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METODE ANALISIS

ELEKTROKIMIA

ANALISIS FARMASI I
2013/2014
ELEKTROKIMIA

 Mempelajari hubungan antara reaksi kimia


dan elektrisitas/listrik

 Mempelajari interkonversi energi kimia dan


energi listrik melalui reaksi redoks

 Proses elektrokimia melibatkan transfer


elektron dari satu komponen ke komponen
lain
ELEKTROKIMIA
Spesi Elektroaktif

 Spesi yang mengalami reaksi oksidasi atau


reduksi

 Dapat berupa suatu senyawa komplek, molekul,


atau ion

 Baik dalam larutan air atau non-air


METODE ANALISIS ELEKTROKIMIA

 The use of electrochemical techniques to


characterize a sample
 Deals with the relationship between electricity and
chemistry
 Analytical calculations are based on the
measurement of electrical quantities (current,
potential, charge, or resistance) and their
relationship to chemical parameters
Elektrokimia adalah metode analisis kualitatif maupun
kuantitatif senyawa kimia, yang reaksinya dipengaruhi
oleh arus listrik, beda potensial, dan daya hantar listrik.
History of Electroanalytical Methods

• Michael Faraday: the law of


electrolysis
▫ “…the amount of a substance deposited
from an electrolyte by the action of a
current is proportional to the chemical Michael Faraday Walter Nernst
equivalent weight of the substance.” (1791-1867) (1864-1941)

• Walter Nernst: the Nernst


equation (Nobel Prize 1920)
• Jaroslav Heyrovsky: the
invention of polarography:
(Nobel Prize 1959)
Jaroslav Heyrovsky
(1890-1967)
ELECTROANALYTICAL CHEMISTRY
Advantages

 Measurements are easy to automate as they are


electrical signals

 Low concentrations of analytes are determined


without difficulty

 Far less expensive equipment than spectroscopy


instruments
Applications
• Study Redox Chemistry
▫ electron transfer reactions, oxidation, reduction,
organics & inorganics, proteins
▫ Adsorption of species at interfaces
• Electrochemical analysis
▫ Measure the Potential of reaction or process
E = const + k log C (potentiometry)
▫ Measure the Rate of a redox reaction; Current (I)
= k C (voltammetry)
• Electrochemical Synthesis
Organics, inorganics, materials, polymers
Potensimeter berdasar atas perbedaan
potensial kedua elektrode yang dinyatakan
dalam milivolt atau mV.

Metode Amperemeter berdasar timbulnya arus listrik


yang dinyatakan dalam amper atau mili
analisis amper
elektroki
mia Voltameter mempunyai prinsip yang sama
tetapi elektrode yang digunakan agak
berbeda
Konduktometer berdasar pada daya hantar
listrik atau konduktivitas
PRINSIP-PRINSIP DASAR ELEKTROKIMIA
Redox Reaction
o Oxidation-reduction reaction
o Reactions in which electrons are transferred
from one substance to another

Oxidation
o Loss of electrons

Reduction
o Gain of electrons
Oxidized Reduced
Species Species

The species that loses The species that gains


electrons electrons

The reducing agent Oxidizing agent


(reductant) (oxidant)

Causes reduction Causes oxidation

Fe(s) ↔ Fe2+(aq) + 2e- Cu2+(aq) + 2e- ↔ Cu(s)


HALF REACTIONS
- Just the oxidation or the reduction is given
- The transferred electrons are shown

Oxidation Half-Reaction Reduction Half-Reaction


Electrons are on the Electrons are on the reactant
product side of the equation side of the equation
Fe(s) ↔ Fe2+(aq) + 2e- Cu2+(aq) + 2e- ↔ Cu(s)
Fe2+ ↔ Fe3+ + e- Cl2(g) + 2e- ↔ 2Cl-
Electrochemical Cells
• Electrochemical cells are composed of two
electrodes – solid electrical conductors,
each immersed in an suitable electrolyte
solution (aqueous electrical conductor)
• The positive electrode is defined as the
cathode and the negative electrode is
defined as the anode
▫ The electrons flow through the external
circuit from the anode to the cathode.
▫ To test the voltage of a battery, the red(+)
lead is connected to the cathode (+
electrode), and the black(-) lead is
connected to the anode (- electrode)
Electrochemical Cells
Voltmeter

e-
e-

Salt bridge
(KCl)

