Fusion enthalpies of benzoic acid derivatives, aromatic and heteroaromatic carboxylic acids as a tool for estimation of sublimation enthalpies at 298.15 K

Accepted Manuscript Fusion enthalpies of benzoic acid derivatives, aromatic and heteroaromatic carboxylic acids as a tool for estimation of sublimation enthalpies at 298.15 K Boris N. Solomonov, Ruslan N. Nagrimanov, Mikhail I. Yagofarov PII:

S0378-3812(16)30451-4

DOI:

10.1016/j.fluid.2016.09.016

Reference:

FLUID 11264

To appear in:

Fluid Phase Equilibria

Received Date: 17 May 2016 Revised Date:

8 August 2016

Accepted Date: 11 September 2016

Please cite this article as: B.N. Solomonov, R.N. Nagrimanov, M.I. Yagofarov, Fusion enthalpies of benzoic acid derivatives, aromatic and heteroaromatic carboxylic acids as a tool for estimation of sublimation enthalpies at 298.15 K, Fluid Phase Equilibria (2016), doi: 10.1016/j.fluid.2016.09.016. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT Fusion enthalpies of benzoic acid derivatives, aromatic and heteroaromatic carboxylic acids as a tool for estimation of sublimation enthalpies at 298.15 K Boris N. Solomonov1, Ruslan N. Nagrimanov, Mikhail I. Yagofarov.

Kazan, Russia

Abstract

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Department of Physical Chemistry, Kazan Federal University, Kremlevskaya str. 18, 420008

In this work a method of estimation of sublimation enthalpies of benzoic acid derivatives

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and aromatic or heteroaromatic carboxylic acids was developed. The method is based on calculation of sublimation enthalpy from fusion enthalpy of studied compound and of benzoic

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acid at corresponding melting temperatures and sublimation enthalpy of benzoic acid at 298.15 K.

Calculated sublimation enthalpy values of benzoic acid derivatives containing CH3-, CH3O-, F-, Cl-, Br-, I-, NO2- and other substituents, 1- and 2-naphthoic acids and heteroaromatic carboxylic acids (38 compounds in total) were compared with literature data (at 298.15 K)

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obtained by conventional methods. In most cases, divergence does not exceed 2-3%.

Keywords: Enthalpy of sublimation; Enthalpy of fusion; Benzoic acid derivatives, Naphthoic

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acids, Heteroaromatic carboxylic acids.

1

To whom correspondence should be addressed, E-mail: [email protected] (B.N. Solomonov)

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1. Introduction

Determination of phase transition enthalpies is one of the most difficult and actual problems in chemical thermodynamics. Experimental values of vaporization, sublimation and fusion enthalpies are of a great interest for such disciplines as chemistry, physics and ecology. One of these quantities (sublimation enthalpy) may be measured by various conventional methods [1, 2]. However, the usage of conventional methods causes a number of problems that

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affect sublimation enthalpy magnitude [1-3]. It is especially manifested when the measurements are spent with thermally unstable compounds or at elevated temperatures.

Recently, in our laboratory a method for determination of sublimation enthalpy at 298.15 K without transfer of the substance to the gas phase [3-9] was developed. Method is based on

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well-known relation between sublimation/vaporization enthalpy at 298.15 K on the one hand and solution and solvation enthalpies at 298.15 K on the other hand. We have elaborated various

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methods of calculation of solvation enthalpies of aromatic and heteroaromatic compounds. These data together with the solution enthalpies (298.15 K) allowed determining the sublimation and vaporization enthalpies of more than 100 compounds [3-9].

An interesting fact about equality of fusion enthalpies at melting temperature and solution enthalpies in benzene at 298.15 K of aromatic and heteroaromatic compounds was discovered in [10-12]. It was shown that such relation is possible if two conditions are respected.

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Firstly, enthalpy of fusion for the studied compound weakly depends on temperature. Secondly, enthalpy of solution of such compound in hypothetical liquid state in benzene at 298.15 K is close to zero. As a result, we obtained relations, which tie vaporization enthalpy of the studied compound and enthalpy of solvation in benzene at 298.15 K as well as sublimation

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enthalpy at 298.15 K with solvation enthalpy in benzene and fusion enthalpy at melting point. Thus, the approach for calculating the enthalpy of sublimation at 298.15 K from the fusion

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enthalpy at the melting temperature and the solvation enthalpy was proposed. Solvation enthalpies of investigated compounds were calculated according to an additive scheme [10-12]. This approach was successfully applied for calculation of sublimation enthalpies of more than 100 compounds [10-12]. However, a number of systems with athermal liquid-liquid dissolution at 298.15 K, for

which this approach can be used, is limited. Therefore, in this work we proposed a new scheme for evaluation of sublimation enthalpies using fusion enthalpies at melting point. The scheme was verified by the comparison of calculated sublimation enthalpies of benzoic acid derivatives, naphthoic and heteroaromatic carboxylic acids at 298.15 K with literature data.

2. Methodology.

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Sublimation enthalpy ( ∆ gcr H mAi (298.15 K)) of solid compound Ai at 298.15 K is bound with solution enthalpy of solute Ai in solvent S ( ∆ soln H Ai /S (298.15 K) ) and solvation enthalpy of solute Ai in solvent S ( ∆ solv H Ai /S (298.15 K) ) by the following equation:

∆ gcr H mAi (298.15 K) = ∆ soln H Ai /S (298.15 K) − ∆solv H Ai /S (298.15 K)

(1)

According to the group-contribution method, the solvation enthalpy of aromatic or

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heterocyclic aromatic compound (Ar(Xi)n) in any solvent is calculated as a sum of solvation enthalpy ( ∆ solv H Ai /S ) of the reference unit (aromatic hydrocarbon, heterocyclic aromatic compound without substituents) and contribution of the substitution of the hydrogen atoms in the

following equation:

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reference unit by any other group (Xi) ( ∆ solv H Xi → H/S ). This procedure can be described by the ∆ solv H Ar(Xi )n /S = ∆solv H ArH/S + n ⋅ ∆solv H Xi →H/S

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where n is the number of the substituents.

