Exercise No.

8
Determination of Activity and Activity Coefficient from Cell EMF

Gerry Mark Gubantes, John Patricia Mae Centeno, Joshua P. Movilla, Jo Darryl Fillaro, Jose
Carmelo P. Tinio, Alyssa Zen Aguillana
Date Performed: April, 2018; Date Submitted: May 09, 2018; Lab Section: 3L;
Instructor: King Bryan C. Gabog

Abstract

The activity and activity coefficients of varying concentrations of HCl

solution were calculated and determined using potentiometric method.
The activity coefficient was observed to deviate from the ideal value of
unity upon an increase in concentration of HCl values of each solution.
Both the activity and activity coefficient were observed to decrease
with increasing concentration.

I. Introduction Where mi is the molal concentration of

Electrochemical potential is a thermodynamic
quantity that involves the concepts of stored
energy in the form of chemical potential and
electrostatics. It measures the mechanical
work done in bringing one mole of a certain ion
from a standard state to a specified
concentration.
Essentially, potential is equal to a standard-
state potential plus a term that consists of RT
times the logarithm of a composition variable:
substance i. The ratio ai/mi is thus a measure
of the departure from ideal or ideally dilute
behavior and is also known as the activity
coefficient, γi, so that
a i = γi x i (8.4)
Since the potential Ei is temperature,
pressure, and composition (mole faction –
dependent then the activity and the activity
coefficient of substance i also depend on
these variables (Levine, 2002).

Ei = Ei 0 + RT ln(ai ) (8.1) In this exercise, the potential of cells would be

determined via potentiometry using
where Ei0 is the potential of substance i in the electrochemical cells.
appropriate standard state and where this
equation defines ai, the activity of substance i. Specifically, electrochemical cells are device
Activity is a dimensionless quantity that is in which the passage of electric current is
equal to unity if the substance is in its standard accompanied by the progress of a chemical
state (Mortimer, 2008). The activity of reaction. There are two types of
substance i in any solution (non-ideal or ideal) electrochemical cells: the galvanic and
by: electrolytic cell. Galvanic cell differs from
0 electrolytic cell since it produces electricity as
ai = e(Ei−Ei )/RT (8.2) a result of the spontaneous reaction occurring
inside the cell. On the other hand, electrolytic
Generally, the difference between a real and cell has a non-spontaneous reaction driven by
ideal solution is an external source of current. However, for
both cells, flow of electron is always from the
Ei − Ei ideal = RT ln(ai ) − RT ln(mi ) = anode to the cathode.
RT ln(ai /mi ) (8.3)
The exercise aims to determine the activity
and activity coefficient of HCl solutions of
varying conditions from the measured cell emf.
II. Methodology
HCl solutions (0.025 M and 0.005 M) were
prepared in duplicate and were allowed to
equilibrate at 25°C in water bath for 15
minutes. Emf develops in each solution was
measured using pH meter in mV scale and the
density of each prepared solutions were
determined using pycnometer. Furthermore,
10 mL aliquot of the solutions were titrated
(two trials) with standardized 0.010M NaOH to
determine the actual molal concentration of
the solutions.
III. Results and Discussion
Potentiometry is the determination of cell
potentials from electrochemical cells under
controlled conditions. Electrochemical cells
are devices that are driven by oxidation-
reduction (redox) reactions in order to
generate electrical energy (galvanic cell) or
facilitate a redox reaction by utilizing electricity
(electrolytic cell). The cell potential, on the
other hand, is the amount of electrical energy
stored in an electrochemical cell (Skoog et al.,
2007).
An electrochemical cell consists of two
electrical conductors called electrodes, each
immersed in a suitable electrolyte solution. For
a current to develop in a cell, it is necessary
that (i) the electrodes be connected externally
with a metal conductor, (ii) that the two
electrolyte solutions are in contact to permit
movement of ions from one to the other, and
(iii) an electron transfer reaction can occur at
each of the two electrodes. The reference
electrode (cathode) is used to determine the
potential of the other half cell in an
electrochemical cell; this must be highly stable
even when exposed to changes in
temperature and concentration. Some
common examples of reference electrodes
include SHE, SCE, and Ag-AgCl. An indicator
electrode (anode), on the other hand, is used
to determine the activity of the analyte in a
solution. An example is the glass electrode
that is used to determine hydrogen ion activity
(Skoog et al., 2007).
The electrochemical cell specifically used
to determine the potential of HCl solutions was
a glass calomel cell:
Ag, AgCl sol’n of known pH| glass | sol’n of
unknown pH | KCl(sat’d), Hg2Cl2
The reference electrode is the calomel
electrode:
Hg2Cl2(s) + 2e- → 2Hg + 2Cl-
In Standard Calomel electrode, a platinum
wire is in contact with liquid mercury, a paste
of mercurous chloride (calomel), KCl, mercury,
and filling solution (usually saturated KCl and
mercurous chloride). This electrode has a
standard potential of 0.242V vs the standard
hydrogen electrode (SHE). Other commonly
used reference electrode is the Ag/AgCl
electrode consisting of a silver wire coated
with a layer of AgCl in a saturated solution of
KCl and AgCl filling solution. This electrode
has a standard potential of 0.199V versus the
standard hydrogen electrode. The SHE
(standard hydrogen electrode) consists of a
platinum electrode immersed in a solution with
a hydrogen ion concentration of 1.00M. The
platinum electrode is made of a small square
of platinum foil which is platinized (known as
platinum black). Hydrogen gas, at a pressure
of 1 atmosphere, is bubbled around the
platinum electrode. The platinum black serves
as a large surface area for the reaction to take
place, and the stream of hydrogen keeps the
solution saturated at the electrode site with
respect to the gas (Skoog et al., 2007).
The indicator electrode for the
electrochemical cell is the glass electrode
consisting of a tube with a thin membrane of
pH sensitive glass containing a chloride
solution of known pH and an internal reference
electrode which is usually a SCE or Ag/AgCl
reference. The glass membrane is interactive
with hydrogen ions. Equilibrium is established
with hydrogen ions on the inner and outer
surfaces which produces a potential. The
hydronium activity difference between the
solution inside the electrode and the external
one is measured as electric potential
difference (Skoog et al., 2007).
The potential of a glass electrode is given
as:
2.303𝑅𝑇 𝑅𝑇
𝐸 = 𝐸0 + 𝜁
𝑝𝐻 = 𝐸0 − 𝜁
ln 𝑎𝐻+ (8.1)

