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Transcript of 1 General Chemistry 4 th edition, Hill, Petrucci, McCreary, Perry Hall © 2005 Prentice Hall © 2005...
1
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Turn in:
– Nothing
• Our Plan:– Test Results– Videos/Notes– Investigation 10 Pre-Lab
• Homework (Write in Planner):– Be prepared for Investigation 10 next class and
have report started.
2
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Introduction to Chemical Kinetics
• What is Kinetics? I’ll let Hank explain…
http://www.youtube.com/watch?v=7qOFtL3VEBc• Stop at 3:20
3
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Kinetics in Action…
• Clock Reactions…• http://
www.youtube.com/watch?v=BqeWpywDuiY
4
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Unit Preview…Some Reactions
• Are fast:– Acid/base
neutralization– Sodium + water – PPT reactions
• Are slow: – Aluminum oxidation– Iron oxidizing– Plastic bottle
decomposing
5
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
And some depend…
• On temperature: fireflies• On conditions: Iron oxide (humid or
desert) • On enzymes: many processes in our body• On a catalyst:
2CO + 2NO --> 2CO2 + N2 (automobile
pollution and catalytic converters)
6
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
• Chemical kinetics is the study of:– the rates of chemical reactions– factors that affect these rates– the mechanisms by which reactions occur
• Reaction rates vary greatly – some are very fast (burning, precipitation) and some are very slow (rusting, disintegration of a plastic bottle in sunlight).
Chemical Kinetics: A Preview
7
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Variables in Reaction Rates
• Concentrations of reactants: Reaction rates generally increase as the concentrations of the reactants are increased.
• Temperature: Reaction rates generally increase rapidly as the temperature is increased.
• Surface area: For reactions that occur on a surface rather than in solution, the rate increases as the surface area is increased.
• Catalysts: Catalysts speed up reactions and inhibitors slow them down.
8
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Think of it like this…
• http://ed.ted.com/lessons/how-to-speed-up-chemical-reactions-and-get-a-date
9
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Theories of Chemical Kinetics: Collision Theory
• Before atoms, molecules, or ions can react, they must first collide.
• An effective collision between two molecules puts enough energy into key bonds to break them.
• The activation energy (Ea) is the minimum energy that must be supplied by collisions for a reaction to occur.
• A certain fraction of all molecules in a sample will have the necessary activation energy to react; that fraction increases with increasing temperature.
• The spatial orientations of the colliding species may also determine whether a collision is effective.
10
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Distribution of Kinetic Energies
At higher temperature (red), more molecules
have the necessary activation energy.
11
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Key Point Orientation of
molecules at the time of their collision will determine whether they react or not!
12
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Analogy - Car Crash Example
Energy and orientation of cars during a car
crash can establish the change that occurs to the
cars.
13
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Importance of Orientation
One hydrogen atom can approach another from any direction …
… and reaction will still occur; the spherical symmetry of the atoms means
that orientation does not matter.
Effective collision; the I atom can bond to the C atom to form CH3I
Ineffective collision; orientation is important
in this reaction.
14
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Transition State Theory
• The configuration of the atoms of the colliding species at the time of the collision is called the transition state.
• The transitory species having this configuration is called the activated complex.
• A reaction profile shows potential energy plotted as a function of a parameter called the progress of the reaction.
• Reactant molecules must have enough energy to surmount the energy “hill” separating products from reactants.
15
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Activated complex• Species formed as a result of collisions
between energetic molecules that is an intermediate between the reactants and the products of a reaction. Once formed the activated complex dissociates either into products or back to the reactants
16
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Reaction Profile• A graphical representation of a
chemical reaction in terms of the energies of the reactants, activated complexes and products
17
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Reaction Profile
18
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Exothermic
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Endothermic
20
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
CO(g) + NO2(g) CO2(g) + NO(g)
A Reaction Profile
21
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
An Analogy for Reaction Profiles and Activation Energy
22
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Stop!• Investigation 10 - We’re going to test
the effect of different variables on the rate of reaction next class.
