DEPARTMENT OF CHEMISTRY

CHM 301 (Main Group Chemistry) --- - - Prof. Adeniyi, AA

HYDROGEN
The element: Although air contains almost no free hydrogen, hydrogen atoms are
very abundant in nature. One reason for this is that they are found in water, which
is widely distributed over the earth, another is that, combined with carbon, they are
found in all living matter. Hydrogen is also found in space. It plays a crucial role in
stars (such as our sun) and in nuclear fusion reactions.

Some properties of hydrogen

Relative atomic mass 1.008
Electronic structure 1s1
Ionization energy 1312 kJ/mol
Electron Affinity -72 kJ/mol
Molecular Formula H2
M.pt 14 K (-259 oC)
B.pt 20 K (-253 oC)
Density at S.T.P 0.09 g/dm3
Bond energy, H-H 436 kJ/mol
Bond length, H-H 74 pm
It is colourless, odourless and tasteless.

Isotopes: Hydrogen has three isotopes: (protium, H), (deuterium, D) and

(tritium, T). Deuterium occurs naturally (0.014%), tritium (7x10-16 %) and
protium (99.986%). Tritium is radioactive and decays by -emission.

Manufacture of hydrogen
1. From methane
CH4 (g) + H2O (g) CO (g) + 3H2 (g)
CO (g) + H2O (g) CO2 (g) + H2 (g)

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2. Cracking of hydrocarbons
C6H12 (g) C6H6 (g) + 3H2 (g)

3. Electrolysis
Very pure hydrogen (99.9% pure) is made by electrolysis of water or solutions of
NaOH or KOH. This is the most expensive method. Water does not conduct
electricity very well, so it is usual to electrolyse aqueous solutions of NaOH or
KOH in a cell with Ni anodes and Fe cathodes.
Anode 2OH- H2O + 1/2O2 + 2e-
Cathode 2H2O + 2e- 2OH- + H2
Overall H2O H2 + 1/2O2

4. Bosch Reaction
1st Stage: H2O (g) + C (s) CO (g) + H2(g)
(Steam is passed over white hot coke)
nd
2 Stage: H2O (g) + CO (g) CO2 (g) + H2 (g)
(Water gas is mixed with more steam and passed over Fe catalysts)
3rd Stage: Under pressure the CO2 is dissolved in water, thus leaving the
H2 available for further use
5. Laboratory preparation: Zn(s) + 2H+ (aq) Zn2+ (aq) + H2 (g)
That is mixing dilute H2SO4 with zinc granules.

Uses of Hydrogen
1. Making NH3 in the Haber process
N2 (g) + 3H2 (g) 2NH3 (g) ∆Hɵ = -92 kJ/mol
2. Production of margarines from vegetable oils

3. In welding: The gas is passed through an electric arc, which splits the
molecules into atoms. When the atoms recombine to produce molecules a
great deal of heat is generated. This heat is used to melt and fuse metal

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 surfaces together. Because it does not use oxygen, oxidation of the metals is
prevented, which is a great advantage in many processes.
4. Fuel cells: Hydrogen has find use as a potential fuel. When hydrogen burns
in air it produces significant amounts of energy, and it has the virtue of being
pollution free. Cars have been built that use H2 as a fuel rather than petrol.
Hydrogen-oxygen fuel cells are useful devices for converting the energy of
the reaction: 2H2 (g) + O2 (g) 2H2O (l). The reverse reaction is potentially
very useful as fuel.
Position in the Periodic Table: H is the first element in the periodic table and it’s
unique. There are only two elements in the 1st period, H and He. H is quite
reactive, but He is inert. The structure of H atom is in some ways like that off the
alkali metals. The group 1 metals also have just one electron in their outer shell,
but they tend to lose this electron in reactions and form +ve ions M +. Though H+
are known, H, has a much greater tendency to pair the electron and form a covalent
bond.
The structure of H atoms is in some ways like that of the halogens (group 17),
since both are one electron short of a noble gas structure. In many reactions, the
halogens gain an electron and form –ve ions, X-. Hydrogen does not typically form
a –ve ion, although it does form ionic hydrides M+H- (e.g. LiH and CaH2) with a
few highly electropositive metals.
Similarly, in some ways the structure of H resembles that of the group 14 elements.
Since both have a half filled shell of electrons (That is 1 as against 2 (doublet) and
4 as against 8 (octet) respectively). However, this similarity is not compelling
enough to place H in group 4/14.

