GROWTH AND CHARACTERIZATION OF UREA - THIOUREA MIXED CRYSTAL

Submitted by Ms. SUREKA.G Reg No : 21010 Under the Guidance of Dr. Sr. GERARDIAN JEYAM, Ph.D
HOLY CROSS COLLEGE (AUTONOMO NAGERCOIL 4

ABSTRACT
 Crystal growth and characterization studies found to be a fascinating field in advancing Science and Technology.  Pure and Mixed Crystals are of wide application in different areas of developments.  Characterization studies were carried out by collecting powder xray diffraction pattern.  Assigned the miller indices and calculated the lattice parameters using the PXRD data verified the result with that of expected structure.  FT-IR spectroscopic analysis carried helps to determine the chemical functional groups present in the sample. 

UV studies were carried for both pure and mixed crystals.

INTRODUCTION
Crystals are the unacknowledged pillers of modern technology. It used for semiconductors, superconductors, polarizers. The metal complex of thiourea is called semi organics. It includes the advantages of both organics and inorganic materials. There are two stages involved in this project Growth of pure and mixed crystals using slow evaporation method. Characterization studies.

MATERIALS AND METHODS

PROPERTIES OF UREA IUPAC name Molecular formula Molar mass

: Urea : CH4N2O : 60.06 g/mol

USES Fertilizer, fuel in power generation, Urine therapy

PROPERTIES OF THIOUREA IUPAC name : Thiourea Molecular formula : CH4N2S Molar mass : 76.12 g/mol USES Sulphur sources for making semiconductor cadmium sulfide nanoparticle

SOLUTION PREPARATION


Pure urea-thiourea and urea-thiourea mixed crystals were crystallized by the slow evaporation method.  pure urea, pure thiourea, urea-thiourea (1:9) mixed crystal, (9:1) mixed crystal, (1:3) mixed crystal, (2:3) and (3:2) mixed crystals respectively were grown by using deionized water.

 40 ml saturated solution of urea and thiourea was prepared at 40rC with agitation by a magnetic stirrer continuously for about two hours.  Then heat was applied using a heater-cum-stirrer and the obtained supersaturated solution was filtered. The above 40ml supersaturated solution of urea and thiourea was transferred into a beaker labeled A and B.  C is obtained by pouring supersaturated solution of urea-thiourea (1:9) stirred continuously for about two hours while D,E,F,G crystallites are prepared by the same process by adding different compositions.  Nucleation ie) tiny crystals nucleates at the centre of the beaker within two weeks, large crystals were obtained after 10 days.

Photograph of the grown crystals

RESULTS AND DISCUSSION

X RAY DIFFRACTION ANALYSIS
The grown crystals were characterized by powder. X-ray diffraction analysis (XRD) to confirm the identity of a solid material and determining crystallinity and phase purity. In the present study, 6 sets of XRD were taken for urea thiourea pure and mixed crystals. These studies were compared with JCPDS values  In XRD pattern the intensity in counts is taken along Y-axis and 2 along Xaxis.

XRD pattern of as grown urea crystal

FROM JCPDS d-spacing (Ar)

4.704 3.9916 3.6137 3.0435 2.8225 2.5245 2.4202 2.3520

Int
15 999 237 254 68 114 94 16

hkl
001 110 101 111 200 210 201 002

FROM PRESENT WORK Relative Lattice d-spacing intensity parameters (Ar) (%) (Ar)
4.71042 4.00117 3.62243 3.05021 2.83115 2.53086 2.42660 2.35517 055 100 11.97 17.54 7.35 15.84 8.14 0.99 a = 5.662 b = 5.662 c = 4.710

XRD pattern of as grown thiourea crystal

FROM JCPDS d-spacing (Ar)

4.6061 4.4173 4.2680 3.0895 2.050 2.8143 2.7355 60 807 999 590 192 420 60

Int
011 101 020 201 211 220 002

hkl

FROM PRESENT WORK Relative Lattice d-spacing (Ar) intensity parameters (%) (Ar)
4.62810 4.47009 4.28307 3.09246 2.95519 2.85846 2.75027 6.48 75.50 100 77.24 27.61 41.94 12.94 a = 7.486 b = 8.566 c = 5.501

