DIBORANE

DIBORANE
Diborane (B2H6) is a compound of boron and hydrogen. It is a colorless, very toxic gas with an unpleasant, rather pungent smell, somewhat resembling much diluted sewer gas or household fuel gas. It is extremely flammable, burning with a bright green flame when ignited (the pure gas may ignite spontaneously), the flame color characteristic of boron, forming boron trioxide (B2O3) and water vapor. In poor supply of air, the flame tends to be blue and some boron is formed. . Synonyms include boroethane, boron hydride, and diboron hexahydride. Diborane is a poisonous, flammable, high-pressure gas mixture. Diborane is incompatible with oxidizers, aluminum, halogens, and water.

DIBORANE
Diborane is a key boron compound with a variety of applications. The compound is classified as "endothermic," meaning that its heat of formation, Hf is positive (36 kJ/mol). Despite its thermodynamic instability, diborane is kinetically robust and exhibits an extensive chemistry, much of it entailing loss of hydrogen. CAS 19287-45-7

HISTORY
Diborane was first synthesised in the 19th century by hydrolysis of metal borides, but it was never analysed. From 1912 to 1936, the major pioneer in the chemistry of boron hydrides, Alfred Stock, undertook his research that led to the methods for the synthesis and handling of the highly reactive, volatile, and often toxic boron hydrides. He proposed the first ethane-like structure of diborane.[6] Electron diffraction measurements by S. H. Bauer initially appeared to support his proposed structure. Because of a personal communication with L. Pauling (who supported the ethane-like structure), H. I. Schlessinger did not specifically discuss 3-center-2-electron bonding in his then classic review in the early 1940s.[9] The review does, however, discuss the C2v structure in some depth, "It is to be recognized that this formulation easily accounts for many of the chemical properties of diborane..."

HISTORY
In 1943 an undergraduate student at Balliol College, Oxford, H. Christopher Longuet-Higgins, published the currently accepted structure together with R. P. Bell.[10] This structure had already been described in 1921.[11][12][13] The years following the Longuet-Higgins/Bell proposal witnessed a colorful discussion about the correct structure. The debate ended with the electron diffraction measurement in 1951 by K. Hedberg and V. Schomaker, with the confirmation of the structure shown in the schemes on this page. William Nunn Lipscomb, Jr. further confirmed the molecular structure of boranes using X-ray crystallography in the 1950s, and developed theories to explain its bonding. Later, he applied the same methods to related problems, including the structure of carboranes on which he directed the research of future Nobel Prize winner Roald Hoffmann. Lipscomb himself received the Nobel Prize in Chemistry in 1976 for his efforts.

PHYSICAL PROPERTIES
Molecular weight : 27.67 g/mol Appearance : Colourless gas Density 1.216 g dm-3 Melting point 165 C, 108 K, -265 F Boiling point -92 C, 181 K, -134 F Critical temperature : 16.6 C Critical pressure : 40.53 bar Auto ignition temperature : 38 C

CHEMICAL PROPERTIES
Diborane ignites spontaneously in moist air at room temperature. It is stable only at low temperatures.

When heated at temperature between 373 K and

575 K, diborane changes into higher boranes.

CHEMICAL REACTIONS OF DIBORANE

With oxygen It undergoes spontaneous combustion in air due to strong affinity of boron with oxygen forming boric anhydride.

Hydrolysis It gets hydrolysed easily by water, liberating dihydrogen gas.

CHEMICAL REACTIONS OF DIBORANE

With alkalies Diborane dissolves in strong alkalies to produce metaborates and dihydrogen gas.

With alkali metal hydrides Alkali metal hydrides react with B2H6 in ether to form borohydride complex.

CHEMICAL REACTIONS OF DIBORANE

With halogens B2H6 reacts with halogens under different conditions to form halodiboranes.

With halogen acids Halogen acids react with diborane to form halodiborane and dihydrogen gas.

CHEMICAL REACTIONS OF DIBORANE

With ammonia Diborane reacts with ammonia under different conditions to give different products.

