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This presentation is a very basic overview of the kinetics section from a standard Advanced Physical Chemistry course.

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**Chemical kinetics looks at dynamics-details of process of how system
**

gets form one state to another and time required to do so - complex area

of study

Equilibrium thermodynamics - static viewpoint - interested only in initial

and final states of a system - can tell with precision the extent of reaction

kinetics - more crudely predicts rates of reaction

- explains rate in terms of reaction mechanism

- reaction mechanism describes relative positions of all microscopic

particles as f(time) whose motion is necessary for reaction to occur

Also look at theoretical models for predicting rxn rates based on

Arrhenius conclusion: most commonly observed relationship between

rate of rxn and T implies that there exists an energy barrier to progress

of rxn

- kinetic molecular theory & activated complex theory

**Techniques to Study Kinetics (come up with mechanisms)
**

ultimately - conc as f(time)

1. pressure changes

- at least one component must be gas

2. spectroscopy

- use Beer's law A a c

- only one species must absorb at particular l

3. Electrochemical methods

- can monitor change in pH or conductivity of solution

4. Other more sophisticated methods

**Assuming closed systems:
**

aA + bB cC + dD

moles of i : ni = ni(t) = nio + i

i = stoichiometric coef. - unitless - rcts, + pdts

dni =id

noi = constant

dni

d

i

dt

dt

const. V

= extent of rxn = mol

dni /V i d dci

dt

V dt dt

i d dci

For const. V: rate ui =

= rate of species i

V dt

dt

**Example: N2 + 3H2 = 2NH3
**

u = rate of reaction =

dc

1 d

2 1

V dt

dt

3

dc

dc

dc

rate of formation NH3 =

dc

H

2 1

dt

2

dc

NH

3

dt

N

1

1

2 u

u

u NH

N

H

dt

2

2 3

2

3

rate of disappearance N2=

rate of disappearance H2=

N

H

3

2 u

3

u

u NH

H

N

dt

2

2

2

3

NH

2

3 u

2

u

u H2

NH3

N

dt

3

2

**u(t) = rate of rxn is related to concentrations of various chemical
**

species present at time

t. This relationship called rate law.

**which components of rxn are kinetically active, i.e. a
**

change in its concentration will alter the rate of rxn. or

included in rate law

Rate law often looks like following:

u = k[A]a[B]b

k = rate constant = f(T) c

must be determined experimentally, cannot be deduced

from stoichiometry of rxn.

Example:

rate law

Br2 + I2 = 2BrI

d [ BrI ]

k[ Br2 ][ I 2 ]

dt

Br2 + H2 = 2HBr

d[ HBr ]

k[ Br2 ]1/ 2[ H 2 ]

dt

1 k '[ HBr ] /[ Br2 ]

In general:

[A]a[B]b[D]d

**a = order with respect to species A
**

b = order with respect to species B

d = order with respect to species D

(a+b+d) = overall order of rxn

a can be fraction, negative

For 1st rxn: order w.r.t. Br2 and I2 is 1, overall order =2

rate law happens to reflect rxn stoichiometry

For 2nd rxn: concept of order does not apply

rate law is complicated and rxn occurs by multistep process

**If concentration of any kinetically active species is
**

nearly constant it can be incorporated into k and we get

pseudo nth order rxn. C = catalyst for instance:

d [ A]

k AB C

dt

(3rd order)

if [C]~ constant

d [ A]

k ' AB

dt

(pseudo 2nd order)

can use to determine the order (isolation method)

Co

Conc.

equilibrium

time

**• to find rate of reaction at any time, measure change of
**

concentration with time at constant T

• rate at any time = slope of curve at that time

• easier to compare integrated rate expression

**First Order Reactions
**

A products

d [ A]

= k[A]

u(t) =

dt

d[ A]

kdt

[ A]

ln

[A]

kt

[A]o

Plot ln[A] vs t

A + B products

or

d[ A] k t dt

[ A]

[ A]o

0

[ A]

