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THEORETICAL EXAMINATION
J L! "#, "#$% MO&CO', R &&IA

(eneral )*rect*ons

Write down your name and code number on each page. You have 5 h to fulfill the tasks. Failure to stop after the S !" command may result in #ero points for the current task. Write down answers and calculations within the designated bo$es. %ive your work where re&uired. 'se only the pen and calculator provided. (f you need draft paper use the back side of the paper. (t will not be marked. here are %+ pages in the booklet including the answer bo$es) *over Sheet and "eriodic able. he official +nglish version is available on demand for clarification only. ,eed to go to the restroom - raise your hand. You will be guided there. A,ter the &TO- s*gnal put your booklet in the envelope .don/t seal0) leave at your table. 1o not leave the room without permission. You have additional 15 minutes to read the whole set.

-hys*cal Constants, n*ts, Formulas an. E/uat*ons 3vogadro4s constant 'niversal gas constant Speed of light "lanck4s constant Faraday constant %ravity of +arth Standard pressure 3tmospheric pressure Aero of the *elsius scale N3 5 6.7221 1728 mol-1 R = 9.81:5 ;<=-1<mol-1 c = 2.>>?> 179 m<s-1 h= 6.6261 17-8: ;<s F 5 >6:95 *<mol-1 g = >.91 m<s-2 p 5 1 bar 5 175 "a 5 ?57 mm@g 1 atm 5 1.718 175 "a 5 ?67 mm@g 2?8.15 =

1 nanometer .nm0 = 17-> m 1 1a 5 1 atomic mass unit 1 electron volt .eB0 5 1.672217-1> ; 5 >6:95 ;<mol-1 +nergy of a light &uantum with wavelength +nergy of one mole of photons %ibbs energy Delation between e&uilibrium constant and standard %ibbs energy Delation between standard %ibbs energy and standard emf *lapeyron e&uation for phase transitions (ntegrated *lausius-*lapeyron e&uation for phase transitions involving vapor E 5 hc C Em 5 hcN3 C G 5 H - TS

G o K 5 e$p RT

G o 5 nFE o
dp H 5 dT T V
ln p2 H 1 1 5 p1 R T1 T2 aprod areag
)

1ependence of %ibbs energy of reaction on concentration or pressure

G 5 G o+ RT ln

a 5 c C .1 molCE0 for the substances in solution) a 5 p C .1 bar0 for gases

Bolume of a sphere of radius R Surface area of a sphere of radius R @ydrostatic pressure

V=

: 8 R 8

S 5 :R2 p 5 Fgh

-ro0lem $1 Clathrate gun 2+ 3o*nts4

Guestion Harks 1 2 2 1 8 8 : 5 5 6 6 2 otal 1>

The only gun that is able to kill all living people in one shot !n the floors of oceans and seas there are vast reserves of methane in the form of clathrate compounds called methane hydrates. hese reserves can be mined and serve as a source of energy or raw materials for organic synthesis. @owever) scientists are seriously worried about the possibility of spontaneous decomposition of hydrates caused by the raising ocean temperature. (t is believed that if a sufficient amount of methane is released into the atmosphere) the oceans will warm up &uicker due to the greenhouse effect) further accelerating the decomposition of clathrates. 1ue to the e$plosion of the resulting methane-air mi$ture andCor changes in the composition of the atmosphere) all living creatures may become e$tinct. his apocalyptic scenario is called a clathrate gun. 'pon decomposition of 1.77 g of a methane hydrate with a fi$ed composition at 25 I* and atmospheric .171.8 k"a0 pressure) 275 mE of methane is released. 1. 1etermine n .not necessarily integer0 in the formula of methane hydrate) *@:n@2!.

*alculationsJ

3nswerJ

Deal methane hydrate has a non-stoichiometric composition close to *@ :<6@2!. 3t atmospheric pressure) methane hydrate decomposes at -91 I*. @owever) under high pressures .e.g. on the ocean floor0 it is stable at much higher temperatures. 1ecomposition of methane hydrate produces gaseous methane and solid or li&uid water depending on temperature. 2. Write down the e&uation of decomposition of 1 mole of *@:<6@2! producing solid water .ice0 @2!.s0.

he enthalpy of this process e&uals 1?.:? k;<mol -1. 3ssume that the enthalpies do not depend on temperature and pressure) the volume change upon decomposition of hydrate is e&ual to the volume of released methane) and methane is an ideal gas. 8. 3t what e$ternal pressure does decomposition of methane hydrate into methane and ice take place at -5 I*K *alculationsJ

