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Buffers and Acid-Base Titrations

Reading: from chapter 18 of Petrucci, Harwood and Herring


(8th edition):
Required: Sections 18-2 through 18-6.
Recommended: Section 18-1.
Examples: 18-3 through 18-9.
Problem Set:
Chapter 18 questions: 5, 6, 7, 8, 9, 26, 27a-e, 32.
Additional problems from Chapter 18: 54, 55.

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Adding Base to a Weak Acid Solution
HF is a weak acid; it partially ionizes in water:
HF + H2O W H3O+ + F- pKa = 3.18
What effect does adding NaOH have on this equilibrium?
NaOH 6 Na+ + OH- complete ionization
H3O+ + OH- 6 H2O neutralization
Consequences:
C Adding NaOH consumes H 3O+.
C The HF equilibrium shifts to the right to partially
offset the change (replaces some H3O+).
C The increase in pH is less than if the same amount of
NaOH was added to pure water.
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Adding Acid to a Salt of a Weak Acid
NaF is a salt of a weak acid (HF). It hydrolyzes in water:
F- + H2O W OH- + HF pKb = 10.82
What effect does adding HCl have on this equilibrium?
HCl + H2O 6 H3O+ + Cl- complete ionization
H3O+ + OH- 6 H2O neutralization
Consequences:
C Adding HCl consumes OH-.
C The hydrolysis equilibrium shifts to the right to partially
offset the change (replaces some OH-).
C The decrease in pH is less than if the same amount of
HCl was added to pure water.
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Solution of a Weak Acid and its Salt
Example: Solution of HF and NaF in water.
HF + H2O W H3O+ + F- pKa = 3.18
C Adding acid shifts the equilibrium to the left. This
partially offsets the reduction in pH.
C Adding base shifts the equilibrium to the right. This
partially offsets the reduction in pH.
C Significant amounts of acid or base can be neutralized
since the solution contains substantial [HF] and [F -].
C The pH is kept nearly constant. This solution is a buffer.

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Applications of Buffer Solutions
Many chemical processes require control of pH.
C The rates and mechanisms of many chemical reactions
are sensitive to pH.
C pH affects the structure of and charges on proteins.
C The activity of enzymes is very sensitive to pH.
C Human blood is buffered to a pH of 7.4
C Many industrial chemical processes require a
controlled pH.

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Acid-Base Buffers
An acid-base buffer is a solution that is resistant to
changes in pH. In other words, when an acid or base is
added to a buffer, the pH changes only slightly.
For a solution to be a buffer, it must contain:
C comparable concentrations of a weak acid its conjugate
base:
0.1×[acid] < [conjugate base] < 10×[acid]
C a concentration of the conjugate base at least 100 times
the value of Ka for the acid:
[conjugate base] > 100 Ka

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pH of a Buffer Solution
Reaction HA + H 2O W H 3O + + A-
Initial [HA]0 - 0 [A-]0 M
Change -x - x x M
Equil. [HA]0-x - x [A-]0+x M
Simplifying assumptions: x n [HA]0 and x n [A-]0
Y Ka = [H3O+][A-]/[HA] . x [A-]0 / [HA]0
Y [H3O+] = x = Ka [HA]0 / [A-]0
Check that the assumptions are valid:
C Since [A-]0 > 100Ka, x < 0.01[HA]0.
C Since [A-]0 > 100Ka and [HA]0 < 10[A-]0, x < 0.1[A-]0.
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pH of a Buffer Solution - continued
In a buffer, we have:
[H3O+] = Ka [HA] / [A-]
Take the negative logarithm of both sides:
-log[H3O+] = -logKa - log([HA]/[A-])
pHbuffer = pKa + log([A-]/[HA])
This is called the Henderson-Hasselbalch equation.
C Relates the pH of a buffer to its composition.
C Uses initial concentrations of acid and conjugate base.
C Don't memorize - it is easy to mess up but easy to derive.

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Buffer Range
To have a buffer, we must have:
0.1 < [A-] / [HA] < 10
Taking logarithms:
-1.0 < log([A-]/[HA]) < 1.0
Substitute into the Henderson-Hasselbalch equation:
pHbuffer = pKa + log([A-]/[HA])
pHbuffer = pKa ± 1.0
Conclusion: A particular weak acid can used to prepare
buffers with pH values within 1 unit of the acid's pKa.

