Question

You are part of a team working on the development of a process in which a mineral species (labeled A for proprietary reasons) undergoes a reaction to form a new pigment to be used in house paints. In a series of experiments in a large well-mixed stirred tank reactor, you fill a tank with a known quantity of an inert liquid, bring the liquid up to a specified temperature, add a known quantity of A, and measure the concentration of A in the tank as a function of time. The reaction gives off heat as it progresses, but cooling water circulating in a jacket around the reactor keeps the temperature of the reacting mixture constant. The following data are recorded.

	Concentration of A, CA(mol A/L)
t(min)	T = 94°C	T = 110°C	T = 127°C	T = 142°C
10	9.30×10−2	5.19×10−2	2.10×10−2	9.87×10−3
20	6.17×10−2	2.35×10−2	1.33×10−2	5.55×10−3
30	4.41×10−2	1.91×10−2	8.15×10−3	3.97×10−3
40	3.12×10−2	1.45×10−2	5.92×10−3	2.45×10−3
50	2.58×10−2	1.01×10−2	4.48×10−3	2.27×10−3
60	9.30×10−2	9.50×10−3	4.36×10−3	1.83×10−3

A research article indicates that concentration of A should vary with time according to the following expression:

CA(t)=11CA0+kt

(1)

where CA0 (mol/L) is the initial concentration of A in the reactor [CA(t=0)] and k is called the reaction rate constant. Despite being called a constant, k is a strong function of the absolute temperature in the reactor:

k(T)=k0 exp−EaRT(K)

(2)

In this equation (known as the Arrhenius equation after the Swedish chemist who proposed it), k0 is a constant, Ea(J/mol) is the reaction activation energy, and R=8.314 J/(mol·K) is the universal gas constant. Your task will be to verify that the expressions for CA(t) and k(T) fit the data, and if they do, to determine the parameters CA0 and k at each temperature and then the constants k0 and Ea.

(a)

What are the units of k, k0, and Ea if CA is in mol/L and t is in min?

(b)

Transform Equation 1 into an equation of the form y=at+b, so that if Equation 1 is valid, a plot of yvs. t would be a straight line. How would you determine CA0 and k from the slope and intercept of the line?

(c)

Create an Excel spreadsheet with the structure shown as Rows 1-10 in the figure at the end of this problem statement, and fill in the data table in Columns A-I. Then create the four scatterplots shown in Rows 15-21. In the “Trendline” options of each plot, check the boxes for “Display equation on chart” and “Display R-squared value on chart” but not the one for “Set intercept.” R2 is the coefficient of determination (it has several other names as well), and provides a measure of how well a straight line fits a set of data: the closer it is to 1, the better the fit. What can you conclude about Equation 1 from the four plots?

(d)

From the four trendline equations, calculate the values of k and CA0 for each of the four experimental temperatures and fill in Columns B-I in Rows 12 and 13 of the spreadsheet.

(e)

Enough A was initially added to the tank to make the initial concentration CA0=0.25 mol/L, yet you calculated four different values of CA0 in Part d. How do you explain this result?