Organic Chemistry, 6e (Smith)

Chapter 6 Understanding Organic Reactions

1) Which of the following statements about substitution reactions is true?

A) Substitution reactions involve π bonds.
B) Substitution reactions involve σ bonds.
C) One σ bond breaks and another forms at a different carbon atom.
D) One π bond breaks and another forms at the same carbon atom.

2) What kind of reaction does the conversion of A to B represent?

A) Addition reaction
B) Substitution reaction
C) Elimination reaction
D) Acid-base reaction

3) Which of the following statements about elimination reactions is true?

A) Two σ bonds are broken.
B) Two σ bonds are formed.
C) Two π bonds are broken.
D) Two π bonds are formed.

4) What kind of reaction does the conversion of A to B represent?

A) Addition reaction
B) Elimination reaction
C) Substitution reaction
D) Oxidation-reduction reaction

5) Which of the following statements about addition reactions is true?

A) Two π bonds are formed.
B) Two π bonds are broken.
C) Two σ bonds are formed.
D) One π bond is formed.

1
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
6) What kind of reaction does the conversion of A to B represent?

A) Acid-base reaction
B) Elimination reaction
C) Substitution reaction
D) Addition reaction

7) Which of the following statements about bond breaking is true?

A) Homolysis and heterolysis require energy.
B) In homolysis, the electrons in the bond are divided unequally.
C) In heterolysis, the electrons in the bond are divided equally.
D) Homolysis generates charged intermediates.

8) Which of the following statements about bond breaking is not true?

A) Homolysis generates uncharged reactive intermediates with unpaired electrons.
B) Homolysis require energy but heterolysis does not require energy.
C) Heterolysis generates charged intermediates.
D) Heterolysis involves unequal sharing of bonding electrons by atoms.

9) Which of the following statements is true?

A) Ionic intermediates are formed in radical reactions.
B) Radicals are intermediates in polar reactions.
C) Carbocations are electrophiles.
D) Radicals are nucleophiles.

10) Which of the following statements is not true?

A) In polar reactions, a nucleophile reacts with an electrophile.
B) Carbocations are electrophiles.
C) Carbanions are nucleophiles.
D) A half-headed curved arrow shows the movement of an electron pair.

11) Which of the following statements is not true?

A) Bond breaking is endothermic.
B) The bond dissociation energy for bond breaking is always negative.
C) Bond making is exothermic.
D) The bond dissociation energy for bond formation is always negative.

2
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
12) Which of the following statements is true?
A) Bond dissociation energies increase down a column of the periodic table.
B) When DH° is positive, more energy is released in forming bonds than is needed to break
bonds.
C) When DH° is negative, more energy is needed to break bonds than is released in forming
bonds.
D) Bond dissociation energies decrease down a column of the periodic table.

13) Using the bond dissociation energies given, calculate DH° for the following reaction.

Bond A-B DH° KJ/mol

(CH3)3C-Cl 331
H-OH 498
(CH3)3C-OH 401
H-Cl 431

A) +3 KJ/mol
B) -3 KJ/mol
C) -67 KJ/mol
D) +70 KJ/mol

14) Using the bond dissociation energies given, calculate DH° for the following reaction.

Bond A-B DH° KJ/mol

CH3CH2-Br 285
H-OH 498
CH3CH2-OH 393
H-Br 368

A) +108 KJ/mol
B) -130 KJ/mol
C) -22 KJ/mol
D) +22 KJ/mol

3
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
15) Which of the following statements about the equilibrium constant, Keq, is true?
A) When Keq > 1, the equilibrium favors the reactants.
B) When Keq < 1, the equilibrium favors the products.
C) The size of Keq tells about the position of equilibrium.
D) For a reaction to be useful, the equilibrium must favor the reactants.

16) Which of the following statements about equilibrium is true?

A) Equilibrium favors the products when the energy of the products is higher than the energy of
the reactants.
B) Equilibrium favors the reactants when the energy of the product is lower than the energy of
the reactants.
C) Equilibrium favors the products when they are less stable than the starting material of a
reaction.
D) Equilibrium favors the products when they are more stable than the starting material of a
reaction.

