15 Chem Kinet
15 Chem Kinet
15 Chem Kinet
Chemical kinetics: the study of reaction rate, a quantity conditions affecting it, the molecular events during a chemical reaction (mechanism), and presence of other components (catalysis). Factors affecting reaction rate: Concentrations of reactants Catalyst Temperature Surface area of solid reactants or catalyst What quantities do we study regarding chemical reactions?
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t Define reaction rate and explain Average reaction rate Instantaneous reaction rate (2 tangents shown) Initial reaction rate 15 Chemical Kinetics
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t
2
2 N2O5 = 4 NO2 + O2
Solution: (0.93 1.24)e-2 0.31e-2 M Decomposition rate of N2O5 = = 1200 600 600 s = 5.2e-6 M s-1.
Note however, rate of formation of NO2 = 1.02e-5 M s-1. rate of formation of O2 = 2.6e-6 M s-1.
Be able to do this type problems
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barometer
The reaction is 1st order wrt all three reactants, total order 3.
rate
First order, rate = k [A]
[A] = ___?
The variation of reaction rates as functions of concentration for various order is interesting.
15 Chemical Kinetics Mathematical analysis is an important scientific tool, worth noticing. 7
Learn the strategy to determine the rate law from this example.
Figure out the answer without writing down anything.
Solution next
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Exprmt 1 2 3 4
Initial rate M s-1 1.15e-6 2.30e-6 1 for H2O2 2.30e-6 1 for I1.15e-6 0 for H+
1.15e-6 = k [H2O2]x [I-]y [H+]z 1.15e-6 k (0.010)x(0.010)y(0.0050)z ----------- = ------------------------------------2.30e-6 k (0.020)x(0.010)y(0.0050)z x=1 exprmt 1 exprmt 2 1 ---- = 2
( )
1 --- x 2
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The rate is the same as the rate constant k, when concentrations of reactants are all unity (exactly 1), doesnt matter what the orders are.
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Solution: Please note the stoichiometry of equation and how the rate changes. d[I]/dt = 3 d[H2O2]/dt = 3* 0.0115 [H2O2] [I] = 0.0345 * 0.5 * 0.5 = 0.0086 M s-1
In order to get a unique rate constant k, we evaluate k for the reaction a A + b B product this way rate = -1/a d[A]/dt = -1/b d[B]/dt = k [A]x [B]y
15 Chemical Kinetics Note the reaction rate expression and the stoichiometry of equation. 11
This example illustrates the strategy to determine, and a reliable method to solve rate-law experimentally.
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Solution next
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Assume rate = k [A]x[B]y[C]z Therefore 8 = 2x log 8 = x log 2 x = log 8 / log 2 =3 0.800 k 0.2x 0.1y 0.1z ----- = ---------------------0.100 k 0.1x 0.1y 0.1z
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d[A] / dt = k
d[A] = k [A] dt d[A] = k [A]2 dt
[A] = [A]o k t
[A] = [A]o e k t or ln [A] = ln [A]o k t 1 1 = k t [A] [A]o [A] conc at t
[A]o conc at t = 0
Describe, derive and apply the integrated rate laws Learn the strategy to determine rate-law Kinetics 15 Chemical
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[A] = [A]o e k t
ln [A] = ln [A]o k t
t
t
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or
ln [A]
k t1/2 = ln 2 = 0.693
relationship between k
Radioactive decay usually follow 1st order kinetics, and half life of an isotope is used to indicate its stability.
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Solution next
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Calculate k (What is the rate constant? k = 0.0499) Calculate the half life (What is the half life? Half life = 13.89) Calculate [A] when t = 5 min. (What is the concentration when t = 5 min?) Calculate t when [A] = 0.0100. (Estimate the time required for 90% of A to decompose.)
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The rate constant k at some temperature is 0.100 /min. The initial concentration of butadiene [B] is 2.0 M.
Calculate the time required for [B] = 1.0 and 0.5 M
Solution next
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1 1 [B] [B]o
=kt
t=
10
15
30
35
0.29
0.25
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1/[B]
t=
10
15
30
0.29
35
0.25
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Plot of [B] vs. t & 1/[B] vs. t for 2nd Order Reactions
t= 1 5 10 15 30 0.29 35 0.25 [B] = 1.67 1.0 0.67 0.50
[B]
[B]o [B] = [B]o k t + 1
1 [B]
1 [B]
1 = k t [B]o
t
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k=Zfp
Z: collision frequency constant p, the fraction with proper orientation f, fraction of collision having sufficient energy for reaction f is related to the potential energy barrier called activation energy, Ea. f e Ea / RT or exp ( Ea / R T) Thus,
Potential energy
Ea
reaction
k = A e Ea / RT
constant
P+D
k1 Ea 1 1 ln = k2 R T1 T2
1903 Nobel Prize citation in recognition of the extraordinary services he has rendered to the advancement of chemistry by his electrolytic theory of dissociation
How does temperature affect reaction rates? Derive and apply these relationship to solve problems, 15 and recall the Clausius-Clapeyron Chemical Kinetics equation.
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Ea / R T
Make sure you know how to transform the formula into these forms.
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ln (A / k) = Ea / R T
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The rate constant k = 1.0e-10 s-1 at 300 K and the activation energy Ea = 111 kJ mol-1. What are A, k at 273 K and T when k = 1e-11?
