Growth of Copper Sulfate Pentahydrate Single Crystals by Slow Evaporation Technique

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Growth of Copper Sulfate Pentahydrate Single Crystals by Slow Evaporation


Technique

Article · March 2017


DOI: 10.24297/jap.v13i2.5963

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ISSN 2347-3487
Volume 13 Number 2
Journal of Advances in Physics

Growth of Copper Sulfate Pentahydrate Single Crystals


by Slow Evaporation Technique
Nabeel A. Bakr1, Tariq A. Al- Dhahir2, and Saja B. Mohammad1
1
Department of Physics, College of Science, University of Diyala, Diyala, Iraq
2
Department of physics, College of Education for Pure Science (Ibn AlHaitham),
Baghdad University, Baghdad,Iraq
nabeelalibakr@yahoo.com, nabeelalibakr@sciences.uodiyala.edu.iq

ABSTRACT
Single crystals of CuSO4.5H2O (CSP) were grown by slow evaporation solution technique at room temperature from its
3
aqueous solution with molarity (0.25, 0.5 and 1.5) M. The sizes of the crystals were up to (39×12×3) mm ,
3 3
(33.05×30.5×4.7) mm and (19.12×15.3×5.5) mm respectively. XRD patterns were recorded for powder of single crystals
to find the parameters of crystals. FTIR studies confirm the presence of various functional groups in the crystals. The
optical absorption was study by using UV-Vis analysis. The spectra show low absorbance in the range between 300 nm
and 550 nm. Energy gap (Eg) of crystals was found to be (4.17, 4.19 and 4.25) eV at the molarity of (0.25, 0.5 and 1.5) M
respectively.

Indexing terms/Keywords
CuSO4.5H2O, single crystals, slow evaporation, XRD, FTIR, UV-Vis

Academic Discipline and Sub-Disciplines


Physics, Material Science

1. INTRODUCTION
Growth of crystals is the basis for many technological developments and the solution method is a very important process
because it's used in many applications and industry [1,2]. Solid bodies in which the elementary building blocks are
arranged regularly in the space lattice with specific geometrical symmetry are called crystals [3]. The kinetics of crystal
growth and nucleation in connection with the quantity of material available for growth of crystal determine the produced of
number and volume of the crystals [4]. The pentahydrate form of copper sulfate (CuSO4·5H2O) is a bright blue in colour
1
belonging to the space group Ci and it has triclinic system [5,6]. The single crystal of copper sulfate is used as broadband
UV optical filters by Manomenova et al. in (2013) [7]. The aim of this paper is to give report about the growth of copper
sulfate (CSP) single crystals with different molarities by slow evaporation method. The XRD diffraction and FTIR spectral
analysis for the powdered samples are used to identify the structural properties of single crystals. The grown crystals are
polished to thickness of (2 mm) to record the optical absorption.

2. Experimental
CuSO4.5H2O powder provided by [BDH Chemicals Ltd Poole England] with "minimum assay (ex Cu) 98.5%, maximum
limits of impurities, Alkalis (sulphated) 0.5%, Chloride (Cl) 0.005%, Iron (Fe) 0.08%", is used to grow CuSO4.5H2SO4 single
crystals by slow evaporation method with molarities of 0.25, 0.5 and 1.5 M using double distilled water as a solvent. The
mixture of distilled water and CSP salt at different molarities is placed in a magnetic stirrer and mixed up well to get
homogenous solution. The solution was filtered using filter paper and allowed for slow evaporation at room temperature.
The good quality crystals were collected after 82, 91 and 42 days for molarities 0.25, 0.5 and 1.5 M respectively. The
grown crystals are shown in Fig. 1. The starting of nucleation, the time of growth and the size of these crystals are shown
in the table (1).

Fig. 1: As grown crystals of (CSP).

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ISSN 2347-3487
Volume 13 Number 2
Journal of Advances in Physics

Table 1: Time of crystallization and size of crystals.


The time of the beginning of The time of completion of
Molarity of solution nucleation crystal The size of large crystal
3
(M) (mm )
(days) (days)
0.25 78 82 39×12×3
0.5 76 91 33.5×30.5×4.7
1.5 2 42 19.12×11.38×8

3. Results and Discussion


X-ray Diffraction Analysis
The powdered forms of the grown crystals were subjected to powder X-ray diffraction analysis. The X-ray diffraction data
were recorded using "XRD 6000" which has the properties, "Source: Cu kα, Wavelength 1.5406 Å, Scan model continues
scan, range (10-50) degrees". The recorded PXRD patterns of (CSP) are shown in Fig. 2. The parameters of unit cell are
in agreement with the (ICDD) card number 11-0646. The narrow peaks in the XRD patterns show the good quality
crystalline nature of the grown crystals [8]. The highest peak of the samples occurs at 2θ~ 18° which is referred to
plane. From Fig. 2, it is clear that the increase in the molarity leads to a change in the intensity of peaks when compared
with each other because the planes of particles in the powder are not aligned so the reflections intensities were not equal
in all direction [9]. From PXRD diffraction analysis, it has been confirmed that the grown crystals belong to triclinic system.
The comparison of the cell parameter values of crystals is shown in table (2).

