Pollutant mixtures: investigation of resulting changes in the single compounds water solubility : Luận văn ThS. Công nghệ hóa học

1 HANOI UNIVERSITY OF SCIENCE TECHNICAL UNIVERSITAT DRESDEN PHAM THI BICH NGOC INVESTIGATION OF A LYSIMETER USING THE SIMULATION TOOL SiWaPro DSS AND ADAPTATION OF THIS PROGRAM TO VIETNAMESE REQUIREMENTS MASTER THESIS Tutor: Prof Dr Ing habil Peter Wolfgang Graeber Dipl Ing Rene Blankenburg Technical University Dresden Institute of Waste Management and Contaiminated Site Treatment HANOI – VIETNAM, DECEMBER 2008 TECHNISCHE UNIVERSITÄT DRESDEN INSTITUTE OF WASTE MANAGEMENT AND CONTAMINATED SITE TREATMENT Master Thesis Pollutant mixtures: Investigation of resulting changes in the single compounds water solubility Supervisor: Dipl.-Ing Dipl.-Ing Jens Fahl TU Dresden, Institute for Waste Management and Contaminated Site Treatment Hanoi, 2008 Acknowledgment First of all, I would like to express my thankfulness for Jens Fahl, my supervisor for your knowledge and enthusiasm Without your encouragement and advice I can not complete this work I also gratefully acknowledge Dr Axel Fischer for all you have done for me Special thanks for Marene, you are very kind and patient for me Thanks for Stefan, Claudia, I'm very grateful for your support I would like to thank Prof Dr Bilitewski, Prof Dr Nguyen Thi Diem Trang and Assc Prof Dr Bui Duy Cam for great effort to establish and develop this program I also would like express my gratitude to the following organizations for supporting me throughout the course - The Committee on Overseas Training Project- Ministry of Education and Training of Vietnam - Hanoi University of Science - Vietnam National University - Institute for Waste Management and Contaminated Site Treatment – TU Dresden - German Academic Exchange Service (DAAD) Warmly thanks to Mai, Christian, Hai Minh for your help Thanks to all my colleagues who shared a good time with me Finally, thanks to my family, my parent, my mother in law, my husband and my little son who always along with me, encourage and share difficulties and pleasure as well Hanoi, 10th December, 2008 Vu Huyen Phuong Table of contents Acknowledgment Table of contents Abbreviations Figures and pictures Tables Summary 10 INTRODUCTION 11 1.1 Some important definition related to solubility 16 1.2 Factors influencing solubility 17 1.2.1 Temperature effects: 17 1.2.2 Pressure effects 19 1.2.3 Salting out effect 20 1.2.4 Cosolvent effects 20 1.3 Estimation of solubility 21 MATERIALS AND METHODS 27 2.1 Materials 27 2.2 Experimental procedure 30 2.3 Analyzing method 33 2.3.1 Ethylbenzene and Toluene 33 2.3.2 Anthracene and Naphthalene 33 2.3.3 Phenol 34 2.3.4 Tetradecane 34 2.4 Assessment of experimental data 37 RESULTS AND DISCUSSIONS 39 3.1 Preliminary experiments 39 3.2 Water solubility of studied organic compounds in pure form 45 3.2.1 Solubility of Ethylbenzene in water 46 3.2.2 Solubility of Phenol in water 50 3.2.3 Solubility of Anthracene and Naphthalene in water 52 3.3 Water solubility of studied organic compound mixtures 55 3.3.1 Mixture of Ethylbenzene and Toluene 56 3.3.2 Mixture of Ethylbenzene and Phenol 58 3.3.3 Ethylbenzene – Anthracene – Naphthalene Mixture 60 3.3.4 Ethylbenzene – Toluene - Anthracene – Naphthalene Mixture 61 3.3.5 Phenol - Tetradecane Mixture; Naphthalene – Tetradecane Mixture and Special Mixture 64 PROSPECT 66 CONCLUSIONS 67 References 68 Statement under oath 71 Appendix 72 Abbreviations HOC: Hydrophobic Organic Chemical PMOS: Partially Miscible Organic Solvent IUPAC: International Union for Pure and Applied Chemistry VOC: Volatile Organic Compound PAH: Polycyclic Aromatic Hydrocarbon UNIFAC: Universal Quasi Chemical Functional Group Activity Coefficient BTEX: Benzene – Toluene – Ethylbenzene – Xylene GC: Gas Chromatograph HPLC: High Performance Liquid Chromatograph Figures and pictures Figure 1: Ranges in water solubility of some organic compound classes Figure 2: Water solubility as a function of temperature Figure 3: Experimental and predicted value for mixture