Corrosion engineering

Working of Potentiostat and its Importance in Corrosion Study

Submitted to Prof. Dr. Akhlaq Ahmed Submitted by Muhammad Naeem Redg. No. 2011-MS-MME-22

De artme!t of Metallurgi"al a!d Material# E!gi!eeri!g $!i%er#ity of E!gi!eeri!g & 'e"h!ology (ahore
Working of Potentiostat and its importance in Corrosion study
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Potentiostat
An electronic instrument that measures and controls the voltage difference between a Working Electrode and a Reference Electrode. It measures the current flow between the Working and Counter Electrodes. Potential or Voltage (E sometimes V!" #nit" Volt $he Potential is the driving force for the redo% reaction. $he &otential is related to the thermod'namics of the s'stem" () * +n F (E(negative () is s&ontaneous! Potential is alwa's measured versus a Reference Electrode. A &ositive voltage is o%idative and a negative voltage is reductive. , Volts is not nothing- Redo% reactions ha&&en at , volts that do not ha&&en at ./ volt. $here is no correlation between the thermod'namics of the chemical s'stem and the kinetics (rate! of the reaction.

What is Current Current (i!" #nit" Ampere

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Electron flow is the result of a redo% reaction. Current measures the rate of the reaction (electrons per second!. 0ero current is nothing i.e. if the current is 1ero no redo% reactions are occurring (that2s not 3uite true in corrosion-!. Anodic (o%idation! and cathodic (reduction! currents have different &olarit' (signs!. Current ma' be e%&ressed as current or current densit'. Electrodes A Potentiostat works with three electrodes immersed in a conductive electrol'te. Working Electrode

A sam&le of the corroding metal being tested. Reference Electrode

An electrode with a constant electrochemical &otential. Counter Electrode

A current+carr'ing electrode that com&letes the cell circuit. Why does a Potentiostat have three electrodes? We would like to stud' the electrochemical events taking &lace at one s&ecific electrode4the Working Electrode. $he use of a three+electrode &otentiostat with a se&arate Reference and Counter Electrode allows the &otential at the WE and the current at the WE to be measured with little or no 5interference6 or 5contribution6 from the other electrodes. Pay pecial Attention to the !eference Electrode" A Potentiostat needs a low im&edance Reference Electrode#se large 7unction reference electrodes Re&lace isolation frits regularl' Avoid narrow 8uggin Ca&illaries Potentiostats are less forgiving of high+im&edance Reference Electrodes than &9 :etersIf there2s an &roblem with the cell it2s almost alwa's the Reference Electrode#he Analog Potentiostat
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Potentiostat
C CA V
i

Control Amp

V R %&E Converter
m

Electrometer Cell 'itch

WE

R E

CE

#hree Primary Components of a Potentiostat Control Am&lifier" ;u&&lies the &ower to maintain the controlled &otential between the Working and Reference Electrodes. Electrometer" :easures the &otential difference between the Reference and Working Electrodes. Current+to+Voltage Converter" :easures the current between the Working and Counter Electrodes.

$asic relationships
A &otentiostat is a control and measuring device. It com&rises an electric circuit which controls the &otential across the cell b' sensing changes in its resistance var'ing
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accordingl' the current su&&lied to the s'stem" a higher resistance will result in a decreased current while a lower resistance will result in an increased current in order to kee& the voltage constant as described b' <hm=s law.

As a result the variable s'stem resistance and the controlled current are inversel' &ro&ortional

Is the out&ut electrical current of the &otentiostat Is the voltage that is ke&t constant Is the electrical resistance that varies.

Principles of (peration
;ince />?@ when 9ickling built the first three electrode &otentiostat
ABC

substantial

&rogress has been made to im&rove the instrument. 9ickling=s device used a third electrode thereference electrode to control the cell &otential automaticall'. #& until the &resent da' his &rinci&le has remained in use. At a glance a &otentiostat measures the &otential difference between the working and the reference electrode a&&lies the current through the counter electrode and measures the current as an over a series resistor ( in Dig. /!. voltage dro&

$he control am&lifier CA is res&onsible for maintaining the voltage between the reference and the working electrode as closel' as &ossible to the voltage of the in&ut source . It ad7usts its out&ut to automaticall' control the cell current so that a

condition of e3uilibrium is satisfied. $he theor' of o&eration is best understood using the e3uations below. Prior to observing the following e3uations one ma' note that from an electrical &oint of view the electrochemical cell and the current measurement resistor ma' be

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regarded as two im&edances (Dig. @!.

includes

in series with the interfacial

im&edance of the counter electrode and the solution resistance between the counter and the reference. re&resents the interfacial im&edance of the working electrode in

series with the solution resistance between the working and the reference electrodes.

Dig. ;chematic of a &otentiostat with electrochemical cell re&laced b' two im&edances. $he role of the control am&lifier is to am&lif' the &otential difference between the &ositive (or noninverting! in&ut and the negative (or inverting! in&ut. $his ma' be translated mathematicall' into the following e3uation" . (/! where is the am&lification factor of the CA. At this &oint the assum&tion ma' be made that a negligible amount of current is flowing through the reference electrode. $his correlates to &h'sical &henomenon since the reference electrode is connected to a high im&edance electrometer. $hus the cell current ma' be described in two wa's"

(@! and . (E! Combining E3s. (@! and (E! 'ields E3. (?!"

