Carbon dioxide equilibria, equations

At 800° C. reaction (2) appears to proceed slowly in either direction, while (1) is very rapid. The fact that the degree of dissociation in (1) is. independent of the amounts of carbon dioxide and carbon disulphide present, shows that carbon monoxide and sulphur are primary products of the decomposition of carbonyl sulphide and are not formed secondarily from the carbon dioxide and carbon disulphide. At temperatures below 400° C. decomposition according to equation (1) is not evident, while at 900° C. it reaches a maximum (64 per cent.) reaction (2) reaches a maximum at about 600° C., at which point 43 per cent, of the carbonyl sulphide is decomposed in this way and 16 per cent, according to reaction (1). The carbon monoxide equilibrium depends upon the pressure, whilst the carbon dioxide equilibrium does not. Nearly all the reactions involved in the thermal decomposition of carbonyl sulphide depend greatly on catalytic influences. Quartz is a pronounced catalyst for reaction (2), but has little influence on reaction (1). Carbonyl sulphide is comparatively rapidly decomposed in quartz vessels, but is stable when kept in glass apparatus. The viscosity of gaseous carbonyl sulphide is as follows x... 

An application of Eq. (11) is shown in Fig. 2, which gives the solubility of solid carbon dioxide in compressed air at a low temperature. The solubility is calculated from the equation of equilibrium... 

Schwartzentruber J., F. Galivel-Solastiuk and H. Renon, "Representation of the Vapor-Liquid Equilibrium of the Ternary System Carbon Dioxide-Propane-Methanol and its Binaries with a Cubic Equation of State. A new Mixing Rule", Fluid Phase Equilibria, 38,217-226 (1987). 

In heterogeneous equilibria, not all the species present are in the same state. An example of a heterogeneous equilibrium reaction is heating calcium carbonate in a closed system so that the carbon dioxide gas produced cannot escape and equilibrium is established. The equation for the reaction is ... 

C 0 and H O, unavoidable by-products of alcohols synthesis. Considering chemical reactions of table H, water and carbon dioxide appear as equiva-lentby-products due to shift conversion equilibrium, equation (1). Most other low temperature alcohol synthesis catalysts have a rather high shift activity as well. CO removal fhom reacted syngas of synthesis loop, before recycling to reactor, leads to a significant decrease of water formation which, in turn, results in a lower water content in the raw alcohols, leading to simplified fhactionation-dehydration processes. 

The alkylation of quinoline by decanoyl peroxide in acetic acid has been studied kineti-cally, and a radical chain mechanism has been proposed (Scheme 207) (72T2415). Decomposition of decanoyl peroxide yields a nonyl radical (and carbon dioxide) that attacks the quinolinium ion. Quinolinium is activated (compared with quinoline) towards attack by the nonyl radical, which has nucleophilic character. Conversely, the protonated centre has an unfavorable effect upon the propagation step, but this might be reduced by the equilibrium shown in equation (167). A kinetic study revealed that the reaction is subject to crosstermination (equation 168). The increase in the rate of decomposition of benzoyl peroxide in the phenylation of the quinolinium ion compared with quinoline is much less than for alkylation. This observation is consistent with the phenyl having less nucleophilic character than the nonyl radical, and so it is less selective. Rearomatization of the cr-complex formed by radicals generated from sources other than peroxides may take place by oxidation by metals, disproportionation, induced decomposition or hydrogen abstraction by radical intermediates. When oxidation is difficult, dimerization can take place (equation 169). 

The total amount of energy liberated, i.e. the heat of explosion Q in the water-gas equilibrium, depends upon the relative proportions of the reactants (carbon dioxide and hydrogen) to the products (carbon monoxide and water). This can be seen from Equation 6.1 where the heat of formation for carbon dioxide emits more energy than that for carbon monoxide and water ... 

