The rate of a first-order reaction is followed by spectroscopy, monitoring the absorbance of a colored reactant at 520 nm. The reaction occurs in a 1.00-cm sample cell, and the only colored species in the reaction has an extinction coefficient of 5.60 * 103 M-1 cm-1 at 520 nm. (c) Calculate the half-life of the reaction.
Ch.14 - Chemical Kinetics
Chapter 14, Problem 103
Cyclopentadiene (C5H6) reacts with itself to form dicyclopentadiene (C10H12). A 0.0400 M solution of C5H6 was monitored as a function of time as the reaction 2 C5H6 → C10H12 proceeded. The following data were collected: Time (s) | [C5H6] (M) 0.0 | 0.0400 50.0 | 0.0300 100.0 | 0.0240 150.0 | 0.0200 200.0 | 0.0174 Plot [C5H6] versus time, ln[C5H6] versus time, and 1/[C5H6] versus time. (b) What is the value of the rate constant?

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Step 1: Begin by plotting the concentration of cyclopentadiene, [C5H6], against time. This will help determine the order of the reaction by visual inspection. If the plot is linear, it indicates a zero-order reaction.
Step 2: Next, plot the natural logarithm of the concentration, ln[C5H6], versus time. A linear plot here would suggest a first-order reaction, where the rate of reaction is directly proportional to the concentration of C5H6.
Step 3: Then, plot the inverse of the concentration, 1/[C5H6], against time. A linear relationship in this plot would indicate a second-order reaction, where the rate is proportional to the square of the concentration of C5H6.
Step 4: Determine which of the three plots is linear. The linearity of the plot will indicate the order of the reaction: zero-order, first-order, or second-order.
Step 5: Once the order of the reaction is determined, use the slope of the linear plot to calculate the rate constant, k. For a first-order reaction, the slope of the ln[C5H6] vs. time plot is -k. For a second-order reaction, the slope of the 1/[C5H6] vs. time plot is k.
Related Practice
Textbook Question
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Textbook Question
The rate of a first-order reaction is followed by spectroscopy, monitoring the absorbance of a colored reactant at 520 nm. The reaction occurs in a 1.00-cm sample cell, and the only colored species in the reaction has an extinction coefficient of 5.60 * 103 M-1 cm-1 at 520 nm. (d) How long does it take for the absorbance to fall to 0.100?
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Open Question
A colored dye compound decomposes to give a colorless product. The original dye absorbs at 608 nm and has an extinction coefficient of 4.7 * 10^4 M^-1 cm^-1 at that wavelength. You perform the decomposition reaction in a 1-cm cuvette in a spectrometer and obtain the following data: Time (min) Absorbance at 608 nm 0 1.254 30 0.941 60 0.752 90 0.672 120 0.545. From these data, determine the rate law for the reaction 'dye → product' and determine the rate constant.
Open Question
The first-order rate constant for the reaction of a particular organic compound with water varies with temperature as follows: Temperature (K) Rate Constant (s⁻¹) 300 3.2 × 10⁻¹¹, 320 1.0 × 10⁻⁹, 340 3.0 × 10⁻⁸, 355 2.4 × 10⁻⁷. From these data, calculate the activation energy in units of kJ/mol.
Textbook Question
At 28 C, raw milk sours in 4.0 h but takes 48 h to sour in a refrigerator at 5 C. Estimate the activation energy in kJ>mol for the reaction that leads to the souring of milk.
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Open Question
The following is a quote from an article in the August 18, 1998, issue of The New York Times about the breakdown of cellulose and starch: “A drop of 18 degrees Fahrenheit [from 77 _x001E_F to 59 _x001E_F] lowers the reaction rate six times; a 36-degree drop [from 77 _x001E_F to 41 _x001E_F] produces a fortyfold decrease in the rate.” (b) Assuming the value of Ea calculated from the 36 _x001E_ drop and that the rate of breakdown is first order with a half-life at 25 _x001E_C of 2.7 yr, calculate the half-life for breakdown at a temperature of -15 _x001E_C.