Ligand Field Strength

A.
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).
Figure 2. d-orbitals and their orientation with relation to ligands in an

octahedral complex
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).
Figure 3. Ligand-field diagram for the octahedral complex [Ti(H2O)6]3+
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
ligands, and those that produce a small splitting are called weak field
ligands.
An abbreviated spectrochemical series is:
Orbital overlap. Referring to the molecular orbital diagram above,

we see that the splitting between d-electron levels reflects the antibonding
interaction between the eg metal orbitals and the ligands. Thus, we expect
ligand field strength to correlate with metal-ligand orbital overlap. Ligands
that bind through very electronegative atoms such as O and halogens are
thus expected to be weak field, and ligands that bind through C or P are
typically strong field. Ligands that bind through N are intermediate in
strength. Another way to put this is that hard bases tend to be weak field
ligands and soft bases are strong field ligands.
Energy units. Energy can be calculated in a number of ways and it is
useful to try to relate the splitting energy ΔO to more familiar quantities like
bond energies.
When ΔO is measured optically, a photon of wavelength λ is absorbed
as an electron is promoted from a t2g to an eg orbital. The photon energy is
related to its wavelength and frequency by:
E = hν = hc/λ = hc𝑣
Here ν is the frequency of the electromagnetic radiation, h is Planck's
constant (6.626 × 10-34 J*s), and c is the speed of light. 𝑣̅ is called the
"wavenumber" and is the inverse of the wavelength, usually measured in
cm-1. Energy gaps are often expressed by spectroscopists in terms of
wavenumbers (Cleeton & Williams, 1934).
Table 1. ΔO depends on both the metal and the ligand
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.
3. Colors of transition metal complexes

A simple, qualitative way to see the relative crystal field splitting
energy, ΔO, is to observe the color of a transition metal complex. The higher
the energy of the absorbed photon, the larger the energy gap. However, the
color a complex absorbs is complementary to the color it appears (i.e., the
color of light it reflects), which is opposite the absorbed color on the color
wheel.
Figure 4. Complementary colors are across the color wheel from each
other.
Examples: (all d7 Co2+ complexes)
[Co(H2O)6]2+ looks purple in its salts and in concentrated solution because

it absorbs in the green range.
[Co(NH3)6]2+ is straw-colored because it absorbs in the blue range.
[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.
This method is applicable to most transition metal complexes, as the

majority of them absorb somewhere in the visible range (400-700 nm =
25,000 to 14,300 cm-1), or have UV transitions that tail into the visible,
making them appear yellow; however there are complexes such as
[Rh(CN)6]3- that appear colorless because their d-d transitions are in the
ultraviolet. Other complexes such as [Mn(H2O)]62+ are weakly colored
because their d-d transitions involve a change in the spin state of the
complex (Li, Zhou, & Mak, 2008).
E. TOOLS AND SUBSTANCES

Tools
1. Measured flask 10 mL 1 pcs
2. Beaker glass 50 mL 3 pcs
3. Test tube 4 pcs
4. Pipettes 5 pcs
5. Test tube rack 1 pcs
6. Tissue 1 pcs
7. Spectrophotometer 1 pcs
Substances
1. Cu2+ soution (0,1 M) ± 6 mL
2. Ammonium 1 M ± 7,5 mL
3. Aquadest (H2O) sufficiently
F. LANES WORK
1. Absorbance of Cu2+ diluted into water
2 mL Cu2+ 0,1M
- Entered into measured flask 10 mL

- Diluted using water until the sign
Cu Solution
- Observed the absorbance by using

spectrophotometer UV-VIS or
wavelength 700-850 nm
- If the absorbance bigger than 1, dilute it
until the absorbance maximum is 1
- Observed the graph
The wavelength
Reactions:
a. Cu2+ + H2O(l) → Cu2+ + H2O(l)
2. Absorbance of Cu2+ diluted into ammonium (50:50)
2 mL Cu2+ 0,1M

- Added 5 mL ammonium 1 M
Cu Solution : ammonium (50:50)
- Observed the absorbance by using spectrophotometer

UV-VIS or wavelength 350-700 nm
- If the absorbance bigger than 1, dilute it until the
absorbance maximum is 1
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)
c. Absorbance of Cu2+ diluted into ammonium (75:25)
2 mL Cu2+ 0,1M

