SCH 300 COMPARATIVE STUDY OF s- & p- BLOCK ELEMENTS

Course outline

General properties of the s- and p- block elements; important formal oxidation states of the various
elements. Occurrence and metallurgy. Some examples of applications of the elements and their
compounds. Comparative study of the chemistry as illustrated by halides, oxyhalides, oxides and
hydrides, with comparisons along the periods, down the groups and diagonally. The borane chemistry.

Practicals to include preparation of selected compounds and analysis of complex and soil samples.

Reference books

1 F. A. Cotton & G. Wilkinson, ‘Advanced Inorganic Chemistry – A Comprehensive Text’. 3 rd

edition (1992) Wiley Eastern Limited.
2 J. D. Lee, ‘Concise Inorganic Chemsitry’.

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GENERAL PROPERTIES OF THE ELEMENTS

These include;

 Elements in groups 1, 2 are also called s block elements: valence electrons fill in s orbitals.
 Elements in groups 13 to 18 are also called p block elements: valence electrons fill in p orbitals.

Lecture 1
Lecture Objectives
At the end of this unit you should be able to;

(a) explain the group and period number

(b) discuss the periodicity of the periodic table

Introduction

1.0 Periodic Table

1 Elements are arranged with increasing atomic number in rows (called periods) and columns
(called groups).

2 Elements in Groups 1 and 2 are also called s block elements: valence electrons fill in s orbitals.

3 Elements in Groups 13 to 18 are also called p block elements: valence electrons fill in p orbitals.

4 Elements in Groups 1, 2 and 13 - 18 are called main group elements.

5 Elements in Groups 3 - 11 are called transition metal because they have partially filled d orbitals.
Elements in Groups 3 - 12 are called d block elements because valence electrons filled in d
orbitals.

6 f block elements (also called Lanthanides and Actinides): valence electrons filling in f orbitals.

7 Elements in each group have similar valence-electron (electons in the outermost shell)
configuration and therefore similar properties.

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Figure 1.1. The structure of the periodic table (diagram from Atkins & Shriver).

Figure 1.2. The modern periodic table

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 1.1 Periodic Trends of Atomic Parameters
 Atomic properties such as effective nuclear charge, atomic radii, ionization energies, electron
affinity and electronegativity are important in accounting for the chemical properties of an
element.

1.2 Shielding
1. In atoms with more than one electrons, the effect of electron-electron repulsion depends on where
the various electrons are located in the atom.

 electrons in the outer shell (higher n) are pushed away by electrons in the inner shell (lower n).
As a result, the net nuclear charge (or effective nuclear charge, Z eff) felt by an outer electron is
substantially lower than the actual nuclear charge (Z). We say that the outer electrons are
shielded from the full charge of the nucleus by the inner electrons.

 Electrons in the same shell (same n) have an immediate effect in shielding the nuclear charge.

 Electrons in the outer shell (higher n) do not shield the nuclear charge from the inner electrons
(lower n)

 In 1930, Slater formulated a set of rules for the effective nuclear charge felt by electrons
in different atomic orbitals based on experimental data. The effective nuclear charge Z eff
can be calculated by the following equation:

 Zeff = Zactual - S

 Z: atomic number (number of protons);

 S: Slater screening constant;

 The values of S are estimated as follows:

 Write out the electron configuration of an element in groups of : (1s), (2s, 2p), (3s, 3p), (3d), (4s,
4p), (4d), (4f), (5s, 5p) etc.

 Electrons with higher n do not shield those in lower n; S = 0.

 If the electron in question resides in an s or p orbitals:

 Each of the other electron in the same ns, np group, S = 0.35.

 Each electron in the (n - 1) shell, S = 0.85.

 Each electron in the (n - 2) and lower shell, S = 1.00

 If the electron in question resides in a d or f orbitals:

 Each of the other electron in the same nd, nf group, S = 0.35.

 Each electrons in the (n - 1) shell, S = 1.00

Example:

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 1. Calculate the effective nuclear charge for the outermost electron in Oxygen.

Given: Electron configuration of O: 1s22s22p4.

2. Calculate the effective nuclear charge on a 3d electron in a Nickel atom.

Given: Electron configuration of Ni: 1s22s22p63s23p63d84s2.

1.3 Periodic Trend in Effective Nuclear Charge

Below is a table of the values of effective nuclear charge (Zeff) for s and p electrons in elements
Li - Ne:

Element Li Be B C N O F Ne

Z 3 4 5 6 7 8 9 10

1s 2.69 3.68 4.68 5.67 6.66 7.66 8.65 9.64

2s 1.28 1.91 2.58 3.22 3.85 4.49 5.13 5.76

2p 2.42 3.14 3.83 4.45 5.10 5.76

1. In the same atom, each electron with different n and l values can have a different Z eff because the
repulsive effects due to the other electrons is different. E.g., the Z eff for the B atom: 1s >>2s > 2p
and the size of orbitals is: 1s <<2s < 2p
2. For the same n and l value, Zeff increase across a period (e.g., from Li to Ne) as Z increases. As a
result, the size of the orbital decreases (electrons gets closer to the nucleus) and the size of the
atoms decreases. E.g. the Zeff for the 2p orbitals: B < C < N < O < F < Ne and the size of the 2p
orbitals is: B > C > N > O > F > Ne

1.4 Sizes of Atoms and Ions

 Since electrons can only be located by probability, there is no real boundary to an atom.
 Radii of atoms and ions are obtained experimentally from measuring bond lengths in molecules,
metals and ionic crystals by X-ray diffraction.

1. Covalent radii rcov:

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  defined as the half-distance between the nuclei of two atoms of the same element joined by a
covalent bond.

 E.g., Cl2: bond distance = 198 pm, atomic radius of Cl = (198)/2 = 99 pm.

2. Van der waal radius rvdw:

 Defined as the half-distance between the nuclei of two non-bonded atoms or molecules.

 Obtained from the closest approach between two non-bonded atoms or molecules in the solid
state.

 E.g., van der waal radius of Cl = 180 pm.

 In general, rvdw > rcov.

3. Ionic radius:

 defined as the distance between the nuclei of adjacent cations and anions in a purely ionic lattice.

In general, ranions > rcov > rcation for any given element.

 Cations: rNa+ = 116 pm; covalent radius rNa = 154 pm;

 Why? From Na (1s22s22p63s1) to Na+ (1s22s22p6): Zeff increases since no. of electrons decreases.

 Anions: the covalent radius rCl = 97 pm; rCl- = 167 pm;

 Why? From Cl(1s22s22p63s23p5) to Cl- (1s22s22p63s23p6): Zeff decreases since no. of electrons
increases.

1.5 Periodic Trend in Atomic Radii

 Across a row, the atomic radius deceases because the n value for the outer shell remains the same
but Zeff is increasing.
o E.g. For row stared by Na outer shell is 3s 1, 3s2, 3s23p1, 3s23p2 ….,3s23p6, atomic radius
decreases (from Na to Ar) because the Z value is increasing and the added electron do not
completely shield the increase in Z.
 Down a group, the increase in Zeff does not completely counteract the fact that the outer electrons
are in orbitals with higher n, so radius increase down a group.
o E.g. For group headed by Be outer shell is 2s 2, 3s2 , 4s2 , 5s2, 6s2, 7s2 , atomic size
increases from Be to Ra.
Table. Covalent radii (pm) of some selected elements

Li Be B C N O

132 89 82 77 77 73

Na Mg Al Si P S

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 154 136 118 111 106 102

K Ca Ga Ge As Se

203 174 126 122 120 117

Rb Sr In Sn Sb Te

216 191 144 140 140 136

Atomic Number

1.6 Periodic Trend in Ionic Radii

Going down a group in cations and anions:

 e.g , Mg2+(2s22p6)--> Ca2+(3s23p6)--> Sr2+(4s24p6)--> Ba2+(2s22p6)

 e.g , F-(2s22p6)--> Cl-(3s23p6)--> Br-(4s24p6)--> I-(2s22p6)
 n value of outer orbital increase but not counteracted by the increasing Z eff.
Size of isoelectronic series (ions/atoms containing the same number of electrons):

 e.g , O2-(2s22p6)--> F-(2s22p6)--> Ne(2s22p6)--> Na+(2s22p6) --> Mg2+(2s22p6)

 Zeff increasing --> Since same no. of electrons and Z increasing.
 R)O2-)> r(F-)> r(Ne)> r(Na+)> r(Mg2+)
Ionic radii (pm) of some selected main group ions

Li+ Be2+ O2- F-

60 31 140 136

Na+ Mg2+ Al3+ S2- Cl-

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 95 65 50 184 181

K+ Ca2+ Ga3+ Se2- Br-

133 99 62 198

Rb+ Sr2+ In3+ Sn4+ Te2- I-

248 113 81 71 221 216

In summary

The atomic size decreases across the period from left to right.

 Due to increase in effective nuclear charge (Z eff)

 And electrons are added to the same energy level

The atomic size increases down the group.

 Due to addition of an extra energy level charge (Zeff)

 Shielding of the outer electrons by the inner electrons (the increase in Z eff does not completely
counteract the increase in electrons in higher energy level.

Cations are usually smaller than the corresponding neutral atom (why?)

Atom Atomic radii/ Å ionic radii/Å

Na 1.52 Na+ 0.98
Fe 1.17 Fe2+ 0.76
Fe3+ 0.64

Anions are usually larger than the corresponding neutral atom (why?)

Atom Atomic radii/ Å ionic radii/Å

Cl 1.40 Cl- 1.81

1.7 Periodic Trend in the First Ionization Energy

The ionization potential of an atom is the minimum energy required to remove an electron from a gaseous
atom in its ground state. The magnitude of ionization potential is a measure of the effort required to force

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an atom to give up an electron, the higher the ionization energy, the more difficult it is to remove the
electron.

