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Van der Waals Equation of State

1873
  • Johannes Diderik van der Waals
19th-century laboratory with Van der Waals equation and scientific instruments.

An equation of state for a fluid that modifies the ideal gas law to approximate the behavior of real gases. It introduces two parameters: ‘a’ to account for long-range intermolecular attractive forces (Van der Waals forces) and ‘b’ for the finite volume occupied by the gas molecules. The equation is \((P + \frac{an^2}{V^2})(V – nb) = nRT\).

The Van der Waals equation of state was a groundbreaking development in thermodynamics, providing the first realistic description of real gases and their condensation into liquids. It starts with the ideal gas law, \(PV = nRT\), and applies two crucial corrections. The first correction addresses the volume. In an ideal gas, particles are treated as points with no volume. The Van der Waals equation subtracts a term ‘nb’ from the container volume \(V\), where ‘b’ is the volume excluded by a mole of particles. This term, \((V – nb)\), represents the actual free volume available for the molecules to move in.

The second, more significant correction accounts for intermolecular attractive forces. These forces reduce the pressure exerted by the gas on the container walls because molecules near the wall are pulled inwards by their neighbors. This reduction in pressure is proportional to the square of the particle density (\(n/V\)), leading to the correction term \(a(n/V)^2\) which is added to the measured pressure \(P\). The parameter ‘a’ is a measure of the average attraction between particles. By incorporating these two parameters, the equation can successfully model the liquid-gas phase transition and predict the existence of a critical point, above which no distinct liquid and gas phases exist. It was for this work that van der Waals received the Nobel Prize in Physics in 1910.

UNESCO Nomenclature: 2212
– Thermodynamics

Type

Mathematical Model

Disruption

Foundational

Usage

Widespread Use

Precursors

  • Ideal Gas Law (Boyle’s Law, Charles’s Law, Avogadro’s Law)
  • Kinetic Theory of Gases developed by Clausius and Maxwell
  • Early concepts of intermolecular forces and finite atomic size

Applications

  • modeling of real gases and their deviation from ideal behavior
  • prediction of liquid-vapor phase transitions and critical points
  • thermodynamic property calculations in chemical engineering
  • foundational model for more complex equations of state

Patents:

NA

Potential Innovations Ideas

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Related to: Van der Waals equation, real gas, equation of state, intermolecular forces, molecular volume, critical point, thermodynamics, phase transition, pressure, volume.

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Historical Context

(if date is unknown or not relevant, e.g. "fluid mechanics", a rounded estimation of its notable emergence is provided)

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