RATE LAWS Time dependence measurement of P (reactant/product consumption)

Zero order (α =0 ¿ : v=k Given reaction A →Y + Z 2 the extent of rxns is given as ξ

Integrated rate law: [ A ] =[ A ]0 −kt 1
For A: P0 (1−ξ) and for Y: P0 (ξ) and for Z: P (ξ )
[ A ]0 2 0
Half-life = t 1 =
2
2k Rate = k [P¿¿ 0 (1−ξ )]¿
Differential rate method v 0=k [ A ] 0 integration gives ln v 0=ln k + α ln [ A ]0
α
First order (α =1 ¿ : v=k [ A]
Integrated rate law: [ A ] =[ A ]0 e−kt c
Temperature dependence of rate constants ln k =B−
ln [ A ]−ln [ A ] 0=−kt T
Half-life & time constant = −1 2 d
0th:
t 1=
ln 2 ln e 1 st M −1
s EMPERICAL ARRHENIUS LAW AND EA E a=R T
dt
ln k = Ea is the energy
and τ= = 1 =s
2
k k k nd barrier for the rxn to proceed.
2 =
Second order (α =2 ¿ : −1 −1 Ea is the minimum energy to supply reactants w/ for rxn to proceed. It is also
M s
v=k [ A ] or v¿ k [ A ] [B ] proportional to k when:
2

Ea = small = rxn rate high fast rxn AND Ea = large = rxn rate low, slow rxn
[ A ]0
Integrated rate law: [ A ] =
1+ [ A ] 0 kt CONSECUTIVE ELEMENTARY RXNS A k 1 B k 2 C @t=0
→ →
1 −d
Half- life: t 1 = [ A ] =[ A ]0 and every other [ ] = 0 1st order [ A ] =k 1 [ A ]
2 k [ A ]0 dt
d
Complex order [ B ]=k 1 [ A ] −k 2 [B ]1st order d [ C ] =k 2 [B]
dt dt
−d
@ ANY T [ A ] 0= [ A ] + [ B ] +[C] and integrating for [ A ] gives
dt
[ A ] =[ A ]0 e−kt which can be replaced in the integration:
d k [A]
[ B ]=k 1 [ A ] −k 2 [ B ]= [ B ] = 1 0 ( e−k t−e−k t ) then can solve for [C]
1 2

dt k 2−k 1
[ A ] 0 −k t −k t
¿ [ A ] 0−( [ A ] + [ B ] ) Where [ C ] =[ A ] 0− (e −e ) 1 2

k 2−k 1

Pseudo-First order: one of the reactants is held

constant for rxn A+ B → Z
v=k obs [ A ] 0 with B constant and PARALLEL RXNS
v=k obs [ B ]0with A constant. COMPETING = one reactant, two products
−d
Third order (α =3 ¿ : And two k values (k1 and k2) [ A ] =(k 1 +k 2)[ A ] and int. gives
dt
d
v= [ A ]=K [Order
A]
of completion d
[ A ] =[ A ]0 e−(k +k )t which can be subts. in [ B ]=k 1 [ A ] =k 1 ( [ A ]0 e ( ) )
− k +k t 1 2
α =0> 1> 2
1 2
2dt dt
integration yields 2 kt=
1 1
( −
1
2 [ A ]2 [ A ]20
and
) int. gives [ B ] =
k1 [ A ]0
K 1+ k 2
(1−e ( ) ) It can also be for d/dt[C] but with k2 which gives
− k +k t 1 2

k [ A]
isolating for t gives t=
1
4k ([ 1
2
1
− 2
A] [A 0 ] )
[ C ] = 2 0 (1−e−(k + k ) t ) @ any time kinetic control of rxn
K 1 +k 2
1 2
[ B] k 1
=
[C] k 2

CONCURENT = pathways to same product. [A]0 + [B]0 = [A] + [B] + [X]

REVERSIBLE RXNS A K 1 / K−1 B where −d
⇔
For [A] and [B] can be subst. in which are found by integrating [ A ] and −d [B]
−d dt dt
the rate law v= [ A ] =k 1 [ A ] −k−1 [B ]
dt MAXIMUM CONC. OF [I]
which is rateconsumption – rate formation k a [ A ] 0 −k t −k t
[ A ] 0= [ A ] + [ B ] and isolate for [ I ]= ( e −e ) treat fraction
a b

k b−k a
[ B ] =[ A ] 0−[ A ] substitute for [B] in rate as constant C therefore;
law above; v=k 1 [ A ] −k −1 ( [ A ] 0−[ A ] ) d
[ I ] =C ( −k a e−k t +k b e−k t )=0 at
a b