(2),

It was shown [10, 11] that enthalpies of solution of benzene-like derivatives in benzene at 298.15 K are approximately equal to the fusion enthalpies of these substances at melting temperature (Tm). Relationship between ∆ soln H Ai /S (298.15 K) and ∆ lcr H Ai (Tm) may be analyzed.

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Solution enthalpy of solid Ai at 298.15 K in the solvent S ( ∆ soln H Ai /S (cr, 298.15 K)) may be represented as a sum of the fusion enthalpy of Ai at 298.15 K ( ∆ lcr H Ai (298.15 K)) and enthalpy of solution of compound Ai in a hypothetical liquid state in a solvent S at 298.15 K

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( ∆ soln H Ai /S (l, 298.15 K)) (3):

∆ soln H Ai /S (cr, 298.15 K)= ∆ lcr H Ai (298.15 K)+ ∆ soln H Ai /S (l, 298.15 K)

(3)

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If solute and solvent have similar physical-chemical properties and structure, ∆ soln H Ai /S (l,

298.15 K) is close to zero. There are many examples (Solomonov et al, 1984 [13], Fuchs et al, 1985 [14]) when the enthalpies of solution of various benzene derivatives in benzene do not exceed 1 kJ·mol-1. Thus, according to Eq. (3) ∆ soln H Ai /S (cr, 298.15 K) is approximately equal to ∆ lcr H Ai (298.15 K). However, pursuant to works [10, 11] fusion enthalpies at Tm are approximately equal to the enthalpies of solution of aromatic hydrocarbons and its derivatives. Therefore, a new equation for calculation of sublimation enthalpy where, in contradistinction to Eq. (1), ∆ soln H Ai /S (298.15 K) is replaced by ∆ lcr H Ai (Tm) was proposed. Additionally, considering all polymorphic transitions enthalpies ( ∆ trns H Ai (Ttrns)) happening between 298.15 K and melting temperature, we may write the following equation:

ACCEPTED MANUSCRIPT ∆ H (298.15 K) = ∆ crl H Ai (Tm ) + ∑ ∆ trns H Ai (Ttrns ) − ∆solv H Ai /S (298.15 K) g cr

Ai

(4)

Obviously, the enthalpies of solution in benzene of compounds that are self-associated due to hydrogen bonding (for example, carboxylic acids, phenols, anilines, amides) should differ from zero because solution under infinite dilution is accompanied by the rupture of solute-solute hydrogen bonds. Benzene is the weaker proton acceptor and it cannot compensate breaking

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hydrogen bonds. Currently available data on solution enthalpies of liquid m-fluorophenol and aniline in benzene at 298.15 K (7.5 kJ·mol-1 [15] and 5.2 kJ·mol-1 [16] respectively) prove this supposition. In accordance with Eq. (3), ∆ soln H Ai /S (cr, 298.15 K) differs from fusion enthalpy of compound Ai at Tm by the value equal to ∆ soln H Ai /S (l, 298.15 K). Eq. (4) cannot be used for

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computation of sublimation enthalpy under such conditions.

In the present work, we propose a way to overcome this problem. It may be shown on the

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example of calculation of sublimation enthalpies of benzoic acid (BA) derivatives using fusion enthalpies at Tm. Solvation enthalpy of benzoic acid in benzene is the difference between its enthalpy of solution in benzene at 298.15 K ( ∆soln H BA/C6 H6 (298.15 K)) and enthalpy of sublimation at 298.15 K ( ∆ gcr H BA (298.15 K)):

∆ solv H BA/C6 H6 (298.15 K) = ∆soln H BA/C6 H6 (298.15 K) - ∆ gcr H BA (298.15 K)

(5)

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We assume that, excluding the enthalpy of solid-solid transitions from 298.15 К to Tm, ∆soln H BA/C6 H6 (cr, 298.15 K) may be represented as a sum of the fusion enthalpy at Tm

( ∆ lcr H BA (Tm)) and the solution enthalpy of benzoic acid (in liquid state at 298.15 K) in benzene

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( ∆soln H BA/C6 H6 (l, 298.15 K)):

∆soln H BA/C6 H6 (cr, 298.15 K)= ∆ lcr H BA (Tm)+ ∆soln H BA/C6 H6 (l, 298.15 K)

(6)

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Combining (5) and (6), we may write the enthalpy of solvation of benzoic acid in benzene through the following equation: ∆ solv H BA/C6 H6 (298.15 K)= ∆ lcr H BA (Tm)+ ∆soln H BA/C6 H6 (l, 298.15 K)- ∆ gcr H BA (298.15 K) (7)

On the other hand, according to Eq. (2), solvation enthalpies of benzoic acid derivatives in benzene ( ∆ solv H BA(Xi )n /C6 H6 ) may be expressed as follows: ∆ solv H BA(Xi )n /C6 H6 (298.15 K)= ∆ solv H BA/C6 H6 (298.15 K)+ n ⋅ ∆ solv H Xi →H/C6 H6 =

= ∆ lcr H BA (Tm)+ ∆soln H BA/C6 H6 (l, 298.15 K)- ∆ gcr H BA (298.15 K)+ n ⋅ ∆ solv H Xi →H/C6 H6 According to Eq. (8) and considering Eqs. (1) and (6), we can write the following equation: ∆ gcr H BA(Xi )n (298.15 K) = ∆ lcr H BA(Xi )n (Tm)+ ∆ soln H BA(Xi )n /C6 H6 (l, 298.15 K) - [ ∆ lcr H BA (Tm)+

(8)

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+ ∆soln H BA/C6 H6 (l, 298.15 K)- ∆ gcr H BA (298.15 K)]- n ⋅ ∆ solv H Xi →H/C6 H6

(9)

We expect that the substituents in the aromatic ring weakly influence on ∆ soln H BA(Xi )n /C6 H6 (l, 298.15 K): ∆ soln H BA(Xi )n /C6 H6 (l, 298.15 K) ≈ ∆soln H BA/C6 H6 (l, 298.15 K)

(10)

Eq. (10) may be explained by the fact that magnitudes of hydrogen bonds between

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studied compounds and benzene are not absent but weak. Consequently, the effect of substituents on the enthalpy of hydrogen bond is negligible. It should be borne in mind that insertion of substituent that is capable of hydrogen bonding (-OH, -COOH, -NHR, -NHCOOR) strongly increases specific interactions energy with solvent while influence of another substituents is

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vanishing even in case of much more basic solvents than benzene [7].