3nswerJ :. What is the minimum possible depth of pure li&uid water at which methane hydrates can be stableK o answer this &uestion) you should first deduce at which minimum temperature methane hydrate can coe$ist with li&uid water. *hoose the correct answer. 2?2.> L 2?8.15 L 2?8.: L

*alculationsJ

3nswerJ

Earge methane hydrate stocks on the floor of Maikal lake) the largest freshwater lake in Dussia and in the world) have been discovered in ;uly 277> by the crew of a deep-submergence vehicle NHir-2O. 1uring the ascent from the depth of 1:77 m methane hydrate samples started to decompose at the depth of 8?2 m. 5. 1etermine the temperature in Maikal lake at the depth of 8?2 m. he enthalpy of fusion of ice is 6.71 k;<mol-1. *alculationsJ

3nswerJ otal amount of methane in hydrates on +arth is no less than 5<1711 tons. 6. My how many degrees would the +arth atmosphere heat up) if such amount of methane is burned by reacting with atmospheric o$ygenK he enthalpy of combustion of methane is 99> k;<mol-1) the total heat capacity of the +arth/s atmosphere is about :<1721 ;<L-1. *alculationsJ

3nswerJ

-ro0lem "1 Brea5 .o6n 3hotosynthes*s 7 the H*ll react*on 28 3o*nts4

Guestion "oints 1 1 2 2 a 2 8 b 2 : c 8.5 a 1 b 2 5 8 6 2.5 otal 1>

(n the history of photosynthesis research) there were some breakthrough e$periments which added much to our knowledge of this very comple$ process. !ne of such e$periments was performed in 1>87s by an +nglish biochemist Dobert @ill. (n this problem) we consider some of his data together with the data of more recent e$periments. 1. (n plants) under illumination) carbon dio$ide is reduced to carbohydrates .denote as P*@2!Q0 and o$ygen is produced. Write the overall e&uation of photosynthesis in plants.

Huch of the photosynthesis takes place in chloroplasts - organelles found in plant cells and containing chlorophyll - the light-absorbing substance. @ill isolated chloroplasts from the cells by grinding the leaves in the sucrose solutions. he cell-free chloroplasts did not produce o$ygen under illumination even in the presence of *! 2. @owever) upon adding potassium ferrio$alate =8RFe.*2!:08S .with the e$cess of potassium o$alate0 to the chloroplast suspension @ill observed o$ygen liberation under illumination even without *!2. 2. @ill/s e$periment enabled to determine the source of o$ygen during photosynthesis. Write the formulas of the o$idant and the reducing agent in the photosynthesis inside the plant cells and in the cell-free chloroplasts .the @ill reaction0. ,atural photosynthesis !$idant Deducing agent @ill reaction !$idant Deducing agent

@ill measured the amount of evolved o$ygen using muscle haemoglobin .@ill denoted it @b0 which binds all molecular o$ygen in a 1J1 ratio to form @b! 2. he initial concentration of @b was 7.617-: H. =inetic curves corresponding to different ferrio$alate concentrations are shown in the figure .the upper curve corresponds to 2.717-: H0.

he fraction of bound haemoglobin @b!2 .with respect to the initial amount of @b0 as function of time. *rosses denote the end of reaction .Figure 2a from the original @ill/s paperJ R. Hill. !ygen p"oduced by isolated chlo"oplasts. # $"oc. R. Soc. %& '()(& v. '*+& pp. '(*,*'-0 8. a. From the figure) estimate the Fe C !2 mole ratio at the end of reaction. 1o not take into account the iron from @b. b. Write the e&uation of @ill reaction assuming that it proceeds with a high yield. c. 'sing the table of standard electrode potentials) determine the %ibbs energy of the @ill reaction at T 5 2>9 =) o$ygen pressure 1 mm@g) p@ 5 9 and standard concentrations of other species. (s this reaction spontaneous at such conditionsK @alf-reaction !2 T :@T T :e 2@2! *!2 T :@T T 9e P*@2!Q T @2! Fe8T T e Fe2T Fe8T T 8e Fe7 RFe.*2!:08S8- T e RFe.*2!:08S:RFe.*2!:08S:- T 2e Fe T 8*2!:2a. *alculations E) B T1.28 -7.71 T7.?? -7.7: T7.75 -7.5>

