KIMIA ORGANIK FISIK

PENGANTAR REAKSI, KONTROL

KINETIK DAN TERMODINAMIK
 Electronegativity of Some Common
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Elements
• Higher numbers indicate greater electronegativity
• Carbon bond to more elektronegative elements cause it
has a partial positive charge (+)
Polarity

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4
 And a few more:
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 Polarizability
• Polarization is a change in electron distribution as a
response to change in electronic nature of the
surroundings
• Polarizability is the tendency to undergo polarization
• Polar reactions occur between regions of high
electron density and regions of low electron density

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 Generalized Polar Reactions
• An electrophile (like to electrons), an electron-
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poor species (Lewis acid), combines with a

nucleophile (like to nucleus), an electron-rich
species (Lewis base)
• The combination is indicated with a curved arrow
from nucleophile to electrophile
 Electrophiles & Nuclephiles
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 Problem : Is BF3 electrophile or
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nucleophile?
 An Example of a Polar Reaction: Addition of
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HBr to Ethylene
 An Example of a Polar Reaction: Addition of
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HBr to Ethylene

• HBr adds to the  part of C-C double bond

• The  bond is an electron-rich, allowing it to
function as a nucleophile
• H-Br is electron deficient at the H since Br is much
more electronegative, making HBr an electrophile
P-Bonds as Nucleophiles:

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 Mechanism of Addition of HBr to
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Ethylene
• HBr electrophile is attacked by  electrons of
ethylene (nucleophile) to form a carbocation
intermediate and bromide ion
• Bromide adds to the positive center of the
carbocation, which is an electrophile, forming a C-Br
 bond
• The result is that ethylene and HBr combine to form
bromoethane
• All polar reactions occur by combination of an
electron-rich site of a nucleophile and an electron-
deficient site of an electrophile
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 Using Curved Arrows in Polar
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Reaction Mechanisms
• Curved arrows are a way to keep track of
changes in bonding in polar reaction
• The arrows track “electron movement”
• Electrons always move in pairs in polar
reactions
• Charges change during the reaction
• One curved arrow corresponds to one step in
a reaction mechanism
 Rules for Using Curved Arrows
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• The arrow goes from the nucleophilic reaction site to the

electrophilic reaction site
• The nucleophilic site can be neutral or negatively charged
• The electrophilic site can be neutral or positively charged
Rule 1: electrons move from Nu to E

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Rule 2: Nu: can be negative or
neutral

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Rule 3: E can be positive or neutral

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Rule 4: Octet rule!

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 Practice Prob. : Add curved arrows to
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the reactions
 Solution:
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 Describing a Reaction: Equilibria, Rates,
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and Energy Changes
• Reactions can go in either direction to reach
equilibrium
– The multiplication of concentrations of the
products divided by the multiplied concentrations
of the reactant is the equilibrium constant, Keq
– Each concentration is raised to the power of its
coefficient in the balanced equation.

aA + bB cC + dD
Keq = [Products]/[Reactants] = [C]c [D]d / [A]a[B]b
 Magnitudes of Equilibrium Constants
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• Keq > 1 = most of materials are products

• Keq > 1 = most of materials are reactans

 For example:

Reactans Product

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 Free Energy and Equilibrium
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• The ratio of products to reactants is controlled by

their relative Gibbs free energy
• This energy is released on the favored side of an
equilibrium reaction
• The change in Gibbs free energy between products
and reacts is written as “DG”
• If Keq > 1, energy is released to the surrounding
(exergonic reaction)
• If Keq < 1, energy is absorbed from the surroundings
(endergonic reaction)
 Free Energy and Equilibrium
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 Numeric Relationship of Keq and Free
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Energy Change
• The standard free energy change at 1 atm pressure
and 298 K is DGº
• The relationship between free energy change and an
equilibrium constant is:
– DGº = - RT lnKeq where
– R = 1.987 cal/(K x mol) (gas constant)
– T = temperature in Kelvins
– ln = natural logarithm
• The exponential form: Keq = e-DG/RT
 Energy Changes in Equilibrium Reactions
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• Free energy changes (DGº) can be divided

into
– a temperature-independent part called entropy
(DSº) that measures the change in the amount of
disorder in the system
– a temperature-dependent part called enthalpy (DHº)
that is associated with heat given off (exothermic) or
absorbed (endothermic)
• Overall relationship: DGº = DHº - TDSº
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 Ethylene + HBr

DGº = DHº - TDSº

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 Describing a Reaction: Bond
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Dissociation Energies
 Bond dissociation energy (D): Heat change that
occurs when a bond is broken by homolysis
 The energy is mostly determined by the type of
bond, independent of the molecule
 The C-H bond in methane requires a net heat input
of 105 kcal/mol to be broken at 25 ºC.
 Table 5.3 lists energies for many bond types
 Changes in bonds can be used to calculate net
changes in heat
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More homolytic BDE’s:

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 Calculation of an Energy Change from Bond
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Dissociation Energies
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Describing a Reaction: Energy Diagrams
and Transition States

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 Describing a Reaction: Energy Diagrams
and Transition States

• The highest
energy point in a
reaction step is
called the
transition state
• The energy
needed to go
from reactant to
transition state is
the activation
energy (DG‡)

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 First Step in the Addition of HBr
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• In the addition of
HBr the transition-
state structure for
the first step
• The  bond
between carbons
begins to break
– The C–H bond
begins to form
– The H–Br bond
begins to break
Energy Diagram for step 1

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 Describing a Reaction:
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Intermediates
• If a reaction occurs in more than one step, it must
involve species that are neither the reactant nor the
final product
• These are called reaction intermediates or simply
“intermediates”
• Each step has its own free energy of activation
• The complete diagram for the reaction shows the
free energy changes associated with an intermediate
 Formation of a Carbocation
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Intermediate
• HBr, a Lewis acid, adds to the  bond
• This produces an intermediate with a positive
charge on carbon - a carbocation
• This is ready to react with bromide
 Reaction Diagram for Addition of HBr
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to Ethylene
 Two separate
steps, each
with a own
transition state
 Energy
minimum
between the
steps belongs
to the
carbocation
reaction
intermediate.
Kinetic and Thermodynamic Control
• Addition to a conjugated diene at or below room
temperature normally leads to a mixture of products in
which the 1,2 adduct predominates over the 1,4 adduct
• At higher temperature, product ratio changes and 1,4
adduct predominates
Kinetic vs. Thermodynamic Control of
Reactions