Conductance studies on complex formation of nano Cu(NO3)2.2.5H2O with 4,6-diacetylresorcinol in mixed solvents

Article abstract of DOI:10.1016/j.molliq.2019.111602

The different complexation thermodynamic parameters for example, formation constants (K_f), free energies of formation (?G_f), enthalpies of formation (?H_f) and entropies of formation (?S_f) for nano copper nitrate hemi pentahydrate (Cu(NO₃)₂.2.5H₂O) with 4,6-diacetylresorcinol as a ligand in pure DMF and in mixed solvents of DMF and water are calculated at different temperatures, 293.15, 303.15, 313.15 and 323.15 K by using conductance measurements. By drawing the relation between molar conductance and ratio of metal to ligand, the figures indicate the formation of two types of complexes with M:L ratios 1:2 and 1:1 stoichiometric complexes.

Full text of DOI:10.1016/j.molliq.2019.111602

Journal of Molecular Liquids 294 (2019) 111602
Contents lists available at ScienceDirect
Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Conductance studies on complex formation of nano Cu(NO3)2.2.5H2O
with 4,6-diacetylresorcinol in mixed solvents
⁎
Sameh G. Sanad , Magdy Shebl
Department of Chemistry, Faculty of Education, Ain Shams University, Roxy, Cairo, Egypt
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 June 2019
Received in revised form 14 July 2019
Accepted 20 August 2019
Available online 22 August 2019
The different complexation thermodynamic parameters for example, formation constants (Kf), free energies of
formation (ΔGf), enthalpies of formation (ΔHf) and entropies of formation (ΔSf) for nano copper nitrate hemi
pentahydrate (Cu(NO3)2.2.5H2O) with 4,6-diacetylresorcinol as a ligand in pure DMF and in mixed solvents of
DMF and water are calculated at different temperatures, 293.15, 303.15, 313.15 and 323.15 K by using conduc-
tance measurements. By drawing the relation between molar conductance and ratio of metal to ligand, the fig-
ures indicate the formation of two types of complexes with M:L ratios 1:2 and 1:1 stoichiometric complexes.
© 2019 Elsevier B.V. All rights reserved.
Keywords:
Formation thermodynamic parameters
Formation constants
Gibbs free energy
Enthalpy
Entropy
Nano copper nitrate
4,6-Diacetylresorcinol
1. Introduction
Conductance (conductivity) of an electrolyte solution is a measure of
the ability of solution to conduct electricity. Conductance depends on
In the human body, copper is one of the most bounteous metallic el-
ements. More than a dozen of enzymes depend on copper for their work
[1]. Furthermore, copper (II) complexes have attracted an immense in-
terest because of their important biological applications such as antimi-
crobial, antitumor, antioxidant activities, DNA-binding properties as
well as other different applications [2–15].
many factors such as, the nature of the ions, size of ions, charge of
ions, mobility of ions, dielectric constant of solvent and viscosity of
solvent.
Conductivity measurements are widely used in industry. Some im-
portant applications are; water treatment: raw water as it comes from
a lake, river, or the tap is rarely suitable for industrial use.
Study of the complexation of metal cations with ligands in mixture
of different solvents become more important in analytical applications
and to determine the mechanism of biological transport and molecular
recognition [16].
Surface complexation reactions have an important role in the precip-
itation and dissolution of minerals. Also, complexation reactions used to
transport and transformation of metals and organic contaminants. Com-
plexes form by the combination of cations, anions, and sometimes mol-
ecules [17–19].
Many researches on complex formation have been done recently.
There are many physico-chemical methods and techniques which can
be used in the study of complex formation reactions like, polarography,
calorimetry, conductometry, spectrophotometry and spectrometry [20].
Conductometry is the most useful technique from these different tech-
niques because it is more sensitive and cheap method [21].
Formation constant is an important parameter for the investigation
of equilibrium in solution. Thermodynamic parameters of formation
play an important role in many fields such as industry, environment,
medicinal studies and analytical chemistry [22–25]. Therefore complex-
ation reactions of metal ions with many ligands have been widely stud-
ied [26–28]. Determination of thermodynamic parameters of formation
is the fundamental approach to understand the behaviour of metal ions
in aqueous solution in the presence of some chelating agent [29].
The organic compound; 4,6-diacetylresorcinol (Scheme 1) has
attracted a considerable interest due to its flexibility and the possibility
to use it in synthesis of diverse polydentate chelating agents (Schiff
bases, hydrazones and other chelating agents) [30–43]. In addition,
solid complexes of alkaline earth, transition, lanthanide and actinide
ions with 4,6-diacetylresorcinol have been synthesized and character-
ized [44–48]. However, no conductometric measurements on 4,6-
diacetylresorcinol with copper nitrate were carried out. Thus, the aim
of the present work is to study the complexation thermodynamic pa-
rameters; formation constants, free energies of formation, enthalpies
and entropies of formation of 4,6-diacetylresorcinol with (Cu(NO3)
⁎
Corresponding author.
E-mail addresses: Sameh_gamal010@yahoo.com, Sameh_Gamal@edu.asu.edu.eg
(S.G. Sanad).
https://doi.org/10.1016/j.molliq.2019.111602
0167-7322/© 2019 Elsevier B.V. All rights reserved.

