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Chemical Kinetics
Chemical kinetics is the study of the factors
that affect the rates of chemical reactions
Such as temperature
Example 13.1: For the reaction given, the [I] changes from 1.000 M to 0.868 M in the first 10 s. Calculate the average rate in the first 10 s and the D[H+]. H2O2 (aq) + 3 I(aq) + 2 H+(aq) I3(aq) + 2 H2O(l)
solve the rate equation for the rate (in terms of the change in concentration of the given quantity)
solve the rate equation (in terms of the change in the concentration for the quantity to find) for the unknown value
Tro: Chemistry: A Molecular Approach, 2/e 6 Copyright 2011 Pearson Education, Inc.
Practice If 2.4 x 102 g of NOBr (MM 109.91 g) decomposes in a 2.0 x 102 mL flask in 5.0 minutes, find the average rate of Br2 production in M/s 2 NOBr(g) 2 NO(g) + Br2(l)
Factors Affecting Reaction Rate: Temperature Increasing temperature increases reaction rate
chemists rule of thumbfor each 10 C rise in temperature, the speed of the reaction doubles
for many reactions
of a reaction without being consumed Most catalysts are used to speed up a reaction; these are called positive catalysts
catalysts used to slow a reaction are called negative catalysts.
Homogeneous = present in same phase Heterogeneous = present in different phase How catalysts work will be examined later
Tro: Chemistry: A Molecular Approach, 2/e 10 Copyright 2011 Pearson Education, Inc.
Factors Affecting Reaction Rate: Reactant Concentration Generally, the larger the concentration of
reactant molecules, the faster the reaction
increases the frequency of reactant molecule contact concentration of gases depends on the partial pressure of the gas
higher pressure = higher concentration
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The rate law must be determined experimentally!! The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
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Reaction Order
The exponent on each reactant in the rate law
is called the order with respect to that reactant The sum of the exponents on the reactants is called the order of the reaction The rate law for the reaction
2 NO(g) + O2(g) 2 NO2(g) is Rate = k[NO]2[O2] The reaction is
The bottom reaction is autocatalytic because a product affects the rate. Hg2+ is a negative catalyst; increasing its concentration slows the reaction.
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Example: The rate equation for the reaction of NO with ozone is Rate = k[NO][O3]. If the rate is 6.60 x 105 M/sec when [NO] = 1.00 x 106 M and [O3] = 3.00 x 106 M, calculate the rate constant Given: Find: Conceptual Plan: Relationships: Solve:
[NO] = 1.00 x 106 M, [O3] = 3.00 x 106 M, Rate = 6.60 x 106 M/s k, M1s1
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Practice The rate law for the decomposition of acetaldehyde is Rate = k[acetaldehyde]2. What is the rate of the reaction when the [acetaldehyde] = 1.75 x 103 M and the rate constant is 6.73 x 106 M1s1?
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Rate = k[A]n
If a reaction is Zero Order, the rate of the reaction
is always the same
doubling [A] will have no effect on the reaction rate
Example 13.2: Determine the rate law and rate constant for the reaction NO2(g) + CO(g) NO(g) + CO2(g) given the data below
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Practice Determine the rate law and rate constant for the reaction NH4+ + NO2 N2 + 2 H2O given the data below
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Half-Life
The half-life, t1/2, of a
reaction is the length of time it takes for the concentration of the reactant to fall to its initial value The half-life of the reaction depends on the order of the reaction
22 Copyright 2011 Pearson Education, Inc.
Rate = k[A]0 = k
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Example 13.4: The reaction SO2Cl2(g) SO2(g) + Cl2(g) is first order with a rate constant of 2.90 x 104 s1 at a given set of conditions. Find the [SO2Cl2] at 865 s when [SO2Cl2]initial = 0.0225 M Given: [SO2Cl2]init = 0.0225 M, t = 865, k = 2.90 x 10-4 s1 Find: [SO2Cl2]
Conceptual Plan: Relationships:
[SO2Cl2]init, t, k
[SO2Cl2]
Solution:
Practice The reaction Q 2 R is second order in Q. If the initial [Q] = 0.010 M and after 5.0 x 102 seconds the [Q] = 0.0010 M, find the rate constant
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t1/2 = ln(2)/k
inversely proportional to the initial concentration increasing the initial concentration shortens the half-life
t1/2 = 1/(k[A]init)
