CHE 310 : CHEMISTRY OF s- and p-Block ELEMENTS

General Trends in Main Group Chemistry

Physical Properties

The main group elements (s and p) complete their electron configurations using s and p
electrons. These elements range from the most metallic to the most non-metallic with elements
of intermediate properties, the semi-metals (Also known as metalloids) in between.

On the far left, the alkali metals and alkaline earths exhibit the metallic characteristics of luster,
high ability to conduct heat and electricity, and malleability. At the far right are the non-metals.
Metals contain loosely bound valence electrons that are relatively free to move hence conduct
current. In most cases, non-metals contain much more localized lone electron pairs and
covalently bonded pairs that are less mobile. An exception is graphite, a form of carbon that has
a much greater ability to conduct than most non-metals because of delocalized electrons.

Elements along a rough diagonal from boron to polonium are intermediate in behavior, in some
cases having both metallic and non-metallic allotropes (elemental forms). These elements are
designated as metalloids or semi-metals. Some elements such as silicon and germanium are
capable of having their conductivity finely tuned by the addition of small impurities and are of
enormous importance in the manufacture of semi conductors in the computer industry.

Some of the columns of the main group elements are designated by common names e.g

Group 1. Alkali metals

Group 2. Alkaline earths

Group 6.Chalcogens (O, S gp)

Group 7. Halogens

Group 8. Noble gases

Electronegativity

Is the ability of an atom to attract electrons from a neighboring atom to which it is bonded.
Electronegativity increases toward the right hand corner of the periodic table. The most
electronegative element is fluorine (4.0). Electronegativity decreases down the groups and its
lowest on the left hand corner of the periodic table.
Ionization energy

Ionization energy, also known as ionization potential is the energy required to remove an
electron from a gaseous atom or ion. Ionization energies of the main group elements exhibit
trends similar to those of electronegativity. The general trend across a period is an increase in
ionization energy as the nuclear charge increases. However, there are some deviation for
example, group 3 elements have lower ionization energies than the preceding group 2 elements,
and several group 6 elements have lower ionization energies than the preceding group 5
elements. For example, the ionization energy of boron (gp 3) is lower than that of berylium (gp
2) and the ionization energy of oxygen (gp 6) is lower than that of nitrogen (gp 5).

H/W – Find out why this deviation occurs?

Overall, the trends are toward higher ionization energy from left to right in the periodic table.
Down the groups of the periodic table, there is a decrease in I.E fromtop to bottom.

Atomic and Ionic Radii

The sizes of atoms and ions are related to the ionization energies. As the nuclear charge
increases, the electrons are pulled in towards the centre of the atoms and the size of any
particular orbital decreases. This results in gradual decrease in atomic size across each period.
The noble gas atoms are smaller than the neighboring halogen atoms (eg Ne is smaller than F) as
a consequence of a greater effective nuclear charge. This charge which attracts noble gas
electrons strongly toward the nucleus leads to high electronegativities predicted for the noble
gases. Down the groups, there is an increase in atomic size because extra shells of electrons are
added to atoms.

Ionic radii – Formation of ions also causes changes in their sizes. A positive ion formed by
removal of one or more electrons from the outermost shell results in a dramatic decrease in size.
As a result of electron removal, the ratio of positive charges on the nucleus (protons) to the
number of electrons is increased hence the effective nucleur charge is increased and the electrons
are pulled closer to the nucleus. On the other hand, negative ions are formed when one or more
electrons are added to the atom resulting in a fall in the effective nucleur charge and hence an
expansion of the electron cloud leading to an increase in size. Thus across a period, there is no
obvious trend regarding ionic radii. As with atomic radii, ionic radii increase as we go down any
group.

Electron affinity – It is the energy involved when an electron is added to a neutral gaseous atom.
The electron affinity values may be either positive or negative.

Electropositivity – It is the tendency of an atom of an element to lose electrons. It is therefore a

measure of metallic character. It increases down any group and decreases along a period. The
higher the electropisitivity, the lower the ionization energy.
HYDROGEN

Hydrogen is the simplest of the elements with its one valency orbital and single electron. It can
react by gaining, losing or sharing an electron and its behavior is fairly uncomplicated. Hydrogen
combines with almost all the other elements and as its electronegativity value comes in the
middle of the range; its bonds have a wide range of polarity from the strongly positive hydrogen
of the hydrogen halides to the negative anionic hydrogen in the active metal hydrides.

Hydrogen does not fit into any of the groups of the periodic table and is best regarded as an
introductory element to the periodic classification. However, it does show analogies to three of
the other groups:

1. In common with the alkali metals, it may lose an electron to form a cation.This position is
not satisfactory because its chemical and physical properties are different from those of
alkali metals. In particular hydrogen is not a metal under normal conditions.
2. In common with the halogens, it has a tendency to gain an electron to form the hydride
ion H−. However their similarities are very limited.
3. In common with the carbon group elements, hydrogen has a half-filled valency shell to
form covalent bonds with a wide range of polarities.

There are three isotopes of hydrogen: Hydrogen (1H); Deuterium, (D, 2H); and tritium
(T, 3H).

Naturally occurring hydrogen is 99.8% 1H, D,2H 0.02% and Tritium is 10-7%.

Production

The main commercial process for the production of hydrogen is steam reforming, the
catalyzed reaction of water and hydrocarbons (mostly methane) at high temperatures.

CH4 + H2O ---1000°C----------- CO + 3H2

A similar reaction but with coke as the educing agent is called water gas reaction

C + H2O ----1000°C--------------- CO + H2

Reactions of Hydrogen

Molecular hydrogen reacts slowly with most elements, partly because of its high bond
enthalpy (436 kJ mol-1) and hence high activation energy for reaction. However under special
conditions the reactions are rapid. These include:

1. The activation of the molecule by homolytic dissociation on a metal surface

2. Heterolytic dissociation by a surface or a metal ion.
3. Initiation of a radical chain reaction.
 An example of homolytic dissociation is chemisorption on platinum. This is where finely
divided platinum metal is used to catalyze the hydrogenation of alkenes.

An example of heterolytic dissociation is the reaction of H2 with a ZnO surface, which

appears to produce a Zn(II) –bound hydride and an O-bound proton.

