Group 1 Elements

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GROUP 1 ELEMENTS

(THE ALKALI METALS)

Group 1 elements also known as the Alkali metals are the most reactive metallic
elements, readily loosing the ns1 valence electrons to form compounds in the +1
oxidation state.

Group 1 consists of the elements: Lithium-Li, Sodium-Na, Potassium-K, Rubidium-Rb,


Caesium-Cs and Francium-Fr.

Table 1: Properties of the Group 1 metals

Property Li(3) Na(11) K(19) Rb(37) Cs(53)


Electronic [He]2s1 [Ne]3s1 [Ar]4s1 [Kr]5s1 [Xe]6s1
configuration
Atomic wt. 6.969 22.898 39.102 85.47 132.905
Ionic 60 95 133 148 169
radius(pm)
B.pts(oC) 1336 883 762 700 670
M.pts(oC) 179.5 97.8 63.5 38.7 37.8
Density(g/cm3) 0.54 0.972 0.859 1.525 1.903
At 0oC
I.E (KJmol-1) 5.20 4.96 4.19 4.03 3.75
EN (Pauling) 1.0 0.9 0.8 0.8 0.7
Hardness 0.06 0.07 0.04 - 0.02
M(aq)+e- m(s) -3.05 -2.71 -2.95 -2.99 -3.02
std electrode Pt (V)
Flame colour Crimson Yellow Lilac Red Blue
Reactivity Increasing
Basicity Increasing

Occurrence
The alkali metals are highly reactive, so they do not occur in the free state in nature. They
occur in the combined state in the following abundance: Na-2.27%, K-1.84% and Li, Rb,
and Cs in trace amounts.

Some Physical properties

1. Possess the weakest metallic bonding of all group metals and strength decreases on
descending the group because only one electron per ion is available in the electron sea
between ions. Hence their m.pts & b.pts are relatively low and decreases down the Gp.
2. Due to the weak bonding, they are soft (can be cut by knife).
3. Their IEs are the lowest of all groups and decrease down the group.
4. When heated (in hot Bunsen flame) they produce characteristic flame colour,
which is used in the flame test and spectroscopy to identify alkali metals.

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Due to low IEs of group I metals, electrons are easily excited to higher energy levels.
when they drop back to the lower energy states they emit visible light of characteristic
colours.
E.g. Yellow colour of Na flame is produced by the transition
[Na]3p1 [Na]3s1
CHEMICAL PROPERTIES

1. Gp 1 metals are the most electropositive.


2. Easy of the ion formation increases down the group which is reflected in the general
decrease (becoming more negative) of the standard redox potentials down the group
i.e. they are powerful reducing agents and very reactive reacting with water and most
non-metals.

NOTE: Lithium has very negative redox potential. Because of its small Li+ ion, it is
strongly hydrated in aqueous solutions. Although it is a very strong
reducing agent in solution than other alkali metals, yet it is a much poorer
reducing agent when solvation can’t take place.
3. Reaction with air at room Temp.
Li reacts the least with air; it slowly tarnishes in damp air.
Na and K tarnish rapidly. Rb & Cs catch fire on exposure to air. Therefore Li, Na, & K
are usually stored in paraffin or kerosene while the rest are kept in a vacuum.

Alkali metal compounds


The electronegativities of the alkali metals are some of the lowest among the elements,
indicating that they form predominantly ionic compounds.
Generally, properties vary uniformly within the group as is expected from periodic law.
However, there are irregularities which are found with Lithium the first member of the
group; and are as follows:
1. Low solubility of Lithium salts of anions of high/large charge density than those of
other alkali metals.i.e. Its carbonates, fluorides, hydroxides & phosphates.
2. Lithium forms stable salts with anions of high charge density owing to their high
lattice energy. E.g.
Li forms normal oxide (Li2O), whereas others form higher oxides (peroxide or
superoxide).
Lithium reacts with nitrogen and acetylene (carbon) to form nitride (Li3N) and carbide
(Li2C2) respectively, the others do not react.
Lithium hydride is more stable than the other hydrides.
3. Since the small Li+ ion has a high charge density and hence a high polarising power
for anions, the Li compounds have more covalent character than those of other alkali
metals.
Thus, Li halides are more covalent than the other halides and are more soluble in non-
polar organic solvents.
Li forms more stable complex compounds. E.g. Li cannot be recovered unchanged
From its liquid ammonia solution, owing to the formation of [Li(NH3)4]+
4. Li forms no solid bicarbonate (HCO3-), triiodide, hydrogen sulphide and superoxide

