Wat. Res. Vol. 32, No. 10, pp.

3188±3191, 1998
# 1998 Elsevier Science Ltd. All rights reserved
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TECHNICAL NOTE

NEW RAPID TEST FOR EVALUATION OF SCALE

INHIBITORS
I. DRELA*, P. FALEWICZ and S. KUCZKOWSKA
Laboratory of Technical Electrochemistry and Corrosion, Technical University of Wroclaw,
Wyb. St. Wyspianskiego 27, 50-370 Wroclaw, Poland

(First received July 1997; accepted in revised form February 1998)

AbstractÐA new method of evaluation of scale inhibitors eciency has been developed and tested.
This method is based upon solution conductivity measurement. It consists of determining a supersatura-
tion level of any scale forming compound in a given water, at de®ned conditions, in the presence of a
speci®ed amount of scale inhibitor and also without inhibitor. This method allows the stabilizing fea-
tures of compounds under investigation to be di€erentiated. With this method the eciency of prevent-
ing CaCO3 precipitation from aqueous solutions was determined for three phosphonate compounds
which are e€ective as corrosion inhibitors of mild steel in neutral water: 2-phosphonobutane-1,2,4-tri-
carboxylic acid (TBTC), ethylenediaminetetramethylenephosphonic acid (EDTMP) and phosphono-N-
methylenephosphonic derivative of polycaproamide (PMPP). It was ascertained that the above com-
pounds are e€ective in preventing CaCO3 crystallization from water. EDTMP showed the best stabiliz-
ing properties and PBTC what poorer ones. # 1998 Elsevier Science Ltd. All rights reserved

Key wordsÐscale inhibitors, water stabilization, phosphonate compounds, conductivity

