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Related Concept Videos

Thermodynamics: Activity Coefficient01:24

Thermodynamics: Activity Coefficient

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Activity is the measure of the effective concentration of the species in solution. It can be expressed as the product of the molar concentration of the species and its activity coefficient. The activity coefficient is a dimensionless quantity and depends on the total ionic strength of the solution.
The activity coefficient is a measure of the deviation from ideal behavior. When the ionic strength of the solution is minimal, the activity coefficient of an ionic species is close to unity, making...
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The Thermodynamics of Mixing01:28

The Thermodynamics of Mixing

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Mixing is a fascinating phenomenon in thermodynamics, particularly when considering the Gibbs energy of a mixture at constant temperature and pressure. This energy, denoted as G, tends to decrease during spontaneous mixing processes, offering insights into the composition changes that occur.Imagine two ideal gases, initially separated in different containers, with amounts nA and nB, respectively, both at a temperature T and pressure p. The chemical potentials of these gases have their 'pure'...
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Thermodynamic Properties of Ideal Solutions01:19

Thermodynamic Properties of Ideal Solutions

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For an ideal liquid solution, the standard state of each component is defined as the pure liquid at the temperature and pressure of the solution. Similarly, for solid solutions, the standard state is the pure solid. The chemical potentials of the components in the ideal solution are compared to the chemical potentials of the pure substances in their standard states. These standard states provide a reference point for calculating the thermodynamic properties of ideal solutions.For ideal...
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Aqueous Solutions and Heats of Hydration02:42

Aqueous Solutions and Heats of Hydration

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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.
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Entropy and Solvation02:05

Entropy and Solvation

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The process of surrounding a solute with solvent is called solvation. It involves evenly distributing the solute within the solvent. The rule of thumb for determining a solvent for a given compound is that like dissolves like. A good solvent has molecular characteristics similar to those of the compound to be dissolved. For example, polar solutions dissolve polar solutes, and apolar solvents dissolve apolar solutes. A polar solvent is a solvent that has a high dielectric constant (ϵ...
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In convection, thermal energy is carried by the large-scale flow of matter. Ocean currents and large-scale atmospheric circulation, which result from the buoyancy of warm air and water, transfer hot air from the tropics toward the poles and cold air from the poles toward the tropics. The Earth’s rotation interacts with those flows, causing the observed eastward flow of air in the temperate zones. Convection dominates heat transfer by air, and the amount of available space for the airflow...
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Updated: Mar 16, 2026

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Thermodynamics of complex coacervation.

A Basak Kayitmazer1

  • 1Department of Chemistry, Bogazici University, Bebek, Istanbul 34342, Turkey.

Advances in Colloid and Interface Science
|August 8, 2016
PubMed
Summary

Isothermal titration calorimetry (ITC) reveals complex thermodynamic drivers in macromolecular coacervation. Advanced models are crucial for understanding electrostatics, counterion release, and other forces governing these interactions.

Area of Science:

  • Physical Chemistry
  • Materials Science
  • Biophysics

Background:

  • Isothermal titration calorimetry (ITC) is a standard technique for studying complexation and coacervation thermodynamics.
  • Traditional ITC models often assume independent binding sites, which may not accurately represent macromolecular interactions.
  • Non-covalent interactions and steric factors in macromolecules necessitate more sophisticated analytical approaches.

Purpose of the Study:

  • To explore advanced thermodynamic models for analyzing macromolecular complexation and coacervation using ITC.
  • To identify the primary driving forces behind polyelectrolyte interactions with oppositely charged species and surfactants.
  • To investigate the influence of various environmental and molecular parameters on coacervation thermodynamics.

Main Methods:

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  • Application of advanced ITC models, including overlapping binding sites and Satake-Yang's two-state binding models.
  • Analysis of ITC data to interpret coacervation as two-stage structuring processes.
  • Comparative analysis of ITC with other techniques like surface plasmon resonance and capillary electrophoresis.

Main Results:

  • Electrostatic interactions and counterion release were identified as key forces in polyelectrolyte complexation.
  • Hydrogen bonding and hydrophobic interactions may also contribute to the observed thermodynamics.
  • ITC data for surfactant-polyelectrolyte systems showed distinct phases for polymer-induced and free micelle formation.
  • Coacervation thermodynamics are sensitive to pH, ionic strength, charge density, molecular weight, concentration, and mixing order.

Conclusions:

  • Advanced ITC models provide deeper insights into the thermodynamics of macromolecular coacervation.
  • Understanding the interplay of electrostatic, counterion release, and other forces is critical for coacervation.
  • Environmental and molecular parameters significantly modulate coacervation behavior, offering avenues for control.