V. ORGANIC REACTIONS (cont.

)
Chem211E Organic Chemistry
Engr. KBDimalanta
1. Writing Equations
for Organic Rxns
• It is a schematic representation of the energy changes
that take place as reactants are converted to
2. Kinds of Organic
Rxns
products.
• It plots energy (y-axis) vs. the progress of reaction or
3. Bond Creation &
Bond Breaking the reaction coordinate (x-axis).
4. The Energy
Diagram • Many details can be gleaned from the energy diagram
such as:
5. Kinetics of
Organic Rxns ✓ How readily a reaction proceeds?
6. Catalysts in
✓ How many steps are involved?
Organic Rxns ✓ How the energies of the reactants, products, and
intermediates compare?
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns • The energy difference between the reactants and
products is Δ𝐻°. Because the products are at lower
2. Kinds of Organic
Rxns energy than the reactants, the reaction for the diagram
shown is exothermic and energy is released.
3. Bond Creation &
Bond Breaking

4. The Energy
• The energy difference between
Diagram the starting material and the
5. Kinetics of
transition state is called the
Organic Rxns energy of activation, Ea or the
6. Catalysts in activation energy.
Organic Rxns
1. Writing Equations
for Organic Rxns
• The transition state corresponds to point with the
maximum unstable energy in a chemical reaction.
2. Kinds of Organic
Rxns
➢ It indicates the transition when the bond between A
and B is only partially broken, and the bond
3. Bond Creation &
Bond Breaking between B and C is only partially formed
4. The Energy
Diagram NOTE:
• At the transition state, the bond between A and B can
5. Kinetics of
Organic Rxns still re-form to regenerate the starting material OR the
6. Catalysts in
bond between B and C can form to generate the
Organic Rxns product.
 Drawing the Transition State
1. Writing Equations o The transition state must be drawn in between the
for Organic Rxns
structures of the starting material and product.
2. Kinds of Organic o Any bond that is partially broken or formed is drawn with a
Rxns
dashed line.
3. Bond Creation & o Any atom that gains or loses a charge contains a partial
Bond Breaking
charge in the transition state.
4. The Energy o Transition states are drawn in brackets, with a superscript
Diagram ‡
double dagger ( ).
5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 Drawing the Transition State
1. Writing Equations
for Organic Rxns
EXAMPLES:
Draw the structure for the transition state in each
2. Kinds of Organic
Rxns
reaction.
3. Bond Creation &
Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 Activation Energy (𝑬𝒂 )
1. Writing Equations
for Organic Rxns
• The activation energy is also defined as the
minimum amount of energy needed to break bonds in
2. Kinds of Organic
Rxns
the reactants.
→ In short: it represents the energy barrier that must
3. Bond Creation &
Bond Breaking be overcome for a reaction to occur.
4. The Energy
Diagram ➢ A slow reaction has large activation energy.
5. Kinetics of
Organic Rxns ➢ A fast reaction has low activation energy.
6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns
For any energy diagram:
2. Kinds of Organic
Rxns
▪ 𝐸𝑎 determines the height
of the energy barrier
3. Bond Creation &
Bond Breaking
▪ Δ𝐻° determines the
4. The Energy
Diagram relative position of the
reactants and products in
5. Kinetics of
Organic Rxns terms of energy.
6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns
• Two reactions can have identical values for Δ𝐻° but
very different 𝐸𝑎 values.
2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns
• The energy diagrams in (a) and (b) both depict exothermic
6. Catalysts in reactions with the same negative value of Δ𝐻°.
Organic Rxns
• 𝐸𝑎 in (a) is lower than 𝐸𝑎 in (b), which means that the
reaction (a) proceeds faster than reaction (b).
1. Writing Equations EXAMPLE:
for Organic Rxns
Compound A can be converted to either B or C. The energy
2. Kinds of Organic diagrams for both processes are drawn on the graph below.
Rxns
a) Label each reaction as
3. Bond Creation &
Bond Breaking endothermic or exothermic.
b) Which reaction is faster?
4. The Energy c) Which reaction generates the
Diagram
product lower in energy?
5. Kinetics of d) Which points on the graphs
Organic Rxns correspond to transition states?
6. Catalysts in e) Label the energy of activation
Organic Rxns for each reaction.
f) Label the ΔH° for each reaction.
1. Writing Equations
for Organic Rxns
ILLUSTRATION
▪ Overall reaction:
2. Kinds of Organic
Rxns
▪ Two-step reaction:
3. Bond Creation &
Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns Each step has its own energy barrier, with a
transition state at the energy maximum.
1. Writing Equations ILLUSTRATION (cont.):
for Organic Rxns

