Chapter3 6 Chemical Reactivity and Mechanisms '13 BW Modified

Can you remember?
"
Chapter 6. Chemical Reactivity ! and Mechanisms! !

Junha Jeon !
Department of Chemistry ! University of Texas at Arlington ! Arlington, Texas 76019 ! " ! Chem 2321, Fall 13 !
Nature of Atomic Orbital Overlap: Two Theories

: How is a covalent bond formed from the overlap of atomic overlap?
! Valence bond theory! ! ! Molecular orbital theory! ! ! !
"
Valence Bond (VB) Theory!

A bond: simply viewed as the sharing of electron density between two atoms as a result of the constructive interference of their atomic orbitals.! For example,! ! sigma (") bond! In fact, all single bond are sigma (") bond.!
H H H H H H
Valence Bond Theory!

A bond: simply viewed as the sharing of electron density between two atoms as a result of the constructive interference of their atomic orbitals.! For example,! ! sigma (") bond! In fact, all single bond are sigma (") bond.!
H H H H H H
Molecular Orbital (MO) Theory!

Valence bond theory is good, yet not perfect (only use constructive interference). ! Molecular orbitals: mathematically combined atomic orbitals that extend over the ! entire molecule. The mathematical method is called the linear combination of ! atomic orbitals (LCAO).! ! MOs are a more complete analysis of bonds because they include both ! constructive and destructive interference.! ! The number of MOs created must be equal to the number of atomic orbitals that ! were used.! ! H2 MOs!
A Bond to Make!
H!
H!
stabilization !
HH!
1 !
A Bond to Break!
A Bond to Break!
H!
H!
destabilization! !
H!
H!
destabilization! ! : need kinetic energy "
HH!
HH!
6.1 Enthalpy!
Enthalpy (#H or q)! ! The kinetic energy exchange between the reaction and its surroundings at constant pressure!"(q = heat)! " " " ! The amount of energy necessary to break the bond homolytically.! !
Enthalpy!
Homolytic bond cleavage:! ! ! !
Heterolytic bond cleavage:! ! !
Enthalpy!
Homolytic bond cleavage:! ! ! !
Enthalpy!
Enthalpy (#H or q)! !# The kinetic energy exchange between the reaction and its surroundings at constant pressure!" ! The amount of energy necessary to break the bond homolytically.! ! Bond dissociation energy (BDE), #H" !
Heterolytic bond cleavage:! ! !
Homolytic bond cleavage: !
2 !
Bond Dissociation Energies !
Heat of Reaction (#H) !

Most reactions involve multiple bonds breaking and forming. ! ! If during a chemical reaction the reaction temperature decreases, the reaction causes the surrounding temperature to decreases.! : Exothermic process the system gives energy to the surroundings (#H is negative).! ! If during a chemical reaction the reaction temperature increases, the reaction causes the surrounding temperature to increases.! : Endothermic process the system receives energy to the surroundings (#H is positive).! ! ! !
3 !

Most reactions involve multiple bonds breaking and forming. ! ! If during a chemical reaction the reaction temperature decreases, the reaction causes the surrounding temperature (e.g. solvent) to decreases.! : Exothermic process the system gives energy to the surroundings (#H is negative).! ! If during a chemical reaction the reaction temperature increases, the reaction causes the surrounding temperature to increases.! : Endothermic process the system receives energy to the surroundings (#H is positive).! ! ! !

Most reactions involve multiple bonds breaking and forming. ! ! If during a chemical reaction the reaction temperature decreases, the reaction causes the surrounding temperature (e.g. solvent) to decreases.! : Exothermic process the system gives energy to the surroundings (#H is negative).! ! If during a chemical reaction the reaction temperature increases, the reaction causes the surrounding temperature to increases.! : Endothermic process the system receives energy to the surroundings (#H is positive).! ! ! !

Most reactions involve multiple bonds breaking and forming. ! ! If during a chemical reaction the reaction temperature decreases, the reaction causes the surrounding temperature to decreases.! : Exothermic process the system gives energy to the surroundings (#H is negative).! ! If during a chemical reaction the reaction temperature increases, the reaction causes the surrounding temperature to increases.! : Endothermic process the system receives energy to the surroundings (#H is positive).! ! ! !

