J Inorg Organomet Polym
DOI 10.1007/s10904-016-0454-z
Synthesis, Characterization and Thermal Property of Phosphate
and Sulfate Mixtures
Trilochan Swain1 · Gouri Sankhar Brahma2
Received: 28 August 2016 / Accepted: 5 October 2016
© Springer Science+Business Media New York 2016
Abstract Two inorganic mixtures of copper and sodium
compounds have been synthesized and characterized with
different measurement techniques. The thermal property
of these mixtures has been studied to low temperature up
to 223 from 573 K with DSC. The specific heat capacity
of this mixture has been measured in atmospheric O2 at a
rate of 10 K min−1 from 573 to 223 K and vice versa in
two thermal cycles. The net specific heat capacity of these
mixtures is found endothermic in first and second thermal
cycles. The net specific heat capacity of 0.5Cu2(PO4)(OH);
3.5CuH(PO4)2·H2O; 2NaHSO4·H2O (CuPHS) during first
thermal cycle is −71203.05 J kg−1 K−1 and in second ther-
mal cycle is −73881.67 J kg−1 K−1 between temperature
range of 303–223 K. The net specific heat capacity of mix-
ture 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4(CuPS)
in first thermal cycle is −21158.37 J kg−1 K−1 and in
second thermal cycle is−45739.92 J kg−1 K−1 between
temperature range of 298–573 K. As both mixtures are
endothermic in nature in all cycles, it can be used as heat
storage material.The average crystallite size of mixture
0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 2NaHSO4·H2O
and 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4 is ~47 and
~17.3 nm, respectively.
Electronic supplementary material The online version of this
article (doi:10.1007/s10904-016-0454-z) contains supplementary
material, which is available to authorized users.
Trilochan Swain
scienceorissa@rediffmail.com
1
Indic Institute of Design and Research, Khurda, Odisha,
India
2
Faculty of Science & Technology, IFHE, Hyderabad,
Telangana, India
Keywords DSC · Specific heat capacity ·
Nanophosphate · Optical property · Sensible heat
1 Introduction
Nowadays phosphate materials are widely used due to their
large applications such as laser host, ceramic, dielectric,
electric, magnetic, food additives, fuel cells, pigments,
fertilizers, metal surface treatment, detergent, catalytic
processes, solar cell for enhancing the power conversion
efficiency etc. [1–6]. There are various types of materials
containing different types of phosphate groups such as poly-
phosphate, cyclo-phosphate and ultraphosphate. The prop-
erties of these phosphate materials depend on particle size,
surface area and morphology. The nanostructure phosphate
materials improve the various functional properties than the
bulk form and thin layers. The increase of various activi-
ties is thermal and chemical stabilities, densification kinet-
ics due to their large surface area [7–9]. Nowadays, there
is a rapid development in nanoscience and nanotechnology
which is increasing the effort of study on phosphate based
nanostructure materials [5, 8, 9]. The specific heat capac-
ity increases considerably by using phosphate cement,
KMgPO4·6H2O, [10] as binders for slag P and slag B aggre-
gates than other binders [11]. This tempted me to prepare
some phosphate based materials which can act as a binder
for enhancement of specific heat capacity. The energy stor-
age is an important parameter to improve the efficiency of
energy utilization in different economic aspects. It is the
main route of bridging the time gap between the energy
supply and the energy demand. In order to mitigate this the
mixture CuPHS was prepared using metaphosphoric acid
and copper(II) sulfate pentahydrate at room temperature by
a wet preparation method. The mixture CuPS was prepared
13
2 J Inorg Organomet Polym
by heating the above mixture at 343 K for 24 h. This method
is simple, cost effective and nontoxic route to synthesize
nanophosphate base compound. However, these phosphate
complexes of copper can be used as thermal storage materi-
als as long-chain n-alkylammonium dihydrogen phosphate
(n = 8, 9 and 10) [12]. Alonso et al. studies the solar redox
reactions of CuO for thermochemical energy storage and
demonstrated successfully in a solar furnace [13]. Copper
nanoparticles are used as fabrication of the solar cells [14].
In this work, the evaluation of thermal storage material is
limited to a calorimetric investigation. The objective of this
paper is to characterize and study the thermal properties of
this mixture for using as thermal storage material.
1.1 Experimental
In a typical synthesis of these compounds, 0.02 mol (5 gm.)
of CuSO4.5 H2O and 0.02 mol of metaphosphoric acid (60 %
HPO3 + 40 % NaPO3) were dissolved in 20 cc of double dis-
tilled water. Both solutions were mixed at room temperature
and stirred under ambient conditions till homogeneous. The
stirred solution was left for 120 h. The resulting product was
filtered, washed and dried in desiccators. Highly purified de-
ionized water was used in all solution preparation. Second
