Indian Institute of Science Education and

Research, Kolkata

CH2103
Inorganic and Spectroscopy Laboratory

Laboratory Manual

2017
 CH 2103 - Inorganic and Spectroscopy Laboratory
III Semester, July 2017 - December - 2017
Time: 10:00 – 13:00

General Instructions
1. Attendance is mandatory. In case of illness etc. the student must contact the instructor and
fix a schedule for making up the missed lab. All labs must be completed in order to get a
passing grade.
2. All data and results should be recorded directly in the lab notebook. The recording should
include, title of the experiment, date of experiment, working formula, data in tabulated
forms, results and calculations.
3. The instructor should sign the data, before the student leave the lab.
4. Graph papers and computer print outs may be directly pasted on the lab notebook.
5. The lab notebook must be submitted to the instructor with the completed work before the
student leaves the lab.

Grading :
The marks distribution for the lab course will be as follows:

1. Two Mid-semester examination……………………………………………….40

2. Lab notebook………………………………………………………………….10

3. Attendance…………………………………………………………………....10

4. Final examination……………………………………………………………..40

2
 List of Experiments

Sl. Experiments Page

No. No.

1. Preparation of Potassium Trioxalatoferrate(III): Synthesis, Spectra and 4

Photochemistry.

2. Synthesis of Silver Nanoprisms with Variable Size and Investigation of Their 7

Optical Properties

3. Synthesis and Optical Characterization of Cadmium Sulfide Nanoparticles 11

4. Synthesis and Characterization of Linkage Isomers, [Co(NH3)5ONO]Cl2 and 13

[Co(NH3)5NO2]Cl2

5. Synthesis and Characterization of cis and trans-dichloro-bis(ethylenediamine) 16

Co(III) Chloride

6. Salicylate Detection by Complexation with Iron(III) and Optical Absorbance 21

Spectroscopy

7. Controlled Synthesis of Two Copper Oxalate Hydrate Complexes: Kinetic versus 27

Thermodynamic Factors.

8. Calculation of Racah Parameter from Absorption Spectra.

3
Experiment No. 1

Preparation of Potassium trioxalatoferrate(III):

Synthesis, Spectra and Photochemistry
Objective: This experiment involves the synthesis of a sparingly soluble iron(II) oxalato complex
and its conversion to a soluble iron(III) oxalato complex. In the second part, the photodecomposition
reaction on exposure to sunlight /UV-light will be studied.

Equipments: UV- Chamber, Heater and stirrer, electronic balance.

Reagents: Oxalic acid dihydrate, ferrous ammonium sulphate, 30% hydrogen peroxide, potassium
oxalate monohydrate, 95% ethanol, aluminium foil.
Glass Apparatus: Beaker, measuring cylinder, glass rod, Buchner funnel, funnel, conical flask.

Experimental Procedure:
1. Dissolve (warm if required) 2.5g oxalic acid dihydrate in 25 mL of water. Add this solution to a
well stirred solution of 5g of ferrous ammonium sulphate in 20 mL water, containing 1 mL of
dilute sulphuric acid taken in a beaker.
2. Slowly heat and stir the mixture until it boils. Cool and allow the yellow precipitate to settle.
3. Decant the supernatant liquid through a Buchner funnel and discard it. Add 15 mL of hot water
to the solid, stir and filter. Drain well and then transfer all the precipitate from the paper back
into the beaker along with 10 mL of hot water.
4. Add 3.5g solid potassium oxalate monohydrate to the beaker and heat to approximately 40ºC for
2 minutes. Add 9 mL of 30% hydrogen peroxide slowly using a dropper to the solution. A brown
suspension will come. (If the precipitate looks yellowish and not brown and settles readily,
decant the supernatant, add a solution of 0.2-0.4g potassium oxalate monohydrate in 1-2 mL of
water and then H2O2 dropwise until the precipitate dissolves. Then add the decanted
supernatant).
5. Heat to boiling for 2 minutes, (dim the lights in the lab from now onwards) and add a solution of
2g oxalic acid dihydrate in 30 mL of water.
6. Boil the solution down to a volume of 40-50 mL. (If the solution is not clear, filter carefully).
Add 95% ethanol (30 mL) slowly until a precipitate starts to form. Redissolve any crystal or
solid as and when it forms by heating on a water bath preferably.

4
7. Cover the sides and top of the beaker with aluminium foil or black paper. Allow the clear
solution to cool down to room temperature. Label and store the beaker till next laboratory class
to complete crystallization.
8. Filter and wash the crystals using the Buchner flask quickly with 1:1 ethanol:water mixture and
finally with acetone. Dry in the air and weigh. The complex is photosensitive and should not be
exposed to light unnecessarily. Store in a sample bottle wrapped in aluminium foil.

Photochemical reactions of potassium trioxalatoferrate (III) trihydrate

1. Dissolve a weighed sample of about 1g of the ferric oxalate complex in 15 mL of 10% (v/v)
acetic acid in a test tube to get a clear yellow-green solution. Expose this solution to bright
sunlight for 45 mins or keep in a UV chamber for the same period. Note down your
observations.
2. Prepare a solution containing 0.2g of the ferric oxalate complex in 15 mL of dilute sulfuric
acid. Dilute the solution to approximately 50 mL with distilled water and expose bright
sunlight for 45 mins or keep in a UV chamber. (carefully note down the observations)
3. Prepare freshly a solution with 0.2 g of the sample under identical dilution.
4. Treat the UV-radiated and the freshly prepared sample solutions with freshly prepared
potassium ferricyanide solution. Note down your observation.

Things you must know:

Chelation and entropy : The multidentate ligands form more stable metal complexes (chelates)
than those formed by similar monodentate ligands. It means the stability constants for the formation
of chelates are much higher than those for similar monodentate ligands. This is due to a positive
entropy term makes the free energy of formation more negative and K more positive. The formtion
of chelates produces a large positive entropy changes which stabilizes the chelate. This is known as
chelate effect.
Isomerism : Optical Isomers
Optical isomers are related as non-superimposable mirror images and differ in the direction with
which they rotate plane-polarised light. These isomers are referred to as enantiomers or
enantiomorphs of each other and their non-superimposable structures are described as being
asymmetric.

