SOLAVITE

WATER TREATMENT SYSTEMS

THEORETICAL EXPLANATION

AND EVALUATION

By Chaim Yosef J. F. Mariategui-Levi, PhD.

Inorganic Chemist

New York – USA - +August, 1989

 SUMMARY
The goal of this work is to provide the informed reader with the general principles that
govern the functioning of SOLAVITE equipment.

The chemical and electrochemical systems of water treatment will be described, as well
as the functional process of SOLAVITE equipment, and the principal factors that
affect its performance.

Also summarized are some chemical reactions that occur in the use of SOLAVITE for
removal of incrustations due to carbonates and other mineral deposits. These will be
expanded upon in subsequent works.

This paper should be read sequentially in order to maximize one’s understanding of

how SOLAVITE works.

1
 INDEX
PART I: COMPOUNDS IN WATER AND THEIR TREATMENT

1. Compounds found in water

2. Water classification
2.1 Hard water/Soft water
2.2 Alkaline/Acidic water

3. Water types for industrial use

3.1 Clarified water
3.2 Process water
3.3 Demineralized water

4. Water quality problems in industrial equipment

4.1 Scale
4.2 Foaming
4.3 Priming
4.4 Sludge
4.5 Corrosion
4.6 Embrittlement

5. Chemical systems in water treatment

5.1 Introduction
5.2 Water classification for chemical treatment
5.3 Types of chemical water treatment
5.4 External water treatment
5.5 Internal water treatment
5.5.1 Introduction
5.5.2 Corrective internal treatments
5.5.3 Internal treatment with inorganic products

2
PART II: SOLAVITE FLUID TREATMENT .
THEORY AND OPERATION

1. Operation

2. Physical description and operational details of the Solavite system

3. Theory of operation
3.1 Electrical activity in SOLAVITE
3.2 Magnetic activity in SOLAVITE
3.3 Flow effect in SOLAVITE

4. The Magnetic treatment of water

4.1 Introduction
4.2 Experimental findings
4.3 Summary

5. Crystallization, scaling, cleaning

5.1 Introduction
5.2 How scaling occurs

6. Theory of nucleation
6.1 Introduction
6.2 Formation of nuclei
6.3 Crystallization
6.4 Summary of Experimental Results

3
PART III: EXPERIMENTAL RESULTS, CONCLUSIONS AND
RECOMMENDATIONS

1. Experimental results
1.1 SOLAVITE treatment crystals
1.2 Scale crystals

2. Description of observations

3. Interpretation of results

4. Conclusions
4.1 Proven effectiveness of SOLAVITE
4.2 No major changes in pH
4.3 Creation of crystal embryos
4.4 Induction of nucleation

5. Recommendations

4
PART I: COMPOUNDS IN WATER AND THEIR TREATMENT

1. INTRODUCTION: COMPOUNDS FOUND IN WATER

The existing compounds in water can be divided into two fundamental categories:

A. INSOLUBLE COMPOUNDS: These are substances that are found suspended in

water and are easily identified by the naked eye-- such as oils, materials in
suspension, sand, ashes, etc. These substances are usually removable from water
through physical operations such as filtration, decantation, sedimentation, etc.

B. SOLUBLE COMPOUNDS: These are mineral substances and gases which are
found totally or partially dissolved in water-- examples are CO (carbonic gas), H2S
(hydrogen sulfide), SiO2 (silica), NaHCO3 (sodium bicarbonate), CaCO3 (calcium
carbonate), etc. These substances are only removable from water through chemical
or physical-chemical means such as ionic exchange, electrochemical precipitation,
dialysis, etc.

5
 2. WATER CLASSIFICATION

Generally speaking, water can be divided as to the substances dissolved in them:

A: Hard or soft water
B: Acidic or alkaline water

2.1 HARD WATER/SOFT WATER

Water classified as hard or soft refers to the greater or lesser quantity of soluble
compounds (mineral salts and gases) dissolved in water.
The U.S. Geological Service’s classification of water can be cited as an example.
______________________________________________________________
Table 1: Classification of water as to hardness by the U.S. Geological Service Source:
ref. (1)

Class Hardness, ppm Classification

1 0 to 55 Soft water
2 56 to 100 Fairly hard water
3 101 to 200 Moderately hard water
4 201 to 500 Hard water
Note: ppm: parts per million
______________________________________________________________

The terms soft or hard water usually refer to the greater of lesser capacity of the water
to produce foam when soap or detergent is added to it. The greater the quantity of salts
dissolved in water (more hardness), the lesser the capacity of the soap to produce foam
when dissolved in water. This phenomenon occurs because the calcium and magnesium
salts dissolved in water react to the soap, becoming insoluble. Thus the water does not
produce foam.

6
2.2 ACIDIC/ALKALINE

The classification of water as acidic or alkaline refers to the quality of the salts or gases
dissolved in the water. Here, water containing hydroxides, carbonates, bicarbonates,
etc. as dissolved salts, is classified as alkaline water, since these compounds confer an
alkaline characteristic to the water(pH.> 7.0)

On the other hand, water which contains dissolved gases types SO2, H2S, CO2, etc.
presents an acidic characteristic, since these compounds confer an acidic characteristic
to the water (pH > 7.0).

IMPORTANT NOTE: The hardness of the water, as well as its alkalinity, varies from
place to place and region to region, and can be present in the most varied of
compositions.

7
 3.TYPES OF WATER FOR INDUSTRIAL USE

Water that is used industrially can be classified into three basic types:
A: Clarified water
B: Process water
C: Demineralized water

3.1 CLARIFIED WATER:

This is water exempt of suspended solids, oils, silica, sand, ashes, but which contains
dissolved chemical compounds, mineral salts and gases.
In industry, this type of water is used for general consumption and for equipment
cleaning, such as producing thermal heat exchange (cooling and/or heating) in
industrial equipment that does not require much thermal charge, usually in equipment
which operates under temperature of up to 100 C.
Examples: Open refrigerated systems, heat exchangers which operate under low
pressure, cooling molds of industrial machines, cooling towers, etc.
3.2 PROCESS WATER:
This is clarified water which was submitted to previous chemical or physical-chemical
treatments, in order to reduce its hardness or acidity.
Process water is usually utilized to generate steam or effectuate thermal exchange
(cooling or heating) in equipment of high thermic performance, generally industrial
equipment which operates in temperature above 100 C.
Examples: Boilers, chemical reactors, high altitude compressors, distillation columns,
heat exchangers, cooling of plastic injection molds and expulsion machines, etc.

