Reaction
Reaction Rates
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Reaction Rates
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Reaction Rates
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Reaction Rates
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Factors Affecting Reaction Rates
Concentration of reactants.
More often than not, the rate of a reaction increases
when the concentration of a reactant is increased.
Increasing the population of reactants increases the
likelihood of a successful collision.
In some reactions, however, the rate is unaffected by
the concentration of a particular reactant, as long as
it is present at some concentration.
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Factors Affecting Reaction Rates
Concentration of a catalyst.
A catalyst is a substance that increases
the rate of a reaction without being
consumed in the overall reaction.
The catalyst generally does not appear in
the overall balanced chemical equation
(although its presence may be indicated by
writing its formula over the arrow).
2 H 2O2( aq )
2 H 2O(l ) O2( g )
HBr ( aq )
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Factors Affecting Reaction Rates
Concentration of a catalyst.
Figure 14.2 shows the HBr catalyzed
decomposition of H2O2 to H2O and O2.
2H 2O 2( aq ) HBr( aq )
2 H 2O ( l ) O 2 ( g )
A catalyst speeds up reactions by reducing the
activation energy needed for successful reaction.
A catalyst may also provide an alternative
mechanism, or pathway, that results in a faster
rate.
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Factors Affecting Reaction Rates
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Factors Affecting Reaction Rates
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Definition of Reaction Rate
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Definition of Reaction Rates
D[O 2 ]
where the
symbol, D (capital Greek delta), means
the change in.
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Definition of Reaction Rates
In the reaction
The concentration of
O2 increases over time.
You obtain the
instantaneous rate
from the slope of the
tangent at the point of
the curve
corresponding to that
time.
Definition of Reaction Rates
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Figure 14.5 Calculation of the average rate.
D[O 2 ] 1 D[N 2O 5 ]
Dt
2
(

Dt
)
Since two moles of N2O5 decompose for each
mole of O2 formed, the rate of the
decomposition of N2O5 is twice the rate of the
formation of O2.
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Experimental Determination of
Reaction Rates
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Experimental Determination of
Reaction Rates
2N 2O5 (g ) 4NO2 (g ) O 2 (g )
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Experimental Determination of
Reaction Rates
Colorimetry
Consider the reaction of the hypochlorite ion with
iodide.
ClO (aq) I (aq) IO (aq) Cl (aq)
The hypoiodate ion, IO, absorbs near 400 nm. The
intensity of the absorbtion is proportional to [IO], and
you can use the absorbtion rate to determine the
reaction rate.
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Dependence of Rate on
Concentration
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Dependence of Rate on
Concentration
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Dependence of Rate on
Concentration
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Dependence of Rate on
Concentration
Reaction Order
The reaction order with respect to a given
reactant species equals the exponent of the
concentration of that species in the rate law, as
determined experimentally.
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Dependence of Rate on
Concentration
Reaction Order
Consider the reaction of nitric oxide with
hydrogen according to the following equation.
2NO(g ) 2H 2 (g ) N 2 (g ) 2H 2O(g )
The experimentally determined rate law is
Rate k[NO] [H 2 ]
2
Reaction Order
Although reaction orders frequently have
whole number values (particularly 1 and 2),
they can be fractional.
Zero and negative orders are also possible.
The concentration of a reactant with a zero
order dependence has no effect on the rate
of the reaction.
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Dependence of Rate on
Concentration
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A Problem to Consider
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A Problem to Consider
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A Problem to Consider
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A Problem to Consider
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A Problem to Consider
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Change of Concentration with Time
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ConcentrationTime Equations
D[ A]
Rate k[ A ]
Dt
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ConcentrationTime Equations
[ A]t
ln  kt
[ A]o
Here [A]t is the concentration of reactant A at time t,
and [A]o is the initial concentration.
The ratio [A]t/[A]o is the fraction of A remaining at
time t.
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A Problem to Consider
[N 2O 5 ]t
ln  kt
[N 2O 5 ]o
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A Problem to Consider
[N 2O 5 ]t
ln 2
 (4.80 10 s ) (825 s)
4 1
1.65 10 mol / L
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A Problem to Consider
[N 2O 5 ]t
ln 2
 0.396
1.65 10 mol / L
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A Problem to Consider
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A Problem to Consider
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ConcentrationTime Equations
D[ A]
Rate k[ A ]2
Dt
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ConcentrationTime Equations
1 1
kt
[ A]t [A]o
Here [A]t is the concentration of reactant A
at time t, and [A]o is the initial concentration.
