Measurement of Activity Coefficients at Infinite Dilution for Alcohols in [BMIM][CH<sub>3</sub>SO<sub>4</sub>] using HS-SPME/GC-FID

Elias, A. M.; Santana, V. C. N.; Coelho, G. L. V.

doi:10.1590/0104-6632.20170343s20150640

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COBEQ-IC-2015 • Braz. J. Chem. Eng. 34 (3) • July 2017 • https://doi.org/10.1590/0104-6632.20170343s20150640 copy

Measurement of Activity Coefficients at Infinite Dilution for Alcohols in [BMIM][CH₃SO₄] using HS-SPME/GC-FID^* * This is an extended version of the work presented at the 11th Brazilian Congress of Chemical Engineering on Undergraduate Scientific Mentorship, COBEQ-IC 2015, Campinas - SP, Brazil

Authorship SCIMAGO INSTITUTIONS RANKINGS

ABSTRACT

The activity coefficient at infinite dilution (&IN1) and distribution ratios at infinite dilution (&IN2) were determined for alkanols (methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, and 2-methyl-2-propanol) in the ionic liquid (IL) 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][CH₃SO₄]) by HS-SPME (Headspace - Solid Phase Micro Extraction) at four temperatures (298.15, 313.15, 333.15, and 353.15K) using headspace - solid phase microextraction (SPME-HS). The results showed significant agreement with literature data. In addition, partial molar excess enthalpies at infinite dilution (&IN3), excess Gibbs energies (&IN4), and excess entropies (&IN5) were calculated from the (&IN6) values.

Keywords:
Solid-phase microextraction; 1-butyl-3-methylimidazolium methyl sulfate; ionic liquid.

Chemicals	Purities in massfraction
	Provided by producer	GC analysis
methanol	0.9900	0.9968
ethanol	0.9900	0.9959
1-propanol	0.9950	0.9980
1-butanol	0.9900	0.9977
2-butanol	0.9950	0.9961
2-methyl-2-propanol	0.9950	0.9974
o-xylene	0.9800	0.9922

Solute	B₁₁ m³ ·mol^-1 ·10³	&IN10 m³ . mol^-1 ·10⁸	&IN7 Pa
T= 298.15 K
Methanol	-0.9	4182.8	16953.5
Ethanol	-1.3	5258.8	7894.6
1-Propanol	-1.9	6451.5	2806.2
1-Butanol	-2.6	7965.4	894.9
2-Butanol	-2.2	8267.4	2270.1
2-Methyl-2-propanol	-1.9	8204.2	5596.2
T= 313.15 K
Methanol	-0.8	4279.0	35462.1
Ethanol	-1.1	5381.4	17950.8
1-Propanol	-1.6	6589.0	6989.2
1-Butanol	-2.2	8118.8	2468.3
2-Butanol	-1.9	8441.6	5967.9
2-Methyl-2-propanol	-1.6	8400.4	13774.8
T= 333.15 K
Methanol	-0.7	4.4195	84583.9
Ethanol	-0.9	5.5605	47052.9
1-Propanol	-1.3	6.7880	20279.9
1-Butanol	-1.8	8.3389	7990.6
2-Butanol	-1.6	8.6936	18057.5
2-Methyl-2-propanol	-1.3	8.6879	38621.8
T= 353.15 K
Methanol	-0.6	4576.9	180867.8
Ethanol	-0.8	5761.1	108659.3
1-Propanol	-1.1	7008.2	50836.6
1-Butanol	-1.5	8579.6	21834.2
2-Butanol	-1.3	8972.4	46104.6
2-Methyl-2-propanol	-1.1	9011.3	92300.9

Temperature K	a g·cm^-3	b g·cm^-3 ·K^-1	ρ_s g·cm^-3
298.15	1.4119	-6.772·10^-4	1.2100
313.15			1.1998
333.15			1.1863
353.15			1.1727

