Investigation of the equilibria of the reaction: CH3(CH2)4OH + (CH3)2C:CH2 = CH3(CH2)4OC(CH3)3

Article abstract of DOI:10.1016/0021-9614(90)90119-B

Equilibria have been studied of the reaction of synthesis of amyl t-butyl ether (ATBE) from n-pentan-1-ol and 2-methylpropene in the liquid (313 to 413 K) and gas (399 to 447 K) phases.It has been found that in the liquid phase (ATBE + n-pentan-1-ol + 2-methylpropane) is non-ideal.Its mole-fraction equilibrium product K_x depends on the composition of the reaction mixture at constant temperature.With n(C5H11OH)/n<(CH3)2C:CH2> <*> 2 in the starting mixture, K_x is approximately constant.It has been shown that the values of K_x found for n(C5H11OH)/n<(CH3)2C:CH2> =4 can be used for the establishment of the enthalpy of reaction without corrections for non-ideality of the mixture.An ebulliometric method was used to find the vapour pressure of ATBE. Δ_rH_m⁰ = -(67.09 +/- 4.94) kJ*mol^-1 and Δ_rS_m⁰ = -(173.1 +/- 11.6) J*K^-1*mol^-1 were found for the reaction: CH3(CH2)4OH + (CH3)2C:CH2 = CH3(CH2)4OC(CH3)3 in the gas phase for T = 423 K.The following values of thermodynamic quantities of ATBE have been found both from chemical equilibria and (p,T) results: Δ_fH_m⁰(298.15 K,g) = -(380.6 +/- 6.8) kJ*mol^-1; Δ_vapH_m(298.15 K) = (46.89 +/- 0.99) kJ*mol^-1, and Δ_vapH_m = (39.1 +/- 3.1) kJ*mol^-1 at the normal boiling temperature, 419.156 K.