Styphnate

Lead styphnate is a weak primary explosive because of its high metal content (44.5%) and therefore is not used in the filling of detonators. It is used in ignition caps, and in the ASA (i.e. lead azide, lead styphnate and aluminium) mixtures for detonators. Some of its properties are shown in Table 2.4. 

Colour Molecular weight Melting temperature/°C Decomposition temperature/°C Thermal ignition temperature/°C Density at 20 °C/g cm Enthalpy of formation/kJ mol Energy formation/kJ mol Orange-yellow to dark brown crystalline solid 468.305 260-310 235 330 3.02 -836.80 -818.22  

Lead azide can exist in two allotropic forms the more stable a-form which is orthorhombic, and the /1-form which is monoclinic. The a-form is prepared by rapidly stirring a solution of sodium azide with a solution of lead acetate or lead nitrate, whereas the /1-form is prepared by slow diffusion of sodium azide in lead nitrate solutions. The /1-form has a tendency to revert to the a-form when its crystals are added to a solution containing either the a-form crystals or a lead salt. If the /1-form crystals are left at a temperature of 160 °C they will also convert to the a-form. Some of the properties of lead azide are presented in Table 2.3. 

1 In this book the term sensitiveness is used to describe the response of an explosive to accidental initiation, i.e. friction, impact, etc., whereas sensitivity is used when the explosive is initiated by non-accidental methods, i.e. shock from a primary explosive. 

Colour Orange-yellow to dark brown crystalline solid 

Lead styphnate is a weak primary explosive because of its high metal 

Lignin occurs as a large percentage of the noncellulosic part of wood. Newer laboratory processes yield quality lignin with molecular weights of 200 to 1000, but kraft process lignin has a molecular weight of 1000 to 50,000 and is altered chemically by sulfonation. 

Presently it is mostly used as a fuel, but as petroleum becomes increasingly scarce and expensive, proposals and experimental plants for using this material begin to appear. One such process uses fluid-bed hydrocracking and dealkylation to produce phenols and benzene. 

Lignin derivatives, sulfonated alkali lignin and sulfite lignosulfonates, are being used to increase tertiary oil recovery in pumped out oil wells replacing more expensive synthetic detergents. 

The uses of lignosulfonates include the manufacture of binders, adhesives, surfactants, animal feed additives, and vanilla. 

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Styphnates. Aromatic hydrocarbons (and also some amines and heterocyclic bases) form 1 1-addition products with styphnic acid (2 4 6-trinitroresorcinol),... 

Benzene must be employed as the solvent for anthracene styphnate since most other solvents lead to dissociation. 

Hydrocarbon B.P. M.P. 20- 4 20 Picrate Aroyl- benzolc Acid Compound with 1 3 5-Trlnltro-benzene Styphnate Other Derivatives... 

Property Mercury fiihninate Lead azide Silver azide Normal lead styphnate DDNP Tetrazene... 

Lead styphnate monohydrate is precipitated as the basic salt from a mixture of solutions of magnesium styphnate and lead acetate followed by conversion to the normal form by acidification using dilute nitric acid (97—99). 

B. F. Hasten, Basic Eead Styphnate, Fine Milling, NAVORD OD 23996, Washiagton, D.C., 1963. 

Exothermic Decompositions These decompositions are nearly always irreversible. Sohds with such behavior include oxygen-containing salts and such nitrogen compounds as azides and metal styphnates. When several gaseous products are formed, reversal would require an unlikely complex of reactions. Commercial interest in such materials is more in their storage properties than as a source of desirable products, although ammonium nitrate is an important explosive. A few typical exampes will be cited to indicate the ranges of reaction conditions. They are taken from the review by Brown et al. ( Reactions in the Solid State, in Bamford and Tipper, Comprehensive Chemical Kinetics, vol. 22, Elsevier, 1980). 

Styphnic acid is a nitrogen compound. Lead styphnate monohydrate was found to detonate at 229°C (444°F), but the course of decomposition could be followed at 228°C and below. 

Benzo[ghi]perylene (1,12-benzoperylene) [191-24-2] M 276,3, m 273°, 277-278.5°, 278-280°, Purified as light green crystals by recrystn from CfiH6 or xylene and sublimes at 320-340° and 0.05mm [UV Helv Chim Acta 42 2315 7959 Chem Ber 65 846 1932 Fluoresc. Spectrum J Chem Soc 3875 7954]. 1,3,5-Trinitrobenzene complex m 310-313° (deep red crystals from C6Hg) picrate m 267-270° (dark red crystals from CgH6) styphnate (2,4,6-trinitroresorcinol complex) m 234° (wine red crystals from CgH6). It recrystallises from propan-l-ol [J Chem Soc 466 7959]. 

