02 18 2014 IChO46 Preparatory Problems

Preparatory Problems
46
th
International Chemistry Olympiad (IChO - 2014)
Editorial Board
Nguyen Tien Thao, Editor in Chief
Nguyen Minh Hai
Nguyen Van Noi
Truong Thanh Tu
Hanoi University of Science, Vietnam National University, Hanoi
Tel: 00! !"#!0$%#%& 'a(: 00! !"#!0$%#% Email: icho)0%!*re*+hus,edu,vn
Febrary 1!
th
" 2014 (#e$ised)

46
th
International Chemistry Olympiad Preparatory Problems
%anoi" &ietnam - 2014
Contributing Authors
Le Minh Cam, Hanoi National University of Education
Vu Viet Cuong, Hanoi University of Science, VNU-Hanoi
Pham he Chinh, !nstitute of Chemistry, V"S
Nguyen Huu #inh, Hanoi National University of Education
ran hi #a, Hanoi National University of Education
Nguyen Van #au, Hanoi University of Science, VNU-Hanoi
#ao Phuong #ie$, Hanoi National University of Education
Pham Huu #ien, Hanoi National University of Education
Nguyen Hien, Hanoi National University of Education
Hoang Van Hung, Hanoi National University of Education
Nguyen Hung Huy, Hanoi University of Science, VNU-Hanoi
u Vong Nghi, Hanoi University of Science, VNU-Hanoi
rieu hi Nguyet, Hanoi University of Science, VNU-Hanoi
#o %uy Son, Vietnam "tomic Energy !nstitute
a hi hao, Hanoi University of Science, VNU-Hanoi
Nguyen ien hao, Hanoi University of Science, VNU-Hanoi
Lam Ngoc hiem, Hanoi University of Science, VNU-Hanoi
Ngo hi huan, Hanoi University of Science, VNU-Hanoi
Vu %uoc rung, Hanoi National University of Education
#ao Huu Vinh, Hanoi University of Science, VNU-Hanoi
Acknowledgements
&e 'ould li(e to e)$ress our dee$ gratitude to the mem*ers of the !nternational Steering
Committee for their valua*le comments and suggestions and to #r+ Vu Viet Cuong, #r+ Nguyen
Hung Huy, and #r+ Pham Van Phong for their (ind colla*orations+

Sincerely yours,
Editors
Chemistry: The flavor of life
)

46
th
Preface
We are happy to provide Preparatory Problems for the 46
th
International Chemistry
Olympiad. These problems were prepared with reliance on fundamental topics firmly
covered in high school chemistry courses along with some advanced topics for the
chemistry olympiad competition. These topics are listed under Topics of Advanced
Difficulty, and their applications are given in the problems. Solutions will be sent to
Head Mentors on February 20
th
, 2014 and updated on '''(i)ho2014(hs(ed($n on
May 31
st
, 2014. Although a lot of efforts have gone to making this Booklet, some
mistakes, typos may still be there. We welcome any comments, corrections, or questions
about the problems to i)ho2014prep*hs(ed($n(
We hope that these problems will be motivating for students to participate in the
IChO-2014 competition. We believe that IChO-2014 will not only be a chemistry
competition, but also a pleasant time for you to know about Vietnamese culture.
-e look forward to seeing you in Hanoi and at Hanoi University of Science, Vietnam
National University in Hanoi.
Hanoi, January 31
st
, 2014
Editor in Chief
Nguyen Tien Thao
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, "

46
th
February 18
th
, 2014 (Revised)
Contents
Fields of Advanced Difficulty 6
Physical Constants, Symbols and Conversion Factors 7
Part 1. Theoretical Problems 8
Pro*lem ,+ Polar and non-$olar molecules -
Pro*lem .+ Calculations of lattice energy of ionic com$ounds ,/
Pro*lem 0+ " frog in a &ell ,.
Pro*lem 1+ Electrons in a .,0-#imensional 2o) ,1
Pro*lem 3+ ug of 'ar ,4
Pro*lem 4+ 5adiochemistry ,6
Pro*lem 6+ "$$lied thermodynamics ,7
Pro*lem -+ Com$le) com$ounds ./
Pro*lem 7+ Lead com$ounds .1
Pro*lem ,/+ "$$lied electrochemistry .4
Pro*lem ,,+ Phos$horic acid .6
Pro*lem ,.+ 8inetic chemistry .-
Pro*lem ,0+ 8inetics of the decom$osition of hydrogen $ero)ide 0/
Pro*lem ,1+ Magnetism of transition metal com$le)es 0,
Pro*lem ,3+ Structure and synthesis of "l-8eggin ion 01
Pro*lem ,4+ Safrole 03
Pro*lem ,6+ !mida9ole 0-
Pro*lem ,-+ Small heterocycles 07
!

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Pro*lem ,7+ Vitamin H 1,
Pro*lem ./+ No $erfume 'ithout :asmine 11
Pro*lem .,+Vietnamese cinnamon 16
Pro*lem ..+ Cinnamic acid 17
Pro*lem .0+ ris;trimethylsilyl<silane and a9o*isiso*utyronitrile
3/
Pro*lem .1+ ;-<-Menthol from ;=<->-0-carene
3.
Pro*lem .3+ Cefalotin 30
Pro*lem .4+ " heterocyclic com$ound 33
Pro*lem .6+ Lotus 34
Pro*lem .-+ NM5 S$ectra 37
Pro*lem .7+ !5 S$ectra 4/
Part 2. Practical Problems 62
Practical Problems, Safety 62
Pro*lem 0/+ Condensation *et'een valinin and *en9ylamine 40
Pro*lem 0,+ Synthesis of eugeno)y acetic acid 43
Pro*lem 0.+ Com$le)ometric titration 4-
Pro*lem 00+ #etermination of 9inc and lead in 9inc o)ide $o'der 6.
Pro*lem 01+ Pre$aration of co$$er;!!< acetylacetonate 64
Pro*lem 03+ 8inetic analysis of the hydrolysis of as$irin 67
Pro*lem 04+ Com$le) formation of ferric ion and salicylic acid -3
Appendices 90
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46
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ields o! Ad"anced #i!!icult$
+heoreti)al
Kinetics: .ntegrated first3 and second3order rate e4uation& analysis of moderately
com*le( reactions mechanisms using the steady state a**ro(imation, the use of the
5rrhenius e4uation,
Thermodynamics: Electrochemical cells, the relationshi* 1et6een e4uili1rium
constants, electromotive force and standard 7i11s energy, the variation of the
e4uili1rium constant 6ith tem*erature,
Quantum mechanics: 0article3in3a31o( calculations, or1ital3overla*s, s*in3or1it
cou*ling,
Sectroscoy! .nter*retation of .8 s*ectra and relatively sim*le
%
H,
%"
C, and
)9
5l
NM8 s*ectra: chemical shifts, multi*licities, cou*ling constants and integrals,
"dvanced #nor$anic! Trans effect& the use of sim*le crystal field theory to e(*lain
electronic configurations in octahedral and tetrahedral com*le(es& calculation of
the magnetic moment using the s*in3only formula, solid state structures, *ac:ing
arrangement,
"dvanced %r$anic! Stereoselective transformations& aromatic nucleo*hilic
su1stitution& *olycyclic aromatic com*ounds and heterocycles,
$

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Pra)ti)al
&asic synthesis techni'ues: Thin layer chromatogra*hy, E(traction, 'iltration,
;rying, Titration,
() * )is sectroscoy+
Physi)al Constants" ,ymbols and Con$ersion Fa)tors
5vogadro<s constant, ,
5
= $,0))%>%0
)"
mol
?%

@oltAmann constant, -
@
= %,"09>%0
?)"
2BC
?%

Universal gas constant, R . ,"%!# 2BC
?%
Bmol
?%
- 0,0)0# atmBDBC
?%
Bmol
?%

S*eed of light, c . ),EE9E>%0
mBs
?%

0lanc:<s constant, h . $,$)$%>%0
?"!
2Bs
'araday constant, F = E,$!#""EE>%0
!
C
Mass of electron, m
e
= E,%0E")%#>%0
?"%
:gBmol
3%
Standard *ressure, / = % 1ar = %0
#
0a
5tmos*heric *ressure, /
atm
= %,0%")#>%0
#
0a = 9$0 mm Hg = 9$0 Torr
Fero of the Celsius scale, )9",%# C
% *icometer GmH = %0
?%)
m& %I = %0
3%0
m& nanometer GnmH . %0
?E
m
% eV = %,$ > %0
3%E
2
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46
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Periodi) +able o. Elements 'ith #elati$e /tomi) 0asses
1
18
1
H
1.008
2
13 14 15 16 17
2
He
4.003
3
Li
6.941
4
Be
9.012
5
B
10.81
6
C
12.01
7
N
14.01
8
O
16.00
9
F
19.00
10
Ne
20.18
11
Na
22.99
12
Mg
24.31
3 4 5 6 7 8 9 10 11 12
13
Al
26.98
14
Si
28.09
15
P
30.97
16
S
32.07
17
Cl
35.45
18
Ar
39.95
19
K
39.10
20
Ca
40.08
21
Sc
44.96
22
Ti
47.87
23
50.94
24
Cr
52.00
25
M!
54.94
26
Fe
55.85
27
C"
58.93
28
Ni
58.69
29
C#
63.55
30
$!
65.38
31
%a
69.72
32
%e
72.64
33
A&
74.92
34
Se
78.96
35
Br
79.90
36
Kr
83.80
37
'(
85.47
38
Sr
87.62
39
)
88.91
40
$r
91.22
41
N(
92.91
42
M"
95.96
43
Tc
*98+
44
'#
101.07
45
',
102.91
46
P-
106.42
47
Ag
107.87
48
C-
112.41
49
.!
114.82
50
S!
118.71
51
S(
121.76
52
Te
127.60
53
.
126.90
54
/e
131.29
55
C&
132.91
56
Ba
137.33
57
La
138.91
72
H0
178.49
73
Ta
180.95
74
1
183.84
75
'e
186.21
76
O&
190.23
77
.r
192.22
78
P2
195.08
79
A#
196.97
80
Hg
200.59
81
Tl
204.38
82
P(
207.2
83
Bi
208.98
84
P"
32094
85
A2
32104
86
'!
32224
87
Fr
32234
88
'a
226.0
89
Ac
32274
104
'0
32614
105
Ha
32624
58
Ce
140.12
59
Pr
140.91
60
N-
144.24
61
P5
31454
62
S5
150.36
63
6#
151.96
64
%-
157.25
65
T(
158.93
66
78
162.50
67
H"
164.93
68
6r
167.26
69
T5
168.93
70
)(
173.05
71
L#
174.97
90
T,
232.04
91
Pa
231.04
92
9
238.03
93
N:
237.05
94
P#
32444
95
A5
32434
96
C5
32474
97
B;
32474
98
C0
32514
99
6&
32544
100
F5
32574
101
M-
32564
102
N"
32544
103
Lr
32574
PA%T 1. T&'(%'T)CA* P%(+*',-
Problem 1. Polar and non-polar molecules
.n chemistry, a molecule is considered non0o1ar 6hen its *ositive charge
center and negative charge center coincide, i,e, the charge distri1ution is
symmetrical in the molecule, /n the other hand, 6hen a molecule has t6o distinct
centers for *ositive and negative charges, it is considered o1ar,
This charge distri1ution *ro*erty is measured 1y a 4uantity called the dio1e
moment 6hich is defined as the magnitude of the charge 4 and the distance 1
1et6een the charges:
1 '
=

46
th
The di*ole moment is a vector *ointing from the *ositive charge center to the
negative one,
The di*ole moment is often e(*ressed in de1yes G;H, The relationshi* 1et6een
de1yes G;H and coulom1 meters GCBmH in S. units is as follo6s: % ; = ","">%0
?"0
CBm,
1, The di*ole moment is closely related to the molecular geometry, .n order to
calculate the net di*ole moment of multi3atomic molecules, 6e can add the
di*ole moment vectors for individual 1onds, .n this case, an individual 1ond is
considered to have its o6n di*ole moment called the 1ond moment,
'or a non3linear molecule 6ith three atoms, 5@C, the net di*ole moment can 1e
calculated 1y adding vectors in 6hich
% and
) are the 1ond moments for 5@ and

5C 1onds, and is the 1ond angle, ;etermine the general e4uation for calculating
the net di*ole moment,
2( The directions of the individual 1ond moments should 1e considered,
),% The molecule of C/
)
is linear, Calculate the net di*ole moment of the
molecule,
),) 5 non3linear molecule of 5
)
@ such as H
)
S has the net di*ole moment 0,
;etermine for H
)
S if
SH
= ),$%>%0
?"0
CBm and the 1ond angle = E),0
o
,
1( The 1ond angle HCH in the formaldehyde molecule is determined
e(*erimentally to 1e a**ro(imately %)0
o
& the 1ond moments for C3H and C3/
1onds are H C
J
= 0,! ; and / C
J
= = )," ;, res*ectively,
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",% ;etermine the or1ital hy1ridiAation of C and / atoms, and *lot the
overla*s of or1itals in the formaldehyde molecule,
",) Calculate the net di*ole moment GJH of the formaldehyde G;H, given the order
of the electronegativity as H C /
K K K > >
, G2ints! 31ectrone$ativity is the abi1ity
o4 an atom in a mo1ecu1e to attract shared e1ectrons to itse14H,
4( The di*ole moments of 6ater and dimethylether in gaseous state are determined
as %,! ;, and %,)E ;, res*ectively, The 1ond angle formed 1y t6o 1ond moments
of /3H in the 6ater molecule is %0#
o
, The 1ond angle formed 1y t6o 1ond
moments of /3C in the ether molecule is %%0
o
,
Estimate the 1ond angle formed 1y the 1ond moments of /3H and C3/ in the
methanol molecule, given that the di*ole moment of methanol molecule is %,$E ;,
5ssume that individual 1ond moments are unchanged in different molecules,
Problem 2. Calculations of lattice energy of ionic compounds
1( Dithium is the lightest metal and does not e(ist in *ure form in nature due to its
high reactivity to 6ater, moisture, o(ygen,,, Dithium readily forms ion 6ith a %L
charge 6hen reacting 6ith nonmetals, -rite do6n the follo6ing chemical
reactions at room tem*erature:
%,% Dithium reacts 6ith 6ater,
%,) Dithium reacts 6ith halogens, e,g, Cl
)
,
%," Dithium reacts 6ith dilute sulfuric acid and concentrated sulfuric acid,
2( The change in enthal*y of a *articular reaction is the same 6hether it ta:es *lace
in one ste* or in a series of ste*s GHessMs la6H, Use the follo6ing data:
Su1limation enthal*y of DiGsH, N
S
H = %#E :2Bmol
?%
,
.oniAation energy of DiGgH, . = #,!0 eV,
%0

46
th
;issociation enthal*y of Cl
)
, N
;
H = )!) :2Bmol
?%
,
Electron affinity of ClGgH, E = 3",! eV,
'ormation enthal*y of DiClGsH, N
f
H = ? !0)," :2Bmol
?%
,
$) , 0 =
+
5i
r
I&
" , % =
61
r
I& N
5
= $,0)>%0
)"
mol
?%
,
),% Esta1lish the @orn3Ha1er cycle for lithium chloride crystal,
),) Calculate the lattice energy U
o
G:2Bmol
3%
H using the @orn3Ha1er cycle,
1( .n *ractice, e(*erimental data may 1e em*loyed to calculate lattice energies in
addition to the @orn3Ha1er cycle, /ne of the semi em*irical formulae to calculate
the lattice energy U
o
for an ionic com*ound, 6hich 6as *ro*osed 1y Ca*ustins:ii,
is as follo6s:
U
0
= 3 )9,)
+
+
+
r r
Z Z

+
r r
"!# , 0
%
6here: is the num1er of ions in the em*irical formula of ionic com*ound,
r
L
and r
3
are the radii of the cation and anion, res*ectively, in I,
F
L
and F
3
are cation and anion charges, res*ectively,
U
0
is the lattice energy, in :cal
B
mol
3%
,
Use the Ca*ustins:ii em*irical formula to calculate U
o
Gin :2Bmol
?%
H

of DiCl crystal,
given that % cal = !,%! 2,
4( @ased on the results of t6o calculation methods in sections ) and ", choose the
a**ro*riate 1o(:
5ccording to the @orn3Ha1er cycle and Ca*ustins:ii em*irical formula
for lithium chloride crystal structure, 1oth methods are close to the
e(*erimental value,
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, %%

