Chemical Kinetics Reaction Orders

Introduction Consider the reaction for the combustion of hydrogen gas: 2H2(g) + O2(g) 2H2O(l) At room temperature and pressure, H for this reaction is: 2H
o f

!H2O(l)" # $2H

o f

!H2(g)" + H

o f

!O2(g)"%

& 2(#2'()'* +,-mol) & #(./)00 +,-mol (strongly e1othermic)

2he products are energetically fa3ored) 2he reactants are entropically fa3ored (Sgas 44 Sli5uid)) 6ill this reaction proceed spontaneously7 2o ans8er this 5uestion, 8e must resort to 2nd la8 ideas, in particular, to the 9ibbs free energy) At room temperature and pressure, G & H # TS for this reaction is: 2G
o f

!H2O(l)" # $2G

o f

!H2(g)" + G

o f

!O2(g)"%

& 2 (#2*.)/* +,-mol) & #:.:)20 +,-mol ;ince G < = for this process, thermodynamics predicts that this reaction 8ill proceed spontaneously) Ho8e3er, 8hen H2(g) and O2(g) are mi1ed at ordinary room temperature and pressure, no obser3able 5uantity of H2O(l) is formed, because the rate of formation of H2O(l) is 3ery slo8) 2hermodynamics tells us nothing about reaction rates) Indeed, time as a 3ariable does not enter into any thermodynamic e5uations) 2he realm of reaction rates is go3erned by the science of chemical kinetics) >efinitions Consider the model reaction A ?

and let !A" and !?" represent the concentrations of the reaction participants at any gi3en time t during the course of the reaction) 2he easiest 8ay to 5uantify ho8 fast the reaction proceeds (the rate of the reaction) is to monitor the rate of formation of product, or e5ui3alently, the rate of consumption of reactant) 2he rate of formation of product is gi3en by v? &
d !?" dt

and a typical graph trac+ing the concentration of species ? o3er time might loo+ li+e this: !? "

t ;ince ? is a product, !?" al8ays increases as the reaction proceeds, so positi3e, i)e), v? is positi3e) 2hus, the rate of the reaction A ? is v? &
d !?" dt d !?" is al8ays dt

Analogously, the rate of consumption of reactant is gi3en by vA & #

d !A" dt

and a graph sho8ing ho8 !A" changes 8ith time might loo+ li+e this: !A "

t ;ince A is a reactant, !A" al8ays decreases as the reaction proceeds, so negati3e, i)e), vA & # by the formula
2

d !A" is al8ays dt

d !A" is positi3e) 2hus, the rate of the reaction A ? is also gi3en dt

vA & #

d !A" dt

@ote that vA & v?, i)e), the rate of formation of ? e5uals the rate of consumption of A) Aor a slightly more complicated reaction, e)g), 2H2 + O2 2H2O the rate of formation of H2O & 2 rate of consumption of O2 ?B2 the rate of formation of H2O & rate of consumption of H2C Ho8 do 8e define the rate of this reaction7 reaction rate v
d !O 2 " / d !H 2 O" / d !H 2 " & & 2 dt dt 2 dt

In general, then, for any chemical reaction aA + b? cC + d> the reaction rate is defined as: v &
/ d !A" / d !?" / d !C" / d !>" & & & a dt b dt c dt d dt

))) (/)

Date Ea8s Often, one finds e1perimentally that the rate of a reaction is proportional to the concentrations of the reactant(s) raised to a po8er, e)g) for a reaction A + ? C
*

it may be found that v & k!A"2 v & k!A"!?" v & k v & k!A"!?"2 v & k!A"F!?" ))) etc) 2hese e5uations describing the relation bet8een the reaction rate and concentrations of the reactants are +no8n as rate laws (or rate equations or rate expressions)) 2he constant k in these e1pressions is called the rate constant, 8hich is independent of reactant concentration, but is dependent on temperature) 2he po8er to 8hich the concentration of a species is raised in a rate la8 is the order of the reaction 8ith respect to that species) 2he sum of the orders of all the concentrations in the rate la8 is called the o3erall order of the reaction) Aor e1ample, if a rate la8 for a reaction is found e1perimentally to be v & k!A"!?"G!C"F the reaction is said to be /st order in !A", G order in !?" and F order in !C") 28o fundamentally important facts must be +ept in mind at this stage) 1. H5uations (/) define the rate of a chemical reaction) 2he rate of any chemical reaction can be defined based on the balanced chemical e5uation for the reaction) 2. H5uations (2) are experimentally determined e5uations describing the rate of a chemical reaction and its dependence on reactant concentrations) 2he order of the reaction 8ith respect to any species has nothing to do 8ith the stoichiometry of the reaction) ou cannot predict the rate law for a reaction from the balanced chemical equation for the reaction. An e1ample 8ill help clarify this distinction) Consider the simple reaction H2 + ?r2 2H?r It is a straightfor8ard matter to define the reaction rate for this reaction based on the balanced e5uation Iust gi3en: ))) (2)

