CATtech- 4 Déng hoc phan teng xtic tac Kinetics of catalytic reactions Ndi dung 1. 2. Néng dé trén bé mat ciia chét bj hp phy 3. Cac mé hinh (model) phan img trén xc tac ran. 4, Cch xay dyng phwong trinh téc 6 ova. ova. Slope = 35 kalo Slope = £28 In rate) WVTemperature ova.1. GIO! THIEU a Reaction rate = rate of slowest step Rate-determining step Which step? (1-7) 1. GIO! THIEU a C6 4 bude c6 thé la “Rate-determining step” 1) Khuéch tan (ngoai) ciia tac chat va san pham gira dang Ivu chat va bé mat ngodi cia hat xtc tac 2) Khuéch tan (trong) cla tac chat va san pndm_ xuyén qua chu tric pore ciia chat xuc tac 3) Hap phy tac chat trén bB mat ch: xi tac va gid hap san phdm 44) Phan Ung hoa noe cia mot hay nhibu cu ti nap phy 1. GIO! THIEU a 1. GIO! THIEU a “Rate-determining ‘ ae 8. ne pra tec ao + Rat nhiéu trrdng hop: step”: vBfol apart, ee by (4) la rate-determining step, (3) xay ra nhanh Bop ictesos coal aaa aaiauars (cB) 2) Khuéch tan {trong) thé thoe ddy emanh e&c qua 5) Hip pruagainie "nn wuon s 4) Phan tng + (8) & (4%: dc trung riér ba chal xe tae trong phan ng va ae ken phan Gng cu the Phuong trinh dong hoc (rate law) dura theo: - Langmuir-Hinshelwood mocel - Rideal- Eley model1. GIO! THIEU a Vi du: Déi v6i phan img dong thé pha khi, tc 46 ‘ca mot phan ting bie hai so cap (elementary bimolecular reaction): A+B > San phim are MOleCues reacted _K-.¢, = 4e"*™C,€, (time volume) Plucomg tinh Archenius A: HG s6 trae ly tira, duge xem la Khng phy thuge T Es ing lugng hogt ha bigu kién ym 3 1. GIO! THIEU a + Mot cach twong ty, mot biéu dign dom gin cua tbe 46 phan dmg trong xGe te dj thé gitta A va B nur sau A+B > San phim Kare= ct Fh NC OR ie (imexvolume) Eps) hl da mg Kh phy hue Pv mt én cach se ie. AC Cy) ha ng a le chdt phn sg ange nh ie ie eu be 65 phn ig. ym as] 2. Néng d6 trén bé mat cua chatbi hp phy 4) + Xét qua hdp phy héa hoe: A+SoAS + Liccén bang: x, = Cus CoPa Ky: Hing 96 C8 Chg: Hoy do ea vd nd py Ae CB (Luong A da hd ph tren mot dom v tnd ong XT) 4: ng d6 ca tam hoat tinh trén b8 mat X" ee CB (Lixgng tam host tinh con tréng trén met don vi Kh long XT) 2. Néng d6 trén bé mat cua chatbi hp phy 4) ec as ATSC AS Kune Dai lvgng “D6 che phui bé mat”(@): (0, Phd tém hoat inh bi hdp phu bai tae chit ie C8 (1-0,) phan t&m host tinh én B8 ml bn tng te CB Cas = Kas-8y (1-84) py a2. Néng d6 trén bé mat cua chatbi hp phy 4) A+S@AS oa = -8)-P, KPa 1+K p, (PT Langmuir) 2. Nong dé trén bé mat cia chatbi hdp phy >) + Phuong trinh Langmuir: =KaPa ““1+K,p, + Cie diéu kiér gid sit trong phurong trinh Langmuir = Nang lrgng ding nha trén b mgt — Cc tm hoa! inh 18 nu nha tong gud win hp png 2. Nong dé trén bé mat cia chatbi hdp phy >) Khi cé 2 chiit A va B dong thoi hap phy ©,: Phan tm hoat tinh bj hap phy boi A 6,: Phan tim hoat tinh bj hap phy boi B (1-0,- 6,): Phin tam hogt tinh con tréng A+S OAS == K, 4, B+S OBS = Ke aap, ova. 2. Néng d6 trén bé mat cua chatbi hp phy 4) Khi cé 2 chiit A va B dong thoi hip phy nO =8,-9,).Ps KPa 14K ypytKoPy KsPo PUK pst Kas2. Néng dé trén bé mat ciia chat bj hdp phy Khi cé “n” chat déng thoi hép phy 9, -KaPa > "UFEK Pa K Pow LEK Pa 2. Néng dé trén bé mat ciia chat bj hdp phy Khi chit A hap phy phan ly A, +28 <> 2AS Hogs 2G ‘Tanetensae ———Osrerson 2. Néng dé trén bé mat ciia chat bj hdp phy Khi chit A hap phy phan ly A, +28 <> 2AS 3. Cac mé hinh phan tng trén xic tac ran ‘M6 hinh Langmuir- Hinshelwood (1921) Phin sg ludns chit (bimolecular reaction):A+ B > C3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Vidy: Phan ting: A+B-> C theo mé hinh L-H: A+S OAS Oo) B+S BS @ AS+BS>CS+S (3) CS@C+s 4) id str chi c6 A, B Ia hdp phy, C khéng hép phy 