3.

Boron Group
C t t Content
3.1 Occurrence
3.2 Properties
Group
13 IIIA
3.3 Boron-Elemental Structures
3.4 Synthesis and Chemical Behaviour
3.5 Applications
5
B
13 or IIIA
pp
3.6 Boron-Oxygen Compounds
3.7 Boranes
3 8 Boron Halides
31
13
Al
B
3.8 Boron Halides
3.9 Boron-Nitrogen Compounds
3.10 Aluminium-Oxygen Compounds
3 11 AluminiumHydrides
31
Ga
49
In
3.11 Aluminium Hydrides
3.12 Aluminium Halides
3.13 Gallium and Indium
3 14 Th lli d h I P i Eff
In
81
Tl
113
3.14 Thallium and the Inert-Pair Effect
3.15 Biological Aspects
Triels
113
Uut
Slide 1 Inorganic Chemistry I
Prof. Dr. T. Jstel

3.1 Occurrence
Th El t f th Thi d M i G D N t E i t A El t B f Th i The Elements of the Third Main Group Do Not Exist As Elements, Because of Their
High Reactivity (Aluminium Is the Most Abundant Metal of Earths Crust)
B N B O 10H O B Boron Na
2
B
4
O
7
.
10H
2
O Borax
Mineral: Borax Na
2
B
4
O
7
.
4H
2
O Kernite
NaCaB
5
O
9
.
8H
2
O Ulexite
Aluminium (alumen) Al
2
O
3
Corundum, sapphire, ruby
Lat.: Alaun Al(OH)
3
Hydrargillite
AlO(OH) Diaspore boehmite AlO(OH) Diaspore, boehmite
Al
2
(OH)
4
[Si
2
O
5
] Kaolinitic clay
Na
3
[AlF
6
] Cryolite
Gallium (gallia) rare, normally accompanied by other elements, e.g. Zn
Lat.: France limited resources
Indium rare, mostly accompanied by Zn (ZnS) Indium rare, mostly accompanied by Zn (ZnS)
Indigo spectral line limited resources
Thallium (thallus) TlAsS
2
Lorandite
Greek: green twig
Slide 2 Inorganic Chemistry I
Prof. Dr. T. Jstel
g g
3.2 Properties
B I th M t El t iti N M t l (M S i M t l) All Oth Boron Is the Most Electropositive Non-Metal (More a Semi-Metal). All Other
Members of the Group Are Metals
B Al Ga In Tl B Al Ga In Tl
Atomic number 5 13 31 49 81
Electronic [He] [Ne] [Ar] [Kr] [Xe]4f
14
configuration 2s
2
2p
1
3s
2
3p
1
3d
10
4s
2
4p
1
4d
10
5s
2
5p 5d
10
6s
2
6p
1
configuration 2s
2
2p
1
3s
2
3p
1
3d
10
4s
2
4p
1
4d
10
5s
2
5p 5d
10
6s
2
6p
1
Electronegativity 2.0 1.5 1.8 1.5 1.4
Ionisation energy [eV] 8.3 6.0 6.0 5.8 6.1
Standard potential Standard potential
Me/Me
3+
[V] -0.87 -1.68 -0.53 -0.34 +0.72
Oxidation states +3 +3 (+1), +3 (+1), +3 +1, +3
Melting point T
m
[C] 2080 660 30 157 304 Melting point T
m
[ C] 2080 660 30 157 304
Boiling point T
b
[C] 3860 2518 2200 2080 1457
Density [g/cm
3
] 2.34 2.70 5.91 7.31 11.85
The most stable oxidation state of B, Al, Ga and In is +3 as one would expect
Ga
+
and In
+
are strong reducing agents
Tl
3+
is a strong oxidising agent
Slide 3 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.3 Boron - Elemental Structures
F C lli M difi i f B A K Wh i Th C Four Crystalline Modifications of Boron Are Known, Wherein The Common
Structural Unit Consists of B
12
-Icosahedrons (20 Facets)
o-rhombohedral boron
Cubic closed packing of B
12
-icosahedrons
o-tetragonal boron
Hexagonal closed packing of B
12
-icosahedrons + individual boron atoms
-rhombohedral boron
Complex structure with 105 B atoms per unit cell
-tetragonal boron
Complex structure with 190 B atoms per unit cell
