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Metal Hydrides

Contents
1. 2. 2.1 Introduction Products and Properties Alkali Hydrides - Lithium Hydride and Sodium Hydride Lithium Hydride Sodium Hydride Binary Hydrides of Boron Lithium Borohydride, Sodium Borohydride, Potassium Borohydride Lithium Borohydride Sodium Borohydride Potassium Borohydride Binary Hydrides of Aluminum Lithium Aluminum Hydride (LAH) Complex Hydrides of Lithium and Boron Lithium Triethylborohydride (LTEBH) Complex Hydrides of Sodium and Boron Sodium Triacetoxyborohydride (STAB) Complex Hydrides of Lithium and Aluminum Lithium Tri(tbutoxy)aluminum Hydride (LTTBA) Safe Handling Storage Storage in the Laboratory Behavior of Hydrides towards Air Reaction with Water Handling of Solid Hydrides Fire Fighting 3.6 3.7 3.8 4. 4.1 4.2 4.3 5. 6. 6.1 Protection of Personnel First Aid Disposal of Residues Packaging and Transport Solid Products Products in Solution Packaging Transport

2.1.1 2.1.2 2.2

2.2.1 2.2.2 2.2.3 2.3

Analysis Analysis of Solid Hydrides 6.2 Analysis of LAH Solutions Disclaimer

2.4

2.5

2.6

3. 3.1 3.1.1 3.2 3.3 3.4 3.5

Metal Hydrides 1. Introduction


Metal hydrides form a large variety of compounds with diverse structures, bonding types, and chemical properties. While some of these hydrides are only of pure academic interest others are used on a large industrial scale. A good review over the variety of hydrides is given in an article in Ullmanns Encyclopedia of Industrial Chemistry1. The industrial use of hydrides has been growing over the last decades and Chemetall has acquired a broad know-how in the manufacture and handling of commercial quantities. The purpose of this brochure is to give an overview of the metal hydrides available from Chemetall and to share our technical knowledge with our customers. It is our intention to make our customers familiar with the properties of the various hydrides and to give a general handling instruction. A short overlook over their chemical behaviour is given in a trifold leaflet available from Chemetall. For more details please refer to the chemical literature. Because of the importance of lithium aluminium hydride it is described in detail in a separate special brochure which is also available from Chemetall. Additional information is available from Chemetall through our product data sheets, MSDS, as well as our brochure on packaging.

Visit also our website: www.chemetalllithium.com for further information and updates.
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Peter Rittmeyer, Ulrich Wietelmann, Ullmanns Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag, Weinheim 2002

Metal Hydrides 2. Products


The following products available from Chemetall are described in this brochure:

2.1 Alkali Hydrides Lithium Hydride and Sodium Hydride


Lithium Hydride and Sodium Hydride both form ionic hydrides because of the strong electropositive character of the cation.

In general they are not used as reducing agents but as a strong base instead. Another application is their capability to store hydrogen. As a consequence they are used to manufacture further complex metal hydrides. Chemetall supplies these hydrides in industrial quantities.

Table 1 Product Availability Product No. Conc. abt.


[%]

Density abt.
[g/cm3]

Bulk density abt.


[kg/l]

Molarity Abt.

Lithium hydride Sodium hydride Lithium borohydride Sodium borohydride

Powder Sieved Dispersion, abt. 60 % in mineral oil Solution, 5 % in THF Powder Granular

401613 401606 408164 401652 401251 401254

min. 97 min 97 57 - 63 4.5 5.5 min. 98 min. 98

0.78 0.78

0.29 0.43 0.60

abt. 2

0.89 1.074 1.074 0.4 - 0.5 0.4 0.5

Potassium borohydride Lithium aluminum hydride (LAH)

Powder Powder Tablets THF, abt. 4 % THF, abt. 10 % 2-MeTHF, abt. 10 % THF/toluene, abt. 15 % Diethyl ether, abt. 20 %

