ELECTROANALISIS

(Elektrometri)
Potensiometri, Amperometri and Voltametri
 Electroanalysis

• Mengukur berbagai parameter listrik

(potensial, arus listrik, muatan listrik,
konduktivitas) dalam kaitannya dengan
parameter kimia (reaksi ataupun konsentrasi
dari bahan kimia)

• Konduktimetri, Potensiometri (pH, ISE),

Koulometri, Voltametri, Amperometri
 Potensiometri
Pengukuran potensial listrik dari suatu Sel Elektrokimia
untuk mendapatkan informasi mengenai bahan kimia
yang ada pada sel tsb (conc., aktivitas, muatan listrik)

Mengukur perbedaan potensial listrik antara 2

electroda:
Elektroda Pembanding (E constant)
Elektroda Kerja/Indikator(sinyal analit)
 Elektroda Pembanding
- +

Ag/AgCl
Salt bridge

Pt

KCl Fe2+ , Fe 3+

AgCl(s) + e - <=> Ag(s) + Cl - Fe3+ + e - <=> Fe2+

E0 =0.222V + E0 =0.771V
-
E(KCl sat.)=0.197V

Ag
Pt
Soln. aq. satd
Ag/AgCl: in KCl + AgCl
Ag(s) | AgCl (s) | Cl-(aq) || ..... AgCl

AgCl + KCl Fe2+ , Fe 3+

Porous glass
 Elektroda Pembanding
SCE:
Pt(s) | Hg(l) | Hg2Cl2 (l) | KCl(aq., sat.) ||.....

Pt

Hg(l) Hg2 Cl 2 + 2e - <=> 2Hg(l) + 2Cl -

Hg, Hg 2 Cl 2 et KCl E0 =0.268V

Glass wool E(KCl sat.)=0.241V

Soln. sat. in KCl
KCl

Porous glass
 Elektroda Pembanding
• Reaksi/Potensial setengah selnya diketahui
• Tidak bereaksi/dipengaruhi oleh analit yang diukur
– Reversible dan mengikuti persamaan Nernst
– Potensial Konstan
– Dapat kembali ke potensial awal

• Elektroda Calomel
– Hg in contact with Hg(I) chloride
– Ag/AgCl
 Electroda Kerja
• Inert:
Pt, Au, Carbon. Tidak ikut bereaksi.

Contoh: SCE || Fe3+, Fe2+(aq) | Pt(s)

• Elektroda Logam yang mendeteksi ion logamnya sendiri

(1st Electrode)
(Hg, Cu, Zn, Cd, Ag)

Contoh: SCE || Ag+(aq) | Ag(s)

Ag+ + e-  Ag(s) E0+= 0.799V

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

E = 0.799 + 0.05916 log [Ag+] - 0.241 V

 Electroda Kerja
• Ecell=Eindicator-Ereference
• Metallic
– 1st kind, 2nd kind, 3rd kind, redox

1st kind
– respond directly to changing activity of electrode
ion
– Direct equilibrium with solution
 2nd kind
• Precipitate or stable complex of ion
– Ag for halides
– Ag wire in AgCl saturated surface

• Complexes with organic ligands

– EDTA

3rd kind
– Electrode responds to different cation
 Metallic Redox Indictors

 Inert metals
– Pt, Au, Pd
• Electron source or sink
• Redox of metal ion evaluated
– May not be reversible
Membrane Indicator electrodes
– Non-crystalline membranes:
• Glass - silicate glasses for H+, Na+
• Liquid - liquid ion exchanger for Ca2+
• Immobilized liquid - liquid/PVC matrix for Ca2+ and
NO3-
– Crystalline membranes:
• Single crystal - LaF3 for FPolycrystalline
• or mixed crystal - AgS for S2- and Ag+
 Properties
o Low solubility - solids, semi-solids and polymers
o Some electrical conductivity - often by doping
o Selectivity - part of membrane binds/reacts with analyte
Glass Membrane Electrode
 Ion selective electrodes (ISEs)
A difference in the activity of an ion on either side of
a selective membrane results in a thermodynamic
potensial difference being created across that
membrane
+ -
0 .0 1 M Ca2 + 0 .1 M Ca2 + ( 0 . 1 + ) M Ca +
2
( 0 . 1 - ) M Ca2 +
Ca2 + Ca2 +
+ -

-
+
0 .0 2 M Cl - 0 .2 M Cl - 0 .0 2 M Cl - 0 .2 M Cl -
+ -

Calcium selective
molecular
recognition ligand
 ISEs
A1
G   RT ln   nFE
A2
RT A1 0.0592 A1
E ln  log
nF A2 n A2
(@ 25C)
Combination glass pH Electrode
+ -

