2. ELECTROCHEMISTRY
It is a speciality of classical physics
&chemistry which deals with oxidation &
reduction reactions with transfer of
chemical energy into electrical energy &
vice versa
3. BASIC TERMS
OXIDATION—loss of electron(s) by a species;
increase in oxidation number; increase in
oxygen.
REDUCTION—gain of electron(s); decrease in
oxidation number; decrease in oxygen;
increase in hydrogen.
OXIDIZING AGENT—electron acceptor;
species is reduced.
REDUCING AGENT—electron donor; species
is oxidized.
4. Electrochemical Cells
An apparatus that allows a
redox reaction to occur by
transferring electrons through
an external connector.
Product favored reaction --->
voltaic or galvanic cell ---->
electric current
Reactant favored reaction ---
> electrolytic cell ---> electric
current used to cause
chemical change.
Batteries are voltaic cells
6. •Electrons travel thru external wire.
Salt bridge allows anions and cations to
move between electrode compartments.
Zn --> Zn2+ + 2e- Cu2+ + 2e- --> Cu
<--Anions
Cations-->
Oxidation
Anode
Negative
Reduction
Cathode
Positive
RED CAT
7. Electromotive Force (emf)
The potential difference between the
anode and cathode in a cell is called the
electromotive force (emf).
It is also called the cell potential, and is
designated Ecell.
8. Zn/Cu Electrochemical Cell
Zn(s) ---> Zn2+(aq) + 2e- Eo = +0.76 V
Cu2+(aq) + 2e- ---> Cu(s) Eo = +0.34 V
---------------------------------------------------------------
Cu2+(aq) + Zn(s) ---> Zn2+(aq) + Cu(s)
Eo = +1.10 V
Cathode,
positive,
sink for
electrons
Anode,
negative,
source of
electrons
+
9. H2 input
1.00 atm
inert
metal
We need a standard electrode to
make measurements against!
The Standard Hydrogen Electrode (SHE)
Pt
1.00 M H+
25oC
1.00 M H+
1.00 atm H2
Half-cell
2H+ + 2e- H2
Eo
SHE = 0.0 volts
10. H2 1.00 atm
Pt
1.0 M H+
Cu
1.0 M CuSO4
0.34 v
cathode half-cell
Cu+2 + 2e- Cu
anode half-cell
H2 2H+ + 2e-
KCl in agar
+
Now let’s combine the copper half-cell with the SHE
Eo = + 0.34 v
11. H2 1.00 atm
Pt
1.0 M H+
1.0 M ZnSO4
0.76 v
cathode half-cell
2H+ + 2e- H2
anode half-cell
Zn Zn+2 + 2e-
KCl in agar
Zn
-
Now let’s combine the zinc half-cell with the SHE
Eo = - 0.76 v
12. Assigning the Eo
Al+3 + 3e- Al Eo = - 1.66 v
Zn+2 + 2e- Zn Eo = - 0.76 v
2H+ + 2e- H2 Eo = 0.00 v
Cu+2 + 2e- Cu Eo = + 0.34
Ag+ + e- Ag Eo = + 0.80 v
Write a reduction half-cell, assign the voltage
measured, and the sign of the electrode to the
voltage.
Increasing
activity
13. TABLE OF STANDARD
REDUCTION POTENTIALS
2
Eo (V)
Cu2+ + 2e- Cu +0.34
2 H+ + 2e- H 0.00
Zn2+ + 2e- Zn -0.76
oxidizing
ability of ion
reducing ability
of element
To determine an oxidation from a
reduction table, just take the opposite
sign of the reduction!
14.
15. +
-
battery
Na (l)
electrode half-
cell
electrode half-
cell
Molten NaCl
Na+
Cl-
Cl- Na+
Na+
Na+ + e- Na 2Cl- Cl2 + 2e-
Cl2 (g) escapes
Observe the reactions at the electrodes
NaCl (l)
(-)
Cl-
(+)
23. POTENTIOMETRY
Measurement of an electrical potential
difference between two half cells in an
electrochemical cell when the cell
current is zero .
Galvanic cell
Left side – reference electrode
Right side – Indicator (measuring )
electrode
24. Characteristics of Ideal Reference Electrode:
1) Reversible and follow Nernst equation
2) Potential should be constant with time
3) Should return to original potential after being subjected to
small currents
4) Little hysteresis with temperature cycling
5) Should behave as ideal nonpolarized electrode
25. CELL POTENTIAL – Sum of all potential
gradients existing between different phases
of cell
VARIOUS POTENTIAL GRADIENTS
Redox potential
Membrane potentials
Diffusion potentials
26.
