Comment/Reply pubs.acs.org/jced
Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Reply to “Comment on ‘Determination and Correlation of Dipyridamole p‑Toluene Sulfonate Solubility in Seven Alcohol Solvents and Three Binary Solvents’” Mengya Li,†,‡ Shiyuan Liu,†,‡ Si Li,†,‡ Yang Yang,†,‡ Yingdan Cui,†,‡ and Junbo Gong*,†,‡,§ †
School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin, 300072, China ‡ Collaborative Innovation Center of Chemistry Science and Engineering, Tianjin, 300072, China § Key Laboratory Modern Drug Delivery and High Efficiency, Tianjin University, Tianjin, 300072, China ABSTRACT: The Comment on “Determination and Correlation of Dipyridamole p-Toluene Sulfonate Solubility in Seven Alcohol Solvents and Three Binary Solvents” is appreciated. According to the comments, we make a deep analysis and discussion of our article again. The reason for large deviations between the back-calculated value presented in our paper and the backcalculated value calculated by Acree is that we mixed up the coefficients calculated by two programs and the wrong Apelblat equation coefficients were submitted in our paper instead of the corrected ones. Therefore, the model parameters of the Apelblat equation and the calculated mole fraction solubilities of dipyridamole p-toluene sulfonate in all solvents at the temperature ranging from 288.15 to 328.15 K were recalculated by the corrected program and show satisfactory correlation results with the experimental values. he comments on “Determination and Correlation of Dipyridamole p-Toluene Sulfonate Solubility in Seven Alcohol Solvents and Three Binary Solvents” (J. Chem. Eng. Data 2017, 63, 208−216)1 from by Dr. William Acree are very valuable and helpful to improve the quality of our paper.1,2 We have seriously considered the comments and made a discussion of our article again. The solubility of dipyridamole p-toluene sulfonate, as an important medical intermediate, plays a major role in the whole synthesis of dipyridamole. However, the thermodynamic data of this important medical intermediate in some alcohol solvents which are industrial commonly used have not been systematically reported yet. In our recent paper,1 the solubility of dipyridamole p-toluene sulfonate in seven monosolvents (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol) and binary solvent mixtures (methanol + ethanol, methanol + 1-propanol, methanol +1-butanol) was determined. Besides, the Apelblat equation, CNIBS/R-K model, and the combined version of the Jouyban−Acree model (Apel-JA) were used to correlate the experimental results. The errors pointed out in comment were confirmed by our group, and we found the reason for large deviations between the back-calculated value presented in our paper and the backcalculated value calculated by Dr. William Acree. We mixed up the coefficients calculated by two programs:2 the program written by ourselves in the beginning was found to contain small mistakes, which were corrected afterward, and the new one was then used for recalculation. However, due to our carelessness, the wrong Apelblat equation coefficients were submitted in our paper, instead of the corrected ones, resulting in the significant difference from the back-calculated value. We guarantee the reliability of all experimental mole fraction solubilities of dipyridamole p-toluene sulfonate in our paper, as the same experiment was repeated at least three times.