2. Kinds of Organic
Rxns Step [1] is endothermic because
energy is needed to cleave the A–B
3. Bond Creation & Energy Diagram for Step [1]
Bond Breaking
bond, making ΔH° a positive value
and placing the products of Step [1]
4. The Energy at higher energy than the starting
Diagram
materials. In the transition state, the
5. Kinetics of A–B bond is partially broken.
Organic Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations ILLUSTRATION (cont.):
for Organic Rxns

2. Kinds of Organic Step [2] is exothermic because

Rxns energy is released in forming the B–
3. Bond Creation & Energy Diagram for Step [2] C bond, making ΔH° a negative
Bond Breaking value and placing the products of
Step [2] at lower energy than the
4. The Energy
Diagram
starting materials of Step [2]. In the
transition state, the B–C bond is
5. Kinetics of partially formed.
Organic Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns
ILLUSTRATION (cont.):
The complete energy diagram for the two-step conversion of:
2. Kinds of Organic 𝐴 − 𝐵 + 𝐶:− ⟶ 𝐴:− +𝐵 − 𝐶
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
**In a multistep mechanism, the step with the highest energy
transition state is called the rate-determining step.
1. Writing Equations
for Organic Rxns
ILLUSTRATION (cont.):
✓ The overall process is represented in a single energy
2. Kinds of Organic
Rxns diagram that combines both steps.
3. Bond Creation &
✓ The transition states are located at energy maxima,
Bond Breaking while the reactive intermediate B+ is located at an
4. The Energy
energy minimum.
Diagram ✓ Each step is characterized by its own value of ΔH° and Ea.
5. Kinetics of ✓ The overall energy difference between starting material
Organic Rxns
and products is called ΔH°overall.
6. Catalysts in ✓ Since Step [1] has the higher energy transition state, it is
Organic Rxns
the rate-determining step.
1. Writing Equations
for Organic Rxns
EXAMPLE:
Consider the following energy diagram.
2. Kinds of Organic
Rxns a. How many steps are involved in
this reaction?
3. Bond Creation &
Bond Breaking b. Label ΔH° and Ea for each step,
and label ΔH°overall.
4. The Energy
Diagram c. Label each transition state.
d. Which point on the graph
5. Kinetics of
Organic Rxns
corresponds to a reactive
intermediate?
6. Catalysts in e. Which step is rate-determining?
Organic Rxns
f. Is the overall reaction
endothermic or exothermic?
1. Writing Equations
for Organic Rxns
• Thermodynamics relates energy and equilibrium.
➢ How do the energies of the reactants and the products
2. Kinds of Organic compare?
Rxns
➢ What are the relative amounts of reactants and
3. Bond Creation & products at equilibrium?
Bond Breaking

