CHE 1302 Tro 2nd Ed.

Chapter 16: Aqueous Ionic Equilibrium

Dr. Bruce E. Hodson

The Common Ion Effect

1. Consider a solution of the WEAK acid acetic acid, CH3COOH.

3. LeChteliers principle: What happens to [H3O+] ?

2. then add acetate ion as a second solute

NaC2H3O2

Na+ + CH3COO

Ionization of the weak acid is suppressed: pH INCREASES

The Common Ion Effect

Common ion effect : the suppression of the ionization of a weak electrolyte by the presence of a common ion from a strong electrolyte

CH3COOH(aq) at equilibrium: a few H3O+ ions and a few CH3COO ions

Add CH3COO , reestablish equilibrium: more acetate ions, fewer H3O+ ions

The Common Ion Effect

1. Consider a solution of the WEAK base ammonia, NH3 .

3. LeChteliers principle: What happens to [OH] ?

2. then add ammonium ion (a COMMON ION) as a second solute

NH4Cl

NH4+ + Cl

EXAMPLES

Ionization of the weak base is suppressed

16.2 Buffers: Solutions that Resist pH Change

16.2 Buffers: Solutions that Resist pH Change

Pure water has no buffer capacity

In contrast, for a buffer solution the pH barely changes

16.2 Buffers: Solutions that Resist pH Change

A buffer solution is one whose pH changes very little when small amounts of strong acid or strong base are added, or when diluted

Weak acid and a salt of its conjugate base Weak base and a salt of its conjugate acid

16.2 Buffers: Solutions that Resist pH Change

A weak acid and a salt of its conjugate base

16.2 Buffers: Solutions that Resist pH Change

Note that the COMMON ION EFFECT .. is in effect

Buffer pH higher than pure acid and lower than pure salt

16.2 Buffer Solutions Why do they work ?

A buffer maintains approximately constant pH because of the acid and base components which are present at all times ..

weak acid HC2H3O2

conjugate base C2H3O2

Na+ spectator ions

Added OH reacts with acid present

Added H3O+ reacts with base present

HC2H3O2 H2O + C2H3O2

C2H3O2 H2O + HC2H3O2 10

16.2 Buffers: Solutions that Resist pH Change

A weak base and a salt of its conjugate acid

16.2 Buffer Solutions Why do they work ?

A buffer maintains approximately constant pH because of the acid and base components which are present at all times ..

weak base NH3

conjugate acid NH4+

Cl spectator ions

Added OH reacts with acid present NH4+ H2O + NH3 Added H3O+ reacts with base present NH3 H2O + NH4+
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16.2 Buffers: Solutions that Resist pH Change

So. Buffers contain components which can neutralize (small amounts of) added strong acids and bases

Buffers only work because the components do not completely neutralized each another e.g HCl + NaOH doesnt work .

H3O+ + OH 2 H2O

pH of a Buffer: Equilibrium Approach EXAMPLE

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16.2 Buffers: Solutions that Resist pH Change

The Henderson-Hasselbalch equation gives the pH of a weak acid + salt of conjugate base buffer directly:

[conjugate base] pH = pKa + log [weak acid]

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16.2 Buffer Solutions The BUFFER CONDITION

Generally, a buffer is most effective if [weak acid] = [conjugate base] .. Under these conditions, the pH of the buffer is approx. equal to the pKa of the weak acid

[conjugate base] pH = pKa + log [weak acid] pH = pKa

.. and within a range of 2 pH units, meaning 0.1 through 10 for the ratio base to acid
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16.2 Buffer Solutions - CAPACITY

Capacity of a buffer is the amount of strong acid, or strong base, it can consume before it no longer acts as a buffer More Buffer EXAMPLES

.the more concentrated the buffer components in a solution, the more added acid or base the solution can neutralize 16

16.4 Titration and pH Curves 4.8 Acid-Base Titrations (Stoichiometry in Solutions)

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4.8 Titrations (Stoichiometry in Solutions)

A titration is a method for determining the concentration of a solute in a sample of known volume
Add a known volume (L) of a known concentration (mol/L) reactant A (titrant)

1. Add enough A to react completely with B

2. Calculate moles of A added 3. Use a balanced equation to find moles of B present

Known volume (L) of unknown concentration (mol/L) reactant B (analyte)

4. Moles B / volume B = molarity of B

Titrations can be applied to precipitation, acid-base, or redox reactions

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4.8 Acid Base Titration

A TITRANT of known concentration is added until the ANALYTE solution becomes neutral..

