Kinetics Investigation - The Reaction Between Propanone and Iodine in Acid Solution

Kinetics of the reaction between propanone and Iodine in acid solution
Aria Fard Kinetics of the reaction between propanone and Iodine in acid solution Candidate Number: 5208
Section 1
Equation for the reaction: I2(aq) + CH3 COCH3(aq) CH3 COCH2I(aq) + H+(aq) + I (aq) Iodine + Propanone Iodopropanone + Hydrogen (cation) + Iodide (anion)
Introduction: Chemistry of the reaction: Propanone and Iodine react together in an irreversible redox reaction to form Iodopropanone. This reaction is catalysed by aqueous Hydrogen ions (protons) produced from the Sulphuric acid. As the reaction proceeds the dark brown colour of Iodine in solution gradually turns colourless. This is due to the concentration of Iodine in solution decreasing as it is being used up reacting to produce colourless Iodide ions and the Iodopropanone. I have chosen to monitor the progress of this reaction by measuring the absorbance value of this colour change in a digital Colourimeter.
Aims: 1). I aim to individually vary the concentrations of each reactant (Iodine and Propanone) including the acid catalyst (Sulphuric acid) in solution and measure its effect on the rate of reaction in Absorbance (Beer-Lambert Law) using Colourimetry. All of data collected will be used to construct line graphs for each concentration of reactant investigated per experiment. Using the trends of these line graphs, the initial rates of reaction method can be used by drawing tangents from the starting plots of the reaction progress curve to calculate each rate of reaction (A/s-1). Finally these values of rate of reaction can be plotted against concentration of the reactant being investigated to deduce the order of reaction with respect to that reactant - this process will be carried out for each reactant. 2). Using the orders of reaction and the rate equation, I aim to calculate a mean rate constant (at room temperature). Through addition of reactant orders (m+n) the overall order of reaction can be deduced. Independent Variable(s): - Concentration of Iodine (in situ) (mol dm-3) - Concentration of Propanone (mol dm-3) - Concentration of Sulphuric acid (mol dm-3) Dependent Variable Absorbance
3). Using two forms of the Arrhenius equation, I aim to calculate the activation enthalpy (Ea) of the reaction by varying temperature (Kelvin) - conditions ranging from 293-323 Kelvin. Independent Variable Temperature of reactants in reaction (Kelvin) Dependent Variable Absorbance 4). Using the orders of reaction with respect to Iodine, Propanone and Sulphuric acid as an indication, I intend to propose a possible mechanism for the entire reaction.
Relevant chemical theory Collision Theory: The basic explanation surrounding why reactions occur is that reactant particles must successfully collide with the correct molecular orientation and a combined minimum kinetic energy - known as activation enthalpy (Ea) - to enable the bonds in the reactants to break and to allow product bonds to form. In the example of this reaction we are referring to the collisions that could occur between three species - the diatomic Iodine molecule, the molecule of Propanone (acetone) and H+ particles produced via de-protonation of Sulphuric acid molecules . The frequency of these collisions are dependent on the number of particles of these reactants within a given volume (mol dm-3) As particles approach and collide, kinetic energy is converted into potential energy and the potential energy of the reactant rises. A plot can be drawn of reaction progress against enthalpy enthalpy profile. However even with the correct orientation between the species they will not react without the required activation enthalpy; the species will bounce apart on deflect from one another. Only the species with enough combined kinetic energy on collision to overcome the repulsive energy barriers (Ea) will go on to react and produce products. (Activation enthalpy is displayed below in the enthalpy profile of a standard exothermic reaction by the red arrow in the diagram)
The proportion of colliding reactants with sufficient kinetic energy to overcome the Ea depends on the temperature of the solution. At higher temperatures, there are a much larger proportion of colliding pairs with enough energy to react. Particles within a reaction will have a variety of different energy values. For gases this distribution can be displayed on the Maxwell-Boltzmann Distribution Curve: (a plot of the number of particles having each particular energy) Note: The Maxwell-Boltzmann graph only applies to gases, but the conclusions that can be drawn from it can also be applied to reactions involving liquids considering that both the reactants and catalyst are in a homogenous liquid state this makes it relevant chemical theory.
The area that is underneath the curve is representative of the amount of total number of particles present. The Maxwell-Boltzmann Distribution curve is often used to display the proportions of particles that do and do not have the required activation enthalpy to react:
This graph provides a visual representation of the ratio of particles that do have the sufficient activation enthalpy to react and or dont. A conclusion that can be drawn from this graph is that
more reactant species do not react than do react. This is useful in demonstrating the typical principles of particle reactivity to apply to my investigation. Note: To increase the number of particles within the Ea: - I can lower the activation energy (further to the left) through use of a catalyst - I can change the shape of the graph by varying temperature of the reaction (K) The Arrhenius Equation: (Proposed by Dutch chemist J.H van t Hoft (1884); later developed into physical justification via Swedens Svante Arrhenius) The Arrhenius equation determines the relationship between the rate equation and its temperature (Kelvin):
Note: Reactant molecules have a higher probability of collision at higher temperatures; higher collision rate results in greater levels of kinetic energy. This has a direct effect on the activation energy of the reaction.
(Logarithmic form of Arrhenius equation Right hand side) The Factors Chemical reaction rate constant units: s-1 (1st order rate constant) OR M-1s-1 (2nd order rate constant) Pre-exponential factor specifically relates to molecular collision (so therefore is temperature dependent); this deals with the frequency of reactant molecules colliding in the correct orientation and with Ea. It is determined experimentally (as it varies with different reactions). Units: s-1(1st order rate constant) M-1s-1(2nd order rate constant) OR s-1(for 1st order rate constant)
Activation Energy is the threshold energy that reactants must acquire before reaching a transition state. Units: kJ/mol Note: Ea/RT resembles the Boltzmann distribution law. Gas Constant - 8.314 (J mol K) Temperature (at which the reaction takes place) (Kelvin) Using the Linear Arrhenius Equation: The Arrhenius equation is actually the equation of a straight line (y= mx + c) Ea of the reaction can be calculated by first working out the rate constant of the reaction at a variety of temperatures and plotting the Arrhenius Plot of lnk against 1/T.
Extrapolating the graph will deduce both the gradient of the Arrhenius plot and show the intersection of on the y axis (lnA). The equation below gives the Arrhenius Equation rearranged in terms of activation enthalpy (Ea):
Ea=(lnk-lnA)RT
In this investigation, temperature (K) will be varied through the use of a manual water bath to observe and record the effects of temperature conditions ranging from 293-323 Kelvin on the rate of reaction. Through naturally logging the equation, the data collected can be plotted onto an Arrhenius plot to deduce activation enthalpy from.
The comparative form of Arrhenius equation can also be used to calculate Ea:
Catalysed reaction and Arrhenius Equation: The Arrhenius Equation states that the rate of an uncatalysed reaction is more affected by temperature than the rate of a catalysed reaction. This is because the activation energy of an uncatalysed reaction is greater than the activation energy of the corresponding catalysed reaction. Being an acid catalysed reaction, this is a factor that could be considered. Order of reactions and the rate equation: Recap: The rate of reaction is the change of concentration of a substance in a given time whether that is reactants disappearing or products appearing. In the case of this investigation, rate is measured in A/s-1(absorbance change per second). Note: The rate equation can be used for any chemical reaction provided that experiments are conducted to find out how the rate depends on the concentrations of the reactants. This investigation intends to utilise the rate equation to investigate how Iodine, Propanone and Sulphuric each individually impact the rate of reaction (or whether their concentration no effect at all) (In the example given below A and B are reactants in a general reaction)
Where m and n are the powers to which concentration need to raised they usually have values of 0, 1 or 2. This is because the superscript is representative to the order of reaction with respect to that reactant. Note: the values m and n can only be deduced via experimentation and have nothing to do with the molarity of reactants in the balanced reaction equation. The initial rate method: The rate of reaction can be obtained using the Initial rates method. The initial rates method
involves drawing tangents from the first two plots of data at the assumed start of the progress curve on a line graph displaying Absorbance against Time (seconds). From this tangent, the instantaneous rate of reaction can be deduced by working out the gradient of the slope. The gradient of the slope can be calculated using the simple equation . Beneath is a typical example of how to conduct the initial rates method:
Note: The gradient from the initial tangent of data = the initial rate of reaction Unit for this investigation: A/s-1 - Absorbance change per second When varying the concentration of a single reactant, the data obtained from each condition can use the initial rate method to deduce a rate of reaction value. This rate of reaction value can be plotted against concentration (mol dm-3) to distinguish the order of reaction. Orders of reaction: - graph axes: x (concentration) y (rate) In a zero order reaction: The rate is constant since anything to the power of 0 is 1. Therefore the rate of reaction does not change over time and the [A] changes linearly.
In a first order reaction: The rate and concentration are proportional. This means that if the concentration is doubled, the rate will double.
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In a second order reaction: If the concentration is doubled, the rate will increase by a factor of 4
Chemical Ideas covered (synoptic reference) Chemical Ideas Moles RMM Redox Rates factors affecting rates The effect of temperature on rate Orders with respect to reactants Catalysts The p block: group 7 Ketones Colourimetry Chapter CI 1.1 CI 1.1 CI 9.1 CI 10.1 CI 10.2 CI 10.3 CI 10.5 / CI 10.6 CI 11.4 CI 13.7 Appendix 1: C Module F331 F331 F332 F332 F332 F334 F332 F332 F334 AS/A2 AS AS AS AS AS A2 AS AS A2 -
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Experimental Theory Colourimetry A colourimeter works on the principle that coloured solutions absorb specific wavelengths of light (e.g. purple solutions will absorb orange light strongly). The light source in a Colourimeter is produced by one of the several light emitting diodes (different filters of colour use different light emitting diodes). So, in the case of my investigation I would be looking at using a Blue filter setting as this is the specific wavelength (465nm), complementary to the Brown colour of Iodine. This light passes 10mm through the reaction sample inside the standard plastic 4.5 cm3 cuvette and is detected by the photodiode. The amount of light detected compared with the initial amount of light emitted is used to calculate a value known as Absorbance. This process is displayed in the basic diagram below:
Absorbance is defined as: log10(Io/I), or 2 log10T% There is a linear relationship, (Beer-Lambert Law), between absorbance and the concentration of the light-absorbing substance in the sample (Iodine). Absorbance is determined by the amount of light that is absorbed by the solution inside the cuvette, and is quantifiably measured as a 3 decimal place value. So ultimately a colourimeter can be used to determine the concentration of a coloured solution (in the case of my investigation, Iodine). So therefore I can utilise this linear relationship to determine the concentration of Iodine throughout its catalysed reaction with Propanone in real time. Methodology: 1). Choose the filter colour that selects the band of wavelengths which are most strongly absorbed by the coloured solution. In the case of Iodine being a Dark-Brown colour the selected filter is Blue (465nm). 2). Zero the colourimeter using a cuvette that is filled with distilled water. This acts as a base value for minimal absorbance of light as distilled water is transparent and this procedure eliminates error. Theoretically if all of the Iodine in solution reacts the absorbance value should match that of water with a value of 0.000.
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Appropriateness: The colorimeter is a relatively simple instrument and requires little maintenance. They are generally of a small size and are quite portable which is important in regards to desk space and being able to work around the equipment. When compared to an alternative experimental technique like Sample testing (e.g. Quenching and titrating), Colourimetry takes up less time as there is minimal preparation of equipment involved as to prepare a Colourimeter takes seconds as opposed to setting up a burette with takes minutes. The use of Colourimetry can be justified by the margin of error that the equipment produces. A Colourimeter that measures the nearest 0.001 will have an error of 0.001 (Absorbance) as you are only taking a single reading (not including repeats). Compare this to the error you would achieve using a Quench and Titrate method: a burette records to the nearest 0.05 cm3 consequently the error will be 0.05, however considering that you would take two reading for this method (initial and final titre) the error doubles to 0.1 cm3 this error is considerably higher than Colourimetry and is not as appropriate in regards to recording accurate data.
Serial Dilution: In the event that I desire to use a more concentrated solution that is not supplied in the stock solutions or if I have to produce intermediate concentrations between two stock solution concentration I will use the Serial Dilution equation displayed and explained below:
MiVi = MfVf
Initial Molarity (mol dm) x Initial Volume (dm) = Final Molarity (mol dm) x Final Volume (dm) Example: I wanted to attempt using 5.0 mol dm Propanone in the reaction I first have to calculate the concentration of the Pure Propanone I am going to be diluting from: 1). Density of Propanone = 0.791 g/cm (791 g/dm) 2). Mr of Propanone = 58g/mol 3). Density Mr = (791 58) = 13.6 mol dm (Molarity of Pure Propanone) Using MiVi = MfVf I can to calculate the required volume of Pure Propanone (labeled a ) to dilute in a 250 cm volumetric flask. 13.6M x = 5M x 250 cm
= 91.91 cm 12
Planned Experiments: (Modified) 4 variables will be investigated for the acid catalysed reaction between Propanone and Iodine: Varying the concentration of Iodine (in situ) (mol dm) Varying the concentration of Propanone (mol dm) Varying the concentration of the Sulphuric acid catalyst (mol dm) Varying temperature of the reaction (K)
For each different investigation a minimum of 4 different conditions will be created with the intention of developing a range of data to test the independent variable in each experiment. Within each condition, 3 repeats will be carried out to help identify any anomalous data to be ignored from mean value calculations increasing reliability. Varying the concentration of Iodine: (This experiment is designed to investigate how rate of reaction is effected by Iodine concentration, to calculate the order of reaction with respect to Iodine) Apparatus: - Measuring Graduated Pipette (5ml) - Graduated Pipette (10ml) - Manual Pipette Filler - Dropper Pipette - Boiling tube rack - Boiling tube (x3) - Rubber Boiling tube bung - Distilled Water bottle - 4 glass beakers (100ml) - Digital Colourimeter (Mystrica) Blue filter (465nm) - Plastic cuvettes 4.5 cm3 - Cuvette stand and cuvette lids Quantities to measure out: Experiment Volume of 5.0M Propanone (cm3) 2.00 2.00 2.00 Volume of 0.02M Iodine (cm3) 2.00 3.00 4.00 Volume of 2.0M Sulphuric acid (cm3) 2.00 2.00 2.00 Volume of Water (cm3) Total Volume of solution (cm3) 20.00 20.00 20.00
1 2 3
14.00 13.00 12.00
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2.00
5.00
2.00
11.00
20.00
The justification behind using greater volumes of distilled water within this investigation was due to the fact that when varying 0.01M Iodine volumes, the initial absorbance readings were too low. Therefore 0.02M Iodine was used instead, however on its own the absorbance values proved to be too high for the Colourimeter to read. By further diluting the solution with more water instead, the volumes could be varied from 2-5 cm3 of Iodine much more easily when compared with 0.01M Iodine.