Further, ∆ lcr H BA (Tm)- ∆ gcr H BA (298.15 K)= 18.0 [17]-89.7 [17]=-71.7 kJ·mol-1. Therefore, the enthalpies of sublimation of benzoic acids derivatives may be expressed as follows:

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∆ gcr H BA(Xi )n (298.15 K)= ∆ lcr H BA(Xi )n (Tm)-(-71.7)- n ⋅ ∆ solv H Xi →H/C6 H6

(11)

In the presence of polymorphic transitions between 298.15 K and Tm it is necessary to add the enthalpy of each transition to sublimation enthalpy.

Eq. (11) must be modified to calculate the sublimation enthalpies of aromatic and heteroaromatic carboxylic acids. The value of -71.7 kJ·mol-1 substantially represents the

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enthalpy of solvation of benzoic acid in benzene plus ∆soln H BA/C6 H6 (l, 298.15 K), consequently: ∆ soln H BA/C6 H6 (l, 298.15 K) = 71.7+ ∆ solv H BA/C6 H6 (298.15 K)

(12)

Then, in accordance with Eqs. (11) and (12), the enthalpy of sublimation of aromatic or

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heteroaromatic carboxylic acid ( ∆ gcr H ArCOOH ) may be calculated by the following equation: ∆ gcr H ArCOOH (298.15 K)= ∆ lcr H ArCOOH (Tm)- ∆ solv H ArH/C6 H6 (298.15 K)- n ⋅ ∆ solv H Xi →H/C6 H6 +36.9 (13),

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where ∆ lcr H ArCOOH (Tm) - enthalpy of fusion at Tm, ∆ solv H ArH/C6 H6 - solvation enthalpy of aromatic or heteroaromatic compound in benzene, ∆ solv H Xi →H/C6 H6 - solvation enthalpy of group contribution, 36.9 kJ·mol-1– difference between -71.7 kJ·mol-1 and -34.8 kJ·mol-1 (solvation enthalpy of benzene in benzene that is equal to negative vaporization enthalpy of benzene at 298.15 K [6]). Solvation enthalpies of substituted aromatic and heteroaromatic hydrocarbons in benzene are calculated using Eq. (2). Sublimation enthalpies of dicarboxylic acids were calculated as a sum of the values of 36.9 kJ·mol-1, 71.7 kJ·mol-1 and fusion enthalpy of dicarboxylic acid. Enthalpies of polymorphic phase transitions should be also considered. The details of the calculations are fully described in Supplementary material. Calculated sublimation enthalpies of

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benzoic acid derivatives and aromatic or heteroaromatic carboxylic acids ( ∆ gcr H ArCOOH ) at 298.15 K are presented in Table 1. Table 1

3. Results and discussion In appliance with Eqs. (11) and (13), the quality of convergence of results represented in

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the last two columns (Table 1) depends on both the ∆ lcr H Ai (Tm) and ∆ gcr H Ai (298.15 K) literature values. Unfortunately, analysis of published data on fusion and sublimation enthalpies gives no opportunity to make a choice in favor of one or another magnitude. For example, in [18] seven fusion enthalpy values of nicotinic acid spread from 12.4 to 30.0 kJ·mol-1 and five

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sublimation enthalpy values are in the range from 103.8 to 124.4 kJ·mol-1. The newer data on this compound is also available (Table S1). Apparently, it is pointless to use average values of

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phase transition enthalpies in such cases. Therefore, we use average values of the fusion enthalpies when the divergence of literature values is less than 3 kJ·mol-1. In addition, such ambiguous results shutter confidence in the values measured once or limited number of times. If the divergence of literature data exceeds 3 kJ·mol-1, then sublimation enthalpies were calculated separately for each ∆ lcr H Ai (Tm) value (Table 1). All data necessary for evaluation of average

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values are given in Table S1. Literature data of sublimation enthalpies of substituted benzoic acids at 298.15 K are compiled in Table 2.

For a number of acids the strongly underestimated sublimation enthalpy values may be found in the literature. We put such values in the Table 2, but did not consider it in the statistical

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treatment. Five benzoic acid derivatives (4-iodobenzoic acid, 2,3-dimethylbenzoic acid, 2,5dibromobenzoic acid, 3-methylbenzoic acid, 4-nitrobenzoic acid) show bad convergence with

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the scheme. The comparison graph with markers of these (red points) and other benzoic acid derivatives and aromatic or heteroaromatic carboxylic acids is provided (Fig 1). Fig. 1

Uncertainties of experiments for each compound are calculated as a variance of mean

literature data if several points were available. Average absolute deviation between experimental and estimated sublimation enthalpy values is 1.9 kJ·mol-1. Table 2 We also made a comparison between the values obtained by our method and the results of a paper-based scheme proposed by Monte et. al. [48], which uses linear regression analysis.

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Good convergence of values in this comparison also shows robustness of our method and of its underlying assumptions. We divided benzoic acids into several classes and analyzed each of them. The difference of 3 kJ·mol-1 between calculated and literature values of sublimation enthalpies is assumed to be satisfactory; if the scatter exceeds 3 kJ·mol-1, it is unacceptable. Value (3 kJ·mol-1) was estimated as an average uncertainties of Eqs. (11) and (13) combined from uncertainties of the

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solvation enthalpy values (approx.1 kJ·mol-1), uncertainty of Eq. (6) (approx. 1.4 kJ·mol-1), uncertainty of Eq. (10) and uncertainties of the fusion enthalpies (approx. 0.5 kJ·mol-1).

