Mechanism and kinetics of the electrosorption of sulphate anions on the (111) face of silver
Mehanizam i kinetika elektrosorpcije sulfatnih anjona na (111) pljosni srebra
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The processes of adsorption of sulphate anions onto the (111) face of silver have been investigated by analysis of the cyclic voltammetry and potcntiostatic pulse results. It was shown, by fitting the experimentally recorded θ - E dependences, that the adsorption of anions follows Frumkin adsorption isotherm. The adsorbed structure was found to be less dense than expected for the dense packed anion monolayer and the process was characterized by high value of the interaction parameter and the Gibbs energy of adsorption (f = 16.5 and ΔGoads.θ→0 = - 64 kJ mol 1). From the slope of the Ep.a - log (c0) dependence it was concluded that complete charge transfer between the adsorbed anions and the silver substrate occurs. This is supported by the Ep.a - log v linear dependence in the region of high sweep rates (v > 10 V s 1) with rational value of line slope (≈ 60 mV dec 1) which is possible only if the complete charge transfer reaction occurs. The elcctrosorption process of sulphate anions wa...s found to be complex electrochemical reaction, taking place through three steps. It was proposed that the rate-determining step is the second step, i.e., the electrochemical formation of (SO4)ads species.
Proučavan je proces adsorpcije sulfatnih anjona na (111) pljosni monokristala
srebra metodama ciklične voltametrije i potenciostatskih pulseva. Na osnovu eksperimentalno određenih q–E zavisnosti pokazano je da se na adsorpciju može primeniti Frumkinova adsorpciona izoterma. Nađeno je da je gustina adsorbovanog sloja
manja nego kada bi sloj bio maksimalno moguće gusto pakovan kao i da adsorpciju
karakterišu visoke vrednosti Frumkinovog parametra interakcije (f = 16,5) i Gibsove
energije adosrpcije (DGºads,q®0 = –64 kJ mol). Na osnovu nagiba zavisnosti Ep,a –log (c0)
zaključeno je da se pri elektrosorpciji odigrava i potpuna izmena naboja anjona sa
supstratom. Ovaj zaključak podržava dobijena linearna zavisnost Ep,a – log v u oblasti
velikih brzina promene potencijala (v>10 V s–1) sa racionalnom vrednošću nagiba (»60
mV dek–1), a koja se može dobiti samo pri odigravanju potpune razmene naboja. Utvrđeno
je da je elektrosorpcija sulfatnih anjona složena elektrohemijska reakcija ko...ja se
odigrava u tri stupnja. Stupanj koji određuje brzinu ukupne reakcije je drugi stupanj,
elektrohemijsko stvaranje intermedijera (SO4)ads.
Keywords:
(111) face of silver / Complete charge transfer / Frumkin adsorption isotherm / Mechanism and kinetics of electrosorption / Sulphate anionsSource:
Journal of the Serbian Chemical Society, 1999, 64, 9, 539-552Publisher:
- Belgrade : Serbian Chemical Society
Funding / projects:
- The Ministry of Science and Technology of the Republic of Serbia
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Institution/Community
IHTMTY - JOUR AU - Jović, Borka M. AU - Dražić, Dragutin M. AU - Jović, Vladimir D. PY - 1999 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/4410 AB - The processes of adsorption of sulphate anions onto the (111) face of silver have been investigated by analysis of the cyclic voltammetry and potcntiostatic pulse results. It was shown, by fitting the experimentally recorded θ - E dependences, that the adsorption of anions follows Frumkin adsorption isotherm. The adsorbed structure was found to be less dense than expected for the dense packed anion monolayer and the process was characterized by high value of the interaction parameter and the Gibbs energy of adsorption (f = 16.5 and ΔGoads.θ→0 = - 64 kJ mol 1). From the slope of the Ep.a - log (c0) dependence it was concluded that complete charge transfer between the adsorbed anions and the silver substrate occurs. This is supported by the Ep.a - log v linear dependence in the region of high sweep rates (v > 10 V s 1) with rational value of line slope (≈ 60 mV dec 1) which is possible only if the complete charge transfer reaction occurs. The elcctrosorption process of sulphate anions was found to be complex electrochemical reaction, taking place through three steps. It was proposed that the rate-determining step is the second step, i.e., the electrochemical formation of (SO4)ads species. AB - Proučavan je proces adsorpcije sulfatnih anjona na (111) pljosni monokristala srebra metodama ciklične voltametrije i potenciostatskih pulseva. Na osnovu eksperimentalno određenih q–E zavisnosti pokazano je da se na adsorpciju može primeniti Frumkinova adsorpciona izoterma. Nađeno je da je gustina adsorbovanog sloja manja nego kada bi