表面反应控制 ●不可逆反应A+B→R+S A+a分 Ao KP,=64 B+分 Bo KRP2b,=6 Ao+Bo->Ro+So r=k, 0B Ro今R+0 RP 日.=6, SoS+σ sPs,=8s 04+88+8R+6s+6 6, 1+∑K;P K;P26 ∑ K,p
–表面反应控制 ⚫ 不可逆反应 A+ B → R+ S A A v A A+ A K p = B B v B B+ B K p = r A B A + B ⎯→ R + S r = k R R+ KR pR v = R S S + KS pS v = S A + B + R + S +v = 1 + = = + = − = i i i i i i i i v i i i i v i K p K p K p K p 1 1 1 1
表面反应控制 ●不可逆反应A+B→R+S k, KKBPaPB (1+KP+KePB+KRPR+KsPs paPA (1+KAPa+KBPB+KRPR+KsPs PaPB +∑K1P1)2 若表面覆盖率很低,则 ∑K1P ppB 为幂函数型动力学方程
–表面反应控制 ⚫ 不可逆反应 –若表面覆盖率很低,则 • 为幂函数型动力学方程 2 2 2 (1 ) (1 ) (1 ) + = + + + + = + + + + = = i i i A B A A B B R R S S A B A A B B R R S S r A B A B r A B K p kp p K p K p K p K p kp p K p K p K p K p k K K p p r k A+ B → R+ S A B i i i K p 1 r = kp p
表面反应控制 ●可逆反应A+B分→R+S A+a分 Ao KP,=64 B+分 Bo KRP2b,=6 Ao+bofa>Ro+so k06.-k6.0 Ro今R+ RP 日.=6, S分S+KsDs,=b 04+88+8R+6s+6 6, 1+∑K;P K;P26 ∑ K,p
–表面反应控制 ⚫ 可逆反应 A+ B R+ S A A v A A+ A K p = B B v B B+ B K p = R R+ KR pR v = R S S + KS pS v = S r A B r R S A B R S r k k ' + ⎯→ + = − A + B + R + S +v = 1 + = = + = − = i i i i i i i i v i i i i v i K p K p K p K p 1 1 1 1
表面反应控制 ●可逆反应A+B兮R+S k,6A6g-k,626s k, KKBPaPB-k KRKsprPs (1+KPa+KsPB+KRPr+ksPs+K,Pi k(Pp PRP (+Kp+kBPB+KPr+ksps+Kpi) k(PPr-PRPs K (+∑K
–表面反应控制 ⚫ 可逆反应 A+ B R+ S 2 2 2 ' ' (1 ) ( ) (1 ) ( ) (1 ) + − = + + + + + − = + + + + + − = − = i i i R S A B A A B B R R S S I I R S A B A A B B R R S S I I r A B A B r R S R S r A B r R S K p K p p k p p K p K p K p K p K p K p p k p p K p K p K p K p K p k K K p p k K K p p r k k
表面反应控制 ●可逆反应A+B分R+S 若A、R吸附,而B、S不吸附 A+a分 Ao KP6.=64 Ao+ BRo+s r=k, PB-k, BRPs Ro今R+ P 04++O,=1→=1-∑ 1+∑Kp 8=K: P: 8 ∑K r=k, 04PB-k, RPs k, KPAPB-k KRPRPs (+KAPa+KRP k(PPB prp SK k(PAPB PRP (1+KPA+KRPR)2 (1+>KP:)
–表面反应控制 ⚫ 可逆反应 –若A、R吸附,而B、S不吸附 A+ B R+ S A A v A A+ A K p = r A B r R S A B R S r k p k p ' + ⎯→ + = − R R+ KR pR v = R A + R +v = 1 + = = + = − = i i i i i i i i v i i i i v i K p K p K p K p 1 1 1 1 2 2 2 ' ' (1 ) ( ) (1 ) ( ) (1 ) + − = + + − = + + − = − = i i i R S A B A A R R R S A B A A R R r A A B r R R S r A B r R S K p K p p k p p K p K p K p p k p p K p K p k K p p k K p p r k p k p