H2 + Zn-O-Zn-O ----------- Zn-----O----Zn----O

This reaction is thought to be involved in the catalytic hydrogenation of carbon monoxide

to methanol

CO + 2H2 ----Cu/ZnO/Al2O3------ CH3OH

Radical chain mechanism account for the thermally or photochemically initiated reactions
between H2 and the halogens.

Initiation Br2 -Heat or hv-------- Br. + Br.

Propagation Br. + H2 -----HBr + H.
H. + Br2 ------------ HBr + Br.

Termination H. + H. ---- H2
Br. + Br. ---- Br2

Compounds of Hydrogen

Chemically hydrogen behaves as a typical non-metal, forming covalent compounds with

other non-metals and salts with very reactive metals. Binary compounds containing
hydrogen are called hydrides and there are three classes.

1. The ionic (or salt like) hydrides – these are formed when hydrogen combines with the
most reactive alkali metals eg Na and Li.

2Na + H2 ------- 2NaH

Li + H2 ------LiH

They contain hydride ions (H-) and metal cations. The hydride ion is a very strong
reducing agent (easily loses electrons). The presence of two electrons in the small s
orbital leads to a large e-e repulsions.
For example when ionic hydrides are placed in water, a violent reaction takes place. This
reaction results in the formation of hydrogen gas.
 LiH + H2O -------H2 + LiOH

2. Covalent/molecular hydrides – when hydrogen combines with other non-metals, e.g HCl,
NH3, H2O etc. The most important covalent hydride is water.

H2 + O2 ------- H2O

Molecular compounds of hydrogen are divided into three categories:

a) Electron precise in which all valence electrons of the central atom are used in bonds
e.g CH4
b) Electron deficient – there are too few electrons to be able to write a Lewis structure
for the molecule e.g BH3
c) Electron rich – there are more electron pairs on the central atom than are needed for
bond formation. There are lone pairs of electrons on the central atom. E.g NH3.

Electron deficient hydrogen compounds exhibit Lewis acidity, while electron rich
compounds such as NH3 and H2O with lone pairs of electrons exhibit Lewis basicity.
Which is more basic b/w water and ammonia and why?

An important consequence of the presence of highly electronegative atoms (N, O, and

F) and lone pairs in the electron rich compounds is the possibility of forming
hydrogen bonds. The E-H bond b/w an electronegative element E and hydrogen is
highly polar, E—H, and the partially positively charged H atom can interact with a
lone pair on the electron rich compound. Thus a hydrogen bond consists of a H atom
b/w atoms of more electronegative non-metallic elements. Evidence for hydrogen
bonding is provided by the trends in boiling points which are unusually high for the
strongly hydrogen bonded molecules such as water, ammonia and HF.
H/W (Find out why the boiling point of HF is higher than that of HCl)?

3. Metallic (interstitial) hydrides – are formed when transition metals are treated with
hydrogen gas. The hydrogen molecules dissociate at the metals surface. Metallic hydrides
have metallic lustre and most are electrically conducting. They are less dense than the
parent metal and are brittle.

Industrial Uses of hydrogen

1. Used in the manufacture of ammonia

Hydrogen reacts with nitrogen to generate ammonia gas which when dissolved in
water yields ammonia solution.
3H2 + N2 ----- 2NH3
 Used in the preparation of margarine by a process called hydrogenation. Liquid oils
from plants are hardened by using hydrogen gas.

H-H + H2C=CH2 ------- H2C-CH2H

GROUP 1 ELEMENTS

The elements in this group (alkali metals) are lithium (Li), sodium (Na), potassium (K),
Rubidium (Rb), Ceasium (Cs) and Francium (Fr). Francium is highly radioactive and exists
naturally in small quantities and will not be discussed.

All the group 1 elements are metals with electron configuration ns1. They conduct electricity and
heat, are soft, and have low melting points that decrease down the group. 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. All the metals form alloys.

The chemical properties of the group 1 elements correlate with the trend in their atomic radii.
The increase in atomic radius from lithium to francium leads to decrease in first ionization
energy down the group because the valence shell is increasingly distant from the nucleus.
Because their first ionization energies are low, the metals are reactive and form M+ ions readily
and increasingly down the group. Thus lithium reacts gently with water, sodium reacts
vigorously, potassium reacts so exothermally that the hydrogen released is ignited and rubidium
and caesium react explosively.

2M + 2H2O ------- 2MOH + H2

The metals are readily oxidized and thus are excellent reducing agents. All the elements must be
stored under a hydrocarbon solvent to prevent reaction with atmospheric oxygen.

Most of the trends in the chemical properties of the elements within the periodic table are
discussed in vertical trends within groups or horizontal trends across periods. However, the first
element in each group displays a diagonal r/ship with the element to the lower right of it in the
periodic table. Diagonal r/ships arise because the atomic radii and hence many of the chemical
properties of the two elements are similar.

Examples of the similarities b/w lithium and magnesium are:

1. Many lithium and magnesium salts exhibit a high degree of covalent character in their
bonding
2. They both react with nitrogen to form nitride. Other group 1 elements do not form nitride.

6Li + N2 -------2Li3N
3Mg + N2 -------Mg3N2
 3. They both react with oxygen to form normal oxides (monoxide) as the only oxide, other
group 1 elements form peroxides and superoxides.

Li + O2 ------Li2O
Mg + O2 ------MgO

4. Both are used in the preparation of organometallic compounds

5. Their carbonates decompose on heating to give the metal oxide, and carbon dioxide; the
carbonates of other alkali metals do not decompose when heated.

EXTRACTION

The group 1 elements are extracted by electrolysis. The most abundant mineral for lithium is
spodumene, LiAlSi2O6 from which lithium is commonly extracted. Spodumene is first converted
to LiCl and electrolyzed to lithium metal.

Sodium occurs as the rock salt (NaCl) and in salt lakes and sea water. The metal is extracted by
Downs process, the electrolysis of molten sodium chloride.

2NaCl (l) ------ 2Na (l) + Cl2 (g)

Compounds

All the group 1 elements form simple compounds with hydrogen and oxygen, and the halogens
and also form salts of oxo-acids. The compounds are predominantly ionic.

