PapersFlow Research Brief
Thermodynamic properties of mixtures
Research Guide
What is Thermodynamic properties of mixtures?
Thermodynamic properties of mixtures refer to measurable characteristics such as density, viscosity, surface tension, and excess molar volumes of binary and aqueous liquid mixtures, along with molecular interactions including hydrogen bonding.
Research in thermodynamic properties of mixtures examines density, viscosity, surface tension, excess molar volumes, refractive indices, and speed of sound in liquid mixtures. The field includes 53,753 papers with a focus on interactions and hydrogen bonding in binary mixtures and aqueous solutions. Key models address excess Gibbs energies and local compositions in these systems.
Topic Hierarchy
Research Sub-Topics
Excess Molar Volumes in Binary Liquid Mixtures
This sub-topic measures and models excess molar volumes (V^E) of binary mixtures over wide temperature and composition ranges using densitometry. Researchers apply Redlich-Kister polynomials and Prigogine-Flory-Patterson theory to interpret molecular packing effects.
Viscosity of Aqueous Electrolyte Solutions
This sub-topic examines concentration and temperature dependencies of viscosity in aqueous salt solutions, including ion-pairing effects. Researchers correlate data with Jones-Dole parameters and extended hydrodynamic models for industrial applications.
Surface Tension in Organic-Aqueous Mixtures
This sub-topic investigates surface tension isotherms, critical micelle concentrations, and adsorption at liquid-vapor interfaces of alcohol-water systems. Researchers use Gibbs adsorption equation and molecular dynamics to study hydrophobic effects.
Speed of Sound Measurements in Liquid Mixtures
This sub-topic derives isentropic compressibilities from ultrasonic speed of sound data in binary and ternary mixtures. Researchers test theoretical predictions like free-length theory and analyze intermolecular interactions via excess properties.
Hydrogen Bonding in Alcohol-Water Mixtures
This sub-topic explores hydrogen bonding strength, stoichiometry, and temperature effects in water-alcohol binaries through excess properties and spectroscopy. Researchers quantify hydrophobic hydration and clathrate formation using association models.
Why It Matters
Thermodynamic properties of mixtures enable accurate modeling of phase equilibria and transport in chemical processes, such as distillation and extraction in the chemical industry. Renon and Prausnitz (1968) introduced local composition concepts in "Local compositions in thermodynamic excess functions for liquid mixtures," improving predictions of activity coefficients for non-ideal mixtures with over 6,569 citations. Soave (1972) modified the Redlich-Kwong equation in "Equilibrium constants from a modified Redlich-Kwong equation of state," facilitating vapor-liquid equilibrium calculations in hydrocarbon processing, cited 6,097 times. Abrams and Prausnitz (1975) developed the UNIQUAC model in "Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems," applied in pharmaceutical and petrochemical separations with 4,582 citations.
Reading Guide
Where to Start
"Local compositions in thermodynamic excess functions for liquid mixtures" by Renon and Prausnitz (1968) provides an accessible entry via its derivation of excess Gibbs energy models from two-liquid concepts, foundational for understanding non-ideal mixtures.
Key Papers Explained
Renon and Prausnitz (1968) in "Local compositions in thermodynamic excess functions for liquid mixtures" establish local composition for excess functions, which Abrams and Prausnitz (1975) extend to UNIQUAC in "Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems" using quasi-chemical analysis. Soave (1972) complements these with equation-of-state modifications in "Equilibrium constants from a modified Redlich-Kwong equation of state" for phase equilibria. Kirkwood (1935) in "Statistical Mechanics of Fluid Mixtures" supplies pair distribution foundations, while Weeks et al. (1971) in "Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids" refines structural insights.
Paper Timeline
Most-cited paper highlighted in red. Papers ordered chronologically.
Advanced Directions
Foundational models from 1935-1975 dominate, with 53,753 papers but no recent preprints or news in the last 12 months. Researchers pursue integrations of dielectric spectroscopy from Cole and Cole (1941) with excess property measurements. Extensions to related molten salt chemistry remain active.
