期刊
ANALYTICA CHIMICA ACTA
卷 1269, 期 -, 页码 -出版社
ELSEVIER
DOI: 10.1016/j.aca.2023.341427
关键词
Plumbane generation; Tetrahydridoborate; Potassium hexacyanoferrate(III); Atomic fluorescence spectrometry; Gas chromatography mass spectrometry; Mechanisms
The mechanisms controlling the generation of PbH4 in the reaction of Pb(II) with NaBH4 were investigated, with and without the presence of K3Fe(CN)6. PbH4 was identified for the first time using gas chromatographic mass spectrometry. It was found that without the additive, Pb(II) is converted to solid species and no volatile lead species can be detected. In the presence of K3Fe(CN)6, PbH4 is formed by the direct transfer of hydride from borane to lead atoms.
The mechanisms controlling the generation of PbH4 by reaction of inorganic Pb(II) with aqueous NaBH4 were investigated both in the presence and in the absence of the additive K3Fe(CN)6. For the first time PbH4 has been identified in analytical chemical vapor generation (CVG) by using gas chromatographic mass spectrometry (GC -MS), which allows the use of deuterium labelled experiments. In the absence of the additive, under reaction conditions typically employed for trace lead determination by CVG, Pb(II) is converted to solid species and no volatile lead species can be detected by either atomic or mass spectrometry for Pb(II) concentration up to 100 mg L-1. In alkaline conditions Pb(II) substrates are unreactive towards NaBH4. In the presence of K3Fe(CN)6, deuterium labelled experiments clearly indicated that the generated PbH4 is formed by the direct transfer of hydride from borane to lead atoms. Kinetic experiments were carried out to evaluate the rate of reduction of K3Fe (CN)6 by NaBH4, the rate of hydrolysis of NaBH4 both in the presence and in the absence of K3Fe(CN)6, and the rate of dihydrogen evolution following NaBH4 hydrolysis. The effect of delayed addition of Pb(II) to NaBH4-HCl- K3Fe(CN)6, and K3Fe(CN)6 to NaBH4-HCl-Pb(II) reaction mixtures on the efficiency of plumbane generation was investigated by continuous flow CVG coupled with atomic fluorescence spectrometry. The collected evidences, complemented with thermodynamic considerations and literature data, have made it possible to clarify long-standing controversial aspects related to the mechanism of plumbane generation and the role of K3Fe(CN)6 additive.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据