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Related Concept Videos

Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or...
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Anionic Chain-Growth Polymerization: Overview01:20

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
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Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Assembly and Characterization of Polyelectrolyte Complex Micelles
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Polymer complexation: Partially ionizable asymmetric polyelectrolytes.

Souradeep Ghosh1,2, Soumik Mitra1, Arindam Kundagrami1,2

  • 1Department of Physical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, India.

The Journal of Chemical Physics
|May 25, 2023
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Summary
This summary is machine-generated.

This study introduces a molecular-level model for asymmetric polyelectrolyte complexation, revealing how chain length and charge density impact coacervate properties. The findings enhance understanding of polymer complexation thermodynamics.

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Area of Science:

  • Polymer Science
  • Physical Chemistry
  • Materials Science

Background:

  • Bulk coacervation theories overlook single-molecule thermodynamics crucial for equilibrium.
  • Simulations often simplify interactions to pairwise Coulomb forces.
  • Research on asymmetric polyelectrolyte complexation is less common than for symmetric systems.

Purpose of the Study:

  • To develop a theoretical model for asymmetric polyelectrolyte complexation at the molecular level.
  • To account for all entropic and enthalpic contributions and interactions.
  • To investigate the impact of asymmetry on complex properties and thermodynamic drive.

Main Methods:

  • Constructed a theoretical model based on Edwards and Muthukumar's Hamiltonian.
  • Included mutual segmental screened Coulomb and excluded volume interactions.
  • Minimized system free energy, considering polyion configurational entropy and free-ion entropy, assuming maximal ion-pairing.

Main Results:

  • Effective complex charge and size increase with asymmetry in polyion length and charge density.
  • Thermodynamic drive for complexation rises with ionizability and decreases with length asymmetry.
  • Crossover Coulomb strength depends on dielectric environment and salt, not significantly on charge density.

Conclusions:

  • The model provides a framework to calculate thermodynamic dependencies of complexation on experimental parameters.
  • Results align with simulation trends, offering predictive capabilities.
  • Enhances understanding of coacervate equilibrium and polymer pair interactions.