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Comments on “Solubility and thermodynamic properties of 5-nitrofurazone form γ in mono-solvents and binary solvent mixtures”
Accepted Manuscript Comments on “Solubility and thermodynamic properties of 5-nitrofurazone form γ in mono-solvents and binary solvent mixtures”
William E. Acree PII: DOI: Reference:
S0167-7322(18)36263-9 https://doi.org/10.1016/j.molliq.2018.12.086 MOLLIQ 10162
To appear in:
Journal of Molecular Liquids
Received date: Accepted date:
1 December 2018 14 December 2018
Please cite this article as: William E. Acree , Comments on “Solubility and thermodynamic properties of 5-nitrofurazone form γ in mono-solvents and binary solvent mixtures”. Molliq (2018), https://doi.org/10.1016/j.molliq.2018.12.086
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.
ACCEPTED MANUSCRIPT Comments on “Solubility and thermodynamic properties of 5-nitrofurazone form γ in monosolvents and binary solvent mixtures” William E. Acree, Jr.*
IP
T
Department of Chemistry, University of North Texas, Denton, TX 76203, USA
CR
Abstract
US
A polemic is given concerning the thermodynamic dissolution properties in the published paper by Li and coworkers [J. Mol. Liq. 275 (2019) 815-828]. The published numerical values do not
AN
obey the standard thermodynamic relationship given by ΔdissG = ΔdissH - T ΔdissS, where ΔdissG,
PT
Key Words and Phrases:
ED
M
ΔdissH and ΔdissS refer to the Gibbs energy, enthalpy and entropy of dissolution.
Thermodynamic mixing properties; Thermodynamic dissolution properties; Solubility;
AC
CE
Thermodynamic consistency
________________________________________________________________________ *To whom correspondence should be addressed. (E-mail: [email protected]); fax: 940-565-4318.
ACCEPTED MANUSCRIPT In a recent paper published in The Journal of Molecular Liquids, Li and coworkers [1] reported the solubility and thermodynamic properties for dissolving the γ-form of 5-nitrofurazone in water, in eight organic mono-solvents, and in binary (water + N,N-dimethylformamide) and binary (N,N-dimethylformamide + isopropanol) solvent mixtures. Solubilities were determined at
T
several temperatures from 278.15 K to 313.15 K using a spectrophotometric method of analysis.
IP
The authors calculated the Gibbs energy (ΔmixG), enthalpy (ΔmixH) and entropy (ΔmixS) of mixing
CR
based on the NRTL model and experimental mole fraction solubility data.
Dissolution
US
thermodynamic properties were also reported in the published paper based on Eqns. 1 - 3 (Eqns. 30 - 32 in reference 1):
AN
ΔdissH = xN ΔfusH + ΔmixH
M
ΔdissS = xN ΔfusS + ΔmixS
ED
ΔdissG = ΔdissH - T ΔdissS
(1) (2) (3)
PT
where xN, ΔfusH and ΔfusS refer to the mole fraction solubility, enthalpy of fusion (ΔfusH = 32971 J mol-1) and entropy of fusion (ΔfusS = 64.79 J K-1 mol-1) of the γ-form of 5-nitrofurazone.
CE
In reading the published paper I found numerous arithmetic errors. First, the authors’
AC
tabulated thermodynamic dissolution properties given in Table 11 [1] do not obey the standard thermodynamic relationship given by Eqn. 3. For example, substitution of the numerical values of ΔdissH = 913 kJ mol-1 and ΔdissS = 253.0 J K-1 mol-1 from Table 11 for the binary (water + N,Ndimethylformamide) solvent mixture at xDMF = 0.9005 and T = 278.15 K into Eqn. 3 gives: ΔdissG = 913,000 J mol-1 - (278.15 K) (253.0 J K-1 mol-1)
(4)
ΔdissG = 842,628 J mol-1
(5)
ACCEPTED MANUSCRIPT ΔdissG = 842.628 kJ mol-1
(6)
which differs significantly from the value of ΔdissG = - 0.9457 kJ mol-1 that the authors list in Table 11. All sets of thermodynamic dissolution values in Table 11 show similar inconsistencies. Interchange of the numerical values in the ΔdissH and ΔdissS in the above calculation gives:
IP
T
ΔdissG = 253,000 J mol-1 - (278.15 K) (913.0 J K-1 mol-1)
(8)
CR
ΔdissG = -0.951 kJ mol-1
(7)
which is good agreement with the value of ΔdissG = - 0.9457 kJ mol-1 in Table 11. It is possible to
US
nearly eliminate the internal inconsistencies by interchanging the numerical values in the ΔdissH
AN
and ΔdissS columns of Table 11.
