THE GROUP 1 ELEMENTS:

THE ALKALI METALS

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 Intro
• alkali metal cations are extremely difficult to
reduce to get metal.

• Davy electrolyzed KOH(l) to extract the first of the

alkali metals.

• Perey (French), isolated the one alkali metal that

exists only as radioactive isotopes, francium

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 11.1. Group Trends
All of the alkali metals are shiny (silver-colored), and have
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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Low m.p

Low mp and soft is due to

Weak metalic bonding from
the 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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 Low density

½ water density!

most metals ‘ densities = 5 – 15 g/cm3

No!
reactive with water

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• 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

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• dramatic reaction with water  supermetals

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 11.2. 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-)

KMnO4

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

Na through Cs are the only cations that form solid hydrogen carbonate salts:

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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:
c.d ion ↑  U ↑.

• U favors the loss of an ion’s 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.
charge density of the ions strengthen of the ion-dipole attraction

• Here, high charge density usually favors retention of all or part of the hydration
sphere in the solid phase, while salts of low-charge ions tend to be anhydrous.

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 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

Jurusan Kimia Mg2+ = 1920 kJ/mol

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Flame Colors Characteristic flame color of alkali metal salt in a flame.

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 11.3. Solubility of alkali metal salts
 so useful as reagents in the laboratory of the required anions.

Fact,
why ?

1. ΔH (U and ∆Hhydration of the cation and anion)

Solubility  2. ΔS

Jurusan Kimia soluble, ΔG0 < 0

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Where, ΔG0=ΔH0 - TΔS0
 Solubility 
• ΔH (the lattice energy and the enthalpy of hydration of the cation and anion)
• ΔS

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Where, ΔG0=ΔH0 - TΔS0
 The lattice energy
and hydration
enthalpy terms are
essentially equal.

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Chemistry Department
Jurusan Kimia
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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 11.4. Lithium

• the least dense metal (0.53 g.cmˉᶟ )

• 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 

density (g•cm-3): releases more energy than any other element when it is
Lithium = 0.53 oxidized.
Al = 67,5
Iron = 7.874 g·cm−3
Iridium = 22.65 Li⁺ (aq) + e⁻ → Li(s) E⁰ = -3.05

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 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, C17H35COOLi,
(Water resistant, not harden at cold, stable at high T).

• Extensive organometallic chemistry of Li

density (g•cm-3):
Lithium = 0.53
Al = 67,5
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Iron = 7.874
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Iridium = 22.65
Lithium batteries
As anode material:
Ø Eo >>>
Ø Low density (1/20 of Pb)  mass saving.
Ø very low mass per unit of stored energy 
compact high-voltage cells.

Lead acid battery :

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Lithium batteries

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 11.5. Sodium
Uses Of Sodium:

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

2. The production of the gasoline additive tetraethyllead (TEL).

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 The Industrial Extraction of Sodium

Downs process

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 11.6 Potassium
• K in the environment is a bit radioactive (0.012% of
K are K-40 radioactive).  human body radiation.
•
• K-40 to Ar-40 ratio for dating rocks.

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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(NO2)6]3-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 850⁰ C) :

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

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 11.7 Oxides

• Only Li forms a normal oxide :

4Li(s) + O₂ (g) → 2Li2O(s)

• Na2O2 (sodium peroxide),

containing the dioxide (2-) ion, O2²⁻ (=peroxide ion)
2Na(s) + O2(g) → Na2O2 (s)

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

dioxides(1-) (traditionally named superoxides) :

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 Dioxide(2-)

Sodium dioxide(2-) :
• diamagnetic,
• bond length is about 149 pm

Dioxygen :
• paramagnetic,
• bond length is about 121 pm

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 dioxide(1-)

used in submarines, self-contained breathing

equipment.

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 11.8 Hydroxides
Alkali metal hydroxides are :

• absorb moisture from the air until they dissolve in the

excess water- a process known as deliquescence.

• hazardous because the hydroxides ion reacts with skin

protein to destroy the skin surface.

• absorb carbon dioxide from the atmosphere:

• Water soluble --> are sources of the OH-

NaOH (caustic soda) --> inorganic chem,
KOH (caustic potash)--> organic chemistry (more soluble in organic solvents).

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The Industrial Synthesis of Sodium Hydroxide

electrolysis of brine (aqueous sodium chloride) :

2H2O(l) + 2e⁻ → H₂ (g) + 2OH⁻ (aq)
2Cl⁻ (aq) → Cl₂ (g) + 2e⁻

Diaphragm cell

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Commercial Uses of Sodium Hydroxide
• Reagent , synthesis of other inorganic chemical, pulp
and paper industry, and etc .

• NaOH : reaction with greases (in ovens, clogging

drains) some commercial drain-treatment products,
aluminum metal is mixed with the sodium hydroxide :

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 to evaporate seawater
11.10 Sodium Chloride

• Seawater = solution NaCl 3%

 table salts

• Today, extracted from underground

deposits,

the earliest commodities to be traded.

salt (sal)— salary

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Chemistry Department
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Chemistry Department
 11.10 Potassium chloride
• KCl is recovered from ancient dried lake
deposits (like NaCl).

• Only use for feritilizer; 4.5x107 tonnes/year.

N – nitrogen: pertumbuhan vegetatif, terutama

daun.
P – fosfor: pertumbuhan akar dan tunas
K – kalium: pembungaan dan pembuahan
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 11.11 Sodium Carbonate
• exists as anhydrous state (soda ash),
monohydrate, Na2CO3.H2O, and decahydrate,
Na2CO3.10H2O (washing soda).

• made by the Solvay, or ammonia-soda, process :

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 Uses of Sodium Carbonate

• in glass manufacture:

• water “softening.” : to remove alkaline earth metal ions

(Ca2+) from water byto give insoluble carbonates:

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 11.12 Sodium Hydrogen Carbonate

• NaHCO3 is less water-soluble than Na2CO3., prepared by:

• Dry powder fire extinguishers :

• to cause bakery to rise (as a mixture (baking powder : NaHCO3

and Ca(H2PO4)2):

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Chemistry Department
 11.13 Ammonia Reaction
• The alkali metals if dissolved in liquid
ammonia to yield solutions deep that
conduct current :

• When concentrated by evaporation, the solutions have a bronze color

and behave like a liquid metal.

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Chemistry Department
 11.14 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
 11.15 Biological Aspect
• Na+ and K+ are essential to life.
• at least 1 g of Na+ per day in our diet --> OK
• less K+ in food, --> bananas and coffee.

Na+ and K+
1. to balance the negative charge of protein
units in the body.
2. maintain the osmotic pressure within cells,
preventing them from collapsing.
3. to produce electrical potential across the cell
membrane for heart’s generation of rhythmic
electrical signals, the kidney’s unceasing
separation of vital and toxic solutes in the
blood, and the eye’s precise control of the
lens’s refractive index.
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Chemistry Department
 • 10 W of power produced by the human brain results from the Na+/K+
ATP enzyme pumping K+ into and Na+ out of brain cells.
• When we “go into shock”, it is a massive leakage of the alkali metal
ions through the cell walls that causes the phenomenon.

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Chemistry Department
 11.16 Element Reaction flowcharts

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Chemistry Department