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Acknowledgements: Many of the images are adopted from Tro’s textbook, the only purpose of which is to enhance student learning. Key terms, concepts, skills: Refer to pp 599 – 601. Review questions: 3 – 24. Suggested problems: 25, 27, 33, 39, 43, 53, 57, 59, 69, 73, 75, 81, 93, 103. 13.1 & 2 Introduction to the Rate of a Chemical Reaction • kinetics is the study of the factors that affect the speed of a reaction and the mechanism by which a reaction proceeds. • experimentally it is shown that there are 4 factors that influence the speed of a reaction: nature of the reactants, temperature catalysts concentration • • rate of a chemical reaction is generally measured in terms of how much the concentration of a reactant decreases in a given period of time or product concentration increases for reactants, a negative sign is placed in front of the definition
as time goes on, the rate of a reaction generally slows down because the concentration of the reactants decreases. at some time the reaction stops, either because the reactants run out or because the system has reached equilibrium.
Reaction Rate and Stoichiometry • in most reactions, the coefficients of the balanced equation are not all the same H2(g) + I2(g) → 2 HI(g) • for the above reaction, for every 1 mole of H2 used, 1 mole of I2 will also be used and 2 moles of HI made, therefore the rate of change will be different • in order to be consistent, the change in the concentration of each substance is multiplied by 1/coefficient ∆[H 2 ] ∆[I 2 ] ⎛ 1 ⎞ ∆[HI] Rate = − =− = +⎜ ⎟ ∆t ∆t ⎝ 2 ⎠ ∆t • the average rate is the change in measured concentrations in any particular time period, linear approximation of a curve • the larger the time interval, the more the average rate deviates from the instantaneous rate • the instantaneous rate is the change in concentration at any one particular time, i.e., the slope at a given point of the curve • determined by taking the slope of a line tangent to the curve at that particular point, first derivative of the function. • Refer to Example 13.1 and Practice 13.1 for problem solving help and hint.
II. For the reaction 2 A(g) + B(g) → 3 C(g) a. The instantaneous rate of the reaction at 25 s. Consider the following reaction: 2 HBr(g) → H2(g) + Br2(g) a. Express the rate of the reaction with respect to each of the reactants and products. c. the concentration of HBr dropped from 0. The instantaneous rate of formation of HBr at 50 s.0 s of the reaction? Q# 27.100 M/s.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 2 of 13 Q# 25. Determine the expression for the rate of the reaction with respect to each of the reactants and products. When A is decreasing at a rate of 0.500 M to 0. If the volume of the reaction vessel in part b was 0. . a. how fast is B decreasing? How fast is C increasing? Q# 33. Make a rough sketch of a curve representing the concentration of HBr as a function of time.0 s of this reaction. In the first 15. Use the graph to calculate the following I.455 M.500 L. Calculate the average rate of the reaction in this time internal. b. III. The graph below shows the concentration of Br2 as a function of time. Consider the following reaction: H2(g) + Br2(g) → 2 HBr(g). b. The average rate of the reaction between 0 and 25 s. what amount of Br2 (in moles) was formed during the first 15. b. Assume that the initial concentration of HBr is zero.
the faster the reaction increases the frequency of reactant molecule contact concentration of gases depends on the partial pressure of the gas higher pressure = higher concentration • concentration of solution depends on the solute to solution ratio (molarity) 13. • homogeneous = present in same phase. sampling of the mixture at various times can be used when sampling is used..for each 10°C rise in temperature. powdered solids are more reactive than “blocks”: more surface area for contact certain types of chemicals are more reactive than others – e.3 Rate Law: Effect of Concentration on Rate • the Rate Law of a reaction is the mathematical relationship between the rate of the reaction and the concentrations of the reactants as well as homogeneous catalysts • the rate of a reaction is directly proportional to the concentration of each reactant raised to a power • for the reaction aA + bB → products the rate law would have the form Rate = k[A]n [B]m n and m are called the orders for each reactant k is called the rate constant .Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 3 of 13 Measuring Reaction Rate • measure the concentration of at least one component in the mixture at many points in time • there are two ways of approaching this problem (1) for reactions that are complete in less than 1 hour. the speed of the reaction doubles • there is a mathematical relationship between the absolute temperature and the speed of a reaction discovered by Svante Arrhenius which will be examined later Factors Affecting Reaction Rate:Catalysts • catalysts are substances which affect the speed of a reaction without being consumed • most catalysts are used to speed up a reaction. the component absorbs its complimentary color • total pressure – the total pressure of a gas mixture is stoichiometrically related to partial pressures of the gases in the reaction Factors Affecting Reaction Rate: Nature of the Reactants small molecules tend to react faster than large molecules. the larger the concentration of reactant molecules. catalyst is in the same phase as the reactants • heterogeneous = present in different phase. often the reaction in the sample is stopped by a quenching technique • polarimetry – measuring the change in the degree of rotation of plane-polarized light caused by one of the components over time • spectrophotometry – measuring the amount of light of a particular wavelength absorbed by one component over time.g. the activity series of metals ions react faster than molecules – no bonds need to be broken Factors Affecting Reaction Rate: Temperature • increasing temperature increases reaction rate chemist’s rule of thumb . these are called positive catalysts. it is best to use continuous monitoring of the concentration. or (2) for reactions that happen over a very long time. catalyst is in different phase as the reactant Factors Affecting Reaction Rate – Reactant Concentration • generally. gases tend to react faster than liquids which react faster than solids. catalysts used to slow a reaction are called negative catalysts.