Cu electrode
Zn electrode
0.010M CuSO4
0.010M ZnSO4 solution
solution

Zn  Zn2+ (aq) + 2e- Cu2+ (aq) + 2e-  Cu(s)


a Zn 2+ = 0.010 a Cu 2+ = 0.010
Anode Cathode
Electrochemical Cells
• Electrons serve as carriers (e.g. moving from Zn
through the conductor to the Cu)
• In the solution, electricity involves the movement
of cations and anions
▫ In the salt bridge both chloride and potassium ions
move
• At the electrode surface: an oxidation or a
reduction occurs
▫ Cathode: the electrode at which reduction occurs
▫ Anode: the electrode at which oxidation occurs
Electrochemical Cells
• Galvanic cell: a cell that produces electrical
energy

• Electrolytic cell: a cell that consumes


electrical energy

• Chemically-reversible cell: a cell in which


reversing the direction of the current
reverses the reactions at the two electrodes
ELECTROLYSIS CELL

- Voltage is applied to drive a redox reaction that


would not otherwise occur
- Nonspontaneous reaction
- Requires electrical energy to occur
- Consumes electricity from an external source

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

Conditions for Non-reversibility


- If one or more of the species decomposes
- If a gas is produced and escapes
GALVANIC CELL
Oxidation Half-Reaction
- Loss of electrons
- Occurs at anode (negative electrode)
- The left half-cell by convention

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+

Zn2+ Salt bridge (KCl) Cu2+


Anode Cathode
Oxidation Reduction
Zn(s) → Zn2+(aq) + 2e- Cu2+(aq) + 2e- → Cu(s)
GALVANIC CELL

Line Notation

Phase boundary: represented by one vertical line

Salt bridge: represented by two vertical lines

Zn(s) ZnSO4(aq) CuSO4(aq) Cu(s)


anode chatode

ZnZnSO4(aZn 2+=0.0100)   CuSO4(aCu 2+=0.0100)Cu


Electrode Potentials
 Jika suatu logam dicelupkan ke dalam larutan elektrolit
ionnya  cenderung mengalami oksidasi atau reduksi 
dinyatakan sebagai POTENSIAL ELEKTROKIMIA atau
POTENSIAL ELEKTRODE STANDAR (E0)

 E0 Zn = -0,76 V ditulis : Zn2+ + 2e → Zn E = -0,76V


 E0 Cu = 0,34 V ditulis : Cu2+ + 2e → Cu E = +0,34V

 Standard electrode potential (E0): the potential


associated with a reduction reaction at an
electrode at standard ambient conditions (298K,
solutes at a concentration of 1 M, and gas
pressure at 1 atm).
Electrode Potentials
Bagaimana cara mengukut potensial elektrode
standar ?

 Potensial absolut tidak dapat diukur  hanya


potensial relatif yang dapat diukur
 Potensial
elektrode standar diukur dengan cara
membandingkannya dengan elektrode
pembanding/reference
STANDARD POTENTIALS

Standard Reduction Potential (Eo)

- Used to predict the voltage when different cells are


connected
- Potential of a cell as cathode compared to standard
hydrogen electrode
- Species are solids or liquids
- Activities = 1
- Concentrations = 1 M (use concentrations for
simplicity)
- Pressures = 1 bar
H 2 (g)  2Ag   2H   2Ag(s) Ecell  Ecathode  Eanode   0.799V
Pt, H 2 1.0 atm  H  (a  1.00) Ag  (a  1.00) Ag

SHE Ag  (a  1.00) Ag
STANDARD POTENTIALS
Standard Hydrogen Electrode (SHE)

- Reference electrode half-cell


- Used to measure Eo for half-reactions (half-cells)
- Connected to negative terminal (anode)
Consists of
- Platinized Pt electrode immersed in a solution of 1M HCl
- H2 gas (1 atm) is bubbled over the Pt electrode

2H+(aq, 1 M) + 2e- ↔ 2H2 (g, 1 bar)

Assigned Eo = 0.000 under standard state conditions


(T = 25 oC, concentration = 1M, pressure = 1 atm, pure solid or
liquid)
The 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