T
© XXXX American Chemical Society
Still, a correction about the model parameters should be made in Tables S1 and S2, together with some of the backcalculated value calculated by eq 4 in Tables 2 to 5 of the paper.1 The Apelblat model has been widely used to evaluate the relationship between temperature and the mole fraction solubility of solute,3,4 and it could be expressed by eq 1 as follow: ln x1 = A +
B + C ln T T
(1)
where T represents the absolute temperature (K), x1 is the mole fraction of the solute at T and A, B, and C are semiempirical constants. Therefore, the model parameters of the Apelblat equation and the calculated mole fraction solubilities by eq 1 of dipyridamole p-toluene sulfonate in seven monosolvents and three binary solvents at temperatures ranging from 288.15 to 328.15 K were recalculated by the program we corrected; all of the revised data are shown in bold in Tables 1 to 6. When the corrected Apelblat equation coefficients were substituted into eq 1, the calculated x1 are reasonable. Although there is still a little difference between the calculated and experimental values, we believe that these predictions are rational, of which the maximum ARD (average relative deviation) value is 6.26% and the maximum RMSD (root-mean-square deviations) value is 8.91 × 10−5 in the Apelblat equation. We sincerely appreciate the valuable comments suggested by Acree to help us improve our paper, which could be better Received: March 16, 2018 Accepted: April 24, 2018
A
DOI: 10.1021/acs.jced.8b00208 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Comment/Reply
cal Table 1. Experimental (xexp 1 ) and Calculated (x1 ) Mole Fraction Solubilities of Dipyridamole p-Toluene Sulfonate in Seven Mono-Solvents at Temperature T and Pressure P = 0.1 MPaa
T/K 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 288.15 293.15
104xexp 1 Methanol 15.40 18.38 24.04 27.82 30.83 37.29 44.32 53.24 65.11 Ethanol 4.80 6.22 7.38 8.81 10.30 12.62 13.80 16.95 19.83 1-Propanol 3.71 4.19 4.66 6.02 6.73 7.98 9.56 13.83 16.96 2-Propanol 1.74 2.18 2.73 3.05 3.69 4.25 4.95 6.22 7.27 1-Butanol 2.08 2.32 3.10 3.70 4.37 5.22 5.98 7.28 8.76 Isobutyl Alcohol 2.49 2.87 3.34 4.21 5.20 5.90 6.09 7.35 8.40 2-Butanol 1.22 1.49
Table 1. continued T/K 298.15 303.15 308.15 313.15 318.15 323.15 328.15
104xcal 1 (eq 1) 15.67 18.77 22.45 26.80 31.94 38.01 45.16 53.57 63.43
104xexp 1
104xcal 1 (eq 1)
2-Butanol 1.80 2.31 3.01 3.84 4.27 5.00 6.02
1.90 2.37 2.92 3.56 4.29 5.12 6.05
a
x1exp is the experimental solubility; x1cal (eq 1) is the calculated solubility according to eq 1. The standard uncertainty of T is u(T) = 0.1 K. The relative uncertainty of the solubility is ur(x1) = 0.01. The relative uncertainty of pressure is ur(P) = 0.01. cal Table 2. Experimental (xexp 1 ) and Calculated (x1 ) Mole Fraction Solubilities of Dipyridamole p-Toluene Sulfonate in Methanol (x2) + Ethanol (1 − x2) at Temperature T and Pressure P = 0.1 MPaa
4.92 6.02 7.30 8.77 10.44 12.34 14.47 16.84 19.48
x2 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
3.75 4.17 4.76 5.58 6.68 8.19 10.24 13.04 16.91
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
1.79 2.15 2.58 3.08 3.67 4.35 5.15 6.08 7.17
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
2.02 2.47 3.00 3.62 4.34 5.19 6.17 7.31 8.63
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
2.42 2.93 3.52 4.17 4.88 5.65 6.48 7.36 8.29
0.10 0.20 0.30 0.40 0.50
1.18 1.51 B
104xexp 1 T = 288.15 5.73 6.26 7.01 8.41 8.92 10.10 11.24 12.93 13.99 T = 293.15 6.73 7.31 8.59 10.14 10.59 12.08 13.82 15.03 16.22 T = 298.15 8.10 9.02 10.69 11.67 12.66 13.37 15.66 16.89 20.11 T = 303.15 10.08 11.38 12.65 13.42 14.24 15.35 17.52 20.26 23.08 T = 308.15 11.94 13.31 14.04 15.91 17.24
