Hamaker constant from bulk properties

The van der Waals forces scale up from atomic distances to colloidal distances undiminished. How the molecular forces scale up in the case of large objects, expressions for such forces, definition of the Hamaker constant, and theories based on bulk material properties follow in Sections 10.5-10.7. 

As the structure of the surface, and hence U° and S , are unique for each liquid and completely determined by the nature of the molecules and their interactions, it follows that this also applies to ycmd dy/dT. Therefore, it makes sense to search for molecular interpretations of both of these quantities. However, direct relationships between the surface tension and bulk properties, such as energy densities or Hamaker constants, are basically incomplete unless they take the interfacial rearrangements into account. At best one can say that bulk properties and the surface tension are different manifestations of the same interaction. From the data in sec. 1.12 and app. 1, it is concluded that neglecting the TS° term cam lead to errors of several tens of a percent. 

The chemical nature of a solid determines its adsorptive and wetting properties. Now, the energy of immersion mainly depends on the surface chemistry but also, to some extent, on the nature of the bulk solid. For example, the interaction between water and silica has contributions from the bulk Si02 together with contributions from the silanol groups of the interface. Polar molecules are very sensitive to the local surface chemistry, whereas nonpolar molecules are more sensitive to the bulk composition. Interactions between a bulk Hquid and a bulk solid through an interface are often described in terms of Hamaker constant [16]. Immersion calorimetry in apolar liquids was proposed to estimate the Hamaker constant [17]. The sensitivity of immersion calorimetry to the surface polarity has justified its use for characterising the surface sites. 

From a knowledge of the adsorption, immersion, and wetting properties of solid particles, we have examined the influence of particle-particle and particle-liquid interactions on the stability and structure formation of suspensions of hydrophobic and hydrophilic Aerosil particles in benzene-n-heptane and methanol-benzene mixtures. For the binary mixtures, the Hamaker constants have been determined by optical dispersion measurements over the entire composition range by calculation of the characteristic frequency (Vk) from refractive index measurements [7,29,36,64], The Hamaker constant of an adsorption layer whose composition is different from that of the bulk has been calculated for several mixture compositions on the basis of the above results. Having the excess isotherms available enabled us to determine the adsorption layer thickness as a function of the mixture composition. For interparticle attractive potentials, calculations were done on the basis of the Vincent model [3-5,39]. In the case of hydrophobic particles dispersed in benzene- -heptane and methanol-benzene mixtures, it was established that the change in the attractive potential was in accordance with the interactions obtained from rheological measurements. 

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