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Molecular motion
Topic 81 Diffusion Discussion questions 81.1 Describe the origin of the thermodynamic force. To what extent can it be regarded as an actual force?
81.2 Account physically for the form of the diffusion equation.
Exercises 81.1(a) The diffusion coefficient of glucose in water at 25 °C is
6.73 × 10−10 m2 s−1. Estimate the time required for a glucose molecule to undergo a root mean square displacement of 5.0 mm.
concentration of sucrose molecules at 10 cm above the original layer at (a) 10 s, (b) 24 h? Assume diffusion is the only transport process and take D = 5.216 × 10−9 m2 s−1.
81.1(b) The diffusion coefficient of H2O in water at 25 °C is 2.26 × 10−9 m2 s−1.
81.2(b) A layer of 10.0 g of iodine is spread uniformly over a surface of area
Estimate the time required for an H2O molecule to undergo a root mean square displacement of 1.0 cm.
10.0 cm2 and covered in hexane to a depth of 10 cm. What will be the molar concentration of sucrose molecules at 5.0 cm above the original layer at (a) 10 s, (b) 24 h? Assume diffusion is the only transport process and take D = 4.05 × 10−9 m2 s−1.
81.2(a) A layer of 20.0 g of sucrose is spread uniformly over a surface of area 5.0 cm2 and covered in water to a depth of 20 cm. What will be the molar
Problems 81.1 A dilute solution of potassium permanganate in water at 25 °C was
prepared. The solution was in a horizontal tube of length 10 cm, and at first there was a linear gradation of intensity of the purple solution from the left (where the concentration was 0.100 mol dm−3) to the right (where the concentration was 0.050 mol dm−3). What is the magnitude and sign of the thermodynamic force acting on the solute (a) close to the left face of the container, (b) in the middle, (c) close to the right face? Give the force per mole and force per molecule in each case. 81.2 A dilute solution of potassium permanganate in water at 25 °C was
prepared. The solution was in a horizontal tube of length 10 cm, and at first there was a Gaussian distribution of concentration around the centre of 2 the tube at x = 0, c(x ) = c0 e −ax , with c0 = 0.100 mol dm−3 and a = 0.10 cm−2. Determine the thermodynamic force acting on the solute as a function of location, x, and plot the result. Give the force per mole and force per molecule in each case. What do you expect to be the consequence of the thermodynamic force? 81.3 Instead of a Gaussian ‘heap’ of solute, as in Problem 81.2, suppose that 2 there is a Gaussian dip, a distribution of the form c(x ) = c0 (1−e −ax ). Repeat the calculation in Problem 81.2 and its consequences. 81.4 A lump of sucrose of mass 10.0 g is suspended in the middle of a spherical
flask of water of radius 10 cm at 25 °C. What is the concentration of sucrose at the wall of the flask after (a) 1.0 h, (b) 1.0 week? Take D = 5.22 × 10−10 m2 s−1. 81.5 Confirm that eqn 81.11 is a solution of the diffusion equation with the correct initial value. 81.6 Confirm that
by eqn 81.12 (that of a solute initially suspended at the centre of a flask of solvent)? Hint: Use ∇ = i∂/∂x + j∂/∂y + k∂/∂z. 81.8 The diffusion equation is valid when many elementary steps are taken in the time interval of interest, but the random walk calculation lets us discuss distributions for short times as well as for long. Use eqn 81.15 to calculate the probability of being six paces from the origin (that is, at x = 6λ) after (a) four, (b) six, (c) twelve steps. 81.9 Use mathematical software to calculate P in a one-dimensional random
walk, and evaluate the probability of being at x = nλ for n = 6, 10, 14, …, 60. Compare the numerical value with the analytical value in the limit of a large number of steps. At what value of n is the discrepancy no more than 0.1 per cent? 81.10 Supply the intermediate mathematical steps in Justification 81.2. 81.11 The diffusion coefficient of a particular kind of t-RNA molecule is D = 1.0 × 10−11 m2 s−1 in the medium of a cell interior. How long does it take molecules produced in the cell nucleus to reach the walls of the cell at a distance 1.0 μm, corresponding to the radius of the cell? 81.12‡ In this problem, we examine a model for the transport of oxygen
from air in the lungs to blood. First, show that, for the initial and boundary conditions c(x,t) = c(x,0) = co (0 < x < ∞) and c(0,t) = cs (0 ≤ t ≤ ∞), where co and cs are constants, the concentration, c(x,t), of a species is given by c(x , t ) = co + (cs − co ){1− erf (ξ )}
ξ (x , t ) =
x (4 Dt )1/2
is a solution of the diffusion equation with convection (eqn 81.10) with all the solute concentrated at x = x0 at t = 0 and plot the concentration profile at a series of times to show how the distribution spreads and its centroid drifts.
where erf(ξ) is the error function (see Integral G.6 in the Resource section) and the concentration c(x,t) evolves by diffusion from the yz-plane of constant concentration, such as might occur if a condensed phase is absorbing a species from a gas phase. Now draw graphs of concentration profiles at several different times of your choice for the diffusion of oxygen into water at 298 K (when D = 2.10 × 10−9 m2 s−1) on a spatial scale comparable to passage of oxygen from lungs through alveoli into the blood. Use co=0 and set cs equal to the solubility of oxygen in water. Hint: Use mathematical software.
81.7 The thermodynamic force has a direction as well as a magnitude, and in a three-dimensional ideal system eqn 81.2 becomes F = −RT∇(ln c) . What is the thermodynamic force acting to bring about the diffusion summarized
81.13 Derive eqn 81.17c for the mean radius reached in a random walk in three dimensions. Use eqn 81.12 and an argument similar to that presented in Example 81.1.
c( x , t ) =
c0 2 e −( x − x0 −vt ) /4 Dt (4 πDt )1/2
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Exercises and problems
795
Integrated activities F16.1 In a series of observations on the displacement of rubber latex spheres of radius 0.212 μm, the mean square displacements after selected time intervals were on average as follows:
t/s
30
60
90
120
1012〈x2〉/m2
88.2
113.5
128
144
These results were originally used to find the value of Avogadro's constant, but there are now better ways of determining NA, so the data can be used to find another quantity. Find the effective viscosity of water at the temperature of this experiment (25 °C).
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F16.2 Use mathematical software, a spreadsheet, or the Living graphs (labelled LG)
on the website of this book to carry out the following exercises:
(a) LG
Refer to Fig. 78.4. Plot different distributions by keeping the molar mass constant at 100 g mol−1 and varying the temperature of the sample between 200 K and 2000 K. (b) Evaluate numerically the fraction of molecules with speeds in the range 100 m s−1 to 200 m s−1 at 300 K and 1000 K. Based on your observations, provide a molecular interpretation of temperature. (c) Generate a family of curves similar to that shown in Fig. 81.3 but by using eqn 81.12, which describes diffusion in three dimensions.
