Group 13, the

Boron Family

Thallium(I) is intensely
poisonous because its
ionic radius
is very similar to that of
potassium and sodium
ions: it enters cells and
disrupts the mechanisms
of potassium and sodium
transport
 Representative
Representative Elements
Elements

Groups 13 through 18
• The elements in Groups 13-18 are not all solid
metals like the elements of Groups 1 and 2. In
fact, a single group
can contain metals,
nonmetals, and
metalloids and have
members that are
solids, liquids, and
gases.
 Representative
Representative Elements
Elements

Group 13—The Boron Family

• The elements in Group
13 are all metals except
boron, which is a brittle,
black metalloid.
• Cookware made with
boron can be moved
directly from the
refrigerator into the
oven without cracking.
 Representative
Representative Elements
Elements

Group 13—The Boron Family

• Aluminum is used to make
soft-drink cans, cookware,
siding for homes, and
baseball bats.
• Gallium is a solid metal,
but its melting point is so
low that it will melt in
your hand.
• It is used to make
computer chips.
Produksi Alumunium Dunia
Produksi Galium Dunia
Penggunaan Boron dan
Alumunium
 The Elements
• Al is very inert on account of the presence of a
passivating surface oxide film.
• Aluminium has a high reflectance, which is maintained in
the powdered form, making it a useful component of
silver-coloured paints. It is a good thermal and electrical
conductor.
• Gallium is brittle at low temperatures but liquefies at
30C. Its low melting point is attributed to its crystal
structure, in which each Ga atom has only one nearest
neighbour and six next-nearest neighbours: thus, the Ga
atoms tend to form GaGa pairs.
 The Elements
• Gallium has the widest liquid range (30 - 2420°C) of any
element with the exception of Hg and Cs.
• Unlike Hg, Ga wets glass and skin, making it more
difficult to handle.
• Gallium readily forms alloys with other metals and
diffuses into their lattices, making them brittle.
• Indium forms a distorted ccp lattice and Tl is hexagonal
close packed.
 The Elements
• Boron di alam: borax
(Na2B4O5(OH)4.8H2O) dan kernite
(Na2B4O5(OH)4.2H2O
• Aluminium di alam: lempung dan mineral
aluminosilikat, khususnya bauxite, a
complex mixture of hydrated aluminium
hydroxide and aluminium oxide
 The Elements
• Gallium oxide occurs as an impurity in
bauxite and is normally recovered as a
byproduct of the manufacture of
aluminium.
• Indium and thallium occur in trace
amounts in many minerals.
Sifat-sifat Unsur Gol. 13
Sifat-sifat Unsur Gol. 13
 Boron
• anhydrous sodium
tetraborate,
Na2B4O7 Mineral
Borax
• sodium tetraborate
pentahydrate,
Na2B4O7·5H2O
• setraborate
decahydrate, Struktur anion
[B4O5(OH)4]2−
Na2B4O7·10H2O
 Boron
• Ulexite : NaCa[B5O6(OH)6].5 H2O
• Borax: Na2[B4O5(OH)4]. 8 H2O
• Colemanite: Ca2[B3O4(OH)3]2.2
H2O)
• Kernite: Na2[B4O5(OH)4].2 H2O Mineral
Borax
• Borates do have complex
structures, but common to all is
that Boron is contained as trigonal
BO3 or tetragonal BO4 units.
Struktur anion
[B4O5(OH)4]2−
 Boron
• Borax + asam menjadi • When borax is added to a
asam birat (boric acid) flame, it produces a
dand senyawa borat yellow green color.
lainnya. • Borax is not used for this
• Reaksi dengan HCl: purpose in fireworks due
Na2B4O7·10H2O + 2 HCl → 4 to the overwhelming
H3BO3 + 2 NaCl + 5 H2O yellow color of sodium.
• The "decahydrate" is • Boric acid is used to color
sufficiently stable to find methanol flames a
use as a primary standard transparent green.
for acid base titrimetry.
 Boron
• Isolation of the element:
• Boron is made in 95-98% purity as an
amorphous powder by reduction of the
oxide B2O3 with Mg
B2O3 + 3 Mg → 2 B + 3 MgO
• or Zn
2 BCl3 + 3 Zn → 3 ZnCl2 + 2 B
 Penggunaan Boron
• Borosilicate glass- • Pyrotechnics
pyrex • Used in production
• Detergents of impact resistant
• Flame retardants steels
• Ceramics • Control rods in
nuclear reactors
 Ikatan pada Boron
• 2c-2e- B-H
• 3c-2e- B-H-B
• 2c-2e- B-B
• 3c-2e- B-B-B
Boron
Boron
The first member of each
group differs from its
congeners → small atomic
radius. However, B have a
pronounced diagonal
relationship with Si:
1. Boron and silicon form
acidic oxides, B2O3 and
SiO2; aluminium forms an
amphoteric oxide.
2. Boron and silicon form
many polymeric oxide
structures and glasses.
3. Boron and silicon form
flammable, gaseous
hydrides; aluminium hydride
is a solid.
• Boron amorf → serbuk
coklat
• Boron kristal → hard,
refractory and shiny black
crystals.
• The three solid phases
for which crystal
structures are available
contain the icosahedral Boron Amorf
(20-faced) B12 unit as a
building block
Allotrop Boron
Allotrop Boron
Allotrop Boron
• This icosahedral unit is a
recurring motif in boron
chemistry
• Boron is inert, and under
normal conditions finely
divided B is attacked only
by F2 and HNO3.
 Senyawa
Unsur Golongan 13

