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Ladder Diagrams: Complexation Equilibria01:07

Ladder Diagrams: Complexation Equilibria

403
Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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EDTA: Auxiliary Complexing Reagents01:26

EDTA: Auxiliary Complexing Reagents

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EDTA titrations are usually carried out in highly basic conditions, where the fully deprotonated form of EDTA, Y4−, actively complexes with the free metal ions in the solution. Several metal ions precipitate as hydrous oxide (hydroxides, oxides, or oxyhydroxides) under these conditions, lowering the concentration of free metal ions in the solution. For this reason, auxiliary complexing agents or ligands such as ammonia, tartrate, citrate, or triethanolamine are used in EDTA titrations to...
648
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism01:37

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism

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Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
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Electrodeposition01:08

Electrodeposition

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Electrodeposition is a technique used to separate an analyte from interferents by electrochemical processes. Here, the analyte is a metal ion that can be deposited on an electrode immersed in the sample solution. The electrochemical setup consists of an anode and a cathode. When an electric current is applied to the setup, oxidation occurs at the anode. At the cathode, which consists of a large metal surface, metal ions undergo reduction and deposit onto the surface.
Electrodeposition can...
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Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
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Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
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低座標銅複合体による電気触媒によるアンモニア酸化.

Md Estak Ahmed1,2, Mahdi Raghibi Boroujeni2, Pokhraj Ghosh1,2

  • 1Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, United States.

Journal of the American Chemical Society
|November 9, 2022
PubMed
まとめ

新しい銅触媒は,アンモニアを効率的に二酸化して二酸化窒素に変換し,アンモニアを持続可能な燃料と水素源として使用するための重要なステップです. この強力な電気触媒は,安定性とN-N結合形成の有効なメカニズムを示しています.

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科学分野:

  • 電気化学 電気化学について
  • カタリシス カタリシス カタリシス
  • 無機化学 無機化学とは

背景:

  • 二酸化窒素へのアンモニアの酸化は,アンモニアを燃料および水素源として利用するために不可欠です.
  • このプロセスは,強いN-H結合を破ってN-N結合を形成することを必要とし,重要な触媒的課題を提示します.

研究 の 目的:

  • アンモニアの酸化のための強力な電気触媒として,新しいβ-ディケチミナート銅複合体を報告する.
  • 銅触媒によって媒介されるアンモニア酸化のメカニズムを調査する.

主な方法:

  • サイクルボルトメトリー (CV) と制御ポテンシャル電解 (CPE) を含む電気化学的特徴付け.
  • 新しいβ-ディケチミナート銅複合体の合成と特徴付け.
  • 反応経路と熱力学的障壁を解明するための密度関数理論 (DFT) 分析.

主要な成果:

  • 合成された銅複合体 ([Pr2NNF6]CuI-NH3) は,高回転周波数 (TOFmax = 940 h-1) で,適度な超電位 (700 mV) でアンモニアの酸化を効率的に触媒化する.
  • 触媒は,長時間電解 (>5時間) 中の優れた安定性を示した.
  • 機理学的な研究では,N-N結合形成に不可欠な反応性銅 ((II) - アミド中間体の形成が明らかになり,高濃度のアンモニアで電気触媒的に無活性な種が特定されました.

結論:

  • 報告された銅複合体は,アンモニアを二酸化窒素にするために,頑丈で効率的な電気触媒です.
  • 銅アミド中間物質の役割や,高いアンモニア濃度での無活性化経路を含む,メカニズム的経路を理解することは,触媒設計の鍵です.
  • この研究は,アンモニアベースのエネルギーアプリケーションのための触媒の開発に有望な道を提供します.