APPLICATION OF GALVANIC CELLS EMF

MEASUREMENT FOR PHYSICAL

AND CHEMICAL PROPERTIES

Author:
MSc Diana Rymuszka

Editors:
Prof. dr hab. Emilian Chibowski
Dr hab. Agnieszka Ewa Wiącek
Task 36

APPLICATION OF GALVANIC CELLS EMF

MEASUREMENT FOR PHYSICAL
AND CHEMICAL PROPERTIES

I. Aim of the task

The aim of the task is:
– determination of solubility ratio of sparingly soluble salts AgX using EMF meas-
urements of appropriate cells,
– determination of half-cell Ag|Ag+ standard potential and silver ion activity coeffi-
cient using EMF measurements of appropriate cell.

II. Introduction

1. Definitions: galvanic cell, half-cell, cell EMF, half-cell potential, electrolytic cell.
2. Galvanic half-cell types: electrode reactions, cell schemes, the potential expression.
3. Concentration cells: classification, exemplary cells scheme, electrode reaction equa-
tions, cell SEM, potential of diffusion, formation mechanism, electrolytic key.
4. Application of EMF measurement for thermodynamic parameters determination: solu-
bility product, standard cell EMF and standard half-cell potential, average electrolyte
activity coefficient.

References:
1. P. W. Atkins, Physical Chemistry, 4th edition, Oxford University Press
1992, 249-270.
2. D.W. Rogers, Concise Physical Chemistry, Wiley 2011, 220-234.
3. H. Kuhn, H-D. Försterling, D.H. Waldeck, Principles of Physical Chemistry,
2nd edition, Wiley, 2009.
–3– Task 36 – Application of galvanic cells EFM measurement

I. Theory

III. 1. Electromotive force of galvanic cells

The energy effect of chemical reaction can manifest itself as a heat of reaction, me-
chanical work or electric work. The source generating electricity in a chemical reaction are
redox reactions related with the electron transfer from the molecule of one compound to an-
other molecule. This process takes place not through the direct exchange, but through an out-
side conductor connecting the circuit between the cell electrodes.
An electrochemical cell consists of two electrodes (electricity conductors) dipped in an
electrolyte (electrolytic conductor). The electrode dipped in the electrolyte is a half-cell. Half-
cells can have different or the same electrolyte. In the case of the same electrolyte, the solu-
tions of both half-cells can contact directly with the liquid interface formation or via ion con-
ductive solution (electrolytic bridge).
In this case, the electrolytic bridge allows to eliminate (almost completely) the effects
associated with the liquid interface (diffusion potential). When the cell electrodes are dipped
in two different electrolytes, the electrical contact between them can be obtained for example
by using the electrolytic bridge.
An electrochemical cell in which a spontaneous chemical reaction proceeds, there-
upon the electricity is produced, is called the galvanic cell. If as a result of voltage applied
between two electrodes in the electrolytic cell unspontaneous chemical reaction is enforced,
then the electrolysis is observed.
During the current flow in the galvanic cell partial oxidation and reduction reactions
on the electrodes can be set. Electrons released in the oxidation reaction set on the lower po-
tential electrode:
Mred → Mutl + nē (1)
flow by the external circuit to the higher potential electrode and the reduction reaction pro-
ceeds:
Mutl + nē → Mred (2)
where n – the number of electrons taking part in the cell’s reaction.
The substance which takes part in the reduction reaction gets the electrons from the
electrode, thus imparts positive charge, corresponding to a higher potential value. On the oth-
er electrode, during the oxidation reaction the electrons are evolved causing negative charge
appearance (corresponding to lower value of the electrode potential).
Analysing the processes taking place in the galvanic cells two types of cells can be
distinguished:
– chemical cells - the source of electricity is chemical reaction,
– concentration cells - the source of electricity is the electrolyte activity change (the
electrolytic concentration cell - in both half - cells the electrolyte concentration is
different; the electrode concentration cell - different electrolyte concentrations, e.g.
Physical Chemistry –4–

gaseous electrodes with different gas pressure or amalgam electrodes of different

amalgam concentration).
The galvanic cells schemes:

E M ||M E


E M |M  E
 (3)

E M ⋮ M  E

where: (–) (+) – the negative and positive cell electrode, | - the interface: electrode (E) - the
electrolyte solution (M), ||- the interface at which the diffusion potential was eliminated (elec-
trolytic bridge), - the fluid interface (diffusion potential).

Fig. 1. The example of the concentration cell.

