School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 260 Chapter 7A Photosensitized Reaction of 4 & 5 – Methylthiazole and Benzophenone Abstract: The photosensitized reaction of the 4 – Methylthiazole (4-MT) & 5 – Methylthiazole (5-MT) with benzophenone (BP) in alkaline medium using visible light has been studied. 4-MT & 5-MT show the λmax at 245 nm and at 240 nm in the pH range of 2 -12 respectively. The triplet – triplet energy transfer from the triplet excited state of the aromatic ketone benzophenone to the substrate molecule takes place during the photo sensitized reaction. The triplet excited 4-MT/5-MT breaks down on further exposure and photo product formation takes place. The reaction shows the participation of singlet oxygene during the photo reaction. The sulfate has been observed as photo product. The rate of the reaction has been calculated and the effect of pH, concentration of the sensitizer, the light intensity on the rate of the reaction has been studied. The quantum efficiency of the photo chemical reaction is calculated using potassium ferri oxalate actinometer and the effect of the concentration of the substrate on the quantum efficiency is calculated. The reaction mechanism and the excited states involved have been suggested. 7A.1 Introduction 4 – Methylthiazole is a Colorless to straw pale yellow to dark yellow clear liquid and occurs in asparagus, cooked pork, coffee, roasted peanut. It has been used as pharmaceutical intermediate, pesticide intermediate and as a flavor ingredient in the food flavors, nut flavors, vegetable and vegetative flavors, baked goods, dairy products, beverages. The thiazoles trimethylthiazole, 2-methylthiazole and 2-ethylthiazole have been used as gelation inhibitors in the polymer industry [1, 2]. Trimethylthiazole has also been used as a promoter for the carbonylation of butadiene to 3-pentenoic acid [3]. 2-methylthiazole and 4-methylthiazole have been used for the prepration of pyridine free Karl-Fisher reagent [4]. 4-Methyl-5-vinylthiazole has been used as a lubricant [5] and as a high water content hydrogel [6]. 2-acetylthiazole has been used as oxytocin antagonist [7] , 2-methylthiazole has been used in the development of an inhibitor for the gastric acid secretion [8], 4, 5-dimethylthiazole as a raw material in the development of neuroprotective drugs [9].
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School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 260
Chapter 7A
Photosensitized Reaction of
4 & 5 – Methylthiazole
and Benzophenone
Abstract: The photosensitized reaction of the 4 – Methylthiazole (4-MT) & 5 – Methylthiazole (5-MT) with benzophenone (BP) in alkaline medium using visible light has been studied. 4-MT & 5-MT show the λmax at 245 nm and at 240 nm in the pH range of 2 -12 respectively. The triplet – triplet energy transfer from the triplet excited state of the aromatic ketone benzophenone to the substrate molecule takes place during the photo sensitized reaction. The triplet excited 4-MT/5-MT breaks down on further exposure and photo product formation takes place. The reaction shows the participation of singlet oxygene during the photo reaction. The sulfate has been observed as photo product. The rate of the reaction has been calculated and the effect of pH, concentration of the sensitizer, the light intensity on the rate of the reaction has been studied. The quantum efficiency of the photo chemical reaction is calculated using potassium ferri oxalate actinometer and the effect of the concentration of the substrate on the quantum efficiency is calculated. The reaction mechanism and the excited states involved have been suggested.
7A.1 Introduction
4 – Methylthiazole is a Colorless to straw pale yellow to dark yellow clear liquid and occurs in
asparagus, cooked pork, coffee, roasted peanut. It has been used as pharmaceutical intermediate,
pesticide intermediate and as a flavor ingredient in the food flavors, nut flavors, vegetable and
[20] Backstrom L. I., Z. Physik. Chem. Abt. B, 25, (1934), 99-138.
[21] Jawaid Iqbal, Adil Husain and Anamika Gupta, Acta Chim. Slov. 2005, 52, 455–459
[22] C.Marti, O.Jurgens, O.Cuenca, M.Casals and S. Nonell, J.Photochem. Photobiol. A:
Chemistry 97, (1996), 11-18.
[23] K.Yamada, M.Sato, K. Tanaka, A. Wakabayashi, T. Igarashi and T. Sakurai, Journal
of Photochemistry and Photobiology A: Chemistry, 183(1-2), (2006), 205-211
[24] R. G. Brinson and P. B. Jones, J. Photochem. PhotoBio. C, 175(2-3), (2005), 118-124.
[25] Teijiro Ichimura, T. Suzuki, M. Nagano and S. Watanabe, J. Photochem. Photobiol. A:
Chemistry, 136, (2000), 7 - 13
[26] S. Jockusch, H. J. Timpe, W. schnabel and N. J. Turro, J. Phys. Chem., A. 101(4),
(1997), 440.
