ORGANIC - BROWN 6E

CH.4 - ACIDS AND BASES

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: FREE ENERGY DIAGRAMS

□ Atoms save energy by forming bonds. Free energy diagrams show overall changes in potential energy during reactions.

□ Free energy diagrams give us information on the spontaneity and rate of reactions

● Thermodynamics describes favorability. Determined by Gibbs Free Energy

● Kinetics describes rate. Determined by the activation energy of the rate determining step.

EXAMPLE: Describe the favorability and rate of the following free energy diagrams.

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: GIBBS FREE ENERGY

□ Predicts ____________________________ of reactions. Composed of three terms.

● Enthalpy is the sum of bond dissociation energies for the reaction.

_____ = ___________ bonds = Exothermic _____ = ___________ bonds = Endothermic

● Entropy is a measure of disorder in the system.

_____ = More ordered _____ = More disordered

● Temperature amplifies the effect of entropy on the overall favorability.

□ Some reactions require more than one step to go to completion. The ΔG⁰ is the sum of all the steps.

● Transition states ____________ be isolated. They involve bonds being broken and made at the same time.

● Intermediates ____________ be isolated. They rest at a higher energy state than normal.

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: OVERVIEW OF CHEMICAL REACTIONS

There are 4 types of common chemical reactions that we need to be familiar with in organic chemistry 1.

□ Acid-Base Reactions: Two molecules of opposite charges react to exchange a ____________ (usually).

□ Substitution Reactions: An acid-base reaction where an atom (or group of atoms) other than _____ are exchanged

□ Elimination Reactions: Two single bonds are removed to create one double bond

□ Addition Reactions: One double bond becomes two single bonds

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: THE MECHANISM- REACTIVITY

The currency of organic chemistry is ____________________________

● Stability and reactivity generally have an ___________________ relationship.

● The 4 common indicators of reactivity:

1. ____________________________ 2. ____________________________

3. ____________________________ 4. ____________________________

EXAMPLE: Identify which of the following molecules would be expected to be reactive.

We can categorize almost all reactive molecules into two massive subtypes. These will display similar behaviors.

● Negatively charged species are known as ___________________

● Positively charged species are known as ____________________

The side of the dipole with the ______ bonding preference can be used to predict nucleophilicity or electrophilicity

EXAMPLE: Identify which of the above molecules are nucleophilic or electrophilic

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: THE MECHANISM- ELECTRON MOVEMENT

Reactive molecules share electrons to become more stable. _________ are used to show which direction they are going.
● Arrows always move from regions of _________ electron density to _________ electron density

● By that logic, _________________________ must always attack ____________________________

● Each attacking arrow represents ____ electrons being shared. Replace that arrow with a new ____ - __________

EXAMPLE: Determine the initial direction of electron movement by drawing the first arrow of each mechanism:

a.

b.

c.

□ Bond breaking is sometimes also required in mechanisms, but only when it is required to preserve octets.
There are two ways to break chemical bonds:

EXAMPLE: Identify which of the above reactions require bond breaking and/or more arrows to satisfy all octets.
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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: ACID and BASE DEFINTIONS

Before we get started: Remember your strong six!

(HCl, HBr, HI, HNO3, H2SO4, HClO4)

□ Lewis definition: Same as ________________ □ Brønsted-Lowry definition:

● Acid is an electron pair ____________ ● Acid is a proton ___________

● Base is an electron pair ____________ ● Base is a proton ___________

EXAMPLE: Properly identify the following molecules:

a. b. c.

d. e. f.

Equilibrium: A base will always attack an acid to produce _______________________ in the following chemical pattern:

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

PRACTICE: Move electrons using arrows to predict and label the products of the following reaction:

a.

b.

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: EQUILIBUIM CONSTANT and pKa

●In general chemistry, we used pH to measure __________________________________

● In organic chemistry, we use _______ to measure the tendency for a molecule to _______________________________

□ Strong acids have a _____ dissociation constant (they _______________ dissociate in aqueous solution)

□ Weak acids have a _____ dissociation constant (they ________________ dissociate in aqueous solution)

●p= Ka = ( ) Therefore, the ____ Ka, the _____ the pKa

EXAMPLE: Calculate the pKa’s of the following acids and indicate which is the stronger acid.

