6. Thermodynamics and Kinetics

The reaction of tert-butyl chloride with methanol

is found to follow the rate equation

rate = k_r[(CH₃)₃C—Cl]

b. What is the kinetic order with respect to methanol?

Draw a reaction coordinate diagram for the following transformation. Label all product, intermediates, and substrates.

Draw a reaction-energy diagram for the following reaction:

•CH₃ + Cl₂ → CH₃Cl + Cl•

The activation energy is 4 kJ/mol (1 kcal/mol), and the overall ΔH° for the reaction is –110 kJ/mol (–27 kcal/mol).

•CH₃ + Cl₂ → CH₃Cl + Cl•

The activation energy is 4 kJ/mol (1 kcal/mol), and the overall ΔH° for the reaction is –110 kJ/mol (–27 kcal/mol).

b. Give the equation for the reverse reaction.

c. What is the activation energy for the reverse reaction?

The bond angles in a regular polygon with n sides are equal to 180° - 360°/n

a. What are the bond angles in a regular octagon?

b. What are the bond angles in a regular nonagon?

Draw a reaction-energy diagram for a one-step exothermic reaction. Label the parts that represent the reactants, products, transition state, activation energy, and heat of reaction.

On a single graph, draw the reaction coordinate diagram for the addition of one equivalent of HBr to 2-methyl-1,3-pentadiene and for the addition of one equivalent of HBr to 2-methyl-1,4-pentadiene. Which reaction is faster?

Under certain conditions, the bromination of cyclohexene follows an unusual rate law:

b. What is the kinetic order with respect to bromine?

For rotation around a bond, the rate constant is equal to the reaction rate. Why?

Within the following pairs, pick which reaction you would expect to be faster based on having a higher value of the frequency factor (A).

(b)

Identify the nucleophile and the electrophile in the following acid–base reactions:

a.

b.

The acid dissociation constant (K_a) for loss of a proton from cyclohexanol is 1 × 10^–16.

a. Draw a reaction coordinate diagram for loss of a proton from cyclohexanol.