5
 Figure 1. The absolute configuration of [Co(en)3]3+
Various methods have been used to denote the absolute configuration of optical isomers such as R
or S, Λ or Δ or C and A. The 1970 IUPAC rules suggest that for octahedral complexes helixes are
defined and then designated Lambda Λ (left-handed) and Delta Δ (right-handed) in much the same
way as we would look at three-bladed propellors and determine whether they would trace out a left
or right handed helix. For tetrahedral complexes R and S is used in a similar method to tetrahedral
Carbon species.
The two isomers have identical chemical properties and just denoting their absolute
configuration does NOT give any information regarding the direction in which they rotate plane-
polarised light. This can ONLY be determined from measurement and then the isomers are further
distinguished by using the prefixes laevo ((-) or l) and dextro ((+) or d) depending on whether they
rotate left or right. The use of l- and d- is not recommended.

Reference:

1. A.J. Elias, A Collection of Interesting General Chemistry Experiments, Universities Press, 2002.

2. N. N. Greenwood, A. Earnshaw, Chemistry of the Elements (2nd ed.). Butterworth–Heinemann,

1997

6
Experiment No. 2

Synthesis of Silver Nanoprisms with Variable Size and Investigation of

Their Optical Properties
Objective: To synthesize a series of silver nanoprisms of varying sizes, study their absorbance
spectra.

Theory
Nano means on the order of 10−9, so one nanometer would be one billionth of a meter. The physical
properties of nanoscale-sized metal particles differ from those of the corresponding bulk material
because unlike electrons in a large continuous piece of metal, those in a nanoparticle are
geometrically restrained and so behave differently. The variation in physical properties caused by
this confinement is known as a quantum-size effect. An important example of such size effects in
metal nanoparticles is Localized Surface Plasmon Resonance (LSPR), which describes the collective
interaction of geometrically constrained, delocalized electrons with light. Confinement of
delocalized electrons is different from a more familiar quantum-size effect in semiconductors, where
an excited delocalized electron can be visualized as “a particle in a box”, and nanocrystals serve as a
“box”. With LSPR, the conducting electron cloud of the nanoparticle oscillates as quantized waves
and absorb electromagnetic radiation of a particular energy.

Nanoparticles of different sizes and shapes display different plasmon resonances and as a
consequence absorb light of different wavelengths, thereby giving rise to different colors of
nanoparticle dispersions. As a result, the size of the particles of colloidal silver of a known shape
can be estimated by measuring λmax from the absorbance spectrum. Most commonly prepared silver
nanoparticles are nonshape-selected quasi-spherical particles with a Plasmon resonance maxima
around 400 nm and a characteristic yellow color. Controlling the shape and size of the particles in
one or two dimensions, as in rods and platelets, respectively, enables maneuvering of plasmon
resonances through the entire visible and near IR spectrum. This experiment demonstrates size and
shape control of 2-D silver nanoprisms. Depending on their size, silver nanoprisms display different
colours in solution

7
 a) b)

Figure 1. (a) Transmission Electron Microscopy (TEM) Image of Silver Nanoprisms (top view), the
prisms shown exhibit a blue colour in solution (40-70 nm side length).(b) Scanning Electron
Microscopy (SEM) Image of Silver Nanoprisms (side view).

In the method used by this experiment to produce silver nanoprisms, sodium borohydride is added to
reduce Ag+(aq) to Ag0(s). As the silver ions are reduced, metallic silver begins to aggregate, forming a
nanoparticle in the presence of surface stabilizing (capping) and shape- and size-modifying agents.
Hydrogen peroxide is used to facilitate formation of shape-selected nanoparticles, by oxidizing
Ag0(s) back to Ag+(aq). This etches the newly formed silver nanoparticles, reaching an equilibrium
between silver being reduced by sodium borohydride and oxidized by hydrogen peroxide. This
ensures that only the most stable shape of nanoparticles survives, which is a prism (platelet) under
the experimental conditions outlined in the procedure section of this experiment.

NaBH4 (aq) + 8 AgNO3(aq) + 4H2O (l) Na[B(OH)4] (aq) + 8 Ag(s) + 8 HNO3

2 Ag0(s) + H2O2 (aq) + 2 H+ (aq) 2 Ag+ (aq) + 2 H2O (l)

Excess sodium citrate acts as a buffer to maintain neutral or weakly basic pH of the solution by
reaction with the nitric acid as it is generated:

Na3C3H5O(COO)3 (aq) + HNO3 Na2HC3H5O(COO)3 (aq) + NaNO3

In addition to acting as a buffer, sodium citrate charge-stabilizes the

+
silver nanoprisms. First, citrate complexes silver then associates O OH O 3 Na
with Ag+ on a surface of a growing nanoparticle rendering the
-O O
surface negative and electrostatically preventing nanoparticles from
O O
Sodium Citrate
8
aggregating. Without proper stabilization, reduction of silver ions leads either to a bulk metal (e.g.
the well-known silver mirror reaction) or heavily aggregated nanoparticles (blackish precipitate).

Potassium bromide can be added to the reaction to alter the size at which the particle stops growing.
At higher concentrations, potassium bromide limits the growth of the nanoparticle to a larger degree,
leading to smaller sizes of nanoprisms being produced. Br- is known to strongly bind to the silver
surface forming silver bromide that arrest growth of the metal silver surfaces. This strong binding
of Br− can be rationalized in terms of the low Ksp of silver bromide and the fact that silver
nanoparticles always have some Ag+ on their surface.

The volume and concentrations of the reagents used in this experiment have been tailored to produce
a high yield of silver nanoprisms. Other shapes of silver nanoparticles, such as cubes, octahedra,
decahedra, bipyramids and icosahedra can be formed under different experimental conditions.

Synthesis of Silver Nanoprisms

PROCEDURE

1. Label four 15 mL test tubes with stopper as 1, 2, 3 and 4.

2. Using pipette add the following chemicals to each test tube:

2.0 mL of 0.0125 M sodium citrate (Na3C6H5O7)
5.0 mL of 0.000375 M silver nitrate (AgNO3)
5.0 mL of 0.05 M hydrogen peroxide (H2O2)

3. Using a micropipette add 0.001 M potassium bromide (KBr) to the vials in the following
volumes:
Test Tube 1: 0 μL
Test Tube 2: 20 μL
Test Tube 3: 25 μL
Test Tube 4: 40 μL
4. Add 2.5 mL of fresh 0.005 M sodium borohydride (NaBH4) to each test tube, place the stopper
on them, and shake to mix the reactants. Allow 5 minutes for the reaction to reach completion,
then record observations. Measure absorption spectrum of the four solutions.