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: pKa VALUES

We can use pKa values to help us determine the relative acidity of common organic molecules.

EXAMPLE: Identify all of the relevant pKa values for the indicated protons. Rank them in order of increasing acidity.

PRACTICE: Rank the following organic compounds in order of increasing pKa

PRACTICE: Rank the following organic compounds in order of increasing acidity

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: ACID and BASE EQUILIBRIUM

Ultimately, we can use pKa information to determine the overall direction and favorability of an acid base reaction.

STEPS: 1. Identify the Lewis acid and base

● Many times charges or a known acid will be present (+)___________ (-)___________

● Dissociate ALL spectator ions, these are the cations _______, _______ and _______

● If both compounds are still neutral, assign the one with the lowest pKa as the acid

2. Label the conjugate acid and base

3. Compare the acidity/pKa of the Lewis Acid to the ______________. Must go from ___________ to __________

EXAMPLE: Would the following reactions go to the right or the left? Label ALL species. Draw arrows in the correct direction.

a.

b.

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: FACTORS AFFECTING ACIDITY- ELEMENT EFFECTS

There are 5 major factors of acidity. We use these factors to determine relative acidity in the following two situations:

1. pKa information is _____________________ for a molecule

2. The pKas of two molecules are ________________ to make a determination of highest acidity.

□ When analyzing these 5 factors of molecules, look at the stability of the ________________________ ____________.

● The more stable the _______________________, the more willing the acid will be to donate a proton.

1. Element Effects:
● The element effects determine how loosely or strongly a particular element bonds with ____________
● We can use these effects to compare different protonated elements to each other. (i.e. NH 3 vs SH2)
● Consists of two trends:
1. Electronegativity – the stronger the electronegativity, the more willing to accept a lone pair.
2. Size – the bigger (squishier) the atom, the more willing it will be to accept a lone pair.

EXAMPLE: Without using pKa values, which of the following pairs is more acidic?

1. NH3 or SH2 2. H2O or CH4

3. 4.

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: FACTORS AFFECTING ACIDITY- INDUCTIVE EFFECTS

Inductive effects describe the stabilizing properties that __________________________ atoms NOT CONNECTED to the
acidic hydrogen have on the overall acidity.

● Whenever a charge can be ________________ over more than one atom, the more stable that charged species will be .

● Electronegative entities on other parts of the molecule can help “spread out” the negative change of the conjugate base
through inductive effects.

EXAMPLE: Draw rough sample electron clouds over the following pairs of conjugate bases of their respective alcohols.
Which is more stable? Which alcohol would have had the lower pKa?:

Factors that increase inductive effects:

1. Strength of the electronegative entities ________________________________________
2. Number of electronegative entities ___________________________________________
3. Proximity of electronegative entities ___________________________________________
EXAMPLE: Without using pKa values, which of the following pairs is more acidic?

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

CONCEPT: FACTORS AFFECTING ACIDITY- OTHER EFFECTS

Resonance Effects:
Definition: Whenever the donation of a proton leads to the formation of a possible ______________________________,
that conjugate base will be _________ stable, and the molecule will be a ___________ acid.

EXAMPLE: Which of the following pairs of acids would have the lower pKa? Explain why.

Hybridization Effects:
Definition: The more s-character in the acid, the closer to the nucleus extra lone pairs will be held to it, making the conjugate
base ________ stable.
Acidity Trend = sp C – H ______ sp2 C – H ______ sp3 C – H

EXAMPLE: Which of the following hydrocarbons is the most acidic?

Steric Effects:
Particularly with alcohols, the more easily solvated the conjugate base is, the more stable it will be.
● The smaller the R group, the more ___________ the alcohol
● The bigger the R group, the more ___________ the alkoxide

EXAMPLE: Which of the oxides is the most basic?

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ORGANIC - BROWN 6E
CH.4 - ACIDS AND BASES

PRACTICE: Would the following reactions go to the right or the left? Draw the products and label ALL species. Provide the
full mechanism.

a.

b.

c.

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