eutech-instruments cyanide epoxy User Manual

Page of 18
Cyanide Electrode 
 
Instruction Manual
 
 
10
Using Table 3, the maximum ratio is: 
 
       [Br
-1
    ———— = 5X10
3
 
      [CN
-1
  
      [Br
-1
] = 5X10
3
 [CN-1]                   
                = (5X10
3
) (1X10
-5
 
      [Br
-1
] = 5X10
-2
M = maximum bromide concentration for no interference 
 
 
Complexation 
 
Total concentration, Ct, consists of free ions, Cf, and complexed or bound ions, Cc, in solutions: 
 
                          Ct = Cf + Cc 
 
Since the electrode only responds to free ions, any complexing agent in the solution reduces the 
measured concentration of ions. 
Hydrogen ions and many metal ions form complexes with cyanide ions. The presence of any 
complexing agent lowers the measured concentration. Since the electrode measures only free 
cyanide ions, use of 10M NaOH (ISA) is essential, since it eliminates complexation by hydrogen. 
 
EDTA can be used to break up cyanide complexes formed with many metal ions, including 
cadmium, copper, nickel, and zinc. To a sample whose cyanide concentration is not more than 10 
ppm, or about 1X10
-3
M, add acetic acid to make the sample solution's pH 4. Add EDTA (disodium) 
to about 0.02M (or about 0.76 grams Na
2
 EDTA per 100 ml sample).  In a hood, heat the mixture to 
about 50
o
C for about five minutes to speed up the decomplexation. After cooling the solution, add 
10M NaOH (ISA) until the pH 13. The cyanide remains free long enough for concentration 
measurements to be made, since EDTA complexes of the metals break up very slowly. 
 
This method will not work for silver, mercury, gold, or cobalt, since they will bind the cyanide too 
strongly. 
 
Temperature Influences 
 
Samples and standards should be within ±1
o
C of each other, since electrode potentials are 
influenced by changes in temperature. A 1
o
C difference in temperature results in a 2% error at the 
1.0X10
-3
M concentration level. Because of the solubility equilibrium on which the electrode 
depends, the absolute potential of the reference electrode (or reference portion of the combination 
electrode) changes slowly with temperature. The slope of the electrode, as indicated by the factor 
"S" in the Nernst equation, also varies with temperature. Table 4 gives values for the "S" factor in 
the Nernst equation for the cyanide ion.