42.00 mL of 0.150 M NaOH(aq) added

An INDICATOR is added which changes color at its END POINT

At the EQUIVALENCE POINT, the acid and base have been brought together in exact stoichiometric proportions

H+

HCl(aq) ? conc. (50.00 mL)

Neutral Solution

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16.4 Acid-Base Indicators

A pH indicator is a weak acid that is one color when protonated (HIn), and another color when deprotonated (In) (the conjugate base)

HIn(aq) + acid

HIn(aq) + base

HIn + H2O
RED

In + H3O+
PURPLE
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Adding H3O+ to HIn(aq) (pink) favors HIn (RED) Adding OH to HIn(aq) (pink) favors In (PURPLE)

16.4 Acid-Base Indicators

Adding H3O+ favors HPhenolphthalein

HPhenolphthalein + H2O

Phenolphthalein + H3O+
Adding OH favors Phenolphthalein 21

16.4 Acid-Base Indicators

Different indicators have different values of Ka, so they exhibit color changes at different values of pH

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16.4 Titrations: Strong Acid with Strong Base (MONOPROTIC) So Ideally we want the indicators color change (end point) to be centered around the equivalence point Titration Curve

HCl + NaOH NaCl + H2O

Bromthymol blue changes color at the equivalence point (approx. 20.0 mL NaOH(aq) added)
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16.4 Titrations: Strong Acid with Strong Base (MONOPROTIC) pH values can be calculated at any point by assessing moles of acid and base present and using a balanced equation for the neutralization

HCl + NaOH NaCl + H2O

pH >> 7

pH << 7
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16.4 Titrations: Strong Base with Strong Acid (MONOPROTIC)

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16.4 Titrations: Weak Acid with Strong Base (MONOPROTIC)

HC2H3O2 + NaOH

NaC2H3O2 + H2O

pH >> 7

pH = pKa 1: buffer solution (weak acid and its conjugate base): H-H equation

Equivalence-point pH is NOT 7.00

pH low
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16.4 Titrations: Weak BASE with Strong Acid (MONOPROTIC) Titration curve for the titration of 0.100 M NH3 with 0.100 M HCl EXAMPLES

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16.4 Titrations: Weak Acid with Strong Base (POLYPROTIC) Titration of 50.0 mL of 0.10 M H3PO3 with 0.10 M NaOH H3PO3 + NaOH H2PO3 + NaOH H2PO3 + H2O

HPO32 + H2O

(Multiple Equivalence points)

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16.5 Solubility Equilibria and the Solubility Product Constant

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Equilibria Review
For a saturated solution ..
Eventually, the rates of dissolving and of crystallization are equal; no more solute appears to dissolve.

Solid begins to dissolve

As solid dissolves, some dissolved solute begins to crystallize

Longer standing does not change the amount 30 of dissolved solute

16.5 The Solubility Product Constant, Ksp

Many ionic compounds do not dissolve well in aqueous solution these are termed sparingly soluble rather than insoluble

A Dynamic Equilibrium is established between the solid solute and the 31 ions of that solute in solution

16.5 The Solubility Product Constant, Ksp

The Solubility Product, Ksp , is the equilibrium constant for the dissolution of a sparingly soluble ionic compound

FeS(s)

Fe2+(aq) + S2(aq)

Ksp = [Fe2+] [S2]

One mole of solid is the only reactant and the concentration of the solid is not included in the Ksp expression
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16.5 The Solubility Product Constant, Ksp

Ksp values for a wide variety of sparingly soluble ionic compounds are known for a given temperature (25 C in the table below)

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16.5 Relationship between Ksp and Molar Solubility

Molar solubility is simply the solubility of a compound in moles per liter it can be computed directly from Ksp and vice versa

AgCl(s)

Ag+(aq) + Cl (aq)

Ksp = 1.77 1010

Ksp = [Ag+] [Cl]

1 mol AgCl 1 mol Ag+ 1 mol Cl

Molar Solubility = S = [Ag+] = [Cl]

Ksp = [Ag+] [Cl] = S S = S2

S= Ksp = 1.77 1010 = 1.33 105 M
EXAMPLES
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16.5 The Common Ion Effect and Solubility Equilibria

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18.3 The Common Ion Effect and Solubility Equilibria

If we add one of its ions to a saturated solution of a sparingly soluble compound, we predict that precipitate will form :

K2CrO4 added PbCrO4(s) Pb2+(aq) + CrO42-(aq) PbCrO4(s) Pb2+(aq) + CrO42-(aq)

This follows Le Chateliers principle (more product shifts equilibrium to the left)

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18.3 The Common Ion Effect and Solubility Equilibria

PbCrO4(s) Pb2+(aq) + CrO42-(aq)

EXAMPLES

When K2CrO4 is added to the saturated solution of PbCrO4 (aq)

CrO42

Pb2+

[Pb2+] attains a new, lower equilibrium concentration as Pb2+ reacts with CrO42 to produce PbCrO4 (s)

The solubility of a slightly soluble ionic compound is lowered when a second solute that furnishes a common ion is added to the solution 37

16.5 Solubility and pH

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16.5 Solubility and pH

One way to dissolve a sparingly soluble compound is often to add a strong acid .

