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The tabulated data show the rate constant of a reaction mea- sured at several different temperatures. Use an Arrhenius plot to determine the activation barrier and frequency factor for the reaction. $$ \begin{array}{cl} \text { Temperature (K) } & \text { Rate Constant (1/s) } \\ \hline 310 & 0.00434 \\ \hline 320 & 0.0140 \\ \hline 330 & 0.0421 \\ \hline 340 & 0.118 \\ \hline 350 & 0.316 \\ \hline \end{array} $$

Short Answer

Expert verified
Calculate the activation barrier (Ea) from the negative slope (m) of the best-fit line on the Arrhenius plot by using the relation Ea = -mR. Calculate the frequency factor (A) by taking the exponential of the y-intercept (c), A = e^c.

Step by step solution

01

Understand the Arrhenius Equation

The Arrhenius equation relates the rate constant (k) to the temperature (T), activation energy (Ea), and frequency factor (A). It can be written as: \[ k = A e^{\frac{-E_a}{RT}} \]where R is the gas constant, and T is the temperature in Kelvin. Taking the natural logarithm of both sides gives us a linear equation:\[ \ln k = \ln A - \frac{E_a}{R} \left(\frac{1}{T}\right). \]
02

Prepare the Data for Plotting

To make an Arrhenius plot, we plot \(\ln k\) on the y-axis against \(\frac{1}{T}\) on the x-axis. Prepare the tabulated data by calculating \(\ln k\) and \(\frac{1}{T}\) for each given temperature and rate constant pair.
03

Plot the Data on an Arrhenius Plot

Using the prepared data, plot the points \(\left(\frac{1}{T_i}, \ln k_i\right)\) on a graph. The slope of the resulting line will be \(-\frac{E_a}{R}\), and the y-intercept will be \(\ln A\).
04

Perform Linear Regression

Use linear regression on the points to find the best-fit line. The equation of the best-fit line will be in the form\[ y = mx + c \]where \(m\) corresponds to \(-\frac{E_a}{R}\) and \(c\) to \(\ln A\).
05

Calculate the Activation Barrier and Frequency Factor

Determine the activation barrier, \(E_a\), by taking the negative slope of the best-fit line multiplied by the gas constant, R. The frequency factor, A, is found by taking the exponential of the y-intercept:\[ E_a = -mR \] and \[ A = e^c. \]

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Activation Energy
Activation energy, often denoted as Ea, is a critical concept in chemical kinetics. It represents the minimum amount of energy required for reactants to transform into products during a chemical reaction. Imagine a hill: Reactants must climb over an energy barrier—the top of the hill—before they can roll down and transform into products. This 'climbing' requires energy, which is the activation energy. A higher Ea means that fewer molecules have enough energy to react at a given temperature, often resulting in a slower reaction rate. Understanding the activation energy helps chemists control reaction speeds and design catalysts that lower the Ea to make processes more efficient.

