Synthesis of Cis and Trans-Potassiumdioxalatodiakuochromate (III)

A. BACKGROUND
1. GENERAL REVIEW
Apart from forming molecular compounds with water (hydrate) certain salts have the properties
of combining with the second salt either with or without water. In this combination, the
character of each salt is somewhat modified but not completely changed. Because that's the
name, "double salt". In physical properties such as crystal shape, solubility, and, in some cases,
color, double salt crystals differ from simple salts. This compound follows the laws of certain
proportions. Ammonium sulfate crystallizes from the solution as anhydrous salt, (NH4)2SO4;
copper sulfate as hydrate, CuSO4-5H2O; but when an equivalent amount of two salts is in a joint
solution of double salt, (NH4) 2SO4-CuSO4-6H2O, separate first because it is more soluble than
each single salt (Arthur et al, 1922: 61).
This is a very large group consisting mainly of organic crystalline material, but a number
of inorganic substances, such as iodine. These substances that melt easily, and can sublime
events, indicate the existence of relatively weak forces. They do not conduct electricity in a
dense or fused state which indicates that the electrons are localized in strong bonds. This bond,
however, do not permeate the entire structure, as in diamonds, and between and between the
forces of their constituents, but weak intermolecular forces. In liquid or giant substances at
ordinary temperatures, the tensile strength between particles is so weak that enough thermal
vibrations are enough for them to break. These substances can be converted into solids by
cooling to reduce heat energy. After Dalton, in 1807, chemists began to look for the causes and
mechanisms of trade unions. Many ideas were put forward during the following years, after the
discovery of atomic structures, it was realized that atomic nuclei were not affected by chemical
combinations and that the union of atoms must be an interaction between extranuclear electrons.
Kossel and Lewis, who worked independently in 1916, recognized that there was an external
quantum level containing eight electrons; they suggest that this arrangement must be related to
stability and activity, as each element achieves a noble gas configuration. Rearranging electrons
into stable octets can occur in two ways: (a) by giving or receiving electrons or (b) by sharing
electrons (Chambers, and Holliday, 1975: 27-28).
The presence of two substituents on different carbons of a cycloalkane allows for the
possibility of cis–trans isomerism similar to the kind we saw for alkenes. These cis–trans
isomers are also stereoisomers because they differ from each other only in the arrangement of
their atoms in space. Consider 1,2-dimethylcyclopropane as an example.
The planarity of the cyclopropane ring makes the cis–trans isomerism obvious. In the first
structure the methyl groups are on the same side of the ring; therefore, they are cis. In the second
structure, they are on opposite sides of the ring; they are trans. Cis and trans isomers such as
these cannot be interconverted without breaking carbon–carbon bonds. They will have different
physical properties (boiling points, melting points, and so on). As a result, they can be separated,
placed in separate bottles, and kept indefinitely (Solomons and Craig, 2011: 171).
To determination of potassium as potassium tetraphenylborate a
solution of sodium tetraphenylborate Na[B(C6H5)4] is probably the best precipitant for
potassium, but it is expensive. Precipitation may be effected at a temperature below 20°C in
dilute mineral acid solution (pH 2), in which interference from most foreign ions is negligible.
The precipitate is granular and settles readily; it is washed with a saturated aqueous solution of
the precipitate (prepared independently), and the potassium tetraphenylborate (TPB) is dried at
120°C and weighed. The compound decomposes at temperatures above 265°C, The precipitate
is of constant composition K[B(C6Hs)4] , and is sparingly soluble in water (= 5.1 mg L -1 of
potassium at 20 QC). Very few elements interfere with the determination: these include the ions
of silver, mercury(II), thallium(I), rubidium, and caesium; ammonium ion, which forms a
slightly soluble salt, can be removed by ignition prior to the addition of the reagent (Jeffery et
al. 1979: 464-465).
On each diagram, the atomic orbitals of the two atoms are represented on the right - and
the left hand diagram with the MOs in the middle. Correlation lines that connect atomic and
molecular orbitals are built to read diagrams that can be interpreted. Now consider the situation
for triatomic molecules such as CO2. Molecular orbitals contain four sets of orbitals and one
atomic orbital of three atoms. An explanation of the bond in CF4 involves five sets of atomic
orbitals and a set molecular orbitals, that is a six-component problem. Similarly, SF6 is an eight
component problem. It is clear that MOs are complicated and, perhaps, difficult to build and
interpret. To overcome this difficulty, it is common to resolve MO descriptions of polyatomic
molecules into three-component problems, a method known as the ligand orbital group (LGO)
approach (Housecroft and Sharpe, 2001: 107).
2. REVIEW OF RESULTS
Based on experiments conducted (Setiawan, et al. 2017: 2) qualitative tests of nitrate
ions were carried out by reacting the solution of complex compounds with concentrated iron
(II) ammonium sulfate and concentrated sulfuric acid. (Vogel, 1979). Calculation of free energy
is done by optimizing the possibility of the structure of complex compounds using the Gaussian
vol program. 5.0. The crystals of complex compounds produced are colorless because the
