CHM 302 - Inorganic Chemistry III – 3 Units

LECTURE 2
Dr Thompson Izuagie

1
Electronic structure, general properties and
comparative study of Group 1 elements

3
Li
11
Na

19
K
37
Rb
55
Cs

87
Fr
 Outline
 Properties of Group 1 elements
 Atypical (Anomalous) properties of Lithium
 Occurrence and extraction
 Simple compounds
• Hydrides
• Halides
• Hydroxides
• Oxides and Related compounds
• Sulfides, nitrides and carbides
• Compounds of oxoacids
 Coordination compounds of Group 1 elements
 Organometallic compounds of Group 1 elements
 Uses of Group 1 elements and their compounds
 Objectives
• To understand the occurrence and extraction of Group 1
elements

• To understand trends in properties in Group 1 elements

• To become more familiar with the reactions of Group 1

elements and their compounds
• To understand the properties of the Group 1 elements

• To become more familiar with the applications of Group 1

elements and their compounds
 Review of Lecture 1
 An overview of the Periodic Table of the Elements
 Abundance and electronic configuration of Hydrogen
 Isotopes of Hydrogen
 Properties and Reactions of Hydrogen
 Production of Hydrogen
 Uses of Hydrogen
 Hydrogen bonding
 Binary compounds of Hydrogen
 PRE-LECTURE QUESTIONS
 Describe the structures of NaCl and CsI
 With examples, explain the terms (i) Hard and Soft Acids and (ii) Hard and
Soft Bases.
 With equations, explain how the following can be prepared:
 Li2CO3
 NaHCO3
 Na2SO4
 KNO3
 Group 1 Elements – Alkali Metals

Lithium Sodium Potassium Rubidium Caesium Francium

(cesium)
1

3
Li
11
Na

19
K
37
Rb
55
Cs

87
Fr
 All the elements are metals and form simple ionic compounds, most of which
are soluble in water.
 The elements form a limited number of complexes and organometallic
compounds.
 Properties
 All the Group 1 elements are metals with valence electron configuration ns1.
Selected properties of the Group 1 elements
Li Na K Rb Cs
Electronic configuration 1s22s1 [Ne]3s1 [Ar]4s1 [Kr]5s1 [Xe]6s1
Metallic radius/pm 152 186 231 244 262
Ionic radius/pm (coordination 59(4) 102(6) 138(6) 148(6) 174(8)
number)
Ionization energy/kJmol–1 519 494 418 402 376
Standard potential/V –3.04 –2.71 –2.94 –2.92 –3.03
Density/g cm–3 0.53 0.97 0.86 1.53 1.90
Melting point/oC 180 98 64 39 29
∆hydHꝊ (M+)/(kJmol–1) –519 –406 –322 –301 –276
∆subHꝊ/(kJmol–1) 161 109 90 86 79
 They conduct electricity and heat, are soft, and have low melting points that
decrease down the group.
 Their softness and low melting points is because their metallic bonding is
weak because each atom contributes only one electron to the valence
 band.
All the elements adopt a body-centered cubic (bcc) structure and because
that structure-type is not close-packed and their atomic radii are large, they
have low densities.
 Properties
 The chemical properties of the Group 1 elements correlate with the
increasing atomic radius and corresponding decrease in first ionization
energy from Li to Cs.
 This is because the valence shell is increasing distant from the nucleus as
shown below

3
Li Na
11 19
K Rb
37
Cs
55 Fr
87

 The metals readily form alloys among themselves, for example NaK, and
with many other metals, such as sodium/mercury amalgam.
 Flame tests are commonly used for the identification of the presence of the
alkali metals and their compounds due to characteristic electronic transitions.
Li Na K Rb Cs
Crimson yellow red to violet violet blue
 Properties
 The metals are all reactive due to their low first ionization energies.
 They also form M+ ions increasingly readily down the group.
 Their reaction with H2O show this increasing reactivity trend down the group
2 M(s) + 2 H2O(l) → 2 MOH (aq) + H2(g)
Li Na K Rb Cs
Gently vigorously vigorously with ignition explosively explosively
 All the elements must be stored under a hydrocarbon oil to prevent reaction
with atmospheric oxygen, although Li, Na, and K can be handled in air for
short periods; Rb and Cs must be handled under an inert atmosphere at all
times.

