Rogeni Misaelle M.

Petinglay Date performed: March 30, 2017

B.S. in Chemistry II Date submitted: April 10, 2017

Experiment No. 7
Hydrocarbons

I. Summary of Results

Table 1. Solvents and Samples Used with their Physical Properties

Solvent/Sample Physical properties
H2O Colorless, odorless
NaOH Colorless, more viscous than water, odorless
H2SO4 Golden brown
DCM Colorless, odorless
Cyclohexane Colorless
Cyclohexene Yellowish, pungent odor
Benzene Colorless, gasoline-like odor
Toluene Colorless, paint thinner smell
Baeyers Reagent Dark violet
Ammoniacal Silver Nitrate Colorless with small black precipitates

Table 2. Solubility Behaviour

Solvent Sample Observations
Cyclohexane Miscible, cloudy white, slightly turbid
Cyclohexene Miscible, cloudy yellow
Benzene Miscible, cloudy white
DCM
Toluene Immiscible, 2 layers formed
Cyclohexane Immiscible, colorless upper layer, cloudy white bottom layer
Cyclohexene Immiscible, yellowish upper layer, colorless bottom layer
Benzene Immiscible, gelatinous white upper layer, colorless bottom layer
H2O Immiscible, slightly cloudy white upper layer, colorless bottom
Toluene
layer
Immiscible, formation of bubbles on the upper layer, colorless
Cyclohexane
bottom layer
Immiscible, yellowish upper layer with formation of bubbles,
Cyclohexene
colorless layer with some particles settled at the bottom part
Immiscible, white colored and rapid bubble formations on the upper
% NaOH Benzene
layer, colorless with some white precipitate on the bottom layer
Immiscible, white cloudy upper layer with very rapid bubble
Toluene
formations, colorless bottom layer with some white precipitate
Concentrated Immiscible, saturated white upper layer, golden brown bottom layer,
Cyclohexane
H2SO4 exothermic
Immiscible, 2 layers formed heat formation (exothermic rxn),
Cyclohexene
formation of white precipitate
 Immiscible, light brown upper layer, cloudy white upper layer,
Benzene
Concentrated exothermic
H2SO4 Immiscible, slightly cloudy white upper layer, light brown bottom
Toluene
layer, exothermic

Table 3. Halogenation: Reaction with Bromine

Sample Unwrapped Test tube Result Unwrapped Test tube Result
Slightly cloudy white, odorless,
Slightly cloudy white,
Cyclohexane Negative same appearance on the Negative
odorless
unwrapped test tube
Cloudy yellow, same
Cyclohexene Cloudy yellow Negative appearance on the unwrapped Negative
test tube
More cloudy white than
Benzene Negative Yellowish solution Positive
cyclohexane reaction
Most cloudy white of all
Toluene Negative Cloudy yellow solution Positive
the unwrapped test tubes

Table 4. Oxidation: Reaction with Baeyers reagent

Sample Observations Result
Cyclohexane No color change, still colored violet solution Negative
Dark red solution, formation of brown
Cyclohexene Positive
precipitate
No color change, still colored violet solution
Benzene Negative
with bubble suspensions
No color change, still colored violet solution
Toluene Negative
with bubble suspensions

Table 5. Reaction with Ammoniacal Silver Nitrate

Sample Observations
Cyclohexane Slightly cloudy solution, formation of small gray precipitates
Cyclohexene Very light yellow solution, formation of small gray precipitates
Benzene Colorless solution, formation of small brown precipitates
Toluene Cloudy white solution, formation of small white precipitates

Table 6. Preparation and Testing of Acetylene Gas

Solvent Observations
A. DCM Colorless liquid with small black precipitates
H2O Colorless liquid, no changes
NaOH Colorless liquid, no changes
H2SO4 Colorless liquid, no changes
B. 0.05 M Br2/CCl4 (unwrapped) Colorless liquid with oily layer
0.05 M Br2/CCl4 (wrapped) Colorless liquid yellowish liquid
Violet bloody red brown,
C. Baeyers reagent
with small brown precipitates, bubble formations
 Colorless liquid with small brown precipitates and
D. Ammoniacal AgNO3
yellowish flake formations on the surface

II. Results and Discussion

A. Investigation of Hydrocarbons

1. Solubility Behavior

In this part of the experiments, the miscibility of each sample was tested to the DCM,
10% NaOH, concentrated H2SO4, and H2O solvents. The samples used were cyclohexane,
cyclohexene, benzene, and toluene.

Dichloromethane (DCM). In this solvent, all of the samples were miscible except
toluene. Toluene is a nonpolar molecule while DCM is a polar molecule that is why it is
insoluble in the solvent. The reaction of cyclohexane, cyclohexene and benzene with DCM made
a cloudy solution with a homogenous phase indicating that these samples are miscible with the
solvent.

