Phase Transition Thermodynamic Properties of 2-Methylquinoline, 2- Chloroquinoline and 2-Phenylquinoline

doi:10.21203/rs.3.rs-2289244/v1

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Phase Transition Thermodynamic Properties of 2-Methylquinoline, 2- Chloroquinoline and 2-Phenylquinoline

https://doi.org/10.21203/rs.3.rs-2289244/v1

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Quinoline derivatives are extremely used in medicine and industry. Therefore, the thermodynamic properties of them are essential to know their quality and stability in use. In this work, the thermodynamic characters of 2-methylquinoline (quinaldine), 2-chloroquinoline, and 2-phenylquinoline were investigated. Moreover, the evaporation enthalpy of the compounds were determined the solution calorimetry-additivity scheme approach at 298.15 K. The solution calorimetry was used to measure solution enthalpies of the compounds in benzene solvent at 298.15 K. While, the solvation enthalpy of the compounds were calculated by additivity scheme approach. In addition, the transpiration method was applied to determine the vapor pressure at various temperatures for 2-Chloroquinoline for the first time. As a result, the thermochemical properties; enthalpy, entropy, and Gibbs energy for 2-methylquinoline, 2-chloroquinoline and 2-phenylquinoline were determined from crystalline/liquid to gas phase. Moreover, the thermochemical characteristics values exhibited smaller uncertainties than those in literature data. Consequently, the phase transition thermodynamically studied on 2-position of the quinoline compound when substituted methyl, chloro and phenyl groups.

quinoline

evaporation enthalpy

solvation enthalpy

solution calorimetry

additive scheme approach and transpiration method.

Quinoline derivatives are used in a wide range in medicine and in industries [1]. The quinolines were applied in preparation of drugs of Influenza B-Mass virus because they have antibacterial activity. Furthermore, the quinolines are used to treatment the diseases like cancer, malaria and anti-inflammatory [2][3], antidotes against poisoning, antidiabetic activities and antiviral HCV [4]. In addition, the quinolines were applied for electro-optical display devices [5] and research on magnetic properties, [6] photochemistry, [7] materials science, solution studies, and homogeneous catalysis owing to the versatility of their steric and electronic properties [8]. Therefore, thermochemical study on quinolines is essential before using them. Thermochemical properties of the basic compounds in drugs and the devices are detected the quality and stability of drugs and the manufacture devices.

The thermodynamic properties of phase transition presents transfer (enthalpy, entropy and Gibbs energy) from liquid or crystalline state to the gas phase at constant temperature and pressure. Of course, evaporation enthalpy is a chemical thermodynamics property that the evaporation enthalpy is measured directly by calorimetric methods [9], [10] or indirectly from determination vapor pressure as a function to temperature [11], [12]. As consequence, solution calorimetry was employed to determine the evaporation enthalpy of various compounds in specific solvents from solution enthalpy and solvation enthalpy values [13]. In this method, the solution enthalpy was measured from solution calorimetry and additivity scheme approach was used to calculate solvation enthalpy at 298.15 K [14]–[16] according to the following equation;

$${\varDelta }_{cr,liq}^{g}{H}_{m}^{0}={\varDelta }_{soln}{H}_{m}^{Ai/Bz}-{\varDelta }_{solv}{H}_{m}^{Ai/Bz}$$

Where, ${\varDelta }_{cr,liq}^{g}{H}_{m}^{0}$ is the evaporation enthalpy of a quinoline derivative compound at standard state, ${\varDelta }_{soln}{H}_{m}^{Ai/Bz}$is solution enthalpy of a quinoline compound in benzene solvent and ${\varDelta }_{solv}{H}_{m}^{Ai/Bz}$is the solvation enthalpy of quinoline solute in benzene solvent. Then, solvation enthalpy of the compounds were calculated by additive scheme approach. In addition, the transpiration method was applied to determine vapor pressures to temperature dependency for the organic and inorganic compounds. Consequently, the chemical thermodynamic characters were measured through equations used from the transpiration method.

