Ch.

11: 1
The Group 1 elements
1. Part A: The Essentials
a. The Group 1 elements, the alkali metals, are lithium, sodium, potassium,
rubidium, caesium (cesium), and francium
b. All the elements are metals and form simple ionic compounds, most of which are
soluble in water
2. 11.1 The elements
a. Properties
i. The trends in the properties of the Group 1 metals and their compounds can
be explained in terms of variation in their atomic radii and ionization energies
ii. All the Group 1 elements are metals with valence electrons configuration ns1
iii. They conduct electricity and heat, are soft, and have low melting points that
decrease down the group
iv. Their softness and low melting points stem from the fact that their metallic
bonding is weak because each atom contributes only one electron to the
molecular orbital band
v. As the atomic number increases, m/b point decreases because more
electrons are being added
1. Electrons become more free, less attraction, weaker bonds
vi. All the elements adopt a body-centered cubic structure and because that
structure-type is not closely-packed and their atomic radii are large, they
have low densities
vii. The chemical properties of the Group 1 elements correlate with the trend in
their atomic radii. The increase in atomic radius from Li to Cs leads to a
decrease in first ionization energy down the group because the valence shell
is increasingly distant from the nucleus
viii. The metals are readily oxidized standard potentials of couples M+/M are all
large and negative
ix. The enthalpies of sublimation and ionization both decrease down the group
(making oxidation more favorable)
3. 11.2 Simple compounds
a. The binary compounds of the alkali metals contain the cations of the elements and
exhibit predominantly ionic bonding
b. Group 1 elements form ionic (saline) hydride with the rock-salt structure; the anion
present is the hydride ion, Hc. All the Group 1 elements form halides, MX
d. Group 1 elements react vigorously with oxygen
e. All the hydroxides are white, translucent, deliquescent solids
f. All the common salts of the Group 1 metals and soluble in water, although most of
their solid salts are anhydrous
g. The Group 1 elements ions are hard Lewis acids and complexes are formed mainly
with small, hard donors such as O or N atoms
h. The lighter Group 1 elements form organometallic compounds which are highly
reactive, hydrolyzed by water, liberating hydrogen, and are pyrophoric
(spontaneously igniting) in air

Ch. 11: 2

4. 11.3 The atypical properties of lithium

a. Group 1 and Li differences
i. The chemical properties of Li are anomalous due to its small ionic radius and
tendency to exhibit covalent bonding
ii. Lithium can exhibit a high degree of covalent character in its bonding. This
covalent character is due to the high polarizing power of the Li+ ion
associated with high charge-density
iii. Lithium forms the normal oxide when burnt in oxygen whereas other Group 1
elements form peroxides or superoxides
iv. Lithium is the only alkali metal to form a nitride, Li3N, when heated in
nitrogen and a carbide, Li2C2, when heated with graphite
v. Some lithium salts such as the carbonate, phosphate, and fluoride have very
low solubilities in water. Other lithium salts crystallize as hydrates or are
hygroscopic
vi. Lithium forms many stable organometallic compounds
vii. Lithium nitrate decomposes directly to the oxide whereas the other alkali
metals initially form nitrites, MNO2
viii. Lithium hydride is stable to heating to 900 C whereas the other hydrides
decompose above 400 C
b. Lithiums very low molar mass, which makes it the least dense metal, leads to
application where low weight is important
i. Rechargeable batteries
5. Part B: The Detail
a. 11.4 Occurrence and extraction Group 1 elements can be extracted by electrolysis
i. Lithium
1. The name lithium comes from the Greek lithos for stone
2. Most abundant mineral is spodumene, LiALSi2O6
ii. Sodium
1. Name derives from Latin natrium
2. Occurs as the mineral rock salt (NaCl) and in salt lakes and seawater
3. The metal is extracted by Downs process, the electrolysis of molten
sodium chloride:
a. 2NaCl (l) -> 2 Na (l) + Cl2 (g)
b. The sodium chloride is kept molten at 600 C, a temperature
considerably below its melting point of 808 C, by the addition of
calcium chloride
c. The electrolysis liberates liquid sodium metal at the cathode,
which rises to the surface of the cell where it is collected under
an inert atmosphere
iii. Potassium

