Solubility of Thiotriazinone in Binary Solvent Mixtures of Water+

Jul 6, 2012 - The stepwise regression method was used to simplify the modified Jouyban−Acree equation. □ INTRODUCTION. Thiotriazinone (5 ...
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Solubility of Thiotriazinone in Binary Solvent Mixtures of Water + Methanol and Water + Ethanol from (283 to 330) K Haiyan Ma,† Yixin Qu,*,† Zhimao Zhou,† Shui Wang,† and Lizhong Li‡ †

College of Chemical Engineering, Beijing University of Chemical Technology, Beijing, China 100029, People’s Republic of China Shijiazhuang Hejia Health Products Co., Ltd., Shijiazhuang Hebei 052160, People’s Republic of China

‡

ABSTRACT: The solubility of thiotriazinone in water, methanol, ethanol, water + methanol, and water + ethanol has been measured under temperatures ranging from (283 to 330) K with a laser technique. The results of these measurements were correlated with semiempirical equations. The calculated results have showed fine representativity of experimental data. The stepwise regression method was used to simplify the modified Jouyban−Acree equation.

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(293 to 343) K.4 In this study, the solubility of thiotriazinone in water, methanol, and ethanol solvents and water + methanol and water + ethanol binary mixtures were experimentally measured from (283 to 330) K using a laser monitoring observation technique.

INTRODUCTION Thiotriazinone (5,6-dioxo-2-methyl-3-thioxo-perhydro-1,2,4triazine, abbreviated as TTZ, C4H5N3O2S, molecular weight: 159.13, CAS Registry No. 58909-39-0) is an important intermediate which is widely used in synthesis of medicament for ceftriaxone and other antibiotics.1 Its structural formula is given in Figure 1.

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EXPERIMENTAL SECTION Materials. A white crystalline powder of thiotriazinone with a purity of 99.5 % was supplied by Shijiazhuang Hejia Health Productions Co., Ltd. Distilled deionized water was obtained from the market. Methanol and ethanol of analytical reagent grade were purchased from Tianjin Damao Chemical Reagent Factory. Their mass fraction purities are better than 99.5 % and are used without further purification. Apparatus and Procedures. The solubility of thiotriazinone was measured by apparatus similar to that described in literature.5 A 100 mL jacketed vessel was used to determine the solubility, the temperature was controlled to be constant (fluctuates with 0.05 K) through a thermostat water bath. The temperature of the inner chamber of the vessel was measured by a calibrated mercury-in-glass thermometer (uncertainty of ± 0.05 K). The dissolution of the solute was examined by the laser beam penetrating the vessel. To prevent the evaporation of the solvent, a condenser vessel was introduced. The masses of the samples and solvents were weighted using an analytical balance (Sartorius CP224S, Germany) with an uncertainty of ± 0.1 mg.

Figure 1. Chemical structure of thiotriazinone.

Thiotriazinone is synthesized by the cyclization of 2-methylthiosemicarbazide and diethyl oxalate or dimethyl oxalate. The reaction is carried out in the presence of sodium methoxide with appropriate alcohol and usually methanol. Finally, thiotriazinone is produced in the mixtures of water + methanol or water + ethanol by cooling crystallization. Purification of thiotriazinone is obtained by recrystallization in water.2,3 Considering the production and purification process of thiotriazinone, it is obvious that the solubility of thiotriazinone in water, methanol, ethanol, and their mixtures is important basic data for determining the proper solvent and designing an optimized crystallization process in production. In the open literature, there is only one report concerning the solubility of thiotriazinone in some monosolvents measured with temperatures ranging from © XXXX American Chemical Society

Received: October 27, 2011 Accepted: June 21, 2012

A

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In our experiments, the fluid in the glass vessel was monitored by a laser beam. At first, predetermined amounts of solvent were transferred into the jacketed vessel. The solution was stirred continuously with a magnetic at a required temperature. The highest intensity of the laser penetrated through the solution was regarded as the maximum. Then we started to add thiotriazinone to the vessel. Along with the dissolution of the particles of the solute, the intensity of the laser beam increased gradually. When the solute dissolved completely, the solution was clear, and the laser intensity reaches the previous value, another addition was made. This procedure was repeated until the penetrated laser intensity could not return to maximum or, in other words, the last addition of solute could not dissolve completely. The total amount of thiotriazinone added was used to compute the solubility. The reported solubility was the average of three-time repeated measurements. The uncertainty in the solubility values which can be due to the temperature measurements, weighing procedure, and instabilities of the water bath is estimated to be less than 2 %.

