Group 2A : Alkaline earth metals

Outline
• Occurrence, extraction
• Isotopes
• Uses
• Physical properties
• The metals
• Compounds :
– Halides
– Oxides
– Hydroxides
– Salts of oxoacids
– Complex ions in aqueous solution
– Complexes with amido or alkoxy ligands
• Diagonal relationships
 Elements

British chemist and inventor French chemist and biologist

Sir Humphry Davy FRS Antoine-Laurent de Lavoisier Marie Curie (1867-1934) French physicist Pierre
(1778 - 1829) (1743 – 1794). Curie (1859 – 1906)
Abundances
 Occurence
• Beryllium occurs principally as the silicate mineral beryl, Be3Al2[Si6O18]
• Magnesium and calcium are the eighth and fifth most abundant
elements, respectively, in the Earth’s crust.
• Mg, the third most abundant in the sea.
• The elements Mg, Ca, Sr and Ba are widely distributed in minerals and
as dissolved salts in seawater; some important minerals are
– dolomite (CaCO3.MgCO3),
– Magnesite (MgCO3),
– olivine ((Mg,Fe)2SiO4),
– carnallite (KCl.MgCl2.6H2O),
– CaCO3 (in the forms of chalk, limestone and marble),
– gypsum (CaSO4.2H2O),
– celestite (SrSO4),
– strontianite (SrCO3) and
– barytes (BaSO4).
• The natural abundances of Be, Sr and Ba are far less than those of Mg
and Ca
 Isotopes
• Be-7 and Be-10 are found as trace
isotopes
• Ca  actually there are 22
isotopes but most of which are
highly radioactive and have half-
lives in the several millisecond to
several day range. The only
notable exception is barium-133
which has a half-life of 10.51 years.
• Sr-89 is a short-lived artificial
radioisotope that is used in the
treatment of bone cancer.
• Sr-90 (half-life = 28.9 years) is a by-
product of nuclear fission and
found in nuclear fallout.
• Ra  All of the 25 isotopes of
radium are radioactive, and while
radium-223, radium-224, and
radium-228 are found in nature as
decay products of either uranium
or thorium, they are only present
in trace amounts.
 Appearance
• Be & Mg  greyish metals
• Ca & Sr soft and silver-coloured
• Malleable, ductile and quite brittle
• In air the shiny surface of each metal quickly
tarnishes
 Extraction - Mg
• Of the group 2 metals, only Mg is
manufactured on a large scale.
– Dolomite is thermally decomposed to a mixture of
MgO and CaO, and MgO is reduced by ferrosilicon
in Ni vessels; Mg is removed by distillation in
vacuo.
– By electrolysis of fused MgCl2 : precipitation from
dolomite  product : Mg(OH)2, neutralization and
evaporation
 Extraction - Be
• 2 ways :
– Reduction of BeF2
(Be is obtained from beryl by first heating with Na2SiF6 
products : BeF2 and Be(OH)2)

– Electrolysis of BeCl2
reaction?
• Be and Mg are possible to be ontained by reducing
their oxides with the carbon
BeO + C  Be + CO
MgO + C  Mg + CO
 Extraction – Ca, Sr, Ba
• Ca  By electrolysis of fused CaCl2 and CaF2
• Sr and Ba 
– by reduction their oxides by Al
– By electrolysis of MCl2 (M = Sr, Ba)
 Properties

atomic properties

12/20/2018 physical properties

11
Group 1A
Group 2A
 Discuss about their …
- (comparing with the alkali metals-group 1A) -

• Atomic size  increasing down the group; smaller than alkali metal
• Ionic size  increasing down the group; smaller than alkali metal
• density property  decreases slightly upto Ca after which it increases; more denser,
heavier and harder than alkali metal
• melting point, boiling point  higher than alkali metals
• Ionization energy  IE1 decreasing down the group; higher than alkali metals, IE2
decreasing down the group; higher than alkali metals
• Electropositive  increasing down the group; less electropositive character than alkali
metals
• Electronegativity  decreasing down the group; higher than alkali metals
• Oxidation number/valency  hint : higher degree of hydration ; electron configuration