46
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/nly the calculated result of the @orn3Ha1er cycle is close to the
e(*erimental value,
/nly the calculated result of the Ca*ustins:ii em*irical formula is close
to the e(*erimental value,
7ata: 7iven the e(*erimental value of lattice energy for DiCl is !E,0! :2Omol,
2( .n the formation of DiCl crystal, it is found out that the radius of lithium cation is
smaller than that of chloride anion, Thus, the lithium ions 6ill occu*y the
octahedral holes among si( surrounding chloride ions, 5dditionally, the 1ody edge
length of DiCl cu1ic unit cells is #,%! I, 5ssume that Di
L
ions Pust fit into
octahedral holes of the closest *ac:ed chloride anions,
#,% Calculate the ionic radii for the Di
L
and Cl
3
ions,
#,) Com*are the calculated GtheoreticalH radii 6ith the e(*erimental radii given
1elo6, and choose the a**ro*riate 1o(:
@oth calculated radii of lithium and chloride ions are close to the
e(*erimental values,

/nly the calculated radius of lithium ion is close to the e(*erimental value
/nly the calculated radius of chloride ion is close to the e(*erimental value,
The e(*erimental radii of Di
L
and Cl
?
are 0,$) I and %," I, res*ectively,
Problem 3. A frog in a well
The energy levels of an electron in a one3dimensional 1o( are given 1y:
%)

46
th
)
)
n )
h
E n
mD
= n: %, ), "Q
in 6hich h is the 0lanc:Ms constant, m is the mass of the electron, and D is the
length of the 1o(,
1( The electrons in a linear conPugated neutral molecule are treated as
individual *articles in a one3dimensional 1o(, 5ssume that the electrons are
delocaliAed in the molecular length 6ith the total num1er of N electrons and
their arrangement is governed 1y the *rinci*les of 4uantum mechanics,
%,% ;erive the general e(*ression for NE
DUM/ ? H/M/
6hen an electron is e(cited
from the H/M/ to the DUM/,
%,) ;etermine the 6avelength of the a1sor*tion from the H/M/ to the DUM/,
2( 5**ly the model of electrons in a one3dimensional 1o( for three dye
molecules 6ith the follo6ing structures Gsee the structural formulaH, 5ssume
that the electrons are delocaliAed in the s*ace 1et6een the t6o *henyl grou*s
6ith the length D is a**ro(imately e4ual to G): L %HG0,%!0H nm, in 6hich : is
the num1er of the dou1le 1onds,
aH %,!3di*henyl3%,"31utadiene
Gdenoted as B3H
1H %,$3di*henyl3%,",#3he(atriene
Gdenoted as %+H
cH %,3di*henyl3%,",#,93octatetraene
Gdenoted as O+H
),% Calculate the 1o( length D GIH for each of the dyes,
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46
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),) ;etermine the 6avelength GnmH of the a1sor*tion for the molecules
of the investigated dyes,
1( 8ecalculate the 1o( length D GIH for the three dye molecules, assuming that the
electrons are delocaliAed over the linear conPugated chain 6hich is *resented
as a line *lotted 1et6een the t6o *henyl grou*s Gsee the structural formulaH,
The 1ond angle C ? C ? C is %)0
o
and the average length of C ? C 1ond is 0,%!0
nm,
4( 7ive the follo6ing e(*erimental data on the 6avelength of a1sor*tion,
!,% ;etermine the 1o( length D GIH of the linear conPugated chain for each of the
three investigated dyes,
!,) Ta1ulate the values of the 1o( length D for the dyes calculated a1ove 1y the
three different methods, denoted as 1, 2, and 1, Choose the method 6hich is the
most fit to the e(*erimental data,

Problem 4. Particles in 2, 3 - Dimensional o!
1( .n 0ro1lem ", the energy E of *article in one3 dimensional 1o( is calculated as:
)
)
)
h
E =n
mD
6here h is 0lanc:Ms constant& m is the mass of the *article& D is the 1o( length&
n is the 4uantum num1er, n = %, ), "Q
Su1stance B3 %+ O+
GnmH
"),# "#0,E #$,%
%!

46
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5n electron in a %0 nm one3dimensional 1o( is e(cited from the ground state to a
higher energy level 1y a1sor1ing a *hoton of the electromagnetic radiation 6ith a
6avelength of %,"9!>%0
3#
m,
%,% -hat is the energy ga* GNEH of the t6o mentioned transitionsR
%,) ;etermine the final energy state for this transition,

2( The treatment of a *article in a one3 dimensional 1o( can 1e e(tended to a t6o3
dimensional 1o( of dimensions D
(
and D
y
yielding the follo6ing e(*ression for
energy:

)
) )
y
(
) )
( y
n
n h
E =
m D D

+

The t6o 4uantum num1ers inde*endently can assume only integer values,
Consider an electron confined in a t6o3dimensional 1o( that is D
(
= ,00 nm in the
( direction and D
y
= #,00 nm in the y direction,
),% -hat are the 4uantum num1ers for the first three allo6ed energy levelsR -rite
the first three energy, E
(y
, in order of increasing energyR
),) Calculate the 6avelength of light necessary to move an electron from the first
e(cited state to the second e(cited one,
1( Similarly, the treatment of a *article in a one3dimensional 1o( can 1e e(tended
to a rectangular 1o( of dimensions D
(
, D
y,
and D
A
, yielding the follo6ing e(*ression
for energy:

)
) ) )
y
( A
) ) )
( y A
n
n n h
E =
m D D D

+ +

!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, %#

46
th
The three 4uantum num1ers n
(
, n
y,
and n
A
inde*endently can assume only
integer values, 5n o(ygen molecule is confined in a cu1ic 1o( of volume ,00 m
"
,
5ssume that the molecule has an energy of $,%9" > %0
?)%
2& tem*erature T = )E C,
",% -hat is the value of
)
%
) ) )
H G
8 y 9
n n n n + + =
for this moleculeR
",) -hat is the energy se*aration 1et6een the levels n and n L %R
4( .n 4uantum mechanics, an energy level is said to 1e degenerate if it corres*onds
to t6o or more different measura1le states of a 4uantum system, Consider a
*article in a cu1ic 1o(, -hat is the degeneracy of the level that has energy )%O"
times that of the lo6est levelR

Problem ". #ug of war
Tug of war is a sport that directly pits two teams against each other in a test of strength.
This is also a traditional game of Vietnamese people
The follo6ing ta1le gives the standard molar 7i11s energy at different
tem*eratures for the reaction G%H 1elo6:
S/
"
GgH S/
)
GgH L S /
)
GgH G%H
TO
o
C #)9 ##) $)9 $0 9)9
N
r
7
o
O:2Bmol
?%
)%,90! )0,$)$ %!,)%0 E,)E! !,#!
1( Use the Van HoffMs e4uation to estimate the lnC
*%
at each tem*erature,
2( 0lot lnC
*%
against %OT to determine the value of N
r
H
o
in :2Bmol
?%
assuming that
N
r
H
o
does not vary significantly over the given tem*erature range,
%$

46
th
1( Using the 1est3fit line to *lot a lnC
*%
versus %OT, determine the C
*)
for the
follo6ing reaction G)H at $#%,""
o
C:
)S/
"
GgH )S/
)
GgH L /
)
GgH G)H
4( 5n amount of %#,%E g of iron G..H sulfate 6as heated in an evacuated %,00 D
container to $#%,""
o
C, in 6hich the follo6ing reactions ta:e *lace:
'eS/
!
GsH 'e
)
/
"
GsH L S/
"
GgH L S/
)
GgH G"H
)S/
"
GgH )S/
)
GgH L /
)
GgH G!H
-hen the system has reached e4uili1rium, the *artial *ressure of o(ygen is of
)%,) mmHg, Calculate the e4uili1rium *ressure of the gases and the value of C
*"
for the reaction G"H at e4uili1rium,
2( Calculate the *ercentage of 'eS/
!
decom*osedR
Problem $. %adioc&emistry
Fircon GFrSi/
!
H is a mineral found a1undantly in *lacer de*osits located in the
central coast of Vietnam, @esides 1eing 6idely utiliAed in the ceramic industry,
Aircon is also used as a ra6 material for the manufacture of Aircaloy 6hich is used
to 1uild fuel rods that hold the uranium dio(ide GU/
)
H fuel *ellets in nuclear
reactors, Fircon ore contains a trace amount of uranium, and it is not a via1le
source of uranium in *ractice, Ho6ever, Aircon crystals ma:e a *erfect storage
medium to avoid the loss of uranium and lead G01H isoto*es 1ecause of its sta1le
crystal structure, This allo6s develo*ing uranium3lead dating method,
There are " naturally occurring decay series:
3 The thorium series 1egins 6ith
)")
Th and ends u* 6ith
)0
01,
3 The uranium series Galso referred to as the uranium3radium seriesH is headed
1y
)"
U, The half3life Gt
%O)
H of
)"
U is !,!9 > %0
E
years,
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, %9

46
th
3 The actinium series is headed 1y
)"#
U 6ith the half3life of 9,0" >
%0
years,
'our sta1le isoto*es of 01 e(ist in nature:
)0!
01,
)0$
01,
)09
01, and
)0
01, The natural
a1undance of each isoto*e is sho6n in the follo6ing ta1le,
)0!
01
)0$
01
)09
01
)0
01
%,! )!,% )),% #),!
5n analysis of a Aircon mineral sam*le gives the follo6ing mass ratios of U and 01
isoto*es:
mG
)"
UH : mG
)"#
UH : mG
)0$
01H : mG
)0!
01H = EE,)9# : 0,9)% : %!,"0 : 0,)99
1( .ndicate the sta1le isoto*e of 01 6hich is not involved in the a1ove decay series,
2( ;etermine the mass ratio of
)"
U to
)"#
U 6hen the Aircon mineral 6as first
formed, 5ssume that the mineral already contained natural 01 right at the onset of
its formation+
1, 0roduction of uranium from lo63grade 6ill encounter many difficulties, nota1ly
large concentration of im*urities and lo6 concentrations of uranium in leach
solutions, Various technological advances have 1een a**lied to overcome the
aforementioned *ro1lems& these include fractional *reci*itation, li4uid3li4uid
e(traction, or ion e(change methods,
.n an e(*eriment to e(tract uranium from sam*le of lo6 uranium content using
diluted H
)
S/
!
, in the *reliminary treated leach solutions, the concentration of
uranyl sulfate GU/
)
S/
!
H is 0,0% M and the concentration of ironG...H sulfate
G'e
)
GS/
!
H
"
H goes u* to 0,0# M, The se*aration of uranium from iron and other
im*urities can 1e carried out 1y the fractional *reci*itation method,
Calculate the *H necessary to *reci*itate EET of 'e
"L
6ithout losing uranium
ions, 5ssume that the adsor*tion of uranium onto 'eG/HH
"
is negligi1le, Under the
%

46
th
e(*erimental conditions, the solu1ility *roduct values for U/
)
G/HH
)
and 'eG/HH
"
are %,0 > %0
?))
and ",>%0
?"
,

res*ectively,
4( /ne of the *ro*er methods to o1tain a rich uranium solution is the li4uid3li4uid
e(traction 6ith the organic *hase containing the e(tracted agent of
tri1utyl*hos*hate GT@0H diluted in :erosene, -hen e(tracting uranium in the form
of uranyl nitrate GU/
)
GN/
"
H
)
H under a**ro*riate conditions, the relationshi*
1et6een the concentrations of uranium in 6ater and organic *hases is given 1y:
;istri1ution coefficient: ; =
, or$
a'
6
6
= %0
6here: C
org
and C
a4
are the e4uili1rium concentrations GMH of U/
)
GN/
"
H
)
in organic
and a4ueous *hases, res*ectively,
Calculate the mole *ercentage Gin com*arison 6ith the initial concentrationH of
U/
)
GN/
"
H
)
remaining in the a4ueous *hase after e(tracting %,0 D of the solution
G6ith an initial concentration of 0,0% MH 6ith #00 mD of organic solvent,
2( 0ro*ose a scheme to e(tract E$T of U/
)
GN/
"
H
)
from %,0 D of the a4ueous *hase
into #00 mD of the organic *hase, 5ssume that the distri1ution coefficient remains
constant throughout the e(traction *rocess G; = %0H,
Problem '. Applied t&ermodynamics
1( .n a**lied thermodynamics, 7i11s free energy *lays an im*ortant role and can
1e calculated according to the follo6ing e(*ression:
U7
o
)E
= UH
o
)E
? TUS
o
)E
U7
o
)E
3 standard free energy change
UH
o
)E
3

standard enthal*y change
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, %E

46
th
US
o
)E
3 standard entro*y change
The 1urning of gra*hite is re*resented 1y t6o reactions:
C Ggra*hiteH L S /
)
GgH V C/ GgH G%H
C Ggra*hiteH L /
)
GgH V C/
)
GgH G)H
The de*endence of UH
o
, US
o
on tem*erature is as follo6s:
8eaction G%H: UH
o
T
G%H G2Bmol
3%
H = ?%%))E, L #,E!T&
US
o
T
G%H G2BC
3%
Bmol
3%
H = #!,0 L $,)%lnT
8eaction G)H: UH
o
T
G)H G2Bmol
3%
H = ? "E"9!0,% L 0,99T&
US
o
T
G)H G2BC
3%
Bmol
3%
H = %,#! ? 0,99lnT
@ased on the a1ove data:
%,% ;erive the e(*ression for the 7i11s free energy as a function of tem*erature,
U7
o
T
= fGTH for each reaction,
%,) 0redict the changes of U7
o
T
6ith an increase in tem*erature,
2( 5ssume that at %!00
o
C, during the course of reactions G%H and G)H, C/ gas might
continue to react 6ith /
)
to form the final *roduct C/
)
,
),% -rite do6n the reaction G"H for the formation of C/
)
from C/ gas,
),) Calculate U7
o
T
G"H,
)," ;etermine the e4uili1rium constant K
*
for reaction G"H at the given tem*erature,
1( .n an e(*eriment, Ni/ *o6der and C/ gas 6ere *laced in a closed container
6hich 6as then heated u* to %!00
o
C, -hen the system reached e4uili1rium, there
6ere four s*ecies *resent: Ni/GsH, NiGsH, C/GgH and C/
)
GgH, The mole *ercentages
of C/ and C/
)
are % T and EE T, res*ectively, and the *ressure of the system is
%,0 1ar G%0
#
0aH,
",% -rite do6n the reactions in the a1ove e(*eriment,
",) @ased on the e(*erimental results and the a1ove thermodynamic data, calculate
the *ressure of /
)
in the e4uili1rium 6ith Ni/ and Ni at %!00
o
C,
)0

46
th
Problem (. Comple! compounds
Ethylenediamine tetraacetic acid GE;T5H is used as a reagent to titrate the
metal ions in the com*le(ometric titration,
E;T5 is a tetra*rotic acid, a11reviated as H
!
W, 6ith the structure:
5s E;T5 is s*aringly solu1le in 6ater, a more solu1le sodium form, Na
)
H
)
W, is
usually used and H
)
W
)X
is commonly :no6n as E;T5, E;T5 forms strong %:%
com*le(es 6ith most metal ions M
nL
,
1( Ho6 many atoms of an E;T5 molecule are ca*a1le of 1inding 6ith the metal
ion u*on com*le(ationR
%,% Chec: in the a**ro*riate 1o(,

) ! $
%,) ;ra6 the structure of the com*le( of a metal ion M
)L
6ith E;T5,
2, Com*le(ation reaction 1et6een W
!X
form of E;T5 and metal ion M
nL
has a large
formation constant Gsta1ility constantH Y:
M
nL
L W
!X
MW
G!XnHX
Z Z[ [
Z [
!
H ! G
+

=
: ;
;:
n
n
@esides com*le(ation reaction 1et6een W

!X
form of E;T5 and metal ion M
nL
,
other *rocesses in the solution also develo* such as formation of hydro(o
com*le(es of the metal ion, acid31ase e4uili1rium of H
)
W
)X
Q To account for such
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, )%

46
th
*rocesses conditional formation constant YM is used for the calculations,
YM is determined from Y as the follo6ing e(*ression:
nL !3
M W
Y = Y,\ ,\
6here:
!3
W
\
and
nL
M
\
are fractions of W
!?
G
!3
W
\

=
4
[ Y ]
[ Y] '
H and free metal ion M
nL
G
nL
M
\ =
[M]
[M] '
H, 6ith [WZ
M
and [MZ
M
1eing the total concentrations of all forms of W
!X
and M
nL
, e(cluding MW
G!XnHX
, 7iven that: H
!
W has *K
a%
= ),00& *K
a)
= ),$9& *K
a"
=
$,%$& and *K
a!
= %0,)$ (K
a
va1ues 4or 2
<
:
=
and

2
>
:
2=
are i$nored),

)
sGMgG/HH H
*C
=%0,E#&
$E , log
)
=
;$:

Mg
)L
L H
)
/ Mg/H
L
L H
L

]
? = %,#>%0
3%"
& G*C
a
= 3logC
a
& *C
s
= 3logC
s
H
.n a ty*ical e(*eriment, %,00 mD of 0,%0 M MgCl
)
solution and %,00 mD of 0,%0 M
Na
)
H
)
W solution are mi(ed together, *H of the resulting solution is adPusted to
%0,)$ 1y an NH
"
ONH
!
L
1uffered solution,
),% Calculate conditional formation constant GMH of the MgW
)X
com*le( at *H =
%0,)$ given that acid31ase e4uili1rium of H
)
W
)X
and formation of mononuclear
hydro(o com*le( of Mg
)L
occur in the solution,
),) ;oes the MgG/HH
)
*reci*itate in this e(*erimentR Chec: in the a**ro*riate 1o(,

