簡易檢索 / 詳目顯示

研究生: 李昕穎
論文名稱: 以吹氣捕捉系統量測氨及一級脂肪胺之亨利常數
Determination of Henry's law constants of ammonia and primary aliphatic amines by purge-and-trap system
指導教授: 吳劍侯
口試委員:
學位類別: 碩士
Master
系所名稱: 原子科學院 - 生醫工程與環境科學系
Department of Biomedical Engineering and Environmental Sciences
論文出版年: 2010
畢業學年度: 98
語文別: 中文
論文頁數: 60
中文關鍵詞: 銨離子一級胺亨利常數離子強度
外文關鍵詞: Ammonium, Primary amine, Henry's law constant, Ionic strength
相關次數: 點閱:1下載:0
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 亨利常數(KH; M atm-1)對於探討化學物質於環境中的分布及宿命為一重要的參數。本論文使用一自製吹氣捕捉系統,利用銨離子(NH4+)於鹼性環境下會轉變成氨(NH3(g))的特性,搭配離子層析儀及鄰苯二甲醛(OPA)螢光衍生法量測氨於1 M氫氧化鈉濃度時溫度範圍在283□323 K之KH,並與先前於0.1及10 M氫氧化鈉濃度時所量測的結果作比較,發現隨著離子強度增加會因產生鹽析反應而使所量測之KH變小,利用Setschenow方程式修正可得到25oC離子強度可忽略時氨的KH為50 M atm-1;40oC時氨的KH為19 M atm-1。同時氨在含有1M氫氧化鈉濃度時的KH對溫度T(K)的關係為log KH=-6.36+2352.7/T,T為283□323 K。此系統並嘗試利用OPA螢光衍生搭配高效液相層析儀(HPLC)應用於同時量測C2-C9 一級脂肪胺的亨利常數。


    The Henry’s law constant (KH; M atm-1) plays an important role on the study of the distribution and the fate of chemicals in the environment. In principle ammonium ion (NH4+) becomes gaseous ammonia (NH3(g)) in aqueous solutions at alkaline environment. The Henry’s law constant of ammonia in 1 M sodium hydroxide (NaOH) over a temperature range of 283□323 K can be precisely determined using a homemade purge-and-trap system with ion chromatography and o-phthaldialdehyde (OPA) derivatization fluorescence as analysis method. The results were also compared with KH previously measured in 0.1 and 10 M NaOH and showed that the values of KH of ammonia decreased with increased ionic strengths of solution as a result of salting-out effect. The corrected experimental KH in deionized water was 50 M atm-1 at 298 K and 19 M atm-1 at 313 K by using Setschenow equation. The relation of KH with temperature was described by the equation: log KH= -6.36+2352.7/T, T= 283□323K. This system could also be applied to measure KH of C2-C9 primary amines simultaneously by using OPA derivatization HPLC with fluorescence detection.