[A] = [A]oe-kt

slope = -k

**Half-life: time required for half of the specified
**

reactant to disappear

t = t1/2 when [A] = [A]o/2

For first order reaction:

ln [ A]o / 2 kt 1

2

[ A]o

1

ln kt1

2

2

ln 2

k

t 1 f (conc.)

t1

2

2

**Second Order Reactions
**

A products

or

A + B products

d [ A]

= k[A]2

u(t) =

dt

[ A]

d[ A] k t dt

d[ A]

kdt

[ A]2

2

[ A]o

0

[ A]

1

1

kt

[A] Ao

1

1

[ A] Ao

1

1

kt

[ A] Ao

Plot 1/[A] vs t

kt

slope = k

**Half-life for Second Order Reaction
**

t = t1/2 when [A] = [A]o/2

2

1

[ A]o Ao

t1

2

1

k Ao

kt 1

kt 1

2

2

1

[ A]o

t 1 f (initial conc.)

2

Second Order Reactions

d [ A]

d [ B]

u(t) =

= k[A][B]

dt

dt

d[ A]

kdt

AB

**need to integrate but we have a problem
**

need to know how [B] varies with [A]

[A] = [A]o - /V and [B] = [B]o - /V

/V = [A]o-[A] so [B] = [B]o -[A]o+[A]

d[ A]

kdt

ABo Ao A

method of partial fractions: for [B]o

[A]o

1

p

q

ABo Ao A A Bo Ao A

1 = p([B]o -[A]o+[A] ) + q[A] = p([B]o -[A]o) +(p+q)[A]

1= p([B]o -[A]o)

0 = p+q

1

p

Bo Ao

1

q

Bo Ao

A

1

A o AB o Ao A

A

d A

d A

A o AB o Ao A o B o Ao B o Ao A

A

1

A

1

B o Ao A

ln

ln

kt

Bo Ao Ao Bo Ao

Bo

1

Ao B o Ao A

1

Ao B

ln

kt

ln

Bo Ao

Bo Ao ABo

ABo

**Second Order Autocatalytic Reaction
**

AB

d

[

A

]

d

[

B

]

u(t) =

= k[A][B]

dt

dt

d[ A]

kdt

AB

[A] = [A]o - /V and [B] = [B]o + /V

/V = [A]o-[A] so [B] = [B]o + [A]o- [A]

d[ A]

kdt

ABo Ao A

method of partial fractions: for [B]o

[A]o

1

p

q

ABo Ao A A Bo Ao A

1 = p([B]o +[A]o-[A] ) +q[A] = p([B]o +[A]o) - (p-q)[A]

1= p([B]o + [A]o) 0 = p-q

p=q

1

p

Bo Ao

A

1

A o AB o Ao A

A

d A

d A

A o AB o Ao A o B o Ao B o Ao A

A

**Bo Ao A
**

1

A

ln

ln

kt

Bo

Bo Ao Ao Bo Ao

1

1

AB o

ln

kt

B o Ao Ao B

AB o A B kt

B

e

Ao

o

o

**• if no B is present initially, [B]o = 0, reaction will not
**

proceed - S shaped curve typical of autocatalytic rxns

and many growth processes (populations) autocatalytic

kinetics common in biochemical processes

Concentration

CB

o

[B]

if [B]o = 0, reaction will not proceed

time

Third order: lead to more complicated integrations

**Determining the Rate Law
**

1. Take c vs. t , guess n, plot as discussed

1st order ln c vs. t straight line n=1

2nd order 1/c vs. t straight line n = 2

2. Isolation method:

log

d A

a

b

k A B D

dt

d A

log k a log A b log B log D

dt

- perform experiment at const. T where [B] and [D] are in excess

d A

a

k ' A

dt

where k' includes [B] and [D]

**- can determine k' and a
**

- do for other components as well

**2 ½. Method of Initial Rates
**

uo k'

- measure rates at initial concentrations

- run experiment at series of initial concentration

rates plot log uo vs. log [A]o slope = a

**3. Half-life Method
**

nth order:

d [ A]

