Beruflich Dokumente
Kultur Dokumente
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Will the reaction occur? Ch. 5, 19 How fast will the reaction occur? Ch. 14 How far will the reaction proceed? Ch. 15
Review: concentration units, graphing (line, slope) Work with reaction rates. Determine a rate law for a given reaction from experimental data. Work with rate laws. Understand the factors that affect the rate of a chemical reaction. Calculate the activation energy.
C(s, diamond)
H
rxn
C(s, graphite)
studies the rates at which chemical reactions occur. gives information about how the reaction occur, that is, the reaction mechanism Determining the reaction mechanism is the overall goal of kinetic studies. (sect. 6)
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Physical state of the reactants states that promote contact have faster rates; homogeneous vs. heterogeneous Concentration of the reactants: conc. , rate (or pressure for gases) Temperature: temp. , rate due to higher molecular energy and speed (section 5) Catalysts: rate by changing the mechanism and reaction energy (section 7) Other physical things like stirring and grinding solid reactants.
rate
Reaction rate change in concentration per unit time; M/s or mol/Ls Rates are determined by monitoring concentration as a function of time. Rates are positive quantities; for reactant A:
1 time
rate
[ A] t
final initial
In this reaction, the concentration of butyl chloride, C4H9Cl, was measured at various times.
rate
[ A] t
Instantaneous rate rate at a specific time Average rate [A] over a specific time interval Initial rate instantaneous rate at t = 0 Note: Rates and rate laws are not based on stoichiometry!! They must be determined experimentally.
The molar ratios between reactants and products correspond to the relative rates of the reaction. Relative rates relationship between rates of reactant disappearance and product appearance at a given time. 2 HI(g) H2(g) + I2(g)
rate
1 [ HI ] 2 t
[H 2 ] t
[I 2 ] t
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2.
aA + bB cC + dD
General form of rate law: [A], [B] conc. in M or P rate = k[A]m[B]n k rate constant; units vary m, n reaction orders Reaction orders and, thus, rate laws must be determined EXPERIMENTALLY!!! Note: m a and n b Overall order = sum of individual orders Rate constant is independent of concentration.
2
3 2
2X
3X 4X
2nd (2)
9X
X
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What is the order with respect to NO? What is the order with respect to H2? What is the overall order? If [NO] is doubled, what is the effect on the reaction rate? If [H2] is halved, what is the effect on the reaction rate? What are the units of k?
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2.
Exp. #
[NH4+]o
[NO2]o
1
2
0.100
0.100
0.0050
0.0100
1.35 x 10-7
2.70 x 10-7
0.200
0.0100
5.40 x 10-7
Exp. # 1 2
0.20
0.20
1.45
[Br]o 0.10
[H+]o 0.10
2 3 4
1st order
integrate
rate
[ A] t
k[ A]
ln[ A]t
Plot: ln[A] vs. t slope = k
y = mx + b
kt ln[ A]o
[ A]o ln [ A]t
[ A]o
2nd
order
integrate
rate
[ A] t
k[ A]2
1 [ A]t
y = mx + b
1 kt [ A]o
1 [ A]t
1 [ A]o
[ A]o
zero order
integrate
rate
[ A] t
k[ A]
[ A]t
Plot: [A] vs. t slope = k
kt [ A]o
y = mx + b
[ A]o [ A]t
[ A]o
2,000 5,000
8,000 12,000
335 180
95.5 41.7
15,000
22.4
39 80
140 210
0.274 0.238
0.190 0.146
[ A]t
[ A]0 2
[ A]t [ A]0
1 @ t1/ 2 2
kt kt1/ 2
0.693 kt1/ 2
Note: Radioactive decay follows 1st order kinetics.
t1/ 2
0.693 k
t1/ 2
1 k [ A]0
Zero half-life
All half-lives different length of time Dependent on initial concentration
t1/ 2
[ A]0 2k
Order
zero Rate law rate = k 1st rate = k[A] 2nd rate = k[A]2
Integrated [A]t=kt+[A]0 ln[A]t=kt+ln[A]0 1/[A]t=kt+1/[A]0 rate law Straight[A] vs. t ln[A] vs. t 1/[A] vs. t line plot Slope k k k
Half-life (t1/2)
[A]o/2k
0.693/k
1/k[A]0
BLB 39
Generally, as temperature increases, so does reaction rate. This is because k is temperature dependent.
Collision theory
In a chemical reaction, bonds are broken and new bonds are formed. In order for molecules to react, they must collide. Collisions are either effective or ineffective due to orientation of molecules. Collisions must have enough energy to overcome the barrier to reaction, the activation energy. Temperature affects the number of collisions.
Molecular Collisions
Energy barrier (hump) that must be overcome for a chemical reaction to proceed Activated complex or transition state arrangement of atoms at the top of the barrier
Energy difference between the reactant and the highest energy along the reaction pathway Reaction specific Rate of reaction is dependent upon the magnitude of Ea; Ea , rate (generally) Temperature independent
Maxwell-Boltzman Distribution
Svante Arrhenius developed an equation for the mathematical relationship between k and Ea. Ea RT
Ae
k ln k ln k
y
Ae
Ea RT
Ea ln A RT Ea 1 R T
= m x
where :
ln A
+ b
R 8.3145 T in K
J mol K
Ea R
Ea
m R
y x
ln k 2 ln k1 or 1 1 1 T2 T1 T2
k2 ln k1 1 T1
Reactions occur in a series of elementary steps collectively called a mechanism. Determining the reaction mechanism is the overall goal of kinetic studies. One step, the rate-determining step, is much slower than the other. Usually, an intermediate (isolable) or a transition state (non-isolable) is formed at some point during the reaction. molecularity the number of molecules that participate in a reaction
Catalysts increase the rate of a reaction without being consumed or changing chemically Accomplished by lowering the activation energy and changing the reaction mechanism. Heterogeneous vs. homogeneous catalysis Examples:
Catalytic converter (p. 608) Enzymes in the body (pp. 609-611) Ozone depletion (pp. 774-775)