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E-ISSN: 2278-
3229
IJGHC, September -2013-November 2013; Vol.2, No.4, 908-915.
International Journal of Green and
Herbal Chemistry
An International Peer Review E-3 Journal of Sciences
Available online at www.ijghc.com
Green Chemistry
Research Article
CODEN (USA): IJGHAY
908
IJGHC, September -2013-November 2013; Vol.2, No.4, 908-915.
Acetamide Estimation Using Sodium Nitroprusside
by Photochemical Ligand Exchange
Reaction Method
Hardik Bhatt
1
, Gayatri Prasad
2
, Vaibhav Bhatt
3
and Ajay Sharma
4*
1
Department of Chemistry, PAHER University, Udaipur (Raj.)
2
Post graduate Department of Chemistry, Govt. P.G. College, Sirohi (Raj.) India
3
Zydus cadila Pharmaceutical, Dholka, Ahmedabad( Guj.) India
4
Department of Chemistry of Chemistry, Govt. P.G. College, Sirohi, (Raj.)India
Received: 25 August 2013; Revised: 8 September 2013 Accepted: 12 September 2013
Abstract: Determination of Acetamide using photochemical exchange reaction of sodium
nitroprusside (SNP) has been investigated. It is an inexpensive, faster and convenient
quantitative method. Sodium nitroprusside is a photolabile complex which undergoes
photochemical ligand exchange reactions rapidly. Some recent efforts have been made to
utilise such reactions for the estimation of some nitrogen containing anions and electron
rich organic molecules. The progress of the reaction is observed spectrophotometrically.
The effects of different parameters like pH, change of concentration of sodium
nitroprusside, concentration of ligands, light intensity etc. on percentage error was
investigated. The efforts were made to minimise the percentage error and some optimum
conditions were obtained. Such reaction can be used for the determination of Acetamide in
the range of millimoles to micromoles; hence it is important to know whether such
estimations can be done successfully and that too with the desired accuracy.
Keywords: Acetamide, SNP, photochemical exchange reaction, quantitative, percentage
error.
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IJGHC, September -2013-November 2013; Vol.2, No.4, 908-915.
INTRODUCTION
Photochemistry of biological reactions is a rapidly developing subject and helps in understanding of
phenomena like Photosynthesis, Phototaxis, Photoporiodism, Photodynamic action, vision and mutagenic
photo effect of light. Photochemistry plays a pivotal role in a number of chemical and biological processes.
Photosensitized reactions are widely used in many technical and biological areas. Photosynthesis is such an
important photochemical reaction controlled by nature, which still exists as a challenge to the
photochemists. Generally photochemistry is the chemistry of excited electronic states of molecules. An
electronic excitation is simply regarded as a process, whereby an electron is removed from an orbital with
certain bounding characteristics and reinserted in another orbital with different characteristics and these
excited states are generated by excitation of compounds, atoms or molecules using appropriate
wavelengths in the ultraviolet or visible region of the spectrum. It is apparent that the absorption or
emission of radiation to/from these states is the concern of spectroscopists as well as the photochemists.
Photo oxidation of eosin under visible light can be more effectively carried out by using PbS sensitized
TiO
2
as semiconductor reported by Brahimi et al.
1
. Effect of ring methylation on the photophysical,
photochemical and photobiological properties of cis-dichlorobis (1, 10-phenanthroline) rhodium (III)
chloride was observed by Lognathan and Morrison
2
. Kobayashi et al.
3
reported hydrothermal synthesis and
photocatalytic activity of whisker-like rutile-type titanium dioxide. Action spectra and the mechanism of
photoinduced formation of hydrogen and oxygen on potassium niobates has been investigated by
Zakharenko and Bogdanov
4
. Photocatalytic degradation of 4, 4′ - biphenol in TiO
2
suspension in the
presence of cyclodextrins by a trinity integrated mechanism by was reported by Zhang et al.
5
.
Passalía et al.
6
reported a methodology for modeling photocatalytic reactors for indoor pollution control
using previously estimated kinetic parameters. Photocatalytic destruction of gaseous toluene by porphyrin-
sensitized TiO
2
thin films was reported by Yao et al.
7
. Han et al.
8
carried out synthesis and photocatalytic
application of oriented hierarchical ZnO flower-rod architectures. Evaluation of the adsorption and rate
constants of photocatalytic degradation by means of HS-MCR-ALS, study of process variables using
experimental design was studied by Fernández et al.
9
.
Application of azo dyes as dosimetric indicators for enhanced photocatalytic solar disinfection
(ENPHOSODIS) was investigated by Bandala et al.
10
.Bio-mediated synthesis of TiO
2
nanoparticles and
its photocatalytic effect on aquatic biofilm was studies by Dhandapani and Maruthamuthu
11
. The
photophysics of salicylic acid derivatives in aqueous solution has been reported by Pozdnyakov et al.
