1. 1 ITK-329 Kinetika & Katalisis (3 SKS) Dicky Dermawanwww.dickydermawan.net78.netdickydermawan@gmail.com

2. 2 Sylabus Review on basic concept & terminology Methods in collecting & analysis of rate data Interpretation of batch reactor data Nonelementary reaction kinetics Heterogeneous reaction kinetics

3. 3 Textbooks & References RI Masel, Chemical Kinetics & Catalysis, Wiley (2001) HS Fogler, Elements of Chemical Reaction Engineering, PHPTR (1999) CG Hill, Kinetics & Reactor Design (1977) O. Levenspiel, Chemical Reaction Engineering, 2 nd ed., Wiley (1972)

4. 4 Score & Grade 20 4 all homework & quiz 25 4 1 st midterm exam 25 4 2 nd midterm exam 30 4 final term examination  A 4 74.5 ++  B 4 59.5 ++  C 4 49.5 ++  D 4 39.5 ++

5. 5 Auxiliary: Computer Programs Microsoft Excel MathCAD

6. 6 Dicky Dermawan Chapter 1 Review on Chemical Kinetics Basic Concept & Terminology

7. 7 Common Jargon (1) Rate of reaction Rate equation, rate law, kinetic expression Empirical vs Mechanistic) Reaction order: first order, second order, half order, etc. overall order, pseudo- Rate constant Preexponential Activation barrier, activation energy Arrhenius’ law

8. 8 Common Jargon (2) Homogeneous reaction Heterogeneous reaction Elementary reaction Nonelementary reaction Reaction Mechanism Molecularity Molecular Dynamics Catalyst & Inhibitor

9. 9 Rate of Reaction & Stoichiometry Example: Ethane emissions from cars: 7 O 2 + 2 C 2 H 6  4 CO 2 + 6 H 2 O

10. 10 Factors Affecting Reaction Rate (acc. 2 Van’t Hoff) Concentrations of all of the reactants, products, and other species in the system Temperature The presence of solvents The presence of catalysts

11. 11 Effect of Concentration Comparing First- and Second- Order Reactions Consider a first-order reaction and a second-order reaction: How much would the rate change if you diluted the reactants by a factor of 3? Determining Reaction Order Under some conditions the platinum-catalyzed reaction: CO + ½ O 2  CO 2 Follows the rate equation: a. What is the order of the reaction? b. If K 2 C CO >> 1, what is the order of the reaction? c. If K 2 C CO << 1, what is the order of the reaction?

12. 12 Effect of Temperature Arrhenius’ law applies only to elementary reactions, NOT OVERALL E a [=] kcal/molecule E a [=] kcal/mole Still, Dunbar, McMahon (1998): Perrin (1919): Usually  3. molecule -1. sec -1 …second order …first order  6. molecule -2. sec -1 …third order

13. 13 Fitting Data 2 Equation 2.23 Yang, Lee & Wang, Int. J. of Chemical Kinetics, 27, (1995), 1111 examined the rate of the reaction: NCO + NO 2  CO + 2 NO As a function of temperature. Their data are given in Table P2.23. In the table, the rate constant is defined as rate/([NCO][NO2]) and is measured in units of 10 -11 cm 3 /(molecule.second) a. Are the units of the rate constant correct? b. Fit the data to Arrhenius’ law. How well do they fit? c. Is the fit improved with Still,Dunbar,McMahon eqn? d. How do you interpret the sign of the activation barrier? e. On the basis of your fits and the error bars in Excel, how much confidence do you have in the value of the activation barrier?

14. 14 Fitting Data 2 Equation 2.24 Eberhard & Howard, Int. J. of Chemical Kinetics, 28, (1996) 731 examined the rate of the reaction CH 3 CH 2 OO + NO  H 3 CH 2 O + NO 2 As a function of temperature. Their data are given in Table P2.24. In the table, the rate constant is defined as rate/([CH3CH2OO][NO]) and is measured in units of 10 -12 cm 3 /(molecule.second) a)Are the units of the rate constant correct? b)Fit the data to Arrhenius’ law. How well do they fit? c)Is the fit improved with Still,Dunbar,McMahon eqn? d)How do you interpret the sign of the activation barrier? e)On the basis of your fits and the error bars in Excel, how much confidence do you have in the value of the activation barrier?