• Reducing character  standard oxidation potential increasing down the group; less
powerful than alkali metals
 Flame tests
• Ca = orange-red but pale green when viewed through blue glass
• Sr = crimson but violet through blue glass
• Ba = apple green
 Uses - Be
• Light, strong metal, good conductor
of heat and electricity
• To add strength to other metals
without adding much weight
• Beryllium copper—used to make
tools which are to be used in
hazardous environment,-
productions of bullets, precision
measurement devices and in
aerospace
• Very costly, £ 10,000 /kg
 Mg
• Moderate light stregth to weight ratio
• Good conductor of heat and electricity
• Similar with Be, Mg is used in alloys to add
strength without adding much weight
• Mg-Al-Cu (duralumin)  used in aircraft, car,
bike frames and small boats
• Alloys with rare earth minerals, it becomes
temperature resistant to build car engines
• Other Mg alloys are used in the production of
household material
• Mg is used as flares and distress signals (guess
why?)
• Mg bombs were dropped on Germany during
WWII
• MgO  used in refractory lining material
• MgSO4 is used as epson salts (artificial snow),
fertilizers
• Mg(OH)2 as an antacid
• As a constituent od chlorophyll
Ca
• Low strength to weight ratio
• Good conductor of heat and electricity
• Most Ca found in CaCO3
• Found in human body (bones, teeth, etc)
• Used in toothpaste, vitamins, antacid, etc
• Gypsum (CaSO4.2H2O)
• CaCO3  in limestone, chalk,
• marble is very important in the construction
industry (as decorative stone)
• Lime is used in paper making, food, cosmetic,
pharmaceutical, toothpaste, chewing gum, and
vitamins. It is also used for treating industrial
waste.
• CaH2  used as irreversible drying agent
• Other drying agents  MgSO4, CaCO4, CaCl2,
Na2SO4, K2CO3
• CaCl2  de-icer
 Sr
• Good conductor of
heat and electricity
• Used in fireworks and
flares
• Used as a glas
additive
 Ba
• BaSO4  as lubricating mud in drilling
operations
• Alloys : Ba-Ca-Pb
• Barium meal  relatively opaque to X-rays
and shows particulary well on X-ray
photographs
 Ra
• Used in medical field
• as cancer treatment, and as a tracer for
medical imaging, although because safer
radioactive elements have been discovered it
is rarely used any more.
Reactivity

Reactivity
increases

Size of the atom

increases
• The metals reduce O2 to form oxides:
Δ
– 2M(s) + O2(g) → 2MO(s) (M = Be, Mg or Ca)
– 2M + O2  MO2 (M = Sr, Ba)
• The larger metals reduce water to form H2 gas:
– 2M(s) + H2O(l) → 2M2+(aq) + 2OH-(aq) + H2(g) (M = Ca, Sr, Ba)
• The metals reduce halogens to form ionic halides:
Δ
– M(s) + X2 → MX2(s) [X = F (not with Be), Cl, Br, I]
• Most of the elements reduce H2 to form ionic hydrides:
– M(s) + H2(g) → MH2 (s) (M = all except Be)

• The elements reduce nitrogen to form ionic nitrides:

Δ
– 3M(s) + N2(g) → M3N2(s)

• Except for BeO, the element oxides are basic:

– MO(s) + H2O(l) → M2+(aq) + 2OH-(aq)
• The elements reduce nitrogen to form ionic nitrides:
Δ
– 3M(s) + N2(g) → M3N2(s)

• Except for BeO, the element oxides are basic:

– MO(s) + H2O(l) → M2+(aq) + 2OH-(aq)

• All carbonates undergo thermal decomposition:

Δ
MCO3(s) MO(s) + CO2(g)

• Reacting with sulfur

Δ
– 8M + S8 8MS

• Reacting with C
Δ
– 2Be(s) + C(s) → Be2C(s)
Δ
– M(s) + 2C(s) → MC2(s) (contains )
• Mg2C3contains the linear [C3]4-, isoelectronic
with CO2 formed by heating MgC2 or by
reaction of Mg dust with pentane vapour at
950 K

• Reaction of Mg2C with water produces

MeC≡CH
 Compounds
• Halides
• Oxides
• Hydroxides
• Salts of oxoacids
• Complex ions in aqueous solution
• Complexes with amido or alkoxy ligands
 Halides
• Beryllium halides  covalent; others are ionic
• BeF2  very soluble in water
• BeX2  colourless, deliquescent crystals
• BeCl2 But…

Linear  dimer  polymer

Planar  ……  ….
Explain why?
• A deliquescent substance absorbs water from
the surrounding air and eventually forms a
liquid.

