亚硫酸氢钠溶液稳定性的探讨

从溶液的酸度、空气及光照、温度等因素对亚硫酸氢钠溶液的稳定性及滴定反应进行实验探讨,选择三乙醇胺(TEA)、甲醛、二乙胺四乙酸二钠(EDTA-2Na)、盐酸羟胺四种常用的螯合剂或强还原剂进行试验,结果表明EDTA-2Na作为溶液的稳定剂效果最好,其次是甲醛,最后是盐酸羟胺。TEA因为其强碱性会降低溶液的稳定性而不宜作为稳定剂。     

Extraction of manganese(II) with dithizone and potassium thiocyanate on foam sorbents for spectrophotometric determination in silicates

A method for selective extraction of Mn(II) with dithizone and potassium thiocyanate has been described. The method involves formation of a Mn(II)-thiocyanate-dithizone complex in a hexamine medium containing potassium thiocyanate (2.8M), dithizone (5.5-6.5 x 10(-5)M) and hydroxylamine hydrochloride (0.25%) at pH approximately 6 followed by extraction of the complex on polyurethane foam using batch squeezing mode within 1 hr. The sorbed Mn-thiocyanate-dithizone complex is eluted with acetone and made alkaline with 0.5 ml of a stabilizer solution (19 ml 2M NH(3) solution + 1 ml 5% hydroxylamine hydrochloride). The absorbance of the solution is measured at 506 nm. The adverse effect due to Pb may be obviated by separating the Pb as the sulphate during decomposition of sample and that due to iron may be removed before extraction of Mn by any suitable method. The other interfering elements (Cd, Zn, Ni, Co, Cu, etc.) are masked with KCN (6 x 10(-3)M optimum) solution. The method obeys Beer's Law from 0.1 to 2.0 mug Mn/ml. The method has been applied to various silicates, carbonates and glasses.     

The determination of metallic iron,nickel and cobalt in reduced ores and oxides

A procedure is described for the determination of metallic iron, nickel and cobalt in reduced ores and oxides. The metallic phases are dissolved in brominemethanol solution, excess of bromine is destroyed by reaction with hydroxylamine hydrochloride and the analysis is completed by atomic absorption spectrophotometry. Solution of oxide phases is not observed if free or combined water is removed from the samples. Results are presented for an ore and standard alloys.     

超声辐射下水溶液中芳醛肟的合成

在没有催化剂条件下, 芳香醛与盐酸羟胺的水溶液经超声辐射于室温反应, 可以72%～98%收率得到肟. 该方法具有操作简便、反应条件温和、反应时间短、对环境友好等优点.     

A chemical concentration x-ray determination of selenium in copper-, nickel-and iron-base alloys

A method is described for the determination of selenium in various metals and alloys at concentrations of 3-100ppm. A chemical separation is made by filtration after reduction of the selenious acid to elemental selenium with hydroxylamine hydrochloride. The pure selenium product is readily analysed by X-ray fluorescence; the method is free from errors due to matrix effects. The relative standard deviation is 6 % for a copper-nickel alloy at the 60 ppm level.     

紫尿酸–Fe(Ⅲ)分光光度法测定盐酸羟胺

在碱性介质及溴化十六烷基吡啶存在条件下,盐酸羟胺与Fe(Ⅲ)–紫尿酸体系发生显色反应形成离子缔合物,该离子缔合物在635 nm波长处有一个吸收峰,其表观摩尔吸光系数ε=2.05×104 L/(mol·cm),据此建立了测定盐酸羟胺的间接分光光度法。盐酸羟胺的质量浓度在0~2.4 mg/L范围内与吸光度与呈良好的线性,线性相关系数r=0.999 8,方法的检出限为0.01 mg/L。将该方法用于盐酸羟胺的测定,其测定结果与国标法测定结果相吻合,加标回收率为95.0%~104.0%,测定结果的相对标准偏差为0.51%~1.29%(n=5)。该方法灵敏度高,操作简便,可用于盐酸羟胺含量测定。     

Chemical method for removal of impurities impairing the quality of commercial 1,4-butanediol produced by the reppe method

Quantitative dependence of the amount of impurities in commercial 1,4-butanediol that affect the carbonyl number, γ-hydroxybutyraldehyde and its acetate with 1,4-butanediol, on the service life of the catalyst was determined. Hydrazine hydrate, 2,4-dinitrophenylhydrazine, and hydroxylamine hydrochloride were studied as reagents binding these impurities and raising the content of the main substance in the target product. A procedure is suggested for obtaining purified 1,4-butanediol. The optimal reagent is a mixture of a 30% aqueous solution of hydrazine hydrate with hydrochloric acid.     

