Understand The Construction of The Laboratory and Field Used Reference Electrodes and Its Conversion As Per ASTM G215.
Understand The Construction of The Laboratory and Field Used Reference Electrodes and Its Conversion As Per ASTM G215.
Understand The Construction of The Laboratory and Field Used Reference Electrodes and Its Conversion As Per ASTM G215.
Construction
Standard Electrode Potential (SHE) is Pt rode in acidic environment. Hydrogen ions in
acidic solution (Electrolyte) have unit activity (aH+ = 1) at 25℃ and 1 atm pressure. (as
shown in Figure 3)
Principle
Equilibrium reaction is;
2H+ (aq)+ 2e- ↔ H2 (g) ↑ Eo = 0V vs SHE
Platinum itself act as catalyst.
Uses
SHE is used for standard potentials measurement. We can also measure single electrode
potentials experimentally in a wide variety of electrochemical fields.
Figure 4: Copper-copper sulphate electrode (CCSE)
Hydrogen gas released is flammable, therefore SHE is not practicable in laboratories.
Alternatively, four reference electrodes are used. They are potable. But fail at high temperature.
1. Copper-Copper Sulphate Electrode (CSE) or (CCSE)
2. Silver-Silver Chloride Electrode (SSCE)
3. Saturated Calomel Electrode (SCE)
4. Mercury-Mercury Sulphate Electrode
3. Reference Electrodes
A standard electrode having fixed value of potential is called Reference electrode or Half-cell
electrode. Used to calculate the value of potential of electrode under observation.
In Reference electrodes four factors are observed:
1. Electrode reaction
2. Electrode (which metal)
3. Electrolyte (Concentration)
4. Ionic conduction/ ionic plug/ frit/ salt bridge.
Types of Reference Electrodes
They are of two types.
1. Permanent Electrode.
2. Non-Permanent/ Potable Electrode (Copper-Copper Sulphate Electrode, Silver-Silver
Chloride Electrode, Saturated Calomel Electrode, Mercury-Mercury Sulphate Electrode)
Copper–Copper Sulphate reference Electrode (CCSRE)
Construction
The copper–copper sulfate reference electrode consists of metallic copper immersed in saturated
copper sulphate. The commercial reference electrode is a plastic tube holding the copper rod and
saturated solution of copper sulphate. A porous plug on one end is in contact with copper
sulphate electrolyte and ultimately with the earth is made. It is easily recharged when it becomes
contaminated. The copper rod protrudes out of the tube as shown in figure 4 The two standard
tips available are the Flat Tip and the Pointed Tip. Both the Flat and Pointed tips are made to
maximize the total surface area of the tip to ensure good contact area with the electrolyte. There
is no performance difference between the two types of tip. The Flat tip may be more versatile, as
a flat surface can be useful on a variety of electrolytes, such as soils, liquids and concrete.
A voltmeter negative lead is connected to the copper rod. The half-cell reaction is
Cu2+(aq) + 2e- → Cu(s) Eo red= 0.342V vs SHE
E Cu/Cu+2 = E Cu/Cu+2 + 0.059 log 10 aCu+2
Figure 5: Silver-silver chloride electrode (SSCE)
The saturated calomel reference electrode is extensively used standard reference electrode, in the
laboratory. The word calomel is the combination of Mercury and Mercurius chloride i.e. Hg 2Cl2.
Is a liquid reference electrode because mercury is liquid at room temperature. It consists of a
small glass tube in which silver wire is placed. Wire is immersed in Hg over which black color
power of Hg2Cl2 is poured. One end of the glass tube is sealed by cotton plug. This whole
assembly is placed in another glass tube, which is sealed with the porous plug that is immersed in
a saturated KCl solution as shown in figure 6.
The mercury-mercury sulphate electrode is used where a chloride free electrode is required. It is
especially used in experiments to do with lead–acid batteries. The electrode is usually
constructed from a platinum wire inserted into a mixture of Hg 2SO4 and liquid mercury, with an
electrolyte solution of H2SO4 / K2SO4 and porous ceramic frit acts as junction of electrode and
liquid as shown in figure 7. Half-cell reaction is
2.303 RT
E = E° - log [SO4-] 2
2F
The mercury-mercury sulphate electrode can operate on high temperatures of as much as 100
̊C.it is used in anodic protection and becomes inactive in only one use.
Experimental Procedure
3. The reference electrode connected with the black terminal of high impedance voltmeter
which act as anode and red terminal connect with metal sample which act as cathode.
4. Observe polarity and voltage.
5. Always replace the vinyl cover on the electrode after each usage to prevent moisture loss
in the ceramic plug.
Result
Al is most active (anodic) metal and Zn is most noble (cathodic) metal among given metals.
Discussion:
The galvanic series lists metals according to their electrical potential in an electrolyte. As
mentioned, metals that are anodic will corrode at a more rapid rate than passive or cathodic
metals. According to galvanic series from experimental readings, Al has the highest value of
negative reduction potential while Zn has less value of negative reduction potential as mention in
Table 2. But in reality, zinc is most active metal while copper is most noble metal so that Zn will
corrode more rapidly than other given metals according to the standard. To convert this potential
to a value on the scale in which the hydrogen electrode has a potential of zero, it is necessary to
add 0.318 volt to the potential that was measured, making it -0.641 volt vs. SHE. Human error
may be the cause.
B. Corrosion potential measurement of metals in simulated sea water with silver-silver
chloride reference electrode (sea water) and their galvanic series.
Experimental work
In this experiment Nickel, Lead, zinc, copper, aluminium and iron is immersed in simulated sea
water (3.5% NaCl). The Ag/AgCl reference electrode was kept at the corner of the simulated
seawater container, in which the black terminal was connected with the reference electrode and
red terminal was connected with the samples. Measured the electrode potential of all these
sample one by one using high impedance voltmeter. (Figure 9).
Result
Zn is most active (anodic) metal and copper is most noble (cathodic) metal among given metals.
Discussion
According to standard galvanic series trend from most active to most noble is Zn, Al, iron, Pb,
Ni and Cu. But galvanic series made from readings was different as mentioned in table 4, This
variation is due to human error and the voltmeter reading was not stable during performing the
experiment.
Observations
Electrolyte: sea water Reference Electrode: Silver-Silver Chloride
Table 3: Metals in sea water with reference to Silver-Silver Chloride
Observations
Electrolyte: sea water (external), Sat. KCL (internal)
Reference Electrode: Silver-Silver Chloride
Table 6: Metals in sea water with reference to Silver-Silver Chloride saturated KCl
Table 9: Standard galvanic series showing reduction half-cell potential by decreasing order of
potential
References
https://www.bing.com/search?
q=tinker+and+rasor+company+referance+electrode&qs=n&form=QBRE&sp=-
1&pq=tinker+and+rasor+company+refer&sc=0-
30&sk=&cvid=6AD5EAD998824115907633958D6B7F5F
www.tinker-rasor.com