Chemistry 163 MiniLab 6 Spring 2021 page 1 of 6

MIniLab 6 Report Form

Nickel Complexes and Colors - 20 pt

1. Ni(H2O)62+ complex – hexaaquanickel(II) (Figure 1a)
 Prepare a solution of Ni(H2O)62+ by dissolving 1.84 g of NiSO4•6H2O in the 100.0 mL of
water.
 Remember that Ni2+(aq) is really the complex ion Ni(H2O)62+(aq).

1.a. Color observed for Ni(H2O)62+ :

Light aqua green

1.b. Color of light absorbed:

Red

1.c. Calculate the concentration of Ni(H2O)62+ in this solution. (Assume the final volume is
100. mL)
g g g g
Molar mass of NiSO4: 58.6934 + 32.065 + 4 * 15.9994 = 154.756
mol mol mol mol
g g g
Molar mass of H2O: 2 * 1.0079 + 15.9994 = 18.0152
mol mol mol
1.84 g
g g = 0.00070002648 mol Ni(H2O)62+ ≈ 0.00700 mol Ni(H2O)62+
154.756 +6∗18.0152
mol mol
0.00700 mol
[Ni(H2O)62+] = = 0.0700 M
0.100 L

1.d. Draw the d orbital splitting diagram for this complex (label each d orbital).

Is this complex diamagnetic or paramagnetic?

Paramagnetic
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Lab 6 cont.

2. Ni(NH3)62+ complex – hexaamminenickel(II) (Figure 1b)

 Add 15 mL of 5 M aqueous ammonia solution to the beaker containing Ni(H2O)62+
and stir.
Ni(H2O)62+(aq) + 6 NH3 (aq) → Ni(NH3)62+(aq) + 6 H2O Kf = 1.2 x 109

2.a. Color of the Ni(NH3)62+ complex:

Deep blue

2.b. Color of light absorbed:

Orange-yellow

2.c. Ligand: Does the crystal field splitting energy for Ni(NH3)62+ increase or decrease compared
to Ni(H2O)62+? What is the evidence?
The crystal field splitting energy for Ni(NH3)62+ increases compared to Ni(H2O)62+ . Evidence can
be found because of the color. Ni(NH3)62+ absorbs higher energy/shorter wavelength (orange-
yellow color), hence its deep blue appearance. Because of the weak field of the H2O ligand, it
absorbs in lower energy/longer wavelength (red color), hence its light aqua green appearance.
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Lab 6 cont.

3. Ni(en)32+ complex - tris(ethylenediamine)nickel(II) (Figure 1c)

 Add 10 mL of a 30% ethylenediamine (en) solution to the beaker and stir.

Ni(NH3)62+(aq) + 3 en(aq) → Ni(en)32+ (aq) + 6 NH3 (aq) K = 1.1 x 109

3.a. Color of the Ni(en)32+ complex:

Purple

3.b. Color of light absorbed:

Yellow

3.c. Ligand: Why are there only three ethylenediamine ligands instead of the six ammonia
ligands in the previous step? What is the geometry of Ni(en)32+?
There are only three ethylenediamine ligands instead of the six ammonia ligands in the previous
step due to ethylenediamine being a bidental ligand. However, NH3 is a monodentate ligand;
that’s why for NH3, 6 ligands are needed whereas the ethylenediamine only needs 3 (two dents to
bind for each).
The geometry of Ni(en)32+ is octahedral.

3.d. What does the magnitude of the equilibrium constant for this step tell you about the
reaction?
The magnitude of the equilibrium constant for this step is quite high. K is very large, so it has a
very little reverse reaction and could be very near to completion. At equilibrium, there will be
more products than reactants. We see that on the left side of the equilibrium equation, there are 4
molecules, while on the right, there are 7 molecules.
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Lab 6 cont.

4. Ni(Hdmg)2 complex - bis(dimethylglyoximato)nickel(II) (Figure 1d)

Ni(en)32+ (aq) + 2 dmgH2(aq) → Ni(dmgH)2 (s) + 3 en (aq) + 2 H+ (aq) K = 1.35 x 105

 Dimethylglyoxime, C4H8N2O2, dmgH2, will chelate a large number of metals. The video
abbreviates the original dimethylglyoxime as dmgH2. When it binds to a metal cation, it
is bidentate, losing one H+ to form the related -1 anion, abbreviated dmgH1-. Careful,
most sources will abbreviate dimethylglyoxime as simply dmg and the anion as dmg1- but
we’ll follow the video. Only two dmgH1- ions are required per metal center because
Ni(dmgH)2 has a square-planar geometry due to hydrogen bonds connecting the two
ligands.
 Add 200 mL of 1% dimethylglyoxime in ethanol to the aqueous complex.

4.a. Color observed for the Ni(dmgH)2 complex:

Red

4.b. Color of light absorbed:

Green

4.c. Ligand: This complex is insoluble. What is different about this complex compared to all the
other complexes in this lab – in other words, why is this complex insoluble when the others are
soluble?
Unlike all the other complexes in this lab, this complex does not have a charge. The water has a
very poor interaction with this complex, hence the substance’s insolubility. It is “complete” and
“wants nothing to do with” the water, so it is insoluble.

4.d. Magnetism: This complex is diamagnetic. Draw the d orbital splitting diagram for this
complex.
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Lab 6 cont.

5. Ni(CN)42- complex - tetracyanonickel(II) (Figure 1e)

 The cyanide ion (CN-) is a monodentate strong field ligand. Cyanide is a very strong field
ligand because there is both σ-bonding from the ligand to the metal and π-back bonding
from the metal to the ligand.
 Add 30 mL of 1 M KCN solution to the solution in the beaker.
 Note: Working with cyanide salts must be done with great care. Addition of acid may
result in the formation of lethal hydrogen cyanide gas.
Ni(dmgH)2 (s) + 4 CN- (aq) - → Ni(CN)42- (aq) + 2 dmgH1-(aq) K = 6.3 x 107
5.a. Color observed for the Ni(CN)42- complex:
Orange-yellow (due to the remains of the red solid mixed in there, but the solution in itself alone
would be yellow as noted in the video).

5.b. Color of light absorbed:

Violet blue

5.c. Which is the stronger field ligand, cyanide or dmgH1-? List two pieces of evidence that
support your answer.
Cyanide is the stronger field ligand than dmgH1- because the K value from question 4 (relating to
dmgH1-) is less than that of the K value from question 5 (relating to cyanide). The stronger field
ligand has a higher K value.
Additionally, another piece of evidence is the color of the Ni(CN)42- complex (containing the
cyanide ligand) where it has an orange-yellow color and absorbs violet blue, which means it is
absorbing higher energy/lower wavelength than the Ni(dmgH)2 complex (containing the dmgH1-
ligand). On the other hand, the color of the Ni(dmgH)2 complex (containing the dmgH1- ligand)
has a red color and absorbs green, which means it is absorbing lower energy/higher wavelength
than of the Ni(CN)42- complex (containing the cyanide ligand). Therefore, it makes cyanide the
stronger field ligand than dmgH1-.
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Lab 6 cont.

5.d. Draw the d orbital splitting diagram for this complex. Is it diamagnetic or paramagnetic?

Diamagnetic

5.e. Rank all the ligands in this experiment from weakest to strongest:

Weakest: Ni(H2O)62+ < Ni(NH3)62+ < Ni(en)32+ < Ni(dmgH)2 < Ni(CN)42- :Strongest