UNIT-I Types of electrolytic conductors

ELECTROCHEMISTRY Strong electrolytes: Completely dissociate into ions in solution

Examples: HCl, NaOH, NaCl, KCl
Weak electrolytes: Which dissociate only to some extent in
Electrochemistry deals with Chemical applications of electricity
solution
i.e., Chemical reactions produced by passing electric current
Non – electrolytes: Do not ionise in solution
through an electrolyte or production of electric curerent through a
chemical reaction
Cell Terminology
Conductors: Material which allows free flow of electricity
i. Current : Flow of electrons through a conductor
Examples: All metals, graphite, fused salts, solution of electrolytes,
ii. Electrode : Electrode is a material (rod, bar, strip)
Non-conductors (Insulators): Materials which cannot conduct
which conducts electrons
electrical current
iii. Anode : Electrode at which oxidation occurs
Examples: wood, plastics, most of non metals
iv. Cathode : Electrode at which reduction occurs
Types of conductors
v. Electrolyte : Water soluble substance forming ions in
(i) Metallic conductors : All solid material, which
solution and conducts electric current
conduct electric current due to the movement of
vi. Anode compartment: Compartment of the cell in
electron from one end to the other end
which the oxidation half reaction occurs. Contains the
(ii) Electrolytic conductors : Conduct electric current due
anode
to the movement of ions
vii. Cathode compartment: Compartment of the cell in
which the reduction half reaction occurs. Contains the
Differences between metallic conduction and electrolytic
cathode
conduction
viii. Half – cell: Part of the cell, which contains an
Metallic conduction Electrolytic conduction
electrolyte dipped in an electrolyte. If oxidation occurs
Involves flow of electrons Involves movement of ions in
in this half, then it is called the oxidation half cell. If
a solution
reduction occurs at the cell, it is called the reduction
Does not involve any transfer Involves transfer of electrolyte
half cell
of matter in the form of ions
ix. Cell: Device consisting of two half cell. The two half
Conduction decreases with Conduction increases with cells are connected by a conductor
increase in T increase in T
No change in the chemical Chemical changes occur aat
properties of the conductor the two electrodes
Electrode Potential Standard electrode potential (E0): Tendency of a metallic
electrode to lose or gain electrons when it is in contact with a
When a metal (M) is placed in a solution of its own salt (Mn+) one solution of its own ions of 1M Concentration.
of the two processes are possible. Nernst Equation for Electrode Potential
(i) +ve metal ions may pass into solution Consider the redox reaction : M Mn+ + ne-
M Mn+ + ne- (Oxidation) For such redox reversible reactions, the free energy change (∆G)
(ii) +ve metal ions from solution may deposit on the metal and its equilibrium constant (K) are related by
Mn+ + ne- M (reduction)
G   RT ln K  RT ln
 Pr oduct 
 Re ac tan t 
+
Zn electtrode Cu electtrode  G 0 RT ln
 Pr oduct  (1)
+  Re ac tan t 
+ + +
+ + ∆G0 = Standard free energy change
+ +
+ ZnSO4
Cu2+
CuSO4 The above equation is Van’t Hoff Isotherm
solution solution
(i) In the cell, if the reaction involves the transfer of ‘n’ electrons, ‘n’
When Zn electrode is dipped in ZnSO4 solution, Zn goes into faraday of electricity will flow.
solution as Zn2+ ions. If E is the emf of the cell, the total electrical energy produced will
(iii) When Cu electrode is dipped in CuSO4 solution, Cu2+ be
ions from solution deposit on the metal. G  nEF (or) G 0  nE 0 F (2)
A layer of + or – ve ions if formed on the metal, Helmholtz
electrical double layer due to which a difference of potential is Comparing (1) & (2) - nEF  - nEF0 RT ln
M  (3)
 M n  
setup between the metal ions and the solution.
At equilibrium, the potential difference becomes a constant value Dividing (3) by – nF and knowing that [M] = 1
(Electrode potential of the metal). RT 1 RT
E=E 0  ln (or) E=E 0  ln  M n  
