You are on page 1of 28

9

Group IA Elements:
The Alkali Metals
PERIODIC TRENDS
Group IA elements or alkali the alkali metals have one electron in their valence shell outside
the noble gas kernel: Li, (He) 2s1 ; Na, (Ne) 3s1 ; K, (Ar) 4s1 ; Rb , (Kr) 5s1 ; Cs , (Xe) 6s1 ; and
francium Fr, (Rn) 7s1.
Due to the effective screening of the nucleus by the noble gas kernel , the ns1 electron in
these elements is held rather weakly. Hence, these elements have low ionization energies, low
electron affinity and low electronegativity. As a result these elements are highly electropositive
and form monopositive cations readily by losing their ns1 electron.
These elements are characterized by a weak metallic nature as only one electron is available
for the metallic properties. The elements have low melting and boiling points.
The alkali metal are soft, silvery white (caesium has a golden colour) and are good conductor
of heat and electricity. Their valence shell electrons can be ionized even with electromagnetic
(light) radiations, so that these element are photosensitive and show photoelectric properties.
The valence shell electron can be excited even with flame temperatures, and these elements
impart colour to a Bunsen flame. This is due to the emission of visible radiation when the
excited electrons fall from higher orbital to the valence shell orbitals.
The physicochemical properties of the alkali metal are given in Table 9.1.

Chemical Reactivity
The alkali metals are very reactive and are strong reducing agents (E0 = -2.71 to – 3.04 V).
The reactivity increases with the size of the element, except for Li.
With water, lithium reacts slowly, sodium smoothly, but potassium catches fire forming
MOH and H2.
2M + 2H2O  2MOH + H2
With hydrogen, all the alkali metals form ionic M+ H-. Their stability decreases from LiH to
CsH (Chapter 8). In air, Li form monoxide, Na form peroxide, but K and other members form
superoxide MO2. With halogens, sulphur, phosphorus, and arsenic, the alkali metal form ionic
halides, polysulphides, M2Sn (n = 1 to 6), phosphides and arsenides respectively.
The alkali metals dissolve in mercury to form amalgams. When heated with graphite,
inclusion compounds CnM (n = 8, 24, 36, 48 or 60) are formed.
The metals are strong reducing agents, and reduce metal oxide, and halides (Al2O3, TiCl4,
MgO etc.) to elemental metal. With ammonia at room temperature, the alkali metals dissolve
forming amides with the liberation of hydrogen. In liquid ammonia, the metals dissolve forming
strongly reducing solutions which contain solvated electrons.

Compounds

1
Group IA Elements: The Alkali Metals 2

All simple compounds of alkali metals are water soluble. A few lithium salts are exceptions
and resemble magnesium salts due to the diagonal relationship.
Due to small size, Li+ is heavily hydrated in salts. Many sodium salts and a few potassium
salts are hydrated. No hydrated rubidium or caesium salt is known.
For the fluorides, carbonates, and hydroxides, the decrease in the lattice energy (U) of the
ionic salts is more than the decrease in the hydration energy of the ions (U for LiF = 1000, NaF =
890; hydration energy for Li+ = 515, Na+ = 450 kJ mol-1) down the group. Hence, solubility
increases from Li+ to Na+ and to Cs+ salts. For other common anions, the decrease in U is less
than that in hydration energy (lattice become comparatively more stable), so that the solubility
decreases, e.g. for chlorides, bromides, nitrates, iodides, etc.
Due to the highly electropositive nature of the metal ions, oxyanion salts are quite stable.
The carbonates and hyroxides are stable, and except for lithium sals, melt without any
decomposition. Further, the alkali metals are the only metals which form solid bicarbonates
MHCO3 .
The hydroxides are strong bases and give strongly alkaline solutions. (Hence these elements
are called the alkali metals). The base strength increases down the group due to increasing ionic
nature in the order: LiOH < NaOH < KOH < RbOH < CsOH. The carbonates and bicarbonates are
water soluble and are weak bases.
All the alkali metals form ionic hydrides. Their stability decreases down the group.
Three series of binary compounds of alkali metals, with oxygen are known: monoxides M2O,
peroxides M2O2, and superoxides MO2. Their stability decreases with increasing charge density
on the cations and decreasing charge density on anions:

Li2O2 < Na2O2 < K2O2 < Rb2O2 < Cs2O2

monoxide > peroxide > superoxide

It appears that (i) due to the high polarizing power of small Li+ ions, the negative charge on
the O22- or O2- ions gets polarized on one oxygen atom, setting free the other oxygen atom from
the diatomic anions: and (ii) the larger cations (Cs+) form a closer packed lattice with large
anions increasing their lattice energy.
The oxides are obtained by the direct combination of the elements in ammonia solvent
(under pressure and at low temperatures for Li+ and Na+ superoxides). Their colour deepens
with increasing molecular weight of the compounds:

Li2O K2O Rb2O Cs2O

In cold: White White Pale, yellow Orange red

In hot: White Pale Golden Purple, and then black

yellow yellow

Na2O Na2O2 NaO2

In cold:White Pale yellow Yellow


Group IA Elements: The Alkali Metals 3

The monoxides are water soluble and form strongly alkaline solutions. The alkalinity
increases down the group. The peroxides are powerful oxidants, while the superoxides are
stronger oxidants than even fluorine.
All the alkali metals form hydrosulphides MSH, monosulphides M2S, and polysulphides M2Sn
(n = 2 to 6). These can be obtained by the direct combination of the elements or by the
interaction of H2S with alkalis in aqueous, ammonia or ethanol sulutions; sulphur is added for
polysulphides.
The stability of the sulphides increases from Li+ to Cs+. For Li+ and Na+, the tetrasulphide is
the most stable polysulphide. For the rest, it is the pentasulphide. Both these trends show that
bigger anions are stabilized by the bigger cations with lower charge density (cf. oxides).
The ionic halides can be prepared by (a) direct combination of elements, (b) halogen +
alkali solutions; (c) HX + MOH or M2CO3 reactions. The halides are white solids. Their covalent
character increases with increasing anion size (F- < Cl- < Br- < I- ) and decreasing cations size (Li+
> Na+ > K+, etc). (Fajan’s rules). LiX is soluble in alcohol and in pyridine, Also, KI is alcohol
soluble, but KCl or NaI is not. Their solubility in water is in the order:
LiF < NaF < KF < RbF < CsF (decreasing U)
LiF < LiCl <LiBr < LiI (decreasing U)
KF < KCl < KBr < KI (decreasing U)

Except for Li+ and Na+, other alkali metal ions form polyhalides with I3-, ICl2-, ICl4-, IBrF- etc. It
may be that charge density on Li+ and Na+ ions polarizes the polyatomic anions (similar to
peroxides, superoxides, etc.).
Amides, known as waxy solids, are obtained by M + dry NH3 reaction.
The alkali metal ions do not show any complexation tendency in solutions. The ionic salts,
e.g. sulphite, nitrite, nitrate, phosphate, etc. are completely ionized in aqoues solutions and
give characteristic reactions of the respective anions and cations. However, due to smaller size
Li+ and, to a much less extent, Na+ form some complexes. Li+ shows a coordination number of
four, e.g. [Li(NH3)4]+I-, [Li(acac)(H2O)2], [Li(acac)(Hacac)], etc. (acac = acetylacetonate). Sodium
is shows both four as well as six coordination: [Na(NH3)4]+I-, [Na(acac)(H2O)4],
[(Hacac)Na(acac)(H2O)2], etc. The few complexes of K+ are with salicylaldoxime and salicylic acid
in which the cation is four as well as six coordinated: [K(L)(HL)], [K(L)(H2O)2] and [K(L)(HL)2]
where LH = salicylaldehyde or salicylic acid.
Cyclic polyethers with sterically placed donor atom (called cryptates, e.g. 2,5, 8, 15, 18, 21-
hexaoxatricyclo-[20.4.0.0] hexacosane, abbreviated to cyclohexyl-18-crawn-6) form compexes
with bigger K+ and Rb+ ion, but not with Na+ or Li+ ions.
The alkali metals form ionic alkyls and related compounds. The ionic character increase
down the group. Lithium alkyls are mostly covalent and involve multicentred bonds between
lithium and carbon atoms.

