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8.

Chemical Kinetics

objectives of chemical kinetics
1) Determine empirical rate laws

H2 + I2 −→ 2 HI
How does the concentration of H2, I2, and HI change
with time?
2) Determine the mechanism of the reaction

H2 + I2 −→ 2 HI
is a stoichiometric statement
reactants −→ intermediates −→ products
elementary reaction: the stoichiometric equation
reflects what actually happens to the molecules
mechanism: series of elementary reactions that
constitute the stoichiometric equation
PChem I

8.1

example

2 H2 + O2 −→ 2 H2O
some intermediate steps:

H2 + O2 −→ HO2 + H
H2 + HO2 −→ OH + H2O
OH + H2 −→ H2O + H
O2 + H −→ OH + O
H2 + O −→ OH + H
3) Empirical study of elementary reactions
important intermediates are often unstable, shortlived species: H, OH, . . .
4) Predict rates of reactions
theoretical calculations
5) Chemical dynamics
study the dynamics of collisions and reactions of individual molecules; high vacuum
PChem I

8.2

reaction rates

2 NO + O2 −→ 2 NO2
d[NO]

,
dt

time dependence:

d[O2]

,
dt

d[NO2]
dt

ambiguity: NO reacts twice as fast as O2
chemical reaction

P

νJJ = 0

νJ positive for products
νJ negative for reactants
extent of the reaction ξ

dn J ≡ νJdξ
Using numbers of moles in the definition of the extent
of the reaction, we ensure that it is general and that
it applies even to non-constant volume reactions.

dn NO = −2dξ
dn O2 = −dξ
dn NO2 = 2dξ
PChem I

8.3

reaction rate: ξ˙ =


dt

(rate of conversion)

dn J = νJdξ
1 d nJ
˙
ξ=
νJ d t

=⇒

dn J
dt

= νJξ˙

single rate for reaction

can follow the time-dependence of any component
If V = const, then the reaction rate can be expressed
by the rate of concentration change

v≡


ξ for V = const
V

v = reaction velocity
dn J
dt

= νJξ˙

PChem I

¯
¯1
¯
¯V
8.4

then that species is called a catalyst if v% as [catalyst] % and an inhibitor if v& as [inhibitor] % If v depends on one or more products. and the reaction is self-inhibiting if v & as [product] %. PChem I 8. then the reaction is autocatalytic if v % as [product] %.1 dn J d(n J/V ) νJ ˙ = = ξ if V = const V dt dt V d[J] dc J νJ ˙ vJ ≡ = = ξ = νJ v reaction velocity of species J dt dt V V ˙ ξ = vJ νJ v J = νJ v rate law: v = f (concentrations) If v depends on the concentration of some species that does not appear in the stoichiometric equation.5 .

are integers. elementary reaction¯ are ¯ called kinetically simple: order of reactant Ji = ¯νi ¯. typically but not always integers x + y + z + · · · = overall order For elementary reactions. .often v = k[A]x [B] y [C]z · · · k : rate constant (depends on T ). . . k > 0 x. Such reactions are also said to obey the Law of Mass Action action or to have PChem I 8. y.6 . the x .: order of the reaction. y . . z. . A −→ D v = k[A] unimolecular A + B −→ D A + B + C −→ D v = k[A][B] bimolecular v = k[A][B][C] termolecular (rare) Reactions that behave kinetically just like a singlestep. .

the equation is kinetically simple and looks like a bimolecular elementary reaction but H2 + Br2 −→ 2 HBr empirical rate law: v =k [H2][Br2]3/2 [Br2] + k 0[HBr] The reaction is first order in H2. the stoichiometric equation looks like an elementary reaction. and no overall order is definable. i.e. no order is definable for Br2 or HBr. PChem I 8. but generally it is not elementary.7 .. Example: H2 + I2 −→ 2 HI empirical rate law: v = k[H2][I2]. The reaction is self-inhibiting. That means.mass action kinetics.