A = k eEa / R T = 1e-10 s-1 exp (111000 J mol-1 / (8.314 J mol-1 K 1*300 K)) = 2.13e9 s-1
k = 2.13e9 s-1 exp ( 111000 J mol-1) / (8.314 J mol-1 K 1*273 K) = 1.23e-12 s-1 T = Ea / [R* ln (A/k)] = 111000 J mol-1 / (8.314*46.8) J mol-1 K-1 = 285 K
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Use graphic method to discuss the variation of k vs. T variation of k vs 1 / T variation of ln(k) vs T variation of ln(k) vs 1 / T
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Br + Br + Ar Br2 + Ar*
rate = k [Br]2[Ar]
Caution: Derive rate laws this way only for elementary reactions.
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Write down the rate laws and describe them as uni- bi- or ter-molecular steps yourself, please.
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35
slow fast
Solution
The slow step determines the rate, and the rate law is:
rate = k1 [H2O2] [I ]
Since both [H2O2] and [I ] are measurable in the system, this is the rate law.
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Solution: The fast equilibrium condition simply says that k1 [Br2] = k-1 [Br]2 and [Br] = (k1/k-1 [Br2]) The slow step determines the rate law, rate = k2 [H2] [Br] Br is an intermediate = k2 [H2] (k1/k-1 [Br2]) = k [H2] [Br2] ; k = k2 (k1/k-1) M- s -1 total order 1.5
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The slow step determines the rate, rate = k2 [NO2] [NO3] From 1, we have [NO2] [NO3] = K [N2O5]
Thus, rate = K k2 [N2O5]
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Deriving rate laws from mechanisms The steady-state approximation is a general method for deriving rate laws when the relative speed cannot be identified. It is based on the assumption that the concentration of the intermediate is constant.
steady-state approximation
[Intermediate] Rate of producing the intermediate, Rprod, is the same as its rate of consumption, Rcons.
Rprod > Rcons Be able to apply the steadystate approximation to derive rate laws
Rprod = Rcons
time
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Lets assume the mechanism for the reaction. Steady-state H2 + I2 2 HI approximation as follows. Step (1) I2 k1 2 I Step (1) 2 I k-1 I2 Step (2) H2 + 2 I k2 2 HI Derive the rate law. Derivation: rate = k2 [H2] [I] 2 (cause this step gives products) but I is an intermediate, this is not a rate law yet. Since k1 [I2] (= rate of producing I) Steady state = k-1 [I]2 + k2 [H2] [I]2 (= rate of consuming I) Thus, k1 [I2] [I]2 = k-1 + k2 [H2] rate = k1 k2 [H2] [I2] / {k-1 + k2 [H2] }
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Steady-state approximation - 3
From the previous result: k1 k2 [H2] [I2] rate = {k-1 + k2 [H2] } Discussion: (i) If k-1 << k2 [H2] then {k-1 + k2 [H2]} = k2 [H2] , then rate = k1 k2 [H2] [I2] / {k2 [H2] } = k1 [I2] (pseudo 1st order wrt I2) using large concentration of H2 or step 2 is fast (will meet this condition). (ii) If step (2) is slow, then k2 << k1, and if [H2] is not large, we have {k-1 + k2 [H2]} = k-1 and rate = k1 k2 [H2] [I2] / k1 = k2 [H2] [I2]
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Steady-state approximation - 4
In an alkaline solution, peroxydisulfate oxidizes sulfite to yield sulfate, S2O82- + SO32- + 2 OH- 3 SO42- + H2O. The following mechanism has been proposed: i S2O82- + SO32- k1 S2O72- + SO42ii S2O72- + H2O k2 2 SO42- + 2 H+ iii H+ + OH- k3 H2O (fast equilibrium to be discussed) Steady-state approximation follows these steps: What is or are the intermediates I? Use which step to give the rate law that may involve [I]? Express the rates of producing and consuming intermediate(s) Express [I] of intermediate(s) in terms of [Reactants] Derive the rate law in terms of [Reactants] Discuss See page 607Kinetics Text 15 Chemical PHH
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Catalysis
Energy A catalyst is a substance that changes the rate Uncatalyzed rxn of a reaction by lowing the activation energy, Ea. It participates a reaction in forming an intermediate, but is regenerated. Enzymes are marvelously selective catalysts.
A catalyzed reaction, NO (catalyst) 2 SO2 (g) + O2 2 SO3 (g) via the mechanism i 2 NO + O2 2 NO2 (3rd order) ii NO2 + SO2 SO3 + NO
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Catalyzed rxn
rxn
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When the catalyst is in a different phase than reactants (and products), the process involve heterogeneous catalysis. Chemisorption, absorption, and adsorption cause reactions to take place via different pathways. Platinum is often used to catalyze hydrogenation
Catalytic converters reduce CO and NO emission.
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Heterogeneous catalysts
Ceryx's vision is to design, produce, and commercialize advanced systems that balance Cost, Performance, Emissions Reduction, and Fuel Penalty to make the economics of pollution control viable. We explore new ways to look at the air quality challenges faced by industry and search for potential solutions by combining proven technologies with state-of-the-art science. Catalyzed reactions: CO + O2 CO2 2 NO N2 + O2
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X-ray 3-D structure of fumarate reductase. It reduces fumerate, an important role in the metabolism of anaerobic bacteria, 50 from Max Planck Inst.
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