APPLICATIONS
Applications of Diborane in the industry are as follows: Rocket propellants: Diborane forms explosive mixtures with air over a wide range, the LEL and UEL values are 0.8 and 88% by volume of air respectively. It explodes in contact with fluorine or chlorine, producing boron halide; halogenated hydrocarbons such as carbon tetrachloride or chloroform; and oxygenated surfaces. It ignites with fuming nitric acid. Tremendous increase in energy content was highly attractive to people designing jet and rocket engines. But owing to its high cost, it is not on large scale.

APPLICATIONS
As a flame-speed accelerator As a doping agent for the production of semiconductors. It is used as an intermediate in the production of highly pure boron for semiconductor production. It is also used for studying the mechanisms of its reactions with organic chemicals. As a rubber vulcaniser: Diborane is used as an initiator in vulcanization of rubber. As a catalyst for hydrocarbon polymerisation:

METHODS OF PREPERATION
Early preparation of diborane: Alfred Stock Invented one of the early preparation methods of diborane: Magnesium Boride Mixed Boron Hydrides B2H6 Early diborane synthesis was gave low yield and tedious. Early Schlesinger group diborane synthesis: 2 BCl3+ 6 H2 B2H6+ 6 HCl

 Later Schlesinger group diborane synthesis: 2 BF3+ 6 LiH B2H6+ 6 LiF Modified version of this method is used as the industrial process for the preparation of Diborane.

LABORATORY METHODS OF PREPERATION OF DIBORANE

By the reaction of iodine with sodium borohydride in a high boiling solvent.

By reduction of BCl3 with LiAlH4

By passing silent electrical discharge through BCl3 and H2

 Mixture of higher boranes can be prepared by action of phosphoric acid on magnesium boride.

NOVEL METHOD
NOVEL METHOD: RAW MATERIALS: Aluminum, Ethyl chloride, Boron oxide, Triethyl amine, Hydrogen. OPERATING CONDITIONS: Temp: 80C CHEMICAL REACTIONS: 4Al+ 6EtCl+B2O3 2Et3B + 2AlCl3 + Al203 ... (1) 2Et3B + 3H2 + 2Et3N 2Et3N.BH3 + 6C2H6... (2) 2Et3N.BH3 + 2AlCl3 B2H6 + 2E3N.AlCl3 (3)

NOVEL METHOD
OVERALL REACTION4AI + 6EtCl+ B203+3H2+ 2Et3N B2H6+ Al203+ 2Et3N.AICl3 + 6C2H6

PROCESS DESCRIPTION The novel method is described for the preparation of diborane from aluminum, ethyl chloride, boron oxide and hydrogen via three steps: I. deoxyalkylation of boron oxide II. hydrogenation of triethylboron and III. liberation of diborane.

NOVEL METHOD
The triethylboron was prepared from aluminium, ethyl chloride and boron oxide directly at 85-110C in 88% yield, with aluminum trichloride as by-product in 95% yield. In the presence of triethylamine and a hydrogen pressure of 130 kg/cm2, the triethylboron was hydrogenated at 200C for 2 hours to produce borane-triethylamine complex in 92% yield. The borane-triethylaaniine complex was treated again at 80C with the aluminium trichloride collected from the first step to liberate diborane in 94% yield. The overall reaction yield was 76%.

NOVEL METHOD
The triethylamine can be recycled. The consumable starting materials of this method therefore involve only aluminum, ethyl chloride, boron oxide, and hydrogen. ADVANTAGES: 1. Shorter process with only three steps and in good yield of the overall reaction. 2. Cheap and easily available starting materials, and

NOVEL METHOD
3. Elimination of boron trifluoride or its ethyl ether complex so as to avoid corrosion of the equipment.

DISADVANTAGE: The reaction mixture is highly explosive.

INDUSTRIAL PROCESS
RAW MATERIALS: boron trichloride,metal hydride, hydrogen, water , carbon

CATALYST: aliuminium trihalide (gives high yield of diborane and faster reaction) in presence of anhydrous solvent(ether)
OPERATING CONDITIONS: TEMP: -10C to 200C; PRESSURE: 1 atm

INDUSTRIAL PROCESS
REACTION:

Reaction Steps: o Magnesium prepared from magnesium oxide and carbon in carbothermic magnesium process. Here C is the reductant Impuritirescarbon, magnesium oxidedo not have effect on reaction React magnesium oxide n carbon @ temp above 1800C n press. Of 1 atm to produce gaseous magnesium n gaseous carbonmonoxide

INDUSTRIAL PROCESS
To avoid reversion of reduction to carbon n magnesium oxide that occurs on slow cooling, a rapid quench technique utilizing methane, hydrogen, fuel oil etc. gases is employed to prepare a solid product Consisting of approx. 52% Mg, 11% C, 37% MgO. Gases shock cooled from methane. Shock cooling leads to 66.4% conversion to Mg.

