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Rates and Mech
Rates and Mech
C.P. Huang
University of Delaware
1
Content
1. Introduction
2. Reaction rate
3. Rate laws
4. Analysis of rate equations
5. Rate theories
6. Reaction mechanisms
1. Complex
2. Catalysis
3. Chain
7. Reactions in solution
8. Reactions at interface
2
1. INTRODUCTION
3
Objectives
4
Why kinetics
5
2. REACTION RATE
6
Definition of reaction rate
• Rate – change in some variable per unit time
Rate 1/time
• Reaction rate – change in concentration per unit time;
M/s or mol/(L-s)
• Rates are determined by monitoring concentration as
a function of time
• Rates are negative for reactants and positive
quantities for products
7
Types of reaction rate
• Instantaneous rate – rate at a specific time
• Average rate – ∆[A] over a specific time interval
• Initial rate – instantaneous rate at t = 0
8
Factors affecting reaction rate
• Kinetics are very difficult to describe from first
principles
– Structure, elements, behavior
• Rate of reaction describes how fast reactants are
used up and products are formed
• There are 4 basic factors that affect reaction rates
– Nature of reactants
– Effective concentrations
– Temperature
– Presence of catalysts
– Number of steps
9
Nature of reactants: particle size
• The degree of intimacy among particles obviously
depends on the physical nature of the particles.
• Particles in the liquid state are closer than in the
solid state.
• Likewise, particles in a finely divided solid will be
closer than in a chunk of the solid
• In both situations, there is a larger surface area
available for the reaction to take place
• This leads to an increase in rate.
The smaller the particles the faster the reaction rates
10
Nature of reactants: bonding
• Ions react rapidly:
Ag+ + Cl- AgCl(s) Very fast
• Reactions which involve bond breaking are slower:
NH4+ + OCN- OC(NH2)2
• Redox reactions in solutions are slow
• Transfer of electrons are faster than those of atoms.
• Reactions between covalently bonded molecules are
slow:
2 HI(g) H2(g) + I2(g)
11
Concentration
• For every reaction the particles must come into
intimate contact with each other.
• High concentrations by definition implies that
particles are closer together (than dilute
solutions).
• So rate increases with concentration.
• Surface area
– larger surface area increases reaction
• Mixing increases interaction
• Need to minimized precipitation or colloid
formation
12
Temperature
• Temperature affects rate by affecting the
number and energy of collisions
• So an increase in temperature will have the
effect of increasing reaction rate
13
Reaction rates and stoichiometry
• Rate has units of moles per liter per unit time
- M s-1, M h-1
• Consider the hypothetical reaction
aA + bB cC + dD
• We can write 1 [ A] 1 [ B ]
r
a t b t
1 [C ] 1 [ D]
c t d t
14
Example
At a given time, the rate of C2H4 reaction is 0.23
M/s. What are the rates of the other reaction
components?
C2H4(g) + 3 O2(g) → 2 CO2(g) + 2 H2O(g)
0.23 M/s ? ? ?
15
3. RATE LAW
16
Rate law
• Consider the following reaction
aA + bB products
Rate = k[A]m[B]n
where k is called the rate constant
17
Concentration and rate
aA + bB → cC + dD
• General form of rate law:
rate = k[A]m[B]n
[A], [B] – concentration, in M or P
k – rate constant; units vary
m, n – reaction orders
18
Reaction order
• Rate = k[A][B]0 m = 1 and n = 0
- reaction is first order in A and zero order in B
- overall order = 1 + 0 = 1
- usually written: Rate = k[A]
19
Rate law
20
Rate Law
• An exponent of 1, rate is directly proportional to the
concentration of that reactant
- if concentration is doubled, rate doubles
- reaction is first order in that reactant
21
Reaction orders
For the reaction: A →B, the rate law is:
rate = k[A]m
22
Example
2 NO(g) + 2 H2(g) → N2(g) + 2 H2O(g)
rate = k[NO]2[H2]
23
Example
PtCl2(NH3)2 + H2O PtCl(H2O)(NH3)2 + Cl-
25
Measurement of reaction rate
26
Measurements of reaction rate
C
C
C
Initial rates Instantaneous rate
nc nc
C1 nt
C2
C3
t t
t t1 t2 t3
Here nc is true order, with respect to concentration
and nt is order with respect to time.
