Chinese Journal of Chemistry, 2009, 27, 1249—1253 Full Paper

Novel Synthesis of β-FeOOH Nanofluid and Determination of

Its Heat Capacity by an Adiabatic Calorimeter
,a b b
NAN, Zhaodong* (南照东) ZHANG, Pingping (张平平) YU, Aijun (于爱军)
a c c
WEI, Chengzhen (魏成振) SHI, Quan (史权) TAN, Zhicheng (谭志诚)
a
College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China
b
College of Chemical Science, Qufu Normal University, Qufu, Shandong 273165, China
c
Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian, Liaoning 116023, China

A novel and facile method for preparation of stable nanofluid is introduced, in which FeCl3•6H2O and urea were
used as reactants without any surfactants. The obtained solid sample was proved to be β-FeOOH by XRD technol-
ogy and spindle-shaped by TEM technology. The coexisting NH3 molecules may be the main reason for the stable
nanofluid. The weak bonding between nitrogen and iron atoms would be formed. The investigation on the excess
heat capacity of the obtained nanofluid sustains this opinion. The heat capacities of the obtained β-FeOOH particles
and the nanofluid were determined by an adiabatic calorimeter. And these obtained results will help the applications
of β-FeOOH and the nanofluid to industry, and the establishment of the model of thermal conductivity of nanofluid.
The thermodynamic properties of the obtained β-FeOOH particles and the nanofluid were calculated based on the
obtained functions of heat capacity with respective to thermodynamic temperature and the relationships between the
thermodynamic properties.

Keywords nanofluid, β-FeOOH, heat capacity, thermodynamic property, adiabatic calorimetry

Introduction of temperature is a source of important information

Nanofluids, produced by dispersing nanoparticles
into conventional heat transfer fluids such as water,
glycol, or oil, were coined by Choi in 1995 at Argonne
National Laboratory of USA and large enhancements of
up to more than 100% in effective thermal conductivity
of such fluids have been reported.1 The promising pros-
pect for nanofluids triggered many researchers to inves-
tigate on the best combination of particles and sol-
vents2-8 and to elucidate the governing mechanisms9-14
as well. However, the thermodynamic properties on
nanofluids have not been reported as we know. The lack
of thermodynamic properties on nanofluids should
block the application of this kind of high conductivity
medium. At the same time, the investigation on their
thermodynamic properties will help to elucidate the
mechanism of conductivity. And the heat capacity of
nanofluids will need to be determined for the estab-
lished conductivity model of nanofluids.15 Heat capacity
is one of the more valuable thermophysical quantities to
be considered when studying pure liquids and liquid
mixtures. Accurate values are needed in many areas of
physics, chemistry, and chemical engineering for estab-
lishing energy balances, obtaining entropy and enthalpy
values, or for studying phase transitions. Moreover, as-
certainment of the heat capacity of liquids as a function
concerning their molecular structure and is essential for
checking the efficiency of estimation models used in
industry.16
In this study, β-FeOOH nanofluid was synthesized
through a facile and template-free method. The heat
capacities of the nanofluid and β-FeOOH were deter-
mined by using an adiabatic calorimeter, which is
thought to be one of the most accurate methods to de-
termine heat capacity of sample. The thermodynamic
properties of the nanofluid and β-FeOOH were given.
Experimental
Experimental materials
All the chemicals, including urea, and FeCl3•6H2O
were of the analytical grade and used without further
purification. Doubly deionized water was used as the
solvent.
Synthesis procedure
In a typical synthesis of nanofluid, 3 mmol of
FeCl3•6H2O and 0.5 mmol of urea were solved in 50
mL of doubly deionized water. The aqueous solution
was put into a Teflon-lined stainless-steal autoclave,
which was maintained at 80 ℃ for 5 h, and subse-

* E-mail: zdnan@ yzu.edu.cn

Received September 14, 2008; revised January 10, 2009; accepted March 9, 2009.
Project supported by the National Natural Science Foundation of China (No. 20753002).

© 2009 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1250 Chin. J. Chem., 2009, Vol. 27, No. 7 NAN et al.

