A VELOCITY CONSTANT BY TITRATION METHOD

Aims and Objectives: 1. To determine the velocity constant (rate constant) of a reaction by the method of titration. 2. To determine the rates at which the reactions occur. 3. To be able to determine the orders of reactions. INTRODUCTION Chemical Kinetics is the branch of chemistry which is concerned with the study of the rates of chemical reactions. The rate of a reaction is a measure of how quickly the reactants are turned into products over a given period of time. This area of study directly complements the study of thermodynamics which focuses exclusively upon the energetic favourability of reactions. The rate of a chemical reaction depends usually on: the nature of the reactants; the temperature; the presence of a catalyst; the concentration of the reactants in the solution; the physical state of the reactants and pressure. For a reaction to occur, the atoms, molecules, or ions must come into contact with one another with enough energy to rearrange chemical bonds in some way. Concentration plays a very important role in reactions, because, according to the collision theory of chemical reactions, molecules must collide in order to react together. As the concentration of the reactants increases, the frequency of the molecules colliding increases, striking each other more frequently by being in closer contact at any given point in time. For example lets take two reactants in a closed container: All the molecules contained within are colliding constantly. Upon increasing the amounts of one or both of the reactants, the collisions occur more frequently, increasing the reaction rate. Some reactions, such as an explosion TNT, inherently tend to proceed rapidly. Others, such as the reaction of solid limestone with carbon dioxide in water to form calcium hydrogen carbonate, tend to proceed slowly. It may take centuries for underground steam to form caverns by reaction with limestone for a given reaction, chemists have no control over the nature of the reactants. The 'rule of thumb' that the rate of chemical reactions doubles for every 10 C temperature rise is a common misconception. This may have been generalized from the special case of biological systems, where the temperature coefficient is often between 1.5 and 2.5. Theory In this reaction, potassium persulphate is used to oxidize the iodide ions in the potassium iodide to iodine. Sodium thiosulfate is used to reduce iodine back to iodide before the iodine can complex with the starch to form the characteristic blue-black colour. 1. The iodide is oxidized: 2I(aq) + S2O82(aq) I2 (aq) + 2SO42(aq) The Sodium thiosulphate is used to reduce iodine back to iodide before the iodine can complex with the starch to form the characteristic blue-black colour 2. Iodine is reduced: I2 (aq) + 2S2O32(aq) 2I(aq) + S4O62(aq) Once all the thiosulfate is consumed the Iodine may form a complex with the starch. The rate equation may be expressed in the form of: c = R (A) n1(B)n2 (1) t where R is the velocity constant of the reaction. The order of the reaction n is the sum of the exponents in the rate equation, i.e. n = n1 + n2 + n3

In the second order reaction involving the oxidation of iodide with persulphate 2I- + S208 I2 + 2SO4-2 The rate equation may be written c = K2 (a-x) (b-x) t (2)

Where a and b are the initial concentrations of potassium persulphate and potassium iodide respectively. However, in this experiment one of the reactants in in excess to the extent that its concentration remains more or less the same. If this is the case, the reaction will follow first order kinetics. Assuming the iodide is the reactant in excess in the above reaction, the rate equation can now be written as such. c = k2 (a-x) b (3) t By applying calculus, integrate and apply the condition that when t = 0, x = 0, we have bk2 = - 1 ln a t a-x ln (a-x) = - kt + lna Where k = b.k2 Eqn (4) has the form of a linear equation, y = mx + c Where m = slope of the line y = ln (a-x) m = -k x Chemicals And Apparatus Saturated solution of potassium persulphate 10 ml Pipette 0.4N potassium iodide solution Beaker 0.01N sodium thiosulphate solution Large amounts of distilled water Conical flask Graduated cylinder Stop watch

(4)

PROCEDURE 1. 50ml of the 0.4N potassium iodide solution is delivered into a conical flask from a pipette. 2. 20ml of saturated potassium persulphate solution is diluted in 80.0ml of water. 3. 50ml of the diluted potassium persulphate solution is placed in a conical flask. 4. When the temperatures of the solutions became steady at 25C, the 50 ml potassium iodide solution was poured into the 50 ml of diluted potassium persulphate solution and the stop watch started simultaneously.