=k[A]n for n > 2

dt

t1

2

Ao

a

(2(n-1) - 1)

k(n - 1)[A]on -1

Determining rate law: need 2 different [A]o at const. T (k is same)

(2(n-1) - 1)

t 1 Ao 1 k(n - 1)[A]n -1 1 [A]n -1 2 [A] 2 n 1

o

o

o

2

(n-1)

(2 - 1)

t 1 Ao 2

[A]on -1 1 [A]o 1

2

k(n - 1)[A]on -1 2

solve for n knowing [A]o(1), t½ (1), [A]o(2), t½ (2) from experiments

rate law must be of form d [ A] = k[A]n

dt

Reversible Reactions

- usually study reactions far from equilibrium where

reverse reaction is not important

A = B

AB

BA

k1, k-1

k1

k-1

d [ A] d [ B]

k1[ A]

For forward rxn:

dt

dt

d [ A]

d [ B]

For reverse rxn:

k1[ B]

dt

dt

For both rxns: d [ A] d [ B] k1[ A] k1[ B]

dt

dt

[A] = [A]o - 1/V + 2/V and

[B] = [B]o+ 1/V - 2/V = [B]o+[A]o-[A]

assume [B]o= 0

d [ A]

= -k1[A] + k-1([B]o+[A]o-[A]) = -(k1+k-1)[A] + k-1[A]o

dt

t

d A

dt

0

A o k -1[A]o - (k 1 k -1 )[A]

A

1

A

ln k1Ao (k1 k -1 ) A| A t

o

(k1 k -1 )

k Ao (k k ) A

1

-1

ln 1

(k1 k -1 )t

k1 Ao

Solve for [A]

k e (k1 k -1 )t k A

1

1

o

1

(k1 k -1 )t

k1 Ao e

A

k1 Ao

(k1 k -1 )

(k1 k -1 )

At eqm. t =

k1Ao

Aeqm

(k1 k -1 )

k

1

[B]eqm = [B]o + [A]o - [A] = [B] = [A]o-[A]eqm = Ao 1

(k k )

1

-1

Beqm

KC

Aeqm

k

1

(k k ) k

1 -1 1

k

k -1

1

(k k )

1 -1

1

Another way to look at it:

d [ A] d [ B]

k1[ A] eqm k1[ B] eqm 0

dt

dt

Beqm k1

k1[ A]eqm k1[B]eqm

KC

Aeqm k -1

At eqm.

**Effect of Temperature on Reaction Rate
**

- most common relationship is exponential one

- reaction rate increases by a factor of 2 or 3 for each 10o rise in T

expt'ly we see: plot of ln k vs. 1/T is linear

Ea

d ln k

dT

RT 2

integrate

Arrhenius eqn. - empirical relationship

Ea

ln k

ln A

RT

or

k Ae

Ea

RT

Ea = activation energy f(T) - energy needed for rct to proceed to products

**A = preexponential factor or frequency factor
**

A has units of k

1st order

k = s-1

2nd order

k = M-1s-1

The higher Ea, the stronger the T dependence of k

**Ea = 0 means rate independent of T
**

Ea < 0 means rate

as T

will talk more about significance of A and Ea later

Elementary Reactions

- rxns that occur in a single step - only involve 1 or 2

molecules

- most rxns do not take place in a single collision but have

mechanisms that involve several elementary reactions

molecularity of rxn - # of particles involved in simple collisional

process for elementary rxn

- theoretical concept, whereas order is empirical

unimolecular - one that takes place w/o collision

- spontaneous disruption or transformation

- radioactive disintegration

- absorption of radiation to give energy

bimolecular - 2 molecules collide

**Rate law of elementary rxn based on chemical rxn alone:
**

unimolecular:

aA P

bimolecular: aA + bB P

1 d A

d P

a

k A u

a dt

dt

1 d A

a

b

k A B

a dt

**only dependent on reactants & their stoichiometric coef.
**

reaction mechanism - theory that has been devised to

explain currently known experimental facts, such as

overall stoichiometry, dependence of rxn rate on conc., T,

P, or other variables

- major goal of kinetics is to determine mechanisms of

complex rxns.