sloj bio maksimalno moguće gusto pakovan kao i da adsorpciju karakterišu visoke vrednosti Frumkinovog parametra interakcije (f = 16,5) i Gibsove energije adosrpcije (DGºads,q®0 = –64 kJ mol). Na osnovu nagiba zavisnosti Ep,a –log (c0) zaključeno je da se pri elektrosorpciji odigrava i potpuna izmena naboja anjona sa supstratom. Ovaj zaključak podržava dobijena linearna zavisnost Ep,a – log v u oblasti velikih brzina promene potencijala (v>10 V s–1) sa racionalnom vrednošću nagiba (»60 mV dek–1), a koja se može dobiti samo pri odigravanju potpune razmene naboja. Utvrđeno je da je elektrosorpcija sulfatnih anjona složena elektrohemijska reakcija koja se odigrava u tri stupnja. Stupanj koji određuje brzinu ukupne reakcije je drugi stupanj, elektrohemijsko stvaranje intermedijera (SO4)ads. PB - Belgrade : Serbian Chemical Society T2 - Journal of the Serbian Chemical Society T1 - Mechanism and kinetics of the electrosorption of sulphate anions on the (111) face of silver T1 - Mehanizam i kinetika elektrosorpcije sulfatnih anjona na (111) pljosni srebra VL - 64 IS - 9 SP - 539 EP - 552 DO - 10.2298/jsc9909539j ER -
@article{ author = "Jović, Borka M. and Dražić, Dragutin M. and Jović, Vladimir D.", year = "1999", abstract = "The processes of adsorption of sulphate anions onto the (111) face of silver have been investigated by analysis of the cyclic voltammetry and potcntiostatic pulse results. It was shown, by fitting the experimentally recorded θ - E dependences, that the adsorption of anions follows Frumkin adsorption isotherm. The adsorbed structure was found to be less dense than expected for the dense packed anion monolayer and the process was characterized by high value of the interaction parameter and the Gibbs energy of adsorption (f = 16.5 and ΔGoads.θ→0 = - 64 kJ mol 1). From the slope of the Ep.a - log (c0) dependence it was concluded that complete charge transfer between the adsorbed anions and the silver substrate occurs. This is supported by the Ep.a - log v linear dependence in the region of high sweep rates (v > 10 V s 1) with rational value of line slope (≈ 60 mV dec 1) which is possible only if the complete charge transfer reaction occurs. The elcctrosorption process of sulphate anions was found to be complex electrochemical reaction, taking place through three steps. It was proposed that the rate-determining step is the second step, i.e., the electrochemical formation of (SO4)ads species., Proučavan je proces adsorpcije sulfatnih anjona na (111) pljosni monokristala srebra metodama ciklične voltametrije i potenciostatskih pulseva. Na osnovu eksperimentalno određenih q–E zavisnosti pokazano je da se na adsorpciju može primeniti Frumkinova adsorpciona izoterma. Nađeno je da je gustina adsorbovanog sloja manja nego kada bi sloj bio maksimalno moguće gusto pakovan kao i da adsorpciju karakterišu visoke vrednosti Frumkinovog parametra interakcije (f = 16,5) i Gibsove energije adosrpcije (DGºads,q®0 = –64 kJ mol). Na osnovu nagiba zavisnosti Ep,a –log (c0) zaključeno je da se pri elektrosorpciji odigrava i potpuna izmena naboja anjona sa supstratom. Ovaj zaključak podržava dobijena linearna zavisnost Ep,a – log v u oblasti velikih brzina promene potencijala (v>10 V s–1) sa racionalnom vrednošću nagiba (»60 mV dek–1), a koja se može dobiti samo pri odigravanju potpune razmene naboja. Utvrđeno je da je elektrosorpcija sulfatnih anjona složena elektrohemijska reakcija koja se odigrava u tri stupnja. Stupanj koji određuje brzinu ukupne reakcije je drugi stupanj, elektrohemijsko stvaranje intermedijera (SO4)ads.", publisher = "Belgrade : Serbian Chemical Society", journal = "Journal of the Serbian Chemical Society", title = "Mechanism and kinetics of the electrosorption of sulphate anions on the (111) face of silver, Mehanizam i kinetika elektrosorpcije sulfatnih anjona na (111) pljosni srebra", volume = "64", number = "9", pages = "539-552", doi = "10.2298/jsc9909539j" }
Jović, B. M., Dražić, D. M.,& Jović, V. D.. (1999). Mechanism and kinetics of the electrosorption of sulphate anions on the (111) face of silver. in Journal of the Serbian Chemical Society Belgrade : Serbian Chemical Society., 64(9), 539-552. https://doi.org/10.2298/jsc9909539j
Jović BM, Dražić DM, Jović VD. Mechanism and kinetics of the electrosorption of sulphate anions on the (111) face of silver. in Journal of the Serbian Chemical Society. 1999;64(9):539-552. doi:10.2298/jsc9909539j .
Jović, Borka M., Dražić, Dragutin M., Jović, Vladimir D., "Mechanism and kinetics of the electrosorption of sulphate anions on the (111) face of silver" in Journal of the Serbian Chemical Society, 64, no. 9 (1999):539-552, https://doi.org/10.2298/jsc9909539j . .