CHAPTHER II

LITERATURE REVIEW
II.1
II.1.1

Basic Theory
Deffinition of Potentiometry
Nernst equation gives the relative potential relationship between an

electrode and the corresponding concentration of ionic species in solution.

With a reversible electrode potential measurements, the calculation of the
activity or concentration of a component can be done (Khopkar, 1990).

Picture II.1 Scheme Potentiometric

Potensiometri is a direct application of the Nernst equation by
measuring the potential of two electrodes are not polarized at zero flow
conditions. Thus, in conditions that have current zero (Khopkar, 1990).
Conditions of Ag+ on the vessel left to be determined . Vessel that
connects the middle of KCl solution contained in the saturated calomel
electrode with a vessel containing a solution of silver through the salt
bridge containing agar and NH4NO3. If a potential measuring device is
connected to two electrodes , Ag into the positive electrode , while the
saturated calomel electrode , SCE is the negative electrode. By using the
Nernst equation (Khopkar, 1990):

I-1

Ag

E Ag=E Ag+

2,303 (

Literature Review
RT
ln
nF

RT
F ) tribal is worth 0,0591 at 25C, which should be remembered

in the calculation (Khopkar, 1990).

If the same two electrodes placed on the cylinder containing the
same solution , ( but different concentration ) and connected by a salt
bridge , the potential between two electrodes in accordance with the ratio
of the concentration.This is known as the cell concentration (Khopkar, 1990).
II.1.2 pH Measurement

Picture II.2 pH meters

For the determination of pH, made cell with electrodes that one
equilibrium with H+ ions and put into the solution under investigation.
More usually a calomel electrode. As a junction with a salt bridge or
directly enter a calomel electrode into the solution under investigation. Of
Ecell measured with a potentiometer can be obtained by E electrodes are
reversible with H+ ions, it can be determined from the pH (Sukardjo, 2013).
By using the pH=-log H+ relation, the measurement of H+ can be
simplified. For the example pH of 0,05 M based on operational pH is
(Khopkar, 1990):

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pH=4,000+

1 t15
2 100

jika = 0 sampai 55C

For pH measurement, required an electrode having a reversible

response to the concentration of hydrogen ions H+. For example, a
hydrogen electrode (Khopkar, 1990):
+
H

standar

+
H

tidak diketahui

Esel =0,0591 log

and if the concentration of H+ standart derived from NHE (Normal Hidrogen

Elekroda) whose concentration is 1 N, then (Khopkar, 1990) :

+
H
Esel =0,0591 log
pH=

E sel
0,059

1. Quinone and hydroquinone

Equimolar mixture solution of quinone and hydroquinone cause an
equilibrium that involves both electrons and hydrogen ions (Khopkar,
1990):

Picture II.3 Quinone and Hydroquinone

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Kuinhidron electrodes can not be used for solutions with pH>9,0,

because hydroquinone can be neutralized by a base. Likewise,
should be avoided from the reductant and oxidant strong (Khopkar,
1990).

2. Antimony Electrode
Another electrode which can be used to determine the pH is
antimonya electrode . This electrode when immersed in an aqueous
solution can be disguised by oxidation and provide a response to the
H+ (Khopkar, 1990).
Eg (Potential electrode) formed of unequal voltage on the inner
surface and the outer surface of the membrane. If E sel from
antimony= 0,145 V and use buffer pH= 7, then there is no voltage
can not be read as a result of potential electrode can not be used
(Khopkar, 1990).

ESel= ESel= -0,059 pH

Esel=0,145= -0,059 pH
3. The Glass Electrode
Glass electrode is an electrode that is most sensitive to H + ions and
two electrons are separated by a thin membrane , then (Khopkar,
1990):

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+
H

+
H

RT
E g=0,0591(
pH 2ln
pH
E g=
1)
nF

Picture II.4 Glass Electrode

Glass electrode is an electrode that is most often used because it shows a
fairly accurate pH measurements but with the range pH 2-12 glasses even
then depending on the materials used . In general, interference occurs
above pH 12 Na+ ions while under 2 formed gel thus reducing movement
or circulation between ions (Khopkar, 1990).
II.1.3

Potentiometric Titration
Emf measurements can be used to determine the endpoint. In the

acid-base titration, the pH will rise slowly to the addition of base. The very
sharp rise in pH near the equivalent point, after it is running slow again.
The increase in pH can be followed by a potentiometer, by inserting
electrodes equilibrium with H + ions and combine with kolomel electrodes.
Since the second electrode was fixed, then the increase in accordance with
the increase emf E and the first electrode is directly proportional to the pH
of the solution (Sukardjo, 2013).
II.1.3.1 Terms of potentiometric titration process

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Titration

process

can

again

be

followed

by

potential

measurements still have the following requirements (Khopkar, 1990). :

1. The reaction must involve a change or reduction of some ions in
accordance with the type of electrode.
2. Potential measurements began shortly after the addition of a
small amount of titrant in a row or continuous
3. Precision can be increased by comparing the process with a
concentration cell
II.1.3.2 Kind of Titration
Kind of titration which can be determined by potentiometric titration
(Khopkar, 1990) :

a. Titration Neutralization
Acid-base titration can be followed by the indicator electrode glass
electrode. Ionization constants must be less than 10-8 (Khopkar,
1990).

