 # Part I: Unidirectional Kinetics 1. NOx and SOx. Two important cont...

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Part I: Unidirectional Kinetics 1. NOx and SOx. Two important contributors to air pollution are nitrogen oxides and sulfur oxides, toxic gases with significant impacts on human health in large urban areas around the world In the presence of water, these gases also serve as common precursors to highly caustic acids that constitute acid rain. One such reaction that contributes significantly to the formation of sulfuric acid rain follows the reaction of NO2 and SO2 in the presence of wateri NO2 (aq) + SO2 (aq) - products 1.2 1.0 The optical transmittance of an aqucous solution of excess SO2 was measured at a os wavelength of 400 nm corresponding to 0.1. NO2) asa function of time during the fast injection of a small, fixed amount of NO2 0.4 as shown in the figure at right. 02 *data attached Optical absorbance, A, and transmittance. 0.0 0.00 0.05 0.10 0.15 0.20 0.25 T, are related exponentially, as lime (ms) 1 A = = The Beer-Lambert Law relates the optical absorbance, Ai, of some speciesi to its concentration, as where U is the molar absorptivity of species i and I is the path length of the spectrometer. a Determine the order of this "isolated" reaction in terms of NO2. b. What is the order of the overall reaction, given that it is first order in SO2? C. Determine the rate constant of the overall reaction, knowing that ENO2 is 17.5 L mol-1 cm³¹, I was 2.00 cm for the spectrometer, and [SO2(aq) was fixed at 0.250 M during the measurements shown above. d. Determine the half-life of the NO2-limited "isolated" reaction by inspection and compare this value to its theoretical value. Explain the result. 2. Kinetic Rate Orders. Determine the order and theoretical (fitted) half-life of the following reactions using the data provided, assuming that all reactions follow the simple formi A products a Gaudreau Precipitation b. Lafleur Reduction C Selänne Combustion d. Conn Smythe Reaction Part II: Equilibrium Kinetics 3. Simple Reversible Reaction Consider the following simple reversible reaction A(g) - B(g) The individual (irreversible) rate laws for the forward and reverse reactions are Tforward (t)= ky[A] (1*t order) Treverse (t) (1storder) a Write the overall, reversible reation rate law (Treversible (t)) in terms of [A] and [B]. b. If the initial mixture (at t =0) is comprised of both A and B in the initial concentrations [A]° and [B]o, express the reaction rate as the derivative of [A] with respect to tin terms of [A], t, and necessary constants only (i.e, not [B]). C. Solve the differential equation derived in part b by separating variables (t and [A]) and integrating from the initial state (at t = 0) to marbitrary final state- Simplify and compare your result to Equation 28.40 in the text. Hints follow the general procedure described in Problem 28.32 in the text, although note that this problem is slightly different since [B]o= Oin this case. Simplify until an expression is reached where some function of [A] is linear with respect to t. d. Write the moregeneral expression for "Equation 1" in Problem 28.32 in the text (where [B]0 is a non-zero constant in this case). c. Determine k, and kr in units of Hz given that the equilibrium constantat this temperature is Ka = 5.23, and using the provided reaction rate data-

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