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Revista Colombiana de Ciencias Químico - Farmacéuticas

Print version ISSN 0034-7418On-line version ISSN 1909-6356

Rev. colomb. cienc. quim. farm. vol.49 no.1 Bogotá Jan./Apr. 2020  Epub Nov 10, 2020

https://doi.org/10.15446/rcciquifa.v49n1.87038 

Scientific Research Articles

Thermodynamic analysis and applications of the Abraham solvation parameter model in the study of the solubility of some sulfonamides

Análisis termodinámico y aplicaciones del modelo de parámetros de solvatación de Abraham en el estudio de la solubilidad de algunas sulfonamidas

Joaquín H. Blanco-Márquez1  2 

Yina Andrea Quigua-Medina3 

José Darwin García-Murillo3 

Jennifer Katiusca Castro-Camacho4 

Claudia Patricia Ortiz5 

Nestor E. Cerquera6 

Daniel Ricardo Delgado7  * 

1Universidad Surcolombiana, Environmental Management and Engineering, Neiva, Huila, Colombia.

2Research Group of Science, Engineering and Innovation, Crimarpez S.A.S, Calle 12 Sur # 6-45, Neiva, Colombia.

3Universidad Antonio Nariño, Programa de Odontología, Sede Buganviles Calle 19 # 42-98, Neiva, Huila, Colombia.

4Universidad Surcolombiana, Faculty of Engineering, Agroindustrial engineering Program, Hydro Engineering and Agricultural Development Research Group (GHIDA), Avenida Pastrana Borrero Carrera 1, Neiva, Huila, Colombia

5Corporación Universitaria Minuto de Dios, Programa de Administración en Seguridad y Salud en el Trabajo, Grupo de Investigación en Seguridad y Salud en el Trabajo, Neiva, Huila, Colombia

6Universidad Surcolombiana, Faculty of Engineering, Agricultural Engineering Program, Hydro Engineering and Agricultural Development Research Group (GHIDA), Avenida Pastrana Borrero Carrera 1, Neiva, Huila, Colombia.

7Universidad Cooperativa de Colombia, Department of Engineering, Industrial Engineering Program, GRIAUCC Research Group, Calle 11 # 1-51, Neiva, Huila, Colombia


SUMMARY

Solubility of sulfadiazine (SD), sulfamerazine (SMR) and sulfamethazine (SMT) in cosolvent mixtures octanol+methanol was investigated to 278.15 K, 298.15 and 313.15 K. In all cases, the lowest solubility of each drug was obtained in pure octanol at 278.15 K. The maximum solubility depends on the polarity of the drug, thus SMR and SMT reached their maximum solubility in cosolvent mixtures methanol-rich.

The solution thermodynamic functions were calculated from the experimental solubility data, using the van't Hoff and Gibbs equations, following the approach proposed by Krug et al. The enthalpy of solution is positive in all cases, which is an indication of the endothermic process with a marked entropic favor. Theoretical solubility and mean lethal concentration were calculated using the Abraham model.

Key words: Sulfonamides; Solubility; van't Hoff; Abraham model; lethal median molar concentration

RESUMEN

Se investigó la solubilidad de sulfadiazina (SD), sulfamerazina (SMR) y sulfametazina (SMT) en mezclas codisolventes de octanol + metanol a 278,15 K, 298,15 y 313,15 K. En todos los casos, la solubilidad más baja de cada fármaco se obtuvo en octanol puro a 278,15 K. La solubilidad máxima depende de la polaridad del fármaco, por lo que SMR y SMT alcanzaron su máxima solubilidad en mezclas cosolventes ricas en metanol. Las funciones termodinámicas de solución se calcularon a partir de los datos experimentales de solubilidad, utilizando las ecuaciones de van't Hoff y Gibbs, siguiendo el enfoque propuesto por Krug et al. La entalpia de la solución es positiva en todos los casos, lo cual es una indicación del proceso endotérmico con un marcado favorecimiento entrópico. La solubilidad teórica y la concentración letal media se calcularon utilizando el modelo de Abraham.

