R.C. Rhees, Ph.

D
Vice President Research

CON Systems, Inc.

3770 Howard Hughes Parkway, Suite 340
M Las Vegas, NV 89109
Telephone: (702) 735-2324
Fax: (702) 735-9456
 GENERAL ELECTROCHEMISTRY

R. C. Rhees

PEPCON Systems, Inc. of Nevada has been using electrochemical processes in their plant since 1958 when the
first commercial lead dioxide anodes were patented and applied to our manufacture of oxychlorine compounds. The
application of electrochemical processes for treatment of waste gas and liquid discharges was a natural outgrowth of
this earlier work. PEPCON commenced development of electrolytic waste treatment systems in 1968. This work has
resulted in installations for various purposes throughout the world.

All chemical processes involve the loss, gain, or redistribution of electrons on an atom or group of atoms. Elec-
tricity is the movement of electrons along a conductor. It is no wonder then that chemical changes can be made to occur
by passing an electric current through a solution containing atoms or groups of atoms which will accept or give up
electrons. Processes which pass an electrical current through a solution to effect chemical changes are called
electrochemical processes.

The necessary components of a system to carry out electrochemical processes are:

1. A source of direct electrical current. This may be a battery but most usually is a rectifier which converts the
normal alternating current electricity to direct current.

2. An electrolytic cell. The cell has the following necessary parts:

a. Container
b. Electrodes
anode - positive electrode- electron deficient.
cathode - negative electrode - electron rich.
c. Electrolyte
Water plus an acid, base or salt. These are substances which ionize in water to give positive ions (Cations-
because they are attracted to the negative cathode) and negative ions (Anions -because they are attracted
to the positive anode).

3. Electrical connectors-copper cable or bus bar to connect the rectifier (or battery) to the electrodes (positive
terminal to the positive anode and the negative terminal to the negative cathode).

When the power is turned on the rectifier, electrons are removed from the anode and forced onto the cathode. This
develops an electrical potential between the two electrodes inasmuch as the excess electrons on the cathode would like
to find some way of getting off and the electron deficient anode would like to get the electrons. Such electron transfer
can be made to occur by chemical reactions at the electrodes. These reactions may involve

1. Dissolution of the anode.

2. Oxidation of an anion at the anode.
3. Reduction of a cation at the cathode.
a. by deposition of a metal ion.
b. by reduction of water to hydrogen.
c. by forcing an atom or molecule to take one or more electrons without either deposition or hydrogen
generation.
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 Useful electrochemical processes have been developed involving combinations of all of the above electron transfer
possibilities. Frequently several modes of electron transfer occur at the same time.

The objective of any electrochemical process is to control the conditions in the electrolytic cell so that the cathode
reaction and the anode reaction caused by the electron transfer produces only the desired products.

Basic to all electrochemical processes is the quantitative relationships which were first expressed by Michael

The number of electrons transferred from the cathode to the solution by electrochemical reaction is exactly
equal to the number of electrons transferred from the solution to the anode.
For the same electrolyte, the amount of electrolysis is proportional to the quantity of electricity which
passes.
The amounts of substances liberated at the electrodes, when the same quantity of electricity passes through
solutions of different electrolytes, are proportional to their chemical equivalents.

Thus in electrolysis 95,600 coulombs (ampere seconds) of electricity produce a chemical change of one gram-
equivalent of products at both the anode and cathode. The quantity 96,500 coulombs is referred to as one faraday.

Now if every electron transferred went to produce the desired product, one gram equivalent of product would be
produced for every faraday of electricity passed through the cell and the current efficiency in producing the desired
product would be 100%. In actual practice, however, other electrochemical reactions than the desired one may occur
or some of the current may pass through the cell in other ways than by electrolysis (electrical short). The result is that
less product is made than would be calculated theoretically using Faraday’s law. The current efficiency in production
electrolytic processes is then always less than 100% providing that the correct electrochemical equivalence is used
in the calculation.

The primary objective of all electrochemical R&D work is to develop an electrolytic cell and associated equipment
together with the conditions for operation which will give the highest current efficiency at the lowest practical voltage.

