Boron
Boron
Boron
org
Boron
Contents
1 Introduction
2 History and etymology
3 Characteristics
o
3.1 Allotropes
o
3.2 Chemistry of the element
Black - brown.
1 Introduction :
Boron is the chemical element with atomic number 5 and the
chemical symbol B. Boron is a metalloid. Because boron is not
produced by stellarnucleo synthesis, it is a low- abundance element in
both the solar system and the Earth's crust. However, boron is
concentrated on Earth by the water-solubility of its more common
naturally occurring compounds, the borate minerals. These are mined
industrially as evaporate ores , such as borax and kernite .
Chemically uncombined boron is not found naturally on Earth.
Industrially, very pure isolated boron is produced with difficulty, as
boron tends to form refractory materials containing small amounts of
carbon or other elements. Several allotropes of boron exist:
amorphous boron is a brown powder and crystalline boron is black,
extremely hard (about 9.5 on Mohs' scale), and a poor conductor at
room temperature. Elemental boron is used as a dopant in the
semiconductor industry.
The major industrial-scale uses of boron compounds are in
sodium per borate bleaches, and the borax component of fiberglass
insulation. Boron polymers and ceramics play specialized roles as
high-strength lightweight structural and refractory materials. Boron
compounds are used in silica-based glasses and ceramics to give them
resistance to thermal shock. Boron-containing reagents are used for
the synthesis of organic compounds, as intermediate in the synthesis
of fine chemicals. A few boron-containing organic pharmaceuticals
2
Boron , B , 5
metalloid
13, 2, p
11
[He] 2s2 2p1
2, 3
solid
2.08 gcm3
2076 C
3927 C
50.2 kJmol1
480 kJmol1
11.087 Jmol1K1
3, 2, 1 (mildly acidic oxide)
2.04 ( Pauling scale)
1st : 800.6 kJmol1
2nd : 2427.1 kJmol1
3rd : 3659.7 kJmol1
90 pm
84 3 pm
3
192 pm
diamagnetic
(20 C) ~106 m
27.4 Wm1K1
(25 C) ( form) 57 [3]
mm1K1
(20 C) 16,200 ms1
~9.5
iso NA
half-life
DM DE (MeV)
10
10
B 19.9 % *
B is stable with 5 neutrons
11
11
B 80.1 % *
B is stable with 6 neutrons
*Boron -10 content may be as low as 19.1% and as
high as 20.3 % in natural samples. Boron-11 is
the remainder in such cases.
DP
Sassolite
Boron compounds were known thousands of years ago. Borax
was known from the deserts of western Tibet, where it received the
name of tincal, derived from the Sanskrit. Borax glazes were used in
China from AD300, and some tincal even reached the West, where
the Persian alchemist Jbir ibn Hayyn seems to mention it in 700.
4
Marco Polo brought some glazes back to Italy in the 13th century.
Agricola, around 1600, reports the use of borax as a flux in
metallurgy. In 1777, boric acid was recognized in the hot springs
(soffioni) near Florence, Italy, and became known as sal sedativum,
with mainly medical uses. The rare mineral is called sassolite, which
is found at Sasso, Italy. Sasso was the main source of European borax
from 1827 to 1872, at which date American sources replaced it.
Boron compounds were relatively rarely used chemicals until the late
1800s when Francis Marion Smith's Pacific Coast Borax Company
first popularized these compounds and made them in volume and
hence cheap
Boron was not recognized as an element until it was isolated by
Sir Humphry Davy and by Joseph Louis Gay - Lussac and Louis
Jacques Thnard In 1808 Davy observed that electric current sent
through a solution of borates produced a brown precipitate on one of
the electrodes. In his subsequent experiments he used potassium to
reduce boric acid instead of electrolysis. He produced enough boron
to confirm a new element and named the element boracium. GayLussac and The nard use iron to reduce boric acid at high
temperatures. They showed by oxidizing boron with air that boric acid
is a oxidation product of boron . Jns Jakob Berzelius identified boron
as an element in 1824 . Pure boron was arguably first produced by the
American chemist Ezekiel Weintraub in 1909 .
3 Characteristics :
3 1 - Allotropes :
Boron is similar to carbon in its capability to form stable
covalently bonded molecular networks. Even nominally disordered
(amorphous) boron contains regular boron icosahedra which are,
however, bonded randomly to each other without long-range order.
Crystalline boron is a very hard, black material with a high melting
point of above 2000 C. It exists in four major polymorphs: , ,
and T. Whereas , and T phases are based on B12 icosahedra, the phase can be described as a rock salt - type arrangement of the
icosahedra and B2 atomic pairs.[20] It can be produced by compressing
5
Boron phase
Symmetry
Atoms/unit
12
cell
~105
28
Density
(g/cm3)
2.46
2.35
2.52
Vickers
hardness
(GPa)
42
45
5058
Bulk
modulus
(GPa)
185
224
227
Bandgap
(eV)
1.6
2.1
2.36
between the 11B and 10B and traditionally expressed in parts per
thousand, in natural waters ranging from 16 to +59. There are 13
known isotopes of boron, the shortest-lived isotope is 7B which
decays through proton emission and alpha decay. It has a half-life of
3.51022 s. Isotopic fractionation of boron is controlled by the
exchange reactions of the boron species B(OH)3 and [B(OH)4].
Boron isotopes are also fractionated during mineral crystallization,
during H2O phase changes in hydrothermal systems, and during
hydrothermal alteration of rock. The latter effect results in
preferential removal of the 10B(OH)4 ion onto clays. It results in
solutions enriched in 11B(OH)3 and therefore may be responsible for
the large 11B enrichment in seawater relative to both oceanic crust
and continental crust; this difference may act as an isotopic signature.
The exotic 17B exhibits a nuclear halo, i.e. its radius is appreciably
larger than that predicted by the liquid drop model.
The 10B isotope is good at capturing thermal neutrons . Natural
boron is about 20% 10B and 80 % 11B. The nuclear industry enriches
natural boron to nearly pure 10B. The less-valuable by-product,
depleted boron, is nearly pure 11B.
3 3 - 1 - Commercial isotope enrichment
Because of its high neutron cross-section, boron-10 is often used
to control fission in nuclear reactors as a neutron-capturing substance.
Several industrial-scale enrichment processes have been developed,
however only the fractionated vacuum distillation of the di methyl
ether adduct of boron tri fluoride (DME-BF3) and column chromate
graphy of borates are being used.
