ELEC4810: Introduction to

Biosensors and Bioinstrumentation

Lecture Notes – Set #5

ELEC4810

Textbook: Chapter 5
 Chapter 2
Biopotentials: the Origin and Measurements

Main Topics:
Electrical Activity at Cellular Level
• bioelectric phenomena at the cellular level
• volume conductor potential distributions
• typical bioelectric sources: heart, brain, muscle, etc.

Recordings of bioelectric signals

• electrocardiogram (ECG)
• electromyogram (EMG)
• electroencephalogram (EEG)

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 2.7 Biopotential Electrodes
• An interface between the body and machine
• General problem: How to transduce ionic currents in the electrolytes in
the body fluid into electronic currents in wires?

The first table-model Enithoven electrocardiograph manufactured by the

Cambridge Scientific Instrument Company of London in 1911.
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 2.7 Biopotential Electrodes
• An interface between the body and machine
• General problem: How to transduce ionic currents in the electrolytes in
the body fluid into electronic currents in wires?

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 2.7 Biopotential Electrodes: an interface between the body and machine
A general model to record the electrocardiographic signal:
𝑍𝑍1
Bio-voltage 𝑍𝑍𝐴𝐴

𝑍𝑍2 Amplifier

• Our first impression is that this is a rather simple function to achieve and that biopotential electrodes
should be relatively straightforward – place a pair of metal electrodes on body surface.
• When we consider the problem in more detail, we see that the electrode actually carries out a
transducing function, because in the body current is carried by ions, whereas in the electrode and its
lead wire it is carried by electrons.

Electrode–electrolyte interface:
• The passage of electric current from the body to
an electrode can be understood by examining the
electrode–electrolyte interface
• The current crosses it from left to right. The
electrode consists of metallic atoms C. The
electrolyte is an aqueous solution containing
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cations of the electrode metal C+ and anions A-.
 2.7 Biopotential Electrodes: an interface between the body and machine
• The electrolyte represents the body fluid containing
ions.
• A net current that crosses the interface, passing from
the electrode to the electrolyte, consists of
1. electrons moving in a direction opposite to that
of the current in the electrode
2. cations (denoted by C+) moving in the same
direction as the current
3. anions (denoted by A-) moving in a direction
opposite to that of the current in the electrolyte.

Chemical reactions at interface:

Oxidation
→ Dissolution
𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝐶𝐶 ↔ 𝐶𝐶 𝑛𝑛+ + 𝑛𝑛𝑒𝑒 − 𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸
Production 𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝐴𝐴𝑚𝑚− ↔ 𝐴𝐴 + 𝑚𝑚𝑒𝑒 − 𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸
of electron Reduction
Where n is the valence of C and m is the valence of A. → Precipitation

6 Requirements: no chemical and mechanical hazards.

 2.7 Biopotential Electrodes: an interface between the body and machine

Half-cell potential:
• Electrolyte surrounding the electrode is at different electric potential from the rest of the solution.
• Half-cell potential is dependent on the metal involved and concentration of its ion in the electrolyte.
Large mount of free electrons

The half-cell potential of electrode can affect the

performance to detect the potential signal.

𝐸𝐸0 = 𝐸𝐸ℎ𝑐𝑐𝑐 − 𝐸𝐸ℎ𝑐𝑐𝑐

Surface electrode charge distribution

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 2.7 Biopotential Electrodes: an interface between the body and machine

Half-cell potential:
• Electrolyte surrounding the electrode is at different electric potential from the rest of the solution.
• Half-cell potential is dependent on the metal involved and concentration of its ion in the electrolyte.

Measurement of half-cell potential

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 2.7 Biopotential Electrodes: an interface between the body and machine
Open-circuit half-cell potential:
Nernst equation for electrode-electrolyte interface:

𝐾𝐾𝐾𝐾 𝑎𝑎1
𝐸𝐸 = − ln( )
𝑞𝑞 𝑎𝑎2

where a1,2 are the activity of ions in the electrode and electrolyte.
• The ionic activity is the availability of the ions for the reaction.
• For a metal, a = 1. For low ion concentration, a≈concentration of ion.