401666 401614 401616 401625 401634 401632 401630 401631 401749 401729

min. 98 min. 97 min. 97 3.9-4.5 9.5 10.5 9.5 10.5 14.5 15.5 18.0 22.0 11.0 13.0 19.0 21.0

1.175 0.9 0.9 0.90 0.90 0.87 0.89 0.76 0.89 0.89 0.4 0.4

abt. 1 abt. 2.4 abt. 2.2 abt. 3.5 abt. 4 abt. 1 abt. 1.6

Lithium triethylboro hydride (LTEBH) Sodium triacetoxyborohydride (STAB) Lithium tri-(tbutoxy)aluminum hydride (LTTBA)

THF, abt. 12 % THF, abt. 20 %

Powder Tablets Powder

401667 401668 401620

min. 97 min. 97 95 110

0.35

0.5

THF, abt. 30 %

401624

29.0 31.0

0.90

abt. 1.05

2.1.1 Lithium Hydride


Lithium hydride is available from Chemetall in solid form as a milled powder (grain size < 100 m) or as sieved granulate with a grain size of 3 -25 mm. The appearance of the granulate is light grey to blue whereas the powder is grey to white. Lithium hydride is thermally very stable with a melting point of 688 C without decomposition. It has the highest hydrogen content of any alkaline hydride (theor. 12.7 %). Lithium hydride is used in limited quantities for the manufacture of high purity monosilane and as hydrogen source for various purposes. To date the largest application remains as a raw material for the manufacture of lithium aluminum hydride (see 2.3) and other complex hydrides. A detailed description of the packaging is given in chapter 4.

Properties of lithium hydride


CAS No. EINECS No. Molecular weight Product no. lithium hydride powder (< 100 m) Product no. lithium hydride sieved (3-25 mm) Appearance 7580-67-8 231-484-3 7.95 401613

401606

bluish to gray grains, white to grey powder 0.78 g/cm3 approx. 0.29 kg/l (powder) approx. 0.43 kg/l (grains) LiH min. 97 % Na max. 0.8 % K max. 0.04 %

Density Bulk density

Specification

Properties of sodium hydride


CAS No. EINECS No. Molecular weight Product no. Sodium hydride dispersion, abt. 60 % in mineral oil Appearance Density Bulk density Specification 7646-69-7 231-587-3 24.00 408164

2.1.2 Sodium Hydride


Sodium hydride is used commercially as a strong base for deprotonation reactions. It can be used for condensation reactions of carbonyl compounds like Claisen, Dieckmann, Stobbe etc. Furthermore it serves as starting material for the production of sodium borohydride (see 2.2.2). Sodium hydride is a poor reducing agent because of its high basicity and its insolubility in inert organic solvents. Because of its properties, i.e. spontaneous ignition of the pure material in humid air it is commercially available only as a ca 60 % dispersion in mineral oil. The particle size of abt. 10 m leads to a highly reactive material which must be handled under the exclusion of air. Therefore sodium hydride is packed in solvent soluble bags (either soluble in toluene or in Chemetalls Secubag). For more details see 4. Packaging.

light gray, tacky powder 1.396 g/cm3 Approx. 0.6 kg/l NaH 57-63%

2.2 Binary Hydrides of Boron Lithium Borohydride, Sodium Borohydride, Potassium Borohydride
The three species of binary hydrides of boron - Lithium borohydride, sodium borohydride, potassium borohydride are used on different industrial scales. Whereas sodium borohydride is manufactured on a multi thousand tons scale, the other two representatives are used to a much smaller extent only. Their reaction behavior is strongly depending on the cation. This can be seen in the decreasing stability, i.e. decreasing reactivity from Li > Na > K.

2.2.1 Lithium Borohydride


Lithium borohydride has one of the highest energy densities of chemical carriers. However the proposed use as rocket fuel remains only academic. It is used for the selective reductions of esters, carboxylic acids, amides and epoxides. The addition of a stoichiometric amount of alcohols (methanol or ethanol) considerably enhances the reactivity. Because of the extreme hygroscopicity of solid lithium borohydride it is currently only available as a 5 % (2 m) solution in THF. Packaging is described in chapter 4.