n.Fe0 C n.!20 5

b. Deaction e&uationJ

U. *alculations

VG 5 he reaction is spontaneous not spontaneous

,ow) the name W@ill reactionX denotes photochemical o$idation of water by any o$idant other than carbon dio$ide which is sensiti#ed by plant cells or isolated chloroplasts. (n another e$periment .1>520) &uinone in an acid solution was used as an o$idant in the @ill reaction initiated by light flashes in the .hlo"ella algae. +$perimental data are shown in the figure. he volume of o$ygen .in mm8) at temperature 17 o* and pressure ?:7 mm@g0 per one gram of chlorophyll per one flash was determined as a function of light intensity for natural photosynthesis and for isolated chloroplasts. (t was found that the ma$imum yield of o$ygen is the same for natural photosynthesis and the @ill reaction.

>

.Figure 1 fromJ H. Eh"/ant"aut& E. Rabinovitch. Kinetics o0 Hill "eaction. # 1"chives o0 %ioche/ist"y and %iophysics& '(2*& v. )3& pp. 4+,350 : a. 1etermine the reaction order of a photochemical @ill reaction with respect to light intensity at low and high intensity. For each case choose one of three valuesJ Deaction orderJ Eow intensity 7 1 2 7 @igh intensity 1 2

b. @ow many chlorophyll molecules participate in the formation of one o$ygen molecule in the saturation limit of the @ill reactionK . he molecular mass of chlorophyll is about >77 1a0. *alculationsJ

17

n.*hl0 C n.!20 5

he &uantum re&uirement of the light redo$ reactions is defined as the average number of light photons .not necessarily integer0 needed for the transfer of one electron from a reducing agent to an o$idant. he isolated chloroplasts were irradiated during 2 hours by a monochromatic light .wavelength 6?2 nm0 with the energy input 7.578 m;Cs) and the total volume of o$ygen formed was :?.6 mm8 .under the same conditions as in &uestion :0. 5. *alculate the &uantum re&uirement for the @ill reaction. *alculationsJ

Guantum re&uirementJ

6. ry to make conclusions from the above e$periments .&uestions 2-50. For each of the following statements choose e*ther 9!es: or 9No:. !es (n natural photosynthesis) water o$idation and *!2 reduction are separated in space. (n chloroplasts) !2 is produced from *!2. !$idation of water in chloroplasts re&uires light illumination. Host of chlorophylls in chloroplasts participate directly in the photochemical !2 production. (n isolated chloroplasts) every absorbed photon causes transfer of one electron. No

11

-ro0lem %1 Meer6e*n;&chm*.t;-onn.or,;<erley react*on 2+ 3o*nts4

Guestion Harks a ? 1 b 8 2 9.5 8 6 : 9 otal 82.5

Heerwein-Schmidt-"onndorf-Berley .HS"B0 reaction is a useful tool for reduction of carbonyl compounds to alcohols. he reaction is the reduction of carbonyl compounds by low molecular weight alcohols in the presence of alko$ides of aluminium or other metalsJ
D1 ! D2 !@ 3l.!i"r08 D1 !@ D2 !

.10 he mechanism of the reaction includes coordination of carbonyl compound by aluminium alko$ide) hydride transfer in the inner sphere of the comple$ and subse&uent transalko$ylation. (t can be schematically represented as follows .transalko$ylation is shown as a one-step process for brevity0J
D1 D1 ! D2 ! 3l ! ! ! ! 3l ! ! D2 @ D1 ! ! 3l ! ! D2 @ i"r!@ ! 3l ! ! !@ D1 D2 !

.20 he reaction is reversible and shifting the e&uilibrium to the desired product re&uires some e$cess of the reductant. (n some cases .e.g. in the case of reduction of aromatic aldehydes and ketones0 the e&uilibrium constant is so large that the reverse reaction can be neglected. he table below contains standard entropies and standard enthalpies of formation of li&uid substances at 2>9 =. he boiling points of the substances at 1 bar are also given. Substance V0Ho2>9) k;Cmol So2>9) ;C.mol<=0 tvap) YZ 3cetone -2:9.: 277.: 56 (sopropanol -819.1 197.6 92 *yclohe$anone -2?1.2 22>.7 156 *yclohe$anol -8:9.2 278.: 161 1a. *alculate the minimum isopropanolJcyclohe$anone mass ratio which is re&uired to reach a >>[ yield of reaction at 2>9 =. 3ssume that a0 the reaction mi$ture eventually gets at e&uilibrium and b0 no products are initially present. *alculationsJ