INTRODUCTION At present, research concerning water stabiliz-

Precipitation and scale deposition present an im- ation which is to lower the tendency to evolve pre-
portant problem in operating water cooling and cipitates, focuses on physical and chemical methods.
heating installations. Deposits formed may cause Physical methods include water treatment in mag-
severe crevice corrosion attack, growth of microor- netic or electric ®elds and by using sonic waves
(Limpert and Raber, 1985). Chemical methods are
ganisms and may deteriorate conditions of the heat
methods consisting of adding small amounts (i.e. at
exchange (Bond, 1990).
a level of grams per 1 m3) of agents into water.
Enormous progress in science and technology,
Those agents are usually composed of organic com-
made in the area of new technics and apparatus, is
pounds. Chemical methods are more versatile, as
often bound up with intensi®cation of heat
they o€er more possibilities for ecient water treat-
exchange processes in chemical industries, metal-
ment over a wider variety such as water parameters
lurgy, power industry, etc. Traditional methods of
and technical speci®cations of operating systems.
water treatment for industrial purposes (®ltration,
Crystallization results from three processes which
coagulation, decarbonization, outgassing, ion
interact mutually: supersaturation, nucleation and
exchange) have become more and more expensive
crystal growth. Water stabilizing chemicals (e.g.
due to the general degradation of the environment
complexones) may in¯uence each of these processes.
and also are often of low e€ectiveness. By prevent-
There is a lack of references as to the mechanism of
ing precipitation and deposition on exchange sur-
crystallization inhibition of sparingly soluble salts
faces intensi®cation of the heat exchange may be
by using complexones. In one of the few articles
obtained. Any e€ective means of water stabilization
concerning these problems (Tomson and Matly,
would allow the use of natural water of lower qual-
1989) nucleation of CaCO3, CaSO4 and BaSO4
ity and/or reused water and would lead to a re-
under in¯uence of complexone types like phospho-
duction of water consumption because of the
nates and polyacrylates were presented. Based on
possibility of concentrating it signi®cantly in circu- analyses of the di€usion rate into crystal being in
lation systems. the nucleation stage, two ways of a€ecting crystal
nucleation, i.e. increasing supersaturation and
*Author to whom all correspondence should be addressed. decreasing interfacial tension, were presented. A rel-
3188
 Technical Note
evant equation describing this process was pro-
posed. That equation was veri®ed experimentally
afterwards. Complex forming of these compounds
together with cations present in water impedes
supersaturation and in this way reduces the rate of
nucleation and crystal growth (Zielinski, 1981).
Even if a complete water stabilization does not
appear at given conditions, the presence of these
compounds causes suspended solids to dispergate
and to liquefy through adsorption, which changes
the structure and properties of scale. Deposits
which are being formed are better dispergated and
of lower hardness as adhesion of individual par-
ticles is weak.
In reports from the last few years several organic
compounds, which have the properties mentioned
above, have been introduced. These compounds
have been used to stabilize water. Compounds of
the class of phosphonate-, aminoalkylphosphonate-,
polycarboxypolyphosphonate-complexones and also
light molecular weight acryl- and aminoacryl-poly-
mers have been mentioned the most frequently
(Marshall, 1987; Marshall and Germann, 1987;
Tomson and Matly, 1989).
Published data and our own previous research
(Kubicki et al., 1989, 1995; Falewicz and
Kuczkowska, 1992) point out that chemical water
treatment using phosphonate complexones o€ers a
good possibility of stabilizing water together with
reduction of its corrosivity.
Laboratory research of water stabilization usually
includes only qualitative evaluation of stabilizing
properties of a given substance under de®ned con-
ditions (Amjad, 1989). This evaluation does not
allow determination of the quantitative relation-
ships between the concentration of a stabilizing
agent and the stabilization e€ectiveness of the
agent. That is why the authors of this paper devel-
oped an original test method of complexone proper-
ties to stabilize water. The new test is described in
Section 2.
Nucleation is the ®rst step of precipitation. The
homogenous nucleation rate is a€ected by the
degree of supersaturation (S) which is de®ned as a
ratio of the crystallizing substance concentration to
the concentration of saturation (solubility).
Although nuclei formation is possible at each super-
saturation (S>1), its rate increases rapidly only
when a speci®c value of the supersaturation is being
exceeded, i.e. at a critical supersaturation. The
nucleation rate is almost zero below this value. For
most compounds which crystallize from aqueous
solution the critical degree of supersaturation is
very high and reaches a value of 102±103. The
quantity of the critical degree of supersaturation
reached is especially important in water systems
where the problem of precipitation and deposit
forming often exists. Calcium carbonate and sulfate
are main scale compounds in most types of usable
water. In this paper the in¯uence of chosen phos-
3189
phonate compounds on the critical degree of super-
saturation for only calcium carbonate in water is
presented. This new test uses conductivity measure-
ments while calcium carbonate is being precipitated
from calcium chloride solution by addition of
sodium carbonate.
Based on many tests, it was ascertained that
using 0.1 M CaCl2 as a titrated solution and 0.1 M
Na2CO3 as the titrating solution was the most con-
venient set of solutions.
MATERIALS AND METHODS
The test setup, presented in Fig. 1, consists of a test cell
thermostated and provided with conductivity sensor and
magnetic stirrer. This setup includes also the CC-551
microcomputer conductivity meter (Elmetron) and the U-1
thermostat (MLW PruÈfgeraÈte-Werk).
The tests consisted of putting 60 cm3 of bi-distilled
water, 3 cm3 of 0.1 M CaCl2 and a variable amount of
phosphonate compounds in the thermostated vessel of
100 cm3 in volume. Then, the conductivity sensor was
installed and after the temperature stabilized at
2520.18C, the solution was titrated by using 0.1 M
Na2CO3. The titrating solution was added in portions of
0.2 cm3 each. The conductivity value was read after 1 min
