Diamond-graphite conversion

Theoretically at least, diamond is not forever graphite would be better qualified. However, in all fairness, the rate of the diamond-graphite conversion is infinitesimally small at ordinary temperatures and, for all practical purposes, diamond is stable, as evidenced by the presence of natural diamonds in some alluvial deposits which were formed overa billion years ago and have not changed since. The carbon phase diagram, illustrated in Fig. 2.20 of Ch. 2, shows the relationship between these two allotropes of carbon. 

Thus, the formation of graphite from diamond is favored under standard-state conditions at 25°C. However, the rate of the diamond to graphite conversion is very slow (due to a high activation energy) so that it will take millions of years before the process is complete. 

There is always interest in the possible conversions of graphite to diamond. Graphite is the thermodynamically more stable phase with an enthalpy of transition of diamond to... 

Even though graphite is thermodynamically more stable than diamond, the conversion of diamond to graphite is kinetically so slow that it does not occur at any measurable rate. 

Figure 4 A part of carbon phase diagram 1, a triple point 2, melting of graphite 3, diamond graphite transformation 4, Liepunski s prediction for indirect conversion (Fe—C) 5, Bundy s minimum for diamond formation from Fe—C 6, synthesis of diamond from glassy carbon (12) 7, the same according to Ref. 13.

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). 

AH = 2.9 kj mol-1 at 300 K and 1 atm, there is no low-energy pathway for the transformation, so the process is difficult to carry out. However, synthetic diamonds are produced on a large scale at high temperature and pressure (3000 K and 125kbar). The conversion of graphite to diamonds is catalyzed by several metals (i.e., chromium, iron, and platinum) that are in the liquid state. It is believed that... 

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.

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... 

It has been reported that when Ceo is rapidly and nonhydrostatically compressed above 20 GPa at room temperature, it transforms into polycrystalline diamond [524]. Although Ceo can be considered as a folded graphite sheet, we must take into account that in the pentagons there is an important tetrahedral distortion making the transformation of Ceo into diamond likely easier than the HP-HT conversion from graphite, and it is possible to use this reaction for industrial production of diamonds. 

In practice, the primary objective of chemical thermodynamics is to estabhsh a criterion for determining the feasibility or spontaneity of a given physical or chemical transformation. For example, we may be interested in a criterion for determining the feasibility of a spontaneous transformation from one phase to another, such as the conversion of graphite to diamond, or the spontaneous direction of a metabohc reaction that occurs in a cell. On the basis of the first and second laws of thermod5m-amics, which are expressed in terms of Gibbs s functions, several additional theoretical concepts and mathematical functions have been developed that provide a powerful approach to the solution of these questions. 

A quite different set of dynamic high-pressure techniques are based on the use of chemical or nuclear explosions to produce transient shock waves of high peak pressure but short duration. With such methods, one can often penetrate the high-T, P regions where kinetic barriers become unimportant and a catalyst is unnecessary. However, the same kinetics that allows facile conversion of graphite to diamonds as the shock front arrives also allows the facile back-conversion as the shock wave passes. As a pioneer of shock-wave diamond synthesis remarked ruefully, We were millionaires for one microsecond [B. J. Alder and C. S. Christian. Phys. Rev. Lett. 7, 367 (1961) B. J. Alder, in W. Paul and D. M. Warschauer (eds). Solids under Pressure (McGraw-Hill, New York, 1963), p. 385]. 

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