Method: (Modified)
1). Pour the appropriate concentrations of Iodine, Propanone and Sulphuric acid and distilled water from their containers into separate labeled glass beakers for measuring out the required reactant volumes. Measure out stated volumes of Propanone and Sulphuric (cm3) using the appropriate graduated pipette and manual pipette filler into a boiling tube (A) - rinsing the graduated pipette with the reactant to be measured before measuring that reactant out (when transferring different reactants with the same pipette) to avoid cross contamination of chemicals.
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2). Measure out the stated volume of Iodine and distilled water into a separate boiling tube (B). Repeat these first two stages twice producing 3 sets of boiling tubes (A+B) for the 2 repeat experiments to follow. Keep the tubes on a boiling tube rack for convenience. Be sure to shake the contents in both sets of boiling tubes to ensure the reactants are mixed prior to being added together for the reaction. 3). Set up the Colorimeter; ensure the appropriate Blue colour filter (2) is set for the colour change of Iodine (orange); Zero the colorimeter using a cuvette filled with distilled water, remove the cuvette of distilled water. Ensure that there is a shady environment for the colorimeter to function adequately (avoid light exposure from lab windows) or use a colorimeter cap/lid. 4). Reaction: Simultaneously start the stopwatch whilst pouring the entirety of the contents of boiling tube A into boiling tube B and bump the lips of the two boiling tubes (with mild force) to ensure the final droplets of reactants are added. Immediately after this firmly secure a rubber bung in the top of the boiling tube and invert the tube four times to ensure that the reaction mixture is mixed thoroughly; ensure that the same level of agitation is applied in any repeat practical so the reactant samples are theoretically mixed equally. Place the tube into the test tube rack; using a dropper pipette, transfer the reaction mixture into an empty clean cuvette. Immediately after this place the cuvette into the colorimeter ensuring that the ribbed faces are not facing the light source. (This should take approximately 20 seconds if performed efficiently) 5). Record the absorbance on the colorimeter at 30 seconds on the stopwatch. Continue to record the absorbance at set intervals of 15 seconds over a total of 345 seconds (5 minutes 45 seconds). Note: repeat stages 3-5 for each repeat ensuring all equipment is cleaned to prevent contamination and remembering to zero the colourimeter between experiments. All of my results for each investigation will be recorded in the style results table displayed below: Absorbance Run 2
Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195
Run 1
Run 3
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210 225 240 255 270 285 300 315 330 345 Varying the concentration of Propanone: (This experiment is designed to investigate how rate of reaction is effected by Propanone concentration, to calculate the order of reaction with respect to Propanone) Exactly the same method is used as shown above in the varying Iodine concentration, however using different volumes and concentrations of reactants, as displayed below: Quantities to measure out: Volume of Propanone (cm3) 2.00 Volume of 0.02M Iodine (cm3) 2.00 Volume of 2.0M Sulphuric acid (cm3) 2.00 Volume of Water (cm3) Total Volume of solution (cm3) 20.00
14.00
Preparing up the different concentrations of Propanone using Pure Propanone: Desired Concentration (mol dm) 2.5 5.0 7.5 10.0 Volume of Pure Propanone required in a 50 cm3 volumetric flask dilution (cm3) (2 d.p.) 9.19 18.38 27.57 36.76
Note: Pour out each 50 cm3 concentration of Propanone from the volumetric flask into separate appropriately labeled containers with secured lids, as Propanone is an extremely volatile substance especially at high concentration - it needs to be contained when not being used. Varying the concentration of Sulphuric Acid: (This experiment is designed to investigate how rate of reaction is effected by Sulphuric acid
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concentration, to calculate the order of reaction with respect to Sulphuric acid)
The same method is used as displayed in the section for varying Iodine concentration however due to the lesser total volume of solution (cm3), test tubes are used instead of boiling tubes (so a test tube bung is required) and also the distilled water measurement is added to tube A whereas Iodine solitarily added to test tube B. The different stated volumes of reactants to be measured out and different concentrations used for this experiment are displayed below: Volume of Propanone 5.0M (cm3) 2.00 Volume of 0.01M Iodine (cm3) 5.00 Volume of Sulphuric acid (cm3) 2.00 Volume of Water (cm3) 1.00 Total Volume of solution (cm3) 10.00
Preparation of different concentrations of Sulphuric acid using 2M Sulphuric acid: Note: 1M and 2M Sulphuric acid do not need to be made via serial dilution as they are available in stock solutions Desired Concentration (mol dm) 1.4 1.6 1.8 Volume of 2M Sulphuric acid required in a 50 cm3 volumetric flask dilution (cm3) 35 40 45
Note: Pour out each 50 cm3 intermediate concentration of Sulphuric from the volumetric flask into separate appropriately labeled containers with secured lids, as concentrated Sulphuric acid poses as a high risk chemical and precautions must be taken after dilution. Varying the Temperature of reaction: (This experiment is designed to investigate how rate of reaction is affected by changes in temperature to deduce a value for Activation enthalpy using the Arrhenius equation) Apparatus: - Thermometer (273-373K) - Boiling Kettle - (Access to a cold water tap) - Plastic tub (Approximate Diameter 15cm) - Glass Rod - Measuring Graduated Pipette (5ml) - Manual Pipette Filler - Dropper Pipette
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Aluminum test tube rack Test tube (x3) Boiling tube (x3) Rubber Boiling tube bung Distilled Water bottle 4 glass beakers (100ml) Digital Colourimeter (Mystrica) Blue filter (465nm) Plastic cuvettes - 4.5 cm3 Cuvette stand and cuvette lids
Justification for using a kettle and plastic tub: This manual form of varying temperature was used, through trial and error, due the fact that a water bath was not available equipment for my investigation. This method was the closest way of replicating the effect of a water bath considering the plastic material insulates against heat loss more efficiently when compared with the option of using a glass beaker. Temperatures being investigated (Kelvin) 293 303 313 323 Justification of choice of Temperature conditions: The maximum temperature (323 Kelvin) was selected due to the fact that Propanone has a boiling temperature of 329K and so at any higher temperature it is likely that experiment would not have worked large volumes of this reactant would have been lost before the reaction had begun. Quantities to measure out: Volume of Propanone 5.0M (cm3) 2.00 Method: Volume of 0.01M Iodine (cm3) 5.00 Volume of 2.0M Sulphuric acid (cm3) 2.00 Volume of Water (cm3) Total Volume of solution (cm3) 10.00
1.00
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1). Pour the appropriate concentrations of Iodine, Propanone and Sulphuric acid and distilled water from their containers into separate labeled glass beakers for measuring out the required reactant volumes. Measure out stated volumes of Propanone, Sulphuric acid and water (cm3) using the appropriate graduated pipette and manual pipette filler into a test tube (A) rinsing the graduated pipette with the reactant to be measured before measuring that reactant out (when transferring different reactants with the same pipette) to avoid cross contamination of chemicals 2). Measure out the stated volume of Iodine into a separate test tube (B). Repeat these first two stages twice producing 3 sets of test tubes (A+B) for the 2 repeat experiments to follow. Keep test tubes in the Aluminium test tube rack for convenience. 3). To create the water bath effect: boil a kettle filled with tap water; this should take approximately 3 minutes. During this period of time prepare the plastic tub by placing the thermometer in the tub. Once the kettle has boiled pour the hot water to fill up the tub by approximately a third of its capacity, and add the cold water accordingly to reach approximately 5K over the desired temperature condition ensure the heat distribution in the water is even by stirring the tub with a glass rod. Make sure that the tub is no more than half full remove some water if necessary. 4). Submerge the Aluminium test tube holding the reactants rack into the water bath slowly being cautious of water displacement. Leave for a couple of minutes to allow the reactant temperature to acclimatise. Record the temperature of both reactants using the thermometer remembering to wash and dry thermometer in between to avoid cross contamination - prior to the reaction to ensure they are at the desired temperature. 5). Set up the Colorimeter; ensure the appropriate Blue colour filter (2) is set for the colour change of Iodine (orange); Zero the colorimeter using a cuvette filled with distilled water, remove the cuvette of distilled water. Ensure that there is a shady environment for the colorimeter to function adequately (avoid light
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exposure from lab windows) or use a colorimeter cap/lid. 6). Reaction: Simultaneously start the stopwatch whilst pouring the entirety of the contents of boiling tube A into boiling tube B and bump the lip s of the two boiling tubes (with mild force) to ensure the final droplets of reactants are added. Immediately after this firmly secure a rubber bung in the top of the boiling tube and invert the tube four times to ensure that the reaction mixture is mixed thoroughly. Place the tube onto the test tube rack and using a dropper pipette transfer the reaction mixture into an empty clean cuvette. Immediately after this place the cuvette into the colorimeter ensuring that the ribbed faces are not facing the light source. (This should take approximately 20 seconds if performed efficiently) 7). Record the absorbance on the colorimeter at 30 seconds on the stopwatch. Continue to record the absorbance at set intervals of 15 seconds over a total of 345 seconds (5 minutes 45 seconds).
Planned Analysis of Data collected: Deducing Orders of reaction with respect to each reactant: The line graphs drawn constructed from the effects of varying reactant concentration and Absorbance can be used to deduce the rate of reaction using initial rates method. This initial rates method consists of drawing a tangent from the first two plots of data on the progress curve of reaction. Using the tangent the gradient of the slop can be calculated as: or
The value of slope gradient = the rate of reaction (A/s) Note: This process will be applied to each varied concentration per reactant being investigated The rate of reaction values obtained from each concentration variant will be plotted against concentration (in situ) (mol dm) for each reactant being investigated to produce a graph displaying the relationship between these factors. Working out concentration in situ: Concentration of reactant (in situ) = concentration of reactant A line of best fit of this graph can be analysed to determine the order of reaction with respect to that reactant. The order of reaction with respect to each reactant can be deduced this way. Deducing the Rate constant:
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Using the orders of reaction and rate equation, the rate constant can be calculated: The rate equation can be rearranged to calculate the rate constant for that reaction (on the principle that neither the catalyst of temperatures changed):
k=[
] [ ]
By entering the relevant data into the rate equation, rate constants can be calculated for each concentration of reactants that are in the rate equation itself ([A] and [B]), and proceeding this a mean value constant can be worked out for each [A] and [B] and then the mean between these two values can be calculated this is to try and produce the most accurate and reliable value for the rate constant using all of the data from the investigation. Deducing activation enthalpy using the Arrhenius equation: Using the data collected from varying temperature (K) of the reaction, the same method of initial rates will be used to work out how rate of reaction changes with temperature. By natural logging the Arrhenius equation, the activation enthalpy can be calculated by entering the relevant date into the equation in either the linear or comparative form:
Using the linear form will allow for the graphical calculation of activation enthalpy using data from every temperature condition investigated using the Arrhenius plot constructed as OR
This comparative form will allow for non-graphical calculation of activation enthalpy by using data from the largest and smallest temperatures to calculate a theoretical value for Ea. Proposing a mechanism: The orders of reaction can be analysed to help propose a possible reaction mechanism in consideration to which reactants are involved in the initial rate of reaction the rate determining step as this will be a reflection on how the reaction initiates and occurs in conjunction with acid catalysis.
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Risk Assessment: Note: Lab coats, eye protection and rubber gloves should be warn at all time when handling the following chemicals Name of Substance Highest concentration (mol dm3) being used
0.02 mol dm-3
Risk
Dangers
Safety Precautions taken
Iodine
> 1 mol dm-3 Is not considered to be harmful or an irritant
Potentially harmful if you inhale and in contact with skin.
Wear eye protection (even with solutions less than 1 mol dm-3) Avoid spillages as they can cause staining of skin, books, paper and bench surfaces Dont leave exposed Iodine out for prolonged periods of time as it can cause eye irritation Wear eye protection and handle with care When discarding wash down a foulwater drain with plenty of water Wear eye protection Never use a naked flame to heat Propanone
Iodopropanone (product of the reaction)
N/A
Strongly lachrymatory IRRITANT
Propanone (Acetone)
Pure Propanone (13.6mol dm-3)
HIGHLY FLAMMABLE
Repeated exposure may cause skin dryness or cracking Vapours may cause drowsiness and dizziness
IRRITANT
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Sulphuric acid
2.0 mol dm-3
CORROSIVE
Can severely irritate or burn the skin if coming into contact Potentially reacts dangerously with water
Wear eye protection and gloves when handling Sulphuric acid When diluting Sulphuric acid using water make sure to cool the water to lower temperatures and add slowly
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References: 1. Michael J. Clugston, Josolind Flemming, Advanced Chemistry, 2000, Pg264, Pg268 (ISBN 0199146330) 2. G.l. David, Analytical Chemistry, 2001, Pg130 (ISBN 8173713855) George Burton, Chemical Ideas, Volume 4, 2000, Pg 210-215,Pg 242, Pg247 (ISBN 0435631209) Eric V. Anslyn, Dennis A. Dougherty, 2006, Pg383 (ISBN 1891389319) Dr. Geoffrey Neuss, IB Chemistry Study Guide, Oxford University, 2007, Pg35, Pg37-38 (ISBN 978019915142) Emil J. Solwinski, Wayne C. Wolsey, Robert C. Rossi, Iodination of Propanone Activation energy, 10th edition, Pg150 Cleapss 4th edition, Hazcards Anne Hodgson, Chemistry Review, September 2011,Volume 21, Number 1, p19 Web links: http://www.riskassessmentservices.co.uk/HazardSheets.html (06/11/12) http://www.chemguide.co.uk/physical/basicrates/introduction.html http://www.chemicalaid.com/element.php?symbol=I (06/11/12) Iodine chemguide, activation enthalpies, Maxwell-Boltzmann Distribution (13/12/12) http://www.chemguide.co.uk/physical/basicrates/experimental.html chemguide, experimental methods: orders of reaction (13/12/12) http://www.mystrica.com/Colorimeter.aspx Colourimeter (03/01/13) http://www.files.chem.vt.edu/chem-ed/spec/beerslaw.html Beer-Lambert Law (03/01/13) http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinetics/Reaction_Rates/Temperature_Depen dence_of_Reaction_Rates/Arrhenius_Equation
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natural logging the Arrhenius equation (03/01/13) http://scienceaid.co.uk/chemistry/physical/kinetics.html Rates of reaction (06/01/13) http://www.slideshare.net/wkkok1957/ib-chemistry-on-collision-theory-maxwell-boltzmanndistribution-curve-and-arrhenius-equation-12307945 (06/01/13/) http://web.centre.edu/che/che131_lab/volumetricGlassware.htm Error values (07/01/13)
Section 2
Preliminary Work
The Preliminary Work that I carried out consisted of experiments that investigated both the highest concentration and lowest concentration of each individual investigation (varying concentration of Propanone, Iodine and Sulphuric acid). My reasoning behind this was that it would immediately indicate if there was a key methodological problem with my planned experiments (e.g. if a concentration reacted too quickly to record accurate results or if a concentration reacted too slowly to provide a wealth of data).
Problems faced Method (Concentrations)

