THERMODYNAMIC PROPERTIES OF NONAQUEOUS SINGLE SALT SOLUTIONS USING THE Q-ELECTROLATTICE EQUATION OF STATE

Zuber, A.; Checoni, R. F.; Castier, M.

doi:10.1590/0104-6632.20150323s00003389

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Brazilian Journal of Chemical Engineering

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Selected papers from the VII Brazilian Congress of Applied Thermodynamics (CBTermo) • Braz. J. Chem. Eng. 32 (3) • Jul-Sep 2015 • https://doi.org/10.1590/0104-6632.20150323s00003389 copy

THERMODYNAMIC PROPERTIES OF NONAQUEOUS SINGLE SALT SOLUTIONS USING THE Q-ELECTROLATTICE EQUATION OF STATE

Authorship SCIMAGO INSTITUTIONS RANKINGS

Abstract

The correlation of thermodynamic properties of nonaqueous electrolyte solutions is relevant to design and operation of many chemical processes, as in fertilizer production and the pharmaceutical industry. In this work, the Q-electrolattice equation of state (EOS) is used to model vapor pressure, mean ionic activity coefficient, osmotic coefficient, and liquid density of sixteen methanol and ten ethanol solutions containing single strong 1:1 and 2:1 salts. The Q-electrolattice comprises the lattice-based Mattedi-Tavares-Castier (MTC) EOS, the Born term and the explicit MSA term. The model requires two adjustable parameters per ion, namely the ionic diameter and the solvent-ion interaction energy. Predictions of osmotic coefficient at 298.15 K and liquid density at different temperatures are also presented.

Keywords:
Methanol; Ethanol; Electrolytes; Equation of state

Solvent	d ₁	d ₂	d ₃	d ₄	d ₅	T (K)
Methanol	1.0462x10²	1.0x10³	9.0108x10^-2	-2.5998x10^-3	4.8503x10^-6	176.60 - 318.15
Ethanol	1.7572x10²	-3.0699	-3.5350x10^-1	-2.0285x10^-3	5.0644x10^-6	288.15 - 328.15

	Diameter (Å)
Ion	In Methanol^a a This work;	Pauling Bare Ion^b b (Horvath, 1985);	In Water^c c (Zuber et al., 2014);	In Ethanol^a a (Gmehling, 2012);
Li⁺	0.14	1.20	1.85	3.96
Na⁺	0.58	1.90	2.32	4.62
K⁺	1.36	2.66	3.45	5.40
Ca²⁺	2.28	2.36	2.82	4.86
Cl^-	2.46	3.62	2.35	0.64
Br^-	2.68	3.90	2.95	1.70
I^-	1.14	4.32	3.63	6.61

Salt	Vapor Pressure^a a (Gmehling, 2012);				MIAC^a a (Gmehling, 2012);			Density^b b (Pasztor and Criss, 1978; Held et al., 2012);			OC^a a (Gmehling, 2012);
	Np	m_max	T	AARD	Np	m_max	AARD	Np	m_max	AARD	Np	m_max	AARD
		(mol/kg)	(K)	(%)		(mol/kg)	(%)		(mol/kg)	(%)		(mol/kg)	(%)
Methanol
LiCl	90	6.18	298.15 - 323.15	1.47	8	0.73	11.49	9	0.32	0.15	32	4.18	7.08
LiBr	232	6.87	298.15 - 333.15	3.61	-	-	-	16	3.49	1.02	27	3.90	12.06
Lil	-	-	-	-	5	0.60	5.99	-	-	-	5	0.60	6.70
LiNO₃	102	5.24	298.15 - 323.15	1.19	-	-	-	-	-	-	11	8.52	10.65
LiClO₄	26	3.75	298.15	1.48	-	-	-	-	-	-	48	5.06	13.17
NaCl	33	0.20	298.15	2.00	8	0.02	5.47	14	0.13	0.09	-	-	-
NaBr	26	0.60	298.15	1.74	-	-	-	13	1.11	0.53	19	1.57	18.22
NaI	30	4.34	298.15 - 313.15	4.84	-	-	-	22	1.03	1.32	-	-	-
NaClO₄	22	1.29	298.15	1.88	-	-	-	-	-	-	-	-	-
KCl	-	-	-	-	7	0.05	5.67	-	-	-	-	-	-
KBr	23	0.13	298.15	2.08	-	-	-	14	0.16	0.17	8	0.82	8.40
KI	46	0.73	298.15	2.47	10	0.50	6.84	25	0.88	1.44	-	-	-
RbCl	-	-	-	-	8	0.09	7.09	-	-	-	-	-	-
RbI	46	0.44	298.15	2.24	-	-	-	-	-	-	-	-	-
CsI	41	0.13	298.15	2.14	-	-	-	-	-	-	-	-	-
CaCl₂	84	2.60	298.15 - 323.15	1.04	-	-	-	-	-	-	25	3.73	14.88
Ethanol
LiCl	66	3.76	298.15 - 323.15	1.37	11	3.20	10.65	2	1.23	1.25	25	1.94	11.98
LiBr	-	-	-	-	6	1.50	6.33	2	0.60	0.80	6	1.50	4.22
LiI	84	8.62	298.15 - 323.15	10.40	-	-	-	2	0.39	0.97	-	-	-
LiNO₃	66	2.22	298.15 - 323.15	2.57	-	-	-	-	-	-	19	2.11	31.93
NaCl	-	-	-	-	1	0.01	13.20	-	-	-	1	0.01	8.62
NaBr	-	-	-	-	3	0.23	25.92	2	0.22	0.32	3	0.23	17.02
NaI	24	1.91	298.15	0.25	-	-	-	2	0.35	1.92	-	-	-
KI	3	0.03	288.15	0.97	-	-	-	-	-	-	-	-	-
CaCl₂	79	2.12	298.15 - 358.15	1.34	-	-	-	-	-	-	25	2.37	36.61
Ca(NO₃)₂	16	2.43	298.15	2.07	-	-	-	-	-	-	17	3.19	36.27

