Alkali Metals Alkali Metals Alkali Metals The Characteristic Flame Colouration

Alkali Metals - Overview
Silvery, soft metals with a low melting point (Li is shown below)
Very reactive – powerful reducing agents.

The reactivity increases from Li Æ Cs
Alkali Metals - History
English chemist. He discovered, by electrolysis, the metallic

elements sodium and potassium in 1807, and calcium, boron,
magnesium, strontium, and barium in 1808. In addition, he
established that chlorine is an element and proposed that
hydrogen is present in all acids. He invented the safety lamp
for use in mines where methane was present, enabling miners
to work in previously unsafe conditions. He also discovered the
anaesthetic properties of laughing gas. He was knighted for his
work in 1812 and made baronet in 1818.
Lithium was discovered in 1817 by Johan August Arfvedson

(1792 – 1841) at Stockholm, Sweden. The metal itself was first
isolated in 1821.
Humphrey Davy Cesium was discovered in 1860. Gustav Kirchhoff and Robert
(1778 – 1829) Bunsen found the element by looking at the line spectrom of
many elements in the mineral water from Durkheim. They
came upon an element with a line spectrum of two bright lines
that has never been seen before and named the element
caesium. They named it caesium because of the latin
meaning, heavenly blue.
Flame Test for Alkali Metals
(Video: http://www.cci.ethz.ch)
The heating of alkali metals in a Bunsen flame imparts a characteristic flame emission
colour, as the outer electrons are easily promoted to a higher energy level. The analytical
determination of the alkali metals through flame photometry, atom emission spectroscopy
(AES) or atom absorption spectroscopy (AAS) is based on this phenomenon.
The Glowing Cucumber
The characteristic flame colouration of alkali metal salts is due to the

most intensive spectral lines, which, in the case of sodium are two yellow
lines at 589.0 and 589.6 nm. Gherkins contain sodium chloride and, as
the current passes there is is strong local heating which vapourises the
sap in the gherkin tissue which contains a high concentration of sodium
chloride. Sodium atoms which have been thermally excited emit the
intense yellow colour as they return to the ground state.
Technical Production of Sodium
• Sodium is produced by
electrolysis of NaCl.
• To reduce the melting temp.

Of NaCl (808 °C), 60 %
CaCl2 is added (~ 600 °C).
• The cell design keeps the

sodium and chlorine apart
so that they can’t react with
each other.
‘Downs Cell’
Technical Production of Lithium and Kalium
• Lithium is produced by electrolysis • Kalium is produced by reduction

of an eutectic mixture of LiCl and of molten KCl with metallic Na.
KCl at 450 °C. First, a Na-K alloy is obtained from
which K is obtained by destillation.
KCl : Mp.: 776°C; LiCl : Mp.: 613°C;

KCl (60 mol%) / LiCl (40 mol%): Mp.: 384°C.
Alkali Metal Alloys
Chemistry: With the exception of lithium, alloys of alkali metals can be

made up at any ratio. The ternary alloy, 12% Na, 47% K and 41% Cs,
exhibits the lowest known melting point of any metallic system (Mp: -78°
C). The binary alloy 23% Na and 77% K has a melting point of -12° C
(eutectic mixture) and is of enormous value in synthetic chemistry as it is
a highly effective reductant. This alloy is a far more powerful reductant
than either of the pure parent metals.
Alkali Metals and Water
2 M + 2 H2 O 2 M+ + 2 OH- + H2
Lithium reacts with water without

melting and without ignition of the
hydrogen; sodium melts in the
reaction, without ignition of the
Potassium and water. hydrogen (for small pieces).
(Video: http://www.cci.ethz.ch) Potassium (as well as the heavier
alkali metals) reacts so violently that
the hydrogen is ignited and burns
producing a violet flame.
Alkali Metals and Liquid NH33
Alkali metals dissolve in liquid NH3 to

give a ‘solvated electron’ solution that
is blue when dilute and bronze when
concentrated.
Alkali Metal Hydrides
• Alkali metals react with hydrogen to form stoichiometric hydrides (MH). They
are salts (NaCl structure) with a lattice energy between MF and MCl.
• LiH is obtained form the elements at 600 °C. With water, hydrogen is
generated. In ether, LiH reacts with many halides to form double hydrides.
Li + 0.5 H2 LiH
LiH + H2O LiOH + H2
4 LiH + AlCl3 LiAlH4 + 3 LiCl
• NaH is obtained form the elements at 300 °C. With water, it reacts stronger
than LiH (drying agent). NaH is used as a reducing agent.
Na + 0.5 H2 NaH
4 NaH + AlBr3 NaAlH4 + 3 NaBr

Alkali Metal Halides
Alkali metal halide salts generally

show a good solubility in water.
Lattice enthalpy effects are
important when comparing the
solubilities: a mismatch between
cation and anion size leads to an
increased repulsion between like-
charged ions, decreasing lattice
enthalpy.
CsCl vs. NaCl
Each Cs+ is coordinated to 8 Cl- and Each Na+ is coordinated to 6 Cl-

each Cl- is coordinated to 8 Cs+. and each Cl- is coordinated to 6
Similar: CsBr and CsI. Na+. Similar: all other alkali metal
halides except CsBr and CsI.
Sodium Chloride
• Mostly mined, extracted with water from

underground salt deposits or obtained by
evaporation of sea water.
• Industrially important for the production of