The power cost of the process is directly related to the number of kilowatt hours of power required per pound of
product produced. The kWh/lb. of product is related to current efficiency and voltage in the following way:
kWh/lb. product = 1216 x volts (single cell)
-----____--
% current efficiency x EE
Where EE is the electrochemical equivalent in grams of product per faraday.

The following other factors besides low power cost, however, have significant influence on final design of the

Cost of materials in electrolyte (water, salt, etc.).

Cost to fabricate system.
Life.
Reliability.
Ease of operation.
Maintenance.
Safety considerations.
Formation of undesirable by-products.

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 The application of these general principles will be illustrated by specific discussion of PEPCON on-site
hypochlorite generators and PEPCON odor control systems. However, electrochemical applications to waste
treatment is much broader than these specific applications. We have investigated electrolytic flotation, electrolytic
coagulation, and direct electrochemical destruction of hydrogen sulfide, cyanide, ammonia and phenol in industrial
waste streams. Units are operating for the oxidation of odorous compounds in supematant effluent from anaerobic
digestors.

Electrochemical processes are thus finding more and more applications in pollution control.

PEPCON HYPOCHLORITE SYSTEM

Electrolyte

Chloride is the essential ion in the electrolyte solution for the production of hypochlorite. This ion is added to the
water in brine systems as sodium chloride (ordinary salt). The brine system’s solid salt is added as required to a brine
tank and water is introduced at the rate the brine is to be used in the system. The water in passing through the solid
salt becomes essentially saturated with NaCl and approaches a concentration of 300 g NaCI/l. This concentrated salt
solution is then diluted by fresh water so that the concentration in the electrolyte to the cells is in the 20 to 30 g NaCl/
1 range. The exact target concentration chosen is dependent on the relative cost of power and salt and on the final
concentration of NaOCl desired in the product.

Seawater, when available, can be used as the source of chloride ion for making the electrolytic hypochlorite.
Normal seawater has a chloride concentration of 18,980 mg Cl-/l. This is equivalent to an NaCl concentration of 31
g NaCl/l and is very suitable for use as the cell electrolyte without further modification except for filtration to remove
solids. Frequently seawater sources are from estuaries or other locations where the seawater is diluted with fresh water.
Such sources are still usable providing (1) dilution with fresh water is not excessive, (2) only low concentration of
hypochlorite is required and (3) objectionable substances are not introduced with the dilution water.

There are extensive salt deposits in some areas and in some instances brine wells are available as a source of
electrolyte.

We like to see an analysis of the water and salt to be used in the electrolyte for the cells. Generally other salts than
NaCl in the water are not objectionable. In fact, they may reduce the operating voltage of the hypochlorite unit with
beneficial effect on power costs. However, we are concerned about two types of contaminants in the water or the salt.

1. Heavy metals - copper, cobalt, nickel and iron are decomposition catalysts for hypochlorite and should
not be present. Only rarely will these substances be found in either the water or the salt, thus heavy metals
are of minor concern.

2. Hardness ions - calcium and magnesium are commonly found in salt (NaCl) and water. These hardness
ions are of considerable concern because they can promote formation of calcium and magnesium carbonate
scale on the cathode of the cell. Such scale formation interferes with the electrolyte flow, the operating
efficiency and the life of the cell.
Calcium and magnesium can be removed from the water using conventional water softeners. The concentration
of calcium and magnesium in the salt is controlled by selection of salt source. Typical composition of salt from various
sources is given in the table below. However, there is considerable variation within the classifications included in the
table.

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 On the basis of analyses only, it will be noted that the order of preference would be (1) granulated, (2) crude solar,
(3) southern rock salt, and (4) northern rock salt. Cost of the salt varies greatly depending on grade of salt, distance
and mode of transportation between source and point of use. Selection of salt source, therefore, becomes a trade-off
between purity and cost.