The chemical thermodynamic properties distinguish the stability and quality of drugs and devices were manufactured from the chemicals (quinolones in this study). Especially, the phase transition thermodynamic properties; enthalpy, Gibbs energy and entropy. In this work, the thermochemical properties were estimated for the compounds 2-methylquinoline, 2-chloroquinoline and 2-phenylquinoline (Fig. 1). According to the chemical structure they are differ in 2-cite on the quinoline compound where substituted to methyl, chloro and phenyl groups.

Furthermore, the solution calorimetry-additive scheme approach and the transpiration method were applied in this work to determine the phase transition thermochemical properties of the compounds. The evaporation enthalpy was determined at 298.15 K to the three compounds from solution calorimetry-additivity scheme methodology. Besides, the thermochemical properties study of phase transition on these compounds were also investigated. After that, there was estimated the impact of the substituted groups of methyl, chloro and phenyl on the 2-position of the quinoline compound.

2.1. Materials

The quinoline derivatives were from different commercial origin materials. The quinoline solute compounds were in high mass fraction purity, which were more than 97% (Table 1). Benzene was used as solvent and its origin was local commercial origin. Additionally, the benzene solvent was purified by standard methods [17] through fraction distillation. The purity of the solvent was raised to the mass purity 99% which tested by gas chromatography GC Agilent 7820 A.

Table 1

CAS number, origin and purity of the quinolines.
Compound	CAS	Origin	Purity %
2-Methylquinoline	91-63-4	Alfa Aesar	97+
2-Chloroquinoline	612-62-4	SIGMA-ALDRICH	99
2-Phenylquinoline	612-96-4	ACROS ORGANICS	99+

2.2. Solution Calorimetry

For measuring enthalpy of solution quinoline compounds was used commercial TAM III solution calorimetry (TA Instruments). First, small amount of a quinoline derivative (Quinaldine (2-methylquinoline), 2-Chloroquinoline or 2-phenylquinoline) was dissolved in the benzene solvent to get infinite dilution solution into solution calorimetry glass cell. Then, there are two different procedures according to the state of the material (crystalline and liquid) to measure solution enthalpy by solution calorimetry technique at 298.15 K. Moreover, the crystalline compound, first it was grinded to make like powder then weighted about 500 mg and it dissolved into the glass cell, which it contained about 90 mL of the solvent. While, the liquid samples, small portions of the liquid compound between 50–300 µL were injected electronically by operated syringe connected with long gold cannula immersed into the solvent [13].

The solution calorimetry was calibrated up on the standard crystalline and liquid compounds. The standard crystalline compound was potassium chloride. The KCl standard crystalline was dissolved in a purified water (distillated twice and deionized) into the calorimetry cell, its solution enthalpy at 298.15 was 17.475 ± 0.08 kJ.mol^− 1, and in the literature solution enthalpy of KCl was 17.205 kJ.mol^− 1 at same temperature [18]. Identically, the liquid compounds, the calorimetry was tested by propan-1-ol as standard liquid solute in purified water and the value solution enthalpy was − 10.16 ± 0.05 kJ.mol^− 1 as well as the propanol-1 solution enthalpy value in the literature was − 10.18 ± 0.03 kJ.mol^− 1 [19]. Therefore, the values of solution enthalpies of our standards were well agree with the literature values.

2.3. Transpiration Method

Vapor pressure was measured over the liquefied compound of 2-chloroquinoline as a function to temperature through the transpiration method. First, about 0.5 g of the sample was mixed with glass beads and placed into the U-tube thermostatic at constant temperature ± 0.1 K. Then, the amount of the evaporated compound into the thermostat tube at a definite temperature carried out by Nitrogen gas flow stream with known rate and specific time. After that, the sample condensed into the second cooling part tube. The amount of condensed compound m_i was measured by the gas chromatography at each temperature with respect to an organic standard liquid compound. The nitrogen flow stream in a definite flow rate passed through the tube at selected temperature T_i. Definitely, the amount of saturated vapor pressure of the sample condensed in the cold trap was measured at definite time to know the volume V_N2 transported of nitrogen gas at the specific rate according to general gas law, the procedure described elsewhere [11], [13], [20], [21].