For many-electron atom, the amount of energy required to remove the first electron from the atom in its
ground state is called the first ionization energy (I1)

The second ionization energy (I2) and the third ionization energy (I3) are shown in the following equations

M M+ + e- i First ionization energy or I1

M+ M2+ + e- i2 Second ionization energy or I2

M2+ M3+ + e- i3 Third ionization energy or I3

Where X is the element and (g) denotes the gaseous state.

Higher ionization potentials labelled I 2, I3, I4 and so on will correspond to the successive removal of
additional electrons. The table below gives the first ionization energies of the first 21 elements.

Table 1-2; Ionization Potential (Energy) for the First 20 Elements

Z Element First Second Third Fourth Fifth Sixth

1 H 1312
2 He 2373 5248
3 Li 520 7300 11808
4 Be 899 1757 14850 20992
5 B 801 2430 3660 25000 32800
6 C 1086 2350 4620 6220 38000 47232
7 N 1400 2860 4580 7500 9400 53000
8 O 1314 3390 5300 7470 11000 13000
9 F 1680 3370 6050 8400 11000 15200
10 Ne 2080 3950 6120 9370 12200 15000
11 Na 495.9 4560 6900 9540 23400 16600
12 Mg 738.1 1450 7730 10500 13600 18000
13 Al 577.9 1820 2750 11600 14800 18400
14 Si 786.3 1580 3230 4360 16000 20000
15 P 1012 1904 2910 4960 6240 21000
16 S 999.5 2250 3360 3660 6990 8500

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 17 Cl 1251 2297 3820 5160 6540 9300
18 Ar 1521 2666 3900 5770 7240 8800
19 K 418.7 3052 4410 5900 8000 9600
20 Ca 589.5 1145 4900 6500 8100 11000

Ionization potentials are positive quantities.

If the ionization Energy was plotted against the atomic number, the periodicity will be clearly evident.
The 1st Ionization energy generally increases across the period.

Group I elements (alkali metals) have the lowest ionization energies. This is because the elements have
one valence electron that is effectively shielded by the completely filled inner shells. Consequently, it is
energetically easy to remove an electron from the atom of an alkali metal to form unipositive ion (Li +,
Na+, K+ …………….).

On the other hand non-metals have much higher ionization energies. The ionization energies of the
metalloids usually fall between those of metals and non-metals. This explains why metals readily form
cations while non-metals form anions.

However, there are irregularities in the increase of the ionization energy across the periods. For example
going across group 2 to 3, thus from Be to B and from Mg to Al. The group 3 elements have a single
electron in the outermost sub level (ns 2 np1), which is well shielded by the inner electrons and the ns 2
electrons.

Less energy is therefore needed to remove a paired s electron from the same principle energy level. This
brings about the lower ionization energies in group 3 elements

compared with those in group 2 in the same period.

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 Periodic trends

Atomic Number
Figure. Ionization energies of the first 55 elements

o Increase across each row, e.g. from Li to Ne; Na to Ar; K to Kr and so on (because Zeff increases
and the electrons in a given orbital are held more tightly, therefore, to remove the electron from
the atom requires more energy).
o Group 1 Alkaline metals (i.e. Li, Na, K, Rb, Cs and Fr) have minimum I.E. (due to only single
loosely held electron in the valence shell ns 1).
o Group 18 Noble gases (i.e. He, Ne, Ar, Kr, Xe and Rn) have the highest I.E. (due to filled valence
shell, ns2np6; high Zeff valence electrons are tightly held).
o Minor irregularity occur from group 12 to group 13 elements also from group 15 to group 16
elements:
o E.g. I.E. of Be (899.4 kJ/mol>I.E. of B (800.6 kJ/mol): due to completely filled ns2
configuration (2s2 in Be vs 2s22p1 in B);
o I.E of N (1402.3 kJ/mol> I.E. of O (1313.9kJ/mol): due to half filled p orbital in N
(2s22p3 in N vs 2s22p4 in O);
o I.E decreases down a group, e.g. Li>Na>K>Rb>Cs>Fr; He>Ne>Ar>Kr>Xe>Rn.
o Due to electrons filling in larger shell (larger n), further away from the nucleus.
Therefore, valence electrons are well shielded from the nucleus by inner shell electrons
and are loosely held.
o The ionization energy increase only slightly across a row in the transition or lanthanides
an actinides series.

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In summary

Factors affecting ionization energy

i) Size of an atom, the larger atom, imply low ionization energy

ii) Effective nuclear charge
iii) Screening effect of the inner electrons and type of electron

Across the period the ionization energy increase (why?)

Down the group the ionization energy decrease (why?)

3.9 Periodic Trend in Electron Affinity

Electron Affinities

The electron affinity of an atom is defined as the energy change obtained when a neutral atom in the
gaseous state captures an electron. Thus, the energy is released by the reaction represented below: -

X(g) + e-(g) →X- (g) + energy

It is the reverse of the 1st ionization potential and may be looked at as the ability of an atom to accept one
or more electrons. The largest electron affinities are those of the halogens. This is as expected since the
addition of one electron yields the stable octet configuration of the 18 th group elements-the noble gases.

X is an atom of an element. We assign a negative value to the affinity when energy is released. The more
negative the electron affinity, the greater the tendency of the atom to accept an electron.

The tendency to accept electrons increases as we move from left to right across the periodic table. Thus
Electron Affinity becomes more negative. The E.A of metals are generally more positive (or less
negative) than those of non-metals. The values differ little within a group, but the halogens have the most
negative E.A values, while the noble gases that have filled outer s and p sub shells have no tendency to
accept electrons. The E.A of oxygen has a negative value, which means that the process

O (g) + e- O- (g) is favourable

While that of the O- is

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O- (g) + e- O2- (g) is positive (780kj/mol) meaning that this process is not favourable
in the gas phase.

3.10 Periodic Trend in Electronegativity

Electronegativity χ

The tendency of an atom to attract electrons to itself in a chemical bond is referred to as

electronegativity. The greater the electronegativity of an atom, the more strongly the atoms attracts the
electrons of a bond. This concept was proposed by Linus Pauling in 1937.

Electronegativity cannot be calculated accurately or measured directly. However, we expect it to depend

on the magnitude of the charge and on the distance of the bonding pair of electrons from the nucleus.
There are two important trends in electronegativity within the periodic table: -

(a) electronegativity increases across a period as the charge increases

(b) electronegativity generally decreases from top to bottom in a group; because with
each successive shell, the bonding electrons are further from the nucleus.
Because the electronegativity of an atom cannot be defined quantitatively, it cannot be given a precise
value but approximate values. Table shows the electronegativity values

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Table; Electronegativity χ of some elements

Group 1 2 13 14 15 16 17 18

Period

1 H He

2.2 -

2 Li Be B C N O F Ne

1.0 1.5 2.0 2.5 3.1 3.5 4.1 -

3 Na Mg Al Si P S Cl Ar

1.0 1.2 1.3 1.7 2.1 2.4 2.8 -

4 K Ca Ga Ge As Se Br Kr

0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1

5 Rb Sr In Sn Sb Te I Xe

0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4

Increase of electronegativity-----------------------------------------→

Important application: Could use χ to estimate bond polarity

 Atoms with similar electronegativity (   0.4 ) form nonpolar bonds.

 Atoms whose electronegativity differs by more than 2 form ionic bonds.
 Atoms whose electronegativity differs by less than 2 form polar covalent bonds.

3.11 Common Oxidation State of the Elements

Oxidation number is the apparent charge assigned to an atom in a molecule or in a compound.

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Some oxidation numbers are fixed:

Elements Oxidation number

O -2 except in peroxide

H +1 except in hydride

Group 1 metals +1

Group 2 metals +2

Halogens -1 except in oxygen compounds

Study questions

 Because Zeff increases and the electrons in a given orbital

HORIZONTAL, VERTICAL AND DIAGONAL RELATIONSHIPS IN PERIODIC TABLE

In the previous section we have discussed horizontal (across the period) and vertical (down the group)
relationship. There is another relationship that is occurs, called diagonal relationship

Li Be B C

Na Mg Al Si

Diagonal relationship occurs generally to lighter atoms (for example, there is diagonal relationship
between Li and Mg, Be and Al, B and Si)

Reasons for diagonal element similarities

Polarizing power (read about Fajan Rules)

Covalence is increased by:-

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  Small cation+ large anion or large cation+ small anion
 Large charge density

The diagonal elements have generally similar polarizing power

For example Li & Mg, Be & Al or B & Si.

That is Li & Mg have almost the same polarizing power.

 As you move from Li to Be, there is an increase in polarizing power.

 Be to Mg there is reduction in polarizing power.

The two effect virtually cancel one another resulting to comparable conditions.

Valences

 In group 1, elements usually acquire valence 1by losing one electron. Exception, Li sometimes
form covalent ie valence=group number
 In group, 2 elements usually acquire valence 2 by losing two electrons. Exception Mg
sometimes form covalent
 In group 13, elements usually acquire valence 3.
 In group 14, elements usually acquire valence 4.
 In group 15, elements usually acquire valence 3 or 5.
 In group 16, elements usually acquire valence 2. There are few exceptions.
 In group 17, elements usually acquire valence 1. There are few exceptions.

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 Lecture 2
Lecture Objectives
At the end of this unit you should be able to;

(a) explain the General properties of group 1 elements, Occurrence and metallurgy.

(b) compare the chemistry of group 1 elements down the group

c) state some examples of applications of the group 1 elements and their compounds

d) describe the diagonal relationship of Li & Mg.

2.0 Group 1 Elements: Li, Na, K, Rb, Cs and Fr

Introduction
The closely related elements Li, Na, K, Rb, Cs, and Fr often termed the alkali metals, have a single
electron outside a noble a noble-gas core. Some relevant data are listed in table 1 below.