31 Copyright 2011 Pearson Education, Inc.
Example 13.6: Molecular iodine dissociates at 625 K with a firstorder rate constant of 0.271 s1. What is the half-life of this reaction? Given: k = 0.271 s1
Find: t1/2
Conceptual Plan: Relationships:
t1/2
Solution:
Practice The reaction Q 2 R is second order in Q. If the initial [Q] = 0.010 M and the rate constant is 1.8 M1s1 find the length of time for [Q] = [Q]init
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The Effect of Temperature on Rate Changing the temperature changes the rate
constant of the rate law Svante Arrhenius investigated this relationship and showed that:
where T is the temperature in kelvins R is the gas constant in energy units, 8.314 J/(molK)
A is called the frequency factor, the rate the reactant energy approaches the activation energy
Ea is the activation energy, the extra energy needed to start the molecules reacting
Tro: Chemistry: A Molecular Approach, 2/e 34 Copyright 2011 Pearson Education, Inc.
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Arrhenius Plots
The Arrhenius Equation can be algebraically
solved to give the following form:
this equation is in the form y = mx + b where y = ln(k) and x = (1/T) a graph of ln(k) vs. (1/T) is a straight line
Example 13.7: Determine the activation energy and frequency factor for the reaction O3(g) O2(g) + O(g) given the following data:
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Example 13.7: Determine the activation energy and frequency factor for the reaction O3(g) O2(g) + O(g) given the following data:
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Example 13.8: The reaction NO2(g) + CO(g) CO2(g) + NO(g) has a rate constant of 2.57 M1s1 at 701 K and 567 M1s1 at 895 K. Find the activation energy in kJ/mol
Given: T1 = 701 K, k1 = 2.57 M1s1, T2 = 895 K, k2 = 567 M1s1 Find: Ea, kJ/mol
Conceptual Plan: Relationships:
Ea
Solution:
Check: most activation energies are tens to hundreds of kJ/mol so the answer is reasonable
Tro: Chemistry: A Molecular Approach, 2/e 42 Copyright 2011 Pearson Education, Inc.
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Effective Collisions
Collisions in which these two conditions are
met (and therefore lead to reaction) are called effective collisions The higher the frequency of effective collisions, the faster the reaction rate When two molecules have an effective collision, a temporary, high energy (unstable) chemical species is formed the activated complex
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Reaction Mechanisms
The probability of more than 3 molecules colliding
at the same instant with the proper orientation and sufficient energy to overcome the energy barrier is negligible Most reactions occur in a series of small reactions involving 1, 2, or at most 3 molecules Describing the series of reactions that occurs to produce the overall observed reaction is called a reaction mechanism Knowing the rate law of the reaction helps us understand the sequence of reactions in the mechanism
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H2(g) + 2 ICl(g) 2 HCl(g) + I2(g) 1) H2(g) + ICl(g) HCl(g) + HI(g) 2) HI(g) + ICl(g) HCl(g) + I2(g)
Notice that the HI is a product in Step 1, but then a reactant in Step 2 Because HI is made but then consumed, HI does not show up in the overall reaction Materials that are products in an early mechanism step, but then a reactant in a later step, are called intermediates
48 Copyright 2011 Pearson Education, Inc.
Molecularity
The number of reactant particles in an
elementary step is called its molecularity A unimolecular step involves one particle A bimolecular step involves two particles
though they may be the same kind of particle
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Mechanisms with a Fast Initial Step When a mechanism contains a fast initial step,
the rate limiting step may contain intermediates When a previous step is rapid and reaches equilibrium, the forward and reverse reaction rates are equal so the concentrations of reactants and products of the step are related
and the product is an intermediate
An Example
1. 2 NO(g) N2O2(g) 2. H2(g) + N2O2(g) H2O(g) + N2O(g) 3. H2(g) + N2O(g) H2O(g) + N2(g)
k1 k1
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Practice Mechanism
Determine the overall reaction, the rate determining step, the rate law, and identify all intermediates of the following mechanism 1. 2. A + B2 AB + B A + B AB Slow Fast
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Catalysts
Catalysts are substances that affect the rate of a
reaction without being consumed Catalysts work by providing an alternative mechanism for the reaction
with a lower activation energy
Fast Slow
Practice Mechanism
Determine the overall reaction, the rate determining step, the rate law, and identify all catalysts and intermediates of the following mechanism 1. HQ2R2 + R Q2R2 + HR Fast 2. Q2R2 Q2R + R Slow
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Catalysts
Homogeneous catalysts are in the same
phase as the reactant particles
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