Determination of hydroxylamine

Von Breymann et al. [306] have described a method for the determination of hydroxylamine in seawater based on gas chromatography with electron capture detection. 

The structures of these molecules show the effects of intramolecular electrostatic interactions. Two examples are the lone pair—lone pair repulsion that is an important determinant of hydroxylamine and oxime conformations, and the intramolecular hydrogen bonding in hydroxamic acids that promotes the near-planarities of their —C(=0)—NO frameworks. 

Yashpe, J., Y. S. Halpern and N. A. Grossowicz quantitative method for the differential determination of hydroxylamine and (3-aspartyl hydroxamate in mixtures. Anal. Chem. 32, 518 (1960). 

Fig. 8-59. Determination of hydroxylamine in a weakly basic cleansing agent. - Separator column IonPac CS3 eluent 0.03 mol/L HC1 flow rate 1 mL/min detection D.C. amperometry at a Pt working electrode oxidation potential +0.8 V injection 50 pL sample (1 2000 diluted).

FLOW INJECTION ANALYSIS CHEMILUMINESCENCE DETERMINATION OF HYDROXYLAMINE HYDROCHLORIDE... 

Fig. 1. Analytical calibration graph for determination of hydroxylamine (conditions 1.20xl0 M hydrochloride acid, 5.00xl0 2M Na202 and 2.00 mL/min...

Flow Injection Chemiluminescence Determination of Hydroxylamine Hydrochloride 175... 

Table 3. Determination of hydroxylamine added to water samples (conditions 1.20 10 M hydrochloric acid, 5.00 10 2M Na202 and 2.00 mL/min flow rate).

The proposed method, based on the CL reaction between hydroxylamine and Na202, provides a simple and sensitive approach for the determination of hydroxylamine. No sample pre-treatment is necessary and the procedure is very rapid using the FIA technique. The dynamic range of the method is 3.00 10 7 - 5.00><10 6 M hydroxylamine with detection limit of 1.60><10 8 M hydroxylamine. 

G. C. M. Bourke, G. Stedman, and A. P. Wade, The Spectrophotometric Determination of Hydroxylamine Alone and in the Presence of Hydrazine by Flow Injection Analysis. Anal. Chim. Acta, 153 (1983) 277. 

Hydror lamines and amines. Sodium nitroprusside easily exchanges ligands photochemically, and this has been exploited for a sensitive method for the determination of hydroxylamine, with which it... 

Dissolve 5 g. of hydroxylamine hydrochloride in 10 ml. of water in a small conical flask and add a solution of 3 g. of sodium hydroxide in 10 ml. of water. Cool the solution in cold or ice water, and add 6 g. (7-6 ml.) of acetone slowly. Cool the flask, shake well, and leave overnight, during which time the oxime may crystallise out. If no crystals appear, cork the flask and shake vigorously when the acetoxime usually separates as colourless crystals. Filter the crystals at the pump, dry rapidly between filter paper (yield 2- 6 g.) and determine the m.p. (59°). Extract the filtrate with two 20 ml. portions of ether, and remove the solvent a further 0 - 5 g. of acetoxime (m.p. 60°) is obtained. Recrystallise from light petroleum, b.p. 40-60° CAUTION inflammable) to obtain the pure acetoxime, m.p. 60°. Acetoxime sublimes when left exposed to the air. 

The purity of a synthetic preparation of methylethyl ketone (C4H8O) can be determined by reacting the ketone with hydroxylamine hydrochloride, liberating HCl (see Table 9.10). In a typical analysis, a 3.00-mL sample was diluted to 50.00 ml and treated with an excess of hydroxylamine hydrochloride. The liberated HCl was titrated with 0.9989 M NaOH, requiring 32.68 ml to reach the end point. Report the percent purity of the sample, given that the density of methylethyl ketone is 0.805 g/mL. 

However, as the pH—rate plot shows, at very low pH the observed rate actually decreases. Because, as the preceding argument shows, rate-determining dehydration should result in a pH-dependent rate at low pH, this decreased rate must mean that the rds has changed. This is reasonable, for at pH values well below the pKg of hydroxylamine, the decreasing proportion of the hydroxylamine in the unprotonated form will decrease the rate of the initial addition. At some pH, then, the rate of the addition step will fall below that of the dehydration step, and the observed rate curve will lie lower than the rate predicted for the dehydration. 

