Experiment 1 Date: 1 August 2006

Title
Gravimetry: Determination of Nickel

Abstract
The main objective of this experiment is to determine the concentration of nickel (II) ion in a nickel
sample solution of unknown concentration. Gravimetric method is used whereby dimethylglyoxime
(1% in alcohol) is added to precipitate the analyte which is later separated from the solution and dried.
The concentration of the sample solution has been calculated as 0.109 mg/mL.

1.0 Introduction
1.1 Background Information of Method
The gravimetric method used in this experiment is among the most accurate methods but
time-consuming. Overall, this method includes precipitation of the analyte in aqueous
solution which is then separated from the mother liquor, washed, heated to constant
weight and weighed as compound of definite composition.

1.2 Rationale / Purpose of Experiment

This experiment aims to determine the concentration of the nickel (II) ion (Ni 2+) in a
sample solution that contains it.

1.3 Background Information of Analyte

The analyte in this experiment is Ni 2+. As an element, it is one of the transition metals
alongside copper, zinc, iron, manganese, etc. In ionic form, it usually possesses a charge
of +2 and gives the solution containing it a green colour. When in contact with basic
chemicals, such as aqueous sodium hydroxide (NaOH) and ammonia, it precipitates into a
green nickel salt compound; this means nickel (II) solution is acidic. In this experiment, it
comes in contact with dimethylglyoxime (DMG, C4H6(NOH)2) and precipitated as nickel
dimethylglyoximate (Ni(DMG)2) in red.

2.0 Materials and Methods

2.1 Apparatus
Volumetric flask (100 mL), beaker (400 mL), labelling tape, pipette (20 mL), measuring
cylinder, microwave oven, thermometer, dropper, electronic weigh, glass rod, basin,
sintered glass crucibles, dessicator, tongs, blue litmus paper, aspirator, side-arm filtering
flask, retort stand, retort clamps.

2.2 Chemicals and Reagents

Nickel (Ni2+) sample solution, distilled water, dimethylglyoxime (DMG, 1% in alcohol),
nitric acid (HNO3, 6 M), urea, oxalic acid, dilute ammonium hydroxide (NH 4OH).

2.3 Experimental Procedures

A sample of nickel solution in a 100 mL volumetric flask is obtained and diluted to the
mark with distilled water. The flask is shaken to mix the solution thoroughly and three
aliquot samples (20 mL) are transferred into separate 400 mL beakers using a pipette.
Each replicate is labelled as 1, 2 and 3 respectively and added distilled water
(approximately 150 mL) before being heated to around 80°C in a microwave oven. DMG
(10 mL) is added slowly to each replicate which their acidity are later checked with blue
litmus paper. HNO3 (6 M) is added dropwise if any of the replicates is not acidic. Urea (3
g) is weighed and added to each replicate and stirred. The mixture is heated to boil for 3
minutes and cooled down to room temperature in a water-filled basin. Each replicate
containing precipitate is added a few drops of dilute NH 4OH. If the drop does not form
red coloration upon mixing with the solution, precipitation is considered complete.
 Three clean sintered glass crucibles, labelled 1, 2 and 3 respectively, are placed in a
dessicator using tongs and weighed separately. The crucibles are then attached to the
mouth of filtering flasks which are connected to the aspirator. The supernatant liquid (100
mL) of the mixture is decanted through the respective crucibles and the mixture in each
replicate is stirred before being filtered through the crucibles using suction (vacuum
filtration) for about 10 minutes. All the red precipitate is made sure to have been
transferred into the crucible. The precipitate is washed with a few portions of distilled
water (10 mL) before being dried in the oven until constant weight. When the experiment
is completed, the crucibles are washed and rinsed in oxalic acid to remove unwashed
precipitate.

3.0 Results and Discussion

Overall, the experiment was conducted without any unfortunate incidents. A few errors
occurred during the conduct of experiment, which will be explained further in the discussion
section.

3.1 Experimental Results and Calculations

When DMG is added to the nickel sample solution and later added urea, red precipitate is
produced. Below are the quantitative results:

Sintered glass crucible

Quantity
1 2 3
Final weight (crucible + precipitate) (g) 31.0303 29.6026 31.6563
Initial weight (empty crucible) (g) 31.0291 29.5917 31.6526
Net weight of precipitate (mg) =
(final weight – initial weight) (g) × 1000 1.2 10.9 3.7
mg/g
precipitate (mg)
Concentration (mg/mL) = 0.012 0.109 0.037
100 mL

0.012  0.109  0.037

Average concentration = mg/mL
3
= 0.053 mg/mL

Standard deviation, s =
(x
i
i  x)2

N 1
x = 0.053 mg/mL, N = 3,
 s=
(0.012  0.053) 2  (0.109  0.053) 2  (0.037  0.053) 2
3 1
= 0.05036 mg/mL (4 significant figures)

3.2 Discussion
The overall reaction between Ni2+ and DMG, buffered by ammonia in urea is illustrated
below:
 dimethylglyoxime nickel dimethylglyoximate

Diluted nickel sample solution is heated up to produce a higher reaction rate when DMG
is added later. An alcoholic solution of DMG is used as the precipitating reagent here as
DMG is slightly soluble in water. Furthermore, DMG enables the separation of nickel
from most elements and is selective towards nickel when the pH value of the mixture is
controlled between 5 and 11. As the sample solution is acidic itself, Ni 2+ will be
precipitated in the form of Ni(DMG) 2 when added DMG. 10 mL DMG is added to each
replicate as excessive DMG may cause crystallization of Ni(DMG) 2. Furthermore,
Ni(DMG)2 is slightly soluble in alcoholic solutions and therefore only small volumes of
DMG are required.