3 3 - 2 - Enriched boron ( boron -10 )
Enriched boron or 10B is used in both radiation shielding and in
boron neutron capture therapy. In the latter, a compound containing
10
B is attached to a muscle near a tumor. The patient is then treated
with a relatively low dose of thermal neutrons. This causes energetic
and short range alpha radiation from the boron to bombard the tumor.
11
Neutron cross section of boron ( top curve is for 10B and bottom
curve for 11B )
In nuclear reactors , 10B is used for reactivity control and in
emergency shutdown systems. It can serve either function in the form
of borosilicate control rods or as boric acid. In pressurized water
reactors, boric acid is added to the reactor coolant when the plant is
shut down for refueling. It is then slowly filtered out over many
months as fissile material is used up and the fuel becomes less
reactive.
In future manned interplanetary spacecraft, 10B has a theoretical
role as structural material (as boron fibers or BN nano tube material)
which would also serve a special role in the radiation shield. One of
the difficulties in dealing with cosmic rays, which are mostly high
energy protons, is that some secondary radiation from interaction of
cosmic rays and spacecraft materials is high energy spallation
neutrons. Such neutrons can be moderated by materials high in light
elements such as poly ethylene, but the moderated neutrons continue
to be a radiation hazard unless actively absorbed in the shielding.
Among light elements that absorb thermal neutrons, 6Li and 10B
appear as potential spacecraft structural materials which serve both
for mechanical reinforcement and radiation protection .
3 3 - 3 - Depleted boron ( boron -11 )
Cosmic radiation will produce secondary neutrons if it hits
spacecraft structures. Those neutrons will be captured in 10B, if it is
11
Borax crystals
12
14
Diamond
cubicBC2N
cubicBC5
cubicB4C ReB2
BN
Vickers hardness
115
(GPa)
76
71
62
38
Fracture
toughness
m1/2)
4.5
9.5
6.8
3.5
(MPa 5.3
22
18
19
5 9 - Research areas
Magnesium di boride is an important super conducting material
with the transition temperature of 39 K . Mg B2 wires are produced
with the powder-in-tube process and applied in superconducting
magnets.
Amorphous boron is used as a melting point depressant in
nickel - chromium braze alloys .
Hexagonal boron nitride forms atomically thin layers, which
have been used to enhance the electron mobility in graphene devices .
It also forms nano tubular structures ( BNNTs ) , which have with
high strength, high chemical stability, and high thermal conductivity,
among its list of desirable properties .
6 - Biological role :
There is a boron-containing natural antibiotic , boro mycin ,
isolated from streptomyces . Boron is an essential plant nutrient,
required primarily for maintaining the integrity of cell walls.
Conversely, high soil concentrations of > 1.0 ppm can cause marginal
and tip necrosis in leaves as well as poor overall growth performance.
Levels as low as 0.8 ppm can cause these same symptoms to appear in
plants particularly sensitive to boron in the soil. Nearly all plants,
even those somewhat tolerant of boron in the soil, will show at least
some symptoms of boron toxicity when boron content in the soil is
21
greater than 1.8 ppm. When this content exceeds 2.0 ppm, few plants
will perform well and some may not survive. When boron levels in
plant tissue exceed 200 ppm symptoms of boron toxicity are likely to
appear.
As an ultra trace element , boron is necessary for the optimal
health of rats, although it is necessary in such small amounts that ultra
purified foods and dust filtration of air is necessary to induce boron
deficiency, which manifest as poor coat or hair quality. Presumably,
boron is necessary to other mammals. No deficiency syndrome in
humans has been described. Small amounts of boron occur widely in
the diet, and the amounts needed in the diet would, by analogy with
rodent studies, be very small. The exact physiological role of boron in
the animal kingdom is poorly understood.
Boron occurs in all foods produced from plants. Since 1989 its
nutritional value has been argued. It is thought that boron plays
several biochemical roles in animals, including humans . The U.S.
Department of agriculture conducted an experiment in which
postmenopausal women took 3 mg of boron a day. The results
showed that supplemental boron reduced excretion of calcium by
44%, and activated estrogen and vitamin D , suggesting a possible
role in the suppression of osteoporosis. However, whether these
effects were conventionally nutritional, or medicinal, could not be
determined. The US National Institutes of Health quotes this source:
Total daily boron intake in normal human diets ranges from
2.1 4.3 mg boron / day.
6 1 - Analytical quantification :
For determination of boron content in food or materials the
colorimetric curcumin method is used. Boron has to be transferred to
boric acid or borates and on reaction with curcumin in acidic solution,
a red colored boron - chelate complex, rosocyanine, is formed .
21
23
Allotropes of boron
Amorphous boron
Contents
1 Introduction
2 Summary of properties
3 - rhombo hedral boron
4 - rhombo hedral boron
5 - boron
6 Tetragonal boron phases
7 High - pressure super conducting phase
8 Amorphous boron
1 Introduction :
T
Rhombohedral Rhombohedral Orthorhombic Tetragonal
Symmetry
Atoms/unit cell
12
~105
28
192
3
Density (g/cm )
2.46
2.35
2.52
2.36
Vickers hardness (GPa) 42
45
5058
Bulk modulus (GPa) 224
184
227
Bandgap (eV)
2
1.6
2.1
Structure of -boron
Structure of -boron
25
Structure of -boron
3 - - rhombohedral boron :
-rhombohedral boron has a unit cell of twelve boron atoms.
The structure consists of B12 icosahedra in which each boron atom has
five nearest neighbors within the icosahedrons . If the bonding were
the conventional covalent type then each boron would have donated 5
electrons. However, boron has only 3 valence electrons, and it is
thought that the bonding in the B12 icosahedra is achieved by the socalled 3-center electron-deficient bonds where the electron charge is
accumulated at the center of a triangle formed by 3 adjacent atoms.[12]
The isolated B12 icosahedra are not stable; thus boron is not a
molecular solid, but the icosahedra in it are connected by strong
covalent bonds.
4 - - rhombohedral boron
- rhombohedral boron has a sub cell containing 105108
atoms or a unit cell of 320 atoms. Many atoms form B 12
icosahedra, but there are also a large number of non-icosahedral
atoms as well. For long time, it was unclear whether the or phase
is most stable at ambient conditions; however, gradually a consensus
was reached that phase as the thermodynamically stable allotrope.
