Carbon graphite-diamond conversion

From a thermodynamic point of view, the transformation of graphite is accessible with the available experimental apparatuses, but it is kinetically impossible. Geological times, hundreds of years, are required for spontaneous formation of diamond in appropriate conditions, and kinetic factors prevent the observation of the reaction in any practical time scale. H. T. Hall has demonstrated that for graphite diamond conversion, carbon-carbon bonds must be broken in a solvent and on December 1954 realized the first synthesis of diamond, at approximately 2000 K and 10 GPa, in molten troilite (FeS) solvent, using a belt-type high-pressure-high-temperature apparatus [516-519]. Since then, many substances, minerals, and transition metals, in particular, have been... 

Fig. 10-1. Carbon phase diagram. Shaded area is the most favorable for catalyzed graphite-diamond conversion. [Adapted from F. P. Bundy, J. Chem. Phys., 1963, 38,...

Crystal Structure. Diamonds prepared by the direct conversion of well-crystallized graphite, at pressures of about 13 GPa (130 kbar), show certain unusual reflections in the x-ray diffraction patterns (25). They could be explained by assuming a hexagonal diamond stmcture (related to wurtzite) with a = 0.252 and c = 0.412 nm, space group P63 /mmc — Dgj with four atoms per unit cell. The calculated density would be 3.51 g/cm, the same as for ordinary cubic diamond, and the distances between nearest neighbor carbon atoms would be the same in both hexagonal and cubic diamond, 0.154 nm. 

At 25°C and 1 atm, graphite is the stable form of carbon. Diamond, in principle, should slowly transform to graphite under ordinary conditions. Fortunately for the owners of diamond rings, this transition occurs at zero rate unless the diamond is heated to about 1500°C, at which temperature the conversion occurs rapidly. For understandable reasons, no one has ever become very excited over the commercial possibilities of this process. The more difficult task of converting graphite to diamond has aroused much greater enthusiasm. 

It follows from the definition just given that the standard enthalpy of formation of an element in its most stable form is zero. For instance, the standard enthalpy of formation of C(gr) is zero because C(gr) — C(gr) is a null reaction (that is, nothing changes). We write, for instance, AHf°(C, gr) = 0. However, the enthalpy of formation of an element in a form other than its most stable one is nonzero. For example, the conversion of carbon from graphite (its most stable form) into diamond is endothermic ... 

As we saw in Section 5.1, a single substance can exist in different phases, or physical forms. The phases of a substance include its solid, liquid, and gaseous forms and its different solid forms, such as the diamond and graphite phases of carbon. In one case—helium—two liquid phases are known to exist. The conversion of a substance from one phase into another, such as the melting of ice, the vaporization of water, and the conversion of graphite into diamond, is called a phase transition (recall Section 6.11). 

Figure 36, P-T phase and reaction diagram of carbon as results from Refs. 509 and 510. Solid lines represent equilibrium phase boundaries. The dashed line is the threshold for conversion of hexagonal diamond and both hexagonal and rhombohedral graphite into cubic diamond.

It is well known that graphite is the stable form of carbon at ambient conditions, and studies have been undertaken to find pressure and temperature conditions where diamond becomes stable, and as a consequence, graphite would convert spontaneously to diamond. The process is fraught with difficulty, and for many years the conversion was not successful. The... 

The successful conversion of graphite to diamond involves crystallizing the diamond from a liquid melt. The solvent most often used is nickel metal, or alloys of nickel with other ferrous metals. The reason for this success can be seen by referring to Figure 15.7, the binary (solid + liquid) phase diagram for (nickel + carbon).u8 We note from the figure that (Ni + C) forms a simple... 

From Table 7-1, the formation of diamond from graphite (the standard state of carbon) is accompanied by a positive AH of 1.88kJ/mol at 25°C. From Problem 16.1(f), AS for the same process is negative. Since 25°C is not the transition temperature, the process is not a reversible one. In fact, it is not even a spontaneous irreversible process, and (16-2) does not apply with the inequality sign. On the contrary, the opposite process, the conversion of diamond to graphite at 1 atm, is thermodynamically spontaneous. The AS for this process would obey (16-2) with the inequality sign. This means that diamonds are NOT forever The term spontaneous does not cover the speed... 

For a reaction studied under conditions of constant pressure, we can obtain the enthalpy change by using a calorimeter. However, this process can be very difficult. In fact, in some cases it is impossible, since certain reactions do not lend themselves to such study. An example is the conversion of solid carbon from its graphite form to its diamond form ... 

In principle, you can determine A// for any chemical reaction by using a calorimeter to measme the heat evolved or absorbed during the reaction. However, consider the reaction involving the conversion of carbon in its allotropic form diamond to carbon in its allotropic form graphite. 

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