Information • Textbooks • Media • Resources

Textbook Deficiencies: Ambiguities in Chemical Kinetics

Rates and Rate Constants
Keith T. Quisenberry and Joel Tellinghuisen*
Department of Chemistry, Vanderbilt University, Nashville, TN 37235; *joel.tellinghuisen@vanderbilt.edu

In chemical kinetics, one determines reaction rate laws Similarly, for the reaction in eq 2
and rate constants by following the temporal changes in the
concentrations or pressures of reactants or products. For ex- ∆[ NO2 ] 2
= −2 k2 [NO2 ] (8a)
ample, two gas-phase reactions that feature prominently in ∆t
most general and physical chemistry textbooks are and
2 N2O5(g) 4 NO2(g) + O2(g) (1)
∆[ O2 ] 2
= k2 [NO2 ] (8b)
and ∆t
2 NO2(g) 2 NO(g) + O2(g) (2) On the other hand, if these reactions are rewritten as
The reactants and products are consumed and generated with N2O5(g) 2NO2(g) + 1 2 O2(g) (1´)
rates proportional to their stoichiometry coefficients. Thus
in the reaction in eq 1, consumption of 2 mol of N2O5 leads and
to production of 4 mol of NO2 and 1 mol of O2, so at any
time the absolute rates of change of these three are in the NO2(g) NO(g) + 1 2 O2(g) (2´)
ratio 2:4:1. Similarly, in the reaction in eq 2, the absolute
the rate law expressions change to, for example,
rates of change of NO2, NO, and O2 are in the ratio 2:2:1.1
To define reaction rates and rate constants unambigu- ∆[ N2 O5 ]
ously with respect to these different physical rates, it is nec- = − k1′ [ N2 O5] (7a´)
essary to adopt a convention. As recommended by the ∆t
IUPAC, for the generic reaction, and
bB + cC dD + eE (3) ∆[ NO2 ] 2
= − k2′ [NO2] (8a´)
the convention consists in defining the reaction rate as ∆t

1 d [B ] 1 d[C ] 1 d[D] 1 d[ E ] The quantities on the left hand sides of eqs 7 and 8 are physi-
rate = − = − = = (4) cal rates that cannot depend upon how we choose to write
b dt c dt d dt e dt
the reactions. On the other hand, the reaction rates and rate
where the rate is a product of the rate constant k and some constants constitute conventional quantities, since their val-
function of the concentrations of reactants and products. This ues are tied to the written reaction through the convention
function must be determined experimentally and constitutes of eq 4. Thus, k1´ = 2k1 and k2´ = 2k2; and hence rate1´ = 2 rate1
the rate law. For the reactions in eqs 1 and 2, the rate laws and rate2´ = 2 rate2. Clearly, the reaction rate and rate con-
have been found to be stant are ambiguous without explicit reference to the written
reaction.2
rate1 = k1 [N2 O5] (5) Probably all texts correctly recognize that reactants and
products disappear and appear with rates proportional to their
and
stoichiometry numbers, and most seem to correctly state the
2 convention of eq 4 (in finite difference form for general chem-
rate 2 = k2 [NO2] (6)
istry). However, it has come to our attention that many gen-
The convention is often stated in the form of eq 4 in eral chemistry texts manage to “snatch defeat from the jaws
physical chemistry texts. In general chemistry, it is common of victory” in the leap to the integrated rate laws that follow
practice to introduce the rate concept with finite differences from eqs 7 and 8 and other cases where the stoichiometry
in place of differentials, so ∆’s appear in place of the d ’s. Ac- numbers are not unity. This may be because they seldom ac-
cordingly, for the reaction in eq 1, the rate law appears as tually solve the differential forms of these equations, rather
just state the results for first- and second-order reactions, usu-
∆[ N2 O5 ] ally in the generic forms,
= −2 k1 [ N2O5] (7a)
∆t [A] = [ A ]0 e −k t (9)
or and