104xcal 1 (eq 1) K 5.75 6.22 7.26 8.53 9.02 10.03 11.30 12.78 14.34 K 6.90 7.60 8.68 9.97 10.59 11.72 13.27 14.83 16.59 K 8.23 9.18 10.33 11.64 12.43 13.73 15.60 17.31 19.36 K 9.79 10.99 12.22 13.58 14.60 16.13 18.37 20.33 22.79 K 11.58 13.02 14.38 15.84 17.15 DOI: 10.1021/acs.jced.8b00208 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Comment/Reply
Table 2. continued x2 0.60 0.70 0.80 0.90 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
Table 3. continued 104xexp 1 T = 308.15 19.43 21.31 23.88 27.14 T = 313.15 13.77 15.40 16.71 18.61 20.83 23.08 26.05 28.64 31.71 T = 318.15 15.28 17.50 19.36 21.38 23.09 26.07 30.28 34.20 39.67 T = 323.15 18.87 20.28 23.01 25.09 27.55 31.21 35.75 40.69 45.77 T = 328.15 21.91 23.94 26.20 29.24 32.77 37.17 41.81 48.86 57.74
104xcal 1
x2
(eq 1)
K 0.70 0.80 0.90
18.98 21.65 24.01 27.03 K
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
13.64 15.30 16.83 18.48 20.14 22.39 25.53 28.50 32.30 K
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
16.01 17.83 19.61 21.54 23.64 26.46 30.13 33.99 38.84 K 18.72 20.62 22.73 25.09 27.76 31.31 35.57 40.70 47.00
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
21.81 23.66 26.24 29.21 32.58 37.12 42.02 48.94 57.19
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
K
a exp x1
is the experimental solubility; xcal 1 (eq 1) is the calculated solubility according to eq 1. The standard uncertainty of T is u(T) = 0.1 K. The relative uncertainty of the solubility is ur(x1) = 0.01. The relative uncertainty of pressure is ur(P) = 0.05. The relative uncertainty of the initial mass fraction of methanol in the binary solvents is ur(x2) = 0.002.
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
cal Table 3. Experimental (xexp 1 ) and Calculated (x1 ) Mole Fraction Solubilities of Dipyridamole p-Toluene Sulfonate in Methanol (x2) + 1-Propanol (1-x2) at Temperature T and Pressure P = 0.1 MPaa
x2
104xexp 1
104xcal 1 (eq 1)
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
T = 288.15 K 0.10
4.12
4.01
0.20
4.29
4.20
0.30
5.17
4.84
0.40
5.99
5.88
0.50
7.37
7.35
0.60
8.87
8.88 C
104xexp 1 T = 288.15 10.03 12.18 13.53 T = 293.15 4.60 5.14 5.90 7.03 8.50 10.30 11.98 14.27 16.49 T = 298.15 5.51 6.10 7.13 8.34 10.09 11.77 13.97 16.62 19.19 T = 303.15 6.22 7.08 8.47 9.93 12.14 13.92 16.33 19.72 22.96 T = 308.15 7.55 8.51 10.38 11.62 13.72 16.46 19.30 23.03 27.06 T = 313.15 9.28 10.71 12.31 14.36 16.70 19.56 22.47 27.08 31.39 T = 318.15 11.02 13.07 15.46 17.26 20.01 22.93 27.63 32.90 38.75
104xcal 1 (eq 1) K 10.30 12.59 14.19 K 4.63 5.04 5.92 6.99 8.55 10.18 11.81 14.24 16.27 K 5.41 6.06 7.21 8.33 10.02 11.82 13.73 16.39 18.93 K 6.40 7.30 8.74 9.97 11.84 13.87 16.15 19.18 22.31 K 7.65 8.81 10.52 11.95 14.08 16.45 19.21 22.79 26.63 K 9.25 10.66 12.61 14.35 16.85 19.69 23.09 27.46 32.14 K 11.28 12.91 15.04 17.28 20.28 23.79 28.03 33.52 39.22 DOI: 10.1021/acs.jced.8b00208 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Comment/Reply
Table 3. continued x2 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
Table 4. continued 104xexp 1 T = 323.15 K 14.46 15.93 18.27 21.34 25.28 30.33 35.25 41.77 48.56 T = 328.15 K 16.98 18.85 20.76 24.91 29.52 35.09 42.04 51.83 60.20
104xcal 1
x2
(eq 1)
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
13.88 15.67 17.86 20.84 24.54 28.98 34.32 41.43 48.33
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
17.23 19.04 21.10 25.18 29.83 35.59 42.37 51.79 60.10
a exp x1
is the experimental solubility; xcal 1 (eq 1) is the calculated solubility according to eq 1. The standard uncertainty of T is u(T) = 0.1 K. The relative uncertainty of the solubility is ur(x1) = 0.05. The relative uncertainty of pressure is ur(P) = 0.05. The relative uncertainty of the initial mass fraction of methanol in the binary solvents is ur(x2) = 0.003.
