Experiment 7: Titration – Acid/Base Equilibrium and Buffers

PURPOSE In the first part of this experiment, your goal is to develop a titration curve for a weak acid, HC2H3O2,
with a base of known concentration. The reaction equations are shown below in net ionic form.

HC2H3O2(aq) + OH– (aq) → H2O(l) + C2H3O2– (aq)

Alternative chemical formula:
CH3COOH (aq) + OH– (aq) → H2O (l) + CH3COO– (aq)

You will use a pH meter as you titrate. The region of most rapid pH change will then be used to determine the
equivalence point. The volume of NaOH titrant used at the equivalence point will be used to determine the pKa and
the ionization constant (Ka) of the weak acid.

During the second part of the experiment, you will prepare a buffer composed of acetic acid and sodium acetate and
test the buffering capacity of the buffer with small amounts of strong acid and strong base.

OBJECTIVES
In this experiment, you will
1) Perform dilution calculations
2) Accurately conduct weak acid-strong base titration.
3) Determine the equivalence point of a weak acid-strong base titration.
4) Calculate the pKa and Ka of the weak acid.
5) Prepare and test an acid buffer solution.
6) Determine the buffer capacity of the prepared buffer.

PRINCIPLES
Dilutions
It is often necessary in a lab procedure to perform a dilution of a concentrated solution to a less concentrated
solution. The relationship M1V1 = M2V2 is the appropriate relationship for dilution calculations:

M 1V 1 = M 2V 2
• M1 = the initial (more concentrated) solution.
• V1 = the volume of M1 used in the dilution.
• M2 = the final (less concentrated) solution.
• V2 = the final volume (V1 + the volume H2O added to V1)

Example 1: If 10.0 mL of 12.0 M HCl is added to enough water to give 100. mL of solution, what is the
concentration of the solution?

M 1V1 = M 2 V2
M 1 = 12.0M
12.0 M × 10.0 mL = M 2 × 100.0 mL
V1 = 10.0 mL
12.0 M × 10.0 mL
M2 =? M2 =
100.0 mL
V2 = 100.0 mL = 1.20 M

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Example 2: What volume of 18.0 M sulfuric acid is required to make 2.50 L of a 2.40 M sulfuric acid solution?
What volume of water is added to make the 2.40 M sulfuric solution?

M 1 = 18.0M M 1 V1 = M 2 V2
V1 = ? mL M 2 × V2
V1 =
M1
M 2 = 2.40 M
2.50 L × 2.40 M
V2 = 2.50 L V1 =
18.0 M
= 0.333 L or 333 mL

Volume of H2O added: 2.50 L – 0.333 L = 2.17 L

Weak acid equilibria

Weak acids and bases ionize or dissociate partially, much less than 100%. Let’s look at the dissolution of acetic
acid, a weak acid, in water as an example. The equation for the ionization of acetic acid is:


→ CH 3COO − ( aq ) + H 3O + ( aq )
CH 3COOH ( aq ) + H 2O( l ) ←


The equilibrium constant for this ionization is expressed as:

 H 3O +  CH3COO − 
Kc = 
[CH3COOH ][ H 2O]

The water concentration is many orders of magnitude greater than the ion concentrations. Thus the water
concentration is essentially that of pure water. Recall that the activity of pure water is 1.

 H3O+  CH3COO− 
Kc [ H2O] = 
[CH3COOH]
 H3O+  CH3COO− 
K ≈ 
[CH3COOH]

We can define a new equilibrium constant for weak acid equilibria that uses the previous definition.
This equilibrium constant is called the acid ionization constant. The symbol for the ionization constant is Ka.

 H 3O +  CH 3COO − 
Ka =  = 1.8 × 10 −5
[CH 3COOH ]
for acetic acid

In simplified form the dissociation equation and acid ionization expression are written as:

→ H 3O+ + CH 3COO ─

CH 3COOH ←


 H 3O+  CH 3COO ─ 

Ka =  = 1.8×10 ─ 5
[CH 3COOH ]

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The generic version of a weak acid dissociation equation and weak acid ionization expression are written as:
→ H 3O + + A ─

HA ←


 H 3O +   A ─ 
Ka = 
[ HA ]
Where HA represents any weak acid and H3O+ represents the hydronium ion and A- is the strong conjugate base of
the weak acid.

Example: The pH of a 0.10 M solution of a weak monoprotic acid, HA, is found to be 2.97. What is the value for
its ionization constant?
pH = 2.97 therefore [H+] = 10–pH

 H 3O +  =10 −2.97
 H 3O +  =1.1×10−3 M

We can eliminate the concentration of hydrogen ions that are produced from the acid because it is very small
compared to the original concentration of the acid.

HA 
→
←
 H 3 O + + A−
Equil. []'s ( 0.10-1.1× 10-3 ) 1.1× 10-3 1.1× 10-3
≈ 0.10
Calculate the ionization constant from this information.

 H 3O +   A〡  (1.1×10〡 ) (1.1×10〡 )
3 3

Ka = =
[ HA ] ( 0.10 )
K a = 1.2×10〡5

Buffers
In many systems, buffers are critical. Blood plasma, a natural example in humans, is a bicarbonate buffer that keeps
the pH of blood between 7.2 and 7.6. A buffer is a mixture of a weak acid and its conjugate base (a soluble salt of
the weak acid), or a weak base and its conjugate acid (the soluble salt of the weak base). A buffer’s function is to
absorb acids (H+ or H3O+ ions) or bases (OH– ions) so that the pH of the system changes very, very little.

The Common Ion Effect and Buffer Solutions

If a solution is made in which the same ion is produced by two different compounds, the common ion effect is
exhibited. Buffer solutions are solutions that resist changes in pH when acids or bases are added to them due to the
common ion effect.
There are two common kinds of buffer solutions:
1. Solutions made from a weak acid plus a soluble ionic salt of the weak acid.
2. Solutions made from a weak base plus a soluble ionic salt of the weak base.

