Kinetics

Thermodynamics: what happens eventually H2 + O2 gives H2O + heat Reaction rate: how fast to you make products Kinetics

Should I care

Concentrations as a function of time Road Map from React to Products

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Kinetics
Rate law - concentrations related to their changes- differential integral form - conc as function of time [A](t) Rate law from reaction mechanism:path from Reac to Prod Reaction Mechanism- Sequence of Elementary Steps A+B > C; C+D> E overall A+B+D>E Rate determining step compareA+B vs C+D Collision theory TEMPERATURE Steady state approximation something about C Arrhenius A factor and E act MB Distribution as a pdf

Reaction profile - Activation energy

Auto catalytic and cyclic reactions:Some things are worth doing 2 over and over

Rate constant k(T,P) - Arrhenius Rate laws - mechanistic interpretation Microscopic theory of chemical reaction rates Reaction paths Maxwell-Boltzman Distribution and activation energy
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Rate Laws Instantaneous Rate laws - relation between concentrations and their rate of change (reaction rate) differential equations Integrated rates laws concentrations as function of times
Instantaneous Rate law > Integrated rate law
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Rate Law
relates Rate to instantaneous concentrations aA + bB cC + dD

Expectation the more A and B the more C produced in a given time ie Rate is proportional to concentration

To a power!

Measuring reaction rates One of several choices. Do I need to measure all of them?

NO2 + CO

NO + CO2
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Reaction Rates
Rate = d A(t) dt
x
[A](t)

B+C

A+D

Re-phrasing What is the relation between rate and stoichiometry

t(s)
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Stiochiometry and Rates

aA + bB cC + dD 1 d [C](t) c dt 1 d [D](t) d dt - 1 d [A](t) - 1 d [B](t) a dt b dt

What does overall reaction tell you about rate law

Stiochiometry gives ratios of A, B, C, D

Not

reaction mechanism
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Rate Law
Relates rate to instantaneous concentrations aA + bB
n

cC + dD
n n nd

Rate(t) = k {[A](t)} a {[B](t)} b{[C](t)} c{[D](t)}

Order of reaction = na+ nb+ nc+ nd

Rate constantnot a function of time but k(T,P) -1 d A(t) = rate(t) a dt So rate law is a diff. eq.
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First Order Rate Law Unimolecular Decay

A products Examples:Photodissociation O2+ hv > O2* > O + O absorb high frequency photons O3+ hv > O3*> O2+O absorb uv
ONLY ACTIVATED STATE DECAYS
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First Order Rate Law Unimolecular Decay

A products -d [A](t) = k [A](t) dt - 1 d[A](t) = k dt [A](t)
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Differential to Integrated rate law

Divide by [A]

dln(x)=dx/x

-d ln [A](t) = k dt Integrate from (t=0 A(0)) to (t=t, A(t)) ln(A(t))- ln (A(0))=-kt A(t)/A(0) = exp(-kt) lnB-lnA=lnB/A

0.5*A(0)/A(0) = exp(-k t) ln2/k= t

Half life : t for which A( t) = A(0)/2

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[A]=c d ln c = (1/c)dc -lnc t

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Second Order Rate Law

-d [A](t) = 2k [A](t)2 dt - 1 d[A](t) = 2k dt [A](t)2
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2A

products

Note: convenient to include 1/2 otherwise rate is for loosing 2 As

[ A](t ) = c(t ) - dc = 2 kdt 2 c( t )

c(t ) t - dc 0 ) c2 = 2k 0 dt c( c(t )

1 1 1 c( 0 ) - c( t ) = = 2 kt = c(0)c(t ) c c(0) c( t ) c( 0 ) 2 ktc(0) = c(0) / c(t ) - 1

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Half Life 2ktc(0)=c(0)/c(t)-1

2kt1/2 c(0)=c(0)/c(0)/2-1=1 t1/2=1/(2kc(0)) Concentration dependent

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Half life: -1/(c0/2)+1/c0=-2kt 1/ c0=2kt

Half life depends on c0

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2000 Words
-lnc t 1/c t

First order

second order

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Chemical Deceit
Initial Conditions can make things appear other than they are

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A+B
c0A c0B initial concentrations

products
x= amount/V of A reacted

c0A-x= concentration of A at time t = [A](t) c0B-x= concentration of B at time t = [B](t) -d[A]/dt= k [A](t) [B](t) =k(c0A-x)(c0B-x)

(dx/dt)

dx/ [(c0A-x)(c0B-x )]=kdt

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1/ [(c0A-x)(c0B-x )] = C/ [c0A-x]+D/ [c0B-x ] 1= D [c0A-x]+C [c0B-x ] multiply by [(c0A-x)(c0B-x )] is the previous line (underdetermined So that C=-D and 1/(c0A- c0B)=D OK only if initial concentrations are distinct -dx / [c0A-x]+dx/ [c0B-x ] =(c0A- c0B)kdt = Kdt dln[c0A-x] - dln [c0B-x ] = Kdt (c0A-x)/(c0B-x )=eKt for c0A c0B Effective rate constant depends concentration