Most reactions involve multiple bonds breaking and forming. ! ! If during a chemical reaction the reaction temperature decreases, the reaction causes the surrounding temperature to decreases.! : Endothermic process the system receives energy to the surroundings (#H is positive).! ! If during a chemical reaction the reaction temperature increases, the reaction causes the surrounding temperature to increases.! : Exothermic process the system gives energy to the surroundings (#H is negative).! ! ! ! !
Predicting #H of a Reaction!
! Reaction coordinate: the progress of the reaction! ! !
4 !
!H = 139 kJ/mol!
+ 623!
762!
+ 623!
762!
6.2 Entropy!
What is the ultimate measure for determining whether or not a reaction can occur?! Enthalpy and Entropy must both be considered when predicting whether a reaction will occur.! ! ! Entropy ($S): dened as molecular disorder, randomness, freedom! : particularly statistical thermodynamics (probability)! ! ! Entropy may most accurately be thought of as the number of states that a molecules energy can be distributed over. !
6.2 Entropy!
5 !
6.2 Entropy!
6.2 Entropy!
Entropy: Free Expansion of a Gas!

! Molecules exhibit vibrational, rotational, and translational motion.! ! Motion within molecule! ! If ! the energy of molecules can be distributed in a higher number of vibrational, # Vibrational motion: motion that changes the shape of molecule ! ! rotational, and translational states, the sample will have athe greater entropy. stretching, bending, and rotation of bonds! ! Motion of whole molecule! ! # Rotational motion: whole molecule spins around an axis in three dimensional ! space ! ! # Translational motion: whole atom/molecule changes its location in three ! dimensional space ! a higher state of entropy" !

! Molecules exhibit vibrational, rotational, and translational motion.! ! If the energy of molecules can be distributed in a higher number of vibrational, rotational, and translational states, the sample will have a greater entropy.!
a higher state of entropy"

! Molecules exhibit vibrational, rotational, and translational motion.! ! If the energy of molecules can be distributed in a higher number of vibrational, rotational, and translational states, the sample will have a greater entropy.!
Entropy!
! #$%"total entropy change will determine whether a process is spontaneous (favors the forward direction, an increase):! ! ! ! consider #Ssys: the reaction, #Ssurr: usually solvent! The Second Law of Thermodynamics! ! a higher state of entropy" ! For chemical reactions, we must consider the entropy change for both the system (the reaction) and the surroundings (the solvent usually).!
6 !
Entropy!
! #$%"total entropy change will determine whether a process is spontaneous (favors the forward direction, an increase):! ! ! ! consider #Ssys: the reaction, #Ssurr: usually solvent! The Second Law of Thermodynamics! ! For chemical reactions, we must consider the entropy change for both the system (the reaction) and the surroundings (the solvent usually).!
Entropy of System!
! #Ssys : the large state of possible state; freedom! ! ! ! ! Example I: will #Ssys be positive or negative?!
Entropy of System!
! #Ssys : the large state of possible state; freedom! ! ! ! ! Example I: will #Ssys be positive or negative?!
Entropy of System!
! #Ssys : thee large state of possible state; freedom! ! ! ! ! Example II: will #Ssys be positive or negative?!
6.3 Gibbs Free Energy!

! The spontaneity of a process depends only on #Stot!
Gibbs Free Energy!

! ! #Ssys can be measured or estimated.!
7 !
Gibbs Free Energy!

Gibbs Free Energy!

! ! #Ssys can be measured or estimated.! ! #$%"measurement of #Ssurr?! ! ! !
! ! #Ssys can be measured or estimated.! ! #$%"measurement of #Ssurr?! ! ! !
Gibbs Free Energy!
Gibbs Free Energy!

! 1. The sign of #Ssurr depends on the direction of the heat ow: !

At constant temperature, an exothermic process in the system causes heat to ow into surroundings, increasing the random motions and thus the entropy of surroundings.!
! #Ssys can be measured or estimated.! ! #$%"measurement of #Ssurr?! ! ! ! see, slide ! 28 for #Gsys!
! 2. The magnitue of #Ssurr depends on the temperature: !

