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th

37 IChO Theoretical Examination

- use only the pen provided

- time

5 hours

- problem booklet

26 pages (including this cover sheet)

- answer sheets:

28 pages (including cover sheet, and fives pages at

the end with only a box.

Use if necessary.

Write

down the problem number inside the box

- draft paper (will not be marked):

5 sheets (more are available on request)

- total number of points:

279 (They are equally weighted in the final

score)

- your name and student code

write on every answer sheet

- atomic masses

use only the periodic system given

- constants

use only the values given in the table

- answers

only in the appropriate boxes of the answer

sheets. Nothing else will be marked

- questions ask for show works

no point will be given to no showing work

- restroom break

ask your supervisor

- official English-language version

available on request, for clarification only, ask your

supervisor.

- after the stop signal

put your answer sheets in the correct order (if they

arent), put them in the envelope (dont seal), deliver
them at the exit

- examination booklet

keep it, together with the pen and calculator.

GOOD

LUCK

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Fundamental Constants, Equations and Conversion Factors

Atomic mass unit

1 amu = 1.6605 10
23

kg

-1

Avogadros number

N = 6.02 10 mol

Boltzmanns constant

k = 1.3806503 10

Electron charge

e = 1.6022 10

-19

-27

-23

JK

-1

-1

Faradays constant

F = 9.6485 10 C mol

Gas constant

R = 8.314 J K mol = 0.08205 L atm K mol

Mass of electron

me = 9.11 10

Mass of neutron

mn = 1.67492716 10

-1

Mass of proton

-1

-31

kg

mp = 1.67262158 10

Plancks constant

h = 6.63 10
8

-34

-1

-27
-27

kg
kg

Js

-1

Speed of light

c = 3 10 m s

Nernst equation (T = 298 K)

E = E (0.0592 / n) log K

Arrhenius equation

k = Ae

Clausius-Clapeyron equation

ln P = - Hvap / RT + B

De Broglie relation

h / mv
=

Ideal gas equation

PV = nRT

Free energy

G = H TS

-Ea/RT

E = hv
G = G + RT ln Q

G = - nFE

U = q + w

w = - PV

V(cylinder) = r2h
V(sphere) = 4/3 r3
A(sphere) = 4 r2
1

= 10

-10

m
2

1W=1Js

1 J = 1 kg m s

-2

-1

-1

1 cal = 4.184 J
-2

-2

1 Pa = 1 kg m s = 1 N m

1 bar = 10 Pa

1 atm = 1.01325 10 Pa = 760 mmHg (torr)

1 eV / molecule = 96.4853 kJ mol

-1

Standard atmosphere = 101325 Pa

RT at 298.15 K

= 2.4790 kJ mol

Pi ()

= 3.1415927

-1

-1

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Problem 1: Chemistry of Amides and Phenols

Total Scores: 38 points
1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8
Points

Condensation of a carboxylic acid with an amine gives an amide product.

For example,

condensation of formic acid with dimethylamine forms N,N-dimethylformamide (DMF), which can be
described as the following resonance structures.

O
C

CH3

CH3

1-1

O
C

CH3
N
CH3

Predict the order of melting points among N,N-dimethylformamide (compound A),

N-methylacetamide (CH3CONHCH3, compound B), and propionamide (CH3CH2CONH2,
compound C).

Express your answer from high to low melting point as follows:

____ > ____ > ____

1-2

(Insert compound codes A, B, C)

Carbonyl groups are usually identified by their characteristic strong absorptions in

the infrared spectra.

The position of the absorption is dependent on the strength of

the C=O bond, which in turn is reflected in their bond lengths. In amides, the strength
of the carbonyl groups can be shown by the resonance structure noted above.

For

-1

example, cyclohexanone shows an absorption at 1715 cm for the carbonyl group

(C=O).

In comparison with cyclohexanone, predict the absorption band for the

carbonyl group in propionamide.

Select your answer from the following choices.

-1

(a) 1660 cm because of the shorter carbonyl bond length

(b) 1660 cm-1 because of the longer carbonyl bond length
(c) 1740 cm-1 because of the shorter carbonyl bond length
(d) 1740 cm-1 because of the longer carbonyl bond length

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Glycine (H2N-CH2-COOH) is an -amino acid.

