CHM 217 Experiment # 8

Cis-Trans Isomerism in Alkenes

Objective
• Interconversion of cis-trans isomers – Conversion of Maleic acid to Fumaric acid.
• Determination of melting point of Maleic acid and Fumaric acid.

Introduction
Cis-trans isomerism (also known as geometric isomerism or E-Z isomerism) is a form
of stereoisomerism and it occurs in only 2 classes of compounds- Alkenes and Cyclic systems.
Cis-trans isomerism in alkenes is a consequence of restricted rotation at carbon-carbon
double bond which is due to the overlap of parallel p-orbitals that constitute π bond.

Cis-trans isomers are stereoisomers, that is, a pairs of molecules which have the same
formula but whose functional groups are rotated into a different orientation in three-
dimensional space
Consider an example 2-butene. The isomer with methyl groups on the same side of
the double bond is called cis isomer, while the isomer with methyl groups located on
opposite sides is called the trans isomer.

Alkenes are also named by E-Z system. In this system the two groups attached to
each carbon of the double bond are assigned a priority (1 or 2) based on the atomic number.
If the highest-priority groups attached to each carbon of the double bond are on the same
side of the double bond, the compound is Z and if it is on the opposite side of the double

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bond the compound is E. If you can’t decide using the first atoms attached, go to the next
atoms attached until a priority can be assigned.

* If an alkene has two identical substituents on one of the double bond carbons cis-trans or
E-Z isomers are not possible. Compounds shown below are identical and are not cis-trans
isomers.

Cis-trans isomers are diastereomers. Unlike enantiomers which are mirror images of each
other and non-superimposable, diastereomers are not mirror images of each other
and non-superimposable. They differ in all types of physical and chemical properties like
solubility, stability, melting point, boiling point, polarity etc. They have two or more stereo
genic centers.

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Interconversion of cis-trans isomers

In general rotation about a carbon-carbon single bond occurs rapidly at room temperature.
Unlike σ bonds, π bonds do not rotate (due to the overlap of parallel p-orbitals that
constitute π bond) and it requires 50-60 kcal/mole to break the π bond. Thus the rotation
about carbon-carbon double bonds does not happen at reasonable temperatures. Cis-trans
isomers can be interconverted or isomerized if the double bond is temporarily converted to
carbon-carbon single bond that can undergo a bond rotation to give either the cis or
trans isomer and then the 𝜋𝜋bond must be able to reform. This is possible under a variety of
conditions like heat, photolysis or by using a catalyst depending on the molecule.

For example, addition of an electrophile E+ or a free radical R. to the double bond results in
the formation of an intermediate carbocation or radical respectively, which allow the
rotation about carbon-carbon single bond. Elimination of the added electrophile or radical
then gives the isomerized alkene.

Conversion of Maleic acid to Fumaric Acid

A simple example of cis-trans isomerization is the conversion of maleic acid to fumaric acid.
Maleic acid is cis isomer (two –COOH groups are on the same side of C=C bond) and
fumaric acid is trans isomer (two –COOH groups are on the opposite side of C=C bond) of
butenedioicacid (C4H4O4).

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This isomerization is possible by photolysis in the presence of a small amount of bromine or
with the use of HCl as a catalyst.

Conversion of Maleic acid to Fumaric Acid by Free Radical Reaction

When an aqueous solution of maleic acid containing little amount of bromine is irradiated it
is rapidly isomerized to fumaric acid. Light converts elemental bromine into
bromine radicals, which attacks C=C double bond to form bromo-alkane radical, which
then can undergo free rotation about its central C to C bond. Upon loss of the bromine
radical from this intermediate (being unstable), the more stable fumaric acid is formed.
Since the solubility of fumaric acid in water is very low it crystallizes from the solution as it is
being formed.