Anomalous properties of Lithium

 Li, the lightest member of Group 1 shows some anomalous properties from
its cogeners
 This atypical behavior of Li is because of its small ionic radius and tendency
to exhibit covalent bonding.
 Thus, Li shows some similarity in properties with Mg in Group 2.
 Anomalous properties of Lithium
 This phenomenon is called diagonal relationship and is common in groups
of the periodic table. For Li, the following are observed:
 Lithium can exhibit a high degree of covalent character in its bonding.
This is due to the high polarizing power of the Li + ion associated with
high charge density.
 Lithium forms the normal oxide when burnt in oxygen, whereas other
Group 1 elements form peroxides or superoxides.
 Lithium is the only alkali metal to form a nitride, Li3N, when heated in
nitrogen, and a carbide, Li2C2, when heated with graphite.
 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.
 Lithium forms many stable organometallic compounds.
 Lithium nitrate decomposes directly to the oxide, whereas the other
alkali metals initially form nitrites, MNO2.
 Lithium hydride is stable to heating to 900oC, whereas the other
hydrides decompose on heating above 400oC.
 Occurrence and Extraction

Lithium Sodium Potassium Rubidium Caesium Francium

most abundant occurs as the occurs (cesium) exists
minerals is mineral rock naturally as only in
spodumene, salt (NaCl) potash Rubidium and minute
LiAlSi2O6, and and in salt (K2CO3) and cesium occur as quantity
lepidolite, lakes, carnallite minor constituents and is
approximate seawater and (KCl.MgCl2.6H of mineral radioactiv
formula the residue of O). lepidolite. e.
2
K2Li3Al4Si7O21(F ancient dried-
,OH)3. Li is now up saline
lakes that are
most commonly
often buried
obtained from
underground.
brines as
lithium
carbonate.

 the Group 1 elements can be extracted by ELECTROLYSIS.