CaF2(s)

Ca2+(aq) + 2 F(aq)

H3O+(aq) + F (aq)

HF(aq) + H2O(l)

Added H3O+ reacts with, and removes F; LeChteliers principle says more F forms

If the anion of the compound is the conjugate base of a weak acid, the H3O+ added will react with it lower its concentration

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16.5 Solubility and pH

What about Ksp and Qsp ? Adding H3O+ reduces the [F], hence Qsp < Ksp Remove product

CaF2(s)

Ca2+(aq) + 2 F(aq)

Ksp = [Ca2+] [F]2 = 5.3 109

Qsp = [Ca2+] [F]2

< Ksp

equilibrium shifts to the right Some CaF2 (s) dissolves (increase [F] and [Ca2+]), so that Qsp becomes 40 equal to Ksp. Continues until all acid is consumed or all solid dissolves.

16.5 Solubility and pH

This method will not work when the anion of the sparingly soluble compound is the conjugate base of a strong acid ..

AgCl(s)

Ag+ (aq) + Cl (aq)

NO REACTION

H3O+(aq) + Cl (aq) BaSO4(s)

Ba2+ (aq) + SO42 (aq)

NO REACTION

H3O+(aq) + SO42 (aq)

EXAMPLES .. because the anion is therefore a very weak base

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Limitations of the Ksp Concept

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Limitations of the Ksp Concept

Ksp can only be used for sparingly soluble compounds if we wish to use molarities in the equilibrium constant expression .

Ksp = [A+] [B]

if [AB] = 1.0 105 M is [A+] = [B] = 1.0 105 M ???

in more concentrated solutions, stoichiometric and effective 43 concentrations (activities) are not equal

Limitations of the Ksp Concept

Ions that are not common to the precipitate can affect solubility (and hence Ksp values) :
H2O
Ca2+

Na2SO4 (aq) SO42

Ca2+

SO42
Na+

F
Na+

Na+

CaF2 is more soluble in 0.010 M Na2SO4 than it is in water due to inter-ionic attractions

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16.6 Precipitation

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16.6 Criteria for Precipitation and its completeness

To determine if precipitation will occur, we calculate the Ion Product Reaction Quotient, Qsp, and compare it to Ksp

FeS(s)

Fe2+(aq) + S2(aq)

Ksp = [Fe2+] [S2] Qsp > Ksp Qsp < Ksp

precipitation should occur (reaction shifts left)
precipitation will not occur (reaction shifts right)

Qsp = Ksp

solution is just saturated (equilibrium)

. the Qsp expression takes the same form of the Ksp expression, but 46 concentrations are not equilibrium values

16.6 Criteria for Precipitation and its completeness

We generally consider precipitation to be complete if about 99.9% of the target ion is precipitated (0.1% or less left in solution)

In calculations, assume as much ppt. has formed as possible, calculate concentrations of remaining ions and then equilibrium is reached from that point
EXAMPLES

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16.6 Selective (Fractional) Precipitation

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16.6 Selective (Fractional) Precipitation

We can often completely precipitate one ion while leaving another ion in solution Selective Precipitation

AgNO3 added to a mixture containing Cl and I

EXAMPLES for this to work, there must be a fairly significant difference in the 49 solubilities (Ksp values) of the substances being separated

16.8 Equilibria Involving Complex Ions

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16.8 Equilibria Involving Complex Ions

Complex ions have a more complex structure than the ions we have previously considered

3+
Attached groups (LIGANDS) are ions or molecules with at least one lone pair of electrons Common ligands: Cl, OH, H2O, NH3

Ligands are LEWIS BASES, the central metal atom/ion is a LEWIS 51 ACID. Coordinate covalent bonds are formed.

16.8 Equilibria Involving Complex Ions

The formula of a complex ion is written in square [!!!!!] brackets, any charge is placed superscript right

2+

[AgCl2]

[Cu(NH3)4]2+
A coordination compound is one which contains a complex ion, e.g. 52 Na[AgCl2] or [Cu(NH3)4]Cl2

16.8 Equilibria Involving Complex Ions

The production of a complex ion can be described by an equilibrium reaction..

