THE GROUP 1 ELEMENTS:

THE ALKALI METALS

Read in the name your God who created

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Inorganic Chemistry 3

Jurusan Kimia

Chemistry Department

Intro
alkali metal cations are extremely difcult to reduce
metal
Davy (British) electrolyzed KOH(l) to extract the
rst of the alkali metals.

Perey (French), isolated the one alkali metal that

exists only as radioactive isotopes, francium

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Chemistry Department

Group Trends
All of the alkali metals :
- shiny, silver-colored metals.
- high electrical and thermal conductivities.
But, they are also very atypical :
Ex: the alkali metals are very soft, and they become softer
as one progresses down the group :
Thus, Li can be cut with a knife, whereas
K can be squashed like soft butter.

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Chemistry Department

Low m.p

Low mp and soft is due to :

- Weak metalic bonding
- Small enthalpy of atomization

For typical metals, Hatomization = 400 - 600

kJ/mol

High thermal conductivity and low m.p of Na

heat transfer material in nuclear reactors

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Chemistry Department

Low mp and soft is due to :

- Weak metalic bonding
- Small enthalpy of atomization
(for typical metals, Hatomization = 400 600 kJ/mol)

( most metals densities = 5 15 g/cm3)

water density!

No!
reactive with
water

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Chemistry Department

Must be stored under oil

exposed to air a thick coating of oxidation

products covers the lustrous surface very rapidly :

-react with most nonmetals :

white smoke

- dramatic reaction with water supermetals

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Chemistry Department

Feature of alkali metal compounds

All are metals have common features.
Ions ox.nu = +1,
compounds : stable, ionic solids, colorless (without colored anion CrO4-, MnO4-)

Stabilization of Large Anions

Cations of the alkali metals (except Li+) :
the largest sizes lowest charge densities,
stabilize large low-charge anions.

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Chemistry Department

Ion Hydration
All ions are hydrated when dissolved in water.
However, this is not always true in the solid phase.
Hydration in the crystalline solid balance of lattice energy (U) and
Hhydration of ions
U = electrostatic attraction between the cations and anions:
ion c.d U .
U favors the loss of an ions hydration sphere on crystallization to give the
small (U ) anhydrous ion.
But Hhydration depends on the attraction between the ion and the
surrounding polar water molecules.
A major factor contributing to the strength of the ion-dipole attraction is the
charge density of the ions.
In this ionic tug-of-war, we nd that high charge density usually favors
retention
Jurusan
Kimia of all or part of the hydration sphere in the
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solid phase, while salts of low-charge ions tend to be anhydrous.

Ion Hydration
Low charge densities (compared to other metals).
majority of solid alkali metal salts are anhydrous !

c.D of Li+ & Na+ are high enough to

form of a few hidrated salts : LiOH.8H2O.
The lowest c.d of all metals,
very few K, Rb and Cs salts are hydrated
The low c.d are reflected in
the trend in Hhidration among
the alkali metals
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Chemistry Department

Mg2+ = 1920 kJ/mol

Flame Colors

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characteristic flame color of alkali metal salt in a flame.

Solubility of alkali metal salts

so useful as reagents in the laboratory of the required anions.

Fact,
why ?

1. H ( U and Hhydration of the cation and anion)

S

Solubility 2.

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soluble, G0 < 0
Where, G0=H0 - TS0

Solubility
1. H (the lattice energy and the enthalpy of hydration of the cation and anion)
2. S

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Chemistry Department

soluble, G0 < 0
Where, G0=H0 - TS0

The lattice energy

and hydration
enthalpy terms are
essentially equal.

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Chemistry Department

Amazing...

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Chemistry Department

Solubility vs M+ a smooth curve.

very different in sizes more soluble

Although there is a strong dependence of
lattice energy on ionic charge, there is a
secondary relationship to the cation/anion
radius ratio; mismatch in ionic sizes will lead
to a lower than expected lattice energy.

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Chemistry Department

Lithium

density (gcm-3):
Lithium = 0.53
Al = 67,5
Iron = 7.874 gcm3
Iridium = 22.65

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Chemistry Department

the least dense metal (0.53 g.cm )

bright silvery, but turning black if exposed to moist air :

react with dinitrogen

(due to the greatest Li charge density of the group)

Li (l) is the most corrosive material known

the most negative Eo of any element

releases more energy than any other element when it is oxidized.
Li (aq) + e Li(s)

E = -3.05

Uses of Lithium
-

Aerospace alloy
Density of alloy LA 141
(14%Li,1%Al, 85%Mg)=1.35 g/cm3 (=1/2 Aldensity )

lithium greases-in automotive greases.

lithium stearate, CHCOOLi,
(Water resistant, not harden at cold, stable at high T ).

Extensive organometallic chemistry of Li

Mobil

density (gcm-3):
Lithium = 0.53
Al = 67,5
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Iron = 7.874
Chemistry Department
Iridium = 22.65

Lithium batteries
As anode material:
Eo >>>
Low density (1/20 of Pb)
mass saving.
very low mass per unit of
stored energy compact highvoltage cells.

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Chemistry Department

Lithium-ion Batteries

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Chemistry Department

Sodium
Uses Of Sodium
1.

Extraction of other metal (Th, Zr, tantalum and Ti.

ex : TiCl(l) + 4Na(s) Ti(s) + 4 NaCl(s)

2.

