IChO 1999, Теория — Задача 4. Problem 4
Thirty-first International Chemistry Olympiad — 1999 — Theoretical problems (Volume 2, 2009)
Внимание: Бележка към темата
Attributed archive/compiler teaching source. Retain the Volume 2 attribution and native copying conditions; the printed teaching grant does not establish a broader commercial licence. This 2009 collection is not an unchanged complete jury packet: the editorial preface describes recreated presentation and schemes, numerical corrections, brief keys and omitted practical material. Printed errors, absent measurements, incomplete methods, missing forms and missing answers remain disclosed.
Compilation edition and teaching attribution
Anton Sirota (editor), The Competition Problems from the International Chemistry Olympiads, Volume 2, IChO International Information Centre, Bratislava, IUVENTA, 2009.
Attributed archive/compiler teaching source. Retain the Volume 2 attribution and native copying conditions; the printed teaching grant does not establish a broader commercial licence. This 2009 collection is not an unchanged complete jury packet: the editorial preface describes recreated presentation and schemes, numerical corrections, brief keys and omitted practical material. Printed errors, absent measurements, incomplete methods, missing forms and missing answers remain disclosed.
Native copyright and teaching-copy conditions
THE COMPETITION PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS,
Volume 2
21st – 40th IChO (1989 – 2008)
Editor: Anton Sirota
ISBN 978-80-8072-092-6
Copyright © 2009 by IUVENTA – IChO International Information Centre, Bratislava, Slovakia
You are free to copy, distribute, transmit or adapt this publication or its parts for unlimited teaching purposes,
however, you are obliged to attribute your copies, transmissions or adaptations with a reference to "The
Competition Problems from the International Chemistry Olympiads, Volume 2" as it is required in the
chemical literature. The above conditions can be waived if you get permission from the copyright holder.
Issued by IUVENTA in 2009
with the financial support of the Ministry of Education of the Slovak Republic
Number of copies: 250
Not for sale.
International Chemistry Olympiad
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811 04 Bratislava 1, Slovakia
Phone: +421-907-473367
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E-mail: anton.sirota@stuba.sk
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Native editorial preface
Preface
Preface
Preface
Preface
This publication contains the competition problems (Volume 2) from the 21st – 40th
International Chemistry Olympiads (IChO) organized in the years 1989 – 2008 and is a
continuation of the publication that appeared last year as Volume 1 and contained
competition problems from the first twenty IChOs. The whole review of the competition
tasks set in the IChO in its fourty-year history is a contribution of the IChO International
Information Centre in Bratislava (Slovakia) to the development of this world known
international competition. This Volume 2 contains 154 theoretical and 46 practical
competition problems from the mentioned years. The review as a whole presents
altogether 279 theoretical and 96 practical problems.
In the elaboration of this collection the editor had to face certain difficulties because
the aim was not only to make use of past recordings but also to give them such a form
that they may be used in practice and further chemical education. Consequently, it was
necessary to make some corrections in order to unify the form of the problems. However,
they did not concern the contents and language of the problems.
Unfortunately, the authors of the particular competition problems are not known and
due to the procedure of the creation of the IChO competition problems, it is impossible to
assign any author's name to a particular problem. As the editor I would appreciate many
times some discussion with the authors about any critical places that occurred in the text.
On the other hand, any additional amendments to the text would be not correct from the
historical point of view. Therefore, responsibility for the scientific content and language of
the problems lies exclusively with the organizers of the particular International Chemistry
Olympiads.
Some parts of texts, especially those gained as scanned materials, could not be used directly and thus, several texts, schemes and pictures had to be re-written or created again. Some solutions were often available in a brief form and necessary extent only, just for the needs of members of the International Jury.
Recalculations of the solutions were made in some special cases only when the numeric results in the original solutions showed to be obviously not correct. Although the numbers of significant figures in the results of several solutions do not obey the criteria generally accepted, they were left without change.
In this publication SI quantities and units are used and a more modern method of
chemical calculations is introduced. Only some exceptions have been made when, in an
effort to preserve the original text, the quantities and units have been used that are not SI.
There were some problems with the presentation of the solutions of practical tasks,
because most of the relatively simple calculations were based on the experimental results
of contestants. Moreover, the practical problems are accompanied with answer sheets in
the last years and several additional questions and tasks have appeared in them that were
not a part of the text of the original experimental problems. Naturally, answer sheets could
not be included in this publication and can only be preserved as archive materials.
When reading the texts of the IChO problems one must admire and appreciate the work of those many known and unknown people – teachers, authors, pupils, and organizers – who contributed so much to development and success of this important international competition.
I am sure about the usefulness of the this review of the IChO problems. It may serve not only as archive material but, in particular, this review should serve to both competitors and their teachers as a source of further inspiration in their preparation for this challenging competition.
Bratislava, July 2009
Anton Sirota, editor
Условие
Ligand L forms complexes with many transition metals. Heat bipyridine, glacial acetic acid and hydrogen peroxide at for three hours. Product L crystallizes as fine needles, molecular mass 188. The analogous pyridine reaction is shown.

