OBJECTIVES

1. To make a comparison between the rate of conversion between primary alcohol and
secondary alcohol to alkyl bromide.
2. To analyse the factors that affect the rate of conversion of the alcohols.
3. To differentiate the molecular structure of 1-pentanol and cyclopentanol and their
reactivity.

INTRODUCTION

Alkyl halide is one of a class of organic compounds that has general formula R-X that
represents R as a carbon chain and X as a halogen. The structural components of alkyl halide
include a halogen attached to an alkyl group. Alkyl halide can be synthesized by a few methods
such as hydrogen halide addition to an alkene, free radical halogenation and reaction of
alcohols with hydrogen halides. In this experiment we were able to convert alcohols to alkyl
bromides by unimolecular nucleophilic substitution reaction (SN1) and bimolecular
nucleophilic substitution reaction (SN2) depending on the structure of the starting alcohol.
When alcohols react with hydrogen halide, a substitution takes place producing alkyl halide
and water:

R−OH + H-X → R−X + H2O (1)

The reaction is categorized as acid catalysed which alcohols will react with strongly
acidic halides such as HCl, HBr and HI. The starting alcohols that being used in this
experiments are 1-pentanol and cyclopentanol which are primary alcohol and secondary
alcohol respectively while the hydrogen halide used is 48% hydrobromic acid. 1-pentanol and
cyclopentanol react with 48% hydrobromic acid to form alkyl bromides. 1-pentanol and
cyclopentanol will either react by the reaction of SN1 or SN2 that depends on the structure of
the R group and the reaction conditions.

Both mechanisms have the same first step which are protonation of alcohol to an
oxonium ion and converting the OH group into good leaving group. The next step is determined
by the behaviour of the alkyl group R whether the R group can form stable carbocation
intermediate or not. Secondary alcohol appear to react by mechanism that involves the
formation of a stable carbocation intermediate which is SN1 mechanism while primary alcohol
undergoes SN2 which the halide ion displaces a molecule of water from the carbon. The order
of the reactivity of the alcohols is tertiary > secondary > primary.
 These two mechanisms have their own rates of conversion as both reactions are affected
by the structure of substrate, the concentration of nucleophile for bimolecular reaction, effect
of solvent and nature of leaving group. In this experiment, the rate of conversion is obtained
by measuring the depth of the layer of alkyl bromide product that forms at top layer with ruler
as a function of time.

MATERIALS AND APPARATUS

Materials Apparatus

 48% hydrobromic acid  Beaker

 Concentrated sulfuric acid  Measuring cylinder
 1-pentanol (amyl alcohol)  Glass tube
 Cyclpentanol  Thermometer
 Ruler

PROCEDURE

1. A 400 ml beaker filled with water was heated to 98±1 °C which just below the boiling
point.
2. 1.0 ml of 1-pentanol and cyclopentanol were measured exactly and poured into two
small beaker while the temperature of water bath has stabilised.
3. The beakers were cooled in ice, 2.0 ml of 48% hydrobromic acid was added to each
one and then 1.0 ml of concentrated sulfuric acid was slowly added with gentle swirling.
4. The respective reaction mixtures were poured into two labeled glass tube with sealed
at one end.
5. The tubes were clamped in a vertical position in the water bath.
6. As the insoluble layer of alkyl bromide separated, the height of the layer was measured
with millimetre-graduated ruler as close as possible to the nearest 0.5 mm and the time
noted as well.
7. Initial readings were taken at 1 min-intervals and later ones at 2-min intervals after the
forth minutes.
8. The measurement were discontinued when the level of alkyl halide no longer increased.
 OBSERVATION AND DATA

Table 1.0
Alcohol Observation

Ice bath Water bath

1-pentanol
Orange color to pale yellow 2 layers were formed, upper
layer was pale orange, lower
layer was cloudy

cyclopentanol

2 layers were formed, upper

Pale yellow to cloudy layer was black in color, lower
layer was pale orange in color.

Table 1.0 shows the molecular structure of 1-pentanol and cyclopentanol and their
observations in ice bath and water bath.
 Table 2.0
Alcohol Time (min) Height of alkyl bromide ℎ∞
lnℎ
layer (mm) ∞−ℎ

1- pentanol 0 0.00 0
1 0.01 0.182
2 0.01 0.182
3 0.01 0.182
4 0.01 0.182
6 0.01 0.182
8 0.01 0.182
10 0.01 0.182
12 0.01 0.182
14 0.01 0.182
16 0.01 0.182
18 0.01 0.182
20 0.02 0.405
22 0.02 0.405
24 0.05 1.792
26 0.05 1.792
28 0.05 1.792
30 0.06 0.00
32 0.06 0.00
34 0.06 0.00
36 0.06 0.00
38 0.06 0.00
40 0.06 0.00
42 0.06 0.00
44 0.06 0.00
Cyclopentanol 0 0.00 -3.219
1 0.02 -3.912
2 0.03 -4.605
3 0.03 -4.605
4 0.04 0.00
6 0.04 0.00
8 0.04 0.00
10 0.04 0.00
12 0.04 0.00
14 0.04 0.00
16 0.04 0.00
18 0.04 0.00
20 0.04 0.00

