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Acid-Base Equilibria and Solubility Equilibria

Chapter 16

Common ion effect:

The presence of a common ion ____________ the ionization of a weak acid or a weak base. Consider mixture of CH3COONa (strong electrolyte) and CH3COOH (weak acid).

CH3COONa (s) CH3COOH (aq)

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Na+ (aq) + CH3COO- (aq) H+ (aq) + CH3COO- (aq)

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Consider mixture of salt NaA and weak acid HA. NaA (s) HA (aq) [H+] = Na+ (aq) + A- (aq) H+ (aq) + A- (aq) Ka [HA] [A-] Ka = [H+][A-] [HA]

Buffer solution is a soln of: 1. 2.

[HA] -log [H+] = -log Ka - log [A-] -log [H+] [A-] = -log Ka + log [HA] pH = pKa + log pKa = -log Ka
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A buffer soln has the ability to resist changes in pH upon the addition of small amounts of either acid or base. Consider an equal molar mixture of CH3COOH and CH3COONa [conjugate base] [acid] Add strong acid H+ (aq) + CH3COO- (aq) Add strong base OH- (aq) + CH3COOH (aq) CH3COOH (aq) CH3COO- (aq) + H2O (l)
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[A-] pH = pKa + log [HA]

HCl HCl + CH3COO-

H+ + ClCH3COOH + ClTitration:

Titrations

Equivalence point Indicator

Slowly add base to unknown acid UNTIL The indicator changes color ( )

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Strong Acid-Strong Base Titrations Alternative Method of Equivalence Point Detection NaOH (aq) + HCl (aq) OH- (aq) + H+ (aq) H2O (l) + NaCl (aq) H2O (l)

monitor pH

Weak Acid-Strong Base Titrations CH3COOH (aq) + NaOH (aq) CH3COOH (aq) + OH- (aq) At equivalence point (pH > 7): CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq) CH3COONa (aq) + H2O (l) CH3COO- (aq) + H2O (l)

Strong Acid-Weak Base Titrations HCl (aq) + NH3 (aq) H+ (aq) + NH3 (aq) NH4+ (aq) + H2O (l) NH4Cl (aq) NH4Cl (aq) NH3 (aq) + H+ (aq)

At equivalence point (pH < 7):

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Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq) [HIn] 10 Color of acid (HIn) predominates [In-] [HIn] 10 Color of conjugate base (In-) predominates [In-]

Solutions of Red Cabbage Extract

pH
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The titration curve of a strong acid with a strong base.

Which indicator(s) would you use for a titration of HNO2 with KOH ?

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Solubility Equilibria
AgCl (s) Ksp = [Ag+][Cl-] MgF2 (s) Ag2CO3 (s) Ca3(PO4)2 (s) Ag+ (aq) + Cl- (aq)

Ksp is the solubility product constant Ksp = [Mg2+][F-]2 Ksp = [Ag+]2[CO32-] Ksp = [Ca2+]3[PO43-]2

Mg2+ (aq) + 2F- (aq) 2Ag+ (aq) + CO32- (aq) 3Ca2+ (aq) + 2PO43- (aq)

Dissolution of an ionic solid in aqueous solution: Q < Ksp Q = Ksp Q > Ksp
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Molar solubility (mol/L): Solubility (g/L):

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The Common Ion Effect and Solubility

What is the molar solubility of AgBr in (a) pure water and (b) 0.0010 M NaBr?

pH and Solubility
The presence of a common ion decreases the solubility. Insoluble bases dissolve in acidic solutions Insoluble acids dissolve in basic solutions
remove add

Mg(OH)2 (s)

Mg2+ (aq) + 2OH- (aq) At pH less than 10.45

Ksp = [Mg2+][OH-]2 = 1.2 x 10-11 Ksp = (s)(2s)2 = 4s3 4s3 = 1.2 x 10-11 s = 1.4 x 10-4 M [OH-] = 2s = 2.8 x 10-4 M pOH = 3.55 pH = 10.45

Lower [OH-] OH- (aq) + H+ (aq) H2O (l) Increase solubility of Mg(OH)2 At pH greater than 10.45 Raise [OH-] Decrease solubility of Mg(OH)2
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Complex Ion Equilibria and Solubility

A complex ion Co2+ (aq) + 4Cl- (aq) CoCl2- (aq) 4

Effect of Complexation on Solubility AgNO3 + NaCl Add NH3

The formation constant or stability constant (Kf):

2[CoCl4 ] [Co2+][Cl-]4

2+ Co(H2O)6

CoCl24

Kf =

HCl

Kf

stability of complex

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Ag(NH3)2+ AgCl

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Qualitative Analysis of Cations

Flame Test for Cations

lithium
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sodium

potassium

copper
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