Objective

The goal of this experiment is to use an electro gravimetric method to determine the amount of
copper in a given sample. It also teaches the electrogravimetric method and its working
mechanism.
Theoretical Background
Electrogravimetry is a quantitative electroanalysis technique that is used to separate and quantify
ions in a sample. By electrolyzing the analyte solution, the analyte is electrochemically reduced
and deposited on the cathode. To calculate the mass of the analyte in the original solution, the
mass of the cathode must be measured both before and after the experiment. It is critical to
regulate the electrode's potential to ensure that only the metal under test is deposited on the
electrode.
Electrogravimetry is a technique that involves electroplating a metal into a previously weighed
electrode and then reweighing to determine the amount of metal initially present in solution. A
sufficient voltage is applied to the electrochemical cells for a long enough period of time to
quantitatively remove the metal from solution and salt solutions of the very base metals.
Nitrogen gas (N2) is liberated from the alkali and alkaline earth metals, as well as from the acid
solution. The passage of current through salt solutions of metals such as Zn, Fe, Ni, Cu, Cd, Pb,
Ag, and Hg results in metal deposition at the cathode. However, if the anode is made of the
aforementioned attachable metals, the current flow is accompanied by the passage of material
from the anode into the solution and then to the cathode. However, if the anode is inert (e.g., Pt),
oxygen is liberated from nitrate, sulphate, phosphate, and other solutions, and halogen (except
fluorine) is liberated as gas from halide solutions. If the solution contains two or more of the
metals listed above, As a constituent, metal ions with positive reduction potentials can be
separated from metal ions with negative reduction potentials without the need for external
control of the cathode potential. If both metals have a positive reduction potential and their
difference is large, electron separation is simple; otherwise, it is difficult. In general, a potential
slightly greater than the decomposition potential of the electrolyte under study is used. For
example, if both Zn and Cu are present in a solution (as in our experiment), and Cu is to be
deposited on the cathode, a potential of at least greater than must be present.
Ohm’s Law
Electrochemical cells, like metallic conductors, obstruct the flow of charge. Ohm's law
explains how resistance affects both types of conduction. The ohmic potential, also known
as the IR drop of the cell, is the result of a cell's resistance, measured in ohms, and its
current, measured in amperes.
When Eapplied = Ecell, no current flows through the cell. When the applied voltage is
gradually increased, a small current enters the circuit. When this current flows through the
cell, it encounters resistance R, resulting in a voltage drop of IR volts. Alternatively, the
applied potential must be IR volts greater than the theoretical cell potential.
E applied=E cell – IR=Ecathode −E anode −IR
 E applied=E cell – IR=Ecathode −E anode −IR

Ecell can be calculated using the Nernst equation.

Faraday’s Law
Michael Faraday postulated two fundamental laws expressing the relation between the amount of
current passed through the solution and the amount of metal deposited on the electrodes.
According to the first law, the mass of an element released at the electrodes during electrolysis is
directly proportional to the amount of electrical charge (Q) that passed through the electrolyte. If
m is the mass of a substance deposited by an I ampere current in t seconds, then the first law of
electrolysis states that
m ∝Q

m ∝ I∗t

m=ZIt

Here, Z is a proportional constant.

Faraday’s Second Law of Electrolysis

According to the first law, the mass of an element released at the electrodes during electrolysis is
directly proportional to the amount of electrical charge (Q) that passed through the electrolyte. If
m is the mass of a substance deposited by an I ampere current in t seconds, then the first law of
electrolysis states that.
M
m∝
n

where m is the amount of mass deposited/evolved, M is the molar mass and n is the valency
number of ions of that substance. So,

m 1 n1 m 2 n2
=
M1 M2

The reason of using HNO3 in this reaction is to prevent the liberation of hydrogen ions instead of
copper in the electrode. Copper and zinc react with HNO3 and produce nitrate ions.

Cu + 4HNO3 ⇌ Cu2+ + 2NO3- + 2NO2 + 2H2O

Zn + 4HNO3 ⇌ Zn2+ + 2NO3- + 2NO2 + 2H2O

Then it reacts with the hydrogen ions to form ammonium ions.

