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ChemI 4 Chemical Kinetics

The document discusses chemical kinetics and factors that affect reaction rates such as the physical state and concentration of reactants, temperature, and presence of catalysts. It also covers reaction rates, rate laws, reaction orders, activation energy, reaction mechanisms, catalysis, and spectroscopic methods for monitoring reactions.

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Kuo Sarong
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124 views5 pages

ChemI 4 Chemical Kinetics

The document discusses chemical kinetics and factors that affect reaction rates such as the physical state and concentration of reactants, temperature, and presence of catalysts. It also covers reaction rates, rate laws, reaction orders, activation energy, reaction mechanisms, catalysis, and spectroscopic methods for monitoring reactions.

Uploaded by

Kuo Sarong
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as DOC, PDF, TXT or read online on Scribd
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Chapter 14

📍 chemical kinetics
- chemistry that is concerned with the speeds or rates or reactions

📍 Factors that affect reaction rate


physical state of reactants
� the more readily molecules collide w/ each other! The more rapidly they react
concentration of the reactants
� As concentration increases, the frequency w/ w/c the reactant molecules collide increases
leading to increased rates.
the temperature at w/c reaction occurs
�rates of chemical reaction increase as the temperature is increased
the presence of catalyst
catalyst- agents that increase reaction rates w/o being used up
enzymes- protein molecules that act as catalyst
✏ in general, reaction rates depend on the frequency of collisions between particles: greater
frequency of collisions greater rate of reaction

📍 Reaction rates- speed of chemical reaction; the change in the concentration of reactants or
products per unit time
� can be expressed as rate of disappearance of reactant or rate of appearance of product.
☝ by convention, rates are always expressed as positive quantities

📍 change of rate with time


☝ it is typical for rates to decrease as a reaction proceeds, because the concentration of the
reactants decreases.

📍 Instantaneous rate- rate at a particular moment in the reaction


� determined from the slope of the curve at the point of interest
☝ instantaneous rate at t= 0 is called the initial rate of the reaction

📍 reaction rates and stoichiometry


aA + bB → cC + dD
Rate = - (1/a) ((∆[A])/∆t) = - (1/b) ((∆[B])/∆t) = (1/c) ((∆[C])/∆t) = (1/d) ((∆[D])/∆t)
* not true ifsubstances C and D are formed in significant amounts during reaction

📍 Rate law - shows how rate depends on the conc of the reactants
Rate = k•([reactant1]^m)•([reactant2]^n),
where k is rate constant and m&n are reaction orders

overall reaction order (z) - sum of the orders with respect to each reactant in the rate law: =
m+n

📍 units of rate constant


� depend on the overall reaction order of the rate law
Units rate constant = (units of rate)/ (units of conc)^z
☝ zero order, changing conc will have no effect on the rate
☝ rate of reaction depends on conc but rate constant does not
☝ rate constant is affected by temperature and the presence of catalyst

📍order of reactions
first order reaction
� rate depends on the conc of a single reactant raised to the first power
Rate = - ∆[A]/∆t = k•[A]
↑ differential rate law- expresses how rate depends on conc
if with function "ln" it is called integrated rate law
ln( [A]t / [A]0 ) = -kt
general form of the equation y= mx + b
ln ([A]t) = -k•t + ln ([A]0)
� graph is a straight line in ln([A]t) vs time

Second order reaction


� rate depends on the reactant concentration to the second power or on the 2 diff reactants
Rate = - ∆[A]/∆t = k•[A]²
1/ ([A]t) = k•t + 1/([A]0)
� graph is a straight line in 1/([A]t) vs time

Half life (t½)


� time read for the reaction for the conc of a reatpctant to reach ½ of its initial value
� convenient way to describe how fast is the reaction occurs
half life of first order
t½ = 0.693/k
✏ in a first order reaction, thebconc of reactant decreasesvby ½ in each of a series of
regularly spaced intervals namely t½
half life of second order
t½ = 1/ k[A]0
✏ half life depends on the initial conc of reactants

rate constant, rate of tpreaction, increases rapidly w/ temperature approx doubling for 10°C rise

📍 collision model- based on kinetic molecular theory accounts for concentrations of reactants and
temperature effects in rate at the molecular level
� central idea is that molecules must collide to react
� greater collisions, greater reaction rates
📍 orientation factor - relative orientations during collisions determine whether the atoms are
suitably positioned to form new bonds

