Hydrazinium metal chloride

Kumar, N.R.S. (1990) Synthesis, spectra and structure of hydrazinium metal chloride and thiocyanate complexes. Ph.D Thesis, Indian Institute of Science, Bangalore. 

Hydrazinium Metal Chloride Hydrates -(N2H5)2MCl4-2H20, M = Transition Metal... 

Hydrazinium metal chloride hydrate complexes are generally prepared by the reaction of aqueous solutions of metal chlorides with N2H5CI or N2H6CI2 in dilute HCl. Preparative methods for individual complexes vary mainly with the mole ratios of the reagents employed [23]. 

The electronic spectral and magnetic moment values of hydrazinium metal chloride hydrates are comparable to those reported for octahedral complexes of Co(II), Ni(II), and Cu(II) and square-planar complexes of Pt(II) and Pd(II) (Table 5.11). The magnetic moment values correspond to spin-only values for cobalt(II), nickel(II), and copper(II) ions. 

The reaction of copper, zinc, manganese, and iron chlorides with hydrazinium chloride (N2H5 or NiHg ) yields anhydrous hydrazinium metal chlorides of different compositions [25,26]. All the complexes are hygroscopic and air sensitive. The zinc complex in particular is deliquescent in nature. 

Hydrazinium metal haUde complexes are of two types anhydrous and hydrated. The hydrazinium chloride complexes, which are the most prevalent, are discussed here. 

The reaction between metal thiocyanates and hydrazinium thiocyanates cannot be used to prepare hydrazinium metal thiocyanate complexes. Consequently, an alternate method is employed, namely, the decomposition of hydrazinium metal hydrazine carboxylates with dilute thiocyanic acid (<5%) [27,28]. Hydrazinium metal hydrazine carboxylates complexes N2H5M(N2H3C00)3 H20, where M = Co and Ni, are prepared from metal nitrates, sulfates, or chlorides and hydrazine hydrate saturated with carbon dioxide. The dilute thiocyanic acid is prepared by adding barium thiocyanate trihydrate to dilute sulfuric acid. 

The solution should be free from the following, which either interfere or lead to an unsatisfactory deposit silver, mercury, bismuth, selenium, tellurium, arsenic, antimony, tin, molybdenum, gold and the platinum metals, thiocyanate, chloride, oxidising agents such as oxides of nitrogen, or excessive amounts of iron(III), nitrate or nitric acid. Chloride ion is avoided because Cu( I) is stabilised as a chloro-complex and remains in solution to be re-oxidised at the anode unless hydrazinium chloride is added as depolariser. 

In the application of the polarographic method of analysis to steel a serious difficulty arises owing to the reduction of iron(III) ions at or near zero potential in many base electrolytes. One method of surmounting the difficulty is to reduce iron(III) to iron(II) with hydrazinium chloride in a hydrochloric acid medium. The current near zero potential is eliminated, but that due to the reduction of iron(II) ions at about - 1.4 volts vs S.C.E. still occurs. Other metals (including copper and lead) which are reduced at potentials less negative than this can then be determined without interference from the iron. Alternatively, the Fe3 + to Fe2+ reduction step may be shifted to more negative potentials by complex ion formation. 

Military propellants are based on relatively powerful oxidisers and fuels of high calorihc value in order to develop an improved thrust or impulse. Thus the most commonly-used oxidisers are potassium perchlorate, ammonium perchlorate or more esoteric compounds such as hydrazinium nitroformate. Metallic fuels include aluminium, magnesium and beryllium, while binders are mainly hydrocarbons such as polybutadiene, polyisobutylene, polyurethane or poly(vinyl chloride) (PVC) as presented in Table 3.2. 

FERRIC OXIDE (1309-37-1) FcjO, Violent reactions with powdered aluminum (thermite reaction), hydrogen peroxide, calcium disilicide (thermite reaction), ethylene oxide (may cause explosive polymerization), calcium hypochlorite, hydrazine, hydrogen trisulfide, powdered magnesium. Contact with carbon monoxide may cause fire or explosion. Incompatible with calcium carbide (powdered), chlorides, guanidinium perchlorate, metal acetylides. Contact with the explosive hydrazinium diperchlorate or ammonium perchlorate can increase heat-, mechanical shock-, or friction sensitivity. Incompatible with aluminum-magnesium-zinc alloys. Spent material... 

FERROUS CHLORIDE TETRA-HYDRATE (7758-94-3) FeCl Contact with ethylene oxide may initiate polymerization. Reacts violently with reducing agents, including hydrides, nitrides, and sulfides acrolein, alcohols, chlorine trifluoride, ethers, fluorine, hydrazine, hydrazinium perchlorate, hydrogen peroxide, finely divided aluminum or magnesium, peroxyfuroic acid, sodium acetylide. Sensitizes most organic azides which are unstable shock and heat-sensitive explosives. Forms explosive materials with l,3-di(5-tetrazoyl)triazene, potassium,sodium. Incompatible with glycidol, isopropyl chlorocarbonate, nitrosyl perchlorate, sodium borohydride. Aqueous solution attacks metals. 

MERCURY(n) NITRATE (10045-94-0, anhydrous 7783-34-8, monohydrate) Hg(N03)2 H,0 Noncombustible solid. Light sensitive. A powerful oxidizer accelerates the burning of combustible materials. Violent reaction, or may form explosive materials, with reducing agents, including hydrides, nitrides, phosphorus, stannous chloride, and sulfides alkyl esters (forms explosive alkyl nitrates) combustible materials (especially if finely divided), phosphinic acid, hypophosphoric acid, metal powders petroleiun hydrocarbons. Forms heat- and/or shock-sensitive compounds with acetylene (forms explosive mercmy acetylide), ethanol and other alcohols (may form explosive mercury fulminates), ferrocene, isobutene, phosphine gas (forms heat- and shock-sensitive precipitate) potassiiun cyanide, sulfur. Incompatible with strong acids, acetic anhydride, ammonia, ammonium hexacyanofenate(II), organic azides, citric acid, hydrazinium perchlorate, isopropyl chlorocarbonate, nitrosyl perchlorate, sodium thiosulfate, sulfamic acid, thiocyanates, hydrozoic acid, methyl isocyanoacetate, sodium peroxyborate, trinitrobenzoic acid, urea nitrate. Aqueous solution corrodes metals. 

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