When starting to carry out my Preliminary experiments I first attempted a rough experiment by adding the reactants together to observe how long the reaction took for an obvious colour change to see if my selection of time intervals was appropriate. The volumes and concentrations I used for this are displayed below: Volume of Propanone 1.0M (cm3) 2.00 Volume of Iodine 0.01M (cm3) 5.00 Volume of Sulphuric acid 1.0M (cm3) 2.00 Volume of distilled water (cm3) 1.00 Total Volume of solution (cm3) 10.00
These conditions produced a reaction that did not produce any significant colour change within an hour of practical session.
Adaptations made Method (Concentrations)
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To resolve this problem of a slow reaction I first tried replacing the 0.01 mol dm Iodine solution with 0.02 mol dm Iodine solution in the hope that this would increase the rate of reaction with respect to Iodine. However, I immediately noted that the colour intensity of 0.02M Iodine was much greater than 0.01M Iodine and when the reaction mixture was put into the Colourimeter, the Absorbance value was greater than 2.00 and so could not be quantifiably measurable by the equipment I had chosen. I alternatively tried increasing the concentration of Propanone in the hope that it would increase the rate of reaction but not increase the Initial Absorbance value (being a colourless solution). However within the laboratory, the maximum stock solution provided was only 2.0 mol dm of Propanone, which I assumed would not be concentrated enough to speed up the reaction to a matter of minutes. To overcome this problem I went about doing a Serial Dilution from Pure Propanone using the equation:
MiVi = MfVf
Initial Molarity (mol dm) x Initial Volume (dm) = Final Molarity (mol dm) x Final Volume (dm) Note: I wanted to attempt using 5.0 mol dm Propanone in the reaction I first had to calculate the concentration of the Pure Propanone I was going to be diluting from: 1). Density of Propanone = 0.791 g/cm (791 g/dm) 2). Mr of Propanone = 58g/mol 3). Density Mr = (791 58) = 13.6 mol dm (Molarity of Pure Propanone) Using MiVi = MfVf I needed to calculate the required volume of Pure Propanone (labelled as ) to dilute in a 250 cm volumetric flask. 13.6M x = 5M x 250 cm
= 91.91 cm
So therefore, I was measuring out 91.91 cm of pure Propanone into a 250 cm volumetric flask using a Burette. Once measured out I filled the rest of the volumetric flask with distilled water until the meniscus was resting on the graduated line using a dropper pipette. I then inverted the flask several times for a couple of minutes to ensure that it mixed thoroughly producing a flask full of 5 mol dm Propanone. Using the 5 mol dm from this Serial Dilution method, the reaction proceeded over 5 minutes which I deemed adequate to use in my investigation as opposed to using 1.0 mol dm Propanone.
26
Problems faced Equipment (Colourimeter)

Note: During my Preliminary experiments I used the standard Colourimeter provided within the laboratory. When recording the Absorbance during a reaction I faced the problem that the meter needle on the Colourimeter would begin to randomly fluctuate back and forth on its own accord. Initially I believed that it could have been methodological error by facing the ribbed face of the cuvette into the light path in the sample holder of the Colourimeter (as opposed to the clear side) and the light was refracting in its course edges and distorting the reading. From this point I ensured the cuvette orientation was correct and that the cuvette itself was clean. However the fluctuations continued despite this, and despite further efforts of turning the device off and back on and trying to zero the colourimeter with distilled water. This Colourimeter had a meter needle that pointed to the absorbance value, and the meter ranged from 0.00-2.00. The meter, however, only recorded to the nearest 0.05, and the space between these marking measurements on the meter were approximately 2-3mm; whenever the needle lay within this space I had to guess intermediate values of 0.025 or 0.075 despite the colourimeter only recording to 2 decimal places (2.d.p.). This assumption left room for a large amount of error. The Colourimeter had an overt sample holder that did not have a cover slide or lid to it. This design would have led to background light exposure influencing the readings and distorting the results I recorded. To temporarily overcome this problem I quite basically casted a shaded environment over the sample holder by placing a folded sheet up paper to create a tent-like effect and minimalise background light interference. Towards the end of a reaction, I observed that the Colourimeter displayed an Absorbance reading of 0.00 indicating that it was colourless like the cuvette of distilled water used to zero the device initially. However, when I removed the cuvette at this stage I noticed that there was still a relatively strong straw-like colour to the reaction mixture suggesting the Colourimeter was inaccurate at recording lower Absorbance values. Despite attempting to zero Colourimeter during the reaction (as well as before) it still made no difference to this limiting factor.
Adaptations made Equipment (Colourimeter)