distillation was carried out from alkaline KMnO4 using an
all-glass distillation apparatus. The mixture CuPS was pre-
pared by heating the mixture CuPHS at 343 K for 24 h. The
Differential Scanning Calorimetry (DSC), Mettler Toledo
DSC 822e, was performed in ST&IC, Cochin University of
Science and Technology, Cochin. The specific heat capac-
ity of CuPHS mixture was measured at 10 K/min from 303
to 223 K and from 298 to 573 K for CuPS in two thermal
cycles. The X-ray crystallography measurement of pow-
der sample was carried out in Panalytical’s X’Pert Pro by
SAIF Chandigarh, Panjab University. inductively coupled
plasma-atomic emission spectrometry (ICP-AES) measure-
ment was performed using Thermo Electron IRIS Intrepid II
XSP DUO system for Cu, Na, S and P determinations. The
mixture was dissolved in 10 ml HNO3 of 30 % (v/v) and
made up into 100 ml using HPLC grade water for elemental
analysis. C–H–N–S was measured in Elementar Vario EL
III. The IR spectra were taken by a Perkin Elmer make, Par-
agon 5000, FT-IR spectrometer in SAIF Chandigarh, Panjab
University. Thermogravimetric analysis (TGA) and differ-
ential thermal analysis (DTA) of the mixtures were done
using Perkin Elmer STA 6000 thermal analyser at the tem-
perature range of 313–1002 K. The Ultraviolet–Visible and
near Infrared (UV–Vis–NIR) Absorption Spectrophotom-
etry was carried out in Varian Cary 5000 from wavelength
range 224.00–1976.00 nm at room temperature in bulk solid
state of the mixtures. Transmission electron microscopy
(HRTEM) was carried out using a JEOL JEM-2100 micro-
scope with an accelerating voltage of 200 kV. The magnetic
13
characterization was performed with a vibrating sample
magnetometer (VSM) having Lake Shore Model 7410 in
SAIF, IIT Madras. Zero field-cooled (ZFC) and field-cooled
(FC) scans of magnetization as a function of temperature
were performed from 20 to 300 K with an external field of
5000 Oe. The UV-Vis-NIR, HRTEM, C–H–N–S, TG-DTA
and ICP-AES studies were performed in ST&IC, Cochin
University of Science and Technology, Cochin.
2 Results
2.1 FTIR Analysis
2.1.1 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O;
2NaHSO4·H2O
The FTIR spectrum is displayed in Fig. 1a. The vibra-
tional bands of phosphate anion are observed at 1034, 1003
and 564 cm−1. These bands are assigned to the asymme-
try stretching (υas), symmetry stretching (υs) and bending
(δs) of PO43− ion, respectively. These bands are assigned
according to the literature of Onmura et al. and Abadzhieva
et al. [15, 16]. The bands 1665 and 3232 cm−1 (broad) are
assigned to water bending and asymmetry stretching vibra-
tion of O–H, (H2O), respectively [17]. This indicates the
presence of crystalline hydrate. The vibrational bands below
700 cm−1 are assigned to the symmetric and asymmetric
bending of SO42− group. The asymmetric stretching (υas) of
SO42− group is assigned to 1105–1164 cm−1 [17].
2.1.2 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4
The FTIR spectrum is displayed in Fig. 1b. The symmetric
stretching frequency of the P–O bonds in the PO22− radi-
cal is 1190 cm−1. The asymmetric and symmetric stretch-
ing frequencies of the P-O-P bridge are 1097 and 769 cm−1,
respectively. The symmetric stretching frequency of the
PO22− radical is higher than those in the P–O–P bridge
because the P–O bond strength in the PO22− radical is stron-
ger than the P–O–P bridge. The bending modes of PO22−
and P–O–P bridge are 559 and 473 cm−1, respectively. The
asymmetric bending of SO4 group is 615 cm−1.The struc-
ture of Cu2(PO4)(OH), CuH(PO4)2 and Na2SO4 is given in
Fig. 9.
2.2 X-ray Crystallography
2.2.1 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O;
2NaHSO4·H2O
Crystal data and experimental details of the title mixture are
collected in Supplementary Table 1. The compared XRD
J Inorg Organomet Polym
Fig. 1 a FTIR spectrum of mixture 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 2NaHSO4·H2O. b FTIR spectrum of mixture 0.5Cu2(PO4)(OH);
3.5CuH(PO4)2; 2Na2SO4
patterns of libethenite Cu2(PO4)(OH) (PDF Index Name:
Copper Phosphate:01-083-1557) and CuH(PO4)2·H2O
(PDF: 00-012-0520) (b—red), sodium hydrogen sulphate
monohydrate (J CPDS NO. 22-1379) (a—black) and pow-
der mixture (c—blue) is displayed in Fig. 2a. The diffrac-
tion patterns are in good agreement with reported in the
literatures [18, 19]. From this XRD pattern, it is concluded
that the mixture consists of three inorganic compounds such
as Cu2(PO4)(OH), CuH(PO4)2·H2O and NaHSO4·H2O.
3
2.2.2 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4
The compared XRD patterns of libethenite Cu2(PO4)(OH)
(PDF Index Name: Copper Phosphate:01-083-1557) and
CuH(PO4)2·H2O (PDF: 00-012-0520) (b—red), sodium
sulfate (PDF: 37-1455) (c—green) and powder mixture
(a—blue) is displayed in Fig. 2b. The diffraction patterns
are in good agreement with reported in the literatures [18,
20]. The literature of Rodriguez-Navarro is used for X-ray
13
4 J Inorg Organomet Polym

