Chemistry Individual Investigation

Yann Perusset 13F

Kinetics of the Acid Catalysed reaction between Iodine and Propanone

I shall base my investigation around the following reaction: I2(aq) + CH3COCH3 (aq) CH3COCH2I (aq) + H (aq) + I (aq)

Aims of the investigation

By the end of this investigation I hope to have worked out the rate equation and the rate constant for the above reaction. From the rate equation I will than propose a possible mechanism of the reaction. Lastly, with all information and data already gathered, I will calculate the activation enthalpy of the reaction. The general steps that I will take to achieve my aim are: 1. With use of a colorimeter, I will measure the absorbance of known concentrations of iodine solutions to plot a calibration curve of absorbance against concentration of iodine 2. To deduce the orders of reaction with respect to Iodine, Sulfuric Acid and Propanone a graph of concentration of solution against time would be created again with use of a colorimeter. I can then work out the rate equation and rate constant. (via initial rates method) 3. Propose a possible mechanism which is consistent with the rate equation 4. Finally, I will vary the temperature of the reaction and record new rate constants in order to calculate the activation enthalpy by using the Arrhenius Equation.

Background Theory
Collision Theory The basic idea of collision theory is that reactions occur when the particles of the reactants collide, provided they collide with a combined minimum kinetic energy that must be supplied to enable the bonds in the reactants to stretch and break. This minimum amount of kinetic energy is known as the activation enthalpy (EA). The graph below shoes an enthalpy profile for an exothermic reaction.
1

The theory also helps explain that the more collisions that occur above the activation enthalpy the faster the reaction is as there are more successful collisions. The graph below helps show the concept:

Chemistry Individual Investigation

Yann Perusset 13F

To increase the number of particles with enough energy for a successful collision the temperature can be increased. This concept is again shown in the distribution curve shown above, with T1 being the colder temperature and T2 being the warmer. The area under the curve past the E A shows the number of particles with enough energy to form a successful collision. Basically, reactions go faster at higher temperatures because a larger proportion of the colliding molecules have the minimum activation enthalpy needed to react. Many factors can affect the overall rate of a reaction, the main factors being concentration, temperature, particle size and the presence of a catalyst. When I come to working out the rate equation and I increase the concentration of one of the reactants it is important to keep all other factors the same to determine what effect that particular solution has on the rate without any outside influences. An increase in the concentration of a solution increases the amount of particles within it, the more particles there is, the more likely a successful collision. Order of reaction, rate constants and rate equations Rate Equations and rate constant With a rate equation, it is possible to see how the concentration of each of the reactant affects the rate of a reaction. An example of a simple rate equation is shown below.
2+3

Rate=k[A]x[B]y
The total order of a reaction is the sum of the orders of the individual reactants. So for this reaction it would be the sum of x and y. From the rate equation it is also possible to find out the rate-determining step. From looking at the order of each of the substances it will tell you the relative number of moles of each substance involved in the rate determining step. For example, assume substance A in the equation above is first order, this means that there will be one substance in the rate-determining step. From this, it would then be possible to create a mechanism for the reaction. The rate constant can be calculated by rearranging the rate equation. Below is an example of the rate equation above but rearranged in terms of the rate constant, k:

k=
To obtain a reliable value for the rate the initial rates method would be used (shown below) Once the rate equation is worked out, it can be easily linked to the reaction mechanism by looking at the rate determining step. Colourimetery The rate of a reaction is the change in concentration of a reactant or product divided by the time taken for the change to occur. Therefore to calculate the rate, you have to be able to measure the concentration of a solution. To do so I shall use the process of Colourimetery. A colorimeter can be used to measure the change in colour of a reaction. It works on the principle that coloured solutions (like iodine that I will be using) absorb certain wavelengths of light. The amount of light that is absorbed by the solution is known as the absorbance of the solution. The absorbance is proportional to the concentration of the solution used (Abs Conc) Known concentrations of the coloured solution are used to produce a calibration curve which can then be used to find the concentration of any absorbance value that has that coloured solution within it.
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Theory of initial rates (initial rates method) Initial rates are used to measure the rate of reaction before any of the reactant has been used up. This is done by drawing a tangent at t=0 on a time against concentration graph, and working out the rate from the gradient of the tangent while assuming that the reactants have not changed from their starting concentrations. The graph below shows how to obtain an initial rate from a tangent:

Once the initial rate of a reaction is worked out, a graph of rate against concentration of reactant can be drawn. This would give the order of reaction with respect to a particular chemical. The graphs below show what the graph would look like depending on its order.

