For any chemical reaction of ‘reactants going to products’, e.g., 𝑎𝐴 + 𝑏𝐵 → 𝑑𝐷 + 𝑒𝐸, we can define the rate law: 𝑟𝑎𝑡𝑒 = 𝑘[𝐴]𝑥 [𝐵]𝑦 …where the exponents ‘𝑥’ and ‘𝑦’ are NOT simply equal to the stoichiometric coefficients ‘𝑎’ and ‘𝑏’ in the balanced equation above. One of the many jobs of chemists is to measure chemical reaction kinetics and, from those data, derive the rate law, including the exponents ‘𝑥’ and ‘𝑦’ (which sum to the ‘total order of the reaction) and the reaction rate constant, ‘𝑘’. In the lecture portion of the course, you have been (or will be) shown how to determine the rate law for a reaction by comparing its initial rate for various initial reactant concentrations. For example, consider the reaction 𝐴 + 3𝐵 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 and the following data:
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑅𝑎𝑡𝑒 𝑇𝑟𝑖𝑎𝑙 # [𝐴]0 (𝑀) [𝐵]0 (𝑀) (𝑀 𝑠 −1 )
1 5.46 0.100 0.100
2 12.28 0.150 0.100
3 5.49 0.100 0.200
We can determine the orders of reaction for 𝐴 and 𝐵, as well as the total reaction order and rate constant using these data above. This is based on the fact that we know the dependence of reaction rate on concentration (even if we don’t yet know the exponents); therefore, we can compare the results of any of the two trials above. If, say, we compare Trials 1 and 2: 𝑥 𝑦 𝑥 [𝐵] 𝑦 𝑟𝑎𝑡𝑒1 𝑘[𝐴(1)]0 [𝐵(1)]0 𝑟𝑎𝑡𝑒 = 𝑘[𝐴] → = 𝑟𝑎𝑡𝑒2 𝑘[𝐴(2)]0 𝑥 [𝐵(2)]0 𝑦
Activity #1 – Page 1 Notice that the rate constants, ‘𝑘’, in the numerator and denominator should cancel and you will be left with ratios of reactant concentrations. We can simplify much further if one reactant’s initial concentration is the same for both trials. Note that, when comparing Trials 1 and 2, [𝐵]0 doesn’t change!
Here, we used a nice trick with logarithms to isolate and solve for ‘𝑥’, the reaction order with respect to reactant “𝐴”… This expression for ‘𝑥’ cannot be simplified any further. So, we plug in the data from Trials 1 and 2 in the table, 5.46 log � � 𝑥= 12.28 = 1.999 ≈ 2 0.100 log � � 0.150 …rate orders are typically integers or half-integers.
We do the same for reactant “𝐵”, comparing Trials 1 and 3:
…so the reaction is second order in 𝐴, zeroth order in 𝐵, has a total reaction order of 2 + 0 = 𝟐. Now we need only need to solve for the rate constant. Input the two exponents into the general rate law expression and we get the complete rate law expression for our system:
𝑟𝑎𝑡𝑒 = 𝑘[𝐴]2 [𝐵]0 = 𝑘[𝐴]2
We can choose any of the three trials to calculate ‘𝑘’. For example, using the initial rate data from Trial 1:
2 [𝐵]0 2 𝑟𝑎𝑡𝑒 5.46 𝑀 ∙ 𝑠 −1 𝑟𝑎𝑡𝑒 = 𝑘[𝐴] = 𝑘[𝐴] → ∴𝑘= = = 546 𝑀−1 ∙ 𝑠 −1 [𝐴]2 (0.100 𝑀)2 …notice the units of the final answer.
Activity #1 – Page 2 Part 1b: The Rate Law – Your Turn #1 Consider the substitution reaction, 𝐶𝐻3 𝐵𝑟 + 𝑂𝐻 − → 𝐶𝐻3 𝑂𝐻 + 𝐵𝑟 − . The rate law for this reaction is:
𝑟𝑎𝑡𝑒 = 𝑘[𝐶𝐻3 𝐵𝑟]𝑥 [𝑂𝐻 − ]𝑦
Based on the data given in the table below, determine the orders with respect to each reactant, the total reaction order, and the rate constant (with correct units). Show your work in the space below.
