CHM 302 - Inorganic Chemistry III – 3 Units

LECTURE 3
Dr Thompson Izuagie

Electronic structure, general properties and

comparative study of Group 2 elements
2
4
Be

Mg
12

20
Ca
38
Sr
56
Ba

88
Ra
 PRE-LECTURE QUESTIONS
 Describe the structures of MgCl2
 With equations, explain how the following can be prepared:
 BaCO3
 Ca(HCO3)2
 CaSO4
 Mg(NO3)2
 Review of Lecture 2
 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
 Outline
 Properties of Group 2 elements
 Atypical (Anomalous) properties of Berylium
 Occurrence and extraction
 Simple compounds
• Hydrides
• Halides
• Hydroxides
• Oxides and Related compounds
• Sulfides, nitrides and carbides
• Compounds of oxoacids
 Coordination compounds of Group 2 elements
 Organometallic compounds of Group 2 elements
 Uses of Group 2 elements and their compounds
 Objectives
• To understand the occurrence and extraction of Group 2
elements

• To understand trends in properties in Group 2 elements

• To become more familiar with the reactions of Group 2

elements and their compounds
• To understand the properties of the Group 2 elements

• To become more familiar with the applications of Group 2

elements and their compounds
 Group 2 Elements – Alkaline Earth Metals

Beryllium Magnesium Calcium Strontium Barium Radium

2
4
Be

Mg
12

20
Ca
38
Sr
56
Ba

88
Ra

 All the elements are silvery white metals and their compounds are usually
ionic.
 The elements have a ground-state valence-electronic configuration of ns2
 The elements are denser, harder and less reactive than the elements of
Group 1 but are still more reactive than many typical metals.
 Properties
 All the elements occur as M(II) or M2+ in their simple compounds, which is
consistent with their ns2 valence-electron configuration.
 The greater mechanical hardness and higher melting points of the Group 2
compared with the Group 1 elements indicates an increase in the strength
of metallic bonding on going from Group 1 to Group 2, which is due to the
increased number of electrons available.
 The most important factors influencing the chemical properties of the group
2 elements are their ionization energies and ionic radii.
Selected properties of the Group 3 elements
Be Mg Ca Sr Ba Ra
Electronic configuration 1s22s2 [Ne]3s2 [Ar]4s2 [Kr]5s2 [Xe]6s2 [Rn]7s2
Metallic radius/pm 112 150 197 215 217 220
Ionic radius, r (M2+/pm 27(4) 72(6) 100(6) 126(8) 142(8) 170(12)
(coordination number)
First ionization 900 736 590 548 502 510
energy/kJmol–1
EꝊ(M2+, M)/V –1.85 –2.38 –2.87 –2.89 –2.90 –2.92
Density, ρ/g cm–3 1.85 1.74 1.54 2.62 3.51 5.00
Melting point/oC 1280 650 850 768 714 700
∆hydHꝊ (M2+)/(kJmol–1) –2500 –1920 –1650 –1480 –1360 –
∆subHꝊ/(kJmol–1) 321 150 193 164 176 130
 Properties
 The atomic radii of the Group 2 elements are smaller than those of Group 1.
This reduction between the groups is responsible for their higher densities
and ionization energies.
 This decrease in ionization energy down the group reflects trend in increase
reactivity. Thus, whereas calcium, strontium, barium, and radium react
readily with cold water, magnesium reacts only with hot water:
M(s) + 2 H2O(l) → M(OH)2(aq) + H2(g)

 As with the Group 1 elements, flame tests are commonly used for the
identification of the presence of the heavier Group 2 elements and their
compounds:
Ca Sr Ba Ra
Orange-red Crimson Yellowish-green Deep red
 Anomalous behaviour of Beryllium
 Beryllium exhibits a diagonal relationship with aluminum and its compounds
show a high level of covalency.
 This is because of the small size of Be2+ (ionic radius 27 pm) and its
consequent high charge density and polarizing powder.
 Some anomalous behaviour of Be, the 1st member of the Group 2 elements
(which are similar to the properties of Al, the 2nd member of Group 13) are:
• Be forms covalent hydrides and halides; the analogous compounds of
the other Group 2 elements are predominantly ionic.
• The oxide of Be is amphoteric whereas the oxides of the rest of the
Group 2 elements are basic.
• In the presence of excess OH– ions, Be forms [Be(OH)4]2– like [Al(OH)4]–,
formed by Al; no equivalent chemistry is observed for Mg.
• Be forms carbide that contain the C4– ion and produce methane on
reaction with water; the other Group 2 carbides contain the C 22– ion and
produce ethyne on reaction with water.
 Occurrence and Extraction