central atom Cd (II) has d orbitals which are filled with electrons so there is no transition d-d.
The reaction between cadmium nitrate and 1,3-bis (difenilfosfino) propane (dppp) with
stoichiometry 1:1 in methanol solvents produces complex monomer compounds [Cd(ONO2)2
(dppp)] with distorted tetrahedral structures. Dppp acts as a bidentate septic ligand and nitrate
ion acts as a monodentate ligand.
Based on (Monti, et al. 2015: 7) experiments, All of the investigated complexes are
stable in both CH3CN and CH2Cl2 solutions for months and do not show any degradation under
standard experimental conditions, including irradiation. The room-temperature UV-vis
absorption spectra of complexes trans-1-5 and cis-3 in CH3CN. The spectral window between
200 and 300 nm is characterized by strong absorption bands with molar absorptivities (ε) higher
than 2 × 104 M-1 cm-1. These bands originate from spin-allowed 1(π-π*) ligand-centered (LC)
transitions involving both the cyclometalating and the ancillary ligands. The most intense
absorption band in this spectral window is observed for trans-5, due to the presence of the strong
π-π* transitions centered on the bathophenanthroline (4,7-diphenyl-1,10-phenanthroline)
ancillary ligand (Scheme 2). At longer wavelengths (λ > 300 nm; magnified region), several
weaker and broader bands are present in all cases and are attributed to charge-transfer
transitions with mixed metal-to-ligand and ligand-to-ligand charge transfer (MLCT and LL′CT)
character with both singlet and triplet spin multiplicity, due to the high intersystemcrossing
efficiency promoted by the Ir(III) metal ion.7,8 To corroborate the attribution of the
experimental absorption bands, the first 100 singlet vertical excitations calculated by TDDFT
are reported for trans-3-4 and cis-3; they compare well with their corresponding experimental
absorption spectra.
It is well established that colchicine exhibits very slow unbinding kinetics. In contrast,
cis-CA-4 displays fast unbinding kinetics.5 To provide insight into this difference, we carried
out metadynamics simulation of the unbinding process for both colchicine and cis-CA-4 in
complex with tubulin. We found two similar pathways for the two ligands, which we refer to
as ‘‘slow’’ and ‘‘fast’’. Given that unbinding occurs more favorably across lower energy
barriers, we focused on the fast unbinding mechanism, which was observed three times for both
ligands. Our simulations showed that the preferential unbinding mechanism involves
displacement of the βT7 loop of tubulin, followed by release of the ligand into the solvent. They
further predict that, whereas cis-CA-4 causes a relatively small perturbation of βT7 upon
unbinding, colchicine requires the complete displacement of this loop for the ligand to be able
to exit the protein. This result provides a possible mechanistic explanation for the difference in
unbinding kinetics between cis-CA-4 and colchicine (Gaspari, et al. 2017:108).
Single crystal X-ray structure determination for Ni-R-L1 (1R) and Ni-S-L1 (1S) shows
that there are two symmetry-independent molecules in each asymmetric unit, that is, molecule
A with Ni1 and molecule B with the Ni2 centre in each unit. In each structure, two bidentate
N^O-chelate Schiff base ligands coordinate to the nickel atom with a square planar N2O2
coordination sphere around the metal atom. The two nitrogen atoms (and subsequently the two
oxygen atoms) are trans positioned. The Ni–O/N bond lengths and O–Ni–N bond angles are
listed in table and are as expected for analogous Ni(II)-Schiff base complexes. Despite the
presence of aromatic rings in the complexes Ni-R-L1 (1R) and Ni-S-L1 (1S), there are no
detectable π–π interactions but intermolecular C–H⋯π contacts are evident in the packings; a
detailed analysis is reported in the ESI (Enamullah, et al. 2015: 670).
Based on (Zhang, et al. 2016: 5) In conclusion, we have studied the cis/trans
isomerization and optical properties of the cis and trans isomers of various TPE-based AIEgens.
With a free hydroxy group, TPETH-OH undergoes cis/trans isomerization under acidic
conditions but not under basic conditions, which was ascribed to ketoenoltautomerization. By
replacing the proton of the hydroxy group in TPETH-OH with an alkyl group, the pure cis and
trans isomers of TPETH-MAL were obtained and characterized by HPLC and NMR
spectroscopy. cis-TPETH-MAL and trans-TPETH-MAL have roughly the same spectroscopic
properties at room temperature. However, cis-TPETH-MAL emits yellow fluorescence and
trans-TPETH-MAL emits red fluorescence when they are stored in DMSO at ¢208C for a few
hours. The differences in the photophysical properties can be ascribed to the higher steric
hindrance in cis-TPETHMAL than in trans-TPETH-MAL. Finally, the geometry of TPETH
MAL is maintained in a thiol–ene reaction, and the generated probe, cis-TPETH-cRGD, can
selectively stain integrin-overexpressing cancer cells. This study improves our fundamental
understanding of the cis/trans isomerization and photophysical properties of TPE derivatives,
which offers new opportunities to explore the unique properties of
AIEgens.
B. OBJECTIVE OF EXPERIMENT
Studying the making and properties of cis and trans isomers of potassium
dioxalodiakuochromate(III) complex salts.
C. APPARATUS AND CHEMICALS
1. APPARATUS
a. Beaker glass of 100 mL and 200 mL
b. Analytical balance
c. Spatula
d. Stirring rod
e. Funnel
f. Vaporizer cup
g. Measuring pipette
h. Buchner Funnel
i. Vacuum Pump
j. Erlenmeyer flask 250 mL
k. Drop pipette
l. Watch glass
m. Spray bottle
2. CHEMICALS
a. Oxalic acid crystals (H2C2O4)
b. Potassium dichromate crystals (K2Cr2O7)
c. Alcohol (C2H5OH) 96%
d. Oxalic acid dihydrate crystals (H2C2O4.2H2O)
e. Aquades (H2O)
f. Filter paper
g. Whatman filter paper

