Volumetric Properties of Local Anesthetical Drug Lidocaine

Article pubs.acs.org/jced

Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Volumetric Properties of Local Anesthetical Drug Lidocaine Hydrochloride in Aqueous and in Aqueous NaCl Solutions at Different Temperatures Vasim R. Shaikh, Vidya R. Salunke, Karishma P. Behare, Sayali E. Patil, Amulrao U. Borse, and Kesharsingh J. Patil* School of Chemical Sciences, North Maharashtra University, Jalgaon, Maharashtra 425001, India ABSTRACT: We report in this communication, the data on density measurements of binary aqueous solutions of lidocaine hydrochloride LC·HCl (0.00978 to 0.25412 mol·kg−1) as well as for ternary aqueous solutions containing a fixed concentration (0.09787 mol·kg−1 and 1.00764 mol·kg−1) of sodium chloride (NaCl) and varying the concentration (0.02046 to 0.24929 mol·kg−1) of LC·HCl at 288.15, 293.15, 298.15, 303.15, and 308.15 K. The density data are used to determine apparent molar volume (Vϕ) of the drug LC·HCl molecule at finite concentrations as well as apparent molar volume at infinitely dilute solutions (V0ϕ) in water and in aqueous NaCl solutions. The limiting apparent molar expansivity (E0ϕ) parameter of LC·HCl in binary and ternary aqueous NaCl solutions at 293.15, 298.15, and 303.15 K have also been computed. The transfer volumes ΔtrV0ϕ, that is, volume change occurring when LC·HCl is transferred from water to aqueous NaCl solutions, are calculated. All these results are analyzed and discussed on the basis of solute−solvent, lidocaine cation−cation, and embrionic micelle forming interactions in aqueous salt solutions. Pauling13 had proposed a formation of a clathrate−hydrate type of equilibria for water in the brain in the presence of an anesthetical agent such as chloroform to explain the probable anesthesial effects and understanding of the mechanism involved. Lidocaine (an aromatic amide) acts as a local anesthetical agent and is commonly used in anesthesia for intradermal infiltration and peripheral nerve blocks.14−16 Lidocaine hydrochloride inhibits voltage−gated sodium channels and affects potassium channels, GABAA receptors, and NMDA receptors.15 Ansari et al.17 have successfully developed the silver nanoparticles embedded with lidocaine hydrochloride to act as a colorimetric nanosensor which would help with onspot determination of lidocaine hydrochloride in forensic toxicological drug screening. However, our literature survey reveals that there are only few reports available for volumetric properties of lidocaine hydrochloride in aqueous solutions18−21 as well as on the activity and activity coefficient studies of lidocaine hydrochloride in aqueous binary solutions at 298.15 K.22 The data on osmotic and activity coefficients and volumetric properties of some local anesthetical drugs including lidocaine hydrochloride with α-cyclodextrin in aqueous solutions at 298.15 K have also been reported.23,24 Considering this we thought of obtaining volumetric data for lidocaine hydrochloride (LC·HCl) in aqueous sodium chloride

1. INTRODUCTION The biological activity of drug molecules plays a very important role in finding out a remedial measure to cure a disease. To understand the mechanism of drug action and the activity of drugs at the molecular level for biological systems, the physicochemical properties of drug solutions lead to the understanding of forces involved in terms of solute−solvent and solute−solute (ion−ion) interactions. It is very difficult to understand the drug−solvent interactions directly in biological systems because such interactions vary with temperature as well as perhaps being altered by adding salt, osmolytes, surfactants, alcohols, proteins, and carbohydrates, etc. which act as cosolutes.1−3 However, it is possible to study and examine the effect of temperature and co-solutes on drug−solvent interactions if appropriate theoretical background is available.4−11 Body fluid is generally a saline solution in which salting-in and salting-out effects, depending upon the interactions of solute ion or protein or amino acid such as solute−solute, solute ions−amino acids, ion−solvent, cation−anion, and solvent-enforced cation−cation attraction (hydrophobic interaction), are being observed. The nature of such interactions is very subtle for normal functioning and general health of an individual. The study of thermophysical properties of drugs in aqueous salt solution is useful to understand ion−ion, hydrophilic−ionic, ion−hydrophobic, electrostatic interactions, and structure making/breaking ability in such systems.8,10,12 © XXXX American Chemical Society

Received: December 5, 2017 Accepted: March 1, 2018

A

DOI: 10.1021/acs.jced.7b01059 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Chemical Name, Provenance, CAS Number, Mass Fraction Purity, Purification Method, and Molar Mass of Studied Drug

a

chemical name

provenance

mass fraction puritya

CASRN

purification method

molar mass (kg·mol−1)

lidocaine hydrochloride (monohydrate)

Sigma-Aldrich

≥0.97

6108-05-0

none

0.28881

Mass fraction purity was obtained experimentally by doing chloride estimation potentiometrically as well as water analysis by TGA−DSC analysis.