12

3nswerJ /.*8@9!0 J /.*6@17!0 5

1b. *hoose the appropriate way.s0 to increase the cyclohe$anol yield. 6a"ning7 e""oneously ticked bo!es 8ill "esult in penalty points (ncrease the temperature up to 57Y* using a reflu$ (ncrease the temperature up to 67YZ) evaporating .distilling0 the acetone 3dd some ethanol to the reaction mi$ture 3dd some ethanal to the reaction mi$ture

2. !ften the rate-limiting step in the HS"B reaction is the hydride transfer or the alcoholysis of the alko$ide after hydride transfer. For these two cases) using the above mechanism .20) derive an e$pression for the rate of reaction as a function of current concentrations of a carbonyl compound) isopropanol and a catalyst. (n both cases determine the rate orders in the reactants and the catalyst. 3ssume that all reaction steps before the limiting step are fast and reversible. 'se e&uilibrium appro$imation) if necessary. For brevity use the following notationJ A for carbonyl compound) B for isopropanol) C for catalyst. 1enote intermediates as you wish.
18

Rate,li/iting step is the hyd"ide t"ans0e" 1erivationJ

r=

3nswer !rder in carbonyl compoundJ \\\\\\\\ !rder in isopropanolJ \\\\\\\\ !rder in the catalystJ \\\\\\\\

Rate,li/iting step is the t"ansalko!ylation o0 the alcoholate by isop"opanol 1erivationJ

1:

r=

3nswer !rder in carbonyl compoundJ \\\\\\\\ !rder in isopropanolJ \\\\\\\\ !rder in the catalystJ \\\\\\\\

HS"B reaction can be used to obtain chiral alcohols) if the chiral catalyst is employed. For instance) *ampbell et al. used the catalyst based on the chiral 2)2/-dihydro$y-1)1/-binaphtyl .M(,!E0) which is synthesi#ed in situ from binaphtol and trimethylaluminiumJ
!@ !@ 3l.*@808 ! 3l ! ! 3l ! !

i"r!@

.M(,!E03l.!i"r0

.80 he chirality of M(,!E is due to the sterically hindered rotation around the *-* bond. hough perfectly stable at room temperature) M(,!E may racemi#e when heated. 8. Which of the phenols below can form stable .at room temperature0 enantiomers so that they can be used in the same fashion to produce a chiral catalystK 6a"ning7 e""oneously ticked bo!es 8ill "esult in penalty points Substance
!@ !@ !*@8 !*@8

*an be used

Substance
!@ !@

*an be used

15

!@ !@ !*@8 !*@8 !@ !@ !@ !@ @! *@8! !*@8 !@

:. Enantio/e"ic e!cess) ee) is used to characteri#e the enantiomeric purity of the substance. his &uantity e&uals ratio of the difference of concentrations of enantiomers R and S to their sumJ
ee = R RS R S S R RS + R S S

+nantiomeric e$cess of the pure R isomer is unity) ee of the racemic mi$ture is #ero. When using the enantiomerically pure .M(,!E03l.!i"r0 as a catalyst for reduction of ]bromoacetophenone) the ee of the product e&uals 91[. What is the ee of the product if the catalyst ee e&uals 57[K "rovide your calculation with an illustration or derivation of the final formula.

1erivationJ

16

ee 5

1?

-ro0lem >1 A s*m3le *norgan*c e?3er*ment 2@ 3o*nts4

Guestion Harks 1 5 2 12 8 ? otal 2:

*ompound A which contains metal X is a colorless crystalline solid and highly soluble in water. (t is used as a reagent in analysis and gives in alkali media a binary compound B containing 6.> [ .mass0 of o$ygen. 'nder heating A decomposes with a mass loss of 86.5[. 1. 1etermine the metal X and compounds A) B.

Your workJ

X 5\\\\\\

A 5 \\\\\\

B 5 \\\\\\

2. 'pon adding some amount of sodium thiosulphate to the solution of A the color immediately becomes red) then changes to reddish-brown) and after some minutes a darkbrown precipitate C forms .reaction 10. he solution over it is colorless. Meing heated on air at 677^*) C gives a grey powder X .reaction 20) so as 7.>7 g of residue can be obtained from 1.17 g of C. 3 gas evolved by heating C in vacuum .reaction 80 can be absorbed by calcium hydro$ide suspension .reaction :0. Meing stored for a long time under saturated solution of barium perchlorate in 7.1 _ @*l!:) the color of the precipitate becomes lighter) while the use of magnesium perchlorate doesn/t give such effect. What is CK Write the e&uations of the reactions .1 - :0.

