The most

Buffers
Buffers and Titrations Highly resistant to changes in pH brought
important pH
buffer system in
the blood
about by addition of strong acid or strong base involves
carbonic acid (a
Made from: weak acid
A weak acid and a salt containing its formed from the
carbon dioxide
conjugate base dissolved in
blood) and
A weak base and a salt containing its bicarbonate ions
conjugate acid (the
corresponding
The presence of the salt “suppresses” the conjugate base)
dissociation of the weak acid further (related
to Le Chatelier’s Principle)(see next slide for
example)
Best range of buffering ability occurs when the
pH to be buffered is close to the pKa of the
weak acid being used.

Example: (Suppression of Acid Dissociation) How Conjugate Acid-

Acid-Base Pairs Work as Buffers
Calculate the hydronium ion concentration and pH for:
a) A solution containing only .200M acetic acid. Given a weak acid (HA) and a salt containing its
b) A solution containing .200M acetic acid and 0.100M conjugate base (A-)
sodium acetate. Na+ is a spectator ion. Example: acetic acid (HC2H3O2) and sodium
acetate (NaC2H3O2)
The Ka for acetic acid is 1.8x10-5
If a strong base (such as NaOH) is added:
HA(aq) + OH-(aq) → A-(aq) + H2O(l)
Answer:
a) 1.8x10-5 = (x)(x)/(.200M-x) (H+)(C2H3O2-)/(HC2H3O2) If a strong acid (such as HCl) is added:
x = 1.89x10-3 pH=2.72 H3O+(aq) + A-(aq) → HA(aq) + H2O(l)

b) 1.8x10-5 = (x)(x+.100)/(.200M-x)
x = 3.60x10-5 pH=4.44
Note that there is much less hydronium (x) in this
solution

Visual Interpretation of Buffer Systems “Exhausting”

Exhausting” a Buffer:
(Using acetic acid / acetate) When making a buffer solution, the molarity of the
conjugate acid-base pair must be high enough to buffer
the anticipated strong acid / strong base that might be
added
If a buffer component runs out, the pH will change
drastically.

IMPORTANT NOTE: Buffers do not keep the pH of

solutions from changing when strong acids or bases are
added. They only “minimize” the effect of the acid or
base.

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 Buffers and the Henderson-Hasselbalch Equation
Steps for producing a
buffer solution
[ H 3O + ][ A− ] Why is it best to use a weak
acid with a pKa close to the
Ka = pH? Can you see why from
[ HA] the Henderson-Hasselbalch
equation.

K [ HA]
[ H 3O + ] = a −
[A ]
[ A− ] Henderson-Hasselbalch
pH = pK a + log Equation

[ HA]

Example: Example:
A student wants to prepare a buffer for a solution at pH Determine the pH of a buffer solution that is .115M in
= 3.2. Which of the following combinations would be sodium acetate and .100M in acetic acid (Ka = 1.8x10-5)
best to use?
Is this solution better at buffering acids or bases?
HClO; LiClO Ka = 2.8x10-8
HSO4-; K2SO4 Ka = 1.0x10-2 Answer:

HF; NaF Ka = 6.9x10-4 pH = pKa + log ([C2H3O2-]/[HC2H3O2])

HC2H3O2; NaC2H3O2 Ka = 1.8x10-5 pH = 4.74 + log(.115/.100)

pH = 4.80
Answer: The HF; NaF combination has a pKa (= 3.16) Since the buffer has a higher concentration in acetate
that is closest to the solution pH and would therefore be ion (the conjugate base), it will be better at buffering
best. acids.

A 500.mL volume of a solution is 0.500M in both formic Acid-Base Indicators

acid and potassium formate. Calculate the before and
after pH of the solution if 40.0mL of .500M HCl is
added to the solution. Ka for formic acid (HCHO2) is
1.9x10-4
Answer:
pKa = -log(1.9x10-4) = 3.72
Before: pH = 3.72 + log(.500/.500) = 3.72

After:
Mol HCl = (.0400L)(.500M) = .0200mol HCl
Mol formic acid = (.500L)(0.500M) + .0200 = .27mol
Mol formate = (.500L)(0.500M) - .0200 = .23mol
pH = 3.72 + log(.23/.27) = 3.65
Substances (usually weak organic acids or bases) that change color at different pH
levels. Useful for identifying specific pH values in solution.