9
SAFETY HAZARDS

Sodium citrate may cause irritation to skin, eyes and respiratory tract. Silver nitrate is poisonous,
corrosive and a strong oxidizer. As a strong oxidizer, hydrogen peroxide is corrosive, causing burns
to the eyes, skin and respiratory tract. Potassium bromide is harmful if swallowed or inhaled.
Sodium borohydride is a corrosive, flammable solid that is dangerous when wet and may release
hydrogen gas. Solution of borohydride should not be kept in tightly sealed vials to avoid possible
explosions. The vials with the freshly synthesized nanoprisms should not be tightly capped due to
possible gas release from unreacted borohydride and hydrogen peroxide.

Reference

A. J. Frank, N. Cathcart, K. E. Maly, and V. Kitaev, J. Chem. Educ., 2010, 87 (10), p 1098

10
Experiment No. 3

Synthesis and Optical Characterization of Cadmium Sulfide Nanoparticles

Objective: In this experiment, you will synthesize yellow CdS nanoparticles, and study their
absorption characteristics.

Theory

Semiconductors have electrical behavior between that of a metal and an insulator. The electronic
band structure of semiconductor consists of a band gap between the valence and the conduction
band. The difference with insulators is the smaller band gap in semiconductors, where the electrons
can be excited across the band gap from the valence to the conduction band even at room
temperature. Semiconductor nanoparticles (NPs) are important because of their numerous
technological applications ranging from biological labels, photovoltaics, light emitting diodes to
optoelectronic transistor components and other optical devices. Among the semiconductors, CdS
exists in cubic crystal structure and in a more stable hexagonal structure. CdS has a direct band gap
of 2.42 eV, which explains its yellow color. Since most of the properties of CdS NPs strongly
depend on their size, size distributions and crystal structure, the manipulation of shape and size at
the nanometer scale is necessary.

The size and shape of CdS NPs can be controlled if synthesized by wet chemical methods either in
organic or aqueous solution. A surfactant should be added to the reaction medium in order to
stabilize the NPs and prevent their aggregation. The ratio of the surfactant to the metal salt solution
determines the size of the CdS NPs. The smaller the NP, the larger will be the band gap and
consequently shorter the emitted wavelength. Hence the emission wavelength of CdS NPs can be
varied over the entire visible spectrum by controlling the size of the NPs.
In this experiment you will synthesize CdS NPs by chemical precipitation method at room
temperature.

11
Experimental Procedure:
1. Prepare 10 ml of 3 mM solution of SDS (MW = 288.38)
2. Add a certain volume of an aqueous Na2S (MW = 78.05) solution to the 10 ml of an aqueous
surfactant (SDS) solution so as to make the final concentration of 1.4 mM of Na2S.
3. Keep the solution for half an hour for equilibration.
4. Add an aqueous CdCl2 (MW = 183.32) solution to the above solution with gentle shaking to
obtain a final Cd2+ concentration of 0.7 mM.
The molar ratio of CdCl2 : Na2S is to be maintained at 1 : 2.
The appearance of light yellow colorations indicates the formation of CdS NPs.
5. Record the UV absorption spectrum of the CdS NP solution.
6. Calculate the band gap (in eV) from the absorption spectrum.

Optical Properties
The UV absorption spectrum will expectedly show an absorption onset in the range of 470–490 nm.
The exact position of the spectral absorption edge will depend on the surfactant used, since the latter
will influence the size of the NP. The UV-absorption of bulk CdS is 540 nm and the apparent blue
shift in the absorption of CdS NPs is due to the quantum size effect.

Hazard Issues
The students must be careful not to touch the chemicals with bare hands.

Reference
S. Kumar, M. Gradzielski, S. K. Mehta, RSC Adv. 2013, 3, 2662-2676.

12
Experiment No. 4

Synthesis and Characterization of Linkage Isomers. [Co(NH3)5ONO]Cl2 and

[Co(NH3)5NO2]Cl2
Objective : To synthesize linkage isomers [Co(NH3)5ONO]Cl2 and [Co(NH3)5NO2]Cl2 and
characterize them by UV-Vis and IR spectroscopy.
Introduction:

The cobalt 2+ ion is more stable than the cobalt 3+ ion for simple salts of cobalt. Only a few
salts of Co(III) such as CoF3 are known. However, complexation stabilizes the higher oxidation
state, and a number of very stable octahedrally coordinated complexes of cobalt(III) are known. In
this experiment, you will prepare two classical linkage isomer compounds [Co(NH3)5ONO]Cl2 and
[Co(NH3)5NO2]Cl2 from [Co(NH3)5Cl]Cl2.

Equipments: Hot-plate, electronic balance, UV-Vis Spectrophotometer, IR-Spectrometer.

Reagents: CoCl2.6 H2O, conc. NH3, conc. HCl, 30% H2O2, ethanol, 2M HCl, 6M HCl.
Glass Apparatus: 100 mL Erlenmeyer Flask, 100 mL beaker, measuring cylinder, glass rod,
Buchner funnel.