[27] K.Yamada, M.Sato, K. Tanaka, A. Wakabayashi, T. Igarashi and T. Sakurai, Journal
of Photochemistry and Photobiology A: Chemistry, 183(1-2), (2006), 205-211
[28] R. G. Brinson and P. B. Jones, J. Photochem. PhotoBio. C, 175 (2-3) ,(2005), 118-124.
[29] R. E. Galian, Pastor perez L., M.A. Miranda and J.Perez-pgieto, J.Am.Chem.Soc. 127,
(2005), 255-269.
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 292
[30] X.Cai, M. Hara, K. Kawai, S. Tojo and T. Majima, Chem. Phy. Lett., 371, (2003), 68-
73.
[31] R.N.Goyal, Rajeshwari and N.C.Mathur, J.Indian Chem.Soc., LVX, (1988), 490-494
[32] M. V. Encinas and J. C. Scaiano, Reaction of benzophenone triplets with allylic hydrogens. A
laser flash photolysis study, J. Am. Chem.Soc., 1981, 103, 6393–6397.
[33] K. K. Rohatgi-Mukherjee, “Fundamentals of photochemistry”, 3rd Eds., New age
international (P) limited, New Delhi, India, (1997)
[34] Wang Erjian, Li Miaozhen, chang zhiying and Feng Xinde, Chinese Journal of Polymer
science, No 3, 1987, 214 – 219.
[35] P. K. Freeman, Jung-Suk Jang and N. Ramnath, J. Org. Chem. 56, (1991), 6072
[36] Charles Tanielian, Claude Schweitzer,‡ Rachid Seghrouchni, Marc Esch and Robert Mechin,
Photochem. Photobiol. Sci., 2003, 2, 297–305
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 293
Chapter 7B
Photosensitized Proton Abstraction
Reaction of 2–Methyl 2-Thiazoline
with Benzophenone
Abstract
The photosensitized reaction of the 2 – Methyl 2 - thiazoline (2-MTh) with benzophenone (BP) in alkaline medium using visible light has been studied. The spectrum of the 2-MTh shows λmax at 260 nm in the acidic medium while in the alkaline medium it absorbs at 230 nm and 245 nm nearly in equal concentration. The two tautomeric forms of 2-MTh are in equilibrium in the pH range 8 – 12. The triplet – triplet energy transfer from the triplet excited state of the aromatic ketone benzophenone to the substrate molecule takes place during the photo sensitized reaction. The triplet excited 2-MTh breaks down on further exposure and photo product formation take place. The thiocyanate has been observed as photo product. The rate of the reaction has been calculated and the effect of pH, concentration of the sensitizer, the light intensity on the rate of the reaction has been studied. The quantum efficiency of the photo chemical reaction is calculated using potassium ferri oxalate actinometer and the effect of the concentration of the substrate on the quantum efficiency is calculated. The reaction mechanism and the excited states involved have been suggested.
7B.1 Introduction
2 Methyl 2- thiazoline (2-MTh) is pale yellow liquid to solid having sulfurous musty meaty nutty
odor. It has m.p. at 62.0°C and boiling Point at 143.0 to 145.0°C @ 760.00 mm Hg. It is in
flammable and is irritating to skin and eyes.
2-MTh is an industrially important compound used in manufacturing of flavoring agents and in the
products like dairy products, fats, oils, and fat emulsions, processed fruit, processed vegetables,
confectionery, cereals and cereal products, for particular nutritional uses, non-alcoholic ("soft")
beverages, dairy products, alcoholic beverages, incl. alcohol-free and low-alcoholic counterparts,
ready-to-eat and composite foods (e.g. casseroles, meat pies, mincemeat).
Lang et. al. [1, 2] have investigated the opening of the ring of 2-methyl- thiazoline to give the
sulfhydryl compound N- acetyl- P-mercaptoethylamine and its S-acetyl isomer. Calvin [3] have
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 294
reported that the thiazoline ring formation occurs in strongly acid solutions of glutathione and this
has been supported by Garfinkel [4] and Martin [5]. The rate of hydrolysis of 2-methyl 2-thiazoline
has been studied by Martins et. al. [6] as a function of pH from concetitrated HC1 to buffer
solutions at pH 9.
Matsuura et. al. [7] have reported that the photoaromatization of 2-methyl 2- thiazoline gave N –
vinylthioacetamide as a photoproduct in acetone solution.
Sharma et. al. [8] have reported the photochemical reaction of indol-2, 3-dione derivatives with 2-
thiazoline-2-thiol. Pardasan et. al. [9] reported the reaction of indol-2.3-dione derivatives with 2-
thiazoline-2-thiol under thermal as well as photochemical conditions.
Smith et. al. [10] have reported the hydrolysis of 2-methyl-2-thiazoline-4-carboxylic acid. Sheehan
et. at. [11] have reported the reaction of 2 – methyl 2 – thiazoline with phthaloglycyl acid. Durstan
et. al. have reported the acylation of 2 – methyl 2 – thiazoline [12].
