2008 ICHO38 Preparatory Problems Final

38th International Chemistry Olympiad * Preparatory Problems
Problem 1: A brief history of life in the universe

Chemistry is the language of life. Life is based on atoms, molecules and complex chemical reactions in ol ing atoms and molecules. It is only natural then to as! "here atoms came from. #ccording to a "idely accepted model, the uni erse began about $% billion years ago in a big bang and has been expanding e er since. &he history of the uni erse as a "hole can be ie"ed in terms of a series of condensations from elementary to complex particles as the uni erse cooled. Of course, life as "e !no" it today is a special phenomenon that ta!es place at moderate temperatures of the 'arth. Light elements, mostly hydrogen and helium, "ere formed during the first se eral minutes after the big bang in the rapidly expanding and, therefore, rapidly cooling early uni erse. (tars are special ob)ects in space, because temperature drop is re ersed during star formation. (tars are important in chemistry, because hea y elements essential for life are made inside stars, "here the temperature exceeds tens of millions of degrees. &he temperature of the expanding uni erse can be estimated simply using* T + $,$, - t$-. "here T is the a erage temperature of the uni erse in /el in 0/1 and t is time 0age of the uni erse1 in seconds. #ns"er $2$ through $23 "ith one significant figure. 4ound off if you "ant. $2$. 'stimate the temperature of the uni erse "hen it "as $ second old at "hich time the temperature "as too high for fusion of protons and neutrons into helium nuclei to occur. $2.. 'stimate the temperature of the uni erse "hen it "as about 3 minutes old and the nuclear synthesis of helium "as nearly complete. $23. 'stimate the age of the uni erse "hen the temperature "as about 3,,,, / and the first neutral atoms "ere formed by the combination of hydrogen and helium nuclei "ith electrons. $25. &he first stable molecules in the uni erse "ere possible only after the temperature of the expanding uni erse became sufficiently lo" 0approximately $,,,, /1 to allo"
atoms in molecules to remain bonded. 'stimate the age of the uni erse "hen the temperature "as about $,,,, /. $2%. 'stimate the a erage temperature of the uni erse "hen the uni erse "as about 3,, million years old and the first stars and galaxies "ere born. $23. 'stimate the temperature of the uni erse presently and note that it is roughly the same as the cosmic micro"a e bac!ground measurement 03 /1. $26. Order the follo"ing !ey condensations logically, consistent "ith the fact that o er 778 of atoms in the expanding uni erse are hydrogen or helium. a20 120 120 120 120 120 120 120 120 1 a. 9uar!s : proton, neutron b. $,$5 cells : human being c. ;, C, <, O : ;., C;5, <;3, ;.O 0in interstellar space1 d. proton, helium nucleus = electron : neutral ;, ;e atoms e. proteins, nucleic acids, membrane : first cell f. proton, neutron : helium nucleus g. ;., ;e, C;5, <;3, ;.O, dust : solar system h. ;, ;e atoms : reioni>ation, first generation stars and galaxies i. proton, helium nucleus 0light elements1 : hea y elements such as C, <, O, P, (, ?e, @A superno a explosion ). ;., C;5, <;3, ;.O, etc. : amino acids, sugars, nucleotide bases, phospholipids on 'arth
Problem 2: Hydrogen in outer space

;ydrogen is the most abundant element in the uni erse constituting about 6%8 of its elemental mass. &he rest is mostly helium "ith small amounts of other elements. ;ydrogen is not only abundant. It is the building bloc! of all other elements. ;ydrogen is abundant in stars such as the sun. &hus the Bil!y Cay galaxy, consisting of o er $,, billion stars, is rich in hydrogen. &he distance bet"een stars is se eral light years on the a erage. ;ydrogen is also the ma)or constituent of the interstellar space. &here are about $,, billion galaxies in the uni erse. &he empty space bet"een galaxies is ast. ?or example, the Bil!y Cay galaxy is separated from its nearest neighbor, the #ndromeda galaxy, by . million light years. ;ydrogen again is the primary constituent of the intergalactic space e en though the number density is much less than in the interstellar space. &he a erage density of matter in the intergalactic space, "here the current temperature is the cosmic bac!ground energy of ..6 /, is about $ atom-m3. .2$. Calculate the a erage speed, 08RT- M1$-., of a hydrogen atom in the intergalactic space. .2.. Calculate the olume of a collision cylinder s"ept out by a hydrogen atom in one second by multiplying the cross2sectional area, d., by its a erage relati e speed "here d is the diameter of a hydrogen atom 0$ x $,28 cm1. Bultiply the a erage speed by s9uare root of . to get the a erage relati e speed. Bolecules "hose centers are "ithin the cylinder "ould undergo collision. .23. Calculate the number of collisions per second experienced by a hydrogen atom by multiplying the abo e olume by the number density. ;o" many years does it ta!e for a hydrogen atom to meet another atom in the intergalactic spaceD .25. Calculate the mean free path of hydrogen in the intergalactic space. is the a erage distance tra eled by a particle bet"een collisions. ;ydrogen atoms are relati ely abundant in interstellar regions "ithin a galaxy, there being about $ atom per cm3. &he estimated temperature is about 5, /. .2%. Calculate the a erage speed of hydrogen atom in the interstellar space.
.23. Calculate the mean free path 01 of hydrogen in the interstellar space. .26. Chat do these results imply regarding the probability of chemical reactions in spaceD
Problem 3: Spectroscopy of interstellar molecules

#toms in interstellar space seldom meet. Chen they do 0most li!ely on ice surfaces1, they produce radicals and molecules. &hese species, some of "hich presumably played a role in the origin of life, ha e been identified through the use of different spectroscopic methods. #bsorption spectra of interstellar species can be obser ed by using the bac!ground radiation as the energy of excitation. 'mission spectra from excited species ha e also been obser ed. (imple diatomic fragments such as C; and C< "ere identified in interstellar space o er 3, years ago. 32$. &he bac!ground electromagnetic radiation in the interstellar space has a characteristic energy distribution related to the temperature of a blac!body source. #ccording to CienEs la", the "a elength 0 1 corresponding to the maximum light intensity emitted from a blac!body at temperature T is gi en by T + ..7 x $,23 m /. LetEs consider a region near a star "here the temperature is $,, /. Chat is the energy in )oule of a photon corresponding to the pea! emission from a blac!body at $,, /D Chen molecules "ith non2>ero dipole moments rotate, electromagnetic radiation can be absorbed or emitted. &he spectroscopy related to molecular rotation is called micro"a e spectroscopy, because the electromagnetic radiation in ol ed is in the micro"a e region. &he rotational energy le el of a diatomic molecule is gi en by EJ + J0J=$1h.-8 .I "here J is the rotational 9uantum number, h is the Planc! constant, I is the moment of inertia, R.. &he 9uantum number J is an integer increasing from , and the reduced mass is gi en by m$m.-0m$=m.1 for diatomic molecules 0m$ and m. are masses of the t"o atoms of the molecule1. R is the distance bet"een the t"o bonded atoms 0bond length1. 32.. Carbon monoxide is the second most abundant interstellar molecule after the hydrogen molecule. Chat is the rotational transition 0change of J 9uantum number1 "ith the minimum transition energyD Chat is the minimum transition energy of the $.C$3O rotation in )ouleD &he bond length of CO is $$3 pm. Compare the transition energy of CO "ith the radiation energy in problem 32$. Chat does the result implyD &he distribution of molecules in different energy le els is related to the bac!ground temperature, "hich affects the absorption and emission spectra.
?igure 32$. Oscillogram for the lo"est rotational transition of $.C$3O at $$%,.6, B;>. &he upper cur e "as ta!en at the temperature of li9uid air, the lo"er at the temperature of dry ice. 04eference* O. 4. Filliam, C. B. Gohnson and C. Fordy. Phys. Rev. ol. 68 0$7%,1 p.$5,.1 323. &he e9uation for the rotational energy le el is applicable to the rotation of the hydrogen molecule. ;o"e er, it has no dipole moment so that the transition of J + $ by radiation is not allo"ed. Instead a ery "ea! radiati e transition of J + . is obser ed. Calculate the temperature of interstellar space "here the photon energy at the maximum intensity is the same as the transition energy of the hydrogen molecule 0$;.1 bet"een J + , and .. &he ;2; bond length is 65 pm.
Problem : !deal gas la" at the core of the sun

Life on 'arth has been made possible by the energy from the sun. &he sun is a typical star belonging to a group of hydrogen2burning 0nuclear fusion, not oxidation1 stars called main se9uence stars. &he core of the sun is 338 hydrogen 0$;1 and 358 helium 05;e1 by mass. @nder the high temperature and pressure inside the sun, atoms lose all their electrons and the nuclear structure of a neutral atom becomes irrele ant. &he ast space inside atoms that "as a ailable only for electrons in a neutral atom becomes e9ually a ailable for protons, helium nuclei, and electrons. (uch a state is called plasma. #t the core of the sun, the estimated density is $%8 g-cm3 and pressure ..% x $,$$ atm. 52$. Calculate the total number of moles of protons, helium nuclei, and electrons combined per cm3 at the core of the sun. 52.. Calculate the percentage of space occupied by particles in hydrogen gas at 3,, / and $ atm, in li9uid hydrogen, and in the plasma at the core of the sun. &he density of li9uid hydrogen is ,.,7 g-cm3. &he radius of a nuclear particle can be estimated from r + 0$.5 x $,2$3 cm10mass number1$-3. #ssume that the olume of a hydrogen molecule is t"ice that of a hydrogen atom, and the hydrogen atom is a sphere "ith the Hohr radius 0,.%3 x $,28 cm1. 'stimate your ans"er to $ significant figure. 523. @sing the ideal gas la", estimate the temperature at the core of the sun and compare your result "ith the temperature re9uired for the fusion of hydrogen into helium 0$.% x $,6 /1.
Problem #: Atmosphere of the planets

&he solar system "as born about 5.3 billion years ago out of an interstellar gas cloud, "hich is mostly hydrogen and helium "ith small amounts of other gases and dust. %2$. &he age of the solar system can be estimated by determining the mass ratio bet"een Pb2.,3 and @2.38 in lunar roc!s. Crite the o erall nuclear reaction for the decay of @2.38 into Pb2.,3. %2.. &he half2life for the o erall reaction is go erned by the first alpha2decay of @2.38 0
2 3 8 9 2
2 3 4 9 0
&h =
4 2
;e1, "hich is the slo"est of all reactions in ol ed. &he half2life
for this reaction is 5.%$ x $,7 yr. 'stimate the mass ratio of Pb2.,3 and @2.38 in lunar roc!s that led to the estimation of the age of the solar system. 'lemental hydrogen and helium are rare on 'arth, because they escaped from the early 'arth. 'scape elocity is the minimum elocity of a particle or ob)ect 0e.g., a gas molecule or a roc!et1 needed to become free from the gra itational attraction of a planet. 'scape elocity of an ob)ect "ith mass m from the 'arth can be determined by e9uating minus the gra itational potential energy, 2GMm-R, to the !inetic energy, 0$-.1mv., of the ob)ect. <ote that the mEs on both sides cancel and, therefore, the escape elocity is independent of the mass of the ob)ect. ;o"e er, it still depends on the mass of the planet. G* the uni ersal constant of gra itation + 3.36 x $,2$$ < m. !g2. M* 'arthEs mass + %.78 x $,.5 !g R* 'arthIs radius + 3.36 x $,3 m %23. Calculate the escape elocity for the 'arth. %25. Calculate the a erage speed, 08RT- M1$-., of a hydrogen atom and a nitrogen molecule at ambient temperature. Compare these "ith the escape elocity for the 'arth. <ote that the temperature of the upper atmosphere "here gases can escape into space "ill be some"hat different. #lso note that photolysis of "ater apor by ultra iolet radiation can yield hydrogen atoms. 'xplain "hy hydrogen atoms escape more readily than nitrogen molecules e en though the escape elocity is independent of the mass of the escaping ob)ect.
&he chemical composition of the atmosphere of a planet depends on the temperature of the planetEs atmosphere 0"hich in turn depends on the distance from the sun, internal temperature, etc.1, tectonic acti ity, and the existence of life. #s the sun generated heat, light, and solar "ind through nuclear fusion of hydrogen to helium, the primiti e inner planets 0Bercury, Jenus, 'arth, and Bars1 lost most of their gaseous matter 0hydrogen, helium, methane, nitrogen, "ater, carbon monoxide, etc.1. #s the hea y elements such as iron and nic!el "ere concentrated at the core through gra ity and radioacti e decay produced heat, internal temperature of the planets increased. &rapped gases, such as carbon dioxide and "ater, then migrated to the surface. &he subse9uent escape of gases from the planet "ith a gi en escape elocity into space depends on the speed distribution. &he greater the proportion of gas molecules "ith speed exceeding the escape elocity, the more li!ely the gas is to escape o er time. %2%. Circle the planet name "here the atmospheric pressure and composition are consistent "ith the gi en data. 'xplain. # erage surface temperature and radius of the planet are as follo"s* Jenus* 63, /A 3,,%. !m Gupiter* $3% /A 6$,5,, !m pressure 0in atm1 a. b. c. d. e. K $,, 7, ,.,,6 $ $,2% 'arth* .88 /A 3,368 !m Pluto* 5. /A $,$3, !m planet 0Jenus, 'arth, Bars, Gupiter, Pluto1 0Jenus, 'arth, Bars, Gupiter, Pluto1 0Jenus, 'arth, Bars, Gupiter, Pluto1 0Jenus, 'arth, Bars, Gupiter, Pluto1 0Jenus, 'arth, Bars, Gupiter, Pluto1 Bars* .$8 /A 3,373 !m
composition 081 ;.08.1A ;e0$61 CO.073.51A <.03.51 CO.07%.61A <.0..61 <.0681A O.0.$1 C;50$,,1
%23. Crite the Le"is structure for ;., ;e, CO., <., O., and C;5. Lepict all alence electrons. %26. #ll of the abo e atmospheric components of the planets are atoms and molecules "ith lo" boiling point. Hoiling point is primarily determined by the o erall polarity of the molecule, "hich is determined by bond polarity and molecular geometry.
<onpolar molecules interact "ith dispersion force only and, therefore, ha e lo" boiling points. Met there are differences in boiling points among nonpolar molecules. #rrange ;., ;e, <., O., and C;5 in the order of increasing boiling point. 'xplain the order.
$,
Problem $: %iscovery of the noble gases

