Accepted Manuscript

The velocity dependence of viscosity of flowing water

Ke Ni, Hongwei Fang, Zhiwu Yu, Zhaosheng Fan

PII: S0167-7322(18)35968-3
DOI: https://doi.org/10.1016/j.molliq.2019.01.055
Reference: MOLLIQ 10286
To appear in: Journal of Molecular Liquids
Received date: 16 November 2018
Revised date: 8 January 2019
Accepted date: 10 January 2019

Please cite this article as: Ke Ni, Hongwei Fang, Zhiwu Yu, Zhaosheng Fan , The
velocity dependence of viscosity of flowing water. Molliq (2019), https://doi.org/10.1016/
j.molliq.2019.01.055

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 ACCEPTED MANUSCRIPT

The velocity dependence of viscosity of flowing

water
Ke Nia, Hongwei Fanga,*, Zhiwu Yub, Zhaosheng Fanb

a
State Key Laboratory of Hydro-science and Engineering, Department of Hydraulic
Engineering, Tsinghua University, Beijing 100084, China
b
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry

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of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China

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ABSTRACT

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As one of the fundamental physical properties of pure liquids, viscosity is considered to be
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dependent on pressure and temperature only. In this work, we design an infrared spectroscopy
experiment for flowing water. By relating the viscosity of water with the wavenumber of
oxygen-hydrogen (O-H) stretching vibration, we found clear velocity dependence of viscosity,
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which is different from conventional understanding. A relationship between velocity and viscosity
is developed, and the probable reasons for this phenomenon is discussed.
Keywords: viscosity; velocity; flowing water; hydrogen bonds
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1. Introduction
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As the most ubiquitous fluid on the earth, water plays a vital role in many chemical and
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biological reactions, as well as in the transportation processes of mass and energy [1-5]. It is well
accepted that viscosity, which is originated by the intermolecular forces, determines the fate of
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water transportation [6, 7]. Experiments on the viscosity of water show that temperature [7, 8] and
pressure [7] are the only parameters that change the magnitude of viscosity. Some theories based
on chemical reaction rates [9-11] are proposed to fit the Arrhenius-type behavior of the
temperature dependence of viscosity, if the break of hydrogen bonds are treated as a process of
breaking of covalent bonds. As one of the typical thermodynamic transport coefficients, viscosity
is usually studied using molecular simulations [12-16] based on Green-Kubo equation.
As a matter of fact, the standard equipment [17, 18] for measuring viscosity is only
appropriate for static water or flow regime of low Reynolds number leading to the commonly-used
assumption that viscosity remains constant under different flow regime [19-21]. Simulations of
turbulent flow from microscopic view usually assume that the flow velocity has no effects on the

*
Corresponding author.
E-mail address: fanghw@tsinghua.edu.cn (HW Fang).
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molecular fluctuation. Fei et al [22] and Fan and Ching [23] introduced an information velocity for
large amount of molecules to calculate macroscopic quantities and a molecular velocity for
calculating the motion trail of molecules. These two kinds of velocity do not affect each other.
Komatsu et al [24] used a Gaussian distribution for determining the particle momentum and the
macroscopic velocity was only position-dependent. In the numerical simulations of large eddies,
turbulent viscosity is always introduced empirically in place of viscosity mentioned above to
decrease the computational cost [25-27]. Although no specific physical significance of turbulent
viscosity is given [28], it can be used to present the connections between different scales of eddies
and produces good results sometimes [29, 30]. We wonder whether the viscosity of liquid water
really changes in turbulent regime.

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Hydrogen bonds dominate the intermolecular forces in liquid water [31, 32], and the viscosity
of liquid water is greatly related to the structural configuration of hydrogen bonding network [33,

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34]. Therefore, detecting the information of hydrogen bonds can help us reveal the regularity of
viscosity. Different methods are utilized to detect the structural information of water. Vibration

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spectroscopy, including infrared [35] and Raman [36], has been used to probe the structure of
hydrogen bonds. X-ray scattering measurement provides information on the radial distribution
function of oxygen-oxygen atoms [37], while neutron diffraction experiments supplement the
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X-ray scattering data with information on the radial distribution functions of H-H and H-O atoms
[38]. In infrared spectrometer, the absorption cell for liquid water should be thinner than several
microns due to the strong absorption of light by water [39, 40]. Therefore, most spectroscopic
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studies on liquid water are focused on static water sample [40, 41]or flows at nanoscale [42, 43].
To the best of our knowledge, little work has so far been done on the viscosity of water under
flow regime of high Reynolds number due to the limitation of experimental measurements, while
the viscous force dominates the flow process in the viscous layer [22, 44, 45]. In this work, we
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improved the absorption cell for infrared spectroscopy and made it possible to obtain the
information of hydrogen bonds in turbulent flow. Then, we analyzed the velocity dependence of
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water viscosity according to the relationship between hydrogen bonds and viscosity [46], which
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we have discussed in details in our previous paper. We further discussed the probable reasons for
this phenomenon.
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2. Materials and Methods

