42nd International Chemistry Olympiad

Official Report

July 19-28, 2010, Japan 42nd International Chemistry Olympiad Closing Ceremony Remarks

It is a pleasure to see you again. I hope you have enjoyed the 42nd International Chemistry Olympiad.

Louis Pasteur once said, “Science has no borders, but scientists have their own fatherlands.” Science is objective. But making scientific discoveries and accumulating scientific knowledge are human activities.

Every region and ethnic group has its own culture, and the world’s scientists have grown up in these diverse cultures. But for the scientists of the 21st century, I believe we have a mission to work in close solidarity, while respecting our diverse cultures, for the sustaining of humankind. We must build a civilization that accepts and respects diverse cultures.

The 20th century was an era of international competition, symbolized by war and economic rivalry. In the 21st century, however, we must cooperate for the survival of humanity within the limitations of our planet earth. Every nation has a different history and sometimes our interests clash. But no country can exist on its own. Everything begins with understanding between individuals. Friendships across the seas and firm relationships of trusts are the cornerstones of international security.

You young people here today will be the next generation of leaders. It is my hope that learning will be a process of joy for you and that you will develop a firm grounding in whatever specialty you may undertake in the future. But this alone is not enough. You must also acquire a thorough understanding of society’s conventions and ethics, and the skills to work with other people. Society needs all kinds of people. We all have different talents and values. What society needs are people who are highly motivated and have diverse skills. I hope to see you mature into the kind of person who can make significant contribution to society.

Now that the Olympiad is over you will be departing Japan for your various home countries and regions. Please build on the networks of friendship and science that you have formed here. I hope that you will never forget this time in Tokyo and that the experience will be a stepping stone to your future and to the world.

Finally, I would like to close by expressing my appreciation to everyone who worked so hard to make this event possible.

Thank you.

Ryoji Noyori, IChO Chair

July 27, 2010

1

Official report “Report of the 42nd IChO” Contents

Closing Ceremony remarks 1 Contents 2 Overview of the 42nd IChO 3 Hosts and Sponsors 3 Venues, Participants, and Results 5 Participating Countries 6 Programs Students 7 Mentors 8 Guests 9 Tasks 10 Translation Languages 10 Practical Problems 11 Theoretical Problems 38 Final Results and Ranking 70 Statistical Analysis of the Problems 77 Minutes of the International Jury and Steering Committee Meetings 85 Regulations of the International Chemistry Olympiad (IChO) 89 List of Participants 107 Head mentors, Mentors, Observers, and Guests 107 Students 114 Country Participation Fees 121 Budget of the 42nd IChO 122 List of Organizers 123

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Overview of the 42nd IChO

42nd International Chemistry Olympiad 19-28 July 2010, Japan

Hosts IChO Japan Committee Waseda University The University of Tokyo The Association for the Progress of New Chemistry Catalysis Society of Japan The Ceramic Society of Japan The Chemical Society of Japan The Electrochemical Society of Japan Japan Chemical Industry Association The Japan Institute of Energy Japan Oil Chemists' Society The Japan Petroleum Institute Japan Science Foundation The Japan Society for Analytical Chemistry Japan Society for Bioscience, Biotechnology, and Agrochemistry The Pharmaceutical Society of Japan The Society of Chemical Engineers, Japan The Society of Polymer Science, Japan The Society of Synthetic Organic Chemistry, Japan

Ministry of Education, Culture, Sports, Science and Technology Ministry of Economy, Trade and Industry Science Council of Japan Japan Science and Technology Agency Japan Chemical Innovation Institute Japan Society of Physics and Chemistry Education Zenkoku Tyugakkou Rikakyouiku Kenkyukai Japan Broadcasting Corporation The Asahi Shimbun The Chemical Daily The Chunichi Shimbun The Mainichi Newspapers Nikkei Inc. Sankei Shimbun Co. The Science News Ltd The Yomiuri Shimbun

Sponsors Adeka Corporation Air Water Inc. Asahi Glass Co., Ltd. Asahikasei Corporation Astomos Energy Corporation Bando Chemical Industries, Ltd. Brighestone Corporation Casio Computer Co., Ltd. Central Glass Co., Ltd. Cosmo Oil Co., Ltd. Daicel Chemical Industries, Ltd. Daicel-Evonik Ltd. Daikin Industries, Ltd. Dainichiseika Color & Chemicals Mfg. Co., Ltd Dainippon Tosho Publishing Co., Ltd. Daiso Co., Ltd. Denki Kagaku Kogyo Kabushiki Kaisha DIC Corporation Dow Corning Toray Co., Ltd. Du Pont-Mitsui Fluorochemicals Company, Ltd. Du Pont-Mitsui Polychemicals Co., Ltd Du Pont-Toray Co., Ltd. Ebara Corporation Exxon Mobil Corporation Fujifilm Corporation Fujitsu Limited Fukuvi Chemical Industry Co., Ltd. Fuso Chemical Co., Ltd. Gun Ei Chemical Industry Co., Ltd. Harima Chemicals, Inc. Hitachi Chemical Co., Ltd. Hitachi, Ltd. Hodogaya Chemical Co., Ltd. Honshu Chemical Industry Co., Ltd. Idemitsu Kosan Co., Ltd. Inabata & Co., Ltd. Japan Energy Corporation Japan Oil Transportation Japan Steel Drum Association Japan U-Pica Company Ltd. Japan Vilene Company, Ltd. JSP Corporation JSR Corporation Kagaku-Dojin Publishing Co., Inc. Kaneka Corporation Kao Corporation Kinden Corporation Kobe Steel, Ltd. Kodansha Ltd. Koei Chemical Co., Ltd. Konishi Co., Ltd. Kuraray Co., Ltd. Kureha Corporation Kygnus Sekiyu K.K.

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Kyokutou Kai Kyowa Chemical Industry Co., Ltd. Kyushu Oil Co., Ltd. Lanxess K.K. Lion Corporation Marubeni Corporation Maruishi Chemical Trading Co., Ltd. Maruzen Co., Ltd. Maruzen Petrochemical Co., Ltd. Matsumoto Yushi-Seiyaku Co., Ltd. Meiwa Industry Co., Ltd. Meiwa Plastic Industries, Ltd. Microsoft Corporation Mitsubishi Chemical Corporation Mitsubishi Corporation Mitsubishi Engineering-Plastics Corporation Mitsubishi Gas Chemical Company, Inc. Mitsubishi Heavy Industries, Ltd. Mitsubishi Materials Corporation Mitsubishi Materials Electronic Chemicals Co., Ltd Mitsubishi Plastics, Inc. Mitsubishi Rayon Co., Ltd. Mitsui & Co., Ltd. Mitsui Chemicals, Inc Mitsui Engineering & Shipbuilding Co., Ltd. Mitsui Mining & Smelting Co., Ltd. Mitsui-Soko Co., Ltd. Mitsui Sumitomo Insurance Co., Ltd. Nagoya Asahi Kai Nanbu Plastics Co., Ltd. NEC Corporation Nihon Medi-Physics Co., Ltd Nihon Millipore K.K. Nihon Oxirane Co., Ltd. Nippon Kasei Chemical Company Limited Nippon Kayaku Co., Ltd. Nippon Oil Corporation Nippon Paint Co., Ltd. Nippon Paper Industries Co., Ltd. Nippon Polyurethane Industry Co., Ltd. Nippon Sheet Glass Co., Ltd. Nippon Shokubai Co., Ltd. Nippon Soda Co., Ltd. Nissan Chemical Industries, Ltd. Nitto Denko Corporation NOF Corporation Oji paper Co., Ltd. Organo Corporation Osaka Kyokusou Kai Osaka Organic Chemical Industry Ltd. Panasonic Corporation Sanki Sankyu Inc. Sanyo Chemical Industries, Ltd. Sekisui Chemical Co., Ltd. Sekisui Jushi Corporation Sekisui Plastics Co., Ltd. Shin-Etsu Chemical Co., Ltd. Shinto Paint Co., Ltd. Shiseido Co., Ltd. Shoko Co., Ltd Showa Denko K.K Showa Engineering Co., Ltd. Showa Highpolymer Co., Ltd. Showa Paxxs Corporation Showa Tansan Co., Ltd. Soda Aromatic Co., Ltd. Sumika Chemical Analysis Service, Ltd. Sumika Color Co., Ltd. Sumitomo Bakelite Co., Ltd. Sumitomo Chemical Co., Ltd. Sumitomo Chemical Engineering Co., Ltd. Sumitomo Corporation Sumitomo Seika Chemicals Company Limited Sunallomer Ltd. Taiheiyo Cement Corporation Taiyo Nippon Sanso Corporation Taiyo Oil Company, Limited Taiyo Vinyl Corporation Takasago International Corporation Taoka Chemical Co., Ltd. Teijin Limited The Japan Steel Works, Ltd. The Japan Wool Textile Co., Ltd. The Nippon Synthetic Chemical Industry Co., Ltd. Toagosei Co., Ltd. Toho Chemical Industry Co., Ltd. Tokuyama Corporation Tokyo Chemical Industry Co., Ltd. Tokyo Electric Power Company, Inc. Tokyo Gas Co., Ltd. Tokyo Ohka Kogyo Co., Ltd. Tokyo Printing Ink Mfg. Co., Ltd. TOLI Corporation Toray Fine Chemicals Co., Ltd. Toray Industries, Inc. Toray Research Center, Inc. Toshiba Corporation Toshiba Mitsubishi-Electric Industrial Systems Corporation Tosoh Corporation Toyo Engineering Corporation Toyo Ink Mfg. Co., Ltd. Toyoda Gosei Co., Ltd. Toyota Motor Corporation Ube Industries, Ltd. Ube Material Industries, Ltd. Ube-Mitsubishi Cement Corporation Ube-Nitto Kasei Co., Ltd. UMG ABS, Ltd. Unitika Ltd. Yamatake Corporation Yokogawa Electric Corporation ZKAI Co., Ltd.

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Venues

Practical Exam, Closing Ceremony: Waseda University

Theoretical Exam: The University of Tokyo

Students Accommodations, Opening Ceremony: National Olympics Memorial Youth Centre (NYC)

Mentors Accommodations: Overseas Vocational Training Association (OVTA)

Participants

Countries:

68 Participating Countries

3 Observing Countries: Liechtenstein – 2nd year Nigeria – 1st year Serbia – 1st year

Unable to send students but sent observers: Saudi Arabia

Invited but did not participate: Egypt

Observation approved but no registration nor delegation arrived: Uzbekistan

Number of participants:

Students: 267 Head Mentors, Mentors: 133 Observers: 65 Guests: 37

Results

Gold Medalists: 32 Silver Medalists: 58 Bronze Medalists: 86 Honorable Mentions: 9 IUPAC Awardees: 2

5

Participating Countries Country Code Country Code 1 Argentina ARG 35 Kuwait KWT 2 Armenia ARM 36 Kyrgyzstan KGZ 3 Australia AUS 37 Latvia LVA 4 Austria AUT 38 Lithuania LTU 5 Azerbaijan AZE 39 Malaysia MYS 6 Belarus BLR 40 Mexico MEX 7 Belgium BEL 41 Moldova MDA 8 Brazil BRA 42 Mongolia MNG 9 Bulgaria BGR 43 Netherlands NLD 10 Canada CAN 44 New Zealand NZL 11 China CHN 45 Norway NOR 12 Chinese Taipei TPE 46 Pakistan PAK 13 Costa Rica CRI 47 Peru PER 14 Croatia HRV 48 Poland POL 15 Cuba CUB 49 Portugal PRT 16 Cyprus CYP 50 Romania ROU 17 Czech Republic CZE 51 Russian Federation RUS 18 Denmark DNK 52 Singapore SGP 19 Estonia EST 53 Slovakia SVK 20 Finland FIN 54 Slovenia SVN 21 France FRA 55 Spain ESP 22 Germany DEU 56 Sweden SWE 23 Greece GRC 57 Switzerland CHE 24 Hungary HUN 58 Syria SYR 25 Iceland ISL 59 Tajikistan TJK 26 India IND 60 Thailand THA 27 Indonesia IDN 61 Turkey TUR 28 Iran, I. R. of IRN 62 Turkmenistan TKM 29 Ireland IRL 63 Ukraine UKR 30 Israel ISR 64 United Kingdom GBR 31 Italy ITA 65 United States USA 32 Japan JPN 66 Uruguay URY 33 Kazakhstan KAZ 67 Venezuela VEN 34 Korea KOR 68 Viet Nam VNM

Egypt EGY Saudi Arabia SAU Liechtenstein LIE Nigeria NGA Serbia SRB Uzbekistan UZB

6 Program: Students Time Monday Tuesday Wednesday Thursday Friday Saturday Sunday Monday Tuesday Wednesday 19-Jul 20-Jul 21-Jul 22-Jul 23-Jul 24-Jul 25-Jul 26-Jul 27-Jul 28-Jul 7:00 Breakfast Breakfast 7:30 Breakfast Breakfast Breakfast Breakfast Breakfast Breakfast 8:00 Breakfast Transfer 8:30 Arrivals 9:00 Transfer Sports and Excursion to Nikko 9:30 Move Excursion Traditional Transfers Japanese to Kamakura Arts 10:00 Lab safety Culture (NYC) Departures 10:30 Registration Opening instruction Experience Theoretical (Tosho-gu 11:00 Ceremony (Gajo-en) Exam Transfer Free Time (Tsurugaoka Lunch Shrine) 11:30 (NYC) (Univ. of (Lunch) in Tokyo Shrine) 12:00 Tokyo) Judo watching 12:30 Transfer Lunch (Lunch) (Lunch) Lunch at and Experience 13:00 OVTA Welcome (Lunch) (Kodokan) 13:30 Practical Lunch(NYC) (Edomura: 14:00 Registration Exam Lunch Transfer 7 Experience of 14:30 (Waseda Sightseeing and (Lunch) Move to Tokyo Tokyo2 the Life in the 15:00 (Great Univ.) Social Event Closing NYC Age of Bushi) 15:30 Budha) (Univ. of Sports and Ceremony (Tokyo (National 16:00 Tokyo) Traditional (Okuma Tower) Science Arts Auditorium, 16:30 Museum) Transfer (NYC) Waseda 17:00 (Asakusa) Univ.) 17:30 Strolling

18:00 Yokohama Dinner 18:30 Dinner Dinner (Dinner) Dinner Bay Area Dinner (Waseda (Dinner) 19:00 at NYC at NYC at NYC at NYC Farewell Univ.) party 19:30 Reunion (Rihga 20:00 Transfer Party Drum Royal Hotel

20:30 (Yokohama) Performance Tokyo) 21:00 (Kijima Taiko) 21:30 22:00 22:30 Transfer Transfer

23:00 Program: Mentors Time Monday Tuesday Wednesday Thursday Friday Saturday Sunday Monday Tuesday Wednesday 19-Jul 20-Jul 21-Jul 22-Jul 23-Jul 24-Jul 25-Jul 26-Jul 27-Jul 28-Jul 7:00 Breakfast 7:30 Breakfast Breakfast Breakfast Breakfast Breakfast Breakfast Breakfast Breakfast 8:00 8:30 Transfer to 9:00 Arrivals NYC (Transfer

9:30 Sightseeing to Waseda) Transfers Excursion Marking Task 10:00 Tokyo Translation Translationto Kamakura Arbitration Departures 10:30 Opening Registration 11:00 Ceremony (Imperial Palace (Tsurugaoka Excursion to 11:30 (NYC) Square) Shrine) the Rural Area Free Time 12:00 of Chiba Lunch Lunch Lunch 12:30 Transfer (Lunch) (Lunch) (Lunch) 13:00 (Lunch) 13:30 Lunch at Welcome OVTA Lunch (NYC) (Asakusa) 14:00 (Shinsho-ji 8 14:30 Transfer (Great Temple, Narita) Budha) 15:00 Lab Inspection (Boso-no-mura Closing 15:30 (Waseda univ.) Museum: Ceremony 16:00 Transfer to Meet with Registration Experience of (Okuma OVTA Authors 16:30 Traditional Auditorium 17:00 Villege Life) Waseda Univ.) 17:30 Meet with (20:00limit) (20:00limit) Strolling 18:00 Authors Yokohama 18:30 Bay Area Dinner Dinner Dinner Dinner Dinner Farewell party 19:00 (Dinner) Dinner Reunion (Rihga Royal 19:30 Party Hotel Tokyo) 20:00 1st Jury 2nd Jury (Yokohama) 3rd Jury 20:30 Meeting 4th Jury Meeting Meeting 21:00 re: Practical Transfer to Meeting Transfer to re: Business Exam OVTA OVTA 21:30 Theoretical

22:00 Exam 22:30 (Night Time)

23:00 Program: Guests Time Monday Tuesday Wednesday Thursday Friday Saturday Sunday Monday Tuesday Wednesday 19-Jul 20-Jul 21-Jul 22-Jul 23-Jul 24-Jul 25-Jul 26-Jul 27-Jul 28-Jul 7:00 Breakfast 7:30 Breakfast Breakfast Breakfast Breakfast Breakfast Breakfast Breakfast Breakfast 8:00 Transfer 8:30 to 9:00 Arrivals (Transfer NYC 9:30 Sightseeing to Waseda) Transfers 10:00 Tokyo 2 Excursion to Kamakura Departures 10:30 Opening Registration Excursion (Imperial Excursion Ceremony 11:00 to the base Palace to (Tsurugaoka (NYC) Excursion to 11:30 of Mt. Fuji Square) Kawagoe Shrine) Free Time the Rural Area 12:00 of Chiba 12:30 Transfer (Lunch)

(Lunch) (Lunch) (Lunch) (Lunch) 13:00 Welcome (Lunch) Lunch 13:30 Lunch Souvenir at OVTA 9 14:00 (NYC) (Shinsho-ji (Kawaguchi (Asakusa) (Visiting (Great Hunting Temple, Narita) (Schuttle to 14:30 Lake) the old Budha) Lalaport 15:00 Tokyo 1 City Area) Closing (Boso-no-mura Shopping 15:30 (Sumida Ceremony Museum: Complex) 16:00 Registration (Tokyo (Oshino River (Okuma Experience of Tower) Hakkai Cruising) Auditorium, 16:30 Traditional Forest) Waseda 17:00 Villege Life) (Korakuen Univ.) 17:30 Strolling Garden) 18:00 Yokohama (Dinner) 18:30 Bay Area Dinner Farewell 19:00 Dinner party Reunion 19:30 Dinner Dinner Dinner (OVTA) Dinner (Rihga Royal Party (OVTA) (OVTA) (OVTA) (OVTA) Hotel Tokyo) 20:00 (Yokohama) 20:30 21:00 Transfer to Transfer to 21:30 OVTA OVTA 22:00 22:30 (Night Time)

23:00

Translation Languages

Country Languages Country Languages 1 Argentina Spanish 35 Kuwait Arabic 2 Armenia Armenian 36 Kyrgyzstan Russian 3 Australia English 37 Latvia Latvian, Russian 4 Austria German 38 Lithuania Lithuanian 5 Azerbaijan English, Russian 39 Malaysia English 6 Belarus Russian 40 Mexico Spanish 7 Belgium Dutch, French 41 Moldova Russian 8 Brazil Portuguese 42 Mongolia Mongolian 9 Bulgaria Bulgarian 43 Netherlands Dutch 10 Canada English 44 New Zealand English 11 China Chinese 45 Norway Norwegian 12 Chinese Taipei Traditional Chinese 46 Pakistan English 13 Costa Rica Spanish 47 Peru Spanish 14 Croatia Croatian 48 Poland Polish 15 Cuba Spanish 49 Portugal Portuguese 16 Cyprus Greek 50 Romania Romanian 17 Czech Republic Czech 51 Russian Federation Russian 18 Denmark Danish 52 Singapore English 19 Estonia Estonian, Russian 53 Slovakia Slovak 20 Finland Finnish 54 Slovenia Slovenian 21 France French 55 Spain Spanish 22 Germany German 56 Sweden Swedish 23 Greece Greek 57 Switzerland French, German 24 Hungary Hungarian 58 Syria Arabic 25 Iceland Icelandic 59 Tajikistan English, Russian 26 India English 60 Thailand Thai 27 Indonesia Indonesian 61 Turkey Turkish 28 Iran, I. R. of Farsi 62 Turkmenistan English, Russian 29 Ireland English 63 Ukraine Russian 30 Israel Hebrew 64 United Kingdom English 31 Italy Italian 65 United States English 32 Japan Japanese 66 Uruguay Spanish 33 Kazakhstan Russian 67 Venezuela Spanish 34 Korea Korean 68 Viet Nam Vietnamese

10 Instructions

Examination Procedures

• You have 5 hours to complete Tasks 1, 2, and 3. You may perform the tasks in any order you choose. • There will be an additional 15 minutes reading time before the start. • DO NOT begin working on the tasks until the START command is given. • When the STOP command is given at the end of the 5 hours, you must stop your work on the tasks immediately. A delay in doing so may lead to your disqualification from the examination. • After the STOP command has been given, wait in your lab space. A supervisor will check your lab space. The following items should be left behind: 9 The problem booklet (this booklet) 9 The answer booklet 9 Your chosen TLC plates in zipper storage bags A and B with your student code (from Task 1) 9 Your product and glass microfiber filter sheet in a crystallization dish with a lid in zipper storage bag C with your student code (from Task 1) • Do not leave the examination hall until you are instructed to do so by the supervisors.

Safety

• Safety is the most important issue in the laboratory. You are expected to follow the safety rules given in the IChO regulations. Safety glasses and lab coats must be worn at ALL TIMES. • If you behave in an unsafe manner, you will receive one warning before you are asked to leave the laboratory. If required to leave due to a second warning, you will receive a score of zero for the entire experimental examination. • NO eating or drinking is allowed in the laboratory. • In case of emergency, follow the instructions given by the supervisors.

Notes on the booklets and answer methods

• The problem booklet comprises 23 pages including cover page. • The answer booklet comprises 6 pages. Do not attempt to separate the sheets. 11 • You should confirm your student code inscribed on the booklets and write your name and student code on every answer sheet. • Use only the pen provided for filling in the answer sheets. You may also use the calculator and the ruler provided. Use the mechanical pencil provided only for experiments in Task 1. Do not use the mechanical pencil for filling in the answer sheets. • All results must be written in the appropriate areas on the answer sheets. Results written elsewhere will not be graded. If you need to do rough calculations, etc., use the back of the sheets. • You should take care to report answers to an appropriate number of significant figures. • Keep your answer booklet in the envelope provided. Take out the booklet only when you write the answers. Do not seal the envelope.

Notes on the Examination

• You may need to reuse some glassware during the examination. If this is the case, clean it carefully in the sink closest to you. • Contact a supervisor near you if you have any questions regarding the tasks or if you need a refreshment/toilet break. • Use the labeled waste containers under the hood or near the windows for disposal of liquids and solids. A waste container (plastic beaker) is also available on each bench for aqueous waste. Discard used glass capillaries into a labeled plastic tube . • Replacement of chemicals and laboratory ware will be provided if necessary. Other than the first, for which you will be pardoned, each such incident will result in the loss of 1 point from your 40 practical points. Refilling of washbottle water is permitted with no loss of points. • An official English version of this examination is available upon request if you require clarification.

12 Periodic table with relative atomic masses

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

1 2 H He 1.01 4.00

3 4 5 6 7 8 9 10 Li Be B C N O F Ne 6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18

11 12 13 14 15 16 17 18 Na Mg Al Si P S Cl Ar 22.99 24.30 26.98 28.09 30.97 32.06 35.45 39.95

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.64 74.92 78.96 79.90 83.80

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 85.47 87.62 88.91 91.22 92.91 95.96 - 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29

55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Cs Ba 57-71 Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 132.91 137.33 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 - - -

87 88 104 105 106 107 108 109 110 111 Fr Ra 89-103 Rf Db Sg Bh Hs Mt Ds Rg ------

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 138.91 140.12 140.91 144.24 - 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr - 232.04 231.04 238.03 ------

13 Apparatuses Apparatuses Number For multiple tasks (on the desk or in Box 1): 20-mL beaker for taking a small portion of liquid to rinse inside of 1 glassware Paper 3 2-mL pipette bulb 1 5-mL pipette bulb 1 Pipette rack 1 200-mL plastic beaker for waste 1 Safety bulb 1 Spatula 1 Stand 1 100-mL washbottle 1 500-mL washbottle 1 For Task 1 (in Box 1, on the desk or on pipette rack): Büchner funnel with rubber adapter 1 Clamp with muff (clamp holder) 1 200-mL conical beaker 1 300-mL conical beaker 1 Diaphragm vacuum pump with tubing and connecter 1 Glass capillary tube (in a plastic tube) 8 Glass microfiber filter sheet in a crystallization dish with lid 1 2-mL graduated pipette 3 5-mL graduated pipette 1 Magnetic stirrer 1 10-mm magnetic stirring bar 1 22-mm magnetic stirring bar 1 10-mL measuring glass 1 pH test paper (in a zipper storage bag) 3 10-mL plastic graduated cylinder 1 Plastic tube for used glass capillary 1 Suction flask 1 10-mL test tube 1

14 100-mL test tube 1 TLC developing chamber with lid 1 TLC plate (in a zipper storage bag) 4 Tweezers 1 Zipper storage bags A and B for submission of TLC plates 1 for each Zipper storage bag C for submission of glass microfiber filter sheet in a 1 crystallization dish For Task 2 (in Box 2, on the desk or on pipette rack): 2-mL graduated pipette 1 5-mL graduated pipette 1 Label (in a zipper storage bag) 4 LED light box (in a zipper storage bag: do not remove from the bag at any 1 time.) Nessler tube 5 Nessler tube rack 1 50-mL volumetric flask 2 5-mL volumetric pipette 1 10-mL volumetric pipette 1 For Task 3.1 (in Box 2 or on pipette rack): Burette 1 Burette clamp 1 100-mL conical beaker 6 Glass funnel (for transferring chemicals to a burette) 1 1-mL graduated pipette 2 5-mL volumetric pipette 1 20-mL volumetric pipette 1 For Task 3.2 (in Box 2): 10-mL vial (in a zipper storage bag) 10 Plastic Pasteur pipette 1 Shared equipment: Gloves of various sizes UV lamp Cleaning tissue

15 Chemicals on Each Desk

Chemical Quantity Container R phrases S phrases For multiple tasks (in Box 1):

0.5 mol L-1 hydrochloric acid 50 mL Plastic bottle None listed None listed (0.5 mol L-1 HCl)

For Task 1 (in Box 1): 1,4-dihydro-2,6-dimethylpyridine-3,5 -dicarboxylic acid diethyl ester 1 g Vial 36/37/38 26

(C13H19NO4; 1,4-DHP_powder) 1,4-DHP for TLC 3 mg Vial 36/37/38 26 (1,4-DHP_TLC)

Ethanol (C2H5OH) 10 mL Glass bottle 11 7-16

Ethyl acetate (CH3COOC2H5) 25 mL Glass bottle 11-36-66-67 16-26-33

11-38-50/53-65- 9-16-29-33- Heptane (C H ) 20 mL Glass bottle 7 16 67 60-61-62

Potassium iodide (KI) 150 mg Glass bottle None listed None listed

Sodium metabisulfite (Na2S2O5) 1 g Glass bottle 22-31-41 26-39-46 Saturated sodium hydrogencarbonate solution 25 mL Glass bottle None listed None listed

(Sat. NaHCO3 solution) Urea hydrogen peroxide 17-26- 1 g Vial 8-34 36/37/39-45 (CH4N2O•H2O2; UHP) For Task 2 (in Box 2): Sample solution (labeled as 30 mL Plastic bottle None listed None listed “Sample solution”) 2+ Standard Fe(bpy)3 solution 1 (containing 2.0 mg of iron in 1 L 50 mL Plastic bottle None listed None listed solution) (labeled as “Standard 2+ Fe(bpy)3 solution 1”) 2+ Standard Fe(bpy)3 solution 2 (containing 3.0 mg of iron in 1 L 50 mL Plastic bottle None listed None listed solution) (labeled as “Standard 2+ Fe(bpy)3 solution 2”) Acetate buffer solution (pH 4.6, 1:1 mixture of acetic acid 50 mL Plastic bottle None listed None listed and sodium acetate;

CH3COOH-CH3COONa solution)

16 0.1 mol L-1 disodium hydrogenphosphate solution 25 mL Plastic bottle None listed None listed -1 (0.1 mol L Na2HPO4) 0.2 %(w/v) 2,2’-bipyridine aqueous solution 25 mL Plastic bottle None listed None listed

(0.2 %(w/v) C10N2H8) Sodium thioglycolate 20 mg Vial 22-38 36 (C2H3NaO2S)

For Task 3.1 (in Box 2 or on the desk):

Polysaccharide solution (labeled as 50 mL Plastic bottle None listed None listed “Polysaccharide solution”) Poly(diallyldimethylammonium chloride) aqueous solution (PDAC)

CH2 CH2 240 mL Glass bottle None listed None listed

N+ H3C CH3 Cl- n Potassium poly(vinyl sulfate) aqueous solution (0.0025 mol L-1; monomer unit concentration) (0.0025 mol L-1 PVSK) 240 mL Glass bottle 36/37/38 26-36 CH2 CH O O S O O-K+ n 0.5 mol L-1 sodium hydroxide aqueous solution 50 mL Plastic bottle 34 26-37/39-45 (0.5 mol L-1 NaOH) 1 g L-1 toluidine blue (TB) aqueous Dropper solution 6 mL None listed None listed -1 bottle (1 g L C15H16N3SCl)

17

For Task 3.2 (in Box 2):

Dropper Solution X-1 (X: A-H) 10 mL bottle

Dropper Solution X-2 (X: A-H) 10 mL bottle

Dropper Solution X-3 (X: A-H) 10 mL 36/37/38 26-36 bottle

Dropper Solution X-4 (X: A-H) 10 mL bottle

Dropper Solution X-5 (X: A-H) 10 mL bottle

18 Risk Phrases

Number Special Risks 8 Contact with combustible material may cause fire. 11 Highly flammable 22 Harmful if swallowed 31 Contact with acids liberates toxic gas. 34 Causes burns 36 Irritating to eyes 38 Irritating to skin 41 Risk of serious damage to eyes 65 Harmful: may cause lung damage if swallowed. 66 Repeated exposure may cause skin dryness or cracking. 67 Vapors may cause drowsiness and dizziness.