ethanol – cyclohexane Figure 4: Ethylbenzene concentrations in aqueous phase of three time sampling Figure 5: Anthracene concentrations in aqueous phase of two time sampling Figure 6: Comparison of water solubility of Ethylbenzene in different temperature Figure 7: Comparison of water solubility of Toluene in different temperature Figure 8: Comparison of water solubility of Phenol in different temperature Figure 9: Solubility of Anthracene in water of selected data 10 18 25 Picture 1: Glass vial 20ml with special silicone septum Picture 2: Glass vessel 100ml with special rubber cap Picture 3: Glass vessel 500ml with special rubber cap Picture 4: Samples is kept at 20oC Picture 5: Store samples in room 5oC Picture 6: Store samples in room 10oC Picture 7: Taking sample by microliter syringe 50μl Picture 8: Taking sample by syringe 2ml Picture 9: Preparation sample for GC/headspace Picture 10: Preparation sample for HPLC Picture 11: GC/headspace Picture 12: GC System Picture 13: Spectrometer Picture 14: HPLC System Picture 15: Experiment to determine stirring needed or not to get maximum solubility 29 29 30 31 32 32 32 32 36 36 36 36 36 36 41 42 43 47 50 51 53 Tables Table 1: Chemical/physical properties of selected substances in this work 12 Table 2: Difference of solubility in different temperature 19 Table 3: Effect of pressure on the solubility of Xylene 19 Table 4: Purity of studied substances 28 Table 5: Concentration of Ethylbenzene and Anthracene at different times 39 Table 6: Ethylbenzene concentrations (mg/l) in stirring and non-stirring condition 41 Table 7: Anthracene concentrations (μg/l) in stirring and non-stirring condition 41 Table 8: Solubility of Ethylbenzene at different temperature (mg/l) 46 Table 9: Comparison of experimental data and literature data of Ethylbenzene 46 Table 10: Solubility of Toluene at different temperature (mg/l) 48 Table 11: Comparison of experimental data and literature data of Toluene 48 Table 12: Solubility of Phenol at different temperature (mg/l) 50 Table 13: Average value of phenol solubility in water 51 Table 14: Solubility of Naphthalene and Anthracene at 20oC 52 o Table 15: Comparison of experimental data and literature data of Antharacene at 20 C 52 Table 14: Comparison between experimental data and literature data of Naphthalene at 54 20oC Table 15: Aqueous concentration of Ethylbenzene and Toluene in their mixture at 56 20oC Table 16: Aqueous concentration of Ethylbenzene and Toluene in their mixture at 5oC 57 Table 17: Comparison of experimental and calculated solubility of Ethylbezene and 58 Toluene at 20oC Table 18: Aqueous concentration of Ethylbenzene and Phenol in their mixture at 20oC 59 Table 19: Aqueous concentration of Ethylbenzene and Phenol in their mixture at 5oC 59 Table 20: Aqueous concentration of Ethylbenzene – Anthracene – Naphthalene in the 60 o mixture at 20 C Table 21: Aqueous concentration of Ethylbenzene – Anthracene – Naphthalene in the mixture at 5oC 60 Table 22: Accuracy of experimental values for components in the mixture 61 Ethylbenzene – Anthracene – Naphthalene Table 23: Aqueous concentration of Ethylbenzene – Toluene - Anthracene – 62 o Naphthalene in the mixture at 20 C Table 24: Aqueous concentration of Ethylbenzene – Toluene - Anthracene – 62 Naphthalene in the mixture at 5oC Table 25: Accuracy of experimental values of component of mixture Ethylbenzene – 63 Anthracene – Naphthalene Table 26: Comparison of experimental and calculated solubility of each component in 63 o mixture Ethylbenzene – Toluene - Anthracene – Naphthalene at C Table 27: Aqueous concentration of components of the mixture Phenol - Tetradecane 65 and Naphthalene and Tetradecane at 20oC Table 28: Aqueous concentration of components in Special Mixture at 5oC and 20oC 65 10 Summary The study of water solubility of contaminants has become important in the practice of contaminated site management, assessment and remediation At the contaminated site it is not often found only one contaminant, many other substances can mix each other