2
S.G. Sanad, M. Shebl / Journal of Molecular Liquids 294 (2019) 111602
Calc.: C, 61.85; H, 5.19. Found: C, 61.7; H, 5.3. The solvents are DMF
from Merck company (with purity 99.8%) and distilled water.
2.2. Preparation of nano copper nitrate
Nano copper nitrate hemi pentahydrate was prepared from the mill-
ing of bulk copper nitrate hemi pentahydrate using ball mill of type
Retsch MM 2000 swing mill with two balls of stainless steel with diam-
eter of 12 mm. Ball milling was performed at 20225 Hz and room tem-
perature. The temperature was kept lower than 30 °C.
O
O
2.3. Measurements
CH
CH
The elemental analtses were carried out at the Microanalytical Cen-
ter, Cairo University, Giza, Egypt. FT-IR spectra (4000–400 cm−1) were
recorded as KBr discs using a Shimadzu 4000 FT-IR spectrophotometer.
Electronic spectra were recorded at room temperature on a Jasco model
V-550 UV/Vis spectrophotometer as solution in DMF. 1H NMR spectra
were recorded at room temperature in DMSO d6 on a Bruker WP 200
SY spectrometer using TMS as an internal reference. D2O was added to
every sample to test for the deuterated samples. Mass spectra were re-
corded at 290 °C and 70 eV on a Hewlett-Packard mass spectrometer
model MS-5988. The X-ray diffraction was obtained using Bruker AXS
D8 Advance diffractometer equipped with a graphite monochromator,
variable divergence and antiscatter slits, and a scintillation detector.
The data collection was carried out in air, at room temperature. The
TEM images of nano copper nitrate were obtained in ethanol by using
JEOL HRTEM – JEM 2100 (JAPAN). For conductance measurements, 1
× 10−4 M solution of nano copper nitrate was placed in a titration cell
at a given temperature. Then the conductivity of the solution was mea-
Scheme 1. Molecular structure of the ligand; 4,6-diacetylresorcinol.
2.2.5H2O) in different mixed solvents at different temperatures. Also,
determine the types of complexes which able to form and the most sta-
ble one using the conductance measurements data.
2. Experimental
2.1. Materials
Copper nitrate hemi pentahydrate (Cu(NO3)2.2.5H2O) was obtained
from Merck company (with purity 99.5%). 4,6-Diacetylresorcinol was
synthesized according to the literature method [49] as follows: to 10 g
(73.4 mmol) of zinc chloride and 5 g resorcinol (45.5 mmol), 9.28 g of
acetic anhydride (91.0 mmol) was added dropwise with continuous
stirring. The mixture was heated under reflux at 140 °C in a paraffin
oil path for ~1 h. After cooling, the mixture was poured onto 50% dil.
HCl (~140 mL) where an orange precipitate was formed, which was
then filtered, washed with distilled water till the color of the filtrate is
nearly colorless. The product was recrystallized from ethanol and the
crystalline ligand was kept in a desiccator until used. The yield was
6.88 g (78%); m.p. 179 °C; M. wt.:194.19; elemental analysis data:
sured by addition of (1
×
10−3 M) solution of ligand 4,6-
diacetylresorcinol [50–57]. The titration of nano copper nitrate occurs
step by step and the conductance of the solution was measured after
each addition of ligand. The specific conductance (Ks) of solution was
measured by using a conductivity bridge of type (JENCO – 3173
COND) which has cell constant equal to 1. The temperatures used are
(293.15, 303.15, 313.15 and 323.15 K). Different concentrations of
DMF with water and pure DMF were used in the calculations (70%
DMF, 80% DMF, 90% DMF and 100% DMF).
Fig. 1. IR spectrum of the ligand; 4,6-diacetylresorcinol.

