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Article  in  International Journal of Nanomechanics Science and Technology · January 2016

DOI: 10.1615/NanomechanicsSciTechnolIntJ.v7.i3.30

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 Nanomechanics Science and Technology: An International Journal 7(3), 247–259 (2016)

STRUCTURE OF CaCO3 NANOCRYSTALS

ON THE HEAT EXCHANGER WALL
AND IN A SUPERSATURATED
AQUEOUS SOLUTION

S. I. Koshoridze & Yu. K. Levin∗

Institute of Applied Mechanics, Russian Academy of Sciences (IAM RAS),

7/1 Leningradsky Ave., Moscow, 125040, Russia

*Address all correspondence to: Yu. K. Levin, E-mail: iam-ras@mail.ru

An analysis of thermodynamics of CaCO3 phase transition in a supersaturated aqueous solution

showed that the formation of scale in the form of calcite on the channel wall in the absence of
magnetic treatment of a water flow is related to a smaller Gibbs energy of the generation of the
crystalline phase mentioned. Moreover, such a character of CaCO3 crystallization is caused by
the fact that the magnitude of crystallographic mismatch between the crystallized salt (calcite or
aragonite) and the surface (iron oxide and iron carbonate) is several times higher for aragonite.
On considering the process of homogeneous generation in the aqueous bulk, it was found that
nanosized nuclei with a radius over 1 nm also had the calcite phase, and those with a radius
less than 1 nm have the aragonite phase. This effect was caused by a higher density of the
aragonite phase. The results of the analysis of the thermodynamics of CaCO3 phase transition
allow one to explain manifestations of the magnetic treatment antiscale effect observed in real-life
heat-and-power installations.

KEY WORDS: Gibbs energy, solution concentration, magnetic treatment of water, an-
tiscaling effect, critical nucleus, calcite and aragonite as polymorphic phases of CaCO3

1. INTRODUCTION

It is known that during crystallization calcium carbonate CaCO3 forms polymorphic

structures, such as calcite and aragonite (Cefalas et al., 2008; Levin, 2014), with
calcite principally depositing on the heat exchanger wall. However, magnetic treat-
ment of a water flow leads to increased concentration of crystals in the aragonite
phase that are suspended in the aqueous bulk. Deposition layers in the calcite
phase have a dense structure that is difficult to remove from the heat exchange
surfaces.
Considering a high practical significance of this effect (a 1-mm-thick scale layer
reduces the heat transfer efficiency by 10%), it is expedient to clarify the causes
of generation of one or another crystallographic phase of CaCO3 on the heat ex-

1947-5748/16/35.00
2016 by Begell House, Inc. 247

248 Koshoridze & Levin

changer wall and in the aqueous bulk. The urgency and the features of this prob-
lem are also related to the fact that the effects manifested in a macro-world have
their own causes inherent in the properties and behavior of nanosized objects.

2. THERMODYNAMICS OF CaCO3 PHASE TRANSITION

IN A SUPERSATURATED AQUEOUS SOLUTION

We shall analyze CaCO3 crystallization, i.e., the formation of the solid phase in a
supersaturated solution, as well as the probability of generation of such CaCO3
crystallographic phases on the heat exchanger wall and in the aqueous bulk. Crys-
tallization of CaCO3 in any specific polymorphic modification is related to the
thermodynamics of the process mentioned.
The chemical reaction of scaling is as follows:

Ca2+ (aq) + 2HCO3− (aq) → CaCO3 (s) + H2O (lq) + CO2 (g) , (1)

where aq is the dissolved phase, s is the solid phase, lq is the liquid phase, and g
is the gaseous phase.
The possibility of spontaneous reaction can be determined by comparing the total
Gibbs energy of its initial and final components. The values of the Gibbs energy
for specific components of reaction (1) are listed in Table 1.
The values of the Gibbs energy G t for the formation of chemical elements are
presented in Table 1 for the standard conditions (Dean, 1999) (temperature
T0 = 298 K, pressure P0 = 1 atm) for the unitary solution molality (1 mole of ions
per kilogram of water) of Ca2+ and HCO3− ions. In reality, the conditions differ
from the standard conditions; therefore, the tabulated data should be recalculated
for the specific reaction conditions when calculating the energy balance. Accord-
ingly, the value of G t for CO2, presented in Table 1, should be recalculated to
some partial pressure P above the liquid–gaseous phase interface. Similarly to this,
the values of G t for Ca2+ and HCO3− ions, presented in Table 1, should also be
recalculated in conformity with the value of their real concentration C in the solu-
tion. In doing so, we shall consider only the effect of thermodynamic charac-
teristics of the CaCO3 crystallographic phases (calcite and aragonite), ignoring the
factor of crystallographic mismatch between the surface, onto which the scale is
deposited, and the crystallographic characteristics of the phases mentioned.