quently cooled down to room temperature. The color of

the solution changed from red-brown to yellow. No pre-
cipitation was found. The yellow nanofluid was ob-
tained, which was stable for more than three weeks. The
solid sample was obtained by centrifuging the nanofluid
and washing several times with distilled water and al-
cohol, respectively.
Characterization
Transmission electron microscopy (TEM) images
were taken on a JEM-2000EX transmission electron
microscope. The patterns of XRD were recorded on a
Rigaku D/MAX-XA powder X-ray diffraction meter Figure 2 XRD pattern of the obtained solid sample.
with Cu Kα radiation (λ＝1.5405 Å) at a scanning rate
－
of 0.1 s 1. Scanning electron microscopy (SEM) images without any urea, while the other experimental condi-
were taken with a JEOL JSM-6700FXIB scanning elec- tions were the same as given in experimental part. No
tron microscope, fitted with a field emission source and stable nanofluid was obtained and yellow sediments
working at an accelerating voltage of 20 kV. were found when the experiment was over. The SEM
A precision automatic adiabatic calorimeter was image of the obtained sediments is shown in Figure 3.
used to measure heat capacities of the compound over The obtained results demonstrate that the coagulation of
the temperature range 290 K≤T≤400 K. The calo- solid particles was fabricated without urea as reactant.
rimeter was established in the Thermochemistry Labo- The hydrolysis of urea in aqueous solutions was widely
ratory of Dalian Institute of Chemical Physics, Chinese investigated.20,21
Academy of Sciences, China. The principle and struc-
ture of the adiabatic calorimeter were described in detail
elsewhere.17,18
The solid sample mass used for calorimetric meas-
urements was 1.2151 g, which was equal to 0.01368
－
mol in terms of its molar mass, M＝88.858 g•mol 1.
The liquid sample volume used for calorimetric meas-
urements was about 40 mL.

Results and discussion

Figure 3 SEM image of the obtained solid sample in the ab-
Fabrication of stable nanofluid sence of urea in the reaction system.
Figure 1 gives the TEM image of the obtained solid
sample. The results show that the obtained particle is CO(NH2)2 → NH3＋HNCO → NH＋
4 ＋NCO
－
(1)
dispersed and spindle-like with about 15—30 nm in
width and 90—140 nm in length. The XRD pattern is NCO－＋OH－＋H2O → NH3＋ CO32- (2)
shown in Figure 2. In comparison with their standard
JCPDS files, Figure 2 can be indexed as β-FeOOH. The The hydrolysis of FeCl3 in the reaction system may
as-obtained solid particles have similar shape with the take the following procedure:
reference reported.19
In order to elucidate the effects of urea on the ob- Fe3＋＋2H2O → β-FeOOH＋3H＋ (3)
tained solid sample, β-FeOOH was also synthesized
NH3＋H＋  NH＋
4 (4)

CO32－ ＋H  HCO－
＋
3 (5)

HCO－
3 ＋H  H2CO3
＋
(6)

NH＋4 ion was proved to exist in the fluid by chemi-

Figure 1 TEM image of the as-obtained solid particles dis-
persed in the fluid.
cal analysis. The nucleation number of β-FeOOH may
become greater than that without the assistance of urea,
so that the particle size of β-FeOOH may be smaller.
The particle size of the obtained β-FeOOH in the
present work is smaller than that reported in reference.19
It is easy for nanoparticles to coagulate and difficult to
disperse in water due to the high surface energy

© 2009 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
β-FeOOH Chin. J. Chem., 2009 Vol. 27 No. 7 1251

of nanoparticles. Therefore, controlling the coagulation

of nanoparticles in the nanofluid has become the pri-
mary issue for the initial research of nanofluid. It is also
important to investigate the stability of nanofluids in
order to exploit their potential benefits and applications.
Why was the stable fluid obtained by the assistance of
urea? The interaction between iron atoms and nitrogen
atoms would be formed as shown in Figure 4. The
formed weak bonding between Fe and N atoms may be
the main reason for the stable nanofluid. The similar
results were reported for Au nanoparticles capped by
amino acid.22
Figure 6 Molar heat capacities of the obtained nanofluid (●)
and liquid (○) samples.

the obtained β-FeOOH and nanofluid samples from 290

to 340 K.
For the obtained β-FeOOH sample:
Cp,m ＝0.9014X4 ＋1.342X3 ＋1.0066X2 ＋4.3478X＋
89.80 (7)
－ －
where Cp,m is molar heat capacity (J•K 1•mol 1), X＝(T
－ 316.63)/23.88, and T thermodynamic temperature.
Figure 4 Schematics of the interaction between iron and nitro- The correlation coefficient for the fitting is R2＝0.9997.
gen atoms in the nanofluid. For the obtained nanofluid sample:
Heat capacity of the nanofluid
Cp,m＝0.0017X4＋0.0107X3－0.0269X2＋0.0467X＋
The heat capacities of the fabricated solid, nanofluid
77.10 (8)
and liquid samples were determined by the adiabatic
calorimeter, while the liquid sample was obtained by where X ＝ (T － 309.54)/15.70, T is thermodynamic
removal of the solid sample from the nanofluid. The temperature. The correlation coefficient for the fitting is
results are shown in Figures 5 and 6. Figure 5 shows R2＝0.9998.
that the molar heat capacity of the obtained β-FeOOH The molar heat capacities of the obtained β-FeOOH
increases with experimental temperature increase. The and nanofluid samples from 290 to 340 K are listed in
molar heat capacity of β-FeOOH has not been reported Tables 1 and 2, respectively, at 5 K intervals.
as we know. Figure 6 shows that the molar heat capacity The excess molar heat capacity for the obtained
of the nanofluid is greater than that of the liquid sample nanofluid was calculated by using the following equa-
at the same experimental temperature. The molar heat tion:
capacities of the obtained nanofluid and liquid samples
do not change significantly with experimental tempera- Table 1 Thermodynamic properties of the obtained β–FeOOH
ture increase. The functions of the molar heat capacities
Cp,m/ (HT—H298.15)/ (ST—S298.15)/
with the experimental temperature were established for T/K
(J•K－1•mol－1) (kJ•mol－1) (kJ•K－1•mol－1)
290 85.73 －399.2 －1.357
295 86.29 －157.3 －0.5304
300 87.02 94.17 0.3149
305 87.81 355.4 1.178
310 88.64 626.6 2.060
315 89.50 908.1 2.961
320 90.43 1200 3.881
325 91.51 1502 4.819
330 92.87 1816 5.777
335 94.66 2141 6.753
340 97.10 2477 7.750
298.15 86.74 0 0
Figure 5 Molar heat capacity of the obtained solid sample at
different experimental temperatures.

