Chemical Kinetics in Real Tim Using the Differential Rate Law and Discovering the Reaction Orders A Physical Chemistry Laboratory Experiment B.R. Ramachandran and Arthur M. Halpern Department of Chemistry, Indiana State University, Terre Haute, IN 47809 Laboratory experiments that illustrate and test the fundamental principles of chemical Kinetics are justifi- ably regarded as an indispensable part of the physical chemistry Iaboratory curriculum. In analyzing chemical rate data, however, one iovitably encounters & basic di- Jemma, Experimentally, one usually measures the time dlependenes of « property, such as absorbance, that is re- lated to the concentration of a chemical species, for ex- ample, [XI(. These data represent the integrated rate Taw forthe reaction being studied. Yet from a theoretical point of view, ne uses the ifferential rate law to express the fundamental kinetic properties ofthe reaction, for it js through this approach that one can obtain insight into the mechanism of the reaction and the conditions that affect st. A detailed discussion of the methodological ad- ‘vantages of using the differential rate law has been pre- Sented by Steel and Naqvi (1). Teis in order to reconcile the difference between theo- retical and exporimental"languages” that one is motivated {oderivethe integeated ratelave from the differential rate laweThus one transforms the fandamental dilferential rate law into a form that conforms to the conditions appropri- fate to measured information so that the rate law ean be tested and further used to abtain necessary kinetic pa- rameters (reaction orders) and rate constant ‘Although the expression of the integrated rate law from various differential rate law schemes is often straightforward mathematically and physical chemistry textbooks place considerable emphasis on these math- ematical exercises (2-4), their actual application to the experimental domain can be problematical. One good and fairly common example of this situation is the reaction between two different species A + BB ~ Products) In the ease where the reaction is first-order with respect to both A and B, three experimental scenarios are identified: (Case 1, The reaction i intially (and subsequently) flooded with one reactant, ¢g., [Alp >> [Blp, in which case the reaction exhibits pseudo-first-order behavior, and the integrated rate law (involving [B]() in this example), which is exponential in time, is easily managed, (Case 2. The reaction is carried out under the stoichiomet- vic houndary constraint, b[Alp = alBlo, whereupon the reaction foliows simple second-order kineties, and the analysis of the [AJ or [Bl rate data is straightfor- ward; eg, VAI vs. is linear. Case 3. Neither boundary condition in 1 or 2 pertains, and the simplicity in analyzing the integrated rate law is accordingly lost. But one pays a price forthe simplifications that arise from conditions 1 and 2. In the first ease, the presonee of 686 Journal of Chemical Education ‘an appropriate excoss of a reactant may alter the reac- tion conditions sufficiently to affect the actual mechanism, in which case the rate constant measured may deviate from its intrinsic value, Moreover, in ease 1, the strict va- lidity of the simplified integrated rate law used depends oon the degree to which the inequality, for example, [Alp >> [Blo,can be established; in some instances, this condi tion is limited because of reactant solubilty: In addition, forsuch psoudo-first-ordor conditions, soveral kinetic runs are needed for the determination of the rate dependence fon the excess reactant, concentration. In ease 2, the cor- reetnoss of the simple second-order integrated rate law depends on the experimental accuracy employed for es- ‘ablishing the exact ratio of initial reactant concentra- tions. ‘The need to exploit the simplifications gained by the specialized initial concentrations diseussed above is no Tonger, however, compelling. Indeed, there is now a strong ‘tivation, and ample justifieation, to avoid those artifi cial requirements becaise of the ease and convenience of obtaining kinetic data—that is, (X}®—in digital form. ‘These data can readily be numerically differentiated and then directly applied to the fundamental differential rate law: a ‘where [P] represents the product concentration, which is ‘monitored as a function of time, and a and 8 are the reae- tion orders with respect to A and B, fone already knows the reaction orders, oq Lean be ceast into @ polynomial of order (c+ B), since both (Aj and {B) can be linked to the measured quantity, [P], Thus vs ing the reaction stoichiometry cited above, eq I becomes ALPVde = {Alo —alP)M(Blo-21PP (2) As a clearer example, we can use the ease where. 