Hydrides

They form ionic, saline hydrides with the rock salt structure; the anion present is the hydride ion,
H−. The hydrides react violently with water:

NaH + H2O ------ NaOH + H2O

Halides

All the group 1 elements form halides MX, by direct combination of the elements. Most of the
halides have the 6,6 –co-ordinate rock salt structure, but CsCl and CsBr and CsI have the 8,8 co-
ordinate ceasium chloride structure.

The halides are all soluble in water except LiF, which is sparingly soluble. This low solubility is
due to a small difference in the radii of the cation and anion. Solubility is higher if there is a
large difference between radii of cation and anion.

Question: Which of these two salts is more soluble and why? LiI and CsF.
Oxides

All the group 1 elements react vigorously with oxygen. Only lithium reacts directly with oxygen
to give the oxide, LiO.

4Li + O2 ------- 2 Li2O

Sodium reacts with oxygen to give the peroxide, Na2O2 which contains the peroxide ion, O22−.

2Na + O2 -------- Na2O2.

The other group 1 elements form the superoxides, O2−.

K + O2 --------- KO2

Rb + O2 ----- RbO2

Cs + O2 ----- CsO2

All the oxides are basic and react with water to give the hydroxide ion:

Li2O + H2O ------- 2Li+ + 2OH−

Na2O + 2H2O ---------- 2Na+ + 2OH- + H2O2

2KO2 + 2H2O ---------- 2K+ + 2OH- + H2O2 + O2

Hydroxides

All the hydroxides are white, and deliquescent solids. They absorb water from the atmosphere in
an exothermic reaction. The solubility of the hydroxides makes them a ready source of OH- ions
in the lab. and in industry. KOH is soluble in ethanol and the ethanolic KOH is a useful reagent
in organic synthesis.

Compounds of Oxoacids

They form salts with most oxo-acids. The most industrially important group 1 salts of oxo-acids
are sodium carbonate, soda ash and sodium hydrogen carbonate, sodium bicarbonate.

Carbonates

The group 1 elements form the only soluble carbonates although lithium carbonate is only
sparingly soluble.

2NaCl + CaCO3 ------ Na2CO3 + Ca Cl2 - Solvay process

Hydrogencarbonates

Sodium hydrogen carbonate (sodium bicarbonate) is less soluble than sodium carbonate in water
and can be prepared by bubbling CO2 through a saturated solution of the carbonate.

Na2CO3 + CO2 + H2O -------2NaHCO3

The reverse of this reaction occurs when the bicarbonate is heated

2NaHCO3 ----------Na2CO3 + CO2 + H2O

This reaction provides the basis for the use of sodium hydrogen carbonate as a fire extinguisher.
The powdered salt decomposes in the heat to liberate carbon dioxide and water. This reaction is
also the basis for use of NaHCO3 during the baking process, as the CO2 and water vapour
released cause the product to rise.

Nitrides

Lithium is the only member in the group that forms a nitride by direct reaction with nitrogen

6Li + N2 -----2Li3N

Solubility and hydration

All the common salts of the group 1 metals are soluble in water. The most soluble are those for
which there is a great difference b/w the radii of the cation and the anion. Thus the solubilities of
the lithium halides increase from the fluoride to the bromide.
Solutions in Liquid ammonia

Alkali metals dissolve in liquid ammonia and other donor solvents such as aliphatic amines
(NR3, R = alkyl) to give blue solutions believed to contain solvated electrons.

Na + NH3 ---- Na+ + e−(NH3)

Because of the solvated electrons, dilute solutions of alkali metals in ammonia conduct
electricity better than dissociated ionic compounds in aq. Solutions.

Solutions of alkali metals in liquid ammonia are excellent reducing agents, for example

RC=CH (triple bond) + e -------- RC=C− + 1/2H2

NH4+ + e ---------------- NH3 + 1/2H2

Coordination Compounds

Alkali metal atoms have very low ionization energies and lose their outermost electron to form
ions of 1+ charge. They are hard Lewis acids. These ions can form complexes with a variety of
Lewis bases (Ligands) – molecules with donor O or N atoms. Of particular interest are cyclic
Lewis bases that have several donor atoms that can trap cations. Most of the complexes they
form arise from coulombic interactions with small hard donors such as those possessing O or N
atoms. Examples of these bases are the crown ethers and cryptands which donate electron
density to metals through their oxygen atoms. Crown ethers such as 18-crown-6, 15-crown-5 and
12-crown-4 form complexes with alkali metal ions.

(structures of crown ethers)

Organometallic compounds

Group I elements form a number organometallic compounds that are unstable in the presence of
water and pyrophoric in air. They are prepared in organic solvents such as tetrahydrofuran (THF)
or dichloromethane.

Lithium alkyls and aryls are by far the most important group I organometallics. They low
melting solids are the most thermally of the entire group and are soluble in organic nonpolar
solvents such as THF. They are prepared from alkyl halide and lithium metal or by reacting the
organic species with butyllithium, BuLi.

BuCl + 2Li ---------- BuLi + LiCl

BuLi + C6H6 ---------- Li(C6H5) + C4H10

Uses of Group I elements

Applications of lithium are due to its low atomic mass and thus low density.

Lithium is used in aircraft alloys and in several types of batteries.

Sodium is used in the extraction of rare metals such as titanium from titanium(IV) chloride.

NaCl is used in road de-icing and production of NaOH

Sodium metal is used in street lamps

KOH is used in soap manufacture

KCl and K2SO4 are used as fertilizers

Sodium carbonate is used in glass manufacture

Rb and Cs are used in the same applications and one element may be substituted for the other.

Group II Elements

Group II elements (alkaline earth) are Beryllium (Be), magnesium (Mg), calcium (Ca), strontium
(Sr), barium (Ba) and radium (Ra). All the elements are silvery white metals but chemical
properties of beryllium are like those of metalloid. The elements are harder, denser and less
reactive than the elements of group I.

The increase in mechanical hardness of the group II compared with group I elements indicates an
increase in the strength of metallic bonding b/w groups 1 and 2, which can be attributed to the
increased number of electrons. The atomic radii of group II elements are smaller than those of
group I. This reduction in atomic radius b/w the group is responsible for the higher densities and
ionization energies. The ionization energies of the elements decrease down the group as the
radius increases. The elements become more reactive and more electropositive down the group
as it becomes easier to form the +2 ions.