36/37/38 Irritating to eyes, respiratory system and skin Very toxic to aquatic organisms, may cause long term adverse effects in the 50/53 aquatic environment.

19 Safety Phrases

Number Safety Recommendations 7 Keep container tightly closed. 9 Keep container in a well ventilated place. 16 Keep away from sources of ignition - No Smoking. 17 Keep away from combustible material. In case of contact with eyes, rinse immediately with plenty of water and seek 26 medical advice. 29 Do not empty into drains. 33 Take precautionary measures against static discharges. 36 Wear suitable protective clothing. 37 Wear suitable gloves. 39 Wear eye/face protection. In case of accident or if you feel unwell, seek medical advice immediately. (Show 45 the label where possible.) 46 If swallowed, seek medical advice immediately and show the container or label. 60 This material and its container must be disposed of as hazardous waste. Avoid release to the environment. Refer to special instructions/ material safety data 61 sheet. If swallowed, do not induce vomiting: seek medical advice immediately and show 62 the container or label

24/25 Avoid contact with skin and eyes. 36/37/39 Wear suitable protective clothing, gloves and eye/face protection. 37/39 Wear suitable gloves and eye/face protection

20 Task 1

1e 1a 1b 1c 1d Total i ii iii 4 4 2 2 2 2 24 40

Reaction of Hantzsch Ester with Urea Hydrogen Peroxide In this experiment, you are required to synthesize a pyridinedicarboxylate derivative from 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid diethyl ester (1,4-DHP or Hantzsch ester) by oxidation with urea hydrogen peroxide (UHP), an environmentally-friendly oxidant. O

H H N N O O H H O O CH3CH2 CH CH 2 3 CH CH O O UHP H 3 2 CH2CH3 O O O O H H3C N CH3 H H3C N CH3 KI 1,4-DHP Procedures (1) Place a 22-mm magnetic stirring bar in a 100-mL test tube. Fix the test tube on a magnetic stirrer using a clamp. Add 1,4-DHP (1 g) (labeled as 1,4-DHP_powder), and potassium iodide (150 mg) to the test tube, followed by ethanol (5 mL), with a 5-mL graduated pipette. (2) Add 1 g UHP (wear gloves) and stir the mixture. (Caution: this reaction is exothermic.) (3) For thin layer chromatography (TLC) analysis, prepare a mixture of ethyl acetate:heptane (1:2 in volume) with a measuring glass and place an appropriate amount of the mixture in a TLC developing chamber. Add 1 mL of ethyl acetate to the vial (labeled as 1,4-DHP_TLC) to dissolve 1,4-DHP (3 mg). (4) Check your TLC plates before using. If they are damaged, they can be replaced without penalty. Draw a start line on the lower portion of a TLC plate with a pencil (see Fig. 1.1). (5) During the reaction, the reaction mixture becomes clear (usually within 20 min). When the reaction mixture becomes clear (the precipitates may form when it cools, but precipitates will not affect the TLC analysis), take a small portion of the mixture using a 21 glass capillary and load it to make two spots in the center and right positions on the TLC plate. Load an appropriate amount of the 1,4-DHP solution prepared in procedure (3) in the center and left positions, so that there are three spots on the plate, with the center spot containing both the reaction mixture and 1,4-DHP (see Fig. 1.1). Develop the TLC plate in the TLC chamber (see Figs. 1.1 and 1.2). Mark the solvent front with the pencil. Visualize the spots using a UV lamp (254 nm) and draw a line around the UV-active spots on the TLC clearly with the pencil. Assess the completion of the reaction based on the TLC results. Repeat the TLC analysis after ten minutes, if you find significant amounts of 1,4-DHP in the reaction mixture. [Note that you will perform TLC analysis again in procedure (8).] Place the last TLC plate in a zipper storage bag marked “A.”

XX+YY

Fig. 1.1 Spots on the TLC plate before Fig. 1.2 TLC plate placed in the development; TLC developing X: 1,4-DHP, Y: Reaction mixture. chamber.

(6) Set up the suction filtration equipment (see Fig. 1.3). Connect the suction flask to the diaphragm vacuum pump. Place a Büchner funnel fitted with a rubber adapter onto the suction flask. Place a glass microfiber filter sheet on the funnel. (7) Add water (5 mL) to the reaction mixture using a 10-mL plastic graduated cylinder. Add sodium metabisulfite (1 g), transfer the contents of the tube (including the stirring bar) into a 200-mL conical beaker and wash the test tube with water (30 mL). Place the Fig. 1.3 Suction filtration equipment: i, Büchner funnel; ii, rubber adopter; iii, 200-mL conical beaker on the magnetic stirrer suction flask; iv, diaphragm vacuum pump. 22 and stir the solution. Add saturated sodium hydrogencarbonate solution in small portions using a 2-mL graduated pipette until the pH of the aqueous phase becomes just over 7 (check the pH with pH test paper). Filter the precipitate formed through the Büchner funnel with suction using the diaphragm vacuum pump, and wash the precipitate with a small portion of water. Suck air through the precipitates for a minute to dry the product. (8) Transfer the filtrate from the suction flask to a 300-mL conical beaker. Transfer the filtrate (2 mL) to a 10-mL test tube using a 2-mL graduated pipette. Place a 10-mm magnetic stirring bar in the test tube and fix it securely with the clamp. Add 1 mL of ethyl acetate to the test tube using a 2-mL graduated pipette and stir the solution vigorously for 30 seconds on the magnetic stirrer. Stop stirring and wait for the solution to separate into two layers. Analyze the upper layer by TLC to see if there is any product remaining in the filtrates. Spot the filtrates on the plate in the same way as procedure (5). Mark the solvent front and the spot(s), if any. Place the TLC plate in a zipper storage bag marked “B.” If you detect the product on the TLC plate, add more saturated sodium hydrogencarbonate solution. (9) At this stage, if you find a precipitate formed, filter and wash it. If you find no precipitate, skip this filtration process. (10) Suck air through the precipitate for 10 minutes to dry the product. Place your product and the glass microfiber filter sheet in the crystallization dish. Cover the dish with the lid marked with your code. Avoid placing the stirring bar in the dish. Place the crystallization dish with the lid in a zipper storage bag marked “C.” a) Copy (sketch) the TLC plate in bag “A” on your answer sheet.

Indicate the solvent front line and the base line.

1) If there are less than three spots loaded on the

base line, 3 points will be subtracted.

2) If the spots are not separated on the TLC after

development, 2 points will be subtracted.

3) If the solvent front line and/or the base line is

missing, 1 point will be subtracted for each.

23 b) Determine and record the Rf values (to the 2nd decimal place) of the spots on the TLC plate in bag “A.”

Spot Rf value

1,4-DHP 0.32-0.42

Product 0.61-0.71

Two points each will be awarded for Rf values (to the 2nd decimal place) in the ranges shown above. No points will be awarded for values outside the ranges. A score of 1 will be given if the value is reported down to the 1st decimal place. c) Draw the structural formula of the organic cation before adding sodium hydrogencarbonate.

If the correct structural formula is drawn as is shown below, 2 points will be

awarded.

O O CH CH CH CH 3 2 O O 2 3

H3C N CH3 H d) What is (are) the final product(s) derived from UHP? Give the chemical formula(e) of the product(s).

If correct chemical formulae are written as shown below, 1 point each will be

awarded.

H2O and CH4N2O

e) Submit the following: i) TLC plate in bag “A” ii) TLC plate in bag “B” iii) Your product and filter paper in the crystallization dish placed in bag “C” iv) TLC plate in bag “A” If the outline to be drawn with a pencil around the UV-active spots is unclear or missing, 1 point will be subtracted.

24 v) TLC plate in bag “B” 1) If the outline to be drawn with a pencil around the UV-active spots is unclear or missing, 1 point will be subtracted. 2) If the solvent front line and/or the base line is missing, minus 1 point for each will be subtracted. vi) Your product and filter paper in the crystallization dish stored in bag “C” 1) The scientific committee will measure the percent yield after drying at 60 °C.

2) In most cases, the sample is pure and dissolved in CDCl3 completely. The following calculation based on the percent yields obtained will be applied only if no 1,4-DHP or byproducts is observed in the 1H NMR spectrum and the product is

completely soluble in CDCl3.

If 80.0 ≤ %yield <92.0, 0-24 points If 92.0 ≤ %yield < 99.0, 24 points. If 99.0 ≤ %yield < 102.0, 24-0 points.

3) If there are peaks of 1,4-DHP (ca δ 2.19 ppm) and the corresponding pyridine product (ca δ 2.85 ppm) in the 1H NMR spectrum and the percent yield is 100% or less, the actual percent yield is calculated by the following equation:

Sample mass (g) (Integral at δ 2.85 ppm) x 251.3 x x 100 Theoretical yield (g) (integral at δ 2.19) x 253.3 + (integral at δ 2.85 ppm) x 251.3

1 4) If insoluble material remains after the addition of CDCl3 for H NMR measurement, 6 points will be subtracted. 5) If byproducts are detected evidently in the 1H NMR spectrum, 6 points will be subtracted.

25 Task 2 2a 2b 2c 2d 2e 2f Total i ii 2 2 15 15 3 3 5 45

Determination of Fe(II) and Fe(III) by visual colorimetry In this experiment, you are required to determine Fe(II) and Fe(III) in a given sample solution which simulates a dissolved magnetite ore by visual colorimetric analysis involving a color reaction between Fe(II) and 2,2’-bipyridine (bpy) to form an intensely red complex, 2+ Fe(bpy)3 . 2+ The amount of Fe(bpy)3 complex can be quantified by visual colorimetric measurement using Nessler tubes. This is a quite simple technique that was employed before photoelectric instruments were generally available, but an accuracy of less than ±5% can be achieved. In this technique, a pair of Nessler tubes is used; one is filled with a reference solution, and the other is filled with a solution to be tested. The depths of colors of the two solutions are balanced by adjusting the heights of liquid columns of the solutions. When the colors look the same, the concentration can be calculated from that of the reference solution with a known concentration and the height of the column of each solution based on the Lambert-Beer law: A = εcl where A is the absorbance, c is the concentration, l is the pass length and ε is the molar absorption coefficient. First, you will learn to employ this technique by conducting measurements A and B, and then you will determine the concentrations of Fe(II) and Fe(III) with measurements C and D.

Procedures (1) Add 5 mL of acetate buffer solution, 5 mL of disodium hydrogenphosphate solution (to mask Fe(III)), 5 mL of 2,2’-bipyridine solution and 10.00 mL of sample solution into a 50-mL volumetric flask using appropriate pipettes for each and dilute the resulting solution with water to the 50-mL mark. Then stopper the flask and mix the solution well. Allow it to stand for at least 20 min to fully develop color. This solution is named “sample 1.” (2) Add 5 mL of acetate buffer solution, 5 mL of 2,2’-bipyridine solution and 5.00 mL of sample solution into a 50-mL volumetric flask. Then add 20 mg of sodium thioglycolate

26 powder (in excess) to reduce Fe(III) to Fe(II). Dilute the solution with water to the 50-mL mark, stopper the flask and mix the solution well. Allow it to stand for at least 20 min. This solution is named “sample 2.” (3) Perform visual colorimetric measurements A – D based on the “Instructions for visual colorimetric measurement” shown below.

Instructions for visual colorimetric measurement Set a pair of Nessler tubes on a Nessler tube rack placed on an LED light box (do not remove it from the bag at any time) and turn on the light (see Fig. 2.1). Pour the 2+ provided “standard Fe(bpy)3 solution 1” into one tube to an appropriate height (70 – 90 mm is recommended) from the bottom (etched marks on the tube indicate fixed heights from the bottom in mm) and use this as a reference for measurements A - D. Pour the solution to be measured into the other tube, and then compare its depth of color with that of the reference solution by looking downward through the solutions toward the LED light box. Adjust the height of the liquid column of the test solution by adding or removing the solution with a graduated pipette until the depth of color in the two tubes is identical. Estimate your reading to at least 1 mm. Note that the depths of color in a certain range may be recognized as identical to human eyes. The appropriate value for the height of the test solution, h, should be determined by taking the range into the consideration. For example, if you adjust the height of the liquid column of the test solution only by increasing (or Fig. 2.1 Visual colorimetric decreasing) the volume, you could reach a lower measurement: i, Nessler tube; ii, (or higher) value than the true one. A possible Nessler tube rack; iii, LED light box in a zipper storage bag; iv, way to estimate the true value is to take an power switch. average between the values of lower and higher limits.

2+ Measurement A: Perform a measurement using “standard Fe(bpy)3 solution 1” as both the reference and the test solutions. In this measurement, pour the reference

27 solution into a Nessler tube to achieve an appropriate height, and then pour the test solution into the other Nessler tube until the colors of the two solutions match each other. (When the colors match, the heights should IDEALLY be the same.) Then add more test solution until you recognize that the colors have become different from each other. Report both the lower and higher limits of the height of the liquid column of test solution with the same depth of color as the reference solution. a) Report your results for measurement A using the table provided on the answer sheet.

h' (height of Lower limit of Higher limit of h (estimated standard h /mm h /mm height of test solution 1) / solution) / mm mm

Measurement A Any value Any value Any value Any value

Two points will be awarded, except when there is no answer.

2+ Measurement B: Perform a measurement of “standard Fe(bpy)3 solution 2” as a test 2+ solution using “standard Fe(bpy)3 solution 1” as a reference. b) Report your results for measurement B using the table provided on the answer sheet.

h' (height of standard h (estimated height of test solution 1) / mm solution) / mm

Measurement B Any value Any value Two points will be awarded, except when there is no answer.

Measurement C: Perform measurement of sample 1. c) Report your results for measurement C using the table provided on the answer sheet.

h' (height of standard h (estimated height of test solution 1) / mm solution) / mm

sample 1: 1.23 h'

Measurement C Experimental value of h' sample 2: 1.16 h'

sample 3: 1.10 h'

28 Measurement D: Perform measurement of sample 2. d) Report your results for measurement D using the table provided on the answer sheet.

h' (height of standard h (estimated height of test solution 1) / mm solution) / mm

sample 1: 0.763 h'

Measurement D Experimental value of h' sample 2: 0.725 h'

sample 3: 0.749 h'

For 2c and 2d, a full score of 15 points will be awarded for values within a ±5% error range. A score of zero will be given if the absolute error is 15% or more. A linear point scale will be applied for scores from zero to 15; points will be calculated by the following equation: 15

⎡ MV − h − MV ⋅ 0.05 ⎤ P = 15⎢ 1 − ⎥ 10 ⎢ (MV ⋅ 0.15) − (MV ⋅ 0.05)⎥ ⎣ ⎦

Points h'⋅2.0 (mg L−1) 5 MV = c P : Points (no negative value; zero if P < 0) 0 MV : Master value of h (mm) -20 -15 -10 -5 0 5 10 15 20 h : Experimental height of liquid column of the % error test solution (mm) h’ : Experimental height of liquid column of reference solution (mm) c : Concentration of Fe in correctly prepared test solutions (mg L-1) for 2c, c = 1.63,1.72 and 1.82 for Sample 1, 2 and 3, respectively. for 2d, c = 2.62, 2.76, and 2.67 for Sample 1, 2 and 3, respectively. e) Express the concentration of the test solution, c, using the concentration of the reference solution, c’, and the height of each liquid column, h and h’.

c'h' c = h

3 points. Any equivalent formula is acceptable.

29 f) Calculate the concentrations of Fe(II) and Fe(III) in the original sample solution in mg L-1.

For Fe2+, 2.0(mg L−1)× h' × 50(mL) [Fe2+ ] = C hC ×10(mL)

[Fe2+]: concentration of Fe2+ in the sample solution (mg L-1)

hC: experimental height (mm) of the liquid column of the test solution in the measurement C

h’C : experimental height (mm) of the liquid column of the standard solution in the measurement C

If the concentrations are calculated correctly from the experimental data, full marks will be awarded 3 points.

For Fe3+ 2.0(mg L−1)× h' × 50(mL) [Fe3+ ] = D − [Fe2+ ] hD × 5(mL)

[Fe3+]: concentration of Fe3+ in the sample solution (mg L-1)

hD : experimental height (mm) of the liquid column of the test solution in the measurement D

h’D : experimental height (mm) of the liquid column of the standard solution in the measurement D

If the concentrations are calculated correctly from the experimental data, full marks will be awarded 5 points.

Concentrations of Fe2+ and Fe3+ in each original sample solution [Fe2+] / mg L-1 [Fe3+] / mg L-1 Sample 1 8.16 18.0 Sample 2 8.60 19.0 Sample 3 9.08 17.7

30 Task 3 3.1a 3.1b 3.1c 3.1d 3.1e 3.1f 3.2 Total 4 10 1 10 1 4 20 50

Polymers in Analysis Polymers can be used in various analyses. In this task, you are first required to analyze a polysaccharide using a polymer-polymer interaction, which will then be utilized to identify polymers in the second part.

3.1 Analysis of Polysaccharide by Colloid Titration - You are provided with a solution of a polysaccharide containing sulfonate (-SO3 ) and carboxylate (-COO-) groups. You are asked to determine the concentrations of these two groups by colloid titration under the basic and acidic conditions based on the differences in the protonation behavior of these acid groups. A back-titration technique is utilized. When these acid groups are ionized, the polysaccharide becomes a polyanion. Upon addition of polycation, poly(diallyldimethylammonium) (provided as its chloride salt, PDAC), it forms a polyion complex. PDAC solution is standardized using the standard solution of potassium poly(vinyl sulfate) (PVSK). At the endpoint of colloid titration, the number of anionic groups becomes equal to that of cationic groups.

Procedures (1) Take precisely 20 mL of the PDAC solution using a volumetric pipette into a 100-mL conical beaker. Add 2 drops of toluidine blue (TB) into the conical beaker. Titrate the resulting blue solution with the 0.0025 mol L-1 PVSK (monomer unit concentration) standard solution. At the endpoint, the color turns purple. Note that the solution becomes gradually turbid as the endpoint approaches. The endpoint is determined when the color remains purple for 15-20 seconds. Repeat if necessary.

1a) Report the PVSK solution volume (in mL) consumed in the standardization of PDAC. Record your reading to 0.05 mL. PVSK solution volume consumed in MV(z) = 20.06 mL the standardization of PDAC:

z mL 31 A full score of 4 points will be awarded if the answer is MV(z) ± 0.15 mL. (MV: Master Value) A score of zero will be given if the answer is less than (MV(z) – 0.5) mL or greater than (MV(z) + 0.5) mL. A linear point scale will be applied for answers in between. Two points will be subtracted if the value is not reported down to the 2nd decimal place (in mL). mark

‐0.5 ‐0.4 ‐0.3 ‐0.2 ‐0.1 0 0.1 0.2 0.3 0.4 0.5 ΔV (2) Take precisely 5 mL of the polysaccharide solution and 20 mL of the PDAC solution using volumetric pipettes into another conical beaker. Add 0.4 mL of 0.5 mol L-1 NaOH and 2 drops of TB to the solution. Titrate the resulting blue solution with the PVSK standard solution in a similar manner. Repeat if necessary. (The appearance of coagulation may be different, depending on the pH of the solution.)

1b) Report the PVSK solution volume (in mL) consumed in the titration under basic conditions. Record your reading to 0.05 mL. PVSK solution volume consumed Sample A: MV(x) = 13.14 mL under basic conditions: Sample B: MV(x) = 12.07 mL

x mL Sample C: MV(x) = 10.91 mL

A full score of 10 points will be awarded if the answer is MV(x) ± 0.25 mL. A score of zero will be given if the answer is less than (MV(x) – 0.6) mL or greater than (MV(x) + 0.6) mL. A linear point scale will be applied for answers in between. Two points will be subtracted if the value is not reported down to the 2nd decimal place (in mL). A score of zero will be applied if the value becomes negative after the subtraction.

1c) Mark the acid group(s) ionized under the basic conditions on the answer sheet.

conditions acid group basic □X -SO3H □X –COOH

Total 1 point.

(3) Repeat procedure 2 above with the addition of 0.5 mL of 0.5 mol L-1 HCl instead of 0.5 mol L-1 NaOH.

32 1d) Report the PVSK solution volume (in mL) consumed in the titration under acidic conditions. Record your reading to 0.05 mL.

PVSK solution volume consumed Sample A: MV(y) = 15.26 mL under the acidic conditions: Sample B: MV(y) = 14.61 mL y mL Sample C: MV(y) = 13.59 mL

A full score of 10 points will be awarded if the answer is MV(y) ± 0.25 mL. A score of zero will be given if the answer is less than (MV(y) – 0.6) mL or greater than (MV(y) + 0.6) mL. A linear point scale will be applied for answers in between. Two points will be subtracted if the value is not reported down to the 2nd place of decimals (in mL). A score of zero will be applied if the value becomes negative after the subtraction.

1e) Mark the acid group(s) fully ionized under acidic conditions on the answer sheet.

conditions acid group acidic □X -SO3H □ –COOH

Total 1 point.

- - 1f) Calculate the concentrations of the -SO3 (or -SO3H) groups and the -COO (or -COOH) groups (in mol L-1) in the given polysaccharide solution.

- -SO3 (or -SO3H) group: 0.0005(z - y) mol L-1 -COO- (or -COOH) group: 0.0005(y - x) mol L-1

Total 4 points, 2 points for each. A score of 2 is given to the values within (calculated value) ± 0.2. A score of 1 is given to the values which were outside the above allowance (± 0.2 mol L-1) and within (calculated value) ± 0.5 mol L-1.

33 3.2 Identification of compounds You are provided with five solutions (X-1~5, “X” designates your sample code, which is a letter in the Roman alphabet from A to H), and each solution contains one of the compounds below (all of which are used). The concentration is 0.05 mol L-1 (for polymers, monomer unit concentration). Your task is to identify all the compounds by carrying out the following procedures.

HOCH2CH2OCH2CH2OCH2CH2OH (TEG)

CH3

CH2CH2O CH2 C n COONa n (PEO) (PMANa)

CH CH 2 CH2 CH2

N+ SO Na H C CH 3 n 3 Cl- 3 n (PSSNa) (PDAC)

[Abbreviations: TEG, triethylene glycol; PEO, poly(ethylene oxide); PMANa, poly(sodium methacrylate); PSSNa, poly(sodium 4-styrenesulfonate); PDAC, poly(diallyldimethylammonium chloride) MW. stands for molecular weight.]

Helpful comments 1) Aggregates observed in Task 3.1 could be observed when mixing two polymer solutions in an appropriate combination, in which an interaction takes place between the two polymers. They can be utilized to identify polymer samples. 2) The volume of a solution measuring 5 mm in height from the bottom of the vial is approximately 1 mL. Remind that you have only 10 mL of each solution.

34 Procedures (1) Mix similar volumes of two solutions together in a vial.

(2) If necessary, you can acidify the resulting mixture. Ten drops of hydrochloric acid (0.5 mol L-1 HCl) from a plastic Pasteur pipette are sufficient for this purpose.

Identify the compound in each solution based on the experimental results. For each solution, mark one of the five boxes to indicate your identification. You are also asked to fill in the blanks with one of the letters in the Roman alphabet, from A to H, to indicate your sample code.

Sample code

-1 □ TEG □ PEO □ PMANa □ PSSNa □ PDAC

-2 □ TEG □ PEO □ PMANa □ PSSNa □ PDAC

-3 □ TEG □ PEO □ PMANa □ PSSNa □ PDAC

-4 □ TEG □ PEO □ PMANa □ PSSNa □ PDAC

-5 □ TEG □ PEO □ PMANa □ PSSNa □ PDAC

Before (upper rows) and after (lower rows) the addition of HCl TEG PEO PMANa PSSNa PDAC

TEG - PEO - - - PMANa - + - - - PSSNa - - - - - + + PDAC - - - + +: Precipitation, -: No precipitation (or the precipitate disappears) 35 PMANa and PSSNa are polyanions, and they interact with a polycation (PDAC) to form a precipitate. Under acidic conditions, the carboxylate (-COO-) groups in PMANa undergo protonation, and PMANa changes to protonated poly(methacrylic acid) (PMA). The resulting carboxy (-COOH) groups interact with the ether oxygen atoms in PEO through hydrogen bonding to form a precipitate. Since protonated PMA is no longer a polyanion, the precipitate (the complex between PMANa and PDAC) disappears after the addition of HCl. On the other hand, PSSNa does not exist as the protonated form, even under acidic conditions, and no precipitate is observed with PEO at a lower pH. Since TEG is a small molecule, its interaction with PMA is not strong enough to form a precipitate.

1) For each correct answer, 4 points will be awarded. 2) If two or more boxes are marked for one sample, 0 points will be given for that sample even if the correct answer is included in the marked compounds. 3) If the same box is marked for more than two samples, 0 points will be given for these samples even if the correct answer is included in the marked samples.

Table List of samples in Task 3.2 TEG PEO PMANa PSSNa PDAC A-3 A-2 A-1 A-4 A-5 B-2 B-1 B-5 B-3 B-4 C-1 C-5 C-4 C-2 C-3 D-5 D-4 D-3 D-1 D-2 E-3 E-2 E-1 E-4 E-5 F-2 F-1 F-5 F-3 F-4 G-1 G-5 G-4 G-2 G-3 H-5 H-4 H-3 H-1 H-2

36 HOCH2CH2OCH2CH2OCH2CH2OH (TEG)

CH3

CH2CH2O CH2 C n COONa n (PEO) (PMANa)

CH CH 2 CH2 CH2

N+ SO Na H C CH 3 n 3 Cl- 3 n (PSSNa) (PDAC)

[Abbreviations: TEG, triethylene glycol; PEO, poly(ethylene oxide); PMANa, poly(sodium methacrylate); PSSNa, poly(sodium 4-styrenesulfonate); PDAC, poly(diallyldimethylammonium chloride)

37

Instructions

• Ensure that your name and student code are written in the spaces provided at the top of each answer sheet. • You have 5 hours to work on the problems. • Use only the pen and the calculator provided. • All results must be written in the appropriate boxes. Anything written elsewhere will not be graded. Use the reverse of the sheets if you need scratch paper. • Write any relevant calculations in the appropriate boxes when necessary. If you provide no working and only the correct result for a complicated calculation, you will receive no marks. • Numerical answers are meaningless without the appropriate units. You will be heavily penalized if units are not given where required. • You must stop work immediately when the STOP command is given. A delay in doing this may lead to your disqualification from the exam. • When you have finished the examination, you must put your papers into the envelope provided, and seal the envelope by yourself. • Do not leave your seat until permitted by the supervisors. • This examination has 22 pages. The answer booklet comprises 17 pages. • The official English version of this examination is available on request only for clarification.

