The Condensation Equation

We saw in Chapter 12 that the rate of change of the mass of a particle of diameter Dp as a result of transport of species i between the gas and aerosol phases is 

Let us define the condensation growth rate Iv(v) as the rate of change of the volume of a particle of volume v. Assuming that the aerosol particle contains only one species, it will 

FIGURE 13.1 Schematic of differential mass balance for the derivation of growth equation for a particle population. 

Equation (13.7) is called the condensation equation and describes mathematically the rate of change of a particle size distribution n(v,t) due to the condensation or evaporation flux / ( , /), neglecting other processes that may influence the distribution shape (sources, removal, coagulation, nucleation, etc). A series of alternative forms of the condensation equation can be written depending on the form of the size distribution used or the expression for the condensation flux. For example, if the mass of a particle is used as the independent variable, one can show that the condensation equation takes the form 

Finally, if the diameter is the independent variable of choice, the number distribution is given by no Dp, t) and the condensation equation is 

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The condensation rate in the condenser L, changes as the pressure in the condenser varies since the condensing temperature depends on pressure. Thus depends on column pressure, overhead vapor composition, and the temperature of the coolant in the condenser. Equation (S.33) assumes ideal gas behavior, which is usually adequate in these low-pressure columns where pressure changes are significant. 

The water precipitated from solution os the condensate cools to 18°C mu t be absorbed by the pipeline gas and is equivalent to an odditionol 22 mg/m of gas woter content. Similory each 0.01% by volume of residuol free woter in the condensate equates to an additional 18 mg/m of water in the gas phose. 

Referring to Figure 2.2 for MVC column configuration, the model equations for the rectifying section are the same (except the reboiler equations) as those presented for conventional batch distillation column (Type III, IV, V in section 4.2). The model equations for the stripping section are the same (except the condenser equations) as those presented for inverted batch distillation column (Type III, IV, V in section 4.3.2). However, note that the vapour and liquid flow rates in the rectifying and stripping sections will not be same because of the introduction of the feed plate. 

The vapor pressures of benzene and toluene at 80°C are determined from the Antoine equation to be 757.7 mm Hg and 291.2 mm Hg, respectively. Assuming that nitrogen is insoluble in the condensate. Equation 6.4-8 gives... 

The condensation equation assuming continuum regime growth, unity accommodation coefficient, and constant gas-phase supersaturation can be written using (13.10) and (13.13) as... 

Returning to the solution of the condensation equation, the constant value of F(Dp,t) along each characteristic curve can be determined by its value of t = 0, that is... 

In the absence of nucleation (Jq(v) = 0), sources (S(v) = 0), sinks (R(v) = 0), and growth [/( ) = 0], we have the continuous coagulation equation (13.61). If particle concentrations are sufficiently small, coagulation can be neglected. If there are no sources or sinks of particles then the general dynamic equation is simplified to the condensation equation (13.7). 

When vapor is totally condensed, a cylindrical, horizontal reflux drum is commonly employed to receive the condensate. Equations (13-9) and (13-11) permit estimates of the drum diameter and length Ly by assuming an optimum LylD of four and the same liquid residence time suggested for a vertical drum. 

Replacing the volume by the molar volume of the gas, = Yin, i.e., the volume per unit amount of substance expressed in m moT , we obtain the condensed equation of state of ideal gases ... 

Provided the reflux is returned to the column at its bubble point, i.e. there is no subcooling by the condenser, Equations (12.18) and (12.22) can be plotted on the McCabe-Thiele diagram. These are shown in Figure 12.8 they lie between the vapour and liquid hues. By establishing a realistic reflux we have increased the number of theoretical trays required. We have saved energy but now require a taller column. Column design is therefore a trade-off between operating cost and cost of construction. 

In a number of experiments substrate temperature is kept to be so low, that mean life time of adatoms exceeds the time of maximum supersatmation formation (so-called regime of complete condensation). In this case one is to solve the condensation equation together with the non-stationary diffusion equation describing the growth of clusters. Taking to = oo gives the following bedance equation... 

In a binary liquid solution containing one noncondensable and one condensable component, it is customary to refer to the first as the solute and to the second as the solvent. Equation (13) is used for the normalization of the solvent s activity coefficient but Equation (14) is used for the solute. Since the normalizations for the two components are not the same, they are said to follow the unsymmetric convention. The standard-state fugacity of the solvent is the fugacity of the pure liquid. The standard-state fugacity of the solute is Henry s constant. 

