離子液體吸收硫化氫的熱力學(xué)研究

1、Supplementary MaterialThermodynamic Validation of 1-Alkyl-3-methylimidazoliumCarboxylates as Task-Specific Ionic Liquids for H 2sAbsorptionKuan Huang, Da-Niu Cai, Yong-Le Chen, You-Ting Wu , Xing-Bang Hu , Zhi-BingZhangSeparation Engineering Research Center, Key Laboratory of Mesoscopic Chemistry of

2、 MOE, School of Chemistry and Chemical Engineering, Nanjing University,Nanjing 210093, P. R. ChinaThis file contains:Synthesis and characterization of ILs.Absorption data of H2s in ILs at different temperatures and pressuresCalculated chemical and physical absorption capacity.Linear correlation of l

3、nK2 vs 1/T.Linear correlation of lnH vs 1/T.S1Synthesis and characterization of ILsPreparation of emimAce7.52 g emimBr was dissolved in 50 ml ethanol/water (1:1v/v) and added to a 250 mL round bottom flask, which was equipped with a magnetic stirbar. The flask was placed in an ice-water bath on a ma

4、gnetic stirplate. To this mixture was added 6.57 g of AgAc by portion and the reaction mixture was allowed to stir in dark for about 24 h. The product mixture was filtered, and the volatile solvents were removed from the filtrate under vacuum with a rotary evaporator at 333 K. Resulting crude produc

5、t was dried in vacuo over PO5 at 353 K for 72 h to remove trace of solvents. 1H NMR(300MHz, CDCl3, 25c, TMS),占 1.45ppm(3H, t), 1.84ppm(3H, s), 3.94ppm(3H, s), 4.25ppm(2H, q), 7.32ppm(1H, s), 7.34ppm(1H, s), 10.76ppm(1H, s); 1313C NMR(300MHz, DMSO-d6, 25 C, TMS),ppm):15.67, 26.11, 35.94, 44.42, 122.4

6、1, 123.98, 137.66, 174.56; Elemental Analysis, Calculated for C8H14N2O2： C56.45%, H8.29%, N16.46%, Found: C56.81%, H8.80%, N16.62%; MS: 110.75 for C6HnN2+ (calculated: 111.17), 58.45 for QH3O2- (calculated: 59.04).1.2 Preparation of emimPro4.86 g of Ag2O was suspended in 50 mL ethanol/water (1:1v/v)

7、 and added to a 250 mL round bottom flask, which was equipped with a magnetic stirbar. The flask was placed in an ice-water bath on a magnetic stirplate. To the stirred slurry of Ag2O was slowly added 3.11 g propionic acid. To this mixture was added 8.02 g of emimBr and the reaction mixture was allo

8、wed to stir in dark for about 24 h. The productS2 mixture was filtered, and the volatile solvents were removed from the filtrate under vacuum with a rotary evaporator at 333 K. Resulting crude product was dried in vacuo over P2O5 at 353 K for 72 h to remove trace of solvents._ _一_H NMR(300MHz, CDCl3

9、, 25c, TMS),占 0.90ppm(3H, t), 1.36ppm(3H, t), 2.00ppm(2H, q), 3.86ppm(3H, s), 4.18ppm(2H, q), 7.31ppm(1H, s), 7.33ppm(1H, s), 10.44ppm(1H, s); 13C NMR(300MHz, DMSO-d 6, 25C , TMS),即pm): 11.80, 15.68, 31.91,35.87, 44.35, 122.44, 123.99, 138.02, 177.43; Elemental Analysis, Calculated for C9H16N2O2： C5

10、8.67%, H8.75%, N15.21%, Found: C58.68%, H8.80%, N15.19%; MS: 110.75 for C6H11N2+ (calculated: 111.17), 72.50 for 0*。2- (calculated: 73.07).1.3 Preparation of emimLac4.98 g of Ag2O was suspended in 50 mL ethanol/water (1:1v/v) and added to a 250 mL round bottom flask, which was equipped with a magnet

11、ic stirbar. The flask was placed in an ice-water bath on a magnetic stirplate. To the stirred slurry of Ag2O was slowly added 3.87 g lactic acid. To this mixture was added 8.21 g of emimBr and the reaction mixture was allowed to stir in dark for about 24 h. The product mixture was filtered, and the

12、volatile solvents were removed from the filtrate under vacuum with a rotary evaporator at 333 K. Resulting crude product was dried in vacuo over P2O5 at 353 K for 72 h to remove trace of solvents.11H NMR(300MHz, CDCl3, 25c, TMS), 占 1.22ppm(3H, d), 1.45ppm(3H, t), 3.83ppm(1H, q), 3.93ppm(3H, s), 4.23