3. RESULTS 3.1. Density and Apparent Molar Volume. The experimental density (ρ) data for binary aqueous solutions of LC·HCl in the concentration range of 0.00978 to 0.25412 mol· kg−1 and for ternary aqueous solutions containing a fixed concentration (0.09787 mol·kg−1 and 1.00764 mol·kg−1) of NaCl and varying the concentration (0.02046 to 0.24929 mol· kg−1) of LC·HCl at 288.15, 293.15, 298.15, 303.15, and 308.15 K are collected in Table 2, Table 3, and Table 4, respectively. The comparison of densities of aqueous LC·HCl solutions with the literature20 at all studied temperatures is shown in Figure 1. The densities of aqueous solutions of LC·HCl at 298.15 K are also in good agreement with the literature data.18,19,21 The variation of ρ data as a function of molality of drug LC·HCl in both studied ternary systems (LC·HCl + water + 0.09787 mol· kg−1 NaCl and LC·HCl + water + 1.00764 mol·kg−1 NaCl) at all studied temperatures is shown in Figure 2. The experimental density data obtained were further used to calculate the apparent molar volumes (Vϕ) of LC·HCl in binary and ternary systems at finite concentration by using the equation:

(NaCl) solutions at different temperatures so that some mechanism on molecular interactions can be advanced. In this work, we report the densities of binary aqueous solutions as well as ternary aqueous solutions containing a fixed concentration (0.09787 mol·kg−1 and 1.00764 mol·kg−1) of NaCl and varying concentration of LC·HCl at 288.15, 293.15, 298.15, 303.15, and 308.15 K. The calculations of apparent molar volume (Vϕ), partial molar volume of solute (V̅ 2), transfer volume (Δ trV ϕ0 ), and limiting apparent molar expansivity (E0ϕ) parameters were made. The results of all these are presented and discussed in following pages.

2. EXPERIMENTAL WORK The details of chemical name, provenance, CAS number, mass fraction purity, purification method, and molar mass of studied drug lidocaine hydrochloride LC·HCl monohydrate are given in Table 1. The studied drug was used without further purification. The amount of water of hydration in the supplied sample was estimated using the thermo-gravimetric analysis, and has been reported earlier.24 The water of hydration for lidocaine hydrochloride LC·HCl (monohydrate) was considered in calculations of molalities of LC·HCl in binary as well as in ternary solution. The purity of LC·HCl was determined by doing a chloride estimation by potentiometric titration with 0.1 mol·kg−1 AgNO3. For this, we set up an electrochemical cell was as Ag |LC·H+Cl| |KNO3 salt bridge| |Hg2Cl2(s)|Hg, and appropriate titration was carried out. The results from potentiometric titration indicated that the LC·HCl contains one water molecule, which is in agreement with that estimated from thermal data, while the mass fraction purity is of the order of ≥0.97. Sodium chloride (NaCl) of AR grade (Merck) was dried under vacuum at 393.15 K for 24 h before use. All the solutions were prepared freshly on a molality basis using quartz doubly distilled water and were converted to the molarity scale whenever required with the help of density data. The molality of LC·HCl calculations were made by taking into account the hydrate water appropriately. A Shimadzu AUW220D balance having a readability of 0.01 mg was used for weighing. The density measurements were made using an Anton Paar digital densitometer (DMA-5000) at 288.15, 293.15, 298.15, 303.15, and 308.15 ± 0.01 K. The densitometer was calibrated using air and water at the studied temperatures. After the humidity and lab pressure corrections were applied, the uncertainty in the density measurements was found to be ±3· 10−3 kg·m−3. The reliability of the density data was ascertained by making measurements of aqueous binary solutions of NaCl at 298.15 K, which is in good agreement with the literature data.25 Similarly, the calculated apparent molar volumes (Vϕ) of NaCl in aqueous solutions at 298.15 K, plotted in the form of (Vϕ − 1.868c1/2) against the concentration of salt (c/mol· dm−3), when extrapolated to infinite dilution, yield limiting apparent molar volumes (V0ϕ) as (16.51 ±0.16) × 10−6 m3· mol−1 which is in good agreement with the literature data value (=16.62 × 10−6 m3·mol−1).25

Vϕ =

(ρ0 − ρ) mρρ0

+

M ρ

(1)

where ρ0 and ρ are the densities of solvent (for binary system: water and for ternary system: 0.09787 mol·kg−1 and 1.00764 mol·kg−1 aqueous NaCl solution) and solution, respectively, (kg·m−3), m is molality of drug molecule in binary and in ternary systems (mol·kg−1) and M is the molar mass of the solute (kg·mol−1). The Vϕ data of LC·HCl in aqueous solutions and LC·HCl in aqueous 0.09787 mol·kg−1 and 1.00764 mol·kg−1 NaCl solutions along with their uncertainties at the studied temperatures are collected in Table 2, Table 3, and Table 4, respectively. The Vϕ data can also be expressed as26,27 Vϕ = V ϕ0 + AV c1/2 + BV c

(2)