4. The Energy • Equilibrium constant (𝑲𝒆𝒒 ) is a mathematical

Diagram
expression that relates the amount of starting material
5. Kinetics of
Organic Rxns to the products at equilibrium.
6. Catalysts in
Organic Rxns • Kinetics describes the reaction rates.
➢ How fast are the reactants converted to the products?
1. Writing Equations
for Organic Rxns
• Remember:
2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns
• Concentration and temp. also affect reaction rate
➢ The higher the concentration, the faster the rate.
2. Kinds of Organic Increasing concentration increases the number of
Rxns
collisions between reacting molecules, which in turn
3. Bond Creation & increases the rate.
Bond Breaking
➢ The higher the temperature, the faster the rate.
4. The Energy Increasing temperature increases the average kinetic
Diagram
energy of the reacting molecules. Because the kinetic
5. Kinetics of energy of colliding molecules is used for bond
Organic Rxns
cleavage, increasing the average kinetic energy
6. Catalysts in increases the rate.
Organic Rxns
 Equilibrium Constant (𝑲𝒆𝒒 )
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking • When Keq > 1, equilibrium favors the products (C and
D) and the equilibrium leans to the right as the
4. The Energy
Diagram equation is written.
• When Keq < 1, equilibrium favors the starting materials
5. Kinetics of
Organic Rxns (A and B) and the equilibrium leans to the left as the
6. Catalysts in
equation is written.
Organic Rxns
For a reaction to be useful, the equilibrium must
favor the products, and Keq > 1.2.
 Gibbs Free Energy (𝑮𝒐 )
1. Writing Equations
for Organic Rxns
• The Gibbs free energy denotes the relative energies
of the reactants and products that would determine
2. Kinds of Organic
Rxns
which way equilibrium leans toward.
3. Bond Creation &
Bond Breaking • The change in Gibbs free energy (∆𝐺°) is the overall
energy difference between reactants and products.
4. The Energy
Diagram → It determines whether the starting materials or
products are favored at equilibrium.
5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 𝑮𝒐 vs. 𝑲𝒆𝒒
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking
• When Keq > 1, log Keq is positive, making ∆𝑮° negative,
4. The Energy
Diagram
and energy is released. → Equilibrium favors the products
when the energy of the products is lower than the energy
5. Kinetics of
Organic Rxns
of the reactants.
• When Keq < 1, log Keq is negative, making ∆𝑮° positive,
6. Catalysts in and energy is absorbed. Thus, equilibrium favors the
Organic Rxns
reactants when the energy of the products is higher than
the energy of the reactants.
 𝑮𝒐 vs. 𝑲𝒆𝒒
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 𝑮𝒐 vs. 𝑲𝒆𝒒
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in Even small changes in energy correspond to large

Organic Rxns
differences in the relative amount of starting material and
product at equilibrium.
 𝑮𝒐 vs. 𝑲𝒆𝒒
1. Writing Equations
for Organic Rxns
EXAMPLES:
2. Kinds of Organic
Rxns
1. Which Keq corresponds to a negative value of ΔG°,
Keq = 1000 or Keq = .001?
3. Bond Creation &
Bond Breaking 2. Which Keq corresponds to a lower value of ΔG°, Keq =
10–2 or Keq = 10–5?
4. The Energy
Diagram 3. Given each of the following values, is the starting
material or product favored at equilibrium?
5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 𝑮𝒐 vs. 𝑲𝒆𝒒
1. Writing Equations
for Organic Rxns
EXAMPLES:
2. Kinds of Organic
Rxns
4. Given each of the following values, is the starting
material or product lower in energy?
3. Bond Creation &
Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 Energy Changes and Conformational Analysis
1. Writing Equations
for Organic Rxns
ILLUSTRATION:
2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 Energy Changes and Conformational Analysis
1. Writing Equations
for Organic Rxns
EXAMPLE:
The equilibrium constant for the conversion of the axial
2. Kinds of Organic
Rxns
to the equatorial conformation of methoxycyclohexane is
shown below.
3. Bond Creation &
Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns
a. Given this, which conformation is present in the larger
6. Catalysts in amount at equilibrium?
Organic Rxns
b. Is ΔG° for this process positive or negative?
c. Approximate the size of ΔG°.
 ∆𝑮𝒐 vs. Enthalpy (∆𝑯𝒐 ) and Entropy (∆𝑺𝒐 )
1. Writing Equations The free energy change (ΔG°) also depends on the enthalpy
for Organic Rxns
change (ΔH°) and the entropy change (ΔS°).
2. Kinds of Organic
Rxns • Enthalpy It is denoted the amount of heat released or
3. Bond Creation & absorbed by a reaction related to the PV work done.
Bond Breaking • On the other hand, the change in entropy is the change
4. The Energy in the amount of disorderliness between reactants and
Diagram products.
5. Kinetics of
➢ ΔS° is (+) when the products are more disorderly than
Organic Rxns the reactants.
6. Catalysts in
➢ ΔS° is (–) when the products are less disordered (more
Organic Rxns ordered) than the reactants.

Reactions resulting in an increase in entropy are favored.

