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

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...

Electron Affinity

Electron Affinity

The electron affinity (EA) is the energy change for adding an electron to a gaseous atom to form an anion (negative ion).

2° Amines to N-Nitrosamines: Reaction with NaNO2

2° Amines to N-Nitrosamines: Reaction with NaNO₂

Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.

Electrophilic Aromatic Substitution: Nitration of Benzene

Electrophilic Aromatic Substitution: Nitration of Benzene

The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.

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

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...

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

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.

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Related Experiment Video

Updated: Jun 16, 2026

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

Published on: August 5, 2016

On the electron affinity of nitromethane (CH3NO2).

James N Bull¹, Robert G A R Maclagan, Peter W Harland

¹Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140, New Zealand.

The Journal of Physical Chemistry. A

|February 17, 2010

Summary

Accurate electron affinity of nitromethane (CH(3)NO(2)) was determined using advanced multireference methods. This resolves discrepancies, yielding a value consistent with recent experimental data.

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

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Nitrogen Compound Characterization in Fuels by Multidimensional Gas Chromatography

Nitrogen Compound Characterization in Fuels by Multidimensional Gas Chromatography

Published on: May 15, 2020

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Last Updated: Jun 16, 2026

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

Published on: August 5, 2016

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

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

Published on: February 16, 2022

Nitrogen Compound Characterization in Fuels by Multidimensional Gas Chromatography

Nitrogen Compound Characterization in Fuels by Multidimensional Gas Chromatography

Published on: May 15, 2020

Area of Science:

Computational Chemistry
Quantum Chemistry
Theoretical Chemistry

Background:

Discrepancies exist in reported theoretical and experimental values for nitromethane's electron affinity.
Standard computational methods like Density Functional Theory (DFT) struggle with electron attachment due to self-interaction errors.

Purpose of the Study:

To accurately determine the adiabatic valence electron affinity of nitromethane (CH(3)NO(2)).
To resolve conflicting values reported in the scientific literature.

Main Methods:

High-level systematic computational study employing multireference methods.
Utilized aug-cc-pVTZ basis sets for calculations.
Employed 3S-MCQDPT2 and 7S-MCQDPT2 levels of theory, including polynomial extrapolation.

Main Results:

Multireference methods with appropriate basis sets are necessary for accurate results.
Calculated electron affinity values of 0.188 eV and 0.176 eV (0.170 eV extrapolated).
These results show excellent agreement with the recent experimental value of 0.172 +/- 0.006 eV.

Conclusions:

The study establishes a reliable value for nitromethane's electron affinity.
Confirms the inadequacy of DFT for accurately describing electron attachment in such systems.
Highlights the importance of multireference approaches for accurate electron affinity calculations.