Palavras-chave: Sulfonamidas; solubilidad; van't Hoff; modelo de Abraham; concentración letal media

INTRODUCTION

Sulfonamides, first synthetic antimicrobial drugs [1], have been extensively used for human health treatment, in animal husbandry and management [2, 3]. Sulfonamides are effective against Gram-positive bacteria, and their spectrum of actions includes many Gram-negative bacteria, as well as some protozoa and fungi [4]. Sulfonamides also experience other pharmacological activities, namely antitumor [5], diuretic [6], anti-neuropathic pain [7] and anti-carbonic anhydrase [8] actions.

Owing to its extensive use, sulfonamides have become a relatively serious environmental problem, and it is one of the emerging pollutants with a greater presence in wastewater, aquifers, and bodies of water such as lakes. This could eventually put aquatic ecosystems at high risk [9]. This makes these antimicrobial agents one of the most dangerous emerging contaminants for beneficial aquatic microorganisms due to its toxicity, with the corresponding risk for human health as well [10].

Although the solubility studies are of great importance for the activities of the design and development of medicines, due to the environmental problems that have been generated by their release into the environment. A clear example is the significant fraction of the pharmaceutically active compounds sold each year find their way into the environment as the result of human/animal urine and feces excretion (excreted unchanged drugs or as drug metabolites). Or by direct disposal of unused household drugs by flushing into sewage systems, accidental spills and releases from manufacturing production sites, and underground leakage from municipal sewage systems and infrastructures. Currently, several thousand tons of medicinal compounds find their way into aquatic environments on an annual basis. The occurrence of pharmaceutical residues and metabolites in the environment is of significant public concern. Therefore, reports from the NORMAN network, promote that solubility studies have regained importance in environmental studies and/or development of more efficient methodologies for remediation processes. In this context, another area where the solubility has incurred is cleaner production [11].

Therefore, the primary objectives of this investigation were to determine the solubility of SD, SMR and SMT (figure 1) in {octanol (1) + methanol (2)} {OcOH (1) + MeOH (2)] cosolvent mixtures at nine different temperatures from 278.5 K to 313.15 K and to evaluate its thermodynamic behavior using the van't Hoff and Gibbs equations.

Figure 1 Molecular structure of sulfadiazine (R1 = H, R2 = H), sulfamethazine (R1 = CH3, R2 = H) and sulfamethazine (R1 = CH3, R2 = CH3). 

EXPERIMENTAL

Reagents

The following reagents were used in this investigation: Sulfadiazine, sulfamerazine and sulfamethazine (Sigma-Aldrich, USA, approximate purity 0.990 in mass fraction); methanol, ethanol, and octanol (Merck AR, Germany, approximate purity 0.998 in mass fraction).

Preparation of the solvent mixture

The {OcOH (1) + MeOH (2)} mixtures were prepared in quantities of 10 g, using an analytical balance with sensitivity ±0.0001 g (RADWAG AS 220.R2, Poland). The mass fractions of OcOH varied by 0.10 from 0.10 to 0.90. Each mixture was prepared in triplicate.

Determination of solubility

The method used for determining the solubility of the three sulfonamides (SD, SMR and SMT) was the bottle-shaking method proposed by Higuchi and Connors [12] and previously reported in several investigations by our research groups [13, 14]. This method consists of placing approximately 10 g of pure solvent or solvent mixture in an amber glass bottle and then adding excess sulfonamide until a solid phase is reached at the bottom of the bottle. Subsequently, the flasks (solvent + solute) are placed in a thermostatized recirculation bath (Medingen K-22/T100, Germany) for 72 h, stirring periodically until reaching the saturation equilibrium (constant solubility). A sample of the saturated solution is taken after 72 h using a syringe under isothermal conditions and filtered using a membrane with 0.45 fzm pore size to ensure the absence of solid particles in the sample, which will be tested. The concentration of the drug in each sample was determined using UV/Vis spectrophotometry (EMC-11-UV UV/ VIS spectrophotometer, Germany), making the corresponding dilutions with ethanol to avoid the precipitation of the drug during the dilution. Each solubility experiment was performed three times.