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Example: Buffer composition

CH3COOH (aq) + NaCH3COO


→ CH 3COO − (aq ) + Na + ( aq )
CH 3COOH ( aq ) ←


NH3 (aq) + NH4Cl


NH 3 (aq) ←→ NH 4+ (aq ) + Cl − (aq)


One example of this type of an acid buffer system is:

The weak acid - acetic acid CH3COOH
The soluble ionic salt - sodium acetate NaCH3COO

There are two sources of acetate ions (CH3COO−). The acetic acid (the weak acid), which undergoes very little
ionization will contribute a very small amount of acetate ions in the buffer solution. Adding the salt of acetic acid,
sodium acetate, on the other hand , produces a relatively high concentration of acetate ions in the buffer solution.

The pH of the buffer solution (weak acid + salt of weak acid) is less acidic than a solution just comprised of the
weak acid alone. Adding additional acetate ions to a solution that is in equilibrium will cause the increase of
CH3COO− to react with the H3O+ and shift the equilibrium to the left to reform CH3COOH.


→
CH 3COOH ← H 3O
+
+ CH 3COO − + additional CH 3COO −
( from weak acid ) ( from salt of weak acid )
weak acid conjugate base conjugate base

H 2O
NaCH 3COO  → Na + + CH 3COO − ⇒ 100%
add to
H 2O

CH 3COOH + ← → H 3O + + CH 3COO − ⇒ K a = 1.8 x 10−5

By design, a buffer is an equilibrium system. For example, a buffer can be prepared with hydrofluoric acid, HF and
sodium fluoride. The weak acid and the salt of the weak acid establish an aqueous equilibrium as shown below.

H2O
HF (aq) + NaF 
← → H3O + (aq) + F– (aq) + Na+ (aq)

The equilibrium constant expression is shown below.

[H 3O + ][F− ]
Ka =
[HF]

Calculations with buffered solutions:

Example: What is the pH and [H3O+] of a solution that is 0.20 M HF and 0.10 M NaF? The ionization constant for
the weak acid (hydrofluoric acid) is: Ka = 7.2 x 10−4

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

NaF H 2O
→ Na + + F− ⇒ 100%
0.10 M 0.10M 0.10 M

H O
HF + ←
2
→ H 3O + +
 F− ⇒ K a = 7.2 x10−4
(0.20 − x) M + xM + xM
_______________________________________
(0.20 − x) M + x M + (0.10 + x) M

Since the ionization constant (10−4) is very small relative to the concentration of hydrofluoric acid and the fluoride
ion, we can eliminate the unknown amount of ionization (x) from HF and from the [F−] provided by the salt.

[H 3O + ][F− ] x (0.10 + x)
\ Ka = = 7.2 × 10−4 =
[HF] (0.20 − x)

7.2 ×10 −4 =
( 0.10 ) x
0.20
0.00144 M = x = [ H 3O + ]
pH = 2.84

What is the difference in pH if no sodium fluoride is added to a 0.20 M hydrofluoric acid solution?
H2 O

HF + ← → H3O+ + F− ⇒ Ka = 7.2x10−4
(0.20 − x) M + xM + xM
(0.20 − x) M + xM + xM

[H 3O + ][F− ]
Ka = pH = − log [H 3O + ]
[HF]
−4 ( x )( x ) = − log (1.2 x 10−2 )
7.2 × 10 =
0.20 = 1.92
0.012 = x
0.012 = x = [H 3O + ]

The ΔpH = 2.84 (buffered sol’n) – 1.92 (weak acid solution) = 0.92

As can be seen, the buffered solution is not as acidic as the solution made with only hydrofluoric acid.

Henderson-Hasselbalch Equation for Buffers

A variation of the equilibrium expression above, called the Henderson-Hasselbalch equation, is the best reference in
preparing a buffer solution.

[conjugate base]
pH = pKa + log
[acid]
⇒ for buffers with weak acids and salts of weak acids

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

[conjugate acid]
pOH = pK b + log
[base]
⇒ for buffers with weak bases and salts of weak bases

For buffered solutions:

• [acid] = [weak acid]
• [conjugate base] = [salt of the weak acid] (Remember that the conjugate base is mostly contributed by the
salt of the weak acid.)

• [base] = [weak base]

• [conjugate acid] = [salt of the weak base] (Remember that the conjugate acid is mostly contributed by the
salt of the weak base.)

For our hydrofluoric acid/sodium fluoride buffer example, the Henderson-Hasselbalch equation is shown below.

[F- ] moles/liter or moles

pH = pKa + log
[HF]

For example: Question (from above), what is the pH and [H3O+] of a solution that is 0.20 M HF and 0.10 M NaF?
[acid] = [weak acid]
[HF] = 0.20 M
[conjugate base] = [salt of the weak acid]
[F−] = [NaF] = 0.10 M
Ka (HF) = 7.2 x 10−4
pKa = – log Ka = − log (7.2 x 10−4) = 3.14

[conjugate base] [H3O+ ] = 10−pH

pH = pKa + log
[acid] = 1.4 × 10−3
 0.10 
= 3.14 + log  
 0.20 
= 3.14 + ( −0.30 )
= 2.84
The pH range in which a buffer solution is most effective is generally considered to be ±1 of the pKa.

In this experiment, you will use the Henderson-Hasselbalch equation to determine the amount of acetic acid and
sodium acetate needed to prepare an acidic buffer solution. You will then prepare the buffer and test its buffer
capacity by adding solutions of NaOH and HCl.

