APPROVAL SHEET

The complete report of Anorganic Chemistry I Experiment with the title

“Preparation of Cis and Trans of Potassium Dioxalatodiaquochromate(III)” was
made by:
class : ICP A of Chemistry
group : IV (Four)
members : 1. Khairunnisa M
2. Risdah Damayanti N
3. Yuli Astuti
After checked and consulted by Assistant or Assistant Coordinator. So, this report
was accepted.

Makassar, June 20th 2016

Assistant Coordinator Assistant

Ida Mashita Susilo Sudarman Desa

Known by
Responsibility Lecturer,

Ahmad Fudhail, S.Pd., M.Si

ID. 19881012 201504 1 002
A. TITLE OF EXPERIMENT
Preparation of Cis and Trans of Potassium Dioxalatodiaquochromate(III)

B. OBJECTIVES
In the end of experiment, apprentice should be understanding and competent
in studying the preparation and characteristics of cis and trans isomer from
potassium dioxalatodiaquochromate(III) complex salt.

C. PREVIEW OF LITERATURE
Compounds of metal ions coordinated by ligands are referred to as metal
complexes. Most ligands are neutral or anionic substances but cationic ones, such
as the tropylium cation, are also known. Neutral ligands, such as ammonia, NH 3, or
carbon monoxide, CO, are independently stable molecules in their free states,
whereas anionic ligands, such as Cl- or C5H5-, are stabilized only when they are
coordinated to central metals. Common ligands or those with complicated chemical
formula are expressed in abbreviated forms. Those ligands with a single ligating
atom are called monodentate ligands, and those with more than one ligating atoms
referred to as polydentate ligands, which are also called chelate ligands. The
number of atoms bonded to a central metal is the coordination number. Molecular
compounds which consist of d-block transition metals and ligands are referred to as
complexes or co determined by the size of the central metal, the number of d
electrons, or steric effects arising from the ligandsWhen four ligands coordinate to
a metal, tetrahedral (Td) coordination is the least ongested geometry, although a
number of square planar (D4h) complexes are known. [CoBr4]2-, Ni(CO)4, [Cu] of
tetrahedral complexes. here are a few known examples of square planar complexes
with identical ligands, such s [Ni(CN) 4]2-, or [PdCl4]2-. In the case of mixed ligand
complexes, a number of square lanar complexes of d8 ions, Rh+, Ir+, Pd2+, Pt2+, and
Au3+, have been reported. Examples was clude [IrCl(CO)(PMe 3)2], [NiCl2(PEt3)2],
and [PtCl2(NH3)2] (Et = C2H5) (Saito, 2004: 111-113).
A complex in general is any species formed by specific association of
molecules or ions by donor-acceptor interactions. In aqueous solution the most
important complexes are those formed between a metal cation and ligands, which
may be ions (e.g. halides, cyanide, oxalate) or neutral molecules (e.g. ammonia,
pyridine). The ligand acts as a donor and replaces one or more water molecules
from the primary solvation sphere, and thus a complex is distinct from an ion pair,
which forms through purely electrostatic interactions in solvents of low polarity.
Although complex formation is especially characteristic of transition metal ions it is
by no means confined to them. Successive stepwise formation constants often
decrease regularly K1>K2>…of the maximum value being determined by the
number of ligands that can be accommodated: this is often six except for chelating
ligands. The decrease can be understood on entropic (statistical) grounds, as each
successive ligand has one less place available to attach. Exceptional effects may
result from the charge and size of ligands, and a reversal of the normal sequence
can sometimes be attributed to specific electronic or structural effects. It is
important to remember that each ligand replaces one or more solvating water
molecules. For example, in the Cd2+/Br− system K4>K3 as the octahedral species
[Cd(H2O)3Br3]− is converted to tetrahedral [CdBr4]2− with an entropy gain resulting
from increased freedom of three water molecules (Cox, 2004: 137-138).
A complex ion will have a central atom, normally a transition metal, with
one or more ligands. A ligand is a Lewis base that reacts with the central atom. The
most common numbers of ligands are four and six. If a species does not contain a
lone pair of electrons, it cannot be a Lewis base, which means it cannot be a ligand.
Some ligands are chelating ligand. A chelating ligand behaves as a Lewis base
more than once to the same central atom. An example of a chelating ligand is
ethylenediamine, NH2CH2CH2NH2. This molecule donates a pair of electrons from
each of the nitrogen atoms. Three ethylenediamine ligands count the same as six
“normal” ligands. Another common chelating ligand that behaves like
ethylenediamine is the oxalate ion, C2O42-. The ligand ethylenediaminetetraacetate,
EDTA4-, chelates by donating six electron pairs. The six electron pairs make this
ligand equivalent to six “normal” ligands. The general equation for the formation of
a complex is:

