45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions

45th Austrian Chemistry Olympiad

National Competition

Theoretical Tasks
May 30th, 2019

Solutions
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Problem 1 25 bp ≙ 7 rp

Mendeleev and the Elements

A. Mendeleev and his Rare Element

1.1 Calculate the binding energy of the 45Sc nucleus in MeV
21 ∙ 11 p +24 ∙ 10n → 45
21Sc

∆ m=( 21∙ 1.0072+ 24 ∙1.0087 )−44.9559=0.4041 u=6.712 ∙10−28 kg

2
E=∆ m∙ c 2=( 6.712∙ 10−28 ) ∙ ( 2.998 ∙ 108 ) =6.033 ∙ 10−11 J =3.764 ∙108 eV =376 MeV 2 bp

1.2 Calculate the coordination number of Scandium.

12 0.5 bp
1.3 Determine the number of atoms in the unit cell.
1
8 ∙ +1 ∙1=2 0.5 bp
8
1.4 Calculate the density of Scandium.
Number of Atoms per UC ∙ M 2 ∙ 45
ρ= = =2.989 g/cm 3 1 bp
N a ∙V 23
6.022∙ 10 ∙ 5 ∙10 −23

1.5 Add empirical formulae, names and general product names to the table below.
Name incl. oxidation no. of the cation Formula Product

Scandium(III) nitrate 0.5 bp Sc(NO3)3 Salt 0.5 bp

Scandium(III) oxide Sc2O3 0.5 bp a Salt

Hexafluoridoscandate(III) 0.5 bp [ScF6]3- Complex 0.5 bp

Chelate complex 0.5

Trioxalatoscandate(III) [Sc(C2O4)3]3– 0.5 bp
bp

1.6 Formulate a balanced equation for this reaction.

2 ScF3 + 3 Ca  2 Sc + 3 CaF2 1 bp

1.7 Determine the molar mass of Pretulite.

4M m 4M 1 4 m 4
m= →n= = ∙ = → =
NA M NA M NA M NA
m 4∙ M 1
ρ= = ∙
V N A a2 ∙ c
2
ρ ∙ N A ∙ a2 ∙ c 3.7 ∙ 6.022∙ 1023 ∙ ( 6.5806 ∙10−8 ) ∙ ( 5.806 ∙ 10−8 )
M= = =140 g/mol 3 bp
4 4
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
1.8 Elementary analysis revealed that Pretulite contains 32% (m/m) Scandium.
Determine the empirical formula of Pretulite.

0.32∙ 140
=1 Sc
45
∆ M =95 g / mol → P O43−¿ ¿
Sc [PO 4 ] 2 bp

1.9 Formulate an equation for this nuclear transformation.

45
Sc + 10n → 45 1
20 Ca+ 1 p or Sc(n,p) Ca
45 45
21 1 bp

1.10 Formulate the equation for this nuclear decay and state the type of decay.

46
Sc → 46 0
21 22 Ti + −1e + ν́

β– decay 1.5 bp

B. From Scandium to Titanium

1.11 Label the Pauli valence binding diagram and complete it for the given complex.

      

3d 4s 4p 2 bp
1.12 Determine hybridization of the central atom.
d2sp3 0.5 bp
1.13 Specify the magnetic behavior of the complex.
Paramagnetic 0.5 bp
1.14 Specify the spatial structure of the complex.
Octahedral 0.5 bp
1.15 Name the complex.
Hexaaquatitanium(III) 0.5 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
1.16 Draw the energy level diagram showing the configuration of the d electrons of the
metal ion in the complex and denominate the respective types of the energy states.

1 bp
1.17 Calculate the wavelength of the light the complex absorbs.