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Vidu: A+B>C + Xt ning hop phn img bé mat gita hei phn whip phy (3) 1a phan dmg Khng che (rate- determining step). Ki R=k0,0, 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Vidu: A+B>C Khi C khéng hép phy thi KsPo TFKyp,+Kyp, |R=#0.0 =| EK Ky DP Po (4K Pit KuPo) EPP C+ KP + K pia)” 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Vidu: A+B>C le Khi A, B déu hap phy yéu: K,, Ky rat ho R= "PaPs Phin tng bac 1 voi A vi B3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Vidu: A+B>C Je= Pal Khi A hp phy yéu, B hip phy ang Kart nh; Ky rat on R=k"p,/ DP, Phan ting bac 1 voi Ava (-!) voi B 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Vidu: A+B >C en & ‘Tradag hop ning Af can B rAtia vo vai can AP K py<C Je= Pal TK Kp| 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Cac phan img trong céng nghiép: 1) Orion of CO on Pt catalysts 2) Methanol synthesis on 20 catalysts co+:H, —> chon 3) Hydrogenation of ethylene on Cu catalysts Cathet > Cotte3. Cac mé hinh phan tng trén xic tac ran M6 hinh Langmuir- Hinshelwood (1921) Cac phan img trong céng nghiép: 4) Reduction of NJO with Hy on PL or Au catalysts N04, > Ns +180 5) Oxidtio of elon acetaldehyde 0 Pa cays Crs * Us > CHLCHO ym EA 3. Cac mé hinh phan tng trén xic tac ran Pham ing long chit (bimolecular reaction): A+ B > C 3. Cac mé hinh phan tng trén xic tac ran ‘M6 hinh Eley-Rideal (1943) Vidy: Phan ting: A+B-> C theo mé hinh E-R: A+S @AS a) AS+B 9CS (2) CS 6C+S @) Gid str chi c6 A hip phy; B,C khéng hép phy ym a 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Eley-Rideal (1943) + Xét trong hop phan wng bé mat gidva hai phan ti hap phy (2) la phan tng khéng ché . Khi do: R=kO,.p,3. Cac mé hinh phan tng trén xic tac ran M6 hinh Eley-Rideal (1943) Vidu: A+B >C = hee Raha Eki ree Ree 1+K yp, me a 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Eley-Rideal (1943) Vidu: A+B>C Khi A hip phy yéu: K, rit no R= k'.pPs| Phin tng bac 1 voi A vi B ym x 3. Cac mé hinh phan tng trén xic tac ran M6 hinh Eley-Rideal (1943) Vidu: A+B>C ar ‘Tewémg hop ndng d@ B lén (xem nhw p, khéng adi) EPs 1+ K ape 3. Cac mé hinh phan tng trén xic tac ran Rate,3. Cac mé hinh phan tng trén xic tac ran M6 hinh Eley-Rideal (1943) Cac phan img trong céng nghiép: 1) Oxidation of etylene to etylene onde casos" — cry-crh Oo 2) Reduion of COs with He CO1o+H* —* H,0+C0 3) Oxidation of ammonia on Pt catalysts 2NI-3203* —> N+ 3186 3. Cc mé hinh phan dng trén xic tac rin hy) M6 hinh Eley-Rideal (1943) Cac phan img trong céng nghiép: 4) Hydrogenation of eyelohexene: +nt — [ 5) Selective hydrogenation of acetylene on Ni or Fe catalysts: HC=CH+Hyt > HC=CHy 4, Cch xay dung phuong trinh t6c do. ty, (1): Phan ng phan hdy, san phdm khéng hép phy A> san phim Téc d6 phan ng: R =k. Og KPa = 1+ KP, 4, Cch xay dung phuong trinh t6c do. ty, (1): Phan ng phan hdy, san phdm khéng hép phy A> sin pham T+K Khi panhé: > R =k’. Py > phan tng bac 1 Khip,lén: >R=k > phan tng bac 0 Khi p, tng dan: Bac phan tng giam dan 1 > 0 Khi A hdp phy rétyéu (K, rt nhd): R=k’. py, > phan tng bac 14, Cch xay dung phuong trinh t6c do. ty, (1): Phan ng phan hdy, san phdm khéng hép phy Asin pham = |r hi A hap ph rityéu (Ky et nbd): R= k's phan teng bac 4 hi A hap phy rétmanh (Ky rt in): R= k > phan tng bac 0 4. Cach xay dung phuong trinh t6c do (2): Phan tng phan hy, san phdm hap phy ADB+C Do B, C aw ndp phy nén yéu cdu phai cb 1 tam can tréng. Téc do phan ing: R =k. O,09 (4-1-#,-0,-4) Ke eee nee +R PAK Pe KP TK pat Kapa Rep KPa OF Kip Kup * Kor 4, Cch xay dung phuong trinh t6c do. ty, (3): Phan tng lvéng phan tir, sn pham h4p phy A+B9C T60 66 phan ung: R= k. 0,05