PART 22

BULK ELECTROLYSIS:
ELECTROGRAVIMETRY and
COULOMETRY

1
• Electrolysis technique is widely used in practical life and industry to obtain
aesthetic and durable metal coatings.

• Britanium: Sn+Cu+Sb, Over: Cu Ni Ag Au (Oscar)

• The determination of the concentration of the analyte by determining the

amount of metal deposited on the surface of an electrode is called
electrogravimetry.

• The determination of the amount of metal collected in the electrode by the

amount of electric charge passing through the circuit is also called
coulometry.

2
A. THE EFFECT OF CURRENT ON CELL POTENTIAL

• When a current flows through the electrochemical cells, the measured potential
difference between the two electrodes is not expressed by the Nernst equation.

• When current flows in both electrolytic and galvanic cells, two phenomena called IR
drop and polarization occur.

• Therefore, a potential greater than the thermodynamic potential must be applied to

operate an electrolytic cell.

• In a galvanic cell, a smaller potential (voltage) appears than would theoretically be

expected.

• Current is the rate of charge flow in a circuit or solution. One ampere of current is a
charge flow rate of one coulomb per second (1 A = 1 C/s).
• Voltage, the electrical potential difference, is the potential energy that results from
the separation of charges. One volt of electrical potential results when one joule of
potential energy is required to separate one coulomb of charge (1 V = 1 J/C).
3
• For example, let's examine the cell used for the electrogravimetric or
coulometric determination of Cd(II) in hydrochloric acid solution.

Ag I AgCl(s), Cl-(0.2 M) , Cd2+(0.005M) I Cd

• The electrode on the right is the cathode where Cd2+ ions are reduced,
and it is a copper electrode (working electrode) covered with a cadmium
layer.

• The potential of the silver/silver chloride electrode on the left remains

constant throughout the run and therefore is called the reference
electrode.

Cd2+ + 2Ag(s) + 2Cl- Cd(s) + 2AgCl(s) Ecell = - 0.734 V

• Since the Ecell is (-), the reaction is not spontaneous and a more negative
potential than –0.734 V is required for the reduction of Cd2+ ions.
4
 Electron
and
electric
current?

Current
is zero

!!
In fact, the
right should
be the anode
and the left
should be the
cathode.

An electrolytic cell for Cd2+ determination

5
A.1. Ohmic Potential: IR Drop

• Electrochemical cells resist charge flow like metals.

• In a cell; The product of resistance R (ohm-Ω) and current I (ampere-A) is

called the cell's ohmic potential or IR drop (Ohm's law).

• In order to generate a current of I amperes in this cell, we must apply a

potential that is IR volts more negative than the thermodynamic cell
potential .

Eapplied = Ecell – IR (Ecell = Eright - Eleft)

• In a cell, R or I values are kept low to minimize IR drop in a cell (R; high
ionic strength and I; three-electrode cell).

6
Example : A cell used for the determination of cadmium ions by
electrogravimetry and coulometry in the presence of chloride ions is as
follows.

Ag I AgCl(s), Cl-(0.2 M), Cd2+(0.005 M) I Cd

(a) Calculate the external potential required so that no current flows

through the cell when the two electrodes are connected (zero current!).

(b) Find the external potential (Eapplied) that must be applied for a current of
2.0 mA to occur. The cell internal resistance is 15 Ω.

Answer : Standard electrode potentials are found in the relevant tables.

Cd2+ + 2e- Cd(s) E0 = - 0.403 V

AgCl(k) + e- Ag(s) + Cl- E0 = 0.222 V

7
(a) The potential of the cadmium electrode :

The potential of the silver electrode :

Eapplied = Ecell = Eright - Eleft (no current flows!!)

= - 0.471 – 0.263 = - 0.734 V

Since the current will be 0.00 mA, IR = 0 and a voltage of –0.734 V must
be applied to the cell to prevent current flow.