LiBH4 Melting point Decomposition


280 C > 200 C

NaBH4
505 C >400 C

KBH4
585C > 500C

Nucleophilicity decreases in the order LiBH4 > NaBH4 > KBH4

Properties of lithium borohydride solution, abt. 5 % in THF


CAS No. EINECS No. Molecular weight Product no. lithium borohydride, abt. 5 % in THF Appearance Density (20 C) Specification Molarity 16949-15-8 241-021-7 21.78 401652

2.2.2 Sodium Borohydride


Sodium borohydride is by far the most commonly used species of the borohydrides group. Sodium borohydride is manufactured mainly for bleaching of pulp and paper on a several thousand tons scale as a 12 % alkaline aqueous solution (for the in situ production of sodium dithionite). The solid form is used as a versatile reducing agent in the organic chemical and pharmaceutical industry. For packaging details please refer to chapter 4.

colorless, slightly turbid solution 0.89 g/cm3 4.5 5.5 % 1.8 2.2

Properties of sodium borohydride


CAS No. EINECS No. Molecular weight 16940-66-2 241-004-4 37.83

Product no. sodium borohydride, 408254 granular Product no. sodium borohydride, 408251 powder Appearance white granulate or white, slightly hygroscopic powder 1.074 g/cm3 0.4 0.5 kg/l 0.5 2.0 mm Min. 97 % Max. 0.5 % Max. 0.5 %

Density Bulk density Grain size granulate Specification NaH H2O

2.2.3 Potassium Borohydride


Potassium borohydride is completely stable in air and not hygroscopic. The hydrolysation reaction in humid air is extremely slow. The solubility compared to the other binary borohydrides is much lower. The reactivity is slightly lower compared to sodium borohydride but it is much less used as a reducing agent in organic and pharmaceutical chemistries. It can be used for the chemoselective reduction of aldehydes, ketones, acid chlorides, or azides. Packaging is described in chapter 4.

Properties of potassium borohydride


CAS No. EINECS No. Molecular weight Product no. potassium borohydride Appearance Density Specification 13762-51-1 237-360-5 53.94 401666

white, crystalline powder 1.175 g/cm3 min. 98 %

Properties of lithium aluminum hydride


CAS No. EINECS No. 16853-85-3 240-877-9

2.3 Binary Hydrides of Aluminum Lithium Aluminum Hydride (LAH)


Lithium Aluminum Hydride (LAH) is the strongest reducing agent and is widely used in organic and pharmaceutical synthesis. Due to the weaker Al-H bond it is a much more powerful reducing agent than sodium borohydride. It is most commonly used for the reduction of e.g. esters and carboxylic acids. Because of its importance and the flexibility in handling, lithium aluminum hydride is described in greater detail in a separate brochure which is available from Chemetall. The following is only a summary of the important points. For packaging details see chapter 4 or the dedicated brochure on LAH.

Molecular weight 37.95

Solid LAH
Product no. lithium aluminum hydride, crystalline powder Product no. lithium aluminum hydride, tablets Appearance Density Bulk density Specification 401614

401616

white to light grey 0.917 g/cm3 abt. 0.4 kg/l min. 97 %

LAH solutions Product Product no. Concentration Density abt.


[20C]

Molarity abt.

LAH, abt. 4 % in THF LAH, abt. 10 % in THF LAH, abt. 10 % in 2-MethylTHF LAH, 15 % in THF/toluene LAH, 20 % in diethyl ether

401625 401634 401632 401630 401631

3.9 4.5 % 9.5 10.5 % 9.5 10.5 % 14.5 15.5 % 18.0 22.0 %

0.9 g/cm3 0.9 g/cm3 0.87 g/cm3 0.89 g/cm3 0.76 g/cm3

1 2.4 2.4 3.5 4.0

2.4 Complex Hydrides of Lithium and Boron Lithium Triethylborohydride (LTEBH)


Lithium triethylborohydride, also known under the brand name Super-Hydride is one of the more frequently used alkyl substituted complex borohydrides. It is commercially available as a 12 % (1 m) or as a 20 % solution in THF and is stable under the exclusion of humidity and air. It is a stereoselective reducing agent for e.g. bicyclic imides, isoquinolines, and pyridines. Packaging is described in chapter 4.

