CH 3001 Electroanalytical Methods and Chemical Sensors • • • • • • Introduction Voltametry Potentiometry Coulometry and Electrogravimetry Conductimetry Electrochemical Sensors

in brief

Mass transfer
mass transport occurs by: 1. diffusion = movement due to concentration difference 2 migration of charged species due to potential gradient 3. convection (mechanical stirring or agitation)

M+n

Electrolysis
(-) (+)

M+n A-m

M + n + ne  M →

− reduction − cathod

A− m  A + me − oxidation − anode →

Faradic Current (Non-Charging Current)
(-)

M+n e

Current due to the transfer of electron from the electrode to the ion makes the ion to get reduced and the current produced by such processes is known as Faradic Current. This current obeys the Faraday’s law. This is also known as “noncharging current”.

Charging Current (Non-Faradic Current)
++++++++++++++++++ -----------------------Built-up of electrical charge in the form of a double layer. Current due to the migration of ions through the double layer is known as “Charging Current”. This current does not follow the Faraday’s law. Therefore it is known as “NonFaradic Current”.

Metal

M+n

Voltammetry
• Measurement of current as a function of potential. • Measurement of current under condition of complete concentration polarization. • A minimal consumption of analyte. • Use of mercury as a electrode in this method is known as “Polarography”.

Voltammetry and Polarography
Voltammetry is the electrochemical technique in which the current at an electrode is monitored as a function of potential applied to that electrode. The plot between current and the measured potential is known as “Voltamograme”. In this technique, three-electrode-system is used. Working Electrode: Where the redox reaction takes place: usually-> Hg electrode Reference Electrode: Used to measure the potential of the working electrode Auxiliary Electrode: Used to measure the current at the working electrode

A Modern Polarograph

Principle in Polarograpy
Charging

charged

Reduction e Current

M+

Faradaic Cureent Charging Current Time

+n +n M ( bulk ) → M electrode

Mass transfer

+n M electrod + ne → M electrode Ch arg e transfer

Three ways of mass transfer when a potential is applied to the working electrode:
1. Migration of ions under the influence of the electric field – Migration Current, imig 2. Convection current due to the movement of ions under the influence of hydrodynamic forces – Convection Current, icon 3. Diffusion of ions from higher to lower concentration – Diffusion Current, idif inet = imig + icon + idif Diffusion rate of the ions α Concentration of the ions α diffusion current α inet

DC Polarography
Here, the applied potential is DC voltage The plot between current and the applied potential is known as a Polarogrph
i il

E1/2

Eapp

Powerful Variations of Voltametric Methods:
• • • • • AC Polarography Normal-Pulse Polarography (NPP) Differential Pulse Polarography (DPP) Anodic Stripping Voltammetry (ASV) Cyclic Voltametry (CV)

Faradic Current (Non-Charging Current)
(-)

M+n e

Current due to the transfer of electrons from the electrode to the ion makes the ion to get reduced and the current produced by such processes is known as Faradic Current. This current obeys the Faraday’s law. This is also known as NonCharging Current.

Charging Current (Non-Faradic Current)
++++++++++++++++++ -- - - - - - - - - - - - - - - - - - - - - - Built-up of electrical charge in the form of a double layer. Current due to the migration of ions through the double layer is known as charging current. This current does not follow the Faraday’s law. Therefore known as Non-Faradic Current.

Metal

M+n

Polarography Instrument

DC Polarograph

Oxygen Interferences

How to overcome oxygen interference
• Bubbling of solution with pure nitrogen gas. • Bubbling should be done before the commencement of the analysis. • Through out the analysis nitrogen atmosphere is maintained.