12
Zhang and Maggard
13
investigated photocatalyti- cally active hydrated forms of amorphous titania, TiO
2
center dot nH
2
O. Sharma et al.
14
have studied estimation of thiosalicylic acid using photochemical
exchange reaction. Estimation of m-Phenylene Diamine using sodium nitroprusside by photochemical
method has been studied by Bhatt et al.
15
.
Maddigapu et al.
16
reported photochemical and photosensitised reactions involving 1-nitronaphth- alene
and nitrite in aqueous solution. Pozdnyakov et al.
17
had investigated photolysis of sulfosalicylic acid
in aqueous solutions over a wide pH range. Mehmoud et al.
18
investigated selective spectrophotometric
and spectrofluorometric methods for the determination of amantadine hydrochloride in capsules and
plasma via derivatization with 1,2-naphthoquinone-4-sulphonate. Estimation of hydroxylamine
hydrochloride using sodium nitroprusside by photochemical ligand exchange reaction has been reported by
Bhatt et al.
19
. Zhang and Shao
20
studied about Bi
2
MoO
6
ultrathin nano-sheets on ZnTiO
3
nano-fibers, a 3D
open hierarchical hetero structures synergistic system with enhanced visible-light-driven photocatalytic
activity. Dolat and Quici
21
investigated one-step, hydrothermal synthesis of nitrogen, carbon co-doped
titanium dioxide (N,C-TiO
2
) photocatalysts. They also investigated effect of alcohol degree and chain
Acetamide... Hardik Bhatt et al.
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IJGHC, September -2013-November 2013; Vol.2, No.4, 908-915.
length as carbon dopant precursors on photocatalytic activity and catalyst deactivation. Results from a first
autonomous optically adapted photocatalytic–photovoltaic module for water purification were reported by
Fuentes and Vivar
22
. Effects of TiO
2
based photocatalytic paint on concentration and emission of pollutants
and on animal performance in a swine weaning unit was observed by Costa and Chiarello
23
.
EXPERIMENTAL
A 100 mL stock solution of acetamide (M/100) and 100 mL stock solution of sodium nitroprusside
(M/100) were prepared by dissolving 0.00590 g of acetamide and 0.2979 g of sodium nitroprusside in
doubly distilled water. 20 mL of stock sodium nitroprusside solution was diluted to 100 mL to form M/500
concentration and then it was divided into five equal parts (20 mL each). In each beaker the solution of
(M/100) acetamide was mixed as 0.4 mL, 0.8 mL, 1.2 mL, 1.6 mL and 2.0 mL and all the beakers were
exposed to a 200 W tungsten lamp for 20 minutes.
A change in colour of solution was observed from light yellow to dark green. An aliquot of 5.0 mL
solution was taken out from each reaction mixture and change in optical density was observed
spectrophotometrically at λmax = 208 nm. A graph was plotted between optical density and known
concentration of acetamide i.e.[1.96 x 10
-4
M, 2.91 x 10
-4
M, 3.84 x 10
-4
M, 5.66 x 10
-4
M, 7.42 x10
-4
, 8.23
x 10
-4
M]. A straight line was obtained, which was used later on as a calibration curve. 1.0 mL sample
solution of known acetamide concentration was mixed in 20 mL of sodium nitroprusside (M/500) and it
was exposed to tungsten lamp under identical conditions. The optical density was measured
spectrophotometrically and the concentration of sample solution was determined by the calibration curve.
From this determined concentration the percentage error was calculated for acetamide sample solution.
Effect of Ph: The photochemical reaction of sodium nitroprusside in presence of acetamide may be
affected by the variation in pH value and as such the determination of acetamide may also be affected
accordingly. Therefore the effect of pH on quantitative determination of acetamide was studied at different
pH range. The results are reported in Table - 1 graphically shown in Figure - 1.
Table - 1: Effect of Ph
[SNP] = 2.10 x 10
-
2
M [ACETAMIDE] = 4.50 x 10
-
3
M
Light Intensity = 11.0 mWcm
-
2
λ
max
= 208 nm
pH (%) Error
5.0 5.4
6.0 4.3
7.0 3.4
8.0 2.7
8.5 1.9
9.0 2.2
9.5 2.6
10.0 3.2
10.5 3.8
11 4.0
11.5 5.2
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Fig. 1: Effect of Ph
The minimum error was observed in the determination of acetamide at pH = 8.5 i.e. only 1.9. The pH
required for minimum error was observed to be 8.5, which indicates that this acetamide will replace some
other ligand from the coordination sphere of ion to form dark green complex. As the pH was increase,
more availability of acetamide results in minimum error but as the pH was increase further, percentage
error increases again indicating that greater availability of acetamide hinders the complex formation.