to form a contaminant mixture In fact, in one field site we have a product phase which contaminated the soil This phase consist of mineral oil, BTEX-compounds, PAH-compounds and phenol If we use the solubility of these substances in literature, we would expect the water solubility for benzene with values of 1.7 g/l, for example But on the site we only find benzene concentrations of 50 mg/l That’s the reason to investigate which affect the water solubility of each component in the mixture This work presents briefly theory of solubility, researches relating to water solubility of single compound and mixture, how to calculate water solubility of components in a mixture This work determined the water solubility of six substances including Ethylbenzene, Toluene, Anthracene, Naphthalene, Phenol and Tetradacane at temperatures 5-10-20oC Water solubility of mixtures of these substances was observed at temperatures and 20oC Solubility of single compounds compared to those in literature for determining accurate and precise received data Water solubility of single compounds and mixture also compared them each other The difference between these data was explained following solubility’s theory Water solubility of some mixtures was calculated and compared to experimental value Behaviours of components in the mixture also predict from experimental data 58 than estimated values for Ethylbenzene and Toluene 17% and 10%, respectively The difference is no greater than experimental uncertainty of analyzing method and this deviation is positive In a research of Banerjee (1984) on solubility of organic mixture has pointed out that this deviation caused by the combination of an increase in the activity coefficient of the component in the organic phase and a decrease in the aqueous phase [5] That means activity coefficient could be greater than In fact, in his work he found measured value of chlorobenzenes mixture in water exceeded value calculated by equation (9) about 10-20% Table 17: Comparison of experimental and calculated solubility of Ethylbezene and Toluene at 20oC Ethylbenzene Toluene Number of mole 0.0024 0.0084 Mole fraction in organic phase Calculated value (mg/l) 0.223 0.776 40.37 429.67 Experimental value (mg/l) 47.23 473.41 3.3.2 Mixture of Ethylbenzene and Phenol Mixture of Ethylbenzene and Phenol was made from 300µl Ethylbenzene, 5g Phenol and 10ml sterilized water All was placed in to glass tube 20ml Experimental values of water solubility of the mixture in two points of temperature are in Table 18 There is a change of Ethylbenzene’s solubility between temperature 20oC and 5oC Water solubility of Ethylbenzene in presence of Phenol at 20oC and 5oC were reduced to about 44% and 57%, respectively compared to their solubility in water Phenol concentration in aqueous phase is observed to be either enhanced or depressed at 20oC and 5oC And this concentration is slightly reduced compared to its water solubility in pure form 59 Table 18: Aqueous concentration of Ethylbenzene and Phenol in their mixture at 20oC Sampling time Ethylbenzene (mg/l) Phenol (mg/l) [P.S] [P.S] [P.S] [P.S] [P.S] [P.S] 97.344 93.210 85.686 100.285 103.471 99.850 110.061 105.080 109.595 100.259 95.394 98.871 1st sampling (7th day) nd sampling (21th day) Standard Deviation Average Value Deviation coefficient Confident interval 9.77 2.61 100.16 99.69 0.098 0.026 5.89 1.57 (P.S: Parallel sample) Table 19: Aqueous concentration of Ethylbenzene and Phenol in their mixture at 5oC Sampling time Ethylbenzene (mg/l) Phenol (mg/l) Exp Exp Exp.3 Exp Exp Exp 79.184 73.863 82.175 95.652 98.605 93.865 77.840 76.860 70.679 97.048 102.879 105.531 1st sampling (7th day) nd sampling (21th day) Standard Deviation Average Value Deviation coefficient Confident interval (P.S: Parallel sample) 4.04 4.45 76.77 98.93 0.053 0.045 2.44 2.68 60 3.3.3 Ethylbenzene – Anthracene – Naphthalene Mixture Mixture of Ethylbenzene, Anthracene and Naphthalene consists of 1.5ml Ethylbenzene, 300µg Anthracene, 300mg Naphthalene and 75ml sterilized water, all were