All of the elements form hydrides, oxides, and halides in the +3 oxidation
state. The +1 oxidation state becomes more stable down the group and is
the most stable oxidation state for compounds of thallium.
 Hidrida Boron
• Ciri khas:
konfigurasi
elektron ns2np1
• The binary
hydrogen
compounds of B
are called boranes
diboran
 Hidrida Boron
• Tetraboran
• It is easily oxidized
→ must be kept
under vacuum.
• Tetraborane ignites
when it comes in
contact with air,
oxygen, and nitric
acid.
 Hidrida Boron
• Boranes → very
toxic and are
biologically
destructive.
• A small daily
exposure of the
chemical to rabbits
and rats resulted in
fatality
dodecaborane
 Hidrida Boron
• Semua hidrida • Alkali metal
Boron → green tetrahydridoboranat
flame es, NaBH4 and
• several of them LiBH4, → general
ignite explosively reducing agents
on contact with air. and as precursors
for most
boronhydrogen
compounds.
 Halida Boron
• BX3 → of trigonal-planar • The electron deficiency is
molecules and monomeric in partially removed by XB π
the gas, liquid, and solid states. bonding between the halogen
• BF3 & BCl3: gases, BBr3 : atoms and the B atom, giving
volatile liquid, and BI3 : solid → rise to the partial occupation of
consistent with the increase in the vacant p orbital on the B
strength of dispersion forces atom by electrons donated by
with the number of electrons in the halogen atoms.
the molecules. • The trend in Lewis acidity
• BX3 → incomplete octet and stems from more efficient XB π
are Lewis acids. The order of bonding for the lighter, smaller
Lewis acidity is BF3 < BCl3 ≤ halogens, the FB bond being
BBr3. one of the strongest single
bonds known.
Hidrida Boron
 Boron
• The hydrides of Boron:
• Diborane:

• Lab quantities:

• Industrial Quantities:
Boron
 Boron
• Reactions of Boranes:
 Boron
• Deca boranes:
 Boron
• Borohydrides of many metals have been
made and some representative syntheses
are:
Boron Hydrides

Housecroft, C. E.; Sharpe, A. G.

inorganic Chemistry. New York:
 Housecroft, C. E.; Sharpe, A. G.
inorganic Chemistry. New York:
Pearson Education Limited, 2001.
272.
 Wade’s Rules
• n = number of B atoms in parent closo-
deltahedron
• Always n+1 bonding e- pairs and n+1
bonding MOs
– nido has n-1 vertices
– arachno has n-2 vertices
– hypho has n-3 vertices
 Using Wade’s Rules
 Find total available bonding e-s:
 Each B-H unit gives 2 e-s
 Each additional H gives 1 e-
 Overall charge
 Find parent closo-deltahedron
 n+1 bonding e- pairs
 Is it closo, nido, arachno, hypho?
 Lose highest connectivity B first then lose adjacent sites
 Determine number of remaining hydrogen atoms
 Each vertex has a H
 “sew up” hole with H atoms
 Bridging H atoms
 Low connectivity B atoms can get another 2c-2e - B-H bond
 Try to keep it as symmetrical as possible
Huheey, J. E.; Keiter, E. A.; Keiter,
R. L. Inorganic Chemistry:
 Boron Neutron Capture Therapy
(BNCT)
• 10B has large cross-section for neutron
capture
• 10B +   + 7Li

• Products can kill cells

• Cancer treatment
• Cages - need high [10B] in cell
 Boron
The main resemblances to silicon and differences from the
more metallic aluminum are as follows:

1. The oxide B2O3 and B(OH)3 are acidic. The compound

Al(OH)3 is a basic hydroxide, although it shows weak
amphoteric properties by dissolving in strong NaOH.