The complexity of the structures is a result of the shortage of electrons
of boron which possess 4 valence orbitals but only 3 electrons
open and closed 2-electrons-3-center bonds (2e3c)
Slide 4 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.3 Boron Elemental Structures
i S f A i ifi i Typical For the Structures of the Allotropic Boron Modifications and For the
Boranes Are Two- and Three-Center-Bonding
Three-Center-Bonding
B
B B
sp
3
sp
3
sp
3
sp sp sp
B
B B
sp
3
p sp
3
H
B B
sp
3
s sp
3
Slide 5 Inorganic Chemistry I
Prof. Dr. T. Jstel
p p
3.4 Synthesis and Chemical Behaviour
BBoron
Synthesis
Reduction of boron halides: 2 BCl
3
(g) + 3 H
2
(g) 2 B(s) + 6 HCl(g)
M t ll th l d ti f b id B O + 3 M 2 B + 3 M O Metallothermal reduction of boron oxide: B
2
O
3
+ 3 Mg 2 B + 3 MgO
Chemical behaviour
At room temp B reacts sluggishly and solely oxidising acids can oxidise it to boric acid At room temp. B reacts sluggishly and solely oxidising acids can oxidise it to boric acid
Formation of metal borides: Mn
4
B, CrB, TiB
2
, MgB
2
, WB
4
, CaB
6
, YB
66
Aluminium Aluminium
Synthesis (annual production 1990: 18.5
.
10
6
t, 2009: 36.9
.
10
6
t)
F. Whler 1827: AlCl
3
(s) + 3 K(s) Al(s) + 3 KCl(s)
1 Step: Al O -Formation from bauxite (AlO(OH) + Fe O ) by Bayer-process 1. Step: Al
2
O
3
-Formation from bauxite (AlO(OH) + Fe
2
O
3
) by Bayer-process
AlO(OH)(s) + Fe
2
O
3
(s) + NaOH(s) Na[Al(OH)
4
](aq) + Fe
2
O
3
(s)
2 Na[Al(OH)
4
] + Al(OH)
3
-Seed cystal 2 NaOH + 2 Al(OH)
3
Al
2
O
3
(s) + 3 H
2
O(l)
2. Step: Fused-salt electrolysis of Al
2
O
3
with the addition of cryolite (Na
3
AlF
6
) as a flux
AT
2. Step: Fused salt electrolysis of Al
2
O
3
with the addition of cryolite (Na
3
AlF
6
) as a flux
(eutectic at 18.5 mol-% Al
2
O
3
: T
m
= 935 C)
Cathode: Al
3+
+ 3 e
-
Al(l)
Anode: 2 O
2-
+ C(s) CO
2
(g) + 4 e
-
Slide 6 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.4 Synthesis and Chemical Behaviour
Aluminium
Chemical behaviour
Oxidation: 4 Al(powder) + 3 O
2
(g) 2 Al
2
O
3
(s) :AH
R
= -3352 kJ/mol Oxidation: 4 Al(powder) 3 O
2
(g) 2 Al
2
O
3
(s) :AH
R
3352 kJ/mol
flash lamp for photography
With diluted acids: 2 Al(s) + 6 H
3
O
+
(aq) 2 Al
3+
(aq) + 3 H
2
(g) + 6 H
2
O(l)
With idi i id P i ti th h id ti f th f With oxidising acids: Passivation through oxidation of the surface
In alkaline solution: 2 Al(s) + 2OH
-
(aq) + 6 H
2
O(l) 2 [Al(OH)
4
]
-
(aq) + 3 H
2
(g)
In diluted aqueous solutions Al
3+
forms a hexaaqua aluminate ion which reacts as an acid:
[Al(H
2
O)
6
]
3+
(aq) + H
2
O(l) [Al(OH)(H
2
O)
5
]
2+
(aq) + H
3
O
+
(aq)
Solubility of Al
3+
:
pH < 4 [Al(H O) ]
3+
pH < 4 [Al(H
2
O)
6
]
4 < pH < 9 Al(OH)
3
pH > 9 [Al(OH)
4
]
-
Slide 7 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.5 Applications
Boron

10
B exhibits high neutron capturing cross-section moderator in nuclear power plants
Deoxidising agent in metallurgy g g gy
Ferroboron for the tempering of steel
Aluminium Aluminium
Low density (2.7 g/cm
3
): aviation/automotive industry, engineering, containers, pack.