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as are unstable at room temperature, whereas those of other alkali metals require a
higher temperature to effect their decomposition.
5. Li salts of large polarisable anions are less stable than those of other alkali metals.
E.g. Li carbonate decomposes at 950K, whereas no decomposition of Na carbonate
takes place below 1050K.

The anomalous nature of lithium is explained on the basis of the small radius of Li+ and
its charge density i.e. the high ratio of cation charge to cation radius of Li+. The nuclear
charge of the Li+ is screened only by a shell of two electrons.

Diagonal relationship. Li Vs Mg
Although Li shows a strong resemblance to other alkali metals, still it has many
similarities to Mg. This is due to its ionic radius [Li+ (0.68Ao)] which is closer to Mg2+
(0.65Ao) than to Na+ (0.97Ao). So Li is more similar to Mg than to Na in a number of
respects.
Note
In general, the elements of the 2nd row show differences from other elements in the same
group, the first three members of the 2nd row exhibit many similarities to those elements
located diagonally below them in the periodic table.

Li Be B C

Na Mg Al Si

The elements Li and Mg, for example are said to exhibit a diagonal relationship.

This phenomenon is due to two factors namely charge density and polarisation.
When moving from left to right across the period the charge of the ions increases and
their sizes decrease. Thus, their polarising power increases. When going down the group,
the size increases while the charge of the ions remains the same (constant). On moving
diagonally (i.e. to the right and down at the same time) the two effects roughly cancel
each other. Thus, there is not much change in properties.

Oxides and Hydroxides


All alkali metals burn in air to form ionic oxides. Three types of oxides are formed.
Li: Forms a monoxide – a normal oxide- Li2O. This is due to its small ionic size
compared to the other alkali metals (small cation stabilizes small anions).
Na: forms a peroxide – Na2O2
K, Rb & Cs: Form superoxide – MO2 due to their larger ionic sizes (capable of stabilizing
an ion composed of two oxygen atoms; large cations form more stable
compounds with large anions).

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All the superoxides are paramagnetic because of the presence of an unpaired electron; the
peroxides on the other hand are diamagnetic.

All the three types of oxides are strongly basic and react vigorously with water giving
hydroxides:
Li2O + H2O 2LiOH (less violent)
Na2O2 + 2H2O 2NaOH + H2O2
2MO2 + 2H2O 2MOH + H2O2 + O2 (Where M is K, Rb and Cs)
The peroxides and the superoxides on reaction with water give H2O2 which in turn is a
powerful oxidising agent. Thus, the peroxides and the superoxides are also oxidising in
nature.
The basic strength of the hydroxides increases down the group. As the charge density of
the cation decreases from Li+ to Cs+, attraction between M+ and OH- also decrease. So,
OH- can be liberated readily into the solution, as we go down the group.

Hydrides

The alkali metals react with hydrogen and form ionic hydrides, M+H-. These hydrides on
reaction with water liberate hydrogen. Thus, they are useful source of hydrogen:
MH + H2O MOH + H2
Lithium hydride on reaction with AlCl3 in ether solution forms lithium aluminium
hydride which is a useful reducing agent in organic chemistry.
4LiH + AlCl3 LiAlH4 +3LiCl
Similarly, sodium hydride forms sodium borohydride which is also used as a reducing
agent.