1 and a= 6 = 1.The right-hand side ofeq 2 can now be seen ‘to be a second-order polynomial in [P LP Vat = k({Alo— 1PD) (Blo LP) ‘The rate constant is then obtained through a straightfor- ‘ward nonlinear regression analysis of the derivative data expressed as a function of [P| Application to a Specific Reaction One classie reaction that satisfies several pedagogi- cal purposes is the coupling between 2,4-dinitrochloro- benzene (DNCB) and piperidine (Pip) to form 24- 4initrophenylpiperidine (DNPP) in ethanol (or 95% etha- rol) solution. This reaction is an example of the relatively ‘uncommon nueleophilie aromatic substitution process and,‘thus, is of interest to students studying organic chemis- try aa well. The balanced equation is DNCB + 2Pip + DNPP + Pip-HCL ‘This renetion follows overall second order kinetics. Tho 1:2 stoichiometry between the reactants arises because a second Pip molecule acts as a base that abstracts an H* ion from the 1:1 zwitterion complex, known as the Meisenheimer intermediate, formed between DNCB and Pip in a prior, slow step, as shown in the following scheme. 2.89 A useful feature of this reaction is that itis clean and quantitative; also, despite the relative eomploxity of the detailed mechanism, itis kinetically simple. Moreover, at ambient temperatures, the reaction proceeds slowly, per- ‘mitting the process tobe studied in real time using simple instrumentation and conventional data acquisition tech- ‘niques. Thus, because the experiment is carried out using, fa very straightforward procedure, the student is able to place more attention on the interpretation and analysis ‘of the data, with the objective of confirming (or finding) the rate law and the rato constant. ‘An experimental procedure that has been previously reported involves quenching the reaction with ethanolic HCl at measured time intervals and measuring the DNPP concentration (5-8). In that case, an appropriate inte- igrated rate law must be used for the data analysis, The DNPP product is a bright-yellow compound. Because the absorption spectea of DNCB and Pip donot interfere with that of DNPP, the reaetion rate is readily studied spectrometrically by following the inerease in the prod- ‘uct absorbanee with time. "The reaetion between DNCB and Pip is known to fal: low overall second-order kinetis: [DNPPYdt = k((DNCB)y ~ [DNPP) (Piplo- 2(DNPP) (3) ‘or more explicitly (6) Using this approach, students can first determine o.and 8 and thus confirm thatthe reaction is indeed first order With respect to each reaetant. Once «and 6 have been found, the rate data are analyzed according to eq I (here ), and & is thus found. For example, the three- Darametor regression analysis on the rate data for [DNCBfp = 0.00510 M and (Piply =0.0206 M returned the flowing values c= 1 096(6-0.018) = 0.9 (0= 0.04), and f= 0.690 (0 = 0.068) 3? min-i, Those values indie cate thatthe reaction is indeed first-order with respect to ‘each reuciant, and hence the rate equation simplifies to ‘eq 4. A subsequent single-parameter regression analysis returned the Value of 0.695 6 = 0.001) M~! min“ for the rate constant & Another important advantage in analyzing the kinetic ata using the differential rate law, aside from being rid of the need to conform to the inital houndary eonditions in reactant concentrations as outlined in eases 1-8 above, {s thatthe time lag between the mixing of reactants (ie, the onset of reaction) and the acquisition of data is of no consequence, To see this point more clearly, note that all ofthe integrated laws that might beused in the data analy- Sis (cases 1-3) are derived with the boundary condition [DNPP| = 0 when ¢ = 0. Since in most experimental cit cumstances encountered by the students [DNPP\0) #0, fn additional time-lag parameter, , must be used tinue = fap * ©) otherwise, “Toreesitting” the data will rosull in value of that is compromised. Alternatively, fone can employ a correction term with (P),) data that is based on the reactant concentration and the appropriate integrated rate equation. “Tublo 1 lists the outeome of our differential rate law analysis ofthe DNCB-Pip reaetion a 295 K under differ ent kinetic conditions (cases 1-2) The rate constants ob- tained from the “conventional” integrated rate laws are also given for comparison. Tt can be seen that thoro is excellent agreement between the rate constants obtained by these different methods. ‘igure 1 shows the plot of AIDNPPYAt vs. (DNPP] and also the best fit obtained for [DNCBlp = 0.00510 M and [Piplp = 0.0208 M.A plot of the residuals is also given, Initial “Guoss” of the Rate Constant {for Regression Procedure In using nonlinear regression procedures itis neces- sary to furnish an initial guess of the parameter(s) being sought. Thus, an initial value ofthe rate constant & has to beentered in the analysis. he regression algorithm, which Jooks for the minimum in a highly complex error surface that is a function of the parameter k, should in principle return the same optimized value of k regardless of the initial guess. However, in practice, the regression procoss ‘may end up trapped in a local minimum in the error sur- face, which may be far removed from the “true” minimum, and consequently return a spurious value of the rate con- 688 Journal of Chemical Education stant. This difficulty can be circumvented ifthe initial ‘guoss is aceoptably close to its true value. This experi- ‘ment can serve as a good introduetion to this important aspect af regression analysis. Thus, the student