d !H 2 " d !?r2 " / d !H?r" & & 2 dt dt dt

Ho8e3er, it too+ years of painsta+ing e1perimental measurements on this system for researchers to establish that the rate of this reaction is gi3en by the rate la8

k!H 2 "!?r2 " 2 v & !?r2 " + k! !H?r"

It 8ould ha3e been patently impossible, by merely loo+ing at the chemical e5uation for this reaction, to ha3e come up 8ith this rate la8 for the reaction bet8een H2 and ?r2) @ote that as far as the order of this reaction is concerned, one can only say that it is first order in H2J it is impossible to state the order of this reaction 8ith respect to ?r2, or the o3erall order of the reaction) @ote also that the concentration of the product H?r appears in the rate la8, and that there are t8o rate constants k and k"C 2hese are not uncommon occurrences in the study of real reactions) 6e no8 turn our attention to reactions of specific order) Airst Order Deactions Consider the reaction A 2? + C #y definition, the rate of the reaction is: v &
d !A" / d !?" d !C" & & dt 2 dt dt

;uppose 8e find by experiment that this reaction obeys the rate la8: v & k!A" 2hus, the reaction is first order in !A") 6e can e5uate the t8o e1pressions for v, to find:
d !A" & k!A" dt

2his is a differential e5uation in the 3ariables !A" and t) Dearranging,

d !A" & #kdt !A"

Integrating both sides of this e5uation,

t / d !A" kdt & !A" !A"o =

!A"

ln!A" # ln!A"o & #k(t) ln!A" & #kt + ln!A"o

!A" ln !A" o = kt

))) (/) ))) (2) ))) (*)

!A" & !A"oe#kt ))) (:) 2hese four e5uations are different, e5ui3alent forms of the inte$rated rate law for a first order reaction) 2his integrated rate la8 clearly states the time dependence of the concentration of reactant A, namely that !A" decays e1ponentially 8ith time) A plot of !A" against time is sho8n belo8 for a couple of different 3alues of k) @ote that the larger the 3alue of k, the faster the reaction proceeds) [A]
!A"o

k small k large

t 2he half%life, tF, of a reactant is the time re5uired for its concentration to drop to half its initial 3alue) In the abo3e reaction, for e1ample, it is the time re5uired for the molarity of A to decrease from !A"o to F!A"o) It should be noted that all radioacti3e decay processes follo8 first order +inetics) 2he idea of a halfKlife can be e1pressed mathematically using e5uation (*):

/ 2 !A"o ln !A" o

= kt /2

ln ( / 2) = t /2 k
t /2 = ln2 k

(ln2 =)0L*)

Aor a first order reaction, therefore, the halfKlife is independent of the initial reactant concentration) A less fre5uently used parameter called the relaxation time for a first order reaction is defined as:
= / k

;econd Order Deactions Consider the reaction A + ? 2C ?y definition, the rate of this reaction is: v &
d !A" d !?" / d !C" & & dt dt 2 dt

;uppose 8e find by e1periment that this reaction obeys the rate la8: v & k!A"2 2hus, the reaction is second order in !A") 6e can once again e5uate the t8o e1pressions for v, to find:
d !A" & k!A"2 dt

Dearranging this e1pression as before, 8e obtain

d !A" & #kdt !A"2

?oth sides of this e5uation can be integrated:

t / d !A" kdt & 2 !A"o !A" =

!A"

/ / !A" !A"o

& #k(t)

/ / !A" !A"o

& kt

/ / & kt + !A" !A"o

))) (()

6hen analyMing a +no8n second order reaction, one 8ould plot /-!A" against t, 8hich 8ould gi3e the rate constant k as the slope) ;ol3ing e1plicitly for !A", ho8e3er, yields the formula !A" &
!A"o / + kt!A"o

