Ligand Field Strength
Ligand Field Strength
Ligand Field Strength
TITLE OF EXPERIMENT
Ligand Field Strength
B. DATE OF EXPERIMENT
Wednesday, 29th October 2019 / 09:30 – 12:00 WIB
C. PURPOSE OF EXPERIMENT
1. Studying the difference in ligand field strength between ammonia and water
ligands
2. Knowing how to find the wavelength at maximum absorbance
3. Knowing the variables that affect the maximum wavelength
D. BASIC THEORIES
1. Crystal Field Theory
Crystal field theory is one of the simplest models for explaining the
structures and properties of transition metal complexes. The theory is based
on the electrostatics of the metal-ligand interaction, and so its results are
only approximate in cases where the metal-ligand bond is substantially
covalent. But because the model makes effective use of molecular
symmetry, it can be surprisingly accurate in describing the magnetism,
colors, structure, and relative stability of metal complexes.
Consider a positvely charged metal ion such as Fe3+ in the "field" of
six negatively charged ligands, such as CN-. There are two energetic terms
we need to consider. The first is the electrostatic attraction between the
metal and ligands, which is inversely proportional to the distance between
them:
The second term is the repulsion that arises from the Pauli exclusion
principle when a third electron is added to a filled orbital. There is no place
for this third electron to go except to a higher energy antibonding orbital.
This is the situation when a ligand lone pair approaches an occupied metal
d-orbital:
1 | (L i g a n d F i e l d S t r e n g t h )
(Janes, Moore, & Open University., 2004)
Figure 1. A Fe3+ ion has five d-electrons, one in each of the five d-orbitals
In a spherical ligand field, the energy of electrons in these orbitals rises
because of the repulsive interaction with the ligand lone pairs. The orbitals
split into two energy levels when the ligands occupy the vertices of an
octahedron, but the average energy remains the same.
The energy difference between the eg and t2g orbitals is given the
symbol ΔO, where the "O" stands for "octahedral." We will see that this
splitting energy is sensitive to the degree of orbital overlap and thus depends
on both the metal and the ligand. Relative to the midpoint energy (the
barycenter), the t2g orbitals are stabilized by 2/5 ΔO and the eg orbitals are
destabilized by 3/5 ΔO in an octahedral complex (Janes et al., 2004).
2 | (L i g a n d F i e l d S t r e n g t h )
What causes the d-orbitals to split into two sets? Recall that the d-
orbitals have a specific orientation with respect to the Cartesian axes. The
lobes of the dxy, dxz, and dyz orbitals (the t2g orbitals) lie in the xy-, xz-, and
yz-planes, respectively. These three d-orbitals have nodes along the x-, y-,
and z-directions. The orbitals that contain the ligand lone pairs are oriented
along these axes and therefore have zero overlap with the metal t2g
orbitals. It is easy to see that these three d-orbitals must be degenerate by
symmetry. On the other hand, the lobes of the dz2 and dx2-y2 orbitals (the eg
orbitals) point directly along the bonding axes and have strong overlap with
the ligand orbitals. While it is less intuitively obvious, these orbitals are also
degenerate by symmetry and have antibonding character (Miessler & Tarr,
2004).
2. Spectrochemical series
Strong and weak field ligands. The spectrochemical series ranks
ligands according the energy difference ΔO between the t2g and eg orbitals
in their octahedral complexes. This energy difference is measured in the
spectral transition between these levels, which often lies in the visible part
of the spectrum and is responsible for the colors of complexes with partially
filled d-orbitals. Ligands that produce a large splitting are called strong field
3 | (L i g a n d F i e l d S t r e n g t h )
ligands, and those that produce a small splitting are called weak field
ligands.
An abbreviated spectrochemical series is:
4 | (L i g a n d F i e l d S t r e n g t h )
Important trends in ΔO:
• Co3+ complexes have larger ΔO than Co2+ complexes with the same
ligand. This reflects the electrostatic nature of the crystal field splitting.
• Rh3+ complexes have larger ΔO than Co3+ complexes. In general,
elements in the 2nd and 3rd transition series (the 4d and 5d elements)
have larger splitting than those in the 3d series.