initial compositions increases with increasing temperature. For monosolvents, the solubility of thiotriazinone is ranked as methanol > ethanol > water. This phenomenon may be mainly due to the polarity of the solvents. The solubility of thiotriazinone in the water + methanol mixtures increased with increasing amounts of methanol at a given temperature. Among the experimental data, the solubility of thiotriazinone in the binary mixtures of water + ethanol shows a maximum at a liquid composition of ethanol x0B = 0.6103. This phenomenon may be a result of intermolecular hydrogen bonding between thiotriazinone and the water or cosolvent or a result of the polarity and ideality or nonideality of the mixed solvents.6,7 The primary reason is still unclear and needs further study. Data Correlation. The Apelblat equation, λh equation, and NRTL equation were widely used to correlate the solubility data in monosolvents. In recent research articles, the modified Apelblat equation could best correlate the solid−liquid equilibrium data for regular solution,8 and the modified Apelblat equation is expressed as:

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ln xA = A +

RESULTS AND DISCUSSION Solubility Data. The experimental solubility of thiotriazinone in binary solvent mixtures is listed in Tables 1 to 3 and

102 xA

283.25 288.17 293.05 298.00 302.87

0.08628 0.1012 0.1228 0.1439 0.1705

283.15 288.55 293.05 298.05 302.93

1.355 1.604 1.851 2.137 2.450

283.65 288.75 293.15 298.15 303.05

0.8216 0.9828 1.130 1.334 1.477

102 xcal A

T/K

Water 0.08628 307.95 0.1022 312.95 0.1211 318.25 0.1441 323.00 0.1712 328.25 Methanol 1.339 308.35 1.614 314.15 1.863 319.05 2.159 323.75 2.463 328.65 Ethanol 0.8309 308.05 0.9838 313.75 1.125 318.25 1.296 323.45 1.470 328.65

102 xA

102 xcal A

0.2055 0.2481 0.2933 0.3549 0.4313

0.2054 0.2459 0.2980 0.3543 0.4293

2.831 3.259 3.549 3.845 4.135

2.815 3.203 3.534 3.850 4.174

1.637 1.841 2.010 2.228 2.457

1.654 1.868 2.037 2.231 2.420

n

ln xA = x B0 ln(xA )B + xC0 ln(xA )C + x B0xC0 ∑ i=0

x B0 =

mB /MB mB /MB + mC /MC

Ji T

(x B0 − xC0)i (4)

x0B

x0C

In which and refer to the initial mole fraction of the binary solvent mixtures, (xA)i is the mole fraction solubility of the solute in monosolvents i. T is the absolute temperature, and Ji is the model constant. n refers to the number of “curve-fit” parameters (usually 3, n = 2). Zhou et al.10 proposed a modified Jouyban− Acree model correlating the solubility in binary solvent mixtures. In the experiment, x0C = (1 − x0B). The temperature dependence of the solubility of a solute in a monosolvents i ((xA)i) can be described with the modified Apelblat equation:

graphically plotted in Figures 2 and 3 as well. The solubility of thiotriazinone in mole fraction (xA) in different binary solvent mixtures could be obtained from eq 1, and the initial mole fraction concentrations of binary solvent mixtures (x0B) were calculated according to eq 2. mA /MA xA = mA /MA + mB /MB + mC /MC

(3)

In this study, the relationship between temperature and solubility in monosolvents is correlated with eq 3. Solubility models such as modified separation of cohesive energy density (MOSCED), universal functional activity coefficient (UNIFAC), nonrandom two-liquid segment activity coefficient (NRTL-SAC), and the Jouyban−Acree model were used for solubility correlation or prediction in binary solvent mixtures. Among these models, the Jouyban−Acree model is perhaps one of the more versatile models to describe the solubility of a solute with the variation of both temperature and initial composition of binary solvent mixtures.9 The basic Jouyban− Acree model is:

Table 1. Solubility of Thiotriazinone (xA) in Mono-Solvents Water, Methanol, and Ethanol from (283 to 330) K and Calculated Solubility (xcal A ) Obtained from eq 3 T/K

B + C ln T T

ln(xA )B = a1 +

b1 + c1ln T T

(5)

ln(xA )C = a 2 +

b2 + c 2 ln T T

(6)

