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ARGENTOMETRI

ARGENTOMETRI

Definisi : Analisis titrimetri dengan


baku AgNO3
Dasar Reaksi : Reaksi Pengendapan
dengan ion Ag+ Reaksi
presipitasi
Perlu pemahaman hasil kali kelarutan
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Precipitation Reactions
Precipitation is the formation of a solid in
a solution
solid formed is called the precipitate
A precipitation reaction occurs when
water solutions of two different ionic
compounds are mixed and an insoluble
solid separates out of solution.
Cl- solutionPrecipitating agent precipitate

Eg
KCl
KNO3

AgNO3

AgCl +

Solubility of precipitate
Solubility of a compound = concentrations
of a soluble species at equilibrium with its
insoluble form.
If the compound is sparingly soluble, it will
produce cation & anion.
Eg AgCl slightly dissolved in water. So AgCl
has a specific solubility, s = solid phase aq
= aqueous phase
AgCl (s)

Ag+ (aq)+ Cl- (aq)

The equilibrium constant for the reaction is


known as solubility product constant.
Ksp (AgCl) = [Ag+][Cl-]
Concentration of any solid (AgCl) is
constant and is combined in the
equilibrium constant to give Ksp
Solubility product constants are used to
describe saturated solutions of ionic
compounds of relatively low solubility.
A saturated solution is in a state of
dynamic equilibrium between the
dissolved, dissociated, ionic compound
and the undissolved solid.

Precipitation titration
Precipitation titration is a titration method
based on the formation of precipitate,
which is slightly soluble
Titration with precipitating agents is useful
for determining certain analytes, provided
the equilibrium will take place rapidly and
suitable means of detecting equivalent
points is available
Titration curve plot of the changes in
analyte concentration againts titrant
volumes.

Consider titration of Cl- with a standard


solution of AgNO3.
Titration curve prepared by plotting pCl
(-log[Cl-]) againts the volume of AgNO3
in a manner similar to acidbase
titration.
Before titration started only have Cl-.
pCl = - log[Cl-]
Titration proceed part of Cl- is removed
from solution by precipitation as AgCl.
pCl = -log [remaining Cl-]

At equivalence point - we have


solution a saturated solution of AgCl.
[Cl-]= Ksp
Excess AgNO3 added excess Ag+.
[Cl-] is determine from the
concentration of Ag+ and Ksp.
[Cl-] = Ksp/[Ag+]

Example 1
Calculate pCl for the titration of
100.0 ml 0.100 M NaCl with 0.100 M
AgNO3 for the addition of 0.0, 20.0,
99.0, 99.5, 100.0 and 110.0 ml
AgNO3. Ksp AgCl is 1.0 x10-10

solution
a) Addition of 0.0 ml Ag+
[Cl-] = 0.100 M
pCl = -log [Cl-]
= -log 0.100
=1

b) Addition of 20.0 ml Ag+


Initial mmol Cl- = 100.0 ml x 0.100 M =
10.0 mmol
mmol added Ag+= 20.0 ml x 0.100 M =
2.0 mmol
mmol Cl- left
= 8.0
mmol
[Cl-] left =
8.0
= 0.0667 M
(100+20) ml
pCl = -log [Cl-]
= -log 0.0667

c) Addition of 99.0 ml Ag
Initial mmol Cl- = 100.0 ml x 0.100 M =
10.0 mmol
mmol added Ag+= 99.0 ml x 0.100 M =
9.9 mmol
mmol Cl- left
= 0.1
mmol
[Cl-] left =
0.1
= 5.01 x10-4 M
(100+99)ml
pCl = -log [Cl-]
= -log 5.01 x10-4

d) Addition of 100.0 ml
Initial mmol Cl- = 100.0 ml x 0.100 M =
10.0 mmol
mmol added Ag+= 100.0 ml x 0.100 M=
10.0 mmol
Equivalence point is reached. The solution contain
saturated AgCl solution

Ksp = [Ag+][Cl-] = 1.0 x10-10


[Cl-] = Ksp = 1.0 x10-10
= 1.0 x 10-5
-5

Addition of 100.5 ml Ag+


Initial mmol Cl = 100.0 ml x 0.100 M =
10.0 mmol
mmol added Ag+= 100.5 ml x 0.100 M
=10.05 mmol
mmol Ag+ excess =
= 0.05
mmol
[Ag+] excess = 0.05/200.5 ml = 2.5 x 10-4
M
Ksp = [Ag+][Cl-] = 1.0 x10-10
[Cl-] = Ksp
= 1.0 x10-10

= 4.0 x

Titration curve for the titration of 100.0 mL of 0.100 M NaCl with


0.100 M AgNO3

40

80

12
0

16
0

20
0

Titration Curves for Argentometric Methods


Plots of titration curves are normally sigmoidal curves
consisting of pAg (or pAnalyte) versus volume of AgNO3 solution
added.
Example: Titration of chloride with silver.

