Solubilities of 5, 10, 15, 20-Tetraphenylporphyrin and 5, 10, 15, 20

Article pubs.acs.org/jced

Solubilities of 5,10,15,20-Tetraphenylporphyrin and 5,10,15,20Tetra(p‑chlorophenyl)porphyrin in Binary N,N‑Dimethylformamide + Water Solvent Mixtures Chunlin Li,† Qinbo Wang,*,† Binwei Shen,‡ Zhenhua Xiong,‡ and Chuxiong Chen‡ †

Department of Chemical Engineering, Hunan University, Changsha 410082, P. R. China Quzhou Qunying Chemical Technology Co. Ltd., Quzhou 324002, P. R. China

‡

ABSTRACT: The mole fraction solubilities of 5,10,15,20-tetraphenylporphyrin (TPP) and 5,10,15,20-tetra(p-chlorophenyl)porphyrin (p-ClTPP) in binary system N,N-dimethylformamide (DMF) + water solvent mixtures were measured at atmospheric pressure by using the static method. The temperature and effects of mole fraction of DMF in the solvent mixtures on solubility were studied. The results show that the solubilities of TPP and p-ClTPP increase with the increasing temperature for a certain solvent composition, and the solubilities show a maximum in pure DMF, then the solubilities decrease when the water was added to the system. The experimental data were correlated with modified Apelblat equation. The solubilities calculated by the model were in good agreement with experimental observations. Thermodynamic parameters such as dissolution enthalpy, isobaric heat capacity and Gibbs energy were obtained from the solubility data by using the Clark−Glew equation together with the modified Apelblat equation. The result demonstrated that the dissolving process of TPP and p-ClTPP in DMF + water solvent mixtures is endothermic and not spontaneous.

1. INTRODUCTION Porphyrins and their metallic derivatives are one kind of the stable tetrapyrrolic macrocycle compounds. Among those porphyrins, 5,10,15,20-tetraphenylporphyrin and 5,10,15,20tetra(p-R substituted)porphyrin, have been widely studied and well investigated for several decades due to their rapid developments in physics and chemistry such as molecular electronics and sensors,1,2 photodynamic therapy,3,4 information storage elements,5 functional organic materials,6 medical agents,7 and catalysts.8 Among this kind of porphyrins, 5,10,15,20-tetraphenylporphyrin (TPP; chemical structure shown in Figure 1;9,10 CAS no. 917-23-7) and 5,10,15,20-tetra(p-chlorophenyl) porphyrin (p-ClTPP; chemical structure shown in Figure 2;11 CAS no. 22112-77-2) might be regarded as the most important because

Figure 2. Chemical structure of 5,10,15,20-tetra(p-chlorophenyl)porphyrin.

of their wide applicability in physics and chemistry, and they could react with metal salts to produce metalloporphyrins easily because of their simple structure and small steric hindrance. The metalloporphyrins are gradually taking the place of traditional catalysts in catalyzing the inert hydrocarbon bond because of their excellent biocatalytic effect; this effect is similar to cytochrome P-450 monooxygenase.8 Received: January 30, 2015 Accepted: September 3, 2015

Figure 1. Chemical structure of 5,10,15,20-tetraphenylporphyrin. © XXXX American Chemical Society