Further examples of empirical rate laws: C2H4O −→ CH4 + CO CH3CHO −→ CH4 + CO N2O5 2 O3 −−−−→ 3 O2 v = k[C2H4O] v = k[CH3CHO]3/2 v = k[O3]2/3[N2O5]2/3 Pt 2 SO2 + O2 −→ 2 SO3 Pt 2 N2O −−−−−→ 2 N2 + O2 741◦ C v = k[SO2][SO3]−1/2 v= k[N2O] 1 + k 0[N2O] Experimental determination of rate laws One cannot measure v J directly.8 . make connection between [J](t) ˙ ) and [J](t two possibilities: differentiate the data or integrate the rate law 1) Differential method A −→ P PChem I 8. measurements: [J](t).

plot ln v A versus ln[A].d[A] [A](t 2) − [A](t 1) ∆[A] = ≈ dt t2 − t1 ∆t ∆[A] average velocity ∆t o 1n [A] = [A](t 1) + [A](t 2) 2 v A([A]) = − n If the rate law has a simple order. then ln v A = ln k + n ln[A]. Method has a major inherent difficulty: d[A] ∆[A] ≈ if ∆t dt ∆t is small but then ∆[A] is small also: division of two small numbers =⇒ need very high precision in the concentration measurement 2) Method of initial velocities (variant of the differential method) example: say PChem I v A = k[A]x [B] y 8. say v A = k[A] . so to determine n .9 .

0 versus ln[A]0 is equal to x keep [A]0 fixed and vary [B]0: slope of ln v A.0 versus ln[B]0 is equal to y problems with this method: H2 + Br2 −→ 2 HBr v0 = k [H2]0[Br2]3/2 0 [Br2]0 + k 0 [HBr]0 | {z } = k[H2]0[Br2]1/2 0 =0 •method does not work for multistep mechanisms •method does not work for complex reactions with initial transients and induction periods 3) Method of integrated rate laws d[J] = v J = νJ f (concentrations) dt PChem I 8.0 = k[A]0x [B]0 ln v A.10 .t =0: y v A.0 = ln k + x ln[A]0 + y ln[B]0 keep [B]0 fixed and vary [A]0: slope of ln v A.

11 .rate law = differential equation solve (integrate) the differential equation (analytically or numerically). A zero-order is PChem I 8. a plot of [A](t ) versus t yields a straight line. then fit data Zero-order reaction k A −→ P v =k d[A] = νA v = −v = −k dt d[A] = −kdt Z [A](t ) Z t d[A] = −k dt [A]0 0 [A](t ) − [A]0 = −kt [A](t ) = [A]0 − kt For a zero-order reaction. Note: Reactions cannot be of zero order for all times — there are no true zero-order reactions — because the reactant concentration cannot become less than zero. which would occur at t = [A]0/k .

a plot of ln([A](t )/[A]0) versus t results in a straight line with slope −k .12 . First-order reaction k A −→ P v = k[A] d[A] = νA v = −v = −k[A] dt d[A] = −kdt [A] Z [A](t ) Z t d[A] = − kdt [A] [A]0 0 ¶ µ [A](t ) = −kt ln [A]0 [A](t ) = [A]0 exp(−kt ) For a first-order reaction. Second-order reaction k A −→ P PChem I v = k[A]2 8.an approximation. which is valid only as long as the reactant is in excess.

Note: If the reaction is k A + A −→ P v = k[A]2 then d[A] = νA v = −2v = −2k[A]2 dt PChem I 8.13 .d[A] = νA v = −v = −k[A]2 dt d[A] = −kdt 2 [A] Z [A](t ) Z t d[A] = − kdt 2 [A] [A]0 0 1 1 − + = −kt [A](t ) [A]0 [A](t ) = 1 1 + kt [A]0 [A]0 = 1 + kt [A]0 For a second-order reaction. a plot of 1/[A](t ) versus t results in a straight line with slope k .

14 . [B](t ) = [B]0 − z(t ) d[A] dz =− dt dt dz = k([A]0 − z) · ([B]0 − z) dt dz = kdt ([A]0 − z) · ([B]0 − z) Z z(t ) dz = kt ([A] − z) · ([B] − z) 0 0 0 µ ¶ Z z(t ) 1 1 1 − dz = kt [B] − [A] [A] − z [B] − z 0 0 0 0 0 · µ ¶ µ ¶¸ 1 [A]0 − z(t ) [B]0 − z(t ) − ln + ln = kt [B]0 − [A]0 [A]0 [B]0 PChem I 8. k A + B −→ P v = k[A][B] d[A] = νA v = −v = −k[A][B] dt [A](t ) = [A]0 − z(t ).and k has to be replaced by 2k in the expressions above.

