Preparation of Alkyl Halides by Nucleophilic Aliphatic Substitution.

NaI and AgNO 3 Tests

for Alkyl Halides
Riyushi Mahadik
March 20, 2014
Methods and Background
The objective of this lab is to prepare tertiary alkyl halide by SN1 reaction, primary alkyl halide
by SN2 reaction. The other objectives are to isolate a liquid product by simple distillation, to
properly use a serpartory funnel and to distinguish between tertiary, secondary and primary alkyl
halides through NaI and AgNO3 tests and finally to calculate the percent yield of a isolated
product through a synthesis reaction.
As shown in Figure 1, nucleophilic aliphatic substitution reaction involves the conversion
between different functional groups in which Nu: represents a nucleophile and L: represents a
leaving group. Nucleophiles are either neutral or negatively charged. The nonbonding pairs of
electrons on the nucleophile are donated to an electrophilic atom which results in the formation
of a new covalent bond during the process of substitution reaction. This reaction is like a Lewis
acid-base reaction in which the electrophilic carbon atom acts as a Lewis acid and nucleophile
acts as a Lewis base. The leaving group may be neutral or negatively charged and must accept
the pair of bonding electrons from the carbon atom when the C-L bond breaks. Thus, the rate of
substitution reaction depends on the leaving ability of a particular group L: If the better the
leaving group is better at leaving the substance, the faster the reaction will occur. Similarly,
conjugate bases of strong acids are also known for good leaving groups whereas those of weak
acids are poor leaving groups.

Figure 1: Nucleophilic Aliphatic Substitution Reaction

Figure 2: Summary of Reactions in this lab

As shown in Figure 2, nucleophilic substitution reaction is classified into two types based on
their different mechanistic pathways: SN1 and SN2 reaction. SN1 reaction is an endothermic
process in which the first step of SN1 reaction is much slower than the second step and involves
heterolytic cleavage or ionization of the C-L bond to generate an unstable carbocation. The
breakage of the C-L bond requires higher energy. The intermediate carbocation formed during
the first step can undergo rearrangement to form a more stable carbocation, form an alkene
through elimination reaction or react with the nucleophile to form a stable substitution product.
The second step of SN1 reaction is relatively fast because it is an exothermic process which
involves bond formation between the carbocation and the nucleophile. The first step of the SN1
reaction is the rate-determining step (rds) and the rate of the overall reaction depends only on the
concentration of the substrate R-L which is completely independent of the concentration of the
nucleophile. Thus, SN1 reaction is called a unimolecular reaction because its rate determining
step involves only one species which is the substrate R-L. This concept is further explained by a
rate equation Rate = k1[R-L] where k1 is the first order rate constant. Since the transition state in
SN1 reaction involves the formation of a stable carbocation, these types of reactions favors
compounds with a leaving group from tertiary-bonded carbons due to its stability, which is
tertiary > secondary >>primary. According to Le Chateliers principle, if equilibrium is
disturbed, then conditions in the reaction will change to keep it at equilibrium. Therefore, if the
concentration of the reactants increases, the reaction will shift to the right resulting in the
formation of the product.

Figure 3: SN1 versus E1

As shown in Figure 3, unimolecular elimination reaction, E1, competes with SN1 substitution
reactions. The reaction depends on the nature of the nucleophile. Substitution can occur in the
weakly basic conditions and also highly polarizable nucleophiles such as I-, Br-, Cl-, H2O, and
Ch3CO2-. For elimination, strongly basic and only slightly polarizable nucleophiles condition
should be met when RO-, H2N-, H-, and HO- are used. Moreover, larger nucleophiles tend to favor
elimination because the hydrogen atom is more sterically available than is the carbon atom
bearing the leaving group. In this experiment, tertiary alkyl halide, 2-chloro-2-methylbutane will
be prepared through SN1 reaction by reacting 2-methyl-2-butanol with hydrochloric acid. In this
reaction,OH is a poor leaving group which is protonated by hydrochloric acid and oxonium ion
is formed. Since H2O is a good leaving group, it results in the formation of a carbocation which
at the end is attacked by the nucleophilic chloride ion. The below Sn1 reaction mechanism is
shown in Figure 4.

