Mekdela Amba University

MEKDELA AMBA UNIVERSITY

COLLEGE OF NATURAL AND COMPUTATIONAL SCIENCES

DEPARTMENT OF CHEMISTRY

PHYSICAL ORGANIC CHEMISTRY(Chem4041)

CHAPTER TWO

ENERGETICS, KINETICS AND INVESTIGATION OF REACTION

MECHANISM
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2.1. REACTION MECHANISM

 Reaction mechanism describes the reactant involved, the intermediate formed, and the
products

 It refers to sequence of elementary reaction to give a desired product

 Reaction intermediates are formed in one step and then consumed in a later step of the
reaction mechanism.

 A mechanism is the actual process by which a reaction takes place:

 Which bonds are broken, in what order;

 How many steps are involved;

 The relative rate of each step, etc.

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2.2. Energetic of Reaction

 Energetics is the study of energy change during the course of the reaction

 Most chemical reactions are accompanied by energy changes.

 Some absorbs energy while some releases it.

 All chemical reactions involve energy change:

 Enthalpy (ΔH)

 Entropy(ΔS)

 Gibbs free energy (ΔG)

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 2.2.1. Enthalpy (ΔH)

 The enthalpy term (ΔH) is the heat given off or the heat consumed during the course of a
reaction.
 In a molecule or compound the atoms are held together by bonds.

 It measures the relative strength of bonding of the reactants and products

 The energy exchange between the chemical reaction and the surroundings is called
Enthalpy change (ΔH)

 When new bonds are formed, heat is given off and when bonds are broken, heat is consumed.
 Thus, ΔH is a measure of the bond-making and bond-breaking processes that occur as
reactants are converted into products.

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2.2.1. Enthalpy (ΔH)

 Enthalpy change is the amount of heat energy taken in or given out during

 any change in a system provided the pressure is constant.

 If weak bonds are broken and strong bonds are formed during the reaction,
heat is evolved and the reaction is an exothermic reaction

 If strong bonds are broken and weak bonds are formed, heat is consumed
and the reaction is an endothermic reaction

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2.2.1. Enthalpy (ΔH)

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2.2.2. Exothermic reaction

 Heat is give off from the system

 As a a reasult of the release of heat energy from the system (reactant), surrounding will have
increaase in temprature

 A reaction that causes the temperature of the surroundings to increase.

 In an exothermic change energy is transferred from the system (chemicals) to the

surroundings.

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 Cont…
 Energy is lost, or released, in the reaction, as the enthalpy of the products is less than the
enthalpy of the reactants.
 The products of the reaction end up with less energy than the reactants. This means that
the enthalpy change for the reaction, ∆H, will be negative.
 The products are more thermodynamically stable than the reactants
EX. Combustion, Oxidation, Neutralisation reactions exothermic reactions

Exothermic reactions 8
 2.3. Entropy

 Entropy (S°) is a measure of randomness and disorder; high entropy means high disorder
and low energy.
 It refers to a measure of how spread out or dispersed the system’s energy is
 Change in enthalpy (ΔS°) is the change in disorder between starting materials and products.
 More spread out or dispersed = increased entropy (ΔS > 0)
 Nature tends to move towards states corresponding to an increase in entropy.

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 2.3. Entropy

 Entropy (S), that is dependent on heat flow between the system and surroundings

and temperature. It will be used to determine spontaneity.

 Entropy is an additive function : the entropy of a universe is a sum of entropies of a

system and its surroundings: Suniv = Ssys + Ssur

 S° for the gas phase is greater than the liquid or solid phase of the same substance

 H 2 O(g) has greater S° than H 2 O(l)

 More complex structures have greater S° because more types of motion are possible

 C 2 H 6 (g) greater than CH4 (g)

 Note: the ∆Ssys decreases when heat is transferred from the system to surroundings and
increases when heat transferred from surroundings to the system. 12
 2.3. 4. Gibbs free energy

 Gibbs free energy refers to the energy associated with a chemical reaction that is available

after accounting for entropy

 Gibbs free energy is usable energy or energy that is available to do work.

 It is an indicator of whether the reaction will proceed spontaneously.

 The a negative ΔG associated with a reaction indicates that it can happen spontaneously.

 If ΔG is negative the product is thermodynamically stable compared to reactant and the

reaction is said to be exergonic reaction.

 If ΔG is positive the product is thermodynamically unstable compared to reactant and the

reaction is said to be endergonic reaction. 13

 Cont…

ΔG = ΔH - TΔS
 ∆G < 0 product-favored
 ∆G > 0 reactant-favored
 ∆G = 0 equilibrium
 ∆G vary with ∆H, ∆S and T?
 A large negative ∆H makes a reaction more spontaneous.
 A large positive ∆S makes a reaction more spontaneous.
 The effect of T depends on the sign of ∆S.
 If ∆s is positive, higher T makes a reaction more spontaneous
 If ∆S is negative, higher T makes a reaction less spontaneous

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 Cont…

 How does ∆G vary with ∆H, ∆S and T?