A

DOI: 10.1021/acs.jced.5b00092 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Usually, 5,10,15,20-tetraphenyl metal porphyrin is synthesized by the reaction of TPP with metal salts, and 5,10,15,20tetra(p-chlorophenyl) metal porphyrin is synthesized by the reaction of p-ClTPP with metal salts under atmospheric pressure. During the reaction process, usually the solvent is N,N-dimethylformamide (DMF),12 and the TPP and p-ClTPP added to the solvent should be dissolved completely. The solubility of TPP and p-ClTPP in DMF is a crucial factor in optimizing the reaction conditions. Besides the solvent of DMF, another solvent introduced into the system is water, which comes from the hydrated metal salts. Although the content of water in terms of mole fraction in the solvent is usually less than 0.2, preliminary experiments show the small amount of water influence the solubility of TPP and p-ClTPP in DMF greatly. In this sense, the solubility of TPP and pClTPP in binary DMF-riched DMF + water solvent mixtures at different temperatures is extremely important. In our present study, the solubilities of p-ClTPP in propionic acid + water solvent mixtures,13 p-ClTPP in ethanol + water solvent mixtures,14 and TPP in ethanol + water solvent mixtures have been published.15 In this work, the mole solubility of TPP in binary DMFriched DMF + water mixtures at (303.2 to 343.2) K and pClTPP in binary DMF-riched DMF + water mixtures at (303.2 to 353.2) K were investigated at atmospheric pressure. Considering a wider application area, the mole fraction of water in the binary DMF + water solvent mixtures ranges from 0.0000 to 0.5035. The modified Apelblat equation was applied to correlate the experimental data. Thermodynamic parameters such as dissolution enthalpy, isobaric heat capacity, and Gibbs energy were obtained from the solubility data by using the Clark−Glew equation together with the modified Apelblat equation.

Figure 3. XRD patterns of TPP.

Figure 4. XRD patterns of p-ClTPP.

Table 1. Suppliers and Mass Fraction Purity of the Materials

2. EXPERIMENTAL SECTION 2.1. Materials. TPP and p-ClTPP were synthesized by the method described in detail elsewhere.16,17 The purity of TPP checked by HPLC is higher than 0.980 in mass fraction, and the purity of p-ClTPP checked by HPLC is higher than 0.960 in mass fraction. N,N-Dimethylformamide (DMF) was purchased from Aladdin Chemistry Co., Shanghai, the purity of DMF verified by GC is higher than 0.999 in mass fraction. The water content in DMF was verified to be less than 0.1% by the Karl Fischer method. The water was purified to the resistivity of 18.2 MΩ·cm by a laboratory ultrapure water machine (Master-Q, purchased from Shanghai Hitech Instrumens Co. Ltd., Shanghai). The X-ray powder diffraction (XRD) patterns of TPP and pClTPP are shown in Figures 3 and 4. The TPP and p-ClTPP solids were crystallized from dichloromethane. Powder X-ray diffraction analysis were measured by using Cu Kα (λ = 0.15406 nm, 40 kV, 30 mA) radiation on a Shimadzu XRD6100. The samples were recorded between 2θ = 10° and 2θ = 40° with a step size of 0.02° and a scanning rate of 1°·min−1 at ambient conditions. Except for the TPP and p-ClTPP used for the standard samples, all the other chemicals were used without further purifications. For TPP and p-ClTPP used for the standard samples, the samples were purified by column chromatography at least twice, and the purity was confirmed by HPLC to be higher than 0.99 in mass fraction. The detailed information on the materials is given in Table 1.

materials

sources

mass fraction

analysis method

TPPa p-ClTPPb N,Ndimethylformamide

synthesized by ourself synthesized by ourself Aladdin Chemistry Co.

> 0.980 > 0.960 > 0.999

HPLCc HPLCc GCd

a 5,10,15,20-tetraphenylporphyrin. b5,10,15,20-tetra(p-chlorophenyl)porphyrin. cHigh-performance liquid chromatography. dGas chromatograph.

2.2. Apparatus and Procedures. The solubility measurment apparatus and procedures used are similar to those in our previous work.13−15,18 Briefly, an excess amount of TPP or pClTPP was taken into 100 mL glass bottles, the bottles were filled with known mole fraction of DMF + water solvent mixtures, and then were sealed by rubber stoppers to stop the solvent from evaporating. The bottles were placed in a constant temperature bath, the bath was heated to the desired temperature (with uncertainty of ± 0.1 K). The mixtures were stirred continuously with Teflon-coated magnetic stirrers to accelerate the dissolution. Preliminary experiments indicated that at least 3 h of magnetic stirrer was required to reach solid− liquid equilibrium. After the magnetic stirrer was stopped, the mixtures were allowed to settle in the following several hours. In order to verify the attainment of solid−liquid equilibrium, the clear supernatant solutions were sampled once an hour, and the concentration of TPP or p-ClTPP was determined. Results B



