Course Name: Catalysis and Catalytic Processes Course Code ...
Course Name: Catalysis and Catalytic Processes Course Code : CHPE550 Dr. Qazi Nasir Office No: 5D-40, College of Engineering [email protected] 1 Rate Law
Homogenous reaction Reaction which involves only one phase Heterogeneous reaction Reaction which involves more then one phase Irreversible reaction Reaction which proceeds only in one direction Reversible reaction Reaction which can proceed in either direction 2
Rate Law Molecularity of reaction The number of atoms, ions or molecules involved in reaction step Unimolecular reaction Bimolecular Termolecular reaction 3
Rate Law Relative rates of reaction Can be obtained from the ratio of stoichiometric coefficients 4 Rate Law Example If NO2 is formed at a rate of 4 mol/m3/s
The rate of formation of NO The rate of disappearance of NO is The rate of disappearance of O2 is 5 Rate Law The reaction order and the rate law The rate of disappearance of A, -rA depends on temperature and composition. It can written as product of rate constant kA &
function of concentration of various species Rate law of kinetic expression 6 Rate Law Power Law models Dependence of the reaction rate (-rA) on concentration fn(Cj) is determined by experimental observation
Alternatively, power law models are used The exponents of concentration is reaction order 7 Rate Law Power Law models Units of rA are in terms of concentration per unit time but units of specific reaction rate kA depends
on reaction order Consider the following reaction 8 Rate Law Elementary reaction The one that evolves a single step such as biomolecular reaction The stoichiometric coefficient in this reaction are
identical to the power it the rate law Nonelementary reaction 9 Rate Law Nonelementary reaction Large number of both homogenous and heterogeneous reactions don not follow simple rate laws
Homogeneous Reactions The over all order does not have to be an integer 10 Rate Law Nonelementary reaction Heterogeneous Reactions In many gas-solid reaction, it is often practice to write rate laws in terms of partial pressures rather
than concentration e.g. hydrodemethylation of toluene (T) to form benzene (B) and methane (M) over solid catalyst The rate of disappearance of toluene per mass of catalyst, -rT, follows Langmuir-Hinshelwood kinetics and rate law found experimentally to be 11 Rate Law Nonelementary reaction
Heterogeneous Reactions Where KB and KT are the adsorption constants with units of kPa-1 (atm-1) and specific reaction rate has units Rate of reaction in terms of concentration rather then partial pressure can be written as 12 Rate Law
The Reaction Rate Constant The reaction rate constant k is not truly a constant It merely independent of concentration It is almost strong function of temperature It may be function of total pressure (gas phase-R) In liquid system it is function of other parameter e.g. ionic strength, choice of solvent 13
Rate Law The Reaction Rate Constant Swedish chemist Arrhenius first suggested the temperature dependence of the specific reaction rate, kA could be correlated in equation 14 Rate Law Activation Energy
Most atoms and molecules undergoes reaction, there is an activation energy Couples of reason The molecules need energy to distort or stretch their bonds so that they break them to form new bonds The steric and electron repulsion forces must be overcome as the reacting molecules come close together 15
Rate Law Activation Energy One way to view the barrier to a reaction is through the use of the reaction coordinates The coordinates denotes the potential energy of the system as a function of the progress along the reaction path as we go from reactant to an intermediate to product
16 Rate Law Activation Energy 17 Rate Law Activation Energy
Example: Determination of the Activation Energy Calculate the activation energy for the decomposition of benzene Diazonium chloride to give chlorobenzene and nitrogen using the table information 18 Rate Law
Activation Energy The equation that best fit the data The slope of the line 19 Batch System Batch reactor are primarily used for the production
of specialty chemicals and to obtained reaction rate data in order to determine reaction rate laws and rate law parameters such as k, the specific reaction rate 20 Batch System At time t=0, open the reactor and place a number of moles of species A, B, C, D and I (NAO, NBO, NCO,
NDO and Nt) into the reactor 21 Batch System At time t=0, open the reactor and place a number of moles of species A, B, C, D and I (NAO, NBO, NCO, NDO and Nt) into the reactor
22 Batch System Equation of Batch Concentrations The concentration of A is the moles of A per unit volume CA = NA/V. Similarly, for other components 23
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