INTRODUCTION

Gravimetric analysis is a method in analytical chemistry to determine the quantity of an analyte

based on the mass of a solid. Principle behind the gravimetric analysis that the mass of an ion in a
pure compound can be determined. Later used to find the mass percent of the same ion in a known
quantity of impure compound  Gravimetric analysis does not require a sampling step, so that the
change in the mass of particles would directly provide the information about the averaged growth of
particle.(Byun J et’al 2019)

The principle of gravimetric analysis can also be based upon the precipitation of a metal cation as an
insoluble complex, by use of a suitable complexing agent. The separation of nickel from other ions
in a sample is a good example of specificity in quantitative analysis (Liu T et’al 2011). The amount
of nickel can be determined by precipitation with dimethylglyoxime from a slightly ammoniacal
solution filtering out the precipitate then drying it and the weighing it when it is dry. The formation
of the red chelate occurs in a solution in which the pH is buffered in the range of 5-9. The chelation
reaction that occurs goes as follows:

This reaction shows a metal (nickel) forming a compound with a ligand (dimethylglyoxime) which
is bidentate meaning coordination to the metal ion occurs through both nitrogen atoms. For ligands
and metal;

K1=[M2+][L-]2/[ML2]

The ligands the form a neutral complex with the metal which is insoluble in polar solvents, thereby
the following equilibrium co-existing in the solution;

ML2(aq) ====== ML2(SOLID) wth K2 = [ML2(Aq)] / [ML2(Solid)]

Since the concentration of the precipitate is a constant,K1K2 can be combined thus giving off a new
constant K3 and hence;
[M2+][L-]2= K3

Provided that the ion product is greater or exceeds K 3 precipitation will occur. Successful
gravimetric analysis can be obtained this way where by K1K2 product is small and hence the aim of
this experiment is to successfully use gravimetric analysis to determine or estimate the amount of
nickel II using the ligand dimethylglyoxime.

REAGANTS AND APPARATUS

 Precipitation reagent 1% solution of dimethylglyoxime in alcohol

 Ammonia solution: 1:1 ammonia solution
 Washing solution: distilled water heated up to 70 to 80oC
 Unknown sample solution of nickel (II)
 Methyl red
 Dilute acetic acid
 Measuring cylinder
 Beaker
 Stirring rod
 Water bath
 Filtration equipment
 Oven
 Sintered crucible
 Desiccator weighing balance

PROCEDURE

100 ml of distilled water and 1 ml of methyl red were added to a 25 ml given sample. Then dilute
ammonia solution was added drop wise till colour changed from red to yellow as mineral acid was
neutralised. Dilute acetic acid was then added to acidify the solution. The solution was heated to 70°
C and 30 ml of 1% dimethylglyoxime was added with constant stirring. Then 1:1 ammonia
solution was added drop wise till colour changed from red to yellow confirming alkalinity
and the precipitate digested on a water bath for an hour. The solution mixture was then cooled for
about an hour. Complete precipitation was then tested by adding a few drops of dimethylglyoxime
to clear supernatant liquid. The solution mixture was then cooled for an hour. The mixture was then
filtered by transferring the supernatant to a weighed sintered crucible and the precipitate washed
four times with hot water. The washings were transferred to the crucible making use a policeman to
remove any adhering precipitate from the beaker. The precipitate on the sintered crucible washed
again with hot water to remove free Cl- and SO4²- ions. The precipitate was then dried in the
oven at 110 - 120°C, cooled and then weighed. The drying in the oven followed by weighing was
repeated until a constant mass value was obtained. The amount of nickel was then calculated. The
drying cooling and weighing was repeated until a constant weight was observed.

RESULTS AND ANALYSIS

The results that were obtained from the experiment were recorded in the table below

Table 1; showing the results obtained in the experiment

Mass of empty Mass of crucible + Mass of crucible + Mass of crucible +

cruicible (g) nickel precipitate 1 (g) nickel precipitate 2 (g) nickel precipitate 3 (g)
67.2560 g 67.5155 g 67.5116 g 67.5056 g
Mass of precipitate 0.2595 g 0.2556 g 0.2496 g

Mass of precipitate ; (mass of crucible + nickel precipitate) – mass of empty crucible

Molar mass of nickel – dimethylglyoxime (Ni(DMG)2) = C8H14N4NiO4, therefore:

Molar mass = [(8 X 12.011) + (14 X 1.00794) + (4 X 14.00674) + (1 X 58.6934) + (4 X

15.9994)] = 288.91 g/mol.