Article

Table 2. Mole Fraction Solubilities, x2, and Thermodynamic Functions of the Dissolution of TPP in DMF + Water Solvent Mixtures at Temperature from (303.2 to 343.2) K and under Atmospheric Pressurea T

105x2

105xc2b

K

ΔsolH0

RD

−1

%

ΔsolG0 −1

ΔsolC0p J·mol−1·K−1

kJ·mol

kJ·mol

3.80 7.69 11.6 15.5 19.4

23.2 23.8 24.3 24.6 24.8

390

7.58 11.1 14.7 18.3 21.8

24.7 25.2 25.6 25.9 26.0

357

10.3 13.6 16.9 20.1 23.4

26.1 26.5 26.9 27.1 27.3

328

12.2 15.3 18.3 21.3 24.3

27.4 27.8 28.2 28.4 28.6

303

13.5 16.3 19.1 22.0 24.8

28.6 29.1 29.4 29.7 29.9

281

14.4 17.0 19.6 22.2 24.8

29.8 30.3 30.7 31.0 31.2

261

14.9 17.3 19.7 22.2 24.6

31.0 31.4 31.9 32.2 32.5

244

15.1 17.3 19.6 21.9 24.2

32.0 32.6 33.0 33.4 33.7

228

15.0 17.2 19.3 21.5 23.6

33.0 33.6 34.1 34.5 34.9

214

14.9 16.9 18.9

34.0 34.6 35.2

201

c

303.2 313.2 323.2 333.2 343.2

9.76 10.7 12.0 13.6 16.6

9.90 10.6 11.9 13.9 16.7

303.2 313.2 323.2 333.2 343.2

5.76 6.27 7.30 8.66 10.7

5.62 6.32 7.37 8.86 10.9

303.2 313.2 323.2 333.2 343.2

3.34 3.85 4.55 5.53 6.82

3.25 3.78 4.53 5.57 7.00

303.2 313.2 323.2 333.2 343.2

1.96 2.25 2.70 3.37 4.42

1.92 2.29 2.79 3.48 4.43

303.2 313.2 323.2 333.2 343.2

1.19 1.40 1.73 2.26 2.77

1.17 1.41 1.74 2.19 2.80

303.2 313.2 323.2 333.2 343.2

0.710 0.858 1.08 1.44 1.81

0.729 0.889 1.10 1.39 1.79

303.2 313.2 323.2 333.2 343.2

0.469 0.555 0.699 0.899 1.19

0.464 0.568 0.708 0.894 1.14

303.2 313.2 323.2 333.2 343.2

0.302 0.362 0.447 0.589 0.767

0.303 0.372 0.464 0.584 0.745

303.2 313.2 323.2 333.2 343.2

0.207 0.242 0.297 0.389 0.506

0.202 0.248 0.308 0.387 0.490

303.2 313.2 323.2

0.135 0.165 0.201

0.138 0.169 0.208

X1 = 1.0000 1.43 −0.93 −0.83 2.21 0.60 X1 = 0.9236 −2.43 0.80 0.96 2.31 1.87 X1 = 0.8554 −2.69 −1.82 −0.44 0.72 2.64 X1 = 0.7942 −2.04 1.78 3.33 3.26 0.23 X1 = 0.7391 −1.68 0.71 0.58 −3.10 1.08 X1 = 0.6894 2.68 3.61 1.85 −3.47 −1.10 X1 = 0.6437 −1.07 2.34 1.29 −0.56 −4.20 X1 = 0.6023 0.33 2.76 3.80 −0.85 −2.87 X1 = 0.5641 −2.42 2.48 3.70 −0.51 −3.16 X1 = 0.5289 2.22 2.42 3.48