8
In this case, which is called zero current, the voltage read from the
voltmeter is equal to the ECell value.

(b) Since 2.0 mA = 2.0x10-3 A,

Eapplied = Ecell – IR

Eapplied = - 0.734 – 2.0x10-3 A x 15.0 Ω

Eapplied = - 0.734 – 0.030 = - 0.764 V

Accordingly, a potential of –0.764 V must be applied to the cell in order for

a current of 2.0 mA to flow through the circuit.

9
A.2. Polarization Effects

• If the current (I) is drawn in the Eapplied = Ecell – IR equation given above,
the following equation is obtained.

(y = - mx + b)

It can be seen from this equation that when the current against the
externally applied potential is plotted in an electrolytic cell, a straight line
will be obtained.

• Also, it is understood from the equation that the slope of this line is -1/R
and its initial ordinate will be Ecell/R.

• When this graph is examined; when the applied voltage rises above a
certain value, it will be seen that the current deviates from linearity.

10
 overvoltage

Experimental current/voltage curve for operation of the cell. (Dashed line is the theoretical curve
assuming no polarization. Overvoltage P is the potential difference between the theoretical curve
and the experimental.) 11
• When current flows through the cell, the deviation of the electrode potential
from the value calculated by the Nernst equation is called polarization.

• Such a cell is called polarized, and the degree of polarization is given by

overvoltage or overpotential (denoted by Π).

Eapplied = Ecell – IR – Π

• Polarization is an electrode phenomenon that can affect any or both

electrodes in a cell and depends on the following factors.

(1) electrode size and composition

(2) composition of the electrolyte solution

(3) temperature and stirring rate

(4) current intensity

(5) physical state of the species involved in the cell reaction

12
a) Concentration Polarization

• Electron transfer between the electroactive species and the electrode

can take place only from the interfacial region located immediately
adjacent to the surface of the electrode.

• This film is several nanometers thick and contains a limited number of

electroactive ions or molecules.

• Concentration polarization occurs when reactant species do not arrive

at the surface of the electrode or product species do not leave the surface
of the electrode fast enough to maintain the desired current.

• Substances are transported to or away from the electrode surface by three

mechanisms: (1) diffusion, (2) migration, and (3) convection.

13
[Cd2+]0
[Cd2+]solution

I=0A

current

Graphical representation of the concentration

change in the Cd electrode 14
• Diffusion is the movement of a species under the influence of a
concentration gradient. It is the process that causes ions or molecules to
move from a more concentrated part of a solution to a more dilute (1).

• This event continues until the concentration difference disappears.

• As the current increases, the concentration difference increases and this

continues until the concentration at the surface decreases to zero.

• This maximum possible value of current is called limiting current.

• The equilibrium concentration ([Cd2+]0) on the cathode surface at any

instant is calculated from the electrode potential and the Nernst equation.

Cd2+ + 2e- Cd(s)

15
 The electrode is fully polarized

Euygulanan Ehücre
I= - +
R R

Larger (-) values

Current-potential curve for electrolysis showing the linear or ohmic region, the onset of
polarization, and the limiting current plateau. In the limiting current region, the electrode is said to
be completely polarized since its potential can be changed widely without affecting the current.
16
• The movement of ions under the
influence of an electric field is called
migration (2).

• This event, which is the main cause of

mass flow in the solution inside the cell,
is seen in the figure on the right.

• As a result of migration, anions are

attracted towards the positive electrode
and cations towards the negative
electrode.

• When migration of the analyte is not

Migration
desired, an inert supporting electrolyte is
added to the medium.
17
• The mechanical transport of ions or molecules in a solution by mixing,
shaking or temperature change is called convection (3).

• Forced convection, created by stirring or shaking, reduces the diffusion

layer thickness on the electrode surface.

• The temperature and density difference also contributes to the transport of

particles (natural convection), reducing the concentration polarization.

• Concentration polarization requires the application of a potential greater

than the theoretical value (!) to obtain a desired current in the cell.

• This effect of concentration polarization is undesirable in some

applications, while it is particularly desirable in some applications.

18
b) Kinetic Polarization

• In a kinetically polarized cell, the magnitude of the current depends on

the electron transfer rate rather than the mass transfer rate.

