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advancedintermediate25-30 hours

Acid-Base Equilibrium Mastery

Deep dive into acid-base chemistry covering pH calculations, Ka/Kb, buffer design, and titration analysis. Master the Henderson-Hasselbalch equation and predict solution properties.

Learning Objectives

  • Calculate pH for strong and weak acid/base solutions
  • Apply Ka and Kb to predict acid-base behavior
  • Design and analyze buffer solutions
  • Interpret titration curves and identify equivalence points

1. Acid-Base Definitions

Arrhenius: acids produce H+, bases produce OH-. Bronsted-Lowry: acids donate protons, bases accept protons. Lewis: acids accept electron pairs, bases donate electron pairs. The Bronsted-Lowry definition is most commonly used in general chemistry.

Key Points

  • Bronsted-Lowry: acid = proton donor, base = proton acceptor
  • Conjugate acid-base pairs differ by one H+
  • Lewis acids have empty orbitals; Lewis bases have lone pairs
  • Water is amphoteric (can act as acid or base)

2. Strong vs Weak Acids and Bases

Strong acids completely dissociate: [H+] = [HA]initial. The 7 common strong acids are HCl, HBr, HI, HNO3, H2SO4, HClO3, HClO4. Most acids are weak and require equilibrium calculations using Ka. Likewise, strong bases (NaOH, KOH) dissociate completely.

Key Points

  • Strong acids: 100% dissociation, no equilibrium needed
  • Weak acids: partial dissociation, use Ka expression
  • Strong bases: metal hydroxides (NaOH, KOH, Ba(OH)2)
  • Weak bases: ammonia and amines

3. pH Calculations

For strong acids: pH = -log[H+]. For weak acids: set up Ka equilibrium, solve for [H+]. If Ka << [HA]initial, use approximation [H+] = sqrt(Ka x C). Check that x < 5% of C; if not, use quadratic formula. Remember: pH + pOH = 14 at 25C.

Key Points

  • Strong acid: pH = -log[acid concentration]
  • Weak acid: pH = -log(sqrt(Ka x C)) if approximation valid
  • Quadratic needed if x > 5% of initial concentration
  • For bases: calculate pOH first, then pH = 14 - pOH

4. Buffer Solutions

Buffers resist pH change when acid or base is added. They contain a weak acid and its conjugate base (or weak base and conjugate acid). The Henderson-Hasselbalch equation: pH = pKa + log([A-]/[HA]). Maximum buffer capacity occurs when [A-] = [HA], i.e., pH = pKa.

Key Points

  • Buffer = weak acid + conjugate base (or weak base + conjugate acid)
  • Henderson-Hasselbalch: pH = pKa + log([base]/[acid])
  • Best buffer capacity when [A-] ≈ [HA]
  • Buffer range: pKa plus or minus 1

5. Titration Curves

Titration curves plot pH vs volume of titrant. Strong acid-strong base: steep rise at equivalence, pH = 7. Weak acid-strong base: equivalence pH > 7 (conjugate base is basic). At half-equivalence point: pH = pKa because [HA] = [A-].

Key Points

  • Strong-strong equivalence: pH = 7
  • Weak acid-strong base equivalence: pH > 7
  • Weak base-strong acid equivalence: pH < 7
  • Half-equivalence point: pH = pKa, [HA] = [A-]

6. Polyprotic Acids

Polyprotic acids have multiple ionizable protons (H2SO4, H3PO4, H2CO3). Each proton has its own Ka value, and Ka1 > Ka2 > Ka3. The first proton is easiest to remove. For titration, each equivalence point corresponds to one proton.

Key Points

  • Ka1 >> Ka2 >> Ka3 (each proton harder to remove)
  • Treat each dissociation separately
  • Multiple equivalence points in titration
  • The pH after first equivalence depends on Ka2

High-Yield Facts

  • Kw = [H+][OH-] = 1.0 x 10^-14 at 25°C
  • Ka x Kb = Kw for a conjugate acid-base pair
  • Strong acid added to buffer: HA increases, A- decreases
  • Percent ionization = ([H+]eq/[HA]initial) x 100%
  • Indicators change color when pH equals their pKa plus or minus 1

Practice Questions

1. What is the pH of 0.10 M acetic acid? (Ka = 1.8 x 10^-5)
[H+] = sqrt(Ka x C) = sqrt(1.8 x 10^-5 x 0.10) = sqrt(1.8 x 10^-6) = 1.3 x 10^-3 M. pH = -log(1.3 x 10^-3) = 2.89. Check: 1.3 x 10^-3 / 0.10 = 1.3% < 5%, so approximation is valid.
2. Design a buffer at pH 5.00 using acetic acid (pKa = 4.74) and sodium acetate.
Use Henderson-Hasselbalch: 5.00 = 4.74 + log([Ac-]/[HAc]). log([Ac-]/[HAc]) = 0.26. [Ac-]/[HAc] = 10^0.26 = 1.82. Use any concentrations with this ratio, e.g., 0.182 M sodium acetate and 0.100 M acetic acid.

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FAQs

Common questions about this topic

Use it when your approximation (x = sqrt(Ka x C)) gives x > 5% of the initial concentration. This typically happens when Ka is relatively large or the acid is very dilute. Set up Ka = x^2/(C-x) and solve the quadratic.

Choose an indicator whose color change range (pKa plus or minus 1) includes the equivalence point pH. For strong acid-strong base (eq. pt. pH 7), use bromthymol blue. For weak acid-strong base (eq. pt. pH > 7), use phenolphthalein.

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