Ag

Soln. aq. satd

in KCl + AgCl

AgCl porous
AgCl(s) + KCl(s) glass

0.1M HCl in
AgCl sat.
 Proper pH Calibration
• E = constant – constant.0.0591 pH
• Meter measures E vs pH – must calibrate both slope & intercept on
meter with buffers
• Meter has two controls – calibrate & slope
• 1st use pH 7.00 buffer to adjust calibrate knob
• 2nd step is to use any other pH buffer
• Adjust slope/temp control to correct pH value
• This will pivot the calibration line around the isopotensial which is set to
7.00 in all meters
Slope/temp control pivots
mV line around isopotensial
without changing it
Calibrate knob raises
and lowers the line
without changing slope 4 7
pH
Liquid Membrane Electrodes
 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
 voltametri
The measurement of variations in arus listrik
produced by variations of the potensial applied to a
working electrode
polarography:
• Heyrovsky (1922): first voltametri experiments using
a dropping mercury working electrode

In voltametri, once the applied potensial is

sufficiently negative, electron transfer occurs
between the electrode and the electroactive species:
Cu2+ + 2e → Cu(Hg)
 Why Electrons Transfer
Reduction Oxidation

EF Eredox
E E
Eredox E
F

• Net flow of electrons from • Net flow of electrons from

M to solute solute to M
• Ef more negative than Eredox • Ef more positive than Eredox
• more cathodic • more anodic
• more reducing • more oxidizing
Steps in an electron transfer event
 O must be successfully transported
from bulk solution (mass transport)
 O must adsorb transiently onto
electrode surface (non-faradaic)
 CT must occur between electrode and
O (faradaic)
 R must desorb from electrode surface
(non-faradaic)
 R must be transported away from
electrode surface back into bulk
solution (mass transport)
 Mass Transport or Mass Transfer
• Migration – movement of a muatan listrik listrik particle in a
potensial field
• Diffusion – movement due to a concentration gradient. If
electrochemical reaction depletes (or produces) some species
at the electrode surface, then a concentration gradient
develops and the electroactive species will tend to diffuse
from the bulk solution to the electrode (or from the electrode
out into the bulk solution)
• Convection – mass transfer due to stirring. Achieved by some
form of mechanical movement of the solution or the
electrode i.e., stir solution, rotate or vibrate electrode
Difficult to get perfect reproducibility with stirring, better to
move the electrode
Convection is considerably more efficient than diffusion or
migration = higher arus listriks for a given concentration =
greater analytical sensitivity
 Nernst-Planck Equation

x
J
D

Cx
i
 
z
F
i
C
D
  
x
C
x
 
i i

xRT i i
x i

Diffusion Migration Convection

Ji(x) = flux of species i at distance x from electrode (mole/cm2 s)

Di = diffusion coefficient (cm2/s)
Ci(x)/x = concentration gradient at distance x from electrode
(x)/x = potensial gradient at distance x from electrode
(x) = velocity at which species i moves (cm/s)
 Diffusion
Fick’s 1st Law

I = nFAJ

Solving Fick’s Laws for

particular applications
like electrochemistry
involves establishing
Initial Conditions and
Boundary Conditions
 Simplest Experiment
Chronoamperometri

time
Simulation
Recall-Double layer
 Double-Layer charging
• Charging/discharging a capacitor upon application
of a potensial step

E  t / RC 
Ic  e
R

Itotal = Ic + IF
 Working electrode choice
• Depends upon potensial window desired
– Overpotensial
– Stability of material
– Conductivity
– contamination
 The polarogram
points a to b
I = E/R
points b to c
electron transfer to the
electroactive species.
I(reduction) depends on
the no. of molecules
reduced/s: this rises as a
function of E
points c to d
when E is sufficiently
negative, every molecule
that reaches the electrode
surface is reduced.
 Dropping Mercury Electrode
• Renewable surface
• potensial window expanded for reduction
(high overpotensial for proton reduction at
mercury)
 Polarography
A = 4(3mt/4d)2/3 = 0.85(mt)2/3
Density of Mass flow rate of drop
drop

We can substitute this into Cottrell Equation

i(t) = nFACD1/2/ 1/2t1/2
We also replace D by 7/3D to account for the compression of the diffusion
layer by the expanding drop
Giving the Ilkovich Equation:
id = 708nD1/2m2/3t1/6C
I has units of Amps when D is in cm2s-1,m is in g/s and t is in
seconds. C is in mol/cm3

This expression gives the arus listrik at the end of the drop life. The average arus listrik is

obtained by integrating the arus listrik over this time period

Polarograms

E1/2 = E0 + RT/nF log (DR/Do)1/2

(reversible couple)

Usually D’s are similar so half

wave potensial is similar to formal
potensial. Also potensial is
independent of concentration and
can therefore be used as a
diagnostic of identity of analytes.
 Other types of Polarography

• Examples refer to polarography but are applicable to other

votammetric methods as well
• all attempt to improve signal to noise
• usually by removing capacitive arus listriks
 Normal Pulse Polarography

• arus listrik measured at a single instant in the lifetime of each drop.

