Chapter 16: Aqueous Ionic Equilibrium

Ch 16.1 of 77

16.1

Introduction

Aqueous solutions are extremely important

Acids and bases are aqueous solutions

Equilibria inuence aqueous solutions

For example, we can describe the strength of an acid or base in terms of equilibrium

How does equilibrium affect mixtures of acids and bases? How does equilibrium affect the solubility of compounds in water?

Ch 16.2 of 77

Buffers
The pH of blood must be maintained between about 7.3 and 7.5 to avoid death Aqueous equilibria in the blood control pH A buffer is a substance that resists changes in pH
A buffer reacts with added acid or base with little change in overall pH

In blood, the major components of the buffer are H2CO3 and HCO3How are these related to each other?
Ch 16.3 of 77

Buffer Composition
Buffers contain signicant quantities of an acid and its conjugate base (or a base and its conjugate acid)
Carbonic acid (H2CO3) + bicarbonate (HCO3-) Ammonia (NH3) + ammonium ions (NH4+) Acidic Basic

Consider an acetic acid (HCH3CO2) and (its conjugate base) acetate (CH3CO2-) buffer: 1. Added base is neutralized by the acid HCH3CO2 2. Added acid is neutralized by the conjugate base CH3CO2Ch 16.4 of 77

How Buffers Work

1. Added base is neutralized by the acid HCH3CO2 OH-(aq) + HCH3CO2(aq) CH3CO2-(aq) + H2O(l) Addition of OH- shifts the equilibrium right
As long as the amount of OH- added is small compared with the amount of HCH3CO2, it is almost completely neutralized CH3CO2- is weakly basic so pH would rise slightly

Ch 16.5 of 77

How Buffers Work

2. Added acid is neutralized by the conjugate base CH3CO2H+(aq) + CH3CO2-(aq) HCH3CO2(aq) Addition of H+ shifts the equilibrium right
As long as the amount of H+ added is small compared with the amount of CH3CO2-, it is almost completely neutralized HCH3CO2 is weakly acidic so pH would drop slightly Acetic acid by itself is not a good buffer because the amount of CH3CO2- available is very small
Ch 16.6 of 77

How Buffers Work

Buffer made by mixing acetic acid and sodium acetate Addition of acid: HCl(aq) + NaCH3CO2(aq) HCH3CO2(aq) + NaCl(aq) Addition of base: NaOH(aq) + HCH3CO2(aq) NaCH3CO2(aq) + H2O(l) Any acetate works
Ch 16.7 of 77

Calculating Buffer pH
At rst sight, calculating the pH of a mixture of acid and base might seem difcult But the common ion effect simplies the problem HCH3CO2(aq) H+(aq) + CH3CO2-(aq) Adding extra conjugate base (the common ion) suppresses ionization of the acid (Le Chtelier) The initial concentrations of the acid and added conjugate base dont change signicantly
Ch 16.8 of 77

Calculating Buffer pH
HCH3CO2(aq) H+(aq) + CH3CO2-(aq) To nd pH we need [H+]eqm
[CH3 CO 2 ]" [H+ ] [A! ]" [H+ ] Ka = = [HCH3 CO 2 ] [HA] K a " [HA] [H ] = [A! ] K a " [HA]initial # ! [A ]initial
+ !

Because of common ion effect, concentrations of acid and conjugate base dont change much upon reaching equilibrium!
Ch 16.9 of 77

Calculating Buffer pH
K a ! [HA]initial [H ] = [A" ]initial
+

Take logs

# K a ! [HA]initial & log[H ] = log % " ( $ [A ] '

+ initial

Separate terms Multiply by -1

" [HA]initial % log[H ] = logK a + log $ ! ' # [A ] &

+ initial

" [HA]initial % ! log[H ] = ! logK a ! log $ ! ' # [A ] &

+ initial
Ch 16.10 of 77

Simplifying Calculating Buffer pH

" [HA]initial % ! log[H ] = ! logK a ! log $ ! ' # [A ] &
+ initial

" [A! ]initial % pH = pK a + log $ # [HA] ' &

initial

We have arrived at the Henderson-Hasselbalch equation It allows us to calculate pH from initial concentrations of acid and conjugate base It should only be used for buffers
Ch 16.11 of 77

