FINAL REPORT

INORGANIC LABWORK
THE STABILITY OF TRANSTITION METAL COMPLEXES TO
CHLORIDE IONS

BY

Name

: Zulvana Anggraeni Harvian

Number of student

: 12/327756/PA/14373

Day,Dates

: Jumat, 6 Maret 2015

INORGANIC CHEMISTRY LABORATORY

FACULTY OF MATHEMATICS AND NATURAL SCIENCES
UNIVERSITAS GADJAH MADA
YOGYAKARTA
2015

RATIFICATION PAGE

LABWORK REPORT

THE STABILITY OF TRANSITION METAL COMPLEXES TO

CHLORIDE ION
Has been prepared and compiled by

Zulvana A. Harvian
12/327756/PA/14373

Has been collected and checked by Assistant

on March 17th 2015

Assistant

Practicant

Benny Wahyudianto

Zuvaana A. Harvian

THE STABILITY OF TRANSITION METAL COMPLEXES TO

CHLORIDE ION
ZULVANA ANGGRAENI HARVIAN
12/327756/PA/14373
ABSTRACT

The aims of the experiments is To learn the effect of chloride ion

concentration in the forming of chlor complex from iron metal ion and nickel in
ion exchange resin.
In the laboratory, the Anion Exchange Resin had already set up by the
assistant. So firstly prepared the HCL in some different concentration and
prepared the mixing solution of Fe3+,Co2+,Ni2+. Let the solution just one space up
to the border. HCL added again three times and put the eluate in different test
tubes labeled based on th concentration.
For checking the Fe3+ ion used KCNS the result would be dark red. For
checking the Co2+ ion used NH4CNS 10% in acetone and the result would be blue.
For checking the Ni2+ ion it needed to change the solution was being in basic
condition first by the addition of Ammonia and identified by the lakmus paper
then added the reagent of dimethyl gliocyn.
From the qualitative test was obtained that the Fe2+, Co2+, and Ni2+ metal
was eluted from resins by the HCl in concentration of 1 M. The metal that eluted
from the resins has unstable structure then it can not attached to the resins.
Keyword : anion exchange resin, Chloride ion, complex compound

THE STABILITY OF TRANSTITION METAL COMPLEXES TO

CHLORIDE IONS
I.)

THE AIMS OF EXPERIMENTAL SESSION

To learn the effect of chloride ion concentration in the forming of chlor
complex from iron metal ion and nickel in ion exchange resin

II.)

THEORITICAL BACKGROUND

Crystal Field Theory

The crystal field theory, in spite of age and relative simplicity, is a
powerful tool to elucidate many spectroscopic, magnetic, and
thermodynamic properties of transition-metal complexes and solidstate compounds. It finds application in the field of inorganic and
materials chemistry, catalysis, metallorganic, and bioinorganic
chemistry and a vast literature is available on the topic. (Morpurgo,
2007)
Notwithstanding the problem of spinorbit coupling, the crystal
field theory is based on two main approximations, namely the
weak-field and the strong-field approximations, depending on the
relative weight of interelectronic repulsion and crystal field as
energy contributions. Symmetry and spin multiplicity of the
spectroscopic terms of a given transition-metal complex are
independent of the field strength and depend only (i) on the dn
electron configuration of the transition metal involved and (ii) on
the geometrical properties (point group) of the complex itself. The
relative energy of the terms depends, instead, on the field strength
(Morpurgo, 2007)
In Crystal Field Theory, it is assumed that the ions are simple
point charges (a simplification). When applied to alkali metal ions
containing a symmetric sphere of charge, calculations of bond
energies are generally quite successful. The approach taken uses
classical potential energy equations that take into account the
attractive and repulsive interactions between charged particles (that
is, Coulomb's Law interactions). (Lancashire R. , 2000)

with

E the bond energy between the charges and

q1 and q2 are the charges of the interacting ions and

r is the distance separating them.

For example, consider a molecule with octahedral geometry.

Ligands approach the metal ion along the x, y, and z axes.
Therefore, the electrons in the dz2 and dx2y2 orbitals (which lie
along these axes) experience greater repulsion. It requires more
energy to have an electron in these orbitals than it would to put an
electron in one of the other orbitals. This causes a splitting in the
energy levels of the d-orbitals. This is known as crystal field
splitting. For octahedral complexes, crystal field splitting is
denoted

by o (or oct).