${p}_{i}$ = m_i·R·Ta / V·M_i (2)

Where; V = V_N2 + V_i = (n_N2 + n_i)·R·T_a / P_a

Where V is the volume of the gas phase consisting of the n_N2 moles of the carrier gas and n_i mole of gaseous compound under study at the atmospheric pressure P_a and the ambient temperature T_a. The volume of the carrier gas V_N2 was calculated through a digital flow rate microcontroller. The digital flow rate sensor was worked in an uncertainty at the level of 2.5%. The flow rate of the nitrogen stream was also controlled by using soap bubble flow pipette and optimized in order to reach the saturation equilibrium of the transporting gas at each temperature under study. The volume of the carrier gas V_N2 read from the calibrated digital flow rate sensor.

Solution calorimetry-additivity scheme approach and transpiration method were applied to measure the evaporation enthalpy to the three compounds the 2-position substituted quinolines at 298.15 K. In consequence, the other thermochemical properties of the compounds were estimated to the 2-chloroquinoline compound from the transpiration method and for the other compounds were collected in the literature data. The chemical thermodynamic characters values of the quinolines are established the stability and thermochemical energy of the compounds as well as the impact of substituted groups at 2-position of the quinoline compound. Consequently, the stability and quality of the drugs and the devises, which made from the studied quinolines could be known.

Hence, the evaporation enthalpy of the studied compounds was measured by the solution calorimetry-additive scheme approach and the transpiration methods at 298.15 K. Then, from solution calorimetry-additive scheme method was determined vaporization/sublimation enthalpy for quinoline derivatives according to Eq. (1). While, the solution enthalpy was determined directly from the solution calorimetry at 298.15 K and the solvation enthalpy was calculated by additivity scheme approach.

3.1. Solution enthalpy

Solution enthalpy was determined directly from solution calorimetry at 298.15 K for the studied compounds. Solution enthalpy is enthalpy of a compound in standard state (solid or liquid) to dissolve in solvent to make a solution infinite dilute solution at standard temperature and pressure 0.1 µPa. Moreover, according to the solution enthalpy values (Table 2) indicates that all three compound exist the endothermic affect when they dissolve in the benzene solvent. Furthermore, the low value solution enthalpy 2-methylquinoline due to the high interaction with the benzene solvent as well as it is in liquid state. While, the solution enthalpy values 2-chloroquinoline and 2-phenylquinoline were close to each other because they were in crystalline state, the solution enthalpy values contain destroy crystalline lattice then process heat of solvation into the solvent.

3.2. Solvation enthalpy

Solvation enthalpy is the enthalpy transfer of a compound from gaseous state to the solvent in the liquid phase at standard temperature and pressure 0.1 µPa. Solvation enthalpy is another phase transition chemical thermodynamic character indicates the solubility effect of the a compound in its solvent. In this work, the solvation enthalpy was measured to the three quinolines with respect to additivity scheme approach. According to the additive scheme approach, the solvation enthalpy was estimated for the quinolines from follow equations.

Solvation enthalpy was calculated for the quinoline;

${\varDelta }_{solv}{H}^{Ai/S }$ = ${\varDelta }_{solv}{H}^{ArH/S }$ + Σ ${\varDelta }_{solv}{H}^{Xi\to CH/S}$ (3)

Where ${\varDelta }_{solv}{H}^{Ai/S }$is the solvation enthalpy of quinoline compound Ai in solvent S, ${\varDelta }_{solv}{H}^{ArH/S }$is the solvation enthalpy of the naphthalene compound (removed nitrogen group into the quinoline ring) in the solvent S and ${\varDelta }_{solv}{H}^{\text{X}\text{i}\to \text{C}\text{H}/S}$ is the solvation enthalpy of the substituted group with CH means it is azo group into the quinoline compound in solvent S. As notify, the solvents S must be same solvent to all components of a compound.

