The Analytica Societas Journals

Metal Determination on a Mixture Sample through Electrogravimetry.

2
Malolot, Ryan Dave*, 2Barbaza, Marjette, 2Dela Paz, Xech Rafael, 1De Castro-Cruz Kathlia**,

1
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology;
2
Student (s), CHM115L/A12, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology

ARTICLE INFO

Article History:
Volume No.: 2
Issue No.: 2
ABSTRACT
Date of Submission: 30 August 2017
Date of Acceptance: 31 August 2017
Electrogravimetry is an electroanalytical method used to separate and quantify ions of
a substance, usually metals. Analyte solutions are electrolyzed, and the reduction
Keywords:
causes the analyte to be deposited on the cathode. In this experiment, the
Electrogravimetry
electrogravimetric technique was applied in the determination and separation of Co,
Electrodeposition Cu, and Ni from solutions containing these metals individually or in mixture. Aqueous
solutions of divalent salts of the metals were electrolyzed with a constant current, and
Constant Weighing. the cathode where the metal deposited was dried to obtain a constant mass. The students
analyzed solutions of Cu, Co, Ni, mixture of Cu/Co, and Cu/Ni at different currents. It
Overpotential was then compared to true value to determine the success of electrolysis. The students
were able to electrolyzed the individual metal ions to sample and able to observed the
Electroanalyzer
separation in mixtures but unable to weigh the metal ion separately.

Introduction Two types of electrogravimetric methods are

In classical gravimetric analysis, the determination of the
amount of metal analyte depends primarily on the mass-
measuring or weighing process after the analyte has been
precipitated from a solution containing it. However, in
electrogravimetry, the amount of metal is determined by
utilizing concepts in electrochemistry. The analysis is done by
depositing the metal analyte on a pre-weighed electrode, where
the amount of metal may be calculated from the gained mass of
the electrode where the metal has deposited. Electrogravimetric
techniques are commonly utilized and are well-known, due to
the fact that they have moderately high sensitivity, high
accuracy, and do not require preliminary calibration against
standards, and thus, absolute analysis of the analyte content of
unknown solutions is possible (Harvey, 2000).
commonly used in analyses of analyte metals: constant current
electrolysis and constant potential electrolysis. As its name
suggests, in the process of constant current electrolysis, the
current is set to a constant value and the potential is allowed to
vary and increase. No control of the potential of the working
electrode is done and the applied potential is kept constant:
however, it should provide sufficient current to complete the
electrolysis of the analyte in a reasonable length of time. This
electrogravimetric method is primarily used in the deposition of
metals from a solution known to contain a single metal only, as
it cannot be used in the separation of metals. If separation of
metals is desired, the latter method, constant potential analysis,
is primarily utilized. This method is actually the simplest way
of performing an analytical electrolysis, and as its name
suggests, it is based on keeping the working electrode potential
constant. It is used in the separation of metal components in
mixture, provided that the values for the decomposition
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potentials of the metals present are not widely separated. The
instrument for constant current electrolysis consists of a
suitable cell and a direct-current power supply, while that of the
latter consists of two independent electrical circuits that share a
common electrode (the working electrode) at which the analyte
is deposited (Amrita Vishwa Vidyapeetham University, 2016).
Electrogravimetric methods have several applications,
which include the determination of the amount or concentration
of metals and other elements with significantly high accuracy
and precision in quantitative analysis, separation of components
of a mixture in a solution by selectively plating one of its
components onto the cathode, removal of interferences in
analyte solutions to obtain more accurate results, and many
more. In this experiment, electrogravimetric analysis was used
to determine the amount of Ni, Cu, and Co in solutions
containing NiCl2, CuCl2, and CoCl2, respectively, with
varying currents. Moreover, the technique was also applied in
the separation of these same metals in a solution containing a
mixture of two of them. The experiment aims to utilize the
aforementioned gravimetric methods in the determination of
amount of metal and in the separation of metal components in
mixture of analyte solutions.
for 10 minutes or no more fumes are visible. Dilute the mixture
with 65 mL distilled water and add 36 mL of concentrated
NH4OH and 0.5 mL of 85% hydrazine hydrate. Heat the
solution to 70 C.
The next sample digested is nickel. Place sample in 100ml tall-
form beaker. Slowly add 2.3ml conc. H2SO4. Place in hot plate.
Heat to near boiling or vapor condensation is observed.
Continue heating for 5 minutes after the indicated color change
(solid light green). Dilute the mixture with 65 mL distilled
water and add 35mL of conc. NH4OH and heat the solution to
70 C
The other samples are metal mixtures in which the prepared
individual samples are mixed forming a combination of copper
and cobalt, and a copper and nickel mixture.
As the solutions were prepared or digested, the researchers
proceed to the next step which is the electrolysis part. Each of
the electrodes are weighed first and then using an
Electroanalyzer, the samples were subjected to a current of
about 1.2 to 2.4 amperes and electrolysis was performed. After
the color dissipates, the electrodes will be weighed.