0reci*itation No *reci*itation

1( .n order to titrate metal ions 1y E;T5, the conditional formation constant GMH
of the com*le( metal ? E;T5 GMW
G!XnHX
H must 1e large enough, usually M %,00 >
%0

3 %,00 > %0
E
, To determine the concentrations of Mn
)L
and Hg
)L
in an analytical
sam*le, t6o e(*eriments are carried out,
))

46
th
39eriment 1! 5dd )#,00 mD of 0,0!0 M E;T5 solution to )0,00 mD of the
analytical solution, 5dPust the *H of the resulting solution to %0,#0, Titrate the
e(cess E;T5 6ith a suita1le indicator and %),00 mD of 0,0)# M Mg
)L
solution is
consumed,
39eriment 2! ;issolve %,!00 gram of CCN into )0,00 mD of the analytical
solution Gassuming that the volume is unchanged u*on dissolutionH and then add
)#,00 mD of 0,0!0 M E;T5 solution, Titrate the e(cess E;T5 in the resulting
mi(ture at the *H of %0,#0& )0,00 mD of 0,0)# M Mg
)L
solution is consumed,
",% 0rove that: in the e(*eriment ), Hg
)L
cannot 1e determined 1y titration 6ith
E;T5 in the *resence of CCN in solution Gor Hg
)L
is mas:ed in the com*le(
form of HgGCNH
!
)3
H,
",) -rite do6n chemical e4uations for the reactions in the t6o e(*eriments and
calculate molar concentrations of Mn
)L
and Hg
)L
in the analytical solution,
7iven that:
"# , E & E9 , " log & 0 , )% log
H G
H G
)
!
)
= = =

26, a
6, 2$ 2$:
K
G/ther *rocesses of Hg
)L
are ignored& the *C
a
values of H
!
W are *rovided in
4uestion )

H,
4( .n the titration of *oly*rotic acids or 1ases, if the ratios of consecutive
dissociation constants e(ceed %,00>%0
!
, multi*le titrations are *ossi1le 6ith an
error less than %T, To ensure the allo6ed error, only acids or 1ases 6ith
e4uili1rium constants larger than %,00>%0
3E
can 1e titrated, To find the end3*oint,
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, )"

46
th
*H range of the indicator must 1e close to that of the e4uivalence *oint
G*H
E0
H& the *oint at 6hich the stoichiometric amounts of analyte and titrant has
reacted, Titrate %0,00 mD of 0,)# M Na
)
H
)
W solution 1y 0,)0 M Na/H solution in
a ty*ical e(*eriment,
!,% -rite do6n the chemical e4uation for the titration reaction,
!,) ;etermine the value of *H
E0
,
!," Choose the most suita1le indicator Gchec: in the a**ro*riate 1o(H for the a1ove
titration from the follo6ing: 1romothymol 1lue G*H = 9,$0H& *henol red G*H =
,)0H& *henol*htalein G*H = E,00H,

@romothymol 1lue 0henol red 0henol*htalein
!,! Titration error ' defined as the difference 1et6een the titrant amount added and
the titrant amount needed to reach the e4uivalence *oint is e(*ressed as:
T %00 T %00
)
) %
)
) %
=
)
) )
) 6
) 6 ) 6
'
,a%2
,a%2 ,a%2
)!

46
th
6here C
Na/H
is the Na/H concentration& V
%
: End3*oint volume of Na/H& V
)
:
e4uivalence *oint volume of Na/H,
Calculate the consumed volume of Na/H solution and the titration error if the final
*H is 9,$0,
Problem ). *ead compounds
1( Consider the follo6ing nuclide:
)0E
@iG.H,
)0
01G..H,
)09
01G...H,
)0$
01G.VH, -hich
nuclide is the last mem1er of the decay series for
)"
UR Chec: in the a**ro*riate
1o(,

G.H G..H G...H G.VH
2( There are three natural decay series, They 1egin 6ith Th3)")G.H, U3)"G..H, U3
)"#G...H and end 6ith 013)0, 013)0$, 013)09, .n 6hich decay chain are there $ @
decays and ! ?

decaysR Choose the correct ans6er 1y chec:ing in the a**ro*riate
1o(,

G.H G..H G...H None
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, )#

46
th
1( 01GN/
"
H
)
solution is slo6ly added into )0,00 mD of a mi(ture
consisting of 0,0)0 M Na
)
S/
!
& #,0>%0
X"
M Na
)
C
)
/
!
& E,9>%0
X"
M C.& 0,0# M CCl
and 0,00%0 M C./
"
, -hen the 1right yello6 *reci*itate of 01.
)
1egins to form,
)%,$0 mD of 01GN/
"
H
)
solution is consumed,
",% ;etermine the order of *reci*itationR
",) Calculate the concentration of 01GN/
"
H
)
solutionR
7iven that:
!
sG01S/ H
*C
= 9,$$&
" )
sG01G./ H H
*C
= %),$%&
)
sG01. H
*C
= 9,$&
) !
sG01C / H
*C
= %0,0#&
99 , !
H G
)
=
/b61 s
K
, (%ther rocesses o4 the ions are i$nored)+
4( /ne of the common reagents to detect 01
)L
s*ecies is C
)
Cr/
!
, giving yello6
*reci*itate 01Cr/
!
, 6hich is solu1le in e(cess of Na/H, The solu1ility of 01Cr/
!
de*ends not only on *H 1ut also on the *resence of coordinating s*ecies,,, 7iven
that the solu1ility of 01Cr/
!
in % M acetic acid solution is s = ),E>%0
X#
M,
calculate the solu1ility *roduct C
s*
of 01Cr/
!
,
& 9$ , !
H G
"
=
6%%2 62 a
K

& $ , ) lg
H G
"
=
+
6%% 62 /b

& 0 , ! lg
) "
H G
=
6%% 62 /b

# , $
H G
!
=
26r% a
K

01
)L
L H
)
/ 01/H
L
L H
L

]
? = %0
39,

Cr
)
/
9
)3
L H
)
/ )Cr/
!
)3
L )H
L
K = %0
3%!,$!
2( Dead3acid 1attery, commonly :no6n as lead 1attery consists of t6o lead *lates a
*ositive electrode covered 6ith a *aste of lead dio(ide and a negative electrode
made of s*onge lead, The electrodes are su1mersed in an electrolyte consisting of
6ater and sulfuric acid H
)
S/
!
, -rite the chemical e4uations for *rocesses on each
electrode, overall reaction as the 1attery discharges and the cell diagram,
7iven that:
& %)$ , 0
0
O
)
) 3
/b /b
=
+
)
)
0
O
%,!## &
/b% /b
3 )
+
=

& 00 , )
H G
!
=
2S% a
K

& $$ , 9
H G
!
=
/bS% s
K
at )#
o
C:
)
F
RT
0#E) , 0 "0" , ) =
6( Calculate:
)$

46
th
$,%
!
0
01S/ O01
E &
) !
0
01/ O01S/
E
$,) The *otential V of the lead 1attery if
) !
H S/
6
%, M,
Problem 1+. Applied electroc&emistry
1( 8eduction3o(idation reactions have *layed an im*ortant role in chemistry due to
their *otential to 1e valua1le sources of energy for technology and life, -rite do6n
chemical e4uations for the follo6ing reactions:
%,% /(idation of glucose GC
$
H
%)
/
$
H 6ith CMn/
!
solution in the *resence of
sulfuric acid to form gaseous C/
)
,
%,) /(idation of 'eS/
!
6ith CMn/
!
in an acidic medium Gsulfuric acidH to form
'e
)
GS/
!
H
",
%," @ased on the reaction in section %,), determine the anodic reaction and
cathodic reaction and the relevant cell diagram,
%,! ;erive the e(*ression for electromotive force E of the cell,
2( .n the thermodynamics *oint of vie6, 7i11s free energy 7 at constant 0, T
condition is closely related to electromotive force E of a redo( reaction according
to 1elo6 e(*ression:
G nFE =
G
E
nF
=
6here: n ? num1er of electrons transferred,
' ? 'araday constant,
The correlation of the standard reduction *otential 1et6een Mn ions in acidic
medium is:
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, )9

46
th

+ + + +

) #% , % " R
)
R )
!
#$ , 0
!
0
!
0
"
;n ;n ;n% ;n% ;n%
) 3 3 )
L%,9V L%,)"V
),% ;etermine the standard reduction *otential of the *air
)
)
!
;n%
;n%

),) ;etermine the standard reduction *otential of the *air
+ "
)
;n
;n%
1( 5 *rocess is s*ontaneous if 7i11s free energy is negative, @ased on the
thermodynamic data:
",% ;etermine 7i11s free energy of the follo6ing reaction:
"Mn/
!
)3
L !H
L
)Mn/
!
3
L Mn/
)
L )H
)
/
",) .s the reaction s*ontaneousR
"," Calculate K
c
for the reaction,
Problem 11. P&osp&oric acid
/ is a solution of H
"
0/
!
6ith *H of %,!$,
1( Calculate the molar concentrations of all s*ecies in solution /, 7iven that K
a
values for H
"
0/
!
are 9,#>%0
X"
& $,)>%0
X
and !,>%0
X%"
, res*ectively,
2( Mi(ing of #0 ml of solution / and #0 ml of 0,! M NH
"
solution results in %00
ml of solution B, Calculate *H of solution B G
)! , E
!
=
+
,2
K
H,
1( %00 mD of solution B is mi(ed 6ith %00 ml of 0,) M MgGN/
"
H
)
solution,
;etermine if *reci*itate of NH
!
Mg0/
!
forms, The hydrolysis of Mg
)L
is ignored
and *reci*itation of NH
!
Mg0/
!
is assumed to 1e the only reaction, given that K
s*
=
),#>%0
X%"
,
4, Calculate the solu1ility GmolBD
X%
H of Ca
"
G0/
!
H
)
, given K
s*
= ),))>%0
X)#
,
(2int! The hydro1ysis o4 6a
2=
is i$nored)+
)

46
th
Problem 12. C&emical ,inetics
Thermal decom*osition of dinitrogen *ento(ide GN
)
/
#
H in the gas *hase has time3
inde*endent stoichiometry,
) N
)
/
#
GgH V ! N/
)
GgH L /
)
GgH G%H
5 :inetic measurement for N
)
/
#
at $","
o
C is sho6n in 'igure % 1elo6,
0,00EL00
#,00E30!
%,00E30"
%,#0E30"
),00E30"
),#0E30"
",00E30"
",#0E30"
!,00E30"
0 %00 )00 "00 !00 #00 $00 900 00 E00
+ime4 s
5
6
2
O
2
7
4
m
o
l
(
d
m
-
1
56
2
O
2
7
Fi$ure 1, Concentration of N
)
/
#
versus time,
1( -hat is the half3life Gt
%O)
H for the decom*osition of N
)
/
#
at $","
o
CR
2( The reaction order for the reaction G%H can 1e determined 1y *lotting of ln
[N
)
/
#
Z
0
O[N
)
/
#
Z
t
versus time or ^[N
)
/
#
Z
0
O[N
)
/
#
Z
t
3%_ versus time,
),% 0lot the gra*hs into the t6o figures 1elo6 to determine the reaction orderR
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!,
Time
GsH
[N
)
/
#
ZO
molBdm
X"
0 ",0>%0
X"
#0 ",)!>%0
X"
%00 ),$">%0
X"
%#0 ),%">%0
X"
))# %,##>%0
X"
"#0 E,)0>%0
X!
#%0 !,90>%0
X!
$#0 ),$%>%0
X!
00 %,"E>%0
X!
)E

46
th
),) -rite do6n the rate la6 and integrated rate e4uation,
0
0,#
%
%,#
)
),#
"
",#
!
0 %00 )00 "00 !00 #00 $00 900 00 E00
TimeO s
l
n
^
5
6
2
O
2
7
0
4
5
6
2
O
2
7
t
_
Fi$ure 2( 5 re3*lot of the data in 'igure % as function of ln ^[N
)
/
#
Z
0
O[N
)
/
#
Z
t
_ versus time
0
#
%0
%#
)0
)#
"0
0 %00 )00 "00 !00 #00 $00 900 00 E00
+ime4 s
8
5
6
2
O
2
7
0
4
5
6
2
O
2
7
t
9
-
1
Fi$ure A+ 5 re3*lot of the data in 'igure % as function of ^[N
)
/
#
Z
0
O[N
)
/
#
Z
t
3%_ versus time
1( ;etermine the rate constant for the reaction G%H,
4( The rate constant : for G%H at !#
o
C is of #,0)>%0
3!
s
X%
, Calculate the activation
energy GE
a
H and *re3e(*onential factor G5H for the reaction G%H assuming that the
activation energy and *re3e(*onential factor are tem*erature inde*endent,
2( The follo6ing mechanism is *ro*osed for the reaction G%H:
"0

46
th
N
)
/
#
N/
)
L N/
"
G)H
N/
)
L N/
"
N/
)
L /
)
L N/ G"H
N/ L N/
"
) N/
)
G!H
Using this mechanism, derive the rate la6 for 3d[N
)
/
#
ZOdt assuming that the
intermediate concentrations can 1e treated 1y the steady3state a**ro(imation,
Problem 13. ,inetics of t&e decomposition of &ydrogen pero!ide
.n order to decom*ose hydrogen *ero(ide GH
)
/
)
H 6ith iodide ion as catalyst in
neutral solution, the " T H
)
/
)
solution G6hich a**ro(imately corres*onds to "0 g
of H
)
/
)
in % D of solutionH is mi(ed 6ith 0,% M C. solution and 6ater at different
volumetric ratios& and the volume of the o(ygen gas released
H G
)
m5 )
% is
measured,
E(*eriment
H G
) )
m5 )
% 2
H Gm5 )
K#
H G
)
m5 )
% 2
minH O G
)
m5 )
%
at )E C and % atm
% )# #0 9# !,!
) #0 #0 #0 ,#
" %00 #0 0 %9,#
! #0 )# 9# !,)#
# #0 %00 0 %$,#
1( ;etermine the reaction order 6ith res*ect to H
)
/
)
,

and .
3
, res*ectively,
2( -rite do6n the chemical reaction, and determine the rate la6,
1( Calculate the molarity of H
)
/
)
at the 1eginning of the e(*eriment `! and after ! min,
4( The reaction mechanism involves a series of the follo6ing ste*s:
H
)
/
)
L .
X

%
-
H
)
/ L ./
X
G%H
./
X
L H
)
/
)

)
-
/
)
L .
X
G)H
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, "%

46
th
;o the t6o a1ove ste*s have the same rate or different ratesR -hich ste*
determines the overall rate of the o(ygen releaseR 2ustify your ans6er,
Problem 14. -agnetism of transition metal comple!es
5 transition metal com*le( containing diamagnetic ligands can 1e overall
diama$netic Gall electrons are *airedH or arama$netic Ghaving un*aired
electronGsHH de*ending on the electronic configuration of the central metal ion, the
nature of the ligand, and geometry of the ligand s*here, The magnitude of
*aramagnetism of a metal com*le( is commonly re*orted in terms of the effective
magnetic moment GJ
eff
H 6hich can 1e o1tained from the e(*erimental measurement
of molar magnetic susce*ti1ility GK
m
H and is commonly e(*ressed in @ohr
magneton G@MH,
Theoretically, the magnetic moment is contri1uted 1y t6o com*onents, the s*in
angular momentum and the or1ital angular momentum, 'or many com*le(es of
first ro6 d31loc: metal ions, ho6ever, the contri1ution of the second com*onent
can 1e ignored, Thus, the so3called s*in only magnetic moment can 1e determined
1y the num1er of un*aired electrons, n:
1( The o1served effective magnetic moment of t6o octahedral com*le(es,
C
!
[MnGCNH
$
Z,"H
)
/ and C
!
[MnGSCNH
$
Z are ),% @M and $,0$ @M, res*ectively,
%,% Calculate num1er of un*aired electrons in each com*le(, -hich com*le( is
lo6 s*inR -hich com*le( is high s*inR
%,) 8ationaliAe your ans6ers 1y a**lying crystal field theory,
")

46
th
2( Calculate the J Gs*in onlyH of com*le( [NiGH
)
/H
$
ZCl
)
,
1( .n *ractice, the e(*erimentally o1served J
eff
value of [NiGH
)
/H
$
ZCl
)
is ",)# @M,
This is not sur*rising due to the fact that magnetic moment of octahedral
com*le(es of Ni
)L
Gd
H usually does not o1ey the s*in only formula, .n these cases,
the contri1ution of or1ital angular momentum should 1e ta:en into account, The
sim*lification of s*in3or1it cou*ling model can 1e a**lied to calculate their
magnetic moment:
6here a is s*in3or1it cou*ling constant of Ni
)L
and has the value of "%# cm
X%
N
oct
is the crystal3field s*litting *arameter
Calculate the effective magnetic moment of [NiGH
)
/H
$
ZCl
)
ta:ing into account
s*in?or1it cou*ling, N
oct
of [NiGH
)
/H
$
Z
)L
is #00 cm
3%
,
4( ;i1enAoylmethane G;@MH is a 6ell :no6n chelating b3/,/3ligand 6hich can
form sta1le com*le(es 6ith many transition metal ions,
3B0
8eaction of NiGCH
"
C//H
)
,!H
)
/ 6ith ;@M in Et/H 3 H
)
/ solution gives light
green crystalline com*le( / 6hich loses $, T of mass on heating at )%0
o
C in the
air to form green solid B, The su1stance B is 4uantitatively converted to 1ro6n
*rismatic crystals C 1y re3crystalliAation in dry toluene, B and C are t6o
*olymor*hic forms and their inter3conversion is reversi1le, The c3ray single
crystal structure of C sho6s a s4uare *lanar geometry 6ith the chemical
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, ""

46
th
com*osition of [NiG;@MH
)
Z, -hile B is *aramagnetic 6ith effective
magnetic moment of ",)9 @M, the com*le( C is diamagnetic, -hen B and C are
:e*t in the air, they slo6ly convert to /( This ha**ens much faster in the *resence
of some organic solvents G#nor$+ 6hem+, 2001, 40, 1>2>01>A>H,
!,% ;ra6 the s*litting diagram of the d or1itals of Ni
)L
in C and confirm its
diamagnetic *ro*erty,
!,) -hat is the molecular formula of /R 5ssume that / is a mononuclear
com*le(,
!," The effective magnetic moment of / is ",%% @M GSynth+ React+ #nor$+ ;et+ %r$+
6hem+, 200B, AB, >B40C0A), -hat is the most suita1le molecular geometry of /R
G5ssuming that .f 5 is an octahedral com*le(es, N
oct
of / is similar to that of
[NiGH
)
/H
$
Z
)L
H,
!,! ;ra6 all *ossi1le isomers of /(
!,# -hat do you e(*ect for the molecular geometry of BR
Problem 1". .tructure and synt&esis of Al-,eggin ion
1( 5 molecular dimer of aluminum chloride in gas *hase has the structure:
"!