In addition, the solvation enthalpy of Quinoline with substituted group was measured as from the following equation;

${\varDelta }_{solv}{H}^{AiX/S }$ = ${\varDelta }_{solv}{H}^{ArH/S }$ + ${\varDelta }_{solv}{H}^{X/S}$ (4)

Where ${\varDelta }_{solv}{H}^{AiX/S }$is the solvation enthalpy of the substituted quinoline compounds AiX in solvent S, ${\varDelta }_{solv}{H}^{ArH/S }$ is solvation enthalpy of the compound without any attached group (quinoline in this work) in solvent S, ${\varDelta }_{solv}{H}^{\text{X}/S}$ is solvation enthalpy of the branched group (methyl, chloro and phenyl in this study) in the same solvent. Notably, the S solvent must be the same to all parts of the study compound.

The two above equations (3) and (4) were applied to the 2-methylquinoline and 2-chloroquinoline to measure solvation enthalpy then the evaporation enthalpy for the two compounds. While, Eq. (5) was used in calculation enthalpy of solvation for the 2-Phenyl quinoline compound, because the 2-phenyl quinoline compound didn’t obey to the two above equations due to high deviation of the solvation enthalpy value as well as it has three aromatic rings because it was calculated as poly aromatic compound with respect to the additive scheme methodology [22]. Therefore, in this work, equations (5) and (3) were used to determine solvation enthalpy;

${\varDelta }_{solv}{H}^{2PQ/Bz }$ = ${n.1/6.\varDelta }_{solv}{H}^{Bz/Bz }+1.08 . Y$ (5)

Where ${\varDelta }_{solv}{H}^{2PQ/Bz }$ is the solvation enthalpy of 2-phenylquinoline in benzene solvent, ${\varDelta }_{solv}{H}^{Bz/Bz }$is solvation enthalpy of benzene in benzene solvent, n is the number of carbon atoms and Y is the difference between carbon and hydrogen atoms. Consequently, the solvation enthalpy value for the 2-phenylquinoline compound was − 82.68 kJ.mol^− 1 (Table 2). Therefore, the sublimation enthalpy value of the 2-phenylquinoline compound agree with those in the literature values (Table 4).

Table 2

solution enthalpy, solvation enthalpy and evaporation enthalpy in kJ.mol^− 1 at 298.15 K.
Compound	${-\varDelta }_{solv}{H}_{m}^{Ai/Bz}$ ^b	${\varDelta }_{soln}{H}_{m}^{Ai/Bz}$ ^c	${\varDelta }_{liq,cr}^{g}{H}_{m}$^a
2-Methylquinoline	63.8	1.45	65.25 ± 0.13
2-Chloroquinoline	66.4	21.21	87.61 ± 0.89
2-Phenylquinoline	82.68	19.92	108.0 ± 0.04

^a the values of standard uncertainty were calculated from standard deviation of repeating experiments of the solution calorimetry. ^b the values were calculated from equations (3), (4) and (5). ^c the values were directly measured from solution calorimetry technique in this work.

