Journal of Molecular Structure 938 (2009) 15–19

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

The effects of magnetic fields on water molecular hydrogen bonds

Ran Cai, Hongwei Yang *, Jinsong He, Wanpeng Zhu
Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, the experimental results on the effects of a magnetic field on water are reported. Purified
Received 3 June 2009 water was circulated at a constant flow rate in a magnetic field. After this treatment, the physicochemical
Received in revised form 27 August 2009 properties of water were changed, shown as the decrease of surface tension and the increase of viscosity
Accepted 27 August 2009
over the treatment time. The water is more stable by magnetic treatment with less molecular energy and
Available online 2 September 2009
more activation energy, as shown from the calculation based on the results. The correlation time sc was
calculated in terms of spin–lattice relaxation time of proton NMR, which verified that the rotational
Keywords:
motions got slow down after magnetic treatments. A two-phase model was set up to prove that the pro-
Magnetic field
Hydrogen bond
portion of free water molecules was reduced. The results suggested that the average size of water clusters
Water molecule became larger by magnetic treatments.
Water cluster Ó 2009 Elsevier B.V. All rights reserved.
NMR

1. Introduction
The magnetic treatment has remained a controversial process
for industrial and domestic water treatment for over 50 years [1].
This type of physical treatment helps to prevent the use of chem-
icals such as polyphosphates or corrosive substances that are
expensive and can be harmful to human life or disruptive to the
environment. Independent review of the performance of the mag-
netic treatment has been highly controversial, while the increase in
the number of commercial magnetic treatment devices might
seem to be an indicator of the effectiveness of magnetic fields in
the water processing. Many claims have been made that magnetic
fields (MFs) change the physicochemical properties of water, or
prepared laboratory solutions [2,3], by influencing pH value,
nucleation and growth, surface tension and chemical equilibria.
Tombácz et al. have tested both flowing and static systems, and
concluded that only in a flowing system is the magnetic effect
observed [4]. The magnetic flux density ranges from 0.1 to 0.8 T
among those magnetic treatment experiments. Kobe et al. took
0.5 T as the magnetic flux density in their experiments to obtain
successful treatment results [5]. Chang and Weng investigated
the effects of the MF on the hydrogen-bonded structure of water
and found that the number of hydrogen bonds increased by
approximately 0.34% when the MF strength increased from 1 to
10 T [6]. This is consistent with the findings of Hosoda et al. who
suggested that the enhancement in the hydrogen-bonded strength
under the MF of 10 T was caused by increased electron delocaliza-
tion in the hydrogen-bonded molecules [7]. The magnetic induc-
* Corresponding author. Tel.: +86 106 277 2987; fax: +86 106 277 2987.
E-mail address: yanghw@tsinghua.edu.cn (H. Yang).
tion and the exposure time are paid much attention as magnetic
treatment parameters, while the fluid velocity exerts no significant
influence [8].
The most commonly raised criticism about magnetic water
treatment revolves around the low reproducibility of the results
[8], especially those reported in various industrial studies. And
the fact that the mechanism through which magnetic fields exert
the influences on the processes of scaling and the characteristics
of scaling compounds is as yet not adequately explained.
Most works on the mechanism concentrated on how magnetic
treatments influenced the solutes or substances in water, espe-
cially on antiscaling and crystallisation. And many mechanisms
developed focus on the effects of magnetic fields on the ions in
water. But as a matter of fact, the magnetic treatment also had
an impact on water molecules themselves. On the other hand,
the change of water molecular structure could also work on aque-
ous solutes in turn.
Basically, various properties of water or aqueous solution have a
very close connection with the structure of water molecules. Liquid
water forms a continuous network of hydrogen bonds because its
molecules have two donors and two acceptor sites. The presence
of spatial network of hydrogen bonds is the main property of liquid
water [9]. Many models for the structure of liquid water have been
suggested, most of which are represented by the continuum (uni-
form) models and the mixture (cluster) models [10]. In general,
cluster models describe liquid water as an equilibrium mixture
of species which are distinguishable in an instantaneous picture.
For many years they have been used to explain the properties of
water and aqueous solutions. Most cluster models assume that
water molecules exist in a few (often two) classes of more or less
well-defined structural entities [11,12]. For a two-entity model, it

