Page | 1

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

Volume No. 3 Issue No. 2

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

Dr. Kathlia De-Castro Cruza ; Elijah P. Ugaddanb

ABSTRACT
Electrogravimetry or commonly referred to as electrodeposition has been a conventional
method in quantitative analysis of of species such as metal ions. The quantity of the analyte
is directly proportional to the applied charge to pursue an electrochemical reaction.
Although this proves to be efficient, not all metal ions can be subjected in this analysis.
Metals used are Cu, Ni and Co in their aqueous solutions of divalent salts. Prior to
electrolysis, the samples were prepared such that the presence of chlorine in their divalent
salt solution is eliminated through digestion of acid and in excess nitric acid as to the
instant for Cu or ammoniacal solution which is in the case of Co and Ni. Electrodeposition
is prone to certain phenomena known as IR drop, concentration overpotential and
cathodic potential. This may affect the applied voltage towards the cell and incur
significant deviation in the results. Elimination of it is done through constant stirring, the
addition of depolarizers and complete removal of chlorine atoms. Range of percentage
error obtained from subjecting individual metal solution in the Eberbach Electroanalyzer
exhibited (1.27% - 4.11%). Separation of mixtures i.e. Cu-Co and Cu-Ni mixture is feasible
although a very high percentage error is obtained.

Keywords:

electrochemistry, electrogravimetry, electrolysis, cathodic potential,

concentration overpotential, Faradays Law, IR drop

INTRODUCTION

principle

In quantitative analysis of ions

specifically metals, most commonly used
technique

is

electrolytic

electrogravimetry.

deposition

Ordinarily,

metal

underlying

this

analysis

is

electrochemistry predominantly the Ohms

Law, Faradays Law and redox reaction.

or

The Ohms Law states that the relation of

is

current to voltage is directly proportional

deposited on the electrode and an increase

in the mass of electrode is determined. The
a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

Page | 2

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

and inversely proportional to resistance. It

There

are

two

general

types

of

is mathematically expressed as:

electrogravimetric method: one of which is

controlled current and controlled potential

V
I=
R

method.

The first is maintaining the

current and kept at a constant value while

Where V is the potential measured in V; R is

resistance in ohms
(Equation 2.1)
The Faradays Law states that the amount at
which the sample deposits in the electrode
is relatively directly proportional to the

the potential of the indicator electrode is

varied. On the other hand for a controlled
potential, the current is varied usually
starting at a highest value while the cell
potential

between

electrodes

is

held

constant. This is suitable for separating

various metals in mixtures.

amount of the charge passed through it.

The first part of the experiment will be

This is expressed as

applying

the

constant

current

electrogravimetric method. Its apparatus is

q=nFN

given in Figure 2.1. In this electrolytic cell,

Where q is the charge measure in C; n is the

mol of the analyte; F is the Faradays
constant; N is the number of e-s involved in
the redox reaction

the anode is where oxidation occurs and

most of the deposited metals will be
accumulated in the Pt cathode where
reduction of the metal occurs.

(Equation 2.2)

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

Page | 3

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

Figure 2.1 Apparatus used in Constant Current

Co2+ + 2e- Co(s)

Method

In the anode the half- cell reaction is given

by:

On the other hand in order to separate the

mixtures given as Cu- Ni and Cu-Co, the
second method, controlled potential is to be

4OH- O2 + 2H2O + 4e

used. The purpose of the experiment is to

be able to determine the amounts of metal

And on the cathode half-cell reaction are the

following metals (Cu, Ni and Co) used:
Cu2+ + 2e- Cu(s)

in the aqueous solution from their divalent

salts using electrogravimetric techniques
and to be able to separate the mixture given
by Cu-Ni and Cu-Co aqueous solution.

Ni2+ + 2e- Ni(s)

MATERIALS AND METHODOLOGY

Materials

NH4OH,

85%

hydrazine

hydrate

and

aqueous solution of CuCl2, CoCl2 and NiCl2.