V0ϕ

where is apparent molar volume of the drug at infinite dilution, AV is Debye−Hückel limiting law coefficient (1.697, 1.782, 1.868, 1.955 and 2.046·10−6 (mol·mm−3)−3/2 for 1:1 electrolyte solutions at 288.15, 293.15, 298.15, 303.15, and 308.15 K),27 c is the concentration of the drug in aqueous solutions and aqueous NaCl solutions (mol·dm−3) and BV is a deviation parameter (m6·mol−2) indicating the deviations from Debye−Hückel limiting law. The variation of (Vϕ−AVc1/2) parameter as a function of concentration (c/mol·dm−3) of LC·HCl in aqueous solutions as well as in aqueous 0.09787 mol·kg−1 and 1.00764 mol·kg−1 NaCl solutions at 288.15, 293.15, 298.15, 303.15, and 308.15 K are shown in Figures 3−5. The smooth extrapolations of (Vϕ− AVc1/2) parameter to infinitely dilute solutions enabled us to obtain limiting apparent molar volume (V0ϕ) of the drug and slope of the graph yielding the value of the parameter BV. The B



Article

Table 2. Molality m, Density ρ, Apparent Molar Volume Vϕ, (Vϕ − ΑV·c1/2), Partial Molar Volume of Solute and Solvent V̅ 2 and V̅ 1 Data for Aqueous Solutions of LC·HCl at 288.15, 293.15, 298.15, 303.15, and 308.15 K and at Ambient Pressure of 101.325 kPaa ρb

mb mol·kg

−1

kg·m

106·Vϕ −3

106·(Vϕ − ΑV·c1/2)

−1

m ·mol 3

−1

106·V̅ 2 −1

106·V̅ 1 m3·mol−1

m ·mol

m ·mol

233.70 234.55 233.43 233.72 234.71 234.04 236.12 235.33 235.80 235.49 234.79

233.65 235.04 234.17 234.66 236.39 236.25 238.34 237.33 237.09 234.71 231.08

18.03 18.03 18.03 18.03 18.03 18.03 18.03 18.03 18.03 18.03 18.03 18.03

235.31 236.92 237.98 236.05 235.25 235.79 236.03 235.62 235.61 235.57 236.14

236.36 237.67 238.54 236.44 234.93 234.77 234.80 234.38 234.71 236.02 238.76

18.05 18.05 18.05 18.05 18.05 18.05 18.05 18.05 18.05 18.05 18.05 18.05

239.66 239.01 235.97 236.43 235.70 237.24 237.70 236.98 237.85 236.82 237.16

239.21 238.37 236.73 237.25 236.76 238.58 239.19 238.59 239.64 238.86 239.41

18.07 18.07 18.07 18.07 18.07 18.07 18.07 18.07 18.07 18.07 18.07 18.07

242.94 237.71 236.79 239.65 238.34 239.03 238.37 238.17 238.30 237.94 237.52

243.04 237.86 236.95 239.70 238.40 239.12 238.47 238.28 238.43 238.10 237.70

18.09 18.09 18.09 18.09 18.09 18.09 18.09 18.09 18.09 18.09 18.09 18.09

240.06 242.23 240.34

240.19 242.32 240.40

18.12 18.12 18.12 18.12

3

3

a

T = 288.15 K 0.00000 0.00978 0.02058 0.02578 0.03030 0.05111 0.08179 0.10291 0.12242 0.15323 0.20386 0.25412

999.106 999.468 999.847 1000.061 1000.218 1000.918 1002.031 1002.554 1003.278 1004.211 1005.863 1007.582

233.87 234.79 233.70 234.01 235.09 234.52 236.65 235.91 236.45 236.23 235.62

± ± ± ± ± ± ± ± ± ± ±

10.12 4.81 3.84 3.27 1.94 1.21 0.96 0.81 0.65 0.49 0.39 T = 293.15 Ka

0.00000 0.00978 0.02058 0.02578 0.03030 0.05111 0.08179 0.10291 0.12242 0.15323 0.20386 0.25412

998.205 998.553 998.901 999.048 999.252 999.998 1001.002 1001.677 1002.360 1003.360 1004.974 1006.390

235.4910.12 237.17 ± 4.81 238.26 ± 3.84 236.35 ± 3.27 235.65 ± 1.94 236.30 ± 1.21 236.60 ± 0.96 236.24 ± 0.81 236.30 ± 0.65 236.35 ± 0.49 237.01 ± 0.39 T = 298.15 Ka

0.00000 0.00978 0.02058 0.02578 0.03030 0.05111 0.08179 0.10291 0.12242 0.15323 0.20386 0.25412

997.044 997.352 997.702 997.944 998.086 998.825 999.742 1000.370 1001.062 1001.898 1003.609 1005.030

239.84 239.28 236.27 236.76 236.12 237.77 238.29 237.62 238.57 237.64 238.08

± ± ± ± ± ± ± ± ± ± ±

10.12 4.81 3.84 3.27 1.94 1.21 0.96 0.81 0.65 0.49 0.39 T = 303.15 Ka

0.00000 0.00978 0.02058 0.02578 0.03030 0.05111 0.08179 0.10291 0.12242 0.15323 0.20386 0.25412