Three glycine molecules can form a

tripeptide Gly-Gly-Gly via amide linkages, accompanied by elimination of two water

molecules.

1-4

Draw the structural formula of this tripeptide.

When an -amino acid contains a substituent, there is a possibility of optical isomers.

For example, L-alanine and D-alanine are two enantiomers.

What is the number of all

possible linear tripeptides that can be formed from the following three amino acids:
glycine, L-alanine and D-alanine as the starting materials in the condensation
reaction?

O
H2N

O
H2N

OH

H H

H2N

OH

H CH3

Glycine (Gly)
1-5

O
OH

H3C H

L-Alanine (L-Ala)

D-Alanine (D-Ala)

Among the tripeptides synthesized in 1-4, how many are optically active?

Nowadays, polyacrylamide gel associated with electrophoresis (PAGE) was widely used in
analyses of proteins and nucleic acids.

However, one of the first applications of polyamide gel is

the separation of phenol compounds on thin-layer chromatography.

bearing different substituents have varied acidities.

The phenol compounds

The higher acidity results in stronger binding

to PAGE gel.
1-6

Predict the binding affinity of phenol (compound D), 4-methylphenol (compound E)

and 4-nitrophenol (compound F) with a polyamide gel.

Express your answer from

high to low binding affinity as follows:

>

>

(Insert compound codes D, E, and F)

The absorption maximum of a molecule in its ultraviolet and visible spectrum (UV-vis spectrum) is
related to the number of conjugated double bonds in a chain.

A compound containing more than 5

conjugated double bonds tends to absorb visible light, and hence shows the complementary color.
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For example, phenolphthalein is a commonly used acid-base indicator, which is colorless in acidic
and neutral solutions, but reddish pink in basic solutions (pH 8.3-10.0).
O
O
G

concentrated H 2SO4
2
o

OH

180 C, 5 h

OH

OH

H+

HO
Phenol
Phenolphthalein

Phenol

Phenolphthalein

For translation: concentrated

1-7

Draw the structural formula of H derived from phenolphthalein that is attributable to

the reddish pink color in aqueous NaOH solution.

1-8

A simple way to prepare phenolphthalein is via condensation of compound G with 2

equivalents of phenol. What is the most effective reagent for G to accomplish this
transformation?

(a)

(b)

O
H
H
O

Select your answer from the following compounds.

(c)

(d)

H
OH

H
OH

O
O

(e)

O
O
O

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Problem 2: Organic Synthesis and Stereochemistry

Total Scores: 48 points
2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8
Points

Natural carbohydrates are generally produced by photosynthesis in plants.

carbohydrates can be prepared by organic synthesis.

However, unnatural

The following outline is a synthetic scheme

for the unnatural L-ribose (compound I).

CO2Me

100 0C

O +
CO2Me

O
CO2Me

pig liver
esterase

CO2Me

MeO2C

sealed tube

HO
HO

CO2Me

CO2H

O
+

D (minor)

H+, CH3COCH3

CO2Me

Me2C(OMe)2

CO2Me

O
CO2H O3

O
E (major)

CO2Me MeOH

MeO2C
O O CO2Me
O CO2Me
4
H3O+
4
(1) MeOH/H+
1
MCPBA
O 1
3
3
2
2
H
O
O (2) LiAlH4, then H2O
O
O

For translation

HO
1

CH2OH

HO

OH

I (L-ribose)

2-1

OsO4

sealed tube =

pig liver esterase =

(minor) =

(major) =

Compound A has the molecular formula of C10H10O5.

Draw the structural formula of

A.

2-2

Given the chemistry described for reaction sequence A to C, indicate whether the
following statements are true or false (Use T to represent true and F to represent
false).
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(a) OsO4 is an oxidizing agent in the reaction of A to B.
(b) MeOH is generated as a by-product in the reaction of B to C.
(c) Protons act as the catalyst in the transformation of B to C.
(d) C will still be formed albeit in lower yields in the absence of Me2C(OMe)2.

Pig liver esterase is an enzyme that can hydrolyze esters to carboxylic acids.