Iron and chromium complexes are (A) and (B).
| Table 4a: complex | Elemental analysis / wt.% |
|---|---|
| A | Fe 5.740; C 37.030; H 3.090; Cl 10.940; N 8.640 |
| B | Cr 8.440; C 38.930; H 2.920; Cl 17.250; N 9.080 |
Atomic numbers: Cr 24, Fe 26. Relative atomic masses: H 1, C 12, N 14, O 16, Cl 35.45, Cr 52, Fe 55.8.
| Table 4b: complex | Magnetic moment / B.M. | Colour |
|---|---|---|
| A | 6.13 | Yellow |
| B | Not measured | Purple |
| Table 4c: absorbed wavelength / nm and colour | Complementary colour |
|---|---|
| 400, violet | Yellow green |
| 450, blue | Yellow |
| 490, blue green | Orange |
| 500, green | Red |
| 570, yellow green | Violet |
| 580, yellow | Blue |
| 600, orange | Blue green |
| 650, red | Green |
Ligand and complexes
4.1
Write L's molecular formula.
4.2
If L is bidentate and chelating, draw the bipyridine used and L.
4.3
Does L have a net charge?
4.4
Draw one molecule L bound to metal ion M.
4.5
Use Table 4a to determine A's empirical formula. Find ; write its complete formula in usual IUPAC notation. Find the cation:anion ratio on dissolution in water.
4.6
Find Fe's oxidation number and d-electron count in A. Write possible high- and low-spin configurations. Which is correct, and what is the best supporting evidence?
4.7
Estimate A's in nm from Table 4c.
4.8
Detailed analysis shows B contains Cr³⁺. Calculate its spin-only magnetic moment.
4.9
B is a 1:1 electrolyte. Determine its empirical formula and .
Source notes
Attributed Volume 2, Anton Sirota / IChO International Information Centre / IUVENTA, Bratislava, 2009; physical318–322, printed720–724. The key prints C₂₁ rather than O₂₁ in A's empirical formula and Cr₂₀ rather than a Cr/C₂₀ sequence in B's formula. The elemental table and both literal formulas remain visible without a silent correction. Native diagrams, resonance alternatives, electron arrows and supplied data are retained. Teaching copying, distribution and adaptation require Volume 2 attribution; no blanket commercial permission is asserted.
Решение
4.1
Bipyridine is simply oxidized to bipyridine oxide. Bipyridine has molecular mass 156, versus 188 for L. The difference 32 represents two oxygen atoms: .
4.2
The native key retains bipyridine and three drawings of L, including charge-separated representations.

4.3
L has no net charge.
4.4

4.5
| Calculation for A | Fe | C | H | Cl | N | O |
|---|---|---|---|---|---|---|
| % | 5.740 | 37.030 | 3.090 | 10.940 | 8.640 | 34.560 |
| mol | 0.103 | 3.085 | 3.090 | 0.309 | 0.617 | 2.160 |
| mol ratio | 1.000 | 29.959 | 30.00 | 2.996 | 5.992 | 20.971 |
| atom ratio | 1 | 30 | 30 | 3 | 6 | 21 |
Oxygen percentage is by difference. The next native sentence prints the empirical formula as , despite the table's oxygen column. Since it has one Fe atom, empirical and molecular formulas are equivalent here. With L's formula obtained previously (referred to as “(4a) and (4b)” in the key), .
Complete formula: . Cation:anion ratio is 1:3. Three perchlorates dissociate freely, giving and in solution.
4.6
Fe oxidation state is +3 (III); it has five d electrons. The native configurations are retained.

High spin is correct. Best evidence is magnetic moment. The spin-only relation is , with unpaired electrons. High spin gives B.M.; low spin gives B.M. The measured 6.13 B.M. is in the high-spin range.
4.7
Absorbed colour is complementary to observed colour, giving nm.
4.8
Cr³⁺ has , so B.M.
4.9
The native empirical formula is printed ; .
Оригинал в Архива: IChO 21st-40th.pdf · решение от архива: IChO 21st-40th.pdf · допълнителни данни: IChO 21st-40th.pdf · допълнителни данни: IChO 21st-40th.pdf