The tendency of the electrode to lose electrons is Oxidation nF  M n
nF
potential.
Tendency of an electrode to gain electrons is reduction potential.
2.303RT
E=E 0  log  M n   (4)
nF
Single electrode potential (E): Tendency of a metallic electrode
When, R = 8.314 J/K/mole; F = 96,500 coloumbs, T = 298 K the
to lose or gain electrons when it is in contact with a solution of its
above equation becomes
own ions.
 It is represented as
0.0591 In the cell, when SHE acts as anode, the electrode reaction is
E=E 0  log C  (Nernst equation for single H2(g) 2H+ + 2e-
n
electrode potential) When it acts as cathode, the electrode reaction is
2H+ + 2e- H2(g)
Applications of Nernst equation Limitations
i. To calculate unknown electrode potentials i. requires hydrogen gas and is difficult to set up and
ii. Prediction of corrosion tendency of metals transport
iii. To construct emf series ii. requires large volume of test solution
iii. The solution may poison the surface of Pt electrode
Measurement of single electrode potential iv. Potential of the electrode is dependent on atmospheric
It is not possible to evaluate the absolute value of a single electrode pressure.
potential. Potential difference between two electrodes can be
measured. For this purpose a reference electrode is used. Secondary reference electrode: Saturated calomel electrode
Saturated hydrogen electrode (SHE) is a common reference (SCE)
electrode whose potential is fixed as zero (Primary reference
electrode) Pt wire Construction: Calomel electrode
The emf of the cell with SHE and the electrode under test as consists of a glass tube containing Hg at
the bottom over which mercurous
electrodes will be equal to the potential of the electrode chloride paste is placed. The tube is
Setting up of SHE is difficult filled with a saturated solution of KCl. A
Pt electrode is dipped in. The side tube
Saturated calomel electrode is used as a secondary reference is for making contact via a salt bridge.
electrode The electrode potential of this electrode
is +0.2422 V. It is represented as:
Hg, Hg2Cl2(s), KCl (sat. solution)
Primary reference electrode: Saturated hydrogen electrode
(SHE)
In the cell, when SCE acts as anode, the electrode reaction is
Construction: Hydrogen electrode
consists of a Pt foil that is connected to a Pt 2Hg(l) Hg22+ +2 e -
H2 gas wire sealed in a glass tube. Hydrogen gas When it acts as cathode, the electrode reaction is
is passed through the arm of the
HCl surrounding gas tube. The electrode Hg22+ +2 e - 2Hg(l)
solution dipped in 1N HCl and hydrogen is passed
Pt foil at 1 [Link] SHE
Pt , H2 (1atm) / H+n(1M) ; E0 = 0V
 The electrode potential (cathode) is given by Electrochemical series
RT
E( calomel )  E (0calomel )  ln aCl 
2F Electrode Electrode E0 Nature
The electrode potential depends on the activity of Cl – and reaction (V)
+
Temperature. Li /Li Li+ + e Li -3.01 Anodic
Mg2+/Mg Mg2+ +2 e Mg -2.37
a Kcl emf a Kcl emf (V) a Kcl emf (V) 2+
Pb /Pb Pb2+ +2 e Pb -1.12
0.1 0.3338 1.0 0.2800 Saturated 0.2422 2+
Zn /Zn Zn 2+
+2 e Zn -0.76
Values at 298 K
Fe2+/Fe Fe2+ +2 e Fe -0.44
2+
Measurement of single electrode potential of Zn using SCE Sn /Sn Sn2+ +2 e Sn -0.136 Pt-
Pt wire H+/H2 2H+ + 2e H2 0.00 Reference:
V Zn electrode is coupled with calomel
2+
Zn electrode. Since, the reduction potential of Cu /Cu Cu2+ +2 e Cu +0.34
electrode Zn electrode is less than E0Cal ; calomel +
electrode will act as cathode and the reaction Ag /Ag +
Ag + e Ag +0.80
Hg2Cl2(s) 2Hg(l) + 2C l- Au+/Au Au+ + e Au +1.50
Cathodic
Ecell  Eright
0
 Eleft
0
; Ecell  Ecal  EZn
0 0
½ F2/F- ½ F2 + e F- +2.87
0
EZn  Ecal
0
 Ecell  0.2422  1.0025  0.7603V
1 M Zn2+ Significance of emf series (or) Application of electrochemical
series (or) Applications of Nernst equation
Electrode potentials of metals with respect to SHE
(Electrochemical series (or) EMF series) i. Calculation of standard emf of the cell
E0can be calculated if the standard electrode potential values are
Definition: known
When the various metals are arranged in the order of their Ecell  Eright
0
 Eleft
0

