p-block elements

 in p-block elements the last electron enters the outermost p orbital

— sincethere are 3 p orbitals, the maximum number of electrons that can be
accommodated in a set of p orbitals is six
— consequently, there are six groups of p–block elements in the periodic table
numbering from 13 to 18
 boron, carbon, nitrogen, oxygen, fluorine and helium head the
groups
— their valence shell electronic configuration is ns2np1-6 (except for He)
— the inner core electronic configuration may however differ; this greatly
influences their physical and chemical properties
— consequently, a lot of variation in properties of elements in a group of p-
block is observed
 p-block elements
 the maximum oxidation state is equal to the total number of
valence electrons (i.e., the sum of the s-and p-electrons)
— hence, the number of possible oxidation states increases towards the right of
the periodic table
— in addition to this so-called group oxidation state, p-block elements may show
other oxidation states which normally, but not necessarily, differ from the total
number of valence electrons by unit of two
p-block elements
 p-block elements
 in boron, carbon and nitrogen families the group oxidation state is
the most stable state for the lighter elements in the group
— however, the oxidation state two unit less than the group oxidation state
becomes progressively more stable down the group
— the occurrence of oxidation states two unit less than the group oxidation
states are sometime attributed to the ‘inert pair’ effect

 inert pair effect is reluctance of the s-electrons of the valence shell

to take part in bonding
— arises from poor on ineffective shielding by inner d and f electrons
 p-block elements
 in each group the first member differs from the remaining members
of their respective groups
— much smaller size - all properties that depend on size are affected (see s
block elements)
— the effect of d and f -orbitals in the valence shell of heavier elements (3rd
period onwards) and their lack in second period elements
— 1st members are restricted to a max valence of 4 (using 2s and three 2p
orbitals)
— in contrast, the third period elements have vacant 3d orbitals lying between
the 3p and the 4s levels of energy
— using these d-orbitals the third period elements can expand their covalence
above 4
 p-block elements
 in each group the 1st member differs from the other members
— much smaller size - all properties that depend on size are affected (see s
block elements)
— the effect of d and f -orbitals in the valence shell of heavier elements (3rd
period onwards) and their lack in second period elements
— 1st members are restricted to a max valence of 4 (using 2s and three 2p
orbitals)
— in contrast, the third period elements have vacant 3d orbitals lying between
the 3p and the 4s levels of energy
— using these d-orbitals the third period elements can expand their covalence
above 4
❖ for example, while boron forms only [BF4]–, aluminium gives [AlF6]3– ion
 p-block elements
 explanation
— aluminium has electronic configuration [Ne]3s23p1
❖ Al has vacant d-orbits to fit in more electrons, thus Al can coordinate with 6
F- ions to form [AlF6]3-.

— boron has electronic configuration [He]2s22p1

— but B doesn't have d-orbitals to fit more electrons and thus coordinates with
only 4F- ions to form [BF4]-
 p-block elements
 the 1st member of each group differs from the heavier members in
its ability to form p - p multiple bonds:
— to itself (e.g., C=C, C≡C C=C, N≡N)
— and to other second row elements (e.g.=O, C=N, C≡N, N=O)
 p-block elements
 this type of  –bonding is not particularly strong for the heavier p-
block elements
— the heavier elements do form  bonds but this involves d orbitals (d – p or
d –d )
— as the d orbitals are of higher energy than the p orbitals, d – p or d –d
orbitals contribute less to the overall stability of molecules than does p - p
bonding of the second-row elements
Group 13 – The Boron family
 Group 13 – The Boron family
1. B is a metalloid and always forms covalent bonds
— usually forms 3 bonds using sp2 hybridised orbitals (120o)
— no tendency to form univalent compounds
— all BX3 compounds are electron deficient – cf Lewis acids