1= D c0A+C c0B 0= D x+Cx difference of these two equations

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Plot

ln (c0A-x)/(c0B-x )=Kt
Two cases: A or B in excess

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A in excess
ln (c0A-x)/(c0B-x )=Kt

-ln(c0B-x )=Kt- ln (c0A-x) ~ Kt- ln (c0A)

-ln[B] Looks like unimolecular decay of B t

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Complex Rate Laws

Building blocks are Elementary Reactions

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Elementary Reaction
Definition:Stoichiometry gives rate law
aA + bB> cC + dD -(1/a)d/dt[A](t)=k [A](t) a [B](t) b[C](t) c[D](t)
n n n nd

na=a nb=b nc=0 nd=0

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Beyond Forward Reactions

A+B > C+D as soon as C and D exist C+D > A+B

Overall rate of single reaction is forward rate - backward rate

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Kinetics and Equilibrium Detailed Balance

Detailed balance at equilibrium the forward and backward rates of each elementary reaction are balanced

A+B

C + D kf [A][B] = kb[C][D]
K= kf / kb
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Reaction Mechanism

D(12)

Sequence of Elementary Reactions Elementary Reaction DEFINITION Stoichiometry gives rate law nA + mB+cC> products
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d/dt[Prod] = k [A]n [B]m[C]c

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Complex mechanism
Observed reaction: 2A+2B> C+D
Elementary Steps: A+A<> F F+B>G consider forward and Back consider forward Why some forward only some both REACTION PATH

G+B>C+D consider forward SUM 2A+2B>C+D

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Rules
Rate law for individual steps unaffected by existence other steps Concentration of any species is the net of all reactions in which it is involved; Net=sources - sinks
!d/dt[C] = k3[G][B] !d/dt[F]=k1[A]2 k-1[F]k2[F][B] A+A<> F F+B>G G+B>C+D
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RATE LAW is deduced from !d/dt[C] = k3[G][B] But how to get [G]?

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Determining Rate Laws

Simplifying assumptions
Rate determining step (prior equilibrium) Steady state approximation (Reactive intermediate)
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Rate determining step

Slow step in a reaction mechanism

Rate of reaction is rate of this step

Prior steps reach equilibrium Subsequent step(s) fast/irrelevant

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Building a reaction
2NO+O2 > 2NO2 Built from NO+NO <> N2O2 in equilibrium N2O2 + O2 > 2NO2 rate determining

Note sum of elementary reactions is the overall reaction Rate=1/2d/dt[NO2] = k2[N2O2][O2]

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2NO+O2 Three body collisions rare

2NO2

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Classic Example
H2 + I2 But hv + I2 2HI rate=k[ H2][ I2]

2I dramatically increased rate!!!!

M + I2 I + H2 H2I + I

I+I+M H2I 2HI

fast K 1 = [I]2/[I2]! fast K 2 = [H2I] /[H2][I] slow rate= [H2I] ][I]

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rate= k[H2I] ][I]

K 2 = [H2I] /[H2][I] K 2 [H2][I]= [H2I]

rate= kK2 [H2][I] [I] = kK2 [H2][I]2 =kK2K1[I2] [H2] K1 = [I]2/[I2]

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Steady State Approximation

No rate determining step Applies to (an) intermediate I d [I](t) = sources - sinks = 0 dt

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Lindemann Activated Complex Mechanism: Collisional Activation

Observation: A in an inert gas ( buffer gas) decomposes rate constant is unimolecular(sum of exponents=1) for normal gas pressure for low gas pressure rate is bimolecular( sum of exponents =2)

EXPLAIN

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Steady- State Approximation and Lindemann Activated Complex Mechanism: Collisional Activation
A+M A* A* + M products

NET: A > prod

d [A*](t) = 0 dt

k1[A][M] -k-1 [A*][M]-k2[A*] = 0

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k1[A][M} / {k-1 [M]+k2}=[A*]

rate=k2[A*]=k2k1[A][M]/{k-1[M]+k2}

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N2O5 > 2NO2 + 1/2 O2 Steady- State Approximation and Lindemann Activated Complex Mechansim N2O5 +M <> N2O5*+M N2O5* > 2NO2 + 1/2 O2

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M = N 2O 5

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EnzymeCatalysis MichaelisMenton Eq
Finish start

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Testing a Mechanism

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Verifying Mechanisms D13 Test predicted rate law NO2 + CO > NO + CO2 Chemical methods- isotopic substitution
12C18O

( no 18O in NO)

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Collision theory

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Microscopic description of A+A -----> products

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Rate equation from collision theory # of Collisions Start with 1 particle - sweeping out a volume collisions = volume times density volume = x section velocity (> per unit time) velocity = MB-velocity total collisions mult by N particles / volume /2 since A collides with A-A Units: [A] = density/N0 d[A]/dt = -twice the collision frequency
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Collision Theory
Area x velocity= volume/time

u from MB

V x density(almost)=# of collisions
Average velocity

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(8RT/(Mp)) = <u>

Collision frequency =collisions/time= Z1 Vol swept out/time {[ pd2<u>]} density2 = Z1 = 4d2r(pRT/M) particles in vol swept out
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Total collision rate/vol N Z1 /Vx1/2

Notational caveat kN0 = R

N such molecules so

Total number of collisions/time/vol = Total number of collisions/time 1/2 N/V Z1 = 1/2r Z1 = 1/2 N Z1 =1/2r4d2r(pRT/M)= ZAA
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One collision eliminates two As (1/V)dN/dt= -2ZAA [ ] = Molar density = r/N0 d[A]/dt= -2ZAA/N0 Rate= (-1/2) d[A]/dt= ZAA /N0 2d2r2 (N0 /N02)(pRT/M)= [A]2 [2d2N0(pRT/M)]=k [A]2
=

A+A > products

p k = [2d2N0(pRT/M)]

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Does every collision cause a reaction?