Picture II.5 Titration Curve

b. Titration complex formation and deposition
c. Deposit formation or complex formation of hydrated ions from a
solution freed in general . Electrodes used is the electrode Ag , Hg
sedangkana pentitrannya is EDTA used for various metal ions
(Khopkar, 1990).

Image II.6 Titration complex formation and deposition

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d. Redox Titration
Redox titration is usually used as the electrode is a platinum
electrode can be used in redox titration with oxidizing agents strong oxidizing agents such as KMnO4, K2Cr7O7 , Co(NO3)3 to form a
metal oxide layer that must be freed by the reduction reaction (to
liberate metals from okidasinya) is cathodic in solution aqueous
(Khopkar, 1990).

MnO

Mn + O2

2Cr2O3

4Cr + 3O2

2 Co2O3

4Co + 302

Picture II.7 Redox Titration

e. Titration in non-aqueous solvent
For example, 2,4 dinitrophenol hydrazine acting as an acid when
dissolved in pyridine. Penetration of tetrabutyl ammonium hydroxide
used in benzene (C6H6) or pure C2H5OH working electrode used is a
glass electrode, while the electrode potential in comparison to the
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calomel electrode (E-sel) indirectly measured with a voltmeter
voltmeter is interesting because the work flow of the cell to be
measured potentiometer equipment (Khopkar, 1990).

Picture II.8 Potentiometer Nernst Stone Bridge

In this potentiometer W so that there is a potential regulator layout
XW and YW will show the proportion comparable to the distance between
both of them. To determine an unknown cell potential, cell tersebt will be
connected in series with gawanometri (G) which is placed between the
point and W is shifted so that it can be concluded within the XW = cell
potential unknown (Khopkar, 1990).
Galvanic cell potential depends on the activity of certain ionic
substances in solution so that the cell potential measurement cell is very
important in analytical chemistry. In many ways a cell can be arranged
that potential depends on the activity of a single kind of ionic substances
in solution. One of the cell electrodes must be such that potential depends
on the activity of the ion to be determined; This is called the indicator
electrode. The other electrode is a benchmark, such as calomel, whose
potential is known and fixed during measurement (Day &Underwood, 2002).
Excess potentiometric methods, including low cost. Voltmeter and
electrode is much cheaper than the instruments of the most modern
scientific. The models are suitable for direct potentiometric field far from
the laboratory are an inexpensive, compact, robust, and easy to use.
Potentiometric basically bersid = fat nondestructive to the sample in the
sense that the insertion of the electrode does not change the composition
of the test solution (except for a slight leakage of electrolyte from the
reference electrode). If the species indicator electrode responded by
participating in the equilibrium solution, the activity is measured when it is
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present, without disturbing the equilibrium itself, thus the direct
potentiometric often very useful to define the equilibrium constant. Stable
potentials are often obtained with fairly quickly, and the voltage is
recorded as continuous monitoring and unsupervised for samples such as
communal water, industrial process streams, waste water flowing to the
pH and other ions such as fluoride, nitrate , sulfide, and cyanide (Day
&Underwood, 2002).

But

one

of

the

limitations

in

the

accuracy

of

the

direct

potentiometric seen in nurses equation itself. Because analyte activity

appeared in the form of logs, a change of ten times in accordance with
changes in cell voltage of only about 59 mV in the best case, where n (the
number of electrons in the electrode) is 1. But it should be recalled that
this is not'm really be a problem. Accuracy of measurement voltage is
usually not so ignored in direct potentiometric (Day &Underwood, 2002).
II.1.4 Types of Electrodes
According to Sukardjo (2013) from Kimia Fisika book, electrodes are
divided into:
a. Metal-Ion Electrode Metal
This electrode consists of a metal equilibrium with the metal ions
such as Zn, Cu, Cd, Na, and so on.
b. Amalgam Electrodes
Similar to the metal-metal ion electrode, but used amalgam, more
active and lower metal activity because diluted Hg.
c. Non-metal-non-gas
This electrode can be prepared by placing the substance concerned
in the tube, then on it was given a solution of the corresponding
ions. Relationship with water can be carried out with an inert metal
such as Pt.
d. Gas
Gas electrode consists of condensed gas bubbled into the solution
containing the ion equilibrium with it, as relations with the outside
usually used Pt Pt coated black.
e. Metal-insoluble salts
In this regard include:
- Electrode kolomel
- Silver-silver chloride electrodes
- Electrode lead-lead sulfate
- Electrode silver-silver bromide

