"CHEMISTRY REVIEW" PROJECT PAGES

This Project Page first appeared in the November 1996 issue of Chemistry Review, Volume 6, Number 2, Pages 14 and 15. Chemistry Review is published four times during the academic year by Philip Allan Updates and is a journal for post-16 students. It contains a variety of interesting and colourful articles aimed at 16-19 year-olds ta ing mainly !" and !# courses in chemistry. NOTE: Proje t Page is designed to hel! you thin" about your investigation# $t is not intended to be a set o% instru tions %or !ra ti al wor" and does not in lude a list o% sa%ety !re autions# C&'($)*R+ R'V$', a e!ts no res!onsibility i% Proje t Page is used in any way as a set o% instru tions#

Clock reactions
If you choose a project that e$plores the inetics of a chemical reaction you %ill need a %ay of measuring the rate of the reaction. &loc reactions provide an interesting %ay of doing this for some systems. In a typical reaction the first part of a graph sho%ing the concentration of product against time is appro$imately a straight line 'see (igure 1). If you choose any value of concentration that lies on this straight line 'say 1- the initial rate of reaction can be found by dividing this concentration by the time ta en to reach it .t1-#

&oncentration of products

c1 Initial rate of reaction *c1+t1

t1

Time

Figure 1 If you measure the time ta en for the same concentration to be reached in a series of reactions, you %ill be finding the time for the same amount of product to be formed for each reaction. The shorter the time, the faster the reaction is occurring. -ou can therefore ta e 1/t as a relative measure of the initial rate of reaction. The tric , of course, is no%ing %hen the fi$ed amount of product has been formed. The follo%ing e$amples illustrate ho% this can be done. Appearing blue There are a number of so called .iodine cloc . reactions in %hich molecular iodine is one of the products. Probably the most famous of these is the reaction involving hydrogen pero$ide and iodide ions in acid solution/ 0#1# 2 #I3 2 #02 4 I# 2 #0#1

The inetics of this reaction %ere first investigated by 5ernon 0arcourt and 6illiam 7ssen, and the reaction is still referred to as the 0arcourt-7ssen reaction. In your project you %ill need to add the same, fi$ed amount of sodium thiosulphate solution together %ith a little starch solution to your reactants in each e$periment. The molecular iodine produced by the main reaction bet%een hydrogen pero$ide, iodide and acid immediately reacts %ith the thiosulphate ions/ I# 2 #"#18#3- 4 "916#3 2 #I3 6hen all of the thiosulphate has been used up, the iodine accumulates in the solution and reacts %ith the starch to give a distinctive blue-blac colour. The time from mi$ing the reactants to the appearance of the blue colour is therefore the time for a fi$ed amount of iodine to be formed. The appearance of the blue colour is li e a motor race che:uered flag; it tells %hen a particular amount of product has been formed ho%ever long it ta es for this to happen. -ou can simply use 1/t as a measure of the rate of reaction. No% that you have a method of monitoring the rate of reaction you can loo at ho% different factors affect it. -ou could separately change the concentrations of each reactant, you could try the e$periment at different temperatures or investigate the effects of a catalyst such as ammonium molybdate'5I). !nother iodine cloc reaction is that bet%een pero$ydisulphate'5I) and iodide ions/ "#1<#3 2 #I3 4 #"19#3 2 I#

!gain, the same, small, fi$ed amount of thiosulphate ions and some starch solution are added to the reaction mi$ture in each e$periment. If you measure the time from mi$ing to appearance of the blueblac starch-iodine comple$ you can again use 1/t as your initial reaction rate. !s %ell as loo ing at the effects on the rate of changing concentrations and ternperature, you might li e to e$plore %hich d bloc ions catalyse the reaction. 6hen you first learnt about catalysts you might have been told that the amount of catalyst does not matter. =oes it matter in this reaction> Disappearing pink The ne$t e$ample is a ?bromine cloc @ reaction. -ou can use it to e$plore the inetics of the reaction bet%een bromide and bromate'5) ions in acid solution/ ABr3 2 Br183 2 602 4 8Br# 2 80#1

