Ch. 4 Flashcards

1
Q

Where is the electron in a free radical?

A

The p orbital

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2
Q

Initiation

A

Make radicals from nonradicals

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3
Q

Propagation

A

Radical reacts with nonradical

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4
Q

Termination

A

Two radicals react to form nonradicals

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5
Q

Keq (products and reactants)

A

[products]. [C]c[D]d
= —————– = ————
[reactants]. [A]a[B]b

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6
Q

What is ∆G

A

the amount of energy available to do work; energy of products - energy of reactants

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7
Q

∆G formula

A

∆Gº = -RT(lnKeq); ∆Gº = ∆Hº - T∆Sº

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8
Q

Enthalpy

A

Change in bonding energy

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9
Q

Entropy

A

Change in disorder

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10
Q

Do cyclic molecules or acyclic molecules have more entropy?

A

Acyclic because cyclic molecules have restricted bond rotation

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11
Q

What does ∆E equal to

A

∆Gº

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12
Q

Bond dissociation ________ energy, bond formation ________ energy

A

requires, releases

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13
Q

Homolytic cleavage

A

When the bond breaks, each atom gets one electron

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14
Q

Heterolytic cleavage

A

When the bond breaks, the most electronegative gets both electrons

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15
Q

What range do most BDE fall between

A

60-100 kcal/mol

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16
Q

Rate law equation (for A+B –> C + D)

A

rate = kr[A]a[B]b

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17
Q

What is order

A

Order is the number of molecules of that reactant which is present in the rate-determining step of the mechanism

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18
Q

Rate constant formula

A

kr = Ae^(-Ea/RT)

19
Q

What is activation energy

A

the minimum kinetic energy needed to react

20
Q

What is the value of R (gas constant)

A

8.314 J/Kmol

21
Q

Intermediates

A

Short-lived species on the way to a product

22
Q

Transition states

A

the highest point in energy between two chemicals

23
Q

Rate Determining Step

A

The slowest step in the reaction will have the highest energy transition state

24
Q

With ____ Ea, rate decreases

A

increasing

25
With ______ temperature, rate increases
increasing
26
_______ reacts explosively
Fluorine
27
_____ must be heated to react
Bromine
28
_______ reacts at a moderate rate
Chlorine
29
_______ does not detectibly react
Iodine
30
Is a tertiary radical or primary radical more stable
tertiary
31
With increasing degree, dissociation energy gets ________
weaker
32
What does it mean that bromination is highly selective
Prefers tertiary over secondary over primary
33
In an endothermic reaction the transition state resembles the _____; in an exothermic reaction, the transition state resembles the _________.
product; reactant
34
Hammond Postulate
Transition state looks like what it is closest in energy to
35
Bromination is exo/endo thermic, Chlorination is exo/endo thermic
Bromination: endo Chlorination: exo
36
Bromination has a _______ difference in Ea, Chlorination has a ______ difference in Ea
large, small
37
What degree carbocation is most stable
tertiary
38
What are the two ways carbocations are stabalized by alkyl substituents
Inductive effect, hyperconjugation
39
Inductive effect
Donation of electron density along the sigma bonds
40
Hyperconjugation
Overlap of sigma bonding orbitals with empty p orbitals
41
Carbanions
Eight electrons: six bonding, one lone pair Negative charge Nucleophilic and basic
42
What degree is most stable for carboanions
Methyl, then primary
43
Carbenes
Have a neutral carbon Vacant p orbital, so it can react as an electrophile Has a lone pair in the sp2 orbital so it can react as a nucleophile