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These electrodes equilibrium with the residual acid ions of
the salt concerned.
f. Metal-oxide insoluble
These electrodes equilibrium denngan OH- ions in solution. Of this is
a matter of electrode Sb / Sb2O3 (s), OH.
g. Oxidation-oxidation
This electrode consists of Pt metal included in the solution formed
oxidation and reduction.
II.2 Aplikasi Industri
Potentiometric Method Application Study On Determination of
Total Organic Carbon Content of Soil
Abdul Haris Watoni and Buchari
Department of Chemistry, State University of Haluoleo Department of
Chemistry, Faculty of ITB
Elemental carbon in the soil are within 4 form, which form carbonate
minerals, solid elements such as charcoal, graphite and coal, humus form
as the remains of plants and animals and microorganisms that have
undergone a change, yet are relatively resistant to weathering and form
the final form the remains of plants and animals that have undergone
decomposition in the soil. In connection with the beings of the element
carbon in the soil, then the determination of the carbon content of the soil
is done based on the total organic carbon content. Some researchers have
carried out measurements of the total organic carbon content of the soil
with conventional methods, is regular titrimetric method. Titrimetric
method has a fundamental weakness especially fowl determination of the
end point of the titration. This weakness is often the case in an analysis
workmanship resulting bias measurement results obtained, in addition to
the weaknesses due to errors occurring at different stages of the process.
Based on these reasons, it is necessary to have an alternative method that
can be applied in the determination of total organic carbon content of the
soil. In this study has tried determination of total organic carbon content of
the soil by the potentiometric method using CO 2 selective electrode. As a
comparison has been done also the determination of total organic carbon
content of soil with regular titrimetric method.

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A

calibration

curve

as

comparison

curve

for

the

determination of total soil organic carbon is made of redox reaction

between a mixture of oxalic acid solution of 0.1 M and 0.1 M H 2SO4 with
KMnO4 0.1 M, so that the CO 2 is obtained with a concentration of 5 x 10 -4
M, 5 x 10-3 M, 10-2 M, 5 x 10-2 M and 0.1 M while measuring the potential
response along with doing stirring. Next create a graph of potential (mV)
against -log [CO2] as a calibration curve. Measurement of CO 2 potential
response oxidation results in total soil organic C with KMnO 4 solution in
acidic conditions conducted by three (3) parameters, namely on the
weight and volume of soil samples fixed H 2SO4 (parameter 1), the sample
weight variable and fixed volume H2SO4 (parameter 2 ), and the weight of
the sample fixed but varies the volume of H 2SO4 (parameter 3). For the
determination of the potentiometric method, 2 grams of dried soil sample
is inserted into a glass beaker containing 25 ml. H 2SO4 0.1 M, then titrated
with 0.1 M KMnO4 in excess while stirring and measured its potential, to
obtain the greatest potential CO2 when measured by CO2 selective
electrode.

This

potential

price

subsequently

incorporated

into

the

regression equation of the calibration curve that has been made.

The results of measurements of the optimum conditions of soil
samples with parameters 1, 2 and 3 show that for the degradation of soil
total organic carbon to CO2 is absolutely necessary KMnO 4, while the
greater number of soil samples were degraded the more KMnO 4 necessary,
so that the greater the concentration of CO2 produced . The amount of
H2SO4 most good for the ongoing degradation of 2 grams of soil samples
with KMnO4 was 30 mL. In this condition, the potential value of its CO 2
reaches the largest value which means that the redox reaction takes place
most effectively. Retrieved also the concentration of CO 2 and at the same
time the total soil organic carbon concentration-order A, B, C and D with
successive potentiometric method was 2.86 x 10-3 M, 3.72 x 10-3 M, 3.43 x
10-3 M and 6.68 x 10-4 M or 0.045%, 0.06%, 0.056% and 0.01%, while the
measurement results with titrimetric method is 0.097%, 0.147%, 0.120%
and 0.071%. The difference in these results indicate that the total soil
organic carbon determination by potentiometric method is lower than the
usual titrimetric method. It was alleged that K MnO 4 added not only react
with organic compounds but also react with inorganic reducing agent
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present in the soil, among other compounds of iron (II). From this
vantage point method for determining total organic carbon in the soil is
more accurate than the titrimetric method.
CO2- selective electrode can be used to determine the CO2 in solution
concentration of analyte in th area 9.09 x 10-4 M to 3.8 x 10-1 M with Nernst
factor at a temperature of 250C for 53 mV / decade and a detection limit of
4.5 x 10-4 M, while the condition of potential measurements of CO2 are best
done at pH 4.8. The presence of ions CH3COO- and H2PO4- with
concentrations of 10-2 M or more in the analyte solution can interfere with
the measurement of CO2 potential response. Potentiometric method can
be used as an alternative method is more accurate than the titrimetric
method for the determination of total organic carbon content of the soil.

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