RESULTS AND DISCUSSION

Solubility of SD, SMR and SMT in {octanol (1) + methanol (2)} cosolvent mixtures

Table 1 shows the solubility of SD, SMR and SMT in {OcOH (1) + MeOH (2)} cosolvent mixtures at three temperatures (278.15, 293.15 and 313.15) K and nine cosolvent mixtures (0.10 < w 1 < 0.90 and varying by 0.10 in mass fraction) and the two pure solvents, MeOH and OcOH.

Table 1 Solubility of SD, SMR and SM (3) expressed in mole fraction (x 105)b in {octanol (1) + methanol (2)} cosolvent mixtures at different temperatures (K). 

W 1 a SD SMR SMT
278.15 293.15 313.15 278.15 293.15 313.15 278.15 293.15 313.15
0.00 32.31 13.76 7.91 123.60 68.78 46.91 375.25 147.57 81.24
0.10 26.19 12.71 6.05 135.58 78.72 47.98 384.98 166.54 82.86
0.20 21.14 9.03 4.86 134.16 81.13 46.76 391.29 186.73 81.13
0.30 15.19 7.07 3.22 123.82 63.17 40.68 381.65 172.08 77.64
0.40 12.34 5.49 2.48 97.17 48.16 30.92 375.13 145.84 73.33
0.50 9.31 3.55 1.75 61.55 31.07 17.47 299.34 121.23 56.04
0.60 7.73 3.42 1.37 35.27 17.43 8.17 247.51 105.66 45.35
0.70 5.55 1.74 0.85 29.32 11.64 6.71 176.86 62.90 31.13
0.80 4.67 1.52 0.70 24.42 10.18 4.87 117.77 44.52 19.62
0.90 3.91 1.34 0.56 17.49 6.79 3.41 63.61 24.77 10.70
1.0 3.31 1.07 0.45 14.72 6.15 2.55 44.19 23.85 8.10
Ideal 150 254 494 287 482 924 524 888 1725

aw 1 is the mass fraction of OcOH in the cosolvent mixture free of solute.

b The standard uncertainty of temperature is u(T) = 0.05 K; The relative standard uncertainty of solubility is u τ (x 3 ) = 0.05.

Figures 2, 3 and 4 show the behavior of the solubility of SD, SMR and SMT in the cosolvent mixture octanol + methanol three temperatures, in all cases, the solubility increases because of temperature increments, implying that the drugs solution process in the cosolvent mixtures {octanol (1) + methanol (2)} is favored by supplying power to the system. Further, demonstrating that the process is endothermic, where the minimum solubility values of the all sulfonamides are obtained in pure octanol at 278.15 K and the maximum solubility, which depends on the polarity of the sulfonamide. In the case of SD, it is obtained in pure methanol (δ SD = 28.89 MPa; δ 2 = 29.3 MPa [15]) at 318.15 K; for SMR in the cosolvent mixture w 1 = 0.1 (δ SMR = 28.10 MPa [16]; δ w =o.i = 28.14 MPa [17]) at 318.15 K; and for SMT in the cosolvent mixture w 1 = 0.2 (δ SMT = 27.42 MPa [18]; δ w = 0A = 27.64 MPa [17]) at 318.15 K. In all cases, the maximum solubility of the substances studied is reached in the solvent or cosolvent mixtures whose polarity is like that of each of the sulfonamides.

Figure 2 Solubility of SD (3) expressed in mole fraction (x 105) in {octanol (1) + methanol (2)} cosolvent mixtures at different temperatures (♦ = 278.15 K, • = 293.15 K and ▲ = 313.15 K). 

Figure 3 Solubility of SMR (3) expressed in mole fraction (x 105) in {octanol (1) + methanol (2)} cosolvent mixtures at different temperatures ( = 278.15 K, = 293.15 K and ▲= 313.15 K). 