Table 1.Some properties of group 1`elements

Element Electronic Atomic radius Ionization potentials, eV E0 a

configuration Å 1st 2nd (V)
Li [He]2s1 1.52 5.390 75.62 -3.02
Na [Ne]3s1 1.86 5.138 47.29 -2.71
K [Ar]4s1 2.27 4.339 31.81 -2.92
Rb [Kr]5s1 2.48 4.176 27.36 -2.99
Cs [Xe]6s1 2.65 3.893 23.40 -3.02
Fr [Rn]7s1

a
For M+(aq) + e → M(s)

They have one electron in the outer energy level. The outermost electron is in the s orbital.
Are soft, low density, highly reactive, univalent and form colourless ionic compounds. Li show
considerable differences from the rest of the group.

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General properties
 Are the largest in each period
 Are soft- they have very small cohesive forces due to very few valence of electrons.

 Low density

 They have low first ionization energy, very reactive

 They have very low electronegativity values
 Li has high melting point as compared to the rest.

Occurrences
Sodium and potassium are in high abundance (2.6% and 2.4%) in the lithosphere and occur in large
deposits of sodium chloride (NaCl) and carnallites, (KCl·MgCl 2·6H2O). Lithium, rubidium and cesium
have much lower abundances and occur mainly in a few silicate minerals. Francium is radioactive and
has a half-life of 21 minutes.

Chemical properties
 Very reactive.
 Reacts in air to form oxide (stored in oil)

M + O2 Oxide

 Lithium react with nitrogen to form Li3N

6Li + N2 2Li3N (Red)

(Li usually attack N2 in air rather O2)

Li3N + 3H2O NH3 + 3LiOH

heat
Li3N 6Li + N2

Na-Cs do not form nitride

 Reaction with water

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They react vigourously with water

Na + H 2O NaOH + H2

These elements usually form the strongest bases. Higher energy is given out when Li react with water
(energetically) than the rest.

 Reduction potential (standard electrode potential)

These metals have high negative standard reduction potential (They are not easily reduced).

The high electrode potential value of Li is due to very high hydration energy. Li is very poor conductor
of electricity in solution as compared to other. Li is very much hydrated in solution, hence become very
heavy.

Oxides
These elements usually form oxides

Oxidation state
of oxygen
O2- Li + O2 Li2O Monoxide

2-
O O 2Na + O2 Na2O2 peroxide

O2- M + O2 MO2 superoxide

(where M= K, Rb & Cs)

The superoxide usually contain unpaired electron, implying they are paramagnetic most superoxide are
coloured, and partly due to defect in their crystals.

The peroxides could be coloured due to defect in their crystals.

LiO2 is never formed. Also it is difficult to form Cs2O2.

Recall Fajan rules

Small cations+ large anions→low lattice energy

large cations+ large anions→high lattice energy

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 Small cations+ small anions→high lattice energy

large cations+ small anions→low lattice energy

The other oxides are prepared by dissolving the metal in liquid ammonia and causing it to react with the
appropriate amount of oxygen.

These oxides are strong bases.

Oxides + H2O → Strong bases

With the exception to LiOH which is a weak base

Most of these bases are soluble in water except LiOH, hence the name alkali.

Most of these bases are thermally stable (not decomposed by heat). This is illustrate the strong
electropositive nature of the metals.

The peroxides and superoxides are oxidizing agents. They react with water to form H 2O2 and O2.

Li2O + H2O 2LiOH

Na2O2 + 2H2O 2NaOH + H2O2

2KO2 + 4H2O 2KOH + 2H2O2 + O2

Why does Li form monoxide and K form superoxide

Lattice energy (comparative size of ions)

Hydrides
The hydrides of this group are salt like.

2M + H2 → 2M+H-

It is easy for Li atom than Cs to form hydride. The reason for this is the comparative size of H atom and
metal involved. For large cation such as Cs, the lattice energy is very small. Stability of hydrides
decreases down the group.

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Reaction of hydrides with water
LiH + H2O LiOH + H2

Electrolysis of LiH gives hydrogen at the anode and Li at the cathode. It is a very useful source of
hydrogen. Since it has low molecular mass, more hydrogen is evolved than hydride itself.

Li[AlH4] –useful reducing agent mostly in organic chemistry

4LiH + AlCl3 Li[AlH4] + 3LiCl

Halides
They form ionic halides e.g. LiF, LiCl, LiBr etc

NaF, NaCl, NaBr etc

Li+ is very small, it is heavily hydrated for example LiX 3·H2O. Other alkali metal halides e.g. NaCl,
NaBr, KCl form anhydrous crystals.

 All the halides of group 1 adopt the NaCl type of structure. Na + surrounded by 6Cl- with
coordination number 6.
 Exception. Cs halide, e.g. CsCl type of structure have coordination number of 8. This could be

attributed to difference in size of cation and anion. i.e.

 Metal halide react with other halogen or interhalide compounds, for example

KI + I2 K[I3] i.e K+I3-

KBr + ICl K[BrICl]

KF + BrF3 K[BrF4]

Organic Compounds of Group 1 Elements

React with organic acids to form salts

RCOOH + M RCOOM

M= Na , K etc

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Sodium salts of long chain carboxylic acids e.g. palmitic, stearic, oleic and linoleic acids are important as
soaps.

Group 1 metals form alkyl and aryl compounds, for example Li(CH 3)4. This compound is covalent and
soluble in organic solvents. This is usually tetrameric or hexameric. It usually sublime on heating.

Preparation

ether
RCl + 2Li LiR + LiCl

If R= n-butyl you get n-butyl lithium. This is used in organic chemistry in preparation of other
compounds

LiR + RI R R + LiI

LiR + H+ RH + Li+

LiR + Cl2 RCl + LiCl

3LiR + BCl3 BR3 + 3LiI

LiR + HgI2 HgR2 + 2LiI

Li+R- are extremely reactive. Catch fire in air. React violently with most compound with exception
nitrogen and saturated hydrocarbon.

Solubility and hydration

 All simple salts of group 1 elements are soluble in water.
 Li+ is the smallest; it is expected to conduct electricity faster than the larger Cs + ion. Conductivity
decrease Cs+>Rb+>K+>Na+>Li+.
o Explanation: Li+ is heavily hydrated while Cs+ is the least hydrated.

There is a decrease in hydration from Li→Cs.

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Nearly all salts of Li are hydrated.

A few salts of Na are hydrated while few of K are hydrated.

Rb and Cs have no hydrated salts.

Li+ is tetrahedrally surrounded

H H
H O
H
+
O Li
O
H O
H H H

Could have two of secondary shells

Ion ΔH hydration
kJ/mol
Li+ -519
Na+ -405
K+ -322
Rb+ -293
Cs+ -263

Solubility

 Down the group – solubility is expected to decrease.

o Solubility depends on lattice energy and hydration energy.
o For salt to dissolve, hydration energy should be greater than lattice energy.
o The solubility of fluoride and carbonate increase down the group

Salt Total hydration energy lattice energy Solubility

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 kJ/mol kJ/mol g/kg H2O
LiF -1034 -1039 2.7
NaF -921 -919 42.2
KF -832 -817 923
RbF -808 779 1306.0
CsF -779 -730 3670.0

Down the group the cation size increase- hence a decrease in hydration energy. Down the group sizes of
cation and anions are not comparable.

 LiF is not soluble since lattice energy is greater than hydration energy.

Difference between lithium and the members of group 1

 Similar polarizing power of Li and Mg.

The

1. Melting point and boiling points of Li are comparably higher.

2. Li is much harder than other group 1 elements.
3. Li reacts least readily with O2 forming monoxide, the higher oxide being unstable.
4. Li is much less electropositive, therefore many of its compounds are less stable; Li 2CO3, LiNO3
and LiOH all form the oxide on gentle heating and no solid bicarbonate is known.
5. Unlike group 1 elements, but like group 2, Li forms a nitride, Li 3N.
6. Unlike group 1 elements, Li react directly with C to form an ionic carbide. Group 2 elements all
similarly react with C.
7. Li has a greater tendency to form complexes than the heavier elements and ammoniated salts such
as Li(NH3)4I exists as solids.
8. Like the corresponding Mg salts, Li 2CO3, Li3PO4 and LiF are insoluble and LiOH is only
sparingly soluble in water.
9. Due to their covalent nature, the halides and alkyls of Li and Mg are soluble in organic solvents.
10. The lithium ion and its compounds are more heavily hydrated than those of the rest of the group.

24
Extraction of metals
 Group 1 elements are the strongest chemical reducing agents
i) Typical metals (e.g Fe) are extracted by reducing the oxide at high temperature using
carbon (coke). This method is not applicable to group 1 elements.
ii) Electrolysis of aqueous solution. Hg is used as the electrode to form sodium almagam
iii) Electrolysis of fused halides. To extract these metals halides e.g. chlorides are fused and
then electrolyzed. These halides melt at very high temperature due to high lattice energy.
E.g NaCl melts at 803 ºC. To lower the melting point, CaCl 2 is added to the mixture to
get eutectic mixture (NaCl+CaCl2) which melt at 505 ºC. The electrolysis is done at this
temperature. At the cathode Na and Ca are deposited and at the anode Cl 2 is evolved. Na
and Ca are separated.

25
 Lecture 2
Lecture Objectives
At the end of this unit you should be able to;

(a) explain the General properties of group 2 elements, Occurrence and metallurgy.

(b) compare the chemistry of group 2 elements down the group

c) state some examples of applications of the group 2 elements and their compounds

d) describe the diagonal relationship of Be & Al.

2.0 Group 2 Elements: Be, Mg, Ca, Sr, Ba and Ra

Introduction
The closely related elements Be, Mg, Ca, Sr, Ba, and Ra often termed the alkali-earthmetals, have two
single electrons outside a noble a noble-gas core. Some relevant data are listed in table 1 below.