Differences between Lithium and Other Alkali Metals


Due to (i) incomplete shielding of the valence shell electron by the two electrons in the K shell,
(ii) small size, and (iii) absence of any low-energy vacant orbital for the expansion of the
valence shell to beyond octet, the first member of the representative group of the periodic
Group IA Elements: The Alkali Metals 4

table always shows anomalous properties. For Groups I to III, it shows diagonal relation to the
element placed diagonally opposite to it in the next group. Consider, for e.g. the size. The size
decreases along a period (from Li to Be) and increases down the group (from Be to Mg). Hence,
Li and Mg have similar size. This can be applied to all the periodic properties, and h ence
diagonal resemblances occur.
Some of the differences between lithium and the other alkali metals (element and in
combined state) are:
1. Lithium has highest specific heat, shows lithium bonding (similar to hydrogen bonding)
in LiF solutions, and is the least metallic of all the known elements. Its vapor is highly
corrosive and cuts through glass (small size).
2. Due to incomplete shielding of the nucleus by K shell of electrons, the 2s electron is not
completely transferred to the anion even in the most ionic compounds. Its halides
(exept LiF) show covalence and are soluble in alcohol, ether and pyridine. Other alkali
metal halides are not soluble in ether or pyridine.
3. The experimental ionic radius of Li+ ion is much larger than the theoretical (Bragg-Slater)
radius of 48 pm. All the lithium compounds violate the radius ratios rule.
4. Lithium salts are heavily hydrated to form tetrahedral [Li(H2O)4]+ ion. Due to high charge
density on Li+, Li+-OH2 bond is so polarized that almost coordinated bonds exist in the
hydrated ion. Due to the further solvation of the [Li(H2O)4]+ ion, the effective ionic radius
of Li+ in water is the largest of all the alkali metal ions. It has, therefore, the lowest ionic
mobility and ionic conductance.
5. Lithium has lowest reduction potential. The high hydration energy of Li + more than
compensates the higher IE of Li. However, where solvation is not possible, e.g. in dry air,
lithium is much less reactive than the other alkali metals. It does not react in dry air
unless heated above 390 K whereas other metals get tarnished in dry air even at 300 K.
6. Lithium combines direcly with nitrogen to form Li3N; and with graphite to from carbide
Li2C2 (due to the high polarizing power of Li+ ion). It is only alkali metal to form stable
imide Li2NH.
7. When ammonia solutions of alkali metals are evaporated, other alkali metals are
recovered unchanged, but lithium forms Li(NH3)4. Incomplete shielding of nuclear
charge attracts the LPs of ammonia molecules to form stable lithium ammoniate.
8. Lithium chloride, perchlorate, nitrate, etc. are deliquiscent solids and form hydrates, e.g.
LiCl.nH2O (n = 1, 2, 3). LiOH.H2O can be crystallized from aqueous solutions. Hydrates of
other alkali metal salts are generally inferred from their phase diagrams: only a few
hydrates are known.
9. Lithium does not form solid LiHCO3 and LiSH, but gives insoluble LiF, Li2CO3, Li2C2O4,
Li3PO4 and Li3BO3.
10. The oxyanion salts of Li+ (LiNO3, Li2CO3, LiClO4, Li2C2O4, and even LiOH) are thermally
unstable and decompose to oxide. Other alkali metal salts are either stable (MOH and
M2CO3) or give halides or oxyanions with some loss of O2, e.g. MClO4 gives MCl + O2, but
MNO3 decomposes to MNO2 + O2.

11. Organometallic compounds of lithium are covalent and contain lithium atoms in a
tetrahedral coordination. Other alkyls are ionic, e.g. Na+Me- or Cp- Na+.
Group IA Elements: The Alkali Metals 5

Diagonal relationship between lithium and magnesium


Due to similar nature of ions and ionic radii, Li+ (60-66 pm) and Mg2+ (66 pm) form similar
compounds. Due to different ionic charges, similarity is in nature and not in stoichiometry.
Whenever lithium differs from the alkali metals, it is similar to magnesium. Thus,

(a) The halides are covalent, deliquiscent and solube in organic solvents.
(b) Direct combination with nitrogen gives nitrides Li3N and Mg3N2; with graphite, carbides
Li2C2 and MgC2 are formed.
(c) Both burn in air to form only the monoxides.
(d) Oxyanion salts decompose thermally to oxides.
(e) Bicarbonates are soluble in water, but cannot be isolated in solid state.
(f) Carbonates, oxalates, phosphates, fluorides, etc. can be precipitated by double
decomposition from solutions.
(g) Monoxides form only weakly alkaline aqueous solutions.

THE ELEMENTS
Occurrence
Lithium (0,0065 percent of lithosphere) occurs chiefly as the phosphate ores amblygonite (Na,
Li) AlPO4 (F, OH), or as silicate ores petalite (Li, Na) AlSi4O10; spodumene LiAlSi2O6; and lepidolite
or lithium mica (K, Na, Li)3 (Al, Si)4 (F, OH)2O10. The ores contain only 2 to 7 percent Li by weight
(low atomic weight of Li).
Sodium and potassium (2,63 percent and 2,4 percent in lithosphere) occur chiefly as soluble
chlorides as rock salt NaCl, carnallite KCl.MgCl2.6H2O; nitrate as Indian saltpetre KNO3; and Chile
saltpetre NaNO3; or sulphate as kainite K2SO4, MgSO4.MgCl2.6H2O. Sea or lake waters contain
up to 0,04 percent K and 1,14 percent Na, and are useful sources for these element. in addition,
sodium carbonate occurs in arid regions of hot countries (sajji mitti).
Rubidium and caesium occurs as impurities in potassium ores. Pollucite is a rare caesium
aluminosilicate mineral.

Extraction of the Element


The alkali metals can be extracted by (a) electrolysis of chloride solutions using mercury
cathode (electrolysis proceeds due to high overpotential or hydrogen on mercury and lowering
or reactivity of alkali metals by amalgamation); (b) electrolysis of fused alkali halides in CaCl2 or
NaCl metals or of fused KOH; or (c) reduction of anhydrous chlorides with metallic calcium.

Lithium
Group IA Elements: The Alkali Metals 6

The extraction of lithium from its ores is based upon (i) the solubility of LiCl in pyridine and
ether, (ii) precipitation of Li2CO3 or Li2C2O4 from aqueous solutions and (iii) electrolysis of fused
LiCl in NaCl + CaCl2 melts.
The chief methods of obtaining LiCl from lithium ores are the following:
(a) Acid digestion Powdered petalite (2-3 per cent Li) spodumene (4-5 per cent Li) or
ambiygonite (7-10 per cent Li) is digested with HCl or H2SO4. Silica gets precipitated. The alkali
metals salts and Fe3+/Al3+ salts are extracted with water. FeCl3 is added to precipitate
phosphates, and Al3+ and Fe3+ in the filtrate are precipitated as hydroxides at pH 4. Blowing hot
air then precipitates any manganese as MnO2. After concentrating the filtrate, lithium is
precipitated as Li2CO3 from alkaline solutions. Treating the carbonate suspension with lime
gives a solution of LiOH. Upon crystallization, LiOH.H2O is obtained. This is dissolved in HCl and
LiCl is obtained upon crystallization.
(b) Fusion with BaCO3, BaSO4 and K2SO4 results in the separation of the ore into two layers.
The upper layer contains alkali metal sulphates, the lower layer contains sulphates and silicates
of barium and aluminium. The upper layer is separated, dissolve in water, and treated with
BaCl2 to precipitate BaSO4. The filtrate consists of alkali metal chlorides. It is evaporated to
dryness. Dissolving the solid in pyiridine gives a solution of LiCl. Distillation of pyridine leaves
pure LiCl.
(c) Fusion of silicate ores with CaCl2 + CaCO3 at 1500 K gives slag of calcium silicates and
aluminates and volatilized LiCl from the melts.
(d) The phosphate minerals are digested with HCl. The phosphoric acid is precipitated as
FePO4 by adding FeCl3, and the filtrate is evaporated to dryness. The residue is extracted with
water and Mn2+ is precipitated by adding BaS. Excess of Ba2+ is removed by adding H2SO4. The
sulphate solution is then evaporated with oxalic acid to precipitate Li 2C2O4. Ignition of oxalate
gives Li2CO3+Li2O which is converted inti LiCl with HCl and then purified with pyridine.
(e) Lithium can be obtained by the electrolysis of LiCl in moisture free pyridine or acetone.
Industrially, LiCl + KCl (60+40) melt is electrolyzed at 750-770 K in a thick porcelain crucible
using gas-coke splinter anode and iron wire-screen as cathode.
Lithium metal is stored after greasing as it is extremely reactive towards both oxygen and
nitrogen (air).