Carbides

Lithium reacts with carbon to form ionic carbide Li2C2 whereas similar carbides of other
metals are not formed on reacting them with carbon.
Na2C2 can be formed on heating the metal with acetylene or when acetylene is passed
through a solution of the metal liquid ammonia:

Liq.NH3
Na + C2H2 NaHC2 Na2C2

These carbides contain the carbide ion (C C)-. On hydrolysis they give acetylene. Hence,
they are termed as acetylides:
Na2C2 + 2H2O 2NaOH + C2H2
K, Rb and Cs react with carbon forming non- stoichiometric interstitial compounds in
which the metal atom enters between the plains of carbon atoms in the graphite layer
structure.

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Nitrides

Lithium is the only alkali metal which reacts with nitrogen gas to form Lithium nitride –
Li3N. (Ngas = N3-).
6Li(s) + N2(g) 2Li3N(s)
The other alkali metals do not combine with nitrogen at all.

Sulphides

Alkali metals react with sulphur to form two types of sulphides: simple sulphides Na2S
and polysulphides like Na2Sn where n = 2,3,4,5 or 6. These polysulphides have zigzag
chain structure.
Table 2: Summary of the main reactions of the Group 1 elements.

2Li + O2 Li2O The higher metals form Na2O2, KO2, RbO2, CsO2.

2M + S M2 S Very vigorous reaction. Polysulphides are also formed.

M + H2O MOH + ½H2 With Li fairly slow, whereas K explodes.

M + ROH MOR + ½H2 Vigorous (R=alkyl, aryl).With Li fairly slow.

M + ½H2 MH At high temps, ionic hydrides.LiH is the most stable.

M + ½X2 MX X = halogen. The higher members can form


Polyhalides, e.g.KI3.

3Li + ½N2 Li3N Slow at room temp, rapid at elevated temperatures.

M +NH3(l) [M(NH3)n]+ + e-(NH3) M+NH2- + ½H2

2M + C(or C2H2) M2C2 (acetylides) C2H2

M + Hg amalgams.

Hydration of the alkali metal ions (M+ ions)

Solvation occurs when the metal ion is surrounded by the solvent molecules. When the
solvent is water the phenomenon is called hydration.
The alkali ions are highly hydrated. The smaller the size of the ion, the greater is its
degree of hydration. This is because the smaller the size, the more will be its charge

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density and the more will be its attraction for polar solvent molecules. Thus, Li+ ion,
which is the smallest gets more hydrated than Na+ ion and so on. The degree of hydration
decreases on moving down the group. As a result of differences in their degree of
hydration, the hydrated ionic radii of the alkali metal ions decrease as we go down the
group from lithium to caesium. Li+ ion has the largest hydrated radius while Cs+ has the
smallest hydrated radius in group 1.
The smaller the size of the ion, the lighter it is, the more will be its mobility and thus
conductance. In this regard we should expect the highest conductance for Li+ which is the
smallest of the alkali metals but this is not so. As explained above that the hydrated
radius of Li+ is the largest of all the alkali metal ions, in solution. Therefore, Li+ ion is the
least conducting in solution. The ionic conductance in solution actually decreases in the
order Cs+ > Rb+ > K+ > Na+ > Li+.

Table 3: Data on Hydration of Aqueous Group I ions

Li+ Na+ K+ Rb+ Cs+


o
Crystal radii A 0.68 0.97 1.33 1.47 1.67
Hydrated radii ( ) Ao 3.40 2.76 2.32 2.28 2.28
hydration Nos 25.3 16.6 10.5 10.0 9.9
Hydration Energies KJmol-1 534 421 334 304 274
Ionic mobilities (at dil, 18o) 33.5 43.5 64.6 67.5 68

Solubility of Alkali metals in Liquid Ammonia

All of the alkali metals dissolve in pure liquid ammonia to give solutions that are blue if
dilute and bronze if concentrated. The bronze solutions conduct electricity about as well
as many metals; and the blue solutions conduct electricity somewhat better than solutions
of strong electrolytes. The solutions also possess magnetic and optical behaviours.

The very dilute solutions are paramagnetic suggesting that unpaired electrons are present
in the system. With increasing concentration the solutions become less paramagnetic,
indicating that a spin-pairing process must occur.