µ ¶ [A]0 · [B](t) 1 ln = kt [B]0 − [A]0 [A](t ) · [B]0 If [B]0 = [A]0. x = 6 1 x − 1 [A](t )x−1 [A]0x−1 PChem I 8. then d[A] = −k[A]2 dt Reactions of other orders k A −→ P v = k[A]x d[A] = νA v = −v = −k[A]x dt d[A] x = −kdt [A] Z t Z [A](t ) d[A] kdt x =− [A] 0 [A]0 Z t Z [A](t ) d[A][A]−x = − kdt [A]0 0 ª 1 © 1−x 1−x [A](t ) − [A]0 = −kt .15 . x 6= 1 1−x ( ) 1 1 1 − = kt .

Example: k A + B −→ P v = k[A][B]3/2 [B]0 À [A]0 : d[A] = −k[A][B]3/2 dt u −k[B]3/2 0 [A] = −k eff[A] pseudo-first order [A]0 À [B]0 : d[A] = −k[A][B]3/2 dt u −k[A]0[B]3/2 = −k eff[B]3/2 pseudo-one-and-a-half order PChem I 8.For more complicated rate laws. Focus on one species. prepare all other species in large excess. use the method of isolation or method of “flooding”.16 .

17 . A −→ P: µ1 ¶ [A]0 ln 2 = −kt 1/2 [A]0 ln 2 t 1/2 = = 0. A −→ P: t 1/2 = PChem I 2x−1 − 1 (x − 1)k[A]0x−1 8.693k −1 k Second-order reaction. A −→ P: 1 [A]0 [A]0 = 2 1 + kt 1/2[A]0 kt 1/2[A]0 = 1 1 t 1/2 = k[A]0 Reactions of order x (x 6= 1).Information on rate laws from half-life data 1 half-life t 1/2 : [A](t 1/2) = [A]0 2 First-order reaction.

radical recombination reactions. A pre-exponential factor In the Arrhenius law.Temperature dependence of reaction rates µ ¶ Ea k = A exp − Arrhenius law RT E a activation energy. if E a is large.. though in applications they are often not strictly constant but vary slowly with temperature. then the rate is largely independent of temperature Include backward reactions Reversible first-order reaction k1 − * A− ) − −B k −1 Reversible has a different meaning in kinetics than in thermodynamics! PChem I 8.g. e.18 . then k is very sensitive to changes in temperature if E a is zero. E a and A are considered to be constants.

d[A] f = νA v f + νbA v b dt f νA = −1. but if K > 100. v f = k 1[A] νbA = +1. v b = k −1[B] d[A] = −k 1[A] + k −1[B] dt d[B] f = νB v f + νbB v b dt d[B] = k 1[A] − k −1[B] dt Add the two rate equations: d[A] d[B] + = −k 1[A] + k −1[B] + k 1[A] − k −1[B] dt dt ´ d³ [A] + [B] = 0 dt [A](t ) + [B](t ) = const = [A](0) + [B](0) = C PChem I 8.19 . this fact can usually be ignored for purposes of chemical kinetics.All chemical reactions are reversible to some extent.

20 .[B](t ) = C − [A](t ) d[A] = −k 1[A] + k −1{C − [A](t )} dt d[A] = k −1C − (k 1 + k −1)[A] dt equilibrium: d[A]eq =0 dt 0 = −k 1[A]eq + k −1[B]eq [B]eq k1 = = Kc [A]eq k −1 C − [A]eq [A]eq [A]eq = = k1 = Kc k −1 k −1 C k 1 + k −1 d[A] = k −1C − (k 1 + k −1)[A] dt ½ ¾ k −1 = −(k 1 + k −1) [A] − C k 1 + k −1 PChem I 8.