• It is necessary to apply additional potential or overvoltage to suppress the

kinetic polarization, that is, to overcome the energy barrier to the half-
reaction.

• The kinetic polarization becomes more in the processes on the electrodes

on which gaseous products are formed.

• The kinetic effects are generally reduced by increasing the temperature

or decreasing the current density.

• The overvoltage of H2 on Cu, Zn, Pb, Hg metals is important.

19
 The lead/acid storage battery
discharging
Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O

20
Example: Calculate the initial potential required for a current of 0.078 A to
flow through the cell below with a resistance of 5.0 Ω.

Co I Co2+(6.4x10-3 M) II Zn2+(3.75x10-3 M) I Zn

Answer: Standard electrode potentials are found in the relevant tables.

Co2+ + 2e- Co(s) E0 = - 0.277 V

Zn2+ + 2e- Zn(s) E0 = - 0.763 V

0,0592 1
Esağ = - 0,763 - log
2 3,75 .10-3
0,0592
Esağ = - 0,763 + ( log 3,75 + log 10 -3 )
2
= - 0,763 - 0,072 = - 0,835 V

21
 0,0592 1
Esol = - 0,277 - log
2 6,4 .10-3
0,0592
Esol = - 0,277 + ( 0,806 - 3)
2
= - 0,277 - 0,065 = - 0,342 V

Eapplied = Eright – Eleft – IR

Eapplied = - 0.835 – (- 0.342) – (0.078) 5

Eapplied = - 0.883 V Theoritically:

Ecell = Eright – Eleft
Ecell = - 0.835 – (- 0.342)
Ecell = - 0.493 V

22
B. THE SELECTIVITY OF ELECTROLYTIC METHODS

• Electrolytic methods are reasonably selective for the separation and

determination of many ions.

• The theoretical conditions necessary to make a particular separation can

be easily derived from the standard electrode potentials of the
respective species.

Example: Can Cu2+ and Pb2+ ions be separated electrolytically in a solution

containing these ions at 0.1 M concentration? What should be the potential
range (SCE) to be applied to the cathode?

Answer: The following values are found for standard electrode potentials
from the relevant tables.

23
 Cu2+ + 2e- Cu(s) E0 = 0.337 V

Pb2+ + 2e- Pb(s) E0 = - 0.126 V

Cu with a large electrode potential begins to accumulate earlier. The

potential required to reduce the copper concentration by 10-4 times,

As soon as lead starts to accumulate, the cathode potential is found as

follows.

Quantitative separation occurs if the cathode potential against the

standard hydrogen electrode (SHE) is set between 0.189 V and -0.156 V.
Initial 0,0592 1 0,0592
potantial E = 0,337 - log = 0,337 - = 0,337 - 0,030 = 0,307 V
2 0,1 2
24
 From these values, the cathode potentials against the SCE are found as
follows.

Ecell = Ecathode – ESCE = 0.189 – 0.244 = - 0.055 V (Cu depositing!)

Ecell = Ecathode – ESCE = - 0.156 – 0.244 = - 0.400 V (Pb depositing)

The cathode potential against the SCE must be kept between -0.055 V
and - 0.400 V to accumulate copper without precipitation of lead.

• In this way, the theoretical value of the standard electrode potential can be
calculated for the determination of an ion without the interference of other
ions.

• In conclusion; The way to separate the different species is to

continuously measure the cathode potential against a known reference
electrode and adjust the Ecell to keep the cathode potential at the desired
level. 25
Example: Calculate the potential required to initiate the accumulation of
Tl2O3 on the anode surface from a solution buffered to [Tl+] = 4x10-3 M and
pH = 8.0 at 25oC. The Cu2+ concentration used as the cathode depolarizer
in the solution is 0.01 M.

Answer: The corresponding half-reaction is as follows.

Tl2O3(s) + 3H2O + 4e- 2Tl+ + 6OH- E0 = 0.020 V

During the process, the reverse of this reaction will occur and Tl2O3(s) will
precipitate and there will be oxidation, that is, the anode half-reaction (left
electrode).

Cu2+ + 2e- Cu(s) E0 = 0.337 V (cathode half-rxn.)