Properties of lithium triethylborohydride


CAS No. EINECS No. Molecular weight Product no. lithium triethylborohydride, abt. 12 % solution in THF Product no. lithium triethylborohydride, abt. 20 % solution in THF Appearance Density (20 C) Specification 22560-16-3 245-076-8 105.95 401749

401729

colorless to light turbid solution 0.89 g/cm3 11 13 % resp. 19-21 %

2.5 Complex Hydrides of Sodium and Boron Sodium Triacetoxyborohydride (STAB)


Sodium triacetoxyborohydride is comparable in performance to the toxic counterpart sodium cyanoborohydride. Sodium triacetoxyborohydride (STAB) is a mild reducing agent and an ideal alternative for the toxic cyanoborohydride. STAB is used for reductive aminations, the reduction of heterocycles, and the selective reduction of aldehydes in the presence of ketones. Though STAB does not react with ketones even with an excess of reagent, it can be used for the stereoselective reduction of - and -hydroxyketones to the corresponding anti-diols. STAB thus offers a wide range of applications in organic synthesis. Packaging is described in chapter 4.

Properties of sodium triacetoxyborohydride


CAS No. EINECS No Molecular weight Product no. sodium triacetoxyborohydride powder tablets Appearance 56553-60-7 211.94 401667 401668 colorless, light, fluffy powder or tablets 0.956 g/cm3 approx. 0.35 kg/l min. 97 %

Density Bulk density Specification

Properties of lithium tri-(t-butoxy)aluminum hydride 2.6 Complex Hydrides of Lithium and Aluminum Lithium Tri-(t-butoxy)aluminum Hydride (LTTBA)
CAS No. EINECS No. Molecular weight Lithium tri(t-butoxy)aluminum hydride (LTTBA) is a milder reducing agent than the nonsubstituted LAH. Therefore it is also more stable (sublimation at 280 C) and decomposes at > 300 C only. It is very suitable for the selective reduction of ketones or acid chlorides to aldehydes whereas LAH reduces to the corresponding alcohol. It is available as white crystalline powder or as a 30% solution in THF. For packaging details see chapter 4. Product no. lithium tri(t-butoxy) aluminum hydride, solution Product no. lithium tri(t-butoxy) aluminum hydride, powder Appearance 17476-04-9 241-490-8 254.28 401624

401620

clear to slightly turbid solution or white to light grey powder 0.9 g/cm3 solution abt. 0.5 kg/l solid 29-31 % solution 95-110 % solid

Density (20 C) Bulk density Specification

Metal Hydrides 3. Safe Handling 3.1 Storage 3.1.1 Storage in the Laboratory
The products LAH, LTTBA, LiBH4 and LTEBH are available as ready to use solutions. For laboratory use they are available in glass bottles of 500 ml and 1 l content equipped with a special septum and a screw cap. Safe handling of these solutions requires some precautions which are due to the specific properties of complex metal hydrides.

these are dangerous and may easily explode. Therefore the solvent soluble bags containing e.g. LiAlH4-powder or NaH should not be opened in air. If LiAlH4 in solid form must be handled in air, the use of LiAlH4-tablets is recommended instead. The solid borohydrides are less sensitive towards air. All hydrides are hygroscopic and, due to their reaction with atmospheric moisture and carbon dioxide, will degrade when exposed to humid air. On contact with dry air, they will also lose activity, but at a much slower rate. Spilled solutions of hydrides normally do not ignite as they are protected by the formation of a hydroxide-layer on their surface. Nevertheless self-ignition cannot be ruled out. An increase in the risk of self-ignition will result if ethereal solutions of LAH, LTTBA, LiBH4 or LiBEt3H are spilled onto a porous surface (e. g. clothing). Rapid evaporation of the solvent leads to the formation of a very finely divided hydride. In such a case, self-ignition might easily occur.

