Electrodes
 Electrodes play an important role in making

satisfactory records of bioelectric signals and their choice requires careful consideration.  They should be comfortable for the patients to wear over long periods of time and should not produce any artefacts.  Another desirable factor is the convenience of application of the electrodes.

 The mechanism of electric conductivity in the body

involves ions as charge carriers.  Thus, picking up bioelectric signals involves interacting with these ionic charge carriers and transducing ionic currents into electric currents required by wires and electronic instrumentation.

electrode-electrolyte interface
 This transducing function is carried out by electrodes

that consist of electrical conductors in contact with the aqueous ionic solutions of the body.
 This introduces the “electrode-electrolyte interface”

process, electrode characteristics and different types of electrodes to be used for measuring ECG,EMG,EEG and other bio potentials.

 Due to this contact between a metal and electrolyte solution. are placed on or inside the body. they come in contact with body fluids which may be considered as “ELECTROLYTES”.  The chemical reactions that occur between metals and electrolytes influence the performance of Biopotential electrodes. an electrochemical reaction produces a difference of potential between the metal and solution. .The Electrode-Electrolyte Interface  When electrodes in their simplest form made of pieces of metal.

and (3) anions (denoted by A-) moving in a direction opposite to that of the current in the electrolyte. . passing from the electrode to the electrolyte. (2) cations (denoted by C+ ) moving in the same direction as the current. A net current that crosses the interface. consists of (1) electrons moving in a direction opposite to that of the current in the electrode. The electrolyte represents the body fluid     containing ions.

. The electrolyte is an aqueous solution containing cations of the electrode metal and anions.Electrode–electrolyte interface The electrode consists of metallic atoms C.

 What actually occur are chemical reactions at the interface. which can be represented in general by the following reactions: where n is the valence of C and m is the valence of A . For charge to cross the interface—there are no free electrons in the electrolyte and no free cations or anions in the electrode—something must occur at the interface that transfers the charge between these carriers.

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.  Since it is a good conductor of electricity. making the neutral electrode positively charged with respect to the electrolyte. some of these enter the solution. has an abundance loosely held free valance electrons. The figure shows a silver electrode in an electrolyte (salt) solution.

R is the universal gas constant. This relationship is known as the Nernst equation Where a 1 and a 2 are the activities of the ions on either side of the membrane. n is the valence of the ions.3 V.  The value of this half-cell voltage for a silver electrode is approximately 0.Half-cell Potential  This results in a potential difference called a “half-cell potential”. .8 V and for copper electrode it is approximately 0. and F is the Faraday constant. T is the absolute temperature.

since the half-cell potentials for the silver and copper electrodes are 0.5V. . the PD between the electrodes equals 0.8&0.3V respectively. The following figure shows both the electrodes placed in the electrolyte and. both the electrodes being positive with respect to the electrolyte.

Silver-copper electrodes Half-cell Potentials 0.5 v Silver Copper + ve + ve electrolyte .

. wherein one type of charge is dominant on the surface of the metal and the opposite charge is distributed in excess in the electrolyte lying adjacent to the electrode.Electrical Double Layer  Some sort of separation of charges exist at the metal- electrolyte interface which results in an Electrical Double Layer.

Oxidation or reduction reactions at the electrode-electrolyte interface lead to a double-charge layer .

 2) The concentration of its ions in solution and  3) The temperature  Half cell potential cannot be measured without a second electrode. which is determined by the  1) Metals involved. .  The half cell potential of the standard hydrogen electrode has been arbitrarily set to zero.Half-cell Potential  The knowledge of the half-cell potential.

Half-cell Potentials for Common Electrode Materials at 250C The metal undergoing the reaction shown has the sign and potential E0 when referenced to the hydrogen electrode .

 The metals will develop equal half cell potentials. if chemically identical. .  The difference of potential between the terminals of biopotential electrodes in contact with the body is called the “electrode offset voltage”. which act as an electrolyte. the resulting PD between electrodes will equal to Zero.Electrode offset potential with silver electrodes applied on to the skin surface  The cross section of two silver plates used as biopotential electrodes on the surface of the skin.

.  This offset voltage will thus also be amplified along with the physical variable picked up from the body.8 V half-cell potential is approximately 1000 times greater. which is in the range of 1mV.  If an ECG is being recorded. The offset would be zero if the electrodes are chemically identical. the 0. in practice this is not so and some value of the offset voltage is usually present between the terminals of the applied biopotential electrodes.  However.

. but this current is a displacement current.  This classification refers to what happens to an electrode when a current passes between it and the electrolyte. two types of electrodes are possible: those that are perfectly polarizable and those that are perfectly nonpolarizable.  Perfectly polarizable electrodes are those in which no actual charge crosses the electrode–electrolyte interface when a current is applied. and the electrode behaves as though it were a capacitor. there has to be current across the interface.  Of course.POLARIZABLE AND NONPOLARIZABLE ELECTRODES  Theoretically.

 Perfectly nonpolarizable electrodes are those in which current passes freely across the electrode–electrolyte interface. for perfectly nonpolarizable electrodes there are no overpotentials.  Thus.  Electrodes made of noble metals such as platinum come closest to behaving as perfectly polarizable electrodes. requiring no energy to make the transition. .

the concentration overpotential. it is difficult for them to oxidize and dissolve.  The electrical characteristics of such an electrode show a strong capacitive effect. so a majority of the overpotential seen from this type of electrode is a result of Vc.  Thus current passing between the electrode and the electrolyte changes the concentration primarily of ions at the interface. . Because the materials of these electrodes are relatively inert.

may thus interfere with the desired biosignals and result in undesired artefacts.Ag-AgCl electrode: perfectly nonpolarizable electrode  A large offset voltage due to chemically unmatched electrodes.  Both the half-cell potential and noise from the electrodes. may be reduced by a proper choice of electrode material and by chloriding the silver electrode-called the Silver-Silver-Chloride (Ag-AgCl) electrode. . due to chemical activity taking place with in them.