Papers at a Glance
| # | Paper | Year | Venue | Citations | Open Access |
|---|---|---|---|---|---|
| 1 | Dispersion and Absorption in Dielectrics I. Alternating Curren... | 1941 | The Journal of Chemica... | 9.8K | ✕ |
| 2 | Local compositions in thermodynamic excess functions for liqui... | 1968 | AIChE Journal | 6.6K | ✕ |
| 3 | Equilibrium constants from a modified Redlich-Kwong equation o... | 1972 | Chemical Engineering S... | 6.1K | ✕ |
| 4 | On the Temperature Dependence of Cooperative Relaxation Proper... | 1965 | The Journal of Chemica... | 5.7K | ✕ |
| 5 | Role of Repulsive Forces in Determining the Equilibrium Struct... | 1971 | The Journal of Chemica... | 5.1K | ✕ |
| 6 | Statistical thermodynamics of liquid mixtures: A new expressio... | 1975 | AIChE Journal | 4.6K | ✕ |
| 7 | The Viscosity of Concentrated Suspensions and Solutions | 1952 | The Journal of Chemica... | 4.4K | ✕ |
| 8 | Broadband Dielectric Spectroscopy | 2003 | — | 4.2K | ✕ |
| 9 | Molecular Transport in Liquids and Glasses | 1959 | The Journal of Chemica... | 3.9K | ✕ |
| 10 | Statistical Mechanics of Fluid Mixtures | 1935 | The Journal of Chemica... | 3.4K | ✕ |
Frequently Asked Questions
What are excess molar volumes in mixtures?
Excess molar volumes quantify deviations from ideal mixing volumes in liquid mixtures, arising from molecular interactions like hydrogen bonding. They are measured alongside density and speed of sound in binary and aqueous solutions. These properties inform models of non-ideal behavior in thermodynamic studies.
How do local compositions improve excess Gibbs energy models?
Local compositions account for nonrandom molecular arrangements in "Local compositions in thermodynamic excess functions for liquid mixtures" by Renon and Prausnitz (1968). This approach derives equations based on two-liquid models, enhancing activity coefficient predictions. It applies to binary mixtures beyond ideal solutions.
What is the UNIQUAC equation?
The UNIQUAC equation, from "Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems" by Abrams and Prausnitz (1975), generalizes Guggenheim's quasi-chemical analysis using local area fractions. It models excess Gibbs energy for partly miscible systems. The model uses two parameters for combinatorial and residual contributions.
How does the modified Redlich-Kwong equation handle mixtures?
Soave (1972) in "Equilibrium constants from a modified Redlich-Kwong equation of state" adapts the equation for vapor-liquid equilibria in mixtures. It improves equilibrium constant predictions for non-polar systems. The modification enhances accuracy over the original for hydrocarbons.
What role do repulsive forces play in mixture structure?
Weeks, Chandler, and Andersen (1971) in "Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids" separate repulsive and attractive forces in Lennard-Jones liquids. Repulsive forces primarily determine the pair correlation structure. This informs statistical mechanics of fluid mixtures.
What is the current state of research on mixture viscosities?
Brinkman (1952) derived expressions for viscosity in "The Viscosity of Concentrated Suspensions and Solutions" by treating added solute in continuous media. Studies extend to concentrated binary mixtures. No recent preprints available indicate steady foundational focus.
Open Research Questions
- ? How can local composition models be extended to predict hydrogen bonding in aqueous solutions beyond binary systems?
- ? What refinements to the UNIQUAC equation improve accuracy for excess molar volumes in high-concentration mixtures?
- ? How do cooperative relaxation properties from Adam and Gibbs (1965) influence dynamic thermodynamic properties like viscosity in glass-forming mixtures?
- ? Can repulsive force separations from Weeks et al. (1971) predict surface tension deviations in complex liquid mixtures?
- ? What integrates Kirkwood's (1935) pair distribution functions with modern equations of state for multicomponent mixtures?
Recent Trends
The field maintains 53,753 works with no specified 5-year growth rate; highly cited papers from 1935-1975, such as Renon and Prausnitz at 6,569 citations, indicate reliance on established models.
1968No preprints or news in the last 6-12 months suggest stable focus on binary mixture properties like density and viscosity without major shifts.
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