Oxalates, effect

Knight, W. G., Dudley, L. M. Jurinak, J. J. (1992). Oxalate effects on solution phosphorus in a calcareous soil. Arid Soil Research Rehabilitation, 6, 11-20. 

In addition to catalyzing the oxidation of many compounds, LiP is also able to catalyze reductive reactions in the presence of electron donors such as EDTAor oxalate (Fig. 7) (6, 77). Veratryl alcohol is a free radical mediator in these reactions. The electron donors appear to be oxidized by a LiP generated veratryl alcohol cation radical. The resulting anion radical can catalyze the reduction of good electron acceptors such as cytochrome c, nitroblue tetrazolium, and oxygen. Evolution of CO2 from EDTA or oxalate effectively drives the reductive reactions. Similar reactions have also been observed with the manganese dependent peroxidases in the presence of quinones (20). Early work performed in our laboratory showed that these reductive mechanisms are not involved in TNT reduction. However, these reactions may be involved in other steps in TNT metabolism. 

Two nucleation processes important to many people (including some surface scientists ) occur in the formation of gallstones in human bile and kidney stones in urine. Cholesterol crystallization in bile causes the formation of gallstones. Cryotransmission microscopy (Chapter VIII) studies of human bile reveal vesicles, micelles, and potential early crystallites indicating that the cholesterol crystallization in bile is not cooperative and the true nucleation time may be much shorter than that found by standard clinical analysis by light microscopy [75]. Kidney stones often form from crystals of calcium oxalates in urine. Inhibitors can prevent nucleation and influence the solid phase and intercrystallite interactions [76, 77]. Citrate, for example, is an important physiological inhibitor to the formation of calcium renal stones. Electrokinetic studies (see Section V-6) have shown the effect of various inhibitors on the surface potential and colloidal stability of micrometer-sized dispersions of calcium oxalate crystals formed in synthetic urine [78, 79]. 

The residue was dissolved in MeOH (20 cm ) and added slowly, with stirring, to a solution of anh. Oxalic acid (5.40g, 60mmol) in MeOH. Complete precipitation was effected by adding Et O (50 cm ) to the mixture and cooling it to -2(fC."... 

Diethyl oxalate (29.2 g, 0.20mol) and 4-bromo-2-nitrotoluene (21.6 g, O.lOmol) were added to a cooled solution of sodium cthoxide prepared from sodium (4.6 g, 0.20 mol) and ethanol (90 ml). The mixture was stirred overnight and then refluxed for 10 min. Water (30 ml) was added and the solution refluxed for 2h to effect hydrolysis of the pyruvate ester. The solution was cooled and concentrated in vacuo. The precipitate was washed with ether and dried. The salt was dissolved in water (300 ml) and acidified with cone. HCl. The precipitate was collected, washed with water, dried and recrystallizcd from hexane-EtOAc to give 15.2 g of product. 

Time—intensity emission profiles have provided quantitative mechanistic information on the effects of the oxalate stmcture, catalyst, oxidant, and... 

In acidic solution, the degradation results in the formation of furfural, furfuryl alcohol, 2-furoic acid, 3-hydroxyfurfural, furoin, 2-methyl-3,8-dihydroxychroman, ethylglyoxal, and several condensation products (36). Many metals, especially copper, cataly2e the oxidation of L-ascorbic acid. Oxalic acid and copper form a chelate complex which prevents the ascorbic acid-copper-complex formation and therefore oxalic acid inhibits effectively the oxidation of L-ascorbic acid. L-Ascorbic acid can also be stabilized with metaphosphoric acid, amino acids, 8-hydroxyquinoline, glycols, sugars, and trichloracetic acid (38). Another catalytic reaction which accounts for loss of L-ascorbic acid occurs with enzymes, eg, L-ascorbic acid oxidase, a copper protein-containing enzyme. 

The pH effect in chelation is utilized to Hberate metals from thein chelates that have participated in another stage of a process, so that the metal or chelant or both can be separately recovered. Hydrogen ion at low pH displaces copper, eg, which is recovered from the acid bath by electrolysis while the hydrogen form of the chelant is recycled (43). Precipitation of the displaced metal by anions such as oxalate as the pH is lowered (Fig. 4) is utilized in separations of rare earths. Metals can also be displaced as insoluble salts or hydroxides in high pH domains where the pM that can be maintained by the chelate is less than that allowed by the insoluble species (Fig. 3). 

Oxalic acid Beneficial reduces effects of CO2, salt water, dilute acetic acid... 

Novolacs are usually made under acidic conditions. Oxalic, sulfuric, toluene sulfonic, phenyl sulfonic, methane sulfonic, hydrochloric, and phosphoric acids are the most common catalysts, though nearly any moderately strong acid will probably do. Often selection of the acid has significant effects on the resultant polymer structure or performance. Sometimes acids are selected for their volatility, as it may be necessary to distill the acid off in some processes. 

The reactor has been successfully used in the case of forced precipitation of copper and calcium oxalates (Jongen etal., 1996 Vacassy etal., 1998 Donnet etal., 1999), calcium carbonate (Vacassy etal., 1998) and mixed yttrium-barium oxalates (Jongen etal., 1999). This process is also well adapted for studying the effects of the mixing conditions on the chemical selectivity in precipitation (Donnet etal., 2000). When using forced precipitation, the mixing step is of key importance (Schenk etal., 2001), since it affects the initial supersaturation level and hence the nucleation kinetics. A typical micromixer is shown in Figure 8.35. 

