How Do Molecules Add Across Double Bonds

Isabelle Renee Salinas, Christian Matthew Silva and Hannah Michaela Son
College of Science, University of Santo Tomas, Manila, Philippines

Abstract
The experiment conducted aims to understand the concepts of adding molecules across
double bonds by using the Addition Reaction Mechanism. Additionally, the following techniques
were used namely, Reflux Method, Vacuum Filtration, Recrystallization, Percent Yield, and
Melting Point Determination. The initial theoretical yield calculated was 1.247g and the actual
yield weighed was 0.1284g, resulting in a percent yield of 10.2967%. The compound that was
determined from the melting point of 136.4​°​C was a ​cis​ 2,3-dibromo-3-phenylpropanoic acid.

Introduction
Alkenes are one of the most common functional groups that are seen in organic
compounds. Generally, it consists of two atoms that are connected to each other by two bonds, a
pi bond and a sigma bond. When described by ChemLibreTexts​TM​, it is a class of hydrocarbons
that are found in an unsaturated compound and requires at least one carbon-to-carbon double
bond. Another term that can be used to describe Alkenes is the word ​olefins.​ A
​ lkenes can easily
be distinguished from alkanes by a simple chemical test which includes adding it to bromine. If
the mixture remains colourless, it is an alkene.

Retrieved From: https://en.wikipedia.org/wiki/Cinnamic_acid

Fig 1.1 Trans-cinnamic acid molecular geometry

As the main compound that will be used in the experiment, Cinnamic acids are actually
important in the formation of complex phenolic compounds (Swanson, 2003). This compound is
also known to be a monocarboxylic acid that acts as a plant metabolite, meaning it is a precursor
for the synthesis of a number of plant substances such as lignin, tannins, and others as mentioned
in the Encyclopedia of Food Sciences and Nutrition (Second Edition). Additionally, the
compound is said to be found in Cinnamomum cassia (Pubchem, 2020). As for its physical
properties, it is an odorless white crystalline acid that is slightly soluble in water indicating its
nonpolar property. In the case of the experiment the compound given was a ​trans-​ cinnamic acid,
which is the more common form of cinnamic acids. The compound is often used in
manufacturing methyl, ethyl, and benzyl esters for perfumes (ACS.org, 2014)

The addition reaction mechanism, a main theme in the experiment, is classified as one of
the four major classes of reactions in Organic Chemistry. This simple reaction occurs between
two reactants and yields one product that has all the atoms that were present in the reactant side
(Siyavula.com, 2020), though there are rare occasions where the addition reaction yields two
products; however, not in equal amounts. The addition reaction formula usually follows this
pattern:

Retrieved From: https://byjus.com/chemistry/addition-reaction/

Fig 1.2 Addition Reaction Pattern

When described in the Organic Chemistry lab manual, it tells how from an alkene,
normally, unsaturated state the compound becomes more saturated. Furthermore, a very detailed
mechanism of the movement of bonds is described, where the pi bond of the alkene is converted
into a sigma bond by movement of electrons. It is important to note that when attempting to use
this reaction, only molecules that are part of a multiple bond are affected (Master Organic
Chemistry, 2019), the reactions basically break a pi bond and form two new single bonds. Due to
this, this reaction is often used to convert the alkenes or alkynes in unsaturated compounds into
other functional groups.

Recrystallization is a method of purifying nonvolatile organic solvents. During

recrystallization, the attractive forces between solute molecules are overcome during the
recrystallization process however, it does not break any chemical bonds.The procedure includes
dissolving the material to be purified in an appropriate hot solvent. The hot solvent must have a
higher temperature coefficient, dissolve the impurities readily or not at all and must not react
with the solvent. The solute must be relatively insoluble in the solvent at room temperature and
be much more soluble in the solvent at higher temperatures. As the solvent cools, the solution
becomes saturated with the solute and it crystallizes and reforms a solid. If there is no visible
particulate matter in the solution, the solution can undergo vacuum filtration. As the crystal
forms, any impurities are removed from the crystal lattice structure thus completing the
purification process.