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
cal Table 4. Experimental (xexp 1 ) and Calculated (x1 ) Mole Fraction Solubilities of Dipyridamole p-Toluene Sulfonate in Methanol (x2) + 1-Butanol (1-x2) at Temperature T and Pressure P = 0.1 MPaa
x2 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
104xexp 1 T = 288.15 K 3.01 4.23 5.04 6.52 7.71 9.07 11.07 13.15 14.40 T = 293.15 K 4.50 5.56 6.53 8.18 9.38 11.21 13.09 15.55 17.03 T = 298.15 K 5.36 6.89 8.13 9.56 11.43 13.23 16.12 19.12 21.11
104xcal 1
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
(eq 1)
3.65 4.68 5.55 7.02 8.39 9.63 11.53 13.58 15.13
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
4.37 5.43 6.61 8.21 9.52 11.07 13.38 15.79 17.39
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
5.17 6.26 7.77 9.53 10.82 12.73 15.50 18.35 20.12
104xexp 1 T = 303.15 6.79 7.26 9.92 11.90 13.18 15.17 18.75 21.87 23.93 T = 308.15 7.07 8.10 10.29 12.75 14.35 16.68 20.76 24.32 27.71 T = 313.15 7.92 8.79 11.39 13.97 15.66 18.76 23.22 28.61 32.73 T = 318.15 8.51 10.71 13.00 15.05 17.86 22.00 27.32 33.59 38.35 T = 323.15 9.69 11.96 14.95 17.39 20.71 25.68 31.73 38.08 44.13 T = 328.15 11.82 13.38 16.81 20.10 24.92 29.33 36.68 45.30 56.01
104xcal 1 (eq 1) K 6.04 7.19 9.04 10.95 12.33 14.63 17.94 21.33 23.45 K 6.98 8.21 10.40 12.49 14.08 16.82 20.73 24.77 27.51 K 7.99 9.33 11.84 14.13 16.10 19.32 23.93 28.76 32.45 K 9.05 10.55 13.37 15.86 18.45 22.20 27.57 33.38 38.49 K 10.16 11.89 14.95 17.69 21.18 25.49 31.73 38.73 45.89 K 11.30 13.35 16.57 19.59 24.34 29.26 36.46 44.90 54.95
a exp x1
is the experimental solubility; xcal 1 (eq 1) is the calculated solubility according to eq 1. bThe standard uncertainty of T is u(T) = 0.1 K. The relative uncertainty of the solubility is ur(x1) = 0.08. The relative uncertainty of pressure is ur(P) = 0.05. The relative uncertainty of the initial mass fraction of methanol in the binary solvents is ur(x2) = 0.003. D
DOI: 10.1021/acs.jced.8b00208 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Comment/Reply
Table 5. Model Parameters of Apelblat Equation for Dipyridamole p-Toluene Sulfonate in Seven Mono-Solvents
a
solvents
10−2A
10−3B
10−1C
ARDa/%
105RMSDb
methanol ethanol 1-propanol 2-propanol 1-butanol isobutyl alcohol 2-butanol
−0.9794123 0.6522319 −7.115866 −0.6865668 −0.2588632 1.492086 1.167984
1.395060 −6.061599 29.13516 −0.01686952 −2.090265 −9.645575 −9.000208
1.529819 −0.9146878 10.63988 1.060972 0.4349910 −2.190573 −1.670515
2.75 2.02 3.05 2.39 2.37 3.30 2.94
8.91 2.30 3.79 1.06 1.14 2.09 1.41
ARD is the average relative deviation. bRMSD is the root-mean-square deviation.