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Preparing Buffer Solutions
Chemists and biologists often need to prepare solutions
with a specific, constant pH.
To make a buffer with a specific pH:
C Find an acid with a pKa within 1 unit of the required pH.
C Use the acid ionization constant to determine the
required ratio of acid to conjugate base.
C Make the buffer solution.
C Use a pH meter to check the pH. Add acid or base as
needed to get the correct pH.

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Preparing a Buffer - Example
To prepare a buffer with pH = 3.50:
Acid pKa
Citric Acid 3.13 » Closest to desired pH.
Benzoic acid 4.20 Find ratio of acid to base:
Acetic acid 4.77 [HA]/[A-] = [H3O+]/Ka = 10pKA-pH
Carbonic acid 6.36 [HA]/[A-] = 103.13-3.50 = 0.43
Ammonium ion 9.25
if [A-] = 0.10 M (>100Ka)
Phenol 9.89 then [HA] = 0.043 M.
For one liter, use 0.143 mol H3C6H5O7 plus 0.100 mol NaOH.

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Adding Acids or Bases to a Buffer
Henderson-Hasselbalch equation:
pH = pKa + log([A-]/[HA])
C Adding an acid decreases [A -] and increases [HA]. So it
lowers the pH.
C Adding a base decreases [A -] and increases [HA]. So it
raises the pH.
C Qualitatively, this is just like any other solution. But in
a buffer, the pH changes are much smaller.
Q: How much does the pH change when acid or base is added?
A: Calculate the changes in [HA] and [A-].

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pH Change in a Buffer
Given a citric acid-citrate buffer with [A -]0 = 0.100 M,
[HA]0 = 0.043 M, and pH = 3.50 ([H3O+] = 3.16×10-4 M).
Find the pH after adding 3.0×10-3 mol HCl to 1.0 liter of
this buffer.
Solution: Calculate the changes in [HA] and [A-].
[A-] = [A-]0 - 3.0×10-3 M = (0.100-0.003) M = 0.097 M
[HA] = [HA]0 + 3.0×10-3 M = (0.043+0.003) M = 0.046 M
pH = pKa + log([A-]/[HA]) = 3.13 + log(0.097/0.046)
pH = 3.45 Y [H3O+] = 3.55×10-4 M
The change in [H3O+] equals 1.3% of the added HCl.
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Effect of Buffer Concentration
Given a citric acid-citrate buffer with [A -]0 = 0.100 M,
[HA]0 = 0.043 M, and pH = 3.50.
What happens to the pH if we double both [A-]0 and [HA]0?
Answer: No change since pH = pKa + log([A-]/[HA]).
(Only approximately true since we really should be using
activities instead of concentrations.)
However, the buffer capacity will increase, therefore:
C The effect of added acid or base will be smaller.
C More acid or base could be added before the buffer
stops working.

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Buffer Solutions - Summary
C A buffer solution contains a weak acid and the conjugate
base of that acid in comparable amounts.
C The acid neutralizes added base and the conjugate base
neutralizes added acid.
C A buffer dramatically reduces the pH changes produced
by adding an acid or base.
C The pH of a buffer is close to the pKa of the weak acid.
C The pH of a buffer solution is readily calculated from the
equilibrium condition
Ka [HA] = [H3O+][A-]

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Determining pH
Two widely used methods:
C A pH meter uses an electrode that produces a voltage
that is a linear in pH.
C Acid-base indicators change color depending on pH.
An indicator is a weak acid that has a different color
than its conjugate base.
HIn + H2O W H3O+ + In-
acid color base color
Acid color dominates for pH < pKa - 1.
Base color dominates for pH > pKa + 1.
Easy to use, but results are less precise.
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Acid-Base Indicator Examples
pH =
Phenolphthalein
pKa = 9.1

pH =
Bromthymol blue
pKa = 7.1

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Acid-Base Titrations
Acid-base titrations are used to analyze the quantity of acid
or base in an unknown sample.
Acid + Base W H2O + salt
At the equivalence point:
moles of acid = moles of base Y CAVA = CBVB
VA = volume of acid of unknown concentration CA
CB = known concentration of the base
VB = volume of base added at equivalence.
Y CA = CBVB / VA

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Acid-Base Titrations - continued
C The titrant is the strong acid or strong base solution that is
added in a measured volume.
C The equivalence point can be detected by using a pH meter.
C The end point is an experimental approximation of the
equivalence point, identified with an acid-base indicator.
C The titration error is the difference between the
equivalence point and the end point.
How close is the end point to the equivalence point?
What indicator should be used?

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Titration Curve of a Strong Acid

Titration of 25.00 ml of 0.100 M HCl with 0.100 M NaOH.