Your workJ

19

C 5 \\\\\\\

Deaction e&uationsJ

8. he compound C being stored under the mother li&uor .containing an e$cess of A0 its color changes to yellow due to the transformation into ). (f barium ions are added to the suspension of C in the mother li&uor) a mi$ture of ) and of a white precipitate forms. "ropose the formula of )) taking into account that it contains ??.5[ .mass0 of X. %ive the e&uation of ) formation. Your workJ

) 5 \\\\\\\

Deaction e&uationJ

1>

-ro0lem A1 &*m3le est*mates o, gra3hene 3ro3ert*es 28 3o*nts4

Guestion Harks a 2 1 b 2. 5 2 : 8 5.5 otal 1:

%raphene is a two-dimensional) one atom thick carbon material .Fig.1 a0. Hany layers of graphene stack together to form graphite .Fig. 1b0.

(b)

S = 5,16 *10-20 m2

(a)

Fig. 1. .a0 he structure of graphene. Spheres are carbon atoms. hey are arranged in he$agons. he area of one carbon he$agon is 5.16<17-27 m2 .b0 *rystal lattice of graphite. hree graphene layers are shown Such atomic structure was long considered to be unstable. @owever) in 277: 3ndrey %eim and =onstantin ,ovoselov have reported production of the first samples of this unusual material. his groundbreaking invention was awarded by ,obel pri#e in 2717. +$perimental studies of graphene are still restricted. "roduction of massive portions of the new substance still is a challenging synthetic problem. Hany properties of graphene were esti/ated. 'sually) there is not enough information for rigorous calculations) so we have to make assumptions and neglect unimportant factors. (n this problem) you will estimate the adsorption properties of graphene.

27

1a. +stimate the specific surface of graphene open for adsorption in units m 2 Cg. *onsider that graphene plane is separated from any other solid or li&uid substance. *alculationsJ

S 5 \\\\\\\\\ m2Cg he single layer of nitrogen molecules adsorbed on the outer surface of graphite is shown in Fig. 2. 3ssume that the same arrangement of nitrogen molecules is formed on a graphene surface.

Fig. 2. ,itrogen molecules ,2 .grey circles0 on the outer surface of graphite 1b. @ow many grams of nitrogen can be adsorbed on 1 gram of graphene assuming that the graphene layer is placed onto the surface of a solid supportK +stimate the volume occupied by these nitrogen molecules after the complete desorption from 1 g of graphene .pressure 1 bar) temperature 2>9 =0. *alculationsJ

/,2 5 \\\\\\\ g

21

V, 2 = \\\\\\\ . Eet us consider adsorption as a common chemical e&uilibrium 3ads ) .10 3 gas .3gas are molecules 3 in the gaseous state) 3ads are the same molecules on the surface0 with the e&uilibrium constant KJ n3ads .molCm 2 0 9= p3gas .bar0 .such assumption holds if a small number of molecules is adsorbed on the surface0 3dsorption properties of graphene can be estimated from the data for adsorption on a regular three-dimensional graphite. he enthalpy of adsorption .VHo of reaction .100 of any molecule 3 on graphene is on average by 17[ less negative compared to that on graphite. !n graphite) the adsorbed molecule is bound more strongly due to the interaction with the lower graphene layers in the lattice .Fig. 1b0 and hence the enthalpy of adsorption is more negative. he standard entropies of adsorption on graphene and graphite are assumed to be the same. 2. @ow many moles) n) of **l: are adsorbed on 1 g of graphene at p.**l:0 5 17-: bar if 2.717-? mol of **l: are adsorbed on 1 m2 of graphite at p.**l:0 5 6.617-5 barK 3ssume that graphene is placed onto the surface of a solid support and the interaction of **l : with the support does not change the enthalpy of adsorption of **l : on graphene. he temperature in both cases is 2>8 =. VHo of adsorption of **l: on graphite is -85.1 k;Cmol. *alculationsJ

n.**l:0 5 \\\\\\\

he graphene films are e$pected to be sensitive gas detectors. (f 17> particles of a gas are adsorbed on 1 cm2 of a graphene surface this is enough to measure an electrical resistivity change of the graphene layer and to detect the presence of a gas in the environment. 8. 1etermine the minimal content of ethane) Z 2`6) in the air .in mol.[0 at atmospheric pressure .T 5 2>8=0 at which a graphene sensor will detect this gas. he known data for the
22

adsorption of alkanes on graphite are shown in Fig 8. 3ssume that air doesn4t affect the adsorption properties of ethane.
-7 -8