Experimental Section Results and Discussion

The reagents used were Conc. H2SO4, conc. HNO3, conc. The students were able to meet the objectives of the experiment.
NH4OH, 85% hydrazine hydrate and sample CuCl2, CoCl2, The findings were the following;
and NiCl2.
Table 1: Metal Deposited
The apparatus used were Hot plate, pipet (10ml), beaker, and Metal Sample Current (A) Metal deposited (g) Time (sec)
Electroanalyzer. Cu 1.2 0.580± 0.063 960
Co 2.2 0.608± 0.0186 1680
The Electroanalyzer is the equipment used as the source of the Ni 2.2 0.573± 0.0157 2520
current and potential being applied to the analyte. Cu/Ni 1.2/ 2.2 0.753± 0.041 4320
Cu/Co 1.2/ 2.2 0.973± 0.0139 2820
The experiment can be divided into two parts in which the first Cu 1 0.644± 0.012 1080
part is the preparation and digestion of sample and the second Co 2 0.557± 0.02 1800
part is the electrolysis. Ni 2 0.668± 0.019 2700
Cu/Ni 1/ 2 0.567± 0.159 4500
For the sample digestion in copper, Place sample in 100ml tall- Cu/Co 1/ 2 0.749± 0.017 3000
form beaker. Slowly add 2.3ml conc. H2SO4. Place in hot plate. Cu 1.4 0.686± 0.008 900
Heat to near boiling or vapor condensation is observed. The Co 2.4 0.616± 0.010 1320
solution will turn pale green after 2 minutes. Add 1 mL of Ni 2.4 0.539± 0.008 4200
HNO3 while the solution is pale green. Continue heating to Cu/Ni 1.4/ 2.4 0.852± 0.0059 2400
assure complete removal of chloride ion. Dilute the solution Cu/Co 1.4/ 2.4 0.971± 0.0086 4200
with 100 mL distilled water *only the 1st five set of data was computed by The Analytica Societas,
others were collected from other groups
On the digestion of cobalt, Place sample in 100ml tall-form
beaker. Slowly add 4.1ml conc. H2SO4. Place in hot plate. Heat The grams of metal was obtained by subtracting the final weight
to near boiling or vapor condensation is observed. The solution of the electrodes upon electrodeposition from its initial weight.
will turn dark, bluer solution with a pink solid. Continue heating
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The mixtures prepared were copper and cobalt mixture and Cu/Co 1/ 2 38.85 3.63
copper and nickel mixture. The researchers observed the Cu 1.4 7.93 34.72
separation of metal ions in electrolysis but they were not able Co 2.4 4.53 64.18
to weigh the metal deposited separately.
Ni 2.4 8.17 422.39
Cu/Ni 1.4/ 2.4 30.28 9.96
Table 2: Metal Deposited true values
Cu/Co 1.4/ 2.4 20.72 92.42
Metal Sample Current (A) Metal deposited (g) Time (sec)
Cu 1.2 0.6356 1608.4
The percent error was computed by
Co 2.2 0.58933 877.1
Ni 2.2 0.58693 877.1
|𝑒𝑥𝑝. 𝑣𝑎𝑙𝑢𝑒 − 𝑡𝑟𝑢𝑒 𝑣𝑎𝑙𝑢𝑒|
Cu/Ni 1.2/ 2.2 1.222 2485.5 𝑥 100
Cu/Co 1.2/ 2.2 1.22479 2485.5 𝑡𝑟𝑢𝑒 𝑣𝑎𝑙𝑢𝑒
Cu 1 0.6356 1930.1
Equation 2: percent error calculation
Co 2 0.58933 964.9
Ni 2 0.58693 964.8
The errors may arise from the fluctuation of current and/or the
Cu/Ni 1/ 2 1.222 2895
electrodes itself. It can also be a human error because
Cu/Co 1/ 2 1.22479 2894.9
sometimes, the Electroanalyzer was left unattended.
Cu 1.4 0.6356 1378.7
Co 2.4 0.58933 804.0
Ni 2.4 0.58693 804.0
Conclusion
Cu/Ni 1.4/ 2.4 1.222 2182.7
The experiment was successful in the application of constant
Cu/Co 1.4/ 2.4 1.22479 2182.7
current electrogravimetric method in the determination of the
amount of metal present in a metal chloride solution.
The true value of metal was determined by molar mass of metal
ion divided by metal ion sample volume. The true value of time Electrolysis of the sample allowed the deposition of the metal
was based on true value of metal deposited. It was computed by due to the reduction reaction, and the amount was directly
measured by weighing by difference. Moreover, the experiment
1
𝑔 𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛 𝑥 𝑥 was also successful in applying the aforementioned technique
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛 in the separation of metal components in a solution containing
𝑛𝑢𝑚. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 96485 𝐶
𝑥 𝑥 a mixture. Varying the current also changes the reaction that
𝑚𝑜𝑙 𝑛𝑢𝑚. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒𝑙𝑒𝑡𝑟𝑜𝑛 occurs at the cathode: the one that may maintain the magnitude
1
of the current applied will be favored.
𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑎𝑝𝑝𝑙𝑖𝑒𝑑
In this experiment, applying higher current will result to faster
Equation 1: gram of metal ion to time conversion electrolysis.

