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ELEKTROKIMIA
ANALISIS FARMASI I
2013/2014
ELEKTROKIMIA
Oxidation
o Loss of electrons
Reduction
o Gain of electrons
Oxidized Reduced
Species Species
e-
e-
Salt bridge
(KCl)
Cu electrode
Zn electrode
0.010M CuSO4
0.010M ZnSO4 solution
solution
Examples
- Production of aluminum metal from Al3+
- Production of Cl2 from Cl-
GALVANIC CELL
- Spontaneous redox reaction produces electrical energy
- Can be reversed electrolytically for reversible cells
- Also known as voltaic cell
- One reagent is oxidized and the other is reduced
- The 2 reagents must be separated (cannot be in contact)
- Electrons flow through a wire (external circuit)
Example
Rechargeable batteries
Reduction Half-Reaction
- Gain of electrons
- Occurs at cathode (positive electrode)
- The right half-cell by convention
GALVANIC CELL
Salt Bridge
- Connects the two half-cells (anode and cathode)
- Filled with gel containing saturated aqueous salt
solution (KCl)
- Ions migrate through to maintain electroneutrality
(charge balance)
- Prevents charge buildup that may cease the
reaction process
GALVANIC CELL
For the overall reaction
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
e- Voltmeter e-
Zn electrode
- + Cu electrode
Cl-
K+
Line Notation
SHE Ag (a 1.00) Ag
STANDARD POTENTIALS
Standard Hydrogen Electrode (SHE)
2H (aq) 2 e H 2 (g)
H ([H ] x M) H 2 (p 1.00 atm), Pt
ESHE 0.00 volt s
STANDARD POTENTIALS
Half Reaction Eo (V)
Oxidizing F2 + 2e- ↔ 2F- Reducing 2.890
agents MnO4- + 5e- ↔ Mn2+ agents 1.507
Ce4+ + e- ↔ Ce3+ (in HCl) 1.280
O2 + 4H+ + 4e- ↔ 2H2O 1.229
Increasing oxidizing power
Hg2Cl2(s) + 2e - 2 Cl - + 2Hg(l)
CELL POTENTIALS
Ecathode Ag e Ag(s)
Ag (0.0200 M) Ag
Eanode Cu 2 2e Cu(s)
Cu 2 (0.0200 M) Cu
Junction Potential
O + ne- ↔ R
2.3RT O
E EO log
nF R
E = electrode potential
Eo = standard potential for the redox reaction
R = gas constant = 8.314 J/K-mol
T = absolute temperature in Kelvin
F = Faraday’s constant = 96,485 C/mol
n = number of electrons transferred
NERNST EQUATION
aA + ne- ↔ bB
EE
O 2.3RT
log
B b
EE
O RT
ln
B b
a a
nF A nF A
0.05916 B b
EE O
log
n A a
NERNST EQUATION
aA + bB ↔ cC + dD
EE
O 0.05916
log
C c
D d
b
A B
a
n
NERNST EQUATION
E = Eo when [O] = [R] = 1M
Electrodes
Working (indicator) electrode, reference electrode,
counter electrode
ELECTROANALYTICAL METHODS
Potentiometric Technique
Potentiostatic Technique
Controlled-potential technique
Ag/AgCl:
Ag(s) | AgCl (s) | Cl-(aq) || .....
INDICATOR ELECTRODES
Electrode that responds to change in analyte
activity
Generally show high degree of selectivity
Examples
pH electrode
Calcium (Ca2+) electrode
Chloride (Cl-) electrode
INDICATOR ELECTRODES
ION-SELECTIVE ELECTRODES (ISE)
Advantages
Internal reference
electrode
Internal (filling)
solution
Ion-selective membrane
INDICATOR ELECTRODES
ION-SELECTIVE ELECTRODES (ISE)
Three groups of ISEs
Glass Liquid
Electrode Electrodes
Solid
Electrodes
INDICATOR ELECTRODES
GLASS ELECTRODES
E K β(0.05916)ΔpH
E K - 0.05916 log(a H )
β ≈ 1 (typically ~ 0.98)
(measured by calibrating electrode in solutions of known pH)
pH Nonglass Electrodes
- Quinhydrone electrode (quinone – hydroquinone couple)
- Antimony electrode
INDICATOR ELECTRODES
SOLID-STATE ELECTRODES
Solid membranes that are selective primarily to
anions
Solid-state membrane may be single crystals (most
common), polycrystalline pellets or mixed crystals
Ionic solid contains the target ion
Solid is sealed to the end of a polymer tube
Contains internal reference electrode and filling
solution
Concentration difference across the membrane
causes migration of charged species across the
membrane
Can measure concentrations as low as 10-6 M
INDICATOR ELECTRODES
SOLID-STATE ELECTRODES
Examples
0.05916
Cell potential is given by EK log(a Ca )
2
INDICATOR ELECTRODES
LIQUID MEMBRANE ELECTRODES
Examples
IEE for polycationic species (polyarginine,
protamine)
IEE for polyanionic species (DNA)
IEE for detection of commonly abused drugs
(large organic species)
INDICATOR ELECTRODES
LIQUID MEMBRANE ELECTRODES
Anion-Selective Electrodes
Examples of Anions
- Phosphate