3.1 Halogen-substituted benzoic acids

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The differences between the calculated and literature sublimation enthalpies (Table 2) of o- and m-fluorobenzoic acids are slightly less than 3 kJ·mol-1. The values of p-fluorobenzoic acid

fusion enthalpy determination.

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are in good agreement, considering the experimental errors associated to the sublimation and

Calculations results for chloro- and bromo-substituted are in agreement with literature (Table 2), considering the dispersion of known values. The only large difference is observed in the case of o-bromobenzoic acid (4.2 kJ·mol-1).

Our approach also presents an acceptable congruence in the case of o-iodobenzoic acid (if

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the average fusion enthalpy 26.9 kJ·mol-1 (Table S1) is used) and m-iodobenzoic acid. However, a minimal difference is found between calculated and literature values for p-iodobenzoic acid: 7.1 kJ·mol-1 (Table 2).

Comparison of published data and the values obtained by our approach for 2,5-

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dibromobenzoic and 3,5-dibromobenzoic acids gives a good agreement in the case of 3,5-

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dibromobenzoic acid. However, results for 2,5-dibromobenzoic acid differ by 6.6 kJ·mol-1.

3.2 Alkyl-substituted benzoic acids Generally our method demonstrates a reliable agreement with literature (Table 2) in case

of alkylsubstituted benzoic acids. Compared to the other alkyl-substituted acids, incongruence with literature for m-methylbezoic acid (5.9 kJ·mol-1) and 2,3-dimethylbenzoic acid (7.6 kJ·mol1

) can be hardly explained rationally.

3.3 Methoxybenzoic acids All the experimental values for the three isomers of methoxybenzoic acids show a good correspondence with literature data and sublimation enthalpies calculated according to Eq. (11) (Table 2).

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difficult to explain.

3.5 Monomethylbenzodicarboxylates

Divergence of 3.0 kJ·mol-1 is observed for monomethyl phthalate. In the case of

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monomethyl isophthalate the concordance is acceptable. Two literature sublimation enthalpies were found in the literature for monomethyl terephthalate: 124.1 kJ·mol-1 [33] and 130.41

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kJ·mol-1 [34]. The calculated value (129.7 kJ·mol-1) is closer to the latter value.

3.6 Naphthoic acids

Calculated and literature values for 1-naphthoic acid are in good agreement, considering

experimental error of sublimation and fusion enthalpies determination. Three values of sublimation enthalpy are known for 2-naphthoic acid: 124.6 kJ·mol-1 [35], 117.2 kJ·mol-1 [37]

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and 115.6 kJ·mol-1 [36]. Our value of 115.6 kJ·mol-1 is closer to the latter two results.

3.7 Carboxyl containing heterocyclic compounds There is a large spread of the fusion and sublimation enthalpies of nicotinic acid. It is

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difficult to draw conclusions about the concordance of results in this instance. However, the calculated sublimation enthalpies of furanecarboxylic and thiophenecarboxylic acids fit with

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published values well (Table 2).

3.8 Dicarboxylic acids

Sublimation enthalpies of dicarboxylic acids were determinated. However, reliable

determined fusion enthalpies are necessary. A large spread of literature fusion enthalpies from 33.1 [49] or 43.2 kJ·mol-1 [50] to 49.1 kJ·mol-1 [51] for isophthalic acid and from 41.5 kJ·mol-1 [49] to 63.4 [52] kJ·mol-1 for terephthalic acid. For calculation of sublimation enthalpies of isophthalic and terephthalic acids the fusion enthalpies were take from [49].

3.9 Summary of results of usage of proposed method

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Each of analyzed classes shows a good convergence. Sporadic disparities within some of classes now can be hardly explained. They do not correlate with substituent position and are not specific for concrete substituent. To sum up, we can conclude that Eqs. (11) and (13) demonstrate reliable consilience of the calculated and experimental values. This equation based on substantially experimental data connects the sublimation enthalpy under the standard conditions and fusion enthalpy at the

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melting point. Thus, it can be applied to estimate or validate one of these values if the other one is already approved.

Conclusion

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A new approach for estimation of the enthalpy of sublimation of carboxyl containing aromatic and heteroaromatic compounds with use of their fusion enthalpy at the melting point is

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proposed. Estimation of the fusion enthalpy may be also a non-trivial task for some compounds. In such cases, this value may be calculated through experimental sublimation enthalpy considering polymorphic phase transitions.

Acknowledgements

Authors would like to acknowledge Prof. Sergey P. Verevkin from the University of

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Rostock for the consultation of values of sublimation enthalpies determined by conventional methods.

This work has been performed according to the Russian Government Program of Competitive Growth of Kazan Federal University and Russian Foundation for Basic Research

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No. 15-03-07475. B.S. gratefully acknowledges the financial support by the Russian Ministry of

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Education and Science.

References

[1] S.P. Verevkin, 2 Phase changes in purecomponent systems: Liquids and gases, in: R.D. Weir, T.W.D. Loos (Eds.) Experimental Thermodynamics, Elsevier, 2005, pp. 5-30. [2] A.R.R.P. Almeida, M.J.S. Monte, A brief review of the methods used to evaluate vapour pressures and sublimation enthalpies, Struc. Chem. 24 (2013) 1993-1997. [3] B.N. Solomonov, M.A. Varfolomeev, R.N. Nagrimanov, V.B. Novikov, D.H. Zaitsau, S.P. Verevkin, Solution calorimetry as a complementary tool for the determination of enthalpies of vaporization and sublimation of low volatile compounds at 298.15 K, Thermochim. Acta 589 (2014) 164-173.