0 order

1 Order

st

2 Order

Chemistry Individual Investigation

5+6+9

Yann Perusset 13F

The Arrhenius Equation The Arrhenius Equation was first proposed my Dutch chemist J.H van t Hoft in 1884 but later developed into a physical justification by Swedens Svante Arrhenius, the Arrhenius equation links the rate equation with reaction temperature. The equations is shown below: Where k is the rate constant, Ea is the activation enthalpy, A is the pre-exponential factor, R is the gas constant and T is the temperature in Kelvin. The Ea of the reaction can be calculated by first working out the rate constant of the reaction at a variety of temperatures and plotting a graph of Ink against 1/T. The gradient of the graph would give you the Ea of the reaction. (below) The equations below give the Arrhenius Equation rearranged in terms of Ea. This can also be used to calculate the Ea of the reaction.

Ea=(lnk-lnA)RT
The gradient gives the activation enthalpy of the reaction

Chemistry Individual Investigation

Yann Perusset 13F

Method
Method for constructing calibration curve -3 1. Make up 0.005, 0.0005, 0.00005, 0.000005, 0.0000005 moldm of iodine solution into small 3 3 test tubes via distilling 10cm of the previous concentration into a 100cm volumetric flask 2. Label each small test tubes with allocated concentrations 3 3. Add 5cm of distilled water to a very clean small test tube and reference the colorimeter 3 -3 4. Add 5cm of 0.05 moldm iodine solution into a small test tube and take a reading (a reading of 1.70 and 1.90 is needed for the most concentrated iodine solution) 5. Repeat readings for all concentrations (reference the colorimeter each time) 6. Plot a graph for absorbance against concentration (for a better scale log[-I2] is used) Apparatus Used Colorimeter with a 420-490nm filter- iodine absorbs strongly between these wavelengths 3 10cm glass pipette- to make accurate concentrations with minimal uncertainty 3 100cm volumetric flask- to thoroughly dilute the iodine Small test tubes- to fit in the colorimeter Deducing the order of reaction with respect to iodine -3 -3 3 3 1. Dilute the 0.05moldm iodine solutions into 0.01moldm and fill around 20cm into a 50cm glass beaker -3 3 3 2. Get 2.00moldm sulfuric acid and fill around 20cm into a 50cm glass beaker 3. With one experiment at a time, use the volumes shown in the table below to fill small glass test tubes. (dont add the propanone until step 7) Experiment Volume of Volume of Volume of Volume of Total volume -3 0.01 2.00 moldm 100% neat distilled water of mixture -3 3 moldm sulfuric acid propanone (cm ) 3 3 iodine solution (cm ) solution (cm ) 3 solution (cm ) 1 3.0 1.5 0.5 0 5.0 2 2.5 1.5 0.5 0.5 5.0 3 2.0 1.5 0.5 1.0 5.0 4 1.5 1.5 0.5 1.5 5.0 5 1.0 1.5 0.5 2.0 5.0 6 0.5 1.5 0.5 2.5 5.0 4. Shake iodine, acid and water to mix 5. Reference the colorimeter as described above 6. Add the allocated amount of propanone quickly but carefully into the mixture and place in the colorimeter (quick shake to insure the propanone doesnt stay at the top) and start recording the absorbance every 10 seconds. Time (s) Abd (expt1) Abd (expt2) Abd (expt3) Abd (expt4) Abd (expt5) Abd (expt6) 0 10 20 30 40 50 60 70 80 90 100 110 120 7. Repeat for all 6 experiments 8. With use of the calibration curve graph, for each experiment complete the table below

Chemistry Individual Investigation

Yann Perusset 13F

Time (s)

Abs

Corresponding log[-I2] concentration

0 10 20 30 40 50 60 70 80 90 100 110 120

9. Draw a graph for each experiment of concentration of iodine against time, working out the rate of the reaction with use of the initial rates method (in background theory section) 10. A graph of rate of reaction against initial concentration can now be drawn. The shape of the graph should indicate the order of reaction with respect to iodine Repeat readings should be carried out until a set of two/three close matching results are achieved.