N A ∙ hc
Δ O=
λ
3 6.022∙ 1023 ∙6.626 ∙ 10−34 ∙2.998 ∙ 108
234 ∙ 10 =
λ
λ=511 nm
1.5 bp

1.18 Determine the color of an aqueous solution of this complex.

Reddish purple 0.5 bp

1.19 Sketch two possible spatial structures of [TiMe 5]– (Me … Methylide anion). Name the
respective geometrical shapes.

trigonal-bipyramidal and quadratic pyramidal, respectively

2 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Problem 2 87 bp ≙ 21 rp

Organic Chemistry and Music

A. AB(B)A – „Take a Chance on Me“

A.1. Synthesis of ABA (refer to the scheme on the next page):

O 1,5 bp
O O E
OEt
O
OEt KOH (cat.)
A EtOH O C
OEt

O 1,5 bp O
O
OEt
H2SO4 CH2OHCH2OH
1 bp B O D

O
O
3 bp
DIBAL-H OEt
Br CO2Me O
O 1,5 bp 1,5 bp
intoluene
in Toluen
O O Zn
O G O F
O

O
H

mCPBA

2 bp 2 bp z
+
H3O OH
CO2H
O O O O O
O O O
Abscisinsä ure
O
J
Abscisic acid
O I

m C P B A = m e t a - C h l o r p e r b e n z o e s ä u r e

mCPBA … meta-chloroperbenzoic acid

D I B A L - H = D i i s o b u t y l a l u m i n i u m h y d r i d

DIBAL-H … Diisobutyl aluminium hydride

45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions

2.1 Determine the structural formula of A (reaction scheme) and assign both 1H- and 13C-
shifts to the respective atoms. Hemiacetal
Aldehyde

O O O O
200 168
61
4,1 30 50 14
2,3 3,4 1,2 O
O
5 bp

2.2 Draw the structural formula of A when using a 1:1 mixture of D 2O/CD3CN as the
solvent during NMR measurements.

O O

OEt
D
D 2 bp

2.3 Give the empirical formula of J.

C15H20O4 2 bp

2.4 Determine the structural formulae B to J. Keep the correct stereochemistry in mind
(reaction scheme). 14 bp

2.5 Suggest a reagent z to transform J to Abscisic acid (reaction scheme).

NaOH 1bp

2.6 The step from E to F comprises introducing a widely used protective group. Which
concrete reaction during the following reaction process does it prevent from
happening?
AN with metalloorganic compounds from G to H / Oxidation of the ketone to the ester by
mCPBA 2bp

2.7 Demonstrate the reaction mechanism leading from E to F. Do not draw the entire
molecule, but only the respective functional group and the corresponding residues.
H
O
R'OH
+
OH OR'
O H+ - H+
R + R'OH H R R H
H H + OHR'
O OH
Halbacetal
Aldehyd
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Hemiacetal
Acetal

OR' H+ OR' -H2 O OR' +R'OH OR' -H+ OR'

R H R H R + H
R H R H
OH O O OR'
+ R'
H
+
H H Acetal
Halbacetal 4bp
2.8 Which reaction mechanism do the two reactions below follow? Use standard
acronyms.
F→G: Red G→H: AN / El 2 bp

2.9 Assign the respective wave numbers to the corresponding functional group by writing
them to the correct position of the respective structure of each of the three isomers.

2 bp

2.10 Well-known effects in Organic chemistry cause the differences in the spectral range at
1700 cm–1. Which of the following statements is true, and which one is false? Write “t”
for “true” and “f” for “false”.

t/f Statement
f Band shift to wavenumber 1730 cm-1 is a consequence of the –I
effect.
t C=O groups binding to two Alkyl groups absorb at lower
wavenumbers, than C=O groups binding to one alkyl group.
f Band shift to wavenumber 1680 cm-1 is a consequence of the –I
effect.
f Band shift to wavenumber 1730 cm-1 is a consequence of the +M
effect.
t Band shift to wavenumber 1680 cm-1 is a consequence of the +M
effect.
f Conjugation shifts wavenumbers to higher values.
f An absorption band of F2C=O occurs at lower wavenumbers, than
that of (CH3)2C=O.
t Conjugation shifts wavenumbers to lower values.
2 bp

A.2. Determining the structure of ABA:

45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
2.11 Calculate the empirical formula of ozonolysis product X.
C10H14O7 2.5 bp
2.12 Give the structural formulae of ozonolysis products X, Y and Z.