Hydrolysis of C by

the pig liver esterase afforded an enantiomeric mixture of D and E, in which E was the major
component.

20

The optical rotation of the mixture was []D

recrystallization gave pure E with the optical rotation

2-3

20
[]D

= -37.1 .

Further purification by

= -49.0 .

What is the molar ratio of D/E in the product mixture before the recrystallization?
Show your work.

2-4

Reaction of F with meta-chloroperbenzoic acid (MCPBA) afforded G as the product.

Indicate whether the following statements are true or false (Use T to represent true
and F to represent false).
(a)

The reaction was to oxidize compound F.

(b) The oxygen atom inserted originated from MCPBA.

(c)

The R/S notation of C-1 remained unchanged before and after the reaction.

The molecular formula of H is C9H16O5.

Proton NMR data of H are listed as follows:

H NMR (CDCl3) 1.24 (s, 3H), 1.40 (s, 3H), 3.24 (m, 1 H), 3.35 (s, 3H), 3.58 (m, 2H), 4.33 (m, 1H);

4.50 (d, J = 6 Hz, 1H), 4.74 (d, J = 6 Hz, 1H), 4.89 (s, 1H).

2-5

Draw the configurational formula of H.

2-6

Assign R/S notations for compound I at C-1, C-2, C-3 and C-4.
as follows:
C-1: ____; C-2: ____; C-3: ____; C-4: ____.

Give your answers

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What are the identities of P, Q, R, S, T and U in the Fischer projection of compound I

(L-ribose)?

CHO
P
Q
R
S
T
U
CH2OH
Disaccharides are compounds with two monosaccharide subunits linked together by a glycosidic
bond.

Polysaccharides contain as few as ten, or as many as thousands, monosaccharide

subunits. An example of a disaccharides is as follows:

H OH H
HO
HO

H
H

OH

H OH H

HO

glycosidic bond

O
OH

OH
H

2-8 How many diastereoisomers would be obtained for pentasaccharide J, if it is derived

from five units of D-glucose?

H OH H
H

O
HO

H
H

OH H

pentasaccharide J derived from D-glucose

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Problem 3: Organic Photochemistry and Photophysics

Total Scores: 36 points
3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8
Points

Crown ethers show size-dependent binding capability to alkali metal ions.

+

For example, the

azacrowns A and B exhibit different binding constants for Na , K , and Cs .

O
O

N
CH2

O
N
CH2

B
Binding constant (log10 K)

Metal ion

Radius (pm)

Compound A

Compound B

Na+

98

2.49

3.57

K+

133

1.83

5.00

Cs+

165

1.37

3.39

For translation: Binding constant

Metal ion

Radius (pm)

Compound

Anthracene exhibits strong fluorescence with emission wavelength centered at 325 nm.
Combining the binding selectivity of azacrowns for alkali metal ions and the highly fluorescent
anthracene, a metal ion selective fluorescent sensor E has been developed.

3-1

Provide the structural formula of C and D in the following synthesis.

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H

O
(1) NaBH4

pyridine
O

O
N
CH2

toluene
D

(2) t-BuO-K+
HO(CH2)2NH(CH2)2OH

K2CO3

HO

SO2Cl

(1)
OH

(2) PCl5 /benzene

For translation: benzene:

pyridine:

toluene:

For comparison studies, the anthracene derivatives F and G shown below were also synthesized.
These compounds E, F, and G are almost non-fluorescent in neutral conditions due to the strong
photoinduced electron transfer (PET) quenching process arising by donating nitrogen lone-pair
electron to the anthracene excited-state.

O
OH
O

H2C

H2C

3-2

OH

Upon adding aqueous HCl, which compound will exhibit strong fluorescence? Select
your answer from the following choices.
(a) none of them

3-3

(b) E and F only

(c) G only

(d) all of them

-5

By adding one equivalent of potassium acetate into a dilute solution (10 M) of E, F,

and G in methanol, respectively, which compound will show the strongest
fluorescence? Select your answer from the following choices.
(a) E

(b) F

(c) G

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Upon adding one equivalent of metal acetate to a dilute solution of F, which metal
acetate will cause the strongest fluorescence? Select your answer from the following
choices.
(a) sodium acetate

(b) potassium acetate

(c) cesium acetate

(d) doesnt make any

difference

Upon irradiation with ultraviolet light, trans-stilbene is transformed into an intermediate H, which
undergoes a photocyclization to form dihydrophenanthrene I.