28
Time, s [C4H9Cl], M Average rate, M/s
0 0.1000
50 0.0905 1.9E-4
100 0.0820 1.7E-4
150 0.0741 1.6E-4
200 0.0671 1.4E-4
300 0.0549 1.22E-4
400 0.0448 1.01E-4
500 0.0368 0.8E-4
800 0.0200 0.56E-4
10,000 0
29
C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)
Initial rate
30
Determination of rate law
The method of initial rate
• Measuring the initial rates as a function of the initial
concentrations
• Avoids problems of reversible reactions
• Initially there are no products so they cannot affect
the measured rate
• This method is chosen to check the effect of a single
reactant on the rate
31
Bench-Top Reactors
32
Atlas Reactors
http://www.syrris.com/batch-products/atlas-parallel-system
33
Stopped-Flow Technique
http://www.hi-techsci.com/techniques/stoppedflow
34
Temperature Jump
http://www.hi-techsci.com/techniques/stoppedflow
35
Quench-Flow Technique
http://www.hi-techsci.com/techniques/stoppedflow
36
Summary of Experimental Methods
37
4. ANALYSIS OF RATE LAW
38
Types of rate laws
39
First order
Log [A]
1 d[ A]
R k (T ,I )[ A ]
ν A dt
1.0
[ A ] [ A ] o e k ( T ,I )t
0.1
k ( T ,I )
log[ A ] log[ A ] o t
2.303
0.01
0.001 t
1 2 3
40
Second order
1 d[ A ]
R k ( T )[ A ] 2
A dt
1 1
ν i k ( T )t
[A] [ A ]0
[ A ]o A [B]o [B]o
ln B ln A B [B]o A [ A ]o k(T )t
[A] [ A ]o
41
Third order
1 d[ A ]
R k(T )[ A ][B ][C ]
A dt
A B C 1 1 1
2
2
2k(T )t
[A] [ A ]o
[ A ]o [B]o [C]o
42
Summary Rate Equations
2nd order
k = M-1-s-1
43
Half-life
• The half-life, t1/2, is defined as the time it takes for
the reactant concentration to drop to half its
initial value
44
Half-Life
• Half-life (CH3)2N2(g) N2(g) + C2H6(g)
– A =Aoe-t Time Pressure (torr)
0 36.2
– = ln2/t1/2 30 46.5
– If a rate half life is known,
t A B C
fraction reacted or 0 36.2 0 0
remaining can be 30 36.2(1-x) 36.2x 36.2x
calculated
46.5 = 36.2(1-x+2x)=36.2(1+x)=36.2+36.2x
Ct =Coe-kt
46.5-36.2 = 36.2x x = 0.285
kt0.5=ln(2)
to.5 = - [ln(2) t]/[ln(Ct/Co)] A = 36.5(1-0.285) = 25.9
2t0.5
t0.53
46
5. RATE THEORY
47
ARRHENIUS’ EQUATION
49
Arrhenius Equation
Or
log k = log A –Ea/(2.303 R) (1/T)
Y=mx+b
51
To find slope, m
Ln k
Ea/3R
k2
k
ln
1
m= 1 1
T
2 T1
1/T
52
Arrhenius’ Equation
• This is Arrhenius’ Equation
• Can be arranged in the form of a straight line
• ln k = (-Ea/R)(1/T) + ln A
• Plot ln k vs. 1/T slope = -Ea/R
Log [k]
1.0 EA/2.303
= dlog K/d(1/T)
54
Temperature Effects
Maxwell-Boltzmann Distribution
T1To k 310)(300 k
Ea ln 0 (8.34) ln o 53594(J / mol)
T o T1 k 1 (300 310) 2k o
56
Summary of A and Ea
Reaction A Ea(kJ/mol)
57
Example
It is given for a specific reaction, k =0.00123 /ms at
290oK and 0.0394/ms at 350oK. What is its Ea and k
at 308oK?
Ea (350)(298) 0.0394
ln k 1 ln A Ea (8.34 ) 57811( J / mol) 57.8(kJ / mol)
RT1 350 298 0 . 00123
57811 1 1
k E 1 1 ln k ln(0.00123 ) 8.70 0.578 5.94
ln 2 a 8.324 308 298
k1 R T2 T1
TT k
k e 5.94 0.00263 2.63x10 3 (1/ ms)
E a 1 2 R ln 2
T2 T1 k1
58
Collision Theory
59
M. Silberberg
Molecular Orientation and Effective
Collisions
60
Molecular Collisions
Before collision
No-effective collision
61
Collision Theory
two identical gas molecules colliding with each other at a velocity,
v (molecules/cm3-s) [N.C. Leuis (1918) and Eyring (1935)]
E
v z AA e RT
zAA = # collision/(s-cm3)
1
z AA 2 d 2 cn 2 molecules/(cm3-s)
2
8κT
c = average velocity of each molecule
πm
m: mass of each molecules
k = Boltzmann constant
1 8 T T
z AA 2d2n2 2n2 d2
2 m m
1
2 m A mB 2 RT
E
v n A nB d AB 8T e dAB: average distance, sum of radii 62
m A mB
Collision Theory
1
m A mB RT
2 E
v n A nB d 2
AB 8T e
k = k’Na (cm3/mol-s) m A mB
1
v m m
2E
k' d 2AB 8T A B
e
RT
n A nB m A mB
1
m m 2
E
k Na d 2AB 8T A B
e
RT
m A mB E
1
k PZe RT
2 m A mB 2
A Na d AB 8T Z
m A mB
1 E
Z
k BT e 2 RT B
T 63
Example
Estimate he rate constant for the decomposition of HI(g)
molecules at 321.4oC according to the collision theory.