Calcium, strontium and barium react readily with cold water, magnesium reacts only with hot
water

M (s) + 2H2O -------- M(OH)2 + H2

All the elements occur as M (II) in their compounds, which is consistent with ns2 valence
electron configuration. The compounds are predominantly ionic, with the exception of those of
beryllium which are predominantly covalent because of the small size of the Be2+ ions and the
corresponding high charge density.
There is a strong diagonal r/s b/w beryllium and aluminium:

-Be and Al form covalent hydrides, halides, and oxides; the analogous compounds of magnesium
are predominantly ionic

-Be and aluminium hydroxides are amphoteric, magnesium oxide is basic

-Be and Al form carbides that contain the C4− ion and produce methane on reaction with water.

-Both metals dissolve in alkali with evolution of hydrogen gas

-The halides form polymeric solids, beryllium halides form chains and aluminium halides form
dimmers.
-They have similar redox potentials, Be2+/Be = -1.70 V, Al3+/Al = -1.67 V.
-Both elements form hydrides and alkyls which polymerize through electron deficient bridges.

Extraction

Be is extracted by heating beryl (Be3Al2(SiO3)6 with sodium hexafluorosilicate, Na2SiF6 to

produce BeF2 which is then reduced to the element by magnesium

Magnesium is extracted by electrolysis of molten magnesium chloride:

Cathode: Mg2+ + 2e ------ Mg (s)

Anode: 2Cl− ------- Cl2 + 2e

Calcium,Sr and Ba are also extracted by electrolysis of their molten chlorides.

Compounds

All the group II elements form simple compounds with hydrogen, oxygen and halogens. The
properties of the compounds are predominantly ionic, with the exception of Be which is
covalent. Be and its compounds are extremely toxic and special precautions are required in heir
handling.

Hydrides

Like the group I elements the group II elements with the exception of Be, they form ionic, saline
hydrides that contain the H− ion. They are prepared by direct reaction b/w the metal and
hydrogen. BeH2 is covalent. It has a chain structure with bridging hydrogen atoms.

Put structure of BeH2 chain here

The ionic hydrides of the heavier elements react violently with water to produce hydrogen gas

MgH2 + 2H2O ------- Mg(OH)2 + 2H2

Halides

All the halides of Be are covalent. BeCl2 is a Lewis acid readily forms adducts with electron pair
donors such as diethyl ether (BeCl2(OEt2)2.

Magnesium halides are prepared by direct combination of the elements.

All the fluorides except BeF2 are sparingly soluble, the solubility increases down the group

As the radius of the cation increases from Be to Ba, the cation coordination number increases
from 4 to 8.

The most important fluoride of the group II elements is CaF2. Its mineral form is fluorspar.

All the group II elements are deliquescent and form hydrates.

Oxides and hydroxides

The group II elements react with oxygen to form the oxides. The oxides react with water to form
the basic hydroxides.

Be oxide is obtained by ignition of the metal in oxygen. It’s a white insoluble solid. The oxides
of the other group II elements are obtained by direct combination of the elements but are
commonly obtained by decomposition of the carbonates

MCO3 ----heat--------- MO + CO2

The oxides of the elements from Mg to Ba all adopt the rock salt structure. Their melting points
decrease down the group.
Both BeO and MgO have very high thermal conductivity with low electrical conductivity.

The group 2 elements form a number of complex oxides such as perovskite, CaTiO3 and spinel,
MgAl2O4.

All the hydroxides are formed by reaction of the oxides with water. The hydroxides become
more basic down the group with increasing metal character of the element. Be(OH)2 is
amphoteric. The solubility in water increases from Mg(OH)2 to Ba(OH)2; Mg(OH)2 is sparingly
soluble and forms a mildly basic solution because a saturated solution contains a low
concentration of the OH ions. An aq suspension of Mg(OH)2 is used as an antacid (milk of
magnesia). Ca(OH)2 is more soluble than Mg(OH)2 so a saturated solution contains a higher
concentration of OH ions and the solution is described as being moderately basic. A saturated
solution of Ca(OH)2 is called lime water. Barium hydroxide is soluble and aq solution described
as strongly basic.

H/W – Explain why Mg(OH)2 is a better antacid than calcium or barium?

Carbides

All the group 2 elements form carbides. Beryllium carbide, Be2C contain the methide ion C4-.
The carbides of Mg, Ca, Sr and Ba have the formula MC2 and contain the dicarbide (acetylide)
anion C22-. They are prepared by heating the oxide or carbonate in a furnace at 2000°C

MO + 3C ------MC2 + CO2

2MCO3 + 5C -------2MC2 + 3CO2

All the carbides react with water to yield a hydrocarbon; Be carbide produces methane, whereas
the other elements yield acetylene (ethyne)

Be2C + 4H2O ------- 2Be(OH)2 + CH4

CaC2 + 2H2O -------- Ca(OH)2 + C2H2

Salts of oxoacids

The most important oxo compounds of group 2 elements are the carbonates, hydrogen carbonates
and the sulfates.

Carbonates and hydrogencarbonates

The carbonates of group 2 elements are sparingly soluble and are decomposed to the oxide on
heating
MCO3 ----------- MO + CO2

The decomposition temperature increases down the group. The group 2 carbonates are less
thermally stable than the group 1 carbonates.

Calcium carbonate is the most important oxo compound of the group 2 elements. It occurs
widely in nature as limestone, chalk or marble.

The group hydrogen carbonates are more soluble in water than the corresponding carbonates.
Temporary hardness (removed by boiling) is caused by the presence of magnesium and calcium
hydrogencarbonates. These ions are precipitated as carbonate on boiling.

