表面反应控制 ●若A为解离吸附,对反应A分>R A+20今24 P62=02 →Ra+ar=k,02-k,6 RG分R+KRP2,=6n 64+bn+0 →日=1-∑a +√KAP4 Pr K +√KAp4+K2P KRPR 1+√KAP4+KAP2 k, KP-k, Krpr kp k.04-k00 K +KD,+kD)=(+、k,D1+k
–表面反应控制 ⚫ 若A为解离吸附，对反应 A R 2 2 2 1 2 2 A A v A A+ A K p = r A r R v A R r k k 2 ' 2 1 2 ⎯→ + = − R R v R R R+ K p = A + R +v = 1 A A R R R R R R R v A A R R A A A A A v i A A R R v i K p K p K p K p K p K p K p K p K p K p + + = = + + = = + + = − = 1 1 1 1 1 2 2 ' 2 ' (1 ) ( ) (1 ) A A R R R A A A R R r A A r R R r A r R v K p K p K p k p K p K p k K p k K p r k k + + − = + + − = − =
吸附控制 对A+B台R+S,若为A的吸附控制,则相 应的机理可写为: A+o<Ao r=ro-rd=kaP8-ke B+0今Bo BPBO, =8B Ao+ Boe ro+so e PRP K, BB K,Kg PB RG冷R+ KRPRE,=b Soes+o s6,=6
–吸附控制 ⚫ 对 ，若为A的吸附控制，则相 应的机理可写为： A+ B R+ S a d a A v d A A+ ⎯→ A r = r − r = k p − k B+ B KB pB v = B v B R S r B R S r B R S A p p p K K K K K A B R S + + = = R R+ KR pR v = R S S + KS pS v = S
吸附控制 对A+B分R+S,为A的吸附控制 64+bn+6n+6+b,=1 →KBD2,+K2b,+Ksps0,+ks,PPs.日,+8 K, Kg PB →b. +K PRPS+ KBPB+Kp+ksps PB PB 1+A PRPs + KBps+KRPr+ KsPs PB
–吸附控制 ⚫ 对 ，为 A的吸附控制 B B R R S S B R S RS B R S RS A B B R R S S B R S RS v v v B R S r B R S B B v R R v S S v K p K p K p pp p K pp p KK p K p K p pp p K pp p K K K K K p K p K p + + + + = + + + + = + + + + = 11 1 1 A+ B R+ S A + B + R + S +v = 1
吸附控制 对A+BR+S,为A的吸附控制 kapa-ka PRPs k,PB-k,0 KRS PB 1+A PRPs+ABPB +KRPR+Ksps PRPS K 1f。PBS+KB+ARP+KsS P
–吸附控制 ⚫ 对 ，为 A的吸附控制 B B R R S S B R S RS B R S A B B R R S S B R S RS B R S a A d RS a d a A v d A K p K p K p pp p K K p p p k p K p K p K p pp p K pp p k p k K r r r k p k + + + + − = + + + + − = − = − = 1 ( ) 1 A + B R + S
吸附控制 ●若A为解离吸附且为控制步骤时:A分>R A+2<A>2A =kP02-k102 2A1分R+akbb → Ro分R+ O KRPRE,=n 64+bn+b,=1 R P t R 1+ P +K, K P k,Pu-k, K k(p ,p02-k02 (1+ P +K)(1+ P +Krp
–吸附控制 ⚫ 若A为解离吸附且为控制步骤时： A R 2 2 2 2 2 1 ka pA v kd A A+ ⎯→ A r = − v r R R r R v A A R v r K K p K A R K + = = = 2 2 1 2 R R+ KR pR v = R A + R +v = 1 R R r R R r R R A R R r R R v K p K K p K K p K p K K p + + = + + = 1 1 1 2 2 2 2 (1 ) ( ) (1 ) R R r R R R A R R r R R r R R a A d a A v d A K p K K p K p k p K p K K p K K p k p k r k p k + + − = + + − = − =