XRD pattern of 1:9 mixed crystal

FROM JCPDS d-spacing (Ar)

4.6061 4.4173 4.2680 3.0895 2.9050 2.8143 2.7355 60 807 999 590 192 420 60

FROM PRESENT WORK hkl

011 101 020 201 211 220 002

Int

d-spacing (Ar)
4.64585 4.48687 4.29772 3.09970 2.96106 2.86489 2.75439

Relative intensity (%)

8.24 77.96 100 87.88 30.54 52.43 15.41

Lattice parameters (Ar)

a = 7.495 b = 8.595 c = 5.508

XRD pattern of 1:3 mixed crystal as grown thiourea crystal

FROM JCPDS d-spacing (Ar)

4.6061 4.4173 3.0895 2.9050 2.8143 2.7355 2.5243 2.4603 60 807 590 192 420 60 221 385

Int
011 101 201 211 220 002 031 112

hkl

FROM PRESENT WORK Relative Lattice intensity parameters d-spacing (Ar) (%) (Ar)
4.52059 4.32869 3.11075 2.97703 2.88111 2.76369 2.54863 2.49097 77.46 80.78 95.37 40.86 75.08 15.09 46.81 57.86 a = 7.509 b = 8.657 c = 5.527

XRD pattern of 2:3 mixed crystal as grown thiourea crystal

FROM JCPDS d-spacing (Ar)

4.6061 4.4173 4.2680 3.0895 2.050 2.8143 2.7355 2.5243 60 807 999 590 192 420 60 221

Int

hkl
011 101 020 201 211 220 002 031

FROM PRESENT WORK Relative Lattice d-spacing intensity parameters (Ar) (%) (Ar)
4.64467 4.48583 4.29721 3.09899 2.96073 2.86430 2.75347 2.53799 6.50 75.55 100 81.18 30.03 51.62 11.61 37.88 a = 7.488 b = 8.594 c = 5.506

XRD pattern of 3:2 mixed crystal as grown thiourea crystal

FROM JCPDS d-spacing (Ar)

4.6061 4.4173 4.2680 3.0895 2.050 2.8143 2.7355 2.5243 60 807 999 590 192 420 60 221

Int
011 101 020 201 211 220 002 031

hkl

FROM PRESENT WORK Relative Lattice d-spacing intensity parameters (Ar) (%) (Ar)
4.61661 4.46160 4.27413 3.08937 2.95075 2.85694 2.74859 2.53269 6.14 95.74 41.95 55.06 31.37 34.03 9.14 21.85 a = 7.482 b = 8.548 c = 5.497

FOURIER TRANSFORM INFRARED SPECTRAL ANALYSIS  It was used to analyze qualitatively the presence of functional groups in grown crystals. The FTIR spectra are recorded in the region 400-4000cm-1
 It is used to calculate the absorbance value. Absorbance A = log Where, To, Ts p from the FTIR spectrum  It is also used to calculate the composition of the mixed crystals.

A1 = a1x + b1 (1-x) Where, A1 p absorbance value of mixed crystals. a1 p absorbance value of pure urea crystals. b1 p absorbance value of pure thiourea crystals. x p finding the composition value.

FTIR spectrum of urea crystal

WAVE NUMBE R (cm-1)

3401.88 5.01 56 1.048

ABSORBANCE TS TO VALUE A=Log(TO/TS)

2937.07

48.32

80

0.218

2353.52

92.48

98

0.025

1703.92

29.01

42

0.160

1635.01

31.52

78.5

0.396

1375.92

22.81

62.5

0.437

1233.08

48.24

65

0.129

1065.51

26.01

89

0.534

FTIR spectrum of thiourea crystal

WAVE NUMBER (cm-1)

3714.58 25.09 34

ABSORBANCE TS TO VALUE A=Log (TO/TS)

0.131

3519.45

25.87

27

0.018

3286.92

20.09

22

0.039

2353.25

14.36

18.2

0.102

2114.68

14.81

20.1

0.132

1816.65

35.73

50.2

0.147

1611.53

6.47

13

0.303

721.82

23.45

34.2

0.163

627.78

17.23

18.

