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S. B. Piepho, 2002

How to Determine the Rate Law from Experimental Data There are two general methods to determine the rate law from experimental data. The first is the method of initial rates which is appropriate when the reaction is relatively slow so that the initial rate v0 may be determined as a function of initial concentrations. The second method, which makes use of integrated rate equations, is applicable when the reaction is sufficiently fast so that concentration versus time data may be collected over several half-lives. The half-life of a substance is the time needed for its concentration to fall to one-half its initial concentration. Method I: Method of Initial Rates

m n The reaction is assumed to have a rate law in the form rate = v = k[ A] [ B] so that the initial

rate is given by

m n initial rate = v 0 = k [ A]0 [ B ]0

(1)

We want to find the order of the reaction m in [A]0 and the order n in [B]0 . Data is gathered for experiments in which [B]0 (the initial concentration of B) is kept constant and the initial rate v0 is determined for different values of [A]0 (the initial concentration of A). If [B]0 is held constant and [A]0 is increased by the factor f, the rates for the two runs will be

m n v 0, run 1 = k[ A]0 [ B ]0

(2)

n 0

v 0, run 2 = k ( f [ A]0 ) [ B ]

m

(3)

n 0, 2 k ( f [ A]0 ) m [ B ]0 = = fm m n 0, 1 k [ A]0 [ B ]0

(4)

m By comparing the factor f by which [A]0 was increased with the ratio of the initial rates f from Eq(4), the reaction order in [A] can be determined as shown in the table below:

Reaction Order in [A] zeroth order, m = 0 first order, m = 1 second order, m = 2 Eq(4) Ratio Initial Rate Result

f = f =1 f m = f1 = f fm = f2

Page 1 of 9

S. B. Piepho, 2002

Suppose that in going from run 1 to run 2, [A]0 is doubled so f = 2. Then, for example, if the initial rate is constant ( v 0, run 2 = v 0, run 1 ) the reaction is zeroth order in [A] (i.e., m = 0 in the rate law). If v 0, run 2 = 2 v 0, run 1 when [A]0 is doubled, the reaction is first order in [A] (m = 1 in the

2 rate law). Finally, if v 0, run 2 = 2 v 0, run 1 = 4 v 0, run 1 when [A]0 is doubled, the reaction is second

order in [A] (m = 2 in the rate law). An analogous process may be used to find n, the order of the reaction in [B] using runs where [A]0 is held constant but [B]0 is varied. In general, if the initial concentration of a substance is increased by a factor f (while all other initial concentrations are held constant), the initial rate v0 will increase by f n if the reaction has an order of n for the substance. Experimentally, to find each initial rate v0 we need to make up a solution with the desired initial concentrations, [A]0 and [B]o. The concentration of a reactant (or product) is then measured as a function of the time t. A graph of concentration versus time is made with the data, and the initial rate v0 is found from the slope of the graph (which should be linear at this initial stage of the reaction). _____________________________________________________________________________ _ Problem Using the Method of Initial Rates 1. The following data were obtained for the reaction A + B + C products: Initial rate, v0 Experiment [A]0 [B]0 [C]0 (mol L-1 s-1) 1 2 3 4 5 1.25 x 10-3 M 2.50 x 10-3 M 1.25 x 10-3 M 1.25 x 10-3 M 3.01 x 10-3 M 1.25 x 10-3 M 1.25 x 10-3 M 3.02 x 10-3 M 3.02 x 10-3 M 1.00 x 10-3 M 1.25 x 10-3 M 1.25 x 10-3 M 1.25 x 10-3 M 3.75 x 10-3 M 1.15 x 10-3 M 0.0087 0.0174 0.0508 0.457 ?

(a) Write the rate law for the reaction. Explain your reasoning in arriving at your rate law. [Hint:

Table 1 is useful here.]

(b) What is the overall order of the reaction? (c) Determine the value of the rate constant. [Hint: Use your rate law from (a) and appropriate data.] (d) Use the data to predict the reaction rate for experiment 5.

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S. B. Piepho, 2002

2 2 rate = v 0 = k[ A]0 [ B ]0 [C ]0 .

In runs 1 and 2, [B]0 and [C]0 are constant; when [A]0 doubles (f = 2), r0 increases by f = 2 = 21: thus 1st order in [A]0. In runs 1 and 3, [A]0 and [C]0 are constant; when [B]0 increases by the factor f = 2.416, v0 increases by a n factor of f = 5.839 = (2.416)2: thus 2nd order in [B]0.

In runs 3 and 4, [A]0 and [B]0 are constant; when [C]0 increases by a factor of f = 3, v0 increases by a factor n of f = 9 = 32: thus 2nd order in [C]0. (b) Fifth order overall. (c) k = 2.85 x 1012 L4 mol-4 s-1. (Use the rate law from (a) above and the data from any run to calculate k. (d) rate = v0 = 0.0113 mol L-1 s-1.