O O O O

OH OH HO
HO
COOH
O O O HO

Z Y
X 4.5 bp

2.13 Write the stereodescriptor(s) of Abscisic acid into the figure.

S, 2Z, 3E 1.5 bp
2.14 How many enantiomers of Abscisic acid exist?
2 enantiomers 1 bp
2.15 How many stereoisomers exist for the constitutional formula of Abscisic acid?
23 = 8 stereo isomers 1.5 bp

A.3. ABA Mechanism of action

2.16 Name the functional groups labeled with 1, 2, and 3, respectively.
1 = Lactam, 2 = Ester, 3 = Acetal 1.5 bp
2.17 Determine the stereo descriptors of the C atoms labeled a and b.
a:R b: S 3bp
2.18 Determine the number of stereogenic centers and label them with an asterisk (*) in
the structural formula.
8 stereogenic centers 1 bp

2.19 Calculate the maximum number of possible stereoisomers of this catabolite based on
the assumption that glucose is always present in its D-configuration and can only form
different anomers.
4
2 =16 stereo isomers
(all stereo centers in glucose are fixed, except for the anomeric C atom; plus three
further chiral centers  4 chiral centers) 2 bp

2.20 Assign the numbered signals in the 600 MHz-NMR-Spektrum to the respective
structure by writing the numbers to the respective protons. It is not possible to assign
all 7 signals explicitly.
4,5,6 and 7: Protons of the four methyl groups
3: Protons of the methoxy group
2: Protons af the vinyl group
1: Proton of the aldehyde function 2 bp
2.21 The structure contains hydrogen atoms, whose signals are not visible when recording
the NMR spectrum in a protic deuterated solvent, such as CD 3OD. Mark those
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
hydrogen atoms by encircling them in the structural formula.

2 bp

2.22 Determine the stereodescriptor at the position of the arrow.

Z configuration 1 bp

2.23 State which type of isomerism is present.

Diastereomerism, geometrical isomerism 1 bp

2.24 Correctly assign „Catabolite 1“ and „Oxidation product“ to the spectra.

Oxidation product Catabolite 1 2 bp

2.25 Deduce the color of each derivative.

Oxidation product: yellow Catabolite 1: colorless
2 bp

2.26 One of the two compounds requires less energy for electronic excitation. Calculate the
the energy of the photon that excites at the absorption maximum. Explicitly state the
wavelength underlying your calculation. State the color of the exciting light.
h ∙ c 6.6267015∙ 10−34 ∙ J ∙ s ∙ 299792458 ∙m ∙ s−1 −19
E= = =4.51∙ 10 ∙ J
λ −7
4.4 ∙ 10 ∙ m
Excitation light: blue 1.5 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
B. „Let´s twist again“

1,5 bp 2 bp
LiAlH4 1.MeSO2Cl

2.NaCN
CO2Et A B
OH CN

C9H14 O
H3O+

1 bp
I 3 bp
1,5 bp
H2, Pt, NEt3 I2

O
-HI NaHCO3
O
E C
COOH
O D
O

1,5 bp 1,5 bp
MeSO2 Cl, Py
CrO3
O
F OH
OH
G H
OSO2Me OSO2Me
OH

NaH DMF

1,5 bp
b
O

Twistan
Twistane

2.27 Determine the structural formulae A-E and G-I (reaction scheme) taking into account
correct stereochemistry. 13.5 bp

2.28 Name the reaction mechanism in the second step of A→B! Draw the structure of the
transition state.

NC C OSO2Me

SN2 2.5 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
2.29 Suggest reagents b for transforming I to Twistane; How is this name reaction called
und what is the underlying mechanism (first step)?
N2H4 / KOH
Wolff-Kishner reduction
AN 2 bp

2.30 What role does NaH play during step H→I? Tick the correct answer(s).

□ Oxidant
□ Reductant
□ Acid
◼ Base
□ Protective group
□ Catalyst
1 bp

2.31 Determine the symmetric elements of Twistane.

C2 axis, inversion center 2 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Problem 3 14 bp ≙ 4 rp

Electrochemistry: Copper and Other Metals

A. Composition of a 10-cent coin.

3.1 Formulate balanced equations for dissolving the soluble components of the coin in
diluted hydrochloric acid.
2 Al + 6 H3O+  2 Al3+ + 3 H2 + 6 H2O
Zn + 2 H3O+  Zn2+ + H2 + 2 H2O
Sn + 2 H3O+  Sn2+ + H2 + 2 H2O 1.5 bp

