MEASUREMENTS AND THERMODYNAMIC MODELING OF VAPOR-LIQUID EQUILIBRIA FOR BINARY SYSTEMS OF ISOPROPYL CHLOROACETATE WITH CYCLOHEXANE, ISOPROPANOL AND BENZENE AT 101.3 kPa

Xu, Dongmei; Li, Rui; Zhang, Lianzheng; Ma, Yixin; Gao, Jun; Wang, Yinglong

doi:10.1590/0104-6632.20190364s20190112

Dongmei Xu

Shandong University of Science and Technology, College of Chemical and Environmental Engineering, Qingdao, China. E-mail: gao@sdust.edu.cn

http://orcid.org/0000-0002-5770-0513

Rui Li

Shandong University of Science and Technology, College of Chemical and Environmental Engineering, Qingdao, China. E-mail: gao@sdust.edu.cn

Lianzheng Zhang

Shandong University of Science and Technology, College of Chemical and Environmental Engineering, Qingdao, China. E-mail: gao@sdust.edu.cn

http://orcid.org/0000-0003-4827-7941

Yixin Ma

Shandong University of Science and Technology, College of Chemical and Environmental Engineering, Qingdao, China. E-mail: gao@sdust.edu.cn

http://orcid.org/0000-0003-0894-5909

Jun Gao

Shandong University of Science and Technology, College of Chemical and Environmental Engineering, Qingdao, China. E-mail: gao@sdust.edu.cn

http://orcid.org/0000-0003-1145-9565

Yinglong Wang

Qingdao University of Science and Technology, College of Chemical Engineering, Qingdao, China.

http://orcid.org/0000-0002-3043-0891

* Corresponding author: Jun Gao - E-mail: gao@sdust.edu.cn

Name	CAS	Supplier^c	Mass fraction	T_b/K^b		Analysis method
Name	CAS	Supplier^c	Mass fraction	This work	Literature	Analysis method
Isopropyl chloroacetate	105-48-6	(1)	≥0.980	422.85	422.63 (Dorris et al., 1934)	GC^a
Isopropanol	67-63-0	(2)	≥0.997	355.11	355.45 (Chen et al., 2011)	GC^a
Cyclohexane	110-82-7	(2)	≥0.995	353.83	353.65 (Gupta and Lee, 2012)	GC^a
Benzene	71-43-2	(3)	≥0.995	353.23	353.25 (Li et al., 2017)	GC^a

Name	Characteristic	Description
Column	Type	DB-WAX, 30 m × 0.53 m × 0.5 µm
Column	Temperature	393.15 K
Carrier gas	Type	Nitrogen
	Flow rate	10 mL/min
	Pressure	0.3 MPa
Injector	Injection volume	0.2 μL
Injector	Temperature	443.15 K
Detector	Type	Flame ionization detector (FID)
Detector	Temperature	433.15 K

T (K)	x₁	y₁	γ₁	γ₂	G^E (J·mol⁻¹)
Cyclohexane (1) + Isopropyl chloroacetate (2)
353.83	1.0000	1.0000	-	-	0.00
355.65	0.9333	0.9894	1.0046	1.6575	112.32
357.64	0.8000	0.9685	1.0818	1.5090	431.71
360.60	0.7001	0.9519	1.1149	1.3574	503.03
366.02	0.5667	0.9239	1.1470	1.1921	468.21
370.33	0.4870	0.8961	1.1503	1.1599	444.25
376.60	0.3932	0.8549	1.1510	1.0789	317.42
381.35	0.3297	0.8162	1.1603	1.0393	237.34
385.20	0.2835	0.7755	1.1645	1.0352	217.65
389.60	0.2366	0.7215	1.1662	1.0344	201.46
394.96	0.1837	0.6508	1.1932	1.0125	139.85
400.25	0.1403	0.5634	1.1976	1.0116	117.18
405.30	0.1035	0.4668	1.2017	1.0100	94.14
410.45	0.0700	0.3560	1.2117	1.0043	59.49
416.85	0.0323	0.1903	1.2270	1.0041	36.62
418.96	0.0215	0.1325	1.2288	1.0011	19.18
422.85	0.0000	0.0000	-	-	0.00
Isopropanol (1) + Isopropyl chloroacetate (2)
355.11	1.0000	1.0000	-	-	0.00
356.22	0.9393	0.9921	1.0204	1.3246	106.71
357.35	0.8894	0.9858	1.0240	1.2454	134.78
359.79	0.7955	0.9716	1.0260	1.2157	180.56
362.53	0.7006	0.9545	1.0305	1.1879	218.83
368.66	0.5283	0.9102	1.0383	1.1638	280.17
371.49	0.4636	0.8865	1.0411	1.1587	301.70
375.45	0.3785	0.8511	1.0657	1.1285	309.71
380.45	0.2962	0.8063	1.0888	1.0777	246.29
385.90	0.2273	0.7512	1.1060	1.0379	165.69
390.95	0.1734	0.6897	1.1351	1.0164	115.13
399.05	0.1055	0.5654	1.1980	1.0059	80.69
405.45	0.0662	0.4446	1.2493	1.0053	66.31
409.75	0.0457	0.3548	1.2820	1.0016	43.87
415.00	0.0235	0.2283	1.3933	1.0011	30.60
422.85	0.0000	0.0000	-	-	0.00
Benzene (1) + Isopropyl chloroacetate (2)
353.23	1.0000	1.0000	-	-	0.00
356.77	0.8825	0.9868	1.0039	1.1169	48.72
359.88	0.7916	0.9734	1.0063	1.1131	81.69
361.80	0.7342	0.9633	1.0150	1.1121	117.83
368.34	0.5828	0.9251	1.0192	1.1114	168.89
373.95	0.4761	0.8834	1.0214	1.1093	200.30
378.05	0.4102	0.8490	1.0217	1.0944	194.90
385.05	0.3141	0.7789	1.0223	1.0706	171.97
389.55	0.2590	0.7234	1.0297	1.0602	164.84
396.65	0.1875	0.6209	1.0294	1.0445	134.57
401.45	0.1414	0.5418	1.0655	1.0230	95.11
407.85	0.0892	0.4121	1.1125	1.0132	72.75
413.65	0.0456	0.2718	1.2652	1.0057	55.55
415.90	0.0262	0.2089	1.6134	1.0023	51.07
418.85	0.0135	0.1272	1.7921	1.0022	34.98
422.85	0.0000	0.0000	-	-	0.00