The equilibrium constant expression, Kf, is

 (Moore, 2007: 287).
The stability constants of the complex species that were formed in the
systems investigated here allow us to quantitatively define the ability of pectin and
polygalacturonic acid to sequester cadmium(II) and copper(II) ions. This
information is useful when planning the removal of toxic metal ions from
contaminated waters, either by using these biopolymers directly in solution or in a
gel phase. quantitative stability data for the formation of complex species of
copper(II) and cadmium(II) with the polymer ligands considered here. Using
several polarographic techniques, Garrigosa et al. [33] obtained the following Cd-
PGA complex formation constants in 0.01 mol L-1 KNO3 at pH = 6: log K=4.38
(by Reverse Pulse Polarography, RPP), log K = 4.35 (by Alternating Current
Polarography, ACP), and log K = 4.18 (by Differential Pulse Polarography, DPP),
yielding an average value of 4.30. Data comparisons can also be made by
considering the interaction of Cd2+ and Cu2+ ions with alginic acid (AA), which, like
pectin, is an acidic polysaccharide. Alginic acid consists of monomer units of
mannuronic and guluronic acids, which are very similar in structure to galacturonic
acid, the main component of natural pectins. The only quantitative data on the
protonation of alginate and the stability of species in the Cu/Cd-alginate system
were reported previously by our laboratories [35,18] (Cataldo, 2012).
The cis and trans products was achieved by means of TLC, and solution IR
and NMR spectroscopy on the products after the reaction, revealed the formation of
the isomer materials. The isomerisation reactions for the new complexes were
studied and the general trend was for the isomerisation reaction to occur from the
trans to the cis isomer dependent on electronic factors associated with ligand
orientation effects. An ex- tension of the work was on the formation of the products
mixture on pelleting either the cis or the trans isomer of the complex. The cis or the
trans isomer gave the same IR spectra i.e a mixture of cis and trans isomer of the
complex.
It was established that pelleting can generate enough heat to set up a chemical
reaction. Therefore on forming a suitable pellet using different diluents of group I
metal salts leads to the isomerisation reactions of transforming cis to trans and the
reverse, until isomeric mixture of cis/trans (30/70) is achieved (Adeyemi, 2012).
The equilibrium constants of the reaction of CisK[Cr(ox) 2(H2O)2].H2O with
Alanine at different temperatures are shown to be very close to that reported for the
reaction of the trans-K[Cr(ox)2(H2O)2].3H2O with Alanine and other amino acids
[5], which indicate the formation of the same final product Cis-K[Cr(ox) 2(ala)] and
has a high stability constant( logKeq ≈ 5). The first order plot of substitution
reaction of CisK[Cr(ox)2(H2O)2].H2O with alanine, ln(At – A∞) vs time passed,
show one straight line with slop equal to the observed rate constant (kobs). This
result insure that the mechanism of the substitution is different from the substitution
of the Trans-[Cr(ox)2(H2O)2]- with alanine which showed two straight cross-over
lines with two different slops correspond to two competitive substitution reaction of
the trans-form of the complex. The lability of the Trans-form of the complex was
related to a first hydrolysis step of the complex to a monohydroxy form in the Trans
position of the complex and the effect of the OH- group on the opposite H 2O group
on the other side of the complex to be more loosely bonded to the central chromium
atom and be more easy to be substituted, that the observed rate constants are higher
for the trans-complex than that of the cis-complex and the activation energies are
smaller.