3.2 Specify the electrolyzed metal and calculate its mass fraction in the alloy.
Copper
n(Cu) = 0,0574 mol
M ∙ I ∙ t ∙ η 63.55 g mol−1 ∙13 A ∙16.71 min ∙ 60 s min−1 ∙ 0.85
m Cu =
( ) = =3.649 g
z ∙F 2∙ 96485 As mol−1
3.649
Cu: =89.0 % 2.5 bp
4.100

3.3 Calculate the mass fraction of tin in the coin.

m 0.213
n ( Komplex ) = = =0.0003457 mol=n(Sn)
M 616.11
m ( Sn ) =n ( Sn ) ∙ M ( Sn )=3.457 ∙10−4 ∙118.71 ≈ 0.0410 g
0.041
Sn: =1.0 % 1.5 bp
4.100

3.4 Calculate the mass fractions of the remaining two metals in the coin.

p ∙V 1.013 ∙105 Pa∙ 363.9 ∙10−6 m3

n ( H 2)= = ≈ 0.01488mol
R∙T 8.314 J mol−1 K −1 ∙ 298 K

n(H2) from Zn and Al: n(H2)total – n(Sn) = 0.01453 mol

n(H2) from Zn: x ; and n(H2) from Al: 1.5 y => x + 1.5 y = 0.01453

m(Zn) + m(Al) = 0.41 g => 65.41 x + 26.98 y = 0.41

From these two equations x and y can be calculated as:

x = 3.13·10-3 mol Zn ⇒ m(Zn) = 3.13·10-3  65.41 = 0.205 g
y = 7.60·10-3 mol Al ⇒ m(Al)=7.60·10-3  26.98 = 0.205 g
0.205 0.205
Zn: =5.0 % Al: =5.0 % 4.5 bp
4.100 4.100
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions

B. Electrochemistry of Real Gold

+¿+ 1,83 Au ¿
3+¿ x Au →
¿
Au →

+1.517

3.6 Calculate the missing potential x.

3 ∙1.517−1.83
x= =1.36 V 1 bp
2

3.7 Calculate the complex forming constant of [AuCl 4]– at 298 K from the given standard
potentials.
(1) Au3+ + 3 e– → Au EO1 = + 1.517 V ΔG O1 =– 439.1 kJ /mol
(2) [AuCl4]– + 3 e– → Au + 4 Cl– EO2 = + 1.002 V ΔGO2 =– 290.0 kJ /mol
One needs to calculate the equilibrium (=complex forming)constant β for the reaction:
(3) Au3+ + 4 Cl- ⇄ [AuCl4]-
(3) = (1) – (2) => Δ E 0 = 1.517 V – 1.002 V = 0.515 V
∆ GO3 = – 3∙F∙0.515 = –1.545∙F J / mol = –149.1 kJ/mol
1.545 ∙ F
∆ G O3 =−R ∙T ln β ⇒ ln β= =60.17 3 bp
R ∙T
β = 1.35∙1026
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Problem 4 32 bp ≙ 10 rp

Energy and Conjugated Systems

A. Propene
4.1 Calculate ΔrH°, ΔrS°, and ΔrG°, as well as Kp at 298K..
Δ r H ° =2⋅ 20.4−52.4 +7.7=−3,9 kJmol −1
Δ r S ° =2⋅266.8−219.3−301.0=13.3 Jmo l−1 K −1
Δ r G° =−3900−298 ⋅ 13,3=−7863 Jmo l−1=−7.9 kJmo l−1
−Δ R G

Kp=e RT
=¿ 23.9
4 bp

4.2 Calculate the heat that is set free at isobaric conditions when producing 1000kg
Propene at 436K.
Δ r C p =2⋅64.3−80.2−42.9=5.5 Jmol −1 K−1
Δ r H ° 436 = Δr H ° 298 + Δ r C p ⋅ ( 436−298 ) =−3141 Jmo l−1
M Propen =42.09 gmol−1 ⇒ 1000 kg ¿^ 2.376 ⋅104 mol
0.5 ∙ 2.376⋅10 4 mol ⋅−3141 Jmol −1 =¿ 3.73⋅10 7 J set free. 3.5 bp

