Predicting solvent effects on the 1‐dodecene hydroformylation reaction equilibrium

Abstract

This work investigates solvent effects on the reaction equilibrium of the 1-dodecene hydroformylation in a decane/N,N-dimethylformamide solvent system. The reaction was performed at different decane/N,N-dimethylformamide ratios and at temperatures between 368 K and 388 K. The equilibrium concentrations of all reactants and products were determined experimentally. The enthalpy and Gibbs energy of this reaction at the ideal-gas standard state were determined by quantum-chemical calculations in good agreement with literature data. Moreover, quantum-chemically calculated standard Gibbs energies of reaction at infinite dilution in liquid decane/DMF-solvent mixtures allowed a qualitative prediction of the solvent effect on the equilibrium concentrations. Based on the standard Gibbs energy of reaction at the ideal-gas standard state and on fugacity coefficients calculated using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), the equilibrium concentrations of reactants and products for the 1-dodecene hydroformylation performed in decane/N,N-dimethylformamide mixtures of different compositions could be predicted in very good agreement with experimental data.

The thermochemistry of long chain olefin isomers during hydroformylation

“…and this has to be assigned to the slower convergence with basis set size for these correlated wavefunction calculations which was also shown for the thermochemistry of the hydroformylation reaction. 57 For the cis-configuration, all methods (except MP2 and B2PLYP) give cis-2-decene to be the most stable which agrees with the experimental findings. For trans-isomers, most of the methods predict either trans-2-decene or trans-4-decene (in agreement with experiment) to be the most stable one.…”

“…We have previously estimated the non-ideality of a decane/DMF solvent system and their effect on the reaction enthalpy of the hydroformylation of dodecene. 57 Significant activity a i and fugacity coefficients j i were needed to rationalize the equilibrium concentrations of reactants and products. For energy differences, however, these effects are assumed to cancel out.…”

Mechanism and Control of the Palladium‐Catalyzed Alkoxycarbonylation of Oleochemicals from Sustainable Sources

“…Thermodynamics and reaction equilibria are of critical importance when it comes to the simulation of chemical reaction networks and processes. Properties such as reaction enthalpy, Gibbs free energy and solvation energy of an ideal system are often not available in literature but can be obtained computationally and then later can be combined with the other thermodynamic approaches to account for the non‐ideality of complex reaction mixtures at process conditions . Quantum chemical calculations of thermodynamic data pose a challenge in terms of accuracy .…”

Computational investigation of the control of the thermodynamics and microkinetics of the reductive amination reaction by solvent coordination and a co-catalyst

“… 47 Standard thermodynamic parameters such as reaction enthalpy and Gibbs free energy of the ideal system are often not available in the literature but can be obtained computationally and then later combined with other thermodynamic approaches to account for the non-ideality of complex reaction mixtures at process conditions. 35 Solvent effects on the kinetics 48 and thermodynamics 49 of the hydroformylation reaction of 1-dodecene were already investigated experimentally and combined with the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) to model the reaction of dodecene with syngas (CO/H 2 ) in a solvent mixture of DMF/decane at 90 °C and 21 bar. Quantum chemical calculations of thermochemical data pose a challenge in terms of accuracy and standard DFT functionals were not suitable to obtain accurate data for the hydroformylation of long chain olefins but MP2 calculations gave reliable thermodynamic equilibrium constants K f .…”

“…Quantum chemical calculations of thermochemical data pose a challenge in terms of accuracy and standard DFT functionals were not suitable to obtain accurate data for the hydroformylation of long chain olens but MP2 calculations gave reliable thermodynamic equilibrium constants K f . 49 The reaction thermodynamics DG r of the reductive amination reaction of aldehydes of various carbon chain lengths and diethylamine were calculated in the gas phase and in an implicit solvent environment. The free energy of the reaction was À14.7 kcal mol À1 and only slightly affected by presence of a solvent to become À15.1 and À15.3 kcal mol À1 in either DMF and decane (see Table 1).…”