995.647 995.926 996.337 996.533 996.601 997.309 998.223 998.932 999.555 1000.473 1002.041 1003.607

0.00000 0.00978 0.02058 0.02578

994.033 994.343 994.638 994.837

243.13 237.99 237.10 239.99 238.78 239.59 238.99 238.84 239.05 238.81 238.47

± ± ± ± ± ± ± ± ± ± ±

10.12 4.81 3.84 3.27 1.94 1.21 0.96 0.81 0.65 0.49 0.39 T = 308.15 Ka

240.27 ± 10.12 242.52 ± 4.81 240.66 ± 3.84 C



Article

Table 2. continued mb

ρb

106·Vϕ

mol·kg−1

kg·m−3

m3·mol−1

106·(Vϕ − ΑV·c1/2)

106·V̅ 2

106·V̅ 1

m3·mol−1

m3·mol−1

m3·mol−1

239.47 240.03 238.91 239.70 239.26 239.01 238.46 238.00

239.51 239.98 238.74 239.49 239.02 238.77 238.29 238.01

18.12 18.12 18.12 18.12 18.12 18.12 18.12 18.12

a

T = 308.15 K 0.03030 0.05111 0.08179 0.10291 0.12242 0.15323 0.20386 0.25412 a

995.002 995.626 996.644 997.216 997.848 998.799 1000.385 1001.946

239.82 240.49 239.48 240.35 239.96 239.79 239.36 239.00

± ± ± ± ± ± ± ±

3.27 1.94 1.21 0.96 0.81 0.65 0.49 0.39

Standard uncertainties u are u(Τ) = 0.01 K; u(p) = 10 kPa. bStandard uncertainties u are u(m) = 0.00005 mol·kg−1; u(ρ) = 0.1 kg·m−3.

Table 3. Molality m, Density ρ, Apparent Molar Volume Vϕ, (Vϕ − ΑV·c1/2) Data for Ternary (H2O + 0.09787 mol·kg−1 NaCl + LC·HCl) System at 288.15, 293.15, 298.15, 303.15, and 308.15 K and at Ambient Pressure of 101.325 kPaa ρb

mb mol·kg

−1

kg·m

106·Vϕ −3

−1

/m ·mol 3

T = 288.15 K

a

0.00000 0.02046 0.02578 0.03002 0.05040 0.08093 0.10018 0.12186 0.15498 0.19883 0.24929

1003.080 1003.851 1004.091 1004.198 1004.791 1005.778 1006.546 1007.353 1008.235 1009.521 1011.197

0.00000 0.02046 0.02578 0.03002 0.05040 0.08093 0.10018 0.12186 0.15498 0.19883 0.24929

1001.075 1001.551 1001.776 1001.847 1002.450 1003.452 1003.892 1004.761 1005.423 1006.902 1008.836

0.00000 0.02046 0.02578 0.03002 0.05040 0.08093 0.10018 0.12186 0.15498 0.19883 0.24929

997.934 998.504 998.611 998.832 999.375 1000.351 1000.759 1001.574 1002.644 1003.869 1005.423

106·(Vϕ − ΑV·c1/2) −1

m ·mol 3

ρb kg·m

106·Vϕ −3

a

m3·mol−1

m ·mol

T = 293.15 K

232.33 ± 230.75 ± 232.69 ± 235.82 ± 236.19 ± 234.77 ± 234.12 ± 235.69 ± 236.25 ± 235.69 ± T = 298.15 Ka

4.84 3.84 3.30 1.96 1.22 0.99 0.81 0.64 0.50 0.40

232.09 230.48 232.40 235.44 235.72 234.23 233.53 235.04 235.51 234.87

1001.961 1002.676 1002.812 1003.053 1003.674 1004.545 1005.176 1005.869 1006.917 1008.492 1009.712

247.17 ± 243.20 ± 244.65 ± 242.95 ± 240.62 ± 241.76 ± 239.44 ± 241.46 ± 239.86 ± 237.60 ± T = 308.15 Ka

4.84 3.84 3.30 1.96 1.22 0.99 0.81 0.64 0.50 0.40

246.90 242.90 244.33 242.53 240.10 241.18 238.80 240.74 239.05 236.69

999.550 1000.226 1000.307 1000.387 1001.129 1002.161 1002.532 1003.292 1004.085 1005.449 1006.524

± ± ± ± ± ± ± ± ± ±

4.84 3.84 3.30 1.96 1.22 0.99 0.81 0.64 0.50 0.40

242.95 244.49 240.74 241.84 240.21 241.71 239.78 238.92 239.06 238.40

243.24 244.82 241.10 242.30 240.78 242.35 240.48 239.71 239.95 239.39

106·(Vϕ − ΑV·c1/2)

−1

3

a

235.29 ± 4.84 237.18 ± 3.84 233.78 ± 3.30 236.01 ± 1.96 237.85 ± 1.22 237.54 ± 0.99 237.39 ± 0.81 237.24 ± 0.64 236.01 ± 0.50 237.46 ± 0.40 T = 303.15 Ka 237.69 241.34 242.81 239.18 238.00 240.41 239.29 240.54 239.81 241.23