Bolecules such as ;., <., O., CO., and C;5 in Problem % are formed through chemical bonding of atoms. ' en though alency "as !no"n in the $7 th century, the underlying principle behind chemical bonding had not been understood for a long time. Ironically, the disco ery of the noble gases "ith practically >ero chemical reacti ity pro ided a clue as to "hy elements other than the noble gases combine chemically. $88., 4ayleigh decided to accurately redetermine gas densities in order to test ProutIs hypothesis. 32$. Chat is ProutIs hypothesisD Chat e idence did he use to support his hypothesisD 0(earch the Internet or other sources.1 &o remo e oxygen and prepare pure nitrogen, 4ayleigh used a method recommended by 4amsay. #ir "as bubbled through li9uid ammonia and "as passed through a tube containing copper at red heat "here the oxygen of the air "as consumed by hydrogen of the ammonia. 'xcess ammonia "as remo ed "ith sulfuric acid. Cater "as also remo ed. &he copper ser ed to increase the surface area and to act as an indicator. #s long as the copper remained bright, one could tell that the ammonia had done its "or!. 32.. Crite a balanced e9uation for the consumption of oxygen in air by hydrogen from ammonia. #ssume that air is 688 nitrogen, .$8 oxygen, and $8 argon by olume 0un!no"n to 4ayleigh1 and sho" nitrogen and argon from the air in your e9uation. 323. Calculate the molecular "eight of nitrogen one "ould get from the density measurement of nitrogen prepared as abo e. <ote that argon in the sample, initially un!no"n to 4ayleigh, did contribute to the measured density. 0atomic "eight* < + $5.,,36, #r + 37.7581 4ayleigh also prepared nitrogen by passing air directly o er red2hot copper. 325. Crite a balanced e9uation for the remo al of oxygen from air by red2hot copper. #gain sho" nitrogen and argon from the air in your e9uation.
$$
32%. Calculate the molecular "eight of nitrogen one "ould get from the density measurement of the nitrogen prepared by the second method. 323. &o 4ayleighEs surprise, the densities obtained by the t"o methods differed by a thousandth part N a difference small but reproducible. Jerify the difference from your ans"ers in 323 and 32%. 326. &o magnify this discrepancy, 4ayleigh used pure oxygen instead of air in the ammonia method. ;o" "ould this change the discrepancyD 328. <itrogen as "ell as oxygen in the air "as remo ed by the reaction "ith heated Bg 0more reacti e than copper1. &hen a ne" gas occupying about $8 of air "as isolated. &he density of the ne" gas "as about 0 1 times that of air.
327. # pre iously unseen line spectrum "as obser ed from this ne" gas separated from % cc of air. &he most remar!able feature of the gas "as the ratio of its specific heats 0Cp-C 1, "hich pro ed to be the highest possible, %-3. &he obser ation sho"ed that the "hole of the molecular motion "as 0 monatomic gas. 0$1 electronic 0.1 ibrational 031 rotational 051 translational 1. &hus, argon is a
32$,. Calculate the "eight of argon in a $, m x $, m x $, m hall at (&P. In $875, 4ayleigh and 4amsay announced the disco ery of #r. Lisco ery of other noble gases 0;e, <e, /r, Oe1 follo"ed and a ne" group "as added to the periodic table. #s a result, 4ayleigh and 4amsay recei ed the <obel Pri>es in physics and in chemistry, respecti ely, in $7,5. 32$$. 'lement names sometimes ha e Free! or Latin origin and pro ide clues as to their properties or means of disco ery. Batch the element name "ith its meaning. helium neon argon !rypton ne" stranger la>y hidden
$.
xenon
sun
$3
Problem &: Solubility of salts

&he solubility of metals and their salts played an important role in 'arthIs history changing the shape of the 'arthIs surface. ?urthermore, solubility "as instrumental in changing the 'arthIs atmosphere. &he atmosphere of the primiti e 'arth "as rich in carbon dioxide. (urface temperature of the early 'arth "as maintained abo e the boiling point of "ater due to continued bombardment by asteroids. Chen the 'arth cooled, it rained and a primiti e ocean "as formed. #s metals and their salts dissol ed the ocean became al!aline and a large amount of carbon dioxide from the air dissol ed in the ocean. &he CO. part of most carbonate minerals is deri ed from this primiti e atmosphere. #s life arose about 3.8 billion years ago and photosynthetic bacteria e ol ed about 3 billion years ago, molecular oxygen "as produced as a by2product of photosynthesis. #s oxygen reacted "ith the metal ions in the ocean, metal oxides "ith lo" solubility "ere deposited on the ocean floor "hich later became dry land through plate tectonic motion. Iron and aluminum ores "ere, and still are, of particular importance as ra" materials in human ci ili>ation. LetIs consider a solubility problem using sil er halides. Ksp alues for #gCl and #gHr are $.8P$,2$, and 3.3P$,2$3, respecti ely. 62$. 'xcess #gCl "as added to deioni>ed "ater. Calculate the concentration of Cl2 in e9uilibrium "ith solid #gCl. 4epeat the calculation for Hr2 assuming that #gHr "as added instead of #gCl. 62.. #ssume that ,.$,, L of $.,,P$,23 B #g= solution is added to a Cl2 solution of the same olume and concentration. Chat is the concentration of Cl2 in the solution once e9uilibrium has been establishedD Chat percentage of the total chloride is in solutionD 623. #ssume that ,.$,, L of $.,,P$,23 B #g= solution is added to a Hr2 solution of the same olume and concentration. Chat is the concentration of Hr2 in the solution once e9uilibrium has been establishedD Chat percentage of the total bromide is in solutionD
$5
625. 'xperimental erification of the ans"ers in 62. and 623 is difficult, because the exact olume and concentration of the solutions are un!no"n. 4epeat the calculations in 62. and 623 assuming that the concentration of the #g= solution is $.,$P$,23 B. <o" letIs assume that $.,,P$,23 B #g= solution is slo"ly added "ith constant stirring to a ,.$,, L solution containing both Cl2 and Hr2 at $.,,P$,23 B concentration. 62%. Chich sil er 0I1 halide "ill precipitate firstD Lescribe the situation "hen the first precipitate appears. 623. Letermine the percentage of Hr2, Cl2, and #g= ions in solution and in the precipitate after addition of $,,, .,,, and 3,, mL of #g= solution. Vadd $,, mL .,, mL 3,, mL 8 Hr 8 Hr in 8 Cl 8 Cl in 8 #g 8 #g in precipitate precipitate precipitate in solution in solution in solution
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Problem ': Physical methods for determination of Avogadro(s number

# ogadroIs number is a fundamental constant in chemistry. ;o"e er, an accurate determination of this alue too! a long time. # ogadro 0$6632$8%31 himself did not !no" # ogadroIs number as it is !no"n today. #t about the time of his death, # ogadroIs number determined from gas properties, such as diffusion coefficient and iscosity, approached % x $,... # ogadroIs number as "e !no" it today 03.,. x $, .31 became a ailable only in the early .,th century. LetIs consider three separate approaches. 82$. #t thermal e9uilibrium, the probability of finding a molecule "ith a mass m at height h is proportional to the Holt>mann factor, exp02E0h1-kBT1, "here E0h1 is the gra itational potential energy 0mgh, "here g is 7.8$ m-s.1 and kB is the Holt>mann constant. &hus, the number density at h follo"s QbarometricQ distribution*
( h) mg( h ho ) = exp k T B (h0 )

0a1 (pherical particles of diameter ,.% Rm and density $.$, g-cm3 are suspended in "ater 0density $.,, g-cm31 at .,SC. Calculate the effecti e mass m of the particles corrected for buoyancy. 0b1 <o" the number density of the particles "ith effecti e mass "ill follo" barometric distribution. In an experiment "here a ertical distribution of such particles "as measured, it "as obser ed that the number density at h decreased to $-e times the number density at ho o er a Holt>mannEs constant. 0c1 Calculate # ogadroIs number using Holt>mannEs constant and the gas constant. 04 + 8.3$5 G-mol /1 82.. # ogadroIs number can also be determined by single crystal O2ray crystallography. &he density of sodium chloride crystal is ..$3% g-cm3. &he sodium chloride lattice is sho"n belo" 0?igure 82$1. &he distance bet"een the centers of ad)acent <a= and Cl2 ions "as determined to be ..8$7 x $,28 cm. Calculate # ogadroIs number. ertical distance of 3.5,P$,23 cm. Calculate
$3
?igure 82$. Lattice structure of sodium chloride In the roc!2salt structure one finds a face2centered cubic array of anions and the same array of cations. &he t"o arrays interpenetrate each other. # unit cell contains 5 anions 08 centered at the apexes are each shared by 8 unit cells thus gi ing $ anion, and 3 positioned at the face centers are each shared by . unit cells gi ing 3 anions1. # unit cell also contains 5 cations. 823. In a celebrated oil drop experiment, Billi!an determined in $7$3 that the basic unit of electric charge is $.%73 x $,2$7 coulombs. Calculate # ogadroIs number from this alue and ?araday, "hich is electric charge per e9ui alent 0$ ?araday + 73,573 coulomb as used by Billi!an1.
$6
Problem ): An electrochemical method for determination of Avogadro*s number

Hy definition, # ogadroIs number is the number of atoms in exactly $. g of carbon2$.. # ogadroIs number recommended by COL#&# 0Committee on Lata for (cience and &echnology1 in .,,. is 3.,..$5$%0$,1P$,.3 mol2$, "here the number in parenthesis represents one standard de iation in the last t"o digits. # ogadroIs number can be determined electrolytically. Current and time are measured in order to obtain the number of electrons passing through the electrochemical cell from T + IUt 0charge + current x time1. Copper electrodes "ere used for electrolysis of ,.% B ;.(O5. Luring electrolysis, copper is lost from the anode as the copper atoms are con erted to copper ions. &he copper ions pass through the solution. #t the surface of the cathode, hydrogen gas is liberated through reduction of hydrogen ions in the acidic solution. 'xperimental results are as follo"s* decrease in anode mass* ,.3%%5 g constant current* ,.3,$ # time of electrolysis* $8,. s <ote that $ # + $ C-s or $ #Us + $ C and the charge of one electron is $.3,. x $,N$7 C. 72$. Crite the reactions at both the anode and cathode. 72.. Calculate the total charge that passed through the circuit. 723. Calculate the number of electrons in ol ed in the electrolysis. 725. Calculate the mass of a copper atom. 72%. Letermine # ogadroIs number. #tomic "eight of copper is 33.%53 g-mol. 723. Chat is the percent error in this measurement of # ogadroIs numberD 726. It is also possible in principle to collect the hydrogen gas e ol ed and use its "eight to determine # ogadroIs number. Calculate the "eight of e ol ed hydrogen gas. Is this determination of # ogadroIs number from the "eight of e ol ed hydrogen practicalD
$8
Problem 1+: ,nthalpy- entropy- and stability