High thermal conductivity: frying pans and cookware
Moderate electronic conductivity: high voltage cable Moderate electronic conductivity: high voltage cable
Gallium, Indium
Form semi-conducting III/V-compounds: (In,Ga)N, (In,Ga)P, (In,Ga)As LEDs
Alloying constituent in babbit metal
Thallium
Of some importance in forensics (Tl-verification in case of intoxication)
Tl/Hg-alloys with 8.7% Tl freezes at -60 C: low-temperature thermometer
Slide 8 Inorganic Chemistry I
Prof. Dr. T. Jstel
g y % p
3.6 Boron-Oxygen Compounds
i A i i i Boric Acids and Boron Trioxide
Ortho-boric acid H
3
BO
3
Structure of crystalline ortho-boric acid
B(OH) (aq) + H O(l) H
+
(aq) + [B(OH) ]
-
B(OH)
3
(aq) + H
2
O(l) H
+
(aq) + [B(OH)
4
]
Acts as mono-protonic acid
reacts with alcohols and sugars to esters
B(OH)
3
(s) + 3 MeOH(l) B(OMe)
3
(l) + 3 H
2
O(l) ( )
3
( ) ( ) ( )
3
( )
2
( )
T = 150 C: H
3
BO
3
(s) HBO
2
(s) + H
2
O(g)|
T = 300 C: 4 HBO
2
(s) H
2
B
4
O
7
(s) + H
2
O(g)|
Meta boric acid HBO Meta-boric acid HBO
2
Hydrolysis leads to H
3
BO
3
T = 500 C: 2 HBO
2
(s) B
2
O
3
(s) + H
2
O(g)|
Boron oxide B
2
O
3
Hydrolysis leads to H
3
BO
3
B
2
O
3
+ MO M(BO
2
)
2
Borax bead
B O + L O 2 L BO L S Y L L B
2
O
3
+ Ln
2
O
3
2 LnBO
3
Ln = Sc, Y, La - Lu
SrO + 2 B
2
O
3
SrB
4
O
7
Doping with Eu
2+
gives a UV-A phosphor
(
max
= 366 nm)
Slide 9 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.6 Boron-Oxygen Compounds
Borates
Ortho-borates
Structure of [B
4
O
5
(OH)
4
]
2-
Ortho-borates
Isolated trigonal planar [BO
3
]
3-
-units
Polymorph LnBO
3
-phases are isomorph to
C CO difi ti ( l it t it it ) CaCO
3
-modifications (calcite, vaterite, aragonite)
Meta-borates
BO
3
-units are combined to rings by oxygen atoms
Hydroxo borates such as [B
3
O
3
(OH)
5
]
2-
and [B
4
O
5
(OH)
4
]
2-
are hydrolysed meta borates
Structure of [B
2
(O
2
)
2
(OH)
4
]
2-
are hydrolysed meta-borates
Per-borates
Contain [B
2
(O
2
)
2
]-units
Application as sodium per-borate in detergents (presentations)
Slide 10 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.7 Boranes
B H d C d i t f Th C t B di (O t t R l ) Si Boron Hydrogen Compounds consist of Three-Center-Bondings (Octet Rule) Since
They Suffer from Electron Deficiency and Are Thus Highly Reactive
Diborane B H Diborane B
2
H
6
Synthesis: 2 BF
3
(g) + 6 NaH(s) B
2
H
6
(g) + 6 NaF(s)
Hydrolysis: B
2
H
6
(g) + 6 H
2
O(l) B
2
O
3
(s) + 3 H
2
(g)
Oxidation: B
2
H
6
(g) + 3 O
2
(g) B
2
O
3
(s) Oxidation: B
2
H
6
(g) + 3 O
2
(g) B
2
O
3
(s)
Structure
Sodium tetrahydridoborate NaBH
4
Only borane that is used on greater scale
Reducing agent in organic chemistry: aldehydes primary alcohols
ketones secondary alcohols
Slide 11 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.8 Boron Halides