Garside, J., Brecevic, Lj. and Mullin, J.W., 1982. The effect of temperature on the precipitation of calcium oxalate. Journal of Crystal Growth, 57, 233-240. 

Table 1. Effect of Temperature of Decomposition of the Product of Reaction of Pentafluorophenyllithium with Dimethyl Oxalate on Product Distribution [JJ]...

The crystal structure of many compounds is dominated by the effect of H bonds, and numerous examples will emerge in ensuing chapters. Ice (p. 624) is perhaps the classic example, but the layer lattice structure of B(OH)3 (p. 203) and the striking difference between the a- and 6-forms of oxalic and other dicarboxylic acids is notable (Fig. 3.9). The more subtle distortions that lead to ferroelectric phenomena in KH2PO4 and other crystals have already been noted (p. 57). Hydrogen bonds between fluorine atoms result in the formation of infinite zigzag chains in crystalline hydrogen fluoride... 

The classical methods used to separate the lanthanides from aqueous solutions depended on (i) differences in basicity, the less-basic hydroxides of the heavy lanthanides precipitating before those of the lighter ones on gradual addition of alkali (ii) differences in solubility of salts such as oxalates, double sulfates, and double nitrates and (iii) conversion, if possible, to an oxidation state other than -1-3, e g. Ce(IV), Eu(II). This latter process provided the cleanest method but was only occasionally applicable. Methods (i) and (ii) required much repetition to be effective, and fractional recrystallizations were sometimes repeated thousands of times. (In 1911 the American C. James performed 15 000 recrystallizations in order to obtain pure thulium bromate). 

However, solubility, depending as it does on the rather small difference between solvation energy and lattice energy (both large quantities which themselves increase as cation size decreases) and on entropy effects, cannot be simply related to cation radius. No consistent trends are apparent in aqueous, or for that matter nonaqueous, solutions but an empirical distinction can often be made between the lighter cerium lanthanides and the heavier yttrium lanthanides. Thus oxalates, double sulfates and double nitrates of the former are rather less soluble and basic nitrates more soluble than those of the latter. The differences are by no means sharp, but classical separation procedures depended on them. 

In contrast to the facile condensation of o-nitrotoluene with diethyl oxalate, other a-alky] nitrobenzenes are sluggish to react with diethyl oxalate or fail to react at all. It has been suggested that this is due both to steric and electronic factors effected by the alky] group, which destabilizes the methylene group in regard to formation of the carbanion. ... 

Meyers has demonstrated that chiral oxazolines derived from valine or rert-leucine are also effective auxiliaries for asymmetric additions to naphthalene. These chiral oxazolines (39 and 40) are more readily available than the methoxymethyl substituted compounds (3) described above but provide comparable yields and stereoselectivities in the tandem alkylation reactions. For example, addition of -butyllithium to naphthyl oxazoline 39 followed by treatment of the resulting anion with iodomethane afforded 41 in 99% yield as a 99 1 mixture of diastereomers. The identical transformation of valine derived substrate 40 led to a 97% yield of 42 with 94% de. As described above, sequential treatment of the oxazoline products 41 and 42 with MeOTf, NaBKi and aqueous oxalic acid afforded aldehydes 43 in > 98% ee and 90% ee, respectively. These experiments demonstrate that a chelating (methoxymethyl) group is not necessary for reactions to proceed with high asymmetric induction. 

Figure 8 Effect of acid concentration on the grafting of cotton linters. [KMn04] = 0.06 N [monomer] = 1 mol/g cell liquor ratio 1 50 T = 50°C t = 1 h. (—) Oxalic acid (----) sulfuric acid.

Molybdenum tends to be protected by vanadium in aerated 7 1 % hydrochloric acid and it receives a high degree of protection when coupled with copper in this medium. Molybdenum corrodes somewhat faster than normal in 3 1 % nitric acid when coupled with tungsten. It is not affected by contact with titanium in 3-1% nitric acid. It is protected by aluminium and copper in aerated 10% formic acid and by aluminium in air-aerated 9% oxalic acid. In the latter solution, copper had only a slight protective effect when coupled with molybdenum. 

On the other hand, the provision of vast numbers of minute nuclei assists the phosphate coating reaction to start at a multitude of centres, resulting in a finely crystalline coating. This effect can be obtained chemically by a predip in a solution of sodium phosphate containing minutely dispersed traces of titanium or zirconium salts or in weak solution of oxalic acid. This type of pre-dip entirely eliminates any coarsening effect due to previous treatment in strong alkalis or acids. 

Comparison of Ca3(POi)2, Ca(C204), and Mg3(P04)2. The effects of cation and anion composites were tested by comparing the dissolution of Ca3(P04)2, Ca(C204), andMg3(P04)2 at pH 7 (Table 10). The dissolution of Ca3(P04)2 is achieved more effectively with X than with EDTA. However, when the anion is oxalate, the dissolution of Ca2+ is drastically reduced with X. EDTA can dissolve Ga(C204) to the same extent as Ca3(P04)2, i.e. the anion effect is insignificant. A better separation of Ca2+ from oxalate anion may be achieved by EDTA. 

Dissolution of Human Urinary Calculi in Vitro. Five human urinary calculi containing various proportions of Ca3(P04)2, Ca(C204), CaC03, and MgNH4(P04) were subjected to similar dissolution tests at pH 7 (Table 11). The same dissolution patterns as those of the model phosphate and oxalate calculi are found. That is, for phosphate calculi no. 1-4, X is more effective than [18]aneN6 or EDTA and for oxalate calculus no. 5, EDTA is best. 

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