∆[ NO2 ] 1 1
= 4 k1 [ N 2O5 ] = + kt (10)
(7b) [A ] [ A ]0
∆t

510 Journal of Chemical Education • Vol. 83 No. 3 March 2006 • www.JCE.DivCHED.org

 Information • Textbooks • Media • Resources

respectively. These forms are correct for reactions written A Accordingly, the integrated rate laws become
→ products, which means that eq 9 is correct for most first-
order processes, which usually are written this way. However,
for the reaction in eq 1, the correct integrated expression is 1 1
[A] = [ A ]0 exp ( −a k1st t ) and = + ak 2 nd t (17)
−2 k1 t [A] [ A ]0
[ N2 O5 ] = [ N2 O5 ] e
0
(11)
and the half-lives are
and since second-order processes are almost always written
in the form 2A → products (e.g., eq 2), eq 10 is wrong for ln 2 1
these. Instead it should read t 1st
1 = 1st
and t 12nd = 2nd (18)
2 ak 2 ak [ A]0
1 1
= + 2 kt (10´)
[A] [ A ]0 We have examined a dozen general chemistry texts of
the sort widely used in the instruction of science and pre-
One of the main reasons for giving students the inte- medical students (1–12) and have concluded that only two
grated rate expressions of eqs 9 and 10 is the desire to ac- of these have all aspects of this problem essentially correct—
quaint them with the concept of fractional life, especially those by Whitten et al. (1) and Oxtoby et al. (2).3 And even
half-life. Thus, for example, by noting that t1/2 is the time these fail to emphasize that while the half-life is a physical
needed for [A] to fall to 1/2[A]0, one readily obtains from eqs property of the system, the rate constant and its relation to
9 and 10 the commonly given expressions, the half-life depend upon how the reaction is written. With
respect to the N2O5 decomposition, Oxtoby commits a mi-
ln 2
t 1st
1 = (12a) nor flaw by writing the reaction as shown in eq 1´ and then
2 k two pages later (in Example 14-5) asking students to find k
and for “the first-order decomposition of N2O5(g)” without ac-
1 tually stating the reaction. Presumably it is to be taken as eq
t 12nd = (12b) 1´ above; but the authors have actually adopted for the sake
2 k [ A ]0 of the example a half-life that is incorrect, as the k it yields
at 25 ⬚C agrees with the literature value for k1, not k1´ (13).
But these expressions are not correct for the reactions in eqs Of the other texts, several either fail to state the con-
1 and 2, where the correct versions are vention of eq 4 or give it and then announce that it will be
n2
ln ignored! In addition to the examples given in eqs 1 and 2,
t1 = (13a) errors occur in connection with the discussion of the first-
2 2 k1
order decomposition of H2O2(aq) and the (pseudo) second-
and order recombination of I atoms. The texts by Petrucci et al.
1 (6) and Brown et al. (8) bypass the problem by assiduously
t1 = (13b) sticking to coefficients of unity in their use of the integrated
2 2 k2 [NO2]0
rate laws and half-lives. In the case of Brown, this appears to
be a conscious attempt to correct this problem in earlier edi-
respectively. In going from eqs 12 to 13, it is not the half-life tions; and Petrucci et al. slip up in their Table 15.4 by listing
that is changing but the rate constant. Like the rates that ap- eq 1 but then giving a half-life and k that are correctly re-
pear on the left-hand sides of eqs 7 and 8, the half-life is a lated for eq 1´, not 1.
physical property of the system and cannot depend upon how As was already noted, physical chemistry texts state the
the reaction is written. convention in differential form; but most make some of the
The foregoing results can be summarized in more com- same errors of omission and commission in applications. The
pact form by using stoichiometry numbers νi and labeling topic is treated very clearly by Levine (14), through his Prob-
all reactants and products as Ai. Then the balanced chemical lem 17.5 (17.1 in the 4th edit.), in which the implications
reaction reads of eqs 1 and 1´ are compared directly. Levine also provides a
useful simplification of eqs 16–18, by defining kA = ak.
∑ νi Ai = 0 (14)
As was noted earlier, in general chemistry texts the prob-
where νi is negative for reactants and positive for products; lem arises in part because the integrated rate expressions of
and eq 4 becomes eqs 9 and 10 are just stated, not derived. Since texts like those
we examined are used in courses for science, engineering, and
1 d[Ai ] premedical majors, there seems little reason not to include
rate = (15) the derivations. In their differential forms, eqs 7 and 8 con-
νi dt
stitute the simplest kind of differential equations, solvable
In the simplest case, where a single reactant A (unsubscripted) by separating variables and integrating. Such equations are
determines the rate law, let us take a = ᎑νA. Then the first- introduced to calculus students in their first encounter with
and second-order rate laws of eqs 7 and 8 read integration. This usually comes before they study kinetics in
chemistry, which is typically in their second semester. The
∆[ A ] ∆[ A ] 2 sidebox approach used by some authors is a reasonable com-
= −ak1st [A ] and = −ak 2 nd [A ] (16) promise and requires little page space.
∆t ∆t

www.JCE.DivCHED.org • Vol. 83 No. 3 March 2006 • Journal of Chemical Education 511

