A gas phase reaction between nitrogen dioxide and fluorine is proposed to occur by the following mechanism: step 1 slow: NO2 + F2 → NO2F + F step 2 fast: F+ NO2 → NO2F (1) What is the equation for the overall reaction? Use the smallest integer coefficients possible. If a box is not needed, leave it blank. 2NO2 2NO,F + (2) Which species acts as a catalyst? Enter formula. If none, leave box blank: F (3) Which species acts as a reaction intermediate? Enter formula. If none, leave box blank: (4) Complete the rate law for the overall reaction that is consistent with this mechanism. (Use the form k[A]™[B]^... , where '1' is understood (so don't write it) for m, n etc.) k[NO,][F,] Rate =

A gas phase reaction between nitrogen dioxide and fluorine is proposed to occur by the following mechanism: step 1 slow: NO2 + F2 → NO2F + F step 2 fast: F+ NO2 → NO2F (1) What is the equation for the overall reaction? Use the smallest integer coefficients possible. If a box is not needed, leave it blank. 2NO2 2NO,F + (2) Which species acts as a catalyst? Enter formula. If none, leave box blank: F (3) Which species acts as a reaction intermediate? Enter formula. If none, leave box blank: (4) Complete the rate law for the overall reaction that is consistent with this mechanism. (Use the form k[A]™[B]^... , where '1' is understood (so don't write it) for m, n etc.) k[NO,][F,] Rate =

Chemistry for Engineering Students

4th Edition

ISBN:9781337398909

Author:Lawrence S. Brown, Tom Holme

Publisher:Lawrence S. Brown, Tom Holme

Chapter11: Chemical Kinetics

Section: Chapter Questions

Problem 11.30PAE: The rate of the decomposition of hydrogen peroxide, H2O2, depends on the concentration of iodide ion...

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The Raschig reaction produces the industrially important reducing agent hydrazine, N2H4, from ammonia, NH3, and hypochlorite ion, OCl−, in basic aqueous solution. A proposed mechanism is Step 1: Step 2: Step 3: What is the overall stoichiometric equation? Which step is rate-limiting? What reaction intermediates are involved? What rate law is predicted by this mechanism?
The rate of the decomposition of hydrogen peroxide, H2O2, depends on the concentration of iodide ion present. The rate of decomposition was measured at constant temperature and pressure for various concentrations of H2O2and of KI. The data appear below. Determine the order of reaction for each substance, write the rate law, and evaluate the rate constant. Rate [H2OJ [Kll (mL min-’) (mol L ’) (mol L ’) 0.090 0.15 0.033 0.178 0.30 0.033 0.184 0.15 0.066
11.64 HBr is oxidized in the following reaction: 4 HBr(g) + O2(g) —• 2 H2O(g) + 2 Br,(g) A proposed mechanism is HBr + O2 -* HOOBr (slow) HOOBr + HBr — 2 HOBr (fast) HOBr + HBr — H2O + Bn (fast) Show that this mechanism can account for the correct stoichiometry. Identify all intermediates in this mechanism. What is the molecularity of each elementary’ step? Write the rate expression for each elementary' step. Identify the rate-determining step.
11.51 Peroxyacetyl nitrate (PAN) has the chemical formula CtHjNOj and is an important lung irritant in photochemical smog. An experiment to determine the decomposition kinetics of PAN gave the data below. Determine the order of reaction and calculate the rate constant for the decomposition of PAN. Time, t (min) Partial Pressure of PAN (torr) 0.0 2.00 X 10~’ 10.0 1.61 X 10~} 20.0 1.30 X 10_J 30.0 1.04 X 10"’ 40.0 8.41 X 10-4 50.0 6.77 x 10-4 60.0 5.45 X 10-4
11.41 For a drug to be effective in treating an illness, its levels in the bloodstream must be maintained for a period of time. One way to measure the level of a drug in the body is to measure its rate of appearance in the urine. The rate of excretion of penicillin is first order, with a half-life of about 30 min. If a person receives an injection of 25 mg of penicillin at t = 0, how much penicillin remains in the body after 3 hours?
The frequency factor A is 6.31 108 L mol1 s1 and the activation energy is 10. kJ/mol for the gas-phase reaction NO(g)+O3(g)NO2(g)+O2(g) which is important in the chemistry of stratospheric ozone depletion. (a) Calculate the rate constant for this reaction at 370. K. (b) Assuming that this is an elementary reaction, calculate the rate of the reaction at 370. K if [NO] = 0.0010 M and [O3] = 0.00050 M.
The label on a bottle of 3% (by volume) hydrogen peroxide, H2O2, purchased at a grocery store, states that the solution should be stored in a cool, dark place. H2O2decomposes slowly over time, and the rate of decomposition increases with an increase in temperature and in the presence of light. However, the rate of decomposition increases dramatically if a small amount of powdered MnO- is added to the solution. The decomposition products are H2O and O2. MnO2 is not consumed in the reaction. Write the equation for the decomposition of H2O2. What role does MnO2 play? In the chemistry lab, a student substituted a chunk of MnO2 for the powdered compound. The reaction rate was not appreciably increased. WTiat is one possible explanation for this observation? Is MnO2 part of the stoichiometry of the decomposition of H2O2?
The initial rate ( [NO]/ t] of the reaction of nitrogen monoxide and oxygen NO(g) + 2O2(g) NO2(g) was measured for various initial concentrations of NO and O2 at 25 C. Determine the rate equation from these data. What is the value of the rate constant, k, and what are its units?
Chlorine dioxide oxidizes iodide ion in aqueous solution to iodine; chlorine dioxide is reduced to chlorite ion. 2ClO2(aq)+2I(aq)2ClO2(aq)+I2(aq) The order of the reaction with respect to ClO2 was determined by starting with a large excess of I, so that its concentration was essentially constant. Then Rate=k[ClO2]m[I]n=k[ClO2]m where k= k[I]n. Determine the order with respect to ClO2 and the rate constant k by plotting the following data assuming first- and then second-order kinetics. [Data from H. Fukutomi and G. Gordon, J. Am. Chem. Soc., 89, 1362 (1967).] Time (s) [ClO2] (mol/L) 0.00 4.77 104 1.00 4.31 104 2.00 3.91 104 3.00 3.53 104 5.00 2.89 104 10.00 1.76 104 30.00 2.4 105 50.00 3.2 106
Hundreds of different reactions occur in the stratosphere, among them reactions that destroy the Earths ozone layer. The table below lists several (second-order) reactions of Cl atoms with ozone and organic compounds; each is given with its rate constant. For equal concentrations of Cl and the other reactant, which is the slowest reaction? Which is the fastest reaction?
Can a reaction mechanism ever be proven correct? Can it be proven incorrect?