S.G. Sanad, M. Shebl / Journal of Molecular Liquids 294 (2019) 111602
3
Fig. 2. 1H NMR spectra (δ ppm) of the ligand; 4,6-diacetylresorcinol [A: in DMSO, B: after addition of D2O].
3. Results and discussion
3.1. Characterization of the ligand
The structure of the ligand was characterized by elemental analyses,
IR, electronic, mass and 1H NMR spectra. The IR spectrum of the ligand
(Fig. 1) showed four characteristic bands at 3430, 1654, 1586 and
1045 cm−1, which may be assigned to ν(OH) phenolic, ν(C=O),
ν(C=C) and ν(C\\O) phenolic groups, respectively. The electronic
spectrum of the ligand in DMF exhibited two bands at 300 and
370 nm. The higher energy band may be assigned to π-π* transitions
of the aromatic benzene ring while the lower energy band may be
assigned to n-π* transitions and/or charge transfer transitions within
the molecule. The mass spectrum of the ligand showed the molecular
ion peak at m/z 194, confirming its formula weight (F.W. 194.19). 1
H
NMR spectral data (δ ppm) of the ligand relative to TMS (0 ppm) in
DMSO d6 (Fig. 2) supported the suggested structure of the ligand. The
Fig. 3. The X-ray of nano copper nitrate.