Sodium
Industrially, sodium is obtained by the electrolysis of fused NaOH (Castner process) or NaCl
in CaCl2 melt (Down’s process).

The Castner Process Molten NaOH is electrolyzed in cylindrical iron vessels using iron cathode
surrounded by a nickel anode (Fig. 9.1). The two electrodes are separated by a nickel
diaphragm (wire gauze). During the electrolysis, molten sodium rises to the surface (it is lighter
than NaOH) from where it is withdraw periodically.
Group IA Elements: The Alkali Metals 7

Fig. 9.1 Castner’s cell for electrolysis of sodium hydroxide

The electrode reactions are:


NaOH  Na+ + OH- (ionization)
At anode: 4OH-  4OH + 4e-
4OH  2H2O + O2
(O2 escapes, water dissolves in melt)
At cathode: Na+ + e-  Na
H+ + e-  H (from water)
followed by 2H  H2
Hydrogen evolved at the cathode keeps the metal unoxidized. Byproducts from the process are
oxygen and hydrogen gases.
Down’s Cell The electrolyte used is NaCl + CaCl2 in the ratio 2 to 3. Addition of CaCl2 helps in (i)
lowering the melt temperature from the mp of NaCl (1070 K) to 870 K so that corrosion and
volatility of sodium metal is reduced; and (ii) lowers the discharge potential of Na+. The
electrolysis is done in a steel shell lined with refractory bricks. A massive graphite cylinder, the
anode, is surrounded by two semicircular steel cathodes. The electrodes are separated by steel
gauze cylinder. On electrolysis, Cl2 is evolved at the anode, whereas molten sodium collects on
top of cathode cylinders. A small amount of calcium may also get discharged, but dissolves in
NaCl-CaCl2 eutectic so that pure sodium collects at the cathode. The byproduct is chlorine.
Group IA Elements: The Alkali Metals 8

Anode: (positive carbon electrode)


2Cl-(l) → Cl2(g) + 2e

Cathode: (negative iron electrode)


Na+(l) + e → Na(l)

Overall REDOX Reaction:


2Cl-(l) + 2Na+(l) → Cl2(g) + 2Na(l)

Fig. 9.2 Down’s cell for the electrolysis of fused


sodium chloride to obtain sodium metal

Potassium
Potassium cannot be obtained by the electrolysis of KCl-CaCl2 melts as (i) discharge potential
of K+ and Ca2+ is similar. (ii) molten potassium is soluble in the melt and conducts electricity so
that the cell gets short-circuited; (iii) pure KCl melts at a temperature (1049 K) higher than the
bp of potassium (1035 K). Hence, the metal is obtained by the electrolysis of fused KOH (mp
633K) in a cell similar to the Castner cell.
Chemically, potassium can be obtained by the (i) reduction of KF by CaC2 or silicon; or (ii)
reduction of KCl by Na vapours. The Na + K mixture is separated by fractionation.
2KF + CaC2 2K + CaF2 + 2C
4KF + Si  4K + SiF4
KCl + Na  NaCl + K
Rubidium and caesium are similar to potassium. They can be isolated by reducing (a) carbonate
with coke, (b) chloride with calcium, (c) hydroxide with Mg, or (d) electrolysis of fused cyanides
in barium cyanide.
2Rb2CO3 + C  4Rb + 3CO2
2CsOH + Mg  2Cs + MgO + H2O
2 MCl + Ca  2 M + CaCl2 (M = K, Rb, Cs)

Properties and Uses


The properties of the alkali metals have been discussed earlier. Some important uses of the
alkali metals are the following:
Alloys Li-Pb alloys are used for bearing and electric cable sheathing; Zn-Al-Li as mild steel; Pb-
Na in the manufacture of PbEt4; Na-K for high temperature thermometers.
Group IA Elements: The Alkali Metals 9

Lithium metal is used as a scavenger (absorp O2 and N2) in the metallurgy of Cu and Ni.
Sodium and potassium can be used as reducing agents for the extraction of Ti, V etc., as heat
transfer media for cooling jets and nuclear reactors, and in street lighting tubes and lamps.
Potassium and caesium are used as photoelectric materials in photocells.

SOLUTION IN LIQUID AMMONIA


The alkali metals dissolve in liquid ammonia with considerable increase in voume and form two
immiscible phase: (i) a dilute, but heavier blue solution of < 0.05 M metal, and (ii) a lighter, but
bronze coloured solution with > 0.005 M metal in ammonia, Caesium, however, form only the
blue solution. These solutions have properties as given.
Blue solutions Very dilute solutions are paramagnetic and have unpaired ammoniated
(solvated) electrons [e(NH3)n]-. The paramagnetism decreases with increasing concentration of
the alkali metal due to the electron pairing at higher concentrations forming [e(NH3)n.e(NH3)m]2-
.
The blue solutions have a featureless broad absorption band at ca 14,500 Å (1450 nm).
These solutions show electric conductance expected for electrolytic solutions. The
differences in conductance of different alkali metal solutions can be explained on the basis of
differences in the conductance of M+ ions in ammonia.
The properties are, therefore, compatible with the equation
M + nNH3  [M(NH3)x]+ + [e(NH3)y]- (n = x + y)
Where the M+ ions and the electrons are stabilized by solvation by ammonia molecule.
Similar blue solutions are formed by other metals with low IE like the alkaline earth metals,
Eu and Sm in ammonia and in organic amines as solvents.
The bronze solutions These are lighter solutions and show metallic conduction. For sodium,
the conductivity is half that of mercury. These are considered to be the solutions of solvated
electrons (ammoniated) in the metal interstices similar to alloys. The mobility of the anion is
about 200 times that of the cation, however.

Properties
Both the blue as well as the bronze solutions are stable and decompose only about 1 per
cent per day at 233 K into MNH2 + H2.
The solutions are strong reducing agents due to the presence of free electrons. They reduce
O2 to O2¯ and then to O22¯ sulphur to polysulphides; cad to the clustered Pb94¯ ; Cu2+ to
elemental Cu ; and [Ni(CN)4]2¯ to [Ni(CN)4]4¯ having Ni (O).
Typical reactions with organic compounds are:

C6H5OC6H5 + 2Na + NH3  C6H5O¯ Na4 + C6H6 + Na+ NH2¯


C6H5COC6H5 + 2Na + 2NH3  C6H5CHOHC6H5 + 2Na+ NH2¯
2R ̶ X + 2Na + 2NH3  RH + RNH2 + 2Na+ X¯
R ̶ CH = CH2 + 2Na + 2NH3  RCH2-CH3 + 2Na+ NH2¯
Group IA Elements: The Alkali Metals 10

Metal hydrides, alkyls and halogenometal alkyls (GeH4, SnEt4, Me3 SnBr) form the alkali
metal derivative with the liberation of alkane, hydrogen, or formation of halides.
Me3SnBr + 2Na → Me3Sn-Na+ + Na+Br-
The exact mechanism of reductions is not known, but may involve a primary attack by the
electrons.
X ̶ Y + e¯  X¯ + Y. or X. + Y¯
X ̶ Y + 2e¯  X¯ + Y¯
This is followed by abstraction of a proton from NH3 or the reagent HZ
X¯ + NH3  XH + NH2¯
X¯ + HZ  XH + Z¯
Or the free radicals may propagate the chain reactions:
X. + HZ  XH + Z.
Or bring about dimerzation as
X.  .X  X ̶ X
The solvated electron can be prepared in ammonia by the electrolysis of onreducible
campounds. It exists in alkali metal solutions in polyethers, amines, ethylene, dimethylglycol
(diglyme) etc.