Boron Halides Are Electron Deficiency Compounds As Well and Form t-Bonds
Monomers and Trigonal Planar Built
Synthesis Synthesis
B
2
O
3
(s) + 6 HF(g) 2 BF
3
(g) + 3 H
2
O(l)
Ph-NN
+
+ BF
4
-
Ph-F + BF
3
+ N
2
B O 3 C 3 Cl 2 BCl 3 CO
The o-bonding system in BF
3
is formed by
B
2
O
3
+ 3 C + 3 Cl
2
2 BCl
3
+ 3 CO
Reactions with water
linear combination of the three atomic orbitals
of boron, 2s, 2p
x
and 2p
y
, and three 2p -
orbitals of the fluorine atoms. Additionally, 4
4 BF
3
+ 3 H
2
O HBF
4
+ 3 H
3
BO
3
BX
3
+ 3 H
2
O 3 HX + H
3
BO
3
t-MOs are formed through the interaction
between the 2p
z
-orbital of boron with the three
2p
z
-orbitals of the fluorines.
Slide 12 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.9 Boron-Nitrogen Compounds
i i Boron Nitride
2 BBr
3
+ 6 NH
3
2 B(NH
2
)
3
2 B(NH)
1.5
(BN)
x
polymeric boron nitride
3 3
(
2
)
3
( )
1.5
( )
x
p y
Technical synthesis
B
2
O
3
+ 2 NH
3
2 BN + 3 H
2
O 800 1200 C in Ca
3
(PO
4
)
2
- matrix B
2
O
3
2 NH
3
2 BN 3 H
2
O 800 1200 C in Ca
3
(PO
4
)
2
matrix
B
2
O
3
+ 3 C + N
2
2 BN + 3 CO 1800 1900 C
Structures Structures
o-BN hexagonal (similar to graphite)
-BN cubic (diamond-like structure)
BN meta stable (wurtzite structure) -BN meta-stable (wurtzite structure)
Properties
l l colourless
no electronic conductor (in contrary to graphite)
thermally extremely stable (T
m
= 3270 C)
Slide 13 Inorganic Chemistry I
Prof. Dr. T. Jstel
high-temperature lubricant, fire-proof coatings/linings
3.9 Boron-Nitrogen Compounds
Borazine
Borazine is sometimes also called inorganic benzene Borazine is sometimes also called inorganic benzene
Synthesis
F dib d NH t 250 300 C From diborane and NH
3
at 250-300 C
3 B
2
H
6
+ 6 NH
3
6 H
3
B-NH
3
6 H
2
B=NH
2
6 HBNH 2 (HBNH)
3
-6 H
2
-6 H
2
trimerisation
(diborane) (borazane) (borazene) (borazine)
Structure Structure
Properties
Polar B-N bond leads to higher reactivity in
comparison to benzene
Ready addition of Br
2
or HCl
Slide 14 Inorganic Chemistry I
Prof. Dr. T. Jstel
eady add t o o
2
o C
3.10 Boron-Oxygen Compounds
A i i O i A i Aluminium Oxide and Aluminates
Synthesis: see production of aluminium y p
Al
2
O
3
-modifications
-Al
2
O
3
forms from Al(OH)
3
at 400 C Al
2
O
3
forms from Al(OH)
3
at 400 C
insoluble in water, soluble in strong acids and bases
catalyst, catalyst substrate, T < 600 C, OH groups
o-Al O forms during tempering of -Al O at T > 1000 C o-Al
2
O
3
forms during tempering of -Al
2
O
3
at T > 1000 C
(corundum) abrasive, polishing agent, fire-resistant material (T
m
= 2055 C)
artificial gemstone (ruby: o-Al
2
O
3
+ 0.2% Cr
2
O
3
at T > 2200 C)
Al O = NaAl O layered structure with good Na
+
ion conductivity -Al
2
O
3
= NaAl
11
O
17
layered structure with good Na
+
-ion conductivity
Alum M
I
M
III
(SO
4
)
2
.