• For a given metal in one oxidation state (e.g., Co3+), the trend in ΔO
follows the spectrochemical series. Thus ΔO is larger for [Co(CN)6]3-,
which contains the strong field CN- ligand, than it is for [Co(H2O)6]3+
with the weak field ligand H2O.
Figure 4. Complementary colors are across the color wheel from each
other.
5 | (L i g a n d F i e l d S t r e n g t h )
[Co(CN)6]4-, looks red, absorbs in the violet and ultra-violet part of the
spectrum. This is consistent with the idea that CN- is a stronger field ligand
than NH3, because the energy of a UV photon is higher than that of a red-
orange photon.
Substances
1. Cu2+ soution (0,1 M) ± 6 mL
2. Ammonium 1 M ± 7,5 mL
3. Aquadest (H2O) sufficiently
6 | (L i g a n d F i e l d S t r e n g t h )
F. LANES WORK
1. Absorbance of Cu2+ diluted into water
2 mL Cu2+ 0,1M
Cu Solution
The wavelength
Reactions:
a. Cu2+ + H2O(l) → Cu2+ + H2O(l)
2 mL Cu2+ 0,1M
The wavelength
Reactions:
a. Cu2+ + H2O(l) → Cu2+ + H2O(l)
b. [Cu(H2O)6]2+(aq) + 2NH3(aq) → [Cu(H2O)4(NH3)2]2+(aq) + H2O(l)
7 | (L i g a n d F i e l d S t r e n g t h )
c. Absorbance of Cu2+ diluted into ammonium (75:25)
2 mL Cu2+ 0,1M
The wavelength
Reactions:
a. Cu2+ + H2O(l) → Cu2+ + H2O(l)
b. [Cu(H2O)6]2+(aq) + 2NH3(aq) → [Cu(H2O)4(NH3)2]2+(aq) + H2O(l)
Aquadest
8 | (L i g a n d F i e l d S t r e n g t h )
G. OBSERVATION RESULT
Experiment Result
No. Procedure Prediction/Reaction Conclusion
Before After
1. Absorbance of Cu2+ diluted into water • Cu2+ 0.1 M • Cu2+ + H2O = light blue Reactions: The Dq of this
- As much as 2 mL of Cu2+ 0,1 M solution = light (-) solution Cu2+ + H2O(l) → Cu2+ + H2O(l) experiment is
entered into measured flask 10 mL blue solution • Wavelenght = 812.0 nm 35.2 kkal/mol
- Diluted using water until the sign • Aquadest = ▪ Absorbance = 0.2756
- Formed Cu Solution colorless solution
- Observed the absorbance by using ▪ Ammonium 0.1 M
spectrophotometer UV-VIS or solution =
wavelength 700-850 nm colorless solution
- If the absorbance bigger than 1, dilute
it until the absorbance maximum is 1
- Observed the graph
- Obtained the wavelength
2. Absorbance of Cu2+ diluted into • Cu2+ solution = • Cu2+ + ammonium = Reactions: The Dq of this
ammonium (50:50) light blue solution dark blue solution (+) a. Cu2+ + H2O(l) → Cu2+ + experiment is
- As much as 2 mL of Cu2+ 0,1 M H2O(l) 46.87 kkal/mol
entered into measured flask 10 mL
9 | (L i g a n d F i e l d S t r e n g t h )
Experiment Result
No. Procedure Prediction/Reaction Conclusion
Before After
- Added 5 mL of ammonium • Aquadest = • Cu2+ + ammonium + b. [Cu(H2O)6]2+(aq) + 2NH3(aq)
- Diluted using water until the sign colorless solution water = dark blue → [Cu(H2O)4(NH3)2]2+(aq) +
- Formed Cu Solution : ammonium ▪ Ammonium 0.1 M solution (+) H2O(l)
(50:50) solution = • Wavelenght = 610.0 nm
- Observed the absorbance by using colorless solution ▪ Absorbance = 0.5197
spectrophotometer UV-VIS or
wavelength 350-700 nm
- If the absorbance bigger than 1, dilute
it until the absorbance maximum is 1
- Observed the graph
- Obtained the wavelength
3. Absorbance of Cu2+ diluted into • Cu2+ solution = • Cu2+ + ammonium = Reactions: The Dq of this
ammonium (75:25) light blue solution dark blue solution (+) a. Cu2+ + H2O(l) → Cu2+ + experiment is
- As much as 2 mL of Cu2+ 0,1 M • Aquadest = • Cu2+ + ammonium + H2O(l) 46.34 kkal/mol
entered into measured flask 10 mL colorless solution water = dark blue b. [Cu(H2O)6]2+(aq) + 2NH3(aq)
- Added 2,5 mL of ammonium solution (+) → [Cu(H2O)4(NH3)2]2+(aq) +
- Diluted using water until the sign H2O(l)
10 | (L i g a n d F i e l d S t r e n g t h )
Experiment Result
No. Procedure Prediction/Reaction Conclusion
Before After
- Formed Cu Solution : ammonium ▪ Ammonium 0.1 M • Wavelenght = 617.0 nm
(75:25) solution = ▪ Absorbance = 0.3840
- Observed the absorbance by using colorless solution