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Table 2. continued T

105x2

105xc2b

K 333.2 343.2

0.252 0.315

0.260 0.327

303.2 313.2 323.2 333.2 343.2

0.0995 0.120 0.149 0.178 0.220

0.0960 0.117 0.144 0.178 0.222

RD

ΔsolH0

ΔsolG0

ΔsolC0p

%

kJ·mol−1

kJ·mol−1

J·mol−1·K−1

20.9 22.9

35.6 36.0

14.5 16.4 18.3 20.2 22.1

34.9 35.6 36.2 36.7 37.1

X1 = 0.5289 3.17 3.81 X1 = 0.4965 −3.52 −2.50 −3.36 0.00 0.91

189

a

Standard uncertainty u is u(T) = 0.1 K, relative uncertainties ur are ur(p) = 0.02, ur(x) = 3 %, ur(ΔsolG0,ΔsolH0,ΔsolC0p) = 3 %. bxc2 is calculated by the obtained Apelblat parameters with eqs 6 and 7. cX1 is the mole fraction of DMF in DMF + water mixture solvent.

When determining the concentration of TPP or p-ClTPP in sampled DMF + water solution, the corresponding absorbance was determined, and according to eq 1 or eq 2, the concentration of TPP or p-ClTPP in sampled DMF + water mixtures was determined. To verify the reliability of the analysis method, 10 mixtures of TPP + DMF and p-ClTPP + DMF of known concentration were analyzed. To check the repeatability, the ten solutions were measured at least five times, and the repeatability was evaluated with a mean relative deviation of less than 2 %. The estimated associated relative uncertainty of the measured solubility values based on this error analysis and repeated observations was within ± 3 %.

show that 6 h was required after stirring stopped to allow the solid phase to precipitate down because repetitive measurements during the following several hours indicated the results were reproducible within ± 3 %. For assurance, after stirring was stopped at each temperature, the solutions were kept isothermal and undisturbed for at least 24 h to ensure that the solutions have fully settled. For each solubility measurement, a 25 mL volumetric flask (uncertainty of ± 0.01 mL) was charged with about 5 mL of DMF before sampling. Then, an appropriate volume of the clear upper (for TPP, about 0.03 to 0.6 mL; for p-ClTPP, about 0.05 to 1.2 mL) was sampled from the glass bottle using a 2 mL syringe each time. The total weight of the syringe before sampling was weighed and recorded as m1. After sampling, the total weight of the syringe and the sample was weighed again and recorded as m2, and then immediately discharged into the volumetric flask. The difference between m2 and m1 is the amount of sampled saturated solution. To collect the possibly crystallized solute in the syringe, the syringe was washed with DMF at least five times. The solution in the volumetric flask was diluted with DMF to 25 mL. The concentration of solute TPP or p-ClTPP in solution (denoted as mass fraction c) could be determined by the method introduced in Section 2.3, and then the solubility of TPP or p-ClTPP in binary DMF + water solvent mixtures could be determined. The solubility experiments were measured three times to check the repeatability. The uncertainty of mass measurement was ± 0.0001 g, and the uncertainty of temperature was ± 0.1 K. To verify the reliability of the experimental apparatus and method, we did one other experiment in which the solubility of benzoic acid in water was determined. The experimental value different from the literature value by less than 2 %.13−15,18 2.3. Analysis. The concentration of TPP or p-ClTPP in the solution was determined by an UV/visible spectrophotometer (UV-4802, Shanghai Unico Instrument Co., Ltd. Shanghai, China). For TPP, the maximum absorption wavelength of TPP in DMF is 417.5 nm. According to the Lambert−Beer law, the relationship of absorbance (y1) and the concentration of TPP in DMF (c1) expressed as

y1 = 0.7907c1

3. RESULTS AND DISCUSSION 3.1. Experimental Results. The mole fraction of DMF (X1) in the binary system DMF + water solvent mixture can be obtained from eq 3 X1 =

(3)

where mDMF and mwater are the masses of DMF and water in the solution, respectively, and MDMF and Mwater are the molecular weight of DMF and water, respectively. The determined mole fraction solubility of TPP (x2) or p-ClTPP (x3) in binary DMF + water solvent mixtures is expressed as x2 =

