LABORATORY REPORT

YEAR 1
INORGANIC CHEMISTRY
EXPERIMENT A3

NAME : TEH CHIN MAN

MATRIC NO. : U2103300/1
SESSION : 2021/2022
OCCURRENCE :1
TITLE : GRAVIMETRIC DETERMINATION
AND IR-CHARACTERIZATION OF
NICKEL COMPLEX
DATE OF EXPERIMENT : 22/11/2021
DATE OF SUBMISSION : 05/12/2021
LECTURER : DR. NOR ASRINA BINTI SAIRI
TABLE OF CONTENTS Page
Title……………………………………………………………………………………….3
Objective………………………………………………………………………………….3
Introduction…………………………………………………………………………….3-4
Method
Part A…………………………………………………………………………………4
Part B……………………………….………………………………………………5-7
Result
Part A…………………………………………………………………………………8
Part B……………………………….……………………………………………..9-10
Discussion……………………………………………………………………………11-12
Question & Answer (Q&A) …………………………………………………...…….13-14
Conclusion…………………………………………………….........................................14
References…………………………………………………………………….................14

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Title: Gravimetric Determination and IR-Characterization of Nickel Complex
Objective:
1) To enable the understanding of the concept of gravimetric analysis
2) To enable derivation of the mass of nickel calculated from the mass of precipitation
Introduction:
Gravimetric analysis is a technique through which the amount of an analyte (the ion
being analyzed) can be determined through the measurement of mass. Gravimetric analyses
depend on comparing the masses of two compounds containing the analyte. The principle behind
gravimetric analysis is that the mass of an ion in a pure compound can be determined and then
used to find the mass percent of the same ion in a known quantity of an impure compound.
Gravimetric analysis is different from volumetric analysis. Volumetric analysis is a type of
quantitative analysis in which we can measure the amount of an unknown compound using its
volume. The units measurement of volumetric analysis are “L, mL, m3, dm3 ” while units
measurement for gravimetric analysis are “mg, g, kg”. To sum up, volumetric analysis measures
the quantity of an analyte using volume whereas the gravimetric analysis measures the quantity
of an analyte using the weight.
Gravimetric analysis can be applied in real life for many users say, for example, to
monitor levels of lead in water for human consumption, which if not monitored could cause lead
poisoning and death. Some more examples of daily usage are the nutritional information tables
on foods printed on their packages because many of the components listed are analyzed in a lab
and % composition measured by mass. One more application is determining the mineral content
of your drinking water, and minerals such as lead as mentioned above, fluoride, mercury,
calcium, etc. Determination of total suspended solids in water is yet another gravimetric
application. One very valuable, as well as a very useful application, is making sure the gold
content in your jewelry is true to the jewelry shop seller's description. Determining the amount of
fat in milk can be done by gravimetric analysis. Even a patient being weighed at the doctor's
office is a form of gravimetric analysis, as recorded weight changes over a period of time could
be a sign of illness.
Nickel is a naturally occurring, lustrous, silvery-white metallic element used by
humankind for some 2,000 years. It was only identified as an element in the 18th century. It then
came to prominence in plating and in alloys. Stainless steel was discovered in the early 20th
century and nickel was found to have a beneficial role. Alloys based on nickel have excellent
corrosion and heat resistance, making them ideal for uses in harsh environments such as
chemical plants, jet engines and desalination facilities. While nickel metal is the most important
form of nickel by volume, nickel compounds nevertheless have critical uses. They are essential
to a wide range of industrial sectors including transport, aerospace, marine and architectural
applications and for the manufacture of many consumer goods. Nickel compounds also play a
key role in environmentally-friendly technologies. Most people do not realise the importance of
nickel compounds in the functioning of everyday products like cars and electronics because,
when they are used in manufacturing processes, they are transformed into metal, other
substances or integrated into products. Nickel compounds are never directly accessible to the
user.