0022-2860/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2009.08.037
16 R. Cai et al. / Journal of Molecular Structure 938 (2009) 15–19

implies a hydrogen bond forming and breaking equilibrium [13]. In
recent years, the frequently used methods for water molecular
structure include Raman scattering, infrared spectrum, X-ray, neu-
tron scattering and NMR [12,14–18].
Although there has been a lot of study on liquid water structure,
few works focus on the change of water itself by magnetic treat-
ments. The study of water molecules will provide a possibility
for the mechanism of magnetic treatments on scaling and
crystallization.
In this work, we study the impact that magnetic treatment ex-
erts on water microstructure using proton NMR spectroscopy. The
magnetic water treatment was used to examine the effects on the
physicochemical properties (surface tension and viscosity) of
water passing through a magnetic field orthogonally in circulation,
and determine the formation or reorientation of hydrogen bonds
and the restructure of water cluster based on the change of water
intermolecular energy. Finally, the present data demonstrated the
variation of the mean size of water clusters after magnetic
treatments.
2. Material and methods
2.1. Magnetization
The water used in this study was high-level purified water,
which was produced by a Milli-Q Millipore System (Milli-Q Advan-
tage A10) and had a resistivity of about 18.2 MX, 298 K. The total
organic carbon and dissolved oxygen of the water were below
0.05 mg/L and 5.0 mg/L, respectively.
The stationary magnetic field was generated by an adjustable
permanent magnet (KC-70C) manufactured by Shanghai Jieling
Magnetic & Devices Co., Ltd, China. The permanent magnet is sin-
tered NdFeB with the maximum magnetic flux density as 1000
(±10%) mT and the effective magnetic flux area is 26  75 mm.
The adjustable magnetic flux density ranges from 10 to 1000
(±10%) mT.
A certain volume (V) of purified water was circulated in a close
loop from a thermostatic closed glass tank through a perspex tub-
ing (section area s=0.07 cm2, total length 150 cm) owing to a peri-
staltic pump. The flow rate was settled around 1 m/s. A part of the
tubing (l=7.5 cm) was inserted between the polar pieces of the
magnetic device, which was the length of the MF. This length can
be doubled by passing twice the pipe between the polar pieces.
The magnetic induction density was tuned at 0.50 T, which was
measured by a digital teslameter (HT100, Ningbo Bestway Magnet
Co., Ltd., China). The effective magnetic treatment time (teff ) was
directly proportional to the frequency of water going through the
MF vertically.
The total time of operation tT was between 3 and 40 h. In this
configuration, t eff as the time of exposure of water to the MF is
chemical rinsing to always obtain the same roughness and
cleanliness.
2.3. Measurement of viscosity
The rheological measurements were carried on a commercially
available Modular Compact Rheometer (PHYSICA MCR300, Paar
Physica, Germany) with a double gap cylinder (DG 26.7) for viscos-
ity measurements. All measurements were performed at 298 K.
2.4. Measurement of 1H-NMR
NMR relaxation measurements were performed on a Bruker
Avance DRX-400 spectrometer (Bruker Instrument, Inc., Billerica,
MA) operating at a proton resonance frequency of 400 MHz. All
measurements were performed at 298 K. The temperature was
controlled with an accuracy of ±0.5 K. A 5 mm diameter NMR sam-
ple tube was used with a capillary tube filled with deuteroxide ap-
plied for the frequency lock. High-resolution 1H NMR spectra of
solutions were recorded using a BBO probe.
The classical inversion-recovery method using 180°–s–90°
pulse sequence was performed to determine T 1 . There repetition
delay (RD) was chosen to be at least ten times T 1 . Maximum ampli-
tude values (A) from the longitudinal relaxation curves were re-
corded at 24 variable delay times (s) ranging from 500 s to 1.5 s.
The 90° pulse width (PW) was 11.5–11.6 s. Eight scans were ac-
quired for each measurement. T 1 was calculated according to the
following equation to fit the s vs. A data.
  
