Heat Capacities and Ion-interaction of Lithium Tetraborate Aqueous Solution System†

doi:10.7503/cjcu20150594

Abstract

Abstract:

The heat capacities of aqueous solution systems(Li₂B₄O₇-H₂O) with molality of Li₂B₄O₇ of 0.00415—0.4208 mol/kg at 298.15, 308.15 and 323.15 K were determined experimentally using microcalorimeter. On the basis of experimental data, the apparent molar heat capacities at different concentrations and temperatures were calculated, and the relationship equations between apparent molar heat capacity and solution concentration of lithium tetraborate at 298.15, 308.15 and 323.15 K were obtained. The Pitzer single salt parameters of lithium tetraborate at different temperatures were fitted based on the Pitzer ion-interaction theory on the apparent molar heat capacity of electrolytes.

Key words: Lithium tetraborate, Heat capacity, Calorimetric method, Electrolyte solution, Pitzer single salt parameter

CLC Number:

O642.3

TrendMD:

LI Long, ZHANG Sisi, LIU Yuanhui, GUO Yafei, DENG Tianlong. Heat Capacities and Ion-interaction of Lithium Tetraborate Aqueous Solution System^†[J]. Chem. J. Chinese Universities, 2016, 37(2): 349.

Figures/Tables 6

Table 1 Heat capacity and apparent molar heat capacity of Li2B4O7-H2O systema

Temperature/K	No.	m^b/(mol·kg^-1)	$C p c$ /(kJ·K^-1·kg^-1)	$C p, ? d$ /(J·K^-1·mol^-1)
298.15	1	0.35130	4.0022	324.04967
	2	0.27547	4.0258	277.74831
	3	0.26051	4.0344	281.04659
	4	0.23503	4.0576	325.25692
	5	0.20947	4.0727	338.55548
	6	0.18467	4.0821	324.64582
	7	0.16067	4.0921	312.33649
	8	0.11079	4.1142	279.00489
	9	0.06393	4.1490	416.32652
	10	0.01569	4.1723	569.15031
	11	0.00415	4.1805	1749.20571
308.15	1	0.35130	3.9860	280.37480
	2	0.32638	3.9961	272.02999
	3	0.25319	4.0260	238.34864
	4	0.20610	4.0520	235.57748
	5	0.18223	4.0641	225.84663
	6	0.08936	4.1020	27.12426
	7	0.04477	4.1291	-175.33711
	8	0.02210	4.1511	-224.36395
	9	0.00440	4.1641	-1595.53866
323.15	1	0.4208	3.9681	318.0696
	2	0.3912	3.9923	347.4161
	3	0.3119	4.0302	356.7374
	4	0.2422	4.0637	366.7468
	5	0.2302	4.0696	369.4891
	6	0.1977	4.0835	365.6931
	7	0.1615	4.0962	341.3357
	8	0.1450	4.1000	311.3234
	9	0.1294	4.1059	294.2946
	10	0.1129	4.1127	276.0213
	11	0.09678	4.1220	279.4053
	12	0.06466	4.1313	143.8652
	13	0.04836	4.1411	111.3430
	14	0.3228	4.1491	-6.9188
	15	0.01604	4.1565	-412.8703

Table 1 Heat capacity and apparent molar heat capacity of Li2B4O7-H2O systema

Temperature/K	No.	m^b/(mol·kg^-1)	$C p c$ /(kJ·K^-1·kg^-1)	$C p, ? d$ /(J·K^-1·mol^-1)
298.15	1	0.35130	4.0022	324.04967
	2	0.27547	4.0258	277.74831
	3	0.26051	4.0344	281.04659
	4	0.23503	4.0576	325.25692
	5	0.20947	4.0727	338.55548
	6	0.18467	4.0821	324.64582
	7	0.16067	4.0921	312.33649
	8	0.11079	4.1142	279.00489
	9	0.06393	4.1490	416.32652
	10	0.01569	4.1723	569.15031
	11	0.00415	4.1805	1749.20571
308.15	1	0.35130	3.9860	280.37480
	2	0.32638	3.9961	272.02999
	3	0.25319	4.0260	238.34864
	4	0.20610	4.0520	235.57748
	5	0.18223	4.0641	225.84663
	6	0.08936	4.1020	27.12426
	7	0.04477	4.1291	-175.33711
	8	0.02210	4.1511	-224.36395
	9	0.00440	4.1641	-1595.53866
323.15	1	0.4208	3.9681	318.0696
	2	0.3912	3.9923	347.4161
	3	0.3119	4.0302	356.7374
	4	0.2422	4.0637	366.7468
	5	0.2302	4.0696	369.4891
	6	0.1977	4.0835	365.6931
	7	0.1615	4.0962	341.3357
	8	0.1450	4.1000	311.3234
	9	0.1294	4.1059	294.2946
	10	0.1129	4.1127	276.0213
	11	0.09678	4.1220	279.4053
	12	0.06466	4.1313	143.8652
	13	0.04836	4.1411	111.3430
	14	0.3228	4.1491	-6.9188
	15	0.01604	4.1565	-412.8703

Table 2 Polynomial coefficients for the equations of m versus Cp,ϕ at different temperatures

T/K	a₀	a₁	a₂	a₃	a₄	a₅	a₆	SD	r
298.15	316.0077	-37.6463	5.7704	-840.4368	0.0015	-1.0264×10^-5	-106.1326	0.0010	0.9999
308.15	350.8727	-148.2711	11.2706	-1.5586	0.0169	-0.0012	-233.7575	0.0002	0.9999
323.15	625.9910	-338.7045	53.7625	-9.5775	0.7399	-0.0240	-353.8408	0.0310	0.9999

Fig.1 Relative apparent molar heat capacities of the system Li2B4O7-H2O versus m at 298.15 K

Fig.2 Relative apparent molar heat capacities of the system Li2B4O7-H2O versus m at 308.15 K

Fig.3 Relative apparent molar heat capacities of the system Li2B4O7-H2O versus m at 323.15 K

Table 3 Pitzer parameters and apparent heat capacity in the infinitely dilute solution of lithium tetraborate at different temperatures

T/K	$β MX 0 J$	$β MX 1 J$	$β MX 2 J$	$C MX J$	σ	r	$C p θ$ /(J·K^-1·mol^-1)
298.15	-0.00205	0.00425	1.44190	0.00085	0.00634	0.99986	4173.9472
308.15	0.00457	-0.00878	-2.91442	-0.00189	0.01106	0.99982	-8013.8049
323.15	0.00427	-0.00893	-10.39665	-0.00155	0.01285	0.99847	-31010.8639

Table 3 Pitzer parameters and apparent heat capacity in the infinitely dilute solution of lithium tetraborate at different temperatures

T/K	$β MX 0 J$	$β MX 1 J$	$β MX 2 J$	$C MX J$	σ	r	$C p θ$ /(J·K^-1·mol^-1)
298.15	-0.00205	0.00425	1.44190	0.00085	0.00634	0.99986	4173.9472
308.15	0.00457	-0.00878	-2.91442	-0.00189	0.01106	0.99982	-8013.8049
323.15	0.00427	-0.00893	-10.39665	-0.00155	0.01285	0.99847	-31010.8639

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