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FOCUS 17 ON Chemical kinetics Topic 82
Topic 83
Topic 84
Topic 86
Reaction rates
Integrated rate laws
Reactions approaching equilibrium
Reaction mechanisms
Topic 85 Focus 9 Molecular spectroscopy
The Arrhenius equation
Focus 18
Focus 19
Focus 20
Reaction dynamics
Processes in fluid systems
Processes on solid surfaces
‘Chemical kinetics’ is the study of reaction rates. The rate of a chemical reaction might depend on variables under our control, such as the pressure, the temperature, and the presence of a catalyst, and we may be able to optimize the rate by the appropriate choice of conditions. Here we begin to see how such manipulations are possible, preparing us for the study of more complicated or more specialized cases. Topic 82 discusses the definition of reaction rate and outlines the techniques for its measurement with tools from Molecular spectroscopy. The results of such measurements show that reaction rates depend on the concentration of reactants (and products) and ‘rate constants’ that are characteristic of the reaction. This dependence can be expressed in terms of differential equations known as ‘rate laws’. ‘Integrated rate laws’ are the solutions of the rate laws and give concentrations as a function of time (Topic 83). We explore simple yet very useful integrated rate laws that appear throughout this group of Topics. An important case is the inclusion of both the forward and reverse reactions, giving rise to expressions that describe the approach to equilibrium, when the forward and reverse rates are equal (Topic 84). A result of this analysis is a useful relation between the equilibrium constant of the overall process and the rate constants of the forward and reverse reactions in the proposed mechanism. The rate constants of most reactions increase with increasing temperature. We see that the ‘Arrhenius equation’ captures this empirically determined temperature dependence by using only two parameters (Topic 85). This equation is developed theoretically in our discussion of Reaction dynamics. The study of reaction rates also leads to an understanding of the ‘mechanisms’ of reactions, their analysis into a sequence of ‘elementary steps’ (Topic 86). Here we see how to construct rate laws from a proposed mechanism. The elementary steps themselves have simple rate laws which can be combined by invoking the concept of the ‘rate-determining step’ of a reaction or either making the ‘steady-state approximation’ or assuming the existence of a ‘pre-equilibrium’. The stage is now set for detailed study of Processes in fluid systems and Processes on solid surfaces.
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What is the impact of this material? Synthetic polymers, such as nylon and polystyrene, are manufactured by stringing together and in some cases cross-linking smaller units known as ‘monomers’. In Impact 17.1 we explore the formation of polymers and show how the kinetics of their formation affects their properties and through those properties their technological applications.
To read more about the impact of this material, scan the QR code or go to http://bcs.whfreeman.com/webpub/chemistry/qmc2e/impact/qchem_ impact17.html.
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TOPIC 82
Reaction rates Contents 82.1
Monitoring the progress of a reaction (a)
(b)
82.2
799 General considerations 799 Example 82.1: Monitoring the variation in pressure 800 Special techniques 800
The rates of reactions (a)
(b)
(c)
(d)
The definition of rate Brief illustration 82.1: Reaction rates from balanced chemical equations Rate laws and rate constants Brief illustration 82.2: Rate constants with different units Reaction order Brief illustration 82.3: Rate laws The determination of the rate law Example 82.2: Using the method of initial rates
Checklist of concepts Checklist of equations
801 801 802 802
Monitoring the progress of a reaction
803 803 803 803 804
The first steps in the kinetic analysis of reactions are to establish the stoichiometry of the reaction and identify any side reactions. The basic data of chemical kinetics are then the concentrations of the reactants and products at different times after a reaction has been initiated.
805 805
➤ Why do you need to know this material? Studies of the rates of disappearance of reactants and appearance of products allow us to predict how quickly a reaction mixture approaches equilibrium. Furthermore, studies of reaction rates lead to detailed descriptions of the molecular events that transform reactants into products.
➤ What is the key idea? Reaction rates can be expressed mathematically in terms of the concentrations of reactants and, in some cases, products.
➤ What do you need to know already? To understand the experimental techniques used to study the progress of chemical reactions, you should review the basic concepts of spectroscopy (Topic 40).
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This Topic introduces the principles of chemical kinetics, the study of reaction rates, by showing how the rates of reactions may be measured and interpreted. The results of such measurements show that reaction rates depend on the concentration of reactants (and products) in characteristic ways that can be expressed in terms of differential equations known as rate laws.
82.1
(a)
General considerations
The rates of most chemical reactions are sensitive to the temperature, so in conventional experiments the temperature of the reaction mixture must be held constant throughout the course of the reaction. This requirement puts severe demands on the design of an experiment. Gas-phase reactions, for instance, are often carried out in a vessel held in contact with a substantial block of metal. Liquid-phase reactions, including flow reactions, must be carried out in an efficient thermostat. Special efforts have to be made to study reactions at low temperatures, as in the study of the kinds of reactions that take place in interstellar clouds. Thus, supersonic expansion of the reaction gas can be used to attain temperatures as low as 10 K. For work in the liquid phase and the solid phase, very low temperatures are often reached by flowing cold liquid or cold gas around the reaction vessel. Alternatively, the entire reaction vessel is immersed in a thermally insulated container filled with a cryogenic liquid, such as liquid helium (for work at around 4 K) or liquid nitrogen (for work at around 77 K). Non-isothermal conditions are sometimes employed. For instance, the shelf-life of an expensive
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pharmaceutical may be explored by slowly raising the temperature of a single sample. Spectroscopy is widely applicable to the study of reaction kinetics, and is especially useful when one substance in the reaction mixture has a strong characteristic absorption in a conveniently accessible region of the electromagnetic spectrum. For example, the progress of the reaction H2(g) + Br2(g) → 2 HBr(g) can be followed by measuring the absorption of visible light by bromine. A reaction that changes the number or type of ions present in a solution may be followed by monitoring the electrical conductivity of the solution. The replacement of neutral molecules by ionic products can result in dramatic changes in the conductivity, as in the reaction (CH3)3CCl(aq) + H2O(l) → (CH3)3COH(aq) + H+(aq) + Cl−(aq). If hydrogen ions are produced or consumed, the reaction may be followed by monitoring the pH of the solution. Other methods of determining composition include emission spectroscopy (Topic 46), mass spectrometry, gas chromatography, nuclear magnetic resonance (Topics 47–49), and electron paramagnetic resonance (for reactions involving radicals or paramagnetic d-metal ions; see Topic 50). A reaction in which at least one component is a gas might result in an overall change in pressure in a system of constant volume, so its progress may be followed by recording the variation of pressure with time.
Example 82.1
Monitoring the variation in pressure
Predict how the total pressure varies during the gas-phase decomposition 2 N2O5(g) → 4 NO2(g) + O2(g) in a constantvolume container. Method The total pressure (at constant volume and temperature and assuming perfect gas behaviour) is proportional to the number of gas-phase molecules. Therefore, because each mole of N2O5 gives rise to 25 mol of gas molecules, we can expect the pressure to rise to 25 times its initial value. To confirm this conclusion, express the progress of the reaction in terms of the fraction, α, of N2O5 molecules that have reacted. Answer Let the initial pressure be p0 and the initial amount of
⎛ 3 ⎞ p = ⎜ 1 + α ⎟ p0 ⎝ 2 ⎠ When the reaction is complete, the pressure will have risen to 5 2 times its initial value. Self-test 82.1 Repeat the calculation in Example 82.1 for 2 NOBr(g) → 2 NO(g) + Br2(g). ⎛ 1 ⎞ Answer: p = ⎜ 1 + α ⎟ p0 ⎝ 2 ⎠
(b)
Special techniques
The method used to monitor concentrations depends on the species involved and the rapidity with which their concentrations change. Many reactions reach equilibrium over periods of minutes or hours, and several techniques may then be used to follow the changing concentrations. In a real-time analysis the composition of the system is analysed while the reaction is in progress. Either a small sample is withdrawn or the bulk solution is monitored. In the flow method the reactants are mixed as they flow together in a chamber (Fig. 82.1). The reaction continues as the thoroughly mixed solutions flow through the outlet tube, and observation of the composition at different positions along the tube is equivalent to the observation of the reaction mixture at different times after mixing. The disadvantage of conventional flow techniques is that a large volume of reactant solution is necessary. This makes the study of fast reactions particularly difficult because to spread the reaction over a length of tube the flow must be rapid. This disadvantage is avoided by the stopped-flow technique, in which the reagents are mixed very quickly in a small chamber fitted with a syringe instead of an outlet tube (Fig. 82.2). The flow ceases when the plunger of the syringe reaches a stop, and the reaction continues in the mixed solutions. Observations, commonly using spectroscopic techniques such as ultraviolet–visible absorption and fluorescence emission (all introduced in Topics 40, 45, and 46), are made on the sample as a function of time. The technique allows for the study of reactions that occur on the millisecond to second timescale. The suitability of the stopped-flow
N2O5 molecules present be n. When a fraction α of the N2O5 molecules has decomposed, the amounts of the components in the reaction mixture are:
Amount:
N2O5
NO2
n(1 − α)
2αn
O2 1 αn 2
Total ⎛ 3 ⎞ n ⎜ 1+ α ⎟ ⎝ 2 ⎠
When α = 0 the pressure is p 0, so at any stage the total pressure is
Mixing chamber Driving pistons
Movable spectrometer
Figure 82.1 The arrangement used in the flow technique for studying reaction rates. The reactants are injected into the mixing chamber at a steady rate. The location of the spectrometer corresponds to different times after initiation.