Increasing reducing power


Ag+ + e- ↔ Ag(s) 0.799
Cu2+ + 2e- ↔ Cu(s) 0.339
2H+ + 2e- ↔ H2(g) 0.000
Cd2+ + 2e- ↔ Cd(s) -0.402
Fe2+ + 2e- ↔ Fe(s) -0.440
Zn2+ + 2e- ↔ Zn(s) -0.763
Al3+ + 3e- ↔ Al(s) -1.659
K+ + e- ↔ K(s) -2.936
Li+ + e- ↔ Li(s) -3.040
STANDARD POTENTIALS

- Elements that are more powerful reducing agents than hydrogen


show negative potentials

- Elements that are less powerful reducing agents than hydrogen


show positive potentials

- Metals with more negative Eo are more active

- More active metals displace less active metals from solution

Fe will displace Cu2+ out of solution


Zn dissolves in HCl but Cu does not
Practical Reference Electrodes

Silver/Silver Chloride Electrode


Prepared by applying an oxidizing potential to a
silver wire immersed in a dilute solution of
hydrochloric acid The potential of this electrode is
about 0.222 V positive with respect to the standard
hydrogen electrode.
The electrode half-reaction is
AgCl(s) + e - Cl - + Ag(s)
Practical Reference Electrodes

The Saturated Calomel Electrode (SCE)


Consists of a pool of mercury in contact with a
solution that is saturated with mercury(I) chloride
(calomel) as well as potassium chloride. The
potential of this reference is about 0.268 V positive.
The electrode reaction is

Hg2Cl2(s) + 2e - 2 Cl - + 2Hg(l)
CELL POTENTIALS

Perbedaan potensial listrik antara anode dan katode


disebut :
 Cell voltage
 Electromotive force (emf)
 Cell potential

• The potential for a cell containing a specified


concentration of reagent other than 1 M
• Standard Cell Potential : Eocell = Eocathode – Eoanode
• Cell Potential : Ecell = Ecathode – Eanode
• Ecell is positive for spontaneous reactions
• Half-reaction is more favorable for more positive Eo
Half-Cells= Half-cell reaction
Cu(s)  2Ag   Cu 2  2Ag(s)
Cu Cu 2 (0.0200 M) Ag  (0.0200 M) Ag

Ecell  Eright  Eleft


Ecell  Ecathode  Eanode

Ecathode Ag   e   Ag(s)
Ag  (0.0200 M) Ag
Eanode Cu 2   2e   Cu(s)
Cu 2  (0.0200 M) Cu

By convention, all Half-Cell reactions


are written as reduction half-reactions
CELL POTENTIALS

Determining if redox reaction is


spontaneous :
E0cell = +  spontaneous reaction
E0cell = 0  equilibrium
E0cell = -  n0n-spontaneous reaction
CELL POTENTIALS

Junction Potential

- Is produced when there is a difference in concentration


or types of ions of the two half-cells
- Is created at the junction of the salt bridge and the
solution
- Is a source of error
- Minimized in KCl salt bridge due to similar mobilities
of K+ and Cl-
Standard Cells and Cell Potentials #1
• Example: What is the standard potential of the cell
represented below:

1. Determine the cathode and anode


2.Determine the overall cell reaction

3.Determine the standard cell potential


Standard Cells and Cell Potentials #2
• Example: What is the standard potential of an
electrochemical cell made of a cadmium electrode in a 1.0
mol/L cadmium nitrate solution and chromium electrode in
a 1.0 mol/L chromium(III) nitrate solution?