• Complete steps 1 – 6 on the lab handout and be prepared to conduct the lab next class.
23
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Turn in:
–Nothing• Our Plan:
–Investigation 10• Homework (Write in Planner):
–Lab Report Due Friday
24
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Turn in:
–Lab Report (rubric on top)• Our Plan:
–Notes & Practice• Homework (Write in Planner):
–Work on the Ch. 13 Homework
25
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
The Meaning of Rate
• The rate of a reaction is the change in concentration of a product per unit of time (rate of formation of product).
• Rate is also viewed as the negative of the change in concentration of a reactant per unit of time (rate of disappearance of reactant).
• The rate of reaction often has the units of moles per liter per unit time (mol∙L–1∙s–1 or M∙s–1)
26
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
If the rate of consumption of H2O2 is 4.6 M/h, then …
… the rate of formation of H2O must also be 4.6 M/h, and …
… the rate of formation of O2 is 2.3 M/h
27
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
2 H2O2 --> 2 H2O + O2
… 0.1850 mol H2O2 reacted in 60 s.
Rate =0.1850 mol H2O2/L
60 s
= 0.00131 M H2O2 s–1
1 L
2.960 g O2 (0.09250 mole) produced in 60 s means …
28
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.1
Consider the hypothetical reaction
A + 2B --> 3C + 2D
Suppose that at one point in the reaction, [A] = 0.4658 M and 125 s later [A] = 0.4282 M. During this time period, what is the average (a) rate of reaction expressed in M∙s–1 and (b) rate of formation of C, expressed in M∙min–1.
29
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Try It Out!
EX 13.1 A: Consider the hypothetical reaction
2A + B → 2C + D
Suppose that at some point during the reaction [D] = 0.2885 M and that 2.55 min (that is 2 min 33 sec) later [D] = 0.3546 M.
a) What is the average rate of reaction during this time period, expressed in M min-1?
b) What is the rate of formation of C expressed in M s-1?
30
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Rate of Reaction Expressed as the negative of the Slope of a Tangent Line
• Average rate (green dotted line)
• Initial Rate ( blue solid line)• Instantaneous Rate (red line)• Question: Over what time
interval are the instantaneous rates greater than the average rate measured for the 600 sec period?
31
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Average vs. Instantaneous Rate
Instantaneous rate is the slope of the tangent to the curve at a particular time.
We often are interested in the initial instantane-ous rate; for the initial concentrations of reactants and products are known at this time.
32
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.2
Use data from Table 13.1 and/or Figure 13.5 to
(a) determine the initial rate of reaction and
(b) calculate [H2O2] at t = 30 s.
33
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Try It Out
EX 13.2 A: From Figure 13.5,
a) Determine the instantaneous rate of reaction at t = 300 s.
b) Use the result of a) to calculate a value of [H2O2] at t = 310 s.
34
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
The Rate Law of a Chemical Reaction
• The rate law for a chemical reaction relates the rate of reaction to the concentrations of reactants.
• The exponents (m, n, p…) are determined by experiment.• Exponents are not derived from the coefficients in the
balanced chemical equation, though in some instances the exponents and the coefficients may be the same.
• The value of an exponent in a rate law is the order of the reaction with respect to the reactant in question.
• The proportionality constant, k, is the rate constant.
aA + bB + cC …→ products rate = k[A]n[B]m[C]p …
35
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Rate Law Examples
Rate = k[A]1 = k[A] Reaction is first order in A
Rate = k[A]3 Reaction is third order in A
Rate = k[A]2 Reaction is second order in
A
If we triple the concentration of A in a second-order reaction, the rate increases by a
factor of ________.
36
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Effect of Concentration on RateOrder of Rxn Concentration
ChangeEffect on Rate
0 Double/Triple… Nothing (20)
1 Double Double (21)
1 Triple Triple (31)
2 Double Quadruple (22)
2 Triple 8x (32)
2 Quadruple 16x (42)
3 Double 9x (23)
3 Triple 27x (33)
37
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
More About the Rate Constant k
• The rate of a reaction is the change in concentration with time, whereas the rate constant is the proportionality constant relating reaction rate to the concentrations of reactants.
