ARGENTOMETRY

argentometryisatypeoftitration

involvingthesilver(I)ion.Typically,itis
usedtodeterminetheamountofchloride
presentinasample
Accordingtotheindicatorused,three
methodscanbedescribed:
Mohr'smethod
Fajansmethod
VolhardMethod

i) Guidance in precipitation titration

calculation
FindVe(volumeoftitrantatequivalence
point)
Findy-axisvalues:
-Atbeginning
-BeforeVe
-AtVe
-AfterVe

Example:Forthetitrationof50.0mLof
0.0500MClwith0.100MAg+.The
reactionis:
Ag+(aq)+Cl(aq)AgCl(s)Ksp=1.81010
FindpAgandpClofAg+solutionadded
(a)0mL(b)10.0mL(c)25.0mL(d)35.0
mL

Solution

0.0500 mmol Cl 1 mmol Ag

Ve 50.0 mL Cl

1 mL Cl
1 mmol Cl
1 mL Ag

25
.
0
mL
Ag
0.100 mmol Ag

(a) 0mLAg+added(Atbeginning)
[Ag+]=0,pAgcannotbecalculated.
[Cl]=0.0500,pCl=1.30
10mLAg+added(BeforeVe)
mmol Cl Left original mmol Cl precipitat ed mmol Cl
0.0500 mmol Cl
0.100 mmol Ag 1 mmol Cl

10.0 mL Ag

50.0 mL Cl

1 mL Cl
1 mL Ag
1 mmol Ag

1.50 mmol Cl
Vtotal 50.0 mL 10.0 mL 60.0 mL

1.5 mmol Cl
[Cl ]
2.50 10 2 M
60.0 mL
K sp
1.8 10 10

[ Ag ]

7.2 10 9 M

2
[Cl ] 2.50 10
pCl 1.60
pAg 8.14

(c) 25mLAg+added(AtVe)
AgCl(s) Ag+(aq) + Cl(aq)
s = [Ag+]=[Cl]
Ksp = 1.81010 = s2
[Ag+]=[Cl]=1.35x105
pAg = 4.89
pCl = 4.89

Ksp = 1.81010

35mLAg+added(AfterVe)
mmol Ag Left original mmol Ag precipitat ed mmol Ag withVe of Ag

0.100 mmol Ag
0.100 mmol Ag

25.0 mL Ag

35.0 mL Ag

1 mL Ag
1 mL Ag

1.00 mmol Ag
Vtotal 50.0 mL 35.0 mL 85.0 mL

1.00 mmol Ag
[ Ag ]
1.18 10 2 M
85.0 mL
K sp
1.8 10 10

8
[Cl ]

1
.
53

10
M

2
[ Ag ] 1.18 10
pCl 7.82

pAg 1.93

ii) Construct a titration curve

Example:Titrationof50.0mLof0.0500
MClwith0.100MAg+
pCl

pAg

dy/dx

d2y/dx2

iii) Diluting effect of the titration curves

25.00mL0.1000MI
titratedwith0.05000M
Ag+
25.00mL0.01000MI
titratedwith0.005000
MAg+
25.00mL0.001000MI
titratedwith0.0005000
MAg+

v) Ksp effect of the titration curves

25.00mL0.1000M
halide(X)
titratedwith0.05000M
Ag+

The effect of Reaction Completeness on Titration Curves

Figure 13-5 Effect of reaction completeness on precipitation curves . For each curve ,
50.00 mL of a 0.0500M solution of the anion was titrated with 0.1000 M AgNO3 . Note that
smaller values of Ksp give much sharper breaks at the end point

Example:A25.00mLsolutioncontainingBrand
Clwastitratedwith0.03333MAgNO3.
Ksp(AgBr)=5x1013,Ksp(AgCl)=1.8x1010.
(a)Whichanalyteisprecipitatedfirst?
(b)Thefirstendpointwasobservedat15.55mL.
Findtheconcentrationofthefirstthat
precipitated(BrorCl?).
(c)Thesecondendpointwasobservedat42.23mL.
Findtheconcentrationofthesecondthat
precipitated(BrorCl?).

Solution:
(a)
Ag+(aq)+Br(aq)AgBr(s) K=1/Ksp(AgBr)=2x1012
Ag+(aq)+Cl(aq)AgCl(s) K=1/Ksp(AgCl)=5.6x109
Ans:AgBrprecipitatedfirst

15.55
mL
Ag
1
L
Ag
0.3333
mol
Ag
(b)

1
1000 mLAg
1 L Ag

1 mol Br
1
1000 mL

0.02073
M
Br
1 mol Ag 25 mL
1L

(c) (42.23 - 15.55) mL Ag

1 L Ag
0.3333 mol Ag

1000 mLAg
1 L Ag

1 mol Cl
1
1000 mL

0.03557
M
Cl
1 mol Ag 25 mL
1L

Figure : Titration curves for

50.00mL of a solution 0.0800 M in
Cl- and 0.0500 M in I- or Br-

Volhard method:Acoloredcomplex(back
titration).AnalysingClforexample:
Step1: AddingexcessAg+intosample
Ag++ClAgCl(s)+leftAg+
Step2: RemovingAgCl(s)byfiltration/washing
Step3: Adding Fe3+intofiltrate(i.e.,theleftAg+)
Step4: TitratingtheleftAg+bySCN:
Ag++SCNAgSCN(s)
Step5: Endpointdeterminationbyredcolored
Fe(SCN)2+complex.(whenallAg+hasbeen
consumed,SCNreactswithFe3+)
SCN+Fe3+Fe(SCN)2+(aq)
Total mol Ag+ = (mol Ag+ consumed by Cl)
+ (mol Ag+ consumed by
SCN)

AgCl(s)+SCNAgSCN(s)+Cl-

Mohr Method:Acoloredprecipitateformed
byAg+withanion,otherthananalyte,once
theVereached.AnalysingClandadding
CrO42forexample:
PrecipitatingCl:
Ag++ClAgCl(s) Ksp=1.8x1010
Endpointdeterminationbyredcolored
precipitate,Ag2CrO4(s):
2Ag++CrO42Ag2CrO4(s) Ksp=1.2x10
12

3) Fajans Method:Anadsorbed/colored
indicator.TitratingClandadding
dichlorofluorosceinforexample:
BeforeVe
AgCl(s) Cl
(Clexcess)
1st
Greenish
layer
yellow
solution
AgCl(s) Ag+ In
AfterVe
pink
(Ag+excess)
1st
layer

Daridataexperimendiperolehkonsentrasi

Fe(SCN)2+ketikamembentukwarna
adalah6,4x10-6M.jikatitrasi50mLAg+
dengan0,1MKSCN,berapakonsentrasi
Fe3+yangdigunakanuntukmeminimalkan
kesalahantitrasitingkatkesalahanNol)?
(KspAgSCN=1,1x10-12danKfFe
(SCN)2+=1,4102)