CHAPTER 16
Aqueous Ionic Equilibrium
Buffers
• Buffers: solutions that resist pH change upon addition of strong
acid or strong base
• Buffer solutions contain significant quantities of both a weak acid
and its conjugate base (or weak base and its conjugate acid)
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Buffers
How do buffer solutions resist pH change?
• A buffer contains a weak acid (HA) and its conjugate base (A-)
• Adding a small amount of strong base (OH-) neutralizes some HA
and converts it to A- :
−
𝐻𝐴 𝑎𝑞 + 𝑂𝐻(𝑎𝑞) → 𝐻2 𝑂 + 𝐴−
(𝑎𝑞)
• All the OH- reacts and the rise in pH is very small
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Buffers
• Adding a small amount of strong acid (H3O+) neutralizes some A-
and converts it to HA :
𝐴−𝑎𝑞 + 𝐻3 𝑂(𝑎𝑞)
+
→ 𝐻2 𝑂 + 𝐻𝐴(𝑎𝑞)
• All the H3O+ reacts and the drop in pH is very small
• As long as the amount of added strong acid/base is relatively small
compared to amounts of HA/A- the pH change will be small
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Henderson-Hasselbalch equation
• For buffer solutions (significant and approximately equal
concentrations of HA and A-) the following equation can be used to
estimate buffer pH:
𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( )
𝐻𝐴
• Derivation is in the textbook, comes about from using the simplifying
assumption for both HA and A-
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Henderson-Hasselbalch equation
𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( )
𝐻𝐴
Equation can only be used for buffer solutions where the following is
true:
• [HA] and [A-] are both at least 100x higher than Ka
• [HA] and [A-] are both within an order of magnitude of each other
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Henderson-Hasselbalch equation
𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( )
𝐻𝐴
• When [A-] = [HA] , pH pKa
• When [A-] > [HA] , pH pKa
• When [HA] > [A-] , pH pKa
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Henderson-Hasselbalch equation
𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( )
𝐻𝐴
• Amounts of HA and A- in moles can also be used instead of
concentration:
𝑛𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( )
𝑛𝐻𝐴
• The volume of the buffer solution cancels out during the conversion
8
pH changes in buffers
• Two part calculation in determining pH change to a buffer when a
strong acid/base is added
Part 1: Reaction between H3O+ and A- (or OH- and HA) , calculate
number of moles that react based on limiting reagent and find new
amounts of HA and A-
Part 2: Calculate pH of resultant solution based on new HA and A-
amounts
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Worked example
A 1.0 L buffer solution contains 0.100 M CH3COOH and 0.100 M CH3COONa
(pKa of CH3COOH = 4.74)
Calculate the pH of this solution before AND after the addition of 0.010 mol of
OH- to the solution.
Before addition of OH-
𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( )=
𝐻𝐴
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Worked example
The reaction that takes place when OH- is added :
− −
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝑂𝐻(𝑎𝑞) → 𝐻2 𝑂 + 𝐶𝐻3 𝐶𝑂𝑂(𝑎𝑞)
Before Addition
Addition
After Addition
The resultant solution is still a buffer, but now A- > HA so pH will be a
bit higher
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Worked example
Use the Henderson-Hasselbalch equation to calculate the pH of the
resultant solution:
𝑛𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( ) =
𝑛𝐻𝐴
• Converting back to concentrations will also work
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Weak base buffers
• To calculate pH, use the H/H equation as before, but convert pKb of
the weak base to the pKa of its conjugate acid
• Recall: pKa + pKb = 14 for a conjugate acid/base pair
H/H equation as previously stated:
𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + log( )
𝐻𝐴
More general form for a conjugate acid/base pair:
𝑏𝑎𝑠𝑒
𝑝𝐻 = 𝑝𝐾𝑎 + log( )
𝑎𝑐𝑖𝑑
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Buffer effectiveness and capacity
• A buffer is most effective at resisting pH change when [acid] =
[base] for a conjugate acid/base pair (pH = pKa)
• Buffers are generally considered effective when pH = pKa ± 1
• pH = pKa ± 1 corresponds to [acid] and [base] being within an order
of magnitude of each other
• More concentrated buffer solutions are more effective at resisting pH change
(ex: 0.100 M HA / 0.100 M A- vs. 1.00 M HA / 1.00 M A-) – higher buffer capacity
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Titrations
• The main use of a titration is to determine the concentration of an
acid or base in solution using a solution of acid or base of known
concentration
• pH meter or indicator used to track the experiment as the known
solution is added to the unknown solution using a burette
• At the equivalence point, nacid = nbase
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Titrations
• A titration curve shows the progress of the experiment if a pH meter
is used
• Equivalence point corresponds to the
steepest (inflection) point on the curve
• Equivalence point does not always
occur at pH = 7
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Titrations
Titration of a strong acid with a strong base
• Consider titration of 25.0 mL of 0.100 M HCl with 0.100 M NaOH
(this means NaOH is in the burette and being added to the HCl
solution)
What volume of NaOH must be added to reach the equivalence
point?