Equation (115) is the same as (6) studied by James and co-workers (62) in the CO reduction of RhCl3.] The labeling experiment also revealed information on the stability of the hydroxycarbonyl intermediate in (115). If this species, Rh—COOH, was formed in an equilibrium concentration, then proton transfer and the reverse reaction would lead to incorporation of labeled oxygen in the carbonyl ligand and therefore to the observation of doubly labeled C02. However, comparison of the abundances of the three isotopic carbon dioxide molecules found (masses 44, 46 and 48) with distributions calculated assuming (i) equilibrium formation of the hydroxycarbonyl and (ii) immediate decomposition of the intermediate clearly showed that the hydroxycarbonyl intermediate reacts to form C02 immediately after it is formed, with no indication of a substantial equilibrium or incorporation of lsO in the carbonyl ligand. 

For the calculations, averages of the results of the two 5. -equilibrium models of Ca2+ = 35 p.p.m., Mg2+ = 7 p.p.m., and alkalinity = 1.55 X 10 3 equiv./liter are used. Solubility data of Larson and Buswell (11), carbon dioxide solubility data of Hamed and Davies (2), and the carbonate ionization data of Hamed and Hammer (3) and Hamed and Scholes (4) are used. Linear interpolations are made for dolomite between pK(soly) = 16.3(5°C.) and 17.0(25°C.). Equations outlining the calcite and dolomite calculations are ... 

When the reaction is carried out in a closed container, three phases are present at equilibrium solid calcium carbonate, solid calcium oxide, and gaseous carbon dioxide. If we were to write the usual equilibrium equation for the reaction, including all the reactants and products, we would have... 

The absorption rate of carbon dioxide increases in the presence of amines or ammonia. Therefore, the reaction kinetics of NH3 and C02 has been considered in the model equations, too. The rate constant as a function of the temperature has been determined according to Ref. 136. The coefficients for the calculation of the chemical equilibrium constants in this system of volatile weak electrolytes are taken from Ref. 137. 

The relations between the chemical potential of the carbonic acid given in Equation (11.40) and that of carbon dioxide given in Equation (11.46), between the corresponding chemical potentials, and between the two equilibrium constants still need to be defined in order to make the two methods consistent. By use of the methods developed in Section 8.15, we can show that... 

When applying an equation of state to both vapor and liquid phases, the vapor-liquid equilibrium predictions depend on the accuracy of the equation of state used and, for multicomponent systems, on the mixing rules. Attention will be given to binary mixtures of hydrocarbons and the technically important nonhydrocarbons such as hydrogen sulfide and carbon dioxide -Figures 6-7. 

Experimental results are presented for high pressure phase equilibria in the binary systems carbon dioxide - acetone and carbon dioxide - ethanol and the ternary system carbon dioxide - acetone - water at 313 and 333 K and pressures between 20 and 150 bar. A high pressure optical cell with external recirculation and sampling of all phases was used for the experimental measurements. The ternary system exhibits an extensive three-phase equilibrium region with an upper and lower critical solution pressure at both temperatures. A modified cubic equation of a state with a non-quadratic mixing rule was successfully used to model the experimental data. The phase equilibrium behavior of the system is favorable for extraction of acetone from dilute aqueous solutions using supercritical carbon dioxide. 

Figure 2. Phase equilibrium behavior for the binary system carbon dioxide - acetone. Experimental, 313 K (A) experimental, 333 K ( ) literature, 313 K (x) modified Peng-Robinson equation of state (—). Literature data are from reference (10).

Unfortunately values cannot be directly calculated from retention volume measurements by Equation 3 since the interfacial surface area is changing as a function of pressure due to the carbon dioxide sorption. However, the relative magnitude of the equilibrium shift of the sorbate from the solid adsorbent into the gaseous phase can be estimated by calculating the capacity factor, k, according to Equation A as given below ... 

The purposes of our research were to evaluate the feasibility of supercritical carbon dioxide extraction of lemon oil near ambient temperature, generate equilibrium data for carbon dioxide with multicomponent essential oil constituents, and evaluate the ability of the Peng-Robinson equation of state ( ) to model this multicomponent supercritical system. 

Before proceeding, a few general comments will be helpful. In most cases at least one of the four carbonate system analytical quantities (total alkalinity, total CO2, carbon dioxide partial pressure, and pH) will be known. The equilibrium equations relating these quantities, along with those for water and calcite, will be used frequently in calculations. Also, in cases where calcite dissolution and... 

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