C. WORK PROCEDURE
1. Making a trans potassiumdioxahalodiakuochromate (III) isomers

5 6 7 5 6 7
4 4
3 8 3 8
21 11 9 2 9
1 1
0

Dissolve with H2C2O7

Weigh 12 g aquadest
H2C2O4.2H2O solution
 5 6 7 5 6 7
4 4
3 8 3 8
21 11 9 2 9
1 1
0

Dissolve with hot

Weigh 4 g K2Cr2O7 solution
aquadest
K2Cr2O7

K2Cr2O7 solution

45 67 45 67
31 11 8 3 8
2 9 2 9
1 1
0

H2C2O7 When the reaction takes evaporated until 1/2 Let it evaporated at room
solution places volume temperature until 1/3 volume

dry it cooled with alcohol wash with aquadest filter crystals

5 6 7 5 6 7
4 4
3 8 3 8
21 11 9 2 9
1 1
0

weigh the crystal

formed

2. Manufacture of cis-potassiumdioxahalodiakuochromate(III) isomers

K2Cr2O7 H2C2O4

5 6 7 5 6 7 5 6 7 5 6 7
4 4 4 4
3 8 3 8 3 8 3 8
21 11 9 2 9 21 11 9 2 9
1 1 1 1
0 0
1 drop aquadest
weigh 4 g weigh 12 g
K2Cr2O7 H2C2O4.2H2O
 20 mL ethanol