Further oxidation of I gives

phenanthrene.

oxidation

For translation:

H H
I

heat

trans-Stilbene
a

Phenanthrene

trans-Stilbene

heat

oxidation

3-5

Draw the structural formula of compound H?

3-6

What is the relative stereochemistry of the two H-atoms shown (cis or trans) in
compound I?

Dihydroazulene derivative J exhibits interesting photochromic behavior.

Upon irradiation,

colorless dihydroazulene J undergoes photoinduced rearrangement to the corresponding

vinylheptafulvene K.

The vinylheptafulvene undergoes thermal reversion to dihydroazulene.

NC 1 CN

CH3
CN
CN

For translation:

6
8

J
a

heat
12

CH3

10

heat

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Which compound will absorb light with longer wavelength?

Select your answer

from the following choices.

(a) J

3-8

(b) K

Compound K can react with one equivalent of CF3CO2H to generate a stable aromatic
salt.

Which position of K is most likely protonated?

following choices.
(a) C-2 (b) C-3 (c) C-4 (d) C-5

13

Select your answer from the

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Problem 4: Gold Capital of Asia

Total Score: 42 points
4A-1

4A-2

4A-3

4A-4

4A-5

4A-6

4B-1

4B-2

Points

4B-3 4B-4
2

4B-5
8

A
Chiufen, the old mining town located within the hills in the northeast Taiwan, is a place where you
can really experience Taiwan's historical legacy.
Asia.

It was the site of one of the largest gold mines In

Accordingly, Chiufen is often referred to as the Gold Capital of Asia.

traditionally used to extract gold from ore.

of air to form

Au(CN)2 ,

The compound KCN is

Gold dissolves in cyanide (CN ) solutions in the presence

which is stable in aqueous solution.

4 Au(s) + 8 CN(aq) + O2(g) + 2 H2O(l)

4 Au(CN)2(aq) + 4 OH(aq)

4A-1

Draw a structure for Au(CN)2 showing the spatial arrangements of the atoms.

4A-2

How many grams of KCN are needed to extract 20 g of gold from ore? Show your
work.

Aqua regia, a 3:1 mixture (by volume) of concentrated hydrochloric acid and nitric acid, was
developed by the alchemists as a means to dissolve gold.

The process is actually a redox

reaction with the following simplified chemical equation:

Au(s) + NO3(aq) + Cl(aq)

4A-3

AuCl4(aq) + NO2(g)

Write down the half reactions, and use them to obtain a balanced redox reaction for
this process.

4A-4

What are the oxidizing and reducing agents for 4A-3 process?

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Gold is too noble to react with nitric acid.

complex ion AuCl4 forms.

However, gold does react with aqua regia because the

Consider the following half-reactions:

Au3+(aq) + 3 e
AuCl4(aq) + 3 e

Au(s)

E = +1.50 V

Au(s) + 4 Cl(aq)

E = +1.00 V

An electrochemical cell can be formed from these two redox couples.

4A-5

Calculate the formation constant for AuCl4 at 25C:

3+

K = [AuCl4 ] / [Au ] [Cl ]4

4A-6

The function of HCl is to provide Cl.

reaction.

What is the purpose of the Cl for the above

Select your answer from the following choices.

(a) Cl is an oxidizing agent

(b) Cl is a reducing agent
(c) Cl is a complexing agent
(d) Cl is a catalyst

B
Gold Nanoparticles
The synthesis and characterization of gold nanoparticles is currently an active research area.

The

Brust-Schiffrin method for the synthesis of gold nanoparticle (AuNP) allows the facile preparation of
thermally stable and air-stable AuNPs of reduced polydispersity with a controlled size distribution
ranging in diameter between 1.5 and 5.2 nm.
follows.
bromide.

The preparative procedure is briefly described as

An aqueous solution of HAuCl4 is mixed with a toluene solution of tetra-n-octylammonium

The solution is mixed with dodecanethiol and is treated with an excess of NaBH4.