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 The prepared compound will be characterized by Fourier Transform Infrared
Spectroscopy, also known as FTIR Analysis or FTIR Spectroscopy, which is an analytical
technique used to characterize organic, polymeric and in some cases, inorganic materials. The
FTIR analysis method used infrared light to scan test samples and observe chemical properties.
FTIR offers quantitative and qualitative analysis for organic and inorganic samples. FTIR
identifies chemical bonds in a molecule by producing an infrared absorption spectrum. The
spectra produce a profile of the sample, a distinctive molecular fingerprint that can be used
to screen and scan samples for many different components. FTIR is an effective analytical
instrument for detecting functional groups and characterizing covalent bonding information.
FTIR analysis helps clients understand materials and products. Analytical testing sample screens,
profiles and data interpretation are available on a global basis from our experts who deploy FTIR
to identify chemical compounds in consumer products, paints, polymers, coatings,
pharmaceuticals, foods and other products.

Method:
Part A:
1) 25 mL of a nickel (II) sulfate solution was pipetted into each of the two 400-ml beakers.
2) 5 mL of dilute hydrochloric acid (2M) was added and the solution was diluted to 200 mL
with distilled water. The solution was heated to 60-80°C.
3) About 20 mL of dimethylglyoxime solution (1%) was added to the hot solution, followed
by dropwise addition, with stirring, of ammonium hydroxide until precipitation had
occurred and the solution was slightly basic (about 2 mL of excess ammonium
hydroxide). The completeness of precipitation was tested by adding more
dimethylglyoxime solution (1%).
4) The precipitate was warmed for 30 minutes. The precipitate was cooled to room
temperature and was filtered through a weighed No.4 sintered glass crucible previously
dried at 110°C.
5) The precipitate was washed with cold distilled water until it is free from any chloride
(tested with silver nitrate solution) and was dried overnight.
6) The crucible in a desiccator was cooled and weighed to constant weight.
7) From the weight of the precipitate and a knowledge of the theoretical quantity of nickel
in bis(dimethylglyoximato)nickel(II), the concentration (in g L-1) of nickel (II) ions in the
solution.

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Part B:
Preparation Method 1: Nujol mull

1) The samples were grounded in a 2) 5 to 10 mg of finely ground sample

mortar. were placed onto the face of a KBr
plate.

3) A small drop of mineral oil was added. 4) The second window was placed on top.

5) With a gentle circular and back-and-forth rubbing motion of the two windows, the mixture
was evenly distributed between the plates. The mixture was appeared slightly translucent,
with no bubbles, when it was properly prepared.

6) The sandwiched plates were placed in the spectrometer and a spectrum was obtained. The
strongest bond had a transmission of 0 to 10% and was not absorbing for more than 20cm-1.

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Preparation Method 2: KBr pellet/disk

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Preparation Method 3: ATR

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Result:
Part A:
Below is the table shows the weight of weighed No.4 sintered glass crucible with
bis(dimethylglyoximato)nickel(II)
Table 1: Table of the weight of weighed No.4 sintered glass crucible with
bis(dimethylglyoximato)nickel(II)
Mass of empty
Mass of empty Mass of Average mass of
Crucible crucible and
crucible (g) precipitate (g) precipitate (g)
precipitate (g)
A 29.0878 29.3227 0.2349
0.2237
B 30.1277 30.3402 0.2125

Relative molecular mass of Ni(C4H7O2N2)2 is 288.9 g/mol

From equation,
Ni2+ + 2C4H8O2N2 → Ni(C4H7O2N2)2 + 2H+

1 mole Ni2+ ≡ 1 mol Ni(C4H7O2N2)2

𝑚𝑎𝑠𝑠
Number of moles of Ni(C4H7O2N2)2 =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

0.2237𝑔
=
288.9 𝑔/𝑚𝑜𝑙

= 7.7432 x 10-4 mol

Concentration of nickel in solution

7.7432×10−4 𝑚𝑜𝑙
= × 𝑀𝑟𝑁𝑖 2+
(25/1000)𝐿

7.7432×10−4 𝑚𝑜𝑙
= × 58.69𝑔/𝑚𝑜𝑙
(25/1000)𝐿

= 1.8178 g/L

*𝑀𝑟𝑁𝑖 2+ = Relative Formula mass of Ni2+

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Part B:
Below is the table of group absorption frequency and the major functional group
determined in the IR Spectrum of Sample A based on Table 3.
Table 1: IR Spectrum Table based on Sample A
Group Absorption Frequency (cm-1) Major Functional Group
2923.39 C−H
2164.05 C≡C
1788.74 =C−H
1568.48 C=C

