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37th International Chemistry Olympiad

Taipei, Taiwan

Practical Examination Tuesday, 19 July !!"

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Language: Important #emar$s

The plastic bag you got upon entering the laboratory is the unknown samples for experiment 2. Put it inside the basket on your bench for later use. At all times while you are in the laboratory you should wear safety spectacles or your own spectacles if they have been approved. Eating of any kind of food is strictly prohibited in the laboratory. When you enter the laboratory check the place of the safety shower. Participants are expected to work safely to behave socially and to keep e!uipment and work environment clean. "o not hesitate to ask a laboratory assistant if you have any !uestions concerning safety issues. %or$ may only &e'in when the start si'nal is 'i(en) #ou have $ hours to complete all of the experimental tasks and record your results on the answer sheets. There will be a pre%warning &' minutes before the end of your time. #ou must stop your work immediately after the stop command is given. A delay in doing this by $ minutes will lead to cancellation of the current task and will result in (ero points for that task. This practical examination comprises two experiments) In order to use the a(aila&le time e**iciently, you will start wor$in' on the or'anic chemistry experiment up to the point where you are instructed to wor$ on the analytical chemistry experiment) Then you will *inish the wor$ on the or'anic chemistry experiment) The second part o* the or'anic experiment +experiment 1, will need at least 1 hour) -se only the pen and calculator pro(ided) Write your name and personal identification code )in the back of your name card* on every answer sheets. All results must be written in the answer boxes on the answer sheets. "ata written elsewhere will not be marked. "o not write anything in the back of your answer sheets. +f you need more paper for working or a replacement answer sheet re!uest it from the laboratory assistant. When you have finished the examination you must put all answer sheets into the envelope provided. ,nly papers in the envelope will be marked. "o not leave the examination room until you have permission to do so. -se only the tools provided. There are total " pages of answer sheets . for organic and 1 for analytical experiment respectively. . blank draft papers )will not be marked* are provided more are available on re!uest
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An official English%language version is available only on re!uest.

/isposal o* waste chemicals, spills, and 'lassware

There are three waste containers in the lab one for organic filtrates and organic washings one for solid wastes and one for broken glass.

Cleanin' up Please keep your work area clean. Wipe your lab bench with a wet tissue when you are finished.

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Language: Or'anic synthesis

Equipment list
e!uipment 0ot plate1stirrer with stand 3tirrer /o. 2 2 e!uipment Weighing paper 3ample vial )2' m4* /o. 2' 2

(blue label labelled with your student code and 1H NMR)

3tirrer retriever 3hared by 2 persons 3ample vial )2' m4* 2

(pink label labelled with your student code and []D)

6lass rod 2

5iltration pump

3hared by 2 persons

7lamp with holder thermometer Pasteur pipette Pipette bulb 6raduated cylinder )2' m4* 6raduated cylinder)2$ m4* 8ound bottom flask )2$ m4* 8ound bottom flask )$' m4* 5ilter 5ritted )$' m4*

& 2 $ 2 2 2 2 2 2

3patula 3epta Water bath )stainless steel* +ce bath )3tyrofoam* /eedle Water bottle with "eioni(ed 02, 6love )cotton* 6love )latex* on central bench 5lask holder

2 2 2 2 2 2 2 pair

2 pc

(labelled with your student code)

5ilter 5ritted )9' m4* 2 Paper towel 2 roll

(labelled with your student code)

5iltration flask with rubber )2$' m4* 7ondenser Teflon sleeve for condenser (you can trim off 1 cm from the smaller end for a better fit) 3afety goggles 2 ;eaker ).'' m4* 2 2 2 2 :imwipes 6lass funnel ;eaker )<'' m4* 2 box 2 2

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Chemical list
chemicals ethanol pre%mixed solvents ethylene glycol>ethanol )2>?* ben(oylformic acid ammonium formate " 4%phenylglycine 7<0=,& 07,2/0. 7<0?/,2 formula 720$,0 )702,0*2

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formula weight .=.'9 % 2$'.2& =&.'= 2$2.2=

amount $' m4 $' m4 written on sample vial 9.$9 g written on sample vial )to be provided for step 2*

8isk 22 22 &=1&91&< &=1&91&< %

3afety 9%2= % 2=%2<%&= 2=%&= 22%2.12$

statements statements

Pentamethylcyclopentadien yl%rhodium)+++* chloride dimer )2S*%)B*%2'% camphorsulfonic acid )B*% )73A*

@)70&*$7$8h 7l2A2 72'02=,.3

&9.2 mg

2'122122 &=1&91&<

2= &=

2&2.&'

2.<' g

&.