    目錄 中文摘要 I 英文摘要 II 謝誌 III 目錄 IV 圖目錄 VII 表目錄 IX 第一章 前言 1 1-1 簡介 1 1-2 研究目的 1 第二章 文獻回顧 4 2-1 氨及C2□C9一級脂肪胺基本性質 4 2-2 亨利常數 6 2-2-1 亨利常數的影響因素 7 2-2-2 亨利常數的決定方法 9 2-2-2-1 物化性質推算 9 2-2-2-2 官能基或鍵結估算 10 2-2-2-3 實驗方法測量 12 2-2-3 氨及一級脂肪胺的亨利常數量測 13 2-3 吹氣捕捉系統模式探討 14 第三章 實驗材料、設備與方法 20 3-1實驗藥品 20 3-1-1 實驗藥品及試劑 20 3-1-2 藥品配製 21 3-2 儀器設備 22 3-2-1 高效液相層析儀 22 3-2-2 離子層析儀 23 3-2-3 螢光光譜儀 25 3-2-4 吹氣捕捉裝置 25 3-2-5 其他實驗器材 27 3-3 利用吹氣捕捉系統測量亨利常數之實驗流程 28 3-3-1 氨 28 3-3-2 C2-C9一級脂肪胺 29 3-4 氨的分析方法 30 3-5 C2-C9一級脂肪胺的分析方法 31 3-5-1 螢光光譜儀 31 3-5-2 HPLC—OPA螢光衍生法分析條件 31 第四章 結果與討論 34 4-1 氨的亨利常數 34 4-1-1 理論模型推導氨的亨利常數 34 4-1-2 1 M NaOH 下量測氨的亨利常數對溫度的變化 36 4-1-3 不同離子強度下氨的亨利常數對溫度的變化 38 4-1-4 氨的亨利常數對離子強度的變化 41 4-1-5 kg值探討 44 4-2 利用吹氣捕捉系統量測C2-C9一級脂肪胺的亨利常數 46 4-2-1 吹氣瓶材質 46 4-2-2 捕捉液之選擇 47 4-2-3 NaOH濃度對吹除效率的影響 50 4-2-4 吹除時間探討 51 4-2-5 理論模型推導C2-C9一級脂肪胺的亨利常數 52 第五章 結論與展望 54 參考文獻 55 附錄 AP1 A. 1 M NaOH時不同溫度(283-323 K)氨之吹除時間與檢量線關係 AP1 B. 不同氫氧化鈉濃度(3, 7 M)時氨之吹除時間與檢量線關係 AP6 C. 不同溫度下亨利常數與離子強度及氫氧化鈉濃度的關係 AP8 D. 添加不同濃度NaCl時氨之吹除時間與檢量線關係 AP9 E. 添加不同濃度KCl時氨之吹除時間與檢量線關係 AP11 F. 添加2 M KNO3時氨之吹除時間與檢量線關係 AP13 G. 不同濃度胺在不同捕捉液濃度下之檢量線關係 AP14 H. 不同濃度胺在不同氫氧化鈉濃度下之檢量線關係 AP19 I. 不同濃度胺在不同吹除時間下之檢量線關係 AP21 圖目錄 圖2-1 C2-C9一級脂肪胺之沸點、熔點與碳數的關係 4 圖2-2 NH3(aq)與NH4+(aq)的分佈與pH的關係 5 圖2-3 氣提裝置 13 圖2-4 雙層膜理論水相中揮發性化合物之揮發過程 15 圖2-5 銨離子從液相中釋放至氣相中的質量平衡模型 17 圖3-1 高效液相層析儀(HPLC)裝置圖 23 圖3-2 離子層析儀裝置圖 24 圖3-3 吹氣捕捉系統示意圖 25 圖3-4 吹氣捕捉系統測量氨亨利常數的實驗流程圖 28 圖3-5 吹氣捕捉系統測量胺亨利常數的實驗流程圖 29 圖3-6 離子層析儀(IC)與OPA螢光衍生法(FL)分析銨離子之方法比較 30 圖3-7 HPLC搭配螢光分析裝置流程圖 31 圖4-1 1 M NaOH下氨在283-323 K對時間的吹除效率 37 圖4-2 kapp在不同氫氧化鈉濃度下與溫度之比較 38 圖4-3 kabs在不同氫氧化鈉濃度下與溫度之比較 39 圖4-4 不同氫氧化鈉濃度氨的最終吹除效率與溫度之比較 39 圖4-5 不同氫氧化鈉濃度氨的亨利常數對溫度作圖並與文獻值比較 41 圖4-6 不同氫氧化鈉濃度及離子強度下氨的亨利常數 43 圖4-7 水作為捕捉液時之對C2-C9 一級脂肪胺之捕捉效率 47 圖4-8 OPA-NAC衍生試劑作為捕捉液時對C2-C9 一級脂肪胺之捕捉效率 48 圖4-9 不同濃度酸與水作為捕捉液對C2-C9 一級脂肪胺之捕捉效率 50 圖4-10 吹氣捕捉系統中吹氣瓶之氫氧化鈉濃度與吹除效率比較圖 51 圖4-11 氮氣吹除時間對吹除效率比較圖 52 表目錄 表1-1 氨及C2-C9一級脂肪胺之基本性質與亨利常數文獻值 3 表2-1 鍵結貢獻值 11 表2-2 官能基與鍵結模式貢獻預測C2-C9 一級脂肪胺之亨利常數比較 11 表3-1 離子層析儀儀器設定參數 24 表3-2 吹氣捕捉系統最佳參數 27 表3-3 HPLC—螢光分析C2- C9一級脂肪胺之設定參數與實驗條件 32 表3-4 HPLC動相層析條件 33 表4-1 系統中之常數項 36 表4-2 1 M NaOH, 283 K-323 K之氨的亨利常數及各項參數 38 表4-3 氨在不同溫度及氫氧化鈉溶液中之的亨利常數實驗值 40 表4-4 本系統與不同文獻值中氨於298 K的亨利常數 41 表4-5 加入不同鹽類對亨利常數的影響 44 表4-6 考慮kg與否之亨利常數值比較 45 表4-7 不同材質吹除瓶之吹除效率 46 表4-8 不同濃度捕捉液之pH值 49 表4-9 氨之各項參數及亨利常數實驗值與文獻值比較 53

    Ábalos, M.; Bayona, J. M.; Ventura, F., Development of a Solid-phase microextraction GC-NPD procedure for the determination of free volatile amines in wastewater and sewage-polluted waters. Anal. Chem. 1999, 71, 3531-3537.