Ortho and Para Molecular Hydrogen: The H2 molecule exists in two different
forms known as ortho and para hydrogen. The nucleus of an atom has nuclear spin,
in a similar way to electrons having a spin. In the H2 molecule, the two nuclei may
be spinning in either the same direction or in opposite directions. This gives rise to
spin isomerism that is two different forms of H2 may exist. These are called ortho
and para hydrogen.

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There are considerable differences between physical properties (e.g. boiling points,
specific heats and thermal conductivities) of the o- and p- forms. There are also
differences in the internal band spectra of the two forms.

The para form has the lower energy and at absolute zero, the gas contains 100 % of
the para form. As the temperature is raised, some of the para form changes to
ortho. At high temperatures, the gas contains about 75 % ortho hydrogen.

Para hydrogen is usually prepared by passing a mixture of the two forms of H 2

through a tube packed with charcoal cooled to liquid air temperature. Para H2
prepared in this way can be kept for weeks at room temperature in a glass vessel
because ortho-para conversion is slow in the absence of catalysts. Suitable
catalysts include activated charcoal, atomic metals such as Fe, Ni, Pt and W and
paramagnetic substances or ions (which contained unpaired electrons) such as O2,
NO, NO2, Co2+ and Cr2O3.

Hydrogen bonding: The H-bond is most simply regarded as a weak electrostatic

attraction between a lone pair of electrons on one atom and a covalently bonded H
atom that carries a fractional charge δ+. H-bonds are inter-molecular and are

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formed only with the most electronegative atoms (F, O, N and Cl are the four most
important). These bonds are very weak and are typically about 10 kJ/mol, but
could vary between 4 – 45 kJ/mol compared with a C-C covalent bond of 347
kJ/mol. H-bond has a striking effect on physical properties such as melting
points, boiling points and the enthalpies of vaporization and sublimation. The
boiling point of H20 is much higher than would be expected with comparison with
H2S, H2Se and H2Te (all hydrides of group16). Strong evidence for H-bonding
comes from structural studies especially X-ray crystallographic studies.

H---H bond: These are essentially intra-molecular in nature. Recently it has been
proposed that non-covalent bonds can be formed between X-H groups (X mostly O
or N) with partially positive hydrogen atoms and the hydrogen atoms of some M-H
moieties. Specific examples are provided below, which are largely intra-molecular
cases.

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Similarly, inter-molecular interactions of the same types have been proposed, e.g.
phenol with WH(CO)2(NO)PMe3, on the basis of infrared spectra and other
indirect evidences.
Chemical properties:
1. Formation of hydrides with many elements.
(a) Hydrides of non-metals are covalent:
3H2+N2 2NH3
2H2 + O2 2H20
H2 + Cl2 2HCl
4BCl3 + 3Li[AlH4] 2B2H6 + 3AlCl3 + 3LiCl
Al4C3 + 12HCl 3CH4 + 4AlCl3
2Mg3B2+ 4H3PO4 → B4H10 + 2Mg3(PO4)2 + H2

(b) Hydrides of metals are ionic:

LiH + H20 LiOH + H2
S1Cl4 + 4NaH SiH4 + 4NaCl
PbSO4 + 2CaH2 PbS + 2Ca(OH)2
4LiH + AlCl3 Li[AlH4] + 3L1Cl
4NaH + B(OCH3)3 Na[BH4] + 3NaOCH3
2. Explodes with O2 if ignited
2H2(g) + O2(g) → 2H20
3. A reducing agent; will reduce oxygen from many oxides
CuO(s) + H2(g) → Cu(s) + H20 (g)
4. Liberated from acids by many metals
Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2(g)

Assignment 1

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(1) Suggest reasons for and against the inclusion of H in the main groups of the
periodic table.
(2) Describe four ways in which H2 is produced on an industrial scale. Give one
convenient method of preparing H2 in the lab.
(3) Give an account of the main uses of H2
(4) Differentiate between ortho- and para- hydrogen.
(5) Differentiate between H - -H and H-bonding.
(6) Describe the hydrides of non-metals and metals using three examples each.