3.3 DEMINERALIZED WATER:

This is process water which is submitted to a specific chemical or physical-chemical
treatment in order to obtain water totally exempt of mineral salts and gases. This water
is also known as deionized water.
This type of water is only utilized when water purity is a critical factor in the
production process.
Examples: Water for cooling nuclear reactors, production of electronic
components, chemical products of high purity, etc.

8
4- WATER QUALITY PROBLEMS IN INDUSTRIAL EQUIPMENT

Following in table 2 are the main problems caused by water’s constituents in industrial
equipment, listed in a general manner:
_____________________________________________________________________________________
Table 2: Problems caused by water contaminants in industrial equipment

Constituents Resulting Problems

Solids in suspension Priming, foaming, sludge
Silica Scale
Calcium carbonate Scale
Calcium bicarbonate Scale
Calcium sulphate Scale, corrosion
Calcium chlorate Scale
Magnesium carbonate Scale
Magnesium bicarbonate Scale
Magnesium chlorate Scale, corrosion
Sodium chlorate Inert, but under certain
conditions, results in corrosion
Sodium bicarbonate Priming, foaming, embrittlement
Sodium carbonate Same
Sodium hydroxides
Calcium, Aluminum
and Magnesium Scale
Dissolved gases Corrosion
Acids in general Corrosion
Grease, oils and
organic Material Corrosion, deposits, scaling,
priming, foaming

____________________________________________________________

9
IMPACT OF RESULTING PROBLEMS ON OPERATING
EQUIPMENT

The following are the primary problems caused by deposits (scale), foaming, mud and
sludge, corrosion, priming, and embrittlement in industrial equipment:

4.1 SCALE:
The formation of scale in plates, surfaces, pipes and other parts of industrial equipment
causes the following problems in operational terms :

Greater consumption of energy to transport water or steam : A decrease in the pipe’s

internal diameter due to the formation of scale deposits on the pipe’s walls necessitates
an increase in pressure in the fluid transport (water or steam). This in turn requires
greater pump capacity to compensate for the loss of the line’s capacity, resulting in a
greater consumption of energy.

Greater consumption of energy to reach the required operational heat level : The
resistance to heat transmission increases with the formation of deposits over metallic
surfaces. More time is therefore required to reach the operational thermic exchange
regime, which in means a greater consumption of fuel.

4.2 FOAMING:
The formation of foam causes a greater consumption of electrical energy and fuel oil.
An increase of the liquid’s viscosity due to the surface tension causes the formation of
foam. Increased consumption of fuel oil is also due to the increase of the water’s
viscosity by the solids dissolved in it, which in turn causes an increase in resistance to
heat exchange.

10
4.3 PRIMING:
The abrasion of industrial equipment occurs because instead of transporting only the
water, we are also transporting partially dissolved solids through pipes and equipment.
The transport of more solid fluid through pipes results in friction of the dissolved solid
molecules in the water with the walls of the pipes, creating abrasion by friction in the
pipes. This situation, in operational terms, produces :

- Greater consumption of electrical energy and fuel oil, because the system in which
the transport and thermic exchange is being carried out is water and solids, instead of
only water.

- Favorable conditions for the initiation of equipment corrosion, in acidic or alkaline

medium, causes an increase in the cost maintenance and a decrease in the life-span of
the equipment.

4.4 SLUDGE:
The formation of mud, sludge, etc., results in a greater consumption of electrical
energy and fuel oil in the transport operation and the thermal exchange, besides causing
abrasion, deposit formations, obstruction, etc.

4.5 CORROSION:
The corrosion of industrial equipment is caused generally by the characteristics of the
water, acidic or alkaline, greater or lesser quantities of solids and dissolved gases in
water, the type of water treatment adopted, the equipment’s operational conditions,
temporary or permanent hardness, etc. The main problems caused by corrosion in
industrial equipment is as follows:

- Decrease, in the life-span of the equipment

- Increase in maintenance costs
- Increase of the operational costs due to constant maintenance interruptions
- In some cases serious accidents, including human injury and loss of life

4.6 EMBRITTLEMENT:
A preliminary condition, in which constant abrasion causes conditions favorable to
corrosion and it’s results.

11
 5. CHEMICAL SYSTEMS OF WATER TREATMENT

5.1 INTRODUCTION
In this section the main types of chemical water treatment used in industry will be
summarized. A familiarity with this topic is helpful in understanding the superiority
of Solavite over other treatments, all of which demand the use of toxic chemicals.

5.2 CLASSIFICATION OF WATER FOR CHEMICAL TREATMENT

The classification of water for chemical treatment is made according to the nature and
quantity of gases and dissolved or contained salts, being classified as:

- Water of carbonate hardness

- Water of non-carbonate hardness

Water of carbonate hardness usually contains the following dissolved salts:

- Magnesium and calcium bicarbonates
- Magnesium and calcium carbonates

In non-carbonate water, we have the following dissolved salts:

- Calcium and magnesium sulphate
- Calcium and magnesium chlorates
- Calcium and magnesium nitrates

Water that contains magnesium and calcium salts in the form of carbonates and
bicarbonates is called water of temporary hardness. Water containing dissolved calcium
and magnesium salts in the form of sulphates, chlorates, nitrates and others, is called
water of permanent hardness.

12
5.3 TYPES OF CHEMICAL WATER TREATMENT

Chemical water treatments can be divided in a general way-- External treatments and
Internal treatments.

External water treatment is aimed at reducing the levels of temporary and permanent
hardness (see table 1)

Internal water treatment is aimed at minimizing the formation of deposits, foam,

corrosion, abrasion, etc.

Internal water treatment is specific to the equipment, thermic exchange system, and
other operational conditions, and therefore differs greatly from external treatments.