𝐾𝐾𝐾𝐾
Half-cell potential: 𝐸𝐸 = 𝐸𝐸0 + ln(𝑎𝑎𝑐𝑐+ )
𝑞𝑞

Half cell potential at standard condition

→ high 𝐶𝐶 + concentration, 𝑎𝑎𝐶𝐶 + ~1

𝐾𝐾𝐾𝐾 𝑎𝑎1 𝑎𝑎2𝑠𝑠 𝐾𝐾𝐾𝐾 𝑎𝑎1 𝐾𝐾𝐾𝐾 𝑎𝑎2𝑠𝑠

Derivation: 𝐸𝐸 = − ln( � )=− ln( ) − ln( )
𝑞𝑞 𝑎𝑎2 𝑎𝑎2𝑠𝑠 𝑞𝑞 𝑎𝑎2𝑠𝑠 𝑞𝑞 𝑎𝑎2

𝐾𝐾𝐾𝐾 𝐾𝐾𝐾𝐾
𝐸𝐸 = 𝐸𝐸0 + ln 𝑎𝑎2 − ln(𝑎𝑎2𝑠𝑠 ) 𝑎𝑎2𝑠𝑠 ~1
9 𝑞𝑞 𝑞𝑞
 2.7 Biopotential Electrodes: an interface between the body and machine
Overpotential:
• The difference between the observed half cell potential and the equilibrium zero-current
half-cell potential is known as overpotential.
Three mechanisms:
1. Ohmic overpotential: a direct result of the resistance of the electrolyte; a random variable
depends on current, temperature, non-linearity, individual and etc.
2. Concentration overpotential: the equilibrium state of ion concentration in the vicinity of
the electrode-electrolyte interface will be changed when current is not the zero.
3. Activation overpotential: the oxidation reaction may need different activation energy as
reversed reduction reaction. => change the equilibrium state.

𝑉𝑉𝑝𝑝 = 𝑉𝑉𝑟𝑟 + 𝑉𝑉𝑐𝑐 + 𝑉𝑉𝑎𝑎

where
Vp = total overpotential, or polarization potential, of the electrode
Vr = ohmic overpotential
Vc = concentration overpotential
Va = activation overpotential

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 2.7 Biopotential Electrodes: an interface between the body and machine
Polarizable and non-polarizable electrodes:
• A perfectly polarizable electrode respond a current as an perfect capacitor would.
 no charge crosses the electrode-electrolyte interface.
 capacitive: displacement current only.
 Noble metals (like Au, Pt) or other metal electrode of oxidized surface
make good polarizable electrodes

𝑑𝑑𝑑𝑑
𝑖𝑖 = 𝐶𝐶
𝑑𝑑𝑑𝑑

Current and voltage are

not linearly related.

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 2.7 Biopotential Electrodes: an interface between the body and machine
Polarizable and non-polarizable electrodes:
• A perfectly non-polarizable electrode would respond a current as a perfect conductor would.
 current passes freely across electrode/electrolyte interface
 resistive: low voltages develops across the electrodes
 idea for potential signal measurement
 reactive metals act as non-polarizable electrodes. e.g. Ag-AgCl electrode is nearly non-
polarizable electrode.
𝑉𝑉 Current and voltage
𝐼𝐼 = are linearly related.
𝑅𝑅

Equivalent electrode circuit:

• Even the best available

electrocardiographic electrode
is polarizable to some extent.

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 2.7 Biopotential Electrodes: an interface between the body and machine

• Series-parallel circuit for electrode pair:

Idea case: two electrodes are

electrically identical → same half-
cell potential → cancellation of half-
cell potential. ← equality, a rare
condition.

In practice, the half-cell potentials

are not the same; they depend on
electrode corrosion, change of ion
concentration as time and location,
temperature fluctuation, skin
contact, current, etc. → time
varying offset; can not be removed
from the signal.

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 2.7 Biopotential Electrodes: an interface between the body and machine

• Silver/silver chloride (Ag/AgCl) electrode: Reactions occur at the interface:

Oxidation
𝐴𝐴𝐴𝐴 ↔ 𝐴𝐴𝐴𝐴+ + 𝑒𝑒 − → Dissolution

Reduction
𝐴𝐴𝐴𝐴+ + 𝐶𝐶𝐶𝐶 − ↔ 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 ↓ → Precipitation