s
A ¼ A0 1  exp  ð2Þ
T1
2.5. Statistical analysis
Statistical analysis was performed using the DeltaGraph, Ver-
sion 5 package for Mac (SPSS Inc., USA). In order to visualize the re-
sults from multiple experiments, the average values and standard
deviations were analyzed on three measurements with different
samples.
3. Results
3.1. Effects of magnetic field on the surface tension of water
The surface tension of water over treatment time through the
MF was measured as an important physicochemical index to show
whether the structure of water was changed by a MF. A surface
74
Surface tension (mN/m)

0.04
independent of the flow rate: 72

70
sl 0.00
t eff ¼ tT ð1Þ
V 68
/EAInner
0

66 -0.04
ΔE Inner
A

2.2. Measurement of surface tension 64

-0.08
Water surface tension was measured by the plate method 62
(Krüss K12 tension meter, Krüss Gmbh, Hamburg Germany). The 60 -0.12
measuring precision of the tension meter was 0.01 mN/m. The 0 2 4 6 8 10 12 14
immersion velocity was fixed at 6 mm/min. The measurements
Effective treatment time (min)
were carried out at a room temperature of 298 K and at an RH level
of 40–50%. The platinum sheet ((20  10  0.2) mm3 in radial, tan- Fig. 1. The effect of MF on the surface tension ( ) and the relative variation of
gential, and longitudinal direction, respectively) was prepared by molecular energy EInner
A (DEInner
A =EInner
A0 , ) of water.
 R. Cai et al. / Journal of Molecular Structure 938 (2009) 15–19 17

energy is equivalent to a surface tension or line tension. As shown 1.20

in Fig. 1, the surface tension of magnetic water decreased sharply
with the effective treatment time ranged from 1 min to 13 min. 1.18

Viscosity (mPa•s)
And it got a minimum surface tension around 9% down at the point 1.16
of 13 min.
The surface tension of a liquid is a reflection of the energy of the 1.14
liquid. The dependence of surface tensions and cohesive energy on
1.12
the molecular interaction is illustrated as the following Eq. [19]:
wAA z 1.10
DE ¼ ESurface
A ¼ EInner
A ¼ m ð3Þ
2 1.08
where DE is the energy required to transport one molecule from the
1.06
inner to the surface, ESurface
A is the energy per molecule present at the
liquid–air surface, EInner
A is the cohesive energy per molecule in the 0 2 4 6 8 10 12 14
inner liquid, wAA is a negative quantity signifying the attraction en- Effective treatment time (min)
ergy between the molecules, z is the number of neighbors and the
fraction of nearest neighbors in a plane above, respectively below Fig. 2. The effect of MF on the viscosity of water.
this plane is m.
DE in Eq. (3), assuming if scaled by the cross-sectional area per
molecule (aA ), is equal to the surface energy, where entropic con- was, the more viscous water was (Fig. 2) from our experimental re-
tributions are ignored, and equal to the surface free energy or sults. A more than 10% increase was found at the 13 min point.
the surface tension [19]: Based on the Eq. (6) the activation energy E was also raised up
when the water viscosity increased, which indicated that it
DE wAA EInner m required more energy to create a hole to receive a molecule. For
cA ¼ ¼ zm ¼ A ð4Þ
aA 2aA aA a very large of liquids including water [20]
And then the relative variation rate of EInner
A is equal to the relative E  ð0:3—0:4ÞL; ð9Þ
variation rate of cA :
cA  cA0 EInner where L is the latent heat of vaporization. The magnetized water
DcA
¼ ¼ AInner ð5Þ needed more energy to vaporize in terms of Eq. (9). And it was
cA0 cA0 EA0 embodied directly that DE=E0 ascended with the effective magnetic
The declination of the surface tension cA indicated the decrease treatment time in Fig. 3. The energy for vaporization is primarily ap-
of molecular energy EInner from Eq. (4). It was also reflected in Fig. 1. plied to break up the hydrogen bonds. So it can be deduced that
A
According to these, it could be inferred that the inner structure of new hydrogen bonds were formed during the magnetic processes
water turned to be more stable with less molecular energy EInner , which led to the higher latent heat of vaporization.
A
which verified that new hydrogen bonds were formed during the
magnetic treatment processes. 3.3. 1H-NMR relaxation of magnetized water