38

Constants and Formulae

Avogadro N = 6.022 x 1023 mol–1 Ideal gas equation: pV = nRT constant: A

Gas constant: R = 8.314 J K–1 mol–1 Gibbs energy: G = H – TS

–1 o o Faraday constant: F = 96485 C mol ΔrG = −RT logeK = −nFEcell

–34 o RT cox Planck constant: h = 6.626 x 10 J s Nernst equation: E = E + loge zF cred Energy of a hc Speed of light: c = 2.998 x 108 m s–1 E = = hν photon: λ Zero of the I 273.15 K Lambert-Beer law: A = log 0 = εcl Celsius scale: 10 I

In equilibrium constant calculations all concentrations are referenced to a standard concentration of 1 mol L-1. Consider all gases ideal throughout the exam.

39

Periodic table with relative atomic masses

1 18 1 2 H He 1.01 2 13 14 15 16 17 4.00

3 4 5 6 7 8 9 10 Li Be B C N O F Ne 6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18 11 12 13 14 15 16 17 18 Na Mg Al Si P S Cl Ar 22.99 24.30 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.64 74.92 78.96 79.90 83.80 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 85.47 87.62 88.91 91.22 92.91 95.96 - 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29 55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 57- Cs Ba 71 Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 132.91 137.33 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 - - - 87 88 104 105 106 107 108 109 110 111 89- Fr Ra 103 Rf Db Sg Bh Hs Mt Ds Rg ------

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 138.91 140.12 140.91 144.24 - 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr - 232.04 231.04 238.03 ------

40

Problem 1 8% of the total

1a 1b 1c 1d 1e 1f 1g 1h 1i Task 1 2 4 2 1 1 1 3 2 1 17

In 1894, Lord Rayleigh reported that the mass of chemically prepared nitrogen was different from that of nitrogen extracted from the atmosphere, as shown in Tables 1 and 2. Later, this difference was attributed to the presence of argon in atmospheric nitrogen. The masses of gases were measured by using a glass vessel with a known volume under atmospheric pressure (1.013 × 105 Pa).

Table 1. Mass of Chemical Nitrogen in the Vessel

From nitric oxide 2.3001 g From nitrous oxide 2.2990 g From ammonium nitrite purified at a red heat 2.2987 g From urea 2.2985 g From ammonium nitrite purified in the cold 2.2987 g

Mean 2.2990 g

Table 2. Mass of Atmospheric Nitrogen in the Vessel

O2 was removed by hot copper (1892) 2.3103 g O2 was removed by hot iron (1893) 2.3100 g O was removed by ferrous hydrate (1894) 2.3102 g 2 Mean 2.3102 g

a) Calculate the volume V [m3] of the vessel used by Rayleigh from the mean mass of chemical nitrogen, which must have been pure nitrogen. Assume that the measurements were carried out at a temperature of 15.0 °C.

–1 The amount n of the pure nitrogen (chemical nitrogen), M = 28.02 g mol , is m 2.2990 n = = = 8.205 × 10–2 mol. [or equivalent] (1 pt) M 28.02 nRT Then, from the ideal gas law, V = p

8.205⋅× 10−2 8.314 × 288.15 = = 1.940 × 10–3 m3. (1 pt) 5 1.013⋅ 10

V = m3

41

b) Estimate the mole fraction x of argon in Rayleigh's atmospheric nitrogen, by assuming that argon and nitrogen were the only constituents. Use the mean masses of the atmospheric and chemical nitrogen for the calculation.

The equation for the ratio of the mass of atmospheric nitrogen to the mass of

chemical nitrogen is

28.02(1−+xx ) 39.95 2.3102 = . [or equivalent] (1 pt) 28.02 2.2990 Transformation gives (2.3102− 2.2990) / 2.2990 x =×28.02 [or equivalent] (2 pt) 39.95− 28.02 = 1.14 × 10–2 (or 1.14%) (1 pt)

x =

Ramsay and Clève discovered helium in cleveite (a mineral consisting of uranium oxide and oxides of lead, thorium, and rare earths; an impure variety of uraninite) independently and virtually simultaneously in 1895. The gas extracted from the rock showed a unique spectroscopic line at around 588 nm (indicated by D3 in Figure 1), which was first observed in the spectrum of solar prominence during a total eclipse in 1868, near the well- known D1 and D2 lines of sodium.

587588589 590 nm

D3 D2 D1 He Na

Figure 1. Spectral lines around 588 nm c) Calculate the energy E [J] of a photon with the wavelength of the D3 line of helium shown in Figure 1.

According to Figure 1, the wavelength of the D3 line is approximately 587.7 nm (no punishment if 587.8 or 588 is used). hc The corresponding photon energy is E = λ

6.626⋅× 10−34 2.998 ⋅ 10 8 = (1 pt) −9 587.7⋅ 10 = 3.380 × 10–19 J. (1 pt)

E = J

42

Figure 2 shows an energy diagram of the atomic orbitals of helium. The arrows indicate the "allowed" transitions according to the spectroscopic principle.

3p 3d 3s 3.6 3.6 [D] [E]

3.4 3.4 [C] 2p

J

8

1

–

0

1 3.2 3.2 / 2s E [B] 3.0 [A] 3.0

0.0 1s

Figure 2. Energy diagram of atomic orbitals of helium when an electron resides in the 1s orbital.

d) Identify the transition relevant to the D3 line of helium among the transitions [A] to [E] indicated in Figure 2. Mark one on the answer sheet:

[E] The energy, 3.382 × 10–19 J, matches with the energy of the transition [E]

between the 2p and 3d orbitals. (1 pt) –19 cf.) Energy difference [10 J] = [A]:33.6, [B]:36.9, [C]:5.1, [D]:2.8, [E]:3.4

e) Which equation explains the occurance of helium in cleveite among [A] to [D] below? Mark one on the answer sheet:

[A] 238U → 234Th + α

[B] UHe2 → U + 2He [C] 240U → 240Np + β– [D] 235U + n → 95Y + 139I + 2n

[A] Considering that the α particle is the nucleus of helium, α-decay [A] is the relevant source of helium in such rocks. No compound of He such as UHe2 in [B] is known to be stable at ambient temperature. [C] is a radio active 240 235 decay of U in the thorium series. [D] is a nuclear fission reaction of U occuring in nuclear reactors. The correct answer is [A]. (1 pt)

43

Argon is also found in minerals such as malacon.

f) Which equation explains the occurance of argon in rocks among [A] to [D] below? Mark one on the answer sheet.

[A] ArF2 → Ar + F2 [B] ArXe → Ar + Xe [C] 40K → 40Ar + ε/β+ (electron capture / positron emission) [D] 126I → 126Ar + β–

[C] [C] is a well-known radioactive decay reaction occurring with a half-life of the order of the age of the earth. No stable compound of Ar, such as ArF2 or 126 – ArXe, can be expected. Products of [D] should be Xe + β . The correct answer is [C]. (1 pt)

One of the strongest evidences for the monoatomicity of argon and helium is the ratio of the heat capacity under constant pressure to that at constant volume, γ = Cp / CV, which is exactly 5/3 (1.67 ± 0.01) for a monoatomic gas. The ratio was derived from the measurement of speed of sound vs by using the following equation, where f and λ are the frequency and wavelength of the sound, and R, T, and M denote the molar gas constant, absolute temperature, and molar mass, respectively. γ RT v ==f λ s M For an unknown gas sample, the wavelength of the sound was measured to be λ = 0.116 m at a frequency of f = 3520 Hz (Hz = s–1) and temperature of 15.0 °C and under atmospheric pressure (1.013 × 105 Pa). The density ρ of the gas for these conditions was measured to be 0.850 ± 0.005 kg m–3.

g) Calculate the molar mass M [kg mol–1] of this gas.

nM The density ρ is given by ρ = . [or equivalent] (1 pt) V

By combining with the ideal gas law gives:

ρRT 0.850× 8.314× 288.15 M = = [or equivalent] (1 pt) 5 p 1.013⋅ 10 = 2.01 × 10–2 kg mol–1. (20.1 g mol–1) (1 pt)

M = kg mol–1

44

h) Calculate the heat capacity ratio γ for this gas sample.

γ RT From the equation for the sonic velocity, f λ = , M M 2.01⋅ 10−2 γ = ()f λ 2 =×(3520 0.116)2 [or equivalent] (1 pt) RT 8.314× 288.15

= 1.40 (1 pt)

M ρ ρ 2 0.850 2 (or, using = , γ = ()f λ =×(3520 0.116) = 1.40) RTp p 5 1.013⋅ 10

γ =

i) Which is this gas among [A] to [D]? Mark one on the answer sheet:

[A] HCl [B] HF [C] Ne [D] Ar

[B] From M = 20.1 g mol–1, this gas must be HF or Ne. From γ = 1.4 (≠ 5/3≈1.67), this is NOT a monoatomic gas (i.e., HCl or HF). Thus, this gas must be [B] HF. (1 pt) Note: It is not possible to distinguish between HF (M = 20.01) and Ne (M = 20.18) from the molar mass only, which is 20.10±0.12 by taking into account the uncertainty of ρ (±0.005 / 0.850 = ±0.6%). However, the precision of γ = 1.40 is enough to exclude the possibility of monoatomic gas (γ = 5/3≈1.67).

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Problem 2 6% of the total

2a 2b 2c 2d 2e Task 2 4 4 4 3 5 20

Crystal structure of alkali metal halide In crystals of ionic compounds, cations are generally arranged in the interstices of the closest packed lattice of anions. The structure of an ionic crystal such as sodium chloride becomes stable when the cations are in contact with the nearest anions. a) In the crystal of sodium chloride, both Na+ and Cl- ions form a face-centered cubic lattice. Give the numbers of Na+ and Cl- ions in a unit cell and the coordination numbers of Na+ and Cl- ions in sodium chloride crystal.

Number of ions Na+: 4 Cl-: 4

Coordination number Na+: 6 Cl-: 6

[Total 4 pts] [2 pt] Both number of Na+ and Cl- ions are correct. + - [1 pt] Each coordination number of Na and Cl ions is correct. b) The ionic radii of Na+ and Cl- ions in the crystal of sodium chloride are 0.102 nm and 0.181 nm, respectively. Calculate the density [kg m-3] of the sodium chloride crystal.

[Total 4 pts]

Length of lattice l: l = 0.102 × 2 + 0.181× 2 = 0.566 nm [2 pt]

Density ρ: (22.99 + 35.45) × 4 6 −3 3 −3 ρ = = 2.1408 ×10 g m = 2.14 ×10 kg m (0.566 ×10 −9 )3 × 6.022 ×10 23 [1 pt for the equation of density, 1 pt for final answer.]

Density of NaCl crystal (kg m-3): 2.14 × 103 kg m-3

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Born-Haber cycle and lattice enthalpy In ionic inorganic compounds such as sodium chloride, the heat of lattice formation from gaseous ions is very high, and the contribution of the change in entropy is small. Therefore, the lattice formation enthalpy is estimated from enthalpy data by using a Born-Haber cycle. c) The figure below shows the Born-Haber cycle of NaCl. The labels “g” and “s” represent “gas” and “solid” states respectively. Show chemical equations in the A and F steps.

+ - Na (g) + Cl (g) + e

D: Dissociation of Cl2 (g) E: Electron gain by Cl (g)

C: Ionization of Na (g)

F: Dissociation of NaCl (s) B: Sublimation of Na (s)

A: Formation of NaCl (s) from elemental substances.

NaCl (s)

A: Na (s) + 1/2Cl2 (g) → NaCl (s) [2 pt]

F: NaCl (s) → Na+ (g) + Cl- (g) [2 pt]

d) Calculate the enthalpy of the lattice formation of NaCl [kJ mol-1] by using the following enthalpy data of the respective steps in the above Born-Haber cycle.

Formation of Sublimation Ionization of Dissociation Electron gain NaCl (s) of Na (s) Na (g) of Cl2 (g) by Cl (g) –411 kJ mol-1 109 kJ mol-1 496 kJ mol-1 242 kJ mol-1 –349 kJ mol-1

[Total 3 pts] Enthalpy conservation condition: –A + B + C + D/2 = F – E [1 pt] From the above equation, –(–411) + 109 + 496 + (242/2) = F + 349, thus, F=788 [1 pt] The lattice formation enthalpy of NaCl is –F, thus, –788 kJ mol-1 [1 pt] Lattice formation enthalpy of NaCl (kJ mol-1): –788 kJ mol-1

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Synthesis of sodium carbonate by the ammonia-soda process (Solvay process) Sodium carbonate (anhydrous soda ash) is a raw material in the manufacture of glass, medicaments, alkaline detergents, etc. e) The total chemical reaction in the ammonia-soda process is represented as follows:

2NaCl + CaCO3 → Na2CO3 + CaCl2

This reaction between sodium chloride and calcium carbonate does not proceed directly. The process comprises the following five reactions involving ammonia:

Δ CaCO3 → [ A ] + [ B ]

NaCl + NH3 + [ B ] + H2O →[ C ] + [ D ] Δ 2 [ C ] → Na2CO3 + H2O + [ B ]

[ A ] + H2O → [ E ]

[ E ] + 2 [ D ] → CaCl2 + 2H2O + 2NH3

where Δrepresents applying heat treatment. Insert the chemical formulas of the appropriate compounds in the blank spaces [ A ]–[ E ] in the above reactions.

A: CaO

B: CO2

C: NaHCO3

D: NH4Cl

E: Ca(OH)2

[Total 5 pts] 1 pt for one correct chemical formula.

48

Problem 3 7% of the total

3a 3b 3c 3d Task 3 2 3 1 3 9

The chemical oxygen demand (COD) refers to the amount of oxidizable substance, such as organic compounds, in a sample solution, and it is used as an indication of water quality in seas, lakes, and marshes. For example, the COD of service water is kept below -1 -1 1 mg L . The COD (mg L ) is represented by mass of O2 (mg) which accepts the same amount of electrons which would be accepted by the strong oxidizing agent when 1 L of a sample solution is treated with it. An example of the operation is presented below.

****************************************************** Analytical Operation A 1.00-L sample solution was acidified with a sufficient amount of sulfuric acid, and chloride ions were removed by the addition of silver nitrate solution. To the sample solution, 1.00 × 10-1 L of 5.00 × 10-3 mol L-1 potassium permanganate solution was added, and the mixture was heated for 30 min. Further, 1.00 × 10-1 L of 1.25 × 10-2 mol L-1 disodium oxalate (Na2C2O4 or NaOOC-COONa) standard solution was added, and the mixture was stirred well. Oxalate ions that remained unreacted were titrated with 5.00 × 10-3 mol L-1 potassium permanganate solution; 3.00 × 10-2 L of the solution was used for the titration. ****************************************************** a) Give the equation of the redox reaction of potassium permanganate and disodium oxalate.

2KMnO4 + 5Na2C2O4 + 8H2SO4 → 2MnSO4 + 5Na2SO4 + K2SO4 + 10CO2+ 8H2O or 2KMnO4 + 5H2C2O4 + 3H2SO4 → 2MnSO4 + 10CO2 + 8H2O + K2SO4 or - 2- + 2+ 2 MnO4 + 5C2O4 + 16H → 2Mn + 10CO2 + 8H2O

[Total 2 pts]

b) Calculate the amount of O2 (mg) that will oxidize the same number of moles of oxidizable substance as 1.00 × 10-3 L of 5.00 × 10-3 mol L-1 potassium permanganate does.

The reactions of potassium permanganate and O2 are as follows: - + - 2+ MnO4 + 8H + 5e → Mn + 4H2O + - O2 + 4H + 4e → 2H2O 49

Hence, 1 mol of KMnO4 amounts to 1.25 mol of O2. 5 × 5.00 × 10-3 (mol L-1) × 10-3 (L) = 4 × X / 32 (mol) [Underlined (or equivalent) where X is the amount of O2 (g). equation: 2 pt]

Thus, X = 2.00 × 10-4 g. → 2.00 × 10-1 mg [1 pt] [Total 3 pts]

c) From the following choices, select the most appropriate reason for the removal of chloride ions: [A] Some of the chloride ions react with potassium permanganate, resulting in an error in COD. [B] Some of the chloride ions react with disodium oxalate, resulting in an error in COD. [C] Some of the chloride ions react with organic compounds in the sample solution, resulting in an error in COD. [D] A color is developed during titration, resulting in an error in COD.

[A] [Total 1 pt]

d) Calculate the COD (mg L-1) of the sample solution described in the analytical operation above.

The amounts of electron used for reduction and oxidation are equal, then 5 × 5.00 × 10-3 (mol L-1) × (1.00 × 10-1 + A) (L) = 2 × 1.25 × 10-2 (mol L-1) × 1.00 × 10-1 (L) + X (1) [Underlined (or equivalent) where A (mL) is the amount of potasium permanganate equation: 2 pt] used for the final titration, and X (mol) is the amount of electron for the oxidizable substance. Eq.(1) gives X = 2.50 × 10-2 × A. At A = 3.00 ×10-2 (L), X = 7.50 × 10-4 (mol). Hence, COD = (32/4) (g mol-1) × 7.50 × 10-4 (mol) × 103(mg/g) × 1/1(L-1) = 6.00 mg L-1. [1 pt] [Total 3 pts] or

The amount of potasium permanganate consumed for the oxidizable substance, B (mL), is 5 × 5.00 × 10-3 × (1.00× 10-1 + A − B) = 2 × (1.25 ×10-2) × (1.00 × 10-1). [2 pt] At A = 3.00 ×10-2 L, B equals to 3.00 ×10-2 L. From the solution to question b) above, COD = (2.00 ×10-1) / (1.00 ×10-3) (mg/L) × 3.00 × 10-2 (L) × 1/1(L-1) = 6.00 mg L-1. [1 pt] [Total 3 pts]

50

Problem 4 6% of the total

4a 4b 4c 4d Task 4 2 3 2 1 8

The rechargeable lithium ion battery has been developed in Japan. The standard electromotive force of the battery is 3.70 V. Assume that the half-reaction at the cathode is + - CoO2 + Li + e → LiCoO2, and the half-reaction at the anode is + - LiC6 → 6C + Li + e . a) Write the total reaction equation of the battery and calculate the value of the standard Gibbs energy of the reaction [kJ mol-1]. Total reaction equation: CoO2 + LiC6 → LiCoO2 + 6C (1 pt)

The standard Gibbs energy of the reaction: ΔG0 = –nFE0 = –1 × 96485 C mol-1 × 3.70 V = –357 kJ mol-1 (1 pt)

b) The battery cell is constructed using LiCoO2 and graphite (C) as the electrode materials. Calculate the mass of the anode in the completely charged state and that in completely discharged state if 10.00 g of LiCoO2 and 10.00 g of graphite (C) are present initially. In the completely charged state: 10.71 g (2 pt) The amount of LiCoO2 is 10.00/97.87 = 0.1022 mol. The amount of C is 10.00/12.01 = 0.8326 mol, which is larger than 0.1022 mol × 6 = 0.6132 mol. Thus, the mass in the completely charged state of the anode is 10.00 + 0.1022 × 6.94 = 10.709 g = 10.71 g.

In the completely discharged state: 10.00 g (1 pt)

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c) Calculate the maximum energy generated per mass of the lithium ion battery cell [kJ kg-1]. Assume that the correct ratio for complete reaction between the cathode and anode materials is used and the sum of the mass of electrodes is 50.0% of the total mass of the battery cell. In comparison, the energy density of lead-acid batteries used for vehicles is about 200 kJ kg-1.

The mass of 1 mol LiCoO2 is 97.87 g The mass of 6 mol C is 12.01 × 6 g = 72.06 g The total mass of the electrode is (97.87 + 72.06) g = 169.93 g The mass of the cell is 169.93 / 0.500 g = 340 g The maximum energy generated is 357 kJ. Thus, the maximum energy per unit mass of the cell is 1050 kJ kg-1 (2 pts)

d) Because an aqueous solution cannot be used as an electrolyte, an organic solution is used in the lithium ion battery cell. Give the chemical formula of the gas generated if water is present in the electrolyte.

H2 or H2 and O2 (1 pt)

52

Problem 5 7% of the total

5a-1 5a-2 5b 5c 5d 5e 5f Task 5 1 1 2 2 3 4 5 18

When an atom X absorbs radiation with a photon energy greater than the ionization energy of the atom, the atom is ionized to generate an ion X+ and the electron (called a photoelectron) is ejected at the same time. In this event, the energy is conserved as shown in Figure 1, that is,

Photon energy (hν) = ionization energy (IE) of X + kinetic energy of photoelectron.

When a molecule, for example, H2, absorbs short-wavelength light, the photoelectron is + ejected and an H2 ion with a variety of vibrational states is produced. A photoelectron spectrum is a plot of the number of photoelectrons as a function of the kinetic energy of the photoelectrons. Figure 2 shows a typical photoelectron spectrum when H2 in the lowest vibrational level is irradiated by monochromatic light of 21.2 eV. No photoelectrons are detected above 6.0 eV. eV is a unit of energy and 1.0 eV is equal to 1.6 × 10-19 J.

Kinetic energy of photoelectron

+ IE Photoelectron spectrum of H X 2 h ν = 21.2 eV

hν

Intensity (arb.) Intensity

X 6.0 5.0 4.0 3.0 Kinetic energy of photoelectron (eV)

Figure 1. Schematic diagram of Figure 2. Photoelectron spectrum of H2. The energy of the photoelectron spectroscopy. incident light is 21.2 eV.

53

+ a-1) Determine the energy difference ΔEA1 (eV) between H2 (v = 0) and H2 (v ion = 0) to the first decimal place. v and v ion denote the vibrational quantum numbers of H2 and + H2 , respectively.

+ + a-2) Determine the energy difference ΔEA2 (eV) between H2 (v ion = 0) and H2 (v ion = 3) to the first decimal place. a-1) & a-2) The spectral peak at 5.8 eV in Fig. 2 corresponds to the electron with the highest kinetic + energy, which is generated by the reaction H2(v = 0) → H2 (vion = 0) + e. Accordingly,

ΔEA1 = 21.2 eV – 5.8 eV = 15.4 eV + One can estimate from Fig. 2 that the energy difference ΔEA2 between H2 (v ion = 0) and + H2 (v ion = 3) is approximately 0.8 eV.

ΔEA1 (eV) = 15.4 eV 1 pt

ΔEA2 (eV) = 0.8 eV 1 pt

H b) The electronic energy levels En of a hydrogen atom are given by the equation

H Ry En = − 2 ()n = 1, 2, 3Λ n . Here n is a principal quantum number, and Ry is a constant with dimensions of energy. The energy from n = 1 to n = 2 of the hydrogen atom is 10.2 eV. Calculate the ionization energy EB (eV) of the hydrogen atom to the first decimal place.

The ionization energy corresponds to n = ∞. Accordingly, 3 ∆E = Ry n=2←n=1 4

∆En=∞←n=1 = Ry Thus, the energy required for the ionization is 4/3 times larger than the transition energy of the Lyman α line. 4 EB =×=10.2 eV 13.6 eV 3 EB (eV) = 13.6 eV 2 pts

54

c) The energy threshold for the generation of two electronically excited hydrogen atoms H* (n = 2) from H2 (v = 0) has been derived to be 24.9 eV by an experiment. Determine the bond energy EC (eV) of H2 to the first decimal place.

24.9 eV = the binding energy of a hydrogen molecule + 10.2 eV + 10.2 eV. Thus, the binding energy of a hydrogen molecule = EC = 4.5 eV.

EC (eV) = 4.5 eV 2 pts

+ d) Considering an energy cycle, determine the bond energy ED (eV) of H2 to the first decimal place. If you don’t have the values for EB and EC, then use 15.0 eV and 5.0 eV for EB and EC, respectively.

From Figure 3 below, ED = EB + EC – ΔEA1 =13.6 + 4.5 – 15.4 = 2.7 eV.

ED (eV) = 2.7 eV 3 pts

e) Calculate the threshold energy EE (eV) of the following dissociative ionization reaction to the first decimal place: - H ⎯⎯→=++ H* (n 2) H+ e. 2 If you don’t have the values for EB and EC, then use 15.0 eV and 5.0 eV for EB and EC, respectively.

H + H+ + e-

ED = 2.7 eV H + + e- 2 E =13.6 eV B ΔEA1=15.4 eV H + H EC=4.5 eV H 2

From Figure 3 above, the threshold energy for the dissociative ionization reaction + － H2 → H* (n = 2) + H + e is EB + EC + 10.2 eV = 13.6 + 4.5 + 10.2 = 28.3 eV. EE (eV) = 28.3 eV 4 pts

f) When H2 absorbs monochromatic light of 21.2 eV, the following dissociation process occurs at the same time. 55

H ⎯⎯→ 21.2⎯⎯ eV⎯ H (n = 1) + H (n = 1) 2

Two hydrogen atoms move in opposite directions with the same speed. Calculate -1 the speed u (m s ) of the hydrogen atoms generated in the above reaction. H2 is assumed to be at rest. If you don’t have the value for EC, then use 5.0 eV for EC.

The excess energy is 16.7 eV (= 21.2 eV – 4.5 eV). Because two hydrogen atoms are generated upon photodissociation, half of this excess energy is released as translational energy of the hydrogen atoms. 1 mu 2 = 8.35 eV = 1.34 ×10 -18 J 2 (2 pts) 1.008 ×10 -3 kg mol -1 m = = 1.67 ×10 −27 kg 6.022 ×10 23 mol -1 Then, u 2 = 1.6 ×109 m2 s-2 u ≈ 4.0 ×10 4 m s-1 u (m/s) = 4.0 × 104 m/s 5 pts

56

Problem 6 6 % of the total

6a 6b 6c 6d Task 6 5 4 6 11 26

Read the description of four kinds of isomeric organic compounds of A, B, C, and D. All have C8H10O and contain a benzene ring. Answer the questions that follow. If there are stereoisomers, give all structural formulas. Note that any wrong isomers will be penalized. z (1)At room temperature, a piece of sodium metal was added to A, B, and C in test tubes and the evolution of hydrogen gas was observed only in the case of C. z When an iron(III) chloride aqueous solution was added to C and D, no coloration was observed in C, whereas D was colored. z A was oxidized when (2)aqueous potassium permanganate was added to it and the mixture was heated; the acidification of the heated mixture and its isolation afforded benzoic acid. z Let’s imagine that (3)a hydrogen atom in the benzene ring is replaced by a chlorine atom, it is possible to obtain four kinds of monochlorinated structural isomers from B, while only two kinds of such isomers can be obtained from D. z Hydrogenation of the benzene ring in C and D using a catalyst gave saturated alcohol(s). It was found that the saturated alcohol(s) obtained from C has no stereogenic carbons, but the one(s) from D has stereogenic carbon(s). a) Among all the isomeric organic compounds of C8H10O having a benzene ring, give the structural formulas of all the isomers that do NOT yield hydrogen gas in the underlined procedure (1), in which a piece of sodium is added to the neat samples in the case of the liquid samples and to the concentrated solution of the samples in an aprotic solvent in the case of the solid ones.

O O O O O

1pt each wrong isomer: -1pt each total pts ≥ 0 (not negative)

b) Among all the isomeric organic compounds of C8H10O having a benzene ring, give the structural formulas of all the isomers that yield benzoic acid in the underlined procedure (2).

57

OH OH OH O

1pt each wrong isomer: -1pt each total pts ≥ 0 (not negative)

c) Among all the isomeric organic compounds of C8H10O having a benzene ring, give the structural formulas of all the isomers that could yield four different mono- chlorinated structural isomers when the underlined transformation in (3) is performed.

OH OH OH OH O O

1pt each wrong isomer: -1pt each total pts ≥ 0 (not negative)

d) Give the structural formulas of A, B, C, and D. When several isomers can be considered, give the structural formulas of all of them. A B O O O

1pt 1pt each wrong isomer: -1pt each wrong isomer: -1pt each total pts ≥ 0 (not negative) total pts ≥ 0 (not negative)

OH OH C OH D OH

2pts each 2pts each wrong alcohol/phenol: -1pt each wrong alcohol/phenol: -1pt each ether: -2pts each ether: -2pts each total pts ≥ 0 (not negative) total pts ≥ 0 (not negative)

58

Problem 7 7% of the total

7a 7b 7c 7d Task 7 4 9 6 5 24

Certain varieties of puffer fish, Fugu in Japanese, are highly prized as foods in Japan. Since the viscera (especially ovaries and livers) of the fish contain a potent toxin (tetrodotoxin), food poisoning often results from its ingestion. Studies on tetrodotoxin (1) have been performed from the beginning in the 20th century; its chemical structure was elucidated in 1964. O– HO H O H N H O 2 N OH N H H HO OH H H H OH tetrodotoxin (1) a) The guanidine group in tetrodotoxin exhibits strong basicity. The guanidinium ion resulting from protonation on the guanidine group is stabilized by the existence of the following resonance. Draw two resonance structures B and C.