Azam et. al. have reported the metallation of 2-methyl-2-thiazoline at a triosmium cluster at
ambient temperature [13].
The photo-degradation may play an important role in the elimination of 2-methyl-2-thiazoline from
aquatic environment. The photodegradation study of substited 2-methyl 2-thiazoline using aromatic
ketone as a sensitizer in the presence of visible light is not reported elsewhere.
The present study reports the photochemical reaction of methyl thiazoline in the aqueous alkaline
medium on irradiation with visible light. The aromatic ketone, benzophenone has been used as a
photo sensitizer [14-16] in a number of photochemical reraction. It shows energy transfer process
by photo – oxygenation mechanism and by proton abstraction mechanism. There are very few
report in the literature for the sensitized study of methyl thiazoline.
Benzophenone has been used as photo sensitizer by a number of worker with different type of
compound. Canonica et. al. [17] have reported the aqueous oxidation of phenylurea herbicides by
triplet excited state of aromatic ketones via singlet O2. A laser flash photolysis study for the
reactivity of aromatic amines with triplet 1, 8 dihydroxy anthraquinone has been reported by Y.Pan
et. al. [18]. Morsi et. al. [19] have reported the photo-oxidation of cis-polyisoprene by singlet
oxygen in the presence of the sensitizer benzophenone by UV radiation. Backstrom [20] has
presented the mechanism for the benzophenone-photosensitized oxygenation of alcohols and
aldehydes. Iqbal et. al. [21] have reported the photo oxygenation of tinosponone with singlet
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 295
oxygen using different combinations of sensitizers, solvents and singlet oxygen scavengers. Nonell
et al. [22] have reported that aromatic ketones as standards for singlet molecular oxygen
photosensitization.
Benzophenone shows proton abstraction [23] and electron transfer reactions [24] in the excited
triplet state. Teijiro Ichimura et al [25] has reported kinetic study by the quenching the rate of DPA
by triplet benzophenone photo sensitizer and have also reported that the excitation energy effect on
the reaction with 2- bromo methyl naphthalene. S. Jockusch et al [26] have reported that Photo-
induced energy and electron transfer processes between ketone triplet state and organic dyes
(methylene blue, thiopyrinine, safranine and phenosafranine). Yamada et. al. [27] have reported that
Nitrile-forming radical elimination reactions of 1-naphthaldehyde O-(4-substituted benzoyl) oximes
activated by triplet benzophenone. Brinson et. al. [28] have reported the proton abstraction and
electron transfer photo reaction by anthraquinone. Galian et. al. [29] have reported that the
intramolecular electron transfer between tyrosin and tryptophan photo sensitized by aromatic
ketone. Cai et. al. [30] have suggested mechanism of sensitized reaction by benzophenone in the
triplet excited state.
The present study reports the photosensitized reaction of the 2-MTh with the benzophenone (BP) as
a sensitizer in the aqueous alkaline medium in the presence of the visible light. The reaction is
monitored by measuring the spectrum change of 2-MTh. The kinetics of the photo reaction and the
mechanism of the photo sensitized reaction have been studied.
7B.2 Results
7B.2.1 Spectral characteristics
The UV spectrum of the pure 2-MTh (1.5 X 10-4 M) was recorded at different pH, to determine the
different species present at the different pH of the aqueous solution. The pH of the solution was
maintained using suitable concentration of the HCl or the NaOH in the solution.
The initial spectrum of 2-MTh (1.5 X 10-4 M) in the aqueous acidic solution in the pH range 2 - 6 is
represented by the continuous line in Fig 7B.1 which exhibits one well-defined maximum at 260
nm (ε = 5,300 L mol-1 cm-1).
2-MTh shows (Fig 7B.1) maximum at 230 nm (ε = 2,700 L mol-1 cm-1) and at 245 nm (ε = 2,653 L
mol-1 cm-1) in the aqueous alkaline solution in the pH range 8 – 12 (dash line).
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 296
Spectrum of 2-MTh
200 220 240 260 280 300 320
0.000
0.100
0.200
0.300
0.400
0.500
0.600
0.700
0.800
0.900
Acidic Medium
Alkaline Medium
Wavelength (nm)
Ab
so
rba
nc
e
Fig 7B.1 Spectrum of 2-MTh (1.5 × 10-4
M)
(a) In acidic medium at pH 2 (
)
(b) In alkaline medium at pH 11.5 (----)
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 297
The spectrum of the 2-MTh is stabilised in the acidic medium and shows only one λmax at 260 nm.