13、ppm(2H, q), 7.33ppm(2H, s), 10.36ppm(1H, s); 1313C NMR(300MHz, DMSO-d6, 25C , TMS),即pm): 15.62, 22.03, 35.99, 44.48,S367.57, 122.44, 124.01, 137.44, 177.76; Elemental Analysis, Calculated for CH16N3O2: C53.98%, H8.05%, N13.99%, Found: C54.04%, H8.06%, N14.10%; MS: 110.75 for C6H11N2+ (calculated: 11

14、1.17), 88.55 for GH5O3- (calculated: 89.07).1.4 Preparation of bmimAce7.68 g bmimBr was dissolved in 50 ml ethanol/water (1:1v/v) and added to a 250 mL round bottom flask, which was equipped with a magnetic stirbar. The flask was placed in an ice-water bath on a magnetic stirplate. To this mixture w

15、as added 6.47 g of AgAc by portion and the reaction mixture was allowed to stir in dark for about 24 h. The product mixture was filtered, and the volatile solvents were removed from the filtrate under vacuum with a rotary evaporator at 333 K. Resulting crude product was dried in vacuo over PO5 at 35

16、3 K for 72 h to remove trace of solvents.H NMR(300MHz, CDCl3, 25C, TMS), 占 0.81ppm(3H, t), 1.22ppm(2H, m), 1.73ppm(2H, m), 1.84ppm(3H, s), 3.93ppm(3H, s), 4.16ppm(2H, t), 7.22ppm(1H, s), 7.31ppm(1H, s), 11.04ppm(1H, s); 13C NMR(300MHz, DMSO-d6, 25 C, TMS), appm): 13.63, 19.21, 26.49, 31.96, 35.83, 4

17、8.62, 122.81, 124.03, 138.56, 173.91; Elemental Analysis, Calculated for C10H18N2O2: C60.58%, H9.15%, N14.13%, Found: C60.68%, H9.06%, N14.19%; MS: 139.80 for C 8H15N2+ (calculated: 139.22), 58.45 - for C2H3O2 (calculated: 59.04).1.5 Preparation of hmimAce7.96 g hmimBr was dissolved in 50 ml ethanol

18、/water (1:1v/v) and added to aS4250 mL round bottom flask, which was equipped with a magnetic stirbar. The flask was placed in an ice-water bath on a magnetic stirplate. To this mixture was added 5.87 g of AgAc by portion and the reaction mixture was allowed to stir in dark for about 24 h. The produ

19、ct mixture was filtered, and the volatile solvents were removed from the filtrate under vacuum with a rotary evaporator at 333 K. Resulting crude product was dried in vacuo over PO5 at 353 K for 72 h to remove trace of solvents.NMR(300MHz, CDCl 3, 25 C , TMS), 占 0.60ppm(3H, t), 1.041.09ppm(6H, br),

20、1.62ppm(2H, t), 1.71ppm(3H, s), 3.81ppm(3H, s), 4.02ppm(2H, t), 7.17ppm(1H, s), 7.31ppm(1H, s), 10.75ppm(1H, s); 13C NMR(300MHz, DMSO-d6, 25c, TMS), ppm): 14.19, 22.35, 25.62, 26.32, 29.98, 31.04, 35.88, 48.96, 122.76, 124.02, 138.36, 174.07; Elemental Analysis, Calculated for C12H22N2O2: C63.68%, H

21、9.79%, N12.38%, Found: C63.79%, H9.56%, N12.19%; MS: 166.80 for C10H19N2+ (calculated: 167.27), 58.45 for GH3O2- (calculated: 59.04).Absorption data of RS in ILs at different temperatures and pressures2.1 Solubilities of H 2s in emimAce293.15 K303.15 K313.15 K323.15 K333.15 KP(100kPa)mol/kguncertain

22、tyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertainty0.0140.740一一-22.1 10 20.0090.635一 一一-22.0 10 20.0140.6702.0 M0-20.0210.5931.9 M0-20.0490.6761.8 M0-20.0641.4042.1 10-20.0471.1162.0 10-20.0871.2692.0 M0-20.1161.1571.9 M0-20.2131.211.8 M0-20.232

23、2.021-22.1 100.1461.551-22.0 100.2371.674-22.0 M020.3031.563-21.9 M020.4921.604-21.8 M020.5162.6262.1 10-20.3231.9682.0 10-20.4472.0272.0 M0-20.5271.8621.9 M0-20.8281.9391.8 M0-20.8563.167-22.1 100.5862.403-22.0 100.6922.352.0 M0-20.7562.1211.9 M0-21.1602.2091.8 M0-21.1413.5962.1 10-20.8682.7852.0 1