The Henderson-Hasselbalch Equation

Calculate the pH of a solution of 0.34 M lactic acid (Ka = 1.4x10-4) and 0.22 M potassium lactate We must recognize this as a buffer solution with [HA] = 0.34 M and [A-] = 0.22 M Using the Henderson-Hasselbalch equation
How do we nd this?

" [A! ]initial % pH = pK a + log $ # [HA] ' &

initial

! 0.22 $ pH = pK a + log # " 0.34 & %

Ch 16.12 of 77

The Henderson-Hasselbalch Equation

Remember pKa = -log(Ka) = -log(1.4x10-4) = 3.85
Check that x is small? Cant because assumption is built in

! 0.22 $ pH = 3.85 + log # " 0.34 & % = 3.85 + log(0.647) = 3.85 ' 0.19 = 3.66

When [HA] = [A-] then pH = pKa because log(1) = 0

The Henderson-Hasselbalch equation works best where x is small is appropriate

Ch 16.13 of 77

Calculating Changes in Buffer pH

While buffers resist changes in pH upon addition of strong acid or base, the pH does change slighty We nd out how much by breaking the pH calculation into two parts: 1. Stoichiometry calculation
Use stoichiometry to nd out how much conjugate base is neutralized by addition of strong acid or Use stoichiometry to nd out how much acid is neutralized by addition of strong base

2. Equilibrium calculation
Use Henderson-Hasselbalch calculation
Ch 16.14 of 77

Calculating Changes in Buffer pH (1)

Calculate the pH of a solution of 1.00 L of 0.34 M lactic acid (Ka = 1.4x10-4) and 0.22 M potassium lactate after addition of 0.05 L of 1.0 M HCl 1. Stoichiometry calculation Addition of strong acid uses up some of the conjugate base and makes more lactic acid H+(aq) + A-(aq) HA(aq)
Remember HA is a weak acid so equilibrium lies mostly on the right
Ch 16.15 of 77

Calculating Changes in Buffer pH (1)

Its easiest to work in terms of moles rather than concentration
Moles [A-] = 1.00 L x 0.22 M = 0.22 moles Moles [HA] = 1.00 L x 0.34 M = 0.34 moles Moles [H+] added = 0.05 L x 1.00 M = 0.05 moles

H+(aq) Initial Addition Final 0.00 mol 0.05 mol 0.00 mol

A-(aq) 0.22 mol Decreases 0.17 mol

HA(aq) 0.34 mol Increases 0.39 mol

Ch 16.16 of 77

Calculating Changes in Buffer pH (1)

H+(aq) Initial Addition Final 0.00 mol 0.05 mol 0.00 mol + A-(aq) 0.22 mol Decreases 0.17 mol HA(aq) 0.34 mol Increases 0.39 mol

How do you know whether the [HA] concentration increases or decreases? The addition of strong acid increases [HA] The addition of strong base increases [A-]
Ch 16.17 of 77

Calculating Changes in Buffer pH (1)

2. Equilibrium calculation Well convert the moles back into concentration
[HA] = 0.39 mols / 1.05 L = 0.37 M [A-] = 0.17 mols / 1.05 L = 0.16 M

and use the Henderson-Hasselbalch equation

" [A! ]initial % pH = pK a + log $ # [HA] ' &
initial

! 0.16 $ pH = 3.85 + log # & = 3.49 " 0.37 %

Small 4.6% change from 3.66

Ch 16.18 of 77

Calculating Changes in Buffer pH (2)

