DETERMINATION OF ACTIVITY AND ACTIVITY

COEFFICIENT FROM CELL EMF

Marina Angela M. Teleron, Daisy S. Torres
Department of Pure and Applied Chemistry, College of Arts and Sciences, Visayas State University, Visca, Baybay,
Leyte

Abstract: The chemical reaction that takes place in a galvanic cell is the redox reaction. One electrode acts as anode
in which oxidation takes place and the other acts as the cathode in which reduction takes place. The best example of
a galvanic cell is the Daniel cell. In the Daniel cell, copper and zinc electrodes are immersed in a solution of copper
(II) sulfate and zinc (II) sulfate respectively. The two half cells are connected through a salt bridge. When a metal
electrode is dipped in a solution containing its metal ions, a potential difference is developed at the metal solution
interface. This potential difference is called the electrode potential. In this experiment, the potential of the cell was
determined at different concentrations (1, 0.5, 0.25, 0.125 and 0.0625 M) for each half cell. As the concentration of
zinc sulfate decreased at constant copper sulfate concentrations, the cell potential increased. Meanwhile, as the
concentration of copper sulfate decreased at constant zinc sulfate concentrations, the cell potential decreased. The
activity and activity coefficient was determined using the Nernst equation. The calculated activities for the system
ranged from 0.99 to 1.00 M and the activity coefficient measured how much the solution differed from the ideal
solution.

Keywords: galvanic cell, copper sulfate, zinc sulfate, cell potential, activity, activity coefficient

1. Introduction reaction, and always have a positive voltage. The

Electrochemistry is the study of chemical
processes that cause electrons to move. This
movement of electrons is called electricity, which
can be generated by movements of electrons from
one element to another in a reaction known as an
oxidation-reduction ("redox") reaction.
In 1793, Alessandro Volta discovered
that electricity could be produced by placing
different metals on the opposite sides of a wet
paper or cloth. He made his first battery by
placing Ag and Zn on the opposite sides of a
moistened cloth with salt or weak acid solution.
Therefore, these batteries acquired the name
voltaic cells. Voltaic (galvanic) cells are
electrochemical cells that contain a spontaneous
electrical energy released during the reaction can
be used to do work. A voltaic cell consists of two
compartments called half-cells. The half-cell
where oxidation occurs is called the anode. The
other half-cell, where reduction occurs, is called
the cathode. The electrons in voltaic cells flow
from the negative electrode to the positive
electrode—from anode to cathode. For an
oxidation-reduction reaction to occur, the two
substances in each respective half-cell are
connected by a closed circuit such that electrons
can flow from the reducing agent to the oxidizing
agent. A salt bridge is also required to maintain
electrical neutrality and allow the reaction to
continue.
When a metal is in contact with its own
ion solution it develops a potential with respect to concentrations and;
the electrolyte. The potential difference c) calculate the activity and activity
developed at the anode - electrolyte interface is coefficient of the electrodes in the
called oxidation potential and the potential galvanic cell using the Nernst equation.
difference developed at the cathode -electrolyte
3. Materials and Methods
interface is called reduction potential. The
potential difference between the anode and 3.1 Chemicals
cathode is called the EMF of the cell. The 1 M CuSO4 solution, 1 M ZnSO4 solution, copper
potential difference measured at standard metal, zinc metal, NaNO3 solution
conditions (1 atm pressure, 298K) is called
standard electrode potential. Standard electrode 3.2 Apparatus
potential gives the tendency of the electrode to get 50 mL beaker, connecting wires, voltmeter, filter
oxidized or reduced. If the electrolytes are paper, sand paper
different the two compartments are joined by a
3.3 Preparation of Galvanic cell
salt bridge, which is a tube containing a
concentrated electrolyte solution in agar jelly that One M copper sulfate solution was
completes the electrical circuit and enables the prepared in a 50 mL beaker and 1 M zinc sulfate
cell to function. solution was prepared in another separate beaker.
Copper and zinc strips were obtained and cleaned
In chemical thermodynamics, activity a)
using a sand paper. The copper strip was dipped
is a measure of the effective concentration of a
into the beaker containing the 1 M copper sulfate
species under non-ideal (e.g., concentrated)
solution while the zinc strip was also dipped into
conditions. This determines the real chemical
the beaker containing 1 M zinc sulfate solution.
potential for a real solution rather than an ideal
A salt bridge was prepared by using a filter paper
one. An activity coefficient is a factor used in
dipped into a solution of sodium nitrate. The salt
thermodynamics to account for deviations from
bridge was used to connect the two solutions. A
ideal behaviour in a mixture of chemical
voltmeter was obtained and connecting wires
substances. In an ideal mixture, the microscopic
were used to connect the copper strip to the
interactions between each pair of chemical
positive terminal and the zinc strip to the negative
species are the same (or macroscopically
terminal. The position of the pointer in the
equivalent, the enthalpy change of solution and
voltmeter was noted and the reading was
volume variation in mixing is zero) and, as a
recorded. The process was repeated by taking
result, properties of the mixtures can be expressed
different concentrations (0.5, 0.25, 0.125, and
directly in terms of simple concentrations or
0.0625 M) of zinc sulfate with constant
partial pressures of the substances present e.g.
concentration of 1 M for copper sulfate solution
Raoult's law. Deviations from ideality are
and vice versa. Figure 1 shows the set up for the
accommodated by modifying the concentration
galvanic cell in the experiment.
by an activity coefficient.
2. Objectives
This experiment aimed to:
a) prepare a set-up of a galvanic cell;
b) determine the EMF of the cell at varying