Fig. 2 a XRD pattern

of mixture 0.5Cu2(PO4)
(OH); 3.5CuH(PO4)2·H2O;
2NaHSO4·H2O. b XRD pat-
tern of mixture 0.5Cu2(PO4)
(OH); 3.5CuH(PO4)2; 2Na2SO4.
(Color figure online)

powder diffraction pattern of sodium sulfate. The observed (1) 0.9λ

pattern of the mixture also matched very well with Rodri- β cosθ = + 4ε sinθ
DWH
guez-Navarro [21]. From this XRD pattern, it is concluded
that the mixture consists of three inorganic compounds such where, λ (0.154056 nm) is the Cu kα radiation wavelength
as Cu2(PO4)(OH), CuH(PO4)2·H2O and Na2SO4. of the X-ray, β is the full width at half maximum (FWHM)
of the peak, DWH is the average crystallite size, ε is the strain
2.3 Crystal Size Determination and θ is the half of the diffraction angle. A graph is plot-
ted between β cos θ versus sin θ and found with equation
The crystallite size and strain are calculated from detail Y = 0.0006 X + 0.003 for the mixture CuPHS. The calcu-
analysis of X-ray diffraction (XRD) line profile using Wil- lated crystallite size for the mixture CuPHS is 46.2 nm.
liamson–Hall (WH) method [22] and modified Scherrer The modified Scherrer equation is given below.
Equation [23]. According to WH method, the individual
contribution of the nanocrystals to the XRD peak broaden- K ×λ 1
ln β = ln
(2) + ln
ing can be expressed as D cosθ