Group 1- The Alkali metals

Element Symbol Electronic Metallic radius Ionic radius Density
configuration (Å) (Å) (g/cm3)
Lithium Li [He]2s1 1.52 0.76 0.54

Sodium Na [Ne]3s1 1.86 1.02 0.97

Potassium K [Ar]4s1 2.27 1.38 0.86

Rubidium Rb [Kr]5s1 2.48 1.52 1.53

Cesium Cs [Xe]6s1 2.65 1.67 1.90

*Francium Fr [Rn]7s1
*naturally radioactive
The elements of group I illustrate clearly than the size of atoms or ions elements,
the effects of increasing the size of atoms or ions on the physical and chemical
properties. The elements are metals, excellent conductors of electricity, typically
soft and highly reactive. They have one loosely held valence electron in their outer
shell, and typically form univalent, ionic and colourless compounds. The
hydroxides and oxides are very strong bases and the oxo-salts are very stable.
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Li, the 1st element in the group, shows considerable differences from the rest of the
group. In the entire main groups the 1st element shows a number of differences
from the lower elements in the group. Some exhibit the so-called diagonal
relationship with members of the preceding groups.

Occurrence: 1. Li, obtained as spodumene Li Al (SiO3)2

2. Na, obtained as rock salt (NaCl); borax (Na2B4O7); trona
(NaHCO3.2H2O); salt petre (NaNO3)
3. K, obtained as sylvite (KCl); carnallite (KCl.MgCl2.6H2O)

There is no convenient source of Rb. It is obtained along with Cs as by-products

from Li processing.

Francium is obtained by the radioactive decay of 227Ac as shown below:

+
223
Fr has a ½ life of 21 minutes.

The metals are isolated by the electrolysis of a fused salt, usually the fused halide.
Direct electrolysis is impracticable because of the position of the elements in the
electrochemical series.

Uses

Li In small, long-life batteries e.g. for use in digital watches,

calculators and computers.
In the reducing agents LiH and LiAlH4
Specialist chemicals in a wide range of industries e.g. making glass

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 and organic chemicals.
Na Liquid Na has been used for heat transfer in nuclear power stations
as a reducing agent in the manufacture of some elements e.g. Ti
In alloys
In batteries
K Manufacture of KO2 for oxygen generation

The other metals, Rb, Cs, Fr have but few uses at the moment. Sodium chloride is
useful in the chlor-alkali industry in the manufacture of heavy chemicals.
Biological Importance: Living organisms require at least 27 elements of which 15
are metals. Metals require in major quantities are K, Mg, Na and Ca. Minor
quantities of Mn, Fe, Cu, Cu, Zn and Mo and trace amounts of V, Cr, Sn, Ni and
AI, are required by at least some organisms.
Bulk quantities of group 1 and 2 metals are required, mainly to balance the
electrical charges associated with negatively charged organic macro-molecules in
the cell and also to maintain the osmotic pressure inside the cell, to keep it turgid
and prevent its collapse.
The close similarity of the chemical properties of Na and K not withstanding their
biological functions are very different. Na+ are actively expelled from cells,
whereas, K+ are not. This ion transport is sometimes called a sodium pump, and it
involves both the active expulsion of Na+ and the active take-up of K+. Analysis of
the fluids inside and outside animal cells shows that ion transport really does
occur.
The different ratio of Na+ to K+ inside and outside cells produces an electrical
potential across the cell membrane, which is essential for the functioning of nerve
and muscle cells. The movement of glucose into cells is associated with Na+ ions.