Apparatus Used -Colorimeter with a 420-490nm filter- iodine absorbs strongly between these wavelengths. Has to be the same one as use for the calibration curve. 3 3 -10cm glass pipette- to create the 5cm mixtures in the small test tubes 3 100cm volumetric flask- to thoroughly dilute the iodine and propanone Small test tubes- to fit in the colorimeter 3 50cm glass beakers Stopwatch Deducing the order of reaction with respect to Sulfuric Acid and Propanone The exact same process is used again but instead only varying the solution of either the Sulfuric Acid. The tables below show what measurements to use: For deducing the order of reaction with respect to sulfuric acid Experiment Volume of Volume of Volume of -3 0.005 2.00 moldm 100% neat -3 moldm sulfuric acid propanone 3 3 iodine solution (cm ) solution (cm ) 3 solution (cm ) 1 0.5 3.0 1.5 2 0.5 2.5 1.5 3 0.5 2.0 1.5 4 0.5 1.5 1.5 5 0.5 1.0 1.5 6 0.5 0.5 1.5

Volume of distilled water

Total volume of mixture 3 (cm )

0 0.5 1.0 1.5 2.0 2.5

5.0 5.0 5.0 5.0 5.0 5.0

Deducing the order of reaction with respect to propanone can be found online as repeating the same experimental process would be unnecessary.

Chemistry Individual Investigation

Yann Perusset 13F

Deducing the activation enthalpy of the reaction

This is what the small test tubes contain. Experiment Volume of Volume of -3 0.01 2.00 moldm -3 moldm sulfuric acid 3 iodine solution (cm ) 3 solution (cm ) 1 3.0 1.5

Volume of 100% neat propanone 3 solution (cm ) 0.5

Total volume of mixture 3 (cm )

5.0

For this reaction it is the same process as before. Yet done at different temperatures. 1. In small test tubes, create as many mixed solutions that will fit in an aluminium test tube rack 2. Put the solutions into a water bath and use the dial to heat up the water bath 3. In a separate test tube, the propanone has to be heated at the same temperatures as the iodine sulfuric acid solution 4. The temperature of the small test tube solutions has to be taken and not the temperature of the water bath as they would vary 5. Reference the colorimeter with distilled water and a clean test tube. 6. When the test tube solution reaches the allocated temperature, it is taken out of the water bath, wiped dry, and placed in the colorimeter as quickly and as safely as possible 7. With use of a graduated 1cm pipette get 0.5 cm of propanone at the same temperature as the iodine/sulphuric acid solution and add it to the small test-tube in the colorimeter. 8. Once propanone is added, start the stopwatch, and quickly shake the small test tube to ensure the propanone does not stay at the top 9. Take absorbance readings every 10 seconds This is to be repeated for all temperatures from 25C to 50C going up in 5C each time. The reason why the water bath cant be heated above 50C because the boiling point of propanone is around 54C so the experiment wouldnt work. With use of the Arrhenius Equation, the EA can be worked out. Apparatus Used Colorimeter with a 420-490nm filter (same as used for the calibration curve) Water bath Thermometer 2cm graduated pipette for Sulphuric Acid 5cm graduated pipette for Iodine solution 1cm graduated pipette for propanone Stopwatch Apparatus used and why Graduated pipettes- for high accuracy and minimal percentage error when creating test solutions at a small scale Water bath- a controlled way to get to a wanted temperature and heat up solutions Volumetric flasks- an accurate way to make solutions of a wanted concentration

Chemistry Individual Investigation

Yann Perusset 13F

Risk Assessment7+8
Chemicals Used

Propanone: Hazard/Risk Contact with the eyes can cause serious, permanent damage. Propanone is highly flammable, and presents a serious fire risk Propanone is harmful if you swallow or inhale it. Long-term exposure, for example through breathing in the fumes, can cause liver damage Repeated skin exposure may lead to defatting and irritation Control Measures Always wear safety glasses Ensure that ventilation is good so that you do not breathe in the vapour Remove all sources of ignition from the working area Always store bottles of propanone in a flame-proof cabinet Do not leave propanone, or solutions containing it, standing unattended on a bench where they might get knocked over or set alight

