Question 2 : Explain in details about hydrogenation of alkene and dehydrogenation of

alkane. Support your explanation with suitable chemical equations.

Hydrogenation is the reaction of the carbon-carbon double bond in alkenes with hydrogen in
the presence of a metal catalyst. The application of this reaction is includes the manufacture
of margarine from animal or vegetable fats and oils. One of the hydrogenation simplest cases
is the hydrogenation of ethane. Ethene reacts with hydrogen in the presence of a finely
divided metal catalyst such as nickel, platinum, palladium and rhodium at a temperature of
about 150°C.




This reaction is an example of a heterogeneous catalysis process which the reaction
takes place on the surface of the metal. Ethene molecules are adsorbed on the surface of the
metal catalyst, nickel. The double bond between the carbon atoms breaks and the electrons
are used to bond it to the nickel surface.



Hydrogen molecules are also adsorbed on to the surface of the nickel. When this
happens, the hydrogen molecules are broken into atoms. These can move around on the
surface of the nickel.



If a hydrogen atom diffuses close to one of the bonded carbons, the bond between the
carbon and the nickel is replaced by one between the carbon and hydrogen.


That end of the original ethene now breaks free of the surface, and eventually the
same thing will happen at the other end.



As before, one of the hydrogen atoms forms a bond with the carbon, and that end also
breaks free. There is now space on the surface of the nickel for new reactant molecules to go
through the whole process again



Whereas, dehydrohalogenation is a reverse reaction of
hydrogenation/halogenations/halo in order to obtain alkenes. For example, an organic
reaction in which alkyl halide when boiled with alcoholic alkali gives corresponding alkene.
It is also called a β-Elimination reaction and is a type of elimination reaction.
In this reaction, the halogen on the carbon in the alkyl halide reacts with hydrogen
present on the β-carbon releasing hydrogen halide. Hence an alkene is formed due to
formation of a double bond between the α- and β-carbon.Zaitsev's rule helps to
explain regioselectivity for this reaction type. The opposite transformation is called
hydrohalogenation.

Reactions



Here ethyl chloride reacts with potassium hydroxide dissolved in ethanol,
giving ethene. Likewise, 1-chloropropane and 2-chloropropane give propene. Chlorobenzene
does not react with potassium hydroxide due to the presence of the benzene ring, which, due
to stabilization as a result of aromaticity, does not give conventional elimination, as it would
lead to a very unstable benzyne intermediate. In general, the above reaction of
haloalkane with potassium hydroxide would compete with an Sn2 nucleophilic
substitution reaction (minor product) because OH
-
is a strong, sterically unhindered
nucleophile. Perhaps a better reagent would be a deprotonated alcohol such as potassium tert-
butoxide ([CH
3
]
3
CO
-
K
+
) or, because it is an oxide anion and thus a strong
base and nucleophile, potassium ethoxide (CH
3
CH
2
O
-
K
+
), and because of steric hindrance,
thereby promoting an elimination mechanism instead of a substitution mechanism.

Question 2 : What is Lucas’s reagent and how it can be used to differentiate primary,
secondary and tertiary alcohol?

Lucas' reagent is a solution of anhydrous zinc chloride in concentrated hydrochloric acid.
This solution is used to classify alcohols of for low molecular weight alcohols and it
distinguishes the rates of reaction of alcohols. The reaction is a substitution in which the
chloride replaces a hydroxyl group. Positive indicator of the reaction is the formation of a
water insoluble alkyl chloride as cloudiness or a precipitate, signalling formation of
a chloroalkane. The formation of an alkyl chloride with tertiary alcohol is very rapid,
followed by the secondary alcohol that may take from 5 to 20 minutes to form visible
cloudiness. Primary alcohols do not react with Lucas reagent or it may show very little result
in a very long time. The chemical reaction involves replacing the –OH group of the alcohol
with a chloride ion from hydrochloric acid (HCl), forming an alkyl chloride, as shown in the
following equation.
ROH + HCl → RCl + H
2
O

The differing reactivity reflects the differing ease of formation of the
corresponding carbocations. Tertiary carbocations are far more stable than secondary
carbocations, and primary carbocations are the least stable. An equimolar mixture of
ZnCl
2
and HCl is the reagent. The mechanism start when the alcohol is protonated by this
mixture, and H
2
O group attached to carbon is replaced by the nucleophile Cl
-
, which is
present in excess. Tertiary alcohols react immediately with Lucas reagent as evidenced
by turbidity owing to the low solubility of the organic chloride in the aqueous mixture.
Secondary alcohols react within five or so minutes (depending on their solubility). Primary
alcohols do not react appreciably with Lucas reagent at room temperature. Hence, the time
taken for turbidity to appear is a measure of the reactivity of the class of alcohol, and this
time difference is used to differentiate between the three classes of alcohols:
 no visible reaction at room temperature and cloudy only on heating: primary, such as
normal amyl alcohol (1-Pentanol)
 solution turns cloudy in 3–5 minutes: secondary, such as sec-amyl alcohol (2-Pentanol)
 solution turns cloudy immediately, and/or phases separate: tertiary, such as tert-amyl
alcohol (2-Methyl-2-butanol)

Question 3 : Explain how propyl ethanoate can be prepared in the laboratory.

