Structure, properties and uses

of Industrially important
oxides of Boron
Presented By

Deepika Varshney,
Ishmita Kaur
16-Sep-2019
General Classification of Boron Oxides
• Boron oxides are the chemical compounds which primarily has Boron
and oxygen. These are the mostly naturally occurring compounds of
Boron
• Four forms are there based on the B & O ratio
1. Boron monoxide ( BnOn)
2. Di-boron monoxide (B2nOn)
3. Boron Suboxide (BmOn) where m/n>2
4. Boron Trioxide (B2O3)
 Boron Monoxide (BnOn)
• (B2O2)n cage oligomers are constructed from polyhedra by locating their
B–B bonds at edge midpoints and three oxygen atoms at each 3 degree
vertex.
• They contains the tetrahedron cavity of B2nOn, which causes the ring
strain (n>3 rings are stable).
• Boron monoxide dimer, acts as a building block for boroxine based bucky
balls and related cages.
• (B2O2)30-B8O4, (B2O2)36,(B2O2)90 – B10O5cavities
• These are formed in the rocket fuels which
gets solidifies
Di-Boron Monoxide (B2nOn)
• Non flammable.
• Boron is in +1 O.S.
• Very unstable in the monomeric form, B-O-B ; doesn’t exist, but less stable in
polymeric form which is graphite-like, where Boron is bonded with three 3C-
2e− bond and making a sheet like structure.
• Least used for manufacturing and in industries.
• B2O + 2 H2O -> 2 H3BO3
Boron Suboxides (BmOn);m/n>2
• Most superior form of oxide.
• B6O is mostly studied of all boron suboxides. It has Icosahedral B12 cluster, and follows (n+1)
Wade rule- closo structure.
• 6-B atoms creates a very tightly packed compact bond among them, having just 1-O atom
inserted in a small notch.
• It has very short interatomic bond lengths and strongly covalent character.
• Superb resistance, hardness is close to that of Diamond, low mass density, high thermal
conductivity, high chemical inertness, and excellent wear resistance.
• Excellent stability at very high temperature.
• Ideal for the Industrial purposes like wear reduction coating for high speed cutting tools, p-
doped semiconductors.
• Oxygen deficient boron suboxides (B6Ox, x<0.9) have poor crystallinity. Amorphous suboxides
contains vitreous open structured B2O3 glassy domains which reduces the mechanical property.
• Boron trioxides when heating with Boron at very high temperature(>1400°C), gives rise to boron
suboxides.
 Boron Suboxides (B6O)
• Each O makes B–O sigma bonds to three icosahedra.
• It also makes six direct B–B sigma bonds to adjacent icosahedra.
• α=72.0° and β=72.0°
• The boronyl (BO) group mainly behaves as an electron-
withdrawing substituent reducing the binding energy and
resonance energy of the oxides. The boron oxides
conserve some of the properties of the parent boron
clusters such as the planarity and multiple aromaticity.
Boron Trioxides (B2O3)
• It is a white, glassy solid with the formula B2O3. It is almost always found as
the vitreous (amorphous) form; however, it can be crystallized after
extensive annealing (i.e., under prolonged heating) to make compound sturdier
and stronger.
• Odourless, colourless but has a bitter flavour.
• m.p. 450°C & b.p. 2250°C
• Mostly found in the vitreous state as (B2O3)n, monomer is prepared by the
dehydration of boric acid.
• Boron is in +3 O.S.
• Reduces with magnesium to form mossain Boron.
• Reacts with HX to fom BX3.
• Reacts with activated carbon to form boron carbide.
Boron Trioxides (B2O3)-Structure
Boron Trioxides B2O3 -Uses
• Most widely used in the glass industry.
• Borosilicate glass (SiO2-80%, B2O3 -13%, Na2O-4%, Al2O3-4%) is
known for its small coefficient of thermal expansion because of which
it can withstand harsh temperature conditions and can therefore
overcome the stress of sudden changes in temperature.
• Optical fiber, panes of glass, enamel.
• Alkali free LCD glasses.
• Display panels of devices due to its durability, transparency, chemical
resistance and thermal properties.
• Gorilla glass-crack and scratch resistant , toughened and reinforced.
• Bonds with boron nitride which is then used in ceramics.
• Insectiside
Borates based on different types of oxo-boron clusters

