Faculty of Engineering Technology

Physics and Basic Sciences Department

Instrumental chemistry lab

Course number: 30206335

EXP(1): Potentiometric Titration (Part 1)

Student name:

Student number:

Submission Date:
 Experiment (1)
Potentiometric Titration (pH titration)
Objective:

In this experiment, you will use a pH meter to follow the course of acid-basetitrations. In
the first part of the experiment a weak acid (acetic acid) will be titrated with a standard
base solution (NaOH). From the resulting titration curve, you will determine the
concentration of an acidic solutions as well as the acid-ionization constant of a weak
acid (Ka).

Experiment duration:120 minutes

Materials and equipment:

Glass ware: 500 ml volumetric flask, 250 ml conical flask, beaker, glass rod , burette,

Chemicals: standard solution of 0.1M NaOH, standard solution of Acetic acid solution, distilled
water

Equipment : pH-meter

Introduction:
You have performed acid-base titrations in the past to determine the concentration
of an acidic or basic solution using a colored indicator. However, there are times
when an appropriate indicator does not exist, or where the color of the solution
would obscure any color change associated with the endpoint. In such cases, a pH
meter can be used to monitor the acidity of the solution throughout the titration.
Recall the definition of pH:

pH = –log [H3O+]

■ The pH Meter
A pH meter works like a voltmeter and measures the voltage (electrical potential)
produced by a solution (whose acidity were interested in) and compares it with the
voltage of a known solution and uses the difference in voltage (the potential difference)
between them to deduce the difference in pH units.

Th pH meter consists of two electrodes: a glass electrode, which is sensitive to the

concentration of hydronium ions in solution, and a reference electrode, which
supplies a constant potential.

The potential of the glass electrode is proportional to the logarithm of the ratio of
[H3O+] inside and outside the electrode.

pH meters are accurate and easy-to-use device for determining the pH of a solution.
For this experiment, the pH meter you will use in this experiment has only one
probe, both of the glass and the reference electrodes are built inside for simplicity
and convenience.

■ Potentiometric titrations

Figure (1) on the next page shows a plot of pH versus volume of base added for the
titration of a strong acid with a strong base. There is very little change in pH when
the base is initially added. Below the equivalence point, the pH is a function of the
amount of excess acid present. Above the equivalence point, the pH is a function of
the amount of excess base present. The equivalence point for the titration of a
strong acid with a strong base occurs when [OH–] exactly equals [H3 O+] in the
solution; pH = 7.0.

The situation in the case of the titration of a weak acid with a strong base is
somewhat different due to the fact that a weak acid is only partially ionized in
aqueous solution. A dynamic equilibrium exists, which is represented by the
following equation:

HA + H2O H3O+ + A–
 pH

Volume of titrant (standard NaOH) solution

Figure 1. Titration curve for the titration of a strong acid with a strong base.

Theory
Weak acids are acids that do not dissociate completely in water. Weak acids have
ph values between 3 and 6. Acetic acid (CH3COOH) and oxalic acid (C2H2O4) are
examples of weak acids.
An acid dissociation constant (Ka) is quantitative measure of the strength of an acid,
the larger the value of pKa the smaller the extent of dissociation. Ka is the
equilibrium constant for the dissociation of a weak acid:

HA + H2O H3O+ + A–

Ka = [H3O+][ A–]
[HA]

HA (aq) + NaOH (aq) H2O (l) + NaA (aq)

In the titration of a weak acid with strong base, the conjugate base of the weak acid will
make the pH of the equivalence point greater than 7.

In this experiment you will also titrate a sample of a weak acid (acetic acid) using
a standard solution of NaOH.

CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)

The presence of both CH3COOH and its salt, CH3COONa (its conjugate base)
creates a buffer system, which resists a large change in ph. (REVISE
HANDERSON HASSELBALCH EQUATION)

The ratio of [CH3COOH]/ [CH3COO–] changes only slightly; the change in [H3O+] (or
pH) must also be small. The pH increases slowly until the equivalence point is
approached
 Figure 2. Titration curve for the titration of a weak acid with a strong base.

At the halfway point in the titration, exactly half of the CH3COOH originally present
will have been neutralized, and therefore the concentrations of CH3COOH and
CH3COO– will be equal.

Thus, the ionization constant of a weak acid is equal to the hydronium ion
concentration at the halfway point in the titration;
pKa = pH1/2

The subsequent rapid increase in pH and the inflection in the titration curve at the
equivalence point can be accounted for. As the equivalence point is approached,
the concentration of unreacted CH3COOH becomes progressively smaller so that
successive increments of NaOH neutralize a greater fraction of the CH3COOH
remaining. This produces a large change in the [CH3COOH]/[CH3COO–] ratio and,
therefore, in the pH of the solution.