Vacuum filtration, also known as Suction filtration, is a technique that speeds up the rate
of filtration as compared to the usual gravity filtration. Vacuum filtration is used in
recrystallisation experiments. The process utilizes a b​üchner funnel which is placed into a
b​üchner flask held together by a rubber bung. The suction from an aspirator creates a partial
vacuum in the flask.

The reflux method is used to allow liquid to boil and condense without letting the
condensed liquid escape and return back to the flask. Its set up is similar to the distillation set up
but the condenser is placed vertically instead of horizontally. In a reflux setup, the evaporated
solvent is confined within the condenser therefore the concentration of reactants remain constant
throughout the whole process. The setup also allows greater control over the temperature of the
solution when heating.
 Melting point determination allows for the identification of an unknown sample and can
indicate whether a substance is pure. Impurities in a substance will increase or decrease the
melting range by 1-2​ºC as it disrupts the consistency and organization of the crystal lattice at the
molecular level. The melting range is defined as the span of temperature from the point at which
the crystals first begin to liquefy to the point where the entire sample is now liquid.

Percent yield is often used in determining how much of the actual substance will be
gained from the reaction. More often than not, the actual yield is less than the theoretical yield
due to various external factors that interfere with the experiment. Additionally, scientists use this
formula to see how effective the reaction was because it is shown how much of the reactants
were used when performing the experiment. When calculating for the percent yield, the actual
yield is put over the theoretical yield and the dividend is multiplied by 100%. Although there are
instances where the actual yield will go over 100%, in which case this only shows that there were
additional compounds that added to the impurities of the substance.

Through this experiment, the researchers aim to effectively understand the addition
reaction mechanism and its functions in the section of Organic Chemistry, with the use of
trans-cinnamic acid, bromine, and CH​2​Cl​2​. As well as learn and master the following techniques:
reflux method, recrystallization, vacuum filtration, and melting point determination; where the
reflux method is used as an aid for the addition reaction mechanism and the processes of
recrystallization and melting point determination is used for purification.

Experimental
The lab apparatus used in the experiment included the following: 50mL, 100mL and 250
mL beakers, pear-shaped flask with two necks, condenser, 2 rubber tubings, wire gauze, pipette,
funnel, small stirring rod, heating plate, complete vacuum filter set, 10mL graduated cylinder,
Buchner funnel, iron stand with iron clamps, alcohol burner, metal desiccator, 2 capillary tubes,
and a mortar and pestle. As for the chemicals that were used for the experiment they include:
0.6g of ​trans​-cinnamic acid, distilled water, 1 mL of 10% Bromine (Br​2​), 10mL of dry
dichloromethane (CH​2​Cl​2​), and 2 boiling chips.

To start off the experiment, 0.6007g of ​trans-​ cinnamic acid was measured in a 50mL
beaker using an analytical weighing balance. It is important to note that before weighing any
compounds inside the analytical weighing balance, one should tare and calibrate the balance with
the beaker inside to ensure that only the substance is weighed. Once weighing is done, the
trans-​ cinnamic acid was placed inside the pear-shaped flask along with the 1mL of 10% Br​2 and
10mL of dry CH​2​Cl​2​, that must be measured beforehand using a graduated cylinder. A water bath
was prepared in a big basin for the reflux set-up. To prepare the reflex set-up, connect 2 rubber
tubings to the areas where the water is to go in and out the condenser. Then, attach one of the
rubber tubings to the water pump, while the other rubber tubing should be connected to a funnel
where it will be placed in a water bath to ensure a smooth flow of water. The bottom of the
condenser was connected to one opening of the pear-shaped flask, while the other opening of the
flask was covered by a cork. Next, an iron stand was prepared close to the heating plate and the
iron clamps were affixed with the condenser at a reasonable height on the iron stand. Then,
another iron clamp was placed right above the heating plate where the pear-shaped flask was
fastened. A 250mL beaker was prepared with ice cold water and 2 boiling chips that were placed
inside the flask; a wire gauze was placed on the heating plate where the 250mL beaker full of ice
water was placed. The pear-shaped flask was fastened with the iron clamp, while making sure
that it is considerably immersed inside the 250mL ice bath. Before the heating plate was turned
on, a thermometer was placed inside the 250mL beaker to take note of the temperature
throughout the reflux process. The heating plate and water pump was turned on and the
temperature was observed until it reached 50℃. After which the researchers kept the temperature
at 50℃ for 20 minutes. A change of color, from orange to transparent, was noted and the
contents of the pear-shaped flask were transferred to a 50mL beaker where it will be covered by
a film and stored in a locker that is at room temperature. At this point of the experiment, it is
expected to have the theoretical yield calculated for and written down in the logbook.