decanted until it settles

ethanol

dried
filtered

3. Isomer Purity Test

Crystal Ammonia
isomer
complex

DATA ANALYSIS
Knowed: Mass H2C2O4 = 12,0 grams
Mw H2C2O4 = 126 grams/mole
Mass K2Cr2O7 = 4,0 grams
Mw K2Cr2O7 = 294 grams/mole
Mw K[Cr(C2O4) 2(H2O) 2] = 303 grams/mole
Mass of trans crystal practice = 0 gram
Mass of cis crystal practice = 10.783 grams
Asked : Crystal Rendement = …?
Solution :
a. Trans
n H2C2O4. 2 H2O = m H2C2O4. 2 H2O
Mw H2C2O4. 2 H2O
= 12.0 grams
126 grams/mole
= 0.0952 mole
n K2Cr2O7 = m K2Cr2O7
 Mw K2Cr2O7
= 4.0 grams
294 grams/mole
= 0,0136 mole
Reaction :
7 H2C2O4.2H2O + K2Cr2O7 2 K[Cr(C2O4) 2(H2O) 2] + 6CO2 + 2H2
Initial : 0,0952 mole 0,0136 mole - - -
Reaction : 0,0952 mole 0,0136 mole 0,0278 mole 0,0813 mole 0,0278 mole
Meaning : - - 0,0278 mole 0,0813 mole 0,0278 mole

mass of K[Cr(C2O4)2(H2O)2] = n x Mw
= 0,0278 mole x 303 grams/mole
= 8,4234 grams
% Crystal trans Rendement = m practice x 100%
m theory
= 0 gram x 100%
8,4234 grams
=0%
b. Cis
n H2C2O4. 2 H2O = m H2C2O4. 2 H2O
M2 H2C2O4. 2 H2O
= 12,0 grams
126 grams/mole
= 0,0952 mole
n K2Cr2O7 = m K2Cr2O7
Mw K2Cr2O7
= 4,0 grams
294 grams/mole
= 0,0136 mole
Reaction :
7 H2C2O4.2H2O + K2Cr2O7 2 K[Cr(C2O4) 2(H2O) 2] + 6CO2 + 2H2
Initial : 0,0952 mole 0,0136 mole - - -
Reaction : 0,0952 mole 0,0136mole 0,0278 mole 0,0813 mole 0,0278 mole
Meaning : - - 0,0278 mole 0,0813 mole 0,0278 mole
mass of K[Cr(C2O4)2(H2O)2] = mole x Mw
= 0,0278 mole x 303 grams/mole
= 8,4234 grams
% Crystal cis rendement = m practice x 100%
m theory
= 10. grams x 100%
8,4234 gr
= 128.01%

I. DISCUSSION
Pada percobaan ini bertujuan untuk mempelajari pembuatan dan sifat-sifat isomer cis
dan trans dari garam kompleks kalium dioksalatodiakuokromat (III). Campuran kompleks
bentuk cis dan trans dapat dibuat dengan cara mencampur komponen-komponen non-kompleks
atau penyusun kompleks. Berdasarkan pada perbedaan kelarutan antara bentuk cis dengan trans
maka kedua jenis isomer itu dapat dipisahkan.
1. Pembuatan isomer trans – kalium dioksalatudiakuokromat (III)
Pada percobaan pembuatan isomer trans kalium
dioksalatodiakuokromat (III) dapat dilakukan dengan melarutkan
12 gram H2C2O4 . 2H2O dengan setetes H2O kemudian 4 gram
K2Cr2O7 yang dilarutkan dengan beberapa setetes H2O panas,
campuran dimasukkan ke dalam gelas kimia, dan campuran
bereaksi dengan cepat membentuk larutan berwarna hitam. Karena
kelarutan isomer trans rendah, baik asam oksalat maupun kalium
dikromat terlebih dahulu dilarutkan dengan setetes air sebelum
keduanya dicampur agar dapat bereaksi dengan cepat. Reaksi
berlangsung ditandai dengan berubahnya warna campuran menjadi hitam dan mengeluarkan
uap, campuran ditutup menggunakan gelas arloji agar isomer trans tidak terkontaminasi dengan
unsur-unsur lain yang dapat mempengaruhi sifat trans dan mencegah agar kalor yang berasal
dari aquades panas tidak keluar serta mencegah berkurangnya reaktan akibat terjadinya
percikan-percikan saat reaksi berlansung . Adapun reaksi yang terjadi adalah:
K2Cr2O7 + 7H2C2O4.2H2O → 2K[trans-Cr(H2O)2(C2O4)2].3H2O+ 6CO2+ 13H2O
Proses terjadinya perubahan warna dari orange dan putih menjadi kehitaman karena
terbentuknya senyawa kompleks kalium dioksalatodiakuokromat (III), dimana dalam senyawa
kompleks tersebut ada dua macam ligan yaitu C2O4 dan H2O serta satu atom pusat Cr dari logam
transisi.
Selanjutnya larutan diuapkan yang bertujuan untuk
melepaskan uap air dan karbon dioksida sebagai hasil sampingan
seperti pada reaksi yang terjadi. Setelah diuapkan, larutan disaring
menggunakan kertas saring kemudian endapan yang diperoleh
dicuci dengan etanol untuk mengikat sisa air yang terkandung
dalam endapan. Endapan ditimbang menggunakan neraca analitik
dan diperoleh kristal sebanyak 0 gram dengan rendemen sebesar 0
% artinya pereaksi tidak bereaksi sempurna, sedangkan secara teori
seharusnya diperoleh kristal sebanyak 8,2457 gram .
Gambar geometri molekul kompleks trans kalium
dioksalatodiakuokromat(III)

