Construction of Ag | AgCl Reference

Electrode and Application

Valentin Uzunov (author), Tom Ronay (lab partner) and Hans Harshfield (lab partner)
PSU ID#: 964100377
CHM 229H, Lab 269, Submitted: 5/8/2014
ABSTRACT
The current experiment investigated the use and validity of an economically constructed Ag | AgCl
reference electrode to determine and compared the standard reduction potentials for of Zinc, Iron and
Copper against the literature established standard reduction potentials. A voltaic cell was setup consisting
of two half-cells, the constructed Ag | AgCl reference electrode (cathode half-cell) and a metal anode
electrode (anode half-cell), both partially immersed into a 0.1 M salt solution of the corresponding metal,
connected by a high-impedance voltmeter. The mean cell potentials measured against the Ag | AgCl
reference electrode were +0.088 0.0078 (2 sd) for copper, -0.808 0.054 (2 sd) for zinc, and -0.614
0.0035 (2 sd) for iron. Using the Nernst equation to convert the results in terms of standard reduction
potentials showed, a close match between experimental results and copper, with a -1.2% difference from
literature. Results for Zinc and Iron were significantly less accurate with -23.7% and -12.0% differences
respectively.

EXPERIMENTAL
The cathode half-cell (Ag | AgCl reference electrode) was constructed following the method
described by Ahn, Reuland, and Chadd (1992) published in the journal of Chemical Education. The end
of a 10 cm long, 6 mm diameter soda glass tube was rotated in a Bunsen burner flame until the opening
was almost sealed. The tube was allowed to cool and a small amount of glass wool and wet filter paper
were packed into the almost sealed end. The tubing was then filled with a saturated KCl solution to a
height of 7-8 cm and 3 drops of 0.1 M AgNO
3
solution were added. The electrode consisted of a 13 cm
long, 1.0mm diameter pure silver wire (Ag/Cu 90/10 would also work). Before adding the electrode to the
tubing one end was dipped (2-3 cm) briefly into a 1:1:1 mixture of H
2
O: concentrated HNO
3
:
concentrated HCl, until the metal surface was uniformly tarnished. The tarnished end of the wire was then
inserted into the glass tubing and secured at the top with parafilm. The anode half-cell simply consisted of
a polished metal wire. A voltaic cell was then setup by partially immersing both half-cells into 100 mL of
0.1 M solution of the metal salt and connected to a voltmeter. The anode was connected to the common
and the cathode to the dc-voltage input. The same voltaic cell setup was used to measure the difference
potential for Iron, Zinc and Copper half-cells in reference to the Ag | AgCl reference electrode
Table 1 Measured potential difference against Ag | AgCl reference electrode.
Anode
Current
results (V)
Aggregate Results (V)
0.1 M Cu
2+
| Cu +0.087 +0.089 +0.093 +0.084
0.1 M Zn
2+
| Zn -0.815 -0.768
*
-0.827 -0.822
0.1 M Fe
2+
| Fe -0.614 -0.525
*
-0.615 -0.615
* Suspected outliers
RESULTS
Table 2 Summary experimantal standard reduction pontentials
Anode Mean E
cell
2sd

(V) E
red
for M
z+
| M (V) E
red
(V) % difference
0.1 M Cu
2+
| Cu +0.088 0.0078 +0.285 + 0.336 -1.2
0.1 M Zn
2+
| Zn -0.808 0.054 -0.611 - 0.581 -23.7
0.1 M Fe
2+
| Fe -0.614 0.0035 -0.417 - 0.387 -12.0

Table 2 shows a summary of the results from the data set in table 1. Suspect outliers were screened
using a simple Q-test analysis at 95% confidence level [2] and removed is necessary from data set prior to
subsequent calculations.
For

, if Q
exp
> Q
crit
Xn (at 95% confidence level), then X
n
is an outlier
Example: (Fe data outlier) data in ascending order: 0.525, 0.612, 0.615, 0.615

= 0.9667 > Q
crit (at 95% CL)
= 0.829
Reduction potentials for each metal half-cell ( M
z+
| M ) in reference to HSE was determined from Eqn 1.

[Eqn 1]
Example: E
Zn2+
= -0.808 V + 0.197 V = -0.611 V
Where the cell potential for the Ag | AgCl reference electrode was +0.197 V [1] and E
cell
were the mean
values from experimental results. From this, the standard reduction potential for

[Eqn 2]
was calculated at room temperature with the Nernst equation

]
[Eqn 3]
Example:

[]
= -0.581 V

DISCUSSION
The following experiment aimed to test the practical use and validity of an economically constructed
Ag | AgCl reference electrode in determining the difference potentials of Zinc, Iron and Copper. A voltaic
cell was setup to measure the voltage between the Ag | AgCl reference electrode (cathode) and the
metal anode electrode using a high-impedance voltmeter. The results of the experiment are
summarized in table 2. Cell potentials measured were converted to cell reduction potentials in reference
to the standard hydrogen electrode, before standard reduction potentials were calculated using the
Nernst equation. Result in table 2 show an excellent agreement in the difference potential measured for
copper, + 0.336 V 0.0078 V (2 sd) and the literature value of 0.34 V [5] (-1.2% difference). The standard
reduction potentials for Iron and Zinc however, were significantly less accurate, at - 0.581 0.054 (2 sd)
for Zinc and - 0.387 0.0035 (2 sd) for Iron, corresponding to a percent difference of -23.7% and -12.0%
compared to literature values [5]. The current results are consistent with the reported cell potentials
measured by Ahn et al using similar experimental methodology. These results suggest that the Ag | AgCl
reference electrode design is a reliable and cost effective experimental tool, useful for practical teaching
means.
The large experimental error for zinc and iron compared to literature values, maybe may be
attributed to: Human error in handling and treatment of the more reactive metal electrodes prior to use
and the leveling effect with water [1]. Oxidation of the exposed metal surfaces after sanding with
atmospheric oxygen is sufficiently slow at room temperature and humidity that it can be ruled out [3, 4].
However, inadequate polishing or contamination of metals prior to use should be considered. Any areas
of the metal wire not adequately sanded will reduce the interfacing surface area between the metal and
solution, reducing the overall potential area for oxidation to occur. It is also likely that the results were
affected by the leveling effect, due to the possibility of reducing the solvent, water [1]:
2H
2
O(l) + 2e
-
H
2
(g) + 2OH
-
(aq) E = -0.83 V
Both of these effects will reduced the overall potential difference measured, resulting in more positive
difference potentials. The effects are more evident in Zinc than Iron, as the Zinc is a much more reactive
metal and thus more likely to be effected.

CITATIONS
[1] - Ahn, M K; Reuland, D J; and Chadd, K D: Electrochemical measurements in general chemistry lab
using a student-constructed Ag-AgCl reference electrode", Journal of Chemical Education, 1992, 69(1),
74
[3] - Dixon's Q-test: Detection of a Single Outlier. (n.d.). Retrieved from
http://www.chem.uoa.gr/applets/AppletQtest/Appl_Qtest2.html
[3] - Corrosion of Zinc :: KEY to METALS Articles. (n.d.). Retrieved from
http://www.keytometals.com/Article40.htm
[4] - Corrosion and Electrochemistry of Zinc - Xiaoge Gregory Zhang - Google Books. (n.d.). Retrieved
from Google Books
[5] - Standard electrode potential (data page). (2014, April 17). In Wikipedia, The Free Encyclopedia.
Retrieved 02:52, May 8, 2014,
from http://en.wikipedia.org/w/index.php?title=Standard_electrode_potential_(data_page)&oldid=604
601832