The

energies

of

the dz2 and dx2y2 orbitals increase due to greater interactions

with the ligands. The dxy, dxz, and dyz orbitals decrease with
respect to this normal energy level and become more stable.
(Lancashire R. , 2000)

c
o
n
s
e
q
u
e

nce of
Figure 1. To understand the splitting of d orbitals in a tetrahedral
crystal field, imagine four ligands lying at alternating corners of a
cube to form a tetrahedral geometry, as shown in the figure below.
The dx2-y2 and dz2 orbitals on the metal ion at the center of the cube
lie between the ligands, and the dxy, dxz, and dyz orbitals point
toward the ligands. As a result, the splitting observed in a
tetrahedral crystal field is the opposite of the splitting in an
octahedral complex.
Crystal Field Theory is that the distribution of electrons in the d
orbitals may lead to net stabilization (decrease in energy) of some
complexes depending on the specific ligand field geometry and
metal d-electron configurations. It is a simple matter to calculate
this stabilization since all that is needed is the electron
configuration and knowledge of the splitting patterns. The Crystal
Field Stabilization Energy is defined as the energy of the electron
configuration in the ligand field minus the energy of the electronic
configuration in the isotropic field. (Lancashire, 1998)
CFSE=E=E ligand fieldE isotropic field
The CSFE will depend on multiple factors including:

Geometry (which changes the d-orbital splitting patterns)

Number of d-electrons

Spin Pairing Energy

Ligand character (via Spectrochemical Series)

Anion Exchange Resin

Ion exchange resins are polymers that are capable of
exchanging particular ions within the polymer with ions in a

solution that is passed through them. This ability is also seen in

various natural systems such as soils and living cells. The synthetic
resins are used primarily for purifying water, but also for various
other applications including separating out some elements. Ion
exchange materials are insoluble substances containing loosely
held ions which are able to be exchanged with other ions in
solutions which come in contact with them. These exchanges take
place without any physical alteration to the ion exchange material.
Ion exchangers are insoluble acids or bases which have salts which
are also insoluble, and this enables them to exchange either
positively charged ions (cation exchangers) or negatively charged
ones (anion exchangers). (Alchim, 2003)

F
i
gure 2 : Cation Exchange Resin Schematic Showing Negatively
Charged Matrix and Exchangeable Positive Ions
Physical Properties of Resins Conventional ion exchange
resins consists of a cross-linked polymer matrix with a relatively
uniform distribution of ion-active sites throughout the structure. A
cation exchange resin with a negatively charged matrix and
exchangeable positive ions (cations) is shown in Figure 2. Ion
exchange materials are sold as spheres or sometimes granules with

a specific size and uniformity to meet the needs of a particular

application. The majority are prepared in spherical (bead) form,
either as conventional resin with a polydispersed particle size
distribution from about 0.3 mm to 1.2 mm (50-16 mesh) or as
uniform particle sized (UPS) resin with all beads in a narrow
particle size range. In the waterswollen state, ion exchange resins
typically show a specific gravity of 1.1-1.5. The bulk density as
installed in a column includes a normal 35-40 percent voids
volume for a spherical product. Bulk densities in the range of 560960 g/l (35-60 lb/ft3) are typical for wet resinous products.
Chemical Properties of Resins Capacity. Ion exchange
capacity may be expressed in a number of ways. Total capacity,
i.e., the total number of sites available for exchange, is normally
determined after converting the resin by chemical regeneration
techniques to a given ionic form. The ion is then chemically
removed from a measured quantity of the resin and quantitatively
determined in solution by conventional analytical methods. Total
capacity is expressed on a dry weight, wet weight or wet volume
The water uptake of a resin and therefore its wet weight and wet
volume capacities are dependent an the nature of the polymer
backbone as well as an the environment in which the sample is
placed. (R.M Wheaton, L.J Lelvere, 2000)
Strong Base Anion-Exchange Resins. The amine resins
that had been developed with