The two tautomeric forms are observed in the alkaline medium which absorb at 230 nm and 245 nm
nearly in equal concentration. The two tautomeric forms of 2-MTh are in equilibrium in the pH
range 8 – 12. The marked changes have been observed in the spectrum of 2-MTh in the aqueous
acidic and in the aqueous alkaline medium. Martin et. al. [6] have reported that the spectrum of the
free base in water is very close to that of the pure liquid, whereas marked differences occur on the
addition of a proton to the nitrogen of the thiazoline ring.
Goyal et al [31] have reported that the UV spectral behaviour at pH < pKa and pH > pKa is
essentially the same in the case of substituted thiazole compound. The λmax and molar
absorptivities of the tautomeric forms of 2-MTh in the acidic and in the alkaline aqueous medium
are quoted in Table 7B.1.
The exposure of the solution containing only 2-MTh (2 X 10-4 M) in the pH range 2 – 12 to the
visible radiation does not result in the change of the original spectrum of the solution. The direct
photolysis of 2-MTh on irradiation by the visible light does not occur in the acidic or in the alkaline
medium and 2-MTh is photo stable.
The reaction mixture of 2-MTh with the suitable concentration of BP was prepared and the pH of
the solution was maintained from 2 to 12. The solutions were kept in the dark and their spectrums
were recorded against a reagent blank which matched with the original spectrum of the 2-MTh for
the solution having pH value 2 – 6. 2-MTh and BP do not interact in the ground state in the aqueous
acidic solution.
The spectrum of 2-MTh with the suitable concentration of BP shows difference from the original
spectrum of 2-MTh only in the aqueous alkaline medium in the pH range 8 - 12. 2-MTh and BP do
not interact in the ground state in the aqueous alkaline medium but it shows only one broad band
due to the merging of two separate bands in the aqueous alkaline medium instead of two bands at
230 nm and 245 nm.
The solutions containing 2-MTh (2 X 10-4 M) and BP (1 X 10-4 M) maintained at different pH
between 2 to 12 were exposed to the visible radiation and the spectrum of the solutions were
recorded against the reagent blank. The solutions having pH 2 to 6 show very small change in the
spectrum but solutions having pH 8 to 12 show much faster change in the spectrum of 2-MTh
undergoes very slow reaction in the acidic medium with BP when exposed to the visible radiation
but it shows much faster photoreaction in the presence of BP used as a sensitizer in the alkaline
medium.
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 298
Absorption spectra of the photosensitized reaction of 2-MTh with BP
200 210 220 230 240 250 260 270 280 290 300
0.000
0.100
0.200
0.300
0.400
0.500
0.600
0.700
T0
T30
T60
T90
T120
T150
T180
T210
T240
Wavelength (nm)
Absorb
ance
Fig 7B.2 Absorption spectra of the photosensitized reaction of 2-MTh with BP on exposure at 11 pH.
2-MTh (2 × 10 -4
M)
BP (1 × 10-4
M)
Time interval: 30 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 299
The change in the spectrum of 2-MTh is observed when the reaction mixture containing a suitable
concentration of BP in the aqueous alkaline medium is exposed to the visible radiation.The
spectrum of the photo sensitized reaction was recorded against the reagent blank. (Fig 7B.2) The
absorbance of the broad band decreased and an intence band at 220 nm was observed. The product
of the photo-reaction absorbs at a shorter wavelength in comparison to the starting material. The
decrease of the absorbance with the time was monitored and an isobestic point was not observed.
Table 7B.1 λmax and molar absorptivity of 2-MTh in the acidic and alkaline aqueous
medium
Medium λmax Molar Absorptivity
Acidic (pH 3) 260 nm 5,300 L mol-1 cm-1
Alkaline (pH 11) 230 nm
245 nm
2,700 L mol-1 cm-1
2,653 L mol-1 cm-1
Table 7B.1 λmax and molar absorptivity of 2-MTh in the aqueous solution of the pH range
2-12, Substrate: 2-MTh: (1.5 × 10 -4
M), Acid Medium: pH 3, Alkaline Medium:
pH 11
7B.2.2 Determination of the rate constant
The progress of the photosensitized reaction was monitored by recording UV spectra of 2-MTh (2
X 10-4 M) with BP (1 X 10-4 M) in the range 200 - 400 nm at different time interval. The spectrum
of the 5ml aliquot of the exposed solution, withdrawn after 10 min time intervals in the range of 200
nm – 400 nm against the reagent blank were recorded. The absorbance of the solution was also
measured at 230 nm.
The absorbance decreases at the broad band of 2-MTh and a band at 220 nm is observed on
irradiation of the reaction mixture and becomes constant after 210 mins exposure. The absorbance
shows different rate of decrease of 2-MTh broad band having λmax at 230 nm and 245 nm. It is
observed that the absorbance at 245 nm decreases at a faster rate than at 235 nm. The decrease of
the absorbance with time for 2-MTh at the λmax 245 nm have been used to calculate the rate of the
reaction. The results of a typical run for the change in the absorbance of 2-MTh with time have
been presented in Fig 7B.3.
