Transformation of Graphite to Diamond

Another notable solid-solid equilibrium is the graphite-to-diamond transition in the element carbon. Graphite is fairly common in the earth's crust but the rarity of diamond is the origin of its value. Under normal terrestrial conditions (300 K, 1 atm) the two forms of carbon are not in equilibrium and so, thermodynamically speaking, only one form should exist. The stable form is the one with the lowest Gibbs free energy. At 300 K, the enthalpy difference between diamond and graphite is Ahd-g = 1900 J/mole, with diamond less stable than graphite in this regard. Being a highly ordered structure, diamond has a molar entropy lower than that of graphite, and Asd-g = -3.3 J/mole-K (see Fig. 3.6). This difference also favors the stability of graphite. The combination of the enthalpy and entropy effects produces a free-energy difference of:

Agd-g = gdiamond - ggraphite = Ahd-g -TAsd-g = 1900 - 300(-3.3) = 2880 J/mole

Since the phase with the lowest free energy (graphite) is stable, diamond is a metastable phase. It exists only because the kinetics of transformation to graphite is extremely slow at ambient temperature. How then does diamond form?

The phase diagram of carbon is shown in Fig. 5.5. At low pressure, graphite is stable at all temperatures up to the melting point. In order to transform graphite into diamond at constant temperature, the pressure must be very high. This is how, deep under the earth, diamond was created.

There is a considerable industrial market for synthetic diamonds, and the pressure required for the transformation can be read from the phase diagram of Fig. 5.5, or it can be calculated by applying the fundamental differential dg = vdp at constant temperature to both phases and taking the difference:

"dAgdV

Getting Started With Solar

Getting Started With Solar

Do we really want the one thing that gives us its resources unconditionally to suffer even more than it is suffering now? Nature, is a part of our being from the earliest human days. We respect Nature and it gives us its bounty, but in the recent past greedy money hungry corporations have made us all so destructive, so wasteful.

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