 Simple Compounds

Hydrides Halides Hydroxides Oxides and Sulfides, nitrides

related and carbides
Hydrides compounds
 Group 1 elements reacts with H2 to form ionic (saline) hydrides, MH (e.g.
LiH, NaH) 2Na(s) + H2(g) → 2NaH(s)
 The hydrides react violently with water: NaH(s) + H2O(l) → NaOH(aq) + H2(g)
Halides
 Group 1 elements form halides, MX. They can be obtained by direct
combination of the elements or more normally from solutions e.g. reaction of
metal hydroxide or carbonate with hydrohalic acid (HX, X = F, Cl, Br, I).
2 Na(s) + Cl2(g) → 2 NaCl(s)
Hydroxides
 All the hydroxides are white translucent, deliquescent solids. They are
soluble in water and readily absorb water from the atmosphere in an
exothermic reaction. Their solubility makes them a ready source of OH –
ions in the lab and in industry.
 Alkali metal hydroxide solutions rapidly absorb carbon dioxide from the air
and solutions left open to the air rapidly become contaminated with
carbonate.
Oxides and related compounds
 The Group 1 elements react vigorously with oxygen. Only Li reacts directly
with oxygen to give a simple oxide, Li2O. 4 Li(s) + O2(g) → 2
 Na reacts with oxygen to give the peroxide, Na2O2, which contains the
Li2O(s)
peroxide ion, O22–. 2 Na(s) + O2(g) → 2 Na2O2(s)
 The other Group 1 elements form the superoxides, which contain the
paramagnetic superoxide ion, O2–. K(s) + O2(g) → 2 KO2(s)
 All the varieties of oxides are basic and react with water to give the OH – ion
by extraction of H+ from H2O in a Lewis acid-base reaction:
Li2O(s) + H2O → 2 Li+(aq) + 2 OH–(aq)
Na2O2(s) + 2H2O → 2 Na+(aq) + 2OH–(aq) + H2O2(aq)
2 KO2(s) + 2 H2O(l) → 2 K+(aq) + 2 OH–(aq) + H2O2(aq) + O2(g)
Ozonides
 Ozonides, compounds that contain the ozonide, O 3–, exist for all the Group
1 elements. The ozonides of K, Rb, and Cs are obtained by heating the
peroxide or superoxides with ozone. Sodium and lithium ozonides may be
prepared by ion exchange of CsO3 in liquid ammonia. These compounds
are very unstable and explode violently: 2KO3(s) → 2 KO2(s) + O2(g)
Sulfides, nitrides and carbides
 The metals react with sulfur to form compounds with formula M2Sx, (x = 1 - 6).
 Lithium readily forms a nitride, Li3N, when it is heated in N2 (or more slowly at
room temperature), but the other alkali metals do not react with nitrogen gas.
 Only Li reacts directly with carbon to form a carbide (Li2C2) and containing the
dicarbide (acetylide) anion, C22–. Similar carbides are formed by the other
alkali metals by heating them in ethyne.
Compounds of oxoacids
 The Group 1 elements form salts with most oxoacids. The most industrially
important compounds are sodium carbonate (soda ash), and sodium
hydrogen carbonate (sodium bicarbonate).
 The sulphates and nitrates of Group 1 elements are also important, e.g.
Na2SO4 and NaNO3.
Coordination Compounds
 The Group 1 ions, particularly Li+ and K+, are hard Lewis acids. Therefore,
most of the complexes they form arise from Coulombic interactions with small
hard donors, such as those possessing O or N atoms. Their hardness
decreases down the group with increasing ionic radius
Organometallic Compounds
 The lighter group 1 elements form organometallic compounds which are
highly reactive; hydrolysed by water, liberating hydrogen; and pyrophoric
(spontaneously igniting) in air.
 Uses of Group 1 elements and their compounds
 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.
 The low molar mass of lithium (6.94 gmol–1), only 3.3 percent that of lead,
coupled with the strongly negative standard potential of the Li +/Li couple,
make lithium batteries an attractive alternative to lead-acid batteries.
 Lithium carbonate is widely used to treat bipolar conditions (manic
depression) and lithium stearate is widely used lubricant in the automotive
industry.
 The high polarizing power of Li+ means that some complex oxides, such as
LiMO3, M = Nb or Ta, show important nonlinear optical and acosto-optical
effects, and are widely used in mobile communication devices.
 Sodium and potassium are essential for physiological function, and a major
use of NaCl is in flavouring food. Sodium is used in the extraction of rarer
metals, such as Ti from titanium(IV) chloride. Other major uses of NaCl are
road de-icing and production of NaOH for the chloralkali industry.
 Sodium hydroxide is one of the 10 most important industrial chemicals in
terms of annual tonnage produced.
 Uses of Group 1 elements and their compounds
 Other common applications of sodium and its compounds include the use of
the metal in some kinds of street lamps, which produce a distinctive yellow
glow when an electrical discharge is passed through sodium vapour, table
salt, baking soda, and caustic soda (NaOH). Sodium salts and compounds
with ion-exchangeable Na+ are also widely used in water-softening
equipment.
 Potassium hydroxide is used in soap manufacture to make ‘soft’ liquid
soaps. Potassium chloride and sulfate are used as fertilizers; the nitrate
and chlorate are used in fireworks. Potassium bromide has been used as
an anaphrodisiac (a compound that reduces libido). Potassium cyanide
is used in the metal extraction and plating industries to obtain or aid in
the deposition of copper, silver and gold.
 The nitrates of Group 1 elements are used as fertilizers and explosives.
 Rubidium and cesium often substitutes each other in their applications,
which includes glass for fibre optics in the telecommunications
industry, night-vision equipment, and photoelectric cells. The ‘cesium
clock’ (atomic clock) is used for the international standard measure of
time and for the definition of the second and the meter. Cesium salts are
also used as high-density drilling fluids: the high density of the
solutions arises from the high atomic mass of Cs.