#ll chemical changes in li ing and non2li ing systems obey la"s of thermodynamics. &he e9uilibrium constant of a gi en reaction is determined by changes in Fibbs free energy, "hich is in turn determined by enthalpy change, entropy change, and the temperature. $,2$. ?ill in the blan!s 0a2f1 "ith all that apply from the follo"ing* e9uilibrium constant, Ke9 entropy change, VS enthalpy change, VH free energy change, VG a. strongly temperature2dependent b. closely related to bond strength c. measure of change in randomness d. related to the 9uantity of reactants and products e. measure of spontaneity of a reaction f. measure of heat released or absorbed 0 0 0 0 0 0 1 1 1 1 1 1
&he follo"ing e9uilibrium exists in the apor phase dissociation of molecular addition compounds of donor molecules, L, and boron compounds, HO3. L HO30g1 W L0g1 = HO30g1 Kp + XLYXHO3Y-XLUHO3Y $,2.. Lissociation constants 0Kp1 at $,,SC of the molecular addition compounds Be3<UHBe3 and Be3PUHBe3 are ,.56. and ,.$.8 atm, respecti ely. Calculate the standard free energy change of dissociation at $,,SC for both compounds. Chich complex is more stable at this temperatureD $,23. &he standard entropy change of dissociation, VSS, is 5%.6 cal-mol / for Be3< HBe3 and 5,., cal-mol / for Be3P HBe3. Calculate the standard enthalpy change of dissociation for both compounds. Chich compound has the stronger central bondD #ssume that VH and VS are temperature2independent.
$7
$,25. Chich is more critical in determining the o erall stability of these addition compounds at $,,SC, enthalpy term 0VH1 or entropy term 0T VS1D $,2%. #t "hat temperature does Be3< HBe3 become more thermodynamically stable than Be3P HBe3D #ssume that VH and VS are temperature2independent.
.,
Problem 11: .e"is acids and bases

#cids and bases are essential for life. #mino acids ha e both acidic and basic groups. L<# and 4<# are nucleic acids that contain bases such as adenine, guanine, thymine, cytosine, and uracil. &hus, understanding acid2base chemistry is essential for understanding life. Oxygen "as so named by La oisier because of its acid2forming natureA the acid2forming nature of oxygen is a manifestation of its high electronegati ity. Le"is extended the definition of acids and bases, and electronegati ity is again central in understanding Le"is acidity and basicity. $$2$. Lescribe the molecular structure of HO3. Chat is the hybridi>ation of the boron orbitalsD $$2.. ;o" does this hybridi>ation change "hen the boron halide forms an adduct "ith a base such as pyridine 0C%;%<1D Is the structural change around boron upon adduct formation more fa orable "hen O is ? or ID List H?3, HCl3, and HHr3 in the order of increasing Le"is acidity based on the abo e structural consideration. $$23. 'lectronegati ity is another important consideration in predicting Le"is acidity. List H?3, HCl3, and HHr3 in the order of increasing Le"is acidity, based only on the electronegati ity of the halogen elements 0inducti e effect1. $$25. Is adduct formation bet"een the boron halide 0Le"is acid1 and pyridine 0Le"is base1 exothermic or endothermicD Chich Le"is acid "ill sho" the greatest enthalpy change upon adduct formationD $$2%. #lthough the gaseous state "ould be best for computing the relati e strengths of the three boron halides under consideration, the li9uid state of these materials could be used as a satisfactory reference state since the boron halides are relati ely non2polar li9uids or gases. &he enthalpy changes "hen mixing li9uid boron halide "ith nitroben>ene, H$, and "hen mixing the nitroben>ene2boron halide solution "ith pyridine also in nitroben>ene, H., are gi en belo". HO30li9.1 = C3;%<O.0li9.1 : C3;%<O. HO3 0soln.1 C3;%<O. HO30soln.1 = C%;%<0soln.1 : C%;%< HO30soln.1 = C3;%<O.0soln.1 H$ H.
.$
H?3 VH$ 0!cal-mol1 VH. 0!cal-mol1 2 3.6 2 .%.,
HCl3 2 8.6 2 3,.8
HHr3 2 $..% 2 3..,
Calculate VH3 for the follo"ing reactions. Lo they agree "ith your prediction in $$25D HO30li9.1 = C%;%<0soln.1 : C%;%< HO30soln.1 $$23. Horon halides also sho" ery different reacti ity "ith "ater. H?3 forms stable addition compounds "hereas HCl3 and HHr3 react reactions. H?3 = ;.O : A HCl3 0or HHr31 = 3;.O : / = 0 $$26. Chat !ind of extra bond can be formed in HO3 bet"een the central boron and one of its halides possessing lone pair electrons in order to fulfill the Zoctet ruleED 'xplain ho" this extra bond affects the Le"is acidity of HO3. iolently "ith ;.O at temperatures belo" .,SC. Predict the products, A, /, and 0, for the follo"ing
..
Problem 12: Solubility e1uilibrium in a buffer solution

Hiochemical reactions ta!e place in buffered a9ueous en ironments. ?or example, the p; of the blood is maintained around 6.5 by the buffering action of carbonate, phosphate, and proteins. Bany chemical reactions in the laboratory are also carried out in buffer solutions. In this problem, letEs consider the solubility e9uilibrium in a buffer solution. $.2$. ;.( gas occupying 55, mL at (&P can be dissol ed in $,, mL of "ater at .%oC. Calculate the molar concentration of ;.( in "ater saturated "ith ;.(. #ssume that there is no olume change in "ater upon dissolution of ;.(. $.2.. #ssume that e9uilibrium is established after a ,.,$, B ?eCl. solution is saturated "ith ;.( by continuously bubbling ;.( into the solution. Ksp0?e(1 + X?e.=YX(.2Y + 8., x $,2$7 at .%oC ?or acid dissociation of ;.(, K$ + X;=YX;(2Y-X;.(Y + 7.% x $,28 K. + X; YX( Y-X;( Y + $.3 x $, ?or self ioni>ation of "ater, K" + X;=YXO;2Y + $ x $,2$5 051
= .2 2 2$5
0$1
0.1 031
In the solution, the positi e charge is balanced by the negati e charge* X;=Y = .X?e.=Y + XCl2Y = XO;2Y = X;(2Y = .X(.2Y 0%1
Cross out terms that are negligibly small in the charge balance e9uation, 0%1, in order to determine X;=Y and X?e.=Y. Could you increase or decrease the p; of the solution to precipitate more ?e(D ;o" does the increase of $ in p; affect the concentration of ?e.= ionD $.23. ;o" "ould you ad)ust the final p; of the solution saturated "ith ;.( to reduce the concentration of ?e.= from ,.,$, B to $., x $,28 BD
.3
$.25. Mou "ant to use acetic acid 0;O#c1-sodium acetate 0<aO#c1 buffer to achie e $., x $,28 B concentration of ?e.= as described abo e. (uppose that you are ma!ing the buffer by mixing acetic acid and sodium acetate in "ater in a olumetric flas!. 'nough acetic acid "as added to ma!e the initial concentration ,.$, B. Considering that the precipitation reaction produces ;= 0?e.= = ;.( : ?e(0s1 = .;=1, ho" "ould you ad)ust the initial concentration of sodium acetate to obtain $., x $,28 B ?e.= after e9uilibrium is establishedD &he acid dissociation constant for acetic acid at .%oC is $.8 x $,2%. $.2%. Chat is the p; of the buffer before ;.( is introduced and ?e( is precipitatedD
.5
Problem 13: 2edo3 potential- 4ibbs free energy- and solubility

&he proton, neutron, and electron are the three sub2atomic particles important in chemistry. &hese particles occupy t"o regions. Proton and neutron occupy the central place of the nucleus and electron the ast space outside the nucleus. <eutron transfer does not ta!e place in ordinary chemical reactions. Proton 0hydrogen ion1 transfer constitutes acid2base reactions. 'lectron transfer constitutes oxidation2reduction reactions. Oxidation2reduction reactions are essential for life. Photosynthesis and respiration are t"o prime examples. Oxidation2reduction reactions also allo" !ey thermodynamics 9uantities to be measured as demonstrated in this problem. Fi en the follo"ing information* #g=0aq1 = eN : #g0s1 #gHr0s1 = eN : #g0s1 = HrN0aq1 VGfS0<;30aq11 + N.3.%, !G-mol VGfS0#g0<;31.=0aq11 + N$6.$. !G-mol =$.55$ J ES + ,.6773 J ES + ,.,6$3 J
V ;OHr +1.584 V Hr.0aq1 ? HrN0aq1 HrO3N0aq1 +1.491

$32$. Calculate VGfS0#g=0aq11. $32.. Calculate the e9uilibrium constant for the follo"ing reaction at .%SC. #g=0aq1 = . <;30aq1 : #g0<;31.=0aq1 $323. Calculate the K(P alue of #gHr0s1 at .%SC. $325. Calculate the solubility of #gHr in a ,.$,, B a9ueous solution of ammonia at .%SC. $32%. # gal anic cell using the standard hydrogen electrode as an anode is constructed in "hich the o erall reaction is
.%
Hr.0 1 = ;.0g1 = . ;.O0 1 : . HrN0aq1 = . ;3O=0aq1. (il er ions are added until #gHr precipitates at the cathode and X#g=Y reaches ,.,3,, B. &he cell oltage is then measured to be $.6.$ J. Calculate VES for the gal anic cell. $323. 'stimate the solubility of bromine in the form of Hr.0aq1 in "ater at .%SC.
.3
Problem 1 : 5easuring the o6one level in air

O>one both helps protect and leads to damage of life forms. #s the oxygen le el in the 'arthEs atmosphere built up significantly about . billions years ago during "hich time the, o>one le el in the upper atmosphere also increased. &his o>one layer effecti ely bloc!ed ultra iolet radiation and made life on land possible. &oday, the o>one layer appears to be depleting 2 de eloping a large hole 2 thus, the fate of this layer is of great concern. On the other hand, o>one is a health ha>ard in our immediate en ironment at ground le el. It is a !ey constituent of photochemical smog. # simple method for measuring the concentration of o>one in the ground2le el atmosphere is as follo"s. #ir is bubbled through an acidic a9ueous solution containing iodide and the atmospheric o>one oxidi>es iodide to triiodide unbalanced reaction* O30g1 = I[0a91 : I320a91 = O.0g1 0$1 ia the follo"ing
#t the end of the sampling period, the triiodide concentration is determined "ith a @JN Jis spectrophotometer at .%5 nm. #ir "as bubbled for 3,., min into $, mL of an a9ueous solution containing excess of /I under the follo"ing atmospheric conditions* pressure + 6%, torr, temperature + .78 /, flo" rate + .%, mL min2$. &he absorbance of the resulting I32 solution "as measured in a $.$2cm cell by using a spectrophotometer e9uipped "ith a photocell. &he photocell resistance is in ersely proportional to the light intensity. 4esistance alues for the blan! and the sample solution "ere $..$ ! and $7.5 ! , respecti ely. &he molar absorption coefficient of the I32 solution "as determined to be ..5 x $,% B2$ Ucm2$. In arious useful units, the uni ersal gas constant is* 4 + 8.3$556. G U /2$ U mol2$ + ,.,8.,%653 L U atm U /2$ U mol2$ + 3..3336 L U torr U /2$ U mol2$ + $.786 cal U /2$ U mol2$ $52$. Halance e9uation 0$1. $52.. Lra" the Le"is structure for o>one. $523. Calculate the number of moles of o>one in the sampled air. $525. #ssuming that the gases beha e ideally under the conditions used, calculate the concentration in !!" of o>one present in the sampled air.
.6
Problem 1#: .ifesaving chemistry of the airbag

