An Electromagnetic Hypothesis of the Kinetics of Heterogeneous Equilibrium, the Structure of Liquids, and Cohesion.

Harkins, William D.; King, H. H.

doi:10.1021/ja02227a007

Cited by 27 publications

(4 citation statements)

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“…The drop volume method is a common experimental technique for measuring interfacial tensions. It is based on an empirical equation, originally advanced by Harkins and Brown, relating the weight of the falling drop to the interfacial tension force acting at the orifice where R 0 is the radius of the orifice and V d is the volume of the drop. ×a6 H - B is an empirical factor introduced to make allowance for the difference between the radius of the orifice and the minimum radius of the neck.…”

Section: Pendant Dropmentioning

confidence: 99%

Mesoscopic Simulation of Drops in Gravitational and Shear Fields

et al. 2000

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In seeking validation of Dissipative Particle Dynamics (DPD) for the mesoscopic modeling of multiphase fluid-fluid systems in external fields, simulations of a pendant drop and a drop in simple shear flow have been performed. The shape profile of the simulated pendant drop was found to be in perfect agreement with that computed by solving the Laplace equation. At increased values of the gravitational force (g), the drop underwent considerable elongation, developing a "neck" between the solid support and its bulk part. Further increases in g resulted in thinning of the neck, which ruptured as g exceeded a certain value, leading to the detachment of the drop. This picture of the detachment process is consistent with the experimental observations published in the literature. Also, the simulations reproduced the drop volume experiment quantitatively. For the drop in shear flow, the degree of deformation was found to be a linear function of the capillary number (Ca) in the region Ca e 0.11, in good agreement with Taylor's theory; this is despite the fact that the hydrodynamic regime in the simulations (Re ∼ 1-10) is quite different from that assumed in the theory (Re , 1). At increased shear rates the results showed positive departure from linearity, in agreement with theory and experiment. Further increases in Ca resulted in the drop assuming a dumbbell like shape, the middle part of the "dumbbell" gradually stretching to form a thin neck. The rupture of the neck was occasioned by the instabilities manifested in the form of stochastic oscillations which magnified as the critical point was reached. The time evolution of the shape of the drop as it underwent the breakup process in our simulations bears remarkable similarity to the experimental observations of Torza et al. The critical value of the capillary number obtained in the simulations is in reasonable agreement with the experimental figure.

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Section: Pendant Dropmentioning

confidence: 99%

Mesoscopic Simulation of Drops in Gravitational and Shear Fields

et al. 2000

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“…I n the ring method the force f to detach a ring of weight w and radius Y from a liquid surface is measured: f = w + 47rry. The straightforward application of these two methods gives considerable errors (Harkins andBrown 1919, Harkins andJordan 1930) and empirical corrections are necessary. Tables relating the correction factors with dimensionless ratios of geometric dimensions of the drop and the ring are available (Fox andChrisman 1952, Lando andOakley 1967).…”

Section: )mentioning

confidence: 99%

Liquid surfaces: theory of surface tension

Navascués¹

1979

Rep. Prog. Phys.

117

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The theory of equilibrium liquid surfaces is reviewed from the macroscopic (thermodynamic) and microscopic (statistical) points of view. Although emphasis is placed on the surface tension, other surface thermodynamic quantities are treated, especially the contact angle and work of adhesion. The Gibbs scheme is used to describe the surface thermodynamics. The equivalent hydrostatic approach, the curvature dependence of the surface tension and its relation to other surface quantities are presented. T h e effect of solid surface topology on the contact angle is discussed, together with the controversial Young's equation. Good's and Fowkes' theories are described and criticised from the statistical point of view, The surface tension theories for simple liquids (Kirkwood and Buff), simple metals (Evans) and solid-fluid interphases (NavascuCs and Berry) are deduced from a single statistical mechanical formalism. The van der Waals theory of the liquid vapour interphase is presented. Thermodynamic perturbation theory for the interphase (Toxvaerd, Abraham) and the analysis of the free energy density as a functional of the interphase density (Yang, Flemming and Gibbs) are discussed. Theoretical predictions for the surface tension of argon are compared with both laboratory experimental and computer 'experimental' data. A statistical mechanical theory of wetting is presented. Other topics such as the temperature dependence of the surface tension are also discussed in this review. Experimental methods of determining the surface tension and contact angle are briefly described.

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“…Other investigators have, in isolated instances, compared the adsorption of an organic solute between water and air and between water and an organic liquid. Thus, Harkins and King (8) found that the maximum adsorption of butyric acid between water and benzene is the same as that between water and air, but that for equal concentrations of butyric acid in the aqueous phase, the adsorption of the butyric acid is greater at the surface of water than it is at the interface between water and benzene. Harkins and McLaughlin (9) state that the maximum adsorption of butyric acid between water and hexane is approximately the same as between water and benzene.…”

mentioning

confidence: 99%