At the equivalence point, the acid and base have reacted completely to yield the
salt, CH3COONa. The pH at the equivalence point is determined by the strength of
the base, CH3COO–. The conjugate base of a weak acid is a strong base. It will
react with water to produce hydroxide ions (hydrolysis)

CH3COO– (aq) + H2O (l) CH3COOH (aq) + OH– (aq)

For this reason, it is not surprising to see a pH that is greater than 7 at the
equivalence point.

Beyond the equivalence point, the pH is determined by the ion product for water:

Kw = [H3O+][OH–]

The first small excess of NaOH greatly increases the concentration of OH –,

concomitantly decreasing the H3O+ concentration, and causing the pH to continue to
increase. Well past the equivalence point, the concentration of OH – becomes so
large that only slight changes in pH are produced.

From your titration curve, you will be able to determine the concentration of acetic
acid and the acetic acid ionization constant (Ka).

Part (2) pH titration of a mixture of HCl solution and H3PO4 solution

Phosphoric acid is weak polyprotic (triprotic) acid, it is normally encountered as a

colorless, syrup of 85% concentration in water. the pure compound is colorless solid

The titration curve of with NaOH shows two inflection points and it could be titrated as a
monoprotic or diprotic acid,
the third end point is not
detectable in water
because it occurs at high pH.
The pH is too high because the
thir
H3PO4 + H2O ↔ H2PO4 - + H3O+ Ka1 = 7.5 x 10-3

H2PO4- + H2O ↔ HPO42- + H3O+ Ka2 = 6.2 x 10-8

HPO42- + H2O ↔ PO43- + H3O+ Ka3 = 4.2 x 10-13

The HCl proton and the first proton of H3PO4 will react with the base simultaneously
(HCl actually reacts first, but no distinct endpoint is observed). The result is that the
volume of standard base used to reach the first endpoint represents the sum of the HCl
and H3PO4 concentrations, while the volume of base used to get from the first endpoint
to the second is a measure of the H3PO4 concentration alone. From this information, the
concentrations of both HCl and H3PO4 may be calculated. This paragraph is important,
if you don't understand it, read it again! The endpoints for this experiment cannot be
easily detected using a visual (color) indicator; however, the endpoints are clear when
you measure the potential of a suitable electrode as a function of titrant volume
The first endpoint is due to NaOH neutralizing both acids, but the second endpoint is
due only to the neutralization of the phosphoric acid. (Note that both acids react 1:1 with
NaOH.) For each titration run, use the volume of NaOH needed to titrate from the first
endpoint to the second endpoint, to calculate the number of moles of NaOH that reacted
with phosophoric acid at the second endpoint, and hence the number of moles of
phosphoric aci

Procedure:

- Fill the buret with the standardized (approximately 0.1 M) NaOH solution
provided.

- Record the initial volume of NaOH in your notebook.

- Using a carefully cleaned and rinsed transfer pipette dispense a 25.00 mL

acetic acid solution into a clean, dry 250 mL beaker (do not pipet directly
from the bottle).

- Thoroughly rinse the electrode of the pH meter with distilled water, shake off
the drops of water and place it in the acetic acid solution.

- Begin titration by titrating the acid solution with NaOH solution and stir the
solution with pH electrode (be careful not to break the glass tip) then record
the pH after each addition of NaOH standard solution (titrant is added in
small portions)

- Collect enough data to draw a titration curve pH vs volume of NaOH)

- All of the solutions in this experiment may be poured down the sink.
 VOLUME OF TITRANT pH ΔpH ΔV ΔPH/ ΔV Δ(ΔPH/ ΔV)

Data and observation:

Draw the pH curve using the data you collected during potentiometric titration of acetic acid with
standard NaoH solution showing the X and Y axis of the curve

Molarity of standard NaOH solution = _________________

Volume of acetic acid solution = ____________________

From the pH curve above

A. Calculate the molar concentration of acetic acid

 B. Calculate Ka of the acid.

Plot the first and second derivatives for the collected data to find the end point of titration.

First derivative (ΔPH/ ΔV) versus volume of base added

Second derivative (Δ(ΔPH/ ΔV)) versus volume of base added

Calculate the concentration of acetic acid using the first and second derivative (show your work)

a. Concentration of acetic acid (from first derivative)

 b. Concentration of acetic acid (from second derivative)

C. Write your conclusions

Questions