446 Practice Exam 3 Part I Solutions

Problem 1.)
There are nine reactions below which you must identify as elementary (as written) or not, and if not, why not. These reactions occur every day in your body, so you should know by heart if they are elementary or not, right? 1.) A2 -> 2A Elementary. 2.) A + B -> A-B (A bonded to B) Elementary. 3.) A + (1/2) B -> (A-B) (A bonded to B) Not Elementary. Fractions are not allowed. 4.) 4 A -> 2A2 Not Elementary. A 4-body collision is not allowed. 5.) 2A2+2 B -> 4A + B2 Not Elementary. A 4-body collision is not allowed. Possibly too many bonds formed/broken simultaneously as well. 6.) A2 (gas) + 2S* -> 2(A-S*) Elementary. Disassociative chemisorption. 7.) A2 (liq) +2 S* -> 2(A-S*) Elementary. Disassociative chemisorption. 8.) A (gas) + B (liq) + S* -> A + (B S*) Elementary. A 3-body collision is allowed if a liquid species is present during an adsorption process unto an empty catalyst site. 9.) A (gas) + B (gas) + S* -> A + (B S*) Not Elementary. A 3-body collision is not allowed if no liquid species are present during an adsorption process unto an empty catalyst site.

Problem 2.)
Another long senior design homework has been assigned. Dr.Confetti has only given you two days to complete this assignment, as usual. You (A) decide to get started on the homework (S*). Normally, you would attach yourself to your work (A-S*) for hours until the task was complete. This process is a similar one that student (B) follows. Being social butterflies, you and student B, both glued to your homework (A-S* and B-S*), decide to work together on the assignment. After a long day, you both have become good friends. You both hold hands in harmony (A-B), and walk out the door with two stacks of homework papers finished (2S*). While working alone, you got distracted, but managed to keep productivity up (e.g., you were in equilibrium with your work); however, your friend lagged behind because of his lack of productivity (e.g., he was slower than you..perhaps you can call him, ratelimiting). Combined, you two were in equilibrium with your work. Using this scenario, answer the questions below: Step 1: A + S* -> (A-S*) Step 2: B +S* -> (B-S*) Step 3: B-S* + A-S*-> A-B + 2S* (In equilibrium) (reversible, RLS) (In equilibrium)

a.) Is this an open sequence or a closed one? It is an open sequence because it is most likely that these steps are not the only ones that make up this process (e.g., there are more elementary steps involved that are not shown). Further steps would be required to explain how Dr.Confetti created the homework (S*) in step 1. b.) What are the Active Students? What is the empty homework? Hint: Think of the students as being centered individuals, and the homework as being something they can adsorp to. The Active Students/Centers are: A-S* and B-S*. The empty homework is S*. c.) Assume that these steps are elementary as written. Following the RLS procedure (regardless of open/closed sequence), write the rate of homework completion if Step 2 is the RLS. rate(a-b) = rates* = k2[B][S*] k2*B-S*] For Step 1: K1[A][S*] = [A-S*] where K1 = k1/k1 For Step 3: Treat the reverse reaction as the forward reaction ([A-B][S*]2)/K3 = [B-S*][A-S*] Plug in what [A-S*] is: ([A-B][S*]2)/K3 = [B-S*] K1[A][S*]

{([A-B][S*]2)/K3} / K1[A][S*] = [B-S*] Simplify: ([A-B][S*]) / (K3K1[A]) = [B-S*] Do a total site balance on S*: [St*] = [S*] + [A-S*] + [B-S*] [St*] = [S*] +({K1[A][S*] + ([A-B][S*]) / (K3K1[A]) } [St*] = [S*]{1+K1[A]+ [A-B]/(K3K1[A])} [S*] = [St*] / A where A ={1+K1[A]+ [A-B]/(K3K1[A])} rate(a-b) = rates* = {k2[B] k2[A-B]/(K3K1[A]) } *[St*]/A d.) Now suppose student B does not get distracted (e.g., he is no longer reversible), but he still remains working slower than you. Write the rate of homework completion if Step 2 is the RLS. The only difference in this part is that the second step is irreversible. This actually simplifies the work needed to be done to derive the rate of formation of A-B. rate(a-b) = rates* = k2[B][S*] Plug in [S*] in terms of [St*] from Problem 2: rate(a-b) = rates* = k2[B] * [St*]/A where A is {1+K1[A]+ [A-B]/(K3K1[A])}.

Problem 3.)
Using the same scenario as in Problem 2, lets now assume your friend has just drank a Fanta soda drink that helps their brain focus. At the same time, your girlfriend/boyfriend has just left, and now you are totally focused on your homework. Nothing can reverse you or your friends productivity on the homework, while you two are working individually. However, when you two join up to work together, you distract each other to some degree (e.g., productivity is somewhat reversible). Step 1: A + S* -> (A-S*) Step 2: B +S* -> (B-S*) Step 3: B-S* + A-S*-> A-B + 2S* (irreversible) (irreversible) (reversible)

Assume that these steps are elementary as written. Following the proper procedure (regardless of open/closed sequence), outline how you would derive the rate of homework completion. Select Step 3 to be the rate of formation step.

Perform the SSA on the formation [A-S*] and on [B-S*]. Add the rates and set the sum of the rates (after doing the SSAs) equal to zero, thus solving for either [A-S*] or [B-S*]. Plug in what you just solved into one of the SSA expressions to solve for the other [X-S*] term (e.g., after you solved for [A-S*], plug it into one of the SSA expressions to solve for [B-S*]. Do a site balance, and finally plug in all the solved variables into the rate expression for the rate of formation.

Problem 4.)
Ms.Fiche Alot has just reached the battle grounds of a major bass hunting competition. She is so skilled at catching bass that she will be taking on the entire team of Team Beeg Ceets by herself. There will be 2 fishing zones: X and Y. Beeg Cheets will be stationed at zone X, and zone Y will be Ms.Fiches. Beeg Cheets have decided on sabotaging the poor, innocent bass in zone Y. They dumped a lethal chemical A into zone Y. Chemical A, when consumed by the fish, quickly decomposes to chemical B. B then decomposes to form a neurotoxin, C. This neurotoxin will paralyze the fins of the bass, rendering them motionless and not able to be caught by Ms.Fiche if she attempted to fish them out. However, Beeg Cheets skipped their Kinetics classes, and they did not realize that at the fishing conditions in zone Y, B decomposes faster to D, which is transformed by the basses bodies into chemical R. Chemical R causes the bass to be physically attracted to all metal hooks and fishing rods in general. The reactions can be written as follows: A -> B B -> C B -> D -> R a.) Write one out of the two series reactions for the above reactions. Either one of these two answers is acceptable: A > B -> C or B -> D -> R b.) Write the parallel reaction(s) that occur(s) above. B -> C B -> D c.) What is the chemical species (e.g., A, B, C, D, or R) that participates in the mixed reaction set?