VAN KREVELEN

D. W. Van Krevelen, Properties of Polymers, 3rd ed., Elsevier Scientific Publishing Co., Amsterdam, the Netherlands, 1990. 

Estimation of for Irreversible Reactions Figure 14-14 illustrates the influence of either first- or second-order irreversible chemical reactions on the mass-transfer coefficient /cl as developed by Van Krevelen and Hoftyzer [Rec. Trav. Chim., 67, 563 (1948)] and as later refined by Periy and Pigford and by Brian et al. [Am. Inst. Chem. Eng. /., 7, 226(1961)]. 

The Van Krevelen-Hoftyzer relationship was tested experimentally for the second-order system in which CO9 reacts with either NaOH or KOH solutions by Nijsing et al. [Chem. Eng. ScL, 10, 88 (1959)]. Nijsing s results for the NaOH system are shown in Fig. 14-15 and are in excellent agreement with the second-order-reaction theory. Indeed, these experimental results can be described very well by Eqs. (14-80) and (14-81) when values of V = 2 and T)JT = 0.64 are employed in the equations. 

Van Krevelen, D.W. (1990) Properties of Polymers, 3rd edition (Elsevier, Amsterdam). 

The voluminous experimental information about the linkage between structural variables and properties of polymers is assembled in books, notably that by van Krevelen (1990). In effect, such books encapsulate much empirical knowledge on how to formulate polymers for specific applications (Uhlherr and Theodorou 1998). What polymer modellers and simulators strive to achieve is to establish more rigorous links between structural variables and properties, to foster more rational design of polymers in future. 

Numerous reports of comparable levels of success in correlating adhesion performance with the Scatchard-Hildebrand solubility parameters can be found in the literature [116,120-127], but failures of this approach have also been documented [128-132J. Particularly revealing are cases in which failure was attributed to the inability of the Scatchard-Hildebrand solubility parameter to adequately account for donor-acceptor (acid-base) interactions [130,132]. Useful reviews of the use of solubility parameters for choosing block copolymer compatibilizers have been prepared by Ohm [133] and by Gaylord [134]. General reviews of the use of solubility parameters in polymer science have been given by Barton [135], Van Krevelen [114], and Hansen [136]. 

Hansen [137-139], and later van Krevelen [114] proposed the generalization of the solubility parameter concept to attempt to include the effects of strong dipole interactions and hydrogen bonding interactions. It was proposed that the cohesive energy density be written as the sum of three terms, viz. 

As a matter of convenience. Van Krevelen suggests that the dispersion and polar solubility parameter terms be rolled together into a van der Waals term, <5,v, such that... 

General scheme of kerogen evolution from diagenesis to metagenesis in the van Krevelen diagram. 

Van Krevelen et al. [529,530] in rising temperature studies of coal pyrolysis, used the rate equation... 

Mention of the approach given by van Krevelen et al. [529,530] has already been made. Other methods based on points of inflection have been described but in some treatments it would seem probable that the integration constant has been omitted [559]. Doyle s treatment [533] avoids this error by using a characteristic temperature, 0 = T— Tm, where Tm is the temperature at which the reaction rate reaches a maximum. Doyle writes... 

Pag), where y o mole fraction of A in bulk gas phase can be determined iteratively, yAi = mole fiaction of A in gas inlet. Equations (1) to (6) were solved using fourth order Runge-Kutta method [1, 8]. The value of enhancement factor, E, was predicted using equation of Van Krevelen and Hoftijzer [2]. 

Catalytic oxidations on the surface of oxidic materials usually proceed according to the Mars-Van Krevelen mechanism [P. Mars and D.W. van Krevelen, Chem. Eng. Sci. 3 (1954) 41], as illustrated in Fig. 9.17 for the case of CO oxidation. Instead of a surface reaction between CO and an adsorbed O atom, CO2 is formed by reaction between adsorbed CO and an O atom from the metal oxide lattice. The vacancy formed is filled in a separate reaction step, involving O2 activation, often on defect sites. 

Figure 9.17. Mars-Van Krevelen mechanism for the oxidation of CO on a metal oxide surface. A characteristic feature is that lattice oxygen is used to oxidize the CO, leaving a defect that is replenished in a separate step by oxygen from the gas phase.

Dumesic et al. proposed a model involving six steps based on the general Mars-van Krevelen mechanism for oxidations ... 

Explain the Mars-van Krevelen mechanism. In what sense does it differ from a metal-catalyzed reaction ... 

Can the hydrodesulfurization reaction also be considered to be a Mars-van Krevelen reaction ... 

Transition metal oxides represent a prominent class of partial oxidation catalysts [1-3]. Nevertheless, materials belonging to this class are also active in catalytic combustion. Total oxidation processes for environmental protection are mostly carried out industriaUy on the much more expensive noble metal-based catalysts [4]. Total oxidation is directly related to partial oxidation, athough opposes to it. Thus, investigations on the mechanism of catalytic combustion by transition metal oxides can be useful both to avoid it in partial oxidation and to develop new cheaper materials for catalytic combustion processes. However, although some aspects of the selective oxidation mechanisms appear to be rather established, like the involvement of lattice catalyst oxygen (nucleophilic oxygen) in Mars-van Krevelen type redox cycles [5], others are still uncompletely clarified. Even less is known on the mechanism of total oxidation over transition metal oxides [1-4,6]. 

In the cases of the selective oxidation reactions over metal oxide catalysts the so-called Mars-van Krevelen or redox mechanism [4], involving nucleophilic oxide ions 0 is widely accepted. A possible role of adsorbed electrophilic oxygen (molecularly adsorbed O2 and / or partially reduced oxygen species like C , or 0 ) in complete oxidation has been proposed by Haber (2]. However, Satterfield [1] queried whether surface chemisorbed oxygen plays any role in catalytic oxidation. 

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