& Reaction rate & molecular kinetics Chapter 5 & 6 * a Content & PU eccreer scent PAB CRO MSIELE CRK CEOS Perera 4, Determination of reaction order Sivierecnmes OE etanst ites a a é & 2H, +0, > 2H,0 Actual: no H,O formed when mixing H, and O, at 25°C& 1.5H, +0.5N, —> NH, Gy NH) - 16.5 ksmol AM (NH) 6.1 Kame Actual operation temperature: 400-500 °C & Thermodynamics vs. Kinetics + THERMODYNAMICS: tell us direction of reaction, + But THERMODYNAMICS aives us no info. on. HOW FAST reaction goes from reactants to products. + KINETICS — the study of REACTION RATES ‘and their relation ta the way the reaction proceeds, ie.., its MECHANISM. & Thermodynamics vs. Kinetics + Reaztions can be one of the following: 1. Not therrrodynamically favored (reactant favored) 2. Thermodynamically favored (product favored), but not kinetically favered (slow) 3, Thermodynamically favored (product favored) and kinetically favored (ast) & Thermodynamics vs. Kinetics Sid, > Si+0, AG (S10,) == 805 kde! + Not thermodynamically favored (reactant favored) + Sand (SiO) will not decompose inte Si and Oy& Thermodynamics vs. Kinetics Diamond > graphite AG" (Diamond) = 2.9 ksfmal AG" (Graphite) = 0 kJ/mol + Thermodynamically favored (groduct favored), but not kinetically favored (slow) + Diamonds will tu into graphite, but the Thermodynamics vs. Kinetics C+0,>CO, AG og (CO) 3944 kulmol ‘6m mov + Thermodynamically favored (product favored) and kinetically favored (fast) + Burning of paper in air will turr to ash very Factors affect reaction rate: concentrations, temperature, catalysts, etc. > Optimization of reactor design reaction occurs very slowly. 7 quickly pe S an ec & Concepts j Reactants Products Intermediates Reaction rate Rate laws Reaction mechanism (molecular kinetics) + Simple reactions + complex reactions Roeauiang Unimolecular Bimolecular Termolecular Reaction order + Reaction mechanism + Elementary reactions oeSimple reactions ° (One-step reactions: Hy (k) + 1k) = 2H i Elementary Complex reactions | reaction/stop NO, +0, N,0,=N,0, + 0, NOs +N-Os = 4NO, Reaction mechanism Malti-step reactions: 2N,O, Numbers of molecul & collide/combine to. make a chemical change (reaction) £ J yv Taxman Molecularity Molecularity a +A molecule decomposes by itself is a unimolecular reaction (step) 0,5 0,+0 rate = k [04] + two molecules collide and react is a bimolecular reaction (step) NO, +NO, > NO, +NO rate = k [NOP + three molecules collide and react Is a termolecular reaction (step). Br+Br+Ar—> Br +Arr rate = (BrP a Reaction rate & + The reaction rate for a chemical reaction can be expressed as either: the increase of concentration of a product as a functon of time, =the decrease of concentration of a reactant as a furction of time8 Reaction rate © 8 Reaction rate © Unit aA+bB ~dD+cE mollis es a4 Kn _ LCs) ees na dba “dt edt {is a product S a & & Rate laws Law of mass action (Reaction rate equations/Kinetic equations) An equation express the relation between reaction rate and reactants/products’ concentration. R=f(C) Reaction rate of an elementary reaction is proportional to the product of the concentrations of the reactants. Cato M. Guldberg and Peter Waage (between 1864 and 1879)& A+B > products a Rate laws & + For a generalized homogeneous chemical Rate laws must be determined experimentally You CANNOT determine the rate law by looking at the coefficients in the balanced chemical equation! R=kC,. Cy reaction: aA+bB > dD +eE For > General form of the rate law is lomentaryeimple a Teaco oo R= kC,* Cyy where : K= rate constant : reaction-order with respect to A y: reaction-order wit respect to B (sty): overallikinetic reaction-order a a & & Rate laws Oa OIE: iac, le Straight line plot of Cay vs. ¢ =Cyy~ hot Slope is - k, (mol.lit".s) Concentration/Time relationships Zero order reactions & Gy slope = Half-life time (t,z): time when reactant remaining is ¥% of original amount te typ: Cy =Cyl2 Concentration/Time relationships Concentration/Time relationships Zero order reactionsConcentration/Time relationships 1s order reactions KC, BD 1c, =n - ke nee Cao Straightline plot of Cy vs. Slope is - k, (s*) ae & Inc, nC slope =-h Concentration/Time