26
In this case, the cell potential is:

0,0592 1
Esağ = 0,337 - log
2 (0,01)

= 0,337 - 0,0592 = 0,2778 V

0,0592 ( 4.10 -3 )2( 10 -6 )6

E sol = 0,020 - log
4 1,0

0,0592
E sol = 0,020 - ( - 40,796)
4
= 0,020 + 0,604 = 0,624 V

Eapplied = Eright – Eleft= 0.278 – 0.624 = - 0.346 V

What is the electrode potential for the Tl+ ion to be finished

analytically?
27
Example: A solution at 25oC contains [Co2+] = 0.150 M and [Cd2+] = 0.075
M. Make the following calculations.

a) What is [Co2+] in solution at the moment when Cd(s) starts to

decompose?

b) What is the Ecathode required to reduce to [Co2+] = 1.0x10-5 M?

c) According to the information in a and b, can these ions be separated

quantitatively?

Answer: The corresponding half-reactions are as follows.

Cd2+ + 2e- Cd(s) E0 = - 0.403 V

Co2+ + 2e- Co(s) E0 = - 0.277 V

a) First, Co(s) starts to decompose. At the moment when Cd(s) begins to

decompose, the electrode (cathode) potential is:

28
 0,0592 1
Ekatot = - 0,403 - log
2 0,075

Ekatot = - 0.403 – 0.0296 log 13.33

= - 0.403 – 0.0333 = - 0.436 V

When Ecathode reaches this value, [Co2+] in the medium is found as follows.

0,0592 1
- 0,436 = - 0,277 - log
2 [Co2+ ]

- 0.159 = - 0.0296 (- log [Co2+])

log [Co2+] = - 5.37

[Co2+] = 10-5.37 [Co2+] = 4.27x10-6 M

29
b) The cathode potential required to reduce [Co2+] = 1.0x10-5 M.

0,0592 1
Ekatot = - 0,277 - log
2 1. 10 -5

Ecathode = - 0.277 – 0.0296 log 105

= - 0.277 – 0.148 = - 0.425 V

c) If the reduction of the initial concentration to 10-4 times for Co2+ is considered
sufficient for separation, it means a reduction to

0.15 x 10-4 = 1.5x10-5 M

However, when Cd(s) starts to separate, it decreases to [Co2+] = 4.27x10-6 M.

Accordingly, cations can be separated.

30
ELECTROGRAVIMETRY AND CULOMETRY

C. ELECTROGRAVIMETRIC METHODS

1. Electrogravimetry without Potential Control

2. Controlled-Potential Electrogravimetry

D. COULOMETRIC METHODS

1. Controlled-Potential Coulometry (Potentiostatic Coulometry)

2. Controlled-Current Coulometry(Coulometric Titration )

31
C. ELECTROGRAVIMETRIC METHODS

C.1. Electrogravimetry without Potential Control

• In these processes, the potential applied to the cell is kept at an almost

constant value during electrolysis.

• The system, which is used without controlling the cathode potential,

consists of a suitable cell and a 6-12 V direct current source.

• In this type of analytical electrolysis, the applied potential is first

adjusted with a potentiometer (R) so that a current of several 1/10 A
flows.

• Then, the potential is kept at its initial value until the deposition at the
electrode is complete (the current decreases along with the analyte in the
process!).
32
 Potential
switching
≈ 0.1-0.3 A
resistor
(potentiometer)
Apparatus for
electrodeposition of metals
without cathode-potential
control. Note that this is a
two-electrode cell.

33
• The precipitated metal should be firmly attached to the surface, dense and
smooth. If this happens, it can be washed, dried and weighed without loss.

• The main factors affecting the physical properties of the precipitates

are current density, temperature, mixing and complexing agents.

• In precipitation in metal complex solutions, many metals form

smoother and more tightly bound films.

• Reduction of hydrogen during electrolysis usually prevents the precipitate

from adhering to the electrode, which is not a favorable situation.

• This can be resolved by adding a depolarizer (a substance that is easily

reduced or oxidized) such as a nitrate ion.

