Zumdahl's Chapter 15: Applications of Aqueous Equilibria

Zumdahls Chapter 15
Applications of Aqueous Equilibria
Chapter Contents
Acid-Base Equilibria

Solubility

Common Ion Effect Buffers Titration Curve Indicators
Solubility Product Common Ion Effect pH and Solubility Complexes and Solubilities
Complex Equilibria
Acid-Base Titrations
Le Chtlier: restoration of equilibrium replaces species lost. QK
E.g., H2O is a weaker electrolyte than virtually any other weak acid, so Titrating weak acid with strong base binds proton in water, removing product! such titrations are quantitative.
Common Ion in Acid-Base
Le Chtlier: restoration of equilibrium consumes addends. QK
Addition of an ion already in equilibrium (Common Ion Effect) restores K by consuming the common ion. NH3 + H2O NH4+ + OH Kb=1.8105 0.1 M NH3 [OH] [1.81050.1] = 4103 Make it 0.1 M NH4+ and [OH] 1.8105 !
Buffer Solutions

Kb = [BH+][OH]/[B]
If [B]=[BH+], then [OH] = Kb If [HA]=[A], then [H+] = Ka
Ka = [H+][A]/[HA]
Furthermore, in either case, excess H+ or OH finds abundance of its reactant!
Associated robust pH, a buffer hallmark.
Buffer Calculation
0.1 M ea. [NH4+] & [NH3]; pOH = 4.74 100 mL of this buffer contains 10 mmol of each of those species. React fully 5 mmol OH (in same 100 mL)
Kb = (0.10.05+x) (0+x) / (0.1+0.05x) x = [OH]new (3 Kb) or pOHnew = 4.27
5% rule OK due to starting point of full reaction!
pOH = 0.47 trivial given even a 50% addend!
Titration Curves
(0.1 M acetic)
Titration: Weak Acid by Strong Base
14 12 10 8
pH
While [HA]/[A] or [B]/[BH+] not near zero, buffering makes pH near pK
pH changes slowly near completion.
Near endpoint, those ratios vanish making [H+] very sensitive to titrant.
6 4 2 0 0 0.05 0.1 0.15 0.2 0.25 Volume of Base
pH changes very rapidly near endpoint!
Strong/Strong Titration Curve

V base 0 50 90 95 99 99.9 100 V total 100 150 190 195 199 199.9 200 [H+] 1M .5/1.5 .1/1.9 .05/1.95 .01/1.99 .001/1.999 0/2 pH 0 0.48 1.28 1.59 2.30 3.30 7.00
Acid-Base Indicators
Indicators: molecules whose acid-base conjugates have distinct colors.
Color change occurs as acid/base ratio nears 1, i.e., as pHpKa (of indicator!)
Extreme sensitivity of pH to titrant
volume near endpoint makes use of indicators quantitative.
Match pKindicator to pH at equivalence.
pH at Equivalence
Sample is gone, replaced by conjugate at original number of moles.

[conjugate]0 = [sample]0 (V0 / Vtotal) F [conjugate]equilibrium = F x (back rxn with water)
Kconjugate = x2 / (F x) or x [FKc] pHequivalence = px or 14 px = 8.72

(acetic)
pKindicator pHequivalence is [Ind]/[Ind]1.
pH in the Buffer Region

Ka = [H+] [A ] / [HA] = [H+] [S ]/[HA] log Ka = log[H+] + log( [S]/[HA] ) pKa = pH log( [S]/[HA] ) pH = pKa + log( [S]/[HA] ) neither S nor HA=0
Henderson-Hasselbalch Equation
pOH = pKb + log( [BH +]/[B] ) Concentration ratios = mole ratios!
Solubility Product
AxBy(s) x Ay+(aq) + y Bx(aq) Q = [Ay+]x [Bx]y for arbitrary concentrations
K = [Ay+]eqx [Bx]eqy for saturation conc. Q < K implies no solid Q = K implies saturated solution Q > K super saturation difficult to achieve! Spontaneously precipitates.
Calculating Solubility Product

