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PHYSICAL CHEMISTRY III

THERMODYNAMIC EMF CELL


Created by:
Ni Wayan Riska Rianthi

(1213031009)/ V A

Ni Putu Rahayu Kusuma Pratiwi

(1213031014)/ V A

I Wayan Suriadi

(1213031052)/ VA

CHEMISTRY EDUCATION DEPARTMENT


FACULTY OF MATHEMATICS AND NATURAL SCIENCES
UNIVERSITAS PENDIDIKAN GANESHA
2014
PREFACE

Thanks to the God Almighty who has bless us to finishing this paper with the title
Thermodynamic EMF Cell. This paper is made for our assignment in Physical Chemistry
III lesson.
In process to create this paper, the authors found some problem. It is because of our
knowledge still need an improvement. But, because of the guidance and big support from
many peoples, so we can finish it. Therefore, the authors want to say thanks to the:
1. Drs. Nyoman Retug, M.Si as our lecture who has guidance us
2. Our friends in RKBI Class who has supported us.
3. And many others who has supported us.
This paper is still need improvement and still contain many mistake, because of that
we need advice and critics to make this paper will be better and can useful for many people.
Singaraja, September 2014

Authors

TABLE OF CONTENTS
Preface ............................................................................................................................. ii
Table of Contents ............................................................................................................ iii
Chapter I. Introduction ................................................................................................... 1
1.1 Background ........................................................................................................ 1
1.2 Problem Statement ............................................................................................. 1
1.3 Objectives .......................................................................................................... 1
Chapter II. Discussion ..................................................................................................... 2
2.1 Electromotive Force (EMF) ...............................................................................2
2.2 Thermodynamics EMF Cell .............................................................................. 3
Chapter III. Closing ......................................................................................................... 7
3.1 Conclusion ......................................................................................................... 7
References

CHAPTER I
INTRODUCTION
1.1 Backgrounds
Electrochemistry is the study of the exchange between electrical and chemical
energy has important applications in everyday life stretching from the battery that powers
your portable radio to the electro refining that produces the copper pipes carrying your
drinking water. Those electrochemical processes utilize oxidation and reduction
reactions. An oxidation involves the loss of one or more electrons from a chemical
species while a reduction is the gain of one or more electrons by a chemical species.
When an oxidation and a reduction are paired together in a redox reaction, electrons can
flow from the oxidized species, the reducing agent, to the reduced species, the oxidizing
agent or oxidant. That electron flow can either be spontaneously produced by the
reaction and converted into electricity, as in a galvanic cell, or it can be imposed by an
outside source to make a non-spontaneous reaction proceed, as in an electrolytic cell.
The potential between cathode and anode are different, so it can be calculated by
voltmeter. The usage of usual voltmeter is also to meassure the EMF, but it is not
efective because there is current from the cell passing the voltmeter which caused the
change of EMF. This paper will describe about the electromotive force (EMF) and
thermodynamics of EMF cell.
1.2 Problem Statements
Based on the background above, can be concluded some problems statements, there are:
1. What is the electromotive force (EMF)?
2. How the thermodynamics of EMF cell?
1.3 Purposes
Based on the problem statements above, it can be concluded some purposes, there are:
1. To understand the electromotive force (EMF).
2. To understand about the thermodynamics of EMF cell.

CHAPTER II
DISCUSSION
2.1 Electromotive Force (EMF)
Electromotive force (EMF) is the different of potential from cell in reversible state,
where there is no flowing electric current. This state can be reached by balancing the cell
potential with the external potential. It done by using potentiometer.
The potential different or electromotive force (EMF) can be measurred by using
usual votlmeter. The usage of usual voltmeter to meassured the EMF is not efective
because there is current from the cell passing the voltmeter which caused the change of
EMF. The more efective meassurement is conducted by using tools as follow.
1) Highly hold up voltmeter
2) Valve voltmeter (DC amplifiers)
3) Potentiometer
The measurement of EMF by using this tools causes no current or little current is taken
from the cell.
In this paper only discussed the meassurement of cell EMF by using potentiometer.
The usage of potentiometer in meassure EMF uses the tool devise base on the
Poggendrofs principle. Based on this way, the meassured EMF is balanced by the same
EMF from another resources, such in Figure 1.

Picture 1. EMF Measurement


BC is a uniform hold up wire which connected to battery A. U is cell of EMF
which will be measured. G is galvanometer, D is shift contact. The contact D is shifted to
prevent current passing G (I = 0) so that, the cells EMF is balanced by potential
2

EMFcell BD

EMF A BC

lowering between B and C. Therefore

. Then the cell is substituted by

another cell which has known EMF. The standard cell used is usually Weston cell with
EMFcell = 1.018 volt at 25oC. In each process above occurred the equilibrium when:
EMFcell
BD

EMF s tan dard BX

2.2 Thermodynamics EMF Cell


Heat that produced is comparable to quadrate electricity (I 2) and resistance (R) as
well as to I2Rt. Because of R = V/I, so heat is comparable to VIt , thus:
q=VIt