compounds

such as

m-

phenylenediamine were capable of anion exchange only if the

amine was protonated; that limited their use to acidic solutions.
The presence of covalently bound quaternary ammonium sites on
the polymer allowed anion exchange from neutral and alkaline
solutions since the positive charge on the nitrogen did not depend
upon protonation. These resins were referred to as strong base
resins in order to distinguish them from the weak base resins that
had tertiary amine sites in alkaline solutions. Amberlite IRA-400

was the strong base resin produced by the Rohm & Haas Co.11
The affinity for a series of anions with this resin was determined to
be: citrate > sulfate > oxalate > iodide > nitrate > chromate >
bromide > thiocyanate > chloride > formate > hydroxyl > fluoride
> acetate. Dowex 1 and Dowex 2 were the quaternary amine resins
produced by the Dow Chemical Co. and reported to remove
carbonic acid, silicic acid, amino acids, H2S, and phenol from
aqueous solutions.12 Dowex 2 was applied in a plant that
processed 2,500,000 gallons of water per day and it reduced the
silica level to <0.05 ppm (Alexandratos, 2009)

III.)

EXPERIMENTAL DESIGN
i.)

Tools and Material

In tools, it needed one set of anion exchange resin as the main
equipment, some of beaker glasses for putting the solution, then it
needed twetleve test tubes for testing the identification of metal
ions, for measure the solution it also needed volumetric glass and
one piece of glass.
For the materials, it used HCL in some different concentration of
9 M, 5 M, 2 M, and 1 M.Then the Fe3+ solution, Co2+ solution,
Ni2+ solution for the testing materials, then KCNS solution,
NH4CNS 10% in acetone, ammonia solution for making the
solution became base and dimethyl gliocyn,

ii.) Procedures
In the laboratory, the Anion Exchange Resin had already set up by
the assistant. So firstly prepared the HCL for 50 mL in some
different concentration started from 1 M,5 M and 9 M and
prepared the 2 mL of mixing solution of Fe3+,Co2+,Ni2+. In the
resin already put by 2 M of HCL so poured the 9 M of HCL until
1 space of the border resins material. Then added 2 mL of the
mixing solution. Let the solution just one space up to the border.
HCL 9 M added again but in 5 mL in three times and put the
eluate in different test tubes labeled by 5-1,5-2,5-3.With the same
treatment, it done by 5 M and M of HCL in 5 mL but did in four
time.After all of it, Check the metal ion but dropped the solution
in every test tube with the some solution addition on the piece of
glass.
For checking the Fe3+ ion used KCNS 0.1 M and the result would
be dark red. For checking the Co2+ ion used NH4CNS 10% in
acetone and the result would be blue. For checking the Ni2+ ion it
needed to change the solution was being in basic condition first by
the addition of Ammonia 15 M and identified by the lakmus paper
then added the reagent of dimethyl gliocyn.

IV.)

RESULT AND DISCUSSION

i.)

Table of Result
Concentration

/ Fe3+

Co2+

Ni2+

Metal Ions
9 M (1)

No color

No color

+1

9 M (2)

No color

No color

+1

9 M (3)

No color

+1

+1

5 M (1)

No color

No color

+1

5 M (2)

No color

No color

+1

5 M (3)

No color

No color

+2

5 M (4)

No color

No color

+2

1 M (1)

+1

+2

No color

1 M (2)

+2

+3

No color

1 M (3)

+3

+3

+2

1 M (4)

+4

Red +3

+4

Table 1 : Table of Result

ii.)

Discussions
Ion

exchange

materials

are

insoluble

substances

containing loosely held ions which are able to be exchanged

with other ions in solutions which come in contact with them.
These exchanges take place without any physical alteration to
the ion exchange material. Ion exchangers are insoluble acids
or bases which have salts which are also insoluble, and this
enables them to exchange either positively charged ions (cation
exchangers) or negatively charged ones (anion exchangers).
The affinity of sulphonic acid resins for cations varies with the
ionic size and charge of the cation. Generally the affinity is
greatest for large ions with high valency.

Suppose a resin has greater affinity for ion B than for ion
A. If the resin contains ion A and ion B is dissolved in the water
passing through it, then the following exchange takes place, the
reaction

proceeding

to the right (R

represents

the resin):
When the resin exchange capacity nears exhaustion, it will
mostly be in the BR form. A mass action relationship applies
where the bracketed entities represent concentrations:
[
[

][ ]
][ ]

Q is the equilibrium quotient, and is a constant specific for

the pair of ions and type of resin. This expression indicates that if a
concentrated solution containing ion A is now passed through the
exhausted bed, the resin will regenerate into the AR form ready for
re-use, whilst ion B will be eluted into the water. All large scale
applications for ion exchange resins involved such exhaustion and
regeneration cycles.