    Akyüz, M., Simultaneous determination of aliphatic and aromatic amines in ambient air and airborne particulate matters by gas chromatography-mass spectrometry. Atmos.Environ. 2008, 42, 3809-3819.
    Altschuh, J.; Brüggemann, R.; Santl, H.; Eichinger, G.; Piringer, O. G., Henry's law constants for a diverse set of organic chemicals: Experimental determination and comparison of estimation methods. Chemosphere 1999, 39, 1871-1887.
    Askari, M. D. F.; Maskarinec, M. P.; Smith, S. M.; Beam, P. M.; Travis, C. C., Effectiveness of purge-and-trap for measurement of volatile organic compounds in aged soils. Anal. Chem. 1996, 68, 3431-3433.
    Balamuru, V. G.; Ibrahim, O. M.; Barnett, S. M., Simulation of ternary ammonia-water-salt absorption refrigeration cycles. Int. J. Refrig. 2000, 23, 31-42.
    Bamford, H. A.; Poster, D. L.; Baker, J. E., Henry's law constants of polychlorinated biphenyl congeners and their variation with temperature. J. Chem. Eng. Data 2000, 45, 1069-1074.
    Barsanti, K. C.; McMurry, P. H.; Smith, J. N., The potential contribution of organic salts to new particle growth. Atmos. Chem. Phys. 2009, 9, 2949-2957.
    Bullock, K. R.; Teja, A. S., Henry's constants of volatile organic compounds in aqueous salt solutions. Ind. Eng.Chem. Res. 2003, 42, 6494-6498.
    Cabeza, A. S.; Martinez, Y. M.; Legua, C. M.; Falcó, P. C., Rapid fluorimetric assay for primary amine groups in water samples. Anal. Bioanal. Chem. 2003, 376, 918-922.
    Campillo, N.; Viñas, P.; López-García, I.; Aguinaga, N.; Hernández-Córdoba, M., Determination of volatile halogenated organic compounds in soils by purge-and-trap capillary gas chromatography with atomic emission detection. Talanta 2004, 64, 584-589.
    Chai, X.-S.; Falabella, J. B.; Teja, A. S., A relative headspace method for Henry's constants of volatile organic compounds. Fluid Phase Equilibr. 2005, 231 239-245.
    Chen, C. C.; Britt, H. I.; Boston, J. F.; Evans, L. B., Extension and application of the pitzer equation for vapor-liquid equilibrium of aqueous electrolyte systems with molecular solutes. Am. Inst. Chem. Eng. J. 1979, 25, 820-831.
    Christie, A. O.; Crisp, D. J., Activity coefficients of the n-primary, secondary and tertiary aliphatic amines in aqueous solution. J. Appl. Chem. 1967, 17, 11-14.
    Chung, M. Y.; Muthana, S.; Paluyo, R. N.; Hasson, A. S., Measurements of effective henry's law constants for hydrogen peroxide in concentrated salt solutions. Atmos. Environ. 2005, 39, 2981–2989.
    Clegg, S. L.; Brimblecombe, P., Solubility of ammonia in pure aqueous and multicomponent solutions. J. Phys. Chem. 1989, 93, 7237-7248.
    Dasgupta, P. K.; Dong, S., Solubility of ammonia in liquid water and generation of Trace Levels of Standard Gaseous Ammonia. Atmos. Environ. 1986, 20, 565-570.
    Davis, M. L.; Masten, S. J., Principles of Environmental Engineering and Science New York, McGraw-Hill Science, 2004.
    De Preter, V.; Van Staeyen, G.; Esser, D.; Rutgeerts, P.; Verbeke, K., Development of a screening method to determine the pattern of fermentation metabolites in faecal samples using on-line purge-and-trap gas chromatographic-mass spectrometric analysis. J. Chromatogr. A 2009, 1216, 1476-1483.
    Demou, E.; Donaldson, D. J., Adsorption of atmospheric gases at the air−water interface. 4:  the influence of salts. J. Phys. Chem. A 2002, 106, 982-987.
    Edwards, T. J.; Maurer, G.; Newman, J.; Prausnitz, J. M., Vapor-liquid equilibria in multicomponent aqueous solutions of volatile weak electrolytes. AlChE Journal 1978, 24, 966-976.