Apply a sudden perturbation to the equilibrium..ª © d[A] = −(k 1 + k −1) [A] − [A]eq dt Z [A](t ) d[A] = −(k 1 + k −1)t [A] − [A] [A]0 eq à ! [A](t ) − [A]eq ln = −(k 1 + k −1)t [A]0 − [A]eq [A](t ) − [A]eq [A]0 − [A]eq © ª = exp −(k 1 + k −1)t ¡ [A](t ) = [A]eq + [A]0 − [A]eq ¢ © ª exp −(k 1 + k −1)t relaxation methods: relaxation = return of a system to equilibrium Relaxation methods are used to measure rate constants.g. e.21 . Then for a re* versible first-order reaction A − ) − B. Let x be the deviation from equilibrium. and monitor the relaxation. our results show PChem I 8. a temperature jump or a pressure jump.

Combine the measurement of the equilibrium constant K c = k 1/k −1 with a measurement of the relaxation time τ to obtain the forward and backward rate constants k 1 and k −1. k1 A −→ B k2 A −→ C d[A] = −k 1[A] − k 2[A] dt PChem I 8.22 . the system relaxes exponentially with a rate 1/τ = k 1 + k −1. Parallel first-order reactions Assume the reactions are irreversible for the moment. after a temperature jump at t = 0.that x(t ) = [A](t ) − [A]eq = x(0) exp(−t /τ) with 1 τ= k 1 + k −1 i.e..

23 .d[B] = k 1[A] dt d[C] = k 2[A] dt add the three equations: ´ d³ [A] + [B] + [C] = 0 dt [A](t ) + [B](t ) + [C](t ) = const = [A](0) + [B](0) + [C](0) = [A]0 if initially only the reactant A is present conversion of reactant into products: [A](t ) = [A]0 exp{−(k 1 + k 2)t } d[B] = k 1[A] = k 1[A]0 exp{−(k 1 + k 2)t } dt ª k 1[A]0 © [B](t ) = 1 − exp[−(k 1 + k 2)t ] k1 + k2 ª k 2[A]0 © [C](t ) = 1 − exp[−(k 1 + k 2)t ] k1 + k2 PChem I 8.

24 .•yield (t → ∞) YirrB = [B](∞) k1 = [A]0 k1 + k2 [C](∞) k2 Yirr = = [A]0 k1 + k2 C •selectivity [B](t ) k 1 = S irr = [C](t ) k 2 for all times What happens if the reactions are reversible? k1 * A− ) −B k −1 k2 * A− ) −C k −2 d[A] = −k 1[A] + k −1[B] − k 2[A] + k −2[C] dt d[B] = k 1[A] − k −1[B] dt PChem I 8.

25 .. the concentrations no longer change with time: d[A] = −k 1[A] + k −1[B] − k 2[A] + k −2[C] = 0 dt d[B] = k 1[A] − k −1[B] = 0 dt d[C] = k 2[A] − k −2[C] = 0 dt k 1[A]eq = k −1[B]eq k 2[A]eq = k −2[C]eq [B]eq [A]eq PChem I = k1 = K c.d[C] = k 2[A] − k −2[C] dt [A](t ) + [B](t ) + [C](t ) = const = [A]0 can eliminate on variable. The reaction reaches equilibrium. i.1 k −1 8.e. say [C]: [C](t ) = [A]0 − [A](t ) − [B](t ) Consider the case t → ∞.

2[A]eq = [A]0 [A]0 [A]eq = 1 + K c.2[A]0 1 + K c.1 + K c.26 .2 k −2 [A]eq + [B]eq + [C]eq = [A]0 [A]eq + K c.1 + K c.1 + K c.1[A]eq + K c.2 K c.2 8.2 •yield (t → ∞) B Yrev = C Yrev = PChem I [B]eq [A]0 [C]eq [A]0 = = K c.2 K c.2 1 + K c.1 + K c.1[A]0 1 + K c.1 + K c.[C]eq [A]eq = k2 = K c.2 [B]eq = [C]eq = K c.1 1 + K c.

•selectivity S rev = [B]eq [C]eq Srev = Sirr · = K c. For long times.27 . PChem I 8.1 [B] S = −−−−−→ = Srev [C] t → ∞ K c.2 = k 1 k −2 k 1 k −2 · = · k −1 k 2 k 2 k −1 k −2 k −1 The selectivity S = [B] k 1 = = S irr [C] k 2 will be observed for short times. the selectivity approaches the equilibrium value K c. as along as the backward reactions are negligible: The reaction is under kinetic control.1 K c.2 The reaction is under thermodynamic control.