. Ion-exchange resins were modified in order to expand

their applicability by binding a metal ion onto a resin through ion
exchange and then reducing it to the zerovalent metal.
The complex is less stable will be eluted (detached) at high
HCl concentration 9 M, if the concentration of chloride ions then
lowered for example to 5 M, the complex chloride ion equilibrates
with aqua complex (ligand water molecules) that are not strongly
bound by the resin and can be separated out of the column. While
the metal ions that form the most stable complexes will not elute
until the chloride ion concentration reached 1 M.
For the explanation based on the reaction above :
1. HCl Concentration at 9 M
a. Fe Metal Ion
[Fe(H2O)6]3+ + 6 Cl- [FeCl6]3-

b. Ni Metal Ion
[Ni(H2O)6]2+ + 6 Cl- [NiCl6]4- + 6
H2O

c. Co Metal Ion
[Co(H2O)6]2+ + 6 Cl- [CoCl6]4- + 6 H2O

2. HCl Concentration at 1 M
a. Fe Metal Ion
[FeCl4]- + 6 H2O [Fe(H2O)6]3+ + 4 Cl-

b. Ni Metal Ion
[NiCl4]- + 6 H2O [Ni(H2O)6]2+ + 4 Cl-

c. Co Metal Ion
[CoCl4]- + 6 H2O [Co(H2O)6]2+ + 4 Cl-

3. HCl Concentration at 5 M
They reached equilibrium because the amount of ligands H2O
and Cl are the same, so that the metal ions formed chlor
complex and aqua complex.

The LFSE of the complexes below are resulted as [FeCl6]3complex is 0 and the PEB = 0, for complex [CoCl6]4- LFSE = -1,2
and PEB = 2. And for complex [NiCl6]2- LFSE = -0,8 and PEB = 3.
Those are for the concentration of 9 M but for 5 M and 1 M resuted
LFSE value for [Fe(H2O)6]3+ complex is -2,0 and PEB = 2, for
[C(H2O)6]2+ complex LFSE = -1,8 and PEB = 3, and for
[Ni(H2O)6]2+ complex LFSE = -1,2 and PEB = 3. Based on
experimental data proved that Ni is the less stable and the order
obtained is Fe3+ > Co2+ > Ni2+
Based on experimental data the metal ion mostly detected
at the concentration of 1 M because at that concentration happened
equilibrium between Chlor ligand and aqua ligands. So that the
metal detected easily and removed easily from the resin. It has the
same as the related theory.

V.)

CONCLUSIONS
The aims of the experiments is To learn the effect of chloride ion
concentration in the forming of chlor complex from iron metal ion and
nickel in ion exchange resin so that based on experimental data and
from the tes obtained that the Fe2+, Co2+, and Ni2+ metal was eluted
from resins by the HCl in concentration of 1 M. The metal that eluted
from the resins has unstable structure then it can not attached to the
resins.

VI.)

REFERENCES

Alchim, D. (2003). Ion Exchange Resin. Article of Drew New Zealand.

Alexandratos, S. D. (2009). Ion-Exchange Resins: A Retrospective from
Industrial and Engineering Chemistry Research. Ind.Eng.Chem.Res, 4.
Lancashire, P. R. (1998, December). Crystal Field Stabilization Energy. Retrieved
March Sunday 8th, 2015, from ChemWiki:
http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Field_Theory/I
ntroduction_to_Crystal_Field_Theory/Crystal_Field_Stabilization_Energy
Lancashire, R. (2000, - -). Crystal Field Theory. Retrieved March Sunday 8th,
2015, from CHEMWIKI:
http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Field_Theory/
Crystal_Field_Theory
Morpurgo, S. (2007). Group Theory and Crystal Field Theory. Journal of
Chemical Education.
R.M Wheaton, L.J Lelvere. (2000). Ion Exchange Resin. Amsterdam: Dow Liquid
Seperation Office.