Table 1.Some properties of group 1`elements

Element Electronic Atomic radius Ionization potentials, eV E0 a

configuration Å 1st 2nd (V)
Be [He]2s2 0.89 9.32 18.21 -1.85
Mg [Ne]3s2 1.36 7.64 15.03 -2.37
Ca [Ar]4s2 1.76 6.11 11.87 -2.87
Sr [Kr]5s2 1.91 5.69 10.98 -2.89
Ba [Xe]6s2 1.98 5.21 9.95 -2.90
Ra [Rn]7s2 5.28 10.10 -2.92

a
For M2+(aq) + 2e → M(s)

They have two electrons in the outer energy level. The outermost electrons are in the s orbital.
Usually form divalent ion M2+ ion.
Are highly reactive but relatively less reactive than group 1 elements
They usually form colourless compounds.
They are diamagnetic.

26
 Beryllium form covalent compounds.
Be show considerable differences from the rest of the group, it have diagonal relationship with
aluminium.

General properties
 Be is different from the other members of the group because its size and has high
electronegativity value.
 Group 2 elements are large , but smaller than group 1 elements
 Ionization energy.
o They have higher first ionization energy than group 1. Reasons: large Z eff and stability
associated with filled ns2 orbital has extra stability associated with it.
o Second ionization is higher compared to the first ionization energy (Explain the
difference)
 Two electrons are used in metallic bonding. Implying strong metallic bonding [harder and
denser). They have higher melting points. The melting point does not vary regularly. The
reason for this is that these metals adopt different packing.

To form M2+, four times group 1 ionization energy is required. This is offset by the high hydration energy
which is favoured by high charge and smaller size. Lattice energy is four times that of group 1.
Hydration energy is 4 times greater than those of group 1. This is due to smaller size and increased
charge.

ΔH hydration decrease down the group 2

Solid compounds are heavily hydrated. For example MgCl 2·6H2O, CaCl2·6H2O and BaCl2·6H2O

Ion Hydration energy

/kJ mol-1
Be2+ -2494
Mg2+ -1921
Ca2+ -1577
Sr2+ -1443
Ba2+ -1385

The ions have gas configuration; no unpaired e -(s), hence they are diamagnetic and form colorless
compound unless the acid radical is coloured.

27
Anomalous behaviour of Berylium
Reasons

 Small size &

 High charge

Recall

 Small cation favour covalency &

 Large anion favour covalency

Example of Be salts. [Be(H2O)4]NO3, [Be(H2O)4]SO4 , [Be(H2O)4]Cl2

 Its salts are extensively hydrolyzed to give the tetrahedral complex in [Be(H 2O)4]2+
 Hydration increases the effective size of Be ion. Most Be salt occurs in form e.g. [Be(H 2O)4]NO3,
[Be(H2O)4]SO4 , [Be(H2O)4]Cl2 . Such compounds as BeSO4 do not exist.

Electronic structure of Be atom 1s22s2

2s 2p
↑↓
Be

2s 2p
Be2+

Be ion having gained 4 lone pairs of e from 4 oxygen atoms in water molecules

2s 2p
↑↓ ↑↓ ↑↓ ↑↓

Sp3 hybridization (tetrahedral)

Be−O bond is strong, and this weakens the O−H bond, hence there is a tendency to lose protons

2+
H
+
(H2O)3Be O +
(H2O)Be O + H
H H

28
Be salts are usually acidic in pure water.

 Others salts of group 2 do not interact so strongly with and do not hydrolyze appreciably.
 Be salts never have more than 4 molecules of H 2O of crystallization, because there are
only 4 orbitals available in the second shell of electrons whereas Mg can have a
coordination number of 6 by using 3d orbitals as well as the 3s and 3p orbitals.

3s 3p 3d
                 
3 2
Sp d hybridization (octahedral)

 Mg in the presence of highly electronegative atom, e.g. Cl -. The chlorine contract the 3d orbital
and hence the 3d orbital is made available for bonding

Solubility and Lattice energy

The solubility of most salts in group 2 decreases with increasing atomic weight. The only exceptions are
fluorides and hydroxides (while for group 1 the exceptions are fluorides and carbonates).

 Reasons: Down the group there is reduction of lattice energy as the size of cations increases; the
packing of ions become very poor.

Chemical Properties
 Less electronegative than those in group 1 elements. Hence, less reactive than group 1 elements.
But still react with water to form hydrogen and metal hydroxide, but the rate of reaction is
relatively low.
 Be is not typical, however the reaction

Be + H 2O BeO + H2 is very doubtiful

Mg + 2H2O Mg(OH)2 + H2
steam

Ca + 2H2O Ca(OH)2 + H2
cold

Ba + 2H2O Ba(OH)2 + H2
cold

Be(OH)2 is amphoteric (act both as acid and base). While the other increase in basic strength in order

Mg → Ba.

 Solutions of Ca(OH)2 (lime water) and Ba(OH)2 (Barta water) are usually used to detect CO 2 gas.

29
 Ca(OH)2 + CO2 CaCO3+ H2O
white precipitate

Ca(OH)2 + H2O + CO2 Ca(HCO3)2

(excess) soluble
colourless solution

Ca(HCO3)2 stable in solution, when left to stand it decompose to CaCO 3 . This accounts for the formation
of stalaGmite and stalActite in caves of rock salts.

Oxides
 All the elements form MO (monoxide). Peroxides and superoxides are formed only under forced
conditions. The oxides are not formed by direct heating of metal with oxygen, but by thermal
decomposition of MCO3, M(OH)2 and MSO4.
 Mg → Ba oxides are ionic.
 BeO is covalent. This can be explained by Fajans rule.
o BeO is insoluble in water
o Dissolves in acids to give salts
o Dissolves in alkali to give beryllates
 Beryllates on standing precipitate the Be(OH) 2.

MgO + H2O Mg(OH)2 weakly basic

The hydroxide increase the basic strength down the group.

Carbonate Decomposition
temp. /ºC
BeCO3 <100
MgCO3 540
CaCO3 900
SrCO3 1290
BaCO3 1360

 Most of these carbonates are always ionic except BeCO3, which has the formula [Be(H 2O)4]CO3,
hydrated form.

30
Halides
M + X → MX2

Direct combination at appropriate temperature. They can also be formed by direct reaction of halogen
and metal or carbonate.

2HCl + MCO3 → MCl2 + CO2

Beryllium halides

 Are covalent and very hygroscopic

 Usually fumes in air due to hydrolysis
 They do not conduct electricity and usually sublime on heating

Anhydrous beryllium halides in solid form are polymeric but in vapour state they are monomeric BeCl2
or dimeric (BeCl2)2, usually resemble (BeH2)m

The bonding is three centre bonding. BeCl 2 is linear Cl−Be−Cl (monomer) while Beryllium dimer is
three centre bonding.

Cl
Cl Be Be Cl

Cl dimer

Cl Cl
Cl Cl
Cl
Be Be Be Be
Cl
Cl Cl Cl Cl
polymer

 Fluorides of group 2 elements are insoluble

 Other halides are ionic and readily soluble in H2O.
 The solubility of halides decreases down the group (except the fluorides)
 CaCl2 is usually used as drying agent, while MgCl2 is used in electrolytic extraction e.g. Mg.

Reaction with N2
When you expose (burn) group 2 metals in air they react with oxygen to form monoxide, peroxide and
superoxide. Group 2 elements burns in air to form nitrides, M 3N2.

N2 + 3M → M3N2

31
The reaction require a lot of energy to convert the stable N 2 molecules into N33- (nitride) ion. The energy
is recovered from the high lattice energies resulting from the doubly charged ions in group 2 or the ver
small size ion in the case of Li.

 Be compound (Be3N2) is volatile while (Mg3N2) are not volatile. Mg3N2 form crystallized solid
which decompose to N2 and Metal on heating.
 The nitride on reaction with water, you get ammonia and metal oxide or metal hydroxide
 Mg3N2 + 6H2O → 3Mg(OH)2 + 2NH3

Organometallic Compound
Grignard reagent RMgX

 Versatile reagent in organic chemistry

Mg + (alkyl halide or aryl halide → Grignard reagent
(absolutely dry organic solvent eg diethyly ether)
Mg + RBr → RMgBr (Grignard reagent)
Et2O, 35 C

Grignard reagent are usually solvated or polymetlized with halogen bridges

R OEt2
Mg
Br OEt2

Some typical reaction

C6H5MgBr + CO → C6H5COOH

H2O

RMgBr + R2CO → R3COH (tertiary alcohol)

H2O

RMgBr + RCO → R2COH (secondary alcohol)

H2O

RMgBr + I2 → RI

RMgBr + H+ → RH

2RMgBr + BeCl2 → BeR2

RMgBr + BCl3 → BR3

32
 RMgBr + SiCl4 → SiCl3R, SiCl2R2, SiClR3 and SiR4

RMgBr + BeCl2 → BeR2 if R is methyl group

Be(CH3)2 dimeric in vapour state and form a polymeric solid state. The type of structure resemble those
of BeCl2 [three cntre bridge]

Be(CH3)2 + BeCl2 → 2ClBe(CH3)

Complex
 Group 2 elements are usually not noted for their ability for formation of complex
 Complex formation is favoured by
o Small highly charged ion
o Suitable empty orbital or appropriate energy
 Be forms many complexes (size of cations is very small)
 Ba form very few complexes
 BeF2 readily coordinate extra fluoride ion forming
[BeF3]- or BeF4]2- it only use sp3 hybridization

2s 2p
↑↓ ↑↓ ↑↓ ↑↓

Sp3 hybridization (tetrahedral)

Tetrafuoroberyllate M22+[BeF4]2- very well known, resemble sulphates in properties.

Be
F
F
F Tetrahedral

 Be also form many chelate compounds e.g. when Be(OH) 2 is evaporated with a acetic acid, basic
beryllium acetate is formed Be4O(CH3COO)6.
 Covalent in nature
 Centarl atom is O
 O atom is surrounded by 4 Be atom tetrahedrally
 The six acetate groups being arranged along the six edges of tetrahedron

33
 Be O R

O
Be
Be
O

Be O
R O
O
Be4O(Ac)6
R

 Other chelate compounds include, beryllium oxalate, catechol and acetyl acetone.