placed in glass bottle 100ml Experimental values of water solubility of the mixture at temperature 20oC and 5oC are in Table 20 and 21 Table 20: Aqueous concentration of Ethylbenzene – Anthracene – Naphthalene in the mixture at 20oC [P.S] Sampling time 1st sampling (7th [P.S] EB Anth Naph EB Anth Naph (mg/l) (μg/l) (mg/l) (mg/l) (μg/l) (mg/l) 144.621 19.6 21.35 150.004 22.8 18.24 159.258 21.5 15.98 158.112 21.5 12.69 153.136 - 13.59 157.861 - 14.27 day) 2nd sampling st (21 day) 3rd sampling (30th day) Table 21: Aqueous concentration of Ethylbenzene – Anthracene – Naphthalene in the mixture at 5oC [P.S] Sampling time EB Anth Naph EB Anth Naph (mg/l) (μg/l) (mg/l) (mg/l) (μg/l) (mg/l) 16.81 137.072 1st sampling (7th day) 2nd sampling [P.S] 154.124 12.86 136.068 - 9.86 165.316 - 14.98 177.314 - 9.50 137.072 - 12.72 st (21 day) 3rd sampling (30th day) (P.S: Parallel sample) 61 Table 22: Accuracy of experimental values for components in the mixture Ethylbenzene – Anthracene – Naphthalene Standard Deviation Average Value Deviation coefficient Confident interval Ethylbenzene at 20oC Naphthalene at 20oC Ethylbenzene at 5oC Naphthalene at 5oC 5.727 3.267 17.322 2.842 153.832 16.02 151.27 12.79 0.037 0.204 0.115 0.222 3.451 1.968 10.437 1.713 Ethylbenzene concentrations at two point of temperature was observed and found unchanged behavior Naphthalene concentration has changed, decreasing with temperature decrease Both Ethylenzene and Naphthalene in the mixture has reduced their water solubility in pure form 3.3.4 Ethylbenzene – Toluene - Anthracene – Naphthalene Mixture Mixture of Ethylbenzene, Toluene, Anthracene and Naphthalene consists of 1.5ml Ethylbenzene, 4.5ml Toluene, 300µg Anthracene and 300mg Naphthalene and 75ml sterilized water All were placed in glass bottle 100ml Observed values at 20oC and 5oC of the mixture are presented in Table 23 and 24 The values shows all components, except Anthracene in mixture Ethylbenzene – Toluene - Anthracene – Naphthalene have decreased of water solubility in which Ethylbenzene and Naphthalene has significant reduction compared to those in pure form There is no significant change of solubility of Ethylbenzene, Toluene and Naphthalene between studied temperature ranges 62 Table 23: Aqueous concentration of Ethylbenzene – Toluene - Anthracene – Naphthalene in the mixture at 20oC [P.S] Sampling time 1st sampling [P.S] EB Toluene Anth Naph EB Toluene Anth Naph (mg/l) (mg/l) (μg/l) (mg/l) (mg/l) (mg/l) (μg/l) (mg/l) 42.921 407.863 18.4 5.11 46.650 418.503 17.3 5.24 47.533 382.462 - 5.46 49.414 423.782 - 6.22 39.302 441.435 - 5.955 45.842 399.879 - 6.06 (7th day) 2nd sampling (21th day) 3rd sampling (30th day (P.S: Parallel sample; EB: Ethylbenzene; Anth.: Anthracene; Naph.: Naphthalene) Table 24: Aqueous concentration of Ethylbenzene – Toluene - Anthracene – Naphthalene in the mixture at 5oC Sampling time 1st sampling [P.S] [P.S] EB Toluene Anth Naph EB Toluene Anth Naph (mg/l) (mg/l) (μg/l) (mg/l) (mg/l) (mg/l) (μg/l) (mg/l) 40.931 425.955 - 5.07 39.534 416.000 - 4.85 42.509 448.236 - 3.59 39.544 404.958 - 3.60 39.745 411.234 - 3.60 39.613 414.893 - 3.44 (7th day) 2nd sampling st (21 day) 3rd sampling (30th day) (P.S: Parallel sample; EB: Ethylbenzene; Anth.: Anthracene; Naph.: Naphthalene) 63 Table 25: Accuracy of experimental values of component of mixture Ethylbenzene – Anthracene – Naphthalene Standard Deviation Average Value Deviation coefficient Confident interval EB at 20oC Toluene at 20oC Naph at 20oC EB at 5oC Toluene at 5oC Naph at 5oC 3.624 20.413 0.463 1.201 15.347 0.730 45.277 412.321 5.67 40.313 420.213 4.02 0.080 0.050 0.082 0.030 0.037 0.181 2.183 12.299 0.279 0.724 9.247 0.440 (EB: Ethylbenzene; Anth.: Anthracene; Naph.: Naphthalene) Table 26: Comparison of experimental and calculated solubility of each component in mixture Ethylbenzene – Toluene - Anthracene – Naphthalene at 5oC Ethylbenzene Toluene Naphthalene Number of mole 0.0024 0.0084 0.0023 Mole fraction in organic 0.184 0.639 0.176 Calculated value (mg/l) 33.25 353.95 3.55 