Given for the HI(g) molecules the following prosperities:
64
Example
k =9.72x10-27
(cm3/moleculesx)(6.023x1023)(molecules/mol)
= 5.86x10-3 (cm3/mol-s)
=5.86x10-3x(1000) 65
=5.85x10-6 (L/mol-s)
Example
Collision of two water molecules at room temperature, 298 oK,
given:
d = 0.30 nm, T=298oK;
mA=mB=18(g-mol-1)/6.023x1023 =2.99x10-26 kg;
=1.38x10-23 J/oK
81.38x10 298
1
23 2
Z 0.3x10
9 2
2.99x10 / 6x10
26 2
26
2.37x10 16 (m 3 / molecules s)
66
Example
Reaction k’ k
(cm3-molecules-1-s-1) (L-mol-1-s-1)
CH4+OHCH3 + H2O 8.14x10-15 4.9x1012
67
Transition State Theory
• During a chemical reaction, reactants do not suddenly
convert to products
• The formation of products is a continuous process of
bonding breaking and forming
• At some point, a transitional species is formed containing
“partial” bonds
• This species is called the transition state or activated
complex
68
Transition State Theory
• The transition state is the configuration of atoms at the
maximum of the reaction energy diagram
• The activation energy is therefore the energy needed to
reach the transition state
• Note also that the transition state can go on to form
products or break apart to reform the reactants
rA uA
R
b
uBC
rB 69
Transition State Theory
A + B = AB* C
r = [AB*]; (s-1); [AB*](molecules/cm3)
*AB
r K * [ A][ B ]
A B
K = 1.38x10-16 erg/oK
G*
K* e RT
T = 6.624x10-27 erg/s
70
Transiton Theory
T *AB S * / R H * / RT
r e
A B
T *AB S */ R
A e
A B
T *AB S */ R H */ RT
r e e
A B
T
f e S */ R e H */ RT
TZe H */ RT E =H*
71
Summary of Rate Theory
72
6. REACTION MECHANISMS
73
Reaction Mechanisms
• Reactions occur in a series of elementary steps
collectively called a mechanism.
• Determining the reaction mechanism is the overall goal
of kinetic studies.
• One step, the rate-determining step (RDS), is much
slower than the other.
• Usually, an intermediate (isolable) or a transition state
(non-isolable) is formed at some point during the
reaction.
• molecularity – the number of molecules that participate
in a reaction
74
Reaction Mechanism
75
Reaction Mechanism
76
Elementary Steps and Molecularity
Molecularity Elementary Reaction Rate Law
77
Steady-state Approach
78
2N2O5 4NO + O2
k1
N2O5 NO2 + NO3
k-1
k2
NO3 + NO NO + NO2 + O2
k3
NO3 + NO 2NO
d [ NO ]
k 2 [ NO3 ][ NO ] k3 [ NO3 ][ NO ] 0
dt
k 2 [ NO3 ][ NO2 ]
[ NO ]
k3 [ NO3 ]
d [ NO3 ]
k1[ N 2O5 ] k 2 [ NO3 ][ NO2 ] k3 [ NO3 ][ NO ] k 1[ NO2 ][ NO3 ] 0
dt
k1[ N 2O5 ]
[ NO3 ]
k 2 [ NO3 ][ NO2 ] k3[ NO3 ][ NO ] k 1[ NO2 ][ NO3 ]
79
k1[ N 2O5 ]
[ NO3 ]
k 2 [ NO2 ] k3 [ NO] k 1[ NO2 ]
k1[ N 2O5 ]
k
(k 2 k 1 )[ NO2 ] k3 2 [ NO2 ]
k3
k1[ N 2O5 ]
(2k 2 k 1 )[ NO2 ]
d [O2 ]
r k 2 [ NO3 ][ NO2 ]
dt
k k k [ N O ][ NO2 ]
1 2 3 2 5
(2k 2 k 1 )[ NO2 ]
k1k 2 k3 [ N 2O5 ]
k '[ N 2O5 ]
(2k 2 k 1 )
80
Catalysis
• Catalyst – increases the rate of a reaction without being
consumed or changing chemically
• Accomplishes this by lowering the activation energy by
changing the reaction mechanism.
