Organic Chemistry Jasperse Acid-Base Practice Problems

T A. Identify each chemical as either an “acid” or a “base” in the following reactions, and
identify “conjugate” relationships.
-You should have one acid and one base on each side
-You should have two conjugate pairs

CH3CH2OH + NaOH CH3CH2ONa + H2O

1.

CH3CH2NHLi + CH3OH CH3CH2NH2 + CH3OLi

2.

CH3CH2CO2H + CH3MgBr CH3CH2CO2MgBr + CH4

3.

+ H2O + CH3OH2+
4. CH3OH + H3O

CH3CH2NH3+ + CH3OH CH3CH2NH2 + CH3OH2+

5.
T
B. Choose the More Basic for Each of the Following Pairs (Single Variable). You can use
stability to decide.

6. NH3 NaNH2 Keys:

1. Charge
2. Elecronegativity
7. NaOH H2 O 3. Resonance

NH O
8.

NHNa ONa
9.

10. Ph O Ph O

NHNa NHNa

11. O
T C. Rank the basicity of the following sets: Multiple Variable Problems

12. CH3MgBr CH3NHNa CH3NH2

13. O O OH

ONa
ONa NHNa OH
14. O

O
O NH OH
15. O

T
D. Choose the More Acidic for Each of the Following Pairs: Single Variable Problems

NH3 NH4
16.

17. OH2 OH

OH NH2 CH3
18.

NH2

19. OH

OH
20. OH

NH2 NH2
21.
 E. Rank the acidity of the following sets: Multiple Variable Problems

T OH OH2 OH
HF
22. O O

NH3 OH
NH2
H2O
23. O O

OH OH NH2

24. O

OH NH3 NH2 NH2

O
25. O

OH
T HeO OH NH2
26. O

F. Draw arrow to show whether equilibrium favors products or reactants. (Why?) Keys:
O O
1. Charge
H2O + 2. Elecronegativity
OH +
27. H OH H O 3. Resonance

OH + NH O + NH2
28.

G. For the following acid-base reaction,

a. put a box around the weakest base in the reaction
b. put a circle around the weakest acid
c. draw an arrow to show whether the equilibrium goes to the right or left. (4pt)

OH + NHNa ONa + NH2

29.
 Chem 341 Jasperse Ch. 1 Structure + Intro 12

Acid-Base Chemistry (Section 1.13-18)

Acidity/Basicity Table
T Acid Base Base
Entry Class Structure Ka Strength Base Strength Stability

1 Strong Acids H-Cl, H2SO4 102 O

Cl , HO S O
O

2 Hydronium H3O+, ROH+ 100 H2O, HOR

cationic neutral

3 Carboxylic O 10-5 O
Acid
R OH R O

4 Ammonium 10-12 R
R H
Ion (Charged) N N
R R R R
Charged, but only Neutral, but basic!
weakly acidic!

5 Water HOH 10-16

HO
T
6 Alcohol ROH 10-17
RO

7 Ketones and O 10-20 O

Aldehydes ! H !

8 Amine (N-H) (iPr)2N-H 10-33

(iPr)2N Li

9 Alkane (C-H) RCH3 10-50 RCH2

Quick Checklist of Acid/Base Factors

1. Charge T 1. Cations more acidic than neutrals; anions more basic than neutrals
2. Electronegativity
e 2. Carbanions < nitrogen anions < oxyanione < halides in stability
3. Resonance/Conjugation
x 3. resonance anions more stable than anions without resonance
T t
 When neutral acids are involved, it’s best to draw the conjugate anionic bases, and
then think from the anion stability side.

• The above three factors will be needed this semester. The following three will also
become important in Organic II.

4. Hybridization
5. Impact of Electron Donors/Withdrawers
6. Amines/Ammoniums
 Chem 341 Jasperse Ch. 1 Structure + Intro 13

More Detailed Discussion of Acid/Base Patterns/Factors to remember

1. Charge Factor: central atom being equal, cations are more acidic than neutrals (H3O+
> H2O, NH4+ > NH3), and anions more basic than neutrals (hydroxide > water).
T
2. Electronegativity Factor:
• Acidity H-C < H-N < H-O < H-X (halogen)

• Anion Stability

• Basicity

• Electronegativity

• Why: All neutral acids produce an anion after losing an H

• The more stable the anion Z- that forms, the more acidic the parent H-Z will
be. (The Product Stability/Reactivity principle).
• The anion stability correlates the love for electrons (electronegativity).
• Summary of Key Relationships:
• ANION STABILITY and the ACIDITY of a neutral acid precursor.
• ANION STABILITY and the BASICITY of the anion (inverse relationship)
T • ANION BASICITY and the ACIDITY OF THE CONJUGATE ACID are
inversely related (the stronger the acidity of the parent acid, the weaker the
basicity of the conjugate anion)
• KEY: WHEN THINKING ABOUT ACIDITY AND BASICITY, FOCUS ON
THE STABILITY OF THE ANION.

3. Resonance/Conjugation: Anion resonance is stabilizing, so an acid that gives a

resonance-stabilized anion is more acidic. And an anion that forms with resonance
will be more stable and less basic.

• Oxygen Series Examples:

Acidity: sulfuric acid > carboxylic acid > water or alcohol
O O
Anion Basicity: < <
HO S O O
O
O
T O O
> >
Anion Stability: HO S O O
O
O

• Note: Resonance is normally useful as a tiebreaker between oxygen anions,

nitrogen anions, or carbon anions