Saturday, 10 May 2014

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How does salt such as NaCl maintain their crystalline structure?

Crystalline materials are made up of periodic structures. We're only going to primarily focus on binary compounds where there is not a high degree of covalency. There are several ways to think about this problem, but let's start with the melting of a crystal.

Traditionally we interpret this as saying that there is a thermally-driven increase in entropy when we melt a highly ordered crystal into a liquid which more than offsets the energy cost associated with the enthalpies of the interactions holding that crystal together. A chemist tends to learn early on that the reverse is not necessarily true: at some definite temperature a perfect crystal rarely forms from the liquid. 

Sodium and chlorine atoms form the particular structure of face-centered cubic because the relative size of the ions -- small for sodium large for chlorine -- makes that arrangement less stressful (energetically favorable). However, if you change the relative sizes of the ions, face-centered cubic is no longer guaranteed.

The formation of an ionic crystal such as sodium chloride is a delicate balance between electrostatic attraction and Pauli repulsion. Electrostatic attraction says that between two different charges, q+ and q, there is a Coulomb force 

A repulsive force due to a quantum mechanical principle called the Pauli Exclusion Principle overpowers the attraction. An equilibrium results in which the atoms sit a certain distance from one another so that, if you will humor me, the "forces" between them balance out. This is why we traditionally represent crystal packing using marbles with a unique radii. The radii of the hard marble represents where the Pauli repulsion overpowers the attraction.









F=kq+q



r2



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