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Problem 12.8

At high temperatures, cyclopropane is converted into the material from which polypropylene plastics are made:

[tex]\[
\begin{array}{c}
CH_2 \\
H_2C - CH_2 \rightarrow CH_3- CH = CH_2 \\
\text {Cyclopropane}
\end{array}
\][/tex]

Given the following concentration data, test whether the reaction is first-order and calculate the value of the rate constant.

[tex]\[
\begin{array}{c|cccccc}
& \text{Time (min)} & 0 & 5.0 & 10.0 & 15.0 & 20.0 \\
\hline
\text{[Cyclopropane] (M)} & 0.098 & 0.080 & 0.066 & 0.054 & 0.044
\end{array}
\][/tex]


Sagot :

To determine the order of the reaction and calculate the rate constant, we start by analyzing the given concentration data for cyclopropane at different times.

Given data:
- Times (in minutes): [tex]\(0, 5.0, 10.0, 15.0, 20.0\)[/tex]
- Concentrations of cyclopropane (in mol/L): [tex]\(0.098, 0.080, 0.066, 0.054, 0.0\)[/tex]

We are given the following analysis results:

1. Times: [tex]\(0, 5.0, 10.0, 15.0, 20.0\)[/tex]
2. Concentrations: [tex]\(0.098, 0.080, 0.066, 0.054, 0.0\)[/tex]
3. Natural Logarithm of Concentrations: [tex]\(\ln (0.098), \ln(0.080), \ln(0.066), \ln(0.054)\)[/tex]
Corresponding values: [tex]\(-2.3228, -2.5257, -2.7181, -2.9188\)[/tex]
(Note: The last concentration is zero and thus its logarithm isn't calculated)

From the given results, we identify:
4. Slope of the regression line: [tex]\(-0.039606\)[/tex]
5. Intercept of the regression line: [tex]\(-2.3242987\)[/tex]
6. Rate constant [tex]\(k\)[/tex]: [tex]\(0.039606 \, \text{min}^{-1}\)[/tex]

### Solution Steps:

1. Checking the Reaction Order:
- We assume the reaction is first-order and thus plot [tex]\(\ln[\text{Cyclopropane}]\)[/tex] vs. time. If the plot is linear, it's a first-order reaction.
- The results show a linear relationship between [tex]\(\ln[\text{Cyclopropane}]\)[/tex] and time, confirming first-order reaction behavior.

2. Calculating the logarithms of the given concentrations:

[tex]\[ \begin{aligned} \ln(0.098) & \approx -2.3228, \\ \ln(0.080) & \approx -2.5257, \\ \ln(0.066) & \approx -2.7181, \\ \ln(0.054) & \approx -2.9188. \end{aligned} \][/tex]

3. Performing Linear Regression:
- Using the times [tex]\(0, 5.0, 10.0, 15.0\)[/tex] and the corresponding logarithms:
[tex]\[ \begin{aligned} t (min) & : 0, 5.0, 10.0, 15.0, \\ \ln[\text{Cyclopropane}] & : -2.3228, -2.5257, -2.7181, -2.9188. \end{aligned} \][/tex]

- The slope ([tex]\(m\)[/tex]) of the linear fit line can be determined:
[tex]\[ \text{slope} \approx -0.039606. \][/tex]

4. Calculating the Rate Constant [tex]\(k\)[/tex]:
- For a first-order reaction, the rate constant [tex]\(k\)[/tex] is the negative of the slope of the [tex]\(\ln[\text{Cyclopropane}]\)[/tex] vs. time plot.
[tex]\[ k = - (\text{slope}) = 0.039606 \, \text{min}^{-1}. \][/tex]

### Conclusion:
- The reaction is confirmed to be first-order.
- The rate constant [tex]\(k\)[/tex] for the decomposition of cyclopropane is [tex]\(0.039606 \, \text{min}^{-1}\)[/tex].