Experimental value (mg/l) 40.31 420.21 4.02 phase Similar to the mixture of Ethylbenzene and Toluene, the mixture of Anthracene and Naphthalene in presence of Ethylbenzene and Toluene has experimental exceeding value compared to estimated values for Ethylbenzene, Toluene and Naphthalene Correlative ratios are 21%, 18% and 13% This explain by activity coefficient of organics in the mixture could be greater than And this fact is appropriate with Banerjee’s explanation about deviation range from 10-20% between estimated and experimental values 64 3.3.5 Phenol - Tetradecane Mixture; Naphthalene – Tetradecane Mixture and Special Mixture These mixtures have been created as the following description Equilibrium is take place in closed glass bottles 500ml Bottles keep at room temperature, around 20oC  Phenol – Tetradecane mixture: 50μl Tetradecane + 100g Phenol + 300ml sterilized water  Naphthalene – Tetradecane mixture: 50μl Tetradecane + 1.2g Naphthalene + 300ml sterilized water  Special mixture: 5ml Ethylbenzene + 15ml Toluene + 1.2mg Anthracene + 1.2g Naphthalene + 50μl Tetradecane + 100g Phenol + 300ml sterilized water Initial results of water solubility of Phenol - Tetradecane and Naphthalene – Tetradecane mixture and special mixture are presented in Table 27 and 28 Each mixture had two parallel samples and studied at two ranges of temperature Except Tetradecane, all components of the mixtures were three parallel sampled for the first sampling day Due to limited volume of sample (each sampling for analysis needs 50ml sample), Tetradecane was only one sampled All data shows in Table 27, 28 is average of three parallel sampled of each sample and Tetradecane data is average of three injection of one sample Pure Tetradecane concentration in water was determined and the give value is 3.7μg/l This value falls in the range of listed value in literature A research of Chris Sutton and John A Calder showed solubility of Tetradecane is 2.2 ppb (2.2μg/l) with mole fraction 2.0 x 10-10 Franks (1966) shows the value 6.94 μg/l using chromatography to determine Tetradecane solubility at 25oC Study of Mackay, D.; Shiu (1973) shows the higher value 25.9μg/l using GC/FID, but the temperature is not specified 65 Table 27: Aqueous concentration of components of the mixture Phenol - Tetradecane and Naphthalene and Tetradecane at 20oC Phenol – Tetradecane Mixture Naphthalene – Tetradecane Mixture Phenol (g/l) 91.512 Naphthalene (mg/l) 12.27 Tetradecane (μg/l) 6.6 Tetradecane (μg/l) 37.8 (the first sampling, 7th day) Table 28: Aqueous concentration of components in Special Mixture at 5oC and 20oC Tem 20oC Ethylbenzene (mg/l) 19.819 Toluene (mg/l) 409.297 5oC 22.821 394.861 (the first sampling, 7th day) Anthracene Naphthalene (μg/l) (mg/l) 3.351 - 1.639 Phenol (g/l) 99.767 Tetradecane (μg/l) 3.0 133.421 0.3 66 Prospect Due to limited time of this thesis, some works have not been finished Mixture of Phenol - Tetradecane; Naphthalene – Tetradecane and Special Mixture have been waiting for the next samplings Other mixtures also have been stored for further study Received value will be analyzed to assess the trend of component’s solubility in the mixture Sample preparation for Tetradecane analysis will be more practiced to have the best procedure More practices for analyzing Anthracene will be carried out to shield interferences which could be influenced Anthracene analyzing results Study behaviours of pollutant mixtures need a longer time to have better understanding The valuable data of water solubility of components in the mixture will be used as important one of input for modelling behaviours of pollutants in the environment 67 CONCLUSIONS In this work, water solubility of six compounds in pure form at 5oC, 10oC, 20oC and the mixtures among them at 5oC and 20oC has been studied The experimental and sampling procedure has been set up Optimal conditions in the laboratory for obtaining maximum water solubility also studied Experiments were carried out without stirring condition and aqueous samples were taken