13
J Inorg Organomet Polym 5

The description of symbols λ, θ and β are similar to Eq. (1).
K is the shape factor 0.9 and D is the average crystallite
size. A graph is plotted between lnβ versus ln(1/cosθ) and
found with equation Y = 2.8625 X − 2.5448. The calculated
average crystallite size is 48.6 nm for the mixture CuPHS.
The crystallite size can also be estimated from peak
broadening of XRD using well known Debye–Scherrer’s
formula
K ×λ
D=
(3)
β cosθ
The description of symbols λ, θ and β are similar to Eq. (1).
K is the shape factor 0.9 and D is the crystallite size. The
average crystallite size is 46.7 and 17.3 nm for the mixture
of CuPHS and CuPS respectively.
2.4 Elemental Analysis
2.4.1 C, H, N, S Analysis
The elemental analysis of the mixture was found consis-
tence with the theoretical values. Anal. Calcd. for mixture
{0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 2NaHSO4·H2O,
mol. wt. = 1286.28 gm.} is H 1.32 %; found H 1.78 %.
2.4.2 ICP-AES Analysis
mixture 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4, mol.
wt. = 1231.12 g, was carried out twice with ICP-AES. We
took the average of the two analyses. The detail of elemental
composition is inserted in Table 1.
2.5 UV–Visible–NIR Absorption Spectroscopy
The room temperature absorption spectra of the mixtures
in solid state are presented in Fig. 3. Both spectra shows
an absorption band at about ~800 nm which is due to the
Cu2+ ions being in octahedral sites. The low intensity of
this absorption band is further explained by the position
of copper in a perfect octahedron. From this low intensity
of the absorption band, it appears that copper is situated in
a nearly perfect square planer surrounding formed by the
equatorial oxygen atoms of a tetragonally distorted octahe-
dron with elongated bonds perpendicular to this plane [24].
The absorption spectrum of mixture, CuPHS, shows one
sharp and one broad peak. These two peaks show absorp-
tion bands at 268 and 799 nm having absorbance 1.222
and 0.526, respectively. The calculated band gap from λmax
268 nm is 4.63 eV. In case of mixture CuPS, the absorption
spectrum shows one sharp and two broad peaks. These three
peaks show absorption bands 270, 803 and 1941 nm having
absorbance 0.913, 0.686 and 0.208 respectively. The calcu-
lated band gap from λmax 268 nm is 4.59 eV. Hence, both the
mixtures are insulator at room temperature.

The elemental analysis of this mixture was carried out
with ICP-AES. The Cu, P, S and Na were also consis-
tent with the theoretical values. Anal. Calcd. for mixture
{0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 2NaHSO4·H2O,
mol. wt. = 1286.28 g}. The elemental analysis of
2.6 TG-DTA Analysis
The mixtures undergo thermal decomposition in several
not well-separated stages in Tg profiles. Derivative of Tg
curves reveal that the weight loss in the temperature range

Fig. 3 UV–Vis–NIR spec- Wave length versus Absorbance

trum of mixture 0.5Cu2(PO4)
(OH); 3.5CuH(PO4)2·H2O 1.2
2NaHSO4·H2O (1)
and 0.5Cu2(PO4)(OH);
3.5CuH(PO4)2; 2Na2SO4 (2) in 1
solid state in solid state 1
Wavelength(nm) Abs (2)
0.8 2 270.000 0.912
Absorbance

802.000 0.686
0.6 866.000 0.642

0.4

0.2 Wavelength (nm) Abs(1)

268.000 1.222

0
230 430 630 830 1030 1230 1430 1630 1830
Wavelength (nm)

13
6 J Inorg Organomet Polym

a Weight loss versus Temperature sulfite lost from the mixture along with moisture. The 3.5
100 moles of CuH(PO4)2·H2O converted to the corresponding
anhydrous CuH(PO4)2 with removal of 3.5 moles of water.
80
The remaining three moles of water and a sulfite lost from
Weight loss / %

the decomposition of two moles sodium hydrogen sulfate

60
monohydrate. This compound converted to sodium sulfate
(Na2SO4) through sodium pyrosulfate (Na2S2O7).
40
There are three peaks in DTG curve of mixture CuPS.
These three peaks are at 342.94, 816.10 and 891.84 K
20
(Fig. 4b). From Tg analysis, the mass loss up to the above
0
temperature are 0.12, 1.79 and 2.28 respectively. From DTA
310 410 510 610 710 810 910 1010 curve, this mixture is found endothermic in nature (Fig. 5b).
Temperature/K
The mass loss up to temperature 993.36 K is 2.64 %. Up to
b Weight loss versus Temperature 993.36 K, only the moisture is lost from the mixture.
100

