Country: Language:: 37 Icho Theoretical Examination
Country: Language:: 37 Icho Theoretical Examination
Country: Language:: 37 Icho Theoretical Examination
Language:
th
5 hours
- problem booklet
- answer sheets:
Use if necessary.
Write
- atomic masses
- constants
- answers
- restroom break
- examination booklet
GOOD
LUCK
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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
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
E = E (0.0592 / n) log K
Arrhenius equation
k = Ae
Clausius-Clapeyron equation
ln P = - Hvap / RT + B
De Broglie relation
h / mv
=
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
= 2.4790 kJ mol
Pi ()
= 3.1415927
-1
-1
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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
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
-1
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1-4
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.
to PAGE gel.
1-6
>
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.
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
1-8
(a)
(b)
O
H
H
O
(c)
(d)
H
OH
H
OH
O
O
(e)
O
O
O
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However, unnatural
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 =
(minor) =
(major) =
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
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
The R/S notation of C-1 remained unchanged before and after the reaction.
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
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: ____.
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CHO
P
Q
R
S
T
U
CH2OH
Disaccharides are compounds with two monosaccharide subunits linked together by a glycosidic
bond.
H OH H
HO
HO
H
H
OH
H OH H
HO
glycosidic bond
O
OH
OH
H
H OH H
H
O
HO
H
H
OH H
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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
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
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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
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
(c) G only
-5
(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
difference
Upon irradiation with ultraviolet light, trans-stilbene is transformed into an intermediate H, which
undergoes a photocyclization to form dihydrophenanthrene I.
phenanthrene.
oxidation
For translation:
H H
I
heat
trans-Stilbene
a
Phenanthrene
trans-Stilbene
heat
oxidation
3-5
3-6
What is the relative stereochemistry of the two H-atoms shown (cis or trans) in
compound I?
Upon irradiation,
NC 1 CN
CH3
CN
CN
For translation:
6
8
J
a
heat
12
CH3
10
heat
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3-8
(b) K
Compound K can react with one equivalent of CF3CO2H to generate a stable aromatic
salt.
following choices.
(a) C-2 (b) C-3 (c) C-4 (d) C-5
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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.
Au(CN)2 ,
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.
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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Au3+(aq) + 3 e
AuCl4(aq) + 3 e
Au(s)
E = +1.50 V
Au(s) + 4 Cl(aq)
E = +1.00 V
3+
4A-6
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.
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.
(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
Which
(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
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
(b) 10
(c) 10
(d) 10
4B-5
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5-2
5-3
5-4
5-5
Points
5-1
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.
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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Similarly, what is the geometry around the C-atom? Select your answer from
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
N
S
65o
All the N, H atoms are coplanar with S, C atoms, and the dihedral angle between the OSO plane
5-5
Draw the Lewis structure and resonance forms that are consistent with the geometry
determined.
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Points
6-1
6-2
6-3
6-4
6-5
6-6
6-7
6-8
2CO3 ,
2-
CO3 , and OH .
2-
Relevant chemical
CO2(g) CO2(aq)
KCO2 = 3.44x10
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
6-1
[HCO3 ]
: 1.00 :
2[CO3 ]
(b) .
The ratio of
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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
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
If you are unable to solve this problem, assume that equilibrium constant Keq = 5.00x10-5 for
further calculations.
2+
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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
6-8
In an underground lake saturated with CaCO3, the water has a high content of CO2.
2+
The concentration of Ca
the lake and the air above is a closed system, calculate the effective pressure of CO2
2+
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Points
7-1
7-2
7-3
7-4
7-5
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
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
rapidly, its concentration may be given by the equilibrium constant of the reaction (1).
The second step is rate determining.
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Another assumption frequently made is that the rates of oxygen atom production and
consumption are equal (this is called 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)
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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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.
K(T)
where N and U denote the folded state (native state) and the unfolded state (denatured state) of the
protein, respectively.
8-1
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
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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.
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
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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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