Cd2+(aq) Cd(s) Cr2+(aq) Cr(s) H2O(l)


cathode anode
E0 cell = E0r cathode – E0r anode
= (-0.40V) - (-0.91V)
= + 0.51V

The E0 cell is positive, therefore the reaction is


spontaneous.
NERNST EQUATION
Gives relationship between the potential of an electrochemical
cell and the concentration of reactants and products

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

For the half reaction

aA + ne- ↔ bB

The half-cell potential (at 25 oC), E, is given by

EE 
O 2.3RT 

log 
B b

 EE 
O RT 

ln 
B b


a  a 
nF  A  nF  A 

0.05916  B b 
EE  O
log  
n  A  a

NERNST EQUATION

For the overall reaction

aA + bB ↔ cC + dD

The potential at 25 oC is given by

2.3RT  C D 


c d RT  C cD d 
EE  log   EE  O
ln  
b 
nF  A B 
O
b 
 A B 
a a
nF

EE 
O 0.05916 
log 
C c
D  d


b 
 A B 
a
n
NERNST EQUATION
 E = Eo when [O] = [R] = 1M

 Concentration for gases are expressed as pressures in


bars or atm

 Concentrations for pure solids, liquids, and solvents are


omitted (activity = 1)

 Reduction is more favorable on the negative side of Eo

 When a half reaction is multiplied by a factor, Eo remains


the same
ELECTROANALYTICAL METHODS

Two main types


 Potentiometric and Potentiostatic
 The type of technique reflects the type of
electrical signal used for quantitation
 Techniques require at least two electrodes and an
electrolyte (containing solution)

Electrodes
Working (indicator) electrode, reference electrode,
counter electrode
ELECTROANALYTICAL METHODS

Potentiometric Technique

 Based on a static (zero-current) situations

 Based on measurement of the potential


established across a membrane

 Used for direct monitoring of ionic species


(Ca2+, Cl-, K+, H+)
ELECTROANALYTICAL METHODS

Potentiostatic Technique

 Controlled-potential technique

 Based on dynamic (non-zero-current) situations

 Deals with the study of charge transfer


processes at the electrode-solution interface

 Chemical species are forced to gain or lose


electrons
REFERENCE ELECTRODES
An ideal reference electrode :

Has a fixed potential over time and


temperature

Long term stability

Ability to return to the initial potential after


exposure to small currents (reversible)

Obey the Nernst Equation


REFERENCE ELECTRODES
• Terdiri dari logam Pt yang dicelupkan ke
Standard dalam larutan asam
Hydrogen • Dijenuhkan dengan gas hidrogen pada
Electrode tekanan 1 atm
(SHE) • E = 0.000 V

• Composed of metallic mercury in contact with


saturated solution of mercurous chloride
Saturated (calomel, Hg2Cl2)
Calomel • Pt wire is in contact with the metallic
Electrode mercury, Calomel is in contact with saturated
(SCE) KCl solution
• E = +0.244 V at 25 oC

Ag/AgCl • Consists of silver metal coated with silver chloride


paste, immersed in saturated KCl and AgCl solution
Electrode • E = +0.199 V at 25 oC
REFERENCE ELECTRODES
SCE:
Pt(s) | Hg(l) | Hg2Cl2 (l) | KCl(aq., sat.) ||.....
REFERENCE ELECTRODES

Ag/AgCl:
Ag(s) | AgCl (s) | Cl-(aq) || .....
INDICATOR ELECTRODES
 Electrode that responds to change in analyte
activity
 Generally show high degree of selectivity

Types of indicator electrodes


o Metallic electrodes (metal wire, mesh, or strip)
 tipe I
o Metal coated with its sparingly soluble salt
(Ag/AgCl)  tipe II
o Electrode gas
o Redox indicator electrode (measures redox
reactions)
INDICATOR ELECTRODES
• Inert:
Pt, Au, Carbon. Don’t participate
in the reaction, example:
SCE || Fe3+, Fe2+(aq) | Pt(s)

• Certain metallic electrodes:


detect their ions (Hg, Cu, Zn, Cd,
Ag) example :
SCE || Ag+(aq) | Ag(s)
Ag+ + e-  Ag(s) E0+= 0.799V

Hg2Cl2 + 2e  2Hg(l) + 2Cl- E0- = 0.241V


E = 0.799 + 0.05916 log [Ag+] - 0.241 V
INDICATOR ELECTRODES
ION-SELECTIVE ELECTRODES (ISE)
 Are indicator electrodes
 Respond directly to the analyte
 Used for direct potentiometric measurements
 Selectively binds and measures the activity of
one ion (no redox chemistry)

Examples
pH electrode
Calcium (Ca2+) electrode
Chloride (Cl-) electrode
INDICATOR ELECTRODES
ION-SELECTIVE ELECTRODES (ISE)
Advantages