Iodine: Hazard/Risk Iodine is very toxic if swallowed or inhaled Iodine has a significant vapour pressure at room temperature which can lead to the build-up of dangerous levels of iodine vapour Exposure to iodine may lead to reproductive damage Iodine may be absorbed through the skin Control Measures Wear safety glasses Wear gloves if skin contact is likely

Sulfuric Acid: Hazard/Risk Contact with the eyes or skin can cause serious permanent damage Concentrated solutions of acid are extremely corrosive Control Measures Always wear safety glasses Do not allow the acid or a solution of it to come into contact with your skin When diluting acid always wear eye protection, and ALWAYS add acid to water (not the reverse) slowly and with great care. Use constant stirring (sulfuric acid is much denser than water, and if you do not stir when adding acid to water, a layer of concentrated acid may form at the bottom of the beaker, creating a substantial temperature gradient where acid and water meet)

Chemistry Individual Investigation

Yann Perusset 13F

Reaction of propanone with iodine: Hazard/Risk The product (iodopropane) is strongly irritant to the eyes. Control Measures Dispose of it immediately by pouring it down a foul-water drain. Wear eye protection

Apparatus Used Glass Pipettes Hazard/Risk Rick of breakage and injury to hand when inserting into pipette fillers Control Measures Insert carefully and hold the pipette as close as possible to the pipette filler Thermometer Hazard/Risk The mercury inside the thermometer is highly toxic Control Measures The thermometer must be handled with absolute care to prevent breakage Water Bath Hazard/Risk There is a rick as the plug may get in contact with water Control measures Insure the bath isnt overfilled and everything is kept dry

References
1. 2. 3. 4. 5. 6. 7. 8. 9. Salters Advanced Chemistry: Chemical Ideas, eds. D.Denby, C. Otter and K. Stephenson, Heineman, Oxford, Third Edition, 2008, p.210-215 Salters Advanced Chemistry: Chemical Ideas, eds. D.Denby, C. Otter and K. Stephenson, Heineman, Oxford, Third Edition, 2008, p.217-220 Kenneth Connors, Chemical Kinetics, 1990, VCH Publishers, pg. 14 Salters Advanced Chemistry: Chemical Ideas, eds. D.Denby, C. Otter and K. Stephenson, Heineman, Oxford, Third Edition, 2008, p.372 Laidler, K. J. (1997) Chemical Kinetics,Third Edition, Benjamin-Cummings http://old.iupac.org/goldbook/A00446.pdf http://cartwright.chem.ox.ac.uk/hsci/chemicals/hsci_chemicals_list.html Hazcards http://www.chem.fsu.edu/chemlab/chm1046course/activation.html

Chemistry Individual Investigation

Yann Perusset 13F

Analysis
Making and using the calibration curve Below are the results I gained for constructing a calibration curve. The log was used to turn the standard log into positive figure making the graph easier to follow.
Conc of Iodine 0.009 0.005 0.001 0.0005 0.00025 0.0001 0.00005

Conc Log -2.04576 -2.30103 -3 -3.30103 -3.60206 -4 -4.30103

Conc -log[-I2] / moldm-3 2.045757491 2.301029996 3 3.301029996 3.602059991 4 4.301029996

Absorbance 1.99 1.44 0.42 0.25 0.14 0.09 0.03

Calibration Curve Absorbance

2.5 2 Absorbance 1.5 1 0.5 0 2 2.5 3 3.5 4 4.5

y = 81.929e-1.772x

Conc -log[-I2] / moldm-3

The graph created from these results gave a good exponential calibration curve. By plotting the graph in excel, it also gave the equation of the curve, which was . Yet by rearranging the equation in terms of x, the concentration of iodine can be calculated with a given absorbance figure. In terms of x, the equation is log of the concentration of Iodine in the solution, meaning that [I 2] formula for the concentration of iodine in a solution as: . Yet this would only give the . This gives an overall

[I2]
Where Abs is the absorption reading obtained from the colorimeter with a 290nm filter. By using this equation, the concentration of Iodine in the solution can be calculated accurately and without human error by trying to read it from a graph. It can also be quickly calculated in a spreadsheet making it a lot quicker to calculate multiple concentrations instead of doing each one individually. The spreadsheet formula to use is =10^-(((LN(E5))-(LN(81.929)))/(-1.772)) where E5 is the absorption reading obtained from the colorimeter.