TABLE 1: Values of the Gibbs energy

Ca2+, HCO3−, CaCO3, CaCO3, H2O, CO2,

aq aq s.calcite s.aragonite lq g
G t, J/mole –553 540 –586 850 –1 129 100 –1 128 200 –237 40 –394 90

Nanomechanics Science and Technology: An International Journal

Structure of CaCO3 Nanocrystals 249

3. CRYSTALLIZATION OF CaCO3 ON THE CHANNEL WALL

FROM A SUPERSATURATED AQUEOUS SOLUTION

For a solid phase, it is not required to recalculate the value of G t when we con-
sider crystallization on a flat surface; however, such recalculation is required for
critical nuclei.
As is known, the relation of the Gibbs energies G(P) and G0 of the CO2 gas at
different partial pressures P and P0 is determined by the expression

G (P) = G0 + RT ln (P ⁄ P0) , (2)

where R = 8.3 J/(mole⋅K) is the universal gas constant.

A similar expression is used to describe the dependence of G(C) on the solution
concentration C for Ca2+ and HCO3− ions:

G (C) = G0 + RT ln (C ⁄ C0) . (3)

Using (2) and (3), we can present the energy balance of reaction (1) in order to
determine the reaction direction (crystallization or dissolution), which is determined
by the sign of the difference ∆G of the Gibbs energies on the right- and left-hand
sides of Eq. (1) for calcite

∆GC = GCO2 (g) + GH2O (lq) + GCaCO3 (s, C) − GCa2+ (aq) − GHCO3− (aq) , (4)

and aragonite

∆GA = GCO2 (g) + GH2O (lq) + GCaCO3 (s, A) − GCa2+ (aq) − GHCO3− (aq) , (5)

The reaction occurs in such a way that the value of the Gibbs energy could de-
crease, i.e., from left to right when ∆G < 0 and from right to left when ∆G > 0.
We consider first the formation of scale on a flat surface (wall of the channel)
at different concentrations C of the dissolved Ca2+ ions.
The summands of formulas (4) and (5), after recalculation of their tabulated val-
ues (designated by the superscript t), are as follows:

0.1
t
GCO2 (g) = GCO2 (g)
+ RT ln , (6)
101325

C
t 2+
GCa2+ (aq) = GCa (aq) + RT ln , (7)
1000

2C
t
GHCO3− (aq) (aq) = GHCO −
3 (aq)
+ RT ln . (8)
1000

Volume 7, Issue 3, 2016

250 Koshoridze & Levin

FIG. 1: Dependence of the Gibbs energy ∆G of the formation of calcite and aragonite cys-
tals with different r on the concentration of calcium ions Ca2+ in water. Curves 1 are for
a macroscpic crystal (the upper curve is aragonite and the lower is calcite); curves 2 for a
nanocrystal with r = 3 nm (the upper curve is aragonite and the lower is calcite); curve 3
for a nanocrystall with r = 1 nm (curves for calcite and aragonite coincide); curve 4 for a
nanocrystall with r = 0.6 nm (the upper curve is calcite and the lower is aragonite)

By substituting expressions (6)–(8) in formulas (4) and (5) we can determine the
dependences of the Gibbs energies ∆GC and ∆GA on the concentration C of the
dissolved Ca2+ ions. The calculation results are presented in Fig. 1 by curves 1:
the upper for aragonite and the lower for calcite; hence, we draw a conclusion on
the higher probability of calcite deposition on a flat surface.
It should be noted that the values of concentration C, at which ∆GC = 0 and
∆GA = 0 (the points of intersection of the pair of these curves with the axis of ab-
scissas in Fig. 1), correspond to the solubility of calcite C0C and aragonite C0A, re-
spectively. In this analysis, the partial pressure P = 0.1 Pa of the CO2 gas was
selected so that the solubility of calcium carbonate in water at T = 298 K, calcu-
lated in terms of thermodynamics, coincided with the known values for calcite
(C0C = 0.058 mole/m3) and for aragonite (C0A = 0.077 mole/m3) (Dean, 1999; Pri-
syazhnyuk, 2003).