Since the electrode makes use of saturated

KCl solution, its potential is constant. Then at
25ºC the equation is reduced to:
𝐸 = 𝐸 0𝑔 − 0.0592 𝑙𝑜𝑔𝑎𝐻+ (8.2)
where
𝑎𝐻+ = 𝑎± = 𝛾± 𝑚± = 𝛾± 𝑚 (8.3)
for univalent solutions like HCl, evaluation of
the equation yields:
𝐸 = 𝐸 0𝑔 − 0.0592 𝑙𝑜𝑔𝛾± − 0.0592 𝑙𝑜𝑔𝑚
(8.4)
Debye-Huckel limiting law further states that
𝑙𝑜𝑔𝛾± = −0.511√𝑚 (8.5)
Thus general equation 8.1 for glass electrode
can be written as:
𝐸 = 𝐸 0𝑔 + 0.03025√𝑚 − 0.0592 𝑙𝑜𝑔𝑚
or
𝐸 + 0.0592 𝑙𝑜𝑔𝑚 = 𝐸 0𝑔 + 0.03025√𝑚
E°g can then be determined from
experimental potential values, emf (E) and
molality (m). Experimental values of molality
for each HCl solution was calculated from
experimental values obtained in the titration of
HCl with standardized NaOH.
Figure 8.1. A typical SCE and Ag/AgCl
electrode.
In this experiment, the activity and coefficient
of activity of various HCl solutions were
determined from the measured cell emf.
The emf of a cell is the sum of the electric
potential differences produced by a separation
of charges that occur at each phase boundary
of the cell. The magnitude of each depends on
the chemical nature of the two contacting
phases. At the interface between two different
(8.6) metals, some electrons will have moved from
the metal with a higher free energy of electrons
to the metal with a lower free energy of
electrons. The resultant charge separation will
(8.7)
produce a potential difference that, at
equilibrium exactly opposes further electron
flow.
First, HCl solutions with nominal
concentrations of 0.005M, 0.010M, 0.015M,
0.020M and 0.025M were prepared. Then, the
prepared solutions were equilibrated in a 25oC
water bath for 15 minutes. Next, the potential
of each solution were obtained. Also, the
density of each solution was obtained using
the pycnometer. Each solution was then
titrated with 0.010M NaOH and the
concentration of each solution in molality was
determined. The experiment was done in
duplicate.