Figure 4: SN1 Reaction Mechanism

In SN2 reaction, primary alcohols reacting with a hydrogen halide H-X (X= Cl, Br, or I) to obtain
primary alkyl halides. In compare to SN1 reaction, SN2 reaction consists of only one step which is
also the rate-determining step and does not go through carbocation formation. In SN2, reaction,
the nucleophile attacks the carbon atom on the opposite side of the leaving group. When the
nucleophile attaches the carbon atom, the leaving group cleaves the carbon atom. The carbon
atom takes bonding pair of electrons. The rate determining step of this reaction is dependent on
the concentrations of both the substrate, R-L, and the nucleophile, Nu:, since this reaction is
bimolecular reaction. This concept is explained by a rate equation Rate = k2[R-L][Nu:]where k2
is the second order rate constant. In these reactions, the nucleophile attacks the substrate which is
directly behind the leaving group. Therefore, the more sterically hindered a carbon atom is, the
less chances to undergo an SN2 reaction. Therefore, SN2 reactions favor compounds with a
leaving group from primary-bonded carbons due to its stability, which is primary > secondary >>
tertiary. Based on the stability of the transition state, leaving groups from secondary-bonded
carbon, the reaction can proceed either pathway, SN1 or SN2. According to Le Chateliers
principle, the reaction will be favored by increasing the concentration of the reactants. By
increasing the amount of nucleophile, the concentration of the compound in the transition state
increases which increases the rate of product formation. The SN2 reaction prefers leaving groups
that are weaker bases, since they have greater leaving ability.

Figure 5: SN2 versus E2

As shown in Figure 5, SN2 reaction competes with bimolecular elimination reaction to produce
alkenes. In this experiment, primary alkyl halide, 1-bromobutane will be prepared through SN2
reaction by reacting 1-butanol with sodium bromide and sulfuric acid. OH is a poor leaving
group which is protonated by sulfuric acid and thus oxonium ion is formed. Since H2O is a good
leaving group, the nucleophilic chloride ion does a backside attack on the molecule. The reaction
mechanism for S N2 is shown in Figure 6.

Figure 6: SN2 Reaction Mechanism

In order, to verify whether the substitution product is primary, secondary, or tertiary alkyl halide,
the sodium iodide (NaI) and the silver nitrate (AgNO3) test will be done. The reaction of silver
nitrate and alky halide is an SN1 reaction because its rate-determining step involves only one
molecule. Silver chloride is formed as one of the products, which precipitates in ethanol as
shown in Figure 7. Formation of the precipitate determines whether or not a halide is present.
The rates of precipitation of silver halide in this test increases with increasing carbocation
stability and substitution (tertiary > secondary >> primary). Another method that distinguishes
halides into primary, secondary, and tertiary halides is the sodium iodide test dissolved in acetone
(Figure 8). In this test sodium bromide and chloride are not very soluble in acetone in compare
to sodium iodide. The reaction of sodium iodide with alkyl halides is SN2 reaction in which
iodide ion is the nucleophile. The order of reactivity of this reaction is primary > secondary >>
tertiary. In this test, sodium bromide quickly forms a precipitate at room temperature, whereas
primary and secondary chlorides must be heated to form precipitates. Secondary and tertiary
alkyl halides also react at higher temperatures but tertiary chlorides does not react in relative
time.