Formation of the AuNPs is evidenced by the immediate, pronounced darkening of the toluene phase.
After ca. 24 h, the toluene solvent is removed with a rotary evaporator and the resulting solid washed
on a frit with ethanol and hexane to remove excess thiol.

These AuNPs can be repeatedly isolated

and re-dissolved in common organic solvents without irreversible aggregation or decomposition.

4B-1

Is the methodology for this fabrication referred to a top-down or a bottom-up

approach?

Select your answer from the following choices.

(a) top-down approach, which entails reducing the size of the smallest structures to
the nanoscale
(b) bottom-up approach, which involves manipulating individual atoms and molecules
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into nanostructures
4B-2

The trimethyl-n-octylammonium bromide can also be used as a phase-transfer

reagent.

It can carry AuCl4 from an aqueous phase to an organic phase.

Which

property does trimethyl-n-octylammonium bromide possess to function as an

efficient phase-transfer reagent?

Select your answer from the following choices.

(a) one side of the molecule is electropositive, the other side is electronegative.
(b) one side of the molecule is hydrophilic, the other side is hydrophobic.
(c) one side of the molecule is acidic, the other side is basic.

4B-3

What is the function of NaBH4 in this preparation?

Select your answer from the

following choices.
(a) reducing agent
(b) oxidizing agent
(c) neutralization agent
(d) complexing agent

4B-4

If the average diameter of a gold nanoparticle is 3 nm, what is the estimated number
of Au atoms in each nanoparticle? (the atomic radius of Au is 0.144 nm).

Select your

answer from the following choices and show your work.

(a) 10

(b) 10
(c) 10

(d) 10

4B-5

What is the estimated percentage of Au atoms on the surface of a nanoparticle?

Select your answer from the following choices and show your work.
(a) 20-30%
(b) 40-50%
(c) 60-70%
(d) 80-90%

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Problem 5: Lewis Structure

Total Score: 21 points
5-1

5-2

5-3

5-4

5-5

Points

5-1

Draw one Lewis structure for each of the following molecules.

(a) N2
(b) NH3
(c) O3
(d) SO3

5-2

Draw the Lewis structure of carbon monoxide and assign formal charges and
oxidation states to both the carbon and oxygen atoms in carbon monoxide.

Thiourea-S,S-dioxide, O2SC(NH2)2, has the following skeletal structure

H

O
S

5-3

Draw the Lewis structure of thiourea-S,S-dioxide with zero formal charges on all
atoms.

5-4

Based on the Valence Shell Electron Pair Repulsion (VSEPR) model, what is the
geometry around the sulfur, carbon, and nitrogen according to the Lewis structure
you predicted from 5-3?
5-4a

What is the geometry around the sulfur atom? Select your answer from the

following choices.
(a) trigonal pyramidal
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(b) triangular planar

(c) T-shape
5-4b

Similarly, what is the geometry around the C-atom? Select your answer from

the following choices.

(a) trigonal pyramidal
(b) triangular planar
(c) T-shape
5-4c

Finally, what is the geometry around the N-atom? Select your answer from the

following choices.
(a) trigonal pyramidal
(b) triangular planar
(c) T-shape

Molecular structure in the solid state is usually determined by X-ray diffraction analysis.

According

to this method, the structure of thiourea-S,S-dioxide is shown below:

N
S

65o

All the N, H atoms are coplanar with S, C atoms, and the dihedral angle between the OSO plane

and the SC(NH2)2 plane is 65 .

5-5

Draw the Lewis structure and resonance forms that are consistent with the geometry
determined.

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Problem 6: Alkalinity of Water and Solubility of CO2

Total Scores: 40 points

Points

6-1

6-2

6-3

6-4

6-5

6-6

6-7

6-8

The capacity of water to accept H ions is called alkalinity.

and in the chemistry and biology of natural waters.
HCO3 ,

alkalinity in water are

significantly from alkalinity.

HCO3 ,

2CO3 ,

2-

CO3 , and OH .