The Nernst equation for a general oxidation-reduction reaction

𝛼𝛼𝐴𝐴 + 𝛽𝛽𝛽𝛽 ↔ 𝛾𝛾𝛾𝛾 + 𝛿𝛿𝛿𝛿 + 𝑛𝑛𝑒𝑒 −

𝐴𝐴 𝐶𝐶 +𝑝𝑝
𝑛𝑛𝑒𝑒 − 𝛾𝛾 𝛿𝛿
𝐵𝐵 𝐷𝐷+𝑚𝑚 𝐾𝐾𝐾𝐾 𝑎𝑎𝐶𝐶 𝑎𝑎𝐷𝐷
𝐸𝐸 = 𝐸𝐸0 + ( )
𝑛𝑛𝑛𝑛 𝑎𝑎 𝛼𝛼 𝑎𝑎 𝛽𝛽
𝐴𝐴 𝐵𝐵
𝐸𝐸
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 2.7 Biopotential Electrodes: an interface between the body and machine
• Silver/silver chloride (Ag/AgCl) electrode:

Reactions occur at the interface:

𝐴𝐴𝐴𝐴 ↔ 𝐴𝐴𝐴𝐴+ + 𝑒𝑒 − → Conducts current

𝐴𝐴𝐴𝐴+ + 𝐶𝐶𝐶𝐶 − ↔ 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 ↓ → Slightly soluble, slow reaction, stable

rate for precipitation and
dissolution, charge neutrality

Silver chloride's rate of precipitation and

dissolution is a constant measured by the
solubility product:
𝐾𝐾𝑠𝑠 = 𝑎𝑎𝐴𝐴𝐴𝐴+ × 𝑎𝑎𝑐𝑐𝑐𝑐− ~ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐

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 2.7 Biopotential Electrodes: an interface between the body and machine
• Silver/silver chloride (Ag/AgCl) electrode:

The measured 𝐾𝐾𝑠𝑠 ~ 10−10 in the electrolyte has relatively high concentration of 𝐶𝐶𝐶𝐶− ions (activity ~ 1).
→ activity of Ag ion must be very low ~ 𝐾𝐾𝑠𝑠
𝐾𝐾𝑠𝑠 = 𝑎𝑎𝐴𝐴𝐴𝐴+ × 𝑎𝑎𝑐𝑐𝑐𝑐− ~ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Half-cell potential:

𝐾𝐾𝐾𝐾 𝐾𝐾𝐾𝐾 𝐾𝐾𝑆𝑆

𝐸𝐸 = 𝐸𝐸𝐴𝐴𝐴𝐴 0 + ln 𝑎𝑎𝐴𝐴𝐴𝐴+ = 𝐸𝐸𝐴𝐴𝐴𝐴 0 + ln
𝑞𝑞 𝑞𝑞 𝑎𝑎𝐶𝐶𝐶𝐶−

0 𝐾𝐾𝐾𝐾 𝐾𝐾𝐾𝐾
= 𝐸𝐸𝐴𝐴𝐴𝐴 + ln 𝐾𝐾𝑠𝑠 − ln 𝑎𝑎𝐶𝐶𝐶𝐶−
𝑞𝑞 𝑞𝑞
C C

In body fluid, the concentration of chloride ion is relatively high and stable. The half-cell potential
of silver/silver chloride electrode is not strongly dependent on the silver ion concentration which
varies as the current or oxidation reaction.

→ Electrical characteristics of silver/silver chloride electrode are relatively stable.

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 2.7 Biopotential Electrodes: an interface between the body and machine
• Making of Ag/AgCl electrode by using electrolytic deposition :

Hydrochloric acid (HCl) + Salt (NaCl)

Anode reaction (+): Ag + 𝐶𝐶𝐶𝐶 − => 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴. ↓ + e-

Cathode reaction (-): 2H+ + 2e- => 𝐻𝐻2 ↑ (It is not possible to make use
of Ag+ ions to combine with e- because none are
present.)
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 2.7 Biopotential Electrodes: an interface between the body and machine

• Electrical characteristics of Ag/AgCl electrode:

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 2.7 Biopotential Electrodes: an interface between the body and machine

• Compact Ag/AgCl electrodes for biopotential measurements

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 2.7 Biopotential Electrodes: an interface between the body and machine

• The Electrode-Skin Interface:

Total equivalent circuit

• Epidermis: a constantly changing layer, the outer surface consisting of dead material, stratum
corneum has different electrical properties.
• The deeper layers are similar to other tissues.
→ To achieve better result, the stratum corneum should be removed.
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 2.7 Biopotential Electrodes: an interface between the body and machine

• The Electrode-Skin Interface:

Variation of resistance of skin/electrolyte/electrode with time

< 0.5%

>10%

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 2.7 Biopotential Electrodes: an interface between the body and machine
Have fun with biopotentials
Electromyogram (EMG)

Electrocardiogram (ECG)

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