Oxidation of chloride ion occurs at the anode

2Cl- - Cl, + 2e-

followed by rapid hydrolysis of the chlorine

Cl, + H2O - HOCI + HCI

Reduction of sodium ion occurs at the cathode

Na+ +e- _Na

followed by rapid reaction of the sodium with water

Na+H,O- 1/2 H2 + NaOH

The acid s(HCl an dHOCl) produced at the anode react with the bas (NaOHe ) produced at the cathode
HCI + NaOH -NaCI + H2O and
HOCI + NaOH - NaOCl + H2O

The net reaction on electrolysis in the cell then is

NaCl + H,OL NaOCl + H2

and the amount of hypochlorite produced is related to the amount of direct electrical current passed through the
cell.
Unfortunately other reactions occur which lower the amount of hypochlorite actually measurable in the product
below that theoretically produceable from the amount of D.C. current passed through the cell. Some electrolysis of
water occurs so that oxygen rather than chlorine is produced at the anode.
H2O _ l/2 02 + 2H+ + 2e-

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 The hypochlorite produced may be (1) oxidized further to higher oxychlorine compounds, (2) reduced at the
cathode back to chloride or (3) may be decomposed to NaCl + l/2 02.

Cell design and operating conditions are picked to give best production of NaOCl at the lowest overall cost. The
system and mode of operation vary depending on the source of the brine solution (seawater or commercial salt and
water) and the target concentration of NaOCl in the final product. The major factors influencing unit design and
operation will be discussed later.

It was previously mentioned that salt-water electrolyte high in hardness ions might form objectionable scale on
the cathode of the cell. The reactions for scale formation are as follows:

HCO3 + NaOH + CO,= + H2O + Na+

The carbonate ion reacts with the calcium present to form the very insoluble calcium carbonate

Ca++ + CO,= - CaCO3

The calcium carbonate forms an adherent scale on the cathode if the concentration of calcium and carbonate ions
in the electrolyte at the cathode exceed the solubility product of calcium carbonate (Ksp = 2.8 x 10 -9 ).

When, however, the bicarbonate ion is low in comparison to the calcium and particularly the magnesium ion, the
solids formed at the cathode are soft and non-adherent and control of flow characteristics through the cell will generally
prevent accumulation of an adherent scale on the cathode.

This situation occurs in normal seawater where the magnesium concentration is 1272 mg/l, the calcium
concentration is 400 mg/l and the bicarbonate concentration is 142 mg/l. If all the bicarbonates present were converted
to calcium carbonate, only 93 mg calcium per liter would be removed and none of the magnesium would be removed.
Now when this solution is exposed to the high pH at the cathode surface, the soft non-adherent hydroxides are the
principal solids precipitated.
Ca++ = 2NaOH +Ca (OH), + 2Na+
Mg++ = 2NaOH - M g ( O H ) , + 2Na+
The small amount of CaCO3 formed is carried away with the non-adherent hydroxides and scaling can be
controlled.

In cases where the adherent calcium carbonate scale forms it must be removed periodically by cutting the current
to the cells way back and recirculating nitric acid through the system. The calcium and magnesium carbonates are
converted to the soluble nitrates.

CaCO3 + 2HNO3 ____) Ca (NO,), + H2O + CO 2

Factors Influencing Unit Design

When a D.C. electric current is applied across an electrolytic cell through which salt solution is circulating, the
concentration of hypochlorite increases with electrolysis time. Initially the increase is close to that theoretically
expected. This is shown in Figure 1. The solid curve represents the observed results and the dashed line represents
the change in concentration with time if the faradic current efficiency were 100%. As the concentration of hypochlorite
increases, reactions involving conversion of hypochlorite to other compounds increase so that the measured
concentration deviates further and further from the theoretical value. At some electrolysis time the hypochlorite is used
up as fast as it is produced and the concentration no longer increases with time. In fact, on extended electrolysis the
concentration of hypochlorite will decrease as the sodium chloride in the electrolyte approaches exhaustion.
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 (1) Configuration of the cell
(2) Characteristics of the anode and the cathode
(3) Current density
(4) Electrolyte volume
(5) Mode of operation
(6) Temperature
(7) Concentration of NaCl in electrolyte
(8) Flow rate through cell

J 20 40 60 80 100
(9) Flow rate to and from the system
(10) Other substances besides NaCl present in the water.