Note: Due to the fact that the standard Colourimeter proved problematic and was subject to several errors and limitations I decided to invest in a different Colourimeter. The Colourimeter (Mystrica) did not face the same problem of having meter needle fluctuations as it displayed 3 decimal place (3 d.p.) values for Absorbance on a digital display ranging from 01.999. This digital display eliminated any guessing work that was implemented during my Preliminary working. This Colourimeter also provided readings that were 1 decimal place more precise than the previous standard Colourimeter. The Mystrica Colourimeter has a plastic detachable cap/lid for the sample holder so the measurements are covert and free from background light exposure eliminating the effect of a possible confounding variable. However when the Absorbance reading of the Colourimeter was 0.000 I removed the cuvette to find that again there was still some straw-like colour to the mixture I had to accept that this problem must be common in most teaching laboratory Colourimeters.
27
Problems faced Method

During my Preliminary experiments I observed that the initial absorbance readings of repeats of the same experiment differed despite the fact they should have theoretically be the same.
Adaptations made Method

I had several theories as to how this problem could have occurred and consequently approached this problem from several different angles: This problem was most likely to do with how well mixed the reactants were in solution prior to being dropper-pipetted into the cuvette and transferred into the Colourimeter. Initially I was shaking the test tube for 3 seconds; however this alone may not have been sufficient. I altered my method: once the reactants were added into the same test tube I secured a stopper bung into the test tube and inverted the solution 4 times to ensure that the reaction mixture was mixed thoroughly before being transferred. When clearing away test tubes at the end of practical sessions I quite frequently noticed that there was a fractional amount of the reactant left at the bottom of the tube from where it had not been completely poured out this most likely occurred due to the reactant adhering to the lip of the test tube. To overcome this, when pouring the reactant into the same test tube I vertically contacted the test tubes with mild force (not enough to damage the glass of equipment) to make sure the last droplets of reactants are added within the 30 second time constraint. The problem could have also been caused due to contamination of the equipment when measuring out the set volumes of reactants in preparation of the experiments. I used a measuring graduated pipette (5ml) to measure out each of the reactants into the 2 separate test tubes whilst washing this equipment out with distilled water when changing to measuring a separate reactant. However when observing closer, I noticed that from the washing of the equipment, some distilled water remained adhering to the interior surface of the pipette and so when I went to measure out the next set of reactants they would have been mildly diluted within the pipette itself distorting the actual concentration of reactant being added. To overcome this I simply used an excess of the reactants by washing out the graduated pipette with the reactant itself prior to measuring out the actual volume to be used (e.g. washing the pipette with Iodine before measuring out the Iodine).
Results
Varying Sulphuric acid catalyst concentration:
Volume of Propanone 5.0M (cm3) Volume of Iodine 0.01M (cm3) Volume of Sulphuric acid 1.0M (cm3) Volume of distilled water (cm3) Total Volume of solution (cm3)
28
2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345 Volume of Propanone 5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135
5.00
2.00 Absorbance Run 2 1.791 1.775 1.755 1.733 1.712 1.690 1.667 1.645 1.623 1.599 1.574 1.548 1.524 1.498 1.473 1.446 1.391 1.363 1.334 1.303 1.272 1.240 Volume of Sulphuric acid 1.4M (cm3) 2.00 Absorbance Run 2 1.786 1.750 1.716 1.678 1.644 1.611 1.573 1.533
1.00
10.00
Run 1 1.790 1.774 1.754 1.729 1.708 1.684 1.663 1.638 1.613 1.589 1.564 1.534 1.512 1.484 1.458 1.429 1.403 1.373 1.341 1.312 1.281 1.247 Volume of Iodine 0.01M (cm3) 5.00
Run 3 1.789 1.760 1.740 1.721 1.701 1.679 1.657 1.636 1.613 1.589 1.566 1.542 1.518 1.492 1.467 1.438 1.413 1.385 1.357 1.327 1.297 1.266 Volume of distilled water (cm3) 1.00 Total Volume of solution (cm3) 10.00
Run 1 1.786 1.760 1.726 1.687 1.650 1.613 1.573 1.530
Run 3 1.786 1.767 1.724 1.690 1.657 1.622 1.587 1.547
29
150 165 180 195 210 225 240 255 270 285 300 315 330 345 Volume of Propanone 5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315
1.490 1.446 1.402 1.355 1.307 1.258 1.204 1.151 1.092 1.032 0.968 0.906 0.842 0.774 Volume of Iodine 0.01M (cm3) 5.00
1.493 1.452 1.472 1.367 1.323 1.275 1.226 1.177 1.123 1.071 1.012 0.948 0.892 0.823 Volume of Sulphuric acid 1.6M (cm3) 2.00 Absorbance Run 2 1.744 1.718 1.670 1.625 1.574 1.524 1.467 1.413 1.351 1.289 1.224 1.154 1.084 1.008 0.931 0.848 0.767 0.675 0.587 0.493
1.509 1.468 1.426 1.386 1.339 1.295 1.248 1.199 1.146 1.092 1.039 0.981 0.924 0.862 Volume of distilled water (cm3) 1.00 Total Volume of solution (cm3) 10.00
Run 1 1.746 1.707 1.658 1.609 1.560 1.512 1.461 1.407 1.353 1.293 1.233 1.170 1.106 0.968 0.890 0.816 0.740 0658 0.577 0.491
Run 3 1.740 1.704 1.655 1.609 1.563 1.513 1.463 1.408 1.353 1.292 1.231 1.165 1.095 1.026 0.950 0.877 0.796 0.716 0.629 0.543
30
330 345 Volume of Propanone 5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345 Volume of Propanone 5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60
0.409 0.320 Volume of Iodine 0.01M (cm3) 5.00
0.402 0.306 Volume of Sulphuric acid 1.8M (cm3) 2.00 Absorbance Run 2 1.743 1.731 1.660 1.607 1.547 1.494 1.431 1.362 1.298 1.227 1.149 1.072 0.986 0.893 0.808 0.715 0.615 0.516 0.409 0.294 0.207 0.122 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance Run 2 1.708 1.655 1.598
0.450 0.358 Volume of distilled water (cm3) 1.00
Total Volume of solution (cm3) 10.00
Run 1 1.720 1.670 1.615
Run 3 1.730 1.691 1.634
31
75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345
1.566 1.500 1.434 1.368 1.296 1.221 1.139 1.052 0.965 0.869 0.774 0.675 0.568 0.458 0.352 0.244 0.120 0.083 0.055
1.538 1.476 1.410 1.338 1.258 1.179 1.091 1.021 0.903 0.805 0.698 0.592 0.477 0.366 0.252 0.153 0.080 0.051 0.045
1.577 1.513 1.447 1.376 1.304 1.223 1.141 1.053 0.959 0.868 0.761 0.657 0.545 0.438 0.319 0.215 0.124 0.075 0.060
Varying Iodine concentration (in situ):

Volume of Propanone 5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 Volume of Iodine 0.02M (cm3) 2.00 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance Run 2 0.900 0.881 0.858 0.834 0.812 0.789 0.764 0.741 0.718 0.693 0.668 0.644 0.619 Volume of distilled water (cm3) 14.00 Total Volume of solution (cm3) 20.00
Run 1 0.896 0.878 0.855 0.831 0.810 0.785 0.764 0.741 0.716 0.693 0.668 0.643 0.619
Run 3 0.896 0.877 0.855 0.832 0.812 0.786 0.764 0.741 0.717 0.692 0.667 0.643 0.618
32
225 240 255 270 285 300 315 330 345 Volume of Propanone 5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345 Volume of Propanone
0.593 0.567 0.542 0.517 0.491 0.465 0.438 0.411 0.383 Volume of Iodine 0.02M (cm3) 3.00
0.594 0.568 0.542 0.515 0.488 0.462 0.434 0.408 0.379 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance Run 2 1.332 1.313 1.294 1.274 1.255 1.235 1.216 1.196 1.176 1.156 1.135 1.114 1.093 1.071 1.049 1.028 1.004 0.982 0.966 0.939 0.916 0.894 Volume of Sulphuric acid
0.592 0.567 0.542 0.514 0.488 0.460 0.432 0.404 0.376 Volume of distilled water (cm3) 13.00 Total Volume of solution (cm3) 20.00
Run 1 1.330 1.311 1.293 1.273 1.255 1.235 1.216 1.194 1.177 1.157 1.137 1.117 1.097 1.076 1.054 1.033 1.010 0.989 0.966 0.943 0.922 0.898 Volume of Iodine 0.02M
Run 3 1.330 1.312 1.293 1.272 1.253 1.232 1.215 1.195 1.175 1.156 1.136 1.115 1.094 1.070 1.050 1.031 1.006 0.986 0.966 0.940 0.918 0.896 Volume of distilled water Total Volume of solution (cm3)
33
5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345 Volume of Propanone 5.0M (cm3) 2.00 Results Time (seconds) 30 45 60 75 90 105 120
(cm3) 4.00
2.0M (cm3) 2.00 Absorbance Run 2 1.681 1.679 1.651 1.622 1.595 1.577 1.553 1.531 1.519 1.500 1.485 1.468 1.445 1.429 1.412 1.389 1.377 1.359 1.342 1.320 1.301 1.282 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance Run 2 1.702 1.689 1.674 1.662 1.648 1.635 1.624
(cm3) 12.00
20.00
Run 1 1.703 1.690 1.677 1.659 1.642 1.631 1.620
Run 3 1.716 1.705 1.697 1.683 1.668 1.656 1.646
34
135 150 165 180 195 210 225 240 255 270 285 300 315 330 345
1.607 1.595 1.587 1.571 1.558 1.545 1.534 1.521 1.508 1.495 1.482 1.470 1.457 1.443 1.430
1.611 1.597 1.585 1.570 1.557 1.545 1.531 1.518 1.505 1.491 1.477 1.461 1.447 1.438 1.419
1.634 1.625 1.610 1.600 1.586 1.574 1.563 1.551 1.539 1.527 1.515 1.501 1.489 1.475 1.463
Varying Propanone concentration:

Volume of Propanone 2.5M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 Volume of Iodine 0.02M (cm3) 2.00 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance Run 2 1.942 1.938 1.935 1.931 1.927 1.923 1.916 1.913 1.909 1.909 1.898 1.895 1.891 1.888 1.885 1.878 1.875 Volume of distilled water (cm3) 14.00 Total Volume of solution (cm3) 20.00
Run 1 1.928 1.924 1.921 1.917 1.913 1.910 1.903 1.903 1.886 1.892 1.889 1.885 1.879 1.875 1.869 1.865 1.862
Run 3 1.930 1.928 1.922 1.919 1.915 1.911 1.905 1.902 1.886 1.899 1.892 1.887 1.880 1.876 1.870 1.866 1.861
35
285 300 315 330 345 Volume of Propanone 5.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345 Volume of Propanone 7.5M (cm3) 2.00 Results:
1.856 1.853 1.846 1.843 1.840 Volume of Iodine 0.02M (cm3) 2.00
1.871 1.868 1.862 1.856 1.852 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance Run 2 1.930 1.923 1.912 1.905 1.894 1.884 1.874 1.865 1.852 1.843 1.833 1.822 1.810 1.799 1.788 1.777 1.764 1.754 1.742 1.730 1.718 1.705 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance
1.855 1.851 1.844 1.840 1.838 Volume of distilled water (cm3) 14.00 Total Volume of solution (cm3) 20.00
36
Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345 Volume of Propanone 10.0M (cm3) 2.00 Results: Time (seconds) 30 45 60 75 90 105 120 135 150 165 180
Run 2 1.850 1.841 1.829 1.820 1.806 1.797 1.784 1.771 1.760 1.745 1.738 1.721 1.712 1.699 1.686 1.671 1.652 1.641 1.628 1.615 1.599 1.585 Volume of Sulphuric acid 2.0M (cm3) 2.00 Absorbance Run 2 1.851 1.836 1.821 1.804 1.784 1.766 1.748 1.729 1.710 1.688 1.669
Run 1 1.870 1.857 1.841 1.823 1.809 1.792 1.776 1.760 1.743 1.723 1.707
Run 3 1.870 1.856 1.839 1.821 1.807 1.790 1.772 1.758 1.740 1.718 1.699
37
195 210 225 240 255 270 285 300 315 330 345
1.692 1.670 1.652 1.635 1.614 1.594 1.574 1.534 1.533 1.512 1.491
1.647 1.626 1.606 1.581 1.560 1.536 1.515 1.490 1.465 1.442 1.416
1.688 1.666 1.645 1.629 1.610 1.590 1.571 1.553 1.532 1.512 1.490
Varying Temperature (K) of reaction

(Measurements below are the same for each temperature condition) Volume of Volume of Volume of Volume of Propanone Iodine 0.01M Sulphuric acid distilled water 5.0M (cm3) (cm3) 2.0M (cm3) (cm3) 2.00 5.00 2.00 1.00 Total Volume of solution (cm3) 10.00
293K
Results: Absorbance Run 2 1.719 1.656 1.599 1.541 1.476 1.409 1.340 1.260 1.180 1.089 1.020 0.900 0.804 0.696 0.592 0.472 0.367
Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270
Run 1 1.720 1.669 1.615 1.570 1.498 1.430 1.371 1.293 1.220 1.140 1.053 0.965 0.868 0.771 0.671 0.568 0.460
Run 3 1.728 1.693 1.621 1.576 1.516 1.449 1.376 1.301 1.223 1.141 1.051 0.960 0.871 0.758 0.655 0.545 0.440
38
285 300 315 330 345
0.351 0.241 0.119 0.080 0.055
0.249 0.153 0.046 0.051 0.045
0.316 0.212 0.120 0.075 0.060
303K
Results: Absorbance Run 2 1.683 1.573 1.468 1.339 1.199 1.087 0.939 0.764 0.639 0.492 0.343 0.210 0.118 0.077 0.066 0.059 0.053 0.050 0.051 0.051 0.051 0.051
Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345
Run 1 1.676 1.559 1.444 1.322 1.195 1.061 0.921 0.752 0.632 0.480 0.330 0.202 0.111 0.079 0.067 0.063 0.052 0.051 0.050 0.051 0.051 0.051
Run 3 1.666 1.543 1.422 1.301 1.160 0.983 0.901 0.744 0.627 0.479 0.319 0.196 0.106 0.068 0.059 0.055 0.052 0.052 0.051 0.051 0.051 0.051
313K
Results: Time (seconds) Run 1 Absorbance Run 2 Run 3
39
30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345
1.413 1.287 1.120 0.948 0.754 0.563 0.356 0.183 0.077 0.054 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051
1.500 1.349 1.196 0.967 0.761 0.575 0.360 0.192 0.079 0.053 0.052 0.052 0.052 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051
1.455 1.299 1.133 0.983 0.777 0.589 0.377 0.200 0.093 0.060 0.053 0.053 0.051 0.050 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051
323K - Due to how quickly the reaction completed at 323K, I adjusted the time intervals to
every 10 seconds (starting at 20 seconds) to collect adequate amounts data Results: Absorbance Time (seconds) Run 1 Run 2 Run 3 20 0.897 0.940 0.799 30 0.502 0.531 0.486 40 0.221 0.250 0.201 50 0.099 0.090 0.065 60 0.061 0.058 0.061 70 0.053 0.052 0.054 80 0.052 0.052 0.051 90 0.052 0.052 0.050 100 0.051 0.051 0.051 110 0.050 0.051 0.051 120 0.051 0.051 0.051
Mean Values
40
Varying Concentration of Iodine (in situ) (mol dm-3) Mean Absorbance Values Time (Seconds) Vol. Iodine Vol. Iodine Vol. Iodine Vol. Iodine 2cm3 3cm3 4cm3 5cm3 30 0.897 1.331 1.661 1.707 45 0.879 1.312 1.649 1.695 60 0.856 1.293 1.629 1.683 75 0.832 1.273 1.607 1.655 90 0.811 1.254 1.586 1.653 105 0.787 1.234 1.569 1.641 120 0.764 1.216 1.550 1.630 135 0.741 1.195 1.531 1.617 150 0.717 1.176 1.520 1.606 165 0.693 1.156 1.505 1.594 180 0.668 1.136 1.488 1.580 195 0.643 1.115 1.471 1.567 210 0.619 1.095 1.453 1.555 225 0.593 1.072 1.435 1.543 240 0.567 1.051 1.417 1.530 255 0.542 1.031 1.399 1.517 270 0.515 1.007 1.382 1.504 285 0.489 0.986 1.365 1.490 300 0.462 0.966 1.343 1.477 315 0.435 0.941 1.323 1.481 330 0.408 0.919 1.304 1.452 345 0.379 0.896 1.285 1.437 Varying Concentration of Propanone (mol dm-3) Mean Absorbance Values Time (Seconds) Conc. Conc. Conc. Conc. 2.5M 5.0M 7.5M 10.0M 30 1.930 1.930 1.832 1.850 45 1.926 1.922 1.820 1.834 60 1.922 1.914 1.811 1.816 75 1.918 1.906 1.797 1.800 90 1.915 1.896 1.786 1.783 105 1.908 1.886 1.775 1.765 120 1.906 1.876 1.762 1.749 135 1.894 1.865 1.750 1.731 150 1.900 1.853 1.736 1.710 165 1.893 1.844 1.724 1.692
41
180 195 210 225 240 255 270 285 300 315 330 345
1.889 1.883 1.880 1.845 1.840 1.866 1.861 1.857 1.851 1.846 1.843 1.843
1.833 1.822 1.812 1.799 1.788 1.777 1.766 1.756 1.744 1.730 1.718 1.705
1.711 1.700 1.688 1.673 1.656 1.642 1.631 1.616 1.603 1.587 1.573 1.573
1.676 1.654 1.634 1.615 1.595 1.576 1.553 1.526 1.510 1.489 1.466 1.466
Varying Concentration of Sulphuric acid (mol dm-3) Mean Absorbance Values Time (Seconds) Conc. Conc. Conc. Conc. Conc. 1.0M 1.4M 1.6M 1.8M 2.0M 30 1.790 1.786 1.743 1.743 1.719 45 1.770 1.759 1.710 1.706 1.672 60 1.750 1.722 1.661 1.647 1.616 75 1.728 1.685 1.614 1.589 1.560 90 1.707 1.650 1.566 1.530 1.496 105 1.684 1.615 1.516 1.470 1.430 120 1.662 1.578 1.464 1.404 1.361 135 1.640 1.537 1.409 1.333 1.286 150 1.616 1.497 1.352 1.264 1.208 165 1.592 1.455 1.291 1.187 1.124 180 1.568 1.433 1.229 1.105 1.042 195 1.541 1.369 1.163 1.023 0.942 210 1.518 1.323 1.095 0.933 0.847 225 1.491 1.276 1.001 0.839 0.744 240 1.466 1.226 0.924 0.745 0.641 255 1.438 1.176 0.847 0.646 0.530 270 1.402 1.120 0.768 0.540 0.421 285 1.374 1.065 0.683 0.437 0.308 300 1.344 1.006 0.598 0.328 0.204 315 1.314 0.945 0.509 0.223 0.108 330 1.283 0.886 0.420 0.139 0.070 345 1.251 0.820 0.328 0.080 0.053
42
Varying Temperature of reaction (Kelvin) Mean Absorbance Values Time (Seconds) Temp. Temp. Temp. Temp. 293 303 313 323 30 1.722 1.675 1.456 (20)s: 0.879 45 1.673 1.558 1.312 (30s): 0.506 60 1.612 1.445 1.150 (40s): 0.224 75 1.562 1.321 0.966 (50s): 0.085 90 1.497 1.185 0.764 (60s): 0.060 105 1.429 1.044 0.576 (70s): 0.053 120 1.362 0.920 0.364 (80s): 0.052 135 1.285 0.753 0.192 (90s): 0.051 150 1.208 0.633 0.083 (100s):0.051 165 1.123 0.484 0.056 (110)s:0.051 180 1.041 0.331 0.052 (120)s:0.051 195 0.942 0.203 0.052 210 0.848 0.112 0.051 225 0.742 0.075 0.051 240 0.639 0.64 0.051 255 0.528 0.59 0.051 270 0.422 0.52 0.051 285 0.305 0.51 0.051 300 0.202 0.51 0.051 315 0.095 0.51 0.051 330 0.069 0.51 0.051 345 0.053 0.51 0.051 -
Section 3
Orders of reaction:
One aim of this investigation was to calculate orders of reaction with respect to each reactant (Iodine and Propanone) and with respect to the acid catalyst (Sulphuric acid) through using the rate equation: Rate o = k[ ] [ ] The proposed rate equation that was empirically tested by the investigation is displayed below: ] [ ] [ ] Rate o = k[ The order of reaction cannot be deduced simply by assuming it is to do with molar ratio of the balanced reaction equation; orders of reaction can only be calculated through experimentation. The 3 variables investigated were sub divided into 3 separate experiments: - Varying the concentration of Iodine (in situ) (mol dm-3) - Varying the concentration of Propanone (mol dm-3)
43
Varying the concentration of Sulphuric acid (mol dm-3)
By individually varying concentrations of each reactant, their effect on the rate of reaction (A/s1 ) was quantifiably measured. The rate of reaction for this investigation was measured using initial rates method.
Order of reaction with respect to Iodine:

The quantities used in these experiments are as displayed below: Experiment Volume of Volume of Volume of Volume of 5.0M 0.02M Iodine 2.0M Water (cm3) Propanone (cm3) Sulphuric 3 (cm ) acid (cm3) 1 2.00 2.00 2.00 14.00 2 2.00 3.00 2.00 13.00 3 2.00 4.00 2.00 12.00 4 2.00 5.00 2.00 11.00
Total Volume of solution (cm3) 20.00 20.00 20.00 20.00
Quantitative analysis:
As 3 repeats were taken for each condition in the experiments, mean values were calculated (ignoring anomalous values) to increase the reliability of the data used in any calculations or graphs. The mean values were used to construct line graphs, using the initial rates method, tangents were drawn from the first two plots of data at the assumed start of the reaction and from this tangent the gradient was calculated using: . The gradient of the graph is -1 representative of the rate of reaction as A/s . This unit is proportional to mol dm-3/s-1 according to Beer-Lamberts Law, which states there is a linear relationship between the two measurements. The concentration of Iodine (in situ) (mol dm-3) can be calculated from the experiments conditions: Concentration of Iodine (in situ) = concentration of Iodine So therefore: Concentration of Iodine (in situ) = 0.02M Experiment 1 2 3 4 Calculation 0.02 0.02 0.02 0.02 0.10 0.15 0.20 0.25 Concentration of Iodine (in situ) (mol dm-3) 0.0002 0.0003 0.0004 0.0005
The rates of reaction (gradient) (A/s-1) deduced from the mean values of each experiment are displayed in the table below: (to 3 significant figures)
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Experiment 1 2 3 4
Rate of reaction (A/s-1) -0.00130 -0.00120 -0.00111 -0.00104
Rate of reaction was plotted over concentration to deduce the order of reaction from the shape of the line graph with respect to Iodine:
45
Qualitative interpretation:
The findings of this graph are relatively surprising and unexpected. If the scale used on the y axis is increased the plots appear to be in a relatively flat line suggesting 0 order with respect to
46
Iodine. However, the y axis measurement used was deliberately proportional in each graph drawn so that findings were comparable and not distorted in any way. Going on the interpretation that the line is flat enough to be classified zero order, this means that the rate of reaction is independent of Iodine and therefore Iodine is cannot be included in the rate equation nor be involved in a rate determining step. However the findings of these experiments seem to show a slight positive gradient from the line of best fit suggesting that as the concentration of Iodine increases the rate of reaction decreases. These findings go against the basic explanations of Collision theory: the higher the concentration of reactant within a fixed volume the more frequent successful collision between reactant species and the faster the rate of reaction. There is the chance that the data is not valid and the results have been distorted by an unknown variable (e.g. contamination) that was progressively enhanced after each experiment. Contradictory to this, it must be noted that reflecting on my data journal, the experiments were not performed sequentially like the method suggests.
Order of reaction with respect to Propanone:

The quantities used in these experiments are as displayed below: Volume of Volume of Volume of Volume of Total Volume Propanone 0.02M Iodine 2.0M Water (cm3) of solution 3 3 (cm ) (cm ) Sulphuric (cm3) 3 acid (cm ) 2.00 2.00 2.00 14.00 20.00 The individual stock concentrations of Propanone used (mol dm-3) 2.5 5.0 7.5 10.0
Quantitative Analysis:
As 3 repeats were taken for each condition in the experiments, mean values were calculated (ignoring anomalous values) to increase the reliability of the data used in any calculations or graphs. The mean values were used to construct line graphs, using the initial rates method, tangents were drawn from the first two plots of data at the assumed start of the reaction and from this tangent the gradient was calculated using: . The gradient of the graph is -1 representative of the rate of reaction as A/s . This unit is proportional to mol dm-3/s-1 according to Beer-Lamberts Law, which states there is a linear relationship between the two measurements. The concentration of Propanone (in situ) (mol dm-3) can be calculated from the experiments conditions:
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Concentration of Propanone (in situ) = concentration of Propanone So therefore: Concentration of Propanone (in situ) = Experiment 1 2 3 4 Calculation 2.5 0.1 5.0 0.1 7.5 0.1 10.0 0.1 Concentration of Propanone (in situ) (mol dm-3) 0.25 0.50 0.75 1.00
The rates of reaction (gradient) (A/s-1) deduced from the mean values of each experiment are displayed in the table below: (to 3 significant figures) Experiment Rate of reaction (A/s-1) 1 -0.00028 2 -0.00054 3 -0.00064 4 -0.00108 Rate of reaction was plotted over concentration to deduce the order of reaction from the shape of the line graph with respect to Propanone:
48
Qualitative Interpretation:
This graph displays clear proportionality between Propanone concentrations and the rate of reaction. Due to the distinct shape of the graph, it can be deduced that the order of reaction with respect to Propanone is 1st order. In terms of the rate equation, this means rate of initial reaction is dependent on the concentration of Propanone suggesting that Propanone is involved in a rate determining Whereas Iodine is not.
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Order of reaction with respect to Sulphuric acid catalyst:

The quantities used in these experiments are as displayed below: Volume of Volume of Volume of Volume of Total Volume 3 Propanone 0.01M Iodine Sulphuric Water (cm ) of solution 5.0M (cm3) (cm3) acid (cm3) (cm3) 2.00 5.00 2.00 1.00 10.00 The individual stock concentrations of Sulphuric acid used (mol dm-3) 1.0 1.4 1.6 1.8 2.0
As 3 repeats were taken for each condition in the experiments, mean values were calculated (ignoring anomalous values) to increase the reliability of the data used in any calculations or graphs. The mean values were used to construct line graphs, using the initial rates method, tangents were drawn from the first two plots of data at the assumed start of the reaction and from this tangent the gradient was calculated using: . The gradient of the graph is -1 representative of the rate of reaction as A/s . This unit is proportional to mol dm-3/s-1 according to Beer-Lamberts Law, which states there is a linear relationship between the two measurements. The concentration of Sulphuric acid (in situ) (mol dm-3) can be calculated from the experiments conditions: Concentration of Sulphuric acid (in situ) = concentration of Sulphuric a.
So therefore: Concentration of Sulphuric acid (in situ) = Experiment 1 2 3 4 5 Calculation 1.0 1.4 1.6 1.8 2.0 0.2 0.2 0.2 0.2 0.2 Concentration of Sulphuric acid (in situ) (mol dm-3) 0.20 0.28 0.32 0.36 0.40
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The rates of reaction (gradient) (A/s-1) deduced from the mean values of each experiment are displayed in the table below: (to 3 significant figures) Experiment Rate of reaction (A/s-1) 1 -0.00130 2 -0.00179 3 -0.00240 4 -0.00280 5 -0.00317 Rate of reaction was plotted over concentration to deduce the order of reaction from the shape of the line graph with respect to Propanone:
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52
Qualitative Interpretation:
Quite surprisingly this graph displays the distinct shape of a 1st order reaction with respect to Sulphuric acid. Being a catalyst, the expected order of reaction with respect to Sulphuric acid would be 0 order as catalysts are not used up within a reaction. In terms of the rate equation, this means rate of initial reaction is dependent on the concentration of H+ ions produced from the sulphuric acid during the start of the reaction. This is quite a strong indication that both Sulphuric acid and Propanone are the two species involved in the rate determining step of the reaction as they are both 1st order and effect the initial rate of reaction. Using the above findings, it can be deduced that the rate equation for the acid catalysed reaction between Iodine and Propanone is:
] [
] ] [ ] + n:
OR
Note: [H+] refers to the hydrogen ions produced from the sulphuric acid during acid catalysis of the reaction This means that the overall order can be calculated simply through m Overall order of reaction = 2
nd
Order
Calculating Rate constants:

Now that the rate equation has been established, it can be rearranged to calculate the rate constant at Room temperature:
k=[
] [
To calculate the most reliable value for K, rate constants were calculated for each concentration condition for both Propanone and Sulphuric being the only reactants that affect the rate of reaction. From these constants a mean value can be established: Propanone: Concentration [P][S] (in situ) Rate (A/s-1) K 0.25 X 0.2 -0.00028 -0.00560 0.50 X 0.2 -0.00054 -0.00540 0.75 X 0.2 -0.00064 -0.00427 1.00 X 0.2 -0.00108 -0.00540 M-1s-1) Sulphuric acid: Concentration [P][S] (in situ) 0.20 X 1.00 0.28 X 1.00 0.32 X 1.00 Rate (A/s-1) -0.00130 -0.00179 -0.00240 K -0.00650 -0.00639 -0.00750
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0.36 X 1.00 0.40 X 1.00
-0.00280 -0.00317
-0.00778 -0.00793
(-0.00722 M-1s-1) Finally, by calculating the mean of these two means the rate constant will be representative to all relevant data relevant to the rate equation:
K = (-0.00620 M-1s-1)
Deducing the activation enthalpy (Ea) of the reaction using the linear form of the Arrhenius equation:
The quantities used when varying Temperature (K) are displayed below Volume of Volume of Volume of Volume of Propanone Iodine 0.01M Sulphuric acid Water (cm3) 3 3 3 5.0M (cm ) (cm ) 2.0M (cm ) 2.00 5.00 2.00 1.00 Total Volume of solution(cm3) 10.00
These conditions were repeated over temperature intervals of 10K from 293-323K. From the results obtained, graphs of Absorbance of Iodine can be drawn, from these, using the initial rates method; the rate of reaction of each experiment at different temperatures can be calculated. Below is the table of rate of reaction at different temperatures. Note: the temperature values will not work in the Arrhenius equation unless they are in Kelvin The gradient of these graphs were: (to 3 significant figures) Temperature (Kelvin) Rate (A/s-1) 293 -0.00358 303 -0.00666 313 -0.00916 323 -0.0416 Using these rates of reaction, rate constants can be calculated for each different reaction temperature using the equation: [ ] [ ] Note: the concentrations used in the rate equation refers to the reactant concentrations in situ of the total volume of reaction (10 cm3)
Varying the temperature of reaction: (Rate Constants)

Temperature (Kelvin) 293 Constant Calculation ( k = ) Constant value -0.00895
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303 313 323
-0.01670 -0.02290 -0.10400
The constant values displayed in the table above are a clear indication that the k constant in the rate equation increases when temperature (k) is increased
The Arrhenius equation