increasing values of standard reduction potential on the hydrogen

scale, the arrangement is called the electrochemical series
ii. Relative ease of oxidation or reduction
Higher (+ve) value of standard reduction potential, greater is the
tendency for reduction.
Metals on the top (- value) are more easily oxidized.
Fluorine has higher +ve value of standard reduction potential Galvanic series
(+2.87V) and shows higher tendency for reduction. Magnesium Oxidation potential of various
Lithium has highest – ve value (-3.02V) and shows higher Magnesium alloys metals alloys are measured by
immersing them in sea water.
tendency towards reduction. Zinc SCE is used as the reference
Alluminium electrode. The values are
iii. Displacement of one element by the other arranged in decreasing order of
Alluminium alloys activity and the series is Galvanic
Metals which lie higher in the series can displace those which lie Copper series
below them in the series. Copper – nickel
Copper will displace silver from its solution. alloys
Iron will displace copper from its solution. Gold
iv. Determination of equilibrium constant (K) for a reaction Platinum

G 0  RT ln K  2.303RT log K This series provide more practical information on the
G 0
nFE 0
relative corrosion tendencies of different metals and alloys. The
log K    G 0  nFE 0 
2.303RT 2.303RT speed of corrosion depends on the difference in potential between
From the value of E0, the equilibrium constant for the reaction can the anodic and cathodic metals in contact.
be obtained
Electrolytic cells
v. Hydrogen displacement behaviour Chemical changes are brought about by using electrical energy in
Metals with – ve reduction potential (metals placed above H2) in electrolytic cells
emf series will displace hydrogen from acid solutions. Electrolysis
Zn will displace H2 from dilute acids whereas, silver cannot. Process of chemical decomposition of an electrolyte by passage of
electricity
vi. Predicting the spontaneity of redox reactions Example: Electrolysis of HCl
If E0 of a cell is +ve the reaction is spontaneous Mechanism
If E0 of a cell is -- ve the reaction is not possible HCl will dissociate into H+ and Cl – in water
On passing electric current the following reactions
1N HCl occur at the electrodes
-
At anode: 2Cl Cl2 + 2 e (oxidation)

