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Effect of the ionic strength on the redox reaction of dicyanobis(bipyridine)iron(III)‐iodide in binary and ternary solvent systems
International Journal of Chemical Kinetics ( IF 1.5 ) Pub Date : 2020-08-27 , DOI: 10.1002/kin.21419
Rozina Khattak 1 , Muhammad Sufaid Khan 2 , Rizwan Ullah 3 , Zainab 1 , Sony 1 , Mahnoor Ali 1 , Wajeeha Rahman 1 , Faryal Hakeem 1 , Kainat Ayaz 1 , Zainab Bibi 1
Affiliation  

The redox reaction between dicyanobis(bipyridine)iron(III) and iodide ion follows first‐order kinetics in 10% (v/v) tertiary butyl alcohol‐water. The reaction was found first and zero order in iodide and dicyanobis(bipyridine)iron(III), respectively, at 0.06 M ionic strength and 293 ± 1 K. The thermodynamic parameters of activation such as EA (16.07 kJ mol−1), A (1 × 10−4 M s−1), ΔH# (13.6 kJ mol−1), ΔS# (−329.81 J K−1 mol−1), and ΔG# (90.1 kJ mol−1) were determined. The effect of the ionic strength on the rate constant leads to recognizing the stabilization or destabilization of the transition state complex that forms during the rate‐determining step of the reaction. The value of the zero‐order rate constant was decreased with increasing ionic strength that yielded a negative value of the slope in each binary and ternary solvent systems. This negative sign refers to the electron transfer between opposite charge carriers such as [FeIII(bpy)2(CN)2]+ and I during the rate‐determining step. The destabilization of the transition state complex is surfaced by the increasing slope, that is, 5 < 10 < 15% (v/v) tertiary butyl alcohol‐water with a gradual decrease in the rate constant. However, its stability emerges by relatively small values of the slope in 17.5 < 25 ≤ 30% (v/v) tertiary butyl alcohol‐water and 8:2:90 < 6:4:90% (v/v) dioxane: tertiary butyl alcohol: water with reasonably fast rate of reaction.

中文翻译:

离子强度对二元和三元溶剂体系中双氰基双(联吡啶)铁(III)-碘化物氧化还原反应的影响

双氰基双(联吡啶)铁(III)与碘离子之间的氧化还原反应遵循在10%(v / v)的叔丁醇-水中的一级动力学。在离子强度为0.06 M和293±1 K的碘化物和二氰基双(联吡啶)铁(III)中分别发现反应的第一级和零级。活化的热力学参数,例如E A(16.07 kJ mol -1),A(1×10 -4  M s -1),ΔH (13.6 kJ mol -1),ΔS (-329.81 JK -1  mol -1)和ΔG (90.1 kJ mol -1))确定。离子强度对速率常数的影响导致人们认识到在反应速率确定步骤中形成的过渡态络合物的稳定或不稳定。零阶速率常数的值随着离子强度的增加而减小,从而在每个二元和三元溶剂系统中产生的斜率均为负值。这个负的符号是指如[铁相反电荷载波之间的电子转移III(BPY)2(CN)2 ] +及我-在速率确定步骤中。过渡态络合物的失稳作用是通过增加的斜率显示出来的,即5 <10 <15%(v / v)的叔丁醇-水,速率常数逐渐降低。但是,在叔丁醇-水17.5 <25≤30%(v / v)和二恶烷:8:2:90 <6:4:90%(v / v)中,斜率的值相对较小,可以显示其稳定性。丁醇:水,反应速度相当快。
更新日期:2020-08-27
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