Certain chemical reactions can protect people from serious in)ury or death. &he follo"ing chemical reactions used to be utili>ed to rapidly produce large amounts of nitrogen gas inside an automobile airbag* .<a<3 : .<a = 3<.0g1 $,<a = . /<O3 : /.O = %<a.O = <.0g1 /.O = <a.O = (iO. : al!aline silicate 0\glassQ1 0$1 0.1 031
$%2$. Crite the Le"is structure for the a>ide anion and nitrogen molecule. $%2.. ;o" many grams of sodium a>ide and potassium nitrate are needed to generate enough nitrogen to fill a $%2liter airbag at %,oC and $..% atmD $%23. (eparately, "rite a balanced e9uation for the decomposition of nitroglycerine. ?inally, "rite a balanced e9uation for the decomposition of lead a>ide used for detonation. In "hat "ays are the reactions for sodium a>ide, nitroglycerine and lead a>ide similarD $%25. Crite a balanced e9uation for the reaction of sodium a>ide "ith sulfuric acid to form hydra>oic acid 0;<31 and sodium sulfate. $%2%. Chen 3, g of sodium a>ide reacts "ith $,, mL of 3 B sulfuric acid, ho" many grams of hydra>oic acid are producedD
.8
Problem 1$: 0atalysts for the synthesis of ammonia

&he synthesis of ammonia is a prime example of ho" chemistry can be used to impro e human life. ' en though primiti e li ing systems had been \fixing] nitrogen to ma!e compounds of nitrogen for hundreds of millions of years, human beings learned to prepare ammonia only about $,, years ago. #mmonia is a source of nitrogen atom re9uired for all amino acids and is essential in the production of fertili>er. #mino groups can be easily transformed into nitro groups found commonly in explosi es such as &<&. Bore than $,, million tons of ammonia are produced annually "orld"ide, second only to sulfuric acid. ;o"e er, <ature produces e en more ammonia than the chemical industry. #mmonia is synthesi>ed from nitrogen and hydrogen, ho"e er, the chemical bond of the nitrogen molecule is extremely stable, !eeping ammonia from being synthesi>ed "ithout proper conditions or use of catalyst. In the early .,th century, ;aber2Hosch method "as de eloped for ammonia synthesis using high pressure and temperature, "hich is still employed in todayEs chemical industry. ;aber 0$7$81 and Hosch 0$73$1 "ere a"arded the <obel Pri>e in chemistry for these contributions. $32$. ?irst, let us see if the reaction is feasible from a thermodynamic standpoint. Calculate the standard entropy change of the system in the follo"ing reaction* <.0g1 = 3;.0g1 .<;30g1 &he standard entropy is $7$.3, $3,.6, and $7..% G-0/ mol1 for <., ;., and <;3, respecti ely. Loes the entropy of the system increase or decreaseD If it decreases, "hat must be the case for the reaction to proceed spontaneouslyD $32.. &o see if the reaction is li!ely to be exothermic, consider a similar reaction bet"een oxygen and hydrogen to ma!e "ater. Is that reaction exothermicD Batch the compounds "ith the standard enthalpy of formation 0VHfo1 in !G-mol. ;.O0g1 ;?0g1 <;30g1 2 53.$$ 2 .5$.8. 2 .6$.$
.7
$323. @sing the alue of VHfo you selected abo e, calculate the entropy change at .%oC of the system and the surroundings combined. $325. 4eaction rate is another important consideration. &he rate determining step of the reaction, <.0g1 = 3;.0g1 .<;30g1 is the atomi>ation of the nitrogen molecule. #ssuming that the acti ation energy of the atomi>ation is the bond energy of the nitrogen molecule 075, !G mole2$1 and that the # factor of the rate determining step is $,$3 sec2$, calculate the rate constant of atomi>ation at 8,,oC using the #rrhenius rate la". Calculate the rate constant at the same temperature "hen the acti ation energy is lo"ered by half "ith a catalyst. &he amount of catalyst used by the chemical industry is enormous. Bore than $,, tons of catalyst are used in a factory "here $,,, tons of ammonia can be produced daily. In addition to the ?e catalyst that has been used since ;aber and Hosch, a 4u catalyst is used in ammonia synthesis. Betal complex binding "ith elemental nitrogen and hydrogen is also studied as homogeneous catalyst for ammonia synthesis in solution. $32%. 4eactions bet"een reactants and undissol ed metal catalyst can occur at the metal surface so that the catalyst surface area affects the catalysis rate. Calculate the mole number of nitrogen molecules adsorbed on $ !g of ?e catalyst. #ssume that the catalyst is composed of $ m3 cube 0 ery fine po"der1 and that all six faces of the cube are a ailable for nitrogen adsorption. &he density of ?e is 6.83 g-cm3 and the adsorption area for a nitrogen molecule is ,.$3 nm.. $323. If a soluble, homogeneous catalyst "ith BC of %,, g-mole is synthesi>ed for nitrogen molecule binding, ho" many nitrogen molecules bind to $ !g of catalystD #ssume one catalyst molecule binds one nitrogen molecule. Compare the result "ith the number of nitrogen molecules adsorbed on the ?e surface in Problem $32 .. $326. Chile ammonia is synthesi>ed under high pressure and temperature in the chemical industry, natural ammonia is synthesi>ed from atmospheric nitrogen, ^,.8 atm. 'n>ymes for ammonia synthesis in nature called nitrogenases are proteins "ith cofactors that contain ?e or Bo. &he ammonia synthesis reaction by nitrogenases is an electron transfer reaction* <.0g1 = 8;= = 8e2 .<;30g1 = ;.0g1. $3 #&P molecules are consumed in the reaction. #&P molecule decomposes into
3,
#LP and inorganic phosphate, and releases an energy of 3,.% !G-mole. Calculate the energy re9uired to synthesi>e $ mole of ammonia using nitrogenase. #t least 5,, !G of energy is used for the synthesis of $ mole of ammonia in the chemical industry these days.
3$
Problem 1&: 7rom sand to semiconductors

Chemistry enables life. Chemistry also enriches life. ?or thousands of years, human beings ha e been putting sand to good use. Flass "as made from sand. Lenses "ere made from glass and "ere used to ma!e telescopes, microscopes, eyeglasses, and glass"are for chemical experiments. Bore recently, sand became a starting material for semiconductors. One of the most abundant elements in the 'arthIs crust is silicon, "hich is found in compounds containing (i2O bonds. (ilica 0(iO.1 is present in abundance at the earthEs surface.
?igure $62$. _2cristobalite, one structure of silica. $62$. ;o" many (i and O atoms exist in the unit cell of _2cristobaliteD $62.. (uggest the hybridi>ed orbital of (i for this structure and guess the bond angle of O2(i2O. (iO. is ery unreacti e, yet it reacts "ith ;?. &he reaction "ith ;? may be used to etch glass or in semiconductor manufacturing* (iO.0s1 = 3;?0a91 : A0a91 = .;=0a91 = .;.O0l1 $623. Lra" the molecular structure of A. (ilicon can be obtained by heating silica and co!e 0a form of carbon1 at 3,,,SC in an electric arc furnace.
3.
$625. Crite a balanced e9uation for the reaction of (iO. "ith carbon. In this case, assume that only one !ind of gas is formed "hose Le"is structure should sho" formal charges. $62%. (!etch the molecular orbitals of the gas formed from the reaction abo e. &o obtain ultrapure silicon, crude silicon is treated either "ith Cl. gas to gi e \/ or "ith ;Cl gas to gi e \0. $623. Crite a balanced e9uation for the reaction of (i "ith Cl.. $626. Predict the molecular structure of \/. $628. Is the product \0 from the follo"ing reaction 0$1 polar or notD Lra" the 32 dimensional structure of 0 and s!etch the direction of its dipole moment, if any* (i0s1 = 3;Cl0g1 : \0 0g1 = ;.0g1 0$1
&he re erse reaction of 0$1 is spontaneous at $,,,oC, depositing ultrapure silicon. &he final purification of the silicon ta!es place by a melting process called >one refining. &his process depends on the fact that the impurities are more soluble in the li9uid phase than in the solid phase 0?igure $62.1. &he >one refining procedure can be repeated until the desired le el of purity 0less than ,.$ ppb impurity1 is obtained.
33
?igure $62.. `one refining of silicon $627. ;o" many atoms per gram in the silicon "afer ha e been replaced by impurity atoms "hen the impurity le el is ,.$ ppbD Li!e all semiconductors, high2purity silicon fails to conduct electrical current until a minimum electrical oltage is applied, but at higher oltages it conducts moderately "ell. (emiconducting properties of silicon can be impro ed significantly by doping. Loping is the addition of a minor amount of a different element. $62$,. Chen a small number of boron atoms replace silicon atoms in solid silicon, "hat is the charge carrierD Chat is the name for this type of doped2semiconductorD $62$$. Lra" a band diagram that can explain conducti ity impro ement upon replacement of some silicon atoms "ith boron atoms. (ho" in your dra"ing the band gap change after doping.
35
Problem 1': Self8assembly

@seful and essential structures can be made by self2assembly. In fact, life2forms "ere first made possible by the self2assembly of cell membranes about 5 billion years ago. (elf2assembly is a fundamental principle that generates structural organi>ation on all scales from molecules to galaxies. (elf2assembly is defined as re ersible processes in "hich pre2existing parts or disordered components of a pre2existing system form stable structures of "ell2defined patterns. (ome transition metal complexes can participate in the self2assembly. ?or example, a <i complex "ith a long al!yl chain can be formed from many separate parts in the follo"ing reaction.
$82$. Predict the structure around the <i0II1 cation. $82.. Letermine "hether #.= is paramagnetic or not, using the d2orbital splitting pattern of <i0II1 in this structure. $823. Indicate the hydrophobic portion in #.=.
3%
?igure $82$. &he molecular structure for #.= and the pac!ing structure of #0ClO51. ;.O. $825. Chat is the dri ing force for such assemblyD 0;int* Its ionic compound, #0ClO51. ;.O, is found to float on the surface of "ater although its density is greater than $.,.1 Betal complexes of &C<T 06,6,8,82tetracyano2p29uinodimethane1 ha e been studied due to magnetic and electric conducting properties.
0&C<T +
&he infrared spectrum is diagnostic for the formal oxidation state and the coordinati e status of the &C<T molecules. $82%. ?or &C<T as pictured, "hich bond 0among a2e1 has the highest fre9uencyD ibrational
33
$823. Point out the bond0s1 0among a2e1 "hich might be shortened "hen &C<T is reduced to form the radical anion. &he &C<T deri ati e of #.= 0X#.=0&C<T1.Y0&C<T1 0C;3COC;311 also sho"s an interesting structural feature as sho"n in ?igure $82..
?igure $82.. &he molecular structure for #.= and the pac!ing structure of X#.= 0&C<T1.Y0&C<T C;3COC;31 $826. Chat is the coordination number for <i in the &C<T deri ati e of #.=D $828. In this structure, &C<T molecules o erlap one another. Chat is the dri ing force for such organi>ationD
36
Problem 1): Stereochemistry 9:rganic synthesis ; 1<

&he fermentation of starch "ith malt produces ethyl alcohol. Luring this process, the hydrolysis of starch is cataly>ed by the en>yme diastase present in malt to produce maltose, a disaccharide. Baltose 0C$.;..O$$1 reduces &ollensE and ?ehlingEs reagents and it is oxidi>ed by bromine in "ater to maltobionic acid 00C$$;.$O$,1COO;1, a mono carboxylic acid. In order to deduce its structure, maltose "as sub)ected to series of reactions*
!al"#$e (C12H22O11) Br2 H2O
H+ H2O
2 B (C%H12O%)
HNO3
N
(C%H10O8) #p"i(all+ a("i,e
!al"#&i#'i( a(i)
Me2 O4 NaOH
C ((C19H3*O10)COOH)
H+, H2O
D
(C10H20O%) HNO3 CrO3 LiAlH4
E
(C10H20O*)
[I]
i'"er!e)ia"e
F
(C4H%O5)
F'
(C5H10O4) #p"i(all+ a("i,e
G
(C%H10O%)
H
(C3H%O3)
#p"i(all+ a("i,e
J
(C10H22O%)
K
(C10H22O%) Me2 O4 NaOH
Me2 O4 NaOH
L
(C12H2%O%) #p"i(all+ a("i,e
M
(C12H2%O%) #p"i(all+ i'a("i,e
$72$. Lra" structures /, %2= in a ?isher pro)ection. $72.. Lra" structures for maltose, maltobionic acid and 0 in a ;a"orth pro)ection.
38
Problem 2+: >otal synthesis 9:rganic synthesis ; 2<