At cathode:
2H+ + 2 e - H2 (reduction)
Bright
Pt electrodes
Electrochemical cells (Galvanic cells) Representation of a galvanic cell (Cell diagram)
Chemical energy is converted to electrical energy in i. Galvanic cell consists of two electrodes, anode and
electrochemical cells cathode
Example: Daniel Cell through the voltmeter. ii. Anode is written on the LHS and cathode on RHS
iii. The anode is written with the metal first and then the
V electrolyte which are separated by a vertical line
Salt bridge
Example: Zn/Zn2+ (or) Zn/ZnSO4
Zn Cu
electrode electrode iv. The cathode is written with the electrolyte first and then
the metal Example : Cu2+/Cu (or) CuSO4/Cu
v. The two half cells are separated by a salt bridge, which
ZnSO4 CuSO4
solution is indicated by two vertical lines.
solution
Using the above representation, the galvanic cell is represented as
Cell device (construction) Zn/ZnSO4 (1M) //) CuSO4 (1M) /Cu
Consists of Zn electrode dipped in 1M ZnSO4 solution and a Cu electrode
dipped in 1M CuSO4 solution. Each electrode is a half cell. The solutions
are inter connected by salt bridge and the two electrodes are connected by Differences between electrolytic cells and electrochemical cells
wire Electrolytic cell Electrochemical cell
Electrical energy converted to Chemical energy converted to
Reactions occuring in the cell At anode: oxidation takes place chemical energy electrical energy
Zn Zn2+ + 2e (at anode) with the liberation of e-.
At cathode: Reduction takes place Anode carries +ve charge Anode carries – ve charge
Cu2+ + 2e Cu (at cathode)
by the acceptence of e - .
The electrons liberated in oxidation Cathode carries – ve charge Cathode carries + ve charge
Cu2+ + Zn Zn2+ +Cu (nett cell reaction flow through external wire
reaction) and are consumed by the copper Electrons are supplied to the Electrons are drawn from the
ions at the cathode. cell from an external source cell
Amount of electricity is Emf produced is measured by
Salt bridge: It consists of a U-tube containing a saturated solution measured by coulometer potentiometer
of KCl or (NH4)2NO3 in agar – agar gel. It connects the two half Extent of chemical change is The e.m.f of the cell depends
cells. governed by Faraday’s laws on the concentration of the
Functions electrolyte and chemical
i. Eliminates liquid junction potential nature of the electrode
ii. Provides a path for the flow of electrons between two
half cells
Standard cell Cu(s) | CuNO3(C1M)(dilute) || CuNO3(C2 M)(concentrated) |
A standard cell is the one which
gives constant emf. It is a souce Cu(s)+; C1<C2
Cathode: Cu2+( C2 M) + 2e– → Cu(s)
of constant potential.
Weston cadmium cell consists of
a H – shaped glass vessel. The
Saturated soloution
CdSO4
bottom of the glass tubes are Anode: Cu(s) → Cu2+( C1M) + 2e–
sealed with Pt wires.
CdSO4.8/3H20 +ve electrode (left arm) contains Net: Cu2+(C2 M) → Cu2+(C1 M)
Crystals Hg over which a paste of Hg2SO4
is placed
Hg+Hg2SO4 The transport of cupric ion from a region of higher oncentration to
paste
Hg one of lower concentration.
Cd - Hg + _ ● E° for a concentration cell is always zero, since this would be
amalgam
the potential of a cell in which the electro active species are at
unit activity in both compartment.
The – ve electrode (right arm) contains Hg – Cd amalgam over
which crystals or CdSO4.8/3H2O is placed. 0.0592V logC2/C1
Remaining part of the cell is filled with a saturated solution of Ecell = -------------------------------------------
CdSO4. The upper ends of the tubes are closed with corks. n
The emf of the cell is 1.0807 V. Ex: Oxygen concentration Cell (differential aeration
Representation corrosion).
Cd in Hg/3CdSO4.8H2O // CdSO4.Hg2SO4 / Hg
Ion-Selective Electrodes (ISE)
Concentration Cells ● Electrodes possess certain selectivity towards certain ions.
● Ion Selective Electrodes (ISE) are membrane electrodes that
●The transport of ions due to concentration gradient of the respond selectively to ions in the presence of others
electrolyte at both half-cells is accompanied by a fall in ● The potential developed at the membrane surface is related to
free energy. the concentration of the species of interest.
The loss in free energy produces electrical energy ● The sensing part of the electrode is an ion-specific membrane
● electrolyte (concentrated) → electrolyte (dilute) which is permeable to specific ion and also known as a specific
● No net chemical reaction. ion electrode (SIE).
● Concentration cell is made up of two half-cells having
identical electrodes, identical electrolyte, except that the
concentrations of reactive ions at two electrodes are
different.
Classification: ● When the electrode is immersed in a test solution containing
Depending upon the nature of membranes used hydrogen ions the external ions diffuse through the membrane
Polymer Membrane electrodes: until an equilibrium is reached between the external and
Consist of various ion exchange materials in an inert internal concentrations
matrix such as PVC, polyethylene or silicone rubber. Electrodes of ● Thus there is a build up of charge on the inside of the
this type include Potassium, Calcium and Nitrate. membrane which is proportional to the number of hydrogen
Solid State Electrodes: ions in the external solution.
Utilize relatively insoluble inorganic salts in a membrane. ● The glass membrane functions as an ion exchange resin, and an
Potentials are developed at the membrane surface due to the ion equilibrium set up between Na+ ions of the glass and H + ions
exchange process. Examples of this type of electrode include silver in the solution.
/ sulfide, chloride and fluoride. ● E G = E0 G - 0.0592VpH
Gas Sensing Electrodes:
Gas sensing electrodes are available for the measurement of Construction:
ammonia, carbon dioxide, and nitrogen oxide. This type of ● Ion Selective Electrodes are available as half-cells (mono) and
electrode has a gas permeable membrane and an internal buffer combination electrodes where the reference is built into the
solution. The pH of the buffer solution changes as the gas reacts same probe.
with it. The change is detected by a combination pH sensor within ● Combined electrode: Both glass electrode and reference
the housing. electrode are combined as a single electrode.
Glass Membrane Electrodes:
Glass membrane electrodes are formed by the doping of the
silicon dioxide glass matrix with various chemicals. The most Combined Glass Electrode
common of the electrode of this type is the pH electrode. Glass
membrane electrodes are also used for sodium ions.
Advantages of ion selective electrodes:
 The cost of initial setup to make analysis is relatively low.
 ISE determinations are not subject to interferences such as
color in the sample

