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    ChemReac NoreQt

    Uploaded by

    JusztinAquino
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    © All Rights Reserved
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    CTHRE-A. LECTURE 4- FUNDAMENTALS OF CHEMICAL KINETICS Chemical Reaction Engineering CCRE) 16 the field that studies the Gates andy Tiieenaniéme of chemical reactions and the [desigh of the reactions) in which they take place. HOW Do WE KNOW IF A CHEMICAL SPECIES HAS REACTED? = lost of lehemnical identity? 4 kind, number and configuration of that species’ atoms. © the reactant is converted into product. THREE WAYS FOR A SPECIES TO LOSE ITS IDENTITY! 4. DECOMPOSITION CligCy = Hot WoC = CHD = chemical breakdown = product specie ig more than compare to reactant specie 2. COMBINATION N20? 2NO = synthesis reaction an = combining +Wo or mofe reactants 4o form single compound or product 3. ISOMERIZATION CotsCH = Cio 7 Ce =CCCHs)2 = compound is transformed in any of its isomeric forms or | isomers.” G chemical species with same chemical composition but with different, structure or configuration- ao AW a 4. IRREVERSIBLE 140 AVE = also called uni-directional reaction, since We are converting reactanis to products j_and product cannot be back to reactant again. = forward reaction ex! combustion reaction cor g 02 ™ COg 2. ee CHAE RFE “equilibium anow = reactants and products are never fully consumed, #hus they are constantly Teacting and being produced at a certain rate. = they _lead_to equilibrium ex: ao a8 os Ge GP Ge Cot HeO = COot He = forward and reverse reaction are both favorable. _Bidyat namic equi funy = feactams ate formed at the came rate to the products Limelight Scanned with CamScanner 3. SIMULTANEOUS / PARALLEL Roe > teactants are converted into both products competitively ond simulaneousty. + _also_known as side reaction. ex: Bromination Br eee, Br fe + RGr O- dibromobenzene a (0) +8to — LTO} + her P- dibromobenzene 4. CONSECUTIVE / SERIES LHO A NVHESItS x: CHE CH4 Hp 7 Cp = Chota — CH3CHs Wikeording to Movecularity ly numver of molecules that come together to react in single step reaction: Tyifocused on reactants” ly only speaks on singie step reaction | 4_UNIMOLE CULAR AaB ex! | > * ISomerization of xylene * Thermal decomposition of calcium carbonate Cs | a Cacos Aa-Caor€0, | o- xylene cig _ p-xylene 2. BIMOLECULAR = Wo reactant moieaule Two cases * a. Two distinct molecules AtB AC ex! Clg B CH tHe “3 CH3CHy Two identical _moiecules 2A 41 B \| ex: 2HT 4 Het Tp | 3B. TERMOLECULAR / TRIMOLECULAR Possible cases * a. Three distinct molecuies AiBrc 3 OD | ais Limelight | Scanned with CamScanner b. Two identical _and one distinct molecules 2A+8 40 At26-40 exi_2NO4 02 4 2NOg ©. tnree identical moiecuies | saa B (Te Hecoraing to Phases) | 1G dictinet and homogencous state of the system with visible boundary Separating it into parts. 4. HOMOGENEOUS C Single phase) * Non- catalytic? most gas phase reactions T withoud invoWement of ony inflUencing material relating t0 +e speed ot rate of the reaction: ex: He C9) + Brag) S 2HGr C9) * Catalytic + most liquid phase teactions ex: Ciatton0n Caa) + R068) “EC Cy Wiz 4 cqucose) Cad) + Colin06 c fructose) A) 2. HETEROGENEOUS C two of mote phases) = typically they are catalytic fe: = feaction happens in the boundary or interface ext gas - Gdlid : HCN synthesis from Nis, Chy and ait Ccataytic) | 945~ liquid: absorption of CO2 from amine solution C non- catalytic) liquid liquid? synthesis of adipic acid from cyclohexanone ond HNO» C oxaty tic) 02/4212022 10:45 pm [RATESOFICHEMICALTREACTIONS) [chemical Kinetics is the branch of physical chemistry that deals with the Gludy of rate of reactions and the factors governing tate of reaction. Important application of Kinetics studies ¢ 4. In determination of rates of reactions and factors governing fates. 