The production of the gasoline additive

tetraethyllead (TEL).
4NaPb(s) + 2CHCl(g) (CH)Pb(l) + 3 Pb(s) + 4NaCl(s)
alloy

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Chemistry Department

The Industrial Extraction of Sodium

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Chemistry Department

Potassium
K in the environment is a bit
radioactive (0.012% isotop K-40
radioactive).
human body radiation
K-40 / Ar-40 is one way of dating
rocks

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Chemistry Department

Insoluble Potassium Compounds

The least soluble : the greatest similarity in ion size.
very large anion would form the least soluble salts with the large
cations of group 1.
The salts of very large [Co(NO)]with :
Li and Na : soluble,
K, Rb, Cs : insoluble.
Test of Na+ or K+ in solution :

yellow
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The industrial Extraction of Potassium

Electrolysis would be hazardous because of the extreme

reactivity of the metal.

So, chemical process: (at 850C) :

Na(l) + KCl(l)
K(g) + NaCl(l)
Le Chtelier to get more K gas

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Chemistry Department

OXIDES

Of the alkali metals, only Li forms a normal oxide :

4Li(S) + O(g) 2LiO(s)

NaO (sodium peroxide),

containing the dioxide (2-) ion, O (=peroxide ion)
2Na(s) + O(g) NaO(s)

The other three alkali metals react with an excess of O2 to form

dioxides(1-) (traditionally named superoxides) :

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HYDROXIDES
The solid hydroxide are white, translucent solids that absorb
moisture from the air until they dissolve in the excess water-a process
known as deliquescence.
Alkali metal hydroxides are all extremely hazardous because the
hydroxides ion reacts with skin protein to destroy the skin surface.

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Chemistry Department

The Industrial Synthesis of Sodium Hydroxide

electrolysis of brine (aqueous sodium chloride).
2HO(l) + 2e H(g) + 2OH(aq)
2Cl(aq) Cl(g) + 2e

The diaphragm cell

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Chemistry Department

Commercial Uses of Sodium Hydroxide

1.
2.
3.
4.

Reagent in organic chemical plants,

Synthesis of other inorganic chemical.
pulp and paper industry,
30 percent is used in hundreds of other ways.

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Chemistry Department

SODIUM CHLORIDE
Seawater is NaCl 3% solution, table salts by using the
Suns energy to evaporate seawater

Salt was one of the earliest commodities to be traded

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Chemistry Department

Potassium chloride
KCl is recovered from ancient
dried lake deposits,
the deposits also contain NaCl,
KMgCl3.6H2O; MgSO4.H2O; and
many other salts.

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Chemistry Department

Separation The Components

differences in solubility
adding the mixture of crystals to saturated brine
electrostatic process

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Chemistry Department

potassium chloride is
used as fertilizer.

Potassium ion is essential element for

plant growth and about 4.5 x 107
tonnes of potassium chloride are used
worldwide for this purpose every year,
so it is a major chemical product.

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Chemistry Department

Sodium Carbonate
In North America, sodium carbonate is
obtained
from
the
mineral
trona,
Na2CO3.NaHCO3.2H2O
(sodiumsesquicarbonate). Sesqui means
one and one-half, and it is the number
of sodium ions per carbonate unit in the
mineral.

In the monohydrate process

of extraction, trona is mined
about 400 m underground,
crushed, and then heated
(calcined) in rotary kilns.

Sodium carbonate is made by the

Solvay, or ammonia-soda, process.

This process involves the reaction
of sodium chloride with calcium
carbonate:
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Chemistry Department

Uses of Sodium Carbonate

- used in glass manufacture.
the sodium carbonate is
reacted with silicon dioxide
(sand) and other components
at about 1500C.
- used to remove alkaline earth
metal ions from water
supplies
by converting them to their
insoluble
carbonates,
a
process
called
water
softening.
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Chemistry Department

Sodium Hydrogen Carbonate

Sodium hydrogen carbonate is less watersoluble than sodium carbonate.
Thus, it can be prepared by bubbling carbon
dioxide through a saturated solution of the
carbonate:

Heating
sodium
hydrogen
carbonate
causes
it
to
decompose back to
sodium carbonate:
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Chemistry Department

The main use is in the food industry (baking

powder) , to cause bakery products to rise.

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Chemistry Department

Ammonia Reaction
The alkali metals themselves have the
unusual property of dissolving in liquid
ammonia to yield solutions that are
deep blue when dilute
When concentrated by evaporation, the solutions
have a bronze color and behave like a liquid
metal. presence of a transition metal catalyst,
the solutions decompose to yield the amide salt,
NaNH2, and hydrogen gas:

38

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Chemistry Department

Ammonium Ion as
Pseudo-Alkali-Metal Ion
A polyatomic ion whose behavior in many ways mimics that
of an ion of an element or of a group of elements.

ammonium ion is a polyatomic cation containing two

nonmetals, it behaves in many respects like an alkali
metal ion.
The ammonium ion resembles an alkali metal ion in its
precipitation reactions.

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Chemistry Department

Biological Aspect
The alkali metal ions
-balance the negative charge
associated with many of the
protein units in the body.
-help to maintain the osmotic
pressure within cells, preventing
them from collapsing.

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Chemistry Department

Cells pump sodium ions out of the

cytoplasm and pump potassium ions in. It is
this difference in total alkali metal ion
concentrations inside and outside cells that
produces an electrical potential across the
cell membrane.

The potential difference underlies many basic processes,

- the hearts generation of rhythmic electrical signals
- the kidneys unceasing separation of vital and toxic solutes in the blood,
- the eyes precise control of the lenss refractive index.

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Chemistry Department

Element
Reaction
flowcharts

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Chemistry Department