46
th
%,% -hat is the hy1ridiAation of the 5l atoms in a dimerR
%,) ;etermine the distance 1et6een t6o 5l atoms,
2( 5luminum chloride dissociates in 1asic solution yielding several 5l3*olycations,
5 ty*ical 5l3Ceggin ion 6ith the molecular formula of [5l
%"
/
)
H
)!,
%)H
)
/ZCl
n
6as
formed at a hydrolysis ratio [/H
3
ZO[5l
"L
Z of %,# to ),#, .t is only com*osed of
tetrahedral and octahedral 5l cations, The
)9
5l NM8 s*ectrum of an 5l
%"
ion is
sho6n 1elo6, The shar* signal at $! **m is due to the very symmetrical
environment of the corres*onding 5l atomGsH in the Ceggin cation,
),% ;etermine the a1solute value of GnH in the 5l
%"
Ceggin ion,
),) 5ssign
)9
5l NM8 signals in the s*ectrum to the a**ro*riate 5l cationGsH in the
right figure,
)," .n an 5l
%"
3Ceggin ion, 5l tetrahedronGsH isGareH only lin:ed 6ith other 5l atoms
1y the o(ygen 1ridge, 0ro*ose the structural formula for the 5l
%"
3Ceggin ion,
),! ;etermine the num1er of o(ygen atoms 1ridging adPacent octahedra,
),# -rite do6n the overall e4uation to *re*are 5l3Ceggin ions from the reaction
1et6een Na/H and 5lCl
"
solution,
1( 5l
%"
3Ceggin ions have recently 1een *re*ared 1y solid 3 solid interaction
referred to as mechanochemical synthesis [D+ 6ata1+ 24< (200C) A4>& #nor$+ 6hem+
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, "#

46
th
6ommun+ 11 (2008) 112<Z, 5 mi(ture of GNH
!
H
)
C/
"
O[5lGH
)
/H
$
ZCl
"
6as
1lended together in a silicon car1ide cruci1le G6ith the inner volume of %9 cm
"
H in
the *resence of three hardened silicon car1ide 1alls G6ith the radius of 0,#!) cmH in
atmos*heric condition G)#
o
C, % atmH, The milling 6as :e*t for a *eriod of time at
)#
o
C until the *ressure gauge remains at constant value of ),#0 atm (2int! The
vo1ume o4 so1ids is ne$1i$ib1e)+
",% -rite do6n the overall reaction 1et6een aluminum he(ahydrate chloride and
ammonium car1onate to yield the 5l
%"
3Ceggin ions,
",) ;etermine the num1er of molecular 5l
%"
3Ceggin cations in the cruci1le,
Problem 1$. .afrole
Safrole G!3allyl3%,)3methylendio(y1enAeneH is o1tained from oil e(tracted from
sassafras, an evergreen tree gro6ing in the central and northern regions of
Vietnam, Safrole has interesting functionality and chemical reactivity suggesting
its use as an efficient and versatile natural synthon in the synthesis of numerous
1iologically active com*ounds, [0tClGSafrole3%HHG0yridineHZ is a com*le( 6ith a
similar activity to the anticancer drug Cis*latin, [0tClGSafrole3%HHG0yridineHZ has
1een synthesiAed for the first time 1y chemists at the ;e*artment of Chemistry,
Hanoi National University of Education, The reaction scheme is given 1elo6,
Some s*ectral signals of uncoordinated safrole and coordinated safrole in /, B and
C are given 1elo6,
"$

46
th
I#
a1sor*tion,
d
CE3C%0
, cm
3%
%
H NM8 signals of aromatic *rotons, e G**mH
Uncoordinated %$"0
Coordinated in
/
%#%0
Coordinated in
B
%!E#
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, "9

46
th
Coordinated in
C
%#00
1( -rite 1alanced e4uations for the three reactions in the a1ove scheme,
2, -hat information a1out the coordination of safrole 6ith 0t in /, B and C can 1e
o1tained from the .8 and
%
H NM8 dataR
1, ;ra6 the structures of /, B and C, given that in C *yridine is in the cis0*osition
6ith res*ect to the allyl grou* of safrole,
4( -hat is the driving force of each of the reactions G%H, G)H and G"HR
2, -hy does reaction " not seem to o1ey the trans e44ectR
Problem 1'. /mida0ole
Heterocyclic chemistry is one of the most im*ortant fields of organic chemistry
and 1iochemistry, 5**ro(imately ##T of *u1lications in organic chemistry are
related to the field, and the num1er of heterocyclic com*ounds recently found is
far more than that of homocyclic com*ounds, The five3mem1ered ring com*ounds
6ith t6o heteroatoms are often *resent in many su1stances that are im*ortant for
life, 'or e(am*le, imidaAole ring is *resent in the essential amino acid, histidine,
and its decar1o(ylation *roduct, histamine, Histidine residues are found at the
active sites of ri1onuclease and of several other enAymes and *lay a vital *art in the
structure and 1inding functions of hemoglo1in, Several drugs are 1ased on the
imidaAole ring such as nitroimidaAole, cimetidine, aAomicin, metronidaAole,
medaAolam,
"

46
th
1( ;ra6 the structures of %,"3diaAole GimidaAole, C
"
H
!
N
)
H, imidaAol3%3ide anion,
imidaAolium cation, %,"3o(aAole Go(aAole, C
"
H
"
N/H and %,"3thiaAole GthiaAole,
C
"
H
"
NSH, -hich structureGsH can 1e considered aromaticR
2( 5rrange imidaAole, %,"3o(aAole and %,"3thiaAole in decreasing order of melting
and 1oiling *oints and Pustify your order,
1( Using structural formulae, 6rite do6n e4uations for the ioniAation of imidaAole,
o(aAole, and thiaAole in 6ater, 5rrange the su1stances in decreasing order of 1ase
strength and Pustify your ans6er,
4( 0ro*ose a reaction mechanism sho6ing the catalytic 1ehavior of imidaAole in
hydrolyAing 8C//8M 6ithout a *artici*ation of /H
?
, 2ustify this 1ehavior 1ased
on the structure of imidaAole,
2( 0ro*ose a reaction mechanism for the formation of %,%M3car1onyldiimidaAole
GC
9
H
$
N
!
/, C;.H from imidaAole and *hosgen GC/Cl
)
H,
6( E(*lain 6hy the C=/ stretching fre4uency in %,%M3car1onyldiimidaAole is %00
cm
?%
higher than that of %,%M3car1onyldi*yrrolidine GC/GC
!
H
NH
)
H,
:( -rite do6n reaction e4uations for the *re*aration of C;. GaH using a mi(ture of
! mol imidaAole and % mol *hosgene and G1H using a mi(ture of ) mol imidaAole, %
mol *hosgene, and ) mol Na/H, E(*lain 6hy reaction GaH is *refera1le,
!( C;. is often used for the activation of car1onyl grou* for the cou*ling of amino
acids in *e*tide synthesis,
,% Use curly arro6 mechanisms to com*lete the scheme 1elo6, sho6ing the
formation of the active com*ound ; from C;. and 5lanine,
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, "E

46
th
,) 0ro*ose a reaction mechanism for the formation of di*e*tide 5la37ly from ;
and 7lycine,
Problem 1(. .mall &eterocycles
Heterocyclic com*ounds containing the C'
"
grou* are interesting targets of
advanced researches to generate 1iologically active com*ounds, .t is 4uite difficult
to 1ring the trifluoromethyl grou* into saturated heterocyclic structures, es*ecially
heterocycles containing nitrogen, Ho6ever, these heterocyles 1earing C'
"
grou*s
have several *romising a**lications, Therefore, studies of such com*ounds have
1een carried out 1y many chemists,
Trifluoroacetaldehyde G/H 6as treated 6ith ethanol and then reflu(ed 6ith
1enAylamine in toluene to afford com*ound B GC
E
H
N'
"
H, The reaction of
com*ound B 6ith ethyl diaAoacetate in diethyl ether 6ith 1orontrifluoride etherate
G@'
"
,Et
)
/H as a catalyst at 39
o
C for ! hours *rovided com*ound C GC
%"
H
%!
N/
)
'
"
H,
The reduction of com*ound C 1y Di5lH
!
in TH' at room tem*erature for ) hours
formed com*ound 3, Then, 3 reacts 6ith hydrogen in the *resence of 0dG/HH
)
as
!0

46
th
a catalyst in CH
)
Cl
)
at room tem*erature for $0 hours to o1tain E GC
!
H
$
N/'
"
H,
Com*ound E 6as then allo6ed to react 6ith ) e4uivalents of tosyl chloride GTsClH
in dicloethane 6ith the catalytic Et
"
N and amount of !3dimetylamino*yridine
G;M50H, The reaction 6as carried out at room tem*erature for ) hours, then "
hours of reflu(, to furnish com*ound F, F reacted 6ith %,) e4uivalents of *henol in
the *resence of C
)
C/
"
in ;M' to form com*ound ; GC
%9
H
%$
NS/
"
'
"
H,
5 derivative of ; can 1e synthesiAed according to the follo6ing diagram:
1( Com*lete synthetic schemes from B to <,
2( -rite reaction mechanisms from B to C,
1( -rite reaction mechanisms from F to ;,
Note:
@nNH
)
: 1enAylamine, C
$
H
#
NH
)&
@n: @enAyl, C
$
H
#
CH
)
3, TH': tetrahydrofuran
DiHM;S: Dithium 1isGtrimethylsilylHamide, Et: C
)
H
#
3&
E4ui: e4uimolarity
Problem 1). 1itamin 2
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, !%

46
th
Vitamin H or 1iotin is a highly effective gro6th *romoter 6hich *lays an
im*ortant role in many organisms, for instance 1a:erMs yeast GSaccharomyces
corevisiaeH, Human 1eings have different demand in 1iotin de*ending on age, Dac:
of 1iotin can lead to diseases such as dermatitis, a1sence of a**etite, fatigue,
muscular *ain and nerve *ertur1ance,
@iotin 6as first found in %E0% 1y -ildiers as a gro6th3*romoting vitamin of
yeasts, Thereafter, it 6as found in egg yol: G1y Cfgl, %E"$H and in liver G1y SAent3
7yfrgyi, %E"$H, The a1solute configurations of chiral car1ons of 1iotin 6ere
esta1lished 1y Trotter and Hamilton in %E$$ 1y the single3crystal c38ay
diffraction, The molecule of 1iotin has three chiral car1ons, Hence, there are
theoretically eight diastereomers, /nly the GAaS, 4S, >aRH3(7)3GLH31iotin, ho6ever,
sho6s the high 1ioactivity,
.n %E), researchers from Hoffmann3Da 8oche *u1lished an elegant synthesis
*rocedure for G7H3GLH3@iotin from the methyl ester of the amino acid D3Cysteine
6ith the follo6ing ste*s,
1( The thiol grou* of the methyl ester of D3cysteine 6as transformed into a
disulfide S3S 1ond Gcom*ound /H in an o(idation reaction, / 6as then treated 6ith
he(3#3inoyl chloride to give com*ound B 6hich 6as su1se4uently reduced 1y
FnOCH
"
C//H to afford a thiol, This com*ound 6as cycliAed 1y the addition of the
!)

46
th
?SH grou* to the terminal al:yne under atmos*heric condition, resulting in the
formation of C 6ith a ten3mem1ered ring containing a GEH C=C dou1le 1ond, -rite
do6n the structural formulae of /, B and C in the hereunder scheme,
2( The reduction of C 1y diiso1utylaluminium hydride GGi3@uH
)
5lH, ;.@5DH
resulted in the formation of G3H, The condensation reaction 1et6een 3 and
1enAylhydro(ylamine in dichloromethane *roduced nitrone E Ga nitrone is an
organic com*ound 6hich contains a g C=N
L
3/
3
grou*H, E under6ent a %,"3di*olar
intramolecular cycliAation reaction to afford *olycyclic com*ound F of 6hich the
t6o heterocycles, iso(aAolidine G%,)3o(aAolidineH and tetrahydrothio*hene, shared
a common 1ond, The cycliAation reaction resulted in the GSH configurations of the
t6o car1ons at the common 1ond and the GRH configuration of the car1on
connected to the o(ygen, -rite do6n the structural formulae of 3, E and F(

1( -hen F 6as reduced 6ith Fn *o6der in acetic acid, the N3/ 1ond of the
heterocycle iso(aAolidine 6as 1ro:en to give com*ound ;, The reaction 1et6een
; and chloroformate in the *resence of Na
)
C/
"
in TH' resulted in the formation
of com*ound %, The treatment of % in a hot solution of @aG/HH
)
in dio(ane,
follo6ed 1y an acidic 6or:3u* yielded the 1icyclic e3hydro(y acid I containing all
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, !"
5ir, )#
o
C

46
th
the chiral centers of G7H3GLH3@iotin 1ut 6ith an he(cessivei 3/H grou*,
;ra6 the structures of ;, % and I and e(*lain the formation of I from %,
4( I 6as treated 6ith S/Cl
)
to yield the corres*onding chloride acid =, given that
the configuration of the car1on attached to the he(cessivei 3/H is maintained in =,
Ester < 6as formed 6hen = 6as reacted 6ith methanol, < 6as reduced 6ith
Na@H
!
in dimethylformamide at 0
o
C to give ester 0 6hich 6as hydrolyAed in
a4ueous acidic solution of H@r to give o*tically *ure G7H3GLH3@iotin, ;ra6 the
structures of I, =, < and 0 and the intermediates to e(*lain the influence of the
sulfur atom on the stereochemical outcome of =,
Problem 2+. 3o perfume wit&out 4asmine
The S*anish Pasmine originated from the valleys of Himalaya, This so called
Dasminum $randi41orum D,, 6hich 6as grafted on the 6ild Daminum o44icina1e D,
has the *ossi1ility to resist against the cold of the mountain climate, .n %E$), E,
;emole and E, Dederer successfully isolated and clearly determined the structures
of the im*ortant flavor com*onent of the essential oil of Pasmine, .t 6as actually a
mi(ture of t6o diastereomers GEH3GAR,CRH methyl Pasmonate and GEH3GAR,CSH
methyl Pasmonate 6ith the structures sho6n 1elo6,
!!