NHR1 B C 2 H2N NHR A B C NHR1 NHR1 2 2 H2N NHR H2N NHR

2 pts each. b) Many derivatization reactions were performed in structure studies of tetrodotoxin. Treatment of tetrodotoxin (1) with ethanolic potassium hydroxide upon heating afforded quinazoline derivative 2, which provided an insight into the nature of the fundamental skeleton of tetrodotoxin. The reaction mechanism can be described as follows. First, tetrodotoxin is hydrolyzed into carboxylate 3. Then the hydroxyl group highlighted with a frame is eliminated by the base to give intermediate D. A retro- aldol reaction of D cleaves a carbon-carbon bond to provide intermediates E and F. Finally, dehydration and aromatization from E produce quinazoline derivative 2. Draw structures of the postulated intermediates D, E, and F.

59

– O HO OH OH HO H O COO– H OH 2 H OH H O base HO HN OH H2N H H2N H O N OH N OH H N N OH H 2 H N H N H HO OH H HO OH – OH H H HO COO H H H OH H H OH 3 1 3

dehydration base (-H2O) N OH base base intermediate E intermediate D H2N N dehydration & F retro-aldol reaction OH aromatization 2 D E F OH OH OH OH H H OH H OH – HN OH HN OH O COO

H2N N H2N N H H O O HO COO– H

3 pts each. Other stereoisomers are acceptable. Each free form is acceptable. Tautomors concerning guanidine moiety are all acceptable. Enol form is acceptable. E: dehydrated products and zwitterionic structure are acceptable.

c) Although biosynthesis of tetrodotoxin still remains to be clarified, it is proposed that tetrodotoxin may be biologically synthesized from L-arginine and isopentenyl diphosphate. Among the carbons included in tetrodotoxin, circle all the carbons that are expected to be of L-arginine origin.

NH2 O O – COO –O P O P O tetrodotoxin (1) H2N N H O– O– NH2 L-arginine isopentenyl diphosphate

O– HO H O H N H O 2 N OH N H H HO OH H H H OH

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6 pts. 1 pt each for correct carbon. Deduct 1 pt for each carbon over 6. 0 pts for all carbons circled. d) In the 1990s, an alternative biosynthetic pathway of tetrodotoxin was proposed. Condensation between 2-deoxy-3-oxo-D-pentose and guanidine provides intermediate G with cyclic guanidine moiety (molecular formula C6H11N3O3). Tetrodotoxin may be biologically synthesized from intermediate G and isopentenyl diphosphate. Draw a structure of the postulated intermediate G showing the stereochemistry.

HO NH O OH 2 G ( C6H11N3O3) HN NH2 O tetrodotoxin (1) 2-deoxy-3-oxo-D-pentose O O –O P O P O O– O– HO OH isopentenyl diphosphate CHO

O G

OH H HO N NH

NH

OH

5 pts (enantiomer at C4, 3 pts, C4 stereochemistry is unclear, 3 pts).

OH OH OH H HO N NH H HO N NH HO N NH NH HO HO NH N OH acceptable Each zwitterionic structure (and protonated structure) like below is acceptable. OH H HO N NH2 NH

O– Tautomers concerning guanidine moiety are all acceptable.

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Problem 8 6% of the total

8a-1 8a-2 8a-3 8b-1 8b-2 Task 8 2 4 3 4 7 20

The esterification reaction between bi-functional molecules gives one of the typical linear chain polymers as shown in eq.(1) by polycondensation (often called “condensation polymerization”). The control of polymerization conditions and procedures determines the length of polymer strands, i.e., the average degree of polymerization, X (note that X = 2n in the present instance). Because X (and also n ) is an averaged number, it is not always an integer but a value with decimal figures.

1 2 1 2 n HOOC-R -COOH + n HO-R -OH → HO-[COR CO-OR O]n-H + (2n－1)H2O (1)

X can be estimated from the consumption of functional groups (here, -COOH and -OH).

Let us define the degree of reaction, p, as p = (N0 - N) / N0 (≦ 1), where N0 and N denote the total numbers of functional groups before and after the polymerization, respectively. For each functional group of the dicarboxylic acid molecules (A) and diol molecules (B), we add the suffixes of “A” or “B” such as NA0, NB0, NA or NB, respectively, i.e., N0 = NA0 +

NB0 and N = NA + NB. When the initial feed is unbalanced such as NA0 ≦ NB0, X is expressed by pA and r as shown in eq.(2), where r = NA0 / NB0 (≦ 1) and pA = (NA0 – NA) / NA0. If r = 1, pA is identical to p and eq.(2) becomes the same to the Carothers equation.

X = (1 + r) / (1 + r - 2pAr) (2)

a) Some nylon-6,6 sample was prepared by polycondensation between an equimolar mixture of adipic acid (hexanedioic acid) and hexamethylenediamine (hexane-1,6- diamine).

a-1) Show the chemical structure of this nylon-6,6 sample. [Caution: what are the end groups when polycondensation was started from the equimolar mixture?]

HO-[CO(CH2)4CO-NH(CH2)6NH]n-H or equivalent structures are all OK. Total 2 pts. -0.5 pt for lacking “n,” another -0.5 pt for lacking each of the end group(s).

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a-2) When this nylon-6,6 sample carries an average molecular weight, M, of 5507.25 (g mol-1), give its X value to the second decimal place.

Calculation procedures must be shown by suitable equation(s) (otherwise, no score will be provided):

The unit molecular weight, Mu, is calculated to be, Mu = (12.01 × 12 + 1.01 × 22 + 14.01 × 2 + 16.00 × 2) / 2 = 226.36 / 2 = 113.18 X = (5507.25 - 18.02) / Mu = (5507.25 - 18.02) / 113.18 = 48.50, or X = 2n = 2 × [(5507.25 - 18.02) / 226.36] = 48.50

X = 48.50

Black parts are prewritten in the answer boxes (same to all questions in Problem 8). Underlined (or equivalent) calculation procedures are required. Total 4 pts. -1 pt for calculation mistakes.

a-3) Give the p value necessary to prepare this nylon-6,6 sample of M = 5507.25 (g mol-1) to the fifth decimal place. If you get no numerical answer in a-2), use 52.50 instead.

From eq.(3) at r = 1 (Carothers eq.), X = 48.50 = 1 / (1 - p), then p = 0.979381 ≒ 0.97938

p = 0.97938 (0.98095 when X = 52.50.)

Total 3 pts. -1 pt for calculation mistakes.

b) The low-molecular-weight polyester (oligoester) is prepared from the mixture of 36.54 (g) of adipic acid (hexanedioic acid) and an unknown amount [W (g)] of butane-1,4-diol (Bdiol). Under the condition of pA→１, the oligoester with X = 11.00 carrying Bdiol units in both chain ends is obtained.

b-1) Show the precise chemical structure of this oligoester of X = 11.00.

[HO(CH2)4O]1.000-[CO(CH2)4CO-O(CH2)4O]5.000-H or HO(CH2)4O-[CO(CH2)4CO-O(CH2)4O]5.000-H is accurate, however, HO(CH2)4O-[CO(CH2)4CO-O(CH2)4O]5-H is acceptable.

Total 4 pts, -1 pt for lacking the number of unit repeating or writing “n” instead of “5.00 (or 5)”. Another -1 pt for lacking HO- and/or -H end group(s). No point if lacking the left- most HO(CH2)4O- group.

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b-2) Calculate the unknown amount, W (g), to the first decimal place.

Calculation procedures must be shown by suitable equation(s) (otherwise, no score will be provided):

Mw(adipic acid) = 146.16, Mw(Bdiol) = 90.14

Ans.1 Since X = 11.00, the oligoester contains 5.00 units of adipate and 6.00 units of Bdiol. [cf) 5.00 + 6.00 = 11.00 = X] When pA→1, the initial molar feed ratio of the monomers is equal to the molar composition of the resulting oligoester. [adipic acid]0 / [Bdiol]0 = 5.00 / 6.00, W = 90.14 × (6.00 / 5.00) × (36.54 / 146.16) = 27.042 ≒ 27.0 (g)

Ans.2 From eq.(2), when pA→1, X = (1 + r) / (1 - r). Therefore, 11.00 = [1 + {(36.54 / 146.16) / (W / 90.14)}] / [1 - {(36.54 / 146.16) / (W / 90.14)}] = [(W / 90.14) + 0.2500] / [(W / 90.14) - 0.2500] 11.00 × [(W / 90.14) - 0.2500] = [(W / 90.14) + 0.2500], 10.00 × (W / 90.14) = 3.000 W = 3.000 × 90.14 / 10.00 = 27.042 ≒ 27.0 (g)

W = 27.0 (g)

Either calculation procedures are acceptable. Underlined (or equivalent) calculation procedures are required. Total 7 pts, -1 pt for calculation mistakes.

64

Problem 9 7% of the total

9a 9b 9c 9d 9e 9f Task 9 4 2 8 4 8 8 34

α-Cyclodextrin (αCyD), which is a cyclic oligosaccharide of six α(1 → 4) linked α-D- glucopyranoside units, can be topologically represented as toroids (Figure 1). α-D- glucopyranoside units in αCyD are usually in the most stable chair conformation.

α αCyD Figure 1. Space filling model of αCyD. Left: αCyD view through the hole. Right: side view.

a) Give the absolute configuration (R or S) at stereogenic carbons C-2 and C-5 of D- glucose. Also, draw a stereostructure of the open chain form of D-glucose.

Absolute configuration at C-2: Chain form: R 1 pt O H H OH HO H Absolute configuration at C-5: OH OH O H OH HO H OH R 1 pt H OH OH or OH 2 pts (carbon skeleton: 1 pt; others: 1 pt)

65

b) Choose the most stable conformation from the four incomplete α-D-glucopyranose formulas given in the answer box and enclose it in a box. Also, add four OH groups and four H atoms to complete the α-D-glucopyranose formula. H H

OH OH O O

H

O

O OH H

OH

Answer: H OH H O HO H 4 HO 2 pts ( C1 : 1 pt; -OH: 1 pt) H OH H OH

HO

H OH H O 4 H OH 1 pts ( C1 : 0 pt; -OH: 1 pt) H

H OH OH

Others 0 pt

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αCyD in water is able to host hydrophobic molecules. When the host/guest (H/G) stoichiometry is 1/1, the inclusion complexation can be given by the following equilibrium.

k1 G ＋ HHG(1) k-1

where k1 and k-1 are the rate constant for the forward and backward reaction, respectively. The complexation of a guest to αCyD causes a chemical shift change in 1H NMR spectra. Figure 2 shows a part of 1H NMR spectra (signals from H-1 of αCyD) showing the chemical shift change in the presence of varying amounts of 1,10-bis(trimethylammonium)decane diiodide (BTAD). The doublet peak at 5.06 ppm is from H-1 of free αCyD, while the doublet at 5.14 ppm is from H-1 of αCyD complexed with BTAD. (Note that the spectra given in Figure 2 were measured in the complexation equilibrium state.)

BTAD

Figure 2. Expanded 1H NMR spectra (signals from H-1 of αCyD) of solutions containing 5.0×10-3 mol L-1 αCyD and 0-3.0 ×10-2 mol L-1 BTAD. c) In the spectrum of 5.0 x10-3 mol L-1/5.0 x10-3 mol L-1 αCyD/BTAD, the relative peak areas of the doublets at 5.06 and 5.14 ppm are 0.41 and 0.59, respectively. Calculate, to 2 significant figures, the concentration equilibrium constant, K for the inclusion complexation of αCyD/BTAD.

-3 [HG] [αCyD]0×a5.14 5.0 x10 M × 0.59 K = ------= ------= ------= 0.70 x103 -3 2 [H][G] [αCyD]0 × a5.06 × {[BTAD]0 – [αCyD]0 × a5.14} (5.0x10 M × 0.41)

1 pt 3 pts 3 pts 1 pt

a5.06: relative area of the peak at 5.06 ppm = mole fracrion of free αCyD

a5.14: relative area of the peak at 5.14 ppm = mole fracrion of αCyD complexed with BTAD K: 7.0 × 102 8 pts in total

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Complexation of αCyD with hexyltrimethylammonium bromide (HTAB) appears in NMR spectra in a way different from the αCyD/BTAD complexation. Figure 3 shows a part of 1H NMR spectra (H-6 signal of HTAB) in αCyD/HTAB solutions. The signal appears as one triplet (not two triplets), which shifts depending on the concentration of αCyD from the position of free HTAB to the position of αCyD/HTAB in proportion to the fraction of the complex in the solution. The H-6 signals from free HTAB and HTAB complexed with αCyD are triplets at 0.740 ppm and 0.860 ppm, respectively.

HTAB

Figure 3. Expanded 1H NMR spectra (H-6 signal of HTAB) of solutions containing 1.0×10-2 mol L-1 HTAB and 0-3.0×10-2 mol L-1 αCyD.

d) The signal of HTAB in αCyD/HTAB solutions appears as one triplet, which shifts depending on the concentration of αCyD. Choose the rational interpretation(s) just from these spectra.

hint: When a guest molecule move in and out of αCyD rapidly and repeatedly, only one signal of the guest is observed at the weighted average of the chemical shifts of the free guest and the shift of the guest included in αCyD.

a. k1 of αCyD/HTAB > k1 of αCyD/BTAD b. k1 of αCyD/HTAB < k1 of αCyD/BTAD c. K of αCyD/HTAB > K of αCyD/BTAD d. K of αCyD/HTAB < K of αCyD/BTAD

a 4 pts (additional choice : –2 pts for each)

68

e) The signals of HTAB in 1.0 x10-2 mol L-1/1.0 x10-2 mol L-1 αCyD/HTAB are positioned at 0.815 ppm. Calculate, to 2 significant figures, K for the complexation of αCyD/HTAB. In 1.0 x10-2 mol L-1/1.0 x10-2 mol L-1 αCyD/HTAB,

s10/10 – sfree 0.815 – 0.740 f10/10 = ------= ------= 0.625 scomplex – sfree 0.860 – 0.740 3 pts

sfree, scomplex: chemical shift of HTAB in free, and complexed state s10/10: chemical shift of HTAB in 10.0 mM/10.0 mM αCyD/HTAB f10/10: mole fraction of complexed HTAB in 10.0 mM/10.0 mM αCyD/HTAB

[HG] K = ------[H][G]

-2 -1 [HTAB]0 × f10/10 1.0 x10 mol L × 0. 625 = ------= ------2 -1 2 {[αCyD]0 – f10/10 [HTAB]0}[HTAB]0(1 – f10/10) [1.0 x10 mol L × (1 – 0. 625)] 2 pts 2 pts = 4.4 × 102

K: 4.4 × 102 1 pt 8 pts in total f) At 40.0 ºC and 60.0 ºC, K for the complexation of αCyD/HTAB are 3.12 × 102 and 2.09 × 102 respectively. Calculate, to 2 significant figures, the enthalpy change, ∆Hº [kJ mol-1], and the entropy change, ∆Sº [J K-1 mol-1]. (Ignore the temperature dependence of ∆Hº and ∆Sº.) From ΔGº= –RT ln K, ΔGº (40.0 oC) = –8.314 × 313.2 ln (3.12 × 102) = –14.94 × 103 J mol–1 ΔGº (60.0 oC) = –8.314 × 333.2 ln (2.09 × 102) = –14.79 × 103 J mol–1 2 pts each

From ΔGº=ΔHº-TΔSº –14.94 × 103 = ΔHº – 313.2 × ΔSº –14.79 × 103 = ΔHº – 333.2 × ΔSº 2 pts

ΔSº = –7.5 J K–1 mol–1, ΔHº = –17 kJ mol–1

ΔSº: –7.5 J K–1 mol–1 1pt ΔHº: –17 kJ mol–1 1pt 8 pts in total

69

Final Results and Ranking Practical Theoretical Total Rank Name Country Medal (max 40) (max 60) (max 100) 1 Xianghang Shangguan China 36.960 59.611 96.571 Gold Russian 2 Daniil Khokhlov 39.350 56.567 95.917 Gold Federation 3 Pilkeun Jang Korea 37.077 57.625 94.702 Gold 4 Robert Pollice Austria 36.389 58.200 94.589 Gold Seyed Amirhossein 5 I. R. of Iran 37.404 56.370 93.774 Gold Nasseri 6 Qilei Zhu China 35.725 57.403 93.128 Gold 7 Alif Noikham Thailand 35.503 57.482 92.985 Gold United 8 Ruth Franklin 36.089 56.890 92.979 Gold Kingdom 9 Khetpakorn Chakarawet Thailand 35.234 57.635 92.869 Gold Chinese 10 Yu-Chi Kuo 35.885 56.924 92.809 Gold Taipei 11 Zhiyao Zhou China 32.974 59.708 92.682 Gold 12 Assaf Mauda Israel 35.623 56.936 92.559 Gold 13 Manoel Manuputty Indonesia 36.285 56.222 92.507 Gold 14 Ruyi Wang China 32.668 59.769 92.437 Gold Rafael Angel Rodriguez 15 Costa Rica 36.392 55.894 92.286 Gold Arguedas Pinnaree 16 Thailand 32.200 60.000 92.200 Gold Tea-Mangkornpan 17 Hayate Saitoh Japan 37.359 54.787 92.146 Gold 18 Eszter Najbauer Hungary 34.225 57.499 91.724 Gold 19 Ken-Ichi Endo Japan 32.672 58.825 91.497 Gold 20 Gleb Široki Estonia 34.675 56.694 91.369 Gold 21 Colin Lu United States 36.155 54.756 90.911 Gold 22 Alexander Siegenfeld United States 33.705 56.859 90.564 Gold 23 Máté Somlyay Hungary 35.637 54.881 90.518 Gold 24 Hyeonjae Lee Korea 34.297 56.167 90.464 Gold Czech 25 Ondrej Hak 37.075 52.870 89.945 Gold Republic 26 Fong Jie Ming Nigel Singapore 34.364 55.495 89.859 Gold 27 Lum Jian Yang Singapore 33.936 55.744 89.680 Gold Czech 28 Frantisek Petrous 32.145 57.498 89.643 Gold Republic Nicolas Villagran 29 Argentina 33.040 56.208 89.248 Gold Dos Santos 30 Jaehyun Lim Korea 38.236 50.908 89.144 Gold 31 Vladimiras Oleinikovas Lithuania 35.372 53.531 88.903 Gold Chinese 32 Ming-Ko Cho 30.608 58.148 88.756 Gold Taipei 33 Diptarka Hait India 31.867 56.568 88.435 Silver 34 Deniz Caglin Turkey 34.469 53.941 88.410 Silver Czech 35 Pavel Svec 38.050 50.110 88.160 Silver Republic 36 Constantin Giurgiu Romania 33.496 54.506 88.002 Silver 70

Practical Theoretical Total Rank Name Country Medal (max 40) (max 60) (max 100) 37 Florian Berger Germany 34.692 52.896 87.588 Silver 38 Hiroki Uratani Japan 37.134 50.376 87.510 Silver 39 Binh Nguyen Duc Viet Nam 35.851 51.162 87.013 Silver 40 Mehmet Cem Sahiner Turkey 31.826 55.101 86.927 Silver Levindo Jose Garcia 41 Brazil 35.442 51.406 86.848 Silver Quarto Jiraborrirak 42 Thailand 33.781 52.948 86.729 Silver Charoenpattarapreeda Chinese 43 Wei-Che Tsai 28.048 58.533 86.581 Silver Taipei 44 Attila Sveiczer Hungary 35.159 51.263 86.422 Silver 45 Tng Jia Hao Barry Singapore 29.352 56.506 85.858 Silver 46 Witold Hoffmann Poland 37.719 47.940 85.659 Silver Chinese 47 Bo-Yun Gu 28.458 57.024 85.482 Silver Taipei 48 Manuel Eberl Germany 31.505 53.510 85.015 Silver 49 Connie Zhao Canada 34.218 50.427 84.645 Silver 50 Kornel Ocytko Poland 29.314 55.273 84.587 Silver 51 Luca Zucchini Italy 31.910 52.658 84.568 Silver 52 Richard Li United States 32.825 51.612 84.437 Silver 53 Won Jae Kim Korea 26.245 58.029 84.274 Silver 54 Vranješević Filip Croatia 31.562 52.554 84.116 Silver 55 Marek Buchman Slovakia 36.790 46.699 83.489 Silver 56 Ladislav Hovan Slovakia 26.526 56.881 83.407 Silver 57 Nikunj Saunshi India 31.751 51.551 83.302 Silver 58 Mads Bøttger Hansen Denmark 32.564 50.456 83.020 Silver Mohammadreza 59 I. R. of Iran 28.281 54.594 82.875 Silver Amirmoshiri Czech 60 Ondrej Henych 30.600 52.228 82.828 Silver Republic 61 Fatih Alcicek Turkey 31.316 51.438 82.754 Silver 62 Anton Topchiy Ukraine 28.337 54.377 82.714 Silver 63 Surendra Kotra India 31.216 51.485 82.701 Silver 64 Kengo Kataoka Japan 30.076 52.587 82.663 Silver 65 Brian Bi Canada 25.268 57.325 82.593 Silver 66 Dominik Štefanko Slovakia 29.098 53.463 82.561 Silver 67 Leonard Hasenclever Germany 33.312 49.048 82.360 Silver 68 Khu Boon Hou Derek Singapore 28.460 53.804 82.264 Silver 69 Áron Szigetvári Hungary 27.137 54.896 82.033 Silver Russian 70 Alexander Kochnev 31.034 50.230 81.264 Silver Federation Russian 71 Kirill Sukhoverkov 28.307 52.838 81.145 Silver Federation 72 Rémi Olivier Patin France 28.322 52.806 81.128 Silver 73 Cyril Tang Australia 26.653 54.041 80.694 Silver 74 Richard Liu Canada 27.240 53.180 80.420 Silver

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Practical Theoretical Total Rank Name Country Medal (max 40) (max 60) (max 100) United 75 Joshua Stedman 34.396 45.962 80.358 Silver Kingdom 76 Quang Luu Nguyen Hong Viet Nam 29.736 50.462 80.198 Silver 77 Dzianis Kuliomin Belarus 27.194 52.985 80.179 Silver 78 Dominykas Sedleckas Lithuania 33.044 46.857 79.901 Silver 79 Jarkko Timo Olavi Järvelä Finland 30.029 49.798 79.827 Silver 80 Roberts Bluķis Latvia 33.638 46.183 79.821 Silver 81 Hossein Dadashazar I. R. of Iran 26.330 53.219 79.549 Silver 82 Vidmantas Bieliunas Lithuania 33.240 46.297 79.537 Silver 83 Alimatun Nashira Indonesia 25.887 52.783 78.670 Silver 84 Sergiy Shyshkanov Ukraine 25.238 52.941 78.179 Silver 85 Yeoh Keat Hor Malaysia 35.490 42.607 78.097 Silver United 86 David Edey 31.020 46.987 78.007 Silver Kingdom 87 Baptiste Couet France 30.606 47.003 77.609 Silver 88 Hanieh Safari I. R. of Iran 24.419 53.080 77.499 Silver 89 Kucanda Kristina Croatia 32.102 45.150 77.252 Silver 90 Sebastian Gogg Austria 36.369 40.810 77.179 Silver 91 Stewart Alexander New Zealand 31.984 44.924 76.908 Bronze 92 Stuart Ferrie Australia 32.109 44.686 76.795 Bronze 93 Kelvin Cheung Australia 28.933 47.858 76.791 Bronze 94 Utsarga Sikder United States 22.115 54.446 76.561 Bronze 95 Maciej Gryszel Poland 36.638 39.819 76.457 Bronze 96 Pablo Giomi Spain 35.240 40.960 76.200 Bronze 97 Tudor Balan Romania 23.087 52.809 75.896 Bronze 98 Maksim Mišin Estonia 22.472 53.407 75.879 Bronze 99 Lujia Xu New Zealand 29.246 46.204 75.450 Bronze 100 Emilis Bruzas Lithuania 26.047 49.354 75.401 Bronze 101 David Bellamy New Zealand 21.264 53.717 74.981 Bronze 102 Alexandru Sava Romania 24.635 50.336 74.971 Bronze 103 Abylay Shakhizadayev Kazakhstan 20.559 54.203 74.762 Bronze 104 Alain Vaucher Switzerland 26.840 47.669 74.509 Bronze 105 Ilya Skripin Kazakhstan 28.386 46.080 74.466 Bronze 106 Amarsanaa Davaasuren Mongolia 29.657 44.784 74.441 Bronze 107 Wepa Roziyev Turkmenistan 25.933 48.499 74.432 Bronze 108 Žiga Perko Slovenia 31.742 42.539 74.281 Bronze 109 Marcin Malinowski Poland 31.208 42.831 74.039 Bronze 110 Árni Johnsen Iceland 31.564 41.321 72.885 Bronze 111 Viktors Pozņaks Latvia 28.510 44.203 72.713 Bronze 112 Ioana Moga Romania 28.899 43.098 71.997 Bronze 113 Stephen Yuwono Indonesia 27.265 44.355 71.620 Bronze 114 Lizaveta Durovich Belarus 25.252 46.267 71.519 Bronze 115 Nejc Petek Slovenia 32.996 38.143 71.139 Bronze 116 David Ahlstrand Sweden 30.742 40.349 71.091 Bronze Russian 117 Maxim Kozlov 22.878 48.069 70.947 Bronze Federation 118 Agung Hartoko Indonesia 29.761 41.069 70.830 Bronze 72

Practical Theoretical Total Rank Name Country Medal (max 40) (max 60) (max 100) 119 Dmytro Frolov Ukraine 28.592 42.109 70.701 Bronze 120 Valter Bergant Slovenia 29.861 40.699 70.560 Bronze 121 Johannes Hellwagner Austria 26.373 44.048 70.421 Bronze 122 Zhalgas Serimbetov Kazakhstan 20.069 50.349 70.418 Bronze 123 Anandagopal Srinivasan Ireland 31.027 39.278 70.305 Bronze 124 Ezequiel Maidanik Argentina 22.608 47.518 70.126 Bronze 125 Ivan Jakovlev Estonia 27.136 42.921 70.057 Bronze 126 Mikhail Kavalchuk Belarus 15.822 53.291 69.113 Bronze 127 Tuan Le Anh Viet Nam 26.388 42.625 69.013 Bronze 128 Cuc Mai Thu Viet Nam 24.133 44.508 68.641 Bronze 129 Lukas Wagner Germany 27.902 40.454 68.356 Bronze 130 Alan Carrasco-Carballo Mexico 33.339 34.160 67.499 Bronze 131 Michael Michelachvili Israel 23.295 44.130 67.425 Bronze 132 Yannick Suter Switzerland 27.566 39.806 67.372 Bronze 133 Konstantin Krautgasser Austria 30.577 36.608 67.185 Bronze 134 Markovic Igor Croatia 34.209 32.634 66.843 Bronze 135 Christos Anastassiades Cyprus 19.253 47.490 66.743 Bronze 136 Makbule Esen Turkey 26.701 39.938 66.639 Bronze 137 Alexander Blokhuis Netherlands 23.991 42.522 66.513 Bronze 138 Andre Silva Franco Brazil 26.683 39.791 66.474 Bronze 139 Jessica Kazumi Okuma Brazil 23.243 43.098 66.341 Bronze 140 Mario Rugiero Argentina 29.476 36.583 66.059 Bronze 141 Agil Azimzada Azerbaijan 23.945 41.649 65.594 Bronze 142 Vasil Vasilev Bulgaria 21.030 44.425 65.455 Bronze 143 Kadi Liis Saar Estonia 22.166 43.169 65.335 Bronze United 144 David Wade 21.705 43.146 64.851 Bronze Kingdom 145 Eviatar Degani Israel 18.723 46.103 64.826 Bronze 146 Daniel Quill Ireland 25.620 38.960 64.580 Bronze 147 Ingrid Eidsvaag Andersen Norway 21.411 43.151 64.562 Bronze 148 Anatolij Babič Netherlands 27.621 36.604 64.225 Bronze 149 Antton Curutchet France 24.863 38.851 63.714 Bronze 150 Cédric Martin France 27.489 36.174 63.663 Bronze 151 Istvan Kleijn Netherlands 28.170 35.416 63.586 Bronze 152 Rahym Ashirov Turkmenistan 23.978 39.043 63.021 Bronze 153 Andreu Tortajada Navarro Spain 28.172 34.775 62.947 Bronze 154 Buiucli Serafim Moldova 23.548 38.468 62.016 Bronze 155 Allan Chau Australia 24.806 37.204 62.010 Bronze 156 Ivan Bojidarov Dimov Bulgaria 17.944 43.952 61.896 Bronze 157 Miras Bekbergenov Kazakhstan 13.523 48.162 61.685 Bronze Jesús Alvaro Gómez 158 Spain 26.625 35.017 61.642 Bronze Iregui Niels Christian Holm 159 Denmark 32.001 29.387 61.388 Bronze Sanden 160 Natallia Yelavik Belarus 14.564 46.262 60.826 Bronze 161 Amit Panghal India 18.673 41.878 60.551 Bronze