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801
82 Reaction rates
Stopping piston
Driving pistons Fixed spectrometer
Figure 82.2 In the stopped-flow technique the reagents are driven quickly into the mixing chamber by the driving pistons and then the time dependence of the concentrations is monitored.
method to the study of small samples means that it is appropriate for many biochemical reactions, and it has been widely used to study the kinetics of protein folding and enzyme action. Very fast reactions can be studied by flash photolysis, in which the sample is exposed to a brief flash of light that initiates the reaction and then the contents of the reaction chamber are monitored. The apparatus used for flash photolysis studies is based on the experimental design for time-resolved spectroscopy, in which reactions occurring on a picosecond or femtosecond timescale may be monitored by using electronic absorption or emission, infrared absorption, or Raman scattering (Topic 40). In contrast to real-time analysis, quenching methods are based on stopping, or quenching, the reaction after it has been allowed to proceed for a certain time. In this way the composition is analysed at leisure and reaction intermediates may be trapped. These methods are suitable only for reactions that are slow enough for there to be little reaction during the time it takes to quench the mixture. In the chemical quench flow method, the reactants are mixed in much the same way as in the flow method but the reaction is quenched by another reagent, such as a solution of acid or base, after the mixture has travelled along a fixed length of the outlet tube. Different reaction times can be selected by varying the flow rate along the outlet tube. An advantage of the chemical quench flow method over the stopped-flow method is that spectroscopic fingerprints are not needed in order to measure the concentration of reactants and products. Once the reaction has been quenched, the solution may be examined by ‘slow’ techniques, such as gel electrophoresis, mass spectrometry, and chromatography. In the freeze–quench method, the reaction is quenched by cooling the mixture within milliseconds, with the concentrations of reactants, intermediates, and products measured spectroscopically.
(a)
The definition of rate
Consider a reaction of the form A + 2 B → 3 C + D, in which at some instant the molar concentration of a participant J is [J] and the volume of the system is constant. The instantaneous rate of consumption of one of the reactants at a given time is −d[R]/dt, where R is A or B. This rate is a positive quantity (Fig. 82.3). The rate of formation of one of the products (C or D, which we denote P) is d[P]/dt (note the difference in sign). This rate is also positive. It follows from the stoichiometry of the reaction A + 2 B → 3 C + D that d[D] 1 d[C] d[A] 1 d[B] = =− =− dt 3 dt dt 2 dt so there are several rates connected with the reaction. The undesirability of having different rates to describe the same reaction is avoided by using the extent of reaction, ξ (xi, the quantity introduced in Topic 73), ξ=
nJ − nJ ,0 J
Definition
(82.1)
Extent of reaction
where νJ is the stoichiometric number of species J (Topic73), and defining the unique rate of reaction, v, as the rate of change of the extent of reaction: v=
1 dξ V dt
Definition
(82.2)
Rate of reaction
where V is the volume of the system. It follows that v=
1 1 dnJ × J V dt
(82.3a)
(a) Tangent, rate = slope Molar concentration, [J]
Mixing chamber
Product
(b) Tangent, rate = –slope
Reactant Time, t
82.2
The rates of reactions
Reaction rates depend on the composition and the temperature of the reaction mixture. The next few sections look at these observations in more detail.
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Figure 82.3 The definition of (instantaneous) rate as the slope of the tangent drawn to the curve showing the variation of concentration of (a) products, (b) reactants with time. For negative slopes, the sign is changed when reporting the rate, so all reaction rates are positive.
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Chemical kinetics
(Remember that νJ is negative for reactants and positive for products.) For a homogeneous reaction in a constant-volume system the volume V can be taken inside the differential and we use [J] = nJ/V to write v=
1 d[J] J dt
(82.3b)
For a heterogeneous reaction, we use the (constant) surface area, A, occupied by the species in place of V and use σJ = nJ/A to write 1 dσ J v= J dt
(82.3c)
In each case there is now a single rate for the entire reaction (for the chemical equation as written). With molar concentrations in moles per cubic decimetre and time in seconds, reaction rates of homogeneous reactions are reported in moles per cubic decimetre per second (mol dm−3 s−1) or related units. For gasphase reactions, such as those taking place in the atmosphere, concentrations are often expressed in molecules per cubic centimetre (molecules cm−3) and rates in molecules per cubic centimetre per second (molecules cm−3 s−1). For heterogeneous reactions, rates are expressed in moles per square metre per second (mol m−2 s−1) or related units. Brief illustration 82.1
with each concentration raised to the first power. The coefficient kr is called the rate constant for the reaction. The rate constant is independent of the concentrations but depends on the temperature. An experimentally determined equation of this kind is called the rate law of the reaction. More formally, a rate law is an equation that expresses the rate of reaction as a function of the concentrations of all the species present in the overall chemical equation for the reaction at some time: v = f ([A],[B],…)
General form
Rate law in terms of concentrations
(82.5a)
For homogeneous gas-phase reactions, it is often more convenient to express the rate law in terms of partial pressures, which are related to molar concentrations by pJ = RT[J]. In this case, we write v = f ( pA , pB ,…)
General form
Rate law in terms of partial pressures
(82.5b)
The rate law of a reaction is determined experimentally, and cannot in general be inferred from the chemical equation for the reaction. The reaction of hydrogen and bromine, for example, has a very simple stoichiometry, H2(g) + Br2(g) → 2 HBr(g), but its rate law is complicated: v=
ka [H2 ][Br2 ]3/2 [Br2 ]+ kb[HBr]
(82.6)
In certain cases the rate law does reflect the stoichiometry of the reaction, but that is either a coincidence or reflects a feature of the underlying reaction mechanism (see Topic 86).
Reaction rates from balanced
chemical equations If the rate of formation of NO in the reaction 2 NOBr(g) → 2 NO(g) + Br2(g) is reported as 0.16 mmol dm −3 s −1, we use ν NO = +2 to report that v = 0.080 mmol dm −3 s −1. Because ν NOBr = −2 it follows that d[NOBr]/dt = −0.16 mmol dm−3 s −1. The rate of consumption of NOBr is therefore 0.16 mmol dm−3 s −1, or 9.6 × 1016 molecules cm−3 s −1. Self-test 82.2 The rate of change of molar concentration of
CH 3 radicals in the reaction 2 CH 3(g) → CH 3 CH 3(g) was reported as d[CH 3]/dt = −1.2 mol dm−3 s −1 under particular conditions. What is (a) the rate of reaction and (b) the rate of formation of CH3CH3?