Ch. 11: 3
1. Name derives from Latin kalium
2. Occurs naturally as potash and carnallite
3. In principle, potassium could be extracted electrolytically but the high
reactivity of the element makes this far too hazardous
4. Instead, molten sodium and molten potassium chloride are heated
together and potassium and sodium chloride are formed
5. Na (l) + KCl (l) <-> NaCl (l) + K (g)
a. At the temperatura of operation, potassium is a vapour and
removing it from the system drives the equilibrium to the right
iv. Rubidium
1. Derives from the Latin rubidus for deep red
2. Occur as minor constituents of the mineral lepidolite, from which they
are obtained from the extraction of lithium
3. 2 RbCl (l) + Ca (s) -> CaCl2 (s) + 2 Rb (s)
4. The metals are obtained from the molten chloride by reduction with
calcium or barium
v. Caesium
1. Derives from caesium for sky blue
2. Occurs as the mineral pollucite
3. The element is extracted from the mineral by leaching with sulfuric
acid then converted to the sulfate by roasting with carbon
4. Caesium metal can also be obtained by the electrolysis of molten CsCN
b. 11.5 Uses of the elements and their compounds
i. Lithium
1. Common uses of lithium and related to its low density; the most widely
used compounds of Group 1 are sodium chloride and sodium hydroxide
2. The applications of lithium metal are in large part due to its low atomic
mass and consequently low density. It is used in alloys where weight is
of a premium concern, such as aircraft parts
3. Li make lithium batteries an attractive alternative to lead acid
batteries
a. Lithium carbonate is widely used to treat bipolar conditions
(maniac depression) and lithium stearate is a widely used
lubricant in the automotive industry
ii. Na and K essential for physiological function
1. Used in the extraction of rarer metals, such as Ti form titanium (IV)
chloride.
2. Na
a. NaCl
i. The major uses of NaCl are road de-icing agent,
alternative material using less NaCl being sought. Sodium
for street lamps
ii. Table salt
iii. Electrolyte in physiology
iv. De-icing
v. Production of NaOH by electrolysis in water
b. Metal in street lamps (yellow emission
c. NaOH
i. 10th in tonnage used in industry
3. Potassium
a. KOH
i. Is used in soap manufacture to make soft liquid soaps.

Ch. 11: 4
b. KCl and K2SO4
i. Potassium chloride and sulfate are used as fertilizers
c. NO3 and KClO3
i. Nitrate and chlorate are used in fireworks.
d. KBr
i. Potassium bromide has been used as an antaphrodisiac (a
compound that reduces libido).
e. KCN
i. Used in the metal extraction and plating industries to
obtain or aid in the deposition of copper, silver, and gold
iii. Rb and Cs
1. Glass for fiber-optics in the telecommunications industry, night vision
equipment, and photoelectric cells
2. Caesium salts are also used as high-density drilling fluids: the high
density of the solutions arises from the high atomic mass of Cs
c. 11.6 Hydrides
i. The hydrides of the Group 1 elements are ionic and contain the H- ion
ii. The Group 1 elements react with hydrogen to form ionic (saline) hydride with
the rock-salt structure; the anion present is the hydride ion, Hiii. The hydrides react violent with water:
1. NaH (s) + H2O (l) -> NaOH (aq) + H2 (g)
a. Finely divided sodium hydride can ignite if it is left exposed to
humid air
iv. Hydrides are useful as non-nucleophilic bases and reductants:
1. NaH (s) + NH3 (l) -> NaNH2 (am) + H2 (g)
d. 11.7 Halides
i. On descending the group, the enthalpy of formation becomes less negative
for the fluorides but more negative for the chlorides, bromides, and iodides
ii. All the Group 1 elements form halides, MX, by direction combination of the
elements
iii. The enthalpies of formation of all the halides are large and negative,
becoming less negative from the fluoride to iodide for each element
iv. The enthalpies of formation become less negative for the fluorides on
descending the group but become more negative for the chlorides, bromides,
and iodide
v. As the radius of the anion increases form F- to I-, the lattice enthalpy
becomes smaller
vi. The halides are all soluble in water with the exception of LiF, which is only
sparingly soluble. This low solubility of LiF can be traced to the fact that the
high lattice enthalpy due to the small ionic radii is not offset by the enthalpy
of hydration
vii. Enthalpy of Formation
1. fH = subH + ionH + disH + egH + LH
e. 11.8 Oxides and related compounds
i. All the Group 1 elements react vigorously with oxygen. Only Li reacts directly
with excess oxygen to give just the oxide, Li2O, which adopts the antifluorite
structure
1. 4Li (s) + O2 (g) -> 2Li2O (s)
ii. Sodium
1. Reacts with oxygen to give the peroxide, Na2O2, which contains the
peroxide ion, O22-

Ch. 11: 5
iii.

iv.

v.

f.

11.10
i.

ii.
iii.

iv.

v.
vi.

vii.
g. 11.11
i.
ii.