- several mechanisms may be consistent with data

**Consecutive Elementary Reactions
**

239U

239Np

23.5 min

AB

k1

BC

k2

A Ao e

k1t

239Pu

2.35 day

d A

k1 A

dt

d B

k1 A k2 B

dt

dC

k2 B

dt

d B

k1 Ao e k1t

k 2 B

dt

k1

B

e k1t e k 2t Ao

k 2 k1

[C] = [A]o –[A] – [B]

(good luck)

assuming [B]o = 0

if [B]o & [C]o = 0

1

k1t

k 2t

C Ao 1

k2e k1e

k1 k2

must integrate:

1

k1t

k 2t

C Ao 1

k2e k1e

k1 k2

[A]o

[C]

[A]

Conc.

[B]

eqm.

time

**Can calculate time at which [B] = max by setting d B 0
**

dt

**Parallel 1st Order Reactions
**

AU

AV

AW

d A

k1 A k2 A k3 A k1 k2 k3 A k A

dt

ln [ A] kt

[ A]o

[A] = [A]oe-kt

d U

k1 A k1 Ao e kt

dt

U

- k1

k1

- kt

Ao e Ao

d U k1 Ao e dt [U] - Uo

k

k

U

0

o

t

kt

k1

[U] Uo 1 - e-kt Ao

k

k2

[V] Vo

1 - e-kt Ao

k

k3

If [U]o = [V]o = [W]o = 0

[W] Wo

1 - e-kt Ao

k

[W] k 3

[V] k 2

and

U k1

U k1

[A]o

[U]

eqm.

Conc.

[V]

[W]

[A]

time

**products are in a constant ratio to each other
**

dependent on time, [A]o and k's.

**Steady State Approximation
**

A = Bk1, k-1

BC

k2

d A

k1 A k1 B

dt

d B

k1 A k1 B k2 B

dt

d C

k2 B

dt

**steady state approximation - assumes that the conc. of
**

all rxn intermediates (B) remain constant thruout exp't.

- usually intermediates are very reactive & thus are

present in small conc.

d B

k1 A k1 B k2 B

dt

k1 A

B

k1 k2

d B

0

dt

d C k1k 2 A

k 1 k 2

dt

k1

k1k2 A

d A

k1k1 A

d C

k1 A

k1 A

1

k1 k2

dt

dt

k1 k2 k1 k2

A Ao e

k1k 2

k k t

1

2

**Eqm. approximation: if A & B are in eqm.
**

k1 Beqm

KC

k1 Aeqm

k1 A

B

k1 k2

k1 A

B

k 1

(2)

from (1)

**when k2 << k-1 both [B] agree
**

- which says B forms A much faster than it forms C

If k2 << k-1 rate determining step (slow step) is k2

d C k1k 2 A

d A

k 2 K C A k 2 B

dt

k 1

dt

Chain Reactions

-rxn where intermediates are produced which generate

more intermediates thus propagating the rxn.

3 main rxn types:

1. initiation - unimolecular or bimolecular (can be

photoinitiated)

2. chain propagation - often bimolecular - one

intermediate and one substrate - intermediate is

product

3. termination - converts chain propagating

intermediates to stable molecules

4. inhibition - rxn where product is destroyed, i.e. is rct

(intermediate is destroyed & no new one produced)

Example:

Ethane decomposition

C2H6 C2H4 + H2

C2H6

CH3. + C2H6

C2H5.

H. + C2H6

H. + C2H5

2CH3.

k1

CH4 + C2H5.

C2H4 + H.

H2 + C2H5.

