Density Functional Theory Studies on the CO2 Absorption by 1-Ethylamine-3-methylimidazolium Tetrafluoroborate†

doi:10.7503/cjcu20160337

Abstract

Abstract:

CO₂ absorption mechanism by ionic liquids 1-ethylamine-3-methylimidazolium tetrafluoroborate, which was formulated as [NH₂e-mim][BF₄], was described via density functional theory(DFT). The structure of ionic liquids [NH₂e-mim][BF₄], their reaction intermediates, transition states and products, were optimized using the B3LYP/6-311++G(d, p) basis method, with the optimized configuration parameters, vibration frequencies and thermodynamics data obtained. Furthermore, the natural bond orbital atomic charge assignments were also calculated via the natural bond orbital(NBO) method. The computational results demonstrated that the divalent cation [NH₃e-mim]²⁺, which was produced by the autoprotolysis of cation [NH₂e-mim]⁺, could be easily combined with anion [BF₄]^-, with stronger ionic bond formed. According to the calculation results of standard Gibbs free energy(ΔG^0—) and enthalpy(ΔH^0—), it could be inferred that the absorption of CO₂ onto ionic liquids [NH₂e-mim][BF₄] was step by step, in accordance with the theoretical molar ratio of 2:1. During the absorption process, the energy barrier of 52.51 kJ/mol should be overcome for proton transfer reaction.

Key words: Ionic liquid, CO₂, Density functional theory(DFT), Absorption mechanism

CLC Number:

O641

TrendMD:

ZHANG Hui, ZHANG Hongmei, WANG Lianjun, SHEN Jinyou. Density Functional Theory Studies on the CO₂ Absorption by 1-Ethylamine-3-methylimidazolium Tetrafluoroborate^†[J]. Chem. J. Chinese Universities, 2016, 37(9): 1660.

Figures/Tables 10

References 34

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Species	[NH₂e-mim][BF₄]	[NH₂e-mim]⁺	[BF₄]^-	CO₂
C1—H1	0.1078	0.1078
C4—H6	0.1095	0.1103
N3—H5	0.1018	0.1013
N3—H4	0.1014	0.1011
N3—C4	0.1462	0.1453
C4—H6	0.1095	0.1103
B—F1	0.1434		0.1413
B—F2	0.1421		0.1414
B—F3	0.1436		0.1413
B—F4	0.1369		0.1414
C5—O1				0.1161
C5—O2				0.1161
∠H1—C1—N1	126.05	125.51
∠H1—C1—N2	124.89	125.47
∠H4—N3—H5	106.88	107.88
∠O2—C5—O1				180
∠H1—C1—N1—C3	176.57	179.60
∠N1—C1—N2—C2	-0.490	-0.24
∠N1—C3—C2—N2	-0.37	-0.17

Species	[NH₂e-mim][BF₄]	[NH₂e-mim]⁺	[BF₄]^-	CO₂
C1—H1	0.1078	0.1078
C4—H6	0.1095	0.1103
N3—H5	0.1018	0.1013
N3—H4	0.1014	0.1011
N3—C4	0.1462	0.1453
C4—H6	0.1095	0.1103
B—F1	0.1434		0.1413
B—F2	0.1421		0.1414
B—F3	0.1436		0.1413
B—F4	0.1369		0.1414
C5—O1				0.1161
C5—O2				0.1161
∠H1—C1—N1	126.05	125.51
∠H1—C1—N2	124.89	125.47
∠H4—N3—H5	106.88	107.88
∠O2—C5—O1				180
∠H1—C1—N1—C3	176.57	179.60
∠N1—C1—N2—C2	-0.490	-0.24
∠N1—C3—C2—N2	-0.37	-0.17