Calculate the pH of a solution of 1.00 L of 0.34 M lactic acid (Ka = 1.4x10-4) and 0.22 M potassium lactate after addition of 0.05 L of 1.0 M NaOH 1. Stoichiometry calculation Addition of strong base uses up some of the acid and makes more lactate OH-(aq) + HA(aq) A-(aq) + H2O(l)
Addition of OH- pushes the equilibrium to the right

Ch 16.19 of 77

Calculating Changes in Buffer pH (2)

Its easiest to work in terms of moles rather than concentration
Moles [A-] = 1.00 L x 0.22 M = 0.22 moles Moles [HA] = 1.00 L x 0.34 M = 0.34 moles Moles [OH-] added = 0.05 L x 1.00 M = 0.05 moles

OH-(aq) + HA(aq) Initial Addition Final 0.00 mol 0.05 mol 0.00 mol 0.34 mol Decreases 0.29 mol

A-(aq) 0.22 mol Increases 0.27 mol

Ch 16.20 of 77

Calculating Changes in Buffer pH (2)

2. Equilibrium calculation Well convert the moles back into concentration
[HA] = 0.29 mols / 1.05 L = 0.28 M [A-] = 0.27 mols / 1.05 L = 0.26 M

and use the Henderson-Hasselbalch equation

" [A! ]initial % pH = pK a + log $ # [HA] ' &
initial

! 0.26 $ pH = 3.85 + log # & = 3.82 " 0.28 %

Small 4.4% change from 3.66

Ch 16.21 of 77

16.3

Buffer Range

Changes in buffer pH upon addition of a strong acid or base are smallest when: 1. The concentrations of HA and A- are equal
The buffer has reserves of both acid and base with which to neutralize additions HA and A- concentrations should be within a factor of 10 Buffers work best when the pH = pKa of the acid

2. The concentrations of HA and A- are large

The concentrations of HA and A- dont change much upon additions of strong acid and base
Ch 16.22 of 77

Buffer Range
HA and A- concentrations should be within a factor of 10 for a reasonably good buffer
" [A! ] % pH = pK a + log $ # [HA] ' &
! [10] $ pH = pK a + log # " [1] & % (1) pH = pK a + 1
How does pH vary if we change ratio?

! [1] $ pH = pK a + log # " [10] & % (2) pH = pK a ' 1

The buffer range (the range of pH over which the buffer is effective) is pKa1
Ch 16.23 of 77

Buffer Capacity
The buffer capacity is the amount of strong acid or base that can be added to the buffer before it is destroyed
This means either the acid or conjugate base is completely used up

Buffer capacity increases as [HA] and [A-] increase

A 0.5 M HA + 0.5 M A- buffer has a higher buffer capacity than a 0.1 M HA + 0.1 M A- buffer A 0.5 M HA + 0.5 M A- buffer has a higher buffer capacity than a 0.5 M HA + 0.1 M A- buffer
Ch 16.24 of 77

Buffer Capacity
A buffer is comprised of 0.10 mols HCH3CO2 and 0.05 mols NaCH3CO2. Which of the following additions will destroy the buffer? 0.05 mols of NaCH3CO2?
No - this will simply increase [A-]

0.05 mols of NaOH?

No - this will use up half of the acid but leave half remaining

0.05 mols of HBr?

Yes - this will use up all of the conjugate base leaving only the weak acid (not a buffer)
Ch 16.25 of 77

16.4

Titrations and pH Curves

In an acid-base titration, an acid of known quantity and concentration is reacted with a base of unknown concentration The endpoint or equivalence point is reached when an added indicator just changes color Care must be taken not to exceed the endpoint
The acid is exactly neutralized by the base

The information about the substance added can be used to determine the concentration of the titrant (the substance added)
Ch 16.26 of 77

Titrations
At the endpoint, enough base has been added to exactly neutralize the acid H+(aq) + OH-(aq) H2O(l) At the endpoint the moles H+(aq) and moles OH-(aq) are equal
Ch 16.27 of 77