The extent to which B3O3 rings

catenate into more complex
structure or hydrolyse into smaller
units such as [B(OH)4]-, depends
on the following parameters
1. Activity of water in thesystem.
2. Stoichiometric ratio of metal
ions to Boron
3. Temperature (TΔS)
 Borax; Na2B4O7.10H2O
• It’s the precursor for all other well known B-O compounds.
• The actual form is Na2[B4O5(OH)4].8H20, having 2 anionic tetra-
coordinated boron atom.
• Used in detergent, enamel and cosmetics
• Fire retardant and mildly alkaline.
• Added in the fertilizers as the micronutrient for plants.
• Forms a glass in metallurgy(purifying agent)-used as flux to
reduce the m.p. of that batch so that less energy is consumed to
carry out the process.
• Timborizing (wood is inserted in hot borax solution to make
protective layer against wood boring insets).
• Substitute for toxic Hg in gold extraction process-Hg poisons the
gold miners.
 Borax; Na2B4O7.10H2O
• Borax bead test-
Na2B4O7 · 10H2O       Na2B4O7 + 10H2O ↑
Na2B4O7        2NaBO2 + B2O3
CuCO3      CuO + CO2↑
Or
CuNO3        CuO + NO2 + 1/2 O2↑
Cu(OH)2         CuO + H2O↑
CuO + B2O3 → Cu(BO2)2
2NaBO2 +2Cu(BO2)2 + C  → CO2 + 2Na2B4O7 + 2Cu  
 Sodium Perborate - NaBO3.nH2O
• Borax when treated with NaOH, gives NaBO3.nH2O where
n=1,4.
• Highly water soluble and is a source of active oxygen.
• Uses:
• Detergent, chlorine free mild bleaches
• Disinfectant
• Teeth brightening gels (H2O2 forms in 0.035%)
• Organic Reactions to oxidize; aldehyde-> acid, Ketone->
ester, nitriles to amides etc.
• Generates in sit per carboxylic acid in benzil benzillic
reactions or epoxideation reaction.
 Orthoboric acid-H3BO3 / (B(OH)3
• It’s the product of hydrolysis of most of the boron compounds.
• Usually made by acidification of aqueous solution of borax.
• It forms the flaky white, transparent crystal in which planar array of BO3 unit
is joined by unsymmetrical H-bonding
• In contrast to O H---H distance of 272 pm, consecutive layers are separated
by 318 pm which gives the pronounced basal cleavage of the waxy, plate like
structure and their low density.
• It’s a very weak acid pka-9.25, which arises due to hydroxyl ion acceptance.
• It is slightly less toxic than the common table salt and soluble in water.
• It is widely used in the medical field as an antiseptic, otherwise it is most
commonly used as insecticide, antiseptic and cleaning agent, preservative,
lubricant, in nuclear power plant, in many manufacturing industries and also
in pyrotechnics. It is also used to cure eye infections.
• Its alkyl or aryl substituted form, called Boronic acids (R-B(OH)2) are used in
Pd catalysed Suzuki coupling reaction. Boronic acid is non toxic, inexpensive,
forms the reversible covalent complexes which makes the good reagent to
carry out trans-metallation reaction.
 Meta boric acid (HBO2)

Meta borates reacts with transition metal complexes and gives somewhat unique color in Bead test
References:
• Wisegeek.com/what-is-boron-oxide.htm
• Chemistry of Elements, N. N. Greenwood, Second Edition, 2010, Elsevier India,
ISBN: 978-8181478061
• The Chemistry of the p-block Elements - Syntheses, Reactions, and Applications,
A. J. Elias, First edition, 2018, Universities Press (India), ISBN: 978-9386235718
• R. B. King et al., Chemical Communication, 2017
• http://dictionary.sensagent.com/Boron%20suboxide/en-en/
• Murat Durandurdu, J.A.Cer.S., 2019
• William A. Goddard III et al., Nature communication,2016
• https://www.brainyresort.com/wp-content/uploads/2016/03/BORAX-BEAD-
TEST.png
• https://courses.lumenlearning.com/chemistryformajorsxmaster/chapter/the-
solid-state-of-matter-2/
Thank you….
• Inequality Symbols: <, >, ≤, ≥