Introducing = (1 − and (xA)i from eqs 5 and 6 into eq 4 and subsequent rearrangements result in eq 7: x0C

(1)

x0B)

b1 + c1 ln T + [a1 − a 2]x B0 T x0 + (b1 − b2 + J0 − J1 + J2 ) B + (3J1 − J0 − 5J2 ) T (x B0)2 (x B0)3 (x 0)4 + (8J2 − 2J1) + ( −4J2 ) B T T T

ln xA = a1 + (2)

where mA, mB, and mC represent the mass of thiotriazinone (A), organic solvent (B = methanol, ethanol), and water (C). MA, MB, and MC are the respective molecular weights. From Tables 1 to 3 and Figures 2 and 3, it can be seen that the solubility of thiotriazinone in binary solvent mixtures with given

+ (c1 − c 2)x B0 ln T B

(7)

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Table 2. Solubility of Thiotriazinone (xA) in Water (C) + Methanol (B) at Various Contents of Methanol (x0B) from (283 to 330) K, and Calculated Solubility (xcal A ) Obtained from eq 8 102 xA

T/K

102 xcal A

T/K

102 xA

102 xcal A

T/K

102 xA

x0B = 0.0000 283.25 288.17 293.05 298.00 302.87

0.08628 0.1012 0.1228 0.1439 0.1705

283.34 288.35 293.53 298.02 303.57

0.09451 0.1189 0.1458 0.1766 0.2196

283.15 288.25 293.49 297.95 303.45

0.1130 0.1463 0.1803 0.2201 0.2796

283.16 288.51 293.11 298.37 303.27

0.1586 0.2036 0.2497 0.3031 0.3749

283.05 288.55 293.29 298.35 303.38

0.2281 0.2871 0.3494 0.4369 0.5296

283.34 288.21 293.20

0.3547 0.4335 0.5315

0.0714 307.95 0.0882 312.95 0.1088 318.25 0.1349 323.00 0.1668 328.25 x0B = 0.06133 0.09308 308.53 0.1148 313.53 0.1427 318.27 0.1725 323.35 0.2181 328.65 x0B = 0.1242 0.1236 308.57 0.1522 313.47 0.1885 318.35 0.2262 323.45 0.2833 328.65 x0B = 0.1943 0.1726 308.63 0.2133 313.53 0.2559 318.60 0.3149 323.25 0.3818 328.45 x0B = 0.2733 0.2486 308.62 0.3069 313.50 0.3676 318.50 0.4451 323.40 0.5376 328.45 x0B = 0.3650 0.3738 308.13 0.4473 313.63 0.5366 318.45

0.2055 0.2481 0.2933 0.3549 0.4313

0.2084 0.2595 0.3279 0.4045 0.5104

0.2642 0.3276 0.3951 0.4870 0.5884

0.2692 0.3330 0.4073 0.5056 0.6335

0.3441 0.4241 0.5269 0.6522 0.7994

0.3493 0.4268 0.5209 0.6412 0.7923

0.4748 0.5874 0.7276 0.9006 1.102

0.4710 0.5704 0.6947 0.8319 1.017

0.6658 0.8228 1.013 1.245 1.510

0.6536 0.7830 0.9410 1.125 1.351

0.9436 1.163 1.403

0.9130 1.105 1.304

x B0

In which xA is the mole fraction solubility of the solute in binary solvent mixtures, T is the absolute temperature, Ai is the model parameter, and x0B is the initial mole fraction of the binary solvent mixtures. The parameter values of eqs 3 and 8 are directly obtained by the linear least-squares method from the experimental data. The mean percentage deviation (MPD) between experimental and calculated xA values are considered as an accuracy criterion. MPD is defined as: 100 N

∑

|xAcal − xA| xA

102 xA

102 xcal A

298.47 303.42

0.6461 0.7833

283.25 288.15 293.29 298.45 303.37

0.5159 0.6127 0.7395 0.8918 1.060

283.44 288.31 293.35 298.27 303.57

0.6941 0.822 0.9736 1.137 1.345

283.15 288.25 293.29 298.25 303.42

1.060 1.214 1.381 1.568 1.797

282.65 287.75 293.19 298.65 303.57

1.157 1.368 1.618 1.902 2.163

283.15 288.55 293.05 298.05 302.93

1.355 1.604 1.851 2.137 2.450

0.6487 323.35 0.7736 328.35 x0B = 0.4572 0.5261 308.17 0.6266 313.50 0.7501 318.45 0.8957 323.25 1.058 328.35 x0B = 0.5675 0.7348 308.53 0.8691 313.53 1.029 318.25 1.209 323.35 1.432 328.65 x0B = 0.6934 0.9434 308.47 1.119 313.45 1.318 318.25 1.538 323.35 1.797 328.95 x0B = 0.8299 1.108 308.95 1.312 314.00 1.556 319.45 1.831 323.95 2.106 329.25 x0B = 1.0000 1.366 308.35 1.624 314.15 1.860 319.05 2.144 323.75 2.442 328.65