3.2. Effects of magnetic field on the viscosity of water The proton spin–lattice relaxation time T 1 is approximately re-
lated to the viscosity g. The relationship [21]
Viscosity is another basic physicochemical parameter of water,
which was measured simultaneously with surface tension in the T 1 / T=g / expðE=RTÞ; ð10Þ
same experiments. According to the Eyring theory of liquid viscos-
ity [20], the dependence of liquid viscosity g and the molar activa- with a common activation energy E is expected to hold provided the
tion energy E is demonstrated in Eq. (6): rotational and translational motions are controlled by a single ki-
  netic process.
hN A E Assuming that there are two components as ‘‘free” water mole-
g¼ exp ; ð6Þ
Vm RT cules and ‘‘hydrogen-bonded” ones, a two-phase model is set up
and then with the equilibrium [21]:

DE ¼ RTðln g  ln g0 Þ; ð7Þ
0.030
DE ln g  ln g0
¼ : ð8Þ 0.025
E0 ln g0  ln hN
V
A
m

where h is Planck’s constant, NA Avogadro’s number, V m the volume 0.020

ΔΕ/ Ε 0

per mole of the liquid, and the temperature was kept at 298 K.
Eyring suggests that in order to transpose a molecule from one po- 0.015
sition to another against the attractive forces of neighbors it has to
0.010
surmount a potential energy barrier, and E is the molar activation
energy for the barrier.
0.005
The barrier energy E may also be regarded as the energy to cre-
ate a hole in the liquid big enough to receive a molecule. This 0.000
ought, therefore, to be comparable with the latent heat of vapori- 0 2 4 6 8 10 12 14
zation; however, because there is already some free volume in Effective treatment time (min)
the liquid, the work to open up a molecular hole is less than this.
It was suggested that the longer the magnetic treatment time Fig. 3. The effect of MF on the relative variation of activation energy E of water.
18 R. Cai et al. / Journal of Molecular Structure 938 (2009) 15–19

H2 Oð\hydrogen-bonded"Þ
H2 Oð\free"Þ
k4
ð11Þ 160
k3

140
K ¼ k4 =k3 ¼ ½H2 Oð\free"Þ=½H2 Oð\hydrogen-bonded"Þ ð12Þ
120

τc (ps)
and define k2 as the rotation rate of ‘‘free” water molecule and k1 as
the rotation rate of a water molecule in a cluster lattice site. For the
100
case where the rate of chemical or phase exchange is faster relative
to the rotation rate, i.e., k3 and k4  k1 and k2 , it turns to be 80
1 1 1 k3 þ k4
1=T 1 / ½ þ ¼  : ð13Þ 60
k2 k2 K k2 k4
We specified c as the proportion of free water molecules 0 2 4 6 8 10 12 14
k4 Effective treatment time (min)
c¼ / T1; ð14Þ
k3 þ k4
Fig. 5. The effect of MF on the molecular correlation time sc of water.
and
Dc c  c0 T  ðT 1 Þ0 magnetic treatment. The slower rotation motion indicated the
¼ ¼ ð15Þ
c0 c0 ðT 1 Þ0 strengthening of hydrogen bonds.