4. Results and Discussion
A galvanic cell was set up by connecting
a half-cell of CuSO4 with a half-cell of ZnSO4
using a salt bridge. The electrode for the cells
were copper rod and zinc rod respectively. The
cathode in this reaction is the copper rod where
reduction occurs while the anode is the zinc rod
where oxidation occurs. The zinc rod would
spontaneously lose electrons while the Cu(II)
would spontaneously gain electrons. This process
can be expressed as two half-reactions that sum
to yield the overall reaction:
1st half reaction. Zn (s) --> Zn+2
(aq) +2e
2nd half reaction. Cu+2 (aq) + 2 e- --> Cu (s)
overall net reaction. Zn (s) + Cu+2 (aq) --> Cu (s) +
Zn+2 (aq)
A salt bridge is necessary for charge balance: in
this case sulfate ions flow from the copper to the
zinc compartment. Its main function is to prevent
the potential difference that arise between the two
solutions when they are in contact with each
other. This potential difference is called the liquid
junction potential. It also completes the electrical
circuit by connecting the electrolytes in the two
half cells, prevents the diffusion of solutions from
one half cell to the other and maintains the
electrical neutrality of the solutions in the two
half cells. The salt bridge used to connect the two
half-cells was a filter paper soaked in NaNO3. In
the case of the cell in the experiment, zinc
oxidizes at the anode and passes into the solutions
as Zn2+ ions, so there will be accumulation of
positive charge in the solution. To maintain the
electrical neutrality of the solution, the salt bridge
provides negative ions, NO3-. In the cathodic half
cell, there will be accumulation of negative ions
formed due to the reduction of positive ions. To
maintain the electrical neutrality, salt bridge also
provides positive ions. The Cu2+ ions from the
CuSO4 solution is reduced by the electron formed
by the oxidation of zinc, and deposited on the
copper cathode. As a result, the concentration
Cu2+ ions decreases in the solution and that of SO4
2-
ions (sulphate ions) increases. So there will be
an accumulation of negatively charged sulphate
ions around the cathode. To maintain the
electrical neutrality, salt bridge provides positive
ions, Na+. The electrochemical cell shown in
Figure 1 can be represented by the following
shorthand:
Zn (s) |Zn+2 (aq) || Cu+2 (aq) | Cu (s)
Electrons that are generated at the anode of an
electrochemical cell are driven toward the
cathode by a thermodynamic tendency called the
electromotive force (emf), measured in volts
using the voltmeter.
Ecell = E Cu+2| Cu – E Zn |Zn+2 eq. 1
The theoretical electrical potential between the
two electrolytes is 1.10V under standard state
conditions - gases at 1 atm pressure, solutions at
1 M concentrations, and temperatures at 25oC
while the electrical potential collected from the
experiment was 1.00 V as shown on Table 1.
 Table 1. Cell potential of constant [CuSO4] and
varying [ZnSO4]