Figure 4 Solubility of SMT (3) expressed in mole fraction (x 105) in {octanol (1) + methanol (2)} cosolvent mixtures at different temperatures (♦ = 278.15 K, • = 293.15 K and ▲ = 313.15 K). 

Activity coefficients

The activity coefficient (table 2) is calculated through equation 1, and can be interpreted based on possible molecular interactions solute-solute, solvent-solvent and solute solvent according to equation 2 [19].

Table 2 Activity coefficients (ү 3) of SD, SMR and SMT in cosolvent mixtures {octanol (1) + methanol (2)} at different temperatures (K). 

w a SD SMR SMT
278.15 293.15 313.15 278.15 293.15 313.15 278.15 293.15 313.15
0.00 4.64 18.45 62.43 2.32 7.01 19.70 1.40 6.02 21.29
0.10 5.73 19.98 81.69 2.12 6.12 19.26 1.36 5.33 20.88
0.20 7.09 28.12 101.65 2.14 5.94 19.76 1.34 4.76 21.32
0.30 9.88 35.95 153.31 2.32 7.63 22.71 1.37 5.16 22.28
0.40 12.16 46.27 199.05 2.95 10.01 29.88 1.40 6.09 23.59
0.50 16.11 71.56 282.18 4.66 15.52 52.89 1.75 7.33 30.87
0.60 19.40 74.33 361.77 8.14 27.65 113.11 2.12 8.40 38.15
0.70 27.03 145.96 582.00 9.79 41.41 137.66 2.96 14.12 55.57
0.80 32.14 167.05 704.43 11.75 47.37 189.84 4.45 19.95 88.18
0.90 38.37 189.75 878.83 16.41 71.03 270.64 8.24 35.85 161.68
1.00 45.37 238.10 1097.18 19.49 78.36 362.72 11.86 37.24 213.51

a w 1 is the mass fraction of OcOH in the cosolvent mixture free of solute.

Regarding SD, the activity coefficients increase from pure methanol to pure octanol; however, they diminish with and decrease in temperature. For SMR and SMT, the coefficient of activity, decrease from pure methanol to w 1 = 0.1 or w 1 = 0.2 and the activity coefficient values increase from w 1 = 0.1 or w 1 = 0.2 to pure octanol.

Although in all cases the solute-solute and solvent-solvent (e 22) molecular interactions are greater regarding the solute-solvent molecular interactions (e 12), according to the results analyzed from Eq. (2) , the unfavorable interactions (e n and e22) decrease to such an extent that the solution behaves almost as an ideal solution, where the solute-solute and solvent-solvent molecular interactions are equal to the solute-solvent molecular interactions.

Thermodynamic functions of solution

Thermodynamic functions (tables 3-5) are calculated from experimental solubility data (table 1), using the van't Hoff and Gibbs equations, following the approach proposed by Krug et al. [20-22]:

)

where Δsoln H°, Δsoln G° and Δsoln S° denote the enthalpy, Gibbs energy and entropy of the solution, respectively. T hm denotes the harmonic average of the study temperatures, and R denotes the universal constant of the gases. The intercept (a) corresponds to the linear equation of the plot of ln x 3 vs (T -1 - T hm -1).

Table 3 Apparent thermodynamic functions relative to solution process of SD in cosolvent mixtures {octanol (1) + methanol (2)} at 294.12 K. 

a w 1 is the mass fraction of OcOH in the cosolvent mixture free of solute.

Table 4 Apparent thermodynamic functions relative to solution process of SMR in cosolvent mixtures {octanol (1) + methanol (2)} at 294.12 K. 

a w 1 is the mass fraction of OcOH in the cosolvent mixture free of solute.

Table 5 Apparent thermodynamic functions relative to solution process of SMT in cosolvent mixtures {octanol (1) + methanol (2)} at 294.12 K. 

a W 1 is the mass fraction of OcOH in the cosolvent mixture free of solute.