&he first total synthesis of an organic compound "as accomplished in the $7 th century by /olbe starting from carbon and sulfur as depicted in the follo"ing scheme.
heat Cl. light
(8
C(.
CCl5
heat
acetic acid
`n
O;2
Cl Cl
Cl Cl
' en in modern organic synthesis, a similar synthetic strategy has been applied in the synthesis of amino acids.
O < H CCl3 O H; O <32 BeO;
O; CCl3
O;2
0C8;3OCl.1
0C7;7<3O.1
0C8;3<3OCl1 i1 ;.O ii1 ;., Pd-C
0C8;7<O.1
Lra" the structures of A2, and designate the a"s# $te stereochemistry of % and , using the 4-( con ention.
37
Problem 21: ,namine chemistry 9:rganic synthesis ; 3<

'namine is formed bet"een !etone and secondary amine in the presence of acid catalyst.
O = < ;
= ;=
<
0$1
.$2$. Propose a mechanism for enamine formation in the presence of acid catalyst 0e9uation $1. .$2.. &his process exhibits a bell2shaped p; dependence in the presence of acid catalyst. &he maximum rate of formation occurs at p; 325. Propose a plausible reason "hy this dependence occurs. .$23. 'namine reacts "ith con)ugated enones such as methyl inyl!etone to form a $,%2 dicarbonyl compound after the hydrolysis of enamine 0e9uation .1.
O <
0.1
&he product of this reaction no" has one chiral center. (uggest conditions of special amine to ma!e stereospecific product as sho"n in e9uation ..
5,
Problem 22: :3idation and reduction in organic synthesis

In the manipulation of organic compounds, oxidation reaction and reduction reaction are the most important reactions. 'specially, a chemo2selecti e, region2selecti e or stereo2selecti e reduction-oxidation is ery important in designing an efficient organic synthesis of a target molecule. Chile nature achie es such selecti ity through specific design of acti e sites of en>ymes, chemical transformation mostly relies on subtle difference in reacti ity by changing the nature of reagents. &he follo"ing scheme is a good example of chemo2selecti e reduction and oxidation reactions starting from ethyl cyanoacetate.
NaBH4 - FeCl3
'tOOC
C<
EtOH
:
A (C5H11NO2)
PhCOCl K2CO3 H2O
B (C12H15NO3)
: ! :Ac Ac: :Ac
B (C12H15NO3)
(DMP)
C (C12H13NO3)
..2$. Chen ethyl cyanoacetate "as treated "ith a reducing agent <aH; 5 in presence of ?eCl3, a selecti e reduction of a functional group "as obser ed. Chen the product # "as reacted "ith ben>oyl chloride, $ e9ui alent of ben>oyl chloride "as consumed to form H. Chat are the structures of # and HD ..2.. Less2Bartin Periodinane 0LBP1 is a strong but mild oxidi>ing agent, and can oxidi>e arious functional groups in a selecti e manner. Chen H "as oxidi>ed "ith LBP a clean oxidation occurred to form C. $;2<B4,
$3
C2<B4, I4 and mass
spectra "ere obtained. &hese spectra sho"ed that a clean transformation occurred to form a single product. In the $;2<B4 a doublet bet"een %^3 ppm sho"s the coupling constant G+8.8 ;>. Lra" the structure of C. ..23. In the $;2<B4, the chemical shift of one pea! sho"ed up near a + $$.% ppm. #ssign the proton in the structure C for this chemical shift. Chat is the reason for the chemical shift for the assigned proton that does not appear in the region 0a + b^ 8 ppm1 for ordinary protons of that functional groupD
5$
$;2<B4 of C
$3C2<B4 of C
I4 of C
Bass spectrum of C
5.
53
Problem 23: Antifree6e proteins

&he temperature belo" ,oC occurs commonly on earth. ;o" can organisms sur i e in conditions "here "ater free>esD ?or many insects exposed to prolonged subfree>ing conditions, cryoprotectant synthesis begins in their bodies during early autumn, and these substances are cleared in early spring. ?igure $ sho"s the seasonal content of glycerol in a free>e2a oiding insect.
?igure .32$. Laily maximum and minimum temperatures and glycerol content in the free>e2a oiding lar ae of the goldenrod gall moth. &he structure of glycerol is gi en on the right. 04eference* /.H. (torey and G.B. (tory $788 Physiol. 4e . 38*.61 .32$. Chat is the "eight percent of glycerol in the insect if it could a oid free>ing at N .,oC due to glycerol concentration aloneD #ssume the insect beha es as an ideal solution. Chat "ould be the osmotic pressure at this glycerol concentrationD Comment on the resulting alues. &he free>ing point depression constant for "ater is Kf +$.83oC-0mol-!g1.
55
.32.. Chat is the actual fraction of amount of glycerol aloneD
glycerol in the insectEs "et "eight in GanuaryD
Chat "ould be the free>ing point of "ater in the insect in Ganuary considering the
.323. In addition to free>ing point depressants, \antifree>e proteins] are !no"n to act to a oid free>ing in animals including cold2"ater fish and many insects. &he colligati e free>ing point depression due to antifree>e proteins is 9uite small. 'xperiments suggest that antifree>e proteins inhibit the gro"th of small ice particles. If some threonine or aspartate side chains composing the protein are chemically modified, the antifree>e acti ity disappears. Chat !ind of interactions bet"een antifree>e proteins and ice particles are probably responsible for the antifree>e acti ityD
Protein backbone Side chains
5%
Problem 2 : >he human body

&he human body consists of cells, "hich in turn consist of atoms. #bout t"o thirds of body "eight is "ater, "hich means that about t"o thirds of cell mass is "ater. .52$. # human body "eighing 3, !g consists of about $,0
1
atoms. Consider the
a erage atomic "eight of the three atoms in a "ater molecule. ?or your o"n information, consider the a erage atomic "eight of atoms in other molecules such as proteins, fats, and carbohydrates. .52.. # human body consists of about $,, trillion 0$,$51 cells. #ssume that all human cells are cubic and identical in si>e. 'stimate the si>e of an a erage human cell 0length of the edge of the cube1 in one significant figure. .523. #ssume that all atoms in a cell are uniformly distributed. 'stimate the distance bet"een t"o atomic nuclei in a cell. .525. 'stimate the distance bet"een the centers of mass of t"o "ater molecules in pure "ater. .52%. 'stimate the a erage distance bet"een atomic nuclei in pure "ater. Compare your result "ith ans"ers in .523 and .525.
53
Problem 2#: Hemoglobin

#nother important class of compounds in the human body is proteins. Bany proteins carry out catalytic functions. ;emoglobin, on the other hand, transports oxygen from the lung to remote parts of the body. .%2$. &he molecular "eight of hemoglobin is about 36,,,, g-mol. &he a erage amount of hemoglobin in erythrocytes in $,, mL of blood is $% grams. &he concentration of hemoglobin in blood is 0 1 B.
.%2.. 'stimate the a erage distance bet"een t"o oxygen molecules in the air "e breathe. #ssume frigid air at ,oC in "hich .$8 of air is oxygen. .%23. ;enryEs la" is "ritten solubility + k; x partial pressure 0k;* ;enryEs constant1 ;enryEs constant for oxygen is $.3 x $,23 mol L2$ atm2$. 'stimate the a erage distance bet"een t"o oxygen molecules in "ater in e9uilibrium "ith air. .%25. # hemoglobin molecule can bind up to four oxygen molecules. 'stimate the a erage distance bet"een t"o oxygen molecules in blood "hen all of the hemoglobin is saturated "ith oxygen. Compare your result "ith ans"ers in .%2. and .%23 and note ho" efficiently hemoglobin concentrates and transports oxygen to tissues "here the partial pressure of oxygen is lo". .%2%. &here are about 0 1 amino acids in hemoglobin. 'stimate using a erage
molecular "eight of amino acids and chec! against literature alues. .%23. &here are about 0 1 different !inds of amino acids in hemoglobin.
.%26. &rypsin hydroly>es peptide bonds at the carboxyl group of arginine and lysine. Consider, for example, the follo"ing peptide. ;3<=2gly2phe2arg2ala2ala2tyr2leu2phe2his2pro2lys2gly2trp2glu2ile2asp2phe2COO2 @pon complete hydrolysis by trypsin, the follo"ing set of peptides "ill result.
56
;3<=2gly2phe2arg2COO2 ;3<=2ala2ala2tyr2leu2phe2his2pro2lys2COO2 ;3<=2gly2trp2glu2ile2asp2phe2COO2 @pon complete hydrolysis of hemoglobin after reduction of the disulfide bonds and al!ylation, you expect to find on the a erage about 0 peptide 0peptide resulting from hydrolysis by trypsin1. .%28. &he a erage molecular "eight of the tryptic peptides is about 0 1. 1 amino acids in a tryptic
58
Problem 2$: 5ass spectrometry of hemoglobin

.32$. If you li ed in the $7th century, "hat method "ould you use to determine the molecular "eight of hemoglobinD 'xplain. Hrea!throughs in molecular "eight determinations of biopolymers such as proteins "ere recogni>ed "ith the .,,. <obel Pri>e in chemistry a"arded to ?enn for de eloping electrospray ioni>ation mass spectrometry 0'(I B(1 and to &ana!a for pioneering "or! leading to matrix2assisted laser desorption-ioni>ation time2of2flight mass spectrometry 0B#LLI2&O? B(1. In B#LLI2&O? B(, proteins are embedded in a crystal of @J2absorbing matrix molecules and desorbed-ioni>ed upon irradiation "ith a @J laser pulse. (ingly charged protonated protein ion, XB=;Y=, is produced as a ma)or species from a protein "ith mass B. .32.. Consider hemoglobin "ith a 36,535 La molecular "eight. #fter desorptionioni>ation, the XB=;Y= ion is accelerated by .,.,,, !J. Calculate the energy of the protein ion in )oule. 0coulomb x olt + )oule10e + $.3,.$8 x $,2$7 coulomb1 .323. &he accelerated protein ion is then allo"ed to tra el $.,,,, m in an e acuated flight tube to a detector. #ll electrical energy is con erted to !inetic energy 0mv.-.1. If the flight time of the protein ion "as determined to be $.3.$7 x $,25 s, "hat is the molecular "eight of hemoglobin calculated from the flight time measurementD Chat is the mass accuracy in ppmD .325. &he flight tube is maintained under a high acuum at .%oC. Chat is the residual pressure in the flight tube at "hich the mean free path of air molecules is the same as the length of the flight tubeD (ee Problem . for definition of mean free path. #ssume that all air molecules are spheres "ith a diameter of . angstroms.
57
Problem 2&: Post8translational modification

<ature uses ., amino acids to ma!e di erse proteins. ;o"e er, since the di ersity from ., amino acids sometimes is not enough, chemical modifications are carried out mostly at the side chains of amino acids to generate more di erse functional groups by many natural en>ymes. Bany types of these post2translational modifications are important in recognition of protein2protein, protein2L<#, protein24<# molecules. &hese modifications are used as turn2on 0off1 s"itches, transferring messages, !no"n as signal transduction in li ing cells. 4ecently, methylation "as found to be as important as other !no"n post2translational modifications, such as phosphorylation and glycosylation. Li!e other modifications, there is a re erse reaction, demethylation. &he t"o processes "or! oppositely, turning signals on and off 0off and on1, li!e phosphorylation and glycosylation. ;o"e er, processes of methylation and demethylation in nature are 9uite different. In other "ords, the mechanisms of the t"o facilitating en>ymes are not the re erse of each other. .62$. Considering the functional groups of side chains existing in ., amino acids, "hat !ind of functionality is suitable for generating more di ersity o"ing to methylation and demethylationD <ame t"o amino acids. .62.. In methylation of an amino acid side chain, (2adenosylmethionine 0(#B1 is used as a cofactor. (#B is made from methionine and #&P. Leduce the structure of (#B.
<;. < O O O ;O P O P O P O O O O < O < <
O ;.< C;C O; C;. C;. ( C;3 Bethionine 0Bet1
O; O; #denosine triphosphate 0#&P1
.623. Propose a mechanism of amino acid methylation "ith (#B.
%,
.625. &"o steps ma!e up the proposed mechanism for demethylation. &he en>yme uses ?#L as a cofactor for the first step. Propose plausible mechanisms for demethylation.
<;. < O; ;O O O O P O P O O O < O O; O; < <
< <
O; < O < O
?la in2adenine dinucleotide 0?#L1
%$
Problem 2': >ransition state in en6ymatic reactions

