Ni (II)-Citrate complexing equilibrium and the correlation with electrolysis in nickel-citrate plating baths were studied. From absorption spectra, pH buffer capacity, and calculated simulation studies, it has been revealed that various complexes, NiHCit
0, NiCit
-, NiCit
24-, Ni (H
-1Cit)
2- etc., were formed in nickel citrate solutions, and the concentration distributions of these complexes were varied by the changes in the compositions and/or pH of the solutions. Above pH 4, the formation of 1:1 complex (NiCit
-) was recognized. In the pH range of 5 to 8, the proportion of NiCit
- decreased and that of NiCit
24-, which has lower molar absorptivity, increased with an increase in the Cit/Ni ratio in the solution. Above pH8, nickel-tetraionized citrate complex Ni (H
-1Cit)
2-, which has large molar absorptivity, was formed, and the pH value of formation of this complex became higher with an increase in the Cit/Ni ratio in the solution.
Electrolysis studies have revealed that, in neutral or alkali solutions, nickel-citrate equilibrium affected nickel deposition from nickel citrate solutions, and NiCit
24- and Ni (H
-1Cit)
2- were more electrochemically innert than NiCit
-. In acidic solutions, the addition of citrate accelerated the evolution of hydrogen, and decreased the current efficiency of nickel deposition.
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