2-
O

C
O O
C
Be
O O

C C

O O

Beryllium oxallate

 Be is extremely toxic- probably due to

o Ease of complex formation [mojor factor]
o Its high solubility
 Complex formed by Mg eg Chlorophyll
 Ca form complex with EDTA and acetyl acetone

34
Extraction of the elements
 They are strong reducing agents
 Not easy to extract by chemical reduction because they are strong reducing agents. Cannot be
reduced by carbon.
o Usually form carbides with carbon
 They are strongly electropositive, aqueous solutions cannot be used for displacing metal by
another or by electrolysis. Reasons: Reaction of metal with water.
 A mercury cathode can be employed in this electrolysis, but the recovery of the metal from
amalgam is difficult.
 All metals can be obtained by electrolysis of fused chloride. In this situation NaCl is added to
lower the melting point, {with Ba, & Sr it form colloidal, not appropriate}.
 BeO os usually extracted from beryl Be3Al2Si6O18.

Beryl → BeSO4

(Heat, H2SO4, NaOH)

BeSO4 + NH4OH → Be(OH)2 → BeO

(heat)

BeO has ceramic properties and is usually used in nuclear reactor

Nowaday, the extraction of Be is

Beryl + HF → Na[BeF4] → hydroxide → oxide

(NaOH)

Be(OH)2 →BeCl2 →electrolysis →Be

(C+Cl2) (fuse)

Reduction of Be with magnesium

BeF2 + Mg → MgF2 + Be

Be is transparent to x-ray, hence used in X-ray equipment eg. Window.

35
Mg is extracted by heating MgO with carbon

MgO + C ↔ Mg + CO (shock cooling fast cooling, the gas to avoid equilibrium)

Calcium is obtained by heating CaCO3 to give CaO

CaO + NH4Cl → CaCl2

CaCl2 fuse → electrolysis

Sr and Ba, we obtain their oxide. We use Al to reduce their oxide

Sr or Ba →Al2O3 +Sr or Ba

(Al thermal reduction)

Differences between beryllium and the other group 2 elements

Berllium is amolous in many of its properties and show diagonal relationship to aluminium in groups 13.

1) Be is very small and has a high charge density

 Shows a strong covalency tendency (fajans rules)
 Melting points of its compounds are lower
 BeF2 mpt =800 °C, rest of the group mpt>1300 °C.
 Be compounds are usually soluble in oxygenic solvents
 Most of Be compound hydrolysis in water rather like the compounds of aluminium.
2) Be forms many complexes not typical of group 1 and 2
3) Be like Al is rendered passive by nitric acid
4) Be is amphoteric, liberating H2 with NaOH and forming beryllates. Al forms aluminate.
5) Be(OH)2 like Al(OH)3 is amphoteric.
6) The salts of Be are extensively hydrolyzed
7) Halide of Be are polymeric with multi-centre bonding associated with electron deficiency. BeCl 2
usually forms chain but also exist as a dimer. AlCl3 is a dimer.
8) The hydrides and alkyl compounds of Be are also polymeric
9) Be salts are among the most soluble known
10) Be2C like Al4C3 yield methane on hydrolysis.

36
 Lecture 3
Lecture Objectives
At the end of this unit you should be able to;

(a) explain the General properties of group 13 elements, Occurrence and metallurgy.

(b) compare the chemistry of group 13 elements down the group

c) state some examples of applications of the group 13 elements and their compounds

d) describe the diagonal relationship of Al & Si.

2.0 Group 13 Elements: B, Al, Ga, In, and Tl

Introduction
The closely related elements B, Al, Ga, In and Tl have three single electrons outside a noble a noble-gas
core. Some relevant data are listed in table 1 below.

Table 1.Some properties of group 13 elements

Element Electronic Atomic Ionization potentials, eV E0 a

configuration radius 1st 2nd 3rd 4th (V)
Å
B [He]2s22p1 0.80 8.30 25.15 37.92 259.30 Not
measurable
Al [Ne]3s23p1 1.25 5.98 18.82 18.44 119.30 -1.66
Ga [Ar]3d104s24p1 1.25 6.00 20.43 30.60 63.80 -0.53
In [Kr]4d105s25p1 1.50 5.79 18.79 27.90 57. -0.34
Tl [Xe]4f145d106s26p1 1.50 6.11 20.32 29.70 50.50 +.72
a 3+
For M (aq) + 3e → M(s)

In+(aq) + e → In(s) E=-0.147

Tl+(aq) + e → Tl(s) E=-0.336

37
General properties
They have three electrons in the outer energy level. The outermost electrons are in the p orbital.
Usually form trivalent ion M3+ or monovalent ion.
Boron non metal. Metallic character increase down the group.
Al is the 3rd most abundant element on earth crust
o It occurs as bauxite Al2O3∙H2O or aluminosilicate rock or clays.
o
The small size of ions, their high charge and the large values for the sum of the three ionization
energy suggest that the elements are largely covalent.
Boron forms covalent bonds, AlCl3 and GaCl3 are covalent in their anhydrous state.

Chemical properties
Aluminium ion is usually surrounded by water molecules [Al(H 2O)6]3+, which is sp3d2 hybridization,
octahedral structure.

M−O bond is very strong Be−O and Al−O

 It is acidic

H 3+ 2+
(H2O)5M O (H2O)5M O + H+
H H

Most Al salts are acidic.

Ga has filled 3d10, d shell has very low screening effect. The size of Al and Ga are almost the same.

Ga to In there is filled 4d10 shell. There is an increase in size.

From In to Tl. There is 4f145d10 These two shell have low screening effects. Tl [Xe] 4f145d106s26p1. The
metallic character increase from B to Al. Then decrease down the group. In group 13, they exhibit
valence 1 or 3. Thallium has higher tendency to form univalent ion (+1).

38
Explanation

The electron (6s2) in the outermost shell remain paired. They do not take part in chemical reaction. The
energy required to unpair these two electrons is very high. This is refered as “inert pair effect”.

 Empirical formula of GaCl2, one may conclude that gallium is divalent but in actual fact, this
compound has the form Ga+[GaCl4]-, oxidation state +1 and +3. (mixed valence compound).
o The molecular formula is Ga2Cl4. The two Ga atoms are not the same

Boron
There are two types of boron:

 Amorphous and Crystalline

 The amorphous boron is impure, burn in air to form oxide and nitride. React with hydrogen
to form trihalides. It also reduces HNO3 and H2SO4 and liberates H2 with NaOH.
 Crystalline boron is very unreactive except at high temperature and with reagent such as conc
H2SO4 and Na2O2.
 Al, Ga, In and Tl are silvery white metals.
 Al is stable in air- This is because it forms a thin oxide layer which protect metal from further
attack. If the oxide is removed e.g. when amalgamated with mercury (Hg) the metal is rapidly
oxidized and reacts with cold water.
 Ga and In are stable in air and are not attacked by water except when free oxygen is present.
o The electronegativity of Al is highest in the group.
o Thallium is a little more reactive and is oxidized in air.

Electropositive character
Electropositive character increases from B to Al. From Al to Tl, the electropositive character decrease
down to Thallium. The trend in electropositive character is related to atomic size. Ga, In and Tl caome
after d block elements while B and Al come after s block elements.

In group 13 ionization energy increase are much lower than expected. The IE between Ga nad Al—It
should be expected Ga to have low IE than Al.

39
Oxides
Usually form sesquioxides M2O3. Made by heating the group 13 element in oxygen.

B2O3 is made by dehydrating boric acid.

100 oC red heat

H3BO3 HBO2 B2O3
orthoboric metaboric
acid acid

Boron is a no-metal

B2O3 is non-metallic oxide, hence it is acidic. It is considered as anhydride of boric acid. On heating
with metal oxides, it usually give metaboric acid which have characteristic colour.

Borax bead test

CoO + B2O3 Co(BO)2

cobalt metaborate

B2O3 react with very strong acidic oxides of P, As to form phosphate and arsenate respectively.

P2O5 + B2O3 2PBO4

phospahte

Boron sesquioxides and the borates

B2O3 is considered as anhydride of boric acid

100 oC red heat

H3BO3 HBO2 B2O3
orthoboric metaboric
acid acid

Orthoboric acid (H3BO3) is a weak monobasic acid.

H3BO3 + H2O H+ + [B(OH)4]-

metaborate ion

At high concentration, polymericmetaborate species are formed e.g

2H3BO3 H+ + [B2O3(OH)4]- + 2H2O

40
Addition of certain organic compounds (polyhdroxyl compounds), e.g. glycerol , manital or sugar makes
the H3BO3 a strong monobasic acid.

This polyhydroxyl compound must have OH groups at the cis positions.

C OH
cis position
C OH

This removes the metaborate ion thus shifting the equilibrium to the right resulting into production of
more H+ ions. Thus the acidity of H3BO3 is increased.

C OH HO
OH C O OH
+ B B
C OH HO OH C O OH

In the simple borates, each B is bonded to 3 oxygen atoms arranged at the corners of a equilateral triangle

2s 2p
↑↓ ↑
B

2s 2p
↑↓ ↑↓ ↑↓
B*

Sp2 hybridization (trigonal planar)

B
O O

41
Orthoboric acid contains triangular BO33- units which are hydrogen bonded together into two dimension
sheets

H H

O O
H B H
H H
O O
O
B H H B H
H
O O O O

H H H
H

O O O O H
H
B H H B
O
O O
H B H H
H
O O

H
H
Hydrogen bonded structure of orthoboric acid

Metaborates units are joined together forming a variety of chains or ring structures.

 Borax, Na2B4O7∙10H20- used as a primary standard

Al2O3 made by dehydrating Al(OH)3.