Effect of Acetamide Concentration: The effect of the concentration of acetamide on the determination
was also observed by taking different concentration of acetamide and keeping all other factors identical.
The results are reported in Table - 2 graphically shown in Figure - 2.
Table – 2: Effect of Acetamide Concentration
[SNP] = 2.10 x 10
-
2
M pH = 8.5
Light Intensity = 11.0 mWcm
-
2
λ
max
= 208 nm
[Acetamide] x 10
3
M (%) Error
1.60 4.8
2.80 4.0
3.00 3.4
3.50 3.2
4.00 2.4
4.50 1.9
5.20 2.3
6.40 2.9
7.40 3.4
8.00 4.1
It was observed that the minimum error in the determination of acetamide is found at acetamide
concentration 4.50 x 10
-3
M i.e. only 1.9% which is within permissible limit. On increasing the
concentration of acetamide above 4.50 x 10
–3
M, the movement of acetamide may be hindered by its own
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IJGHC, September -2013-November 2013; Vol.2, No.4, 908-915.
larger concentration. It still not permit acetamide to form the desired complex within the time of exposure
and as a consequence, the percentage error increases.
Figure 2: Effect of Acetamide Concentration
Effect Of Sodium Nitroprusside Concentration: The effect of variation of concentration of sodium
nitroprusside on the quantitative estimation of acetamide percentage error was observed by taking different
concentration of sodium nitroprusside keeping all other factors identical. The results are reported in Table
- 3 graphically shown in Figure - 3.
Table – 3: Effect of Sodium Nitroprusside Concentration
[Acetamide] = 4.50 x 10
-
3
M pH = 8.5
Light Intensity = 11.0 mWcm
-
2
λ
max
= 208 nm
[SNP] x 10
2
M (%) Error
0.80 4.8
0.90 4.0
1.00 3.6
1.20 3.2
1.40 2.8
1.70 2.3
2.10 1.9
2.20 2.4
2.30 2.6
2.40 3.2
2.50 3.8
It was found that the minimum error in the determination of acetamide is found at sodium nitroprusside
concentration 2.10 x 10
-2
M i.e. only 1.9 % which is within permissible limit. As the concentration of
sodium nitroprusside increases the complex formation tendency increases, it reaches maximum at sodium
Acetamide... Hardik Bhatt et al.
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IJGHC, September -2013-November 2013; Vol.2, No.4, 908-915.
nitroprusside concentration 2.10 x 10
-2
M but if the concentration is further increased it will start acting like
a internal filter and it will not permit the desired light intensity to reach sodium nitroprusside molecule in
the bulk of the solution, as a consequence only limited number of sodium nitroprusside molecule will be
excited to participate in the complex formation resulting into increase in percentage error.
Figure 3: Effect of Sodium Nitroprusside Concentration Effect of Light Intensity
The effect of light intensity on the percentage error in the estimation of acetamide when it is
photochemical reaction with sodium nitroprusside has been observed by varying the distance between the
exposed surfaces of the reaction mixture tungsten lamp (light source). The result for tungsten lamp is
tabulated in Table - 4 graphically shown in Figure - 4.
Table -4: Effect of Light Intensity
[Acetamide] = 4.50 x 10
-
3
M pH = 8.5
[SNP] = 2.10 x 10
-
2
M
λ
max
= 208 nm
Light Intensity (mWcm
-
2
) (%) Error
6.0 3.6
7.0 3.4
8.0 3.0
9.0 2.4
10.0 2.0
11.0 1.9
12.0 1.9
14.0 1.9
16.0 1.9
18.0 1.9
It is observed that the minimum error in the determination of acetamide is found at tungsten lamp intensity
= 11.0 mWcm
-2
i.e. only 1.9 % which is within permissible limit. As the light intensity was increased the
number of photons striking per unit area per second will also increase. As a result the complex formation
became little bit easier on increasing light intensity, on further increasing the light intensity beyond 11.0
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IJGHC, September -2013-November 2013; Vol.2, No.4, 908-915.
mWcm
-2
the error remains almost constant indicating that the desired light intensity for maximum
(complete) formation of complex requires this much intensity and any increase will not increase the
amount of complex formed. This will result into a constant error above this intensity.
Figure 4: Effect of Light Intensity
Optimum Conditions: The photochemical reaction between sodium nitroprusside and acetamide was
carried out. It was observed that if the determination of acetamide is carried out under these given
conditions the percentage error observed is minimum (1.9 %) and within permissible limit.
The optimum conditions are given below:–
1. pH = 8.5
2. [Sodium Nitroprusside] = 2.10 x 10
–2
M
3. [Acetamide] = 4.50 x 10
–3
M
4. Light Intensity = 11.0 mWcm
-2
.
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*Corresponding Author: Hardik Bhatt
Department of Chemistry,
PAHER University, Udaipur – 313024 (Raj.)