(m TPP /M TPP) (m TPP /M TPP) + (mDMF /MDMF) + (m water /M water) (4)

x3 =

(mp‐ClTPP/Mp‐ClTPP) (mp‐ClTPP/Mp‐ClTPP) + (mDMF/MDMF) + (mwater /M water) (5)

where mTPP and mp‑ClTPP are the mass of TPP and p-ClTPP in the saturated solution, MTPP and Mp‑ClTPP are the molecular weight of TPP and p-ClTPP. The measured solubilities of TPP and p-ClTPP in binary DMF + water solvent mixtures are presented in Tables 2 and 3. Both the solubility of TPP and pClTPP increases with increasing temperature at constant solvent composition. Another important conclusion that could be obtained from Table 2 and Table 3 is that water influences the solubility of TPP and p-ClTPP in DMF. For example at temperature T =

(1)

For p-ClTPP, the maximum absorption wavelength of pClTPP in DMF is 418.5 nm, the relationship of absorbance (y2) and the concentration of p-ClTPP in DMF (c2) was expressed as

y2 = 0.6347c 2

(mDMF /MDMF) (mDMF /MDMF) + (m water /M water)

(2) D



Article

Table 3. Mole Fraction Solubilities, x3, and Thermodynamic Functions of the Dissolution of p-ClTPP in DMF + Water Solvent Mixtures at Temperature from (303.2 to 353.2) K and under Atmospheric Pressurea T