3.3. Evaporation enthalpy

The sublimation/vaporization enthalpy was determined for 2-methyl quinoline, 2-chloro quinoline and 2-phenyl quinoline solution calorimetry-additivity scheme approach at standard temperature. Moreover, the sublimation/vaporization enthalpy values in this work were in high accuracy obtained in the solution calorimetry at 298.15 K according to equations (1), (3), (4) and (5) (see Tables 2 and 4) with respect to standard uncertainty values. In addition, to establish values from solution calorimetry-additivity scheme mehtodology of the 2-chloroquinoline and because it had only one literature value on its thermochemical properties (sublimation enthalpy), therefore, the thermochemical properties were determined through the transpiration method. In this method, the thermodynamic parameters were indirectly calculated in relation between temperature change and vapor pressure values of the studied compound via applying Clark-Glaw equation, in consequence Eq. (7);

$$Rln{(P}_{t}/{P}_{0})=-\frac{{\varDelta }_{cr,liq}^{g}{G}_{m}^{0}}{{T}_{0}}+{\varDelta }_{cr,liq}^{g}{H}_{m}^{0}\left(\frac{1}{{T}_{0}}-\frac{1}{T}\right)+{\varDelta }_{cr,liq}^{g}{C}_{p,m}^{0}\left(\left(\frac{{T}_{0}}{T}\right)-1+ln\left(\frac{T}{{T}_{0}}\right)\right)$$

$$R{ln}{p}_{i}=a+ \frac{b}{T}+{\varDelta }_{liq,cr}^{g}{C}_{p,m}^{o}ln\left(\frac{T}{{T}_{0}}\right)$$

Where R is the general gas constant (8.31447 J.mol^− 1.K^− 1), p_i is vapor pressure of compound i, a and b are adjustable constants, ${\varDelta }_{liq,cr}^{g}{C}_{p,m}^{o}$ is molar heat capacity change of a compound from liquid or crystalline state to the gaseous phase at constant pressure and standard temperature, and T, T_o are temperatures at selected and reference temperatures (298.15 K) respectively. Moreover, the heat capacity change value of the three compounds were calculated from Acree, Jr. and S. Chickos estimation equations for liquid and crystalline states respectively [23];

$${{\varDelta }_{liq}^{g}C}_{p,liq}=10.58+0.26{C}_{p,liq}$$

$${{\varDelta }_{cr}^{g}C}_{p,cr}=0.75+0.15{C}_{p,cr}$$

Consequently, from Eq. (7) calculated molar heat capacity change and a, b constants. Therefore, from molar heat capacity change and constant b at T temperature was measured the vaporization enthalpy for 2-chloroquinoline;

$${\varDelta }_{liq,cr}^{g}{H}_{m}^{o}\left(T\right)=-b+{\varDelta }_{liq,cr}^{g}{C}_{p,m}^{o}T$$

Where, ${\varDelta }_{liq,cr}^{g}{H}_{m}^{o}\left(T\right)$ is the evaporation enthalpy of 2-chloroquinoline compound at T temperature then, from the Eq. (10) was calculated the vaporization/sublimation enthalpy. The vapor pressure to temperature dependency, vaporization enthalpy, entropy change and Gibbs energy change values were determined by transpiration method (Eq. 6) in this work for the 2-chloroquinoline compound at the selected temperature and at suitable nitrogen flow rate to obtain the amount of evaporated vapor over the sample (table 3). Vapor pressures over 2-chloroquinonline was measured for the first time and its thermochemical properties at reference temperature 298.15 K, also were determined.

Table 3 vapor pressure of liquid 2-Chloroquinoline from transpiration method.

$$\text{ln} (p/{p}^{○})=\frac{249.39}{R}-\frac{73847.58}{RT}-\frac{48.8}{R}\text{l}\text{n}\frac{T}{298.15}$$