The true value of mixtures was the addition of the time for both
metal ions present. References

Table 2: Metal Deposited percent errors. 1] Harley, Q. (2005, January 24). Determination of Copper by
Electrogravimetry. Retrieved from Department of Chemistry
Metal Sample Current %error Metal %error
University of Kentucky:
(A) deposited Time
http://www.chem.uky.edu/courses/che226/Labs/080-
Cu 1.2 8.75 40.31
Electrograv_Cu.pdf
Co 2.2 3.17 85.66
Ni 2.2 2.37 91.54 2] Skoog, D. (2007). Principles of Instrumental Analysis 6th
Cu/Ni 1.2/ 2.2 38.38 73.81 Edition. Toronto: Thomson Higher Education.
Cu/Co 1.2/ 2.2 20.56 13.46
Cu 1 4.47 44.04 3] Amrita Vishwa Vidyapeetham University. (2016).
Co 2 5.49 11.93 Electrogravimetric Estimation of Metals. Retrieved September
Ni 2 13.81 179.82 7, 2016, from Virtual Amrita Laboratories Universalizing
Cu/Ni 1/ 2 53.60 55.44
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Education:
http://vlab.amrita.edu/?sub=2&brch=190&sim=367&cnt=1.

Supporting Information

Sample Computation
Raw data

Trial 1 Copper 1.2 Amp.

Weight of Small Electrode Weight of Big Electrode

24.422 38.366
WSE with Deposit WBE with Deposit
24.951 38.501 Figure 2: Digested Individual and Mixture Samples of Metal
(photo taken from the laboratory)

Difference of SE Difference of BE

0.529 0.135
Total Weight Deposited

0.664

Sample Computation

Weight Deposited
(24.951- 24.422) + (38.501- 38.366) = 0.664g

Figure 1: Reactions involved in experiment