Thermodynamic diamond

In the attempt at diamond synthesis (4), much unsuccesshil effort was devoted to processes that deposited carbon at low, graphite-stable pressures. Many chemical reactions Hberating free carbon were studied at pressures then available. New high pressure apparatus was painstakingly buHt, tested, analy2ed, rebuilt, and sometimes discarded. It was generally beheved that diamond would be more likely to form at thermodynamically stable pressures. 

Metastable growth of diamond takes place from gases rich in carbon and hydrogen at low pressures where diamond would appear to be thermodynamically unstable. The subject has a long history, beginning with work in the United States and Russia as early as 1962 (30—32) but not achieving widespread interest and acceptance until about 1986 after successful work in Japan. 

A distinction between a solid and liquid is often made in terms of the presence of a crystalline or noncrystalline state. Crystals have definite lines of cleavage and an orderly geometric structure. Thus, diamond is crystalline and solid, while glass is not. The hardness of the substance does not determine the physical state. Soft crystals such as sodium metal, naphthalene, and ice are solid while supercooled glycerine or supercooled quartz are not crystalline and are better considered to be supercooled liquids. Intermediate between the solid and liquid are liquid crystals, which have orderly structures in one or two dimensions,4 but not all three. These demonstrate that science is never as simple as we try to make it through our classification schemes. We will see that thermodynamics handles such exceptions with ease. 

One of the first attempts to calculate the thermodynamic properties of an atomic solid assumed that the solid consists of an array of spheres occupying the lattice points in the crystal. Each atom is rattling around in a hole at the lattice site. Adding energy (usually as heat) increases the motion of the atom, giving it more kinetic energy. The heat capacity, which we know is a measure of the ability of the solid to absorb this heat, varies with temperature and with the substance.8 Figure 10.11, for example, shows how the heat capacity Cy.m for the atomic solids Ag and C(diamond) vary with temperature.dd ee The heat capacity starts at a value of zero at zero Kelvin, then increases rapidly with temperature, and levels out at a value of 3R (24.94 J-K -mol-1). The... 

Solid carbon exists as graphite, diamond, and other phases such as the fullerenes, which have structures related to that of graphite. Graphite is the thermodynamically most stable of these allotropes under ordinary conditions. In this section, we see how the properties of the different allotropes of carbon are related to differences in bonding. 

To deposit diamond by CVD, the carbon species must be activated since, at low pressure, graphite is thermodynamically stable and without activation only graphite would be formed. Activation is obtained by two energy-intensive methods high temperature and plasma. CVD processes based on these two methods are continuously expanded and improved and new ones are regularly proposed. 

If 14 or more carbons are present, the product may be diamantane or a substituted diamantane. These reactions are successful because of the high thermodynamic stability of adamantane, diamantane, and similar diamond-like molecules. The most stable of a set of C H isomers (called the stabilomer) will be the end product if the reaction reaches equilibrium. Best yields are obtained by the use of sludge ... 

As a result of the mobility of the electrons in n orbitals, graphite is a conductor of electricity. It is also the form of carbon used as the thermodynamic standard state. On the other hand, diamond contains carbon atoms that are bonded to four others, so all of the electrons are used in localized bonding, and it is a nonconductor that has the structure shown in Figure 13.12. 

Figure 5.4 The phase diagram of carbon showing the two solid-state extremes of diamond and graphite. Graphite is the thermodynamically stable form of carbon at room temperature and pressure, but the rate of the transition C iamond) — C aphite) is virtually infinitesimal...

There is a wealth of information on this thermodynamic transformation, e.g. in most textbooks of physical chemistry. The site http //chemistry.about.comAibrary/weekly/ aa071601a.htm has copious links, while the short Web page http //members.tripod. com/graphiteboy/Graphite Diamond.htm cites a few nice details... 

Katz, Y. and Diamond, J. M. (1974). Thermodynamic constants for nonelectrolyte partition between dimyristoyl lecithin and water, J. Membr. Biol., 17, 101-120. 

Figure 5 Relationship among loci of structural, dynamic, and thermodynamic anomalies in SPC/E water. The structurally anomalous region is bounded by the loci of q maxima (upward-pointing triangles) and t minima (downward-pointing triangles). Inside of this region, water becomes more disordered when compressed. The loci of diffusivity minima (circles) and maxima (diamonds) define the region of dynamic anomalies, where self-diffusivity increases with density. Inside of the thermodynamically anomalous region (squares), the density increases when water is heated at constant pressure. Reprinted with permission from Ref. 29.

High-pressure experiments promise to provide insight into chemical reactivity under extreme conditions. For instance, chemical equilibrium analysis of shocked hydrocarbons predicts the formation of condensed carbon and molecular hydrogen.17 Similar mechanisms are at play when detonating energetic materials form condensed carbon.10 Diamond anvil cell experiments have been used to determine the equation of state of methanol under high pressures.18 We can then use a thermodynamic model to estimate the amount of methanol formed under detonation conditions.19... 

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