• higher signal because there is more electroactive species around each
drop of mercury.
• somewhat more sensitive than DC polarography.
• data obtained have the same shape as a regular DCP.
 NPP advantage

• IL = nFAD1/2c/(ptm)1/2
• (tm = arus listrik sampling t)
• IL,N.P./IL,D.C. = (3t/7tm)1/2
• Predicts that N.P.P.
5-10 X sensitive than D.C.P.
Differential pulse voltametri
 DPP
• arus listrik measured twice during the lifetime of each drop
difference in arus listrik is plotted.
• Results in a peak-shaped feature, where the top of the peak
corresponds to E1/2, and the height gives concentration
• This shape is the derivative of the regular DC data.
• DPP has the advantage of sensitive detection limits and
discrimination against background arus listriks. Traditionally,
metals in the ppm range can be determined with DPP.
• Derivative improves contrast (resolution) between
overlapping waves
 DPP vs DCP
Ep ~ E1/2 (Ep= E1/2±DE/2)

where DE=pulse amplitude

nFAD 1/2 c 1 - 
Ip 
(t m  1  

s = exp[(nF/RT)(DE/2)]

Resolution depends on DE
W1/2 = 3.52RT/nF when D E0

Improved response
because charging arus listrik
is subtracted and adsorptive
effects are discriminated against.
l.o.d. 10-8M
Resolution
Square wave voltametri
SWV
SWV Response
 SWV

• advantage of square wave voltametri is that the entire scan

can be performed on a single mercury drop in about 10
seconds, as opposed to about 5 minutes for the techniques
described previously. SWV saves time, reduces the amount
of mercury used per scan by a factor of 100. If used with a
pre-reduction step, detection limits of 1-10 ppb can be
achieved, which rivals graphite furnace AA in sensitivity.

• data for SWV similar to DPP

• height and width of the wave depends on the exact
combination of experimental parameters (i.e. scan
rate and pulse height
 Stripping voltametri
• Preconcentration technique.

1. Preconcentration or accumulation step. Here the analyte species is

collected onto/into the working electrode
2. Measurement step : here a potensial waveform is applied to the electrode
to remove (strip) the accumulated analyte.
Deposition potensial
ASV
ASV or CSV
 Adsorptive Stripping
voltametri

• Use a chelating
ligand that adsorbs
to the WE.
• Can detect by redox
process of metal or
ligand.
Multi-Element
Standard Addition
 Cyclic voltametri
• Cyclic voltametri is carried out at a stationary
electrode.
• This normally involves the use of an inert disc
electrode made from platinum, gold or glassy carbon.
Nickel has also been used.
• The potensial is continuously changed as a linear
function of time. The rate of change of potensial with
time is referred to as the scan rate (v). Compared to a
RDE the scan rates in cyclic voltametri are usually
much higher, typically 50 mV s-1
 Cyclic voltametri
• Cyclic voltametri, in which the direction of the potensial
is reversed at the end of the first scan. Thus, the
waveform is usually of the form of an isosceles triangle.
• The advantage using a stationary electrode is that the
product of the electron transfer reaction that occurred in
the forward scan can be probed again in the reverse
scan.
• CV is a powerful tool for the determination of formal
redox potensials, detection of chemical reactions that
precede or follow the electrochemical reaction and
evaluation of electron transfer kinetics.
Cyclic voltametri
Cyclic voltametri

For a reversible
process
Epc – Epa = 0.059V/n
The Randles-Sevcik equation Reversible systems
 The Randles-Sevcik equation Reversible systems
i p  0.4463nFAC  nFvD RT 
12

 5

i p  2.687 10 n v D AC 32 12 12

• n = the number of electrons in the redox reaction

• v = the scan rate in V s-1
• F = the Faraday’s constant 96,485 coulombs mole-1
• A = the electrode area cm2
• R = the gas constant 8.314 J mole-1 K-1
• T = the temperature K
• D = the analyte diffusion coefficient cm2 s-1
The Randles-Sevcik equation Reversible systems

As expected a plot of peak height vs the square root of the scan rate
produces a linear plot, in which the diffusion coefficient can be obtained
from the slope of the plot.
Cyclic voltametri
Cyclic voltametri
Cyclic voltametri
 Cyclic voltametri – Stationary Electrode
• Peak positions are related to formal potensial of redox
process
• E0 = (Epa + Epc ) /2
• Separation of peaks for a reversible couple is 0.059/n volts
• A one electron fast electron transfer reaction thus gives
59mV separation
• Peak potensials are then independent of scan rate
• Half-peak potensial Ep/2 = E1/2  0.028/n
• Sign is + for a reduction
 Cyclic voltametri – Stationary Electrode
• The shape of the voltammogram depends on the transfer
coefficient 
• When   deviates from 0.5 the voltammograms become
asymmetric -cathodic peak sharper as expected from Butler
Volmer eqn.