Nitrate interactions

Hydrogen Peroxide. An explosion occurred 10 minutes after a sample of permonosulfonic acid, which was prepared by reacting chlorosulfonic acid and 90% hydrogen peroxide and then stored overnight at 0°C, was removed to a test-tube rack.4 Phosphorus. Explosive reaction with yellow phosphorus above 25°C.5 Silver Nitrate. Interaction with chlorosulfonic acid is violent, with nitrosulfuric acid being formed.6... 

Flynn, K. J., and Fasham, M. J. R. (1997). A short version of the ammonium-nitrate interaction model. 

This report also describes two new examples of nitrato-metallate coordination compounds which involve a phosphorus-containing ligand. One is the complex [AgL2N03] and the other the blue diamagnetic cobalt(I) complex anion [CoL(N03)2] Of the more than 100 compounds reported in the literature, which are suspected to contain coordinated nitrate, the 12 examined by x-ray diffraction technics are listed in Table II. Two reviews on metal-nitrate interactions have appeared recently (3, 19), so only some general observations will be made here. 

Evidence to support this "counterion modified" model comes from the investigation of hydrated Ln(NC>3)Cl2 prepared in the usual way in water (LnCl3, AgN03). The lanthanide(III) chlorides themselves show little or no catalytic activity for nitrations. A possible rationale for this is obtained by noting that HC1 is a poor activator of nitric acid in nitration chemistry since it is not sufficiently acidic to protonate nitric acid. However, the IR spectra of the Ln(NC>3)Cl2 salts are essentially identical to those of Ln(N03)(0Tf)2 indicating that the chloride ions are outer sphere in these complexes. Additionally the nitrate bands show the same trend as demonstrated for the triflate series (e.g., for La(N03)Cl2 the characteristic nitrate stretch is observed at 1459 cm1 and for Yb(NC>3)Cl2 the band appears at 1497 cm-1)- This indicates that the lanthanide chlorides are capable of activating nitric acid (via metal-nitrate interactions) but critically, the counterion (i.e. chloride) is incapable of fulfilling its role (in whatever capacity that may be) and hence no nitration occurs. 

The influence of marine aerosol was manifested in several locations by a clear contribution of sea salt to the mass of PMio in the region and chloride deficit is due to the reaction of sea salt with acidic anions like sulfates and nitrates. Also, nitrate interacts with mineral dust to lead to N2O5 high by hydrolysis converts into nitric acid in the atmosphere. 

O Rourke M, JiangX-J. Sildenafil/nitrate interaction. Circulation (2000) 101, e90. 

The lanthanide-nitrate interaction in anhydrous acetonitrile was investigated by means of conductimetry, vibrational spectroscopy, and luminescence measurements which are very sensitive to changes in the first solvation sphere of the metal ion (Bunzli and Choppin 1989). Conductimetiic data on 0.0001-0.01 M solutions of europium or terbium trinitrate in anhydrous acetonitrile indicate that no dissociation occurs. The vibrational spectra show the presence of coordinated acetonitrile and the nitrato group frequencies are consistent with bidentate anions of approximate C2v local symmetry (Bunzli et al. 1978). When the concentration of nitrate is increased, the formation of [R(N03) ] "b species (n>3) is clearly evidenced in the FT-IR spectra (Mabillard 1983). The coordination numbers determined for Nd, Eu, Tb and Er in solutions containing an excess of nitrate are constant (9.9 0.3) and correspond to the formation of pentanitrato [R(N03)5] species, in which the nitrate ions are bonded in a bidentate fashion and which do not contain any coordinated acetonitrile molecule. The strong nitrate/europium interaction is evidenced when water is added to acetonitrile solutions of europium trinitrate. The first two acetonitrile molecules are quantitatively replaced by water molecules, but the replacement of the remaining solvent molecules is difficult to achieve and requires... 