Ca(HCO3)2 ---heat-----CaCO3 + CO2 + H2O

Temporary hardness may also be removed by adding Ca(OH)2 which precipitates the
hydrogencarbonate

Ca(HCO3)2 + Ca(OH)2 ------ 2CaCO3 + 2H2O

Sulphates

Permanent hardness (not removed by boiling) is caused by Mg and Ca sulphates. In this case, the
water is softened by passing through an ion exchange resin, which replaces the Mg2+ and Ca2+
ions with Na+ ions. Calcium sulphate is the most important of the group 2 sulphates. It occurs as
gypsum, CaSO4·2H2O. When the dehydrate is heated above 150°C it loses water to form a
hemihydrate, CaSO4.1/2H2O known as plaster of Paris. When mixed with water, plaster of paris
expands as it forms the dihydrate and forms a strong structure used to make castes for broken
limbs.

Solubility and hydration

The compounds of group 2 elements are generally much less soluble in water than those of
group1 elements.

With the exception of the fluorides, the salts of mononegative anions are usually soluble in water
and those of dinegative anions are usually sparingly soluble. The carbonates and sulphates have
very low solubility. This insolubility is responsible for the large deposits of ca and mg containing
minerals such as limestone and gypsum.

Coordination and Organometallic Compounds

All the group 2 elements except Be form non-labile complexes with polydentate, chelating
ligands. The most important organometallic compounds of the group are the magnesium-based
Grignard reagents.
Coordination Compounds

The group 2 cations form complexes with crown ethers and cryptand ligands. The most stable
complexes are formed with charged polydentate ligands such as ethylenediaminetetraacetate
(edta) ion.

Structure of EDTA

[Mg(edta)H2O]2-

Many complexes of Ca2+ and Mg2+ occur naturally, for example magnesium complex is the
macrocyclic complex chlorophylls.

Organometallic Compounds

Grignard reagents are some of the most important main group organometallic compounds.

Organometallic compounds of beryllium are pyrophoric in air and unstable in water. They are
prepared by transmetallation from methylmercury in a hydrocarbon solvent

Hg(CH3)2 (sol) + Be ------- Be(CH3)2

Alkyl and arylmagnesium halides are known as Grignard reagents with general formula RMgX,
X = is a halide and are widely used in synthetic organic chemistry where they behave as a source
of R-. They are prepared from magnesium metal and an organohalide.

Mg (s) + RBr (sol) ----- RMgBr (sol)

Example in organic synthesis:

CH3CH2MgCl + CH3Cl ------ CH3CH2CH3 + MgCl2

The reagents are very unstable and are stored in solvents such as ether or THF.

H/W

Explain why group 1 hydroxides are more corrosive than group 2 hydroxides

How do gp 2 salts give rise to scaling from hard water?

Uses of group 2 elements and compounds

Be is light and is unreactive in air being resistant to corrosion, it is used to make alloys for
aircraft and missiles
Mg is a component of chlorophyll. Like Be, it is used in alloys for aircraft.

It is alo used in fireworks as it burns in air with an intense white flame

Mg(OH)2 is used as an antacid for indigestion

Organomagnesium compounds are used in organic synthesis as Grignard reagent

Calcium oxide as lime or quicklime is a major component in cement.

Ca(OH)2 is used to neutralize acidic soils

Barium compounds are effective at absorbing X-rays and are used as barium meals to investigate
intestinal tract.

P- Block Elements

The first element in each ‘p’ group of the periodic table is in many ways not typical of the group.

The valency shell configuration of the first row elements of the p group is 2s22pn. The first row
elements are restricted to a maximum coordination number of four (using the 2s and the three 2p
orbitals). In contrast, the second element of a p group with the configuration 3s23pn, has the 3d
orbitals lying between the 3p level and the 4s level in energy. The second row elements make use
of these 3d orbitals in bonding. For this reason, coordination numbers greater than four occur; for
example fluorine complexes of boron and aluminium are BF4- and AlF6- respectively.

Also the first row elements in p block have the ability to form strong double bonds using only p-
orbitals (pπ-pπ bonds). The other members in the second row form compounds with single bonds.
For example, in carbon and silicon dioxides, carbon dioxide has double bonds, while in silicon
dioxide; silicon forms a single bond to four oxygen atoms

Group III Elements

The elements of gp 3 are Boron (B), Aluminium (Al), Gallium (Ga), Indium (In), and Thalium
(Tl). They have interesting and diverse chemical properties. The first member of the gp boron is
non-metallic whereas the properties of the heavier members are metallic.

Whereas the elements of the s and d block are metallic, the elements of the p block range from
nonmetals through metalloids to metals. This variety results in diversity of chemical properties
and some trends which can be rationalized by consideration of atomic radii and electronic
configurations. There is an increase in metallic character from boron to thalium: boron is a
nonmetal, aluminium is metallic although it is classified as a metalloid because of its amphoteric
character and gallium, indium and thalium are metals. Associated with this trend is a variation
from covalent to ionic bonding in the compounds of the elements that can be explained in terms
of increase in atomic radius and related decrease in ionization energy down the group. Because
the ionization energies of the heavier elements are low, the metals form cations increasingly
readily down the group. In contrast to the expected trend in electronegativity, gallium is more
electronegative than aluminium. This anomaly in the general trend to lower electronegativity is
known as inert pair effect and is a consequence of increased effective nuclear charges of the p
elements due to the presence of their poorly shielding 3d electrons. Also electropositivity of
group III elements increases from boron to aluminium then decreases from aluminium to thalium
due to the presence of d and f orbitals where d and f- electrons have less effective screening
effect compared with electrons in s and p orbitals. This enables the nucleus to attract the outer
electrons strongly. Electropositivity decreases from aluminium to thalium because the valence
electrons are not easily removed.

The chemical properties of boron have diagonal r/sp with silicon in group 4:

Boron and silicon form acidic oxides, B2O3 and SiO2; aluminium forms an amphoteric oxide

Boron and silicon form many polymeric oxide structures

Boron and silicon form flammable gaseous hydrides; aluminium hydride is a solid.

The valence electron oxidation configuration of the group 3 elements is ns2np1 and all the
elements adopt a +3 oxidation state in their compounds. However the heavier elements of the
group also form compounds with the metal in the +1 oxidation state, and this state increase in
stability down the group. The most common oxidation state of thalium is Tl(I). The relative
stability of an oxidation state in which the oxidation number is 2 less than the group oxidation
number is called inert pair effect. It is ascribed to the large energy needed to remove the ns 2
electrons after np1 electron has been removed.

