Reaction mechanism and reaction order：级反应机理和反应.ppt

Reaction mechanism and reaction order Chemical reaction: single or sum of many steps =reaction mechanism A step: (elementary reaction) one, two or three reacting molecules = molecularity unimolecular: isomerization, decomposition bimolecular: energy transfer, combination termolecular: energy transfer + combination Reaction order vs. molecularity Reaction takes place in an elementary reaction unimolecular: first order bimolecular: second order termolecular: third order Is a first order reaction is always an unimolecular reaction? Consecutive reaction processes RX + H2O = ROH + H+ + X- Unaffected by the PH of solution, SN1 reaction RX ? R+ + X- R+ + H2O ? ROH + H+ RX + OH- = ROH + X- Alkaline solution RX ? R+ + X- R+ + OH- ? ROH What happen for 2nd order reaction? Consecutive reaction processes A ? B k1, B ? C k2 -d[A]/dt = k1 [A]; -d(a-x)/dt = k1 (a-x) d[B]/dt = k1(a-x) - k2[B] = k1 a e-k1t - k2[B] d[B]/dt + k2[B] = k1 a e-k1t Plot of concentrations of A, B, C in consecutive process Maximum [B] Formation of an intermediate complex A + B ? X (1) X ? A + B(2) X ? C + D(3) Principles of Stationary state 1913 Chapman: the net rate of formation of a reaction intermediate may be put equal to zero. X so reactive, [X] is low Formation of an intermediate complex A + B ? X .. k1; X ? A + B … k-1 X + C ? P + Q … k2 Third body effect in atomic recombination Two atoms ?molecule + lot of vibrational energy short life time production: needs a collision with other molecular species to shed some excessive energy X + X + M ? X2 + M before first vibration (10-13 s) ? effective collision effective molecule=highly negative activation energy higher temperature: lower reaction rate efficiency is different depend on molecule large molecule Porter’s interpretation(1961) I + M = I.M (K1); I.M + I ? I2 + M(k2) I.M: spectroscopically identified for benzene [I.M]=K1[I][M] d[I2]/dt = k2[I][I.M] = K1k2[I]2[M] RT ln K = -?G = -?(H-TS) k = A exp[-Ea/RT] Parallel reacti