should have an idea ofthe rate constant even before its value ia ‘determined by using regression analysis! Here we describe a simple procedure for estimating the rate constant from the half-life of a reaction. The half. life typ, ofa reaction may be defined asthe time required for half of the “limiting” reagent to be consumed in the process. The halflife of a DNCB-Pip run can be easily estimated from the spectrometrie data by noting the time needed forthe absorbance to rise to about one-half ofthe absorbance expected for 100% conversion, The relation: ship betweon fyp and ktakos a diferent functional form depending on the kinctic conditions ofthe reaction (cases 1-5) and also on which reactant is the limiting reagent. ‘he interested studont can derive those equations with itl diel We feel that for a rough estimate ot how- ever, those exact equations are not really neceseary and suggest that eqs 6 would serve the purpose. It can be im- mediately recognized that these equations correspond to simple socond ordor conditions (caso 2)-When simple sce- ‘ond order conditions donot apply (i... 2(DNCBly (Pipl) ‘tho equation that involves the concentration of the re: agent in excess should be used, k~VADNCBlotya) or # ~ U(Piplotya) @ Table 1. Second-Order Rate Constant of the DNCB-Pip Reaction in Ethanol at 203 K Using the Differential and Integrated Rate Equations ONCE} Ppl EEF “0.0108 0.0206 <2 «(0.6764 0.0009 0.6688 0.0008 0.0081 0.0208 3 016951 0.0006 0.6887 0.0002 0010s 0104 3 06759 0.0014 0.6574 0.0007 0.00218 0.1015 1 07497 0.0008 0.7228 0.0007 0.0520 0.004071 a7iai Fate cnstarts are reporied in nis I mi tenn kottaiad nthe epession, ‘Outcome of knee antes using the dren steam ‘Outcome okt anes using the appropatertegaed rato ew ON eR a Figure 1, Plot of oJONPPYAt obtained from numercal dterenta- tion of the data, ve, [NPP] at 299 K. The regression value fork ‘obtained irom 24 6, 0.885 Mi mir”Figure 2. Arrrenus plot of k obtained for [NCB], = 0.0103 M and [Pip = 0.0206 M, and analyzed using oq 6. The regression value for is 47.8 ksmol. ‘Temperature Dependence of the ONCB-Pip Reaction Rate Constant “The tamperature dependonce ofthe rate eonstant of ‘the DNCB-Pip reaction in ethanol was studied between 268 and 388 K.To this end, simple second order reaction conditions, with [DNOB]p = 0.0108 M and [Pipl = 0.0206 MM, were employed. The rate constants exhibit Arrhenius behavior (see Fig. 2); thus we find k = exp(19.224 ~ 5748 1), The Arrhenius parameters for the reaction are A= 2.233 10° Mt mine! and By = 47.8 kd mol, from ‘which the values of AIM and AS® at 298 K are caleulated tobe 45.4 kd mol” and 127 J K+ mol, respectively. These data may bo compared with A = 2.00 x 108 M2 min-! and By = 47-2 kd mol based on & values reported at bwo temperatures (6) ‘Scope of Several Undergraduate Research Projects ‘Various amines are known to reaet with DNCB with remarkably different rate constants that eannot be ac- ‘counted for by the differences in their basicities; Brady ‘and Cropper have suggested that steric factors might play aan important role in these reactions (5). We believe that ‘the kinetios of the reaction of DNCB with a series of pri- ‘mary amines with different degrees of branching on the nitrogen-containing carbon atom would make an inter- ‘sting project; the students can determine the Arrhenius parameters of these reactions and can try to understand, the structure-reactivity relationships in these substitu. fon processes. study of solvent effets would also be ‘Summary The reaction between 2,4-dinitrochlorobenzene DCB) and piperidine to yield 2,4-dinitrophenylpiper- line (DNPP) is very suitable for an undergraduate physi- cal laboratory experiment. The student can analyze the data by using the differential rate law. This method offers students a chance to “discover” the order of the reaction, thereby motivating them to obtain further insight into the mechanism of the process. These experimental meth- ods may be used in excellent undergraduate physical chemistry projects. ‘Acknowledgment Partial funding of the spectrophotometer was pro- vided by the National Science Foundation through the In- strament and Laboratory Improvement Program (USE- 9151048). We also acknowledge C. Steel for helpful sug- gestions, Literature Cited 1 See Cag 8 Poe Ca 98) 1719-0718 2 Leona N Bneal Choma ed aes Now Yk 1859 = 2 king we het os WH ema: New Yak 18679 on KJ. Chen! Kinin 2d: Marge & Rows Rom irk 575018 ‘Beanie Cth Hea Cho ee 6 6 Tilers Mo Hoe gern Pha! Chit eat, dso bce Chm Se 8 5 16 Find it on the Web: http://jchemed.chem.wisc.edu/ JCE Internet—Chemistry Textbooks in Print Index You will find up-to-date textbook info at any time as part of the Chemical Education Resource Shelf. Hal Harris of the University of Missouri, St. ‘Louis is the editor. The Index lists information about approximately 450 ‘extbooks from analytical through general and organic to physical. Harris beginning to add secondary school, crystallography, histary, and polymer texts; software listing als on JCE Online, pperlinks to publishers; and more links to materi- Volume 73. Number7 July 1996 689