Chem. Kinetics
Chem. Kinetics
Chem. Kinetics
Chemical kinetics: the study of reaction rate, n 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
change (t Define reaction rate and explain Average reaction rate Instantaneous reaction rate (2 tangents shown) Initial reaction rate 15 Chemical Kinetics
([ ]
t
2
barometer
The reaction is 1st order wrt all three reactants, total order 3.
[A] = ___?
The variation of reaction rates as functions of concentration for various order is interesting.
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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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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 n exprmt 1 n exprmt 2 1 ---- = 2
( )
1 --- x 2
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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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Describe, derive and apply the integrated rate laws Learn the strategy to determine rate-law Kinetics 15 Chemical
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t t
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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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If the rate-law is known, what are the key parameters? Apply the right model and work out all the parameters.
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Solution next
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1 1 [B] [B]o
=kt
t=
10
15
30 0.29
35 0.25
[B] = 1.67 1.0 0.67 0.50 Work out the formulas and then evaluate values
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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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Potential energy Ea
reaction
k = A e Ea / RT
constant
R+Ap (H exothermic
15 Chemical Kinetics Explain the various terms and energy changes in a chemical reaction
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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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Use the formula derived earlier: 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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Add these two equations led to the overall reaction NO2 + CO = NO + CO2 (overall reaction) A mechanism is a proposal to explain the rate law, and it has to satisfy the rate law. A satisfactory explanation is not a proof. Explain terms in red
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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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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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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
time
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Lets assume the mechanism for the reaction. Steady-state H2 + I2 p 2 HI approximation as follows. Step (1) I2 k1p 2 I Step (1) 2 I k-1p I2 Step (2) H2 + 2 I k2p 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 2 + k [H ] [I]2 = k-1 [I] (= rate of consuming I) 2 2 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- p 3 SO42- + H2O. The following mechanism has been proposed: i S2O82- + SO32- k1p S2O72- + SO42ii S2O72- + H2O k2p 2 SO42- + 2 H+ iii H+ + OH- k3p 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 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 p 2 SO3 (g) via the mechanism i 2 NO + O2 p 2 NO2 (3rd order) ii NO2 + SO2 p SO3 + NO
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Uncatalyzed rxn
Catalyzed rxn
rxn
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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 pCO2 2 NO p 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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