The acidity of the mixture has to be checked because if pH value falls below the
equilibrium pH range (pH = 5 – 11), Ni(DMG) 2 might dissolve back due to formation of
Ni2+. To prevent the pH value from dropping below 5, the mixture is buffered by addition
of urea which contains ammonia (base). Addition of urea also serves to improve the
compactness of Ni(DMG)2 as it is bulky in nature and might cause inconvenient handling
when transferral for filtration. The mixture is heated to boil in order to generate ammonia
via urea hydrolysis so that the pH value increases and gradually precipitates the
Ni(DMG)2 complex. The mixture replicates are cooled as filtration of hot mixture can
cause error up to 0.5%. Dilute NH 4OH is added to ensure that all Ni 2+ in the mixture has
been reacted. Before filtration, the mixture is stirred to facilitate transferral of precipitate
through the sintered crucible. The beaker and glass rod are washed with distilled water to
ensure the whole precipitate is filtered. The crucibles are dried in the oven and placed in
the dessicator to absorb any residual moisture traces. The drying process is repeated for a
few times to improve measurement accuracy. The nickel content of the solution is
computed stoichiometrically from the precipitate weight.

As observed from tabulated experimental results, the concentration value calculated for
crucibles 1 and 3 are far less compared to crucible 2. 1 mL of DMG 1% in alcohol is
actually sufficient for the precipitation of 0.0025 g of the complex, which means 10 mL
of the reagent will ideally precipitate 0.0250 g. Such results owe to a few errors that
occurred during the experiment. After stirring the mixture of DMG and nickel solution in
beaker 3, the glass rod used was washed immediately with pipe water, thereby discarding
the Ni(DMG)2 that might be still left on the rod and therefore decreasing the amount of
precipitate obtained. For beaker 1, the loss of precipitate might have occurred during
cooling of the heated mixtures, whereby excessive water in the basin has caused the
beakers to nearly capsize. In the process, beaker 1 might have been the worst affected
since a small amount of cooling water entered the beaker causing traces of precipitate
washed out. Throughout the experiment, beaker 2 was kept intact and therefore the high
concentration value.
 Smaller amounts of precipitate in beakers 1 and 3 might have also been caused during
addition of DMG after the heating of the solution replicates. All replicates were heated
simultaneously but as the glassware used to contain the DMG was limited, the reagent
was added to the replicates one after another. This causes the DMG to react with the
solution at different temperatures and thereby affecting the amount of precipitate
produced. Replicate 2 was added DMG first at the ideal temperature and thereby the
higher concentration value. During the filtration of precipitate, a small amount of the
mixture of replicate 3 had spilled out of the crucible due to hasty pouring of the mixture
into the crucible, thereby decreasing the amount of precipitate filtered.

However, in the calculations, the calculated average concentration value is far smaller
than the ideal value (0.250 mg/mL) and the standard deviation is deemed too large (The
smaller the standard deviation, the more closely the data are clustered about the average
value). Therefore, in this case, the average value is discarded and the concentration value
of replicate 2 (0.109 mg/mL) is taken as the concentration of Ni 2+ of the sample solution
since it is not only nearest to the ideal value, but it is also considered the best handled
replicate sample throughout this experiment. This means that every millilitre of the
sample solution contains 0.109 mg of Ni2+.

4.0 Conclusion
Gravimetric determination of nickel via reaction of nickel solution with dimethylglyoxime
precipitates nickel dimethylglyoximate which its weight is stoichiometrically proportional with
the nickel amount. The concentration of the nickel solution is determined analytically as 0.109
mg/mL.

5.0 References

Kodama, Kazunobu (1963), “Methods of Quantitative Inorganic Analysis” 1st ed. New York:
John Wiley & Sons Ltd., 16, 263 – 264.

Tan, Yin Toon (1991), “Jadual Berkala Tingkatan 4 dan 5 KBSM” 1 st ed. Malaysia: Penerbit
Fajar Bakti Sdn. Bhd.

Mohd. Marsin Sanagi, Azli Sulaiman, Wan Aini Wan Ibrahim (2004), “Principles of Chemical
Analysis” 1st ed. Skudai: Department of Chemistry, Faculty of Science, Universiti Teknologi
Malaysia, 32.

Truman State University (2002) “The Gravimetric Determination of Nickel” Retrieved August
1, 2006, from http://www2.truman.edu/~blamp/chem222/manual/pdf/nickelgrav.pdf

Terrett, Richard (2005), “Gravimetric Determination of Nickel via Formation of

Dimethylgyoxime Complex” Retrieved August 1, 2006, from http://users.tpg.com.au/terrett/
Downloads/CHEMDocs/Chem2103Lab02culled.pdf