• A hygroscopic solid absorbs water from the

surrounding air but does not become a liquid.
 Halides of Mg, Ca, Sr and Ba
• MgF2, CaF2, SrF2 and BaF2  ionic, high
melting points, sparingly soluble in water, the
solubility increasing slightly with increasing
cation size
Inverse polarization

Quasilinear  a species for which the calculated energy difference between linear and bent structures
(with a change in angle of >208) is less than 4 kJ mol-1.
 The reason of the bent of MX2 molecules

• Inverse polarization
• Participation of d atomic orbitals
• MgX2 (X = Cl, Br, I)
– its hydrate salts will partially hydrolyzed when heated
– Its anhydrous salts can be prepared by dehydration of
hydrated salts  hygroscopic
• CaCl2  by-product of solvay process

Crystalline complexes in
pyridenine, THF 
 Oxides
• Have general formula MO and are basic
• BeO  insoluble white solid;
• prepared by thermal decomposition of corresponding
carbonate or hydroxides releasing CO2 gas
• They have high lattice
energies and melting points
• MgO is suitable as a
refractory material  why?
• Refractory materials are
suitable for use in furnace
linings; such a material has a
high melting point, low
electrical conductivity and
high thermal conductivity,
and is chemically inert at the
high operating temperatures
of the furnace.
• The action of water on MgO slowly converts it to Mg(OH)2
which is sparingly soluble.
• Oxides of Ca, Sr and Ba react rapidly and exothermically with
water, and absorb CO2 from the atmosphere.

• The conversion of CaO to calcium carbide and its subsequent

hydrolysis is industrially important

• BeO and MgO insoluble and sparingly soluble in water 

why?
• BeO dissolves in acid and alkali give salts
• MO2  M = Mg, Ca, Sr and Ba; the stability (decomposition
reaction) increases with the size of M2+ ion. r+ increases  ∆latticeHo
(MO,s) is always more negative than ∆latticeHo (MO2,s)

• BeO2  failed to be prepared

• strong oxidizing agents
• MgO2  prepared by reacting MgCO3 or MgO with H2O2
• CaO2  prepared by dehydration of CaO2.8H2O which prepared
from

• SrO2 and BaO2  SrO (or BaO) + O2

• Reactions peroxides with acids  products: hydrogen peroxides
 Lattice energy of alkaline metals
oxides
• The lattice energies of SrO and SrO2 are -3220 and -3037
kJ/mol
• Why does SrO2 have more negative lattice energy than SrO?
(estimate from : Kapustinskii equation)
 Hydroxides
• The stabilities of M(OH)2 (M = Mg, Ca, Sr, Ba)
increase down the group

• Mg(OH)2  weak base

• Ca(OH)2, Sr(OH)2, Ba(OH)2  strong base
• An oxoacid is an acid that
– contains oxygen
Oxoacids
– contains at least one
other element
– has at least one hydrogen
atom bound to oxygen
– forms an ion by the loss
of one or more protons.
• BeCO3+H2O  [Be(H2O)4]2+
• Basic beryllium acetate
 Hard Water
• Rainwater is not chemically pure water.
– Contains dissolved atmospheric gases.
– Once on the ground it may pick up a few to about
1000 ppm of dissolved substances.
– If the water contains ions capable of forming a
precipitate we say that the water is hard.
• Hardness may be permanent or temporary.
 Temporary Hard Water
• Contains HCO3- ion.
– When heated gives CO32-, CO2
and H2O.
– The CO32- reacts with
multivalent ions to form
precipitates.
(for example CaCO3, MgCO3)
• Soften water by precipitating the
multivalent ions using slaked lime.
 Permanent Hard Water
• Contains significant concentrations of anions other than
carbonate.
– For example SO42-, HSO4-.
– Usually soften by precipitating the Ca2+ and Mg2+ using
sodium carbonate leaving sodium salts in solution.