spectrophotometer UV-VIS or
wavelength 350-700 nm
- If the absorbance bigger than 1, dilute
it until the absorbance maximum is 1
- Observed the graph
- Obtained the wavelength
4. Absorbance of blank solution • Aquadest = • Wavelenght = 400.0 nm
- Aquadest enetered into cuvete colorless solution ▪ Absorbance = 0.00
- Observed the absorbance by using
spectrophotometer UV-VIS or
wavelength 400-600 nm
- Noted the maximum absorbance
- Obtained maximum absorbance of
aquadest
11 | (L i g a n d F i e l d S t r e n g t h )
H. ANALYSIS
The "Ligand Field Strength" experiment aims to determine the difference
in ligand field strength between ammonium ligands and water in Cu as the
central metal. There are 3 variations of the solvent used in the test solution. This
aims to be able to explain the effect of maximum wavelength, both seen from
the type of ligand that is bound or the number of ligands that will be substituted
by Cu metal. To find out the maximum wavelength of each test solution UV-
Vis spectrophotometers are used at different wavelengths according to the color
of the solution formed with the color of the complement. Furthermore, the
maximum value obtained will be substituted with the equation:
1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙 1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Formula 10Dq = V × 349.75 𝑐𝑚−1 = 𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥 × 349.75 𝑐𝑚−1
12 | (L i g a n d F i e l d S t r e n g t h )
In this solution water functions as a ligand, while Cu is the central
metal. If the bond is between a metal and a ligand, the compound formed is
called a complex compound. Where the complex compound that is formed
is [Cu(H2O)6]2+ or hexaaquocopper ion (II). This shows that common ions
are in aqueous solution (and some are also in a crystalline state) in
aquocomplex form. The reaction is shown as follows:
Cu2+(aq) + 6H2O(l) → [Cu(H2O)6]2+(aq)
Hybridization of complex compounds above according to VBT
(Valence Bond Theory) where there are 6 H2O ligands as follows.
H2O H2O H2O H2O H2O H2O
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 812 × 349.75 𝑐𝑚−1
= 35.2 kkal/mol
The Dq value obtained from the first test solution is low, this is
because there is only substitution of H2O ligands, which is an aquocomplex
form. So it can be concluded that the ligand field strength of H2O is small,
where this low energy will make splitting eg and t2g orbitals smaller. Small
splitting indicates that the incoming ligand is a weak ligand.
13 | (L i g a n d F i e l d S t r e n g t h )
2. Absorbance of Cu2+ diluted into ammonium (50:50)
In the second test solution, prepare 2 mL of Cu2+ 0.1M solution which
is put into a 10 mL volumetric flask, the solution is light blue. Then added
with 5 mL of ammonium (by the ratio 50:50), formed dark blue solution .
Then diluted with distilled water until its reach the mark. Dilution produces
a dark blue solution where the blue color formed absorbs the
complementary color of orange with a wavelength of around 590-620 nm.
The volume of distilled water used in the dilution process is related to the
number of ligands to be substituted by Cu metal.
In this solution water and ammonia functions as a ligand, while Cu is
the central metal. If the bond is between a metal and a ligand, the compound
formed is called a complex compound. Where the complex compound that
is formed is [Cu(H2O)3(NH3)3]2+ or triaminatriaquo copper(II) ion. Because
of the addition of water and ammonia in the same ratio, stable Cu2+ ions in
water [Cu(H2O)6]2+ are substituted by 3 H2O ligands and 3 NH3 ligands. The
reaction is shown as follows:
[Cu(H2O)6]2+(aq) + 3NH3(aq) → [Cu(H2O)3(NH3)3]2+(aq)
Hybridization of complex compounds above according to VBT
(Valence Bond Theory) where there are 3 H2O and 3 NH3 ligands as follows.