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Chemistry Individual Investigation

Yann Perusset 13F

Deducing orders of reactions

The aim of the investigation was to deduce the overall order of the reaction as well as the order of reaction to each individual reactant involved. Later, this would help in calculating the rate constant. The rate equation before any orders of reaction are calculated is: (the H ions coming from the sulfuric acid) Deducing the order of reaction with respect to Iodine Experiment Volume of 0.01 -3 moldm iodine 3 solution (cm ) 3.0 2.5 2.0 1.5 1.0 0.5 Volume of -3 2.00 moldm sulfuric acid 3 solution (cm ) 1.5 1.5 1.5 1.5 1.5 1.5 Volume of 100% neat propanone 3 solution (cm ) 0.5 0.5 0.5 0.5 0.5 0.5 Volume of distilled water Total volume of mixture 3 (cm )
+

1 2 3 4 5 6

0 0.5 1.0 1.5 2.0 2.5

5.0 5.0 5.0 5.0 5.0 5.0

The Iodine graphs correspond to the experiments listed in the table above and the results from the results section. The gradient of the line equals the rate of the reaction because rate=conc/time and the gradient of the line gives conc/time. Below gives the found gradient and therefore the rate for each experiment.

Run1 Experiment 1 2 3 4 5 6

Rate(moldm-3s-1) 0.0000242 0.0000175 0.0000163 0.0000217 0.0000205 0.0000188

Run2 Experiment 1 2 3 4 5 6

Rate(moldm-3s-1) 0.0000276 0.000025 0.0000246 0.000025 0.000025 0.0000214

Each experiment number corresponds to a concentration of Iodine. This can be calculated by: Overall concentration of iodine =conc x (volume of iodine/total volume) The concentration used was 0.001 moldm-3 and the total volume was cm-3 Experiment 1 2 3 4 5 6 Concentration of Iodine 0.006 0.005 0.004 0.003 0.002 0.001

From this, a graph of concentration of iodine against rate of reaction can be drawn.

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Run1 0.00003 0.000025 Rate/moldm-3s-3 0.00002 0.000015

0.00001
0.000005 0 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007

Concentration of Iodine/moldm-3

Run2 0.00003 0.000025 Rate/moldm-3s-3 0.00002 0.000015 0.00001 0.000005 0 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007

Concentration of Iodine/moldm-3

The two graphs show a relatively flat line, hence showing that the order of reaction with respect to iodine is 0 order as when the concentration of Iodine increases in the reaction, the rate remains unchanged at an average of 0.0000198 moldm-3s-1 for Run 1 and 0.0000248 for Run 2. Therefore, Iodine is not included in the rate equation as no matter what the concentration of iodine is used, the rate of reaction remains unchanged.

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Deducing the order of reaction with respect to Sulfuric Acid Experiment Volume of Volume of Volume of -3 0.005 2.00 moldm 100% neat -3 moldm sulfuric acid propanone 3 3 iodine solution (cm ) solution (cm ) 3 solution (cm ) 1 0.5 3.0 1.5 2 0.5 2.5 1.5 3 0.5 2.0 1.5 4 0.5 1.5 1.5 5 0.5 1.0 1.5 6 0.5 0.5 1.5

Volume of distilled water

Total volume of mixture 3 (cm )

0 0.5 1.0 1.5 2.0 2.5

5.0 5.0 5.0 5.0 5.0 5.0

The Sulfuric Acid graphs correspond to the experiments listed in the table above and the results from the results section. The gradient of the line equals the rate of the reaction because rate=conc/time and the gradient of the line gives conc/time. Below gives the found gradient and therefore the rate for each experiment.