5 - boron :
28
Boron Ore
Important Boron Ore are :
I . Borane
II . Borax
III . Kernite
I - Borane
Contents :
1 Introduction
2 Generic formula of boranes
3 Naming conventions
4 Cluster types
5 Bonding in boranes
6 Chemistry of boranes
o
6.1 Properties and reactivity trends
o
6.2 Synthesis and general reactivity
7 History
1 Introduction :
Diborane, B2 H6
Decaborane-[14], B10H14
B12H122-
B6H10 is a typical example. Its geometry is, in essence, a 7boron framework (pentagonal bipyramid), missing a vertex that had
the highest number of near neighbors , e.g. , a vertex with 5 neighbors
The extra hydrogen atoms bridge around the open face. A notable
exception to this general scheme is that of B 8H12, which would be
expected to have a nido- geometry ( based on B9H92 missing 1
vertex), but is similar in geometry to B8H14, which is based on
B10H102.
The names for the series of boranes are derived from this
general scheme for the cluster geometries:32
5 - Bonding in boranes :
Boranes are electron - deficient and pose a problem for
conventional descriptions of covalent bonding that involves shared
electron pairs. BH3 is a trigonal planar molecule ( D3h molecular
symmetry ) . Diborane has a hydrogen - bridged structure, see the
diborane article. The description of the bonding in the larger boranes
formulated by William Lipscomb involved:
34
36
II - Borax
IUPAC name :
Sodium tetra borate deca hydrate
Na2B4O7 10 H2O or
Molecular Formula
Na2[B4O5(OH)4] 8H2O
Molar Mass
381 ( deca hydrate)
Appearance
white solid
Density
1.73 g / cm (solid)
Melting point
743 C (anhydrous)
Boiling point
1575 C
1 Introduction
2 Uses
o
2.1 House hold products
o
2.2 Buffer
37
1 Introduction :
Borax, also known as sodium borate, sodium tetra borate, or
disodium tetra borate , is an important boron compound, a mineral,
and a salt of boric acid. It is usually a white powder consisting of soft
colorless crystals that dissolve easily in water.
Borax has a wide variety of uses. It is a component of many
detergents, cosmetics, and enamel glazes. It is also used to make
buffer solutions in biochemistry, as a fire retardant, as an anti-fungal
compound for fiber glass, as an insecticide, as a flux in metallurgy, a
texturing agent in cooking, and as a precursor for other boron
compounds.
The term borax is used for a number of closely related minerals
or chemical compounds that differ in their crystal water content, but
usually refers to the deca hydrate. Commercially sold borax is usually
partially dehydrated.
The word borax is Persian and originates in the Middle-Persian
brak.
Borax first came into common use in the late 19th century when
Francis Marion Smith's Pacific Coast Borax Company began to
market and popularize a large variety of applications under the
famous 20 Mule Team Borax trademark, named for the method by
which borax was originally hauled out of the California and Nevada
deserts in large enough quantities to make it cheap and commonly
available.
38
2 - Uses :
2 1 - House hold products :
Borax is used in various household laundry and cleaning
products, including the "20 Mule Team Borax" laundry booster and
"Boraxo" powdered hand soap. However, despite its name,
"Borateem" laundry bleach no longer contains borax or other boron
compounds.
Borax is also present in some tooth bleaching formulas.
2 2 - Buffer
Sodium borate is used in biochemical and chemical laboratories
to make buffers, e.g. for gel electrophoresis of DNA, such as TBE or
the newer SB buffer or BBS (borate buffered saline) in coating
procedures. Borate buffers (usually at pH 8) are also used as
preferential equilibration solution in DMP-based crosslinking
reactions.
2 3 Co - complexing
Borax as a source of borate has been used to take advantage of
the co - complexing ability of borate with other agents in water to
form complex ions with various substances. Borate and a suitable
polymer bed are used to chromatograph non - glycosylated
hemoglobin differentially from glycosylated hemoglobin (chiefly
HbA1c), which is an indicator of long term hyperglycemia in diabetes
mellitus. Borate and a proprietary synthetic amino acid, Deselex
(from Henkel) have been used to complex water "hardness" cations to
make a non - precipitating water "softener". Borate alone does not
have a high affinity for "hardness" cations, although it has been used
for that purpose.
2 4 Flux :
A mixture of borax and ammonium chloride is used as a flux
when welding iron and steel. It lowers the melting point of the
unwanted iron oxide (scale), allowing it to run off. Borax is also used
39
41
3 - Natural sources :
Borax occurs naturally in evaporite deposits produced by the
repeated evaporation of seasonal lakes. The most commercially
important deposits are found in Turkey; Boron, California; and
Searles Lake, California. Also, it has been found at many other
locations in the Southwestern United States, the Atacama desert in
Chile, and in Tibet and Romania. Borax can also be produced
synthetically from other boron compounds. Naturally occurring
Borax, (known by the trade name Rasorite - 46 in USA and many
other countries) is refined by a process of re-crystallization .
4 Toxicity :
Borax , sodium tetra borate deca hydrate , is not acutely toxic.
Its LD50 (median lethal dose) score is tested at 2.66 g / kg in rats: a
significant dose of the chemical is needed to cause severe symptoms
or death. The lethal dose is not necessarily the same for humans.
Sufficient exposure to borax dust can cause respiratory and skin
irritation. Ingestion may cause gastrointestinal distress including
nausea, persistent vomiting, abdominal pain, and diarrhea. Effects on
the vascular system and brain include headaches and lethargy, but are
less frequent. "In severe poisonings, a beefy red skin rash affecting
palms, soles, buttocks and scrotum has been described. With severe
poisoning, erythematous and exfoliative rash, unconsciousness,
respiratory depression, and renal failure " .