relationships 1s order reactions ee ak, Concentration/Time relationships 2” order reactions Case 1: One reactant (A) Ratan »> Straight line plot of 1/Cyy vs. t Slope is + k, (mol lit.) )& 2 slope = AIC, Concentration/Time relationships 2* order reactions Case 1: Concentration/Time relationships 24 order reactions Case 2: Two reactants (A,B) #1 1¢ dt Co Concentration/Time relationships 2™ order reactions Case lac sieric a 10% Co= CoosConcentration/Time relationships 2” order reactions Case 2: pe ©. dt 4 AkC,Cy Concentration/Time relationships 2" order reactions Case 2: Cy # Co mm & In(oy0,) 9 slope = (Cap Cal In(Ca/Cx)| Concentration/Time relationships 2” order reactions Case 2: ifCyg *Cyq ‘For reaction: 1A + 1B > Product cea Ca=b Extent of esction=CC, =X = 548 = AKa-0) nota]Reversible reactions Parallel reactions Consecutive reactions Independent rule Reversible reaction + Ifmany elemertary reactions occur in the system, k each reaction follows “law of mass action’ and occurs aA + bB > dD +eE independently Total change o* each substance is equal to the sum of k all change in the reactions. aA+bBSdD+eE — R=kCIC; dD+eESaA+bB R=:Reversible reaction aA +bB 5 dD +eE At equilibrium: Renu ahce R=R' —equil, Const Cin (relation 1) & Reversible reaction 1-1 reversible reactions: A <= B Reversible reaction 1-1 reversible reactions: A<> B j= Cy =x Cg = Cryo +X AC,-k'C, (relation & Reversible reaction 1-1 reversible reactions: A <= B 3]Ho, KL tae, +4) & Reversible reaction & 1-2 reversible reactions: A <> B+ D 2-2 reversible reactions: 2A <> B + D Parallel reactions Parallel reactions B ag yc Inc, een tk, sh IC, s Ina : = -{k, +k’,) ~ foarte) INC, =InC yy (6, +h) ‘relation 1) uae use i caea Parallel reactions & Parallel reactions a= dCp/dt = ky.C, t=0: — Cgy= Coy = 0 tet: Cy = Cg tg +e AC g/day = kik", =P CylCo = kyl’ (Ceo = Coo = 0) Parallel reactions =, Re B e Pc INCI (kt kt =P C=C, HK cette, an Ro= dCpldt = k,.Cy, Coa Cotte] K bt ek Relation 2 FC wll") Ro= dCo/dt = k’,.C, = Cette)Parallel reactions = m——19 $s ate 2. g -dC dt = ky.Cy + Ky. Cy.Cy § ~dCa/dt = ky.C,.Cq Reaction time & Parallel reactions ky A c LA A+B — > D k Mb C Cun 42 a C+, + An Se E & 2} Series/ Consecutive reactions k, ky G (B: intermediate) Ceo= Coo = 0 tet: Cag Cy + Cg tC & 6]& MS sat At+B+c| Series/ Consecutive reactio1 -dC dt = ky.C, dC /dt = ky.Cy —k'y.Cy dCc/dt = k’,.Cy Consecutive 1* order reactions & a C| a aE mak Consecutive 1* order reactions & Consecutive 1% order reactions & AS BoC A ‘poe 2 dCy/dt =0 eSiean B! Stable intermediate ‘Step 2: rate-determining step Ky << Ky! Comac* Conti) B: unstable intermediate Step 1: rate-determining step |Consecutive 1% order reactions & at+n-sc) ICHIN t ee i 1k, = const, Ky >>: > tn, Small ky [Ky const, (Ky Ky) < ting large > Time wner (Cy Can) 5 ong + Steady state (Aft ~0): Steady state approximation © ky >> ky Cec Glowandesenty constant Concentration of unstable intermediates are small, =| steady state conditions are Consecutive reactions with two intermediates k, ky Generation rate of B = Consumptior rate of B. obtained (Useful for obtaining rte laws of a complex reactions) a a & & Consecutive reactions with two intermediates Cole") Cyple -e*) 1 Cy Cra & Consecutive reactions with two intermediates tty oCy/t =O B ie \e / tetly! dCg/dt =0 a & Consecutive reactions with two intermediates ky ky ky A" ey fe €,=Cye¥ = a & Consecutive reactions with two intermediates Ay ky ky a —. p—.¢ —*.d eas00 in| cai bet200. enss0on & Steady state approximation Concentration of unstable internediates are small, steady state conditions ere obtained dC, inmemediae _ Q) dt8 Steady state approximation * Ex: Consider A + B = 2C with mechanism: A> 2ML (ky) M1+BC#M2 (k) M2+AC+ML (ks) M1+M13A (k,) Determine rate equation if M1, M2 are unstable intermediates. Steady state approximation ac +h a & ey, 1 neu, : 2h.C,-2,Ch, ee rE orc! , hein f 2 Cy hiCysls a Steady state approximation & aoa z OBE tls kyl n= fc, $b CC, i a UyCy Bhp, =O BAe 0n +h CnC) a & Oe RaeDetermination of reaction order ion eens zero order " eee 2! onder n= order with respect to A=? a & Determination of reaction orders R= - dC,/dt Ink tga=n InR=Ink+ninc, | Ink IMC, Determination of reaction orders Assume 1* order: tga= Hk, @AIG, IC 9 ta= ky ¢ ¢ Determination of reaction orders Determination of reaction orders Roky Rk Gy Assume zero order: Determination of reaction orders (/q-conversion time method: q=2) Re-dCyitek. Oy oe Ing, =(=n) nC, ~In ‘ gD i eetua = wh Ing, , =(—n)InC,.