Fig 1.3 Moving the trans-cinnamic acid to the Fig 1.4 Reflux setup
pear-shaped flask

Fig 1.5 Beakers with trans-cinnamic acid were placed

inside the metal desiccator

The beaker was taken out once all, previously liquid, contents had been turned into
crystals. A 1:1 solution of 10mL of ethanol and 10mL of distilled water was prepared and heated
on a heating plate. Whilst the solution was being prepared, a filter paper was procured and was
cut to effectively match the size of the funnel that was prepared. Before any of the solution was
placed onto the funnel or into the crystals, the solution was to reach a boiling state first. Once the
solution of ethanol and distilled water started to boil, a good portion of it was used to dissolve
the crystallized ​trans-​ cinnamic acid, and rinse the filter paper in warm solution with a pipette.
The dissolved acid was poured into the funnel with the filter paper and into another beaker. Next,
a Buchner funnel was prepared as well as an appropriately sized filter paper that was to be fit
inside the funnel. A rubber stopper was placed onto the opening of the vacuum filter to ensure no
escape of air and the funnel was placed atop it. The ​trans​-cinnamic acid was carefully poured
into the funnel and was subject to the vacuum filter for about 3 mins. Then the filter paper was
patted dry and transferred into another beaker once again for weighing, after which it will be
stored in the metal desiccator. With the weight of the pure ​trans​-cinnamic acid, the percentage
yield was calculated and written down in the logbook.

Fig 1.6 Vacuum filtration setup Fig 1.7 Drying of pure trans-cinnamic
acid

For the Melting point determination test, the pure ​trans-​ cinnamic acid was grinded and
pulverized using a mortar and pestle to achieve a powder. Two capillary tubes were also
prepared, on the side, and had their non-colored endings sealed using an alcohol burner. After
which the pure ​trans-​ cinnamic acid powder was carefully placed inside the capillary tube and
was dropped inside a long glass tube to ensure that the powder is secured inside the tube. The
process was repeated until the level of powder inside the capillary tube reached 3-5 mm. To
prepare for the melting point test setup, a 100 mL beaker filled with oil was placed on a heating
plate, while the two capillary tubes were attached to a thermometer via a rubber band. The
thermometer was attached to the iron clamp and was partially submerged, along with the
capillary tubes, in the oil bath. The heating plate was turned on and the boiling point of oil bath
and melting point of the pure ​trans​-cinnamic acid was observed. As such, recordings were
written down in the logbook.

Fig 1.8 Powderizing the trans-cinnamic Fig 1.9 Pouring of the trans-cinnamic
acid acid solution into a funnel
 Fig 1.10 Beaker with oil bath and capillary Fig 1.11 Melting point determination setup
tubes

Fig 1.12 Schematic Diagram for Addition Reaction Mechanism, Purification, and Melting point determination of
trans-cinnamic acid
Results and Discussion
Testing for Theoretical yield and Percentage yield
Given that 0.6007g of ​trans​-cinnamic acid was added to 1ml of 10% diatomic bromine
(Br​2​) ,with the molecular weight of Br​2 ​being 308.0g/mol in a solution ratio of 1:1. Additionally,
with dichloromethane (CH​2​Cl​2​) acting as a solvent for the ​trans​-cinnamic acid to effectively
dissolve all solid particles of the acid. In the end, the theoretical yield that was calculated was
1.247g.

