Department Of CHEMISTRY

Advance Lab Report-I

Submitted By: Umm-e-Rubab (001)

Laiba Ali (003)

Rabbia Islam (008)

Umm-e-Habiba(009)

Malaika Yousaf (011)

Submitted To: Mam Tahira Amir

Course Code : CHM-477

Group Leader : Umm-e-Habiba

Date of submission : 2nd Nov,2023

 Group Members Work Distribution Detail

In Lab Performance

• Instructor: Laiba Ali

• Apparatus, Chemical and Procedure Writing: Rabbia Islam
• Apparatus Collecting: Umme-Habiba & Malaika Yousaf
• Chemicals Collecting: Umm-e-Rubab & Laiba Ali
• Readings & Observations: Malaika Yousaf & Umm-e-Habiba
• Weighing Product & Washing Apparatus: Umm-e-Rubab
• Pictures Taking: Rabbia Islam
• Experiment Perform: All members
• Lab Report: Malaika Yousaf

In Lab Report
• Abstract: Umm-e-Rubab
• Introduction: Laiba Ali
• Chemicals & Materials: Rabbia Islam
• Procedure: Malaika Yousaf
• Result & Discussion: Umm-e-Habiba
• Conclusion: Rabbia Islam
• References: All members
• Printing: Umm-e- Rubab, Umm-e-Habiba,Laiba Ali
• File Cover: Malaika Yousaf & Rabbia Islam
• Typing: Malaika yousaf
 Cobalt(III) Complexes
And
their Coordination with Chloride Ion
Abstract:
We have performed this experiment to confirm either chloropentaammine cobalt(lll)chloride and
hexaammine cobalt(lll)chloride form complexes with chloride or not. In this experiment,first of all when
we add the CoCl3.6H2O in NH4Cl and distilled water then add charcoal and NH3 in it brown slurry is
formed . Later on when we add H2O2 in this after Maintaining the temperature upto 60'C the orange
product is obtained by filtration. while in second experiment, we add NH4Cl and COCl3.5H2O in beaker
when brown slurry is form we add H2O2 in it maintain the temperature and add conc. HCL in it we
obtained purple product by filtration then we measure the molar conductivity of both complexes which
is 115.7mS/cm (COCl3.5H2O) and 138.4mS/cm (CoCl3.6H2O). According to Werner theory, We concluded
that in [Co(NH3)6]Cl3, 3-chloride ions precipitates which act as primary valency and 6NH3 molecules act
as secondary valency. Similarly, in [Co(NH3)5Cl]Cl2, 2-chloride ions act as primary valency, the remaining
1-chloride ion and 5NH3 ions act as secondary valency.

Introduction:
Hexaammine cobalt(III) chloride and chloropentaammine cobalt(III) chloride represent
two significant cobalt(III) coordination complexes that have been extensively studied in the field of
inorganic chemistry. These compounds exemplify the profound influence of ligand variations on the
structural, electronic, and reactivity properties of coordination complexes, which is fundamental in
understanding their applications across various scientific and industrial domains.Cobalt(III) can form
complexes with chlorine due to its ability to exhibit various oxidation states and its electron
configuration. In these complexes, cobalt typically forms coordinate bonds with chlorine atoms, forming
stable coordination compounds due to the Lewis acid-base interaction between the electron-deficient
cobalt and the electron-rich chlorine atoms.
Hexaamminecobalt(III) chloride is a coordination complex that forms when hexaamminecobalt(III) cations
([Co(NH3)6]3+) react with chloride ions (Cl-). This complex is the result of a coordination reaction, in which
the central cobalt(III) ion coordinates with six ammonia (NH3) ligands to form a complex cation. The
chloride ions are typically present in the solution or as a counterion to balance the charge of the complex
cation.The formation of coordination complexes like hexaamminecobalt(III) chloride is governed by the
principles of coordination chemistry. In this case, the cobalt(III) ion has a coordination number of 6,
meaning it can bond with up to six ligands. Ammonia molecules serve as the ligands in this complex,
coordinating with the cobalt(III) ion to satisfy its coordination number.Chloride ions, when present in the
reaction, can serve as counterions to balance the charge of the complex. When hexaamminecobalt(III)
cations form, they have a +3 charge. To achieve electrical neutrality in the overall complex, chloride ions
(Cl-) are often used as counterions because they have a -1 charge. By including three chloride ions, the
overall charge of the complex becomes neutral.The reaction for the formation of hexaamminecobalt(III)
chloride can be represented as follows:

[Co(NH3)6]+ + 3 Cl- → [Co(NH3)6]Cl3

Chloropentaamminecobalt(III) chloride,[Co(NH3)5Cl]Cl2, is a coordination complex where the central

cobalt ion is surrounded by five ammonia (ammine) ligands and one chloride ion. The complex is formed
by the substitution of one ammine ligand from hexaamminecobalt(III) chloride ([Co(NH3)6]Cl3) with a
chloride ion. The reason for the complex to include a chloride ion is due to the chemical reactivity and the
nature of the coordination properties of cobalt. In coordination chemistry, transition metal ions like cobalt
have the ability to form coordination complexes by accepting electron pairs from ligands, which can be
ions or molecules with lone pairs of electrons. In the case of chloropentaamminecobalt(III) chloride, the
substitution of an ammine ligand with a chloride ion alters the coordination sphere around the central
cobalt(III) ion. This change in the ligands surrounding the cobalt atom results in a distinct complex, leading
to a distorted octahedral geometry.

The inclusion of the chloride ion in the complex influences its properties, reactivity, and overall behavior.
This coordination with the chloride ion is an intrinsic aspect of the chemical structure of
chloropentaamminecobalt(III) chloride and plays a role in the electronic structure and stability of the
complex.

The reaction for the synthesis of chloropentaamminecobalt(III) chloride be represented as:

[Co(NH3)6]Cl3 + Cl- -> [Co(NH3)5Cl]Cl2 + NH4+[Co(NH3)6]Cl3 + Cl- -> [Co(NH3)5Cl]Cl2 + NH4+

Werner Theory:
Werner theory is related to pentaammine cobalt (III) chloride and hexaammine
cobalt (III) chloride complexes.Werner produced a theory to explain the structures, formation and nature
of bonding in the coordination compounds.
He postulated that metals exhibit two types of valencies
(i) primary valency and (ii) secondary valency.
The primary valency is ionizable and non-directional. It must satisfy negative ions in simple salts such as
NaCl, CaCl2 , CoCl3 . It represents the oxidation state of metals and is present outside the coordination
sphere.The secondary valence is non-ionisable directional and satisfies both negative ions and neutral
molecules. It represents the coordination number of the metals and is present inside the coordination
sphere.Werner also explained the Structure and properties of complexes of Co (III) chloride with
ammonia.
Compounds No. of No. Of ions
Old New Formulae Colour Old Name Charges on Cation Anion Total Conductivity
Formulae Complex ion

CoCl3.6H2O [Co(NH3)6Cl3] Yellow Luteo +3 1 3 4 138.4Ms/cm

Complex
CoCl3.5H2O [Co(NH3)5Cl]Cl2 Purple Purpure +2 1 2 11.57 mS/cm
Materials:
250ML Conical flask (To hold and measure chemical liquid samples) ,Pipette (To measure
out or transfer small quantities of liquid) ,Filter paper (For the separation of solid particles
from liquids or gases) ,Ice (To explore physical changes) ,Beakers ( For holding liquids,
chemical reaction, measuring liquids and heating) ,Thermometer ( Measure temperature)
,Hot plate ( To Heat sample) ,Measuring cylinder (to measure the volume of different
liquids).
Experiment:
Chemical required:
 Hexaammine cobalt(III) chloride: 0.5g of CoCl3.6H2O ,0.33g of NH4Cl ,7ml
Distilled water, 0.1g of Charcoal, 4.5ml of Conc. Aqueous NH3, 0.4ml 0f H2O2.
,1ml of cold conc. HCL
 Chloropentaammine cobalt(III) chloride: 1g of CoCl3.6H2O ,0.5g of NH4Cl ,7ml
Distilled water, 3ml of Conc. Aqueous NH3, 1ml 0f H2O2. ,3ml of conc. HC