105x3

105xc3b

K

ΔsolH0

RD

−1

%

ΔsolG0 −1

ΔsolC0p J·mol−1·K−1

kJ·mol

kJ·mol

16.5 20.9 25.2 29.6 33.9 38.3

26.5 26.7 26.9 26.8 26.7 26.4

435

19.9 23.8 27.8 31.7 35.6 39.6

28.1 28.3 28.4 28.4 28.2 27.9

393

22.2 25.7 29.3 32.9 36.4 40.0

29.7 29.8 29.9 29.9 29.7 29.5

357

23.5 26.8 30.1 33.3 36.6 39.8

31.1 31.3 31.4 31.4 31.2 31.0

326

24.3 27.3 30.3 33.2 36.2 39.2

32.4 32.6 32.7 32.8 32.7 32.6

298

24.6 27.3 30.0 32.8 35.5 38.2

33.6 33.9 34.0 34.1 34.1 34.0

274

24.5 27.0 29.5 32.0 34.5 37.0

34.8 35.1 35.3 35.4 35.5 35.5

252

24.1 26.4 28.7 31.1 33.4 35.7

35.8 36.2 36.5 36.7 36.8 36.9

232

c

303.2 313.2 323.2 333.2 343.2 353.2

2.64 3.51 4.56 6.16 8.67 12.2

2.74 3.48 4.57 6.20 8.66 12.4

303.2 313.2 323.2 333.2 343.2 353.2

1.42 1.95 2.59 3.54 4.96 7.41

1.43 1.89 2.56 3.57 5.08 7.38

303.2 313.2 323.2 333.2 343.2 353.2

0.776 1.06 1.47 2.04 2.86 4.44

0.779 1.05 1.46 2.07 2.98 4.35

303.2 313.2 323.2 333.2 343.2 353.2

0.438 0.626 0.865 1.20 1.78 2.66

0.443 0.610 0.854 1.22 1.76 2.57

303.2 313.2 323.2 333.2 343.2 353.2

0.262 0.372 0.526 0.734 1.05 1.56

0.262 0.364 0.512 0.729 1.05 1.53

303.2 313.2 323.2 333.2 343.2 353.2

0.161 0.226 0.321 0.444 0.638 0.931

0.161 0.224 0.315 0.447 0.640 0.923

303.2 313.2 323.2 333.2 343.2 353.2

0.102 0.136 0.192 0.267 0.390 0.573

0.102 0.142 0.198 0.279 0.396 0.564

303.2 313.2 323.2 333.2 343.2 353.2

0.0661 0.0918 0.128 0.176 0.242 0.351

0.0669 0.0921 0.128 0.178 0.250 0.353

X1 = 1.0000 3.79 −0.85 0.22 0.65 −0.12 1.64 X1 = 0.9236 0.70 −3.08 −1.16 0.85 2.42 −0.40 X1 = 0.8554 0.39 −0.94 −0.68 1.47 4.20 −2.03 X1 = 0.7942 1.14 −2.56 −1.27 1.67 −1.12 −3.38 X1 = 0.7391 0.00 −2.15 −2.66 −0.68 0.00 −1.92 X1 = 0.6894 0.00 −0.88 −1.87 0.68 0.31 −0.86 X1 = 0.6437 0.00 4.41 3.13 4.49 1.54 −1.57 X1 = 0.6023 1.21 0.33 0.00 1.14 3.31 0.57

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Table 3. continued T

105x3

105xc3b

K 303.2 313.2 323.2 333.2 343.2 353.2

0.0447 0.0613 0.0844 0.115 0.158 0.225

0.0449 0.0613 0.0842 0.116 0.161 0.224

303.2 313.2 323.2 333.2 343.2 353.2

0.0310 0.0421 0.0572 0.0778 0.106 0.142

0.0309 0.0418 0.0567 0.0773 0.106 0.145

303.2 313.2 323.2 333.2 343.2 353.2

0.0217 0.0294 0.0397 0.0534 0.0718 0.0962

0.0218 0.0291 0.0390 0.0525 0.0707 0.0954

RD

ΔsolH0

ΔsolG0

ΔsolC0p

%

kJ·mol−1

kJ·mol−1

J·mol−1·K−1

23.5 25.6 27.8 29.9 32.1 34.2

36.8 37.2 37.6 37.9 38.1 38.2

215

22.8 24.7 26.7 28.7 30.7 32.7

37.8 38.2 38.6 39.0 39.3 39.5

199

21.9 23.7 25.6 27.4 29.3 31.1

38.7 39.2 39.6 40.1 40.4 40.7

184

X1 = 0.5641 0.45 0.00 −0.24 0.87 1.90 −0.44 X1 = 0.5289 −0.32 −0.71 −0.87 −0.64 0.00 2.11 X1 = 0.4965 0.43 −0.89 −1.77 −1.74 −1.52 −0.83

a

Standard uncertainty u is u(T) = 0.1 K, relative uncertainties ur are ur(p) = 0.02, ur(x) = 3 %, ur(ΔsolG0,ΔsolH0,ΔsolC0p) = 3 %. bxc3 is calculated by the obtained Apelblat parameters with eqs 6 and 7. cX1 is the mole fraction of DMF in DMF + water mixture solvent.

303.2 K, the solubility of p-ClTPP will decrease about 50 % when 2 % mass fraction of water is introduced into the solvent DMF, will decrease about 94 % when 10 % mass fraction of water is introduced, and will decrease about 99 % when 20 % mass fraction of water is introduced. It indicates the water content in DMF−H2O solvent mixtures is a crucial factor in optimizing the reaction conditions. In order to improve the reaction efficiency, the reactant TPP or p-ClTPP should be dissolved in as high a concentration of DMF as possible, which means it is better to remove water simultaneously in the synthesis of metalloporphyrins. 3.2. Correlation of Experimental Data. The solubilities of TPP and p-ClTPP in DMF + water solvent mixtures were correlated by the modified Apelblat equation.19−21 The modified Apelblat equation was previously put forward by Apelblat to associate the mole fraction of solute with temperature for a saturated solution and can be expressed as ln x = A +

B + C ln T T

Table 4. Parameters of the Modified Apelblat Equation 7 for TPP and p-ClTPP in DMF + Water Solvent Mixtures Ai

AARD

i=0 i=1 i=2

−49.697 −176.82 −95.834

i=0 i=1 i=2

−20.290 −210.80 −123.93

TPP 2093.0 778.27 10880 p-ClTPP 1166.1 −835.21 13534

3.9000 33.202 9.7581

2.0

−0.85789 39.707 13.438

1.3

parameter estimation program was the Nelder−Mead Simplex approach,23 which had been described in detail in our previous work.13−15,18 Function f minsearch in the optimization toolbox of Matlab (Mathworks, MA) uses the Nelder−Mead Simplex approach and can be employed for the minimization of the objective function, which is the average absolute relative deviation (AARD) between the experimental and calculated solubility, which is expressed as

