Worksheet — Reaction Mechanisms The sequence of elementary steps that leads to the formation of products is called the reaction mechanism. There are three types of elementary steps: unimolecular A ~ product rate = KA] bimolecular A+A or A¥B — product rate = K{A)? or K(Al[B] termolecular AtA+Aor AtA#B~ product —_rate = kA}? or k{A}[B] etc. These describe literally what is happening at the atomic scale. The sum of the elementary steps must give the overall balanced equation. They must also explain the experimentally determined rate law. The slowest . step in the reaction mechanism will determine the overall rate of the reaction and . is called the rate determining step. 4. The Kinetics of the reaction: 2X+Y—Z was studied and the results are’ [Expt [Xo (M) | [¥Jo(M) | initial rate (W/s)| @. Deduce the rate law including the 1 [020 [0.10 |7.0x10 value of k with units i 2 0.20 [0.20 | 1.4x 10 bavta’s (B0\% y- 9% @zl Cy) 3 [040 [020 [14x10 Fxio* Thay 4 [060 [060 [42x10 iC z ake ‘ CY poe g-o CX) Atk ss J k E10) ge Ge pon bts” are ce ee s b. The following 3 mechanism have been proposed. The species M and N are called intermediates, they are formed in early steps and consumed in later steps. What is the overall reaction for each mechanism? What is the molecularity of each step? What is the rate law derived from each? Which mechanism is consistent with the rate law from part a? fae nar Mechanism | x+y (low ate 4 COT p, hg X+M—-Z (fast) e tri cluemeb axt¥ oz cre stricuy . t uct Mechanism II J. eg ue ty = Tae XiM=Z_ (fast ame a voy 5 stnaduem £G — A yet - u vee 2 Mechanism i > Yom (slow) tv cyla os —— M+X—N (fast) a +X+Z_ (fast) ey ree 5 Pad etyThere are often equilibrium steps in mechanisms. We will usually assume that they are not rate limiting. The concentration of the species involved can be determined by setting up the equilibrium expression: K = [product)? /[reactant]' so that, for example, [reactant]' = K [product]? 2. Given the following mechanism: step1 2NOSNM& step 2 Nate +HO (slow nates & CMe) ch) step 3_‘Ny@+ Ha > No + HO a. Determine the overall reaction. 7NO4 2H, > 2H)0 + No b. Are there any intermediates in this reaction mechanism? N20, , Med c. Determine the rate law. Intermediates may not appear in rate laws. Use the equilibrium expression to write the rate law only in terms of reactants). 7, fs ICH] SS a CMofeeGneale nde LKOMGS CH, Je L'CUGY' Cs T d. What is the overall order of the reactions? , nd nder . What is the molecularity of the rate determining step? -/-)"- rclecolr UO +, = Nrot boAnother common component of reaction mechanisms is a catalyst. These are ‘compounds that change the reaction mechanism and provide a pathway with a lower activation energy, and correspondingly faster reaction rate. They are a reactant in an early step in the mechanism and a product in a later step. They do not appear in the overall reaction, but do appear in the rate law. 3. A reaction occurs by the following mechanism. step 1 Cet 4 Mn? + Ce + ar step 2 Ce Mn + Ce Mn step 3 Th eM TR + Mane a. Write the overall reaction i 2cet++I*-2 acer +71 b. Identify each of the components as a reactant, product, intermediate or mediate tocart product Ce*= moduct . Assuming that the catalyst is involved in the rate determining step, : what is the rate law for this reaction? yn?! vo ceteloet / Step lo 6G nete > hk (Ce* un*!) note d. Why is the uncatalyzed reaction so slow? (Hint: look at the Cee moleculatty) —ypp4) Tt 2Ces 4 TIHt famelteutea 4 AA 4, Under certain conditions, the reaction: 2NO + Ch + 2 NOCI is found to be second order in NO and first order in Clo. 2 ak cut) Ad Given the following mechanism, step 1 NO + Ch 5 NOCk step 2 NOCI + NO +2 NOCI what are the relative rates of the two elementary steps under these conditions? 4 step 12 ne detoaminy rate 4c0n0) CHI 2 Jat ndtr « NO tf ny L Arte cketonnmy act = Wl AIO] Cav Yat) rt rde CG = ACK), Ct) by Zehy ba bade ve NO Int adirch5. The rate of the reaction shown below was studied: 2.NO + H2 > N20 + HO It was found that the rate doubled when the [Hz] was doubled. It was also found that the rate increased by a factor of four when the NO concentration was doubled. Which of the following mechanisms is/are consistent with these data? nde k Ct, JGU0]” step 1 NO +H, N+H:O (slow p.ter ACMICH,] step2. N+NO+N,O y 2 co iL E22) Cow} KOM —" o— a step 1 NO +NO 5 N02 (2 2 N2O2 + Hp *NzO +20 (slow) Cul’ ale» & CMC) > LE CMY CAD ye oo rk? CH step 1 H, 52H . step 2 H+2NO—N,0+0H (slow) ae step 3 OH+H=>H,0 tte 2 ACH ICN kK" CWC OT step 1 NO +NO= NO» +N (slow) step 2 NO; + Hz + NO + H20. step 3 N+NO+N,O > 40w4) Nk