I.

TITLE OF EXPERIMENT :
Making Cis and Trans Potassium Dioxalato Diaquo Chromium (III)
II. DATE OF EXPERIMENT : Monday, April 23rd 2018
III. PURPOSE OF EXPERIMENT :
 To learn how to make salt complexes of potassium dioxalato diaquo chromium
(III)
 To learn the characteristic of cis and trans complexes salt of potassium dioxalato
diaquo chromium (III)
IV. BASIC THEORY :
Geometric isomerism (also known as cis-trans isomerism or E-Z isomerism) is
a form of stereoisomerism. This page explains what stereoisomers are and how you
recognise the possibility of geometric isomers in a molecule. somers are molecules
that have the same molecular formula, but have a different arrangement of the atoms
in space. That excludes any different arrangements which are simply due to the
molecule rotating as a whole, or rotating about particular bonds. Where the atoms
making up the various isomers are joined up in a different order, this is known as
structural isomerism. Structural isomerism is not a form of stereoisomerism, and is
dealt with on a separate page (Clark, 2012).
Cis–trans isomerism, also known as geometric isomerism or configurational
isomerism, is a term used in organic chemistry. The prefixes "cis" and "trans" are
from Latin. In the context of chemistry, cis indicates that the functional groups are on
the same side of the carbon chain while trans conveys that functional groups are on
opposing sides of the carbon chain (Charlton, 1879).
Cis-trans isomers are stereoisomers, that is, pairs of molecules which have the
same formula but whose functional groups are rotated into a different orientation in
three-dimensional space. It is not to be confused with E–Z isomerism, which is
an absolute stereochemical description, and only to be used with alkenes. In general,
stereoisomers contain double bonds that do not rotate, or they may contain ring
structures, where the rotation of bonds is restricted or prevented (Charlton, 1879).
 cis-but-2-ene trans-but-2-ene

In one, the two chlorine atoms are locked on opposite sides of the double
bond. This is known as the trans isomer. (trans : from latin meaning "across" - as in
transatlantic). In the other, the two chlorine atoms are locked on the same side of the
double bond. This is know as the cis isomer. (cis : from latin meaning "on this side")

Picture 1. The example of Cis and Trans

The characteristic of cis and trans are :

Table 1. The characteristic of Cis and Trans

In each case, the higher melting or boiling point is shown in red. It notice that:

 the trans isomer has the higher melting point; and

 the cis isomer has the higher boiling point.

There must be stronger intermolecular forces between the molecules of the

cis isomers than between trans isomers. Taking 1,2-dichloroethene as an example:
Both of the isomers have exactly the same atoms joined up in exactly the same order.
That means that the van der Waals dispersion forces between the molecules will be
identical in both cases. The difference between the two is that the cis isomer is a polar
molecule whereas the trans isomer is non-polar (Charlton, 1879). Both molecules
contain polar chlorine-carbon bonds, but in the cis isomer they are both on the same
side of the molecule. That means that one side of the molecule will have a slight
negative charge while the other is slightly positive. The molecule is therefore polar.

Picture 2.Electronegativity and Electropositively

Because of this, there will be dipole-dipole interactions as well as dispersion

forces - needing extra energy to break. That will raise the boiling point. A similar
thing happens where there are CH3 groups attached to the carbon-carbon double bond,
as in cis-but-2-ene. Alkyl groups like methyl groups tend to "push" electrons away
from themselves. You again get a polar molecule, although with a reversed polarity
from the first example.

Picture 3. Electrons push away

By contrast, although there will still be polar bonds in the trans isomers,
overall the molecules are non-polar. The slight charge on the top of the molecule (as
drawn) is exactly balanced by an equivalent charge on the bottom. The slight charge
on the left of the molecule is exactly balanced by the same charge on the right. This
lack of overall polarity means that the only intermolecular attractions these molecules
experience are van der Waals dispersion forces. Less energy is needed to separate
them, and so their boiling points are lower.

Picture 4. Less energy is needed to separate them

 You might have thought that the same argument would lead to a
higher melting point for cis isomers as well, but there is another important factor
operating. In order for the intermolecular forces to work well, the molecules must be
able to pack together efficiently in the solid. Trans isomers pack better than cis
isomers. The "U" shape of the cis isomer doesn't pack as well as the straighter shape
of the trans isomer. The poorer packing in the cis isomers means that the
intermolecular forces aren't as effective as they should be and so less energy is needed
to melt the molecule - a lower melting point (Clark, 2012).

Cis and trans isomers often have different physical properties. Differences
between isomers, in general, arise from the differences in the shape of the molecule or
the overall dipole moment. These differences can be very small, as in the case of the
boiling point of straight-chain alkenes, such as pent-2-ene, which is 37 °C in the cis
isomer and 36 °C in the trans isomer . The differences between cis and trans isomers
can be larger if polar bonds are present, as in the 1,2-dichloroethenes. The cis isomer
in this case has a boiling point of 60.3 °C, while the trans isomer has a boiling point
of 47.5 °C. In the cis isomer the two polar C-Cl bond dipole moments combine to
give an overall molecular dipole, so that there are intermolecular dipole–dipole forces
(or Keesom forces), which add to the London dispersion forces and raise the boiling
point. In the trans isomer on the other hand, this does not occur because the two C−Cl
bond moments cancel and the molecule has a net zero dipole (it does however have a
non-zero quadrupole) (March, 1999).