- Added 2,5 mL ammonium 1 M
Cu Solution : ammonium (75:25)

- If the absorbance bigger than 1, dilute it
until the absorbance maximum is 1
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)
d. Absorbance of blank solution
Aquadest

spectrophotometer UV-VIS on
- Noted the maximum absorbance
Maximum absorbance of aquadest
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
- 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
Experiment Result
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
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)
Experiment Result
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
4. Absorbance of blank solution • Aquadest = • Wavelenght = 400.0 nm
- Aquadest enetered into cuvete colorless solution ▪ Absorbance = 0.00
- Noted the maximum absorbance
- Obtained maximum absorbance of
aquadest
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
According to crystal field theory, d orbitals that are decomposed by ligands

are called crystalline or splitting descriptions. This splitting consists of energy
levels of eg and t2g orbitals with an energy level difference of 10 Dq. So from
the value of 10 Dq obtained from each test solution, it can determine the
difference in the strength of the ligand field between the ammonium ligand and
water in Cu as the central metal.
In theory, if the ligand is stronger, then 10 Dq will also be even greater. If
10 Dq is small, the ligand is a weak ligand. Strong ligands can replace weaker
ligands. And then, it will be examined between reading the value of 10 Dq
produced with the spectrochemical series. Next is the spectrochemical
sequence:
I- < Br- < SCN- ~ Cl- < F- < OH- ~ NO- < C2O42- < H2O < CS- < EDTA4- <
NH3 ~ pyr ~ en < phen < CN- ~ CO.
1. Absorbance of Cu2+ diluted into water
In the first 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 diluted
with distilled water until its reach the mark. Dilution produces a fainter blue
solution than before where the blue color formed absorbs the
complementary color of red with a wavelength of around 610-800 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 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
From the hybridization above it can be seen that the hybridization

complex [Cu(H2O)6]2+ is sp3d2 with octahedral molecular geometry because
PEI = 6 and is paramagnetic. The solution was then tested with a UV-Vis
spectrophotometer at a wavelength of 700-850 nm, and a maximum
wavelength of 812.0 nm was obtained with an absorbance of 0.2756. These
results are in accordance with the theory that the complementary green color
in the range of 610-800 nm.
The price of 10Dq can be found by entering a maximum wavelength
of 812.0 nm in the following formula.
1 1 𝑘𝑘𝑎𝑙/𝑚𝑜𝑙
Solution A 10 Dq = × 349.75 𝑐𝑚−1
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
= 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.
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)
(Valence Bond Theory) where there are 3 H2O and 3 NH3 ligands as follows.
H2O H2O H2O NH3 NH3 NH3
3.

complex [Cu(H2O)3(NH3)3]2+ is sp3d2 with octahedral molecular geometry
because PEI = 6 and is paramagnetic. The solution was then tested with a
UV-Vis spectrophotometer at a wavelength of 350-700 nm, and a maximum
wavelength of 610.0 nm was obtained with an absorbance of 0.5197. This
result is in accordance with the theory that the greenish blue complement is
Solution B 10 Dq = 𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑚𝑎𝑥
× 349.75 𝑐𝑚−1
= 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.

In the third 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 2.5 mL of ammonium (by the ratio 25:75), 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)4(NH3)2]2+ or diaminatetraaquo copper(II) ion.
Because the addition of water is smaller than ammonia, stable Cu2+ ions in
water [Cu(H2O)6]2+ are substituted by 4 H2O ligands and 2 NH3 ligands. The
reaction is shown as follows:
[Cu(H2O)6]2+(aq) + 2NH3(aq) → [Cu(H2O)4(NH3)2]2+(aq)
(Valence Bond Theory) where there are 4 H2O and 2 NH3 ligands as follows.
H2O H2O H2O H2O NH3 NH3
1.