C2H6

k5

methane is a byproduct

initiation

k2 initiation

k3 propagation

k4 propagation

termination

d C2 H 6

-k1[C2H6 ] - k2[CH3][C2H6] -k4[H][C2H6] +k5[C2H5][H]

dt

**1. d H k3[C2H5] -k4[H][C2H6] -k5[C2H5][H] =0
**

dt

d CH 3

2k1[C2H6] - k2[CH3][C2H6] = 0

2.

dt

[CH3 ] = 2k1/k2

d C2 H 5

k2[CH3][C2H6]-k3[C2H5]+k4[H][C2H6]-k5[C2H5][H]=0

3.

dt

1+3 k2[CH3][C2H6]-2k5[C2H5][H]=0

Plug in for [CH3]

**2k1[C2H6]=2k5[C2H5][H]
**

From (1)

k3 C2 H 5

H

k 4 [C2 H 6 ] k5 [C2 H 5 ]

**2k1 C2 H 6 k1 C2 H 6 k 4 [C2 H 6 ] k5 [C2 H 5 ]
**

C2 H 5

2k5 H

k3 k5 C2 H 5

rearrange

C2 H 5

k

k3k5[C2H5]2 - k1k5[C2H6][C2H5] - k1k4[C2H6]2 = 0

k1k5 [C2 H 6 ]

k1k5

k1k5[C2 H 6 ]2 4k1k3k4 k5[C2 H 6 ]2

2k 3 k 5

k1k5 2 4k1k3k4 k5 2 H

2k3 k5

k[C2 H 6 ]

k3 k C2 H 6

k'

k 4 [C2 H 6 ] k5 k[C2 H 6 ]

d C2 H 6

k 3k[C 2 H 6 ][C 2 H 6 ]

k 2 2k 1

-k 1[C 2 H 6 ] [C 2 H 6 ] - k 4

k 5 k' k[C 2 H 6 ]

dt

k2

k 4 [C 2 H 6 ] k 5 k[C 2 H 6 ]

d C2 H 6

=k”[C2H6]

dt

first order

**Fluorescence Exp’t and Steady State Approximation
**

tris(2,2’-bipyridine) ruthenium +2 = R+2

R+2 + h R+2*

R+2* R+2

**absorption (rate: Iabs)
**

fluorescence

R+2* + Fe+3 R+3 + Fe+2

quenching (rate constant:kq)

d R 2*

I abs k s R 2* k q R 2* Fe 3 0

dt

R k

2*

I abs

3

k

Fe

s

q

Intensity of fluorescence a [R+2*]

**I o intensity when no quencher present ([Fe+3]=0)
**

=

intensity when quencher present

I

Io

I abs / k s

3

I I abs / k s kq [ Fe ]

k s kq [ Fe3 ]

ks

kq

Io

1 [ Fe3 ]

I

ks

Io

=

I

**intensity when no quencher present ([Fe+3]=0)
**

intensity when quencher present

Io

I abs / k s

3

I I abs / k s kq [ Fe ]

kq

Io

1 [ Fe3 ]

I

ks

k s kq [ Fe3 ]

ks

Unimolecular Reaction

(Lindemann-Hinshelwood Mechanism)

- unimolecular rxns seen as complicated rxn involving

multistep mechanism

- collisions are bimolecular, how can a rxn be first order

- from expt’l data, it has been seen that rate laws are often

1st order at high concentrations, but 2nd order at low

concentrations – look at Lindemann-Hinshelwood

Mechanism tp help explain this

Lindemann-Hinshelwood Mechanism

1. A + A A* + A

k1

activation

2. A* + A A + A

k-1

deactivation

3. A* P______

k2

spontaneous decay- unimolecular

A P

k

overall rxn

**step 1: excitation due to collision, A's translational
**

kinetic E or with an inert molecule N2 or Ar

step 2: loss of energy due to collision of A* with A

step 3: truly unimolecular rxn.

assume steady state approximation

d A *

k1[A ]2 - k -1[ A*]A - k 2 [A*] 0

dt

2

k1[A ]2

d

P

k

k

[A

]

A *

0

k 2 [A*] 1 2

- k -1A k 2

k [ A] k

dt

-1

2 limiting cases:

