PCH-3852

ELECTRO ANALYTICAL METHODS

WORKING ELECTRODES
IN VOLTAMMETRY
INTRODUCTION:

• CHEMIST JAROSLAV HEYROVSKÝ

• IT WAS INVENTED IN 1922 BY CZECH CHEMIST

JAROSLAV HEYROVSKY, FOR WHICH HE WON
THE NOBEL PRIZE IN 1959.
CONTENTS:
➤WHAT IS VOLTAMMETRY AND IT’S INSTRUMENTATION

➤DIFFERENT TYPES OF WORKING ELECTRODES

➤DEFINITION, STRUCTURE AND WORKING OF DME

➤TYPES OF MERCURY ELECTRODE

➤ADVANTAGES & DISADVANTAGES OF DME

➤WHY WE NEED OF THREE ELECTRODES

➤PRECAUTIONS CAN BE TAKEN WHILE USING DME
 VOLTAMMETRY

IT IS AN ELECTRO-ANALYTICAL TECHNIQUE.
IT GIVES INFORMATION ABOUT THE ANALYTE
WE CAN EVEN MEASURE THE AMOUNT OF CURRENT BY
VARYING THE VOLTAGE.
• THE CHANGE IN CURRENT WITH THE VARYING VOLTAGE
GIVES THE
• PLOT AND IS KNOWN AS VOLTAMMOGRAM
• THERE IS A MINIMUM POTENTIAL REQUIRED TO INITIATE
AN
INSTRUMENTATION:

• IT IS A THREE ELECTRODE SYSTEM.

1. WORKING ELECTRODE
2. REFERENCE ELECTRODE
3. AUXILIARY ELECTRODE
 WORKING ELECTRODES

• RANGES FROM SMALL MERCURY

DROP TO FLAT PLATINUM DISK
• OTHER COMMONLY USED ELECTRODE MATERIALS
GOLD, PLATINUM AND GLASSY CARBON
 REFERENCE ELECTRODE :

USUALLY STANDARD ELECTRODE IS

USED AS REFERENCE ELECTRODE

ITS POTENTIAL IS CONSTANT

IT PROVIDES POTENTIAL TO THE

WORKING ELECTRODE
• COMMON REFERENCE ELECTRODE
ARE CALOMEL ELECTRODE AND
AG/AGCL ELECTRODE
 AUXILIARY ELECTRODE:

IT IS USUALLY A THIN PLATINUM WINE

IT SERVES MERELY TO CARRY THE CURRENT FLOWING THROUGH THE CELL

• USUALLY REDOX REACTION OCCUR SIMULTANEOUSLY AT THE AUXILIARY
ELECTRODE.
 WORKING ELECTRODES:
DEPENDING ON THE CHOICE OF WORKING
ELECTRODE, THE TYPE OF VOLTAMMETRY IS DECIDED.
EXAMPLE:
WE USE DROPPING MERCURY ELECTRODE (DME) IN
POLAROGRAPHY TECHNIQUE
WE USE PLATINUM ELECTRODE IN CYCLIC
VOLTAMMETRY
WE USE GLASSY CARBON AS ELECTRODE IN LINEAR
SWEEP VOLTAMMETRY.
 WHAT IS DME?

• THE DROPPING MERCURY ELECTRODE (DME) IS A WORKING

ELECTRODE ARRANGEMENT FOR POLAROGRAPHY IN WHICH
MERCURY CONTINUOUSLY DROPS FROM A RESERVOIR THROUGH A
CAPILLARY TUBE INTO THE SOLUTION. THE OPTIMUM INTERVAL
BETWEEN DROPS FOR MOST ANALYSES IS BETWEEN 1-5 SEC. THE
UNIQUE ADVANTAGE TO THE USE OF DME IS THAT THE CONSTANT
RENEWAL OF THE ELECTRODE SURFACE, EXPOSED TO THE TEST
SOLUTION ELIMINATES THE EFFECTS OF ELECTRODE POISONING.
STRUCTURE OF DME:
 WORKING OF DME:

1. DROPPING MERCURY ELECTRODE IS A POLARIZABLE ELECTRODE AND ACT AS

A BOTH ANODE AND CATHODE.

2. THE POOL OF MERCURY ACTS AS COUNTER ELECTRODE I.E. ANODE IF DME IS

CATHODE CATHODE IF DME IS ANODE

3. THE COUNTER ELECTRODE IS NON-POLARIZABLE ELECTRODE.

4. THE ANALYTE SOLUTION, ELECTROLYTE LIKE KCI IS ADDED I.E. 50-100 TIMES
OF SAMPLE CONCENTRATION.

5. PURE NITROGEN GAS IS BUBBLED THOUGH THE SOLUTION TO EXPEL OUT

OXYGEN.
6. EX: IF THE ANALYTE SOLUTION CONTAIN, CADMIUM IONS THEN CADMIUM
IONS DISCHARGED AT CATHODE
7. THEN GRADUALLY INCREASING VOLTAGE IS APPLIED
TO THE POLAROGRAPHIC CELL AND CURRENT IS
RECORDED.
8. GRAPH IS PLOTTED BETWEEN APPLIED VOLTAGE AND
CURRENT THIS GRAPH IS CALLED AS POLAROGRAM AND
THE APPARATUS IS KNOWN POLAROGRAPH.
9. THE DIFFUSION CURRENT PRODUCED IS DIRECTLY
PROPORTIONAL TO CONCENTRATION OF ANALYTE AND
THIS IS USE FOR QUANTITATIVE ANALYSIS.
10. THE HALF WAVE POTENTIAL IS CHARACTERISTIC OF
 TYPES OF MERCURY
ELECTRODE:

1] DME(DROPPING MERCURY
ELECTRODE)

THE MERCURY DROP FORMS AT THE

END OF THE CAPILLARY THROUGH
GRAVITY. IT GROWS CONTINUOUSLY
AS THE MERCURY FLOWS THE
RESERVOIR AND HAS A FINITE
LIFETIME OF SEVERAL SECONDS. IT IS
THEN DISLODGED AND REPLACED BY
A NEW DROP.
2)SMDE :

SMDE (STATIC MERCURY DROP

ELECTRODE)
• THIS ELECTRODE USES A SOLENOID
PLUNGER TO CONTROL THE FLOW OF
MERCURY. ACTIVATION OF THE
SOLENOID MOMENTARILY LIFTS THE
PLUNGER ALLOWING MERCURY TO
FLOW THROUGH THE CAPILLARY
FORMING A SINGLE HANGING HG-DROP.
3)HMDE:

HDME (HANGING MERCURY DROP

ELECTRODE)
• THE DROP OF MERCURY IS EXTENDED
BY ROTATING A MICROMETER SCREW
THAT PULSES THE MERCURY FROM A
RESERVOIR THROUGH A NARROW
CAPILLARY.
 ADVANTAGES OF DME:
THE SURFACE OF MERCURY DROP IS SMOOTH, CONTINUOUSLY RENEWED AND SURFACE AREA
IS REPRODUCIBLE. THIS ELIMINATES PASSIVITY AND POISONING EFFECT.

MERCURY FORMS AMALGAM WITH MANY METALS.

THE SURFACE AREA CAN BE CALCULATED FROM THE WEIGHT OF THE DROPS. SINCE THE
ELECTROLYTE IS CONTINUOUSLY RENEWED, SERIES OF SCAN BE ESTIMATED IN THE GIVEN
SOLUTION.

THE DIFFUSION CURRENT ASSUMES A STEADY VALUE

• IMMEDIATELY AFTER EACH CHANGE OF THE APPLIED POTENTIAL,

• AND IS REPRODUCIBLE.

IT CAN BE OVER THE RANGE OF +0.4 TO -2.0 VOLT WITH REFERENCE TO THE SATURATED
CALOMEL ELECTRODE.
 DISADVANTAGES OF DME:
CAPILLARY IS VERY SMALL AND THUS CAN BE EASILY BLOCKED.

MERCURY IS VERY TOXIC.

SURFACE AREA OF EACH DROP OF MERCURY IS NEVER CONSTANT.

IT CANNOT BE USED AT HIGHER POSITIVE POTENTIAL DUE TO OXIDATION OF

MERCURY.

THE AREA OF MICROELECTRODE IS CONSTANTLY CHANGING AS THE SIZE OF THE

DROPS CHANGES.

MERCURY MAY BE EASILY OXIDIZED AND THAT DME CAN BE USED ONLY FOR THE
ANALYSIS OF REDUCIBLE OR VERY EASILY OXIDISIBLE SUBSTANCES.
• THE ELECTRODE GENERATE SOME SMALL CURRENTS LIKE RESIDUAL AND
MIGRATION CURRENT, WHICH CAUSES ERROR IN THE CURRENT MEASUREMENT.
 WHY WE NEED THREE ELECTRODE SYSTEM:
THE THREE ELECTRODE SYSTEM REMEDIES MANY OF THE ISSUES OF THE TWO ELECTRODE
CONFIGURATION. THE THREE ELECTRODE SYSTEM CONSISTS OF A WORKING ELECTRODE,
COUNTER ELECTRODE, AND REFERENCE ELECTRODE. THE REFERENCE ELECTRODE’S ROLE
IS TO ACT AS A REFERENCE IN MEASURING AND CONTROLLING THE WORKING ELECTRODE
POTENTIAL, WITHOUT PASSING ANY CURRENT. THE REFERENCE ELECTRODE SHOULD HAVE
A CONSTANT ELECTROCHEMICAL POTENTIAL AT LOW CURRENT DENSITY. ADDITIONALLY,
SINCE THE REFERENCE ELECTRODE PASSES NEGLIGIBLE CURRENT, THE IR DROP BETWEEN
THE REFERENCE AND WORKING ELECTRODE IS OFTEN VERY SMALL. THUS WITH THE THREE
ELECTRODE SYSTEM, THE REFERENCE POTENTIAL IS MUCH MORE STABLE, AND THERE IS
COMPENSATION FOR IR DROP ACROSS THE SOLUTION. THIS TRANSLATES INTO SUPERIOR
CONTROL OVER WORKING ELECTRODE POTENTIAL. THE MOST COMMON LAB REFERENCE
ELECTRODES ARE THE SATURATED CALOMEL ELECTRODE AND THE AG/AGCL ELECTRODE.
• IN THE THREE ELECTRODE CONFIGURATION, THE ONLY ROLE OF THE COUNTER
ELECTRODE IS TO PASS ALL THE CURRENT NEEDED TO BALANCE THE CURRENT
OBSERVED AT THE WORKING ELECTRODE. THE COUNTER ELECTRODE WILL OFTEN
SWING TO EXTREME POTENTIALS IN ORDER TO ACCOMPLISH THIS TASK.
 PRECAUTION TO BE TAKEN WHILE USING
DME
PURE AND TRIPLE DISTILLED MERCURY SHOULD BE USED IN DME.

TIP OF DME SHOULD BE ALWAYS IMMERSED IN WATER WHEN NOT IN

USE.

TIP OF DME SHOULD BE CLEANED BY DIPPING IN NITRIC ACID.

THE DME ASSEMBLY SHOULD BE MOUNTED VERTICAL ON A HEAVY

STAND TO BE FREE FROM VIBRATIONS.

IT IS ESSENTIAL TO USE CLEAN AND DUST FREE TUBING WHILE

SETTING THE DME.
• THERE SHOULD BE SUFFICIENT MERCURY IN RESERVOIR SO THAT
THE PRESSURE CHANGES ARE NEGLIGIBLE.
THANK YOU FOR YOUR
CONCERN.
• TASKINFATMA M.SAIYED
• 22-PCH-075
• M.SC.
• SEM-3