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- ====

AgCl (white crystal)

Ag+ + SCN- AgSCN(s)

Fe3+ + SCN- FeSCN2+(aq)

End Point : white crystal in reddish solution

Fajans Methods: Indicator fluororescense (Fl)
Ag+ + Cl- AgCl(s)

(AgCl).Ag-+ X-
Primary
layer secondair Cl- exceed
layer
HFl H+ + Fl- E.P :

(AgCl).Ag+ Fl- (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+] = ——————————————— = 9,1 x 10-3 M

60,0 + 50,0

pAg = 2,04
KURVA TITRASI
 Metode Mohr :

Ag+(aq) + Cl- (aq) AgCl(s)

Ksp = 1 x 10-10
2Ag (aq) + CrO4 (aq) Ag2CrO4(s)
+ NO3-  AgCl(s) + Na+(aq) + NO3-(aq)
Na+(aq) ++ Cl-(aq) + Ag+(aq) 2-

Ksp = 2 x10-12

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
• Can used other silver salt
• Which one is simpler? Acid-based or
argentometric?
• pAg ~ pH?
• Applications: ppm, how can we identify?
• Other indicator for fajans? Eosin