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K+ ions inside the cell are essential for the metabolism of glucose, the synthesis of
proteins and the activation of some enzymes.
Size and Density: Group 1 atoms are the largest in their horizontal periods in the
periodic table when the outer electron is removed to give a +ve ion. The size
decreases considerably - (1) the outermost shell of electrons has been completely
removed and (2) having removed an electron, the positive charge on the nucleus is
now greater than the charge on the remaining electrons, so that each of the
remaining electrons is attracted more strongly towards the nucleus. This reduces
the size further. Because of large atoms group 1 elements have remarkably low
densities.

Ionization Energy (I.E), Electronegativity (EN) and Bond Type: The 1st
ionization energies for the atoms in this group are appreciably lower than those for
any other group in the periodic table. The atoms are very large, so the outer
electrons are only held weakly by the nucleus; hence the amount of energy needed
to remove the outer electron is not very large. On descending the group from
Li → Cs the size of the atoms increases: the outermost electrons become less
strongly held, so the I.E decreases.

Ionization Energy

1st I.E (kJ/mol) 2nd I.E kJ/mol

Li 520.1 7296

Na 495.7 4563

K 418.6 3069

Rb 402.9 2650

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Cs 375.6 2420

The electronegativity values for the elements in this group are very small. Thus
when these elements react with other elements to form compounds, a large
electronegativity difference between the two atoms is probable and ionic bonds are
formed e.g.

Na EN 0.9
Difference 2.1
Cl EN 3.0

Melting and boiling points: The generally low values for the cohesive energy are
reflected in the very low melting and boiling points in the group. The cohesive
energy decreases down the group. And melting and boiling point generally
decreases down.

Melting and boiling points

Melting point ( ) Boiling point ( )

Li 181 1347

Na 98 881

K 63 766

Rb 39 688

Cs 28.5 705

Chemical Properties

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(1) Reaction with Air: Chemically, group I elements are very reactive, and
tarnish rapidly in dry air, Na, K, Rb and Cs form oxides of various types, but Li
forms a mixture of the oxides and the nitride Li3N.

(2) Oxides, Hydroxides and Peroxides

Li2O + H2O 2LiOH

Na2O + H2O 2NaOH
K2O + H2O 2KOH
NaOH + HCl NaCl + H2O
2NaOH + CO2 Na2CO3 + H2O
NaOH + NH4Cl NH3 + NaCl + H2O
6NaOH + 2[CO(NH3)6]Cl3 12NH3 + Co2O3 + 3NaCl +3H2O
NaOH + H2S NaSH Na2S
NaOH + EtOH NaOEt + H2O
sodium ethoxide

Na2O2 + 2H2O 2NaOH + H2O2

2Na2O2 + 2CO2 Na2CO3 + O2
3. Sulphides

The metals reactt with sulphur, forming sulphides such as Na2S and poly-sulphides
Na2Sn where n = 2, 3, 4, 5 or 6. The poly-sulphide ions are:

Na2SO4 + 4C Na2S + 4CO

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Na2S + H2O NaSH + NaOH
4. Halides

KI + I2 K[I3]
Poly-halides [I – I – I]-
KBr + ICl K[BrICl]
KF + BrF3 → K[BrF4]
LiCl, LiBr, CsCl, CsI are also formed.

5. Hydrides

LiH + H2O LiOH + H2

4LiH + AlCl3 Li[Al H4] + 3LiCl
4NaH + B(OCH3)3 Na [BH4] + 3NaOCH3

Differences between Li and the other Group I elements

1. The melting and boiling points of lithium metal are much higher than those
for the other Group I elements
2. Li is much harder than the Group I metals
3. Li reacts the least readily with oxygen, forming the normal oxide. It forms
peroxide only with great difficulty and the higher oxides are unstable.
4. LiOH is less basic than the other hydroxides in the group and therefore many
of its salts are less stable. Li2CO3, LiNO3 and LiOH all form the oxide on
gentle heating, though the analogous compounds of the rest of the group are
stable.
5. Li forms a nitride Li3N. None of the other group I elements form a nitride,
but group 2 elements form nitrides.