Procedure:
Hexaammine cobalt(III) chloride

Take 0.5g CoCl3.6H2O, 0.33g NH4Cl and 7ml distilled water in the flask, Add 0.1 g charcoal and 4.5ml NH3 it
and mix it well until brown slurry is form, Then place it on ice bath and cool to 0'C ,Add 0.4 ml H2O2 in
it.Maintain the temperature of the mixture to 10'C ,Heat the mixture on hot plate to 60'C and maintain
this temperature for 30 minutes, Cool the mixture to 0'C and product precipitate out then filter it, Take
the product in conical flask add 10ml hot water, 1ml cold conc. HCl, Heat the mixture upto 70' C and filter
it when it is still hot, Place the filtrate in ice bath and add 1 ml cold conc. HCl, Orange precipitate will form
which is obtained by filtration.

0.5g of 0.1g of Brown place it on Add 0.4 ml Maintain Heat the Filter the 1ml of Again cool the orange
CoCl3.6H2 Charcoal, slurry is ice bath H2O2 . the mixture solution. cold conc. filter. filter color and
O ,0.33g 4.5ml of form. and cool temperatu on hot HCL in the solution. precipitat
of NH4Cl Conc. to 0'C . re of the plate to filtrate e out.
,7ml Aqueous mixture to 60'C and solution.
NH3. 10'C . maintain
this
temperatu
re.
 Chloropentaammine cobalt(III) chloride
Take 0.5ml NH4Cl and 3ml Aq. NH3 in the flask, stirr NH4Cl solution with adding using magnetic stirrer 1g
finely divide CoCl3.6H2O in small portions, Add 1 ml 30% H2O2 to Brown Cobalt slurry(An addition two
drops per second is usually sufficient but care required because high exothermic effervescence
produce)turn off the magnetic stirrer to prevent the overflow of the solution ,when effervescence is
ceased add 3ml conc.HCl with continuous stirring.(pour 1-2ml at a time) ,Heat the mixture on hot plate to
60'C with stirring. Hold temperature 55'C-65'C for 25 minutes, Add 7ml distilled water and allow to cool
at room temperature ,collect the purple product (By filtration).

0.5ml NH4Cl using magnetic Add 1 ml 30% Add 3ml Hold Add 7ml collect the
and 3ml stirrer 1g finely H2O2 to conc.HCl. temperature distilled water. purple product
Aq.NH3 in the divide Brown Cobalt 55'C-65'C for (By filtration).
flask. cocl2.6H2O in slurry. 25 minutes.
small portions.

Result and Discussion:

Cobalt(III) can form complexes with chlorine due to its ability to exhibit
various oxidation states and its electron configuration. In these complexes, cobalt typically forms
coordinate bonds with chlorine atoms, forming stable coordination compounds due to the Lewis acid-
base interaction between the electron-deficient cobalt and the electron-rich chlorine atoms.
Hexaamminecobalt(III) chloride is a coordination complex that forms when hexaamminecobalt(III) cations
([Co(NH3)6]3+) react with chloride ions (Cl-). This complex is the result of a coordination reaction, in which
the central cobalt(III) ion coordinates with six ammonia (NH3) ligands to form a complex cation. The
chloride ions are typically present in the solution or as a counterion to balance the charge of the complex
cation.The formation of coordination complexes like hexaamminecobalt(III) chloride is governed by the
principles of coordination chemistry. In this case, the cobalt(III) ion has a coordination number of 6,
meaning it can bond with up to six ligands. Ammonia molecules serve as the ligands in this complex,
coordinating with the cobalt(III) ion to satisfy its coordination number.Chloride ions, when present in the
reaction, can serve as counterions to balance the charge of the complex. When hexaamminecobalt(III)
cations form, they have a +3 charge. To achieve electrical neutrality in the overall complex, chloride ions
(Cl-) are often used as counterions because they have a -1 charge. By including three chloride ions, the
overall charge of the complex becomes neutral.The reaction for the formation of hexaamminecobalt(III)
chloride can be represented as follows:

[Co(NH3)6]3+ + 3Cl- → [Co(NH3)6]Cl3

The orange color observed at the end of the synthesis of hexaammine cobalt(III) chloride is due to the
formation of the complex itself, which possesses unique optical properties. During the synthesis, as the
reaction progresses, hexaammine cobalt(III) chloride is formed through the reaction between a cobalt(III)
salt (such as cobalt(III) chloride) and ammonia. This complex is characterized by a central cobalt(III) ion
surrounded by six ammine ligands and a chloride ion. The specific arrangement of the ligands around the
cobalt(III) ion causes the complex to absorb certain wavelengths of light in the visible spectrum. In the
case of hexaammine cobalt(III) chloride, the absorption of light corresponds to the orange region of the
spectrum.The reason for the orange coloration lies in the complex's electronic structure. This complex
absorbs light in the blue-green region of the visible spectrum due to the electronic transitions of the
ligands and the central cobalt ion within the coordination sphere. The absorbed light in the blue-green
portion results in the complementary color, which is orange, being transmitted or reflected. Therefore,
the observed orange color is a result of the specific electronic transitions within the complex, causing it
to absorb light in the blue-green range and appear orange to the human eye.In summary, the orange color
observed at the end of the synthesis of hexaammine cobalt(III) chloride is a consequence of the specific
electronic transitions occurring within the complex, leading to the absorption of certain wavelengths of
light and the perception of an orange hue.

Experimental product Actual product

Our product is in liquid form because we did not wash our product with ice cold ethanol and allow to air
dry, because our desire color is observed. Due to liquid product we could not determine the percentage
yield. If we got solid product then we will find percentage yield.
Chloropentaamminecobalt(III) chloride is a coordination complex where the central cobalt ion is
surrounded by five ammonia (ammine) ligands and one chloride ion. The complex is formed by the
substitution of one ammine ligand from hexaamminecobalt(III) chloride with a chloride ion. The reason
for the complex to include a chloride ion is due to the chemical reactivity and the nature of the
coordination properties of cobalt. In coordination chemistry, transition metal ions like cobalt have the
ability to form coordination complexes by accepting electron pairs from ligands, which can be ions or
molecules with lone pairs of electrons. In the case of chloropentaamminecobalt(III) chloride, the
substitution of an ammine ligand with a chloride ion alters the coordination sphere around the central
cobalt(III) ion. This change in the ligands surrounding the cobalt atom results in a distinct complex, leading
to a distorted octahedral geometry.
The inclusion of the chloride ion in the complex influences its properties, reactivity, and overall behavior.
This coordination with the chloride ion is an intrinsic aspect of the chemical structure of
chloropentaamminecobalt(III) chloride and plays a role in the electronic structure and stability of the
complex. The reaction for the synthesis of chloropentaamminecobalt(III) chloride be represented as:

[Co(NH3)6]Cl3 + Cl- -> [Co(NH3)5Cl]Cl2 + NH4 + [Co(NH3)6]Cl3 + Cl- -> [Co(NH3)5Cl]Cl2 + NH4+
The purple color observed in the preparation of chloropentaaminecobalt(III) chloride, [Co(NH3)5Cl]Cl2, is
due to the electronic transitions that occur within the complex when it absorbs light in the visible
spectrum. The color is a result of the interaction between the cobalt(III) ion (Co^3+) and the ligands
(ammonia and chloride ions) in the complex.In this complex, cobalt(III) is surrounded by five ammonia
(NH3) ligands and one chloride (Cl-) ligand. The cobalt(III) ion has a partially filled d-orbital with an
electronic configuration of [Ar] 3d6. When ammonia and chloride ligands coordinate to the central cobalt
ion, they interact with the d-orbitals, causing d-d electronic transitions. These transitions involve the
promotion of electrons from the lower-energy d orbitals to higher-energy d orbitals, and they correspond
to the absorption of specific wavelengths of light in the visible spectrum. The energy difference between
the ground state and excited states of the complex determines the color observed. In the case of
chloropentaaminecobalt(III) chloride, this energy difference corresponds to light in the violet and blue
regions of the visible spectrum. When violet and blue wavelengths of light are absorbed by the complex,
the complementary color, which is purple, is what we perceive. The specific shade of purple can vary
depending on the ligands and their arrangement around the cobalt(III) ion, but the overall purple color is
a result of the electronic transitions within the complex. The coloration of coordination complexes like
this one is a well-studied aspect of coordination chemistry and provides insights into the electronic
structure of the complex.