Determination of chromium in low-alloy steels by atomic-absorption spectrophotometry

Iron causes severe depression of the signal in determination of chromium by atomic-absorption spectrophotometry in an air-acetylene flame. This effect can be eliminated by addition of hydroxylamine hydrochloride and use of a fuel-rich flame. Addition of iron to the standard solutions is not necessary for up to 300 ppm of iron in the test solution.     

Reducing elution method for copper(II) in cation-exchange chromatography by hydroxylamine hydrocloride solution

The cation-exchange Chromatographic behaviour of copper and several other metals in hydroxylamine hydrochloride solution has been investigated. At 50 degrees copper(II) is reduced to copper(I) which is eluted quickly in a narrow band and easily separated from other metals such as zinc, nickel, cobalt and iron.     

Sequential and rapid determination of Po-210, Bi-210 and Pb-210 in natural waters

A sequential and rapid separation method for the determination of radon daughter nuclides, Pb-210, Bi-210 and Po-210 has been developed for application to natural waters. Rapid separation is attained by the use of the same hydrochloric acid solution. After isolation of the three radionuclides from the sample by co-precipitation with added Fe³⁺, polonium isotopes are first spontaneously deposited onto a silver disc from a 0.5N hydrochloric acid solution. Next, bismuth isotopes are electrodeposited onto a platinum net cathode coupled with a platinum coil anode at 1.2 V. Finally, lead isotopes are electrodeposited onto a platinum net cathode at 1.8 V from the remaining solution by adding hydroxylamine hydrochloride as an anodic depolarizer. This method can be applied to meteorological precipitation samples where these three nuclides are separated within 10 hr after the sampling with chemical yields of more than 80% for Po-210 and Bi-210 and more than 70% for Pb-210. This method is applicable to other environmental water samples.     

Benzocaine Determination in Pharmaceutical Preparations

Abstract

A new sensitive method for rapid and accurate determination of benzocaine via hydroxamic acid formation is described. The solution of hydroxylamine hydrochloride is reacted with benzocaine in alkaline medium to give corresponding hydroxamic acid (II) which forms the purple coloured complex with FeCl₃ in acidic medium, having a maximum absorbance at 530 nm. The commonly present additives such as Tyrothricin, Propylene glycol, Glycerin do not show any interference except Quiniodochlor whose interference was eliminated by extracting it with alcohol and removal of waxy substances with a mixture of water and HCL (17.5 :2.5).     

盐酸羟胺的间接分光光度法测定

拟定了在铁（Ⅲ）—２－［２－（６－甲基苯并噻唑）偶氮］－５－二乙氨基苯甲酸（６ＭｅＢＴＡＥＢ）络合物和十二烷基硫酸钠存在下盐酸羟胺的间接分光光度测定方法,回收试验表明该法准确可靠,方便快捷。同时测定了盐酸羟胺与Ｆｅ（Ⅲ）－６＿Ｍｅ＿ＢＴＡＥＢ络合物的反应比。     

Comparison of the thermal decomposition behavior for members of the hydroxylamine family

In the present work the thermal stability of some members of the hydroxylamine family was studied using adiabatic calorimetry. The study included aqueous solutions of hydroxylamine free base, hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine-o-sulfonic acid of concentrations typically used in industry. Also, the catalytic effect of metal surfaces of stainless steel, carbon steel, and titanium was studied. From the solutions studied HA is the most reactive with higher maximum temperature, pressure, non-condensable pressure, and lower time to maximum rate. HA maximum heat rate is at least ∼3 times higher than that of the other solutions studied, and the pressure generation rate is ∼13 times higher. All decompositions were catalyzed by stainless steel, but only HA was catalyzed significantly by titanium metal. Solid hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine-o-sulfonic acid exhibited stability up to ∼60 °C. Hydroxylamine 100% was not studied because it is not readily available, is not used industrially, and is known to be unstable at room temperature. A violent reaction was measured for solid hydroxylamine sulfate that generated a heat rate >500 °C/min and pressure rate >5200 psia/min before the sample cell was completely destroyed by the generated pressure.     

