EXERCISE 2

SPECTROSCOPY OF COMPLEXES

I. INTRODUCTION
II. MATERIALS AND METHODS
A. LIST OF NECESSARY APPARATUS AND OTHER MATERIALS

50-mL volumetric flasks Spatula

50-mL beakers 10-mL pipet
100-mL beaker Cuvette
250-mL beaker Wash bottle
400-mL beaker Tissue
Weighing bottle Single-beam spectrophotometer

B. LIST OF NECESSARY CHEMICALS

AMOUNT HAZARDS, PRECAUTIONS,

PHYSICAL
CHEMICAL REAGENT AND FIRST AID AND
PROPERTIES
PURPOSE ANTIDOTE
H: May cause or intensify fire;
Causes severe skin burns and
Copper(II) nitrate eye damage; Harmful if
MF: Cu(NO3)2
swallowed
MM: 187.554 g/mol
Source of the MP: 255-256 deg C
P: Wear appropriate clothing.
copper BP: sublimes
complex to be Appearance: Large,
FA: INHALATION: move to
prepared for blue-green,
fresh air. INGESTION: give
spectroscopic orthorhombic crystals
large amounts of water;
analysis Density: 2.32 at 68 F
EYES: flush with water for at
Solubility: Sol in water,
least 15 min.; SKIN: flush
ethyl acetate, dioxane
with water.

D: D499
H: Flammable; Causes severe
skin burns and eye damage;
MF: C2H8N2
Harmful if swallowed
MM: 60.1 g/mol
Ethylenediamine MP: 11 C
P: Wear appropriate clothing.
BP: 117 C
Solvent for
Appearance: clear
preparation of FA: Eye: Irrigate immediately
colorless liquid
some Skin: Water flush immediately
Density: 0.898 at 77 F
complexes Breathing: Respiratory
Solubility: Sol in
support
benzene unless
Swallow: Medical attention
insufficiently dried;
immediately
slightly sol in ether
D: G703
Source of the MF: Ni(NO3)2 H: May cause or intensify fire;
nickel MM: 182.701 g/mol Causes severe skin burns and
complex to be MP: 56.7 C eye damage; Harmful if
Nickel(II) nitrate
prepared for BP: 136.7 C swallowed
spectroscopic Appearance: green
analysis crystalline solid P: Wear appropriate clothing.

Cobalt(II) nitrate hexahydrate
Pentaamminechlorocobalt(III)
chloride
Potassium permanganate
Density: 2.05 at 68 F
Solubility: Sol in water FA: INHALATION: move to
fresh air. INGESTION: give
large amounts of water;
EYES: flush with water for at
least 15 min.; SKIN: flush
with water.
D: D499
H: May cause or intensify fire;
Causes severe skin burns and
eye damage; Harmful if
swallowed
MF: Co(NO3)26H2O
Source of the MM: 291.031 g/mol
P: Wear appropriate clothing.
cobalt MP: 55 C
complex to be BP: N/A
FA: INHALATION: move to
prepared for Appearance: Red
fresh air. INGESTION: give
spectroscopic crystals
large amounts of water;
analysis Density: 1.88 g/cm
EYES: flush with water for at
Solubility: Sol in water
least 15 min.; SKIN: flush
with water.
D: D499
H: May cause or intensify fire;
Causes severe skin burns and
eye damage; Harmful if
MF: [CoCl(NH3)5]Cl2
swallowed
MM: 250.438 g/mol
One of the MP: N/A
P: Wear appropriate clothing.
complexes to BP: dec. above 150 C
be prepared Appearance: red-violet
FA: INHALATION: move to
for rhombic-shaped
fresh air. INGESTION: give
spectroscopic crystals
large amounts of water;
analysis Density: 1.78 g/cm
EYES: flush with water for at
Solubility: 0.4 g/100
least 15 min.; SKIN: flush
mL sol in water
with water.
D: D499
H: May cause or intensify fire;
MF: KMnO4 Causes severe skin burns and
MM: 158.032 g/mol eye damage; Harmful if
One of the
MP: >240 C swallowed; Burns and stains
complexes to
BP: N/A the skin dark brown.
be prepared
Appearance: purplish
for
colored crystalline solid P: Wear appropriate clothing.
spectroscopic
Density: 2.7 g/cm
analysis
Solubility: Soluble in FA: INGESTION: induce
many organic solvents vomiting and follow with
thorough gastric lavage,
 demulcents, glucose I.V.,
fluid therapy, and antibiotics.

D: E501
Potassium dichromate One of the MF: K2Cr2O7 H: may intensify fire; harmful
complexes to MM: 294.182 in contact with skin; causes
be prepared Appearance: bright serious eye damage; fatal if
for orange-red triclinic inhaled; may cause allergy or
spectroscopic crystals asthma symptoms or
analysis Odor: odourless breathing difficulties
Taste: bitter. metallic
BP: decomposes at P: Avoid contact with any
about 500 part of the body; do not
MP: 398 inhale; keep away from fire,
Solubility: 12g/100 mL flame and oxidizable
at 20C substances; wear appropriate
Density: 2.676 at 25C clothing

First Aid:
Eye: flush with water
immediately
Breathing: move to fresh air;
artificial respiration
Skin: rinse with plenty of
water for 15 minutes
Swallow: rinse mouth; give
water to drink

Antidotes: orotrachaeal or
nasotrachaeal intubation for
airway control; use 0.9%
saline (NS) or lactated
Ringers (LR) if signs of
hypovolemia are present; use
proparacaine hydrochloride to
assist eye irrigation

Disposal: D405
Potassium One of the MF: K3[Cr(C2O4)3] Disposal: D405
tris(oxalato)chromate(III) tris(oxalato)m 3H2O
trihydrate etallates(III) MM: 487.396
complexes
synthesized
from Exer 1;
subject for
spectroscopic
analysis

Potassium tris(oxalato)ferrate(III) One of the MF: K3[Fe(C2O4)3] Disposal: D499

trihydrate tris(oxalato)m 3H2O
etallates(III) MM: 491.2449
complexes
synthesized
 from Exer 1;
subject for
spectroscopic
analysis

Potassium One of the MF: K3[Co(C2O4)3] Disposal: D499

tris(oxalato)cobaltate(III) tris(oxalato)m 3.5H2O
etallates(III) MM: 503.3411
complexes
synthesized
from Exer 1;
subject for
spectroscopic
analysis

C. SCHEMATIC DIAGRAM OF THE PROCEDURE

0.0938 g 0.01 M Cu(NO3)2 * in 50-mL beaker

Dissolve in small amount of distilled H2O**.