Equilibration was done to satisfy the

assumption of the experiment since dilute
solutions of HCl would allow the Debye – Table 8.1. Standardization of 0.010M NaOH.
Huckel Limiting Law to hold. I II
Mass of 0.0308 0.0251
KHP, g
Volume of 0.0099 0.00675
NaOH
used, L
Molarity of 0.015234116 0.018208395
NaOH
Average
0.016721256
Molarity

Table 8.2. Data on the determination for moles and mass of HCl.

Concentration vol NaOH mol HCl mass HCl

0.005 0.75 1.25409E-05 0.00045728

0.01 3 5.01638E-05 0.001829121

0.015 11 0.000183934 0.006706779

0.02 15 0.000250819 0.009145607

0.025 18 0.000300983 0.010974729

The actual mass of the aliquots used were using pycnometer. Table 8.3 lists the densities
calculated using the density values calculated calculated

Table 8.3. Data on the density measurement of HCl.

Mass of Solution Average Density
concentration, Trial 1 Trial 2
M

0.005 24.2466 24.2386 24.2426 2.41701168

0.01 24.1648 24.2436 24.2042 2.413183161

0.015 24.2556 24.2431 24.24935 2.417684662

0.02 24.2427 24.2437 24.2432 2.417071501

0.025 24.2451 24.2418 24.24345 2.417096426

Mass of water = 10.0003g; ρH2O: 0.99704

A pH meter was used to determine the increase as the concentration increases. At

electromotive force (emf) of the solutions in higher concentration, formation of greater
mV scale. Theoretically, the emf should number of ions in the solution will be favored,
thus, there will be a greater tendency to have
charge carriers and therefore high emf
(Levine, 2002).
The standard electrode potential was
calculated as well as other electrochemical
parameters such as the activity coefficient, γ±,
for the different HCl solutions of varying
molality. The activity of HCl solutions, αH+
was calculated also. From these, it can be
observed that the activity coefficient
decreases with increasing molality as well as
its activity.

Table 8.4. Calculated molality.

Concentration Mass of Aliquot, g Mass of solvent,
g
molality
0.005 24.1701168 24.16965952 0.000518871
0.01 24.13183161 24.13000249 0.002078896
0.015 24.17684662 24.17013984 0.007609961
0.02 24.17071501 24.1615694 0.0103809
0.025 24.17096426 24.15998953 0.012457894

Table 8.5. Data on the determination of E0g

√𝒎 0.0592 log(m) E E + 0.0592 log (m)
0.022778746 -0.194468471 0.203 0.008531529
0.045594912 -0.1587843 0.262 0.1032157
0.087235088 -0.125422161 0.282 0.156577839
0.101886701 -0.117438888 0.291 0.173561112
0.111614938 -0.112749677 0.296 0.183250323

Table 8.6. Data on the regression parameters for the determination of E0g.
slope 1.819187399
0
y-int (E g) -0.009268892
R 0.960754127
R^2 0.923048493

Figure 8.2. The plot for the determination of the E0g.

Determination of Eg
0.25
E + 0.0592 log (m)

0.2 y = 1.81918740x - 0.00926889

R² = 0.92304849
0.15
0.1
0.05
0
0 0.02 0.04 0.06 0.08 0.1 0.12
√𝑚
Table 8.7. Activity and activity coefficient of the HCl solutions.
Concentration 𝜸± 𝒂±
0.005 0.500399893 0.000259643
0.01 0.012587006 2.61671E-05
0.015 0.001579556 1.20204E-05
0.02 0.000815935 8.47014E-06
0.025 0.00055974 6.97318E-06

Figure 8.3. shows the activity of the solution Errors in the experiment can be attributed to
as the concentration increases. The activity of impurities, errors in the preparation of the
a dissolved species in solution is the solutions, reading of buret, determination of
effective concentration of that species. In an endpoints during titration and malfunction of
ideal solution, the molecules in the solution do the apparatus used for emf determination.
not interact with each other and the
concentration and the activity are almost
approaching to be identical. This is the case for Activity vs Concentration
very dilute solutions. The activity can be 0.0003
expressed as the product of an activity 0.00025
coefficient and the concentration. On the other 0.0002 y = -0.01046074x + 0.00021957
hand, activity coefficient is a factor used to R² = 0.56132511
Activity
0.00015
account for deviations from ideality. In an ideal 0.0001
mixture, the interactions between each pair 0.00005
of chemical species are the same and, as a 0
result, properties of the mixtures can be -0.00005 0 0.01 0.02 0.03
expressed directly in terms of -0.0001
simple concentrations or partial pressures of Concentration, M
the substances present. Deviations from
ideality are accommodated by modifying the Figure 8.3. Plot of activity vs. concentration.
concentration by an activity coefficient (Levine,
2002).
Activity Coefficient vs Concentration
Figure 8.4. shows the plot of activity coefficient
0.6
vs concentration. The activity coefficient is a
0.5
Activity Coefficient