1.681 2.001

1.541 1.823

1.254 1.499 1.794 2.117 2.495

1.241 1.476 1.731 2.014 2.360

1.592 1.853 2.165 2.523 2.931

1.670 1.944 2.236 2.592 3.011

2.056 2.331 2.651 3.021 3.435

2.081 2.393 2.726 3.118 3.594

2.438 2.717 3.046 3.407 3.814

2.436 2.775 3.172 3.526 3.971

2.831 3.259 3.549 3.845 4.135

2.796 3.199 3.557 3.913 4.296

in Tables 1 to 3 and plotted in Figures 2 and 3. The values of their parameters are presented in Tables 4 to 6 together with the MPD. The MPD for the modified Apelblat eq 3 is 0.61, 0.78, and 1.05. The MPD for the eq 8 in water + methanol and water + ethanol are 4.18 and 4.87, respectively. This findings showed that the modified Apelblat model fitted very well to the experimental solubility data of thiotriazinone in the monosolvents water, methanol, and ethanol, and the modified Jouyban−Acree model fitted very well to the experimental solubility data of thiotriazinone in the binary water + methanol and water + ethanol solvent mixtures at all initial composition ranges of water content between (283 and 330) K. Model Simplification. Stepwise regression is a statistic technique widely used for variable selection. Generally, some independent variables do not have an important effect on the dependent variables in a model. Thus, it is a simplification to keep only the statistically significantly variables in the model. In this work, the stepwise regression method was taken to study the significance of each independent variable for the regression equation.11 The significant variables were added, while the insignificant variables were removed. The conditions of adding independent variables are: the independent variable is the most prominent among all the independent variables by the inspection of partial regression square. Because of the adding or removing new independent variable, the significance of the other variables

(x B0)2

A2 + A3 ln T + A4 x B0 + A5 + A6 T T T 0 3 0 4 (x ) (x ) + A 7 B + A8 B + A 9x B0 ln T (8) T T

MPD =

T/K

x0B = 0.3650

Introducing a constant term to eq 7, it can be further simplified as: ln xA = A1 +

102 xcal A

(9)

where xA is the experimental data, xcal A is the solubility calculated from the hybrid model eq 8, and N is the number of experimental points. The solubility of thiotriazinone in monosolvents and binary solvent mixtures has been calculated by eqs 3 and 8 and is listed C

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Table 3. Solubility of Thiotriazinone (xA) in Water (C) + Ethanol (B) at Various Contents of Ethanol (x0B) from (283 to 330) K, and Calculated Solubility (xcal A ) Obtained from eq 8 T/K

102 xA

102 xcal A

T/K

102 xA

102 xcal A

T/K

102 xA

x0B = 0.0000 283.25 288.17 293.05 298.00 302.87

0.08628 0.1012 0.1228 0.1439 0.1705

283.32 288.59 293.23 298.02 303.55

0.09477 0.1177 0.1461 0.1803 0.2298

283.49 288.31 292.95 298.87 303.17

0.1068 0.1333 0.1774 0.2313 0.2863

283.25 288.35 292.94 298.65 303.15

0.1896 0.2289 0.2876 0.3705 0.4521

283.44 288.91 292.75 298.22 303.27

0.2542 0.3308 0.4073 0.5135 0.6440

283.05 288.85 292.59

0.4022 0.5059 0.5982

0.0637 307.95 0.0805 312.95 0.1014 318.25 0.1278 323.00 0.1603 328.25 x0B = 0.04964 0.09690 308.23 0.1233 313.48 0.1521 318.30 0.1886 322.85 0.2411 327.96 x0B = 0.08932 0.1325 308.63 0.1640 313.53 0.2010 318.30 0.2598 322.85 0.3125 327.96 x0B = 0.1432 0.1909 308.57 0.2370 313.45 0.2873 319.00 0.3641 323.25 0.4379 327.96 x0B = 0.2076 0.2839 308.71 0.3541 313.03 0.4128 318.85 0.5122 323.35 0.6234 328.75 x0B = 0.2808 0.4025 308.67 0.5031 313.45 0.5797 318.95