The transfer of a given quantity of energy as heat produces a much greater percent change in the randomness of the surroundings at a low temperature than it does at a high temperature.!
Gibbs Free Energy!

Gibbs Free Energy!
! ! Multiply both sides by negative temperature (T): The Gibbs Free Energy, #G: simply #G = T#Stot! ! ! ! Spontaneity of a process: ! #Stot: positive! The Gibbs Free Energy, #G: negative!
8 !
Gibbs Free Energy!
Gibbs Free Energy!
! Spontaneity of a process: ! #Stot: positive! The Gibbs Free Energy, #G: negative!
! Spontaneity of a process: ! #Stot: positive! The Gibbs Free Energy, #G: negative! " The second law of thermodynamics"
Gibbs Free Energy: Example!
1. Predict the sign (+ or ) for #Ssys.! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or -) of $Hsys.! 3. Predict the sign (+ or -) for $Ssurr.! 4. Predict the sign (+ or -) for $G.! 5. How will the spontaneity of the reaction depend on temperature?!
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or -) of $Hsys.! 3. Predict the sign (+ or -) for $Ssurr.! 4. Predict the sign (+ or -) for $G.! 5. How will the spontaneity of the reaction depend on temperature?!
Enthalpy!
Enthalpy (#H or q)!
slide 13!
!# The kinetic energy exchange between the reaction and its surroundings at constant pressure!" ! The amount of energy necessary to break the bond homolytically.! 1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. (overall, three pi bonds to one pi and two sigma bonds.) ! (hint: see the next page.)! ! Bond dissociation energy (BDE), #H" ! Homolytic bond cleavage: !
9 !
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. (overall, three pi bonds to one pi and two sigma bonds.) ! !
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. Negative (exothermic)! ! 3. Predict the sign (+ or -) for $Ssurr.! 4. Predict the sign (+ or -) for $G.! 5. How will the spontaneity of the reaction depend on temperature?!
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. Negative (exothermic)! 3. Predict the sign (+ or ) for #Ssurr. ! 4. Predict the sign (+ or -) for $G.! 5. How will the spontaneity of the reaction depend on temperature?!
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. Negative (exothermic)! 3. Predict the sign (+ or ) for #Ssurr. ! 4. Predict the sign (+ or -) for $G.! 5. How will the spontaneity of the reaction depend on temperature?!
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. Negative (exothermic)! 3. Predict the sign (+ or ) for #Ssurr. Positive! ! 4. Predict the sign (+ or -) for $G.! 5. How will the spontaneity of the reaction depend on temperature?!
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. Negative (exothermic)! 3. Predict the sign (+ or ) for #Ssurr. Positive, for #Ssys. Negative.! ! 4. Predict the sign (+ or -) for $G.! 5. How will the spontaneity of the reaction depend on temperature?!
10 !
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. Negative (exothermic)! 3. Predict the sign (+ or ) for #Ssurr. Positive, for #Ssys. Negative.! 4. Predict the sign (+ or ) for #G.! 5. How will the spontaneity of the reaction depend on temperature?!
1. Predict the sign (+ or ) for #Ssys. Negative! 2. In the reaction, two pi bonds are converted into two sigma bonds. Predict the sign (+ or ) of #Hsys. Negative (exothermic)! 3. Predict the sign (+ or ) for #Ssurr. Positive! 4. Predict the sign (+ or ) for #G.! 5. Depending on temperature!!!
Gibbs Free Energy: Exergonic vs. Endergonic!