2=% &=1&91&?% .$

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8 22 8 2' 8 22 8 2$ 8 &2 8 &2 8 &. 8 &$ 8 &= 8 &9 8 &< 8 .' 8 .2 8 .& 8 $' 8 $2 8 $& 0ighly flammable. 0armful by inhalation. 0armful if swallowed. Toxic if swallowed.

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7ontact with acids liberates toxic gas. 7ontact with acid liberates very toxic gas. 7auses burns. 7auses severe burns. +rritating to eyes. +rritating to respiratory system. +rritating to skin. 4imited evidence of a carcinogenic effect 8isk of serious damage to the eyes. Cay cause sensiti(ation by skin contact. Dery toxic to a!uatic organisms. 0armful to a!uatic organisms. Cay cause long%term adverse effects in the a!uatic environment.

7ombination of risk statements

8 2'122122 8 &=1&91&< 0armful by inhalation in contact with skin and if swallowed. +rritating to eyes respiratory system and skin.

3afety statements
39 3 2& 3 2= 3 22 3 2& 3 2&.2 3 2. 3 2= 3 2< 3 &' :eep container tightly closed. :eep away from food drink and animal foodstuffs. :eep away from sources of ignition % /o smoking. "o not breathe dust. "o not breathe gas1fumes1vapour1spray )appropriate wording to be specified by the manufacturer*. "o not breathe vapor. Avoid contact with skin. +n case of contact with eyes rinse immediately with plenty of water and seek medical advice. After contact with skin wash immediately with plenty of soap%suds. /ever add water to this product. !

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3 &= 3 &9 3&? 3 .2 3 .$ 3 =' 3 =2

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Wear suitable protective clothing. Wear suitable gloves. Wear eye 1 face protection. +n case of fire and1or explosion do not breathe fumes. +n case of accident or if you feel unwell seek medical advice immediately )show the label where possible*. This material and its container must be disposed of as ha(ardous waste. Avoid release to the environment. 8efer to special instructions 1 3afety data sheets.

7ombination of safety statements

3 2.12$ 3 &=1&91&? 3 &=1&9 3 &91&? Avoid contact with skin and eyes. Wear suitable protective clothing gloves and eye1face protection. Wear suitable protective clothing and gloves. Wear suitable gloves and eye1face protection.

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Language: Experiment 1

The 0ynthesis o* /,12Phenyl'lycine and Its Enantiomeric #esolution

,ne of the enantiomeric forms of phenylglycine is an important raw material for the preparation of %lactam antibiotics. +ndustrial production of optically active phenylglycine is prepared by the Andeno process. The starting ben(aldehyde was treated with 07/1/0 & following hydrolysis to give the racemic " 4%phenylglycine. The desired enantiomeric phenylglycine was then resolved by )B*% camphorsulfonic acid @)B*%73AA.
#
70,

1$ H%N& NH3 2$ Hydrolysis (+ndeno )rocess)

D&'()henyl*lycine

Rh catalyst H%##NH4 #

#H

;en(aldehyde

" 4%phenylglycine

;en(oylformic acid

+n this experiment you are going to synthesi(e racemic " 4%phenylglycine )also referred to as 8% and 3% isomers respectively* from an alternative method called reductive amination. Treatment of ben(oylformic acid under 8h metal cataly(ed conditions gives " 4%phenylglycine. The racemic " 4%phenylglycine is resolved by the treatment of )B*%73A in water. The solubility of "% phenylglycine)B*%73A salt is $.9$ g12''g 02, while that of 4%phenylglycine)B*%73A salt is E2$' g12''g 02, at 2$ F7. The chemical yield and the optical purity of the diastereomeric salt will be measured. E3PE#I4E5T61 P#OCE/-#E Caution7 8ou ha(e to wear latex 'lo(es durin' all operation *or practical tas$ 1) 0tep 1) Preparation o* /,12phenyl'lycine

The following pre-weighted chemicals can be used directly without further weighing: Benzoylformic Acid; Ammonium Formate; Rh Catalyst; !"-camphorsulfonic acid # !"C$A%&