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Practical Theoretical Total Rank Name Country Medal (max 40) (max 60) (max 100) 162 Edvard Sargsyan Armenia 19.759 40.778 60.537 Bronze 163 Rashad Yusifov Azerbaijan 19.282 40.972 60.254 Bronze Matias Lanus Mendez 164 Argentina 28.846 31.143 59.989 Bronze Elizalde 165 Vladyslav Panarin Ukraine 20.531 39.427 59.958 Bronze 166 Jari Tapio Huisman Finland 27.185 32.628 59.813 Bronze 167 Suvi Kaarina Klapuri Finland 21.119 38.478 59.597 Bronze 168 Kristian Holten Møller Denmark 28.252 31.131 59.383 Bronze Raymundo 169 Mexico 27.822 30.510 58.332 Bronze Esquer-Rodriguez 170 Manuel Van Rijn Netherlands 30.004 28.276 58.280 Bronze 171 Jaimin Choi New Zealand 16.652 41.287 57.939 Bronze Fani Georgieva 172 Bulgaria 24.246 33.141 57.387 Bronze Madzharova 173 Alberto Branchi Italy 19.601 37.763 57.364 Bronze 174 Luciano Barluzzi Italy 19.940 37.328 57.268 Bronze 175 Oscar Salomon Kivinen Finland 23.536 33.401 56.937 Bronze Raul Bruno Machado 176 Brazil 15.058 41.575 56.633 Bronze Da Silva 177 Saidali Kholzoda Tajikistan 27.467 28.231 55.698 Hon. Men. 178 Ulugbek Barotov Tajikistan 19.231 36.129 55.360 Hon. Men. 179 Philip Sohn Canada 21.525 33.774 55.299 Hon. Men. 180 Oscar Garcia Montero Costa Rica 26.869 28.382 55.251 Hon. Men. Jorge Pedro Martins 181 Portugal 25.641 29.283 54.924 Hon. Men. Nogueiro 182 Marek Vician Slovakia 26.645 27.989 54.634 Hon. Men. 183 Panayiota Katsamba Cyprus 19.094 35.488 54.582 Hon. Men. 184 Božidar Aničić Slovenia 17.734 35.736 53.470 Hon. Men. 185 Tania Lizeth Lopez-Silva Mexico 28.779 24.433 53.212 Hon. Men. Gonçalo Vitorino 186 Portugal 23.280 28.616 51.896 Bonifácio Oscar Hans Emil 187 Sweden 24.427 27.460 51.887 Mickelin 188 Jakob Bank Kodal Denmark 21.848 29.859 51.707 189 Negrescu Dan Moldova 23.042 28.656 51.698 190 Nicholas Thong Li Jie Malaysia 27.963 23.543 51.506 191 Espen Auseth Nielsen Norway 14.857 36.647 51.504 192 Muhammad Anus Pakistan 15.738 35.550 51.288 193 Enkhbat Myagmar Mongolia 14.034 36.873 50.907 194 Tsvetan Hristov Tarnev Bulgaria 27.009 23.634 50.643 195 Lars Moen Strømsnes Norway 22.364 28.159 50.523 196 Gantulga Batbayar Mongolia 14.559 35.491 50.050 197 Dmitrijs Jevdokimovs Latvia 22.926 26.460 49.386 198 Michelle Frei Switzerland 25.562 23.113 48.675 199 Jeroen Van Cleemput Belgium 19.678 28.280 47.958 200 Viktor Mattias Johansson Sweden 22.186 25.238 47.424 201 Myrat Annamuhammedov Turkmenistan 16.227 30.875 47.102 74

Practical Theoretical Total Rank Name Country Medal (max 40) (max 60) (max 100) 202 Maartje Iris Romijn Norway 26.915 19.929 46.844 203 Dermot Gillen Ireland 13.958 32.849 46.807 María Victoria Moreno 204 Venezuela 28.372 18.349 46.721 Hernández 205 Selenge Enkhtuya Mongolia 15.819 30.674 46.493 206 Anael Ben Asher Israel 15.432 30.969 46.401 207 Alisher Rakhimov Tajikistan 12.790 33.581 46.371 208 Giuseppe Recchia Italy 22.544 23.801 46.345 Oscar 209 Mexico 15.265 30.225 45.490 Palomino-Hernandez 210 Izhar Ali Pakistan 23.060 22.422 45.482 211 Artur Aslanyan Armenia 12.814 32.651 45.465 Marconi Nicolás Peñas 212 Spain 18.577 26.624 45.201 De Frutos Rabi 'Atul Adibah 213 Malaysia 20.074 25.122 45.196 'Allauddin 214 Jonathan Wilson Ireland 21.229 23.144 44.373 215 Wainer Camacho Araya Costa Rica 25.459 18.244 43.703 Ramón Lorenzo Panades 216 Cuba 5.726 37.909 43.635 Barrueto 217 Sigtryggur Kjartansson Iceland 21.445 21.955 43.400 218 Vahagn Tamazyan Armenia 9.655 32.873 42.528 219 Stelios Chatzimichail Cyprus 10.225 32.241 42.466 220 Azizbek Usvaliev Kyrgyzstan 11.956 30.472 42.428 Siti Fatma Hawaria 221 Malaysia 22.344 19.877 42.221 Mokhtar 222 Helgi Björnsson Iceland 22.934 19.211 42.145 223 Nikolaos Kaplaneris Greece 19.421 22.550 41.971 224 Shakhboz Zulfaliev Tajikistan 11.031 30.846 41.877 225 Petricevic Fran Croatia 16.988 24.709 41.697 Tachmajal Corrales 226 Costa Rica 21.569 18.601 40.170 Sanchez 227 Jānis Briška Latvia 16.481 23.162 39.643 228 Michele Oliosi Switzerland 10.369 29.077 39.446 229 Konráð Þór Þorsteinsson Iceland 16.584 20.002 36.586 230 Stefanos Tyros Greece 15.363 21.007 36.370 231 Vugar Mirzakhanov Azerbaijan 12.722 23.637 36.359 232 Dosca Anastasia Moldova 11.098 24.782 35.880 Luis Fernando Merma 233 Peru 17.364 18.033 35.397 Paucar 234 Emil Marklund Sweden 14.726 20.619 35.345 235 Kevin Renier Belgium 20.666 14.030 34.696 236 Hafiz Hassan Ali Pakistan 15.819 18.755 34.574 Marta Cristina Neves 237 Portugal 10.597 23.867 34.464 Aguiar Sebastian Andres 238 Uruguay 17.120 17.080 34.200 Martinez

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Practical Theoretical Total Rank Name Country Medal (max 40) (max 60) (max 100) 239 Minahil Sana Qasim Pakistan 13.884 20.228 34.112 Arnaldo Enmanuel Marin 240 Venezuela 15.059 18.476 33.535 Suárez 241 Michael Matalliotakis Greece 8.598 24.391 32.989 242 Alexandre Faia Carvalho Portugal 19.630 12.816 32.446 243 Andreas Sofokli Cyprus 10.084 21.105 31.189 244 Norberto Andres Canepa Uruguay 13.869 16.185 30.054 Carlos Javier Berrio 245 Venezuela 14.633 14.518 29.151 Barrera Erwin Wilfredo Mora 246 Venezuela 13.198 15.801 28.999 Flores 247 Georgios Papadimitriou Greece 11.878 17.111 28.989 248 Mohammad Shubat Syria 19.962 8.382 28.344 249 Jasmine De Becker Belgium 13.838 14.221 28.059 250 Agil Safaralizade Azerbaijan 5.720 22.150 27.870 251 Melissa Bariani Uruguay 12.638 14.959 27.597 252 Florence Thiry Belgium 14.404 13.146 27.550 253 Pîrău Tudor Moldova 8.024 19.433 27.457 254 Saltanat Mambetova Kyrgyzstan 11.268 14.719 25.987 255 Sagynbek Dadybaev Kyrgyzstan 6.764 18.642 25.406 256 Hessah Alquraishi Kuwait 15.570 9.612 25.182 257 Alejandro Rodriguez Uruguay 8.658 15.200 23.858 Anthony John Salcedo 258 Peru 7.419 14.847 22.266 Meza Mohammad 259 Kuwait 12.529 9.033 21.562 Alabdulrazzaq 260 Begmyrat Cholukov Turkmenistan 4.591 14.162 18.753 261 Davit Arzumanyan Armenia 4.193 12.372 16.565 262 Kalysbek Abykeshov Kyrgyzstan 1.950 12.798 14.748 263 Shahad Albaloul Kuwait 8.368 6.330 14.698 264 Mariam Aldarweesh Kuwait 5.114 6.304 11.418 265 Rouaa Al Nan Syria 4.947 1.712 6.659 266 Ali Issa Syria 0.000 5.850 5.850 267 Ali Mourtada Syria 3.520 1.221 4.741

76 Statistical Analysis of the Problems

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Minutes of the International Jury Monday 19th – Tuesday 28th July 2010 (Recorded by Duckhwan Lee)

1. 1st International Jury Meeting(20:00-01:30 20th July at the Auditorium of OVTA)

- The Business section was chaired by Duckhwan Lee.

1) A brief summary of the Cambridge IChO was presented. 2) Liechtenstein, Serbia and Nigeria were introduced. 3) The members of the SC were introduced: - Elected members: Vadim Eremin(Russia), Wolfang Hampe(Germany), Gabor Magyarfalvi(Hungary, not present for personal reason), John Kiappes(USA), Mark Ellison(Australia), Duckhwan Lee(Korea) - Organizers: Peter Wothers (UK, 2009), Tadashi Watanabe [Ito Masato] (Japan, 2010), Jale Hacaloglu(Turkey, 2011), G. Bryan Balazs(USA, 2012) - Coopted members: Carlos Castro-Acuna(Mexico), Manfred Kerschbaumer(Austria), Anton Sirota (Slovakia) * The underlined members are up for re-election at the closing of the 42st IChO 4) The schedule for the SC meetings was announced. 5) The discussions on the practical tasks were chaired by Professor Sugahara.

2. The SC Meeting (13:00-14:30 Tuesday 21st July at Rm 3019 of OVTA)

- Future hosts 9 Finalized: Turkey(2011), USA(2012), Vietnam(2014) 9 To be finalized at the December meeting: Russia(2013)

- Observing countries: 9 Liechtenstein: will participate with students in 2011 9 Nigeria: will have to observe IChO-2011 [§ 2(3)… Incoming countries must send observers to two consecutive Olympiads before its pupils can participate in IChO (see also § 3, section 5).]

- Request of Uzbekistan for appointing Vadim as their observer 9 Voted not to accept the request since it would be a direct violation of the Regulation. 9 A letter will be sent to the Government of Uzbekistan.

- Election Procedure 9 The position of Gabor will be replaced by a new member with two-year term. 9 The election procedure for Europe(3 positions) and Americas(1 position) will be announced at the beginning of the 2nd International Jury Meeting. 9 A form for the listing of candidates will be posted in front of the dining room until 20:00 on Friday. 9 Each candidate will have a minute to announce his/her candidacy at the 3rd International Jury.

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9 Each head mentor will write on the prepared ballot the names of that country’s selected candidates, but no more than the number of open positions.

- Miscellaneous 9 A printed version of the proposals for revision of the Regulation will be distributed before the 3rd International Jury Meeting. 9 The co-opted member should not be selected solely on the basis of his/her native languages. 9 We may need some sort of guidelines in order to resolve issues with registration rates arising from the constantly changing exchange rates.

3. 2nd International Jury Meeting (20:00-00:30 Sunday 22nd July at the Auditorium of OVTA)

- The election procedures were announced. - The revision procedures were announced and the printed copy of the proposals for revision were distributed to the head mentors.

4. 3rd International Jury Meeting (20:00-21:30 Sunday 25th July at the Auditorium of OVTA)

The business session was chaired by Duckhwan Lee.

1) Announcement of the arbitration schedule.

2) Future hosts:

¾ The recommendation for Vietnam as the host of IChO-2014 was approved unanimously. ¾ O. Yavuz Ataman and Bryan Balazs introduced the plans for IChO-2011 and 2012. ¾ Vadim explained the Russian plan for presenting the official document for the December SC. ¾ Spain (Juan Antonio) is working for the IChO-2015.

3) Election of SC members

¾ Sasha Gladilin(Russia), Peter Wothers(UK), Wolfgang Hampe(Germany), and John Kiappes(USA) were elected for Europe and Americas through secret vote.

4) Revision of the IChO regulations

¾ The proposal prepared by the December SC meeting was distributed through the Prep. Problems as well as the hand-outs at the beginning of the Tokyo Olympiad. ¾ The Proposal A and C were approved without discussion by qualified majority of 59 votes out of 68. ¾ The Proposal B was approved as presented by qualified majority of 59 votes out of 68.

5) The elected members and the hosts (Japan, Turkey, USA) re-elected Duckhwan Lee(Korea) as the Chair. The Co-opted member will be decided before the 4th Jury with the recommendation of the Turkey host.

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5. 4th International Jury Meeting (20:00-21:00 Monday 26th July at the Auditorium of OVTA)

The business session was chaired by Duckhwan Lee.

1) Steering Committee (August 2010 – July 2011). - elected members: Wolfang Hampe(Germany, 2008, [email protected]) Peter Wothers (UK, 2010, [email protected]) Sasha Gladilin(Russia, 2010, [email protected]) John Kiappes(USA, 2008, [email protected]) Mark Ellison(Australia, 2007, [email protected]) Duckhwan Lee(Korea, 2007, [email protected], Chair) - Organizers: Tadashi Watanabe (Japan, 2010, [email protected]) Jale Hacaloglu(Turkey, 2011, [email protected]) G. Bryan Balazs (USA, 2012, [email protected]) Representative of IChO-2014(Vietnam) - Coopted members: Manfred Kerschbaumer(Austria, [email protected]) Carlos Castro-Acuna(Mexico, [email protected]) Olivier Plaidy(France, [email protected])

2) IUPAC Travel Fund

Country Participation Fee Travel Expenses Total 2010 Venezuela $ 1800 $ 1800 Croatia $ 2000 $ 2000 Tajikistan $ 700 $ 2400 $ 3100 Argentina $ 2853 $ 2853 2009 Uruguay $ 1100 $ 1800 $ 2900 Peru $ 600 $ 600 Cuba $ 1700 $ 1300 $ 3000 2008 Cuba $ 1600 $ 1200 $ 2800 Kyrgystan $ 900 $ 900 $ 1740 Peru $ 500 $ 500 Tajikistan $ 1150 $ 1150 Uruguay $ 1000 $ 1000 $ 2900 Venezuela $ 900 $ 900

9 It was explained that the support for travel expenses should not be more than the actual fares for travel for which clear receipts such as air fare tickets should be submitted to the Organizer.

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9 The support should be used for paying the participation fee and/or the actual travel expenses for one extra student or mentor, never for observer or guest. 9 The request for support must be submitted to the Ankara Organizer no later than the end of November. 9 The contact information for the IUPAC will be delivered to Jale from Ito.

3) Miscellaneous 9 A list of participants with e-mail addresses would be helpful. (Sasha) 9 We need a clear guideline for the number of significant figures in theoretical tasks. (Wolfgang) 9 There was an appeal by the Nigerian observer that they had experienced difficulties in observing last two year even though they have had National Olympiad in Nigeria, and that they really want to participate with their students. (Sunday Adedeji, the observer of Nigeria)

4) Report of Arbitration and Medal Allocation 9 Postponed to Jul 27 due to the mix-ups in the marking of the final results. 9 The Science Committee was informed that they have to stick to the markings that the HM signed. 9 Plan for July 27 7:00 Breakfast 7:45 Distribution of the Markings 8:00 5th Jury Meeting for the Report and Medal Allocation

6. 5th International Jury Meeting (8:00-9:00 Tuesday 27th July at the Auditorium of OVTA)

1) Report on Arbitration (Professor Onaka) 9 The double penalty cases have been taken care of after the arbitration for 9.4% of the students.

2) Medal Allocation (Professor Sugahara) 9 The total number of students was 267. 9 32 (11.6%) for Gold, 58(21.0%) for Silver, 86(31.2%) for Bronze, 9 for Honorable Mention

3) On request by Peter, a letter, signed by all members of SC, explaining the need for the second year of observation by the Regulation, was delivered to the Nigeria Observer before they can send students to participate in the Olympiad..

88 Regulations of the International Chemistry Olympiad (IChO)

General Statement

§ 1 Aims of the competition The International Chemistry Olympiad (IChO) is a chemistry competition for students at secondary school level with the aim of promoting international contacts in chemistry. It is intended to stimulate the activities of students interested in chemistry by way of the independent and creative solution of chemical problems. The IChO competitions help to facilitate cordial relations between young adults of different nationalities; they encourage cooperation and international understanding.

Organization of the IChO

§ 2 Organization and invitation (1) The IChO is organized every year, as a rule at the beginning of July, in one of the participating countries by the Education Ministry or an appropriate institution of the organizing country (hereafter referred to as the organizer). (2) Unless directed otherwise by the International Jury, the organizer is obliged to invite all countries that participated in the preceding IChO competition. The official invitation to participate in the forthcoming IChO should be sent to countries by the November preceding the competition. The countries invited must confirm their participation in the IChO according to requirements of the organizer. (3) Countries that wish to take part in the IChO must apply to the organizer by the end of November preceding the Olympiad. The organizer has the right to invite the countries only with the agreement of the organizers of the two subsequent IChO competitions. Invited countries must send an observer to two consecutive Olympiads before its pupils can participate in the IChO.

§ 3 Delegations (1) Each participating country's delegation consists of competitors and accompanying persons (also known as mentors). It is expected that there are four competitors and two mentors in the delegation. Furthermore, the countries may include two scientific observers as part of their delegation. (2) The competitors must not be university students. They can only be students of secondary schools that are not specialized in chemistry and, if they have already graduated before the 1st of May of the year of the competition, the organizer must be informed as to the month and year of their graduation. Moreover, they must be under the 20 years of age on the 1st of July of the year of the competition. The competitors must be passport holders of the country they represent or have taken part in the secondary school educational system of this country for more than one academic year. All members of a delegation must provide themselves with medical insurance for the journey to and from the organizing country and for the period of their stay in the organizing country. (3) The mentors act as members of the International Jury (see § 6). One of the mentors is designated as the head of delegation (head mentor). 89 (4) The mentors: a) must guarantee the fulfillment of those conditions specified in section 2 of this paragraph, b) must be capable of translating the text of the competition tasks from English into the language used by their students and be able to judge the set of tasks and correct the work of the students. c) have the right to enter a protest which should be addressed to the Chair of the International Jury or the Steering Committee and, when necessary, ask for a resolution of the problem at the next meeting of the International Jury.

§ 4 Obligations of the Organizer (1) The organizer provides: a) the itinerary of the IChO, b) transportation from/to an airport/station (which is designated by the host country) on the day of arrival and departure, c) that the organization of the competition will adhere to the regulations, d) accident insurance for all participants in connection with the itinerary, e) the opportunity for the mentors to inspect the working room and practical apparatus to be used for the practical tasks before the competition takes place, f) all necessary arrangements for the observance of safety regulations, g) the medals, certificates and prizes, which are presented at the official closing ceremony, h) a report on the competition to be distributed not later than six months after the competition. (2) A meeting of the Steering Committee must be hosted in the organizing country in the December prior to the IChO. The organizing country will provide some travel assistance.

§ 5 Financing (1) The participating country covers the return travel costs of the students and the accompanying persons to the designated airport/station or to the location where the competition is held. (2) Participating countries must pay a participation fee, the amount of which must be approved by the International Jury. (3) All other costs incurred in connection with the organized program, including the costs of accommodation for all competitors and members of the International Jury, are covered by the organizer. (4) The organizers of the next two consecutive Olympiads may send two observers to the current IChO with their expenses covered by the host as mentioned in § 5, section 3.

Institutions of the IChO

§ 6 International Jury (1) The International Jury consists of its chair and members. The chair of the International Jury is nominated by the organizer. The members of the International Jury are the two mentors from the individual delegations and the chair of the Steering Committee (see § 8).

90 (2) The chair of the International Jury or his/her delegate calls and chairs the meetings of the International Jury concerning the current competition, while the business sessions concerning general problems of the IChO are chaired by the SC chair. (3) Resolutions of common International Jury sessions or its split sessions are passed by the International Jury when they are agreed by a simple majority of votes in the presence of at least 75% of the delegations. Each participating country has one vote. Changes in the regulations can only be made at the common sessions of the International Jury and require a qualified majority of two thirds of the votes. The chair has a casting vote in the event of a tie. The decisions of the International Jury are binding for both organizer and participants. (4) The working language of the International Jury is English.

§ 7 Responsibilities of the International Jury (1) The International Jury: a) is in charge of the actual competition and its supervision according to the regulations, b) discusses in advance the competition tasks presented by the organizer, their solutions and the marking guidelines, gives comments and takes decisions in case of changes, c) supervises the marking of the examination papers and guarantees that all participants are judged by equal criteria, d) determines the winners and decides on prizes for the competitors, e) monitors the competition and suggests changes to the regulations, organization and contents for future IChOs, f) makes decisions on the exclusion of a participant or an entire team from the competition (see also § 11, section 7), g) elects members of the Steering Committee of the IChO, h) may form working groups to solve specific chemistry related problems of the IChO. (2) The members of the International Jury: a) are obliged to maintain a professional discretion about any relevant information they receive during the IChO and must not assist any participants, b) keep the marking and results secret until announced by the International Jury.

§ 8 Steering Committee (1) The long term work involved in organizing the International Chemistry Olympiads is coordinated by the Steering Committee. (2) Members of the Committee are elected by the International Jury by a secret ballot to serve a two year term. There must be at least one person from each of the following regions: the Americas, Asia and Europe. Other three members can come from any region. The term of the elected committee begins on the 1st day after the IChO. Members are elected for no more than two consecutive terms. (3) There are the following ex-officio members of the Steering Committee: a) a representative of the current IChO, b) a representative of the immediately preceding IChO, c) representatives of the subsequent two IChOs, d) the immediate past chair of the SC (for one year only) (4) The incoming Steering Committee elects its own Chair from among its elected members at a meeting held before the committee’s term begins. 91 The Chair: a) calls and chairs the meetings of the Steering Committee, b) calls and chairs the business meetings of the International Jury dealing with general problems of future International Chemistry Olympiads, c) may invite non-voting guests to the meetings of the Steering Committee after consultation with the host of the meeting, d) has the right to call extraordinary meetings of the International Jury when necessary. (5) The Steering Committee: a) provides organizational oversight for the International Chemistry Olympiad, b) proposes items for consideration at the International Jury sessions. c) may co-opt 1–3 non-voting members for their particular expertise for periods of one year. d) may invite representatives of confirmed future IChOs. (6) The Steering Committee is not empowered to make any decisions affecting the International Chemistry Olympiad that would interfere with the duties and responsibilities of the International Jury (see § 6 and 7).

§ 9 International Information Center There is an International Information Center of the International Chemistry Olympiads gathering and providing (when necessary) all the documentation of the IChOs from the beginning of the Olympiad to the present. The seat of the Office is in Bratislava, Slovakia.

Competition

§ 10 Preparation for the IChO competition (1) The organizer distributes a set of preparatory tasks written in English to all participating countries in January of the competition year. The preparatory tasks are intended to give students a good idea of the type and difficulty of the competition tasks, including safety aspects (see §12 and Appendix “B”). SI units should be used throughout the preparatory tasks. (2) The total number of theoretical and experimental tasks in the set of preparatory problems cannot be lower than 25 and 5, respectively. (3) Appendix C of the regulations contains a list of concepts and skills expected to be mastered by the participants. Organizers may freely include questions and tasks in the theoretical or experimental competition based on the knowledge listed there. The organizer can include problems in the exams based on the use of concepts and skills from not more than 6 theoretical and 2 practical fields outside this list, if a minimum of 2 tasks from each field is included and the necessary skills demonstrated in the set of preparatory problems. Examples of such external fields are listed in Appendix C. Fields not already listed should have a breadth similar to the examples. These 6 theoretical and 2 practical fields must be stated explicitly at the beginning of the Preparatory problems. If an equation not covered by the listed fields is required for the solution of the exam questions, then this should be defined in the exam text. (4) Appendix D contains an outline of the factual knowledge supposedly familiar to the competitors. If specific facts, not included in Appendix D, are required for the solution of the exam questions, then these should be included in the exam text or in the preparatory problems and their solutions. 92 (5) Training or any other special instruction, that is carried out for a selected group of 50 or fewer students, containing the IChO team, must be no longer than two weeks.

§ 11 Organization of the IChO Competition (1) The competition consists of two parts: a) part one, the practical (experimental) competition, b) part two, the theoretical competition. (2) A working time of four to five hours is allotted for each part. There is at least one day of rest between the two parts. (3) Competitors receive all relevant information in the language of their choice. (4) There must be no contact between mentors and competitors once the mentors have received the competition tasks for consideration. Information regarding the competition tasks must not be passed to the competitors directly or indirectly prior or during the competition. (5) When pocket calculators are not provided by the organizer, only non-programmable pocket calculators may be used in the competition. (6) The safety regulations announced by the organizer are binding for all participants. (7) Breaking of any of the rules given in the preceding paragraphs (§ 3. section 2, § 10 section 5, § 11 sections 4, 5, and 6) has as its consequence exclusion from the whole or a part of the competition.

§ 12 Safety (1) During the experimental part, the competitors must wear laboratory coats and eye protection. The competitors are expected to bring their own laboratory coats. Other means of protection for laboratory work are provided by the organizer. (2) When handling liquids, each student must be provided with a pipette ball or filler. Pipetting by mouth is strictly forbidden. (3) The use of very toxic substances (designation T+) is strictly forbidden. The use of toxic substances (designation T) is not recommended, but may be allowed if special precautions are taken. Substances belonging to the categories R 45, R 46, R 47 must not be used under any circumstances (see Appendix B for definitions of these categories). (4) Detailed recommendations involving students´ safety and the handling and disposal of chemicals can be found in Appendices A 1, A 2, and B. These appendices are based on the directives of the European Communities and are updated automatically with these directives. a) Appendix A 1: Safety Rules for Students in the laboratory. b) Appendix A 2: Safety Rules and Recommendations for the Host Country of the IChO. c) Appendix B contains: B 1: Hazard Warning Symbols and Hazard Designations; B 2: R-Ratings and S-Provisions: Nature of special risks (R) and safety advice (S); B 3: Explanation of Danger Symbols (for use of chemicals in schools);

93 § 13 Competition Tasks (1) The organizer is responsible for the preparation of competition tasks by competent experts/authors, who constitute the Scientific Board of the IChO. They propose the methods of solution and the marking scheme. (2) The tasks, their solutions and the marking schemes are submitted to the International Jury for consideration and approval. The authors of the tasks should be present during the discussion. (3) The Chair of the International Jury may put the Chair of the Scientific Board in charge of the proceedings when the tasks are considered. (4) The total length of the theoretical or experimental tasks, including answer sheets, should be kept to a minimum and not exceed 25,000 characters. The number of characters must be stated at the end of each exam paper. SI units should be used throughout the competition tasks. (5) In the experimental part of the competition the following conditions must be fulfilled: a) The experimental part must contain at least two independent tasks. b) The marking cannot require subjective interpretation by the staff. c) Competitors must receive the same substances when solving the tasks from qualitative analytical chemistry. d) When solving tasks from quantitative analytical chemistry competitors must receive the same substances but with different concentrations. e) In evaluating the quantitative tasks the master values must not be based on an average of the results of the competitors. f) The great majority of the grade in quantitative tasks must be given to the mean value as reported by the competitors while some marks may also be given to the corresponding equations, calculations, or explanations directly related to the work. Points must not be awarded for reproducibility.

