Kinetics. Review- Collision Theory. Reaction Rate. Page 1
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1 Kcs Th sudy f c s. Spus cs cs h wll hpp - bu w c ll hw fs. Dmd wll spusly u gph vully. Rc mchsm- h sps by whch c ks plc. Rvw- lls Thy Pcls hv clld c. v h hd ugh Thgs h cs hs cs gh mp fs c gh cc fs c Smll pcls = g sufc ms fs c Rc R As h c pgsss h cc 2 gs dw R = c. f A 2 -c. f A R = [A] hg cc p u m F hs c N N 3 c [ 2 ] N N 3 Tm As h c pgsss h cc N 2 gs dw 1/3 s fs As h c pgsss h cc N 3 gs up 2/3 ms c [ 2 ] [N 2 ] N N 3 c [ 2 ] [N 3 ] [N 2 ] N N 3 Tm Tm Pg 1 1
2 lculg Rs Avg s k v lg vls Isus s dmd by fdg h slp f l g h cuv y gv p bcus h c chg v m Dvv. c Avg slp mhd [ 2 ] Tm c Isus slp mhd. [ d[ 2 ] d Tm Dfg R W c df ms f h dsppc f h c ms f h f ppc f h pduc. I u xmpl N N 3 [ 2 ] = 3 [N 2 ] [N 3 ] = -2 [N 2 ] R Lws Rcs vsbl. As pducs ccumul hy c bg u bck cs. Ely h wll dpd ly h mu f cs ps. W w msu h cs s s s hy mxd. Ths s clld h Il mhd. R Lws Tw ky ps Th cc f h pducs d pp h lw bcus hs s l. Th d (xp) mus b dmd xpmlly, c b bd fm h qu Pg 2 2
3 2 NO 2 2 NO + O 2 2 NO 2 2 NO + O 2 Yu wll fd h h wll ly Th f ppc f O2 c b dpd h cc f h sd b. cs. (Illy) R' = [O 2 ] = k'[no 2 ] R = k[no 2 ] Ths s clld lw xpss. Bcus h 2 NO 2 f ch O 2 k s clld h cs. R = 2 x R' s h d f h c -usully S k[no 2 ] = 2 x k'[no 2 ] psv g. S k = 2 x k' Typs f R Lws Dffl R lw - dscbs hw dpds cc. Igd R Lw - Dscbs hw cc dpds m. F ch yp f dffl lw h s gd lw d vc vs. R lws c hlp us b udsd c mchsms. Dmg R Lws Th fs sp s dm h fm f h lw (spclly s d). Mus b dmd fm xpml d. F hs c 2 N 2 O 5 (q) 4NO 2 (q) + O 2 (g) Th vs c w ply l bcus h gs lvs [N 2 O 5 ] (ml/l) Tm (s) Nw gph h d T fd w hv fd h slp 0.1 w ps 0 W wll us h g mhd Pg 3 3
4 A.80 M h s ( ) = 0.20 =- 5.0x ( ) A.40 M h s ( ) = 0.20 =- 2.5 x ( ) Sc h wc s fs wh h cc s wc s bg h lw mus b.. Fs pw R = - [N 2 O 5 ] = k[n 2 O 5 ] 1 = k[n 2 O 5 ] W sy hs c s fs d N 2 O 5 Th ly wy dm d s u h xpm. Th mhd f Il Rs Ths mhd qus h c b u svl ms. Th l ccs f h cs vd. Th c s msud jus f h cs mxd. Elms h ffc f h vs c. A xmpl F h c BO B B O Th gl fm f h R Lw s R = k[bo - 3 ] [B - ] m [ + ] p W us xpml d dm h vlus f,m,d p Il ccs (M) R (M/s) BO - 3 B x x x x 10-3 Nw w hv s hw h chgs wh cc Pg 4 4
5 Igd R Lw Expsss h c cc s fuc f m. Fm f h qu dpds h d f h lw (dffl). hgs R = [A] W wll ly wk wh =0, 1, d 2 Fs Od F h c 2N 2 O 5 4NO 2 + O 2 W fud h R = k[n 2 O 5 ] 1 If cc dubls dubls. If w g hs qu wh spc m w g h Igd R Lw l[n 2 O 5 ] = - k + l[n 2 O 5 ] 0 l s h ul l [N 2 O 5 ] 0 s h l cc. Fs Od Gl fm R = [A] / = k[a] l[a] = - k + l[a] 0 I h fm y = mx + b y = l[a] m = -k x = b = l[a] 0 A gph f l[a] vs m s sgh l. Fs Od By gg h sgh l yu c pv s fs d Of xpssd Fs Od By gg h sgh l yu c pv s fs d Of xpssd [ ] l A [ A] 0 = k lf Lf Th m qud ch hlf h gl cc. If h c s fs d [A] = [A] 0 /2 wh = 1/2 Pg 5 5
