You are on page 1of 6

Indian Journal of Pure & Applied Physics

Vol 46, July 2008, pp. 507-512

Growth and characterization of struvite crystals


Chetan K Chauhan, K C Joseph, B B Parekh# & M J Joshi*
Crystal Growth Laboratory, Department of Physics, Saurashtra University, Rajkot 360 005 (Gujarat)
*E-mail: mshilp24@rediffmail.com
Received 2 August 2006; revised 6 December 2007; accepted 17 January 2008
Struvite or ammonium magnesium phosphate hexahydrate (AMP) containing urinary stones are infection stones
associated with urea splitting organisms, which are more common in women. Struvite crystals having different
morphologies were grown by single diffusion gel growth technique in silica gel. The crystals were characterized by powder
XRD, FT-IR, TGA and dielectric study. Kinetic and thermodynamic parameters were evaluated from thermogram.
Dielectric study showed that the value of dielectric constant is found to decrease as the frequency increased. The ac
resistivity and ac conductivity were also evaluated at different frequency.
Keywords: Struvite crystals, Crystal growth, FT-IR, Thermal study, Kinetic and thermodynamic parameters, Dielectric study

1 Introduction
Struvite or ammonium magnesium phosphate
hexahydrate (AMP) containing urinary stones are
usually found in women. These struvite stones are
infection stones associated with urea generating
organisms1. A study of struvite precipitation and
urease activity in bacteria isolated from patients with
urinary infections and their possible involvement in
the formation of renal calculi has been reported by
Rivadeneyra et al2. The in-vitro inhibition of struvite
crystal growth by acetohydroxyamic acid has been
reported by Downey et al3. They have grown struvite
crystals by Proteus mirabilis in artificial urine in the
presence of urease inhibitors acetohydroxyamic acid
(AHA). In the absence of AHA, struvite crystals
assumed dendritic growth along (100) axis but in the
presence of AHA the growth was reduced and the
crystals achieved octahedral morphology.
Struvite or AMP, (NH4)MgPO4. 6H2O, possesses
orthorhombic unit cell with cell dimensions, a =6.945
, b = 11.208 and c = 6.135 with space group4
Pmn21. These crystals have been grown by single
diffusion gel growth technique and characterized by
powder XRD, FT-IR, thermogravimetry analysis and
dielectric study. The kinetic and thermodynamic
parameters for dehydration as well as decomposition
are obtained from the thermogram.
_______________
#

Presently, Institute of Diploma Studies,


Nirma University of Science and Technology,
Ahmedabad 382 481

2 Experimental Details
Sodium metasilicate (SMS) solutions of specific
gravity range from 1.05 to 1.08 were used to prepare
the gel. Aqueous solutions of ammonium dihydrogen
phosphate (ADP) of 0.25, 0.5, 1.0 and 1.5 M
concentrations were mixed with the SMS solution in
appropriate amount so that the pH values 5.0, 5.5, 6.0,
6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 and 10.0 could be set
for the mixture. The gel solutions were transferred
into the test tubes of 140 mm length and 25 mm
diameter. Magnesium acetate solution of 1.0 M and
1.5 M concentration was gently poured on the set gels
in test tubes. AMP crystals were found to be growing
after one day of pouring solutions for 6.0 to 10.0 pH
values. The growth was completed within a period of
25 days. Crystals with different morphologies were
obtained for different conditions. Rectangular platelets
were obtained for specific gravity 1.07, 0.5 M ADP
and 1 M magnesium acetate concentration at 7.0 pH.
For specific gravity 1.08, 1.5 M ADP and 1.5 M
magnesium acetate concentration at 7.0 pH dendritic
type crystals were obtained. In case of specific gravity
1.07, 0.5 M ADP and 1.0 M magnesium acetate
concentration at 6.5 pH, transparent, prismatic shape
crystals were obtained. Whereas for specific gravity
1.05, 0.5 M ADP and 1.0 M magnesium acetate
concentration at 6.5pH, star shape crystals were
obtained. Elongated dendritic type crystals were
obtained for specific gravity 1.08, 0.5 M ADP and
1.0 M magnesium acetate concentration at 7.5 pH and
needle type crystals were obtained for specific gravity

508

INDIAN J PURE & APP PHYS, VOL 46, JULY 2008

1.06, 0.5 M ADP and 1.0 M magnesium acetate


concentration at 10 pH. Some of the morphologies of
grown struvite crystals are shown in Figs1(a-d).
The powdered crystalline samples were analyzed
by powder XRD using Philips X Pert MPD system.
The XRD pattern was analyzed by computer software
powder X. Using this software the h, k, and l
parameters as well as d and 2 values are generated in
such a way that these values match with the powder
X-ray diffraction pattern. The FT-IR spectrum was
recorded on Shimadzu FT-IR 8400 in the
400-4000 cm-1 range using pressed powder samples in
KBr medium. The TGA was carried out on Pyrif 1,
Perkin-Elmer, in the atmosphere of air from room
temperature to 900C at a heating rate of 15C/min.
The dielectric study was carried out by measuring
capacitance of the pressed pellets of samples of
known dimension at room temperature on Agilent
4284 A precession LCR meter using specially
designed sample holder.