! The spontaneity of a process: negative #G " Exergonic process! : favor the products! ! The spontaneity of a process: positive #G " Endergonic process! : favor the reactants! !
6.4 Equilibria!
Consider an exergonic process with a () $G. Will every molecule of A and B be converted into products?! No. An equilibrium will eventually ! be reached.! A spontaneous process will simply ! favor the products meaning there ! will be more products than ! reactants.! !
Equilibria!
Consider an exergonic process with a () $G. Will every molecule of A and B be converted into products?! No. An equilibrium will eventually ! be reached.! A spontaneous process will simply ! favor the products meaning there ! will be more products than ! reactants.! !
Equilibria!
Consider an exergonic process with a () $G. Will every molecule of A and B be converted into products?! No. An equilibrium will eventually ! be reached.! A spontaneous process will simply ! favor the products meaning there ! will be more products than ! reactants!
11 !
Equilibria!
Why doesnt an exergonic process react 100% to give products? Why will some reactants remain? (moles of reactants are present.)! In any reaction, collisions are necessary.! ! As [A] and [B] decrease, collisions between A and B will occur less often.! ! As [C] and [D] increase, collisions between C and D will occur more often.! The more often C and D collide, the more often collisions will occur with enough free energy for the reverse reaction to take place.! ! Recall that EQUILIBRIUM is dynamic and occurs when the forward and reverse reaction rates are equal.!
Equilibria!
Equilibria!
Equilibria!
Equilibria!
Equilibria!
Why doesnt an exergonic process react 100% to give products? Why will some reactants remain? (moles of reactants are present.)! In any reaction, collisions are necessary.! ! As [A] and [B] decrease, collisions between A and B will occur less often.! ! As [C] and [D] increase, collisions between C and D will occur more often.! The more often C and D collide, the more often collisions will occur with enough free energy for the reverse reaction to take place.! ! Recall that equilibrium is dynamic and occurs when the forward and reverse reaction rates are equal.!
12 !
Equilibria!
! Equilibrium is also the state with the! lowest free energy overall.! ! Every system seeks to achieve! a minimum of free energy. ! !
Equilibria!
! Equilibrium is also the state with the! lowest free energy overall.! ! Every system seeks to achieve! a minimum of free energy. ! !
K > 1! K = 1! K < 1!
K > 1! K = 1! K < 1!
Equilibria!
! Keq and $G ! R = gas constant (8.314 J/molK)! !
Equilibria!
! Keq and $G! R = gas constant (8.314 J/molK)! !
K > 1! K = 1! K < 1!
Thermodynamics!
! Keq, $G, $H, and $S: thermodynamic terms! ! Thermodynamics: the study of how energy is distributed under the inuence of entropy.! !
Thermodynamics!
13 !
Thermodynamics!
6.5 Kinetics!
! Spontaneous process: ! thermodynamically favorable, i.e. favoring formation of products ! That does not tell us anything about the rate or kinetics for the process.! ! ! Some spontaneous processes: fast (e.g. explosions)! ! ! Some spontaneous processes: slow [e.g. C%(diamond) " C (graphite)]! ! ! The study of reaction rates: kinetics! ! ! ! !
Kinetics!
Kinetics!
Kinetics!
Kinetics!
! Spontaneous process: ! thermodynamically favorable, i.e. favoring formation of products ! That does not tell us anything about the rate or kinetics for the process.! ! ! Some spontaneous processes: fast (e.g. explosions)! ! ! Some spontaneous processes: slow [e.g. C%(diamond) " C (graphite)]! ! ! The study of reaction rates: kinetics! ! ! Reaction rate: the number of collisions that will result in product production in a given period of time! !
14 !
Kinetics!
! Spontaneous process: ! thermodynamically favorable, i.e. favoring formation of products ! That does not tell us anything about the rate or kinetics for the process.! ! ! Some spontaneous processes: fast (e.g. explosions)! ! ! Some spontaneous processes: slow [e.g. C%(diamond) " C (graphite)]! ! ! The study of reaction rates: kinetics! ! ! Reaction rate: the number of collisions that will result in product production in a given period of time! !
Rate Equations!
! ! ! ! ! ! ! ! ! Reaction constant: specic to each reaction! ! Concentration: proportional to a frequency of collisions of molecules that lead to a reaction! !
Rate Equations!
! ! ! ! ! ! ! ! ! Reaction constant: specic to each reaction! ! Concentration: proportional to a frequency of collisions of molecules that lead to a reaction! !
Rate Equations!
! The degree to which a change in [reactant] will affect the rate is known as the order.! ! The order is represented by x and y in the rate law equation (experimentally determined).! !
Rate Equations!
Rate Equations!
15 !
Factors Affecting the Reaction Rate !