(a)

ln K

-9 -10 -11 -12 -13 -14 -15 2.6

2.8

3.0

3.2

3.4

3.6

3.8

4.0

4.2

4.4

ln M

-1

, kJ mol

-8 -12 -16 -20 -24 -28 -32 -36 -40 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4

(b)

ln M

Fig. 8. hermodynamic properties for adsorption of alkanes on a graphite surface. .a0 ln K PmolCm2CbarQ as a function of ln : .: - molecular mass of alkane in gCmol0a .b0 V Ho of adsorption as a function of ln :. Einear dependences are assumed in both cases *alculationsJ

28

*ontent of Z2@6 5 \\\\\\\\\ mol.[

2:

-ro0lem @1 Cyclo3ro3anes1 &o s*m3le1 &o ,ancyB 2+ 3o*nts4

1 2 8 otal 9 22 ?7 177 *yclopropanes bearing donor and acceptor substituents at the neighboring *-atoms) for e$ample) A)

Guestion Harks

demonstrate high reactivity behaving similar to 1)8-#witterion B.

hus) A$ .b 5 :-!He0 undergoes the three-membered ring opening in the Eewis acid-cataly#ed reaction with 1)8-dimetho$yben#ene as a nucleophile giving the product C. 1. Write down structural formula of C. Structural formula of CC

A$ participates in cycloadditions) annulations) oligomeri#ations) and other processes.

hus) formal

R8T2S-cycloaddition between A$ and :-metho$yben#aldehyde leads to a five-membered ring in ). 1ecarbo$ylation of all carbo$ylic groups in ) produces E .*19@27!80) the molecule of the latter having a plane of symmetry.

2. Write down structural formulae of ) and E indicating their stereochemistry. ) E

3lso) A can undergo various transformations in the absence of any reaction partners e$cept catalysts. Some transformations typical of A$ are shown in the Scheme below. 25

o determine the structures of F;J) a set of physico-chemical data was obtained .see able 1 for some results0. (t was found thatJ a0 F and ( have the same molecular formula as A$a b0 ( is formed as the most stable stereoisomera c0 H and I are structural isomersa d0 H is formed as a single diastereomer with * 2 a$is of symmetry .the molecule looks the same after rotation through the angle of 1970a e0 I is formed as a mi$ture of two diastereomersa f0 J is naphthalene derivative. (n the process leading to I) one molecule of A$ demonstrates the described above common reactivity .analogous to that of B0. he other molecule of A$ behaves differently. 3lso) the latter behavior is demonstrated diastereomers. by cyclopropane A" .dimethyl 2-.8):)5-trimetho$yphenyl0cylopropane-1)1dicarbo$ylatea b in A 5 8):)5-.He!080 when treated with Sn*l: affording D as a mi$ture of two he macor isomer has the center of symmetry. Similar reactivity is shown by A" in Sn.! f02-cataly#ed reaction with ( furnishing L.

Table '. ;n0o"/ation about the co/pounds. Rat*o o, the num0er o, hy.rogen;conta*n*ng grou3s ,on-aromatic 3romatic *@ *@ *@2 *@8 !@ 1 1 1T1T1 7 2T2 1 1 1T1T1 7 2T2 1T1T1 7 2T1 7 2T2 1 1 1T1T1 7 2T2 1T1T1 1T1 2T1T1T1T1 7 2T2T1T1T1 7 7 1T1 1 1T1T1T1T1 1T1 1 2T1T1T1 7 1 1T1T1T1T1 1 2T2T1T1T1T1 7 2T2T1 Em3*r*cal ,ormula .*1:@16!50n .*1:@16!50n .*1:@16!50n .*1:@16!50n .*1:@16!50n .*18@12!:0n .*16@27!?0n .*5@6!20n

A$ F ( H I J D L

8. Write down the structural formulae of F;J, L and the macor isomer of D.

26

D .macor isomer0

2?

-ro0lem 81 )*Eerse 3ermanganatometry 2+ 3o*nts4

Guest. 1 Harks 2 2 2 a : b 2 8 c 2 d 6 : ? a ? 5 b 2 otal 8:

he amount of many reducing agents can be determined by permanganatometric titration in alkaline medium allowing permanganate ion reduction to manganate. 1. Write down the ionic e&uation of the reaction for formate titration with permanganate in an a&ueous solution containing d7.5 H ,a!@.

itration with permanganate in alkaline medium is often supplemented by addition of a barium salt) which leads to precipitation of manganate as MaHn!:. 2. Which side redo$ processes involving manganate is suppressed by the barium saltK Write down an e$ample of e&uation of the corresponding reaction.