- Salicylate
- Thiocyanate
- Carbonate
Liquid Membrane Electrodes
INDICATOR ELECTRODES
OTHER ELECTRODES
- Coated-wire electrodes (CWE)
- Solid-state electrodes without inner solutions
For detection of
amino acids, cocaine, methadone, sodium
Solid State Membrane Electrodes
Ag wire Solid State Membrane Chemistry
Membrane Ion Determined
Filling
solution LaF3 F-, La3+
with fixed
[Cl-] and AgCl Ag+, Cl-
cation that
electrode AgBr Ag+, Br-
responds to
AgI Ag+, I-
Ag/AgCl Ag2S Ag+, S2-
Ag2S + CuS Cu2+
Solid state membrane
Ag2S + CdS Cd2+
(must be ionic conductor) Ag2S + PbS Pb2+
Solid state electrodes
INDICATOR ELECTRODES
GAS SENSING PROBES
For monitoring gases such as CO2, O2, NH3, H2S
Device is known as compound electrode (probe is usually used in
place of electrode)
Highly sensitive and selective for measuring dissolved gases
For environmental monitoring for clinical and industrial applications
Gas permeable membrane (teflon, polyethylene) is immobilized on a
pH electrode or ion-selective electrode
Thin film of electrolyte solution is placed between electrode and
membrane (fixed amount, ~0.1 M)
Inbuilt reference electrode
INDICATOR ELECTRODES
GAS SENSING PROBES
The target analyte diffuses through the membrane and comes
to equilibrium with the internal electrolyte solution
The target gas then undergoes chemical reaction and the
resulting ion is detected by the ion-selective electrode
Electrode response is directly related to the concentration of
gas in the sample
Two types of polymeric materials are used
Microporous and Homogeneous
Membrane thickness is ~ 0.01 – 0.10 mm
Membrane is impermeable to water and ions
INDICATOR ELECTRODES
GAS SENSING PROBES
CO2 Sensors
Membrane
(silicone)
INDICATOR ELECTRODES
GAS SENSING PROBES
NH3 Sensors
H2S
- Makes use of S2- ISE or modified pH electrode
HF
- Makes use of F- ISE or modified pH electrode
INDICATOR ELECTRODES
IMMOBILIZED ENZYME MEMBRANE ELECTRODES
Electrode
Biocatalytic Layer
INDICATOR ELECTRODES
IMMOBILIZED ENZYME MEMBRANE ELECTRODES
Applications
Pengukuran Pengukuran
Langsung tidak langsung
• Direct • Titrasi
potentiometry potensiometri
• Konsentrasi • Pengukuran
analit diperoleh potensial pada
secara langsung berbagai
atau melalui volume titran
kurva kalibrasi
Contoh Soal Titrasi Potensiometri
Sebanyak 5 mL larutan Fe 2+ 0,1 M ditambahkan
50 mL asam sulfat dan dititrasi dengan larutan
Ce4+ 0,1 N. Jika diketahui E0 Fe3+ - Fe2+ = 0,68 V
dan E0 Ce4+ - Ce3+ = 1,44 V, berapakah potensial
pada saat penambahan titran sebanyak :
• A. 1,0 mL
• B. 2,5 mL
• C. 5,0 mL
• D. 10 mL
POTENTIOMETRY
Applications
- Environmental monitoring
- Clinical diagnostics (blood testing, electrolytes in blood)
- Control of reaction processes
- Pengukuran pH
- Pengukuran konsentrasi ion dengan ISE
- Titrasi : asam basa, pengendapan, redoks, kompleksometri
APPLICATIONS OF POTENTIOMETRY
- Used as detectors for automated flow analyzers
(flow injection systems)
- High-speed determination of blood electrolytes in hospitals
(H+, K+, Cl-, Ca2+, Na+)
- For measuring soil samples (NO3-, Cl-, Li+, Ca2+, Mg2+)
- Coupling ion chromatography with potentiometric detection
- Micro ISEs as probe tips for SECM
- Column detectors for capillary-zone electrophoresis
VOLTAMMETRY
- Solution is unstirred
Provides information on
- the thermodynamics of redox processes
- the kinetics of heterogeneous electron transfer reactions
- the kinetics of coupled reactions
CYCLIC VOLTAMMETRY
Characteristic Parameters
- Anodic peak current (ipa)
- Cathodic peak current (ipc)
- Anodic peak potential (Epa)
- Cathodic peak potential (Epc)
CYCLIC VOLTAMMETRY
Applications
For analyzing
- drugs
- herbicides
- insecticieds
- foodstuff additives
- pollutants
POLAROGRAPHY
- Conventional DC
CE = Pt wire or foil
RE = SCE
DC POLAROGRAPHY
At 25 oC
0.05916 i i
E E1/2 log L
n i
Electrolysis
- A process causing a thermodynamically nonspontaneous
oxidation or reduction reaction to occur by application
of potential or current
COULOMETRY
Electrogravimetry
Applications
Applications
- To determine the ionic content of drinking water,
deionized water, solvents, beverages