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 300
Absorption Vs time plot.
0 50 100 150 200 250 300
0.000
0.100
0.200
0.300
0.400
0.500
0.600
Time (min)
Absorb
ance
Fig 7B.3 Absorption Vs time plot on exposure at 11 pH.
2-MTh (2 × 10-4
M)
BP (1 × 10-4
M)
Time interval: 30 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 301
2 + log OD Vs Time plot
0 50 100 150 200 250 300
0.8
1
1.2
1.4
1.6
1.8
2
Time (min)
2 +
log O
D
Fig 7B.4 2 + log OD Vs Time plot of the photosensitized reaction of 2-MTh with BP.
2-MTh (2 × 10-4
M)
BP (1 × 10-4
M)
Time interval: 30 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 302
The change in the absorbance with time has been used for the calculation of the rate of the reaction.
The reaction follows the first order reaction kinetics as the plot of 2 + log OD (optical density) vs.
time is a straight line with a positive slope. (Fig 7B.4) The rate constant has been determined by the
expression:
Rate constant = 2.303 x slope
7B.2.2.1 Effect of the pH on the rate of the reaction
The spectrum of the pure 2-MTh solution (2 X 10-4 M) was recorded at different pH in the range of
200 nm – 400 nm and the effect of the pH on the rate of the photosensitized reaction was carried out
by changing the pH of the solution between pH 2 – 12 and the calculations for the rate of the
reaction were carried out at different pH. (Table 7B.2)
The spectrum of 2-MTh shows the λmax at 260 nm in the acidic medium and a broad band having
the λmax at 230 nm and 245 nm in alkaline medium. The photosensitized reaction takes place slowly
between the pH 2 – 6 but increases till the pH of the solution is 10 and then becomes constant. (Fig
7B.5) The subsequent studies were carried out at pH 11. The photosensitized reaction of 2-MTh
with BP occurs faster in the alkaline medium.
The photo effect of Benzophenone is sensitive to OH- ion concentration of the solution therefore the
increase in OH- ion concentration increases the sensitivity of the sensitizer, which shows higher
proton abstraction capacity of benzophenone [32]. Similar effect of OH- ion concentration has been
observed in the present study.
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 303
Table 7B.2 Effect of pH on the rate of the reaction
pH of the solution 2-MTh Rate of the Reaction (k x 10
-3)
mole / L min [Avg K + 0.4]
2 0.384
4 0.384
6 0.768
8 5.37
10 6.14
11 6.14
11.50 6.14
Table 7B.2 Effect of the pH on the rate of the reaction, Substrate: 2-MTh: (2 × 10 -4
M),
Sensitizer: BP (1 × 10-4
M), Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 304
Effect of the pH on the rate of the reaction
0 2 4 6 8 10 12 14
0.000
1.000
2.000
3.000
4.000
5.000
6.000
7.000
pH of the solution
Rat
e of
the
reac
tion
( K x
10-
3 ) m
ole
/ L m
in
Fig 7B.5 Effect of the pH on the rate of the reaction
2-MTh (2 × 10 -4
M)
BP (1 × 10-4
M)
Time interval: 30 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 305
7B.2.2.2 Effect of the concentration of the sensitizer on the rate of the reaction
The effect of the concentration of the BP on the rate of the photosensitized reaction has been
studied. The study was carried out by varying the concentration of the BP in the range of 0.6 x 10-4
M to 1.6 x 10-4 M.
The rate of the reaction remains constant with the increase of the BP concentration in the reaction
mixture. The results indicate that 1 x 10-4 M BP had an optimal concentration and gave the best
performance under the experimental condition. (Fig 7B.6)
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7B.2.2.3 Effect of the concentration of the substrate on the rate of the reaction
The effect of the initial concentration of 2-MTh on the rate of the reaction was studied. The rate of
the reaction has been calculated with the different initial concentration of the substrate in the range
of (1.6 – 2.4) x 10-4 M. The rate of the reaction remains constant initially and than slightly decreases
at the higher concentration of the substrate. It shows that the reaction is independent of the initial
concentration of the substrate. (Fig 7B.7) The half life time of the reaction has also been calculated
at the different concentration of the substrate and t1/2 value is constant over the above range of the
substrate concentration. The observation suggests that the photochemical reaction is of the first
order. (Table 7B.3)
Table 7B.3 Effect of the concentration of substrate on the rate of the reaction
Concentration of
Substrate C x 10-4
2-MTh Rate of the Reaction
(K x 10-3
) mole / L min
[Avg K + 0.4]
t ½
L min / mole
1.6 6.14 112.87
1.8 6.14 112.87
2.0 6.14 112.87
2.2 6.14 112.87
2.4 5.73 120.94
Table 7B.3 Effect of the substrate concentration on the rate of the reaction at 11 pH,
Substrate: 2-MTh: (2 × 10-4 M), Sensitizer: BP (1 × 10-4 M), Time interval: 30
mins, Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 307
Effect of the sensitizer concentration on the rate of the reaction
4 6 8 10 12 14 16 18
0.000
2.000
4.000
6.000
8.000
10.000
Concentration of Sensitizer (c x 10-5) M
Rate
of
the r
eactio
n (
k x
10-3
) m
ole
/ L
min
Fig 7B.6 Effect of the sensitizer concentration on the rate of the reaction at 11 pH.