For example, water with 45 ppm (soft water) of hardness obtained by external chemical
treatment, feeds two types of industrial equipment, one a boiler and the other a cooling
tower,

Although the feeding water is the same, each type of equipment requires a different
type of internal water treatment. The cooling tower will need biocides and/or
algaecides to prevent the formation of algae and sludge, since conditions that favor the
formation of these substances are present in the cooling tower.

Opposite conditions are present in the boiler. Here we have a pressurized system,
operating in temperatures above 100 C, where no live organism can thrive which can
cause algae or sludge formation. On the other hand, the operational system for the
boiler requires a degassified system under pressure for removal of CO2 (Carbonic
Gas), or the use of hydrazine for the removal of O2 (Oxygen), because both gases under
determinable conditions cause problems in the equipment, which does not occur with
the water system from the cooling tower, since the gases are naturally eliminated upon
contact of the water with the air through the tower.

13
5.4- EXTERNAL WATER TREATMENT

External water treatment aims to obtain clarified water, process water or demineralized
water.

Clarified water is obtained through treatment with aluminum sulphate or ferric

sulphate. The object of this treatment is to remove the water’s temporary hardness due
to magnesium bicarbonates and calcium.

Process water is obtained by treating the clarified water with calcium hydroxide and
sodium carbonate or barium carbonate.

Process water also can be obtained by treating clarified water with the use of ionic
exchange resins of an anionic or cationic nature.

The treatment used in obtaining process water has an objective the removal of some
temporary residual hardness as well as the reduction of the permanent hardness to
lower operational levels.

Demineralized water is obtained by distilling process water, following degassification

(removal of gases).

14
 5.5 INTERNAL TREATMENT OF WATER

5.5.1: INTRODUCTION

The main objectives of internal water treatment are the following:

- Avoid the formation of foam

- Avoid the formation of deposits and incrustations in equipment

- Avoid the internal corrosion of equipment

- Avoid steam contamination

- Avoid the abrasion and fatigue of the metals which are components of the
equipment

These problems are caused by the presence of mineral salts and dissolved gases in
water, as can be evaluated through Table 2.

15
5.5.2 INTERNAL CORRECTIVE TREATMENTS:

The following are the internal corrective treatments and the respective chemical
compounds generally in use:

A: Maintenance of an alkaline pH in the boiler feed water for the control of

corrosion and deposits.
CHEMICALS USED: Caustic soda, sulphuric acid and sodium
carbonate.

B: Prevention of internal incrustations in boilers by the softening of the boiler

feed water .
CHEMICALS USED: Phosphates, sodium carbonate,
sodium aluminate, alginates,
sodium silicates.

C: Avoid the adherence of deposits on the boilers’ internal surfaces.

CHEMICALS USED: Tannins, lignin derivatives,
amides, glicose derivatives.

D: Preventing incrustations in pipes of hot water, steam, economizers,

condensers, etc.
CHEMICALS USED: Polyphosphates, tannins, lignin derivatives,
glicose derivatives.

E: Preventing corrosion by oxygen by deaerating the boiler feed water,

degassification, scrubbers, etc.
CHEMICALS USED: Sulphites, tannins, ferrous hydroxide,
hydrazine, glicose derivatives.

16
F: Preventing corrosion by the formation of protective films over the
equipment’s internal and external metallic surfaces.
CHEMICALS USED: Tannins, lignin and glicose derivatives.

G: Preventing corrosion by condensation

CHEMICALS USED: Polyamides, polyglycoles

H: Inhibiting metallic fatigue and abrasion of metallic parts :

CHEMICALS USED: Sodium sulphate, phosphates, tannins,
nitrates.

5.5.3 INTERNAL TREATMENT WITH INORGANIC

CHEMICAL PRODUCTS:

Internal treatment using inorganic products is aimed at achieving the following:

- Correction of water’s pH and alkalinity

- Deaearation of the water (removal of gases), and the removal of hardness.

17
 BIBLIOGRAPHIC REFERENCES

(1) Netto, Jose M. de Azevedo

Tratamento de Aguas de Abastecimento
Editora da Universidade de São Paulo, 1966

(2) Thomspon and Reents

Ind. Eng. Chem., 51, 1259,(1959)

18
 PART II:

SOLAVITE FLUID TREATMENT:

THEORY AND OPERATION

1-OPERATION:

SOLAVITE is a fluid treatment device which, when used to treat water, reduces
apparent hardness, prevents scale build-up, and removes existing scale in pipes and
boilers without an increase in corrosion or the use of chemicals.

SOLAVITE promotes crystallization of the dissolved species in the form of nucleated

crystals. SOLAVITE can therefore be called a “Physical Catalyst” or a
“Crystallization Promoter”.

The formation of rapidly growing nucleated crystals accounts for the prevention of
scale build-up on the pipes and boilers and the “softening” of treated water.

It also has been verified that SOLAVITE increases the efficiency in the burning of
hydrocarbons leading to a reduction in fuel consumption, but the principles of
operation for SOLAVITE with hydrocarbons are quite different to that of SOLAVITE
with water, and are beyond the scope of this work.

19
 2- PHYSICAL DESCRIPTION AND OPERATIONAL DETAILS OF THE
SOLAVITE SYSTEM

SETTING:
The basic components of SOLAVITE are the cell and the housing. The cell contains a
mixture of diamagnetic species (charcoal, alkalimetal halides) and a volatile solvent to
avoid the presence of oxygen in the cell.

The housing is made of aluminum or bronze. The setting is shown in Figure 1.1. for the
proper operation of SOLAVITE, the cell must be aligned to the magnetic north of the
earth ( + - 15 deg.).