Synthesis of ChloropentaamminecobaIt (III) chloride

The equations of the preparation of [Co(NH ) Cl]Cl are as follows:

3 5 2
2+ 3+
Co + NH4+ + 1/2H2O2 → [Co(NH ) H2O]
3 5
3+ -
[Co(NH3)5 H2O] + 3Cl → [Co(NH3)5Cl]Cl2 + H2O

Experimental Procedure:
1. In a fume hood, add 1.25 g of ammonium chloride to 7.5 mL concentrated aqueous ammonia in
a 100-mL beaker. (The combination of NH4Cl and NH3(aq) guarantees a large excess of the NH3
ligand.)
2. Stir the ammonium chloride solution vigorously while adding 2.5 g finely divided CoCl2⋅ 6H2O
in small portions.
3. Add 2 mL 30% hydrogen peroxide (CAUTION: Hydrogen peroxide is a strong oxidizing agent
that can cause severe burns) to the brown Co slurry. An addition rate of about 2 drops per

13
 second is usually sufficient, but care should be taken to avoid excessive effervescence in this
exothermic reaction.
4. When the effervescence has ceased, add 7.5 mL conc. HCl with continuous stirring, pouring
about 0.5 mL at a time. At this point, the reaction may be removed from the hood. Use a heater
to heat the solution to 60°C with occasional stirring. Hold the temperature between 55 °C and 65
°C for 15 min.; this incubation period is necessary to allow complete displacement of all aqua
ligands.
5. Add 6 mL distilled water, and allow the solution to cool to room temperature. Collect the purple
product by filtration through a Buchner funnel; wash it three times with 2 mL cold distilled
water and twice with 2 mL ice-cold ethanol. (The solutions must be cold to prevent undue loss
of product by redissolving.)
6. Transfer the product to a crystallizing dish, loosely cover with filter paper, and allow to dry until
the following laboratory period. Weigh the product and calculate the % yield.
7. Record UV-Vis and IR spectrum of dried product.

Synthesis of nitritopentaamminecobalt (III) Chloride

The equations for the preparation of [Co(NH3)5ONO]Cl2 and [Co(NH3)5NO2]Cl2 from

[Co(NH3)5Cl]Cl2 can be written as follows:
2+ 3+ -
[Co(NH ) Cl] + H O → [Co(NH ) H O] + Cl
3 5 2 3 5 2
3+ - 2+
[Co(NH ) H O] + NO → [Co(NH ) ONO] + H O
3 5 2 2 3 5 2
2+ 2+
[Co(NH ) ONO] → [Co(NH ) NO ]
3 5 3 5 2
Experimental Procedure:
1. Add 1.6 mL of concentrated aqueous ammonia to 16 mL of water taken in a 100 mL beaker
and heat it on a hot plate. The surface temperature of the hot plate is not critical.
2. While heating and stirring this solution, add 1 g of [Co(NH3)5Cl]Cl2 ( if 1 g of the
chloropentaamminecobalt (III) chloride was not obtained in the previous experiment, adjust the
reactants to the amount you obtained.)
3. Continue heating and stirring until the coloured product dissolves. If a dark brown to black
precipitate of cobalt oxide forms, filter it off.
o
4. Cool the filtrate which should be a clear solution to about 10 C. Add 2M HCl slowly while
keeping the solution cold until it is just neutral to litmus.

14
 5. Add 1 g of sodium nitrite followed by 1 mL of 6M HCl and cool the solution in an ice bath.
After the solution has been in an ice bath for an hour, filter the precipitated salmon pink
crystals of [Co(NH3)5ONO]Cl2 using a Buchner funnel.
6. Wash with 5 mL of ice water, wash with 5 mL of alcohol, and then allow it to dry on the lab
bench for one hour before collecting an IR and UV-Vis spectrum. Do not dry in a drying oven.
The product is not stable and will slowly isomerize to the nitro compound. Weigh the product
and calculate the % yield.

Synthesis of nitropentaamminecobalt (III) Chloride

The nitritopentaaminecobalt (III) chloride in the previous experiment is isomerized to the nitro
compound by heating. The nitrito compound prepared before can be utilized before it is dried.

Experimental Procedure:
1. Bring 20 mL of water to a boil, add a few drops of aqueous ammonia, and add 2.0 g of the
[Co(NH ) ONO]Cl .
3 5 2

2. As this solution cools, add 20 mL of conc. HC1. After cooling the solution, the
[Co(NH ) NO ]CI will crystallize from the solution.
3 5 2 2

3. Filter the product in a Buchner funnel, wash the product with 13 mL of alcohol, and allow it to
dry in air for two hours.
4. Collect the IR spectrum and the UV-Vis spectrum of dry product.

Reference:
1. W. L. Jolly, The synthesis and characterization of inorganic compounds; Prentice-Hall, Inc.:
1970.
2. J. Tanaka, S.L. Suib, Experimental methods in inorganic chemistry; Prentice-Hall, Inc.: 1999;

15
Experiment No. 5

Synthesis of Characterization of cis and trans -dichloro-bis(ethylenediamine)

Co(III) Chloride

Objective:
To synthesize geometrical isomers cis and trans-dichlorobis (ethylenediamine) cobalt (III)
Chloride and characterize them by UV-Vis and IR spectroscopy.

Introduction:

The modern area of inorganic chemistry can be said to have begun at the turn of the 20th century
with Alfred Werner's pioneering work on metal complex structure and coordination. Werner proved
that compounds containing six ligands connected to a central metal atom were indeed octahedral by
an elegant resolution of the complex [(Co(en)2(NH3)X]2+. This type of geometry had been theorized
earlier (1875) by van't Hoff, who suggested that appropriately substituted octahedral molecules
should exhibit geometric isomerism.
Compounds having the same formulas but different structures are isomeric. With geometrical
isomers, it is the arrangement of ligands on the central atom that differs. In an octahedral compound
of formula MA4B2 (M = metal, A and B = ligand), where a central metal is surrounded by four of
one type of ligand and two of another, there are two ways to arrange the groups, as shown in Figure
l.a. In the cis isomer, the two B groups area adjacent to each other, while in the trans isomer, the two
B groups are opposite each other.
Geometrical isomers are totally different compounds, having different physical properties,
and often having different colors. In most synthesis, both isomers are obtained. Separation can be a
problem, but because of the (usually) different solubilities and reactivities of the isomers, separation
is possible. The first geometrical isomers were also identified by Werner, who in 1893 determined
the structure of the inorganic geometric isomer pair cis- and trans-[Pt(NH ) Cl ].
3 2 2

Geometrical isomers frequently contain bidentate ligands, which occupy two coordination
sites. Ethylenediamine (en =H2NCH2CH2NH2 ) is such a bidentate ligand. The two geometrical
isomers of the compound to be synthesized in this experiment,
dichlorobis(ethylenediammine)cobalt(III) chloride, [Co(en) Cl ]Cl, are shown in Figure l.b. This
2 2

pair was also first investigated by Werner.

