Construction and Evaluation of an Inexpensive Reference

Electrode with Internal Electrolyte in Agar Matrix

Leandm Victoria, M. Gloria Ortega, and Jose A. Ibaiiez
Universidad de Murcia, 30071 Murcia, Spain

The use of reference and ion selective electrodes is of great Preparation of Internal
importance in many branches of chemistry (1, 2), and ex- Electrolyte
periments using these electrodes are found in most under- When a polymer is swollen
graduate programs. Thus the introduction of studenta to the with a liquid, a gel is formed
construction of these electrodes is a useful exercise in devel- through which the liquid com-
oping and understanding of electrode design (3-7). In this ponent may move by a comhi-
paper, we show how to construct a reference electrode of Ag/ nation of diffusion and con-
AgCl with an internal electrolyte in agar matrix. This elec- vection. Substances dissolved
trode is less expensive and, in many cases, more stable than i n t h e liquid may also be
the commercially available models. transported through the gel.
In our.electrode, the inter-
The Electrode nal matrix is a gel prepared
The electrode has the configuration with an aqueous solution of
Agar gel-AgCI (saturated),KC1 (3M)lAgIl potassium chloride at concen-
tration 3 M, previously satu-
and is formed of the following parts: an external tuhe, an rated with AgCl, and with
internal tuhe concentric with the former, an active tip, an agar as solute a t 1%.
upper stopper, and an inner reference electrolyte supported The prepared solution is
in a agar gel matrix (Fig. 1). stirred and heated to the hoil-
The external glass tuhe has a hole (1-mm diameter, ap- ing point, this state being
proximately) in its lower part, through which the liquid maintained until the turbid
junction between the internal electrolyte and the solution appearance of the solution
being studied is accomplished. This junction has a very low clears. Afterwards, the solu-
electric resistance and, consequently, a very high capacity to tion is slowly cooled to a point
transport the electric current. This tube contains the gel, near gel formation; a t this
and concentric with it there is another glass tuhe with the point i t is poured into the ex-
active tip. This tip is ashort length of platinum wire (10mm) ternal tuhe of the electrode
fused t o the glass tube hy means of an oxygen-methane and gels there; the process is
torch or by epoxy adhesion. This tip is coated with silver hy accelerated by immersion in a
electrolysis. Platinum wire of 0.4-mm diameter was used. vessel containing the remain-
Inside this central tuhe there is a small quantity of mercu- ing solution of KC1 and AgCl
ry for contact between the active tip and a constantan wire without agar a t ambient tem-
that is welded to a copper wire for the lead. Both tubes are perature. I t is necessary for
supported by a nylon housing; this housing is joined to a the lower hole of the electrode
BNC connector. The three parts of this piece are shown in tuhe to remain filled with gel,
Figure 1: part A is internally threaded to house the outer Figure 1. Dlagrarn of a completed the formation of a gel drop
reference electrode.
tube of the electrode; two ruhher 0 rings in A facilitate the outside the tuhe being conve-
fitting of the central tuhe. Part B is a washer lodged in part nient to prevent the appear-
A, acting as a butt to prevent the upward movement of the ance of air bubbles in the liq-
central tube (this part is stuck to A). Part C is a stopper to uid junction.
couple part A with the BNC connector.
Electrode Evaluation
Preparation of Active Tlp The experimental evaluation of our electrode was accom-
The platinum wire of the active tip is coated with Ag by a plished comparing its hehavior using an indicator (ion selec-
procedure that is a modification of Brown's method (8).The tive) electrode (ISE) for CI- (Orion, model 94-17), with the
silver plating solution was prepared using Basset and Cor- hehavior of a commercial reference electrode (Orion, model
bet's method (9) hut AgN03 was used instead of AgCN, with 90-02) also using an ISE for C1-, measuring the electric
a secondary reaction with KCN in excess. This is possible response of both electrodes by means an ion analyzer (Orion
because of the following complexation process: RA mni
The assembly for measuring this response is
AgNO, + KCN ~t AgCN + KNO,
Reference electrodelASE C1- (1)
AgCN + KCN e K[Ag(CN)],
AgNO, + 2KCN e K[Ag(CN),] + KNO, In this cell, the emf, E , is given hy