Titrations and pH Curves

At the endpoint, [H+] = [OH-] so pH is neutral

After the endpoint, [OH-] is in excess so pH is high

Before the endpoint, [H+] is in excess so pH is low

Ch 16.28 of 77

Titration and pH Curves

We can calculate the pH curve by knowing how many moles of acid has been neutralized after each addition of base We must work in moles (not concentration)
Mols = Concentration (mols / L) !Volume (L)

Which can be rearranged to

Mols Volume (L) = Concentration (mols / L)

Useful equations

Ch 16.29 of 77

Titration and pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCl with 0.100 M KOH Mols H+ = 0.200 M 0.050 L = 0.010 mols At the endpoint mols H+ = mols OH- so
0.010 mols OH! Volume OH! = = 0.100 L 0.100 mols / L

The endpoint occurs after addition of 100 mL of KOH

Ch 16.30 of 77

Strong Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCl with 0.100 M KOH 1. Before addition of any base: HCl(aq) H+(aq) + Cl-(aq) [H+] = 0.200 M
pH = !log[H+ ] = !log(0.200) = 0.70
pH of a strong acid

Ch 16.31 of 77

Strong Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCl with 0.100 M KOH 2. After addition of 10.00 mL base: Some H+ is neutralized H+(aq) + OH-(aq) H2O(l) The moles of H+ neutralized is the same as the moles of OH- added
Mols OH! added = Concentration (M) "Volume (L) = 0.100 M " 0.010 L = 0.001
Ch 16.32 of 77

Strong Acid-Strong Base pH Curves

The moles of H+ left is the original amount (0.010 mols) minus the amount that was neutralized (0.001 mols) = 0.009 mols The [H+] is 0.009 mols + [H ] = = 0.150 M 0.050 L + 0.010 L 50 mL of HCl + And pH is 10 mL KOH added pH = !log[H+ ] pH increases = !log(0.150) as base is = 0.82 added
Ch 16.33 of 77

Strong Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCl with 0.100 M KOH 3. After addition of 20.00 mL base: Some H+ is neutralized H+(aq) + OH-(aq) H2O(l) The moles of H+ neutralized is the same as the moles of OH- added
Mols OH! added = Concentration (M) "Volume (L) = 0.100 M " 0.020 L = 0.002
Ch 16.34 of 77

Strong Acid-Strong Base pH Curves

The moles of H+ left is the original amount (0.010 mols) minus the amount that was neutralized (0.002 mols) = 0.008 mols The [H+] is 0.008 mols + [H ] = = 0.114 M 0.050 L + 0.020 L 50 mL of HCl + And pH is 20 mL KOH added pH = !log[H+ ] pH increases = !log(0.114) as more base = 0.94 is added
Ch 16.35 of 77

Strong Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCl with 0.100 M KOH 4. After addition of 100 mL base (the endpoint): All H+ is neutralized H+(aq) + OH-(aq) H2O(l) The only source of H+ is from the ionization of water [H+] = 1.00x10-7 M so pH = 7.00

Ch 16.36 of 77

Strong Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCl with 0.100 M KOH 5. After addition of 110 mL base (10 mL past the endpoint): All H+ is neutralized but there is an excess of OH 100 mL base is used to neutralize the acid so 10 mL excess has been added
Mols excess OH! = Concentration (M) "Volume (L) = 0.100 M " 0.010 L = 0.001
Ch 16.37 of 77

Strong Acid-Strong Base pH Curves

The [OH-] is
0.001mols [OH ] = = 0.006 M 0.050 L + 0.110 L pOH is 50 mL of HCl + 110 mL KOH pOH = !log[OH! ] added = !log(0.006) = 2.20 pH is basic past And pH = 14.00 - pOH = 11.80 equivalence
!

point
Ch 16.38 of 77

Strong Acid-Strong Base pH Curves

Vol KOH added (mL) 0 10 20 30 40 50 60 70 80 90 100 110 120 pH 0.70 0.82 0.94 1.06 1.18 1.30 1.44 1.60 1.81 2.15 7.00 11.80 12.07
Ch 16.39 of 77