Aluminium has a strong affinity for oxygen

ΔHformationAl2O3 =1700 kJ/mol

It is used in thermite reduction of metal oxide

3Mn3O4 + 8Al 4Al2O3 + 9Mn

2Cr2O3 + 2Al 2Al2O3 + 6Cr

42
Al(OH)3 is a white gelatinous substance. It is amphoteric, but acts principally as a base giving salts that
are hydrated ie. [Al(H2O)6]3+.

Al depicts acidic properties and it react with sodium hydroxide to give aluminate e.g. NaAlO 2∙10H20.
The structure of this change with pH and ion concentrations

o pH above 13 [Al(OH)4]- is tetrahedral

o pH 8-12 the ions polymerize by means OH bridges with each Al being octahedrally
coordinated
o In concentrated solutions above 1.5 M the ion

2- exist
[(HO)3Al O Al(OH)3]

Al(OH)3 is precipitated by CO2 or trace acid

Ga2O3 like Al2O3 is also amphoteric

soluble Alkali
Ga2O3 gallates

Tl and In sesquioxides are basic and do not form either hydrates or hydroxides

Tl Strong base and is soluble in water

Hydrides
 None of the group 13 element reacts directly with hydrogen gas but a number of their hydrides
are known.
 Boron hydrides sometimes called boranes are analogy with alkanes
 There are seven well characterized series which fall into two groups, i.e. B nHn+4 and BnHn+6. (less
stable).

BnHn+4 e.g. B2H6 (diborane); other examples include B5H9 (pentaborane-9); B10H14 (decaborane-14).

BnHn+6. Include B4H10 (tetraborane), B5H11 (pentaborane-11), B6H15 (nanoborane or enneaborane) and
B10H16 (decaborane-16)

43
Diborane

Prepared in a variety of ways

heat
Mg3B2 + H3PO4 mixture of barane mainly B4H10 2B2H6

slight electric
2BCl3 + 6H2 discharge
ii) 2B2H6 + 6HCl

2BCl3 + Li[AlH4]
iii)
2B2H6 + 3AlCl3 + 3LiCl

 Borane do not have enough electrons to form the expected number of covalent bond---They are
electron deficient

1.19
H H
H
B B B2H6
H 1.33A H H

electrons taking part

6 e- from 2B
6 e-rom H Expected number of e- = 16
-
12 e

8 e- are used for normal covalent bond.

The remaining 4 e- , we have each pair of electron being shared by 3 atoms.

There is an sp3 hybridization. Two of sp3 orbitals are used to bond with terminal H. The other sp 3 orbitals
each interact with s orbital of bridging H.

H H H H H
H
B B B B
H H H H H H

Three centre bond

this kind of bond occr in AlCl3 chain

44
Halides
Trihalides

 All the elements form trihalide

 Boron halides are covalent and gaseous
o Sp3 hybridization, implying trigonal planar
o BX3 is a Lewis acid, accept electrons from O, P, N, and S
o BF3 is useful as organic catalyst for Friedal Craft reactions such as alkylation, acylation
and esterification
 The fluorides of Al, Ga, In and Tl are anionic and have high melting point
 Other trihalides are largely covalent when anhydrous e.g. AlCl 3, AlBr3 and GaBr3 existing as
dimmers thus attaining an octet of electrons.

Cl Cl
Cl
Al Al Al Cl Al
Cl Cl Cl 3 centre bond

Dihalides

B2Cl4 unstable, decompose slowly at room temperature

electric discharge
2BCl3 + 2Hg low pressure 2B2Cl6 + Hg2Cl2

Ga and In also form dihalides

2GaCl3 + Ga
3GaCl2

In + 2HCl InCl2 + H2

GaCl2 exist as Ga +[GaCl4]-. The two Ga atoms are not equivalent, one has oxidation 1 and the other 2.
Same apply for In.

Tl form univalent thallium halide. TX are more stable than trihalide (recall inert pair effect)

45
Monohalides

All elements in this group form monohalides. MX are formed in gaseous phase at elevated temperature.

AlCl3 + HI high temp

3AlCl

Monohalides are very unstable. They are usually covalent with exceptions of TlF which is ionic. (BX) n
form polymer

Complexes
Group 13 elements usually forms complexes much more readily than the s block elements . This can be
attributed to the smaller size of ions and increased charge.

For example

Li[AlH4] tetrahedral shape

H[BF4] sp3 hybridization

Halide complexes

[GaCl6]3-, [InCl6]3- and [TlCl6] - tetrahedral

They form complexes with chelating ligands, especially acetlylacetone, oxalate and 8-hydroxyquinoline

CH3

M CH

CH3 3

acetlylacetone complex

46
Organometallic Compounds
 Grignard reagents

AlCl3 + 3C2H5MgI Al(C2H5)3

GaCl3 + 3C2H5MgI Ga(C2H5)3

 Alkyl or aryl compounds

AlCl3 + 3RLi AlR3 + 3Li

GaCl3 + 3RLi GaR3 + 3Li

Al compounds are unusual, most of them form dimers

Reaction of boranes (hydrides of Boron)

B10H14 + RC CR B10H10R2
carborane
Decaborane-14

B10H14 + Me3N + BH3 [MeMH]+[B12H12]-

excess NH3
low temp B2H62NH3 ionic
B 2H 6

excess NH3
high temp (BH)n borone nitride
B2H6

47
 H

B
H N N H

H B B H B3N3H6
N
boraxole (ionic benzene)
H same structure as graphite

Extraction
Boron: Reduction of the sesquioxide B2O3 with Mg or sodium.

Boron exist as borax Na2B4O∙7H2O

Acid heat
Na2B4O710H2O H3BO3 B2O3 B
amorphous boron
5% impurity

Crystal Boron

Obtaine in small amounts by reduction of BCl3 with H2 or the pyrolysis of BI3.

red hod
2BCl3 + 3H2 2B + HCl
W & Ta filament

red hod
2BI3 2B + I
W & Ta filament

Boron is used to increase the hardness in steel.

Aluminium exist as bauxite Al2O3∙H2O

NaOH + Al2O3H2O Sodium aluminate soluble

This separate it from iron ores

Al(OH)3 is precipitated using CO2 or seeding with Al2O3.

48
Ppt of

Heat
Al(OH)3 Al2O3
Calcinated

Al2O3 fuse it with cryolite and alectrolyzed

Al is used to make alloys, paints cooking utensils etc.

49
 Lecture 4
Lecture Objectives
At the end of this unit you should be able to;

(a) explain the General properties of group 15 elements, Occurrence and metallurgy.

(b) compare the chemistry of group 15 elements down the group

c) state some examples of applications of the group 15 elements and their compounds

2.0 Group 15 Elements: N, P, As, Sb, and Bi

Introduction
The closely related elements N, P, As, Sb and Bi have five single electrons outside a noble a noble-gas
core. Some relevant data are listed in table 1 below.

Table 1. Some properties of group 15 elements

Element Electronic Atomic Sum of first three Oxidation state Electronegativity

configuration radius Ionization χ
Å potentials, eV

N [He]2s22p3 0.80 -3, -2, -1, 0, +1, +2, 3.10

+3, +4, +5
P [Ne]3s23p3 1.25 60.4 +3, +5 2.06
10 2 3
As [Ar]3d 4s 4p 1.25 58.0 +3, +5 2.20
Sb [Kr]4d105s25p3 1.50 52.3 +3, +5 1.82
Bi [Xe]4f145d106s26p3 1.50 52.0 +3, +5 1.67
NB/ The underlined oxidation state is the most stable

General properties
They have five electrons in the outer energy level. The outermost electrons are in the p orbital.
When they react with oxygen or chlorine, they exhibit oxidation state +5.
Down the group, the ns2 electrons remain paired favouring the oxidation state +3.

50
 Nitrogen exhibit very many oxidation states, for examples.

Oxidation state Example

-3 NH3
-2 N2H2 hydrazine
-1 NH2OH hydroxylamine
0 N2
+1 N2O nitrogen(I) oxide
+2 NO nitrogen(II) oxide
+3 HNO2 nitrous acid
+4 NO2 nitrogen(IV) oxide
+5 HNO3 nitric acid
Consider the electronegativity value of N=3.1 and for H=2.1. The higher electronegativity makes it
possible for nitrogen to form negative oxidation state.

Bond type
 If all the outermost electrons were to be lost we would get M 5+.
 This does not usually occur
 M3+ are formed in Sb (antimony) and Bi (bismuth). M3+ is formed when they react with F2.

F2 + Sb or Bi ionic bonds

SbF3 and BiF3 are ionic solids

M3+ ion is hydrolyzed in water, to give SbO+ and BiO+.

H2O
Bi
5 M HCl
BiO+

 N, P & As do not form M3+ ion.

 Possible to attain inert gas electronic configuration by gaining 3 electrons. E.g. N 3- requires 2125
kJ/mol (high). Nitride (N3-) are formed by metals with low ionization energy. The lattice
energies have to be high to compensate for high electron affinity and ionization energy. Example
of nitrides include: Li3N, B3N2 , Mg3N2 , and Ca3N2 .
 Phosphorous form covalent nitride- (if it were to react)

51
  Elements in second period do not have d-orbitals available for bond formation. (their d-orbitals
are of high energy). But in the third and other periods, the d-orbitals of suitable energies are
available for bond formation.
o Therefore N has maximum coordination number 4 while phosphorous can have 5 or 6
coordination number e.g. in PCl5 or [PCl6]-.
o PH5 does not exist but PH3 is known to exist. H is not electronegative enough to lower
the energy of d orbitals.
 Nitrogen cannot from complexes by accepting electron pairs from other ligands. But the
subsrquent elements can form such complexes.
 Nitrogen form pπ−pπ multiple bonds ie N≡N.
o This account for the various differences between phosphorous and nitrogen. Compounds
formed as a result of pπ−pπ multiple bond are NO 3-, NO2-, azide N3-, N2, N2O, NO, NO2,
N2O4, CN, azo and diazo compounds.
 N has capacity of forming multiple bonds, in this case N 2O3 and N2O5 are monomeric while P2O3
and P2O5 exist as dimeric.