§ 14 Correcting and Marking (1) A maximum of 60 points is allocated to the theoretical tasks and 40 points to the practical tasks, making a total of 100 points. (2) The competition tasks are corrected independently by the authors and by the mentors. Consequential marking should be used so that students are not punished twice for the same error. Both corrections are then compared; however, the authors present their evaluation first. After a discussion the final score for each participant is reached and agreed by both sides. The organizer retains the original marked manuscripts. (3) The International Jury discusses the results and decides on the final scores. (4) In order to eliminate any doubts about possible mistakes in the processing of the results the organizer must provide the mentors with a list of their students’ total results before the closing award ceremony.

§ 15 Results and Prizes (1) Official results of the competition and the number of medals awarded are decided by the International Jury. (2) The number of gold medals awarded is in the range of 8% to 12%, silver 18% to 22%, and bronze medals 28% to 32% of the total number of competitors. The exact number of medals is decided on the basis of an blind review of the results. 94 (3) Each medalist must receive the medal and a corresponding certificate from the organizer. (4) In addition to the medals other prizes may be awarded. (5) An honorable mention is awarded to competitors who are among the best 10% of non medalists. (6) Each competitor receives a certificate of participation. (7) In the awarding ceremony, the non-medalists are called alphabetically. (8) Team classification is not made. (9) The organizer must provide a complete list of results as a part of the final report.

§ 16 Final Regulations (1) Those who take part in the competition acknowledge these regulations through their participation. (2) This version of regulations has been approved by the International Jury in Tokyo (Japan) in July 2010, and is issued to replace the former regulations approved in Budapest (Hungary) in July 2008. (3) The regulations are valid from the 1st of September, 2010. Changes to the regulations can be made only by the International Jury and require a qualified majority (two third of the votes with regard to total number of participating countries).

95 APPENDIX A

A 1: SAFETY RULES FOR STUDENTS IN THE LABORATORY All students of chemistry must recognize that hazardous materials cannot be completely avoided. Chemists must learn to handle all materials in an appropriate fashion. While it is not expected that all students participating in the International Chemistry Olympiad know the hazards of every chemical, the organizers of the competition will assume that all participating students know the basic safety procedures. For example, the organizers will assume that students know that eating, drinking or smoking in the laboratory or tasting a chemical is strictly forbidden. In addition to the common-sense safety considerations to which students should have been previously exposed, some specific rules, listed below, must also be followed during the Olympiad. If any question arises concerning safety procedures during the practical exam, the student should not hesitate to ask the nearest supervisor for direction.

Rules regarding personal protection 1. Eye protection must be worn in the laboratories at all times. If the student wears contact lenses, full protection goggles must also be worn. Eye protection will be provided by the host country. 2. A laboratory coat is required. Each student will supply this item for himself/herself. 3. Long pants and closed-toed shoes are recommended for individual safety. Long hair and loose clothing should be confined. 4. Pipetting by mouth is strictly forbidden. Each student must be provided with a pipette bulb or pipette filler.

Rules for Handling Materials 1. Specific instructions for handling hazardous materials will be included by the host country in the procedures of the practical exam. All potentially dangerous materials will be labeled using the international symbols below. Each student is responsible for recognizing these symbols and knowing their meaning (see Appendix B 1, B 2 and B 3). 2. Do not indiscriminately dispose chemicals in the sink. Follow all disposal rules provided by the host country.

A 2: SAFETY RULES AND RECOMMENDATIONS FOR THE HOST COUNTRY OF THE INTERNATIONAL CHEMISTRY OLYMPIAD Certainly it can be assumed that all students participating in the IChO have at least modest experience with safety laboratory procedures. However, it is the responsibility of the International Jury and the organizing country to be sure that the welfare of the students is carefully considered. Reference to the Safety Rules for Students in the Laboratory will show that the students carry some of the burden for their own safety. Other safety matters will vary from year to year, depending on practical tasks. The organizers of these tasks for the host country are therefore assigned responsibility in the areas listed below. The organizers are advised to carefully test the practical tasks in advance to ensure the safety of the experiments. This can best be accomplished by having students of ability similar to that of IChO participants carry out the testing.

96 Rules for the Host Country (see also A 1): 1. Emergency first-aid treatment should be available during the practical examination. 2. Students must be informed about the proper methods of handling hazardous materials. a) Specific techniques for handling each hazardous substance should be included in the written instructions of the practical examination. b) All bottles (containers) containing hazardous substances must be appropriately labeled using internationally recognized symbols (see Appendix B 1). 3. Chemical disposal instructions should be provided to the students within the written instructions of the practical examination. Waste collection containers should be used for the chemicals considered hazardous to the environment. 4. The practical tasks should be designed for appropriate (in other words, minimum) quantities of materials. 5. The laboratory facilities should be chosen with the following in mind: a) Each student should not only have adequate space in which to work, but should be in safe distance from other students. b) There should be adequate ventilation in the rooms and a sufficient number of hoods when needed. c) There should be more than one emergency exit for each room. d) Fire extinguishers should be near by. e) Electrical equipment should be situated in an appropriate spot and be of a safe nature. f) There should be appropriate equipment available for clean-up of spills. 6. It is recommended that one supervisor be available for every four students in the laboratory to adequately ensure safe conditions. 7. The organizers should follow international guidelines for the use of toxic, hazardous or carcinogenic substances in the IChO.

97 APPENDIX B

B 1: HAZARD WARNING SYMBOLS AND HAZARD DESIGNATIONS AND THEIR EXPLANATION (Applied for Chemicals in Schools)

1. Explosive substances (E) These are substances which can be caused to explode by exposure to a flame or which are more sensitive to impact of friction than 1,3-dinitrobenzene (e.g. picrates, organic peroxides). In particular they include substances with R ratings R1 - R3 (see B 2), designation E. When using and storing these substances, the S provisions (S15 - S17) must be observed (see B 2).

2. Fire inducing substances, Oxidizing (O) These are substances which can have a strong exothermic reaction on coming into contact with other, particularly flammable substances or organic peroxides. They include in particular substances R 7 to R 9, designation O.

3. Highly flammable, easily flammable and flammable substances (F+, F) In liquid form, highly flammable substances have an ignition point below 0 °C and a boiling point of 35 °C maximum. They are to be designated by the danger symbol F+ and the rating R 12. Substances are easily flammable if they: a) can heat up and ignite at normal air temperature without energy supply, b) are easily ignited in solid state by short exposure to a source of flammation and continue to burn or glow after removal of the latter, c) ignite below 21 °C in liquid state, d) ignite in gaseous state if mixed with air at 101.3 kPa and 20 °C, e) develop easily flammable gases in dangerous quantities when in contact with water or damp air, f) ignite if brought into contact with air when in dustlike state. These substances are to be designated with the danger symbol F and the rating R 11. Flammable substances have in liquid form an ignition point of 21 °C to 55 °C and are to designated with the rating R 10, no danger symbol. When dealing with highly flammable, easily flammable and flammable liquids may only be heated using sealed electrical heating equipment which is not in itself a source of flammation. All substances must be heated in such a way that the dangerous vapours liberated by heating cannot escape into the atmosphere. This does not apply to fire hazardous substances in small quantities for fire demonstrations. The regulations laid down by the state fire authorities must be observed.

4. Toxic substances (T +, T, Xn ) Legislation applying to chemicals distinguishes three categories of toxicants: highly toxic substances (R 26 R 28), danger symbol T+, toxic substances (R 23 R 25), danger symbol T, less toxic substances (R 20 R 22), danger symbol Xn.

98 Highly toxic substances are those which can cause grave acute or chronic health damage or death almost immediately if inhaled, swallowed or absorbed through the skin in small amounts. Toxic substances are those which can cause considerable acute or chronic health damage or death if inhaled, swallowed or absorbed through the skin in small amounts. Less toxic substances (noxious substances) are those which can cause restricted health damage if inhaled, swallowed or absorbed through the skin. If highly toxic or toxic substances are produced in the course of an experiment (e.g. chlorine, hydrogen sulfide), these may only be produced in the quantities necessary for the experiment. in the case of volatile substances, the experiment must be conducted under a hood where the gas can be drawn off. Residue must be appropriately disposed of after the experiment and may on no account be stored. If the facilities for disposal are not available, the experiment may not be conducted. Less toxic substances and preparations may be obtained without a permit. Less toxic substances are also those which contain a highly toxic or toxic substance at a level of concentration below that determined by law as the maximum for classification as noxious. Chlorine water, bromine water and hydrogen sulfide solution in a concentration of up to 1% may therefore be used in instruction.

5. Corrosives and irritants (C, X i ) Caustic or corrosive substances (R 34, R 35), designation C, are those which can destroy living materials by their action upon it. Substances are classed as irritants (R 36 R 38), designation Xi, if they cause inflammation without being corrosive on direct, prolonged or repeated contact with the skin or mucous membranes. The relevant safety recommendations (S 22 S 28) should be observed.

6. Carcinogenic, genotype or embryo damaging, chronically harmful substances Substances may not be used for instruction if they have a proven carcinogenic effect (R 45), if they cause hereditary damage (R 46) or embryo damage (R 47), or if they are chronically damaging (R 48), particularly those substances classed as unmistakably carcinogenic. Such substances must be removed from all school stocks. Storage is not permitted under any circumstances. Further, substances for which there is a well founded suspicion of carcinogenic potential (R 40) may only be used if corresponding safety precautions are taken and only in such cases where they cannot be replaced by less dangerous chemicals.

B 2: R RATINGS AND S PROVISIONS

Nature of special risks (R)

R 1 Explosive when dry. R 2 Risk of explosion by shock, friction, fire or other sources of ignition. R 3 Extreme risk of explosion by shock, friction, fire or other sources of ignition. R 4 Forms very sensitive explosive metallic compounds. R 5 Heating may cause an explosion. R 6 Explosive with or without contact with air. R 7 May cause fire. R 8 Contact with combustible material may cause fire. R 9 Explosive when mixed with combustible material.

99 R 10 Flammable. R 11 Highly flammable. R 12 Extremely flammable. R 13 Extremely flammable liquefied gas. R 14 Reacts violently with water. R 15 Contact with water liberates highly flammable gases. R 16 Explosive when mixed with oxidizing substances. R 17 Spontaneously flammable in air. R 18 In use, may form flammable/explosive vapour air mixture. R 19 May form explosive peroxides. R 20 Harmful by inhalation. R 21 Harmful in contact with skin. R 22 Harmful if swallowed. R 23 Toxic by inhalation. R 24 Toxic in contact with skin. R 25 Toxic if swallowed. R 26 Very toxic by inhalation. R 27 Very toxic in contact with skin. R 28 Very toxic if swallowed. R 29 Contact with water liberates toxic gas. R 30 Can become highly flammable in use. R 31 Contact with acids liberates toxic gas. R 32 Contact with acids liberates very toxic gas. R 33 Danger of cumulative effects. R 34 Causes burns. R 35 Causes severe burns. R 36 Irritating to eyes. R 37 Irritating to respiratory system. R 38 Irritating to skin. R 39 Danger of very serious irreversible effects. R 40 Possible risks of irreversible effects. R 41 Danger of serious eye damage. R 42 May cause sensitization by inhalation. R 43 May cause sensitization by skin contact. R 44 Risk of explosion if heated by occlusion. R 45 May cause cancer. R 46 May cause hereditary damage. R 47 May cause embryo damage. R 48 Danger of chronic damage.

Safety advice (S)

S 1 Keep locked up. S 2 Keep out of reach of children. S 3 Keep in a cool place. S 4 Keep away from living quarters. S 5 Keep contents under .... (appropriate liquid to be specified by the manufacturer). S 6 Keep under .... (inert gas to be specified by the manufacturer). S 7 Keep container tightly closed. S 8 Keep container dry. 100 S 9 Keep container in a well ventilated place. S 10 Keep contents wet. S 11 Avoid contact with air. S 12 Do not keep the container sealed. S 13 Keep away from food, drink and animal feeding stuffs. S 14 Keep away from .... (incompatible materials to be indicated by the manufacturer). S 15 Keep away from heat. S 16 Keep away from sources of ignition No smoking. S 17 Keep away from combustible materials. S 18 Handle and open container with care. S 20 When using do not eat or drink. S 21 When using do not smoke. S 22 Do not inhale dust. S 23 Do not inhale gas/fumes/vapour/spray. S 24 Avoid contact with skin. S 25 Avoid contact with eyes. S 26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice. S 27 Take off immediately all contaminated clothing. S 28 After contact with skin, wash immediately with plenty of .... (to be specified by the manufacturer). S 29 Do not empty into drains. S 30 Never add water to this product. S 31 Keep away from explosive materials. S 33 Take precautionary measures against static discharges. S 34 Avoid shock and friction. S 35 This material and its container must be disposed of in a safe way. S 36 Wear suitable protective clothing. S 37 Wear suitable gloves. S 38 In case of insufficient ventilation, wear suitable respiratory equipment. S 39 Wear eye/face protection. S 40 To clean the floor and all objects contaminated by this material, use .... (to be specified by the manufacturer). S 41 In case of fire and/or explosion do not breathe fumes. S 42 During fumigation/spraying wear suitable respiratory equipment. S 43 In case of fire, use .... (indicate in space the precise type of fire fighting equipment. If water increases the risk, add Never use water). S 44 If you feel unwell, seek medical advice (show the label where possible). S 45 In case of accident or if you feel unwell, seek medical advice (show the label a where

101 B 3: EXPLANATION OF DANGER SYMBOLS

toxic (T) substances flammable (F) substances irritating (Xi) substances and and and very toxic (T+) substances extremely flammable (F+) substances harmful (Xn) substances

explosive (E) substances oxidizing (O) substances

corrosive (C) substances environmentally dangerous (N) substances

102 Appendix C

Concepts and skills expected to be known by all participants: (predominantly equivalent to former number 1 and 2 topics)

Concepts Awareness of experimental errors, use of significant figures;

Maths skills commonly encountered at secondary school level, including solving quadratic equations, use of logarithms and exponentials, solving simultaneous equations with 2 unknowns, the meaning of sine and cosine, elementary geometry such as Pythagoras’ theorem, plotting graphs (more advanced maths skills such as differentiation and integration, if required must be included as one of the advanced topics)

Nucleons, isotopes, radioactive decay and nuclear reactions (alpha, beta, gamma); Quantum numbers (n,l,m) and orbitals (s,p,d) in hydrogen-like atoms; Hund’s rule, Pauli exclusion principle; Electronic configuration of main group and the first row transition metal atoms and their ions; Periodic table and trends (electronegativity, electron affinity, ionization energy, atomic and ionic size, melting points, metallic character, reactivity); Bond types (covalent, ionic, metallic), intermolecular forces and relation to properties; Molecular structures and simple VSEPR theory (up to 4 electron pairs);

Balancing equations, empirical formulae, mole concept and Avogadro constant, stoichiometric calculations, density, calculations with different concentration units;

Chemical equilibrium, Le Chatelier’s principle, equilibrium constants in terms of concentrations, pressures and mole fractions; Arrhenius and Bronsted acid-base theory, pH, self ionization of water, equilibrium constants of acid-base reactions, pH of weak acid solutions, pH of very dilute solutions and simple buffer solutions, hydrolysis of salts; Solubility constants and solubility; Complexation reactions, definition of coordination number, complex formation constants;

Basics of electrochemistry: Electromotive force, Nernst equation; Electrolysis, Faraday’s laws;

Rate of chemical reactions, elementary reactions, factors affecting the reaction rate, rate law for homogeneous and heterogeneous reactions, rate constant, reaction order, reaction energy profile, activation energy, catalysis, influence of a catalyst on thermodynamic and kinetic characteristics of a reaction;

Energy, heat and work, enthalpy and energy, heat capacity, Hess’ law, standard formation enthalpies, solution, solvation and bond enthalpies;

Definition and concept of entropy and Gibbs’ energy, second law of thermodynamics, direction of spontaneous change;

103

Ideal gas law, partial pressures;

Principles of direct and indirect titration (back titration); Acidi- and alkalimetry, acidimetric titration curves, choice and color of indicators for acidimetry; Redox titrations (permanganometric and iodometric); Simple complexometric and precipitation titrations;

Basic principles of inorganic qualitative analysis for ions specified in factual knowledge, flame tests;

Lambert-Beer law;

Organic structure-reactivity relations (polarity, electrophilicity, nucleophilicity, inductive effects, relative stability) Structure-property relations (boiling point, acidity, basicity); Simple organic nomenclature; Hybridization and geometry at carbon centers; Sigma and pi bonds, delocalization, aromaticity, mesomeric structures; Isomerism (constitutional, configuration, conformation, tautomerism) Stereochemistry (E-Z, cis-trans isomers, chirality, optical activity, Cahn-Ingold-Prelog system, Fisher projections); Hydrophilic and hydrophobic groups, micelle formation; Polymers and monomers, chain polymerizations, polyaddition and polycondensation;

Laboratory skills Heating in the laboratory, heating under reflux; Mass and volume measurement (with electronic balance, measuring cylinder, pipette and burette, volumetric flask); Preparation and dilution of solutions and standard solutions; Operation of a magnetic stirrer; Carrying out of test tube reactions; Qualitative testing for organic functional groups (using a given procedure); Volumetric determination, titrations, use of a pipette bulb; Measurement of pH (by pH paper or calibrated pH meter);

Examples of concepts and skills allowed in the exam only if included and demonstrated in the preparatory problems 6 theoretical and 2 practical topics from these or other topics of similar breadth are allowed in a preparatory problem set. It is intended that a topic can be introduced and discussed in a lecture of 2-3 hours before a prepared audience.

• VSEPR theory in detail (with more than 4 ligands); • Inorganic stereochemistry, isomerism in complexes; • Solid state structures (metals, NaCl, CsCl) and Bragg’s law; • Relation of equilibrium constants, electromotive force and standard Gibbs energy;

104 • Integrated rate law for first order reactions, half-life, Arrhenius equation, determination of activation energy; • Analysis of complex reactions using steady-state and quasi-equilibrium approximations, mechanisms of catalytic reactions, determination of reaction order and activation energy for complex reactions; • Collision theory • Simple phase diagrams and the Clausius-Clapeyron equation, triple and critical points; • Stereoselective transformations (diastereoselective, enantioselective), optical purity • Conformational analysis, use of Newman projections, anomeric effect • Aromatic nucleophilic substitution, electrophilic substitution on polycyclic aromatic compounds and heterocycles • Supramolecular chemistry • Advanced polymers, rubbers, copolymers, thermosetting polymers. Polymerization types, stages and kinetics of polymerization; • Amino acid side groups, reactions and separation of amino acids, protein sequencing; • Secondary, tertiary and quaternary structures of proteins, non-covalent interactions, stability and denaturation, protein purification by precipitation, chromatography and electrophoresis; • Enzymes and classification according to reaction types, active sites, coenzymes and cofactors, mechanism of catalysis; • Monosaccharides, equilibrium between linear and cyclic forms, pyranoses and furanoses, Haworth projection and conformational formulae; • Chemistry of carbohydrates, oligo- and polysaccharides, glycosides, determination of structure; • Bases, nucleotides and nucleosides with formulae, Functional nucleotides, DNA and RNA, hydrogen bonding between bases, replication, transcription and translation, DNA based applications; • Complex solubility calculations (with hydrolyzing anions, complex formation); • Simple Schrödinger equations and spectroscopic calculations; • Simple MO theory; • Basics of mass spectrometry (molecular ions, isotope distributions); • Interpretation of simple NMR spectra (chemical shift, multiplicity, integrals); • Synthesis techniques: filtrations, drying of precipitates, thin layer chromatography. • Synthesis in microscale equipment; • Advanced inorganic qualitative analysis; • Gravimetric analysis; • Use of a spectrophotometer; • Theory and practice of extraction with immiscible solvents; • Column chromatography;

105 Appendix D

Outline of the factual knowledge supposed to be known by the competitors: Reactions of s-block elements with water, oxygen and halogens, their color in flame tests; Stoichiometry, reactions and properties of binary non-metal hydrides; Common reactions of carbon, nitrogen and sulfur oxides (CO, CO2, NO, NO2, N2O4, SO2, SO3); Common oxidation states of p-block elements, stoichiometry of common halides and oxoacids (HNO2, HNO3, H2CO3, H3PO4, H3PO3, H2SO3, H2SO4, HOCl, HClO3, HClO4); Reaction of halogens with water; Common oxidation states of first row transition metals (Cr(III), Cr(VI), Mn(II), Mn(IV), Mn(VII), Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), Ag(I), Zn(II), Hg(I), and Hg(II) )and the color of these ions; Dissolution of these metals and Al, amphoteric hydroxides (Al(OH)3, Cr(OH)3, Zn(OH)2); Permanganate, chromate, dichromate ions and their redox reactions; Iodometry (reaction of thiosulfate and iodine); + 2+ 3+ 2+ – 2– 2– Identification of Ag , Ba , Fe , Cu , Cl , CO3 , SO4 ;

Organic: Common electrophiles and nucleophiles Electrophilic addition: addition to double and triple bonds, regioselectivity (Markovnikoff’s rule), stereochemistry Electrophilic substitution: substitution on aromatic rings, influence of substituents on the reactivity and regioselectivity, electrophilic species; Elimination: E1 and E2 reactions at sp3 carbon centers, stereochemistry, acid-base catalysis, common leaving groups; Nucleophilic substitution: SN1 and SN2 reactions at sp3 carbon centers, stereochemistry; Nucleophilic addition: addition to carbon-carbon and carbon-hetero atom double and triple bonds, addition-elimination reactions, acid-base catalysis; Radical substitution: reaction of halogens and alkanes; Oxidations and reductions: switching between the different oxidation levels of common functional groups (alkyne – alkene – alkane – alkyl halide, alcohol – aldehyde, ketone – carboxylic acid derivatives, nitriles – carbonates) Cyclohexane conformations; Grignard reaction, Fehling and Tollens reaction;

Simple polymers and their preparation (polystyrene, polyethylene, polyamides, polyesters); Amino acids and their classification in groups, isoelectric point, peptide bond, peptides and proteins; Carbohydrates: open chain and cyclic form of glucose and fructose; Lipids: general formulae of triacyl glycerides, saturated and unsaturated fatty acids;

106 List of the participated Head Mentors, Mentors, Observers, and Guests

Country Role Name Affiliation HM Maria Laura Uhrig Universidad de Buenos Aires Argentina M Vicente Gregorio Povse Universidad de Buenos Aires HM Lida Sahakyan Yerevan State Medical University Armenia M Vitush Vano Sargsyan Yerevan Institute Plastpolymer HM Tristan Andrew Reekie The Australian National University M Anne Trinh University of Sydney Australia O Mark John Ellison The Australian National University O William Cedar Jackson Australian National University HM Manfred Kerschbaumer Albertus Magnus Gymnasium Austria M Liesbeth Berner retired HM Igrar Nazarov Institute of Petrochemical Processes Azerbaijan M Khammad Asadov Baku State University HM Viktar Khvalyuk The Belarusian State University Belarus M Yauheni Paulechka Belarusian State University HM Hans Vanhoe University of Ghent Belgium M Cédric Malherbe University of Liège O Geoffroy Kaisin University of Liège HM Sergio Maia Melo FUNCAP Brazil M Dantas Jose Arimateia Lopes Universidade Federal do Piaui O Rubens Conilho Junior Colegio Etapa HM Donka Nikolova Tasheva Sofia University “St. Kl. Ohridsky” Bulgaria M Penka Vasileva Tsanova Sofia University “St. Kl. Ohridsky” HM Stanislaw Skonieczny University of Toronto Canada M Jeffrey David Mo Massachusetts Institute of Technology HM Lianyun Duan Peking University M Ping Lu Zhejiang University China O Yingxia Wang Peking University O Qiaohong He Zhejiang University HM I-Jy Chang National Taiwan Normal University M Wann-Yin Lin National Taiwan University O Chingfa Yao National Taiwan Normal University Chinese Taipei O Ya-Ling Chen Taipei Municipal Jianguo High School G Tai-Shan Fang National Taiwan Normal University G Szu-Chi Hsieh Ministry of Education G Tsu-Rong George Shiau College Entrance Examination Center HM Jose Vega Universidad Nacional M Randall Syedd - León Universidad Nacional Costa Rica G Ana - Rocio Madrigal - Gutierrez Universidad Nacional Maria De Los Angeles Arguedas- G Pensionada Madrigal G Rafael Angel Rodriguez - Campos Pensionado

107 Country Role Name Affiliation HM Branka Zorc University of Zagreb Croatia M Tomislav Cvitaš University of Zagreb Cuba HM Rolando Alfonso Valdes IPVCE Ernesto Guevara HM Paraskevas Panteli Ministry of Education Cyprus M Erineos Koromias Ministry of Education HM Petr Holzhauser Institute of Chemical Technology, Prague Czech Faculty of Science, Charles University Republic M Eva Muchova Prague HM Kurt Bjønager Nielsen Ordrup Gymnasium Denmark M Brian Schou Rasmussen University of Copenhagen O Nina Lock Aarhus University HM Uno Mäeorg University of Tartu Estonia M Jaak Nerut University of Tartu HM Jorma Kullervo Koskimies University of Helsinki Finland M Kjell Knapas University of Helsinki O Teemu Samuel Arppe University of Helsinki HM Olivier Plaidy Ministère Education Nationale M Laurence Petit Sciences à l'Ecole France O Christine Hirschler Lycée Jean Mermoz O Alban A. Letailleur Université Pierre et Marie Curie HM Wolfgang Hampe Germany M Alexander Rodenberg University of Zuerich O Timo Gehring Karlsruher Institute for Technology (KIT) HM Nikolas Psaroudakis University of Athens Greece M Eystratios Asimellis 3rd EPAL of Athens, Greece HM Gyorgy Zoltan Tarczay Eotvos University Hungary M Szilard Varga Chemical Researh Center HAS O Attila Villanyi Eotvos Lorand University Menntaskólinn í Reykjavík HM Finnbogi Óskarsson Iceland (Reykjavík Junior College) M Ísak Sigurjón Bragason University of Iceland V.G. Vaze College of Arts, HM Lakshmy Ravishankar Science and Commerce India M Radha Vijay Jayaram Institute of Chemical Technology O Pradeep Tryambakrao Deota M.S. University of Baroda HM Riwandi Sihombing University of Indonesia M Djulia Onggo Bandung Institute of Technology Indonesia O Deana Wahyuningrum Bandung Institute of Technology O Ismunaryo Moenandar University of Indonesia Ministry of Education, Republic of G Hastuti Musikaningsih Indonesia HM Mansour Abedini University of Tehran M Ebrahim Kianmehr University of Tehran I. R. of Iran O Mahin Jabalameli The Young Scholars Club O Alireza Shayesteh University of Tehran

108 Country Role Name Affiliation HM Paraic James Dublin City University Ireland M Matthew John Cook Queen's University Belfast O Michael Anthony Cotter Dublin City University HM Iris Barzilai Technion-Israel Institute of Technology Israel M Miriam Iris Barak Technion-Israel Institute of Technology O Khalil Abo Nofal ST. Joseph High School and Seminary HM Mario Anastasia University of Milan Italy M Raffaele Colombo University of Milan HM Nobuhiro Kihara Kanagawa University M Asao Nakamura Shibaura Institute of Technology Japan O Yasuhiro Yamada Tokyo University of Science O Takeshi Kanazawa Hokkaido Sapporo Nishi High School Kurmangali Batyrbekovich HM Kazakh National University Bekishev Gulnar Mukhangaliyevna Kazakhstan M RSPC Daryn Akimzhanova Almaty Institute of Energetic and G Anna Ivanovna Bekisheva Connection HM Hackjin Kim Chungnam National University M Yunkyoung Ha Hongik University O Bokyoung Lee Yonsei University O Do Hyun Ryu Sungkyunkwan University Korea G Duckhwan Lee Sogang University Ministry of Education, Science and G Eun Soo Kim Technology Korea Foundation for the Advancement of G Won Sun Jung Science & Creativity The Kuwait Foundation for the HM Barak Mehdi Hadi Advancement of Sciences The Kuwait Foundation for the M Fotouh Abdullah Alshamali Advancement of Sciences The Kuwait Foundation for the O Muna Ibrahim Alansari Advancement of Sciences Kuwait O Essa Menhal Alqallaf Ministry of Education G Jasem Osamah Abul Kuwait English School G Meshari Osamah Abul Kuwait English School The Kuwait Foundation for the G Abdulaziz Ibrahim Alquraishi Advancement of Sciences The Kuwait Foundation for the G Khalida Zaid Alzamel Advancement of Sciences Scientific Research Institute on Chemistry HM Minira Batkibekova and Technology at Kyrgyz State Technical University Named after I. Razzakov Kyrgyzstan Karabalty Technological Institute at M Fanargul Abdyldaeva Kyrgyz State Technical University named after I. Razzakov HM Juris Fotins Latvian Institute of Organic Synthesis Latvia M Skaidrīte Pakule University of Latvia

