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Meeting 7 Principles: sedimentation of Ag(I) reaction Analite + Titrant precipitation AgNO3 ARGENTOMETRy Diffuculties of titration: Hard to find the suitable indicators In some cases (mainly in dilute solution ), reaction rate usually slow The composition of sediment sometimes can not be determined • Benefit : Determine Cl-, F-, Br• Reaction: NaCl (aq) + AgNO3 (aq) AgCl (s) + NaNO3 (aq) white Solubility constant (KSp) AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = [Ag+ ] [Cl-] ----- equillibrium Ksp > [Ag+ ] [Cl-] ----- become sediment Indicators in Argentometric titration a. Formation of colorfull sediment: (Mohr methods: pH 6-10) b. Formation of colorfull complexs (Volhard methods, acid pH) c. Using adsoprtion indicators (Fajans Methods Mohr Methods: Indicator chromates • Ag+ + Cl- ==== AgCl (white crystal) • Ag + + CrO4= === AgCrO4 (red crystal surrounding AgCl surface) Volhard methods: Indicator: Fe (III) Ag+ + Cl- ==== Ag+ + SCNFe3+ + SCN- AgCl (white crystal) AgSCN(s) FeSCN2+(aq) End Point : white crystal in reddish solution Fajans Methods: Indicator fluororescense (Fl) Ag+ + ClAgCl(s) (AgCl).Ag-+ Primary layer X- secondair layer HFl (AgCl).Ag+ H+ + Fl- Cl- exceed Fl- E.P : (Pink precipitate) Penyelesaian : Na+(aq) + Cl-(aq) + Ag+(aq) + NO3- AgCl(s) + Na+(aq) + NO3-(aq) a. Pada keadaan awal : pCl- = -log [Cl-] = -log 10-1 = 1,00 [Ag+] = 0 b. Penambahan 10,0 mL AgNO3 jumlah mmol NaCl setelah penambahan AgNO3 [Cl-] = ———————————————————————— volume campuran jumlah mmol NaCl awal – jumlah AgNO3 yg ditambahkan [Cl-] = ————————————————————————————— volume campuran (50,0 x 0,10) – (10,0 x 0,1) [Cl-] = ——————————————— = 0,067 M 50,0 + 10,0 pCl = 1,17 c. Penambahan 49,9 mL AgNO3 (50,0 x 0,10) – (49,9 x 0,1) [Cl-] = ——————————————— = 1,0 x 10-4 M 50,0 + 49,9 pCl = 1,17 d. Pada penambahan 50,00 mL AgCl(s) Ag +(aq) + Cl-(aq) [Ag+][Cl-] = Ksp , pAg + pCl = 10 [Ag+] = [Cl-] [Cl-]2 = 1x 10-10 [Cl-] = 1 x 10-5 pCl- = 5,00 e. Penambahan 60,0 mL (60,0 x 0,10) – (50 x 0,1) [ Ag+] = ——————————————— 60,0 + 50,0 pAg = 2,04 = 9,1 x 10-3 M KURVA TITRASI Metode Mohr : Ag+(aq) + Cl- (aq) Ksp = 1 x 10-10 2Ag (aq) + CrO4 (aq) Ksp = 2 x10-12 AgCl(s) Ag2CrO4(s) Na+(aq) + + Cl-(aq) + Ag+(aq) 2+ NO3- AgCl(s) + Na+(aq) + NO3-(aq) Berapa konsentrasi K2CrO4 yang diperlukan pada titik eakhir titrasi? Konsentrasi K2CrO4 yang diperlukan pada titik akhir titrasi: Kelarutan Ag2CrO4 = 8,4 x 10-5 mol/L Kelarutan AgCl = 1 x 10-5 mol/L Pada titik ekivalen pAg = pCl = 5,0 [Ag2+]2 [CrO42-] = 2 x 10-12 2 x 10-12 [CrO42-] = ————— = 0,02M (1 x 10-5 )2