    Ettre, L. S.; Welter, C.; Kolb, B., Determination of gas-liquid partition coefficients by automatic equilibrium headspace-gas chromatography utilizing the phase ratio variation method. Chromatographia 1993, 35, 73-84.
    Fogg, P. G. T., Some aspects of the solubility of gases in liquids. Monatsh. Chem. 2003, 134, 619-631.
    Hales, J. M.; Drewes, D. R., Solubility of ammonia in water at low concentrations. Atmos. Environ. 1979, 13, 1133-1147.
    Haslam, B. R. T.; Hershey, R. L.; Keen, R. H., Effect of gas velocity and temperature on rate of absorption. Ind. Eng. Chem. 1924, 16, 1224-1230.
    Hine, J.; Mookerjee, P. K., Structural effects on rates and equilibriums. XIX. Intrinsic hydrophilic character of organic compounds. Correlations in terms of structural contributions. J. Org. Chem. 1975, 40, 292-298.
    Howard-Reed, C.; Corsi, R. L., Mass transfer of volatile organic compounds from drinking water to indoor air: the role of residential dishwashers. Environ. Sci. Technol. 1999, 33, 2266-2272.
    Kamarei, F.; Ebrahimzadeh, H.; Yamini, Y., Optimization of solvent bar microextraction combined with gas chromatography for the analysis of aliphatic amines in water samples. J. Hazard. Mater. 2010, 178, 747-752.
    Kan, A. T.; Lu, H.; Tomson, M. B., Effects of monoethylene glycol on carbon dioxide partitioning in gas/monoethylene glycol/water/salt mixed systems. Ind. Eng.Chem. Res. 2010, 49, 5884-5890.
    Kolb, B.; Welter, C.; Bichler, C., Determination of partition coefficients by automatic equilibrium headspace gas chromatography by vapor phase calibration Chromatographia 1992, 34, 235-240.
    Kuo, C.-T.; Wang, P.-Y.; Wu, C.-H., Fluorometric determination of ammonium ion by ion chromatography using postcolumn derivatization with o-phthaldialdehyde. J. Chromatogr. A 2005, 1085, 91-97.
    Lau, F. K.; Charles, M. J.; Cahill, T. M., Evaluation of gas-stripping methods for the determination of Henry's law constants for polybrominated diphenyl ethers and polychlorinated biphenyls. J. Chem. Eng. Data 2006, 51, 871-878.
    Lee, H.; D’eon, J.; Mabury, S. A., Biodegradation of polyfluoroalkyl phosphates as a source of perfluorinated acids to the environment. Envir. Sci. Technol. 2010, 44, 3305-3310.
    Lewis, W. K.; Whitman, W. G., Principles of gas absorption. Ind. Eng. Chem.1924, 16, 1215-1220.
    Lide, D. R., CRC Handbook of chemistry and physics. Boca Raton, FL, 2004.
    Mackay, D.; Shiu, W. Y., A critical review of Henry's law constants for chemicals of environmental interest. J. Phys. Chem. Ref. Data 1981, 10, 1175-1191.
    Mackay, D.; Shiu, W. Y.; Sutherland, R. P., Determination of air-water Henry's law constants for hydrophobic pollutants. Envir. Sci. Technol. 1979, 13, 333-337.
    Malloy, Q. G. J.; Li, Q.; Warren, B.; Cocker Iii, D. R.; Erupe, M. E.; Silva, P. J., Secondary organic aerosol formation from primary aliphatic amines with NO3 radical. Atmos. Chem. Phys. 2009, 9, 2051-2060.
    Martinez, A.; Wang, K.; Hornbuckle, K. C., Fate of PCB congeners in an industrial harbor of lake Michigan. Envir. Sci. Technol. 2010, 44, 2803-2808.
    Meylan, W. M.; Howard, P. H., Bond contribution method for estimating Henry's law constants. Environ. Toxicol. Chem. 1991, 10, 1283-1293.
    Molnár-Perl, I., 2.2.1. HPLC of amines as o-phthalaldehyde derivatives. Journal of Chromatography Library, P. D. Ibolya Molnár-Perl, Ed. Elsevier: 2005; Vol. 70, p405-444.
    Namiesnik, J.; Jastrzebska, A.; Zygmunt, B., Determination of volatile aliphatic amines in air by solid-phase microextraction coupled with gas chromatography with flame ionization detection. J. Chromatogr. A 2003, 1016, 1-9.
    Ni, J., Mechanistic models of ammonia release from liquid manure: a Review. J. Agr. Eng. Res. 1999, 72, 1-17.
    Pitzer, K. S., Activity coefficients in electrolyte solutions. Boca Raton, CRC Press, 1991.