 A large negative ∆H makes a reaction more spontaneous.
 A large positive ∆S makes a reaction more spontaneous.
 The effect of T depends on the sign of ∆S.
 If ∆s is positive, higher T makes a reaction more spontaneous
 If ∆S is negative, higher T makes a reaction less spontaneous

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 2.4. KINETICS OF REACTION
 Chemical reaction kinetics deals with the rates of chemical processes.

 It deals with the rate of reactions, the mechanism, and the influence of various factors of the
reaction rates
 Physical state of the reactants.
 In order to react, molecules must come in contact with each other.
 The more homogeneous the mixture of reactants, the faster the molecules can react.
 Concentration of reactants.
 As the concentration of reactants increases, so does the likelihood that reactant molecules will collide
 Temperature
 At higher temperatures, reactant molecules have more kinetic energy, move faster, and collide more
often and with greater energy
 Presence of a catalyst
 Catalysts speed up reactions by changing the mechanism of the reaction.

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 2.5. REACTION RATES AND FREE ENERGY ACTIVATION

 Chemical reaction is a process of changing substrates into products in certain time

 Reaction rate measures the speed of the chemical reaction, determining how fast or slow it

is.

 It is defined as the change in concentration of reactants or products per unit time

 Rate of reaction is the rate at which reactants are used up, or equivalently the rate at which

products are formed.

 For the given reaction: A +2B → 3C+D
 loss of substrates at any time t is given by instantaneous rate of reaction and can be noted
as:

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 2.5.1. Activation energy
 Many chemical reactions, and almost all biochemical reactions do not occur spontaneously
and must have an initial input of energy (called the activation energy) to get started.
 Activation energy must be considered when analyzing both endothermic and exothermic
reactions

 Exothermic reactions have a net release of energy, but they still require a small amount of
energy input before they can proceed with their energy-releasing steps.

 This small amount of energy input necessary for all chemical reactions to occur is called the
activation nenergy (or free energy of activation)

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 2.5.1. Activation Energy
 For a reaction to occur, molecules must collide.

 The frequency of the collisions affects the rate of the reaction. The frequency can be changed by:

 increasing or decreasing the concentrations of the reactants

 changing the temperature to change the velocities of the molecules.

 Not all properly oriented collisions between molecules result in a reaction.

 The molecules must also have enough energy for the reaction to occur.

 The activation energy is needed because existing bonds must be broken and new bonds must be formed.

 The point in the reaction at which this reconstruction is occurring is called the transition state or

activated complex.

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 2.5.1. Activation Energy

 Activation energy can be defined as the minimum amount of energy that is required to
activate molecules or atoms so that they can undergo chemical transformation.

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 2.5.1. Activation Energy
 Reaction rates can be related directly to their activation energies defined by the Arrhenius

equation

 The Arrhenius equation relates the rate constant of a reaction to its activation energy and

the absolute temperature and has the form k = Ae−E/RT

 The activation energy of a particular reaction determines the rate at which it will proceed.

 The higher the activation energy, the slower the chemical reaction will be.

 For example, iron rusting illustrates an inherently slow reaction.

 This reaction occurs slowly over time because of its high EA.

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 2.6. Kinetics and rate determining step

 The rate determining step is the slowest step of a chemical reaction that determines the speed (rate) at
which the overall reaction proceeds.
 Rate of SN1 reaction depends upon the concentration of alkyl halide and is independent of the
concentration of nucleophile.
 Bond breaking occurs before bond formation.
 Mechanisms for S N1 reaction

 The C-X bond is broken first and then the C-Nu bond is formed, the mechanism has two-steps and a
carbocation is formed as a reactive intermediate.
 The first step is rate-determining, and the rate of such a unimolecular reaction depends on the
concentration of RX only; therefore, the rate equation is first order. 22
 2.6. Kinetics and rate determining step
 This reaction illustrates a similar nucleophilic substitution reaction with t-butyl bromide [(CH 3 )
3CBr], which also leads to substitution of Br - by CH 3CO 2 -.
 Kinetic data show that this reaction rate depends on the concentration of only one reactant, the alkyl
halide; that is, the rate equation is first order.

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 2.6. Kinetics and rate determining step

 Nucleophilic Substitution Bimolecular Reactions (SN2)

 Bond breaking and bond formation occur at the same time.
 the C-X bond is broken as the C-Nu bond is formed, the mechanism has one-step. The rate of
such a bimolecular reaction depends on the concentration of both the reactants; that is, the
rate equation is second order.