Nanomechanics Science and Technology: An International Journal

Structure of CaCO3 Nanocrystals 251

4. HOMOGENEOUS GENERATION OF CaCO3 CRYSTALS

IN THE SUPERSATURATED WATER FLOW

Now, we consider crystallization of CaCO3, i.e., the generation of a critical nu-

cleus in the aqueous bulk. The difference from the above-discussed case lies in the
fact that it is necessary to recalculate the Gibbs energy of a CaCO3 macrocrystal,
given in Table 1, for the case of a nanosized crystal. As is known, the crystal
solubility C(r) depends on its "effective" radius r. Crystallization may become irre-
versible when the critical nucleus reaches the critical radius r, which is related to
the concentration C(r) of the solution by the relationship

2σ0 M
r = , (9)
C (r)
RTρ ln
C0

where M = 0.1 kg/mole is the molar mass of CaCO3 molecules, ρ is the density of
the CaCO3 crystal (for calcite ρC = 2715 kg/m3, and for aragonite ρA = 2930 kg/m3),
and σ0 = 0.16 J/m2 is the surface tension on the flat crystals–water boundary
(Koshoridze and Levin, 2013).
The meaning of formula (9) lies in the fact that the solubility of the CaCO3
crystal, i.e., the equilibrium concentration of the solution near its surface, is related
in a specific manner to the crystal sizes. In such case, the probabilities of the
sorption of CaCO3 molecules on the nucleus surface and of their desorption back
to the solution are the same. In the equilibrium state, the Gibbs energies of the
molecules in the solution near the crystal surface and on the crystal itself are iden-
tical. This allows evaluating the Gibbs energy for the CaCO3 solid phase in terms
of its solubility at a given curvature of the crystal surface.
From expression (9) we obtain

C (r) 2σ0 M
RT ln = . (10)
C0 rρ

Given this explanation and formula (10), the Gibbs energy G(r) of CaCO3 criti-
cal nuclei of radius r is determined by the expression

G (r) = G t + RT ln (C (r) ⁄ C0) , (11)

where G t is the value of the Gibbs energy for a macroscopic CaCO3 crystal, pre-
sented in Table 1.
From (10)–(11) we obtain

2σ0 M
G (r) = G t + . (12)
rρ

Volume 7, Issue 3, 2016

252 Koshoridze & Levin

The energy balance for generation of critical nuclei in reaction (1) is determined,
as before, by expressions (4) and (5), presented above by formulas (6)–(8) for a
flat surface.
Figure 1 (curves 2–4) shows the graphs of the dependence of the Gibbs energy
∆G used to generate crystals of calcite and aragonite with different r on the con-
centration of calcium ions Ca2+ in water, wherefrom it follows that for crystals
with r > 1 nm the generation of calcite is more probable than the generation of
aragonite. For nanosized crystals with r < 1 nm, aragonite is generated mostly. For
the radius r = 1 nm (about 68 molecules for calcite and 73 molecules for arago-
nite), the formation of both structures is equiprobable.

5. COMPARING THE GIBBS ENERGY OF ARAGONITE

AND CALCITE CRYSTALS

In order to give a better understanding of the causes of generation of crystals with

a specific structure depending on the radius of a critical nucleus, we write the dif-
ference of Eqs. (5) and (4):

∆GA − ∆GC = GA (r) − GC (r) , (13)

which retains only the difference of Gibbs energies GA(r) and GC(r) of aragonite
and calcite, respectively, since other terms are mutually annihilated. Hence follows
a conclusion that the shift along the axis of ordinates of the curves for aragonite
relative to the curves for calcite is identical at all values of solution concentration.
Given (12), we determine the dependence of the difference GA(r)−GC(r) of the
mentioned CaCO3 modifications on the crystal radius r:

2σ0 M ⎛ 1 1⎞
GA (r) − GC (r) = GAt − GCt + − . (14)
r ⎜ ρA ρC ⎟⎠
⎝

The graph of dependence (14) is presented in Fig. 2 (curve 1), which confirms
the result of the previously evaluated value of the critical nucleus radius r = 1 nm,
at which the formation of aragonite and calcite structures is equiprobable. Indeed,
curve 3 in Fig. 1, correspondent to Eq. (14), crosses the axis of abscissas at the
above-mentioned value r = 1 nm.
It can be seen from the same graph that for values of the nucleus critical radius
r < 1 nm the right-hand side of Eq. (14) is negative, i.e., the Gibbs energy of
aragonite is smaller and, hence, its generation is more probable than the generation
of calcite. Continuing the same analysis, we should, evidently, obtain the follow-
ing: for high values of the radius r > 1 nm there exists a higher probability for
generation of nuclei in the calcite phase.
It should be noted that, for the sake of simplification, the calculations of the
Gibbs energy did not consider the impact of the interphase layer between the solid

Nanomechanics Science and Technology: An International Journal

Structure of CaCO3 Nanocrystals 253

and liquid phases. The said effect is characterized by Tolman’s constant and leads
to decrease in the surface energy of nanonuclei and alteration of their charac-
teristics, such as dimensions, the number of molecules in a nucleus, and the prob-
ability of nucleus generation. We shall clarify this analysis in the next section.

6. INFLUENCE OF THE INTERPHASE LAYER ON COMPARISON OF THE GIBBS

ENERGY OF ARAGONITE AND CALCITE CRYSTALS

As shown in (Koshoridze and Levin, 2013, 2014c), the characteristics of mass

transfer processes in a supersaturated aqueous solution, when the radius of curva-
ture of the solid–liquid phase interface is comparable with the thickness of the in-
terphase region, are formed with due account of Tolman’s constant δ. As a result,
in expression (14) we use, instead of σ0, the effective value of the surface energy
σ(r) at the liquid–crystal interface:

σ0
σ (r) = . (15)
2δ
1 +
r

In this case, the probability of homogeneous generation of a nanosized nucleus,

defined by the effective value σ(r), increases substantially. Figure 2 presents the
graphs of the dependence of the difference of Gibbs energies of the formation of
crystals with a structure of aragonite and calcite on the radius r of the critical nu-
cleus at different values of Tolman’s constant.
In (Koshoridze and Levin, 2013) the estimated value δ = 0.4 nm was obtained.
For the above value of Tolman’s constant, given also (15), we built curve 4 in
Fig. 2, where the "neutral" value of the crystal radius r, correspondent to the con-
dition GA − GC = 0 (equiprobable generation of calcite and aragonite crystals), is im-
plemented at the values r = 0.16 nm. It should be reminded that without con-
sideration of the interphase layer we obtained a neutral value of the crystal radius
r = 1 nm. Curve 3 in Fig. 2 corresponds to the value of the constant δ = 0.3 and
intersects the axis of abscissas at r = 0.38 nm. Curve 2 in Fig. 2 corresponds to the
value of the constant δ = 0.1 and intersects the axis of abscissas at r = 0.78 nm.
Curve 1 was built ignoring the impact of the interphase layer (δ = 0 nm) and inter-
sects the axis of abscissas at r = 0.96 nm, which corresponds to curve 3 in Fig. 1.
The calculations showed that the condition δ = 0.47 nm, when GA(r) − GC(r) = 0,
corresponds to r = 0. Thus, at δ > 0.47 nm GA(r) − GC(r) > 0 for any r and genera-
tion of aragonite becomes impossible. However, this condition is physically impos-
sible, since the thickness of the interphase layer cannot exceed substantially the
particle sizes.
The results obtained are evidence for considerable influence of the interphase
layer thickness on nucleus dimensions at which the generation of aragonite phase
is substituted by the calcite phase as the nucleus size becomes larger. Nevertheless,

Volume 7, Issue 3, 2016

254 Koshoridze & Levin

FIG. 2: The dependence of the difference of Gibbs energies used to generate crystals with
aragonite and calcite structures on the radius r of the critical nucleus at the following val-
ues of Tolman’s constant: δ = 0.4 nm (4), δ = 0.3 nm (3), δ = 0.1 nm (2), and δ = 0 nm (1)

this does not change the conclusion on the generation of aragonite in the aqueous
bulk, since the initial stage of crystal generation is characterized by its minimal di-
mensions and, consequently, occurs in the form of aragonite. As mentioned above,
this phase is retained when the crystal grows further in the aqueous solution.

