LABWORK REPORT

“LIGAND FIELD STRENGTH”

A. DATE OF LABWORK
March 6th, 2017

B. OBJECTIVES
Study the difference between the ligand field strength of ammonia and water.

C. THEORY
An complex ion (or molecules) consists of one atomic (ionic) center and a number of ligands
bound up with the atomic (ionic) centers. The relative amount of these components in a stable complex
appears to follow a very specific stoichiometry, although this can not be interpreted within the scope of
the classical valence. The central atom is characterized by the coordination number, a round number,
which indicates the amount of ligand (monodentate) which can form a stable complex with the central
atom. (Svehla, 1979)

Negative terrain of the ligand is called the ligand field. Ligand field theory is one of the most useful
theory to explain the complex electronic structure. Originally this theory is the application of the theory
of crystal field on complex systems. Negative electric field around the spherical metal cations will
produce a total energy level that is lower than the energy level of cations freely because there are
electrostatic interactions. Repulsive interactions between electrons in the metal and electrical fields
orbital destabilizes the system and to some extent compensate for stabilization. (Saito, 2004)

In order for a pair of electrons to be donated from a ligand to a metal ion, there must be an empty
orbital on the metal ion to accept the pair of electrons. This situation is quite different from that where
covalent bonds are being formed because in that case, one electron in a bonding pair comes from each
of the atoms held by the bond. One of the fi rst factors to be described in connection with the formation
of coordinate bonds is that of seeing what type(s) of orbitals are available on the metal. (House, 2008)

The principal features of the geometrical structures of metal complexes were identified in the late
nineteenth and early twentieth centuries by Alfred Werner, whose training was in organic
stereochemistry. Werner combined the interpretation of optical and geometrical isomerism, patterns of
reactions, and conductance data in work that remains a model of how to use physical and chemical
evidence effectively and imaginatively. The striking colours of many d- and f-metal coordination
compounds, which reflect their electronic structures, were a mystery to Werner. This characteristic was
clarified only when the description of electronic structure in terms of orbitals was applied to the problem
in the period from 1930 to 1960.

The geometrical structures of metal complexes can now be determined in many more ways than
Werner had at his disposal. When single crystals of a compound can be grown, X-ray diffraction gives
precise shapes, bond distances, and angles. Nuclear magnetic resonance can be used to study complexes
with lifetimes longer than microseconds. Very short-lived complexes, those with lifetimes comparable
to diffusional encounters in solution (a few nanoseconds), can be studied by vibrational and electronic
spectroscopy. It is possible to infer the geometries of complexes with long lifetimes in solution by
analysing patterns of reactions and isomerism. This method was originally exploited by Werner, and it
still teaches us much about the synthetic chemistry of the compounds as well as helping to establish their
structures. A large number of molecules and ions can behave as ligands, and a large number of metal
ions form complexes. We now introduce some representative ligands and consider the basics of naming
complexes. (Atkins, et al., 2010)
 The Beer-Lambert law may be used to describe the absorption of light (ignoring scattering and
reflection of light from cell surfaces) at a given wavelength by an absorbing species in solution:

𝐼0
𝑙𝑜𝑔 = 𝐴 = 𝜀𝑙𝑐
𝐼

Where A = absorbance
𝜀 = molar absorptivity (L mol-1 cm-1) (also known as molar extinction coefficient)
𝑙 = path length through solution (cm)
c = concentration of absorbing species (mol L-')

Absorbance is a dimensionless quantity. An absorbance of 1.0 corresponds to 90% absorption at

a given wavelength,' an absorbance of 2.0 corresponds to 99% absorption, and so on. The most common
units of the other quantities in the Beer-Lambert law are shown in parentheses above.

Spectrophotometers commonly obtain spectra as plots of absorbance versus wavelength. The

molar absorptivity is a characteristic of the species that is absorbing the light and is highly dependent on
wavelength. A plot of molar absorptivity versus wavelength gives a spectrum characteristic of the
molecule or ion in question. This spectrum is a consequence of transitions between states of different
energies and can provide valuable information about those states and, in turn, about the structure and
bonding of the molecule or ion.

