Carbon monoxide equilibrium condition

In the various laboratory studies when the outlet gas composition was not at equilibrium, it was observed that the steam-to-gas ratio (S/G) significantly affected the hydrogen leakage while the carbon monoxide still remained low. On the assumption that various reactions will proceed at different rates, a study was made to determine the effect of S/G on the reaction rate. The conditions for this test are presented in Table VII the findings are tabulated in Table VIII. 

The compound [HRh(C0)(TPPTS)3] is a "precatalyst" and dissociates to the 16e species [HRh(C0)(TPPTS)2]. This oxo-active complex initiates the hydroformylation cycle. Under oxo conditions (presence of CO/H2, H20, and a surplus of TPPTS) the hydroxo complex [(HO)Rh(CO)(TPPTS)2] may be formed and again reversibly converted to [HRh(C0)(TPPTS)3] (equilibrium lies almost completely towards the hydride). However, higher carbon monoxide partial pressures may cause the displacement of TPPTS by CO according to Equation 5.8. 

The presence of water in synthesis gas mixtures along with light components, such as carbon monoxide or hydrogen, has the effect that phase separations may persist even under extreme conditions of temperature and pressure. The need exists to demonstrate that these phase separations, perhaps with simultaneous reaction equilibrium, can be described by models capable of some accuracy. 

The insertion of CO is in many instances thermodynamically unfavourable the thermodynamically most favourable product in hydroformylation and carbonylation reactions of the present type is always the formation of low or high-molecular weight alkanes or alkenes, if chain termination occurs via (3-hydride elimination). The decomposition of 3-pentanone into butane and carbon monoxide shows the thermodynamic data for this reaction under standard conditions. Higher pressures of CO will push the equilibrium somewhat to the left. 

The dianion [Ni6(CO)12]2- is stable to hydrolysis in alkaline aqueous solution however, in acidic conditions (pH = 3-6) it is converted quantitatively into the interstitial hydride complex [Ni12(CO)21H4 B]"- (n = 2,3).5 6 The complex readily reacts in solution with carbon monoxide according to the following degradation-condensation equilibrium 1... 

In order to calculate the heat of explosion for RDX at equilibrium conditions the exact quantities of carbon dioxide, carbon monoxide and water must be determined. These can be calculated from the equilibrium... 

The results do not prove that in the reaction conditions used the alkyl formation is not reversible, but only that, if it is reversible, the carbon monoxide insertion on both diastereomeric rhodium-alkyls must be much faster than the rhodium-alkyls decomposition. Restricting this analysis of the asymmetric induction phenomena to the rhodium-alkyl complexes formation, two 7r-olefin complexes are possible for each diastereomer of the catalytic rhodium complex (see Scheme 11). The induction can take place in the 7r-olefin complexes formation (I — II(S) or I — II(R)) or in the equilibrium between the diastereomeric 7r-olefin complexes (II(r) and... 

Fig. 5. Several metals have been shown to be volatilized by carbon monoxide. A map of the safe (no metal loss) operating conditions ( ) and unsafe ( ) operating conditions for Ni/Al2Oj catalysts. The equilibrium curves for various equilibrium partial pressures of Ni(CO)4 were calculated by using thermodynamic data from the literature (72).

The conditions under which cobalt hydrocarbonyl was reacted with olefin were also found to affect the distribution of products and the extent of isomerization of excess olefin (62, 73, 147). At low temperatures (0° C) under carbon monoxide (1 atm) very little isomerization of excess 1-pentene occurred and the main product was the terminal aldehyde. Under nitrogen or under carbon monoxide at 25° C, extensive olefin isomerization occurred and the branched aldehyde was mainly produced. The olefin isomerization is most satisfactorily accounted for by an equilibrium between alkylcobalt and olefin-hydride cobalt complexes [Eqs. (9) and (10)]. The carbon monoxide inhibition is most easily explained if the isomerization proceeds via the tricarbonyls rather than tetracarbonyls. This also explains why ethylcobalt tetracarbonyl is not in equilibrium with hydrocarbonyl and ethylene under conditions where the isomerization is rapid (62, 73). 