4.3 Calculate ΔrH° and ΔrU° for for this reaction at 298K.
C3H8(g) + 5 O2 → 3 CO2(g) + 4 H2O(l) Δ c H °Propane
3 CO2(g) + 4 H2O(l) → C3H6(g) + 4,5 O2 – Δ c H °Propene
H2O(l) → H2(g) + ½ O2(g) – Δ c H °H 2O
C3H8(g) → C3H6(g) + H2(g) Δ r H❑°
Δ r H ° =−2220+2058+286.5=124.5 kJmol −1
Δ r U ° =Δ r H °− Δr nRT =122 kJmo l−1 3.5 bp

B. Propene in Action – the Allyl System

4.4 State the hybridization of the C atoms in the backbone shown
□ sp X sp2 □ sp3 □ sp3d2 □ die 3 C Atome sind verschiedene Hybride 0.5 bp
4.5 State the number of electrons
for for for
2 0.5bp 4 0.5bp 3 0.5 bp
4.6 State the number of antibonding nodal planes for the  molecular orbitals.
for φ1 for φ2 for φ3
0 0.5bp 1 0.5bp 2 1 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions

4.7 Give the correct term for E2, the energy of φ2. Insert the energy levels E1, E2, and E3 ,as
well as the parameter β including its sign into the diagram. Label them clearly.

E2 = α (2bp)

total 3.5 bp

4.8 Calculate the charges q1, q2, q3 at the C atoms C1, C2, and C3
For the allyl cation
only φ1 is occupied with 2 e
q 1=1−2 ⋅ ( 0.500 )2=0.5
q 2=1−2 ⋅ ( 0.707 )2 =0.0003 ≈ 0
q 3=q 1=0.5 1.5 bp

Draw the mesomeric resonance structures for the allyl cation

0.5 bp
Charges at the mesomeric structures and the calculated values for q1, q2, q3
X correspond □ do not correspond to each other 0.5 bp

For the allyl anion:

φ1 and φ2 are occupied with 2 e each
q 1=1−¿
q 2=1−2 ⋅ ( 0.707 )2 −2⋅0=0.0003 ≈ 0
q 3=q 1=−0.5
2 bp
Draw the mesomeric resonance structures for the allyl anion

0.5 bp
Charges at the mesomeric structures and the calculated values for q1, q2, q3
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions

X correspond □ do not correspond to each other 0.5 bp

4.9 Calculate the bond orders I12 and I23 of the allyl radical.
φ1 occupied with 2 e and φ2 with 1 e
I 12=2⋅ ( 0.500 ) ⋅ ( 0.707 )+1 ⋅ ( 0.707 ) ⋅0=0.707
I 23=2⋅ ( 0.707 ) ⋅ ( 0.500 )+ 1⋅ ( 0 ) ⋅ (−0.707 )=0.707
1.5 bp

C. Hexatriene
4.10 Specify the following points for hexatriene:
Total number of all atomic p-orbitals (attention: e.g. 3p are three orbitals) ∞ 1 bp
Number of atomic p-orbitals relevant for the Hückel approximation 6 0.5 bp
Number of resulting π – molecular orbitals 6 0.5 bp

4.11 Energies of the three orbitals increase as follows (Tick the correct one):
□ φ a , φ b ,φ c □ φb, φc , φa □ φ c , φb , φ a X φ b , φ a ,φ c 1 bp

4.12 Does one of the images show one of the orbitals mathematically expressed above? If
yes, specify, which one (φ a , φ b ,φ c).
A shows __________ B shows __________ C shows φa 0.5 bp

4.13 Specify the numbers of antibonding nodes.

A 2 B 0 C 3 0.5 bp

4.14 Draw the most energy-rich π-molecular orbital of Hexatriene in analogy to the
pictures above.

Backbone with number of nodes correct 1bp; also size ratios visible: 2.5 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Problem 5 27 bp ≙ 7 rp