46
th
;ue to its im*ortant role in *erfume industry as 6ell as its limited natural resource,
the synthesis of Pasmonates has attracted interest of many chemists, The first
synthesis of o*tically *ure GEH3GAR,CSH3methyl Pasmonate 6as carried out in %EE0
1y Helmchen 6ith the follo6ing ste*s:
1( The first ste* in the synthesis is a ;iels35lder reaction 1et6een cyclo*entadiene
/ and ester B of fumaric acid 6ith GSH3ethyl lactate to yield C,
5 cyclo3addition reaction, a :ind of *ericyclic reaction, involves 1onding
1et6een the termini of t6o j systems to *roduce a ne6 ring Gscheme 1elo6H, The
*roduct has t6o more k 1onds and t6o less j 1onds than the reactants, The ;iels3
5lder reaction, or so called [!L)Z, is a common thermally activated cycloaddition
6hose stereoselectivity is syn addition, .n this concerted syn addition, the
stereochemical relationshi*s among the su1stituents are retained in the *roductGsH,
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, !#
methyl Pasmonate methyl Pasmonate

46
th
The hydrolysis of C in 1asic solution follo6ed 1y an acidification ste*
resulted in the formation of 3, ;ra6 the structures of C and 3,
2( The reaction 1et6een 3 and .
)
in C. solution gave rise to the formation of the e3
iodolacton of the endo ?C//H grou*, -hen heated under 1asic condition, E
under6ent a decar1o(ylation3cycliAation reaction to *roduce com*ound F, The
hydrolysis in 1asic medium follo6ed 1y o(idation 6ith Na./
!
O8u/
!
transformed F
into l3:eto acid ;, -rite do6n the structures of E to ;,
1( ; 6as reacted 6ith H. to yield com*ound % containing only five3mem1ered
rings, -hen % 6as reduced 1y FnOCH
)
0/
!
in tetrahydrofuran, it transformed into
car1o(ylic acid I 6hich 6as then o(idiAed in a @ayer3Villiger rearrangement 6ith
meta3chloro*ero(y1enAoic acid Gm3C0@5H to give the maPor *roduct =, = 6as
treated 6ith o(aloyl chloride, follo6ed 1y a 0dO@aS/
!
catalyAed reduction 6ith H
)
G8osenmund reductionH to give <, Com*ound 0 6as se*arated from the -ittig
reaction mi(ture 1et6een < and the yield 0h
"
0 =CH/CH
"
, ;ra6 the structures of
the com*ounds from ; to <,

!$

46
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4( Hydrolysis of 0 in TH'OH
)
/ solution of acetic acid *roduced 6 6hich
under6ent a -ittig reaction 6ith the ylide 0h
"
0 = CHCH
)
CH
"
to form O, The
hydrolysis of O in 1asic solution, follo6ed 1y a neutraliAation ste* and then
treatment 6ith diaAomethane resulted in the formation of P, .n the last ste*, the
target molecule, GEH3GAR,CSH3methyl Pasmonate >, 6as o1tained in the o(idation
reaction of P 6ith *yridinium dichromate, ;ra6 the structures of com*ounds from
6 to P,
Problem 21. 1ietnamese cinnamon

6innamomum 1oureiroi, also :no6n as Vietnamese cinnamon, is an evergreen
tree gro6n in the central and northern regions of Vietnam, 5romatic 1ar: of the
tree has medicinal and culinary value, Essential oil of the 1ar: contains
cinnamaldehyde GG)3H3"3*henyl*ro*3)3enalH as the main com*onent,
Mild o(idation of cinnamaldehyde 6ith NaCl/
)
affords an acid /, / undergoes
su1se4uent esterification 6ith ethanol to form ethyl cinnamate GBH, 8eflu(ing ethyl
cinnamate and 0T hydraAine hydrate solution for %0 h gives C GC
E
H
%0
N
)
/H,
8eflu(ing C and 3nitro1enAaldehyde in ethanol for %) h affords 3 GC
%$
H
%"
N
"
/
"
H,
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, !9

46
th
%
H NM8 s*ectra of C and 3 are given 1elo6 Gthe multi*licity and relative intensity
is sho6n for each signalH,
1( 7ive the structures for /, B, C(
!

46
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2( 5ssign
%
H NM8 signals in the first s*ectrum to a**ro*riate *roton grou*s of C,
1( 0ro*ose a reaction mechanism for the formation of C from B,
4( 5mong four given 1elo6 structures, select one for 3 and give the reasons for
your selection,
2( 5ssign
%
H NM8 signals in the second s*ectrum to a**ro*riate *roton grou*s of 3,
Problem 22. Cinnamic acid
1( Ultraviolet irradiation of trans3cinnamic acid GG3H3"3*henyl*ro*3)3enoic acidH in
solution yielded a mi(ture of cis3cinnamic and trans3cinnamic acids, trans3
Cinnamic acid can 1e crystalliAed in t6o forms: \3form or Y3form, Ultraviolet
irradiation of crystalline trans3cinnamic acid in the \3form yielded \3tru(illic acid
G),!3di*henylcyclo1utane3%,"3dicar1o(ylic acidH, Ultraviolet irradiation of
crystalline trans3cinnamic acid in the Y3form yielded Y3tru(inic acid G),"3
di*henylcyclo1utane3%,!3dicar1o(ylic acidH, \3Tru(illic acid *ossesses a
symmetric center, .n Y3tru(inic acid, the t6o *henyl grou*s are on the same side of
the cyclo1utane ring, and the t6o car1o(yl grou*s are on the o**osite sides,
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%,% 0ro*ose a reaction mechanism for the isomeriAation of trans3
cinnamic acid,
%,) ;ra6 the structure of \3tru(illic acid and all its diastereoisomers,
%," ;ra6 the structure of Y3tru(inic acid and all its diastereoisomers, Sho6 the
structures 6hich have enantiomers,
%,! Suggest ho6 the different *ac:ing arrangements of trans3cinnamic acid in the
\3 and Y3 crystal forms leads to the different structures of \3tru(illic and Y3
tru(inic acid,
%,# -hy does cinnamic acid not dimeriAe in solution u*on ultraviolet irradiationR
2( Hydrolysis of \3tru(illine GC
"
H
!$
N
)
/
, an al:aloid o1tained from Tru(illo cocaH

gives \3tru(illic acid, methanol and an acid / GC
E
H
%#
N/
"
H, /(idation of A Fith
*yridinium chlorochromate G0CCH leads to B, Fhich is readi1y decarbo9y1ated to
4orm otica11y inactive -etone C GC
H
%"
N/H, /(idation of C Fith otassium
erman$anate $ives ,0methy1succinimide+
2.1 Propose the structures of A, B, C. Are A, B optically active or not? Explain.
Why C is optically inactive?
),) 0ro*ose the structure of \3tru(illine, .s \3tru(illine o*tically active or notR E(*lain,
Problem 23. #ris5trimet&ylsilyl6silane and a0obisisobutyronitrile
#0

46
th
.n the late eighties, Chatgilialoglu and co6or:ers introduced
trisGtrimethylsilylHsilane, GTTMSS or GTMSH
"
SiHH as a radical31ased reducing
agent for functional grou* modifications and a mediator for se4uential radical
reactions, The use of GTMSH
"
SiH allo6s reactions to 1e carried out under mild
conditions 6ith e(cellent yields of *roducts and remar:a1le chemo3, regio3, and
stereoselectivity, GTMSH
"
SiH is an effective reducing agent for the removal of a
variety of functional grou*s, E(am*les of dehalogenation GCl, @r and .H and
reductive removal of chalcogen grou*s GS8 and Se8H are 6ell :no6n, The most
*o*ular thermal initiator is aAo1isiso1utyronitrile, ^5.@N, [GCH
"
H
)
CGCNHZ
)
N
)
_
under heating conditions in toluene,
1( 8eactions using TTMSS and 5.@N are given in the hereunder e(am*les,
%,% 8adical cyclisation 6as studied using t6o different reducing agents: tri1utyltin
hydride GT@TH, @u
"
SnHH and trisGtrimethylsilylHsilane GTTMSSH,
N
'<O
2
C
T&
Br
'
TTMSS "r B#
3
S!H
A.BN> 2"l#e!e> 80
"
C
N
T&
'
'<O
2
C
%,) 8adical introduction of a side chain Gal:ylationH
2( TTMSS has found multi*le a**lications in the organic synthesis descri1ed in the
1elo6 reactions:
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, #%

46
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),% The com*ound GIH 6as converted to B and C via the radical
intermediate /,
/
O
TTMSS ? A.BN
Be!@e!e> re0l#A
A
C
'e-#c2iBe :r"-#c2 C8cli&a2i"! :r"-#c2
),) The com*ound GIIH 6as converted to 3(
O
O
Br
O
TTMSS
A.BN>
D
)," The com*ound GIIIH 6as converted to E" and then through several ste*s to
afford GmH 3 vindoline
N
/
MeO
N
3
OB!
Me
TTMSS ? A.BN
T"l#e!e> 2
"
7
OMe
Me
CO
2
Me
N
N
62
OAc
HO
),! Horsfiline G?H is an o(indole al:aloid found in the *lant 2ors4ie1dia suerba,
6hich has analgesic effects, The method for horsfiline synthesis from the
com*ound GI&H 6as descri1ed 1elo6:
N
3
8
MeO /
N
B!
TTMSS ? A.BN
Be!@e!e>
9 :
/
;
C H
C
D N
2
MeO
N
O
B!
NMe
3C?D4DH"r&0ili!e
-rite do6n the structural formulae of all com*ounds / to I given in the a1ove reactions,
#)
GmH3Vindoline

46
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Problem 24. 5<6--ent&ol from 5=6->-3-Carene
Carene, or e3"3carene, is a 1icyclic monoter*ene 6hich occurs naturally as a
constituent of tur*entine, GLH3e3"3Carene has the re4uired structural features to
serve as a starting material for G3H3menthol,
The *rocedure of *re*aration of G3H3menthol from GLH3e3"3carene 6as descri1ed as follo6s,
Catalytic isomeriAation of e3"3carene *rovides the needed GLH3e3)3carene G/H
6hich then 6as *yrolysed to cleave the cyclo*ro*ane ring, The resultant ),3
menthaldien GBH had the right stereochemistry at C% and C! of G?H3menthol,
Treatment of the unconPugated diene B 6ith % e4uivalent mole of HCl gives C and
then, dehydrochlorination leads to a conPugated diene G3H,
CH
3
H
3
C
CH
3
S
'
1S> 6'D3C4D-el2aD3DCare!e
A C D
HCl HO
D
Treatment of 3 6ith hydrogen chloride affords 3chloro3"33menthene GEH 6hich
then reacted 6ith sodium acetate and acetic acid to give mi(ed GcisGtransH *ulegol
esters GFH via allylic dis*lacements, Hydrolysis of F affords G3H3cis and GLH3trans3
*ulegol G;H,
@ecause the a1solute configuration of C3% is fi(ed in this system, reduction of
either *ulegol isomer *rovides menthol isomers 6hich can 1e readily e4uili1rated
to *redominently G3H3menthol,
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, #"

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D
HCl
7 9 :
AcONa
AcOH
HO
D
H
2
CH
3
HO
3D4DMe!2,"l
-rite do6n the structural formulae of the com*ounds / to ;,
Problem 2". Cefalotin
Cefalos*orin is a Y3lactam grou* anti1iotic, Cefalotin, a derivative of
cefalos*orin, has stronger activities on gram G3H and gram GLH 1ateria, 1ut lo6er
to(icity, Therefore, it has 1een studied and a**lied into medical treatment,
Cefalotin has 1een synthesiAed from D3cistein according to the follo6ing diagram:
#!

46
th
H
2
N
HO
2
C
H
SH
ace2"!e
B
C
6
H
11
NO
2
S
2
B#OH
COCl
2
D C
CH
2
N
2
C
11
H
19
NO
4
S C
12
H
21
NO
4
S
E
C
16
H
27
N
3
O
8
S
N
N
MeO
2
C
CO
2
Me
P(3OAc4
4
NaOAc> MeOH
F
C
12
H
21
NO
5
S
MeOSO
2
Cl
NaN
3
G
C
12
H
20
N
4
O
4
S
Al3Hg4
H
Al3OD
i
B#4
3
I
C
11
H
18
N
2
O
3
S
K
C
18
H
23
Cl
3
N
2
O
7
S
CHCO
2
CH
2
CCl
3
OHC
OHC
CF
3
CO
2
H
L
C
10
H
9
Cl
3
N
2
O
4
S
M
S
CH
2
COCl
B
2
H
6
N
Ac
2
O
O
P8ri-i!e
P
$!
AcOH
N
S
O
N
H
O
S
CO
2
H
CH
2
OAc
Ce0al"2i!
1( Com*lete the a1ove synthetic scheme,
2( -rite do6n a reaction mechanism from = to <(
1( Ho6 many o*tical isomers of cefalotin should 1e e(*ectedR
Problem 2$. A &eterocyclic compound
8ecently, several transformations of levulic acid G!3o(o*entanoic acidH have
1een re*orted in the 2ournal of Chemistry GVietnamH, /ne of them is the synthesis
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, ##
t3@u/H

46
th
of three hydraAides G8C/NHNH
)
H from

levulic acid in 6hich 8 is one of
the follo6ings:
Com*ound / Com*ound B
Com*ound C
/ssmin@ that yo ha$eA inor@ani) )hemi)als" le$li) a)id" other a)y)li)
or@ani) )omponds" benBene deri$ati$es (PhC%O" P%6C," 1-
6O
2
C
6
%
4
,O
1
6a)" )atalysts (piperidine" +sO%)" and sol$ents(
1( 0rovide the synthetic scheme to o1tain /, -hat is the *ur*ose of %,"3dio(olan
formationR -rite do6n the reaction e4uation to *re*are Ts/H from toluene,
2( 0rovide the synthetic scheme to o1tain B, -hat is the reation mechanism using
0hNCSR -rite do6n the reaction e4uation to synthesiAe 0hNCS from alinineR
1( 0rovide the synthetic scheme to o1tain C, -hat is the role of "3/
)
NC
$
H
!
S/
"
NaR
-rite do6n the reaction e4uation to *re*are "3/
)
NC
$
H
!
S/
"
Na from 1enAene,
Using signals from *roton nuclear magnetic resonance s*ectrosco*y to *rove that
the reaction 6ith "3/
)
NC
$
H
!
S/
"
Na has occurredR
4( The three hydraAines G/, B, and CH are reacted 6ith 0hCH/ to generate
corres*onding *roducts GE" F, and ;H, ;ra6 a common reaction mechanism for
these transformations, .f !3N/
)
C
$
H
!
CH/ or !3Me
)
NC
$
H
!
CH/ 6as used instead of
0hCH/, should the reactions *roceed more difficult or easierR
Problem 2'. *otus
Dotus is :no6n as the scientific
name of ,e1umbo nuci4era, 8ecently,
#$

46
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Vietnamese researchers colla1orating 6ith Canadian scientists discovered the
a1ility to *romote the *roduction of insuline in Y cells of nuciferine, 6hich may 1e
used to treat the %ypo@ly)emia, GC, Hoa Nguyen, H,;ien 0ham, @,D, 7regoire
Nyom1a et al, D+ o4 3thnoharmaco1o$y, 2012, 142, 48804B<H, There are some
6ays to synthesiAe nuciferine from different reactants, 1ut the synthetic *rocedures
are almost very com*licated and the reaction yield is very lo6, Chia3'u Chang et
al, at Changhua National University GTai6anH re*orted a *rocedure to synthesiAe
the nuciferine through " ste*s using a 1enAaldehyde derivative in Nef reaction,
0ictet3S*engler reaction and radical cycliAation GSynth+ 6ommun+, 2010, 40, A4<20A4>>,H,
3 Nef ns reaction G2ohn Ulric Nef, %E!H:
8
)
CHN/
)
%,Na/H
),H
)
S/
!
8
)
C/ L %O)N
)
/
The mechanism of NefMs reaction:
N
L
8
%
8
)
3
/
/
L /H
3
3 H
)
/
N
L
8
%
8
)
3
/
3
/
L H
L
3 H
)
/
/
8
%
8
)
L %O)N
)
/
E(am*le:
CH
"
CH
)
N/
)
CH
"
CH/

L %O) N
)
/
%,Na/H
),H
)
S/
!

