ARTICLE IN PRESS

Physica B 405 (2010) 2350–2355

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Physica B
journal homepage: www.elsevier.com/locate/physb

Thermodynamics and kinetics of the dehydration reaction of FePO4  2H2O

Banjong Boonchom a,, Spote Puttawong b
a
King Mongkut’s Institute of Technology Ladkrabang, Chumphon Campus, 17/1 M. 6 Pha Thiew District, Chumphon 86160, Thailand
b
Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand

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

Article history: The thermal decomposition kinetics of FePO4  2H2O in dynamical air atmosphere was studied by mean
Received 1 August 2009 TG–DTG–DTA. The stage and product of the thermal decomposition were determined. A number of
Received in revised form kinetic models and calculation procedures were used to determine the kinetic triplet and
18 February 2010
thermodynamic parameters characterizing the dehydration process. The obtained activation energy
Accepted 19 February 2010
and most kinetic model indicate the single kinetic mechanism and three-dimension diffusion as
‘‘Ginstling–Brounstein equation (D4 model)’’, respectively. The thermodynamic functions (DH*, DG* and
Keywords: DS*) of the dehydration reaction are calculated by the activated complex theory and indicate that the
Inorganic compounds process is non-spontaneous without connecting with the introduction of heat. The kinetic and
Thermogravimetric analysis (TGA)
thermodynamic results were satisfactory which present good correlation with a linear correlation
Non-isothermal kinetics
coefficient close to unit a low standard deviation.
Thermodynamic properties
& 2010 Elsevier B.V. All rights reserved.

1. Introduction the preparation of various metals and alloys, cements, ceramics,

Iron (III) phosphate, FePO4 has long been used in many fields such
as catalysts, wastewater purification systems, ferroelectrics, lithium
batteries and steel and glass industries [1]. It has recently been
proposed as the cathode in lithium batteries and lithium metal
phosphates can be used as cathode or anode electrodes in lithium
batteries because it is the next generation of positive-electrode
material for lithium batteries and offer additional advantages in
practical applications due to its lower cost, safety, benign environ-
mental properties, stability and low toxicity [2]. The existence of
several crystalline iron phosphate phases was reported in the
literatures: the orthorhombic heterosite FePO4, obtained from the
delithiated LiFePO4, the monoclinic FePO4, and the orthorhombic
FePO4, hydrated phases include the phosphosiderite (or metastren-
gite) FePO4  2H2O monoclinic and the FePO4  2H2O orthorhombic
forms [3–6]. The successful application of the required material
depends on the morphology and purity, which depend mainly on the
conditions of synthesis. Different synthetic routes have so far been
reported for synthesizing FePO4, LiFePO4 and some of the synthesis
conditions reported in the literature [5–7]. It is well known that FePO4
was prepared by many phases of FePO4  2H2O and FePO4  3H2O
precursors at high temperatures (4800 K) [5–7]. Consequently, the
mechanisms, kinetic and thermodynamic studies of thermal decom-
position reactions are needed in order to take advantage of this
potential, which is a beneficial effect on the manufacturing cost [8,9].
The results obtained can be directly applied in materials science for
glasses, enamels, glazes, polymer and composite materials because
the great variety of factors with diverse effects such as reconstruction
of solid state crystal lattices, formation and growth of new crystal-
lization nuclei, diffusion of gaseous reagents or reaction products,
materials heat conductance, static or dynamic character of the
environment, physical state of the reagents—dispersity, layer thick-
ness, specific area and porosity, type, amount and distribution of the
active centers on solid state surface, etc [5–8].
The aim of the present work is to study the mecha-
nisms, kinetics and thermodynamics of the decomposition of
FePO4  2H2O using TG–DTG–DTA. Non-isothermal kinetic of the
decomposition process of FePO4  2H2O was interpreted by the
Flynm–Wall–Ozawa (FWO) [9] and the Kissinger–Akahira–Sunose
(KAS) [10,11]. The possible conversion function has been
estimated using the Coats and Redfern method which gives the
best description of the studied decomposition process and allows
the calculation of reliable values of kinetic triplet parameter [12].
The thermodynamic (DH*, DS*, DG*) and kinetic (E, A, mechanism
and model) parameters of the decomposition reaction of
FePO4  2H2O have attracted the interest of thermodynamic and
kinetic scientists and are discussed for the first time.
2. Experimental
2.1. Synthesis and characterization