Run1 Experiment 1 2 3 4 5 6

Rate(moldm-3s-1) 0.0001875 0.0001731 0.0001286 0.0001047 0.00007031 0.00003774

Run2 Experiment 1 2 3 4 5 6

Rate(moldm-3s-1) 0.0002045 0.0001731 0.000125 0.00009375 0.00006429 0.00003636

Each experiment number corresponds to a concentration of Sulfuric Acid. This can be calculated by: Overall concentration of Sulfuric Acid =conc x (volume of Sulfuric Acid/total volume) The concentration used was 2.00 moldm-3 and the total volume was cm-3 Experiment 1 2 3 4 5 6 Concentration of Sulfuric Acid 1.2 1.0 0.8 0.6 0.4 0.2

From this, a graph of rate of reaction against concentration of iodine can be drawn.

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Run 1 0.00025

0.0002 Rate/moldm-3s-1

y = 0.000165x

0.00015

0.0001

0.00005

0 0 0.2 0.4 0.6 0.8 1 1.2 1.4

Concentration of Sulfuric Acid /moldm-3

Run 2 0.00025

0.0002 Rate/moldm-3s-1

y = 0.000167x

0.00015

0.0001

0.00005

0 0 0.2 0.4 0.6 0.8 1 1.2 1.4

Concentration of Sulfuric Acid /moldm-3

From these graphs which show proportionality between the concentration of sulfuric acid and the st rate. Hence showing that the order of reaction with respect to Sulfuric Acid is 1 order as when the concentration is increased, the rate increases proportionally. Therefore, sulfuric acid is involved in the rate equation.

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st

Yann Perusset 13F

The order of reaction with respect to propanone is also 1 order meaning that it is also included in the rate equation. This leaves an overall equation of the reaction to be: Meaning that the rate constant, k, can be calculated by rearranging the rate equation to:

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Deducing the rate constant of the reaction

One of my aims was to calculate a rate constant for the reaction between acid catalysed reaction between iodine and propanone. I have all ready worked out the rate equation, , and in terms of k, . In order to calculate the constant as accurately as possible, I can use the rate against concentration graph from Sulfuric Acid. The gradient of the line gives , therefore by combining this into the main rate equation, , where g is the gradient of the rate against concentration for sulfuric acid and [propanone] is the concentration of propanone used. Calculating the concentration of propanone used As I used neat propanone in my experiments, I need to be able to calculate the concentration used before I can work out the rate constant of the reaction. 3 3 The density of liquid propanone is 0.7925 g/cm , meaning that in one dm there is 792.5g. The amount of moles can then be calculated: Molecule formula= C3H6O 1 Mr= 58.08 g mol Mass=792.5g

Moles in 1dm = 13.64mol Therefore the concentration of propanone I used 13.64moldm . 3 Since I used 1.5cm of neat propanone, the concentration used in each experiment: =conc x (volume of Propanone/total volume) -3 3 3 =13.64moldm x (1.5cm /5cm ) -3 =4.092moldm Deducing the rate constant The overall rate constant can now be calculated. The average gradient from the rate against concentration of sulfuric acid from both run 1 and run 2 is 0.000166. The concentration of the -3 propanone used is 4.092 moldm , these figures can be used to calculate the rate.
-3

k=4.057 10-5
So the rate constant, k, for the acid catalysed reaction between iodine and propanone is 4.057 10 .
-5

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Deducing the activation enthalpy, Ea, of the reaction

Experiment Volume of 0.01 -3 moldm iodine 3 solution (cm ) 3.0 Volume of -3 2.00 moldm sulfuric acid 3 solution (cm ) 1.5 Volume of 50% neat propanone 3 solution (cm ) 0.5
o

Total volume of mixture 3 (cm )

5.0

These mixtures were repeated at temperature intervals of 5 . From the results obtained, graphs of concentration of iodine against time can be drawn, from them, using the initial rates method; the rate of reaction for each experiment at different temperatures can be calculated. Below is a table of the rate of reaction at different temperatures. The temperatures have to be converted from Celsius to Kelvin so they work when used in an Arrhenius graph. The gradient of the graphs gave these results: Temperature (C ) 30 35 40 45 50
o

Temperature (K) 303.15 308.15 313.15 318.15 323.15

Rate (moldm s ) 0.000021 0.000033 0.00004 0.0000741 0.0001013

-3 -1

From these rates, the rate constant for each temperature can be calculated. This done with the equation:
-3 -3