Second-order reaction c. first order with respect to [O2]. L–1.[A]o M/s.[A]3 k = rate/[A]3 Rate = k. 0 k = rate =k mol.6 for problem solving help and hint.[A]4 k = rate/[A]4 Q# 37. First-order reaction b.[A]2 k = rate/[A]2 Rate = k.[A] k = rate/[A] s–1 Rate = k. and third order overall • Order of reaction is determined experimentally • Unit of k depends on the order of reaction A Product Order Rate k = rate/[A]m Unit of k m = expression Rate = k.s. What are the units of k for each of the following? a. Zero-order reaction Half-Life • the half-life. t1/2. .6 and Practice 13.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 4 of 13 Reaction Order • the sum of the exponents on the reactants is called the overall order of the reaction • The rate law for the reaction: 2 NO(g) + O2(g) 2 NO2(g) is Rate = k[NO]2[O2] • The reaction is second order with respect to [NO].s–1 1 2 3 4 Rate = k. of a reaction is the length of time it takes for the concentration of the reactants to fall to ½ its initial value • the half-life of the reaction depends on the order of the reaction • Refer to Example 13. mol/L.
m 2x none 0 3x none 2x 2x 1 3x 3x 2x 4x 2 3x 9x 2x 8x 3 3x 27x .Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 5 of 13 13.[A]m Conc. Time (consult Table 13.2 for summary) Zero Order Reactions • • • • Rate = –∆[A]/∆ t = k[A]o = k Linear equation? Slope? half-life? First Order Reactions • • • • Rate = –∆[A]/∆ t = k[A]1 Linear equation? Slope? half-life? Second Order Reactions • • • • Rate = –∆[A]/∆ t = k[A]2 Linear equation? Slope? half-life? Determining the Rate Law • graphically.3-6 and Practice 13. A Product rate law: rate = k. as shown earlier • can only be determined experimentally by comparing effect on the rate of changing the initial concentration of reactants one at a time • Refer to Example 13.3-6 for problem solving help and hint.4 Integrated Rate Law: Concentration vs. increase Rate increase Order.
100 0.103 0. k. B. b. Write the rate law for the reaction.200 0. A reaction in which A. The data below were collected for the following reaction: 2 NO2(g) + F2(g) → 2 NO2F(g) a. and zero order in C. Write a rate law for the reaction.400 0. The following reaction was monitored as a function of time: A → B + C A plot of In [A] versus time yields a straight line with slope –0.411 Q# 51. By what factor does the reaction rate change if [C] is doubled (and the other reactant concentrations are held constant)? f. What is the overall order of the reaction? c. What is the overall order of the reaction? 0. By what factor does the reaction rate change if the concentrations of all three reactants are doubled? Q# 43.051 b. a. If the initial concentration of A is 0. and C react to form products is first order in A. 0. second order in B.026 constant. By what factor does the reaction rate change if [B] is doubled (and the other reactant concentrations are held constant)? e. By what factor does the reaction rate change if [A] is doubled (and the other reactant concentrations are held constant)? d.250 M. What is the half-life? d. what is the concentration after 225 s? .200 0.400 0. What is the value of the rate constant (k) for this reaction at this temperature? b.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 6 of 13 Q# 39.200 0.0045/s. c. a.100 0. Write an expression for the reaction rate [NO2] (M) [F2] (M) Initial Rate (M/s) law and calculate the value of the rate 0.100 0.