(Aziz, 2012).
 Cis-1,4-Dimethylcyclohexane can adopt either of two equivalent chair
conformations, each having one axial methyl group and one equatorial methyl
group. The two are in rapid equilibrium with each other by ring flipping. The
equatorial methyl group becomes axial and the axial methyl group becomes
equatorial. The methyl groups are described as cis because both are up relative to
the hydrogen present at each carbon. If both methyl groups were down, they would
still be cis to each other. Notice that ring flipping does not alter the cis relationship
between the methyl groups. Nor does it alter their up-versus-down quality;
substituents that are up in one conformation remain up in the ring-flipped form. The
most stable conformation of trans-1,4-dimethylcyclohexane has both methyl groups
in equatorial orientations. The two chair conformations of trans-1,4-
dimethylcyclohexane are not equivalent to each other. One has two equatorial
methyl groups; the other, two axial methyl groups. The more stable chair the one
with both methyl groups equatorial is the conformation adopted by most of the
trans-1,4-dimethylcyclohexane molecules. trans-1,4-Dimethylcyclohexane is more
stable than cis-1,4-dimethylcyclohexane because both methyl groups are equatorial
in its most stable conformation. One methyl group must be axial in the cis
stereoisomer. Remember, it is a general rule that any substituent is more stable in
an equatorial orientation than in an axial one. It is worth pointing out that the 7
kJ/mol energy difference between cis- and trans1,4-dimethylcyclohexane is the
same as the energy difference between the axial and equatorial conformations of
methylcyclohexane (Carey, 2000 :110-111).

D. APPARATUS AND CHEMICAL

1. Apparatus
a. Beaker glass 100 mL (2 units)
b. Beaker glass 250 mL (2 units)
c. Watch glass (1 unit)
d. Bunsen burner (2 units)
e. Tripod and gauze (@2 units)
f. Funnel (1 unit)
g. Stirrer (2 units)
h. Evaporation dish (1 unit)
i. Mortar and pestle (@1 unit)
j. Erlenmeyer flask 250 mL (2 units)
k. Spray bottle (1 unit)
l. Analytical balance (1 unit)
m. Drop pipette (4 units)
n. Spatula (1 units)
o. Wood clamp (1 unit)
p. Rough and smooth cloth (@1 unit)
2. Chemicals
a. Oxalic acid dihydrate (H2C2O4 . 2H2O)
b. Potassium dichromate (K2Cr2O7)
c. Aquadest (H2O)
d. Ethanol (C2H5OH)
e. Sodium hydroxide (NaOH)
f. Ammonium hydroxide (NH4OH)
g. Whatman filter paper
h. Filter paper
i. Tissue
j. Matches

E. WORK PROCEDURES
1. Preparation of Trans Isomer Potassium Dioxalatodiaquochromate(III)
a. 12 grams of oxalic acid dihydrate was dissolved with aquadest in beaker glass
200 mL and heated.
b. The solution was added with 4 gram of potassium dichromate that has dissolved
with hot aquadest. The beaker glass was closed by watch glass when the reaction
that happened.
c. The mixture solution was evapotaed until the half of its volume.
d. The mixture solution was evaporated in room temperature until the third of its
volume.
e. The crystals was filtered and washed with cool aquadest and cooled with
ethanol.
f. The crystals was dried and weighed its crystals.
g. The result was noted.
2. Preparation of Cis Isomer Potassium Dioxalatodiaquochromate(III)
a. 4 grams of potassium dichromate and 12 grams of oxalic acid dihydrate was
mixed in evaporation dish.
b. 2 drops of ethanol was dropped into mixture solution and the dish was closed
with watch glass. The reaction was happened with released of water vapour and
CO2. The mixture was guarded so that there is no the constant of cis and trans
isomer.
c. 20 mL of ethanol was added and the solution was stirred until precipitation.
d. The solution was decantired and added again with 5 mL of ethanol until the all
of crystals was formed.
e. The crystals was filtered and dried with Buchner funnel.
f. The crystals was weighed.
3. Purity of Isomer Test
a. The complex crystal was placed in filter paper and several drops dilute of
ammonia was added.
b. Cis isomer was formed fastly dark green solution in filter paper.
c. Trans isomer was formed young brown solid in filter paper but not soluble.

