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Radical reaction kinetics
Radical reactions are very fast- how do we measure rate data?
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Initiation techniques- laser flash photolysis, flow techniques
Concentration over time measurement techniques- absorption spectroscopy, resonance
fluorescence
Temperature measurement techniques- thermocouple, thermometer

Rate of radical formation in the initiation step, rate of radical reaction in the propagation step, and
the rate of radical destruction in the termination step
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One-step reactions can be unimolecular or bimolecular
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The rate of a bimolecular reaction
would be v=kbim[A][B] where the rate constant is limited by the rate of diffusion
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The SSA is a very
useful tool for simplifying rate equation calculations, as we can simplify the rate of change of the
intermediate over time to be zero e
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𝑑[𝑅
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Therefore, the overall rate law for a complex

reaction now only need the concentrations of the [reactant] and the [product]
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The first rate equation is the rate of [A] and [B] going to [C] and back to [A] and [B] e
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𝑑[𝐴]
𝑑[𝐵]
=
= −𝑘1[𝐴][𝐵] + 𝑘 − 1[𝐶]
𝑑𝑡
𝑑𝑡
Then the second rate equation is the rate of change of [C] e
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𝑑[𝐶]
= 𝑘1[𝐴][𝐵] − 𝑘 − 1[𝐶] − 𝑘2[𝐶]
𝑑𝑡
Lastly, rate equation three is the formation of product (rate of change of D) e
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𝑑[𝐷]
= 𝑘2[𝐶]
𝑑𝑡
Arrhenius equation−𝐸𝑎

𝑘 = 𝐴𝑒 ( 𝑅𝑇 )
k- rate constant
A-pre exponential factor
Ea- Activation energy
R-Gas Constant
T- Temperature
In an Arrhenius plot, we plot Ink vs 1/T

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