Tartar Equilibrium

5.1 Give the empirical formula and the molar mass of potassium hydrogentartrate.
M ( K C 4 H 5 O 6 )=188.19 g /mol 1 bp

5.2 Calculate the solubility product of this salt at those conditions.

2.50 g / L
cKC H O = =0.0133 mol/ L
4
188.19 g/mol
5 6

K 17 ° 2
SP =c K C H O =0.000176
4 5 6
2 bp

5.3 Calculate the molar concentration of potassium hydrogentartrate in this wine. For
your calculation assume that the density of wine remains constantly at 1000 g/L
despite changing temperature.
1.13 g /L
cKC H O = =0.00600 mol/ L 1 bp
4
188.19 g/mol
5 6

5.4 How much – i.e. which mass – potassium hydrogencarbonate could one add to the
wine in Problem 5.3 per liter after partially removing potassium hydrogentartrate,
before one could expect that solid potassium hydrogentartrate forms anew. To
simplify the problem, assume that adding potassium hydrogencarbonate to the wine
does not substantially change the pH of wine and that hence the molar concentration
of hydrogentartrate ions does not change either. Use the solubility product calculated
in Problem 5.2. If you did not achieve a result there, use the value K 17 °
SP =¿0.0002.

K 17 °
SP =¿
¿¿
¿¿
m KHC O =¿ ¿ 3
4 bp

5.5 Calculate the sum of concentrations of all tartaric acid species in this wine.
2.50 g / L mol
cKC H O = =0.0133 =¿
4 5
188.19 g/mol
6
L
0.0133∙ 10−3.1
K A 1 =¿ ¿ ⇒ 10
−2.98
=
[C 4 H 6 O 6 ]
⇒ [ C 4 H 6 O6 ] =¿0.0101 mol/L
K A 2=¿ ¿ ⇒ 10 −4.34
=¿ ¿
⇒ ¿0.000764 mol/L

c total =¿
6 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions

5.6 Calculate the concentrations of all tartaric acid species at this pH without considering
precipitation reactions. In case you did not get a result for the total concentration of
all tartaric acid species in Problem 5.5, use c tot =0.03 mol / L for your calculations.

c tot =0.0241 mol /L

[ C 4 H 6 O6 ] =s ¿ ¿
−3.45
K A 1 =¿ ¿ −2.98 h∙ 10
⇒ 10 = (1)
s
K A 2=¿ ¿ −4.34 t ∙ 10−3.45
⇒ 10 = (2)
h
s+h+ t=0.0241 (3)
−3.45
10
s=h ∙ = h ∙ 0.339
10−2.98
10−4.34
t=h ∙ −3.45 =h ∙ 0.129
10
h∙0.339 + h + h∙0.129 =0.0241
h = ¿ = 0.0164 mol/L s =[ C 4 H 6 O 6 ] = 0.00557 mol/L
t = ¿0.00212 mol/L 8 bp

5.7 Now, calculate the mass of solid potassium hydrogen tartrate precipitating after
adding potassium hydrogencarbonate in Problem 5.6. For the sake of simplicity,
assume that no hydrogentartrate is formed or consumed from other tartaric acid
species during this process. Furthermore, assume that all potassium that was initially
present in the wine originates from potassium hydrogentartrate.
Use the solubility product calculated in Problem 5.2. If you did not achieve a result
there, use the value K 17 °
SP =¿0.0002.

1.5 g
nK =0.0133 mol+ =0.0283 mol
gesamt
100.12 g/mol
K 17 °
SP =0.000176= ( 0.0283−x ) ∙ ( 0.0164−x )

x = 0.007811
m = 0.007810∙188.19 = 1.470 g 5 bp
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Problem 6 17 bp ≙ 5 rp

Kinetics

6.1 Determine the order of the reaction regarding the three species. Demonstrate your
line of thoughts.
1st order for [I-]; Comparing lines 1 and 2;
2nd order for [IO3-]; Comparing lines 1 and 3;
2nd order for [H+]; Comparing lines 1 and 4; 2 bp

6.2 Specify the rate law and calculate the rate constant k.
v = k [I-]1 [IO3-]2 [H+]2 = k·0.01·(0.1)2·(0.01)2 = 0.60
k = 0.60/1·10-8 = 6.0·107 mol-4· L4· s-1 1.5 bp