A note on good (or, at least, our) practice We denote a general rate constant k r to distinguish it from the Boltzmann constant k. In some texts k is used for the former and k B for the latter. When expressing the rate constants in a more complicated rate law, such as that in eqn 82.6, we use ka, kb, and so on.
The units of kr are always such as to convert the product of concentrations into a rate expressed as a change in concentration divided by time. For example, if the rate law is the one shown in eqn 82.4, with concentrations expressed in mol dm−3, then the units of kr will be dm3 mol−1 s−1 because
Answer: (a) 0.60 mol dm−3 s −1, (b) 0.60 mol dm−3 s −1
dm3 mol −1 s −1 × mol dm −3 × mol dm −3 = mol dm −3 s −1
(b)
Rate laws and rate constants
The rate of reaction is often found to be proportional to the concentrations of the reactants raised to a power. For example, the rate of a reaction may be proportional to the molar concentrations of two reactants A and B, so we write v = kr [A][B]
(82.4)
In gas-phase studies, including studies of the processes taking place in the atmosphere, concentrations are commonly expressed in molecules cm−3, so the rate constant for the reaction above would be expressed in cm3 molecule−1 s−1. We can use the approach just developed to determine the units of the rate constant from rate laws of any form. For example, the rate constant for a reaction with rate law of the form kr[A] is commonly expressed in s−1.
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82 Reaction rates
Brief illustration 82.2
Rate constants with different units
The rate constant for the reaction O(g) + O3(g) → 2 O2(g) is 8.0 × 10 −15 cm3 molecule−1 s −1 at 298 K. To express this rate constant in dm 3 mol−1 s −1, we make use of the two relations 1 cm = 10 −1 dm and 1 molecule = (1 mol)/(6.022 × 1023). It follows that kr = 8.0 ×10−15 cm3 molecule −1 s −1 −1
⎛ 1 mol ⎞ −1 = 8.0 ×10−15 (10−1 dm)3 ⎜ s 23 ⎝ 6.022 × 10 ⎟⎠ = 8.0 × 10−15 × 10−3 × 6.022 × 1023 dm3 mol −1 s −1 = 4.8 × 106 dm3 mol −1 s −1 Self-test 82.3 A reaction has a rate law of the form k r[A]2[B].
What are the units of the rate constant if the reaction rate is measured in mol dm−3 s −1? Answer: dm6 mol−2 s −1
Brief illustration 82.3
803
Rate laws
The reduction of nitrogen dioxide by carbon monoxide NO2 (g ) + CO(g) → NO(g) + CO2 (g ) has the rate law v = k r[NO2]2 , which is second-order in NO2 and, because no other species occurs in the rate law, secondorder overall. The rate of this reaction is independent of the concentration of CO provided that some CO is present, so it is zeroth-order in CO. The experimentally determined rate law for the gas-phase reaction H 2(g) + Br2(g) → 2 HBr(g) is given by eqn 82.6. Although the reaction is first-order in H 2 , it has an indefinite order with respect to both Br2 and HBr and an indefinite order overall. Self-test 82.4 Repeat this analysis for a typical rate law for the
action of an enzyme E on a substrate S (see Topic 92 for the derivation of this rate law): v = k r[E][S]/([S] + K M), where K M is a constant. Answer: First-order in E; no specific order with respect to S
A practical application of a rate law is that once we know the law and the value of the rate constant, we can predict the rate of reaction from the composition of the mixture. As we shall see later, by knowing the rate law, we can go on to predict the composition of the reaction mixture at a later stage of the reaction. Moreover, a rate law is a guide to the mechanism of the reaction (Topic 86), for any proposed mechanism must be consistent with the observed rate law.
(c)
Reaction order
Many reactions are found to have rate laws of the form v = kr [A]a [B]b …
(82.7)
The power to which the concentration of a species (a product or a reactant) is raised in a rate law of this kind is the order of the reaction with respect to that species. A reaction with the rate law in eqn 82.4 is first-order in A and first-order in B. The overall order of a reaction with a rate law like that in eqn 82.7 is the sum of the individual orders, a + b + …. The rate law in eqn 82.4 is therefore second-order overall. A reaction need not have an integral order, and many gasphase reactions do not. For example, a reaction having the rate law v = kr [A]1/2[B]
(82.8)
is half-order in A, first-order in B, and three-halves-order overall. If a reaction rate is independent of the concentration of one of the reactants, then we say that it is zeroth-order in that reactant (because [J]0 = 1, independent of the value of [J], just as x0 = 1).
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An example of a zeroth-order reaction is the catalytic decomposition of phosphine (PH3) on hot tungsten at high pressures, with the rate law v = kr
(82.9)
The PH3 decomposes at a constant rate until it has almost entirely disappeared. Zeroth-order reactions typically occur when there is a bottleneck of some kind in the mechanism, as in heterogeneous reactions when the surface is saturated and the subsequent reaction slow, and in a number of enzyme reactions when there is a large excess of substrate relative to the enzyme. As we saw in Brief illustration 82.3, when a rate law is not of the form in eqn 82.7, the reaction does not have an overall order and may not even have definite orders with respect to each participant. These remarks point to three important problems: r To identify the rate law and obtain the rate constant from the experimental data. We concentrate on this aspect in this Topic. r To construct reaction mechanisms that are consistent with the rate law. We introduce the techniques for doing so in Topic 86. r To account for the values of the rate constants and explain their temperature dependence. This dependence is treated in Topic 85.
(d)
The determination of the rate law
The determination of a rate law is simplified by the isolation method in which the concentrations of all the reactants
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Chemical kinetics
except one are in large excess. If B is in large excess in a reaction between A and B, for example, then to a good approximation its concentration is constant throughout the reaction. Although the true rate law might be v = kr[A][B], we can approximate [B] by [B]0, its initial value, and write v = kr′[A]
kr′ = kr [B]0
log v0 = log kr′ + a log[A]0
(82.11)
For a series of initial concentrations, a plot of the logarithms of the initial rates against the logarithms of the initial concentrations of A should be a straight line with slope a.
The recombination of iodine atoms in the gas phase in the presence of argon was investigated and the order of the reaction was determined by the method of initial rates. The initial rates of reaction of 2 I(g) + Ar(g) → I2(g) + Ar(g) were as follows:
v0/(mol dm−3 s−1)
1.0
2.0
4.0
6.0
(a) 8.70 × 10−4
3.48 × 10−3
1.39 × 10−2
3.13 × 10−2
(b) 4.35 × 10−3
1.74 × 10−2
6.96 × 10−2
1.57 × 10−1
8.69 × 10−3
3.47 × 10−2
1.38 × 10−1
3.13 × 10−1
(c)
(b)
(a)
–1
–2
–3
0
0.2
0.4 0.6 log [I]0 + 5
0.8
10
0.2
0.4 0.6 0.8 log [Ar]0 + 3
1
Figure 82.4 The plot of log v0 against (a) log [I]0 for a given [Ar]0, and (b) log [Ar]0 for a given [I]0. A note on good practice The units of kr come auto-
matically from the calculation, and are always such as to convert the product of concentrations to a rate in concentration/time (for example, mol dm−3 s−1). Self-test 82.5 The initial rate of a reaction depended on concentration of a substance J as follows:
Using the method of initial rates
[I]0/(10−5 mol dm−3)
1, respectively, so the (initial) rate law is v0 = kr [I]20[Ar]0 . This rate law signifies that the reaction is second-order in [I], firstorder in [Ar], and third-order overall. The intercept corresponds to k r = 9 × 109 mol−2 dm6 s −1.