Solute i	&QT
	T = 298.15 K	T = 313.15 K
Methanol	48.4 ±2.6	29.1 ±0.8
Ethanol	107.3 ±4.3	51.7±0.9
1-Propanol	249.5 ±2.4	117.3 ±0.9
1-Butanol	634.4 ± 31.7	244.4 ± 17.6
2-Butanol	246.0 ± 10.3	126.1 ±3.0
2-Methyl-2-propanol	141.7 ±8.5	77.5 ±1.8
	T = 333.15 K	T = 353.15 K
Methanol	14.5 ±0.9	8.5 ±0.6
Ethanol	26.7 ±0.3	15.4 ±0.2
1-Propanol	55.8 ±2.6	31.9 ±1.7
1-Butanol	98.6 ±8.3	51.8 ±1.5
2-Butanol	57.6 ±2.8	30.5 ±1.8
2-Methyl-2-propanol	37.9 ±1.9	20.8 ±1.9

Solute i	&IN		RSD (%)
Solute i	SPME (Present study)	Dilutor Technique (Dobryakov et al.,2008).
	T = 298.15 K
Methanol	1841 ± 9	1840	0.05
Ethanol	2251 ± 29	2350	4.21
1-Propanol	3958 ± 83	4470	11.45
1-Butanol	7661 ± 157	7844	2.33
2-Butanol	3537 ± 103	3587	1.39
2-Methyl-2-propanol	1564 ± 6	1561	0.19
	T = 313.15 K
Methanol	1022 ± 49	1004	1.79
Ethanol	1088 ± 37	1142	4.73
1-Propanol	1917 ± 24	2044	6.21
1-Butanol	3476 ± 88	3490	0.40
2-Butanol	1555 ± 24	1590	2.20
2-Methyl-2-propanol	723 ± 11	719
	T = 333.15 K
Methanol	508 ± 2	492	1.79
Ethanol	469 ± 22	458	4.73
1-Propanol	866 ± 9	731	6.21
1-Butanol	1424 ± 49	1204	0.40
2-Butanol	611 ± 16	577	2.20
2-Methyl-2-propanol	314 ± 8	292	0.56
	T = 353.15 K
Methanol	280 ± 6	298	6.04
Ethanol	232 ± 2	222	4.50
1-Propanol	454 ± 10	337	34.72
1-Butanol	681 ± 33	525	29.71
2-Butanol	276 ± 3	252	9.52
2-Methyl-2-propanol	145 ± 3	128	13.28

Solute i	&IN		RSD (%)
Solute i	SPME (Present study)	Dilutor Technique (Dobryakov et al., 2008)
	T =298.15 K
Methanol	0.39 ± 0.02	0.39	0.00
Ethanol	0.68 ± 0.01	0.64	6.25
1-Propanol	1.08 ± 0.01	0.96	12.50
1-Butanol	1.75 ± 0.04	1.68	4.17
2-Butanol	1.49 ± 0.02	1.45	2.76
2-Methyl-2-propanol	1.37 ± 0.01	1.38	0.72
	T = 313.15 K
Methanol	0.36 ± 0.02	0.36	0.00
Ethanol	0.65 ± 0.02	0.61	6.56
1-Propanol	0.94 ± 0.01	0.88	6.82
1-Butanol	1.46 ± 0.04	1.44	1.39
2-Butanol	1.35 ± 0.02	1.31	3.05
2-Methyl-2-propanol	1.26 ± 0.02	1.27	0.79
	T = 333.15 K
Methanol	0.33 ± 0.01	0.33	0.00
Ethanol	0.61 ± 0.03	0.62	1.61
1-Propanol	0.76 ± 0.01	0.89	14.61
1-Butanol	1.16 ± 0.04	1.37	15.33
2-Butanol	1.20 ± 0.03	1.27	5.51
2-Methyl-2-propanol	1.10 ± 0.03	1.19	7.56
	T = 353.15 K
Methanol	0.31 ± 0.01	0.38	18.42
Ethanol	0.58 ± 0.02	0.59	1.69
1-Propanol	0.62 ± 0.01	0.82	24.39
1-Butanol	0.94 ± 0.05	1.21	22.31
2-Butanol	1.10 ± 0.01	1.21	9.09
2-Methyl-2-propanol	1.04 ± 0.02	1.22	14.75