2. To a $' m4 round%bottomed flask is added a magnetic stirring bar pre%weighed )approximate

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2.<' g exact mass will be on your sample bottle write down the mass on your answer sheet and get the lab assistant to confirm the weight.* of ben(oylformic acid ) 5OTE7 irritant' do not contact with s(in* 9.$9 g of ammonium formate )07, 2/0.* &9.2 mg of 8h catalyst )5OTE7 the catalyst is wrapped in a wei'hin' paper in a plastic &a') 9andle with care: * and 22 m4 of the pre%mixed solvents at ambient temperature. 2. Put a reflux condenser )use the Teflon sleeveG you can trim off 2 cm from the smaller end for a better fit* into the neck of the flask and plug the condenser with a septum. 5or pressure e!uilibration put a needle in the septum before starting the heating. 7lamp the apparatus tightly to the stand in your hot plate1stirrer. Put the flask onto a hot water bath @hot water provided by the organi(erA and stir the reaction mixture gently. ) 5OTE7 the sol(ent is air cooled, so there is no tap water runnin' throu'h the condenser) * The temperature of the water bath needs to be maintained in the range of =< to 92 F7 by adHusting the thermostat of the hot plate1stirrer. &. The mixture will become cloudy and the color of the solution will change from clear yellowish to dark%greenish when the product starts to precipitate )generally re!uiring 2$ I &$ minutes*. The hot water bath should then be removed and the solution allowed to stir in the water bath )ambient temperature* for an additional 2' minutes. .. Add 2$ m4 of deioni(ed water to the resulting mixture and stir for 2' minutes. $. Pre%weigh the bigger fritted glass funnel )labelled with your student code* and get the lab assistant to confirm the weight. -se the stir bar retriever to remove the stir bar. 7ollect the product by filter suction through a fritted glass funnel under a reduced pressure )rotary aspirator apparatus*. Wash the solid four times thoroughly with ethanol )2' m4 each*. 5or each washing brea( the aspirator pressure use a glass rod to perturb the solid when adding ethanol and reapply the rotary aspirator. =. 5or rapid drying you have to spread the product over the fritted glass funnel. 5or drying give the fritted glass funnel to the lab assistant. The product is dried in the oven at 2'' F7 for 2.$ hour.

)uring the drying period you can start wor(ing on *+periment , Analytical *+periment" and you will be notified when your product is ready& $tep , of e+periment - will need at least - hour&
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9. Weigh the dried product @)" 4*%phenylglycineA record the data and calculate the chemical yield )based on the starting ben(oylformic acid*. 6et the lab assistant to confirm the weight. The purity of the product will be determined by 20 /C8 spectrum analysis. Turn in the product in a vial )&lue la&el with 20 /C8 and your student code* to the lab assistant and receive a new batch of " 4%phenylglycine for step 2. 0tep ) Enantiomeric resolution o* /,12phenyl'lycine &y +;,2camphorsul*onic acid <+;,2C06= 2. To a 2$ m4 round%bottomed flask add the pre%weighed sample of " 4%phenylglycine provided )The exact mass will be on your sample bottle write down the mass on your answer sheet and get the lab assistant to confirm the weight*. To this add the pre%weighed )B*%camphorsulfonic acid @)B*%73AA )2.<' g*. 7lamp the apparatus tightly to a stand in a magnetic stirrer. Add deioni(ed water ). m4* and place the flask in a hot water bath and heat it to a temperature in the range of ?' I 2'' F7. :eep the mixture at this temperature for 2' minutes until it turns clear. 2. 8emove the hot water bath and allow the mixture to cool down to ambient temperature for 2'I2$ minutes. With the flask plugged with a septum cool the flask in ice bath )3tyroform* for 2$ minutes. 7rystals should appear in about 2' minutes if not you may ask for seed crystals to induce the crystalli(ation. &. Pre%weigh the smaller fritted glass funnel )labelled with your student code* and get the lab assistant to confirm the weight. 7ollect the product by filtering the solution through a fritted glass funnel under a reduced pressure. Wash the solid thoroughly two times with ice cooled distilled water )$ m4 each*.

.. 5or drying give the fritted glass funnel to the lab assistant. The product will be dried over in oven at 2'' F7 for 2' min. #ou will be notified when your product is ready. Weigh the product and get the lab assistant to confirm the weight. 8ecord the data and calculate the chemical yield )based on starting " 4%phenylglycine*. $. The optical purity of the diastereomeric salt will be measured using an accurate polarimeter apparatus by the examination committee. Transfer the dried product to a sample vial ) pin$ la&el labelled with @A" and your student code* and give the sample vial to the lab assistant)
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The organi(ation committee will weigh an appropriate amount of the product )'.'$$ I '.'=$g* for measurement of optical purity. The organization committee will weigh the resolved product (from the fritted glass funnel) for students who fail to finish the procedure in time. However, 1 penalty points will be ta!en.