2-MTh (2 × 10-4
M)
BP (0.6 × 10-4
M to 1.6 × 10-4
M)
Time interval: 10 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 308
Effect of the substrate concentration on the rate of the reaction
1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
0.000
2.000
4.000
6.000
8.000
10.000
Concentration of Substrate ( c x 10-4) M
Rat
e of
the
Rea
ctio
n (k
x 1
0-3)
mol
e / L
min
Fig 7B.7 Effect of the substrate concentration on the rate of the reaction at 11 pH.
2-MTh (1.6 × 10-4
M to 2.4 × 10-4
M)
BP (1 × 10-4
M)
Time interval: 10 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 309
7B.2.2.4 Effect of the light intensity
The solutions of the the different concentration of the substrate [2-MTh] and the sensitizer BP were
prepared in the aqueous alkaline solution and irradiated with the visible light for the fixed time
intervals. The rate of the reaction was calculated.
The increase of the light intensity [Einstein / second (E/s)] shows positive effect and the rate of the
reaction increases as the light intensity increases. The higher number of the photons increases the
number of the excited sensitizer molecule and the rate of the reaction also increases. A linear
relationship has been observed between the light intensity and the rate of the reaction. (Table 7B.4)
Table 7B.4 Effect of the Light Intensity on the rate of the reaction and on the quantum
efficiency
Light Intensity
( I × 108
) E/s
2-MTh
(k × 10-3
) mole / L min [K + 0.5]
2-MTh
Quantum Efficiency
5 2.24 0.3305
10 4.86 0.3311
15 6.68 0.3306
20 9.05 0.3307
25 11.97 0.3302
Table 7B.4 Effect of the light intensity and quantum efficiency on the rate of the reaction at
11 pH, Substrate: 2-MTh: (2 × 10 -4
M), Sensitizer: BP (1 × 10-4
M), Time
interval: 30 mins, Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 310
7B.2.2.5 Effect of the anaerobic condition
The reaction was studied in the anaerobic condition to observe the effect of the oxygen on the rate
of the reaction.
The solutions of the the different concentration of the substrate [2-MTh] and the sensitizer BP were
prepared in the aqueous alkaline medium.The solutions of the reaction mixture were de-aerated by
purging with purified nitrogen for 30 min via a needle through the cap. The maximum
deoxygenated reaction mixture of the 2-MTh and the BP was exposed to the visible light. The rate
of the reaction was calculated. The rate of the reaction does not show change and remains the same
as in the aerobic condition. (Table 7B.5)
The φ value of the reaction was also calculated in the anaerobic condition of the reaction which
remains constant and same as in the aerobic condition. This suggests that the singlet oxygen does
not participate in the photosensitized reaction.
Table 7B.5 Effect of the anaerobin condition on the rate of the reaction
Rate of the reaction in aerobic aqueous
alkaline medium K x 10-3
mole / L min
Rate of the reaction in anaerobic aqueous
alkaline medium K x 10-3
mole / L min
2-MTh 6.58 6.23
Table 7B.5 Effect of the anaerobin condition on the rate of the reaction at 11 pH, Substrate:
2-MTh: (2 × 10 -4
M), Sensitizer: BP (1 × 10-4
M), Time interval: 30 mins,
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 311
7B.2.2.6 Effect of the free radical scavenger
The effect of the solvent used as free radical scavenger on the photo sensitized reaction of 2-MTh
was studied by changing the medium from aqueous alkaline to alkaline methanol.
The solutions of the the different concentration of the substrate [2-MTh] and the sensitizer BP were
prepared in the alkaline methanol and irradiated with the visible light. 2-MTh shows the broad band
at the λmax at 230 nm (ε = 2,600 L mol-1 cm-1) with a sholder at 245 nm (ε = 2,250 L mol-1 cm-1) and
a small peak at 266 nm (ε = 1,000 L mol-1 cm-1) in the alkaline methanolic solution. The rate of the
reaction was calculated.
