Title: Determination of Nickel by Gravimetric Analysis

Objective: To determine the weight percent of nickel by gravimetric analysis

Introduction:

Gravimetric analysis is among the most accurate of all the analytical methods available. It is used to
determine the mass of a substance by weighing. Firstly, the radical or element that needs to be
determined is first stabilized to a compound of known composition and the mass of that particular
compound is then determined. 

Precipitative analysis (the type of gravimetric analysis used in this experiment) requires that the
substance of interest to be weighed be readily removed via vacuum filtration. Hence it should be
precipitated, however it should achieve a low supersaturation in order to form larger, easier to filter
crystals rather than having a high supersaturation which would cause small, micro crystals to form that
are extremely tricky to filter. In extreme cases, it may even form a colloid and pass through the filter.

The precipitating agent used should ideally be specific or at least selective towards the substance of
interest. Specific reagents are reagents that react only with a single species, while selective reagents
react with a small limited number of reagents. Furthermore, the precipitating agent used should also
give a product that is easily washed free of contaminants and easily filtered, sufficiently low solubility so
that no significant loss happens during filtration and washing of a known chemical composition once
dried and unreactive towards the atmosphere.

Apparatus & Materials:

Beaker (50 mL, 100 mL, 150 mL), dropper, sintered glass crucible (porosity 3), wash bottle, Nickel
ammonium sulphate (NiSO4(NH4)2SO46H2O), concentrated sulphuric acid (HCl), dimethylglyoxime, dilute
ammonia solution (NH3), cold distilled water
Experimental procedure:

A sample of 0.3-0.4 g (NiSO4(NH4)2SO46H2O) was weighed accurately into a 250 mL beaker. The salt was
dissolved in distilled water and 2-3 mL of HCl to 150 mL. The solution was heated to 70-80 °C and a slight
excess of dimethylglyoxime was added. Dilute ammonia solution was added dropwise with constant
stirring until complete precipitation was achieved. The solution was digested for 20 – 30 minutes. The
precipitate was allowed to cool and was filtered via vacuum filtration. The precipitate was washed with
cold distilled water and then dried for an hour until a constant weight was achieved.

Results and Calculations: 

Mass of (NiSO4(NH4)2SO46H2O) used (g) 0.4106

Weight of empty sintered glass crucible (g) 40.0850

Weight of sintered glass crucible + product (g) 40.1330

Weight of product (g) 0.048

Molar mass of (NiSO4(NH4)2SO46H2O) = 394.99 g/mol

Molar mass of Ni(dmg)2 = 288.9416 g/mol

Mols of (NiSO4(NH4)2SO46H2O) used = (0.4106 g / 394.99 g/mol)

  = 1.040x 10-3 mol

1 mol of (NiSO4(NH4)2SO46H2O) reacts with 2 mols of dimethylglyoxime to product 1 mol of Ni(dmg) 2 

Hence 8.962 x 10-4 mol of (NiSO4(NH4)2SO46H2O) produces 8.962 x 10-4 mol of Ni(dmg)2
Theoretical mass of Ni(dmg)2 = 1.040x10^-3mol x 288.9413 g/mol

= 0.3005 g

Actual mass of Ni(dmg)2 obtained = 0.0480 g

Yield = (0.0480/0.3005) * 100%

          = 16.00 %

Percentage of Nickel in product = 20.32% in Ni(dmg) 2

Theoretical percentage of nickel by weight = 20.32% x 0.3005 g

= 0.0611 g

Actual percentage of nickel by weight = 20.32 % x 0.0480 g = 0.0975 g

Discussion:

In this experiment, the pH is buffered in the range of 5-9 using an ammonia solution in order to form the
red chelate. This reaction occurs due to the donation of electron pairs on the four nitrogen atoms. If the
pH is not buffered appropriately in order to prevent it falling below pH 5, the equilibrium of the reaction
favors the formation of the nickel (II) ion instead, causing the Ni(dmg) 2 to redissolve back into the
mother liquor.

The Dmg solution was added in slight excess to about 2.5 mols, but care should be taken not to add it in
a large excess as to avoid the possibility of the precipitation of the reagent itself as the precipitate will
be soluble in free mineral acids. It is therefore imperative to avoid the large excess addition of the dmg
solution as it may crystallize out along with the chelate.

A slow increase in the concentration of ammonia in the solution causes a slight increase in the pH
gradually and results in the precipitation of the complex. The result is the formation of a denser
precipitate. Once the filtrate has been collected and dried, the nickel content of the solution is
calculated stoichiometrically from the weight of the precipitate.

A yield of 16.00% was obtained from the experiment, which was a quite a low result, however it could
be a misleading result as the product was dried for a too long period. The product was dried for almost 5
days and this could cause some of the product to be evaporated. Furthermore, the result may be
improved if the recovery of the product was improved, as some of the product was loss to the sides of
the beakers that it was stored in and also the recovery during the filtration should be taken care of.
Concentrated HCl is extremely corrosive and gives off toxic fumes and was handled in the fumehood to
avoid inhalation. Ammonia has a strong pungent odor that causes nausea and was covered when not in
use
Conclusion:

The amount of Ni(dmg)2 obtained was 0.0480 g versus a theoretical weight of 0.3005g, with a yield of
16.00% and a percentage nickel by weight of 0.0975 g as compared to the theoretical percentage nickel
by weight of 0.0611 g.

References

1. Girolami,, G. S., Rauchfuss, T. B., & Angelici, R. J. (1999). Synthesis and Technique in Inorganic
Chemistry: A Laboratory Manual (Vol. 3rd Edition). University Science Books.

2. Organic Syntheses. (2016, 08 14). Dimethylgyloxime. Retrieved from Organic Suntheses:

http://www.orgsyn.org/demo.aspx?prep=cv2p0204

3. Universiti Tunku Adbul Rahman. (2016). UDEE1224 Chemistry Laboratory II Lab Manual.
Kampar: UTAR.