0. The concentrations of the reactants! 1. Energy of activation! 2. The temperature! 3. Geometry and sterics! ! ! ! ! !
Factors Affecting the Reaction Rate !

0. The concentrations of the reactants! 1. Energy of activation! 2. The temperature! 3. Geometry and sterics! ! ! ! ! ! related to the rate constant (k) !
Factors Affecting the Reaction Rate (Rate Constant, k) !

1. Energy of activation! : energy barrier between the reactants and the products the minimum amount of energy required for a reaction to occur between two reactants that collide ! !

1. Energy of activation! ! A certain threshold kinetic energy of molecules (Ea)! !

1. Energy of activation! ! A certain threshold kinetic energy of molecules (Ea)! ! Distribution of kinetic energy ! ! !

1. Energy of activation! ! A certain threshold kinetic energy of molecules (Ea)! ! Distribution of kinetic energy ! ! !
16 !

1. Energy of activation! ! A certain threshold kinetic energy of molecules (Ea)! ! Distribution of kinetic energy ! ! Catalysts (and enzymes) ! catalyst: a compound that ! can speed up the rate of a ! reaction without itself being ! consumed by the reaction! alternating a reaction pathway! not changing $Greactants ," $gproducts and the position of " equilibrium! !

1. Energy of activation! ! A certain threshold kinetic energy of molecules (Ea)! ! Distribution of kinetic energy ! ! Catalysts (and enzymes) ! catalyst: a compound that ! can speed up the rate of a ! reaction without itself being ! consumed by the reaction! alternating a reaction pathway! not changing $Greactants ," $gproducts and the position of " equilibrium! !

1. Energy of activation! ! A certain threshold kinetic energy of molecules (Ea)! ! Distribution of kinetic energy ! ! Catalysts (and enzymes) ! catalyst: a compound that ! can speed up the rate of a ! reaction without itself being ! consumed by the reaction! alternating a reaction pathway! not changing $Greactants ," $Gproducts and the position of " equilibrium! !

2. Temperature! : a measure of a systems average kinetic energy" ! !

3. Geometric and Steric ! : the geometry of the reactants and the orientation of their collision can have an impact on the frequency of collisions that lead to a reaction. ! ! ! !

3. Geometric and Steric ! : the geometry of the reactants and the orientation of their collision can have an impact on the frequency of collisions that lead to a reaction. ! ! We are going to discuss this factor in chapter 7.! ! !
17 !
6.6 Energy Diagrams: Kinetics vs. Thermodynamics!
Kinetics vs. Thermodynamics!
! C + D is kinetically and thermodynamically favorable!!
! C + D is thermodynamically favorable!! ! E + F is kinetically favorable!!
! C + D is thermodynamically favorable!! ! E + F is kinetically favorable!! At high temperature, C + D vs. E + F ?? !
Transition States vs. Intermediates!

! Transition states: at all local energy maxima! ! Intermediates: at all local energy minima! !
! C + D is thermodynamically favorable!! ! E + F is kinetically favorable!! At high temperature, C + D vs. E + F ?? !
18 !

! Transition states: at all local energy maxima! transiently exist and cannot be isolated!! bonds are in the process of being ! broken and/or formed simultaneously.!

! Transition states: at all local energy maxima! transiently exist and cannot be isolated!! bonds are in the process of being ! broken and/or formed simultaneously.!

! Intermediates: at all local energy minima! intermediates generally exist long enough to be observed.! bonds are not in the process of breaking or forming. ! !
The Hammond Postulate!

! Two points on an energy diagram that are close in energy should be similar in structure.! ! !
The Hammond Postulate!

! Two points on an energy diagram that are close in energy should be similar in structure.! ! !
6.7 Nucleophiles and Electrophiles!

Three major reaction categories:! ! 1. Ionic (polar) reactions! 2. Radical reactions (chapter 11)! 3. Pericyclic reactions (chapter 17)! ! !
19 !
Nucleophiles and Electrophiles!