17) Which of the following expressions summarizes the correct relationship between the free
energy change, DG°, and the equilibrium constant, Keq?
A) Keq > 1 when DG° > 0
B) Keq > 1 when DG° < 0
C) Keq < 1 when DG° < 0
D) Keq < 1 when DG° = 0

18) Which of the Keq corresponds to the lowest value of DG°?

A) K = 10-3
eq
B) K = 10-2
eq
C) K = 10-1
eq
D) DG° cannot be determined.

19) Which of the Keq corresponds to the highest value of DG°?

A) K = 10-1
eq
B) K = 10-2
eq
C) K = 10-3
eq
D) K = 10-5
eq

20) Which of the Keq corresponds to the most negative value of DG°?
A) Keq = 1
B) K = 101
eq
C) K = 102
eq
4
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
D) K = 103
eq

21) Which of the following statements is true?

A) The product is favored in reaction in which DH° is a positive value.
B) Entropy decreases when an acyclic compound forms a ring.
C) In homolytic bond cleavage, entropy decreases and favors formation of products.
D) The starting material is favored in a reaction in which DH° is a negative value.

22) Which of the following statements is true?

A) The size of the activation energy tells us about the reaction mechanism.
B) The size of the activation energy tells us about the reaction rate.
C) A slow reaction has low activation energy.
D) A fast reaction has high activation energy.

23) Which of the following statements is not true?

A) Two reactions can have identical values for DH° but very different Ea values.
B) The larger the activation energy, the slower the reaction.
C) DH° determines the height of the energy barrier.
D) The lower the activation energy, the faster the reaction.

24) What is the name given to the reaction species that lies at an energy minimum between steps
on a reaction energy diagram?
A) Transition state
B) Activation energy
C) Reactive intermediate
D) Equilibrium product

25) Which of the following statements about a two-step reaction mechanism is true?
A) The transition states are located at energy minima.
B) Each step is characterized by its own value of DH° and Ea.
C) The rate-determining step has the lower energy transition state.
D) The reactive intermediate is located at an energy maximum.

26) Which reaction is fast and has Keq = 1?

A) A
B) B
5
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
C) C

6
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
27) Which reaction has a positive DG°, assuming that entropy changes are negligible compared
to enthalpy changes?

A) A
B) B
C) C

28) Which reaction is slowest?

A) A
B) B
C) C

29) In which reaction is Keq > 1?

A) A
B) B
C) C

7
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
30) How many transition states are present in the reaction in the energy diagram?

A) 0
B) 1
C) 2
D) 3

31) Which of the following letters represents DH° for the forward reaction in the following
energy diagram?

A) A
B) B
C) C
D) D

8
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
32) How many transition states and intermediates would the reaction profile have for the reaction
shown below?

A) Three transition states and three intermediates

B) Two transition states and two intermediates
C) Three transition states and two intermediates
D) Two transition states and three intermediates

33) Which step would most likely have the largest energy of activation?

A) Step one
B) Step two
C) Step three
D) It cannot be determined from the information provided

34) A decrease in which of the following results in an increase in the rate of a chemical reaction?
A) Energy of activation
B) Concentration
C) Temperature
D) Kinetic energy

35) Which of the following reaction quantities will have an effect on reaction rate?
A) DG°
B) DH°
C) Keq
D) Ea

9
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
36) Which of the following statements is true?
A) Fast reactions have small rate constants.
B) Slow reactions have large rate constants.
C) A rate equation contains concentration terms for all reactants involved in a one-step
mechanism.
D) A rate equation contains concentration terms for all the reactants involved in a multi-step
reaction.

37) The equilibrium constant for the conversion of A to D is predicted to be which of the
following?

A) Keq = 1
B) Keq < 1
C) Keq > 1
D) Cannot be determined from the information provided

38) The DG° (free energy change) for the conversion of A to B is predicted to be which of the
following?

A) DG° = 0
B) DG° < 0
C) DG° > 0
D) Cannot be determined from the information provided

39) What kind of reaction does the conversion of A to D represent?