Glass membrane electrodes: measurement of pH

● Glass membrane is the most essential component which is
sensitive and permits the passage of hydrogen ions, but no
other ionic species.
Mono electrodes Potentiometric titration
● Require the use of an additional reference electrode.
● If the membrane is attached to the end of a tube that contains ● Potentiometric titration is a volumetric method in which the
an internal reference electrode like Ag/AgCl, the glass changes in the emf between two electrodes (referent and
electrode acts as a internal reference electrode. indicator electrode) on the addition of titrant of known
Ag | AgCl (s), HCl (0.1M)| Glass|test solution+. concentration (titrant) to a solution of unknown (analyte).
● Otherwise ion glass electrode acts as a simple half cell: ● The indicator electrodes is reversible with respect to one of the
Pt, 0.1 M HCl|Glass + ions of analyte taking part in the titration reaction but does not
● Silver/ silver chloride electrode or calomel electrode is used as take part in the reaction. They are inert electrode made up of Pt
second electrode. Since the potentials of the two reference or Au.
electrodes are constant, any change in cell potential is due to ● During the course of the titration, the concentration of active
change in potential across the membrane. ion in the analyte changes thereby electrode potential of
● Cell configuration: indicator electrode changes.
Ag | AgCl (s), KCl (sat)||test solution+ |Glass| HCl (0.1M)|AgCl (s)|Ag ● Types of potentiometric titration for the determination of
or analytes in solutions include acid-base, redox, precipitation,
Pt|Hg|Hg2Cl2, KCl(sat)||test solution+ |Glass| HCl (0.1M)|AgCl (s)|Ag and complexometric.
● Ecell =Eleft- Eright
I) Redox Titration: Fe2+ against dichromate
Glass Electrode-
Mono  The concentration of an ion such as Fe2+ can be found by
titrating with a strong oxidizing agent such as KMnO4
(Mn7+) or K2Cr2O7 (Cr6+).
 The titration is carried out in one side of a cell whose other
half is a reference electrode: Calomel electrode,
Pt| Hg | Hg 2+ (aq) | KCl ||

● pH = Ecell+E0G -Eref /0.0592

  Cell configuration:
Pt(s)| Hg+ (aq)|Hg2 Cl2 (s) | KCl || Fe3+(aq)| Fe2+(aq)| Pt(s)
 Emeas = EInd-ESCE
 Eind
( E Fe3+ / Fe2+) = E0 Fe3+ / Fe2++ 0 .0591 logFe3+ / Fe2+
where E0 Fe3+ / Fe2+ = 0.77V
 Initially the left cell contains only Fe2+. As the titrant is
added, the ferrous ion is oxidized to Fe3+
 according to the reaction.