 Corresponding author. Tel.: + 66 7750 6422x4565; fax: + 66 7750 6411. FePO4  2H2O crystalline powder was synthesized by wet
E-mail addresses: kbbanjon@gmail.com, kbbanjon@kmitl.ac.th (B. Boonchom). chemistry method [1,2]. In this study, FePO4  2H2O was prepared

0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.02.046
 ARTICLE IN PRESS
B. Boonchom, S. Puttawong / Physica B 405 (2010) 2350–2355 2351

by precipitation from aqueous solution of FeCl3  6H2O and H3PO4 The FWO [9] and the KAS [10,11] methods are two representative
(86.4% w/w) at pH= 6.5 at the ‘‘precipitation end point’’, with ones of model-free, which are convenient to calculate the
ammonium hydroxide solution. During the synthesizing proce- activation energy. The activation energy (Ea) of the dehydration
dure, iron chloride was dissolved in distilled water followed by reaction of FePO4  2H2O can be calculated according to the FWO
adding an equivalent amount of the phosphoric acid (86.4% w/w) and the KAS equations.
with vigorous stirring at room temperature. Finally, the gel The FWO equation:
solution was obtained by adding 2 M ammonia solutions until pH    
AEa Ea
6.5. The white powder was isolated by filtration, then washed ln b ¼ ln 5:33051:0516 ð1Þ
RgðaÞ RT
with deionized water and dried in air for 24 h.
Thermal analysis measurements (thermogravimetry, TG; dif- The KAS equation:
ferential thermogravimetry, DTG; and differential thermal analy-      
b AEa Ea
sis, DTA) were carried out on a Pyris Diamond Perkin Elmer ln 2 ¼ ln  ð2Þ
T RgðaÞ RT
apparatus by increasing temperature from 323 to 1073 K with
calcined a-Al2O3 powder as the standard reference. The experi- where A (the pre-exponential factor) and E (the activation energy)
ments were carried out in air atmosphere at heating rates of 5, 10, are the Arrhenius parameters and R is the gas constant (8.314
Ra
15, and 20 K min  1. The sample mass was added about 6.0– J mol  1 K  1). The gðaÞ ¼ 0 fdðaaÞ is the integral form of the f(a), whi-
10.0 mg in an aluminum crucible without pressing. The structures ch is the reaction model that depends on the reaction mechanism.
of FePO4  2H2O and its final decomposition products (FePO4) were For one dehydration reaction of FePO4  2H2O, the estimation of
studied by X-ray powder diffraction using X-ray diffractometer kinetic function model can be turned into a multiple linear
(Phillips PW3040, The Netherland) with Cu Ka radiation regression problem through the Coats–Redfern method [12] as
(l = 0.1546 nm). The morphology of the selected resulting samples follows:
was examined by scanning electron microscope (SEM) using LEO           
SEM VP1450 after gold coating. The room temperature FTIR gðaÞ AR 2RT Ea AR Ea
ln ¼ ln 1  ffi ln  ð3Þ
spectra were recorded in the range of 4000–370 cm  1 with T2 bEa Ea RT bEa RT
8 scans on a Perkin-Elmer Spectrum GX FT-IR/FT-Raman spectro- Hence, ln(g(a)/T2) calculated for different a values at the single
meter with the resolution of 4 cm  1 using KBr pellets (KBr, Merck, b value on 1000/T must give rise to a single master straight line,
spectroscopy grade). so the activation energy and the pre-exponential factor can be
calculated from the slope and intercept through ordinary least
square estimation. The activation energy and the pre-exponential
2.2. Kinetics and thermodynamics factor can be calculated from the slope and intercept through
ordinary least square estimation, which combined with nine
Decomposition of crystal hydrates is a solid-state process of conversion functions (Table 1) with the best equation [13].
the type [13–16]: A (solid)-B (solid)+ C (gas). The kinetics of such Comparing the kinetic parameters from the Coats and Redfern
reactions is described by various equations taking into account equation, the probable kinetic model may be selected, where the
the special features of their mechanisms. The reaction can be values of Ea and A were calculated with the better linear
expressed through the temperatures corresponding to fixed correlation coefficient and the activation energies obtained from
values of the extent of conversion (a = (mi  ma)/(mi  mf), where the Coats and Redfern equation above were showing good
mi, ma and mf are the initial, actual and final sample mass at agreement to those obtained from the KAS and the Ozawa
moment time, t) from experiments at different heating rates (b). methods with a better correlation coefficient (r2). Hence, the

Table 1
Algebraic expressions of functions g(a) and f(a) and its corresponding mechanism [13,21].

