Buffer Solutions and Henderson-Hasselbalch - Complete Interactive Lesson
Part 1: What Is a Buffer?
๐ก๏ธ What Is a Buffer?
Part 1 of 7 โ Resisting pH Change
Buffer solutions are among the most important concepts in AP Chemistry and biochemistry. They maintain a nearly constant pH even when small amounts of acid or base are added. Your blood, for example, is buffered at pH 7.4!
๐ Buffer Definition
A buffer is a solution that resists changes in pH when small amounts of strong acid or strong base are added.
Composition
A buffer contains two key components:
Buffer Type
Component 1
Component 2
Example
Acidic buffer
Weak acid (HA)
Conjugate base (Aโ)
CH3โCOOH/CH3โCOOโ
Basic buffer
Weak base (B)
Conjugate acid (BH+)
NH3โ
Why Two Components?
The weak acid neutralizes added base: HA+OHโโAโ+H
Neither component is consumed quickly because both are present in significant amounts โ the pH changes only slightly!
What Does NOT Make a Buffer?
Strong acid + strong base โ complete reaction, no equilibrium
Strong acid alone โ no conjugate base reservoir
Weak acid alone (no added conjugate base) โ limited buffering
A salt of a strong acid + strong base (e.g., NaCl)
๐ง How Buffers Maintain pH
Consider the acetic acid/acetate buffer (CH3โCOOH/CH3โCOO):
Buffer Concept Check ๐ฏ
๐ก๏ธ Common Buffer Systems
Buffer System
Weak Acid
Conjugate Base
Approximate pH Range
Acetic acid/Acetate
CH3โCOOH
CH
Buffer Identification ๐
Buffer Component Identification ๐งฎ
For each buffer, identify the missing component:
1) Buffer: HNO2โ / ___. What is the conjugate base? (Enter formula, e.g. NO2-)
2) Buffer: ___ / NH3โ. What is the conjugate acid? (Enter formula, e.g. NH4+)
To make a phosphate buffer at pH โ 7.2, you mix with what? (Enter formula, e.g. Na2HPO4)
Exit Quiz โ What Is a Buffer? โ
Part 2: Henderson-Hasselbalch Equation
โ๏ธ How Buffers Work โ Neutralizing Added Acid or Base
Part 2 of 7 โ Quantitative Buffer Calculations
Now we'll calculate exactly how much the pH changes when acid or base is added to a buffer. The key is treating the neutralization as a stoichiometry problem first, then an equilibrium problem.
๐ The Two-Step Method
Step 1: Stoichiometry (Neutralization)
The added strong acid or base reacts completely with one buffer component:
Adding H+:Aโ (base component consumed)
Part 3: Preparing Buffers
๐ The Henderson-Hasselbalch Equation
Part 3 of 7 โ The Master Buffer Equation
The Henderson-Hasselbalch equation is the most important formula for buffer calculations. It directly relates pH to the pKaโ and the ratio of conjugate base to acid.
๐ Derivation
Starting from the Kaโ expression:
Part 4: Buffer Capacity
๐ฏ Buffer Capacity and Effective Range
Part 4 of 7 โ How Much Can a Buffer Handle?
A buffer doesn't have unlimited ability to resist pH changes. Its buffer capacity tells us how much strong acid or base it can neutralize before the pH changes significantly. Its effective range tells us the pH range where it works well.
๐ก๏ธ Buffer Capacity
Buffer capacity = the amount of strong acid or base that can be added before the pH changes significantly (usually > 1 unit).
Factors That Affect Capacity
Concentration: More concentrated buffers have greater capacity
1.0 M buffer > 0.10 M buffer > 0.010 M buffer
More moles of HA and Aโ = more acid and base can be neutralized
Ratio of components: Buffers work best when
Part 5: Adding Acid or Base to Buffers
๐งช Preparing Buffers
Part 5 of 7 โ Choosing the Right Acid and Designing a Buffer
In the lab, you need to prepare buffers at specific pH values with specific capacities. This requires choosing the right weak acid and calculating the correct amounts of acid and conjugate base.
๐งช Step 1: Choose the Right Weak Acid
Rule: Choose a weak acid whose pKaโ is as close as possible to the desired pH.
Why?
The buffer is most effective at pH= (equal concentrations of and )
Part 6: Problem-Solving Workshop
๐ ๏ธ Problem-Solving Workshop
Part 6 of 7 โ Buffer Solutions & Henderson-Hasselbalch
This workshop features multi-step problems combining buffer identification, pH calculation, capacity analysis, and preparation โ the types of questions that appear on AP Chemistry free-response sections.
๐ก๏ธ Problem 1: Buffer After Multiple Additions
A 1.0 L buffer contains 0.30 mol HCOOH (formic acid, pKaโ=3.75) and 0.30 mol (sodium formate).
Part 7: Synthesis & AP Review
๐ Synthesis & AP Review
Part 7 of 7 โ Buffer Solutions & Henderson-Hasselbalch
This comprehensive review covers all buffer concepts: composition, mechanism, Henderson-Hasselbalch calculations, capacity, effective range, preparation, and multi-step problems.