• The rate constant remains constant throughout a reaction, regardless of the initial concentrations of the reactants.
• The rate and the rate constant have the same numerical values and units only in zero-order reactions.
• For reaction orders other than zero, the rate and rate constant are numerically equal only when the concentrations of all reactants are 1 M. Even then, their units are different.
38
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
To find the overall order of a reaction…
• Add the orders for each compound.• Example:
–rate = [A]2[B]1 is 3rd order overall–How about rate = [A]0[B]1[C]1?
39
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Units of k (p. 536)
Overall Reaction Order
Units of k
Zero M s-1
First s-1
Second M-1 s-1
Third M-2 s-1
40
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Method of Initial Rates
• The method of initial rates is a method of establishing the rate law for a reaction—finding the values of the exponents in the rate law, and the value of k.
• A series of experiments is performed in which the initial concentration of one reactant is varied. Concentrations of the other reactants are held constant.
• When we double the concentration of a reactant A, if:– there is no effect on the rate, the reaction is zero-order in A.– the rate doubles, the reaction is first-order in A.– the rate quadruples, the reaction is second-order in A.– the rate increases eight times, the reaction is third-order
in A.
41
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
The concentration of NO was held the
same in Experiments 1 and 2 …
… while the concentration of
Cl2 in Experiment 2 is twice that of Experiment 1.
The rate in Experiment 2 is twice that in Experiment 1, so the reaction must be first
order in Cl2.
Which two experiments are used to find the order of the
reaction in NO?
How do we find the value of k after obtaining the order of the
reaction in NO and in Cl2?
42
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.3
For the reaction 2 NO(g) + Cl2(g) → 2 NOCl(g) described in the text and in Table 13.2, (a) what is the initial rate for a hypothetical Experiment 4, which has [NO] = 0.0500 M and [Cl2] = 0.0255 M? (b) What is the value of k for the reaction?
43
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
So, when looking at data…..
• Zero order reaction: initial rate is unaffected (20 )
• 1st order reaction: double the concentration, doubles the rate (21 =2)
• 2nd Order Reaction: Initial rate increases fourfold (22 =4)
• 3rd Order Reaction: Initial rate increases eightfold (23 =8)
44
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Try It Out
• Below is some rate data for the hypothetical reaction, 2A + B --> C. What is the rate law for this reaction?
Experiment [A]0 [B]0 Rate (M/s)
1 2.0 M 1.0 M 0.100
2 2.0 M 2.0 M 0.400
3 4.0 M 1.0 M 0.100
45
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Let’s Take a Break
• With your partner, Complete Part 1 of the Partner Review
46
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
•Sum of exponents is equal to zero
47
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Rate of Reaction= k[A]0
•The concentration time graph is a straight line with a negative slope
Zero Order
48
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Zero Order• Rate of the reaction:
–IS equal to k –remains constant throughout the
reaction –is the negative of the slope of the
line when graph Molarity vs. time (see pg. 544)
49
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Rate is independent of initial concentration
A Zero-Order Reaction
rate = k[A]0
= k
50
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Zero OrderIntegrated rate equation:
[A]t = -kt + [A]0
y = mx + b
51
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Zero Order (cont.)
y = [A]t = conc of A at some time
x = t = time
b = [A]0
m = -k (m, the slope of the straight line)
52
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
First-Order Reactions
• In a first-order reaction, the exponent in the rate law is 1.• Rate = k[A]1 = k[A]
Look! It’s an equation for a straight line!
ln [A]t – ln [A]0 = –kt
ln [A]t = –kt + ln [A]0
• At times, it is convenient to replace molarities in an integrated rate law by quantities that are proportional to concentration.
• The integrated rate law describes the concentration of a reactant as a function of time. For a first-order process:
ln[A]t
[A]0
= –kt
53
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Rate of reaction= k[A]1
Integrated rate equation
ln[A]t = -kt + ln[A]0
y = mx + b
54
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
1st Order
• Easy test for a first order reaction is to plot the natural log of reactant conc. vs. time and see if the graph is linear.
