogencarbonates). No other metals form solid bicarbonates, though NH4HCO3 also exists as a
solid. Bicarbonates evolve carbon dioxide and turn into carbonates on gentle warming. This is one
test for bicarbonates in qualitative analysis. The crystal structures of NaHCO3 and KHCO3 both show
hydrogen bonding, but are different. In NaHCO3 the HCO3– a ions are linked into an infinite chain,
whilst in KHCO3 a dimeric anion is formed.

Lithium does not form a solid bicarbonate, though LiHCO3 can exist in solution. All the carbonates
and bicarbonates are soluble in water
ALKALI METALS 39

Over 50000 tonnes of Li2CO3 are produced annually. Most of it is added as an impurity to Al2O3 to
lower its melting point in the extraction of aluminium by electrolysis. Some is used to toughen glass
(sodium in the glass is replaced by lithium). Na2CO3 is used as washing soda to soften water in hard
water areas, and NaHCO3 is used as baking powder.
The nitrates can all be prepared by the action of HNO3 on the corresponding carbonate or hydroxide,
and they are all very soluble in water. LiNO3 is used for fireworks and red-coloured distress flares.
Large deposits of NaNO3 are found in Chile, and are used as a nitrogenous fertilizer. 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). KNO3 is usually obtained from
synthetic nitric acid and K2CO3, but at one time it was made from NaNO3.
2HNO3  K 2 CO3 
 2KNO3  CO 2  H 2O
NaNO3  KCl 
 KNO3  NaCl
Group l nitrates are fairly low melting solids, and are amongst the most stable nitrates known.
However, on strong heating they decompose into nitrites, and at higher temperatures to the oxide.
LiNO3 decomposes more readily than the others, forming the oxide.
LiNO3 
 Li 2 O  O 2  NO 2
500°C


2NaNO3 
 2NaNO 2 + O 2
800°C


4NaNO3 
 2Na 2 O + 5O 2 + 2N 2
2.12 Halides and Polyhalids
Since Li+ is the smallest ion in the group, it would be expected to form hydrated salts more readily
than the other metals. LiCl, LiBr and LiI form trihydrates LiX·3H2O, but the other alkali metal halides form
anhydrous crystals. All the halides adopt a NaCl type of structure with a coordination number of 6 except for
CsCl, CsBr and CsI. The latter have a CsCl type of structure with a coordination number of 8. The alkali
metal halides react with the halogens and interhalogen compounds forming ionic polyhalide compounds.
KI + l 2 
 K [I3 ]
KBr + ICl 
 K [IBrCl]
KF + BrF3 
 K [BrF4 ]
2.13 Hydrides
Group l metals all react with hydrogen, forming ionic or salt-like hydrides M+ H–. However, the ease
with which they do so decreases from lithium to caesium. These hydrides contain the H– ion. It can be
proved that H– ions exist because on electrolysis hydrogen is liberated at the anode.
The hydrides react with water, liberating hydrogen, and lithium hydride is used as a source of
hydrogen for military purposes and for filling meteorological balloons.
LiH  H 2 O 
 LiOH  H 2
Lithium also forms a complex hydride Li[AlH4], called lithium aluminium hydride, which is a useful
reducing agent. It is made from lithium hydride in dry ether solution.
 Li  AlH 4   3LiCl .
4LiH  AlC13 

Lithium aluminium hydride is ionic, and the [AIH4]– ion is tetrahedral. Li[AIH4] is a powerful
reducing agent and is widely used in organic chemistry, as it reduces carbonyl compounds to alcohols. It
reacts violently with water, so it is necessary to use absolutely dry organic solvents, for example ether which
has been dried over sodium. Li[AIH4] will also reduce a number of inorganic compounds.
ALKALI METALS 40

BCl3 + Li  AlH 4  
 B2 H 6 diborane
PCl3 + Li[AlIH 4 ] 
 PH3 phosphine
SiCl4 + Li  AlH 4  
 SiH 4 silane