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 Acid-Base Titrations Titration
Titration: Quantitatively determining the concentration
of a solution by reacting it with another solution of
Apparatus Burette
filled with
titrant
precisely known concentration.
Terminology
Titrant: The solution of known concentration used to
Stopcock valve
titrate a volume of the solution of unknown
concentration. Flask
filled with
Standardized (standard) solution: Solution of precisely sample to
known concentration be titrated
and
Equivalence point: The point at which stoichiometrically indicator
equivalent amounts of reactants have reacted
Endpoint: The point where an indicator (such as pH)
changes color. Note: Burettes are designated TD (to Deliver)

Titrations Involving Strong Acids and Answer:

Strong Bases NaOH + HCl → NaCl + H2O
The pH at the equivalence point is 7 (neutral) Moles of base used:
The salt formed in the neutralization has no strength (.0150M)(.0300L) = 4.50x10-4mol
as a conjugate acid or base Since the ratio is 1:1, there were 4.50x10-4mol of acid
Moles of acid vs. base are calculated using titrated
stoichiometry and the balanced chemical equation for The molarity of the acid is
the neutralization
4.50x10-4mol / .0150L = .0300M
Example:
In a titration, a 15.0mL sample of an unknown molarity
hydrochloric acid is titrated with .0150M NaOH to the
equivalence point. If 30.0mL of the base was used,
what is the molarity of the HCl?

Titration curve for Example:

strong acid titrated A 60.0mL sample of strontium hydroxide is titrated with
with a strong base .200M hydrobromic acid. If 43.5mL is used in the
titration, what is the molarity of the strontium
Note: The colored
hydroxide?
spheres denote
indicator endpoints
Answer:
PP = phenolphthalein
2HBr + Sr(OH)2 → SrBr2 + 2H2O
BB= bromthymol blue
MR = methyl red Moles acid used: (.0435L)(.200M) = 8.70x10-3mol
Moles of Sr(OH)2 titrated = (8.70x10-3)(1/2) = 4.35x10-3mol
Molarity = 4.35x10-3mol/.0600L = .0725M

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Example: Answer:
In making a solution for a titration lab, a teacher a) Balanced Neutralization Equation:
dissolves a certain amount of potassium hydroxide into KOH(aq) + HCl(aq) → KCl(aq) + H2O(l)
enough water to make 700.mL of solution. The teacher
Moles of HCl used in titration:
forgets how much potassium hydroxide they put in and
(.0125M)(.0355L) = 4.44x10-4mol HCl
asks a student to titrate a 15.0mL sample with a
Moles of KOH titrated:
.0125M standardized hydrochloric acid solution. The
4.44x10-4mol HCl (1mol KOH/1molHCl) = 4.44x10-4mol
phenolphthalein indicator reaches its endpoint after
KOH
35.5mL of the titrant is delivered.
Molarity of KOH = (4.44x10-4mol)/(.0150L)= .0296M
a) What is the molarity of the potassium hydroxide
solution?
b) Grams of KOH in 700.mL
b) How many grams of potassium hydroxide were (.0296mol/L)(.700L)(56.11g/mol) = 1.16g KOH
contained in the original 700.mL of solution?

Titration curve for weak Example:

acid titrated with a
In a titration experiment, a 20.0mL sample of nitrous
strong base
acid (Ka = 6.00x10-4) was titrated using sodium
Note pH (basic) at the hydroxide
equivalence point due
a) What is the pH of the solution at the halfway point in
to conjugate base
the titration?
activity from the weak
acid. b) If the endpoint is achieved using 18.2mL of .100M
sodium hydroxide, what is the final pH of the solution?
At the midpoint of the
titration [A-] = [HA] c) What is the name of the salt that is formed in this
Note difference in pH = pKa + log ([A-]/[HA]) neutralization?
curve shape due to
“buffering” from pH = pKa d) Which of the three indicators listed in your textbook
conjugate base (p387 table 14.2) would be best for this titration; methyl
red, bromthymol blue or phenolphthalein?