3 Results and Discussion


The growth and characterizations of struvite
crystals5,6 have been studied earlier. However,
brushite7,8 (calcium hydrogen phosphate dihydrate)
and calcium oxalate monohydrate8,9 type urinary
crystals have already been characterized. Growth and
dissolution of brushite crystals by citric acid solutions
have been reported10,11.
Fig. 2 shows the powder XRD pattern of AMP
crystals with assigned planes indicated therein. The
cell parameters were estimated to be, a = 6.9410 , b
= 6.1370 and c = 11.1990 , which were
corresponding to the reported values4.
Fig. 3 is the FT-IR spectrum of AMP crystals. The
absorptions occurring at 3520.6, 3482.7, 3382.0 and
3276.9 cm-1 are due to OH and N \H stretching
vibrations. This also suggests the presence of water of
hydration. The absorption occurring at 2920.9 cm-1 is
due to NH4+ ion. The absorptions occurring at
1704.7 cm-1 and 1650.8 cm-1 are caused by NH

Fig. 1 (ad) Different morphologies of grown struvite crystals, which are (a) rectangular platelets, (b) prismatic, (c) star, (d) elongated
dendritic.

CHAUHAN et al.: GROWTH AND CHARACTERIZATION OF STRUVITE CRYSTALS

509

Fig. 2 Powder XRD pattern of struvite with assigned planes

Fig. 3 FT-IR spectrum of struvite

bending vibrations. On the other hand, the absorptions


taking place at 1064.7 cm-1 and 1022.1 cm-1 are due to
ionic phosphate. The absorptions taking place at 808.2
cm-1 and 690.9 cm-1 are due to the rocking of N H
bond and absorptions at 552.4 cm-1 and 509.4 cm-1
may be due to metal- oxygen bond. Thus, the FT-IR
spectrum proves the presence of water of hydration,
NH bond, PO bond, NH4+ ion and PO4- ion and
metal-oxygen bond.
Recently, Joshi and Joshi7 have reported thermal
studies of urinary type brushite crystals. Also, Joshi8

has carried out thermal studies of different urinary


crystals and calculi by conducting TGA. Fig. 4 shows
the thermogram of powdered AMP. It can be seen that
above room temperature, the crystal starts dehydrating
and then decomposing and finally, at 650C it
becomes 58.4% of original weight and remains
constant up to the end of the analysis. It is expected
that the final product may be Mg3P2 after evolving
gaseous products such as NH3, H2O, PO2, etc. which
is expected to remain stable up to high
temperatures 12.

INDIAN J PURE & APP PHYS, VOL 46, JULY 2008

510

Table 1Values of different thermodynamic parameters


of AMP crystal
Standard
Entropy
#S

Standard
Enthalpy
#H

Standard Gibbs Standard change


free energy in internal energy
#G
#U

- 106.436 kJ M-1 51.731 kJ M-1 94.093 kJ M-1

values of activation energy E, frequency factor A and


order of reaction n are 58.349 kJ M-1 , 2.289 107 and
2 , respectively.
The value of change in standard entropy is obtained
by:
#S = 2.303 R log10 [A h / k Tm]
(2)

Fig. 4 Thermogram of struvite

Fig. 5 Coats and Redfern plot for n = 2, where Y = -log10 [{1(1-) 1-n}/{T2(1-n)}] and X = 1/T K-1

The kinetic and thermodynamic parameters for


brushite7, cadmium tartrate13 and zinc tartrate14
crystals were reported by applying Coats and
Redferns relation15 to the respective thermograms. In
the present paper, the kinetic parameters have been
evaluated by applying the Coats and Redfern relation
to the thermogram of Fig. 4.
The Coats and Redfern relation 15 is as follows;
1 (1 )1 n
AR
2 RT E
= log

log
1
10

T 2 (1 n )

10

aE

55.04 kJ M-1

2 . 3 RT

(1)
where E is the activation energy of the reaction, A the
frequency factor, the fraction of decomposed
material at time t, n the order of reaction and T is the
absolute temperature. The plots of Y = -log10 [{1-(1-)
1-n
}/{T2(1-n)}] versus X = 1/T were straight lines for
different values of n, however, the best linear fit plot
gives the correct value of n. The value of activation
energy is obtained from the slope of the best linear fit
plot. Fig. 5 shows the Coats and Redfern plot. The

where A is the frequency factor, k Boltzmann constant, h


Plancks constant, R gas constant, Tm absolute
temperature in K and #S is the standard entropy.
Other thermodynamic parameters such as the
standard enthalpy (#H ), standard Gibbs free energy
(#G) and standard change in internal energy (#U)
were calculated by applying well known formulae, as
described in detail by Laidler14 and Vaishnav et al15.
Various thermodynamic parameters are presented in
Table 1.
Here, positive value of #H shows that the
enthalpy is increasing during the process and such
process is an endothermic process. Negative value of
#S shows that the process is non-spontaneous.
Positive value of #G shows that the substance is
thermodynamically unstable.
The dielectric constant was calculated from the
value of the capacitance of the sample using standard
formula18. The variation of dielectric constant with
frequency of applied ac field was studied at room
temperature and is shown in Fig. 6.
It is seen that as the frequency increases, the
dielectric constant decreases. In the usual case, the
variation of dielectric constant with frequency
suggests the presence of higher space charge
polarizability of material in the low frequency
region. As the frequency increases, a point is reached
where the space charge cannot sustain and comply
with the external field. Hence, the polarization
decreases and exhibits the reduction in the values of
dielectric constant as frequency increases. This has
been discussed in detail elsewhere18,19. The variation
of dielectric loss (tan ) versus frequency for struvite
at room temperature is shown in Fig. 7, which
suggests that dielectric loss decreases as frequency
increases.

