Cmrr. Oliveira et al., EFFECT OF DIFFERENT EXPERIMENTAL PARAMETERS ON THE POTENTIOMETRIC EVALUATION OF BLOOD ELECTROLYTES USING K+ AS A TEST CATION, Analyst, 121(12), 1996, pp. 1907-1910
Potentiometric evaluation of ionic concentrations in physiological med
ia has been reported to be significantly affected by the albumin conta
ining matrix, Previous studies have attempted to clarify the origin of
different patterns of variation of E versus albumin concentration at
a constant 0.01 mol dm(-3) KCl, depending on the experimental methodol
ogies, This paper reports on measurements of K+ in albumin (BSA) conta
ining KCl solutions, which have been pursued following different metho
dologies concerning the sequence of measurements, i.e., starting eithe
r from the most concentrated solution (100 g dm(-3)) (A) or from the m
ost dilute solution (20 g dm(-3)) (B), and solution preparation, (a) d
ilution of an initial 100 g dm(-3) albumin solution by successive addi
tion of 0.01 mol dm(-3) KCl, (b) concentration of an initial 20 g dm(-
3) albumin solution by addition of solid substance, (c) independent pr
eparation of each albumin solution (20, 40, 60, 80 and 100 g dm(-3)) o
r (d) preparation of each albumin solution from direct dilution of a 1
00 g dm(-3) stock solution with 0.01 mol dm(-3) KCl, Convenient calcul
ations were made and showed a significant contribution of albumin to t
he liquid-liquid junction potential, The variation of potential with a
lbumin concentration is smaller for hypertonic than for isotonic bridg
e solutions, both for the dilution series (A,a and A,d) and for the co
ncentration series (B,c and B,d), When the method for increasing the c
oncentration is performed by addition of a solid substance to an initi
ally diluted albumin (B,b), the slope of the E versus albumin concentr
ation plot is larger for hypertonic than for isotonic reference electr
olytes. This latter finding is in agreement with Payne's results when
ultrafiltration was used to concentrate a protein solution, These obse
rvations are a clear indication that the method of preparation of conc
entrated protein solutions may significantly affect the results.