Activation energy (Ea) d.5 Effect of Temperature on Reaction Rate • • changing the temperature changes the rate constant of the rate law Svante Arrhenius investigated this relationship and showed that: ⎛ − Ea k = A ⎜ e RT ⎜ ⎝ • ⎞ ⎟ ⎟ ⎠ • activation energy. Enthalpy of reaction (∆Hrxn) . Label each of the following in the diagram: a. Reactants b.42 X 10–4 s–1 at a certain temperature.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 7 of 13 Q# 53. how long will it take for the concentration to decrease to 0. What is the half-life for this reaction? b. energy barrier to the reaction – amount of energy needed to convert reactants into the activated complex. aka transition state the activated complex is a chemical species with partially broken and partially formed bonds – always very high in energy because of partial bonds Q# 57.78 M? d.00 M. If the initial concentration of SO2Cℓ2 is 1.00 x 102 s? 13. a. The decomposition of SO2Cℓ2 is first order in SO2Cℓ2 and has a rate constant of 1.150 M. The following diagram shows the energy of a reaction as the reaction progresses. what is the concentration of SO2Cℓ2 after 2. If the initial concentration of SO2Cℓ2 is 0. How long will it take for the concentration of SO2Cℓ2 to decrease to 25% of its initial concentration? c. Products c.
in order for a reaction to take place. 2. the reacting molecules must collide into each other. a. What is the value of the rate constant at 425 K? Collision Theory of Kinetics • for most reactions. whether the reacting molecules collide in the proper orientation for new bonds to form. whether the collision has enough energy to "break the bonds holding reactant molecules together".7-8 for problem solving help and hint. • once molecules collide they may react together or they may not. Determine the activation barrier for the reaction. the faster the reaction rate • when two molecules have an effective collision. b.called an activated complex or transition state . A reaction has a rate constant of 0. • collisions in which these two conditions are met (and therefore lead to reaction) are called effective collisions • the higher the frequency of effective collisions.7-8 and Practice 13. depending on two factors 1.0117/s at 400 K and 0.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 8 of 13 Arrhenius Plots • the Arrhenius Equation can be algebraically solved to give the following form: ln(k ) = − Ea ⎛ 1 ⎞ ⎜ ⎟ + ln( A) R ⎝T⎠ ⎛k ⎞ E ⎛ 1 1 ⎞ ln⎜ 2 ⎟ = a ⎜ − ⎟ ⎜ k ⎟ R ⎜T T ⎟ 2 ⎠ ⎝ 1⎠ ⎝ 1 (Refer to Example 13. a temporary. high energy (unstable) chemical species is formed .) Q# 69.689/s at 450 K.
the less frequently they will collide with the proper orientation reactions between atomic reactants generally have p = 1 reactions where symmetry results in multiple orientations leading to reaction have p slightly less than 1 for most reactions.8 kJ/mol and the frequency factor is 1. p << 1 there are some reactions that have p > 1 in which an electron is transferred (ionic species) without direct collision Q# 59.5 x 1011/s. which cannot be broken down into simpler steps and the molecules actually interact directly in this manner without any other steps • notice that the HI is a product in Step 1. it does not show up in the overall reaction – these types of species are called intermediates . 13. Calculate the rate constant of the reaction at 25° C.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 9 of 13 Collision Theory and the Arrhenius Equation • A is the factor called the frequency factor and is the number of molecules that can approach overcoming the energy barrier • there are two factors that make up the frequency factor – the orientation factor (p) and the collision frequency factor (z) • • • the proper orientation results when the atoms are aligned in such a way that the old bonds can break and the new bonds can form the more complex the reactant molecules. but then a reactant in Step 2 • since HI is made but then consumed. or at most 3 molecules • reaction mechanism describes the series of steps that occur to produce the overall observed reaction • knowing the rate law of the reaction helps us understand the sequence of steps in the mechanism An Example of a Reaction Mechanism • Overall reaction: H2(g) + 2 ICℓ(g) → 2 HCℓ(g) + I2(g) • Mechanism: 1) H2(g) + ICℓ(g) → HCℓ(g) + HI(g) 2) HI(g) + ICℓ(g) → HCℓ(g) + I2(g) • the steps in this mechanism are elementary steps. the orientation factor is less than 1 for many. The activation energy of a reaction is 56.6 Reaction Mechanisms • we generally describe chemical reactions with an equation listing all the reactant molecules and product molecules • but the probability of more than 3 molecules colliding at the same instant with the proper orientation and sufficient energy to overcome the energy barrier is negligible • most reactions occur in a series of small reactions involving 1. 2.
