Orgo Ch 4 extra
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when two reactants add together to form a single product with no atoms left over
the opposite of addition reactions; occur when a single reactant splits into two products, often with formation of a small molecule and a double bond
when two reactants exchange parts to give two new products
when a single reactant undergoes a reorganization of bonds and atoms to yield an isomeric product
homolytic bond breaking
- one electron stays with each fragment
heterolytic bond breaking
- two electrons stay with one fragment
homogenic bond making
- one elctron donated by each fragment
heterogenic bond making
- two electrons donated by one fragment
rad* + A:B--> Rad:A + *B
radicals are formed
a radical reacts to generate another radical
the radicals are depleted
Change in enthalpy
sum of bonds broken minus sum of bonds formed
BDEs decrease with what (in terms of carbon)
- with more highly substituted
- ex: methy;= 435
- primary radical= 410
- secondary= 397
- tertiary= 381
__ radicals are the easiest to form.
stability of free radicals
tertiary > secondary > primary > methyl
Bromination is __. The secondary carbons are __ as reactive as primary.
__ in __ is highly __.
- rate determining step
How can you distinguish initiation from propagation?
- initiation: creates new free radicals
- propagation: combines a free radical and a reactant to form a product and another free radical
Bond dissociation __ energy.
bond formation __ energy.
The vertical axis in a graph indicates what?
The horizontal axis indicates what?
- reaction coordinate
- or just rxn
Where are the.....
- highest points in an energy diagram
- lowest points after the curve are the intermediates
- highest Ea is rate limiting
Where will Ea be?
between the start point and the energy max
Where will deltaH be?
- between the two species, either reactant with intermediates or intermediate with product
- the total will be between reactant and prodcut
With increasing Ea, rate __.
With increasing temperature, rate __.
Fluorine reacts __.
Chlorine reacts __.
- at a moderate rate
- must be heated to reaect
- does not react
Reaction intermediates are stable as long as what?
they don't collide with another molecule or atom, but they are very reactive
Transition states are at __.
Intermediates are at __.
- energy maximas
- energy minimas
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