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 [Link] and rate determining step

The rate is independent on the power of the nucleophile.

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 2.7. Kinetics and thermodymamic control
 When we look at any chemical reaction, we have to take into account two main
concepts: Energies and rates
 A reaction might be described as favorable or unfavorable, fast or slow, and reversible
or irreversible.
 What does each of these terms mean?
 A favorable reaction:
 Unfavorable:
 Reversible:
 Irreversible:
 In those reactions where two or more different products formed from the same
reactants, each process has its own energy/reaction profile.

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 2.7. Kinetics and thermodymamic control
 In a reaction where several products can be formed the thermodynamic product could
be the same as the kinetic product, or it could be different.
 The energy required for the starting materials to reach the top of the barrier is called
the activation energy ( G‡).
 The arrangement of the reactants at the top of the barrier, where they can go either
backward to starting materials or forward to products, is called the transition state
(TS).
 The rate of a reaction is dependent on the size of the activation barrier, not on the
energy difference between the starting materials and the products.
 A reaction is fast if the activation energy is low, and it is slow if the activation energy
is high.

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 2.7. Kinetics and thermodymamic control
 There are some cases where one product (e.g., A) has a lower energy than a second product
(e.g., B) but the transition state leading to A is less stable than that leading to B.
 The formation of A is thermodynamically favored whereas the formation of B is kinetically
favored.
 The product A is called thermodynamically controlled and B is kinetically controlled.

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 2.7. Kinetics and thermodymamic control

 Kinetics describes the rates of reactions and how fast equilibrium is reached, it gives

no information about conditions once the reaction reaches equillibrium.

 A kinetically controlled reaction involves lower temperatures and shorter reaction

times, which ensures that only the fastest reaction has the chance to occur.

 Kinetic stability is largely dependent on the activation energy for the reaction.

 The activation energy is determined by the chemical potential energy of the reaction

intermediate(s).

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 2.7. Kinetics and thermodymamic control

 If the activation energy is high then at low temperatures the reaction will be slow.

 It can be made faster by increasing the temperature.

 If the activation energy is low then the reaction will be fast even at low temperatures.

Such reactions do increase their rates with increasing temperature as well.

 The smaller the Ea the faster is the reaction.

 Thus, anything that destabilizes the reactant or stabilizes the transition state will make

the reaction go faster.

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 2.7. Kinetics and thermodymamic control

 Thermodynamics is only concerned with the final state of a system and the

mechanism of transformation does not matter at all.

 The thermodynamic quantity is the energy difference resulting from the free energy

(ΔG) given off during a chemical reaction i.e., the stability of the products relative

to the reactants.

 A thermodynamically controlled reaction involves higher temperatures and long

reaction times to ensure that even the slower reactions have a chance to occur, and

all the material is converted to the most stable compound.

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 2.7. Kinetics and thermodymamic control

An energy profile diagram that illustrates the control of kinetic versus

thermodynamic products.
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 2.7. Kinetics and thermodymamic control

Thermodynamics Kinetics
Talks about how stable a material (or system) Considers how quickly or slowly a
is in one state change can occur
Thermodynamics is related to stability. Kinetics is related to reactivity.
Tells that a reaction should go if the products It doesn't tell anything about the final
are more stable than the reactants state
At high temperature, the reaction is under At low temperature, the reaction is
Thermodynamic control. under kinetic control
The thermodynamic product is the most stable The kinetic product is the product that
product. is formed most rapidly
The thermodynamic product predominates The kinetic product predominates
when the reaction is reversible thermodynamic when the reaction is irreversible
control) (kinetic control)

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 2.7. Kinetics and thermodymamic control
 The addition of HCl to 1,3- butadiene can give two products one is 1,2-and another is
1,4- addition product.
 The amount of each will depend upon the reaction conditions.
 The 1,2- product is called kinetic product and 1,4-is thermodynamic product.

 At low temperature -80 or 0 oC the kinetic product is obtained as major due to low Ea.
 At high temperature 40-45oC the thermodynamic product is major, due to greater stability
 The 1,4- addition product is more stable as greater the number of alkyl groups attached to a sp2
carbon more stable it is (more substitute alkene).
 But, 1,2-addition product is formed faster, as the transition state for formation of 1,2-product is
more stable
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 2.7. Kinetics and thermodymamic control

 The transition state for 1,4- addition has positive charge is on lesssubstituted carbon,
therefore its activation energy is large and formed slowly.
 Whereas, thetransition state for 1,2-addition has positive charge on more substituted
carbon, and has lesser activation energy thus formed faster.