Where the concentration of both sulfuric acid = 0.6moldm and propanone =0.682moldm . Temperature, T, (K) 303.15 308.15 313.15 318.15 323.15 Now T has to converted to 1/T (reciprocal of T) and k to lnk (the natural log of k) T 303.15 308.15 313.15 318.15 323.15 k 0.00005132 0.00008065 0.00009775 0.00018109 0.00024756 1/T 0.0032987 0.0032452 0.0031934 0.0031432 0.0030945 against . lnk -9.877 -9.425 -9.233 -8.617 -8.304 Constant calculation Constant, k, value 0.00005132 0.00008065 0.00009775 0.00018109 0.00024756

From the constant values, I can now draw a graph of

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Below shows the graph of lnk against 1/T.

-10 -9.8 -9.6 -9.4 -9.2 y = -7739.7x -9 lnk

-8.8 -8.6
-8.4 -8.2 0.00335 0.0033 0.00325 0.0032 1/T 0.00315 0.0031 0.00305

The gradient of the line hence , where g is the gradient and R is ideal gas constant. By using , the Ea can be calculated:

G=-7739.7 R= 8.314 Jmol-1K-1 Jmol-1 KJmol-1

The activation enthalpy of the reaction was found to be 64.348 KJmol . Yet it is also possible to propose the full Arrhenius expression of the reaction by calculating a value for the pre-exponential factor, A, in the Arrhenius equation. The x intercept on the Arrhenius graph is equal to the natural log of A. The x intercept is 15.637 so . Therefore, . This gives the value of A to be 7 6.18x10 . The overall Arrhenius expression is therefore:
-1

A=6.18x107

Jmol-1 R= 8.314 Jmol-1K-1

(the overall Arrhenius expression)

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Proposing a possible mechanism

Below shows a possible mechanism of the reaction:

After the analysis of the reaction, I have the order of reaction with respect to each reactant and so can prove whether the mechanism is correct or incorrect. As Iodine is zero order, it is not involved in the rate determining step as it has to effect on the rate, + therefore the rate determining step must include propanone and a H (from S2HO4) as those are the only two reactant which affect the rate. The rate determining step also has to be the slowest step, which on the diagrams, is the first. Therefore, the rate determining step is:

This is the rate determining step because is both the slowest and contains the only reactants which can affect the rate. Although there is a significant possibility that this is what does happens in the reaction, it is simply a proposition of the mechanisms which best describes what actually happens.

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Evaluation
General limitation of practical procedure For my experiment there are several limitations to consider. The most troubling limitation would be transferring the propanone to the small test tube. The problem is that as soon as the propanone is added the mixture, the reaction is already taking place. This therefore affects the accuracy of the initial rate. Another unavoidable limitation of the practical procedure is that the mixture has to be quickly shaken before put into the colorimeter to ensure the mixture is thoroughly mixed. This affects the consistency of the experiments as some may be mixed more than others by human error. Regarding the practical procedure in use for the water bath experiments, the limitation is that there is a lot to do in a short space of time, so again consistency of the experiment may not be very good.

Limitation of practical equipment It is impossible to have a 100% accuracy for any practical equipment meaning that there are uncertainties involved. Yet the overall uncertainty can be reduced by selecting the appropriate equipment when necessary. Below shows all the equipment which I used and the limitations involved when using it. Equipment Volumetric flask 3 100cm
3

Uncertainty 0.08

Grad Pipette 5cm

0.05

Grad Pipette 2cm

0.02

Grad Pipette 1cm

0.01

Colorimeter Thermometer Water Bath

3

0.05 0.5

Pipette 10cm

0.04

Limitations Human error involved when assuring the bottom of the 3 meniscus is level with the 100cm line Liquid solution can drip out and the human error involved when assuring the bottom of the meniscus is level with the line Liquid solution can drip out and the human error involved when assuring the bottom of the meniscus is level with the line Liquid solution can drip out and the human error involved when assuring the bottom of the meniscus is level with the line Same colorimeter has to be used throughout to insure your calibration curve works. The amount of light in the room could also potentially affect the absorbance reading. Few limitations apart from the glass tends to steam up making it hard to read the temperature. The only limitation would be that it takes a long time for the solutions to reach the correct desired temperature Simple to use, yet when taking some liquid, extra has to be taken to compensate for some lost when taking the pipette out of the solution.