2. 2Na (s) + O2(g) -> Na2O2 (s)

Superoxides
1. The other Group 1 elements form the superoxides
2. K (s) + O2 (g) -> KO2 (s)
3. These compounds contain the paramagnetic superoxide ion, O2- and
adopt a CaC2 type structure that is based on the rock-salt structure
4. Potassium superoxide, KO2, absorbs carbon dioxide and liberates
oxygen. This reaction is exploited to purify air in applications such as
submarines and breathing apparatus
a. 4 KO2 (s) + 2 CO2 (g) -> 2K2CO3 (s) + 3O2 (g)
b. K2CO3 (s) + CO2 (g) + H2O (g) -> 2KHCO3 (s)
Normal oxides
1. The normal oxides of Na, K, Rb, and Cs can be prepared by heating the
metal with a limited amount of oxygen or by thermal decomposition of
the peroxide or superoxide
2. Na2O2 (s) -> Na2O (s) 1/2O2 (g)
3. The oxides of Na2O, K2O, and Rb2O adopt the antifluorite structure
Ozonides
1. compounds that contain the ozonide ion, O3-, exist for all the Group 1
elements
2. 2 KO3 (s) -> 2 KO2 (s) + O2 (g)
3. All Group I elements form Ozinides, NaO3 unstable and explode
violently
Hydroxides
All the hydroxides of Group 1 elements are white, translucent, deliquescent
solids. They absorb water and carbon dioxide from the atmosphere in an
exothermic reaction
The solubility of the hydroxides makes them a ready source of OH- ions in the
laboratory and in industry
Metal oxides are Basic Anhydrides React with water to yield hydroxides
1. Li2O + H2O 2 LiOH
2. Na2O + 2 H2O 2 NaOH + H2O2
3. 2 KO2 + 2 H2O 2 KOH + H2O2 + O2
NaOH is used in industry for a number of different applications
1. Papermaking
2. Olives are soaked in it to soften the skin
3. Drain cleaner
Lithium hydroxide
1. LiOH, forms the stable hydrate, LiOH.8H2O.
Potassium hydroxide
1. KOH, is soluble in ethanol and this ethanolic KOH is a useful reagent
in organic synthesis
Alkali metal hydroxide solutions rapidly absorb carbon dioxide from the air
1. 2 MOH (aq) + CO2 (g) -> M2CO3 (aq) + H2O (l)
Compounds of oxoacids
The Group 1 elements form salts with most oxoacids
The most industrially important Group 1 salts of oxoacids are sodium
carbonate, commonly called soda ash, and sodium hydrogen carbonate,
commonly known as sodium bicarbonate
1. Carbonates The Group 1 carbonates are soluble and decompose to
the oxide when heated strongly

Ch. 11: 6
a. The Group 1 elements form the only soluble carbonates (with
the exception of NH4+ ion), although lithium carbonate is only
sparingly soluble
b. Sodium carbonate
i. Has been produced by the Solvay process for many years.
The overall reaction, which uses the commonly available
feedstocks of NaCL and CaCO3, can be represented by the
equilibrium
ii. 2 NaCl (aq) + CaCO3 (s) <-> Na2CO3 (s) + CaCl2 (aq)
c. Calcium oxide, is produced by the thermal decomposition of
calcium carbonate, is reacted with ammonium chloride to
generate ammonia
i. 2 NH4Cl (s) + CaO (s) -> 2 NH3 (s) + CaCl2 (s) + H2O (l)
d. Ammonia and carbon dioxide (from the thermal decomposition
of CaCO3 and NaHCO3) are passed into a saturated sodium
chloride solution to form a solution of NH4+, Na+, Cl-, and
HCO3- ions
e. The main uses of sodium carbonate are in glass manufacture,
where it is heated with silica to form sodium silicate,
Na2OxSiO2, and as a water softener, where it removes Ca2+
ions as the calcium carbonate, the scale formed in kettles in
hard water areas.
f. Lithium carbonate decomposes when heated above 650 C
i. Li2CO3 (s) -> Li2O (s) + CO2 (g)
2. Hydrogencarbonates Sodium hydrogencarbonate is less soluble than
sodium carbonate and liberates CO2 when heated
a. Sodium hydrogen carbonate is les soluble than sodium
carbonate in water and can be prepared by bubbling carbon
dioxide through a saturated solution of the carbonate
i. Na2CO3 (aq) + Co2 (g) + H2O (l) -> 2NaHCO3 (s)
ii. Reaction provides the basis for the use of sodium
hydrogen carbonate as a fire extinguisher
3. Other oxosalts The nitrates of Group 1 elements are used as
fertilizers and explosives
a. Sodium sulfate, Na2SO4, is very soluble and readily forms
hydrates
b. The major commercial source of sodium sulfate is as a
byproduct of the production of hydrochloric acid from sodium
chloride
i. NaCl (aq) + H2SO4 (aq) -> Na2SO4 (aq) + 2 HCl (aq)
ii. It is also obtained as a byproduct of several other
industrial processes, including flue-gas desulfurization and
the manufacture of rayon
h. 11.13 Solubility and hydration there is a wide variation in the solubility of the
common salts; only Li and Na form hydrated salts
i. All the common slats of the Group 1 elements are soluble in water
ii. The solubilities cover a wide range of values, some of the most soluble being
those for which there is the greatest difference between the radii of the
cation and anion