Make a saturated solution. Remove it from its precipitate. Evaporate to dryness and weigh solid. Convert to moles n of solid in original V. If AxBy then [Ay+]=x(n/V) ; [Bx]=y(n/V) Ksp = (xn/V)x (yn/v)y
x and y have enormous influence
Solubility and pH
If dissolved ions are conjugates of weak acid, say, both Ksp and Kb must be satisfied.
Ksp fixes [A] at equilibrium value, and Kb establishes [OH] and [HA], for example.
If Ka1 and [H+] can lower [A] below the solubility limit, acid can dissolve the solid. (Assuming solid is limiting reactant.)
Dissolving Oxides
Ag2O + H2O 2 Ag+ + 2 OH (41016) 2 H+ + 2 OH 2 H2O (10+14)2 Ag2O + 2H+ 2Ag+ + H2O (410+12)
Equilibrium lies far to right for modest acid.
Cu2O + H2O 2 Cu+ + 2 OH (41030) Cu2O + 2H+ 2Cu+ + H2O (4102)
Only concentrated acids will suffice.
Complex Equilibria
Empty or unfilled metal d-orbitals are targets for lone pair electrons in dative or coordinate-covalent bonding.
Square planar or octahedral (and beyond) geometries of ligands (e pair donors) bind to metal atoms to make complexes. Ligands can be neutral (H2O, NH3, CO ) or charged (Cl, CN, S2O32 ).
Complex Equilibrium Constant

Exchange of ligands (labile) is governed by equilibrium constants. Solid solubilities are thus influenced by ligand availability.
H2O always available (aq), but its not the strongest ligand. Serial replacement of H2O by other ligands leads to a sequence of equilibrium constants.
vs. K
Polyprotic acid constants proceed proton by proton:
HSO4(aq) H+(aq) + SO42(aq) Ka2=102
Ligand addition constants, , are cumulative instead:
Ag+(aq) + 2 I(aq) AgI2(aq)
2=1011
really Ag(H2O)4+ + 2 I Ag(H2O)2I2 + 2 H2O

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Zumdahls Chapter 15

Applications of Aqueous Equilibria

Common Ion Effect Buffers Titration Curve Indicators

Le Chtlier: restoration of equilibrium replaces species lost. QK

Common Ion in Acid-Base

Le Chtlier: restoration of equilibrium consumes addends. QK

If [B]=[BH+], then [OH] = Kb If [HA]=[A], then [H+] = Ka

Furthermore, in either case, excess H+ or OH finds abundance of its reactant!

Associated robust pH, a buffer hallmark.

Kb = (0.10.05+x) (0+x) / (0.1+0.05x) x = [OH]new (3 Kb) or pOHnew = 4.27

5% rule OK due to starting point of full reaction!

pOH = 0.47 trivial given even a 50% addend!

While [HA]/[A] or [B]/[BH+] not near zero, buffering makes pH near pK

pH changes slowly near completion.

6 4 2 0 0 0.05 0.1 0.15 0.2 0.25 Volume of Base

pH changes very rapidly near endpoint!

Strong/Strong Titration Curve

Indicators: molecules whose acid-base conjugates have distinct colors.

Extreme sensitivity of pH to titrant

volume near endpoint makes use of indicators quantitative.

Match pKindicator to pH at equivalence.

Sample is gone, replaced by conjugate at original number of moles.

[conjugate]0 = [sample]0 (V0 / Vtotal) F [conjugate]equilibrium = F x (back rxn with water)

Kconjugate = x2 / (F x) or x [FKc] pHequivalence = px or 14 px = 8.72

pKindicator pHequivalence is [Ind]/[Ind]1.

pH in the Buffer Region

pOH = pKb + log( [BH +]/[B] ) Concentration ratios = mole ratios!

Calculating Solubility Product

x and y have enormous influence

Equilibrium lies far to right for modest acid.

Cu2O + H2O 2 Cu+ + 2 OH (41030) Cu2O + 2H+ 2Cu+ + H2O (4102)

Only concentrated acids will suffice.

Complex Equilibrium Constant

Polyprotic acid constants proceed proton by proton:

HSO4(aq) H+(aq) + SO42(aq) Ka2=102

Ligand addition constants, , are cumulative instead:

Ag+(aq) + 2 I(aq) AgI2(aq)

really Ag(H2O)4+ + 2 I Ag(H2O)2I2 + 2 H2O

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