${\varDelta }_{liq}^{g}{H}_{298.15 \text{K}}=$ 66.76 ± 0.55 kJ.mol⁻¹

Tm, K	m, mg	V(N₂), L	Gas-flow, L.hr^− 1	P, Pa	${\varDelta }_{liq}^{g}{H}_{Tm K}$ kJ.mol^− 1	${\varDelta }_{liq}^{g}{S}_{Tm}$ J.K^− 1.mol^− 1
313.4	2.40	8.721	4.19	4.19	66.02	126.9
319.5	2.53	5.233	4.19	7.35	65.72	126.6
328.8	2.28	2.428	4.16	14.34	65.27	125.0
331.1	2.81	2.428	4.16	17.65	65.16	125.0
335.7	3.05	1.953	4.19	23.48	64.93	120.7
339.3	3.11	1.535	4.19	30.87	64.76	121.7
340.2	2.28	1.047	4.19	33.23	64.71	121.4
343.0	2.49	0.986	1.69	38.48	64.58	122.0
345.6	2.09	0.704	1.69	45.23	64.45	122.5
348.9	2.06	0.563	1.69	55.87	64.29	122.9
351.7	2.47	0.563	1.69	66.92	64.15	123.7
353.4	2.74	0.563	1.69	74.11	64.07	123.7
357.4	2.59	0.423	1.69	93.31	63.87	124.0

According to the vapor pressure values to temperature dependency (table 3) the 2-Chloroquinoline in transpiration method data was obtained, the enthalpy of vaporization value was 66.76 ± 0.55 kJ.mol^− 1 at reference temperature (298.15 K) as in the method because the compound first liquefied then evaporated into the thermostat tube after that from condensed state measured its vaporized amount. Furthermore, with respect to the work [24] the solution enthalpy (was in the crystalline form of the solute compound) approximately equal to the fusion enthalpy ${\varDelta }_{cr}^{liq}{H}^{Ai}$ at fusion temperature for the same compound. Consequently, sublimation enthalpy ${\varDelta }_{cr}^{g}{H}_{m}^{0}$ for 2-Chloroquinoline as following equations was calculated;

$${\varDelta }_{cr}^{g}{H}_{m}^{0}={\varDelta }_{cr}^{liq}{H}^{Ai}+{\varDelta }_{liq}^{g}{H}_{m}^{0}$$

Where; ${\varDelta }_{soln}{H}_{298.15 K}\approx {\varDelta }_{cr}^{liq}{H}^{Ai}$,

Then, ${\varDelta }_{cr}^{g}{H}_{m}^{0}={\varDelta }_{soln}{H}_{298.15 K }+{\varDelta }_{liq}^{g}{H}_{m}^{0}$ (12)

Therefore, the sublimation enthalpy values of 2-Chloroquinoline were 87.61 ± 0.89 kJ.mol^− 1 and 87.97 ± 0.55 kJ.mol^− 1 at 298.15 K by solution calorimetry-additivity scheme and the transpiration methods respectively. While, the value of sublimation enthalpy for 2-Chloroquinoline by the microcalorimetry method was 84.3 ± 2.6 kJ.mol^− 1 [25] with higher uncertainty than the values in this work (Table 4). Besides, the sublimation enthalpy value of 2-Phenylquinoline was 108.0 ± 0.04 kJ.mol^− 1 in solution calorimetry-additivity scheme methodology. In addition, it was compared with the literature average value was 104.8 ± 2.2 kJ.mol^− 1, when it was done by Knudsen mass-loss effusion method [20], the difference between them was 3.57 kJ.mol^− 1 agree with each other when we look at the uncertainty values. In the present study, the evaporation enthalpies values of the compounds were exist lower standard deviations in compare with those of the literature values. This is indicated that they showed some higher accuracy values solution calorimetry-additivity scheme approach in comparison with other methods in the literature.