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2.7. Kinetics and thermodymamic control

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 2.7. Kinetics and thermodymamic control

 If the Reaction is Irreversible, the Kinetic Product Predominates

 If the Reaction is Reversible, the Thermodynamic Product Predominates

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 2.8. Hammond Postulate
 The Hammond postulate is particularly valuable in situations where intermediates are involved in
reactions.
 What is the difference between Transition state and intermediate ?
 The transition state is an imaginary molecule with no lifespan and cannot be separated.
 It is the state where the system has the highest energy and is the most unstable.
 Direct observation of transition states is impossible, so information about their shapes must be
postulated.

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 2.8. Hammond Postulate

 An intermediate is a species formed in a stepwise reaction, which represents a free energy

minimum.
 The energy of the intermediate is lower than that of the transition state and can be isolated and
studied.
 Intermediates generally exist long enough to be observed and can in principle be isolated.
 Bonds are NOT in the process of breaking or forming within intermediates.

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 2.8. Hammond Postulate

 The relationship of the transition state structure to the structure of reactants,

intermediates, or products is postulated by Hammond in his statement known as

Hammond’s postulate.

 Transition states have a lifespan of zero, making it impossible to isolate and directly

study them.

 Transition states are highly unstable, and partial bonds are formed, due to unstability

transition stars can not be isolated

 In transition state nor all bonds are formed or all bonds are broken

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 [Link] Postulate
 According to the Hammond postulate, the geometry of a transition state for a particular

reaction step is similar to that of the compound (either reactants or products) which it

is closer in free energy

 It means we can predict the geometry structure of the transition state by comparing

its energy to the species

 The Hammond postulate is a useful, qualitative tool that interrelates structural

similarities between reactants, transition structures, and products with the exo-or

endothermicity of reactions

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 [Link] Postulate
 A reaction is endergonic when the free energy change Gr, is greater than zero.)

 Conversely, in an exergonic reaction the transition state is similar to the starting material(s)

with respect to energy and structure.

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 [Link] Postulate

 For the conversion of an alkene to a carbocation by HCl.

 Hammond’s postulate says that the transition state will more closely resemble the product,
higher in energy, that’s the carbocation.
 So the structure of the transition state more closely resembles the carbocation than the alkene.

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 2.8. Hammond Postulate
 The official version of Hammond’s postulate is this:
 If two states, for example, a transition state and an unstable intermediate, occur consecutively
during a reaction process and have nearly the same energy content, their interconversion will
involve only a small reorganization of the molecular structures.
 Assume that the transition states for reactions involving unstable intermediates can be closely
approximated by the intermediates themselves

Diagram depicting the energy Diagram depicting the energy

changes in an endothermic reaction. changes in an exothermic reaction.
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 2.8.1. Application of Hammond Postulate
a) Hammond's postulate can be used to examine the structure of the transition states of a SN1
reaction.
 In particular, the dissociation of the leaving group is the first transition state in a SN1 reaction
 Tertiary carbocation is relatively stable and therefore close in energy to the R-X reactant, then
the tertiary transition state will have a structure that is fairly similar to the R-X reactant.
 In contrast, the energy of a methyl carbocation is very high, and therefore the structure of the
transition state is more similar to the intermediate carbocation than to the R-X reactant.

Reaction coordinates for SN1 reactions 45

 2.8.1. Application of Hammond Postulate
b) It is useful for understanding the relationship between the rate of a reaction and the stability of the products
E1 reactions:
 An E1 reaction consists of unimolecular elimination, where the rate determining step of the
mechanism depends on the removal of a single molecular species.
 The more stable the carbocation intermediate is, the faster the reaction will proceed, favoring the
products.
 According to Hammond's postulate, the more stable diastereomer is formed faster

Reaction coordinates for E1 reactions 46

 2.8.1. Application of Hammond Postulate
c), Electrophilic addition reactions
 Applicable on electrophilic addition reactions which proceed through the formation of
carbocation which formed by protonation of an alkene is an endergonic process.
 The tert-butyl cation is formed faster than the isobutyl cation when 2-methylpropene reacts
with HCl.
 Because the formation of a carbocation is an endergonic reaction, the structure of the TS will
resemble the structure of the carbocation product.

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 2.8.1. Application of Hammond Postulate

d). Explain the selectivity of product formation during bromination and chlorination
of alkanes.
 The hydrogen abstraction for bromine is endothermic, as the TS is close in energy to products.
 TS shows resemblance with an alkyl radical and HBr,
 But hydrogen abstraction for chlorine is exothermic, as the TS is close in energy to reactant
 The TS resembles the alkane and a chlorine atom.

Transition states in chlorination and bromination reactions

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