1. Ionic (polar) reactions! the participation of ions as reactants, intermediates, or products! the force of attraction between opposite charges! ! !

1. Ionic (polar) reactions! the participation of ions as reactants, intermediates, or products! the force of attraction between opposite charges! !

! Nucleophile (nucleophilic reagent): a reagent that forms a bond to its reaction partner (the electrophile) by donating both bonding electrons. (nucleus lover)! ! Nucleophilic center: an electron-rich atom that is capable of donating a pair of electron! !

! Nucleophile (nucleophilic reagent): a reagent that forms a bond to its reaction partner (the electrophile) by donating both bonding electrons. (nucleus lover)! ! Nucleophilic center: an electron-rich atom that is capable of donating a pair of electron! !
an electrophile! center!
a nucleophile! center!
electrophile!
nucleophile!
electrophile!
nucleophile!

! Nucleophile (nucleophilic reagent): a reagent that forms a bond to its reaction partner (the electrophile) by donating both bonding electrons. (nucleus lover)! ! Nucleophilic center: an electron-rich atom that is capable of donating a pair of electron! ! ! ! ! ! ! Polarizability: the ease of distortion of the electron cloud of a molecular entity by an electric eld (such as that due to the proximity of a charged reagent)! affecting the strength of nucleophilicity. ROH vs. RSH! !

! Nucleophile (nucleophilic reagent): a reagent that forms a bond to its reaction partner (the electrophile) by donating both bonding electrons. (nucleus lover)! ! Nucleophilic center: an electron-rich atom that is capable of donating a pair of electron! ! ! ! ! ! ! Polarizability: the ease of distortion of the electron cloud of a molecular entity by an electric eld (such as that due to the proximity of a charged reagent)! affecting the strength of nucleophilicity. ROH vs. RSH! !
20 !

! Electrophile (electrophilic reagent): a reagent that forms a bond to its reaction partner (the nucleophile) by accepting both bonding electrons from its reaction partner. (electron lover)! ! Electrophilic center: an electron-decient atom that is capable of accepting a pair of electrons!

electrophile!
nucleophile!
electrophile!
nucleophile!

carbocation!
6.8 Mechanism and Arrow Pushing!

! Acid-base reaction!
21 !
Four Patterns of Ionic Mechanism !

1. Nucleophilic attack! 2. Loss of a leaving group! 3. Proton transfers (acid/base)! 4. Rearrangements! !

1. Nucleophilic attack! !
a lone pair:! a nucleophilic center! !
empty p orbital:! an electrophilic center! !


a lone pair:! a nucleophilic center! !
empty p orbital:! an electrophilic center! !
a lone pair:! ! a nucleophilic center! !
inductive effect (carbon with a &+ charge):! an electrophilic center! !

1. Nucleophilic Attack!
A. Stepwise view: Resonance contribution! ! ! ! ! ! ! B. One-step electron ow !
a lone pair:! ! a nucleophilic center! !
inductive effect (carbon with a &+ charge):! an electrophilic center! !
22 !
2. Loss of Leaving Group!
3. Proton Transfer!
! Acid-base reaction (protonated)! ! ! ! ! ! or! ! Acid-base reaction (deprotonated)! !
or"
3. Proton Transfer!
3. Proton Transfer!
A. One-step electron ow ! ! ! ! ! ! B. Stepwise view: Resonance contribution ! !
23 !
4. Rearrangement!
Carbocations can be stabilized by neighboring groups through slight orbital overlap called hyperconjugation.! ! ! ! ! ! ! !
4. Rearrangement!
Carbocations can be stabilized by neighboring groups (e.g. alkyl group) through slight orbital overlap called hyperconjugation.! ! ! ! ! ! ! !
4. Rearrangement!
Carbocations can be stabilized by neighboring groups (e.g. alkyl group) through slight orbital overlap called hyperconjugation.! ! ! ! ! ! ! !
4. Rearrangement!
Carbocation stability: depending upon # of alkyl groups attached directly to the carbocation ! ! ! ! ! ! ! ! !
4. Rearrangement!
Carbocation rearrangement! 1. Hydride (H) Shift ! ! ! ! ! ! 2. Methyl Shift! !
4. Rearrangement!
24 !
4. Rearrangement!
4. Rearrangement!
What is the driving force of the Carbocation rearrangement? ! 1. Hydride (H) Shift ! ! ! ! ! ! 2. Methyl Shift! !
4. Rearrangement!
What is the driving force of the Carbocation rearrangement? Stability of C+ ! 1. Hydride (H) Shift ! ! ! ! ! ! 2. Methyl Shift! !
4. Rearrangement!
Carbocation rearrangement? ! !
4. Rearrangement!
4. Rearrangement!
25 !
4. Rearrangement!
Carbocation rearrangements generally do not occur when the carbocation is already tertiary unless a rearrangement will produce a resonance-stabilized carbocation;! !
4. Rearrangement!
4. Rearrangement!
6.9 Combining the Patterns of Arrow Pushing' !
Combining the Patterns of Arrow Pushing' !