of stabilizing. Solutions being tested were stirred at con-
stant intensity with a magnetic stirrer during measure-
ments. Before each titration the vessel, the sensor and the
stirrer were washed with 1 M H2SO4 and bi-distilled water
to remove all traces of deposits which could become crys-
tal nuclei while the measurements were being carried out.
The results obtained are presented as a diagram of the sol-
ution conductivity vs the volume of the titrating agent
added, from which the initial point of the precipitation
was determined.
The following phosphonate compounds were selected to
test their abilities to inhibit CaCO3 precipitation process
in aqueous solutions. These compounds are e€ective in
preventing the corrosion of steel in water environment at
neutral pH:
. 2-Phosphonobutane-1,2,4-tricarboxylic acid (PBTC):
HOOC±CH2 ±CH2 ±C…COOH †…PO3 H2 †±CH2 ±COOH
. Ethylenediaminetetramethylenephosphonic acid
(EDTMP):
…H2 PO3 ±CH2 †2 ±N±…CH2 †2 ±N±…CH2 PO3 H2 †2
. Phosphono-N-methylenephosphonic derivative of
polycaproamide (PMPP):
Fig. 1. Experimental setup for measurement of CaCO3
supersaturation.
3190 Technical Note
ÿ‰±…CH2 †5 ±N…CH2 PO3 H2 †±CO±…CH2 †5
±NH±C…PO3 H2 †2 ±Šn ÿ
All agents used in the tests were of p.a. purity grade
except PMPP which had been synthesized in the labora-
tory from substrates of p.a. purity grade.
RESULTS AND DISCUSSION
The diagram in Fig. 2 is an example of a titration
of the solution containing scale inhibitor. Three lin-
ear segments with increasing slope may be distin-
guished there. At the point of intersection of the
straight lines I and II, solution opalescence was
usually noticed. However, even after waiting a long
time within the second segment (1.4 to 2.8 cm3
0.1 M Na2CO3) no precipitation occurred. The
value of the last point on the straight line II
(arrow-marked one, which relates to the value of
2.8 cm3 of 0.1 M Na2CO3) was taken as the bound-
ary concentration of the titrating agent, which
caused the initiation of CaCO3 precipitation. At the
volume of the titrating agent, represented by the
value of 3.0 cm3 on the diagram, a deviation from
the linear relationship appears and a rapid precipi-
tation begins, from which a rapid decrease of the
conductivity results within a few minutes. Further
titration shows a linear relationship to the concen-
tration again but with an increased slope (line III in
Fig. 2). The relationship between the solution con-
ductivity and the concentration of the precipitating
agent described above only occurs with the presence
of complexones. In the case where the solution con-
tains only CaCl2 with no complexones, there is no
2nd segment, which means solution opalescence and
precipitation appear simultaneously.
Values for the degree of supersaturation
measured for solutions containing phosphonate
compounds were compared to the supersaturation
obtained at similar conditions but without the ad-
dition of the phosphonates. So the values for the
degree of supersaturation in the following are rela-
tive ones (Sr) expressed as a ratio of the supersa-
turation of CaCO3 in the presence of a
Fig. 2. Titration diagram for the solution containing
2 mmol/dm3 PBTC.
Fig. 3. Dependence of degree of water supersaturation
with CaCO3 (Sr) on concentration of phosphonate com-
pounds.
phosphonate compound (Sp), to the value of the
supersaturation under the same conditions for
water alone (S0):
Sp
Sr ˆ
S0
In calculations, both the dilution of phosphonate
compounds and deposit forming ion concentrations
caused by variable critical values of the titrating
agent were taken into account. In the case of the
water solution containing 60 cm3 of distilled water
and 3 cm3 of 0.1 M CaCl2 and without any ad-
ditions, 0.6 cm3 of 0.1 M Na2CO3 was consumed
before opalescence occurred. So the ionic product
of the CaCO3 precipitation at these conditions may
be calculated as follows:
Ð Volume of the solution when turbidity ®rst
occurs, 6.36  10ÿ2 dm3.
Ð Calcium ion concentration ([Ca2+]), 4.71 
10ÿ3 M.
Ð Carbonate ion concentration ([CO2ÿ 3 ]), 9.43 
ÿ4
10 M.
‰Ca2‡ Š  ‰CO2ÿ
3 Š ˆ 4:44  10
ÿ6
From the handbook of physical chemistry the
ionic product of CaCO3 at 258C is 4.8  10ÿ9, so
the value of its supersaturation under test con-
ditions (S0) is 925.
Dependence of the relative degree of supersatura-
tion of CaCO3 in the water solution (Sr) on concen-
trations of the three phosphonate compounds
selected is presented in Fig. 3. It appears from Fig. 3
that in the case of EDTMP and PBTC, the relative
degree of supersaturation of CaCO3, equal to 3.7, is
possible to achieve even at small concentrations of
these agents in water (up to 5 mmol/dm3). A further
increase in concentration, however, causes a smaller
increase in the relative supersaturation. Better
results are obtained using EDTMP than PBTC. The
highest supersaturation, 7 times higher than for
water alone, was obtained for EDTMP but at a
relatively high concentration in water (47 mmol/
 Technical Note
dm3). It is apparent that increasing the EDTMP
concentration 10 times, i.e. from 5 to 50 mmol/dm3,
only allows the degree of supersaturation to double.
As for PMPP, which is the most e€ective in pre-
venting corrosion of the mild steel in neutral water,
its anti-scale properties are much worse than the
other two. So, at the concentration of 10 mmol/dm3,
the supersaturation obtained for PMPP is over 2
times lower than for EDTMP and PBTC.
Taking the supersaturation acquired into account
and also the costs of using anti-scale compounds,
the values of 5 to 10 mmol/dm3 for EDTMP and
PBTC, which correspond to 2.2±4.4 and 1.4±
2.7 mg/dm3, respectively, are optimal concentrations
for gaining a satisfactory stabilizing e€ect.
CONCLUSIONS
The following conclusions can be drawn from the
conducted investigations:
. A new method for evaluation of the e€ective-
ness of scale inhibitors was presented, which allows
their stabilizing properties to be distinguished
quickly and selectively.
. With this method one may determine a quanti-
tative relationship between scale inhibitor concen-
tration and relative supersaturation of scale forming
compounds.
. Small concentrations of EDTMP (2.2 mg/dm3)
and of PBTC (1.4 mg/dm3) give a considerable rela-
tive supersaturation of CaCO3 in water, 3.7 times,
and at higher concentrations of EDTMP (22 mg/
dm3) relative supersaturation may exceed 7 times.
. Results obtained with this method have con-
®rmed known and very good anti-scaling properties
of EDTMP and PBTC.
3191
AcknowledgementÐThe authors thank the State
Committee for Scienti®c Research (grant 3T09B09208) for
supporting this research.
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