Carbon monoxide experimental data

Experimental apparatus Electromagnetic emission source, electromagnetic energy meter (tesla), high frequency mechanical wave recorder, coal and rock strain recorder, methane, ethane, carbon monoxide sensors, data logger. 

The vapor-liquid equilibrium relationships for copper-ammonium salt solutions containing dissolved carbon monoxide have been studied by a number of investigators. Hainsworth and Titus (1921) measured the vapor pressure of carbon monoxide over copper-ammonium carbonate solutions. Experimental data on formate solutions were obtained by Larson and Teitsworth (1922). Zhavoronkov and Reshchikov (1933) studied solutions of chlorides, formates, lactates, and acetates. Zhavoronkov and Chagunava (1940) made a detailed study of formate-carbonate mixtures, including the solution from an operating plant. 

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... 

A sophisticated quantitative analysis of experimental data was performed by Voltz et al. (96). Their experiment was performed over commercially available platinum catalysts on pellets and monoliths, with temperatures and gaseous compositions simulating exhaust gases. They found that carbon monoxide, propylene, and nitric oxide all exhibit strong poisoning effects on all kinetic rates. Their data can be fitted by equations of the form ... 

GP 9[ [R 16]The extent of internal transport limits was analysed for the wide fixed-bed reactor, using experimental data on carbon monoxide conversion and matter and process parameter data for the reactants [78]. The analysis was based on the Weisz modulus and the Anderson criterion for judging possible differences between observed and actual reaction rates. As a result, it was found that the small particles eliminate internal transport limitations. 

Based on the experimental data and some speculations on detailed elementary steps taking place over the catalyst, one can propose the dynamic model. The model discriminates between adsorption of carbon monoxide on catalyst inert sites as well as on oxidized and reduced catalyst active sites. Apart from that, the diffusion of the subsurface species in the catalyst and the reoxidation of reduced catalyst sites by subsurface lattice oxygen species is considered in the model. The model allows us to calculate activation energies of all elementary steps considered, as well as the bulk... 

The functions rj0(T) and experimental data of selected substances which closely follow the theorem of corresponding states.20 Six substances were retained argon, krypton, xenon, methane, carbon monoxide, and nitrogen (neon was discarded on account of quantum translational effects). 

Prior to 1970 our understanding of the bonding of diatomic molecules to surfaces, and in many cases the type of adsorption (i.e., molecular or dissociative) was almost entirely dependent on indirect experimental evidence. By this we mean that deductions were made on the basis of data obtained from monitoring the gas phase whether in the context of kinetic studies based on gas uptake or flash desorption, mass spectrometry, or isotopic exchange. The exception was the important information that had accrued from infrared studies of mainly adsorbed carbon monoxide, a molecule that lent itself very well to this approach owing to its comparatively large extinction coefficient. 

A rate equation was derived on the assumption that in the first step formaldehyde is formed on the catalyst surface from adsorbed carbon monoxide and hydrogen. The subsequent conversion of formaldehyde to methanol was assumed to be the rate-determining step. The experimental data were best expressed by a rate equation of the Langmuir-Hinshelwood type ... 

One source of information on intermolecular potentials is gas phase virial coefficient and viscosity data. The usual procedure is to postulate some two-body potential involving 2 or 3 parameters and then to determine these parameters by fitting the experimental data. Unfortunately, this data for carbon monoxide and nitrogen can be adequately represented by spherically symmetric potentials such as the Lennard-Jones (6-12) potential.48 That is, this data is not very sensitive to the orientational-dependent forces between two carbon monoxide or nitrogen molecules. These forces actually exist, however, and are responsible for the behavior of the correlation functions and - In the gas phase, where orientational forces are relatively unimportant, these functions resemble those in Figure 6. On the other hand, in the liquid these functions behave quite differently and resemble those in Figures 7 and 8. 

In this review the synthetic aspects of asymmetric hydroformylation will be discussed first the experimental data relevant to attempt a rationalization of the results will then be considered. The closely related synthesis of optically active aldehydes by hydroformylation of optically active olefinic substrates in the presence of achiral catalysts7,8 and the different asymmetric hydrocarbonylation reactions, such as the synthesis of esters from olefins, carbon monoxide and alcohols in the presence of optically active catalysts9 , are beyond the scope of this review and will not be discussed here. 

Experimental data show that the difference D m-co — D m-m decreases on descending a subgroup, that is, the D m m term increases more rapidly than Dm-co. In fact, of the following analogous pairs of compounds, only the first member of each pair is degraded by carbon monoxide (in solution at 25°C and 1 atm) ... 

Using molar volumes of hydrogen and carbon monoxide of 14.3 and 30.7 cm /mol respectively (10). k becomes 0.014 cm/s. However, with little experimental data available, estimated values of these mass transfer coefficients have varied widely. Deckwer, et al. (11) assumed a value k 0.02 cm/s and Satterfield and Huff (12) employed a value of 0.024 cm/s, based on early literature, as opposed to k = 0.014 cm/s used in this study. Stern, et al. (13) estimated the hydrogen and carbon monoxide mass transfer coefficients to be 0.21 and 0.019 cm/s, respectively, based on experimental parameters from several sources. 

The ratio of the quenching rate constants for NO and CO calculated from the computer best fits of the experimental pressure dependence is in agreement with earlier data indicating the kinetics and mechanism of the photocatalytic reduction of NO by carbon monoxide on Mo6+/Si02 photocatalysts reported earlier by Shelimov coworkers (Lisachenko et al., 2002 Subbotina et al., 1999,2001). 

This latter conclusion is in agreement with other published reports on the mechanism of carbon black formation. For example, Tesner (42, 43, 44, 45) is most well known for his theories of nucleation and growth of carbon particles. In a communication with Gaydon and Wolfhard (15), Tesner revealed that carbon particles in contact with carbon monoxide in a furnace show no growth whatsoever at any temperature. A mechanism reporting nucleation followed by growth in the carbon black reaction was recently reported by Dahmen (10) however, none of the experimental techniques nor data were presented. 

---