Salt	Np	m_max(kg/mol)	T (K)	AARD(%)
Methanol
LiCl^a a (Takenaka et al, 1994a);	8	0.10	288.15	0.15
	8	0.18	298.15	0.21
	12	0.12	308.15	0.41
	8	0.11	318.15	0.29
LiBr^b b (Glugla et al, 1982);	11	4.50	288.15	0.22
	10	4.28	298.15	0.21
	11	4.50	308.15	0.16
	11	2.78	323.15	0.26
LiI^b b (Glugla et al, 1982);	12	2.51	298.15	1.16
	7	1.97	308.15	1.58
	14	2.51	323.15	1.01
LiClO₄^c c (Barthel et al, 1998);	5	1.34	298.15	2.04
NaCl^a a (Takenaka et al, 1994a);	8	0.19	288.15	0.08
	7	0.14	298.15	0.09
	9	0.17	308.15	0.13
	8	0.20	318.15	0.16
NaBr^d d (Takenaka et al., 1994b);	8	0.10	288.15	0.06
	8	0.22	298.15	0.16
	8	0.38	308.15	0.86
	8	0.10	318.15	0.12
NaI^d d (Takenaka et al., 1994b);	8	0.10	288.15	0.27
	8	0.21	298.15	0.44
	11	0.16	308.15	0.64
	8	0.30	318.15	0.61
NaClO₄^e e (Wawer et al., 2008);	13	0.41	283.15	0.72
	13	0.41	288.15	0.76
	13	0.41	293.15	0.79
	13	0.41	298.15	0.81
	13	0.41	303.15	0.83
	13	0.41	308.15	0.84
	13	0.41	313.15	0.84
KCl^a a (Takenaka et al, 1994a);	8	0.04	288.15	0.05
	8	0.06	298.15	0.05
	8	0.05	308.15	0.09
	8	0.06	318.15	0.10
KBr^d d (Takenaka et al., 1994b);	8	0.06	288.15	0.05
	8	0.06	298.15	0.06
	8	0.11	308.15	0.13
	8	0.09	318.15	0.13
KI^f f (Takenaka et al., 1994c)	8	0.10	288.15	0.24
	8	0.18	298.15	0.48
	8	0.12	308.15	0.39
	8	0.11	318.15	0.32

Salt	Np	m_max(kg/mol)	T (K)	AARD (%)
Ethanol
LiCl^a a (Glugla et al, 1982)	8	2.30	298.15	0.38
LiBr^a a (Glugla et al, 1982)	11	2.83	298.15	0.39
LiBr^a a (Glugla et al, 1982)	12	1.95	323.15	0.68
LiI^a a (Glugla et al, 1982)	11	2.77	298.15	1.35
LiI^a a (Glugla et al, 1982)	13	1.89	323.15	1.11
LiNO₃^a a (Glugla et al, 1982)	8	2.41	298.15	0.24
NaI^a a (Glugla et al, 1982)	6	1.39	298.15	1.72

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[1] *To whom correspondence should be addressed, This is an extended version of the manuscript presented at the, VII Brazilian Congress of Applied Thermodynamics - CBTermo 2013, Uberlândia, Brazil.