Beryllium Magnesium Calcium Strontium Barium Radium

occurs naturally is the 8th most is the 5th most extracted extracted All
as the abundant element abundant element by by isotopes
semiprecious in the Earth’s crust. in the Earth’s crust electrolysis electrolysis are
mineral beryl, Occurs naturally in and occurs widely of molten of molten radioacti
Be3Al2(SiO3)6 dolomite, as limestone, SrCl2 or by BaCl2 ve.
CaCO3.MgCO3, CaCO3. Calcium is reduction
and magnesite, extracted by of SrO with
MgCO3, and is the electrolysis of the Al.
3rd most abundant molten chloride
element dissolved which is itself
in sea water (after obtained as a by-
Na and Cl), from product of the
which it is Solvay process for
commercially the production of
extracted. sodium carbonate.
 Magnesium is the only Group 2 element extracted on an industrial scale;
 Magnesium, calcium, strontium, and barium can be extracted from the
molten chloride.
 Simple Compounds

Hydrides Halides Hydroxides Oxides and Sulfides, nitrides and

related carbides
compounds
Hydrides
 Group 2 elements except Be react with H2 to form ionic (saline) hydrides, MH2
Mg(s) + H2(g) → MgH2(s)
 The hydrides of heavier elements react violently with water to produce H 2:
MgH2(s) + 2H2O(l) → Mg(OH)2(aq) + 2H2(g)
Halides
 The halides of beryllium are covalent.
 All the fluorides, except BeF2, are insoluble in water; all other halides are
soluble.
 CaF2 is the most important fluoride, which exist as the mineral fluorite or
fluorspar, the only large-scale source of fluorine.
 The anhydrous halides of magnesium can be prepared by direct
combination of the elements or, for strontium and barium, dehydration of
the hydrated halide salts;
 All the chlorides are deliquescent and form hydrates; they have lower
melting points than the fluorides. Magnesium chloride is the most important
chloride for industry and applications.
 Both MgCl2 and CaCl2 are used to de-ice roads, where they are more
effective than NaCl for two reasons. (1) dissolution is highly exothermic (2)
lower freezing point.
 Radium has the least soluble halides
Hydroxides
 The hydroxides of all except Be are formed by reaction of the oxides with
water.
 Beryllium hydroxide, Be(OH)2, is amphoteric. The hydroxides become
apparently more basic down the group because their solubility increases
from Mg(OH)2 to Ba(OH)2.
Oxides and related compounds
 All the Group 2 elements form normal oxides by reaction with oxygen,
except Ba, which forms the peroxide; 2Ca(s) + O2(g) → 2 CaO(s)
Ba(s) + O2(g) → BaO2(s)
 The oxides are more commonly obtained by decomposition of the carbonates:
MCO3(s) → MO(s) + CO2(g)
 All the peroxides decompose to the oxides, their stabilities increasing down
the group. 2MgO2 → 2 MgO (s) + O2(g)
 The oxides of the elements from Mg to Ba all adopt the rock-salt structure.
 Their melting points decrease down the group and MgO which melts at
2852oC is used as a refractory lining in industrial furnaces.
 MgO is used as an electrically insulating material around the heating
elements of domestic appliances and in electrical cables because like BeO,
it has a high thermal conductivity coupled with a low electrical conductivity.
This combination of properties leads to its use as an electrically insulating
material.
 The heavier Group 2 elements also form a number of complex oxides such
as perovskite, SrTiO3, and spinel, MgAl2O4.
Sulfides
 The sulfides mostly adopt the rock-salt structure and have applications as
phosphors.
 For example, Barium sulfide exhibits strong phosphorescence and was the
first synthetic phosphor. It is produced by reducing the naturally occurring
barytes, BaSO4, with coke: BaSO4(s) + 2 C(s) → BaS(s) + 2CO2(g)
Nitrides and carbides
 All the elements form nitrides of composition M3N2 when heated in nitrogen.
These react with water to form ammonia and the metal hydroxide:
M3N2(s) + 6H2O(l) → 3M(OH)2(s, aq) + 2 NH3(g)
 The sulphates and nitrates of Group 1 elements are also important, e.g.
Na2SO4 and NaNO3.
 All the elements also form carbides. Beryllium carbide, Be2C, formally
contains the methide ion, C4–. The carbides of Mg, Ca, Sr, and Ba have the
formula MC2 and contain the dicarbide (acetylide) anion, C 22–. The carbides
of Ca, Sr, and Ba are prepared by heating the oxide or carbonate with
carbon in a furnace at 2000oC:
MO(s) + 3C(s) → MC2(s) + CO(g)
MCO3(s) + 4C(s) → MC2(s) + 3CO(g)
 All the carbides react with water to produce the hydrocarbon corresponding
to the carbon ion present: beryllium carbide produces methane, whereas
the other elements produce ethyne (acetylene):
Be2C(s) + 4H2O(l) → 2 Be(OH)2(s) + CH4(g)
CaC2(s) + 2H2O(l) → Ca(OH)2(s) + C2H2(g)
Compounds of oxoacids
 The most important oxo compounds of the Group 2 elements are the
carbonates, hydrogencarbonates, and sulfates.