According to the IUPAC recommendation, a scheme of galvanic cells should be writ-

ten in such a way that the reduction reaction in the scheme always proceeds on the right half-
cell.
The reversible cell is the cell in which the reversible processes at the interface are ob-
served.
The electron transfer during the reaction in the cell is the source of the work which de-
pends on the potential difference between cell electrodes. The electric work can be done by
the cell in which the total reaction does not achieve equilibrium (this reaction makes electrons
flow in the external circuit). If the potential difference between the electrodes of the cell is
high, then the electric work which is the result of electrons flow in the cell is high as well. If
the potential difference between the electrodes is small then the electric work is small. When
the reaction reaches equilibrium in the cell, the potential difference of its half-cell is equal to
zero and such a cell cannot do work (e.g. discharged car battery). Maximum work can be ob-
tained only in the reversible cell. To measure thermodynamic parameters using cell work
measurements, reversible work must be secured. When the potential difference between the
cell electrodes is balanced with opposite external voltage, the spontaneous reaction in the cell
is stopped and the system as the whole will be in equilibrium (the reaction in the cell is not at
equilibrium, but is measured in the equilibrium state) and then the partial processes proceed-
ing in the cell are reversible. The potential difference between the cell electrodes measured
under those conditions is known as the electromotive force of cell (EMF), E or the cell volt-
age under powerless conditions. If both half-cells are under standard conditions (activity or
fugacity of the redox reaction reagents is equal to unity) then EMF of such a cell is called the
–5– Task 36 – Application of galvanic cells EFM measurement

standard electromotive force, Eo. The electromotive force (EMF) can be presented using the
Nernst equation:

E  E  ln Q (4)


where: R – the gaseous constant, T- the temperature [K], F – the Faraday constant,
Q – the reaction quotient, the quotient of the activity (concentration) of ions involved in the
reaction proceeding in the cell.
The electromotive force of the cell can be expressed by two electrodes potential dif-
ference:
E  Π  Π (5)
where: ΠR, ΠL- the potentials of right and left half-cells.
A similar dependence can be expressed for the standard electromotive force of cell as
the potential difference of two standard half-cells:
   Π  Π (6)
where: Π0R, Π0L are the standard potentials of right and left half-cells.
The measurable quantity which characterizes half-cell is its potential. It can be defined
as the electromotive force of the examined half-cell and standard hydrogen half-cell.

III. 2. Galvanic half-cell types

There can be distinguished a few different galvanic half-cell types:

III. 2.1. Half-cells reversible to the cation

Half-cells with the active metal electrode
Half-cell of this type is formed by metal dipped in its ions solution Me|Men+. The reac-
tion proceeds:
Mn+ + nē → Me (7)
and its potential can be expressed:
  
Π  Π   ln   Π  ln a"# (8)
 

where: $%& , $%& ' - metal and its activity, $%&  1.

Fig. 2. Scheme of half-cell with active metal electrode.

Physical Chemistry –6–

Gaseous half-cell
Gaseous half-cell consists of metal (very often noble metal) dipped in a solution satu-
rated with appropriate gas containing the potential-creative ions. The example of that type of
half-cell is the hydrogen half-cell Me|H2|H+, in which there proceeds the reaction:
2H++ 2ē → H2(g) (9)
and its potential can be expressed by the equation:
 ) 
) 
Π ln  ln (10)
 )  )

Fig. 3. Scheme of the hydrogen half-cell.

III. 2.2. Half-cells reversible towards the anion

Gaseous half-cells
An example of this type of half-cell is the chlorine Me|Cl2|Cl- (platinum electrode
rinsed with a chlorine gas stream dipped in a chloride solution), in which the reaction takes
place:
Cl2 + 2ē → 2Cl– (11)
and its potential can be expressed with the equation:
  ,  *+,
Π  Π  
ln *+  Π  
ln (12)
*+
*+ 

Second type half-cells

The second type half-cell is formed from the metal electrode coated with a tight layer
of sparingly soluble metal salt and dipped in a solution containing anions of this salt. The ex-
ample of such a half-cell is silver-chloride half-cell Ag|AgCl|Cl- in which the following reac-
tion takes place:
AgCl + ē → Ag + Cl– (13)
and its potential can be expressed by the equation:
 -. ∙ *+, 
Π  Π  
ln -.*+
 Π  
ln a01, (14)

where from the definition the solid activity aAg = 1 and aAgCl = 1.
–7– Task 36 – Application of galvanic cells EFM measurement

Fig. 4. Scheme of the silver-chloride half-cell.