(82.10)
which has the form of a first-order rate law. Because the true rate law has been forced into first-order form by assuming that the concentration of B is constant, eqn 82.10 is called a pseudofirst-order rate law. The dependence of the rate on the concentration of each of the reactants may be found by isolating them in turn (by having all the other substances present in large excess), and so constructing a picture of the overall rate law. In the method of initial rates, which is often used in conjunction with the isolation method, the rate is measured at the beginning of the reaction for several different initial concentrations of reactants. We shall suppose that the rate law for a reaction with A isolated is v = kr′[A]a ; then its initial rate, v0, is given by the initial values of the concentration of A, and we write v0 = kr′[A]a0 . Taking logarithms gives
Example 82.2
Answer The plots are shown in Fig. 82.4. The slopes are 2 and
log(v0/mol dm–3 s–1)
804 17
The Ar concentrations are (a) 1.0 mmol dm−3, (b) 5.0 mmol dm−3, and (c) 10.0 mmol dm−3. Determine the orders of reaction with respect to the I and Ar atom concentrations, and the rate constant. Method Plot the logarithm of the initial rate, log v 0, against log [I]0 for a given concentration of Ar, and, separately, against log [Ar]0 for a given concentration of I. The slopes of the two lines are the orders of reaction with respect to I and Ar, respectively. The intercepts with the vertical axis give log k r.
[J]0/(mmol dm−3)
5.0
8.2
17
30
v0/(10−7
3.6
9.6
41
130
mol
dm−3 s−1)
Determine the order of the reaction with respect to J and calculate the rate constant. Answer: 2, 1.4 × 10 −2 dm3 mol−1 s −1
The method of initial rates might not reveal the full rate law, for once the products have been generated they might participate in the reaction and affect its rate. For example, products participate in the synthesis of HBr, because eqn 82.6 shows that the full rate law depends on the concentration of HBr. To avoid this difficulty, the rate law should be fitted to the data throughout the reaction. The fitting may be done, in simple cases at least, by using a proposed rate law to predict the concentration of any component at any time, and comparing it with the data. A rate law should also be tested by observing whether the addition of products or, for gas-phase reactions, a change in the surface-to-volume ratio in the reaction chamber affects the rate.
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82 Reaction rates
805
Checklist of concepts ☐ 1. The rates of chemical reactions are measured by using techniques t hat monitor t he concentrations of species present in the reaction mixture. Examples include real-time and quenching procedures, flow and stopped-flow techniques, and flash photolysis.
2. The instantaneous rate of a reaction is the slope of the tangent to the graph of concentration against time (expressed as a positive quantity). 3. A rate law is an expression for the reaction rate in terms of the concentrations of the species that occur in the overall chemical reaction.
Checklist of equations Property
Equation
Comment
Equation number
Extent of reaction
ξ = (nJ − nJ,0)/νJ
Definition
82.1
Rate of a reaction
v = (1/V)(dξ/dt)
Definition
82.2
Rate law (in some cases)
v = kr[A]a[B]b…
a, b, …: orders; a + b + …: overall order
82.7
Method of initial rates
log v0 = log kr′ + a log [A]0
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82.11
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TOPIC 83
Integrated rate laws Contents 83.1
First-order reactions Example 83.1: Analysing a first-order reaction
83.2
Second-order reactions Brief illustration 83.1: Second-order reactions
Checklist of concepts Checklist of equations
806 807 808 809 811 811
numerically. However, in a number of simple cases analytical solutions, known as integrated rate laws, are easily obtained, and prove to be very useful. We examine a few of these simple cases here.
First-order reactions
83.1
As shown in the following Justification, the integrated form of the first-order rate law d[A] = −kr [A] dt
➤ Why do you need to know this material? A complete analysis of the time course of depletion of reactants and appearance of products is a required step in the formulation and verification of the mechanism of a reaction. The practical application of the material is that it enables you to predict the composition of a reaction system at any stage.
➤ What is the key idea? A comparison between experimental data and the integrated form of the rate law leads to the verification of a proposed rate law and the determination of the order and rate constant of a reaction.
(83.1a)
is ln
[A] = −kr t [A]0
[A] = [A]0 e − k t r
Integrated firstorder rate law
(83.1b)
where [A]0 is the initial concentration of A (at t = 0).
Justification 83.1
First-order integrated rate law
First, we rearrange eqn 83.1a into d[A] = −kr dt [A]
➤ What do you need to know already? You need to be familiar with the concepts of rate law, reaction order, and rate constant (Topic 82). The manipulation of simple rate laws requires only elementary techniques of integration (see the Resource section for standard integrals).
This expression can be integrated directly because k r is a constant independent of t. Initially (at t = 0) the concentration of A is [A]0, and at a later time t it is [A], so we make these values the limits of the integrals and write [ A]
d[A] = −kr [ A ]0 [A]
∫ Because rate laws (Topic 82) are differential equations, we must integrate them if we want to find the concentrations as a function of time. Even the most complex rate laws may be integrated
t
∫ dt 0
Because the integral of 1/x is ln x + constant (Integral A.2 in the Resource section), eqn 83.1b is obtained immediately.
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83 Integrated rate laws
Equation 83.1b shows that if ln([A]/[A]0) is plotted against t, then a first-order reaction will give a straight line of slope −kr. Some rate constants determined in this way are given in Table 83.1. The second expression in eqn 83.1b shows that in a firstorder reaction the reactant concentration decreases exponentially with time with a rate determined by kr (Fig. 83.1). A useful indication of the rate of a first-order chemical reaction is the half-life, t1/2, of a substance, the time taken for the concentration of a reactant to fall to half its initial value. This quantity is readily obtained from the integrated rate law. Thus, the time for [A] to decrease from [A]0 to 12 [A]0 in a first-order reaction is given by eqn 83.1b as
807
Another indication of the rate of a first-order reaction is the time constant, τ (tau), the time required for the concentration of a reactant to fall to 1/e of its initial value. From eqn 83.1b it follows that 1 [A] krτ = − ln e 0 = − ln 1e = 1 [A]0
That is, the time constant of a first-order reaction is the reciprocal of the rate constant: τ=
1 kr
First-order reaction
Time constant
(83.3)
1 [A] kr t1/2 = − ln 2 0 = − ln 12 = ln 2 [A]0
Example 83.1
Hence ln 2 t1/2 = kr
First-order reaction
(83.2)
Half-life
(Note that ln 2 = 0.693.) The main point to note about this result is that, for a first-order reaction, the half-life of a reactant is independent of its initial concentration. Therefore, if the concentration of A at some arbitrary stage of the reaction is [A], then it will have fallen to 12 [A] after a further interval of (ln 2)/kr. Some half-lives are given in Table 83.1. Table 83.1* Kinetic data for first-order reactions Reaction
Phase
θ/°C
kr/s−1
t1/2
2 N2O5→ 4 NO2 + O2
g
25
3.38 × 10−5
5.70 h
Br2(l)
25
4.27 × 10−5
4.51 h
700
5.36 × 10−4
21.6 min
C2H6→ 2 CH3
g
1
[A]/[A]0
0.8
0.4
0
kr,large 0
1
kr,smallt
2
3
Figure 83.1 The exponential decay of the reactant in a firstorder reaction. The larger the rate constant, the more rapid the decay: here kr,large = 3kr,small.