Solute i	&IN3 kJ·mol^-1	&IN4 kJ·mol^-1	&IN12 kJ·mol^-1
Methanol	3.67	6.01	-2.33
Ethanol	2.56	3.51	-0.96
1-Propanol	8.89	8.66	0.19
1-Butanol	9.90	8.51	1.39
2-Butanol	4.86	3.88	0.99
2-Methyl-2-propanol	4.56	3.79	0.78

Solute	&IN±SD^b			Statistical tests results
Solute	Fiber 1	Fiber 2	Fiber 3	F-value	Result
Methanol	49.77 ± 0.78	48.70 ± 0.75	49.27 ± 0.67	0.453	OK
Ethanol	110.20±1.60	108.08±1.92	109.26±0.63	1.519	OK
1-Propanol	250.77±0.83	249.23±2.09	250.61±1.01	1.057	OK
1-Butanol	632.51±1.38	633.48±1.49	632.33±1.33	0.585	OK
2-Butanol	239.79±1.00	237.76±1.16	238.09±1.01	3.155	OK
2-Methyl-2-propanol	136.87±1.59	135.60±1.07	138.65±1.33	3.887	OK

Solute	Fiber 1		Statistical tests results
Solute	Before	After	T-value	Result
Methanol	49.03±0.78	49.13±0.47	-0.183	OK
Ethanol	110.20±1.61	109.02±1.31	0.983	OK
1-Propanol	250.77±0.83	250.27±0.56	-1.904	OK
1-Butanol	632.51±1.38	631.72±1.36	0.712	OK
2-Butanol	239.79±1.00	239.19±1.01	0.983	OK
2-Methyl-2-propanol	136.87±1.59	137.91±1.49	-0.828	OK

	Fiber 2		Statistical tests results
	Before	After	T-value	Result
Methanol	48.70±0.75	49.72±0.41	-2.055	OK
Ethanol	108.08±1.92	108.51±0.69	-0.369	OK
1-Propanol	249.23±2.10	250.87±1.34	-1.144	OK
1-Butanol	633.48±1.49	632.60±1.41	0.742	OK
2-Butanol	237.76±4.90	237.97±0.78	-0.265	OK
2-Methyl-2-propanol	135.60±1.07	136.45±1.06	-0.981	OK

	Fiber 3		Statistical tests results
	Before	After	T-value	Result
Methanol	49.27±0.67	49.07±0.55	0.303	OK
Ethanol	109.26±0.63	109.36±1.23	-0.122	OK
1-Propanol	250.61±1.01	249.95±0.81	0.874	OK
1-Butanol	632.33±1.33	633.23±0.99	-0.941	OK
2-Butanol	238.09±1.01	238.20±0.65	-0.153	OK
2-Methyl-2-propanol	138.65±1.34	139.44±0.84	-0.862	OK

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[1] *To whom correspondence should be addressed: G.L.V Coelho, E-mail: coelho@ufrrj.br; Tel.: +55(21) 3787 3742; fax: +55 (21) 3787 3750

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Measurement of Activity Coefficients at Infinite Dilution for Alcohols in [BMIM][CH3SO4] using HS-SPME/GC-FID* * This is an extended version of the work presented at the 11th Brazilian Congress of Chemical Engineering on Undergraduate Scientific Mentorship, COBEQ-IC 2015, Campinas - SP, Brazil

ABSTRACT

Measurement of Activity Coefficients at Infinite Dilution for Alcohols in [BMIM][CH₃SO₄] using HS-SPME/GC-FID^* * This is an extended version of the work presented at the 11th Brazilian Congress of Chemical Engineering on Undergraduate Scientific Mentorship, COBEQ-IC 2015, Campinas - SP, Brazil