Fig. 2: PXRD patterns of grown crystals.


Table 2: Unit cell parameters for samples of crystals grown at room temperature.
Lattica Parameters Molarity (M) Standard
0.25 0.5 1.5 11-0646
) 7.156 7.174 7.250 7.155
) 10.28 10.74 10.88 10.71
) 5.9084 5.9625 6.092 5.955
α (deg.) 96.50 97.48 98.07 97.63
β (deg.) 124.8 125.3 125.5 125.3
γ (deg.) 94.41 94.46 94.20 94.32

FTIR Analysis
The FTIR analysis of (CSP) single crystals were carried out using "IR Affinity-1" spectrophotometer by "KBr" pellet method
-1
in the wave number range of (400 to 4000 cm ). The transmittance spectra of the grown crystals are shown in Fig. 3. The
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ISSN 2347-3487
Volume 13 Number 2
Journal of Advances in Physics

-1 -1 -1
O-H stretching absorption bands appears at 3446 cm , 3448 cm and 3344 cm for molarities 0.25, 0.5 and 1.5 M
-1 -1 -1
respectively [10]. Bending vibration of O-H appears at 1629 cm , 1625 cm and 1633 cm for the molarities 0.25, 0.5, 1
-1 -1 -1
and 1.5 M respectively [11]. The Stretching vibration of S-O group appears at 1151 cm , 1151 cm and 1209 cm for
-1 -1 -1
molarities 0.25, 0.5 and 1.5 M respectively. The SO4 non-degenerate mode appears at 997 cm , 995 cm and 997 cm
+2 -1 -1
for molarity 0.25, 0.5 and 1.5 M [12]. The Vibration mode of metal ion Cu (Cu-O-H) appears at the 785 cm , 785 cm
-1 -1 -1
and 786 cm for 0.25, 0.5 and 1.5 M respectively [13]. The SO4 degenerate mode appears at the 659 cm , 659 cm and
-1 -2 -1
657 cm for molarities 0.25, 0.5 and 1.5 M respectively [14]. The SO4 bending group of sulfate appears at 453 cm , 451
-1 -1
cm and 516 cm for the molarities 0.25, 0.5 and 1.5 respectively [11].

Fig. 3: FTIR transmittance spectrum of (0.25 M) crystal.

Fig. 4: FTIR transmittance spectrum of (0.5 M) crystal.

Fig. 5: FTIR transmittance spectrum of (1.5 M) crystal.


-2
The difference in appearance of modes of ions (SO4 ) is attributed to the chemical reactivity of copper salts on KBr
windows [15]. From table (3) it is clearly seen that all bands shift to higher or lower wavenumbers with changing the
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ISSN 2347-3487
Volume 13 Number 2
Journal of Advances in Physics

molarity and this can be attributed to the external factors such that impurities, temperature and pressure during growth of
crystals.
Table 3: IR bands of CSP grown crystals.
-1
Wave number (cm ) Assignment
0.25 M 0.5 M 1.5 M
3446 3448 3344 O-H stretching
1629 1625 1633 O-H bending
1151 1151 1209 S-O Stretching
997 995 997 SO4 non-degenerate
mode
785 785 786 Cu-O-H Vibration mode
659 659 657 SO4 degenerate mod
-2
453 451 516 SO4 bending group of
sulfate

UV-Vis Spectral Analysis


UV-Visible absorption spectra of (CSP) crystals were recorded by using "UV–Visible 1800 Double beam
spectrophotometer" in the range of 200-800 nm. The crystals of CSP were cut and polished into plates. The spectra are
shown in Fig. 4. Information about the electronic structure of the molecules can be extracted from UV-Visble spectra due to
promotion of the electrons from the ground state to higher states [16]. From the UV-Visible spectra for the crystals of
(CSP) it is noticed that the absorbance does not exceed two units in the entire visible region. The absorbance increases
with decreasing the molarity. There is an abnormal absorption peak at ~340 nm that may be belong to distorted CuO 6
+2 9
octahedron because the copper ion Cu in the electronic configuration d exhibits the Jahn-Teller effect [17]. The spectra
show low absorbance in the visible region but higth absorbance in the infrared region and the ultraviolet region (~ 200-290)
nm, this is in agreement with the results reported by Anne et al. [13]. The (CSP) crystals is transparent in the wavelength
range between 300 nm and 530 nm and it can be used as optical bandpass filters in this range, this result is in agreement
with the results reported by Manomenova et al. [7] and Anne et al. [13]. The indirect band gap value of (CSP) crystals can
1/2
be found by plotting (αh ) versus (h ). The energy gap was found to be 4.17, 4.19 and 4.25 eV for the molarities 0.25,
0.5 and 1.5 M respectively [4,13]. The energy gap plots are shown in Fig. 5.