Conversion of Maleic acid to Fumaric Acid using Hydrochloric acid

When an aqueous solution of maleic acid is heated at reflux with hydrochloric acid,
it converts to more stable fumaric acid. The mechanism of this isomerization is
an electrophilic addition of a hydrogen ion to form a carbocation intermediate followed
by rotation about a carbon-carbon single bond. The intermediate being unstable will
try to lose the proton that favor the formation of more stable trans isomer. Since fumaric
acid is less soluble in aqueous reaction mixture, it crystallizes from solution as the
reaction proceeds

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Maleic Acid vs Fumaric Acid

Fumaric acid is more stable than maleic Acid

Fumaric acid being a trans isomer will have the least steric hindrance as the two bulky
carboxylic acid (–COOH) groups are on the opposite sides of the C=C bond causing
least electron-pair repulsion. In maleic acid the two bulky –COOH groups are on the same
side of the C=C bond hence more steric hindrance and higher electron-pair repulsion.
Thus fumaric acid will be more stable than Maleic acid.

Maleic acid is more acidic than fumaric acid

In maleic acid the conjugate base formed after the loss of H+ ions is stabilized due to intra
molecular H-bonding. This type of H-bonding is possible due to its cis geometry.
But in fumaric acid the conjugate base formed is less stable due to the absence of
intramolecular H-bonding. Intramolecular H-bonding is not possible in trans geometry
because the two –COOH groups are on the opposite side of the C=C bond. If the stability of
conjugate base is higher, then it is more acidic. Hence maleic acid is more acidic.

5
Maleic acid is more soluble in polar solvents.

In maleic acid, presence of two –COOH groups on the same side of the C=C bond (cis
geometry) gives a resultant dipole moment as shown in the figure. But in fumaric acid
these major dipole moments cancel each other because of trans geometry. The dipole
moment is a measure of the polarity of the molecule. So maleic acid will be more polar in
nature and is quite soluble in polar solvents like water (0.79 g/mL of water at 250C).
Solubility of fumaric acid in water is very less (0.007 g/mL at 250C).

Melting point of maleic acid (130 0C) is much lower than that of fumaric acid (287 0C)

The symmetry of the molecule influences the melting point of cis-trans isomers. The more
symmetric the molecule, the easier it is to pack closely and regularly in its crystal lattice.
Closely packed molecules have stronger intermolecular forces, hence more amount of
energy is required to break this bond which results in a higher melting point.
Packing efficiency is higher in fumaric acid due to its trans geometry which results in
a strong intermolecular H-bonding, hence higher melting point.
In maleic acid, the molecules pack poorly due to its cis geometry, which means that the
intermolecular forces aren't as effective as they should be. Hence lower melting point than
fumaric acid. Cis isomer can form intra molecular H-bonding.

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Formation of Maleic anhydride

When maleic acid is heated under vacuum for a short time, just above its melting point
(130 0C), a mole of water is lost and maleic anhydride is formed. But in fumaric acid, the two
carboxyl groups are too far apart to react to foam a monomeric anhydride. It can form
a polymeric anhydride or, by isomerization at high temperatures, maleic anhydride.

Maleic acid Maleic anhydride

Procedure: Conversion of Maleic acid to Fumaric Acid using Hydrochloric Acid

In this experiment, maleic anhydride is hydrolyzed to maleic acid which is then isomerized
to fumaric acid by reflux with Hydrochloric acid.

Caution!!!!
• Maleic anhydride and maleic acids are strong irritants and can cause burns. Avoid
contact with skin, eyes and clothing. Wear disposable gloves.

• Hydrochloric acid is a corrosive liquid. Avoid contact with skin, eyes and clothing.
Wear disposable gloves. If you have an accidental spill, wash immediately with large
amount of water.

1. Weigh about 5g of maleic anhydride in a clean dry 100mL conical flask and add about
10mL of distilled water into the flask.
2. Slightly warm this mixture in a water bath maintained at 60-70 0C. When it turns into a
clear solution take out the flask from the water bath.

* The maleic anhydride first melts (mp-530C) and then reacts with water to form a clear
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 solution of maleic acid.

