NAME: Kwame Sam-Asmah

INDEX NUMBER: 9649206

EXPERIMENT: A.3.1.3

DEMONSTRATOR: J. F. Morrison

DATE: Mon, 10th November, 2008.

DETERMINATION OF NICKEL AS THE DIMETHYLGLYOXIME COMPLEX BY

SPECTROPHOTOMETRY
AIMS

 To be abreast with the principle of solvent extraction

 To determine the amount of nickel in a sample using spectrophotometry.

INTRODUCTION

Nickel is a metallic chemical element with the symbol Ni and atomic number 28. It is corrosion-resistant, finding many
uses as in alloys and as a plating.

Nickel is a silvery-white metal that takes on a high polish. It belongs to the transition metals and is hard and ductile. It
occurs most usually in combination with sulfur and iron in pentlandite, with sulfur in millerite, with arsenic in the mineral
nickeline, and with arsenic and sulfur in nickel glance.

Similar to the massive forms of chromium, aluminium and titanium, nickel is a very reactive element, but is slow to react
in air at normal temperatures and pressures. Due to its permanence in air and its inertness to oxidation, it is used in
coins, for plating iron, brass, etc., for chemical apparatus, and in certain alloys, such as German silver.

Nickel is magnetic, and is very often accompanied by cobalt, both being found in meteoric iron. It is chiefly valuable for
the alloys it forms, especially many superalloys, and particularly stainless steel. Nickel is also a naturally magnetostrictive
material, meaning that in the presence of a magnetic field, the material undergoes a small change in length. [4] In the case
of Nickel, this change in length is negative (contraction of the material), which is known as negative magnetostriction.

The most common oxidation state of nickel is +2, though 0, +1, +3 and +4 Ni complexes are observed. It is also thought
that a +6 oxidation state may exist, however, results are inconclusive.

The unit cell of nickel is a face centered cube with a lattice parameter of 0.352 nm giving a radius of the atom of 0.125
nm.

Nickel-62 is the most stable nuclide of all the existing elements; it is more stable even than iron-56.

Nickel is used in many industrial and consumer products, including stainless steel, magnets, coinage, and special alloys. It
is also used for plating and as a green tint in glass. Nickel is pre-eminently an alloy metal, and its chief use is in the nickel
steels and nickel cast irons, of which there are innumerable varieties. It is also widely used for many other alloys, such as
nickel brasses and bronzes, and alloys with copper, chromium, aluminium, lead, cobalt, silver, and gold.
Dimethylglyoxime is a chemical compound described by the formula CH3C(NOH)C(NOH)CH3. This colourless solid is the
dioxime derivative of the diketone diacetyl (also known as 2,3-butanedione). DmgH 2 is used in the analysis of palladium
or nickel. Its coordination complexes are of theoretical interest as models for enzymes and as catalysts. Many related
ligands can be prepared from other diketones, e.g. benzil.

Dimethylglyoxime can be prepared from butanone first by reaction with ethylnitrite followed by conversion of the
biacetyl monoxime using sodium hydroxylamine monosulfonate:

CH3C(O)CH2CH3 + CH3CH2ONO → CH3C(O)C(NOH)CH3 + CH3CH2OH

CH3C(O)C(NOH)CH3 + HONHSO3Na → CH3C(NOH)C(NOH)CH3 + NaHSO4

Dimethylglyoxime is used as a chelating agent in the gravimetric analysis of nickel. The use of DMG as a reagent to detect
nickel was discovered by L. A. Chugaev in 1905. For qualitative analysis, dmgH2 is often used as a solution in ethanol. It is
the conjugate base, not dmgH2 itself, that forms the complexes. Furthermore, a pair of dmgH - ligands is joined through
hydrogen bonds to give a macrocyclic ligand. The most famous complex is the bright red Ni(dmgH) 2, formed by treatment
of Ni(II) sources with dmgH2. This planar complex is very poorly soluble and so precipitates from solution. This method is
used for the gravimetric determination of nickel, e.g. in ores.

When dimethylglyoxime is added to an alkaline solution of nickel salt which has been treated with an oxidising agent
(such as bromine), a red colouration is obtained. The red soluble complex contains nickel in a higher oxidation state. The
nickel complex formed absorbs at about 445 nm provided absorbance readings are made within 10 minutes of mixing.

Spectrophotometry is the quantitative study of electromagnetic spectra. It is more specific than the general term
electromagnetic spectroscopy in that spectrophotometry deals with visible light, near-ultraviolet, and near-infrared. Also,
the term does not cover time-resolved spectroscopic techniques. Spectrophotometry involves the use of a
spectrophotometer. A spectrophotometer is a photometer (a device for measuring light intensity) that can measure
intensity as a function of the colour, or more specifically, the wavelength of light. There are many kinds of
spectrophotometers

In this experiment, the principle of solvent extraction is going to be used. Solvent extraction is a very common laboratory
separation procedure used when isolating or purifying a product. It involves the distribution of a solute between two
immiscible liquid phases. e.g. in the extraction of a polar extraction organic substance from an organic solvent using an
aqueous solution, the inorganic ions and polar organic compounds are extracted into the aqueous phase whereas the
non-polar organic molecules go into the organic phase. Since nickel exists as an ion, it will be reacted with a complexing
agent, in this case dimethylgloxime. This complex will then be isolate from the aqueous solution using chloroform as the
extracting solvent. This organic phase will separate itself from the aqueous and the separation can be carried using the
separating funnel. The percentage of the nickel will then be determined using the spectrophotometer.