The properties of these solutions suggest strongly that alkali metal atoms ionize in liquid
ammonia to form solvated electrons:-
M(s) + (X + Y)NH3 M(NH3)y+ + e(NH3)X-
Thus;
1. The high conductivity of the solutions and the high mobility of the negative species in
them, the optical properties and the magnetic behaviour of these solutions can be
interpreted in terms of the existence of a stable solvated electron.
2. The decrease in paramagnetism with increasing analytical concentration of metal –
ammonia solutions indicate that solvated electrons undergo a pairing process;
2e(NH3)x- e2(NH3)z2-

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As the concentration of alkali metal increases the system contains less and less free
solvent and it takes on the general characteristic of a molten metal.

The best description for the solvated electron in ammonia is the Cavity model. In this
model, the electron is trapped within a cavity surrounded by ammonia molecules.
Presumably the solvent dipoles are oriented with the hydrogen atoms pointing inward
toward the centre of the cavity i.e. repulsion between the electron and the electrons of the
solvent molecules leads to the formation of the cavity within which the electron has the
highest probability of being found.

In the absence of impurities and metal surfaces, metal-ammonia solutions are stable for
extended periods of time at temperatures where ammonia is still a liquid, but a reaction to
give amide,
Na + NH3(l) NaNH2 + 1/2H2
can occur photochemically and is catalysed by a transition metal salts.
Alkali metal solutions in liquid ammonia are powerful reducing agents and are used for
this purpose in inorganic and organic reactions.

Alkali metal complexes


Complex compound: - is a compound having a central metal atom/ion surrounded by a
group of ions or molecules called ligands.
These ligands are usually bound to the metal by the “coordinate bond” (a bond formed by
the donation of a lone pair of electrons from a ligand to a metal atom/ion).

There are comparatively few complexes of M+ ions. These ions are weakly complexed by
simple anions and hardly at all by monodentate neutral ligands because of their large size
and low charge. Chelation is a necessary condition for significant complexation.
M+ stability of the complexes are in the order Li > Na > K > Rb > Cs.

Organometallic compounds
An Organometallic compound is a compound in which a metal atom or ion is bound to an
organic group. Organometallic compound may have single metal-carbon bonds as in the
Al alkyls Al(CH3)3 or to a pi electrons of a double bond.
The most important Group 1 organometallic compounds are those of Lithium; sodium
and to a lesser extend potassium.

Lithium alkyls and aryls:-


• They are covalent compounds being soluble in hydrocarbons and other non-polar
organic solvents.
• They are generally liquids or solids of low m.pts.
• They react rapidly with oxygen, being usually spontaneously flammable in air,
with liquid water and with water vapour.

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• They are more stable thermally than the corresponding compounds of other alkali
metals.
• The alkyls are polymeric both in solution and in solid state.

Preparation of organolithium:-

1. Using an alkyl or aryl chloride in benzene or petroleum; ether solutions can be used,
but these solvents are attacked slowly by the lithium compounds.
C2H5Cl + 2Li = C2H5Li + LiCl

2. Metal – hydrogen exchange.


Li

Fe = Fe + n-C4H10
n - C4H9Li +

3. Metal – halogen exchange.


Br Li

= + n-C4H9Br
n - C4H9Li +

N N

4. Metal – metal exchange.


2Li + R2Hg = 2RLi + Hg

Organo Sodium and Potassium compounds:-


• They are all essentially ionic alkyls and are not soluble in hydrocarbons.
• They are exceedingly reactive, sensitive to air and hydrolysed vigorously by
water.
• They are stable enough with respect to thermal decomposition and have fairly
high m.pts.

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OTHER IONS WITH +1 OXIDATION STATE

I. Ions with slight similarity in chemical properties with GP 1 metals.


Coinage metals – Cu, Ag, & Au.
• Overall resemblance to the alkali metals is very slight. They have higher
effective nuclear charge and smaller atomic radius than alkali metals. Thus
they have higher ionization energy and are less reactive than alkali metals
• They are close relatives of the transition metals, which they resemble in
much of their chemistry, such as formation of complexes and variable
oxidation state.

