CHAPTER VII

Electrochemical Thermodynamics

Prepared by
Dr. Ehteram A. Noor
Associate Prof. of physical chemistry

Revised by
Dr. Salwa Al-Rashid
Associate Prof. of physical chemistry

Ehteram A Noor- Kng Abdulaziz University

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 Gibbs Function and Electrical Work
Start with the First Law of Thermodynamics and some
standard thermodynamic relations. We find

dE  dq  dw dq = T dS
dw  P dV  dwelectrical
dE  TdS  PdV  dwelectrical
dH P  dEP  PdV

dGT  dH T  TdS
dGT  dET , P  PdV  TdS
dGT  TdS  PdV  dwelectrical  PdV  TdS
dGT,P  dwelectrical
And therefore, the Gibbs function is at the heart of electrochemistry,
for it identifies the amount of work we can extract electrically from a
system. Ehteram A Noor- Kng Abdulaziz University

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 Gibbs and the Cell Potential
Here we can easily see how this Gibbs function relates to a
potential.
welectrical   Potential  Ch arg e   EQ

GT , P  welectrical and Q  nF

GT , P  nFE

By convention, we identify work which is negative with

work which is being done by the system on the
surroundings. And negative free energy change is
identified as defining a spontaneous process.
Note how a measurement of a cell potential directly calculates
the Gibbs free energy change for the process.
Ehteram A Noor- Kng Abdulaziz University

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 Variation of e.m.f with temperature
One of the most rewarding aspects of electrochemistry is that
ΔS values spring directly from studies of the temperature
variation of e.m.f.
dG o dE o
Since o  nF
G  nFE
o
dT dT
o
where (dE / dT ) is the temperature coefficient of the
electrochemical cell
dG o dE o
Look at this equation dT  nF dT
important relationship between numerical factors and Eo can be obtained

Entropy (S)
 G o 
   S o
Thermodynamic relationship  T  P

dE o dE o S o
S  nF
o

dT dT nF Ehteram A Noor- Kng Abdulaziz University

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 Enthalpy (H)
Thermodynamic relationship H o  G o  TS o

dE o
Since o S o  nF
G  nFE
o
dT

dE o
H o  nFE o  T (nF )
dT

dE o
H  nF ( E  T
o o
)
dT

Ehteram A Noor- Kng Abdulaziz University

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 Ehteram A Noor- Kng Abdulaziz University

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 Ehteram A Noor- Kng Abdulaziz
University

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 Ehteram A Noor- Kng Abdulaziz University

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Text resources
J. M. Seddon and J. D. Gale, Thermodynamics and Statistical Mechanics, The Royal
Society of Chemistry, (2001)
G. W. Castellan, Physical Chemistry, 2nd Edn. (1971), Adison-Wesley Publishing
Company, Amesterdam
I. Tinoco, Jr, K. Sauer and J. C. Wang, Physical Chemistry, (1978), Prentice-Hall, Inc.,
New Jersey
W. J. Moore, Basic Physical Chemistry, (1983), Prentice-Hall, Inc., New Jersey
J. R. Wan and A. P. H. Peters, Concise Chemical Thermodynamics, 2nd Edn. (1996),
Taylor & Francis e-Library.http://www.ebookstore.tandf.co.uk/.”
R. J. Silbey and R. A. Alberty, Physic al Chemistry, 3rd Edn. (2001), John wiley &
Sons, New York.
I. N. Levine, Physical Chemistry, 5th Edn. (2003), McGraw-Hill, New York.

Electronic Web resources

mmadou.eng.uci.edu/classes/MAE-212/MAE212.II.pptx

Ehteram A. Noor- King AbdulAziz University