102 xcal A

T/K

102 xA

102 xcal A

1.895 2.236

1.754 2.108

1.393 1.634 1.926 2.257 2.614

1.380 1.630 1.905 2.240 2.644

1.639 1.904 2.211 2.573 2.948

1.696 1.974 2.291 2.651 3.085

1.797 2.057 2.347 2.685 3.047

1.871 2.133 2.461 2.816 3.197

1.782 2.005 2.258 2.566 2.892

1.774 2.000 2.272 2.559 2.851

1.637 1.841 2.010 2.228 2.457

1.634 1.852 2.033 2.252 2.481

x0B = 0.2808 0.2055 0.2481 0.2933 0.3549 0.4313

0.2025 0.2544 0.3232 0.3998 0.5047

0.2820 0.3475 0.4278 0.5267 0.6513

0.2962 0.3723 0.4583 0.5567 0.6912

0.3736 0.4660 0.5834 0.7259 0.8913

0.3940 0.4840 0.5903 0.7120 0.8770

0.5688 0.7094 0.8745 1.078 1.312

0.5454 0.6631 0.8261 0.9756 1.171

0.8079 0.9925 1.225 1.459 1.760

0.7680 0.9046 1.125 1.328 1.617

1.107 1.331 1.609

1.047 1.242 1.506

298.15 303.17

0.7386 0.8947

283.24 288.31 293.45 298.47 303.47

0.5611 0.6753 0.8193 0.9702 1.165

283.20 288.30 293.44 298.40 303.42

0.7303 0.8621 1.016 1.196 1.400

283.14 288.31 293.35 298.27 303.37

0.8758 1.003 1.172 1.338 1.543

282.95 288.30 293.39 298.35 303.42

0.9443 1.072 1.220 1.363 1.551

283.65 288.75 293.15 298.15 303.05

0.8216 0.9828 1.130 1.334 1.477

0.7135 323.35 0.8581 328.75 x0B = 0.3693 0.5667 308.58 0.6818 313.58 0.8195 318.35 0.9774 323.40 1.161 328.65 x0B = 0.4751 0.7347 308.57 0.8762 313.50 1.042 318.45 1.227 323.40 1.442 328.65 x0B = 0.6103 0.8521 308.68 1.009 313.33 1.184 318.55 1.378 323.60 1.604 328.50 x0B = 0.7813 0.8491 308.62 1.003 313.35 1.167 318.55 1.345 323.60 1.546 328.35 x0B = 1.0000 0.8675 308.05 1.005 313.75 1.133 318.25 1.290 323.45 1.455 328.65

Figure 2. Solubility results of thiotriazinone at various temperatures and compositions of water (C) + methanol (B) binary mixtures: *, experimental data points; solid line, calculated from eq 8.

to the equation will be changed, and the process of the stepwise regression will be repeated. When there is an independent variable added or removed, it will take new significant test for each variable,

and then based on the significant test result, further introduction or deletion will be taken. At last, all of the independent variables are significant in the final form of the regression equation. D

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Figure 3. Solubility results of thiotriazinone at various temperatures and compositions of water (C) + ethanol (B) binary mixtures: *, experimental data points; solid line, calculated from eq 8.

Table 4. Parameters for Thiotriazinone in Mono-Solvents by the Modified Apelblat eq 3

Table 6. Parameters of eq 8 for Thiotriazinone in Binary Water + Ethanol Solvent Mixtures

solvent

A

B

C

MPD

parameter

linear regression

stepwise regression

water methanol ethanol

−176.453 183.005 180.932

4892.55 −10445.9 −10286.7

26.9423 −26.6432 −26.4631

0.61 0.78 1.05

A1 A2 A3 A4 A5 A6 A7 A8 A9 R2 F MPD

−129.781 1955.83 20.4588 197.279 −5315.12 −2139.77 −423.909 816.324 −30.0630 0.9941 2119.94 4.87

−86.6690

Table 5. Parameters of eq 8 for Thiotriazinone in Binary Water + Methanol Solvent Mixtures parameter

linear regression

A1 A2 A3 A4 A5 A6 A7 A8 A9 R2 F MPD

−196.092 5146.23 30.2284 298.992 −11673.9 1350.50 −3172.63 1521.62 −44.943 0.9971 4292.32 4.18