Note:
q= joule (J) = kgm2s-2
V= volt (V) = kgm2s-3A-1
I= ampere (A)
t= second (s)
The statements above is true, but there are an error state that heat that produced is
reactions heat (Joule, Helmholtz, William Thomson). Then, the new statement from
William Gibbs states that heat that produced is a change of cell work (Welectricity).
W electricity

= QV =( It )( IR )=I Rt

Work has been done by electrochemistry cells is maximum work in outside the work.PV, same with the thederivation of Gibbs energy.
It can be ilustrate by cell below:
2H+

Cathode : H2
Anode

: Cu2+ + 2e- Cu

Cell

: H2 + Cu2+

2e-

2H+ + Cu

When, one mole of H 2 react with one mole of Cu2+ , two mole of electron flow in
outside the series. According to Faraday Laws, it means there are electric current as
much as {( 2 mole)(6.02 x 10 23 mole-1)(1.6 x 10-19 C)} = 2 x 96.485 C electric. The cell
potential is + 0.3419 volt, so electric work that produce is:
W electricity

= QV
3

= 2 x 96.485 C x 0.3419 volt


= 6.598 x 104 Joule
Work has been done by system. Because of the work of electrochemistry cell same with
the derivation.
If the cell on the reversible cell reaction, free energy (G) system can be expressed
as follows:
G = - nFE and Go = - nFEo
The reaction is spontaneous if G value Ecell positive or G negative.
Example:
For the cell Pt | H2

(1 bar)

| HCl

(aq)

| AgCl

(s)

| Ag, Eocell = 0.2223 volts and Ag-AgCl

electrode as the cathode. Determine the value of Go!


Answer:
Cathode : AgCl(s) +

e-

Anode : H2(g)
Cell

Ag(s)

: AgCl(s) + H2(g)

+ Cl-(aq)

Eo = 0,2223 volt

H+(aq) + e-

Eo = 0

Ag(s) + H+(aq) + Cl-(aq)

volt
Eo = 0,2223

volt
So, the value of Go can be calculated as follow:
Go = -nFEo = -(1) (96485 C mol-1) (0,2223 V)
= -21450 J mol-1
= -21,45 kJ mol-1

For the cell with the reaction equation: aA + bB

cC + dD, and the change of

free energy can be expressed:


G G o + RT ln

aC c a D d
a A a aB b

At equilibrium, G = 0, so that:

Go = - RT ln K

aC c a D d
K
a A a aB b

Go = -RT ln K = -nFEo

Eo =

RT
ln K
nF
4

EMF data cells do not only provide the information value of free energy and
activity coefficients, but also provide much information about the thermodynamic
properties of the other ions in solution. Entropy change (S) can be determined using the
following equation:
G

or

nF

G o

S o
P

nF

While the change in enthalpy (H) cell reaction can be calculated using the following
equation:
E

H G TS nFE nFT

Thus the determination of the EMF of cells in a series of temperature it is possible


to determine G, S, and H for the reaction cell. High accuracy in determining the
amount of electrochemical thermodynamics in this way causes more exact in
determining the equilibrium constant rather than directly or determination of the enthalpy
of the reaction calorimeter.
Example:
A cell: Cd | CdCl2 | AgCl | Ag, Ecell = 0.67533 V at 25oC and the temperature
coefficient = -6.5 x 10-4 VK-1. Calculate the value of G, S, and H at temperature of
25oC for the following cell reaction: Cd + 2AgCl CdCl2 + 2Ag
Answer:
Anode : Cd

Cd2+ + 2e-

Cathode : 2AgCl + 2e- 2Ag + 2ClCell

: Cd + 2AgCl CdCl2 + 2Ag

The electrons involve are two.


G = -nFE
= -(2) (96485 Cmol-1) (0,67533 V)
5

= -130,318 kJmol-1
E

S nF

= (2) (96485 Cmol-1) (-6,5 x 10-4 VK-1)


= 125 JK-1mol-1
E

H nFE nFT

= -(2)(96485 Cmol-1)(0,67533 V) + (2)(96485 Cmol-1)(298)(-6,5x10-4 VK-1)


= -167,58 kJmol-1

CHAPTER III
CLOSING
Conclusion

Electromotive force (EMF) is the different of potential from cell in reversible state,
where there is no flowing electric current.

If the cell on the reversible cell reaction, free energy (G) system can be expressed as
follows:
G = - nFE and Go = - nFEo
The reaction is spontaneous if G value Ecell positive or G negative. At equilibrium, G
= 0, so that:

Go = - RT ln K

aC c a D d
K
a A a aB b

Go = -RT ln K = -nFEo

Eo =

RT
ln K
nF

While the change in enthalpy (H) cell reaction can be calculated using the following
equation:
E

H G TS nFE nFT

References:

Mulyani, S., & Hendrawan. 2005. Kimia Fisika 2. Malang: IKIP Malang
Suardana, I. N., & Retug, I. N. 2003. Kimia Fisika 3. Singaraja: IKIP Negeri
Singaraja