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Related Concept Videos

Standard Enthalpy of Formation02:37

Standard Enthalpy of Formation

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Enthalpy changes are typically tabulated for reactions in which both the reactants and products are at the same conditions. A standard state is a commonly accepted set of conditions used as a reference point for the determination of properties under other different conditions. For chemists, the IUPAC standard state refers to materials under a pressure of 1 bar and solutions at 1 M and does not specify a temperature. Many thermochemical tables list values with a standard state of 1 atm. Because...
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Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis01:13

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Hydrolysis of esters under acidic conditions proceeds through a nucleophilic acyl substitution. In the presence of excess water, the reaction proceeds in a reversible manner, forming carboxylic acids and alcohols.
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
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Free Energy Changes for Nonstandard States03:25

Free Energy Changes for Nonstandard States

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The free energy change for a process taking place with reactants and products present under nonstandard conditions (pressures other than 1 bar; concentrations other than 1 M) is related to the standard free energy change according to this equation:
 
where R is the gas constant (8.314 J/K·mol), T is the absolute temperature in kelvin, and Q is the reaction quotient. This equation may be used to predict the spontaneity of a process under any given set of conditions.
Reaction Quotient...
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Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism01:13

Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism

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Carboxylic acids react with alcohols to yield esters via an acid-catalyzed condensation reaction called Fischer esterification. This is a nucleophilic acyl substitution reaction that proceeds via a tetrahedral intermediate, where a water molecule is eliminated as the leaving group.
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Acid-Catalyzed Hydration of Alkenes02:45

Acid-Catalyzed Hydration of Alkenes

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Alkenes react with water in the presence of an acid to form an alcohol. In the absence of acid, hydration of alkenes does not occur at a significant rate, and the acid is not consumed in the reaction. Therefore, alkene hydration is an acid-catalyzed reaction.
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Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview01:20

Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview

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The Fischer esterification reaction was developed by the German chemist Emil Fischer in 1895. It is a condensation reaction between carboxylic acids and alcohols in an acidic medium to give esters and water.
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Pressurized Formic Acid Dehydrogenation: An Entropic Spring Replaces Hydrogen Compression Cost.

Van K Do1, Nicolas Alfonso Vargas1, Anthony J Chavez1

  • 1Loker Hydrocarbon Research Institute, Wrigley Institute for Environmental Studies, and Department of Chemistry, University of Southern California, Los Angeles, California, 90089, United States.

Catalysis Science & Technology
|May 16, 2023
PubMed
Summary
This summary is machine-generated.

Formic acid dehydrogenation yields high-pressure hydrogen efficiently due to its entropic nature. This study explores homogeneous catalysts for selective formic acid dehydrogenation, enabling on-demand hydrogen production.

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Area of Science:

  • Catalysis
  • Hydrogen Storage
  • Sustainable Energy

Background:

  • Formic acid is a unique liquid organic hydrogen carrier (LOHC) due to its entropically driven dehydrogenation.
  • High-pressure hydrogen is crucial for on-demand applications like vehicle refueling.
  • Hydrogen compression is a significant cost factor, necessitating efficient high-pressure H2 generation methods.

Purpose of the Study:

  • To investigate homogeneous catalysts for selective formic acid dehydrogenation under self-pressurizing conditions.
  • To explore the influence of catalyst structure and ligand framework on performance.
  • To understand the roles of H2 and CO in catalyst activation and stability.

Main Methods:

  • Screening of homogeneous catalysts with diverse ligand frameworks (Noyori-type, bidentate chelates) and metallic precursors.
  • Testing catalysts for the dehydrogenation of neat formic acid under varying pressure conditions.
  • In-situ analysis of catalyst activation, speciation, and the role of H2 and CO.

Main Results:

  • Various homogeneous catalysts demonstrated suitability for formic acid dehydrogenation under self-pressurizing conditions.
  • Catalyst performance varied significantly based on structural differences and pressure tolerance.
  • Identified crucial roles for H2 and CO in catalyst activation, speciation, and extended catalyst lifetime, with CO acting as a 'healing reagent'.

Conclusions:

  • Homogeneous catalysis offers a viable route for producing high-pressure hydrogen from formic acid.
  • Catalyst design can be tailored to optimize performance under pressurized conditions.
  • Understanding the interplay of H2, CO, and catalyst structure is key to developing robust and efficient hydrogen generation systems.