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Chemistry Individual Investigation

Yann Perusset 13F

Percentage Uncertainties
To gain a good indication of the errors involved in the practical procedure, percentage uncertainties can be calculated. Iodine concentration uncertainty As I had to dilute the concentration of iodine to 0.01moldm , there would be uncertainties involved 3 in this made concentration. This involved using a 20cm pipette with an uncertainty of 0.06 and also 3 using a 100cm volumetric flask with an uncertainty of 0.08. Therefore, the uncertainty of the -3 0.01moldm concentration is: =2.4x10
-6 -3

So the uncertainty is very small. Absorbance experiment uncertainty As the colorimeter has an uncertainty of 0.05, there is also an uncertainty involved in the. Below shows an example of what the uncertainty is. Time 0 10 20 30 40 50 60 70 80 90 100 110 120 Abs 1.47 1.43 1.35 1.31 1.25 1.19 1.15 1.09 1.04 1.00 0.93 0.89 % Uncertainty 3.401 3.497 3.704 3.817 4.000 4.202 4.348 4.587 4.808 5.000 5.376 5.618

It is clear to see that when the absorbance is low, the uncertainty is higher. Fortunately, i avoided using experiments which included a low absorbance so that the percentage uncertainty would not be too high therefore improving the accuracy of my practical.

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Chemistry Individual Investigation

Yann Perusset 13F

Method Overall, I feel that my method worked out well as I was able to achieve all my aims which I stated in my plan to a high level of accuracy. Finding various rates of reaction All worked well and I was able to determine the rate and order of reaction with respect to each reactant. Fining the Activation Enthalpy This worked well and gave a good result of out good.

KJmol-1. Although it was difficult to do, it turned

Alterations that I would change If I was to change anything I would probably try and use a data logger to create accurate and on time readings. This would reduce human error. Yet, there is not many things that I would actually change, as the method and practical procedure all went to plan. Reliability I feel that my results are reliable to use, as I repeated experiments until a match was found. From this, a good average could be attained. I also had to experiment to get the perfect combination for the mixture. The graphs showed very few anomalies hence further proving that my results are reliable. Accuracy Accuracy is a measurement of how close the result values are to the true value. The two values which I could compare to true values would be the rate equation and the Ea. The true rate equation is + Rate=k[propanone] [H ]. Mine was found to be the same, showing my results were accurate. -1 Secondly, my activation enthalpy of the reaction. The true value was found to be 68.2kJmol and my value was KJmol-, so only being 5.6% off the true value, it is fair to say my results are highly accurate. The reason that my value may just be a little bit to low was probably because my temperatures were said to be lower than they actually are. Validity Overall, I feel that my results re valid because they have a relatively low percentage uncertainty. Also, my values and results match what they should be.

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Chemistry Individual Investigation

Yann Perusset 13F

Conclusion

Aims of the investigation

By the end of this investigation I hope to have worked out the rate equation and the rate constant for the above reaction. From the rate equation I will than propose a possible mechanism of the reaction. Lastly, with all information and data already gathered, I will calculate the activation enthalpy of the reaction. The general steps that I will take to achieve my aim are: 1. With use of a colorimeter, I will measure the absorbance of known concentrations of iodine solutions to plot a calibration curve of absorbance against concentration of iodine 2. To deduce the orders of reaction with respect to Iodine, Sulfuric Acid and Propanone a graph of concentration of solution against time would be created again with use of a colorimeter. I can then work out the rate equation and rate constant. (via initial rates method) 3. Propose a possible mechanism which is consistent with the rate equation 4. Finally, I will vary the temperature of the reaction and record new rate constants in order to calculate the activation enthalpy by using the Arrhenius Equation. Looking back at my aims I am happy to say that my investigation went very well. I deduced the order of reaction with respect to iodine and propanone, proposed a rate equation and therefore a rate constant, calculated the activation enthalpy of the reaction and lastly proposed a mechanism. Below shows all of the aims of the investigation worked out:

k=4.057 10-5 KJmol-1

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