2. Al, Ga, and In show stable +3 oxidation state

— heavier elements show inert pair effect hence univalent compounds become
increasingly important in the order Ga→In→Tl
— elements more metallic and ionic than B
— many of their compounds are covalent when anhydrous but they form ions
in solution
 Group 13 – The Boron family
 covalency vs ionicity depends on which one is energetically
favorable
— hydration may lead to change from covalency to ionicity – i.e., if the
hydration energy is greater than ionisation energy then ionic character will
dominate
❖ for example
— Al → Al3+; 5137 kJmol-1
— Hhy; -4665 kjmol-1(Al3+) and -381 kjmol-1 (Cl-) = -5808 kJmol-1 in total
which is greater than IE
— therefore, AlCl3 ionises in solution
— hydrated metal ions undergo hydrolysis in solution e.g. AlCl3
 Group 13 – The Boron family
3. increased tendency to form univalent compounds down the group
(see inert pair effect)
— compounds of Ga(I), In(I) and Tl(I) are known
— for Ga and In, the +1 oxidation state is less stable than the +3
— Tl(I) is thallous compounds are more stable than Tl(III) thallic compounds
Group 13 – The Boron family
 Atomic radius
 no regular increase in atomic size down the group (Cf with Gp1
and 2)
— due to interposition of d block elements between Al and Ga and f block
elements between In and Tl
— d and f electrons are poor at shielding outer electrons; effective nuclear
charge experienced by outer electrons much larger than expected from
periodicity considerations

— expected increase in size from period 3 to 4 is effectively counterbalanced

by the large Zeff
 Ionisation energy
 no regular decrease down the group
— observed decrease between B and Al is due to increase in size and hence
decrease in Zeff
— discontinuity between A and Ga; and In and Tl is due to the poor screening
effect of d and f orbitals
— expected increase in size from period 3 to 4 is effectively counterbalanced
by the large Zeff
 Occurrence
 B is a rare element
— 9 ppm of the earth’s crust
— borax (Na2[B4O5(OH)4.8H2O), kernite Na2[B4O5(OH)4.2H2O) and colemanite
(Ca2B6O11) are the major ores

 Al is the most abundant metal and 3rd most abundant element

— 83000 ppm of the earth’s crust
— bauxite (hydrated aluminium oxide i.e. Al2O3.nH2O) is the most important
ore)
— also occurs in aluminosilicate rocks such as micas and feldspars
 Occurrence
 Ga is twice as abundant as boron
— 19 ppm ppm of the earth’s crust

 In (0.24ppm) and Tl(0.5ppm) are much rare

— Ga, In and Tl occur as impurities in sulphides
 Extraction of Boron
 on a large scale, boron is extracted from its minerals, borax
Na2B4O7 or colemanite Ca2B6O11
— the latter is first converted to borax by boiling with a solution of sodium
carbonate

2Ca2B6O11 + 3Na2CO3 + H2O →3Na2B4O7 + 3CaCO3 + Ca(OH)2

— the insoluble calcium carbonate settles down and borax is crystallized from
the mother liquor

 boron is isolated from borax in the following steps

 Extraction of Boron
1. preparation of boron trioxide
— borax is treated with hot concentrated hydrochloric acid, where the sparingly
soluble boric acid slowly separates out
Na2B4O7•10H2O(s) + H2SO4→ 4 H3BO3+ Na2SO4+ 5H2O

2. boric acid is then dehydrated to the oxide (B2O3)

H3BO3(s) + heat→B2O3(s)
 Extraction of Boron
3. reduction of the oxide with magnesium or sodium gives
amorphous boron that is only about 95% pure:
B2O3(s)) +3Mg(s) + heat→2B(s) +3MgO(s)
— difficult to obtain pure crystalline B because it has very high melting point
(2180oC) and the liquid is corrosive
 Extraction of Boron
 small amounts of pure crystalline B can be obtained by:
i. reduction of BCl3 with H2
2BCl3 + 3H2 →2B +6HCl (on a red hot W and Ta filament)

ii. pyrolysis of BI3 (on a red hot W and Ta filament)