A) Addition reaction
B) Substitution reaction
C) Elimination reaction
D) Oxidation-reduction reaction

10
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
40) If the conversion of A to B is slow and B to C is fast, what is the rate equation for this
reaction?

A) Rate = k[(CH3)2CHCl][H2O]
B) Rate = k[(CH3)2CHCl]
C) Rate = k[(CH3)2CH]+[H2O]
D) Rate = k[(CH ) CH]+
3 2

41) Which compound would you predict to be highest in energy?

A) A
B) B
C) C
D) D

11
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
42) Calculate Ea for the conversion of C ® B.

Ea (A ® B) = +10 kcal
Ea (B ® C) = +4 kcal
DH (A ® B) = +8 kcal
DH (B ® C) = -5 kcal
A) +3 kcal
B) +7 kcal
C) +9 kcal
D) None of these

43) The following is an energy diagram for the conversion of A ® B ® C. The energies of
activation and DH's for each step are also given. Calculate DH overall as shown on the energy
diagram for A ® B ® C.

Ea (A ® B) = +10 kcal
Ea (B ® C) = +4 kcal
DH (A ® B) = +8 kcal
DH (B ® C) = -5 kcal
A) +3 kcal
B) +7 kcal
C) +9 kcal
D) None of these

12
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
44) Which of the following statements about a catalyst is true?
A) A catalyst accelerates a reaction by changing the amount of reactant and product at
equilibrium.
B) A catalyst accelerates a reaction by lowering the energy of activation.
C) A catalyst accelerates a reaction by raising the energy of activation.
D) A catalyst accelerates a reaction by lowering the equilibrium constant.

45) Which of the following statements about enzymes is true?

A) Enzymes increase the activation energy for a reaction.
B) Enzymes decrease the equilibrium constant.
C) Enzymes shift the equilibrium to favor the product.
D) Enzymes lower the transition state for the rate-determining step.

46) For which of the following reactions is ΔS° a positive value?

A) I
B) II
C) III
D) IV

47) The conversion of acetyl chloride to methyl acetate occurs via the following two-step
mechanism:

What is the rate equation for this reaction if the first step is rate determining?
A) Rate = k [acetyl chloride] [-OCH3]
B) Rate = k [acetyl chloride]
C) Rate = k [-OCH3]
D) Rate = k [acetyl chloride] [-OCH ]2
3

13
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
 14
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
48) The conversion of acetyl chloride to methyl acetate occurs via the following two-step
mechanism:

If the concentration of -OCH3 were increased 5 times, what would happen to the rate of the
reaction?
A) Rate would become one fifth
B) Rate would increase 25 times
C) Rate would increase 5 times
D) Rate would remain unchanged

49) The conversion of acetyl chloride to methyl acetate occurs via the following two-step
mechanism:

If the concentrations of both -OCH3 and acetyl chloride were increased 2 times, what would
happen to the rate of the reaction?
A) Rate would become one-fourth
B) Rate would increase 4 times
C) Rate would increase 16 times
D) Rate would increase 2 times

50) The conversion of acetyl chloride to methyl acetate occurs via the following two-step
mechanism:

The conversion of acetyl chloride to methyl acetate would be classified as which of the
following?
A) Addition
B) Elimination
C) Substitution
D) None of these
15
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
51) The symbol hν stands for ________ in a chemical reaction.
A) light
B) heat
C) reactant
D) product

52) The symbol Δ stands for ________ in a chemical reaction.

A) light
B) heat
C) reactant
D) product

53) What type of bond cleavage takes place in/what type of intermediate is produced in the
following reaction?

A) Homolysis/Radical
B) Homolysis/Carbocation
C) Heterolysis/Carbocation
D) Heterolysis/Carbanion

54) What type of bond cleavage takes place in/what type of intermediate is produced in the
following reaction?

A) Homolysis/Radical
B) Homolysis/Carbocation
C) Heterolysis/Carbocation
D) Heterolysis/Carbanion

16
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.
55) What type of reaction does the following conversion represent?

A) Addition reaction
B) Elimination reaction
C) Substitution reaction
D) Oxidation-reduction reaction

17
Copyright 2020 © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior
written consent of McGraw-Hill Education.