Introduction brief history

Early work of L F Wihelmy 1850 on sucrose inversion F W Ostwald thirty years later next major move A G Harcourt and W.Essen invoked procedures similar to those used today (1834-1919) Order of reactions Treated first order and second order reactions Macroscopic and microscopic kinetics studied

Systems in thermal equilibrium, Boltzman distribution

A BRIEF HISTORY OF CHEMICAL KINETICS (AND OF CRE)

(Ref.: "The World of Physical Chemistry," by K. J. Laidler, Oxford Univ. Press, 1993) 1850: Wilhelmy (Germany) studied the rate of inversion of sucrose (hydrolysis into D-(+)-glucose and D-(-)-fructose in the presence of an acid) and found it to be proportional to the concentrations of both the sugar and the acid. 1864: Guldberg and Waage (Norway) formulated their "law of mass action," according to which the reaction "forces" are proportional to the product of the concentrations of the reactants: K=[R]r [S]s/([A]a [B]b) where a, b, r and s are the stoichiometric coefficients in the chemical equation A+B=R+S. So the rate of the forward reaction is proportional to [A]a [B]b and that of the reverse reaction is proportional to {R]r [S]s.

History of Kinetics
1865: Harcourt and Esson (UK) analyzed the reactions between H2O2 and HI and between KMnO4 and (COOH)2. They wrote the corresponding differential equations, integrated them and determined the concentration vs. time relationships. They also proposed an equation for the temperature dependence of the reaction rate, k = A TC. 1884: van't Hoff (The Netherlands) published his "Studies of Chemical Dynamics" (tudes de dynamique chimique), in which he generalized and further developed the work of Wilhelmy, Harcourt and Esson. In particular, he introduced the differential method of analysis. He also analyzed the temperature dependence of the equilibrium constant (now called the "van't Hoff equation") and of forward and reverse reaction rates. 1887: Ostwald (Germany; Latvia) introduces the terms "reaction order" and "half-life" in his "Lehrbuch der allgemeinen Chemie." 1889: Arrhenius (Sweden) further analyzed the temperature dependence of reaction rate, k = A exp(-B/T), and gave it an "energy barrier" interpretation; this is now called the "Arrhenius equation. http://www.ems.psu.edu/~radovic/KineticsHistory.html

Scope of Chemical kinetics

Field Biology Chemical Engineering Electrochemistry Geology Inorganic Chemistry Mechanical Engineering Metallurgical Eng. & Materials Science Description Physiological processes Reactor Design Electrode processes Flow processes Reaction mechanisms Physical metallurgy, dislocation mobility Kinetics in solids-diffusion, nucleation growth, migration, growth of phases, PVD, CVD Reaction mechanism Viscosity, diffusion, nuclear processes Drug action

Organic Chemistry Physics Pharmacology

Chemical kinetics- What is involved?

Study of rate and mechanisms by which one species is converted into another Rates considered on specific basis per unit volume of reaction mixture for a homogenous reaction or per unit mass of catalyst for a heterogeneous reaction Mechanism is the sequence of individual events whose overall result produce the observed reaction

Kinetics of Processes- why do this course?

Enable design of equipment used for carrying out processes for materials synthesis/transformations What type and size of equipment is essential to accomplish a desired extent of a materials process?

Operating conditions, provisions for exchange of energy

constitute the process design Cost analysis, choice of construction materials, instrumentation and control define the process

From a simple reaction between molecules to the economical design of a chemical reactor, kinetics and catalysts are the key.

Chemical synthesis in microreactors has the greatest impact for processes requiring precisely-controlled or challenging operating conditions (difficult compounds, energetic intermediates, or high pressures and temperatures) and for on-demand, on-site production. (Jensen Group)

Few steel blast furnaces and steel mills

Kinetics of Processes - How do we do this?

Combine chemical rates with physical processes by writing conservation equations Express physical processes i.e rates of energy transfer and of mass transfer from one chemical species to another Terms for converting one chemical species through intrinsic rate for that conversion step Body of knowledge about variables that affect this intrinsic rate and equations which correlate such data is the kinetics of process

Kinetics of Processes - How do we do this?

Conservation equations depend on the type of reactor and not the reactions Terms of mass and energy transfer are the same for a reactor Ideal reactors are CSTR, plug flow, packed bed Correlations obviate the need for experiments Intrinsic rates must be obtained from expriments From a beaker to a plant scaling up

MM 305: Kinetics of Processes-Admin

Credit structure L T P C 2 1 0 6 Class tests 1+1 (before and after midsem) Dates- Thu. 30 Jan and 20 Mar. (tentative) Submissions at the end of every tutorial class Mid sem Feb. 17-22 End sem Apr. 18-1 MayTotal Marks : (10+5+20+5+10+50) (No re-exam requests will be entertained) Total contact hours : 41 (from the calendar) Tutorials: 11 (generally scheduled on Thursdays) Problem solving is important: ideally two students to a group. To be randomised. TAs: Aditya Kulkarni, 09d11012:Yash Sheth, 09d11024:Sheshank Kumar, 09d11028:
Vaibhav Jain, 09d11031:Ranjeet Singh Banthiya, 09d11025

20 10 20 50 100

Course content
1. Thermodynamics vs kinetics; Homogeneous vs heterogeneous reactions. Chemical reaction kinetics: order of reactions, Arrhenius equation. Rate theories. Homogenous reactions. Ideal batch reactors, continuous stirred tank reactors, plug flow reactors. Residence time & RTD. Mixing. Design of reactors for homogenous Reactions. Heterogeneous Reactions - Elements of mass transfer, diffusion in fluids, mass transport equation, mass transfer coeff. Mass transfer in porous materials, ordinary & Knudsen diffusion, pore size distribution. Adsorption : Physical vs Chemical, Adsorption isotherms, BET method. Surface reactions & their Kinetics. Fluid-fluid reactors with homogeneous& heterogeneous reactions. Fluidsolid contactors / reactors: packed bed, fluidized bed. Heat transfer controlled reactions. Examples from materials processing: CVD/PVD reactors, thin film deposition,. Combustion, oxidation/reduction, drying, calcinations, precipitation etc.

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Texts/References
1. K.J. Laidler, Chemical Kinetics, 3rdEd., Harper and Row, New York, 1987. 2. O. Levenspiel, Chemical Reaction Engineering, 3rdEd., John Wiley, New York, 1999. 3. H.S. Fogler, Elements of Chemical Reaction Engineering, 3rdEd., Prentice Hall of India, New Delhi, 1999. 4. A.W. Adamson and A.P. Gast, Physical Chemistry of Surfaces, 6thEd., Wiley-Interscience, 1997. 5. George Roberts, Chemical reactions and chemical reactors, John Wiley & Sons, 2009. 6. Lanny D. Schmidt, The engineering of chemical reactions, Oxford, 2005 7. Stoichiometry and thermodynamics of metallurgical processes, Y.K.Rao 1985