Metal nitrate hydrazines

Metal nitrate hydrazines are prepared by two different methods [23]. Method I... 

Metal nitrate hydrazines of the type M(N03)2(N2H4) are prepared by the conventional route, which involves the addition of alcoholic hydrazine hydrate to an aqueous solution of metal nitrate. Cobalt nitrate hydrazine, [Co(N03)2(N2H4)3], is prepared in a reaction mixture containing an aqueous solution of cobalt nitrate hexahydrate and hydrazine hydrate (1 3), at room temperature. The product is precipitated instantaneously in 96% yield by the addition of alcohol ... 

Metal nitrate hydrazines can also be prepared by dissolving the respective metal powders in a solution of ammonium nitrate in hydrazine hydrate ... 

The results of chemical analysis of most of the metal nitrate hydrazine complexes reveal that they form trihydrazine complexes of the type M(N03)2(N2H4)3. 

The infrared spectra of all metal nitrate hydrazines are identical. The probable assignments of frequencies are made on the basis of earlier studies on hydrazine and ionic nitrate as reported in Table 3.23. The t N n of N2H4 is observed at 960 cm, indicating the presence of hydrazine bridging between two metal ions. The characteristic infrared absorption frequencies observed at 1390,1050, and 820cm show the presence of ionic N03. The probable structure of the metal ion is an octahedral coordination with all 6N atoms contributed by N2H4 groups. 

The explosive properties of a series of 5 amminecobalt(III) azides were examined in detail. Compounds were hexaamminecobalt triazide, pentaammineazidocobalt diazide, cis- and traw.v-tetraamminediazidocobalt azide, triamminecobalt triazide [1], A variety of hydrazine complexed azides and chloroazides of divalent metals have been prepared. Those of iron, manganese and copper could not be isolated cobalt, nickel, cadmium and zinc gave products stable at room temperature but more or less explosive on heating [2]. Some polyammine azido-metal nitrates of Cr, Ni and Cu were found to be explosively photosensitive. Replacement of ammonia by triethanolamine gave compounds smoothly photodecomposing [3]. 

The use of metal nitrates provides a particularly convenient method for doping a host oxide with luminescent ions. Along with the yttrium nitrate, a luminescent rare earth ion such as Eu3+, can be added as a nitrate salt. In addition to yttria, alumina can also be prepared from aluminum nitrate and hydrazine (Ozuna et al., 2004) ... 

TIN(II) CHLORIDE (7772-99-8) SnClj A powerful reducing agent. Reacts violently with strong oxidizers, strong alkalis, bromine, bromine trifluoride (ignition), calcium carbide, chlorine, chlorine monofluoride, copper nitrate, ethylene oxide fluorine, hydrogen peroxide, nitrates, potassium, potassium dioxide, sodium, with risk of fire and explosions. Incompatible with calcium acetylide, hydrazine hydrate (forms explosive stannous dihydrazine chloride) metal nitrates. On small fires, use dry chemical powder (such as Purple-K-Powder), alcohol-resistant foam, or COj extinguishers. 

Typically, SCS involves a self-sustained exothermic reaction in a solution of metal nitrates (also known as oxidizer) and a reducing agent (fuels, e g. glycine, urea, hydrazine, glucose etc ). The reaction between fuel and oxidizer provides an optimum temperature and reaction enviromnent for synthesizing crystalline materials. The stoichiometric equiUbrium combustion reaction is usually described by the following scheme ... 

The description of crystal type and color of several metallic hydrazine nitrates are summarized in Table 13.8. The density of NHN is 2.07 g cm . Nickel and cobalt hydrazine nitrate are practically insoluble in common organic solvents (e.g., ethanol, acetone) and sparingly soluble in water (0.47 g 1 at 30 °C, 2.31 g 1 at 70 °C). NHN bums upon the action of 96 % sulfiuic acid, but weak acid makes it decompose more gently CoHN explodes in contact with concentrated sulfuric acid. NHN mildly reacts with a 10 % solution of sodium hydroxide and this can be used for producing a chemical decomposition. NHN is stable on exposure to sunlight and it hardly reacts at aU with common metals. Cobalt hydrazine nitrate is unstable and decomposes slowly, even in the presence of traces of moisture, changing in color from brown to greenish [16, 17]. 

The compounds M(N03)2(N2H4)3, where M " = Mn, Fe, Co, Ni, Zn, and Cd, are prepared by mixing hydrazine hydrate and metal nitrate salts in aqueous/alcoholic solution. 

Apart from the above applications, hydrazine hydrate is also used in preparing organic derivatives, like hydrazones and hydrazides such as carbohydrazide (CH), oxalyl dihydrazide (ODH), malonic acid dihydra-zide (MDH), tetra formal tris azine (TFTA) and so on, from the corresponding ketones and aldehydes. Hydrazones have been investigated as solid fuels in hybrid rockets [40]. The hydrazides have been exploited as combustible fuels with metal nitrate oxidizers in the preparation of nanocrystalline oxide materials [41]. 

In the preparation of nickel nitrate hydrazine [Ni(N03)2(N2H4)3] stoichiometric amounts of ammonium nitrate in hydrazine hydrate and nickel metal powder are allowed to react in the ratio of 2 3 1, respectively, at room temperature. The nickel metal dissolves exothermically with the evolution of hydrogen. The solid compound is obtained in 97% yield by the addition of alcohol. 

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. 

Metal hydrazine complexes of azide and nitrate have been investigated as initiators. For example, the synthesis of nickel nitrate hydrazine [Ni (N03)2(N2H4)2] described in Chapter 3 has been commercially developed for use as detonators (blasting caps) in China. 

Numerous explosives are based on hydrazine and its derivatives, including the simple azide, nitrate, perchlorate, and diperchlorate salts. These are sometimes dissolved in anhydrous hydrazine for propeUant appUcations or in mixtures with other explosives (207). Hydrazine transition-metal complexes of nitrates, azides, and perchlorates are primary explosives (208). 

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