Effect of Applied Voltage on Slow-Release of Cu(II) Ions on the Synthesis of Copper(II) Stearate Complex by Electrochemical Technique

Nordin, Norazah; Hasan, Siti Zubaidah; Zakaria, Zuhailie; Baharuddin, Noor Afzalina; Samad, Wan Zurina; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

doi:10.5935/0103-5053.20150074

Cited by 2 publications

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“…Most spectra bands of the carboxylate products correspond to the reference spectra of copper carboxylates (as shown through the synthesis presented in the experimental section of this work) and zinc carboxylates [13]. The main copper carboxylate maximum shows the antisymmetric peak at 1580-1586 cm − 1 and the symmetric one at 1415 (C8) and 1424 cm − 1 (C10-C18) with Δ at ~ 157-168 and cm − 1 (see values for the authentics in Table SI1) which has been assigned to a bridged bidentate dimer with a geometry resembling that of a paddle-wheel [51,52], shown in Scheme 1a. Besides, the line shape of the carboxylate bands depends on the crystallinity of the soap, which may variably depend on the surrounding medium [23,24,71].…”

Section: Discussionmentioning

confidence: 89%

“…Unidentate coordination assumes the highest Δ values, bridging geometries its lowest, while chelates and ionic structures (or salts) show intermediate values [44,49,50]. Besides, copper forms binuclear coordination complexes [51,52] with v as approx. 1580-1587 cm − 1 and the v s at 1415-1422 cm − 1 with a Δv ~ 165 cm − 1 , where a bidentate chelating geometry is obeyed [13,36,48].…”

Section: Introductionmentioning

confidence: 99%

“…Speci cally, the antisymmetric infrared maxima reported for copper carboxylates to be at higher values (1585 cm − 1 ) than those of the zinc carboxylates with an additional one at 1508 cm − 1 , while the symmetric band is found at 1415 cm − 1 [44,51] giving a Δ value of 170 cm − 1 . Additionally, copper carboxylate infrared spectra have been reported to assume multinuclear coordination geometries [41,44,55], although clear data have been shown for the binuclear complexes, where two Cu(II) ions are bridged through four carboxylate units [51,52]. These geometries are established on the basis of multiple carboxylate maxima (or 'multiplets') as shown below.…”

Section: Introductionmentioning

confidence: 99%

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Infrared spectroscopy reveals the reactivity of fatty acids on copper surfaces and its implications for cultural heritage objects

Boyatzis

Fragkos-Livanios

Giannoulaki

et al. 2023

Preprint

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The reactivities of various fatty monoacids and diacids on copper metal-containing surfaces were investigated through reflection-absorption infrared spectroscopy. The formation of copper soaps is detected on pure copper surfaces, while copper and zinc soaps are simultaneously formed as mixtures on brass surfaces. Following the changes of acidic carbonyl and carboxylate infrared bands, it is shown that fatty monoacids C8, and C10 react with clean/polished copper and its zinc alloy within 2–4 hours, while those with chains > C12 react within 15–40 days. An explanation for the above results is offered on a molecular mobility basis, where liquid monoacids at room temperature favour higher reaction rates. Furthermore, it is argued that longer-chain FMAs allow for favourable orientation resulting in self-assembled monolayer (SAM)-type molecular packing on Cu surface, may explain the slower reaction. Fatty diacids, on the other hand, do not form any carboxylate products under these conditions. In light of this interesting result, it is argued that dicarboxylic acids may also pack as self-assembled layers on Cu and ultimately protect it. The implications for fatty organic remains in copper containers are discussed, with emphasis on the stability of archaeological copper metal and carboxylates serving as molecular markers for the presence of fatty monoacids as residues in archaeological containers. Besides, the utilization of fatty acids, based on the above behaviour in copper-based dosimeters, such as those used in the Oddy test, is suggested.

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Section: Discussionmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Infrared spectroscopy reveals the reactivity of fatty acids on copper surfaces and its implications for cultural heritage objects

Boyatzis

Fragkos-Livanios

Giannoulaki

et al. 2023

Preprint

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show abstract

“…Ambient temperature was recorded at 23 °C and RH at 37%; time is given in hours:minutes structures (or salts) show intermediate values [47,52,53]. Besides, copper forms binuclear coordination complexes [54,55] with v as approx. 1580-1587 cm −1 and the v s at 1415-1422 cm −1 with a Δv ~ 165 cm −1 , where a bidentate chelating geometry is obeyed [13,39,51].…”

Section: Absorbancementioning

confidence: 99%

“…Specifically, the antisymmetric infrared maxima reported for copper carboxylates to be at higher values (1585 cm −1 ) than those of the zinc carboxylates with an additional one at 1508 cm −1 , while the symmetric band is found at 1415 cm −1 [47,54] giving a Δ value of 170 cm −1 . Additionally, copper carboxylate infrared spectra have been reported to assume multinuclear coordination geometries [44,46,47], although clear data have been shown for the binuclear complexes, where two Cu(II) ions are bridged through four carboxylate units [54,55]. These geometries are established on the basis of multiple carboxylate maxima (or 'multiplets') as shown below.…”

Section: Absorbancementioning

confidence: 99%

Infrared spectroscopy reveals the reactivity of fatty acids on copper surfaces and its implications for cultural heritage objects

Boyatzis,

Fragkos-Livanios,

Giannoulaki

et al. 2023

Herit Sci

View full text Add to dashboard Cite

The reactivities of various fatty monoacids and diacids on copper metal-containing surfaces were investigated through reflection–absorption infrared spectroscopy. The formation of copper carboxylates is detected on pure copper surfaces, while copper and zinc carboxylates are simultaneously formed on brass surfaces. Following the decrease of acid carbonyl and the formation of carboxylate infrared bands, it is shown that fatty monoacids C8 and C10 react with clean/polished copper and its zinc alloy within 2–4 h, while those with chains > C12 react within days. At the end of the processes, only the corresponding metal carboxylates are detected in all cases. An explanation for the above is offered on a molecular mobility and acidity basis, where the lower monoacids (liquids in room temperature), also having lower pKa values, favor higher reaction rates. Furthermore, it is argued that longer-chain fatty monoacids, when deposited from their solutions, allow for favorable orientation resulting in self-assembled monolayer-type molecular packing on the copper surface, which may additionally rationalize the slower reaction. Interestingly, fatty diacids do not form any carboxylate products under the same conditions, as it is argued that their molecules may efficiently pack as self-assembled multilayers on copper and ultimately protect it. The possible implications of the fatty monoacid and diacid behavior on the archaeological organic residues level and regarding the stability of copper alloys are discussed.

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Effect of Applied Voltage on Slow-Release of Cu(II) Ions on the Synthesis of Copper(II) Stearate Complex by Electrochemical Technique

Cited by 2 publications

References 0 publications

Infrared spectroscopy reveals the reactivity of fatty acids on copper surfaces and its implications for cultural heritage objects

Infrared spectroscopy reveals the reactivity of fatty acids on copper surfaces and its implications for cultural heritage objects

Infrared spectroscopy reveals the reactivity of fatty acids on copper surfaces and its implications for cultural heritage objects

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