4
S.G. Sanad, M. Shebl / Journal of Molecular Liquids 294 (2019) 111602
Fig. 4. TEM images of nano copper nitrate.
signal observed at 12.74 ppm may be assigned to OH groups. The signals
due to aromatic protons were detected as two signals at 8.4 and
6.73 ppm. Finally, the signal observed at 2.64 ppm may be assigned to
CH3 protons.
that nano copper nitrate form small distorted spheres of diameter in
range between 9.63 nm to 34.64 nm. These different sizes were proved
also by X-ray diffraction which gave crystal sizes in the same order. The
non homogeneity in size of crystals is due to ball mill instrument to mill
the salt to nano form.
3.2. X-ray diffraction
3.4. Formation constants of Cu(NO3)2.2.5H2O with 4,6-diacetylresorcinol
The X-ray diffraction of nano copper (II) nitrate is shown in Fig. 3.
From the figure, it was found that there are a lot of diffraction peaks lo-
cated at 14.58°, 20.19°, 28.95°, 31.38°, 32.31°, 35.26°, 39.12°, 42.11°,
43.41°, 48.96°, 51.25°, 53.85° and 58.02° in the XRD pattern. The average
crystal size was calculated from Scherrer equation [58] and it is equal to
28.23 nm.
The molar conductance (Λm) values were calculated using Eq. (1)
[59,60]:
ðKs−KsolvÞ ꢀ Kcell ꢀ 1000
Λm
¼
ð1Þ
C
3.3. TEM images
where Ks and Ksolv are the specific conductance of the solution and the
solvent respectively, Kcell is the cell constant and C is the molar concen-
tration of the Cu(NO3)2.2.5H2O solution.
The TEM images of nano copper (II) nitrate in Fig. 4 were obtained in
ethanol by using JEOL HRTEM – JEM 2100 (JAPAN). TEM images showed
Table 1
Table 2
The molar conductance of the complex and formation constants of Cu(NO3)2.2.5H2O at
293.15 K in presence of 4,6-diacetylresorcinol.
The molar conductance of the complex and formation constants of Cu(NO3)2.2.5H2O at
303.15 K in presence of 4,6-diacetylresorcinol.
Xs of DMF
M:L
[L]
Λobs.
ΛML
Kf
Xs of DMF
M:L
[L]
Λobs.
ΛML
Kf
S.cm2.mol−1
S.cm2.mol−1
S.cm2.mol−1
S.cm2.mol−1
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
9.091 × 10−5
1.176 × 10−4
1.428 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
290.96
291.87
292.49
247.47
253.00
258.42
338.25
340.28
341.98
282.67
289.30
295.82
382.69
385.74
388.48
323.40
330.95
337.18
444.32
448.81
452.98
361.60
370.70
379.69
264
264
264
246
246
246
304
304
304
280
280
280
344
344
344
316
316
316
385
385
385
360
360
360
4.7901 × 103
4.2996 × 103
3.9537 × 103
8.9828 × 105
1.2099 × 105
4.9007 × 104
9.8273 × 103
8.6380 × 103
7.7502 × 103
9.4280 × 105
1.7824 × 105
7.7498 × 104
6.6099 × 103
5.5911 × 103
4.8285 × 103
2.0305 × 105
7.3402 × 104
4.0608 × 104
5.3355 × 103
4.4911 × 103
3.8440 × 103
1.7840 × 106
1.7404 × 105
6.9232 × 104
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
9.091 × 10−5
1.176 × 10−4
1.428 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
9.091 × 10−5
1.176 × 10−4
1.428 × 10−4
333.95
335.88
337.48
286.00
292.42
297.51
382.69
385.74
388.48
315.73
323.40
330.95
409.92
413.61
416.98
336.00
344.30
352.49
497.35
503.08
508.47
411.40
421.63
430.52
300
300
300
278
278
278
340
340
340
310
310
310
360
360
360
330
330
330
440
440
440
400
400
400
5.4613 × 103
4.7402 × 103
4.2080 × 103
1.4299 × 105
5.7542 × 104
3.3197 × 104
4.4408 × 103
3.7280 × 103
3.1913 × 103
3.4700 × 105
9.5715 × 104
4.4262 × 104
4.3125 × 103
3.5987 × 103
3.0578 × 103
3.7066 × 105
1.0053 × 105
4.6321 × 104
4.7672 × 103
3.8321 × 103
3.1372 × 103
1.6268 × 105
6.2259 × 104
3.4298 × 104
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
0.3528
0.4831
0.6774
1.0000
0.3528
0.4831
0.6774
1.0000