𝑛𝑎𝑐𝑖𝑑 = 0.100 𝑀 0.0250 𝐿 = 2.50 × 10−3 𝑚𝑜𝑙 (𝑜𝑟 2.50 𝑚𝑚𝑜𝑙)
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Titrations
Now let’s track the progress of this titration experiment using
calculations
Initial pH before any NaOH is added
[H3O+] = 0.100 M
pH =
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Titrations
pH after adding 5.00 mL of NaOH
• Use stoichiometry to calculate H3O+ remaining
taking into account the increase in volume
+ −
𝐻3 𝑂(𝑎𝑞) + 𝑂𝐻(𝑎𝑞) → 2 𝐻2 𝑂
Before Addition
Addition
After Addition
Volume of solution = 25.0 mL + 5.00 mL = 30.0 mL [H3O+] = 0.067 M, pH = 1.18
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Titrations
pH after adding 25.00 mL of NaOH
• pH = 7 since acid and base have completely neutralized each other
in an exact 1:1 ratio
• Salt solution (Na+ and Cl-) neither acidic nor basic
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Titrations
pH after adding 30.00 mL of NaOH
• Solution will be basic since nbase > nacid
+ −
𝐻3 𝑂(𝑎𝑞) + 𝑂𝐻(𝑎𝑞) → 2 𝐻2 𝑂
Before Addition
Addition
After Addition
Volume of solution = 25.0 mL + 30.00 mL = 55.0 mL
[OH-] = 0.0091 M, pH = 11.96
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Titrations
Titration curve of a strong acid + strong base
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Titrations
Titration of a weak acid with a strong base
• Consider titration of 25.0 mL of 0.100 M HCOOH with 0.100 M NaOH
• pKa (HCOOH) = 3.74
What volume of NaOH must be added to reach the equivalence point?
𝑛𝑎𝑐𝑖𝑑 = 0.100 𝑀 0.0250 𝐿 = 2.50 × 10−3 𝑚𝑜𝑙 (𝑜𝑟 2.50 𝑚𝑚𝑜𝑙)
The volume of the equivalence point does not depend on whether a strong or weak acid is being
titrated
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Titrations
Now let’s track the progress of this titration experiment using
calculations
Initial pH before any NaOH is added
[HCOOH] = 0.100 M
Using ICE table with simplifying assumption
pH = 2.37 (check this!)
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Titrations
pH after adding 5.00 mL of NaOH
• Use stoichiometry to calculate HCOOH and HCOO- after the
addition
− −
𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝑂𝐻(𝑎𝑞) → 𝐻2 𝑂 + 𝐻𝐶𝑂𝑂(𝑎𝑞)
Before Addition
Addition
After Addition
This is a buffer solution since moles of HCOOH ≈HCOO-
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Titrations
pH after adding 5.00 mL of NaOH
Use the H/H equation to calculate the pH of this buffer solution
𝑛𝐻𝐶𝑂𝑂−
𝑝𝐻 = 𝑝𝐾𝑎 + log
𝑛𝐻𝐶𝑂𝑂𝐻
5.00 × 10−4 𝑚𝑜𝑙
𝑝𝐻 = 3.74 + log( −3
)
2.00 × 10 𝑚𝑜𝑙
pH = 3.14
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Titrations
pH after adding 20.00 mL of NaOH
Calculations show this is still a buffer solution
Show that: nHCOOH = 5.00 x 10-4 mol ; nHCOO- = 2.00 x 10-3 mol
2.00 × 10−3 𝑚𝑜𝑙
𝑝𝐻 = 3.74 + log( −4
)
5.00 × 10 𝑚𝑜𝑙
pH = 4.34
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Titrations
pH after adding 25.00 mL of NaOH
This is the equivalence point, nacid = nbase
All HCOOH consumed and converted to HCOO- , not a buffer solution anymore
nHCOO- = 2.50 x 10-3 mol
Vsolution = 25.00 mL + 25.00 mL = 50.00 mL
[HCOO-] = 0.050 M
So what is the pH of a 0.050 M solution of HCOO- ?