The contribution of the energy factors (solution enthalpy) and organizational aspects (entropy) to the Gibbs energy of the solution can be obtained by using Eqs. 7 and 8 [23]:

The Gibbs energy of solution is positive in all the cases. As for the SD, the Gibbs energy increase from pure MeOH to pure OcOH, because the solubility of the SD decreases with the decrease of the polarity of the system, as a consequence of the addition of octanol.

SMR and SMT, the Gibbs energy decrease from pure MeOH to mixture with a mass fraction of 0.10-0.20 OcOH, beginning from this mixture, the Gibbs energy of the solution denotes an increase up to pure OcOH because the solubility decreases, possibly due to the effects of the polarity change of the medium, making it less favorable with respect to SMR and SMT.

On the other hand, the enthapy of soluctión is positive in all cases, therefore the process us always endothermic [24, 25], so, the entropy solution like enthalpy, is positive in all cases favoring the porcess of solution [26-28].

Although, main contributor to the (positive) standard molar Gibbs energy of solution(ζ H > 65%) is the enthalpy, the process presents an important entropic favorice.

Thermodynamic functions of the SD, SMR and SMT mixing

The solute behavior in the dissolution process can generally be divided into two stages, the solute fusion and its subsequent mixing with the solvent, so this hypothetical process can be represented according to the following scheme [29, 30]:

In this way, thermodynamic solution functions can be represented by the following equation:

where f represents the thermodynamic functions (G, H or S) and the subscripts f and mix represent fusion and mixing, respectively.

Thus, the mixing functions are determined as:

where Δf f o is replaced by the ideal thermodynamic functions, which are thus calculated as:

From Perlovich's analysis (figures 5, 6 and 7) [31], the mixing process for the three sulfonamides has a positive Gibbs energy (dotted lines), indicating that the melting process is what drives the solution process. For SD the mixing enthalpy is positive in all cases, so first, it does not favor the dissolution process and is greater in octanol-rich mixtures, possibly due to a higher energy requirement for the formation of the cavity necessary to house the solute. Regarding the mixing entropy, it is negative in MeOH-rich mixtures, which disadvantages the mixing process and is positive in OcOH-rich mixtures favoring the mixing process. The other hand, SMT, in mixtures rich in MeOH, enthalpy contributes to the mixing process and entropy does not contribute to the process, in mixtures rich in OcOH the opposite occurs. Regarding the SMT, both the mixing enthalpy and the mixing entropy are positive, indicating that the mixing entropy is the only thermodynamic function that contributes to the process.

Figure 5 Relationship between the enthalpy (Δmix H o ) and entropy (TΔmix S o ) terms of the mixing process of SD at 294.12 K. The isoenergetic curves of Δmix G o are represented by dotted lines. 

Figure 6 Relationship between the enthalpy (Δmix H o ) and entropy (TΔmix S o ) terms of the mixing process of SMR at 294.12 K. The isoenergetic curves of Δmix G o are represented by dotted lines. 

Figure 7 Relationship between the enthalpy (Δmix H o ) and entropy (TΔmix S o ) terms of the mixing process of SMT at 294.12 K. The isoenergetic curves of Δmix G o are represented by dotted lines. 

Generally speaking, for SD (figure 4), it is concluded that from pure MeOH to w 1 = 0.50 (sector VIII: Δmix H° < 0, TΔmixS° < 0, and | TΔtrS°| < |Δta |), the mixing process is driven by enthalpy; between w 1 = 0.60 and w 1 = pure OcOH (sector I: Δmix H o> TΔmixSo), the mixing process is driven again by enthalpy. For SMR (figure 5), from pure MeOH to w x = 0.4 (sector VI: Δmix H o < 0, TΔmix S o < 0, and |TAtt S o | > |ΔtaH o|) the mixing process is driven by entropy; from w 1 = 0.4 to w 1 = 0.5 (sector VII: Δmix H o > 0, TΔmix S o < 0, and | TΔtr S o | > |Δta H o |) the mixing process is driven by entropy; from w 1 = 0.6 to w 1 = 0.7 (sector III: Δmix H o < 0, TΔmixSo < 0, and | TΔtr S o | < |Δta H o |), the mixing process is driven by enthalpy and from w 1 = 0.8 to pure OcOH (sector VIII: Δmix H o < 0, TΔmixSo < 0, and |TΔtrSo| < |Δta H o |), the mixing process is driven by enthalpy. For SMT (figure 6), from pure MeOH to pure OcOH (sector VIII: Δmix H o < 0, TΔmix S o < 0, and | TΔtr S o | < |Δta H o |), the mixing process is driven by enthalpy [32].