The other example of the second type half-cell is the very widely applied calomel
half-cell Hg|Hg2Cl2|Cl- in which the following reaction takes place:
Hg2Cl2 + 2ē → 2Hg + 2Cl– (15)
and its potential can be expressed by the equation analogous to (14).

III. 2.3. Redox half-cells

Redox half-cells are constructed of chemically neutral metal dipped in a solution con-
taining the oxidized and reduced forms of an ion Me|Me , Me . The electrochemical oxida-
tion-reduction reaction taking place in that type of half-cell runs with contribution of the elec-
trons provided by the metallic electrode which it does not take direct part in the reaction. The
electrode plays here an electric charge conducting role. The potential of such half-cell can be
expressed with the equation:
 
Π  Π   ln 45 (16)
67+

where ared and autl – the activity of the reduced and oxidized forms, respectively.
An example of such a half-cell is Pt|Fe2+,Fe3+ half-cell where there proceeds the reac-
tion:
Fe3+ + ē → Fe2+ (17)
and its potential can be expressed by the equation:
 
Π  Π  ln  8 (18)
 89

or quinhydrone half-cell with non-reactive metal dipped in a saturated quinhydrone solution.

In an aqueous solution of this compound there is an equimolar amount of quinone (q) and
hydroquinone (hq) molecules. The reaction in the half-cell can be expressed as follows:
(q) C6H4O2 + 2H+ + 2 ē → C6H4(OH)2 (hq) (19)
and the potential is equal to:
  ;
Π  Π  lna:  ln  (20)
  <=<

Another group of cells are concentration cells. The source of the electromotive force
here is the work of ions transfer from higher concentration (activity) solution to a lower con-
Physical Chemistry –8–

centration solution. Considering two types of concentration cells, in the transfer cell the di-
rect contact between the electrolyte solutions is present. An example there can be a cell con-
structed from two identical half-cells of different activity electrolyte:

EM
a  ⋮ M 
a E
 (21)
In the case of this cell direct ions migration from higher concentration solution to low-
er concentration solution is possible for example by porous membrane. Due to the diffusion
rate difference of various ions at the two solutions interface, uncompensated charge is accu-
mulated. The ensuing electric field gradient causes rise (for slower moving ion) or lowering
(for faster moving ion) of diffusion rate. As a result, a steady state is achieved in the system
and all the ions move along with the same speed and the potential difference at the interface
does not change. This potential difference is called the diffusion potential. The diffusion
potential is bigger with bigger difference in the concentration of the two solutions, as well
bigger ions mobility difference. The electromotive force of such a cell can be expressed by
the equation:
 
EMF  E  t ∙  ln  (22)

where t – the number of cation or anion transfer.

In the case of cells without transfer, the solutions of each half-cells are separated from
each other (contact is enabled by the electrolytic bridge), which prohibits direct ions migra-
tion between half-cells:
(–) E|Mn+(a1)||Mn+(a2)|E (+) (23)
Because the solutions do not get into contact, the diffusion potential is not formed. The
electromotive force of such cell can be expressed with the equation:
 
EMF  E  
ln  (24)

The quotient of transfer of the cell electromotive force (EMFtransf) and the electromo-
tive force of the cell without transfer (EMF) with the same ion reversible electrodes is called
the ion transfer number:
@"74A BC
t  @" (25)
Measurement of electromotive force appropriate cells allows determination of various
physicochemical properties.

III. 3. Determination of the standard half-cell potential and the

standard cell electromotive force

Determination of the standard half-cell potential value is based on accurate EMF

measurements of appropriate cell at different electrolyte solution concentrations. Consider a
cell with the metallic active electrode Me|Men+ and with the reference half-cell constant po-
tential, e.g. calomel electrode. EMF of that type of cell is equal to the difference of potentials
of the two half-cells:
–9– Task 36 – Application of galvanic cells EFM measurement

  
E  Π  ΠD#E 
Π  ΠD#E   ln c ∙ f 
Π  ΠD#E   ln c  lnf (26)
  

where c – the concentration of potential-determining ions, f – the coefficient of the potential-

determining ions activity.
Expressing the activity coefficient by appropriate function of concentration, depending
on the used concentration range:
logf  A√c (27)
L√M
logf   NO (28)
√M

logf  A√c  C ∙ c (29)

where A, B, C, a – the constants.
Substituting these functions into equation (26) one obtains equation, which allow
standard half-cell potential value determination.
In the case of the simplest function (27) application, the following equation is ob-
tained:
 