3- THEORY OF OPERATION

3.1 ELECTRICAL ACTIVITY IN SOLAVITE

SOLAVITE combines three activities which result in the formation of nucleated
crystals-- electric, magnetic and the flow of the liquid (viscous flow).
All three are necessary for the operation of SOLAVITE in water treatment.
We will now discuss the effects of each:
Having two different metals, it is expected that SOLAVITE will behave as a battery, as
shown in the experimental section.
The voltage of SOLAVITE with aluminum housing is around 1 volt and with the
bronze housing is 0.3 volt
This electrical activity results in certain reactions, such as the reduction of chlorine (or
hypochlorites), which decreases the corrosive properties of the water.
How can SOLAVITE act as a complete cell if its electrodes apparently are insulated ?
Referring to Figure 1, it is true that it appears that there is no connection between the
housing and the cell that will result in a closed circuit.
But if we look closely, we find that there is a chamber where the fluid is stagnant
(Chamber 5)

20
Fig . 1

6 8

9 9

3 4 4 8 7

1. Water (or other fluid) flow

2. Solavite cell
3. Housing (aluminum or bronze)
4. Insulating ring
5. Chamber where fluid is stagnant
6. Nipples ( PVC, CPVC or fiberglass)
7. Housing cap (aluminum or bronze)
8. O-Ring
9. Insulation and cap

21
It is here that concentration of ions rise due to the corrosion of the metals in the
stagnating water, which increases the water’s conductivity.

In order for this conductivity to reach its critical point, there is a need of 3 to 6 days for
the SOLAVITE system to become fully active.

After this period there is sufficient presence of dissolved ions at high concentration in
the stagnant water. Thus, the resistance is lowered, allowing the electrons to flow.

We now we have a system equivalent to a battery connected to a resistor, where the cell
acts as the anode and the housing as the cathode.

Where E = R i
E = volts
R = ohm
i = amp

22
It should be noted that there is a definite need to clean or replace the cell periodically
due to oxidation caused by dissolved oxygen on the cell. This reduces conductivity on
the surface and deactivates the system.

The voltage of the SOLAVITE system (housing & cell) is due to several reactions:

Reactions on the Al electrode (Housing)

2.2 2 A l +3 + 6OH - A l 2 O 3 + 3 H2O + 6e – (High pH)

2.3 2 A l +3 + 3H2O A l 2 O3 + 6H + + 6e– (Low pH)

Reactions on the copper cell

2.4 2H + 2e H2
-
2.5 Cl2 + 2e 2Cl

Other reactions may occur, such as the corrosion of aluminum by H + ions, chlorine
and oxygen and the corrosion of the copper by chlorine and oxygen.
Fe + 3 / Fe +2 ions may help in the electron transfer and in the nucleation of the
crystals as we will see below:

The “battery” behavior of SOLAVITE results in the charged electrodes necessary for
the electrostatic effect.

In this case we have a fluid that is moving between charged plates.

Let us now consider a static system, comparing a SOLAVITE CELL to a condenser

formed by two concentric cylinders.

Whenever we have two charged plates that are parallel to each other, the ions will
concentrate near the surface of the plate of opposite sign ( Positive ions are attracted to
the cathode and negative ions to the anode.) A gradient of concentration will also form
in the immediate vicinity of the plates, as shown in diagrams 2 and 3.

23
2.0 Gradient concentration curves for positive and negative ions.

+ _

(c)
+ _

+ _

+ _

+ _

(D)
positive electrode negative electrode

C = Concentration of ions
D = Distance from the plate

3.0 Pictorial representation of an ionic gradient

Concentration of ions.

+ -
+ -
+ - -
+ - - -
+ - - - -
+ - - - - -
+ - - - - - -
+ - - - - - - - -

Distance from plate.

24
As shown in these diagrams, the concentration of ions decreases sharply with the
distance from the plate.

If we have a condenser formed by two concentric cylinders and a liquid moving

perpendicular to the cylinders we will have the possibility
of “putting together” the two beams of ions of different signs, and crystallization will
result in the formation of embryos.

3.2 MAGNETIC ACTIVITY IN SOLAVITE

A synergistic factor is the weak magnetic field of the earth, now modulated by the
CELL, which is full of diamagnetic species. This results in a non-homogeneous field.
This field then provides a weak force that will act on the charged particles in the
solution.

F = q( v x B )

The force is perpendicular to the plane containing the vectors B and V. The orientation
depends on the sign of the ion. This effect is very weak, but it provides the means to
promote crystallization.

From the battery setting we have an electric field that separates the ions and creates
concentration gradients near the surface of the electrodes (i.e. near the cell or the
housing).

We also now have a force that pushes the ions from the magnetic field into the moving
ions.

These forces, together with the flow effects (see below) are responsible for the
promotion of crystallization.

25
3.3 FLOW EFFECT IN SOLAVITE

The electric field is by nature independent of the motion of the fluid, but the value of
the magnetic force F.B.V. is dependent on three factors: The intensity of the magnetic
field, the velocity of the ions, and the charge of the ions.

For effective crystallization to take place, it is necessary for there to be a minimum

velocity of the flow, which will ensure proper mixing at the outlet of the barrier. This
will initiate the encrystallization process due to statistical fluctuation of free energy in
parts of the system.

4. THE MAGNETIC TREATMENT OF WATER

4.1 INTRODUCTION

The magnetic treatment of water is based on several types of magnet settings.

The water flows through a tube which is surrounded by various arrangements of
electromagnets. These are usually arranged longitudinally NS-SN-NS and in some
cases NS-NS-NS.

These magnets provide the magnetic field B in the equation

> > >

F = q (v x B) .

The fields employed do not need to be very intense, and are in the order
of 0.1 Wb/m.

26
4.2 EXPERIMENTAL FINDINGS
When Ishihara and Bradley used magnetic devices for water treatment they were
surprised to find that the device induced the crystallization of CaCO3 as “snowflake-
life” nucleated crystals.

Our findings with SOLAVITE show that we have also succeeded in producing
nucleated crystals that were formed as the result of the operation of SOLAVITE (see
experimental section)

These findings indicate that both SOLAVITE and magnetic devices promote the
formation of crystal embryos that will cause calcium carbonate and other species to
crystallize in suspension, and not against the walls of piping and boilers.

4.3 SUMMARY
In summary, in the SOLAVITE system each ion present in water is submitted to a total
force due to the magnetic and electric field. This value can be expressed as:

F = q (E + v x B)

where q = charge of the ion, E = electric field, v = velocity of the ions,

B = magnetic field of the earth.