 ∆𝑮𝒐 , ∆𝑯𝒐 and ∆𝑺𝒐
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns
• The equation shows that the total energy change in a
3. Bond Creation &
Bond Breaking reaction is due to two factors: the change in the
bonding energy and the change in disorder.
4. The Energy
Diagram
Importance of entropy changes (∆𝑺°) is evident:
5. Kinetics of
Organic Rxns • When the number of molecules of starting material differs
from the number of molecules of product in the balanced
6. Catalysts in
Organic Rxns chemical equation.
• When an acyclic molecule is cyclized to a cyclic one, or a
cyclic molecule is converted to an acyclic one.
 Entropy in Organic Reactions
1. Writing Equations When a single starting material
for Organic Rxns
forms two products (homolytic
2. Kinds of Organic cleavage of a bond to form two
Rxns
radicals) entropy increases and
3. Bond Creation & favors formation of the products.
Bond Breaking

4. The Energy
Diagram Entropy decreases when an
5. Kinetics of acyclic compound forms a ring,
Organic Rxns because a ring has fewer degrees
6. Catalysts in
of freedom.
Organic Rxns → In this case, the entropy shows
that equilibrium does not favor
formation of the product.
 ∆𝑮𝒐 , ∆𝑯𝒐 and ∆𝑺𝒐
1. Writing Equations
for Organic Rxns
Δ𝐺° = Δ𝐻° − 𝑇Δ𝑆°
Δ𝐺° ≈ Δ𝐻°
2. Kinds of Organic
Rxns
• At low temperatures, the total energy change is
3. Bond Creation &
Bond Breaking approximated by the change in bonding energy only
4. The Energy ➢ The product is favored in reactions in which 𝛥𝐻° is
Diagram a negative value; that is, the bonds in the product
5. Kinetics of are stronger than the bonds in the starting material.
Organic Rxns
➢ The starting material is favored in a reaction in
6. Catalysts in which 𝛥𝐻° is a positive value; that is, the bonds in
Organic Rxns
the starting material are stronger than the bonds in
the product
 ∆𝑮𝒐 , ∆𝑯𝒐 and ∆𝑺𝒐
1. Writing Equations EXAMPLES:
for Organic Rxns
1. Considering each of the following values and neglecting
2. Kinds of Organic entropy, tell whether the starting material or product is
Rxns
favored at equilibrium:
3. Bond Creation & a. Δ𝐻° = 80 𝑘𝐽/𝑚𝑜𝑙
Bond Breaking
b. Δ𝐻° = −40 𝑘𝐽/𝑚𝑜𝑙
4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 ∆𝑮𝒐 , ∆𝑯𝒐 and ∆𝑺𝒐
1. Writing Equations EXAMPLES:
for Organic Rxns
2. For a reaction with ΔH°=40 kJ/mol, decide which of the
2. Kinds of Organic following statements is/are true.
Rxns
a) The reaction is exothermic;
3. Bond Creation & b) ΔG° for the reaction is positive;
Bond Breaking
c) Keq is greater than 1;
4. The Energy d) the bonds in the starting materials are stronger than
Diagram
the bonds in the product; and
5. Kinetics of e) the product is favored at equilibrium.
Organic Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns
• Reaction quantities have no effect on the reaction rate.
• ΔG°, ΔH°, and Keq do not determine the rate of a
2. Kinds of Organic
Rxns
reaction.
→ These quantities simply indicate the direction of the
3. Bond Creation &
Bond Breaking equilibrium reaction and the relative energy of
reactants and products.
4. The Energy
Diagram
• The rate of a chemical reaction is determined by
5. Kinetics of
Organic Rxns measuring the decrease in the conc’n of the reactants
6. Catalysts in
over time, or the increase in the conc’n of the products
Organic Rxns over time.
1. Writing Equations
for Organic Rxns
• The rate equation or rate law is an equation that
shows the relationship between the rate of a reaction
2. Kinds of Organic
Rxns
and the concentration of the reactants.
3. Bond Creation &
Bond Breaking • It is determined experimentally, and it depends on the
mechanism of the reaction.
4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
 The Rate Law
1. Writing Equations
for Organic Rxns
𝒓𝒂𝒕𝒆 = 𝒌 [𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔]
2. Kinds of Organic
Rxns
• The rate constant, k, is a complex mathematical term
that takes into account the dependence of a reaction
3. Bond Creation &
Bond Breaking rate on temperature and the energy of activation.
➢ Fast reactions have large rate constants.
4. The Energy
Diagram ➢ Slow reactions have small rate constants.
• A rate equation also contains concentration terms,
5. Kinetics of
Organic Rxns [X], for all reactants involved in a one-step mechanism.
6. Catalysts in
• A rate equation contains concentration terms for only
Organic Rxns the reactants involved in the rate-determining step in a
multistep reaction
 The Rate Equation
1. Writing Equations
for Organic Rxns
ILLUSTRATION:
2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram Both reactants appear in the transition state of the single step of the
mechanism. The concentration of both reactants affects the reaction
5. Kinetics of rate and both terms appear in the rate equation.
Organic Rxns