Eliminating accidental contact with water should, therefore, be a primary concern when handling or storing hydrides.

3.4 Handling of Solid Hydrides

Do not expose solutions in glass bottles to temperatures above room temperature and light irradiation for extended periods of time Do not use wet syringes for sampling. Residues of water or other protic substances will react with the hydride with evolution of gas. Do not store hydride solutions for more than 6 months. It is recommended to use a bottle within 3 months (see label on glass bottle with date of production). Store the solutions protected from light and heat, preferably in an explosion-proof refrigerator or a safety cabinet

If hydride powders must be handled in air by opening the soluble inner bags, special care has to be taken: The formation of dust must be avoided as an ignition source such as a spark from an electrostatic discharge could easily cause a dust explosion. Therefore all equipment which is used in handling hydrides should be of stainless steel, copper or zinc instead of glass, plastic or iron. Extreme caution should be exercised when the hygroscopic LiAlH4 comes in contact with air. The resulting mixture is rich in hydrogen and prone to ignition by static discharge. Handling larger amounts of hydrides, especially LiAlH4- powder in air is not at all recommended. If it is essential to open the bags containing hydride powders, this can be done without risk under inert gas in a glove-box. The glove-box should be operated under a slight overpressure of some mbar of nitrogen or argon.

3.3 Reaction with Water


All hydrides react with water generating highly flammable hydrogen gas. The borohydrides, especially NaBH4 and KBH4 decompose only slowly in water, especially in alkaline solutions. On the other hand products like LAH, LiH, NaH react violently with water. The large amount of hydrogen formed in this reaction (e.g. 2.36 l H2/g LiAlH4) is highly flammable and can form explosive mixtures with air. Under certain conditions, e. g. when water is sprayed on LiAlH4 in the presence of air, the hydrogen will ignite spontaneously.

3.5 Fire Fighting


Fires of solid hydrides or their solutions should be fought with suitable extinguishers containing powder based on sodium chloride (e.g. Totalit M ). Dry limestone powder is also suitable and should be kept in boxes close to the area where the products are used. (see Fig. 1) The limestone powder can be used not only to cover spilled solutions but also to cover burning

3.2 Behavior of Hydrides towards Air


Commercially available hydrides are normally non-pyrophoric, even on exposure to air with high humidity. However the formation of dust/hydrogen/air-mixtures has to be strictly avoided as

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hydrides. Due to its poor flowing properties, it is not available in extinguishers. Sand is not suitable to cover spilled solutions. Extinguishers containing or developing water, carbon dioxide or halons are not suitable for fire fighting as they react violently with the hydrides. Extinguished fires should be observed until they have cooled down as there is always the risk of re-ignition.

3.6 Protection of Personnel


To ensure safe performance of the reduction with hydrides, operating personnel should be properly trained, instructed and informed of potential dangers and the correct action to be taken in case of spillage or an accident. Operating personnel should wear adequate protective equipment (see figure 2). This includes: Protective clothing
Fig. 1 Fire-fighting equipment

Chemetall personnel wear protective suits from Nomex which has proven to be very satisfactory. For occasional contact with hydrides protective coats from Nomex with an aluminum layer are also suitable. The protective clothing should not have outside pockets where solution could become trapped. Clothing and underclothing made from other synthetic fibers should not be worn because of the possibility of melting when exposed to fire. This safety measure is required in any case since inflammable organic solvents will be used. Cotton overalls or coats are not suitable.

Gloves Dry and clean Nomex gloves serve for protection of the hands. Rubber gloves are not suitable. Eye/Face protection Goggles and / or full face shields are mandatory. Dust mask If it is absolutely necessary to open bags in air, operators should wear dust proof masks. Shoes To prevent the possibility of electrostatic discharges, personnel

should wear safety shoes with conductive soles (maximum resistance 800 K ).