99.5 2.6.1 Differential Scanning Calorimeter

Weight loss/ %

99
98.5
98
97.5
97
300 500 700 900
Temperature/K
1100
Fig. 4 a TG and DTG profile of mixture 0.5Cu2(PO4)(OH);
3.5CuH(PO4)2·H2O; 2NaHSO4·H2Ointhetemperaturerange313–1002K.
b TG and DTG profile of mixture 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2;
2Na2SO4 in the temperature range 311–993 K
313–1002 K consists of three steps in both mixtures. In
DTG curve, these three peaks CuPHS mixture temperature
are 383.18, 426.93 and 553.46 K Fig. 4a. From Tg analysis,
the mass loss up to the above temperature are 4.25, 8.90
and 14.33 %, respectively. From DTA curve, this mixture is
found endothermic in nature at 430.60 K, ∆H = 95.95 J g−1
Fig. 5a. The mass loss up to temperature 1002.82 K
is 19.481 %. Up to 1002.82 K, 6.5 moles of water and a
Fig. 5 DTA profiles of mixture 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O;
2NaHSO4·H2O and 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4 in the
temperature range 313–993 K
The DSC curve of mixture, CuPHS, was plotted between spe-
cific heat capacity versus temperature from 303 to 223 K in
two thermal cycles in Fig. 6a. The total specific heat capacity
of this mixture is 25985.95 J kg−1 K−1 in the first cycle during
cooling from 303 to 223 K and −97189.18 J kg−1 K−1 during
heating in reverse. So, the net specific heat capacity during
1300 1500
first cycle is −71203.05 J kg−1 K−1 while in case of other
phosphate complex such as nickel is 1747.86 J kg−1 K−1
[25]. Hence, the first cycle is endothermic in nature. The
total specific heat capacities in second thermal cycle dur-
ing cooling and heating in the same temperature ranges as
above are 23879.90 J kg−1 K−1and −97761.57 J kg−1 K−1,
respectively. The net specific heat capacity during second
cycle is −73881.67 J kg−1 K−1 and in case of Ni3(PO4)2 is
−6401.38 J kg−1 K−1 [25]. As both cycles are endothermic
in nature, it can be used as heat storage material.
The DSC curve of mixture, CuPS, was plotted between
specific heat capacities versus temperature from 298 to
573 K in two thermal cycles in Fig. 6b. The specific heat
capacities in both cycles each during heating and cool-
ing occurred in two thermal stages. The total specific heat
capacity of this mixture is −3717.12 J kg−1 K−1 in the first
cycle during heating from 298 K to 383.33 K and 19652.8 J
kg−1 K−1 from 384 to 573 K. The net specific heat dur-
ing heating is 15935.68 J kg−1 K−1. The total specific heat
capacity is 3392.85 J kg−1 K−1 during cooling from 573
to 489.33 K and −40486.9 J kg−1 K−1 from 488.66 K to
298 K. The net specific heat during cooling is − 37094.05 J
kg−1 K−1. So, the net specific heat capacity in first cycle is
−21158.37 J kg−1 K−1. Hence, the first cycle is endothermic
in nature. The total specific heat capacity of this mixture
is −11812.3 J kg−1 K−1 in the second cycle during heating
from 298 to 464 K and 19416.13 J kg−1 K−1 from 464.66
to 573 K. The net specific heat during heating is 7603.83 J
kg−1 K−1. The total specific heat capacity is 2842.35 J
kg−1 K−1 during cooling from 573 to 486 K and −56186.1 J

13
J Inorg Organomet Polym 7

a Specific heat capacity versus Temperature the second cycle is endothermic in nature. As both cycles
400 are endothermic in nature, it can be used as heat storage
material.
Specific heat capacity/J kg-1 K-1

200
The by-products of the pyrometallurgical refining pro-

Exo
0
210 230 250 270 290 310 cess of copper have specific heat capacity Cp = 571 J kg−1
-200
1st cycle K−1 (373 K) and Cp = 648 J kg−1 K−1 (373 K) for Slag-P and

Endo
-400 2nd cycle Slag-B [11]. The mixture of CuPS is specific heat capacity
-600 Cp = 144.82 J kg−1 K−1 (373 K) during cooling in first cycle
-800 and the specific heat capacity in second cycle is 225.82 J
-1000 kg−1 K−1 (373 K) during cooling. It is found from the above
Temperature/K
calorimetric discussion that this mixture can be used as a
Specific heat capacity versus Temperature thermal storage material using sensible technique for the
b 400 substitution of other materials Table 2 [11, 26].
Specific heat capacity/Jkg-1K-1

200
2.7 TEM Analysis

0
290 340 390 440 490 540 590 The high resolution TEM (HRTEM) measurements car-
1st cycle
2nd cycle
ried out on synthesized mixture, 0 CuPHS, are shown in
-200
the Fig. 7.
-400
2.8 Magnetic Properties
-600
Temperature/K The magnetic moment measurement was carried out with
field cooled (FC) and zero field cooled (ZFC) of the mixture
Fig. 6 a This is DSC graph of mixture 0.5Cu2(PO4)(OH);
3.5CuH(PO4)2·H2O; 2NaHSO4·H2O between specific heat capacity CuPHS. It is shown in the Fig. 8. The Curie–Weiss tem-
versus temperature in the temperature range 303–223 K and vice versa perature (θ) and Curie constant (C) are calculated from the
in two thermal cycles and kept at 223 K for 3 min. b This is DSC graph formula given below.
of mixture 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4 between spe-
cific heat capacity versus temperature in the temperature range 298–
C
573 K and vice versa in two thermal cycles and kept at 573 K for 1 min χg =
(4)
(T − θ )
kg−1 K−1 from 485.33 to 298 K. The net specific heat during
cooling is −53343.75 J kg−1 K−1. So, the net specific heat where, χg is mass magnetic susceptibility. This equation is
capacity in second cycle is −45739.92 J kg−1 K−1. Hence, for T > θ.

