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Kinetics

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

Concentrations as a function of time


Road Map from React to Products 1

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 Steady state approximation
compareA+B vs C+D something about C
Collision theory TEMPERATURE Arrhenius A factor and E act
Reaction profile - Activation energy MB Distribution as a pdf
Auto catalytic and cyclic reactions:Some things are worth doing
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over and over

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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! 5

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)

Stiochiometry and Rates


aA + bB cC + dD

- 1 d [A](t) - 1 d [B](t) 1 d [C](t) 1 d [D](t)


a dt b dt c dt d dt

What does overall reaction tell you about rate law

Stiochiometry gives ratios of A, B, C, D


Not
reaction mechanism 8

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Rate Law
Relates rate to instantaneous concentrations
aA + bB cC + dD
n 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 constant-
not a function -1 d A(t) = rate(t)
of time but a dt
k(T,P) 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
Differential to Integrated rate law
- 1 d[A](t) = k dt
Divide by [A]
[A](t)

dln(x)=dx/x
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• -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

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


0.5*A(0)/A(0) = exp(-k t)
ln2/k= t
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[A]=c
-lnc
d ln c = (1/c)dc
t

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Second Order Rate Law

2A products -d [A](t) = 2k [A](t)2


dt
Note: convenient to
include 1/2 otherwise
rate is for loosing 2 - 1 d[A](t) = 2k dt
A’s [A](t)2

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

c( t ) 2
= 2 kdt Úc( 0 ) c2 = 2k Ú0 dt
c( 0 ) - c( t )
c(t )
1 1 1
= - = 2 kt =
c c(0) c( t ) c( 0 ) c(0)c(t )

2 ktc(0) = c(0) / c(t ) - 1 15

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: Half life
-1/(c0/2)+1/c0=-2kt depends
on c0
1/ c0=2kt
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2000 Words
1/c
-lnc

t
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 products

c0A c0B initial x= amount/V of A reacted


concentrations

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)


(dx/dt) =k(c0A-x)(c0B-x)

dx/ [(c0A-x)(c0B-x )]=kdt 20

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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 )]
1= D c0A+C c0B 0= D x+Cx difference of these two equations
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 c0Aπ c0B
Effective rate constant depends concentration

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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

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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
n n n nd
-(1/a)d/dt[A](t)=k [A](t) a [B](t) b[C](t) c[D](t)

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
d/dt[Prod] = k [A]n [B]m[C]c 28

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Complex mechanism
Observed reaction: 2A+2B––> C+D
Elementary Steps: Why some
A+A<–––> F consider forward and Back forward only
some both
F+B––––>G consider forward
REACTION
G+B––––>C+D consider forward PATH
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] A+A<–––> F
!d/dt[F]=k1[A]2 – k-1[F]–k2[F][B] 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 2NO2

Three body
collisions rare

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Classic Example
H2 + I2 2HI rate=k[ H2][ I2]
But
hv + I2 2I dramatically increased rate!!!!

•M + I2 I+I+M fast K 1 = [I]2/[I2]!


•I + H2 H2I fast K 2 = [H2I] /[H2][I]
•H2I + I 2HI 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 K1 = [I]2/[I2]
=kK2K1[I2] [H2]

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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* + M
A* products d [A*](t) = 0
NET: A ––––> prod 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 53

Average velocity

÷(8RT/(Mp)) = <u>

Collision frequency
=collisions/time= Z1
Vol swept out/time

{[ pd2<u>]} density÷2 = 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 A+A ––––––> products

(1/V)dN/dt= -2ZAA

[ ] = Molar density = r/N0


d[A]/dt= -2ZAA/N0

k = [2d2N0÷(p
pRT/M)]
Rate= (-1/2) d[A]/dt= ZAA /N0 =

2d2r2 (N0 /N02)÷(pRT/M)=

[A]2 [2d2N0÷(pRT/M)]=k [A]2

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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 no

But in general 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 Ú g(u) f (u)du = g

Fraction of molecules with


energy > Eact decreases like
exp(-Eact/kT)
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k = [2d2N0÷(p
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
f

Ú g(u) f (u)du = g
• u u+du

Ú f (u)du = 1
-•
Normalization
u

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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 Schrödinger Equation

Ú Y * ( x )g( x )Y( x )dx = g


Expectation - average - value
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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 + C––O –––> O–––N + O––C––O
O–– N–– O + O–– C ––––>

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steric factor(P)

k = P

2d2N0÷(p
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)
Rate (k) ~ exp(-E/RT) decreases
increases exponentiallywith T

expExo/RT
exponentiallywith T
exp-E/RT

T
T
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) 2NO2 (g)

NO + NO <––––> N 2O 2 fast
N2O2 + O2 ––––––> 2NO2 slow
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

A bexp-E ab/RT
Ex0
=exp-(E af -E ab)/RT
=expE xo/RT

As T increases k2
increases but K1
expExo/RT

decreases
exp-E/RT

T
k =
T

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


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 83

Lotka-Volterra

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X

d[ A]
= - ka [ A][ X ] A + X Æ 2 X (A Æ X)
dt

rb = - kb [Y ][ X ] Y + X Æ 2Y ( X Æ Y )

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