17.77 mE .VHn0 of 7.7:77 _ .<Hn0 =Hn!: solution was placed in each of flasks F) G) and H and different reactions were conducted in each flask. %. o flask A) a sample solution containing unknown amount of crotonic acid .*30 Z`8Z`5Z`-Zee` .m*30) an alkali and barium nitrate .both in an e$cess0 were added) and the reaction mi$ture was incubated for :5 min. (t is known that each molecule of crotonic acid loses 17 electrons under the e$periment conditions. he molar mass of *3 is 96.7> gCmol. a0 Write down the total ionic e&uation of the reaction.

9.77 mE .V*,0 of 7.7177 _ .c*,0 potassium cyanide solution was further added to the incubated mi$ture. his resulted in completion of the following reactionJ 2Ma2T T 2Hn!:- T *,- T 2!@- 5 2MaHn!: T *,!- T @2! MaHn!: precipitate was then filtered off) and the e$cess of cyanide in the filtrate was titrated with 7.7757 H .c3g0 3g,!8 solution till detectable precipitation was observed. ,ote that both *,- and *,!- are analogs of halide ions) but *,!- affords soluble silver salt.

29

b0 %ive the formula for the comple$ formed when 3g T ions were initially added to the cyanide solution .until the precipitate was formed0.

c0 %ive the formula of the precipitate formed.

d0 *alculate the mass of crotonic acid .in mg0 if 5.:7 mE . V3g0 of the silver salt solution was consumed for the titration to the endpoint.

>1 3nother sample with different concentration of crotonic acid and alkali .in an e$cess0 were added to flask G) this mi$ture lacking barium salt. 3n e$cess of =( .instead of cyanide0 was added as a reducing agent. he mi$ture was further acidified) and the iodine evolved was titrated with 7.1777 _ .cS0 thiosulfate solution. :.>7 mE .VS10 of the titrant was used to reach the endpoint. *alculate the mass of crotonic acid .in mg0.

2>

5. 3 sample containing tin.((0 was added to flask H) and the medium was adcusted to weak alkaline. in.((0 was &uantitatively o$idi#ed to Sn.!@0 62-) whereas a precipitate formed as a result of permanganate reduction. he precipitate was isolated) washed off) dried at 257 Z) weighed .the mass of the water-free precipitate ./prec0) representing a binary compound Hn$!y) was of 29.6 mg0) and dissolved in @2S!: in the presence of an e$cess of potassium iodide. he evolved iodine was titrated with 7.1777 _ thiosulfate solution. 2.57 mE .VS20 of the latter was consumed to attain the endpoint. a0 1etermine $ and y. Write down the reaction of precipitation.

87

DeactionJ

b0 *alculate the mass of tin in the sample .in mg0.

81

-ro0lem +1 n*/ue l*,e o, archaea 2+ 3o*nts4

Guestion Harks 1 2 2 ? 8 8 : 9 5 : 6 : ? 5 9 : a 8 > b 5 otal :5

3rchaea .or archaebacteria0 are single-celled microorganisms significantly differing from bacteria and eukaryotes at the molecular level. +n#ymatic reaction of methylamine with water is the macor energy source for some archaea. (n a particular e$periment) an archaea strain was cultivated at p@ ? under anaerobic .o$ygen free0 conditions with the nutrient medium containing 18Z@8,@2 as the only energy source. 3fter a certain incubation period) the gas over the archaea culture was sampled and analy#ed. (t was found that the gas contains two substances F and B in the molar ratio of 1.77J8.77 correspondingly. he sample density rel. @2 is of 12.7. 1. *alculate the volume fractions .in [0 of F and B in the mi$ture.