7. PHYSICAL MEANING OF THE RESULT OBTAINED

Considering relationship (14) reveals the physical meaning of the obtained result,
which lies in the fact that the sign of ∆G(r) is defined by the total of two quan-
tities: the positive summand (GAt − GCt ) and the negative summand

2σ (r) M ⎛ 1 1⎞
r ⎜ρ − ρ ⎟ .
⎝ A C⎠

The positivity of the first quantity is set by the initial relation GAt > GCt of thermo-
dynamic characteristics of the structures under consideration. The negativity of the
second quantity is defined by a higher density of aragonite ρA > ρC. The nature of
the discussed polymorphic structures is such that the balance of the positive and
negative summands takes place at the above-mentioned value r = 1 nm.

Nanomechanics Science and Technology: An International Journal

Structure of CaCO3 Nanocrystals 255

We remind that the energy calculations for reaction (1) and the construction of
corresponding curves in Fig. 1 were made when the Gibbs energy for CO2 was re-
calculated from the tabular pressure P0 = 1 atm to the partial pressure P = 0.1 Pa.
It is clear that for other partial pressures of CO2 we obtain other graphs in Fig. 1.
However, the size of a critical nucleus, at which the probability of generation of
aragonite and calcite phases is equal, remains unchanged. The probabilities of ho-
mogeneous generation of these phases will change; however, it does not change
the preferred generation of one phase as compared with the other. Thus, the con-
clusions on the phase of crystals generated in the aqueous bulk and on the solid
surface are common and do not depend on the reaction conditions. This is con-
firmed by the graph in Fig. 2.
In this analysis, we did not allow for possible difference in the density of the
surface energy σ(r) of aragonite and calcite. From expression (14) it can be con-
cluded that the "neutral" value of the radius (correspondent to the equiprobable
generation of phases ∆GC = ∆GA) of the critical nucleus will shift towards its
smaller values, if the surface energy σA of aragonite is higher than that of calcite
σC. If the relationship is opposite, σA < σC, the "neutral" value of the critical nu-
cleus radius will shift towards higher values.

8. FIELD OF APPLICATION OF THE RESULT OBTAINED

8.1 Situation in the Absence of Magnetic Treatment of Water

It should be noted that in the case of reaction (1) and the generation of CaCO3
crystal in water at a constant temperature and pressure, the system’s Gibbs energy
decreases by ∆G, but the reaction (further release of the solid phase) will not con-
tinue until the so-called critical nucleus radius r is generated (see (9)) with the
positive Gibbs energy equal to

4πσ ⎛ 2σ (r) M ⎞ 2
G = (16)
3 ⎜⎜ C ⎟⎟
.
⎜ RTρ ln
C0 ⎟
⎝ ⎠

In terms of thermodynamics, the shift of the Gibbs energy towards higher posi-
tive values is a fluctuation, whose probability f decreases exponentially with in-
crease of

⎛ − G Na ⎞
f  exp ⎜ ⎟. (17)
⎝ RT ⎠
Calculations based on formulas (16)–(17) demonstrate that reaction (1) can hardly
occur in the aqueous bulk due to the smallness of f. For instance, at the concen-
tration C = 0.33 mole/m3, corresponding to the equilibrium concentration of the

