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Thermodynamics: Kinetics
what happens eventually Should I care
H2 + O2 gives H2O + heat
Reaction rate:
how fast to you make products
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
3
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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2
Rate Law
relates Rate to instantaneous concentrations
aA + bB cC + dD
To a power! 5
Measuring
reaction
rates
One of several
choices. Do I
need to measure
all of them?
NO2 + CO NO + CO2
3
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)
4
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
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
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[A]=c
-lnc
d ln c = (1/c)dc
t
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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 )
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
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Chemical Deceit
19
A+B products
10
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
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A in excess
ln (c0A-x)/(c0B-x )=Kt
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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)
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Kinetics and Equilibrium
Detailed Balance
Detailed balance
at equilibrium the forward and backward rates of each
elementary reaction are balanced
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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
29
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]
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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
33
Building a reaction
Rate=1/2d/dt[NO2] = k2[N2O2][O2]
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17
2NO+O2 2NO2
Three body
collisions rare
35
Classic Example
H2 + I2 2HI rate=k[ H2][ I2]
But
hv + I2 2I dramatically increased rate!!!!
36
18
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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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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k1[A][M} / {k-1 [M]+k2}=[A*]
rate=k2[A*]=k2k1[A][M]/{k-1[M]+k2}
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21
M
=
N 2O 5
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EnzymeCatalysis MichaelisMenton Eq
Finish start
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Testing a Mechanism
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24
Verifying Mechanisms
D13
Test predicted rate law
49
Collision
theory
50
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Microscopic description of
A+A -----> products
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26
Collision Theory
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)
27
Total collision
rate/vol
N Z1 /Vx1/2
Notational caveat
kN0 = R
(1/V)dN/dt= -2ZAA
k = [2d2N0÷(p
pRT/M)]
Rate= (-1/2) d[A]/dt= ZAA /N0 =
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Does every collision
cause a reaction?
11 more
57
CH3 + CH3 no
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29
Origin of Activation Energy
Marcelin-1915 not all collisions cause reaction
collision partners must have sufficient
energy to react
59
Maxwell-Boltzmann
and reaction profile
60
30
Maxwell-Boltzmann Distribution
÷(8RT/(Mp))
k = [2d2N0÷(p
pRT/M)]exp(-Eact/RT)
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PROBABILITY
DENSITY(distribution) FUNCTION
f(u) ≥ 0
f
Ú g(u) f (u)du = g
• u u+du
Ú f (u)du = 1
-•
Normalization
u
63
Y*(x) Y(x)
* is complex conjugate
32
Rate Constants
Temperature Dependence
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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steric factor(P)
k = P
2d2N0÷(p
pRT/M)
exp (-Eact/RT)
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steric factor(P)
steriochemistry
35
Reaction sequences can
give deviations from
Arrhenius behaviour
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36
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
73
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
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
Algebra
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dln(c0A -x)=-1/(c0A -x) dln(c0P +x)=1/(c0P +x)
C0X =[X]0
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Auto catalytic reactions can be
used as the building block of
cyclic reactions
81
Autocatalytic(AC)-cyclic reaction(CR)
AC––––> CR
Far from equilibrium
‘intermediates’ key
Cant use steady state
approxmation
82
41
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
84
42
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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