Although the quantity most commonly used to describe absorbed light is the wavelength, energy
and frequency are also used. In addition, the wavenumber (the number of waves per centimeter), a
quantity proportional to the energy, is frequently used, especially in reference to infrared light. For
reference, the relations between these quantities are given by the equations :

ℎ𝑐 1
𝐸 = 10𝐷𝑞 = ℎ𝑣 = = ℎ𝑐 ( ) = ℎ𝑐𝑣̅
𝜆 𝜆

where E = energy
h = Planck's constant = 6,626𝑥10−34 𝐽𝑠
c = speed of light = 2,998 x 108 m s-1
v = frequency (s-1)
𝜆 = wavelength (often reported in nm)
1
= 𝑣̅ = wavenumber (cm-1) (Miessler & Tarr, 2004)
𝜆

D. EQUIPMENT AND MATERIALS

Equipment :
- 10 mL volumetric flask
- Volumetric Pipette 2 mL, 5 mL, 10 mL
- 100 mL, 250 mL beaker,
- Dropping pipette
- Stirring bar
- Spray bottle
- Spectrophotometer Spectronic 20
 Materials :
- 1 M ammonia solution
Prepared by dissolving 7,50 mL of 25% NH3 (𝜌 = 0.91 Kg / L) in distilled water until a
volume of 100 mL
- Solution of Cu2+ 0.1 M
Prepared by dissolving 2.4968 grams of CuSO4 · 5H2O in distilled water until the volume of 100 mL

E. WORK INSTRUCTION
Solution A
Solution of Cu2+ 0,1 M
[Dissolving 2,4968 g of
CuSO4.5H2O in distilled
water until the volume 100
mL]

Absorbance Absorbance
Observing the
Absorbance 2+ 2+
Cu (50 Cu (25
absorbance using a
No.Solution
𝜆 (𝑛𝑚)B: Cu2+
water : 50 water : 75
Cu2+ in the solution (water)
of Spectrophotometer
ammonia) ammonia)
Spectronic 20 or
NH3 (50:50) Comparing
1. 550 0,032 1,019 0,871
Spectrophotometer the maximum
[5 mL of 0,1 M solution of
2+ 2. 560 0,039 1,143UV-Vis 0,966
at a
Cu in 10 mL volumetric wavelength
3. 570
flask diluted with 1 M 0,047 1,247 1,043
wavelength of 550-
4.
NH3 solution] 580 0,061 1,331700 nm with 1,104
10 nm
5. 590 0,079 1,319interval 1,093
6. 600 0,099 1,344 1,110
7. Solution
602 C: 1,347 1,109
2+
Cu 8. in the604solution of 1,351 1,113
9.NH3 606(25:75) 1,353 1,112
[2.5 10.
mL of 0,1 608M solution 1,354 1,114
2+
of 11.Cu 610
in 10 mL 0,126 1,355 1,113
volumetric
12. flask diluted
620 0,160 1,352 1,108
with13.
1 M NH 3 solution]0,195
630 1,338 1,092
14. 640 0,243 1,305 1,062
15. 650 0,300 1,262 1,028
F. OBSERVATION
16. 660 DATA0,364 1,209 0,985
- Observation
17. Table 670 0,426 1,150 0,936
Table18.
1. Observation
680 Table Between Wavelength
0,502 1,083 Absorbance of Cu2+ Solution
and0,881
2+ 2+
690 Absorbance
0,579 Cu Absorbance Cu0,830
(50 Absorbance Cu2+ (25
No. 19.𝜆 (𝑛𝑚) 1,017
20. 700 (water)
0,657 water
0,950: 50 ammonia)
0,777 water : 75 ammonia)
1. 21. 550 710 0,032
0,738 1,019 0,871
2. 22. 560 720 0,039
0,818 1,143 0,966
3. 23. 570 730 0,047
0,891 1,247 1,043
4. 24. 580 740 0,061
0,957 1,331 1,104
5. 25. 590 750 0,079
1,016 1,319 1,093
6. 26. 600 760 0,099
1,067 1,344 1,110
7. 27. 602 770 1,105 1,347 1,109
8. 28. 604 780 1,133 1,351 1,113
29. 790 1,162
30. 800 1,167
 9. 606 1,353 1,112
10. 608 1,354 1,114
11. 610 0,126 1,355 1,113
12. 620 0,160 1,352 1,108
13. 630 0,195 1,338 1,092
14. 640 0,243 1,305 1,062
15. 650 0,300 1,262 1,028
16. 660 0,364 1,209 0,985
17. 670 0,426 1,150 0,936
18. 680 0,502 1,083 0,881
19. 690 0,579 1,017 0,830
20. 700 0,657 0,950 0,777
21. 710 0,738
22. 720 0,818
23. 730 0,891
24. 740 0,957
25. 750 1,016
26. 760 1,067
27. 770 1,105
28. 780 1,133
29. 790 1,162
30. 800 1,167
31. 810 1,175
32. 820 1,173
33. 830 1,164
34. 840 1,152

