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Related Concept Videos

Hydrogen Bonds00:26

Hydrogen Bonds

Hydrogen BondsHydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.Hydrogen Bonds Control the World!Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are...
Reduction of Alkenes: Catalytic Hydrogenation02:13

Reduction of Alkenes: Catalytic Hydrogenation

Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation02:47

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Acid Halides to Carboxylic Acids: Hydrolysis01:01

Acid Halides to Carboxylic Acids: Hydrolysis

Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...
Radical Formation: Abstraction00:47

Radical Formation: Abstraction

The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
Even though homolysis produces radicals, it is different from radical...
Hydrogen Bonds01:04

Hydrogen Bonds

A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...

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Hydrogen Abstraction from Hydrocarbons by NH2.

Kamal Siddique1, Mohammednoor Altarawneh1, Jeff Gore2

  • 1School of Engineering and Information Technology, Murdoch University , 90 South Street, Murdoch, WA 6150, Australia.

The Journal of Physical Chemistry. A
|February 23, 2017
PubMed
Summary

This study quantifies thermokinetic parameters for reactions between the amine (NH2) radical and hydrocarbons, crucial for biomass combustion. Calculated rate constants show good agreement with experimental data, validating the methodology for predicting reaction kinetics.

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Published on: December 6, 2021

Area of Science:

  • Chemical Kinetics
  • Combustion Chemistry
  • Theoretical Chemistry

Background:

  • The amine (NH2) radical is key in combustion and pyrolysis of nitrogen-rich fuels like biomass.
  • Understanding NH2 radical reactions with hydrocarbons is vital for accurate combustion modeling.

Purpose of the Study:

  • To investigate thermokinetic parameters for bimolecular gas-phase reactions of the NH2 radical with various hydrocarbons.
  • To provide accurate rate constants and enthalpies for H-abstraction reactions, crucial for biomass combustion and pyrolysis.

Main Methods:

  • Utilized CBS-QB3 level computations and conventional transition-state theory.
  • Accounted for tunneling effects and hindered rotors in rate constant calculations.
  • Employed Evans-Polanyi plots to correlate bond dissociation enthalpies with activation enthalpies.

Main Results:

  • Calculated rate constants for NH2 radical reactions with methane and ethane show good agreement with experimental data across different temperature ranges.
  • The methodology demonstrates high accuracy, with a mean unsigned error of 3.7 kJ mol-1 for enthalpies of reaction.
  • Developed generalized Arrhenius parameters for H-abstraction from various C-H bond types in noncyclic hydrocarbons.

Conclusions:

  • The computational methodology is validated, enabling accurate prediction of kinetic parameters for NH2 radical reactions with hydrocarbons.
  • The findings provide essential data for improving combustion models, particularly for biomass-derived fuels.
  • Generalized parameters facilitate the estimation of reaction rates for a wide range of hydrocarbon-NH2 radical interactions.