Buffering Action
Weak acids and the salt of weak acids
• When a small amount of a strong acid or strong base is added to a buffer solution, the pH of the solution
will not change very much.
• The buffer solution is able to react with the additional H3O+ or OH− ions that may be added.
• This buffering action is due to the increased concentration of conjugate acid ions or conjugate base ions
that are available once the solution has established equilibrium.

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H O

2
CH 3COOH ( aq ) ← →
 CH 3COO − ( aq ) + H 3O + ( aq )
144 42444 3 1442443
high conc . from weak acid high conc . from salt of weak acid

If we add a strong acid, such as HCl, the following occurs:

HCl → H3O+ + Cl– ≈

100%
+
CH3COOH → H3O + CH3COO−

The increase in [H3O+] causes a shift to the left and more CH3COOH is formed. Since there is a sufficiently high
[CH3COO−], almost all of the additional H3O+ is used up.

If we add a strong base, such as NaOH, it will be consumed by the weak acid:

NaOH → OH− + Na+ ≈ 100%

+
CH3COOH → H3O + CH3COO−

The added OH− ions react with the H3O+ ions to form water.

OH− + H 3 O + ⇌ 2 H 2O

The decrease in [H3O+] causes a shift to the right and more CH3COO− is formed. Since there is a sufficiently high
[CH3COOH], almost all of the added OH− is used up.

Example: If 0.020 mole of gaseous HCl is added to 1.00 liter of a buffer solution that is 0.100 M in aqueous
ammonia and 0.200 M in ammonium chloride, how much does the pH change? Assume no volume change due to
addition of the HCl.

1. Calculate the pH of the original buffer solution.

NH 4 Cl ( aq ) 
→ NH 4+ ( aq ) + Cl − ( aq ) ⇒ approximately 100%
0.200 M 0.200 M 0.200 M
H 2O

→ NH ( aq ) + OH −
NH 3 ( aq ) ←

+
4

0.100 M +x +x
( 0.100 − x ) M ( 0.200 + x ) M + x
x <<< [NH3] and [NH4+]
[ salt ]
pOH = pKb + log
[base]
 0.20 
= 4.744 + log  
 0.10 
= 5.05
pH = 8.95

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2. Next, calculate the concentration of all species after the addition of the gaseous HCl.
• The HCl will react with the hydroxide ion to produce water and lower the [OH–]. The equilibrium will
shift to the right to increase the [OH–]. This is another limiting reactant problem.

H O
→
NH 3 ( aq ) ←
2
NH 4+ ( aq ) + OH −
H 2O
H 3O +

Overall: HCl + NH 3 → NH 4 Cl
Initial 0.020 mol 0.100 mol 0.200 mol
Change 〡0.020 mol 〡0.020 mol + 0.020 mol
After rxn. 0 mol 0.080 mol 0.220 mol
0.080 mol
M NH3 = = 0.080 M
1.0 L
0.220 mol
M NH4Cl = = 0.220 M
1.0 L

3. Using the concentrations of the salt and base and the Henderson-Hassselbalch equation, the pH can be
calculated.
[salt]
pOH = pKa + log
[base]
[0.220]
= 4.74 + log
[0.080]
= 5.18
pH = 8.82

Finally, calculate the change in pH.

ΔpH = pH new − pH original

= 8.82 − 8.95
= − 0.13

Buffer solutions may be prepared by mixing solutions of a weak acid with a solution of a salt of the weak acid or
mixing a weak base with a solution of a salt of a weak base. In both instances, the volumes of the mixed solutions
are additive and the concentrations of the solutes change.

For biochemical situations, it is often important to prepare a buffer solution of a given pH.

Example: Calculate the mass of solid ammonium chloride, NH4Cl, which must be used to prepare 1.00 L of a buffer
solution that is 0.10 M in aqueous ammonia, and that has a pH of 9.15.

Because pH = 9.15, the pOH can be determined.

pOH = 14.00 − 9.15 = 4.85

OH -  = 10 −4.85 = 1.4 ×10−5 M

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The appropriate equilibria representations are:

H2 O
NH 3 
← → NH 4+ + OH −
( 0.10 − 1.4 ×10 ) M
−5
1.4 × 10−5 M 1.4 × 10 −5 M
NH 4Cl → NH 4+ + Cl −
xM xM xM
-5 -5 -5
(0.10 – 1.4 × 10 )M (1.4 x 10 + x )M + 1.4 × 10 M

Very small compared to Very large compared to the ionized

the nonionized species species from the weak base

[NH3] = 0.10M The number of moles of NH3 that is lost after equilibrium has been established is very small
compared to the original number of moles of NH3; therefore, we can apply the simplifying assumption that the
concentration of NH3 remains 0.10M.

[NH4+] = x The number of moles of the ammonium ion that is contributed by the NH4Cl is much larger than the
number of moles of NH4+ contributed by ionization of NH3; therefore, we will let x (mol/L) equal the concentration
of NH4Cl needed to make the buffer solution.

Kb = 1.8×10-5
pKb = 4.74

Substitute into the Henderson-Hasselbalch equation for aqueous ammonia.