16
 Numerous complexes of cobalt(III) are known and nearly have octahedral structures. In
solution, these ions undergo ligand substitution reactions rather slowly compared to the complexes
of many other transition metals. Because of this relative stability, they are of particular interest, as
they may be easily studied. Indeed, much of our knowledge of and the theory concerning octahedral
complexes in general was derived from studies of cobalt(III) species.

B B

A B A A

A A A A

A B
cis isomer trans isomer
a

NH 2 Cl
NH2 NH2
NH2
NH2
Co Co NH2
Cl
NH 2 NH2
Cl Cl

Cis isomer Trans isomer

b
Figure 1 a. Cis and trans isomers for octahedral complexes b. cis and trans isomers of the
dichlorobis(ethylenediamine) cobalt(III)ion
Cobalt(III) exhibits a particular tendency to coordinate with ligands containing nitrogen. A
majority of these complexes have ammonia, amines, or nitrogen bonded NCS- groups. Several of
these compounds have cis and trans isomers and one of them dichlorobis(ethylenediammine)
cobalt(III) chloride, is particularly appropriate for demonstrating geometric isomerism in transition
metal complexes. It is of further interest to realize that the cis-isomer of this geometric pair exists as
an enantiomorphic (optically active) pair of isomers. The racemic mixture is obtained when the cis-
isomer is prepared. The trans-dichlorobis (ethylenediammine) cobalt(III) chloride, shown in Figure
l.b, is prepared by air oxidation of an aqueous solution of cobalt(II) chloride hexahydrate and
ethylenediamine, followed by the addition of concentrated hydrochloric acid. The synthesis uses a

17
Co2+ species rather than a Co3+ salt, because the aqueous Co(H2O)63+ ion is very unstable because it
2+
is a powerful oxidizing agent and is reduced by water to Co(H O) .
2 6
3+ 2+ +
Co(H O) + ½ H O → Co(H O) +¼O +H
2 6 2 2 6 2

However, the +3 oxidation state can be stabilized by replacing the coordinated water
- - 3+
molecules with groups such as NH , NO , CN , and NH CH CH NH . Once Co has coordinated
3 2 2 2 2

with ethylenediamine and chloride ligands, it shows little or no tendency to oxidize water.

Equipments: Hot-plate, electronic balance, UV-Vis Spectrophotometer, IR-Spectrometer.

Reagents:. CoCl2 • 6 H2O, 10% ethylenediamine solution, conc. HCl.
Glass Apparatus : Watch Glass, 500 mL Beaker, measuring cylinder, glass rod.

Synthesis of trans-dichlorobis (ethylenediamine) cobalt (III) Chloride

The synthesis of trans-Dichlorobis (ethylenediamine) cobalt (III) Chloride is based on the following
equation.
Cl H2
H2
N N

4 CoCl2.6H 2O + 8 H 2N-CH2-CH2-NH 2 + 4 HCl + O Co Cl + 26 H 2O

2
N
N
H2
H2 Cl

trans
Experimental Procedure:
1. Heat about 250 mL of water in a 500-mL beaker and maintain at a moderate boil.
2. In a 50 mL test tube with side arm, dissolve 2.0 g of cobalt(II) chloride hexahydrate
(CoCl2·6H2O) in 10 mL of distilled water. To this, add 6 mL of 10% ethylenediamine (en).
Clamp the test tube and immerse in the beaker of boiling water. Place a rubber cork fitted with
pasteur pipette inside the test tube such that the tip of the pipette is below the surface of solution.
Connect the side arm of the test tube to aspirator to draw air into the solution. During this
process, the cobalt(II) is oxidized to cobalt(III) by the oxygen in the air. The purple reaction
mixture is maintained under these conditions for a period of one hour, with periodic addition of
water so that the final volume of the solution is approximately one-half the original volume.
3. After one hour disconnect the apparatus, remove the tube from the bath, and allow it to cool to
approximately 60° C.
18
4. Add 4 mL of concentrated HCl. (Note: HCl is corrosive - handle with extreme care.) using a
pasteur pipette through the inlet tube. Reconnect the aspirator and place the tube back in the hot
water bath. Adjust the aspirator so that a steady stream of air is pulled through the solution.
Continue heating until the volume of the solution is reduced to the point that crystals of the
product are evident in the tube.
5. Disconnect the apparatus and place the tube in an ice bath to cool. Scrape solid product in the
tube free from the walls, and isolate by vacuum filtration. Wash the green crystalline solid with
two 5 mL portions of cold isopropanol, which is added to the original filtrate to obtain more
product. Once all the product is isolated wash it with two 5 mL portions of diethyl ether and
allow to air dry. The green crystalline product isolated by this procedure is a hydrated form of
[trans-Co(en)2Cl2]Cl.2H2O

6. Transfer the product, trans-[Co(en)2Cl2]Cl.2H2O, to a previously weighed sample vial. Reweigh

and calculate the yield. Store your product.
7. Record the IR spectra (KBr pellet) and UV-vis spectra for comparison with the cis isomer.

Side Arm Test Tube Apparatus

19
Synthesis of cis-Dichloro bis(ethylenediamine) cobalt (III) Chloride
cis-Dichloro bis (ethylenediamine) cobalt (III) Chloride is obtained by conversion of trans-Dichloro
bis (ethylenediamine) cobalt (III) Chloride to the cis form, by evaporating a solution of the trans-
Dichloro bis (ethylenediamine) cobalt (III) Chloride to dryness on a water bath.
Cl H2
H2 Cl
N Cl H2
N Heat in Solution N
Co Cl Co Cl
NH2
N
N N
H2
H2 Cl NH2 H2

trans cis

Experimental Procedure:

1. Place 0.4 g of the green trans-dichloro bis(ethylenediamine) cobalt (III) chloride in 25 mL

beaker. Dissolve this solid material in 3 ml of water and allow the solution to stand for about 10
min at room temperature.
2. Heat the green solution carefully on a hot plate to evaporate the water without violently boiling
the solution. As the solution evaporates a deep violet sample of the cis isomer will form. Keep
adding water to the solution until the color becomes a persistent purple. Heat the mixture to
dryness. Repeat the process to convert most of trans isomer to the cis isomer, but do not heat to
dryness. Transfer the solution to a vial. Add equal volume of 2-propanol, mix and store the vial
for the cis-isomer to crystallize till next lab class.
3. Filter the solution. Wash crystals obtained with ethanol. Dry the crystals before characterization.
4. Record the IR spectra (KBr pellet) and UV-Vis spectra for comparison with the trans isomer.