3 The radical cycliAation reaction:
8adical initiator: 5.@N [aAo1isiso1utyronitrile, Me
)
CGCNHN=NCGCNHMe
)
Z
The 0ictet3S*engler addition3cycliAation G5mo 0ictet, Theodor S*engler, %E%%H: is
the condensation reaction and then cycliAation 1et6een ?3arylethylamine and
aldehyde or :etone in the *resence of acid catalyst 6ith heating, E(am*le:
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, #9

46
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NH
NH
)
8CH/, H
L
, t
o

NH
NH
8
The reaction scheme for the synthesis of nuciferine is:
,tep 1: Synthesis of ,3metho(ycar1onyl amine,
Me/
Me/
CH/
Ga"H
Me/
Me/
NHC//Me
CH
"
N/
)
5c/NH
!
5c/H
/
1
GC
%0
H
%%
/
!
NH
Di5lH
!
TH'
0
o
C
/
2
GC
%0
H
%#
/
)
NH
G/
1
H
,tep 2: Synthesis of arylacetaldehyde,
CH/
@r
G1"H
@r
CH/
GB
1
H
CH
"
N/
)
5c/NH
!
5c/H
B
1
GC
H
$
/
)
N@rH
B
2
GC
/
)
N@rH
Na@H
!
CH
)
Cl
)
,tep 1: Synthesis of nuciferine
N
Me
Me/
Me/
/
1
L B
1
Di5lH
!
TH'
C
1
GC
)0
H
))
/
!
N@rH
3 H@r
C
2
GC
)0
H
)%
/
!
NH
@'
"
3/Et
)
CH
)
Cl
)
OCHCl
"
G%:%H
AlBN,
@u
"
SnH
Nuciferine
1( ;etermine the structural formulae for /
1
, /
2
, B
1
, B
2
, C
1
, C
2
, reaction conditions
for Ga"H, G1"H and com*lete the a1ove reaction scheme,
#

46
th
2( .ndicate the reaction mechanism for the formation of /
1
from ",!3
dimetho(y1enAaldehyde Gste* %H& C
1
from /
1
L B
1
Gste* "H,
1( ;etermine the structural formulae for t6o isomers of D
1a
, D
1b
and com*ound D
2
1ased on the schematic conversion 1elo6:
Nuciferine
%, CH
"
. e(cessO5g
)
/
), Heated
D
2
GC
)0
H
)%
/
"
NH
CHCl
"
, Na/H #0T
@u
!
NCl
D
1a
GC
)0
H
)"
/
)
NH
D
1b
L
Problem 2(. 3-% .pectra
1( 5t room tem*erature, the NM8 s*ectrum of cyclohe(ane sho6s only a single
resonance *ea:, 5s the tem*erature of the sam*le is lo6ered, the shar* single *ea:
1roadens until at 3$%,0 pC it 1egins to s*lit into t6o 1roaden *ea:s, 5s the
tem*erature is lo6ered further to 3E0 pC, each of the t6o 1ands 1egins to give a
s*litting *attern of its o6n, E(*lain the origin of these t6o families of 1ands,
!$
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H
H
H
H
H
H
H
H
H
H
H
H
2( .n cis3%31romo3!3tert31utylcyclohe(ane, the *roton on car1on3! is found to give
resonance at !,"" **m, .n the trans isomer, the resonance of the C
!
hydrogen is at
",$" **m, -hy do these com*ounds have different chemical shift values for the
C! hydrogenR 2ustify 6hy this difference cannot 1e o1served in the !3
1romomethylcyclohe(anes e(ce*t at very lo6 tem*eratures,
Problem 2). /% spectra
1( Su1stitution of an amino grou* on the ara *osition of aceto*henone shifts the
C=/ fre4uency from a1out %$# to %$#) cm
X%
, 6hereas a nitro grou* attached to
the ara *osition yields a C=/ fre4uency of %$E" cm
X%
, E(*lain the shift for each
su1stituent from the %$# cm
X%
1ase value for aceto*henone,
2( ConPugation of a C=C dou1le 1ond 6ith either a car1onyl grou* or another
dou1le 1ond *rovides the multi*le 1ond 6ith more single31ond character Gthrough
resonance, as the follo6ing e(am*le sho6sH, a lo6er force constant K, and thus a
$0

46
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lo6er fre4uency of vi1ration, 'or e(am*le, the vinyl dou1le 1ond in styrene gives
an a1sor*tion 1and at %$"0 cm
X%
, Esters sho6 a very strong 1and for the C=/
grou* that a**ears in the range of %9#0?%9"# cm
X%
for sim*le ali*hatic esters, The
C=/ 1and is shifted to lo6er fre4uencies 6hen it is conPugated to a C=C or *henyl
grou* G2int!

K
c )
%
=
, H, reduced massI c, seed o4 1i$ht)+
5ssign a structure to each of the s*ectra sho6n, Choose from the follo6ing #3
car1on esters,
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, $%

46
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$)

46
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Part 2. P%ACT)CA* P%(+*',-
+%E ,/FE+D #E<E, /63 #E;E</+IO6,
#e@lations o. the International Chemistry Olympiad (IChO)
,a.ety
G%H ;uring the e(*erimental *art, the com*etitors must 6ear la1oratory coats and
eye *rotection, The com*etitors are e(*ected to 1ring their o6n la1oratory coats,
/ther means of *rotection for la1oratory 6or: are *rovided 1y the organiAer,
G)H -hen handling li4uids, each student must 1e *rovided 6ith a *i*ette 1all or
filler, 0i*etting 1y mouth is strictly for1idden,
G"H The use of acutely to(ic su1stances G7HS haAard statement H"00, H"%0, H""0H
is strictly for1idden, The use of to(ic su1stances is not recommended, 1ut may 1e
allo6ed if s*ecial *recautions are ta:en, Su1stances 6ith 7HS haAard statements
H"!0, H"#0, H"$0 G*roven mutagens, carcinogens, and teratogensH must not 1e
used under any circumstances Gsee 5**endi( @ for definitions of these categoriesH,
G!H ;etailed recommendations involving studentsq safety and the handling and
dis*osal of chemicals can 1e found in 5**endices 5 %, 5 ), and @,
aH 5**endi( 5 %: Safety 8ules for Students in the la1oratory,
1H 5**endi( 5 ): Safety 8ules and 8ecommendations for the Host Country of the
.Ch/,
cH 5**endi( @ contains a reference to the haAard sym1ols and statements of the
7lo1ally HarmoniAed System of Classification of Chemicals G7HSH, the use of
6hich is e(*ected in la1eling and classifying materials used at the .Ch/,
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, $"

46
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Problem 3+. Condensation between ?anillin and ben0ylamine
1( Introd)tion
&anillin is a *henolic aldehyde 6ith the molecular formula C
/
"
, Thus, it has
three ty*es of functional grou*s including aldehyde, ether, and *henol, This
com*ound is often used as a flavoring agent in foods, 1everages, and
*harmaceuticals, Vanillin is the *rimary com*onent of the e(tract of
the )ani11a 1ani4o1ia, .t is :no6n that the aldehyde functional grou* in vanillin
can 1e easily converted into enamine derivatives or imides through the
condensation reaction 1et6een vanillin and amines, The *roducts are synthones
6hich are 6idely a**lied in the synthetic organic chemistry and *harmaceuticals,
2( Chemi)als and #ea@ents
3 Vanillin: %3) g
3 @enAylamine,
3 ;ichloromethane: )0 mD,
3 Sodium sulfate, Na
)
S/
!
1( EFipment and ;lass'are
3 Erlenmeyer flas:s, )#0 mD
3 7raduated cylinders, %0, )#, #0 mD
$!

46
th
3 @eral *i*ets,
3 @ea:ers, #0 mD,
3 Hot *late,
3 S*atulas,
3 @rchner funnel 6ith filter flas: and filter *a*er, se*arating funnel,
3 Melting *oint a**aratus and ca*illary tu1es,
3 Small vials 6ith ca*s,
3 Vials 6ith ca*s, )0 mD
3 Thin layered chromatogra*hy GTDCH s*otters,
3 TDC *lates Gsilica 6ith fluorescent indicator 5)#!H,
3 Cham1er for TDC develo*ment,
3 Magnetic stirrer,
3 .ce 6ater 1ath,
4( EGperimental pro)edre
1, 5dd %,0 g of vanillin into a dry #03mD flas: then add %0 mD of dichloromethane
solvent into the flas:, The mi(ture is stirred for %0 min at room tem*erature, and
then 0,9 g of 1enAylamine and ),0 g of Na
)
S/
!
are simultaneously added into the
flas:,
2, The reaction mi(ture is further stirred at reflu( condition G$#3$9
o
CH for E0 min,
Cool the flas: to room tem*erature,
1, ;ilute the resultant mi(ture 6ith !0 mD and s6irl the flas:,
4, Transfer the mi(ture into a se*arating funnel and then e(tract 6ith "0 mD of
dichloromethane, E(tract the organic *hase ) times more 6ith "0 mD of
dichloromethane,
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46
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2, ;ry the e(tracting organic fraction 6ith MgS/
!
, 'ilter the organic
fraction through a @uchner funnel, ;iscard the solid and collect the filtrate,
6( 8emove the solvent in the filtrate 1y rotary eva*oration to o1tain the *roductGsH,
:( ;etermine the *urity of the crude *roduct 1y thin layer chromatogra*hy method,
Use *recoated silica gel *lates GSilica 7el 0'3)#!H and visualiAe the s*ots 1y UV3
light, Use ethyl acetate: he*tane %#:# mi(ture as an eluent,
Note: #t is recommended to carry out the e9eriment under a hood+
2( >estions and 3ata analysisA
%, -eight the o1tained *roduct,
), ;ra6 the mechanism of imine formation,
", -hat is the role of Na
)
S/
!
in the *resent e(*erimentR
Problem 31. .ynt&esis of eugeno!y acetic acid
1( Introd)tion
Eugeno(yacetic acid G.U05C name: )3metho(y3!3G)3*ro*enylH*heno(yaceticH
is an odorless, colorless and non3cytoto(ic com*ound, .t has sho6n anti3viral and
anti31acteria *ro*erties and is therefore used as antio(idant food *reservative in
food industry, 8ecently, eugeno(yactetic acid and its ester derivatives such as
methyl and ethyl esters have 1een found to 1e the a1ility to inhi1it li*id increasing
6hich leads to their *otential a**lication in the treatment of human
hy*erli*idaemia, .n addition, eugeno(yacetic acid acts as a *romising *lant gro6th
*romoter due to their au(in Garylo(yaceticH structural characteristics,
$$

46
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The nature and living organism friendly *ro*erties of eugeno(yacetic are the result
of the com1ination of acetic moiety 6hich is *resent in vinegar and eugenol moiety
6hich is the main constituent of the essential oil o1tained from clove oil,
Clove is an aromatic *lant in the family Damiaceae 6hich is native to tro*ical areas
and 6ides*read as a cultivated *lant, .n Vietnam, there are t6o s*ecies of clove,
%cimum sanctum D, and %cimum $ratissimum D,, 6hich have 1een used in many
tradtional medicinal *ur*oses 6ithout adverse effects,
.n this *ractical *ro1lem, eugeno(yacetic acid 6ill 1e synthesiAed from eugenol
as sho6n in the scheme 1elo6:
2( Chemi)als and apparats
3 Clove essential oil,
3 Monochloroacetic acid,
3 Na/H,
3 Na
)
C/
"

3 54ueous HCl solution,
3 ;istilled 6ater,
1( /pparats and @lass'are
3 Erlenmayer flas:: #0 mD,
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46
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3 Magnetic stirrer 6ith heater,
3 Magnetic 1ar,
3 @ea:er: %00 mD,
3 @ea:er: )#0 mD,
3 7lass filter: )# mD,
3 7lass filter: #0 mD,
3 Vacuum filter set Gvacuum *um*, 'ilter flas:H,
3 ;ro**ing funnel,
3 S*atula,
3 7lass rode,
4( EGperimental pro)edreA
,tep 1
1( ;issolve 0,$ g Na/H in ",0 ml distilled 6ater in a #0 mD3Erlenmayer flas: and
then add ),0 mD clove essential oil, Cee* the flas: in the 6ater 1ath at 03E0
o
C
6hile stirring 6ith the magnetic stirrer,
2( ;issolve carefully %,0 g monochloroacetic acid in #,0 mD distilled 6ater in a )#
mD 1ea:er& stir the solution 6ith the s*atula, 5dd Na
)
C/
"
slo6ly Pust to the
al:aline reaction GSolution /H,
,tep 2
1, 5dd slo6ly the solution / to an Erlenmayer flas: and :ee* stirring the mi(ture
at E03E#
o
C for $0 min, Cool the reaction mi(ture 6ith 6ater to room tem*erature,
and then acidify 6ith HCl %:% to the acidic reaction Gtest by 1itmus aerH GSolution BH,
2, 5dd a small amount of crushed ice G#3%0 gH to the solution @ and stir until the
yello6 oil turns to the solid, .solate the solid 1y filtration 6ith suction in to a
sintered glass cruci1le, -ash the solid 6ith 6ater to o1tain the crude *roduct as
*ale yello6 solid,
,tep 1
$

46
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1, 0urify the *roduct as follo6s: transfer the crude *roduct to a )#0 mD 1ea:er, add
03%00 mD hot 6ater Ga1out E0
o
CH to the 1ea:er and continue 1oiling for #3%0
min, Cool the solution 6ith 6ater and ice3cold 6ater,
2, .solate the *roduct 1y filtering 6ith suction into a sintered glass cruci1le and
6ash the solid several times to o1tain 6hite needles, ;ry the solid in the drying
oven for $0 min, -eigh the dried *roduct,
2( >estions and data analysisA
%, -rite do6n the reactions occurring in ste* %a, %1 and ),
), Calculate the reaction yield,
", 0ro*ose a mechanism for the reaction in ste* ),
!, E(*lain 6hy the reaction must 1e conducted in al:aline mediumR Should an
e(cess amount of al:aline 1e used in the reactionR
#, Com*are the *ossi1ilities of the chlorine atom in monochloroacetic acid and
those in al:yl chlorides to 1e su1stituted,
$, .f the *ure *roduct o1tained in the e(*eriment a1ove Gm*, 9)
o
CH is re3
crystalliAed in 1enAene, its m*, -ill rise to %00,#
o
C, Suggest an e(*lanation for
this o1servation and *ro*ose method to test your e(*lanation,
9, -hen eugeno(yacetic acid is reflu(ed in C/H solution, and acidified 6ith HCl
G%:%H solution, an isomer of eugeno(yacetic acid, isoeugeno(yacetic acid can 1e
o1tained in the form of t6o stereoisomers, ;etermine the structures of these t6o
isomers and e(*lain the formation of isoeugeno(yacetic acid 6ith a suita1le
reaction mechanism,
Problem 32. Comple!ometric titration of iron, aluminum, and
magnetism in t&e a@ueous solution
!$
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46
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1( Introd)tion
Com*le(ometric titration is one of the most common methods of volumetric
analysis in chemical la1oratories, .n this method, the most 6idely used com*le(ing
agent is disodium salt of ethylenediaminetetraacetic acid GE;T5H, E;T5 is a
*oly*rotic acid GH
!
WH, The solution Na
)
H
)
W is used as a standard solution for
titration of metal ions GM
nL
H:
M
nL
L H
)
W
)3
L )H
)
/ V MW
n3!
L )H
"
/
L
The formation constant GC
f
H of MW
n3!
de*ends on the nature of metal ions, 'or e(am*le:
Metal ions C
f
Titrated at *H
'e
"L
%0
)#,%
),0
5l
"L
,
01
)L
, Fn
)L
%0
%$,%"
!,0 ? #,0
Mg
)L
%0
,$E
E,0 ? %0,0
Metal ions can 1e titrated se*arately due to the formation of MW
n3!
com*le( 6ith
conditional formation constant at a suita1le *H condition, .n *ractical, the
metallochromic indicators are usually used for the detection of the end *oint, These
indicators are the color com*le(ing agents for the metal ions, The color of the
indicator differs from that of the metal3ion3com*le( and metal indicator com*le(
GMindH is much less sta1le than metal3E;T53com*le(, Therefore, the titration of a
metal ion solution is carried out 6ith a given indicator at suita1le *H of the
solution:
M.nd L H
)
W
)3
V MW
n3!
L .nd
This tas: is to hel* *artici*ants to use techni4ues of the volumetric analysis for
the determination of metal cations,
2( Chemi)als and rea@ents
3 Standard solutions of 0,0#0 M E;T5 Gfrom Na
)
H
)
W,)H
)
/H,
3 0,0#0 M FnGN/
"
H
)
,
3 @uffer solutions of %M CH
"
C//H and % M NaCH
"
C// G*H = !,9H,
3 Solution of ) M NH
"
L ) M NH
!
Cl G*H = E,)H,
3 Solution of %M HCl,
90

46
th
3 Solution of %M Na/H,
3 ;istilled 6ater,
3 .ndicators: (ylenol orange G%T in CClH,
3 Eriochrome 1lac: T GET ? 00H G%T in CClH& The congo red G*H indicatorH&
universal *H indicator *a*er& #T solution of sulfosalicylic acid,
3 @urette: #0 mD,
3 Volumetric *i*ette: )# mD,
3 Erlenmeyer flas:: )#0 mD,
3 7raduated cylinder: %0 mD,
3 7lass 1ea:er: )#0 ml"
3 'unnels and filter *a*ers Gthe red ta*eH,
3 ;ro**ers,
3 Hot *late,
,tep 1( ,ample preparation
0re*are a sam*le solution containing three ions of 'e
"L
, 5l
"L
, and Mg
)L
6ithin
concentration range of 0,0% M to 0,% M,
,tep 2( +itration o. iron" alminm" and ma@nesim ions
1. itration of !e
"#
5dd #,00 mD of the sam*le solution into an Elenmeyer flas:, 5dPust the *H of
the solution to ) using Na/H or HCl solution 6ith the Congo red *a*er, Heat the
solution to 0 3 E0
o
C on a hot *late and then add 0,# mD of sulfosalicylic acid as
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, 9%