Water (H2O). Addition of each sample to water formed two layers. Most of the water
was on the bottom layer while the upper layer was composed of the samples. The resulting
solutions were heterogenous which implies that hydrocarbons are immiscible and insoluble in
water. This is due to the principle like dissolves like. Water is a polar compound while
hydrocarbons are nonpolar compounds.

10% NaOH. Separation layers were observed after mixing each sample to this solvent. .
The reaction of each sample made bubble formations or minute emulsions and also white
precipitates. Thus, each sample was clearly insoluble with sodium hydroxide solvent. The same
concept applies like in water. The dipole moment of the OH bond makes NaOH polar while all
the other samples are nonpolar. The general rule in solubility, like dissolves like is also applied
here.

Concentrated H2SO4. All the samples used were immiscible with H2SO4. Mixing with
cyclohexane produced an immiscible mixture with the upper layer clearer than the lower layer
which may be due to the gases evolved from the agitation of the concentrated acid. The same
result was obtained for the cyclohexe, benzene, and toluene, which formed a translucent upper
layer. All samples were immiscible with the solvent because H2SO4 is polar while the samples
are nonpolar. Moreover, all were exothermic.

2. Halogenation: Reaction with Bromine

The reactivity of organic compounds with bromine was tested in this part of the
experiment. Saturated hydrocarbons (alkanes) undergo substitution reactions with halogens when
exposed to ultraviolet light while unsaturated hydrocarbons (alkenes and alkanes) readily
undergo halogenation process.
 In the experiment, 0.05 M Br2/CCl4 was added to the wrapped and unwrapped test tubes
of cyclohexane, cyclohexene, benzene, and toluene. After a few minutes, the tubes were
examined. For the set of unwrapped samples, benzene and toluene had color changes from
translucent white to a yellowish solution while cyclohexane and cyclohexene had no observable
changes. For the set of wrapped tubes, all of them were cloudy white except cyclohexene which
was yellowish in color.

Results showed a negative test for benzene and toluene wherein no color changes took
place. Aromatic hydrocarbons are less reactive towards bromine compared to alkanes. When
bromine approaches benzene or toluene, electrons in the pi bond repel electrons in Br-Br bond
which induces a dipole in the Br2 molecule, it is now polar. Pi-electron pair from the double
bond is now attracted to the slightly positive bromine atom, causing the double bond to break,
forming a new bond between one carbon atom and one bromine atom, forming a positively
charged carbocation. Through heterolytic fission, the bond between the two Br atoms breaks,
forming a bromide ion. The Br- ion is attracted towards the intermediate carbocation, forming a
covalent bond.

In addition, the reactant energy is lowered by dissolving Br2 making the reaction go more
readily because activation energy is lowered. For cyclohexane, UV light acts as a catalyst when
it is absorbed by bromine gas and breaks it into two bromine radicals. The bromine would then
remove and replace one hydrogen from the cyclic ring forming a cyclic halide. HBr is produced
as a by-product.

3. Oxidation: Reaction with Baeyers Reagent

Baeyer's reagent is an alkaline solution of cold potassium permanganate, which is a

powerful oxidant making this a redox reaction. The reaction of cyclohexene with Baeyer's
reagent had color changes from violet to brown due to the reaction with double or triple bonds in
an organic material. A positive result for this kind of test is the decolorization of a violet solution
and formation of brown precipitate (MnO2). Bayers test involves a redox reaction were in Mn7+
is reduced to Mn4+ and alkene is oxidized to a diol. The reaction of alkenes with KMnO4 yields
MnO2 and a diol.

In the experiment, the reaction of cyclohexane with Baeyers reagent had no color
changes, the solution still remained violet, and no layers were formed. Alkanes are saturated,
thus potassium permanganate does not react with it. For benzene, bubble suspension at the top of
the light violet layer was perceived. The same remark also goes with toluene, but only has an
exception, this time it is only lighter than what we have observed in benzene.

4. Reaction with Ammoniacal Silver Nitrate

To determine the presence of a triple bond (alkyne), the Reaction with Ammoniacal
Silver Nitrate must be observed. In the reaction, there is a release of terminal proton of the
alkyne so that the acetylide ion can form an insoluble precipitate with Ag+. For instance,
acetylene reacts with ammoniacal solution of AgNO3 forming acetylide of silver.
 H-C C-H + 2 AgNO3 + 2 NH4OH AgC CAg + 2NH4NO3 + 2H20
(White precipitate)

Addition of ammoniacal AgNO3 to each sample caused precipitates to form. When

ammoniacal AgNO3 was added to cyclohexane and toluene, the solution became cloudy. In
cyclohexene, the solution became light yellow while in benzene, it was colorless. Since the
reaction with ammoniacal AgNO3 is exclusive to alkynes, the cyclohexane, cyclohexene,
benzene and toluene resulted in a negative test in which there is no reaction.