6 lf Lf Th m qud ch hlf h gl cc. If h c s fs d [A] = [A] 0 /2 wh = 1/2 [ A] l 0 = k 1 2 [ A] 0 2 l(2) = k 1/2 lf Lf 1/2 = / k Th m ch hlf h gl cc ds dpd h sg cc. A sy wy fd k Th hghly dcv pluum ucl ws udgs fs-d dcy wh hlf-lf f ppxmly 24,000 ys. w my ys mus pss bf h lvl f dcvy du h pluum flls 1/128h (bu 1%) f s gl pcy? Scd Od R = - [A]/ = k[a] 2 gd lw 1/[A] = k + 1/[A] 0 y= 1/[A] m = k x= b = 1/[A] 0 A sgh l f 1/[A] vs s gphd Kwg k d [A] 0 yu c clcul [A] y m Scd Od lf Lf [A] = [A] 0 /2 = 1/2 1 1 = k [ A] [A] = k1 [ A] [ A] = k1 2 [A] = 1 2 k[a] 0 Z Od R Lw R = k[a] 0 = k R ds chg wh cc. Igd [A] = -k + [A] 0 Wh [A] = [A] 0 /2 = 1/2 1/2 = [A] 0 /2k Pg 6 6
7 Z Od R Lw Ms f wh c hpps sufc bcus h sufc sys cs. Als ppls zym chmsy. c Tm c [A] k = [A]/ Summy f R Lws Tm M mplcd Rcs BO B B O F hs c w fud h lw b R = k[bo 3 - ][B - ][ + ] 2 T vsg hs c w d cl h cds R = k[bo 3 - ][B - ][ + ] 2 W s up h xpm s h w f h cs lg xcss. [BO 3 - ] 0 = 1.0 x 10-3 M [B - ] 0 = 1.0 M [ + ] 0 = 1.0 M As h c pcds [BO 3 - ] chgs cbly [B - ] d [ + ] d Pg 7 7
8 R = k[bo 3 - ][B - ][ + ] 2 Ths lw c b w R = k[bo 3 - ][B - ] 0 [ + ] 0 2 R = k[b - ] 0 [ + ] 0 2 [BO 3 - ] R = k [BO 3 - ] Ths s clld psud fs d lw. k = k [B - ] 0 [ + ] 0 2 Rc Mchsms Th ss f sps h cully ccu chmcl c. Kcs c ll us smhg bu h mchsm A blcd qu ds ll us hw h cs bcm pducs. Rc Mchsms 2NO 2 + F 2 2NO 2 F R = k[no 2 ][F 2 ] Th ppsd mchsm s NO 2 + F 2 NO 2 F + F (slw) F + NO 2 NO 2 F (fs) F s clld md I s fmd h csumd h c Rc Mchsms Ech f h w cs s clld lmy sp. Th f c c b w fm s mlculy. Mlculy s h umb f pcs h mus cm gh. Elmy sps dd up h blcd qu Umlcul sp vlvs mlcul - R s fs d. Bmlcul sp - qus w mlculs - R s scd d Tmlcul sp- qus h mlculs - R s hd d Tmlcul sps lms v hd f bcus h chcs f h mlculs cmg cc h sm m mscul. Mlculy d R Lws A pducs R = k[a] A+A pducs R= k[a] 2 2A pducs R= k[a] 2 A+B pducs R= k[a][b] A+A+B Pducs R= k[a] 2 [B] 2A+B Pducs R= k[a] 2 [B] A+B+ Pducs R= k[a][b][] Pg 8 8