S.G. Sanad, M. Shebl / Journal of Molecular Liquids 294 (2019) 111602
5
Table 3
Table 4
The molar conductance of the complex and formation constants of Cu(NO3)2.2.5H2O at
313.15 K in presence of 4,6-diacetylresorcinol.
The molar conductance of the complex and formation constants of Cu(NO3)2.2.5H2O at
323.15 K in presence of 4,6-diacetylresorcinol.
Xs of DMF
M:L
[L]
Λobs.
ΛML
Kf
Xs of DMF
M:L
[L]
Λobs.
ΛML
Kf
S.cm2.mol−1
S.cm2.mol−1
S.cm2.mol−1
S.cm2.mol−1
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
411.35
415.08
418.48
337.07
345.40
353.62
475.85
481.08
485.98
385.07
394.9
404.62
530.31
536.81
542.97
425.60
436.70
447.69
584.78
592.55
599.97
466.13
478.50
490.76
365
365
365
335
335
335
416
416
416
384
384
384
458
458
458
422
422
422
500
500
500
460
460
460
4.8995 × 103
4.0739 × 103
3.4544 × 103
1.1047 × 106
1.4236 × 105
5.7715 × 104
4.0983 × 103
3.3281 × 103
2.7472 × 103
2.4662 × 106
1.5652 × 105
5.9952 × 104
4.3317 × 103
3.5167 × 103
2.8991 × 103
8.8622 × 105
1.4090 × 105
5.8689 × 104
4.1055 × 103
3.3090 × 103
2.7044 × 103
5.8432 × 105
1.2575 × 105
5.5078 × 104
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
9.091 × 10−5
1.176 × 10−4
1.428 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
6.250 × 10−5
9.091 × 10−5
1.176 × 10−4
3.023 × 10−4
3.182 × 10−4
3.333 × 10−4
9.091 × 10−5
1.176 × 10−4
1.428 × 10−4
526.01
532.41
538.47
433.40
444.29
453.86
576.18
583.75
590.97
459.73
471.90
483.96
624.91
633.62
641.97
496.00
509.29
522.50
679.38
689.35
698.97
551.09
565.57
578.70
470
470
470
420
420
420
495
495
495
455
455
455
535
535
535
485
485
485
590
590
590
530
530
530
1.0275 × 104
8.4390 × 103
7.0844 × 103
2.1884 × 105
8.9518 × 105
5.0905 × 104
3.0080 × 103
2.3459 × 103
1.8471 × 103
6.4361 × 105
1.1592 × 105
4.8753 × 104
5.3381 × 103
4.3459 × 103
3.5942 × 103
3.9854 × 105
1.1806 × 105
5.6122 × 104
5.5744 × 103
4.4491 × 103
3.6109 × 103
1.4547 × 105
6.3214 × 104
3.6135 × 104
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
1:2
1:1
0.3528
0.4831
0.6774
1.0000
0.3528
0.4831
0.6774
1.0000
The relations between the molar conductance (Λm) and molar ratio
of metal to ligand (M:L) indicate that two types of complexes with M:
L ratios 1:2 and 1:1 are formed. The complex formation constant (Kf)
and the molar conductance of the complex (ΛML) were obtained by
computer fitting of Eqs. (2) and (3) to the molar conductance- mole
ratio data using a nonlinear least squares program KINFIT [61]. The for-
mation constants (Kf) for the complexes were calculated for each type of
complexes 1:2 and 1:1 by using Eq. (2) [62,63]:
3.6. Relations between logKf and 1/T
Relations between log Kf and 1/T for nano copper nitrate in presence
of 4,6-diacetylresorcinol as a ligand by different ratios of metal to ligand
(M:L) at different concentrations of DMF–H2O (volume by volume) are
shown in Figs. 9 and 10. The correlation coefficients for the lines in
Figs. 9–10 are in the range 0.993 to 0.999, which means very strong di-
rect relation between log Kf and 1/T.
Λ
M−Λobs
3.7. Gibbs free energies, enthalpies and entropies of formation
Kf
¼
ð2Þ
ðΛobs–ΛMLÞ½Lꢁ
Gibbs free energy of formation is calculated from Eq. (3) [64–69]:
where ΛM is the limiting molar conductance of the salt alone, Λobs is the
molar conductance of solution during titration and ΛML is the molar con-
ductance of the complex.
ΔGf ¼ −RT ln Kf
ð3Þ
The formation constants and the molar conductance of the complex
for nano copper nitrate hemi pentahydrate in presence of 4,6-
diacetylresorcinol as a ligand at different concentrations of DMF–
water at different temperatures are listed in Tables 1–4. The formation
constants for the interaction of nano Cu(NO3)2.2.5H2O with 4,6-
diacetylresorcinol for M:L ratio equal 1:1 complex are more than the
formation constants for M:L ratio equal 1:2 complex which indicate
that the first complex is more stable. These results are consistent with
our previously published data about the solid complex for copper ni-
trate with 4,6-diacetylresorcinol; as the obtained solid complex was of
2:2; M:L (i.e. 1:1) molar ratio [45].
Gibbs free energies of formation of complex M:L with ratio 1:1 are
more negative than those of 1:2 complex which means that 1:1 com-
plex is more easy and more favourable complex to form. The values of
free energies for the two complexes are negative values.
The enthalpies and entropies of formation for nano copper nitrate in
presence of ligand 4,6-diacetylresorcinol in different mole fractions of
mixed DMF – water solvents at different temperatures are tabulated
in Tables 5 and 6. The enthalpies of formation (ΔHf) were calculated
from the slopes of relation between log Ksp and 1/T, (slopes = −ΔH/
2.303R) [70,71]. The entropies of formation (ΔSf) were calculated by
use of Gibbs-Helmholtz Eq. (4) [72–76]:
3.5. Relation between Λm and CM/CL
ΔGf ¼ ΔHf −TΔSf
ð4Þ
The relations between molar conductance Λm and the concentration
of metal to ligand [M]/[L] of nano copper nitrate with 4,6-
diacetylresorcinol in different concentrations of DMF – water (70%,
80%, 90% and 100% DMF by volume) at different temperatures are
shown in Figs. 5–8. From Figs. 5–8, two inflections at CM/CL equal 0.5
and 1 indicating 1:2 and 1:1 metal (M) to ligand (L) complexes are
formed. The correlation coefficients for the curves in Figs. 5–8 are in
the range −0.90 to −0.94, which means strong reversible relation be-
tween molar conductance and [M]/[L].
4. Conclusion
The relations between Λm and CM/CL of nano copper nitrate with 4,6-
diacetylresorcinol as a ligand show that two types of complexes with M:
L ratios 1:2 and 1:1 are formed. The formation constants for the interac-
tion of nano copper nitrate with 4,6-diacetylresorcinol have the