2. Borates and silicates are built on similar structural

principles with sharing of oxygen atoms so that complicated
chain, ring, or other structures result .
 Boron
3. The halides of Band Si (except BF 3) are
readily hydrolyzed. The AI halides are
solids and only partly hydrolyzed by
water. All act as Lewis acids.
4. The hydrides of B and Si are volatile,
spontaneously flammable, and readily
hydrolyzed. Aluminum hydride is a
polymer, (AlH3)n
 Boron
• Crystalline boron is very inert and is
attacked only by hot concentrated
oxidizing agents. Amorphous boron is
more reactive. With ammonia for instance,
amorphous boron at white heat gives (BN)x
a slippery white solid with a layer structure
resembling that of graphite, but with
hexagonal rings of alternating B and N
atoms.
 Boron
Hydrated borates contain polyoxo anions in the crystal,
with the following important structural features:
1. Both BO3 and tetrahedral BO4 groups are present, the
number of BO4 units being equal to the charge on the anion.
2. Anions that do not have BO4 groups, such as metaborate,
B3O63-, or metaboric acid, B3O3(OH)3, hydrate rapidly and
lose their original structures.
3. Certain discrete as well as chain-polymer borate anions
can be formed by the linking of two or more rings by
shared tetrahedral boron atoms.
 Boron

Boric acid:
The acid B(OH)3 can be obtained as white needles
either from borates, or by hydrolysis of boron
trihalides.

When heated, boric acid loses water stepwise to form

one of three forms of metaboric acid, HBO2. If B(OH)3
is heated below 130°C, the so-called form-III is
obtained, which has a layer structure in which B 3O3
rings are joined by hydrogen bonding. On continued
heating of form-III of HBO2, between 130 and 150°C,
HBO2-II is formed.
Boron
 Boron
• Halides:
• Boron trihalide is a gas (bp -101 deg C)
• Boron trihalides are the strongest lewis acids.
• They react with Lewis bases
• B-X bonds are somewhat shorter than is
expected from the sum of the single-bond
covalent radii. This suggests a delocalized π-
bond system
 Al, Ga, In, Tl
• Al is the most common of the elements
• It is produced in pure form by electrolysis, and is
the most dirty of the industrial processes.
• Costs a lot of energy.
• Main source is Bauxite, a hydrous Al –oxide
• Al is attacked by diluted acids, but passivated by
strong acids.
• Al oxides are used to protect metals (anodized)
 Ga,In,Tl
• They are made from their salts by
electrolysis.
• Ga is used mainly in semiconductors with
Group V elements. (GaAs).
• Tl is a trace element and is very toxic.
– Main use to get rid of spies.
 Oxides
• Al has only one oxide formed Al2O3
• There is an alpha and a gamma oxide.
• Difference is the process and the
temperature to get alpha or gamma oxide.
• Mixed Al oxides are ruby (Cr3+)and
sapphire
• (Fe2+,Fe3+, Ti4+)
 Halides
• Halides are formed of all elements, the only one
that is special is TlI3.
• Tl and I2 form rather a Tl1+ and I3- compound
• All halides readily dissolve in benzene
Aqua ions
Hydroxides
 Hydrides
• The most important hydride is LiAlH 4
• It is a strong reducing agent and is mainly
used in organic chemistry
• It is used e.g. to hydrate double bonds
 Summary of group IIIa trends
1. Boron

(a) Forms no simple B3+cation.

(b) Forms covalent compounds almost exclusively,

and all polyatomic ions have covalent bonds.

(c) Obeys the octet rule, the maximum covalence

being four.

(d) Forms trivalent compounds that readily serve as

Lewis acids.
 Summary of group IIIa trends
(e) Frequently forms polyhedral structures: boranes and
borates.
(f) Forms an oxide, B203, and a hydroxide, B(OH)3 both of
which are acidic.
(g) Forms covalent halides that are readily hydrolyzed.
(h) Forms numerous covalent hydrides, all of which are
volatile, flammable, and readily hydrolyzed.
(i) Forms a stable and important hydride anion, BH4-.
 Summary of group IIIa trends
2. Aluminum
(a) Readily forms an important 3+ ion, because it is electropositive.
(b) Is much more metallic than boron, and forms a greater number
and variety of ionic substances.
(c) Forms both molecular and ionic substances, with coordination
numbers of six and higher.
(d) Forms two oxides, only one of which is acidic.
(e) Forms a hydroxide that is weakly amphoteric, although mostly
basic.
(f) Forms solid halides that are only partially hydrolyzable.
(g) Forms a polymeric hydride.
(h) Forms an anionic hydride (AlR-) that is more reactive than BH4-.
 Summary of Group IIIa trends
3. Gallium, Indium, and Thallium
(a) Readily give the M3 + ion in solution, and have a
rich coordination chemistry typical of metals.
(b) Form increasingly stable lower valent compounds,
especially TI+.
(c) Increasinglyformweakercovalent
bondsondeseentofthegroup,enhancing the formation of
monovalent compounds.
(d) Form MX3 halides that are increasingly aggregated
in the solid state (through halide ion bridges) to give
coordination numbers of four, six, and higher.
(e) Do not form important EH4- anions, except perhaps
GaH4-.
This powerpoint was kindly donated to
www.worldofteaching.com

http://www.worldofteaching.com is home to over a

thousand powerpoints submitted by teachers. This is a
completely free site and requires no registration. Please
visit and I hope it will help in your teaching.