55
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Decomposition of H2O2
56
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.4
For the first-order decomposition of H2O2(aq), given k = 3.66 x 10–3 s–1 and [H2O2]0 = 0.882 M, determine (a) the time at which [H2O2] = 0.600 M and (b) [H2O2] after 225 s.
57
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Another ExampleH202 initially at a conc of 2.32 M, is allowed to decompose. What will the [H202] be 1200 s later? Use k = 7.3 x 10-4 s-1 for this first order decomposition.
58
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Try It Out
EX 13.4 A: The decomposition of nitramide, NH2NO2, is a first order reaction:
NH2NO2 (aq) → H2O (l) + N2O (g)
The rate law is rate = k[NH2NO2], with k = 5.62 x 10-3 min-1 at 15ᵒC. Starting with 0.105 M NH2NO2,
a) At what time will [NH2NO2] = 0.0250 M
b) What is [NH2NO2] after 6.00 hours?
59
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Half-lifeTime required for ½ of the
reactant to be consumedEquation:
t1/2 = ln2 = 0.693
k k
60
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.5
• Use data from Figure 13.7 (p. 542) to evaluate the
a) half-life and
b) Rate constant for the first order decomposition of N2O5 at 67 ᵒC:
N2O5 (g) → 2NO2 (g) + ½ O2 (g)
61
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.5 A
Use the result of Example 13.5 to determine
a) The time required to reduce the quantity of N2O5 to 1/16 of its initial value and
b) The mass of N2O5 remaining after a 4.80 g sample of N2O5 has decomposed for 10.0 min.
62
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Sum of exponents = 2
63
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Second-Order Reactions
• A reaction that is second order in a reactant has a rate law in which the exponent for that reactant is 2.
Rate = k[A]2
• The integrated rate law has the form:
• The half-life of a second-order reaction depends on the initial concentration as well as on the rate constant k:
1 1–––– = kt + –––– [A]t [A]0
What do we plot vs. time to get a
straight line?
1t½ = ––––– k[A]0
64
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.7The second-order decomposition of HI(g) at 700 K is represented in Figure 13.9.
HI(g) → ½ H2(g) + ½ I2(g)
Rate = k[HI]2
What are the: (a) rate constant and (b) half-life of the decomposition of 1.00 M HI(g) at 700 K?
65
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Try It Out
EX 13.7 A: If, in the second order reaction A → products, it takes 55 s for the concentration of reactant A to fall to 0.40 M from an initial concentration of 0.80 M, what is the rate constant k for the reaction?
66
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Summary of Kinetic Data
67
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Short Cut!!• [A] vs time (straight line = Zero
order) • ln [A] vs. time ( straight line = first
order) • 1/[A] vs. time (straight line =
second order)
68
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Try it in your note packet!
Time, min [A] ln[A] 1/[A]0 1.05 0.6310 0.4615 0.3625 0.25
69
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Crash Course Review
• http://www.youtube.com/watch?v=7qOFtL3VEBc
• 3:10 – 5:30
70
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Let’s Take a Break
• Complete Part 2 of the Partner Review.
71
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Turn in:
–Get out a piece of notebook paper• Our Plan:
–Scavenger Hunt Review– Investigation 11 Pre-Lab
• Homework (Write in Planner):–Prepare Lab Report–Homework Problems (Due 2/12)
72
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Pre Lab
• Complete steps 1 – 5 on the handout and have your formal lab report started.
• Be prepared to experiment next class.
73
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Turn in:
–Nothing• Our Plan:
–Investigation 11• Homework (Write in Planner):
–Lab Report due Next Class (2/10)
74
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Turn in:
– Lab Report (rubric on top)
• Our Plan:– Review Activity– Elephant Toothpaste Demo– Notes – Catalysts & Rate Determining Steps– Finish Homework Problems
• Homework (Write in Planner):– Homework Problems
75
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Effect of Temperature onthe Rates of Reactions
• In 1889, Svante Arrhenius proposed the following expression for the effect of temperature on the rate constant, k:
k = Ae–Ea/RT
• The constant A, called the frequency factor, is an expression of collision frequency and orientation; it represents the number of collisions per unit time that are capable of leading to reaction.
• The term e–Ea/RT represents the fraction of molecular collisions sufficiently energetic to produce a reaction.
76
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
I like this equation better…
• Look at Eq. 13.16 on p. 551 of the text!
77
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Example 13.9
Estimate a value of k at 375 K for the decomposition of dinitrogen pentoxide illustrated in Figure 13.15, given that
k = 2.5 x 10–3 s–1 at 332 K.
78
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Try it Out
EX 13.9 B: Di-tert-butyl peroxide (DTBP) is used as a catalyst in the manufacture of polymers. In the gaseous state, DTBP decomposes to acetone and ethane by a first-order reaction.
(C4H9)2O2 (g) → 2(CH3)2CO (g) + C2H6 (g)
The half-life of DTBP is 17.5 h at 125ᵒC and 1.67 h at 145ᵒC. What is the activation energy, Ea, of the decomposition reaction?
79
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Reaction Mechanisms
• Analogy: a banana split is made by steps in sequence: slice banana; three scoops ice cream; chocolate sauce; strawberries; pineapple; whipped cream; end with cherry.
• A chemical reaction occurs according to a reaction mechanism—a series of collisions or dissociations—that lead from initial reactants to the final products.
• Like making a banana split, three molecules will not collide simultaneously very often, so steps of a reaction mechanism involve only one or two reactants at a time.
80
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Reaction Mechanisms
• An elementary reaction represents, at the molecular level, a single step in the progress of the overall reaction.
• A proposed mechanism must:– account for the experimentally determined rate
law.– be consistent with the stoichiometry of the
overall or net reaction.
81
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Molecularity
The molecularity of an elementary reaction refers to the number of free atoms, ions, or molecules that collide or dissociate in that step.
Termolecular processes are unusual, for the
same reason that three basketballs shot at the same time are unlikely to collide at the same
instant …
82
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
The Rate-Determining Step
• The rate-determining step is the crucial step in establishing the rate of the overall reaction. It is usually the slowest step.
• Some two-step mechanisms have a slow first step followed by a fast second step, while others have a fast reversible first step followed by a slow second step.
Slow
Fast
Mechanism for
2 NO + O2 --> 2 NO2
83
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
An Example
• Given the reaction:
2A + 2B → C + D rate = k[A]2[B]
Could take place by the following three-step mechanism:
I. A + A ↔ X (fast)
II. X + B → C + Y (slow)
III. Y + B → D (fast)
84
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Intermediates
• X & Y are called intermediates because they appear in the mechanism, but they cancel out of the balanced equation.
• They are products from one reaction and then a reactant in the next.
85
General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
An Example
• The steps of a reaction mechanism must add up to equal the balanced equation with all intermediates cancelling out. Let’s try it with our example.
I. A + A ↔ X (fast)
II. X + B → C + Y (slow)
III. Y + B → D (fast)
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Rate-determining Step
• As in any process where many steps are involved, the speed of the whole process can’t go faster than the speed of the slowest step in the process.
• The slowest step of a reaction is the rate-determining step.
• Because the slowest step is the most important step in determining the rate of a reaction, the slowest step and the steps leading up to it are used to see if the mechanism is consistent with the rate law for the overall reaction.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
An Example
• Let’s look at our reaction again and show that it is consistent with the rate law:
2A + 2B → C + D rate = k[A]2[B]
I. A + A ↔ X (fast)
II. X + B → C + Y (slow)
III. Y + B → D (fast)
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
An Example (p. 199 Cracking AP Chemistry Exam)
1. Write rate law for slow step.
2. X is an intermediate, we need to eliminate it from the rate law.
3. Solve for [X] in terms of [A].
4. Substitute for [X] in our second step.
5. Now we have the rate law.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Fast step: I2 2 I
Slow step: 2 I + H2 2 HI
k1
k–1
k2
Example 13.10 For the reaction H2(g) + I2(g) --> 2 HI(g), a proposed mechanism is below. What is the net equation for the overall reaction, and what is the order of the reaction according to this mechanism?