A reassessment of boric acid/borax by the United States
Environmental Protection Agency Office of Pesticide Programs found
potential developmental toxicity (especially effects on the testes).[21]
Boric acid solutions used as an eye wash or on abraded skin are
known to be particularly toxic to infants, especially after repeated use,
because of the slow elimination rate . At a recent European
Diagnostics Manufacturing Association (EDMA) meeting, several
new additions to the Substance of Very High Concern (SVHC)
candidate list in relation to the Registration, Evaluation, Authorization
and restriction of Chemicals Regulations 2007 (REACH) were
discussed. The registration and review completed as part of REACH
42
III - Kernite
Category
Chemical formula
Molar mass
Color
Crystal habit
Crystal system
Mohs scale hardness
Luster
Streak
Specific gravity
Optical properties
Refractive index
Birefringence
Other characteristics
Inoborates
Na2B4O6(OH)2 3(H2O)
290
Colorless , white
Crystalline - Coarse - Occurs as well formed coarse sized crystals
Monoclinic,
2.5 - 3
Vitreous - Pearly
white
1.9 - 1.92, Average = 1.91
Biaxial (-), 2V=80
n = 1.454,
n = 1.472,
n = 1.488
=0.0340
Non - radioactive, non-fluorescent ,
non - magnetic
Boric acid
Contents
1 Introduction
2 Occurrence
3 Preparation
4 Properties
5 Crystal structure
6 Toxicology
7 Uses
o
7.1 Medicinal
o
7.2 Laboratory
o
7.3 Insecticidal
o
7.4 Preservation
o
7.5 Lubrication
o
7.6 Nuclear power
o
7.7 Industrial
o
7.8 Pyrotechnics
1 Introduction :
Non - flammable.
2660 mg / kg, oral ( rat )
Phase behaviour
Thermodynamic data
Solid , liquid , gas
Spectral data
UV , IR , NMR , MS
2 - Occurrence :
The free acid is found native in certain volcanic districts such as
Tuscany, the Lipari Islands and Nevada, issuing mixed with steam
from fissures in the ground; it is also found as a constituent of many
minerals ( borax , boracites , boronatrocaicite and colemanite ) . The
47
presence of boric acid and its salts has been noted in seawater. It also
exists in plants and especially in almost all fruits.
Boric acid was first prepared by Wilhelm Homberg (1652
1715) from borax, by the action of mineral acids, and was given the
name sal sedativum Hombergi ("sedative salt of Homberg"). However
Borates, including boric acid, have been used since the time of the
Greeks for cleaning, preserving food, and other activities .
3 - Preparation :
Boric acid may be prepared by reacting borax (sodium tetra
borate deca hydrate) with a mineral acid, such as hydrochloric acid :
Na2B4O7 10H2O + 2 HCl
4 B(OH)3 [or H3BO3] + 2 NaCl + 5 H2O
4 - Properties
Boric acid is soluble in boiling water. When heated above 170
C, it dehydrates, forming meta boric acid (HBO2):
H3BO3 HBO2 + H2O
Meta boric acid is a white, cubic crystalline solid and is only
slightly soluble in water. Meta boric acid melts at about 236 C, and
when heated above about 300 C further dehydrates, forming tetra
boric acid or pyro boric acid (H2B4O7) :
4 HBO2 H2B4O7 + H2O
The term boric acid may sometimes refer to any of these
compounds. Further heating leads to boron trioxide.
H2B4O7 2 B2O3 + H2O
Boric acid does not dissociate in aqueous solution as a Brn sted
acid , but is a Lewis acid which interacts with water molecules to
48
B (OH)3 + H2O
B4O 2 7 + 9 H2O
51
7 2 Laboratory :
Tris borate - EDTA (TBE buffer) is widely used for the
electro phoresis of nucleic acids and has a higher buffer capacity than
a Tris acetate - EDTA TAE buffer . It can be used for DNA and
RNA poly acryl amide and agarose gel electro phoresis. Is used as a
reagent and precursor of other substances, e.g. tetra acetyl di borate.
7 3 Insecticidal
Boric acid was first registered in the US as an insecticide in
1948 for control of cockroaches , termites , fire ants , fleas ,
silverfish, and many other insects. The product is generally
considered to be safe to use in household kitchens to control
cockroaches and ants . It acts as a stomach poison affecting the
insects' metabolism, and the dry powder is abrasive to the insects'
exoskeleton .
Boric acid is also made into a paste or gel form as a
powerful and effective insecticide much safer to humans than many
other insecticides. The paste or gel has attractants in it to attract
insects. The boric acid slowly causes dehydration ,
7 4 Preservation
In combination with its use as an insecticide, boric acid also
prevents and destroys existing wet and dry rot in timbers. It can be
used in combination with an ethylene glycol carrier to treat external
wood against fungal and insect attack. It is possible to buy borate impregnated rods for insertion into wood via drill holes where
dampness and moisture is known to collect and sit. It is available in a
gel form and inject able paste form for treating rot affected wood
without the need to replace the timber. Concentrates of borate-based
treatments can be used to prevent slime, mycelium and algae growth,
even in marine environments.
Boric acid is added to salt in the curing of cattle hides,
calfskins and sheep skins . This helps to control bacteria development
and helps to control insects.
51
7 5 Lubrication
Colloidal suspensions of nano particles of boric acid
dissolved in petroleum or vegetable oil can form a remarkable
lubricant on ceramic or metal surfaces with a coefficient of sliding
friction that decreases with increasing pressure to a value ranging
from 0.10 to 0.02. Self - lubricating H3BO3 films result from a
spontaneous chemical reaction between water molecules and B2O3
coatings in a humid environment. In bulk-scale, an inverse
relationship exists between friction coefficient and Hertzian contact
pressure induced by applied load.
Boric acid is used to lubricate carrom and novuss boards,
allowing for faster play.
7 6 Nuclear power :
Boric acid is used in nuclear power plants as a neutron poison
to slow down the rate at which fission is occurring. Fission chain
reactions are generally driven by the amount of neutrons present (as
products from previous fissions). Natural boron is 20 % boron-10 and
about 80% boron-11. Boron-10 has a high cross-section for
absorption of low energy (thermal) neutrons. By adding more boric
acid to the reactor coolant which circulates through the reactor, the
probability that a neutron can survive to cause fission is reduced.
Therefore, changes in boric acid concentration effectively regulate the
rate of fission taking place in the reactor. This method is only used in
pressurized water reactors (PWRs). Boron is also dissolved into the
spent fuel pools containing used uranium rods. The concentration is
high enough to keep neutron multiplication at a minimum.
7 7 Industrial :
The primary industrial use of boric acid is in the manufacture of
mono filament fiber glass usually referred to as textile fiber glass .
Textile fiber glass is used to reinforce plastics in applications that
range from boats, to industrial piping to computer circuit boards.