Cl2 and NaOH.
• Food additive (3 g per day required).
• About 25 % goes to road salting use.
• NaCl is not hydroscopic. If food-salt

becomes ‘wet’ it is due to impurities of
MgCl2.
NaCl – Chemical Transformations
Note: The methods of preparation suggested by this diagram are

not necessarily the preferred industrial methods.
Alkali Metal Oxides
All alkali metals react directly with

oxygen, the product obtained varies
with cation size. Diamagnetic
peroxide and paramagnetic
superoxide are reduction products
of O2 with bond orders of 1.0 and
1.5, respectively.
Na22O22 and KO22
• The hydrolysis of Na2O2 is used as the commercial route to

hydrogen peroxide.
• Potassium oxide is used in submarines, spacecrafts and

mines to produce oxygen from waste CO2.
Sodium Hydroxide
• Caustic soda (sodium hydroxide) is an important

inorganic chemical produced by the electrolysis of
NaCl. The world production of caustic soda is about
45 million tonnes.
• About 70 % is used as a reagent in chemical plants

(aluminium production; NaOCl production).
• Acive incredient in cleaning products (e.g. Drano®).
• Widely used in the food inductry (soften and remove

skins of potatoes; softens olives; the ‘glue’ to stick
NaCl on pretzels).
Technical Prodcution of NaOH
A membrane cell for electrolytic production of Cl2 and NaOH. Chloride ion is oxidized to Cl2
gas at the anode, and water is converted to H2 gas and OH-ions at the cathode. Sodium ions
move from the anode compartment to the cathode compartment through a cation-permeable
membrane. Reactants enter the cell, and products (Cl2 gas, H2 gas, aqueous NaOH) leave
through appropriately placed pipes .
Sodium Carbonate (Na22CO33)
• Important in chemical industry. 70 % are produced

synthetically in the Solvay process but the USA has
large natural sources.
• Primarily used to make sodium-containing glass.
precipitates
NaCl + NH3 + H2O + CO2 NaHCO3 + NH4Cl
200 °C
2 NaHCO3 Na2CO3 + CO2 + H2O
re-used
Sodium Bicarbonate (NaHCO33)
Mainly used:
• As an additive in food an drinks.
• As a baking powder (+ Ca(H2PO4)2).
• As a drug (antiacid).
• As a component of personal care products such as

toothpaste.
• To blow foams such as expanded polystyrene.

Li22CO33
• 1949: Lithium was reported to calm guinea pigs

and to lessen manic symptoms in humans.
• 1970: approval by the Food and Drug

Administration (FDA).
• One of the most frequently used drugs for manic

depression.
• Drug: simply Li2(CO3).
• Suizide rate is reduced by a factor of eight.
• Mode of action not clear.

Radiodating with 40
40K
• 0.012 % is the radioactive isotope 40K (t1/2 = 1.3 x 109 y).
• The decay of 40K occurs by two pathways: electron capture or emission.
• 40Ar that is formed after molten rocks (e.g. magma) became solid is
trapped and the K-Ar ratio can be used to estimate the date of this event.
• Using lasers to melt rock samples now offers a precision of 1 %.

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Alkali Metals - Overview

Very reactive – powerful reducing agents.

English chemist. He discovered, by electrolysis, the metallic

Lithium was discovered in 1817 by Johan August Arfvedson

The characteristic flame colouration of alkali metal salts is due to the

• To reduce the melting temp.

• The cell design keeps the

• Lithium is produced by electrolysis • Kalium is produced by reduction

KCl : Mp.: 776°C; LiCl : Mp.: 613°C;

Chemistry: With the exception of lithium, alloys of alkali metals can be

Lithium reacts with water without

Alkali metals dissolve in liquid NH3 to

4 NaH + AlBr3 NaAlH4 + 3 NaBr

Alkali metal halide salts generally

Each Cs+ is coordinated to 8 Cl- and Each Na+ is coordinated to 6 Cl-

• Mostly mined, extracted with water from

• Industrially important for the production of

• Food additive (3 g per day required).

• About 25 % goes to road salting use.

• NaCl is not hydroscopic. If food-salt

Note: The methods of preparation suggested by this diagram are

All alkali metals react directly with

• The hydrolysis of Na2O2 is used as the commercial route to

• Potassium oxide is used in submarines, spacecrafts and

• Caustic soda (sodium hydroxide) is an important

• About 70 % is used as a reagent in chemical plants

• Acive incredient in cleaning products (e.g. Drano®).

• Widely used in the food inductry (soften and remove

• Important in chemical industry. 70 % are produced

• Primarily used to make sodium-containing glass.

NaCl + NH3 + H2O + CO2 NaHCO3 + NH4Cl

• As a baking powder (+ Ca(H2PO4)2).

• As a component of personal care products such as

• To blow foams such as expanded polystyrene.

• 1949: Lithium was reported to calm guinea pigs

• 1970: approval by the Food and Drug

• One of the most frequently used drugs for manic

• Drug: simply Li2(CO3).

• Suizide rate is reduced by a factor of eight.

• Mode of action not clear.

• 0.012 % is the radioactive isotope 40K (t1/2 = 1.3 x 109 y).

• The decay of 40K occurs by two pathways: electron capture or emission.

• Using lasers to melt rock samples now offers a precision of 1 %.

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