Alkali metals in liquid
Ammonia
Alkali metals in Liquid Ammonia
• Alkali and alkaline earth metals have the unusual property of
dissolving in liquid ammonia
• These metals on dissolving in liquid ammonia, a deep blue
colored solution is obtained but on long standing or in
presence of impurity or transition metal catalyst, the solution
decomposes and form amide and hydrogen gas is released
2M + xNH3 →2M+(am) + 2NH3(l) + 2e- (am) → 2NaNH2(am) + H2(g)
• Dilute solutions survive for long periods at the temperature of
boiling ammonia (-33°C) and in the absence of air.
The blue metal -ammonia solutions are excellent reducing agents. For example,
the Ni(I) complex [Ni2(CN)6]4-, in which nickel is in an unusually low oxidation
state may be prepared by the reduction of Ni(II) with potassium in liquid
ammonia:
2K2Ni(CN)4 + 2K +(am) + 2e-( am) →K4 [Ni2(CN)6](am) + 2KCN
Alkali metal +
Concentration of alkali metal
Ammonia
1. Colour- light blue to dark blue
to bronze layer to finally
Light blue solution bronze
2. Conductivity-high for dil
solution then it diminishes
to minimum value then it
Dark blue solution increases dramatically
approaches to typically liq.
Metals
Bronze coloured layer
appears on the surface of 3. Magnetic susptibility- highest
blue solution(phase in dil solution or paramagnetic
separation) (one free electron per atom)
then it diminishes to
diamagnetic when Conductivity
Bronze solution
is minimum after that
paramagnetism increases
Alkali metals in Liquid Ammonia
• When alkali metal is added to liquid ammonia, initially light
blue color is obtained which intensifies on adding more alkali
metal
• After addition of certain mole ratio of alkali metal to solvent,
phase separation occur(a bronze colored layer start floating
out above blue colored solution)
• As more alkali metal added, the volume of bronze color grows
and at the end only bornze colour will be there and now the
solution behaves like a liquid metal
• On Further addition of alkali metal, no alkali metal will dissolve
Alkali metals in Liquid Ammonia
• All these are different in their colours, conductivity and magnetic susptibility
• When the solution is blue, the solution is paramagnetic and conduct current
electrolytically mainly due to the presence of solvated electrons
• The main species formed are solvated metal ions and solvated electron
M + xNH3 → M+ (am) + e- (am)
• Complete ionization into their ions so the solution is considered as true solution
and highly conductive
• In dil. solution, becoz of high mobality of the electron- coductivity is highest.
Conductivity at this time is 280 times than that of the cation
• Solvated electron has a broad absorption band extending to infrared region with
maxima at 1500nm and a short wavelength tail. This is the tail which gives rise
to the deep-blue color of the solution
• When the solution is bronze colored, it behaves like a liquid metal
Alkali metals in Liquid Ammonia
• Initially the solution is paramagnetic and highly conductive which becomes
diamagnetic and conductivity deminishes to minimum value
• Coductivity decreases as concentration of metal increases. It is because of
the mobile electrons e-(am) is used up in the formation of the complex
M-(am) (in which one metal ion and two ammoniated electrons are present
as ion pair). They are held together via coulambic force.
• M(am) + e-(am) ⇌ M-(am)
• Concurrently, M(am) begins to dimerise to give (M2)am in which the
interaction between the two electrons is sufficiently strong to lead to spin
pairing and become diamagnetic
• 2M(am) ⇌ (M2)(am)
Alkali metals in Liquid Ammonia
• At still higher concentration the system behaves as a molten
metal in which the metal cation are ammoniated
• Further more higher conc., conductivity and magnetic
susptibility increases
• At higher concentration, there is no enough ammonia to
adequately solvate the electron, the solution then be
described as [M+(am)]e- i.e. as a molten expanded metal.
• These solutions of metals in liquid ammonia act as a powerful
reducing agent