Species	ZPE/(kJ·mol^-1)	G/(kJ·mol^-1)	H/(kJ·mol^-1)
CO₂	31.51	-495300.58	-495237.56
[BF₄]^-	39.38	-1114947.46	-1114860.81
[NH₂e-mim]⁺	488.34	-1049798.30	-1049674.90
[NH₂e-mim]⁺[BF₄]^-	530.35	-2165081.82	-2164924.29
[NHe-mim]	441.08	-1048496.05	-1048375.28
[NHe-mim][BF₄]^-	493.59	-2163359.49	-2163199.33
[NH₃e-mim]²⁺	519.85	-1050530.81	-1050257.76
[NH₃e-mim]²⁺[BF₄]^-	567.11	-2166058.50	-2165900.97
R1(2[NH₂e-mim]⁺[BF₄]^-+CO₂)	1100.08	-4824962.74	-4824584.67
IM1^a	1110.59	-4825138.65	-4824834.09
TS1^b	1100.08	-4825096.64	-4824857.72
IM2^c	1102.71	-4825427.45	-4825149.15
P1^d	1113.21	-4825411.70	-4825138.65
R2([NH₂e-mim]⁺[BF₄]^-+CO₂)	564.48	-2660461.16	-2660227.49
TS2^e	556.61	-2660253.74	-2660075.21
P2^f	574.98	-2660324.63	-2660146.10

Species	ZPE/(kJ·mol^-1)	G/(kJ·mol^-1)	H/(kJ·mol^-1)
CO₂	31.51	-495300.58	-495237.56
[BF₄]^-	39.38	-1114947.46	-1114860.81
[NH₂e-mim]⁺	488.34	-1049798.30	-1049674.90
[NH₂e-mim]⁺[BF₄]^-	530.35	-2165081.82	-2164924.29
[NHe-mim]	441.08	-1048496.05	-1048375.28
[NHe-mim][BF₄]^-	493.59	-2163359.49	-2163199.33
[NH₃e-mim]²⁺	519.85	-1050530.81	-1050257.76
[NH₃e-mim]²⁺[BF₄]^-	567.11	-2166058.50	-2165900.97
R1(2[NH₂e-mim]⁺[BF₄]^-+CO₂)	1100.08	-4824962.74	-4824584.67
IM1^a	1110.59	-4825138.65	-4824834.09
TS1^b	1100.08	-4825096.64	-4824857.72
IM2^c	1102.71	-4825427.45	-4825149.15
P1^d	1113.21	-4825411.70	-4825138.65
R2([NH₂e-mim]⁺[BF₄]^-+CO₂)	564.48	-2660461.16	-2660227.49
TS2^e	556.61	-2660253.74	-2660075.21
P2^f	574.98	-2660324.63	-2660146.10

Reaction	ΔG^0—/(kJ·mol^-1)	ΔH^0—/(kJ·mol^-1)
[NH₂e-mim]⁺[BF₄]^- [NH₂e-mim]⁺+ [BF₄]^-	332.65	385.16
2[NH₂e-mim]⁺→[NHe-mim] + [NH₃e-mim]²⁺	553.98	701.01
[NHe-mim] + [BF₄]^-→[NHe-mim][BF₄]^-	97.93	49.88
[NH₂e-mim]⁺+[BF₄]^-→[NH₂e-mim]⁺[BF₄]^-	-332.65	-385.16
[NH₃e-mim]²⁺+[BF₄]^-→[NH₃e-mim]²⁺[BF₄]^-	-571.57	-773.73
2[NH₂e-mim]⁺[BF₄]^-+CO₂→IM1	-175.91	-248.11
2[NH₂e-mim]⁺[BF₄]^-+CO₂→TS1	-133.90	-272.79
2[NH₂e-mim]⁺[BF₄]^-+CO₂→TS2	-463.74	-565.22
2[NH₂e-mim]⁺[BF₄]^-+CO₂→P1	-448.96	-553.19
[NH₂e-mim]⁺[BF₄]^-+CO₂→TS2	207.41	152.28
[NH₂e-mim]⁺[BF₄]^-+CO₂→P2	136.53	81.39

Density Functional Theory Studies on the CO₂ Absorption by 1-Ethylamine-3-methylimidazolium Tetrafluoroborate^†

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