Below is the figure of infrared spectroscopy graph of sample A:

FINGERPRINT REGION

FUNTIONAL GROUP REGION

Figure 1: Infrared Spectroscopy Graph of Sample A

Below is the table of group absorption frequency and the major functional group
determined in the IR Spectrum of Sample B based on Table 3.
Table 2: IR Spectrum Table based on Sample B

Group Absorption Frequency (cm-1) Major Functional Group

2923.22 C−H
2164.27 C≡C
1787.72 =C−H
1567.98 C=C

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 Below is the figure of infrared spectroscopy graph of sample B:

FINGERPRINT REGION

FUNTIONAL GROUP REGION

Figure 2: Infrared Spectroscopy Graph of Sample B

The table below is used to determine the major functional group in the infrared
spectroscopy graph of Sample A and Sample B.
Table 3: IR Spectrum Table

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Discussion:
The quantity of nickel ions in a salt is determined by precipitating the ions with
dimethylglyoxime in an ammoniacal solution. The product is bis(dimethylglyoximato)nickel(II),
chemical formula Ni(C4H7O2N2)2. It is an insoluble red precipitate. The precipitate is collected
and dried, then weighed. The precipitation is affected by the addition of dilute ammonium
hydroxide to a hot solution of the nickel salt and dimethylglyoxime.
Dilute hydrochloric acid (2M) is added to the solution to prevent other unwanted things
from precipitating, therefore won't affect the mass of precipitate. Heating the solution to 60-80°C
helps the precipitate go from colloidal (dispersed throughout solution) to crystalline (clumped
together) to make filtration more effective and accurate. Temperature of the solution is kept
around 60-80 °C so that the rate of chemical reaction is accelerated, and also to increase the
solubility of the solution. Dimethyglyoxime (DMG) is used as the precipitating reagent during
the experiment because dimethyglyoxime is only slightly soluble in water. It is therefore crucial
to avoid the addition of too large an excess of the reagent because it may crystallize out with the
chelate.
To improve the compactness of the precipitate, homogeneous precipitation is often
performed in the analytical scheme. This is accomplished by the adjustment of the pH to 3 or 4,
followed by the addition of ammonium hydroxide. A slow increase in the concentration of
ammonia in the solution causes the pH to rise slowly and results in the gradual precipitation of
the complex. The result is the formation of a denser, easily handled precipitate. Ammonium
hydroxide was added in excess so that it enables the complex to dissolve, so that the precipitate
obtained at the end of the experiment will contain no impurities. In order to test whether the
precipitation is complete, some sample in the beaker can be taken out and tested. The test for
complete precipitation is carried out by adding a drop of dimethylgloxime solution. If
precipitation occurs in the sample solution, the precipitation is not completed. The ammonium
hydroxide need to be added more to complete the precipitation. If the sample solution is
colourless after adding dimethylgloxime, the precipitation is completed.
The precipitate is warmed for 30 minutes as heating the precipitate and solution
provides a third way to induce coagulation. As the temperature increases, the number of ions in
the primary adsorption layer decreases, which lowers the precipitate's surface charge. The
digestion of precipitate help to maximise the amount of precipitate formed. When carrying out
the purification, make sure the precipitate is completely transferred from the beaker to the
sintered glass, so that a precise mass of the precipitate can be obtained. The precipitate is filtered
through No.4 sintered glass crucible and rinsed with cold distilled water to wash away the
impurities, such as chloride, so that the mass obtained consists only the precipitate. After
washing the precipitate with cold distilled water, test with silver nitrate to make sure the
precipitate is free from any chloride. White precipitate (AgCl) will form if there is any chloride
present when test with silver nitrate. The precipitate is then dried overnight in an oven to remove
residual traces of rinse solution and to remove any volatile impurities.

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 In part A experiment, the concentration of nickel(II) ions in the solution can be
determined from the mass of precipitate. In part B experiment, the functional group is
determined by referring the generated infrared spectroscopy graph and the given IR Spectrum
table. The infrared spectroscopy graph can be divided into two regions which are functional
group region and fingerprint region. The regions are separated at 1500 cm-1 at x-axis of the
graph. From the graph of sample A and sample B, the major functional groups determined are
C−H, C≡C, =C−H and C=C.