Electrolysis Time - Minutes

Change In Hypochlorite Concentration
With Electrolysis
FIGURE 1

For example, at very low temperatures near freezing, the real curve is suppressed. Then, as the electrolysis tem-
perature increases, the solid curve rises to a maximum in the 15-20° C range, decreases gradually up to about 35°C,
and then more rapidly as the electrolysis temperature is further increased. Voltage must also be taken into
consideration because the power costs are directly related to the operating voltage of the cell. The voltage decreases
rapidly at first as the electrolyte temperature increases above freezing and then more slowly as the temperature is
increased further. The net effect is that the optimum operating temperature range is 1535°C. Inasmuch as the solution
is heated during electrolysis, heat must be removed from the electrolyte when the desired concentration of hypochlorite
in the product is high. Thus heat exchangers and cooling towers must be provided for systems requiring high
concentrations of hypochlorite in the product electrolyte.

The large number of factors which influence the performance of the system justifies the relatively large number
of questions we ask concerning the specific application so that we can select the best system and mode of operation
for the particular application.

Once the system and mode of operation are selected, however, most of the variables become fixed. Operation of
the unit is not complicated. Performance is reliable and the results are predictable.

The effect of each of the variables listed above will not be discussed here. However, because we do design systems
to operate in three different principal modes, technical considerations will be given here. There are, however,
important engineering considerations related to each mode of operation.

Obviously, there are several ways that the brine electrolyte can be passed through the cell. These are illustrated
in Figures 2.1 - 2.3.

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 4 Cells

Heat
Exchanger
Batch Tank Pump

Batch Operation
FIGURE 2-1
1. Batch Operation (Figure 2- 1)
A batch tank can be filled with salt-water of the appropriate concentration. The brine solution can then be
recirculated from the batch tank through a heat exchanger to control the temperature, through the cells, and back to
the batch tank. This recirculation through the operating cells can be continued until any achievable hypochlorite
concentration is reached. Flow through the cells is in parallel. This modification is seldom used due to the increased
number and size of tanks involved (generally 3) and the increased operator attention required.

2. Feed - Recycle - Overflow Operation (Figure 2-2)

The salt-water electrolyte is fed to a recycle tank. A recycle pump circulates the electrolyte through a heat ex-
changer (if required), through the cells (parallel flow) and back to the recycle tank. Product hypochlorite flows from
the recycle tank at the rate fresh electrolyte is fed to the system. This mode of operation eliminates the batch tank,
is easy to operate and can be designed so that the production rate follows the demand.

I I I

I I I
I
I Hypo to
I
I Use
I I I
I I 1
 3. Series Flow Operation (Figure 2-3)

The brine-water electrolyte is fed through cells or groups of cells in series so that it enters the first cell at zero hy-
pochlorite concentration and leaves the final cell (or cells) of the series at the designed concentration. For high
concentration final product (-8 g NaOCl/l) provision must be made for cooling and gas release. Horizontal cells are
used in series flow systems.

Current Efficiency \
E 60 vs NaOCl concentration
\
2 \
30 g NaCl/l at start, 30°C temp. \
5 \
Solid line-batch or series flow operation \
o 50 Dashed line - Feed Recycle Overflow operation \

Sodium Hypochlorite Concentration g/l

FIGURE 3

Figure 3 shows typical relationship observed between current efficiency and the concentration of hypochlorite
produced for the three modes of operation. The results for batch operation and series flow operation are very nearly
the same and are shown here as the single solid line curve. The dashed-line curve is the result expected from the Feed-
Recycle-Overflow mode of operation.

It will be noted that at low concentrations of hypochlorite the current efficiency is not greatly different from any
of the operational modes, However, as the concentration increases, the current efficiency for operation in the Feed-
Recycle-Overflow mode falls off faster than for the other modes of operation.

When high concentrations of hypochlorite is required in the product,

series flow operation (or batch) is required.

When seawater is available and thus salt costs are low, the engineering
and operational advantages of the Feed-Recycle-Overflow mode of opera-
tion usually makes this mode of operation the most attractive.

The relationship between saltrequiredperpound of sodium hypochlorite

produced and the concentration of sodium hypochlorite in the product is
shown in Figure 4. If salt cost were the only consideration, it is evident that
one would select a low salt concentration and try to make as high a
concentration of NaOCl product as possible.

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