Sodium tetrahydridoborate (sodium borohydride) Na[BH4] is another hydride complex. It is ionic,

comprising tetrahedral [BH4]– ions. It is best obtained by heating sodium hydride with trimethyl borate.
230–270°C
4NaH  B  OCH3 3 
 Na[BH 4 ]  3NaOCH 3

2.14 Solubility and Hydration

(a) Reaction with water (H2O)
All the simple salts dissolve in water, producing ions, and consequently the solutions conduct
electricity. Since Li+ ions are small, it might be expected that solutions of lithium salts would conduct
electricity better than solutions of the same concentration of sodium, potassium, rubidium or caesium salts.
The small ions should migrate more easily towards the cathode, and thus conduct more than the larger ions.
However, ionic mobility or conductivity measurements in aqueous solution give results in the opposite order
Cs+ > Rb+ > K+ > Na+ > Li+. The reason for this apparent anomaly is that the ions are hydrated in solution.
Since Li+ is very small, it is heavily hydrated. This makes the radius of the hydrated ion large, and hence it
moves only slowly. In contrast, Cs+ is the least hydrated, and the radius of the hydrated Cs+ ion is smaller
than the radius of hydrated Li+, and hence hydrated Cs+ moves faster, and conducts electricity more readily.
Some water molecules touch the metal ion and bond to it, forming a complex. These water molecules
constitute the primary shell of water. Thus Li+ is tetrahedrally surrounded by four water molecules. This may
be explained by the oxygen atoms of the four water molecules using a lone pair to form a coordinate bond to
the metal ion. With four electron pairs in the valence shell the VSEPR theory predicts a tetrahedral structure.
Alternatively, using valence bond theory, the 2s orbital and the three 2p orbitals form four sp3 hybrid orbitals
which are filled by the lone pairs from the oxygen atoms.
1s 2s 2p
Electronic structure of
lithium atom
1s 2s 2p
Electronic structure of
Li+ ion

Electronic structure of 1s 2s 2p
Li ion with four water
molecules bonded, using
a lone pair on oxygen
to form a coordinate bond four electrons pairs-tetrahedral
(sp3 hybridization)
With the heavier ions, particularly Rb+ and Cs+, the number of water molecules increases to six. VSEPR
theory predicts an octahedral structure Valence bond theory also indicates an octahedral arrangement using
1s orbital, three p orbitals and two d orbitals for bonding.
ALKALI METALS 41

3d 4s 4p
Electronic structure of potassium full
atom in the ground state inner
shell 3d 4s 4p
Electronic structure of K+ ion

3d 4s 4p
Electronic structure K+ bonded to six
molecules of water

six orbitals-octahedral
(d2sp3 hybridization)

The size of the hydrated ions is an important factor affecting the passage of these ions through cell
walls. It also explains their behaviour on cation exchange columns, where hydrated Li+ ions are attached less
strongly and hence eluted first.
The decrease in hydration from Li+ to Cs+ is also shown in the crystalline salts, for nearly all lithium
salts are hydrated, commonly as trihydrates. In these hydrated Li salts Li+ is coordinated to 6H2O, and the
octahedra share faces, forming chains. Many sodium salts are hydrated, e.g. Na2CO3 · 10H2O, Na2CO3 ·
7H2O and Na2CO3 · H2O. Few potassium salts and no rubidium or caesium salts are hydrated.
The simple salts are all soluble in water, and so in qualitative analysis these metals need to be
precipitated as less common salts. Thus Na+ is precipitated by adding zinc (or copper) uranyl acetate
solution and precipitating NaZn(UO2)(Ac)9 ·H2O sodium zinc uranyl acetate. K+ is precipitated by adding a
solution of sodium cobaltinitrite and precipitating potassium cobaltinitrite K3[Co(NO2)6] or by adding
perchloric acid and precipitating potassium perchlorate KClO4. Group l metals can be estimated
gravimetrically, sodium as the uranylacetate and potassium, rubidium and caesium as tetraphenylborates.
However, modern instrumental methods such as flame photometry and atomic absorption spectrometry are
much quicker and easier to use and are now used in preference to gravimetric analysis.

