Liquid phase Nitration

Liquid phase processes, such as hydrogenation, halogenation, oxidation, nitration, kylation, and so on... 

Similar to the alkylation and the chlorination of benzene, the nitration reaction is an electrophilic substitution of a benzene hydrogen (a proton) with a nitronium ion (NO ). The liquid-phase reaction occurs in presence of both concentrated nitric and sulfuric acids at approximately 50°C. Concentrated sulfuric acid has two functions it reacts with nitric acid to form the nitronium ion, and it absorbs the water formed during the reaction, which shifts the equilibrium to the formation of nitrobenzene ... 

Nitration of alkanes can be carried out in the gas phase at 400°C or in the liquid phase. The reaction is not practical for the production of pure products for any alkane except methane. For other alkanes, not only does the reaction produce mixtures of the mono-, di-, and polynitrated alkanes at every combination of positions, but extensive chain cleavage occurs. A free-radical mechanism is involved. ... 

H3PW12O40 catalyzed liquid phase nitration of aromatics - a green process without using H2SO4... 

HPA catalyzed liquid phase nitration was eairied out in a Teflon-lined stainless autoclave of 200 mL equipped with a magnetic stirrer. Reactants and HPA were quantitatively added to the autoclave, which was sealed and heated in an oil-bath. Products were analyzed by GC with OV-101 30 m capillary column and FID detector by using calibrated area normalization and internal standard method. All products were confirmed by GC-MASS analysis. 

Fig. 1. Temperature effect for liquid phase nitration of (a) benzene, (b) toluene and chlorobenzene.

Keggin type H3PW)2O40 is a stable, recyclable and effective catalyst for H2S04-free liquid phase nitration of bezene, chlorobenzene and toluene with nitric acid as a nitration agent. Higher para-selectivity of nitrotoluene was obtained, and the result implies that HPA can effectively catalyze the liquid phase nitration of various aromatics as an environmentally friendly nitration process. 

Liquid-liquid reactions occur between two or more liquid phases whereby a system consisting of an organic and an aqueous phase is applied most frequently. Usually reaction takes place in one phase only. Phase-transfer catalysts are sometimes used to make transfer of a reactant to the reacting phase easier. Among typical liquid-liquid reactions utilized in fine chemicals manufacture are nitrations with mixtures of nitric and sulphuric acid, conventional hydroxylations performed with hydrogen peroxide, esterifications, alkylations, brominations, and iodinations. 

A homogeneous mixture of diethyl ether and nitric acid decomposes vigorously after a latency period during which the medium splits into two liquid phases. One of them was attributed to the formation of ethyl nitrate, which is unstable. 

Liquid-liquid immiscible liquid phases reactions such as the nitration of toluene or benzene with mixed acids, and emulsion polymerisations. 

Nixan [Nitrocyclohexane] A process for making cyclohexane oxime (an intermediate in the manufacture of nylon) from benzene by liquid phase nitration, followed by hydrogenation of the nitrobenzene. Invented by Du Pont and operated from 1963 to 1967. 

Electrochemical aspects of liquid phase heterogeneous transformations [61-69] have also to be mentioned. In these cases, either the solid phase is a catalyst or the solid phase is a reaction partner. At least two coupled redox partners are present. The catalytic reduction of nitrate with molecular hydrogen in acidic aqueous phase at a solid catalyst... 

Nitrous acid/nitrite can also be oxidized in the aqueous solutions found in the atmosphere in the form of fogs, clouds, and particles. Nitrite is well known to be slowly oxidized in the dark to nitrate by dissolved oxygen in the liquid phase. However, it has been reported that the rate of this oxidation increases remarkably during freezing of the solution containing the nitrite (Takenaka et al., 1992, 1996). Figure 7.11, for example, shows the rate of nitrate formation in a nitrite solution at 25°C and in one with the cooling bath at — 21°C (Takenaka et al., 1992). This unusual phenomenon has also been observed with respect to the... 

Similar to the imidazolium ILs, very low solubility of the ammonium ILs was observed in alkanes. Eor example, the solubility of butyl(2-hydroxyethyl) dimethylammonium bromide, [(Ci)2C4HOC2N]Br, exhibited a simple eutectic system with immiscibility in the liquid phase in the IL mole fraction range from XjL = 0.02 to 0.70 [53] the other ammonium salt, (benzyl)dimethyl-alkylammonium nitrate, [Be(Ci)2C N] [NOJ showed very small solubility in the liquid phase in hexadecane and it was slightly better in hexane (immiscibility from XjL = 10 to 0.90) [99] for the ammonium salt with an alkane substituent only, didecyldimethylammonium nitrate, [(Cio)2(Q)2N][N03], the solubility in the liquid phase was better in hexane (immiscibility from XjL = 10 to 0.50) than in hexadecane, where the immiscibility was observed in the whole IL mole frachon [100]. In all systems with imidazolium and ammonium salts, an increase in the alkyl chain length of the alkane (solvent) resulted in a decrease of solubility. 

Agitation of liquid phases. It is produced by blowing the air or other gas (from a sparger etc) to ihe lower part of the container of liquid. This is usually done in cases when the containers are of such size or of such unsymmetrical shape as to make mechanical agitation ineffective or too expensive. Another case is when mechanical agitation is considered unsafe, as in the preparation of some expls. For instance, in die nitration... 

After shaking, the vials were centrifuged to remove the fines from the supernatant and an aliquot of the supernatant was counted against a standard of the particular formulated liquid phase. All experiments were performed in triplicate, at constant activity and Hg-carrier concentration (20 pg Hg/ ml) with controls (liquid phase without sorbent) to check for possible adsorption losses on the container. The experiments were carried out in nitrate and chloride media at pH 1-10. 

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