II. Ions with chemical behaviour closely resembling that of GP 1 metals


• Most important ions are the ammonium ions: NH4+, RNH3+,…, R4N+.
NH4+ salts generally resemble those of potassium quite closely in their solubilities
and crystal structures.
• Thallium (I) ion, (Tl+) behaves in certain respects as an alkali metal ion [although
in others more like Ag+]. Its ionic radius (1.54Å) is comparable to that of Rb+,
although it is more polarizable.
Thallous hydroxide is a water soluble, strong base, which absorbs CO2 from the
air to form the carbonate.
The sulphate and some other salts are isomorphous with the alkali metal salts.
• A variety of other types of monopositive, essentially spherical cation often
behave like alkali metal ions of comparable size. E.g.
di – ( 5- cyclopentadienyl) cobalt(III) ion i.e. [( 5-C5H5)2Co]+ and its analogues
have precipitation reactions similar to those of Cs+, and [( 5-C5H5)2Co]OH is a
strong base and absorbs CO2 from air and forms insoluble salts with large anions.

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USES
The alkali metals are very good conductors of heat and electricity. But due to their highly
reactive nature, they cannot be used for this purpose.

Uses of elements
Sodium:
• Sodium in polyethylene enclosed cables is used in some underground high
voltage transmission application.
• Because of the high specific heat and thermal conductivity, liquid sodium is used
as a coolant in nuclear reactors.
• Bright yellow lights on streets are sodium vapour lamps.

Lithium:
• Li is used in metal processing as a scavenger, a substance added to molten metals
to remove impurities such as oxygen and sulphur.
• Used in several alloys, e.g. it is added to lead alloys to harden them for use in
bearing and is mixed with Mg to give a strong, light alloy for aerospace
applications.
• Used in organic synthesis and in preparation of LiH and LiNH2

Caesium and Rubidium:


• Used to make photoelectric cells.
Note: Cs has the distinction of being the metal from which electrons are ejected
mostly easily on exposure to light. This phenomenon is called photoelectric effect.
• Used in the manufacture of vacuum tubes as getters, which are placed in vacuum
tubes to remove traces of oxygen.

Uses of compounds
Sodium compounds:
• Sodium Chloride (NaCl) is an essential component of food. NaCl is also used in
the manufacture of NaOH, Na2CO3, Cl2 and H2 gases.
• Sodium hydroxide (NaOH) or caustic soda is used in making soaps, paper, to
refine petroleum and to separate Al2O3 fro its ore.
• Sodium carbonate (Na2CO3) or soda ash is used in making glass. The decahydrate
(Na2CO3.10H2O) or washing soda is used in laundering as a water softener and is
added to detergent preparations.
• Sodium hydrogen carbonate (sodium carbonate) NaHCO3 or baking soda, in
baking powder in medicine and in fire extinguishers.

Lithium compounds:
• The hydrides of Li and Na i.e. LiAlH4 and NaBH4 are used as reducing agents in
synthetic organic chemistry.
• Lithium stearate and Lithium hydroxide are used for the production of lubricating
greases.[CH3(CH2)16COOR – Stearate].

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Potassium compounds:
• Potassium forms a liquid alloy with sodium that can be used as a heat-transfer
agent.
• Potassium hydroxide (KOH) is used in liquid detergent (soft soap).
• Potassium chlorate (KClO3) in matches and explosives.
• Potassium nitrate (KNO3) along with charcoal and sulphur in gun powder. It is
also used as a plant fertilizer.
• Potassium chloride (KCl) as plant fertilizer.
• Potassium superoxide (KO2) in rebreathing gas masks (apparatus). These gas
masks consist of a closed system in which air is circulated through a canister of
KO2. Oxygen is released when moisture in the breath attacks the superoxide.
4KO2(s) + 2H2O(l) 4KOH(s) + 3O2(g)
The potassium hydroxide produced in this reaction removes carbon dioxide (CO2)
From the exhaled air:
KOH(S) + CO2(g) KHCO3(s).

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