H2O H2O H2O NH3 NH3 NH3
3.
14 | (L i g a n d F i e l d S t r e n g t h )
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 610 × 349.75 𝑐𝑚−1
= 46.87 kkal/mol
The amount of Dq value of the second test solution is different from
the first test solution, where the Dq energy of the second test solution will
be greater that is 46.87 kkal / mol. From the comparison of the Dq energy
of the first and second test solutions, the Dq energy of the second test
solution is greater because of the substitution of NH3 ligands, causing Dq
energy to increase, whereas in the first test solution there is only H2O ligand
substitution. So it can be concluded that the strength of NH3 ligand field is
greater than H2O because it causes a large Dq energy, where this large
energy will make splitting eg and t2g orbitals greater. Large splitting
indicates incoming ligands are strong ligands. In this solution NH3 ligand
automatically replaces the weaker ligand, H2O. The strength of the H2O and
NH3 ligand fields correspond to the spectrochemical sequence.
15 | (L i g a n d F i e l d S t r e n g t h )
Hybridization of complex compounds above according to VBT
(Valence Bond Theory) where there are 4 H2O and 2 NH3 ligands as follows.
H2O H2O H2O H2O NH3 NH3
1.
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 617 × 349.75 𝑐𝑚−1
= 46.34 kkal/mol
The value of Dq of the third test solution is different from the second
test solution, where the Dq energy of the third test solution will be smaller,
that is 46.34 kkal/mol. From the comparison of the Dq energy of the third
and second test solutions, the Dq energy of the second test solution is
greater because of the higher NH3 ligand substitution which causes Dq
energy to increase, whereas in the third test solution a more H2O ligand
substitution is formed. So it can be concluded that the strength of NH3 ligand
field is greater than H2O because it causes a large Dq energy, where this
large energy will make splitting eg and t2g orbitals greater. Large splitting
indicates incoming ligands are strong ligands. In this solution the NH3
ligand automatically replaces the weaker ligand, H2O, but the NH3 ligand
that replaces H2O is not as much as the test solution 2.
16 | (L i g a n d F i e l d S t r e n g t h )
4. Absorbance of blank solution
For a blank solution, the first step taken is to taken the aquadest and
inserted into cuvette. Then tested with a UV-Vis spectrophotometer at a
wavelength of 400-600 nm, the absorbance value obtained was 0.00. Blank
solution is used as a comparison solution (control).
I. CONCLUSION
From these experiments, it can conclude that:
1. The greater the wavelength value produced, the smaller the value of Dq, i.e.
• λ max of first test solution > λ max of third test solution < λ max of
second test solution: = 812.0 nm > 617.0 nm < 610.0 nm
• Dq of second test solution > Dq of third test solution < Dq of first test
solution: 46.87 kkal/mol > 46.34 kkal/mol > 35.2 kkal/mol
2. NH3 ligand field strength is greater than H2O, because NH3 has a large Dq
value, resulting in a large splitting as well.
3. The more substituted NH3 ligands, the UV-VIS spectrometry will read a
smaller wavelength, so the Dq value will be even greater.
17 | (L i g a n d F i e l d S t r e n g t h )
REFERENCES
18 | (L i g a n d F i e l d S t r e n g t h )
ATTACHMENTS
A. Calculations
Knowing:
Absorbance A = 0.2756 wavelength max = 812.0 nm
Absorbance B = 0.5197 wavelength max = 610 nm
Absorbance C = 0.3840 wavelength max = 617.0 nm
Asked: 10 Dq =?