The photochemical reaction shows decrease in the alkaline methanolic solution suggests that there
is free radical formation during the reaction. The similar results were obtained using NaN3 as a free
radical scavenger. (Table 7B.6)
Table 7B.6 Effect of the free radical scavenger on the rate of the reaction
Rate of the reaction in aqueous
alkaline medium K x 10-3
mole / L min
Rate of the reaction in alkaline
methanolic medium K x 10-3
mole / L min
2-MTh 6.67 2.321
Table 7B.6 Effect of the free radical scavenger on the rate of the reaction at 11 pH,
Substrate: 2-MTh: (2 × 10 -4
M), Sensitizer: BP (1 × 10-4
M), Time interval: 10
mins, Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 312
7B.3 Quantum efficiency
The quantum efficiency of the photo reaction of the 2-MTh and the BP has been calculated using
potassium ferrioxalate actinometer and was determined with a number of initial concentration of the
2-MTh.
The graph of the different initial concentrations of the 2-MTh and ø-values is a straight line with a
positive slope which suggests that the quantum yield of the reaction is dependent on the substrate
concentration. (Fig 7B.8)
The plot of the inverse of the quantum efficiency versus inverse of the concentration of the
substrate is a straight line with a positive slope which suggests that the triplet excited substrate
decomposes to form a radical of the substrate in the triplet excited state and the product formation is
via triplet excited state of the substrate [33] (Fig 7B.9).
Substrate
Concentartion
( C × 10-4
M )
Quantum Efficiency
(Φ)
Inverse of substrate
concentration
(C × 103)
Inverse of quantum
efficiency
1.6 0.026 6.250 38.46
1.8 0.086 5.556 10.31
2.0 0.135 5.0 7.407
2.2 0.196 4.545 5.102
2.4 0.257 4.167 3.891
2.6 0.330 3.846 3.03
Table 7B.7 Different initial substrate concentration and quantum at 11 pH, Substrate: 2-
MTh: (2 × 10 -4
M), Sensitizer: BP (1 × 10-4
M), Time interval: 10 mins, Source:
100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 313
The plot of quantum efficiency Vs substrate concentration
1.4 1.6 1.8 2 2.2 2.4 2.6 2.8
0.000
0.050
0.100
0.150
0.200
0.250
0.300
0.350
Concentartion of Substrate ( c x 10-4) M
Qua
ntum
Eff
icie
ncy
Fig 7B.8 Plot of quantum efficiency Vs substrate concentration at 11 pH.
2-MTh (1.6 × 10-4
M to 2.6 × 10-4
M)
BP (1 × 10-4
M)
Time interval: 10 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 314
Plot of inverse of the quantum efficiency Vs inverse of the substrate concentration
3.500 4.000 4.500 5.000 5.500 6.000
0.000
2.000
4.000
6.000
8.000
10.000
12.000
1/ concentartion of substrate
1/
qu
an
tum
effi
cie
nc
y
Fig 7B.9 Plot of inverse of the quantum efficiency Vs inverse of the substrate concentration at 11 pH
2-MTh (1.6 × 10-4
M to 2.8 × 10-4
M)
BP (1× 10-4
M)
Time interval: 10 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 315
7B.3.1 Effect of the light intensity on the quantum efficiency
The quantum efficiency of the reaction of 2-MTh with BP as a sensitizer was determined using light
intensity in the range 5 – 25 E/s.
The solutions of the the different concentration of the substrate and the sensitizer BP were prepared
in the aqueous alkaline solution and irradiated with the visible light of different intensity for the
fixed time intervals and the quantum efficiency was calculated.
The φ value remains constant in this range of the light intensity. The graph of φ value vs light
intensity is horizontal line with zero slope suggests a monophotonic reaction. (Fig 7B.10) (Table
7B.4)
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 316
Plot of light intensity Vs quantum efficiency
0.000 5.000 10.000 15.000 20.000 25.000 30.000
-0.100
0.000
0.100
0.200
0.300
0.400
0.500
0.600
Light Intensity (I x 108) E/s
Quantu
m E
ffic
iency
Fig 7B.10 Plot of light intensity Vs quantum efficiency
2-MTh (1.6 × 10-4
M to 2.8 × 10-4
M)
BP (1× 10-4
M)
Time interval: 10 mins
Source: 100 W tungsten lamp
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 317
7B.4 Photo product identification
The λmax and the molar absorptivity of the photo product of the reaction of the 2-MTh and the BP
in aqueous alkaline solution have been evaluated under experimental condition. The molar
absorptivity of the substrate and product has been calculated by measuring the absorbance of a
number of known concentration solutions.
A sharp absorption band having λmax at 220 nm is observed which remains constant. The analysis of
the reaction mixture for photo product shows the presence of organic compound and the test for S-2
and SCN- was found negative with lead acetate and FeCl3 solution. The photo product shows the
absorbance maxima in UV spectrum at 220 nm.