Transfer quantitatively into 50-mL volumetric
flask.
Dilute to mark with dH2O**.

Prepare the remaining solutions according to Table 1.1 following the same procedure above.

Table 1.1. Preparation of complex solutions for UV-Vis spectroscopic analysis.

SOLUTION* MASS OF COMPOUND, g SOLVENT**
0.01 M Cu(NO3)2 0.0938 0.1 M ethylenediamine
0.01 M Cu(NO3)2 0.0938 12 M ethylenediamine
0.2 M Ni(NO3)2 1.8270 Water
0.2 M Ni(NO3)2 1.8270 12 M ethylenediamine
0.1 M Co(NO3)26H2O 1.4552 Water
0.1 M Co(NO3)26H2O 1.4552 12 M ethylenediamine
0.01 M [CoCl(NH3)5]Cl2 0.1252 Water
0.0001 M KMnO4 0.0008 Water
0.0001 M K2Cr2O7 0.0015 water
0.01 M K3[Co(C2O4)3]3.5H2O 0.2517 Water
0.01 M K3[Fe(C2O4)3]3H2O 0.2456 Water
0.01 M K3[Cr(C2O4)3]3H2O 0.2437 Water
UV-Vis Spectroscopic Analysis

D. SET-UP
***No set-ups***

III. CHEMICAL REACTIONS INVOLVED

IV. DATA AND RESULTS

Table 2.2. Observations on the color and wavelength of maximum absorption of different metal complexes.

Complex Color of solution max, nm

[Cu(H2O)6]2+
[Cu(en)2(H2O)2]2+
[Cu(en)3]2+
[Ni(H2O)6]2+
[Ni(en)3]2+
[Co(H2O)6]2+
[Co(en)3]2+
[CoCl(NH3)5]2+
MnO4-
Cr2O72-
[Co(C2O4)3]3-
[Fe(C2O4)3]3-
[Cu(H2O)6]2+

Table 2.3. Metal center, d-configuration and ground term symbol of the metal complexes.
Ground Term
Complex Metal Center dn
Symbol
[Cu(H2O)6] 2+

[Cu(en)2(H2O)2]2+
[Cu(en)3]2+
[Ni(H2O)6]2+
[Ni(en)3]2+
[Co(H2O)6]2+
[Co(en)3]2+
[CoCl(NH3)5]2+
MnO4-
Cr2O72-
[Co(C2O4)3]3-
[Fe(C2O4)3]3-

Table 2.4. Transition assignment, o and energy of the metal complexes.

Complex dn o, cm-1 E, kJ/mol
[Cu(H2O)6] 2+

[Cu(en)2(H2O)2]2+
[Cu(en)3]2+
[Ni(H2O)6]2+
[Ni(en)3]2+
[Co(H2O)6]2+
[Co(en)3]2+
MnO4-
Cr2O72-
[Co(C2O4)3]3-
[Fe(C2O4)3]3-
[Cr(C2O4)3]3-
Calculations:

Mass = M x V x MM

0.01 M Cu(NO3)2 in H2O

(3 )2 = (0.01 ) (0.050 ) (187.554 ) = .

0.01 M Cu(NO3)2 in 0.1 M en

(3 )2 = (0.01 ) (0.050 ) (187.554 ) = .

0.01 M Cu(NO3)2 in 12 M en

(3 )2 = (0.01 ) (0.050 ) (187.554 ) = .

0.2 M Ni(NO3)2 in H2O

(3 )2 = (0.2 ) (0.050 ) (182.701 ) = .

0.2 M Ni(NO3)2 in 12 M en

(3 )2 = (0.2 ) (0.050 ) (182.701 ) = .

0.1 M Co(NO3)2-6H2O in H2O

(3 )2 = (0.1 ) (0.050 ) (291.031 ) = .

0.1 M Co(NO3)2-6H2O in 12 M en

(3 )2 = (0.1 ) (0.050 ) (291.031 ) = .

0.01 [CoCl(NH3)5]Cl2 in H2O

[(3 )5 62 = (0.01 ) (0.050 ) (250.438 ) = .

0.0001M KMnO4 in H2O

4 = (0.0001 ) (0.050 ) (158.032 ) = .

0.0001M K2Cr2O7 in H2O

2 2 7 = (0.0001 ) (0.050 ) (294.182 ) = .

0.01M K3[Co(C2O4)3]3.5H2O

= (0.01 ) (0.050 ) (503.3411 ) = .

0.01M K3[Fe(C2O4)3]3H2O

= (0.01 ) (0.050 ) (491.2449 ) = .

0.01M K3[Cr(C2O4)3]3H2O

= (0.01 ) (0.050 ) (487.396 ) = .

For all preparations, weigh the calculated amount for each compound in a weighing bottle/ 50-mL beaker, and
dissolve in a small amount of indicated solvent. Transfer quantitatively into a 50-mL volumetric flask and dilute
to mark with the indicated solvent.