2. In predicting the conditions for maintaining te reaction rate. B. In determination of yield of reaction in certain time period. , In calculating the fime required for completion of a teaction. 5. In deciding he mechanism of 4 reaction. Limelight Scanned with CamScanner Types of reaction based on reaction rates 4. VERY FAST/ INSTANTANEOUS REACTIONS = occur at very fast rate = _invotwes ionic species = it ony takes 10-145 teaction of ionic reaction. x precipitation tans? AgN0g Cag) t Nacl Cag) > Agel Ce) + NaNOs Cad) neutralization tng! NaO# Caa) t NCI Caq) 7 NaCl Caq) + 42068) 2. MODERATE REACTIONS = proceeds with measurable fates at normal temperature = easy to extract Kinetic data at normal temperature = most are molecular in nature ¢ bond) ext ) decomposition of e09: Ha09 7 H20t 2 hydrolysis of eter! Cy COOCEHs + Nadt 7 CAsCOONa + C2i5 OK inversion of sugar? Cra Wor Ot 7 CoHi20e Cowcose) + Colli2 Oo Csructose) 3. VERY SLOW REACTIONS = it would take months oF Yeats fo chow measurable of observable change = difficult to determine rate of reaction et tusting of ton! Feg Ost xeO 7 Fee Os xted C hydrated ferric oxide) polyethylene degradation of A MIP, a very Smali_time interval. Ploceeds amount of A become little of to signifies, it decreases with time. irate of | Ce. positive Cp means it increases with fime- Hormation of 8 dt Parameter to obtain kenetic data: 1. CONCENTRATION * liquid-liquid teaction 2. PRESSURE - gases reaction 5 P= CRT 5. ABSORBANCE - Coloted_ solution. U. CONDUCTNITY ~ ionic solution (eg. acids, strong bases) Scanned with CamScanner it i The reaction rate is the rate at which @ species looses rate of aC, __* differential i6 used because igappearance € dt We only measure concentration at For the genetic teaction: aA + bB = cl t dd rate Cof reaction) = “aca -dCg tdCe , + dtp adt bat _cdt_d dts ex? Net Sig ™ 2NHs —_teaction sate? “dtna . “dCwe . tdCuns. dt Bd 2ak or = Ach (4x) 3 ( die SF eee at dt dt "AVERAGE RATE and INSTANTANEOUS RATE OF REACTION | AVERAGE RATE = change of concenttation of the ptoduct or reactant divided by time interval cover which the change occur. FOR REACTANT: fove ACR] "{ CRol- CRT) AL fgets 2s For Product: : tov ACP) CPaj- hd At to- 44 INSTANTANEOUS RATE és = derivative was used because it occur on short span of time. For Reactant: Sing =~ ACR] _ slope at For Product 3 Tins = ACP] slope at Exampte For the reaction? N205 -3 NOg t O2 the concentration ve time plots of 205, ne ‘and Og are shown below. Determine: Wo, | Acthe average rate for the decomposition of N205 between 2 min and 6 min. faye, N2o5e AC positive since magnitude at = _Cwros, ¢ = C205, i te- ti You can use Getdata graph digitizer. Limelight Scanned with CamScanner 3 0-011 0.08) MOL =0.015g mol_+ | -ACnaop _ 0-015 mol | 6 2) min Lemin > At Lema |_2. the instantaneous rate for te decomposition of N2o5 at 2 minutes. Taye, Neon 7 AC Nos at o70 Tins, Na05* “dC W205 egtgng-e AY dt + ieee = 0:1365 ©. 0229 __Mol 540 , 3: the initial rate for the decomposition of N2O5 Sing, N20 * ~ dC N205, a a wit mina Youth use Getdata graph digitizer Simple Problems on Chemical Reaction Rates 4: Consider the following balanced chemical equation: He 09 cag) t 3I"caqy + 2H'caq) 4 Ix cag) t 2H20 CE) In the first 10.0 seconds of the reaction, the concentration of I dropped fom 4.000M to 0-868 M- a. Calculate the average rate of this reaction in this time Interval. b. Predict the rate of change in the concentration of Wt, HeO and ts during this time interval. GINEN: Crs, is 000M Crig*® 0-869 M bic 0-05 te® 1005 Te ) fave, txn® ~ACz- _-C0-868- 1.000) M_ | 3M Bat 3C10-0-0.0)5 So atOnag b: == ACwy = aCe me 2a att 8 tare Tea) Limelight Scanned with CamScanner ACuy 2 C4 HOX10' 3 Mis) = [8. 