Alkalinity is important in water treatment

Generally, the basic species responsible for

+

At pH values below 7, H in water detracts

Therefore, the complete equation for alkalinity in a medium where

and OH are the only contributors to alkalinity can be expressed as

-

2-

alkalinity = [HCO3 ] + 2[CO3 ] + [OH ] [H ]

The contributions made by different species to alkalinity depend upon pH.

Relevant chemical

equations and equilibrium constants (at 298 K) are shown below:

-2

CO2(g) CO2(aq)

KCO2 = 3.44x10

CO2(aq) + H2O H2CO3

KH2CO3 = 2.00x10

H2CO3 HCO3 + H
-

Ka1 = 2.23x10

2-

HCO3 CO3 + H
CaCO3(s) Ca

2+

Ka2 = 4.69x10
2-

+ CO3

Ksp = 4.50x10

H2O H + OH

Kw = 1.00x10

-3

-4

-11

-9

-14

Note: Calculations must be shown.

6-1

Natural waters (river or lake water) generally contain dissolved CO2.

[H2CO3 ] :
(a)

[HCO3 ]

: 1.00 :

2[CO3 ]

in a water at [H+] = 1.00 10-7 M will be:

(b) .

Calculate (a) and (b).

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Gaseous CO2 in the atmosphere can be regarded as a contributor to the alkalinity of

water in equilibrium with air.

Calculate the concentration of CO2 (aq) (mol/L) in pure

water that is in equilibrium with the unpolluted air at 1.01 x 105 Pa and 298 K
containing 0.0360% (molar ratio) CO2. (assuming standard pressure = 1.01 x 105 Pa)

If you are unable to solve this problem, assume that concentration of CO2 (aq) = 1.11x10-5 M for
further calculations.

2-

The solubility (S) of CO2 in water can be defined as S = [CO2(aq)] + [H2CO3] + [HCO3 ] + [CO3 ].
The solubility of atmospheric CO2 in water that is in equilibrium with the unpolluted air at 298 K and
1.01 x 105 Pa will vary with alkalinity.

6-3

Find the solubility of atmospheric CO2 in pure water (mol/L).

Neglect dissociation of

water.

6-4

Find the solubility of atmospheric CO2 in water (mol/L) initially containing 1.00x10

-3

mol/L NaOH.

At 298 K, 1.01 x 105 Pa unpolluted air is in equilibrium with natural water saturated with CaCO3. The
following main equilibrium may exist:
CaCO3(s) + CO2 (aq) + H2O Ca

6-5

2+

+ 2HCO3

Calculate the equilibrium constant for the above equation.

If you are unable to solve this problem, assume that equilibrium constant Keq = 5.00x10-5 for
further calculations.

2+

6-6 Calculate the concentration of Ca

(mg/L) in CaCO3-saturated natural water that is in

equilibrium with atmospheric CO2.

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If you are unable to solve this problem, assume that concentration of Ca2+ (aq) = 40.1 mg/L for
further calculations.

6-7

Find the alkalinity (mol/L) of the above solution.

6-8

In an underground lake saturated with CaCO3, the water has a high content of CO2.
2+

The concentration of Ca

in this lake was found to be as high as 100 mg/L. Assume

the lake and the air above is a closed system, calculate the effective pressure of CO2
2+

(Pa) in air which is in equilibrium with this Ca content.

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Problem 7: Kinetic Behavior of Ozone

Total Scores: 28oints

Points

Ozone (O3) is a form of oxygen.

7-1

7-2

7-3

7-4

7-5

It is a natural component of the stratosphere, where it shields the

earth from life-destroying ultraviolet radiation.

On absorbing light in this region, ozone is converted

to dioxygen molecules.
For the overall reaction of ozone decomposition,
2O3 3O2.
One of the proposed mechanisms is expressed as

O3

k1
k -1

O3 + O

(1)

O + O2
k2

(2)

2O 2

where k1, k-1, and k2 are the rate constants.

7-1

According to the above mechanism what are the differential rate equations for the
formation (or consumption) of O3, O2, and O at time t, assuming step 2 is irreversible.

7-2

Simplification in obtaining the rate law may be found by making appropriate

assumptions.

Assuming that the concentration of O atoms reaches equilibrium

rapidly, its concentration may be given by the equilibrium constant of the reaction (1).
The second step is rate determining.