NO3- + 3H+ + 2e- HNO2 + H2O E0 = 0.94 V

• At the end of the electrolysis, the reduction of the metal is completed with
the reduction of hydrogen (!) or nitrate ions (depolrz.).
34
35
C.2. Controlled-Potential Electrogravimetry

• Here, the assumption that the working electrode is the cathode and on
which the analyte is deposited as a metal will be considered.

• The method can also be easily applied to an anodic working electrode

where non-metallic precipitate products are formed. For example, Br-
determination.

• The controlled - potential device is made of two independent electrical

circuits and the working electrode is shared by both circuits.

• The electrolysis circuit consists of a dc source, a potentiometer that

permits the voltage applied between the working electrode and a counter
electrode to be continuously varied, and a ampermeter.

36
 The working
electrode is a
metallic lattice
cylindrical Potantiometer

Apparatus for controlled-potential,

electrolysis. The digital voltmeter
monitors the poten- tial between the
working and the refer- ence
electrode. The voltage applied
between the working and the counter
(control electrode is varied by adjusting
circuit) contact C on the potentiometer to
maintain the working electrode
(high resistance) (cathode in this example) at a
constant potential versus a reference
electrode. The current in the
reference-electrode is essentially
zero at all times.
37
• Control circuit; It consists of a reference electrode (usually SCE), a high-
resistance digital voltmeter and a working electrode.

• Since the electrical resistance of the control circuit is very large, the
electrolysis circuit supplies all the current required for electrolysis.

• The task of the control circuit is to constantly monitor the potential

between the working and reference electrode and adjust it to a certain
value.

• Practically; it uses devices called potentiostats that automatically keep

the potential of the working electrode at a constant value.

• During operation, the cell is mixed mechanically to minimize concentration

polarization.

38
• The controlled-potential method is an efficient way to determine metals
with a difference of several 0.1 V in standard electrode potentials.

• Example: Explain the systematic analysis of a solution containing the

metals Cu, Bi, Pb, Cd, Zn and Sn by the controlled-potential method.

• Answer: First, the first three ions are sequentially separated from the
neutral solution by adding tartrate ions to prevent the precipitation of
Sn(IV).

Cu : - 0.2 V, Bi : - 0.4 V, Pb : - 0.6 V (on Pt electrode)

By adding NH3 to the medium, Cd: -1.2 V and Zn: -1.5 V are also
separated sequentially.

By making the medium strongly acidic, the complex is decomposed and

Sn is precipitated on the clean Pt electrode at -0.65 V (Zn dissolves in
acid!). 39
40
D. COULOMETRIC METHODS

• Analysis methods performed by measuring the amount of electric

charge required to convert the analyte to quantitatively different oxidation
states are called coulometric methods.

• Unlike gravimetric methods, coulometric processes are generally faster

and the product does not need to be a weighable solid.

D.1. Determining the Electrical Charge

• The charge of an electron (or proton) is defined as 1.6022x10-19 coulombs

(C).

• The magnitude of a current of one coulomb per second is one ampere

(A).

41
• Therefore, 1 coulomb is the amount of charge (Q) carried in one second
by a constant current of one ampere.

Q=I.t (1 coulomb = 1 amper x 1 s = 1 A s)

• Faraday is the amount of charge equal to one mole or 6.022x1023

electrons and is equal to 96485 C. (96500 C can be taken!)

• Faraday's law gives the relationship between the number of moles (nA) of
the analyte and the charge (Q). If the species receives n moles of
electrons;

Q nF 1 mol
nA = Q nA
nF

42
• The amount of charge for a variable current I is found as:

(For ac, electric current is denoted by a lowercase i)

• If the current changes with time, the amount of charge at any time t is the
area under the curve.

43
Example: A constant current of 0.80 A is used to release oxygen at
the anode of an electrolytic cell and to deposit copper on the
cathode. How many grams of each product are formed in 15.2
minutes?

Answer: The two half-reactions are as follows.