24、0-20.9572.6562.0 M0-21.0532.4211.9 M0-21.4192.4151.8 M0-21.4163.966-22.1 101.1403.143-22.0 101.2592.9432.0 M0-21.3112.6441.9 10-21.7142.6091.8 M0-21.7374.371-22.1 10 21.4763.519-22.0 10 21.5583.2252.0 M0-21.5542.8671.9 10-22.0072.8141.8 M0-21.9624.6412.1 10-21.7683.8362.0 10-21.8693.525一一一-22.0 M021

25、.8453.09-21.9 M022.2682.967-21.8 M02S52.2014.9412.1-2102.1134.2072.0-2102.1873.7952.0 M0-22.1553.3191.9 M0-22.6153.1901.8 M0-22.5205.3352.1-2102.4614.5412.0-2102.5474.095一一一-22.0 M022.5153.601-21.9 M022.9663.402一一-21.8 M022.8925.7632.110-22.7894.8762.010-22.8414.3362.0 M0-22.8803.8541.9 M0-23.2293.5

26、431.8 M0-23.2086.1222.110-23.1915.2702.010-23.1924.5882.0 M0-23.2484.0951.9 M0-22.2 Solubilities of H 2s in emimPro293.15 K303.15 K313.15 K323.15 K333.15 KP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertainty0.0111.037-21.9

27、 100.0170.982-21.8 M020.0540.993-21.8 M020.1370.744-21.7 M020.1090.820-21.6 M020.0831.8511.9 10-20.1251.6991.8 M0-20.2441.5961.8 M0-20.2481.3461.7 M0-20.3361.2321.6 M0-20.2772.611-21.9 100.3802.3501.8 M0-20.5122.0951.8 M0-20.3241.7591.7 M0-20.5581.4981.6 M0-20.5113.2351.9 10-20.7292.9961.8 M0-20.700

28、2.351.8 M0-20.3872.1011.7 M0-20.8081.7261.6 M0-20.7983.870-21.9 100.9983.4251.8 M0-20.9152.6321.8 M0-20.4262.3121.7 M0-21.0681.9381.6 M0-21.0594.391-21.9 10 21.3323.9031.8 M0-21.1582.9421.8 M0-20.4672.5351.7 M0-21.4492.2311.6 M0-21.3414.9121.9 10-21.6554.348-21.8 M021.4753.300-21.8 M020.5112.77421.7

29、 M021.7252.410-21.6 M021.6395.411-21.9 101.9814.755-21.8 M021.7723.637-21.8 M020.5533.002-21.7 M021.9962.600-21.6 M021.9815.965-21.9 102.3575.2161.8 M0-22.0483.9191.8 M0-20.5913.2081.7 M0-22.3122.8061.6 M0-22.2966.4701.9 10-22.6525.5691.8 M0-22.3074.1631.8 M0-20.6483.5171.7 M0-22.6463.0181.6 M0-22.6

30、046.953-21.9 102.9425.8841.8 M0-22.6364.4891.8 M0-20.6783.6801.7 M0-23.2393.3711.6 M0-22.9597.4901.9 10-23.1966.1881.8 M0-22.9834.8201.8 M0-20.7153.8811.7 M0-23.1677.800-21.9 10 23.2245.0531.8 M0-20.7684.1691.7 M0-22.3 Solubilities of H 2s in emimLac293.15 K303.15 K313.15 K323.15 K333.15 KP(100kPa)m

31、ol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertainty0.0780.6841.8 10-20.0440.4541.7 M0-20.1690.6841.7 M0-20.0770.4101.6 M0-20.1310.4291.5 M0-20.2491.154-21.8 100.1820.8891.7 M0-20.3580.9791.7 M0-20.2720.7541.6 M0-20.2960.6441.5 M0-2

32、0.5141.6381.8 10-20.5401.4981.7 M0-20.5711.2441.7 M0-20.5301.0491.6 M0-20.5330.8591.5 M0-20.7872.033-21.8 100.8451.8981.7 M0-20.8331.5381.7 M0-20.8031.2981.6 M0-20.7761.0541.5 M0-21.0632.3971.8 10-21.1882.2821.7 M0-21.1291.8131.7 M0-21.1781.6081.6 M0-21.0821.2631.5 M0-21.3772.787-21.8 101.5442.6371.