 Information • Textbooks • Media • Resources
One of us (JT) first encountered this ambiguity many
years ago, while trying to understand and use literature re-
sults for the classic termolecular recombination of I atoms
in the gas phase, I + I + M → I2 + M, which has added
potential for confusion in usually being written “I + I” in-
stead of “2I.” Chemistry texts should make it clear that (i)
the rate and rate constant for a reaction are ambiguous with-
out an explicit statement of the reaction for which they are
meant to apply and (ii) while half-lives are physical proper-
ties of the chemical system in question, rate constants are
not. Also, general chemistry students intending careers in sci-
ence or medicine need no longer be sheltered from the mod-
est amount of integral calculus needed to understand the
derivation of the integrated rate laws for the simplest zeroth-,
first-, and second-order reactions.
Notes
1. This strict conservation can be violated at times during the
course of the reaction if there are intermediates that can build up
in significant quantities.
2. The use of noninteger stoichiometry coefficients is often
avoided in kinetics, in recognition of the aim of understanding the
reaction on the molecular level. But the problem still arises through
the writing of reactions like those in eqs 1 and 2 as A → products.
3. We have exercised no “preselection” here: These were texts
that were readily available to us in the form of desk copies from
our shelves and from those of our colleagues and were the only
ones we examined. All 12 fall under the category, introductory
courses (mainly for “majors”), on the online JCE ChemEd Resource
Shelf, http://www.jce.divched.org/JCEWWW/Features/CERS/ (accessed
Dec 2005); the authors represent about a third of those whose books
are listed there.
512 Journal of Chemical Education • Vol. 83 No. 3 March 2006
Literature Cited
1. Whitten, K. W.; Davis, R. E.; Peck, M. L. General Chemistry,
6th ed.; Saunders/Harcourt: Orlando, FL, 2000; Chapter 16.
2. Oxtoby, D. W.; Freeman, W. A.; Block, T. F. Chemistry: The
Science of Change, 4th ed.; Brooks/Cole–Thomson Learning:
Pacific Grove, CA, 2003; Chapter 14.
3. McMurry, J.; Fay, R. C. Chemistry, 4th ed.; Prentice Hall: Up-
per Saddle River, NJ, 2004; Chapter 12.
4. Atkins, P.; Jones, L. Chemical Principles: The Quest for Insight,
3rd ed.; W. H. Freeman: New York, 2005; Chapter 13.
5. Chang, R.; Cruickshank, B. Chemistry, 8th ed.; McGraw–Hill:
Boston, 2005; Chapter 13.
6. Petrucci, R. H.; Harwood, W. S.; Herring, F. G. General Chem-
istry: Principles and Modern Applications, 8th ed.; Prentice Hall:
Upper Saddle River, NJ, 2002; Chapter 15.
7. Chemistry: A Project of the American Chemical Society; Bell, J.,
Ed.; W. H. Freeman: New York, 2005; Chapter 11.
8. Brown, T. L.; Lemay, H. E., Jr.; Bursten, B. E.; Burdge, J. R.
Chemistry: The Central Science, 9th ed.; Prentice Hall: Upper
Saddle River, NJ, 2003; Chapter 14.
9. Zumdahl, S. S.; Zumdahl, S. A. Chemistry, 6th ed.; Houghton-
Mifflin: Boston, MA, 2003; Chapter 12.
10. Silberberg, M. S. Chemistry: The Molecular Nature of Matter and
Change, 3rd ed.; McGraw–Hill: Boston, 2003; Chapter 16.
11. Brady, J. E.; Senese, F. Chemistry: Matter and Its Changes, 4th
ed.; Wiley, Hoboken, NJ, 2004; Chapter 15.
12. Kotz, J. C.; Treichel, P., Jr. Chemistry and Chemical Reactivity,
3rd ed.; Saunders/Harcourt Brace; Fort Worth, TX, 1996;
Chapter 15.
13. Johnston, H. S.; Tao, Y.-S. J. Am. Chem. Soc. 1951, 73, 2948–2949.
14. Levine, I. N. Physical Chemistry, 5th ed.; McGraw-Hill, Bos-
ton, 2002; Chapter 17.
• www.JCE.DivCHED.org