 Exhibit wide response


 Exhibit wide linear range
 Low cost
 Color or turbidity of analyte does not
affect results
 Come in different shapes and sizes
INDICATOR ELECTRODES
ION-SELECTIVE ELECTRODES (ISE)
 Made from a permselective ion-conducting
membrane (ion-exchange material that allows
ions of one electrical sign to pass through)
 Reference electrode is inbuilt
 Internal solution (solution inside electrode)
contains ion of interest with constant activity
 Ion of interest is also mixed with membrane
 Membrane is nonporous and water insoluble
INDICATOR ELECTRODES
ION-SELECTIVE ELECTRODES (ISE)
- Responds preferentially to one species in solution

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

 Responsive to univalent cations

 Employs thin ion-selective glass membrane


INDICATOR ELECTRODES
pH GLASS ELECTRODE

 The most widely used


 For pH measurements (selective ion is H+)
 Response is fast, stable, and has broad range
 pH changes by 1 when [H+] changes by a factor of 10
 Potential difference is 0.05196 V when [H+] changes
by a factor of 10
 For a change in pH from 3.00 to 6.00 (3.00 units)
Potential difference = 3.00 x 0.05196 V = 0.177
INDICATOR ELECTRODES
pH GLASS ELECTRODE
- Thin glass membrane (bulb) consists of SiO4

- Most common composition is SiO2, Na2O, and CaO

Glass membrane contains


- dilute HCl solution saturated in AgCl
- inbuilt reference electrode (Ag wire coated with AgCl)
INDICATOR ELECTRODES
pH GLASS ELECTRODE
Glass Electrode Response at 25 oC
(potential across membrane with respect to H+)

E  K  β(0.05916)ΔpH
E  K - 0.05916 log(a H  )

ΔpH = pH difference between inside and outside of glass bulb

β ≈ 1 (typically ~ 0.98)
(measured by calibrating electrode in solutions of known pH)

K = assymetry potential (system constant, varies with electrodes)


INDICATOR ELECTRODES
pH GLASS ELECTRODE
- Equilibrium establishes across the glass membrane with
respect to H+ in inner and outer solutions

- This produces the potential, E

- Linearity between pH and potential

- Calibration plot yields slope = 59 mV/pH units

- Electrode is prevented from drying out by storing in aqueous


solution when not in use
INDICATOR ELECTRODES
pH GLASS ELECTRODE
Sources of Error

- Standards used for calibration


- Junction potential
- Equilibration time
- Alkaline (sodium error)
- Temperature
- Strong acids
- Response to H+ (hydration effect)
INDICATOR ELECTRODES
OTHER GLASS ELECTRODES
Glass Electrodes For Other Cations
K+ -, NH4+-, Na+-selective electrodes
- Mechanism is complex
- Employs aluminosilicate glasses (Na2O, Al2O3, SiO2)
- Minimizes interference from H+ when solution pH > 5

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

 Most common is fluoride-ion-selective electrode


(limited pH range of 0-8.5) (OH- is the only
interfering ion due to similar size and charge)
 Iodide electrode (high selectivity over Br- and Cl-)
 Chloride electrode (suffers interference from Br-
and I-)
 Thiocynate (SCN-) and cyanide (CN-) electrodes
INDICATOR ELECTRODES
LIQUID MEMBRANE ELECTRODES
o Employs water-immiscible substances impregnated
in a polymeric membrane (PVC)
o For direct measurement of polyvalent cations and
some anions
o The inner solution is a saturated solution of the
target ion
o Hydrophilic complexing agents (e.g. EDTA) are
added to inner solutions to improve detection
limits
o Inner wire is Ag/AgCl
INDICATOR ELECTRODES
LIQUID MEMBRANE ELECTRODES
Ion-Exchange Electrodes

- The basis is the ability of phosphate ions to form stable


complexes with calcium ions
- Selective towards calcium
- Employs cation-exchanger that has high affinity for
calcium ions (diester of phosphoric acid)
- Inner solution is a saturated solution of calcium chloride

