NAME: OSEI

DAVID NANA YAW

INDEX NO:
6142311
EXPERIMENT NO: A.3.1.3
DEMONSTRATOR: STEPHEN BOANDOH
DATE: 5TH
NOVEMBER, 2013.
DETERMINATION OF NICKEL AS THE DIMETHYLGLYOXIME COMPLEX BY
SPECTROMETRY
AIMS OF EXPERIMENT

AIMS OF EXPERIMENT
The aim of the experiment is:
To determination of percentage nickel in the nickel salt of dimethylglyoxime
complex.
INTRODUTION
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 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 sulphur
and iron in pentlandite, with sulphur in millerite, with arsenic in the mineral
nickeline, and with arsenic and sulphur 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.
Spectroscopy is the study of the interaction between radiation and matter as
a function of wavelength () and also the use of visible light dispersed according to
its wavelength, e.g. by a prism.
This idea comprises any measurement of quantity as a function of either their
wavelength or frequency or an alternating field of frequency.
The under lying technique brings about spectrometry which refers to the
assessment of concentration or amount of a given species. In this case, the
instrument that performs such measurements is a spectrometer or spectrograph
which is often used in analytical chemistry for the identification of substances
through the spectrum emitted from or absorbed by them. Such an analytical
process is one that involves a dimethylglyoxime complex with nickel.
Citric acid is sometimes introduced here in the experiment when preparing
the nickel dimethylglyoxime complex since there's an optimum pH range for the
extraction of nickel complex into a suitable organic solvent, heptane. A Citrate
refers either the conjugate base of citric acid, (C3H5O(COO)33), or to the esters of
citric acid. An example of the former, a salt is trisodium citrate; an ester is triethyl

citrate. Since citric acid is a multifunctional acid, intermediate ions exist, hydrogen
citrate ion, HC6H5O72 and dihydrogen citrate ion, H2C6H5O7. These may form salts
as well, called acid salts.
Salts of the hydrogen citrate ions are weakly acidic, while salts of the citrate ion
itself (with an inert cation such as sodium ion) are weakly basic. The citric acid then
as a weak acid is used as a buffer component to maintain the pH of the solution
being prepared at about 7.0. Since dimethylglyoxime complex is a chelating agent,
its molecules readily form bonds with a metal, nickel, forming a complex. The
amount of metal in the complex can be determined by the process of spectrometry
with the underlining principle of absorption of light by the metal. The greater the
amount present, the greater the absorption. In this experiment such a complex
would be prepared with different volumes of a solution containing nickel and it
absorbance would be taken by the spectrophotometer.
CHEMICAL

Dimethylglyoxime

Citric acid

Dilute ammonia solution

Chloroform

Unknown sample

Distilled Water

APPARATUS
Separating funnel
Clamp
Pipette
Burette
Beakers
Ammonium nickel sulphate
Wash bottle
Volumetric flask

PROCEDURE
A
1. A 1 litre solution of 0.27g of pure ammonium nickel sulphate
(NiSO4(NH4)2SO4.6H2O) was prepared.
2. 5ml of the solution was pipette into a 25ml volumetric flask.
3. It was then diluted to the mark and poured in to a beaker.
4. 1.25g of citric acid was then added.
5. Dilute ammonia solution was added drop wise until a pH of about 7.5 was
obtained.
6. The beaker was cooled and the solution was transferred into a separating
funnel.
7. 3ml of dimethylglyoxime solution was added to the solution.

8. It was then left for 2 min. 4ml of chloroform was then added and shaken for 1
minute.
9. The phases were then allowed to separate.
10.The coloured heptane layer was obtained into a beaker.
B
1. 3 other standards were prepared by pipetting 10ml, 15ml and 20 ml of
solution 1 and an unknown solution into four separate beakers.
C
2. A blank solution was also prepared by taking 10ml of distilled water into a
beaker.
3. The procedure for A was repeated for B and C starting from step 3.
4. Six different solutions were obtained and their absorbances were read with
the spectrophotometer.
5. Zero absorbance was set at 465nm with blank and the absorbance for each
solution was taken.
6. A plot of absorbance of the standards against concentration in g/ml was
drawn and the concentration of the unknown was determined from its
corresponding absorbance.

EXPERIMENTAL DATA
Volume/ml
Blank- 0.002M
10- 0.002M
20- 0.004M
30- 0.006M
40- 0.008M
Unknown (10ml)

Absorbance
0.1400
0.5599
1.3121
1.3371
0.7691

CALCULATION
[Ni] in Solution 1
M (NiSO4 (NH4)2SO4.6H2O) = 394.857
m (NiSO4(NH4)2SO4.6H2O) = 0.135g
M (Ni)
= 58.693g/mol
m (Ni) in (NiSO4(NH4)2SO4.6H2O) =
= 20.067mg
[Ni] in Solution 1 = 20.067 mg/L
Conc in g/ml = 20.067 g/ml

C2

Therefore [Ni] in 10ml Solution.

Vol = 10ml
Conc =

[Ni] in 20ml Solution.

Vol = 20ml
Conc =

g/ml

[Ni] in 30ml Solution.

Vol = 30ml
Conc =

g/ml

g/ml

[Ni] in 40ml Solution.

Vol = 40ml
Conc =

g/ml

% of nickel in the nickel salt = (mass of nickel in the nickel salt/ mass of the nickel
salt) 100
% nickel = (0.020067g / 0.135g) x 100 = 14.864%
Theoretical mass = (58.693/394.85) x 0.135g = 0.02006g = 20.067mg
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. Spectrophotometry used for quantitative
determinations depends upon the measurement of the intensity of absorbed
radiation at a specific wavelength. This can be explained using the Beer
Lamberts equation, A= E`cl, where and A= Absorption c= concentration l=

length E= constant. This law proves that the adsorption is directly

proportional to the concentration of the solution. It was observed that the
more concentrated the sample was the deeper the red colour of the nickeldimethylglyoxime complex.
The ammonia solution was added 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. 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. From the graph, the concentration
of the unknown sample was obtained as 30 g/ml.
ERROR ANALYSIS
Operational errors were avoided as such determinate errors were not
noticed. Any possible error is then attributed to indeterminate error as such
being inherent
PRECAUTIONS
1. All glass wares were thoroughly washed before and after use
2. Goggles were worn to prevent accidental contact of fluid to the eye
3. The volume readings were done from the meniscus.
CONCLUSION
The percentage of nickel in the nickel salt was obtained to be 14.862 % and it was
noticed that the more nickel it contained, the more electromagnetic spectrum it
absorbed.
REFERENCES

Modern Analytical Chemistry, Author - David Harvey, Pages 167 to 175