Volume 7, Issue 3, 2016

256 Koshoridze & Levin

nucleus with r = 1 nm (Fig. 1, curve 3), the probabilities of aragonite and calcite
generation are extremely low, equaling to fa  fc  e−26, respectively [even given
the fact that, according to (15), the surface tension at the solid body–water bound-
ary for nanonuclei becomes smaller than for micronuclei, i.e., of the order of
σ = 0.064 J/m2 (Koshoridze and Levin, 2013, 2014a–d)].
Thus, the results obtained refer to a negligibly small amount of substance, i.e.,
to critical nuclei generated during homogenous generation in the aqueous bulk with
a very low probability. Therefore, the molecules of the dissolved CaCO3 salt will
be crystallized from the supersaturated aqueous solution mostly on the channel
walls due to the process of heterogeneous crystal generation.
As regards the causes of the observed effect, i.e., deposition of calcite modifica-
tion on the heat exchanger walls, it was noted in (Prisyazhnyuk, 2003) that scale
formation on the surface of heat exchanging equipment is, by its physical and
chemical nature, a process of crystallization on the solid surface. The driving force
and the primary cause of the process is supersaturation, i.e., the excess of the ac-
tual concentration of the crystallized salt over its solubility under the given ther-
modynamic conditions. The kinetics of crystallization depends on the magnitude of
crystallographic mismatch between the crystallized salt and the surface. In the case
of crystallization, the parameters of crystalline lattices of the surface materials and
of the crystallized substance should not differ by more than 20% (the threshold
value of crystallographic mismatch is 0.20). The smaller the crystallographic mis-
match, the more intensely the surface initiates the generation of nuclei of the crys-
tallized substance and the smaller the supersaturation at which this process occurs.
Since water always contains dissolved oxygen and carbon dioxide, iron oxide and
iron carbonate (siderite) are generated after contact with the steel surface of the
heat exchanger. Crystallographic mismatch of iron oxide/calcite crystals is 0.027,
and that of siderite/calcite is 0.054. Crystallographic mismatch of aragonite is sub-
stantially higher, and is of about 0.191.
Since aragonite has crystallographic mismatch with siderite which is 3.5 times
higher than that of calcite, the latter crystalline structure will be crystallized with
a higher probability on the steel surface of the heat exchanger. In addition, arago-
nite has comparatively low values of adhesion to steel and cohesion between the
crystals. Therefore, the probability of formation and retention of the aragonite crys-
tal on the heat exchanger wall is lower than that of calcite. In this case, following
crystallization on the steel surface, aragonite will be carried away by the liquid
flow in the form of individual crystals because of lower values of adhesion. There-
fore, under normal conditions, the main structure that is crystallized on the heat
exchange surface and is strongly adhered to it is calcite.

8.2 Situation in the Presence of Magnetic Treatment of Water

It may seem that the significance of the obtained results, i.e., the specific features
of homogeneous generation of nuclei, is rather low for analysis of scale formation

Nanomechanics Science and Technology: An International Journal

Structure of CaCO3 Nanocrystals 257

in a practical situation. However, these results are of paramount importance in ana-

lyzing the devices using magnetic treatment of the water flow in order to decrease
the formation of scale. The fact is that during magnetic treatment of water accord-
ing to the Derjaguin–Landau–Vervey–Overbeek (DLVO) theory (Koshoridze and
Levin, 2014c), the double electrical layer of critical nuclei (colloidal particles) is
deformed. This provokes their accelerated coagulation and facilitates the decrease
of concentration of these nuclei in the supersaturated aqueous solution. This, in
turn, accelerates the process of homogeneous generation of the crystalline phase in
the aqueous bulk taking into account the need to maintain thermodynamic charac-
teristics of the solution in stable external conditions. In this case, the number of
crystals, suspended in the aqueous bulk, increases in avalanche, and their area in-
creases compared to the channel surface. Accordingly, the process of crystallization
of the dissolved CaCO3 molecules switches from the channel wall to the surface of
suspended particles. Such decrease of scale on the walls of the heat exchanging
units during their operation is known as the effect of magnetic treatment of water.
When the crystallization process moves into the aqueous bulk, the problems of ho-
mogeneous generation of critical nuclei come to the foreground. The thing is that
the structure of crystals, generated in water, may affect the properties of deposi-
tions on the channel wall and define its heat transfer efficiency. The crystals of
calcite, deposited on the wall, form a dense scale, which is difficult to be removed
and which reduces the heating capacity of the heat exchanger. Aragonite generates
loose deposition on the wall that can be carried away by the water flow, thereby
facilitating self-cleaning of heat transfer surfaces and increasing its operation effi-
ciency. In this situation, the previously obtained results are important for under-
standing the essence of antiscaling efficiency of magnetic treatment of the water
flow, supersaturated with hardness salts, such as CaCO3. Thus, it is possible to as-
sert that the reduction of scale by magnetic treatment of the water flow occurs be-
cause at this time the crystallization processes (generation of a solid phase in the
supersaturated solution) begins in the aqueous bulk, rather than on the wall.
It is quite evident that at the initial stage of the solid phase generation particles
of the smallest sizes are formed, knowingly less than 1 nm. As it was shown
above, the crystalline form of such nuclei is mostly represented by the aragonite
structure. With a further enlargement of the primary nuclei due to crystallization
on them of dissolved CaCO3 molecules, it is natural that the support structure of
aragonite remains. As mentioned before, smaller adhesion of aragonite to the wall
surface and its loose dendrite structure are the factors that decrease the scale on
the surface of hydraulic channels and ensure antiscaling efficiency of magnetic
treatment of water.