INDUSTRIAL PROCESS
o Then we obtain diborane n magnesiumchloride. o Magnesiumchloride is hydrolysed and calcined to form magnesiumoxide and this is recycled to carbothermic magnesium process.

INDUSTRIAL PROCESS
PROCESS: BCl3 N MgH2 in the presence of catalyst are contacted in an agitated reactor for e.g a ball mill reactor (stainless steel) @ temp as low as -10C to the boling point of the particular solvent used. o Reactor type: Time: 16.4 hours Operating conditions: 25C Conversion efficiency53% Pdt ratioMgCl2 : Diborane:: 15:1 Stoichiometry --- 3:2

INDUSTRIAL PROCESS
Effect of catalyst o Rapid reaction and higher yields o Mole ratio of AlCl2 to MgH20.02 and preferably 0.15 o Solventsbenzene,ethyl benzene,hexane. Diethylbenzene etc. o Anhydrous environment is required because of the reactivity of BCl3 and MgH2 o Catalyst: solvent10:30

INDUSTRIAL PROCESS
Recation conditions-- -10C- 200C Preferably 0-50C At 200C, diborane is thermally rearranged ot form higher molecular weight boranes such as deca an penta boranes Reactor loaded at atm pressure Further pressure might build up Continuous agitation is required

INDUSTRIAL PROCESS
SEPARATION: Separtion of gases is done by convevtional method Reaction productsgas and liquid o Gasdiborane o Liquidsolvent is seperated from the unreacted mixture. unreacted MgH and BCl3, MgCl2, MgO, C The mixture is then hydrolysed to form MgOHCl by heating from 30-200c, preferably near 200C. This is then calcined at 300-1000C to MgO. This MgO is then recycled.

INDUSTRIAL PROCESS
ADVANTAGES: Negligible emmition of process gases. Magnesium is recycled in the process, there by reducing raw material cost. DISADVANTAGES: Reaction mixture is highly explosive. Thus precautions have to be taken to prevent any leakage in the system, adding to the product cost.

HEALTH EFFECTS
Diborane gas is irritating to the eyes, skin, and respiratory tract. It may cause burning of the eyes, nose, and throat; cough and constriction and edema of the airway and lungs can occur. Other possible effects include dizziness, headache, weakness, and lack of coordination. Kidney and liver damage may rarely occur. Local irritation is caused by the exothermic nature of the hydrolysis reaction. Individuals with pre-existing respiratory diseases may be more susceptible to exposure to diborane.

Acute Exposure The toxic effects of diborane are primarily due to its irritant properties. The local irritant action of diborane is due to the heat released as a consequence of its reaction with water and products formed by the hydrolysis reaction, such as boron oxide. Symptoms may be apparent immediately or delayed for a few hours.

 Respiratory Exposure to diborane can cause a sensation of tightness of the chest leading to diaphragmatic pain, shortness of breath, cough, and wheezing. These signs and symptoms, which may be delayed for up to 24 hours, can be seen for 3 to 5 days after an exposure.

 Dermal Skin irritation manifested as reddened skin may occur from exposure to diborane vapors. Ocular/Ophthalmic High concentrations of diborane can cause eye irritation, pain, swelling, lacrimation, or photophobia. Neurologic Dizziness, headache, weakness, central nervous system depression, and incoordination have been seen following exposure to diborane.

 Potential Sequelae Weakness and fatigue may follow exposure to diborane. Damage to liver and kidneys may occur in some cases during metabolism and excretion. Chronic Exposure Chronic exposure to low concentrations of diborane were reported to have caused seizures, convulsions, fatigue, drowsiness, confusion, altered EEG responses, and spasms of the voluntary muscles. Others have reported headache, vertigo, chills, ans sometimes fever. Asthmatic bronchitis can also occur.