11 more

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Do all k have dramatic temperature dependence CH3 + CH3 But in general no yes

Why is CH3 + CH3 different?

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Origin of Activation Energy Marcelin-1915 not all collisions cause reaction collision partners must have sufficient energy to react

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Maxwell-Boltzmann and reaction profile

Average is not everything

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Maxwell-Boltzmann Distribution

<u> = average speed = (8RT/(Mp)) where

g(u) f (u)du =

Fraction of molecules with energy > Eact decreases like

exp(-Eact/kT)
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p k = [2d2N0(pRT/M)]exp(-Eact/RT)

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PROBABILITY DENSITY(distribution) FUNCTION

f(u)du is the probability of having u (velocity) between u and u+du f(u) 0

g(u) f (u)du = g
-

f (u)du = 1

u+du

u Normalization

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Coming soon another pdf Y*(x) Y(x) * is complex conjugate Y(x) is the wave function obtained from the solution of Schrdinger Equation

Expectation - average - value

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Y * ( x )g( x )Y( x )dx =

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Rate Constants Temperature Dependence

Arrhenius-1889 k(T)=A exp(-Eact/kT) Eact -activation energy-is independent of T A is the Arrhenius or prefactor. It has as a small temperature dependence. What is the microscopic origin of Eact and the temperature dependence of A.
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Origin of Eact (10 +cl)

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Is the theory complete yet?

k= 2d2N0(pRT/M) exp (-Eact/kT)

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Not all directions of approach are equivalent

O N O + CO O N O + O C > ON + OCO >

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steric factor(P)

k =

p 2d2N0(pRT/M) exp (-Eact/RT)

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Two pieces missing from collision theory

Activation

exp (-Eact/kT) steric factor(P)

steriochemistry

k=P 2d2N0(pRT/M) exp (-Eact/RT)

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Reaction sequences can give deviations from Arrhenius behaviour

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Negative Activation Energy

What is the T-dependence of k?

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Can the RHS occur Rate (k) ~ exp(-E/RT) increases exponentiallywith T Rate (k) ~ exp(E/RT) decreases exponentiallywith T

exp-E/RT

expExo/RT

T = 0 E / RT = exp( - E / RT ) = 0 exp( E / RT ) = T = E / RT = 0 exp( - E / RT ) = 1 exp( E / RT ) = 1

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Negative Activation Energies

2NO(g) + O2(g) NO + NO <> 2NO2 (g) N 2O 2 fast slow

N2O2 + O2 > 2NO2 Rate = k2K1[NO]2[O2]

K1 = k1/k-1 will use Arrhenius k to evaluate K

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- EaF + EaB = Exo > 0

K=Af exp-E af /RT Ex0 A bexp-E ab/RT =exp-(E af -E ab)/RT =expE xo/RT
As T increases k2 increases but K1 decreases
T

exp-E/RT

k = keff ~ exp[ -( Ea 2` - Ex 0 ) / RT ] eff

expExo/RT

k2K1
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S u r f a c e C a t a l y s i s
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Autocatalytic and Oscillatory reactions

Rate= k[A][P] A P
[A]=c0A-x [P]=c0P+x -d[A]/dt = dx/dt= k(c0A-x ) (c0P+x) Usual trick dx/((c0A-x ) (c0P+x))=kdt A decreases with time but P increases
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Algebra
1/ [(c0A-x)(c0P+x )] = C/ [c0A-x]+D/ [c0P+x ] 1= D [c0A-x]+C [c0P+x ] 1= D c0A+C c0P 0= -D x+Cx So that C=D and 1/(c0A+ c0P)=D

+dx / [c0A-x]+dx/ [c0P+x ] =(c0A+ c0P)kdt = adt

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dln(c0A -x)=-1/(c0A -x)

dln(c0P +x)=1/(c0P +x) C0X =[X]0

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Key point:rate starts slow and increases with time

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Auto catalytic reactions can be used as the building block of cyclic reactions

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Autocatalytic(AC)-cyclic reaction(CR)
AC> CR Far from equilibrium intermediates key Cant use steady state approxmation
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Lotka-Volterra Model Auto catalytic reaction

AC feedback AC First order-Not AC

Start with little X and y Steady state condition [A] constant NOT steady state approximation A>B

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Lotka-Volterra

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d[ A] = - ka [ A][ X ] dt

A + X 2 X (A X)

rb = - kb [Y ][ X ]

Y + X 2Y ( X Y )
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