6.3 The activation energy of the reaction above at 25 °C is EA=84 kJ·mol-1. Calculate by
which factor the reaction rate increases, if one decreases the activation energy (e.g.
with a catalyst) by 10 kJ·mol-1.
before: k1 = A·e-EA1/RT; ln k1 = ln A – EAI/RT
after: k2 = A·e-EA2/RT; ln k2 = ln A – EA2/RT
ln (k2/k1) = – EA2/RT + EA1/RT = -74000/(8.314·298) + 84000/(8.314·298)
= - 29.87 + 33.90 = 4.03
k2/k1 = 56.3
The reaction proceeds 56.3 times faster! 2 bp

[ E ] tot ∙[ S]
6.4 Show that these assumptions allow you to derive the expression [ ES]= ,
K M +[S ]
k −a+ k b
where the Michaelis-Menten constant is K M = .
ka
Because of the steady state in ES one can write:
d [ES ]
=0=k a [ E ] [ S ]−k−a [ ES ] −k b [ ES ]=0
dt
[ Etot ]= [ E ] + [ ES ] → [ E ]= [ E tot ]−[ ES]
k a ( [ E tot ]−[ ES ] ) [ S ] =(k ¿ ¿−a+ k b )[ES ]¿
[ Etot ] [ S ] k a−[ ES ] [ S ] k a =(k −a +k b)[ ES]
[ Etot ] [ S ] k a=[ES](k −a+ k b +k a [ S ] )
[ Etot ] [ S ] k a
[ ES ] =
(k−a +k b +k a [ S ] )
[ Etot ] [ S ]
[ ES ] =
k−a + k b
+[S]
ka
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions

[ Etot ] [ S ]
[ ES ] = 4 bp
K M+ [ S ]

6.5 Show that the maximum reaction rate is ( ddt[ P] ) max

=v max=k b ∙ [E ]tot .

v= ( ddt[ P] )=[ ES]∙ k b

as the maximum case is that all E is present as ES, it follows that [ES]max = [E]tot =>
v max=k b ∙[E ]tot
1 bp
v max ∙[S ]
6.6 Derive the Michaelis-Menten equation v= from 6.4 and 6.5.
K M +[S]
d [ P]
v= ( )
dt
=[ ES]∙ k b

[ Etot ] [ S ] k b [ Etot ] [ S ]
nach 6.4: [ ES ] = => v=
K M+ [ S ] K M+ [ S ]

v max ∙ [ S ]
nach 6.5: v max=k b ∙[E ]tot => v= 1.5 bp
K M +[ S ]

6.7 Read the value for KM from the curve below showing v = f([S]).
If v = ½ ∙ vmax in equation 6.6, it follows that KM = [S],
Hence one has to read the [S] value corresponding to v = 1.5∙10 -6 mol L-1s-1.

1 bp
1 KM 1 1
6.8 Show that = ∙ + .
v v max [ S ] v max
v max ∙ [ S ] 1 K M +[ S ] 1 KM 1 1
From eq. 6.6: v= => = => = ∙ + 0.5 bp
K M +[ S ] v v max ∙ [ S ] v v max [ S ] v max

6.9 Determine the Michaelis constant KM and the rate constant kb from the Lineweaver-
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Burk- plot.

[S]0 10–6 in mol L-1 [S]0–1 in mol-1 L v0 10–5 in mol L-1min-1 v0–1 in mol-1 Lmin
3.0 3.33105 1.06 9.43104
5.0 2.00105 1.55 6.45104
10 1.00105 2.37 4.22104
20 0.50105 3.21 3.12104

1 KM 1 1
= ∙ +
v v max [ S ] v max
1 1
Intercept: =0 => =2∙ 104 mol−1 L min => vmax = 510–5 mol L–1min–1
[S ] v max
with [E]tot = 1,0∙10-9 mol L-1 it follows from 6.5 that: kb = 5∙104 min-1
The linear equation yields: KM = 1.1∙10-5 mol/L
2.5 bp
6.10 Calculate the fraction of enzyme molecules (fES) that bind substrate.
v0 [S ]0 3∙ 10−5 mol L−1
f ES = = = =0.67 1 bp
v max K M +[S ]0 1.5 ∙ 10−5 mol L−1 +3 ∙10−5 mol L−1
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
Problem 7 21 bp ≙ 6 rp