๐ Complete Summary
Buffer Essentials
Concept
Key Point
Composition
Weak acid + conjugate base (or weak base + conjugate acid)
Mechanism
HA neutralizes added OHโ; neutralizes added
/
N
H4+โ
2
โ
O
The conjugate base neutralizes added acid: Aโ+H+โHA
โ
When Strong Acid (H+) Is Added:
CH3โCOOโ(aq)+H+(aq)โCH3โCOOH(aq)
The conjugate base consumes the added H+, converting it to weak acid. The pH barely changes because the ratio [Aโ]/[HA] changes only slightly.
The weak acid consumes the added OHโ, converting it to conjugate base. Again, the ratio changes only slightly.
Key Insight
The buffer works because the added strong acid or base is completely consumed by reaction with one buffer component, and the [Aโ]/[HA] ratio changes only slightly if the buffer is concentrated enough.
3โ
CO
Oโ
3.7 โ 5.7
Carbonic acid/Bicarbonate
H2โCO3โ
HCO3โโ
5.4 โ 7.4
Dihydrogen phosphate/Hydrogen phosphate
H2โPO4โโ
HPO42โโ
6.2 โ 8.2
Ammonia/Ammonium
NH4+โ
NH3โ
8.2 โ 10.2
Biological Buffers
Blood: Carbonic acid/bicarbonate system (H2โCO3โ/HCO3โโ), maintained at pH 7.4
Cells: Phosphate buffer system (H2โPO4โโ/HPO4), around pH 7.2
Adding 0.20 mol HCl โ A gone, excess remains โ no longer a buffer
After destruction, treat as a simple strong acid or base problem!
Buffer Reaction Reasoning ๐
Exit Quiz โ How Buffers Work โ
Kaโ=[HA][H+][Aโ]โ
Solve for [H+]:
[H+]=Kaโโ [Aโ][HA]โ
Take โlog of both sides:
โlog[H+]=โlogKaโโlog[Aโ][HA]โ
pH=pKaโ+log[HA][Aโ]โ
pH=pKaโ+log[HA][Aโ]โโ
Key Features
When [Aโ]=[HA]: pH=pKaโ+log(1)=pKaโ
When [Aโ]>[HA]: pH>pKa (more basic)
When [Aโ]<[HA]: pH<pKa (more acidic)
The log term adjusts pH relative to pKaโ
๐ Using the Henderson-Hasselbalch Equation
Example 1: Find pH
Problem: A buffer contains 0.30 M CH3โCOOH and 0.50 M CH3โCOOโ. (pKaโ=4.74)
Solution:
pH=4.74+log0.300.50โ=
Example 2: Find Ratio
Problem: What ratio of [Aโ]/[HA] gives pH = 5.00 for a buffer with pKaโ=?
Solution:
5.00=4.74+log[HA][Aโ]
log[HA][Aโ]โ=0.26
[HA][Aโ]โ=10
So you need about 1.8 times more conjugate base than acid.
Example 3: Equal Concentrations
When [Aโ]=[HA]:
pH=pKaโ+log(1)=pKa
This is a critically important result: the pH of a buffer with equal concentrations equals the pKaโ!
Henderson-Hasselbalch Concept Check ๐ฏ
Henderson-Hasselbalch Drill ๐งฎ
1) Buffer: 0.40 M HF and 0.60 M NaF (pKaโ=3.17). Find the pH. (2 decimal places)
2) What pH does a buffer with pKaโ=9.25 and [NH3โ]/[NH4+โ]=0.50 have? (2 decimal places)
3) For a buffer with pKaโ=4.74 at pH = 5.50, what is [Aโ]/[HA]? (1 decimal place)
๐ก๏ธ Henderson-Hasselbalch for Basic Buffers
For a buffer made from a weak base (NH3โ) and its conjugate acid (NH4+โ):
Method 1: Use pKaโ of the conjugate acid
pH=pKaโ(NH4+
where pKaโ(NH4+โ)=
Method 2: Use pOH form
pOH=pKbโ+log[B]
Then pH=14โpOH.
Both methods give the same answer. Method 1 is usually preferred for consistency.
Henderson-Hasselbalch Reasoning ๐
Exit Quiz โ Henderson-Hasselbalch โ
[Aโ]โ[HA]
Equal concentrations = maximum capacity in both directions
If [Aโ]โซ[HA]: good capacity for added acid, poor for added base
If [HA]โซ[Aโ]: good capacity for added base, poor for added acid
Maximum Capacity
A buffer can neutralize added acid equal to the moles of Aโ present, and added base equal to the moles of HA present. Beyond that, the buffer is destroyed.
๐ Effective Buffer Range
A buffer is effective when the [Aโ]/[HA] ratio stays between 0.1 and 10:
[HA][Aโ]โ=0.1โpH=pKaโ+log(0.1)=pKaโโ1
[HA][Aโ]โ=
The Rule
Effectiveย bufferย range:ย pKaโยฑ1โ
Examples
Buffer System
pKaโ
Effective Range
HF/Fโ
3.17
pH 2.17 โ 4.17
Why pKaโยฑ1?