(?!

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where

is the fraction of the out&ut voltage of the control am&lifier returned to its

negative in&utF namel' the feedback factor"

. Combining E3s. (/! and (?! 'ields E3. (G!"

. (G! When the 3uantit' becomes ver' large with res&ect to one E3. (G! reduces to E3.

(H! which is one of the negative feedback e3uations" . (H! E3. (H! &roves that the control am&lifier works to kee& the voltage between the reference and the working close to the in&ut source voltage.

ignificant features
In electrochemical e%&eriments the electrodes are the &ieces of e3ui&ment that comes in immediate contact with the anal'te. Dor this reason the electrodes are ver' im&ortant for determining the e%&erimental result. $he electrode surface ma' or ma' not catal'1e chemical reactions. $he si1e of the electrodes affects the magnitude of the currents &assed which can affect signal to noise. Iut electrodes are not the onl' limiting factor for electrochemical e%&erimentsF the &otentiostat also has a limited range of o&eration. $he following are a few significant features that var' between instruments. Electric potential range )measured and applied* " while the &otential window is mostl' based on the solvent window the electronics can also limit the &ossible range. Accuracy in potential )measured and applied* " limits of deviations between the actual and re&orted. !ange of scan rate" how slow or fast a &otential window can be scanned this is most im&ortant for e%&eriments that re3uire high scan rates such as those involving ultra microelectrodes.

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ample rate" the rate at which &otential or voltage can be accuratel' sam&led. $his can be im&ortant for e%&eriments that need high scan rates such as those involving ultra microelectrodes. File si+e" a limiting factor can be the file si1e limit. $his would most likel' affect the choice of the &otential range swe&t or the &otential sam&le rate. Electric current range )measured and applied* " the ma%imum range over which current can be sam&led. A&&l'ing large currents is im&ortant for e%&eriments that &ass a great deal of current like a large bulk electrol'sis. :easuring small currents is im&ortant for e%&eriments that &ass small currents like those involving ultra microelectrodes. Current resolution" determines the o&erational range of a s&ecific e%&eriment and the bit resolution of that data in the current dimension. Accuracy in current )measured and applied* " limits of deviations between the actual and re&orted. ,um-er of 'orking channels" how man' working electrodes can the instrument control. A bipotentiostat is necessar' to controlling s'stems with two working electrodes like a rotating ring+disk electrode. A &ol'&otentiostat ma' be im&ortant for controlling some biological e%&eriments with three or more working electrodes. Footprint" &otentiostat include small devices of about @, % /, % B cm weighing well under a kilogram or a sim&le board that can be installed in a deskto& com&uter. A large bench+to& model would be on the order of B, % @, % /, cm and weigh u& to or more than B kilograms. %nterface" can the instrument run inde&endentl' or must the' be slaved to a &ersonal com&uter. 'eep generator" can the s'stem a&&l' an analogue swee& or does it use a digital staircase generator as an a&&ro%imation. If it does use a digital staircase then the resolution of the staircase is im&ortant. !otating electrode" can the instrument o&erate a rotating electrode. $his is intrinsic for e%&eriments that re3uire a rotating disk electrode or rotating ring+disk electrode.

Primar' use
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$his e3ui&ment is fundamental to modern electrochemical studies using three electrode s'stems for investigations of reaction mechanisms related to redo% chemistr' and other chemical &henomena. $he dimensions of the resulting data de&end on the e%&eriment. In voltammetr' electric current in am&s is &lotted against electric &otential in voltage. In a bulk electrol'sis total coulombs &assed (total electric charge! is &lotted against time in seconds even though the e%&eriment measures electric current (am&eres! over time. $his is done to show that the e%&eriment is a&&roaching an e%&ected number of coulombs. :ost earl' &otentiostats could function inde&endentl' &roviding data out&ut through a &h'sical data trace. :odern &otentiostats are designed to interface with a &ersonal com&uter and o&erate through a dedicated software &ackage. $he automated software allows the user ra&idl' to shift between e%&eriments and e%&erimental conditions. $he com&uter allows data to be stored and anal'1ed more effectivel' ra&idl' and accuratel' than historic methods.

ummary.
1. In order to ensure stable &otential control of an electrochemical cell with a double la'er ca&acitance in the boundar' la'er it is essential to have a &otentiostat with &hase com&ensation. $he internal &hase angle of the &otentiostat must not e%ceed >,J u& to about the transit fre3uenc'. @. Dor similar reasons it is necessar' that the internal resistance of the &ower out&ut stage should not &roduce additional &hase shift u& to about the transit fre3uenc'. E. $he time constant of the reference electrode Kca&illar' s'stem $k * Rk Ck should be ke&t small com&ared with the rise time constant of the &otentiostat $ */KLt. ?. $he cell resistance R1 and the resistance Rm and R7 should be made as small as &ossible in order to achieve a large bandwidth. B. If Lg is smaller than Mo Lt there is a rise in the fre3uenc' characteristic which increases when Lg and Mc Lt are further a&art and when the difference between R& and Rs increases. $his rise causes an overshoot in the res&onse to a ste& in&ut and &roduces dam&ed oscillations as the difference between the two values increases.
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