14 12 10 pH 8 6 4 2 0 0 10 20

Endpoint pH = 7.00

pH always increases

100 Volume KOH (mL)

Strong Acid-Strong Base pH Curves

1. At start, calculate the pH of a strong acid 2. Before the endpoint, H+ is in excess
Calculate [H+] from initial moles minus moles neutralized (moles OH-) divided by total volume

3. At the endpoint, H+ comes from water only

pH = 7.00

4. After the endpoint, OH- is in excess

Calculate [OH-] from moles added minus moles neutralized (initial moles H+) divided by total volume

Ch 16.40 of 77

Weak Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCH3CO2 (Ka=1.8x10-5) with 0.100 M KOH Total mols H+ = 0.200 M 0.050 L = 0.010 mols At the endpoint mols H+ = mols OH- so
0.010 mols OH! Volume OH! = = 0.100 L 0.100 mols / L

The endpoint occurs after addition of 100 mL of KOH

Ch 16.41 of 77

Weak Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCH3CO2 (Ka=1.8x10-5) with 0.100 M KOH 1. Before addition of any base: HCH3CO2(aq) H+(aq) + CH3CO2-(aq) [H+] = ? This is a weak acid problem so we need to solve with an ICE table for 0.200 M HCH3CO2

Ch 16.42 of 77

Weak Acid-Strong Base pH Curves

HCH3CO2 Initial Change Equilibrium 0.200 -x 0.200 - x H+ 0 +x x
"

CH3CO20 +x x

[H+ ]! [CH3 CO 2 ] Ka = [HCH3 CO 2 ]

"5 2 2

x x 1.8x10 = # 0.200 " x 0.200 x = [H+ ] = 1.90x10"3 pH = 2.72

x is small

Ch 16.43 of 77

Weak Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCH3CO2 (Ka=1.8x10-5) with 0.100 M KOH 2. After addition of 10 mL of base: HCH3CO2(aq) H+(aq) + CH3CO2-(aq) HCH3CO2(aq) + OH-(aq) H2O(l) + CH3CO2-(aq) Addition of base always converts a stoichiometric amount of the acid to its conjugate base
We ignore the small amounts H+ and CH3CO2- made by the equilibrium
Ch 16.44 of 77

Weak Acid-Strong Base pH Curves

The moles of HCH3CO2 used up and the moles of CH3CO2- made is the same as the moles of OHadded
Mols OH added = Concentration (M) "Volume (L) = 0.100 M " 0.010 L = 0.001
!

Moles HCH3CO2 is initial (0.010 mols) minus that used up (0.001 mols) = 0.009 mols Moles CH3CO2- made is 0.001 mols
Ch 16.45 of 77

Weak Acid-Strong Base pH Curves

We have some acid and some conjugate base This is a buffer!
pKa = -log(1.8x10-5) = 4.74 HendersonHasselbalch equation pH increases because weve added base

" [A! ] % pH = pK a + log $ # [HA] ' & " 0.001mols / 0.060 L % = 4.74 + log $ # 0.009 mols / 0.060 L ' & = 3.79
Total volume = 50 mL + 10 mL

Ch 16.46 of 77

Weak Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCH3CO2 (Ka=1.8x10-5) with 0.100 M KOH 3. After addition of 20 mL of base: HCH3CO2(aq) + OH-(aq) H2O(l) + CH3CO2-(aq) Addition of base converts a stoichiometric amount of the acid to its conjugate base
[HCH3CO2] decreases and [CH3CO2] increases according to amount of OH- added

Ch 16.47 of 77

Weak Acid-Strong Base pH Curves

The moles of HCH3CO2 used up and the moles of CH3CO2- made is the same as the moles of OHadded
Mols OH added = Concentration (M) "Volume (L) = 0.100 M " 0.020 L = 0.002
!