3.7 First Aid


In the event product comes in contact with the skin, it must be brushed off immediately and rinsed with plenty of running water until no traces of alkalinity are detectable with indicator paper. If the eyes have been exposed to hydrides, they should be thoroughly rinsed with plenty of water. A physician should then be consulted immediately

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Fig. 2 Protective Clothing (Nomex Suit)

3.8 Disposal of Residues


For disposal of small amounts of solid hydride waste, the material should first be covered with a high-boiling hydrocarbon such as thermal oil or toluene. Then ethanol or iso-propanol is added carefully while stirring, preferably with cooling, under nitrogen blanketing. After the hydrogen evolution is complete, the agitated alkoxide sludge is hydrolyzed with water and flushed to the plant's waste water treatment facilities. For disposal of hydride solutions, the procedure is the same, except that the addition of

hydrocarbons is omitted if the solution is already sufficiently diluted. Any spill of solution should be covered with limestone or another suitable extinguishing powder. The soaked material should then be taken to a safe outdoor place and be decomposed by standing in air for some days or from a safe distance by a jet of water. The hydrolysis requires an inert gas blanket or, in the event of an emergency, adequate ventilation must be provided to prevent formation of explosive hydrogen-air mixtures. For the disposal of large amounts of hydrides Chemetall should be contacted

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Metal Hydrides 4. Packaging and Transport 4.1 Solid Products


Packaging can be made according to the customers needs. In case of solid products packaging in units up to 10 kg (LiH, NaH, LAH and LTTBA 5 kg) per bag are possible even odd weights can be made. Standard packaging for solid hydrides is as follows:

sealed, is Chemetalls solvent soluble SecuBag except for lithium hydride and the borohydrides which are packed in PE bags. The outer bag, which is normally clipped, is a normal PE bag which does not dissolve in solvents. On request Chemetall is readily prepared to pack solid hydrides according to the customer's need, e. g. odd weights per bag or several bags per can or drum. This special packaging enables the users to introduce the hydride directly into the reactor without exposing it to air. Inside each can or steel drum, used as the outer packaging for the hydride, a tag is enclosed indicating safety advice and the nature of the inner, soluble bag. A special case is LAH and STAB which are also available as tablets. For more details please see the LAH brochure. The following table shows the properties of various solvents commercially used

Product
LiH NaH NaBH4 KBH4 LAH STAB LTTBA

Standard packaging
5 kg PE 5 kg SecuBag 10 kg PE bag 10 kg PE bag 5 kg SecuBag 1.000 ml glass bottle 5 kg SecuBag

Remarks

Development product

The aforementioned SecuBags are solvent soluble plastic bags which allow the material being introduced into the reactor without opening the bag and/or contact with air. In the following table the solution behavior of the Secubags is described.

Hydrides are usually double packed in plastic bags which are then enclosed either in tin cans or for larger quantities, in steel drums. Standard sizes are bags containing 10 g, 25 g, 50 g, 100 g, 250 g, 500 g and 1.000 g in tin cans as well as 2.000 g and 5.000 g in steel drums. The inner plastic bag, which is normally heat

Solvent

Appearance of solution at 25 C
Bigger parts (turbid at 60 C) Bigger parts (clear at 60 C) Clear Clear Turbid Clear Clear Clear Clear Turbid Turbid

Results

Hexane Heptane Cyclohexane Toluene Diethyl ether MTBE THF 2-Methyl-THF Monoglyme Dimethylacetamide DMF

+ + + + + + + + +

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Solvent

Physical constants
mp C bp C

Density solvent
g/ml

THF 2-Methyl-THF Toluene Xylene Di-ethyl ether Di-isopropyl ether Di n-butyl ether MTBE Dioxane

-65 -136 -95 -25 -116 -86 -98 -109 12

65 78 110 114 34.6 69 142 55 101

0.888 0.860 0.867 0.880 0.713 0.724 0.772 0.740 1.034

4.2 Products in Solution


Some of the hydrides are also available in solution form. For this purpose Chemetall uses special returnable steel-cylinders which are described in a separate brochure. The solutions are available in four different sizes of steel cylinders with the following maximum contents of active product

Due to international transportation regulations, the cylinders are filled to only 90 %of their nominal capacity. Inside the cylinders is a nitrogen blanket with a slight overpressure of 20 - 40 mbar. On request the cylinders can be filled with any desired amount of solution defined by the user (up to the maximum as indicated above). Therefore the hydride content can be adjusted to the individual size of the production batch.