The points on the curve can be calculated, given the analyte


concentration, AgNO3 concentration and the appropriate Ksp.

soal
Calculate the titration curve for the
titration of 50.0 mL of 0.0500 M NaCl
with 0.100 M AgNO3 as pCl versus V
AgNO3

HUBUNGAN MOL VS GRAEK

1 Graek ~ 1 mol ion Ag+


Cl + Ag+ AgCl

1 mol halida ~ 1 Graek

CN + Ag+ AgCN
CN+ AgCN Ag(CN)2

2CN+ Ag+ Ag(CN)2

1 mol CN ~ Graek

KIMIA ANALISIS by Wahyu

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Indikator : Ion yang dapat


mengendap dengan ion larutan
baku, memberikan warna yang
mudah larut dibanding ion yang
dianalisis.
Contoh : ~ CrO42- pada titrasi halida
dg Ag+
~ Fe3+ pada titrasi Ag+ dg CNS
KIMIA ANALISIS by Wahyu

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Observations About Argentometric Titrations


High reagent concentrations give sharper, more
dramatic equivalence point changes in pAg and better endpoints.
The smaller the Ksp, the more complete the precipitation reaction and
the sharper the equivalence region changes.
Both Ksp and the reagent concentrations affect the choice and use of
an endpoint indicator.

Endpoint Indicators for Argentometric Titrations


Indicators for argentometric titrations are selected to produce
a color change at or near the equivalence point.
Normally the indicator is selected to react with the added
titrating agent, not the analyte. If A is the analyte, R the titrating
agent and In is the indicator.
A + R
In(color) + R

AR(s)
InR(new color)

To make the indicator change color, excess R must be added.


Obviously, the smaller the excess added to cause the color change, the
smaller the endpoint error.
This means that the indicator should give large color changes at very
low concentrations.

BEBERAPA METODA
ARGENTOMETRI
A. Metode Mohr
Metode titrasi langsung
Suasana larutan netral atau agak
alkalis
Cocok untuk penetapan Cl
Indikator kalium kromat (K2CrO4)
Titik akhir titrasi : terjadi endapan
merah Ag2CrO4
KIMIA ANALISIS by Wahyu

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Reaksi :
Cl + Ag+ AgCl putih
10-10

Ksp AgCl = 1,56 x

CrO42- + 2Ag+ Ag2CrO4 merah Ksp Ag2CrO4 = 9


Catatan
:
-12
x 10
d Suasana tidak boleh asam, sebab dalam
suasana asam CrO42- HCrO4- Cr2O72-,
akibatnya CrO42- berkurang endapan
Ag2CrO4 lambat terbentuk kesalahan
besar
d Jika suasana alkalis (pH>9), ion Ag+ akan
membentuk endapan hitam
KIMIA ANALISIS by Wahyu
Ag+ + OH AgOH
( Ag2O + H20) 22

Ksp AgCl > Ag2CrO4 , tetapi kelarutan AgCl <


Ag2CrO4 karena AgCl biner, sedangkan Ag2CrO4
terner
Ksp AgOH = 2,6 x 10-8
Kalau pada titik akhir [Ag+] = 2,2 x 10-5
agar AgOH mengendap [Ag+] [OH] >
2,6 x 10-8 jadi
[OH] > 1,2 x 10-3
Jadi, pOH < 2,9 pH > 11,1
jika pH < 9, Ag+ tidak mengendap
KIMIA ANALISIS by Wahyu

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B. Metoda Volhard
Metoda titrasi tidak langsung
Suasana harus asam (pH < 3, 0,51,5 N Asam)
Pengasaman selalu digunakan
HNO3
Indikator ion Fe3+, titik akhir warna
merah
Reaksi
:
Titran