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[4] B.N. Solomonov, M.A. Varfolomeev, R.N. Nagrimanov, V.B. Novikov, M.A. Ziganshin, A.V. Gerasimov, S.P. Verevkin, Enthalpies of vaporization and sublimation of the halogensubstituted aromatic hydrocarbons at 298.15 K: Application of solution calorimetry approach, J. Chem. Eng. Data 60 (2015) 748-761. [5] M.A. Varfolomeev, V.B. Novikov, R.N. Nagrimanov, B.N. Solomonov, Modified solution calorimetry approach for determination of vaporization and sublimation enthalpies of branched-

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chain aliphatic and alkyl aromatic compounds at 298.15 K., J. Chem. Thermodyn. 91 (2015) 204-210.

[6] B.N. Solomonov, M.A. Varfolomeev, R.N. Nagrimanov, V.B. Novikov, A.V. Buzyurov, Y.V. Fedorova, T.A. Mukhametzyanov, New method for determination of vaporization and

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sublimation enthalpy of aromatic compounds at 298.15 K using solution calorimetry technique and group-additivity scheme, Thermochim. Acta 622 (2015) 88-96.

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[7] R.N. Nagrimanov, A.A. Samatov, B.N. Solomonov, Non-additivity in the solvation enthalpies of substituted phenols and estimation of their enthalpies of vaporization/sublimation at 298.15K, J. Mol. Liq. 221 (2016) 914-918.

[8] R.N. Nagrimanov, B.N. Solomonov, V.N. Emel’yanenko, S.P. Verevkin, Six-membered ring aliphatic compounds: structure-property relationships in phase transitions, Thermochim. Acta, 638 (2016) 80-88.

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[9] V.N. Emel’yanenko, R.N. Nagrimanov, B.N. Solomonov, S.P. Verevkin, Adamantanes: benchmarking of thermochemical properties, J. Chem. Thermodyn. 101 (2016) 130-138. [10] B.N. Solomonov, M.A. Varfolomeev, R.N. Nagrimanov, T.A. Mukhametzyanov, V.B. Novikov, Enthalpies of solution, enthalpies of fusion and enthalpies of solvation of polyaromatic

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hydrocarbons: instruments for determination of sublimation enthalpy at 298.15 K, Thermochim. Acta 622 (2015) 107–112.

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[11] B.N. Solomonov, R.N. Nagrimanov, M.A. Varfolomeev, A.V. Buzyurov, T.A. Mukhametzyanov, Enthalpies of fusion and enthalpies of solvation of aromatic hydrocarbons derivatives: Estimation of sublimation enthalpies at 298.15 K, Thermochim. Acta 627–629 (2016) 77-82.

[12] B.N. Solomonov, R.N. Nagrimanov, T.A. Mukhametzyanov, Additive scheme for calculation

of

solvation

enthalpies

of

heterocyclic

aromatic

compounds.

Sublimation/vaporization enthalpy at 298.15 K, Thermochim. Acta 633 (2016) 37-47. [13] B.N. Solomonov, A.I. Konovalov, V.B. Novikov, A.N. Vedernikov, M.D. Borisover, V.V. Gorbachuk, I.S. Antipin, Solvation of organic compounds. Molecular refraction, dipole moment, and enthalpy of solvation, J. Gen. Chem. USSR (Engl.Transl.) 54 (1984) 1444-1453.

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[14] W.K. Stephenson, R. Fuchs, Enthalpies of interaction of aromatic solutes with organic solvents, Can. J. Chem. 63 (1985) 2529-2534. [15] R.S. Drago, M.S. Nozari, G.C. Vogel, A procedure for eliminating and evaluating solvent effect on thermodynamic data for donor-acceptor interactions, J. Am. Chem. Soc. 94 (1972) 9094.

solvents, Can. J. Chem. 63 (1985) 2540-2544.

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[16] W.K. Stephenson, R. Fuchs, Enthalpies of interaction of nitrogen base solutes with organic

[17] W.E. Acree, J.S. Chickos, Phase transition enthalpy measurements of organic and organometallic compounds. Sublimation, vaporization and fusion enthalpies from 1880 to 2010, J. Phys. Chem. Ref. Data 39 (2010) 043101-043101.

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[18] E.M. Gonçalves, C.E.S. Bernardes, H.P. Diogo, M.l.E. Minas da Piedade, Energetics and structure of nicotinic acid (niacin), J. Phys. Chem. B 114 (2010) 5475-5485.

M AN U

[19] K.V. Zherikova, A.A. Svetlov, M.A. Varfolomeev, S.P. Verevkin, C. Held, Thermochemistry of halogenobenzoic acids as an access to PC-SAFT solubility modeling, Fluid Phase Equilib. 409 (2016) 399-407.

[20] F.A. Adedeji, D. Lalage, S. Brown, J.A. Connor, M.L. Leung, I.M. Paz-Andrade, H.A. Skinner, Thermochemistry of arene chromium tricarbonyls and the strenghts of arene-chromium bonds, J. Org. Chem. 97 (1975) 221-228.

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[21] V.N. Emel'yanenko, A. Strutynska, S.P. Verevkin, Enthalpies of Formation and Strain of Chlorobenzoic Acids from Thermochemical Measurements and from ab Initio Calculations, J. Phys. Chem. A 109 (2005) 4375-4380.

[22] M.A.V. Ribeiro da Silva, J.M.S. Fonseca, R.P.B.M. Carvalho, M.J.S. Monte,

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Thermodynamic study of the sublimation of six halobenzoic acids, J. Chem. Thermodyn. 37 (2005) 271-279.