K2Cr2O7 + FeSO4+7H2SO4→ Cr2(SO4)3 + 3 Fe2(SO4)3 +7H2 O + K2 SO4

 Once the first drop of Cr6+ (K2Cr2O7) titrant has been

added, the potential of the indicator electrode is controlled
by the ratio of oxidized and reduced iron which causes the
potential to rise as more iron becomes oxidized.
 Near the end-point the ratio changes very rapidly since a
small quantity of of added Mn7+ or Cr6+ removes
considerable proportion of the few remaining Fe2+ ions.
 When the equivalence point is reached, the Fe2+ will have
been totally consumed and the potential will then be
controlled by the concentration ratio of cell couple Cr 6+ /
Cr3+
 The end point is found not by measuring a particular cell
voltage, but by finding what volume of titrant gives the
steepest part of the curve.
 A titration curve has a characteristic sigmoid curve. The
part of the curve that has the maximum change marks the
equivalence point of the titration.
 The first derivative, ∆E/∆V, is the slope of the curve, and
the endpoint occurs at the volume, V', where ∆E/∆V has
the maximum value.
 II) Precipitation Titration- Ag+ Vs Cl – titrants
● Titration involving precipitation can be followed
potentiometrically by the use of active metal (Ag) electrode.
+
● For the measurement of Ag , Ag electrode dipping in unknown
AgNO3 solution is coupled with calomel electrode.
● Cell configuration:
Pt(s)| Hg( | Hg2+ (aq) | KCl(sat)|| Ag+(aq)|Ag(s)
● Emeas = EAg+ / Ag – ESCE
Emeas = E Ag+ / Ag - 0.246 V,
EAg+ / Ag = E0Ag+ / Ag + 0.0591 log [Ag+]
+
● Initially the cellcontain excess Ag ions. As the titrant KCl or
NaCl is added, concentration of Ag+ ion decreases due to the
precipitation of Ag+ ions as AgCl according to the equation Conductometric Titrations
AgNO3 + KCl → AgCl ↓ + KNO3
● The reduction potential of active electrode goes on decreasing ● Method of volumetric analysis based on the change in
progressively on the addition of KCl. conductance of the solution at the equivalence point or end
● At the end point the concentration change of Ag+ is quite rapid point during titration.
and its concentration becomes very small due to slight ● Conductance (C) is the reciprocal of electrical resistance (R).
solubility of AgCl. [C = 1/R].It is a measure of the ability of a solution to conduct
● After the end point, further addition of KCl or NaCl does not electricity.
affect the concentration of Ag+ due to common ion effect . ● The conductance of a solution depends upon the number of free
● A titration curve has a characteristic sigmoid curve. The part ions in the solution ion, the charge on the ions and the mobility
of the curve that has the maximum change marks the of the ions. The conductance of a solution is the sum of the
equivalence point of the titration. conductances of all of the ions that are in the solution. C = Ci
● The first derivative, ∆E/∆V, is the slope of the curve, and the ● The unit of conductance is the Siemens (S), which is the
endpoint occurs at the volume, reciprocal of resistance Ω.
V', where ∆E/∆V has the maximum value ● Specific conductance (K) is the conductance of one cm cube of
Advantages of potentiometric titration material and is usually measured with an alternating current
● They are more accurate and precise. between two identical, platinized platinum electrodes.
● Can be used with colored or opaque solutions and ionic ● Specific conductance is obtained by multiplying measured
concentration down upto 10-3N conductance by cell constant of the conductivity cell. K=cell
● No interference due to other ions. constant x measured conductance
 ● Na+ OH –The end point of the titration corresponds to the
intersection of the extrapolated linear portions of the titration
curve.
Titration of weak acid vs strong base (Acetic acid with NaOH)
● Since acetic acid is dissociated slightly (Ka = 1.8 x 10 –5) in
aqueous solution, the conductance of the acetic acid solution is
initially small.
Conductivity Cell: Specially designed cells in which two plates of ● As sodium hydroxide is added, the hydroxide reacts with the
inert metal (Pt or Au) are provided to serve the flow in and flow acid to form water and acetate. CH3COOH + NaOH →H2O +
out of electron. Na+ CH3COO - + H+ + CH3COO -
● The addition of CH3COO– and Na+ ions to the solution causes
Titration of strong acid vs strong base (hydrochloric acid with the conductance of the solution to increase.
sodium hydroxide)
● The reaction that takes place in the titration vessel is
H+ + Cl– + Na+ OH – → H2O + Na + Cl–
● Before the end point, H+ is removed from the solution by
reaction with OH–, and Na+ is added to the solution.
+
● Since the relative conductance of H is about seven times that
of Na+, the conductance of the solution decreases prior to the
end point.
● After the end point, no H+ is available to react, and the
conductance of the solution increases as a result of the addition
of Na+ and OH–.
● Consequently the titration curve has a V-shape as shown in the After the end point, Na+ and OH– are added to the solution. Since
figure. the relative conductance of OH– is nearly five times that of
C2H3O2–, the conductance of the solution after the end point
increases more rapidly than it did before the end point.
● The end point corresponds to the intersection of the