Experimental product Actual Product

Our product is in liquid form because we did not wash our product with ice cold ethanol and allow to air
dry, because our desire color is observed. Due to liquid product we could not determine the percentage
yield. If we got solid product then we will find percentage yield.

Electrical Conductance Measurement:

Molar conductivity of chloropentaammine cobalt (III) chloride : 115.7 mS/cm
Molar conductivity of hexaammine cobalt (III) chloride: 138.4 mS/cm
"The conductance of solution depends upon the numbers of charge particles present in that solution."
[Co(NH3)6]Cl3→ [Co(NH3)6]+ 3Cl-
[Co(NH3)5Cl]Cl2 → [Co(NH3)5Cl]+ 2Cl-
So, when we measure the electrical conductance of both solutions,hexaammine cobalt (III) chloride has
greater value of electrical conductance as compared to pentaammine cobalt (III)chloride, So that the
electrical conductance of the compound should be the following order which also satisfies the observed
conductance value.
[Co(NH3)6]Cl3 > [Co(NH3)5Cl]Cl3
Calculations:

Limiting Reactant:

2CoCl2.6H2O + 2NH4Cl + 8NH3 +H2O2 2[Co(NH3)5(H2O2)] +12H2O

[Co(NH3)5(H2O)]Cl3 [Co(NH3)5(H2O)Cl]Cl2 + H2O

2 moles of 2CoCl2.6H2O = 2 moles of [Co(NH3)5(H2O)]Cl3

2CoCl2.6H2O act as a limiting reagent.

Molar mass of 2CoCl2.6H2O = 8.73 + 2(35.45) + 6[2(1.01) + 16.00]

= 237.95 gmol-1

= 2.5060g/237.95 gmol-1

=0.01 mole of CoCl2.6H2O

Theoretical yield:

2CoCl2.6H2O + 2NH4Cl + 8NH3 + H2O2 2[Co(NH3)5Cl]Cl2+ 14H2O

Molar mass of 2[Co(NH3)5Cl]Cl2 =250.4 gmol-1

2 moles of NH4Cl =2 moles of 2[Co(NH3)5Cl]Cl2

0.09 moles of NH4Cl = 0.09 moles of [Co(NH3)5Cl]Cl2

0.09 moles of [Co(NH3)5Cl]Cl2 × 250.4 gmol-1 = 22.536g of [Co(NH3)5Cl]Cl2

2 moles of CoCl2.6H2O = 2 moles of Co(NH3)5Cl]Cl2

0.04 mole of CoCl2.6H2O = 0.04 mole of Co (NH3)5Cl]Cl2

0.04 mole of CoCl2.6H2O × 250.4 gmol-1 = 10.016g Co (NH3)5Cl]Cl2

Therefore, CoCl2.6H2O is a limiting reactant

No of moles of CoCl2.6H2O = 10.0427 gmol-1 / 238 gmol-1 =0.042mol

No of moles of CoCl2.6H2O = No of moles of Co(NH3)5Cl]Cl2

Molar mass of Co(NH3)5Cl]Cl2 = 250.4 gmol-1

 Theoretical yield for [Co(NH3)5(H2O)Cl]Cl2 = 0.042 mol × 250.4 gmol-1

= 10.517g

Techniques:
UV-Vis Spectroscopy:
Chloro Pentaamine Cobalt(III) Chloride: UV-Vis spectroscopy is a valuable technique for characterizing
coordination compounds. Chloro Pentaamine Cobalt(III) Chloride typically exhibits a characteristic
absorption spectrum with peaks in the UV-Vis region. The position and intensity of these peaks can
provide information about the electronic transitions in the complex, aiding in its identification and purity
assessment.