The forces applied to the particles in solution, together with the circulation at the back
of the cell, combine to promote growth of the embryos to a critical size.
These actions are responsible for drastic changes in crystallization patterns that result
in suspended particles. This reduces the apparent hardness of the water and inhibits the
scaling properties of the water.

It is interesting to note that our experiments have shown that if the flow is very slow, an
opposite reaction occurs, and an actual increase of scaling was observed.

27
We have found that effective circulation is reached behind the cylinder (cell)
when the Reynolds number (R) is between 10 and 30.

To calculate “R “ we need to know the velocity of the fluid (v), the diameter of the
cell ( D ), the viscosity of the water at a given temperature (T) and its density (p)3

R = ( p/n ) v.D

P = 1000 kg/m3

n = 10 N-M/ sec at 20 C’ (viscosity)

R = measure of viscous flow (Reynold’s number )

For low velocities (R < 10 ), we have found that mixing does not occur, and as a
result the larger nuclei are not formed and this allows the further growth of scale.

28
Flow past a cylinder for various Reynolds numbers

-2
R = 10

(a)

R = 20

(b)

R = 10

(c)

R = 104

(d)

R = 106
( e)

29
 5. CRYSTALLIZATION-SCALING-CLEANING

5.1. INTRODUCTION
Calcium Carbonate is one of the few substances whose solubility in water decreases as
water temperature increases.

This feature is directly related to the formation of scale on pipes, boilers and other
devices carrying water at high temperatures.

In explanation, the depositing of calcium carbonate (and other species) reduces the heat
transfer from combustion gases to boiler water, and at times provides sufficient
insulation to cause overheating of the metal, with disastrous consequences.

If the insulation is not so great, there is a marked reduction of the efficiency of heat
transfer, and a consequent waste of fuel.

It is important to realize that not only CaCO3, but magnesium carbonate, silica,
manganese, iron oxides and other species form mineral deposits in boilers.

30

5.2. HOW SCALING OCCURS

Most species need a surface to start the crystallization process. In the case of CaCO3,
the crystalline imperfections of metal serve as the surface nuclei for the crystallization
process.

Calcium carbonate grows dendrites on surfaces, and the addition of layer after layer
due to selective precipitation on the surfaces result after a certain time in a hard glassy
material.

In water with high concentrations of solids, a rise in temperature in the walls of a tube
can cause supersaturation and on site precipitation of scale-forming salts.

Nonetheless, scaling can occur even at low concentrations of dissolved solids (less than
10 ppm).

31

In 1936, Langelier (4,5) developed an equation to predict the tendency of water to

precipitate or to dissolve calcium carbonate.
This equation is a function of the total of calcium ions (pKa), the pH, the alkalinity
(pAIK) and the temperature (T) that determines the solubility of CaCO3 and other
species.
This equation is valid for 6.5 pH to 9.5 pH and 32 to 200 degrees F.
The equation is written as
pHs = (pK2-pKs) + pCa + pAIK
pHs = The pH at which the water with a given calcium concentration and alkalinity is
in equilibrium with calcium carbonate (in form of scale)
pCa = -Log (Ca +2 ), (Ca +2 ) is the total concentration of calcium in the water.
pAIK = -Log (AIK), alkalinity is a function of the dissolved carbonates and
OH.
Ks, K2, are the solubility products of CaCO3 and the second dissociation constant of
H2CO3, both depend upon the temperature and the total ionic content measured
conductimetrically as total dissolved solids (TDS).
The Langelier saturation index is evaluated as the difference between the measured pH
and the calculated pH. (normally taken from a no’mogram. See references 4 and 5.)
Is = pH – pHs
The saturation index, Is, is a qualitative indication of the tendency of calcium carbonate
to either deposit or dissolve
Is > 0, then scale is formed
Is = 0, then equilibrium results
Is < 0, then scaled is removed
This index measures only the directional tendency of the water but cannot be used as a
quantitative index.
It is sufficient for the purpose of describing the tendencies scale to be either formed or
be removed.

32

5.3 HOW DESCALING OCCURS

Descaling is the process of achieving the dissolution of mineral deposits present in the
inner walls of boilers or pipes.

For dissolution to occur it is necessary either to reduce the pH by acidification or by

other chemical treatments that will solubilize the scale or achieve the depletion of the
contents of the free ions of the elements that form the scale.

SOLAVITE follows this second, chemical free course.

SOLAVITE does not introduce new chemical species into water. Instead it provides
the required embryos or seeds needed for the formation of nucleated crystals.

These species are expected to be partially charged and are of rapid growth. This growth
causes the depletion of the dissolved species, specifically Ca + 2, causing the Langelier
index to turn negative (Is<0).

Under these conditions, the water tends to dissolve the pre-existing scale.

This occurs according to the following expression:

CaCO3 (scale) Ca +2 (aq) + CO3-2 (aq) CaCO3 (nucleated crystals)

CaCO3 results in the form of nucleated crystals.

This equilibrium is shifted to the right because of the growth of the nucleated crystals.

It is important to remember that treatment with SOLAVITE does not change

appreciably the pH of the water and does not introduce any chelating agent into the
water.

33

6 THEORY OF NUCLEATION
6.1. INTRODUCTION:

It has been observed that when water in a boiler is treated with the SOLAVITE system,
scale is not formed and pre-existing scale is removed.

After a certain period of operation with SOLAVITE (2-3 months ) boilers were
cleaned by blow-down. Instead of finding scale there was an observation of small,
nucleated crystals, some in the form of snowflakes (see experimental section).

This finding indicates that SOLAVITE acts as a nucleation control treatment of the
boiler water.

Two questions arise: First, how are the seeds for these nucleated crystals formed ?
Second, by what mechanism is the pre-existing scale dissolved ?

To answer these questions it is necessary to understand how nucleation occurs and the
nature of the crystal seeds or embryos in water.

34

6.2 FORMATION OF NUCLEI:

We still must understand how SOLAVITE causes these small nuclei to be formed.

Scale is formed if there is at least a local saturation of dissolved species near the walls
of pipes or boilers. In saturated stable (or metastable ) solutions it is necessary to
introduce a glass rod, or crystal seeds or to irradiate the system with ultrasound to
cause a saturated solution to precipitate.