12H
2
O e.g. KAl(SO
4
)
2
.
12H
2
O
Al i M O Al O M Al O (M M Z F C ) i l Aluminates MeO + Al
2
O
3
MeAl
2
O
4
(Me = Mg, Zn, Fe, Co) spinels
MeO + Al
2
O
3
MeAl
2
O
4
(Me = Ca, Sr, Ba)
doping with Eu
2+
and Dy
3+
gives Afterglow phosphor
Slide 15 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.11 Aluminium Hydrides
Alane and Alanates
Alane AlH Alane AlH
3
Synthesis: 3 LiAlH
4
+ AlCl
3
3 LiCl + 4 AlH
3
in ether
Properties: white powder, because it is polymeric ((AlH
3
)
x
), CN 6 AlH
6/2
p p p y
3 x 6/2
highly air and moisture sensitive!
three-center-two-electrons-bonding
Alanates MeAlH
4
Synthesis: AlX + 4 LiH LiAlH + 3 LiX (X = Cl Br) Synthesis: AlX
3
+ 4 LiH LiAlH
4
+ 3 LiX (X = Cl, Br)
Properties: strong reducing agent
strong hydration agent
Slide 16 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.12 Aluminium Halides
The Properties of the Aluminium Halides Are Defined by the Polarisability of the
Anions
Ionic charge density Al
3+
= 370 C/mm
3
strong polarising effect!
AlX T [C] St t AlX
3
T
m
[C] Structure _______
X = F 1290 lattice made of AlF
6
-octahedrons
X = Cl 183 (sublimed) solid: lattice, fluid and gaseous phase: Al
2
Cl
6
-dimers
X = Br 97.5 Al
2
Br
6
-dimers
X = I 190 Al
2
I
6
-dimers
AlF
3
+ x MeF Me[AlF
4
], Me
2
[AlF
5
], Me
3
[AlF
6
] Me = Na cryolite
AlCl
3
+ H
2
O Al(OH)
3
+ 3 HCl
structure of Al
2
X
6
AlCl
3
+ R-Cl R
+
+ [AlCl
4
]
-
R
+
+ Ar-H Ar-R + H
+
Friedel-Crafts-Alkylation
Slide 17 Inorganic Chemistry I
Prof. Dr. T. Jstel
3.13 Gallium and Indium
Gallium and Indium Are Metals With Low Melting Points and High Ductility
Formation of III/V-semi conductors (W = wurtzite, hexagonal ZnS; S = sphalerite, cubic ZnS)
GaN GaP GaAs GaSb InN InP InAs InSb
Structure W S S S W S S S
T
m
[C] >1050 1465 1238 712 >300 1070 942 525
E
G
[eV] 3.7 2.3 1.5 0.7 1.9 1.4 0.4 0.2
E
G
[nm] 370 520 830 1800 660 900 3100 6200
Formation of gallates and indates (analogous to aluminates)
SrO + Me
2
O
3
SrMe
2
O
4
(Me = Ga, In)
SrS + Me S SrMe S (Me Ga In) thiogallate and thioindate SrS + Me
2
S
3
SrMe
2
S
4
(Me = Ga, In) thiogallate and thioindate
SrGa
2
S
4
:Eu (
max
= 525 nm) is a prominent phosphor in electro luminescence displays
Stability of the monovalent oxidation state increases: Stability of the monovalent oxidation state increases:
Formation of I/III-compounds: MeCl
2
= Me
I
[Me
III
Cl
4
] (Me = Ga, In)