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2.1. Experiment setup

The absorption cell consists of a polytetrafluoroethylene chamber (40mm×10mm×10mm)

and CaF2 windows, as shown in Figure 1 (a). Since the absorption cell is thicker than the common
cell used in infrared (IR) spectroscopy, carbon tetrachloride (CCl4) is chosen as solvent due to its
relatively low absorption of infrared ray in the intermediate infrared range. In order to dissolve
water into CCl4, some amount of acetone was added into the solvent. The final matching for the
three liquid is 500 mL CCl4, 4 mL acetone and 100 uL water.
The absorption cell was connected by a chemically-stable flexible pipe with a beaker, which
was filled with solution sample. A WT600 peristaltic pump (Baoding, China) were used to

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produce different flow regime. The range of flow rate of the peristaltic pump is 300-3000 mL/min
and the inner diameter of the flexible pipe is 6.4 mm. The schematic of the designed equipment is
shown in Figure 1 (b).
A PerkinElmer Frontier spectrometer (MA, USA), equipped with a general ATR sampling
accessory were used to record IR spectra. The IR spectra data were collected at 4 cm-1 resolution
with 16 scans in the range from 4000 to 2500 cm-1. A light source with continuous wavelength is
used in infrared spectroscopy. Since the vibrational energy level of atoms in a molecule is
quantized, light with specific wavenumbers will be absorbed when the transition between different
vibrational energy levels happens. Therefore, absorption peaks or valleys emerge at the position
corresponding to the wavenumbers in spectrograms (if the vertical coordinate represents

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absorbance, there will be absorption peaks and if the vertical coordinate represents transmittance,
there will be absorption valleys). Transitions between vibrational energy levels are always

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accompanied with transitions between rotational energy levels, which have much smaller energy
gaps compared with vibrational energy level transitions. Theoretically, there should be many

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linearly and isometrically arranged peaks or valleys. As the resolution of the spectroscopy
decreases, those peaks or valleys connect with each other and form an absorption band [47].
The indoor temperature is taken approximately as the temperature of the liquid. When we
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start the experiment at 273K, an open foam box containing mixed ice and liquid water is put
outside the beaker flask to keep the temperature of the inside liquids. At other two temperatures,
we put a thermometer into the beaker flask to monitor the temperature of the liquids and shorten
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the experiment time to possibly get results at constant temperature.

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Fig. 1. Experimental setup with flowing water: (a) The plan view of the chamber and (b) The
schematic of the equipment

2.2. Flow regime conversion

Reynolds number Re is commonly used to ascertain the flow regime and is given by
Re  ul /  (1)
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where u is characteristic velocity, l is characteristic length and ν is coefficient of kinetic viscosity.

It is commonly considered that the flow regime is laminar flow when the value of Re does not
exceed 2300. In our experiment, we choose the height of the chamber as the characteristic length.
The velocity can be calculated as

u  Q /  d 2 / 4  (2)

where Q is the discharge of the flow that is shown on the peristaltic pump, and d is the inner
diameter of the flexible pipe.

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2.3. Detection of hydrogen bonds

The temperature dependence of viscosity for still water has already been adequately

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discussed before. It has been established that the viscosity of a liquid is dominated by
intermolecular forces. For liquid water, the strength of hydrogen bonds is about 10~40 kJ/mol,

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while the strength of van der Waals force is about 1 kJ/mol. Therefore the strength of hydrogen
bonds is an order higher than van der Waals force in liquid water [48]. Thus, it can be concluded
that the viscosity of water is dominated by hydrogen bonds. Stretching vibration is the
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directionally periodic motion of atoms along the valence bonds. Since the oxygen-hydrogen (O-H)
bond stretching vibration and librations of hydrogen bonds are always coupled in water molecules,
we assume that there is a linear relation between the two vibration modes [23]. In our previous
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study, we developed a relationship between viscosity and hydrogen bonds of water, indicating that
viscosity might be proportional to the change of activated energy of the breaking of hydrogen
bonds.
Here, we use the results of O-H bond stretching vibration, instead of librations of hydrogen
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bonds, to correlate the temperature dependence of viscosity.

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3. Results and discussion

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In order to investigate the temperature and velocity dependence of water viscosity, we

conducted several sets of experiments under different temperature and velocity. The temperatures
are 273, 285 and 296 K, while the velocity is from 0 to 2000 ml/min with an interval of 400
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ml/min. As for the viscosity of liquid, we used the results of previous experiments [49].