In a boiler these dissolved species usually will be induced to crystallize by the

crystalline imperfections of the metal of the boiler. The formation of the nucleated
crystals starts in the SOLAVITE systems where a very small fraction of the ions are
pushed together by the weak magnetic and electric forces.

These species attain “maturity” if properly mixed before leaving the SOLAVITE
setting as seen in figure 4.

The growth of the crystals occurs in the (saturated conditions) boiler or through the
pipes.

The kinetics and growth of the nuclei into nucleated crystals depend on the
concentration of dissolved species, the solubility constant of the species at a given
temperature, and the nuclei concentration.

35

6.3 CRYSTALLIZATION:
To explain crystalization we must remember that there is a change from one phase to
another. The energetics of this transition is described by the changes in the Gibbs free
energy equation: (6,7)

G = ( n2 – n1 ) n, for T, P Constant (eq 1)

n = molar substance that changes phase change from 1 to 2 .

n 1 = chemical potential of phase 1

n 2 = chemical potential of phase 2

For convenience we introduce the term ,that represents the molar affinity for the
phase change. is an intensive quantity and is independent of the amount of matter
that undergoes the transformation.

= G / n = n 2 - n1 (eq. 2)

if < 0 the transition from 1 to 2 is spontaneous.

if = 0 there is equilibrium between the phases

if > 0 there transition cannot occur.

For practical purposes, can be defined as

= K T LnS, where

K = the Boltzmann’s constant

T = temperature in Kelvin
S = saturation ration (S = c/s)
c = concentration of solution
s = solubility

36
In very small portions of matter, such as the nuclei of a new crystalline phase, it is
important to consider that the molecules or ions in the surface layer are in a state of
higher potential energy than the interior ions or molecules of the crystal.

This excess energy is not compensated for by a sufficient excess of entropy.

Thus, the G of the substance forming the surface layer is greater than
G for the remainder of the material.

For macroscopic bodies, this excess of surface energy is called surface tension.
This is G’s surface free energy per unit area of surface.

But for nuclei consisting of a small number of ions (10 to 100), the definition of
surface area is ambiguous.

In these cases, it is convenient to use very simple expressions to define them.

For example, the are for the nuclei:

A = p n 2/3 (eq.3)

Where n is the number of molecules in the nucleus and p is a constant which

depends on the composition of the crystals formed.

37
Now G is defined as a function of n, and A, as shown in eq 4.
-A
G = -n + (eq. 4)

Or even better as

G = -n + n 2/3 (eq. 5)
Where , are independent of R, and > >
For > 0 and large n values (over the critical value of nucleation ) G < or = 0 in a saturated or supersaturated solution. But
for small n values, G is always positive. The critical value, or maximum for small n values is estimated by making
d G/ dn = 0

d G/dn = + 2/3n -1/3 = (eq. 6)

n = n* = (2 /3 )) 3 (eq.7)

For a maximum

d2 G/dn2 < 0

d2 G/dn2 = -2/9 n –4/3 < 0, for >0 (eq. 8)

n* is defined as the critical value of nucleation for > O and n = n* = n

Particles with n > n* will grow without limit, those with n < n* will dissolve completely.

38

The latter is calculated by defining G as:

G = -n + n2/3 + K T Ln Xn (eq. 9)
K = Bottzmann’s constant
T = temperature
Xn = molar fraction of embryos
If G = O then
2/3
Xn = exp [ ( n -n ) / KT ] (eq. 10)
and Cn = vo –1 Xn
where Cn = the embryo concentration per unit volume and vo = molecular volume
of the solvent (water)
The concentration of these nuclei is not very high, the order of some few hundreds
per cubic centimeter are enough to cause a decent nucleation rate.
A very important factor in nucleation is presence of iron ions.
Calverley 1 reports that the effectiveness reported by Soviet researchers into
magnetic devices for water treatment depends on impurities in the water,
specifically iron ions.
The studies of Nippon Benkan and Kogyo (Japan) indicates that SOLAVITE
promotes the dissolution of ferric oxide, and the nucleated crystals observed by the
author contain iron, specifically in the center of the nucleated crystals (i. e. the
nucleus).
The function of the iron in the formation of these species is not clear, but a
dispersion of finely divided iron hydrous oxides may be the key to understanding
the nucleation process occuring in the SOLAVITE system.
There are several possibilities: One is that the coloidals particles may absorb
calcium ions under the conditions present in the SOLAVITE system and start a
crystal growth around it.
Another possibility is the formation of a crystalline iron compound in suspension,
able to act as a template or seed for growth of the nucleated crystals, but all this is
an educated guess. Now let us see the experimental results.

39

6.4 SUMMARY OF EXPERIMENTAL RESULTS:

1. Crystallization: When Solavite is applied to water, a slurry of small crystals, easily
removable from the setting is formed. From microscopic observations, it appears
that the crystals grow around a nucleus (darker in pictures) confirming the expected
result of nucleation.

2. Nippon Benkan Kogyo Co., Ltd. (see report) the highlights are:
1- No measurable changes in pH.
2- Removal of scale.
3- Elimination of the constituents of scale in the output.
SEE APPENDIX FOR REPORT

3.Fluid Management, Charts on pH (see figures) confirm what Nippon Benkan and
Kogyo labs have reported about the pH.
SEE APPENDIX FOR CHARTS

4. Measuring of the voltages of the cell: Using a voltmeter (SPECO model F

70), it was determined that the voltage of the cell (with aluminum housing)
was 1.0 volts and for the cell (bronze housing) was .3 volts.

40

PART III: EXPERIMENTAL RESULTS, CONCLUSIONS AND

RECOMMENDATIONS
 1. EXPERIMENTAL RESULTS

Comparison between the crystals formed due to the SOLAVITE treatment of waters
and those of the scale in boilers:

Nature of the samples:

1.1 SOLAVITE treated crystals:

These species were obtained as suspension in water after being removed from a boiler
by blow-downs. The incoming water of the boiler was treated with SOLAVITE. The
crystals were separated from the solution and dried over slides.