9 and Practice 13.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 10 of 13 Molecularity • the number of reactant particles in an elementary step is called its molecularity • a unimolecular step involves 1 reactant particle • a bimolecular step involves 2 reactant particles – though they may be the same kind of particle • a termolecular step involves 3 reactant particles – quite rare in elementary steps Rate Laws for Elementary Steps • each step in the mechanism is like its own little reaction – with its own activation energy and own rate law • the rate law for an overall reaction must be determined experimentally • but the rate law of an elementary step can be deduced from the equation of the step H2(g) + 2 ICℓ(g) → 2 HCℓ(g) + I2(g) 1) H2(g) + ICℓ(g) → HCℓ(g) + HI(g) 2) HI(g) + ICℓ(g) → HCℓ(g) + I2(g) Rate = k1[H2][ICℓ] Rate = k2[HI][ICℓ] Rate Determining Step • in most mechanisms. Consider the following two gas-phase reactions: a. one step occurs slower than the other steps • the result is that product formation cannot occur any faster than the slowest step – the step determines the rate of the overall reaction • we call the slowest step in the mechanism the rate determining step the slowest step has the largest activation energy • the rate law of the rate determining step determines the rate law of the overall reaction Validating a Mechanism • in order to validate (not prove) a mechanism. two conditions must be met: 1. which one would you expect to have the faster rate? .) Q# 71. AA(g) + BB(g) → 2 AB(g) b.9 for problem solving help and hint. the elementary steps must sum to the overall reaction 2. the rate law predicted by the mechanism must be consistent with the experimentally observed rate law (Refer to Example 13. AB(g) + CD(g) → AC(g) + BD(g) If the two reactions have identical activation barriers and are carried out under the same conditions.
What is the predicted rate law?: k1 Cℓ2(g) 2 Cℓ(g) Fast k2 Cℓ(g) + CHCℓ3(g) k3 Cℓ(g) + CCℓ3(g) k4 CCℓ4(g) Fast HCℓ(g) + CCℓ3(g) Slow Q# 81. What is the overall reaction? b.398 c) How long will it take for 90% of the 25.0 0.00 1. The data below were collected at 500 °C for the following reaction CH3CN(g) Answer the following questions.501 (at the initial concentration)? 20.0 0. . What are the intermediates in the mechanism? c. a.0 0. For the three-step mechanism below for a certain reaction answer the following questions.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 11 of 13 Q# 73. Consider the overall reaction which is experimentally observed to be second order in AB and zero order in C:: AB + C A + BC Determine whether the mechanism below is valid for this reaction. a) What are the order of the reaction Time (h) [CH3CN] (M) 0.0 0. AB + AB AB2 + A Slow k1 AB2 + C k2 AB + BC Fast Q# 75.631 b) What is the half-life for this reaction 15.316 CH3CN to convert to CH3NC? CH3NC(g).794 this temperature? 10.000 and the value of the rate constant at 5.0 0.
c) Which step is the rate limiting? d) Is the overall reaction endothermic or exothermic? Q# 103. Consider the following energy diagram showing the energy of a reaction as it progresses and answer the questions. a) Show that both of the proposed mechanisms are valid.Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 12 of 13 Q# 93. products. then regenerated in a later step . Consider the following proposed mechanisms to answer the questions. a) How many elementary steps are involved in this reaction? b) Label the reactants. b) What kind of experimental evidence might lead you to favor mechanisms II over mechanism I? Mechanism I: Mechanism II: k1 H2(g) + I2(g) → 2 HI(g) I2(g) 2 I(g) Fast Single step k2 H2(g) + 2 I(g) → 2 HI(g) Slow k3 13.7 Catalysts • catalysts are substances that affect the rate of a reaction without being consumed • they work by providing an alternative mechanism for the reaction with a lower activation energy • they are consumed in an early mechanism step. Consider the following gas-phase reaction: H2(g) + I2(g) → 2 HI(g) The reaction was experimentally determined to be first order in H2 and first order in I2. and intermediates.
Tro’s Chemistry / Chapter 13 – Chemical Kinetics / Page 13 of 13 Types of Catalysts • homogeneous catalysts are in the same phase as the reactant particles o Cℓ(g) in the destruction of O3(g) • heterogeneous catalysts are in a different phase than the reactant particles o solid catalytic converter in a car’s exhaust system Enzymes (Biological catalysts) • because many of the molecules are large and complex. most biological reactions require a catalyst to proceed at a reasonable rate • protein molecules that catalyze biological reactions are called enzymes • enzymes work by adsorbing the substrate reactant onto an active site that orients it for reaction Enzyme-Substrate Binding: Lock and Key Mechanism .
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