• Bathtub ring is caused by

salts of Mg2+ and Ca2+ of
palmitic acid
(a common soluble soap).
 Water Softening
• Ion exchange.
– Undesirable
cations, Mg2+ Ca2+
and Fe3+ are
changed for ions
that are not as
undesirable, ex.
Na+.
– Resins or zeolites.

Prentice-Hall © 2002
 Hard water
• Contains Mg2+ and Ca2+
• Temporary hardness
– The presence of hydrogencarbonate salts and can be
overcome by boiling or by adding appropriate amount of
Ca(OH)2

• Permanent hardness
– Caused by other Mg2+ and Ca2+ salts (e.g. sulfates)
• Water softening  by passing the hard water through a
cation-exchange resin, zeolite, etc
• A hydrate X.nH2O in which n =1/2 is called a hemihydrate; if
n = 1 1/2, it is a sesquihydrate. (e.g. CaSO4.½H2O)
 Complex ions
- complex with water ligands -

• Solutions of beryllium salts

are acidic
• Aqua species of Mg2+, Ca2+,
Sr2+ and Ba2+
– [Mg (H2O)6]2+
– [Ca (H2O)6]2+
 Complex ions
- complex with ligands other than water -

• With ligands : [EDTA]4- and [P3O10]5-

• Macroligands : crown ethers and cryptands, form stable
complexes with Mg2+, Ca2+, Sr2+ and Ba2+
• the stability constants for complexation with cryptand-222
(cavity radius 140 pm) in water follow the sequence Ba2+ > Sr2+
>> Ca2+ > Mg2+
Complexes with amido or alkoxy ligands
 Diagonal relationship
- Li and Mg; Be and Al -
Li and Mg
Be and Al
• Others… will be dicussed in elements of group
13
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals

Much of the important chemistry of the alkali and alkaline earth metals can be
understood on the basis of their low ionization enthalpies (or electronegativities)
and the favourability of ionic bonding.
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
The s-block elements lose their DH°ie increases
electrons more easily than the

DH°ie decreases
other element in the main group so
they are usually strong reducing
agents and most tend to form ionic
compounds. The stabilization that
is provided by the crystal lattice (or
hydration) energy of the salts they
make helps to favour many
reactions.
One of the stranger consequences of the low ionization enthalpy is observed when
some of the group 1 metals are dissolved in appropriate solvents, such as liquid
ammonia:
E.g.: Na(s) (dissolved in NH3 (l))  Na+(am) + e-(am)
At low concentration this is a blue solution that contains
solvated electrons! If the reaction warms up or is catalyzed,
the free electron reacts with the solvent to reduce some of the
protons in the solvent to produce
Na+(am) +hydrogen gas:
2 (NH2)-(am) + H2(g)
X-ray crystal
This demonstrates the reducing ability of the alkali metals structure of
and is a very common and useful property of these [Cs+L2][e-]
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
The s-block metals are used as reducing agents for an immense number of different
types of compounds.
Reactions of the elements with water:
Group 1: M(s) + H2O(l)  M+(aq) + (OH)-(aq) + ½ H2(g)

Group 2: M(s) + 2 H2O(l)  M+2(aq) + 2 (OH)-(aq) + H2(g)

These reactions are very exothermic and increase in violence from the lightest to the
heaviest elements in the group (enough to ignite the H2 for the heavier elements).
The non-reversible nature of this reaction means that such metals are very useful for
drying many kinds of solvents. More generally:
Group 1: M(s) + HOR  M+ + (OR)- + ½ H2(g)

Group 2: M(s) + 2 HOR  M+2 + 2 (OR)- + H2(g)