Fig. 7 3D visualisations of mixture 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 2NaHSO4·H2O

13
8 J Inorg Organomet Polym

Magnetic moment versus Temperature 2.9 Chemical Test

0.012
Magnetic moment versus Temperature
Magnesia mixture test: Dilute acetic acid was added in 2 ml.

Magnetic moment/emugm-1
0.012
Magnetic moment/emugm-1

0.01
0.01
ZFC sodium extract of mixture CuPHS till effervescence ceases.
0.008
0.008
0.006
A pinch of NH4Cl followed by 2 ml. of magnesium sulfate
0.004 was added in the above solution. A white precipitate was
0.006
0.002 observed after addition of excess of ammonium hydroxide.
0
0.004 10 110 210 310 So, presence of phosphate group is conformed in mixture.
Temperature/K
FC
0.002

0
3 Discussion
10 60 110 160 210 260 310 360
Temperature/K
3.1 Stoichiometry Calculation
Fig. 8 Magnetic moment measurement of mixture 0.5Cu2(PO4)(OH);
3.5CuH(PO4)2·H2O; 2NaHSO4·H2O In the typical synthesis of 0.5Cu2(PO4)(OH);
3.5CuH(PO4)2·H2O; 2NaHSO4·H2O mixture, the following
compounds formed.

The Eq. (4) is further simplified to inverse of mass mag- NaPO3 + H 2 O → NaH 2 PO 4
netic susceptibility. 4.5CuSO4·5H 2O + 7.5NaH 2 PO 4 → 0.5Cu 2 ( PO 4 )( OH )
+ 3.5CuH(PO 4 ) 2·H 2O + 18H 2O + 4.5SO 24 − + 7.5Na + + 16H +
T θ
χ g−1 = −
(5)
C C
NaH 2 PO 4 + 7.5Na + + 4.5SO 24 − + 16H + + 18H 2O
The linear equation of the graph between χ g−1 versus tem-
perature in zero field-cooled is → 4.5NaHSO4·H 2O + PO34− +13.5H + + 13.5H 2O + 4Na +
From the above reaction, the mixture should contain 1:1.5
molar ratio of phosphate: sulfate. According to elemental
χ g−1 = 0.1033T + 1.3559. analysis, the mixture contained 2:1 molar ratio of phosphate
and sulfate compound. The excess sodium hydrogen sulfate
The Weiss constant (θ) and Curie constant (C) are −13.125 K reacted with ethanol, during washing of the mixture, to form
and 9.6805 respectively. ethyl sulfuric acid as follows [27].
The linear equation of the graph between χg−1 versus
temperature in field-cooled (FC) is T <305.3 K
2 NaHSO 4 ·H 2 O + C2 H5 OH ← → C2 H5 HSO 4
+ Na 2SO 4 + 2H 2 O
χ g−1 = 532.84T + 4606. The sodium sulfate formed combine with water present in
the reaction mixture and removed from this mixture during
The Weiss constant (θ) and Curie constant (C) are −8.644 K washing.
and 0.001877 respectively. In the typical synthesis of CuPS mixture, the following
The negative Weiss constant values indicate that the mix- compounds formed.
ture is antiferromagnetism.