Answer:
1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙 1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Formula 10Dq = V × 349.75 𝑐𝑚−1 = 𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥 × 349.75 𝑐𝑚−1
1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Solution A 10 Dq = × 349.75 𝑐𝑚−1
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 812 × 349.75 𝑐𝑚−1
= 35.2 kkal/mol
1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Solution B 10 Dq = × 349.75 𝑐𝑚−1
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 610 × 349.75 𝑐𝑚−1
= 46.87 kkal/mol
1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Solution C 10 Dq = × 349.75 𝑐𝑚−1
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 617 × 349.75 𝑐𝑚−1
= 46.34 kkal/mol
B. Documentations
Absorbance of Cu2+ diluted into water
19 | (L i g a n d F i e l d S t r e n g t h )
Absorbance of cu2+ diluted into ammonium
ammonium
C. Question Answers
1. Explain the difference in ligand field strength between ammonium ligands
and water!
Answer:
H2O is a ligand that is as a weak ligand. Weak ligands in the complex cause
electrons to have a high spin at the energyeg level, because in Cu(II) ions
the electrons in the d orbitals are more easily placed in the direction of
higher orbital energies as silent (unpaired) electrons rather than being placed
in the orbital chambers same, but as paired electrons. Because in the same
room there will be a repulsive force between two electrons when paired up.
Because the energy for rejecting (P) is greater than the price of 10 Dq, there
20 | (L i g a n d F i e l d S t r e n g t h )
is an interaction of the upper energy level with the lower energy causing the
distance t2g and eg to be shorter so that the 10Dq energy becomes smaller.
3. What factors affect the color of the transition metal complex ions?
Asnwer:
The difference in color in transition metals makes it one of the special
features of these metals. This can be explained by crystal field theory. If the
d-orbitals of a complex split into two groups, then when the molecule
absorbs photons from visible light, one or more electrons in the orbitals will
jump from the lower-energy d orbitals to the higher-energy d orbitals,
produce excited states of atoms. The difference in energy between the atoms
in the ground state and those in the state of excitation is the same as the
energy of the photon absorbed and is inversely proportional to the light
waves. Because only certain light waves (λ) can be absorbed (waves that
have the same energy as excitation energy), these compounds will show
complementary colors (light waves that are not absorbed). As explained
above, different ligands will produce crystal fields with different energies,
so that we can see a variety of colors. For a metal ion, a weaker ligand field
will form a complex whose bernilai is of low value, so that it will absorb
light with a longer λ and lower the frequency ν. Conversely a stronger field
will produce greater Δ, absorb shorter λ, and increase ν.
21 | (L i g a n d F i e l d S t r e n g t h )
Graph
Wavelength Vs Absorbance
0.6
0.5 0.5197
Absorbance
0.4 0.384
0.3
0.2756
0.2
0.1
0
812 610 617
Wavelength
Wavelength 10 Dq
(nm) (kkal/mol)
A 812 35.2
B 610 46.87
C 617 46.34
Graph
10 Dq Vs Wavelegth
50
46.87 46.34
40
10 Dq (kkal/mol)
35.2
30
20
10
0
812 610 617
Wavelength (nm)
10Dq Absorbance
A 35.2 0.2756
B 46.87 0.5197
22 | (L i g a n d F i e l d S t r e n g t h )
C 46.34 0.384
Graph
10 Dq Vs Absorbance
0.6 0.5197
0.5
0.384
Absorbance
0.4
0.2756
0.3
0.2
0.1
0
35.2 46.87 46.34
10 Dq (kkal/mol)
5. Calculate the energy size of 10 Dq for the three solutions (use equation 1,
see example of the calculation of complex energy of Ti)!
Answer:
Knowing:
Absorbance A = 0.2756 wavelength max = 812.0 nm
Absorbance B = 0.5197 wavelength max = 610 nm
Absorbance C = 0.3840 wavelength max = 617.0 nm
Asked: 10 Dq =?
Answer:
1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙 1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Formula 10Dq = V × 349.75 𝑐𝑚−1 = 𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥 × 349.75 𝑐𝑚−1
1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Solution A 10 Dq = × 349.75 𝑐𝑚−1
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= ×
812 349.75 𝑐𝑚−1
= 35.2 kkal/mol
1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Solution B 10 Dq = × 349.75 𝑐𝑚−1
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 610 × 349.75 𝑐𝑚−1
= 46.87 kkal/mol
1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Solution C 10 Dq = × 349.75 𝑐𝑚−1
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
23 | (L i g a n d F i e l d S t r e n g t h )
107 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
= 617 × 349.75 𝑐𝑚−1
= 46.34 kkal/mol
24 | (L i g a n d F i e l d S t r e n g t h )