No. Symbol Name of the function f(a) g(a) Rate-determination

mechanism

1. Chemical process of mechanism non-invoking equations

(1) F3/2 One and a haft order 2(1 a)3/2 [1 (1  a)  1/2  1] Chemical reaction
2. Sigmoid rate equations or random nucleation and subsequent growth
(2) A1, F1 Avrami-Erofeev equation (1 a)  ln(1 a) Assumed random
nucleation and its
subsequent growth, n=1
(3) A3/2 Avrami-Erofeev equation (3/2) (1  a)[ ln(1  a)]1/3 [  ln(1  a)]2/3 Assumed random
nucleation and its
subsequent growth, n=1.5
3. Deceleratory rate equations
3.1. Phase boundary reaction
(4) R3, F2/3 Power law 3(1 a)2/3 [1 ln(1  a)]1/3 Contracting volume
(spherical symmetry) or
two-thirds order
3.2. Based on the diffusion
(5) D1 Parabola law (a = kt1/2) 1/2a a2 One-dimension diffusion
(6) D2 Valensi equation [  ln(1  a)]  1 a + (1  a)ln(1  a) Two-dimension diffusion
(7) D3 Jander equation (3/2)(1  a)2/3/[ln(1 a)1/ [1 (1  a)1/3]2 Three-dimension diffusion
3
]
(8) D4 Ginstling–Brounstein (3/2)[(1 a)  1/3  1]  1 [1 (2/3)a  (1  a)2/3] Three-dimension diffusion
Equation
4/3  1/3 2
(9) D5 Zhuravlev Lesokhin (3/2)(1  a) / [(1  a)  1] Three-dimension diffusion
Tempelman Equation [1 (1  a)  1/3]
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2352 B. Boonchom, S. Puttawong / Physica B 405 (2010) 2350–2355
pre-exponential factor A can be obtained by calculating the
average value of A (s  1) from Eq. (3) for different heating rates.
The other kinetics parameters of the process can be calculated
using the fundamental theory of the activated complex theory
(transition state) of Eyring [17–21], the following general
equation may be written:
   
ewkB Tp DS
A¼ exp ð4Þ
h R
where A is the pre-exponential factor obtained from the Coats and
Redfern method; e= 2.7183 is the Neper number; w is the
transition factor, which is unity for monomolecular reactions; kB
is the Boltzmann constant; h is the Plank constant, and Tp is the
peak temperature of DTA curve. The change of the entropy may be
calculated according to the formula
 