Figure 7: Silver Nitrate Test

Figure 8: Sodium Iodide Test

Procedure:
Synthesis of 1-Bromobutane:
11.11g of sodium bromide was transferred to a 100mL round bottom flask with 10 mL of water,
10 mL of 1-butanol, and 1-2 boiling stones. The contents of the flask were mixed by gently
swirling it, and the flask was then placed in an ice-water bath. Then, 10 mL of sulfuric acid was
added to the chilled reaction mixture slowly while swirling it. The reflux apparatus shown in
Figure was set up. The flask was warmed gradually until heating under for 45 minutes. After 45
minutes, the water hoses from the Hempel column were removed and the water was drained from
the outside of the column. Then, the apparatus for simple distillation technique was set up as
show in figure to distill the product mixture until the distillate in the receiving flask was clear.
The flask was kept in ice-water bath at all times. Finally, the distillate was then transferred to
separatory funnel and washed with 10 mL of water. 1-bromobutane (organic layer) is the denser
bottom layer. The two layers were separated and the organic layer was returned to the separatory
funnel which was then sequentially washed with 8 mL of concentrated sulfuric acid, two x 5mL
of 2 M NaOH, 10 mL of water, and 10 mL of saturated sodium chloride (brine). Since
concentrated sulfuric acid is denser than 1-bromobutane, the organic layer was the top layer for
this washing step. NaOH, water, and brine are less dense than 1-bromobutane, and so the organic
layer was the bottom layer for these washing steps. 1-Bromobutane was then transferred to a
clean flask and water was absorbed by using 1.5g of sodium sulfate. The dried 1-bromobutane
was weighed and percent yield was calculated.

Figure 9: Heating under reflux apparatus

Figure 10: Simple Distillation Apparatus

Synthesis of 2-Chloro-2-Methylbutane:
In a separatory funnel, 10 mL of 2-chloro-2-methylbutanol and 25 mL of concentrated (12M)
hydrochloric acid were placed and swirled gently without the stopper. After 1 min, stopper was
placed on the separatory funnel and then inverted at times venting out the excess pressure. The
stopcock was again closed, the funnel was shaken, and the mixture was allowed to separate into
two layers. The bottom organic layer was sequentially washed with 10 mL portions of saturated
aqueous sodium chloride and cold saturated aqueous sodium bicarbonate. When sodium
bicarbonate was added, vigorous gas evolution which was controlled by gently swirling the
funnel. The funnel was then stoppered, shaken vigorously, and vented frequently to release any
gas pressure. The organic layer was separated and washed sequentially with 10 mL portions of

water and aqueous sodium chloride. The aqueous layer was carefully removed and 2-chloro-2methylbutanol was dried using 1.5 g of sodium sulfate. The final product was transferred to
round bottom flask for simple distillation. The fraction was collected when the head temperature
was greater than 75C (760 Torr) to a receiver place in an ice-water bath.
For the tests, silver nitrate and sodium iodide tests were performed on the final products. A silver
nitrate test was performed to verify the obtained alkyl halide. Three small test tubes were
prepared with 5 drops of each of the primary, secondary, and tertiary alkyl halides were added to
2 mL of a 0.1 M solution of silver nitrate in 95% ethanol. Different colored precipitates should
be formed that is silver chloride is white, silver bromide is pale yellow, and silver iodide is dark
yellow. For sodium iodide test, the presence of alkyl chlorides and bromides was checked. Three
small test tubes were prepared with 5 drops of each of the primary, secondary, and tertiary alkyl
halides were added to 1 mL of the sodium iodide-acetone. Precipitate should form within 3 min
at room temperature.
Data Acquisition/Calculation:
Observations:
Products

AgNO3 Test

2-chloro-2methylbutane
(3)

Cloudy, white liquid at Yellow cloudy but

the top and white
became clear
precipitate at the
bottom of the test
tube.
No reaction (clear)
No reaction(clear)

2-chlorobutane
(2)
1-bromobutane
(1)

Cloudy liquid, no
precipitation

NaI Test

Partially cloudy liquid,

white precipitate forms

Percent Yield
The percent yield will help in determining the success of this experiment. The formula for
calculating the percent yield as follows,
Percent Yield = [(Actual Yield) / (Theoretical Yield)] x 100
Chemical
Density
Molar Mass
Used

Table 1: Calculating % Yield for Sn2 Reaction

1-butanol
1-bromobutane
3
0.81 g/cm
1.27 g/cm3
74.12 g/mol
137.02 g/mol
10 mL
from ntp.niehs.nih.gov

Theoretical Yield of 1-bromobutane: Sn2

(10 mL 1-butanol)(0.81g/mL 1-butanol)(mol/74.12g 1-butanol) = 0.109 mol 1-butanol
1 mole 1-butanol makes 1 mole 1-bromobutane (based on stoichiometry--this is a 1:1 reaction)