109 Country Role Name Affiliation Liechtenstein O Karin Andrea Birbaum ETH Zurich HM Rimantas Raudonis Vilnius University Lithuania M Marius Jurgelenas Vilnius University HM Noorsaadah A. Rahman University of Malaya M Sharifuddin Mohd. Zain University of Malaya Malaysia O Ilani Ibrahim Malaysian Institute of Chemistry O Shamsir Jemain Education Department Ramiro Eugenio Dominguez Universidad Nacional Autónoma De HM Danache Mexico Universidad Nacional Autónoma De Mexico M Eugenio Octavio Reyes Mexico Universidad Nacional Autónoma De O Carlos Mauricio Castro Acuña Mexico HM Ion Bulimestru State University of Moldova Moldova M Victor Ţapcov State University of Moldova HM Dorj Daichaa National University of Mongolia Mongolia M Nyamgerel Choijilsuren National University of Mongolia O Davaasuren Sandag National University of Mongolia Gemeentelijk Gymnasium Hilversum/SLO HM Peter De Groot Enschede Netherlands M Emiel De Kleijn SLO O Johan Broens SLO HM Owen John Curnow University of Canterbury New Zealand M Duncan James Mcgillivray The University of Auckland O Sunday Asher Adedeji National Mathematical Centre, Abuja Nigeria O Ayodele Ajayi Akanle Ministry Of Education, Akure O Clement Olajide Adeyemo National Mathematical Centre, Abuja HM Tor Erik Kristensen University of Oslo Norway M Bjørn Dalhus National University Hospital HM Khalid Mohammed Khan University of Karachi Pakistan M Muhammad Raza Shah University of Karachi Peru HM Bertha Beatriz Flores Alor Pontificia Universidad Católica del Perú HM Marek Orlik University of Warsaw Poland M Karolina Agnieszka Pułka University of Warsaw Diana Cláudia Gouveia Alves HM University of Aveiro Pinto Portugal Maria Do Amparo Ferreira M University of Aveiro Faustino HM Marius Andruh University of Bucharest Ministry of Education, Research, Romania M Daniela Bogdan Youth and Sports G Ecaterina Florica Safarica Ecaterina Florica Safarica

110 Country Role Name Affiliation HM Vadim Eremin Moscow State University M Alexander Gladilin Moscow State University O Ilya Glebov Moscow Institute of Open Education O Elena Eremina Moscow State University Russian Shemyakin & Ovchinnikov Institute of Federation G Elena Korchagina Bioorganic Chemistry, Russian Academy ofSciences G Liudmila Levina Tsentrhimpress G Oxana Gladilina ZKS, LLC G Sergey Lyubimov Neochem Ltd O Dhaifallah Mohammed Aldhayan King Saud University (KSU) O Nada Abdulaziz Aljallal King Saud University (KSU) Saudi Arabia G Fahad Albakr Vinnell Arabia G Faisal Albakr Child Serbia O Dušan Sladić University of Belgrade HM Yaw Kai Yan National Institute of Education M Sheng Zhang National University of Singapore Singapore O Untung Edy Rusbandi National University of Singapore O Xuhao Alvin Pek Victoria Junior College G Kok Wei Foo Ministry of Education, Singapore HM Anton Sirota IUVENTA M Martin Putala Comenius University in Bratislava Slovakia O Pavol Tarapčík Slovak Technical University, Bratislava O Ján Reguli Trnava University HM Andrej Godec University of Ljubljana Slovenia M Darko Dolenc University of Ljubljana HM Juan Antonio Rodriguez Renuncio University Complutense at Madrid Maria Del Carmen Causape M Universidad Politecnica de Madrid Spain Cartagena O Marta Enciso University Complutense at Madrid O Vicente Martí Centelles Universitat Jaume I HM Ulf Charles Jaglid Chalmers University of Technology Sweden M Anna Cecilia Stenberg Kungsholmens Gymnasium O Per Henning Lindgren Erik Dahlbergs Gymnasiet HM Dustin Hofstetter ETH Zurich Switzerland M Peter Eladio Ludwig ETH Zürich EPFL (Swiss Federal Institute of O Basile Isidore Martin Wicky Technology, Lausanne) Syrian Youth Federation and SONA HM Emad Mouafak Alazeb (Syrian Science Olympiad National Authority) Mohamad Majed Mohamad Syria M Damascus University Alsabbagh Syrian Youth Federation and SONA O Salah Mahmod Asad (Syrian Science Olympiad National Authority)

111 Country Role Name Affiliation HM Erhan Güler Shelale Educational Corporation Tajikistan M Parviz Khakimov Medical University of Tajikistan HM Ekasith Somsook Mahidol University M Thammarat Aree Chulalongkorn University O Aroonsiri Shitangkoon Chulalongkorn University Thailand O Yongsak Sritana-Anant The University of Chulalongkorn The Institute for the Promotion of G Supunnee Chanprasert Teaching Science and Technology. G Techin Chuladesa Harvard University HM Jale Hacaloglu Middle East Technical University M Osman Ataman Middle East Technical University O Saim Ozkar Middle East Technical University O Metin Balci Middle East Technical University O Ahmet Onal Middle East Technical University Turkey The Scientific and Technological Research O Ibrahim Ozdemiroglu Council of Turkey G Ayse Gulay Ataman Middle East Technical University G Jale Balci Middle East Technical University Retired from Middle East Technical G Nedret Ozkar University HM Guvanchmyrat Paytakov Turgut Ozal High School Turkmenistan M Mametmurat Geldiniyazov Magtymguly University HM Yuriy Kholin V.N. Karazin Kharkiv National University Institute of Innovation Technologies and Ukraine M Galyna Malchenko Content of Education O Dmytro Kandaskalov National Polytechnic Institute HM Andrew Francis Worrall Harrow School United M Ben Samuel Pilgrim University of Oxford Kingdom O Peter David Wothers The University of Cambridge G Laura Dunn Royal Society of Chemistry HM Kimberly A. Gardner US Air Force Academy M Kristin Ayn Fletcher USAFA O Gabriel Bryan Balazs Lawrence Livermore National Laboratory O John Leon Kiappes The Scripps Research Institute United States O Cecilia D. Hernandez American Chemical Society O Natalia L. White University of Maryland O Andrea Elizabeth Morris University of Maryland G Javier E. Hernandez Fuentes Interamerican Investment Corporation Facultad de Quimica-Universidad de la Uruguay HM Gustavo Seoane Muniz Republica Venezuelan Chemistry Olympiad HM Amalia Torrealba Sanoja Venezuela Association M José Rafael Camacho Gutiérrez Universidad Simón Bolívar

112 Country Role Name Affiliation HM Son Do Quy Vietnam Atomic Energy Commision Viet Nam Ministry of Education and M Hien Pham Dinh Training O Dau Nguyen Van National University of Ha Noi O Chinh Nguyen Quoc National University of Ho Chi Minh G Hung Pham Tuan Hai Phong Educational Service Viet Nam G Phuong Mai Chau Lam Son School G Hung Nguyen Van Lam Son School G Nhi Nguyen Thi Nguyen Trai School Viet Nam Ministry of Education and G Kha Nguyen Duy Training Viet Nam Ministry of Education and G Hoa Tran Thi Viet Training G Diep Dao Thi Phuong Hanoi National University of Education

113 List of the competed Students Country Name School Ezequiel Maidanik ORT Nicolas Villagran Dos Santos Instituto Ballester Argentina Mario Rugiero Hipolito Yrigoyen Matias Lanus Mendez Elizalde Escuela Vahagn Tamazyan Quantum Davit Arzumanyan Fizmath School Armenia Artur Aslanyan Usum Edvard Sargsyan Vanadzor Fizmat Stuart Ferrie Melbourne High School Allan Chau James Ruse Agricultural High School Australia Cyril Tang Sydney Grammar School Kelvin Cheung James Ruse Agricultural High School Sebastian Gogg pORg der Ursulinen Graz Johannes Hellwagner HTL Villach Austria Konstantin Krautgasser HTL Villach Robert Pollice GRg Sachsenbrunn Agil Azimzada Lenkoran Private High School Rashad Yusifov Guba Private High School Azerbaijan Agil Safaralizade Dede Gorgud Private High School Vugar Mirzakhanov AZ1065, Pasha Nazarli School 60 Jasmine De Becker Sint-Jozefinstituut Herentals Jeroen Van Cleemput Europese School Brussel II Belgium Kevin Renier Athénée Royal de Huy Florence Thiry Athénée Royal Nivelles Vasil Vasilev MG National High School of Mathematics and Ivan Bojidarov Dimov Science, Sofia Bulgaria National High School of Mathematics and Fani Georgieva Madzharova Science, Sofia National High School of Mathematics and Tsvetan Hristov Tarnev Science, Sofia Lizaveta Durovich Gimnasium 7 Mikhail Kavalchuk School 71 Belarus Dzianis Kuliomin State Lyceum of Minsk Region Natallia Yelavik School 22 Levindo Jose Garcia Quarto Ari de Sa Jessica Kazumi Okuma Colégio Etapa Brazil Raul Bruno Machado Da Silva Colegio Farias Brito Andre Silva Franco Colegio Etapa Connie Zhao University of Toronto Schools Philip Sohn Northern Secondary School Canada Richard Liu University of Toronto Schools Brian Bi Woburn Collegiate Institute

114 Country Name School Michelle Frei Kantonsschule Wettingen Michele Oliosi Gymnase Auguste Piccard Switzerland Yannick Suter Kantonsschule Wettingen Alain Vaucher Collège Sainte-Croix Xianghang Shangguan Changjun Middle School No.1 High School Affiliated to Central Zhiyao Zhou China Normal University China Qilei Zhu Hangzhou No.2 Middle School High School Attached to Nanjing Normal Ruyi Wang University Colegio Cientifico Costarricense de Rafael Angel Rodriguez Arguedas Occidente Colegio Cientifico Costarricense de San Tachmajal Corrales Sanchez Costa Rica Pedro Oscar Garcia Montero Colegio Nueva Esperanza Colegio Científico Costarricense de Wainer Camacho Araya Occidente Cuba Ramón Lorenzo Panades Barrueto IPVCE Eusebio Olivera Panayiota Katsamba Lyceum Agiou Georgiou Larnaka Christos Anastassiades Lyceum Apostolon Petrou & Pavlou Cyprus Stelios Chatzimichail Pagyprio Lyceum Larnaka Andreas Sofokli Lyceum Paphos Ondrej Hak Gymnasium a SOS Husova 1414 Ondrej Henych Gymnasium Jeronymova 27 Czech Republic Frantisek Petrous Gymnasium Jirovcova 8 Pavel Svec Gymnasium Jirovcova 8 Florian Berger Werner-Heisenberg-Gymnasium Manuel Eberl Gymnasium Dingolfing Germany Leonard Hasenclever Wilhelm-Ostwald-Gymnasium Lukas Wagner Max-Planck-Gymnasium Mads Bøttger Hansen Aabenraa Statsskole Jakob Bank Kodal Esbjerg Statsskole Denmark Kristian Holten Møller Slagelse Gymnasium Niels Christian Holm Sanden Ordrup Gymnasium Andreu Tortajada Navarro IES Benaguasil Jesús Alvaro Gómez Iregui Colegio N.S. del Buen Consejo (Logroño) Spain Marconi Nicolás Peñas De Frutos IES Parquesol (Valladolid) Pablo Giomi Liceo Español Luis Buñuel Gleb Široki Tallinna Õismäe Russian Lyceum Maksim Mišin Tallinn Mustamäe Real Gymnasium Estonia Ivan Jakovlev Tallinn Õismäe Russian Lyceum Kadi Liis Saar Tallinn Secondary Sceince School Suvi Kaarina Klapuri Vaasan Lyseon Lukio Oscar Salomon Kivinen Helsingin Suomalainen Yhteiskoulu Finland Jarkko Timo Olavi Järvelä Karkkilan Yhteislyseo Jari Tapio Huisman Jyväskylän Normaalikoulun Lukio

115 Country Name School Rémi Olivier Patin Lycée Montaigne Cédric Martin Lycée Thiers France Antton Curutchet Lycée René Cassin Baptiste Couet Lycée Clemenceau David Edey Alcester Grammar School David Wade Northgate High School United Kingdom Joshua Stedman Abingdon School Ruth Franklin Manchester High School for Girls Nikolaos Kaplaneris 1 Gel Glyfada Michael Matalliotakis 2 Gel Irakleio Crete Greece Georgios Papadimitriou 8 Gel Trikalon Stefanos Tyros Bougas School Vranješević Filip V. Gimnazija, Zagreb Markovic Igor V. Gimnazija, Zagreb Croatia Kucanda Kristina I. Gimnazija Zagreb Petricevic Fran III. Gimnazija Osijek Ciszterci Rend Nagy Lajos Gimnáziuma Eszter Najbauer és Kollégiuma, Pécs Attila Sveiczer Eötvös József Gimnázium, Budapest Hungary Fazekas Mihály Fővárosi Gyakorló Áron Szigetvári Általános Iskola és Gimnázium, Budapest ELTE Apáczai Csere János Gyakorló Máté Somlyay Gimnáziuma Manoel Manuputty SMAK Penabur Gading Serpong Indonesia Alimatun Nashira SMAN 1 Yogyakarta, Indonesis Indonesia Stephen Yuwono SMAN 1 Purwokerto, Indonesia SMA Taruna Nusantara Magelang Agung Hartoko Indonesia Amit Panghal Bhartiya Public School Diptarka Hait Salt Lake School India Nikunj Saunshi Sathaye College Narayana Junior College, Tarnaka, Surendra Kotra Hyderabad Anandagopal Srinivasan Metodist College, Belfast Daniel Quill St. Michael's College Ireland Dermot Gillen Marist College, Athlone Jonathan Wilson Portora Royal School Hanieh Safari Farzanegan Hossein Dadashazar Allameh Tabatabaei I. R. of Iran Seyed Amirhossein Nasseri Shahid Soltani Mohammadreza Amirmoshiri Shahid Madani Árni Johnsen Menntaskólinn við Hamrahlíð Helgi Björnsson Menntaskólinn við Hamrahlíð Iceland Konráð Þór Þorsteinsson Menntaskólinn í Reykjavík Sigtryggur Kjartansson Fjölbrautaskóli Suðurnesja

116 Country Name School Eviatar Degani Hadera High School Michael Michelachvili Hagimnasia Harealit, Rishon Lezion Israel Assaf Mauda Hadera High School Anael Ben Asher Ort Horovitz, Carmiel Liceo Scientifico "G. Marconi" Luciano Barluzzi Di Foligno Italy Luca Zucchini ITIS "T. Buzzi" Di Prato Alberto Branchi ITIS "E. Fermi" Di Mantova Giuseppe Recchia ITIS Hiroki Uratani Shiga Prefactual Zeze High School Ken-Ichi Endo Eiko Gakuen Japan Junior and Senior High School at Komaba, Kengo Kataoka University of Tsukuba Hayate Saitoh NADA Junior and Senior High School Zhalgas Serimbetov Kazakh-turkish High School Ilya Skripin Kazakh-turkish High School Kazakhstan Abylay Shakhizadayev Kazakh-turkish High School Miras Bekbergenov Kazakh-turkish High School Sagynbek Dadybaev Tokmok Turkish High School Kalysbek Abykeshov NARIN Turkish High School Kyrgyzstan JALAL-ABAD Kyrgyz-Turkish High Azizbek Usvaliev School Saltanat Mambetova School-licen N28 Scryabina Jaehyun Lim Seoul Science High School Hyeonjae Lee Gyeonggibuk Science High School Korea Pilkeun Jang Sejong Science High School Won Jae Kim Sejong Science High School AHMAD AL-BISHER ROOMI High Mohammad Alabdulrazzaq School Kuwait Hessah Alquraishi ALNAHDA High School Shahad Albaloul MARYA ALQUTIA High School Mariam Aldarweesh ALYARMOUK High School Vidmantas Bieliunas Vilniaus Gabijos Gimnazija Emilis Bruzas Klaipedos "Azuolyno" Gimnazija Lithuania Vladimiras Oleinikovas KTU Gymnasium Dominykas Sedleckas KTU Gymnasium Roberts Bluķis Riga State Gymnasium No. 1 Viktors Pozņaks Riga 22nd Secondary School Latvia Dmitrijs Jevdokimovs Riga Secondary School No. 40 Jānis Briška Sala Secondary School Negrescu Dan Nicolae Iorga Dosca Anastasia Prometeu-Prim Moldova Buiucli Serafim N. Milescu Spataru Pîrău Tudor LC Magdacesti

117 Country Name School Raymundo Esquer-Rodriguez Instituto Salvatierra Alan Carrasco-Carballo Cobao 02 El Espinal Mexico Oscar Palomino-Hernandez Escuela Hispano Mexicana Tania Lizeth Lopez-Silva CBTIS117 Amarsanaa Davaasuren School No. 11, Ulaanbaatar Selenge Enkhtuya School No. 28, Ulaanbaatar Mongolia Enkhbat Myagmar "Shine Mongol" School, Mongolia Gantulga Batbayar School No. 14, Orkhon Province Yeoh Keat Hor To be announced Nicholas Thong Li Jie To be announced Malaysia Siti Fatma Hawaria Mokhtar To be announced Rabi'Atul Adibah 'Allauddin To be announced Alexander Blokhuis Pleincollege van Maerlant Anatolij Babič Het Stedelijk Lyceum Zuid Netherlands Istvan Kleijn Emelwerda College Manuel Van Rijn RSG Tromp Meesters Maartje Iris Romijn Den Norske Skolen Gran Canaria Espen Auseth Nielsen Adolf Øiens Skole Norway Lars Moen Strømsnes Fauske VGS, avd. Vestmyra Ingrid Eidsvaag Andersen Bergen Katedralskole Stewart Alexander Christchurch Boys' High School David Bellamy Christ's College New Zealand Jaimin Choi Massey High School Lujia Xu Massey High School Izhar Ali Agha Khan Higher Secondary School Minahil Sana Qasim Beacon House Defence Campus Pakistan Hafiz Hassan Ali Fazaia Degree College PAF Base Faisal Muhammad Anus St. Patricks High School Luis Fernando Merma Paucar Pascual Saco Oliveros Peru Anthony John Salcedo Meza Pascual Saco Oliveros I Liceum Ogolnoksztalcace, ul. Kilinskiego Kornel Ocytko 7, 65-508 Zielona Gora, Poland V Liceum Ogolnoksztalcace im. Ks. J. Marcin Malinowski Poniatowskiego, Warsaw Poland VIII Liceum Ogolnoksztalcace im. Adama Witold Hoffmann Mickiewicza, Poznan I Liceum Ogolnoksztalcace im. M. Maciej Gryszel Kopernika, Kolobrzeg Gonçalo Vitorino Bonifácio Secundária José Saramago Alexandre Faia Carvalho Escola secundária de Peniche Portugal Marta Cristina Neves Aguiar Escola Secundária Homem Cristo Escola Secundária com 3º ciclo Emídio Jorge Pedro Martins Nogueiro Garcia

118 Country Name School Tudor Balan Colegiul "COSTACHE NEGRUZZI" IAŞI Liceul Teoretic ’’N.BĂLCESCU” Constantin Giurgiu CLUJ-NAPOCA Romania Colegiul National "VLAICU VODĂ" Alexandru Sava CURTEA DE ARGEŞ Ioana Moga Colegiul National ”E.GOJDU” ORADEA Daniil Khokhlov School 167, St-Petersburg Russian Kirill Sukhoverkov Gimnazium 22, Barnaul Federation Maxim Kozlov Gimnazium of Dimitrovgrad Alexander Kochnev Lyceum 230, Zarechnyi Khu Boon Hou Derek Hwa Chong Institution Tng Jia Hao Barry Raffles Institution Singapore Fong Jie Ming Nigel Raffles Institution Lum Jian Yang Raffles Institution Gymnazium for Extraordinary Gifted Marek Buchman Children Slovakia Ladislav Hovan Gymnazium, Exnárova 10 Dominik Štefanko Gymnázium Andreja Vrábla, Levice Marek Vician Gymnázium V.B. Nedožerského Valter Bergant Šolski Center Rudolfa Maistra Kamnik Božidar Aničić II. Gimnazija Maribor Slovenia Žiga Perko II. Gimnazija Maribor Nejc Petek Gimnazija Litija David Ahlstrand Erik Dahlbergsgymnasiet Viktor Mattias Johansson Ostrabo 1 Sweden Emil Marklund Forsmarks Skola Oscar Hans Emil Mickelin Sodra Latins Gymnasium Distinguished Student School Damascus Ali Mourtada Syria Syria Ali Issa Distinguished Student Mohammad Shubat Distinguished Student Rouaa Al Nan Distinguished Student Pinnaree Tea-Mangkornpan Triam Udom Suksa School Khetpakorn Chakarawet Trium Udom Suksa School Thailand Alif Noikham Mahidolwittayanusorn School Jiraborrirak Charoenpattarapreeda Suankularb Wittayalai Alisher Rakhimov Haji Kemal Tajik-Turkish High School Saidali Kholzoda Haji Kemal Tajik Turkish High School Tajikistan Shakhboz Zulfaliev Mavlono High School Ulugbek Barotov Mavlono High School Wepa Roziyev Bashkent Turkmen-turkish High School Myrat Annamuhammedov Bashkent Turkmen-turkish High School Turkmenistan Rahym Ashirov Bashkent Turkmen-turkish High School Begmyrat Cholukov Beyik S. Turkmenbasy ad. AZCM

119 Country Name School Fatih Alcicek Ozel Yamanlar Fen Lisesi Deniz Caglin Yamanlar Koleji Turkey Makbule Esen Istanbul Ozel Kasimoglu Coskun Fen Lisesi Mehmet Cem Sahiner Ozel Samanyolu Fen Lisesi Yu-Chi Kuo Taipei Municipal Jianguo High School Ming-Ko Cho National Taichung First Senior High School Chinese Taipei Wei-Che Tsai National Taichung First Senior High School Bo-Yun Gu Taipei Municipal Jianguo High School Specialized Sanatorium Boarding School Sergiy Shyshkanov for Gifted Children "Erudit" Specialized Sanatorium Boarding School Vladyslav Panarin for Gifted Children "Erudit" Ukraine 200 Anniversary Lugansk Communal Anton Topchiy Institution Lugansk Secondary Specialized I-III Level Gymnasium No. 60 Lviv Physics and Mathematics Lyceum of Dmytro Frolov Ivan Franko Lviv National University Melissa Bariani Liceo Nº1 Q.F. Heinzen Norberto Andres Canepa The British Schools Uruguay Alejandro Rodriguez PREU Sebastian Andres Martinez Colegio Sagrada Familia Colin Lu Vestal High School Alexander Siegenfeld Hopkins School United States Utsarga Sikder South Brunswick High School Richard Li River Hill High School Carlos Javier Berrio Barrera Liceo Bolivariano Julio Bustamante Arnaldo Enmanuel Marin Suárez Colegio la Salle-Lara Venezuela Erwin Wilfredo Mora Flores Liceo Bolivariano Pedro Fontes María Victoria Moreno Hernández Institutos Educacionales Asociados Binh Nguyen Duc Lam Son Cuc Mai Thu Nguyen Trai Viet Nam Quang Luu Nguyen Hong PTNK Ho Chi Minh Tuan Le Anh Tran Phu

120 Country Participation Fees Fee Fee Years Fee Years Fee Country in in JPN Country in in JPN in USD in USD 2010 Yen 2010 Yen Argentina 16 $1,600 ¥144,000 Kuwait 18 $1,800 ¥162,000 Armenia 5 $500 ¥45,000 Kyrgyzstan 11 $1,100 ¥99,000 Australia 12 $1,200 ¥108,000 Latvia 20 $2,000 ¥180,000 Austria 30 $2,000 ¥180,000 Lithuania 20 $2,000 ¥180,000 Azerbaijan 11 $1,100 ¥99,000 Malaysia 5 $500 ¥45,000 Belarus 15 $1,500 ¥135,000 Mexico 19 $1,900 ¥171,000 Belgium 27 $2,000 ¥180,000 Moldova 4 $400 ¥36,000 Brazil 12 $1,200 ¥108,000 Mongolia 5 $500 ¥45,000 Bulgaria 29 $2,000 ¥180,000 Netherlands 8 $800 ¥72,000 Canada 13 $1,300 ¥117,000 New Zealand 19 $1,900 ¥171,000 China 15 $1,500 ¥135,000 Norway 16 $1,600 ¥144,000 Chinese Taipei 5 $500 ¥45,000 Pakistan 5 $500 ¥45,000 Costa Rica 1 $100 ¥9,000 Peru 7 $700 ¥63,000 Croatia 11 $1,100 ¥99,000 Poland 19 $1,900 ¥171,000 Cuba 18 $1,800 ¥162,000 Portugal 8 $800 ¥72,000 Cyprus 21 $2,000 ¥180,000 Romania 27 $2,000 ¥180,000 Czech Russian 18 $1,800 ¥162,000 3 $300 ¥27,000 Republic Federation Denmark 10 $1,000 ¥90,000 Saudi Arabia 5 $500 - observe Egypt 9 $900 - absent Singapore 21 $2,000 ¥180,000 Estonia 17 $1,700 ¥153,000 Slovakia 18 $1,800 ¥162,000 Finland 22 $2,000 ¥180,000 Slovenia 20 $2,000 ¥180,000 France 20 $2,000 ¥180,000 Spain 15 $1,500 ¥135,000 Germany 6 $600 ¥54,000 Sweden 28 $2,000 ¥180,000 Greece 7 $700 ¥63,000 Switzerland 24 $2,000 ¥180,000 Hungary 2 $200 ¥18,000 Syria 1 $100 ¥9,000 Iceland 9 $900 ¥81,000 Tajikistan 7 $700 - IUPAC India 9 $900 ¥81,000 Thailand 11 $1,100 ¥99,000 Indonesia 11 $1,100 ¥99,000 Turkey 17 $1,700 ¥153,000 I. R. of Iran 18 $1,800 ¥162,000 Turkmenistan 9 $900 ¥81,000 Ireland 13 $1,300 ¥117,000 Ukraine 17 $1,700 ¥153,000 Israel 5 $500 ¥45,000 United Kingdom 1 $100 ¥9,000 Italy 17 $1,700 ¥153,000 United States 18 $1,800 ¥162,000 Japan 0 $0 ¥0 Uruguay 12 $1,200 ¥108,000 Kazakhstan 13 $1,300 ¥117,000 Venezuela 18 $1,800 - IUPAC Korea 4 $400 ¥36,000 Viet Nam 15 $1,500 ¥135,000 121 Budget of the 42nd IChO (Estimation as of September 15.)