 Chloride ions from the salt solution then combine with the silver ions of the electrode and a thin film of chloride molecules is deposited on the silver electrode making it look grey. the positive being connected to the electrode to be chlorided. Chloriding is best done in a dark room for a duration of about three minutes with a 3 volt battery. The coating of chloride is done chemically by placing two pieces if pure silver (one of them the electrode) in a bromide-free sodium chloride solution (of %5 concentration) and connecting the two pieces to a DC voltage. .

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 The second process for producing Ag/AgCl electrodes useful in medical instrumentation is a sintering process that forms pellet electrodes. .

and they are best applied when repeated usage is necessary. which is then removed from the die and baked at 400 0C for several hours.sintering Process  The electrode consists of an Ag lead wire surrounded by a sintered Ag/AgCl cylinder.  The die is compressed in an arbor press to form the powdered components into a pellet.  These electrodes tend to have a greater endurance than the electrolytically deposited AgCl electrodes. It is formed by placing the cleaned lead wire in a die that is then filled with a mixture of powdered Ag and AgCl. .

leaving portions of metallic Ag in contact with the electrolyte. The electrolytically deposited AgCl has a tendency to flake off under mechanical stress. . which can cause the electrode’s half-cell potential to be unstable and noisy.

 It is used primarily as a reference electrode for electrochemical determinations and is frequently applied as the reference electrode when pH is measured.  The calomel electrode is often constructed as a glass tube with a porous glass plug at its base filled with a paste of mercurous chloride or calomel (Hg2Cl2) mixed with a saturated potassium chloride (KCl) solution.calomel electrode  A second kind of electrode that has characteristics approaching those of the perfectly nonpolarizable electrode is the calomel electrode. .

so most of it retains its solid form. the Hg2Cl2 is only slightly soluble in water. .  The tube is filled with a saturated KCl solution so that the Hg2Cl2 layer of the inner tube is in contact with this electrolyte through the porous plug of the inner tube.  A layer of elemental mercury is placed on top of the paste layer with an electric lead wire within it. Like AgCl.  This entire assembly is then positioned in the center of a larger glass tube with a porous glass plug at its base.

. which will add to the electrode half-cell potential.  The porous plug at the bottom of the electrode assembly is used to make contact between the internal KCl solution and the solution in which the electrode is immersed.  This is actually a liquid–liquid junction that can result in a liquid–liquid junction potential. We have a half-cell made up of Hg in intimate contact with an Hg2Cl2 layer that is in contact with the saturated KCl electrolyte.

the characteristics of an electrode are sensitive to the current passing through the electrode. in turn.  Specifically. and.ELECTRODE BEHAVIOR AND CIRCUIT MODELS  The electrical characteristics of electrodes have been the subject of much study. nonlinear elements are required for modeling electrode behavior. and the electrode characteristics at relatively high current densities can be considerably different from those at low current densities.  Often the current–voltage characteristics of the electrode–electrolyte interface are found to be nonlinear. .

. The characteristics of electrodes are also waveform dependent. the characteristics are also frequency dependent.  When sinusoidal currents are used to measure the electrode’s circuit behavior.

of course.  This. For sinusoidal inputs.  The half-cell potential described earlier was the result of the distribution of ionic charge at the electrode–electrolyte interface that had been considered a double layer of charge. should behave as a capacitor—hence the capacitive reactance seen for real electrodes. . the terminal characteristics of an electrode have both a resistive and a reactive component.  Over all but the lowest frequencies. this situation can be modeled as a series resistance and capacitance.

 To avoid this problem.CIRCUIT MODELS  The series resistance–capacitance equivalent circuit breaks down at the lower frequencies. where this model would suggest an impedance going to infinity as the frequency approaches dc. . we can convert this series RC circuit to a parallel RC circuit that has a purely resistive impedance at very low frequencies.

we can arrive at the biopotential electrode equivalent circuit model shown .biopotential electrode equivalent circuit  If we combine this circuit with a voltage source representing the half-cell potential and a series resistance representing the interface effects and resistance of the electrolyte.

Rd and Cd represent the resistive and reactive components just discussed. In this circuit.  Cd represents the capacitance across the double layer of charge at the electrode–electrolyte interface.  These components are still frequency and current- density dependent. .  In this configuration it is also possible to assign physical meaning to the components.

 The parallel resistance Rd represents the leakage resistance across this double layer. and—to a lesser extent—by the material of the electrolyte and its concentration. .   All the components of this equivalent circuit have values determined by the electrode material and its geometry.

 At low frequencies. being Rs + Rd.  The impedance of Ag/AgCl electrodes varies significantly from that of a pure silver electrode at frequencies under 100 Hz.  At frequencies between these extremes. . The equivalent circuit of Figure demonstrates that the electrode impedance is frequency dependent. the electrode impedance is frequency dependent. the impedance is constant at Rs. the impedance is again constant but its value is larger. where 1=wC>>Rd.  At high frequencies. where 1=wC<<Rd.

Impedance as a function of frequency for Ag electrodes coated with an electrolytically deposited AgCl layer. Numbers attached to curves indicate number of mAs for each deposit. The electrode area is 0.25 cm2. .

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