4 0. [A]: solid line. [C]: dot-dash line. conc 1.0005 s−1 Initially B is formed ten times faster than C.2 t 1000 2000 3000 4000 5000 6000 7000 Figure 1: Parallel first-order reversible reactions.1 s−1 0.1 = K c.−1 −1 −1 Example: k 1 = 1 s . k 2 = 0. however K c. 0.8 0.1 s . PChem I 8. k −2 = 0.28 . [B]: dashed line. k −1 = 0.01 s = 100 −1 0.6 0.0005 s −1 = 200 and C is the more stable product.2 = 1 s−1 0.01 s .

conc 1. [B]: dashed line.29 .4 0. 0.6 0.8 0. [C]: dot– dash line. [A]: solid line. PChem I 8.2 t 1 2 3 4 5 6 7 8 9 10 Figure 2: Parallel first-order reversible reactions: Initial stage.

01 0.4 0. meta-xylene.30 .conc 1. [C]: dot-dash line.8 0. 0. [B]: dashed line. and para-xylene: PChem I 8.1 1 10 100 1000 10000 Figure 3: Parallel first-order reversible reactions: concentrations versus log t .6 0.2 t 0. [A]: solid line. In the above parallel-reaction mechanism C can be converted into B only via A. What happens if there is the additional reaction k3 * C− ) −B k −3 (An example are the isomerization reactions between ortho-xylene.

m-xylene − ) − p-xylene. all reactions are elementary. p-xylene − * ) − o-xylene.) Let us assume that the three steps are the mechanism of the reaction. i.* * o-xylene − ) − m-xylene.31 . Is it then possible to establish equilibrium by the cyclic reaction mechanism below? B   A  A  A U  A C d[A] = −k 1[A] + k −2[C] dt d[B] = k 1[A] − k −3[B] dt d[C] = k −3[B] − k −2[C] dt [A](t ) + [B](t ) + [C](t ) = const = [A]0 stationary state: k 1[A] = k −2[C] =⇒ PChem I [C] k 1 = [A] k −2 8.e..

and [C] in terms of [A]0 and the three rate constants. [B].32 .[B] k 1 k 1[A] = k −3[B] =⇒ = [A] k −3 k −3[B] = k −2[C]. any molecular proPChem I 8. The principle of microscopic reversibility: In a system at equilibrium. This stationary state is not an equilibrium state!! It violates the principle of detailed balance. [B] = which follows from the previous two equations k1 [A] k −3 k1 [A] [C] = k −2 [A] + [A] = k1 k1 [A] + [A] = [A]0 k −3 k −2 [A]0 k k 1+ k 1 + k 1 −3 −2 We have determined the stationary concentrations [A].

Principle of detailed balance implies that all elementary reactions must be reversible. in a system at equilibrium each elementary reaction must be individually at equilibrium. In other words.cess and the reverse of that process occur. each collision has its exact counterpart in the reverse direction. Application to the scheme k1 * A− ) −B k −1 PChem I 8. every elementary forward reaction is balanced by its own backward reaction. on the average. at the same rate. so that the rate of every chemical process is exactly balanced by that of the reverse process. =⇒ In a system at equilibrium. implies the principle of detailed balance: In a system at equilibrium.33 .

3 = = [C]eq k −3 The product of the second and third equilibrium constants is K c.1 =⇒ PChem I 8.2K c.3 = [C]eq [B]eq [A]eq [C]eq = [B]eq [A]eq = K c.k2 * A− ) −C k −2 k3 * C− ) −B k −3 equilibrium: k 1[A]eq = k −1[B]eq =⇒ K c.2 = k 3[C]eq = k −3[B]eq [B]eq [A]eq [C]eq [A]eq = k1 k −1 = k2 k −2 [B]eq k3 =⇒ K c.1 = k 2[A]eq = k −2[C]eq =⇒ K c.34 .

this relation is general for this mechanism. since it requires k −1 = k 2 = k 3 = 0. it also holds for all nonequilibrium conditions. which is forbidden by the relation. and the cyclic mechanism is impossible.k2 k3 k1 = k −1 k −2 k −3 or k 1k −2k −3 = k −1k 2k 3 This condition on the six rate constants has been derived by considering chemical equilibrium. Therefore. d[A] = −k 1[A] dt PChem I 8. Consecutive first-order reactions (series reactions) k1 k2 A −−→ B −−→ C Assume the reactions are first order and irreversible.35 . We see that the rate constants can never be chosen independently. but rate constants are concentration independent.