3 103 Yen 10 US $ ($1 = ¥90) Total budget ¥411,992 $4,578 1. Government Sources ¥235,105 $2,612 2. Sponsors ¥153,176 $1,702 3. Country Participation Fees ¥7,506 $83 4. Observer and Guest Fees ¥16,205 $180 Expenditures ¥411,992 $4,578 1. Examination Preparation ¥52,222 $580 1.1 Equipment and Reagents ¥42,017 $467 1.2 Preparatory and Examination Tasks ¥10,205 $113 2. Accommodation and Food ¥55,307 $615 2.1 Students and Guides ¥24,283 $270 2.2 Mentors etc. ¥31,024 $345 3. Transportation ¥20,108 $223 3.1 Students and Guides ¥15,474 $172 3.2 Mentors etc. ¥4,634 $51 4. Ceremonies and Banquet ¥31,648 $352 4.1 Opening and Closing Ceremonies ¥13,246 $147 4.2 Banquet etc. ¥18,402 $204 5. Cultural Program ¥7,442 $83 5.1 Students and Guides ¥6,958 $77 5.2 Mentors etc. ¥484 $5 6. Secretariat ¥81,686 $908 6.1 Staff Costs ¥56,122 $624 6.2 Facilities ¥16,647 $185 6.3 Equipment and Services ¥8,917 $99 7. Guides ¥19,365 $215 8. Public Relations ¥48,890 $543 8.1 Catalyzers ¥5,944 $66 8.2 Souvenirs ¥7,478 $83 8.3 Presentation, Mass Media ¥35,468 $394 9. IT Support ¥5,354 $59 10. Final Report ¥1,200 $13 11. Operational Expenses ¥47,824 $531 11.1 Personnel ¥13,298 $148 11.2 Facilities and Services ¥28,968 $322 11.3 Consumables ¥2,632 $29 11.4 Communication ¥2,926 $33 12. Others ¥14,269 $159 13. Preliminary Events ¥26,677 $296

122

List of Organizers

President Ryoji Noyori (RIKEN)

Organizing Committee Chair: Ryoji Noyori (RIKEN) Deputy Chair: Hiroyuki Nakanishi (Mitsui Chemicals, Inc.) Kuniaki Tatsuta (Waseda University) Tadashi Watanabe (The University of Tokyo) Tetsuji Yanami (Daicel Chemical Industries Limited.) Member: President of Waseda University (Katsuhiko Shirai) President of The University of Tokyo (Hiroshi Komiyama, Junichi Hamada) President of the Association for the Progress of New Chemistry (Mitsuo Ohashi, Ryuichi Tomizawa) President of Catalysis Society of Japan (Makoto Imanari, Takashi Tatsumi, Miki Niwa) President of the Ceramic Society of Japan (Teruyoshi Hiraoka, Eiichi Yasuda, Katsuji Fujimoto, Koichi Niihara) President of the Chemical Society of Japan (Akira Fujishima, Hiroyuki Nakanishi, Yasuhiro Iwasawa) President of the Electrochemical Society of Japan (Zempachi Ogumi, Makoto Yoda, Ken-ichiro Ota, Higashi Ito) President of Japan Chemical Industry Association (Ryuichi Tomizawa, Hiromasa Yonekura) President of The Japan Institute of Energy (Takao Kashiwagi, Koji Ukekawa) President of Japan Oil Chemists' Society (Toshihiro Ito, Hiroyuki Shimasaki) President of the Japan Petroleum Institute (Eiichi Kikuchi, Toshikazu Kobayashi) President of The Japan Society for Analytical Chemistry (Hideaki Koizumi, Hiroki Haraguchi, Hitoshi Watarai, Hiroshi Nakamura) President of Japan Society for Bioscience, Biotechnology, and Agrochemistry (Shuichi Kaminogawa, Akira Isogai, Sakayu Shimizu,) President of The Pharmaceutical Society of Japan (Masakatsu Shibasaki, Hideo Utsumi, Tetsuo Nagano, Norio Matsuki) President of The Society of Chemical Engineers, Japan (Kouichi Miura, Kanji Shono, Takashi Tsuchiya) President of The Society of Polymer Science, Japan (Hiroyuki Nishide, Mitsuo Sawamoto) President of The Society of Synthetic Organic Chemistry, Japan (Takeshi Nakai, Ryozo Sakoda, Fukuyama Tohru) Kenji Tsuboi (Japan Science Foundation) Ken Takahashi (Mitsui Chemicals, Inc.) Masato Ito (Soka University) Takayuki Homma (Waseda University) Kazuaki Kudo (The University of Tokyo) Hiroshi Tachibana (Tokyo Metropolitan University) Makoto Onaka (The University of Tokyo) Yoshiyuki Sugahara (Waseda University)

Observers: Ministry of Education, Culture, Sports, Science and Technology (Kimihiko Oda, Yasutaka Moriguchi, Shinichiro Izumi) Ministry of Economy, Trade and Industry (Tetsuhiro Hosono, Tomofumi Hiraku) Science Council of Japan (Yasuhiro Iwasawa, Akira Fujishima) Japan Science and Technology Agency (Koichi Kitazawa, Toru Amano, Yutaka Hishiki) Japan Chemical Innovation Institute (Akiyoshi Somemiya, Kazuhiko Hiyoshi) Japan Society of Physics and Chemistry Education (Yasuo Tomioka) Zenkoku Tyugakkou Rikakyouiku Kenkyukai (Kunio Ryuzaki, Eiji Seta, Akira Miyashita) Japan Broadcasting Corporation (Nobuo Hayakawa)

123

The Asahi Shimbun (Atsuko Tsuji ) The Chemical Daily (Hiroshi Seta) The Chunichi Shimbun (Hajime Hikino, Tadashi Himeno) The Mainichi Newspapers (Yukiko Motomura, Hidetoshi Togasawa, Kazuhisa Nakai) Nikkei Inc. (Junichi Taki) Sankei Shimbun Co. (Shohei Nagatsuji) The Science News Ltd (Fujita Ikeda) The Yomiuri Shimbun (Shigeyuki Koide, Fumitaka Shibata)

Operating Managers (*: Chair) Tadashi Watanabe (The University of Tokyo)* Hiroyuki Nakanishi (Mitsui Chemicals, Inc.) Kuniaki Tatsuta (Waseda University) Tetsuji Yanami (Daicel Chemical Industries Limited.) Masahiro Kobayashi (IChO Japan Committee Secretary General)

Finance Committee (*: Chair) Tetsuji Yanami (Daicel Chemical Industries Limited.)* Kayo Sakata (Daicel Chemical Industries Limited.) Fumiyuki Asano (Daicel Chemical Industries Limited.) Michio Tanaka (Mitsui Chemicals, Inc.) Keizo Tajima (Mitsui Chemicals, Inc.) Nobuyuki Kawashima (The Chemical Society of Japan) Teruto Ohta (The Chemical Society of Japan) Hiroshi Moriya (Japan Chemical Industry Association) Shigeo Okumura (Japan Chemical Industry Association) Kenzo Tamura (Japan Chemical Industry Association) Ryoichi Nakano (Japan Science Foundation) Masahiro Niwano (The Society of Polymer Science, Japan) Masahiko Iyoda (Tokyo Metropolitan University) Kazunori Kataoka (The University of Tokyo)

Funding Committee (*: Chair) Hiroyuki Nakanishi (Mitsui Chemicals, Inc.)* Satoshi Kamata (Asahi Glass Co., Ltd.) Yuji Mizuno (Asahi Kasei Corporation) Tetsuji Yanami (Daicel Chemical Industries Limited.) Shunji Ehara (DIC Corporation) Shinpei Ikenoue (Fujifilm Corporation) Katsuki Miyauchi (Hitachi Chemical Company, Ltd.) Shuichi Ohmiya (Idemitsu Kosan Co., Ltd.) Hozumi Sato (JSR Corporation) Satomi Takahashi (Kaneka Corporation) Toshiharu Numata (Kao Corporation) Atsushi Baba (Mitsubishi Chemical Corporation) Kuniaki Kawakami (Mitsubishi Gas Chemical Company, Inc.) Hiroshi Tokumaru (Mitsui Chemicals, Inc.) Kan Ueno (Nippon Oil Corporation) Yuichi Kita (Nippon Shokubai Co., Ltd.) Takeshi Yoshida (Sekisui Chemical Co., Ltd.) Koji Kudo (Showa Denko K.K.) Giichi Morita (Teijin Limited) Tamotsu Yahata (Sumitomo Bakelite Co., Ltd.) Hideaki Ezaki (Sumitomo Bakelite Co., Ltd.) Yoshimasa Takao (Sumitomo Chemical Company, Limited) Norio Tsuzumi (The Tokyo Electric Power Company, Inc.) Nobuyuki Kuramoto (Tokuyama Corporation) Norihiko Saito (Toray Industries, Inc.) Hiroshige Wagatsuma (Tosoh Corporation) Makoto Umezu (Ube Industries, Ltd.) Kenji Tsuboi (Japan Science Foundation)

Sub-committee on Fund-raising (*: Chief) Ken Takahashi (Mitsui Chemicals, Inc.)* Tadashi Takamizawa (Asahi Kasei Corporation) Hiroshi Gouda (Asahi Kasei Corporation) Takashizu Minato (Asahi Glass Co., Ltd. Ryutaro Yamaki (Asahi Glass Co., Ltd.) Akiko Matsumoto (Daicel Chemical Industries Limited.) Akira Konishi (DIC Corporation) Takatoshi Ishikawa (Fujifilm Corporation) Shunichi Aida (Fujifilm Corporation) Masahiko Okamura (Hitachi Chemical Company, Ltd.) Keiichiro Yoshi (Idemitsu Kosan Co., Ltd.) Masaru Ohta (JSR Corporation) Hideyuki Matsui (Kaneka Corporation) Toru Tejima (Kao Corporation) Kimihiko Hori (Kao Corporation) Satoshi Kusunoki (Mitsubishi Chemical Corporation) Hiroshi Katayama (Mitsubishi Chemical Corporation) Daiji Tsuchiyama (Mitsubishi Chemical Corporation) Yoshinao Kashima (Mitsubishi Gas Chemical Company, Inc.) Naruyuki Nagaoka (Mitsubishi Gas Chemical Company, Inc.) Yasushi Kanda (Nippon Oil Corporation) Miaki Asakawa (Nippon Shokubai Co., Ltd.) Kiyokazu Kato (Sekisui Chemical Co., Ltd.) Tetsuzo Ishikawa (Showa Denko K.K.)

124

Fumio Kondo (Teijin Limited) Nobuyuki Tamura (Sumitomo Bakelite Co., Ltd.) Kaoru Sato (Sumitomo Chemical Company, Limited) Yuji Masuda (The Tokyo Electric Power Company, Inc.) Yutaka Shiokawa (Tosoh Corporation) Syuichi Nakai (Tosoh Corporation) Kunihiko Fujii (Tokuyama Corporation) Kimikazu Nagase (Toray Industries, Inc.) Tokio Obata (Ube Industries, Ltd.)

Execution Committee (*: Chair) Tadashi Watanabe (The University of Tokyo)* Masato Ito (Soka University) Takayuki Homma (Waseda University) Kazuaki Kudo (The University of Tokyo) Makoto Onaka (The University of Tokyo) Yoshiyuki Sugahara (Waseda University) Kayo Sakata (Daicel Chemical Industries Limited.) Ken Takahashi (Mitsui Chemicals, Inc.) Ryoichi Nakano (Japan Science Foundation)

Subcommittee on General Affairs (*: Chief) Masato Ito (Soka University)* Kensuke Arai (Nihon Pharmaceutical University) Satoshi Arai (Waseda University) Takayuki Homma (Waseda University) Eiji Iwato (Tokyo Gakugei University Senior High School) Hajime Hosoi (Waseda University) Kensei Kobayashi (Yokohama National University) Kenya Kubo (International Christian University) Kazuaki Kudo (The University of Tokyo) Fumitaka Mafune (The University of Tokyo) Makoto Minato (Yokohama National University) Minoru Seki (Chiba University) Akio Shimizu (Soka University) Yoshiyuki Sugahara (Waseda University) Makoto Onaka (The University of Tokyo) Hiroshi Tachibana (Tokyo Metropolitan University)

Subcommittee on Public Relations (*: Chief) Takayuki Homma (Waseda University)* Yoshinobu Aoyama (Japan Chemical Industry Association) Hideki Hayashi (Nagoya Municipal Industrial Research Institute) Ayumu Inoue (Japan Chemical Industry Association) Takaki Kanbara (University of Tsukuba) Masaki Karayama (Toyo University) Shigeru Machida (Tokyo National College of Technology) Atsunori Mori (Kobe University) Chigusa Rao (Japan Science and Technology Agency Shigeo Satokawa (Seikei University) Hiroshi Seta (The Chemical Daily) Yuki Yamasaki (Hosei University)

Catalyzer Editors (*: Chief) Haruo Hosoya* Atsunori Mori (Kobe University) Shigeru Machida (Tokyo National College of Technology) Hiroshi Seta (The Chemical Daily) Daisuke Takeushi (Tokyo Institute of Technology) Akiko Utagawa (Tama University Hijirigaoka High School and Junior High School) Yuki Yamasaki (Hosei University)

Preliminary Task Group (*: Chief) Masaki Karayama (Toyo University)* Yasunao Kuriyama (Yamagata University) Kazuo Fujioka (Suginami Gakuin Junior and Senior High School) Eiji Iwato (Tokyo Gakugei University Senior High School) Shiho Kamiya (Senzoku Gakuen Junior and Senior High School) Kazuhiro Miyamoto (The Kaisei Junior and Senior High School) Tomohiro Watanabe (Rikkyo Niiza Junior and Senior High School) Masakatsu Takamatsu Yuki Yamasaki (Hosei University)

Subcommittee on Events and Transportation (*: Chief) Kazuaki Kudo (The University of Tokyo)* Kazuo Fujioka (Suginami Gakuin Junior and Senior High School) Eiji Iwato (Tokyo Gakugei University Senior High School) Masaki Karayama (Toyo University) Yoshitaka Minai (Musashi University) Masatada Matsuoka (Komaba Toho Junior and Senior High School )

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Tomomi Samejima (Tokyo Gakugei University International Secondary School) Yukihiko Ueno (Waseda University Honjo Senior High School) Akiko Utagawa (Tama University Hijirigaoka High School and Junior High School) Tomohiro Watanabe (Rikkyo Niiza Junior & Senior High School)

Subcommittee on Information Technology (*: Chief) Hiroshi Tachibana (Tokyo Metropolitan University)* Shoji Matsumoto (Chiba University)

Scientific Committee (*: Chair) Kuniaki Tatsuta (Waseda University)

Sub-committee on Practical Exam (*: Chief) Yoshiyuki Sugahara (Waseda University)* Nobuhiro Kanomata (Waseda University) Jun Matsuoka (The University of Shiga Prefecture) Masahiko Murakami (Nihon University) Kazuo Nagasawa (Tokyo University of Agriculture and Technology) Kazuki Nakanishi (Kyoto University) Teruyuki Nakato (Tokyo University of Agriculture and Technology) Kenji Ogino (Tokyo University of Agriculture and Technology) Kenichi Oyaizu (Waseda University) Satoshi Tsukahara (Hiroshima University) Hiroyuki Yamamoto (Waseda University)

Subcommittee on Theoretical Exam (*: Chief) Makoto Onaka (The University of Tokyo)* Yukihiko Hashimoto (The University of Tokyo) Hiroyuki Kagi (The University of Tokyo) Hitoshi Kawaji (Tokyo Institute of Technology) Hiroshi Kondoh (Keio University) Fumitaka Mafune (The University of Tokyo) Masaru Miyayama (The University of Tokyo) Akira Miyoshi (The University of Tokyo) Kazuki Morita (The University of Tokyo) Kiyotaka Shigehara (Tokyo University of Agriculture and Technology) Kiyotake Suenaga (Keio University) Toshiki Sugai (Toho University) Koichi Tsukiyama (Tokyo University of Science) Takeshi Wada (The University of Tokyo) Atsuo Yasumori (Tokyo University of Science) Naoko Yoshie (The University of Tokyo)

Secretary Office (*: Secretary General) Masahiro Kobayashi* Makiko Akaho

Supporting Staffs at Secretary Office Shigeru Endo (Chemical Society of Japan) Jun Miyasaka (Japan Science Foundation) Yusuke Kawase (Chemical Society of Japan) Hiroyuki Okura (Chemical Society of Japan) Hirokazu Shimizu (VIC Computer Support) Chigusa Rao (Japan Science and Technology Agency) Atsuyo Yoshimi (Japan Science and Technology Agency) Ako Imaoka Megumi Tanabe

Guides Students Ayasa Aizawa (Waseda University) Shinichi Akizuki (Soka University) Dashdemberel Batchunag (Tokyo Institute of Technology) Chew Sok Chen (Soka University) Mayumi Chiba (International Christian University) Imon Cho (International Christian University) Andrei Dinu-lonita (Columbia University) Takahisa Fujimori (The University of Tokyo) Miki Fukuda (International Christian University) Shinya Fukuzawa (The University of Tokyo) Mitsuha Furuie (International Christian University) Jambaldorj Ganchimeg (Tokyo Institute of Technology) Norito Hagino (Soka University of America) Nozomi Hayashi (University of Birmingham) Yukei Hirasawa (International Christian University) Leung Wai Hong (Soka University) Yuki Hori (International Christian University) Sayuri Ikeda (International Christian University) Kazuhiko Imai (Soka University of America) Rie Inoue (Osaka University) Sho Ishiwata (International Christian University) Miho Isobe (Soka University of America) 126

Amane Iwai (International Christian University) Taeko Iwamoto (Soka University of America) Seiichi Izumi (Soka University of America) Satsuki Kamihagi (University of Nottingham) Kyohei Kanomata (Tohoku University) Tomoko Kawabe (International Christian University) Kazuki Kimura (Waseda University) Shiori Kitajima (International Christian University) Yasuhito Koda (Tokyo University of Science) Hirotomo Kou (The University of Tokyo) Zahariev Ivan Krasimirov (The University of Tokyo) Eri Kubota (International Christian University) Qu Jun Lan (Soka University) Marina Masuda (International Christian University) Fumiko Matsushima (Soka University) Qu Mengxuan (International Christian University) Sa Migeum (Waseda University) Soetrisno Misawa (DIC Co.) Maiko Miura (Soka University of America) Gorgoll Ricardo Mizoguchi (The University of Tokyo) Mariko Monoi (International Christian University) Moe Murai (International Christian University) Kenichi Nagasawa (Soka University of America) Misato Nakano (Takushoku University) Mari Nakamura (Tokyo University of Agriculture and Technology) Mika Nakaoka (Waseda University) Nobuyuki Nakatomi (Soka University) Minako Nishiyama (Soka University) Mariko Nitta (Waseda University) Remi Nozaki (Aoyama Gakuin University) Mari Ogasa (Ochanomizu University) Haruka Ohtake (International Christian University) Ayako Osada (International Christian University) Naoya Otsuka (University of Tsukuba) Izmailov Ramazan (Takushoku University) Fatemeh Rezaeifar (The University of Tokyo) Naomi Sakai (University of Cambridge） Keiko Sato (Soka University of America) Yuriko Sato (Soka University of America) Shiori Sawasaka (International Christian University) Goh Lee See (Soka University) Aiki Segawa (Soka University of America) Asaka Seki (International Christian University) Shuto Seki (International Christian University) Mia Suda (Takushoku University) Jun Sumida (International Christian University) Miho Suzuki Shunsuke Takagi (Tokyo University of Science) Misaki Takano (International Christian University) Masayuki Takeuchi (Soka University of America) Haruka Tashiro (International Christian University) Terumi Terashima (International Christian University) Minori Tomidokoro (Takushoku University) Riho Ueno (International Christian University) Rina Watanabe (International Christian University) Kanae Yama (International Christian University) Asako Yamada (Tokyo University of Foreign Studies) Chiharu Yamamura (International Christian University) Noyuri Yamamura (International Christian University) Rodrigo Kendy Yamashita (The University of Tokyo) Yukiko Yano (International Christian University) Mitsuhiro Yoshimura (The University of Tokyo) Tomoe Yuasa (Tokyo University of Foreign Studies) Shang Yuying (Keio University)

Mentors, Observers and Guests Hiroko Aiso (Keio University) Xu Chen (International Christian University) Takuya Ishida (The University of Tokyo) Shingo Ishikawa (Hosei University) Yoshie Ishikawa (Soka University) Riku Sato (International Christian University) Yoshiko Sugita (Soka University of America) Nozomu Suzuki (International Christian University) Junko Taira (Soka University of America) Saki Takanashi (Yokohama National University) Miki Takata (Soka University) Ang Foong Yee (Soka University) Atsushi Yoshitake (Tokyo Institute of Technology)

Supporting Staffs NYC Maho Fujita (Tokyo University of Science) Chisa Koda (International Christian University) Sumire Kurosawa (Tokyo University of Pharmacy and Life Sciences) Sumire Ono (The University of Tokyo) Yoshiyuki Takasu (Soka University of America) Yoshiki Tanaka (The University of Tokyo) Nozomi Yoshikawa (Nihon Pharmaceutical University)

OVTA Kazuya Aoki (The University of Tokyo) Miyuki Hashimoto (International Christian University) Yohei Hattori (The University of Tokyo) Satomi Inagaki (International Christian University) Yuki Ito (The University of Tokyo) Katsuyoshi Kimigafukuro (Kobe University) Kazuki Ootaka (The University of Tokyo) Toru Takazawa (Overspec Production Studio)

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Catalyzer Yohei Mark Odagiri (Hosei University) Ryu Kojima (Hosei University) Tomohito Ide (Tokyo Institute of Technology) Masahiro Suzuki (Hosei University ) Yoshitaka Tsuchido (Tokyo Institute of Technology)

Information Technology Batmunkh Erdenebolor (Chiba University) Dai Hirahara (Chiba University) Hirokazu Kageyama (Chiba University) Koji Takagi (Chiba University) Tomoko Tsuji (Chiba University)

Practical Exam Kenichi Aizawa (Waseda University) Tomoko Akama (Waseda University) Yuta Asai (Waseda University) Yusuke Ariake (Waseda University) Wonsung Choi (Waseda University) Tomohiro Fukuda (Waseda University) Shan Gen (Waseda University) Ryotarou Hara (Waseda University) Shinpei Hatano (Waseda University) Masatoshi Hattori (Waseda University) Syou Hideshima (Waseda University) Yuuki Honda (Waseda University) Keiske Iida (Tokyo University of Agriculture and Technology) Seijiro Hosokawa (Waseda University) Shuhei Hotta (Waseda University) Takuya Imaoka (Tokyo University of Agriculture and Technology) Machi Ito (Waseda University) Masanori Ito (Waseda University) Yuki Iwamoto (Waseda University) Yoshie Kaifu (Waseda University) Hisashi Kambe (Waseda University) Taichi Kaneko (Waseda University) Mizuki Kamishiro (Waseda University) Yosuke Kanno (Waseda University) Miki Kanao (Tokyo University of Agriculture and Technology) Yasuhiro Kataoka (Waseda University) Ryo Kawahara (Waseda University) Kazuo Kimura (Waseda University) Nanako Kimura (Waseda University) Chiaki Kobayashi (Waseda University) Manabu Kobayashi (Waseda University) Miyuki Kobayashi (Waseda University) Yuta Kobayashi (Waseda University) Fumitaka Kondoh (Waseda University) Akiko Kubota (Waseda University) Masahiro Kunimoto (Waseda University) Yoshiyuki Kuroda (Waseda University) Masato Matsuda (Waseda University) Kaoru Matsushita (Waseda University) Ayumi Matsuo (Waseda University) Kanao Miki (Waseda University) Yoshihiro Minamino (Tokyo University of Agriculture and Technology) Noriko Mitsui (Waseda University) Katsuyoshi Miura (Waseda University) Takahiro Mochizuki (Waseda University) Toshiyuki Monma (Waseda University) Yuki Mukaeda (Waseda University) Shintaro Nagahama (Waseda University) Mai Nagashima (Waseda University) Makoto Nakabayashi (Waseda University) Sho Nakagawa (Waseda University) Satoshi Nakajima (Waseda University) Chu Nakamura (Waseda University) Atsushi Nakata (Waseda University) Kuniko Nitta (Waseda University) Takashi Niwa (Waseda University) Toshiya Ohba (Waseda University) Mayumi Okamoto (Waseda University) Teruyuki Okayasu (Waseda University) Hiroyoshi Ootsu (Waseda University) Takanari Oouchi (Waseda University) Shimon Osada (Waseda University) Hiroshi Oshio (Waseda University) Hitomi Saito (Waseda University) Heisuke Sakai (Waseda University) Junji Seino (Waseda University) Keisuke Seto (Waseda University) Toshimichi Shibue (Waseda University) Tsuyoshi Shimada (Waseda University) Syunsuke Sueki (Waseda University) Teiichi Someya (Waseda University) Natsuhiko Sugimura (Waseda University) Kazuhiro Sugiyama (Waseda University) Hiromi Sunaga (Waseda University) Katsumi Suzuki (Waseda University) Nagisa Toihara (Waseda University) Chihiro Urata (Waseda University) Chisato Yamazaki (Waseda University) Yuji Takagi (Waseda University) Katsuyuki Takahashi (Waseda University) Nobuyuki Takahashi (Waseda University) Yoshie Takakura (Waseda University) Takeko Takano (Waseda University) Shigeo Tanabe (Waseda University) Jun Tanaka (Waseda University) Shiro Tanie (Waseda University) Masayuki Tera (Waseda University) Sonoko Tokishita (Waseda University) Hitomi Tsukagoshi (Waseda University) Ryo Watabe (Waseda University) 128

Naoko Watanabe (Waseda University) Masamichi Yamada (Waseda University) Yusuke Yamamoto (Waseda University) Naoki Yokoyama (Waseda University) Koji Yasui (Tokyo University of Agriculture and Technology) Shogo Yonemura (Waseda University) Shinpei Yoshida (Waseda University) Yuri Kodachi

Theoretical Exam Kiyohiro Adachi (The University of Tokyo) Mitsunori Araki (Tokyo University of Science) Junta Fuchiwaki (The University of Tokyo) Junichi Furukawa (The University of Tokyo) Daijiro Hayashi (The University of Tokyo) Hidenori Himeno (The University of Tokyo) Yojiro Hiranuma (The University of Tokyo) Ryota Horikawa (The University of Tokyo) Hiroshi Hyodo (Tokyo University of Science) Junichi Ishida (The University of Tokyo) Tomoyuki Iwamoto (The University of Tokyo) Takuya Kaji (The University of Tokyo) Yusuke Kanakubo (The University of Tokyo) Yuji Katagiri (The University of Tokyo) Ryoichi Kira (The University of Tokyo) Yuta Kirihara (The University of Tokyo) Shunsuke Kodama (The University of Tokyo) Yoichi Masui (The University of Tokyo) Akira Matsugi (The University of Tokyo) Hiroaki Matsumoto (The University of Tokyo) Ken Miyajima (The University of Tokyo) Haruko Miyake (The University of Tokyo) Maho Morita (Keio University) Toshiaki Nagata (The University of Tokyo) Naoya Nakajima (Keio University) Tomoki Nishiguchi (The University of Tokyo) Nobuhiro Ooya (The University of Tokyo) Yuki Saito (The University of Tokyo) Motohiro Sakamoto (The University of Tokyo) Kei-ichi Sato (The University of Tokyo) Kazuhiro Shikinaka (Tokyo University of Agriculture and Technology) Ichiro Tanabe (The University of Tokyo) Naru Tanaka (The University of Tokyo) Mituru Tomita (The University of Tokyo) Kosuke Tsuchiya (Tokyo University of Agriculture and Technology) Akira Yamada (The University of Tokyo) Kazuya Yamada (The University of Tokyo) Hirotaka Yamamoto (The University of Tokyo) Sayaka Yanagida (Tokyo University of Science) Hirotaka Yonezawa (The University of Tokyo) Yuki Nakamura (The University of Tokyo) Chigako Yoshida (The University of Tokyo) Eunjin Bae (Tokyo Metropolitan Kokusai H. S.) Winnie Chan (Tokyo Metropolitan Kokusai H. S.) Marina Dan (Tokyo Metropolitan Kokusai H. S.) Sara David (Tokyo Metropolitan Kokusai H. S.) Minami Fujisawa (Tokyo Metropolitan Kokusai H. S.) Jyunka Funaki (Tokyo Metropolitan Kokusai H. S.) Eri Hanzawa (Tokyo Metropolitan Kokusai H. S.) Kei Kaneshiro (Tokyo Metropolitan Kokusai H. S.) Shin Kim (Tokyo Metropolitan Kokusai H. S.) Minori Kunii (Tokyo Metropolitan Kokusai H. S.) Haein Lee (Tokyo Metropolitan Kokusai H. S.) Hiromu Narita (Tokyo Metropolitan Kokusai H. S.) Chokkaku Otobe (Tokyo Metropolitan Kokusai H. S.) Seinan Saku (Tokyo Metropolitan Kokusai H. S.) Gabriel Sato (Tokyo Metropolitan Kokusai H. S.) Safia Sexton (Tokyo Metropolitan Kokusai H. S.) Mutsumi Takase (Tokyo Metropolitan Kokusai H. S.) Kaho Takeda (Tokyo Metropolitan Kokusai H. S.) Nan Tang (Tokyo Metropolitan Kokusai H. S.) Aki Tempaku (Tokyo Metropolitan Kokusai H. S.) Hidehiro Ushijima (Tokyo Metropolitan Kokusai H. S.)

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IChO Japan Committee