Cu2+ + 2e- Cu(s)

2H2O 4e- + O2(g) + 4H+

Q = I . t = 0.80 A x15.2 min x 60 s/min = 729.6 A s = 729.6 C

44
 Cu and O2 masses are calculated as follows.

D.2. Characterizing Coulometric Methods

Two types of methods have been developed based on the measurement of

the amount of load.

a) Controlled-potential (potentiostatic) coulometry

b) Controlled-current coulometry (coulometric titrimetry)

45
a) Controlled-potential (potentiostatic) Coulometry

• In potentiostatic coulometry, the working electrode potential against a

reference electrode is kept constant throughout the electrolysis.

• Then, the amount of analyte is calculated over the amount of electrical

charge required to convert the analyte to the desired product.

• The amount of electrical charge is determined by recording and integrating

the current/time curves during the electrolysis.

• The device used in potentiostatic coulometry consists of an electrolysis

cell, a potentiostat and an instrument (current integrator) that determines
the amount of electricity consumed by the analyte.

46
 Electrolysis cells for potentiostatic coulometry.
(a) platinium gauze (b) mercury pool

Electrode connection

47
• Controlled-potential coulometry can also be used for the electrolytic
determination and synthesis of organic compounds.

• For example, trichloroacetic acid and picric acid are quantitatively reduced
at a mercury cathode whose potential is suitably controlled

48
Example: The Fe(III) in a 0.8202 g sample was determined by coulometric
reduction to Fe(II) at a platinum cathode. Calculate the percentage of
Fe2(SO4)3 (M = 399.88 g/mol) in the sample if 103.2775 C were required for
the reduction.

Answer: Since 1 mol of Fe2(SO4)3 consumes 2 mol of electrons

49
b) Controlled-current Coulometry (Coulometric Titrimetry)

• Coulometric titrations are similar to other titrimetric analysis methods in

which the ratio of association of a standard substance and analyte is
measured.

• In coulometric titrimetry, the reactive is electrons and the standard solution

is a constant current of a certain magnitude, which is provided by a
galvanostat.

• Galvanostat is sensitive to decreases in cell current and increases the cell

potential, keeping the current at its original value (constant).

• Until the end point is reached, electrons are transferred to the analyte or
to other species that will react immediately with the analyte.

50
• For example, the coulometric titration of Fe(II) at the platinum anode is as
follows.

Anodic rxn. : Fe2+ Fe3+ + e- (!) E0 = 0.771 V

• As the Fe2+ concentration decreases, the cell potential rises to maintain a

constant current (concentration polarization).

• Therefore, the anode potential may rise to the point where it separates the
water. This prevents the current from being used 100% for the main event.

2H2O 4e- + O2(g) + 4H+ (!) E0 = -1.229 V

• This can be avoided by initially adding Ce(III) to the medium.

Ce3+ Ce4+ + e-

Ce4+ + Fe2+ Ce3+ + Fe3+

51
• That is, Ce4+ formed at the anode disperses into the solution at the end of
mixing and oxidizes the equivalent amount of Fe2+.

• Electrolysis stops at the end point or as in other titrations, the end point is
determined with an indicator adding into the medium.

• At the end of the study, the amount of analyte is calculated over the
magnitude of the current used and the time elapsed.

• At the next slide,there is a conceptual schematic of the coulometric

titration setup, as well as a typical coulometric titration cell.

• This cell consists of a working electrode in which the reagent is

produced and a counter (auxiliary) electrode to complete the circuit.

52
 1. The circuit is closed, the system is working.
2. The circuit is open.

Galvanostat

Conceptual diagram of a coulometric titration apparatus. Commercial

coulometric titrators are totally electronic and usually computer controlled.
53
 Asid titration Halogen titration
2H2O + 4e- H2(g) + 4OH- Ag(s) + Br- AgBr(s) + e-

Ag(s) Ag+ + e- (precipitation)

Base titration
2H2O 4e- + O2(g) + 4H+ Ag can be used in the presence of Br- and
Cl- instead of Pt cathode.

anode or
cathode
Analyte
solution Reagent is
produced

It prevents the
substance formed in
the electrode from
mixing with the
environment.

A typical coulometric titration cell

54
 Comparing Coulometric and Conventional Titrations

• There are no problems during the preparation, adjustment and storage of

standard solutions (reagents such as Br2 , Cl2).