8hich gi3es the time dependence of the concentration of !A") @ote that it is roughly /-t dependence) 2he plot of !A" against time for this second order reaction sho8s a remar+able similarity to the analogous plot for first order +inetics: [A]
!A"o

k small k large

2he halfKlife for this reaction is defined in the same 8ay as in the first order case) Nathematically, 8e substitute the time and the concentration of A into e5uation (() to get the follo8ing e1pression:

'

/ / & ktF + / !A" o 2 !A"o

2 / & kt F + !A"o !A"o / & ktF !A"o

tF & k !A" o

@ote that the halfKlife of a second order reaction depends on the initial concentration of reactant) @o8 suppose that the reaction 8e ha3e studied, A + ? 2C 8as found e1perimentally to ha3e the rate la8 v & k!A"!?" 2his is also a second order reaction (o3erallJ first order in each reactant)) @o8, proceeding as before, 8e e5uate the defined rate to the e1perimentally determined rate:
d !A" & k!A"!?" dt

))) (0)

2he abo3e differential e5uation has three 3ariables (!A", !?" and t), and cannot be sol3ed as stated) Instead, 8e introduce a ne8 3ariable x, 8here x !A"o # !A" 2he 5uantity x can be recogniMed as the amount of A consumed) @ote that 8e could Iust as 8ell ha3e defined x as !?" o # !?", since A and ? are consumed at the same rate in this reaction) Our differential e5uation (0) no8 becomes
d !A" & k(!A"o # x)(!?"o # x) dt

@o8 8e need to re8rite !A" in terms of x, in order to get a differential e5uation solely in terms of x and t:
L

!A" & !A"o # x

))) (.)

>ifferentiating both sides of (.) 8ith respect to t, 8e obtain

d !A" dx = dt dt

since !A"o is a constant 8hich does not depend on t) H5ui3alently, 8e could 8rite,
d !A" dx = dt dt

6e no8 8rite our differential e5uation (0) entirely in terms of the t8o 3ariables x and t:
dx & k(!A"o # x)(!?"o # x) dt

Dearranging,

(!A"o x )(!?"o x )

dx & kdt

Integrating both sides (x & = at t & =),

(!A"
=

x )(!?"o x )

dx = kdt
=

2his 8or+s out to:

!A"o !?" / ln & kt !?"o !A"o !?"o !A"

2he abo3e integrated rate la8 is 3alid for the reaction A + ? 2C, 8ith rate e1pression v & k!A"!?") @otice that the e5uation blo8s up 8hen !A" o & !?"o) Aor this reaction, the 5uantity ln(!?"-!A") can be plotted against t to obtain the 3alue of k from the slope) 9eneraliMing, for any reaction aA + b? products obeying the rate la8 v & k!A"!?"

the integrated rate la8 is:

!A"o !?" / ln & kt a!?"o b!A"o !?"o !A"

Oeroth Order Deactions Consider the reaction A P ?y definition, the rate of this reaction is gi3en by the formulas v
d !A" d !P" = dt dt

;uppose 8e find by e1periment that this reaction obeys the rate la8 v & k 2hat is, the rate of this reaction has no dependence on the reactant concentration, or the reaction rate is Mero order 8ith respect to the reactant) Oero order +inetics only sho8 up in heterogeneous reactions) @o8, 8e can e5uate the t8o e1pressions for v to obtain
d !A" & k dt

d!A" & #kdt

Integrating both sides,

!A"

!A"o

d !A"

& kdt
=

!A" # !A"o & #k(t) !A" & #kt + !A"o ))) (')

A plot of !A" against t in this case 8ill yield a straight line 8ith slope #k: [A] !A"o k small k large
/

2he halfKlife of a Meroth order reaction is obtained from e5uation ('):

!A"o # !A"o & #ktF 2

!A"o & ktF 2

tF &

!A"o 2k

Deactions of 9eneral Order In general, for a reaction A products, for 8hich, by definition v
d !A" dt

and 8hich follo8s the e1perimentally determined rate la8 v & k!A"n (n /)

the integrated rate la8 is:

/ / n / n / & (n # /)kt !A" !A"o

2he halfKlife in this general case is gi3en by the formula:

2 n / / tF & n / ( n /) k!A"o

@o reactions are +no8n 8ith order n 4 *)