[CuSO4 ] Experimental Theoretical E %

[ZnSO4] E cell (V) cell (V) Error

1M 1M 1.00 1.10 9%
1M 0.5 M 1.00 1.11 10%
1M 0.25 M 1.00 1.12 11%
0.125
1M 1.10 1.13 3%
M
0.0625
1M 1.20 1.14 5% Figure 2.Temperature vs. cell voltage
M
relationship

As the concentration of zinc sulfate decreased, A different observation was determined at

the cell potential increased. The potential of a cell constant zinc sulfate concentrations and at
is dependent on a number of factors: decreasing copper sulfate concentrations. The
concentrations of the substances, the temperature, cell potential decreased at decreasing copper
and pressure. In comparison with the theoretical sulfate concentrations as shown on table 2.
values, the Nernst equation (eq.2) can confirm Table 2. Cell potential of constant [ZnSO4] and
that large concentration differences between the varying [CuSO4]
anions and the cations can cause the voltage to
differ significantly from the standard cell [CuSO4] Experimental Theoretical %
[ZnSO4]
E cell (V) E cell (V) Error
potential, and that such large concentration
1M 1M 1.00 1.10 9%
differences also make the cell potential more
0.5 M 1M 1.00 1.09 8%
temperature dependent.
0.25 M 1M 0.90 1.08 16%
Consider a concentration of 10 -5 M for Zn2+ (aq) 0.125 M 1M 0.90 1.07 15%
and 0.1 Molar for Cu2+ (aq) as a test case for 0.0625
1M 0.80 1.06 24%
temperature dependence. We can see from figure M
2 that the cell potential tends to increase with
temperature, or that a colder cell produces less One implication is that the cell potential will be
voltage - a commonly observed phenomenon reduced from the standard value if the
with dry cell batteries. The variation with concentration of Zn2+(aq) is greater than that of
temperature is linear with temperature, but quite Cu2+(aq) at the standard temperature. An excess
small for this cell. The large variations of concentration of Cu2+(aq) will give a higher
practical output voltage with temperature for dry voltage. The graph at figure 3 shows the increase
cells does not arise from the Nernst equation in cell voltage with increasing concentration of
alone. the cation. Note that the horizontal axis is
logarithmic, and that the straight line variation of
the voltage represents an logarithmic variation
with Q. Note that the cell potential is equal to the
standard value if the concentrations are equal
even if they are not equal to the standard value of
1M, since the logarithm gives the value zero.
Figure 3. Cu2+ concentration vs. Cell voltage
relationship
The experimental result being lower than the
theoretical value may have also been due to
different factors. The electrode may have been
contaminated and we cannot confirm that the
electrodes were the pure form of the metal. It may
have been oxidized due to the exposure to air and
water. The solutions produced may also have
inaccurate measurements. Therefore, the results
were lower than the theoretical value.
Nernst equation relates the equilibrium
potential of a half cell with the standard electrode
potential, temperature, activity and reaction
quotients of the reacting species. It is named after
the German physical chemist Walther Nernst. In
a Daniel cell, the electrode potentials of the half
cells are written as:
eq. 2
Where E(Mn+| M) is the electrode potential of the
half cell,
Eo(Mn+|M)is the standard electrode potential,
[M] is the concentration of the metal,
[Mn+] is the concentration of the metal ion,
R is the universal gas constant (8.314 J/K mole),
n is the number of electron involved in the
reaction,
F is the Faradays constant (96500 C/mole).
So Nernst equation is generally represented as:
eq. 3
Where, ared is the activity (concentration) of
reduced species, and aox is the activity
(concentration) of oxidized species. So the
electrode potential of an electrochemical depends