THE OXIDE
Lithium Monoxide
Lithium monoxide Li2O can be prepared by (i) burning lithium in air, and (ii) therml
decomposition of carbonate, oxalate, hydroxide or nitrate.
4Li + O2  2Li2O
Li2C2O4  LiCO3 + CO
Li2CO3  Li2O + CO2
4LiNO3  2Li2O + 4NO2 + O2
Lithium oxide is a white ionic solid, which dissolves in water to form alkane solutions of LiOH. It
is a basic oxide and forms salt with acidic oxides and acids as usual.
It is an intermediate for metallurgy of lithium.

Sodium Peroxide
Preparation
Group IA Elements: The Alkali Metals 11

Sodium peroxide is prepared by passing hot air over molten sodium at 600 K and above; or
by bubbling oxygen through liquid ammonia solutions of sodium metal

2 Na + O2  Na2O2

It can be crystallized from water as Na2O2.8H2O.

Properties
It is a pale yellow solid, which dissolves in water to form alkaline solutions due to hydrolysis.
O2- + 2H2O ⇋ 2OH- + H2O2
Upon acidification with H2SO4 or H3PO4, it gives H2O2 which can be obtained as a dilute
solution by cooling to crystallize out. Na2SO4. 10H2O or NaH4PO4. H2O.
Na2O2 (aq) + H2SO4  Na2SO4.10 H2O + H2O2
Na2O2 (aq) + 2 H3PO4  2 NaH2PO4.12H2O + H2O2
Stability Solutions of sodium peroxide are unstable and gradually lose oxygen due to the
decomposition of H2O2
2 Na2O2 + 2 H2O → 4NaOH + O2
The composition is rapid in hot solutions.

As oxidizing agent Peroxide is a strong oxidant.


O22- + 4 H+ + 2e- ⇋ 2 H2O (EA0 = 1.776 V)

O22- + 2H2O + 2e- ⇋ 4OH- (EB0 = 0.88 V)

It oxidizes Ag to Ag2O; Pt to PtO2; Fe2+ to Fe(OH)3 in alkalis; Cr(III) to chromate; etc. Acidic
solutions are equivalent to hydrogen peroxide solutions.
The fusion of Na2O2 and alkali with chromite gives chormate, while pyrolusite is oxidized to
manganate

2Fe(CrO2)2 + 7Na2O2  Fe2O3 + 4Na2CrO4 + 3Na2O


MnO2 + Na2O  Na2MnO4
Corrosive nature Sodium peroxide is a corrosive solid due to (i) liberation of nascent oxygen,
and (ii) formation of Na2O which absorbs moisture, forming NaOH. On heating, it attacks silver
and platinum, forming oxides, and dissolves silica forming silicates, and alumina forming
aluminates
2Na2O2 + 2SiO2  2Na2SiO3 + O2
2Na2O2 + 2Al2O3  4NaAlO2 + O2
It thus attacks even glass in fused state.

Absorption of gases It absorbs acidic oxides (SO, SO3, CO2, NO2, etc.) forming sodium salts. Its
absorbs CO also forming sodium carbonate
Group IA Elements: The Alkali Metals 12

Na2O2 + SO2  NaSO4


2Na2O2 + 2CO2  2Na2CO3 + O2
NaO2 + CO  Na2CO3
Uses
Sodium peroxide is used in the manufacture of benzoyl peroxide, perborate and other per
salts (Chapter 14). In submarines, it is used to purify air as it absorbs both CO and CO 2. It is also
used as a bleaching agent, and under the name oxone, as a source of oxygen (water + Na2O2).

HYDROXIDES
Preparation
The alkali metal hydroxides can be prepared by the following processes.
(1) Causticization. Addition of Ca(OH)2 or Ba(OH)2 to Na2CO3 solution precipitates metal
carbonates and forms an aqueous of NaOH (Gossage process).
Na2CO3 + M(OH)2  MCO3 + 2NaOH (M = Ca, Ba)
The reaction is reversible. Yield is 99 per cent with 2 per cent Na 2CO3 but is 91 per cent with a
20 per cent Na2CO3 solution.
(2) Electrolysis of NaCl solution. When an aqueous solution of sodium chloride is
electrolysed, H2 is liberated at the cathode, while chlorine is liberated at the anode
NaCl  Na+ + Cl- (ionization)

and
H2O  H+ + OH-
At cathode: 2 H+ + 2 e-  H2
At anode: 2 Cl-  Cl2 + 2 e-

Addition of these reactions gives the net reaction as


electrolysis
2 NaCl + 2 H2O 2 Na+ + 2 OH- + H2 + Cl2

If chlorine is allowed to come into contact with NaOH, it gets hydrolysed to Cl - and OCl-
Cl2 + 2NaOH  NaCl + NaOCl + H2O
and destroys the alkali produced. Hence the electrolysis is done by separating the cathode and
the anode. The by products are chlorine and hydrogen.
In the old Gibb’s cell, the cathode is two concentric steel sheets fixed to a ring and linked
with asbestos on the opposite faces. A cast iron anode is placed between the cathode rings.
Warm NaCl solution at 363 - 368 K is electrolysed to obtain a 2 : 1 NaCl : NaOH solution. It is
then evaporated to 1/5th volume when NaCl gets precipitated out leaving behind liquor caustic -
50 per cent NaOH, 1 per cent NaCl and 1 per cent NaClO 3 . The chlorate is formed by a slight
interaction of Cl2 with hot alkali solution during the electrolysis and later steps.
In the high capital cost Castner-Neller cell , modified as Kellner–Solvay cell or Solvay
through (Fig. 9.3) purified brine containing 25.5 per cent NaCl is electrolysed at 298 K in
steel through line with ebonite/graphite (Fig. 9.3). The cathode is a thin 3 mm stream of
Group IA Elements: The Alkali Metals 13

mercury while 20 to 150 graphite blocks suspended 2 mm above the mercury surface serve as
the anode.

Fig. 9.3 Kellner-solvay cell for the electrolysis of aqueous


brine using flowing mercury cathode.

Upon electrolysis, Na+ ions get discharged on the mercury surface and form amalgam.
Hydrogen ions are not discharged because of the high overvoltage for the discharge of H+ on
the mercury surface.
The 0.2 per cent sodium amalgam is separated , and treated with water to obtain a dilute
solution of pure NaOH. Mercury is set free and is recycled to the cathode liquid stream. The
process gives pure NaOH.
In the Nelson Cell (Fig. 9.4), the cathode is a U-shaped perforated steel tube line with asbestos
on the inside. The graphite anode is placed in the tube, which is filled with NaCl solution. Upon
electrolysis, Cl2 is evolved at the anode, while Na+ passes through the asbestos and gets
discharged at the steel cathode. After completing the electrolysis, steam is blown on the steel
tube to obtain a solution of NaOH at the bottom of the tank.
Potassium hydroxide also can be prepared similarly using KCl.

Properties
Sodium hydroxide is a white deliquiscent solid which melts to a clear liquid at 591 K without
decomposition. It absorbs moisture and CO2 from air which forms a crust of Na2CO3.
Group IA Elements: The Alkali Metals 14

Fig. 9.4 Nelson’s cell for the electrolysis of brine solution


using steel cathode and asbestos diaphragm

Solubility The alkali metal hydroxides are freely soluble in water. Phase studies indicate the
formation of NaOH.H2O and NaOH.2H2O, but only LiOH.H2O is a stable solid.
The alkalis are soapy (slippery) to touch due to the hydrolysis of the peptide linkage of the
amino acids of skin.
As alkalis The MOH are strong bases and form salts with acidic and amphoteric oxides. Thus,
with CO2 they give HCO3- and CO32- ; with P4O10 form phosphates; with Al2O3 form aluminate
AlO2-; with ZnO give zincate ZnO22- and with PbO form PbO22-.
With metal ions in solution, metal hydroxides M(OH)n are formed. If insoluble, they get
precipitated (Pb(OH)2, Mg(OH)2, Ni(OH)2, etc.). Unstable hydroxides may lose water and give
the oxides (hydrated) (Hg2+, Ag+, Cu2+, Sn2+, Pb2+, Be2+, etc.).