Activity #1 – Page 3 Part 1c: The Rate Law – Your Turn #2 Consider the reaction for nitric oxide with hydrogen gas, forming nitrogen gas and water. Write a balanced equation for this reaction:
Based on the data given in the table below, determine the orders with respect to each reactant, the total reaction order, and the rate constant (with correct units). Show your work in the space below.
Note: This is a more difficult question because there is no pair of trials where the hydrogen concentration is unchanged. Calculating ‘𝑦’ is easy, but ‘𝑥’ is not. How will you go about solving this?
Activity #1 – Page 4 Part 2: Determining Individual Reactant Order and Half-Life from Plotted Data Two points worth recalling from your lecture notes: 1) The time-dependent concentration of “𝐴” for the simple reaction “𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠” depends on the reaction order with respect to “𝐴”: • For zeroth order, [𝐴(𝑡)] = [𝐴(0)] − 𝑘𝑡 • For first order, ln[𝐴(𝑡)] = ln[𝐴(0)] − 𝑘𝑡 • For second order, 1 1 = + 𝑘𝑡 [𝐴(𝑡)] [𝐴(0)] 2) The half-life of a reactant is the time that it takes for one-half of its concentration to disappear. That is, at time 𝑡1/2 , the concentration of reactant is, by definition, one-half the initial concentration.
Consider a chemical reaction, where “𝐴” is one of the reactants. During the course of this chemical reaction, the concentration of 𝐴 was measured as a function of time, and the results were plotted: 1 1) Analyze these plotted data, complete the 0.9 table below. 0.8 0.7 2) Work with these [𝐴(𝑡)] data and MS Excel to [A] (M)
0.6 0.5 determine the reaction order with respect to the 0.4 concentration of “𝐴”. How are you going to 0.3 manipulate the above equations and re-plot 0.2 the tabulated numbers to determine the order? 0.1 0 3) Finally, calculate the rate constant ‘𝑘’ using 0 50 100 150 200 250 300 350 400 450 500 your Excel work and find a way to estimate Time (seconds) half-life of “𝐴” (both with proper units).
Fill out the table below and put your answers at the bottom Keep the Excel file open to show your instructor! 𝑡𝑖𝑚𝑒 (𝑠) [𝐴(𝑡)] (𝑀) 𝑡𝑖𝑚𝑒 (𝑠) [𝐴(𝑡)] (𝑀) 0 1.00 200 25 225 50 250 75 300 100 350 125 400 150 450 175 500
Activity #1 – Page 5 Part 3: Arrhenius Kinetics and Activation Energy Svante Arrhenius proposed an equation (later confirmed by J.H. van’t Hoff) that relates the temperature- dependent reaction rate constant for a reaction to the reaction’s activation energy, 𝐸𝑎 . The so-called Arrhenius equation is:
𝑘(𝑇) = 𝐴𝑒 −(𝐸𝑎 /𝑅𝑇 )
… where the ‘𝐴’ term in this expression is called the ‘pre-exponential factor’ or the ‘frequency factor’, ‘𝑅’ is the molar gas constant (8.314 𝐽 ∙ 𝑚𝑜𝑙−1 ∙ 𝐾 −1 ), and ‘𝑇’ is the reaction temperature (in units of Kelvin, NOT degrees Celsius). Taking the natural logarithm of both sides of the Arrhenius equation gives us: 𝐸𝑎 ln 𝑘(𝑇) = ln 𝐴 − 𝑅𝑇 This is a useful form of the Arrhenius equation, as it doesn’t require a computer to easily fit temperature- dependent rate constant data to extract an activation energy. Discuss with your group members how this new expression has the same format as a straight line. Recall that a straight line obeys the equation ‘𝑦 = 𝑚𝑥 + 𝑏’. Importantly here, if you plotted “ln 𝑘(𝑇)” versus “1/𝑇”, what would the slope be equal to? How about the intercept? (give expressions not numbers):
Using MS Excel, massage and plot these data in such a way that you get a linear plot (Keep the Excel file open to show your instructor!). Using the slope and intercept from this straight-line plot, calculate the activation energy and frequency factor for the reaction (both with correct units), and record these values below.