• Heterogeneous vs. homogeneous catalysis
• Examples:
– Catalytic converter
– Enzymes in the body
– Ozone depletion
81
Catalysis
• Reaction rates are also affected by catalysts
• Catalyst: a substance that increases the rate
of a reaction without being consumed in the
reaction
• Catalysts work by providing alternative
pathways that have lower activation energies
• A catalyst may be homogeneous or
heterogeneous
• Homogeneous: catalyst and reactants are in
the same phase
82
Energy
Uncatalyzed
Ea pathway
Catalyzed
pathway
Ea
products
E
Reactants
Reaction process
83
• Heterogeneous: catalyst in a different phase
• Typically: a solid in a liquid
• An important example: catalytic converters in
automobile
- convert pollutants to CO2 H2O, O2, N2
- usually Pt, Pd, V2O5, Cr2O3, CuO
• Cars must use unleaded fuels – lead poisons the
catalytic bed
84
Enzyme Kinetics
Michaelis-Menten mechanism for enzyme kinetics is:
85
Catalytic efficiency,
= kcat/KM
= k2/[(k-1+k2)/k1]
max, = k1; if k2 >>k-1
k1 = rate of formation of ES
v vmax v
S K M S
1 KM 1
1 S K M K M
v vmax S S v vmax vmax
[S]/v v/[S]
1/v
1/vmax
KM/vmax
1/KM
vmax/KM
KM/vmax
1/vmax
[S] v
1/[S]
87
Hypothetical KM = 20 Vmax = 2 88
Enzyme Inhibition
89
Competitive Inhibition
k1 k2
E S k1 k2 KM
E+S ES E + P ES k1
+ k-1
I E I K
KI EI I
k3
EI E+Q
k-3 Eo [ E ] [ ES ] [ EI ]
[ E ][ S ] [ E ][ I ]
d [ ES ] Eo [ E ]
k1[ E ][ S ] k 1[ ES ] k 2 [ ES ] 0 KM KI
dt
[S ] [I ]
d [ EI ] Eo [ E ]1
k3 [ E ][ I ] k 3[ EI ] k 4 [ EI ] 0 K M K I
dt
Eo
[E]
[S ] [ I ]
1
KM KI
90
1/v
d [ P] [I]
k 2 [ ES ]
dt
KM [I ]
1
d [ P] [ E ][ S ] vmax K I
k2
dt KM
1/vmax
[S]
d [ P] k 2 Eo
[S ]
dt KM 1 [ S ]
[ I ]
1 1 KM [I ] 1
KM KI 1
d [ P] k 2 Eo [ S ]
v vmax vmax K I [S ]
v
dt [I ]
K M 1 [ S ]
KI Inhibitor is replaced
vmax k 2 Eo vmax [ S ]
from the active sites
v by substrate at high [S]
[I ]
K M 1 [ S ]
KI 91
Non-competitive inhabitation
Inhibitor binds to some other binding sites;
Inhibitor combines with both free E and ES
2 possible mechanisms:
v k 2 [ ES ] 1/vmax-app
1 1 [I ] 1/[S]
[S ]
v KM vmax app vmax vmax K I
vmax 1 [ S ] [ I ] [ I ][ S ] 1/vmax-app
KM K I K IKM
Vmax=k2E0
1/(vmaxKI)
Henri-Michaelis-Menton Eq
v [S ]
vmax [S ] [I ]
K M 1 [ S ]1
K M K I 1/vmax 93
[I]
Uncompetitive inhibition
No binding site for inhibitor until substrate is bound to
the enzyme, so only ternary complex is possible
94
1/v
Uncompetitive Inhibition
KM
E+S ES E + P
+
I
KI KM
EIS E + Q vmax
1 [I ]
v k 2 [ ES ] 1
vmax K I
1/[S]
[S ] 1 1 [I ]
v KM v' vmax K I
vmax 1 [ S ] [ I ][ S ] 1/v’
KM K IKM
Vmax=k2E0
1/KI
1 KM 1
1 1 [ I ]
v vmax [ S ] vmax K I
1/vmax
95
[I]
E nS ES n P Eo [ E ] K [ E ][ S ]n
[ ES n ]
K
[ E ][ S ]n Eo
Hill eq. [E]
Yield 1 K [ S ]n
[ ES n ] K [ E ][ S ]n
Y
[ E ] [ ES n ] [ E ] K [ E ][ S ]n [ ES ]
KEo [ S ]n
1 K [ S ]n
Y n: Hill coefficient
K [ S ]n
1 Y
k 2 E o K [ S ]n
Y v k 2 [ ES n ]
log
n log[S ] log K 1 K [ S ]n
1 Y
1 1 K
v k 2 [ ES ] n
v vmax [ S ] vmax
Eo [ E ] [ ES ]
96
97
Chain Reactiosn
Chain reactions usually involve free radicals
H2+Br2=2HBr
The experimental rate law is
1
d [ HBr ] k '[ H 2 ][ Br2 ]
2
dt [ HBr ]
1 k''
[ Br2 ]
98
Initiation Br2 Br Br
ka
Propagation Br H 2
kb
HBr H
H Br2
kc
HBr Br
Termination Br Br
ke
Br2
99
100
101
C2H6 = C2H4 + H2
102
103
The Lindemann Mechanism
N2O5 = NO2 + NO3.