'n>ymes are catalysts for li ing organisms. &hey ha e e ol ed to enable specific chemical reactions necessary for life to thri e more efficiently. In the acti e site of an en>yme, amino acid residues including side chains ha e e ol ed to pro ide space for the transition state 0&(1 of the chemical transformation to exist "ith conformational and electrostatic match. &hus, the binding affinity of this &( to the en>yme is expected to be ery high 0if one can calculate1, stabili>ing the energy of the transition state through an en>yme2&( complex. &his lo"ers the acti ation energy of the reaction and creates rate acceleration. If one can calculate the binding constant o"ing to the complex formation, one could readily deduce ho" efficient the en>yme is by calculating kcat-kuncat. Ban2made en>ymes are holy grails for some chemists, because they can gi e insight about the beha ior of natural en>ymes and can be used as useful synthetic and therapeutic tools. Catalytic antibodies can be one of these !inds of artificial en>ymes. #ntibodies ha e antigen2binding sites, in "hich the target antigen binds "ith high affinity 0KL + $,272$,2$$ B1 and "ith great specificity. &hese properties can be exploited as acti e sites in artificial en>ymes. #ntigen2binding sites may ser e to specifically recogni>e substrates and perform certain chemical reactions. (ince these catalytic antibodies need to accommodate transition state 0&(1 structures in chemical transformations, an antigen that triggers the production of the catalytic antibody must be designed and synthesi>ed )ust li!e the &( structure. ;o"e er, chemists cannot prepare a transition state structure because it is transient. Instead, one can synthesi>e a stable compound that resembles the structure of the transition state. &his ne"ly designed compound is called a transition state analogue 0&(#1. Once a &(# is made, it can be in)ected into mice to generate antibodies. &he half2life of the &(# should be longer than . "ee!s at physiological conditions to obtain an ade9uate immune response. #fter generating as many antibodies as possible, the most tightly binding and specific antibodies are selected as candidates for antibody catalysts. .82$. If one of the selected antibodies has KL + $,2$3 B against the &(#, comparing "ith normal antibody 0KL + $,23 B1 ho" much stabili>ation energy can the &(# gain from the binding to this specific antibodyD .82.. Let us assume that the &(# can be considered as the real transition state 0&(1. &hen, ho" much rate enhancement "ill be obtained "hen "e "ill use this catalytic
%.
antibody for the intended chemical transformationD Lescribe this enhancement by kcat-kuncat. Bost scientists are interested in the specific hydrolysis of the pathogenic proteins or peptides such as _2amyloid as the intended chemical reaction by catalytic antibodies. #ssuming that the follo"ing reaction is the intended reaction by catalytic antibody, &( of the hydrolysis of the amide bond should be considered to ma!e a plausible &(#.
<O. < ; <O. O; = ;.<
O 4
;.O Cat. #b
O 4
.823. Chat is the transition state or reacti e intermediate of the abo e amide bond hydrolysisD .825. Lesign a stable &(# suitable for replacing the &(. 4emember that the &(# should be stable and structurally close to the &(.
%3
Problem 2): =ature(s building bloc?s

<atural rubber is a polymer composed of isoprene, the con)ugated diene .2methyl2$,32 butadiene. Isoprene can be found not only in rubber but in a "ide range of natural products called terpenes, most of "hich ha e carbon s!eletons made up of isoprene units )oined head2to2tail. 4ecognition of this fact 2 the isoprene rule 2 has been great help in "or!ing out structures and determining the biosynthetic origin of terpenes. .72$. ?ind the isoprene units in the follo"ing terpenoid natural products.
O;
O;
#cO
O;
O 4 O O O; OH> O#c
%5
In polymer chemistry, the repeating unit is called a monomer and the repeating units are )oined together through chain reaction polymeri>ation or step2reaction polymeri>ation. # fe" examples of step2reaction polymeri>ation are pro ided belo". .72.. Lra" the repeating unit in each polymer product.
COO; = ;.< <;. salt heat
;OOC
<ylon23,3
<CO = <CO ;O
O;
Polyurethane
O O O = ;O O; O; heat
Flyptal
<ature also "as suspected to ha e used basic building bloc!s such as ;C<, <; 3 and "ater that are obser ed in interstellar space to produce adenine, guanine, cytosine and uracil in the \prebiotic system] as Oro has demonstrated in $73,. .723. Identify the origin of each carbon and nitrogen atoms of these bases from ;C<, <;3 and ;.O
<;. < < ; < < < < ; < O <; <;. ;< O <
<;. ;< O
<
%%
Problem 3+: >rue or false

3,2$. 3,2.. ;ydrogen is the most abundant element at the core of the sun. ;ydrogen is the only element in the periodic table that can exist "ithout a neutron. &his suggests that a neutron is essential for binding positi ely charged protons in the nucleus. 3,23. &he number of neutrons for hea y nuclei exceeds the number of protons, because the electrostatic repulsion bet"een protons is long2range "hereas the strong nuclear force among the protons and the neutrons is short2range. 3,25. ;elium is the second2most abundant element in the uni erse. &he molar ratio bet"een hydrogen nuclei 0proton1 and helium nuclei 0c2particle1 is about 3 to $. 3,2%. ;elium "as first made in the interior of the first star in the history of the uni erse. 3,23. 3,26. &he mass of an c2particle + . x 0proton mass = neutron mass1. <eutral atoms "ere first made before the birth of the first star in the history of the uni erse. 3,28. 3,27. &he disco ery of argon precedes the disco ery of the octet rule. Bendelee Is periodic table precedes the disco ery of argon.
3,2$,. &he disco ery of proton precedes the disco ery of electron. 3,2$$. &he ioni>ation energy of hydrogen is greater than the bond energy of the hydrogen molecule. 3,2$.. &he enthalpy of formation of CO.0g1 is about the same as t"ice the enthalpy of formation of ;.O0g1, because there are t"o electronegati e oxygen atoms in CO. "hereas there is only one in ;.O.
%3
Problem 31: 5olecular "eight determination of carbon dio3ide from density measurements
!ntroduction # ogadroEs principle 0$8$$1 is fundamental. ?or example, molecular "eight determinations from gas densities are based on this principle. Canni>>aro sho"ed in $8%8 that molecular "eights determined from gas density measurements can be used to determine atomic "eight. ?or example, the molecular "eight of nitric oxide, nitrous oxide, and nitrogen dioxide relati e to that of hydrogen gas, "hich Canni>>aro defined to be ., is 3,, 55, and 53, respecti ely. ?rom a large body of such data, one could deduce the atomic "eight of different elements. Fas density measurements led to another ma)or brea!through in the $7th century. 4ayleigh and 4amsay disco ered argon "hile determining the density of nitrogen gas 0see Problem 31. (oon a ne" group "as added to help complete the periodic table. # ogadroEs principle is exemplified in the follo"ing experiment "hich in ol es determining the molecular "eight of carbon dioxide from density measurements. &his experiment also uses the ideal gas la". 5aterials dry ice, "ater Apparatus Halance "ith at least ,.,$ g accuracy, t"o %,, mL flas!s "ith sidearm, rubber tubing, rubber stopper, aluminum foil, cylinder, thermometer, barometer ,3perimental %esign 3$2$. Le ise t"o separate procedures for determining the density of carbon dioxide at room temperature and atmospheric pressure using dry ice as the source of carbon dioxide. 3$2.. Indicate possible sources of error and suggest "ays to minimi>e these errors. 3$23. Calculate the molecular "eight of carbon dioxide 0i1 from its density relati e to that of air and 0ii1 using the ideal gas la".
%6
Procedure A $. 4ecord the ambient temperature 0T1 and atmospheric pressure 0!1. .. Ceigh a flas!. 4ecord %$. %$ + %0flas!1 = %0air1 0$1 3. Place crushed dry ice at the bottom of the flas! and allo" time for sublimation to occur. #fter a "hile, ma!e sure that there is no solid dry ice remaining and measure the temperature inside the flas!. Cait until temperature is e9uali>ed "ith the openings loosely co ered "ith aluminum foil to let carbon dioxide at room temperature and atmospheric pressure fill the flas!, "ipe out condensed "ater on the outer surface of the flas!, and "eigh. 4ecord C.. %. + %0flas!1 = %0CO.1 0.1 5. (eal the opening of the side arm "ith a rubber stopper. ?ill the flas! to the rim "ith "ater and measure olume of the "ater "ith a graduated cylinder. &his is the olume of carbon dioxide in the flas! 0V1. Calculate the "eight of air, %0air1, occupying this olume under the experimental conditions. #ssume that 688 of air is nitrogen, .$8 oxygen, and $8 argon. # mole of air "eighs .7., g. Calculate %0flas!1 from 0$1 and %0air1. &hen calculate %0CO.1 from 0.1 and %0flas!1. %. Letermine the molecular "eight of carbon dioxide from %0CO.1 and %0air1. M%0CO.1 + 0.7.,1X%0CO.1-%0air1Y 3. #lso determine the molecular "eight of carbon dioxide using the ideal gas la". !V + X%0CO.1-M%0CO.1YRT Procedure / $. Connect t"o flas!s through their side arm "ith one piece of rubber tube. 'le ate one flas! and place a sufficient amount of crushed dry ice at the bottom of this flas!. (eal the opening of this ele ated flas! "ith a rubber stopper and let carbon dioxide gas o erflo" through its side arm, and fill the recei ing 0lo"er1 flas!. .. Once a sufficient amount of carbon dioxide has o erflo"ed, "eigh the recei ing flas! filled "ith carbon dioxide after co ering its openings "ith aluminum foil. &he ad antage of this procedure is that carbon dioxide in the recei ing flas! is at room temperature and atmospheric pressure. 3. Letermine the olume, V, and "eight of the flas! as in Procedure #. 5. 4epeat until consistent "eight of carbon dioxide in the flas! is obtained. %. Letermine the molecular "eight of carbon dioxide as abo e.
%8
Problem 32: %etermination of molecular "eight by free6ing point depression

!ntroduction #ccurate measurement of gas density "as used for the determination of molecular "eight of gaseous compounds in the $7th century. ?or li9uid and solid compounds, ho"e er, colligati e properties had to be used. ;ere, free>ing point depression "ill be used to demonstrate ho" $7th century chemists estimated the molecular "eight of an un!no"n compound and determined the molecular formula from a gi en empirical formula. ?ree>ing point depression also can be used to test #rrheniusEs theory of electrolytic dissociation. 5aterials ice, sodium chloride, un!no"n compound # 0glucose1, un!no"n compound H 0sucrose1 Apparatus thermometer or digital temperature sensor 0,.$SC accuracy1, bea!er, test tube, "ire Procedure $. Bix enough sodium chloride "ith ice and "ater in a bea!er to bring the temperature of the ice "ater do"n to about 28 ^ 2$,SC. #dd more ice and salt as necessary to maintain this temperature range. .. #dd se eral milliliters of "ater to the test tube 0.^3 cm in diameter1. Place a thermometer or digital temperature sensor and a "ire bent at one end to form a ring to facilitate mixing. &hen immerse the lo"er half of the test tube assembly into the ice bath and monitor the temperature change for about $, min "hile igorously agitating the "ater "ith the "ire. &he temperature "ill drop sharply to a point of super2cooling and increase slightly to the free>ing point, "here the temperature "ill remain steady. Calibrate the thermometer or the temperature sensor to ,SC at the free>ing point of "ater. 3. Prepare $.,, and ..,, molal solution of sodium chloride in "ater. Letermine the free>ing point of these solutions follo"ing the procedure abo e. @sing the three data points 0origin from >ero point calibration, $.,, and ..,, molal concentration1, construct a cur e sho"ing free>ing point s. molal concentration. Letermine
%7
free>ing point constant, K&, of "ater from the slope and the anEt ;off ' factor for sodium chloride. 2 VTf + Kf m ' 5. Lissol e ., g of un!no"n compound in 8, g of "ater. #lso dissol e ., g of un!no"n compound H in 8, g of "ater. Letermine the free>ing point depression of these solutions and calculate molality. %. ?rom the calculated molality and the number of grams of the compound in $,,,, g of sol ent, calculate the molecular "eight of both compounds. 3. 'lemental analysis sho"ed that the compounds are simple carbohydrates. &he "eight percentages of C, ;, and O 0by difference1 for both compounds "ere similar "ithin experimental error 0C* 5,^5.8, ;* 3^68, O* %$^%581. (uggest molecular formulas for compounds # and H.
3,
Problem 33: 5olecular "eight determination of polymer by titration