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6. Li reacts directly with C to form ionic carbide. None of the other group I
elements do this but group 2 elements all react similarly with C.
7. Li have a greater tendency to form complexes than the other members of the
group.
8. The halides and alkyls of lithium are far more covalent than the others.
9. Lithium ion and its compounds are more heavily hydrated than those of the
rest of the group.
Assignment 2
1. Write short notes on the following: a. chlor-alkali industry. b. biological
importance of sodium and potassium.
2. Highlight the major differences between Li and the other heavier members
of its group.
3. Write notes on the halides, hydrides and sulphides of the alkali metals.
4. a. Describe the occurrence and isolation of the group1 metals. b. Describe
the metallic radii and densities of the group 1 elements.

GROUP 2 - The alkaline earth metals

Elements Symbol Electronic Metallic Ionic radius Density

configuration radius (Å) (Å) (g/cm3)

Beryllium Be [He] 2s2 1.12 0.45 1.85

Magnesium Mg [Ne] s2 1.60 0.72 1.74

Calcium Ca [Ar] 4s2 1.97 1.00 1.55

Strontium Sr [Kr] 5s2 2.15 1.18 2.63

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Barium Ba [Xe] 6s2 2.22 1.35 3.62

*Radium Ra [Rn] 7s2 - 1.48 5.50

* naturally radioactive

The group 2 elements show the same trends in properties as were observed with
group 1. However, Be stands apart from the rest of the group and they are less
reactive than group 1, typically divalent and generally form colourless ionic
compounds.

Uses of group II elements

Be As a moderator in nuclear reactors
Mg In alloys of many kinds – it lends strength with little increase in
weight, hence its use in aircraft structure
Ca In biological systems, it is essential for healthy growth of bones. Its
carbonate is used in the manufacture of cement
Sr Few uses, although its radioactive isotope, is well known (and
feared) because it is produced in nuclear fall-out.
Ba In some alloys with lead and calcium BaS04 is used in medicine as
“barium meal” which patients swallow – the sulphate is relatively
opaque to X-rays so it shows particularly well in X-ray
photographs
Occurrence and Extraction

Be = beryl (Be3Al2Si6O18); phenacite (Be SiO4)

Mg = dolomite (MgCO3.CaCO3), carnallite (KCl.MgCl2.6H2O);
asbestos (Mg3(OH)4.Si2O5)
Ca = calcite (CaCO3); gypsum (CaSO4.2H2O)
Sr = celestite (SrSO4); strontianite (SrCO3)
Ba = barytes (BaSO4)
Ra = uraninite
The metals are obtained by the electrolysis of the fused halides
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Some other physical properties

Element I.E (kJ/mol) E.N Melting point Boiling point (

(
1st 2nd

Be 899 1757 1.5 1287 2506

Mg 737 1450 1.2 649 1105
Ca 590 1145 1.0 839 1494
Sr 549 1064 1.0 768 1381
Ba 503 965 0.9 727 1850
Ra 509 979 - 700 1700

Reaction with H2O

Ca + H2O Ca(OH)2 + H2
Mg + 2H2O Mg(OH)2 + H2
Mg + H2O MgO + H2
Hydroxides: Be(OH)2 is amphoteric, but the hydroxides of Mg, Ca, Sr and Ba are
basic

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

Insoluble Soluble
white ppt.

Solutions of Ca(OH)2 and Ba(OH)2 are called lime water and baryta water
respectively and are used to detect . When is bubbled through these
solutions, they become “turbid” or “milky” due to the formation of a suspension of

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solid particles of CaCO3 or Ba(OH)2. If excess is passed through these
“milky” solutions, then the turbidity disappears as soluble bicarbonates form with
the excess

Hardness of Water

Temporary hardness is due to the presence of Mg(HCO3)2 and Ca(HCO3)2 . It is

called “temporary” because it can be removed by boiling.

+ + O

Thus the bicarbonates decompose into carbonates and the calcium carbonate is
precipitated. If this is filtered off or allowed to settle, the water is free from
hardness. Temporary hardness can also be removed by adding slaked lime to
precipitate calcium carbonate.

