University Of Central Lancashire School of Forensic and Investigative Sciences FZ1025 Experimental techniques

6&7. Synthesis, Characterisation and Stability of an Interhalogen Compound

INTRODUCTION The aim of this experiment is to introduce you to the synthesis and analysis of a compound containing an interhalogen ion. You will also investigate the decomposition of this interhalogen anion to another and accurately establish the stoichiometry of both interhalogen anions using volumetric analysis. Many interhalogen compounds have been synthesised and fully characterised. Stable interhalogen molecules are of the type XYn where n is an odd number and Y is usually the lighter halogen. Examples include ClF, BrF3, IF7 and ICl3. Also, a wide range of cationic and anionic interhalogen species are known. For example, [Br2]+, [I5]+, [ClF2]+, [BrF6]+, [IF8]-, [Cl3]- and [IBrCl]-. Some ions such as [I3]- are stable even in aqueous solution, but most of the larger ions exist only in crystalline salts with large counter-ions. The molecular structures of interhalogen species can be reliably predicted using VSEPR theory.

PRE-LAB QUESTIONS 1. Write balanced equations for the reaction of aqueous iodate (V) with excess iodide in the presence of acid and the reaction of molecular iodine with thiosulphate ions. (4 marks) 2. Why is potassium iodate (V) a good primary standard? (3 marks)

3. This experiment uses chlorine gas. What safety precautions should you take when using this substance? (3 marks)

COSHH ASSESSMENT: Please read the safety information carefully before beginning the practical
Chemical / Process Hazard Severity Grade 1-4 A 2 2 3 Likelihood of occurrence Grade 1-4 B 2 2 2 Risk (A x B) (Likelihood x hazard) 4 4 6 Safety

Dichloromethane Tetrabutylammonium iodide Chlorine

Wear gloves. Harmful by inhalation and in contact with skin. Harmful by ingestion and irritating to the eyes Toxic by inhalation, very irritating to eyes and respiratory system. Strong oxidising agent Extremely flammable keep away from ignition sources. Harmful by skin contact and inhalation

Diethyl ether

Sodium thiosulphate solution Potassium iodate (V) Potassium iodide Sulphuric acid

1 1 1 2

2 2 1 2

2 2 1 4

Harmful by ingestion. Harmful to eyes and lungs Oxidising agent. Harmful by ingestion May be irritating to the eyes and skin Corrosive. Wash with copious amounts of water and consult a physician. Harmful by ingestion Flammable. Wash with copious amounts of water.

Lithium iodide Acetone

1 1

1 2

1 2

EXPERIMENTAL Part 1: Synthesis of the interhalogen compound 1. Prepare an ice bath, add water to the ice to aid heat conduction. Cool 25 ml of dichloromethane in a measuring cylinder. 2. Weigh accurately approximately 2 g (make a note of the actual weight) of tetrabutylammonium iodide and place into a 125 ml conical flask with a stopper. 3. Add the cold dichloromethane to the conical flask and shake gently until the solid dissolves. 4. Cool the solution in the ice bath. Slowly pass chlorine gas over the surface of the solution which should be gently swirled in the flask. 5. When precipitation from the solution has stopped, remove from the chlorine supply. 6. Heat the flask gently on a water bath in the fume cupboard for approximately 5 minutes or until the bubbling due to the evolution of excess chlorine has stopped. (this is to prevent oxidation of your product which can occur if there are any traces of water present). Do not boil the solution (boiling point of dichloromethane is approx.. 40C) but make sure your compound remains in solution by adding drops of dichloromethane should any yellow precipitate be observed. 7. Cool the solution in the ice bath for about 10 minutes or until crystallisation is complete. 8. Filter the cold solution on a Buchner funnel and suck dry for approx. 15 minutes. Wash the crystals with a small amount of diethyl ether to aid drying. 9. Weigh your product accurately and keep in the dark.

Part 2: Light Decomposition 1. Take approx. 1.0 g of your product [nBu4N][ICln] and grind the crystals to a fine powder using a mortar and pestle. 2. Spread the powder as a very thin layer on a watch glass. 3. Place the watch glass in a vacuum desiccator and place under the light source provided and leave overnight.

Part 3: Standardisation of sodium thiosulphate solution 1. Fill your burette with the approximately 0.1 M sodium thiosulphate solution provided 2. Calculate the mass of potassium iodate (V) required to make 250 ml of a 0.02 M solution. Formula weight of potassium iodate (V) is 214 g/mol. 3. Prepare this solution in a 250 ml volumetric flask using deionised water. 4. Remove 20 ml of this solution and place in a 250 ml conical flask. The add 12 ml of 0.5 M potassium iodide solution and 20 ml of 1 M sulphuric acid. 5. Titrate the liberated iodine against the thiosulphate solution. The end point of the titration corresponds to the disappearance of the iodine colour from the solution. 6. Repeat the titration twice until the titres agree within 0.05 ml. Record your titre figures in your notebook and calculate the molarity of the thiosulphate solution.

Part 4: Volumetric analysis of the first product, [nBu4N][ICln]The basis of the analytical method here is that the addition of lithium iodide to [ICl n]- in acetone solution results in the quantitative liberation of iodine according to the equation below. The liberated iodine can then be determined by titration with the previously standardised solution of sodium thiosulphate. 1. Accurately weigh 0.15 g of your [nBu4N][ICln]- product into a 125 ml conical flask and add approximately 0.5 g of lithium iodide. 2. Add approximately 20 ml of acetone and shake until the solids dissolve. 3. Without any delay (to prevent air oxidation of I2) titrate the solution against your previously standardised thiosulphate solution. The end point will correspond to the disappearance of the iodine colour from the solution. 4. Repeat the titration once more and calculate the value of n for the interhalogen anion. Based on the weight of the tetrabutylammonium iodide starting material, calculate the yield of your [nBu4N][ICln]-.

Part 5: Volumetric analysis of the decomposition product, [nBu4N][IClm]Repeat the steps given in part 4 for your decomposition product and determine the value of m in the interhalogen anion.

POST-LAB QUESTIONS 1. Using your results from part 3, calculate the molarity of the sodium thiosulphate solution. 2. Using your titre figures from part 4 and the following equation, calculate the value of n for the interhalogen anion. [ICln]- + n LiI n/2 I2 + n LiCl + I3. Calculate the yield of [nBu4N][ICln]- and use VSEPR theory to calculate the shape of the anion. 4. Using your titre figures from part 5 calculate the value m for the interhalogen anion and use VSPER theory to calculate the shape.

5. Attempts to synthesise Li[ICln] result in the formation of LiCl. Make use of this fact, ideally with an appropriate Born-Haber cycle, to explain why large cations such as [nBu4N]+ are used in the synthesis of interhalogen anions.