F. OBSERVATION RESULTS
1. Preparation of Trans Isomer Potassium Dioxalatodiaquochromate(III)
No. Activities Results
12 grams of oxalic acid (white
1. Colorless solution
crystals) + hot water
4 grams of potassium
2. dichromate (orange crystals) + Orange solution
hot water
3. Colorless solution + orange Blackish purple solution, and
solution produce gas bubble (exotherm
 reaction)
Blackish purple solution was
heated until ½ of initial volume Blackish purple solution and
4.
and then evaporate the solution produce crystals
in the room
The crystals was filtered,
5. washed with cool water and The crystals
ethanol
6. The crystals was weighed Mass = 4.1206 grams
2. Preparation of Cis Isomer Potassium Dioxalatodiaquochromate(III)
No. Activities Results
4 grams of potassium
1. Orange powder
dichromate was weighed
12 grams of oxalic acid
2. White powder
dihydrate was weighed
The powder was melted became
Orange powder + white
3. black, produce gas (exotherm
powder was mixed in crucible
reaction)
Black melting was washed
Solid round and formed sediment is
4. with ethanol and stirred until
black
formed a sediment
5. Ethanol was added again Formed crystals
Crystals was filtered with
6. Black crystals
Buchner funnel
7. The crystals was weighed Mass = 8.0199 grams
3. Purity of Isomer Test
No. Activities Results
Little of complexes trans
Obtained the purple sediment and
1. crystals was putted into filter
not soluble
paper + NH4OH dilute
Little of complexes ciss
Obtained the dark green sediment
2. crystals was putted into filter
that spread quickly and evenly
paper + NH4OH dilute

G. DATA ANALYSIS
Known : m H2C2O4.2H2O = 12 gram
 m K2Cr2O7 = 4 gram
Mr H2C2O4.2H2O = 126 gr/mole
Mr K2Cr2O7 = 294 gr/mole
m practice of trans- = 4.1206 grams
m practice of cis- = 8.0199 grams
Ask : %rendement = ?
Answer :
mass
n H 2 C 2 O 4 .2 H 2 O=
Mr
12 gram
n H 2 C 2 O 4 .2 H 2 O=
gram
126
mole
n H 2 C 2 O 4 .2 H 2 O=0.0952 mole

mass
n K 2 C r 2 O 7=
Mr
4 gram
n K 2 C r 2 O 7=
gr
294
mole
n K 2 Cr 2 O7=0.0136 mole

K2Cr2O7 (aq) + 7H2C2O4.2H2O (aq)  2K [Cr(H2O)2(C2O4)2] (g) + 6CO2 + 17H2O (g)

0.0136 mole 0.0952 mole - - -
0.0136 mole 0.0952 mole 0.0272 mole 0.0816 mole
0.2312 mole
- - 0.0272 mole 0.0816 mole 0.2312 mole
Mass K [Cr(H2O)2(C2O4)2] theory = mole × Mr
= 0.0272 mole × 303 gr/mole
= 8.2416 gram
1. Rendement of trans
mass practice
% trans K [Cr(H2O)2(C2O4)2] = × 100 %
mass theory
4.1206 gram
= 8.2416 gram ×100 %
 = 49.99 %
2. Rendement of cis
mass practice
% cis K [Cr(H2O)2(C2O4)2] = mass theory × 100 %
8.0199 gram
= 8.2416 gram × 100 %