± ± ± ± ± ± ± ± ± ±

4.84 3.84 3.30 1.96 1.22 0.99 0.81 0.64 0.50 0.40

235.03 236.90 233.47 235.61 237.34 236.98 236.78 236.55 235.23 236.59

237.41 241.03 242.47 238.74 237.45 239.79 238.61 239.78 238.95 240.28


⎡ ⎢ 1000 − cVϕ V2̅ = Vϕ + ⎢ dVϕ ⎢⎣ 2000 + c c d c

values of V0ϕ and BV obtained at studied temperatures are given in Table 5. 3.2. Partial Molar Volume. The partial molar volume of solute LC·HCl (V̅ 2) in aqueous solutions have been computed from Vϕ data by using the expression: D

⎤ dVϕ ⎥ ⎥ cd c ⎥⎦

(3)



Article

Table 4. Molality m, Density ρ, Apparent Molar Volume Vϕ, (Vϕ − ΑV·c1/2) Data for Ternary (H2O + 1.00764 mol·kg−1 NaCl + LC·HCl) System at 288.15, 293.15, 298.15, 303.15, and 308.15 K and at Ambient Pressure of 101.325 kPaa ρb

mb mol·kg

−1

kg·m

106·Vϕ −3

−1

/m ·mol 3

T = 288.15 K

a

0.00000 0.01940 0.02487 0.02769 0.04839 0.07771 0.09790 0.11604 0.14535 0.20495

1039.897 1040.292 1040.447 1040.499 1041.042 1041.686 1042.198 1042.685 1043.381 1044.736

0.00000 0.01940 0.02487 0.02769 0.04839 0.07771 0.09790 0.11604 0.14535 0.20495

1036.927 1037.262 1037.338 1037.505 1037.950 1038.663 1039.108 1039.370 1040.190 1041.492

0.00000 0.01940 0.02487 0.02769 0.04839 0.07771 0.09790 0.11604 0.14535 0.20495

1033.312 1033.512 1033.595 1033.742 1034.226 1034.855 1035.316 1035.712 1036.342 1037.549

106·(Vϕ − ΑV·c1/2) −1

m ·mol 3

ρb kg·m

106·Vϕ −3

a

m3·mol−1

m ·mol

T = 293.15 K

241.48 ± 239.83 ± 240.16 ± 238.26 ± 238.71 ± 238.14 ± 237.55 ± 237.44 ± 237.47 ± T = 298.15 Ka

5.11 3.98 3.58 2.05 1.27 1.01 0.85 0.68 0.48

241.24 239.56 239.87 237.88 238.23 237.61 236.97 236.80 236.70

1038.641 1038.561 1038.935 1039.050 1039.600 1040.270 1040.712 1041.073 1041.779 1043.205

245.01 ± 245.70 ± 241.60 ± 241.25 ± 239.97 ± 239.93 ± 241.00 ± 239.52 ± 239.38 ± T = 308.15 Ka

5.11 3.98 3.58 2.05 1.27 1.01 0.85 0.68 0.48

244.75 245.40 241.29 240.83 239.45 239.34 240.36 238.81 238.54

1035.183 1035.421 1035.602 1035.671 1036.205 1036.850 1037.268 1037.648 1038.357 1039.701

± ± ± ± ± ± ± ± ±

5.11 3.98 3.58 2.05 1.27 1.01 0.85 0.68 0.48

252.07 251.01 247.07 243.70 242.53 241.78 241.43 241.05 240.79

252.36 251.34 247.42 244.16 243.11 242.42 242.13 241.83 241.71

106·(Vϕ − ΑV·c1/2)

−1

3

a

264.56 ± 5.11 249.69 ± 3.98 246.93 ± 3.58 242.13 ± 2.05 240.91 ± 1.27 240.63 ± 1.01 240.73 ± 0.85 239.98 ± 0.68 239.03 ± 0.48 T = 303.15 Ka 250.08 245.77 245.03 241.64 241.18 241.23 241.19 240.48 239.97

± ± ± ± ± ± ± ± ±

5.11 3.98 3.58 2.05 1.27 1.01 0.85 0.68 0.48

264.31 249.41 246.63 241.73 240.41 240.07 240.12 239.30 238.22

249.81 245.46 244.70 241.21 240.63 240.62 240.53 239.73 239.09


Figure 1. Comparison of density (ρ) data as a function of molality (m) of LC·HCl in aqueous solutions with the literature,20 Δ: ●, 288.15 K; ■, 293.15 K; ▲, 298.15 K; ⧫, 303.15 K, ○, 308.15 K.

Figure 2. Variation of density (ρ) data as a function of molality (m) of LC·HCl in aqueous 0.09787 mol·kg−1 NaCl solution, ●, 288.15 K; ■, 293.15 K; ▲, 298.15 K; ⧫, 303.15 K, ×, 308.15 K, and of LC·HCl in aqueous 1.00764 mol·kg−1 NaCl solution, ○, 288.15 K; □, 293.15 K; △, 298.15 K; ◊, 303.15 K, +, 308.15 K.