9 w g d f mds Thy c pp h lw. Slw sp dms h d h lw Us h cs h fm hm If h cs fs d vsbl h cc f h md s bsd schmy. If s fmd by vsbl c s h s qul ch h. Fmd vsbl cs 2 NO + O 2 2 NO 2 Mchsm 2 NO N 2 O 2 (fs) N 2 O 2 + O 2 2 NO 2 (slw) = k 2 [N 2 O 2 ][O 2 ] k 1 [NO] 2 = k -1 [N 2 O 2 ] (qulbum) R = k 2 (k 1 / k -1 )[NO] 2 [O 2 ] R =k [NO] 2 [O 2 ] Fmd fs cs 2 IB I 2 + B 2 Mchsm IB I + B (fs) IB + B I + B 2 (slw) I + I I 2 (fs) R = k[ib][b] bu [B]= [IB] bcus h fs sp s fs R = k[ib][ib] = k[ib] 2 2 NO 2 l 2 NO 2 + l 2 (blcd qu) NO 2 l NO 2 + l (slw) NO 2 l + l NO 2 + l 2 (fs) lls hy Mlculs mus clld c. c ffcs s bcus cllss m lkly. Mus clld hd ugh. Tmpu d ld. Oly smll umb f cllss pduc cs. P l E g y Rcs Rc d Pducs Pg 9 9
10 P l E g y Rcs Rc d Acv Egy E Pducs P l E g y Rcs Acvd cmplx Rc d Pducs P l E g y Rcs Rc d } E Pducs P l E g y 2BNO B---NO B---NO Rc d Ts S 2NO + B 2 Tms Acv gy - h mmum gy dd mk c hpp. Acvd mplx Ts S - Th gm f ms h p f h gy b. Ahus Sd h c shuld cs wh mpu. A hgh mpu m mlculs hv h gy qud g v h b. Th umb f cllss wh h cssy gy css xplly. Pg 10 10
11 Ahus Numb f cllss wh h qud gy = z -E /RT z = l cllss s Eul s umb (vs f l) E = cv gy R = dl gs cs ( J/K ml) T s mpu Klv Pblm wh hs Obsvd s smll Du mlcul - h hv b fcg h gh wy w qu s p h sc fc. O N B O N B B N O O N B B N O O N B B B B B O N O N N O O N N Rc Ahus Equ k = zp -E /RT = A -E /RT A s clld h fqucy fc = zp k s h cs l k = -(E /R)(1/T) + l A Ah l!!!! l k vs 1/T s sgh l Wh slp E /R s w c fd E Ad cp l A A c s fud hv cs f 8.60x10-1 sc K d cv gy f kj/ml. Wh s h vlu f h cs 270 K? Whch sm s u ccg h pl f css vus mpus f pcul c? A) A sp slp f h l k vsus 1/T pl s dcv f smll chgs h cs f gv cs mpu. B) Dff scs f h l k vsus 1/T pl shw dff E vlus. ) Th pl f k vsus T shws l cs k s h mpu css. D) A sp slp f h l k vsus 1/T pl s dcv f lg E. E) Th y-cp f h l k vsus 1/T pl s h E vlu f h c Pg 11 11
12 Acv Egy d Rs Th fl sg Mchsms d s Th s cv gy f ch lmy sp. Acv gy dms k. k = A - (E /RT) k dms Slws sp ( dmg) mus hv h hghs cv gy. E Ths c ks plc h sps Fs sp s fs Lw cv gy E E Scd sp s slw gh cv gy Thd sp s fs Lw cv gy Pg 12 12
13 Scd sp s dmg Imds ps Acvd mplxs Ts Ss lyss Spd up c whu bg usd up h c. Ezyms blgcl clyss. mgus lyss h sm phs s h cs. gus lyss dff phs s h cs. w lyss Wk lyss llw cs pcd by dff mchsm - w phwy. Nw phwy hs lw cv gy. M mlculs wll hv hs cv gy. Ds chg E Shw up s c sp d pduc l sp gus lyss ydg bds sufc f ml. Bk - bds P sufc Pg 13 13
14 gus lyss P sufc gus lyss Th dubl bd bks d bds h clys. P sufc gus lyss Th hydg ms bd wh h cb P sufc gus lyss P sufc mgus lyss hlflucbs (Fs) clyz h dcmps f z. Ezyms gulg h bdy pcsss. (P clyss) lyss d lyss wll spd up c bu ly c p. Ps c p ddg m cs w chg h. Z Od Pg 14 14
15 lyss d. R R css ul h cv ss f clys flld. Th s dpd f cc c f cs Pg 15 15
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