= 97.31 %

H. DISCUSSIONS
1. Synthetic Isomer Trans of Potassium dioxalatodiaquochromate(III)
Trans-K[Cr(C2O4)2(H2O)2] has a low solubility level, so as to make it, the
reactants are dissolved in advance so that the equilibrium shifts towards trance. The
notarized trans isomer for the same ligand molecule, located bersebrangan in the
structure of the compound. Crystalline trans- K[Cr(C2O4)2(H2O)2] was made from
K2Cr2O7 and H2C2O4.2H2O that first dissolved in a little water. K 2Cr2O7 was
dissolved in hot water because of their low solubility so it takes energy (heat) to
dissolve it. Thereafter, the orange solution in a beaker covered with a watch glass to
prevent heat release and to prevent equilibrium mixture of cis and trans isomers
(Lecturer Team, 2016: 32). Moreover, it also seeks to clarify the observation of
changes in the reaction occurs. During the reaction, the system undergo exothermic
reaction that is accompanied by the release of gases CO 2 and water vapor as a
byproduct of the reaction.
Dark brown bubbly solution was obtained due to the formation of complex
compounds of potassium dioxalatodiaquochromate(III) which has two kinds of
ligands and the central atom of the transition metal. The resulting dark brown
solution was then evaporated until the volume becomes of ½ its original volume
and continued evaporation at room temperature until the solution volume becomes
1/3 of its original volume. Evaporation is intended to vaporize of H 2O molecules
undesirable so it does not affect the formation of complex compounds of potassium
dioxalatodiaquochromate(III) for the complex consists of two molecules of H 2O
and C2O42- as ligands. After that, a process of cooling the crystals to speed the
formation of crystals. Then, resumed the process of screening and washing crystal
using distilled water and ethanol. Where, distilled water in the washing serves to
bind the residual moisture still contained in the crystal. Meanwhile, the function of
the ethanol in the washing is that the crystals obtained purer, because ethanol can
bind substances that still contained impurities in the crystals. The reaction occurs as
follows:
7 H2C2O4. 2 H2O(aq) + K2Cr2O7(aq) → 2 K[Cr(C2O4)2(H2O)2](s) + 6 CO2(g)↑
(Orange) (Colorless) (Dark brown) + 17 H2O(aq)

Where, H2C2O4.2H2O serves as a provider of ligand C2O42- and H2O, while K2Cr2O7
serves as the central atom provider of Cr. As for the geometric form is octahedral
shape.

H H
O

O C O O
K
C O
Cr

C O
O C O O

O
H H

Geometric shape of isomer trans-

Potassium dioxalatodiaquochromate(III)

Meanwhile, hybridization occurs in isomer trans- K[Cr(C2O4)2(H2O)2 is:

27Cr: [Ar] 3d7 4s2 4p0

27Cr3+: [Ar] 3d5 4s1 4p0

Cr3+ : [Ar]
(in [Cr(C2O4)2(H2O)2]-)

(d2sp3 hibridization = octahedral)

2. Synthetic Isomer Cis of Potassium dioxalatodiaquochromat(III)

Synthetic isomer cis-kalium dioksalatodiakuokromat(III) was conducted
by mixing the powder H2C2O4.2H2O that white color and serves as a provider of
ligand C2O42- and H2O with the orange powder K2Cr2O7 which serves as the central
atom provider of Cr in the vaporizer cup. This is called the cis isomer for the same
ligand molecule, located parallel to the structure of the compounds. Then the
powder mixture is stirred and dropped into distilled water and cover the mixture
with a watch glass during the reaction. In the process of the release of H 2O and CO2
vapour which characterized by the formation of black bubbly solution. Mixed
solution must be maintained in order to avoid equilibrium mixture of cis and trans
isomers (Lecturer Team, 2016: 32). The black solution was then added ethanol to
precipitate / condense the whole of the precipitate to form a black sediment denser.
After that, the addition of ethanol back to enhance the formation of black sludge.
Black precipitate formed is then filtered with a Buchner separation and then dried
and weighed. As for the reactions that occur are:

7 H2C2O4.2H2O (aq) + K2Cr2O7 (aq) K[Cr(C2O4)2(H2O)2] (s) + 17 H2O (aq)

The shape of the geometry of the cis-isomer potassium

dioxalatodiaquochromate(III) is octahedral shape.