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[23] M.L.C.C.H. Ferrão, G. Pilcher, Enthalpies of combustion of the three bromobenzoic acids by rotating-bomb calorimetry, J. Chem. Thermodyn. 19 (1987) 543-548. [24] Z.C. Tan, R. Sabbah, Thermodynamic study of the three isomers of bromobenzoic acid, Sci. China, Ser. B 37 (1994) 641-652. [25] M.J.S. Monte, D.M. Hillesheim, Thermodynamic study on the sublimation of the three iodobenzoic acids and of 2-fluoro- and 3-fluorobenzoic acids, J. Chem. Thermodyn. 32 (2000) 1727-1735. [26] Z.-C. Tan, R. Sabbah, Thermodynamic study of the three isomers of iodobenzoic acid, Thermochim. Acta 231 (1994) 109-120.

ACCEPTED MANUSCRIPT

[27] S. Vecchio, B. Brunetti, Vapor pressures, standard molar enthalpies, entropies Gibbs energies of sublimation and heat capacities of 2,5- and 3,5-dibromobenzoic acids, Fluid Phase Equilib. 338 (2013) 148-154. [28] S.P. Verevkin, D.H. Zaitsau, V.N. Emeĺyanenko, E.N. Stepurko, K.V. Zherikova, Benzoic acid derivatives: Evaluation of thermochemical properties with complementary experimental and computational methods, Thermochim. Acta, 622 (2015) 18-30.

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[29] M. Colomina, P. Jimenez, M.V. Roux, C. Turrion, Thermochemical properties of benzoic acid derivatives XI. Vapour pressures and enthalpies of sublimation and formation of the six dimethylbenzoic acids, J. Chem. Thermodyn. 16 (1984) 1121-1127.

[30] G.L. Perlovich, T.V. Volkova, A.N. Manin, A. Bauer-Brandl, Extent and Mechanism of

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Solvation and Partitioning of Isomers of Substituted Benzoic Acids: A Thermodynamic Study in the Solid State and in Solution, J. Pharm. Sci. 97 (2008) 3883-3896.

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[31] M.A.V. Ribeiro da Silva, M.A.R. Matos, M.J.S. Monte, D.M. Hillesheim, M.C.P.O. Marques, N.F.T.G. Vieira, Enthalpies of combustion, vapour pressures, and enthalpies of sublimation of three methoxy-nitrobenzoic acids. Vapour pressures and enthalpies of sublimation of the three nitrobenzoic acids, J. Chem. Thermodyn. 31 (1999) 1429-1441. [32] S. Vecchio, B. Brunetti, Vapor pressures and standard molar enthalpies, entropies, and Gibbs free energies of sublimation of 2,4- and 3,4-dinitrobenzoic acids, J. Chem. Thermodyn. 41

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(2009) 880-887.

[33] M.J.S. Monte, C.A.D. Sousa, Vapor pressures and phase changes enthalpy and gibbs energy of three crystalline monomethyl benzenedicarboxylates, J. Chem. Eng. Data 50 (2005) 21012105.

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[34] Y.V. Maksimuk, G.J. Kabo, V.V. Simirsky, A.A. Kozyro, V.M. Sevruk, Standard enthalpies of formation of some methyl esters of benzene carboxylic acids, J. Chem. Eng. Data 43 (1998)

AC C

293-298.

[35] M.V. Roux, M. Temprado, R. Notario, S.P. Verevkin, V.N. Emel'yanenko, D.E. Demasters, J.F. Liebman, The energetics of naphthalene derivatives, III: Phenylacetic acid and the isomeric 1- and 2-naphthylacetic acids, Mol. Phys. 102 (2004) 1909-1917. [36] M. Colomina, M.V. Roux, C. Turrión, Thermochemical properties of naphthalene compounds I. Enthalpies of combustion and formation of the 1- and 2-naphthoic acids, J. Chem. Thermodyn. 6 (1974) 149-155. [37] R. Sabbah, M. Gilbert, A. Julg, Détermination de l'énergie de conjugaison des acides naphtoǐques, Thermochim. Acta 10 (1974) 345-351. [38] E.M. Gonçalves, C.E.S. Bernardes, H.P. Diogo, M.E. Minas da Piedade, Energetics and Structure of Nicotinic Acid (Niacin), J. Phys. Chem. B, 114 (2010) 5475-5485.

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[39] R. Sabbah, S. Ider, Can. J. Chem. 77 (1999) 249-257.

[40] J. Bickerton, G. Pilcher, G. Al-Takhin, Enthalpies of combustion of the three aminopyridines and the three cyanopyridines, J. Chem. Thermodyn. 16 (1984) 373-378. [41] M.D.M.C. Ribeiro Da Silva, J.M. Gonçalves, W.E. Acree Jr, Standard molar enthalpy of sublimation of crystalline 3-pyridinecarboxylic acid, J. Chem. Thermodyn. 32 (2000) 1071-1073. [42] M.V. Roux, M. Temprado, P. Jiménez, J. Pérez-Parajón, R. Notario, Thermochemistry of

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furancarboxylic acids, J. Phys. Chem. A 107 (2003) 11460-11467.

[43] I.B. Sobechko, Y.Y. Van-Chin-Syan, V.V. Kochubei, R.T. Prokop, N.I. Velychkivska, Y.I. Gorak, V.N. Dibrivnyi, M.D. Obushak, Thermodynamic properties of furan-2-carboxylic and 3(2-furyl)-2-propenoic acids, Russ. J. Phys. Chem. A 88 (2014) 2046-2053.

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[44] M. Temprado, M.V. Roux, P. Jiménez, J.Z. Dávalos, R. Notario, Experimental and computational thermochemistry of 2- and 3-thiophenecarboxylic acids, J. Phys. Chem. A 106

M AN U

(2002) 11173-11180.

[45] R. Sabbah, L. Perez, Étude thermodynamique des acides phtalique, isophtalique et téréphtalique, Can. J. Chem. 77 (1999) 1508-1513.

[46] A.A. Kozyro, Yu.V. Maksimuk, G.Ya. Kabo, Thermodynamics of vaporization of phthalic acids and additivity of enthalpies and entropies of sublimation of benzocarboxylic acids, Zh. Prikl. Khim. (S.-Peterburg) 73 (2000) 199.