52
Boron Arsenide
1 Introduction :
Boron arsenide is a chemical compound of boron and arsenic.
It is a cubic (sphalerite) semiconductor with a lattice constant of
0.4777 nm and an indirect band gap of roughly 1.5 eV. It can be
alloyed with gallium arsenide.
Boron arsenide also occurs as an icosahedral boride , B12As2. It
belongs to R-3m space group with a rhombohedral structure based on
clusters of boron atoms and two - atom As - As chains. It's a wide
band gap semiconductor ( 3.47 eV ) with the extraordinary ability to
self-heal radiation damage . This form can be grown on substrates
such as silicon carbide.
Molecular Formula
Molar Mass
Density
Melting point
Solubility in water
Band gap
Hazards
EU classification
B As or B12 As 2
86 g / mol
5.22 g / cm3, solid
2027 C
Insoluble
1.50 eV ( B As ) ;
3.47 eV ( B12 As2 )
N/A
2 - Applications :
Solar cells can be fabricated from boron arsenide. It's also an
attractive choice for devices exposed to radiation which can severely
degrade the electrical properties of conventional semiconductors,
causing devices to cease functioning. Among the particularly
intriguing possible applications for B12 As2 are beta cells, devices
capable of producing electrical energy by coupling a radioactive beta
emitter to a semiconductor junction, another space electronics.
54
Boron Carbide
Contents :
1 Introduction
2 Crystal structure
3 Properties
4 Preparation
5 Uses
1 Introduction :
2 - Crystal structure :
Boron carbide has a complex crystal structure typical of
icosahedron - based borides. There, B12 icosahedra form a
rhombohedral lattice unit (space group: R3m (No. 166), lattice
constants: a = 0.56 nm and c = 1.212 nm) surrounding a C - B - C
chain that resides at the center of the unit cell, and both carbon atoms
bridge the neighboring three icosahedra. This structure is layered: the
B12 icosahedra and bridging carbons form a network plane that
spreads parallel to the c-plane and stacks along the c-axis. The lattice
has two basic structure units the B12 icosahedron and the B6
octahedron. Because of the small size of the B6 octahedra , they
56
Padlocks
Personal and vehicle anti - ballistic armor plating.
Grit blasting nozzles.
High - pressure water jet cutter nozzles.
Scratch and wear resistant coatings.
Cutting tools and dies.
57
Abrasives.
Neutron absorber in nuclear reactors.
Metal matrix composites.
High energy fuel for solid fuel Ramjets.
58
1 Introduction
2 Structure
3 Preparation
4 Reactions
5 Ligand
1 Introduction :
4 - Reactions
BF can react with itself to form polymers of boron containing
fluorine with between 10 and 14 boron atoms. BF reacts with BF3 to
form B2F4. BF and B2 F4 further combine to form B3F5. B3F5 is
unstable above -50 and forms B8F12. This substance is a yellow oil.
BF reacts with acetylenes to make the 1,4-diboracyclohexadiene
ring system. BF can condense with 2-butyne forming 1,4- di fluoro 2,3,5,6 - tetra methyl -1,4- di bora cyclo hexadiene. Also it reacts with
acetylene to make 1,4- di fluoro -1,4- di bora cyclo hexadiene.
5 Ligand :
The first case of BF being a ligand on a transition element was
demonstrated in 2009 with the compound (C5H5)2 Ru2 (CO)4 (-BF).
The BF was bound to both ruthenium atoms as a bridge . Vidovic and
Aldridge reacted Na Ru (CO)2(C5H5) with (Et2O):BF3 . Note that the
BF was formed in place rather than added on.
Earlier in 1968 K. Kmpfer , H. Nth , W. Petz , and G. Schmid
claimed that Fe (BF) (CO)4 was formed in the reaction of B2F4 with
Fe(CO)5 , however this has not been reproduced .
61
Boron Nitrate
- Introduction :
Boron nitrate is a boron compound with the formula B (NO3)3.
Like graphene , boron nitrate is a two - dimensional material.
61
Boron Nitride
Contents
1 Introduction
2 Structure
3 Properties
o
3.1 Physical
o
3.2 Thermal stability
o
3.3 Chemical stability
o
3.4 Thermal conductivity
4 Synthesis
o
4.1 Preparation and reactivity of hexagonal BN
o
4.2 Intercalation of hexagonal BN
o
4.3 Preparation of cubic BN
o
4.4 Preparation of wurtzite BN
o
4.5 Production statistics
5 Applications
o
5.1 Hexagonal BN
o
5.2 Cubic boron nitride
o
5.3 Amorphous boron nitride
6 Other BN forms
o
6.1 Boron nitride fibers
o
6.2 Boron nitride nano mesh
o
6.3 Boron nitride nano tubes
o
6.4 Composites containing BN
7 Health issues
1 Introduction :
BN
25 g mol1
Colorless crystals
2.1 (hBN) g cm3 ;
3.45 (cBN) g cm3
2973 C ( sublimes (cBN))
200 cm2/(Vs) (cBN)
1.8 (hBN); 2.1 (cBN)
hexagonal , sphalerite , wurtzite
63
-BN, hexagonal
64
3 Properties :
3 1 Physical :
Properties of amorphous and crystalline BN, graphite and diamond.
Some properties of h-BN and graphite differ within the basal planes
() and perpendicular to them ()
Material
Density (g/cm3)
a-BN
2.28
Mohs hardness
h-BN
~2.1
3.45
3.49
~2.1
3.515
12
~10
~10
12
10
45
34
400
400
Knoop hardness
(GPa)
10
Bulk modulus
(GPa)
100
36.5
Thermal
conductivity
(W/cm K)
0.03
6; 0.3
7.4
Thermal expansion
(106/C)
34
440
220;
620
0.020.8
2.7;
38
1.2
2.7
1.5;
25
0.8
5.5
Bandgap (eV)
5.05
5.2
6.4
4.5
5.5
Refractive index
1.7
1.8
2.1
2.05
Magnetic
susceptibility
(emu/g)
100
0.48;
-17.3
2.4
0.2..2.7; 20..-28
1.6
Ambient
Action
Threshold T (C)
Mo
102 Pa vacuum
reaction
1360
Ni
102 Pa vacuum
wetting
1360
66
Fe, Ni, Co
argon
react
Al
102 Pa vacuum
wetting and
1050
reaction
Si
103 Pa vacuum
wetting
1500
no wetting
1100
no wetting
2200
Al2O3 + B2O3
102 Pa vacuum
14001500
no reaction 1360
3 3 - Chemical stability :
Boron nitride is insoluble in usual acids, but is soluble in
alkaline molten salts and nitrides, such as Li OH , K OH, Na OH ,
Na2CO3, NaNO3, Li3N, Mg3N2, Sr3N2, Ba3N2 or Li3BN2, which are
therefore used to etch BN.