Second there are inconsistencies between the thermodynamic mixing properties given in
M
Table 9 and the thermodynamic dissolution properties given in Table 11. The tabulated numerical
ED
values do not obey Eqns. 1 and 2. For example, substitution of the enthalpy of mixing of ΔmixH =
PT
252.4 kJ mol-1 for the binary (water + N,N-dimethylformamide) solvent mixture at xDMF = 0.9005 and T = 278.15 K, along with the measured solubility xN = 0.01786 from Table 5 and estimated
CE
enthalpy of fusion of ΔfusH = 32971 J mol-1, into Eqn. 1 yields:
AC
ΔdissH = (0.01786) (32.971 kJ mol-1) + 252.4 kJ mol-1 ΔdissH = 252.99 kJ mol-1
(9) (10)
which differs significantly from the value of ΔdissH = 913.00 kJ mol-1 that the authors give in Table 11. All sets of thermodynamic mixing and dissolution values in Tables 9 and 11 show similar inconsistencies. As an information note, the calculated value of 252.99 agrees with the value of
ACCEPTED MANUSCRIPT 253.00 listed in the ΔdissS column, thus providing further evidence that the numerical values in the ΔdissH and ΔdissS columns of Table 11 should perhaps be interchanged. I also note that the numerical values of the enthalpy of mixing that the authors report for dissolving 5-nitrofurazone in binary (water + N,N-dimethylformamide) and binary (N,N-
T
dimethylformamide + isopropanol) solvent mixtures seem abnormally large when compared with
IP
dissolving 5-nitrofurazone in water and in the eight organic mono-solvents. For the organic mono-
CR
solvents the values of ΔmixH were in the ΔmixH = 1 J mol-1 to ΔmixH = 23,000 J mol-1 range, which
US
were much smaller than the values of ΔmixH = 6 kJ mol-1 to ΔmixH = 1,800 kJ mol-1 given for the two binary solvent systems. Readers should exercise caution in using values from Tables 9 and
AN
11 as it is hard to believe that the mixing values for the mono-solvent systems should be so much
M
different from the mixing values for the binary solvent systems. As noted above, there are
ED
problems with the published values in both tables.
CE
X. Li, X. Huang, Y. Luan, J. Li, N. Wang, X. Zhang, S. Ferguson, X. Meng, H. Hao, Solubility and thermodynamic properties of 5-nitrofurazone form γ in mono-solvents and binary solvent mixtures. J. Mol. Liq. 275 (2019) 815-828.
AC
[1]
PT
References
ACCEPTED MANUSCRIPT HIGHLIGHTS Inconsistencies found in authors’ calculated thermodynamic properties of dissolution
Calculated thermodynamic dissolution properties do not obey ΔdissG = ΔdissH - T ΔdissS
Thermodynamic mixing and dissolution properties are also not internally consistent
AC
CE
PT
ED
M
AN
US
CR
IP
T
William E. Acree PII: DOI: Reference:
S0167-7322(18)36263-9 https://doi.org/10.1016/j.molliq.2018.12.086 MOLLIQ 10162
To appear in:
Journal of Molecular Liquids
Received date: Accepted date:
1 December 2018 14 December 2018
Please cite this article as: William E. Acree , Comments on “Solubility and thermodynamic properties of 5-nitrofurazone form γ in mono-solvents and binary solvent mixtures”. Molliq (2018), https://doi.org/10.1016/j.molliq.2018.12.086
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.
ACCEPTED MANUSCRIPT Comments on “Solubility and thermodynamic properties of 5-nitrofurazone form γ in monosolvents and binary solvent mixtures” William E. Acree, Jr.*
IP
T
Department of Chemistry, University of North Texas, Denton, TX 76203, USA
CR
Abstract
US
A polemic is given concerning the thermodynamic dissolution properties in the published paper by Li and coworkers [J. Mol. Liq. 275 (2019) 815-828]. The published numerical values do not
AN
obey the standard thermodynamic relationship given by ΔdissG = ΔdissH - T ΔdissS, where ΔdissG,
PT
Key Words and Phrases:
ED
M
ΔdissH and ΔdissS refer to the Gibbs energy, enthalpy and entropy of dissolution.
Thermodynamic mixing properties; Thermodynamic dissolution properties; Solubility;
AC
CE
Thermodynamic consistency
________________________________________________________________________ *To whom correspondence should be addressed. (E-mail: [email protected]); fax: 940-565-4318.
ACCEPTED MANUSCRIPT In a recent paper published in The Journal of Molecular Liquids, Li and coworkers [1] reported the solubility and thermodynamic properties for dissolving the γ-form of 5-nitrofurazone in water, in eight organic mono-solvents, and in binary (water + N,N-dimethylformamide) and binary (N,N-dimethylformamide + isopropanol) solvent mixtures. Solubilities were determined at
T
several temperatures from 278.15 K to 313.15 K using a spectrophotometric method of analysis.
IP
The authors calculated the Gibbs energy (ΔmixG), enthalpy (ΔmixH) and entropy (ΔmixS) of mixing
CR
based on the NRTL model and experimental mole fraction solubility data.