Moles HCH3CO2 is initial (0.010 mols) minus that used up (0.002 mols) = 0.008 mols Moles CH3CO2- made is 0.002 mols
Ch 16.48 of 77

Weak Acid-Strong Base pH Curves

We have some acid and some conjugate base This is a buffer
" [A! ] % pH = pK a + log $ # [HA] ' & " 0.002 mols / 0.070 L % = 4.74 + log $ # 0.008 mols / 0.070 L ' & = 4.14
Total volume = 50 mL + 20 mL
Ch 16.49 of 77

Weak Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCH3CO2 (Ka=1.8x10-5) with 0.100 M KOH 4. After addition of 100 mL of base (at the endpoint): HCH3CO2(aq) + OH-(aq) H2O(l) + CH3CO2-(aq) At the endpoint, all the weak acid has been converted to conjugate base The solution is a salt in water

Ch 16.50 of 77

Weak Acid-Strong Base pH Curves

The salt is KCH3CO2 in water
K+ is neutral (from a strong base) CH3CO2- is basic (from a weak acid)

The moles of CH3CO2- made are the same as the moles of OH- added
Mols OH added = Concentration (M) "Volume (L) = 0.100 M " 0.100 L = 0.010
!

0.010 mols CH3 CO 2 ! [CH3 CO 2 ] = = 0.0667 M 0.050 L + 0.100 L

Ch 16.51 of 77

Weak Acid-Strong Base pH Curves

We have a weak base dissolved in water CH3CO2-(aq) + H2O(l) HCH3CO2(aq) + OH-(aq) We can solve this equilibrium with an ICE table
CH3CO2Initial Change 0.0667 -x HCH3CO2 0 +x x OH0 +x x

Equilibrium 0.0667 - x

Note, CH3CO2- acts as a base; we need Kb

Ch 16.52 of 77

Weak Acid-Strong Base pH Curves

CH3CO2-(aq) + H2O(l) HCH3CO2(aq) + OH-(aq) CH3CO2- is the conjugate base of HCH3CO2 (Ka = 1.8x10-5) so
KW 1.0x10!14 Kb = = = 5.6x10!10 K a 1.8x10!5
Kb = [OH! ]" [CH3 CO 2 H] [CH3 CO 2 ]
Ch 16.53 of 77

And we can insert values from the ICE table

Weak Acid-Strong Base pH Curves

Inserting values and solving for x (= [OH-])
Kb =
!10

[OH! ]" [CH3 CO 2 H] [CH3 CO 2 ]

2 2 !

x x 5.6x10 = # 0.0667 ! x 0.0667 x = 6.11x10!6

pOH = -log(6.11x10-6) = 5.21 pH = 14.00 - pOH = 8.79

Ch 16.54 of 77

Weak Acid-Strong Base pH Curves

Derive the pH curve for titration of 50 mL of 0.200 M HCH3CO2 (Ka = 1.8x10-5) with 0.100 M KOH 5. After addition of 110 mL base (10 mL past the endpoint): Weak acid is completely neutralized but there is an excess of OH 100 mL base is used to neutralize the acid so 10 mL excess has been added
Mols excess OH = Concentration (M) "Volume (L) = 0.100 M " 0.010 L = 0.001
Ch 16.55 of 77

Weak Acid-Strong Base pH Curves

The [OH-] is
0.001mols [OH ] = = 0.006 M 0.050 L + 0.110 L 50 mL of pOH is HCH3CO2 + pOH = !log[OH! ] 110 mL KOH = !log(0.006) added = 2.20
!