6
S.G. Sanad, M. Shebl / Journal of Molecular Liquids 294 (2019) 111602
A: 70% DMF – 30% water
B: 80% DMF –20% water
C: 90% DMF –10% water
D: 100% DMF –0% water
Fig. 5. The relation between Λm and CM/CL at 293.15 K.
following trend of M:L ratio:
constants and lower values of molar conductance. The values of
free energies of formation for metal to ligand ratio equal 1:1 com-
plex are more negative values than those of 1:2 complex which
means that 1:1 complex is more favourable complex and more
easy to form. All negative values of free energies of the two types
of complexes show that the process is spontaneous. The molar
Kf for 1 : 1 complexNKf for 1 : 2 complex
This indicates that the first complex 1:1 is more stable than 1:2
complex because the first complex has higher values of formation
A: 70% DMF – 30% water
B: 80% DMF –20% water
C: 90% DMF –10% water
D: 100% DMF –0% water
Fig. 6. The relation between Λm and CM/CL at 303.15 K.

S.G. Sanad, M. Shebl / Journal of Molecular Liquids 294 (2019) 111602
7
A: 70% DMF – 30% water
B: 80% DMF –20% water
C: 90% DMF –10% water
D: 100% DMF –0% water
Fig. 7. The relation between Λm and CM/CL at 313.15 K.
A: 70% DMF – 30% water
B: 80% DMF –20% water
C: 90% DMF –10% water
D: 100% DMF –0% water
Fig. 8. The relation between Λm and CM/CL at 323.15 K.

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S.G. Sanad, M. Shebl / Journal of Molecular Liquids 294 (2019) 111602
Table 6
Gibbs free energies, enthalpies and entropies of formation of nano copper nitrate in pres-
ence of 4,6-diacetylresorcinol at different temperatures for M:L = 1:1.
T (K)
X
s of DMF
ΔGf
ΔHf
ΔSf
(kJ/mol)
(kJ/mol)
(kJ /mol.K)
293.15
0.3528
0.4831
0.6774
1.0000
0.3528
0.4831
0.6774
1.0000
0.3528
0.4831
0.6774
1.0000
0.3528
0.4831
0.6774
1.0000
−33.4104
−33.5283
−29.7862
−35.0827
−29.9185
−32.1528
−32.3191
−30.2436
−36.2285
−38.3193
−35.6546
−34.5702
−33.0356
−35.9338
−34.6461
−31.9384
−59.7500
−60.9442
−61.5460
−65.9973
−59.7500
−60.9442
−61.5460
−65.9973
−59.7500
−60.9442
−61.5460
−65.9973
−59.7500
−60.9442
−61.5460
−65.9973
−0.0899
−0.0935
−0.1083
−0.1055
−0.0984
−0.0950
−0.0964
−0.1179
−0.0751
−0.0722
−0.0827
−0.1004
−0.0827
−0.0774
−0.0832
−0.1054
303.15
313.15
323.15
Fig. 9. Relation between log Kf and 1/T by ratio M:L equal 1:2.
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ΔSf
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