Advantages of DME (compared to planar electrodes)
• clean surface generated • rapid achievement of constant current during drop growth • remixing of solution when the drop falls • high Hg overvoltage means even metals with high -ve E0 can be measured without H2 formation

Disadvantages of DME:
• Hg easily oxidized, limited use as anode (E< +0.4 V) Hg2Cl2 + 2e• 2Hg + 2Cl• nonfaradaic residual currents limit detection to >10-5 M • cumbersome to use (toxic mercury) • sometimes produce current maxima for unclear reasons (use maxima suppressor)

Polarographic Maxima
• sometimes produce current maxima • Can be overcome by using maxima suppressor

Powerful improvement of polarography
• • • • • AC polarogrphy Normal pulse polarography Differential pulse polarography Stripping voltametry Cyclic voltametry

AC polarogrphy
• Instead of DC scan an AC scan is used.

Peaks - the selectivity is higher

Normal pulse polarography
In Normal pulse voltammetry (polarography) - a potential wave is applied – an HME is used

The sensitivity is higher due to the absence of charging current

Differential pulse polarography
In Differential pulse voltammetry (polarography) a differential potential wave is applied – an HME is used

Both sensitivity and selectivity are higher due to the absence of charging current and peaks

Differential pulse polarography

pH (Glass Membrane) Electrodes
• One of the simpler ion-selective electrodes (ISE) • Hydrogen Ion imparts a charge across a hydrated glass membrane • Generally include an internal reference electrode (Ag/AgCl) and a separate Ag/AgCl electrode for sensing the charge imparted by the hydrogen ions • Not as simple to use as you think!

Combination Glass Electrode
solution level

external reference electrode
(porous plug)

internal reference electrode glass membranehydrated
(50 µ m thick)

potential develops across membrane due to pH difference

constant pH External solution

Commercial pH meter

Structure of membrane Glass
3D network of silicate groups. There are sufficient cations within the interstices of this structure to balance the negative charge of silicate groups. Singly charged cations such as sodium are mobile in the lattice and are responsible for electrical conductance within the membrane.

Hygroscopicity of Glass membrane
• Surface of the glass membrane must be hydrated to function as a pH electrode. • It can lose pH sensitivity on dehydration, but is reversible and can be restored by soaking the electrode in water. • The hydration involves an ion-exchange between singly charged cations in the glass lattice and protons from the solution.
+ (solu ) + Na + Gl − ⇔ Na + (solu ) + H + Gl − H

Electrical conduction across membranes
Conductance within the hydrated glass membrane involves the movement of Na+ and H+ ions. Na+ - Charge carriers in the dry interior H+ - Charge carriers in the gel interface
H + (solu1 ) + Gl − ⇔ H + Gl − H + Gl − ⇔ H + (solu 2 ) + Gl −

The positions of these equilibrium depend on the H+ concentration on either side and charge on the glass surface giving potential. The potential difference between the two sides is known as the “Boundary Potential”.

The boundary potential
The potentials associated with each side (solution 1 and solution 2) E1 and E2
RT RT E1 = const + ln(a1 ) E 2 = const + ln(a 2 ) F F RT  a1  E1 − E 2 = ln  a  a 2 is s tan dard solution F  2 
The boundary potential depends only upon the hydrogen ion activity of the external

The asymmetry potential
• When glass electrode’s two sides are in contact with identical solutions, we expect zero potential • However a small potential known as the “Asymmetric Potential” is encountered. • This gradually changes with time. • Electrode must be calibrated against one or more standards. RT E1 − E 2 = const + β ln ( a ) F

Basic Nernst Equation of a pH Electrode

RT E1 − E 2 = const + β ln ( a ) F

depends on internal reference electrode and glass membrane behavior, which changes with time

Must calibrate with a buffer!