Enthalpy-Entropy compensation

Changes in the free energy landscape upon tethering can be attributed to changes in entropy or enthalpy [33-35]. Very often, the changes in entropy and enthalpy are coupled. In many cases, a perturbation produced by a change in the solvent composition, leads to a change in the enthalpy of solution processes is correlated with a similar change in entropy in what is commonly referred to as "entropy-enthalpy compensation" [36]. Entropy-enthalpy compensation is reported for many chemical processes and is often accounted for as a general thermodynamic principle. In this case, analysis has been used to identify the mechanism of the co-solvent action [37-39].

Figure 8 Enthalpy-entropy compensation graph Δsoln H o vs Δsoln G o for the solution process of SD, SMR and SMT (3) in {octanol (1) + methanol (2)} cosolvent mixtures at 294.12 K. 

Figure 8 shows that sulfonamides (SD, SMR and SMT) in {OcOH (1) + MeOH(2)} cosolvent mixtures at 294.12 K presents a non-linear Δsoln H vs. Δsoln curve. SD, it presents a positive slope throughout the curve, indicating an enthalpic conduction; SMR, presents an enthalpy-driven (positive slope) [40] in mixtures OcOH-rich and intermediate and an entropy-driven (negative slope) [40] in mixtures MeOH-rich; finally the SMT, presents an entropy-driven (negative slope) in mixtures OcOH-rich and in mixtures MeOH-rich, and an enthalpy-driven in intermediate mixtures (positive slope).

Estimation of solubility and lethal median molar concentration of SD, SMR and SMT towards aquatic organisms from Abraham model solute descriptors

The solubility of each of the sulfonamides (SD, SMR and SMT) can be calculated from Abraham model (equation 14), the solute descriptors can be from were calculated using the page of the Helmholtz Environmental Research Center-UFZ, or from solubility data of each sulfonamide in pure solvents [41].

The numerical values of the solvent coefficients (c p , e p , s p , a p , b p , v p ) are tabulated in table 6 [39].

Table 6 Coefficients of equation (14) for various partitioning and solubility ratio processes at 298.15 K [42]. 

Solvent c p e p s p a p b p v p
Methanol 0.276 0.334 -0.714 0.243 -3.2 3.549
Octanol 0.088 0.562 -1.054 0.034 -3.46 3.814

Descriptors E, S, A, B and Vof the SD, SMR and SMT are presented in table 7 [42].

Table 7 Descriptors E, S, A, B and Vof the SD, SMR and SMT for Abraham model. 

Drug A E S A B V
SD 2.08 2.55 0.65 1.37 1.7225 10.504
SMR 2.1 2.65 0.65 1.42 1.8634 11.027
SMT 2.13 2.53 0.59 1.53 2.0043 11.504

The experimental solubility and the calculated solubility from equation 14 are presented in table 8.

Table 8 Calculated solubility of sulfonamides in {octanol (1) + methanol (2)} mixtures by using Abraham model at 298.15 K. 

Drug Solvent Experimental solubility / mol/L Calculated solubility/ mol/L %Deva
SD Methanol 4.70 x 10-3 [15] 2.93 x 10-3 38
SMR Methanol 2.13 x 10-2 [16] 1.94 x 10-2 9
SMT Methanol 4.90 x 10-2 [23] 5.42 x 10-2 11
SD Octanol 8.80 x 10-5 [36] 7.09 x 10-5 19
SMR Octanol 1.92 x 10-4 [36] 1.46 x 10-4 24
SMT Octanol 1.60 x 10-3 [36] 1.52 x 10-3 5

a Calculated as %Dev = 100x(C 3 Exp - C cal 3 )/C3 Exp [37].

