Page 88 - Pharmaceutical Analytical Chemistry II - Pharm D Clinical- 07-PA202
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COO-  Br-, I-, SCN- with Ag+  7)
               Cl C Cl
                                                                         Pink → reddish-violet
              HO O OH                                                    (Best in acetic acid
                                  +                                      solution useful down
                                                                         to pH 1-2).
Tetrabromofluorescein (eosin)
                                                                         Red → purple
                                     COO-                                (Accurate if
         Br C Br                                                         (NH4)2CO3 is added)
                                                                         Orange red → blue-
HO O OH                                                                  red (pH 4-7)
                    +

           Br Br

Dichloro-tetraiodo-fluorescein (Rose I- in presence of Cl-

Bengal)                                          with Ag+

Di-iodo-dimethyl-fluorescein                     I- with Ag+

Determination of mixtures

a) Chloride-iodide mixture:

          By direct titration using Fajans method, fluorscein indicator fortotal halide then the iodide is determined using eosin.

b) Bromide-iodide mixture:

          This is similar to chloride iodide mixture, total halide with eosin or fluorescein then for I- use diiododimethyl
fluorescein.

c) Chloride-cyanide, bromide-cyanide or iodide-cyanide mixtures:

          Such mixtures are analyzed using a combination of Liebig and Volhard methods. Liebig method determines the cyanide
ion while the total is determined by Volhard method.

                                                             2 CN- + Ag+ ↔ [Ag(CN)2]-
                                                        [Ag(CN)2]- + Ag+ ↔ Ag-Ag(CN)2

                                                                           References

1- Principles of Instrumental Analysis, Douglas A. Skoog, F. James Holler, Stanley
R.Crouch, 7thedition,2007.
2- Quantitative Chemical Analysis, Daniel C.Harris, 9th edition, W.H. Free man and
Company, NY,USA,2015.

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