The most striking feature of the group 3 elements is the electron deficiency and the resulting
Lewis acidity of their neutral compounds. The electron deficiency arises from the ns2np1 electron
configuration which contributes up to a maximum of six electrons in the valence shell when
three covalent bonds are formed. This electron deficiency has vital influence on the structure and
reactions of the compounds of the elements.

Occurrence and Extraction

Boron occurs naturally as borax (Na2B4O5(OH)4.8H2O. The borax is converted to boric acid,
B(OH)3 and then to boron oxide B2O3. The oxide is reduced with magnesium and washed with
alkali and hydrofluoric acid. Pure boron is produced by reduction of BBr3 vapour with H2
2BBr3 + 3H2 ---------- 2B + 6HBr

Aluminium occurs naturally as bauxite, a complex mixture of hydrated aluminium and

aluminium oxide. Gallium oxide occurs as an impurity in bauxite and is recovered as a by-
product of the manufacture of aluminium.

Simple compounds of boron

As the first member of the group, the chemical properties of boron and its compounds are
different from those of its congeners.

Hydrides

Boron forms a range of neutral and anionic hydrides with cage like structures. These species are
electron deficient and act as Lewis acids. The simplest member of the hydrides of boron is the
borane, BH3. Borane does not exist on its own instead it exists as a dimer, B2H6 called diborane
and is electron deficient.

Structure of B2H6

All the boranes are colourless and diamagnetic. They range from gases B2H6 and B4H8 through
volatile liquids B5H9 to solid B10H14.

The lighter boranes are readily hydrolysed by water

B2H6 (g) + 6H2O (l) ----- 2B(OH)3 (aq) + 6H2 (g)

Lewis acidity

Diborane and other light boron hydrides act as Lewis acids and they are cleaved by reaction with
Lewis bases. The cleavage is either symmetric or unsymmetric.

Symmetric cleavage of diborane

B2H6 + 2N(CH3)3 ----- 2BH3-N(CH3)3

Reaction of diborane and ammonia results in unsymmetrical cleavage leading to an ionic

product.
Boron trihalides

All the boron trihalides except BI3 may be prepared by direct reaction between the elements.

Boron trihalides consist of trgonal planar BX3 molecules. They are monomeric in the gas, liquid
and solid states. They have an incomplete octet and are Lewis acids. The order of their strength
is BF3 < BCl3 < BBr3. The electron deficiency is partially removed by X-B π bonding b/w the
halogen atoms and the boron giving rise to partial occupation of the vacant p orbital on the boron
atom by electrons donated by the halogen atoms. All the boron trihalides form simple Lewis
complexes with suitable bases

BF3 (g) + NH3 (g) -------- F3B----NH3 (s)

However, boron chlorides, bromides and iodides are susceptible to protolysis by mild proton
sources such as water, alcohols. (B-F bond is very strong and is only mildly susceptible to
hydrolysis).

BCl3 + 3H2O ----- B(OH)3 + 3HCl

Hydrides of aluminium and gallium

Aluminium hydride AlH3 is a solid that is saline like the hydrides of the s-block elements.

The metathesis of the halides with LiH leads to lithium tetrahydridoaluminate, LiAlH4 or the
analogous tetrahydrogallate, LiGaH4

4LiH + ECl3 ----ether, heat----- LiEH4 + 3LiCl (E = Al, Ga)

LiAlH4 (LAH) is widely used as a strong hydride source and as a reducing agent.

Eg in CH3CHO --LAH--------- CH3CH2OH

Halides

All the elements form trihalides with the metal in its +3 oxidation state. As expected from the
inert pair effect, the +1 oxidation state becomes more common on descending the group and Tl
forms stable monohalides.

Direct reaction of Al, Ga and In with a halogen yields a halide, although the metals also react
with HCl and HBr gas to yield the halide

2Al + 6HCl ----100°C------- 2AlCl3 + H2

The trifluorides have limited solubility in most solvents and they do not act as Lewis acids to
simple donor molecules. The heavier trihalides of Al, Ga and In are soluble in a wide variety of
polar solvents and are good Lewis acids. They exist as M2X6 dimers. The electron deficiency of
the monomeric trihalides is removed by the formation of the dimers in which a coordinate M-X
bond is formed involving a lone pair of electrons on the halogen.

(A hard Lewis base – is hard because of its O donor atoms, Soft Lewis base is soft because of its
S atom).

Halides of heavier p-block elements such as Al may react with Lewis bases to increase
coordination number

AlCl3 + N(CH3)3 --------------- Cl3AlN(CH3)3

Low oxidation state halides

The oxidation state M(I) increases in stability down the group because of the inert pair effect.
GaF and LnF are unstable whereas other monohalides of Ga, In and Tl are stable. Stability
increases from chloride to iodide. They are prepared by heating GaX3 with the metal in a 1:2
ratio.

GaX3 + 2Ga ------- 3GaX (X = Cl, Br, I)

The electropositivity of group III elements increases from boron to aluminium then decreases
from aluminium to thalium. This is due to the presence of d and f orbitals where d and f-
electrons have less effective screening effect (poor shielders) compared with electrons in s and p
orbitals. This enables the nucleus to attract the outer electrons strongly. Electropositivity
decrease from aluminium to thalium because the valence electrons are not easily removed.

Oxo compounds

The most stable form of aluminium oxide is the Al2O3. Depending on the metal impurities
present, aluminium in its mineral form may exist as sapphire, ruby or emerald. Ruby is when a
small fraction of aluminium ions are replaced by Cr3+, Sapphire is when some aluminium ions
are replaced by Fe2+ and Ti4+.

Salts of oxoacids

The most important oxosalts of group 3 are called alums, MAl(SO4)2.12H2O, where M is a
univalent cations such as Na+, K+, Rb+.
Hydrated aluminium ions are acidic in aq. Solutions

Al3+ ion has a high charge density and so it gets hydrated in aq. conditions

Al3+ + 6H2O ------------------- [Al(H2O)6]3+

This can further react with water as follows

[Al(H2O)6]3+ + H2O --------------[Al(H2O)5OH]2+ + H3O+

It is the H3O+ ion which is responsible for making solution acidic, as it contains the H+ ion.