• Selecting a suitable current to titrate small amounts of analyte.

• Production of reagents for precipitation, complex-formation, neutralization,

oxidation/reduction titrations with a current source.

For Example:
2I- I2 + 2e-

55
Example: The phenol content in the wastewater of a facility is
analyzed coulometrically. For this, a 100 mL water sample is made
slightly acidic and excess KBr is added. For the following reaction,
a constant current of 0.0313 A is required for 7 minutes and 33
seconds to produce Br2. Find the result of this analysis as parts per
million of C6H5OH. Water density will be accepted as 1.0 g/mL.

C6H5OH + 3 Br2 Br3C6H2OH(s) + 3HBr

Answer: 1 mol C6H5OH 3 mol Br2 6 mol e–

t = 7 x 60 + 33 = 453 s

Q = I . t = 0.0313 A x 453 s = 14.1789 coulom (A s)

56
 14,1789
ne = = 1,469 .10 - 4 Faraday (mol e - )
96 485

1,469 ,10-4
nC6H5OH = = 2,449 .10-5 mol
6

mphenol = 2.449x10-5 x 94 = 2.3x10-3 gram

[Phenol] = (2.3 mg/100 mL) x 1000 mL = 23 ppm (mg/kg)

57
 HgNH3Y2- is reduced, HY3- is produced

HgNH3Y2- + NH4+ + 2e- Hg(l) + 2NH3 + HY3-

58
59
 Automatic Coulometric Titrations

• Some of these are used for various purposes, while others are used for
the identification of a single species.

• Chloridemeter: Silver ions are produced coulometrically in chloride

titrators. The increase in Ag+ ion creates a sudden increase in current.

• SO2 monitor: Anodically produced Br2 analyte oxidizes to sulfate ions.

(Br2 + SO2 + 2H2O 2Br- + SO4= + 4H+)

• CO2 monitor: The gas is absorbed in monaethanolamine and titrated with

coulometrically produced base.

• Water titrator: The Karl Fischer reagent to titrate the water is produced
electrolytically. (I2 + SO2 + 2H2O 2HI + H2SO4)

60
 • A commercially available
chloridemeter

• This coulometric titrator is

designed for the
determination of chloride in
clinical samples such as
serum, urine and sweat.

• It is used in the diagnosis of

cystic fibros.

• This device is also used in

food and environmental
laboratories.

Its basic principle is based on the production of Ag+ ions in the Ag

electrode.
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 QUESTIONS and PROBLEMS

22-1 22-2 22-3 22-6 22-11 22-14 22-16

22-17 22-19 22-25 22-27

THIS PRESENTATION HAS BEEN PREPARED FROM THE FOLLOWING

TEXTBOOK

SKOOG / WEST HOLLER/CROUCH

9th Edition

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1) What kind of change occurs in the potential values of electrolytic and galvanic cells
when current flows through an electrochemical cell? Explain what you know about it.

2) What does Ohmic Potential mean in an electrochemical cell? What kind of change in
cell potential does it cause? Explain by writing the relevant relation.

3) What does polarization mean in an electrochemical cell? Explain what you know
about it by writing the relevant relation. Give brief information about concentration and
kinetic polarization.

4) Transport of dissolved species to and from the electrode surface occurs by three
separate mechanisms. Briefly explain these.

5) Show schematically the application of an electrogravimetric method in which the

potential is not controlled, that is, the relevant cell. What parameters does the formation
of a good precipitate during processing depend? Please explain briefly.

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6) Draw the controlled-potential electrogravimetry (electrolysis) assembly
schematically and briefly explain the working principle of the method by specifying
the basic elements of the system.

7) Briefly explain what coulometry is. Indicate the types of coulometric methods in
items. Briefly explain the working principle of each.

8) Briefly explain controlled potential coulometry. Simply draw the cells used in this
method. Indicate the elements in the cell on the figure.

9) Write down what you know about coulometric titration. Draw the conceptual
diagram (or simply the cell used) of the apparatus used in the application.

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