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Chapter 13 - Electric Double Layer

This chapter discusses the electric double layer that forms at the interface between an electrode and electrolyte solution. It explains that specific adsorption of ions onto the electrode surface can make the surface potential more negative. The extent of specific adsorption follows the ordering of I->Br->Cl->F from most to least polarizable. Adsorption isotherms like the Langmuir and Frumkin isotherms are presented to relate surface coverage to concentration. The electric double layer can influence reaction rates at the electrode by affecting the potential difference across it.

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195 views5 pages

Chapter 13 - Electric Double Layer

This chapter discusses the electric double layer that forms at the interface between an electrode and electrolyte solution. It explains that specific adsorption of ions onto the electrode surface can make the surface potential more negative. The extent of specific adsorption follows the ordering of I->Br->Cl->F from most to least polarizable. Adsorption isotherms like the Langmuir and Frumkin isotherms are presented to relate surface coverage to concentration. The electric double layer can influence reaction rates at the electrode by affecting the potential difference across it.

Uploaded by

rmramsundar
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© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Chapter 13 Electric Double Layer

Relationship between (M & S), and Cd Specific Adsorption Specific versus nonspecific adsorption Non-specific adsorption provides no mechanism for the electrode potential to vary with the electrolyte concentration. Surface tension plots diverge at E-Epzc > 0 due to specific anion interactions with the surface. I- > Br- > Cl- > F- More polarizable, the greater the tendency to specifically adsorb. Full or partial charge transfer with the electrode, but often the negative charge is retained. Essentially, specific or contact adsorption of an anion makes the surface potential more negative.
-

Chapter 13 Electric Double Layer


1/RT (E+/-/ ln aib)M Concentration (M)
1.0 0.1 0.01 Esin Markov Effect

Epzc (NaF)
-0.472 V -0.472 V -0.480 V

Epzc (KI)

-0.820 V -0.720 V -0.660 V

vs. SCE

Extension of the electrode. Makes potential more negative. More negative E is required to compensate with solution charge.

Much of what is known about the electric double layer structure comes from many measurements: 1. 2. 3. 4. 5. Cd and surface tension Single crystal metals UHV surface science methods STM Radio tracer studies

Chapter 13 Electric Double Layer


Adsorption Isotherms Adsorption isotherm relationship between i, ai, & E or qM aia = aib exp(-Go/RT) = iaib A. Langmuir Isotherm No interactions between adsorbed molecules. No heterogeneities in the surface sites. Monolayer coverage at saturation. s i/(s - i) = iaib /(1-) = iaib = i/s i = siCi/(1 + iCi)
Conc. i

Chapter 13 Electric Double Layer


A. Frumkin Isotherm Interactions between adsorbed species can sometimes occur on a surface. i/(s - i) exp (-2gi/RT) = iaib g 0, Langmuir isotherm approached g = expresses the way in which coverage changes adsorption energy of i. ((J/mol)/(mol/cm2)) g > 0 then interactions are attractive. g < 0 then interactions are repulsive.

GoFrumkin = GoLangmuir - 2gi

Rate of build-up of adsorbed layer depends on the rate of mass transport to the surface. i = siCi = siCi(0,t) i(t) = Di [Ci(x,t)/x]x=0 t

Chapter 13 Electric Double Layer


Double Layer Effects on Reaction Rates ko electrolyte composition Variation in potential in the double layer region Oz + e- Rz-1 A. z 0 Co(x2,t) = Cob exp (-zF2/RT) io = nFAkoCo(1-)CR Surface concentration greater than bulk.

B. Potential driving reactions is not M S = Eappl, but rather M S 2 Effective potential is Eappl 2
kt = ko exp [-(-z)F2/RT] io,t = io exp [-(-z)F2/RT]

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