And pH = 14.00 - pOH = 11.80

Same as for strong acid-strong base since KOH now dominates

pH is very basic past endpoint

Ch 16.56 of 77

Weak Acid-Strong Base pH Curves

Vol KOH added (mL) 0 10 20 30 40 50 60 70 80 90 100 110 120 pH 2.72 3.79 4.14 4.38 4.57 4.74 4.92 5.11 5.35 5.70 8.79 11.80 12.07
Ch 16.57 of 77

14 12 10 pH 8 6 4 2 0 0 10 20

Endpoint pH > 7.00 pKa = 4.74

Buffer range
50 Volume KOH (mL) 100

Weak Acid-Strong Base pH Curves

1. At start, calculate the pH of a weak acid
ICE table for weak acid using Ka

2. Before the endpoint, a buffer solution exists

Use Henderson-Hasselbalch equation Halfway to endpoint, pH = pKa

3. At the endpoint, HA has been converted to its conjugate base

Use ICE table for salt in water using Kb

4. After the endpoint, OH- is in excess

Calculate [OH-] from moles added minus moles neutralized (initial moles H+) divided by total volume
Ch 16.58 of 77

Polyprotic Acid-Strong Base pH Curves

A polyprotic acid produces multiple endpoints in titrations, each endpoint corresponding to the neutralization of each proton Consider sulfurous acid: H2SO3(aq) HSO3-(aq) + H+(aq) Ka1 = 1.6x10-2 HSO3-(aq) SO32-(aq) + H+(aq) Ka2 = 6.4x10-8 In the rst reaction, the rst proton in H2SO3 is neutralized In the second reaction, HSO3- is neutralized
Ch 16.59 of 77

14 12 10 pH 8 6 4 2 0 0 10 20 30 40 50 60 Volume KOH (mL)

1st endpoint Buffer range

Buffer range

2nd endpoint

pKa1 = 1.80

pKa2 = ~7.19

25 mL 0.100 M H2SO3 titrated with 0.100 M NaOH

Ch 16.60 of 77

Indicators
The endpoint of an acid-base titration is always signaled by a rapid change in pH Sometimes it is more convenient to use an indicator, a molecule with an acid and conjugate base that are different colors

Colorless

Pink

Ch 16.61 of 77

Indicators
Indicators are weak acids represented by the generic formula HIn HIn(aq) + H2O(l) In-(aq) + H3O+(aq)
Color 1 Color 2

In acidic conditions, [H3O+] is high and equilibrium shifts left

At low pH the indicator is color 1

In basic conditions, [H3O+] is small and equilibrium shift right

At high pH the indicator is color 2
Ch 16.62 of 77

Indicators
Remember, an equilibrium is present so both HIn and In- will be present all the time but in different concentrations HIn(aq) + H2O(l) In-(aq) + H3O+(aq)
Color 1 Color 2

When [In-]/[HIn] 10 the solution appears color 2 When [In-]/[HIn] 0.1 the solution appears color 1 When [In-]/[HIn] = 1 the solution appears intermediate
Ch 16.63 of 77

Indicators
According to the Henderson Hasselbalch equation
" [In! ] % pH = pK a + log $ # [HIn] ' & " 10 % = pK a + log $ ' # 1& = pK a + 1 Color 2 " [In! ] % pH = pK a + log $ # [HIn] ' & " 1% = pK a + log $ ' # 10 & = pK a ! 1 Color 1

So indicators change color over about 2 pH units centered at the pKa of the indicator
Ch 16.64 of 77

Indicators
What is the pH range over which methyl red indicator (Ka = 7.9x10-6) changes from pink (acid form) to yellow (basic form)? pKa = -log(7.9x10-6) = 5.1 Color changes at pKa1 It will be pink at pH = 4.1 (and below) and yellow at pH 6.1 (and above)

pH = pKa when [In-] = [HIn]

Ch 16.65 of 77

Choice of Indicator

Indicator should be chosen so it changes color exactly at endpoint (where indicator pKa = pH at endpoint) Best for strong acid-strong base titration
Ch 16.66 of 77

16.5

Solubility Equilibria

A substance is soluble if it dissolves and insoluble if it does not But some substances are very soluble and others slightly soluble Equilibrium constants can quantitate solubility PbBr2(s) Pb2+(aq) + 2 Br-(aq) Ksp = [Pb2+][Br-]2 where Ksp is the solubility product constant for PbBr2
Ch 16.67 of 77