Table 4

various techniques to determine evaporation enthalpy.
Compound	M^a	T /K	${\varDelta }_{liq,cr}^{g}{C}_{p,298 K}$^b J.K^− 1.mol^− 1	${\varDelta }_{liq,cr}^{g}{H}_{298.15 K}$ kJ.mol^− 1	${\varDelta }_{liq,cr}^{g}{H}_{T/K}$^c kJ.mol^− 1	Ref.
Quinoline(liq) ^d	IPM,E	298–559			57.9 ± 0.1	[23]
	GS	298		58.1		[23]
	IPM,E	440			50.7 ± 0.1	[23]
	GC				53.3	[23]
	SC		63.59			This work
2-Methylquinoline(liq)	E	319–553			62.6 ± 0.1	[26]
	M	298		66.1 ± 1.9		[23]
	GS	281–313			61.2	[23]
	E	443–521			54.7	[23]
	SC	298.15	70.98	65.25 ± 0.13		This work
2-Chloroquinoline(cr)	CM	298.15			84.3 ± 2.6	[25]
2-Chloroquinoline(cr)	SC	298.15	26.64	87.61 ± 0.89		This work
	T	298.15		87.97 ± 0.55		This work
2-Phenylquinoline(cr)	KM	337–351			105.4 ± 0.9	[27]
	KM	337–351			103.1 ± 0.8	[27]
	KM	298.15		104.8 ± 2.2		[20]
	SC	298.15	36.81	108.0 ± 0.04		This work

^a methods, E = Ebulliometer, M = Microcalorimetric, V = vaporization method, GC = gas chromatography, GS = Gas saturation vaporization method, SC = Solution Calorimetry, CM = Calvet microcalorimetry, T = Transpiration method and KM = Knudsen mass-loss effusion. IPM = Inclined piston manometry. ^b the values were measured from estimation equation method (see text). ^c the values were calculated in literature data at mean temperature. ^d the quinoline compound was set just to comparison with the other compounds in this work.

3.4. Gibbs energy and entropy

Gibbs energy and entropy of the phase transition were estimated for the studied compounds at temperature 298.15 K (Table 5). The Gibbs energy of the phase transition of the compounds from liquid or crystalline state to the gas phase were generally no favorably changed. Moreover, the highest value of the Gibbs energy was 44.3 ± 0.04 kJ.mol^− 1 for the 2-Phenylquinoline compound because it was in most stable crystalline state due to it has the maximum value of sublimation enthalpy. While, the minimum value of Gibbs energy was 13.36 kJ.mol^− 1 was due to the quinoline compound, therefore, it has not any substituted group and it was in liquid state.

In another hand, the evaporation entropy values were also estimated to the quinoline and the substituted quinolines. Moreover, the compounds of 2-Phenylquinoline and 2-Chloroquinoline were present maximum value of sublimation entropy because they were in crystalline state and they exist the highest values of sublimation enthalpy. Furthermore, the entropy change was determined at various temperature for 2-Chloroquinoline through the transpiration method (Table 2) from Clark-Glaw equation. In consequence, according to Clark-Glaw equation, most of the thermodynamic parameters were evaluated and adjusted to the reference temperature 298.15 K.

In addition, the standard uncertainties values were combined in the transpiration method and in the solution calorimetry uncertainties where the vapor pressure and temperature uncertainties adjusted to the reference temperature. The uncertainties of vaporization/sublimation enthalpies combined in literature values assessed with respect to Clark-Glaw equation. Additionally, the transpiration method uncertainties described in detail elsewhere [28].

Table 5

the thermodynamic properties of the quinolines.
Compound	${\varDelta }_{liq,cr}^{g}{H}_{298 K}$ ^a kJ.mol^− 1	${\varDelta }_{liq,cr}^{g}{G}_{298 K}$ kJ.mol^− 1	${\varDelta }_{liq,cr}^{g}S$ J.K^− 1.mol^− 1
Quinoline(liq)	58.1 ^e	13.36 ^g	150.05 ^f
2-Methylquinoline(liq)	65.25 ± 0.13	24.1 ± 0.03 ^d	126.8 ^d
2-Chloroquinoline(cr)	87.61 ± 0.89	28.1 ± 0.05 ^c	199.7 ± 1.9 ^c
2-Phenylquinoline(cr)	108.0 ± 0.04	44.3 ± 0.04 ^b	202.7 ± 2.7 ^b
^a values were measured by solution calorimetry-additive scheme method in this work (Table 1). ^b values were determined from vapor pressure measurements [29]. ^c measured in this work by transpiration method. ^d according to Clark-Glaw equation from reference [30]. ^e from table 3. ^f the value was calculated from equation (${\varDelta }_{liq,cr}^{g}{S}_{298 \text{K}}={\varDelta }_{liq,cr}^{g}{H}_{298 \text{K}}/{T}_{b}$) T_b boiling point from reference [31]. ^g the value was calculated from equation:${\varDelta }_{liq,cr}^{g}{G}_{298 \text{K}}={\varDelta }_{liq,cr}^{g}{H}_{298 \text{K}}-\left(298.15 K\right).{\varDelta }_{liq,cr}^{g}{S}_{298 \text{K}}$