0.05916
Cell potential is given by EK log(a Ca )
2
INDICATOR ELECTRODES
LIQUID MEMBRANE ELECTRODES

Other Ion-Exchange Electrodes


Have poor selectivity and are limited to
pharmaceutical formulations

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

- For sensing organic and inorganic anions

Examples of Anions
- Phosphate
- Salicylate
- Thiocyanate
- Carbonate
Liquid Membrane Electrodes
INDICATOR ELECTRODES
OTHER ELECTRODES
- Coated-wire electrodes (CWE)
- Solid-state electrodes without inner solutions

- Made up of metallic wire or disk conductor (Cu, Ag, Pt)


- Mechanism is not well understood due to lack of
internal reference
- Usually not reproducible

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

• Consists of pH electrode covered by a CO2 selective


• membrane (silicone)
• Electrolyte between electrode and membrane is
• NaHCO3-NaCl solution
• pH of inner solution lowers when CO2 diffuses through
membrane
• Inner glass electrode senses changes in pH
• Overall potential is determined by CO2 concentration in
sample
INDICATOR ELECTRODES
GAS SENSING PROBES
CO2 Sensors
RT
EK ln[CO 2]
F

HCO3- solution pH glass electrode


CO2 + H2O ↔ H+ + HCO3-
H+ lowers pH

Membrane
(silicone)
INDICATOR ELECTRODES
GAS SENSING PROBES

NH3 Sensors

• Consists of pH electrode covered by NH3 selective


• membrane (teflon or polyethylene)
• Electrolyte between electrode and membrane is
• NH4+-KCl solution
• NH3 goes through membrane and raises pH
• Inner glass electrode senses changes in pH
• Increase in pH is proportional to amount of NH3 in sample
INDICATOR ELECTRODES
GAS SENSING PROBES
Other Gas Sensing Devices

NO2 and SO2


- Makes use of modified pH electrode

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

- Enzymes are proteins that catalyze chemical reactions in


living things

- Based on coupling a layer of an enzyme with an electrode


(enzyme is immobilized on an electrode)

- Electrode serves as a transducer

- Very efficient and extremely selective


INDICATOR ELECTRODES
IMMOBILIZED ENZYME MEMBRANE ELECTRODES
- Enzyme (biocatalytic) layer immobilized on an electrode

Electrode

Biocatalytic Layer
INDICATOR ELECTRODES
IMMOBILIZED ENZYME MEMBRANE ELECTRODES
Applications

• Useful for monitoring clinical, environmental, food


samples
• For determination of glucose in blood (glucose sensors)
• For amperometric sensing of ethanol (ethanol
electrodes)
• For sensing urea in the presence of urease enzyme (urea
electrodes)
INDICATOR ELECTRODES
SOLID-STATE DEVICES

- Known as ion-selective field effect transistors (ISFET)


- Are semiconductor devices
- Surface of transistor is covered with silicon nitride
- Absorbs H+ from solution (results in change of
conductivity)
- Provides the ability to sense several ions (Na+, Ca2+,
K+, pH in blood samples, etc)
- For detection of hydrocarbons and NOx in exhaust
ELECTROANALYTICAL METHODS
Potentiometry
Voltammetry
Polarography
Coulometry

 Methods are classified according to the variable being


measured
 One variable (current, voltage, charge) is measured and
the others are controlled
POTENTIOMETRY

• Based on static (zero-current) measurements


• Involves measurement of potential (voltage) of an
electrochemical cell
• Used to obtain information on the composition of an
analyte
• Potential between two electrodes is measured
(indicator electrode and reference electrode)
• Indicator (sensing) electrode responds to the
concentration of the analyte species
POTENTIOMETRY

• The analyte concentration is related to the


potential difference between the indicator
electrode and the reference electrode (by applying
the Nernst equation)
• Indicator electrode is connected to a reference
electrode (SCE, Ag/AgCl) to form a complete cell
• Implies Etotal = Eindicator – Ereference
• Reference electrode is connected to the negative
terminal of the readout device (potentiometer)
POTENTIOMETRY