Solubility Product Constants

A larger Ksp means more soluble
Slightly soluble

Very insoluble
Ch 16.68 of 77

Ksp and Molar Solubility

Ksp values can be used to calculate molar solubility (the solubility in mols/L) What is the molar solubility of lead chloride PbCl2 (Ksp = 1.17x10-5)? PbCl2(s) Pb2+(aq) + 2 Cl-(aq) Since this is an equilibrium problem, well write an ICE table
Dont include PbCl2 in the table because it is a solid and wont enter into expression for Ksp
Ch 16.69 of 77

Ksp and Molar Solubility

PbCl2(s) Pb2+(aq) + 2 Cl-(aq) Writing an ICE table
Pb2+(aq) Initial Change Equilibrium 0.00 +S S Cl-(aq) 0.00 +2S 2S

Well use S (for molar solubility) rather than x

Ch 16.70 of 77

Ksp and Molar Solubility

PbCl2(s) Pb2+(aq) + 2 Cl-(aq) Insert into expression for Ksp
Ksp = [Pb 2+ ]! [Cl" ]2 1.17x10"5 = S ! (2 ! S)2 = S ! (4 ! S2 )
Careful! Molar solubility = 1.43x10-2 mols/L

= 4 ! S3

1.17x10"5 S=3 = 1.43x10"2 4

Ch 16.71 of 77

Ksp and Relative Molar Solubility

Care must be taken when comparing Ksp values
Ksp 3 mols 2 mols Mg(OH)2 FeCO3 2.06x10-13 3.07x10-11 Molar solubility 3.72x10-5 M 5.54x10-6 M

The relationship between Ksp and molar solubility depends on the number of moles of ions made
Ksps can only be compared if the same number of moles of ions are made otherwise compare molar solubility
Ch 16.72 of 77

16.6

Precipitation Reactions

A precipitate forms when two solutions of soluble ions are mixed and at least one of the ionic products is insoluble Na2CrO4(s) 2 Na+(aq) + CrO42-(aq) AgNO3(s) Ag+(aq) + NO3-(aq) Both solids are very soluble on their own If mixed, insoluble Ag2CrO4(s) forms
Really Ag2CrO4 is slightly soluble (Ksp = 1.12x10-12) NaNO3 is soluble (Ksp large) and remains as Na+ and NO3- ions
Ch 16.73 of 77

Precipitation Reactions
Remember, tiny quantities of Ag2CrO4 are soluble As long as Q < Ksp, no precipitate forms (an unsaturated solution) When Q = Ksp, the precipitate just begins to form (a saturated solution)

Ch 16.74 of 77

Precipitation Reactions
Under some circumstances, a supersaturated solution can form where Q > Ksp
Supersaturated solutions are unstable and usually form a precipitate, sometimes suddenly!

Ch 16.75 of 77

Precipitation Reactions
Does a solution of 0.020 M Ca(CH3CO2)2(aq) mixed with 0.004 M Na2SO4(aq) produce a precipitate of CaSO4(s) (Ksp = 7.10x10-5)? We need to compare Q with Ksp Ca(CH3CO2)2(s) Ca2+(aq) + 2 CH3CO2-(aq) [Ca2+] = 0.020 M Na2SO4(s) 2 Na+(aq) + SO42-(aq) [SO42-] = 0.004 M
Ch 16.76 of 77

Precipitation Reactions
The reaction relating to Ksp is CaSO4(s) Ca2+(aq) + SO42-(aq) And
Q = [Ca
2+

]! [SO 4

2"

]
Ksp = 7.10x10-5

= 0.020 # 0.004 = 8x10"5

Since Q > Ksp, we have exceeded the solubility and a small amount of CaSO4(s) should precipitate
Ch 16.77 of 77