[ NH 4+ ]
pOH = pKb + log
[ NH 3 ]
(x )
4.85 = 4.74 + log
0.10
( x)
0.11 = log
0.10
x
100.11 =
0.10
x = 0.13 moles = NH 4+ = NH 4 Cl in a liter

? g NH 4 Cl  53.5 g NH 4 Cl 
=  0.13 mol NH 4 Cl ×  = 6.955 g = 7.0 g NH 4 Cl
L  mol NH 4 Cl 

Buffering Capacity
The capability to resist large changes in pH when additional hydroxide or hydronium ions are added to a buffer is
determined by its buffering capacity. That is, the limit of additional hydroxide and hydronium ions that can be added
to a buffer without a large change in the pH occurring in the solution is the buffering capacity for a specific buffer.
There are several ways in which the buffering capacity of a specific buffer can be reported. For example, recording
the volume of a given concentration of a strong acid or a given concentration of a strong base that, when added to a
buffer solution, resulted in a change of ± 2 pH units. The number of moles of a strong acid or a strong base added to

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a buffer solution that caused a ±2 change in the pH is an alternative means of recording the buffer capacity of a
particular buffer. Although more general, another method of calculating the buffer capacity of a specific buffer,
which is widely accepted, is to determine that the number of moles of the weak acid and the number of moles of the
salt of the weak acid in a buffer, which in turn, determines the maximum moles of hydroxide and hydronium ions
that can be added to the buffer without exceeding a ±2 change in pH of the solution.

For example:
A buffer is comprised of 50.0 mL of 0.250 M hypochlorous acid, HClO, and 75.0 mL of 0.300 M sodium
hypochlorite, NaClO. What is the buffering capacity of this buffer?

←
HClO (aq)  → ClO − (aq) + H 3O + (aq)
from weak acid from salt

We know that the number of moles of the weak acid and the number of moles of the salt of the weak acid are fairly
sizeable in a buffer. It is the high concentration of weak acid and high concentration of its conjugate base in
equilibrium that maintains the pH of the solution as additional OH– or H3O+ ions are added.

When a strong base is added to the buffer, the increase [OH–] stresses the equilibrium because the additional
hydroxide ions are removed by the hydronium ions. The equilibrium shifts to the right to produce more
hypochlorite ions and hydronium ions. The number of moles of OH– ions that can be removed is dependent on the
number of moles of HClO available to ionize. Once the weak acid is exhausted, the solution no longer can resist the
change in pH due to the increase in [OH–].

OH-(aq) + H3O+(aq) → 2H2O (l) -or- H+ (aq) + OH- (aq)→ H2O (l)

The buffer capacity of the OH- ions in the buffer is:

  OH − removed 
(0.0500 L HClO ) 0.250 mol HClO   1 mol  = 0.0125 mol OH − ion can be removed

 L HClO  1 mol HClO available 

The increase [H3O+] stresses the equilibrium by increasing the concentration of hydronium ions. The equilibrium
shifts to the left to produce more hypochlorous acid. The number of moles of H3O+ that can be removed is
dependent on the number of moles of ClO- available to react with the additional hydronium ions. Once the conjugate
base is exhausted, the solution no longer can resist the change in pH due to the increase in [H3O+].

The buffer capacity of the H3O+ ions in the buffer is:

 1 mol H 3 O + removed 
(0.0750 L ClO ) 0.300 mol ClO
−
−   +

L ClO −  1 mol ClO − available  = 0.0225 mol H 3 O ions can be removed

  

The buffer capacity of the HClO/NaClO buffer is equal to 0.0125 mol of OH- ions and 0.0225 mol of H3O+ ions. A
simple way to remember the relationship between the added OH- and H3O+ ions and the species in equilibrium that
are affected by the increase is given below.

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

←→
[ HClO] (aq ) 
← → [ClO − ] (aq ) + H 3O + (aq )
c c
[ OH − ] [ H 3O + ]

The buffer capacity The buffer capacity of

of OH- is equal to H3O+ is equal to
approximately the approximately the
number of moles of number of moles of the
the weak acid in the conjugate base of the
buffer. weak acid in the buffer.

Another method of determining buffer capacity can be determined from the results of adding a strong acid or strong
base to a buffer solution and recording number of moles of H3O+ and/or number of moles of OH-that were added to
change the pH of solution by 2 pH units.

For Example:
A buffer at pH 4 required 15.3 mL of 0.50 M HCl to lower the pH from pH 4.0 to pH 1.9 and 11.2 mL of 0.75 M
NaOH to raise the pH from pH 4.0 to pH 6.2. What is the buffering capacity of the buffer?

(0.0153 L ) 0.50 mol HCl  = 7.7 ×10 −3 mol H 3 O +

 L 
 − 
(0.011.2 L ) 0.75 mol OH  = 8.3 × 10 −3 mol OH −

 L 

Weak Acid/Strong Base Titration Curves

The first part of the experiment involves constructing a titration curve generated by the titration of a weak acid with
a strong base. To analyze the results of the weak acid titration, you will create two graphs, a titration curve and the
2nd derivative from the data collected from your experimental results. From the titration curve and 2nd derivative,
you will have the information to experimentally determine the pKa and Ka of acetic acid.

As an example, consider the titration of 100.0 mL of 0.100 M acetic acid, CH3COOH, (a weak acid) with 0.100 M
NaOH (a strong base). The acid and base react in a 1:1 mole ratio.

1 mol 1 mol 1 mol 1 mol

CH3COOH (aq) + NaOH (aq) 
→ NaCH3COO (aq) + H2O (l)
1 mmol 1 mmol 1 mmol 1 mmol

(weak acid) (salt of weak acid)

1. Determine the pH of the acetic acid solution before the titration is begun.

→ CH 3COO – + H 3O +
CH 3COOH ←

( 0.10-x ) M xM xM
 H   CH 3COO 
+ −

Ka =    =1.8×10 −5
[CH 3COO H ]
Ka =
( x )( x ) =1.8×10 −5
( 0.10 − x )

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The simplifying assumption can be applied.

x 2 = 1.8×10 −6 ∴ x = 1.3×10 −3
 H 3O +  = 1.3×10 −3 ∴ pH = 2.87

Before the equivalence point is reached, both CH3COOH and NaCH3COO are present in the solution. The NaOH
reacts with CH3COOH to form NaCH3COO. A weak acid plus the salt of a weak acid form a buffer.

