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MINGGU LALU

Anoda (up ways)

The anode is the electrode at
which an oxidation takes

Katoda (down ways)

The cathode in an electrochemical cell is
the electrode at which reduction occurs

PRINSIP DASAR : SHE

mV

Test electrode

Gas H2 (1 ba)r

2H+ + 2e- H2
E0 = 0.0 V

catalytic Pt surface in acidic solution (1M)

PRINSIP DASAR : SHE

Types of Electrochemical Cells

Electrochemical cells are either galvanic or electrolytic

Electrolytic

Convert electrical energy into chemical energy

Galvanic

Convert chemical energy into electrical energy

Galvanic

Electrolytic

[Cu2+] increases with time

[Ag+] decrease with time

Eright Eleft decreases with time

mV

The Nernst Equation

e- e- e-
Complete Nernst Equation for cell

Cd(s)

Ag(s)

If the net cell voltage + spontaneous

in the opposite direction

Cd2+

KCl

Electrons flow toward more positive potential

0.01 M

If the net cell voltage + spontaneous

in the forward direction

0.5 M

The Nernst Equation

RT [Reduced]
2.303RT
[Reduced]
0
E E ln
E
log
nF [Oxidized]
nF
[Oxidized]
0

Ket

E = Potential at temperature T
E0 = Standard electrode potential (25C, 1.0M)
R = Ideal gas constant
F = Faradays constant
n = number of electrons transferred

Complete Nernst Equation for cell

If the net cell voltage + spontaneous

in the forward direction
If the net cell voltage + spontaneous
in the opposite direction

The magnitude of the potential difference between the two electrodes is 0.412 V independent of which electrode
is considered the left or reference electrode.
However, no matter how the cell is arranged, the spontaneous cell reaction is oxidation of Cu and reduction
of Ag1, and the free energy change is 79,503 J

POTENSIOMETRI AMPEROMETRI

POTENTIOMETRY
analysis based on measuring the potential of electrochemical cells
without drawing appreciable current (constant current or zero
current).
A reference electrode is a half-cell
having a known electrode potential
that remains constant at constant
temperature and is independent of
the composition of the analyte
solution

An indicator electrode has a potential

that varies in a known way with
variations in the concentration of an
analyte.

By convention, the reference electrode is always treated as the left-hand electrode in potentiometric
measurements

POTENTIOMETRY
The reference electrode (Eref) Juction Potential (Ej)

The Indicator electrode (Eind)

ELECTRODE
Reference Electrodes
Calomel Reference
Electrodes
Silver/Silver Chloride
Reference Electrodes

Indicator Electrodes
Metallic Indicator Electrodes
Electrodes of the first kind,
Electrodes of the second
kind,
Inert redox electrodes
Membrane Indicator
Electrodes

The Calomel Electrode

mV

Test electrode
consist of mercury in contact with a solution that is
saturated with mercury (I) chloride (calomel) and that
also contains a known concentration of potassium
chloride

Calomel paste (Hg0/Hg2Cl2)

Saturated KCl

Hg2Cl2 + 2e- 2Hg0 + 2ClE0 = 0.268V

Liquid junction

RE : SILVER/SILVER CHLORIDE ELECTRODES

mV

Test electrode

Silver wire
this electrode is prepared with either a saturated or
a 3.5 M potassium chloride solution

Saturated
KCl + AgNO3

they can be used at temperatures greater than

60C, while calomel electrodes cannot

Liquid junction

AgCl + e- Ag0 + ClE0 = 0.222V

IE : METALLIC INDICATOR ELECTRODES

Electrodes of the First Kind
Pure metal electrode that is in direct equilibrium with its cation in the
solution
Respond not only to their own
cations but also to other more
easily reduced cations
Many metal electrodes, such
as zinc and cadmium, can only
be used in neutral or basic
Other metals are so easily
oxidized
Do not provide reproducible
potentials
Neutral : Ag/Ag+ and Hg/Hg+2
Deaerated : Cu/Cu+2, Zn/Zn+2, Cd/Cd+2, Bi/Bi+3, Tl/Tl+1, and Pb/Pb+2

IE : METALLIC INDICATOR ELECTRODES

Electrodes of the Second Kind
Metals not only serve as indicator electrodes for their own cations but also respond
to the activities of anions that form sparingly soluble precipitates or stable complexes
with such cations
The potential of a silver electrode, for example, correlates reproducibly with the activity of
chloride ion in a solution saturated with silver chloride

in a solution saturated with silver chloride, a silver electrode can serve as an indicator electrode of
the second kind for chloride ion

