Linear free energy relationships for dechlorination of aromatic chlorides by Pd/Fe.
Reductive dechlorination rate constants for five chlorobenzenes in the presence of Pd/Fe as catalyst were determined experimentally. Linear free energy relationships (LFER) for the dechlorination rate constants of five chlorobenzenes and three chlorophenols were developed by partial least squares (PLS) regression based on quantum chemical parameters computed by PM3 Hamiltonian. The optimal LFER model obtained is logk=-1.63+1.46 x 10(-3)DeltaH(f)-7.69 x 10(-1)E(LUMO)where k stands for the dechlorination rate constants, DeltaH(f) is the standard heat of formation, and E(LUMO) is the energy of the lowest unoccupied molecular orbital. The Q(2)(cum) value of the model is 0.879, indicating good robustness and predictive power of the model.
Liu
Yihui
Y
School of Chemical Engineering, Dalian University of Technology, Zhongshan Road 158, PR China.
Yang
Fenglin
F
Chen
Jingwen
J
Gao
Lina
L
Chen
Guohua
G
D002712:Chlorides / Q000737:chemistry*; D002713:Chlorine / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D007854:Lead / Q000737:chemistry*
D002712:Chlorides; D007854:Lead; D002713:Chlorine; D007501:Iron