33、7 M0-21.5032.1321.7 M0-21.4931.8481.6 M0-21.4571.4931.5 M0-21.6933.1661.8 10-21.8872.9461.7 M0-21.8242.3821.7 M0-21.8072.0631.6 M0-21.7551.6731.5 M0-22.0253.5261.8 10-22.2813.3111.7 M0-22.1572.6471.7 M0-22.1462.2821.6 M0-22.0531.8331.5 M0-22.2933.8201.8 10-22.6483.6311.7 M0-22.4792.8821.7 M0-22.5202

34、.5021.6 M0-22.3802.0081.5 M0-22.5844.140-21.8 102.9943.92_-21.7 M022.8313.13121.7 M022.8322.692-21.6 M022.7152.17221.5 M022.8974.465-21.8 10 23.1904.0651.7 M0-23.1873.3861.7 M0-23.1992.9171.6 M0-22.9432.2821.5 M0-23.2054.7941.8 10-23.2162.4071.5 M0-2S62.4 Solubilities of H 2s in bmimAce293.15 K303.1

35、5 K313.15 K323.15 K333.15 KP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertainty0.0010.4031.8 10-20.0050.6351.7 M0-20.0030.4991.7 M0-20.0040.3451.6 M0-20.0080.3661.5 M0-20.0090.9381.8 10-20.0581.2851.7 M0-20.0170.9191.7 M0-

36、20.0160.7071.6 M0-20.0360.7761.5 M0-20.0271.2811.8 10-20.2391.9061.7 M0-20.1421.5731.7 M0-20.0981.2161.6 M0-20.1211.1651.5 M0-20.0791.6811.8 10-20.4782.4251.7 M0-20.3261.9951.7 M0-20.2261.5461.6 M0-20.2951.5111.5 M0-20.2052.149-21.8 100.8493.078-21.7 M020.5752.388-21.7 M020.4521.890-21.6 M020.5121.7

37、98-21.5 M020.3462.5131.8 10-21.1653.5761.7 M0-20.8112.7171.7 M0-20.7292.2271.6 M0-20.7422.0431.5 M0-20.5232.8991.8 10-21.4783.9391.7 M0-21.0663.0161.7 M0-20.9192.4231.6 M0-21.0142.2931.5 M0-20.8103.4211.8 10-21.8244.3721.7 M0-21.4123.4041.7 M0-21.1862.6851.6 M0-21.3152.5471.5 M0-21.0533.846-21.8 102

38、.1964.7481.7 M0-21.7833.8001.7 M0-21.5443.0041.6 M0-21.6582.8111.5 M0-21.3544.3151.8 10-22.5785.2361.7 M0-22.1454.1481.7 M0-22.0643.4401.6 M0-22.0023.0641.5 M0-21.6374.735-21.8 102.9725.667-21.7 M022.5444.513-21.7 M022.4843.756-21.6 M022.3453.307-21.5 M021.9315.1891.8 10-23.2025.9201.7 M0-23.0554.91

39、41.7 M0-22.7743.9661.6 M0-22.6803.5311.5 M0-22.2445.632-21.8 103.2785.1181.7 M0-23.0994.2101.6 M0-23.0133.7511.5 M0-22.6006.0961.8 10-23.1864.2771.6 M0-23.4154.0031.5 M0-22.9256.533-21.8 103.2196.9361.8 10-22.5 Solubilities of H 2s in hmimAce293.15 K303.15 K313.15 K323.15 K333.15 KP(100kPa)mol/kgunc

40、ertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertaintyP(100kPa)mol/kguncertainty0.0030.614-21.7 100.0050.7541.6 M0-20.0060.6841.6 M0-20.0130.6591.5 M0-20.0060.4371.5 M0-20.0361.3571.7 10-20.0581.4481.6 M0-20.0631.3371.6 M0-20.1231.3781.5 M0-20.0320.8441.5 M0-20.1731.9

41、81-21.7 100.2001.9501.6 M0-20.2411.8641.6 M0-20.3771.8741.5 M0-20.1401.3041.5 M0-20.3872.523-21.7 100.4052.404一一-21.6 M020.5042.333一一-21.6 M020.5572.12421.5 M020.2981.60621.5 M020.6363.0311.7 10-20.6262.794-21.6 M020.8532.827-21.6 M020.7872.40321.5 M020.5381.90321.5 M020.8993.5081.7 10-20.8473.1481.6 M0-21.1813.2461.6 M0-21.0272.6491.5 M0-20.7782.1621.5 M0-21.1873.983-21.7 101.0953.5401.6 M0-21.5483.6621.6 M0-21.3532.9791.5 M0-21.0182.3841.5 M0-21.4894.4501.7 10-21.3743.9211.6 M0-21.9234.0591.6 M0-21.7003.2641.5 M0-21.3292.6471.5 M0-21.7924.900-21.7