[C](0) = 0. and add the three equations: [A](t ) + [B](t ) + [C](t ) = const = [A]0 [A](t ) = [A]0 exp(−k 1 t ) d[B] = k 1[A]0 exp(−k 1 t ) − k 2[B] dt k 1[A]0 [B](t ) = {exp(−k 1 t ) − exp(−k 2 t )} k2 − k1 [C] = [A]0 − [A](t ) − [B](t ) ½ ¾ 1 = [A]0 1 + [k 1 exp(−k 2 t ) − k 2 exp(−k 1 t )] k2 − k1 Consider the case: k 2 À k 1. Then exp(−k 2 t ) ¿ exp(−k 1 t ) PChem I 8.d[B] = k 1[A] − k 2[B] dt d[C] = k 2[B] dt Assume again [A](0) = [A]0.36 . [B](0) = 0.

37 . Illustrate for the consecutive scheme: k 1[A]0 {exp(−k 1 t ) − exp(−k 2 t )} [B](t ) k 2 − k 1 = [A](t ) [A]0 exp(−k 1 t ) = PChem I k1 {1 − exp[−(k 2 − k 1)t ]} k2 − k1 8. A −→ B is the rate-determining step.and k2 − k1 ≈ k2 ½ ¾ 1 [C] ≈ [A]0 1 + · (−k 2) exp(−k 1 t ) k2 = [A]0{1 − exp(−k 1 t )} The formation of C depends only on the rate constant of the first step A −→ B. Motivation for the Steady-State Approximation: After an initial induction period. the concentration and the rate of change of all reaction intermediates are negligibly small.

we obtain d[B] = k 1[A] − k 2[B] dt =⇒ 0≈ k1 [B] = [A] k2 d[C] k1 = k 2[B] = k 2 [A] = k 1[A] dt k2 PChem I 8. to the intermediate B.38 . also known as the quasisteady-state approximation (QSSA).For k 2 À k 1: [B](t ) k 1 k1 ≈ {1 − exp[−k 2 t ]} = | {z } [A](t ) k 2 k2 ≈0 for t À1/k 2 [B](t ) = k1 [A](t ) ¿ [A](t ) k2 d[B] k 1 d[A] d[A] = ¿ dt k 2 dt dt If we apply directly the steady-state approximation (SSA).

39 .= k 1[A]0 exp(−k 1 t ) [C](t ) = [A]0{1 − exp(−k 1 t )} (same as above) Application: decomposition of ozone 2 O3 −→ 3 O2 empirical rate law (M is an inert gas): k[O3]2[M] 1 d[O3] 1 d[O2] = = 0 v =− 2 dt 3 dt k [O2][M] + [O3] proposed mechanism: stoichiometric number k1 O3 + M −−→ O2 + O + M k −1 O2 + O + M −−→ O3 + M k2 O + O3 −−→ 2 O2 PChem I 2 1 1 8.

2 O3 + 2 M + O2 + O + M + O + O3 −→ 2 O2 + 2 O + 2 M + O3 + M + 2 O2 2 O3 −→ 3 O2 intermediate O: steady-state approximation d[O] =0 dt Intermediates do not appear in the rate law!! d[O] = k 1[O3][M] − k −1[O2][O][M] − k 2[O][O3] = 0 dt k 1[O3][M] [O] = k −1[O2][M] + k 2[O3] d[O3] = −k 1[O3][M] + k −1[O2][O][M] − k 2[O][O3] dt n o = −k 1[O3][M] + k −1[O2][M] − k 2[O3] [O] PChem I 8.40 .