2

neither 1st or 2nd order

**1. low P: fewer collisions, A* has time to decompose k2>>k-1[A]
**

uB = k1[A]2 second order

2. high P - more collisions [A] large k-1[A]>>k2

d P

k1k 2 A first order (3rd step rate determining)

u

dt

k 1

**Homogeneous Catalysis (same phase)
**

catalyst - changes rate of desired reaction

- changes mechanism to one with lower Ea

enzymes - biological catalysts - read about MichaelisMenten rxn.

homogeneous catalyst - catalyst in same phase as rxn mixture

heterogeneous catalyst - catalyst in different phase,

i.e. solid in gaseous rxn.

**Gas Phase Catalysis
**

2SO2 + O2 2SO3

slow

termolecular rxn needs to take place in order to occur

2NO + O2 2NO2

fast

termolecular rxn with NO well known

NO2 + SO2 NO + SO3

bimolecular

NO2 oxidizes SO2 in low Ea bimolecular process

In general: uncatalyzed A + B P slow uP=k [A][B]

C = catalyst

catalyzed

k1

A + C X fast

if k2>>k1

k2

X + B P + C fast uP=k1[A][C]

catalyzed rxns often found expt'ly to be 1st order w.r.t. [catalyst]

we spoke of autocatalysis - product accelerates rxn.

**Michaelis-Menten mechanism
**

-enzyme catalyzed reaction

Substrate = S products = P enzyme = E ES = intermediate

k1

d P

k2 ES

dt

k2

E + S = ES P + E

k-1

d ES

k1E S k1[ ES ] k2 [ ES ] 0

dt

Steady-state approximation

k1 E S

ES

k1 k2

[E]o = [E] + [ES]

[S]o = [S] + [ES]

negligible

only a little enzyme is added so [S] >> [E]

**k1 E o ES S o
**

ES

k1 k2

**ES k E S k S ES
**

1

o

k1 k2

k1S o k1 E o S o

ES 1

k1 k2

k1 k2

o

1

o

k1 k2

k1 E o S o

k1 k2

ES

k1 k2 k1 k2 k1S o

k1 E o S o

ES

k1 k2 k1 S o

k1k2 S o E o

d P

Since [S] = [S]o ~ const.

k E o

k2 ES

k1 k2 k1 S o

dt

Rate varies linearly with enzyme conc.

k2 S o

k

K M S o

d P k2 S o E o

dt

K M S o

KM

k1 k2

k1

Michaelis const. mol/L

k2 S o

k

K M S o

d P

k[ E ]o

dt

**rate of formation of product 1st order w.r.t. enzyme not so with substrate
**

when [S]o >> KM k= k2

d P

k2[ E ]o umax

dt

0 order in S: so much substrate, rate is constant

- rate of formation of products is maximum

**- maximum velocity of enzymolysis
**

- S forces eqm. to right so only dependent on P formation

when KM >> [S]o

[S]o low reaction rate a [S]o and [E]o

d P k2 S o E o

dt

KM

d P k2 S o E o

umax

u

dt

K M S o 1 K M

S

rearrange

o

1

u

1 KM

S

umax

o

1

umax

KM

umax[ S ]o

**Lineweaver-Burk plot: 1/u vs 1/[S]o straight line
**

slope=KM/umax

y intercept =1/umax

x intercept = -1/KM

**kcat = # substrate molecules converted to product per unit
**

time when enzyme is fully saturated with substrate

= umax/[E]o = k2 catalytic constant of enzyme

**Theoretcial models for describing how chem rxns occur
**

1. Activated Complex Theory or Transition State Theory

- whether or not rxn occurs determined by movement of atomic

nuclei on a multidimensional potential energy surface

- valleys or holes = energy minima = stable molecular species

- heights or saddle points or cols = energy barrier to rxn

- rate = concentration of activated species x frequency with which

they pass over addle point

- need statistical mechanics to determine [activated species]