since 5th day after mixture creation Carefulness during taking sample process will prevent deviation of analysing results of compounds Water solubility of Ethylbenzene, Toluene at 10oC and 20oC in this work are in good agreement with the best water solubility values in the literature Water solubility of Anthracene, Naphthalene falls within range of reported values in the literature Phenol’s water solubility has an accuracy at all studied temperatures Water solubility as a function of temperatures has been demonstrated in case of Ethylbenzene, Toluene and Phenol Solubility of Ethylbenzene and Toluene in their mixture has a change, Ethylbenzene’s solubility decreases and Toluene’s solubility slightly increases compared to those in water And their solubility tends to be increased in lower temperatures In the mixture between Ethybenzene and Phenol, water solubility of Ethylbenzene has significantly reduced in which Phenol’s solubility has almost unchanged Water solubility of Ethylbenzene and Naphthalene in the mixture Ethylbenzene – Anthracene Naphthalene has reduced compared to those in pure form All components in mixture Ethylbenzene – Toluene - Anthracene – Naphthalene have decreased of water solubility in which Ethylbenzene and Naphthalene has significant reduction compared to those in pure form Solubility of mixture Ethylbenzene – Toluene at 20oC and mixture Ethylbenzene – Toluene - Anthracene – Naphthalene at 5oC were calculated from theory The deviation range from 10-20% between calculated and experimental values can be accepted Mixture between Phenol – Tetradecane; Naphthalene – Tetradecane and special mixture which consist of six studied organic compounds have created, first analyzed and need further study 68 References Yalkowsky, S.H and Banerjee, S (1992), 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Journal of Pharmaceutics, Volume 245, Issues 1-2, 1, Pages 153-166 19 J Gmehling, K Fischer, J Li, M Schiller, (1993), Status and results of group contribution methods, J Gmehling, K Fischer, J Li’, M Schiller, Pure & Appl Cbem., Vol 65, No 5, pp 919-926 20 J Gmehling (2003), Potential of group contribution methods for the prediction of phase equilibria and excess properties of complex mixtures, Pure Appl Chem., Vol 75, No 7, pp 875–888 21 Dortmund Data Bank Software Package, 2007, CalculateX3 - Calculation of Ternary Phase Equilibrium Diagrams 22 Joel H Hildebrand, Theory of Solubility (1922), Abstraction 23 Environmental Health Criteria of Ethylbenzene, Ethylbenzene (EHC186, 1996), 12-20-06, http://www.inchem.org/documents/ehc/ehc/ehc186.htm 24 Environmental Health Criteria of Toluene, Toluene (EHC 52, 1986), 12-20-06, http://www.inchem.org/documents/ehc/ehc/ehc52.htm 25 Environmental Health Criteria of Phenol, Phenol (EHC 161, 1994) , 12-20-06, http://www.inchem.org/documents/ehc/ehc/ehc161.htm 26 Naphthalene (PIM 363, http://www.inchem.org/documents/pims/chemical/pim363.htm 27 Anthracene (IARC Summary & Evaluation, Volume http://www.inchem.org/documents/iarc/vol32/anthracene.html 12-20-06, 32, 1983 28 United States Environmental Protection Agency, EPA 712–C–96–042 August 1996, Product Properties Test Guidelines, OPPTS 830.7860 Water Solubility (Generator Column Method) 70 29 Dana Yaron-Marcovich, Ishai Dror and Brian Berkowitz, (November 2007), Behavior and stability of organic contaminant droplets in aqueous solutions, Chemosphere Volume 69, Issue 10, November 2007, Pages 1593-1601 30 Dialysis, http://www.terracontanks.com/nav/cm.aspx?cmid=379, visited on 14th Nov 2007 71 Statement under oath I hereby declare that this Mater thesis is my own work with the assistance from my supervisor and persons who are mentioned in the acknowledgement section And I only used source listed in References Hanoi, December 10th, 2008 Vu Huyen Phuong 72 Appendix Appendix - Calibration curve of Ethylbenzene and Toluene Appendix – Maximum peak and Calibration curve of Phenol Appendix - Calibration curve of Anthracene and Naphthalene Appendix - Calibration curve of Tetradecane and Dodecane