T Use the table below to determine the rate law for the reaction CO(g) + Cl2(g) → COCl2(g). B [CO] (M) 0.25 [C12] (M) 0.40 initial rate (M/s) 0.696 0.25 0.80 1.97 0.50 0.80 3.94 rate = [CO]²[CI]² rate =[CO]C12] rate = [CO][CI]³/ D rate = [CO][CI]2.8
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- 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?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?
- Candle wax is a mixture of hydrocarbons. In the reaction of oxygen with candle w ax in Figure 11.2, the rate of consumption of oxygen decreased with time after the flask was covered, and eventually' the flame went out. From the perspective of the kinetic-molecular theory, describe what is happening in the flask. FIGURE 11.2 When a candle burns in a closed container, the flame will diminish and eventually go out. As the amount of oxygen present decreases, the rate of combustion will also decrease. Eventually, the rate of combustion is no longer sufficient to sustain the flame even though there is still some oxygen present in the vessel.The decomposition of nitrosyl chloride was studied: 2NOCl(g) 2NO(g) + Cl2(g) The following data were obtained where Rate=[NOCl]t [NOCl]0(molecules/cm3) Initial Rate (molecules/cm3 s) 3.0 1016 5.98 104 2.0 1016 2.66 104 1.0 1016 6.64 103 4.0 1016 1.06 105 a. What is the rate law? b. Calculate the value of the rate constant. c. Calculate the value of the rate constant when concentrations are given in moles per liter.Consider the zero-, first-, and second-order integrated rate laws. If you have concentration versus time data for some species in a reaction, what plots would you make to prove a reaction is either zero, first, or second order? How would the rate constant, k, be determined from such a plot? What does the y-intercept equal in each plot? When a rate law contains the concentration of two or more species, how can plots be used to determine k and the orders of the species in the rate law?
- A study of the rate of dimerization of C4H6 gave the data shown in the table: 2C4H6C8H12 (a) Determine the average rate of dimerization between 0 s and 1600 s, and between 1600 s and 3200 s. (b) Estimate the instantaneous rate of dimerization at 3200 s from a graph of time versus [C4H6]. What are the units of this rate? (c) Determine the average rate of formation of C8H12 at 1600 s and the instantaneous rate of formation at 3200 s from the rates found in parts (a) and (b).Chlorine dioxide, ClO2, is a reddish-yellow gas that is soluble in water. In basic solution it gives ClO3 and ClO2 ions. 2ClO2(aq)+2OH(aq)ClO3(aq)+ClO2(aq)+H2O 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. Obtain the rate law and the value of the rate constant.Nitryl fluoride is an explosive compound that can be made by oxidizing nitrogen dioxide with fluorine: 2 NO2(g) + F2(g) → 2 NO2F(g) Several kinetics experiments, all done at the same temperature and involving formation of nitryl fluoride, are summarized in this table: Write the rate law for the reaction. Determine what the order of the reaction is with respect to each reactant and each product. Calculate the rate constant k and express it in appropriate units.
- For the reaction A+BC, explain at least two ways in which the rate law could be zero order in chemical A.One possible mechanism for the decomposition of nitryl chloride, NO2CI, is What is the overall reaction? What rate law would be derived from this mechanism? What effect does increasing the concentration of the product NO2 have on the reaction rate?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?