2BI3→2B + 3I2

iii. thermal decomposition of diborane or other boron hydrides

B2H6 + heat →2 B + 3H2
 Uses of Boron
 production of boron steel or boron carbide control rods for nuclear
reactors
— high cross-section for capturing neutrons
 boron carbide used as an abrasive
 boron used to make impact resistant steel
 borax is used to make fibreglass for insulation and textiles and to
make perbolates for detergents
 borax is used as a flame retardant etc
 boric acid used in agriculture as liquid fertilizers
 Extraction of aluminium
 aluminium is very difficult to isolate due to the high stability of the
Al3+ ion
— use electrolysis (Hall-Heroult process)
 bauxite contains a number of impurities
— silica,oxides of iron and titanium oxide
❖ therefore, first step involves purification of the ore
 Extraction of aluminium: The Bayer Process
1. ore is heated in sodium hydroxide (170-180 oC)
• SiO2(s) + 2OH-(aq) → SiO32-(aq) + H2O(l)
• Al2O3(s) + 2OH-(aq) → 2AlO2-(aq) + H2O(l)

❖ iron oxide and titanium oxide unaffected and are filtered off

2. treatment of solution with acid

• 2AlO2-(aq) + H3O+(a) → Al(OH)3(s) i.e., bubble CO2 or by seeding the
solution using Al2O3
• silicate ions remain in solution
 Extraction of aluminium: The Bayer Process
3. aluminium hydroxide heated at 125oC to give aluminum oxide
(corrundum)
Al(OH)3(s) → Al2O3(s) + 3H2O(l)

 the mpt of Al2O3 is too high (2015 oC) and its electrical
conductivity too low to make direct electrolysis commercially viable
 Al2O3 is mixed with cryolite (Na3AlF6, containing about 10% CaF2) to
reduce its mpt to about 1000 oC
Extraction of aluminium: The Bayer Process
 Extraction of aluminium: Hall-Héroult Process
 developed by two 22-year-old scientists independently
— Charles Hall: American Chemist
— Paul Heroult: French Metallurgist

 corrundum is reduced to Al in the Hall-Héroult electrolytic cell

— cathode made of carbon (graphite) and constitutes lining inside the cell
— an external electrical potential drives electrons into the graphite cathode
where Al3+ ions are reduced
Al3+(melt) + 3e → Al(l)
— the anode which is also made of graphite is oxidised during electrolysis
2O2-(melt) + C(s) → CO2(g) + 4e
Extraction of aluminium: Hall-Héroult Process
— theanode which is also made of graphite is oxidised during electrolysis
2O2-(melt) + C(s) → CO2(g) + 4e

❖ other products formed at the anode are O2, F2 and carbon compounds of
fluorine ( these erode the anode)
Extraction of aluminium: Hall-Héroult Process
 Extraction of aluminium: Hall-Héroult Process
 the key to the Hall-Héroult Process is
— the use of molten cryolite as a solvent: melts at accessible temperatures;
dissolves Al2O3; and is available in the necessary purity
— the choice of graphite as the anode: provides easy oxidation process which
produces a gas

 the electrolytic production of aluminium is however energy intensive

❖ Reading topic: Uses of aluminium

 Extraction of Ga, In and Tl
 these elements are very rare
— usually obtained as by-products in the processing of other metals

 traces of Ga found in bauxite

— isolated during the purification of alumina through electrolysis

 In and Tl occur in minute quantiles in ZnS and PbS ores

— oresroasted with air in smelter to convert them to ZnO and PbO
— Tl and In recovered from the flue dust and extracted by electrolysis of
aqueous solutions of their salt
❖ Read -uses of Ga, Tl and In
 Compounds of Boron and Oxygen
 most important compounds are sesquioxides and borates
— boron and all other elements of the group when heated in oxygen give
respective sesquioxide
— sesqui means one and half as they have the general formula MO1.5 ( e.g.,
B2O3)
— dehydration of orthoboric acid also gives boron sesquioxide
 Compounds of Boron and Oxygen
 chemical nature of boron sesquioxide
— boron sesquioxide is amphoteric:
❖ it reacts with metallic oxides (bases) forming salts called borates or
metaborates
— in borax bead test boron sesquioxide (or borax) is mixed with a metal oxide
and heated on a flame forming a glass like bead
— the beads of many transition metals are characterized by their colours
— this test provided first proof that vitamin B12 contains cobalt
 Compounds of Boron and Oxygen
 chemical nature of boron sesquioxide
— B2O3 may also behave like a base if reacted with a strongly acidic
compound such as phosphorus pentoxide giving boron phosphate