3.1. The IR result of the mixed liquids

The IR results of the mixed liquids (measured at 296K) and pure liquids (measured at 298K)
are shown in Figure 2. In pure water, the wave number of O-H stretching vibration mode is from
2800 to 3800 cm-1. In this range, there is only one sharp valley (centered at about 3424 cm-1) in
pure acetone, which corresponds to the overtone vibration mode of C=O in acetone, while no
valley is found in pure CCl4. In the mixed liquids, there are some valleys around 3500cm-1. There
is a relatively broader valley at about 3527 and we cannot relate this valley with any one in pure
acetone, therefore we treat this valley as the signal of the O-H stretching vibration in water.
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Fig. 2. The FTIR results of the mixed and pure liquids: (a) carbon tetrachloride (b) acetone (c)
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water (d) mixed liquid

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3.2. Temperature dependence of O-H stretching vibration mode

We reviewed the viscosity of still water for the three temperatures, and the results are shown
in Figure 3. More details are listed in Table 1.

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Fig. 3. The relationship between viscosity and wave number of O-H stretching of water

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The results suggest that the viscosity of liquid water can be linearly related to the wave
number of O-H stretching vibration mode under different temperatures, thus related to hydrogen
bonds. The coefficient of determination (R-squared) is 0.9996. The relationship between the
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wavenumber of O-H stretching vibration and viscosity of liquid water is shown in equation (1),
  0.0264w  94.227 (1)
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where ν is the viscosity of liquid water, in 10 Pa·s, and w is the wavenumber of O-H stretching
vibration, in cm-1.
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The similar tendency of the two properties agrees well with the theory that we proposed
before, indicating that the temperature dependence of viscosity might be well reflected by the
wave number of O-H stretching vibration.
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Table 1. The viscosity[49] and wave number of still water for three temperatures
Wave number Viscosity
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Temperature (T/K)
(w/cm-1) （υ/10-3Pa·s）
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273 3494.98 1.792

285 3516.47 1.236
296 3527.23 0.936
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3.3. Velocity dependence of O-H stretching vibration mode

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The results in Figure 4 show the variation of O-H stretching vibration mode under different
flow velocities. Since the viscosity is linearly related to the O-H stretching vibration mode, the
results may be considered as proof that the viscosity of water really changes if the flow regime
changes. We used Reynolds number, instead of the charge of flow, as the horizontal axis to specify
the influence of the flow regime on the viscosity of water. The conversion between Reynolds
number and charge of flow is as follows.

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Fig. 4. The viscosity of liquid water at the various temperatures under different flow regimes
(solid circles correspond to T = 273K; solid triangles correspond to T= 285K and solid diamond
corresponds to T=296K)
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There is a maximum point in each curve of specific temperature in Figure 4. At 285K and
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296K, the flow regime under which the maximum point is reached corresponds to the dividing
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point (Re≈2000) of laminar flow and turbulent flow.

In laminar flow regime, the increment of flow velocity makes water molecules more
organized, resulting in the more packed structure of water clusters and lower wave number of O-H
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stretching vibration. With the strengthening of hydrogen bonds, the viscosity increases.
When it comes to turbulent flow regime, the fluctuation of flow becomes significant, and the
energy barrier of a water molecule to its neighboring site might decrease, resulting in lower
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viscosity.
We also find that the difference of viscosity under different flow regimes is more significant
at lower temperature. The viscosity changes about 10% from laminar flow to turbulent flow at
273K.

4. Conclusion

We designed a special absorption cell to detect the FTIR signal of flowing water under
different temperatures and found the velocity dependence of the viscosity of liquid water. In this
study, we validate the linear relationship between viscosity and stretching vibration of O-H bond,
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and compare the Reynolds number corresponding to the critical point of the wave number with the
critical Reynolds number. The results show that the hydrogen bonds change with velocity and
make the difference to viscosity as well. The viscosity difference between laminar flow and
turbulent flow can be up to 10% of the total value of viscosity. Some simulations based on
microscopic theory are needed to further explain this phenomenon. In addition, no effective
method for temperature controlling was used in our experiments, especially at 285K and 296K, so
we may take consideration of an effective attachment for temperature controlling to get more
detailed information under denser temperature gradients in our further research.

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Acknowledgements

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This work was supported by the National Natural Science Foundation of China (No.
91647210), National Key Research and Development Program of China (No. 2016YFC0402406),

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and the 111 Project (No. B18031).
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Highlights:
 An infrared spectroscopy experiment is designed for obtaining information of
flowing water.
 Clear velocity dependence of viscosity is found, which is different from
conventional understanding.
 A relationship between velocity and viscosity is developed.

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