The model results show a good approximation to the experimental data. Although deviation percentages of 38% are presented, which could be considered high, any theoretical approach to solubility data is of great importance.

The main advantage that the Abraham model is that can be used to predict other solute properties such as the toxicity of organic compounds towards different aquatic organisms. Yue et al. [35], has compiled Abraham model equation coefficients for predicting the median lethal molar concentration of organic compounds towards five species of fish (fathead minnow, guppy, bluegill, golden orfe and Medaka high-eyes) [43-44] and three species of water fleas (Daphnia magna, Ceriodaphnia dubia and Daphniapulex) [45].

In table 9 show tabulated the predicted median lethal molar concentration of SD, SMR and SMT calculated using equation 15 towards various species of fish and water fleas based the solute descriptors. the results reflect that species like Golden Orfe and Medaka high-eyes, they are extremely sensitive to sulfonamides, which shows the great danger to which some aquatic organisms are exposed, due to the dumping of these substances into the aquatic environment.

Table 9 Predicted median lethal molar concentration of SD, SMR and SMT, as LC50, towards various species of fish and water fleas. 

Aquatic organism Endpoint Drug
SD SMR SMT
Fathead minnow 96 hours 2.55 x 10-3 1.32 x 10-3 1.07 x 10-3
Guppy 96 hours 3.22 x 10-4 1.62 x 10-4 1.14 x 10-4
Bluegill 96 hours 1.19 x 10-3 6.42 x 10-4 6.52 x 10-4
Golden Orfe 96 hours 2.02 x 10-6 8.15 x 10-7 6.19 x 10-7
Medaka high-eyes 96 hours 2.45 x 10-7 9.95 x 10-8 6.88 x 10-8
Daphnia magna 48 hours 7.41 x 10-4 3.47 x 10-4 2.73 x 10-4
Ceriodaphnia dubia 48 hours 1.27 x 10-3 7.52 x 10-4 6.38 x 10-4
Daphnia pulex 48 hours 1.57 x 10-4 6.79 x 10-5 5.93 x 10-5

CONCLUSIONS

The solubility of the three sulfonamides is thermodependent, increasing with increasing temperature, indicating an endothermic process, and the peak of maximum solubility is reached where the cosolvent mixture has a polarity like that of the sulfonamide. Regarding the thermodynamics of solution, both enthalpy and entropy are positive, indicating an entropic conduction of the solution process. The Abraham model, allows the calculation of the solubility of sulfonamides in an acceptable way, the calculation of the LC50, indicates that some aquatic species are extremely sensitive to these drugs and evidences the environmental problem that is being generated by the dumping of drugs to water bodies.

ACKNOWLEDGEMENTS

We thank the National Directorate of Research and National Committee for Research Development of the Universidad Cooperativa de Colombia, for the financial support of the Project "Estudio termodinâmico de la solubilidad de algunas sulfonamidas en mezclas disolventes ciclohexano + etanol a diferentes temperaturas" with code INV1863. Further, we thank the Universidad Cooperativa de Colombia, sede Neiva for facilitating the laboratories and equipment used.

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DISCLOSURE STATEMENT No potential conflict of interest was reported by the authors.

HOW TO CITE THIS ARTICLE J.H. Blanco-Mârques, Y.A. Quigua-Medina, J.D. García-Murillo, J.K. Castro-Cama-cho, C.P. Ortiz, N.E. Cerquera, D.R. Delgado, Thermodynamic analysis, and applications of the Abraham solvation parameter model in the study of the solubility of some sulfonamides, Rev. Colomb. Cienc. Quím. Farm., 49(1), 234-255 (2020).

Received: April 10, 2020; Accepted: April 14, 2020

*Address for correspondence: E-mail: danielr.delgado@ucc.edu.co

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