REACTION MECHANISMS

The aim of the course is to give the essential tools to formulate rational hypotesis of reaction mechanisms taking advantage especially of chemical kinetic data analysis.
Therefore the primary goal is to teach to design suitable experimental trials for deducing a reasonable mechanism for a reaction. In more detail it will be important:
1) to make student aware of the great importance of determining the mechanism of a reaction; 2) to describe which are the different disposable tools to hypothesize, define and prove a reaction mechanism; 3) to learn the concepts, the terminology, and the tools of the chemical kinetics 4) to make student able to combine kinetic and extra-kinetic information to define a reaction mechanism.

1. Knowledge and comprehension:
A) to learn which are the general strategies to determine a reaction mechanism;
B) to learn which are the general strategies for a kinetic study of a reaction;
C) to learn which are the main features of the rate laws;
D) to learn to utilize the extra-kinetic information for confirming a reaction mechanism.

2. Ability to apply knowledge and comprehension:
A) to be able to choose, from time to time, which is the most correct approach for determination of a reaction mechanism;
B) to be able to deduce the rate law from experimental data;
C) to be able to propose a reaction mechanism based on experimental rate law;
D) to be able to collect and interpret extra-kinetic information;

3. Ability of judgment:
A) to be able to agree kinetic with extra-kinetic data for defining the reaction mechanism;
B) to be able to recognize possible errors by a critical analysis of applied procedure.

4. Ability of exposition:
A) to be able to communicate the acquired knowledge and the results of its application utilizing an appropriate terminology both orally and in written form;
B) to be able to interact with the docent and other students during the lesson.

5. Ability of learning:
A) to be able to take notes, selecting information in order of importance and priority;
B) To be able to solve problems of chemical kinetics.

To have attended the mathematic courses (CT0522 and CT0502) and preferably to have passed the relative examinations

The contents of the course are:
Elementary reactions and reactions mechanism. Net reactions and reactions rate. The order of a rate law. Factors influencing reaction rate. Elementary reactions and molecularity. The experimental determination of reactions orders.
First order reactions. Second order reactions. Zeroth-order reactions and fractional order reactions.
Reactions with a complex dependence respect on a single concentration variable. Product-catalyzed reactions. Methods of data analysis. Reversible reactions. Parallel and concurrent reactions. Concurrent reactions of mixtures.
Consecutive reactions. The steady-state approximations. The prior-equilibrium approximation. Catalyzed and enzyme-catalyzed reactions.
Use of Physical properties with kinetic data.
Temperature dependence of reactions rate. Transition state theory. Microscopic reversibility. The chemical interpretation of activation parameters.
Extra-kinetic probes of mechanism. Kinetic isotope effect. Analysis of the products. The study of the intermediates. Stereochemical criteria. Linear free energy relationship. The Hammett and the Taft Correlations.

Lectures notes
Chmical Kinetics and Reaction Mechanism, J. H. Espenson, McGraw-Hill,Inc

Oral examination.
The oral examination consists in a series of questions regarding the part of the program reported in the section “ Contents”. The student will be able to show both the learning of program subjects and the ability to expose them in correct and formal manner. Moreover student will be able to propose a plausible hypothesis of mechanism for a real reaction, using kinetic and/or extra-kinetic data.

Frontal lesson with support of slides.
The slides will be provide to students in electronic format

Italian

Accessibility, Disability and Inclusion
Accommodation and support services for students with disabilities and students with specific learning impairments:
Ca’ Foscari abides by Italian Law (Law 17/1999; Law 170/2010) regarding support
services and accommodation available to students with disabilities. This includes students with mobility, visual, hearing and other disabilities (Law 17/1999), and specific learning impairments (Law 170/2010). In the case of disability or impairment that requires accommodations (i.e., alternate testing, readers, note takers or interpreters) please contact the Disability and Accessibility Offices in Student Services: disabilita@unive.it.

oral

This subject deals with topics related to the macro-area "Climate change and energy" and contributes to the achievement of one or more goals of U. N. Agenda for Sustainable Development