ACHM 351 SUNY At Albany Chemical Kinetic Exam Practice

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May 13th 8-10am EST

Temperature Dependence of Rate constants

Reaction Mechanisms and Rate Laws, Consecutive Reactions

Reaction Mechanisms and Rate Laws, Steady State Approximation

Reaction Mechanisms and Rate Laws, Rate Limiting Step and Pre-equilibria

The Lindemann Mechanism

Collision Theory

Diffusion-Controlled Reactions

Transition State Theory

  1. Transition State Theory and Kinetic Isotope Effect

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Final Exam for Achm 351 -- Part 2 (May 13, 2021) Name___Put your name here___________________________ Here are the things you should know and must follow: • The deadline for completing and submitting your final (both parts 1 and 2) is 10 am this morning. Any late submission gets 5 pts/min deduction. This means that your e-mail submission for part 2 should get to my e-mail box before 10 am this morning. The way I calculate a late submission, hopefully none, is based on when a file arrived at my e-mail box. • Send your work of part 2 to me at lniu@albany.edu. • Type your answers in the word file, and expand the file as necessary. If you have to write it, write it legibly. If your handwriting is sloppy or illegible, you will not receive the full credit. • For submission, your final file should be PDF format or jpg file format. If you use image to show your work, you can either use a scanner to convert your image files into PDF and attach them to this file – send it in a single PDF. Do not send me any other file types. If I cannot open your files or your image is not clear, then your work receives zero credit – I consider you failed to follow the instruction and sent me an illegible file. ___________________________________________________________________________________ 1. (17 pts) For a consecutive reaction scheme as drawn (a) Write out the differential rate expression for each of the terms in this mechanism. k1 k2 ⎯⎯ ⎯→ A + B ⎯⎯⎯ C ⎯⎯→ D k −1 (b) Assuming that the C→D step is rate limiting, by pre-equilibrium approximation, write out the differential rate equation for the production of D (i.e., d[D]/dt = ?) (c) From this point on (or questions c-h), we assume that [B]0 >> [A]0, what is the kobs in the d[D]/dt rate expression? (d) What is the mass balance relationship for this reaction system (i.e., before and during the reaction)? (e) What is the relationship between d[D]/dt and d[A]/dt? (hint: think about the mass balance relationship you have come up with in (b) to derive the answer). (f) Now in the d[A]/dt expression you obtained in (e), what is kobs? (g) BONUS (12 pts): (i) What is the integrated rate law for A as a function of time? (ii) Discuss under what condition, the rate of the reaction is first order with respect to [B], and what condition would make a zero-order with respect to [B]? (iii) What is the unit of k2 from your derivation? (h) Draw a graph to show [A], [B] (again, assuming [B]0 >> [A]0), [C] under this pre-equilibrium approximation, and [D]. 1. (10 pts) In the two reactions, the rate law for each has been experimentally determined. The first reaction produces the desired product R, while the second reaction that generates S is unwanted or side reaction. Answer the following questions. (a) What is the ratio of the rate for the production of R to S? This is really a question for the favorable product distribution. (b) Is the first reaction an elementary reaction? Explain your answer (yes or no does not get your credit without the correct explanation) (c) You have the ability to set up the initial conc of the two reactants. What can you do to maximize the production of R or minimize the product of S? (d) (9 bonus pts) What else can you do to maximize the production of R or minimize the product of S, besides the change of conc? There are at least three other ways you have learned in the class. To earn the credit, choose to discuss two ways in detail. Explain your answer clearly. You have to present the assumption(s) or the condition for each of these two ways.
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