Ah
DS ¼ R ln ð5Þ
ewkB Tp
Since
DH ¼ E RTp ð6Þ
where E* is the activation energy, Ea, obtained from the Coats–
Redfern method. The changes of the enthalpy DH* and Gibbs free
energy DG* for the activated complex formation from the reagent
can be calculated using the well-known thermodynamic equation
DG ¼ DH Tp DS ð7Þ
The heat of activation (DH*), entropy of activation (DS*), free
energy of activation decomposition (DG*) were calculated at T= Tp
(Tp is the DTA peak temperature at the corresponding stage), since
this temperature characterizes the highest rate of the process, and
therefore, is its important parameter.
3. Results and discussion
3.1. Characterization results
TG–DTG–DTA curves of the thermal decomposition of Fe-
PO4  2H2O at heating rate of 10 K min  1 are shown in Fig. 1. The
TG curve shows that the single well-defined decomposition step
relates to the eliminations of water in range of 348–523 K. The
corresponding observed mass loss is 20.27% by mass, which
corresponds to 2.10 mol of water and is close to the theoretical
value for FePO4  2H2O (19.27%, 2.00H2O). An endothermic effect
Fig. 1. TG–DTG–DTA curves of FePO4  2H2O in air at heating rate of 10 K min  1.
on DTA curves is observed at 398 K that agrees with the respective
DTG peak. Further, four exothermic effects at 800, 849, 898 and
947 K without appreciable mass loss is observed on the DTA
curve, which can be ascribed to a transition phase from
amorphous to crystalline form of FePO4 [5–7]. A minor mass
loss is observed, which corresponds to an exothermic peak on DTA
with respective DTG peak at 849 K. The retained mass (89.73%)
and water loss (20.27%) are compatible with the values expected
for the formation of FePO4 and 2 moles water per mole of the
synthesized FePO4, respectively. This indicates that the general
formula should be FePO4  2H2O. The temperature at which
theoretical mass loss is achieved can be also determined from
the TG curve and considered to be the minimum temperatures
needed for the calcinations process. Therefore, FePO4  2H2O
sample was calcined at 673 K for 2 h in the furnace, which is the
lower temperature as compared to those of the other hydrate
precursors [1–5]. However, FePO4 in this work obtained by the
calcined FePO4  2H2O at 623 K shows poor crystallization or
amorphous phase, which is revealed by the observed broad peaks
in XRD patterns (Fig. 2) and is in good agreement with the results
reported in the literature [2,5,6]. Additionally, the crystallinity of
FePO4 occurred at above 873 K of calcination supported a very
stable inorganic framework system of the studied compound. This
result is consistent with a transition phase from amorphous to
crystalline, which is concluded in thermal analysis (DTA peak at
over 947 K). The thermal stability, mechanism and phase
transition temperature of the synthesized FePO4  2H2O reported
in this work are different form those of our previous works
(FePO4  3H2O [7] and AlPO4  2H2O [20]). Based on these results,
we can conclude that the thermal results are caused by the nature
of materials and synthesis conditions.
The XRD patterns of iron phosphate dihydrate FePO4  2H2O
and its dehydration product (FePO4) are shown in Fig. 2. As seen
in Figs. 2a and b, the observed broad peaks in XRD patterns of the
synthesized FePO4  2H2O and FePO4 indicate the predominance of
the poor crystallization or amorphous phase as well as nanopar-
ticles. This result is in good agreement with the results reported
by Refs. [2,4–6], where the AlPO4 transforms from amorphous to a
crystalline phase at about 873 K. It evidenced that this studied
compound is a very stable inorganic framework system.
Additionally, the result is consistent with a transition phase from
amorphous to crystalline, which is concluded in thermal analysis.
Fig. 2. XRD patterns of FePO4  2H2O (a) and its dehydration product (FePO4) (b).
 ARTICLE IN PRESS
B. Boonchom, S. Puttawong / Physica B 405 (2010) 2350–2355