Table 2.0 shows the height of the layer alkyl bromide formed in each tube and the value of
ℎ∞
lnℎ with time (min)
∞−ℎ
 CALCULATION

ℎ∞
1. The calculation for lnℎ at minute of 1 for 1-pentanol is calculated by using the
∞−ℎ
formula:
ℎ∞
Formula: lnℎ
∞−ℎ

h∞ = height of alkyl bromide layer when the reaction is completed.

h= height of alkyl bromide layer at any time.

2. 1-pentanol has the height 0.01 mm (h) at minute of 1 and the height of alkyl bromide
layer when the reaction is completed for 1-pentanol is 0.06 mm (h∞). So, we can
calculate it as:
ℎ∞ 0.06
lnℎ = ln 0.06−0.01
∞−ℎ

=0.182
The calculation at other minutes of 1-pentanol and cyclopentanol were calculated
using the same formula.
3. Thus, we were able to plot the graph based on the Table 2.0 for 1-pentanol and
cyclopentanol.
 GRAPH

Graph ln(ℎ∞/ℎ∞−ℎ)) vs Time (min)

for 1-pentanol
2

1.5
ln(ℎ∞/ℎ∞−ℎ))

y = 0.0515x - 0.1662
1 R² = 0.5711

0.5

0
0 5 10 15 20 25 30
-0.5
Time (min)

Graph 1.0
ℎ∞
Graph 1.0 shows graph lnℎ against Time (min) for 1-pentanol.
∞−ℎ

Graph Time (min) vs ln(ℎ∞/ℎ∞−ℎ))

for cyclopentanol

0
0 0.5 1 1.5 2 2.5 3 3.5
-1
ln(ℎ∞/ℎ∞−ℎ))

-2
y = -0.4851x - 3.3576
-3 R² = 0.8909
-4
-5
-6
Time (min)

Graph 2.0
ℎ∞
Graph 2.0 shows graph lnℎ against Time (min) for cyclopentanol.
∞−ℎ
 DISCUSSION

In this experiment, the starting alcohol assigned to us are 1.0 ml of each 1-pentanol and
cyclopentanol to form alkyl bromide. 2.0 ml of 48% hydrobromic acid is used to each of alcohol
and 1.0 ml of sulfuric acid which acts as a solvent to provide acidic environment for the reaction
to occur. 1-pentanol react with hydrobromic acid to form 1-bromopentane by SN2 while
cyclopentanol react with hydrobromic acid to form 1-bromocyclopentane by SN1. This is
because both of the alcohols are from different group of alcohol. 1-pentanol is a primary alcohol
because its hydroxyl group (OH) is attached to only one single alkyl group. Cyclopentanol is a
secondary alcohol as its hydroxyl group attached to a saturated carbon atom which has two
other carbon atom attached to it.

Based on Table 2.0, the conversion for 1-pentanol to 1-bromopentane consumed 30

minutes for the reaction to complete while cyclopentanol consumed 4 minutes to convert into
1-bromocyclopentane. Thus, cyclopentanol react with hydrobromic acid faster than 1-pentanol
due their structure and certain conditions. We can simplify that SN1 reaction is faster than SN2
reaction in this experiment. Generally, SN2 reaction will react faster compared to SN1 but due
to the certain factors, it was opposite. The factors that affect the rates of conversion of the
alcohols are the structure of the alcohols that typified them into primary alcohol and secondary
alcohol, type of nucleophile used and the effect of the solvents. Cyclopentanol react faster in
this experiment because the nucleophile used is a weak base which is Br-. Next, cyclopentanol
react faster in sulfuric acid because it is polar protic solvent and would stabilize the formation
of carbocation.

One of the factor that leads to the different pathway of conversion alcohols which has
different rate of reaction, is the structure of the alcohols. The structure itself will determine
either the pathway SN1 or SN2 taken. As mentioned in introduction, both mechanisms have the
same first step which are protonation of alcohol to an oxonium ion and converting the OH
group into good leaving group. The next step is proceed either by SN1 or SN2 reaction. The
next step in the conversion of 1-pentanol is progressed by SN2 reaction. The Br- halide ion
displaced the protonated hydroxyl group and departed from the carbon as it is good leaving
group. This produced 1-bromopentane by SN2 reaction. Table 1.0 shows that the colour 1-
bromopentane formed was pale orange.
 Figure 1.0

Figure 1.0 shows mechanisms in the conversion of 1-pentanol in SN2 reaction.