The simplest method to obtain IR spectra of solids is Nujol (mineral oil) mulls between
KBr plates. The samples should grounded in a mortar to reduce the average particle size to 1 to 2
microns. If the bands are distorted, the particle size is too large and some radiation incident on
the mull has been scattered out of the sample bean. Reduce the particle size if a better spectrumis
is required. The other method to obtain IR spectra is KBr pellet. The pellet is much thicker than a
liquid film, hence a lower concentration in the sample is required. Too high concentration
usually causes difficulties in obtaining clear pellets. KBr does not show any absorption spectrum
in IR region because it has a 100% transmission window in the range of wave number (4000-400
cm-1) at the FTIR spectroscopy. That’s the reason KBr is chosen as one of the method to obtain
IR spectra. The method used to obtain IR spectra in this experiment is ATR method. ATR is a
sampling technique used in conjunction with infrared spectroscopy which enables samples to be
examined directly in the solid or liquid state without further preparation. ATR is used for surface
analysis without any extra materials or holder. Thus, it is more convenient.
The possible errors in these experiments:
1) Overheat the solution to above 80°C.
2) Incomplete precipitation results in a low percentage of analyte.
3) Incomplete drying of the sample results in a high percentage of analyte.
4) Incomplete washing of the precipitate affecting the mass of precipitate.
5) Eyes of observer is not perpendicular to the scale of apparatus.
Precaution:
1) Do not heat the precipitate to temperature much greater than 80°C as it could decompose
the compound.
2) Test the completeness of precipitation with silver nitrate solution.
3) Cold distilled water was used to wash the precipitate in order to free from any chloride.
4) Eyes of observer must perpendicular to the scale of apparatus.
5) For Nujol mull preparation method, wipe the windows with tissues, then wash several
times with methylene chloride, then ethanol.
6) For KBr pellet preparation method, the sample must be very finely ground to reduce
scattering losses and absorption band distortions.
7) Gloves must be worn to prevent fogging.

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Q&A:
1) Draw the structural formula of bis(dimethylglyoximato)nickel(II) and describe the type of
hybridization involved.

Structural formula of bis(dimethylglyoximato)nickel(II):

The type of hybridization of bis(dimethylglyoximato)nickel(II) is dsp2. Figure below

explains the hybridization of of bis(dimethylglyoximato)nickel(II).

Figure 3: Hybridization of bis(dimethlglyoximato)nickel(II).

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 2) Explain why the temperature of the solution must be maintained at 60-80°C during the
precipitation process.
Increasing temperature of a solution increases the solubility of the ionic compounds,
improving the likelihood of precipitate formation. Besides that, the boiling point of
dimethylglyoxime solution (1%) is below 80°C, so it’s kept below 80°C so that there’s no
loss of dimethylglyoxime solution (1%). Furthermore, dimethylglyoxime solution is
volatile and it could vaporize immediately once the temperature exceeds 80°C. By this
time, ammonium gas will be released in excess, the basicity of the solution will be
reduced, resulting the solution to be more acidic, and the nickel complex will be
dissolved in acidic solution, affecting the mass of the precipitate obtained.

Conclusion:
1) The concentration of nickel in solution is 1.8178 g/L.
2) The concept of gravimetric analysis is understood.

References:

1) Laboratory Manual, Safety and Basic Laboratory Techniques (SIC1011)

2) https://www.vedantu.com/chemistry/gravimetric-analysis
3) https://www.wiredchemist.com/chemistry/instructional/laboratory-tutorials/gravimetric-analysis
4) https://www.differencebetween.com/difference-between-volumetric-and-gravimetric-analysis/
5) https://nickelinstitute.org/media/2298/ni-compounds-2015-v12-final.pdf
6) https://rtilab.com/techniques/ftir-analysis/
7) https://chemlab.truman.edu/files/2015/07/nickelgrav.pdf
8) https://yeahchemistry.com/questions/discuss-observation-and-possible-error-results-gravimetric-
analysis

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