These reactions make metal alkoxides that are very useful for the synthesis of other
products using metathesis reactions. Metathesis indicates that the reagents
exchange ligands with one another. Such reactions are especially favourable when it
produces a metal halide because of the large exothermicity provided by the lattice or
e.g.’s
hydration energies. MOR + ClPR’2  MCl + R’2POR
MNR2 + ClSiR’3  MCl + R’3SiNR2
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
One of the most important discoveries in synthetic chemistry
was made by Victor Grignard (Nobel Prize 1912) following the
initial work of others. He showed that the reaction of Mg with
organic iodides (RI, later applied to other halides) results in the
insertion of the Mg into the R-I bond. This provides a reagent of
the form R-Mg-I that can be used in nucleophilic or metathesis
Mg(s) + R-I  R-Mg-I
reactions to make new carbon-carbon bonds.
R-Mg-I + I-R  R-R + MgI2
O O
Mg Br + C C + MgBr
O O
Cp*2Mg
Analogous and more reactive reagents can be made with Li and Na.
2 Li(s) + R-X  R-Li + Li-X (X = halide)

R-Li + X-R’  R-R’ + Li-X

Such compounds were among the first that were recognized to
contain bonds between metals and carbon. These were thus
some of the initial examples of organometallic chemistry (one of
(Cp*Na•THF)
the most studied branches of inorganic chemistry today).
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
The s-block metal hydrides are also very useful compounds that can usually
be made by the reaction of the metal with H2(g); this does not work for BeH2 -
you can use a Born-Haber cycle to figure out why. The H atoms are hydrides
(H-), which gives them a totally different kind of chemistry than protons (H+).
All of the s-block hydrides are ionic except for LiH, BeH2 and MgH2, which
Group 1: M(s) + ½
have significant H2(g) character.
covalent MH (s)
H Be H

Group 2: M(s) + H2(g)  MH2(s)

Gas phase

The coordination polymer solid state structure of BeH2 is similar to that of BeCl2

These reagents also react with water in a very exothermic fashion to make gaseous
H2. The non-reversible nature of this reaction means that such metal hydrides
(especially CaH2) are also very useful for drying many kinds of solvents.

More importantly, the group 1 and 2 metal hydrides are excellent reagents for putting
H atoms onto other elements by metathesis reactions:
e.g.’s 3 LiH + PCl3  PH3 + 3 LiCl

2 LiH + BeCl2  BeH2 + 2 LiCl

4 LiH + AlCl3  Li[AlH4] + 3 LiCl

 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
Because of their low electronegativities, most of the s-block metal halide or
chalcogenide compounds are salts with ionic structures. The lattice (or hydration)
energies of such compounds are often used to drive reactions to completion.
 22-2 Group 2: The Alkaline Earth
Metals

Emerald is based on the mineral beryl:

3BeO·Al2O3 ·6SiO2

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 66 of 47

 Group 2
• Principle forms:
– carbonates, sulfates and silicates
• Oxides and hydroxides only sparingly soluble.
– Basic or “alkaline”
• Compounds do not decompose on heating.
– Therefore named “earths”
• Heavier elements compounds are more
reactive and are similar to Group I (also in
other respects).
Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 67 of 47
 Table 22.4 Some Properties of the
Group 2 (Alkaline Earth) Metals

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 68 of 47

 Beryllium
• Unreactive toward air and water.
• BeO does not react with water, all others from
hydroxides.
• Be and BeO dissolve in strongly basic solutions
to form the BeO22- ion (therefore are acidic).
• BeCl2 and BeF2 melts are poor conductors:
– Therefore they are covalent rather than ionic
solids.

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 69 of 47

 Beryllium Chloride

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 70 of 47

 Dow Process for Production of Mg

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 71 of 47

 Electrolysis of Molten MgCl2

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 72 of 47

 Decomposition of CaCO3 (lime)
In the lime kiln:

CaCO3 →ΔCaO + CO2

burnt lime
or
quicklime

In the lime slaker:

CaO + H2O → Ca(OH)2

slaked lime

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 73 of 47

 Stalactites and Stalagmites

CO2 + H2O → H3O+ + HCO3-

Ka = 4.4 10-7

HCO3- + H2O → H3O+ + CO32-

Ka = 4.7 10-11

CaCO3(s) + H2O(l) + CO2(g) → Ca(HCO3)2(aq)

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 74 of 47

 Other Compounds
• Gypsum, CaSO4·2H2O:
– Plaster of paris CaSO4·½H2O by heating bypsum.
– Used in drywall.
• BaSO4 used in X-ray imaging .
• Slaked lime used in mortar:
– CaO absorbs water from the cement to form
Ca(OH)2 which subsequently reacts with CO2 to
form CaCO3.