Samples of hydrides in solution form are sent either in glass bottles of 500 ml or 1 l or in returnable steel cylinders which contain up to 5 l solution. Those steel cylinders are emptied by a dip tube. The description is available on request. Storage of the glass bottles in the lab is described in chapter 3.2.1. All cylinders sizes have the same type number and arrangement of valves

Product
1 l glass bottle

Max content per cylinder (kg active)


5l 40 l 125 l 450 l

LAH 4 % THF LAH 10 % THF LAH 10 % in 2-MeTHF LAH 15 % THF/toluene LAH 20 % in DEE LTEBH 12 % LTEBH 20 % LTTBA 30 % THF

0.03 0.08 0.08 0.12 0.14 0.09 0.17 0.24

0.16 0.36 0.36 0.58 0.61 0.49 0.85 1.22

1.3 3.0 3.0 4.6 4.9 3.5 6.1 8.7

4.0 9.6 9.6 14.5 15.4 11.0 19.0 27.3

14.2 34.6 34.6 52.2 55.3 39.6 68.5 98.4

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Metal Hydrides 5. Transport Product


Lithium hydride Sodium Hydride Lithium borohydride, 5 % in THF Sodium borohydride Potassium borohydride Lithium aluminum hydride, solid Lithium aluminum hydride solutions Lithium triethylborohydride Sodium triacetoxyborohydride Lithium tri-(t-butoxy) aluminum hydride, solid Lithium tri-(t-butoxy)aluminum hydride, solution

Hydrides are classified according to international regulations in the following :

UN No.
1414 1427 1413 1426 1870 1410 1411 3394

PSN
Lithium Hydride Sodium hydride Lithium borohydride Sodium borohydride Potassium borohydride Lithium aluminum hydride Lithium aluminum hydride, ethereal Organometallic substance, liquid, waterreactive, Lithium triethylborohydride, tetrahydrofurane Self reactive solid, Type E, temperature controlled Metal hydrides, water-reactive, n.o.s., lithiumtri-(tert.butoxy) aluminium hydride Organometallic substance, liquid, waterreactive, flammable Lithium-tri(tert-butoxy)-aluminium hydride, tetrahydrofuran

Class
4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.2

Marking
F, C F F, C T, F T, F F, C F, C F, C

3238 1409 3399

4.1 4.3 4.3

F, C F, C F, C

Detailed and up-dated transport regulations is available in the corresponding MSDSs which are available from Chemetall.

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Fig. 3

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Metal Hydrides 6. Analysis 6.1 Analysis of Solid Hydrides


Principle: Solid hydrides are decomposed by aqueous dioxane and the hydrogen thereby produced is measured volumetrically. Apparatus: see fig. 3 Procedure: 0.1 g of the material to be analyzed is weighed in a dry weighing glass to an accuracy of 0.1 mg which is then attached to the hydrolyzing apparatus. Through the dropping funnel 2 ml of dioxane is added followed by 10 ml of water, which has been acidified with about 0.5 ml of conc. hydrochloric acid. This addition should initially proceed dropwise in order to avoid too a vigorous reaction. Hydrogen is collected in the gas burette over saturated sodium chloride solution. After temperature equilibrium has been established, the hydride content of the sample may be calculated from the gas volume reading according to the following equation:

Vapor pressure of a saturated NaCl solution C 15 16 17 18 19 20 21 22 23 24 25 26

mm 9.7 10.3 11.0 11.7 Hg

12.4 13.2 14.1 15.0 15.9 16.9 17.9 19.0

For the various hydrides the following factors apply: LiH NaH LiBH4 NaBH4 KBH4 0.01273 0.03846 0.008729 0.01516 0.02162 LiAlH4 LTEBH STAB LTTBA 0.01521 0.16981 0.33987 0.4077