By natural logging the Arrhenius equation, we can rearrange the equation into a y = mx + c format for linear expression of the equation
T (Temperature) can be changed into its reciprocal value lnA represents where the slope/gradient from the line of best fit intercepts at the y axis (lnK) on the Arrhenius plot. T K 1/T lnK 293 -0.00895 0.00341 -5.68017 303 -0.01670 0.00330 -5.71373 313 -0.02290 0.00319 -5.74620 323 -0.10400 0.00310 -5.77765 Using the above information lnK was plotted over 1/T to produce the Arrhenius plot:
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By extrapolating the graph back to the lnK axis, the point of interception with the y axis gives the value of lnA = -5.666 The gradient of the line is calculated using the basic equation: Gradient = = 313.725
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Note: gradient = Calculation Ea from the Arrhenius plot:
Ea = G x R
Where: G = Gradient = 313.725 R = Gas constant (8.314 J mol K) Therefore, Ea = 313.725 8.314 = 2608.3 J mol
Ea = 2.6083 KJ mol
Result: The activation enthalpy of the acid catalysed reaction between Iodine and Propanone was found to be 2.6083 KJ mol using the linear form of the Arrhenius equation and the Arrhenius plot OR
Deducing the activation enthalpy (Ea) of the reaction using the Comparative form of the Arrhenius equation:
The comparative form of the Arrhenius equation is as follows:
The justification behind using the highest and lowest temperatures (K) was that by having points with values furthest away from each other, this is a better measurement of the slope line. T (Kelvin) K( ) 1 2 293 323 -0.00895 -0.10400
Note: R represents the Gas constant: (8.314 J mol K) Enter the information from the table into the comparative Arrhenius equation: ( )
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Simplify the values with the equation:
( Resultantly,
The equation can be rearranged so that Ea is alone on side by dividing the (0.00031699) from both sides of the equation giving: ( ) (
value
Before doing the same process to the gas constant (8.132), into a number: ( )
) should be expanded
So the equation can rearrange to become: Therefore, Ea = 65.7 J mol
0.0657 KJ mol
Qualitative interpretation:
The activation enthalpy (Ea) calculated using the comparative form of Arrhenius equation was 0.0657KJ mol this value is significantly lower than the value 2.6083J mol calculated using the linear form of Arrhenius equation. The linear form of the Arrhenius equation uses the data and rates of reaction values from every each temperature condition investigated whereas the comparative form of the Arrhenius equation however only compares two temperature conditions which were the highest and lowest temperatures. The linear calculated activation enthalpy is more likely to be representative of my investigation as it incorporates more of the collected data in the calculation. Both values were lower than I would have expected them to be. The explanation surrounding this could be that the acid catalysis of the reaction significantly lowers the activation enthalpy to the low value of 2.6 KJ mol. This can be graphically explained
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in terms of collision theory of enthalpy profiling and the Maxwell-Boltzmann distribution curve: By lowering the Ea through catalysis the enthalpy peak on an enthalpy profile required for reactant species to react successfully is smaller, and in terms of the Maxwell-Boltzmann Distribution the curve the shaded area representative of the Ea is more further left on the x axis meaning a larger area of the distribution is shaded both representations support the idea that through use a catalyst a greater proportion of the reactant species have the minimum required energy to react. This reduction in required energy to react could explain why my value is lower than expected.
Proposed Mechanism
Above is the proposed mechanism of the acid catalysed reaction between Iodine and Propanone. Process: 1). Protonation of oxygen (reversible) (slow) RATE-DETERMINING STEP The rate determining step is the slowest of the entire reaction and refers to the protonation of oxygen within the Propanone structure 2). enol formation isomerism (reversible) (fast) 3). Ketone Halogen attachment (irreversible) (fast) 4). De-protonation of oxygen (irreversible) (fast) Justification: Rate equation:
] [
Many reactions do not go in one step. This is particularly true when there are more than two reactant molecules as the chances of a successful collision between three or more is extremely small. Deducing the orders of reaction was highly insightful in regards to proposing a reaction
59
mechanism for this reaction. Being 0 order with respect to iodine, Propanone and aqueous H+ ions (Sulphuric acid) must be involved in the rate determining step as those are the only two reactants that effect rate. The order of reaction with respect to a reactant is a reflection on the molecularity of the reaction mechanism. As both reactants in the rate equation are 1 st order, this indicates that the reaction mechanism starts with the reactions between one molecules of propanone with one aqueous hydrogen ion. This kinetic observation proves that there must be at least 2 steps to this reaction as Iodine has to react in order to form the produce Iodopropanone suggesting it reacts at a later stage. However an additional two stages are required in the mechanism to explain how H+ ions both cause the rate determining step as well as to de-protonate from Propanone so the catalyst is not used up in the reaction and remains chemically unchanged.
Outcomes of the investigation and initial aims:

AIM 1
1). I aim to individually vary the concentrations of each reactant (Iodine and Propanone) including the acid catalyst (Sulphuric acid) in solution and measure its effect on the rate of reaction in Absorbance (Beer-Lambert Law) using Colourimetry. All of data collected will be used to construct line graphs for each concentration of reactant investigated per experiment. Using the trends of these line graphs, the initial rates of reaction method can be used by drawing tangents from the starting plots of the reaction progress curve to calculate each rate of reaction (A/s-1). Finally these values of rate of reaction can be plotted against concentration of the reactant being investigated to deduce the order of reaction with respect to that reactant this process will be carried out for each reactant.
] [
] ] [ ]
[
AIM 2
OR
2). Using the orders of reaction and the rate equation, I aim to calculate a mean rate constant (at room temperature). Through addition of reactant orders (m+n) the overall order of reaction can be deduced.
K = (-0.00620 M-1s-1) nd Overall order of reaction = 2 Order
AIM 3
3). Using two forms of the Arrhenius equation, I aim to calculate the activation enthalpy (Ea) of the reaction by varying temperature (Kelvin) - conditions ranging from 293-323 Kelvin.
= 2.6083 KJ mol (Linear) 0.0657 KJ mol (Comparative)

AIM 4
4). Using the orders of reaction with respect to Iodine, Propanone and Sulphuric acid as an indication, I intend to propose a possible mechanism for the entire reaction.
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Evaluation
Equipment errors: Equipment Colourimeter (preliminary) Colourimeter (Mystrica) 250ml Volumetric flask 50ml Volumetric flask 50cm3 Burette 10ml graduated pipette 5ml Measured graduate pipette 373K Thermometer Stopwatch Error (unit) 0.025 0.001 0.01ml 0.05ml 0.05cm3 0.04ml 0.005ml 0.2K 0.01s
Justification of equipment: By using a 5ml measured graduated pipette, any volume ranging from 0.5cm3 to 5.0cm3 can be measured using just a single pipette this makes measuring out quantities in experiments a faster process and is generally more convenient (providing you wash the equipment appropriately before changing reactant being measured). The Colourimeter (Mystrica) was used as opposed to the standard provided Colourimeter used in my preliminary tests for the following reasons: - The Colourimeter (Mystrica) did not face the same problem of having meter needle fluctuations as it precisely displays 3 decimal place (3 d.p.) values for Absorbance on a digital display ranging from 0-1.999. This digital display eliminated any guessing work that was implemented during my Preliminary working.
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This Colourimeter also provided readings that were 1 decimal place more precise than the previous standard Colourimeter. The Mystrica Colourimeter has a plastic detachable cap/lid for the sample holder so the measurements are covert and free from background light exposure eliminating the effect of a possible confounding variable.
The 250ml volumetric flask was used to produce the highest concentration of reactant via dilution (e.g. 10M Propanone), and from this 250ml I can make up all the lower concentrations in the 50ml - whilst still having an excess of the highest concentration left for experimentation.
Varying the concentration of Iodine (in situ):

Experiment Volume of 5.0M Propanone (cm3) 2.00 2.00 2.00 2.00 Volume of 0.02M Iodine (cm3) 2.00 3.00 4.00 5.00 Volume of 2.0M Sulphuric acid (cm3) 2.00 2.00 2.00 2.00 Volume of Water (cm3) Total Volume of solution (cm3) 20.00 20.00 20.00 20.00
1 2 3 4
14.00 13.00 12.00 11.00
% errors of all measurements: Note: due to this variable being investigated in situ no dilutions needed to be carried out Measuring out quantities of reactants: (analogue measurement error) Volume of Propanone 2cm3 0.01 (5ml graduated pipette) Volume of Iodine 2cm3 0.01(5ml graduated pipette) Volume of Sulphuric acid 2cm3 0.01(5ml graduated pipette) Volume of Water 4cm4 0.01(5ml graduated pipette) Volume of Water 10cm3 0.04(10ml graduated pipette) 20cm3 0.08cm3 = 0.4% per experiment (measuring out reactants) This calculated error percentage is reassuring, as an error % of 0.4 is quite insignificant when considering that I was working with relatively small quantities. This confirms my belief that, this error uncertainty would not have a negatively impacted the accuracy on my results or outcomes from this method. Recording Absorbance using Colourimeter: (digital measurement error) Random Mean Absorbance value (from experiment 4): 1.683 0.001 Uncertainty calculation from its repeats: 1.677
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1.674 1.697 Uncertainty = 1.683 0.0115 = 0.7% error uncertainty The % error uncertainty calculated from colourimeter repeats was a relatively low figure of 0.7%. However, it has an uncertainty value higher than the measuring process for this investigation. This uncertainty had the greatest potential impact on my results Procedural limitations: The method of initial rates is used to measure the rate of reaction. However once the reactants have been added together they automatically begin to react. By following the method exactly you can only have transferred the reaction sample into the colourimeter to record its Absorbance value at 30 seconds. This means that the first 30 seconds of the reaction is missed whilst carrying out this physical procedure. Considering you are measuring the initial rate of reaction, this compromises this whole concept of initial rate as it cannot be recorded immediately within the constraints of the procedure. This procedural error creates a large source of doubt as to the true validity of my results. Just before the reaction commenced I faced the problem that I could not physically start the timer on the stopwatch whilst adding the contents of test tube A and B together at the same time. I resolved this problem by asking for assistance of a colleague within close proximity of my work space to start the timer for me whilst I added the reactants together. Without assistance you would have to stand one of the test tubes in the test tube rack making the procedure slower leading to scope for error The assumption has to be made that the dropper pipettes used to transfer the reaction sample into a cuvette is clean. This is because its highly impractical to clean dropper pipettes before usage and water adheres to the interior surface and would dilute the reaction sample if used thus potentially decreasing validity of the results. The concentration of each reactant as a function of time, the rate would typically carry markedly with time, decreasing to very low values as the concentration of at least one reactant becomes very low. This makes reaction studies relatively difficult to carry out. 3
Improving Accuracy and Reliability: Accuracy of the investigation could be tested if the values obtained could be crossreferenced with official data sheets or compared with a similar experiment that has produced accurate data. Accuracy of my results could be tested by getting another scientist to replicate identical conditions and methods to see if they achieve similar results. Reliability of the experiment could be improved if a greater number of repeats were taken so anomalous data would become more negligible towards trends or data. Use clean and dry equipment for measuring out quantities for every experiment (including repeats). This suggestion would be impractical in a school laboratory because
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it is high equipment demand however it would virtually eliminate the possibility of cross contamination. Once a reactants mixture has been measured out, it could immediately have a bung placed in the top of the test tube/boiling to create a closed system preventing the evaporation of any volatile liquids.
Varying the concentration of Propanone:

Volume of Propanone (cm3) 2.00 Volume of 0.02M Iodine (cm3) 2.00 Volume of 2.0M Sulphuric acid (cm3) 2.00 Volume of Water (cm3) Total Volume of solution (cm3) 20.00
14.00
Desired Concentration (mol dm) 2.5 5.0 7.5 10.0 % errors of all measurements: Dilution: 9.19 0.05 18.38 0.05 25.57 0.05 36.76 0.05
Volume of Pure Propanone required in a 50 cm3 volumetric flask dilution (cm3) (2 d.p.) 9.19 18.38 27.57 36.76
91.90cm3 0.2cm3 = 0.2% overall dilution error I consider this error uncertainty to have had a negligible potential effect on my results. Measuring out quantities of reactants: (analogue measurement error) Volume of Propanone 2.00cm3 0.01 (5ml graduate pipette) Volume of Iodine 2.00cm3 0.01 (5ml graduate pipette) Volume of Sulphuric acid 2.00cm3 0.01 (5ml graduate pipette) Volume of Water 4.00cm3 0.01 (5ml graduate pipette) Volume of Water 10.00cm3 0.04 (10ml graduated pipette) 20cm3 0.08cm3 = 0.4% per experiment (measuring out reactants) The calculated error uncertainty for varying the concentration of Propanone is identical to that of varying the concentration of Iodine. These outcomes again clarify that the appropriate
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equipment was selected to measure out the set volumes of solution by providing a relatively small error uncertainty. This again would have had a relatively negligible effect on the data obtained. Recording Absorbance using Colourimeter: (digital measurement error) Random Mean Absorbance value: (2.5M) 1.843 0.001 1.840 1.852 1.838 Uncertainty = 1.843 0.007 = 0.4% error uncertainty Quite surprisingly, it appears that again the percentage error for repeat uncertainty is substantially low. This indicates that my repeats were concordant with each other making the results precise. This % error uncertainty is lower than the value for Iodine; this may or may not be significant as the repeats chosen were at random. So I estimate this error uncertainty to have had a negligible effect on the results Procedural limitations: (The same as described in Varying the concentration of Iodine in situ)
Improving Accuracy and Reliability: (The same as described in Varying the concentration of Iodine in situ)
Varying the concentration of Sulphuric acid:

Volume of Propanone 5.0M (cm3) 2.00 Volume of 0.01M Iodine (cm3) 5.00 Volume of Sulphuric acid (cm3) 2.00 Volume of Water (cm3) 1.00 Total Volume of solution (cm3) 10.00
Desired Concentration (mol dm) 1.4 1.6 1.8 % errors of all measurements: Dilution:
Volume of 2M Sulphuric acid required in a 50 cm3 volumetric flask dilution (cm3) 35 40 45
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35 0.05 40 0.05 45 0.05 120cm3 0.15cm3 = 0.1% overall dilution error Measuring out quantities of reactants: (analogue measurement error) Volume of Propanone 2.00cm3 0.01 (5ml graduated pipette) Volume of Iodine 2.00cm3 0.01(5ml graduated pipette) Volume of Sulphuric acid 2.00cm3 0.01(5ml graduated pipette) Volume of Water 1.00cm3 0.01(5ml graduated pipette) 10cm3 0.04cm3 = 0.4% error uncertainty Recording Absorbance using Colourimeter: (digital measurement error) Random Mean Absorbance value: (1.8M) 1.672 0.001 1.670 1.655 1.691 Uncertainty = 1.672 0.02 = 1.0% error uncertainty This is a high % error uncertainty. It could possibly relate to the fact that in this investigation uses a half the total volume of reactants so the error uncertainties were larger in proportion. However this increase in error could have been the cause behind the lack of concordance in the 3 repeats used. This could also be explained as random chance that these 3 repeats have a greater mean uncertainty value than the last two. Procedural limitations: (The same as described in Varying the concentration of Iodine in situ)
Improving Accuracy and Reliability: (The same as described in Varying the concentration of Iodine in situ)
Varying the Temperature of reaction (Kelvin):

Volume of Propanone Volume of 0.01M Iodine Volume of Sulphuric Volume of Water (cm3) Total Volume of solution
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5.0M (cm3) 2.00
(cm3) 5.00
acid 2.0M (cm3) 2.00
(cm3) 1.00 10.00
Measuring out quantities of reactants: (analogue measurement error) Volume of Propanone 2.00cm3 0.01 (5ml graduated pipette) Volume of Iodine 2.00cm3 0.01(5ml graduated pipette) Volume of Sulphuric acid 2.00cm3 0.01(5ml graduated pipette) Volume of Water 1.00cm3 0.01(5ml graduated pipette) 10cm3 0.04cm3 = 0.4% error uncertainty Recording Absorbance using Colourimeter: (digital measurement error) Random Mean Absorbance value: (313K) 1.456 0.001 1.413 1.500 1.455 Uncertainty = 1.456 0.04 = 3% error uncertainty This is the highest % error uncertainty recorded so far. Temperature has a very obvious effect on the rate of reaction and this makes it extremely difficult to record precise data as the reaction proceeds so quickly it is hard to track the values on the Colourimeter. This value highlights how the data from this investigation has a higher overall higher percentage error when compared with varying concentration of reactants suggesting that varying temperature needs a more suitable method for quantitative testing. Procedural limitations: (The same as described in Varying the concentration of Iodine in situ) The most obvious procedural error is that the temperature condition will not remain constant throughout the reaction. Despite the fact that the cuvettes are made of plastic and have lids to contain and indirectly thermally insulate the reaction, the process of transferring the reaction sample drastically decreases the reactant temperature being outside of the water bath. This is a serious limitation of the experiment and it is very likely that the results produced are neither accurate nor as valid as I would have hoped. Another procedural error of varying the temperature of the reaction is that at the highest temperature (323K) the Absorbance reading halves by the time the reaction sample is transferred into the colourimeter, giving an initial Absorbance reading of 0.879. Therefore, for this temperature condition, it is physically impossible within the constraints of my experiment to record the initial rate of reaction. This would have decreased the validity of my results for varying temperature and ultimately distorted
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the gradient on the Arrhenius plot (considering the data is calculated using the initial rates method) and resultantly rendering by definition very probable to be inaccurate. The boiling temperature of Propanone is 329K so if the water bath had an uneven heat distribution which is possible as there was not a constant circulation of the water it is possible that concentration of Propanone in solution decreased during the experimentation of this temperature condition decreasing the validity of my results.
Improving Accuracy and Reliability: By using ice, temperature conditions lower than room temperature could have been established to test this effect on calculating the Activation enthalpy over a wider range of temperatures. If available the use of an electric water bath would prove much more efficient at maintaining temperature than a manual method of using a kettle and plastic tub to simulate this effect. A magnetic stirrer hot plate with stirring bar could have been used to create a constant flow of heat distribution within the water bath leading to a more accurate representative of the desirable temperature being investigated.
Overall evaluation of my investigation

Equipment
Colourimeter: Overall I would argue that the equipment I used was relatively precise and appropriate for measuring Absorbance during my investigation. However the sources of error were: Instrumental deviations occur as the consequence of the manner in which Absorbance measurements are made. (i) Beer Lamberts Law applies only to absorbance measurements with monochromatic radiations (such as lasers, which are not practical for routine analytical measurements). In practise, a polychromatic continuous source is employed in conjunction with a grating or filter that isolates a more or less symmetrical band of wavelengths. (ii) The radiation employed for Absorbance measurements is usually contaminated with small amounts of stray radiation due to instrumental imperfection. Stray radiation is the result of scattering and reflection off the surfaces of gratings, lenses filters and windows. Stray radiation differs greatly from principle radiation, and may not have passed through the analayte or solvent. Another problem with using a Colourimeter is that if you do not carefully calibrate for every use then you could end up with systematic errors in your data even if the true Absorbance value is precise and highly accurate.
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Accuracy of results:
From cross researching my results with those published online I discovered: My proposed rate equation and orders of reaction with respect to the reactants, overall order of reaction and rate constants to be correct or within an accepted range However I could not find a recognised data value for the activation enthalpy of the reaction, and so I cannot specifically comment on the accuracy of my findings using the Arrhenius equation. However, I did compare my calculated value with the standard activation enthalpy of a reaction which is said to be +50 KJ mol - this value highlights the idea that my findings were quite lower than expected, therefore are less likely to be accurate findings. From my findings, it is safe to presume that my methodology for calculating orders of reaction with respect the reactants was more valid and more appropriate than the methodology for varying temperature due to the difference in successful conclusions.
Possible improvements to the investigation:

Possible improvements I would do to my investigation if I were to repeat it: - Equipment I would not use the manual water using the kettle, instead I would choose to either use an electronically controlled water bath or a magnetic stirrer hot plate with bar. Both of these pieces of equipment are advanced at maintaining a set temperature and therefore would more appropriate for the investigation: Varying temperature of reaction. - Following this adaptation I would seek to experiment a greater range of temperatures including temperatures lower than room temperature using ice. I would also intend to use more intermediate temperatures (e.g. 5K intervals) to produce a Arrhenius plot with the most reliable and accurate gradient and therefore activation enthalpy value possible - To resolve the problem of initial rates method and the 30 second delay in my procedure I would replace the use of Colourimetry with a Photometer fitted with a recording output. This piece of equipment is superior to the basic Colourimeter as it can measure Absorbance readings by simply being place into the reaction sample as opposed to having to transfer a reaction sample into it. Resultantly usual initial rates method would become more appropriate and would be more likely to give more accurate results. - A calibration curve could have been constructed by putting known concentrations of Iodine into the colourimeter and plotting them against absorbance to act as markers. Process would enable me to convert the unit of rate from A/s to mol/s. By doing this unit conversion, calculating rate constants would have proved less problematic.
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Kinetics Investigation - The Reaction Between Propanone and Iodine in Acid Solution

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Kinetics Investigation - The Reaction Between Propanone and Iodine in Acid Solution

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Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

14.00 13.00 12.00

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Time (seconds) 30 45 60 75 90 105 120 135 150 165 180 195

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

concentration, to calculate the order of reaction with respect to Sulphuric acid)

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Safety Precautions taken

> 1 mol dm-3 Is not considered to be harmful or an irritant

Potentially harmful if you inhale and in contact with skin.

Iodopropanone (product of the reaction)

Strongly lachrymatory IRRITANT

Pure Propanone (13.6mol dm-3)

Kinetics of the reaction between propanone and Iodine in acid solution

2.0 mol dm-3

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Problems faced Method (Concentrations)

Adaptations made Method (Concentrations)

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Problems faced Equipment (Colourimeter)

Adaptations made Equipment (Colourimeter)

Kinetics of the reaction between propanone and Iodine in acid solution

Problems faced Method

Adaptations made Method

Kinetics of the reaction between propanone and Iodine in acid solution

Run 1 1.786 1.760 1.726 1.687 1.650 1.613 1.573 1.530

Run 3 1.786 1.767 1.724 1.690 1.657 1.622 1.587 1.547

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

0.409 0.320 Volume of Iodine 0.01M (cm3) 5.00

0.450 0.358 Volume of distilled water (cm3) 1.00

Total Volume of solution (cm3) 10.00

Run 1 1.720 1.670 1.615

Run 3 1.730 1.691 1.634

Kinetics of the reaction between propanone and Iodine in acid solution

Varying Iodine concentration (in situ):

Kinetics of the reaction between propanone and Iodine in acid solution

Kinetics of the reaction between propanone and Iodine in acid solution

Run 1 1.703 1.690 1.677 1.659 1.642 1.631 1.620

Run 3 1.716 1.705 1.697 1.683 1.668 1.656 1.646

Kinetics of the reaction between propanone and Iodine in acid solution

Varying Propanone concentration:

Kinetics of the reaction between propanone and Iodine in acid solution