Title Nucleophilic substitution reactions of halogenoalkanes Data Collection, Data Processing and Presentation Experiment 1: Effect of the halogen

atom on the rate of hydrolysis

Table 1: Tubes for experiment 1.

Tube

Content

Time noted for precipitation, (t)

*Rate of hydrolysis, (s-1)

Observation After 1 minute, the mixture changed to yellow precipitate After 4 minutes, the mixture slightly changed to pale yellow solution After 5 minutes, the mixture remains unchanged

1 cm3 ethanol 1 + 2 drops 1Approaching 0 chlorobutane 1 cm3 ethanol 2 + 2 drops 1237.000.21% 0.0040.211% bromobutane 1 cm3 ethanol 3 + 2 drops 162.000.81% 0.0160.806% iodobutane *Rate of hydrolysis can be calculated using this formula. Rate of hydrolysis =
1 time(t )

1. The fastest hydrolysis of halogenoalkane is 1-iodobutane and the slowest is 1chlorobutane. 2. Halogenoalkane that has the most polar carbon-halogen bond is 1-iodobutane. 3. Yes. The differing polarity is the reason for the different rates of hydrolysis. As the polarity of the carbon-halogen bond changes from chlorine to iodine, the rate of hydrolysis increases.
Table 2: Bond energies.

Carbon-halogen bond C-Cl C-Br C-I

Bond enthalpies at 298 K 338 276 238

* August 2001 International Baccalaureate Organization Chemistry Data Booklet. 4. According to Table 2, as the carbon-halogen bond changes from chlorine to iodine, the bond enthalpies at 298 K decrease. This is because the strength of CCl bond is higher compared to C-I. As a result, less energy required to break CCl bond whereas for C-I, more energy is required. Thus, the rate of hydrolysis of 1-iodobutane is faster compared to the rate of hydrolysis of 1-bromobutane and 1-chlorobutane.

Experiment 2: Effect of the structure of the carbon skeleton on the reaction mechanism and reaction rate
Table 3: Tubes for experiment 2.

Tube 1

Content 1 cm3 ethanol + 2 drops 1bromobutane 1 cm3 ethanol + 2 drops 2bromobutane

Time noted for precipitation, (t) 289.000.17%

*Rate of hydrolysis, (s-1) 0.0030.173%

Observation After 5 minutes, the mixture changed to pale cloudy white precipitate After 3 minutes, the mixture slightly changed to cloudy precipitate After 30 seconds, the mixture changed to a very white precipitate

181.000.28%

0.0060.276%

1 cm3 ethanol + 2 drops 23 30.001.67% 0.0331.667% bromo-2methylpropane *Rate of hydrolysis can be calculated using this formula. Rate of hydrolysis =
1 time(t )

1. The fastest bromoalkane being hydrolysed is 2-bromo-2-methylpropane and the slowest is 1-bromobutane. 2. In this experiment, the solvent used is a 1:1 mixture of ethanol and water which means the mechanism that likely to be favoured is SN1 mechanism. This is because the polar solvent, water, will hydrate ions and stabilise the carbocation. Thus, under this circumstance where the carbocation is stable, SN1 mechanism is likely to occur. 3. According to the proposed mechanism above, 2-bromo-2-methylpropane would be the most favoured and 1-bromobutane would be the least favoured. This is because 2-bromo-2-methylpropane is a tertiary carbocation and is more stable compared to 1-bromobutane which is primary carbocation, due to the inductive effect of the alkyl group. Thus, SN1 mechanism is likely to occur if the reaction goes via a tertiary carbocation. 4. From 1-bromobutane to 2-bromo-2-methylpropane, the relative rates of hydrolysis increase. This is because the rates depend on the inductive effect of the alkyl group where as the number of alkyl group increase from 1bromobutane to 2-bromo-2-methylpropane, the inductive effect also increases. As a result, the stability of carbocation increases from 1-bromobutane to 2bromo-2-methylpropane. Thus, the rate of hydrolysis also increases.

Experiment 3: Effect of the solvent on the reaction mechanism and reaction rate (the Finkelstein reaction)
Table 4: Tubes for experiment 3.

Tube 1 2

Content 3 5 cm Finkelsteins reagent + 8 drops 1-bromobutane 5 cm3 Finkelsteins reagent + 8 drops 2-bromobutane 5 cm3 Finkelsteins reagent + 8 drops 2-bromo-2methylpropane

Time elapsed, (t)

Observation The colourless mixture changed to a little amount of precipitate

20 minutes

The colourless mixture slightly changed to yellow solution The colourless mixture changed to pale yellow solution

1. The fastest bromoalkane that undergoes nucleophilic substitution by iodide ions is 1-bromobutane and the slowest is 2-bromo-2-methylpropane. 2. In this experiment, the solvent used is propanone which means the mechanism that likely to be favoured is SN2 mechanism. This is because the solvent used is non-polar solvent, propanone. Thus, under this circumstance SN2 mechanism is likely to occur. 3. According to the proposed mechanism above, 1-bromobutane would be the most favoured and 2-bromo-2-methylpropane would be the least favoured. This is because 1-bromobutane is a primary carbocation that has a single alkyl group attached to its carbon of carbon-halogen. As a result, less inductive effect causes the formation of unstable carbocation. Thus, SN2 mechanism is likely to occur. 4. From 2-bromo-2-methylpropane to1-bromobutane, the relative rates of hydrolysis increase. This is because the rates depend on the inductive effect of the alkyl group where as the number of alkyl group decrease from 2-bromo-2methylpropane to1-bromobutane, the inductive effect also decreases. As a result, the stability of carbocation decreases from 2-bromo-2-methylpropane to1-bromobutane. Thus, the rate of hydrolysis also increases.