2. After a total of 10.0 mL of NaOH solution has been added, the pH is ____?
 100.0 mL CH 3 COOH  0.100 mmol 
mmol CH 3 COOH =    = 10.0 mmol CH 3 COOH
  mL 
 10.0 mL NaOH  0.100 mmol 
mmol NaOH =    = 1.0 mmol NaOH
  mL 

NaOH + CH 3COOH → NaCH 3COO + H 2O

Initial: 1.00 mmol 10.0 mmol
Chg. due to rxn: − 1.00 mmol − 1.00 mmol + 1.00 mmol
After rxn: 0.00 mmol 9.0 mmol 1.00 mmol
9.0 mmol
M CH 3COOH = = 0.082 M
110 mL
1.00 mmol
M CH COO − = = 0.0091 M
3
110 mL

Apply the Henderson-Hasselbalch equation to determine the pH of the buffered solution. Note: Since the units of
volume (mmol/mL or mol/L) cancel in the equation, it is not necessary to convert the salt and acid concentrations to
molarity; the ratio of the moles or mmoles of the salt to the moles or mmoles of the acid remains the same.
[salt]
u sing mmol ratio: pH = pK a + log
acid]
Using mmol ratio:
 1.0 
= 4.74 + log  
 9.0 
= 3.79

3. After a total of 20.0 mL of NaOH solution has been added, the pH is___?

NaOH + CH 3COOH → NaCH 3COO + H 2 O

Initial: 2.00 mmol 10.0 mmol
∆ rxn: − 2.00 mmol − 2.00 mmol + 2.00 mmol
After rxn: 0.00 mmol 8.0 mmol 2.00 mmol
8.0 mmol
M CH 3COOH = = 0.067 M
120 mL
2.00 mmol
M CH COO − = = 0.017 M
3
120 mL

Apply the Henderson-Hasselbalch equation to determine the pH of the buffered solution.

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

Using mmol ratio: [salt]

using mmol ratio: pH = pK a + log
acid]
 2.0 
= 4.74 + log  
 8.0 
= 4.14

4. After a total of 50.0 mL of NaOH solution has been added, the pH is___?

NaOH + CH 3COOH → NaCH 3COO + H 2O

Initial: 5.00 mmol 10.0 mmol
∆rxn: − 5.00 mmol − 5.00 mmol + 5.00 mmol
After rxn: 0.00 mmol 5.0 mmol 5.00 mmol
5.0 mmol
M CH 3COOH = = 0.033M
150 mL
5.00 mmol
M CH COO− = = 0.033M
3
150 mL

Apply the Henderson-Hasselbalch equation to determine the pH of the buffered solution.

Using mmol ratio: [salt]

using mmol ratio: pH = pK a + log
acid]
 5.0 
= 4.74 + log  
 5.0 
= 4.74
pH = pK a

5. After a total of 100.0 mL of NaOH solution has been added, the pH is___?

NaOH + CH 3COOH → NaCH 3COO + H 2O

Initial: 10.00 mmol 10.0 mmol
Chg. due to rxn: − 10.00 mmol − 10.00 mmol + 10.00 mmol
After rxn: 0.00 mmol 0.0 mmol 10.00 mmol
10.00 mmol
M CH COO− = = 0.0500M
3
200. mL

Hydrolysis
Hydrolysis occurs when a substance dissolved in an aqueous solution reacts with water. At the equivalence point, in
the above titration, the solution is 0.0500M NaCH3COO. Sodium acetate is the salt of acetic acid. Because sodium
acetate is a group I metal salt, the strong conjugate base will undergo hydrolysis; it will remove hydrogen from
water to reestablish equilibrium between the weak acid and its conjugate base. As a result of the hydrolysis reaction,
the solution becomes basic and the pH is greater than 7.00 at the equivalence point.

At the equivalence point in the weak acid titration, the salt of the weak acid is produced. Since sodium acetate is
completely soluble, the acetate anion (a strong conjugate base) will react with water to reestablish the equilibrium
between acetic acid and its strong conjugate base, the acetate ion.

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

→ Na + (aq) + CH 3 COO − (aq) ≈ 100%

NaCH 3 COO (aq) 

CH 3 COO − (aq) + H 2 O (l ) ←


→ CH 3 COOH (aq) + OH − (aq) (Hydrolysis – a reaction with water)

Soluble salts produced by a weak acid/strong base neutralization reaction are strong conjugate bases that will
undergo hydrolysis. Soluble salts produced by a weak base/strong acid neutralization reaction are strong conjugate
acids that will undergo hydrolysis.

The anions (strong conjugate bases) of weak acids dissolved in water will undergo hydrolysis; e.g. NO2-, CO32-, F-,
ClO-, ClO2-, and SO32-.

The cations (strong conjugate acids) of weak bases dissolved in water will undergo hydrolysis; e.g. NH4+, CH3NH3+ ,
CH3CH2NH3+, and C6H5NH3+.

e.g. HF (aq) + NaOH(aq) → NaF (aq) + H2O(l)

1.00 mol 1.00 mol
- 1.00 mol - 1.00 mol + 1.00 mol
1.00 mol

NaF (aq) → Na+(aq) + F−(aq) (group I metal salt will completely ionize in dilute aqueous solution)
1.00 mol 1.00 mol

The fluoride ion is an anion of a weak acid and is a strong conjugate base that will react with water to reestablish the
equilibrium of the weak acid, hydrofluoric acid, and as a result, will also produce hydroxide ions.

The anion is a strong conjugate base that

F − (aq) + H 2 O (l) ←

 → HF(aq) + OH − will remove hydrogen from water to
produce hydroxide ions.

Let us calculate the pH at the equivalence point.

The equilibrium constant for the acetate ion, Kb, is called the hydrolysis constant and determined by dividing the Ka
of acetic acid into Kw, the ionization constant for water.