The partial molar volume of solvent (V̅ 1) in aqueous solutions are calculated by using the equation: E



Article

Figure 5. Variation of parameter (Vϕ − ΑV·c1/2) as a function concentration (c/mol·dm−3) of LC·HCl in aqueous 1.00764 mol·kg−1 NaCl solution: ●, 288.15 K; ■, 293.15 K; ▲, 298.15 K; ◆, 303.15 K, ○, 308.15 K.

Figure 3. Variation of parameter (Vϕ − ΑV·c1/2) as a function concentration (c/mol·dm−3) of LC·HCl in aqueous solution: ●, 288.15K; ■, 293.15 K; ▲, 298.15 K; ◆, 303.15 K, ○, 308.15 K.

The data of ΔtrV0ϕ are collected in Table 5 along with the data of V0ϕ (for ternary system) and V0ϕ (for binary system). 3.4. Limiting Apparent Molar Expansivity. The limiting apparent molar expansivity (E0ϕ) has been calculated by using the relation: ⎛ dV 0 ⎞ ϕ ⎟⎟ Eϕ0 = ⎜⎜ ⎝ dT ⎠

(6)

E0ϕ

The calculated values of of LC·HCl in aqueous solutions and in aqueous 0.09787 mol·kg−1 and 1.00764 mol·kg−1 NaCl solutions at studied temperatures are collected in Table 5.

4. DISCUSSION In Figures 1 and 2, the variation of ρ values as a function of molality of drug LC·HCl in binary (LC·HCl + water) and in ternary (LC·HCl + water + NaCl) systems are shown at studied temperatures. An examination of Tables 2−4 and Figures 1 and 2 reveals that the density values increase linearly with an increase in the concentration of drug in a solution at a particular temperature and the density values of the solutions in binary and ternary systems decrease as temperature increases for a given concentration of drug in a solution. The variations of (Vϕ−AVc1/2) parameter as a function of concentration of LC· HCl in the binary and ternary systems at the studied temperatures are shown in Figures 3−5. It is observed from Table 2 and Figure 3 that the Vϕ values of LC·HCl in aqueous solutions at studied temperatures remain more or less constant as a function of concentration. When a co-solute is added, that is, NaCl to aqueous solutions of LC·HCl, the Vϕ values of LC· HCl exhibit a similar trend but indicate a tendency for the BV parameter to become negative in concentrated NaCl solutions at a given temperature. The V0ϕ values of LC·HCl in binary and ternary systems are collected in Table 5 at the studied temperatures. The V0ϕ values of LC·HCl in water at studied temperatures and at 298.15 K are in good agreement with the data reported in the literature.18−21 An examination of Table 5 reveals that the V0ϕ values of LC·HCl in water increases with an increase in temperature, and it is observed that V0ϕ of LC·HCl in aqueous NaCl solutions exhibits an anomalous trend as a

Figure 4. Variation of parameter (Vϕ − ΑV·c1/2) as a function concentration (c/mol·dm−3) of LC·HCl in aqueous 0.09787 mol·kg−1 NaCl solution: ●, 288.15K; ■, 293.15 K; ▲, 298.15 K; ◆, 303.15 K, ○, 308.15 K.

V1̅ =

M1

( ∂∂ρc )

ρ−c

(4)

where M1 is the molecular weight of the solvent, ρ is the densities of drug aqueous solutions (kg·m−3), and c is the concentration of the drug in aqueous solutions (mol·dm−3). The values of V̅ 2 and V̅ 1 for LC·HCl in aqueous solutions at the studied temperatures are collected in Table 2. 3.3. Transfer Partial Molar Volume. Using the data of apparent molar volumes of the drug molecule at infinitely dilute solutions in ternary solutions containing a fixed concentration (0.09787 mol·kg−1 and 1.00764 mol·kg−1) of ΝaCl and apparent molar volumes of the drug molecule at infinitely dilute solutions in binary solutions, the values of transfer volumes (ΔtrV0ϕ) were calculated by using the following equation: Δtr V ϕ0 = V ϕ0(drug in aqueous NaCl solution) − V ϕ0(drug in aqueous solution) (5) F



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Table 5. Limiting Partial Molar Volume V0ϕ, Deviation Parameter BV, and Transfer Volume ΔtrV0ϕ Data for Aqueous Binary Solutions of LC·HCl and Aqueous Ternary Solutions of LC·HCl at 288.15, 293.15, 298.15, 303.15, and 308.15 K and at Ambient Pressure of 101.325 kPa and Limiting Apparent Molar Expansivity E0ϕ at 293.15, 298.15, and 303.15 K and at Ambient Pressure of 101.325 kPaa 288.15 Ka

a

106·V0ϕ (=V̅ 02)/m3·mol−1

234.01 ± 10.12 235.4 ± 0.4b

106·BV/m6·mol−2 106·E0ϕ/m3·mol−1·K−1

7.4

106·ϕ0V(=V̅ 02)/m3·mol−1 106·BV/m6·mol−2 106·ΔtrV0ϕ/m3·mol−1 106·E0ϕ/m3·mol−1·K−1