CHEMICALS AND APPARATUS

 Dimethylglyoxime  Separating funnel

 Citric acid  Clamp
 Dilute ammonia solution  Pipette
 Chloroform  Burette
 Unknown sample  Beakers
 Water  Wash bottle
PROCEDURE

A)
1. 0.135g of pure ammonium nickel sulphate [NiSO4(NH4)SO4.6H2O] was weighed and transferred into
2. 1L volumetric flask. Sufficient distilled water was added to dissolve the salt and diluted exactly to the
mark with distilled water (SOLUTION 1).
3. 5mL of SOLUTION 1 was pipette into a beaker.
4. It was then diluted to 25mL with distilled water.
5. 1.25 g of citric acid was added
6. Dilute ammonia solution was added drop wise until pH was 7.
7. The solution was transferred into a separating funnel.
8. 5mL of dimethylglyoxime solution was added.
9. It was left for about two minutes
10. 3mL of chloroform was added and shaken for a minute.
11. The phases were allowed to separate in the funnel.
12. The red chloroform layer was collected in a beaker
B) Other standards were prepared by pipetting 10mL, 15mL, 20mL of SOLUTION 1 into three separate beakers.
C) A known volume (10mL) of the unknown sample was measured into a 25mL volumetric flask, diluted with
water to the mark and transferred into a separate beaker
D) A blank solution was prepared by taking 25mL of distilled water into a beaker. The procedure A was
repeated for B, C and D starting form step 3.
E) The absorbance was set to zero on the spectrophotometer at 465nm with the blank.
F) The absorbance for each solution was measured at 465nm against the blank.

EXPERIMENTAL RESULTS:

Volume Of Standard Solution/ml Absorbance

5 0.54
10 0.95
15 1.54
20 2.00
Unknown(1.5ml) 0.13
Blank 0.00
CALCULATIONS

For the 5mL vol of ammonium nickel sulphate

Initial conc of Ni2+ , C1= 0.135g/L
Initial vol of Ni2+ , V1 = 5mL
Final vol of Ni2+ , V2 = 25mL
C2 = (C1 V1)/ V2
= (0.135g/L × 5mL) / 25mL
= 0.027 g/L = 27 mg/L

For the 10mL vol of ammonium nickel sulphate

Initial conc of Ni2+ , C1= 0.135g/L
Initial vol of Ni2+ , V1 = 10mL
Final vol of Ni2+ , V2 = 25mL
C2 = (C1 V1)/ V2
= (0.135g/L × 10mL) / 25mL
= 0.054 g/L = 54 mg/L

For the 5mL vol of ammonium nickel sulphate

Initial conc of Ni2+ , C1= 0.135g/L
Initial vol of Ni2+ , V1 = 15mL
Final vol of Ni2+ , V2 = 25mL
C2 = (C1 V1)/ V2
= (0.135g/L × 15mL) / 25mL
= 0.081 g/L = 81mg/L

For the 5mL vol of ammonium nickel sulphate

Initial conc of Ni2+ , C1= 0.135g/L = 135 mg/L
Initial vol of Ni2+ , V1 = 20mL
Final vol of Ni2+ , V2 = 25mL
C2 = (C1 V1)/ V2
= (0.135g/L × 20mL) / 25mL
= 0.108 g/L = 108 mg/L

DISCUSSION

From the calculations, it could clearly be seen that as the volume of the ammonium nickel sulphate
concentration was increased, the concentration of the nickel present in the solution prepared also increased.
Also, the ammonia solution was added in order so that the acidic nature of the solution could be neutralized as
best as possible. It was neutralized to a slightly basic pH of about 7.5.

Since the nickel was in the form of ions in the solution, the best way to get into the organic phase was to first
complex it with a complexing agent in this case the dimethylglyoxime. This complex formed was then dissolved
into the organic phase (chloroform) so that on separation the amount of nickel present in the organic phase
could be determined with the spectrophotometer.

In the determination of the absorbance by the solution collected, the cuvette was wiped clean of any water or
fingerprints to prevent interferences in the absorbance. Also in the collection of the organic phase the aqueous
phase was prevented form entering the organic phase. The graph that was plotted was a straight line graph of
the absorbance against the concentration.

PRECAUTIONS

 The mixture in the separating funnel was shaken vigorously in order to ensure a very high
separation coefficient.
 A little of the red chloroform layer was left at the tip of the funnel in order to prevent some of the
aqueous phase from entering the organic phase that was collected.
 The cuvette was wiped clean with a dry tissue and handled in such a way that no finger prints were
made on it. This will allow correct absorbance of light.
 The apparatus used were washed thoroughly before and after use.
 The ammonia solution was added in a fumehood in order to prevent the gases from entering the
nostrils.

CONCLUSION

From the experiments conducted it could be said that before ions in solution can be extracted, they have to be
complexed with a complexing agent so that they can be obtained in an organic phase which can then be
separated from solution.
The concentration of the nickel obtained was found to be 2mg/L from the graph.
Also, the chloroform used as the organic phase was a good one since it was able to separate out of the
solution.
REFERENCES

 Laboratory Manual, Chem 269, page 12

 Vogel’s Qualitative Inorganic Analysis, 3rd edition, page 462, 181
 Vogel’s Quantitative Chemical Analysis, 5th edition, page 694, 262
 Silberberg, Chemistry, 3rd edition, page 982