E ln c  QΠ  ΠD#E R  ∙ 2.303 ∙ A√c (30)
 
then denoting:

E    lnc  E W (31)
equation (32) is obtained:

E W  Π  ΠD#E 2.303  ∙ A√c (32)

Equation (32) is a straight line dependence of E '= f (√X):

E W  b  aZcL[\]9 (33)
from which by the extrapolation to c = 0, and taking into account the calomel half-cell poten-
tial, standard potential of the examined half-cell can be determined. Similarly, the cell stand-
ard electromotive force can be determined using the measurements for the appropriately se-
lected half-cells system.

III. 4. Ion electrolyte activity rate determination

The electromotive force measurement of concentration cell without transfer with

known electrolyte concentration allows the electrolyte activity coefficient determination from
the equation:

log f  .^^ 
E  E    logc (34)
Physical Chemistry – 10 –

III. 5. Solubility product determination

Knowing the standard potential of an appropriate pair of half-cells of first and second
types of the same metal phase (e.g. Ag|Ag+ and Ag|AgCl|Cl-) the solubility product of a salt
can be determined:

log I  Π``  Π` (35)
.^^ 

The solubility ratio can be determined from measurements of electromotive force of

appropriate concentration cells.
– 11 – Task 36 – Application of galvanic cells EFM measurement

II. Experimental

A. Devices and materials

1. Devices
- digital voltmeter,
- silver electrodes,
- saturated calomel electrode,
- measurement vessels,
- electrolytic bridge,
- 25 cm3 flasks,
- 10 cm3 pipettes,
- 0.5 cm3 pipettes,
- 100 cm3 beaker,
- wash bottle.
2. Materials:
- 0.1 M AgNO3 solution,
- saturated KCl,
- 0.1 M KCl solution,
- 0.1 M KBr solution,
- 0.1 M KI solution,
- 0.1 M KOH solution,
- 0.1 M KSCN solution,
- 0.1 M K2Cr2O7 solution.

B. Solubility product determination

1. Cells preparation
Prepare cells according to the scheme (-) Ag|AgX(sat)||AgNO3(0.1M)|Ag (+)
where X= Cl, Br, I, OH, SCN, Cr2O7.

Fill one of the measurement vessels with 9 cm3

of 0.1M AgNO3. To another vessel put exactly 3
cm3 of 0.1M AgNO3 and 6 cm3 of 0.1M KCl
(KBr, KI, etc.) and mix carefully. Insert silver
electrodes into both measurement vessels and
connect them with the electrolytic bridge.
Physical Chemistry – 12 –

2. EMF determination
Connect the electrodes of the cell with the external sockets of digital voltmeter and
turn on the electric supply of the meter.
Measure EMF of all cells. After each measurement both electrolytic bridge and elec-
trode should be rinsed with distilled water.

C. Standard potential of half-cell Ag|Ag+ and activity coefficient of silver ions

determination
1. Cells preparation
Prepare cells according to the scheme (-)Hg,Hg2Cl2|KCl(sat)||AgNO3(cx)|Ag(+) where
cx = 0.001; 0.002; 0.005; 0.01; 0.05; 0.1M. Dilute 0.1M AgNO3 solution with distilled water
in flasks in order to obtain given solutions. Pour 9 cm3 of AgNO3 solution of appropriate con-
centration into one of measurement vessels and insert the silver electrode into it. Fill another
measurement vessel with saturated KCl solution and put in the calomel electrode. Connect
both vessels with the electrolytic bridge.
2. EMF determination
Connect the electrodes of cell with the external socket of digital voltmeter and turn on
the electricity supply to the meter.
Measure EMF for all cells. After every measurement both the electrolytic bridge and
the electrode should be carefully rinsed with distilled water.

