ANALYTICAL CHEMISTRY CHEM 3811
CHAPTER 15
DR. AUGUSTINE OFORI AGYEMANAssistant professor of chemistryDepartment of natural sciences
Clayton state university
CHAPTER 15
ELECTRODE MEASUREMENTS
INDICATOR ELECTRODES
Chemically Inert Electrodes
- Do not participate in the reaction
ExamplesCarbonGold
PlatinumITO
INDICATOR ELECTRODES
Reactive Electrodes
- Participate in the reaction
ExamplesSilver
CopperIronZinc
INDICATOR ELECTRODES
- Respond directly to the analyte
Two Classes of Indicator Electrodes
- Metal Electrodes
- Surfaces on which redox reactions take place
ExamplesPlatinum
Silver
INDICATOR ELECTRODES
- Respond directly to the analyte
Two Classes of Indicator Electrodes
- Ion-Selective Electrodes
- Selectively binds one ion (no redox chemistry)
ExamplespH electrode
Calcium (Ca2+) electrodeChloride (Cl-) electrode
DOUBLE-JUNCTION REFERENCE ELECTRODES
- With the use of reference electrodes
- KCl solution may slowly leak into solution through the porous plug (salt bridge)
- Cl- may introduce errors(e.g. consumes Ag+ when reagent is Ag+ solution)
- Double-junction reference electrode prevents direct leakage into reagent
JUNCTION POTENTIAL
- When two dissimilar electrolyte solutions come in contact
- Potential difference develops at the interface
- Voltage is very small usually in millivolts
- Very common at the ends of salt bridges
- Observed voltage measurements may include junction potential
JUNCTION POTENTIAL
Eobserved = Ecell + Ejunction
- A result of unequal ion mobilities
- K+ and Cl- have similar mobilities
- Reason why KCl is used in salt bridges
POTENTIOMETRY
- The use of voltage measurements for quantification
Direct Potentiometric Method- Measures absolute potential (concentration)
- A metal in contact with a solution of its cation- Associated with errors due to junction potentials
Examples- Silver wire for measuring [Ag+]
- Potassium ion-selective electrode for measuring [K+]- pH electrode for measuring [H+]
POTENTIOMETRY
- The use of voltage measurements for quantification
Relative Potentiometric Method- Measures changes in potential (concentration)
- Relatively precise and accurate
Example- Measuring changes in potential during titration
ION-SELECTIVE ELECTRODES
- Responds preferentially to one species in solution
Internal reference electrode
Ion-selective membrane
Filling solution
- Selective (preferential) ion is C+
- Membrane is made of poly(vinyl chloride)
- Membrane is impregnated with nonpolar liquid
- Membrane contains ligand L (ion-selective ionophore)
- Membrane contains the complex LC+
- Membrane contains hydrophobic anion R- (ion exchanger)
ION-SELECTIVE ELECTRODES
- [C+] inside the electrode ≠ [C+] outside the electrode
- Produces a potential difference across the membrane
ION-SELECTIVE ELECTRODES
inner
outer
][C
][Clog
n
0.05916E
- n is the charge on the selective ion (negative for anions)
n = +1 for K+
n = +2 for Ca2+
n = -2 for CO32-
at 25 oC
pH GLASS ELECTRODE
- The most widely used
- Selective ion is H+
- Glass membrane (bulb) consists of SiO4
- 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
pH GLASS ELECTRODE
Glass Electrode Response at 25 oC
E = constant + β(0.05916)ΔpH
ΔpH = pH difference between inside and outside of glass bulb
β ≈ 1 (typically ~ 0.98)(measured by calibrating electrode in solutions of known pH)
constant = assymetry potential
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)
COMPOUND ELECTRODE
- Electrode surrounded by a membrane
- Membrane isolates the analyte to which the electrode responds
Examples- Gas sensing electrodes
NH3, CO2, NOx, H2S, SO2
- Enzyme electrodes (highly selective)
ELECTROCHEMICAL METHODS
Applications
- Biosensors (analyte sensors)(Glucose sensors)
- Chromatography detectors- Solar energy storage systems
- Microelectronics- Electrocatalysis of fuel cells and batteries
Electrogravimetric Analysis
- Chemically inert cathode with large surface area is used(in the form of gauze)
- Analyte is electroplated (deposited) on a preweighed cathode
- Cathode is weighed again
- Mass of analyte is determined by difference
Cu2+(aq) + 2e- → Cu(s) (deposited on cathode)
ELECTROCHEMICAL METHODS
Coulometric Analysis
- Amount of analyte is determined from electron count
- Electric current and time required to generate product are measured
- Number of electrons is determined from current and time
- Number of moles of analyte is determined from electron count
Reaction of I2 and H2SI2 + H2S → S(s) + 2H+ + 2I-
ELECTROCHEMICAL METHODS
Three Electrode Cells
- Reference electrode- Working (indicator) electrode- Auxiliary (counter) electrode
- Current flows between working and auxiliary electrodes
- Voltage is measured between working and reference electrodes
ELECTROCHEMICAL METHODS
Amperometry
- The electric current between the pair of electrodes is measured
- Voltage is fixed
- Current is proportional to the concentration of analyte
Biosensors(glucose monitors)
ELECTROCHEMICAL METHODS
Voltammetry
- Voltage between two electrodes is varied as current is measured
- Oxidation-reduction takes place at or near the surface of the working electrode
- Graph of current versus potential is obtained(called voltammogram)
- Peak current is proportinal to concentration of analyte
ELECTROCHEMICAL METHODS
Voltammetry
Polarography- Uses dropping-mercury electrode
Square Wave Voltammetry- Uses waveform which consists of square wave
superimposed on a staircase
ELECTROCHEMICAL METHODS
Voltammetry
Stripping Voltammetry- Analyte is concentrated into a drop of Hg by reduction
- Analyte is reoxidized by making potential more positive- Current is measured during oxidation
Cyclic Voltammetry (CV)- Electrode potential versus time is linear
- Current versus applied voltage gives a cyclic voltammogram trace- Used to study electrochemical properties of analytes
ELECTROCHEMICAL METHODS
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