41 . k = k −1/k 2 If initially we have pure ozone.d[O3] = −k 1[O3][M]+ dt n o + k −1[O2][M] − k 2[O3] = k 1[O3][M] k −1[O2][M] + k 2[O3] 1 × k −1[O2][M] + k 2[O3] n × − k 1[O3][M]k −1[O2][M] − k 1[O3][M]k 2[O3]+ + k −1[O2][M]k 1[O3][M] − k 2[O3]k 1[O3][M] o 2k 1k 2[O3]2[M] =− k −1[O2][M] + k 2[O3] = −2 k k 1[O3]2[M] −1 k2 = −2v [O2][M] + [O3] 0 empirical rate law: k = k 1. then k −1[O2][M] ¿ k 2[O3] PChem I 8.

B.and d[O3] = −2k 1[O3][M] dt =⇒ the first step is rate-determining The reaction is self-inhibiting in O2. k −1 À k 2 A.42 . v & as [O2] % Another approximation method Pre-equilibrium or fast-equilibrium approximation k1 k2 − * A+B − ) − − X −−→ C k −1 k1 À k2. and X are in equilibrium: k 1[A][B] = k −1[X] [X] = k1 [A][B] = K [A][B] k −1 (Note: K = K c !!) PChem I 8.

43 .d[C] = k 2[X] = k 2K [A][B] = k[A][B] dt k2k1 k = k2K = k −1 enzyme reactions Michaelis-Menten mechanism k1 k2 − * E+S − − −→ P + E (ES) )−− k −1 d[P] = v = k 2[(ES)] dt Apply the steady-state approximation: d[(ES)] = k 1[E][S] − k −1[(ES)] − k 2[(ES)] = 0 dt k 1[E][S] [E][S] [(ES)] = = k −1 + k 2 KM KM = PChem I k −1 + k 2 k1 Michaelis constant 8.

d[P] k 2 [E][S] = dt KM conservation of total enzyme concentration: [E]0 = [E] + [(ES)] [E][S] KM µ ¶ [S] = [E] 1 + KM = [E] + [E] = [E]0 1 + K[S] M d[P] k 2 = [E][S] dt KM = k 2 [E]0 · [S] [S] KM 1 + K M k 2[E]0[S] d[P] =v = dt K M + [S] Michaelis-Menten rate law PChem I 8.44 .

and the rate reaches its maximum: v max = k 2[E]0 [Figure: rate versus substrate concentration.At high substrate concentrations.45 . [S] À K M.. d[P] k 2[E]0[S] u = k 2[E]0. dt [S] the reaction is zero order.3] PChem I 8. Fig. Atkins 9th ed. 23.

that intercepts the ordinate axis at 1/v max and the abscissa at −1/K M. If the enzyme obeys Michaelis-Menten kinetics. PChem I 8. with slope K M/v max.The Michaelis-Menten rate law can be written in terms of v max: d[P] v max =v = dt 1 + K M/[S] We rearrange this expression into a form that is amenable to data analysis by linear regression: KM 1 1 1 + = v v max v max [S] µ ¶ A Lineweaver-Burk plot is a plot of the reciprocal of the velocity v versus the reciprocal of the substrate concentration [S] at fixed enzyme concentration.46 . then the plot should yield a straight line.

d[P] k 2[E]0[S] u = k 0[S].[Figure: Lineweaver-Burk plot.. dt KM the reaction is first order.47 .4] At low substrate concentrations. The turnover number or catalytic constant of an enzyme. 23. is the number of catalytic cycles (turnovers) performed by the active site in a given PChem I 8. k cat. Atkins 9th ed. [S] ¿ K M. Fig.

It has units of a first-order rate constant. v max k cat = k 2 = [E]0 The catalytic efficiency. the rate constant for release of product from the enzymesubstrate complex. of an enzyme is given by η= k cat KM The higher the value of η. and for the Michaelis-Menten mechanism is given by k 2. η. the more efficient is the enzyme.48 . 8 9 −1 −1 diffusion-limited: < 10 – 10 M s for enzyme-sized molecules at room temperature PChem I 8. For the Michaelis-Menten mechanism η= k2 k −1 +k 2 k1 = k1k2 k −1 + k 2 η → η max = k 1 if k 2 À k −1 = rate of formation of the enzyme-substrate complex.time interval divided by the duration of that interval.

49 .0 × 108 M−1 s−1: “catalytic perfection” PChem I 8.catalase (decomposition of hydrogen peroxide) η = 4.