(6)

1 AARD = n

A = A 0 + A1X1 + A 2 X12

n

∑ abs(RDi) i=1

⎛x − x ⎞ i⎟ RDi = ⎜⎜ ci ⎟ ·100 x ⎝ ⎠ i

(8)

where n is the total number of experimental points, xci and xi are the ith calculated and experimental solubility, respectively. The correlated results and the corresponding RD are given in Table 2 and Table 3. The values of AARD defined in eq 8 are given in Table 4. For comparison, the experimental and calculated values of TPP and p-ClTPP are plotted in Figures 5 to 8 (for the convenience of clearly reading low solubility of TPP or p-ClTPP in those solvents where the mole fraction of DMF is lower than 0.6894, we divide the figure into two). As

2

C = C0 + C1X1 + C2X12

Ci

%

where x is the mole fraction of solute, T is the absolute temperature, and A, B, C are the empirical model parameters. In order to use eq 6 to correlate the solubility of TPP or p-ClTPP at different solvent compositions, the following empirical quadratic equations were adopted:13−15,22

B = B0 + B1X1 + B2 X1

Bi

(7)

where X1 is the mole fraction of DMF to DMF + water mixtures, and Ai, Bi, and Ci (i = 0, 1, 2) are model parameters. The model parameters were obtained using model eqs 6 and 7, and are given in Table 4. The major algorithm applied in the F



Article

Figure 8. Mole fraction solubilities (x3) of p-ClTPP in DMF + water solvent mixtures with temperature and at different DMF compositions (X1): ▶, X1 = 0.6894; ◆, X1 = 0.6437; ○, X1 = 0.6023; ☆, X1 = 0.5641; ◇, X1 = 0.5289; □, X1 = 0.4965. Solid line, correlated results by eqs 6 and 7.

Figure 5. Mole fraction solubilities (x2) of TPP in DMF + water solvent mixtures with temperature and at different DMF compositions (X1): ■, X1 = 1.0000; ●, X1 = 0.9236; ▲, X1 = 0.8554; ▼, X1 = 0.7942; ◀, X1 = 0.7391. Solid line, correlated results by eqs 6 and 7.

free energy ΔsolG0 (kJ·mol−1) and isobaric heat capacity ΔsolC0p (J·mol−1·K−1) can be obtained by using eqs 9 to 11,24−27 which are calculated by the Clark−Glew equation28,29 together with the modified Apelblat equation, assuming the isobaric heat capacity is temperature-independent for the temperature range studied24,29,30−33 Δsol G° = −RT ln x

Figure 6. Mole fraction solubilities (x2) of TPP in DMF + water solvent mixtures with temperature and at different DMF compositions (X1): ▶, X1 = 0.6894; ◆, X1 = 0.6437; ○, X1 = 0.6023; ☆, X1 = 0.5641; ◇, X1 = 0.5289; □, X1 = 0.4965. Solid line correlated results by eqs 6 and 7.

(9)

Δsol H ° = R(CT − B)

(10)

Δsol Cp0 = CR

(11)

where R is the gas constant, T is the absolute temperature of the solution, and A, B, and C are the Apelblat parameters given in Table 4. The thermodynamic parameters (ΔsolH0, ΔsolG0 and ΔsolC0p) of dissolution for TPP and p-ClTPP in DMF + water solvent mixtures are listed in Tables 2 and 3, and the thermodynamic parameters of solution are illustrated in Figures 9 to 12 as functions of solvent composition at experiment temperatures. The values of ΔsolH0 and ΔsolG0 are positive in all circumstances, which indicates that the dissolving process of TPP and p-ClTPP in DMF + water solvent mixtures is endothermic. It is additionally supported by the results of solubilities increasing with increasing experimental at constant