 All the carbonates are sparingly soluble in water, with the exception of
BeCO3; the carbonates decompose to the oxide on heating most readily
high in the group. The hydrogencarbonates are more soluble than the
carbonates.
 The most important sulfate is calcium sulfate, which occurs naturally as
gypsum and alabaster.
Coordination Compounds
 Only beryllium forms coordination compounds with simple ligands such as
the halides; the most stable complexes are formed with polydentate
chelating ligands such as edta.
Organometallic Compounds
 Alkylberyllium compounds polymerize in the solid phase; Grignard reagents
are some of the most important main-group organometallic compounds.
They are highly reactive; hydrolysed by water, liberating hydrogen; and
pyrophoric (spontaneously igniting) in air.
Uses of Group 2 elements and their compounds
 The inertness and corrosion resistance of Beryllium and being one of the
lightest metals makes it suitable for use in alloys to make precision
instruments, aircraft, and missiles.
 Be is highly transparent to X-rays because of its low atomic number (and
thus electron count) and is used for X-ray tube windows. An alloy of
beryllium with copper and aluminum has excellent fatigue or failure
resistance to spring and stressed functions; applications include automobile
suspension, electromechanical devices, and the springs in computer
keyboards and printers.
 Uses of Group 2 elements and their compounds
 Beryllium is also used as a moderator for nuclear reactions (where it
slows down fast-moving neutrons through inelastic collisions) because the
beryllium nucleus is a very weak absorber of neutrons and the metal has a
high melting point.
 Most of the applications of elemental magnesium are based on the formation
of light alloys, especially with aluminum, that are widely used in construction
in applications where weight is an issue, such as aircraft. A magnesium-
aluminum alloy was previously used in warships but was discovered to be
highly flammable when subjected to missile attack. Some of the uses of
magnesium are based on the fact that the metal burns in air with an intense
white flame, and so it is used in fireworks and flares.
 In medicine, applications of magnesium compounds include ‘Milk of
Magnesia’, Mg(OH)2, which is a common remedy for indigestion, and ‘Epsom
Salts’, MgSO4.7H2O, which is used for a variety of health treatments including
as a treatment for constipation, a purgative, and a soak for sprains and bruises
 Magnesium oxide, MgO, is used as a refractory lining for furnaces.
 Organomagnesium compounds are widely used in organic synthesis as
Grignard reagents.
 The compounds of calcium are much more useful than the element itself.
Calcium oxide (as lime or quicklime) is a major component of mortar and
cement. It is also used in steelmaking and papermaking.
 Uses of Group 2 elements and their compounds
 Calcium sulfate dihydrate, CaSO4.2H2O, is widely used in building materials,
such as plasterboard, and anhydrous CaSO4 is a common drying agent.
 Calcium carbonate is used in the Solvay process for the production of sodium
carbonate and the raw material for production of CaO.
 Calcium fluoride is insoluble and transparent over a wide range of
wavelengths. It is used to make cells and windows for infrared and
ultraviolet spectrometers.
 magnesium and calcium have very important for biological function.
Magnesium is a component of chlorophyll but also it is coordinated by many
other biologically important ligands, including ATP (adenosine triphosphate). It
is essential for human health, being responsible for the activity of many
enzymes. The recommended adult human dose is approximately 0.3 g per
day and the average adult contains about 25 g of magnesium.
 Strontium is used in pyrotechnics, in phosphors and in glasses for the now
rapidly declining market for colour television tubes.
 Barium compounds are used as ‘barium meals’ and ‘barium enemas’ to
investigate the intestinal tract. Barium is highly toxic, so the insoluble sulfate
is used in this application.
 Uses of Group 2 elements and their compounds
 Barium carbonate is used in glassmaking and as a flux to aid the flow of
glazes and enamels. It is also used as rat poison. The sulfide has been
used as a depilatory, to remove unwanted body hair. Barium sulfate is
pure white, with no absorption in the visible region of the electromagnetic
spectrum, and it is used as a reference standard in UV-visible
spectroscopy.
 Soon after its discovery, radium was used to treat malignant tumors; its
compounds are still used as precursors for radon used in similar
applications.
 Luminous radium paint was once widely used on clock and watch faces
but has been replaced by less hazardous phosphorescence compounds.