Reference:
1. J. Springbørg, C.E. Schaffer, “Dianionobis(Ethylenediamine)Cobalt (III) Complexes” Inorganic
Synthesis, 1973; volume 14, pages 63-77.
2. J. C. Bailar, “Cis- and Trans-Dichlorobis-(Ethylenediamine) Cobalt (III) Chloride and the
Resolution of the Cis Form”. Inorganic Synthesis, 1946, volume 2, pages 222-225.
3. B. Douglas, D.H. Daniels and J.J. Alexander, Concepts and Models of Inorganic Chemistry, 2nd
Edition, John Wiley and Sons Inc., New York, 1983.

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Experiment No. 6

Salicylate Detection by Complexation with Iron(III) and Optical

Absorbance Spectroscopy

Background

Spectroscopic analysis is a critical tool in the identification and quantitation of different molecules.
This experiment introduces you to the use of electronic absorption spectroscopy inthe visible region
of the spectrum for the determination of salicylate. There are several uses for salicylate and it is
therefore included in many everyday products. Salicylic acid is the major metabolite of aspirin and
is commonly found in medications that treat acne, warts and other similar ailments. When
acetylsalicylic acid (aspirin) is taken for a headache or inflammation, it is rapidly hydrolyzed in the
stomach. The products of this reaction are salicylic acid and acetic acid. The former is readily
absorbed into the blood stream and is then able to act as an analgesic agent.
In acne treatment, the salicylic acid decreases the shedding of skin cells from hair follicles. These
cells are typically responsible for clogging pores and causing pimples. Salicylic acid also has a
keratolytic (peeling) effect, which causes dead cells to be shed more easily. This facilitates in the
removal of a thin layer of skin and promotes the unclogging of pores. More concentrated solutions
of salicylic acid are used in wart treatment to help soften the wart and to stimulate an immune
response toward the human papillomavirus, responsible for causing wart formation.
Due to the many medical applications of salicylic acid, the development of analytical techniques for
its quantification is important. Indeed, there are a number of methods that have been employed,
including, gas-liquid chromatography (GLC), ultraviolet spectroscopy, and fluorescence
spectroscopy. The most widely used methods in clinical laboratories, however, use colorimetric or
visible spectrophotometry. A version of this method will be applied throughout the experimental
procedure to first quantitate salicylate in a commercial product (face wash), and also in an unknown
solution that you will be given. The second part of the procedure uses spectrophotometry to
investigate the chemical nature of the reaction that yields the colored product you analyze.

21
Theory:

Beer's Law states that the absorbance of a compound is directly proportional to its concentration
(A=εbc). This linear relationship allows us to first construct a calibration curve by collecting the
absorbance values for samples of known concentration at a given wavelength, preferably the λmax,
the wavelength where maximum absorption occurs. The resulting equation for the linear regression
then lets us determine the concentration of an unknown sample by determining its absorbance at the
same wavelength.
Salicylate and salicylic acid do not absorb visible light, creating an experimental challenge. Upon
reaction with iron (III) ions, however, a highly colored species results:

OH
x + yFe
3+ 3+
(Fe )y(Sal) x
O

OH
Iron-Salicylate Complex
Salicylic acid (Sal)
Highly Colored

The complex can be easily detected with a simple spectrophotometer and thus, you will be able to
quantify salicylate in unknown samples. Under the acidic experimental conditions all salicylate will
be protonated as shown in the chemical equation above. The chemical equation shown above
contains the coefficients and subscripts x and y. In the second portion of this experiment, you will
use the method of continuous variation (also called Job's method) to determine these quantities for
the predominant complex. For this procedure, several solutions containing different quantities of
salicylate and Fe3+ will be prepared. While the amount of each reactant is varied, the total moles of
both reagents will remain constant. The solution that yields the greatest absorbance at λmax indicates
the predominant stoichiometry of the iron-salicylate complex.

Safety Hazards
General laboratory safety rules should be followed. Nitric acid is corrosive, and spills should be
cleaned up immediately.

22
Procedure
In this experiment, the concentration of salicylate present in an over the counter acne
medication/face wash and in an unknown sample will be determined by spectrophotometry.
Salicylate itself absorbs ultra-violet radiation and is therefore difficult to measure directly with
simple instrumentation. One method adopted for the measurement of salicylate in clinical situations
involves mixing samples containing salicylate with an excess of ferric ions (FeIII) under acidic
conditions. The resulting complex absorbs strongly in the visible region of the spectrum and can be
easily determined spectrophotometrically. The first section of the experiment involves using this
salicylate-iron complex for the determination of salicylate concentration in an acne medication and
an unknown sample. This will be possible by first generating a calibration curve for salicylate from
several standard solutions of different concentration. In the second section the nature of the
salicylate-iron complex will be investigated by using the method of continuous variation. This
procedure involves varying the amount of each reagent added (salicylate and Fe III) while keeping the
total number of moles constant. The mixture yielding the maximum absorbance corresponds to the
predominant stoichiometry of the complex formation.
Part A: Spectrophotometric Determination of Salicylate in Acne Medication
1. Prepare five standard solutions of sodium salicylate in deionized water. For this task, use a 100
mL volumetric flask to prepare an initial stock solution of 100 mM (0.1M) of sodium salicylate
(you should weigh out sodium salicylate so you will know the exact molarity after you dilute the
volumetric flask to mark). By dilution in appropriate volumetric flasks, prepare standards of 20
mM, 40 mM, 60 mM and 80 mM (10 mL volumetric flasks will give enough of these standards
for this experiment). Prepare 100 mL of a 10 mM standard also in water. The 10 mM solution is
also required in Part B and making a larger quantity now will save time!! (NOTE: Part B
requires that this standard be exactly 10 mM!!) Sodium salicylate has a formula weight of
160.11g/mole. It is important to record the accurate mass of sodium salicylate that you used to
prepare the stock solution, so that you will know the exact molarity of these standards
2. Obtain a sample of acne face wash solution as well as an unknown salicylate sample (solution).
Be sure to record the code of your unknown for your lab report.
3. In separate test tubes, pipet exactly 100 μL of each standard, the acne face wash, and your
unknown. Repeat this procedure two more times for the acne wash and unknown for a total of
three samples for each (to allow for a standard deviation to be generated). It is important to label