The time you %ill need to add a small amount of phenol solution and methyl orange solution to the reaction mi$ture. Colecular bromine produced in the main reaction reacts instantly %ith the phenol to form #,9,6-tribromophenol/

10 Br 8Br# 2

10 Br 2 80
2

2 8Br

Br

!s soon as the main reaction has produced sufficient bromine to react %ith the fi$ed amount of phenol, free bromine %ill appear in the solution. This bromine %ill immediately bleach the methyl orange solution/ Br# 2 methyl orange pin 'acid form) 4 bleached methyl orange 'colourless) 2 #Br3

The disappearance of the pin colour tells you that the fi$ed amount of product has been formed by the main reaction. 1/t is again a measure of the initial rate of reaction, and you can use it to investigate the effects of changing concentration and temperature. Disappearing blue -ou can use a slightly different type of cloc reaction to investigate aspects of the hydrolysis of #-D-#methylpropane %here D is chloro, bromo or iodo. These organic halogen compounds react %ith sodium hydro$ide solution/
&08 &08

08&

&

10

08&

&

10

&08

&08

If only a fraction, say 1EF, of the hydro$ide ions needed to react %ith all the halogen compound are added, the p0 %ill fall as they are used up. If %e have an indicator present, such as bromophenol blue, it %ould change colour %hen the p0 drops to a particular value. The time ta en from adding the sodium hydro$ide solution to the colour change is the time for a fi$ed amount of the halogen compound to react. The e$periment can be repeated using t%ice, three times, etc. as much of the sodium hydro$ide solution %ith the same amount of organic halogen compound. -ou can then plot a graph of the percentage hydrolysis against time. The slope of the straight part of the graph is the initial rate of the reaction. -ou could use this approach to compare the hydrolysis of the chloro, bromo and iodo compounds. To investigate the systems further you could find out ho% they are affected by temperature or by the nature of the solvent in %hich the organic halogen compound is dissolved.

Practical details
"uitable reaction mi$tures %hich you could modify to investigate the four treactions are as follo%s/ Hydrogen peroxide/iodide/acid reaction (Harcourt- ssen reaction! " 1E cm8 1 mol dm-8 sulphuric acid G #A cm8 E.1 mol dm-8 potassium iodide G A cm8 E.1 mol dm-8 hydrogen pero$ide 'this is appro$imately a ?1 volume@ solution) G 1E cm8 E.EEA mol dm-8 sodium thiosulphate G 1 cm8 starch solution Peroxydisulphate(#$!/iodide reaction G A cm8 E.E9 mol dm-8 potassium pero$ydisulphate'5I) G 1E cm8 1 mol dm-8 potassium iodide G 9 cm8 E.E1mol dm-8 sodium thiosulphate G 1 cm8 starch solution %ro&ate(#!/bro&ide/acid reaction G 1E cm8 E.EEA mol dm-8 potassium bromate'5) G 1E cm8 E.E1 mol dm-8 potassium bromide G 1A cm8 1 mol dm-8 sulphuric acid G A cm8 E.EEE1 mol dm-8 phenol G 8 drops of methyl orange indicator '1 g dm-8) Hydrolysis o' halogenoalkanes " 8 cm8 E.1 mol dm-8 #-D-#-methylpropane in a solvent such as propanone or methanol+%ater %here D is chloro, bromo or iodo G E.8 cm8 E.1 mol dm-8 sodium hydro$ide G 6.H cm8 distilled %ater G 8 drops bromophenol indicator 0ere" 0enby 0ere" 0enby is &ead o% Chemistry at 1ohn 2eggott College, ) unthor!e#

The original article was written by Derek Denby. We are grateful to Derek for allowing us to reproduce it here. This page is free for your personal use, but the copyright remains with Philip Allan Updates. Please do not copy it or disseminate it in any way. Chemistry Review is indebted to Don Ainley, who has helped to prepare this article for the Web.