6. Perform a hydrolysis calculation for the acetate ion in solution.

H 2O

CH 3COO − + ← → CH 3COOH + OH –
( 0.0500 − x ) M xM xM

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

K w 1.0 × 10 –14 x = 5.3 ×10−6

Kb = = = 5.6 × 10−10 ( hydrolysis constant )
Ka 1.8 × 10 –5 = OH − 
[CH 3COOH ] OH -  pOH = 5.28
Kb = = 5.6 ×10−10
CH 3COO −
pH = 8.72

Kb =
( x )( x ) ≈ x 2 = 5.6 ×10−10
( 0.0500 − x ) 0.0500
x 2 = 2.8 ×10−11

An example of a titration curve of a weak acid, HA, with a strong base, NaOH, is given below in figure 1.

Do not copy this graph into

your lab notebook.

Figure 1: The titration curve of a weak acid. The half of the volume added at the equivalence point is used to
determine the pKa at the half-equivalence point. The buffering zone in the titration is a result of the existence of
the HA and the salt of the weak acid, NaA, in the solution. The equivalence point is greater than pH 7 due to
hydrolysis of the salt of the weak acid, NaA, which is the only species in solution at the equivalence point.

MATERIALS
pH Sensor 0.500 M sodium hydroxide (from experiment 5)
ring stand 0.0500 M sodium hydroxide solution (diluted from 0.500 M made in expt. 5)
Lab Quest Instrument 0.500 M acetic acid, HC2H3O2 or CH3COOH, solution.
0.0600 M acetic acid, HC2H3O2 or CH3COOH, solution (diluted from 0.500 M
250 mL beaker
acetic acid)
magnetic stirrer and stirring bar distilled water
25 mL graduated cylinder 50 mL burette and burette clamp & utility clamp
50 mL graduated cylinder 5 mL volumetric pipet with pipet bulb or pump
0.500 M acetic acid

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

PART 1: DETERMINING THE IONIZATION CONSTANT OF A WEAK ACID

PRE-LAB EXERCISE
1. Calculate the volume of the 0.500 M standardized NaOH from experiment 5 and the volume of deionized water
necessary to make 100.0 mL of 0.0500 M NaOH. (Use the molarity of the standardized NaOH made in
experiment 5.)
2. Calculate the volume of the 0.500 M acetic acid and the volume of deionized water necessary to make 50.0 mL
of 0.0650 M CH3COOH.

PROCEDURE: This is an individual titration; you will work alone.

There are three trials for this part.

1. Obtain and wear goggles.

2. Use your calculations from the Pre-Lab Exercise to prepare 100.0 mL of 0.0500 M NaOH solution from the
0.500M NaOH solution.

3. Use your calculations from the Pre-Lab Exercise to prepare 50.0 mL of 0.0650 M CH3COOH solution from
the 0.500 M CH3COOH solution.

4. Add 40.0 mL of distilled water to a 100 mL beaker with a graduated cylinder. With a 5.0 mL volumetric
pipette, transfer 10.0 mL of the 0.0650 M CH3COOH solution into the beaker. CAUTION: Handle the
acetic acid with care. It can cause painful burns if it comes in contact with the skin.

5. Place the beaker on a magnetic stirrer and add a stirring bar.

Set up the data collection system.

6. Connect the pH Sensor to LabQuest and choose New from the File menu. DO NOT pull pH sensor from
storage bottle, loosen cap before removing pH Sensor from storage bottle.
7. On the Meter screen, tap “Mode”. Change the data-collection mode to “Events with Entry”. Enter the Name
(Volume) and Unit (mL) and select OK.

8. Use a utility clamp to suspend the pH Sensor on the ring stand.

9. Clean the 50.0 mL burette with distilled water. Rinse the burette with two small volumes of 0.0500 M
NaOH then fill the burette with the 0.0500 M NaOH solution; slowly pour the NaOH solution into a funnel
that has been placed on the top of the burette. Record the initial volume of the NaOH solution in the
burette. CAUTION: Sodium hydroxide solution is caustic. Avoid spilling it on your skin or clothing.

10. Position the pH Sensor so that its tip is immersed in the acetic acid solution but is not struck by the stirring
bar. Gently stir the beaker of acid solution.

Start data collection. (Select start)

11. Before you have added any NaOH solution, tap “Keep” and enter 0 representing the NaOH volume in mL.
Select OK to store the first data pair. (The pH in this step will be recorded in Table 2, column one.)

12. Conduct the titration carefully. Listed below is a suggested method of running a titration.

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

a. Add NaOH in 2.00 mL increments. After each addition tap “Keep”, and enter the volume of
NaOH dispensed as precisely as possible, to two places after the decimal. Select OK to save the
each of the data pair.
b. When the pH begins to increase at faster rate, add 0.200 mL of the NaOH. Continue in this manner
until you have data through the equivalence point.
c. Continue the titration of the acetic acid solution with sodium hydroxide in 1.00 mL increments.
Take several measurements of pH and NaOH volume, you need at least five points before and at
least five points after reaching the equivalence point in order to create a good second derivative
plot.

13. When you have finished the titration, dispose of the reaction mixture as directed. Rinse the pH sensor with
distilled water in preparation for a second titration.

14. Repeat the necessary steps to test the acetic acid solution and analyze the titration data for a second and
third trial. Note: From the results of your first titration, you may determine that you are able to increase the
volume of NaOH used in the increments during the second and third titrations. You need at least five data
points before reaching the equivalence point and five data points after reaching the equivalence point in
order to have a useful second derivative plot (see 12c.)