Br
+ Ag+1.AgNO
AgBr 3berlebih
putih
tertentu/ekses
(V1N1), titran 2.
+

Ag + SCN AgSCN putih Ksp AgSCN =


NH
SCN
-12 (V2N2)
4
1,2 x 10
3+

KIMIA ANALISIS by Wahyu

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pH harus rendah, krn Fe3+ dapat


mengendap pada pH > 3 Fe(OH)3.
Akibatnya titik akhir sukar teramati
Pd penetapan kadar Cl, endapan AgCl
perlu dipisahkan sebelum kelebihan
baku Ag+ dititrasi kembali dengan
NH4SCN, sebab kelarutan AgCl > AgSCN
AgCl + SCN AgSCN + Cl
Pada titrasi ion Br, endapan AgBr
tidak perlu dipisahkan, karena
kelarutan AgBr < AgSCN
Br
Ksp AgBr
=

KIMIA ANALISIS by Wahyu


= 0,66

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Pada titrasi I, endapan AgI juga tidak


perlu dipisahkan karena kelarutan AgI
<<< AgSCN
Tetapi penambahan indikator Fe3+
ditambahkan setelah semua ion I
diendapkan, agar tidak terjadi reaksi :
2 Fe3+ + 2 I 2 Fe2+ + I2

C. Metoda Fajans
Metoda ini mirip pada metoda Mohr,
tetapi indikator yang digunakan berupa
indikator adsorbsi : eosin
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AgCl ppt.

End-Point Detection
1.) Precipitation Titration

Fajans titration
- Uses an adsorption indicator

Precipitate surface is initially


negatively charged due to excess
ClAgCl ppt.

After equivalence point (end point),


have excess Ag+ so surface is now
positively charged.

Anionic dye is attracted to positive charged


surface. Adsorption of dye causes color
change

End-Point Detection
1.) Precipitation Titration

Fajans titration
Anionic dyes
- Maximize surface area higher binding stronger color change
- small particle size low concentration
- most use appropriate pH to maintain negative charge

Changes from greenish yellow to pink

Sharper color transition, binds to tightly to Cl-

D. Metoda Liebig

Titrasi langsung
Prinsip reaksi kompleks
Tanpa indikator, harus bebas NH3
Untuk penetapan kadar ion Sianida

Komentar :
Reaksi :
Ag+ + CN AgCN
AgCN + CN Ag(CN)2
Ag(CN)2 + Ag+ Ag[Ag(CN)2] Sebagai
titik akhir
Harus bebas NH3, sebab NH3 membentuk
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kompleks dengan Ag+ Ag(NH3)2+

Titration Curve Shape

Titration Curve Shape


Shape of Titration Curve
1.) Equivalence point is the steepest point of the curve.

Point of maximum slope inflection point second derivative is zero

Steepest slope :
Inflection po int :

dy
dx
d2y
dx 2

reaches greatest value


0

Titration Curve Shape


Shape of Titration Curve
2.) Affect of Ksp on Titration Curve.

Lowest solubility gives steepest change at equivalence point

Magnitude of concentration
change and ease of
identifying equivalence
point increases with Ksp

Titration of Mixtures
Endpoints are characterized by
inflection points where a curvature
changes sign.
In mixtures leading to two
precipitates, two inflection points are
observed.
The lowest Ksp solid finishes its reaction
by precipitating first. Thus the first
inflection point.
The more soluble solid precipitates last.

Titration of a Mixture
The less soluble product forms first
If there is sufficient difference in
solubility of products
First precipitation is nearly complete
before the second one begins
Separation by precipitation

Coprecipitation
Alters the expected endpoints

Titration of a Mixture
Example

Titrations
End-Point Detection
2.) Typical Applications

Also indicates potential sources of interference


- other ions/analytes may be present in sample

Berapa % kadar kadar NaCl dalam


air laut jika 25,00 ml air laut setara
dengan 12,50 ml AgNO3 0,1000 N?
0,4004 gram sampel yang
mengandung kalium bromida,
dilarutkan dengan 100 mL air,
kemudian dititrasi dengan AgNO3
0,1234 N menggunakan indikator
kalium kromat. Ternyata
dibutuhkan 20,04 mL AgNO3
0,1234 N untuk mencapai titik
akhir titrasi. Berapa % kadar KBr
KIMIA ANALISIS by Wahyu

402,6 mg sampel yang


mengandung KBr, dilarutkan dalam
campuran 40 mL air dan 5 mL asam
nitrat pekat, dan ditambahkan
25,00 mL AgNO3 0,1012 N.
Kemudian dititrasi dengan
ammonium tiosianat 0,1007 N
menggunakan indikator besi (III)
ammonium sulfat. Ternyata
dibutuhkan 16,17 mL ammonium
tiosianat 0,1007 N. Hitung kadar
KBr dalam sampel !
KIMIA ANALISIS by Wahyu

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