The apparatus are 250 mL beaker, (1) hot

The reagents comprises of concentrated

plate, Bunsen burner and a pipet of 10 mL

H2SO4, concentrated HNO3, concentration

specification.

Methodology
I.

Procedure for Cu in CuCl2

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

Page | 4

Place sample in a 100-mL

tall-form (electrolytic
beaker)

Evident color
changes: pale
green to blue gree
to light blue to
light blue having
white solid

Heat 5 to 10
minutes to
remove white sol

Add 2.3 mL concentration

sulfuric acid (*Brown and
white ppt will form.
Evolution of fumes)

Brown & white ppt

will turn green.
Add 1 mL of HNO 33

Dilute with 100

mL dis water with
200 mL vol flask

Place mixture in
hot plate and
heat to near
boiling or until
vapor
condensation
observed

Flame sides of
beaker with
Bunsen burner to
remove internal
condensation

Carry out
electrolysis

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

Page | 5

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

II.

III.

Procedure for Co in CoCl Procedure for Ni in NiCl2

Separation of Metals

Place sample in a 100-mL

Place
sample
in a 100-mL
tall-form
(electrolytic
tall-form
(electrolytic
beaker)
beaker)

Heat for 5 mins

5 to 10of
untilHeat
formation
minutes
white sol to
remove white sol

Follow procedures I, II and III

Add
Add4.1
4.1mL
mLconcentration
concentration
sulfuric
(*Yellow
sulfuric
(*Redppt
to
acidacid
+
fumes)
blue, blue to purple
/with pink sol)

Evident
color
Flame
sides
of
changes:
light
beaker to remove
purple
with pink
condensate
sol to dark bluer
with pink sol

Place mixture in
Place
mixture
hot
plate
and in
Evident color of
hot
plate
and
heat to near
sol changes:
Heat
sol'n for 10
heat or
to until
near
Combine
solutions assigned either
boiling
yellow
to white;
minutes
or more
or
until
Cu+Co
or
Cu
+
Ni
boiling
vapor
white
until to
nolight
more
vapor
condensation
green.visible
fumes
condensation
observed
observed
RESULTS AND DISCUSSION

Dilutewith
with6565mL
mL
Dilute
diswater
water++3636mL
mL
dis
conc
NH
OH
+
0.5
conc NH44 44OH
mL 85% hydrazine
Varryhydrate
current

Heat sol'n to 7000C

Electrolysis
Carry out
electrolysis

Perform electrolysis

CoCl2(aq) + H2SO4(aq) ->CoSO4 (s) + HCl(g)

(pink ppt.)

During the preparation of the solution prior

to electrolysis, CuCl2, CoCl2 and NiCl2 was

The purpose of this is to remove the

digested with concentrated sulfuric acid. In

chloride ions from the original divalent salt

this manner the chloride ions in these

solution since this Cl- will give off erratic

solutions formed the precipitate of CuSO4 ,

results upon electrolysis. The amount of

NiSO4 and CoSO4. The following reactions

metal deposited will not be optimized since

are given below:

Cl- will also attach to the cathode part of the

CuCl2(aq) + H2SO4(aq) ->CuSO4 (s) + HCl(g)

(white ppt.)

Pt electrode and accounts for the mass after

electrolysis.

NiCl2(aq) + H2SO4(aq) ->NiSO4 (s) + HCl(g)

(yellow ppt.)

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

Page | 6

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

Table 2.1 shows the different changes occurring in the

solution after the following processes were done

The solution was then heated to boiling to

dissolve the precipitate in the aqueous

Figure 2.2 shows the current-time relationship in

solution. It is necessary to heat the sides of

electrolysis

the beaker since this is the condensed state

of the HCl that affixed on the beaker. HCl
are then released as fumes in the fumehood.
In order to ensure the complete removal of
HCl, nitric acid was then added for Cu since
HCl forms an azeotrope, boils off any
nitriles and improves plating. Upon which is
subjected to electrolysis. As for the case of
Co and Ni, addition of hydrazine and
concentration NH4OH was done after the
color changes throughout heating.
In electrogravimetry, as time increases,