232.48 ± 4.84 14.5 −1.53

106·ϕ0V(=V̅ 02)/m3·mol−1 106·BV/m6·mol−2 106·ΔtrV0ϕ/m3·mol−1 106·E0ϕ/m3·mol−1·K−1

240.17 ± 5.11 −21.7 6.16

293.15 Ka

298.15 Ka

H2O + LC·HCl 236.40 ± 10.12 237.56 ± 10.12 238.4 ± 0.5b 239.3 ± 0.3b 240.5c 237.83 ± 0.13d 237.1 ± 0.2e −3.6 −2.7 0.36 0.29 H2O + 0.09787 mol·kg−1 NaCl + LC·HCl 235.58 ± 4.84 243.73 ± 4.84 4.7 −27.3 −0.82 6.17 1.23 0.39 H2O + 1.00764 mol·kg−1 NaCl + LC·HCl 244.88 ± 5.11 243.65 ± 5.11 −38.3 −31.5 8.48 6.09 0.35 0.13

303.15 Ka

308.15 Ka

239.34 ± 10.12 241.4 ± 0.5b

240.22 ± 10.12 241.3 ± 1.0b

−7.8 0.26

−9.0

239.50 ± 4.84 −0.4 0.16 0.03

244.05 ± 4.84 −29.0 3.83

246.21 ± 5.11 −44.6 6.87 0.44

248.03 ± 5.11 −46.8 7.81

Standard uncertainties u are u(Τ) = 0.01 K; u(p) = 10 kPa. bReference 20. cReference 18. dReference 19. eReference 21.

function of temperature. In dilute (0.09787 mol·kg−1) aqueous NaCl solutions, the V0ϕ of LC·HCl increases between 288.15− 298.15 K, while it decreases at 303.15 K and further increases to 308.15 K. Probably, this effect may be related to the water structural effect (C and B parameters of Tait equation of state for water).26 The B parameter for water goes through a maximum between 298.15 and 318.15 K and the compressibility of water goes through a minimum at 321.15 K. The effective internal pressure due to charge−water interaction is related to the partial molal volume of the solute. The breaks in Vϕ behavior as a function of concentration for salts in water have been explained by Vaslow in terms of the water structural effect.28 However, such effects seem to occur at comparatively lower concentrations of LC·HCl. These effects are hard to establish firmly, but the data indicate the possibility, and hence we propose the formation of embrionic micelle type equilibria in aqueous solutions containing LC·HCl. The deviation parameter BV of eq 2 which is a measure of ion−ion (cation−cation), cation−anion−cation, interactions are also collected in Table 5. An examination of Table 5 reveals that the BV value of LC·HCl in water at 288.15 K is positive, indicating that lidocaine cations are structure breaking ions (chaotropic effect) while at 293.15−308.15 K these are negative and may be explained in terms of the presence of hydrophobic cation−cation interactions causing an overall water structure making (kosmotropic) effect. This means that drug cations interact with the surrounding water molecules both with electrostatic and hydrophobic interactions at higher temperatures. It is known that the strength of hydrophobic association increases with an increase in temperature.29 Thus, we find very good evidence of hydrophobic association due to stacking interactions in the case of hydration of the lidocaine cation. In the case of LC·HCl in aqueous 0.09787 mol·kg−1 NaCl solutions at 288.15 and 293.15 K, the BV values are positive, and with a further increase in temperature it becomes negative, while for LC·HCl in aqueous 1.00764 mol·kg−1 NaCl solutions at all studied temperatures, the BV values are negative. In

calculating BV values for ternary solutions, we have used the Redlich eq (eq 2) and assumed that the Debye−Hückel limiting law coefficient (AV) at studied temperatures does not change appreciably with changes in dielectric constant of the medium due to the addition of an electrolyte; that is, the addition of NaCl causes a small change in the dielectric constant of water. The temperature derivative of expansivity as discussed by Hepler; that is,

∂Eϕ

∂ 2V2̅

∂T

∂T 2

( ) = ( ) has been shown to be a useful

parameter to decide about the water structure making or breaking effect of the ions.30 Hepler, argued that increasing pressure would break up the bulky structured regions in water, ⎛ ∂C̅ p0 ⎞ and ⎜ ∂p 2 ⎟ would be expected to be negative. He employs the ⎝ ⎠T relationship: ⎛ ∂C̅ 0 ⎞ ⎛ ∂E 0 ⎞ ⎛ 2 0⎞ ⎜ p2 ⎟ = −T ⎜ ∂ V2̅ ⎟ = −T ⎜ ϕ̅ ⎟ ⎜ ∂T ⎟ 2 ⎜ ∂p ⎟ ⎝ ∂T ⎠ p ⎠ ⎝ ⎝ ⎠T

where C̅ 0p2 is the partial molal heat capacity of solute at infinite dilution, and concludes that structure-breaking solutes should ∂α̅20 ∂T