This is called “lime softening” and by operating at pH 10.5

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

Permanent hardness is not removed by boiling and is due mainly to MgSO 4 or

CaSO4 in solution. They are softened by the addition of sodium carbonate:

CaSO4 + Na2CO3 CaCO3 + Na2SO4

Insoluble Soluble

H2O may also be softened by adding various phosphate such as trisodium

phosphate, Na3PO4; sodium pyrophosphate Na4P2O7; sodium tripolyphosphate,
Na5P3O10 or Grahams salt (Calgon), (NaPO3)m.

Sulphates: The solubility of the sulphates in water decreases down the group, B >
Mg >> Ca > Sr > Ba.

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CaSO4.2H2O CaSO4.½H2O CaSO4 CaO + SO3
Plaster of Paris
PPar
MgSO4 MgO + SO3

BaSO4 + 4C BaS + 4CO

Nitrates

Basic beryllium nitrate

Hydrides

2BeCl2 + LiAlH4 → 2BeH2 + LiCl + AlCl3

BeB2H8 + 2PPh3 → BeH2 + 2Phh3PBH3

Halides

BeO + 2NH3 + 4HF (NH4)2[BeF4] BeF2 + 2NH4F

BeO + C + Cl2 BeCl2 + CO

2BeO + CCl4 2BeCl2 + CO2

Carbides

Be2C + 4H2O → 2Be(OH)2 + CH4

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Ca + 2C CaC2

CaO + 3C CaC2 + CO
CaC2 + 2H2O → Ca(OH)2 + C2H2
Acetylene
CaC2 + N2 → CaNCN +C

CaNCN + 5H2O → CaCO3 + 2NH4OH

Diagonal relationship
Beryllium shows many resemblances to aluminium in its chemistry and for exactly
the same reasons that lithium resembles magnesium. The differences between
beryllium and magnesium are even more striking than those between lithium and
sodium. and its similarities to aluminium are so close that it was at one stage
thought to have a valency of three. Among its diagonal similarities with aluminium
can be listed the following:
(a) Both metals are made passive by nitric acid.
(b) Both metals react with sodium hydroxide solution to evolve hydrogen:
Be + 2OH- + 2H2O Be(OH)42- + H2
2AI + 2OH- + 6H2O 2AI(OH)4- + 3H2
an alumininate ion
(c) The oxides and hydroxides of beryllium and aluminium are amphoteric.
(d) The chlorides are covalent polymeric solids when anhydrous, (BeCl2)x and
(AICl3)x. which readily dissolve in organic solvents. They are readily
hydrolysed by water, with the evolution of hydrogen chloride.
(e) Beryllium carbide, Be2C and aluminium carbide Al4C3, give methane on
treatment with water, unlike the ionic carbides of the Group 2 metals. They
are therefore referred to as methides:
Be2C + 4H2O 2Be(OH)2 +CH4
Al4C3+ l2H2O 4Al(OH)3 +3CH4

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(f) Similar complexes of beryllium and aluminium have similar stabilities, e.g.
BeF42- and AlF63-. The former is tetrahedral and the latter octahedral in
shape, in agreement with the simple theory of electron pair repulsion.

Complexes of group II metals

The tendency of the group II metal ions to form complexes decreases with
increasing atomic number. Mg having a smaller ion than calcium forms complexes
more readily. Be having the smallest ion of this group of elements naturally tends
to form complexes the most readily, since the small positively charged ion is able
to exert considerable attraction on other ions or molecules that have lone pairs of
electrons.

Ammonium fluoroberyllate, (NH4+)2BeF42- contains the tetrahedral BeF42- ion; the

hydrated beryllium ion, [Be(H2O)4]2+ is also tetrahedral. Ca and Ba complexes
have also been reported.

Assignment 3

1. Give the equations to show the reactions between Ca and: (a) H2O (b). H2
(c ). N2 (d). C (e). O2 (f). Cl2 (g). NH3
2. The hardness of water may be ‘temporary’ or ‘permanent’. What causes
each of these conditions, and how is each treated?
3. The four general methods of extracting metals are thermal decomposition,
displacement of one element by another, chemical reduction and electrolytic
reduction. How group 2 metals are obtained and why are the other methods
unsuitable.
4. Write short notes on the following: a. Halides b. sulphates c. carbides

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