Titration curve for weak

Answer: base titrated with a
a) pH at halfway point is given by pH = pKa strong acid
pH = -log(6.00x10-4) = 3.22 Note pH (acidic) at the
equivalence point due to
b) Mol NaOH used = (.0182L)(.100M) = .00182mol conjugate acid activity from
This equals moles of NO2- (1:1 mole ratio) the weak base.
molarity of nitrite ion = (.00182mol)/ (.0382L) = .0476M pH = pKa + log ([A-]/[HA])
Kb(nitrite ion) = 1.00x10-14/6.00x10-4 = 1.67x10-11 Or
1.67x10-11 = (x)(x)/(.0476-x) x = [OH-] = 8.91x10-7 pOH = pKb + log ([HA]/[A-])
pOH= -log(8.91x10-7) = 6.05
pH = 14.00-6.05 = 7.95
At the midpoint of the titration
c) Sodium nitrite [Base] = [Conj Acid]
d) Bromthymol blue (endpoint pH =7) would be best, but pH = pKa
phenolphthalein (endpoint pH =9) could be used as well.
Where the Ka is the constant
for the conjugate acid of the
base

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 Answer:
Example:
a. Moles of acid added: (.200M)(.0200L) = .004mol
A 100.mL sample of .200M ammonia (Kb = 1.8x10-5) is (This is also moles of conjugate acid produced)
titrated with .200M hydrobromic acid. Calculate the Moles of base remaining: (.100L)(.200M) - .004mol =
pH: .016mol
a. After 20.0mL of acid has been added Ka of conjugate acid (NH4+) = 1.0x10-14/1.8x10-5 =
5.6x10-10
b. At the midpoint of the titration
pH = pKa + log ([Base]/[Conj acid])
c. Of the salt solution (ammonium bromide) at the = 9.26 + log (.016/.004) = 9.857 = 9.9
equivalence point.

b. At the midpoint, pH = pKa of the conjugate acid:

pH = -log(5.6x10-10) = 9.26 = 9.3

Titration Curves for Polyprotic Acids

c. Since the molarities of acid and base are the same,
it will take 100.mL of the hydrobromic acid to titrate all
This shows the
of the base. Since the total volume will be 200.mL, the titration curve
components of the salt (ammonium and bromide) will for a diprotic
both be ½ their original molarities or .100M NH4Br. acid.

The bromine is a spectator ion (conjugate base of a Note that there

is a separate
very strong acid). The ammonium ion (the conjugate
equivalence
acid of a weak base) will react in water: point for each
NH4+(aq) + H2O(l) ↔ NH3(aq) + H3O+(aq) titrated
hydrogen on the
5.6x10-10 = [H3O+][NH3]/[NH4+] polyprotic acid.
5.6x10-10 = (x)(x)/(.100-x) x = 7.0x10-6
pH = -log(7.0x10-6) = 5.15 = 5.2

Extra Practice Problems A 5.00g quantity of a diprotic acid was dissolved in

The pH of blood plasma is 7.40. Assuming the water to make 250.mL of solution. Calculate the molar
principal buffer system is HCO3-/H2CO3, calculate the mass of the acid if 25.0mL of this solution required
ratio [HCO3-]/[H2CO3]. Is this buffer more effective 11.1mL of 1.00M KOH for neutralization. Assume both
against an added acid or an added base? (Ka for H2CO3 protons were titrated.
= 4.4x10-7)
Answer:
Answer:
Moles KOH used: (.0111L)(1.00M) = .0111mol KOH
Ka of H2CO3 = 4.4x10-7 pKa = 6.36 Moles H+ titrated: 1:1 = .0111mol H+
pH = pKa + log ([HCO3-]/[H2CO3]) Moles of acid: .0111mol H+ (1mol acid / 2mol H+) =
7.40 = 6.36 + log ([HCO3-]/[H2CO3]) .00555mol acid
1.04 = log ([HCO3-]/[H2CO3]) Molarity of acid: (.00555mol)/(.0250L) = .222M
101.04 = [HCO3-]/[H2CO3] = 10.96:1
11:1 Moles acid in 250.mL: (.222M)(.250L) = .0555mol acid
Since it is higher in bicarbonate concentration it is Molar Mass (g/mol) = (5.00g)/(.0555mol) = 90.1g/mol
somewhat better at buffering against acids.