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Titrations
What is the pH of a 0.050 M solution of HCOO- ?
𝐻𝐶𝑂𝑂−𝑎𝑞 + 𝐻2 𝑂 ⇌ 𝑂𝐻(𝑎𝑞)
−
+ 𝐻𝐶𝑂𝑂𝐻(𝑎𝑞)
Kb of HCOO- = Kw / Ka = 5.6 x 10-11
Using an ICE table calculation, show that [OH-] = 1.7 x 10-6 M ; pH = 8.23
Hence pH > 7 at the equivalence point for a weak acid / strong base titration
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Titrations
pH after adding 30.00 mL of NaOH
• Solution will be basic since nbase > nacid
− −
𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝑂𝐻(𝑎𝑞) → 𝐻2 𝑂 + 𝐻𝐶𝑂𝑂(𝑎𝑞)
Before Addition
Addition
After Addition
Volume of solution = 25.0 mL + 30.00 mL = 55.0 mL
[OH-] = 0.0091 M, pH = 11.96
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Titrations
Titration curve of a weak acid + strong base
NOTE: At the half-equivalence point , pH = pKa and nHA = nA-
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Solubility Equilibria
• Solubility of an ionic salt can be represented by an equilibrium process
Example:
𝐶𝑎𝐹2 𝑠 ⇌ 𝐶𝑎2+(𝑎𝑞) + 2 𝐹 − (𝑎𝑞)
• Equilibrium constant is the solubility product constant (Ksp)
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Solubility Equilibria
• Solubility product constants can be looked up in tables, specific for a given
temperature:
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Molar Solubility
• Molar solubility describes the solubility in moles (of solute) per litre
(of solution), not identical to the Ksp
• Molar solubility will depend on the presence of common ions in
solution
Example:
𝐴𝑔𝐶𝑙 𝑠 ⇌ 𝐴𝑔+ (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞) 𝐾𝑠𝑝 = 1.77 × 10−10
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Molar Solubility
• To calculate molar solubility from Ksp , construct an ICE table
Example: What is the molar solubility of AgCl in pure water?
Ksp (AgCl) = 1.77 x 10-10
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Molar Solubility
Example: What is the molar solubility of PbCl2 in pure water?
Ksp (PbCl2) = 1.17 x 10-5
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Molar Solubility – Common Ion Effect
Example: What is the molar solubility of CaF2 in a solution containing 0.100 M
NaF? Ksp (CaF2) = 1.46 x 10-10
• Must take into account the common-ion F- in ICE table setup
37
Molar Solubility – Common Ion Effect
Homework for you: Calculate the molar solubility of CaF2 in pure water and
compare it to the value from the previous slide
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Precipitation
• Mixing two salt solutions can cause precipitate to form if a
cation/anion combination produces an insoluble salt
• Quantitatively, precipitation can be predicted by comparing Q and
Ksp values
• If Q < Ksp, the solution is unsaturated
• If Q = Ksp, the solution is saturated
• If Q > Ksp, the solution is supersaturated
and precipitation occurs
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Precipitation
• Unsaturated solution: no solid present, dissolved ions present and
more solid will dissolve if added
• Saturated solution: solid and dissolved ions are both present, rate of
solvation = rate of precipitation
• Supersaturated solution: equilibrium shifts
left, solid precipitates out until Q = Ksp
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Predicting Precipitation
• To predict whether a precipitate will form, calculate the ion
concentrations after mixing the two solutions
• Make sure dilution (increase in volume) is taken into account when
mixing
• Calculate Q for the ion combination that may form a precipitate and
compare against Ksp to see if a precipitate will form
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Predicting Precipitation
Example: A solution containing Pb(NO3)2 is mixed with another containing NaBr
to form a solution that is 0.0150 mol L-1 in Pb2+ and 0.00350 mol L-1 in Br- . Will a
precipitate form? Ksp (PbBr2) = 4.67 x 10-6
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