Rayleigh distillation

In discontinuous simple open distillation discontinuous partial distillation, Rayleigh Distillation) the distillation still is charged with a liquid mixture. Slow heating to the boiling point partially vaporizes the liquid. The vapor becomes enriched with the more volatile components and is withdrawn from the distillation still. After condensing in a condenser the distillate is stored in a distillate receiver (Fig. 2-3). 

Assuming a Rayleigh distillation process and bulk eclogite/fluid D s for 3 GPa without rutile from Table 2... 

Differential condensation in which the liquid separates from the vapour from which it has condensed. This process is analogous to differential, or Rayleigh, distillation, and the condensation curve can be calculated using methods similar to those for determining the change in composition in differential distillation see Volume 2, Chapter 11. 

Equation 14.7 is known as the Rayleigh Equation and describes the material balance around the distillation pot. 

Rayleigh distillation is a process in which the condensate is immediately removed from the vapor after formation (by fallout of rain and snow in the meteorological case) and leads to a higher... 

This is the fundamental distillation equation, often referred to as the Rayleigh law when in its integrated form (Rayleigh, 1896). As far as Dt is considered to be a function of F, this equation applies to the change of any species concentration in the course of phase separation. Liquid-vapor or solid-solid fractionations are liable to the same formulation. 

The simplest example of batch distillation is a single stage, differential distillation, starting with a still pot, initially full, heated at a constant rate. In this process the vapour formed on boiling the liquid is removed at once from the system. Since this vapour is richer in the more volatile component than the liquid, it follows that the liquid remaining becomes steadily weaker in this component, with the result that the composition of the product progressively alters. Thus, whilst the vapour formed over a short period is in equilibrium with the liquid, the total vapour formed is not in equilibrium with the residual liquid. At the end of the process the liquid which has not been vaporised is removed as the bottom product. The analysis of this process was first proposed by Rayleigh(24). 

In the laboratory experiments of Seyfried et al. (1998), naturally altered sea floor basalt (5 Li = +7.4) was reacted with Li-free alkali-chloride aqueous fluid at 350°C for 890 hours (initial fluid/solid mass ratio 2). Samples of the fluid were taken throughout the experiment, and showed initial rapid influx of isotopically heavy-enriched Li released by early-dissolving alteration minerals. However, with progressive reaction, isotopic composition of the fluid decreased and Li concentration reaehed apparent steady state. Although an equilibrium model applies best to the synthetic results, Rayleigh distillation was considered most likely to apply in hydrothermal reactions occurring in nature. 

Figure 8. Calcium values in vertebrate bone and soft tissue samples versus 6 Ca in dietary source (Skulan and DePaolo 1999). Bone values are systematically about 1.3%o lower than source values. Soft tissue values are more variable. All of the values are hypothesized to reflect the balance between Ca dietary intake and exchange with bone calcium (Fig. 9). The soft tissue values are variable largely because the residence time of Ca in the tissues is short. The high value of the egg white reflects Rayleigh-type distillation the egg white loses light Ca to the shell as the shell forms. The small amount of Ca left in the egg white is highly fractionated. The low 6 Ca value of the seal muscle is interpreted as a sign of distress the seal may have had a dietary Ca deficiency for several days or longer before it died, and hence was deriving most of its Ca from bone dissolution.

The compositional relations discussed above are explained by Rayleigh s distillation process (Rayleigh, 1896), choosing a suitable partition coefficient for the component of interest—i.e., for component An, we can write... 

Of special interest in stable isotope geochemistry are evaporation-condensation processes, because differences in the vapour pressures of isotopic compounds lead to significant isotope fractionations. For example, from the vapour pressure data for water given in Table 1.2, it is evident that the lighter molecnlar species are preferentially enriched in the vaponr phase, the extent depending upon the temperature. Such an isotopic separation process can be treated theoretically in terms of fractional distillation or condensation under equilibrium conditions as is expressed by the Rayleigh (1896) equation. For a condensation process, this equation is... 

On the other hand, a linear combination of 10% of an equilibrium boiling (single-step steam separation) and a Rayleigh distillation... 

In a system undergoing Rayleigh distillation, an isotopic ratio in the liquid will evolve according to... 

In this equation, ,/ and mi/2 are the masses of the two isotopes making up RZ1, and the terms are condensation coefficients for the two isotopes, which are determined experimentally and are typically close to 1. Equation (7.2.1) is valid if a is independent of the evolving composition of the evaporating liquid, and the diffusive transport rate is fast enough to keep the liquid homogeneous. The last condition is violated in solids, where diffusion is very slow relative to the evaporation rate, so solids do not undergo Rayleigh distillation. 

Earlier in this chapter, we discussed isotopic fractionation during evaporation. Under appropriate conditions, where the condensed phase remains isotopically well mixed and the gas phase is removed from the system to prevent back reaction, Rayleigh distillation will occur (Box 7.2), resulting in a condensed phase that is isotopically heavy relative to the starting composition (Fig. 7.9). Isotopic fractionation can occur during both condensation and evaporation, as demonstrated by experiments (Richter el al., 2002). But it is not necessary that isotopes fractionate during evaporation or condensation. It depends on the details of the process. If evaporation occurs into a gas phase that is sufficiently dense, back reactions between gas and liquid can reduce the isotopic fractionation to near the equilibrium value, which is very small. For example, sulfur in chondrules does not show the isotopic fractionation (Tachibana and Huss, 2005) expected during evaporation from a liquid. Also, evaporation from a solid does not produce isotopic fractionation in the solid because diffusion is much too slow to equilibrate the few layers of surface atoms that are fractionated with the bulk of the material. 

We have seen that elements can be separated based on their volatility, either through gas-solid or gas-liquid reactions. There are many types of reactions that form a continuum between equilibrium condensation (or its inverse, evaporation) on the one hand and purely kinetically controlled reactions, such as Rayleigh distillation, on the other. In some cases, isotopic fractionation can assist in identifying the processes involved. 

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