Leptactina senegambica (Rubiaceas). The root-bark contains about 1 per cent, of alkaloids, including leptactinine, m.p. 264f-6°, which forms a picrate, m.p. 258° (dec.), picrolonate, m.p. 196°, and styphnate, m.p. 240-2°. The colour reactions with numerous alkaloidal reagents are recorded, some of which indicate that an indole nucleus is present. Pharmacological effects of an extract of the root bark are described (Paris and Bouquet, Ann. pharm. franc., 1946, 4, 233). 

Magnesium Chlorate. See under Chlorates Magnesium Styphnate or Magnesium Trinitro-... 

Magnesium Triniiroresorcinate. See under Styphnic Acid and Styphnates... 

Azide Powder Styphnate B PETN RDX Tetryl TNT Amatol H alette Tetrytol Ednatol Pentolite... 

NOL No 130 Primer Mixture. See under Lead Styphnate, Basic in Vol 5, D1278-L... 

N 6.07%, OB to C02 —17.33% large, six-sided rhombic prisms mp 112°. V sol in warm ethanol and insol in w. Prepn is by bubbling gaseous bromine into an aq soln of Na styphnate [C6H(N02)3(OH)(ONa)J. Separation from the co-product, bromopicrate, is achieved by washing the ppt with warm ethanol... 

CAHN RG ELECTROBALANCE/SEDIMENTATION ACCESSORY. This app produces a continuous, visible chart record of the sediment weight collected on the balance pan. It has been evaluated for measuring particle size distributions of the primary expls Lead Styphnate, Lead Azide, Tetracene by Hutchinson (Ref 41). 

Four samples of Lead Styphnate were analyzed by dispersing in acet and were found to have average diameters of 15.9 y with a standard deviation of 0.4p. The reproducibility for Tetracene, with average diameter of 35 y, was 2y. Methanol was found to be a satisfactory dispersant for Lead Azide with average particle diameter of 12y... 

PbDNAzP 13, Basic Pb Styphnate 27, double salt of K and Ba nitrate 30, Sb silicide 7, ground glass 23% 2) PbDNAzP 8, Basic Pb Styphnate 22, double salt of K and Ba nitrate 40, Sb silicide 23, Ca silicide 7%... 

Potassium Dinitroazidophenolate (called Potassium Dinitrophenylazide by McNutt). K0,N3.CgH2(N02)2. It was proposed as an ingredient of primer mixts suitable for small srms and artillery ammo, commercial blasting caps, etc. Typical mixts suggested were 1)K Dinitroazidophenolate 16, Basic Pb Styphnate 15, Ba nitrate 40, Sb silicide 29% 2) K Dinitroazidophenolate 17, Basic Pb Styphnate 18, Ba nitrate 35, Pb thiocyanide 5, ground glass 25%... 

Woodring, USP 2206652 (1940) CA 34,7610 (1940) [Primer compn contg Pb, Na or Cd salts of trinitrophloroglucinol with Pb Styphnate and other ingredients] 10) R- Schmitt, SS 38, 149 (1943) [Quant estimation of trinitrophloro-glucinol by pptn with phenyl ad ridine soln]... 

Effect of heat. When anhydrous, it detonates at about 210°. The material with one H20 deflagrates about 230°, when heated slowly, as compared to 275—290° for Pb Styphnate. Contact with flame or a red-hot wire results in immediate detonation if the material is dry, but when wet it is difficult to detonate or ignite Thermal stability and volatility. No loss in wt was observed when stored for 300 days at 50° for 150 days at 70°, or 50 days at 90° Hygroscopicity. More hygroscopic than Pb Styphnate. When stored at 90% RH for Q days it absorbed 0.24% moisture, and for 20 days, 0.90% moisture... 

Compatibility with metals. Moderately moist material does not attack metals it resembles Pb Styphnate in this respect Compatibility with explosives. Mixts with equal parts ui i, rsi, rci m izuyi, ami... 

It forms salts, some of which are expl, eg Basic Lead Salt. PbCgHjOgN, mw 416.32, N 3.36%. Was proposed by Briin for use in mixts with Pb Styphnate, Pb nitrate, etc, in expl compns (Ref 3)... 

Prepd by treating methoxy picric acid with Pb hydroxide. It loses its OCH3 group thru hydrolysis to form normal Pb Styphnate. The OPbOH group displays acidic behavior in soln. 

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