0.037

FTIR spectrum of 1:9 mixed crystal

WAVE NUMBER (cm-1) TS TO

ABSORBANCE VALUE A=Log (TO/TS)

2888.08

13.47

16

0.074

2677.95

12.27

20

0.212

2359.51

21.48

27

0.099

2116.42

19.86

40

0.304

1816.84

47.76

68

0.153

1595.95

5.70

17

0.474

1075.33

6.78

11.2

0.217

711.89

40.37

43

0.027

FTIR spectrum of 9:1 mixed crystal

WAVE NUMBER (cm-1) TS TO

ABSORBANCE VALUE A=Log (TO/TS)

3445.30

12.93

21

0.210

3345.77

16.72

24

0.212

2806.38

81.05

89.1

0.041

2651.78

84.18

92.3

0.039

1620.05

8.10

35

0.635

1462.13

16.73

82

0.690

789.22

89.52

98

0.039

724.20

84.19

92.5

0.040

FTIR spectrum of 1:3 mixed crystal

WAVE NUMBER (cm-1)

3444.09 6.31 15

ABSORBANCE TS TO VALUE A=Log (TO/TS)

0.376

2948.68

70.81

84

0.074

2103.19

93.89

98

0.018

1748.05

70.07

74.3

0.025

1590.14

25.54

88.2

0.538

1354.17

62.45

94.4

0.179

1242.49

67.03

95

0.151

1056.16

89.49

100

0.048

Comparison of FTIR bands of urea thiourea mixed crystals

EARLY REPORTED PROPORTIONS UREA-THIOUREA MIXED CRYSTAL THIOUREA CM-1 UREA CM-1 BAND ASSIGNMENTS

1:9

3319 1595 1381 1075 711

3376 1627 1417 1089 740 3376 1627 1627 1417 1089 3376 3280 3167 1417 1089

1683 3435 1683 1471 3435 1683 -

Yas NH2 Hs (NH2) Yas (C=S) Ys (C-N) Ys (C=S) Yas NH2 Yas NH2 Hs NH2 Hs NH2 Yas CN Yas NH2 Hs NH2 Yas C=S Ys (C-N) Yas NH2 Ys NH2 Ys NH2 Hs NH2 Yas C=S Ys (C-N)

9:1

3445 3345 1674 1620 1462

1:3

3444 1590 1354 1056

2:3

3355 3275 3160 1593 1416 1082

ULTRA VIOLET-VISIBLE SPECTRAL STUDIES

The optical absorption and transmission spectra were recorded for urea thiourea mixed crystal. The spectra were recorded in the wavelength region from 190 to 1190 nm using lambda 35 spectrometer. All the mixed crystals have low absorbance in the visible region. The cut off wavelength of absorbance for all the mixed crystals have 330 nm and 1:3 mixed crystal has 332 nm.

SUMMARY AND CONCLUSIONS Crystals are grown artificially everyday and are more concerned to discover new materials for the purpose of academic and industrial uses, as the need of single crystals is increased in solid state device, scientists interests have turned from pure crystals to impurity (dopant) added and mixed single crystals. In this project crystal growth studies have been carried out on supersaturated aqueous solutions of urea mixed with thiourea in different concentrations. The crystals were characterized by XRD in which the lattice parameters a, b, c were calculated and compared with the standard JCPDS values, X-ray diffraction confirms that the grown crystals belongs to orthorhombic group  The peaks in the FTIR spectra pure, shows the presence of two amine (-NH2) group and C=S bonds. From the FTIR spectra, we calculate the composition of the mixed crystal. It is found that the estimated composition well agreed with original composition. UV studies (ie) optical absorbance and transmittance studies have been carried out for the transparent crystals. It has high transmittance in the visible region. Therefore it is used in Opto electronics.