80x 10°53 Mis At Save, xn © —Aete8 4.4O x40°3 MIs Save, txn£ res 2 4.40x40°3 Mig | 2. Consider the teaction : 2HBF cay “Y He Cg) + Bra Cg) a. Express the rate of the reaction with fespect to each of the reactants and products. = b. In the first 2606 of this reaction, the concentration of HBr dropped from 0-G00M 40 0-542 M. Calculate the average rate of the reaction in this time interval. ¢- If the volume of the reaction vessel in part Cb) WAS 1-50L, what amount of Bre Cin moles) was formed during the Fitst 15-05 of the reaction. Hint: Volume of vessel _is constant. SOLUTION! a. Taverin? ~ACwpr tOCwg | + ACBra 2at At Acme b. e Crpiit 0: G0OM 4iF 0-05, Se Cup, * 0-512 M ft 26-05 ne Ss fave,txn = * SCnee = C 0.512 - 0-00) M gar €25-0-00)5 ~-fasexio? 2] Pes S ip? 3 fave, rxn* +hCpro | Cora, pe Corgi i: _6= 8 i ‘at te ty zy v 0 nBraie npc, n Nefai nd Vag vCte- $0 te = ti B-52x10? Mig *_nBte, F 45 UC15-0 s) [Pare 0:0742 mot 4, 02/ 412022, 10:16 pm Limelight Scanned with CamScanner TURE? 2 FACTORS AFFECTING RATES OF CHEMECAL REACTIONS URa¥ereP reaction is the rate at which chemical reaction proceeds. Reaction Occur When HNO of More Molecules Collide with each other, and must posses Qctivation energy. Chemical teactions in genetal proceeds at different rates. “Factors Affecting Rate of | a 4. Concentration of Reactant - directly proportional to the rate of reaction Q. Temperature - ditecty proprtional 3. Particle Size : 4. Presence of Cataiyst - the lower the activation energy, the fasier +e rate of reaction. TECTOURES: COIFFERENTIAL) RA ON _REAC EFFECT OF CONCENTRATION ES Reaction Rat how We measure tates Rate Laws = how the rate depends on amount of reactants Low concenttation= few collisions High concentration= more Collisions, Removing fhe proportional 1 symbol: ——= cé = za LIMITATION OF THIS Ly constant of proportiona lity. Similarly for aAtbBtcC > dds eE faz KaCh CR CE tet kp CACa CE fe ke CACECE where, K= rate constant C different per reaction, changes with 1émperature) ¥? order of reaction with tespect 0 A y= order of reaction with respect to B Cxtytz)* overalt order of reaction NOTE! % y and z are NOT related to a and p. They can only be determined EXPERTMENTALLY, Limelight Scanned with CamScanner Exampie? For the rate equation: rate = KCaCg What is the order of #ne reaction with tespect to A? SY order with tespect to What is the otder of the teaction with tespect to B? Ans: 24 order with respect to B Whot ig the overall order of tne reaction? Ans: 143 = 3 C3td order overall), What happens 40 the rate @f concentration of B is doubled? C Ca constant) Ang: tate quadruples. What happen to the rate if concentration of A is doubled? C Cp constant) Ans: rate doubles Methods to Determine the conect rate equation 4. Initial Rates 2. Differential ( Numerical Differentiation, Graphical, Polynomial Fit) 3. Iniegtar 4. Excess. 5B. Hatt- fives G. Differential, variable volume. Sei-Up of Reaction Rate determination The Rate Law: Effect of Concentration on Setup of reaction rate determination Batch Reactor 1. Closed system 2. usually liquid phase (p is constant) 3. Well-mixed( A > B, Cy, Cy, and T are uniform) 4. Ca, Cp F change with time LEELA | ie i hen RevcionGrmeering Cope 201 Rear. Maubhan. Aight reverved. Altrademars [Sovimugerequres por notatonand wrt cme Scanned with CamScanner Setup of reaction rate determination Br, (oq) + HCOOH (aq) —+2Br (ea) + 2H" (ag) + CO, @) N20s,) > NO2 w* Pre seen Merze| ae) ‘a AAbsorption Wavelength (am) Consider the rxn: C,HgCl(aq) + H,O(/) — C4HgOH(aq) + HCl(aq) Time, t(s) ICyH3Ct] (M) Time, ts) ICjHACH (M) Average Rate (M/s) 0.1000 00 0.1000 _ You should be 0.0908 soo cso 19 x10" leis 0.0820 100.0 0.0820 Bee cul: 0.0741 150.0 0.0741 16 x 104 eae srt » 2000 0.0671 M4 x 107 these values. | 0.0549 3000 0.0549 Tas ous 4000 048 a 0.0368 500.0 0.0368 0.0200 800.0 0.0200 ——— 0 10,000 0 Q.560 x 10-4 Average tate decreases because as the teaction gots forward, the collisions bet: feactant Molecules becomes Smalier. ‘Time, t(s) ICyH,CH] Average Rate (M/s) op 000 Lf Preferred data. Why? 50.0 0.0905, 4. Since ConceMtration of reactant decrease 100.0 0.0820 it_may be difficult to measure the 1500 0741 changes accurately. = a 2. There are chances that reverse reaction 1.01 x 10% happens. 