Fig. 9 The structure of

CuH(PO4)2, Cu2(PO4)(OH) and
Na2SO4

13
J Inorg Organomet Polym 9

2NaHSO4·H 2O ∆ → 2NaHSO4 + 2H 2O where, fR is the spring constant. The mixture is governed by
~ 353 K
the Hamiltonian
→ Na 2S2O7 + 3H 2O ∆
∆ ~353 K
→ Na 2SO 4 + SO32 − + 3H 2O
P2 f
(9)
HC = + C Q2
3.5CuH(PO4 ) 2 ·H 2 O ∆
~ 353 K
→ 3.5CuH(PO 4 ) 2 + 3.5H 2 O 2M 2

In the case of free particle, oxidation (O2) (spring constant

while the compound 0.5Cu2(PO4)(OH) is remain as such. fc = 0) and of a harmonic oscillator (fc > 0), the coupling
Hamiltonian is given by
3.2 Thermal Discussion
f
H CR = − f R qQ + R Q 2
(10)
The specific heat capacity is found negative in some ther- 2
mal cycles of both mixtures. The negative specific heat was
elucidated by Swain [28–30] from metaphosphatecobalt(II) The mass of a single particle oscillator of instable particle
salt and methionine bridged cobalt(III) and copper(II) com- is m. The mass of mixture is M and the instable particle
plex using the partition function of the dissipative system coupled with mixture harmonically. In my analysis a free
[31–33]. It is defined in terms of partition functions of the particle (O2), by heating from 298 to 573 K in first ther-
coupled system and of the uncoupled system. mal cycle, was in contact with the single degree of free-
dom environment described by Eqs. 8 and 10. Mixture and
Trs + B e − β H instable particles are assumed to stay in thermal equilib-
Z=
(6) rium with each other at the inverse temperature β. Hence,
TrB e − β H B the density matrix of the total system is given by a Gibb’s
state.
where the total Hamiltonian, H = HS + HB + HSB, con-
sisted of contributions from the system, bath and coupling
−1
ρCR = Z CR
(11) exp  − β ( H C + H R + H CR ) 
between them. The Z reduces to the partition function of
the system in the absence of coupling between system and where, Z CR = Tr exp  − β ( H C + H R + H CR )  denotes the
bath. Partition function (6) appears naturally in the Feyn- partition function of the total system.
man–Vernon approach to dissipative systems [31] and can The partition function Z R = Tr exp[− β H R ] of the instable
be related to the equilibrium properties of the system [34]. particle’s degree of freedom is given by
I also find here the same type of negative specific heat as
Swain [28–30]. From Eq. 6, one obtained by means of stan- 1
Z R = Tr exp [ − β H R ] =
dard thermodynamic relations a specific heat [32]. (12)  βω0 
2sin  
 2 
2  Tr e − β H 
2 ∂
C =
(7)k B β ln  s+B  where,
∂β 2  Tr e − β H B 
 B 
2  f 
ω = R 
(13)
where, β = 1/kBT. kB is the Boltzmann constant. The defini-  m
tion of specific heat reduces to the usual definition in the
absence of coupling between system and bath. ω0 is the frequency of instable particle oscillator. From
In Eq. 7, I assumed here that the instability of particles Eq. 7 the specific heat capacity of these instable particles
(atoms or molecules) is consisted of harmonic oscillators are given below.
and the coupling to be bilinear in complex and instable par-
ticles. It is sufficient to consider a stylized minimal model  βω0 
CR = k B g 
(14) 
coordinates, in order to know the appearance of negative  2 
specific heat (Eq. 7), where the instable particles con-
sisted of only a single degree of freedom described by the where,
Hamiltonian.
2
(15)  x 
2 g ( x) =  
P f  sinx 
(8)
HR = + R q2
2m 2

13
10 J Inorg Organomet Polym

Table 1 ICP-AES analysis data of mixtures 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 2NaHSO4·H2O and 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2;
2Na2SO4
0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 2NaHSO4·H2O 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 2Na2SO4
Sl. no. Element Found (%) Calculated (%) Found (%) Calculated (%)

1 Copper (Cu) 23.12 22.22 22.62 23.22

2 Phosphorous (P) 18.17 18.05 18.64 18.86
3 Sodium (Na) 3.71 3.57 8.12 7.46
4 Sulfur (S) 5.21 4.98 4.93 5.20

Table 2 The materials used for the storage of sensible heat

Material Temperature (K) Specific heat Material Temperature Specific heat
(kJ kg−1 K−1) (K) (kJ kg−1 K−1)