The reagent, K[Ag(CN)2],must have a concentration of

1%,and, using this, the platinum wire is coated with silver by where Eind, E,F, and Ej are the potential of the indicator
electrolysis, which takes place over 6 h with a direct current electrode, of the reference electrode, and of the liquid junc-
of 0.5 mA. The tip, when coated, acts as cathode. tion, respectively. If E,,fis constant and Ej is either constant

Volume 67 Number 2 February 1990 179


Figure 2. Emf obtained wilh a chloride ion selective electrode vs. our reference
electrode (a) and a commercial reference electrode (0) for five standard
solutions. Experimenml points and fined straight lines.
or negligible, and using the Nernst equation to express Ejnd
eq 2 becomes
E = E:' --In
RT
F
Ci = E!' - 2.3-RTF log Ci (3)
where Et' = Ei- E,er - (RTIF)In (y;), with yian appropriate
activity coefficient, and Ci the molar concentration of ion
C1-, such as Ci = C, C being the salt concentration.
Equation 3 establishes alinear dependence between E and
log C with a slope that is a function of the temperature,
having a theoretical value of 59.1 mV at 25 ' C .
Figure 2 shows the experimental points (log C, E ) ob-
tained for our electrode ( 0 )and the commercial reference
electrode (0). All experiments were conducted in a thermo-
stated vessel at 25 OC. The fitting of two straight lines to
these points leads to the following equations:
180 Journal of Chemical Education
gel-AgCI, KCI/Ag E = -53.438 log C 100.358+ (4)
AgC1, KCVAg E = -54.918 log C - 14.927 (5)
with correlation coefficients equal to 0.9974 in both cases.
The expected linearity in the Nernst equation is found
and the slope values are near the theoretical one.
We have worked using conditions of constant tempera-
ture, since reproducibility of measurements is limited by
this factor. It has been observed that within the ooeratina
range of our experiments (10-3-10-1 M), and carrying out
several calibrations, the measurements obtained are within
an uncertainty o f f 2%.
When the electrode system (reference-ISE) is removed
from one solution and nlaced in another of different concen-
tration, the response t h e (the time required to reach 990i of
the stable ootential reading) is not affected. This time is of
the order G a fewseconds, always less than 30 s, and depends
on the magnitude and direction of concentration chance; its
value is smaller when the change is from dilute soluti& to
concentrated solutions.
The advantages of the described electrode are:
(1) It is much cheaper. (The total cost is $20; the price of a similar
reference electrode is over $150.)
(2) The liquid junction is favored by the absence of a separating
phase between the inner electrolyte and the problem solution.
(3) The possible contamination in the analyte solution because of
the inner electrolyte is minimal, due to the interaction between
this electrolyte and the agar matrix.
(4) The electrode does not have to he refilled, which means mainte-
nance is easy.
Acknowledgment
The authors acknowledge financial support from the
C.I.C.Y.T. of Spanish Government under grant No. PB85-
0240-CO2-02.
Literature Clted
1. Skom.D. A : West.D. M.P~inci~isso/Instrum~nfolAnolysis:Saundcrr: Philadelphia.
19&: Chapter3 18and 19.
2. Bailey, P. L. Anaiyiris uith Ion-Sd~ctimEieefrodes: Hayden: London, 1976.
3. Lamb.R.E.:Natush,D. E.S.:O'Roiliy.J.E.; Watkins,N. J C h r m E d u r . 1973.50.42-
~ ~~~~.
.
8. B ~ ~ ~ ' A . JCham.
. A ~Snc.
: 1934,56.64664;.
9. Ban3et,A.;Corbel,J. J. Chem. Soc. 19Z9,125, ,660-1663.