9. CONCLUSIONS

An analysis of the thermodynamics of CaCO3 phase transition in a supersaturated

aqueous solution allowed explaining, for the first time, the generation of scale on

Volume 7, Issue 3, 2016

258 Koshoridze & Levin

the channel wall in the form of calcite. This is confirmed by the fact that in the
pair of curves 1 in Fig. 1 the curve correspondent to calcite lies below the curve
for aragonite. This curve is obtained by parallel shift of the curve for aragonite
downwards for a fixed value, i.e., it does not depend on the solution concentration.
Such predisposition to generation of calcite is also noted for crystals of radius
r > 1 nm suspended in the water bulk. At r = 1 nm, both phases have equal prob-
abilities of homogeneous generation. At r < 1 nm, critical nuclei are generated in
the form of aragonite instead of calcite.
It is shown that the conclusion on the equal probability of generation of the said
structures for the critical nucleus size r = 1 nm is common for the result of the
crystallization reaction (1) which does not depend on the conditions of this reac-
tion, for instance, on the partial pressure of CO2. This fully confirms the important
conclusion of this work that, in the case of homogeneous generation of CaCO3
crystals in the supersaturated aqueous solution aragonite is formed, since the initial
phase of crystal nucleus generation has the dimensions that are much smaller than
1 nm, comparable to the dimensions of the molecules. During the subsequent
growth of crystals caused by the fact that it absorbs the dissolved molecules this
structure retains up to the sizes of the critical nucleus, having about 70 molecules
in our case.
This analysis explains the efficiency of magnetic treatment of water in order to
decrease the formation of scale in heat exchangers.
It is also of interest to note that the formation of scale crystals on the walls and
in the aqueous bulk is an obvious and easily tangible macroscaling effect. How-
ever, it was found that the causes of the observed effect are closely related to the
properties and behavior of nanosized objects.

REFERENCES
Cefalas, A.C., Kobe, S., Drazic, G., Sarantopoulou, A., Kollia, Z., Strazistar, J., and Meden, A.,
Nanocrystallization of CaCO3 at solid/liquid interfaces, Appl. Surface Sci., vol. 254, no. 21,
pp. 6715–6724, 2008.
Dean, J.A. (Ed.), Lange’s Handbook of Chemistry, 16th ed., New York: McGraw-Hill, Inc., 1999.
https://www.mineralienatlas.de/index.php
Koshoridze, S.I. and Levin, Yu.K., Determining the range of dimensions of nanomechanics objects,
Nanomech. Sci. Technol.: An Int. J., vol. 5, issue 2, pp. 141–151, 2014a.
Koshoridze, S.I. and Levin, Yu.K., Effect of magnetic field on coagulation of nanosized colloidal
particles, Pisma Zh. Tekh. Fiz., vol. 40, issue 16, pp. 80–87, 2014b.
Koshoridze, S.I. and Levin, Yu.K., Model of scale deposition with magnetic water treatment, Nanomech.
Sci. Technol.: An Int. J., vol. 5, issue 1, pp. 51–71, 2014c.
Koshoridze, S.I. and Levin, Yu.K., The mechanism of scaling decrease in magnetic treatment of
water in heat energy installations, Teploenergetika, no. 3, pp. 74–77, 2013.
Koshoridze, S.I. and Levin, Yu.K., Z-potential of colloidal nanoparticles as a function of magnetic
treatment time and temperature, Nanomech. Sci. Technol.: An Int. J., vol. 5, issue 3, pp. 169–179,
2014d.

Nanomechanics Science and Technology: An International Journal

 Structure of CaCO3 Nanocrystals 259

Levin, Yu.K., Generation of aragonite nanocrystals in a magnetized water flow, Nanomech. Sci. Tech-
nol.: An Int. J., vol. 5, issue 1, pp. 23–31, 2014.
Prisyazhnyuk, V.A., Physical and chemical principles of prevention of salt crystallization on the heat
exchange surfaces, Santekhnika. Otoplenie. Konditsionirovanie (S.O.K), no. 10, pp. 26–30, 2003.

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