CHAUHAN et al.: GROWTH AND CHARACTERIZATION OF STRUVITE CRYSTALS

ac = 2 f cD t

511
(3)

where f is the frequency, c capacitance, D dissipation


factor or dielectric loss or D = tan , t thickness of the
sample and A is the area of the sample.
ac = 1/ac

Fig. 6 Variation of dielectric constant () with logarithm of


frequency (f) for struvite

Fig. 7 Variation of dielectric loss (tan ) with logarithm of


frequency (f) for struvite

Fig. 8 Variation of ac resistivity (ac ) with logarithm of


frequency ( f ) for struvite

The ac resistivity (ac) and ac conductivity (ac)


were evaluated using the following formulae:

(4)

Fig. 8 shows the variations of ac versus frequency.


The plot indicates that the resistivity increases with
the increase in frequency and accordingly it was
found that the conductivity decreases with the
increase in frequency.
4 Conclusions
Struvite crystals of different morphologies such as
rectangular, prismatic, elongated dendritic, dendritic,
needle and star types were grown. The powder XRD
confirmed the orthorhombic crystal structure. The
FT -IR spectrum proves the presence of water of
hydration, NH bond, PO bond, NH4+ ion and PO4ion and metal- oxygen bond. Crystals are unstable
thermally and the loss of water of hydration starts
above room temperature. Kinetic and thermodynamic
parameters are evaluated for the dehydration curve.
The thermodynamic parameters suggest that the
enthalpy increases during the process, the process is
endothermic, non-spontaneous and the substance is
thermodynamically unstable. The variation of
dielectric constant with frequency suggests the
decrease in the value of dielectric constant as
frequency increases. This indicates, further, higher
space charge polarizability at low frequency region
and the space charge fails to sustain and comply with
the frequency of external field. The ac resistivity
increases with the increase in frequency and the ac
conductivity decreases with the increase in
frequency.
Acknowledgement
The authors are thankful to the University Grants
Commission, New Delhi, for the SAP, Prof K N Iyer
for his keen interest, Prof H H Joshi and Dr K B
Modi for dielectric measurements and the author
(BBP) for DBT, New Delhi, for the financial
assistance. The author (CKC) is thankful to the
Principal and the HOD of Physics Department, H &
H B Kotak Institute of Science, Rajkot, for their
encouragement.

512

INDIAN J PURE & APP PHYS, VOL 46, JULY 2008

References
1 Menon M, Parulker B G & Drach G W Urinary lithiasis :
Etiology, Diagnosis and Medical Management, Campbells
Urology, 7th Edn,(W.B. Saunders, New York) 1998, p-26612733.
2 Rivadeneyra M A, Gutierrez Calderon A., Rivadeneyra A
M & Ramos Cormenzana A., Urologia Int, 63 (1999) 188
3 Downey J A, Nickel J C, Clapham L & Mc Lean R J, Br J
Urol., 70 (1992) 355.
4 Encyclopedia of Minerals, 2nd Edn, 1990.
5 Srinivasan N & Natarajan S, Indian J Phys, 70A (1996)563.
6 Joseph K C, Ph D Thesis, Saurashtra University, (2005).
7 Joshi V S & Joshi M J, Cryst Res & Technol, 38 (2003) 817.
8 Joshi V S, Ph D Thesis, Saurashtra University, (2001).
9 Girija E K, Christic Latha S, Kalkura S N, Subramanian C &
Ramasamy P, Mater Chem & Phys, B (1998) 253.

10 Joshi V S & Joshi M J, Indian J Pure & Appl Phys, 41


(2003) 183.
11 Parekh B B & Joshi M J, Indian J Pure & Appl Phys, 43
(2005)675.
12 http:// www.inchem.org/documents/icsc/eisc07444.htm
13 Dabhi R M & Joshi M J, Indian J Phys,76A (2003) 481.
14 Dabhi R M & Joshi M J, Indian J Phys.,76A (2002) 211.
15 Coats A W & Redfern J P, Nature, 201 (1964) 68.
16 Laidler K J, Chemical Kinetics, 3rd Edn., (Harper & Row
New York ) 1987.
17 Vaishnav R M, Maniar L K, Dabhi R M & Joshi M J, Indian
J Phys, 74A (2000) 581.
18 Dabhi R M, Parekh B B & Joshi M J, Indian J Phys, 79
(2005) 503.
19 Arora S K, Patel V, Amin B & Kothari A, Bull Mater Sci, 27
(2004) 141.

You might also like