Synthesis,characterization, and biological activity of N‐(4‐acetylphenyl)maleimide and its oxime,carbazone, thiosemicarbazone derivatives and their polymers

A new type of maleimide monomer, N‐(4‐acetylphenyl)maleimide (NAPMI), was synthesized. The oxime, carbazone, and thiosemicarbazone derivatives of NAPMI were prepared with hydroxylamine hydrochloride, semicarbazide hydrochloride, and thiosemicarbazide hydrochloride, respectively. Radical homopolymerization of NAPMI and its derivatives were prepared at 60 °C in dimethyl sulfoxide solution with azobisisobutyronitrile as an initiator. The monomers and theirs homopolymers were characterized with Fourier transform infrared and NMR techniques. The glass‐transition temperatures, thermal stability, and ultraviolet stability of the polymers are compared. The activation energies of the thermal degradation of polymers were calculated by the Kissinger method. The antibacterial and antifungal effects of the monomers and polymers were also investigated on various bacteria and fungi. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1942–1951, 2003     

A Facile One-Pot Conversion of Aldehydes into Nitriles

A facile one-pot synthesis of nitriles starting with aldehydes has been developed employing hydroxylamine hydrochloride in dimethylsulfoxide at 100°C.     

Reaction of 2-dimethylaminomethylene-1,3-diones with dinucleophiles. X. synthesis of 5-substituted ethyl or methyl 4-isoxazolecarboxylates and methyl 4-(2,2-dimethyl-1-oxopropyl)-5-isoxazolecarboxylate

Reaction of ethyl or methyl 2-dimethylaminomethylene-3-oxoalkanoates with hydroxylamine hydrochloride in methanol solution afforded in high yields the relative esters of 5-substituted 4-isoxazolecarboxylic acids II . These esters were hydrolyzed generally with concentrated hydrochloric acid-acetic acid mixtures to the corresponding carboxylic acids in satisfactory yields. Ethyl or methyl esters II isomerized with sodium ethoxide or methoxide, respectively, to the corresponding esters or hemiesters of 2-cyano-3-oxoalkanoic acids generally in excellent to satisfactory yields. Reaction of methyl 5,5-dimethyl-3-dimethylaminomethylene-2,4-dioxohexanoate with hydroxylamine hydrochloride afforded in moderate yield methyl 4-(2,2-dimethyl-1-oxopropyl)-5-isoxazolecarboxylate, which was converted by acid hydrolysis as above to 4-t-butyl-4-hydroxyfuro[3,4-d]isoxazol-6-(4H)-one.     

Photometric determination of traces of antimony with rhodamine b after sulfide precipitation

A method is described for the colorimetric determination of as little as a few tenths of a part per million of antimony in samples composed primarily of elements of atomic numbers 1–28 (e.g., geo materials).Antimony is isolated by sulfide precipitation in mineral acid medium after reduction of ferric iron with hydroxylamine hydrochloride, with final determination by rhodamine B-benzene extraction. The procedure provides for the presence of gallium, thallium, tungsten and gold.     

A simple method for the alpha-oxygenation of aldehydes

A mild, efficient and general method for the chemospecific alpha-oxygenation of aldehydes is described. Treatment of a series of aldehydes with N-tert-butyl-O-benzoyl hydroxylamine hydrochloride gives the corresponding alpha-oxygenated carbonyl via a proposed pericyclic rearrangement process.     

Isatin (indole-2,3-dione) in urine and tissues. Detection and determination by gas chromatography-mass spectrometry

A simple procedure based upon capillary column gas chromatography-mass spectrometry (GC-MS) is described for the detection and determination of isatin (indole-2,3-dione) in body fluids and tissues. After addition of 5-methylisatin as internal standard to urine or tissue homogenates, organic extracts are dried and derivatized successively with hydroxylamine hydrochloride and the reagent N-tert.-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA). The tert.-butyldimethylsilyl derivatives obtained show good GC-MS properties and allow quantification by selected-ion monitoring of m/z 333 (isatin) and m/z 347 (internal standard). Adult and newborn human urine output values lie in the ranges 0.4-3.2 mg/mmol of creatinine (5-30 mg per 24 h) and 0.002-0.518 mg/mmol of creatinine, respectively. There is a discontinuous regional distribution in rat tissues. The GC-MS properties of a number of derivatives formed by successive reaction of isatin with hydroxylamine hydrochloride (or methoxyaminehydrochloride or ethoxyamine hydrochloride) and MTBSTFA, bis(trimethylsiyl)trifluoroacetamide, pentafluoropropionic anhydride or pentafluorobenzyl bromide are also described.     

Conjugate base catalysed one-pot synthesis of pyrazoles from β-formyl enamides

A novel one-pot synthesis of pyrazoles has been accomplished by the reaction of β-formyl enamides with hydroxylamine hydrochloride catalysed by potassium dihydrogenphosphate in acid medium.