Outside this range, one component is less than 10% of the other. There's not enough of it to provide meaningful buffering.
Buffer Capacity & Range Check ๐ฏ
Buffer Capacity Calculations ๐งฎ
A buffer contains 0.40 mol CH3โCOOH and 0.60 mol CH3โCOOโ in 2.0 L. (pKaโ=4.74)
1) What is the maximum moles of HCl this buffer can absorb? (2 decimal places)
2) What is the maximum moles of NaOH this buffer can absorb? (2 decimal places)
3) What is the pH after adding 0.30 mol NaOH? (2 decimal places)
๐ Effect of Dilution on Buffers
Adding water (dilution) to a buffer:
Does NOT change pH (both [HA] and [Aโ] decrease by the same factor, so the ratio stays the same)
DOES decrease capacity (fewer moles of each component per liter)
Example
Buffer: 0.50 M HA / 0.50 M Aโ in 1.0 L
pH=pKaโ+log(0.50/0.50)=pK
Dilute to 2.0 L: 0.25 M HA / 0.25 M Aโ
pH=pKaโ+log(0.25/0.25)=pK (same!)
But now there's half the buffering capacity.
Buffer Range & Capacity Reasoning ๐
Exit Quiz โ Buffer Capacity & Range โ
p
Kaโ
HA
Aโ
The buffer works in the range pKaโยฑ1
Closer pKaโ to target pH โ closer to 1:1 ratio โ better capacity
Common Buffer Acids and Their pKaโ Values
Target pH
Best Acid
pKaโ
3 โ 4
Formic acid (HCOOH)
3.75
4 โ 5
Acetic acid (CH3โCOOH)
4.74
6 โ 8
H2โPO4โโ (phosphate)
7.21
7 โ 8
Tris buffer
8.07
9 โ 10
NH4+โ (ammonium)
9.25
9 โ 11
HCO3โโ (bicarbonate)
10.33
๐ข Step 2: Calculate the Required Ratio
From the Henderson-Hasselbalch equation:
pH=pKaโ+log[HA][Aโ]โ
log[HA][Aโ]โ=p
[HA][Aโ]โ=10
Worked Example
Prepare 1.0 L of a pH 5.00 buffer using acetic acid (pKaโ=4.74) with a total buffer concentration of 0.20 M.
Step 1: Find the ratio
[HA][Aโ]โ=1
Step 2: Set up equations
Let [HA]=x and [Aโ]=1.82x
x+1.82x=0.20ย M
2.82x=0.20
x=0.071ย M=[HA]
[Aโ]=1.82(0.071)=0.129ย M
Step 3: Calculate moles for 1.0 L
CH3โCOOH: 0.071 mol
NaCH3โCOO: 0.129 mol
Buffer Preparation Concepts ๐ฏ
๐ Alternative Preparation Methods
Method 2: Partial Neutralization
Instead of mixing weak acid + salt, you can add strong base to excess weak acid:
Example: To make an acetate buffer at pH 4.74:
Start with 0.20 mol CH3โCOOH, then add 0.10 mol NaOH:
CH3โCOOH+OHโโCH3โCOO
CH3โCOOH remaining: 0.20โ0.10=0.10 mol
formed: mol
Method 3: Partial Neutralization of Base
Start with weak base + add strong acid:
Start with 0.20 mol NH3โ, add 0.10 mol HCl:
NH3โ+H+โNH4
NH3โ remaining: 0.10 mol
NH4+โ formed: 0.10 mol
Buffer at
Buffer Preparation Calculations ๐งฎ
1) What ratio [Aโ]/[HA] is needed for a buffer at pH 4.00 using acetic acid (pKaโ=4.74)? (2 decimal places)
2) You have 0.30 mol CH3โCOOH. How many moles of NaOH should you add to make a buffer at pH = 4.74? (2 decimal places)
3) To prepare 500 mL of pH 9.55 buffer from NH4โCl and NH3โ (), with total concentration 0.40 M, how many moles of are needed? (3 decimal places)
Buffer Design Reasoning ๐
Exit Quiz โ Preparing Buffers โ
HCOONa
Initial pH:pH=3.75+log(0.30/0.30)=3.75
Add 0.10 mol NaOH:
HCOOH+OHโโHCOOโ+H2โO
After: HCOOH=0.20 mol, HCOOโ=0.40 mol
pH=3.75+log(0.40/0.20)=3.75+0.30=4.05
Then add 0.05 mol HCl:
HCOOโ+H+โHCOOH
After: HCOOโ=0.35 mol, HCOOH=0.25 mol
pH=3.75+log(0.35/0.25)=3.75+0.15=3.90
Your Turn: Sequential Additions ๐งฎ
A 1.0 L buffer has 0.25 mol CH3โCOOH and 0.25 mol CH3โCOOโ (pKaโ=4.74).
First, 0.08 mol NaOH is added. Then, 0.05 mol HCl is added.
1) After adding NaOH, how many moles of CH3โCOOโ are present? (2 decimal places)
2) After adding NaOH, what is the pH? (2 decimal places)
3) After then adding HCl, what is the final pH? (2 decimal places)