❖ boric acid is soluble in water and behaves as a weak monobasic acid

— does not donate protons like most acids but accepts OH- ions; behaves like a
Lewis acid

Trigonal planar tetrahedral

 Compounds of Boron and Oxygen
 in the solid state B(OH)3 units are hydrogen bonded together to
form 2-D sheets (3.18Å apart) with almost hexagonal symmetry

• orthoborates contain discrete

BO33- ions
– examples are : Mg3(BO3)2 and
LnIIIBO3
 Compounds of Boron and Oxygen: Metaborates

 in metaborates simple units join to form a variety of polymeric

chain and ring structures
— BO3 planar triangular units or BO4 tetrahedral

1. pyroborates
— two triangular units join by sharing one corner e.g. Mg2[B2O5] and CoII[B2O5]
❖ cf with pyrophosphates
 Compounds of Boron and Oxygen: Metaborates

2. ring structures
— three triangular units share corners to form a ring
e.g. Na3[B3O6] and K3[B3O6

Structure of the metaborate anion, [B3O6]3-

 Compounds of Boron and Oxygen: Metaborates

3. polymeric structures
— many triangular units polymerise to an infinite chain
e.g. [Ca(BO2)2]n
 Compounds of Boron and Oxygen: Metaborates

• most common metaborate is borax - Na2[B4O5(OH)4.8H2O

— usefulprimary standard for titration against acids
— one of the products H3BO3 is a weak acid; hence need an indicator not
affected by H3BO3 e.g. methyl orange (changes in the pH range 3.1-4.4)

Na2[B4O5(OH)4.8H2O + 2HCl → 2NaCl + 4 H3BO3 + 5H2O

— in water borax forms [B(OH)4]- and B(OH)3 but only the former reacts with
HCl
1. [B4O5(OH)42- + 5 H2O  2B(OH)3 + 2 [B(OH)4]-
2. 2[B(OH)4]- +2H3O+ → 2B(OH)3 + 54H2O
 Metaborates: Sodium peroxoborate

• used as a brightener in washing powders

— it is compatible with enzymes which are added to some biological powders
— in hot water (>80oC) the peroxide linkages O-O break down to give H2O2

• two main preparative methods

— electrolysis of sodium borate (containing some sodium carbonate)
— oxidation of boric acid or sodium metaborate with hydrogen peroxide
2NaBO2 + H2O2 + 6H2O → Na2[(OH)2B(O-O)2B(OH)2.6H2O
 Other Group 13 Oxides

• alumina, Al2O3 exists in two crystalline forms: -Al2O3 (corundum)

and -Al2O3
— corundum is found as a mineral and may also be produced from heating
Al(OH)3 or -Al2O3 above 1000 oC
— corundum is very hard and hence used to polish glass
— impure form of corundum contaminated with iron oxide and silica is called
emery and used to make sand paper – for polishing metals
— corundum not affected by acids and has high mpt (>2000 oC); hence used as
refractory to line furnaces and make containers for high T reactions

❖ -alumina is made be dehydrating Al(OH)3 below 450 oC

❖ it dissolves in acids; absorbs water
 Other Group 13 Oxides

❖ alumina is white but can be coloured by addition of Cr2O3 or Fe2O3

❖ white saphires are gem quality corundum

❖ blue saphires are a mixed oxide containing traces of Fe2+, Fe3+ and Ti4+
 Other Group 13 Oxides

❖ synthetic rubies are made by strongly heating mixture of Al2O3 and Cr2O3 in an
oxy-hydrogen flame
❖ rubies are very hard and hence used for jewellery and to make bearings in
watches and instruments
 Trihalides

 all elements form trihalides

—B trihalides are covalent and electron deficient compounds
— BF3 is a gas; BCl3 is a liquid and BI3 is a solid
— the trihalides especially BF3 and BCl3 are important industrially – used to
prepare B and to promote organic reactions e.g., Friedel-Crafts reaction –
read other uses of BF3

 the fluorides of Al, Ga, In and Tl are ionic and have high mpts
— the other halides are largely covalent when anhydrous
 Trihalides

 AlCl3, AlBr3 and GaCl3 exist as dimers

— toattain octet
— dimeric structure retained when the halides dissolve in non-polar solvents e.g.,
benzene
— broken when dissolved in water – high hydration energies
 Trihalides

 why does BX3 not dimerise?

— attains octet via p-p bonding
— other elements have larger atoms and hence p-p bonding is not as
effective
 Boron hydrides - Boranes

 boranes are synthetic boron-hydrogen compounds

— have the general formula BxHy
— when exposed to air, several of the boranes quickly oxidize, some of them violently
— borane, the parent component BH3, is only known in the gaseous state and dimerizes
to generate B2H6 (diborane)
— the larger boranes are made up of polyhedral boron clusters, some of which are
isomers
— diborane B2H6, pentaborane B5H9, and decaborane B10H14 are the most significant
boranes
— boranes have been investigated as potential fuels, rocket propellants, and automobile
components
 Boron hydrides – diborane (B2H6)

 simplest is borane (B2H6)

— similar formula to ethane but structurally very different
because it is electron deficient
— gets around the problem by forming delocalized bonds
 the B-H-B unit is held together by 2e
— this is called a 3 centre - 2 electron bond (3c2e)

 the orbital basis can be made up of two sp3 hybrids of the

B atoms and two H(1s) orbitals
— the remaining boron orbitals form normal 2c2e bonds to the
terminal H’s
 Boron hydrides – structure of diborane

 there are 12 valence electrons available for

chemical bonding (B has 3, and H has 1, so
2xB + 6xH =12)
 each terminal B–H bond is a normal 2e2c
bond and there are 4 of these, thus
accounting for a total of 8 electrons
 this leaves a total of 4 electrons to share
between the two bridging H
— consequently, 2 B–H–B bridging bonds are
formed, each of which consists of 2 electrons
forming what are called 3c2e bonds– sometimes
called ‘banana’ bonds, as they are not linear but
curved
 Boron hydrides – structure of diborane

 each B atom is sp3 hybridised – 4 orbitals for each B

— two of the 4 sp3 hybrid orbitals form  bonds to the terminal H atoms (1s orbitals)
— that leaves 2 B sp3 hybrid orbitals, one contains an electron, one which is empty

 for each bridge , 1 sp3 orbital from each of the B atoms combines with
the 1s orbital of the bridging H atom to form 3 new molecular orbitals
— (MOs) – n atomic orbitals (AO) form n Mos
— 1 B atom gives its remaining valence e to one bridge, and the other B atom gives to
the other
Boron hydrides – structure of diborane

— each bridge, , has 2 electrons, which fill our new MO scheme starting with the lowest
energy bonding MO other
Boron hydrides – structure of diborane

Bond order = (2-0)/4

= 1/2
 Boron hydrides – structure of diborane

 3c2e bonds are occasionally shown in structural diagrams like this:

 all boranes are electron deficient

— the need to form 3c2e bonds causes the molecules to ‘curl-in’ on themselves
— the more electron deficient the more ‘spherical’ a molecule becomes
 Classification of boranes

 Nomenclature
— in neutral boranes the number of boron atoms is given by a prefix and the number of
H atoms is given in parentheses behind the name
❖ B5H11 = pentaborane(11)
❖ B4H10 = tetraborane(10)

— for ions first the number of H atoms and then the number of B atoms is given, behind
the name; the charge is given in parentheses
❖ [B6H6]2− = hexahydrohexaborate(2-)
 Wades rule: Structures of boranes

 Wades rules help to predict the general shape of a borane polyhedron

from its formula
— count the number of B-H units; every B-H unit contributes two electrons to the skeletal
electrons
— every further H atom contributes a further electron to the skeletal electrons and
— charge contributes electrons corresponding to the charge
— the resulting number of electrons is divided by two to get the number of skeletal
electron pairs within the borane