Evaporating and Cooling

7.1 Calculate the energy necessary to reheat the air in the room to 22°C (at atmospheric
pressure).
Ḿ =28.02 ⋅0.79+32.00 ⋅0.21=28.856 gmol −1; V =300m3
pv 101325 J m−3 ⋅300 m3
n= = =13642 mol cold air
RT 8.314 Jmo l−1 K −1 ⋅268 K
m air =13642 mol ⋅28.856 gmol−1=393664 g
J
q=c p ⋅ m⋅ ΔT =1.008 ⋅393664 g ⋅27 K =1.071⋅ 107 J =10.7 MJ 3 bp
gK

7.2 Calculate the number of gas bubbles occurring per second, assuming a mean bubble
diameter of 2mm.
4 r3 π 3
r = 1mm → V = =4.1888 mm ; → 0.18 L s−1=1.8 ⋅105 mm3 s−1
3
1.8⋅10 5 m m3 s−1 −1
Number of Bubbles = 3
=42972 s 1.5 bp
4.1888 m m

7.3 Tick the correct boxes

When rising through the column, pressure in the gas

□ increases
x decreases

□ Work is performed on the bubbles.

x The bubbles perform work.

This work needs to be

x added to/from the heat transferred by the
□ subtracted
gas to calculate the Enthalpy of Vaporization.
0.5pb each; 1.5 bp

7.4 Calculate the Enthalpy of Vaporization ΔvapH determined during the experiment above.
c p ΔT + Δp 1204 J m−3 K−1 ⋅ 32.5 K + 4128 J m −3 −1
Δ vap H= = =42.0 kJmol 1.5 bp
ρV 1.030 mol m−3
7.5 Use calculation to decide, if air or nitrogen had been used for the experiment.
At p = 1atm = 101325 Pa and T = 21.5°C (294.65K), 1m3 equals to 41.362 mol
1204 J m−3 K −1 −3 −1
−3
=29.1088 Jmo l K
41.362 mol m
29.1088 J mol−1 K −1 −1 −1 29.1088 J mol−1 K −1 −1 −1
−1
=1.039 J g K or −1
=1.008 J g K
28.02 gmol 28.865 gmol
45th Austrian Chemistry Olympiad – National Competition Theoretical Taksks - Solutions
This figure corresponds to that of air. Hence air was used. 3.5 bp

7.6 Calculate the vapor pressure of water above the salt solution from the vapor density
at temperature To.
nRT mol
p= =1.03 3 ⋅ 8.314 J K−1 mol−1 ⋅294.65 K =2523 Pa 2 bp
V m

7.7 Calculate the vapor pressure of pure water at To and tick the correct boxes.
J
Δ vap H ° =2463 ⋅ 18.02 g / mol=44383 Jmo l−1
g
−Δ vap H 1 1
ln p1=
R ( −
T1 T2
−1
)
+ln p2

44383 Jmo l 1 1
¿− −1 −1
8.314 Jmo l K ( −
294.65 K 289.15 K )
+ ln ( 1818.8 )=7.8506=¿ p1=2567 Pa

X The vapor pressure of water decreases by adding salt. 3 bp

7.8 Calculate the cooling power of the setup at this flow rate, i.e. at 150m 3/h.
E
=c p ΔT+ Δp=39130+ 4128=43258 J m−3
V
43258 J m−3 ∙ 150 m 3 h−1
Pcool= =1802.4 W 2.5 bp
3600 s h−1

7.9 Calculate the mechanical power of the air blower.

P=150 m3 ⋅ ( 3600 s )−1 ⋅262 mbar ⋅100 J m−3 mba r−1=1092 W 1 bp
7.10 Calculate the net cooling power of the setup (air blower + bubble evaporator).
2200−1092=1108 W generation of heat
Netto = Cooling – Heating = 1802 – 1108 = 694 W net cooling power. 1.5 bp