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Calculation of surface energy from first principles (for example, density functional theory) is an alternative approach to measurement. Surface energy is estimated from the following variables: width of the d-band, the number of valence d-electrons, and the coordination number of atoms at the surface and in the bulk of the solid. [5] [page needed]
Gibbs emphasized that for solids, the surface free energy may be completely different from surface stress (what he called surface tension): [14]: 315 the surface free energy is the work required to form the surface, while surface stress is the work required to stretch the surface. In the case of a two-fluid interface, there is no distinction ...
Here σ is the surface tension, n, t and s are unit vectors in a local orthogonal coordinate system (n,t,s) at the free surface (n is outward normal to the free surface while the other two lie in the tangential plane and are mutually orthogonal). The indices 'l' and 'g' denote liquid and gas, respectively and K is the curvature of the free surface.
During this process, surface tension decrease as function of time and finally approach the equilibrium surface tension (σ equilibrium). [3] Such a process is illustrated in figure 1. (Image was reproduced from reference) [2] Figure 1: Migration of surfactant molecules and change of surface tension (σ t1 > σ t2 > σ equilibrium).
Here () denotes the surface tension (or (excess) surface free energy) of a liquid drop with radius , whereas denotes its value in the planar limit. In both definitions (1) and (2) the Tolman length is defined as a coefficient in an expansion in 1 / R {\displaystyle 1/R} and therefore does not depend on R {\displaystyle R} .
The surface energy is measured in units of joules per square meter, which is equivalent in the case of liquids to surface tension, measured in newtons per meter.The overall surface tension/energy of a liquid can be acquired through various methods using a tensiometer or using the pendant drop method and maximum bubble pressure method.
If surface tension is high, there is a large free energy required to increase the surface area, so the surface will tend to contract and hold together like a rubber sheet. There are various factors affecting surface tension, one of which is that the composition of the surface may be different from the bulk.
Flatness refers to the shape of a liquid's free surface. On Earth, the flatness of a liquid is a function of the curvature of the planet, and from trigonometry, can be found to deviate from true flatness by approximately 19.6 nanometers over an area of 1 square meter, a deviation which is dominated by the effects of surface tension.