2. Pembuatan isomer Cis – kalium dioksalatudiakuokromat (III)

Pembuatan isomer cis kalium dioksalatodiakuokromat (III)
dilakukan dengan mereaksikan 12 gram asam oksalat dan 4 gram
kalium dikromat dalam cawan penguap selanjutnya ditambahkan
setetes aquades dan menutup dengan gelas arloji selama reaksi
berlangsung. Penambahan setetes aquades yaitu untuk
mempercepat reaksi dan hal ini juga menandakan bahwa isomer
cis sangat mudah larut dibandingkan isomer trans. Hasil reaksi
diperoleh larutan yang berwarna kehitaman. Larutan yang
diperoleh ditambahkan dengan etanol sambil mengaduk sampai
terbentuk endapan berwarna hitam. Fungsi penembahan etanol yaitu untuk megikat air yang
dihasilkan dari reaksi campuran sehingga diperoleh kristal yang murni. Adapun reaksi yang
terjadi :
 K2Cr2O7 + 7H2C2O4.2H2O → 2K[cis-Cr(H2O)2(C2O4)2].2H2O+ 6CO2+ 13H2O

Setelah penambahan etanol, larutan disaring menggunakan

Buchner kemudian dicuci lagi dengan air dan etanol agar
diperoleh kristal yang murni. Berat kristal yang diperoleh
sebanyak 3,4gram dengan rendemen sebesar 41,23 %. Untuk
meguji kemurnian kristal yang diperoleh, maka kristal ditetesi
denghan larutan ammonia encer dan diperoleh endapan yang
menyebar pada kertas saring dan berwarna hijau tua, hal ini
sesui dengan teori bahwa Isomer cis akan membentuk padatan
berwarna hijau tua yang dapat dengan cepat akan menyebar
pada kertas saring jika ditambahkan dengan amonia encer .

3. Uji kemurnian isomer

Uji ini bertujuan untuk membedakan yang sama isomer cis kalium ioksalatudiakuokromat (III)
dan isomer transnya. untuk percobaan ini kita mengambil sedikit Kristal trans dan
menempatkannya dikertas saring lalu dilakukan presentase ammonia encer. Ammonia (NH3)
seperti halnya oksolato ataupun air yang mengikat krom adalah juga merupakan suatu ligan.
penambahannya dapat mensubsidi ligan oksalat atau air, akibatnya dalam percobaan pada
Kristal kompleks, terdapat larutan berwarna coklat tapi tidak terdapat padatan. Sedangkan pada
Kristal cis yang ditetesi dengan ammonia maka beberapa larutan berwarna hijau tua yang
dengan cepat menyebar merata. bagian ini yang disebut sebagai cis kalium
dioksalatudiakuokromat (III). hal ini dapat terjadi karena isomer trans lebih setabil dari
penambahan atau reaksi-reaksi lain sedangkan isomer cis tidak setabil terhadap penagaruh-
pengaruh asam atau potensi lain.

Trans crystal Cis crystal

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