B. Preparation and Testing of Acetylene Gas

The preparation of acetylene gas was done by reacting water to calcium carbide. The
slowly addition of water to calcium carbide resulted in the release of acetylene gas. The chemical
reaction for the preparation of acetylene is:

CaC2(s) + 2H2O (l) Ca(OH)2(s) + C2H2 (g)

Acetylene gas was then released upon the slow addition of water. The collected gas was
then tested for its solubility behaviour with DCM, H2O, 10% NaOH and H2SO4. For DCM, there
was formation of small black precipitate. In H2O, 10% NaOH and H2SO4, there were no
observable changes, still the liquid was colorless. The unwrapped mixture appeared less clear
(oily layer) than the wrapped mixture. For oxidation using Baeyers reagent, acetylene caused
the solution to change in color with bubble formation. And lastly, acetylene was tested with its
reaction with ammoniacal silver nitrate and resulted in the formation of precipitates.

III. Conclusion

Hydrocarbons are compounds that consist only of hydrogen and carbon atoms. Due to the
cancellation of C-H, they become a non-polar compound. To determine the solubility of
hydrocarbons, the general rule, like dissolves like is applied. In the halogenation process, the
reaction with bromine is said to be positive to the free radical substitution if it loses red-orange
color of the molecular bromine and the evolution of gas, hydrogen bromine has occurred. The
Baeyers test is used for double bonds or alkenes. For positive results using KMnO4 it must show
decolorization of a purple solution and formation of a brown precipitate (MnO2). These chemical
reactions such as halogenation and oxidation help us predict what type of hydrocarbon is being
tested (saturated or unsaturated).

IV. Answers to Questions

1. What is the function of CCl4 in the bromination reactions? How can it fulfil this role?
CCl4 serves as an inert solvent for bromine. It allows the two compounds to easily react
since bromine is immiscible with nonpolar hydrocarbon compounds.
2. Explain why terminal alkynes are acidic.
Alkynes are acidic because of its sp hybridization. This causes the alkyne to lose its
Hydrogen and form an H+ ion. The electron pair is nearest to the nucleus in sp hybridized
orbitals making anionic compound stable and a stable conjugate base indicates an acidic
compound.

3. Explain the bromination reaction of benzene, toluene, and cyclohexane.

Benzene and toluene comprise of double bonds and bromine readily reacts with them
even without the prescence of catalysts. Via electrophilic substitution, the Br2 replaces
one of the hydrogen singly bonded to the benzene/toluene ring with HBr produced as a
by-product. While in the case of cyclohexane, no reaction will take place because
saturated hydrocarbons will only react with bromine under free radical conditions, which
involves UV light.

4. Give the reagent and the reaction conditions that would distinguish between the following
compounds. Write the equations for the reactions involved.

a. benzene and ethylbenzene

Baeyers Reagent
Benzene does not undergo oxidation with Baeyers reagent. Oxidizing ethyl
benzene with Baeyers reagent (alkaline KMnO4) gives effervescence of CO2 with
bicarbonate.

No reaction

b. 1-butyne and 2-butyne

Reaction with ammoniacal AgNO3
With the reaction of Ammoniacal AgNO3, it is possible to determine whether the
CC is found at the end of the carbon chain or not. The terminal end of 1-butyne
releases a proton upon addition. Thus, resulting acetylide ion can form an
insoluble precipitate with Ag+. The reaction for 2-butyne is different.
 c. 2-methylpentane and 2-methyl-2-pentene
Reaction with bromine
2-methylpentane is an alkane and 2-methyl-2pentene is an alkene, to distinguish
one from the other, bromine test can be used. 2-methylpentane react with bromine
to produce H-Br gas as a by-product, while 2-methyl-2pentene does not produce
H-Br.

(CH3)2CHCH2CH2CH3 + Br -> (CH3)2CHCH2CH2CH2 + HBr ( For

(CH3)2CHCH2CH2CH3 + Br2 -> (CH3)2CHCH2CH2CH2Br + Br 2-methylpentane )

CH3C(CH3) = CHCH2CH3(g) + Br2 -> CH3C(CH3)CHCH2CH3(l) (For 2-methyl-2-

pentene )
Br Br

d. toluene and 1-methylcyclohexene

Baeyers Test

V. References

Smith, J. G., 2009. Organic Chemistry (3rd ed.) 1221 Avenue of the Americas, New York, NY
10020: The McGraw-Hill Companies, Inc.

Hydrocarbons. (February, 2014). Retrieved April 3, 2017 from https://www.academia.edu/

12417322/Hydrocarbons

Properties of Hydrocarbons. (July, 2011). Retrieved April 3, 2017 from http://www.mendelset.

com/articles/689/properties_hydrocarbons