To illustrate calculations for a binary system containing a supercritical, condensable component. Figure 12 shows isobaric equilibria for ethane-n-heptane. Using the virial equation for vapor-phase fugacity coefficients, and the UNIQUAC equation for liquid-phase activity coefficients, calculated results give an excellent representation of the data of Kay (1938). In this case,the total pressure is not large and therefore, the mixture is at all times remote from critical conditions. For this binary system, the particular method of calculation used here would not be successful at appreciably higher pressures. 

Table 3 shows results obtained from a five-component, isothermal flash calculation. In this system there are two condensable components (acetone and benzene) and three noncondensable components (hydrogen, carbon monoxide, and methane). Henry s constants for each of the noncondensables were obtained from Equations (18-22) the simplifying assumption for dilute solutions [Equation (17)] was also used for each of the noncondensables. Activity coefficients for both condensable components were calculated with the UNIQUAC equation. For that calculation, all liquid-phase composition variables are on a solute-free basis the only required binary parameters are those for the acetone-benzene system. While no experimental data are available for comparison, the calculated results are probably reliable because all simplifying assumptions are reasonable the... 

The second term in Equation (15a) gives the enthalpy of mixing of the condensable components. It is difficult to estimate that enthalpy but fortunately it ma)ies only a small contri-... 

Standard-state fugacities at zero pressure are evaluated using the Equation (A-2) for both condensable and noncondensable components. The Rackett Equation (B-2) is evaluated to determine the liquid molar volumes as a function of temperature. Standard-state fugacities at system temperature and pressure are given by the product of the standard-state fugacity at zero pressure and the Poynting correction shown in Equation (4-1). Double precision is advisable. 

Activity coefficients for condensable components are calculated with the UNIQUAC Equation (4-15)/ and infinite-dilution activity coefficients for noncondensable components are calculated with Equation (4-22). ... 

At first we tried to explain the phenomenon on the base of the existence of the difference between the saturated vapor pressures above two menisci in dead-end capillary [12]. It results in the evaporation of a liquid from the meniscus of smaller curvature ( classical capillary imbibition) and the condensation of its vapor upon the meniscus of larger curvature originally existed due to capillary condensation. We worked out the mathematical description of both gas-vapor diffusion and evaporation-condensation processes in cone s channel. Solving the system of differential equations for evaporation-condensation processes, we ve derived the formula for the dependence of top s (or inner) liquid column growth on time. But the calculated curves for the kinetics of inner column s length are 1-2 orders of magnitude smaller than the experimental ones [12]. 

To first order, the dispersion (a-a) interaction is independent of the structure in a condensed medium and should be approximately pairwise additive. Qualitatively, this is because the dispersion interaction results from a small perturbation of electronic motions so that many such perturbations can add without serious mutual interaction. Because of this simplification and its ubiquity in colloid and surface science, dispersion forces have received the most significant attention in the past half-century. The way dispersion forces lead to long-range interactions is discussed in Section VI-3 below. Before we present this discussion, it is useful to recast the key equations in cgs/esu units and SI units in Tables VI-2 and VI-3. 

Bikerman [179] has argued that the Kelvin equation should not apply to crystals, that is, in terms of increased vapor pressure or solubility of small crystals. The reasoning is that perfect crystals of whatever size will consist of plane facets whose radius of curvature is therefore infinite. On a molecular scale, it is argued that local condensation-evaporation equilibrium on a crystal plane should not be affected by the extent of the plane, that is, the crystal size, since molecular forces are short range. This conclusion is contrary to that in Section VII-2C. Discuss the situation. The derivation of the Kelvin equation in Ref. 180 is helpful. 

The basic assumption is that the Langmuir equation applies to each layer, with the added postulate that for the first layer the heat of adsorption Q may have some special value, whereas for all succeeding layers, it is equal to Qu, the heat of condensation of the liquid adsorbate. A furfter assumption is that evaporation and condensation can occur only from or on exposed surfaces. As illustrated in Fig. XVII-9, the picture is one of portions of uncovered surface 5o, of surface covered by a single layer 5, by a double-layer 52. and so on.f The condition for equilibrium is taken to be that the amount of each type of surface reaches a steady-state value with respect to the next-deeper one. Thus for 5o... 

