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INORGANIC CHEMISTRY I
LAB REPORT 3
Name
: Nur Alisa Binti Muhamad Yamin
Matric No.
: 1612724
Partners Name
: Noriliya Aina Binti Norhisham
Partners Matric No. : 1619150
Kulliyah
: Science (Applied Chemistry Batch 161)
Subject Code
: SCH 1223 (Inorganic Chemistry I)
Semester
: 1, 2016/17
Lecturer
: Dr. Raihan Binti Musa
Title of Experiment
Objective
The objective of this experiment is to understand the concept of coordination chemistry and the ability
of metal ions or atoms from transition metals to coordinate with ligands, thus forming complex ions
that are capable of emitting a variety of colours.
Introduction
Coordination chemistry is an area in chemistry that focuses on the feature of coordination compounds
where it involves coordinate bonds between Lewis acids and bases. In coordination chemistry, metal
atoms or ions act as the Lewis acids and any species that has one or more unshared pairs of electrons
act as the Lewis base. These species are also referred to as ligands. However, electron pair donors can
also include neutral molecules such as H2O and NH3. These electron pair donors will donate their
electrons to the Lewis acids to form coordinate bonds [1] (House, 2008).
Transition metals are unique metals in a sense that they have incomplete or partially filled d-orbitals
which allows them to potentially reveal various colours as metal complexes. These metals are able to
emit colours to the naked eyed due to the complex ions formed when the metal atoms or ions form
coordinate covalent bonds with ligands[2] (Lawrance, 2010).
Ligands can be defined as neutral molecules or ions with lone pairs than can attach themselves directly
to the central metal atom or ion through coordinate covalent bonds. Ligands can attach to the metal
through a single atom (monodentate) or through two or more atoms (bidentate, tridentate, etc). Ligand
strength can be assessed by referring to the spectrochemical series of ligands. Ligands are able to help
raise the energy or promote one or more electron in the lower d-orbital of the metal atom or ion to a
higher level d-orbital, thus absorbing certain colours of light on the electromagnetic spectrum and
revealing the colour that was not absorbed[3] (Miessler, Fischer, & Tarr, 2013).
Complex metal compounds can be categorized as labile and inert whereby labile means that the
coordinate covalent bonds between metal-ligands are easier to break and inert means the opposite.
Generally, metals with higher charges are expected to be more basic and stronger Lewis acids, thus
they should bind to ligands more strongly.
Although the spectrochemical series of ligands is usually used to determine the strength of the ligand,
it does not necessarily explain every ligand exchange phenomenon. Electronegativity of the ligand
also plays a role. If the metal possesses a positive charge, it is more likely to be attracted to a negative
-
ion rather than a positive ion or a neutral compound. In a mixture with Cu 2+ ions, if the ligand Cl was
present alongside the ligand H2O, despite H2O being placed higher in the spectrochemical series, the
-
metal ion would be more attracted to form a coordinate covalent bond with Cl due to its
complementary charge with the copper ions.
In this experiment, various solvents are mixed to prove the formation of complex ions based on the
colour changes of the mixture. The transition metals involved are copper, iron, cobalt, chromium and
nickel. Certain solid anhydrous metal complexes are also compared to demonstrate the difference of
colours due to the metals coordinate covalent bonds with different ligands.
solution
15 M of ammonia solution
Ethylenediamine solution
12 M of HCl solution
solution
Dimethylgloxime solution
potassium sulfate
Measuring cylinder
Droppers
Spatula
Potassium chromium
disulfate solution
0.1 M of Potassium
ferrocyanide solution
chloride
6 M of NaOH solution
Water
1,10-phenanthroline
solid
Ethanol solution
solution
2. The first test tube was added with a few drops of ammonia solution while the second test tube
was added with a few drops of ethylenediamine. The third test tube was added with a solution
of dimethylgloxime.
3. The observations for the final solutions in each test tube were recorded.
Cobalt (II) Complexes:
1. Containers containing the solids [Co(H2O)6]Cl2 and [Co(H2O)6](NO3)2 were located and their
appearance were observed and recorded.
2. Two small test tubes were obtained. The first test tube was added with 0.5mL of ethanol and
the second was added with 0.5mL of water.
3. Both test tubes were added with a small crystal solid of [Co(H2O)6]Cl2.
4. The observations for the colour of the resulting solutions were recorded.
4. Both test tubes were then added with 0.5mL of 0.1M of CoCl2 solution (approximately 10
drops).