**2. Kinetic molecular theory
**

- calculate # of molecular collisions per unit volume per time and fraction of

those collisions whose energy exceeds some threshold energy

- atoms treated as rigid spheres - if collision betw. 2 spheres has enough

energy will react to form products

- does not deal with how large threshold energy must be or effectiveness of a

collision as a function of relative molecular orientation

**Kinetic Model of Gases
**

3 assumptions

1. gas consists of molecules of mass m in ceaseless

random motion

2. size of molecules negligible dmol << ave. distance

traveled between collisions – treated as rigid spheres

3. they undergo perfectly elastic collisions (total

translational kinetic energy is conserved: no energy

transferred to rotational or vibrational modes

**Look at volume swept out by sphere of radius d
**

dB

dB

where d = (dA+dB)/2

d

dA= diam of molecule A

dA

**dB= diam of molecule B
**

dB

**• assume center of one A molecule is at center of cylinder
**

• when the center of a B molecule is within this volume, A & B collide

• a collision occurs when the distance betw. centers becomes as

small as d

B molecule at rest, A molecule moves thru volume

2

Volume swept out per unit time = d crel

crel

crel

= m3/s

**relative mean speed – mean speed with which one molecule
**

approaches another

8k BT

1

2

m A mB

m A mB

= reduced mass

**s = d2 = collision cross-section = m2
**

kB =R/NA = 1.38 x 10-23 J/K

NA = Avogadro’s #

nB = moles B

**If there are (nBNA/V) B molecules per unit volume then the # of
**

collisions of one A molecule with the B molecules in this V is given

by the collision frequency, z

P

molecules

nB N A

z s crel

s crel

k BT

s

V

**If there is not one, but (nANA/V) A molecules in this volume then
**

the # of collisions betw. A and B molecules is given by the

collision frequency, ZAB

1

Z AB

8k BT 2 2

molecules2

nB N A n A N A

N A AB

s crel

s

3

m

s

V V

2

For a single gas molecule A = B

Z AA

1 8k BT

s

2 mA

2

Z AA 10 34

1

2

N A2 A2

mA

mA

2m A

2

**# of collisions of A with other A molecules
**

in this volume. The ½ is included so as

not to count each collision twice

collisoins/m3s for typical gas at std. conditions

**How can we relate to rate laws?
**

u = k2[A][B]

A + B P

**Only a fraction of collisions successful, f
**

- energy must exceed a minimum value E > Ea

8k BT 2 2

d A

N A AB N A

fs

dt

1

rate of rxn. = fZAB=

8k BT 2

d A

N A AB

fs

dt

1

Experimentally we found:

1

8k BT 2

N A

k 2 fs

d A

k2 AB

dt

According to Arrhenius

k2 Ae

Ea

RT

**Ea = activation energy
**

A = preexponential factor

There exists a threshold energy below which rexn will

not proceed. For most rxns E >>kBT

The fraction of molecules with E > Ethreshold is given by

Boltzmann distribution

**prob. that molecules in E E th
**

prob. that molecules in any E

1 E k BT

E k BT e dE

th

1 E k BT

0 k BT e dE

E

e

k BT

E

e

Eth

Eth

k BT

Eth

e k BT

e k BT

0 1

0

Eth

**f = fraction of molecules with E > Eth =
**

1

e

k BT

e

Eth N A

1

8k BT

8k BT 2

N A k 2 s

N Ae Eth N A / RT

k 2 fs

?