extrapolated linear portions of the curve.
Advantages of conductometric titration Classification of chemical sensors:
● No special care is necessary near the end point as the end point  Optical sensors
is ascertained graphically.  Electrochemical sensors
● Colored solution which cannot be titrated by ordinary  Electrical sensors
volumetric methods with the help of indicators can be titrated  Mass sensitive sensors
● The titrations of weak acid against weak bases can be  Magnetic sensors
performed, they cannot be measured in volumetric titration  Thermometric sensors
because they do not produce sharp color change of indicators.
 Others – radiation detecting sensors
● Very dilute solutions can be titrated
Electrochemical sensors : Sensors which transform the effect of
● The method is very accurate in dilute solutions
the electrochemical interaction analyte – electrode into a useful
● It can even be used in colored or turbid solution.
signal are known as electrochemical sensors. Such effects may be
simulated electrically or may result in a spontaneous interaction at
What is a sensor….? the zero current condition.
A sensor is a device that detects events or changes in
quantities and provides a corresponding output. The output is
Types:
usually an electrical or an optical signal.
1. Voltametric – Current is measured in the DC or AC.
Examples: 2. Potentiometric - Potential is measured (reference
 A mercury thermometer converts the measured temperature electrode and working electrode).
Into expansion and contraction of a liquid which can be 3. CHEMFET – Chemically Sensitized Field Effect
visualized on the calibrated glass tube. Transistor.
 A thermocouple converts temperature to an output voltage. 4. Potentiometric Solid Electrolyte Gas Sensors – These
Types: are different from potentiometric sensors because these work in
Physical sensors: A physical sensor is a device that provides high temperature solid electrolytes and are usually applied for gas
information about a physical property of the system. Ex : pressure sensing measurements.
sensors, temperature sensors etc.
Chemical sensors: A chemical sensor is a device that transforms Potentiometric sensors:
chemical information, ranging from the concentration of a specific A potentiometric sensor is a type of chemical sensor that
sample component to total composition analysis, into an may be used to determine the analytical concentration of some
analytically useful signal. Ex: COD, methane , ions etc. components of the analyte gas or solution. These sensors measure
the electrical potential of an electrode when no current is present.
Principle The two main ones are for urea and creatinine. These
The signal is measured as the potential difference (voltage) potentiometric enzyme electrodes are produced by entrapment the
between the working electrode and the reference electrode. The enzymes urease and creatinase, on the surface of a cation sensitive
working electrode's potential must depend on the concentration of (NH4+) ISE.
the analyte in the gas or solution phase. The reference electrode is
needed to provide a defined reference potential.
In potentiometric sensors, the zero-current potential
(relative to a reference) developed at a selective membrane or
electrode surface in contact with a sample solution is related to
analyte concentration.
The main use of potentiometric transducers in biosensors is
as a pH electrode.
Chemical biosignals:
E = Eo + RT/nF ln[analyte] Signals providing information about concentration of
various chemical agents in the body.
 Eo is a constant for the system  Level of glucose (diabetes)
 R is the universal gas constant  Blood oxygen level (asthma, obstructive pulmonary
 T is the absolute temperature disease, heart and kidney failure)
 z is the charge number  Gases in blood and breathing airflow (anesthetic gases,
 F is the Faraday number carbon dioxide etc.)
 ln[analyte] is the natural logarithm of the analyte activity.  pH
The best known potentiometric sensor is the Ion Selective
Electrode (ISE). Glucose sensor:
Solvent polymeric membrane electrodes are commercially Same chemistry as the oxygen sensor, but monitors H2O2 +
available and routinely used for the selective detection of several 6 O2 (opposite chemistry to O2 sensor).The H2O2 is formed from
ions such as K+, Na+, Ca2+, NH4+, H+, CO32- in complex biological glucose, catalyzed by an immobilized enzyme, glucose oxidase,
matrices. glucose + O2 6 gluconic acid + H2O2 (different from glucuronic
The antibiotics nonactin and valinomycin serve as neutral acid)
carriers for the determination of NH4+ and K+, respectively. ISEs Device is similar to oxygen sensor, except that there is a
used in conjunction with immobilised enzymes can serve as the double layered membrane. In a biological fluid, External
basis of electrodes that are selective for specific enzyme substrates. polycarbonate membrane excludes proteins etc; glucose oxidase is
bound to membrane, forms H2O2 with glucose in sample. Internal
membrane allows H2O2 to diffuse to the electrode (anode, in this  Process control industries
case) where it is oxidized to O2.  Environmental monitoring
 Fire detection Alcohol breath tests
 Detection of harmful gases in mines
 Home safety

