Molar enthalpies of formation and vaporization of t-butoxybutanes and thermodynamics of their synthesis from a butanol and 2-methylpropene. I, Equilibria of synthesis reactions of t-butoxybutanes in the liquid phase

The equilibria of the synthesis of 1- t -butoxybutane (I), 2-methyl-1- t -butoxypropane (II), and 1-methyl-1- t -butoxypropane (III) from 2-methylpropene (IV), and butan-1-ol (V), 2-methyl-propan-1-ol (VI), and butan-2-ol (VII) in the liquid phase were investigated at temperatures from 315 K to 423 K. On the basis of experimental equilibrium constants found for n (C 4 H 9 OH)/ n {(CH 3 ) 2 C:CH 2 } = 4, values of Δ r H ° m and Δ r S ° m were calculated. The following results were obtained: Reaction Δ r H m o / ( k J ⋅ m o l − 1 ) Δ r S m o / ( J ⋅ K − 1 ⋅ m o l ) − 1 V + I V = I - 3 4 . 8 ± 2 . 7 - 7 5 . 8 ± 7.7 V I + I V = I I − 36.3 ± 1.8 − 79.6 ± 5.2 V I I + I V = III − 37.7 ± 2.4 − 108.5 ± 7.3