14.0432 −4.76667 3899.42 −2400.95 603.238 0.9939 3414.90 4.96

model was filtered out by the automatic procedure. Usually, the evaluation of the model is made by F statistic and adjusted R2. The greater the F value or adjusted R2 is, the more reliable the results are. For the stepwise regression used for the data of water + ethanol mixed solvent, input the following statements in MATLAB: ≫data = [database]; ≫y = data(:,1); x 1 = data(:,2); x 2 = data(:,3); x3 = data(:,4); x4 = data(:,5); x5 = data(:,6); x6 = data(:,7); x7 = data(:,8); x1 = data(:,2); x8 = data(:,9); ≫x = [x1, x2, x3, x4, x5, x6, x7, x8]; ≫stepwise(x, y) Then the interface appeared like Figure 4. Doing stepwise regression, let all the variables are not included in the equation, and MATLAB will automatically calculate which variable will be introduced at this time, then according to the prompt of “next step” on the right of the interface to input or output the variable, until neither variables input or output. The results of the stepwise regression appear like Figure 5. After stepwise regression, the number of items for the water + methanol binary mixtures does not change, that is to say, through the automatic calculation by MATLAB, all nine variables are statistically significant in the model. But for the water + ethanol

This article use MATLAB for the stepwise regression. The MATLAB stepwise function what is an interactive tool performs a stepwise regression of the input data to uncover statistically significant relationships. The stepwise function provides the user with a graphical interface to step through each step in the regression. Any variable that is determined should be kept in the final model is colored blue while those variables that do not add to the model are colored red. In the graphical interface, it showed the coefficients, t-star, p-value for all variables, and R2, adjusted R2, F, and p values which are measures of statistical significance as well as the intercept of the data are also displayed. Stepwise regression using the stepwise function of MATLAB was performed of random data and correlated data generated in Microsoft Excel, as well as example data from a statistics text. Stepwise regression used for the regressive model, the most significant E

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Figure 4. Stepwise regression analysis interface of MATLAB.

Figure 5. Results of stepwise regression for water + ethanol.

ranging from (283 to 330) K. The solubility of thiotriazinone was found to increase with increasing temperature. In monosolvents water, methanol, and ethanol, the largest solubility of thiotriazinone is in methanol and the lowest is in water. This phenomenon may be mainly due to the polarity of the solvents. In the binary mixtures of water + methanol and water + ethanol, the solubility of thiotriazinone increases with increasing methanol or ethanol content at a given temperature. For the binary mixtures of water + ethanol, there is a maximum solubility at a specific initial composition of ethanol. The calculation solubility by

binary mixtures, the number of items of the equation reduces from nine to six, the parameters for the stepwise regression are listed in Tables 6, and the MPD of water + ethanol binary mixtures increases from 4.87 to 4.96. Obviously, for the water + ethanol binary mixtures, the stepwise regression assured certain accuracy and reliability, while at the same time significantly simplified models.

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CONCLUSION The solubility of thiotriazinone in water, methanol, ethanol, water + methanol, and water + ethanol has been measured in temperatures F

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(11) Tomson, R.; Uhlin, F.; Holmar, J.; Lauri, K.; Luman, M.; Fridolin, I. Development of a method for optical monitoring of creatinine in the spent dialysate. Estonian J. Eng. 2011, 17, 140−150.

eqs 3 and 8 shows good agreement with the experimental values. The modified Jouyban−Acree model can be used to caculate the solubility of thiotriazinone in the water + methanol and water + ethanol binary solvent mixtures with any methanol or ethanol content at temperatures ranging from (283 to 330) K. After stepwise regression, the number of items of the equation for water + ethanol binary solvent mixtures was reduced. The simplified equations include all of the independent variables that have a significant effect on the dependent variable. The stepwise regression in this work significantly simplified the model, while at the same time assured certain accuracy and reliability. The experimental solubility and the equations presented in this work can be used as essential data and models in the practical process of synthesis and purification of thiotriazinone.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +86-10-64434775. Funding

We are indebted to the National High Technology Research and Development Program of China (863 Program, Grant No. 2009AA05Z436) and the Special Fund for Basic Scientific Research of Central Colleges (Grant No. ZZ1107). Notes

The authors declare no competing financial interest.

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REFERENCES

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dx.doi.org/10.1021/je201149u | J. Chem. Eng. Data XXXX, XXX, XXX−XXX