measure of the effectiveness with which that

0.4
species influences equilibrium where it y = -20.22902754x + 0.40662384
0.3
participates. In solutions of low concentration, R² = 0.51845726
0.2
the activity coefficient for a given species is
0.1
independent of the nature of the electrolyte and
0
dependent only on the ionic strength. For a
given ionic strength, the activity coefficient of -0.1 0 0.005 0.01 0.015 0.02 0.025 0.03

an ion departs farther from unity as the charge -0.2

Concentration, M
carried by the species increases. As the ionic
strength increases, however the ion loses
Figure 8.4. Plot of activity coefficent vs.
some of its effectiveness and its activity
coefficient decreases. The activity coefficient of concentration.
a given ion describes its effective behavior in
all equilibria in which it participates (Levine,
2002).
On the other hand, other methods can also be
used to determine the activity and activity
coefficients of a solution. Saleh and Khylstov
(2009) determined the activity coefficients of
semi-volatile organic aerosols using the
integrated volume method. It was used to
determine the activities of adipic acid, pimelic
acid, dioctyl sebacate and ammonium sulfate.
Initially, the mole fraction was estimated
using an iterative computer algorithm. Next, the
change in volume was calculated using the
equation:
Then, the activity coefficient using the Vaan
Laar Equation:
where A and B are experimentally obtained
values from the regression parameters of
Δ𝜈𝑝 𝑣𝑠 𝑥 (Saleh and Khylstov, 2009).
IV. Conclusion
The activity and activity coefficients of
varying concentrations of HCl solution were
calculated and determined using
potentiometric method. Potentiometry is the
determination of cell potentials from
electrochemical cells under controlled
conditions. Theoretically, potential readings
increase with increasing HCl concentrations.
An increase in HCl concentration results to the
presence of more ionic species in solution
hence the number of charge carrier increases
with concentration resulting to an increase in
emf of the cell. Also, the activity of the solution
decreases with increasing HCl concentration
since the activity approaches the value of the
concentration of the molarity with increasing
concentration. Calculated activity coefficients,
also, decreases with increasing molality. The
activity coefficient of an ideal and dilute solution
is in unity and since the value is a measure of
deviation from ideality, it is more appropriate to
say that the activity coefficient deviated from
unity with increasing concentration.
V. References
LEVINE, I. N. 2002. Physical Chemistry, 6th
Ed. New York: McGraw-Hill.
MORTIMER, R.G. 2008. Physical Chemistry.
3rd ed. Canada: Elsevier Academic Press, Inc.
SALEH, R. and KHYLSTOVE, A. 2009.
Determination of Activity Coefficients of
Semi-Volatile Organic Aerosols Using the
Integrated Volume Method. Aerosol Science
and Technology, 43:838–846,
SKOOG, D. A., F. J. HOLLER, and S. R.
CROUCH 2007. Principles of Instrumental
Analysis. 6th Ed. New York: Brooks/Cole
Publishing.
I. Sample Calculations

1. Standardization of 0.010M NaOH (Trial1):

𝑚𝑎𝑠𝑠 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

( )𝐾𝐻𝑃 ( )
𝑀𝑁𝑎𝑂𝐻 = 𝑀𝑀 𝑚𝑜𝑙 𝐾𝐻𝑃
𝑉𝑁𝑎𝑂𝐻

0.0308𝑔 1𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

( ) ( )
204.22𝑔/𝑚𝑜𝑙 𝐾𝐻𝑃 1𝑚𝑜𝑙 𝐾𝐻𝑃
𝑀𝑁𝑎𝑂𝐻 =
0.0253 𝐿

𝑀𝑁𝑎𝑂𝐻 = 0.015234116 𝑚𝑜𝑙/𝐿

𝑇𝑟𝑖𝑎𝑙 2: 𝑀𝑁𝑎𝑂𝐻 = 0.018208395𝑚𝑜𝑙/𝐿

0.015234116 𝑀 + 0.018208395 𝑀
𝑨𝒗𝒆𝒓𝒂𝒈𝒆 𝑴𝑵𝒂𝑶𝑯 = = 𝟎. 𝟎𝟏𝟔𝟕𝟐𝟏𝟐𝟓𝟔 𝑴
2

2. Moles of HCl (0.005M, Trial1):

1 𝑚𝑜𝑙 𝐻𝐶𝑙
𝑛𝐻𝐶𝑙 = (𝑀𝑉)𝑁𝑎𝑂𝐻
1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

mol 1 𝑚𝑜𝑙 𝐻𝐶𝑙

𝑛𝐻𝐶𝑙 = (0.016721256 )(0.075𝐿)𝑁𝑎𝑂𝐻 = 0.0000124509 𝑚𝑜𝑙𝑒𝑠
L 1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