❖ the general structure is defined by the number of skeletal electron pairs

 Wades rule: Structures of boranes

 the polyhedra are always made up of triangular faces, so they are

called deltahedra
— three most common structural types (closo, nido, arachno)

• closo comes from the Greek for cage

• nido the Latin for nest
• arachno the Greek for spider
 Wades rule: Structures of boranes

 Closo boranes
— closed deltahedra without B-H-B 3c,2e bonds
— thermally stable and moderately reactive
— example: [B5H5]2−: the ion builds up a trigonal bipyramidal polyhedron

 Nido boranes
— closo borane with one corner less and addition of two hydrogen-atoms instead
— B-H-B-bonds and B-B-bonds are possible
— thermally stability lies between closo- and arachno-boranes
— example: B5H9
— its structure can be assumed as the octahedral deltahedron of [B6H6]2− without one
corner tetragonal pyramid
 Wades rule: Structures of boranes

 Arachno boranes
— closo borane deltahedron but with two BH-units removed and two H-atoms added.
— it has to have B-H-B 3c, 2e-bonds
— thermally unstable at room temperature and highly reactive
— example: B4H10 the structure can be derived from [B6H6]2−
— deltahedron with two corners less

❖ there are also other structures like the hypho boranes, but they are less important
Wades rule: Structures of boranes
Synthesis of diborane
Synthesis of higher boranes
Properties of diborane
Properties of diborane

 most of the higher

boranes are liquids
— B6H10 and B10H14
are solids
— as the molecular wt
increases, they
gradually become
more stable in air
and less sensitive to
water
Reactions of diborane: Read JD Lee
 Boron-nitrogen compounds

 analogous to C-C compounds

— B-N unit isoelectronic with C-C unit

 C-C compounds similar to B-N compounds but less polar

— covalent radii (N = 0.70; C=0.77; B = 85)
— electronegativity (N = 3.07; C=2.50; B = 2.01)

 three types of B-N compounds

i. amine boranes (analogous to alkanes)
ii. aminoboranes (analogous to alkenes)
iii. borazines (analogous to benzenes)
 1. Amine boranes

 Lewis acid-base adducts containing a boron-nitrogen donor bond

—B and N are tetrahedral and B-N bond length is comparable to C-C bond
length in simple alkanes e.g., ethane
— they are formed by symmetrical cleavage of diborane or by reaction of
ammonium salts
[H3NR]Cl + LiBH4  RH2N→BH3 + LiCl +H2

— the B-N bond strength varies from one adduct to another

— donor-acceptor interaction vs complete sharing

 1. Amine boranes

 steric hindrance can prevent formation of some adducts

— e.g. 2,6-dimethylpyridine and trimethyl borane

— diadducts can also be obtained when bidentate bases are used e.g. en

— thechief reaction of amine boranes is elimination of HX or RH to give

aminoboranes
 2. Aminoboranes

 analogous to alkenes
—B is trigonal and the three substituents at B are planar
— two resonance forms of aminoboranes

— in most cases there is something less than a full double bond

 synthesised by reduction of ammonium salts with tetrahydroborate
reagents
 2. Aminoboranes

 main reaction of amino boranes other than substitution is condensation to

cyclic systems
 3. Borazines

 resemble benzene structurally (C6H6 vs B3N3H6)

— similarphysical properties but borazine is more reactive and readily
undergoes addition reactions

B3N3H6 + HX →(—H2N—BHX—)3; X = Cl, OH, OR etc.

— such reactions do not occur with benzene

 Borazine may be hydrolysed to ammonia and boric acid at elevated

temperatures
— similar to benzene, borazine forms  complexes with transition metals
 3. Borazines

 similar to benzene, borazine forms  complexes with transition metals

 3. Borazines

 Synthesis of borazine and substituted borazines

79

chemistry of aluminium and its compounds (including clay minerals

and zeolites) – see group 14 chemistry