27. ELECTRODES FOR
POTENTIOMMETRIC
APPLICATIONS
REDOX ELECTRODES
Inert metal electrodes
Metal electrodes participating in redox
reaction
ION SELECTIVE ELECTRODES
Glass electrode
polymer membrane electrode
Pco2 electrodes
28. REDOX ELECTRODES
Redox potential – result of chemical equilibrium
involving electron transfer reactions
Oxidised form + ne ↔ Reduced form
redox couple
with respect to SHE
NERNST EQUATION –
E = E0 – N/n x log ared /aox = Eo- .0592v/n xlog ared/ao
N= RT xIn Log 10 /F
29. INERT METAL ELECTRODES
PLATINUM ELECTRODES
GOLD ELECTRODES
HYDROGEN ELECTRODES – pH
measurement
Platinum & gold electrodes r coated with
highly porous platinum( platinum black ) to
catalyze the reaction
ELECTRODE POTENTIAL –
E = E0 – N x log ( f H2)1/2 / aH
34. ION SELECTIVE ELECTRODES
MEMBRANE POTENTIAL
Caused by the permeability of certain types of
membranes to selected anions and cations
Interact with a single ion species
Potential is propotional to the logarithm of the
ionic activity or concentration of the ion
TYPES
GLASS ELECTRODE
POLYMER MEMBRANE ELECTRODE
35. GLASS ELECTRODE
Formulated from
Melts of silicon and aluminium oxide mixed with oxides
of earth or alkali metal cations
- By varying composition , electrodes with selectivity
of various cations can be demonstrated
- Formula for H+ selective glass
72% SiO2, 22% Na2O, 6% CaO
SELECTIVITY ORDER
H+ >>> Na+ > K+ Ph range 7.0 – 8.0
if 71% SiO2, 11% Na2O, 18% Al2O3
H+ >Na+> K+
39. POLYMER MEMBRANE ELECTRODE
WORKING MECHANISM – 3 CATEGORIES
a) CHARGE DISSOCIATED ION EXCHANG
It employs quarternary ammonium(NH4+) salts as
membrane component
Uses
Determinatin of chloride ion in blood & serum
LIMITATIONS –
Anions more lipophilic than chloride in sample may
interfere
Loss of chloride sensitivity with repeated heparin
exposure
40. b) CHARGED ASSOCIATED CARRIER –
Used for Ca+ ion – based on Ca+ selective ion
exchange property of 2-ETHYLHEXYL
PHOSPHORIC ACID dissolved in DIOCTYL
PHENYL PHOSPHONATE .
Reffered as LIQUID MEMBRANE ISE
LATER ON INGREDIENTS WERE INCORPORATED
INTO PVC MEMBRANE
FORMULATION OF PVC MEMBRANE
1 To 3% ionophore - ex TRIFLUROACETONE Gp
64% plasticizer – controls polarity of membrane
30 wt % PVC
< 1wt% additives – ex large lipophilic anions like
TETRAPHENYL BORATE derivatives for cation
selective ISE
41. NEUTRAL ION CARRIER (
IONOPHORE)
INCORPORATION OF NEUTRAL
ANTIBIOTIC VALINOMYCIN – highly
selective for K+ ions
INCORPORATION OF
TRIFLOROACETOPHENONE GROUPS –
Highly selective for carbonate ion
Forms negatively charged adducts
Used for determining total CO2 in
serum/plasma
42. ADVANTAGES OF ISE
Simple
Rapid
Nondestructive
Applicable to a wide range of concentratio
DISADVANTAGES
Interference with other ions
45. VOLTAMMETRY & AMPEROMETRY
VOLTAMETRY – Measurement of current
when an external potential is applied while the
potential varies under potentiostatic control.
Based on the principle of electrolytic cell
Current is directly propotional to the
concentration of the analyte
AMPEROMETRY – Measurement of
current when a constant external
potential is applied
Current is inversely proportional to the
resistance of the the electrolyte
52. ANODIC STRIPPINB VOLTAMMETRY
Used for detecting trace level of toxic
substance in clinical sample
- Carbon working electrode is used
- E app first kept highly negative
- Then scanned more positive
- Reduced metals reoxidize
- Give large anodic current proportional to
ion conc.