6. Catalysts in The order of a rate equation equals the sum of the exponents of the
Organic Rxns concentration terms in the rate equation. Thus, the sum of the
exponents is two and the rate equation is second order (the reaction
follows second-order kinetics).
 The Rate Equation
1. Writing Equations
for Organic Rxns
ILLUSTRATION:
2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Only the concentrations of the reactants affecting the rate-
Organic Rxns determining step appear in the rate equation because only A–B
appears in the rate-determining step. A reaction involving only one
6. Catalysts in reactant is said to be unimolecular.
Organic Rxns
Because there is only one concentration term (raised to the first power),
the rate equation is first order (the reaction follows first-order kinetics).
 The Rate Equation
1. Writing Equations
for Organic Rxns
EXAMPLE:
For the given rate equation, what effect does the indicated
2. Kinds of Organic
Rxns
concentration change have on the overall rate of the
reaction?
3. Bond Creation &
Bond Breaking 1. rate = k [CH3CH2Br][–OH]
a. tripling the concentration of CH3CH2Br only
4. The Energy
Diagram b. tripling the concentration of –OH only
c. tripling the concentration of both CH3CH2Br and –OH
5. Kinetics of
Organic Rxns 2. rate = k [(CH3)3COH]
6. Catalysts in a. doubling the concentration of (CH3)3COH
Organic Rxns
b. increasing the concentration of (CH3)3COH by a
factor of 10
 The Rate Equation
1. Writing Equations
for Organic Rxns
EXAMPLE:
Write a rate equation for each reaction, given the
2. Kinds of Organic
Rxns
indicated mechanism.
3. Bond Creation &
Bond Breaking

4. The Energy
Diagram

5. Kinetics of
Organic Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns
• A catalyst is a substance that speeds up the rate of a
reaction.
2. Kinds of Organic
Rxns
• It is recovered unchanged in a reaction → it does not
appear in the product.
3. Bond Creation &
Bond Breaking ❖ Common catalysts in organic reactions are acids
and metals.
4. The Energy
Diagram

5. Kinetics of Organic
Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations
for Organic Rxns

2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of Organic
Rxns ✓ The catalyst lowers the energy of activation, thus increasing
6. Catalysts in the rate of the catalyzed reaction.
Organic Rxns ✓ The energy of the reactants and products is the same in both
the uncatalyzed and catalyzed reactions, so the position of
equilibrium is unaffected.
1. Writing Equations
for Organic Rxns
EXAMPLE:
Identify the catalyst in each equation.
2. Kinds of Organic
Rxns

3. Bond Creation &

Bond Breaking

4. The Energy
Diagram

5. Kinetics of Organic
Rxns

6. Catalysts in
Organic Rxns
1. Writing Equations ✓ They are biochemical catalysts composed of amino acids
for Organic Rxns
held together in a very specific three-dimensional shape.
2. Kinds of Organic
Rxns
An enzyme contains a
3. Bond Creation & region called its active
Bond Breaking
site, which binds an
4. The Energy
Diagram
organic reactant, called
a substrate.
5. Kinetics of Organic
Rxns
When bound, this unit
6. Catalysts in
Organic Rxns is called the enzyme–
substrate complex.
1. Writing Equations
for Organic Rxns
• An enzyme speeds up a biological reaction in a variety
of ways. It may hold reactants in the proper
2. Kinds of Organic
Rxns
conformation to facilitate reaction, or it may provide an
acidic site needed for a particular transformation.
3. Bond Creation &
Bond Breaking
• Once the reaction is completed, the enzyme releases
4. The Energy
Diagram the substrate and it is then able to catalyze another
reaction.
5. Kinetics of Organic
Rxns

6. Catalysts in
Organic Rxns