In the context of an Arrhenius plot, which is a graph of ln(k) against 1/T, the activation energy can be derived from the slope of the line. A steeper negative slope indicates a higher activation energy, as more energy is required to increase the rate constant, k.
Rate Constant
The rate constant is the proportionality factor in the rate equation of a chemical reaction and is denoted by k. It is a measure of how quickly a reaction occurs. The larger the value of k, the faster the reaction proceeds. The rate constant is influenced by several factors including temperature, which is elegantly shown in the Arrhenius equation. It is also affected by the presence of a catalyst, reactant concentrations, and the physical state of the reactants. In exercises like the one we’re discussing, you'll notice that as the temperature increases, so does the rate constant, illustrating the integral relationship between these two variables.
Arrhenius Equation
The Arrhenius equation provides a quantitative basis for the relationship between the rate constant and temperature. It is written as \( k = A e^{-\frac{E_a}{RT}} \) where R is the gas constant and T is the temperature in Kelvin. The equation comprises two main components: the pre-exponential factor A, also known as the frequency factor, and the exponential term, which includes the activation energy. By taking the natural logarithm of the Arrhenius equation, it is transformed into a linear form, which facilitates the use of linear regression to determine the values of A and Ea from experimental data.
Frequency Factor
In the Arrhenius equation, the frequency factor or pre-exponential factor, A, relates to the frequency of collisions and the proper orientation of reactant molecules. A higher value of A implies that more collisions are successful in producing a reaction. It is important to note that not all collisions lead to a reaction; they must have the correct orientation and enough energy to overcome the activation energy barrier. In practice, determining A directly from experimental data can be challenging, but the Arrhenius plot simplifies this by relating the frequency factor to the y-intercept of the linearized version of the Arrhenius equation.
Linear Regression
Linear regression is a statistical tool to find the best-fit line through a set of data points, which in the context of chemical kinetics, often involves an Arrhenius plot. It involves calculating the equation of a line (\(y = mx + c\)) that minimizes the distance between the data points and the line itself. m represents the slope and c the y-intercept. Applied to our problem, linear regression helps to determine the line that best describes the relationship between ln(k) and 1/T, allowing us to extract the activation energy and frequency factor from the slope and intercept, respectively. It's a cornerstone method for interpreting kinetic data because it simplifies the process of quantifying reaction parameters from experimental observations.
Natural Logarithm
The natural logarithm, often abbreviated as ln, is a mathematical function that is the inverse of the exponential function with the base e, where e is an irrational and transcendental constant approximately equal to 2.71828. In kinetics, taking the natural logarithm of both sides of the Arrhenius equation linearizes the relationship between the rate constant and temperature. This allows for easier interpretation of the data when plotting an Arrhenius graph. The linear form, ln(k) = ln(A) - Ea/R (1/T), suggests a straight line where the slope is related to the negative activation energy and the y-intercept gives the natural logarithm of the frequency factor, showing the deep connection between mathematical functions and chemical phenomena.

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Most popular questions from this chapter

The rate constant \((k)\) for a reaction was measured as a function of temperature. A plot of In \(k\) versus \(1 / T\) (in \(\mathrm{K}\) ) is linear and has a slope of -7445 K. Calculate the activation energy for the reaction.

Consider the tabulated data showing the initial rate of a reaction (A \(\longrightarrow\) products) at several different concentrations of A. What is the order of the reaction? Write a rate law for the reac- tion, including the value of the rate constant, \(k\). $$ \begin{array}{cc} {[\mathrm{A}](\mathrm{M})} & \text { Initial Rate }(\mathrm{M} / \mathrm{s}) \\\ 0.12 & 0.0078 \\ \hline 0.16 & 0.0104 \\ \hline 0.20 & 0.0130 \\ \hline \end{array} $$

Consider this overall reaction, which is experimentally observed to be second order in AB and zero order in C: $$ \mathrm{AB}+\mathrm{C} \longrightarrow \mathrm{A}+\mathrm{BC} $$ Is the following mechanism valid for this reaction? $$ \begin{array}{ll} \mathrm{AB}+\mathrm{AB} \longrightarrow \mathrm{AB}_{2}+\mathrm{A} & \text { Slow } \\ \mathrm{AB}_{2}+\mathrm{C} \longrightarrow \mathrm{AB}+\mathrm{BC} & \text { Fast } \end{array} $$

What units are typically used to express the rate of a reaction?

The reaction \(2 \mathrm{H}_{2} \mathrm{O}_{2}(a q) \longrightarrow 2 \mathrm{H}_{2} \mathrm{O}(l)+\mathrm{O}_{2}(g)\) is first order in \(\mathrm{H}_{2} \mathrm{O}_{2}\) and under certain conditions has a rate constant of \(0.00752 \mathrm{~s}^{-1}\) at \(20.0^{\circ} \mathrm{C}\). A reaction vessel initially contains \(150.0 \mathrm{~mL}\) of \(30.0 \% \mathrm{H}_{2} \mathrm{O}_{2}\) by mass solution (the density of the solution is \(1.11 \mathrm{~g} / \mathrm{mL}\) ). The gaseous oxygen is collected over water at \(20.0^{\circ} \mathrm{C}\) as it forms. What volume of \(\mathrm{O}_{2}\) forms in \(\begin{array}{lllll}85.0 & \text { seconds at a barometric pressure of } & 742.5 & \mathrm{mmHg} ?\end{array}\) (The vapor pressure of water at this temperature is \(17.5 \mathrm{mmHg}\).)

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