- Potential at which peak obs.indicate which
metal is present
53. RAPID SSAN CYCLIC VOLTAMMETRIC
TECHNIQUE
Quantify dopamine in brain tissue in freely
moving animals
Oxidation of dopamine to a quinone sp.at
an implanted microcarbon electrode yields
peak cuffents prop. To concentration of
dopamine levels
54. CONDUCTOMETRY
Measure of ability of ions in solution to carry
current under the influence of potential
diiference
Potential with frequency between 100 to 3000 hZ
IS USED ( PREVENTS ELECTRODE
POLARISATION)
Current is directly propotional to solution
conductance, where conductance is inverse of
resistance
UNIT – SIEMENS ( Ohm-1 )
Depends on-
ionic charge
viscosity
potential applied
55. CLINICAL APPLICATIONS
- Measurement of volume fraction of
erythrocytes
- Electronic counting of blood cells in
suspension ( COULTER PRINCIPLE )
-Titrations ( acid-base , precipitations )
-Tranducer mechanism for some biosensors
56. COULOMETRY
Measures the electrical charge between two
electrodes in a electrochemical cell
Charge is directly proportional to oxidation or
reduction of the substance at one of the electrode
Q =nNF
Q = Charge
n = no of electrons
N = Amount of substance reduced or oxidized
F = Faradays constant (96,487 coulambs/mole)
CLINICAL APPLICATIONS
Cl- ions in serum
Coulometric titrations
Mode of transduction in biosensors
57. OPTICAL CHEMICAL SENSORS
OPTODES
USE – In analytical instruments to measure blood
gases and electrolytes
ADVANTAGES OVER ELECTRODES
- Ease of miniaturization
- Less noise
- Potential long term stability
- No need for reference electrode
BASIC CONCEPT
Optodes used for PO2 Measurement based on
immobilisation of organic dyes ( pyrene
phenantherene, fluoranthrene)
58. METAL LIGAND COMPLEX ( Ruthenium [11]
tris [di pyridine],Pt & Pb metalloporphyrins)
in hydrophobic polymer films ( silicon rubber)
in which O2 is soluble
Decreased intensity of fluorescence is
proportional to PO2
APPLICATIONS
- Used for pCO2 determination
- Optically sense the electrolyte ions eg.
lipophilic ionophore for polymer memb.ISE with
lipophilic Ph indicator ( valinomycin for k+)
change in optical absorption or flourescence
spectrum of polymer layer
59.
60.
61.
62.
63.
64.
65.
66.
67. TECHQNIQUES OF IMMOBILISATION
ENTRAPMENT METHOD
CROSS LINKING OF ENZYME WITH AN
INERT PROTEIN ex- bovine serum albumin
SIMPLE ADSORPTION OF THE ENZYME
TO ELECTRODE SURFACE
COVALENT BINDING OF ENZYME TO
INSOLUBLE CARRIER ex- nylon or glass
BULK MODIFICATION OF ELECTRODE
MATERIAL, mixing enzyme with carbon
paste.which serves as enzyme immobilisation
matrix & electroactive surface
68.
69.
70.
71. ENZYME BASED BIOSENSORS WITH
POTENTIOMETRIC METHOD
UREA ------- 2NH3 + CO2
Urease
LIMITATIONS
High substrate concentration
Local alkaline pH due to hydrolysis of urea
IT IS REDUCED BY
Placing a semipermeable membrane between
enzyme and sample to limit diffusion of urea
72.
73. ENZYME BASED BIOSENSORS WITH
OPTICAL DETECTION
EXAMPLE-
Optical detection for pH & oxygen
Glucose & cholesterol optical sensor
BASED ON
Flourescence
Absorbance
Reflectance
as mode of detectio
74. AFFINITY BASED BIOSENSORS
Immobilised biological recognition element is
a binding protien ,antibody ,(immunosensor)
or oligonucleotide ( eg DNA , aptamers etc
)with high binding specificity & affinity
towards a clinically imp analyte.
Typically single use devices
BASED ON
Electrochemical, optical, thermal,mass,
acoustic detection methods
75. EXAMPLE
ALPHA FETOPROTIEN detected via a quartz
crystal microbalance type mass detector ,
possesing immobilized antialpha-fetoprotien
antibodies
DNA SENSORS – A complementry DNA segment
to the target DNA is immobilized on a suitable
transducer eg.
Genosensor for detecting V Leiden mutations
using capture probeswith inosine substituted
for guanosine nucleic acid
76. ELECTROCHEMICAL O2 SNSORS- carry
out heterogenous enzyme immunoassay
using catalase as labeling enzyme &
immobilizing capture antibodies on the
outer surface of gas permeable membrane.
H2O2 ------ 2H+ + O2
77.
78.
79.
80.
81. IN VIVO & MINIMALY INVASIVE
SENSORS
MINIATURED VERSION OF ELECTROCHEMICAL &
OPTICAL SENSOR DEVICES EMPLOYED IN VIVO
ADVANTAGES
Real time monitoring
Critically ill patients ( Ph /PCO2/PO2 )
LIMITATIONS
Biological response of living system towards sensors
(CLOTTING)
Once inserted no reliable caliberation
82. APPLICATIONS
Measurement of O2 saturation
Measurement of Ph /PCO2 /Po2 based on clark
style design sensor
Glucose sensors – Fully automated
Feed back control of subcutaneos insulin
delivery