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meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H01:13

meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H

All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for the...
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Catalysis

The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
Radical Formation: Homolysis00:54

Radical Formation: Homolysis

A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview01:26

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

Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism01:37

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

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.
Rate-Determining Steps03:08

Rate-Determining Steps

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Nitric oxide decomposition on small rhodium clusters, Rh(n)+/-.

Marie L Anderson1, Mark S Ford, Peter J Derrick

  • 1Department of Chemistry, University of Warwick, Coventry, CV4 7AL, UK.

The Journal of Physical Chemistry. A
|September 22, 2006
PubMed
Summary

This study investigated nitric oxide decomposition on charged rhodium clusters. Reactivity increased with size, with cationic clusters being more reactive, and a surface charge capture model accurately predicted trends.

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Chemiluminescence-based Assays for Detection of Nitric Oxide and its Derivatives from Autoxidation and Nitrosated Compounds
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Chemiluminescence-based Assays for Detection of Nitric Oxide and its Derivatives from Autoxidation and Nitrosated Compounds

Published on: February 16, 2022

Area of Science:

  • Surface Science
  • Physical Chemistry
  • Materials Science

Background:

  • Nitric oxide (NO) decomposition is crucial in catalysis and atmospheric chemistry.
  • Understanding the behavior of small transition-metal clusters is key to developing new catalytic materials.
  • The size and charge dependence of cluster reactivity present complex challenges in surface chemistry.

Purpose of the Study:

  • To investigate the decomposition of nitric oxide on small charged rhodium clusters (Rh(n)(+/-), 6 < n < 30).
  • To determine the influence of cluster size and charge on NO decomposition kinetics and mechanisms.
  • To compare experimental findings with theoretical models like the surface charge capture model.

Main Methods:

  • Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) was used to study the reactions.
  • Kinetic studies were performed to measure reaction rates and identify reaction orders.
  • Analysis of reaction products revealed insights into decomposition pathways and surface coverage.

Main Results:

  • Reaction rates increased smoothly with cluster size for both cationic and anionic rhodium clusters.
  • Cationic clusters exhibited significantly higher reactivity than anionic clusters.
  • NO decomposition primarily yielded nitrogen gas (N2) and oxide clusters for n < 17, with size-dependent limiting oxygen coverages.
  • For n = 13 and n > 16, simple sequential NO adsorption dominated, with no N2 production observed.
  • Rh(13)(+/-) clusters showed anomalous behavior compared to neighboring sizes.

Conclusions:

  • The surface charge capture model effectively explains the observed reactivity trends.
  • Dissociative adsorption of NO and subsequent nitrogen atom mobility are key to decomposition for smaller clusters.
  • Cluster size and structure significantly influence NO decomposition mechanisms, with Rh(13)(+/-) being a notable exception.
  • The study provides a comprehensive understanding of NO decomposition on charged rhodium clusters, informing catalyst design.