Piacenti et al. suggested that the different results at low and high carbon monoxide pressure were due to different catalytic intermediates (A and B) under the two sets of conditions. Thus at low pressures A caused a rapid olefin isomerization and the formation of similar product distributions of aldehydes from 1- and 2-pentene. At high pressures little olefin isomerization occurred and 1-olefin yielded significantly more straight-chain aldehyde than 2-olefin. This would seem consistent with Heck and Breslow s mechanism (62) if A were an acylcobalt tricarbonyl in equilibrium with isomeric olefin-cobalt hydrocarbonyl complexes and B were an acylcobalt tetracarbonyl. 

Originally, Piacenti et al. explained the formation of isomeric products in terms of an equilibrium of alkylcobalt carbonyls with olefin-hydrocarbonyl complexes as in the Oxo reaction. More recently, however, they have noted that the conditions under which n-propyl orthoformate gave no isomeric products (below 150° C, carbon monoxide pressure 10 atm) are conditions under which isomerization occurs readily in the hydroformylation of olefins (115). Since alkylcobalt carbonyls were formed in both reactions they dismissed the possibility that this isomerization was due to alkyl- or acylcobalt carbonyls. The fact that Takegami et al. have found that branched-chain acylcobalt tetracarbonyls isomerize more readily than straight-chain acylcobalt tetracarbonyls would seem to fit in quite well with the results of Piacenti et al., however, and suggests that the two findings may not be so irreconcilable as might at first appear (see Section II, B,2). 

Thermodynamically the insertion of an alkene into a metal-hydride bond is much more favourable than the insertion of carbon monoxide into a metal-methyl bond. The latter reaction is more or less thermoneutral and the equilibrium constant is near unity under standard conditions. The metal-hydride bond is stronger than a metal-carbon bond and the insertion of carbon monoxide into a metal hydride is thermodynamically most often uphill. Insertion of alkenes is also a reversible process, but slightly more favourable than CO insertion. Formation of new CT bonds at the cost of the loss of the ji bond of the alkene during alkene hydrogenation etc., makes the overall processes of alkenes thermodynamically exothermic, especially for early transition metals. 

The reaction is first order in rhodium catalyst concentration, first order in dihydrogen pressure and has an order of minus one in carbon monoxide pressure. In our Scheme 6.1 this would be in accord with a rate-determining step at the end of the reaction sequence, e.g. reaction 6. Since the reaction order in substrate is zero, the rhodium catalyst under the reaction conditions predominates as the alkyl or acyl species any appreciable amount of rhodium hydride occurring under fast pre-equilibria conditions would give rise to a positive depence of the rate of product formation on the alkene concentration. The minus one order in CO suggests that the acyl species rather than the alkyl species is dominant under the reaction conditions. The negative order in CO is explained [20] by equilibrium... 

Figure A.4 Combined equilibrium methane reformer and fuel cells for hydrogen and carbon monoxide at standard conditions, Pq and Tq...

The equilibrium of a hydrogen or carbon monoxide fuel cell operating at high temperature and pressure is defined using a flow sheet, which connects the cell to a fuel store at standard conditions, and to the environment, via combined isentropic and isothermal circulators and a Carnot cycle. 

In this catalyst system, addition of phosphine or decrease in partial pressure of CO (or of total pressure at constant synthesis-gas ratio) shifts the phosphine-carbon monoxide ligand-exchange equilibrium toward the phosphine-substituted species (right to left in scheme 8.13). A decrease in phosphine concentration or an increase in CO pressure shifts it in the opposite direction (left to right). Addition of base shifts equilibrium downward, from the acids to the anions. In the presence of phosphine in an at least moderate excess, thermodynamics strongly favors HCo(CO)3Ph over HCo(CO)4, but Co(CO)4" remains very strongly favored over Co(CO)3Ph under all conditions of practical interest. 

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