400.0 oous 4 oan iss 80x 10% — 800.0 0.0200 ee 10,000 o Se Limelight Scanned with CamScanner inl a a) a a a = Example: The overall chemical equation for the reaction of nitrogen Oxide, NO with chlorine, Cle ig: 2NO+ Cla 4 2NOCI. The initial rates of reaction fof» various concentrations: of the teactonts were measured and recorded at constant temperature aS Follows * 0.25 Os 0.25 1.0 0.50 20 a Determine the rate law of this reaction: Solution: rated KCNor Cone KC 0/5)* C0.5)% fate 2 KON FCoi,e KX CO/25)* (1-0) 9 E> Convince yourself trerink= “ACcx/Bt —— 0.75 — 3.02 _ 24.10 Ly since according to problem, there i6 constant temp. 0-15 MI he 05d. y= 5-02 ne. 1039 > [rate = KGnpC aig | b. Calculate the numerical value of the rate constant. * Select experiment 4. sate 4* KCnos C (0-15 Mine = KCO-25M)CO-5M)? 1 t= 42 MP he ota, NOTE: unit ofK depends on. order of reaction. C: What is the overall order of the reaction ? overall order = xty = 442 =[5°4 order overall | ‘ds What is the rate of appearance of NOCI_when he initial concentrations of the reactant ore Crio™ 0-20M and Coie = 0.50M? Get the initial rate from the given initial condition. rote = 12 M2Che), 0:20) 0-30)? = 0.20 Ml nr rate = +ACnou gat ACuoa . 9 Ae u 7S ECOG Mp) 2 { 0. 432 Mine Limelight Scanned with CamScanner Consider x" order cate law? Reaction’ AB Taking the natural 1og* Tin (dca GX slope = me tee x ¥ ¥_W mCsiope) y-value —_ Cy-inetcept) (Wow to ereale graph? | 4: Create ¥-y graph : 4- axis = In (dCa/ dt) 5 x-axis = In C concentration of A) in C 46R/ ae) 2. Determine Slope = reaction order Ys imercept = In k However, we ate usually given concentration as a function of time From batch Teactor_ experiments. [ime ¢s) o | ti [te [ts | concentration C molf dm?) [Can | Cas | Car | Can | So use Numerical differentiation, graphical and poiynomial fit to get the equation: Example? The reaction of tripheny! metnyi Canty!) chiorid@ CA) and methanol CB) @ Hs) CCl + Cs OW 7 CCot's) sCOCHS+ HCI Awan re Oa retC a) Wag cartied out in a solution of benzene and pysidine at 25°C. Pyridine reacts 2 with HCl that precipitates as Pyridine hydrochloride thereby making the reactions ireversibie- The concentration- time data below was obtained in a batch teacto Cin) o | 60 [| 100 | 150 [| 200 [ 250 CaCO am? x 108) | 50 | 38 | S06 | 25-6 | 222 | 145 The initial concentration of methanol was 0.6 mol dm? @. Determine the reaction order with fespect to A. SOLUTION ® + Postulate a rate taw faz KChCB + Process your data in terms of measured variable Limelight Scanned with CamScanner 43 48 48 48 4 4B 4B 43 19 18 SH _In_this_case, it is Cr * Look for simplification Analyzing the table, CACto?) * 50 Cy? _50 4000 Cape 0.5 MV/dm3 ; Since Cao * agsume_ shat Cp? C80. From step 4 and 3 taz_ kok CH * KCACHS let Kz KCgo C constant) az KOR + The rate equation will become 10C,, CB is reasonably torge than A) you can Concentration of 8 is constant) tar dC, tek TCR * Take the natural log of both sides In (ACA. te yainn ae] phd yeaa Bx + Fina ~ 4a/ae_as a function of Ca from ey a concentration time data _using* a _ Solve + _ EACA = Cai = Cai = Aki tai? baie Sampie _Catcuration + =ACAy = Cay Cag. 38-50 Otis to 50-0 _—__tagrerepiot_ng dota, Then_re-Scaie Cay o.24cio4) ay = @) A CA tu ACW py, x10" Gicane iSoummrommnc) : original 3B. 50 30. 100 igi 25:6 250 _ 29.2 200 4 414.5 250 5 ost Limelight Scanned with CamScanner ifferential Method (Constant volume systems) Equal Area differentiation. i Graphical Method. Plot ~

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