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Language: Experiment Identi*ication o* -n$nown Inor'anic 0amples

5ote )2* This practical exercise is a kind of Jspot testK. #ou can do it on the pallet or on a sheet of black film )for white precipitate*. )2* Please check all items written in the e!uipment and reagent list. )&* Please chec$ care*ully the code num&er o* the un$nown sample with the Chec$ 1ist accompanied with your un$nown samples) ).* The volume of each unknown solution is about 2.$ m4 )about &' drops*. 5o more rea'ents or samples will &e pro(ided. )$* ;e sure to confirm your results before writing your answers in the blanks of the Answer 3heet. )=* Cake sure the switch on the battery box is closed. )9* 8ou will 'et > points *or each correct identi*ication) Introduction There are 22 unknown samples in your plastic bag ? unknown solutions are in droppers and & unknown solids are in vials. All unknown samples are numbered with a & digit code. Please check the number with the 1ist o* -n$nown Inor'anic 0amples carefully then write your student code and name on the list. )The list is accompanied with your unknown samples* Each vial contains about 2' mg of crystals or powder of one pure compound. Each dropper contains about 2.$ m4 solution of one pure compound dissolved in distilled water. The concentration of unknown solutions is in the range of '.'$ to '.$ C )mol14*.

The unknown samples are as follows> 07l /a,0 5ote )2* Two unknown samples are duplicates. )2* The hydrated 02, of crystal is omitted in the formulas listed above. 02,2 /a27,& 023,. /a23,& Ln7l2 ;a7l2 /0.37/ :.5e)7/*=

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,n your lab bench there is a plastic basket which contains the e!uipments unknown samples and reagents to be used in this task. E!uipment list e!uipment Pt wire electrode ;attery case Pallet 3cissors 7offee stirrer 8eagent list 8eagent :+ 5e7l& 7onc. '.2C '.2C 8eagent pp )phenolphthalein* 3tarch solution 7onc. '.'2 '.'2 /o. 2 2 2 2 2 e!uipment Au wire electrode ;attery ;lack film )round* "ropper )2 m4* /o. 2 2 2 $

8isk and safety statements 7hemicals 0ydrochloric acid 3ulfuric acid 3odium hydroxide solution 0ydrogen peroxide solution 3odium carbonate solution ;arium chloride solution 3odium sulfite solution Linc chloride solution Potassium hexacyanoferrate )++* solution Ammonium thiocyanate solution +ron )+++* chloride )solid* 5e7l&
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5ormula 07l 023,. /a,0 02,2 /a27,& ;a7l2 /a23,& Ln7l2 :.5e)7/*=

8isk statements &=1&91&< &$ &$ 22%.2 &= 2'%2$ &2%&=1&91&< 22%&.%$'1$& &2

3afety statements 2= 2=%&'%.$ 2=%&=1&91&?%.$ 2=%&? 22%2= .$ 2=%&= 2=%&=1&91&?%.$%='%=2 22%2.12$

/0.37/

2'122122%&2%$21$& 22%&.

2&%=2 2=%&=1&91&?%.$

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Potassium iodide )solid* 3tarch solution Phenolphthalein indicator :+ %

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% % .' 22%2.12$ M % &=1&9

,-- -se the four reagents provided and mutual reactions among the unknown samples and the simple electrolysis apparatus to identify each unknown sample and write your answer )& digit code* in the blanks of your answer sheet.

Note
+.ter you ha/e .inished your wor0& 1lease 1ut the two electrodes ()t and +u wires) and two batteries bac0 in their ori*inal 1lastic ba*s& res1ecti/ely& then return all e2ui13ent and rea*ents (include un0nown sa31les) to the ori*inal 1laces (in the 1lastic bas0et)$

,-,

+n this practical work you have performed a series of tests to identify )or confirm* the unknowns. 3how the reactions involved by way of chemical e!uations. A. Write the electrolysis e!uation that would help you confirm that an unknown sample is Ln7l2. ;. Write one e!uation that shows how to clean the deposit of Ln on the electrode )limited to the items provided in this task*.

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