Figure 1.13 Initial weight of the trans-cinnamic acid

0.6007g of C9H8O2 1 mol C9H8O2 1 mol Br2 308.0g

T heoretical yield = 1
× 148.1586g of C9H8O2
× 1 mol C9H8O2
× 1 mol Br2
= 1.249g

However, after weighing the actual collected sample at 0.1284g at the end of the
experiment. The percentage yield is shown to be only at 10.2802%.
0.1284g
P ercentage yield = 1.2490g
× 100% = 10.2802%

Figure 1.14 Actual yield of the trans-cinnamic acid

The researchers believe that several external factors such as the transport of the
trans​-cinnamic acid from one container to another, the occurrence of an error during the
experiment and many others affected the amount of actual yield that the group would receive.
Melting point determination
Next, the melting point of the crystals in two capillary tubes were determined. The
temperature at which the crystals started to melt (T​1​) and the temperature where all the crystals
had completely melted (T​2​) was recorded to establish an approximate melting point. The two
tests showed that the two capillary tubes holding the crystal samples had rather consistent values
while only differing in temperature by about 0.1 - 0.2​°C.

Table 1.1 Boiling and Melting points of trans-cinnamic acid

Temperature/​°​C Capillary 1 Capillary 2

T​1 134.2 134.1

T​2 136.2 136.4

Retrieved from: http://chemistry.bd.psu.edu/halmi/chem213brominationF08.pdf

Fig 1.15 Bromination of Trans-Cinnamic Acid

In this part of the experiment, there are three possible types of reaction mechanisms: anti
addition reaction, syn addition reaction or mixture of anti and syn addition reaction. In an anti
addition reaction, the substituents or elements are added to the opposite sides of the double bond.
In a syn addition reaction, the substituents or elements are added to the same side of the double
bond. The product for the anti addition reaction should have a melting point of 93​°C ​to 95​°C and
the product for the syn addition reaction should have a melting point of ​202​°C ​to 204​°C. After
conducting the experiment, the value of melting point of the product was found to be at 136.4°C.
This means that the reaction was a mixture of the Anti and Syn addition reaction mechanisms.

Conclusion and Recommendations

In determining the percent yield of the reaction, one must determine the theoretical and
actual yield of the experiment. The theoretical yield of the is the ideal and maximum amount of
product that can be produced from a reaction (Khan Academy, 2020). But in determining the
theoretical yield, it is necessary to determine the limiting reactant. The limiting reactant is the
reactant that gets used up first (Zumdahl, 2005). After determining the theoretical yield, the
actual yield can be determined through the experiment. The percent yield that was acquired
during the experiment was only about 10.28%. This is very low compared to the 60% to 70%
expected percent yield. The low percent yield can be caused by several factors such as human
error.
 In the experiment, ​cis 2,3-dibromo-3-phenylpropanoic acid was formed due to the
addition of bromine to the double bond of carbon in trans-cinnamic acid. ​There are two possible
types of product which can be made in the reaction. The first product is a compound produced in
an anti addition reaction which will create a product that has a melting point of 202°C to 204°C.
While the second product is an compound produced in an syn addition reaction which will
create a product that has a melting point of 93°C to 95°C. ​After finding the weight of the
product, the melting point was determined to be 134.6​°C. Based from its melting point, it can be
concluded that the reaction was a mixture of both anti and syn addition reaction

The data collected in this experiment could be more accurate; therefore, the group
recommends the following improvements to the experimental design. Firstly, in the process of
cooling the liquid mixture of trans-cinnamic acid and diatomic bromine, ensure that the beaker is
properly covered by the film as it might slow down the crystallization process and might allow
the entry of other substances into the mixture. Secondly, the filter paper that is inserted into the
buchner funnel should be in the exact size so as to minimize crystal loss. Dry the crystals with
filter paper thoroughly so that the weight of the crystals obtained is as accurate as possible.
Lastly, the actual yield could be higher if all the crystals were correctly transferred during the
experimental process. It is recommended that researchers take extra caution when transferring
crystals from different apparatus so as to not waste any of the acid and achieve a successful
actual yield for the calculation of the theoretical yield.

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