Ag+(aq) + 2 NH3 (aq)

[Ag(NH3)2]+ (aq)
Kf = [ [Ag(NH3)2]+ ]

[Ag+] [NH3]2
Pb2+(aq) + 4 I (aq) [PbI4]2 (aq)

Kf =

[ [PbI4]2 ]
[Pb2+] [I]4

The equilibrium constant is the FORMATION CONSTANT, Kf

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16.8 Equilibria Involving Complex Ions

At a molecular level, the actual process (mechanism) is stepwise

NH3

3NH3

M(H2O)42+

M(H2O)3(NH3)2+

M(NH3)42+

The product of individual formation constants for each step gives the overall formation constant, Kf
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16.8 Equilibria Involving Complex Ions

Sparingly soluble compounds can be dissolved by treatment with a complexing agent, which contains a ligand with great affinity for the metal ion

AgI (s) Ag+(aq) + 2 S2O32 (aq) AgI(s) + 2 S2O32 (aq)

Ag+ (aq) + I (aq) [Ag(S2O3)2]3 (aq)

KSP = 5.3 109 Kf = 1.7 1013

[Ag(S2O3)2]3 (aq) + I (aq) Kc = Ksp Kf = 1.4 103

The above process is similar to dissolving sparingly soluble compound in strong acid

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16.8 Equilibria Involving Complex Ions

Similarly for AgCl(s) and NH3 .
2but if the concentration of NH3 is made high enough

1. AgCl is insoluble in water.

3 the AgCl forms the soluble [Ag(NH3)2]+ ion.

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16.8 Equilibria Involving Complex Ions

CaSO4 will not dissolve in strong acid, however adding EDTA .

CaSO4 (s)

Ca2+ (aq) + SO42 (aq) [CaEDTA]2 (aq)

KSP = 9.1 106 Kf = 1.0 1011

Ca2+ (aq) + EDTA 4 (aq)

The complexation reaction competes successfully with the precipitation reaction and CaSO4 dissolves

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16.8 Equilibria Involving Complex Ions

EXAMPLES

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16.8 Equilibria Involving Complex Ions

A hydrated cation (a complex ion) can be a weak acid .

[Fe(H2O)6]3+ (aq) + H2O (l)

[Fe(H2O)5OH]2+ (aq) + H3O+ (aq) Ka = 9.0 104

High charge denisty of the metal ion tends to withdraw electron density from, and hence weaken, the OH bonds e.g. Fe2+(aq), Zn2+(aq), Al3+(aq)59

16.8 Equilibria Involving Complex Ions

Certain metal hydroxides, insoluble in water, are amphoteric; they will react with both strong acids or strong bases

HCl (aq) [Al(H2O)6]3+ (aq) Al(OH)3(H2O)3 (s)

NaOH (aq) [Al(OH)4(H2O)2] (aq)

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16.8 Equilibria Involving Complex Ions

The amphoteric behavior is a result of the balance between acidic and basic behavior of the AlOH unit:

(OH)2Al

(OH)2Al

+ OH

+ H3O+

(OH)2Al

+ (OH)2Al
+ 2 H2O As a base, MO breaks

+ H2O As an acid, OH breaks

In an amphoteric substance, M (Al above) is not strongly electronegative as 61 it is for the oxoacids, nor is it highly electropositive as it is in strong bases

16.7 Qualitative Cation Analysis

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16.7 Qualitative Cation Analysis

QIA is used to identify the cations and anions present in a sample
Add precipitating ion

Add precipitating ion

Centrifuge

It has largely been replaced by modern instrumental methods

Centrifuge

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16.7 Qualitative Cation Analysis

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Step 1 Add NH3(aq) Centrifuge

Step 2 Add HCl

Centrifuge Step 5 Dissolve in HCl and add KSCN
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Step 3 Add NaOH

Step 4 Add HCl, Na2HPO4

Centrifuge

Chapter 16 Summaries
The Solubility Product Constant, Ksp, represents an equilibrium between a slightly soluble ionic compound and its ions in a saturated aqueous solution The Common Ion Effect is responsible for the reduction in solubility of a slightly soluble ionic compound according to LeChateliers principle Precipitation is assumed to be complete if no more than 0.1% of the target ion remains in solution The Solubilities of some slightly soluble compounds depends strongly on pH Certain solutes become more soluble in the presence of species that can serve as ligands (Lewis Bases) in Complex Ions The ability of water to donate protons when acting as a ligand accounts for the acidic character of some complex ions Precipitation, acidbase, redox, complex-ion formation, and amphoteric behavior are all used for the Qualitative Analysis of common cations
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Chapter 16 Summaries
A strong electrolyte that produces an ion common to the ionization equilibrium of a weak acid or a weak base suppresses the ionization of the weak electrolyte this is called the COMMON ION EFFECT

Acidbase indicators are weak acids for which the acid and its conjugate base have different colors

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