Background information for Ni Complex

This experiment helps us understand the process of how to obtain a chemical formula from a newly
synthesized compound. In particular, the experiment will look at a class of compounds called complexes
because they are relative newer substances that are useful in a variety of applications such as
nanotechnology, medicine, and dielectric products. Many transition metals form complexes with ligands
(compounds that attach to the metal). In these cases, the transition metal cation acts as a Lewis acid, and the
ligands donate electron lone pairs to complete the attraction between the metal and ligand.
Ligands can be monodentate or polydentate, meaning that they have one or multiple interactions with the
metal cation.

Figure 1. ethylenediamine is bidentate ligand, while EDTA is polydentate

Complexes are often colorful substances. For example, the crystals below attribute their color to the complex
that makes up most of the jewel.

Figure 2. Jewels that contain transition metal complexes are colorful.

Often the color of the substance indicates that a complementary color of light was absorbed, this can be
understood using the following color wheel. For example, if a substance appears red, then from the color
wheel it means that the substance absorbed the complementary color on the opposite side of the wheel, blue-
green light, such that the light transmitted (observed light) is red.

Figure 3. Complementary colors are those that appear on opposite sides of the wheel.
If an absorbance spectrum is taken of the red (720 – 630 nm) complex, that means the sample will absorb light
with wavelength 520 – 490 nm, and the absorbance peak will appear in that region (490 – 520 nm) of the
spectrum.
Nickel can form complexes with water, where the attractions occur between Ni2+ and the lone pairs of the
oxygens in water. Often the Ni2+ will bind 6 waters, to form an octahedral shaped complex. This will readily
occur when Ni2+ is in the presence of water.

Figure 4. A Nickel complex with water made with Nickel (II) sulfate
Other complexes can be synthesized from this starting structure. For example, a complex that contains
ethylenediamine (H2N-CH2-CH2-NH2), which a bidentate ligand that donates lone pair of electrons from two
nitrogen atoms, will replace two water molecules at a time.
[Ni(H2O)6]SO4 + en → [Ni(en)(H2O)4]
Depending on the extent of reaction and amount of ethylenediamine (en) added then 2 waters, 4 waters, or 6
waters will be replaced. In the experiment, complexes with nickel and x number of ethylenediamines (x=1,2,
or 3) will be made and an experimental analysis will take place to determine the chemical formula, specifically
the empirical formula.
To determine the empirical formula of a substance, experimental results are such that grams of the elements
present in the compound are obtained. These are often reported in mass percentages (mass A/mass sample
*100%) and then the empirical formula in terms of mole quantities of the elements is figured out. For
example, for ethylene glycol, experiments were conducted, and it was determined that it contained 38.70%
carbon, 9.75% hydrogen, and the rest oxygen. To determine the empirical formula, need to assume 100 g of
ethylene glycol, which means there should be 38.70 grams C, 9.75 grams H, and the remainder 51.55 grams is
O. Convert all of these to moles to get the empirical formula:
1 𝑚𝑜𝑙 𝐶
38.79 𝑔 𝐶 × = 3.22 𝑚𝑜𝑙 𝐶
12.01 𝑔 𝐶
1 𝑚𝑜𝑙 𝐻
9.75 𝑔 𝐻 × = 9.67 𝑚𝑜𝑙 𝐻
1.008 𝑔 𝐻
1 𝑚𝑜𝑙 𝑂
51.55 𝑔 𝑂 × = 3.22 𝑚𝑜𝑙 𝑂
16.00 𝑔 𝑂

𝐶3.22 𝐻9.67 𝑂3.22 is the pseudo empirical formula which then becomes CH3O after dividing by 3.22.
3.22 3.22 3.22
Similarly, we can obtain the mass percentages of the substances present in a complex and obtain the relative
mole quantities. In the experiment, reactions will take place between Ni2+, SO42-, H2O, en, and ethanol, so
therefore the complexes formed will contain some or all these substances. The mass percentages then need to
be determined via experiment analysis so that the empirical formula can be obtained.
Complexes with the general formula [Ni(en)x(H2O)6-2x]SO4·yH2O will be synthesized. Then analysis experiments
will be conducted to determine moles, grams, and mass % of each substance. The techniques are: Beer’s law
calibration curve for Ni2+, and SO42-, back-titration HCl with NaOH for en, and visible spectrum will be taken of
all salts A, B, and C to help determine the empirical formulas for all three. Once the mass % of Ni2+, SO42-, and
en are obtained, the mass % H2O can be calculated (100% - [% Ni2++ % SO42-+ % en]). The mole quantities can
then be determined to find the empirical formula and x for en, 6-2x for the water. The remainder of the mole
quantity of water will then determine y for the hydrated water (extra water trapped when solid forms).
In the Beer’s law analysis, a calibration curve will be made from three [Ni(H2O)6]SO4 standards (concentration
known). The absorbance of a sample that contains the unknown salt will analyzed to determine the Ni2+
concentration of the salt. Then using the volume of the sample, the moles of Ni2+, and thus grams of Ni2+ can
be determined. The mass % Ni2+ is then obtained from grams of Ni2+ and initial amount used to make the
solution. The mole of Ni2+ and SO42- need to be equal due to the electro-neutrality principle (define it). So,
moles then grams, then mass % of sulfate will be obtained here as well.
To determine the moles of ethylenediamine (en), the complex salt is dissolved in an acid. If the acid used is
HCl, then it reacts with en to form an acidic product (enH22+) between the two. This requires 2 moles of HCl
per 1 mole of en removed from the complex. If excess HCl is added to dissolve the salt, this ensures all the en
will be removed from the complex. The solution now contains, among other substances, HCl left over. That left
over HCl can then be “neutralized” by conducting a titration with NaOH. This is called a back-titration because
it helps determine how much HCl was used in forming enH22+. The titration will determine how many moles of
NaOH are used to neutralize the left over HCl, which is the number of moles of HCl left over. Since the volume
and concentration of HCl added is known, the total moles of HCl are known. Then moles of HCl used can be
calculated,
moles HCl used = total moles HCl – moles HCl left over
moles of en = ½ (moles HCl used) due to the stoichiometric ratio 1:2
Once moles of en are calculated, then grams, and then mass % of en can be obtained. Obtaining the mass % of
H2O can now be calculated. Statistical analysis on multiple trials for each analytical method should be
conducted to obtain reliable results. Those statistical measures should then be reported.
Once the assigned salt has been analyzed and its empirical formula been determined, the visible spectra taken
of the three salts can be compared. All spectrum will be different, and by looking at peak absorbances and the
salts themselves can each spectrum be assigned a formula [Ni(en)x(H2O)6-2x]SO4, where x = 1, 2, or 3.

Figure 5. Absorbance spectra of [Ni(en)(H2O)4]2+, [Ni(en)2(H2O)2]2+, and [Ni(en)6]2+. The 4th spectrum is for
[Ni(H2O)6]2+, which has two broad peaks between 600 – 800 nm.