7B.4.1 Test for the Methyl thiocyanate: The reaction mixture gave the specific onion
odor. The photoproduct was isolated by the procedure described in the chapter 2 and analysed by
GC-MS. A single peak was observed in the gas chromatogram suggesting that there is only one
photoproduct. The RT of the reaction product matches with the RT of the standard solution of
Methylthiocyanate. (Fig 7B.11 & 7B.12) The mass spectrum of the isolated product shows two
main peaks. The peak at: m/z = 73 (M+1, 100 %) which is the base peak also corresponds to [m+1]
protonated molecular ion. The second is observed at m/z = 72.
It appears the photoproduct of the photo reaction of 2-MTh with BP is methylthiocyanate. The
triplet excited state molecule of 2-MTh undergoes decomposition to give methylthiocyanate as
photo product.
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 318
GC spectra of the photoproduct of the photosensitized reaction of 2-MTh and BP
7B.11 Mass spectra of the photoproduct of the photosensitized reaction of 2-MTh and BP
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 319
7B.12 GCMS spectra of the Methyl thiocyanate from library
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 320
7B.5 Discussion
The photo-reaction product of 2-MTh and BP were isolated and analysed for product identification.
The λmax and molar absorptivity of the photo product has been calculated and compared with
irradiated reaction mixture of the the standard methylthiocyanate with BP in the same reaction
condition and result suggest that methylthiocyanate is the photoproduct.
The 2-MTh shows different λmax and molar absorptivity in the acidic solution and in the alkaline
solution. 2-MTh shows one absorption band at 260 nm in the aqueous acidic medium and two
absorption bands at 230 nm and 245 nm for the two tautomeric forms in the aqueous alkaline
medium. Both the tautomeric forms have nearly equal concentartion and are in equilibrium. The
equilibrium is shifted to the deprotonated form as the deprotonated form of 2-MTh undergoes
degradation in the alkaline medium.
The visible light is not absorbed by the 2-MTh as it's λmax is below 300 nm and is photo stable.
Benzophenone (BP) absorbs visible radiation and is excited to the singlet state and undergoes ISC
to give triplet state which shows photosensitized reaction.
The reaction mixture of the 2-MTh and the sensitizer BP also shows λmax at 260 nm and do not react
in the ground state in the acidic solution but in the alkaline medium reaction mixture shows a broad
peak having λmax at 230 nm & 245 nm. The reaction mixture when exposed to the visible light
shows decrease in the absorbance with time. The absorbance at 245 nm decreases at a faster rate
than at 235 nm and a new λmax appears at 220 nm which remains constant after 210 mins exposure.
The influence of pH on the photo sensitized reaction has been investigated, the pH of the medium
affects the photo chemical reaction. The lone pair of electrons present on nitrogen atom co-ordinate
with the proton in the acidic medium. The protonated form of the benzophenone does not form an
exciplex with the alkyl group of the substrates.
The pH effect study on the rate of the reaction suggests that only deprotonated species of the
benzophenone undergo photo sensitized reaction in the pH range 8 to 12. The rate constant of the
photosensitized reaction has been calculated. It has been observed that the maximum reaction takes
place at pH 10 and above. The rate of the photoreaction is independent of the concentration of the
substrate and the concentration of the sensitizer but is dependent on the light intensity.
The rate of the reaction and the quantum efficiency remain same when the reaction was carried out
in the anaerobic condition as in the aerobic condition. The reaction does not show participation of
O2 and oxidation process is not involved in the product formation.
School of Sciences, Gujarat University, Ahmedabad, INDIA. Page 321
The free radical scavenging effect of the methanol is positive. The photo reaction proceeds via a
free radical mechanism.
Hydrogen abstraction and intramolecular single electron transfer both reactions have also been
observed by Jones et. al [34]. Mohan et al. [35, 36] have reported electron and proton transfer
process in the reaction involving benzophenone.
The plot of the quantum efficiency vs the concentration of the substrate is linear with a positive
slope indicating that the quantum yield of the reaction is dependent on the substrate concentration.
The plot of the inverse of the quantum efficiency vs inverse of the concentration of the substrate is
is a straight line with a positive slope which suggests that the triplet excited substrate decomposes
to form a free radical of the substrate in the triplet excited state and the product formation is via
triplet excited state of the substrate.
The singlet excited state of the BP molecule formed after absorption of the visible light undergoes
ISC and forms triplet excited state which transfers it's energy to 2-MTh and then comes back to the
ground state.
----------- (1)
----------- (2)
Where and
Eq 2 represents the dependance of the inverse of the quantum efficiency upon the inverse of the
concentration of the substrate. The plot of the inverse of the quantum efficiency vs inverse of the
concentration of the substrate is linear with positive slope indicating that the energy transfer from
the triplet excited sensitizer molecule to substrate molecule involves a triplet state of the 2-MTh
without exciplex formation during the reaction.
The horizontal graph of the quantum efficiency vs the light intensity suggest a monophotonic
process during the product formation.
The free radical formation occurs by the fission of the triplet excited substrate to give the triplet