Water, Acids, Bases, and Buffers ▪ Lewis Theory

Water • Acids are e- acceptors

• Bases are e- donors

Strength

• Acid strength

- used to regulate temperature of the body • Base strength

- not good electric conductor

- salt water is good electric conductor Weak vs. strong

- has special molecular structure For strong acids/bases: (arrow is one direction)

H20 – has 4 electron domains (2 h-bonding but the other HCl → H+ + Cl-
2 is lone pairs) NaOH → Na+ + OH-
Hydrogen-bonding or H-bonding For weak acids/bases: (arrow direction is reversible)
- special intermolecular structure CH3COOH ⇌ H+ + CH3COO-
- should have dipole moments and hydrogen should H2PO4- ⇌ H+ + HPO42-
appear on it
HPO42- ⇌ H+ + PO43-
Intermolecular – within the molecule
H3PO4 ⇌H+ + H2PO4-
Effect
Equilibrium – balance between reactant and product in
- more attraction, the harder to separate them given reversibly reaction
(closer proximity with other neighbor molecules) Concentration
- If there is more attraction, it takes more energy to ▪ Molar Concentration
separate
• moles/L
(high volume, high density)
•M
Specific Heat – heat required to raise temperature by
100°C 1 mole = 6.02 x1023 ions/molecules/atoms/molecules
(Avogadro’s number)
High temperature means High solubility
pH
Why ice is floating in water?
- describe the level of acidity or basicity
- because ice is less dense that water
<7 = acid >7 = base =7 = neutral
- volume expands when freezing the water.
▪ puissance d'hydrogen
ACIDS and BASES ▪ In general, p-value = -log([value])
▪ Brønsted-Lowry Theory • pH = -log[H+] - acid
• Acids are H+ donors • pOH = -log[OH-] - base
• Bases are H+ acceptors • pH + pOH = 14
Weak Acids and Weak Bases MAIN FEATURE: Reversibility

• In a solution containing weak acids or bases, its HA ⇌ H+ + A-

basic composition will always
Reaction continually moves forward and backward
come in pairs for equilibrium

• Weak acid – conjugate base EQUILIBRIUM

• Weak base – conjugate acid • For the general acid reaction, HA ⇌ H+ + A-,

In general, • Equilibrium constant K, is written as Ka

HA ⇌ H+ + A-

Examples

• For acetic acid,

CH3COOH ⇌ H+ + CH3COO-

• For ammonia,

NH4+ ⇌ NH3 + H+ • Remember that Ka is the measure of the ratio of

More examples, products to reactants at equilibrium.

• Phosphoric acid, H3PO4 (functioning as an acid) • COMPARE:

H3PO4 → H2PO4 + H+ • Acid strength of acetic acid and ascorbic acid

• Pyridine, C5H5N (functioning as a base) • KaCH3COOH = 1.8 x 10-5

18 [𝐴−][𝐻+]
C5H6N ⇌ C5H5N + H+ 1.8 ∗ 10−5 = 0.000018 = =
1000000 [𝐻𝐴]

CAUTION • KaC6H8O6 = 8.0 x 10-5

• Depending on the setup, some can act either as a • Because of this reversibility, weak acids and weak
base or as an acid bases can prevent drastic pH changes even in the
• Amphiprotic substances addition of a strong acid/base

For example, • This is known as buffer action.

HCl → H+ + Cl- • This follows the concept of Le Chatelier’s Principle.

is actually Le Chatelier’s Principle

HCl + H2O → H3O+ + Cl- • If additional reactant is added the rate of the forward
reaction increases.
where H2O acts as a base.
• As the rate of the reverse reaction is initially
• Phosphoric acid, H3PO4, is a polyprotic acid unchanged, the equilibrium appears to shift
toward the creation of more products.
H3PO4 ⇌ H+ + H2PO4-
• If additional product/(s) is/are added....
H2PO4- ⇌ H+ + HPO42-

HPO42- ⇌ H+ + PO43-
So… Buffering capacity

HA ⇌ H+ + A- • Largely dependent on concentration of buffer

components
• If a strong base (OH-) is added
How do we create buffers for a certain pH?

1. Choose the best buffer system for the target pH

So…
2. Compute for the mole ratio of the components
HA ⇌ H+ + A-
3. Compute for the volume needed for each component
• If a strong base (OH-) is added
Ka pKa

So… H3PO4 ⇌ H+ + H2PO4- a 7.1 * 10-3 2.15

HA ⇌ H+ + A-
H2PO4- ⇌ H+ + HPO42- 6.3 * 10-8 7.20
-
• If a strong base (OH ) is added
HPO42- ⇌ H+ + PO43- 4.2 * 10-13 12.38
• OH reacts with HA

• forming water (neutralization) and the conjugate

How do we create buffers for a certain pH?
base, A
• Henderson-Hasselbach equation

While

HA ⇌ H+ + A-
• What is the mole ratio of H2PO4- and HPO42-to
• If a strong acid (H+) is added prepare buffer with pH 7.40?

• What is asked?
While • What is known? pKa = 7.20, pH 7.40
HA ⇌ H+ + A- • 0.2 = log([A-]/[HA])
• If a strong acid (H+) is added • [A-]/[HA] = 1.58489…. ≈ 1.585
• The added H+ reacts with A- ANSWER: 1.585: 1
• H+ + A- → HA If there is a target total volume...

Example: Desired buffer volume is 1 L

While • 1.585 parts A-: 1 part HA
HA ⇌ H+ + A- • Divide the total volume by the total and multiply by
• If a strong acid (H+) is added the corresponding parts per component.
1.585
• The added H+ reacts with A-, VA-= 1000mL ∗ = 613mL
2.585

• forming HA 1
VHA= 1000mL ∗ =387mL
2.585
Buffering range

• pKa ± 1
OR Polyprotic Acids
Example: Desired buffer volume is 1 L
• The different protons in these molecules
• 1.585 parts A-: 1 part HA
have different acid strengths.
• a total of 2.585 parts
Ka pKa
• Buffer composition is 61.3% base and 38.7%
acid H3PO4 ⇌ H+ + H2PO4- a 7.1 * 10-3 2.15

• Multiply the total volume by the %composition of H2PO4- ⇌ H+ + HPO42- 6.3 * 10-8 7.20
each component
HPO42- ⇌ H+ + PO43- 4.2 * 10-13 12.38
VA-= 1000mL ∗ 0.613 = 613mL

ANSWER: 613 mL of Na2HPO4 and 387 mL of NaH2PO4 Titration curve of H3PO4

Difference between Water, Strong acids, and weak
acids

Dissociation of a Triprotic acid

SUMMARY • It allows for the computation of the acid-base
ratio when preparing buffer solutions. • It allows
the computation of resulting pH upon the addition
• If equilibrium is disturbed, adjustment is done by
of a strong acid or base.
shifting the reaction to the left or right following Le
Chatelier’s Principle.

• If products are increased, shift reaction to the left

(create more reactants)

• If products are decreased, shift reaction to the

right (create more products)

SUMMARY of equations

• p-value = -log(value)

• pH

• pOH

• pKa

• pH + pOH = 14

• Ka describes the extent of dissociation/ionization

of the compound to its respective ions

• Buffering range is limited to pKa ± 1

• Buffering capacity is concentration dependent.

The larger concentration of components, the
greater its resistance to pH changes.

• The Henderson-Hasselbach equation can be used

as follows: