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In the reaction A → B + C the concentration of A decreases exponentially with time. Why can't the rate equation be d[A]/dt = k[B][C]?
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- One experimental procedure that can be used to determine the rate law of a reaction is the method of initial rates. What data are gathered in the method of initial rates, and how are these data manipulated to determine k and the orders of the species in the rate law? Are the units for k. the rate constant, the same for all rate laws? Explain. If a reaction is first order in A, what happens to the rate if [A] is tripled? If the initial rate for a reaction increases by a factor of 16 when [A] is quadrupled, what is the order of n? If a reaction is third order in A and [A] is doubled, what happens to the initial rate? If a reaction is zero order, what effect does [A] have on the initial rate of a reaction?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?Isomerization of CH3NC occurs slowly when CH3NC is heated. CH3NC(g) CH3CN(g) To study the rate of this reaction at 488 K, data on [CH3NC] were collected at various times. Analysis led to the following graph. (a) What is the rate law for this reaction? (b) What is the equation for the straight line in this graph? (c) Calculate the rate constant for this reaction. (d) How long does it take for half of the sample to isomerize? (e) What is the concentration of CH3NC after 1.0 104 s?
- At 573 K, gaseous NO2(g) decomposes, forming NO(g) and O2(g). If a vessel containing NO2(g) has an initial concentration of 1.9 102 mol/L, how long will it take for 75% of the NO2(g) to decompose? The decomposition of NO2(g) is second-order in the reactant and the rate constant for this reaction, at 573 K, is 1.1 L/mol s.At 500 K in the presence of a copper surface, ethanol decomposes according to the equation C2H5OH(g)CH3CHO(g)+H2(g) The pressure of C2H5OH was measured as a function of time and the following data were obtained: Time(s) PC2H5OH(torr) 0 250. 100. 237 200. 224 300. 211 400. 198 500. 185 Since the pressure of a gas is directly proportional to the concentration of gas, we can express the rate law for a gaseous reaction in terms of partial pressures. Using the above data, deduce the rate law, the integrated rate law, and the value of the rate constant, all in terms of pressure units in atm and time in seconds. Predict the pressure of C2H5OH after 900. s from the start of the reaction. (Hint: To determine the order of the reaction with respect to C2H5OH, compare how the pressure of C2H5OH decreases with each time listing.)Hydrogen peroxide, H2O2(aq), decomposes to H2O() and O2(g) in a reaction that is first-order in H2O2 and has a rate constant k = 1.06 103 min1 at a given temperature. (a) How long will it take for 15% of a sample of H2O2 to decompose? (b) How long will it take for 85% of the sample to decompose?
- You are studying the kinetics of the reaction H2(g) + F2(g) 2HF(g) and you wish to determine a mechanism for the reaction. You run the reaction twice by keeping one reactant at a much higher pressure than the other reactant (this lower-pressure reactant begins at 1.000 atm). Unfortunately, you neglect to record which reactant was at the higher pressure, and you forget which it was later. Your data for the first experiment are: Pressure of HF (atm) Time(min) 0 0 0.300 30.0 0.600 65.8 0.900 110.4 1.200 169.1 1.500 255.9 When you ran the second experiment (in which the higher pressure reactant was run at a much higher pressure), you determine the values of the apparent rate constants to be the same. It also turns out that you find data taken from another person in the lab. This individual found that the reaction proceeds 40.0 times faster at 55C than at 35C. You also know, from the energy-level diagram, that there are three steps to the mechanism, and the first step has the highest activation energy. You look up the bond energies of the species involved and they are (in kJ/mol): H8H (432), F8F (154), and H8F (565). a. Sketch an energy-level diagram (qualitative) that is consistent with the one described previously. Hint: See Exercise 106. b. Develop a reasonable mechanism for the reaction. c. Which reactant was limiting in the experiments?In Exercise 11.39, if the initial concentration of N2Oj is 0.100 .\1. how long will it take for the concentration to drop to 0.0100 times its original value? The decomposition of N2O5 in solution in carbon tetrachloride is a first-order reaction: 2N2O5—»4NO2 + O2 The rate constant at a given temperature is found to be 5.25 X 10-4 s-’. If the initial concentration of N2O5 is 0.200 M, what is its concentration after exactly 10 minutes have passed?