K   Na 3 Co  NO 2 6  
 Na   K 3  Co  NO 2 6  potassium cobaltinitrite
   
K   NaClO 4 
 Na   KClO 4 potassium perchlorate

K   Na B  C6 H 5 4  
 Na   K B  C6 H5 4  potassium tetraphenylborate
quantitative precipitate
If a salt is insoluble its lattice energy is greater than the hydration energy. K[B(C6H5)4] is insoluble
because the hydration energy is very small as a result of the large size of its ions.
The solubility of most of the salts of Group l elements in water decreases on descending the group. 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 crystal lattice (lattice energy). Conversely, if the solid is insoluble, the
hydration energy is less than the lattice energy.
The reason why the solubility of most Group I metals decreases on descending the group is that the
lattice energy only changes slightly, but the free energy of hydration changes rather more. For example, the
difference in lattice energy between NaCl and KCl is 67 kJ mol–1, and yet the difference in G (hydration) for
Na+ and K+ is 76 kJ mo1–1. Thus KCl is less soluble than NaCl.
The Group l fluorides and carbonates are exceptional in that their solubilities increase rapidly on
descending the group. The reason for this is that their lattice energies change more than the hydration
energies on descending the group. The lattice energy depends on electrostatic attraction between ions, and is
ALKALI METALS 42

q1q2
inversely proportional to the square of the distance between the ions, that is proportional, to . It follows
r2
that the lattice energy will vary most when r  is small, that is with F–, and will vary least when r– is large
(with I–). The weight of solute dissolving does not provide a very useful comparison of the solubilities,
because the molecular weights differ. The easiest way to compare the number of ions is to compare the
solubilities as molar quantities.
(b) Solubility in Mercury:
The alkali metals dissolve readily in mercury forming what are called amalgams. The process is highly
exothermic.
(c) Reactions with NH3 (gaseous):
When ammonia gas is passed over alkali metals, the corresponding amides are formed.
2M  2NH3 
 2MNH 2  H 2
The alkali amides are also formed when the solutions of alkali metals in liquid NH3 are evaporated.
Solubility in Liquid Ammonia:
All the alkali metals dissolve in anhydrous liquid ammonia giving deep blue solutions. The colour deepens
with increase in concentration of the solution. The concentrated solutions are bronze in colour and possess
metallic lustre. The solutions are good conductors of electricity and are paramagnetic in nature. The
paramagnetic character decreases with increase in concentration.
The dissolution of the metal is accompanied by its ionisation.
 M + e–
M 
When the alkali metals are dissolved in liquid ammonia, the ammonia molecules solvate the cation as
well as the electron, as represented below.
 M   NH3  x  e –  NH 3  y
M  NH 3  in excess 

The values of x and y depend upon the extent of solvation of the alkali metal ion and the electron,
respectively. The exact mechanism for the solvation of electrons is not clear. It is argued, however, that the
electron released by the alkali metal causes polarisation of the charge of the electrons of the surrounding
ammonia molecules and the repulsion between the electron released by alkali metal and the electrons of the
surrounding ammonia molecules causes a ‘hole’ in which the released electron is trapped. It is the
ammoniated electron which is responsible for the blue colour of the solution. The electrical conductivity is
due to the ammoniated cation as well as the ammoniated electron. The dilute solutions are paramagnetic
because they contain free electrons. The decrease in paramagnetic character with increase in concentration
suggests that in concentrated solutions the ammoniated electrons associate to form electron pairs.