!ntroduction Polycaprolactone 0PCL1 is a biodegradable polyester "ith a lo" melting point 0^3,SC1 typically prepared by ring opening polymeri>ation 04OP1 of d2caprolactone 0 2CL1 using a catalyst such as tin0II1 .2ethylhexanoate 0stannous octanoate1.
:
Sn :20
: 80aprolactone
PCL is fully biodegradable. ?urthermore its lo" melting point ma!es PCL a useful component of a composite biodegradable material. ?or example, PCL mixed "ith starch is used to ma!e cheap biodegradable trash bags. PCL is degraded by hydrolysis of its ester lin!ages under physiological conditions and, therefore, has also recei ed a great deal of attention for use as an implantable biomaterial. PCL has been appro ed in certain countries for use in the human body, and may be potentially used in drug deli ery, sutures, adhesion barriers and scaffolds for tissue repair. (o far, a ariety of drugs ha e been encapsulated "ithin PCL beads for controlled release and targeted drug deli ery. 4ecently, it has been reported that the 4OP of 2CL can proceed "ith a heat in the presence of natural amino acids. &herefore, the biocompatibility and in i o safety of PCL thus2obtained could be satisfying for medical and pharmaceutical purposes.
O
+
;.<
COO;
O Capr#la("#'e
Ala'i'e
In this experiment, four 4OP reactions "ill be carried out for different time inter als to prepare polymer samples "ith arying molecular "eights. (ince the degree of polymeri>ation 0LP1 of these samples is relati ely lo" and each polymer molecule
3$
contains an end2group suitable for simple acid2base titration, the a erage molecular "eight of the polymers can be determined by end2group analysis. # main problem in such an approach for molecular "eight determination is finding a sol ent for the polymer that is compatible "ith the titration. ?ortunately, an appropriate sol ent system is a ailable for PCL. PCL can be titrated "ith /O; in isopropyl alcohol-$,52dioxane sol ent 0v-v+$-51 using $8 phenolphthalein solution in pyridine as an indicator. &he a erage molecular "eight, Bn, of the polymer can be calculated as follo"s from the sample "eight and the number of moles of the end group* M( + "eight of polymer sample in g - number of moles from end group analysis &he degree of polymeri>ation at specific reaction time can be obtained from Mn for each polymer sample. LP + Mt-B,, MtA molecular "eight at time t M,A molecular "eight of one monomeric unit 5aterials 0R a(d S )#des re&er t# r'sk a(d sa&ety !hrases &#r the )hem')a s.1 L2alanine, 2caprolactone 0( .32.5-.%1, /O; 04 ..23%, ( .3233-36-3725%1, &etrahydrofuran 0&;?, 4 $$2$7233-36, ( $32.72331, methanol 04 $$2.3-.5-.%237-.3-.5-.%, ( 62$3233-3625%1, isopropyl alcohol 04 $$233236, ( 62$32.5-.%2.31, $,52dioxane 04 $$2$7233-3625,233, ( 72$3233-362531, $8 phenolphthalein solution in pyridine 04 $$2.,-.$-.., ( .32.81 Apparatus Halance "ith at least ,.,$ g accuracy, four %, mL flas!, four .%, mL bea!er, test tubes, %, mL burrette, Pasteur pipette, oil bath, and hot plate stirrer, acuum o en, mg2scale balance
3.
Procedure 1: =eat ring8opening polymeri6ation $. In each of four %, mL $2nec! round bottom flas!s 04H?1, mix ,.$3g L2alanine 0$.% mmol1 and %.$3 g 2caprolactone 05% mmol1 and stir the mixture at $3,SC in an oil bath. Connect the flas!s to nitrogen line to release any pressure de eloped during the heating. .. #fter $, %, $., and .5 h, remo e one of the flas!s from the bath and cool it do"n to room temperature. Lissol e the mixture in % mL tetrahydrofuran 0&;?1 and precipitate the polymer product by pouring the solution into 8, mL methanol-;.O 0v-v+5-$1 solution. 3. ?ilter the precipitated polymer products and dry in a hours. Beasure the "eight of dried polymer products. Procedure 2: >itration "ith @:H $. Prepare a standardi>ed solution of /O; 0about ,.,,8 B1 in isopropyl alcohol-$,52 dioxane 0v-v+$-51. .. Lissol e each polymer sample obtained abo e in %., mL of isopropyl alcohol-$,52 dioxane 0v-v+$-51. #dd 5 drops of $8 phenolphthalein-pyridine solution to $., mL ali9uot of each polymer solution and titrate "ith the standardi>ed /O; solution. 4epeat this titration. 3. Calculate the a erage experimental molecular "eight a erage olume of the titrant. 5. 4epeat steps . and 3 for other polymer samples. Auestions #ssume that $,,8 con ersion of monomer is obtained after .5 h, and all the amino acid 0alanine1 is incorporated into the polymer. 332$. Chat is the structure of the resulting compound if alanine attac!s the caprolactoneD #nd explain the meaning of titration "ith /O;. 332.. #t times of $, %, $., and .5 h, calculate yields, mol of /O; used in titration, the number of polymer chain, a erage experimental molecular "eight alue 0g-mol1 of polymer 0Mn1, and degree of polymeri>ation. alue 0g-mol1 from the acuum o en for se eral
33
$h sample Polymer yield 0g1 olume of /O; solution 0ml1 amount of /O; 0mmol1 amount of polymer 0mmol1 M( 0g-mol1 degree of polymeri>ation
.h sample
%h sample
.5 h sample
3323. Lra" each polymeric product from the $, %, $., and .5 h trials. &he repeat unit in polymer chain can be expressed as an example sho"ed belo". 'xample1 $$2aminoundecanoic acid
;.< COO; 10
35
Problem 3 : Separation and 1uantitative determination of dyes by column chromatography and spectrophotometry
!ntroduction In this experiment, students recei e small olumes of un!no"n li9uid "hich is a mixture of allura red 0C$6;$.<.O8(.<a., a""rev. #41 and bromocresol green 0C.$;$5Hr5O%(, a""rev. HCF1 in their basic forms. #n ali9uot is placed on a small silica gel column, "hich students prepare by filling silica gel in a Pasteur pipet. &he students separate the dyes by ste!*'se elution "ith the sol ents listed in &able $. &he students choose t"o eluents that are expected to gi e the best separation of the dyes. &he samples are then diluted to a !no"n olume and 9uantified by isible spectrophotometry. &he components of the entire experiment N column preparation, separation, calibration cur es, and analysis of the un!no"n N can be underta!en easily if students !no" ho" to perform 9uantitati e serial dilution, operate a spectrophotometer, and !no" ho" to select the analytical "a elengths for the dyes.
OH Br OCH3 NaO3 N N O O All-ra re)

5aterials 4eagent allura red bromocresol green hydrochloric acid triethylamine methanol ethyl acetate silica gel Apparatus
Br Br OH O H 3C Br
HO H 3C
O3Na
Br#!#(re$#l .ree'
Concentration solid solid "0;Cl1 3%8
4 phrases .3235236 $$2.,-.$-.23% $$2.3-.5-.%237-.3-.5-.% $$233233236
( phrases ..2.5-.% .325% 32$32.32.7233-36-3725% 62$3233-3625% $32.3233 ..2.5-.%
solid
3%
isible spectrophotometerA analytical balanceA sample cell 0$,2mm pathlength1A t"el e $,2mL and t"o %,2mL olumetric flas!sA t"o %,2mL bea!ersA three .2mL Pasteur pipetsA one $,,2 L micropipette, pipet filler Procedure 1: Preparation of stoc? solutions of dyes &hese dye solutions tend to decompose o er extended periods of time, so they should be prepared )ust prior to the experiment. $. Hromocresol green. #n accurately "eighed sample 03,, mg1 is dissol ed in ethyl acetate in a %,2mL olumetric flas!, to "hich sufficient triethylamine is added to produce the purple basic form. .. #llura red. #n accurately "eighed sample 0about $,, mg1 is dissol ed in about 3, mL of methanol in a %,2mL olumetric flas!, to "hich triethylamine is added drop"ise until the dye is completely dissol ed. Bethanol is then added to the mar! to dilute the mixture. +#te* #llura red should be pre2purified as follo"s* Lissol e the sodium salt of #4 in methanol and then filter. &o this solution, add an excess of concentrated ;Cl. #fter about 3, min, the resulting crystals of the protonated form can be filtered off. Procedure 2: Preparation of standard solutions of dyes Prepare fi e standard solutions for each dye by diluting the stoc! solution in the same sol ents used for the preparation of the stoc! solutions in $,2mL olumetric flas!s. &o the #4 standard solutions 325 drops of concentrated ;Cl are added to ha e the dye in its acidic form. &he concentration of the standard solutions should be in the range of one tenth to nine tenths of the original concentration of the stoc! solution. Procedure 3: Preparation of calibration curves of dyes Prepare a calibration cur e for each dye using its absorbances at respecti e pea! maximum vs. concentration in ppm.
33
Procedure : Preparation of a chromatographic column Prepare a chromatographic column by placing a small plug of glass "ool 0or cotton1 at the constriction of a .2mL Pasteur pipet. (ilica gel 05%-6, mesh1 slurried in ethyl acetate is added to the pipet to produce 52% cm of pac!ed gel in the column. Procedure #: 0olumn chromatography and 1uantitation $. &ransfer a 5,2 L ali9uot of un!no"n li9uid to the column. .. 4inse the "alls of the column "ith a fe" drops of an eluent selected from &able $, pass the eluent through the column and collect the eluate in a $,2mL olumetric flas! containing .23 drops of triethylamine. 3. Pass a second eluent through the column selected from &able $, and collect the eluate in a separate $,2mL olumetric flas! containing 325 drops of concentrated ;Cl. # small band of impurity may be left behind at the top of the column. 5. Lilute the first fraction in its purple, basic form to olume "ith the first eluent. %. Lilute the second fraction in its acidic, red form to olume "ith the second eluent. 3. ?ind the concentration of each sample, and thus the amount 0mg1 of each dye in the un!no"n from the calibration cur e for each dye. >able 3 81B Possible eluent systems 'luent <o. $ . 3 5 % 3 'luent (et I ethyl acetate methanol ethyl acetate2;Cla 0.,,*$ - 1 ethyl acetate2&'# 0.,,*$ - 1 methanol2;Cl 0.,,*$ - 1 methanol2&'# 0.,,*$ - 1 'luent (et II methanol ethyl acetate methanol2;Cl 0.,,*$ - 1 methanol2&'# 0.,,*$ - 1 ethyl acetate2;Cl 0.,,*$ - 1 ethyl acetate2&'# 0.,,*$ - 1
a. concentrated hydrochloric acid.
36
Auestions 352$. Chat are the concentrations in ppm of #4 and HCF in your sampleD 352.. <ote that separation is performed in the normal phase LC mode. Considering the structures of the dyes, "hich dye "ould you "ant to elute first for best resultsD Chich eluent "ould you use for eluting the first2eluting dyeD 'xplain. 3523. Chich dye "ould be eluted secondD Chich eluent "ould you use for eluting the second dyeD 'xplain.
38
Problem 3#: Synthesis of C8dimethylaminopropiophenone hydrochloride