Group IV Elements

The elements are carbon (C), silicon (Si), germanium (Ge), tin (Sn), and lead (pb). They show
considerable diversity in their chemical and physical properties. Carbon is the building block of
life and central to organic chemistry. It forms man binary compounds with metals and non-
metals. In combination with oxygen and aluminium, silicon is a dominant component of minerals
in the Earth’s crust. Silicon and germanium are vital to modern high technology as
semiconductors and optical fibres.

Carbon and silicon are nonmetals, germanium is a metalloid and tin and lead are metals. There is
an increase in metallic properties on descending the group which is common in the p block. This
is due to the increase in ionic radii and a decrease in ionization energies. Thus the metals form
cations readily down the group.

As the configuration ns2np2 suggests, the +4 oxidation state is dominant in the compounds of the
elements. The major exception is lead for which the most common oxidation state is +2, two less
than the group maximum. This relative stability of the low oxidation state is a result of the inert-
pair effect. The electronegativities of carbon and silicon are similar to that of hydrogen and they
form many covalent and alkyl compounds.

Occurrence and Extraction

Two reasonably pure forms of carbon diamond and graphite are mined. Carbon occurs as carbon
dioxide in the atmosphere and dissolved in natural waters, and as the insoluble carbonates of
calcium and magnesium.

Silicon occurs distributed in the natural environment as sand, quartz, clays etc.

Uses

Silicon and germanium are produced for the manufacture of semiconductor devices.
Carbon in form of coke or coal is used as a fuel and a reducing agent. Graphite is used as a
lubricant and diamond is used in industrial cutting of tools.

Tin is used to plate steel in tin cans because it is resistant to corrosion.

Diamond and graphite

Diamond is effectively an electrical insulator while graphite is a good conductor. Diamond is a

bad conductor of electricity while graphite conducts electricity because in diamond, each carbon
atom is sp3 hybridized and is bonded to four other carbon atoms. All the valence electrons are
used in the formation of strong covalent bonds and no electron is left/free for electrical
conductivity. In graphite, each carbon atom is sp2 hybridized and is bonded to three other carbon
atoms. Three out of four valence electrons are used in the formation of strong covalent bonds and
one electron is left for electrical conductivity. That is in graphite, there are delocalized/free
electrons whereas in diamond, all the electrons are localized.
Other forms of carbon are fullerenes (buckyballs) and nanotubes.

Simple Compounds
All the group 4 elements form simple binary compounds with hydrogen, oxygen, halogens and
nitrogen.

Hydrides
All the elements form tetravalent hydride, EH4.

a) Hydrocarbons – Carbon forms a large range of hydrocarbon compounds (alkanes, alkenes

and alkynes)
b) Silanes – Silicon forms a series of compounds analogous to alkanes (silanes). The silanes
are more reactive than the alkanes and their stability decreases with increasing chain
length.
c) Germane, stannane and plumbane – these hydrides are unstable and this limits
accessibility of their chemical properties.

Compounds with halogens

The group 4 elements react with halogens to form tetrahalides.

Among the silicon tetrahalides, the most important is the tetrachloride prepared by direct reaction
of the elements.

Si (s) + 2Cl2 (g) ------- SiCl4 (l)

Silicon tetrachloride is readily hydrolyzed by water while carbon tetrachloride is not because
silicon atoms are larger and provide greater surface area for attack by nucleophiles. Also silicon
atoms have low lying d orbitals that can act as electron pair acceptors from nucleophiles. In
addition, silicon is less electronegative and is more susceptible to nucleophilic attack.

The high affinity of silicon for oxygen accounts for the existence of a vast array of silicate
minerals.

Oxides of germanium, tin and lead exist. These include GeO, SnO and PbO. The +2 oxide
becomes more stable on going down the group. There is an increase in stability of the 2+
oxidation state for the group IV elements with increasing atomic number. This results from the
inert pair effect in which an element loses all the p electrons in its outermost subshell, leaving a
filled s2 subshell; the pair of s electrons seems inert and less easily removed.

Organometallic compounds
Many organometallic compounds of group 4 are of great commercial importance. Organotin
compounds are used to stabilize PVC, as wood preservative and as pesticide. Tetraethyllead has
been used as an antiknock agent in leaded fuels but is now banned in most countries because of
the toxic effects of lead. Organometallic compounds of the group are tetravalent and have low
polarity.

Group V Elements

The group V elements are Nitrogen (N), phosphorus (P), Arsenic (As), Antimony (Sb) and
Bismuth (Bi). As in the rest of the p- block the element at the head of the group V, Nitrogen
differs from its congeners. Its coordination number is generally lower and it’s the only member
of the group to exist as a gaseous, diatomic molecule under normal conditions.

All the members except nitrogen are solids under normal conditions. The solid elements of group
V exist as allotropes, for example, white phosphorus is a solid consisting of tetrahedral P 4
molecules. White phosphorus is very reactive and bursts into flame in air to yield P 4O10. Arsenic
exists as yellow arsenic and metallic arsenic, where both consist of tetrahedral As4 molecules.

Nitrogen Activation
Nitrogen occurs in many compounds but N2 itself is unreactive. A few strong reducing agents
can transfer electrons to the N2 molecule at RT, leading to scission of the N-N bond, but the
reaction needs extreme conditions. The slowness of the reactions of N2 is the strength of the
N≡N triple bond and hence the high activation energy required to break it.

Nitrogen fixation is the catalytic conversion of nitrogen to ammonia. The fixation of nitrogen in
the soils is the catalytic conversion of nitrogen to NH4+ by the enzyme nitrogenase.

Fixation of nitrogen on the industrial scale:

Ammonia is produced in huge quantities worldwide for use as fertilizer and as primary source of
nitrogen in the production of many chemicals. The Haber process is used for the entire
production. In this process, nitrogen and hydrogen are combined at high temperatures (450°C)
and pressure (100 atm):

N2 (g) + 3H2 (g) -------- 2NH3 (g)

This process is the direct combination of N2 and H2 carried over a promoted iron catalyst; the
promoters are SiO2, MgO and other oxides. The reaction is carried out at high temperatures and
in the presence of a catalyst to overcome the kinetic inertness of N2 and at high pressures to
overcome the thermodynamic effect of unfavorable equilibrium constant at the operating
temperatures.