5. To one test tube, 12M of HCl was added dropwise until the colour change appeared
completely. To the other test tube, 10-15 drops of saturated KSCN solution was added.
6. The observations were recorded.
Chromium (III) Complexes:
1. Containers containing the solids KCr(SO4)212H2O and CrCl36H2O were located.
2. 0.5mL of water was added respectively to two small test tubes.
3. A very small portion of KCr(SO4)212H2O was added to the first test tube and a very small
portion of CrCl36H2O was added to the second test tube.
4. All observations were recorded.
Colour
CuSO45H2O
Blue
CuCl22H2O
Turquoise green
Pairs of Mixtures
0.1M of copper (II) sulfate +
15M of NH3
0.1M of copper (II) sulfate +
Ethylenediamine
0.1M of copper (II) sulfate +
12M of HCl (excess)
0.1M of copper (II) sulfate +
6M of NaOH
0.1M of copper (II) sulfate +
NaNO2
0.1M of copper (II) sulfate +
0.1M of K4[Fe(CN)6]
Colour of
Copper (II) sulfate
Light blue
Final Colour of
Solution
Dark blue
Complex Ion
Formed
[Cu(NH3)4(H2O)2]2+
Light blue
[Cu(H2O)4(en)]2+
Light blue
Yellow
[CuCl4]2-
Light blue
Baby blue
[Cu(H2O)4(OH)2]
Light blue
Dark green
[Cu(NO2)4]2-
Light blue
Dark brown
Cu2[Fe(CN)6]
(Hexahydrate)
Colour
Pale Yellow
[Fe(H2O)6]SO4H2O
Milky yellow
[Fe(H2O)6]
Pairs of Mixtures
0.1M of Fe(NO3)3 +
KSCN
0.1M of Fe(NO3)3 +
K4[Fe(CN)6]
2+
Blood red
[Fe(phen)3]2+
Yellow
Final Colour of
Solution
Dark red
Complex Ion
Formed
[Fe(H2O)5(SCN)]2+
Yellow
Dark blue
Fe4[Fe(CN)6]3
Final Colour of
Solution
Pale blue
Pale green
Light purple
[Ni(H2O)4(en)]2+
Pale green
Pink
Ni(dmg)2
[Ni(NH3)6]2+
Colour
[Co(H2O)6]Cl2
Purple
[Co(H2O)6](NO3)2
Orangish red
Pairs of Mixtures
[Co(H2O)6]Cl2 +
Ethanol
[Co(H2O)6]Cl2 +
Water
Red
[Co(H2O)6]2+
Pairs of Mixtures
Final Colour of
Solution
Light purple
Pale red
Violet
[Co(SCN)4]2-
0.1M of CoCl2 +
12M of HCl
0.1M of CoCl2 +
KSCN
[CoCl4]2-
Dark violet
Final Colour of
Solution
Dark blue
KCr(SO4)212H2O
+ Water
CrCl36H2O +
Water
Dark green
Dark green
[Cr(H2O)5Cl]2+
[Cr(H2O)6]3+
Discussion
There are many properties that need to be determined and considerations to be made before one can
relate and explain why metal-ligands behave the way they do when in contact with a different ligand in
the same solution. However, in this experiment, I will stress on three main reasons in regards to the
transition metal and their metal complexes.
Firstly, as mentioned earlier, electronegativity plays an important role in determining which ligand is
more dominant in the presence of a metal atom or ion. Metal ions are positively charged, thus they are
more attracted to the negatively charged ligands.
Secondly, the denticity of ligands is also taken into consideration. Denticity can be defined as the
number of donor groups in a ligand that binds to the central atom in a coordination complex. When
only one atom in a ligand binds to the metal, the denticity is one, thus the ligand is considered to be
monodentate. Ligands that have more than one bonded atom are often referred to as polydentate or
multidentate. Generally, the stability of a metal complex is proportional to the denticity of ligands.
Ligands with higher denticity bind more strongly to metal ions or atoms than ligands with low
denticity.
Lastly, it is a given that when dealing with ligands, one must refer to the spectrochemical series of
ligands. The spectrochemical series is arranged from the low-field (weaker) ligands to the high field
(stronger) ligands. Clearly, the low-field ligands are -donors while the high-field ligands are acceptors. The neutral ligands that are neither donors nor acceptors, remain in the middle (H 2O and
NH3).