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
EX 13.10 A
The decomposition of nitrosyl choride,
2NOCl (g) → 2NO (g) + Cl2 (g)
Is a first-order reaction. Propose a mechanism for this reaction consisting of one fast step and one slow step.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Catalyst
• A catalyst provides an alternative reaction pathway of lower activation energy
• Participates in a chemical reaction w/o undergoing permanent change
• Speeds up without being consumed in the reaction. It is neither a reactant nor product in a reaction.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Catalysis – how does it work
• In general, a catalyst works by changing the mechanism of a chemical reaction.
• Often the catalyst is consumed in one step of the mechanism, but is regenerated in another step.
• The pathway of a catalyzed reaction has a lower activation energy than that of an uncatalyzed reaction, so more molecules at a fixed temperature have the necessary activation energy.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Effect of Catalyst on Reaction Profile and Activation Energy
A catalyst lowers the activation energy, making it
easier for the reactants to “climb the energy hill” and
form the products.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
A Kinetics Pick Up Line…
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Homogeneous Catalysis
Ozone decomposition catalyzed by chlorine atoms has a much lower activation energy and proceeds much more rapidly than the uncatalyzed reaction
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Heterogeneous Catalysis
• Many reactions are catalyzed by the surfaces of appropriate solids.
• A good catalyst provides a higher frequency of effective collisions.
• Four steps in heterogeneous catalysis:– Reactant molecules are adsorbed.– Reactant molecules diffuse along the surface.– Reactant molecules react to form product molecules.– Product molecules are desorbed (released from the
surface).
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Heterogeneous Catalysis
Hydrogen is adsorbed onto the surface of a
nickel catalyst. A C=C approaches …
… and is adsorbed.
Hydrogen atoms attach to the carbon
atoms, and the molecule is desorbed.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
A Surface-Catalyzed Reaction
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Enzyme Catalysis• Enzymes are high-molecular-mass proteins that usually
catalyze one specific reaction, or a set of similar reactions.• The reactant substance, called the substrate (S), attaches
itself to an area on the enzyme (E) called the active site, to form an enzyme-substrate complex (ES).
• The enzyme–substrate complex decomposes to form products (P), and the enzyme is regenerated.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Factors Influencing Enzyme Activity
The rates of enzyme-catalyzed reactions are influenced by factors such as concentration of the substrate, concentration of the enzyme, acidity of the medium, and temperature.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Mercury Poisoning: An Example of Enzyme Inhibition
When Hg reacts with an enzyme …
… the Hg binds to sulfur atoms …
… changing the shape of the active site, so
that it no longer “fits” the substrate.
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Homogeneous Catalysis
Step 1: A + catalyst → intermediate + C
Step 2: B + intermediate → D + catalyst
Net equation: A + B → C + D
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Identifying Catalysts and intermediate species
O3 + Cl∙ --> ClO∙ + O2
ClO· + O∙ --> Cl∙ + O2
Catalyst?
Intermediate?
Net Equation?
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Crash Course Review
• http://www.youtube.com/watch?v=7qOFtL3VEBc
• 7:15 - end
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Finish the HW All homework problems are due on Wednesday!
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Before Class:
– Mark Homework Questions on the Board
• Our Plan:– Homework Questions/Check HW– Worksheet Race– Study Guide
• Homework (Write in Planner):– Test Next Class– Breakfast Club 6 am on Friday
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Study Guide Changes
•7 – do 39 a only•11 – do 25 a and b only
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General Chemistry 4th edition, Hill, Petrucci, McCreary, PerryPrentice Hall © 2005 Chapter Thirteen
Today…• Turn in:
–Nothing• Our Plan:
–Study Guide Questions–Test
• Homework (Write in Planner):–Complete the POGIL (Day 1 ONLY)