In the experiment of preparing propyl ethanoate in the laboratory, the reaction will be
performing by Fischer esterification. The general mechanism is pictured in Figure 1.


Figure 1. The overall reaction for Fischer esterification.
The overall mechanism for a general acid and alcohol is depicted in Figure 2.

Figure 2. The general mechanism for Fischer esterification.

The overall mechanism follows the normal PADPLD. The acid catalyst is involved in
the first step and regenerated in the last step. The first step is protonation of the carbonyl
oxygen, followed by addition of the alcohol to form a tetrahedral intermediate. The third and
fourth steps involve a proton transfer to form water, a good leaving group. After the water
leaves in the fifth step, there is just the deprotonation of the carbonyl oxygen to form the
neutral species. In your reaction, the synthesis of banana oil – isopentyl acetate, you will be
using isopentyl alcohol (3-methyl-1-butanol) and acetic acid (ethanoic acid, see Figure 3).

Figure 3. The overall reaction for this experiment

Experiment work
Add 5 mL isopentyl alcohol, 7 mL glacial acetic acid, and a couple of boiling stones to a 25
mL round bottom flask. Add 0.5 mL of sulfuric acid with swirling to mix the solution. Attach
the flask to a reflux condenser and heat the mixture to reflux for 60 minutes. After cooling to
room temperature, transfer the contents to a large reaction tube. Add 15 mL of distilled water
to the solution and stir. Let the layers separate. Remove the aqueous layer and discard. Wash
the organic layer with 9 mL portions of a saturated sodium bicarbonate solution until it tests
basic after removing from the reaction tube. Finally, wash the organic layer with 6 mL of a
saturated sodium chloride solution. Dry the organic layer with anhydrous sodium sulfate for
10 to 15 minutes. Transfer the organic layer to a 10 mL flask, filtering it through a cotton
plug. Final volume/weight and IR spectrum are recorded.

Question 4 : There are 2 unlabeled bottles of chemicals in laboratory in which one of the
bottles is pentane and the other one is pentene. Suggest three chemical tests that can help you
to determine which of the two bottles is alkane and alkene.

First test: Addition of bromine
Hydrocarbons are colourless. While, bromine dissolved in water or trichloroethane solvent
forms an orange (yellow/brown) solution. When bromine solution is added to both an alkane
or an alkene, the alkane solution remains orange – which means no reaction. However,
the alkene decolourises the bromine as it forms a colourless dibromo-alkane compound. This
is due to unsaturated molecules in alkenes, which allowed atoms can add to them via
the C=C double bond, so a reaction occurs. Whereas, alkanes are saturated , which means
there is no double bond and atoms cannot be added. Therefore, there is no reaction.

Second test: Alkenes can add hydrogen to form a saturated alkane molecule
Alkenes will react with hydrogen gas over a nickel catalyst to produce margarine from
vegetable oils.

Third test: Addition of water to make alcohols
The alcohol ethanol can be made by passing ethene gas and water vapour over an
acid catalystat 300
o
C. This is an example of an addition reaction and a hydration
reaction because it involves the addition of water to another molecule.

Question 5 : Explain how Tollen’s reagent, Fehling’s solution and Schiff’s reagent can be
used to test aldehyde. State the observation of the reaction of aldehyde with each reagent.

Tollens' reagent is a chemical reagent most commonly used to determine whether a known
carbonyl-containing compound is an aldehyde or a ketone. It is usually ammoniacal silver
nitrate, but can also be other mixtures, as long as aqueous diamminesilver(I) complex is
present. A positive test with Tollens' reagent results in elemental silver precipitating out of
solution, occasionally onto the inner surface of the reaction vessel, producing a characteristic
and memorable "silver mirror" on the inner vessel surface. Aldehydes will be positive in
Tollen's test and a mirror-like material will be formed.



Ball-and-stick model of the diamminesilver(I) cation, [Ag(NH
3
)
2
]
+


Fehling's also can be used to determine whether a carbonyl-containing compound is
an aldehyde or a ketone. The bistartratocuprate(II) complex in Fehling's solution is
an oxidizing agent and the active reagent in the test. The compound to be tested is added to
the Fehling's solution and the mixture is heated. Aldehydes are oxidized, giving a positive
result, but ketones do not react, unless they are alpha-hydroxy-ketones. The
bistartratocuprate(II) complex oxidizes the aldehyde to a carboxylate anion, and in the
process the copper(II) ions of the complex are reduced to copper(I) ions. Red copper(I) oxide
then precipitates out of the reaction mixture, which indicates a positive result i.e.
that redoxhas taken place (this is the same positive result as with Benedict's solution). A
negative result is the absence of the red precipitate; it is important to note that Fehling's will
not work with aromatic aldehydes; in this case Tollens' reagent should be used.



The Schiff test is relatively general chemical test for detection of many organic
aldehydes. The unknown sample is added to the decolorized Schiff reagent; when aldehyde is
present a characteristic magenta color develops. Fuchsin solutions appear colored due to the
visible wavelength absorbance of its central quinoid structure—see also for example viologen
but are "discolorized" uponsulfonation of the dye at its central carbon atom by sulfurous acid
or its conjugate base, bisulfite.

This reaction disrupts the otherwise
favored delocalizedextended pi-electron system and resonance in the parent molecule.










The structure of the "decolorized" Schiff reagent.