This document provides an overview of reaction rates and mechanisms. It defines reaction rates as the change in concentration of reactants or products over time. Reaction rates depend on temperature, catalyst concentration, and surface area. The rate law describes how the reaction rate depends on reactant concentrations and their orders. Determining rate laws involves measuring initial rates while varying one reactant concentration at a time. Integrated rate laws relate concentration over time for first and second order reactions. Reaction mechanisms involve elementary reaction steps and intermediates. The overall rate law depends on the rate determining step.
This document provides an overview of reaction rates and mechanisms. It defines reaction rates as the change in concentration of reactants or products over time. Reaction rates depend on temperature, catalyst concentration, and surface area. The rate law describes how the reaction rate depends on reactant concentrations and their orders. Determining rate laws involves measuring initial rates while varying one reactant concentration at a time. Integrated rate laws relate concentration over time for first and second order reactions. Reaction mechanisms involve elementary reaction steps and intermediates. The overall rate law depends on the rate determining step.
This document provides an overview of reaction rates and mechanisms. It defines reaction rates as the change in concentration of reactants or products over time. Reaction rates depend on temperature, catalyst concentration, and surface area. The rate law describes how the reaction rate depends on reactant concentrations and their orders. Determining rate laws involves measuring initial rates while varying one reactant concentration at a time. Integrated rate laws relate concentration over time for first and second order reactions. Reaction mechanisms involve elementary reaction steps and intermediates. The overall rate law depends on the rate determining step.
This document provides an overview of reaction rates and mechanisms. It defines reaction rates as the change in concentration of reactants or products over time. Reaction rates depend on temperature, catalyst concentration, and surface area. The rate law describes how the reaction rate depends on reactant concentrations and their orders. Determining rate laws involves measuring initial rates while varying one reactant concentration at a time. Integrated rate laws relate concentration over time for first and second order reactions. Reaction mechanisms involve elementary reaction steps and intermediates. The overall rate law depends on the rate determining step.
Experimental Determination of Rate Dependence of Rate on Concentration Change of Concentration with Time Temperature and Rate; Collision and Transition-State Theories. Arrhenius Equation
Reaction Mechanisms Elementary Reactions Rate Law and the Mechanism Catalysis
Reaction Rates Deal with the speed of a reaction and controlled by: Proportional to concentrations of reactants Proportional to catalyst concentration; catalyst = a substance that increases the rate of reaction without being consumed in the reaction. Larger surface area of catalyst means higher reaction rate (more sites for reaction to take place). Temperature: Higher temperature of reaction means faster.
Definition of Reaction Rate
Reaction rate = increase in concentration of product of a reaction as a function of time or decrease in concentration of reaction as a function of time. Thus the rate of a reaction is:
0.090
Concentration, M
Rate A
Concentration vs Reaction Time
A + 2B --> 3C
conc change A [ A ]
time change t [ A ]2 [ A ]1 t 2 t1
Init Rate 0.045
Inst. Rate Ave. Rate
0.000 0
250 Tim e, s
Rates are expressed as positive numbers. For the reaction in
the graph we have: RA
[ A ] t
RB
[B] t
RC
[C] t
500
Reaction Rates and Stoichiometry
A + B C; RC = RA = RB. A + 2B 3C; R 1 R 1 R A
E.g.Calculate the rate of decomposition of HI in the
reaction: 2HI(g) H2(g) + I2(g). Given: After a reaction time of 100 secs. the concentration of HI decreased by 0.500 M. For the general reaction: aA + bB cC + dD a a a R A RB R C RD b c d
E.g. For the reaction 2A + 3B 4C + 2D; determine
the rates of B, C and D if the rate of consumption of A is 0.100 M/s.
Rate Laws and Reaction Order
Rate Law an equation that tells how the reaction rate depends on the concentration of each reaction. Reaction order the value of the exponents of concentration terms in the rate law. For the reaction: aA + bB cC + dD, the initial rate of reaction is related to the concentration of reactants. Varying the initial concentration of one reactant at a time produces rates, which will lead to the order of each reactant. The rate law describes this dependence: R = k[A]m[B]n where k = rate constant and m and n are the orders of A and B respectively. m = 1 (A varied, B held constant) gives R = k[A]. Rate is directly proportional to [A]. Doubling A doubles R m = 2 (A varied, B held constant) gives R = k[A]2. The rate is proportional to [A]2. Doubling A quadruples R.
E.g. Determine order of each reactant:
HCOOH(aq) + Br2(aq) 2H+(aq) + 2Br(aq) + CO2(g) R = k[Br2] E.g. The formation of HI gas has the following rate law: R = k[H2][I2]. What is the order of each reactant?
Experimental Determination of a Rate Law: First
Order Varying initial concentration of reactants changes the initial rate (usually all but one held constant) like one with two unknowns. Initial rate is the initial slope of the graph shown. As the initial concentration of that compound increases so does the rate.
Concentration vs Reaction Time
A + 2B --> 3C
[A] 0, M
0.100
0.000 0
250
500
Tim e, s
Initial Rate vs. [A]o
Initial rate vs. [A]o plotted.