! Two arrow-pushing patterns simultaneously! ! Concerted process: Two or more primitive changes are said to be concerted (or to constitute a concerted process) if they occur within the same elementary reaction. !
6.10 Drawing Curved Arrows!

1. The arrow starts on a pair of electrons (a bonded pair or a lone pair)! ! ! ! ! 2. The arrow ends on a nucleus (as the formation of a lone pair) .! !
26 !

1. The arrow starts on a pair of electrons (a bonded pair or a lone pair)! ! ! ! ! 2. The arrow ends on a nucleus (as the formation of a lone pair) .! !

3. Avoid breaking the octet rule. Never give C, N, O, or F more than 8 valence electrons.! ! ! ! ! ! 4. Draw arrows that follow the four key patterns.! !

3. Avoid breaking the octet rule. Never give C, N, O, or F more than 8 valence electrons.! ! ! ! ! ! 4. Draw arrows that follow the four key patterns.! !
27 !

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Chapter3 6 Chemical Reactivity and Mechanisms &#39;13 BW Modified

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Chapter 6. Chemical Reactivity ! and Mechanisms! !

Nature of Atomic Orbital Overlap: Two Theories

! Valence bond theory! ! ! Molecular orbital theory! ! ! !

Valence Bond (VB) Theory!

Valence Bond Theory!

Molecular Orbital (MO) Theory!

destabilization! ! : need kinetic energy "

Heterolytic bond cleavage:! ! !

Heterolytic bond cleavage:! ! !

Homolytic bond cleavage: !

Bond Dissociation Energies !

Bond Dissociation Energies !

Bond Dissociation Energies !

Bond Dissociation Energies !

Bond Dissociation Energies !

Heat of Reaction (#H) !

Heat of Reaction (#H) !

Heat of Reaction (#H) !

Heat of Reaction (#H) !

Heat of Reaction (#H) !

Heat of Reaction (#H) !

! Reaction coordinate: the progress of the reaction! ! !

Entropy: Free Expansion of a Gas!

Entropy: Free Expansion of a Gas!

a higher state of entropy"

Entropy: Free Expansion of a Gas!

6.3 Gibbs Free Energy!

Gibbs Free Energy!

! ! #Ssys can be measured or estimated.!

Gibbs Free Energy!

Gibbs Free Energy!

! ! #Ssys can be measured or estimated.! ! #$%"measurement of #Ssurr?! ! ! !

! ! #Ssys can be measured or estimated.! ! #$%"measurement of #Ssurr?! ! ! !

Gibbs Free Energy!

Gibbs Free Energy!

! 1. The sign of #Ssurr depends on the direction of the heat ow: !

! 2. The magnitue of #Ssurr depends on the temperature: !

Gibbs Free Energy!

Gibbs Free Energy!

Gibbs Free Energy!

Gibbs Free Energy!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Example!

Gibbs Free Energy: Exergonic vs. Endergonic!

Factors Affecting the Reaction Rate !

Factors Affecting the Reaction Rate !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Factors Affecting the Reaction Rate (Rate Constant, k) !

Chapter3 6 Chemical Reactivity and Mechanisms '13 BW Modified

Chapter3 6 Chemical Reactivity and Mechanisms '13 BW Modified