23
 these test tubes for identification of each solution. Add 10.00 mL of the acidic 10 mM ferric
nitrate solution (stock in lab) to each test tube. Be sure to mix these solutions well!
4. Using the acidic 10 mM ferric nitrate solution as your blank (100%T), collect optical absorbance
spectra for all of the solutions. Collect an absorbance spectrum (400-700 nm) for your most
concentrated standard to determine λmax (remember to save the file!). If the maximum
absorbance is greater than 1, check your λmax by collecting a spectrum with a less concentrated
standard. Once you determine λmax, set the Spec 20 to this wavelength and analyze your
standards and unknowns. Record the absorbance values for all solutions in your notebook. Be
sure that all solutions yield an absorbance of less that 1.0 at the λmax . Absorbance greater than
this cannot be accurately determined with the spectrophotometer. Make sure you rinse the
cuvette out between each measurement and then rinse with small amount of standard/sample
solution first, before filling the cuvette with the given test solution.

Reminder: It is ideal to generate your calibration curve during your data collection. This will allow
time to repeat any measurements during the same lab period. Doing this will likely improve your
accuracy.

Part B: Determination of Reaction Stoichiometry: An Application of the Method of

Continuous Variation
1. Obtain ~20 mL 10 mM acidic ferric nitrate as well as ~50 mL of dilute nitric acid (60 mM). You
will also need the 10 mM sodium salicylate solution prepared in Part A. This salicylate standard
must be exactly 10 mM for the volumes in Table 1 to work properly.
2. Prepare solutions for spectrophotometric analysis by pipetting the appropriate amount of each
solution into a vial (total 1 mL). Use the amounts from the Table 1 below. Label all your vials!!!
Add 4.00 mL of dilute nitric acid to each mixture of salicylate and ferric nitrate to make a total
volume of 5.00 mL.
3. Using the dilute nitric acid as your blank, collect the absorbance values at λmax for each solution.

24
Table 1: Solution Composition for Method of Continuous Variation

Volume of 10 mM Volume of 10 mM Mole Ratio Mole Fraction of

salicylate/mL ferric nitrate/mL Fe(NO3)3:salicylate Fe(NO3)3
0.100 0.900 9.00:1.00 0.900
0.200 0.800 4.00:1.00 0.800
0.250 0.750 3.00:1.00 0.750
0.330 0.670 2.00:1.00 0.667
0.400 0.600 1.50:1.00 0.600
0.500 0.500 1.00:1.00 0.500
0.600 0.400 1.00:1.50 0.400
0.670 0.330 1.00:2.00 0.333
0.750 0.250 1.00:3.00 0.250
0.800 0.200 1.00:4.00 0.200
0.900 0.100 1.00:9.00 0.100

Data Handling
1. The objective for the first section of the experiment is to determine the concentration of
salicylate in unknown samples. Construction of a calibration curve from the absorbance data
collected from the salicylate standard solutions is the first necessary step towards this goal. In
Excel, plot the absorbance value of each standard (at the λmax) versus the standard's
concentration. The data should show a linear relationship. Generate a linear regression line and
equation for this line. Only include data points with an absorbance less than 1.
2. Determine the concentration of salicylate for each of your samples of acne medication and
unknowns from the linear regression line. Find the average and standard deviation for each
determination. In order to compare your data with the value printed on the bottle's label, convert
your face wash data to units of weight percent. Enter this data into the list of class data for
further analysis.
3. The data collected in the second part of this experiment will allow you to examine the nature of
the reaction between FeIII and salicylate. While the mole ratios of reagents were varied in each
mixture, the total number of moles remained the same. Therefore, the mixture that yields the
greatest absorbance represents the predominant reaction stoichiometry. In order to find which
25
 stoichiometry is favored by this complex, plot the absorbance value of each solution (at the λmax)
versus the mole fraction of iron.

Lab Data Report

1. Provide a plot of the salicylate-Fe(III) complex spectrum for the most concentrated standard
solution indicating the λmax.
2. Show the plot of the calibration curve for salicylate (including equation of line with R2 value).
3. Show the "Job plot" of absorbance (at λmax) versus mole fraction of iron (III) that you obtained in
part B of the experiment. From this data, indicate what you believe is the stoichiometry of the
reaction.
4. Report the mean concentration of salicylate in acne face wash (in units of weight percent) with
confidence interval (95%) that you found. Compare your average value to class average using
95% confidence range treating the class average as the true value.
5. Report the average concentration of salicylate in your unknown sample (in units of molarity, or
millimolar) with associated confidence interval. Make sure you indicate your sample code.
Reference:

J. T. Mitchell-Koch, K. R. Reid, M. E. Meyerhoff, J. Chem. Educ. 2008, 85, 1658-1659.

26
Experiment No. 4

Controlled Synthesis of Two Copper Oxalate Hydrate Complexes: Kinetic

versus Thermodynamic Factors
Introduction:

The primary goal of this experiment is to synthesize two different crystals by controlling the
experimental conditions. K2[Cu(C2O4)2]·2H2O (1) can be easily prepared from the reaction of
CuSO4·5H2O with K2C2O4 in a mole ratio of 1:4 at 90C. However, there is a tetrahydrate analog
K2[Cu(C2O4)2]·4H2O (2) that has been prepared by accident. Scheme 1 shows the molecular
structures of the two compounds.

K2[Cu(C2O4)2]·2H2O K2[Cu(C2O4)2]·4H2O

Scheme 1. Molecular structures of complexes 1 and 2.

The oxalate anion, C2O42− acting as either a unidentate, chelating or bridging ligand, is capable of
coordinating with metal ions in different ways, thus forming versatile structures such as bimetallic
dimers, trimers, tetramers, 1D chains, other 2D networks and 3D lattices. The oxalate bridge has the
remarkable ability to transmit magnetic coupling between paramagnetic metallic centers, which
attracts much attention in the field of molecule-based magnets. Therefore, complexes 1 and 2 can be
used as the starting materials for the design of new systems to improve classical physical properties
(ferromagnetism and metal-organic frameworks).