46
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indicator, The solution is titrated 6ith E;T5 solution to a colorless to
yello6 end *oint, 8ecord the volume of the standard solution GV
%
mDH,
2. itration of the total a$ount of !e
"#
an% Al
"#
5dd )#,00 mD of the sam*le solution into an Elenmeyer flas:, 5dd #0 mD of
E;T5 standard solution into the flas:, Heat the solution to 0 3 E0
o
C and add %0 3
%# mD of the 1uffer solution CH
"
C//HO NaCH
"
C// and a small amount of
(ylenol orange, Titrate the remaining amount of E;T5 6ith the Fn
)L
standard
solution until the solution changes from red to yello6 at the end3*oint, 8ecord the
volume of the standard solution GV
)
mDH,
". itration of &'
2#
Ta:e )#,00 mD of the sam*le solution to a glass 1ea:er 5dd slo6ly the NH
"
L
NH
!
Cl 1uffer solution 6hile stirring the mi(ture, 5fter the *reci*itation reaction is
com*lete, add # mD of 1uffer solution and s6irl the mi(ture, 'ilter the solution to
an Elenmeyer flas: through filter *a*er 6ith a funnel, -ash the *reci*itate G"3!
timesH 6ith 6arm 6ater, 'inally, titrate Mg
)L
6ith standard E;T5 solution using
ET ? 00 until the solution changes from 6hite red to 1lue, 8ecord the volume of
the standard solution GV
"
mDH,
2( >estions and 3ata analysis
%, -rite do6n the chemical reactions in each individual ste* of the titration,
), ;erive the formulae for calculating the concentrations of 'e
"L
, 5l
"L
and Mg
)L
in
the sam*le solution,
", Calculate the concentrations of each ion in the sam*le solution,
9)

46
th
Problem 33. Determination of 0inc and lead in 0inc o!ide powder
1( Introd)tion
Finc o(ide Fn/, a soft, 6hite or faintly yello6ish36hite is used in the
vulcaniAation of ru11er, ceramics, *aints, and many other *roducts,
Finc o(ide is *roduced 1y 1urning Ainc metal in air as follo6s:
Fn
GsH
Fn
GlH
Fn
GgH
) Fn
GgH
L /
)
) Fn/
GsH
0urity of the given Ainc has an influence on the 4uality of Ainc o(ide *o6der,
There is a very 6ide range of commercial grades of Ainc o(ide de*ending on
content of im*urities, 'or e(am*le, Ainc o(ide *o6der 37rade ) Ghaving greater
than $0 6t,T of FnH *roduced 1y electro3thermal *rocess contains less than !T
Ca& 0,!T 'e& T 01,
This tas: is to determine the *ercentage of Ainc and lead in commercial Ainc
o(ide *o6der 1y E;T5 and dichromate solution,

2( 0aterials and #ea@ents
3 Finc o(ide *o6der,
3 Sulfuric acid solution, H
)
S/
!
Ga4H, ! M,
3 Nitric acid solution, HN/
"
Ga4H, $ M
3 0,0)# M E;T5 standard solution Gfrom Na
)
H
)
W,)H
)
/H,
3 Sodium thiosulfate: 0,0) M solution Gfrom Na
)
S
)
/
"
B#H
)
/H,
3 'errous sulfate: 0,0)# M solution Gfrom 'eS/
!
,9H
)
/H,
3 Mi(ture of HCl and NaCl: ;issolve ")0 g of NaCl in )00 mD of distilled
6ater, add %00 mD of concentrated HCl "9 6t,T and dilute to %,0 D 6ith
distilled 6ater,
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46
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3 Solution of #T G6OvH C
)
Cr
)
/
9
Ga4H,
3 Mi(ture of *otassium iodide and thiocyanate, C.L CSCN, %0T 6Ov,
3 Mi(ture of CH
"
C//H ) M and NH
!
CH
"
C// %M,
3 5mmonia solution NH
"
$ M,
3 )00 mD of *H %0 1uffer solution of NH
"
ONH
!
Cl,
3 Eriochrome @lac: T GET300H indicator, %T G6O6H in NaClGsH,
3 ;i*henylamine sulfonate indicator, 0,)T G6O6H in 6ater,
3 Starch indicator, %T in 6ater, This solution is *re*ared daily 1y mi(ing 0,# g
solu1le starch 6ith )3" mD distilled 6ater and then *ouring the starch into #0
mD 1oiling distilled 6ater 6ith stirring, Continue heating the solution until the
solution is nearly trans*arent, Cool solution to room tem*erature 1efore use,
3 5nalytical 1alance Gm 0,000% gH
3 Hot*late
3 Erlenmeyer flas:, )#0 mD
3 Volumetric flas:, %00 mD
3 Volumetric *i*ette, %0,00 mD
3 @urette )# mD
3 7lass 1ea:er )#0 mD
3 -hatman 'ilter *a*er, 7rade )V, %%0 mm,
,tep 1
%, 0lace 0,#0 g of a *o6der sam*le in a %00 mD glass 1ea:er, 5dd %0 mD of ! M
H
)
S/
!
into the 1ea:er, 0lace the 1ea:er on a hot *late and 1egin heating the
mi(ture in the hood, Set the hot *late at medium heat, 5s a *ortion of solid
9!

46
th
dissolves, the yello6ish residues still remains in the 1ea:er, 5dd slo6ly " mD of
HN/
"
solution into the 1ea:er and :ee* heating the solution until 6hite
*reci*itate a**ears, Eva*orate the solution in the 1ea:er until 6hite fumes of S/
"
forms, and then sto* heating, Cool the solution to the room tem*erature G2int! in
hood),
'ilter the cooled solution 1y using filter *a*er to a %00 mD volumetric flas:&
rinse the 1ea:er and filter *a*er 6ith % T H
)
S/
!
several times& ma:e u* the
filtrate to the mar: 6ith distilled 6ater and sha:e 6ell Gsolution /H,
), 0lace the funnel together 6ith the filter *a*er on a )#0 mD Erlenmeyer flas:,
0our slo6ly a hot mi(ture of )0 mD of CH
"
C//HL NH
!
CH
"
C// through the
6hite *reci*itate on the filter *a*er until it is dissolved, -ash the filter *a*er
6ith distilled 6ater to get solution B,
,tep 2
%, 5dd %0,00 mD of solution G/H and # mD of NH
"
solution into a )#0 mD
Erlenmeyer flas: using *i*ettes and s6irl to mi(, Then, add %0 mD of NH
"
ONH
!
Cl
1uffer solution G*H = %0H to the mi(ture,
5dd ET300 indicator and a1out %0 mD of deioniAed 6ater, Titrate carefully 6ith
the E;T5 standard solution until the color changes from 6ine red to 1lue, 8ecord
the volume of E;T5 used for this titration,
(2int! "dJust the si8e o4 the a1i'uot on En
2=
as necessary to stay Fithin titration ran$e)+
), 5dd the solution B and # mD of %0 T NaCH
"
C// into a )#0 mD 1ea:er, Heat
the mi(ture slo6ly Gta:ing at least %0 minutesH to E0
o
C and then add gently %0 mD
of C
)
Cr
)
/
9
solution, Cool the mi(ture to room tem*erature and :ee* further at this
condition for % hour, 'ilter the *reci*itate through a -hatman filter *a*er, -ash
the *reci*itate 6ith 6arm distilled 6ater until the filtrate is almost colorless,
Trans*ort the funnel 6ith filter *a*er to a )#0 mD Erlenmeyer flas:, ;issolve
the yello6 *reci*itate 6ith %# mD of 6arm mi(ture HCl LNaCl, 8inse the filter
*a*er 6ith distilled 6ater to get the solution C,
!$
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46
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5dd a1out # mD of ! M H
)
S/
!
, # mD of ! M H
"
0/
!,
and %0 mD of
distilled 6ater to the solution C, ;ro* dro*lets of di*henylamine sulfonate
indicator in the solution C, Titrate carefully 6ith the standard ferrous solution until
the color changes from violet to green, 8ecord the volume of ferrous solution used,
(2int! So1ution 6 can a1so be titrated usin$ the iodometric titration)+
2( >estions and 3ata /nalysis
1, 7ive 1alanced chemical e4uations for the reactions 6hen:
%,% The Ainc o(ide *o6der dissolves in sulfuric acid and nitric acid to form a
6hite solid,
%,) The 6hite *reci*itate is dissolved in a mi(ture of CH
"
C//H ) M3
NH
!
CH
"
C// % M to form a com*le( *roduct C,
%," The *roduct C reacts 6ith C
)
Cr
)
/
9
Ga4H to form a yello6 *reci*itate,
%,! The yello6 *reci*itate dissolves in the mi(ture of HCl and NaCl,
%,# The solution C is titrated 6ith 'e
)L
andOor iodometric titration,
2( Calculate the mass *ercentage of Fn and 01 in the *o6der,
1, .n iodometric titration, S
)
/
"
)3
is used to titrate .
)
*roduced in the reduction of
H
)
Cr
)
/
9
1y .
3
, -hy do 6e not use S
)
/
"
)3
for titration of the H
)
Cr
)
/
9
R
4( 01Cr/
!
is com*letely *reci*itated in the medium 6ith *H of at least # Gacetic
acid3 acetate 1ufferH,
!,% ;oes the addition of %00 mD of %,0>%0
?!
M 01G/5cH
)
to )0 mD of %,0>%0
?"
M C
)
Cr/
!
lead to a *reci*itate formation, given that C
s*
for 01Cr/
!
is %,>%0
3
%!
R
!,) 'ind the e4uili1rium concentration of 01
)L
remaining in solution after the
01Cr/
!
*reci*itates,
Problem 34. Preparation of copper5//6 acetylacetonate
1( Introd)tion
9$

46
th
5cetylacetone GHacacH is the sim*lest of the 1eta3di:etones,
Hacac commonly e(ists in t6o tautomeric forms, :etone and enol, 6hich can
ra*idly interconvert in solution as 6ell as in the gas *hase,
Cetone form Enol form
.n a4ueous solutions, Hacac is in e4uili1rium 6ith hydrogen ions GH
L
H and 6ith
acetylacetonate GenolateH ions Gacac
3
H, The dissociation constant C
a
is %,#%>%0
3E
,
5cetylacetone can form sta1le com*le(es 6ith many transition metal ions, .n most
of the structurally characteriAed com*le(es, Hacac that is singly de*rotonated acts
as a 1identate ligand, and 1inds to the metal via 1oth t6o o(ygen donor atoms to
form si(3mem1ered chelate ring,
5cetylacetone is :no6n to form neutral com*le(es 6ith a1out $0 metals and is
among the most versatile and most used chelating ligand in coordination
chemistry,
Co**er G..H acetylacetonate can 1e synthesiAed in a ligand e(change reaction:
)acac
3
L [CuGH
)
/H
$
Z
)L
[CuGacacH
)
Z,nH
)
/ L G$3nH H
)
/
3 5cetylacetone
!$
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46
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3 0,) M CuS/
!
a4ueous solution
3 )#T NH
"
solution
3 ;iluted HCl solution
3 ;iluted NH
"
solution
3 Universal indicator *a*ers
3 Chemicals for determination of Cu content,
1( /pparatses and ;lass'areA
3 7lass 1ea:ers: %00 mD, #0 mD,
3 0i*ette: # mD,
3 7raduated cylinder: #0 mD,
3 8u11er 1ul1,
3 -atch glass,
3 7lass rod,
3 Magnetic stirrer,
3 Sintered glass funnel,
3 Vacuum *um*,
3 -ash 1ottle,
3 5nalytical 1alance 6ith reada1ility of 0,00% g,
4( EGperimental pro)edreA
,tep 1( Preparation o. )opper (II) a)etyla)etonateA
%, Use )# mD of 0,) M CuS/
!
a4ueous solution to calculate the 4uantities of
chemicals re4uired for synthesis of the com*le(,
9

46
th
), 0re*are the ammonium acetylacetonate GNH
!
acacH solution: 5dd slo6ly )#T
NH
"
a4ueous solution Gd = 0,E0 g,cm
3"
H into li4uid acetylacetone in a #0 mD glass
1ea:er 6ith a molar ratio Hacac : NH
"
of %,0 : 0,E, 5 6hite solid a**ears for
seconds and then dissolves com*letely to o1tain a clear solution,
", 0re*are the co**er G..H acetylacetonate: 5dd the freshly *re*ared NH
!
acac
solution G6ith a #0T e(cessH into a %00 mD glass 1ea:er in 6hich )# mD of 0,) M
CuS/
!
a4ueous solution and a stirring 1ar are *laced, Start stirring the solution on
a magnetic stirrer and adPust the *H of the mi(ture to "3! 1y the addition of dilute
solutions of HCl and NH
"
, The *ale 1lue solid of co**er G..H acetylacetonate is
*reci*itated, The reaction mi(ture is stirred for additional "0 min to com*lete the
*reci*itation, The formed solids are collected on sintered glass funnel 1y a vacuum
filtration, 6ashed " times 6ith small *ortions of distilled 6ater and then
trans*orted to a 6atch glass and dried at %)0
o
C for "0 min, -eigh the *roduct on
the analytical 1alance 6ith the reada1ility of 0,00% g,
,tep 2( 3etermination o. the C )ontent in the )ompleG
%, Students *ro*ose an a**ro*riate *rocedure to determine the Cu content in the
*roduct, (2ints! The 6u
2=
concentrations can be determined by iodometric
titration, com1e9ometric titration Fith 37T"K),
2( >estions and 3ata analysis
1( Calculate the co**er content in the com*le(, Suggest an a**ro*riate molecular
formula of co**er G..H acetylacetonate and then calculate the *ercentage yield of
the synthesis of the com*le(,
2, .n the Ste* %G"H, 6hy is the e(cess of NH
!
acac usedR -hy does the *H need to
1e adPusted to "3!R
1, 0ro*ose the molecular structure of co**er G..H acetylacetonate,
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, 9E

46
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Problem 3". ,inetic analysis of t&e &ydrolysis of aspirin
1( Introd)tion
5s*irin Gacetylsalicylic acidH is an ester of salicylic acid, .t has 1een 6idely used in
medicinal treatment, .t is an effective analgesic G*ain :illerH that can reduce the mild
*ain of headache, toothache, neuralgia Gnerve *ainH, muscle *ain and Point *ain Gfrom
arthritis and rheumatismH, 5s*irin 1ehaves as an anti*yretic drug Git reduces feverH,
and an anti3inflammatory agent ca*a1le of reducing the s6elling and redness
associated 6ith inflammation, .t is an effective agent in *reventing stro:es and heart
attac:s due to its a1ility to act as an anti3coagulant,
5s*irin can 1e easily synthesiAed in la1oratory 1y the esterification reaction 1et6een
salicylic acid and acetic anhydride as sho6n in the reaction 1elo6:
OH
O
O
H
O
O
CH
3
O
CH
3
L
O
O
O
H
O CH
3
L
O
OH
H
3
C
,ali)yli) a)id /)eti) anhydride /)etylsali)yli) a)id /)eti) a)id
.n acidic or 1asic media, as*irin is hydrolyAed to give its active form ? salicylic
acid, The hydrolysis reaction of as*irin, ho6ever, ta:es *lace in 1asic condition much
faster than in acidic condition, This illustrates a very im*ortant *rinci*le: the sta1ility
of drugs and their mechanisms strongly de*end on the *H condition of the 1ody,
.n general, the hydrolysis of esters may 1e catalyAed 1y either acid or 1ase, The
detailed mechanism of hydrolysis reactions has 1een the su1Pect of an enormous
0

46
th
research effort, since they are of such fundamental im*ortance, The generally
acce*ted mechanism of acid31ase3catalyAed hydrolysis is :no6n& ho6ever many
researchers *articularly in 1iotechnology are a**lying this fundamental :no6ledge in
ne6 and more com*licated systems,
This e(*eriment deals 6ith 1oth the synthesis of as*irin and :inetic study of the
hydrolysis of as*irin under a 1asic condition, -or:ing 6ith synthesis of as*irin, the
*re*arative method uses acetic anhydride and an acid catalyst, concentrated sulfuric
acid, to s*eed u* the reaction 6ith salicylic acid, Then the hydrolysis of as*irin 6ill 1e
studied under *seudo3order conditions, This 6ill allo6 the order 6ith res*ect to
as*irin concentration to 1e determined, The order 6ith res*ect to the concentration of
hydro(ide ions 6ill 1e given and from this data you 6ill 1e as:ed to dra6 conclusions
a1out the mechanism,
3 0ure salicylic acid CH
"
C/
)
C
$
H
!
C/
)
H
3 5cetic anhydride CH
"
C
)
/
"
CH
"
3 Concentrated sulfuric acid

H
)
S/
!
3 51solute ethanol C
)
H
#
/H,
3 Standard Na/H solution,
3 UV3Vis S*ectro*hotometer
3 Thermostat
3 Stirrer hot*late
3 5nalytical 1alance Gm 0,000% gH
3 @ea:er glass, %00 mD
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, %