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CH3N2CH3 (g ) → CH3CH3 (g) + N2 (g ) is first-order in azomethane, and find the rate constant, halflife, and time constant at 600 K. t/s
0
1000
2000
3000
4000
p/Pa
10.9
7.63
5.32
3.71
2.59
Method As indicated in the text, to confirm that a reaction is first-order, plot ln([A]/[A]0) against time and expect a straight line. Because the partial pressure of a gas is proportional to its concentration, an equivalent procedure is to plot ln(p/p 0) against t. If a straight line is obtained, its slope can be identified with −k r. The half-life and time constant are then calculated from k r by using eqns 83.2 and 83.3, respectively.
t/s
0
1000
2000
3000
4000
ln(p/p0)
0
−0.357
−0.717
−1.078
−1.437
Figure 83.2 shows the plot of ln(p/p 0) against t. The plot is straight, confirming a first-order reaction, and its slope is −3.6 × 10−4. Therefore, k r = 3.6 × 10−4 s−1.
kr,small
0.2
The variation in the partial pressure of azomethane with time was followed at 600 K, with the results given below. Confirm that the decomposition
Answer We draw up the following table:
* More values are given in the Resource section.
0.6
Analysing a first-order reaction
A note on good practice Because the horizontal and vertical axes of graphs are labelled with pure numbers, the slope of a graph is always dimensionless. For a graph of the form y = b + mx we can write y = b + (m units)(x/units), where ‘units’ are the units of x, and identify the (dimensionless) slope with ‘m units’. Then m = slope/units. In the present case, because the graph shown here is a plot of ln(p/p0) against t/s (with ‘units’ = s) and k r is the negative value of the slope of ln(p/p0) against t itself, k r = −slope/s.
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808 17
Chemical kinetics
Justification 83.2
0
Second-order integrated rate law
To integrate eqn 83.4a we rearrange it into d[A] = −kr dt [A]2
ln(p/p0)
–0.5
The concentration is [A]0 at t = 0 and [A] at a general time t later. Therefore,
–1
− –1.5
0
1
2 t/(103 s)
3
4
Figure 83.2 The determination of the rate constant of a first-order reaction: a straight line is obtained when ln [A]/[A]0 (or, as here, ln p/p0) is plotted against t; the slope gives kr. It follows from eqns 83.2 and 83.3 that the half-life and time constant are, respectively, t1/2 =
ln 2 = 1.9 ×10−5 s 3.6 ×104 s −1
τ=
1 = 2.8 ×10−5 s 3.6 ×104 s −1
Self-test 83.1 In a particular experiment, it was found that the concentration of N2O5 in liquid bromine varied with time as follows: t/s
0
200
400
600
1000
[N2O5]/(mol dm−3)
0.110
0.073
0.048
0.032
0.014
Confirm that the reaction is first-order in N2O5 and determine the rate constant. Answer: k r = 2.1 × 10 −3 s −1
[ A]
d[A] = kr 2 [ A ]0 [A]
∫
[A] 1 1 1 + constant = − =k t [A] [A]0 [A] [A]0 r We can then rearrange this expression into eqn 83.4c.
Equation 83.4b shows that to test for a second-order reaction we should plot 1/[A] against t and expect a straight line. The slope of the graph is kr. Some rate constants determined in this way are given in Table 83.2. The rearranged form, eqn 83.4c, lets us predict the concentration of A at any time after the start of the reaction. It shows that the concentration of A approaches zero more slowly than in a first-order reaction with the same initial rate (Fig. 83.3). It follows from eqn 83.4b by substituting t = t1/2 and [A] = 12 [A]0 that the half-life of a species A that is consumed in a second-order reaction is
Second-order reactions
We show in the following Justification that the integrated form of the second-order rate law d[A] = −kr [A]2 dt
(83.4a)
0
Because the integral of 1/x 2 is −1/x + constant (Integral A.1 in the Resource section), we obtain eqn 83.4b by substitution of the limits
t1/2 =
83.2
t
∫ dt
1 kr [A]0
Second-order reaction
Half-life
(83.5)
Therefore, unlike a first-order reaction, the half-life of a substance in a second-order reaction varies with the initial concentration. A practical consequence of this dependence is that species that decay by second-order reactions (which includes some environmentally harmful substances) may persist in low concentrations for long periods because their half-lives are long
is either of the following two forms: 1 1 − =k t [A] [A]0 r [A] =
Second-order reaction
[A]0 1+ kr t[A]0
Second-order reaction
Integrated rate law
Alternative form of the integrated rate law
where [A]0 is the initial concentration of A (at t = 0).
(83.4b)
(83.4c)
Table 83.2* Kinetic data for second-order reactions θ/°C
kr/(dm3 mol−1 s−1)
g
10
0.80
g
23
7 × 109
CH3OH(l)
20
2.29 × 10−6
Reaction
Phase
2 NOBr → 2 NO + Br2 2 I → I2 CH3Cl + CH3
O−
* More values are given in the Resource section.
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83 Integrated rate laws
1
809
the concentration of B fell to [B] = 0.020 mol dm−3. Because Δ[B] = Δ[A], it follows that during this time interval
0.8
[A]/[A]0
Δ[B] = (0.020 − 0.050) mol dm −3 = −0.030 mol dm −3 Δ[A] = −0.030 mol dm −3
0.6
kr,small
Therefore, the concentrations of A and B after 1.0 h are
0.4
kr,large
[A] = Δ[A] + [A]0 = (−0.030 + 0.075) mol dm −3
0.2 0
= 0.045 mol dm −3
0
1
2
3
kr,small[A]0t
It follows from rearrangement of eqn 83.8 that
Figure 83.3 The variation with time of the concentration of a reactant in a second-order reaction. The dotted lines are the corresponding decays in a first-order reaction with the same initial rate. For this illustration, kr,large = 3kr,small.
when their concentrations are low. In general, for an nth-order reaction (with n neither 0 nor 1) of the form A → products, the half-life is related to the rate constant and the initial concentration of A by (see Problem 83.16) t1/2 =
1 0.020 / 0.050 ln (0.050 − 0.075) mol dm −3 0.045 / 0.075
where we have used 1 hr = 3600 s. Solving this expression for the rate constant gives kr = 4.5 × 10−3 dm3 mol −1s −1 Self-test 83.2 Calculate the half-life of the reactants for the
reaction above. Answer: t1/2(A) = 5.1 × 103 s, t1/2(B) = 2.1 × 103 s
2 −1 (n −1)kr [A]n0−1
nth-order reaction
Half-life
d[A] = −kr [A][B] dt
(83.6)
(83.7)
This rate law cannot be integrated until we know how the concentration of B is related to that of A. For example, if the reaction is A + B → P, where P denotes products, and the initial concentrations are [A]0 and [B]0, then it is shown in the following Justification that at a time t after the start of the reaction, the concentrations satisfy the relation [B]/[B]0 = ([B]0 −[A]0 )kr t [A]/[A]0
Second-order reaction of the type A+B→P
Integrated rate law
(83.8)
Therefore, a plot of the expression on the left against t should be a straight line from which kr can be obtained. As shown in the following Brief illustration, the rate constant may be estimated quickly by using data from only two measurements. Brief illustration 83.1
Second-order reactions
Consider a second-order reaction of the type A + B → P carried out in solution. Initially, the concentrations of reactants were [A]0 = 0.075 mol dm−3 and [B]0 = 0.050 mol dm −3. After 1.0 h
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kr (3600 s) =
n−1
Another type of second-order reaction is one that is first-order in each of two reactants A and B:
ln
[B] = 0.020 mol dm − 3
Justification 83.3
Overall second-order rate law
It follows from the reaction stoichiometry that when the concentration of A has fallen to [A]0 − x, the concentration of B will have fallen to [B]0− x (because each A that disappears entails the disappearance of one B). It follows that d[A] = −kr ([A]0 − x )([B]0 − x ) dt Because [A] = [A]0 − x, it follows that d[A]/dt = −dx/dt and the rate law may be written as dx = kr ([A]0 − x )([B]0 − x ) dt The initial condition is that x = 0 when t = 0, so the integration required is
∫
x
0
dx =k ([A]0 − x )([B]0 − x ) r
t
∫ dt 0
The integral on the right is simply k rt. The integral on the left is evaluated by using the method of partial fractions (see The chemist’s toolkit 83.1):
∫
x
0
dx 1 = ([A]0 − x )([B]0 − x ) [B]0 −[A]0
[B]0 ⎫ [A]0 ⎧ ⎨ln [A] − x − ln [B] − x ⎬ 0 0 ⎩ ⎭
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810 17
Chemical kinetics
The two logarithms can be combined as follows: ln
where a and b are constants, we use the method of partial fractions, in which a fraction that is the product of terms (as in the denominator of this integrand) is written as a sum of fractions. To implement this procedure we write the integrand as
[A]0 [B]0 [A] [B] − ln = ln 0 − ln 0 [A] [B] [A]0 − x [B]0 − x 1 1 = ln − ln [B]/[B]0 [A]/[A]0 [B]/[B]0 = ln [A]/[A]0
1 1 ⎛ 1 1 ⎞ = − (a − x )(b − x ) b − a ⎜⎝ a − x b − x ⎟⎠
where we have used [A] = [A]0 − x and [B] = [B]0 − x. Combining all the results so far gives eqn 83.8. Similar calculations may be carried out to find the integrated rate laws for other orders, and some are listed in Table 83.3.
