Development of Complex Curricula for Molecular Bionics and Infobionics Programs within a consortial* framework**
Consortium leader
PETER PAZMANY CATHOLIC UNIVERSITY
Consortium members
SEMMELWEIS UNIVERSITY, DIALOG CAMPUS PUBLISHER
The Project has been realised with the support of the European Union and has been co-financed by the European Social Fund ***
**Molekuláris bionika és Infobionika Szakok tananyagának komplex fejlesztése konzorciumi keretben
CATHOLIC UNIVERSITY
UNIVERSITY
Organic and Biochemistry
Reaction kinetics (Summary)
semmelweis-egyetem.hu
(Szerves és Biokémia )
(Reakció kinetika összefoglalás)
Compiled by dr. Péter Mátyus
with contribution by dr. Gábor Krajsovszky
Formatted by dr. Balázs Balogh
Table of Contents
semmelweis-egyetem.hu
1. First order reaction 4 – 4
2. Second order reaction 5 – 5
3. Parallel reactions 6 – 6
4. Steady state approximation 7 – 8
5. Temperature dependence of the rate constant 9 – 9
6. Transition state theory 10 – 11
1. First order reaction → monomolecular
Reactivity:
[ ] [ ] [ ] k A
dt A d dt
A - d v
rate = = = =
X A ⎯ ⎯→
[ ] k A dt
A
d = -
[ ] A - kt ln [ ] A0
ln = +
[ ] [ ] A = A 0 e -kt
α
t
[ ] A
0ln
[ ] A
ln
tg α = -k
X
A ⎯ ⎯→ k
AB ⎯ ⎯→ k
BY reactive more
is A k
k
if A > B ⎯ ⎯→
Organic and Biochemistry: Reaction kinetics
semmelweis-egyetem.hu
2. Second order reaction; bimolecular reaction X
B
A + ⎯ ⎯→
[ ] [ ] [ ] [ ][ ] k A B
dt B - d
dt A - d dt
X
d = = =
α
t
tg α = k
≈ A, B
3. Parallel reactions
e.g., S N 2 versus E2 k 2
k 1
Y X A
[A]
t
[Y]
[X]
[A]
[ ] k [ ] A k [ ] A
dt A d
2
1
+
=
[ ] k [ ] A
dt X d
=
1Organic and Biochemistry: Reaction kinetics
semmelweis-egyetem.hu
2 1
k k Y
X =
C C H
Cl
C C H
OH
C C k
S 2k
E2N
4. Steady state approximation: Principle of Stationary State
[I] could be expressed from it and written into equation (1)
k 1 << k -1 , k 2
if k -1 << k 2
X Nu
I + ⎯ ⎯→ k
2A k
1I + L
k
-1[ ][ ] I Nu (1)
dt k dX
=
2[ ] − [ ][ ] [ ] [ ] - - ≈ 0
= k A k I L k I Nu dt
dI
2 -1
1
[ ][ ] [ ] L k [ ] Nu
k
Nu A
k k dt
dX
2 1
1 2
= +
[ ] [ ] A ;
L k k
k k dt
dX
2 1+
= k [ ] A
dt dX
=
1semmelweis-egyetem.hu
A multistep reaction might be of first order kinetically:
e.g., S N 1 versus E1
C C
Cl +
C C
H
Cl k
1k
-1C C + H 2 O
C C OH
k
2S
N[OH]
+[OH]
+[OH]
k
2E1 [OH]
Organic and Biochemistry: Reaction kinetics
E1 k
1 S k E1
k
1 S ROH k
2 N 2
N
=
C C =
semmelweis-egyetem.hu
semmelweis-egyetem.hu
Temperature dependence of the rate constant a. Arrhenius
A T ln
1 R
k E
ln
a⎟ +
⎠
⎜ ⎞
⎝
= ⎛ -
1 R
E
a-
ln k ln A
RT E
aAe
k = -
Theory of the transition state
≠
≠
⎯→
⎟⎟ ⎯
⎠
⎞
⎜⎜ ⎝
⎛ ΔS
R - ΔH
≠
= e RT ΔG Nh
k RT
-T 1
⎟ ⎠
⎜ ⎞
⎝
⎛ T
ln k
≠≠