📍Svante Arrhenius- molecules must possess a certain min. Amount of energy to react
📍 activation energy, Ea - minimum energy reqd to initiate a chemical reaction
� carries from reaction to reaction
� energy diff between that of the starting molecule and the highest energy along the reaction
pathway
� activated complex or transition state- particular arrangement of atoms at the top of the
barrier
☝ energy change for the reaction ∆E does not affect the rate of reaction
☝ the rate depends on the magnitude of Ea; generally, lower Ea is the faster the reaction
� reverse reaction is endothermic and the activation barrier for the reverse reaction is equal to
the sum of ∆E and Ea for the forward reaction

📍 fraction of molecules
f = e^(-Ea/RT)

📍 Arrhenius equation
k = Ae^(-Ea/RT). Where A is the frequency factor, approx constant
3 factors affecting reaction rate
1. Fraction of molecules possessing an energy of Ea or greater
2. Number of collisions occurring per second
3. Fraction of collisions that have the appropriate orientation
✏ reaction rates decrease as Ea increase

📍 determining activation energy


✏From general equation y= mx + b
ln k = — (Ea/RT) + ln A
✏ given k1 and k2
ln (k1/k2) = (Ea/R)[(1/T2)-(1/T1)]

📍 Reaction mechanism - describe in great detail the order in w/c bonds are broken and formed and
the changes in relative positions Of the atoms in the course of the reaction
Elementary reaction (elementary process)
� both processes occur in a single event or step
molecularity- number of molecules that participate as reactants in an elementary reaction
� unimolecular- single molecule is involved
� bimolecular- two reactants molecules involved
�termolecular- three molecules involved ( rare)

multistep mechanism - consist of a sequence of elementary reaction


✏ the chemical equations for the elemtary reactions in a multi step mechanism must always
add to give the chemical equation of the overall process
✏ intermediate- not a reactant or a product but formed in one elementary reaction and
consumed in the next

✏ if a reaction is an elementary reaction, then its rate law is bases directly on its molecularity
rate of a unimolecular process is first order
Rate = k•[A]
rate of a bimolecular elementary step is second order
Rate = k•[A]•[B]

📍 rate-determining step (rate-limiting step)


� slow step limits the overall reaction rate
� governs the rate law for the overall reaction
✏ the slowest step in a multi step reaction limitsbthe overall rate.
�rate of a faster step following the rate determining step does not speed up the overall rate
� the faster preceding steps produce intermediate products that accumulate before being
consumed in the slow step.

✏ whenever a fast step precedes a slow one, we can solve for the concentration of an intermediate
by assuming that an equilibrium is established in the fast step

📍catalyst - substances that changes the speed of chemical reaction without undergoing a
permanent chemical change itself

homegeneous catalyst - catalyst that is present in the same phase as the reacting molecules
✏ catalyst and the intermediates do not appear in the chemical equation for overall reaction.
✏ the catalyst is there at the start of the reaction, whereas the intermediate is formed during the
course of the reaction
✏ a catalyst lowers the overall activation energy for a chemical reaction

heterogeneous catalyst - existbin a different phase from the reactant molecules, usually as a
solid in contact w/ either gaseous reactants or with reactants in a liquid soln.

� adsorption - binding of molecules tons surface


� absortion- uptake of molecules into the interior of another substance

📍 enzymes- efficient biological catalyst


�catalase- enzymes in the blood and livers of mammals which catalyzes the decomposition of
hydrogen peroxide into water and oxygen
active site - location where the reaction is catalyzed
substrates- substances that undergo reaction at this site
lock and key model - provides a simple explanation for the specificity of an ezyme .
� lysozyme -
enzyme substrate complex- combination of the enzyme and the substrate
enzyme inhibitors- the activity of an enzyme is destroyed if some molecule in the solution is
able to bind strongly to the active site and block the entry of the substrate
turnover number -number of individual catalyzed reactions events occurring at a particular
active site.

📍 Spectroscopic methods- technique used to monitor conc of reactant or product


�rely on the ability of substances to absorb (or emit) electromagnetic radiation
📍 Beer's Law- relates amount of light being absorbed to the conc of the substance absorbing light
A= abc,
A is measured absorbance, a is molar absorptivity, b path length through w/c the radiation must
pass, and c is the molar conc of absorbing substances. Thus, concept is proportional to absorbance.
📍 isomerization- transformation to its isomers in first order reaction
✏ isomers- molecules that have the Same atoms arranged differently.
📍 chemiluminescence reaction - one that produces light
( see page 590)

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