Coordination modes of the oxalate anion.

In this experiment, K2[Cu(C2O4)2]·4H2O and K2[Cu(C2O4)2]·2H2O can be selectively prepared by

controlling the concentrations of K2[Cu(C2O4)2] solutions. A dilute solution gives rise to one
compound, while a concentrated solution generates another. The visible and the infrared spectra of
the two compounds are identical. Therefore, it is impossible to distinguish them by spectroscopic
studies. However, crystals of the two compounds have different shapes: flat and needles. Therefore,
27
it is easy to distinguish them by appearance. Thermogravimetric analyses (TGA) show that two
compounds lose their water molecules at 150C, and decompose at 250C (Scheme 2). Interestingly,
the tetrahydrate compound can be converted to the dihydrate compound upon the partial loss of
water molecules in air or in solutions. Therefore, it is possible to obtain both kinetic and
thermodynamic products. It is crucial to control the growth of the crystals because of the easy
conversion. Moreover, this experiment clearly demonstrates that the reaction products depend on the
reaction conditions. This experiment illustrates that reactions (or crystallization in this case) can
proceed via two routes and the concentration of the solutions is a key factor in the formation of
different compounds during crystallization. It shows physically that different products can be
understood with chemical principles. Thus, this complicated process of crystallization will help to
understand some factors that determine the formation of different complexes.

Scheme 2. TGA analysis of compounds K2[Cu(C2O4)2]·4H2O and K2[Cu(C2O4)2]·2H2O

Experiment Overview:

An aqueous solution of KHC2O4 (which is synthesized from H2C2O4 and K2CO3) and CuO was
heated at 80 °C. After complete dissolution of CuO, the solution was filtered while hot. From the
blue filtrate, complexes 1 and 2 of different crystal shapes can be separated by carefully
controlling the concentration of the K2[Cu(C2O4)2] solutions. The reactions involved are as
follows:
2H2C2O4 + K2CO3  2KHC2O4 + H2O + CO2↑
CuO + 2KHC2O4  K2[Cu(C2O4)2](aq) + H2O
When a dilute solution of K2[Cu(C2O4)2] at 80 °C was allowed to cool on the bench to room
temperature, dark blue needle crystals are obtained. Alternatively, when a concentrated solution at
80 °C was cooled on the bench to room temperature, light blue flat crystals are obtained. Water
28
content analyses (by heating the freshly prepared crystals at 200 °C for 30 min) show that the dark
blue needle crystals are the tetrahydrate compound while the light blue flat crystals are the
dihydrate.

K2[Cu(C2O4)2] (conc. solution)  K2[Cu(C2O4)2]·4H2O(needle crystal)↓

K2[Cu(C2O4)2](dilute solution)  K2[Cu(C2O4)2]·2H2O(flat crystal)↓

If the needle crystals of compound 2 are immersed in the mother liquid for more than 1.5 h, the
needles slowly convert to flat crystals of compound 1. The conversion can be accelerated by
shaking. Alternatively, the compound 2 when heated to 90°C completely converts to compound 1.
On this basis, it can be concluded that product crystallization proceeds via two routes (Figure
below).

K2[Cu(C2O4)2]·4H2O, 2, is the kinetic product with a lower activation energy but with less
stabilization energy, while K2[Cu(C2O4)2] 2H2O, 1, is the thermodynamic product with a higher
activation energy but with more stabilization energy.

Experimental Procedure:

Synthesis of CuO. 2.0 g of CuSO4·5H2O (8 mmol) was dissolved in 40 mL of water in a 100 mL

beaker. To this solution, an aqueous solution (10 mL) of NaOH (0.8 g, 20 mmol) was added with
stirring. Heating the mixture gently turned the blue precipitate to black. Afterwards, the product
mixture was kept boiling for 15 min and then filtered while hot. The black solid CuO was washed
twice with deionized water.

Synthesis of KHC2O4. 3.0 g of H2C2O4·2H2O (24 mmol) was dissolved in 40 mL of water in a 250-
mL beaker, and the solution was warmed to 85°C. To this warm solution, solid anhydrous K2CO3
(2.2 g, 16 mmol) was added in small portions. The resulting clear solution was stored for use in
synthesis of K2[Cu(C2O4)2].

Synthesis of a hot solution of K2[Cu(C2O4)2]. CuO prepared above was added to the KHC2O4
solution with vigorous stirring at 80°C. After complete dissolution of CuO, the mixture was rapidly
filtered while hot to remove any insoluble solids (Caution! The suction funnel and bottle should
be warmed beforehand). Then the hot filtrate (ca. 50 mL) was transferred to a 100-mL beaker and

29
used for the crystallization of K2[Cu(C2O4)2]·4H2O or K2[Cu(C2O4)2]·2H2O according to the
procedure shown below.

Synthesis of K2[Cu(C2O4)2]·2H2O: 25 mL of the hot solution of K2[Cu(C2O4)2]·was condensed by

evaporation to 5 mL in a hot water bath. When the residual solution was cooled in air for 10 min, the
light blue flat crystals of (1) are obtained and filtered immediately. Compound (1) was obtained in a
yield of 70 %.

Synthesis of K2[Cu(C2O4)2]·4H2O: 25 mL of the hot solution of K2[Cu(C2O4)2] was condensed by

evaporation to 20 mL in a hot water bath. This residual solution was cooled in air to room
temperature. The dark blue needle crystals obtained should be filtered immediately. The needle
crystals slowly decay at room temperature. Compound (2) was obtained with a yield of 80%.

Characterization

 Water content analyses. Finely ground (in a mortar) crystals of 1 or 2 (0.5 g) were placed in a
ceramic crucible. After heating the sample at 200°C for 30 min, the sample was cooled in air to
room temperature. Weigh the cooled dehydrated sample, calculate the water content, determine
the chemical formula of 1 and 2, and analyze the results.

 ThermoGravimetric Analysis

Reference:

A. Cui, J. Wei, J. Yang, and H. Kou, J. Chem. Educ. 2009, 86, 598-599.

30