H H
O
H

OC O O H

Cr

O
 C O

O O O

Geometric shape of isomer cis-

Potassium dioxalatodiaquochromate(III)
Meanwhile, hybridization occurs in isomer cis-K[Cr(C2O4)2(H2O)2] is:
27Cr: [Ar] 3d7 4s2 4p0

27Cr3+: [Ar] 3d5 4s1 4p0

3+
Cr
: [Ar]
(dalam [Cr(C2O4)2(H2O)2]-)

(d2sp3 hibridization = octahedral)

3. Isomer Purity Test

Testing of isomer trans-dioksalatodiakuokromat(III), was added with
aqueous ammonia and produce a dark brown solids. This indicates that the test is
positive trans. Isomer trans-dioxalatodiaquochromate(III) on the test was resulted
in solid dark brown because of the structure of trans opposite, so there is no
displacement of ligands that cause trans isomer difficult soluble in polar solvents
such as ammonia. The reaction occurs:
K[Cr(C2O4)2(H2O)2] + NH4OH
Testing of isomer cis-dioxalatodiaquochromate(III), was added with
aqueous ammonia and produce a dark green solution. This dark green color comes
from K[Cr(C2O4)2(NH3)2]. This indicates that the test is positive cis. This occurs
because the ligand displacement of water by ammonia ligand. Wherein, the ligand
displacement of water by the ammonia ligand for the bersebrangan cis structure. In
addition, the water including weak ligands, or in other words, ammonia is a ligand
that is more reactive than water. The reaction occurs:
K[Cr(C2O4)2(H2O)2] + NH4OH → K[Cr(C2O4)2(NH3)2] + 4H2O

I. CONCLUSION AND SUGGESTION

1. Conclusions
a. The crystal of trans-potassium dioxalatodiaquochromate(III) that resulted
is the green crystal with rendement 49.99%.
b. The crystal of cis-potassium dioxalatodiaquochromate(III) that resulted is
the dark brown crystal with rendement 97.31%.
c. The purity isomer test of trans-potassium dioxalatodiaquochromate(III)
that resulted was formed young brown solid and cis-potassium
dioxalatodiaquochromate(III) was formed dark green solution and easily
soluble.
2. Suggestions
For the next experiment, apprentice should be carefully when react
the aqudest to potassium dichromate and oxalic acid dihydrate. Because it
can effecting the crystal result.

BIBLIOGRAPHY
Adeyemi, Olalere G and Umaru Salami. 2012. Solid State Transformation of Cis
and Trans methylcyclopentadienyl molybdenum
dicarbonyltriphenylphosphineiodide on Pelleting Utilizing Different
Diluents. Open Journal of Inorganic Chemistry Vol (2) pp: 28-32.
Aziz, Bakhtyar K and Diary I. Tofiq. 2012. Kinetic and Equilibrium Comparison of
The Complexation Reaction of Cis- and Trans- Forms of
Cr(ox)2(H2O)2.xH2O with Alanine. International Journal of Chemical and
Environmental Engineering Vol (3) No (1) pp: 34-38.
Carey, Francis A. 2000. Organic Chemistry Fourth Edition. New York: The
McGraw-Hill Companies.
Cataldo, Salvatore., et al. 2012. Complex Formation of Copper(II) and
Cadmium(II) with Pectin and Polygalacturonic Acid in Aqueous Solution.
An ISE-H+ and ISE-Me2+ Electrochemical Study. International Journal of
Electrochemical Science Vol (7) No (1) pp: 6722 – 6737.
Cox, P.A. 2004. Instant Notes Inorganic Chemistry Second Edition. London: BIOS
Scientific Publishers.
Moore, John T and Richard H. Langley. 2007. Chemistry for the Utterly Confused.
New York: The Mc-Graw Hill Companies.
Saito, Taro. 2004. Inorganic Chemistry. Japan: Kanagawa University.