Mg2+ + 2OH-  Mg(OH)2 (white precipitate)


Ni2+ + 2OH-  Ni(OH)2 (greenish precipitate)

Cu2+ + 2OH-  Cu(OH)2  CuO + H2O


Dirty green Black
ppt. ppt.

heat
Ag+ + OH-  AgOH  Ag2O + H2O
White ppt. Brown ppt.

2OH-
Zn2+ + 2OH-  Zn(OH)2  ZnO22- + H2O
White ppt. exess Soluble

OH-
Group IA Elements: The Alkali Metals 15

Al3+ + 3OH-  Al2O3.xH2O  AlO2- + 2H2O


White ppt. exess

Displacement of a weak base Being strong alkalis, MOH can displace weak bases like NH3 or
PH3 from their salts,
MH4+ Cl- + OH- MH3 + H2O + Cl- (M = N, P)
Reaction with elements Highly electropositive elements with electronegativity below 1.5
form the hydroxide with water present in the alkali solutions (Li, Na, K, La). Element with
electronegativity between 1.5 and 2.0 (Zn, B, Al, Si, Sn, As, Sb) liberate hydrogen gas:

M + 2OH- MO22- + H2 (M = Zn, Sn)


2M + 6OH- 2MO33- + 3H (M = B, Al, As, Sb)
Si + 2OH- + H2O SiO32- + 2H2

Element with electronegativity more than two disproportionate (halogens, sulphur,


phosphorus, etc.):

X2 + 2OH- X- + OX- +H2O (X = Cl, Br, I)


3X2 + 6OH-  5X- + XO3- + 3H2O (X = Cl, Br, I)
S8 + 12OH-  4S2- + 2S2O32- + 6H2O
P4 + 3OH- + 3H2O  PH3 + H2PO2-
Molten alkalies are very corrosive and can attack many minerals like silicates, oxides,
phosphates, etc. giving sodium silicates, phosphates and other oxyanions. Thus, cassiterite
(SnO2) gives stannate (Na2SaO3), alumina gives aluminate, rutile (TiO32-), etc. Barium sulphate
forms barium hydroxide and Na2SO4.
Platinum gets corroded by molten alkalis in the presence of oxidizing agents forming
platinate PtO32- ions. Hence, platinum wares are not used for alkali fusions especially in the
presence of oxidizing agents.
Nickel and iron, however, resist the attack of fused alkalis.

Preparation of Pure NaOH


Chief impurities in NaOH are carbonate, chloride and chlorate. For acidimetry, pure NaOH can
be prepared by:
(a) Dissolving the NaOH sample in alcohol in which only NaOH is soluble, filtering, and then
evaporating the filtrate in silver apparatus to dryness.
(b) Preparing a saturated solution of NaOH in water. Na2CO3, NaCl and NaClO3 are insoluble
in concentrated NaOH, and get precipitated. After 10 - 25 hours, the solution is filtered
and stored away from CO2 using KOH guard tube.

Structure
Alkali metal hydroxides are ionic solids with discrete M+ and OH- ions, LiOH is, however,
covalent the monohydrate has a chain structure (Fig. 9.5) in which each lithium atom is
Group IA Elements: The Alkali Metals 16

tetrahedrally surrounded by four oxygen atoms-two from OH- and two from water molecules.
Each water molecule is linked to two lithium atoms so that each oxygen atom is attached
tetrahedrally to two hydrogen and two lithium atoms. The hydrogen atoms of the water
molecules are then hydrogen bonded to hydroxyl ions of the adjacent chains.

Fig. 9.5 Structure of LiOH.H2O. Each lithium atom


is attached to four oxygen atoms
tetrahedrally. Oxygen atoms have a
coordination number of two for outer and
three (two Li + one H) for bridging atoms.

Uses
Sodium hydroxide is an important industrial chemical and is used in the manufacture of soap,
paper, silk, rayon, dyes, and chemicals like chlorate, nitrite, etc. It is used for the purification of
petroleum.
Potassium hydroxide is used as a soft alkali for making toilet soaps. It is the electrolyte for
the Fe-Ni Edison batteries; and is used for isolating potassium.

CARBONATES AND BICARBONATES


Lithium Carbonate
Lithium carbonate is obtained by double decomposition reaction or by passing CO 2 through
LiOH solution.
2LiCl + Na2CO3 → Li2CO3 + 2 NaCl
2LiOH + CO2 → Li2CO3 + H2O
It is thermally unstable and decomposes to oxide.
Group IA Elements: The Alkali Metals 17

It is a base and dissolves in acids to give lithium salts (cf. Na 2CO3). When CO2 is bubbled
through a suspension of lithium carbonate, a clear solution called lithia water is formed. It
contains LiHCO3. On heating, Li2CO3 gets precipitated out (cf. Calcium and magnesium
carbonates).

Li2CO3 + H2O + CO2  2LiHCO3

Lithium carbonate is an intermediate in the extraction of the metal. Lithia water is used as a
remedy for gout.

Sodium Carbonate and Bicarbonate


Sodium carbonate NaHCO3 can be obtained in the laboratory by passing CO2 through NaOH
solution, when the salt gets precipitated (solubility is 8.4 per cent at 283 K). Thermal
decomposition of NaHCO3 gives the carbonate.
Industrially, these salts are prepared by the Solvay soda-ammonia process. When CO2 is
passed through ammonical brine solutions, there is formation of CO32-, HCO3-, and OH- ions in
addition to Na+, NH4+, and Cl- ions.
OH-
CO2 + OH- HCO3- CO32- + H2O

The least soluble ion combination of NaHCO3, gets precipitated. Thermal decomposition of
NaHCO3 gives Na2CO3.

The process consists of the following steps (Fig. 9.6):

(a) Brine solution is saturated with NH3 in the saturation tank. Some CO2 is bubbled to
precipitate CaCO3 and MgCO3 (from water used).
(b) Carbonation of the brine solutions to precipitate NaHCO3 in carbonation towers.

NaCl + H2O + NH3 + CO2  NaHCO3 + NH4Cl

(c) Calculation of NaHCO3 to get Na2CO3. The CO2 formed is used for the carbonation by
recycling.

Carbon dioxide is obtained by the calcination of limestone, and the quick lime formed (CaO)
is used to decompose the ammonium salts in the mother liquor to NH3.
CaCO3  CaO + CO2
CaO + 2NH4CI  CaCl2 + 2NH3 + H2O

Ammonia formed is used ammoniation in saturation cambers.


Thus, the raw material used are limestone and NaCl with a heating arrangement. The
byproduct CaCl2, however is not of much used industrially.
Alternatively, Na2CO3, can be manufacture by the electrolysis of NaCl in a cell similar to
Nelson’s cell. The liberated sodium metal is treated with steam and CO2 a solution carbonate.
Group IA Elements: The Alkali Metals 18

Fig. 9.6 Solvay soda-ammonia process for sodium


carbonate. A is saturating tank, B is filtration unit
to remove precipitated hydroxides, if any, in A; C
is cooling tower and D the carbonation tower.
Precipitated NaHCO3 is filtered through vacuum
filter E. Limestone is calcined in G, CaO added to
ammonia in recovery tower F and CO2 passed into
D, F and A.