© 2009 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1252 Chin. J. Chem., 2009, Vol. 27, No. 7 NAN et al.

Table 2 Thermodynamic properties of the obtained nanofluid of the excess heat capacity were about a constant (ca.
－ －
Cp,m/ (HT—H298.15)/ (ST—S298.15)/ 0.22 J•K 1•mol 1). The results show that the coagula-
T/K
(J•K－1•mol－1) (kJ•mol－1) (kJ•K－1•mol－1) tion of the obtained β-FeOOH particles would not be
290 76.98 －0.6277 －2.135 enhanced during the experimental temperature range
295 77.03 －0.2427 －0.8182
from 315 to 340 K. The stable nanofluid has been ob-
tained during this temperature range.
300 77.06 0.1426 0.4766
305 77.08 0.5279 1.750 Thermodynamic properties of the obtained nan-
310 77.10 0.9134 3.004
ofluid
315 77.11 1.299 4.238 The thermodynamic properties of the obtained
β-FeOOH particles and nanofluid were calculated based
320 77.12 1.684 5.452
on the Eqs. (7) and (8), and the relationships between
325 77.13 2.070 6.648 thermodynamic properties. The results of thermody-
330 77.14 2.456 7.826 namic functions ΔH298.15＝HT－H298.15 and ΔS298.15＝ST
335 77.16 2.842 8.986 －S298.15 are listed in Tables 1 and 2, respectively. The
340 77.19 3.227 10.13 values of ΔS298.15 increase as the temperature increases
298.15 77.05 0 0 for the two systems. These values show that the mole-
cules of the samples become more active at higher tem-
perature.
C pE,m ＝Cp,m－xCp,m,1－(1－x)Cp,m,2 (9)
Conclusion
where Cp,m,1 and Cp,m,2 are the molar heat capacities for
the obtained β-FeOOH and liquid samples, respectively, A novel and facile method for preparation of stable
and Cp,m is the molar heat capacity of the obtained nan- nanofluid is introduced. The stable mechanism of the
ofluid at the mole fraction of the β-FeOOH x. The re- nanofluid is given. The coexisting NH3 molecules may
sults are shown in Figure 7. The larger the C pE,m , the be the main reason for the stable nanofluid. The weak
more different the interaction between the molecules in bonding between nitrogen and iron atoms would be
the system. Positive C pE,m indicates more structures in formed. The investigation on the excess heat capacity of
the solution.23 The data of the excess molar heat capaci- the obtained nanofluid sustains this opinion. The inter-
ties of the obtained nanofluid are all positive between action between Fe and N atoms became weaker when
290 and 340 K as shown in Figure 7. The positive C pE,m the experimental temperature was increased. However,
data demonstrate that interactions between β-FeOOH the obtained nanofluid in the present work was still sta-
and the liquid are formed, which would be the weak ble. The determined heat capacities of the obtained
bonding between Fe and N atoms. The data of the ex- β-FeOOH particles and nanofluid will help the applica-
cess heat capacity are decreased with the experimental tions of β-FeOOH and the nanofluid to industry, and the
temperature increasing from 290 to about 315 K. The establishment of the model of thermal conductivity of
Brownian motion of the dispersed β-FeOOH particles in nanofluid. At the same time, the present investigation on
the fluid was enhanced when the experimental tempera- the excess heat capacity of nanofluid introduces a kind
ture was increasing. The coagulation of the particles of method to study the change of the stableness of the
would be formed. The interaction between the dispersed nanofluid with the change of the experimental tempera-
β-FeOOH and the liquid became weaker. Thus, the data ture.
of the excess heat capacity became smaller. However,
no precipitation was found. When the experimental References
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(E0809142 Lu, Y.; Lu, Z.)

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