IE : Membrane Indicator Electrodes

Membrane electrodes are sometimes called p-ion electrodes (pfunctions, such as pH, pCa, or pNO3)
The Glass Electrode
The Plastic Electrode
The Solid State Electrode

The most significant drawback of the electrodes is that they are not
specific but only selective for the measurement of individual ion
activities. Therefore they are more correctly referred to as ionselective electrodes

mV

Ecell = ERef(1) + Elj ERef(2)

Ecell EISM

Ref 2

Ref 1

+
+

+
+
+

+
+

Ion-selective
membrane

IE : Membrane Indicator Electrodes

The Composition and Structure of Glass Membranes
exhibit excellent specificity to hydrogen ions
up to a pH of about 9.
At higher pH values, the glass becomes
responsive to sodium as well as to other singly
charged cations

+
K

ion-selective electrode
H
N
H

Valinomycin is an antibiotic that

has a rigid 3-D structure
containing pores with dimensions
very close to the un-hydrated
radius of the potassium ion.
Valinomycin serves as a neutral
carrier for K+.

O
N
O
O

O
O

O
N

+
K

O
O

O
O
N
O

N
H

++
Ca

ion selective electrode

di-p-octylphenyl phosphate
PVC membrane
H3C
O

O
P

H3C

O-

Ca++
O

O-

H3C
P
O
H3C

++
Ca

ion selective electrode

Neutral carrier

Inert membrane

H3C

CH3

CH3

N
O
O
H3C

Ca++
H3C

O
O
O
N
H3C

IE : Membrane Indicator Electrodes

Boundary Potential

exterior of the glass and the

analyte solution
interface between the internal solution
and the interior of the glass

IE : Membrane Indicator Electrodes

Boundary Potential

a1 is the activity of the analyte solution

a2 is the activity of the internal solution
(held constant)

The boundary potential is then a measure of the hydrogen ion activity (pH) of the
external solution.

IE : Membrane Indicator Electrodes

The Glass Electrode Potential
The potential of a glass indicator electrode
The boundary potential,
The potential of the internal Ag/AgCl reference electrode

IE : Membrane Indicator Electrodes

The Alkaline Error
In basic solutions, glass electrodes respond to the
concentration of both hydrogen ion and alkali metal ions

The Acid Error

the typical glass electrode exhibits an error, opposite in
sign to the alkaline error, in solution of pH less than about
0.5

saturation effect that occurs when all the surface sites on

the glass are occupied
with H1 ions

APPLICATION OF POTENTIOMETRY
Direct Potentiometry

Determining the activity of a variety of cations and anions.

Comparison of the potential developed in a cell containing the indicator
electrode in the analyte solution with its potential when immersed in
one or more standard solutions of known analyte concentration
Example : pH measurement

Direct Potentiometry
the potential of a cell can then be expressed in terms of the
potentials developed by the indicator electrode, the reference
electrode, and a junction potential

Direct Potentiometry
Electrode response is related to analyte activity
rather than analyte concentration.
the pH of the standard buffer used for calibration is generally
based on the activity of hydrogen ions

Hal yang perlu diperhatikan

Perhatikan temperatur pengukuran yang dilakukan
Selalu mengaduk larutan (homogenisasi larutan)
Volume larutan cukup sehingga elektroda dari pH meter tercelup
sempurna

Kondisi elektroda
Kondisi elektroda

Stabilitas pengukuran

Slope dan offset

slope: 95-105%
offset: (0-15) mV
Elektroda bagus

slope: 90-94%
offset: (15-35) mV

slope: 85-89%
offset: > 35 mV

Elektroda perlu dibersihkan

Elektroda bermasalah

Kalibrasi
Dilakukan minimal Sekali per 24 jam sebelum melakukan pengukuran
Hal yang diperhatikan
Offset
Slope

Metode
Minimum menggunakan 2 pH buffer standar
Jika pengukuran dilakukan pada rentang pH lebar gunakan 3-5 pH buffer standar

Kalibrasi
Pada pH 7 standar elektroda
akan menghasilkan 0 mV

OFFSET DAN SLOPE

Keadaan nyata, pH 7 tidak sama

dengan 0. Maka perlu dikalibrasi
Nilai offset

mV

mV terukur pada pH 7 dijadikan

nilai nol
pH

mV
Slope baku

Slope pengukuran

TEMPERATURE EFFECT
The value for the gradient will change
depending on the temperature of the
measurement solution
Therefore it is essential that you
calibrate the pH electrode at the same
temperature at which the
measurements are to be performed, to
avoid introducing a systematic error and
that you allow time for the electrode to
equilibrate at that temperature prior to
the measurement.