_____________________________________________________________________________ _

Method II: Use of the Integrated Rate Equations Rate equations are differential equations that in simple cases can be easily integrated using standard methods of calculus. For example, if the rate law has the form rate = d[A] = k [A]n dt (5)

the equation may be integrated (from t = 0 to t, and from [A] = [A]0 to [A]t) for different reaction orders in [A] (i.e., different values of n). The equations given in the table below are obtained for n = 0, 1, and 2. The useful feature of these equations is that they may be written in straight-line form, y = mx + b (where m = slope and b = y-intercept are constants).

Order in Rate Integrated Form, Page 3 of 9 Straight Half-Life

[A] Law y = mx + b Line Plot

S. B. Piepho, 2002

t1/2

rate = k [A]o= k

[A]t = - k t +[A]o

t1/ 2 =

[A]0 2k

rate = k [A]1

ln[A]t = - k t + ln[A]o

t1/ 2 =

ln 2 0.693 = k k

rate = k [A]2

t1/ 2 =

1 k[A]0

Experimental data is collected for a reaction over time to give the concentration of A ([A]t) at a number of times t. These data points are then tested graphically against the various rate equations. The reaction order is determined by deciding which of the plots (see Table 2) gives the best straight line. Note that this method requires data from a single experiment. However the data must be collected over several half-lives. If too little data is collected, all the plots will give a straight line, and it will not be possible to determine the reaction order. Recall that the half-life t1/2 is the time it takes for the concentration to fall to one-half its initial value [A]0. If the reaction is slow, several half-lives will be a great deal of time, and the Method of Initial Rates is more convenient. Other Forms of the First-Order Integrated Rate Equation The first-order rate equation is frequently re-arranged to give [A]t =kt ln [A]0 [A] ln 0 = k t [A]t

or

(6)

These forms are obtained easily from the integrated form of the first-order rate equation in the table above by using the property of logarithms, a ln = ln(a) ln(b) b Another property of logarithms is that if

Page 4 of 9

(7)

S. B. Piepho, 2002

ln(y) = x then y = ex These relations lead to additional forms of the first order integrated rate equation: [A]t =e [A]0

kt

(8) (9)

or

[A]0 =e kt [A]t

(10)

The forms given in Eqs (6) and (10) are useful in solving problems in which the fraction of material left [A]t/[A]o is related to the decay time t of the material. Many chemical decay processes and all nuclear decay reactions follow first-order kinetics. Note that for first-order reactions, the half-life t1/2 is easily determined from the rate constant k, and vice versa (see Table 2 above). _____________________________________________________________________________ _ Problems Using the Integrated Rate Equations 2. A pesticide decomposes following first-order kinetics. (a) If the half-life of the pesticide is 12 years, what is the rate constant k for the decomposition reaction? (b) What fraction of the pesticide will be left after 36 years? (c) What fraction of the pesticide will be left after 100 years? (d) How many years will it take for 99.9% of the pesticide to decompose?

Answers to Problem 2.

Page 5 of 9

S. B. Piepho, 2002

(a) k = 0.05775 yr-1 0.058 yr-1; (b) 36 years = 3 half-lives. Thus 0.125 = 1/8 left; (c) 0.0031 (or 0.31%); (d) When 99.9% is gone, 0.1% is left, so the fraction left = 0.001. To reach this point will take119.6 yr 120 yr.

_____________________________________________________________________________ _ 3. For a chemical reaction A+ 2 B C, a plot of 1/[A]t versus time t is found to give a straight line with a positive slope. (a) What is the order of the reaction? [Hint: See Table 2.] (b) How could you determine the rate constant k for the reaction from your graph?

Answers to Problem 3: (a) Second order; (b) Draw the best straight line through the points of the plot of 1/[A]t versus time t . The slope of the line is equal to the rate constant k.

Time, s [A], mol L-1

0 0.100

5 0.0141

10 0.0078

15 0.0053

20 0.004

(a) Plot the data and determine the order of the reaction.

[Hint: See Table 2. Fill in the table below and make three graphs on graph paper (or using a computer graphing program): (1) Zeroth-order graph: plot [A]t versus t; (2) First-order graph: plot ln[A]t versus t; Second-order graph: plot 1/[A]t versus t .] Time, s [A], mol L-1 ln[A] 1/[A], L mol-1

[Hint: See Table 2. How does the slope m relate to the rate constant k for the reaction order you determined in part (a)?]

Page 6 of 9

S. B. Piepho, 2002

Answers to Problem 4. (a) You should find that the plot of 1/[A]t versus t gives the best straight line, so the reaction is second order; (b) k = 12 L mol-1 s-1.

Page 7 of 9

S. B. Piepho, 2002

Time, s 0 5 10 15 20

[A]

Page 8 of 9

Chang, 7th Edition, Chapter 13, Worksheet #2 First-Order Graph -2.00 -3.00 -4.00 y = -1.483E-01x - 2.953E+00 r

2

S. B. Piepho, 2002

= 8.356E-01

ln[A]

5.00

Second-Order Graph y = 1.196E+01x + 1.000E+01 r 300.00 250.00 200.00 150.00 100.00 50.00 0.00 0.00 5.00 10.00 15.00 20.00 25.00 Time, t

1/[A] 2

= 9.999E-01

Page 9 of 9

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