Properties
Sodium carbonate is a white solid, with is thermally stable. It melts at 1127 K to a clear
liquid. It is fairly soluble in water (21.4 per cent at 98 K). And gives alkaline solutions due
hydrolysis

CO32- + H2O  HCO3- + OH- (pKh = 3.4)

Hence, the solution is alkaline. Phenolphthalein turns pink is sodium carbonate solution.
The hydrolysis of HCO3- is slight, and gives solutions which are slightly acidic (HCO3- is acid
anion).
HCO3- + H2O  CO32- + H3O+ pK2 = 11.6

H2CO3 + H2O  HCO3- + H3O + pK1 = 3.4

Hence the solutions are acidic towards phenolphthalein, and do not turn the indicator red or
pink.
From aqueous solutions, hydrates Na2CO3. 10H2O (below 306 K), Na2CO3.7H2O (at 306-311K)
and Na2CO3.H2O (above 316 K) can be crystallized out. On heating they get dehydrated to
anhydrous salts, which melts without decomposition.
Reaction with meta lion The formation of carbonate can be taken as a measure of the basic
nature of the cation.
(a) Strongly basic cations like Ba2+, Sn2+, or Ca2+ from insoluble carbonates MCO3 with
Na2CO3 solutions but do not give any precipitate with NaHCO3, solution in cold due to the
Group IA Elements: The Alkali Metals 19

formation of soluble bicarbonates. From hot solutions, however, normal carbonates get
precipitated.
(b) Slightly less basic cations like Mg2+, Ni2+, or Zn2+ from basic carbonates with Na2CO3
solution, e.g. MgCO3, Mg(OH)2.3H2O, 2NiCO3, Ni(OH)2.2H2O or 2ZnCO3.Zn(OH)2.2H2O due to the
hydrolysis of the carbonates formed at the pH or Na2CO3 soln.
MCO3 + 2H2O → M(OH)2 + CO2

The hydrolysis is, however, partial. With NaHCO3 solution, normal carbonate is precipitated
(due to lower pH) from warm solutions.
(c) Less basic metal ions like Al3+, Fe3+, Cr3+, etc. are complately hydrolysed to hydroxides in
Na2CO3, solution, with NaHCO3 solution also, these matals precipitate hydroxides completely or
partially.
Formations of Sesquicarbonate When equimolar, solutions of NaHCO3 and Na2CO3 are
crystallized, the double salt Na2CO3.NaHCO3.2HCO3, called sesquicarbonate, is formed.
As standard in acidimetry Anhydrous sodium carbonate is used as standard in acidimerty. It
is a diacidic base
Na2CO3 + HCl  NaHCO3 + NaCl
Na2HCO3- + HCl  NaCl + H2O + CO2

Sodium bicarbonate is amphoteric (forms carbonate with NaOH and CO2 with HCl). It cannot be
used as a primary standard as it is thermally unstable (decomposes to CO2 + Na2CO3) and hence
cannot be made moisture free.

Structure
The decahydrate Na2CO3.10 H2O consists of the dinuclear Na2(H2O)102+ ion and CO32- in ionic
lattice. In the cation, each Na is in octahedral environment with six water molecules (Fig.9.7).
Two water molecules act as bridging ligands through oxygen atoms. In the bicarbonate, the
anion is hydrogen bonded HCO3- ion (Fig. 9.8) in the form of a chain.

H H
H2O OH2
O OH2
H2O
Na Na
H2O
O OH2
H2O OH2
H
H

Fig.9.7 The structure of Na2(H2O)2+10 ion present in Na2CO3.H2O


Group IA Elements: The Alkali Metals 20

O- Na+

O O- Na+
O
C
H
C H
O O
C

O O
O Na+

Fig.9.8 The hydrogen bonded chain anion HCO3- in NaHCO3. The Na+ ions are
held to the chain by electrostatic attractions.

The Na+ ions are held by the electrostatic attraction. Due to the chain anion, NaHCO3 has a low
solubility in water

Uses
Sodium carbonate is used in the manufacture of glass, water, soaps, and caustic soda. It used
in the extraction of chromium and the manufacture of chromates and dichromates. It is used
for many organic syntheses, e.g. of glycerine, iodoform, etc. and as a laboratory reagent.
In crude form, it is used as a cleansing agent under the name of washing soda
Sodium bicarbonate, mixed with Na2H2P2O7 and Ca(H2PO4)2 is used as baking powder, in
effervescent drinks, and in medicine to reduce stomach acidity.

Potassium Carbonate and Bicarbonate


Solvay process cannot be used for the preparation of K2CO3 as KHCO3 is fairly soluble in water.
It is prepared by a modified process, called Precht process. CO2 is passed through KCl solution
containing a suspension of MgCO3.3H2O, where by the precipitate change to
KHCO3.MgCO3.4H2O. On heating gently, the residue change to K2CO3 + MgCO3.
CO2 + 2KCl + 3MgCO3.3H2O → 2KHCO3.MgCO3.4H2O + MgCl2
2KHCO3.MgCO3.4H2O → K2CO3 + 2MgCO3.3H2O + CO2 + 3H2O
Upon leaching the residue with water, a solution of K2CO3 is formed.
Alternately, the precipitate of KHCO3.MgCO3.4H2O is boiled with a suspension of MgO.
2KHCO3.MgCO3.4H2O + MgO → K2CO3 + 3MgCO3.3H2O
The filtrate upon concentration gives K2CO3.
Potassium bicabonate KHCO3 can be obtained by saturating a solution of K2CO3 with CO2 at
283 K and crystallizing the solution below 293 K to avoid thermal decomposition of KHCO3.
Potassium carbonate and bicarbonate are similar to the corresponding sodium salts. K 2CO3 is
more soluble (113 per cent) and has a higher mp (1175 K). It also melts without any
Group IA Elements: The Alkali Metals 21

decomposition. Hydrates K2CO3.nH2O with n = 2, 1.5, and 1 are known and give anhydrous salt
above 400 K.

Whereas Na2CO3.10 H2O is efflorescent, potassium carbonate is deliquiscent.


Potassium carbonate is used for making soft soaps, caustic potash, potassium glass and
other potassium compounds. It is also used for washing wool.

CYANIDES
Potassium and sodium cyanides are important compounds. These can be prepared by the
following methods:
(a) Reducing amide with red hot charcoal.
2MNH2 + C → M2NCN + 2H2 (M = Na, K)
M2NCN + C → 2MCN

(b) Reducing carbonate with coke in a current of nitrogen using iron as catalyst.
Na2CO3 + 4C + N2 → 2NaCN + 3CO

(c) Fusing crude calcium cynamide (nitrolim) with coke and rock salt or sodium carbonate.
2NaCl2 + C + CaCN2 → CaCl2 + 2NaCN
Na2CO3 + C + CaCN2 → CaCO3 + 2NaCN
(d) From crude gas (manufacture) , Destructive distillation of wood gives crude gas
containing some HCN and NH3. This is passed through a solution of copper sulphate, As
a result, Cu(II) gets reduced to [Cu(CN)2]- complex:
CuSO4 + 2HCN  Cu(CN) 2 + H2SO4
2Cu(CN)2  2CuCN + C2N2 (decomposition)
CuCN + HCN  H[Cu(CN)2] (complexation)
C2N2 + H2O  HCN + HOCN (hydrolysis of C2N2)

The C2N2 gas obtained during the decomposition of Cu(CN)2 gets hydrolysis to HCN and
HOCN. The HOCN formed gets reduced to HCN by the H2 gas present in the crude gas
itself.

HOCN + H2  HCN + H2O

The solution is then concentrated to crystallize out (NH4)[Cu(CN)2]. Upon acidification


with H2SO4, HCN gas is evolved which is absorbed in KOH or NaOH to obtain KCN or
NaCN.

2NH4[Cu(CN)2] + 2H2SO4  (NH4)2SO4 + CuSO4 + Cu + 4HCN

HCN + MOH  MCN + H2O (M = Na or K)


Group IA Elements: The Alkali Metals 22

(e) KCN can be obtained by the reduction of K4[Fe(CN)6] with potassium, or by its thermal
decomposition.

K4[Fe(CN)6] + 2K  6KCN + Fe

K4[Fe(CN)6]  4KCN + Fe + 2C + N2

Properties
Sodium cyanide (mp 797 K) and potassium cyanide (mp 908 K) are extremely poisonous
compounds. These are water soluble, but the solutions arc alkaline and smell of bitter almonds
(fumes of HCN) due to hydrolysis.