The chemist’s toolkit 83.1
Then we integrate each term on the right. It follows that I=
1 ⎛ dx dx ⎞ − b − a ⎜⎝ a − x b − x ⎟⎠
∫
Integral A.2
=
∫
1 ⎛ 1 1 ⎞ + constant ln − ln b − a ⎜⎝ a − x b − x ⎟⎠
Integration by the method
of partial fractions To solve an integral of the form I=
1
∫ (a − x)(b − x) dx
Table 83.3 Integrated rate laws Order
Reaction
Rate law*
t1/2
0
A→P
v = kr krt = x for 0 ≤ x ≤ [A]0
[A]0/2kr
1
A→P
v = kr[A]
(ln 2)/kr
[A]0 kr t = ln [A]0 − x 2
A→P
v = kr[A]2 kr t =
A+B→P
A+2 B→P
1 [A] ([B]0 − 2 x ) ln 0 [B]0 − 2[A]0 ([A]0 − x )[B]0
v = kr[A][P] kr t =
3
1 [A]0 ([B]0 − x ) ln [B]0 −[A]0 ([A]0 − x )[B]0
v = kr[A][B] kr t =
A → P with autocatalysis
x [A]0 ([A]0 − x )
v = kr[A][B] kr t =
A+2 B→P
1/kr[A]0
1 [A]0 ([P]0 + x ) ln [A]0 +[P]0 ([A]0 − x )[P]0
v = kr[A][B]2 kr t =
2x 1 [A] ([B]0 − 2 x ) + ln 0 ([A]0 − x )[B]0 (2[A]0 −[B]0 )([B]0 − 2 x )[B]0 (2[A]0 −[B]0 )2
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83 Integrated rate laws
Order
Reaction
Rate law*
t1/2
n≥2
A→P
v = kr[A]n
2n−1 −1 (n −1)kr [A]0n−1
kr t =
811
1 ⎧⎪ 1 1 ⎫⎪ − n −1 ⎨⎩⎪ ([A]0 − x )n−1 [A]0n−1 ⎬⎭⎪
* x = [P] and v = dx/dt
Checklist of concepts ☐ 1. An integrated rate law is an expression for the concentration of a reactant or product as a function of time (Table 83.3).
☐ 2. Analysis of experimental data using integrated rate laws allows for the prediction of the composition of a reaction system at any stage.
Checklist of equations Property
Equation e − krt
Comment
Equation number
First-order, A → P
83.1
Integrated rate law
ln([A]/[A]0) = −krt or [A] = [A]0
Half-life
t1/2 = (ln 2)/kr
First-order, A → P
83.2
Time constant
τ = 1/kr
First-order
83.3
Integrated rate law
1/[A] − 1/[A]0 = krt, or [A] = [A]0/(1 + krt[A]0)
Second-order, A → P
83.4
Half-life
t1/2 = 1/kr[A]0
Second-order, A → P
83.5
nth-order
83.6
Second-order A + B → P
83.8
(2n −1 −1)/(n −1)kr [A]n0−1
Half-life
t1/2 =
Integrated rate law
ln{([B]/[B]0)/([A]/[A]0)} = ([B]0 − [A]0)krt
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TOPIC 84
Reactions approaching equilibrium Contents 84.1
First-order reactions close to equilibrium Brief illustration 84.1: The equilibrium constant from rate constants
84.2
Relaxation methods Example 84.1: Analysing a temperaturejump experiment
Checklist of concepts Checklist of equations
812
unimportant. For this reason, none of the laws considered so far describes the overall rate when the reaction is close to equilibrium. At that stage the products may be so abundant that the reverse reaction must be taken into account.
813 813
First-order reactions close to equilibrium 84.1
814 815 815
➤ Why do you need to know this material? All reactions approach equilibrium, so it is important to be able to describe the changing composition as they approach this composition.
➤ What is the key idea? Both forward and reverse reactions must be incorporated into a reaction scheme to account for the approach to equilibrium, and the analysis of the mechanism shows that there is a relation between the corresponding rate constants and the equilibrium constant.
➤ What do you need to know already? You need to be familiar with the concepts of rate law, reaction order, and rate constant (Topic 82), integrated rate laws (Topic 83), and equilibrium constants (Topic 73). As in Topic 83, the manipulation of simple rate laws requires only elementary techniques of integration.
In practice, most kinetic studies are made on reactions that are far from equilibrium, and the reverse reactions are
We can explore the variation of the composition with time close to chemical equilibrium by considering the reaction in which A forms B and both forward and reverse reactions are first-order (as in some isomerizations). The scheme we consider is A→B B→ A
v = kr [A] v = kr′[B]
(84.1)
The concentration of A is reduced by the forward reaction (at a rate kr[A]) but it is increased by the reverse reaction (at a rate kr′[B]). The net rate of change is therefore d[A] = −kr [A]+ kr′[B] dt
(84.2)
If the initial concentration of A is [A]0, and no B is present initially, then at all times [A] + [B] = [A]0. Therefore, d[A] = −kr [A]+ kr′{[A]0 −[A]} dt = −(kr + kr′ )[A]+ kr′[A]0
(84.3)
The solution of this first-order differential equation (as may be checked by differentiation, Problem 84.1) is [A] =
kr′ + kr e −(k +k ′ )t [A]0 kr + kr′ r
r
(84.4)
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84 Reactions approaching equilibrium
The presence of c< = 1 mol dm−3 in the last term ensures that the ratio of second-order to first-order rate constants, with their different units, is turned into a dimensionless quantity.
1
A
[J]/[J]0
0.8 0.6
Brief illustration 84.1
0.2
B
0
1
(kr + kr’)t
2
3
Figure 84.1 The approach of concentrations to their equilibrium values as predicted by eqn 84.4 for a reaction A B that is first-order in each direction, and for which kr = 2kr′.