Since the current decreases over time, the

IR

drop

(potential

developed

when

resistance is applied) in the cell decreases as

well. In order to sustain the shift in the IR
drop and maintain the applied potential, the
cathode potential (Ecath) is shifting to a
more negative value. Because of this, the
cathode is less likely to be reduced and the
codeposition of the hdyrogen ions in the
anode will then occur. The hydrogen ions in
the anode is said to depolarize the copper in
the cathode.

more metal ions are deposited on the

cathode part of the electrode therefore more
are reduced. After some time, when lesser
metal ions are present in the solution, lesser
current will then be applied to carry out
electrolysis as shown in Figure 2.2.

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

Page | 7

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

Figure 2.3 shows (a) the IR drop decreases as the (b)

Ecathode also shifts to a decreasing value

The reduction of the anode will result to an

erroneous measurement of the amount of
substance that will deposit on the electrode
for this will account the codeposition of the
hydrogen ions via gas bubble formation. In
order to remove this depolarization effect, a
cationic depolarizer is then added to the
solution. This cationic depolarizer is easily
reduced or oxidized and helps to maintain
the applied potential in the cell. Instead of
reducing the hydrogen ions in the anode,
the cationic depolarizer will be more favored
to be reduced. Hydrazine and sulfuric-nitric
acid solution which forms nitrates are
examples of cationic depolarizer that are
used in the experiment.

Table 2.2 shows the results in the mass of metal sample

after electrolysis

In Table 2.2, the % error of the experiment

was obtained through the theoretical value
of the following metals from their aqueous
solution which is at a theoretical value of
2M. From this concentration, the theoretical
weight of the sample deposit was calculated.
It has been shown that Co has shown the
least % error among the other metal
samples,

therefore

Co

was

efficiently

deposited in the electrode throughout the

process. During the electrolysis, a stirrer
was

used in

concentration

order to

overcome the

overpotential.

The

concentration overpotential implies the

diffusion of the metal ions in the Pt
electrode and their relative concentration.
Concentration is not constant all throughout
electrolysis. The proximity of the ions in the
solution to the Pt electrode dictates its
concentration and they are said to be

Figure 2.4 Structure of Hydrazine

directly

proportional.

The

smaller

the

The addition of ammonium hydroxide in

distance is between the ions to diffuse to the

both Ni and Co allows the formation of

electrode, the lesser is the concentration of

complexes which is neutral in solution.

it as compared to those that have greater

Ammonia being the ligand in the Ni and Co

distance from the electrode. This difference

complex allows the formation of their ppt.

between

the

concentration

near

the

electrode and the ones away from the

electrode is known as the concentration
a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

Page | 8

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

overpotential. Taking the case for Cu ions as

electroanalyzer operated for almost 45

seen in Figure 2.5 the [Cu2+] electrode is less

minutes. During the analysis of Co and Ni,

than that of the [Cu ]bulk.

current was increased and maintained

2+

constant at 2A and the machine operated for

almost an hour.
In the half cell reaction at the cathode, it is
given by these following reactions and their
following standard potentials:
Cu2+ + 2e- Cu(s)

E0= + 0.339 V

Ni2+ + 2e- Ni(s) )

E0= -0.236 V

Co2+ + 2e- Co(s) )

E0= -0.282 V

The reason why Cu was operated at a much

Figure 2.5 Concentration overpotential exhibited by
Cu ions in bulk solution

lower current than Ni and Co is because

amongst the three solutions, it is more likely

In order to eliminate the offset in the

to be reduced because of its (+) value on its

measurements caused by this phenomenon,

reduction standard potential. Ni and Co

constant stirring is initiated. Since not all

would prefer more to be oxidized than

atoms are of the same mobility due to their

reduced relative to Cu. Increasing the

proximity in the electrode, it is highly

current for Ni and Co allows the applied

necessary for the solution to be stirred to

potential

maintain a constant concentration between

associated to its standard potential and

the bulk and the electrode.