0.109 mol 1-butanol (137.02g/mol 1-bromobutane) = 14.97 g 1-bromobutane

Actual Yield of 1-bromobutane: 6.99g
Percent Yield of 1-bromobutane: [(6.99g) / (14.97)] x 100 = 46.6%
Table 2: Calculating % Yield for Sn1 Reaction
Chemical
2-methyl-2-butanol
Density
0.805 g/mL
Molar Mass
88.15 g/mol
Used
10 mL

2-chloro-2-methylbutane
0.866 g/mL
106.59 g/mol
from www.chemicalbook.com

Theoretical Yield of 2-methyl-2-butanol: SN1

(10 mL 2-methyl-2-butanol)(0.805 g/mol 2-methyl-2-butanol)(mol/88.15g 2-methyl-2-butanol) =
0.0913 mol 2-methyl-2-butanol
Same thing as Sn1. It is a 1:1 reaction
0.0913 mol 2-methyl-2-butanol (106.59g/mol 2-chloro-2-methylbutane) = 9.73 g 2-chloro-2methylbutane
Actual Yield of 2-chloro-2-methylbutane: 33.62 g 16.43 g =17.19 g
Percent Yield of 2-chloro-2-methylbutane:

[(17.19g) / (9.73g)] x 100 = 177%

Conclusion:
The objective of this lab is to prepare tertiary alkyl halide by SN1 reaction, primary alkyl halide
by SN2 reaction. The other objectives are to isolate a liquid product by simple distillation, to
properly use a serpartory funnel and to distinguish between tertiary, secondary and primary alkyl
halides through NaI and AgNO3 tests and finally to calculate the percent yield of a isolated
product through a synthesis reaction. Simple distillation was also performed and 2-chloro-2methylbutane was collected at a temperature greater than 75C. 1-Brmobutane was prepared by
adding 1-butanol and sulfuric acid with sodium bromide through the SN2 mechanism of the
substitution reaction.
In this lab, silver nitrate reacted with tertiary alkyl halide, then primary and secondary alky
halide because silver nitrate is a good Lewis acid that can easily cleave the bond between carbon
and halogen atoms resulting in the formation of a carbocation. On the other hand, sodium iodide
is not a good Lewis acid, so therefore it attacks the carbocation at the same time the chloride ion
is cleaved. 2-chloro-2-methylbutane is tertiary alkyl halide that when tested with AgNO3, white
liquid and white precipitated very quickly. When 2-chloro-2-methylbutane was tested with
sodium iodide, yellow cloudy precipitation was seen. When 2-chlorobutane was tested with
sodium iodide and silver nitrate, precipitation didnt occur. It needs relative time to show white

percipitates. When 1-bromobutane was tested with AgNO3, it didnt form a precipitate but cloudy
liquid was observed. On the contrast when 1-bromobutane was tested with silver nitrate, a cloudy
white precipitate quickly formed.
The percent yield of the primary and tertiary alkyl halides were calculated to determine the
success of the experiment. The percent yield of 2-chloro-2-methylbutane is 177% and 1bromobutane was 46.6%. There was an error made in weighing the round bottom flask without
the product and with the product. Thus, this happened to produce significantly large percent yield
for 2-chloro-2-methylbutane. The low percent yield for 1-bromobutane could be due to the
extraction step. Some of the 1-bromobutane was not extracted with aqueous solution; due to
volatility of the products. Even though an ice bath was used to prevent the product from
evaporating, there might be possibility some of it evaporated. Since alcohol is soluble in water,
some of the reactants might be washed away with water which resulted in less amount of product
formation. Finally, some of the solution of 1-bromobutane was also spilled on the table and was
taken of care of. Thus, there might be several reasons that why the product was very low in
amount giving the low percent yield. This process can be explained that when alcohol is
protonated and water is produced as a leaving group, mixing alcohol with the water. Thus, it
lowers the concentration of carbocation in the solution. Despite the significantly wrong percent
yields of the products formed, this experiment was performed systematically preventing any
other errors.
Reference
Gilbert, John C., and Stephen F. Martin. Experimental Organic Chemistry. Cengage Learning,
Massachusetts, 2011, 5th Ed, pp. 75-81, 153-161, 93-100.