1.2 Scale Crystals:

These species were collected from several boilers as scale. The scale was carefully
scraped to collect the crystals . A homogeneous sample from various sources was made
to have a representative sample of crystals.

These crystals were suspended in water and set over a glass slide to dry, as above for
the nucleated crystals. Both sample were observed under a microscope and pictures
were taken. The magnification ranges were from 400 to 2000, before developing the
negatives.

41

2. DESCRIPTION OF OBSERVATIONS
Most of the species found in the SOLAVITE-treated blow - off water are small
crystals from 0.5 to 1m. Some species are larger and show very clearly their
growth pattern. In Picture 1 the larger crystal shows a regular dense layer-by-layer
growth starting from the center (nucleus).

In the periphery of the crystal, a more diffuse growth is observed. This more diffuse
growth occurs when the crystal is large enough, due to its surface, to act as a
template for the growth of other crystals.

In Picture 2, several nucleated crystals can be observed. The small ones appear very
compact, but the larger ones display secondary growths in the form of branches
(dendrites).

In Picture 3, (lower magnification x 400) shows larger crystals taking the form of
snowflakes. These species are not as abundant as are the small crystals.

Picture 4, shows large nucleated crystals, some show details as in

picture 1.

Picture 5 and 9 show some small nucleated crystals with a large magnification
( x 2000) no details can be observed.

Pictures 7 and 8 show the dendrite structure of CaCO3. These species were very
rare in the sample. They were probably formed during the evaporation of the solvent
due to residual CaCO3 in solution.

Picture 30 presents a very large number of nucleated crystals.

42
PHOTOS OF SCALE

The crystals from the scale (pictures 10 to 29) show a very different a very different
pattern of growth. These species are flat, and well defined rhombohedral crystals.
These species grow layer by layer as shown in photos 12, 16 and 19.

The darkness in some of the crystals is due to staining with iron and probably
manganese as (Mn O2).

The scale is dissolved due to a depletion of the ions in the solution ( Ca + 2, CO3-2 -,
Mg +2, Fe +2, Fe +3, SO3-2) and not to the addition of a chemical to solubilize the scale.

Using SOLAVITE we have two equilibria that explain the removal of the scale,
probably kinetically controlled.

[CaCO3] scale Ca +2 (aq) + CO3 (aq) (1)

Ca +2 (aq) + CO3 – 2 (aq) [CaCO3] nucleated crystals (2)

The growth of the nucleated crystals depletes the concentration of dissolved calcium
carbonate (eq 2), causing a dissolution of the scale to maintain the equilibrium
(eq 1).

The rapid growth of the nucleated crystals causes species to CO crystallize with
CaCO3, such as Iron oxides, magnesium and calcium silicates and probably some sulfides.
**********************************************************************
ATTENTION : The Photos of Scales are available
separetely.

PHOTOS OF SCALES - ( from Pages : 44 to 47 )

********************************************************************

43

3. INTERPRETATION OF THE RESULTS

 Prior to the advent of SOLAVITE there were two basic techniques to control scale
deposits. Both require the addition of chemicals.
The first technique, which involves the use of chelants/dispersants is a solubilizing
program that uses EDTA alone or in combination with a chelating agent.
A disadvantage of this method is the increased corrosion due to the presence of the
chelating agent.
The second method requires phosphates and a dispersant, usually a synthetic
polymer, to control the size of the crystals. Here, instead of carbonate, phosphates
are formed.
SOLAVITE acts by promoting the formation of rapidly growing nucleated crystals.
The species are formed first as “embryos” or very small crystals of some few
hundred atoms. These initially grow as a layered crystal, and later they take the
form of snowflakes. They thus prevent the formation of species that are able to
become attached to the walls of the boiler.
This action by SOLAVITE makes the process an excellent preventative against the
deposition of both carbonates and silicates on boiler surfaces.
According to a report prepared by Nippon Benkan Kogyo Co. Ltd. about the
confirmation of the effects of SOLAVITE (see report), the calcium carbonate and
other species were removed from the surface of the pipes.
Furthermore, when rusty pipes were treated (initially covered with about 0.2 to 0.21
mg/cm2 of oxides ) this layer was reduced to 0.05 + 0.01 mg/cm2 of rust.
This experiment shows the ability of SOLAVITE to dissolve iron oxide. The
mechanism is not clear, but it may be due to the abrasion caused by the crystals,
plus the fact that the pH does not change appreciably (see charts).
Another explanation is that the ionic strength of the solution decreases,
consequently reducing the amount of dissolved iron.

48

4. CONCLUSIONS

4.1 PROVEN EFECTIVENESS:

 SOLAVITE has been proven effective in the removal of scale from pipes and
boilers without introducing chemicals into the water.
Both silicates and alkaline earth metal carbonates are removed. If rusty pipes are
used, the loose Fe2O3 scale is removed, leaving a thin layer of protecting oxide.
4.2 NO MAJOR CHANGES IN pH
During the operation of SOLAVITE no major changes in pH were observed. The
variation of pH between the incoming water (before treatment) and the outgoing
water was + 0.1 units of pH.
4.3 CREATION OF CRYSTAL EMBRYOS
The most important feature of the SOLAVITE effect on water is the
seeding of crystal embryos. These embryos are responsible for the growth
of nucleated crystals. The rapid growth of nucleated crystals depletes the
concentration of dissolved species in the water inducing the dissolution of
the preexistent scale.
The nucleated crystals due to their shapes (snowflakes or fusiform
crystals) are unable to attach on the surface and are easily removed by
blowdown of a boiler.
Other features of the SOLAVITE treated water are due to a reduction of
the dissolved ions due to the formation of small crystals in suspension. The
most interesting effect is the pseudo soft water behavior in regard to soap.
The presence of very small amounts of Ca +2 ions in solutions is
demonstrated by the scarce formation of insoluble fatty acids salts that
attach to the walls of the sinks and dishwashers as grease.
4.4 INDUCTION OF NUCLEATION:
The nucleation or better the formation of embryos that grow into the
nucleated crystals may be induced basically by two weak forces, -one due
to the electric field of the metals (cell + housing) and the other dependent
in both the movement of the ions and the weak magnetic field of the earth.
It still is not clear how these forces induce the formation of the embryos
but it is interesting to see the scheme of the intensity of the force due to the
magnetic field and the movement of the charged particles (fig. 5,6).
Apparently it is important to consider the effect of mixing at the outlet of
the SOLAVITE system for the successful formation of the embryos.
49

Fig. 5
+
 Cell - --------------------------------------------------------------------- Housing

Intensity of the electric field between the cell and the housing.