The two isomers of butenedioic acid have such large differences in properties
and reactivities that they were actually given completely different names. The cis
isomer is called maleic acid and the trans isomer fumaric acid. Polarity is key in
determining relative boiling point as it causes increased intermolecular forces, thereby
raising the boiling point. In the same manner, symmetry is key in determining relative
melting point as it allows for better packing in the solid state, even if it does not alter
the polarity of the molecule. One example of this is the relationship between oleic
acid and elaidic acid; oleic acid, the cis isomer, has a melting point of 13.4 °C,
making it a liquid at room temperature, while the trans isomer, elaidic acid, has the
much higher melting point of 43 °C, due to the straighter trans isomer being able to
pack more tightly, and is solid at room temperature (Craig, et al., 1997) .
 Thus, trans alkenes, which are less polar and more symmetrical, have lower
boiling points and higher melting points, and cis alkenes, which are generally more
polar and less symmetrical, have higher boiling points and lower melting points. In
the case of geometric isomers that are a consequence of double bonds, and, in
particular, when both substituents are the same, some general trends usually hold.
These trends can be attributed to the fact that the dipoles of the substituents in a cis
isomer will add up to give an overall molecular dipole. In a trans isomer, the dipoles
of the substituents will cancel out due to being on opposite sides of the molecule.
Trans isomers also tend to have lower densities than their cis counterparts. As a
general trend, trans alkenes tend to have higher melting points and lower solubility in
inert solvents, as trans alkenes, in general, are more symmetrical than cis alkenes
(March, 1999).

Picture 5. Different between cis and trans

Usually for acyclic systems trans isomers are more stable than cis isomers.
This is typically due to the increased unfavourable steric interaction of the
substituents in the cis isomer. Therefore, trans isomers have a less exothermic heat of
combustion, indicating higher thermochemical stability. In the Benson heat of
formation group additivity dataset, cis isomers suffer a 1.10 kcal/mol stability penalty.
Exceptions to this rule exist, such as 1,2-difluoroethylene, 1,2-difluorodiazene
(FN=NF), and several other halogen- and oxygen-substituted ethylenes. In these
cases, the cis isomer is more stable than the trans isomer. This phenomenon is called
the cis effect (Craig, et al., 1997).
Based on the type of geometric isomer compound or complex ions can be
divided into types of cis and trans. To the complex there are two types of octahedral

complexes have cis and trans forms, namely MA4B2 and MA3B3. M is an atom or ion

center while A and B is a monodentate ligand.

1. MA4B2 Type

2. MA3B3 Type

If the monodentate ligand is replaced with multidentate, for example bidentate, it

will produce a complex tie ML2B2. L is a bidentate ligand. Isomer structure
becomes:

(Penyusun, 2018)
 A complex mixture of cis and trans forms may be prepared by
mixing the components of non-complex (complex compilers). Based
on the solubility difference between the cis to trans form the two
types of isomers that can be separated. For example, trans-
dioxalatodiaquochrom (II) chloride can be crystallized slowly with
evaporation of a solution containing a mixture of cis and trans forms.
With the evaporation equilibrium cis and trans forms can be shifted to
the right because of the lower solubility of the trans isomer. In
addition, the separation of cis and trans isomers can be done by
arranging conditions such that the complex solution laruta cis and
trans distinct, complex cis-dichlorobis (triethulstibin) palladium can
be crystallized in a solution of benzene though only 6% solution of cis
form.
V. K
I. EQUIPMENT AND MATERIAL
a. Equipment
- Beaker glass 50 mL (2 pieces)
- Beaker glass 100 mL (1 piece)
- Graduated cylinder 10 mL (2 pieces)
- Watch glass (2 pieces)
- Spatula (1 piece)
- Bunsen Burner (1 piece)
- Funnel (1 piece)
- Test Tube (2 pieces)
- Drop pipette (3 pieces)
- Filter paper (4 pieces)
- Analytical balance (1 set)
- Oven (1 set)
b. Material
- Oxalic Acid (H2C2O4)
- Potassium Dichromate (K2Cr2O7)
- Ethanol
- Dilute Ammonium Hydroxide solution (0.1M)

II. PROCEDURE
1. Making Isomer of Trans Potassium Dioxalato Diaquo Chromium (III)

3 gram Dihydrate Oxalic Acid

- Put into beaker glass 50 mL

- Added 1 drop of boiled aqudest
- Added little by little solution of 1 gram potassium
dichromate that dissolved in 1 drop of hot aquadest
- Covered beaker glass with watch glass

Dark Purple Solution with Gas

- Evaporated on the steam bath until the volume half

 Reaction: 4H2C2O4.2H2O (s) + K2Cr2O7 (s)  2K[Cr(C2O4)2(H2O)2]

2. Making Isomer of Cis Potassium Dioxalato Diaquo Chromium (III)

1 gram of Potassium 3 gram Dihydrate

Dichromate Oxalic Acid

- Inserted into evaporate cup or beaker glass

- Added 1 drop of hot aqudest
- Covered with watch glass

Pasta form (Losing CO2 gas)

- Added 5 mL ethanol
- Stirred until formed precipitate
 Reaction: 4H2C2O4.2H2O (s) + K2Cr2O7 (s)  2K[Cr(C2O4)2(H2O)2]

3. Isomer Purification Test

Crystal of Cis and Trans Isomer

- Put in filter paper

- Dropped Ammonium diluted solution

Dark green spread Brown spread in

in filter paper filter paper
 III. OBSERVATION TABLE

VI. a
VII. a
VIII. a
IX.