Fig. 4: In situ Raman spectra on [C4Py]Cl-2AlCl3 reacting with LDPE and n-hexadecane as a model reactant.

a In situ Raman spectra recorded during the cracking-alkylation of LDPE and iC₅ in the presence of TBC additive. b The time-resolved conversion profile of LDPE and the corresponding variation of chloroaluminate species using Equation (Eq. (1)). c The n-C₁₆ consumption as a function of chloroaluminate species in consecutive processes. d the initial rate (calculated as grams of LDPE converted per minute) as a function of Al-adducts concentration. Note: we studied the rates at low conversions <20 wt. %. The changes in concentrations over various time intervals are expressed as ∑[Al-adduct] = ∆[AlCl₄^‒]. Conditions: a-b: LDPE, 200 mg; iC₅, 800 mg; [C₄Py]Cl-2AlCl₃, 2 mmol; TBC, 5 mg; DCM, 3 ml; and temperature, 70 °C. c_: In the 1^st run, 150 mg of n-C₁₆, 600 mg of iC₅ and 5 mg of TBC as an additive were added into the reactor containing 2 mmol of [C₄Py]Cl-2AlCl₃ and 3 ml of DCM. Upon n-C₁₆ was fully converted, the reactor was rapidly cooled under −30 °C and replenish with another 150 mg of fresh n-C₁₆. e–f The standard Helmholtz free energy (ΔF°) of Al₂Cl₇^‒ catalyzed hydride abstraction from iC₅ (e) and AlCl₃-TBC adduct catalyzed hydride abstraction from n-C₁₆ (f) as a function of the molecular distance between reacting molecules, achieving via ab initio molecular dynamics simulations coupled with a Blue Moon ensemble method.