In summing up, the evaporation enthalpy values studied compounds were determined from solution enthalpy values, which directly measured from solution calorimetry at 298.15 K as in the Eq. (1). While, the solvation enthalpy values were calculated additivity scheme approach in the equations (3, 4 and 5) at standard temperature into the same solvent. Meanwhile, the evaporation enthalpy values were determined by solution calorimetry in high accuracy (lowest value of the standard deviation) for the three compounds of Quinaldine, 2-Chloroquinoline and 2-Phenylquinoline. In addition, the transpiration method was applied to determine vapor pressures to temperature dependency and the vaporization enthalpy of 2-Chloroquinoline was determined. Accordingly, for the first time, vapor pressure over 2-Chloroquinoline to temperature dependence and other chemical thermodynamic properties were determined at various temperatures by the transpiration method. Further, in the transpiration method calculated uncertainties of the thermochemical properties of vaporization enthalpy, free energy change and entropy change. By the way, the vaporization enthalpy of liquid 2-Chloroquinoline was changed to sublimation enthalpy as in Eq. (10) without measuring fusion enthalpy instead used solution enthalpy of its solid state at temperature 298.15 K. As well as, the thermochemical properties were calculated to the three compounds with their uncertainties and the values were set in the table (5). The entropy changes from crystalline state to gas phase of 2-Chloroquinoline and 2-Phenylquinoline close to each other. However, the 2-Chloroquinoline and 2-Phenylquinoline considerably had high difference in their free energy change from solid state to gas phase due to the substituted groups of the chloro and phenyl. According to the three compounds were studied, comparatively the thermochemical properties were determined to 2-position substitution of quinolines in comparison to quinoline thermodynamic properties values where substituted to methyl, chloro and phenyl groups.

Evaporation enthalpy for the compounds Quinaldine (2-Methylquinoline), 2-Chloroquinoline, and 2-Phenylquinoline were found using the solution calorimetry-additive scheme approach. In addition, the chemical thermodynamic properties were estimated to the target compounds and the values were adjusted to the standard temperature. Furthermore, the sublimation enthalpy, free energy, and entropy shift from crystalline to gas phase were all maximum for 2-phenylquinoline. In comparison to literature values, the thermochemical values used in this investigation exhibited a reduced level of uncertainty. The 2-position of quinoline compounds was examined in this study, where methyl, chloro, and phenyl groups were replaced. While, the quinoline derivatives have a critical role in medicine, particularly in the production of anti-inflammatory medications. Therefore, from chemical thermodynamic properties can be known the quality and stability of the medicines were made from the quinoline derivatives.

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Phase Transition Thermodynamic Properties of 2-Methylquinoline, 2- Chloroquinoline and 2-Phenylquinoline

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Abstract

Figures

1. Introduction

2. Experimental Part

2.1. Materials

2.2. Solution Calorimetry

2.3. Transpiration Method

3. Results And Discussions

3.1. Solution enthalpy

3.2. Solvation enthalpy

3.3. Evaporation enthalpy

3.4. Gibbs energy and entropy

4. Conclusion

References

Additional Declarations

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