Equation XVII-78 turns out to ht type II adsorption isotherms quite well—generally better than does the BET equation. Furthermore, the exact form of the potential function is not very critical if an inverse square dependence is used, the ht tends to be about as good as with the inverse-cube law, and the equation now resembles that for a condensed him in Table XVII-2. Here again, quite similar equations have resulted from deductions based on rather different models. 

When plotted according to the linear form of the BET equation, data for the adsorption of N2 on Graphon at 77 K give an intercept of 0.004 and a slope of 1.7 (both in cubic centimeters STP per gram). Calculate E assuming a molecular area of 16 for N2. Calculate also the heat of adsorption for the first layer (the heat of condensation of N2 is 1.3 kcal/mol). Would your answer for Vm be much different if the intercept were taken to be zero (and the slope the same) Comment briefly on the practical significance of your conclusion. 

Applying Flartree-Fock wavefiinctions to condensed matter systems is not routine. The resulting Flartree-Fock equations are usually too complex to be solved for extended systems. It has been argried drat many-body wavefunction approaches to the condensed matter or large molecular systems do not represent a reasonable approach to the electronic structure problem of extended systems. 

Since and depend only on die valence charge densities, they can be detennined once the valence pseudo- wavefiinctions are known. Because the pseudo-wavefiinctions are nodeless, the resulting pseudopotential is well defined despite the last temi in equation Al.3.78. Once the pseudopotential has been constructed from the atom, it can be transferred to the condensed matter system of interest. For example, the ionic pseudopotential defined by equation Al.3.78 from an atomistic calculation can be transferred to condensed matter phases without any significant loss of accuracy. 

In the LS analysis, an assembly of drops is considered. Growth proceeds by evaporation from drops withi < R and condensation onto drops R > R. The supersaturation e changes in time, so that e (x) becomes a sort of mean field due to all the other droplets and also implies a time-dependent critical radius. R (x) = a/[/"(l)e(x)]. One of the starting equations in the LS analysis is equation (A3.3.87) withi (x). 

Kramers solution of the barrier crossing problem [45] is discussed at length in chapter A3.8 dealing with condensed-phase reaction dynamics. As the starting point to derive its simplest version one may use the Langevin equation, a stochastic differential equation for the time evolution of a slow variable, the reaction coordinate r, subject to a rapidly statistically fluctuating force F caused by microscopic solute-solvent interactions under the influence of an external force field generated by the PES F for the reaction... 

The following equation shows an example of a mixed Claisen condensation m which a benzoate ester is used as the nonenohzable component... 

Numerous mathematical formulas relating the temperature and pressure of the gas phase in equilibrium with the condensed phase have been proposed. The Antoine equation (Eq. 1) gives good correlation with experimental values. Equation 2 is simpler and is often suitable over restricted temperature ranges. In these equations, and the derived differential coefficients for use in the Hag-genmacher and Clausius-Clapeyron equations, the p term is the vapor pressure of the compound in pounds per square inch (psi), the t term is the temperature in degrees Celsius, and the T term is the absolute temperature in kelvins (r°C -I- 273.15). 

The Clapeyron equation expresses the dynamic equilibrium existing between the vapor and the condensed phase of a pure substance ... 

If the fraction of sites occupied is 0, and the fraction of bare sites is 0q (so that 00 + 1 = 0 then the rate of condensation on unit area of surface is OikOo where p is the pressure and k is a constant given by the kinetic theory of gases (k = jL/(MRT) ) a, is the condensation coefficient, i.e. the fraction of incident molecules which actually condense on a surface. The evaporation of an adsorbed molecule from the surface is essentially an activated process in which the energy of activation may be equated to the isosteric heat of adsorption 4,. The rate of evaporation from unit area of surface is therefore equal to... 

An alternative way of deriving the BET equation is to express the problem in statistical-mechanical rather than kinetic terms. Adsorption is explicitly assumed to be localized the surface is regarded as an array of identical adsorption sites, and each of these sites is assumed to form the base of a stack of sites extending out from the surface each stack is treated as a separate system, i.e. the occupancy of any site is independent of the occupancy of sites in neighbouring stacks—a condition which corresponds to the neglect of lateral interactions in the BET model. The further postulate that in any stack the site in the ith layer can be occupied only if all the underlying sites are already occupied, corresponds to the BET picture in which condensation of molecules to form the ith layer can only take place on to molecules which are present in the (i — l)th layer. 

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