D. Results
1. Solubility ratio determination
a) Calculation of Ag+ ions concentration in half cell for each examined electrolyte.
The cell can be examined as the concentration cell:
(-) Ag | [Ag+](c1) || AgNO3(c2=0.1M) | Ag(+)
and EMF of that cell is:
 M  .
E ln M  ln M (36)
 

where: c1 – the concentration of Ag+ ions in the left half-cell, c2 – the concentration of Ag+
ions in the right half-cell; c2 is the constant equal to 0.1M (AgNO3 concentration).
Concentration of Ag+ ions in the left half-cell c1 can be calculated using equation (36).
b) Solubility product determination.
Solubility product of salts AgX (X= Cl, Br, I, OH, SCN, Cr2O7) is expressed:
LAgX = [Ag+] [X-] (37)
 – 13 – Task 36 – Application of galvanic cells EFM measurement

In the case of Ag2Cr2O7:

LL[ 0D ]b  cAg N dcCr Obg d (38)
The anion concentration is equal to the concentration of precipitant excess, e.g. for
mono-valence anions [X-]:
mol

6 ∙ 10g^ dm^  3 ∙ 10g^ dm^  ∙ 0.1
g
cX d  dm^  1 ∙ 10g mol
3 ∙ 10g^ dm^  6 ∙ 10g^ dm^ 3 dm^
c) Results presentation

Results of calculations should be presented in Table 1.

Table 1. Solubility ratio determination.

Cell scheme E [V] c1 = [Ag+] LAgX Lfrom the table

c1 = const = 0.1M

2. Standard potential of half-cell Ag|Ag+ and activity rate of silver ions determination.
a) Standard potential of half-cell Ag|Ag+ determination
EMF of examined cells can be expressed as the difference between first kind of metal
Ag and calomel half-cells:
RT
EMF  E  ΠL[/L[  Πm0@  ΠL[/L[  lnQaL[ R  Πm0@ 
F

 QΠ L[/L[  Πm0@ R   lnQcL[ ∙ fL[ R  (39)
RT RT
 QΠ L[/L[  Πm0@ R  lnQcL[ R  lnQfL[ R
F F
where: ΠAg/Ag+- the potential of Ag|Ag+ half-cell, Π0Ag/Ag+- the standard potential of Ag|Ag+ half-
cell, ΠSCE- the potential of saturated calomel half-cell, aAg+- the activity of silver ions, cAg+- the
concentration of metal ions, fAg+ - the activity coefficient of metal ions.
Physical Chemistry – 14 –

The potential of Ag|Ag+ half-cell can be determined by graphical extrapolation using

the limiting Debye-Hückel law which allows to express the activity coefficient as a function
of concentration:
log fp  q|rN rg |√s (40)

where: I – the ionic strength of the solution,s  ΣXt rt , z+, z- - the ions valence, A- the con-
stant.
In the case of aqueous electrolyte solutions of type 1:1 (e.g. AgNO3), this dependence
is simplified to:
logfL[  AZcL[\]9 (41)
after introducing equation (41) into (39) we obtain:
 
E lnQcL[\]9 R  QΠ L[/L[  Πm0@ R  2.303 AZcL[\]9 (42)
 

and denoting

EW  E  
lnQcL[\]9 R (43)
we obtain

E W  QΠ L[/L[  Πm0@ R  2.303 AZcL[\]9 (44)

Equation (44) is the equation of straight line dependence of E W  f
ZcL[\]9 :
E W  b  aZcL[\]9 (45)
Plotting equation (45) and extrapolating to c = 0, one obtains the value of potential dif-
ference for the standard silver half-cell and calomel half-cell:
lim√v→  W  Π L[/L[  Πm0@ (46)
Plot the measured experimental results in coordinates of equation (45)
W
E  f
ZcL[\]9  (calculate E' from eq. (43)). The parameters of eq. (46) should be deter-
mined using graphical or least squares method (see Appendix). In the case of least squares
method, determine the theoretical dependence (46) based on determined values of calculated
before parameters. The calculation results should be presented in Table 2.
Knowing that the potential of the saturated calomel half-cell (SCE) against the stand-
ard hydrogen half-cell is equal to:
Πm0@ cVd  0.2415 – 0.00076
T  298 (47)
where T- the temperature [K], the standard potential of Ag|Ag+ half-cell can be determined and
compared with the theoretical tabular value. The constant A from the limiting Debye-Hückel
law should be compared with the theoretical tabular value as well.
b) Determination of activity coefficient of silver ions
Using the measured cell EMF values and the value calculated from equation (Π0Ag/Ag+
- ΠNEK) calculate the activity coefficients of silver ions in the examined system from the equa-
tion:
– 15 – Task 36 – Application of galvanic cells EFM measurement


log fL[  ∙ cE 
Π L[/L[  Πm0@ d  log cL[\]9 (48)
.^^

c) Results presentation
Results of the calculations should be presented in Table 2.

Table 2. Silver ions activity rate determination.

€‚ƒ„ E [V] E’ Z€‚ƒ„ log fAg+ fAg+