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[47] R.M. Stephenson, S. Malanowski, Handbook of the Thermodynamics of Organic Compounds, Elsevier, New York, 1987.

[48] M.J.S. Monte, A.R.R.P. Almeida, A new approach for the estimation of sublimation

2016.

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enthalpies and vapor pressures of crystalline benzene derivatives, Struct. Chem. 24 (2013) 2001-

[49] A.M. Booth, T. Bannan, M.R. McGillen, M.H. Barley, D.O. Topping, G. McFiggans, C.J.

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Percival, The role of ortho, meta, para isomerism in measured solid state and derived sub-cooled liquid vapour pressures of substituted benzoic acids, RSC Advances, 2 (2012) 4430-4443. [50] R. Sabbah, L. Perez, Étude thermodynamique des acides phtalique, isophtalique et téréphtalique, Can. J. Chem. 77 (1999) 1508-1513. [51] E. Martin, S.H. Yalkowsky, J.E. Wells, Fusion of Disubstituted Benzenes, J. Pharm. Sci. 68 (1979) 565-568. [52] L. Dian-Qing, L. Jiang-Chu, L. Da-Zhuang, W. Fu-An, Solubilities of terephthalaldehydic, p-toluic, benzoic, terephthalic and isophthalic acids in N,N-dimethylformamide from 294.75 to 370.45 K, Fluid Phase Equilibr. 200 (2002) 69-74.

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Fig. 1

Comparison of calculated values of sublimation enthalpies of benzoic acid derivatives and aromatic or heteroaromatic carboxylic acids using method proposed in this work and literature data.

Table 1

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Calculated sublimation enthalpies of benzoic acid derivatives and aromatic or heteroaromatic carboxylic acids from the literature data of fusion enthalpies at melting temperature by method proposed in this work.

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Table 2

Compilation enthalpies of sublimation of benzoic acid derivatives and aromatic or

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heteroaromatic carboxylic acids.

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Table 1

Calculated sublimation enthalpies of benzoic acid derivatives and aromatic or heteroaromatic carboxylic acid from the literature data of fusion enthalpies at melting temperature by method proposed in this work. - ∆ solv H ArH/C6 H6 -

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2-fluorobenzoic acid 3-fluorobenzoic acid 4-fluorobenzoic acid 2-chlorobenzoic acid 3-chlorobenzoic acid 4-chlorobenzoic acid 2-bromobenzoic acid 3-bromobenzoic acid 4-bromobenzoic acid 2-iodobenzoic acid

86.4

AC C

EP

TE D

3-iodobenzoic acid 4-iodobenzoic acid 2,5-dibromobenzoic acid 3,5-dibromobenzoic acid 2-methylbenzoic acid 3-methylbenzoic acid 4-methylbenzoic acid 2,3-dimethylbenzoic acid 3,5-dimethylbenzoic acid 2-methoxybenzoic acid 3-methoxybenzoic acid 4-methoxybenzoic acid 2-nitrobenzoic acid 3-nitrobenzoic acid 4-nitrobenzoic acid 2,4-dinitrobenzoic acid 3,4-dinitrobenzoic acid monomethyl isophthalate monomethyl terephthalate 1-naphthoic acid 2-naphthoic acid nicotinic acid

86.4 86.4 89.1 89.1 75.2 75.2 75.2 78.7 78.7 83.3 83.3 83.3 89.6 89.6 89.6 107.5 107.5 92.1 92.1 91.8 91.8 77.1

2-furancarboxylic acid 3-furancarboxylic acid 2-thiophenecarboxylic acid 3-thiophenecarboxylic acid isophthalic acid terephthalic acid

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n ⋅ ∆ solv H Xi →H/C6 H6 +36.9 kJ·mol-1 71.3 71.3 71.3 77.8 77.8 77.8 80.4 80.4 80.4

Compound Ai

∆ lcr H ArCOOH (Tm)a kJ·mol-1

64.3 64.3 71.4 71.4 108.6 108.6

20.2 18.5 21.3 25.7 23.2 32.4 23.9 24.9 30.9 21.4 26.9 28.2 34.3 36.7 29.4 20.0 15.7 22.5 18.3 22.6 23.8 23.4 28.8 28.0 19.3 36.9 30.6 24.6 36.5 37.6 21.3 23.8 12.7 23.1 28.8 23.0 21.3 21.0 18.3 33.1 41.5

∆ gcr H ArCOOH (298.15 K)b kJ·mol-1 91.5 89.8 92.6 103.5 101.0 110.2 104.3 105.3 111.3 107.8 113.3 114.6 120.7 125.8 118.5 95.2 90.9 97.7 97.0 101.3 107.1 106.7 112.1 117.6 108.9 126.5 138.1 132.1 128.6 129.7 113.1 115.6 89.8 100.2 105.9 87.3 85.6 92.4 89.7 141.7 150.1

ACCEPTED MANUSCRIPT b

a

Sublimation enthalpy at 298.15 K calculated using

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Fusion enthalpy at melting temperature. Eqs. (11) and (13).

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Table 2

Compilation enthalpies of sublimation of benzoic acid derivatives and aromatic or heteroaromatic carboxylic acid.