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

- Voltage between two electrodes is varied as current is measured

- Solid working electrodes are used

- Oxidation-reduction takes place at or near the


surface of the working electrode

- Graph of current versus potential is obtained

- Peak current is proportinal to concentration of analyte


VOLTAMMOGRAM
- Current versus potential plot

- Current on vertical axis and excitation potential on


horizontal axis

- Electrode reactions involve several steps and can


be complicated

- The rate is determined by the slowest step and depends


on the potential range
CYCLIC VOLTAMMETRY

- Involves linear scanning of potential of a stationary


electrode using a triangular waveform

- Solution is unstirred

- The most widely used technique for quantitative analysis


of redox reactions

Provides information on
- the thermodynamics of redox processes
- the kinetics of heterogeneous electron transfer reactions
- the kinetics of coupled reactions
CYCLIC VOLTAMMETRY

- Is a three electrode system

- Pretreatment (polishing) of working electrode is necessary

- The current resulting from an applied potential is


measured during a potential sweep

- Current-potential plot results and is known as


cyclic voltammogram (CV)
CYCLIC VOLTAMMOGRAM (CV)

Triangular waveform (left) and CV (right) of ferricyanide


CYCLIC VOLTAMMETRY

- Increase in peak current corresponds to achievement


of diffusion control

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

- Voltammetry in which the working electrode is


dropping mercury

- Makes use of potential ramp

- Conventional DC

- Wide cathodic potential range and a renewable surface

- Hence widely used for the determination of many


reducible species
POLAROGRAPHY

- Initial potential is selected such that the reaction of interest


does not take place

- Cathodic potential scan is applied and current is measured

- Current is directly proportional to the


concentration-distance profile

- Reduction begins at sufficiently negative potential


[concentration gradient increases and current rises
rapidly to its limiting value (iL)]
POLAROGRAPHY

- Diffusion current is obtained by subtracting response due to


supporting electrolyte (background current)

- Analyte species entering region close to the electrode surface


undergo instantaneous electron transfer reaction

- Maximum rate of diffusion is achieved

- Current-potential plot provides polarographic wave


(polarogram)
DC POLAROGRAPHY

- Three electrode system

WE = dropping mercury electrode (DME)

CE = Pt wire or foil

RE = SCE
DC POLAROGRAPHY

Half Wave Potential (E1/2)

- Potential at which the current is one-half its limiting value

- E1/2 is independent of concentration of species


1/2
RT  DR 
E 1/2 E 
o
log  
nF  DO 
DR = diffusion coefficient of reduced species
DO = diffusion coefficient of oxidized species

- Experimental E1/2 is compared to literature values to identify


unknown analyte
DC POLAROGRAPHY

Half Wave Potential (E1/2)

At 25 oC
0.05916 i i 
E  E1/2  log  L 
n  i 

- A graph of E versus log[(iL-i)/i] is linear if reaction is reversible


(Nernstian behavior)

- Slope = 0.05916/n and intercept = E1/2

E = E1/2 when [Ox] = [Red]


COULOMETRY
- Method in which charge is measured
- Species being measured is converted quantitatively to a new species

The Methods Based on Electrolysis


- Electrogravimetry
- Constant-potential coulometry
- Constant-current coulometry (coulometric titrimetry)

Electrolysis
- A process causing a thermodynamically nonspontaneous
oxidation or reduction reaction to occur by application
of potential or current
COULOMETRY
Electrogravimetry

- Product of electrolysis is plated on a pre-weighed electrode

- Electrode is weighed again after process and the amount


plated is determined by difference

- Metal dissolves from the anode and deposits on the cathode


(electroplating, electrowinning, or electrorefining)

Examples of metals commonly determined


Cd, Bi, Co, Cu, Sb, Zn, Ni, In, Ag
COULOMETRY
Controlled Potential Coulometry

- Three electrode system

- Permits applied potential pulse or ramp at the working electrode

- Metal elements are deposited as potential is increased which


increases charge passing through cell

- The instrument is the coulometer which measures q


COULOMETRY
Controlled Potential Coulometry

Applications

- Used to eliminate interferences from other reactions that take


place at different potentials

- Used to determine the number of electrons involved in a reaction

- Used for coulometric titrations


COULOMETRY
Conductometric Analysis

- Measures electrical conductivity between two electrodes


by ions in solution

Applications
- To determine the ionic content of drinking water,
deionized water, solvents, beverages

- Used as a detector for ion chromatography, HPLC

- Used for conductometric titrations (end point determination)


TERIMA KASIH