- Plot the Absorbance (A) vs. Wavelength:

1.400

1.200

1.000
Absorbance

0.800

0.600

0.400

0.200

0.000
0 200 400 600 800 1000
𝜆 (𝑛𝑚)

Image 1. Relationship between wavelength and absorbance of Cu2+ (water)

 1.600

1.400

1.200

1.000
Absorbance

0.800

0.600

0.400

0.200

0.000
0 100 200 300 400 500 600 700 800
𝜆 (𝑛𝑚)

Image 2. Relationship between wavelength and absorbance of Cu2+ (50 water : 50 ammonia)

1.200

1.000

0.800
Absorbance

0.600

0.400

0.200

0.000
0 100 200 300 400 500 600 700 800
𝜆 (𝑛𝑚)

Image 3. Relationship between wavelength and absorbance of Cu2+ (25 water : 75 ammonia)

- Sort the Power of the Ligand:

 Solution A
ℎ𝑐
10𝐷𝑞 = 𝜆
𝑥 𝑁𝐴

6,626𝑥10−34 𝐽𝑠 𝑥 2,998𝑥108 𝑚/𝑠

= x 6,022x1023 𝑚𝑜𝑙 −1
810𝑥10−9 𝑚
= 147685,818 𝐽 𝑚𝑜𝑙 −1
= 147,685 𝐾𝐽 𝑚𝑜𝑙 −1

 Solution B
ℎ𝑐
10𝐷𝑞 = 𝑥 𝑁𝐴
𝜆
 6,626𝑥10−34 𝐽𝑠 𝑥 2,998𝑥108 𝑚/𝑠
= x 6,022x1023 𝑚𝑜𝑙 −1
610𝑥10−9 𝑚
= 196107,397 𝐽 𝑚𝑜𝑙 −1
= 196,107 𝐾𝐽 𝑚𝑜𝑙 −1

 Solution C
ℎ𝑐
10𝐷𝑞 = 𝜆
𝑥 𝑁𝐴
6,626𝑥10−34 𝐽𝑠 𝑥 2,998𝑥108 𝑚/𝑠
= x 6,022x1023 𝑚𝑜𝑙 −1
608𝑥10−9 𝑚
= 196752,488 𝐽 𝑚𝑜𝑙 −1
= 196,752 𝐾𝐽 𝑚𝑜𝑙 −1

G. DISCUSSION
In the experiment on the strength of ligand field aims to find out ligand field strength differences
between ammonium and water ligand on Cu as metal center. There are three variations of the solvent
used in the test solutions. It is intended that could explain the effect of the maximum wavelength, in
terms of the type of ligand that baned or the amount of ligand to be substituted by Cu. For determine the
maximum wavelength of each test solution used UV – spectrophotometer at wavelengths that vary by
color solution formed with a color complement.

In the first solution, Cu2+ diluted only with water that will eventually form the aqua complex of
copper (II). The second solution, Cu 2+ diluted with water and ammonia with a volume ratio of 50:50,
and a third solution, Cu 2+ diluted with water and ammonia with a volume ratio of 25:75.