Hexammine Cobalt(III) Chloride: Similar to Chloro Pentaamine Cobalt(III) Chloride, hexammine

cobalt(III) chloride also displays characteristic UV-Vis absorption bands. By comparing the UV-Vis spectra
of the starting material (hexammine cobalt(III) chloride) and the product, one can identify changes in the
absorption pattern, confirming the formation of the desired complex.

Infrared Spectroscopy (IR):

Chloro Pentaamine Cobalt(III) Chloride: IR spectroscopy can be used to analyze the vibrational modes
of molecules, including coordination compounds. It can help identify the presence of specific functional
groups and ligands in the complex. For Chloro Pentaamine Cobalt(III) Chloride, the appearance or
disappearance of characteristic IR peaks associated with ammonia (NH₃) and chloride (Cl-) ligands can be
indicative of the ligand substitution.

Hexammine Cobalt(III) Chloride: Similar to the product, IR spectroscopy can be employed to

characterize hexammine cobalt(III) chloride and identify the vibrational modes of ammonia ligands.

X-ray Crystallography:
Chloro Pentaamine Cobalt(III) Chloride: If available, X-ray crystallography is a powerful technique to
determine the three-dimensional structure of coordination compounds at the atomic level. It provides
information about bond lengths, bond angles, and the overall geometry of the complex. X-ray
crystallography can confirm the presence of chloride ions in the complex and their arrangement around
the central cobalt ion.

Hexammine Cobalt(III) Chloride: X-ray crystallography can also be applied to determine the crystal
structure of hexammine cobalt(III) chloride, aiding in the understanding of its molecular geometry.

Conclusions:
The orange color of product of hexaammine cobalt(III) chloride and purple color of product
of chloropentaammine cobalt(III) chloride complex was obtained with theoretical yield of 0.01 mole of
CoCl2.6H2O.
Reference:
 Huheey, James E. (1983). Inorganic Chemistry (3rd ed.). p. 360. Bjerrum, J.; McReynolds, J. P. (1946).
"Hexamminecobalt(III) Salts". Inorg. Synth. 2: 216–221.
doi:10.1002/9780470132333.ch69. (Introduction)
 Fremy, M. E. (1852). "Recherches sur le cobalt". Ann. Chim. Phys. 35: 257–312. Lindholm, R. D.; Bause,
Daniel E. (1978). "Complexes of Cobalt Containing Ammonia or Ethylene Diamine:
Hexaamminecobalt(III) Salts". Inorg. Synth. 18: 67–69. doi:10.1002/9780470132494.ch14.(Research
paper)
 Ramakrishnan, B.; Sekharudu, C.; Pan, B.; Sundaralingam, M. (2003). "Near-atomic resolution crystal
structure of an A-DNA decamer d(CCCGATCGGG): cobalt hexammine interaction with A-DNA". Acta
Crystallogr. D59 (Pt 1): 67–72. doi:10.1107/s0907444902018917. PMID 12499541.(result
&Discussion)
 Rudisser, S.; Tinoco, I., Jr. (2000). "Solution structure of Cobalt(III)hexammine complexed to the GAAA
tetraloop, and metal-ion binding to G.A mismatches". J. Mol. Biol. 295 (5): 1211–1232.
doi:10.1006/jmbi.1999.3421. PMID 10653698.(Werner theory concept)
 McPherson, Alexander (2002). Introduction to Macromolecular Crystallography. John Wiley & Sons.
ISBN 0-471-25122-4.10.1080/07391102.1986.10508453(Techniques reading)