2e –  NH3  y 
 e –  NH3 y 
 2

If blue colour is allowed to stand, the colour slowly fades until it disappears owing to formation of
metalamide. At concentration above 3 M, solutions are copper-bronze coloured and have a metallic lustre
because metal clusters are formed. In the presence of impurities or catalysts such as Fe, the alkali metals
react with NH3 to form metal amide and hydrogen.
M + NH 3 
 MNH 2  H 2

If all impurities or catalysts are absent, the group 1 metals dissolve in liquid ammonia.
ALKALI METALS 43

The alkali metal solutions in liquid ammonia are stable and decompose only slowly liberating
hydrogen. The presence of transition metals (such as Fe, Pt, Zn, etc.) even in traces, catalyses the reaction.
Due to the presence of the free or ammoniated electrons, these solutions behave as strong reducing
agents as is evident from the following reactions.
These solutions reduce aerial oxygen to superoxide and peroxide ions without causing cleavage of
O—O bond.
e-  NH  y e –  NH  y
3
O 2  O 2– 
3
 O 22–

These solutions reduce metal ions to their unusually low oxidation states.
e –  NH3 
y
K 2  Ni  CN  4   2K   K 4  Ni  CN 4   Ni is in 0 oxidation state

y
e   NH3 
Mn 2  CO 10  2K   2K Mn  CO 5   Mn is in  1 oxidation state 

y
e   NH3 
Fe  CO 5  2Na   Na 2  Fe  CO 4   CO  Fe is in –2 oxidation state
2.16 Ionic Conductance:
The alkali metal ions in aqueous solution have high electrical conductance. The electrical conductance
+
of Li ion, which is the smallest of alkali metal ions, is expected to be the highest. Since ionic size increases
on moving from Li+ to Cs+. the ionic conductance is expected to decrease in the order.
Li+ > Na+ > K+ > Rb+ > Cs+
However, we find by experiment that ionic conductance of Cs+ is the highest and that of Li+ is the
lowest. Thus, ionic conductance actually decreases in the order.
Cs+ > Rb+ > K+ > Na+ > Li+
This is evidently the reverse of what we expect. This anomaly arises from the fact that alkali metal
ions are hydrated to different extents. The Li+ ion is hydrated to the maximum extent due to its high
charge/size ratio compared to other alkali metal ions. The extent of hydration decreases on moving from Li+
to Cs+. Thus, Cs+ ion is the least hydrated. As a result of the variation in the extent of hydration, Li+ ion due
to heavy hydration is the biggest while Cs+ ion due to much smaller hydration is the smallest. Thus, the ionic
size in aqueous solutions, instead of increasing, actually decreases on moving from Li+ to Cs+ as a result of
which the ionic mobility increases as we move from Li+ to Cs+. Hence, the ionic conductance, instead of
decreasing, actually increases on moving from Li+ to Cs+.
2.17 Role of Na+ and K+ ions in Biological Systems :
Sodium cation is a major cation of extracellular fluids of animals including human beings which is known to
activate certain enzymes in the animal body. Sodium ions are relatively harmless except when present in
excess amounts in which case they may cause hypertension. The saline water containing excessive amounts
of NaCl is harmful to plant and aquatic life because of the toxicity of Na+ ions.
The potassium ion is essential to all organisms with the possible exception of blue green algae. It is a
major cation of intracellular fluid of animal cells. It is moderately toxic to mammals but only when injected
intravenously.
ALKALI METALS 44

The sodium and potassium ions, taken together, constitute what is known as Na+ – K+ pump or simply
as ‘sodium pump’. The functioning of this pump is actually a biological process which goes on occurring in
each and every cell of all animals. It transfers Na+ ions from the intracellular fluids to the extra cellular
fluids with the help of ‘carrier proteins’. Simultaneously it transfers K+ ions from the extra cellular fluids to
the intracellular fluids. Since each operation of the pump (i.e., each cycle of this biological process) pumps
out larger number of sodium ions from the cell than the number of K+ ions that it pumps into the cell, the
interior of the cell acquires an excess negative charge and the exterior of the cell acquires an excess positive
charge. This results in the development of electrical potential gradient across the cell membrane which is
responsible for the transmission of nerve signals in animals. The Na+ – K+ pump also maintains the volume
of the cell. Without the existence of the Na+ – K+ pump in the cell, the latter would have swelled in volume
and ultimately bursted.