Metallic non-metallic character

Element
N non-metal
P non-metal
As metallic
Sb metallic
Bi metal

The oxides of P and N are acidic. Oxides of As and Sb are amphoteric.

 Nitrogen exist as gas, N≡N, while phosphorous exist as tetrahedral molecule P 4.

o P4 exist in two forms, namely white phosphorous and red phosphorous. Above 800 C P 4
molecule dissociate to P2 molecule.
 As and Sb have two allotropic forms.
o As4 and Sb4 structure resemble white phosphorous. The other allotropic form are much
reactive, metallic forms and have layer structure.
 Bi has metallic for and exists as layer structure.

52
Halides of group 15 elements
 Form trihalides MX3 and pentahalide MX5
 Nitrogen forms a series of halides derived from hydrozoic acid (HN 3), fluoroazide (FN3),
chloroazide (ClN3), bromazide (BrN3)and iodazide (IN3). These halides resemble the azide, they
are unstable and explosive.

Trihalides

N, P, As, Sb and Bi form trihalides.

 The nitrogen trihalides are the least stable.

o NF3 very unstable
o NCl3 is explosive, NBr 3 and NI3 are only known as their unstable ammoniated forms.
NBr3∙6H2O and NI3∙6H2O exists,
o Trivalent forms covalent bonds
o With tetrahedral structure sp 3 hybridization. Lone pair of electron occupy one of the
corners of the tetrahedron.

BiF3 is ionic

N  BiCl3, BiBr3, BiI3 and

Cl SbF3 are intermediate

Cl character. Why is NF3

Cl is stable?
 The NF3 does not have donor properties of electron while NH 3 have the donor properties. (why?).
 Trihalides hydrolyze in water but the products are dependent on the elements. NF 3 hydrolyze in
vapour (steam).

53
 2NF3 + 3H2O 6HF +N2O3 (when sparked with vapour)

2NCl3 + 3H2O 2HOCl +NH3

PCl3 + 3H2O H3PO3 + 3HCl

AsCl3 + 3H2O H3AsO3 + 3HCl

SbCl3 + H2O SbO+ + 3Cl+ + 2H+

BiCl3 + H2O BiO+ + 3Cl+ + 2H+

Phosphorous trihalides, AsX and to a lesser extent SbX 3 have donor properties

Ni(CO)4 + 4PF3 Ni(PF3)4 + 4CO

dπ−dπ bonding between Ni and P atom.

o The bond length between P and Ni is shorter than expected

 Some of the trihalides have the acceptor properties

SbF4 + F- [SbF5]- or [Sb2F7]-

Pentahalides

 N cannot form pentahalides because of the absence of d orbitals. Nitrogen cannot extend its
valence beyond 4 (sp3d hybridization is not possible).
 PF5, PCl5, PBr5, AsF5, SbF5, are known (are sp3d hybridization).
o They have trigonal bipyramid structures
o Highly electronegative atoms have to be bonded to P. In order for sp3d hybridization to
occur.

54
 X

X
X P

PH5, PHF4 and PH2F3 do not exist.

Oxides of group 15 elements

 N−O, P−O, As−O, and Sb−O bonds are covalent while Bi3+−O2- is ionic
 N−O, involve pπ−pπ while P−O involve dπ−dπ

Because of pπ−pπ, there are so many oxides of N, which have no analogue in P, As, Sb and Bi. (N 2O,
NO, N2O3, NO2, N2O4, N2O5, NO3=N2O6 [unstable])

P2O3 and P2O5 are expected to exist, but they exist as dimer P4O6 and P4O10 .

P undergo sp3 hybridization.

P
O O

O
P P
O
O
O
P

P4O6

55
 O

O O

O P O P O
O

O O
P

P4O10

Trioxides of As and Sb are like those of P. They occur in dimeric form.

 P is more reactive than Nitrogen

 Phosphorous oxide are obtained when P burn in air.
 B2O3 is not dimeric but ionic.
 The basic strength of oxide increase down the group

Organo-metallic compounds
 Nitrogen form primary, secondary and tertiary amine; RH2N, R2NH and R3N.
 The halides of P, As, Sb and Bi react readily with LiR and RMgBr to form alkyl or aryl
compounds of the elements

PCl3 + 3LiEt PEt3 + 3LiCl

triethylphophine

PCl3 + 3phMgCl Pph3 + 3MgCl2

triphenylphophine

PCl5 + 5MeLi PM35 + 5LiCl

triethylphophine

The structure of Pph3 is the same as the of NH3 (sp3 hybridization)

 The trialkyl compounds of P and As have stronger donor properties.

o They form many compounds with transition metals

56
Extraction of group 15 elements
 N2 comprise 75% of Earth’s atmosphere. Also available in Earth crust as NaNO 3 (nitrate).
o Used in fertilizers, explosive (TNT), making NH3.
o It is essential constituent of proteins.
o N2 obtained commercially by fractional distillation of liquid air (N 2 bpt -196 C, and O2
bpt -183 C) but N2 obtained in this way contain traces of O2 and inert gases.
o In laboratory it is prepared by

NH4Cl + NaNO2 NH4NO2 + NaCl

prepared in situ
heat
NH4NO2 N2 + 2H2O

heat
NaN3 3N2 + 2Na

NH3 + 3Ca(OCl)2 CaCl2 + N2 + H2O

Phosphorous
 Essential component in nucleic acid.
 Used in fertilizers Ca3(PO4)2

electric
CaPO4 + SiO2 furnance CaSiO2 + P4O10

heat
P4O10 + C 4P + 10CO

P is used to make phosphoric acid H3PO4.

 As, Sb and Bi are extracted by the reduction of the oxide by carbon.

o As occur as flue dust in extraction of Fe, Co and Ni
o Sb occur as flue dust in extraction of Zn
o Sb occur as flue dust in roastin of PbS

57
 Lecture 5
Lecture Objectives
At the end of this unit you should be able to;

(a) explain the General properties of group 16 elements, Occurrence and metallurgy.

(b) compare the chemistry of group 16 elements down the group

c) state some examples of applications of the group 16 elements and their compounds

2.0 Group 16 Elements: O, S, Se, Te, and Po

Introduction
The closely related elements O, S, Se, Te and Po have five single electrons outside a noble a noble-gas
core. Some relevant data are listed in table 1 below.

Table 1. Some properties of group 16 elements

Element Electronic Oxidation state Electronegativity

configuration χ
O [He]2s22p4 -2, +2, +4, +6 3.10
S [Ne]3s23p4 -2, +2, +4, +6 2.44
Se [Ar]3d104s24p4 +2, +4, +6 2.48
Te [Kr]4d105s25p4 +2, +4, +6 2.01
Po [Xe]4f145d106s26p4 +2, +4 1.76

General properties
They have six electrons in the outer energy level. The outermost electrons are in the p orbital.
O, S, Se and Te are non-metals.
These elements are referred to as chacogens or forming elements.
The structures of the elements shows that the metallic characters of the elements increase down
the group.

58
 There is an increase tendency to form M 2+ ion and decreasing in the M2- ions down the group.
Ionic bonds are mostly formed by oxygen because of its high electronegativity value. They attain
complete octet by either gaining two electrons or sharing (covalent).

Metal oxides
 Most of these ionic and oygen exists as anion (O2-).
 When S, Se, and Te react with most electropositive elements, rarely does one get compounds
which are more than 50% ionic. This is because, S2-, Se2-, and Te2- are less probable.
 Group 16 elements form compounds which contain two electrons pair (covalent) bonds. H 2O,
Cl2O, H2S, SCl2, not linear, but angular.
 Oxygen mostly form divalent compounds. This is due to non-availability of d orbitals.
 However, S, Se and Te have empty d orbitals. Thus they are capable of forming 4 to 6 bonds, by
using sp3, sp3d1 and sp3d2 hybridization.
 The compounds of S, Se and Te with oxygen are typically tetravalent, but fluorine brings the
maximum oxidation state +5 or +6.
o oxidation +4 state have reducing properties while oxidation state +6 has oxidizing
properties.
 Why H2S is gas while H2O is liquid, though they form similar bond? This can be accounted for
by considering the high electronegativity of oxygen which bring about hydrogen bonding.

H
H

O
H O
H
H
O
H

H O

59
Bond lengths and pπ−dπ bonding
The bond between sulphur and oxygen and Se and O are expected to be single bond. When the bond
length are measured it is found that the bond length is shorter than expected. The measurements show,
that the bond is not single bond but a double bond. The shortening of the bond length is because of the
interaction of either dπ orbitals of S or Se with pπ orbitals of oxygen.

d p

S O

 To obtain pπ−dπ interaction the dπ orbital energy must have d orbitals which are of
comparable size with the p orbitals of oxygen.
 pπ−dπ interaction does not occur in the 2nd period but only occur in 3rd, 4th period etc
 pπ−dπ overlap (bonding) increase across the period. Silicate SiO 4- usual Si−O−Si bonds.
Phosphates pπ−dπ bonding is stronger, although some polymeric phosphates exists.

Oxyacids of sulphur
 π bonding is even stronger and become dominant factor.
 Only a small amount of polymerization occurs. Very few polymeric compounds with
S−O−S linkages. At Chlorine pπ−dπ bonding is so strong that no polymerization of oxygen
occurs.

Difference between oxygen and the other members of the group

 Oxygen is more electronegative than the rest.
 It is more ionic in its compounds.
 Hydrogen bonding is very important for oxygen compounds

60
 o H2O hydrogen bonding (strong)
o H2O hydrogen bonging(weak)
 Oxygen has no available d orbitals. This limit its coordination numbers to 4. The other elements
use d orbitals to increase their coordination number to six (sp3d2 hybridization).