Gravimetric factor = 58.693 g/mol / 288.91 g/mol =0.2032

Mass of nickel in the precipitate = (58.693 x 0.2595)/ 288.91 = 0.05271 g

Concentration of nickel in solution = 0.05271 g / 0.025 L = 2.1084 g/L

ANSWERS TO QUESTIONS

1. To clean the crucibles containing the nickel – dimethylglyoxime complex a small volumeof
concentrated nitric acid is added to the crucibles. This will dissolve the precipitate andthe resulting
solution poured into the nitric acid waste bottle. The crucible is furtherwashed with water.

2. Only a small volume is used so that it does not interfere with precipitation process.

DISCUSSION

The gravimetric factor was calculated based on the molar masses of nickel and the
dimethylglyoxime (Ni(DMG)2 complex and was found to be 0.2032, which was then used to
calculate the mass of nickel in the complex was found to be 0.05271g and the concentration of
nickel in the sample solution which was found to be 2.1084g/L. According to (Carmosini et al.,
1997), the mass found to be 0.04764g/L. This shows that some errors might have occurred

during the experiment. Some errors that may have been encountered are possibly instrumental

errors which might have occurred when delivering reagents using measuring cylinders, instrumental
errors of the analytical balance brought about by presence of air in the analytical balance can be
accounted for the less accuracy of the results. Some results may also be because of weighing the
precipitate when it was not fully cooled and this can mess up the accuracy and precision of the

experiment. Some errors include that some of the precipitate may have been lost

during washing and filtration of the precipitate resulting in low results. Also chemical
interferences in gravimetric analysis may result in either high or low results, depending on the type
of interference (Skoog, D. A., West, D. M., & Holler, 1996).

Advantages of gravimetric analysis include that it is more accurate and precise when using
modern analytical balance.Also possible sources of error are readily checked since filtrates can be
tested for completeness of precipitation and precipitates may be examined for the presence of
impurities. Lastly, it is an absolute method; it involves direct measurement without any form of
calibration being required. It also has some disadvantages which include that it
requires meticulous time consuming. Also since methods are often convoluted and a slight mis-step
in a procedure can often mean disaster for the analysis (colloid formation in precipitation
gravimetry, for example) (Byun et al., 2019).

CONCLUTION

The gravimetric factor was calculated based on the molar masses of nickel and the
dimethylglyoxime (Ni(DMG)2 complex and was found to be 0.2032, which was then used to
calculate the mass of nickel in the complex was found to be 0.05271g and the concentration of
nickel in the sample solution which was found to be 2.1084g/L.

REFERENCES

Skoog, D. A., West, D. M., Holler, F. J., & Crouch, S. R. (2013). Fundamentals of analytical
chemistry. Cengage learning.

Haas, K. L., & Franz, K. J. (2009). Application of metal coordination chemistry to explore and
manipulate cell biology. Chemical reviews, 109(10), 4921-4960.

Liu, T., Guo, Z., Wang, Z., & Wang, M. (2011). Effects of gravity on the electrodeposition and
characterization of nickel foils. International Journal of Minerals, Metallurgy, and Materials, 18(1),
59–65. https://doi.org/10.1007/s12613-011-0400-6

Byun, J., Kim, K. H., Kim, B. K., Chang, J. W., Cho, S. K., & Kim, J. J. (2019). Gravimetric
analysis of the autocatalytic growth of copper microparticles in aqueous solution. RSC Advances,
9(65), 37895–37900. https://doi.org/10.1039/C9RA06842B

Carmosini, N., Ghoreshy, S., & Koether, M. C. (1997). The Gravimetric Analysis of Nickel Using a
Microwave Oven. Journal of Chemical Education, 74(8), 986. https://doi.org/10.1021/ed074p986
 DEPARTMENT OF CHEMISTRY

CHE 314
EXPERIMENT 4

SURNAME: SAMAKWATI

NAME : BOTLHE KGOTLA

ID : 202003096

LAB DAY: WEDNESDAY GROUP B

DATE: 08/003/23

GROUPTIME: 1500-1800 HRS

GRAVIMETRIC ESTIMATION OF NICKEL (II)