Figure 7. Mole fraction solubilities (x3) of p-ClTPP in DMF + water solvent mixtures with temperature and at different DMF compositions (X1): ■, X1 = 1.0000; ●, X1 = 0.9236; ▲, X1 = 0.8554; ▼, X1 = 0.7942; ◀, X1 = 0.7391. Solid line, correlated results by eqs 6 and 7.

shown in Table 3, the AARD value of TPP and p-ClTPP is 2.0 % and 1.3 %, respectively. The calculated results show good agreement with the experimental data, and the modified Apelblat equation can be used to correlate the solubility of TPP and p-ClTPP in DMF + water solvent mixtures. The results shown in Figures 5 to 8 verified the conclusion. 3.4. Thermodynamic Parameters of the Solution. The thermodynamic parameters for the solutions of TPP and pClTPP such as dissolution enthalpy ΔsolH0 (kJ·mol−1), Gibbs

Figure 9. Dissolution enthalpy ΔsolH0 of TPP in DMF + water solvent mixtures with DMF compositions (X1) and at different temperatures: ■, T = 303.2 K; ●, T = 313.2 K; ▲, T = 323.2 K; ▼, T = 333.2 K; ◀, T = 343.2 K. G



Article

the dissolving process of p-ClTPP. The experimental data of TPP and p-ClTPP verified the conclusion.

4. CONCLUSIONS In this work, the solubility of TPP and p-ClTPP in DMF + water solvent mixtures at different temperatures were determined under atmospheric pressure. The effects of experiment temperature and mole fraction of DMF in the solvent mixtures from (0.4965 to 1.0000) on the solubility were studied, with these conclusions: (1) The solubilities of TPP and p-ClTPP increase with increasing temperature for a certain solvent composition, and the solubilities are the largest in pure DMF then decrease apparently with the addition of water. (2) The solubility of TPP is larger than that of p-ClTPP, owing to the TPP and p-ClTPP molecules containing groups of different nature. (3) The solubilities of TPP and p-ClTPP in DMF + water solvent mixtures are usually small at ambient temperatures while increasing rapidly as the temperature grows. Therefore, DMF is a suitable solvent for TPP and p-ClTPP reacting with metal salts to produce metalloporphyrins. (4) The modified Apelblat equation fitted satisfactorily to the experimental data. The experimental solubility and correlation equations in this work can be used for the large-scale synthesis of metalloporphyrins in industry. (5) The thermodynamic parameters (ΔsolH0, ΔsolG0, ΔsolC0p) of solution were obtained by the Clark−Glew equation. The values of ΔsolH0 and ΔsolG0 are positive, which shows that the dissolving process is endothermic and not spontaneous. The values of ΔsolG0 increase with the decreasing mole fraction of DMF, whereas the values of Δ sol H 0 increase to a maximum before consequently decreasing with increasing mole fraction of DMF in solvent mixtures.

Figure 10. Gibbs free energy ΔsolG0 of TPP in DMF + water solvent mixtures with DMF compositions (X1) and at different temperatures: ■, T = 303.2 K; ●, T = 313.2 K; ▲, T = 323.2 K; ▼, T = 333.2 K; ◀, T = 343.2 K.

Figure 11. Dissolution enthalpy ΔsolH0 of p-ClTPP in DMF + water solvent mixtures with DMF compositions (X1) and at different temperatures: ■, T = 303.2 K; ●, T = 313.2 K; ▲, T = 323.2 K; ▼, T = 333.2 K; ◀, T = 343.2 K; ▶, T = 353.2 K.

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AUTHOR INFORMATION

Corresponding Author

*Tel.: 86-731-88664151. E-mail: [email protected]. Funding

The project was granted financial support from Key S&T Special Project of Zhejiang Province (2012C13007-2), the Fundamental Research Funds for the Central Universities and the National Nature Science Fund (21302049). Notes

The authors declare no competing financial interest.

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REFERENCES

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Solubilities of 5, 10, 15, 20-Tetraphenylporphyrin and 5, 10, 15, 20

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