Table 6. Model Parameters of Apelblat Equation for Dipyridamole p-Toluene Sulfonate in Three Binary Solvents
a
x2a
10−2A
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
−0.2857350 0.9102402 0.01978175 −1.130679 −1.291778 −1.835193 −1.535382 −2.649849 −3.226435
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
−4.124690 −2.018172 −0.1803912 −2.037447 −3.013746 −3.879098 −4.084244 −5.044140 −4.389285
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
1.503283 0.1045195 1.461711 0.9608776 −1.578886 −1.076112 −0.8061691 −1.108489 −2.801457
10−3B
10−1C
Methanol + Ethanol −1.687002 0.4761609 −7.150058 −1.299422 −2.977935 0.01991314 2.392256 1.725078 3.023895 1.971808 5.460785 2.783857 4.087692 2.340725 9.124021 4.002103 11.68071 4.865545 Methanol + 1-Propanol 15.57787 6.190302 5.855048 3.067432 −2.456139 0.3342207 6.069102 3.094266 10.64379 4.541735 14.62929 5.828808 15.52038 6.139046 19.91256 7.568339 16.87028 6.600601 Methanol +1-Butanol −9.471771 −2.213696 −2.910591 −0.1415596 −9.193252 −2.149977 −6.761508 −1.410521 4.767062 2.370659 2.385701 1.631266 1.081268 1.237733 2.381402 1.694770 9.929286 4.223434
ARDb/%
105RMSDc
1.96 1.94 1.90 0.74 1.46 2.10 1.65 0.80 1.97
3.07 2.72 2.68 1.15 3.45 4.38 4.12 1.92 6.45
1.92 1.76 2.38 1.04 1.43 1.37 1.66 1.43 1.81
2.41 1.79 2.92 2.22 3.30 5.60 4.37 3.67 4.72
6.26 3.64 3.77 3.24 3.86 2.26 2.13 1.89 2.41
4.50 3.24 4.19 5.00 5.54 3.77 4.64 4.70 8.30
x2 is the initial mass fraction of methanol in the binary solvents. bARD is the average relative deviation. cRMSD is the root-mean-square deviation.
(2015AA021002) and Tianjin Science and Technology Project (15JCZDJC33200).
applied to the crystallization process design in the synthesis of dipyridamole.
■
■
AUTHOR INFORMATION
REFERENCES
(1) Li, M.; Liu, S.; Li, S.; Yang, Y.; Cui, Y. Determination and Correlation of Dipyridamole p-Toluene Sulfonate Solubility in Seven Alcohol Solvents and Three Binary Solvents. J. Chem. Eng. Data 2018, 63, 208−216. (2) Acree, W., Comments on “Determination and Correlation of Dipyridamole p-Toluene Sulfonate Solubility in Seven Alcohol Solvents and Three Binary Solvents. J. Chem. Eng. Data 2018 DOI: 10.1021/ acs.jced.8b00042. (3) Jiménez, D. M.; Cárdenas, Z. J.; Martínez, F. Solubility and solution thermodynamics of sulfadiazine in polyethylene glycol 400+water mixtures. J. Mol. Liq. 2016, 216, 239−245. (4) Wang, L.-C.; Ding, H.; Zhao, J.-H.; Song, C.-Y.; Wang, J.-S. Solubility of Isonicotinic Acid in 4-Methylpyridine plus Water from (287.65 to 361.15) K. J. Chem. Eng. Data 2008, 53, 2544−2546.
Corresponding Author
*Tel.: 86-22-27405754. Fax: +86-22-27374971. E-mail: junbo_
[email protected]. ORCID
Junbo Gong: 0000-0002-3376-3296 Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS The authors are grateful to the financial support of National Natural Science Foundation of China (NNSFC 81361140344 and NNSFC 21376164), National 863 Program E
DOI: 10.1021/acs.jced.8b00208 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