The Spectrochemical Series:
I < Br < S2 < SCN < Cl < NO3 < N3 < F < OH < C2O42 < H2O < NCS < CH3CN < py
(pyridine) < NH3 < en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) <
NO2 < PPh3 < CN < CO
Based on the three reasons mentioned, the answers to the formation of complex ions throughout the
experiment can be determined as tabulated below:
Transition
Equation
Metals
Copper
[Cu(H2O)6]2++ 4NH3 [Cu(NH3)4(H2O)2]2++ 4H2O
Iron
Nickel
Reason
NH3 is a better proton
acceptor than H2O
according to the
spectrochemical series
Ethylenediamine is a better
proton acceptor than H2O
according to the
spectrochemical series
Cl ion is more
electronegative than H2O
OH ion is more
electronegative than H2O
NO2- ion is more
electronegative than H2O
[Fe(CN)6] makes a more
stable complex than H2O
due to its higher denticity
Spectator ions and atoms
were removed during
hydration of solids
1,10-phenanthroline is a
better proton acceptor than
H2O according to the
spectrochemical series
SCN ion is more
electronegative than H2O
[Fe(CN)6] makes a more
stable complex than H2O
due to its higher denticity
NH3 is a better proton
acceptor than H2O
according to the
spectrochemical series
Ethylenediamine is a better
proton acceptor than H2O
according to the
spectrochemical series
Dimethylgloxime makes a
more stable complex than
H2O due to its higher
denticity
Transition
Equation
Metals
Cobalt
When adding water/ethanol to cobalt metal ion/atom:
[Co(H2O)6]2+ + 4Cl [CoCl4]2- + 6H2O
Reason
The equation shifts
according to Le Chateliers
principle when water or
ethanol is added to solid
[Co(H2O)6]Cl2
Cl ion is more
electronegative than H2O
SCN ion is more
electronegative than H2O
The chromium solid is
dissolved into its ionic
complex form
Not all the chromium solid
is able to dissolve into its
ionic complex form most
likely due to the inertness
of the Cr3+ ion. It might
take awhile for the ionic
complex to form
completely
When comparing the solids of certain metal complex compounds, different colours can be seen.
CuSO45H2O Blue
[Co(H2O)6]Cl2 Purple
As mentioned earlier, complex compounds involves the d-orbitals of the transition metals, specifically
the d-d transitions. When ligands help raise the energy of one or more electrons in the d-orbital, it
creates a space between the lower energy level and the higher energy level or d-orbitals . This space is
what causes the transition metal to reflect its colours because this space corresponds to the
wavelengths visible in normal light. According to the wavelength chart (Refer Appendix Fig.3), the
possible wavelengths of the above solids are:
CuSO45H2O 620nm -700nm
CuCl22H2O 580nm -700nm
[Co(H2O)6]Cl2 560nm - 580nm
[Co(H2O)6](NO3)2 430nm - 560nm
Application
Complex compounds has various applications in both our daily lives and in the science industry. For
example, in our blood, the heme unit in hemoglobin involves a rigid chelating ligand. H2O or O2 or
CO can be the 6th ligand. The coordinate-covalent bonds in the heme exist between the central iron
atom and the nitrogens and porphyrin, thus the metal is complex is the iron porphyrin complex. This
complex is well known for its red pigment in the red blood cell.
Other applications would be the chlorophyll that helps to emit green pigments in the leaves.
Chlorophyll is a magnesium porphyrin complex. The porphyrin acts as a ligand to the magnesium
metal ions.
Conclusion
In conclusion, this experiment proves the formation of coordination complex. Transition metals are
indeed able to form coordinate covalent bonds with ligands to form complex ions. Ligands help to
raise the energy of one or more electrons in the partially filled d-orbital of the transition metal atoms
or ions. The complex compounds emit different colours due to the different visible wavelengths from
the
space
between
the
metals
higher
level
d-orbitals
and
lower
level
d-orbitals.
References
1) House, J. E. (2008). Inorganic Chemistry (1st ed.). Bloomington: Academic Press.
2) Lawrance, G. A. (2010). Introduction to Coordination Chemistry. Callaghan: John Wiley and Sons,
Ltd.
3) Miessler, G. L., Fischer, P. J., & Tarr, D. A. (2013). Inorganic Chemistry. Upper Saddler River:
Prentice Hall.
4) Shriver, D., & Atkins, P. (2001). Inorganic Chemistry (3rd ed.). Oxford: Oxford University Press.
5) Silberberg, M. S. (2013). Chemistry: The Molecular Nature of Matter and Change (Global ed.).
New York, United States of America: McGraw-Hill Global Education Holdings.
6) Zundahl, S. (2005). Chemical Principles (5th ed.). Boston: Houghton Mifflin Company.
Appendix