Dissolution
US
thermodynamic properties were also reported in the published paper based on Eqns. 1 - 3 (Eqns. 30 - 32 in reference 1):
AN
ΔdissH = xN ΔfusH + ΔmixH
M
ΔdissS = xN ΔfusS + ΔmixS
ED
ΔdissG = ΔdissH - T ΔdissS
(1) (2) (3)
PT
where xN, ΔfusH and ΔfusS refer to the mole fraction solubility, enthalpy of fusion (ΔfusH = 32971 J mol-1) and entropy of fusion (ΔfusS = 64.79 J K-1 mol-1) of the γ-form of 5-nitrofurazone.
CE
In reading the published paper I found numerous arithmetic errors. First, the authors’
AC
tabulated thermodynamic dissolution properties given in Table 11 [1] do not obey the standard thermodynamic relationship given by Eqn. 3. For example, substitution of the numerical values of ΔdissH = 913 kJ mol-1 and ΔdissS = 253.0 J K-1 mol-1 from Table 11 for the binary (water + N,Ndimethylformamide) solvent mixture at xDMF = 0.9005 and T = 278.15 K into Eqn. 3 gives: ΔdissG = 913,000 J mol-1 - (278.15 K) (253.0 J K-1 mol-1)
(4)
ΔdissG = 842,628 J mol-1
(5)
ACCEPTED MANUSCRIPT ΔdissG = 842.628 kJ mol-1
(6)
which differs significantly from the value of ΔdissG = - 0.9457 kJ mol-1 that the authors list in Table 11. All sets of thermodynamic dissolution values in Table 11 show similar inconsistencies. Interchange of the numerical values in the ΔdissH and ΔdissS in the above calculation gives:
IP
T
ΔdissG = 253,000 J mol-1 - (278.15 K) (913.0 J K-1 mol-1)
(8)
CR
ΔdissG = -0.951 kJ mol-1
(7)
which is good agreement with the value of ΔdissG = - 0.9457 kJ mol-1 in Table 11. It is possible to
US
nearly eliminate the internal inconsistencies by interchanging the numerical values in the ΔdissH
AN
and ΔdissS columns of Table 11.
Second there are inconsistencies between the thermodynamic mixing properties given in
M
Table 9 and the thermodynamic dissolution properties given in Table 11. The tabulated numerical
ED
values do not obey Eqns. 1 and 2. For example, substitution of the enthalpy of mixing of ΔmixH =
PT
252.4 kJ mol-1 for the binary (water + N,N-dimethylformamide) solvent mixture at xDMF = 0.9005 and T = 278.15 K, along with the measured solubility xN = 0.01786 from Table 5 and estimated
CE
enthalpy of fusion of ΔfusH = 32971 J mol-1, into Eqn. 1 yields:
AC
ΔdissH = (0.01786) (32.971 kJ mol-1) + 252.4 kJ mol-1 ΔdissH = 252.99 kJ mol-1
(9) (10)
which differs significantly from the value of ΔdissH = 913.00 kJ mol-1 that the authors give in Table 11. All sets of thermodynamic mixing and dissolution values in Tables 9 and 11 show similar inconsistencies. As an information note, the calculated value of 252.99 agrees with the value of
ACCEPTED MANUSCRIPT 253.00 listed in the ΔdissS column, thus providing further evidence that the numerical values in the ΔdissH and ΔdissS columns of Table 11 should perhaps be interchanged. I also note that the numerical values of the enthalpy of mixing that the authors report for dissolving 5-nitrofurazone in binary (water + N,N-dimethylformamide) and binary (N,N-
T
dimethylformamide + isopropanol) solvent mixtures seem abnormally large when compared with
IP
dissolving 5-nitrofurazone in water and in the eight organic mono-solvents. For the organic mono-
CR
solvents the values of ΔmixH were in the ΔmixH = 1 J mol-1 to ΔmixH = 23,000 J mol-1 range, which
US
were much smaller than the values of ΔmixH = 6 kJ mol-1 to ΔmixH = 1,800 kJ mol-1 given for the two binary solvent systems. Readers should exercise caution in using values from Tables 9 and
AN
11 as it is hard to believe that the mixing values for the mono-solvent systems should be so much
M
different from the mixing values for the binary solvent systems. As noted above, there are
ED
problems with the published values in both tables.
CE
X. Li, X. Huang, Y. Luan, J. Li, N. Wang, X. Zhang, S. Ferguson, X. Meng, H. Hao, Solubility and thermodynamic properties of 5-nitrofurazone form γ in mono-solvents and binary solvent mixtures. J. Mol. Liq. 275 (2019) 815-828.
AC
[1]
PT
References
ACCEPTED MANUSCRIPT HIGHLIGHTS Inconsistencies found in authors’ calculated thermodynamic properties of dissolution
Calculated thermodynamic dissolution properties do not obey ΔdissG = ΔdissH - T ΔdissS
Thermodynamic mixing and dissolution properties are also not internally consistent
AC
CE
PT
ED
M
AN
US
CR
IP
T