2

Ea = EthNA

= Ae-Ea/RT

1

8k BT 2

N A

A s

**Arrhenius assumes A not f(T) here
**

shows slight dependence

RT

Arrhenius found

E

d ln k

a2

dT

RT

If A ~ constant

1

8k B 2

Eth N A 1

sN A

ln k

ln T ln

RT

2

Ea

d ln k Eth N A 1

2

dT

RT

2T RT 2

Ea = EthNA + ½RT

if Ea >> ½ RT can neglect

Then Ea = EthNA

1

8k BT 2

N A

A s

**Arrhenius assumes A not f(T) here
**

shows slight dependence

Steric Effects

- experimental values of A often much less than theoretical

- orientation of molecules may be a factor in rxn

CH3I (g) + Rb(g)

Rb

H

H

H

C

I

(not good)

H

C

I Rb

(good)

**Instead of s use s* reactive cross-section s* = sp
**

p = steric factor p << 1

**- calculate A experimentally, difference due to p
**

p = Aexptl/Ath

takes into account collision geometry

**Activated Complex Theory
**

- look at reaction in terms of potential energy of rcts and

pdts & progress of rxn (reaction coordinate)

- formulate reaction rate in terms of properties of rcts &

activated complex for that reaction

- apply statistical mechanics to reactants & activated

complexes

Partition function for molecule: q

Ei / k B T

e

i

**- probability that molecule will exist in any one of its
**

possible energy states i a q (q is unitless)

q gives indication of the average # of states that are

thermally accessible to a molecule at temperature T

**Can write partition function in terms of partition functions of
**

vibration, rotation, translation, electronic

q = qvqrqtqe

A B C

C

C

DE / RT

K

e

qA,m / N A qB,m / N A

AB

qC,m / N A

o

qom = standard molar partition function

**DEo = difference in ground state of
**

products & reactants

= Eo(C) - Eo(A) – Eo(B)

**Derivation of Rate Equation with Activated Complex Theory
**

Rate of rxn. = # of activated complexes passing over top of

potential energy barrier per second

=

C

**x average frequency with which complex moves to
**

product side, k

C

Potential E

transition state

A B C P

bimolecular

unimolecular decay

**assume rcts in eqm with C
**

A+B

P

rxn coordinate

dP

uk C

dt

**transition state – certain energetic configuration of maximum
**

potential energy

K

C C

AB

where

Experimentally

k

K

q

d P

k2 AB

dt

P 1bar

RT

k2 k K

P

= frequency of vibration of

C

** = transmission coef. = success of vibration to
**

push complex thru transition state ~ 0.5 - 1

qC ,m / N A

A, m

P

RT

d P

RT

AB

k K

dt

P

RT

C K AB

P

C

/ NA q

B ,m

/ NA

e

DEo / RT

N A qC ,m

q

A, m B , m

q

e

DEo / RT

C

**Complex moves to products when a vibration
**

pushes it thru transition state

Look at partition function of vibration

h

1

kB T

If

qv 1 e

h / kB T

1

then

2

h 1 h

h

h / kB T

and

e

1

... 1

kB T 2 kB T

kB T

k BT

qv

qC qr qt qe

Then qC qv qC

where

hu

qC

where

kB T

qC

h

K

Then write

A C ,m

A, m B ,

m

N q

q

q

kB T

K

K

h

e DEo / RT

has one vibrational mode missing

RT

kB T RT

k2 k K

K

P

h P

k BT RT

k2

K

h P

Eyring eqn.

**Thermodynamics of Activated Complex Theory
**

- look at Gibbs Energy, Enthalpy & Entropy of activation

D G RT ln K

k BT RT DG / RT

k2

e

h P

K e D G / RT

D G D H TD S

where

eqm const without vibrational mode of C#

D S / R D H / RT

k2 Be

k BT RT

B

h P

e

Assume ~1

D S / R D H / RT

k2 Be

e

k BT RT

B

h P

kB R

D

S

D

H

2

ln k 2 ln ln T

hP

R

RT

d ln k 2 2 D H

dT

T RT 2

Ea

d ln k2

dT

RT 2

Arrhenius found

Ea D H 2 RT

D S / R 2 Ea / RT

k2 Be

A Be

ee

D S / R 2

e

experimentally

preexpoential factor

k 2 Ae Ea / RT

A

D S R ln hAP / Rk BT e R ln 2

B

D H Ea 2 RT

k BT RT

B

h P

2 2

DG D H TD S

A = preexponential factor

For bimolecular collision 2 molecules form complex

D S 0

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