kinds of reactions mechanisms (polar, non-polar) bond...
TRANSCRIPT
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Organic Reactions
Kinds of Reactions
Mechanisms (polar, non-polar)
Bond Dissociation Energy
Reaction Profiles
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Types of Reactions
• Addition Reactions
• Elimination Reactions
C=CH
H
H
H+ HBr C C
H
H
Br
H
H
H
C=CH
H
H
H
+ NaOHC C
H
H
Br
H
H
H + H2O
+ NaBr
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Types of Reactions
• Substitution:
– Polar
– Non-polar
H
BrH
H + KCN
H
NCH
H + KBr
CH4 + Cl2 CH3Cl + HCllight (hν)
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Rearrangement
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Definitions
• Mechanism: Complete step-by-step of exactly which bonds break and which bonds form and in what order.
• Thermodynamics: The study of the energy changes that occur in chemical transformations. This allows for comparison of stability of reactants and products.
• Kinetics: The study of reaction rates, determining which products are formed most rapidly. One can predict how the rate will change with changing conditions.
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Reaction Profile (Exothermic)
rate = kr[A] [B]a b
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2nd Order Reaction
CH3Br + OH CH3OH + Br
Rate = k[CH3Br][OH ]
second order rate kinetics
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1st Order Reaction
(CH3)3CBr + H2O (CH3)3OH + HBr
Rate = k[(CH 3)3CBr]
First order rate kinetics
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Bond Breaking:Non-polar and Polar
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Bond Forming:Non-polar and Polar
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Non-polar Reaction Involves
Free Radicals
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Free Radicals are Neutral, but
Electron-Deficient
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Free Radical Chlorination
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Experimental Evidence Helps
to Determine Mechanism• Chlorination does not occur at room
temperature in the dark.
• The most effective wavelength of light is
blue that is strongly absorbed by Cl2 gas.
• The light-initiated reaction has a high
quantum yield (many molecules of product
are formed from each photon of light).
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Free Radical Species are Constantly
Generated Throughout the Reaction
Propagation
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Termination: Reaction of any 2 Radicals
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Enthalpy of Reaction (∆∆∆∆Ho)
Measures Difference in Strength of
Bonds Broken and Bonds Formed
Bond Dissociation Energy
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∆∆∆∆Ho = ΣΣΣΣbonds broken-ΣΣΣΣbonds formed
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∆∆∆∆Hrxn = -105 kJ/mol
- 351
+ 435 - 431
+ 242
= - 109 KJ/mol
= + 4 KJ/mol
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Why Not This Mechanism?
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Chlorination of Propane
60%
40%
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H’s are not abstracted at the same rate.
Reactivity of Primary (1o) H abstraction
40%
6H= 6.7
Reactivity of Secondary (2o) H abstraction
60%
2H= 30
Rate of 2o H abstraction : 1o H abstraction
= 4.5:1
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Chlorination of Methylpropane
C
CH3
CH3
CH3 H HCH3
CH3
CH2
C CH3
CH3
CH3
C.++ Cl
.
.
.
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Tertiary H’s removed 5.5 times more
readily than primary H’s in
chlorination reactions
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3o Radicals are Easiest to Form
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Stability of Free Radicals
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Bromination is Very Selective
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RDS in Bromination is highly
endothermic
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Consider the free radical monochlorination of
2,2,5-trimethylhexane. Draw all of the
unique products (ignore stereoisomers; use
zig-zag structures please) and predict the ratio
or percent composition of the products.
The relative reactivity of H abstraction in a
chlorination reaction: 1o: 2o: 3o = 1: 4.5: 5.5
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Chlorofluorocarbons and the
Depletion of Ozone.O3 O2 + O
hν
C Cl
F
F
Cl Cl
F
F
C . .
. .
. .
Cl+
Cl + O3 ClO + O2
ClO + O Cl . + O2
O3 + O 2 O2.net reaction
i)
ii)
hν
ultraviolet
a CFC
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Polar Reactions:
Nucleophiles & Electrophiles
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Nucleophiles are Bases
Electrophiles are Acids
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Addition of HBr to Ethylene
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Reactions Often Go Through
Intermediates
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Transition State
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Addition Reaction is a Two-
Step Mechanism
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How Many Mechanistic Steps?
How Many Intermediates?
How Many Transition States?
Which Step is Rate-Determining?