Cu 2+ solution blue (greenish), the more the content of ammonia contained in the complex solution
of Cu 2+, then the blue color will be more intense look. This is due to differences in the energy levels of
atomic orbitals are bonding in each solution. The color blue is a color that is characteristic of the Cu 2+
complex compound. The colors are complementary colors which are light waves that are not absorbed.
When the blue color is visible, the yellow color is absorbed.

Before taking measurements with the sample absorbance spectroscopy tool, first measured the
absorbance values of the reference solution. For the reference solution, the same composition as the
solution being analyzed but without the samples analyzed. For this experiment, the blank solution was
distilled water. The reference solution with a zero absorbance is used as a standard for measuring the
absorbance of the complex.

Solution A
This solution contains Cu2+ 0.1 M in water distilled solution. As has been said before that in this
solution the water function as ligand, while the Cu is a metal center. If the bond is between metal ligand
compound formed then called complex compounds. Where the complex compound formed is
[Cu(H2O)6]2+ or ion hexaaquocopper (II). This shows that the ion is generally in water solution (and
some also in the crystalline state) in the form of aquocomplex. His reaction is shown as follows:
Cu2+ (aq) + 6H2O (l) → [Cu(H2O)6]2+ (aq)
Hybridization complex compounds above by VBT (Valence Bond Theory) where there are 6 ligand
of H2O as follows:
Cu0 = 4s1 3d10 Cu2+ = 4s0 3d9
↓↑ ↓↑ ↓↑ ↓↑ ↓
3d 4s 4p 4d
↓ hybridized (sp d )
3 2

↓↑ ↓↑ ↓↑ ↓↑ ↓ H2O H2O H2O H2O H2O H2O

 3d 4s 4p 4d
2+ 3 2
From above it is known that hybridization of complexes ion [Cu(H2O)6] is sp d with octahedral
molecular geometry for PEI = 6 and nature paramagnetic.
The solution tested by UV-spectrophotometer at wavelength of 550 – 840 nm, and obtained
maximum wavelength of 810 nm by absorbance 1,175. Price 10Dq of this solution obtained as
147,685 𝐾𝐽 𝑚𝑜𝑙 −1. Dq value obtained from the solution A is low, it is because there is only H2O ligand
substitution alone, whic is a form aquocomplex. So that it can concluded that the ligand field strength of
H2O is small, where low energy will make orbital splitting eg and t2g getting smaller. Small splitting
incoming signaling that the ligand is weak ligand.

Solution B
This solution contains Cu2+ 0.1 M in ammonia 1 M with concentration 50 water:50 ammonia. As
has been said before that in the solution of water and ammonia serves as a ligand, while the Cu is a
metal center. If the bond is the metal with the ligand, the compounds formed are called compound
complex. Where the complex compound formed is [Cu(H2O)3(NH3)3]2+ or triaminatriaquocopper(II) ion.
Because of the addition of water and ammonia the same comparison, the ion Cu2+ stable in water
[Cu(H2O)6]2+ substituted by 3 ligand H2O and 3 ligand NH3. The reaction is as follows:
[Cu(H2O)6]2+ (aq) + 3NH3 (aq) → [Cu(H2O)3(NH3)3]2+ (aq)
Hybridization complex compounds above by VBT where there are 3 ligand H2O and 3 ligand NH3
as follows:
Cu0 = 4s1 3d10 Cu2+ = 4s0 3d9
↓↑ ↓↑ ↓↑ ↓↑ ↓
3d 4s 4p 4d
↓ hybridized (sp d )
3 2