15. Use your titration data to create a second derivative plot in LoggerPro in order to find the volume of NaOH
to reach the equivalence point and the half-equivalence point. (Data Table 1)

16. Use your titration data to create a titration curve. Use the volume determined from the second derivative to
analyze the pH at the equivalence point and the pH at the half-equivalence point on the titration curve.
(Data Table 2)

17. Print one copy of each graph (three titration curves and three second derivative plots) and attach to your lab
report. Print one copy of each graph for each member of the team. Be sure both members’ names are on the
graphs.

DATA TABLE 1 Volume of NaOH (mL) at Volume of NaOH (mL) at Half-

Equivalence point Equivalence point
(2nd derivative) (2nd derivative)
Trial 1

Trial 2

Trial 3

Average

Standard Deviation

Note: The volume of NaOH at the equivalence and half-equivalence point is determined from the second
derivative plot.

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

DATA TABLE 2 * pH at Equivalence

pH before NaOH pH at Half-Equivalence point
point
is added (titration curve)
(titration curve)
Trial 1

Trial 2

Trial 3

Average

Standard Deviation
*
pH of diluted acetic acid prepared in step 4. Determine the pH at the equivalence point and at the half-
equivalence point on the titration curve using the volumes determined from the second derivative plot.

DATA ANALYSIS (SHOW YOUR WORK.)

1. Using the equilibrium expression (Ka) and the concentration of the acetic acid sample, calculate the
theoretical pH of the diluted acetic acid solution before any NaOH was added. Compare the theoretical pH
with the averaged pH data (as determined by the standard deviation) you collected in terms of percent error.
(See example under “Weak Acid/Strong Base Titration Curves” in background reading.) The accepted Ka
for acetic acid is 1.8 × 10−5.
2. (a) Given the volume and concentration of the CH3COOH used in the titration, calculate the theoretical
number of moles of NaOH that should be necessary to reach the equivalence point.
(b) Calculate the moles of NaOH used in the reaction to reach the equivalence point using the average (as
determined by the standard deviation) volume of NaOH that was determined from the second derivative
plot. Compare the theoretical number of moles of NaOH used with the data from your titration in terms of
percent error.
3. (a) Calculate the theoretical pH at the equivalence point. That is, determine the concentration of sodium
acetate produced at the equivalence point and calculate the pH that occurs from hydrolysis. (Remember that
the number of moles of NaOH used to reach the equivalence point is equal to the number of moles of
sodium acetate produced. The concentration of sodium acetate is determined by dividing the moles of
NaCH3COO produced by the total volume of the solution. (See step 5 under “Weak Acid/Strong Base
Titration Curves” in background reading.)
(b) Compare the theoretical pH at the equivalence point with the pH at the equivalence point that was
determined from the averaged titration curves data in terms of percent error.
4. (a) Given that the Ka for acetic acid is 1.8 × 10−5 calculate the theoretical pKa for acetic acid.
(b) Calculate the experimental Ka using the averaged pH before the NaOH was added and by the pKa that
was determined from the titration curve.
(c) Compare the theoretical Ka with the experimental Ka and the theoretical pKa with the experimental pKa
in terms of percent error.
5. Write the chemical formula of the acid and the chemical formula of the conjugate base (anion) of the acids
given in the list below. Determine if the acid is weak or strong and if the conjugate base is weak or strong.
If the acid will undergo hydrolysis when titrated to the equivalence point with sodium hydroxide, write
hydrolysis.
a. hydrobromic acid
b. chloric acid
c. hydrocyanic acid
d. hydrofluoric acid
e. hypochlorous acid

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

E.g. Given:
a) acetic acid
b) hydrochloric acid
write: a) CH3COOH (weak acid) and CH3C OO− (strong conjugate base, hydrolysis)
write: b) HCl (strong acid) and Cl− (weak conjugate base)

MATERIALS
pH Sensor 0.500 M sodium hydroxide, NaOH, solution (from expt. 5)
magnetic stirrer and stirring bar 1.00 M hydrochloric acid, HCl, solution
three 150-250 mL beakers 0.500 M acetic acid, HC2H3O2, solution
100 mL graduated cylinder solid sodium acetate, NaC2H3O2
25 mL graduated cylinder ring stand
50 mL burette and burette clamp utility clamp
balance distilled water
5.0 mL volumetric pipette

PART 2: BUFFERS

PRE-LAB EXERCISE

a. Calculate the volume of the 0.500 M acetic acid and the volume of deionized water necessary to make 50.0
mL of 0.120 M CH3COOH.

b. Calculate the volume of 0.500M NaOH and the volume of deionized water necessary to make 50.0 mL of
0.250 M NaOH to test Buffer B. Using the NaOH from experiment 5.

c. Calculate the volume of 1.00 M HCl and the volume of deionized water necessary to make 50.0 mL of
0.100 M HCl to test Buffer B.

Use the Henderson-Hasselbalch equation to perform the following calculations. The Ka of acetic acid is 1.8 × 10–5.

d. Buffer A: Calculate the mass of solid sodium acetate required to mix with 50.0 mL of 0.120 M acetic acid
to prepare a pH 4.10 buffer. Record the mass in your data table. The molar mass of sodium acetate is
82.03g/mol.

PROCEDURE
Reaction 1: Prepare and Test a Buffer Solution (One test for NaOH and one test for HCl)
1. Obtain and wear goggles.

2. Use your calculations from the Pre-Lab Exercise to make 50.0 mL of 0.120 M acetic acid and label Buffer
A. Weigh out the precise mass of sodium acetate determined by your Pre-Lab calculation and dissolve it in
50.0 mL of 0.120 M acetic acid solution. Assume no change in volume after adding the solid sodium
acetate.