Fig. 6

Variation of the force due to a charge moving between the cell and the housing under a magnetic
field. The graph represents the absolute value of F.
In Fig. 6, the variation of F is due only to the changes in the velocity of the fluid. On the surfaces,
the velocity approaches , and the velocity is Maximum in between the plates (or cylinders).

F = q (V x B)
50

5. RECOMMENDATIONS
MORE EXHAUSTIVE STUDY

As mentioned above (in the conclusion ) the mechanism of formation the crystal
embryos is not clear, therefore, a more exhaustive physical/chemical study needs to
be done. The effect of SOLAVITE is unique and of great theoretical and
practical importance.

STUDY BACTERIOSTATIC EFFECT

There is some evidence of the bacteriostatic effect of SOLAVITE, particularly

when used for cooling towers.
The study of SOLAVITE and the understanding of all its applications has just
begun.
Much research is needed to elucidate the properties and functions of this important
device.

51

REFERENCES
1. Calverley, R. A .: Read, A .D. Magnetic Treatment of Water for Mineral
processing operation: A Critical Study.
Transactions Institutions Mining Metallurgy section.
Vol. 79, 1970. Pp. 0141-0147

2. Ishihara F. Y. , Bradley, S.M. Magnetic conditioning for control of Scaling and

Biogrowth - Journal of Imaging Technology 4,6 154-160 (1988)

3. The Feynman’s Lectures on Physics Vol II Chapter 41,

Feynman, R.P. Leighton R.B. Sands M. Addison Wesley
Publishers, Reading Ms. 1964.

4. Betz, Handbook of Industrial water treatment, 8th edition, 1980

5. Rosa, F.; Water treatment Specification manual.

McGraw-Hill, Inc. N.Y., 1985

6. Nielsen A .E., Kinetics of Precipitation Pergamon Press, N.Y. 1964

7. Laitnen, H.A . ; Harris, W.E.; Chemical Analysis, 2d edition,

MacGraw-Hill – Series in Advanced Chemistry, N.Y., 1975

52

CHAIM YOSEF MARIATEGUI-LEVI, Ph.D.

EDUCATION:
B. S., Chemistry, Catholic University of Peru, 1980 (Minor in Physics)
M. A., Chemistry, Catholic University of Peru, 198
M. S., Chemistry, University of New Mexico, 1985
Ph. D., Inorganic Chemistry, University of Kentucky, 1988
ADDITIONAL STUDIES:
Applied Biochemistry, San Marco University, Lima, Peru
Glass Technology, San Marcos University, Lima, Peru
Radiation Safety Training, University of New Mexico,
Albuquerque, New Mexico
Agricultural Analytical Chemistry, University of Kentucky, Lexington,
Kentucky
Corrosion Engineering, University of Kentucky, Lexington, Kentucky
REGISTRATION: Professional Qualifications, Peru
SPECIALIZATION: Chemistry, Chemical Technology
EXPERIENCE:
1988 to Present: Mount Sinai Hospital. Genetic, Post-Doctorate Fellowship on
protein Chemistry with training in protein purification, immunology, and Enzyme
Assays.
1988 to Present: Fluid Management Company.
Consultant in water treatment devices.
Fall 1985 to March 1988: University of Kentucky,
Department of Chemistry. Research Assistant.
Fall 1983 to Fall 1985: University of New Mexico,
Department of Chemistry. Research Assistant.
January 1983 to Fall 1983: Peru Research. Consultant.
Design of a pilot plant for leaching metal sulphides with
ferric chloride.
January 1982 to January 1983: Minera Pachapaqui, Mining
Laboratory. Supervisor in Quality Control. Supervised and
trained fifteen employees who test sample concentrates and
perform analysis. Complete analysis of approximately 100
samples a day and determination of moisture in each.
January 1982 to January 1983: Catholic University.
Teaching Assistant in Calculus and Physics.
53
1979 to 1980: National University of Engineering, Flotation
Plant. Night Shift Supervisor. Supervised five to six people that
tested floating agents and depressants.
AFFILIATIONS: American Chemical Society, Peruvian Chemical Society,
Peruvian Society of Physics, Society of Professional Chemists of Peru

SELECTED PUBLICATIONS

Mariategui, J.F.J., Niedenzu, K., Complexes of B-Tiethylboroxin with

Ethylendiamine and Derivatives, 1989.

Mariategui, J.F.J., Niedenzu, K., Pyrazaboles of the Type RR’ B(u-pz) BR’R,
Inorganic Chemistry 1987, 26, 3114.

Mariategui, J.F.J., Niedenzu, K., Hydrazine Complexes of B-Triorganylboroxis,

Inorganic Chemistry 1987, 26, 3114.

Mariategui, J.F.J., Niedenzu, K., B-Halogenated Pyrazaboles, Inorganic Chemistry

1987, 26, 2310.

Mariategui, J.F.J., Niedenzu, K., Chemical Behavior and the Structure of Triply
Bridged Pyrazaboles of Type RB (u-pz) 2 (u-OBRO) BR, Inorganic Chemistry 1987,
26, 143.

Mariategui, J.F.J., Leaching of Polymetallic Concentrates Using a Saturated Solution

of Ferric Chloride, Congreso Iberoamericano de Ciencias Quimicas, October 1983.

Mariategui, J.F.J., Synthesis of Amines and Phosphines of Bismuth III Halides,

Thesis, Chemistry 1985.

Mariategui, J.F.J., Reactions of Aluminum, Bromine, and Amonia in Methanol, Thesis, Chemistry
1983.

Mariategui, J.F.J., Synthesis of Amines of Aluminum Chloride, Thesis, Chemistry 1980.

54