—In- in #1, SD [Ins 2G DECE | a) Co tvs Cw & Determination of reaction orders (/q-conversion time method: q=2)& Determination of reaction orders Rokoe Peo = (nal) Dyas? => Gor quiek station) & Determination of reaction orders Determination of reaction orders Rouen Method I: Flooding method Method 2: Logarithmic method Determination of reaction orders Using a large excess of a reactant (Flooding method) R= 1 Cy” R= yo »k.a & Determination of reaction orders Using a large excess of a reactant (Flooding method) R= 1 Cp™ & Determination of reaction orders + Keep initial cone. B = const, change initial conc. A: Ry =k Cy? Gy > MRK + a 4 mINOys Re=K Cys! > RAR + nln INC THR Determination of reaction orders + Keep initial cone. A = const, change initial conc. B: Ry=K.Cy'Cagj" 9 Rank #rlnCyg # mC: 4K Cyan" InRetnk nny # MIN ine R= MINE, ad, > km nae)i A A, aA Effect of temperature & & : Svante Arrhenius Van't Hoff rule When temperature increases 10 °C, reaction rate Nobel prize 1903, increases 2-4 times. Wan tHoff coefficientEffect of temperature ‘Arrhenius equation: a é Ke = Ace Eel BT], aetvation energy Ay Effect of temperature © ink=-F¢ 4 4104 RT NSN Effect of temperature el, a é6. Molecular kinetics & 4 - Collision theory } 2. Transition state theory (TST) | Reaction rate depends on: - Collision Frequency - Direction factor - Activation energy (E,) Reaction rate increase when number of collision increases, depending on: - Concentration - Temperature& Col a ion theory & + Only collision with correct direction can + Only collsion with a certain energy make the reaction occur. (minimum energy) can make the + Ex: Cl-+H-Br— H-Cl +Br Ueaullonene ‘Minimum energy of the reactanss wth which the action Occurs afer colision Rescton doesnot + Energy difference between reactants and the cco Interrediate. aacon doc nt — Activation energy (ts) @) iC) 9 Collision theory ° Fe i ° Transition state: | "ions Arrhenius equation arses : + Reaction rate increase at high ‘arrangement of temperature because: rate | con [A = Molecifes have high kinetic energy state amongtte * =p = More collision reagan en he (ooo ~ Mote colision with high energy ( E,) — Maximum eneigy sions —> | conte reaction ‘energy diagranNumber of collisions Number of collisions of molecules in a unit of volume per unit of time: = cls dometer A&B (08) ge uber of molecules A, Bin am? 1s ameter ofthe molecule + n:nat of te molecdes inc? Roasts -adianen [sear + Ly Reaction rate + 2A products zeny reactions to total R=g2\,=42a0'n ( na lisions. + A+B Products M, M, Reaction rate ° ,2( RT R=ge',=g2d'n'| Gey = 4 (=) La) | R= q2'y=Gd‘ig ney) SART| 4 ea ‘+ Similar form to the “law of mass action”a & Rate constant rae mere mor = Is often very small, depends on: 1. Colson direction: Possibility P = 0,1 -0,0dt 2. Energy: colision with atleast € energy. a= Peexp(-E/RT) Rate constant iq= P.exp(-E/RT) [Almost similar forms to “Arrhenius equation” and na ee Stay ot mass action” | sa a, a & & Transition state ABC" Cla EC or Activated complex theory/model J Tanston state: Forming activated complex& & Transition state Transition state ER ‘Activated complex! transition state AB+C <=" ABC > A4BC IReactones + TST suggested: ‘Slowest step is the formation of the activated CrRaee complex Reaction a Be Rate constant & Rate constant & AB+C =" A + A+BC = According to quantum mechanics: Gx BF co ene ,:caentation ofthe activated cores + teiee of he activated complex (C!cccenation ofthe acvated complex at nultum AB+C A At equilibrium eta) [eae] ar c A+BC Clo = KL Cea a & & Rate constant Rate constant AB+C =" ABC + A+BC AG =-RT.inK, ==) Ky=e™ FL KCC. 2k YC, ire act sar => .-— Noh - a a & & Rate constant Rate constant AB+C = AB.C + A+BC ‘Comparison ku kak Pee \ SSE 3c. 05, 21: cttscern, Ne Se taper ne eT acted cares formation a Noh peg one lo Noh Re ee