chemical kinetics an introduction s 2 o 8 2 - + 2 i - i 2 + 2 s o 4 2 - c o ( g ) + n o 2 ( g ) c...
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Chemical Kinetics
An Introduction
S2O8
2- + 2 I- I2
+ 2 SO42-
CO(g) + NO2(g) CO
2(g) + NO
H2O2(aq) H2O(l) + O2(g)
Questions about reactions
1. What’s happening?The chemical equation
?2. How fast is it happening?
3. To what extent does it occur?
Kinetics
EquilibriumChapters 15-18
2 IO3- + 5 HSO3
- → I2 + 5 SO42- + 3 H+ + H2O
H2O2(aq) → H2O(l) + O2(g) -- slow
H2O2(aq) + catalyst → H2O(l) + O2(g) -- FAST
HC2H3O2 + H2O C2H3O2- + H3O+
Chemical Kinetics
The study of reaction rates and the sequence of steps by which a reaction
occursA Definition
Rates of Reaction• Very fast
– Explosions, neutralizations• Almost instantaneous
• Slow– Formation of diamonds, decay of 235U
• Up to millions of years
• Medium– Cooking, rusting
• minutes to years
Expressing Reaction Rates
Speed of a car:
mph = t
x
tt
xx
12
12
in time change
positionin change
For a chemical reaction we want to track concentration of products or reactants over time:
Concentration of reactants decreasesConcentration of products increases
For the reaction A → B
t
]B[
tt
B of concB of conc
in time change
B ofion concentratin change
12
12
Rate of reaction =
Or…
t
]A[
tt
A of concA of conc
in time change
A ofion concentratin change
12
12
Expressing Reaction Rate Cont’d
Note the sign: A is disappearing
a A + b B → c C + d D
Rate of reaction = rate of disappearance of reactants
=Δ[C]
Δt1c
=Δ[D]
Δt1d
Δ[A]
Δt1a
= -Δ[B]
Δt1b
= -
= rate of appearance of products
General Rate of Reaction
Time(s) [O3](mol/L)
0.0 3.20x10-5
10.0 2.42x10-5
20.0 1.95x10-5
30.0 1.63x10-5
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5
The reaction between ethylene and ozone:
C2H4 (g) + O3 (g) C2H4O(g) + O2 (g)
Rate = - = -[C2H4] t
[O3] t
Rate = - = -3.50 x 10-7mol/L·s
(1.10x10-5mol/L) - (3.20x10-5mol/L)60.0 s - 0.0 s
[O3] tRate = -
An Example
This rate is the average rate for a time period
Does not show that rate is changing with time
Does not show rate at a given instant
Plot of [O3] vs. Time
But Wait! There’s More…
Rate is dependent on concentration!
Can see this experimentally
Plot of [C2H4] and [O2] vs. Time
Instantaneous rate
• Use smaller and smaller increments of time
• The slope of a tangent line to the curve at any point is the instantaneous rate
• Note that reaction rate usually refers to the instantaneous rate
Plot of [O3] vs. Time
Reaction Rate LawFor a chemical reaction:
aA + bB + . . . → cC + dD + . . .
The rate law for the forward reaction has the form:
Rate = k [A]m[B]n . . .
k = the reaction rate constant exponents m & n are the reaction orders defines how rate is affected by concentration
More on this next week
For example, if the rate doubles when the concentration of A doubles, the rate depends on [A]1, so m = 1; if the rate quadruples when the concentration of B doubles, the rate depends on [B]2, so n = 2.
So, what affects reaction rate?
ConcentrationMolecules must collide in order to react.
Reaction rate is proportional to the
concentration of reactants.
Rate = k (collision frequency) = k (concentration)
Factors Affecting Reaction Rate
Physical stateMolecules must mix in order to collide.
The physical state (solid, liquid, gas) will affect
frequency of collisions, as well as the physical size of droplets (liquid) or particles in the case of solids.
Factors Affecting Reaction Rate
Temperature Molecules must collide with enough energy to react.
Raising the temperature increases the reaction rate by increasing the number of collisions per time unit, and
especially, the energy of the collisions.
Factors Affecting Reaction Rate
Nature of the reactantsSome species are more reactive than others.
You have seen this with the periodicity of reactivity.
For example the reactivity of the group 1 metals.
Factors Affecting Reaction Rate
Presence of a catalystCatalysts can provide alternate, lower
energy, reaction pathways. Catalysts generally reroute the pathway of a chemical reaction so that this “alternate” path, although perhaps
more circuitous, has a lower activation energy for reaction than the un-catalyzed reaction.
Lab This Week• Explore several of the factors which
affect reaction rate• Perform in any order• Perform either B or C• CHECK REAGENT
CONCENTRATIONS!• Caution with strong acids• Use waste beakers• Part A.1 use 2M H3PO4
• Part D—Note H2O2 decomposes slowly on its own.
Evidences of a Chemical Reaction
• Color change• Precipitate formation• Temperature change• Gas evolution• Formation of a weak electrolyte
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