CN- + H2O ⇌ HCN + OH-

On keeping, aqueous solutions get slowly converted to ammonium carbonate. Hydrolysis to


ammonia is rapid when boiled with alkalis.

CN- +2H2O  CO32- + NH4-

KCN + KOH + H2O  K2CO3 + NH3

When fused with sulphur, cyanides give thiocyanate SCN-. Upon acidification, thiocyanates
evolve HSCN. Similar reaction takes place with Se and Te, but HScCN and HTeCN are unstable,
and deposit Se or Te releasing HCN.

KCN + E  KCNE (E = S, Sc, Te)

KCNE + HCl  KCl + HECN;

HECN  HCN + E (E=Sc, Te)

As complexing agent The cyanide ion CN- is a powerful complexing agent and forms very stable
complexes with the transition metal ions (Cr3+, Ni2+, Co2+, Fe2+, Fe3+, Mn3+, Cu+, Cu2+, Pd2+, Mo6+,
etc.). Addition of KCN to a metal solution first precipitates the metal cyanide which dissolves in
the excess of KCN to form cyano complexes.

M2+ + 2CN-  M(CN)2

M(CN)2 + 2CN- ⇌ [M(CN)4]2- (M = Cu, Cd, Co, Ni, Zn)

M(CN)2 + 4CN-  [M(CN)6]4- (M= Fe, Mn, Co)


The composition of the complex depend upon the metal ion: [Ag(CN)2]- , [Cu(CN)4]2-, [Ni(CN)4]2-,
[Co(CN)6]3-, etc.
Group IA Elements: The Alkali Metals 23

Because of the high stability of the cyano complexes, copper, silver, and gold dissolve in
aqueous KCN solution.

2M + 4KCN + 2H2O 2K[M(CN)2] + 2KOH + H2 M = Cu, Ag, Au)

When H2S is passed through a solution containing Cu2+ and Cd2+ ions in the presence of KCN,
only CdS is precipitated. The stability of [Cu(CN4]2- is so high that the concentration of the Cu2+
remaining uncomplexed is too low to exceed the solubility product (Ksp) of CuS. So, no CuS gets
precipitated. [Cd(CN4)2- is, however, less stable and gives enough Cd2+ to exceed Ksp of CdS when
H2S is passed. Similarly, Ni2+ and Co2+ can be separated, [Ni(CN)4]2- is much less stable than the
cobalt (II) or cobalt (III) complexes.

As a psuedohalide anion Cyanide is a psuedohalide. It gives a white precipitate of “AgCn”


with silver nitrate, which is soluble in excess of KCN forming [Ag(CN)2]- ions.

AgNO3 + 2NaCN  Na+[Ag(CN)2]- + NaNO3


AgNO3 + Na+[Ag(CN)2]-  Ag+[Ag(CN)2]- + NaNO3
“silver cyanide”

With Cu2+ or with Fe3+, free cyanogen C2N2 is formed.


2Cu2+ + 4CN-  [2Cu(CN)2] 2CuCN + C2N2
2Fe3+ + 6CN-  [2Fe(CN)3] 2Fe(CN)2 + C2N2

When heated with MnO2 and H2SO4, CN- gets oxidized to C2N2 :
2KCN + MnO2 + 2H2SO4  K2SO4 + MnSO4 + 2H2O + C2N2

Uses
Sodium cyanide is used in the metallurgy of Ag, Au, Se, Te, etc. and for electroplating Ag, Au,
Cr, etc. It is a germicide.
Potassium cyanide is used as a reagent for synthetic organic reactions, and for analysis of
metals in laboratory.

POTASSIUM NITRATE
Potassium nitrate KNO2 is obtained by the thermal decomposition of potassium nitrate, or by
heating KNO3 with a calculated amount of lead.

2 KNO3 2 KNO2 + O2

KNO3+ Pb  KNO2+ PbO


101 g 206 g

Interaction of silver nitrate with KCl also gives KNO2.


AgNO2 + KCl  AgCl + KNO2
Group IA Elements: The Alkali Metals 24

Potassium nitrate is a deliquiscent solid. On heating with ammonium-salt or with urea acidic
solutions, nitrogen is evolved.

NO2– + NH4+ → N2 + 2H2O


2NO2– + 2H+ + CO(NH2)2 → 2N2 + CO2 + H2O

As oxidizing agent KNO2 is a strong oxidizing agent in acids and oxidizes Sn(II) to Sn (IV); I-
to I2; S2- to S; etc.
NO2– + 2H+ + e– ⇌ NO + H2O Eo = + 1.00 V.
As reducing agent It can be oxidized to nitrate with stronger oxidizing agents like acidified
permanganate or dichromate, hydrogen peroxide, bromine water, or ozone.
NO3– + 2H+ + 2e– ⇌ NO2– + H2O Eo = + 0.94 V.
As complexing agent Nitrite is a strong complexing anion and can give two series of
isomeric N- or O- nitrito complexes. When a Co2+ solution is boiled with KNO2 in the presence of
a weak acid (acetic acid), Co2+ is oxidized to Co3+ and is then complexed to hexanitritocobaltate
(III) [Co(NO2)6]3–. As its potassium salt is insoluble, a yellow precipitate of K3[Co(NO2)6] mixed
with K2Na[Co(NO2)6] is formed. This is the basis for testing K+, Co2+ and NO2– ions.

NO2– + 2H+ + e– ⇌ NO + H2O


Co2+ ⇌ Co3+ + e–
3K + Co + 6NO2– ⇌ K3[Co(NO2)6]
+ 3+

3K+ + 7NO2– + Co2+ + 2H+ → K3[Co(NO2)6] + H2O

Formation of nitrous acid When KNO2 is acidified with HCl at < 278 K, bluish solutions of
HNO2 are formed. Nitrous acid is useful for a number of organic reactions (Chapter 13).
Potassium nitrite is used in the manufacture of azo dyes and as a reagent in the laboratory.

SODIUM THIOSULPHATE
Preparation
Sodium thiosulphate Na2S2O3.5H2O is prepared by (a) boiling Na2SO2 solution with sulphur
till it becomes neutral (Na2SO3 is alkaline); (b) boiling sulphur with NaOH solution; (c) bubbling
SO2 into Na2S solution; and (d) Springer’s reaction involving oxidation of Na2S + Na2SO3 solution
by iodine.
Na2SO3 + S + 5H2O → Na2S2O3.5H2O
6NaOH + 4S → Na2S2O3 + 2Na2S + 3H2O
2Na2S + 3SO2 → 2Na2S2O3 + S
Na2S + Na2SO3 + I2 → Na2S2O3 + 2NaI
Group IA Elements: The Alkali Metals 25

It is manufactured by passing SO2 into waste liquor of Na2S containing impurities of CO2−3 ,
2− 2−
SO3 , and SO4 . The pentahydrate is obtained by crystallization in the presence of a crystal of
Na2S2O3.5H2O as it tends to form heavily supersaturated solutions.

Properties
Na2S2O3. 5H2O is a white crystalline efflorescent solid. On heating it dissolves in its own
water of crystallization. At 490 K, it loses water and then decomposes into SO2, NA2S and S on
stronger heating.
With acids In cold, acidification gives H2S2O3, which gradually loses sulphur forming H2SO3.
On heating, SO2 is evolved. However, if the solutions are kept cold, polythionic acids H2SnO6 (n
= 2 to 6) are formed.
heat
S2O32- + 2H+ H2S2O3 H2O + S + SO2

SO2
S
H2SnO6 H2S2O6. 4. S + H2O

The solution is called Weekenroder’s solution


With silver nitrate, a white precipitate of Ag2S2O3 is formed by double decomposition. It is
soluble in excess of thiosulphate solutions due to the formation of thiosulphate complexes
[Ag(S2O3)2]3- and [Ag(S2O3)3]5-. On the other hand, if the precipitated Ag2S2O3 is warmed, it
quickly changes to black Ag2S through a series of colour changes from white to yellow, orange,
brown and finally, black.