6.2 Analysis of LAH Solutions


The following description is for LAH solution only the other hydride solutions are measured according to 6.1 Principle: Solutions of LiAlH4 react stoichiometrically with solutions of iodine in tolu- ene (provided that the concentration of LiAlH4 in the reaction mixture is between 0,1 and 1,0 M) consuming four equivalents of iodine per mole of LiAlH4. Hydrogen is evolved simultaneously (Felkin's method)2: Reagents and equipment: Diethyl ether, distilled over LiAlH4 LiAlH4 + 2l2 2 H2 + LiAll4

wt % Hydride = F

V Pcorr. TM

Procedure: 20 ml of 0.4 n solution of iodine in toluene is introduced into the dried titrating flask. When analyzing solutions of lithium aluminum hydride in other solvents than diethyl ether, 1 ml of diethyl ether is added. A sample of LiAlH4 solution which should contain about 1 mmol LiAlH4 is weighed in the dried syringe. The syringe is then introduced into the titrating flask and its contents are emptied through the submerged needle into the iodine solution under gentle agitation. Allow to stand for 5 minutes, then quickly add 100 ml of distilled water and 5 ml of glacial acetic. Excess iodine is titrated with 0.1 n solution of sodium thiosulphate, using zinc iodide/ starch solution as indicator. Evaluation:

F: V: Pcorr.:

Factor hydrogen volume [ml] (atmospheric pressure) (vapor pressure of sat. NaCl-solution at measuring temperature) [mm Hg] measuring temperature [K] mass of sample [g]

T: M:

Toluene, distilled over LiAlH4 0.4 n Solution of iodine in toluene n Sodium thiosulphate solution (standardized with KIO3) Glacial acetic acid Zinc iodide / starch solution 250 ml Titrating flask with ground glass joint NS 29 20 ml and 1 ml Pipettes 5 ml Syringe with needle and stopcock dried at 110 C 10 ml Graduated cylinder 50 ml Burette with 0.1 ml graduation
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% LiAlH4 = 0.37953

C M

M: mass of sample [g] C: consumption of 0.4 n iodine solution [ml] = (initial amount of 0.4 iodine solution in ml) 0.25 - (consumption of 0.1 n thiosulphate solution in ml) Note: Standard solutions of iodine in toluene are not stable and should, therefore, be re-standardized prior to use.
2

H. Felkin, Bull. Soc. Chim. France, 1951, 347.

Disclaimer The above product information has been compiled to the best of our knowledge on the basis of thorough tests and with regard to the current state of our long practical experience. Our statements relating to possible uses of the product do not constitute a guarantee that such uses are appropriate in a particular users case or that such uses do not infringe the patents or proprietary rights of any third party. The user should determine the suitability of the product for the users intended use before commencing such use. We assume no risk or liability whatever in connection with any particular use, if not expressly confirmed by us in writing. No liabilities or guarantees deriving from or in connection with this brochure can be imputed to us. WARRANTY & LIABILITY: In the event our product does not conform to the specifications described in this brochure the purchasers sole and exclusive remedy shall be either the replacement by us of that portion of the product which is non-conforming or the refund by us of the purchase price for the non-conforming portion, in our sole discretion as we may select. The foregoing is our sole warranty in regard to the product: ALL OTHER WARRANTIES, EXPRESS OR IMPLIED, INCLUDING WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE, ARE EXCLUDED. We shall not under any circumstances be liable, either directly or by way of indemnification or contribution, to any person for any direct, indirect, special or consequential damages arising out of the purchase or use of the product, whether the claim of such liability sounds in contract, tort or otherwise; except in case of wilful misconduct.
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Further information regarding this type of reagent and its reactions can be found in our dedicated pocket folders. Please dont hesitate to ask for your copy.

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