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 75 of 47

 22-3 Ions in Natural Waters: Hard
Water
• Rainwater is not chemically pure water.
– Contains dissolved atmospheric gases.
– Once on the ground it may pick up a few to about
1000 ppm of dissolved substances.
– If the water contains ions capable of forming a
precipitate we say that the water is hard.
• Hardness may be permanent or temporary.

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 76 of 47

 Temporary Hard Water
• Contains HCO3- ion.
– When heated gives CO32-,
CO2 and H2O.
– The CO32- reacts with
multivalent ions to form
precipitates.
(for example CaCO3,
MgCO3)
• Soften water by
precipitating the
multivalent ions using
Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 77 of 47
 Permanent Hard Water
• Contains significant concentrations of
anions other than carbonate.
– For example SO42-, HSO4-.
– Usually soften by precipitating the Ca2+ and
Mg2+ using sodium carbonate leaving sodium
salts in solution.

• Bathtub ring is caused by

salts of Mg2+ and Ca2+ of
palmitic acid
(a common soluble soap).
Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 78 of 47
 Water Softening
• Ion exchange.
– Undesirable
cations, Mg2+ Ca2+
and Fe3+ are
changed for ions
that are not as
undesirable, ex.
Na+.
– Resins or zeolites.

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 79 of 47

 Deionizing
• Instead of replacing cations with Na+, they are
replaced with H+.
• Then the anions are replaced with OH-.

H+(aq) + OH-(aq) → H2O(l)

Prentice-Hall © 2002 General Chemistry: Chapter 22 Slide 80 of 47

 Group 2A(2): The Alkaline Earth Metals

• The oxides of Group 2A(2) elements form basic solutions

and melt at extremely high temperatures.
• Group 2A(2) elements have higher ionization energies
than Group 1A(1) elements
– due to their higher effective nuclear charge and smaller size.

• Group 2A(2) elements are strong reducing agents.

 Group 2A(2): The Alkaline Earth Metals Family Portrait

KEY ATOMIC PROPERTIES, PHYSICAL PROPERTIES, AND REACTIONS

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Figure 14.5 Three diagonal relationships in the periodic table.
 Group 1: The Alkali Metals:

Li, Na, K, Rb, Cs (H&S Chapter 10).

Li+ Na+ K+

1Å

Rb+ Cs+
The alkali metals are very reactive, and react
violently with water to give the metal hydroxide and
H2 gas. The standard reduction potentials are very
negative in accord with this:

Li+ (aq) + e = Li(s) Eo = -3.04 V

Li (s) + H2O = Li+(aq) + OH- (aq) + H2(g)

Because of their low charge and large size, the ability

of the group 1 metal ions to form complexes in
solution is limited. Thus, the metal hydroxides are
completely ionized to give metal cations and
hydroxide ions. They are therefore strong bases.
The coordination numbers increase with increasing metal
ion size:
Metal ion: Li+ Na+ K+ Rb+ Cs+
Ionic radius (Å): 0.76 1.02 1.38 1.52 1.67
Coord. No.: 4-6 6-7 6-8 8-9 8-9

Figure 3. A four coordinate complex

of Li+ is seen (left) with
four THF (tetrahydrofuran)
molecules attached to
the Li+.
 Crown ethers and Cryptands
The low electronegativity of the
alkali metals means that they are
very hard in the HSAB sense, and
their chemistry is largely that of
being bound to the hard oxygen
donor atoms, as seen for [Li(THF)4]+
above. The most important aspect
of their chemistry is their ability to
bind to crown ethers and cryptands.
The crown ethers were discovered
in 1967 by Charles Pedersen when
he was working at DuPont. These
are cyclic polyethers called macrocycles
(‘large cycles’). Some examples of
crown ethers and cryptands are
shown below (Figure 4):
 Crown ethers and Cryptands
Figure 4. Cryptands O
and crown ethers. O O
O
O O O O O O O O