One of the most important routes to isoxazole and isoxazoline rings involving the formation of the 1—5 and 2—3 bonds involves the condensation of hydroxylamine with a,/8-unsaturated carbonyl compounds. This method was previously widely used, but it is now of no preparative value, though it has been recently applied to determine the configuration of oximes. " The only new modification of this synthesis is the use of the acetals (27) of a,/8-acetylenic aldehydes for preparation of 5-substituted isoxazoles (28)... 

Two hydrogen-transfer systems have been developed that also give good yields of hydroxylamines. One uses 5% palladium-on-carbon in aqueous tetrahydrofuran with phosphinic acid or its sodium salt as hydrogen donor the other uses 5% rhodium-on-carbon in aqueous tetrahydrofuran and hydrazine as donor. These systems are complementary and which is the better may depend on the substrate (36). The reductions cannot be followed by pressure drop, and both require analysis of the product to determine when the reduction should be terminated. 

Menthylhydroxylamine may be used to form hydroxylamine derivatives for the determination of carbohydrates [20]. 

Aromatic nitro and nitroso compounds are easily reduced at carbon and mercury electrodes. Other nitro compounds such as nitrate esters, nitramines, and nitrosamines are also typically easily reduced. The complete reduction of a nitro compound consists of three two-electron steps (nitro-nitroso-hydroxylamine-amine). Since most organic oxidations are only two-electron processes, higher sensitivity is typically found for nitro compounds. Several LCEC based determination of nitro compounds have been reported... 

Hardcastle JL, Compton RG (2001) The electroanalytical detection and determination of copper in heavily passivating media ultrasonically enhanced solvent extraction by N-benzoyl-N-phenyl-hydroxylamine in ethyl acetate coupled with electrochemical detection by sono-square wave stripping voltammetry analysis. Analyst 126 2025-2031... 

Vollmer et al. [4] compared the Hg(II) acetate method described in the Code of Federal Regulations for the determination of penicillamine in bulk drug and formulations with (i) a nonaqueous lithium methoxide titration, (ii) a nonaqueous HCLO4 titration, and (iii) a colorimetric method with hydroxylamine. Method (ii) was unsatisfactory for bulk determinations. Method (i) was less precise than the Hg(II) acetate method, but gave satisfactory results for bulk drug and capsule samples. Method (iii) was the only method that gave satisfactory results in the presence of EDTA. 

Bajic and Jaselskis [153] described a spectrophotometric method for the determination of nitrate and nitrite in seawater. It included the reduction of nitrate and nitrite to hydroxylamine by the zinc amalgam reactor (Jones reductor) at pH 3.4 and reoxidation of the product with iron (III) in the presence of ferrozine. Interference by high levels of nitrite could be eliminated with azide treatment. Levels of nitrate of 0.1 mg/1 could be detected with a precision of 3% in the presence of large amounts of nitrite and chloride. 

Three fundamental properties that play key roles in determining covalent and/or nonco-valent interactions are the electrostatic potential V(r), the ionization energy 7 (sometimes written IE) and the polarizability a. All three can be obtained experimentally. It is primarily in terms of these properties that we will examine the inter- and intramolecular interactions of hydroxylamines, oximes and hydroxamic acids. Accordingly we shall first briefly discuss F(r), I and a. 

Hydroxylamines, oximes and hydroxamic acids all have adjacent nitrogen and oxygen atoms, as part of their characteristic N—OH group. Since both of these atoms commonly have significant lone pairs, a major determinant of these molecules conformations is the need to minimize the repulsion between these lone pairs. This will be illustrated by the example of hydroxylamine, H2N—OH. 

Shah and Mehta described a calorimetric method for the estimation of diloxanide furoate in pharmaceutical formulations [27]. The method is based on its interaction with hydroxylamine in alkaline solution. This method was used for the determination of the drug either alone or when combined with other agents. 

The precipitation of cuprous acetylide was introduced into analytical chemistry for the quantitative determination of copper. Since cupric acetylide was dangerous to handle, Makowka [108] worked out a method in which cupric salts are previously reduced, e.g. with hydroxylamine, to cuprous salts, when the acetylide is precipitated. Cuprous salts in a solution of hydroxylamine are employed as reagents for acetylene (e. g. Pietsch and Kotowski [114]). 

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