Limitations of the Derjaguin approximation and the Lorentz-Berthelot mixing rule

Jan Forsman1, Clifford E Woodward

  • 1Theoretical Chemistry, Chemical Centre, P.O. Box 124, S-221 00 Lund, Sweden.

Related Concept Videos

The Thermodynamics of Mixing01:28

The Thermodynamics of Mixing

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'...
Calculation of First-Law Quantities II01:24

Calculation of First-Law Quantities II

The first law of thermodynamics establishes that the change in internal energy of a system is given by ΔU = q + w, where q is the heat exchanged, and w is the work performed. For a perfect gas, both internal energy (U) and enthalpy (H) depend solely on temperature. Consequently, for any change of state, whether reversible or irreversible, the internal energy change is determined by integrating the heat capacity at constant volume, and the enthalpy change by integrating the heat capacity at...
Ostwald’s Dilution Law01:25

Ostwald’s Dilution Law

Consider a binary electrolyte AB with a concentration ‘c’ that reversibly dissociates into its constituent ions. The degree of this dissociation is represented by ⍺. This means that the equilibrium concentration of each ionic species can be expressed as ⍺c. As well as this, the fraction of the electrolyte that remains undissociated at equilibrium is given by (1−⍺). The corresponding equilibrium concentration for this undissociated portion is then calculated as (1−⍺)c. For such solutions,...
Mixtures of Gases: Dalton's Law of Partial Pressures and Mole Fractions03:03

Mixtures of Gases: Dalton's Law of Partial Pressures and Mole Fractions

Unless individual gases chemically react with each other, the individual gases in a mixture of gases do not affect each other’s pressure. Each gas in a mixture exerts the same pressure that it would exert if it were present alone in the container. The pressure exerted by each individual gas in a mixture is called its partial pressure.
Reaction Mechanisms: Rate-limiting Step Approximation01:29

Reaction Mechanisms: Rate-limiting Step Approximation

The rate-determining step, or RDS, in a chemical reaction is the slowest step that determines the overall reaction rate. It is identified by using the observed rate law and typically involves approximation methods like the RDS approximation or the steady-state approximation.In the RDS approximation, also known as the rate-limiting-step or equilibrium approximation, the reaction mechanism consists of one or more reversible reactions near equilibrium, followed by a slower RDS, and then one or...
Calculation of First Law Quantities I01:25

Calculation of First Law Quantities I

Thermodynamic systems undergoing phase transitions or temperature changes experience energy transfer in the form of heat (q) and work (w). For a reversible phase change at constant temperature (T) and pressure (p), the process involves no chemical reaction but results in energy exchange between distinct phases.The heat transferred during this process corresponds to the latent heat of transition, which is the amount of heat energy absorbed or released by a substance when it changes from one...