Blood oxygen level- pulse oximetry:

Pulse Oximeter used to measure oxygen saturation in the
body i.e how much of the hemoglobin in the blood is carrying the
Gas sensors: oxygen. Oxygen enters the lungs and then is passed on into blood.
A gas sensor is a device which detects the presence of
The blood carries the oxygen to the various organs in our body.
various gases within an area, usually as part of a safety system.
The main way oxygen is carried in our blood is by means of
This type of equipment is used to detect a gas leak and interface hemoglobin. Normal oxygen saturation values are 97% to 99% in a
with a control system so a process can be automatically shut down. healthy individual on room air.
A gas sensor can also sound an alarm to operators in the area
Working principle:
where the leak is occurring, giving them the opportunity to leave
Pulse Oximetry consists of Red(R) and Infrared(IR) light
the area. Gas sensor measures the concentration of gas in its
emitting LEDs and a photo detector. Oxygenated and
vicinity.
deoxygenated hemoglobin have different light absorption rate.
Most often, these are pH-sensing devices that are calibrated
 Oxygenated hemoglobin absorbs more infrared light
in the units of interest, such as ppbv of CO2, ppbv of SO2. Note
 Deoxygenated hemoglobin absorbs more red light
that this means that they are not specific for a single gaseous
Finger is placed in between the light source and the light detector.
analyte.
Non absorbed light by finger reaches at detector. Light is emitted
Types of gas sensor
from light sources which goes across the pulse oximeter probe and
CO2, SO2, NH3 - Glass membrane, senses pH change
reaches the light detector. The amount of light absorbed depends
HCN, H2S - Ag2S membrane, senses pCN or pS
on three physical properties:
HF - LaF3 membrane, senses pF
1. concentration of the light absorbing substance.
The gas sensor has a thin plastic membrane (often silicone rubber)
2. length of the light path in the absorbing substance.
to admit gas into the sensor. Only a very thin layer of aqueous
3. oxyhemoglobin and deoxyhemoglobin absorbs red and
solution is in contact with the gas, in order to keep response times
infrared light differently
short.
Amount of light absorbed is proportional to the concentration of
the light absorbing substance. Amount of light absorbed is
Some Applications of Gas Sensor:
proportional to the length of the light path. Oxyhemoglobin
absorbs more infrared light than red light & deoxyhemoglobin
absorbs more red light than infrared [Link] this ratio, the pulse
oximeter can then work out the oxygen saturation.
Uses:
 Operating rooms.
 ICU.
 Postanesthesia care units.
 Emergency departments and ambulances.
 Endoscopy suites.
 Sleep laboratories
 Cardiac catheterization laboratories.
 Delivery suites
 Wards.