FT-IR spectra of FePO4  2H2O and its dehydration product
(FePO4) are shown in Fig. 3. Vibrational bands are identified in
relation to the crystal structure in terms of the fundamental
vibrating units namely PO34  , H2O, for FePO4  2H2O and PO34  for
Fig. 3. FT-IR spectra of FePO4  2H2O (a) and its dehydration product (FePO4) (b).
Fig. 4. SEM micrographs of FePO4  2H2O (a) and its dehydration product
(FePO4) (b).
2353
FePO4 [6,22]. FTIR spectra of PO34  in FePO4  2H2O and FePO4
show the antisymmetric stretching mode (n3) in 1000–1200 cm  1
region and the n4 mode in 400–560 cm  1 region. The observed
bands in 1600–1700 cm  1 and 3000–3500 cm  1 region are
attributed to the water bending and stretching vibrations. These
water bands disappear in FT-IR spectra of its dehydration product
(FePO4), which support a very good agreement with the thermal
analysis results. The XRD data along with FTIR spectra confirm
that the calcined FePO4  2H2O at 673 K transforms to FePO4.
The SEM micrographs of FePO4  2H2O and its final decomposi-
tion product FePO4 are shown in Fig. 4. The particle shape and size
are changed throughout the whole decomposition product. The
SEM micrographs of FePO4  2H2O (Fig. 4a) and FePO4 (Fig. 4b)
illustrate coalescence in aggregates of nanoparticles with sizes of
o300 nm. The morphology of FePO4 shows smaller size than that
of FePO4  H2O, which is the effect of the thermal dehydration
process.
3.2. Kinetics and thermodynamics results
According to isoconversional method, the basic data of a and T
collected from the TG curves of the dehydration of FePO4  2H2O at
various heating rates (5, 10, 15 and 20 K min  1) are illustrated in
Table 2. According to Eqs. 1 and 2), the plots of ln b versus 1000/T
(the FWO) and ln b/T2 versus 1000/T (the KAS) corresponding to
different conversions a can be obtained by a linear regression of
least-square method, respectively. The FWO and the KAS analysis
results of four TG measurements below 573 K are presented in
Fig. 5. The activation energies Ea can be calculated from the slopes
of the straight lines with better linear correlation coefficient
(r2 40.99). The slopes change depending on the degree of
conversion (a) for the dehydration reaction of FePO4  2H2O. The
activation energies are calculated at heating rates of 5, 10, 15, and
20 K min  1 via the FWO and the KAS methods in the a range of
0.2–0.8. The activation energies calculated by the FWO and the
KAS methods are close to each other, which are shown in Table 3,
so the results are credible. If Ea values are independent of a, the
decomposition may be a simple reaction, while the dependence of
Ea on a should be interpreted in terms of multi-step reaction
mechanisms [13–16]. Neglecting the dependence of E versus a an
average values of Ea =68.4870.93 kJ mol  1 (FWO) and 65.55 7
0.81 kJ mol  1 (KAS) are obtained. It was considered that the Ea
values are independent of a if the relative error of the slope of the
FWO and the KAS equations straight lines is lower than 10%. The
activation energies change little with a, so we draw a conclusion
that the dehydration reaction of FePO4  2H2O could be a single
kinetic mechanism, which corresponds to an endothermic peak at
398 K in DTA curve. The single kinetic mechanism of the
dehydration of the FePO4  2H2O reported in this work is
different from a multi-step kinetic mechanism of its
Table 2
a  T data at different heating rates, b (K min  1), for the dehydration reaction of
FePO4  2H2O.
a Temperature (K)
b=5 b = 10 b = 20 b = 30
0.2 365.76 372.86 380.66 388.30
0.3 372.81 381.69 390.03 396.05
0.4 379.91 390.11 398.17 404.08
0.5 387.44 398.21 406.64 412.42
0.6 395.73 407.65 417.09 422.12
0.7 405.80 418.91 428.54 433.24
0.8 419.88 434.60 444.47 449.16
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Table 4
Kinetics parameters obtained from the differential method and the integral
method at different heating rates (b = 5, 10, 15 and 20 K min  1).