Simple compounds
The wide variety of possible oxidation states of the group V elements can be understood by
considering the electron configuration of the elements which is ns2np3. This configuration
suggests that the highest oxidation state is +5. According to the inert pair effect, we also expect
the +3 oxidation state to become more stable from nitrogen to bismuth. Nitrogen seldom have
coordination numbers greater than 4 but heavier elements reach coordination numbers 5 and 6 as
in PCl5 and AsF6-.

Hydrides
All the group V elements form simple compounds with hydrogen. Ammonia is of great industrial
importance. All the EH3 hydrides are toxic.

Ammonia
Ammonia is produced by Haber process and it is used to manufacture fertilizers.

Phosphine, Arsine, stibine

Phosphine (PH3), and arsine (AsH3) are poisonous and are of minor importance in chemistry.
All the group V hydrides are pyramidal, but the bond angle decreases down the group.
The bond angles for the hydrides of group V elements are as follows:

NH3 107.8°; PH3 93.6°; AsH3 91.8°; and SbH3 91.3°.

The reason for the decrease in bond angles down the group is due to steric effects – The E-H
bonding pairs of electrons will repel each other and this repulsion is greatest when the central
element, E is small, as in NH3 and the H atoms will be as far away from each other as possible in
a near tetrahedral arrangement. As the size of the central atom is increased down in the group,
the repulsion between the bonding pairs decreases and the bond angle is close to 90°.
Group VI Elements
The group VI elements are oxygen (O), sulphur (S), Selenium (Se), tellurium (Te) and polonium
(Po). They are often called Chalcogens. As in the rest of the p-block, the element at the head of
the group, oxygen, differs from the other lower members of the group. The coordination number
of its compounds is lower, and it is the only member of the group to exist as diatomic molecules
under normal conditions.

The elements
All the members of group VI other than oxygen are solids under normal conditions. Metallic
character generally increases down the group. Thus, oxygen, sulphur, and selenium are non-
metals, tellurium is a metalloid and polonium is a metal.
The group electron configuration of ns2np4 suggests a group maximum oxidation number of +6.
Oxygen never achieves this maximum oxidation state although the other elements do in some
circumstances. The electron configuration also suggests that stability may be achieved with an
oxidation number of −2, which is common for oxygen. The most remarkable feature of sulphur is
that it forms stable compounds with oxidation numbers between −2 and +6.

Oxygen is different chemically from the other members of the group. It is the second most
electronegative element in the periodic table. The small atomic radius of oxygen and absence of
accessible d orbitals contribute to its distinctive chemical character. Oxygen seldom has
coordination numbers greater than 4 in simple molecular compounds but its heavier congeners
reach coordination numbers of 5 and 6, as in SF6.

Oxygen – Oxygen has two allotropes, dioxygen (O2) and ozone (O3). Elemental oxygen makes
up 21% by mass of the atmosphere. Oxygen is readily available as O2 from the atmosphere and is
obtained on a massive scale by the liquefaction and distillation of liquid air. Oxygen is used in
many oxidation processes such as in the production of oxirane (ethylene oxide) from ethene.

Ozone (O3) is an explosive and highly reactive gas. It decomposes into dioxygen:

2O3 ----------------- 3O2

Sulphur - Sulphur occurs as deposits of the element in volcanoes, and hot springs, as the ores
galena, PbS, and as Epsom salts, MgSO4. Also occurs as H2S in natural gas and as organo-
sulphur compounds in crude oil. Unlike oxygen, sulphur (and the other heavier members of the
group) tends to form single bonds with itself rather than double bonds because of the poor π
overlap of its orbitals. Sulphur can exist in a large number of allotropic forms; the yellow
orthorhombic polymorph α-S8 consists of crown-like eight-membered rings.

Sulphur is reactive and interacts directly with many elements at room temp. For example, it
ignites in F2 to form SF6. Most of the sulphur produced is used to manufacture sulphuric acid and
also used in the vulcanization of natural rubber.

Selenium and tellurium occur in metal sulfide ores.

Simple compounds

Hydrides

The hydride of oxygen is water which is a liquid while the hydrides of the heavier elements are
toxic foul-smelling gases.

Hydrogen sulphide is a foul-smelling poisonous gas. The fact that it is a gas under normal
conditions (in contrast to water) demonstrates how the extent of hydrogen bonding is decreased
from H-O----H to H-S—H.

Hydrogen selenide, H2Se, and hydrogen telluride. H2Te are both toxic and foul-smelling gases.

Halides

Oxygen forms many halogen oxides and oxo-anions. The oxidation number of oxygen is −2 in
all its compounds with the halogens other than fluorine. Oxygen difluoride, OF2, is the highest
fluoride of oxygen and contains oxygen in its highest oxidation state (+2). Sulfur, selenium,
tellurium, and polonium have rich halogen chemistry. Some sulphur halides include SF4, SF6 and
S2F10.

Oxides

Oxygen is reactive and forms oxides with most elements. Sulphur forms two common oxides,
SO2 and SO3; SO2 is planar while SO3 is trigonal planar. Selenium and tellurium form SeO2 and
TeO2 respectively.

Group VII Elements

The group VII elements are fluorine, chlorine, bromine, iodine and astatine (At). Fluorine and
chlorine are poisonous gases, bromine a toxic volatile liquid and iodine is sublimable solid.

The elements

They have electron configuration of ns2np5 and they have high ionization energies, high
electronegativities and electron affinities. Fluorine is the most electronegative of all elements and
is never found in a positive oxidation state. The other halogens occur with oxidation numbers
ranging from -1 to +7.
The most striking physical properties of the halogens are their colours. They range from the
almost colourless F2 through yellow-green Cl2 and red-brown Br2, to purple I2.

Fluorine is the most reactive non-metal and is the strongest oxidizing agent among the halogens.

Fluorocarbons

The synthesis of fluorocarbon compounds is of great technological importance because they are
useful in applications ranging from coatings for non-stick cookware and halogen-resistant lab.
vessels to the volatile fluorocarbons used as refrigerants in air conditioners and refrigerators.