The formation of tert-butanol is described by the following chemical equation: (CH3)₂CBr (aq) + OH(aq) · → Br¯ (aq) + (CH3)₂COH (aq) Suppose a two-step mechanism is proposed for this reaction, beginning with this elementary reaction: (CH3)₂ CBr (aq) → (CH3)₂C+ (aq) + Br¯ (aq) Suppose also that the second step of the mechanism should be bimolecular. Suggest a reasonable second step. That is, write the balanced chemical equation of a bimolecular elementary reaction that would complete the proposed mechanism. 0 0-0 Un X 3 4

[4] Consider the following mechanism for the reaction of nitric oxide and hydrogen: kı 2NO(g)+ H2(g) → N;O(g) + H¿O(g) slow k2 N,0(g) + H2(g) → N2(g) + H2O(g) fast (a) Write an equation for the overall reaction. (b) Write the theoretical rate law for the above mechanism. (c) Is a catalyst involved in the above mechanism? If so, what is it? (d) Are there any reaction intermediates? If so, list them.

Consider the mechanism. 2 A = B В +С — D Step 1: equilibrium Step 2: slow Overall: 2A +С — D Determine the rate law for the overall reaction, where the overall rate constant is represented as k. rate =

Consider the following proposed reaction mechanism: (1) CIO (aq) + H,O(1)= HCIO(aq) + OH (aq) [fast] (2)I (aq) + HCIO(aq) → HIO(aq) + Cl¯(aq) [slow] (3) OH (aq) + HIO(aq) → H,O() + 10 (aq) [fast] Ignoring water, how many reaction intermediates are present? O 3 O 1 O 2

Chlorine dioxide, Cl02, is a reddish-yellow gas that is soluble in water. In basic solution it gives Cl03- and CIO2 ions. 2C1O:(aq) + 20н (ад) —> СIО3 (aд) + CIO, (aq) + H;0(1) To obtain the rate law for this reaction, the following experiments were run and, for each, the initial rate of reaction of ClO2 was determined. Initial Concentration Initial Concentration Initial Rate of Cl02 (mol/L) of OH (mol/L) (mol(L's) Exp. 1 0.21 1.6 x 10-2 0.162 Exp. 2 7.0 x 10-2 1.6 x 10-2 1.80 x 10-2 Exp. 3 7.0 x 10-2 4.8 x 10-2 5.39 х 10-2 a Obtain the rate law. (Use k for the rate constant.) Rate law =

Identify each of the following elementary reactions as unimolecular, bimolecular, or termolecular, and write the rate expression. Reaction Molecularity Rate expression (a) NO2 + NO2→2 NO + 02 rate = (b) BrONO- ЭBro + NOz rate = (c) 0+ 02 + M 03 + M rate = unimolecular bimolecular termolecular

For the first-order reaction N2O5( g) 2 NO2 g) + → t1/2= 20.5 h at 20°C and 3.5h at 40°C. (a) Calculate the activation energy of this reaction. (b) If the Arrhenius constant A = 2.5 x 105 s', determine the value of k at 50°C.

Suppose the formation of nitryl fluoride proceeds by the following mechanism: step elementary reaction 1 NO₂ (g) +F₂ (g) → NO₂F (g)+F (g) 2 F (g) + NO₂ (g) → NO₂F (g) Suppose also k₁ << k₂. That is, the first step is much slower than the second. Write the balanced chemical equation for the overall chemical reaction. Write the experimentally- observable rate law for the overall chemical reaction. Note: your answer should not contain the concentrations of any intermediates. 0 rate = & rate constant k₁ k₂

Suppose the reaction between nitric oxide and bromine proceeds by the following mechanism: step elementary reaction 1 NO (g) + Br₂ (g) → NOBr₂ (g) k₁ k₂ 2 NOBr₂ (g) + NO (g) → 2NOBr (g) Suppose also k₁ « k₂ . That is, the first step is much slower than the second. Write the balanced chemical equation for the overall chemical reaction. Write the experimentally- observable rate law for the overall chemical reaction. Note: your answer should not contain the concentrations of any intermediates. 0 rate = k rate constant 010 X Ś

Suppose the reaction between nitric oxide and oxygen proceeds by the following mechanism: step elementary reaction rate constant 1 NO(g) + O,(g) –→ NO2(g) + O(g) k1 NO(g) + O(g) → NO2(g) Suppose also k,«k,. That is, the first step is much slower than the second. Write the balanced chemical equation for the overall chemical reaction: Write the experimentally- observable rate law for the overall chemical reaction. rate = k || Note: your answer should not contain the concentrations of any intermediates. Express the rate constant k for the overall chemical reaction in terms of k1, k2, and (if necessary) the rate constants k.1 and k-2 for k = | %3D the reverse of the two elementary reactions in the mechanism.