permits electrodeposition. According to the

The electrode is made up of platinum (Pt)

because this metal does not readily react
with any other metals and said to be inert.
Therefore when current is applied, no
plating or deposition of Pt will be observed
and results will only be contributed from the
participating

metal

ions.

to

relationship

overcome

between

the

Ohms

(-)

law

values

and

Faradays Law, increasing the current also

increases the amount of time needed for the
Ni and Co solution to complete electrolysis
therefore these two (Co and Ni) have more
reaction time than Cu.
Moreover, completion of electrolysis was

When Cu was subjected to electrolysis, a

determined after the respective colored of

controlled current of 1A was set and the

solutions of each metal became colorless.

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

Page | 9

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

Drying of the electrode and first weighing

Table 2.3 shows the electrolysis results with Cu-Co and CuNi mixture

was done. Afterwards, continuous weighing

was observed to ensure that no more metal

Although the results were not appreciable

will deposit in the Pt electrode.

due to the reasons that the amount of time

At the latter part of the experiment is the

separation of mixtures. Tabulated results
are shown in Table 2.3.

needed for completion in electrolysis where

disregarded, the possibility of separating
this mixture is feasible. Another reason may
also arise from the significant error in the
preparation of the sample.
The method applied was a controlled
potential electrogravimetry. Current was
readjusted from 1A to allow deposition of Cu
to 2A to ensure the deposition of the other
metal, Co and Ni. The difference in their
applied potential allows the separation of
mixtures.

CONCLUSION

Electrodeposition may be subjected to

Electrogravimetry is a quantitative analysis

of

species

particularly

metals

through

electrodeposition. It is classified by two

methods; controlled current and controlled
potential

electrogravimetry.

Although

electrogravimetry still proves to be efficient,

selective metals can only be applied through
this analysis. Cu, Co and Ni are the metals
analyzed along with their divalent salts.
Samples were prepared prior to electrolysis
to

ensure

accurate

measurements

in

determining the quanity of the analyte in

the sample. This quantity is relative to the
current

or

charge

added

into

it.

different phenomena such as IR drop,

concentration overpotential and cathodic
potential that may contribute to erratic
results. Prevention may include constant
stirring, addition of cathodic depolarizers
and elimation of impurities. The variation of
current plays a great role in separation of
mixtures. The amounts of this metals
obtained were in a range of 1.27-4.11% error.
In the separation mixture part of the
experiment, a very high percentage error
was found due to errors in the experimental
methodology.

Although

poses

with

unappreciable result, separation of mixture

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

ELECTROGRAVIMETRIC DETERMINATION OF CU2+, CO2+ and Ni 2+

(Cu-Ni mixture and Cu-Co mixture) is

feasible.

a. Professor of CHM115L, School of Chemistry and Chemical Engineering, Mapua Institute of Technology.
b. Bachelor of Science in Chemistry and Chemical Engineering Student of CHM115L, Mapua Institute of Technology;

P a g e | 10

REFERENCES
[1] D.A. Skoog and J.J. Leary, Principles of Instrumental Analysis, Fourth Ed., Saunders
College Publishing, Orlando, FA, 1992, Chap. 22, particularly pp. 499-511.
[2] Willard, Merritt, Dean and Settle, Jr., Instrumental Methods of Analysis, Seventh Ed.,
Wadsworth, 1988, Chap. 22 and particularly pp. 682-691
[3] Electrogravimetry; In Encyclopedia Britannica, 2011; Retrieved from
http://www.britannica.com/EBchecked/topic/183095/electrogravimetry
[4] Electrogravimetric Estimation of Metals; Value at Amrita, 2011; Retrieved from
http://amrita.vlab.co.in/?sub=2&brch=200&sim=367&cnt=1
[5] Harris, D. C., (1995) Quantitative Chemical Analysis 4th Ed., W. H. Freeman and Company,
New York Chapter 17
[6] D.A Skoog and West, Principles of Analytical Chemistry. Ninth Ed., Saunders College
Publishing, Orlando, FA, 1992, Chap. 21