The lanthanum-nitrate interaction was studied in anhydrous methanol by La NMR (Bunzli et al. 1987), but the absolute stability constants could not be evaluated. The interaction with neodymium, europium and erbium was investigated by UV-VIS spectroscopy in aqueous methanol by Silber et al. (1990) and Silber and Strozier (1987). Stability constants, as well as thermodynamic parameters were calculated. Table 7 lists the stability constants available for solutions with a low water content. 

Dimethylformamide. According to conductimetric measurements, europium or terbium nitrates are 2 1 (<0.02 M), or 1 1 (>0.02 M) electrolytes in DMF solutions (Biinzli and Yersin 1982, Biinzli and Vuckovic 1983). Krishnamurthy and Soundararajan (1966) also determined that the first solvation sphere contains one or two nitrato groups. Abrahamer and Marcus (1968) later deduced from the study of the absorption spectra that the R(Ill)/nitrate interaction in DMF was outer-sphere. Finally, using IR, Raman, and electronic absorption spectroscopic data Biinzli and Vuckovic (1984) concluded to inner-sphere R(IIl)/nitrate interaction in DMF solutions. Upon addition of nitrate, equilibria take place which involve mono-, di-, and possibly trinitrato complexes. For [Nd(N03) ] " + and n = 1, the apparent equilibrium ratio is estimated as K 110 30M . A more complicated situation occurs for Eu(lII) (Biinzli and Yersin 1982). Diluted solutions (0.05 M) contain at least three different solvates the predominant... 

Dimethylacetamide. The stability constants and enthalpy values for lanthanide-nitrate interactions in anhydrous DMA (R=La, Nd) have been determined by means of calorimetric titration (Airoldi et al. 1982). The experimental results support the existence of the iimer-sphere mono- and dinitrato complexes with the following formation constants A i = 17,. 2= 16 for lanthanum and K =25, K2 = 92 for neodymium (cf. table 7). The enthalpies of formation 1 (La 48.2, Nd l.OkJmol" ) and AH2 (La 23.1, Nd 8.3kJmor ) are all endothermic, although rather small. Finally, mononitrate complexes appear to be less stable for both La(III) and Nd(III) ions compared to the corresponding chloro- and bromo complexes (cf. tables 6, 7). 

Nitrate reductases from E. coli and other sources have been reviewed by Stouthamer (1976). When this organism is grown anaerobically on nitrate, the nitrate is capable of acting as the terminal acceptor of its electron transport chain, being reduced to nitrite in the process. Apart from molybdenum, where the nitrate interacts, the enzyme also contains in its molecule several iron-sulfur centers and, in some preparations, heme as well. In the conventional assay, reduced benzyl viologen serves as electron donor. 

With this mode of acetyl nitrate interaction with the acid site proton, further calculations were done to determine stable minima and transition states for the nitration of toluene at the para site and both of the ortho sites. Although the energetics suggest that addition of the nitronium moiety to the toluene to form a tt-complex appears to be equally likely at all three electrophilic attack sites, the stabilization of... 

It is conveniently prepared in the laboratory by the interaction of sulphanil-amide and guanidine (from guanidine nitrate and sodium methoxide solution) the resulting guanidine salt of sulphanilamlde decomposes upon heating at 150-160° into sulphaguanidine and ammonia ... 

The effect of aromatic substrates on the formation of N02" is shown in the considerably increased substrate selectivity over that obtained with NO2+ salts. On the basis of the experimental data it is suggested that in these nitrations a weaker nitrating species than NO2+ must be involved in the primary interaction with the aromatic substrates. This incipient nitronium ion then attaches itself to the aromatics in a step giving high substrate selectivity. Whether the incipient nitronium ion is the nitracidium ion (H2NO3+), protonated acetyl nitrate (CH3COO—HN02 ) or probably a transition state of any of those unstable species to N02, in which water is loosened, but not yet completely eliminated, is difficult to say and no direct physical evidence is available. 

Ph.CH2.OMe, Ph.(CH2)2.0Me, Ph.(CH2)3.0Me (2-3, 3-4, 1-3), does not decrease steadily, but goes through a maximum. These two circumstances point to a specific -interaction in nitrations of the ethers with acetyl nitrate which is important with benzyl methyl ether, more important with methyl phenethyl ether, and not important with methyl phenpropyl ether. This interaction is the reaction with dinitrogen pentoxide already mentioned, and the variation in its importance is thought to be due to the different sizes of the rings formed in the transition states from the different ethers. 