( ), and structure-making solutes should have positive ( ), where α̅ is the limiting expansivity of the salt. have negative ∂α̅20 ∂T

0 2

On this basis, Hepler classified tetraalkylammonium ions as water structure-making ions. Seen in this light, we note that E0ϕ of LC·HCl in water decreases with increase in temperature ⎛ ∂E 0 ⎞ (Table 5); that is, ⎜ ∂Tϕ ⎟ is slightly negative. All this means that ⎝ ⎠ lidocaine cations act as weak water structure-breaking ions. It is observed that E0ϕ values for LC·HCl differ significantly in aqueous 0.09787 mol·kg−1 NaCl solutions as compared to E0ϕ values in neat water. The E0ϕ values of LC·HCl in 0.09787 mol· G



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kg−1 NaCl solutions also decrease with an increase in ⎛ ∂E 0 ⎞ temperature (Table 5); that is, ⎜ ∂Tϕ ⎟ is negative, while in ⎝ ⎠ case of LC·HCl in 1.00764 mol·kg−1 NaCl solutions, the variation is small at lower temperature but increases at the higher temperature of 303.15 K. All these observations point out that LC·HCl becomes solvated in water by hydrophobic interactions. The electrostatics charge effects are comparatively small. In general such compounds form dimer/trimer and higher aggregates (cation−cation interactions) in water, the extent of which increases in aqueous−salt solutions due to the salting-out effect. Earlier, we envisaged that LC·HCl can form micelles at 0.2 to 0.3 mol·kg−1 concentration due to its peculiar structure and the hydrophobic association effects.22 Such an interpretation is in tune with the salting-out of an embrionic micellar-type structure, becoming enhanced or becoming more feasible due to the presence of the high ionic strength of Na+ ions in ternary solutions. All this looks to be plausible, but needs more elaborate spectral measurements (or even a conductivity) to elucidate the structural details of the interactions among lidocaine cation−lidocaine cations in the presence of other salts. The ΔtrV0ϕ that is, volume change due to transfer of LC·HCl drug molecule from infinitely dilute aqueous solutions to a ternary aqueous solution of LC·HCl containing a fixed concentration of NaCl are also obtained. In the case of LC· HCl in 0.09787 mol·kg−1 NaCl solutions, the limiting transfer volumes are found to be negative at lower temperature (288.15 and 293.15 K) while these are positive at higher temperature (298.15, 303.15, and 308.15 K). In the case of concentrated NaCl (1.00764 mol·kg−1) solutions ΔtrV0ϕ are found to be positive at all studied temperatures (Table 5). One has to consider the effect of ion−ion interactions at higher concentration of NaCl in detail. All thermodynamic properties including mean ionic activity coefficient (γ±) show typical behavior at a higher concentrations of salts, in the extreme case of micelles, γ± even goes through a minimum. Such effects are also pronounced in higher valence electrolyte solutions. Seen in this light one can view the dilute NaCl solution, having an ionic strength of 0.1, exhibiting comparatively more ion−solvent interactions, the extent of which goes on decreasing with an increase in ionic strength. The negative transfer volumes calculated for 0.09787 mol·kg−1 NaCl at lower temperature (288.15 and 293.15 K) and for 0.09787 mol·kg−1 NaCl at higher temperature as well as for 1.00764 mol·kg−1 NaCl at all studied temperatures show positive transfer volumes indicating transformation of the property affected by the salting-in and salting-out phenomenon in which all interactions such as ion− solvent, cation−anion, and solvent enforced cation−cation attraction (hydrophobic interaction) must be influencing the phenomena. More detailed studies are necessary to attach meaningful interpretation for these observed results.

salting−out effect causing the aggregation in the form of stacks of lidocaine cation which causes an increase in the extent of Hbonds in surrounding water molecules. The lidocaine cation− cation interaction concept leading to water structure stabilization as well the nature of hydrophobic groups present in the molecule has been utilized to envisage formation of embrionic micelles in the solution phase, the strength and extent of which seem to depend upon temperature. The calculation of the expansivity parameter and transfer volume supports the contention that the lidocaine cations exhibit a hydrophobic interaction effect, the strength of which increases with an increase in temperature causing the salting-out effect in concentrated NaCl solutions.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Kesharsingh J. Patil: 0000-0002-9927-3345 Notes

The authors declare no competing financial interest.

■

REFERENCES

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5. CONCLUSIONS The apparent and partial molar volumes of the LC·HCl in binary and apparent molar volumes in ternary solutions at finite concentrations as well at infinitely dilute solutions at 288.15, 293.15, 298.15, 303.15, and 308.15 K are obtained. The volume change due to transfer of the LC·HCl drug molecule from infinitely dilute aqueous solutions to a ternary solution of LC· HCl containing a fixed concentration of NaCl are also obtained at all studied temperatures. The NaCl (electrolyte) exhibits a H



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Volumetric Properties of Local Anesthetical Drug Lidocaine

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