The gas phase

The thermodynamic properties of gases are given through equations of state (EoS) which in general may be given as 

Using the ideal gas law the Gibbs energy expression becomes 

For any single-component system such as a pure gas the molar Gibbs energy is identical to the chemical potential, and the chemical potential for an ideal gas is thus expressed as 

The value of this standard molar Gibbs energy, p°(T), found in data compilations, is obtained by integration from 0 K of the heat capacity determined by the translational, rotational, vibrational and electronic energy levels of the gas. These are determined experimentally by spectroscopic methods [14], However, contrary to what we shall see for condensed phases, the effect of pressure often exceeds the effect of temperature. Hence for gases most attention is given to the equations of state. 

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Clearly, in the liquid phase much higher concentrations of Cfeed (kmol m ) can be maintained than in the gas phase. This makes liquid-phase reactions in general more rapid and hence leads to smaller reactor volumes for liquid-phase reactors. 

Homogeneous catalysts. With a homogeneous catalyst, the reaction proceeds entirely in the vapor or liquid phase. The catalyst may modify the reaction mechanism by participation in the reaction but is regenerated in a subsequent step. The catalyst is then free to promote further reaction. An example of such a homogeneous catalytic reaction is the production of acetic anhydride. In the first stage of the process, acetic acid is pyrolyzed to ketene in the gas phase at TOO C ... 

The performance of fluidized-bed reactors is not approximated by either the well-stirred or plug-flow idealized models. The solid phase tends to be well-mixed, but the bubbles lead to the gas phase having a poorer performance than well mixed. Overall, the performance of a fluidized-bed reactor often lies somewhere between the well-stirred and plug-flow models. 

The reaction is carried out in the gas phase sind normally operates at around 700°C and 40 bar. Some of the benzene formed undergoes a secondary reversible reaction to an unwanted byproduct, diphenyl, according to the reaction... 

Selenium dichloride, SeCl2, is only stable in the gas phase. 

For a binary mixture of two components A and B in the gas phase, the mutual diffusion coefficient such as defined in 4.3.2.3, does not depend on composition. It can be calculated by the Fuller (1966) method ... 

Gg = partial free energy of component i in the gas phase at temperature T and pressure P [kJ/kmol]... 

The ratio fj/Pyj is written as (/>, and called the partial fugacity coefficient in the liquid phase, this coefficient is written as , and in the gas phase 0. ... 

Catalytic cracking is a key refining process along with catalytic reforming and alkylation for the production of gasoline. Operating at low pressure and in the gas phase, it uses the catalyst as a solid heat transfer medium. The reaction temperature is 500-540°C and residence time is on the order of one second. 

Carbon dioxide (CO2) is a very common contaminant in hydrocarbon fluids, especially in gases and gas condensate, and is a source of corrosion problems. CO2 in the gas phase dissolves in any water present to form carbonic acid (H2CO3) which is highly corrosive. Its reaction with iron creates iron carbonate (FeCOg) ... 

Using this mixture as an example, consider starting at pressure A and isothermally reducing the pressure to point D on the diagram. At point A the mixture exists entirely in the liquid phase. When the pressure drops to point B, the first bubble of gas is evolved, and this will be a bubble of the lighter component, ethane. As the pressure continues to drop, the gas phase will acquire more of the heavier component and hence the liquid volume decreases. At point C, the last drop of liquid remaining will be composed of the heavier component, which itself will vaporise as the dew point is crossed, so that below... 

Unlike gases, liquid viscosity decreases as temperature increases, as the molecules move further apart and decrease their internal friction. Like gases, oil viscosity increases as the pressure increases, at least above the bubble point. Below the bubble point, when the solution gas is liberated, oil viscosity increases because the lighter oil components of the oil (which lower the viscosity of oil) are the ones which transfer to the gas phase. 

For a single stage separator i.e. only one separator vessel, there is an optimum pressure which yields the maximum amount of oil and minimises the carry over of heavy components into the gas phase (a phenomenon called stripping). By adding additional separators to the process line the yield of oil can be increased, but with each additional separator the incremental oil yield will decrease. 

As small droplets of liquid are usually still present in the gas phase, demisting secWons are required to recover the liquid mist before it is carried over" in the gas stream out of the separator. The largest liquid droplets fall out of the gas quickly under the action of gravity but smaller droplets (less than 200 microns) require more sophisticated extraction systems. 