!ntroduction Pro>ac is a famous antidepressant, also !no"n as the \happy drug] as it can help alle iate depression. &he acti e ingredient in Pro>ac is fluoxetine. ?luoxetine is prepared from _2dimethylaminopropiophenone in a four step se9uence.
?3C
O < C;3 C;3
$"ep$
O C;3 < ;
/l-#xe"i' (0r#1a()
&he target molecule can be obtained through a one2pot reaction in ol ing three or more starting compounds, also !no"n as a multicomponent reaction 0BC41. #mong BC4s classic name2reactions ha e de eloped into popular organic2chemical reactions in the pharmaceutical industry for the preparation of compound libraries of lo" molecular drug2li!e compounds. ?or example, the Bannich reaction is a \one pot] combination reaction of three synthetic fragments to ma!e a single product. &his multi2 component reaction can be applied to the synthesis of _2dimethylaminopropiophenone, as paraformaldehyde and dimethylamine hydrochloride are combined in the presence of acetophenone to produce directly _2dimethylaminopropiophenone.
O O C;3 = ; ; = ;< C;3 C;3 ;Cl 'tO;, O < C;3
HCl
C;3
37
5aterials acetophenone 04 ..233, ( .31, concentrated ;Cl 04 .3235236, ( .325%1, dimethylamine hydrochloride 04 ..233-36-38, ( .3233-361, paraformaldehyde 04 .,-..236-3825,25$253, ( .3233-36-3725%1, ethanol 04 $$, ( 62$31, ethyl ether 04 $.2$72..233236, ( 72$32.72331, hexane04 $$238258-.,2%$-%323.23%236, ( 72$32.7233233-3623$23.1, methanol 04 $$2.3-.5-.%237-.3-.5-.%, ( 62$3233-3625%1, ethyl acetate04 $$233233236, ( $32.32331, <a;CO3, acetone /BnO5 04 82..2%,-%3, ( 3,23$1, `nCl. 04 ..2352%,-%3, ( .3233-36-3725%23,23$1 ?eCl3 04 ..23825$, ( .32371, #g<O3 04 352%,-%3, ( .325%23,23$1 <aO; 04 3%, ( .3236-3725%1, <;3 04 352%,, ( .3233-36-3725%23$1 .,52dinitrophenylhydra>ine 04 $2$$2.., ( 3%1, conc. sulfuric acid 04 3%, ( .323,25%1 Apparatus .%2mL round2bottomed flas!, %, mL 'rlenmeyer flas!, stirrer, temperature controller, heating mantle, sand, support stand, clamp, clamp holder, melting point apparatus, capillary tubes, magnetic bar, reflux condenser, hose, Hechner funnel, suction flas!, glass rod, filter paper, $,, mL2bea!er, &LC plate 0silica gel 3, ? .%5, layer thic!ness* .%, Rm, on glass support1, micro2syringe, de eloping chamber "ith a lid, @J lamp Procedure Inside a fume hood, add . mL of acetophenone, ,.3% g of dimethylamine hydrochloride and $.63 g of paraformaldehyde into a .% mL round2bottomed flas!. &o the flas!, add 5 mL of 7%8 ethanol follo"ed by 5, RL of concentrated ;Cl. #dd your magnetic bar and e9uip the flas! "ith a reflux condenser. 4eflux the mixture for . hours by placing the flas! in a sand bath preheated to $.,SC. #llo" the reaction mixture to cool slightly 0to %,^8,SC1 and transfer it to a small 'rlenmeyer flas! 0pour, do not pipette or the material "ill free>e in the pipette1. #dd $3 mL of acetone and allo" the flas! to cool to room temperature. Bix thoroughly "ith a glass stirring rod. Cool the mixture in an ice2 bath to complete the crystalli>ation. ?ilter by suction using a Hechner funnel "ith a filter flas! and "ash the solids "ith 5 mL of acetone. 0Mou can use $ mL acetone to help transfer the last of the solid in the flas!.1 Let the product dry for at least ., minutes on the funnel. Ceigh the products and determine their melting point.
6,
'xtract a free amine into the organic sol ent "ith a9ueous <a;CO3 solution for de eloping &LC. Lissol e about ,.$ g of the product "ith distilled "ater and then transfer the solution into a small separatory funnel. #dd ethyl ether as an organic sol ent. <eutrali>e the "ater layer "ith a9ueous <a;CO3 solution. @se a p; paper. Obtain the organic layer for &LC. Le elop a &LC plate in ethyl acetate* hexane 0.*$, v-v1 or ethyl acetate* methanol 0.*$, v-v1.
Aualitative >ests Perform the follo"ing tests "ith the product and report the obser ation. 1< >he /aeyer >est 9Potassium permanganate<D A.@,=,S A=% A.@E=,S 0 * &his test is useful for indicating the presence of most olefinic or acetylenic functional groups. 1 Lissol e 3, mg of the product in . mL of "ater. #dd ,.$ B /BnO 5 a9ueous solution drop"ise, report the results. 2< .ucas testD A.0:H:.S 0 * &his test is useful for distinguishing among lo"er2molecular2"eight primary, secondary, and tertiary alcohols. 1 Prepare LucasEs reagent by dissol ing $33 g of >inc chloride in 87 mL of conc. ;Cl "ith cooling in ice bath. #dd . mL of LucasEs reagent to 3, mg of the product in a test tube. <ote the time re9uired to form the insoluble al!yl chloride, "hich appears as a layer or emulsion. 3< 7erric chloride testD PH,=:.S 0 * &his test is useful for the recognition of phenols. 1 Lissol e 3, mg of the product in . mL of "ater or a mixture of ethanol and "ater, and add up to 3 drops of the ..%8 a9ueous ferric chloride solution. Bost phenols produce red, blue, purple, or green colorationA enols gi e red, iolet, or tan coloration. < >ollen(s reagent 9silver8Ammonia comple3 ion<D A.%,HE%,S 0 * &his test is useful for distinguishing aldehydes from !etones and other carbonyl compounds. 1
6$
&o a clean test tube, add . mL of the %8 sil er nitrate solution and $ drop of the $,8 sodium hydroxide solution. #dd . B ammonium hydroxide solution drop by drop "ith good sha!ing until the dar! precipitated sil er oxide )ust dissol es. #dd $ drop of the li9uid or 3, mg of the product to be tested, sha!e the tube to mix, and allo" it to stand at room temperature for ., minutes. If nothing happens, heat the tube in a bea!er of "ater at 3% oC for fi e minutes. #< 2- 8dinitrophenylhydra6ine >est D A.%,HE%,S A=% @,>:=,S 0 * &his test is useful for identifying aldehydes and !etones. 1 Prepare .,52dinitrophenylhydra>ine reagent by dissol ing 3 g of .,52dinitrophenyl2 hydra>ine in $% mL of conc. sulfuric acid and adding this solution, "ith good stirring, to a mixture of ., mL of "ater and 6, mL of 7%8 ethanol. Lissol e $,, mg of a solid product in . mL of 7%8 ethanol, and add this solution to . mL of the .,52 dinitrophenylhydra>ine reagent. (ha!e the mixture igorouslyA if a precipitate does not form immediately, let the solution stand for $% min.
2esults 2 2eagents F Products 0(ho" calculations1 4eagents B.C. grams 0g-mol1 0compound names1 0or mL1 used
mmole used
e9ui alent
physical properties
Product* XB.C. + Ceight* Mield* 2 5elting Point*
g-mol Y g 8
o o
C 0Obser ed1 C 04eported in the literature1
2 Rf values 04ecord the Rf alues and the si>e and shape of each spots1* 0(ho" calculations1 &est 4eagent &est result Obser ed expected
6.
$1 /BnO5 0HaeyerEs test1 .1 ;Cl, `nCl. 0LucasEs test1 31 ?eCl3 0?erric chloride solution1 51 #g<O3-<aO;-<;3 0&ollenEs reagent1 %1 .,52dinitrophenylhydra>ine
; < O.< <;. <O.
Auestion &he general mechanism for a Bannich reaction is gi en belo" for an illustrati e example. #ccount for the o erall reaction in a step"ise fashion. &ry depicting the mechanism 0i.e., electron \pushing]1 for the reaction carried out in the test.
; O ; 4 ; 4 ; O 2;.O ; < ; 4 4 .< 4 4 4I O 4I ; < 4 ; ; O ; 4 < ; 4
O ; ;
;=
O ;
4 < ; 4
;=
; ;
63
O C;3
2e"#3e'#l "a-"#!eri$!
;3C O ; ;
O; ; ;
< ;
C;3
H+
+ H2O
O < C;3
A + 4
H+
C;3
65
Problem 3$: ,n6yme ?inetics by catalase

!ntroduction Catalysis is a central concept in chemistry and biology, essential in life and industrial processes. 'n>ymes are catalysts for biochemical reactions. In this experiment, the Bichaelis2Benten !inetics of hydrogen peroxide decomposition 0.;.O. .;.O = O.1 by catalase in potato )uice "ill be in estigated. Catalase is "ell !no"n for its extremely high reaction rate. One catalase molecule can decompose 5, million hydrogen peroxide molecules in one second. (uch a high rate is needed to sca enge reacti e oxygen species and protect cellular components in the oxidati e en ironment. &he figure belo" sho"s a 32dimensional structure of catalase from E. )# ' determined by O2 ray crystallography.
&he number of moles of the e ol ed oxygen gas can be determined from its olume measured using a buret or from the pressure change in an enclosed reaction essel. 4eaction rate can be expressed as the number of moles of oxygen per unit time. #n en>yme 0'1 combines "ith a substrate 0(1 and produces an en>yme2substrate complex 0'(1 "ith a rate constant k$. '( could be decomposed bac! to ' and ( "ith a rate constant k. or concerted to a product 0P1 "ith a rate constant k3. &he steady state condition for '( can be determined by e9uating the follo"ing rate e9uations. dX'(Y-dt + k$0X'Ytot 2 X'(Y1X(Y , 2dX'(Y-dt + k. X'(Y = k3X'(Y X(Y0X'Ytot 2 X'(Y1-X'(Y + 0k. = k31-k$ 0k. = k31-k$ is defined as the Bichaelis2Benten constant, KB. (ol ing the last e9uation for X'(Y, one gets X'(Y + X'Ytot X(Y-0KB =X(Y1. "here X'Ytot + X'Y = X'(Y
6%
Let v be the initial rate for the e olution of oxygen* v + k3X'(Y If the en>yme is present only as '(, v "ill approach a maximum alue, Vmax + k3X'Ytot ?rom these relations, one gets the Bichaelis2Benten e9uation. v + VmaxX(Y-0KB = X(Y1 Ob iously, KB is the alue of X(Y "hen v + Vmax-.. &a!ing the in erse of the Bichaelis2 Benten e9uation one gets the celebrated Line"ea er2Hur! e9uation 0see ?igure1, "hich is one of the most fre9uently used e9uations in chemistry. $-v +0KB-Vmax10$-X(Y1 = $-Vmax
5aterials hydrogen peroxide 04 35, ( .8233-3725%1, fresh potato, catalase Apparatus blender, ice bath, boiling "ater bath
63
Procedure $. Prepare ,.%, $, ., 3, 5, 38 solution of hydrogen peroxide by diluting the gi en 3,8 hydrogen peroxide "ith deioni>ed "ater. .. Ba!e potato )uice by blending pieces of potato "ith approximately e9ual "eight of "ater. (9uee>e the )uice "ith cheesecloth. /eep the )uice in an ice bath. 3. #dd . mL of the )uice to 3, mL of the diluted hydrogen peroxide solutions and sha!e. #s a control, use 3, mL of deioni>ed "ater. 5. Beasure the olume of oxygen produced using a set2up sho"n belo". Ba!e a soap bubble "ith the rubber bulb and measure time needed to produce a certain olume 0., mL for example1 of oxygen gas at room temperature. %. 4epeat "ith 38 hydrogen peroxide using the )uice heated in boiling "ater bath for $, min to denature the en>yme. 3. If pure catalase is a ailable, repeat the "hole experiment using catalase at a !no"n concentration 0$ micromolar, for example1. Auestions 332$. Calculate the molar concentration of hydrogen peroxide, X(Y. 332.. Calculate the number of moles of oxygen produced in a gi en time for each X(Y. 3323. Calculate v for each X(Y. 3325. Plot v against X(Y and see if it approaches a maximum alue. 332%. Le elop a Line"ea er2Hur! plot to determine KB and Vmax. 3323. If X'Ytot is !no"n, calculate k3 from Vmax + k3 X'Ytot. Chat is the turn2o er number of catalase per secondD
66

2008 ICHO38 Preparatory Problems Final

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