reactionmechanismandreactionorder：級(jí)反應(yīng)機(jī)理和反應(yīng)-閱讀頁
2025-01-27 08:32本頁面
【正文】 mentary reaction, four center transition state – Sullivan 1967: 0200?C 。 [A] = [H+] [B]/ Ka.。Ka/(Ka + [H+]) – [A] = a [B] – PH dependent Opposing reaction ? A ? B (k1) B ? A (k1) – dx/dt = k1(ax) k1 x = k1a k1x k1 x – final equilibrium. – k1(axe) = k1 xe k1a = (k1 + k1)xe – dx/dt = (k1 + k1)(xex) – ln {(xe)/(xex)} = (k1+k2)t Isotope exchange reaction ? AX + BX* = AX* + BX – Assume K=1 ? ?G = RT ln K = 0 – [AX]t=0 = a。 [AX*]t=0 = [BX]t=0 = 0 – At equilibrium – x2/(ax)(bx) = 1 x = ab/(a+b) – [AX]?= ax = a2/{a+b}, [BX*]?= bx = b2/{a+b} – [AX*]?= ab/{a+b}, [BX]?= ab/{a+b} – [AX]t+ [AX*]t = a, [BX]t+ [BX*]t = b ?????????? ??????? ??????? ??abxbxbaxadtdx 2??????? ??????? ??????? ??abxbxbaxadtdx 2?– = ?{(a+b)/ab}(xex) – Integration with x=0 at t=0 – ln{xe/(xex)} = ?{(a+b)/ab}t – no information on reaction order for ? ? Determined by initial rate with different a and b ? ? = kn apbq – ln{xe/(xex)} = kn ap1bq1 (a+b)t
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