Ch. 11: 7

i.

j.

iii. Thus, the solubilities of the Li halides increase from the fluoride to the
bromide whereas for Cs the trend is reversed
iv. Not all alkali metal salts occur as their hydrates
1. The lattice enthalpies of hydrates salts are lower than for the
anhydrous salt because the radius of the cation is effectively increased
by the hydration sphere and is further from its surrounding anions
11.14 Solutions in liquid ammonia sodium dissolves in liquid ammonia to give a
solution that is blue when dilute and bronze when concentrated
i. Sodium dissolves in pure, anhydrous liquid ammonia (without hydrogen
evolution) to give solutions that are deep blue when dilute
ii. The color of these metal-ammonia solutions originates from the tail of a
strong absorption band that peaks in the near infrared. The dissolution of
sodium in liquid ammonia to give a very dilute solution is represented by the
equation:
1. Na (s) -> Na + (am) + e- (am)
iii. Concentrated metal-ammonia solutions have a metallic bronze color and
have electrical conductance close to that of a metal
1. These solutions have been described as expanded metals in which e(am) associates witht eh ammoniated cation
iv. The blue meta-ammonia solution are excellent reducing agents
1. The alkali metals also dissolve in ethers and alkylamines to give
solutions with absorption spectra that depend on the identity of the
metal. The dependence on the metal suggests that the spectrum is
associated with the charge transfer from an alkalide ion, M-, to the
solvent
11.16 Coordination compounds the group 1 elements form stable complexes with
polydentate ligands
i. The Group 1 ions, particularly Li+ to K+, are hard Lewis acids. Therefore,
most the complexes they form arise from Coulombic interactions with small,
hard donors, such as those possessing O or N atoms
ii. Monodentate ligands are only weakly bound on account of the weak
Coulombic interactions and lack of significant covalent bonding by these ions.
However, a number of actors (such as the formation of peroxides and
ozonides, rather than oxides, by the heavier alkali metals and the insolubility
of their perchlorates) indicate that the metal become less hard as the group
is desecended
iii. Crown ethers such as 18-crown-6 form complexes with alkali metal ions that
are reasonably stable in nonaqueous solution
iv. Bicyclic cryptand ligands, such as 2.2.1-crypt and 2.2.2 crypt form
complexes with alkali metals that are even more stable, and they can survive
even in aqueous solution
1. These ligands are selective for a particular metal ion, the dominant
factor being the fit between the cation and the cavity in the ligand that
ccomodates it
2. The fit between cation and ligand cavity is through to be responsible
for the transport of Na+ and K+ ions across cell membranes
3. The ions cross the hydrophobic cell membrane by means of embedded
proteins molecules that contain cavities lined with donor atoms

Ch. 11: 8
4. The donor atoms are arranged to form a cavity, the size of which
determines whether Na+ or K+ is bound
5. Such ion channels modulate the Na+/K+ concentration differential
across the cell membrane that is essential for particular functions of
the cell
k. 11.17 Organometallic compounds the organometallic compounds of the Group 1
elements react rapidly with water and are pyrophoric
i. Group 1 elements form a number of organometallic compounds that are
unstable in the presence of water and are pyrophoric in air
ii. Lithium, sodium, and potassium form intensely clored compounds with
aromatic species
1. The oxidation of the metal results in transfer of an electron to the
aromatic system to produce a radical anion, an anion that possesses
an unpaired electron
2. Sodium and potassium alkyls are colorless solids that are in soluble in
organic solvents and, when stable, have fairly high melting
temperatures
3. They are produced by a transmetallation reaction, which involves
breaking a metal-carbon bond and forming a metal carbon bond to a
different metal
4. Organolithium are by far the most important Group 1 organometallic
compounds
a. They are liquids or low melting solids, are the most thermally
stable of the entire group, and are soluble in organic and
nonpolar solvents such as THF. They can be synthesized from an
alkyl halide and lithium metal or by reacting the organic species
with butyllithium, Li(C4H9), commonly abbreviated BuLi
1. BuCl + 2LI -> BuLi + LiCl
2. BuLi + C6H6 -> Li(C6H5) + C4H10