 NO3- + 10H+ + 8e- ⇌ NH4+ + 3H2O

Like nitrates, urea also acts as a depolarizer.

2H+ + 2NO2- + NH2CONH2 = 2N2 + CO2 + 3H2O

Chemical Reactions Involved

Cathode Reaction:
−¿→ Cu¿
¿
Cu2+¿+2 e

Anode Reaction:
−¿¿
−¿→O 2+2 H 2 O +4 e ¿
4 OH

APPARATUS:
1. Beaker
2. Magnetic stirrer
3. Bunsen burner
4. Platinum cathode
5. Fischer electrode
Aside from these, an ammeter and a voltmeter are used in the circuit. One of the cathode
electrodes is made of platinum gauges. The open design promotes liquid circulation while also
increasing available surface area for Cu deposition. The other anode electrode is simply helical
in shape. As a chemical reagent, concentrated hydrochloric acid and nitric acid are used.
CHEMICALS:
1. Brass
2. HNO3
3. H2SO4
4. Distilled water
5. Urea
PROCEDURE:
1. By using an electronic balance weight of brass and platinum gauge cathode were taken.
2. Brass was then taken into a beaker and concentrated HNO3 acid is added drop wise to
dissolve the brass. The color of the solution at that instant was blue.
3. 1 ml of concentrated H2SO4 acid was then added into the beaker.
4. 10 ml distilled water was poured into the above said beaker and it is heated until the
solution becomes concentrated and white fumes are observed.
5. Again 10 ml distilled water and 10 ml 6N H2SO4 was added to the concentrated solution.
6. Urea was added to remove HNO2.
7. The stirrer was switched on and the electrolysis was continued by 0.45A and 4V AC
source, until the blue color the solution has entirely disappeared.
8. The cathode was raised and washed by distilled water.
9. The cathode was sunk into C2H5OH and then kept in open air for quick drying.
10. After drying, the weight of (Cathode + Cu) was taken &
11. From the increase in weight of the cathode, the copper content in brass was calculated.
Observed data and calculation
Weight of brass sample = 0.220 gm.

Initial weight of electrode = 17.944 gm.

Weight of electrode with Cu = 18.033 gm.

Applied Potential V = 3 V

Applied Current I = 0.3 A

Expected weight of copper in brass = ( 60 % × Weight of brass sample ) gm

¿ ( 0.60 ×.220 ) gm=0.132 gm

Weight of copper (Cu) deposited,

=¿

= ( 18.0653−17.9621 ) gm=0.132 gm

Weight of Cu deposited
Percentage of Cu in brass sample ¿ × 100%
Weight of the brass sample
 0.1032
¿ ×100%
0.3004

¿ 40.4 %

Result

The percentage of copper in the brass sample is 40.4%

Discussion

As a result, it is clear that complete Cu deposition is not achieved. This could have happened for
the following reasons:

1. The brass used here is impure.

2. Heating is required to remove excess NO3- as NO2 gas when preparing Cu solution, but in this
case, excess heat was applied, oxidizing Cu into CuO.

Cu + 1⁄2 O2 = CuO.

Since Nitrite ion resists complete deposition, it should be made the HNO3 acid free

fromHNO2 either by addition of urea to the solution,

2H+ + 2NO2- + NH2CONH2 = 2N2 + CO2 + 3H2O.

By boiling the HNO3 before adding it Complete deposition is impossible if any of the
aforementioned measures are not carried out. In this experiment, a dilute solution is prepared;
otherwise, incomplete Cu deposition may occur or the deposition will not adhere satisfactorily to
the cathode. Polarization occurs due to evolution of H2 gas to cathode and it leads to deposition
of spongy and poor-quality copper. Because nitrate ion is reduced to ammonium ion at a copper
surface, Cu deposition is carried out in HNO3 media.

NO3- + 10H- + 8e- = NH4+ + 3H2O.

During electroplating, any appreciable current depletes the concentration of Cu ion at the
electrode relative to the rest of the solution. Concentration over potential is the term for this. To
keep this term as short as possible, a magnetic stirrer is used.