If straight line then reaction is first order and slope is rate constant.
0.0005 0.0004
Ro
Second order rate law determined in
like manner.
0.050
0.0003 0.0002 0.0001 0.0000 0.00
0.03
0.05 [A]o
0.08
0.10
Rate Law for All Reactants
Order for all components done same way. E.g. Determine the reaction order for each reactant from the table. (aq)+5Br(aq)+6H+(aq)3Br2(aq)+3H2O(l) BrO 3
[BrO3 ]o 0.10 0.20 0.10 0.20
[Br]o 0.10 0.10 0.30 0.10
[H+]o 0.10 0.10 0.10 0.15
Ro 1.2 2.4 3.5 5.4
Eg. 2: Determine the reaction orders for the reaction indicated from the data provided. A + 2B + C Products. [A]o 2.06 0.87 0.50 1.00
[B]o 3.05 3.05 0.50 0.50
[C]o 4.00 4.00 0.50 1.00
Ro 3.7 0.66 0.013 0.072
Integrated Rate Law: FirstOrder Reaction
For a first order reaction, Rate = [A]/t = k[A] or RA = d[A]/dt = k[A].
Use of calculus leads to: ln
Allows one to calculate the [A] at any time after the start of the reaction. E.g. Calculate the concentration of N2O remaining after its decomposition according to 2N2O(g) 2N2(g) + O2(g) if its rate is first order and [N2O]o = 0.20M, k = 3.4 s1 and T = 780C. Find its concentration after 100 ms.
Linearized forms: ln[ A ] kt ln[ A ]o or log[ A ]
t log[ A ]o 2.303 Plot ln[A] vs t. Slope of straight line leads to rate constant, k. E.g. When cyclohexane(let's call it C) is heated to 500 oC, it changes into propene. Using the following data from one experiment, determine the first order rate constant.: t,min 0.00 5.00 10.00 15.00 [C],mM 1.50 1.24 1.00 0.83
[A] k [A] or log
t kt [ A ]o 2.303 [ A ]o
Half-Life: First Order Reaction
Half-life of First order reaction, t1/2 = 0.693/k. the time required for the concentration of the reactant to change to of its initial value. i.e. at t1/2 , [A] = [A]o E.g. For the decomposition of N2O5 at 65 C, the half-life was found to be 130 s. Determine the rate constant for this reaction. For n half-lives t = n*t1/2 [A] =
2n
[A]o
1 / 2[ A]o ln k t1/ 2 [ A]o 1 ln k t1/ 2 2 t1/ 2 0.693 / k
1 n ln k n t1 / 2 2 1 ln k tn 2n 1 [ A ]t n [A] 2 o
SecondOrder Reactions: Integrated Rate
Law Rate law: R = k[A]2 and the integrated rate equation is: 1 1 kt [ A ]t [ A ]o
1 Plot of [ A ] vs. t gives a straight line with a slope of k. t
1 Half-life is: t1/ 2 k [ A ] o
E.g. At 330C, the rate constant for the decomposition of
NO2 is 0.775 L/(mol*s). If the reaction is second-order, what is the concentration of NO2 after 2.5x102 s if the starting of concentration was 0.050 M?
Reaction Mechanisms
Give insight into sequence of reaction events leading to product
(reaction mechanism). Each of the steps leading to product is called an elementary reaction or elementary step. Consider the reaction of nitrogen dioxide with carbon dioxide which is second order on NO2: NO2(g) + CO(g) NO(g) + CO2(g) Rate = k[NO2]2. Rate law suggests at least two steps. A proposed mechanism for this reaction involves two steps. Step 1 Step 2 Overall
2NO2(g) NO3(g) + NO(g)
NO3(g) +CO(g) NO2(g) + CO2(g) NO2 + CO NO + CO2
NO3 is a reaction intermediate = a substance that is produced and
consumed in the reaction so that none is detected when the reaction is finished.
The elementary reactions are often described in terms of their
molecularity. Unimolecular One particle in elementary. Bimolecular = 2 particles and Termolecular = 3 particles
Rate Laws and Reaction Mechanisms
Overall reaction order is often determined by the rate determining step.
Use rate law of limiting step; No intermediates! 2NO2(g) NO3(g) + NO(g), NO3(g) +CO(g) NO2(g) + CO2(g) NO2 + CO NO + CO2
R1 = k1[NO2]2
Slow
R2 = k2[NO3][CO]
Fast
Robs = k[NO2]2
E.g. Determine the rate law for the following mechanism:
2*[N2O5(g) NO2 (g) NO3 (g) ]
Fast
k2 NO3(g) +NO2(g) NO2 (g) NO(g) O 2 (g)
Slow
k1
k 1
Fast
k3 NO3 + NO 2NO2 (g) k obs 2N2O5(g)
4NO2 (g) O 2 (g)
Use steady state approximation. at equilibrium rates of forward and
reverse reactions are same. Use to eliminate intermediates from rate law equations. R1 R1 k 1 [N2O5 ] k 1[NO2 ][NO3 ]
