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Radical Formation: Homolysis00:54

Radical Formation: Homolysis

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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.
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Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

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Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
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Acid Halides to Carboxylic Acids: Hydrolysis01:01

Acid Halides to Carboxylic Acids: Hydrolysis

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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...
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Acid Halides to Alcohols: LiAlH4 Reduction01:19

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Acid halides are reduced to alcohols in the presence of a strong reducing agent like lithium aluminum hydride.
The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...
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Ethers to Alkyl Halides: Acidic Cleavage02:18

Ethers to Alkyl Halides: Acidic Cleavage

7.0K
Ethers are generally unreactive and unsuitable for direct nucleophilic substitution reactions since the alkoxy groups are strong bases and, therefore, poor leaving groups. However, ethers readily undergo acidic-cleavage reactions. Ethers can be converted to alkyl halides when heated with strong acids such as HBr and HI in a sequence of two substitution reactions.
7.0K
Aqueous Solutions and Heats of Hydration02:42

Aqueous Solutions and Heats of Hydration

17.5K
Water and other polar molecules are attracted to ions. The electrostatic attraction between an ion and a molecule with a dipole is called an ion-dipole attraction. These attractions play an important role in the dissolution of ionic compounds in water.
When ionic compounds dissolve in water, the ions in the solid separate and disperse uniformly throughout the solution because water molecules surround and solvate the ions, reducing the strong electrostatic forces between them. This process...
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Plasma-Driven Decomposition of HAN-Based Ionic Liquids.

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Nanosecond pulse transient plasma initiates nonthermal decomposition of ionic liquids, enabling rapid on/off control of exothermic reactions. This plasma method generates reactive species, offering a novel pathway for controlled combustion.

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Area of Science:

  • Plasma Science and Engineering
  • Chemical Kinetics
  • Materials Science

Background:

  • Ionic liquids (ILs) offer unique properties but their controlled decomposition for energy release remains challenging.
  • Conventional methods for IL decomposition often rely on thermal energy, which can be difficult to control precisely.
  • Developing novel initiation and control methods for exothermic reactions in ILs is crucial for advanced energetic materials.

Purpose of the Study:

  • To investigate the use of nanosecond pulse transient plasma for initiating and controlling the exothermic decomposition of ionic liquids.
  • To elucidate the underlying plasma-driven decomposition mechanisms, including bubble formation and reactive species generation.
  • To demonstrate the rapid toggling (on/off) capability of plasma-induced ignition and combustion in ILs.

Main Methods:

  • Discharge of nanosecond pulses (20 kV, 20 ns, up to 10 kHz) in a coaxial cylindrical plasma reactor containing ionic liquids.
  • Real-time high-speed imaging to observe plasma initiation, bubble dynamics, and combustion evolution.
  • In situ plasma emission spectroscopy and FTIR emission spectroscopy to identify reactive intermediates and combustion products.

Main Results:

  • Nanosecond plasma successfully initiated nonthermal decomposition and combustion of hydroxylammonium nitrate (HAN) and [EMIM]/[EtSO4] ionic liquid mixtures.
  • High-speed imaging confirmed rapid ignition and extinguishing, with flame toggling possible within 66 ms.
  • Spectroscopic analysis identified key reactive intermediates (H, O, S, NO, CO) and products (CO2, H2O), confirming combustion.
  • Plasma-induced decomposition pathways were found to differ significantly from conventional thermal methods.

Conclusions:

  • Nanosecond pulse transient plasma provides an effective method for initiating and controlling exothermic decomposition of ionic liquids.
  • The plasma-driven mechanism involves bubble formation, dielectric breakdown, and generation of highly reactive radical species.
  • This technique offers precise, rapid control over combustion processes in ionic liquids, distinct from thermal methods.