2.18 Differences Between Lithium and the Other Group 1 Elements

The properties of lithium and its compounds differ far more from those of the other Group l elements.
Group l elements and compounds differ among themselves. Apart from having the same oxidation number
as the rest of Group l, lithium compounds may show closer similarities with Group 2 elements (particularly
magnesium) than they show towards their own group.
Several generalizations may be drawn from this apparently anomalous behaviour of lithium.
1. The melting and boiling points of lithium metal are much higher than those for the other Group l
elements.
2. Lithium is much harder than the other Group l metals.
3. Lithium reacts the least readily with oxygen, forming the normal oxide. It forms a peroxide only
with great difficulty. and the higher oxides are unstable.
4. Lithium hydroxide is less basic than the other hydroxides in the group and therefore many of its
salts are less stable. Li2CO3, LiNO3 and LiOH all form the oxide on gentle heating, though the
analogous compounds of the rest of the group are stable. Another example of the less basic nature
is that though lithium forms a bicarbonate in solution, it does not form a solid bicarbonate, whereas
the others all form stable solid bicarbonates.
5. Lithium forms a nitride Li3 N. None of the other Group l elements forms a nitride, but Group 2
elements form nitrides.
6. Lithium reacts directly with carbon to form an ionic carbide. None of the other Group l elements
do this, but Group 2 elements all react similarly with carbon.
7. Lithium has a greater tendency to form complexes than have the heavier elements, and
ammoniated salts such as (Li(NH3)4]I exist as solids.
8. Li2CO3, Li3PO4 and LiF are all insoluble in water, and LiOH is only sparingly soluble. The rest of
Group 1 form soluble compounds, but the corresponding magnesium salts are insoluble or
sparingly soluble.
9. The halides and alkyls of lithium are far more covalent than the corresponding sodium compounds,
and because of this covalency they are soluble in organic solvents. Similarly, lithium perchlorate
and to a lesser extent sodium perchlorate resembles magnesium perchlorate in their high solubility
in acetone (propanone).
10. The lithium ion itself, and also its compounds, are more heavily hydrated that those of the rest of
the group.
ALKALI METALS 45

The first element in each of the main groups (Li. Be, B, C. N. O and F) differs from the rest of the
group. This is partly because the first element is much smaller than the subsequent elements, and
consequently it is more like to form covalent compounds (Fajans’ rules) and complexes.
The first element in a group can form a maximum of four conventional electron pair bonds. This is
because the outer shell of electrons contains only one s-orbital and three p orhitals. The subsequent elements
can use d orbitals for bonding: they can attain a coordination number of 6. by using one s, three p and two d
orbitals. For this reason the coordination number attained by a complex or a covalent compound of the first
element in a group is commonly 4. and for the subsequent elements the coordination number is commonly 6.
This simple concept is based on a bond consisting of two electrons shared between two atoms. Exceptions
occur when multicentre bonds are formed (as in Li4(CH3)3).
The similarity between lithium (the first member of Group l) and magnesium (the second element in
Group 2) is called a diagonal relationship. Diagonal relationships also exist between other pairs of elements
Be and Al. B and Si as shown.

Period-2  Li Be B C

Period-2  Na Mg Al Si
The diagonal relationship arises because of the effects of both size and charge. On descending a group,
the atoms and ions increase in size. On moving from left to right in the periodic table, the size decreases.
Thus on moving diagonally. the size remains nearly the same. For example, lithium is smaller than sodium.
and magnesium is also smaller than sodium, and hence lithium and magnesium are similar in size. The sizes
of Li+ = 0.76 Å and Mg2+ = 0.72 Å are close, and so in situations where size is important their behaviour
should be similar.
Beryllium and aluminium also show a diagonal relationship. In this case the sizes are not so close
(Be2+ = 0.45 Å and Al3+ = 0.535 Å), but the charge per unit area is similar (Be2+ 2.36 and Al2+ 2.50) because
the charges are 2+ and 3+ respectively.
(ionic charge)
Charge per unit area 
4 2
·  ·  ionic radius 
3
It is sometimes suggested that the diagonal relationship arises because of a diagonal similarity in
electronegativity values.
Li Be B C
1.0 1.5 2.0 2.5

Na Mg Al Si
0.9 1.2 1.5 1.8