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pH during Titration of a Strong Acid
During the titration of a strong acid with a strong base:
C Initial pH is determined by the concentration of the acid.
C During the titration, the acid is gradually neutralized.
Before the equivalence point:
nA = CAVA, nB = CBVB, [H3O+] = (nA-nB) / (VA+VB)
C At the equivalence point: pH = 7.
C Beyond the equivalence point:
[OH-] = (nA-nB) / (VA+VB)
C What about near the equivalence point?

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pH near the Equivalence Point
Titration of 25.00 ml of 0.100 M HCl with 0.100 M NaOH.
At the equivalence point: VB = 25.00 ml and pH = 7.
Find the pH at VB = 24.95 ml (1 drop short of equivalence).
Solution:
nA = (25.00 ml)(0.100 M) = 25.00 mmol
nB = (24.95 ml)(0.100 M) = 24.95 mmol
[H3O+] = (0.05 mmol) / (49.95 ml) = 0.0001 M
Y pH = 4
By same method, one drop past equivalence, pH = 10.
Conclusion: Near equivalence, pH changes very rapidly.
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Titration of a Weak Acid
C The titrant must be a strong base.
C The initial pH is determined by the concentration and
pKa of the acid.
C During the titration, the acid is gradually converted to
its conjugate base. The solution is a buffer.
C At the equivalence point, the solution contains only a
salt of the conjugate base, so pH >7.
C There is a less dramatic pH change near the equivalence
point. Indicators must be chosen with care.

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Titration Curve of a Weak Acid

25.0 ml of 0.100 M HC2H3O2 titrated with 0.100 M NaOH.


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pH during Titration of a Weak Acid
Titrating 25.00 ml of 0.100 M acetic acid (HC2H3O2,
pKa = 4.74) with 0.100 M NaOH.
C Initial pH:
HA + H2O W H3O+ + A-
[H3O+] = [A-] = x [HA] . CA = 0.100 M
x2 = Ka [HA] Y x = 1.35×10-3 M Y pH = 2.87
C Buffer region (10% to 90% neutralized):
pH = pKa + log([A-]/[HA]) = pKa + log(nB/(nA-nB))
where nA = CAVA, nB = CBVB
C At the half-equivalence point: pH = pKa = 4.74

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Titration of a Weak Acid - continued
C At the equivalence point:
The solution is that of a salt of the conjugate base.
This hydrolyzes:
A- + H2O W HA + OH-
Kb = KW/Ka = [HA][OH-]/[A-] = x2/[A-]
[A-] . nA/(VA+VB) = CACB/(CA+CB) = 0.0500 M
x2 = Kb[A-] Y x = 5.24×10-6 M Y pOH = 5.28
Y pH = 8.72 Suitable indicators: thymol blue (pKa=8.8)
phenolphthalein (pKa=9.1)
C Beyond the equivalence point, the pH is determined by
the amount of excess base.

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Titration Curve of a Weak Polyprotic Acid

Titrating 10.0 ml of 0.100 M H3PO4 with 0.100 M NaOH.


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pH during Titration of a Polyprotic Acid
C Initial pH: Same as for a monoprotic acid.
C Buffer regions: There are two or more, with pH.pKa1,
pH.pKa2, etc.
C Last equivalence point: Same as for a monoprotic acid.
C Earlier equivalence points: Not so simple.
Example: For H3PO4 at its first equivalence point, there
are significant amounts of H 3PO4, H2PO4-, and HPO42-.
H3PO4 + H2O W H3O+ + H2PO4- pKa1 = 2.15
H2PO4- + H2O W H3O+ + HPO42- pKa2 = 7.20
Expect pKa1 < pH < pKa1 (small [H 3O+] and [OH-])

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Equivalence Point of a Polyprotic Acid
Find the pH at the first equivalence point of H3PO4.
Solution: Two equilibria - use the general method.
Significant species: H3PO4, H2PO4-, HPO42-, H3O+ (pH<6)
Material balance: [H3PO4] + [H2PO4-] + [HPO42-] / M
Equilibrium constants:
[H2PO4-] = Ka1[H3PO4]/[H3O+]
[HPO42-] = Ka2[H2PO4-]/[H3O+] = Ka1Ka2[H3PO4]/[H3O+]2
Electroneutrality: [Na+] + [H3O+] = [H2PO4-] + 2[HPO42-]
At equivalence: M = [Na+] . [H2PO4-] + 2[HPO42-]
Four equations, four unknowns.
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Polyprotic Acid - continued
Substitute into material balance:
M = [H3PO4]( 1 + Ka1/[H3O+] + Ka1Ka2/[H3O+]2 )
Substitute into electroneutrality:
M = [H3PO4]( Ka1/[H3O+] + 2Ka1Ka2/[H3O+]2 )
Subtract electroneutrality from material balance:
0 = 1 - Ka1Ka2/[H3O+]2 Y [H3O+] = (Ka1Ka2)½
Y pH = (pKa1+pKa2)/2 = (2.15+7.20)/2
pH = 4.68