Figure 84.1 shows the time dependence predicted by this equation, with [B] = [A]0 − [A]. As t → ∞, the concentrations reach their equilibrium values, which are given by eqn 84.4 as [A]eq =
kr′[A]0 kr + kr′
[B]eq = [A]0 −[A]eq =
kr [A]0 kr + kr′
(84.5)
It follows that the equilibrium constant of the reaction is K=
[B]eq kr = [A]eq kr′
(84.6)
(As explained in Topic 72, we are justified in replacing activities with the numerical values of molar concentrations if the latter are low.) Exactly the same conclusion can be reached—more simply, in fact—by noting that, at equilibrium, the forward and reverse rates must be the same, so kr [A]eq = kr′[B]eq
K=
[C]eq / c < ⎛ [C] ⎞ < kr < =⎜ c = ×c < < kr′ ([A]eq /c )([B]eq /c ) ⎝ [A][B]⎟⎠ eq
The rates of the forward and reverse reactions for a dimerization reaction were found to be 8.0 × 108 dm3 mol−1 s −1 (secondorder) and 2.0 × 106 s −1 (first-order). The equilibrium constant for the dimerization is therefore K=
8.0 ×108 dm3 mol −1 s −1 ×1mol dm −3 = 4.0 ×102 2.0 ×106 s −1
Self-test 84.1 The equilibrium constant for the attachment of a drug molecule to a protein was measured as 2.0 × 102 . In a separate experiment, the rate constant for the second-order attachment was found to be 1.5 × 10 8 dm 3 mol−1 s −1. What is the rate constant for the loss of the drug molecule from the protein? Answer: 7.5 × 105 s −1
For a more general reaction, the overall equilibrium constant can be expressed in terms of the rate constants for all the intermediate stages of the reaction mechanism (see Problem 84.4): K=
ka kb × × ka′ kb′
The equilibrium constant in terms of the rate constants
(84.8)
where the ks are the rate constants for the individual steps and the k′s are those for the corresponding reverse steps.
84.2
Relaxation methods
(84.7)
This relation rearranges into eqn 84.6. The theoretical importance of eqn 84.6 is that it relates a thermodynamic quantity, the equilibrium constant, to quantities relating to rates. Its practical importance is that if one of the rate constants can be measured, then the other may be obtained if the equilibrium constant is known. Equation 84.6 is valid even if the forward and reverse reactions have different orders, but in that case we need to be careful with units. For instance, if the reaction A + B → C is secondorder forward and first-order in reverse, then the condition for equilibrium is kr [A]eq [B]eq = kr′[C]eq and the dimensionless equilibrium constant in full dress is
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The equilibrium constant from
rate constants
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0
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The term relaxation denotes the return of a system to equilibrium. It is used in chemical kinetics to indicate that an externally applied influence has shifted the equilibrium position of a reaction, normally suddenly, and that the reaction is adjusting to the equilibrium composition characteristic of the new conditions (Fig. 84.2). We shall consider the response of reaction rates to a temperature jump, a sudden change in temperature. We know from Topic 75 that the equilibrium composition of a reaction depends on the temperature (provided ΔrH< is nonzero), so a shift in temperature acts as a perturbation on the system. One way of achieving a temperature jump is to discharge a capacitor through a sample made conducting by the addition of ions, but laser or microwave discharges can also be used. Temperature jumps of between 5 and 10 K can be achieved in about 1 μs with electrical discharges. The high-energy output of pulsed lasers (Topic 46) is sufficient to generate temperature
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Chemical kinetics
d[A] = − kr [A] + kr′[B] dt = − kr ([A]eq + x ) + kr′ ([B]eq − x )
Concentration, [A]
Final equilibrium
= −(kr + kr′ )x
Exponential relaxation
because the two terms involving the equilibrium concentrations cancel. Because d[A]/dt = dx/dt, this equation is a firstorder differential equation with a solution that resembles eqn 83.1b and is given in eqn 84.9.
Initial equilibrium T1
T2 Time, t
Equation 84.9 shows that the concentrations of A and B relax into the new equilibrium at a rate determined by the sum of the two new rate constants. Because the equilibrium constant under the new conditions is K ≈ kr /kr′ , its value may be combined with the relaxation time measurement to find the individual kr and kr′.
Figure 84.2 The relaxation to the new equilibrium composition when a reaction initially at equilibrium at a temperature T1 is subjected to a sudden change of temperature, which takes it to T2.
jumps of between 10 and 30 K within nanoseconds in aqueous samples. Some equilibria are also sensitive to pressure, and pressure-jump techniques may then also be used. When a sudden temperature increase is applied to a simple A B equilibrium that is first-order in each direction, we show in the following Justification that the composition relaxes exponentially to the new equilibrium composition: x = x0 e −t /τ
τ=
1 kr + kr′
First-order reaction
Relaxation after a temperature jump
(84.9)
where x0 is the departure from equilibrium immediately after the temperature jump, x is the departure from equilibrium at the new temperature after a time t, and kr and kr′ are the forward and reverse rate constants, respectively, at the new temperature.
Justification 84.1
Relaxation to equilibrium
When the temperature of a system at equilibrium is increased suddenly, the rate constants change from their earlier values to the new values k r and kr′ characteristic of that temperature, but the concentrations of A and B remain for an instant at their old equilibrium values. As the system is no longer at equilibrium, it readjusts to the new equilibrium concentrations, which are now given by kr [A]eq = kr′[B]eq and it does so at a rate that depends on the new rate constants. We write the deviation of [A] from its new equilibrium value as x, so [A] = [A]eq + x and [B] = [B]eq − x. The concentration of A then changes as follows:
Example 84.1
Analysing a temperature-jump
experiment The equilibrium constant for the autoprotolysis of water, H2O(l) H+(aq) + OH−(aq), is Kw = a(H+)a(OH−) = 1.008 × 10−14 at 298 K, where we have used the exact expression in terms of activities. After a temperature jump, the reaction returns to equilibrium with a relaxation time of 37 μs at 298 K and pH ≈ 7. Given that the forward reaction is first-order and the reverse is second-order overall, calculate the rate constants for the forward and reverse reactions. Method We need to derive an expression for the relaxation time, τ (the time constant for return to equilibrium), in terms of k r (forward, first-order reaction) and kr′ (reverse, second-order reaction). We can proceed as above, but it will be necessary to make the assumption that the deviation from equilibrium (x) is so small that terms in x 2 can be neglected. Relate k r and kr′ through the equilibrium constant, but be careful with units because Kw is dimensionless. Answer The forward rate at the final temperature is k r[H 2O] and the reverse rate is kr′[H + ][OH − ]. The net rate of deprotonation of H2O is
d[H2O] = −kr [H2O] + kr′[H + ][OH − ] dt We w r ite [H 2 O] = [H 2 O] e q + x , [H + ] = [H + ] e q − x , a nd [OH−] = [OH−]eq − x, and obtain dx = −{kr + kr′([H + ]eq +[OH − ]eq )}x − kr [H2O]eq dt + kr′[H + ]eq [OH − ]eq + kr′x 2 ≈ −{kr + kr′([H + ]eq +[OH − ]eq )}x
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84 Reactions approaching equilibrium
where we have neglected the term in x 2 because it is so small and have used the equilibrium condition kr [H2O]eq = kr′[H + ]eq [OH − ]eq to eliminate the terms that are independent of x. It follows that
(
Hence, kr′ =
At this point we note that
=
K w = a(H )a(OH ) ≈ ([H ]eq /c )([OH ]eq /c ) −
+