Calibration of pH meter
E = E’ – 0.0591β pH

How does the measured voltage, E, vary with pH?
E’ Two point calibration with buffers

E

pH

ISFET A “new” pH electrode

What does 0.05916 mean?
• It is a constant, if there is a one-electron reaction • It can be considered as the equivalent of a constant of 59.16 mV • A pH meter is a highimpedance potentiometer (measures voltage) • A pH change of “1” imparts a change in 59.16 mV to the potential recorded by the pH meter! • 1 pH unit change= 59.16 mV
mV (relative pH readings) 100.00 159.16 218.32 277.48 336.64 395.80 2.00 3.00 4.00 5.00 6.00 7.00

Errors in pH Measurement…
1. Uncertainty in your buffer pH due to normal weighing, diluting errors etc. 2. Junction Potential due to the salt bridge and differences in Junction Potentials over time due to contamination of the junction 3. Overcome by regular recalibration 4. Sodium Error will result in high concentration of sodium solutions. The sodium can also impart a charge across the glass membrane. 5. Acid Error (strong acids) can saturate or contaminate the membrane with hydrogen ions! 6. Equilibration Error is overcome by letting the electrode equilibrate with the solution 7. Dried out glass membrane (ruins electrode) 8. Temperature. Since temperature affects activities, it is best to have all solutions at the same, constant temperature! 9. Strong bases. Strongly basic solutions (>pH 12) will dissolve the glass membrane!

Sodium Electrode
•The change in the composition of the glass membrane permits the determination of cations other than H +. • By modification of the glass membrane, you can make an electrode that is more sensitive to Na+ compared to H3O+. • The modification can be done by incorporating Al2O3 or B2O3.

Ion Selective Electrodes… • Selectivity Coefficient
– Defines how an ISE responds to the species of interest versus some interfering species
• Interferences cause a signal (voltage) to be imparted on the electrode that is NOT the result of the ion or chemical species of interest

– You want the selectivity coefficient to be as SMALL as possible
electrode response X to electrode response A to whereX is theinterferen andA is theanalyte ce k( A, X ) = E = constant β ± 0.05916 log( AA + ∑ (k( A, X ) × AX ) ) n

Examples of Electrodes / Interferences

Solid State Electrodes
• Uses a small amount of a doped crystal to transport charge from the solution to an inner electrode • The inner (sensing) electrode can be a Ag/AgCl electrode, and a separate Ag/AgCl electrode can be present – Combination electrode • You can use a separate reference electrode also.

• Typical equation (Fluoride Electrode):

E = constant β x 0.05916 log(AF- outside) x
• Use:
– Prepare calibration and sample solutions to similar ionic strengths and temperatures – Connect ISE and reference electrode to potentiometer (pH meter in mV mode) – Record potentials of calibration solutions – Prepare calibration curve – Measure potential of sample solutions and calculate fluoride activity!

Liquid membrane electrodes
• Similar to pH electrode except the membrane is an organic polymer saturated with liquid ion exchanger. • Interaction of this exchanger with target ions resulted in a potential across the membrane that can be measured.

Liquid Membrane ISE’s
• Replace the solid state crystal with a liquid ionexchanger filled membrane • Ions impart a charge across the membrane • The membrane is designed to be SELECTIVE for the ion of interest…

Liquid membrane electrodes
• The reservoir forces exchanger into membrane. • The exchanger forms complexes with species of interest. • This results in a concentration difference and the resulting potential difference can be measured.

Gas Sensing Electrodes
• Still considered “ion-selective” • Works by the permeation of gas across a selective membrane • Also called compound electrodes • The gas changes the pH inside the electrode (on the inside of the membrane) and this signal is proportional to the gas concentration.

Gas Sensing Electrodes

Enzyme Electrodes

Enzyme Electrodes

Enzyme Electrodes
EE transducer

Analyte

recognition

signal

Enzyme Electrodes
EE transducer

Analyte

No recognition

No signal

Potentiometric Titrations
ECell

End Point

VTitrant

Potentiometric Titration
• How does the pH change during an acidbase neutralization reaction? • Measure pH as the titrant is added.