4.5

4.0

3.5

3.0
Absorbance (A)

2.5

2.0

1.5

1.0 0.25 M
0.5 M
0.5 1.5 M

200 300 400 500 600 700 800


Wavelength  (nm)

Fig. 4: Absorbance A) versus w velength λ) of CSP) single ryst l.

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Volume 13 Number 2
Journal of Advances in Physics

9 0.25 M

1/2
(h) (eV/cm)
6

1/2
5

4
Eg= 4.17

3
1 2 3 4 5 6 7
Photon energy h (eV)

9 0.5 M

7
1/2
(h) (eV/cm)

5
1/2

Eg= 4.19 eV
3

2
1 2 3 4 5 6 7
Photon energy h (eV)

9 1.5 M

7
1/2

6
(h) (eV/cm)

5
1/2

3
Eg= 4.25 eV
2

1 2 3 4 5 6 7
Photon energy h (eV)

1/2
Fig. 5: The rel tion etween αh ) and (h ) of (CSP) single crystals.
Conclusion
Single crystals of (CSP) were grown by slow evaporation process with solution molarities 0.25, 0.5 and 1.5 M. The slowest
crystallization process occurs at solution molarity of 0.5 M where the time needed for completion of crystallization process
3
was 91 days producing the largest crystal size of 33.5×30.5×4.7 mm . X- ray diffraction analysis is conducted on CSP
crystals using the powdered pattern. The PXRD diffraction analysis revealed that the crystals belong to triclinic system. It is
noticed that the highest peak of the samples occurs at 2θ~ 18° which is referred to plane. The vibrational modes of

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ISSN 2347-3487
Volume 13 Number 2
Journal of Advances in Physics

functional groups were identified using FTIR spectroscopic technique. The UV-Vis spectral study highlights the excellent
transparency of the crystal in the entire visible region. Energy gap (Eg) of crystals is found to be 4.17, 4.19 and 4.25 eV at
the molarities 0.25, 0.5 and 1.5 M respectively. The (CSP) crystals can be used as optical bandpass filters.

References
1. R. Thilagavathi, P. Selvarajan and V. Vasantha Kumari, (2012), J. of advanced scientific and technical research,
6, 2, 164-183.
2. S. Mary Delphine, R. Krishna Priya, T. Lidia Arockia Thai and S. Ajitha, (2014), Scholars Research Library, 6, 4,
157-161.
3. Sandhya Ravi and S.Chenthamarai, (2014), Indian J. Sci. Res., 9, 1, 051-057.
4. Russell A. Judge, Randolph S. Jacobs, Tyralynn Frazier, Edward H. Snell, and Marc L. Pusey, (1999),
Biophysical Journal, 77, 1585–1593.
5. K. Boopathi, P. Ramasamy, G. Bhagavannarayana, (2014), J. of Crystal Growth, 386, 32–37.
6. J. Berger, (1976), J. of Raman Spectroscopy, 5, 103-114.
7. V. L. Manomenova, M. N. Stepnova, V. V. Grebenev, E. B. Rudneva, and A. E. Voloshin, (2013), published in
Kristallografiya, 58, 3, 505–509.
8. J. A. Hudson, C. K. Mahadevan, C. M. Padma, (2014), Int. Journal of Engineering Research and Applications, 4,
257-266.
9. T. A. AL-Dhahir, T. M. AL-Saadi, (2009), J. of college of education, 3, 960-967.
10. M. R. Jagadeesh, H. M. Suresh Kumar, R. Ananda Kumari, (2014), Archives of Applied Science Research, 6,
188-197.
11. Richard A. Nyquist and Ronald O. Kagel, (1971), "Infrared Spectra of Inorganic Compounds", ACADEMIC
PRESS, INC, New York.
12. S. M. Delphine, R. K. Priya, T. L. A. Thai and S. Ajitha, (2014), Scholars Research Library, 6, 4, 157-161.
13. M. M. Anne, S. Perumal, K. M. Prabu, (2015), Research in Engineering and Technology, 04, 07, 41-44.
14. A. Periasamy, S. Muruganand and M. Palaniswamy, (2009), Rasayan J. Chem. , 2, 4, 981-989.
15. J. Berger, (1976), J. of Raman Spectroscopy, 5, 103-114.
16. S. Radhika, C. M. Padma, A. J. Rajendran, S. Ramalingom and T. Chithambara Thanu, (2012), Der Pharma
Chemica, 4, 5, 2014-2023.
17. J. N. Varghese and E. N. Maslen, (1985), Acta Cryst., B41, 184-190.

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