3. Mass of HCl (0.005M, Trial1):

𝑚𝑎𝑠𝑠𝐻𝐶𝑙 = 𝑛𝐻𝐶𝑙 𝑀𝑀𝐻𝐶𝑙

𝑔
𝑚𝑎𝑠𝑠𝐻𝐶𝑙 = 0.0000124509 𝑚𝑜𝑙𝑒𝑠 𝑥 36.458 = 0.00045728𝑔
𝑚𝑜𝑙

4. Density of HCl solutions (0.005M, Trial1):

𝑚𝑎𝑠𝑠𝑝𝑦𝑐+𝑠𝑜𝑙′𝑛 − 𝑚𝑎𝑠𝑠𝑝𝑦𝑐 𝑚𝑎𝑠𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝜌𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑥𝜌𝐻2𝑂 = 𝑥𝜌𝐻2𝑂
𝑚𝑎𝑠𝑠𝑝𝑦𝑐+𝐻2𝑂 − 𝑚𝑎𝑠𝑠𝑝𝑦𝑐 𝑚𝑎𝑠𝑠𝐻2𝑂
24.2426 𝑔
𝜌𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑥0.99704 𝑔/𝑚𝐿
10.0003𝑔

𝜌𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 2.41701168𝑔/𝑚𝐿

5. Mass of aliquot (0.005M, Trial1):

𝑔
𝑚𝑎𝑠𝑠𝑎𝑙𝑖𝑞𝑢𝑜𝑡 = 𝜌𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑉𝑎𝑙𝑖𝑞𝑢𝑜𝑡 = 2.41701168 𝑥10𝑚𝐿 = 24.1701168𝑔
𝑚𝐿

6. Mass of Water (0.005M, Trial1):

𝑚𝑎𝑠𝑠𝐻2𝑂 = 𝑚𝑎𝑠𝑠𝑎𝑙𝑖𝑞𝑢𝑜𝑡 − 𝑚𝑎𝑠𝑠𝐻𝐶𝑙

𝑚𝑎𝑠𝑠𝐻2𝑂 = 24.1701168𝑔 − 0.00045728𝑔 = 24.16965952g

7. Actual Molality (0.005M, Trial1):

𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐶𝑙

𝑚𝑜𝑙𝑎𝑙𝑙𝑖𝑡𝑦𝐻𝐶𝑙 =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 (𝐾𝑔)

0.0000124509 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙𝑒𝑠

𝑚𝑜𝑙𝑎𝑙𝑙𝑖𝑡𝑦𝐻𝐶𝑙 = = 0.000518871
1Kg 𝐾𝑔
24.16965952 g x ( )
1000g

8. Determination of E°g (Trial1):

𝐸 + 0.0592𝑙𝑜𝑔𝑚 = 𝐸°𝑔 + 0.03025 √𝑚

y b m x
plotted values:
x (√𝑚) y ( 𝐸 + 0.0592𝑙𝑜𝑔𝑚)
0.022778746 0.008531529
0.045594912 0.1032157
0.087235088 0.156577839
0.101886701 0.173561112
0.111614938 0.183250323

𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑙𝑖𝑛𝑒: 𝑦 = 1.819187399𝑥 − 0.009268892

𝑬°𝒈 = −𝟎. 𝟎𝟎𝟗𝟐𝟔𝟖𝟖𝟗𝟐

slope 1.819187399
y-int (E0g) -0.009268892
R 0.960754127
R^2 0.923048493

9. Determination of γ± (0.005M, Trial1):

𝐸°𝑔−𝐸−0.0592𝑙𝑜𝑔𝑚
𝛾± = 𝑒 ( 0.0592
)

−0.009268892−0.203−0.0592𝑙𝑜𝑔0.000518871
𝛾± = 𝑒 ( 0.0592
)

𝛾± = 0.500399893

10. Determination of aH± (0.005M, Trial1):

𝑎𝐻+ = 𝛾± 𝑚

𝑎𝐻+ = 0.500399893 𝑥 0.000518871

𝑎𝐻+ = 0.000259643