The  Role  of  Self‐exchange  Reactions  in  Ionic  Diffusion  in 

Thermocells 
IRVIN J. CENTENO, Universidad de Puerto Rico‐ Mayagüez 
Pablo Salazar, Baratunde Cola, Georgia Institute of Technology

Introduction 

A  thermo‐electrochemical  cell  (or  thermocell) 

uses  redox  couples  as  electrolyte  and  symmetric  d
metal  electrodes  to  generate  power  from  a  heat 
source.   k

Figure 2. Self‐exchange reactions schematic. 

Self‐exchange reactions take place between redox 
couples  in  the  bulk  electrolyte  of  thermocells.  A 
self‐exchange  reaction  is  a  chemical  process 
where  an  electron  moves  from  one  chemical 
specie to the other, changing the oxidation states 
Figure 1. Thermocell Schematic 
of  both  species.  These  reactions  are  usually  very 
Voltage  is  driven  by  a  temperature  gradient  fast. The species must diffuse into close proximity 
across the cell.  for the self‐exchange reactions to occur. 

∆
When a redox electrolyte is used in a thermocell, 
diffusion  is  the  process  that  makes  possible  the 
flux  of  ions  in  the  cell  in  order  to  maintain  the 
Equation 1. Cell voltage equation. 
electric current. This diffusion is enhanced by self‐
In  order  for  ionic  transfer  to  occur,  within  a  exchange  currents,  which  effectively  reduce  the 
thermocell, one of the following processes should  distance  over  which  individual  ions  must  diffuse. 
occur;  Convection:  net  velocity  of  ions  and  Using  the  redox  couple  ferri/ferrocyanide  we 
solvent  molecules,  Thermal  diffusion:  its  driving  strive  to  understand  the  balance  of  electronic 
force is a Thermal gradient, Migration: it’s driving  (self‐exchange) and ionic (diffusion) conduction in 
for  is  a  Potential  gradient,  or  Diffusion:  which  is  a  thermocell,  and  discover  ways  to  enhance 
driven by a Concentration gradient.  current and improve the efficiency of thermocells.  

∗ Methods 
∅  
For  self‐exchange  reactions,  we  can  derive  a 
Equation 2. Mass Transfer‐Nernst‐Plank model.  simple  expression  to  evaluate  the  effect  of 
exchange  redox  reactions  on  the  effective 
Other  than  diffusion,  migration,  and  convection  diffusivity (eq.3). 
of  ions,  electron‐transfer  processes  can  also 
contribute  to  ionic  transfer  if  the  solution   
contains an oxidation‐reduction system. 
20 Equation 3. Effective diffusion equation. 
Since Nernst-Einstein equation for mobility (eq.4)
is proportional to the diffusion of the ions we
replace the mobility in the mass transfer equation
(eq.2) for the this equation.

𝐷𝑧𝐹
𝑢=
𝑅𝑇
Equation 4. Nernst-Einstein equation for mobility.

Then we replace the effective diff equation (eq.3) Table 1. Experimental conductance difference values.
on the mass transfer equation and we get the
contribution.
If we were to use the model to find the values of
𝐹 2 𝑑2 𝑘𝐶𝑅 𝐶𝑂 conductance, using 𝑘=1.9𝑥104 𝑀−1 𝑠 −1
𝜎𝑀 − 𝜎𝐴 = 𝜎𝑒 =
𝑅𝑇 and𝑑 = 7 − 8 A, the order of magnitude for the
Equation 5. Derivation of the conductivity difference model experimental conductivity differences at high
(self-exchange reactions contribution). concentrations are in the same range as in the
theoretical model. At a lower concentration there
Materials
seems to be an offset in the values, which can be
Impedance spectroscopy studies, with three attributed to possible reactions occurring at these
electrodes, and the redox couple concentrations.
ferro/ferricyanide were conducted an interpreted
with model available in the literature to help
elucidate the contribution of self-exchange
reactions to the overall flux of ions in the
thermocell.

Figure 3. Experimental Setup.

Graph 1. Concentration vs. conductance difference.
The impedance tests resulted in graphs which
represented the equation of two circles. The
The results also suggest that catalytic dispersants
intersection between the two circles was
such as carbon nanotubes (CNTs) could be used to
measured as the ionic resistance. The inverse of
mediate self-exchange reactions and enhance the
these values was then interpreted as the
effective ionic diffusion in thermocells.
conductance.

Results and Discussion

The studies revealed that the contribution to the
generated current attributed to self-exchange or
electronic conduction is significant compared to
contribution attributed to ionic conduction
(diffusion).
21
Conclusions
Adding carbon nanotubes to the electrolyte
mixture could be used to mediate self-exchange
reactions and enhance the effective ionic
diffusion in thermocells.
Figure 5. Redox mechanism in redox-doped CNT.

By adding CNT we look to increase the effective

electron transfer distance in self-exchange
reactions.

References

1. “Electronic conduction in aqueous

solution” by Harald Dahms (1987)
2. “Application of Diffusion Constant
Measurement to the determination of the
Rate Constant of Electron-Exchange
Reactions” by I. Ruff (1970)
3. “Harvesting Waste Thermal Energy Using
a Carbon-Nanotube-Based Thermo
Electrochemical Cell” by Renchong Hu,
and Baratunde A. Cola (2010)

Acknowledgements

Funds for this research were provided by the

Center on Materials and Devices for Information
Technology Research (CMDITR), and the NSF
Science and Technology Center No. DMR
0120967.

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