Two essential cationic surfactants, dodecyl trimethyl ammonium bromide (DTAB) and cetyl pyridinium chloride (CPC) with differences in the alkyl chain, were investigated as corrosion inhibitors on mild steel (MS) in 0.5 M H2SO4 with weight loss (WL) and the potentiodynamic polarization (PDP) method. Three different temperatures were used to maintain the reported sample solutions (298.15, 308.15, and 318.15 K) for concentrations ranging below, above, and at the optimum critical micelle concentration (CMC) of the cationic surfactants. Results show that 0.5 M DTAB having ammonium group gave higher inhibition efficiency than 0.5 M CPC having pyridinium group by PDP method. The inhibition efficiencies were determined as 98.6% for 0.5 M DTAB and 89.38% for 0.5 M CPC after 24 h immersion at 298.15 K. The extreme inhibition efficiency depends on the chain length and decreases with an increase in temperature as well as increases with the addition of concentration of cationic surfactants. Around CMC, both surfactants CPC and DTAB showed the highest inhibition efficiency which follows the isotherm of Langmuir adsorption and illustrates a mixed type of corrosion inhibitors with the predominance of cathodic reactions. Additionally, the proposed mechanisms of inhibitors showing both physical and chemical adsorption confirmed by the free energy of adsorption (-ΔGads0) for DTAB were >28–34.5 kJ/mol and for CPC were >31.07–42.91 kJ/mol.
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