Then Dc0c was taken as an indicator to represent the relative var-

iation of free water molecules proportion and the converted extent
from free water molecules to water clusters relative to purified
water without magnetic treatment. The Dc0c over effective treatment
time was calculated in terms of the proton spin–lattice relaxation
time. As shown in Fig. 4, the proportion of free molecules relative
to initial state declined, which indicated that more water mole-
cules converted to form clusters via hydrogen bonds when the
magnetic treatment time extended.
Meanwhile, for rotational motions, which is necessary to con-
sider for intramolecular dipole–dipole interactions, the expression
for the proton spin–lattice relaxation time becomes [22]
2
1 2c4 h IðI þ 1Þ sc 4sc
¼ ð þ Þ;
T1 5r 6 1 þ x20 s2c 1 þ 4x20 s2c
where c is magnetogyric ratio, 
h is Planck’s constant, I is spin quan-
tum number, r is the distance of the two hydrogen atoms of one
water molecule in our case, x0 is resonance frequency in radians
per second, and sc is molecular correlation time. The value of sc
can be calculated according to Eq. (16) (calculation software, Maple
Version 12.0). And sc can be denoted as the ‘‘average” time between
molecular clusters for a molecule in some state of motion. It is also
be interpreted as the average time for one molecule rotating per
radian. So the smaller sc is, the faster the molecule rotates. As
shown in Fig. 5, the value of sc had an obvious ascending while
the magnetic treatment time expanded. It suggested that the
rotational motions of water molecules turned to be slow down by
-0.26
-0.28
-0.30
-0.32
Δc/c0
4. Discussion
4.1. Mechanism of magnetization of water
Many claims have been made that magnetic fields change the
physicochemical properties of water [2,23]. Our experimental re-
sults verified again that magnetic treatments have changed some
properties of water. The surface tension was decreased (Fig. 1)
while the viscosity was increased over the magnetic treatment
time (Fig. 2). But still the principle of magnetic water treatment ef-
fects is still not well understood and various contradictory hypoth-
eses were proposed. From the microscopic point of view, the
magnetic field was shown to influence significantly the zeta poten-
ð16Þ
tial and size distribution of the particles formed in solution [24]. It
was often attributed to the Lorentz forces ~ v ~
F ¼ q:~ B exerted
either on moving ions or on charged solid particles [25]. Madsen
suggested that the magnetic field had influenced the proton spin
[26].
The crystalline state of ice is a hexagonal structure, in which a
unit lattice is made up of five molecules. Many experiments veri-
fied that ice crystals exhibit considerable electrical conductivity
and these molecules are arranged orderly as a great number of
hydrogen-bonded chains in ice crystals [27,28]. Pang et al. inferred
that the closed hydrogen-bonded chains of molecules still existed
in water after the first-order phase transition from ice crystals to
water [29]. According to this theory, the closed chains of proton
conductivity exposed to an externally applied MF just like some
‘‘molecular electric currents” or ‘‘small magnets” in a MF. The
external MF exerts Lorentz forces on these ‘‘molecular electric cur-
rents”, and they can interact with each other, thus the liquid water
could be magnetized.
In all, the magnetization of water was caused by proton transfer
in the closed hydrogen-bonded chains based on the theory of pro-
ton conductivity in the hydrogen-bonded chains in ice. Hence, this

-0.34 theory could be hypothesized as a reasonable mechanism of how

magnetic treatments influence water molecules and change the
-0.36
molecular energy.
-0.38
-0.40 4.2. Impact of magnetization on water molecular energy and cluster
structure
-0.42
0 2 4 6 8 10 12 14
Basically, the effect magnetization exerted on water derives
Effective treatment time (min)
from the change of water molecular energy. FerreuxFerreux et al.
Fig. 4. The effect of MF on the relative variation of the proportion of free water has proposed that a magnetic term be involved with the activation
molecules. energy, which allows the critical radius of nucleation to be lowered
 R. Cai et al. / Journal of Molecular Structure 938 (2009) 15–19 19

[30]. In terms of our experimental results the water intramolecular sults suggested that more hydrogen bonds were formed and the
energy decreased (Fig. 1) while the activation energy was en- mean size of water clusters got larger by magnetic treatments.
hanced (Fig. 3) through magnetic treatments. Meanwhile the tem-
perature dependence of sc may be expressed with good accuracy in Acknowledgements
the usual form [22]
We wish to thank the National Natural Science Foundation of
sc ¼ s0 expðEa =RTÞ; ð17Þ
China (Grant No. 50608046) for the opportunity to do the resulting
where Ea is the activation energy for reorientation of the hydroxyl, T research. We would also thank that staff at Tsinghua University for
is temperature. It can be diagnosed from Eq. (17) that Ea goes up making our research a pleasurable one. And, finally, we would like
when sc increases. According to our results, the correlation time to thank senior software engineer ZHENG Jianqiang for his data
sc was enhanced by magnetic treatments (Fig. 5). It proved again processing.
that the activation energy increased over the magnetic treatment
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