首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Carbon Disulfide Reactions with Atomic Transition-Metal and Main-Group Cations:Gas-Phase Room-Temperature Kinetics and Periodicities in Reactivity
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Carbon Disulfide Reactions with Atomic Transition-Metal and Main-Group Cations:Gas-Phase Room-Temperature Kinetics and Periodicities in Reactivity

机译:带有原子过渡金属和主族阳离子的二硫化碳反应:气相室温动力学和反应周期

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摘要

The reactions of 46 atomic-metal cations with CS_2 have been investigated at room temperature using an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer.Rate coefficients and products were measured for the reactions of fourth-period atomic ions from K~+ to Se~+,of fifth-period atomic ions from Rb~+ to Te~+ (excluding Tc~+),and of sixth-period atomic ions from Cs~+ to Bi~+.Primary reaction channels were observed leading to S-atom transfer,CS_2 addition and,with Hg~+,electron transfer.S-atom transfer appears to be thermodynamically controlled and occurs exclusively,and with unit efficiency,in the reactions with most early transition-metal cations (Sc~+,Ti~+,Y~+,Zr~+,Nb~+,La~+,Hf~+,Ta~+,and W~+) and with several main-group cations (As~+,Sb~+) and less efficiently with Se~+,Re~+ and Os~+.Other ions,including most late transition and main-group metal cations,react with CS_2 with measurable rates mostly through CS_2 addition or not at all (K~+,Rb~+,Cs~+).Traces of excited states (< 10%) were seen from an inspection of the observed product ions to be involved in the reactions with Mo~+,Te~+,Ba~+ and Au~+ and possibly Pt~+ and Ir~+.The primary products YS~+,ZrS~+,NbS~+,HfS~+,TaS~+,WS~+,ReS~+ and OsS~+ react further by S-atom transfer to form MS_2~+,and TaS_2~+ reacts further to form TaS_3~+.CS_2 addition occurs with the cations MCS_2~+,MS~+,MS_2~+,CS_2~+,and TaS_3~+ to form M+(CS_2)_n (n <= 4),MS~+(CS_2)_n (n <= 4),MS_2~+(CS_2)_n (n <= 3),(CS_2)_2~+ and TaS_3~+(CS_2).Up to four CS_2 molecules add sequentially to bare metal cations and monosulfide cations,and three to disulfide cations.Equilibrium constant measurements are reported that provide some insight into the standard free energy change for CS_2 ligation.Periodic variations in DELTA G~° are as expected from the variation in electrostatic attraction,which follows the trend in atomic-ion size and the trend in repulsion between the orbitals of the atomic cations and the occupied orbitals of CS_2.
机译:使用电感耦合等离子体/选择离子流管(ICP / SIFT)串联质谱仪在室温下研究了46种原子金属阳离子与CS_2的反应,并测量了第四周期反应的速率系数和产物从K〜+到Se〜+的原子离子,从Rb〜+到Te〜+的第五周期原子离子(不包括Tc〜+),以及从Cs〜+到Bi〜+的第六周期原子离子。在与大多数早期过渡金属阳离子的反应中,S-原子的转移似乎是热力学控制的,并且是唯一发生的,并且具有单位效率,这导致了S-原子的转移,CS_2的添加以及Hg〜+的电子转移。 (Sc〜+,Ti〜+,Y〜+,Zr〜+,Nb〜+,La〜+,Hf〜+,Ta〜+和W〜+),并带有几个主族阳离子(As〜+, Sb〜+),而与Se〜+,Re〜+和Os〜+的效率较低。其他离子,包括大多数较晚的过渡离子和主族金属阳离子,与CS_2的反应速率可测量,主要是通过添加CS_2或根本不添加(K 〜+,Rb〜+,Cs〜+)。T通过观察观察到的参与与Mo〜+,Te〜+,Ba〜+和Au〜+以及Pt〜+和Ir〜+反应的产物离子,可以看到激发态(<10%)。初级产物YS〜+,ZrS〜+,NbS〜+,HfS〜+,TaS〜+,WS〜+,ReS〜+和OsS〜+通过S原子转移进一步反应形成MS_2〜+和TaS_2 〜+进一步反应形成TaS_3〜+ .CS_2与MCS_2〜+,MS〜+,MS_2〜+,CS_2〜+和TaS_3〜+阳离子形成M +(CS_2)_n(n <= 4), MS〜+(CS_2)_n(n <= 4),MS_2〜+(CS_2)_n(n <= 3),(CS_2)_2〜+和TaS_3〜+(CS_2)。最多四个CS_2分子依次添加到裸金属阳离子和一硫化物阳离子,以及三个变为二硫化物阳离子。据报道,平衡常数测量为CS_2连接的标准自由能变化提供了一些见识。DELTA G〜°的周期性变化是由静电引力的变化所预期的。遵循原子离子尺寸的趋势以及原子阳离子的轨道与被占据的轨道之间的排斥趋势ls CS_2。

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