3 4 - Thermal conductivity :
The theoretical thermal conductivity of hexagonal Boron nitride
nano ribbons (BNNRs) can approach 17002000 W/(mK), which has
the same order of magnitude as the experimental measured value for
graphene , and can be comparable to the theoretical calculations for
graphene nano ribbons . Moreover, the thermal transport in the
BNNRs is anisotropic. The thermal conductivity of zigzag - edged
67
Ceramic BN crucible
Hexagonal BN was first used in cosmetics around 1940 in
Japan. However, because of its high price, h-BN was soon abandoned
for this application. Its use was revitalized in the late 1990s with the
optimization h-BN production processes, and currently h-BN is used
by nearly all leading producers of cosmetic products for foundations,
make-up, eye shadows, blushers, kohl pencils, lipsticks and other
skincare products.[11]
Because of its excellent thermal and chemical stability, boron
nitride ceramics are traditionally used as parts of high-temperature
equipment. h-BN can be included in ceramics, alloys, resins, plastics,
rubbers, and other materials, giving them self-lubricating properties.
Such materials are suitable for construction of e.g. bearings and in
steelmaking.[11] Plastics filled with BN have less thermal expansion as
well as higher thermal conductivity and electrical resistivity. Due to
its excellent dielectric and thermal properties, BN is used in
electronics e.g. as a substrate for semiconductors, microwavetransparent windows, and as a structural material for seals.
Hexagonal BN is used in xerographic process and laser printers
as a charge leakage barrier layer of the photo drum . In the automotive
industry, h-BN mixed with a binder (boron oxide) is used for sealing
oxygen sensors, which provide feedback for adjusting fuel flow. The
71
75
Boron Oxide
Boron oxide may refer to :
I . Boron Monoxide
Boron monoxide (B2O) is a chemical compound of boron and
oxygen. Two experimental studies have proposed existence of
diamond - like and graphite - like B2O, as for boron nitride and
carbon solids. How ever , a later , systematic , experimental study of
boron oxide phase diagram suggests that B2O is unstable . The
instability of the graphite - like B2O phase was also predicted
theoretically.
IUPAC name : Boron (I) oxide
Other names : Di- boron monoxide
Molecular Formula
B2 O
Molar mass
38 g / mol
76
Boron trioxide
Contents
1 Introduction
2 Preparation
3 Hardness
4 Applications
1 Introduction :
Melting Point
Boiling Point
Solubility in water
Solubility
Acidity (pKa)
LD50
Thermodynamic
data
Spectral data
450 C (trigonal)
510 C (tetrahedral)
1860 C, sublimates at 1500 C
22 g / L
partially soluble in methanol
~4
3150 mg/kg (oral, rat)
Phase behaviour
Solid, liquid, gas
UV, IR, NMR, MS
2 - Preparation :
Boron trioxide is produced by treating borax with sulfuric acid
in a fusion furnace. At temperatures above 750 C, the molten boron
oxide layer separates out from sodium sulfate. It is then decanted,
cooled and obtained in 96 97 % purity.
Another method is heating boric acid above ~300 C. Boric acid
will initially decompose into water steam and meta boric acid (HBO2)
at around 170 C, and further heating above 300 C will produce
more steam and boron trioxide. The reactions are :
H3BO3 HBO2 + H2O
2 HBO2 B2O3 + H2O
Boric acid goes to anhydrous microcrystalline B2O3 in a heated
fluidized bed. Carefully controlled heating rate avoids gumming as
water evolves. Molten boron oxide attacks silicates. Internally
graphitized tubes via acetylene thermal decomposition are passivated .
Crystallization of molten - B2 O3 at ambient pressure is
strongly kinetically disfavored (compare liquid and crystal densities).
Threshold conditions for crystallization of the amorphous solid are 10
k bar and ~ 200 C .
79
3 - Hardness :
The bulk modulus of - B2 O3 is rather high ( K = 180 GPa ) .
The Vickers hardness of g- B2 O3 is 1.5 GPa and of -B2O3 is 16 GPa.
4 - Applications
Fluxing agent for glass and enamels
Starting material for synthesizing other boron
compounds such as boron carbide
An additive used in glass fibers (optical fibres)
It is used in the production of borosilicate glass
The inert capping layer in the LEC process for the
production of gallium arsenide single crystal
As an acid catalyst in organic synthesis
81
Boron Phosphide
Contents
1 Introduction
2 History
3 Appearance
4 Chemical properties
5 Physical properties [4]
1 Introduction :
BP
42 g / mol
maroon powder
2.90 g / cm3
1100 C ( decomposes )
2 eV ( indirect )
5400 cm2/(V*s) (300 K)
4 W/(cm*K) (300 K)
3.05 (0.63 m)
Zinc Blende
Tetrahedral
2 History :
Crystals of boron phosphide have been synthesized by Henri
Moissan as early as in 1891 .
3 - Appearance
Pure BP is almost transparent, n-type crystals are orange-red
whereas p-type ones are dark red [4].
81
4 - Chemical properties :
BP is not attacked by acids or boiling aqueous alkali water
solutions. It is only attacked by molten alkalis .
5 - Physical properties :
coefficient of thermal expansion ~3x106 /K
heat capacity CP ~ 0.8 J/(g*K) (300 K)
Debye temperature = 1000 K
relatively high micro hardness of 32 GPa (100 g load).
2
electron and hole mobilities of few hundred cm / (V*s)
(up to 500)
82
Boron sulfide
1 Introduction :
Boron sulfide is the chemical compound with the formula B2S3.
This polymeric material that has been of interest as a component of
high-tech glasses and as a reagent for preparing organo sulfur
compounds. Like the sulfides of silicon and phosphorus, B 2S3 reacts
with water, including atmospheric moisture to release H2S. Thus,
samples must be handled under anhydrous conditions.