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ConcentrationTime Equations
[ A] kt [ A]o
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Halflife
1
ln( 2 ) kt 1
2
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Halflife
0.693
t 1
k
2
k
2
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Halflife
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Halflife
t 3.15 10 s
1
2
4
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Halflife
k[ A]o
2
[ A ]o
t1
2
2k
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Graphing Kinetic Data
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Graphing Kinetic Data
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Graphing Kinetic Data
1 1
kt
[ A]t [ A]o
y = mx + b
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Graphing Kinetic Data
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Collision Theory
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Collision Theory
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TransitionState Theory
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TransitionState Theory
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TransitionState Theory
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PotentialEnergy Diagrams for
Reactions
k Zpf
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Collision Theory and the Arrhenius
Equation
3RTabs
velocity or velocity Tabs
Mm
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Collision Theory and the Arrhenius
Equation
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Collision Theory and the Arrhenius
Equation
f e
 Ea
RT
f e
 Ea
RT
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Collision Theory and the Arrhenius
Equation
f e
 Ea
RT
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Collision Theory and the Arrhenius
Equation
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The Arrhenius Equation
k Ae
 Ea
RT
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The Arrhenius Equation
ln k ln A  Ea
RT
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The Arrhenius Equation
ln k ln Ea 1
A  R (T)
y = b +mx
A plot of ln k versus (1/T) should yield a straight line
with a slope of (Ea/R) and an intercept of ln A. (see
Figure 14.15)
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The Arrhenius Equation
ln k 1 ln Ea 1
A  R ( T1 )
and
ln k 2 ln Ea 1
A  R ( T2 )
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The Arrhenius Equation
ln k2
k1 Ea 1
(
R T1 1)
T2
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The Arrhenius Equation
ln k2
k1 Ea 1
(
R T1 1)
T2
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A Problem to Consider
3.5 103
ln
2.7 10 4
Ea 1
1
8.31 J/(mol K) 600K 650K
( )
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A Problem to Consider
Simplifying, we get:
Ea 4
ln (1.30 10 ) 1.11 1
(1.28 10 )
8.31 J/(mol)
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A Problem to Consider
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Elementary Reactions
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Elementary Reactions
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Elementary Reactions
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Molecularity
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Molecularity
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Rate Equations for Elementary
Reactions
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Rate Equations for Elementary
Reactions
Rate k[A]
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Rate Equations for Elementary
Reactions
Rate k[A][B]
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Rate Equations for Elementary
Reactions
Rate k[A][B][C]
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Rate Equations for Elementary
Reactions
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Rate Equations for Elementary
Reactions
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Rate Laws and Mechanisms
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RateDetermining Step
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RateDetermining Step
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RateDetermining Step
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RateDetermining Step
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RateDetermining Step
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RateDetermining Step
N 2O 2 H 2
k
N 2O H 2O 2 (slow)
N 2O H 2
N 2 H 2O k3 (fast)
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RateDetermining Step
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RateDetermining Step
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RateDetermining Step
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RateDetermining Step
Rate k 2 [N 2O 2 ][H 2 ]
(Rate law for the ratedetermining step)
k 2k 1
Rate 2
[NO] [H 2 ]
k 1
If we replace the constants (k2k1/k1)
with k, we obtain the observed rate law:
Rate = k[NO]2[H2].
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Catalysts
2SO 2 (g ) O 2 (g )
2SO 3 (g ) NO ( g )
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Catalysts
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Operational Skills
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Operational Skills
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Figure 14.1:
Combining
product of
formaldehyde
with hydrogen
sulfite ion.
Photo courtesy of
James Scherer.
Return to Slide 2
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Figure 14.9: A plot of ln [N2O5] versus time.
Return to Slide 58
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Figure 14.15:
Plot of ln k
versus 1/T.
Return to Slide 80
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Animation: Decomposition of N2O5
Return to Slide 87
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Figure 14.20: Enzyme action (lock
andkey model).