Model Coats–Redfern method

Ea/kJ mol  1 ln A/s  1 r2

Ea 7 Error ln A 7 Error

F3/2 17.07 1.03  3.91 0.46 0.99535

A1, F1 37.82 1.78 2.79 0.56 0.98176
A3/2 22.96 1.20  2.39 0.52 0.97773
F2/3 32.77 1.57 0.22 0.66 0.97232
D1 55.15 2.39 5.72 0.97 0.95653
D2 62.81 2.71 8.36 1.09 0.96721
D3 72.28 3.11 10.47 1.23 0.97747
D4 65.94 2.84 8.32 1.14 0.97108
D5 14.47 0.93  4.58 0.43 0.98573

than those of the dehydration reaction of FePO4  3H2O

(130.18718 kJ mol  1 for the FWO method and
130.33719 kJ mol  1 for the KAS method) reported in our
previous work [7]. In this respect, these data will be important
for further studies of the studied compound, which include
studies under carefully controlled reaction conditions.
For kinetic function model analysis from the Coat–Redfern
equation (Eq. 3), we can draw a conclusion that the possible
conversion function is the based on the three-dimension diffu-
sion mechanism (D4 model), Ginstling–Brounstein Eq. [f(a)=
(3/2)(1 a)  1/3  1]  1 and g(a) =[1  (2/3)a  (1 a)2/3], which
are shown in Table 4. The correlated kinetic parameters are
Ea = 65.9472.83 kJ mol  1 and ln A= 8.3271.14 s  1. Additionally,
the strengths of molecular binding in the crystal lattice are
different. Consequently, the dehydration temperatures and
kinetic parameters are different. The activation energy for the
losing of crystal water lie in the range of 60–80 kJ mol–1, while the
value for coordinately bounded one are within the range of 130–
160 kJ mol–1 [20]. The energy of activation found in D4 model for
the dehydration reaction suggests that the water molecules are
water of crystallization. This result is different from the most
Fig. 5. FWO analysis (a) and KAS analysis (b) for the dehydration of FePO4  2H2O. kinetic model of the dehydration reaction of FePO4  3H2O (F2.5
model from the Coats–Rendfern method) reported in our pervious
work [7].
Table 3 The calculated values of DH*, DS* and DG* were calculated by
Activation energies (Ea) vs. correlation coefficient (r2) calculated by FWO and KAS Tp (418 K) in the highest heating rate and found to be 130.65 kJ
methods for the dehydration of FePO4  2H2O. mol  1, 30.32 J K  1 mol  1 and 117.98 kJ mol  1, respectively. The
entropy of activation (DS*) value for the dehydration step is
a FWO method KAS method
positive. It means that the corresponding activated complexes
Ea/kJ mol  1 r2 Ea/kJ mol  1 r2 were with lower degree of arrangement than the initial state.
Since the dehydration of FePO4  2H2O proceeds as a single
0.2 67.93 0.9801 65.17 0.9760 reaction, the formation of the activated complex passed in situ.
0.3 68.90 0.9937 66.07 0.9923
In terms of the activated complex theory (transition theory)
0.4 69.42 0.9976 66.49 0.9971
0.5 69.73 0.9983 66.69 0.9979 [15,22–26], a positive value of DS* indicates a malleable activated
0.6 68.18 0.9986 64.91 0.9983 complex that leads to a large number of degrees of freedom of
0.7 68.77 0.9987 65.35 0.9984 rotation and vibration. A result may be interpreted as a ‘‘fast’’
0.8 69.02 0.9984 65.37 0.9980
stage. On the other hand, a negative value of DS* indicates a
Average 68.48 70.93 0.9948 65.55 7 0.81 0.9937
highly ordered activated complex and the degrees of freedom of
rotation as well as of vibration are less than those in the non-
activated complex. This results may indicate a ‘‘slow’’ stage.
Therefore, the dehydration reaction of FePO4  2H2O may be
isostructural (AlPO4  2H2O) reported in our previous work [21]. interpreted as ‘‘fast’’ stage [15,22–26]. The positive value of the
However, the average activation energy of dehydration process of enthalpy DH* indicates the endothermic reaction, which is
FePO4  2H2O reported in this work is close to those of its consistent with an endothermic effects in DTA data (Fig. 1).
isostructural AlPO4  2H2O reported in our previous work Additionally, the positive value of DG* for the dehydration stage
(69.6877 kJ mol  1 for the Kissinger method) [21]. Moreover, shows that it is non-spontaneous process and is necessary to
these activation energy values obtained from this work are lower connect with the introduction of heat. These thermodynamic
 ARTICLE IN PRESS
B. Boonchom, S. Puttawong / Physica B 405 (2010) 2350–2355
functions are consistent with kinetic parameters and thermal
analysis data.
4. Conclusions
FePO4  2H2O decomposes in one step by starting after 300 K
and the final product is FePO4, playing a more and more
important role in the development of advanced rechargeable
lithium ion batteries. A single value of E for different a can be
assigned to a single reaction process, which relates to the
elimination of water of crystallization in the structure. On the
basis of correctly established values of the apparent activation
energy, pre-exponential factor and the changes of entropy,
enthalpy and Gibbs free energy, certain conclusions can be made
concerning the mechanisms and characteristics of the processes.
The data of kinetics and thermodynamics play an important role
in theoretical study, application development and industrial
production of a compound as a basis of theoretical. Consequently,
these data will be important for further studies of the studied
compound and are applied to solve various scientific and practical
problems involving the participation of solid phases.
Acknowledgement
This work is financially supported by the Thailand Research
Fund (TRF), the Commission on Higher Education (CHE) and
Research Grant for New Scholar, Ministry of Education, Thailand.
2355
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