Like the boron oxides, B2S3 readily forms glasses when blended
with other sulfides such as P4S10. Such glasses absorb lower
frequencies of Infra-red energy relative to conventional borosilicate
glasses.
B2S3 converts ketones into the corresponding thiones. For
example, the conversion of benzophenone to its thione proceeds as
follows:
B2S3 + 3 (C6H5)2C= O B2O3 + 3 (C6H5)2C= S
In practice, B2S3 would be used in excess.
IUPAC Name : Boron sulfide
Other Names : Boron tri sulfide
Molecular Formula B2S3
Molar Mass
118 g / mol
Appearance
colorless crystals
Density
1.55 g / cm3, solid
Melting point
563 C
Boiling point
decomposes at high T
Solubility in water
decomposes
Crystal structure
monoclinic
83
2 Synthesis :
Besides other methods the boron sulfide can be obtained by
the reaction of iron or manganese boride with hydrogen sulfide at
temperatures of 300C.
2 Fe B + 4 H2S B2S3 + Fe S + 4 H2
The first synthesis was done by Jns Jakob Berzelius in 1824
by direct reaction of amorphous boron with sulfur vapor.
2 B + 3 S B 2S 3
Another synthesis was favoured by Friedrich Whler and Henri
Etienne Sainte-Claire Deville first published in 1858, starting from
boron and hydrogen sulfide.
2 B + 3 H2S B2S3 + 3 H2
84
1 Introduction
2 Chemical properties
3 Synthesis
4 History
5 Applications
1 Introduction :
DANGER
-18 C
85
2 - Chemical properties :
Boron tri bromide is commercially available and is a strong
Lewis acid. It is an excellent demethylating or dealkylating agent for
ethers, often in the production of pharmaceuticals. Additionally, it
also finds applications in olefin polymerization and in Friedel - Crafts
chemistry as a Lewis acid catalyst. The electronics industry uses
boron tri bromide as a boron source in pre - deposition processes for
doping in the manufacture of semi conductors.
3 - Synthesis :
The reaction of boron carbide with bromine at temperatures
above 300 C leads to the formation of boron tri bromide. The product
can be purified by vacuum distillation.
4 History :
The first synthesis was done by M. Poggiale in 1846 by reacting
boron trioxide with carbon and bromine at high temperatures :
B2O3 + 3 C + 3 Br2 2 BBr3 + 3 CO
An improvement of this method was developed by F. Whler
and Deville in 1857. By starting from amorphous boron the
reaction temperatures are lower and no carbon monoxide is
produced :
2 B + 3 Br2 2 BBr3
5 - Applications :
Pharmaceutical Manufacturing
Image Processing
Semiconductor Doping
Semiconductor Plasma Etching
Photovoltaic Manufacturing
Reagent for Various Chemical Processes.
86
Contents
1 Introduction
2 Production and properties
3 Uses
4 Safety
1 Introduction :
BCl3. It has been used in the field of high energy fuels and rocket
propellants as a source of boron to raise BTU value. BCl3 is also used
in plasma etching in semiconductor manufacturing. This gas etches
metal oxides by formation of a volatile B O Cl x compounds.
B Cl3 is used as a reagent in the synthesis of organic
compounds. Like the corresponding bromide, it cleaves C-O bonds in
ethers.
4 - Safety
BCl3 is an aggressive reagent that releases hydrogen chloride
upon exposure to moisture or alcohols. The dimethyl sulfide adduct
is safer to use, when possible.
89
Contents
1 Introduction
2 Structure and bonding
3 Synthesis and handling
4 Reactions
o
4.1 Comparative Lewis acidity
o
4.2 Hydrolysis
5 Uses
6 Discovery
1 Introduction :
B F3
68 g / mol (anhydrous)
104 g / mol (dihydrate)
colorless gas (anhydrous)
colorless liquid (dihydrate)
0.00276 g /cm3 ( anhydrous gas)
1.64 g/cm3 (dihydrate)
126.8 C
100.3 C
very soluble
soluble in benzene, toluene,
hexane, chloroform and
91
methylene chloride
Hazards
GHS pictograms
GHS signal word
EU classification
Flash point
Template:GHS04
DANGER
Very toxic (T+)
Corrosive (C)
non-flammable
4 2 Hydrolysis :
Boron tri fluoride reacts with water to give boric acid and fluoro
boric acid. The reaction commences with the formation of the aquo
93
adduct, H2O-BF3, which then loses HF that gives fluoboric acid with
boron tri fluoride.
4 BF3 + 3 H2O 3 HBF4 + "B(OH)3"
The heavier tri halides do not undergo analogous reactions,
possibly the lower stability of the tetrahedral ions BX4- (X = Cl, Br).
Because of the high acidity of fluoro boric acid, the fluoro borate ion
can be used to isolate particularly electrophilic cations, such as
diazonium ions, that are otherwise difficult to isolate as solids.
5 Uses :
Boron tri fluoride is most importantly used as a reagent in
organic chemistry, typically as a Lewis acid. Examples :
initiates polymerisation reactions of unsaturated
compounds such as poly ethers
Other uses:
applied as dopant in ion implantation
in fumigation
to prepare diborane
6 Discovery :
Boron tri fluoride was discovered in 1808 by Joseph Louis GayLussac and Louis Jacques Thnard, who were trying to isolate "fluoric
acid" (i.e. hydro fluoric acid) by combining calcium fluoride with
vitrified boric acid; the resulting vapours failed to etch glass, so they
named it fluoboric gas.
94
B I3
391.5 g / mol
crystalline solid
3.35 g / cm3 (50 C)
49.9 C
210 C,
insoluble
-18 C
95
Boronic Acid
1 Introduction
2 Boronic acids
o
2.1 Synthesis
3 Boronate esters
4 Boronic acids in organic chemistry
o
4.1 Suzuki coupling reaction
o
4.2 Chan-Lam coupling
o
4.3 Liebeskind - Srogl coupling
o
4.4 Conjugate addition
o
4.5 Oxidation
o
4.6 Homologization
o
4.7 Electrophilic allyl shifts
o
4.8 Hydrolysis
o
4.9 C- H coupling reactions
5 Boronic acids in supramolecular chemistry
o
5.1 Saccharide recognition
6 Boronic acids and esters
7 Borate salts
1 Introduction :
Molar
mass
Melting
point C
Phenyl
122
216219
Thiophene
128
138140
97
60
9194
86
6570
Trans
boronic acid
86
123127
Propenyl
Methyl
propene
2 - 1 Synthesis :
Boronic acids can be obtained via several methods. The most
common way is reaction of organo metallic compounds based on
lithium or magnesium ( Grignards ) with borate esters. For example
phenyl boronic acid is produced from phenyl magnesium bromide and
tri methyl borate followed by hydrolysis .