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Acid-Base Titrations - Summary
C Acid-base titrations can be used to measure the
concentrations of acid or base in solution.
C The pH changes rapidly at the equivalence point.
C The equivalence point can be determined by using a
pH meter or estimated by using an acid-base indicator.
C The appropriate indicator to use depends on the pKa (or pKb)
of the acid (or base) being titrated.
C A titration curve can be used to determine the pKa of a weak
acid (or pKb of a weak base).

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CO2 in the Atmosphere and Oceans
The partial pressure of CO2 in the atmosphere is increasing.
C Pre-industrial: 2.8×10-4 atm
C Present: 3.7×10-4 atm
C Future: doubled? tripled? more?
CO2 can dissolve in water and act as an acid:
CO2(g) W CO2(aq) Keq = 0.046
CO2(aq) + 2H2O(l) W H3O+ + HCO3- pKa1 = 6.05
HCO3- + H2O(l) W H3O+ + CO32- pKa2 = 9.23
These equilibrium constants are for seawater at 15 °C.
What is the impact of increased CO2 on the oceans?

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Why the Sea is Salt
Rainwater is slightly acidic, pH - 5.
Rainwater gradually dissolves rocks (mostly as ions).
Dissolved material is washed into the oceans.
Water evaporates from the oceans, dissolved material is
left behind along with primordial Na+ and volcanic Cl-.
Composition of seawater:
C Major cations: Na+, K+, Mg2+, Ca2+
C Major anions: Cl-, SO42-, HCO3-, Br-, CO32-
C The atmosphere directly influences HCO3- and CO32- in
seawater. pH is a key factor.

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pH of Seawater
Significant species: CO2(aq), HCO3-, CO32-, H3O+
Electroneutrality: sum of '+' charges = sum of '-' charges
[Na+] + [K+] + ... = [Cl-] + ... + [HCO3-] + 2[CO32-]
[Na+], [K+], [Cl-], etc. are constant, so [HCO3-]+2[CO32-]
is a constant called the alkalinity:
[Alk] / [HCO3-] + 2[CO32-]
Equilibrium conditions: [CO2(aq)] = Keq PCO2
[HCO3-] = Ka1[CO2(aq)][H 3O+]-1 = Ka1KeqPCO2[H3O+]-1
[CO32-] = Ka2[HCO3-][H3O+]-1 = Ka1Ka2KeqPCO2[H3O+]-2
Four equations, four unknowns (PCO2 is assumed known).
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pH of Seawater - continued
Substitute into expression for alkalinity:
[Alk] = Ka1KeqPCO2[H3O+]-1 + 2Ka1Ka2KeqPCO2[H3O+]-2
[H3O+] = Ka1KeqPCO2 (1 + 2Ka2/[H3O+]) / [Alk]
For seawater: [Alk] . 2.0×10-3 M. Constants given earlier.
Simplifying assumption: [H3O+] o 2Ka2 = 1.2×10-9
Y [H3O+]approx = Ka1KeqPCO2 / [Alk] = (2.05×10-5 atm-1)PCO2
Results PCO2 (atm) [H3O+]approx [H3O+]iterate pH
pre-industrial 2.8×10-4 5.7×10-9 M 6.7×10-9 M 8.17
doubled CO2 5.6×10-4 1.1×10-8 M 1.3×10-8 M 7.90

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Acidification of the Oceans
Does it matter? Yes, especially if you are a coral.
Shells and skeletons are made largely of CaCO3, which is
slightly soluble:
CaCO3(s) W Ca2+ + CO32-
In seawater, Q > K, so organisms can extract CaCO3. If
CO32- decreases, this become more difficult.
We have [CO32-] = Ka1Ka2KeqPCO2 / [H3O+]2
and [H3O+] . Ka1KeqPCO2 / [Alk]
so [CO32-] . Ka2[Alk]2 / (Ka1KeqPCO2)
Conclusion: More CO2 in the atmosphere means lower
[CO32-] in the oceans. Possible problem for marine life.
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