Ag2S2O3 + HOH Ag2S + H2SO4

With silver halides Sodium thiosulphate dissolves AgCl and AgBr completely due to the
formation of complexes.

AgX + 2S2O32- [Ag(S2O3)2]3- + X- X - Cl, Br

With other metal ions as a complexing anion Thiosulphate is an ambident ligand: it can
coordinate through S or through O atom. Both the isomeric complexes are known for Co(II).
With Fe (III), a transient purple colour is obtained due to the formation of [Fe(S 2O3)n]3-2n
complexes. The colour fades soon due to the reduction of iron to Fe (II) state.
With halogens Thiosulphate gets oxidized by halogens. Chlorine oxidizes it to SO42- while I2
oxidizes it to tetrathionate S4O62- ion :
Group IA Elements: The Alkali Metals 26

[Cl2 + 2e- 2Cl-] x 5

S2O32- + 5H2O 2SO42- + 10 H+ + 10e-

S2O32- + 5H2O + 5Cl2 2SO42- + 10 H+ + 10Cl-

tapi

I2 + 2e- 2I-
2S2O32- S4O62- + 2e-

2S2O32- + I2 S4O62- + 2I-

The reaction with iodine is used for iodine titration. In iodometry, I 2 is quantitatively generated
by the addition of excess of KI to the sample containing the suitable oxidant, and is titrated
against a standard thiosulphate solution. (Details are given in Chapter 15)

Mild oxidizing agents like Cu2+, Fe3+ or Au3+ oxidize thiosulphate to tetrathionate (cf.
Reaction with iodine). With Cu2+ and Au3+ solutions, thiosulphate forms complexes with the
reduced ions forming [Au(S2O3)2]3-, [Cu(S2O3)2]3- and Cu6(S2O3)54-
Strong oxidizing agents like Cl2, H2O2, acidified permanganate or acidified dichromate oxidize
it to sulphate.

Uses
Sodium thiosulphate is used in photography as a fixer and developer (reaction with AgBr); in
extraction of Au and Ag through complexation; as antichlor for removing Cl2 after bleaching the
fabric with Cl2; and as a laboratory reagent.

Structure
In thiosulphate ion, one oxygen atom of SO42- has been replaced formally by a sulphur atom.
Hence, it contains sulphur atoms in two different oxidation states. The central atom is in VI
state, while the terminal atom is in – II state. As the two sulphur atoms are directly linked,
thiosulphate tends to disproportionate (upon acidification, by SO 2, etc.)

SODAMIDE
Sodamide NaNH2 is obtained by passing dry ammonia over liquid sodium at 570 – 670 K. it is
a waxy solid ( mp 483 K ) which hydrolyses in water to ammonia, absorbs N 2O to form azide and
CO2 to form carbonate and cyanamide CN.NH2
NaNH2 + H2O  NaOH + NH3
NaNH2 + N2O  NaN3 + H2O
2 NaNH2 + 2 CO2  Na2CO3 + CN.NH2 + H2O
Group IA Elements: The Alkali Metals 27

In ammonia solutions, it ionizes to amide NH2- ions, and hence is a strong base. It can be
titrated against NH4+ ions in ammonia solutions using a suitable indicator, or by conductometric
or potentiometric methods to detect the equivalence points;
NH4+ + NH2- → 2 NH3 ( in ammonia solutions )
In ammonia as solvent, sodamide precipitates metal amides M(NH2)2 M = Zn, Sn, Cu, Co, etc )
and M(NH2)3 ( M = Al, Fe, Cr, etc ) in the name way as sodium hydroxide precipitates metal
hydroxides from aqueous solutions. Amphoteric amides dissolve in excess of sodamide forming
soluble amido complexes like [Zn(NH2)4]2- or [Al(NH2)4]-.
Sodamide is used for the manufacture of cynamide, sodium azide, and as strong base for
organic reactions in nonaqueous media (amide is stronger base than hydroxide).

OTHER SALTS
Sodium sulphate is obtained as a byproduct in the manufacture of HCl atom rock salt. The
dechahydrate Na2SO4.10H2O is known as Glauber’s salt. Crystallization below 285 K gives the
heptahydrate. From concentrated H2SO4, hydrogen sulphate NaHSO4 can be crystallized, which
on heating uses water to form disulphate or pyrosulphate Na2S2O7. Potassium sulphate K2SO4
(mp 1325 K) is not very soluble in water. It forms a series of double sulphates called alums with
trivalent metal ions: K2SO4.M2(SO4)3.24 H2O (M = Al, Fe, Cr, Mn, Ti, V, etc.). The sulphate can be
reduced to sulphide with coke.
When aqueous Na2CO3 is saturated with SO2, sodium hydrogen sulphite or sodium bisulphate
NaHSO3 is formed. On evaporating these solutions in SO2, sodium metabisulphite Na2S2O5 is
formed which is used in photography as a reducing agent (developer). Neutralization of NaHSO 3
with Na2CO3 gives sulphite Na2SO3 when crystallized above 295 K and monohydrate below 295
K. It is used as a mild bleaching agent.
Sodium phosphates Na3PO4.12H2O , Na2HPO4, and NaH2PO4.12H2O can be obtained by taking
equivalent amounts of NaOH and H3PO4. These are used as detergents and in baking powder.
The buff coloured sodium sulphide N2S.9H2O prepared by the interaction of H2S or S with
caustic soda, is used for tanning and stripping hair from hide. The polysulphides are used in
horticulture as fungicides.
Sodium choride is an important constituent of our system. It is used as raw material for the
manufacture of sodium compounds (NaOH, Na2CO3, Na2SO4 etc.) and as salting out agent in the
manufacture of soaps. Potassium chloride or potash is used a fertilizer. Potassium bromide and
iodides are used in photography.
The nitrates are used as fertilizers. Potassium nitrate is a constituent of gun powder.

ANALYTICAL CHEMISTRY OF ALKALI METALS


Qualitative reactions
All alkali metals give characteristic flame colours: Li carmine red, Na golden yellow, K lilac.

Lithium
Group IA Elements: The Alkali Metals 28

Lithium solutions give white precipitate with Na2CO3 from concentrated solutions, with
NaH2PO4 in ammonia and with NH4F. In the qualitative analysis, Li+ is detected in group VI along
with Mg2+. With alkaline iron (III) periodate solutions a white precipitate of KLiFe(IO 6) is formed
which is used to detect Li+ in the semimicro analysis.

Sodium
Na+ gives yellow precipitates of NaMg(UO2)3(OCOCH3)9.6,5H2O or as NaZn-(UO2)3
(OCO.CH3)9.6H2O from concentrated solutions (K+ and NH4+ ions interfere). However, tartaric
acid [PtCl]2- or [Co(NO2)6]3- do not precipitate sodium ions (cf. reactions of K+).

Potassium
Potassium ions can be precipitated as yellow K2Na[Co(NO2)6], white hydrogen tartrate or
perchlorate from aqueous ethanol, or yellow chloroplatinate or orange-red disicrylamine salt
from aqueous solutions.

QUANTITATIVE DETERMINATIONS
The alkali metals are best determinate by flame photometric methods by measuring
intensities at 670.8 nm for Li, 589.3 nm for Na, and 766.5 or 404.4 nm for K. In addition, these
ions can be precipitated as tetraphenylborates M+BPh4-

Lithium can be easily separated from other alkali metals as LiCl is soluble in alcohol, pyridine,
n-hexanol, etc. the chloride can be converted into sulphate with H2SO4 dried at 870-970 K and
weighed as Li2SO4. Alternatively, lithium aluminate can be precipitated at pH 12,6-13,0 ignited
to 770-870 K and weighed as 2 Li2O. 5Al2O3.

Sodium can be determined as Na2SO4 or as double Zn2+ or Mg2+ uranyl acetates. Potassium is
determined gravimetrically as sulphate, chloroplatinate or cobaltinitrite complex.

A direct titration of K+ can be done with solutions of Na+BPh4- but is better to add excess of
Na+BPh4- and titrate the excess against standard Hg(NO3)2 solutions.

K+ + Na+BH4-  KBH4 + Na+


(ppt.)

Questions

You might also like