Empirical rate laws.

Master Courses I Semester

Advanced Physical Chemsitry Chemical Kinetics
Assoc. Prof. Eng. Alexandra Csavdri, PhD.
Basic concepts of
chemical kinetics chemical kinetics
Some basic concepts
of chemical kinetics
Advance variable (number of moles,
concentration, conversion)
Limitative component
Reaction rate r Reaction rate r
Rate law (differential, integral)
Significance of reaction order (n) and rate
coefficient (k
obs
)
Rate dependence on T:
i
n
i
i
C
obs
k
dt
i
dC
i
r

= =

=
T R
a
E
A k exp
Examples of rate laws
- Units of k
obs
dependent on n -
n Rate law [k] - example
0 r = k mole.dm
-3
.s
-1
1 r = k [H
2
O
2
] s
-1
1.5 r = k [C
2
H
5
OH]
1.5
mole
-0.5
.dm
1.5
.s
-1
2, I r = k [N
2
O]
2
mole
-1
.dm
3
.s
-1
2, II r = k [CH
3
COOC
2
H
5
][NaOH] mole
-1
.dm
3
.s
-1
3 r = k [NO]
2
[O
2
] mole
-2
.dm
6
.s
-1
2 3 r = k [H
2
O
2
][I

] + k [H
2
O
2
][I

][H
+
] ---
Experimental detn. of n and k
obs
Isolation of reactant - Degeneration of n
Experimental methods:
Differential methods: (C,r) / (P,r) data
Integral methods: (t,C) / (t,P) data
(P = Property of reaction mixture; it reflects the
reaction advance)
Rate dependence on T E
a
Arrhenius type linearization
Experimental information
Reaction mechanism
Partial reaction orders
Experimental rate law
Dependence of rate coefficients on temperature Dependence of rate coefficients on temperature
Activation energy
Influence of solvent (ionic strength, dielectric
constant)
Product distribution
Effect of catalyst / inhibitor
Reaction orders reflected
in reaction mechanisms in reaction mechanisms
Dependence r = f(C) for various n
r = k
obs
C
n
r
n>1
ln(r) = ln(k
obs
) + n ln(C)
ln(r)
Experimental detn. of n and k
obs
Experimental data
C
n=0
n<1
n=1
lnC
ln(k
obs
)
tg = n
Experimental data = POINTS !!
Differential method
Zero
th
Order (n=0), r = k
obs
Species does not affect reaction rate
Species is involved in the reaction mechanism
AFTER the rate determining step
Example:
CH
3
COCH
3
+ I
2
CH
3
COCH
2
I + H
+
+ I

(acid autocalaysis)
r = k [CH
3
COCH
3
] [H
+
] f ([I
2
])
CH
3
COCH
3
+ H
+
[CH
3
C(OH)CH
3
]
+
(fast)
[CH
3
C(OH)CH
3
]
+
CH
3
C(OH)CH
2
+ H
+
(rate determining)
CH
3
C(OH)CH
2
+ I
2
CH
3
COCH
2
I + H
+
+ I

r f ([I
2
]); n
Iodine
= 0
First Order (n=1), r = k
obs
C
Species is involved in the reaction mechanism as
a WHOLE molecule, ONCE, either in the rate
determining step itself or in another step that
precedes it
Stoechiometry of involvement: Stoechiometry of involvement:
1 molecule in 1 step
Example:
CH
3
COOC
2
H
5
+ NaOH CH
3
COONa + C
2
H
5
OH
r = k [CH
3
COOC
2
H
5
] [NaOH]
Second Order (n=2), r = k
obs
C
2
Species is involved in the reaction mechanism as
a WHOLE molecule, TWICE, either in the rate
determining step itself or in another step that
precedes it precedes it
Stoechiometry of involvement:
2 identical molecules in 1 step, or
2 consecutive steps, each involving 1 molecule
Second Order (n=2), r = k
obs
C
2
Example:
2 NO + O
2
2 NO
2
; r = k [NO]
2
[O
2
]
2 NO N
2
O
2
(fast)
N
2
O
2
+ O
2
2 NO
2
(rate determining)
I
NO + O
2
NO
3
(fast)
NO
3
+ NO 2 NO
2
(rate determining)
II
Subunitary Order (n<1), r = k
obs
C
n
I. Parallel Reactions:
- Mechanism contains at least 2 different reaction paths: of n=0
and of n=1 with respect to species
- Mechanism: A + B Products (k
0
)
A + B + Cat. Prod. + Cat. (k
1
)
- rate law: r = k
0
+ k
1
C
Cat 0 1 Cat
II. The Michaelis-Menten Mechanism (enzyme catalysis):
- Species forms a complex prior rate determining step
- Further involved, as COMPLEX, either in the rate determining
step itself or in another step that precedes it
- Mechanism: S + E SE (k
1
,k
-1
)
SE + R P + E (k
2
)
- rate law:
] [ ' 1
] [
S k
S k
r
+
=
Subunitary Order (n=0.5), r = k
obs
C
1/2
Species dissociates in two identical parts
(radicals) prior the rate determining step
Species is involved in the reaction mechanism as
the RADICAL, either in the rate determining step
itself or in another step that precedes it itself or in another step that precedes it
Often indicates reaction mechanisms involving
free radicals
Stoechiometry of involvement:
1 molecule breaks into 2 identical radicals in 1 step
further: 1 radical involved in 1 step
Subunitary Order (n=0.5), r = k
obs
C
1/2
Example:
MB + H
2
A MBH + A + H
+
]
2
[ ] [
2 / 1
]
2
) [(
2
2 / 1
1
] [
+
+ +
= =
A H H MB K kK
dt
MB d
r
(MB
+
)
2
2 MB
+
(K
1
) (fast)
MB
+
+ H
+
MBH
+
(K
2
) (fast)
MBH
+
+ H
2
A Products + H
+
(k) (rate determining)
] [
2
1
+
+
= =
H K
dt
r
MB = metylene blue, H
2
A = ascorbic acid
Overunitary Order (n>1), r = k
obs
C
n
I. Parallel Reactions:
- Mechanism contains at least 2 different reaction
paths: of n=1 and of n=2 with respect to species
- rate law: r = k
1
C + k
2
C
2
II. Combination between first order II. Combination between first order
elementary step and the one plus type
mechanism
- Species involved once, as a WHOLE, in 1 step prior
further involvement in one plus type mechanism
- rate law:
C
C k
C k
r
,
1 +
=
References
1. I. Bldea, Cinetica chimica si mecanisme de
reactie. Baze teoretice si aplicatii, Presa
Universitara Clujeana, Cluj-Napoca, 2002, pg.
11-20, 35-47
2. I. Bldea, Deducerea mecanismului de reactie,
Presa Universitara Clujeana, Cluj-Napoca,
2008, pg. 69-99, 205-211