Under this equilibrium approximation, deduce

the differential rate equation for the O3 depletion as a function of O2 and O3

concentrations.

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7-3

Language:

Another assumption frequently made is that the rates of oxygen atom production and
consumption are equal (this is called steady state).

Under the steady state

approximation,

the

that

is

d[O]/dt

0,

show

that

rate

equation

is:

d [O3 ]
2k1 k 2 [O3 ]
=
.
dt
k 1 [O2 ] + k 2 [O3 ]

One pathway for the destruction of ozone (2O3 3O2) in the upper atmosphere is catalyzed by
Freons.

For instance, when CCl2F2 (Freon-12) migrates to the upper atmosphere, the ultraviolet

photolysis of CCl2F2 may give rise to Cl atoms according to the following reaction:

CCl2F2

7-4

CF2Cl + Cl

(3)

Chlorine atom can act as a catalyst for the destruction of ozone. The first slow step of
a Cl-catalyzed mechanism is proposed as follows:
Cl(g) + O3(g)

ClO(g) + O2(g)

(4)

Assuming a two-step mechanism, propose the second step in the mechanism.

7-5

The activation energy for Cl-catalyzed destruction of ozone is 2.1 kJ/mol, while the
activation energy for the reaction without the presence of catalyst is 14.0 kJ/mol.
Estimate the ratio of the rate constant for the catalyzed reaction to that for the
uncatalyzed reaction at 25 oC. Assume the frequency factor is the same for each
reaction.

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Problem 8: Protein Folding

Total Scores: 26 points

Points

8-1

8-2

8-3

8-4

8-5

8-6

8-7

Most proteins exist usually only in two forms, the native form (N) and the unfolded form (U) when
they are thermally or chemically denatured, without appreciable concentrations of other stable
intermediates in equilibrium with the native and unfolded forms.

For these proteins, the

folding-unfolding equilibrium can be described by the following simple chemical equation:

K(T)

where N and U denote the folded state (native state) and the unfolded state (denatured state) of the
protein, respectively.

8-1

K(T) is the equilibrium constant for the process at absolute temperature T.

What is the equilibrium constant for the process when the native and denatured
states are present in equal proportions at equilibrium?

8-2

What is the standard free energy change of the process (G(T)) when the native and
denatured states are present in equal proportions at equilibrium?

Express your

answer in SI units.

8-3

If (CN)eq and (CU)eq denote the equilibrium concentrations of N and U in solution,

respectively, and C is the total concentration of the protein, the fraction of the total
protein that is unfolded under the equilibrium condition is given by fU = (CU)eq/C.
Deduce an expression for fU in terms of the equilibrium constant K.
on the answer sheet.

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Country:

Language:

When a protein is denatured by increasing the temperature of the solution, the fraction of the
unfolded protein increases with temperature, as shown in the following Figure.

The mid-point of the denaturation curve is given by fU = and T = T.

as the denaturation temperature.

The latter is often referred to

At temperatures higher than T, fU increases above , but at

temperatures lower than T , fU decreases below .

8-4

What is the sign of G(T) at temperatures below and above T? Select your answer
from the following choices.
(a) Negative both below and above T
(b) Positive both below and above T
(c) Positive below T, but negative above T
(d) Negative below T, but positive above T.

8-5

How does the standard Gibbs free energy change for the process vary when the
temperature (i) increases above T1/2 and (ii) decreases below T?
from the following choices.
(a) Decrease in both cases.
(b) Increase in both cases.
(c) Increases above T , but decreases below T
(d) Decreases above T , but increases below T

25

Select your answer

Country:

Language:

The kinetics of unfolding and refolding of a protein has recently become an intense area of study.
We could rewrite the chemical equation for the process as follows:

kf
kb

where kf and kb denote the forward and backward reaction rate constants, respectively., assuming
that both the forward and reverse processes are elementary steps that follow first-order kinetics.

8-6

For the simple chemical equation and elementary kinetic steps used to describe the
protein folding-unfolding process outlined above, what is the relationship between
equilibrium constant K and the rate constants kf and kb?

8-7

Derive a rate law for the overall process, that is dCU/dt in terms of only rate
constants, CU and (CU)eq.

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