Uses and reactivity of the elements

 All elements react with O2 (exception, being some inert gases possibly He, Ne and Ar and
possibly Kr). The reactions of oxygen and other are strongly exothermic.
 Oxygen is essential for respiration and hence to life.
 S, Se, Te are moderately reactive. Usually burn in air to form dioxide.
 They combine with many metals and non-metals. Not attacked by acid except oxidizing agents.

Reason –their non metallic characters

 Polonium—dissovle in sulphuric, HF, HCl and HNO 3. This is further evidence of its increased
metallic character.
 S and Se usually dehydrogenate saturated hydrocarbons
 Sulphur react with olefins and forms sulphur cross links. Used in vulcanization of rubber.
 S is used in preparation of sulphuric acid, sulphite, bisulphites and SO2 are used as bleaching
agents.
 S used in making of fungicides and gunpowder.

Structure of the elements

They usually exist in more than one allotropic forms (They are polymorphs)

 Oxygen exist as O2 (oxygen) and O3 (ozone)

o Ozone mare reactive than oxygen
o Oxygen is paramagnetic while ozone is diamagnetic. O3 is very powerful oxidizing agent.
 S has two crystalline forms
o α or rhombic sulphur (stable at room temperature)
o β or monoclinic (stable above 95 C)

61
 S8 ring

 The packing of these crystals account for the allotropy

 Why S exist as 8 membered ring while oxygen exist as diatomic? (oxygen can form pπ−pπ
bonding sulphur cannot). S6 ring of sulphur exist and is usually very unstable.
 S10 and S12 have been made

H2 S 8 + S4Cl2 2HCl + S12

 All these rings are non-metallic

 Se exist as non-metallic form, red in colour
o Grey (Se) contains infinite spirals, weak metallic interaction, between adjacent (spirals)
chains
 Te, semi-metallic
o Exists as a silvery white form similar to grey Se.
 Po, true metal, but exist as α and β forms. These forms depend on packing of atoms.
 Down the group, the metallic character increase
o O and S insulator
o Se and Te semiconductor
o Po conductor

Hydrides
 All the elements in group 16 form volatile bivalent hydrides H2O, H2S, H2Se, H2Te and H2Po.
 The hydrides are poisonous (except H2O). Have unpleasant smell (except H2O).
 Stability of hydride decrease from H2O to H2Te. This is depicted in the heat of formation

62
 Hydride Heat of formation kJ/mol Bpt C

H 2O -242 100

H2S -20 -60

H2Se 81 -42

H2Te 151 -2.3

The high boiling point of H2O is due to extensive hydrogen bonding formed.

Halides of group 16 elements

 When oxygen react with fluorine, we get binary compounds referred to as oxygen fluoride.
 When oxygen react with Cl2, we get chlorine oxide.
 F2 bring out maximum valence of 6 when it reacts with S, Se and Te. Eg SF 6, SeF6 and TeF6 are
formed by direct combination of fluorine and the element. The hexafluoride are colourless gas
and have octahedral structures (sp3d2 hybridization).
 There is no oxygen hexafluoride, due to non-availability of d orbital. Thes type of hybridization
cannot occur in Po. Since its d orbitals are large and on the other hand Po is metallic.

Element MX6 MX4 MX2 M2X2 M2X Others

O OF2, O2F2 O3F2, O4F2,

Cl2O6, Cl2O7
Cl2O, ClO2
BrO3, I2O4,
Br2O BrO2 I4O9, I2O5

S SF6 SF6 SF2 S2F2

SCl4 SCl2 S2Cl2

S2Br2

Se SeF6 SeF4

SeCl4 SeCl2

63
 SeBr4 SeBr2

Te TeF6 TeF4

TeCl4 TeCl2

TeBr4 TeBr2

Po TeF4

TeCl4 PoCl2

TeBr4 PoBrl2

Most of the halides have relatively low boiling points, this confirm the covalent nature of the bonding.

 SF6 extremely inert

 SeF6 slightly more reactive
 TeF6 hydrolyzed by water

TeF6 + 6H2O 6HF + H6TeO6

The difference in size of F and Te causes it to be unstable.

 SF6 is used as gaseous dielectric in high voltage transformer due to its inertness.
 Coordination number greater than 6 formed in Te, e.g. [TeF7]- and [TeF8]2-.
 Many tetrahalide are known, but are not prepared by direct combination
 SF4 gas
 SeF4 liquid
 TeF4 solid

64
 S + F2 SF4
(dilute with N2)

S + 4CoF3 SF4 + 4CoF2

SeCl4 + 4AgF SeF4 + 4AgCl

TeO2 + 2SeF4 TeF4 + 2SeOF2

The highly reactive tetrafluoride are used as fluorinating agents and SF 4 is useful reagent for replacing
hydroxyl and carbonyl oxygen group.

ROH + SF4 RF

O + SF4 RCF3
R
O H

R
O SF4
+ CF2
R
R R

Hexafluoride SF6 is inert

SF4 + H2O SOF2 + 2HF

Dihalides

SCl2, prepared by saturating S2Cl2 with chlorine. It is sp3 hybridized.

Cl
Cl

65
Oxides of group 16 elements
They form dioxide MO2 and trioxides, MO3.

 SO2, SeO2, TeO2 and PoO2 –made by burning the element in air
o SO2 is discrete molecule pπ−dπ interaction
o SeO2 is solid form infinite chain at elevated temperature
o TeO and PoO2—crystallize into two ionic forms

Reaction of dioxide with water

SO2 + H2O H2SO3

sulphorous acid

SeO2 + H2O H2SeO3

selenous acid

TeO2 is almost insoluble

o Dissolve in alkali to form tellunate

H2SO4 not used

SO3 + H2O
H2S2O7
SO3 + H2SO4
oleum

 At room temperature SO3 is solid

o Forms ice-like and is a cyclic trimer
o Powerful oxidizing agent
 SeO3 formed by electric discharge on Se and oxygen
 TeO3 formed from telluric acid by strong heating

Oxyacids of S, Se and Te
Oxyacids of S are very numerous and very important. They do not exist in crystalline form.

 Acids with name ending with:

o –rous have oxidation state +4

66
 o Salts formed have the name ending with –ite, e.g Na2SO3.
 Name ending with –ic, eg sulphuric acid
o Have oxidation state +6
o Salts formed have name ending with –ate
 The oxyacids of sulphur have strong π bonds, have little tendency to polymerize compared to
phosphate and silicates.
 Se have two oxyacids,
o H2SeO3 selenious acid
o H2SeO4 selenic acid
 TeO2 insoluble in water. Tellunious acid has been characterized

Extraction
 O2 –fractional distillation of liquid air
 S --from coal,
o Deposit of sulphur, Frasch process
 Se occur along with PbS (galena)
 Te---when extracting sulphide
 Po—occur with thorium and Uranium

67
 Lecture 6
Lecture Objectives
At the end of this unit you should be able to;

(a) explain the General properties of group 18 elements, Occurrence and metallurgy.

(b) compare the chemistry of group 18 elements down the group

c) state some examples of applications of the group 18 elements and their compounds

2.0 Group 18 Elements: Ne, Ar, Kr, Xe, and Rn

Introduction
Theese are Ne, Ar, Kr, Xe and Rn. Some relevant data are listed in table 1 below.

Table 1. Some properties of group 16 elements

Element Outer shell First Ionization Normal Bpt in K Promotion energy (eV)
configuration Potential/ eV ns2np6→ns2np5(n+1)s1
He 1s2 24.58 4.18 ___
Ne 2s22p6 27.13 27.13 16.6
Ar 3s23p6 15.76 87.29 11.5
Kr 4s2346 14.00 120.26 9.9
Xe 5s2356 12.13 166.06 8.3
Rn 6s2366 10.75 208.16 6.8

General properties
They are minor constituent of atmosphere
They are obtained by fractional distillation of liquid air
Their outer most energy levels are completely stable as manifested by their large first ionization
potential.
Their ability to enter into chemical combination with other elements are limited, only Kr, Xe and
Rn having so far been induced to do so, and only bonds to F and O are stable.
This ability would be expected to increase with decreasing ionization potential and decreasing
energy of promotion to states with unpaired electrons. According to present knowledge, the
threshold of actual chemical activity is reached only at Kr. The chemical activity of Xe is

68
 markedly greater. That of Rn is presumably still greater, but it is difficult to access because the
222
half – life of the longest lived isotope Rn, is only 3.825 days so that only trace studies can be
made.

Special properties of Helium

 It’s most remarkable feature is that helium has no triple point; that is, there is NO combination of
temperature and pressure at which solid, liquid and gas co-exist in equilibrium
 Helium is the only known substance lacking a triple point
 It is also the only one that cannot be solidified at atmospheric pressure
 It is, however, a unique liquid in exhibiting the phenomena of superconductivity

The Chemistry of the noble gases

N Bertlet (1962) observed that O2 react with PtF6 to give the corresponding [O2]+[PtF6-]

O2 + PtF6 [O2+][PtF6-]
crystalline solid

He suggested that since IP of Xe is almost identical with that of O 2 an analogous reaction might be
expected with He, i.e.

Xe + PtF6 [Xe+][PtF6-]
red crystalline solid

This discovery led rapid and extensive development in the Xenon chemistry.

The Chemistry of Xenon

Xe reacts directly with F2 but oxygen compounds can be obtained from fluorides

Xe + F2 XeF2 linear
excess
solid soluble in H2O, HF. sublime at 25C

69
The hydrolysis is slow in acid solution but rapid in presence of a base

2XeF2 + 4OH- 2Xe + O2 + 4F- + 2H2O

Its solutions are strong oxidizers, converting HCl to Cl 2 and Ce3+ to Ce4+.

+ -
2XeF2 + 2H + 2e Xe + 2HF E=2.64V

XeF2 is a mild fluorinating agent for organic compounds

F
XeF2 +

XeF4 (square planar) isoelectronic with ICl4 and BrF4.

70