3-fluorobenzoic acid 4-fluorobenzoic acid 2-chlorobenzoic acid

TE D

4-chlorobenzoic acid

2-bromobenzoic acid

AC C

EP

3-bromobenzoic acid

4-bromobenzoic acid

2-iodobenzoic acid

3-iodobenzoic acid

J·mol-1·K-1 164.9

93.4±0.6

164.9

60.3±0.1

164.9

101.3 100.0±0.5 105.1±0.4 99.9±0.4

168.8

99.6 100.5±0.4 101.2±0.4 98.8±0.8

168.8

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3-chlorobenzoic acid

∆Cpcr a

∆ gcr H (T) kJ·mol-1 95.3±0.6

298.15 298.15 298.15 298.15 298.15 298.15

101.9 99.3±0.4 103.3±0.5 105.7±0.8

168.8

108.5±0.6 110.9±1.1 95.9±0.4

172.5

105.9±0.7 105.0±1.1 99.2±0.2

172.5

110.1±0.8 107.6±1.1 103.1±0.6

172.5

111.9±0.7 112.8±2.0 92.59±0.2

168.0

110.1±0.6 111.1±1.9 96.4±0.3

∆ gcr H (298.15 K)b kJ·mol-1 95.3±0.6 91.5 93.4±0.6 89.8 93.5±0.6 92.6 101.3 100.6±0.5 105.8±0.4 101.5±0.4 103.5 102.2 101.1±0.4 101.9±0.4 100.6±0.8 101.0 105.0 101.0±0.4 104.5±0.5 107.9±0.8 110.2 108.5±0.6 110.9±1.1 95.9±0.4 104.3 105.9±0.7 105.0±1.1 99.2±0.2 105.3 110.1±0.8 107.6±1.1 103.1±0.6 111.3 111.9±0.7 112.8±2.0 92.59±0.2 103±0.4 107.8 113.3 110.1±0.6 111.1±1.9 96.38±0.29 114.6

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2-fluorobenzoic acid

T K 298.15 298.15 298.15 298.15 298.15 298.15 298.15 323.1 330.2 370.4 298.15 414.0 323.1 330.1 376.3 298.15 413.0 363.1 344.7 378.4 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15

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Compound

168.0

Ref. [19] this work [19] this work [19] this work [20] [21] [22] [21] this work [20] [21] [22] [21] this work [20] [21] [22] [21] this work [22] [23] [24] this work [22] [23] [24] this work [22] [23] [24] this work [19] [25] [26] this work this work [19] [25] [26] this work

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3,5-dibromobenzoic acid

2-methylbenzoic acid 3-methylbenzoic acid 4-methylbenzoic acid 2,3-dimethylbenzoic acid

2-methoxybenzoic acid 3-methoxybenzoic acid

3-nitrobenzoic acid

EP

4-nitrobenzoic acid

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4-methoxybenzoic acid 2-nitrobenzoic acid

AC C

2,4-dinitrobenzoic acid 3,4-dinitrobenzoic acid

monomethyl isophthalate

monomethyl terephthalate

1-naphthoic acid

2-naphthoic acid

168.0

99.3±0.4 133.6±1.0 132.4±3.0

195.9

120.3±1.0 120.4±3.0

195.9

96.2±0.3

176.7

96.8±0.5

176.7

97.0±0.3

176.7

104.6±0.4 102.3±0.3

204.3 204.3

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3,5-dimethylbenzoic acid

110.1±0.6

112.2±0.6 112.9±2.5 99.32±0.36 120.7 133.6±1.0 132.4±3.0 125.8 120.3±1.0 120.4±3.0 118.5 96.2±0.3 95.2 96.8±0.5 90.9 97.0±0.3 97.7 104.6±0.4 97.0 102.3±0.3 101.3 106.6±0.2 107.1 114.7±0.8 108.5±0.7 106.7 112.2±0.4 112.1 118.7±0.5 117.6 110.0±0.4 108.9 119.2±0.6 126.5 134±3.0 138.1 129±3.0 132.1 125.6±1.0 128.6 124.1±1.0 130.4±0.5 129.7 112.3±0.9 112.0 113.6 113.1 124.6±1.0 115.6 117.2

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2,5-dibromobenzoic acid

298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 350.5 298.15 298.15 298.15 355.6 298.15

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4-iodobenzoic acid

106.6±0.2

226.5

114.7±0.8 108.5±0.7

226.5

112.2±0.4

226.5

118.7±0.5

196.2

110.0±0.4

196.2

119.2±0.6

196.2

134±3.0

243.3

129±3.0

243.3

125.6±1.0

217.0

124.1±1.0 130.4±0.5

217.0

112.3±0.9 110.4±0.2 113.6

201.1

124.6±1.0 113.6±0.8 117.2

201.1

[19] [25] [26] this work [27] [27] this work [27] [27] this work [28] this work [28] this work [28] this work [29] this work [29] this work [28] this work [30] [28] this work [28] this work [31] this work [31] this work [31] this work [32] this work [32] this work [33] this work [33] [34] this work [35] [36] [37] this work [35] [36] [37]

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3-furancarboxylic acid 2-thiophenecarboxylic acid 3-thiophenecarboxylic acid

145.5

88.2±1.5 92.8±2.3

123.8

86.6±0.5

123.8

91.2±1.3

132.3

91.9±0.9 142±0.7 134.6±1.6 114.2

132.3

193.2

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isophthalic acid

112.1±0.5 103.8±1.2 123.4±1.2 124.4±0.6 109.2

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2-furancarboxylic acid

298.15 298.15 298.15 298.15 366.5 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 450.0 508.0 298.15 298.15 471.0 538.0 298.15

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nicotinic acid

terephthalic acid

193.2

this work [38] [39] [40] [41] [18] this work this work this work [42] [43] this work [42] this work [44] this work [44] this work [45] [46] [47] this work [45] [46] [47] this work

Calculated according to the procedure developed by Chickos et al [17]. b Estimated sublimation enthalpy by Chickos et al[17].

AC C

EP

TE D

a

146.6±0.5 142.2±1.2 139.2

115.6 112.1±0.5 103.8±1.2 123.4±1.2 124.4±0.6 110.7 89.9 100.2 105.9 88.2±1.5 92.8±2.3 87.3 86.6±0.5 85.6 91.2±1.3 92.4 91.9±0.9 89.7 142±0.7 139.1 120.4 141.7 146.6±0.5 147.3 146.3 150.1

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EP

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SC

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•

Method of estimation of sublimation enthalpy of benzoic acid derivatives was developed.

•

Sublimation enthalpies of 38 benzoic acid derivatives were calculated from the fusion

enthalpies.

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Obtained sublimation enthalpies are in good agreement with the literature data.

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•