46
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3 Erlenmeyer flas:, %00 mD
3 0i*ette, # mD
3 @rchner flas: G'ilter flas:H
3 @rchner filter
3 'ilter *a*er
3 7lass rod
3 Sto*6atch
,tep 1( ,ynthesis o. a)etyl sali)yli) a)id
%, 0re*are a 1ath using a !00 mD 1ea:er filled a1out half36ay 6ith 6ater, Heat to 1oil,
), -eigh ),0 g salicylic acid using an analytical 1alance and *lace it in a %00 mD
Erlenmeyer flas:, Use this 4uantity of salicylic acid to calculate the theoretical or
e(*ected yield of as*irin,
", Carefully add #,0 mD of acetic anhydride 1y *i*ette to the Erlenmeyer flas:
containing the acid,
!, 5dd a1out #3$ dro*s of concentrated sulfuric acid as catalyst,
CationH "cetic anhydride cou1d irritate your eyes+ Su14uric acid cou1d cause burns
to the s-i11+ 2and1e both chemica1s Fith care+
#, Mi( the reagents and then *lace the Erlenmeyer flas: in 1oiling 6ater 1ath, Heat
for %# min, The solid 6ill com*letely dissolve, S6irl the solution occasionally,
$, 5dd %0,0 mD 6ater to the Erlenmeyer flas:, sha:e the flas: thoroughly, and then
*lace it in an ice 1ath for %03%# min to crystalliAe out the entire *roduct,
acetylsalicylic acid, Collect the crystals 1y filtration under vacuum, .f the
crystalliAation ta:es *lace slo6ly, scratch gently inside the flas: 6ith a glass rod,
)

46
th
9, 8e3crystaliAe the crude *roduct as follo6: ;issolve the crude *roduct in %0,0 mD
ethanol, then *our the ethanol solution into $0,0 mD 6arm 6ater and *lace the
o1tained solution in the ice 6ater for %03%# min, 'ilter off the *roduct,
, ;ry the *roduct in an oven at %00
o
C for "0 min, -eigh the dried *roduct,
,tep 2( %ydrolysis o. a)etylsali)yli) a)id
%, 0re*are #0,0 mD of a #>%0
?"
M solution of salicylic acid in )0T ethanol and
a**ro(, Na/H #>%0
?"
M solution as follo6s:
iH -eigh out the re4uired amount of salicylic acid GM = %",% g mol
?%
H in small
1ea:er on an analytical 1alance,
iiH ;issolve the 6eighed acid in %0,0 mD ethanol,
iiiH Transfer this 4uantitatively into a #0 mD volumetric flas: already containing
#,0 mD #>%0
?)
M Na/H, 6ash the vial several times and add 6ater to the mar:,
), 0re*are #0,0 mD of a #>%0
?!
M solution of salicylic acid as follo6s:
iH 0lace %0,0 mD ethanol in a #0 mD volumetric flas:, add 1y *i*ette to this flas: #
mD solution *re*ared in ste* %,
iiH 5dd a re4uired amount of #>%0
?"
M Na/H solution to fill u* to the mar:, 0lace
the flas: in a heated 1ath at "9
o
C,
", Measure the a1sor1ance at )E# nm, This 6ill 1e the 5
s
in the su1se4uent
calculation G,ote: @efore measuring the a1sor1ance of salicylic acid, the UV3Vis
s*ectro*hotometer should 1e Aeroed 6ith standard sam*le, Standard sam*le is a #>%0
?
"
M Na/H solution containing )0T ethanolH,
!, 0re*are #0 mD of a #>%0
3!
M solution of acetylsalicylic acid G)3
CH
"
C/
)
C
$
H
!
C/
)
HH as descri1ed in *arts % and ) a1ove,
#, 0lace the reaction 1ottle in a thermostated 1ath at "9
o
C, Start counting the reaction
time as soon as the solution is *laced in the 1ath,
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, "

46
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$, 'ive minutes after the start of the reaction, transfer a sufficient amount of
the reaction solution into % cm UV3Vis a1sor*tion cuvette and measure the
a1sor1ance at )E# nm, Continue recording the a1sor1ance every # min until the
reaction time reaches $0 min, -rite do6n the o1tained e(*erimental data in the ta1le
TimeOmin # %0 )0 "0 !0 #0 $0 s
51sor1ance
5
2( >estion and data analysisA
%, Calculate the yield of the reaction,
), 5s*irin can irritate the stomach, -hat is usually done in the formulation of the drug
that reduces this side effectR
", Calculate the concentration of Na/H in # > %0
?!
M solution of as*irin,
!, 0lot G5
s
3 5H vs, t, lnG5
s
3 5H vs, t, and vs, t on three se*arate charts,
'rom these *lots determine the order 6ith res*ect to acetylsalicylic acid,
#, ;etermine the value of the *seudo3order rate constant, -
o1s
, Calculate the half3life of
the hydrolysis under the reaction condition used, 'or ho6 many half3lives 6as the
reaction allo6ed to runR
$, .n 1asic solution, acetylsalicylic acid e(ists as an anion,
COO
D
O
O CH
3
The follo6ing mechanism has 1een *ro*osed to account for the 1ase catalyAed
hydrolysis of as*irin, @ased on the order 6ith res*ect to as*irin, and given the order
6ith res*ect to [/H
?
Z = %, derive the rate la6 and indicate 6hich of the follo6ing
reactions is the rate 3 determining ste*,
!

46
th

Problem 3$. Comple! formation of ferric ion and salicylic acid
1( Introd)tion
.n this sim*le e(*eriment 6e 6ill study the com*le( formation of 'e
"L
and
salicylic acid in the a4ueous solution, The em*irical formula of the com*le( 6ill
1e determined and also its sta1ility constant can 1e estimated,
!$
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.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, #

46
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Several sta1le com*le(es 1et6een ferric ion and salicylic acid H
)
Sal
have 1een :no6n, Their structures and com*ositions are much de*endent on *H,
.n acidic solution, a violet com*le( is formed, 5t neutral *H, a different dar:3red
com*le( forms, and in 1asic solution the com*le( that forms is orange, This
e(*eriment 6ill 1e carried out at *H of a1out ), Under this condition, the
hydrolysis of ferric ion is largely su**ressed, To sim*lify the calculations, 6e 6ill
not consider to the dissociation of H
)
Sal during the com*le( formation, Thus,
regardless of the structure of the com*le(, 6e can *resent the com*le( formation
e4uili1rium as:
'e
"L
L n H
)
Sal 'e
"L
GH
)
SalH
n
Thus, the sta1ility constant C
f
is defined as
n
n
4
Sa1 2 Fe
Sa1 2 Fe
K
Z Z[ [
Z H G [
)
"
)
"
+
+
=
G%H
6here the ['e
"L
Z and [H
)
SalZ

refer to the concentrations of the free s*ecies,

The com*le( 'e
"L
GH
)
SalH
n
a1sor1s most strongly at #) nm Gand neither 'e
"L
nor
H
)
Sal a1sor1 at this 6avelengthH, .ts concentration is related to the o*tical
a1sor1ance through @eerMs la6, 6hich is:
5 = ()l) ['e
"L
GH
)
SalH
n
Z
6here t is the molar e(tinction coefficient for the com*le( and l is the o*tical *ath length,
2o1Ms method can 1e used to find the em*irical formula of the com*le(, 'ollo6ing
this method, e4uimolar solutions of 'e
"L
and H
)
Sal are *re*ared, and then mi(ed in
ratios of %:E& ): Q E:%, The total reagent concentrations therefore are the same in
each solution, Ma(imum amount of e4uili1rium com*le( 6ill 1e formed 6hen
the *ro*ortions of reagents em*loyed corres*ond to the em*irical formula of the
com*le( and can 1e deduced through the measurement of o*tical a1sor1ance,
$

46
th
2( Chemi)als and #ea@entsA
3 5 solution of 0,00)# M 'e
"L
made 1y dissolving the a**ro*riate amount of
ferric ammonium sulfate in #00 mD of 0,00)# M sulfuric acid,
3 5 solution of 0,00)# M salicylic acid made 1y dissolving the a**ro*riate
amount of salicylic acid in #00 mD 0,00)# M sulfuric acid,
3 Saturated solution of salicylic acid Ga1out #0 mDH in 0,00)# M sulfuric acid,
1( /pparatses and ;lass'areA
o 7lass 1ea:er: %00 mD, #0 mD
o @urette: )# mD,
o Volumetric flas:: #00 mD,
o -ash 1ottle,
o Electronic 1alance 6ith reada1ility of 0,000% g,
o UV3vis s*ectro*hotometer,
o 7lass cuvettes,
,tep 1( 3etermine the empiri)al .ormla o. the )ompleG by ?obIs-method
%, 0re*are in %00 mD 1ea:ers Gshould 1e dry and )leanH a series of nine mi(tures
of the 0,00)# M ironG...H and the 0,00)# M salicylic acid solutions, *lus %0,0 mD
0,00)# M:
!$
th

46
th
Mi(ture % ) " ! # $ 9 E
V
mD
.ronG...H %,00 ),00 ",00 !,00 #,00 $,00 9,00 ,00 E,00
V
mD
salicylic acid E,00 ,00 9,00 $,00 #,00 !,00 ",0 ),00 %,0
V
mD
0,00)# M
HCl
%0,00 %0,00 %0,00 %0,00 %0,00 %0,00 %0,00 %0,00 %0,00
GNote: (se burette to ta-e vo1umes o4 the so1utionH
), Measure the a1sor1ance of each mi(ture,
", 0lot a1sor1ance versus volume of 'e
"L
, 51sor1ance should 1e highest for the
stoichiometric mi(ture,
,tep 2( 3etermine the molar eGtin)tion )oe..i)ient J o. the )ompleG
%, 0i*ette out %,00, ),00, ",00, !,00, #,00, $,00 mD of 0,00)# M ironG...H solution
into # 1ea:ers G%00 mDH, To each 1ea:er add %0,00 mD of saturated salicylic acid
solution and enough 0,00)# M HCl solution to 1ring the total volume to )0,00 mD,
), Measure the a1sor1ance of each solution,
", 0lot a1sor1ance versus ['e
"L
Z G@ecause the salicylic acid is in e(cess, it is
assumed that the concentration of iron e4uals the concentration of the com*le(H,
!, Calculate t from the linear *lot,
,tep 1( 3etermine the stability )onstant =
.
%, 0re*are Gin %00mD 1ea:ersH three mi(tures of the same volumes of 0,00)# M
.ronG...H and the 0,00)# M salicylic acid solutions and *lus 0,00)# M HCl solution
to total volume of )0 mD:
Mi(ture % ) "
V
mD
0,00)# M .ronG...H #,00 !,00 ",00
V
mD
0,00)# M salicylic acid #,00 !,00 ",00

46
th
V
mD
0,00)# M HCl %0,00 %),00 %!,00
), Measure the a1sor1ance of each solution,
", Calculate the initial concentration of 'eG...H and H
)
Sal in each solution,
!, 'rom the measured a1sor1ance and o1served value determined in ste* )G!HH,
Calculate the concentration of the com*le( in each solution,
#, Calculate the e4uili1rium concentration of 'eG...H and H
)
Sal, 5ssume that:
['e
"L
Z
e4uili1rium
= ['e
"L
Z
initial
3 ['e
"L
GH
)
SalH
n
Z
[H
)
SalZ
e4uili1rium
= [H
)
SalZ
initial
? n > ['e
"L
GH
)
SalH
n
Z
$, Calculate the e4uili1rium constants C
e4
for each solution Gusing e4uation %H and
determine an average value,
2( >estions and /nalysis
1( -hat is the em*irical formula of the com*le(R
2( The a1ove com*le( is normally re*orted as ['eGSalHZ
L
in 6hich the salicylic
ligand is dou1ly de*rotonated,
),% -rite the chemical e4uation in the ionic form to the formation of ['eGSalHZ
L
,
),) Det formulate the sta1ility constant of the ion com*le( ['eGSalHZ
L
from
o1served C
e4
, [H
L
Z, C
a%
and C
a)
of H
)
Sal,
)," *C
a%
and *C
a)
values of H
)
Sal are ),E and %",$0, res*ectively G6R6 2andboo- o4
6hemistry and /hysics, 6R6 /ress, 200A, + 124C)+ Calculate the sta1ility constant GC
f
H
of the ion com*le( ['eGSalHZ
L
for each solution Gin section ),"H and determine an
average value, 5ssume that the dissociation of H
)
Sal can 1e ignored, (2int! L2
=
M
e'
. 0+002< = 2 N n N LFe
A=
(2
2
Sa1)
n
M)+
),!, Comment on your C
f
value and e(*lain the *ro1a1le errorsR
3333333333333333333333333333 EN; 333333333333333333333333333333
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, E

46
th
/PPE63ICE,
/PPE63IC /
A 1: *A!E+ ,-.E* !/, *-0EN* 1N 2E .AB/,A/,+
5ll students of chemistry must recogniAe that haAardous materials cannot 1e
com*letely avoided, Chemists must learn to handle all materials in an a**ro*riate
fashion, -hile it is not e(*ected that all students *artici*ating in the .nternational
Chemistry /lym*iad :no6 the haAards of every chemical, the organiAers of the
com*etition 6ill assume that all *artici*ating students :no6 the 1asic safety
*rocedures, 'or e(am*le, the organiAers 6ill assume that students :no6 that
eating, drin:ing or smo:ing in the la1oratory or tasting a chemical is strictly
for1idden,
.n addition to the common3sense safety considerations to 6hich students should
have 1een *reviously e(*osed, some s*ecific rules, listed 1elo6, must also 1e
follo6ed during the /lym*iad, .f any 4uestion arises concerning safety *rocedures
during the *ractical e(am, the student should not hesitate to as: the nearest
su*ervisor for direction,
E0

46
th
#les re@ardin@ personal prote)tion
%, Eye *rotection must 1e 6orn in the la1oratories at all times, .f the student 6ears
contact lenses, full *rotection goggles must also 1e 6orn, Eye *rotection 6ill 1e
*rovided 1y the host country,
), 5 la1oratory coat is re4uired, Each student 6ill su**ly this item for
himselfOherself,
", Dong *ants and closed3toed shoes are recommended for individual safety, Dong
hair and loose clothing should 1e confined,
!, 0i*etting 1y mouth is strictly for1idden, Each student must 1e *rovided 6ith
*i*ette 1ul1 or *i*ette filler,
#les .or %andlin@ 0aterials
%, S*ecific instructions for handling haAardous materials 6ill 1e included 1y the
host country in the *rocedures of the *ractical e(am, 5ll *otentially dangerous
materials 6ill 1e la1eled using the 7HS sym1ols, Each student is res*onsi1le for
recogniAing these sym1ols and :no6ing their meaning Gsee 5**endi( @H,
), ;o not indiscriminately dis*ose chemicals in the sin:, 'ollo6 all dis*osal rules
*rovided 1y the host country,
A 2: *A!E+ ,-.E* AN0 ,EC/&&EN0A1/N* !/, 2E 2/*
C/-N,+ /! 2E 1NE,NA1/NA. C2E&1*,+ /.+&P1A0
Certainly it can 1e assumed that all students *artici*ating in the .Ch/ have at least
modest e(*erience 6ith safety la1oratory *rocedures, Ho6ever, it is the
res*onsi1ility of the .nternational 2ury and the organiAing country to 1e sure that
the 6elfare of the students is carefully considered, 8eference to the Safety 8ules
for Students in the Da1oratory 6ill sho6 that the students carry some of the 1urden
for their o6n safety, /ther safety matters 6ill vary from year to year, de*ending on
*ractical tas:s, The organiAers of these tas:s for the host country are therefore
assigned res*onsi1ility in the areas listed 1elo6, The organiAers are advised to
carefully test the *ractical tas:s in advance to ensure the safety of the e(*eriments,
!$
th
.Ch/ 0re*aratory 0ro1lems, Hanoi, Vietnam, 2uly )0%!, E%

46
th
This can 1est 1e accom*lished 1y having students of a1ility similar to
that of .Ch/ *artici*ants carry out the testing,
/PPE63IC B
2A3A,0 WA,N1N4 *+&B/.* AN0 2A3A,0 0E*14NA1/N*
Chemicals used in the .Ch/ la1oratory e(*eriments need to 1e la1eled according
to the 7lo1ally HarmoniAed System of Da1elling of Chemicals G7HSH standard
develo*ed 1y the United Nations, The organiAing country should use the locally
legislated 7HS system G*ictograms, haAard statements, etc,H if it e(ists, .f such
rules do not e(ist, the original 7HS directives
Ghtt*:OO666,unece,orgOtransOdangerO*u1liOghsOghsu6elcomeue,htmlH and the 7HS
com*liant documentation 1y the chemical *roviders should 1e used,
E)

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Preparatory Problems

) are the 1ond moments for 5@ and

@esides com*le(ation reaction 1et6een W

, an al:aloid o1tained from Tru(illo cocaH

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