2. 1etermine F and B if there is no , atoms in gas collected. Your workJ

3. Write do n t!e e"#ation o$ en%&mati' rea'tion o$ met!&lamine de('ribed in t!e abo)e e*+eriment #(in, +redominant $orm o$ ea'! (+e'ie(.

it!

ater

+n#ymes containing the residue of ]-amino acid X are found in many archaea. (t is known that XJ is composed of atoms of : elementsa is 19.9 [ o$ygen by massa possesses the single individual tD,3 and is incorporated into proteins during translation.
82

3mino acid =-lysine .see the structure in scheme below0 was identified as the X precursor in archaea. 3ll * and , atoms found in X originate from two starting lysine molecules. 1ifferent isotope-labeled =-lysines were introduced into a model system to clarify the biosynthetic pathways of X. he results are summari#ed in the table. Holecular mass .rounded to integer0 of the X (sotope composition of =-lysine residue RD*@.,@20*!S) bound to tD,3) gCmol ,ormal 289 18 15 3ll carbons Z) all nitrogens , 258 15 f-3mino group with , 28> :. 1etermine the molecular formula of X. *alculationsJ

XC

X is biosynthesi#ed in archaea according to the following scheme .+1-+8 - en#ymes0J

HOOC NH2 NH2 L-lysine E1

E2 -H2O

E3 ?

Spontaneously -H2O

HOOC NH2

NH2 L-lysine

3t the first step) lysine is transformed into its structural isomer .]-amino acid) C0) whereas )
H S. 3ll reaction coefficients in the above contains a peptide bond) and E a formyl group R scheme e&ual 1. 5. %ive the chemical formula of C) ) and E. From the reaction types given hereunder) choose .tick0 only one corresponding to the g8 cataly#ed reaction. C O

88

*alculationsJ

!$idative deaminationa 1ecarbo$ylationa (ntermolecular deaminationa @ydro$ylationa "eptide bond hydrolysis. I contains the fragmentJ
(R,Me,H) (R,Me,H)
4 3 5

(H,Me,R) N

D is a massive substituent .Hh177 gCmol0. he 8 rd * atom is non-asymmetric) :th and 5th * atoms are stereogenic centers. 3ll * atoms in the cycle are bound with at least one @ atom. +ach substituent .@) He and D0 is found only once. 6. 1etermine the positions of substituents @) He) and D. Your workJ

8:

?. 1raw structural formulae of C and X with stereochemical details. here are no stereo centers affected on the way from C to X. Hark every stereocenter of X with either R or S. C X

!nly one codon is responsible for incorporation of X residues into proteins in archaea. he nitrogen bases forming this codon contain two e$ocyclic amino groups and three e$ocyclic o$ygen atoms in total.

9. Fill in the hereunder table to determine the nucleotide composition of the codon encoding X. T*c5 only one 0o? *n each l*ne. Your workJ

,itrogen base 3 * % '

he number of bases in the codon 2 8 7 or 1

1 or 2

he fragment of mD,3 coding se&uence given below contains the codons encoding X residue incorporation into an archaea en#ymeJ 5/i33'3%33''3%*%%33*3%3%%%'%3*i8/

>a. 'sing the table of the genetic code) decide how many amino acid residues are incorporated into the en#yme chain due to this fragment translation. Your workJ
85

,umber of amino acids 5 \\\ >b. Write down the amino acid se&uence translated from this fragment. ,ote that more than one X residue is found in the fragment. Fill in the bo$es with the amino acid abbreviations .from ,- to *-terminus0. ,ote that the number of bo$es is e$cessive. (f there is more than one possibility) write all separated by WCX. (f the translation is stopped in a particular position) write WS !"X and leave all the bo$es to the right empty. Your workJ

86

2a4 RNA Co.ons ,Jr the T6enty Am*no Ac*.s second base

Am*no ac*. a00reE*at*onsC

3la 5 3lanine 3rg 5 3rginine 3sn 5 3sparagine 3sp 5 3spartic acid *ys 5 *ysteine %lu 5 %lutamic acid %ln 5 %lutamine %ly 5 %lycine @is 5 @istidine (le 5 (soleucine Eeu 5 Eeucine Eys 5 Eysine Het 5 Hethionine "he 5 "henylalanine "ro 5 "roline Ser 5 Serine hr 5 hreonine rp 5 ryptophan yr 5 yrosine Bal 5 Baline

C
"he "he Eeu Eeu Eeu Eeu Eeu Eeu (le (le (le Het.start0 Bal Bal Bal Bal Ser Ser Ser Ser "ro "ro "ro "ro hr hr hr hr 3la 3la 3la 3la

A
yr yr S !" S !" @is @is %ln %ln 3sn 3sn Eys Eys 3sp 3sp %lu %lu

(
*ys *ys S !" rp 3rg 3rg 3rg 3rg Ser Ser 3rg 3rg %ly %ly %ly %ly C A ( C A ( C A ( C A (

C A (

hird base

8?

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