Of technical importance is ITO = Indium-Tin-Oxide: SnO
2
:In
3+
for transparent electrodes
Slide 18 Inorganic Chemistry I
Prof. Dr. T. Jstel
Of technical importance is ITO Indium Tin Oxide: SnO
2
:In for transparent electrodes
3.14 Thallium and the Inert-Pair Effect
Tl(III)-Compounds Are Strong Oxidising Agents, while Tl(I)-Compounds Are
Stable
Ionisation- X(g) X
+
(g) + e
-
X
+
(g) X
2+
(g) + e
-
X
2+
(g) X
3+
(g) + e
-
enthalpy
[MJ/mol]
Aluminium 0.58 1.82 2.75
Thallium 0.60 1.98 2.88
Explanation: The 6s-electrons are strongly bound at the nucleus due to the high nucleus
charge
shrinkage of the 6s-orbital stabile s
2
-ions (Tl
+
, Pb
2+
, Bi
3+
)
Chemical Properties
4 Tl + O
2
2 Tl
2
O
Tl
2
O + H
2
O 2 TlOH
2 2
2 TlOH + CO
2
Tl
2
CO
3
+ H
2
O
Tl
+
forms hardly soluble halides: Tl
+
+ X
-
TlX+ (X = Cl, Br, I)
Strong resemblance to lead!
Slide 19 Inorganic Chemistry I
Prof. Dr. T. Jstel
Strong resemblance to lead!
3.15 Biological Aspects
Aluminium
The cation is toxic to humans and animals
5
.
10
-6
mol/l in water suffices to kill fish 5 10 mol/l in water suffices to kill fish
Decrease in pH-value of waters leads to increasing Al
3+
-concentrations
Tea contains a rather high amount of Al
3+
-ions, which can be masked through g g
complexation by the addition of milk or lemon
Acidosis of soils leads to the release of Al
3+
-ions
l t idi il d t th i bilit t th i some plants can grow even on acidic soil, due to their ability to synthesise
citric or malic acid
Thallium
Highly toxic, due to its similarity to K
+
as a big water soluble ion, that can easily
penetrate cells and dist rb en matic processes there penetrate cells and disturb enzymatic processes there
Tl
2
SO
4
is used as rat poison
Tl-salts are popular toxins in Agatha Christies novels
Slide 20 Inorganic Chemistry I
Prof. Dr. T. Jstel
p p g
Overview Boron Chemistry
O i i S 0 Oxidation States: +III, 0, -II, -III
BCl B O B TiB
Mg Ti C/Cl
2
BCl
3
B
2
O
3
B TiB
2
g
OH-
2
[B(OH)
4
]
-
[B
4
O
5
(OH)
4
]
2-
H
3
BO
3
H
+
OH
-
H
+
OH
-
OH
F
-
NaH
H
2
SO
4
/HF
OH
[BF
4
]
-
BF
3
B
2
H
6
F NaH
Slide 21 Inorganic Chemistry I
Prof. Dr. T. Jstel
Overview Aluminium Chemistry
O i i S 0 Oxidation States: +III, 0
AlF
3
Al
2
X
6
F
2
e
-
X
2
with X = Br, Cl, I
F
-
F
2
[AlF
6
]
3-
Al
2
O
3
Al
e
OH
-
H
+
O
2
OH
-
F
-
[Al(OH)
4
]
-
Al(OH)
3
[Al(H
2
O)
6
]
3+
H
+
OH
-
H
+
OH
-
OH
-
OH
-
Slide 22 Inorganic Chemistry I
Prof. Dr. T. Jstel