At t = equilibrium dt
v=k 1 [ A ] e −k −1 ( [ A ] 0− [ A ]e )=0 which after tmax Bring negative value on the other
integration gives side and substitute the equation in [I]max
and cancel stuff out to eventually get
q
k
EXPLOSIONS = radical chain rxns that heat up quick enough Degree of Polymerization = average # of monomers per polymer <n>
to lead to explosions
[ A ]0
Detonation = physical shock wave due to rapid rise in T and P @ ⟨ n⟩ = =1+ [ A ]0 kt the rate of chain polymerization
supersonic velocity [A]
Deflagration = chemical less violent expl. Flame front @ few

Thermal explosion = energy trapped ∴high T and k ↑ and fast

ms-1

rxn contained (exothermic rxn)

v=k p
kt ( )
V I 1 /2
[ M ] and with the catalyst v=k p
kt ( )
k I 1 /2 −1 /2
[ M ][ I ] this is

Chain branching = radicals react w/ eachother exponentially.

the rate of chain polymerization
v rate of chain produc .
1 kp
=k [ M ][ I ] where k =
2
ν= = 1/ 2
v i rate of radical produc . ( ki kt )
Enzyme Catalysis Kinetics E+ S ⇄ ES ⟶ E+ P ka, k-a & kb
[ E ] [S] k −a +k b
(Michaelis-Menten rxn) v=k b [ES ] M. Const. k m= =
[ ES] ka

COLLISION THEORY k =k en × f Ea × f steric

Ave. velocity (
v=k B [ ES ] =
[ E ][ S ]
kM
kB
kM
=
( )
[ E ][ S ] where Alternative formulation of kinetics
k [ ES]
( ) ( ) [ E ] 0= [ E ] + [ ES ]= M
1/ 2
8 KB T 8 RT
1/ 2
mA mA +[ ES]
v rel ¿= = μ= [S]
πμ πM m A + mA
Collision cross section σ =π d =4 π r 2 and
1 2
2

−E −Ea
⟹ [ E ] 0=[ ES ] 1+ ( kM
[ S] )
⟺ [ ES ] =
[ ES ] 0
1+ K m /[S]
where

d= [ d 1+ d 2 ] Arrhenius Eq. k =A e K T = A e RT
a

2
b k [ ES ] 0
CT v=k B [ ES ] = B
¿
Reactive cross (fsteric) σ = p × σ if not given p, p=1 1+k M
¿ −E / RT ¿ TURNOVER FREQUENCY maximum # of cycles performed by active site
CT rate const. k CT =N σ v rel e a
& A=N σ v rel
C. frequency v max v k
v= k cat=k b= max CATALYTIC EFFICENCY = ε = cat
¿
1/ 2
2 σ v rel P 16 P N r 2 π 1 /2 1+ k M ' /[S] [ E ]0 Km
z=N σ v rel = =
( )
KT 1 /2 v max 1 1 kM 1
( RTM ) v= ⟺ = +
1 2 Lineweaver-Burk frmla kM v v max v max [ S ] where
'

C. energy ε = μ v rel C. density Z=N A N B σ v rel 1+

2 [S]
1 N zP
( )
1 1 α '
α Km 1
Z= z = frction of molec. C. =v max (from graph) = +
2 v 2 kT 1/v v v max v max [ S ] 0
E /k T
f ( ε )=f (E a)=e a B
The eq. above is y=b+mx format ^^^^
‡
TST [ C ] =k ‡0 [ A ] [B] where k 0 =¿ 0 for unimolec.
‡
v max
Low [S] [ S] High [S] v max=const .
‡ RT ‡ KM
And k 0 = K EYERING Eq.
Po p Conservation of enzymes
[ ES ] 0
( )
k B T ‡ RT S −1
k tst =K
h
Kp
Gibbs free energy
Po (
kB kM
[ E ] 0= [ ES ] 1+ +
kc [S]
⟺
[ ES ] =
k k
)
1+ b + M
k c [S ]
∆ G=∆ H−T ∆ S
Debye-Huckle Eq
log k =log k + 2 A √ I z a zb
0