As well as preventing liquid carry over in the gas phase, gas carry undef must also be prevented in the liquid phase. Gas bubbles entrained in the liquid phase must be given the opportunity (or residence time) to escape to the gas phase under buoyancy forces. 

Unfortunately, however, one cannot subject a liquid surface to an increased pressure without introducing a second component into the system, such as some inteit gas. One thus increases the density of matter in the gas phase and, moreover, there will be some gas adsorbed on the liquid surface with a corresponding volume change. 

As also noted in the preceding chapter, it is customary to divide adsorption into two broad classes, namely, physical adsorption and chemisorption. Physical adsorption equilibrium is very rapid in attainment (except when limited by mass transport rates in the gas phase or within a porous adsorbent) and is reversible, the adsorbate being removable without change by lowering the pressure (there may be hysteresis in the case of a porous solid). It is supposed that this type of adsorption occurs as a result of the same type of relatively nonspecific intermolecular forces that are responsible for the condensation of a vapor to a liquid, and in physical adsorption the heat of adsorption should be in the range of heats of condensation. Physical adsorption is usually important only for gases below their critical temperature, that is, for vapors. 

Here, if Z is expressed in moles of collisions per square centimeter per second, r is in moles per square centimeter. We assume the condensation coefficient to be unity, that is, that all molecules that hit the surface stick to it. At very low Q values, F as given by Eq. XVII-3 is of the order expected just on the basis that the gas phase continues uniformly up to the surface so that the net surface concentration (e.g., F2 in Eq. XI-24) is essentially zero. This is the situation... 

Finally, it is perfectly possible to choose a standard state for the surface phase. De Boer [14] makes a plea for taking that value of such that the average distance apart of the molecules is the same as in the gas phase at STP. This is a hypothetical standard state in that for an ideal two-dimensional gas with this molecular separation would be 0.338 dyn/cm at 0°C. The standard molecular area is then 4.08 x 10 T. The main advantage of this choice is that it simplifies the relationship between translational entropies of the two- and the three-dimensional standard states. 

Mention was made in Section XVIII-2E of programmed desorption this technique gives specific information about both the adsorption and the desorption of specific molecular states, at least when applied to single-crystal surfaces. The kinetic theory involved is essentially that used in Section XVI-3A. It will be recalled that the adsorption rate was there taken to be simply the rate at which molecules from the gas phase would strike a site area times the fraction of unoccupied sites. If the adsorption is activated, the fraction of molecules hitting and sticking that can proceed to a chemisorbed state is given by exp(-E /RT). The adsorption rate constant of Eq. XVII-13 becomes... 

The course of a surface reaction can in principle be followed directly with the use of various surface spectroscopic techniques plus equipment allowing the rapid transfer of the surface from reaction to high-vacuum conditions see Campbell [232]. More often, however, the experimental observables are the changes with time of the concentrations of reactants and products in the gas phase. The rate law in terms of surface concentrations might be called the true rate law and the one analogous to that for a homogeneous system. What is observed, however, is an apparent rate law giving the dependence of the rate on the various gas pressures. The true and the apparent rate laws can be related if one assumes that adsorption equilibrium is rapid compared to the surface reaction. 

It was pointed out that a bimolecular reaction can be accelerated by a catalyst just from a concentration effect. As an illustrative calculation, assume that A and B react in the gas phase with 1 1 stoichiometry and according to a bimolecular rate law, with the second-order rate constant k equal to 10 1 mol" see" at 0°C. Now, assuming that an equimolar mixture of the gases is condensed to a liquid film on a catalyst surface and the rate constant in the condensed liquid solution is taken to be the same as for the gas phase reaction, calculate the ratio of half times for reaction in the gas phase and on the catalyst surface at 0°C. Assume further that the density of the liquid phase is 1000 times that of the gas phase. 

Traditionally one categorizes matter by phases such as gases, liquids and solids. Chemistry is usually concerned with matter m the gas and liquid phases, whereas physics is concerned with the solid phase. However, this distinction is not well defined often chemists are concerned with the solid state and reactions between solid-state phases, and physicists often study atoms and molecular systems in the gas phase. The tenn condensed phases usually encompasses both the liquid state and the solid state, but not the gas state. In this section, the emphasis will be placed on the solid state with a brief discussion of liquids. 

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