Rate k2[N2O5]2
104
. (16)
Large M
105
7. Elementary Reaction in Solution
• Solvent effect
• Physical transfer
• Chemical effect
106
Reactions in Solution
• Upper limit for bimolecular steps of solution reaction.
Solutes behave like spheres undergoing Brown motion in
a viscous fluid and shows that the number of encounter
per cm3 per second is:
R 4 DA DB rA rB N N
1
E
1
A
1
B
dN 1A
J DA
dx
107
Reactions in Solution
1
dN
Total flux at r from B: RB 4r D A 2 A
dr
1
N A at r=(rA+rB) is 0
N 1A
RB dr
r2
4D A d N 1A
( rA rB ) 0
RB 4 (rA rB ) DA N 1
A
T k est
k diff
D diff
exp( ) 1
6r (T )
z A zBe2
2TN a (rA rB ) 2
(rA rB )T
k diff
3000 (T )rA rB
8 RT
k diff
3000 (T )
8(8.31x107 )(298)
k diff 6.4 x108 ( L / mol s)
3000(0.01)
109
8. REACTION AT INTERFACES
110
Adsorption isotherms
(Langmuir)
A+ S = AS; K N 1AS
pV = nRT K 1 1
n/V =P/RT N ANB
1 1 N 1A = n/V =NaP/RT
N S =(1-) N T
bP
N 1
AS =N 1
1 bP
T
K = RT/(1-)NaP
N a K K 7.34 x10 21 K
T 1 b (atm 1 )
K RT T T
1 N a P
111
Adsorption Isotherm
(Fruendlich)
fi P
f i i
1 bi P
f() = exp()
= fraction of sites with energy of adsorption e between 0 and d.
f( b( ) P
d
1 f( b( ) P
0
Let Eads =
aP m
A+SAS T 2
RS1 SN 1A
1 2m A
8T 2
RE1 S2 N 1A N S1 RS1 k S SN 1A
mS m A 1
mS
mS m A T 2
k s
2 S2 A2 S2 2m A
S = Total surface area of spheres in 1 cm3 1
T 2 T
S ( 4rS2 ) N S1 k s pe
2m A
N 1
S = total number of spheres in 1 cm3 113
Example
Calculate the rate constant for the adsorption of a
metal ion, with molecular weight of 100 g at room
temperature, 298 oK.
1
1.4 x10 x 298 2
16
k s 8.15 x10 9 (cm3 molecules 1 cm 2 s 1 )
2 xx100
8.15 x10 9 x(10 3 ) x(6.023 x10 23 )( L / mol )(1 / cm 2 )(1 / s )
4.91x10 12 ( L / mol )(1 / cm 2 )(1 / s )
1
T 2
k s
2m A
114
Langmuir-Hinshelwood
A S AS ; K A bA PAbB P B
R ks
B S BS ; K B (bA PA bB PB ) 2
AS BS P S ; k s R ks
bA PAbB P B
ks
bA PA
ks '
PA
2
(bB PB ) (bB PB ) PB
R k s [ AS ][ BS ]
bBPB > bAPA
bA PAbB P B bA PAbB P B
R ks R ks k s, PA PB
(1 bA PA bB PB ) 2 1
bA PAbB P B bB P B ' PB bBPB , bAPA <1
R ks 2
ks ks
(bA PA ) bA PA PA
A S AS ; K1
B AS C S ; k s
bA PA
R k s [b][ AS ] k s PB
1 bA PA
bA PA b P
R ks PB k s A A PB k s' PB
1 bA PA PA
bB PA
R ks PB ksbAPA PB ks' PA PB
1 bA PA
116