on the standard electrode potential, temperature,
no. of electrons involved in the chemical reaction
and the concentration of the reacting species.
The activity and activity coefficient of the
electrodes in the galvanic cell can be simplified
using the following formulas respectively.
 𝑎� = 𝑒� ((𝐸� −𝐸�°)/𝑅�𝑇�) eq. 4
where, a = activity
E = chemical potential The calculated effective concentrations for the
system for non ideal conditions only ranges from
E° = standard chemical potential
0.99 to 1.00 M. Activity is more accurate in more
R = gas constant (8.314 J/K mole) concentrated solutions It is satisfactory to use
T = temperature (298 K) concentration for diluted solutions, but when you
are dealing with more concentrated solutions, the
difference in the observed concentration and the
𝑦� = 𝑎�/𝑀� eq. 5 calculated concentration in equilibrium increases.
This is the reason that the activity was initially
created. The calculated activity coefficient also
where, 𝑦� = activity coefficient measured how much the solution differed from
a = activity the ideal solution—i.e., one in which the
effectiveness of each molecule is equal to its
M = molar concentration theoretical effectiveness. The difference ranged
from 0.99 to 16.00.
Table 3 and 4 shows the activity and activity
coefficient calculated for the galvanic cell at 5. Conclusion
different set-ups.
The chemical reaction that takes place in
Table 3. Activity and Activity Coefficient of 1 a galvanic cell is the redox reaction. One
M CuSO4 with varying [ZnSO4] electrode acts as anode in which oxidation takes
[CuSO4] Experimental Activity place and the other acts as the cathode in which
[ZnSO4] Activity
E cell (V) coefficient
reduction takes place. At the anode, zinc
1M 1M 1.00 0.99 0.99 undergoes oxidation to form zinc ions and
1M 0.5 M 1.00 0.99 1.98 electrons. The zinc ions pass into the solution. If
1M 0.25 M 1.00 0.99 3.96 the two electrodes are connected using an
1M 0.125 M 1.10 1.00 8.00 external wire, the electrons produced by the
1M 0.0625 M 1.20 1.00 16.00 oxidation of zinc travel through the wire and enter
into the copper cathode, where they reduce the
Table 4. Activity and Activity Coefficient of 1 copper ions present in the solution and form
M ZnSO4 with varying [CuSO4] copper atoms that are deposited on the cathode.
When a metal electrode is dipped in a solution
[CuSO4] [ZnSO4]
Experimental E
Activity
Activity containing its metal ions, a potential difference is
cell (V) coefficient
developed at the metal solution interface. This
1M 1M 1.00 0.99 0.99 potential difference is called the electrode
0.5 M 1M 1.00 0.99 1.98 potential. The potential of the cell depends on the
0.25 M 1M 0.90 0.99 3.96 concentrations of the substances, the temperature,
0.125 and pressure. As the concentration of zinc sulfate
1M 0.90 0.99
M 7.92
decreased at constant copper sulfate
0.0625
1M 0.80 0.99 concentrations, the cell potential increased.
M 15.84
Meanwhile, as the concentration of copper sulfate
decreased at constant zinc sulfate concentrations,
the cell potential decreased. The activity and
activity coefficient can be determined using the
Nernst equation. The calculated activities for the
system only ranged from 0.99 to 1.00 M due to
the diluted solutions. The activity coefficient
measured how much the solution differed from
the ideal solution. The difference ranged from
0.99 to 16.00.

6. References
https://chem.libretexts.org/Core/Physical_and_T
heoretical_Chemistry/Physical_Properties_of_M
atter/Solutions_and_Mixtures/Nonideal_Solutio
ns/Activity
http://hyperphysics.phy-
astr.gsu.edu/hbase/Chemical/electrode.html
https://www.britannica.com/science/activity-
coefficient
https://www.thefreedictionary.com/activity
https://www
.amrita.olabs.edu.in/?sub=73&brch=8&sim=153
&cnt=1
http://vlab.amrita.edu/?sub=2&brch=190&sim=
361&cnt=1