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chem 157.1 Exp

chem 157.1 Exp

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Experiment # 9
CHEMICAL KINETICS
Diane F. Falculan
Sunshine Charisse Abadilla
Chem 157.1
Prof. Yambot
Department of Physical Sciences and Mathematics
College of Arts and Sciences
University of the Philippines Manila
I. Introduction

Chemical kinetics is a branch of physical chemistry that deals with the study of the rates of chemical reactions. It also includes investigations of how different experimental conditions can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that can describe the characteristics of a chemical reaction. It complements thermodynamics by supplying information about the rate of approach to equilibrium and the mechanism responsible for the conversion of reactants to products.

A mathematical expression relating the rate of a reaction to the concentration of either reactants or products is called the rate law of a reaction. It tells how fast the reaction proceeds and how the reaction rate depends on the concentrations of the chemical species involved.

Usually rate laws take the form,

wherex,y,z, are small whole numbers or simple fractions andk is called the "rate constant." The sum ofx +y +z + . . . is called the "order" of the reaction. The rate equation is a differential equation and it can be

integrated in order to obtain an integrated rate equation that links concentrations of reactants or
products with time.

There are common types of rate laws. A Zero-order reaction has a rate which is independent of the concentration of the reactant(s). Increasing the concentration of the reacting species will not speed up the rate of the reaction. Zero-order reactions are typically found when a material required for the reaction to proceed, such as a surface or a catalyst is saturated by the reactants. The rate law for a zero-order reaction is r = k, where r is the reaction rate and k is the reaction rate coefficient with units of concentration/time. A reaction is zero order if concentration data are plotted versus time and the result is a straight line. The slope of this resulting line is the negative of the zero order rate constant k.

In a first order reaction, the rate is proportional to the concentration of one of the
reactants. That is,v = rate =k [B], where B is a reactant. If a reaction which is known to be first
order in B, such as B + other reactants \u2192 products, the rate law is written as,
The constant,k, in this rate equation is the first order rate constant. A plot of ln[A] vs. timet
gives a straight line with a slope of \u2212k.

In a second order reaction the rate is proportional to concentration squared. For example, possible second order rate laws might be written as Rate =k [B]2 or as Rate =k[A][B]. That is, the rate might be proportional to the square of the concentration of one of the reactants, or it might be proportional to the product of two different concentrations. However, measuring a second order reaction rate can be problematic: the concentrations of the two reactants must be followed simultaneously, which is more difficult; or measure one of them and calculate the other as a difference, which is less precise. A common solution for that problem is the pseudo first order approximation. Ifeither [A] or [B] remain constant as the reaction proceeds, then the reaction can be considered pseudo first order because in fact it only depends on the concentration of one reactant. If for example [B] remains constant then: wherek' =k[B]0 and we have an expression identical to the first order expression above. By collectingk' for many reactions with different (but excess) concentrations of [B]; a plot ofk' versus [B] givesk (the regular second order rate constant) as the slope. Meanwhile, for a third order reaction, a rate law can be written in several different ways. One might have cases where Rate =k[A]3, or Rate =k[A]2[B], or Rate =k[A][B][C],and so on.

Several factors affect the rate of a chemical reaction. With the exception in certain reactions, upon which concentration is without effect, an increase with the initial concentration of reactants also results in an acceleration of the rate. This is in accordance with the collision theory which assumes that for a reaction to occur, the reactant particles must collide. Therefore, increasing the concentration will also increase the frequency of the molecules colliding, striking each other faster by being in closer contact at any given point in time causing collisions to happen more often. However, the rate for a given initial concentration does not remain constant all throughout the reaction rather is highest at the beginning and decreases with time as the reactants are consumed. The rate becomes low after a time that the reaction may be considered complete.

Temperature also has a pronounce effect on the speed of reaction. When reactants in a chemical reaction are heated, atoms or molecules gain more thermal energy and become more energetic giving a greater probability to collide with one another. More importantly however, is the fact that at higher temperatures molecules has more vibrational energy that is, atoms are vibrating much more violently. Raising the temperature therefore, not only increases the number of collisions but also collisions that can result in rearrangement of atoms within the reactant. In

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