PENTING

pH SAMPEL harus BERADA

diantara RENTANG pH BUFFER
STANDAR UNTUK KALIBRASI

4. Bilas kembali elektroda

POTENTIOMETRY TITRATION
Potentiometric titration measurement of
the potential of a suitable indicator electrode as
a function of titrant volume.
more reliable than data from titrations that use chemical
indicators
particularly useful with colored or turbid solutions

the measurement is based on the titrant volume that

causes a rapid change in potential near the
equivalence point,

1. Acid-base titration pH (glass) electrode

2. Redox titration inert electrode (Platinum)
3. Argentometry silver electrode

POTENTIOMETRY TITRATION

POTENTIOMETRY TITRATION
= 1
= 1

Volume Titrant (mL)

pH terukur dari alat

+ 1
=
2

POTENTIOMETRY TITRATION

= (

( = (

+ 1
=
2

 Another method : GRANs PLOT

TUGAS : PLEASE FIND THE GRAN PLOT AND HOW TO FIND PKA WITH
GRANS PLOT!

VOLTAMMETRY
Voltammetry: a group of electroanalytical methods in which by
measuring current in an electrochemical cell as a function of applied
potential
Polarography is voltammetry at the dropping mercury electrode
coulometry, electrons participating in a chemical reaction are
counted to learn how much analyte reacted.
amperometry : voltammetry that observed current that is
monitored at a fixed potential

TERMS
Polarization is the deviation of
the electrode potential from
the value predicted by the
Nernst equation on the
passage of current that is given
by an overvoltage
(overpotential) which is
potential greater than the
theoretical value is required to
give a current of the expected
magnitude

TERMS
A depolarizer is a species that is easily reduced (or oxidized) and
therefore alters the polarization of the electrode. It helps maintain
the potential of the working electrode at a relatively small constant
value and prevents reactions that would occur under more reducing
or oxidizing conditions.
An electroactive species is one that can be oxidized or reduced at an
electrode.

TERMS
A working electrode is the electrode at which the analytical reaction
occurs (oxidation or reduction occurs). The working electrode is
equivalent to the indicator electrode of two-electrode cells. Metal
electrodes are polarizable electrode because the potentials are easily
changed when small current is flowing.
A reference electrode is an electrode that provides fixed reference
potential with negligible current flow. A reference electrode (such as
calomel or Ag|AgCl) is nonpolarizable electrode, because its potential
does not vary much unless a significant current is flowing.

VOLTAMMETRY
Auxiliary electrode that is the
current-carrying partner of the
working electrode.
Current flows between the
working and auxiliary
electrodes.
Voltage is measured between
the working and reference
electrodes.

WORKING ELECTRODES

VOLTAMOGRAM

2C0
C0

Current (mA)

0.5C0

Half-wave potential
Applied potential (V)

Oxygen (pO2) electrode

-0.65V

Reference electrode
(anode)

Platinum wire
(cathode)
Gas-permeable
membrane

Flow cell
O2

Reaction at the platinum electrode

+

O2 + 2H + 2e

Pt
-0.6 V

H2O2

The amount of current (e-) is proportional to the

concentration of O2

The glucose electrode

Glucose + O2

Glucose
oxidase

H2O2 + Gluconic acid

2e-

O2 +

2H-

O2 electrode

(+0.6 V)

The glucose electrode

POLAROGRAPHY
Polarography is voltammetry conducted
with a dropping-mercury electrode
dropping-mercury working electrode,
a Pt auxiliary electrode,
calomel reference electrode.

linear voltage ramp

staircase voltage ramp

COULOMETRIC ANALYSIS
electrons participating in a chemical reaction are counted to learn
how much analyte reacted.

We measure the electric current and the time required to

generate enough I2 to reach the equivalence point

COULOMETRIC ANALYSIS
Find the moles of H2S in an unknown if the end point in following
reaction (b) came after a current of 0.0582 A flowed for 184 s in
reaction (a)
(a)
(b)
The quantity of charge

(0.0582 C/s) x (184 s) = 10.71 C

Because 2 electrons in (a) correspond to 1 mol of H2S in

(b) there must have been 5.55 x 10-5 mol H2S in the
unknown

AMPEROMETRI TITRATION
The current at some fixed potential in the limiting current region is
measured as a function of the reagent volume

if no easily reduced or oxidized species is present in the solution electrode is polarized

easily reduced or oxidized species is present in the solution depolarized