Ph Mg Br + B (OMe)3 PhB (OMe)2 + Me O Mg Br
Ph B (OMe)2 + H2O Ph B (OH)2 + Me OH
Another method is reaction of an arylsilane (RSiR3) with boron
tri bromide (BBr3) in a trans metallation to RBBr2 followed by acidic
hydrolysis.
A third method is by palladium catalyzed reaction of aryl
halides and tri flates with di boronyl esters in a coupling reaction. An
alternative to esters in this method is the use of di boronic acid or
tetra hydroxy di boron ([B(OH2)]2).
3 - Boronate esters
Boronate esters are esters formed between a boronic acid
and an alcohol.
98
Compound
General formula
Boronic acid
RB(OH)2
General structure
168
50 53
(5 mmHg)
Phenyl boronic
tri
acid tri methylene methylene
glycol ester
glycol
162
106
(2 mmHg)
Di iso propoxy
methyl borane
144
105 -107
iso
propanol
4 - 5 - Oxidation
Boronic esters are oxidized to the corresponding alcohols with
base and hydrogen peroxide ( for an example see: carbenoid )
4 - 6 - Homologization
In boronic ester homologization an alkyl group shifts from
boron in a boronate to carbon :
111
Homologization application
In this reaction dichloro methyl lithium converts the boronic
ester into a boronate. A lewis acid then induces a rearrangement of the
alkyl group with displacement of the chlorine group. Finally an
organo metallic reagent such as a Grignard reagent displaces the
second chlorine atom effectively leading to insertion of an RCH2
group into the C- B bond . Another reaction featuring a boronate alkyl
migration is the Petasis reaction.
4 7 - Electrophilic allyl shifts
Allyl boronic esters engage in electrophilic allyl shifts very
much like silicon pendant in the Sakurai reaction. In one study a
diallylation reagent combines both :
112
4 8 - Hydrolysis
Hydrolysis of boronic esters back to the boronic acid and the
alcohol can be accomplished in certain systems with thionyl chloride
and pyridine. Aryl Boronic acids or esters may be hydrolyzed to the
corresponding phenols by reaction with hydroxylamine at room
temperature.
48-
C - H coupling reactions
113
114
general formula
borinic acid
R2BOH
borinate ester
R2BOR
general structure
7 - Borate salts :
Borate salts are ate complexes and have the general structure
R4B M+ for example potassium tetra phenyl borate ( IUPAC name:
potassium tetra phenyl boranuide ) .
-
115
116
1 Introduction
2 History
3 Manufacturing process
4 Physical characteristics
5 Usage
6 Boro silicate nano particles
7 In lamp working
1 Introduction :
118
4 - Physical characteristics :
Borosilicate glass has a very low thermal expansion coefficient
( 3.3 x 10-6/K ) , about one-third that of ordinary glass. This reduces
material stresses caused by temperature gradients which makes
borosilicate the most suitable kind of glass for certain applications
(see below).
The softening point ( temperature at which viscosity is
approximately 107.6 poise ) of type 7740 Pyrex is 820 C .
Boro silicate glass is less dense than ordinary glass.
While more resistant to thermal shock than other types of glass,
borosilicate glass can still crack or shatter when subject to rapid or
uneven temperature variations. When broken, borosilicate glass tends
to crack into large pieces rather than shattering (it will snap rather
than splinter).
Optically, boro silicate glasses are crown glasses with low
dispersion (Abbe numbers around 65) and relatively low refractive
indices (1.511.54 across the visible range).
5 - Usage :
Virtually all modern laboratory glassware is borosilicate glass. It
is so widely used in this application due to its chemical and thermal
resistance and good optical clarity, but the glass can be reacted with
sodium hydride to produce sodium boro hydride , a common
laboratory reducing agent. Fused quartz is also found in some
laboratory equipment when its higher melting point and transmission
of UV are required (e.g. for tube furnace liners and UV cavettos ) ,
but the cost and difficulty of working with quartz make it excessive
for the majority of laboratory equipment.
During the mid-twentieth century, borosilicate glass tubing was
used to pipe coolants (often distilled water) through high power
vacuum tube based electronic equipment, such as commercial
broadcast transmitters.
119
113
Pyrex
A Pyrex flask.
Contents
1 Introduction
2 History of the Pyrex Brand
3 Design
4 Composition
5 Use in laboratory ware
6 Problems With Pyrex
7 Usage in telescopes
1 Introduction :
Pyrex measuring cup, manufactured and sold in the U.S. (circa 1980)
features graduations in both metric and U.S. Customary systems.
Borosilicate glass was first made by the German chemist and
glass technologist Otto Schott, founder of Schott AG in 1893, 22
years before Corning produced the Pyrex brand. Schott AG sold the
product under the name "Duran." In the English-speaking world,
however, in the midst of World War I, Corning's Pyrex brand of
borosilicate glass offered a non-German alternative. Ever since, the
115
4 Composition :
Older Pyrex (pre 1900s), European Pyrex, and Pyrex laboratory
glass ware, is made of borosilicate glass. According to the National
Institute of Standards and Technology, borosilicate Pyrex is
composed of (as percentage of weight) : 14 % boron, 51 % oxygen,
. 3 % sodium, 1 % aluminium, 38 % silicon, and less than 1 %
potassium.
According to glass supplier Pulles and Hannique, borosilicate
Pyrex is made of Corning 7740 glass, and is equivalent in formulation
to Schott Glass 8830 glass sold under the "Duran" brand name. The
composition of both Corning 7740 and Schott 8830 is given as 80.6%
SiO2, 12.6 % B2O3 , 4.2 % Na2O , 2.2 % Al2O3 , 0.04 % Fe2O3, 0.1 %
CaO, 0.05 % MgO , and 0.1 % Cl.
How ever, the Pyrex glass cookware made in Charleroi,
Pennsylvania is made of tempered soda-lime glass.[13]
118
Contents
1 Introduction
2 Preparation and chemistry
3 Structure
4 Uses
1 Introduction :
119