complex [Cu(H2O)4(NH3)2]2+ is sp3d2 with octahedral molecular geometry
because PEI = 6 and is paramagnetic. The solution was then tested with a
UV-Vis spectrophotometer at a wavelength of 350-700 nm, and a maximum
wavelength of 617.0 nm was obtained with an absorbance of 0.3840. This
result is in accordance with the theory that the greenish blue complement is
Solution C 10 Dq = × 349.75 𝑐𝑚−1
= 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.
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.
REFERENCES
Cleeton, C. E., & Williams, N. H. (1934). Electromagnetic waves of 1.1 cm wave-

length and the absorption spectrum of ammonia. Physical Review, 45(4), 234–
237. https://doi.org/10.1103/PhysRev.45.234
Janes, R., Moore, E. (2004). Metal-ligand bonding. Royal Society of Chemistry.
Li, W.-K., Zhou, G., & Mak, T. C. W. (2008). Advanced structural inorganic
chemistry. Oxford University Press.
Miessler, G. L., & Tarr, D. A. (Donald A. (2004). Inorganic chemistry. Pearson
Education.
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:
= 812 × 349.75 𝑐𝑚−1
= 35.2 kkal/mol
Solution B 10 Dq = × 349.75 𝑐𝑚−1
= 610 × 349.75 𝑐𝑚−1
= 46.87 kkal/mol
= 617 × 349.75 𝑐𝑚−1
= 46.34 kkal/mol
B. Documentations
Absorbance of Cu2+ diluted into water
2 mL Cu2+ 0,1 M Diluted into water
Absorbance of cu2+ diluted into ammonium
2 mL Cu2+ 0,1M + 5 mL ammonium Diluted into water until the sign

Absorbance of cu2+ diluted into ammonium
2 mL Cu2+ 0,1M + 2,5 mL Diluted into water until the sign
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
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.
2. Write down the reaction that occurred in the experiment!

Answer:
Cu2+(aq) + H2O(l) → [Cu(H2O)6]2-(aq)
[Cu(H2O)6]2-(aq) + 3NH3(aq) → [Cu(H2O)3(NH3)3]2-(aq)
[Cu(H2O)6]2-(aq) + 2NH3(aq) → [Cu(H2O)4(NH3)2]2-(aq) + H2O(l)
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.
4. Draw a wavelength graph of the absorbance of each of your observations!

Answer:
Wavelength
Absorbance
(nm)
A 812 0.2756
B 610 0.5197
C 617 0.384
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
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:
= ×
812 349.75 𝑐𝑚−1
= 35.2 kkal/mol
Solution B 10 Dq = × 349.75 𝑐𝑚−1
= 610 × 349.75 𝑐𝑚−1
= 46.87 kkal/mol
= 617 × 349.75 𝑐𝑚−1
= 46.34 kkal/mol
6. From the results of the experiment, what can you conclude?

Answer:
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.

Ligand Field Strength

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Ligand Field Strength

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A.

Figure 2. d-orbitals and their orientation with relation to ligands in an

Figure 3. Ligand-field diagram for the octahedral complex [Ti(H2O)6]3+

Orbital overlap. Referring to the molecular orbital diagram above,

3. Colors of transition metal complexes

Examples: (all d7 Co2+ complexes)

[Co(H2O)6]2+ looks purple in its salts and in concentrated solution because

[Co(NH3)6]2+ is straw-colored because it absorbs in the blue range.

This method is applicable to most transition metal complexes, as the

E. TOOLS AND SUBSTANCES

- Entered into measured flask 10 mL

- Observed the absorbance by using

2. Absorbance of Cu2+ diluted into ammonium (50:50)

- Entered into measured flask 10 mL

Cu Solution : ammonium (50:50)

- Observed the absorbance by using spectrophotometer

- Entered into measured flask 10 mL

Cu Solution : ammonium (75:25)

- Observed the absorbance by using

d. Absorbance of blank solution

- Observed the absorbance by using

Maximum absorbance of aquadest

According to crystal field theory, d orbitals that are decomposed by ligands

From the hybridization above it can be seen that the hybridization

From the hybridization above it can be seen that the hybridization

3. Absorbance of Cu2+ diluted into ammonium (75:25)

From the hybridization above it can be seen that the hybridization

Cleeton, C. E., & Williams, N. H. (1934). Electromagnetic waves of 1.1 cm wave-

2 mL Cu2+ 0,1 M Diluted into water

2 mL Cu2+ 0,1M + 5 mL ammonium Diluted into water until the sign

2 mL Cu2+ 0,1M + 2,5 mL Diluted into water until the sign

2. Write down the reaction that occurred in the experiment!

4. Draw a wavelength graph of the absorbance of each of your observations!

6. From the results of the experiment, what can you conclude?

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