5. At 3 minutes 10.0 ml of the resulting solution in procedure 4 was withdrawn with a pipette and allowed to run into a large volume of water (100 ml). 6. The 10.0ml with the 100ml of water was titrated with freshly prepared 0.01M sodium thiosulphate (x ml) where the indicator used was starch. 7. Procedures 5-6 are repeated after the following time intervals: 8, 12,15,20,30,40,50,60 minutes. The following procedures were not performed by my group but by the demonstrator in order to save time and obtain the additional values needed for our calculations: 1. 50ml of potassium iodide solution was mixed with the remainder of the diluted potassium persulphate solution and maintained at 60C for the duration of the experiment. 2. The solution was cooled and maintained at 25C f at least 15 minutes. 3. 10.0ml was titrated with 0.1N sodium thiosulphate (a ml). RESULTS TABLE OF RESULTS Time/mins 3 8 12 15 20 30 40 50 60 V1/ml 0.00 3.30 4.40 6.20 18.10 20.40 23.90 29.60 34.20 V2/ml 3.30 4.40 6.20 7.80 20.40 23.90 29.20 34.20 38.70 V2-V1=x/ml 3.30 1.10 1.80 1.60 2.30 3.50 5.30 4.60 4.50 a/ml 8.10 8.10 8.10 8.10 8.10 8.10 8.10 8.10 8.10 a-x/ml 4.80 7.00 6.30 6.50 5.80 4.60 2.80 3.50 3.60 Log(a-x) 0.6812 0.8451 0.7993 0.8129 0.7634 0.6628 0.4472 0.5441 0.5563

Graph of Results

0.9

0.8

0.7

0.6

0.5

Log (a-x)

Y-Values 0.4 Linear (Y-Values)

0.3

0.2

0.1

0 0 10 20 30 40 50 60 70 Time/mins

Log (a-x) (3 mins) = log (8.10 3.30) = log (4.80) = 0.6812 Calculations & Post lab Log (a-x) (3 mins) = log (8.10 3.30) = log (4.80) = 0.6812 Slope of graph, R = log (a-x) t = 0.5441-0.6628 50-30 = -5.935x 10-3 min -1. Post Lab answers:

1. The order of the reaction could be changed by changing the concentrations of the reactants 2. Other experimental methods for following the kinetics of this reaction include: mathematic method, isolation method and reasoning method. 3. The starch indicator was used since it caused an easily visible blue black colouration which then became colourless at the end point of the titration. DISCUSSION When the 50 ml of potassium iodide was added to 50 ml persulphate solution yellow mixture was obtained which later turned deep orange. The yellow mixture after five drops of starch was added to it changed to a blue black colour. The colour of the mixture turned to blue-black upon addition of starch indicator because starch turns blue-black in iodine. It was also observed that, as the time increased, the value of x ml; (the volume of thiosulphate) also increased steadily as the reaction proceeded, the rate increased more rapidly. This is because with time, persulphate ions reacted with iodide to form more iodine molecules. Since thiosulphate reacts with iodine when introduced, more thiosulphate will be used up. As is made obvious from the graph obtained by my group, there were certain deviations of values obtained in our experiment as a result of errors of some kind. However, we managed to calculate for and draw a line of best fit in order for us to calculate and determine the velocity constant R. Although our value obtained for the velocity constant may not be 100% accurate it still gives us a close enough value to what it is in reality. Plus after further literary research we discovered that our line of best fit and the line graph from our research had the same direction and the value of the velocity constant was also a negative just as we had although the two values were different from each other. The rate constant being negative indicated that the rate of this reaction depended on the concentration of the reactants and as was observed, decreased as the reaction proceeded. After some more research we concluded that the reaction had to be a first order reaction since the slope of the line for a first-order reaction is also negative. SOURCES OF ERROR 1. Due to the absences of stopwatches in the laboratory at the time of the experiment my group had no other choice but to use our analogue wrist watches to record the time intervals. Hence the timings of the experiments were not at all accurate. 2. The burette used during the experiment was leaking and so we were forced to approximate the titre values obtained for the thiosulphate at the end point. 3. The line of best fit passed through only two points because and so does not offer a very accurate result. 4. My group had only one conical flask and so had to make do with the smaller glassware which was a bit too small to contain the large volumes of the solutions. This caused some decent amount of spillage thus made the titration ineffective and therefore affected the endpoint of the solution. PRECAUTIONS 1. The burette was ensured to stand upright in the retort stand to avoid parallax. 2. All burette and pipette readings were taken accurately from the bottom of the meniscus. 3. It was ensured that all bubbles were eliminated from the pipette and burette before undertaking the experiments 4. The glassware was washed with the sample of the solutions before use. 5. Our goggles and lab coats were worn through out the duration of the experiment. 6. Unused exposed chemicals were disposed off properly before leaving the laboratory. 7. Hands were thoroughly washed before leaving the laboratory.

CONCLUSION In conclusion and after additional research we concluded that we probably would have obtained similar results had we not met with those few problems. It is clear from the values obtained that the errors encountered really affected our results but aside from that it is also plain to see that this method is effective in calculating for the velocity constant given the proper equipment and using precise timing.