potensiometri

Potensiometri
• Berdasarkan pengukuran potensial
sel elektrokimia tanpa adanya arus
(metode statik)

 Equipment :
 Elektrode referensi (standar)
 Elektrode indikator (kerja)
 Alat pengukur potensial
 Jembatan garam
Persamaan Nernst
RT
E =E 
0
nF ln Q
 Elektrode referensi

yg ideal :

 reversibel, mengikuti persamaan Nernst

 potensial konstan (tdk bergantung pd
komposisi larutan analit)
 stabil terhadap waktu dan suhu
 reprodusibel
 mudah dipreparasi
 convenient for use
 Elektrode referensi

contoh :
 Elektrode standar hidrogen
 Elektrode standar Ag/AgCl
 Elektrode standar kalomel

 Elektrode standar hidrogen (SHE)

It’s a primary reference electrode
Its potential is considered to be
zero (Eo = 0)
Electrode reaction:
half cell: Pt, H2 / H+ (1N)
Standard hydrogen electrode (SHE)
 Standard hydrogen electrode (SHE)

Advantages Disadvantages

 International standard  Pt black easily poisoned by

E0  0 V organics, sulfide, cyanide, etc.
 Potensial reprodusibel  It needs periodical replating of Pt
( + 1 mV) sheet with Pt black
 Hydrogen explosive
 It is difficult to be used and to
keep H2 gas at one atmosphere
during all determinations
Elektrode kalomel (SCE)
Hg | Hg2Cl2 (jenuh), KCl (x M) ||
Hg2Cl2 (s) + 2 e 2 Hg (l) + 2 Cl 

• mudah dipreparasi
Kelebihan • most polarographic
data ref’d to SCE

Kekurangan • koefisien temperatur tinggi

(potensial bergantung pd T
dE/dT = -0.67 mV/K)
• Hg toxic
Elektrode kalomel (SCE)
 Elektrode
Ag/AgCl

Ag | AgCl (jenuh), KCl (x M) ||

AgCl(s) + e Ag(s) + Cl 
 Kelebihan
Kekurangan
 temperature dependent
• chemical processing dE/dT = -0.73 mV/K
industry has
 It is more difficult to
standardized on this
prepare than SCE
electrode
• convenient  AgCI in the electrode has
• rugged/durable large solubility in
• better thermal stability saturated KCl
• one advantage over  dpt bereaksi dg lbh
SCE : can be used at banyak komponen
temperatures > 60oC contoh (misal, protein) 
• less toxicity menyumbat perbatasan
elektrode-larutan
Elektrode indikator / elektrode kerja
(working electrode)

Dapat merespon dengan cepat dan

reprodusibel dengan adanya
perubahan aktivitas /konsentrasi
analit

Indicator electrodes are classified

according to the process that
produces the electrode potential
• Elektrode indikator logam
develop a potential dependent on
the position of the equilibrium of
the redox half-reaction at the
surface of the electrode

• Elektrode indikator membran

develop a potential determined by the
difference in the concentration of
particular ions across a special thin layer
known as a membrane

 selektif ion
 selektif molekul
Elektrode indikator logam

• Tipe pertama
• Tipe kedua
• Tipe ketiga
• Indikator redoks
logam
 Tipe pertama
Kesetimbangan langsung dg kation dr
elektrode (misal elektrode Cu utk
penetapan Cu2+)

Cu2+ + 2 e Cu(s)

0,0592 1
Eind = E0Cu2+/Cu - log
2 a 2+
Cu

Eind = E 0  0,0592 p Cu
Cu
2
 Tipe pertama

Jarang digunakan

 Kurang selektif
yg digunakan  Hanya pd kondisi tertentu
(netral/basa)
Ag/Ag+  Kebanyakan logam mudah
Hg/Hg22+ teroksidasi
Cu/Cu2+
Zn/Zn2+
Cd/Cd2+ tdk digunakan
Tl/Tl+
Bi/Bi3+ Fe, Cr, Co, Ni
Pb/Pb2+ tdk reprodusibel
 Tipe kedua
• Elektrode merespons aktivitas anion yg dpt
membentuk endapan/ion kompleks yg stabil

misal : Ag utk menetapkan Cl

AgCl(s) + e Ag(s) + Cl E 0 = 0,222 V
Eind = 0,222 + 0,0592 pCl

misal : Hg utk menetapkan anion EDTA, Y4

HgY2 + 2e Hg(l) + Y4 E 0 = 0,21 V

0,0592 a Y4
Eind = 0,21 log a
2 HgY2 Eind = K + 0,0592
2
pY
konstan, karena kompleks HgY2 stabil
 Tipe ketiga
• Elektrode logam dpt merespon thd kation yg
berbeda
misal : elektrode Hg utk penetapan pCa
HgY2 + 2e Hg(l) + Y4
0,0592
Eind = K  log a Y4
2
CaY2 Ca2+ + Y4
0,0592
Eind = K’  pCa
2
 Indikator redoks logam

Misal : elektrode Pt sbg elektrode indikator

utk reaksi redoks Ce(III) mjd Ce(IV)

a Ce3+
Eind = E 0  0,0592 log a 4+
Ce

elektrode transfer e– sering tdk

inert spt Pt reversibel
 Elektrode indikator
membran

Kristalin & nonkristalin

Tunggal (misal : LaF3 utk F )

kristalin Polikristalin / campuran
misal : Ag2S utk S2- & Ag+

Gelas (misal : gelas silikat utk Na+ & H+)

Liquid (misal : liquid penukar ion utk
non Ca2+ & K+)
kristalin Liquid diimobilisasi dlm polimer rigid
misal : matriks polivinil klorida utk
Ca2+ & NO3
Elektrode membran kristalin
Senyawa ionik
Campuran senyawa ionik

kristal ionik
umumnya : isolator / konduktivitas <<

Yg konduktif, hanya yg punya ion mobile dlm

fasa padat

Contoh :
F dlm fluorida tanah jarang tertentu
Ag+ dlm halida/sulfida
Cu+ dlm sulfida
 Ion-selective electrodes (ISE)

Because of their selectivity for

analytes in complex matricies,
ion-selective electrodes are
important sensors for clinical
samples.

The most common analytes

are electrolytes, such as Na+,
K+, Ca2+, H+, and Cl–
Basic structure of a fluoride ion
selective electrode
Liquid Membrane Electrodes

Fill membrane with a

compound that selectively
binds with the analyte
Sifat membran selektif ion
• kelarutan rendah
Membran terbuat dr :
- molekul besar / agregat molekul,
misal : gelas silika / resin polimer
- senyawa anorganik sukar larut (misal : AgCl)

 konduktif
 selektif thd analit
pertukaran ion

mengikat analit kristalisasi

secara selektif
kompleksasi
Elektrode membran selektif
molekul
 enzim (biosensor) : penetapan glukosa, urea, dll
 non enzim : penetapan gas CO2, NH3, dll
(gas sensing probe)

Membran permeabel gas

 mikropori : polimer hidrofobik (PTFE, PP)
 homogen : polimer padat (karet silikon)
an enzyme-based
potentiometric
biosensor for urea