↓↑ ↓↑ ↓↑ ↓↑ ↓ H2O H2O H2O NH3 NH3 NH3

3d 4s 4p 4d
2+ 3 2
From the above it is known that hybridization complexes of [Cu(H2O)3(NH3)3] is sp d with octahedral
molecular geometry for PEI = 6 and its diamagnetic.
The solution tested by UV-spectrophotometer at wavelength of 550 – 700 nm, and obtained
maximum wavelength of 610 nm by absorbance 1,355. Price 10Dq of this solution obtained as
196,107 𝐾𝐽 𝑚𝑜𝑙 −1. The second test solution will be larger than first solution. From the comparison of
energy 10Dq, the test of solution A and solution B, 10Dq energy of solution B larger than solution A
cause NH3 ligand substitution, so Dq energy is growing. Whereas the solution B test only H2O ligand
substitution. It can be concluded that NH3 ligand field strength greater than H2O as it raises the great
energy, where the energy of this will make orbital splitting eg and t2g bigger. Large splitting incoming
signaling ligand is a strong ligand. In this solution automatically ligand NH3 replaces the weaker ligand
H2O.
Ligand field strength H2O and NH3 is in accordance with atomic series. Here is a atomic series:
I < Br- < SCN- ~ Cl- < F- < OH- ~ NO- < C2O42- < H2O < CS- < EDTA4- < NH3 ~ pyr ~ en < phen < CN-
-

~ CO

Solution C
This solution contains Cu2+ 0.1 M in ammonia 1 M with concentration 25 water:75 ammonia. As
has been said before that in the solution of water and ammonia serves as a ligand, while the Cu is a metal
center. If the bond is the metal with the ligand, the compounds formed are called compound complex.
Where the complex compound formed is [Cu(H2O)2(NH3)4]2+ or diaminatetraaquocopper(II) ion. Since
the addition of water smaller than ammonia, then the ion Cu2+ stable in water [Cu(H2O)6]2+ 2 ligand
substitued by H2O and 4 ligand NH3. The reaction is as follows:
[Cu(H2O)3(NH3)3]2+ (aq) + 2NH3 (aq) → [Cu(H2O)2(NH3)4]2+ (aq)
 Hybridization complex compounds above by VBT where there are 4 ligand H2O and 2 ligand NH3
as follows:
Cu0 = 4s1 3d10 Cu2+ = 4s0 3d9
↓↑ ↓↑ ↓↑ ↓↑ ↓
3d 4s 4p 4d
↓ hybridized (sp d )
3 2

↓↑ ↓↑ ↓↑ ↓↑ ↓ H2O H2O NH3 NH3 NH3 NH3

3d 4s 4p 4d
2+ 3 2
From the above it is known that hybridization complexes of [Cu(H2O)4(NH3)2] is sp d with octahedral
molecular geometry for PEI = 6 and its diamagnetic.
The solution tested by UV-spectrophotometer at wavelength of 550 – 700 nm, and obtained
maximum wavelength of 608 nm by absorbance 1,114. Price 10Dq of this solution obtained as
196,752 𝐾𝐽 𝑚𝑜𝑙 −1. Dq value of solution C different from the solution B, where Dq energy of solution
C greater than solution B. This is cause the concentration of NH3 more much compared with H2O in this
solution.

From the paper of “Ligand field splittings in copper(II) compounds” we know that NH3 ligand
stronger than H2O ligand. This is in accordance with the results obtained that 10Dq1 < 10Dq2 < 10Dq3.
10Dq1 contains Cu2+ in H2O. 10Dq2 contains Cu2+ in H2O and NH3 with 50:50. 10Dq3 contains Cu2+ in
H2O and NH3 with 25:75. (Smith, 1972)

H. CONCLUSION
From this experiment can conclude that ligand field strength of water smaller than ammonia. There are
proved that 10Dq1 < 10Dq2 < 10Dq3.

I. SUGGESTION
Practican suggest that when work in this experiment, important when making a solution and when testing
solution with UV-Spectrophotometer.

J. REFERENCES

Atkins, P. et al., 2010. Inorganic Chemistry. 5th penyunt. New York: W. H. Freeman and Company.

House, J. E., 2008. Inorganic Chemistry. London: Academic Press.

Miessler, G. L. & Tarr, D. A., 2004. Inorganic Chemistry. 3th penyunt. Boston: Pearson Education
Int..
Saito, T., 2004. Kimia Anorganik. Tokyo: Iwanami Publishing Company.
Smith, D., 1972. Ligand Field Splittings in Copper(II) Compound. s.l., Springer.
Svehla, G., 1979. Vogel's: Textbook of Macro and Semimicro Qualitative Inorganic Analysis. 5th ed.
New York: Longman Inc..

APPENDIX
Documentation