O O O O O O O O
O O O
18-crown-6 15-crown-5 12-crown-4 24-crown-8
O
O O
O O O O O O

N O O N N O N N O N N O O N

O O O O O O O

cryptand-222 cryptand-221 cryptand-211 cryptand-322

The important aspect of the crown ethers was that these
complexed alkali metal cations in solution. Up until that time
it was considered that the alkali metal ions had very little
ability to form complexes in aqueous solution. This was
important, because ion channels in cell membranes allowed
K+ and Na+ to pass through selectively, and the properties of
the crown ethers suggested how this might be achieved. The
striking feature of crown ethers was their ability to complex
alkali metal ions selectively on the basis of their size.

Figure 5. The D3d

conformer of the free
18-crown-6 ligand,
and its complex with
K+, showing how well
the K+ cation fits
into the cavity
of the ligand.
Thus, the log K1 values for 18-crown-6 with alkali metal ions
vary in aqueous solution as shown below. The diagram shows
that 18-crown-6 has a definite preference for the K+ ion. This
can be understood by looking at a space-filling drawing
(Figure 5) of 18-crown-6, and how the K+ cation can fit into the
cavity in the ligand.

Figure 6. Variation in
log K1 for 18-crown-6
complexes as a function
of metal ion radius for
alkali metal ions.
 Cryptands:

• The cryptands were developed by

Jean-Marie Lehn, and have a
three-dimensional cavity. The
complexes they form with group
1 and 2 metal ions are
thermodynamically much more
stable than those formed by
crown ethers.

O O

O O
N N

O O
Cryptand-2,2,2
K+ cryptand-2,2,2 complex:

K+

cryptand
 The Alkali Earth Metals (group 2). (H&S
Chapter 11)
The alkali earth metal ions resemble the alkali metal ions in
having a low electronegativity, and being very hard in the
HSAB classification. The big difference, though, is their charge,
which makes them stronger Lewis acids. The effect of charge
on log K1 for hard metal ions with EDTA, all having an ionic
radius of about 1.0 Å, makes this point (see next slide for Ca
EDTA complex):

Metal ion: Na+ Ca2+ La3+ Th4+

Ionic radius (Å): 1.02 1.00 1.03 0.94

log K1 (EDTA): 1.86 10.65 15.36 23.2
 We thus find that the metal ions in Group 2 are much better
at complexing with ligands than are those in Group 1. Being
hard, complexing of Group 2 cations is confined largely to
oxygen donors, and to nitrogens, more so where the nitrogen
donors are part of a ligand that also has some oxygen donors,
such as in EDTA.

H2O OH2
O O
O O
O O
Ca
O O
N N

[Ca(EDTA)(H 2O)2]2-
EDTA
The alkali earth metal ions Ca2+, and particularly Sr2+,
and Ba2+ are large enough to fit well into the cavities of
crown ethers and cryptands, and actually form more
stable complexes than large alkali metal ions. Thus, we
can compare log K1 values with some crown ethers and
cryptands for Ba2+ and K+, which are almost identical in
size:

Ligand: 18-crown-6 15-crown-5 cryptand-222

log K1(K+): 2.05 0.75 5.5

log K1(Ba2+): 3.89 1.71 9.6

Thus, even with these ligands, the charge on the metal

ion has an effect on complex stability.
 Group 3. B, Al, Ga, In, Tl.
(H&S Chapter 12).
In group 3 the electronegativity of the metals is getting a bit
higher, and the heavier metals Ga, In, and Tl are actually post-
transition elements (they are close to Au), so have much
higher electronegativity and a very different chemistry from B
and Al. They form trivalent cations that form very strong
complexes:
Metal ion: Al(III) Ga(III) In(III) Tl(III)
ionic radius (Å): 0.58 0.62 0.80 0.89
log K1(OH)- 9.0 11.4 10.6 13.4
log K1(EDTA): 16.4 20.4 25.0 35.3

increasing electronegativity
The Tl(III) ion is stabilized by complexation with
ligands, and is an extremely powerful Lewis acid.
Because of its high electronegativity, Tl(III) is
classified as soft in HSAB, as reflected by its log K1
values with halide ions:

Metal ion:Al3+ Ga3+ In3+ Tl3+

log K1 (F-): 6.42 4.47 3.74 2.6

log K1 (Cl-): -1.0 0.01 2.32 6.72
HARD ← → SOFT
 The inert pair effect in Thallium(I):
For the first time we have to position of
consider the inert pair effect. Thus, lone pair
for Tl, the most stable oxidation
state is not Tl(III) but Tl(I). The Tl(I)
ion has an ionic radius of 1.50 Å,
and so resembles K+ and Rb+ to
some extent in its chemistry. It does
have some tendency towards
covalence (it is soft), and so forms
many complexes where it is bound
to soft donors such as S. At right is
seen the complex of Tl(I) with the
sulfur-donor macrocycle 9-ane-S3. Figure 8. Structure of the
Tl(I) complex with the
S-donor macrocycle
9-ane-S3.
 Boron
Boron is very different in its chemistry from the other members
of the group. While they all have preferred coordination
numbers of 6, with occasional higher coordination numbers of 7
or 8, boron always has a coordination number of four or less.
Thus, B(III) in aqueous solution exists as B(OH)3(aq) at lower pH,
and is too acidic to ever be protonated to yield a B3+ (aq) ion. At
higher pH (9.1) a water coordinated to B(OH)3 (aq) ionizes to
yield the borate anion:

B(OH)3.OH2(aq) = [B(OH)4]- (aq) + H+ (aq) pKa = 9.1

“boric acid” borate anion

This behavior is readily understood in terms of the small size

(ionic radius = 0.11 Å) and high charge on B(III).
B(III) forms compounds of considerable covalency, with
electronegativity = 2.0, and forms a reasonably stable hydride,
as in Li[BH4], lithium borohydride. Here we have a Td [BH4]-
anion, which is used in organic chemistry as a mild reductant.
The chemistry of the boranes, those compounds involving
boron and hydrogen, is enormous. The structure of [B2H6] is
shown below.

Figure 9. B2H6,
showing the
bridging H-atoms,
which donate
electron density
to the adjacent
B atom.
 Group 4. C, Si, Ge, Sn, Pb. (H&S Chapter 14).

Here the group valency is four. The electronegativity

of the elements has risen quite high, with the C atom
having an electronegativity of 2.5. None of these
elements forms an M4+ cation in solution. Carbon
forms the CO32- and HCO3- anions at higher pH, and
at lower pH (<6) breaks up to form CO2(g). Si and Ge
form many compounds with a coordination number
of four, such as SiCl4 or GeCl4. They also readily
expand their coordination numbers to six, as in
complexes such as [SiF6]2- and [GeF6]2-.
 The inert pair effect in Pb(II) and Sn(II):
The high electronegativity of these elements leads to a
strong inert pair in Sn and Pb. For Sn both the Sn(IV)
abd Sn(II) state are relatively stable. For Pb, the Pb(IV)
state is of rather low stability. Important Pb(IV)
compounds are PbO2, which is important in the
lead/acid battery, and Pb(CH2CH3)4 (tetraethyl lead),
which used to be added to gasoline to prevent ‘knock’
(premature ignition on compression). The lead/acid
battery works on the cell:

PbO2(s) + 4 H+(aq) + Pb(s) =

2 Pb2+(aq) + 2 H2O Eo = +1.2 V
The Pb(II) and Sn(II) ions display a sterically active inert pair,
which means that in structures of the complexes of these cations,
there is usually a gap in the coordination geometry which is
occupied by the lone pair. This resembles the structure of NH3 as
predicted by VSEPR, where the structure is derived from a
tetrahedron, with one site occupied by the lone pair. This is seen
in the structures below of the [SnCl3]- and the [Pb(C6H5)3]- anions:

lone pair Pb
phenyl
group
Sn

Cl
Cl
Cl

[SnCl3]- [Pb(C6H5)3]-