Water 273–373 4.19 Cast Iron – 0.54

Thermo-oil Up to 623 2.1 Aluminium – 0.92
53KNO3/40NaNO2/7NaNO3 Up to 723 1.3 Fire clay – 1.0
Na – 1.26 Al2O3 – 1.0
Slag_P 373 0.571 Stone – 0.8–0.9
Slag_B 373 0.648 Concrete – 0.9
CBPC_B 373 0.703 MgO – 1.0
CBPC_P 373 0.655 AP 373 0.630
AB 373 0.640 PP 373 0.623
This work PB 373 0.681
0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O; 303-223-303 71.2
2NaHSO4·H2O First cycle
-do- 303-223-303 73.88
Second cycle
0.5Cu2(PO4)(OH); 3.5CuH(PO4)2; 298-573-298 21.15
2Na2SO4 First cycle
-do- 298-573-298 45.73
Second cycle

In order to obtain a well-defined partition function for the   1 

free particle, I restricted its motion to a region of inside the  βω0 {ς ± (ς 2 − 1) 2 } 
CC = −k B g  (17)
system. Here the system is considered to be sufficiently 
 2 
large such that the energy level spacing can be neglected in  
compared with the thermal energy kBT [32]. Under this con-
dition the space of this system will turn out to be irrelevant The total heat capacity of the system containing this mixture
in the sequel. is given below
The frequency of underdamped complex (ς < 1)
 1 
1  βω0{ς ± (ς 2 − 1) 2 }   βω0 
(16) C = CC + CR = − k B g 
(18)  + kB g  
ω = ω0 {ς ± (ς 2 − 1) 2 } 2  2 
 
 
ς is called as damping ratio. In this case this mixture loses
energy due to the formation of instability on particles and Simplifying further
return to the thermally stable state.
As the damping ratio is <1, the specific heat capacity of
 βω0     
1
2
this mixture by putting the value of ω from Eq. 16 is given (19)
C = −k B g    ς ± (ς − 1) 2  − 1
below.  2     

13
J Inorg Organomet Polym
From Eq. 16, the value of ω0 is given below
ω 3.5CuH(PO4)2; 2Na2SO4.
ω0 =
(20) 1
{ς ± (ς 2 − 1) 2 }
The damping ratio is <1 for underdamped complex, so the
value of ω0 is negative. Hence the system containing this
mixture is negative specific heat capacity.
Hence, the specific heat capacity of the system at high
temperature is negative.
In case of heating from low temperature to high tempera-
ture, the bond stability of atoms or molecules in complex at
low temperature turns into more instability at high tempera-
ture due to increase of different motions of atoms and mol-
ecules. So, the part of the heat supply utilizes for making
instability in complex and others discard. In present case,
the instability of chemical compounds owing to increase of
different motions of atoms and molecules present in mixture
for low temperature heating of CuPHS from 223 to 302.5 K
makes the damping ratio <1. So, specific heat capacity is
negative. In case of high temperature heating of mixture
CuPS in first thermal cycle from 298 to 383 K and second
thermal cycle from 298 to 464 K is also negative specific
heat capacity. In this case, the amount of heat absorbs by
making the instability of bonds between atoms and mol-
ecules present in the mixture. Hence, the damping ratio is
<1 due to increase in different of motions among atoms and
molecules.
In case of positive specific heat capacity, the amount of
energy release is more and makes the mixture more stable
than before. This is due to decrease in instability by reduc-
ing the different motions of atoms and molecules in mix-
ture. The positive specific heat capacity is observed for two
stages in two thermal cycles of cooling from 302.5 to 223 K
in mixture for CuPHS and from 573 to 489.33 K in first
thermal cycle and 573 to 486 K in second thermal cycle of
mixture CuPS.
4 Conclusion
The characterization of these mixtures was carried out by
FT-IR, C–H–N–S, ICP-AES, TG-DTA, UV–Vis–NIR,
HRTEM, VSM, XRD and magnesia mixture test. The cop-
per containing mixtures, CuPHS and CuPS, can be used as
thermal storage material using latent heat technique because
both the mixtures are endothermic in nature in all cycles.
The both mixtures are far superior for using as thermal
storage materials than other materials. The first mixture is
found antiferromagnetism due to negative Weiss constant
value. The band gap of both mixtures at λmax 268 nm is
~4.60 eV. So, both are insulators. The average crystallite
11
size is ~47 nm for 0.5Cu2(PO4)(OH); 3.5CuH(PO4)2·H2O;
2NaHSO4·H2O and 17.3 nm for 0.5Cu2(PO4)(OH);
Acknowledgments The author TS thanks Indic Institute of Design
and Research for providing necessary laboratory facility for the prepa-
ration of this salt. GSB is thankful to the Director, FST, IFHE for grant-
ing permission to get associated with this work.
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