HG Esa 2NO(g) + Br{g) > 2NOBr(e) 3. A rate study of the reaction represented above was conducted at 25°C. The data that were obtained are shown in the table below. Initial Rate of Initial [NO] | Initial [Bro] | Appearance of Experiment | (mol L~!) (mol L“} NOBr (mol L*! 1) 1 0.0160 0.0120 3.24 x 10-4 2 0.0160 0.0240 6.38 x 10-4 3 0.0320 0.0060 6.42 x 10-4 (a) Calculate the initial rate of disappearance of Bra(g) in experiment 1 (b) Determine the order of the reaction with respect to each reactant, Bro(g) and NO(g). In each case, explain your reasoning. (©) For the reaction, (i) write the rate law that is consistent with the data, and (ii) calculate the value of the specific rate constant, k, and specify units. (@) The following mechanism was proposed for the reaction: Br(g) + NO(g) + NOBr,(g) slow NOBr,(g) + NO(g) > 2 NOBK(g) fast Is this mechanism consistent with the given experimental observations? Justify your answer. GOON TO THE NEXT PAGEa Commentary on Free-Response Question 3 Almost three-quarters of the students chose this ques- tion, which was a traditional kinetics question in which data were provided on the rate ofa specific chemical reaction under various conditions. Seudents then had to draw conclusions about the kinetics and the mechanism of the reaction. This question has the highest mean, score of the three problems (Questions 1, 2, and 3). Apparently, many students were more familiar with certain standard kinetics problems and as a result scored better on parts (b) and (6) than on parts (a) and (d). Surprisingly few carried ous the straightforward calcula- tion in part (a) In part (b) most students readily found the order of Br,(g) by divectly compating experiments 1 and 2, However, many found it difficule to determine the order of NO(®), either making computational errors or simply ignoring thac (Br, changed for each experiment. Scudents tried to hold (Br) constant by doubling entire lines of data in che table to determine the rare order. In many instances, students already knew the rate law for this reaction, bur made errors in trying to justify the order of [NO] a5 2. Provided that the rare law stated in past (c) was not inconsistent with earlier work, students were given full credit for calculation of units in part (c) and arguments in part (@) correctly based on the sate law they stated. In ‘part (¢) many scudents los eredit by incorrectly com- puting the units for the rate constant. A number of students wrote equilibrium constant expressions instead ‘of rate laws, In part (4) students assumed that ifthe same chemicals (NO, Br,) appeared in the reaction ot rate law from part (¢), consistency occurred. Many students did not present the rate law from the mecha- nism as an argument for inconsistency (eg, [NO in ‘experimental data, but {NO} in slow step).. In general, many scudents had difficulty correctly relating stoichiometry to kinetics. As examples, many failed to recognize relationships of coefficients to ‘comparative rates change of concentration of species, ‘many treated che overall reaction as iF were a single step in the mechanism and assigned onders accordingly, and a significant number cortectly added the reactions to determine that reactants in the overall equation were in the rate law, but failed to check the slow step for the correct order of each reactant.44 ‘Scoring Guidelines for Free-Response Question 3 Question 3 (@ points) (2) Rate of Brig) loss occurs at V4 the rate of NOBr(g) formation Rate of Bry(g) loss = 224X107 M = 4 69 10-4 Msec! (or mol Lt sec“) Ipt 2sec Note: No penalty for missing units; ignore + or ~ signs (b) Comparing experiments 1 and 2, [NO] remains constant, [Br,] doubles, and rate doubles; Ipt therefore, rate e [Br,]! => reaction is first-order with respect to [Br]. 63810 642x10~ 1 = HNO} Dy) _ MO.o160}*(0.0240) (1) 2, MNOP[Br,] — (0.0320)"[0.0060] (2 4 2 Note: One point eared for a proper set-up, comparing experiments 2 and 3 (as is shown here) or experiments 1 and 3. Second point eamed for solving the ratios correctly and determining that the exponent = 2. Also, credit can be eamed for a non-niathematical approach (e.g., one point for describing the change in [Bra] and subsequent effect on rate, another point for describing the change in [NO] and subsequent effect on rate). 1ny ( ) =) x22. => resction i second-order with respect to [NO} 2pts © @ Rate = KNO}P{Br,) Ipt ‘Note: Point eamed for an expression that is not inconsistent with the answer in part (b) z Gi) ex RHE, 324x104 Mee 195 14-2 geet (or 0ST? mol *sec") pts [NO}*[Br,] (0.0160)*(0.0120) M> (Using rate of Bry(g) loss = 1.62 x 10-4 Msec™* =» k= 52.7 M~* sec“! is also comrect.) ‘Note: One point for solving for the value of the rate constant consistent with the rate-law expression found in part (b) or stated in part (c); one point for the correct units consistent with the rate-law expression found in part (b) or stated in part (). (@ No, itis not consistent with the given experimental observations. Ipt ‘This mechanism gives a reaction that is first-order in [NO], and first-order in (Br), as those are the two reactants in the rate-determining step. Kinetic data show the reaction Ipt is second-order in [NO] (and first-order in [Br,)), 50 this cannot be the mechanism. ‘Note: One point earned for “No” [or for “Yes” if rate = KINO}[Brq) in part (b)]. (One point earned for justifying why this mechanism is inconsistent with the observed rate-law for consistent with rate law stated earlier m response] ‘One point deduction for mathematical eror (maximum once per question) One point deduction for error in significant figures* (maximum once per question) “number of significant figures must be correct within +/—one digit 63 |1444 as Excellent Response (9 points)Vad ee) Good Response (7 points) A. Gore 2086 — O14 2" -0,250 re ay roto” ov tog toy axea4 Q3 Fair Response (5 points) + OgAO 48.5 lor 2% 27 1a Ta yh TOPE yet