For the conversion of cyclopentanol, the next step is proceeded by SN1 reaction because
it is secondary alcohol. The protonated hydroxyl group departs as a good leaving group to form
carbocation and water. Cyclopentanol is then readily forming secondary carbocation as the
second step which is the slow step. This slow step consequently is called as the rate-limiting
step or the rate-determining step. In the third step, the secondary carbocation formed reacts
with the nucleophile which is the halide ion of Br- that comes from hydrobromic acid. Br- halide
ions are good nucleophile because it is strong base that react with the secondary carbocation to
form more stable species which is 1-bromocyclopentane. The overall result is an SN1 reaction.
Table 1.0 indicates that the colour of the 1-bromocyclopentane formed was black in colour.

Figure 2.0

Figure 2.0 shows the mechanisms in the conversion of cyclopentanol in SN1 reaction.
 Based on Graph 1.0 and Graph 2.0, the rate constant for 1-pentanol and cyclopentanol
can be determined. The gradient, m of the tangent line equation is equals to the rate constant
of alcohols, k because the equation is in the form of y=mx+c. The equation for 1-pentanol is
y= 0.0515x-0.1662 and cyclopentanol is y= -0.4851x-3.3576. So the rate constant for 1-
pentanol is 0.0515 min -1 while cyclopentanol -0.4851 min -1 .

The precaution steps in this experiment is make sure the water heated is not exceeding
the boiling point so that the reaction can take place properly. Next, eyes must be perpendicular
to the scale of measuring cylinder when reading the volume of alcohols, hydrobromic acid and
sulfuric acid cylinder. This to ensure that the product can form in the correct amount. The
possible error is systematic error when lag behind in reading the height of the alkyl bromide
sharply on time of the time intervals. Lastly, random error which is unable to make exact
measurement due to the scale of the ruler being used is in cm.

QUESTION

1) Which of the alcohols, 2- propanol, 2-methyl-2-butanol, or 1-hexanol, would be

most likely to follow the described SN1 mechanism? Explain.

2-propanol
2-methyl-2-butanol 1-hexanol
Based on the structure above, 2-propanol is secondary alcohol, 2-methyl-2-butanol is
tertiary alcohol and 1-hexanol is primary alcohol. 2-propanol and 2-methyl-2-butanol
would be most likely to follow SN1 mechanism because they are able to form stable
secondary carbocation and tertiary carbocation respectively. 1-hexanol does not readily
form carbocation.
 2) From your knowledge of the characteristics of the SN2 reaction, what should
happen to the rate constant for the bimolecular displacement in reaction (4) as the
structure R is changed from primary to secondary to tertiary?

The rate constant of SN2 reaction will decreased as the structure of alkyl group is
changed from primary to secondary to tertiary. This is because of tertiary and secondary
carbocation have high steric hindrance that cause the nucleophile Br- difficult to attack the
carbon atom from the back side.

3) Although the alkyl bromides prepared in this experiment all have densities greater
than 1.2 g/ ml they appear as an upper layer in the reaction mixture. Explain.

The reaction mixture is made up from 2.0 ml of alkyl bromides, 1.0 ml of

concentrated sulfuric acid, and 1ml of alcohol. In this mixture, alkyl bromides appear
as an upper layer compared to the others because of its density of alkyl bromides (1.84
g/ ml) is lower than the density of concentrated sulfuric acid. The lowers the density of
solution, the higher position it will be.

CONCLUSION

In conclusion, the secondary alcohol which is cyclopentanol react faster with

hydrobromic acid compared to primary alcohol which is 1-pentanol. This is due to the ability
of cyclopentanol to form stable secondary carbocation which is by the SN1 reaction while 1-
pentanol unable to form carbocation and undergoes SN2 reaction. Thus, structure of substrate
affect the rate of conversion of the alcohols to alkyl bromide. The other factors are weak base
nucleophile which is Br- and polar protic solvent sulfuric acid were used that lead to SN1
reaction faster than SN2 reaction. 1-pentanol and cyclopentanol react with hydrobromic acid to
form 1-bromopentane and 1-bromocyclopentane respectively. The rate constant for 1-pentanol
is 0.0515 min -1 while cyclopentanol -0.4851.min-1 .
 REFERENCE

[1] Solomons, T. W. G., & Fryhle, C. B. (2011). Organic chemistry (10th ed., International
student version.). Hoboken, N.J.: John Wiley & Sons.
[2] Chang, R., & Goldsby, K. A. (2014). General chemistry: The essential concepts (Seventh
Edition.). New York: McGraw-Hill
[3] Making Alkyl Halides From Alcohols. (n.d.). Retrieved February 24, 2018, from
https://www.masterorganicchemistry.com/2015/02/27/making-alkyl-halides-from-alcohols/