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POTENSIOMETRI
Edi Nasra, S.Si., M.Si
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SEL VOLTA
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Potensial Sel
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Example 1: What are the anodic, cathodic and overall reactions responsible for the potensial in the elecrochemical cell shown here? Write the shorthand notation for the electrochemical cell
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Example 2: what is the potential of the electrochemical cell shown in example 1 (Eo
Fe3+/Fe2+ = +0.771 V ; Eo AgCl/Ag = +0.2223 V
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Example 3: what is the concentration of Fe3+ in an electrochemical cell similar to that shown in example 1 if concentration of HCl in the left-hand cell is 1.0 M, the concentration of FeCl2 in the right-hand cell is 0.0151 M and the measured potential is +0.546 V
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Potentiometric Cells84,2 mV
Indicator Electrodes Eind
Salt Bridge, Ej
Refrence Electrodes Eref
Esel = Eind – Eref + Elj
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Liquid Junction Potentials
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Elektroda yang mempunyai harga potensial tetap dan konstan dan tidak dipengaruhi konsentrasi analit dalam larutan
Elektroda Pembanding
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Elektroda Hidrogen Standar
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Elektroda Kalomel
Besarnya potensial sel:• jika digunakan KCl
jenuh + 0.2440 V• jika [KCl] 3.5 M maka E
= +0.2500 V• jika [KCl] 0.1 M maka E
= +0.3356 V
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Elektroda Ag/AgCl
Besarnya potensial:• jika digunakan KCl jenuh E =
0.199 V• jika digunakan KCl 3.5 M maka E
= 0.205 V
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Elektroda Indikator
Elektroda yang potensialnya bergantung pada konsentrasi zat yang sedang diselidiki
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Elektroda Kerja Logam Elektroda Jenis Pertama
Logam yang dicelupkan kedalam larutan ionnyaContoh: logam tembaga yang dicelupkan ke dalam larutan ion Cu2+
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Elektroda Jenis Pertama
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Elektroda Jenis KeduaElektroda logam yang dicelupkan ke dalam larutan yang dijenuhkan dengan garam sukar larut dari ion logam tersebut.
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Elektroda Jenis Kedua
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Example 4:
Calculate the formation constant Kf for Ag(CN)2
- if the cell:SCE || Ag(CN)2
- (7.50 x 10-3 M, CN- (0.0250 M)| Ag develops a potential of -0,625 V
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Elektroda RedoksElektroda logam inert dicelupkan ke dalam larutan yang mengandung ion yang dapat mengalami reaksi reduksi/oksidasi di permukaan elektroda tersebut. Elektroda ini tidak terlibat dalam reaksi tersebut.
Contoh: Fe3+, Fe2+Pt
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Elektroda Membran
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Selektifitas Membran
[A]E dan [I]E adalah konsentrasi analit dan pengganggu yang memberikan nilai potensial sel yang sama
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Penentuan Tetapan Selektifitas
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Elektroda Gelas
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Mekanisme Timbulnya PotensialH+(lar.) + Na+Gl-(mem.) Na+(lar.) + H+Gl-
(mem.)
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Mekanisme Timbulnya PotensialH+Gl-(mem.) H+(lar.) + Gl-(mem.)
Membran
Larutan
BatasMembran-
Larutan
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ESI Kalsium
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Aktivitas vs Konsentrasi
Jika tetap
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Ionic Strength AdjusterKekuatan Ion ()
.......}][][]{[5,0 222 CBA ZCZBZA
3,31
51,0log
2
xZ
Debeye-Huckel
=diameter efektif ion
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Analisis Kuantitatif Method of external standards
What is the concentration of Ca2+
in the water sample if its cell potential is found to be -0.084 V?
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Quantitative Analysis Method of Standard AdditionsContoh: The concentration of Ca2+ in a sample of sea water is determinedusing a Ca ion selective and a one point standard addition. A 10.00 mL sample is transferred to a 100 mL volumetric flask and diluted to volume. A 50.00 mL aliquot of sample is placed in a beaker with the Ca ion-selective electrode and a reference electrode, and the potential is measured as -0.05290 V. A 1.00 mL aliquot of a 5.00 x 10-2 M standard solution of Ca2+ is added, and a potential of -0.04417 V is measured. What is the concentration of Ca in the sample of sea water?
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Titrasi Potensiometri Elektroda kerja dan elektroda pembanding
dicelupkan ke dalam larutan analit. Potensial sel diamati selama penambahan
titran. Titik akhir ditentukan dari kurva titrasi
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Titrasi Potensiometri
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The titration curve