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

3. Set up a burette, burette clamp, and ring stand. Use your calculations from the Pre-Lab Exercise to make
50.0 mL of 0.250 M sodium hydroxide. Rinse then fill the burette with approximately 20.00 mL of the
0.250 M NaOH solution. CAUTION: Sodium hydroxide solution is caustic. Avoid spilling it on your skin
or clothing.
4. Measure 20.0 mL of Buffer A solution into a 250 mL beaker and add 30.0 mL of distilled water, label
Buffer B.

5. Place the beaker on a magnetic stirrer, beneath the burette of NaOH, and add a stirring bar.

6. Use a utility clamp to suspend the pH Sensor on a ring stand. Position the pH Sensor in the buffer solution
and adjust its position so that it is not struck by the stirring bar.

7. You will slowly and carefully add 0.250 M NaOH solution to the sample of the buffer. The steps below are
general suggestions; use your judgment to get the best results.

a. The LabQuest will be used as a pH meter only in this part. Note you will have to record the total
volume of NaOH used in order to determine the buffer capacity of NaOH. Be sure to record the
initial and final volumes of NaOH in your lab notebook.
b. Record the initial pH of the buffer in data table 3.
c. Use small increments of the titrant, 0.50 – 1.00 mL. Continue adding the NaOH solution in
increments that change the pH consistently. Your goal is to change the pH of the buffer by 1.5-2.0
pH units.
d. Record the volume of NaOH that was used to change the pH of the buffer by 1.5-2.0 units in data
table 3.

8. Dispose of the reaction mixture as directed. Rinse the pH sensor with distilled water in preparation for the
second titration. Save the data from the titration.

9. Repeat Step 7, using a fresh 20.0 mL sample of the buffer solution and 30.0 mL H2O. For this second trial,
rinse and fill the burette with approximately 20.0 mL of the 0.100 M HCl solution (dilution calculated in
pre-lab).. Handle the hydrochloric acid with care. It can cause painful burns if it comes in contact with the
skin.

10. Carefully add HCl in small increments until the pH of the solution has been changed by 1.5 units. Record,
in data table 3, the volume of HCl that was used.

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

DATA TABLE 3 Buffer

Mass of NaC2H3O2 used to prepare buffer A (g)

Volume of buffer B prepared (mL)

Molar concentration of CH3COOH in prepared buffer B (M)

Molar concentration of NaCH3COO in prepared buffer B (M)

Initial pH of buffer B (measured)

Volume of NaOH to raise pH by 1.5 – 2 units (mL)

Volume of HCl to lower pH by 1.5 – 2 units (mL)

Show calculations for the molar concentration of CH3COOH in Buffer B and the molar
concentration of NaCH3COO in Buffer B with the correct units and significant figures.

DATA ANALYSIS (SHOW YOUR WORK.)

1. Buffer capacity has a rather loose definition, yet it is an important property of buffers. A commonly seen
definition of buffer capacity is: “The moles of H+ or OH– that can be neutralized before the pH changes to a
significant degree; ± 1.5 - 2 pH units.” Use your data to determine the buffer capacity of the buffer as
determined by the number of moles of NaOH and HCl was used to change the pH 1.5 units.

Say, for example, that you had prepared a buffer, in which you mixed 4.525 g of sodium acetate, NaC2H3O2, with
80.5 mL of 0.600 M acetic acid. (Assume no volume change when the sodium acetate is added to the acetic acid
solution.)
2. What would be the initial pH of the buffer?
3. If you add 10.0 mL of 0.250 M NaOH solution to 50.0 mL of the buffer above, what is the change in pH of
the buffer?

DISCUSSION (Attach written discussion to end of lab report.) 50 points/ 5 points for each question.

You may submit more than two pages for this discussion.

Part I.
1. What was the objective of this experiment? Briefly explain the titration procedure you used in this
experiment.
2. What is a buffer zone? Explain how the chemical reaction between the weak acid and strong base created
the buffer zone that appears on your titration curve. What was the pH range of the buffer zone as
determined by your titration curve? What volume of NaOH was used in the buffer zone?
3. What is an equivalence point? How did you determine the equivalence point of your weak acid-strong base
titration from the 2nd derivative and the titration curve? What was the pH at the equivalence point? What is
hydrolysis and how did it affect the equivalence point of the titration?

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CH204 Experiment 7: Acid/Base Equilibrium and Buffers spring 2015

4. How is the pKa related to the pH? (Explain in terms of the ratio of the ion species at pKa). How did you
determine the pKa of acetic acid from the results of your experiment? What was the pH at the pKa of your
weak acid as determined by the results of your titration curve?
5. Define Ka. How did you determine the Ka of your weak acid from your experimental results? Compare the
actual Ka of the weak acid with the Ka resulting from the two different methods you used to calculate Ka.
Were both of the calculated ionization constants of your weak acid within a reasonable range (between 20-
25%) of the actual values? If not, suggest reasons for the inaccuracy.

Part II.
1. What was the objective of this experiment?
2. Briefly explain the procedure you used to create and test the buffers in this part of the experiment.
3. Compare the change in pH when a strong acid was added to the buffer and the change in pH that occurred
when a strong base was added to the buffer.
4. Explain how it was possible for the buffer to resist the change in pH when small amounts of strong acid or
strong base were added to the buffer; explain in terms of the stress applied to the chemical equilibrium by
the excess hydroxide and hydronium ions and the shift of equilibrium that occurs to relieve the applied
stresses.
5. What is buffer capacity? What was the buffer capacity of the buffer that you tested in the experiment?
Identify the possible errors in part II of this experiment.

Be sure to upload a copy of your discussion into SafeAssign before your next lab period.

References:
Zumdahl, S. S. Chemical Principles, 5th Edition, Houghton Miffin Company, 2005, pp. 227-246, 277-306.

Atkins, P.W.; Jones, L. L. Chemical Principles: The Quest for Insight, 3rd Edition, W. H. Freeman and Company,
2005, pp. 365-390, 408-422.

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