3. a) Transfer half portion of this clear solution (which is saturated with dissolved maleic
acid) into a round-bottomed flask.
b) Rest of the solution - cool to room temperature then place in an ice bath (3minutes)
for the complete crystallization of maleic acid. Perform vacuum filtration to collect
these crystals, dry in an oven about 10 minutes, cool and determine the melting point.
4. Add 7mL of con. HCl into the round-bottomed flask containing maleic acid (step 3a)
and gently reflux the solution until white foams/crystals of fumaric acid appear in the
flask.
5. Cool the solution to room temperature, then in an ice bath for complete
crystallization. Collect these white crystals of fumaric acid by vacuum filtration. Dry this
product in an oven about 10 minutes, cool and determine the melting point.

Waste disposal:

• Dispose all solid products in the labelled solid waste container.

• Dispose all liquid products in the labelled aqueous waste container.
• Dispose all used capillary tubes in the labelled glass container.

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 Experiment #8: Cis-Trans Isomerism in Alkene
PRE_- LABORATORY QUESTIONS
Name: George Piliqusyan AUS ID#: 93276 _
Mrs. Resha
Date: 4/4/23 Lab Instructor: _ Lab Section: I

1. What are cis-trans isomers? What type of compounds can exhibit cis-trans isomerism?
Lis-trans the
isoners are
steerisomers, thatis, a
pair
of molecules which have same formula butwhose functional
groups rotated into differentorientation 3D Can
are
a in
space. occur in alkans & cyclic systems.

2. Draw the structures of cis-trans isomers for each compound given below. Label them
cis and trans. If no cis-trans isomers exist, write none.
a) 1,1-dibromo-1-butene b) 4-methyl-2-pentene c) butenedioic acid

Drag -(It's
=

Ha, c-la Poykou

Bri
=

/ -H trans
(I3
None
trans y ·
(V3
Ok
on
-
CsHz
CL =

Lis
/ -H
H
Lis

4. Write the equation of the formation of fumaric acid from maleic anhydride.

↑ He
cool
H_, _coor
pot 4
f
H

n
"crow orBr+
/ "In
COOM

5. Fumaric acid is more stable than maleic acid. Explain why?

Maleic acid contains

bulky "COOM"groups on
the same side of the carbon double bond so

there of 1
is an increase storic hindrance & electron
more
pair repulsion.
 Experiment # 8: Cis-Trans Isomerism in Alkene
LAB REPORT
Name: Gerrg Piligusyan AUS ID #: 93276

Mrs. Besha I
Date: 4/4/2023 Lab Instructor: Lab Section:

Conversion of Maleic acid to Fumaric acid

Compound Melting point, 0 C

Maleic acid

Fumaric acid

Questions
1. Write the mechanism of acid catalyzed isomerization of maleic acid to fumaric acid.

Heg-coo Ha+coor Un con H

He, -con
j_COOH
+

Is
↓- 4*

"acron
-
!
-

-> Il

/
v coon
- n ! -
n , H
n n'crow crow' LOON

2. The melting point of fumaric acid is higher than maleic acid. Explain why?

Samaric acid has multige

hydrogen bonds

1
3. In this experiment, you could observe the precipitation of fumaric acid from the hot
aqueous mixture. What property of fumaric acid makes it to precipitate? Explain.

High meltingpoint, low

solubility &
polarity

Makic the & fumaric the trans of butenebiric acid. Lis

is sis
is isomer is less stable. Malic acid is soluble in water
where fumaric
as acid is not. This can be explained by the Hydrogen bonding thatis taking place.

4. Draw the structures of E-Z isomers for each compound given below. Label them E and Z.
If no E-Z isomers exist, write none.
a) 2-bromo-2-pentene b) 1-pentene c) 1,2-dichloropropene

Che
·
H -U 2H, -CV2
- (Halls UC e
C
=

L
W
/
Cli
H 1 cl
I

None Exist E-1,2-dichler propene

E-2-brow-2-perfore
2

H -I
2
2 H
= -4
=C
/ -CH
2
12

-Cracks,
I

Br
I
2-1,2-dichlorprogene
2- 2-bromo-petere