Yeni piridinil sübstitüe benzotiyoat ile metal iyonlarının yarışmalı sıvı-sıvı ekstraksiyonu: Deneysel çalışmalar, gerçek matriks uygulamaları ve DFT bulguları

Öz

Bu çalışmada, S,S'-di(2-piridinil)-2,2'-ditiyodibenzotiyoat bileşiğinin metal iyonlarının karışımını içeren ortamlardan yarışmalı sıvı-sıvı iyon çiftleri ekstraksiyonu ile seçiciliği ve gerçek su matrikslerindeki metal giderim özellikleri araştırılmıştır. Zn²⁺, Mn²⁺, Cr³⁺, Fe³⁺, Co²⁺ ve Cu²⁺ iyonlarının karışımını içeren çözeltilerle gerçekleştirilen ekstraksiyon deneylerinde, ligandın özellikle Fe³⁺ iyonuna karşı yüksek seçicilik gösterdiği tespit edilmiştir. Ekstraksiyon verilerinin değişimi ICP-OES ile belirlenmiş ve en iyi ekstraksiyon verimi Fe³⁺ iyonu için (%44.12) elde edilmiştir. Nispi seçimlilik faktörleri, ligandın Fe³⁺ iyonunu diğer metal iyonlarına göre daha yüksek olarak ekstrakte ettiğini göstermiştir. Ayrıca, bileşiğin gerçek su matrislerindeki performansının belirlenmesi amacıyla göl, akarsu ve musluk suyu örneklerine metal giderim çalışmaları uygulanmıştır ve iyonların değişimi ICP-MS tespit edilmiştir. Ayrıca ligandın elektronik yapısı ve ekstraksiyon davranışı arasındaki ilişki yoğunluk fonksiyoneli teorisi (DFT) hesaplamaları ile incelenmiştir. Hesaplanan HOMO–LUMO enerji aralığı, kimyasal sertlik ve diğer küresel reaktivite parametreleri, ligandın özellikle yüksek yük yoğunluğuna sahip Fe³⁺ iyonlarıyla güçlü etkileşimler oluşturduğunu desteklemiştir. Elde edilen sonuçlar, S,S'-di(2-piridinil)-2,2'-ditiyodibenzotiyoat bileşiğinin çevresel su örneklerinden metal iyonlarının seçici uzaklaştırılmasında potansiyel bir ekstraksiyon ajanı olarak kullanılabileceğini göstermektedir.

Anahtar Kelimeler

• Sudan metal uzaklaştırma
• yarışmalı metal ekstraksiyonu
• metal kompleksleşmesi
• içme suyu kalitesi
• DFT.

Competitive liquid–liquid extraction of metal ions with novel pyridinyl-substituted benzothioate: Experimental studies, real matrix applications and DFT insights

Öz

In this study, the selectivity of the compound S,S'-di(2-pyridinyl)-2,2'-dithiodibenzothioate from media containing a mixture of metal ions was investigated using competitive liquid-liquid ion pair extraction, and its metal removal properties were studied in real water matrices. Extraction experiments conducted with solutions containing mixtures of Zn²⁺, Mn²⁺, Cr³⁺, Fe³⁺, Co²⁺, and Cu²⁺ ions revealed that the ligand exhibited particularly high selectivity towards the Fe³⁺ ion. The variation in extraction data was determined by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), and the best extraction efficiency was obtained for the Fe³⁺ ion (44.12%). Relative selectivity factors showed that the ligand extracted the Fe³⁺ ion more efficiently than other metal ions. Furthermore, metal removal studies were conducted on lake, stream, and tap water samples to determine the performance of the compound in real water matrices, and ion exchange was detected by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The relationship between the electronic structure of the ligand and its extraction behavior was also investigated using density functional theory (DFT) calculations. The calculated HOMO–LUMO energy gap, chemical hardness, and other spherical reactivity parameters supported the strong interactions of the ligand, particularly with Fe³⁺ ions, which have a high charge density. The results indicate that S,S'-di(2-pyridinyl)-2,2'-dithiodibenzothioate can be used as a potential extraction agent for the selective removal of metal ions from environmental water samples.

Anahtar Kelimeler

• Metal removal from water
• competitive metal extraction
• metal complexation
• drinking water quality
• DFT

Kaynakça

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