HCl + NaOH  NaCl + H2O
How do we locate the equivalence point? pH Equivalence point pH pH = 7

Volume of titrant (mL NaOH)

HCl + NaOH  NaCl + H2O
What is present at various points? xs NaOH & salt pH Just pH = 7 salt

Just acid

Both acid & salt

Volume of titrant (mL NaOH)

HCl + NaOH  NaCl + H2O
The slope between each pair of data points. pH
7 from increasing to decreasing

inflection point - changed

decreasing slope

increasing slope

How is the slope changing? Volume of titrant (mL NaOH)

Using the derivative to locate the equivalence point
16 14 12

pH

pKa

10 8 6 4 2

The maximum of the derivative locates the equivalence point. 0
0 5 10 15

Electrogravimetry & coulometry
 Both are electrolysis processes  Constant potential electrolysis – potential of the working electrode is held constant  Constant current electrolysis – current at the working electrode is held constant  Complete electrolysis  Amount of material discharge – Electrogravimetry  Amount of electricity required - Coulometry

Electrogravimetry
• Mostly used in metal ion analysis • Deposits on cathode as the metal • Weight of the cathode before and after the complete electrolysis • Electrodes used in the electrolysis must be inactive

Decomposition potential
Increase of the potential at the working electrode leads to give a current at a certain potential.
Current

Decomposition potential

potential

Factors effecting decomposition potential
• Equilibrium potential • Ohmic potential • Overpotential –
activation and concentration

E d = ∆E eq + E op + E aop + E cop

Selectivity in electrolysis
Current

E1

E1

potential

Applied potential between E1 and E2 only one metal ion gets reduced.

Selectivity in electrolysis cont...
The electrolysis under constant potential is selective. The electrolysis under constant current is non-selective.

Apparatus for electrogravimetry

Depolarization of electrodes
• As the current decreases, the potential needs to be increased in order to offset IR drop and then excess ions present in the solution may start to discharge. Under these circumstance, the electrode is said to be depolarized. This will lead to codeposit and can start before the ion interested to complete the deposition. This will lead to interferences.

Interferences in Electrolysis
Example: Mixture of Cu(II) and Pb(II) Deposition of Cu(II) starts at 0.2 V. Due to the IR drop, in order to keep the current constant,potential should be increased. In acidic solutions reduction of H+ occurs and deposition may not adhere to the electrode.

Depolarizers in electrolysis
• In order to avoid H2 evolution from cathode, we add nitrate ions into the solution.

Instead of

1 H +e → H 2 2
+

− NO3 + 10H + + 8e  NH + + 3H 2O → 4

• Here, the nitrate ion is called depolarizer which avoids the reduction of H+.

Electrolysis under constant current
• This is lack of selectivity and do not have any practical importance when a mixture of ions are present in the solution. • However, if a single ion is present, this method is more advantages since the time necessary for complete electrolysis can be controlled.

Electrolysis under constant potential
• The potential of the working electrode can be controlled and kept at a constant value. However as the electrolysis is going on the current is continuously dropping (the rate of discharge is dropping). • It takes a longer time for complete electrolysis, but however interferences can be avoided.

Electrolysis under constant potential
• • • • Mixture of Cu(II) and Pb(II) The deposition potential for Cu(II) – 0.2 V The deposition potential for Pb(II) - -0.15 V By controlling the potential, Cu can be deposited first and then Pb can be determined by taking the weight of the cathode at each occasion.

The quantity of electrical charge
• Under constant current Q = it

• Under constant potential

Q = ∫ idt
o

t

• By measuring the amount of electricity one can calculate the amount of material discharge.

Coulometry
• Two types of methods • Constant potential coulometry - selective • Constant current coulometry- non-selective
• Coulometry is same as electrogravimetry but instead of measuring the weight of discharge material, here, the amount of electricity is measured which can be related to the amount of material according to Faraday’s law.

Coulometric Titration
• Here the titrant is electrically generated. • Example: Analysis of As(III) • The solution containing As(III) was added to excess I- and electrolysis carried out. • The I2 produced will react with As(III)

As(III)  As(V) + 2e → I 2 + 2e  2I − →

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