    Pitzer, K. S.; Kim, J. J., Thermodynamics of electrolytes: Part 2. Activity and osmotic coefficients for mixed electrolytes. J. Am. Chem. Soc. 1974, 96, 5701-5707.
    Povolo, M.; Contarini, G., Comparison of solid-phase microextraction and purge-and-trap methods for the analysis of the volatile fraction of butter. J. Chromatogr. A 2003, 985, 117-125.
    Pratt, K. A.; Hatch, L. E.; Prather, K. A., Seasonal volatility dependence of ambient particle phase amines. Environ. Sci. Technol. 2009, 43, 5276-5281.
    Rampfl, M.; Mair, S.; Mayer, F.; Sedlbauer, K.; Breuer, K.; Niessner, R., Determination of primary, secondary, and tertiary amines in air by direct or diffusion sampling followed by determination with liquid chromatography and tandem mass spectrometry. Environ. Sci. Technol. 2008, 42, 5217-5222.
    Sahasrabuddhey, B.; Jain, A.; Verma, K. K., Determination of ammonia and aliphatic amines in environmental aqueous samples utilizing pre-column derivatization to their phenylthioureas and high performance liquid chromatography. Analyst 1999, 124, 1017-1021
    Setschenow, J. Z., Uber die konstitution der salzlosungenauf grund Ihres verhaltens zu kohlensaure. Physik. Chem. 1889, 4, 117-125.
    Shi, Q.; Davidovits, P.; Jayne, J. T.; Worsnop, D. R.; Kolb, C. E., Uptake of gas-phase ammonia. 1. Uptake by aqueous surfaces as a function of pH. J. Phys. Chem. A 1999, 103, 8812-8823.
    Simon, P.; Lemacon, C., Determination of aliphatic primary and secondary amines and polyamines in air by high-performance liquid chromatography. Anal. Chem. 1987, 59, 480-484.
    Smith, R. M.; Martell, A. E. NIST standard reference database 46, NIST Critically selected stability constants of metal complexes database, Version8.0, US Department of Commerce, National Institute of Standards and Technology, 2004.
    Soria, A. C.; Martinez-Castro, I.; Sanz, J., Study of the precision in the purge-and-trap-gas chromatography-mass spectrometry analysis of volatile compounds in honey. J. Chromatogr. A 2009, 1216, 3300-3304.
    Staudinger, J.; Roberts, P. V., A critical compilation of Henry's law constant temperature dependence relations for organic compounds in dilute aqueous solutions. Chemosphere 2001, 44, 561-576.
    Tsai, C. J.; Huang, C. H.; Wang, S. H., Collection efficiency and capacity of three samplers for acidic and basic gases. Environ. Sci. Technol. 2001, 35, 2572-2575.
    Tykachinskii, I. D.; Kataeva, G. V., Accelerating effect of ammonium sulfate on the glass-melting process. Glass and Ceramics 1958, 15, 46-48.
    Westerholm, R.; Li, H.; Almén, J., Estimation of aliphatic amine emissions in automobile exhausts. Chemosphere 1993, 27, 1381-1384.
    Wilhelm, E.; Battino, R.; Wilcock, R. J., Low-pressure solubility of gases in liquid water. Chem. Rev. 1977, 77, 219-262.
    Winkel, L.; Feldmann, J.; Meharg, A. A., Quantitative and qualitative trapping of volatile methylated selenium species entrained through nitric acid. Environ. Sci. Technol. 2010, 44, 382-387.
    Wong, P. K.; Wang, Y. H., Determination of the Henry's law constant for dimethyl sulfide in seawater. Chemosphere 1997, 35, 535-544.
    Yang, G.; Ran, Y.; Yalkowsky, S. H., Prediction of the aqueous solubility: Comparison of the general solubility equation and the method using an amended solvation energy relationship. J. Pharm. Sci. 2002, 91, 517-533.
    吳靜宜, 水相中銅與胺基酸錯合物之光分解產物研究:氨的定量與分析. 碩士論文, 國立清華大學, 2005.
    林宗儀, 進一步改良吹氣捕捉系統搭配離子層析儀測量高鹽度樣品中銨離子濃度. 碩士論文, 國立清華大學, 新竹, 2008.
    潘奕達, 以吹氣捕捉前處理系統量測寬濃度範圍的氨及其亨利常數. 碩士論文, 國立清華大學, 新竹市, 2009.

    無法下載圖示 全文公開日期 本全文未授權公開 (校內網路)
    全文公開日期 本全文未授權公開 (校外網路)
    全文公開日期 本全文未授權公開 (國家圖書館:臺灣博碩士論文系統)
    QR CODE