EXPERIMENT 4: SELF-ASSEMBLED

MONOLAYERS
Aim
a. To measure the pKa of 3-mercaptopropionic acid in aqueous solution from a
simple acid/base titration method.
b. To measure the pKa of a self-assembled monolayer (SAM) of 3mercaptopropionic acid.

Introduction
Studying the surface properties of nanomaterials enables us to establish the
behavior of the materials themselves. The surfaces environment of a nanomaterial
varies from a bulk solution to a bulk solid phase.
This experiment enables us to examine the properties of flat gold surfaces and
hence investigate changes in the molecules acid dissociation equilibrium as we
attach a molecule to the gold surface. A planar gold surface was used as the
substrate whereas 3-mercaptopropionic acid was used as the adsorbate. The acid
was adsorbed onto the substrate so that a Au-S bond was formed along the process
as gold form as stable covalent bond with sulfur atoms. Since the acid is
chemisorbed onto the surface, a single layer of 3-mercaptopropionic acid is
adsorbed onto the gold surface forming a structure known as self-assembled
monolayer (SAM).

Procedures
Part A: Acid/Base Titration of 3-mercaptopropionic acid in solution
An aqueous solution of 3-mercaptopropionic acid was titrated against NaOH and the
changes in pH were monitored using a pH meter as more NaOH was added into the
solution. The titration curve was the plotted so that the pK s of the acid in solution
can be determined.
Part B: Cylic Voltammetry of Hexacyanoferrate
8 mL of the prepared buffer solution was pipette into a scintillation vial and 2.0 mL
of 5 mM hexacyanoferrate solution was also added. Oxygen was then removed by
means of ultrasonic bath. The working, auxillary and reference electrode was
inserted into the vial and the experiment was run. The peak current of each buffer
solution obtained from each run was plotted against its corresponding pH. Inflexion
point of the curve determined the pKa.

Results and Dicussions

properties

Exercise
1. The structure of 3-mercaptopropionic acid:

Functional groups
Thiol SH
Carboxylic acid -COOH
Strong odour
Strong odour
Lower boiling point than
Higher boiling point than
water
water
Less soluble in water
Water soluble
Polar
Weak acid

2. HSCH2CH2COOH + NaOH

HSCH2CH2COONa + H2O

Titration Curve
10
9
8
7
6
pH

5
4
3
2
1
0
0

0.5

1.5

2.5

3.5

Volume of NaOH added (mL)

Figure 1: Titration curve of 3-mercaptopropionic acid with NaOH solution

From Figure 1, the equivalent point is observed to be at approximately pH 7.7. Since
pKa value is determined at half of the pH at equivalent point, hence pK a = 7.7/2
which is equals to 3.85.

Peak current vs. pH

2
1.5
Current, I (mA)

1
0.5
0
1

pH

Figure 2: Peak current against pH curve