The Gibbs-Dalton Law of Partial Pressures

Physical Review - PHYS REV X 01/1930; 36(1):121-131. DOI: 10.1103/PhysRev.36.121


Various formulations of Dalton's law are investigated thermodynamically. The Gibbs formulation is shown equivalent to the statement: The concentration of a gas is the same at equilibrium on either side of a membrane permeable to it alone. The ordinary form of Dalton's law has only a limited equivalence with the Gibbs form. The Lewis and Randall rule of fugacity is shown in many ways analogous to the Gibbs-Dalton law. Application to experimental data shows that the Gibbs-Dalton law, like the Lewis and Randall rule, though possible for gases which do not follow Boyle's law, is only an approximation. In the cases examined, the errors are opposite in sign to those of the Lewis and Randall rule. An outline is given for the application of the Gibbs-Dalton law to the study of equilibrium in gases, and the useful field of application is indicated.

22 Reads
  • [Show abstract] [Hide abstract]
    ABSTRACT: The merits of the various simple rules for the estimation of gas mixture PVT properties are investigated in terms of the implications inherent in them. The equivalence of a number of estimation procedures is demonstrated.A new rule of the form is proposed and recommendations as to the preferred rules to be adopted in particular circumstances are given.
    Chemical Engineering Science 08/1975; 30(8):819–823. DOI:10.1016/0009-2509(75)80046-7 · 2.34 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Rapid compression machines (RCMs) have been widely used in the combustion literature to study the low-to-intermediate temperature ignition of many fuels. In a typical RCM, the pressure during and after the compression stroke is measured. However, measurement of the temperature history in the RCM reaction chamber is challenging. Thus, the temperature is generally calculated by the isentropic relations between pressure and temperature, assuming that the adiabatic core hypothesis holds. To estimate the uncertainty in the calculated temperature, an uncertainty propagation analysis must be carried out. Our previous analyses assumed that the uncertainties of the parameters in the equation to calculate the temperature were normally distributed and independent, but these assumptions do not hold for typical RCM operating procedures. In this work, a Monte Carlo method is developed to estimate the uncertainty in the calculated temperature, while taking into account the correlation between parameters and the possibility of non-normal probability distributions. In addition, the Monte Carlo method is compared to an analysis that assumes normally distributed, independent parameters. Both analysis methods show that the magnitude of the initial pressure and the uncertainty of the initial temperature have strong influences on the magnitude of the uncertainty. Finally, the uncertainty estimation methods studied here provide a reference value for the uncertainty of the reference temperature in an RCM and can be generalized to other similar facilities.
    Combustion and Flame 06/2015; 162(6). DOI:10.1016/j.combustflame.2015.03.001 · 3.08 Impact Factor