The argtiments of Norman and his co-workers seem to give affirmative answers to the first and second of these questions, but it is doubtful if the available data further require such an answer for the third question. It can be argued that the crucial comparison made between the behaviour of benzyltrimethylammonium ion and protonated benzyl methyl ether is invalid, and that it is possible to interpret the results in terms of nitration by the nitronium ion, modified by protonation of the oxygen atom of the ether a case for the possible involvement of the nitro-nium ion in specific interaction leading to o-substitution has been made. ... 

A similar study of the nitration of 2,5-dichloro- and 2,5-dibromo-nitrobenxene under a variety of conditions has been made. At the very high acidities in oleum the o /)-ratio for nitration was less than unity. It increased with decreasing acidity of the medium and became greater than unity at roughly the acidity represented by 89-90 % sulphuric acid. The results were interpreted in terms of the interaction between the nitronium ion and the nitro group, but the results are complicated and the interpretation not compelling. 

These and other studies of the relative substituent effects of X and CH X in nitration were considered in terms of the transmission factor a of the methylene group. To avoid complications from conjugative interactions, attention was focussed mainly on substitution at the meta-position, and ct was defined in terms of partial rate factors by the equation ... 

Bismuth subcarbonate [5892-10 ] (basic bismuth carbonate) is a white or pale yellow powder that is prepared by interaction of bismuth nitrate and a water-soluble carbonate. The exact composition of this dmg depends on the conditions of precipitation it corresponds approximately to the formula (Bi0)2C02. It has been widely used as an antacid (183). 

Bismuth subgaHate [12552-60-2] (basic bismuth gaHate), Dermatol, is a bright yellow powder that can be prepared by the interaction of bismuth nitrate and gaUic acid in an acetic acid medium. It has been employed as a dusting powder in some skin disorders and as an ingredient of suppositories for the treatment of hemorrhoids (183,185). It has been taken orally for many years by colostomy patients in order to control fecal odors, but the dmg may cause serious neurological problems (186). 

Two techniques for sorption-spectroscopic determination of ascorbic acid have been proposed. The first one is the recovery by silica modified with tetradecyl ammonium nitrate of blue form of molibdophosphoric HPA in the presence of vitamin C. And the second one is the interaction between the ascorbic acid in solution and immobilized on silica ion associate of molibdophosphoric acid with lucigenine. The detection limits of vitamin C are 0.07 and 2.6 mg respectively. The techniques were successfully applied to the determination of ascorbic acid in fmit juices. 

Dividing the nitrate problem into topics is inevitably a somewhat arbitrary process, because of the interactions between the nitrogen fertilizer and the other factors . The various crops, for example, could arguably have come in this section rather than Section 2, while the structure of the soil, discussed in this Section,... 

Comparison of Table 5.4 and 5.7 allows the prediction that aromatic oils will be plasticisers for natural rubber, that dibutyl phthalate will plasticise poly(methyl methacrylate), that tritolyl phosphate will plasticise nitrile rubbers, that dibenzyl ether will plasticise poly(vinylidene chloride) and that dimethyl phthalate will plasticise cellulose diacetate. These predictions are found to be correct. What is not predictable is that camphor should be an effective plasticiser for cellulose nitrate. It would seem that this crystalline material, which has to be dispersed into the polymer with the aid of liquids such as ethyl alcohol, is only compatible with the polymer because of some specific interaction between the carbonyl group present in the camphor with some group in the cellulose nitrate. 

This is one approach to the explanation of retention by polar interactions, but the subject, at this time, remains controversial. Doubtless, complexation can take place, and probably does so in cases like olefin retention on silver nitrate doped stationary phases in GC. However, if dispersive interactions (electrical interactions between randomly generated dipoles) can cause solute retention without the need to invoke the... 

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