Component	C_1i	C_2i	C_3i	C_4i	p_ci/kPa	T_ci/K	T_lower/K	T_upper/K
Isopropyl chloroacetate	-8.3736	2.2903	-3.9060	-3.7705	3420.33	614.00	190.00	614.00
Cyclohexane	-7.0580	1.7024	-2.1203	-3.1898	4070.44	553.40	279.82	553.40
Isopropanol	-8.5396	1.5379	-7.6671	2.3246	4751.67	508.27	185.24	508.27
Benzene	-7.1463	1.9153	-2.2948	-3.2081	4894.12	562.02	278.47	562.02

System	D	J	\|D-J\| < 10
Cyclohexane (1) + Isopropyl chloroacetate (2)	37.73	29.26	8.47
Isopropanol (1) + Isopropyl chloroacetate (2)	37.68	28.61	9.08
Benzene (1) + Isopropyl chloroacetate (2)	37.89	29.19	8.69

System		ΔP < 1	Δy < 1
Cyclohexane (1) + Isopropyl chloroacetate (2)	NRTL	0.16	0.5082
	Wilson	0.15	0.4951
	UNIQUAC	0.15	0.4901
Isopropanol (1) + Isopropyl chloroacetate (2)	NRTL	0.06	0.2745
	Wilson	0.06	0.2495
	UNIQUAC	0.08	0.2745
Benzene (1) + Isopropyl chloroacetate (2)	NRTL	0.09	0.4439
	Wilson	0.06	0.2604
	UNIQUAC	0.08	0.4974

Component	r	q
Isopropyl chloroacetate	4.663	4.064
Cyclohexane	4.047	3.240
Isopropanol	2.914	2.528
Benzene	3.191	2.400

Model	a_ij	a_ji	b_ij / K	b_ji / K	RMSD(y₁)	RMSD（T）
Cyclohexane (1) + Isopropyl chloroacetate (2)
NRTL	-2.7539	0.4169	1533.43	-395.50	0.0060	0.58
Wilson	0.2585	1.7588	53.88	-1074.49	0.0057	0.54
UNIQUAC	0.3081	0.1710	-348.10	84.15	0.0058	0.54
Isopropanol (1) + Isopropyl chloroacetate (2)
NRTL	-10.0839	20.3022	3438.09	-6918.72	0.0038	0.26
Wilson	-12.0894	5.4616	3991.10	-3936.35	0.0035	0.26
UNIQUAC	4.6921	-10.2046	-1827.72	3360.08	0.0037	0.23
Benzene (1) + Isopropyl chloroacetate (2)
NRTL	-10.2641	24.2028	3497.51	-8392.13	0.0064	0.23
Wilson	-16.4172	5.1950	5562.50	-1693.54	0.0043	0.17
UNIQUAC	4.8828	-12.9678	-1552.45	4364.27	0.0066	0.21

ln (p_{i}^{s}) =ln (p_{ci}) + \frac{C_{1i} ({1-T}_{ri}) {+C}_{2i} {{(1-T}_{ri})}^{1 .5} {+C}_{3i} {{(1-T}_{ri})}^{2 .5} {+C}_{4i} {{(1-T}_{ri})}^{5}}{T_{ri}}

\ln γ_{i} = \frac{\sum_{j} x_{j} τ_{j i} G_{j i}}{\sum_{k} x_{k} G_{k i}} + \sum_{j} \frac{x_{j} G_{i j}}{\sum_{k} x_{k} G_{k j}} (τ_{i j} - \frac{\sum_{m} x_{m} τ_{m j} G_{m j}}{\sum_{k} x_{k} G_{k j}})

\ln γ_{i} = \ln \frac{Φ_{i}}{x_{i}} + \frac{z}{2} q_{i} \ln \frac{θ_{i}}{Φ_{i}} - q_{i}^{t} \ln t_{i}^{t} - q_{i}^{t} \frac{\sum_{j} θ_{j}^{t} τ_{i j}}{t_{j}^{t}} + l_{i} + q_{i}^{t} - \frac{Φ_{i}}{x_{i}} \sum_{j} x_{j} l_{j}

Q = \sum_{i = 1}^{N} [{(\frac{T_{i}^{\exp} - T_{i}^{c a l}}{σ_{T}})}^{2} + {(\frac{p_{i}^{\exp} - p_{i}^{c a l}}{σ_{p}})}^{2} + {(\frac{x_{i}^{\exp} - x_{i}^{c a l}}{σ_{x}})}^{2} + {(\frac{y_{i}^{\exp} - y_{i}^{c a l}}{σ_{y}})}^{2}]

[1] * Corresponding author: Jun Gao - E-mail: gao@sdust.edu.cn

Brasil

Brasil

MEASUREMENTS AND THERMODYNAMIC MODELING OF VAPOR-LIQUID EQUILIBRIA FOR BINARY SYSTEMS OF ISOPROPYL CHLOROACETATE WITH CYCLOHEXANE, ISOPROPANOL AND BENZENE AT 101.3 kPa

Abstract