IChO 1990, Експеримент — Задача 4. Problem 4 — Kinetics of an SN1 Reaction

Twenty-second International Chemistry Olympiad — 1990 — Practical 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
International Information Centre
IUVENTA
Búdková 2
811 04 Bratislava 1, Slovakia
Phone: +421-907-473367
Fax: +421-2-59296123
E-mail: anton.sirota@stuba.sk
Web: www.icho.sk

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

In aqueous ethanolic solution, tert-butyl chloride (2-chloro-2-methylpropane) undergoes an SN1\mathrm{S_N1} nucleophilic substitution to form 2-methylpropan-2-ol and hydrochloric acid:

tert-BuCl+H2O=tert-BuOH+HCl.\text{tert-BuCl}+\mathrm{H_2O}=\text{tert-BuOH}+\mathrm{HCl}.

The rate law is:

d[HCl]dt=k1[tert-BuCl].\frac{d[\mathrm{HCl}]}{dt}=k_1[\text{tert-BuCl}].

The aim is to determine k1k_1 at ambient temperature.

Procedure

  1. Pipette 2.0 cm32.0\ \mathrm{cm^3} of tert-butyl chloride (flask 4.1 on the general-use bench) into a clean, dry 250 cm3250\ \mathrm{cm^3} ground-neck Erlenmeyer (conical) flask.
  2. As soon as possible, add 148 cm3148\ \mathrm{cm^3} of the aqueous ethanol solution (flask 4.2 on the general-use bench), measured with a graduated cylinder.
  3. Stopper the flask and stir vigorously with the magnetic stirrer. Start the timer. Carefully note the temperature T(0)T(0) of the solution.
  4. After approximately 55, 1515, 2525, 3535, 4545 and 5555 minutes, determined accurately, pipette 10.0 cm310.0\ \mathrm{cm^3} samples into 20 cm320\ \mathrm{cm^3} of an ice–acetone (propanone) mixture. Add two drops of bromothymol blue and titrate the liberated acid with Y mol dm−3Y\ \mathrm{mol\,dm^{-3}} aqueous sodium hydroxide; YY will be shown on the board.

Questions

4.1
The concentrations of tert-BuCl at t=0t=0 and tt are related by:

ln⁡[tert-BuCl]0[tert-BuCl]t=k1t.\ln\frac{[\text{tert-BuCl}]_0}{[\text{tert-BuCl}]_t}=k_1t.

Establish:

ln⁡V∞V∞−V=k1t,\ln\frac{V_\infty}{V_\infty-V}=k_1t,

where VV is the volume of sodium hydroxide used at time tt and V(8)V(8) is its value at t(8)t(8). The source defines:

t∞=t(8),V∞=V(8).t_\infty=t(8),\qquad V_\infty=V(8).

4.2
Calculate V(8)V(8). Density of tert-BuCl at 20 ∘C20\,{}^\circ\mathrm C: 850 kg m−3850\ \mathrm{kg\,m^{-3}}; molar mass: 92.5 g mol−192.5\ \mathrm{g\,mol^{-1}}.

4.3
Fill in the answer-sheet table with columns:

t (min),V (cm3),V∞,V,V∞V∞−V,ln⁡V∞V∞−V.t\ (\mathrm{min}),\quad V\ (\mathrm{cm^3}),\quad V_\infty,\quad V,\quad\frac{V_\infty}{V_\infty-V},\quad\ln\frac{V_\infty}{V_\infty-V}.

Draw the curve:

ln⁡V∞V∞−V=f(t).\ln\frac{V_\infty}{V_\infty-V}=f(t).

4.4
Determine k1k_1 (give the value of t(0)t(0)).

Source notes

The literal t(8)t(8) and V(8)V(8) notation, explicitly equated to infinity notation, is preserved. Question 4.4 asks for t(0)t(0), while the procedure records T(0)T(0). The key's derivative numerator lacks a dd; its concentration line uses VY10−2/10VY10^{-2}/10 before subsequent aY/10aY/10 expressions; the last expression uses numerator 170170, while n0n_0 uses 1.701.70. These printed differences are retained. No board value YY, measured times, titres, temperature, completed answer table, graph, numerical rate constant or worked answers to 4.3–4.4 are supplied.

Решение

Внимание: Непълно решение

The literal t(8)t(8) and V(8)V(8) notation, explicitly equated to infinity notation, is preserved. Question 4.4 asks for t(0)t(0), while the procedure records T(0)T(0). The key's derivative numerator lacks a dd; its concentration line uses VY10−2/10VY10^{-2}/10 before subsequent aY/10aY/10 expressions; the last expression uses numerator 170170, while n0n_0 uses 1.701.70. These printed differences are retained. No board value YY, measured times, titres, temperature, completed answer table, graph, numerical rate constant or worked answers to 4.3–4.4 are supplied.


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