Professional Documents
Culture Documents
Cl Ag
AgCl
K
o
AgCl K
i
Cl AgCl
AgCl
K
f
2
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
4.) Filterability:
(i) Want product to be large enough to collect on filter:
Doesnt clog filter
Doesnt pass through filter
(ii) Best Case: Pure Crystals
(iii) Worst Case: Colloidal suspension
Difficult to filter due to small size
Tend to stay in solution indefinitely suspended by Brownian motion
- usually 1-100 nm in size
Whether crystals or colloids are obtained depends on conditions used in the precipitation
Brownian Motion
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
5.) Process of Crystal Growth:
(i) Two Phases in Crystal Growth
Nucleation molecules in solution come together randomly and form
small aggregates
Particle growth addition of molecules to a nucleus to form a crystal
Crystal Growth
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
5.) Process of Crystal Growth:
(ii) Nucleation and Particle growth always compete for
molecules/ions being precipitated.
If nucleation is faster than particle growth:
- a large number of small aggregates occur giving
colloidal suspensions
If particle growth is faster than nucleation:
- only a few, large particles form giving pure
crystals
Colloidal suspension
Crystal formation
Want to
Convert to
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
5.) Process of Crystal Growth:
(iii) Methods for Maximizing Crystal Growth (avoid colloids)
Increase temperature of solution
- increase amount of solute that can be in solution at equilibrium
Add precipitating reagent slowly while vigorously mixing solution
- avoids local high concentrations of solution
Keep volume of solution large
- keep concentration of analyte and precipitating reagent low
Precipitate Ionic compounds in presence of electrolyte (0.1 M
HNO
3
)
- overcome charge repulsion and promotes particle growth
Control solubility of solute through chemical means
- by adjusting pH
- adding complexing agents
- example: precipitation of Ca
2+
with C
2
O
4
2-
C
2
O
4
2-
+ H
+
HC
2
O
4
-
Ca
2+
+ C
2
O
4
2-
CaC
2
O
4
(s)
K
sp
Note: As pH ([H
+
])
changes, the solubility
of CaC
2
O
4
changes
Avoid Colloidal
Particle
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Particle Size
Ions in solution = 10
-3
cm
Coloidal particle = 10
-7
10
-4
cm
Crystaline particle = 10
-4
cm
A solutes relative supersaturation, RSS can be expressed as:
RSS = (Q-S)/S
With,
Q = the solutes actual concentration
S = the solutess expected concentration at equilibrium
Q-S = a measure of the solutes supersaturation when precipitation
begins
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
A solutes relative supersaturation, RSS can be expressed as:
RSS = (Q-S)/S
With,
Q = the solutes actual concentration
S = the solutess expected concentration at equilibrium
Q-S = a measure of the solutes supersaturation when precipitation
begins
Large number of RSS = solution is highly supersaturated, unstable solution,
high rates of nucleation, small particles production (coloidal particles),
while
Small RSS = precipitation is more likely to occur by particle growth than
by nucleation (crystaline particles)
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Ukuran koloid dapat ditingkatkan melalui proses :
pemanasan, pengadukan dan penambahan elektrolit
Proses pembentukan partikel berukuran kecil menjadi partikel yang
lebih besar (merubah koloid sehingga dapat disaring) disebut koagulasi
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Coagulation formation
By increasing the concentration of the ions
responsible for secondary adsorption layer
add an inert electrolyte, which increase the concentration of ions in the secondary
adsoprtion layer. More ions available, the thickness of the secondary absorption
layer is decrease. Particles of precipitate may now approach one to another more
closely, allowing the precipitate to coagulate.
By heating the solution
As the increasing of temperature, the number of ions in the primary adsorption
layer decrease, lowering the precipitates surface charge. In addition, increasing
the particles kinetic energy may be sufficient to overcome the electrostatic
repulsion preventing coagulation at lower temperatures
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
6.) Crystal Impurities:
(i) Impurities are undesirable (known as co-precipitation)
Change the chemical composition of the precipitate
Creates errors in gravimetric analysis
(iii) Types of Impurities
Adsorption, Occlusion, Inclusion
Adsorbed to
crystal
surface
Absorbed or
trapped within
crystal pockets
Impurity placed in
crystal instead of
analyte
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
6.) Crystal Impurities:
(iii) Ways to Minimize Impurities
Maximize crystal growth
large pure crystals decrease occlusions and adsorbed impurities
Digestion: allowing precipitate to stand in mother liquor
(precipitating solution), usually while being heated
- promotes removal of impurities from crystal
- increases size of crystals
Wash precipitate, re-dissolve in fresh solvent and re-precipitate
- helps decrease all types of impurities
Add a masking agent to solution
- keeps impurities from precipitating, but not analyte
Mg
2+
+ CPCH Solid
product
Mn
2+
+ 6CN
-
Mn(CN)
6
4-
Masking
agent
precipitant
Color Impurity
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
7.) Final Preparation of Precipitates:
(vi) Washing Precipitates
Precipitates from ionic compounds
- need electrolyte in wash solution
- keep precipitate from breaking up and redissolving (peptization)
Electrolyte should be volatile
- removed by drying
- HNO
3
, HCl, NH
4
, NO
3
, etc.
Illustration:
- AgCl(s) should not be washed with H
2
O, instead wash with dilute
HNO
3
(vii) Drying/Igniting Precipitates
Many precipitates contain varying amounts of H
2
O
- adsorbed from the air (i.e. hygroscopic)
Precipitates are dried for accurate, stable mass measurements
Precipitates are also ignited to convert to a given chemical form
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Representative Gravimetric Analyses
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Berapa jumlah sampel yang mengandung 12 %
klorin (Cl) harus diambil untuk analisis jika
kimiawan tersebut ingin memperoleh suatu
endapan AgCl yang beratnya 0,5 g?
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Penyelesaian:
Reaksi pengendapannya adalah :
Ag
+
+ Cl
-
AgCl(s)
dan mol Cl
-
= mol AgCl
Jika w = gram sampel, maka:
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
EXAMPLE
An ore containing magnetite, Fe3O4, was
anlyzed by dissolving a 1.5419 g sample in
concentrated HCl, giving a mixture of Fe
2+
and
Fe3+. After adding HNO3 to oxidize any Fe2+
to Fe3+, the resulting solution was diluted with
water and the Fe3+ precipitated as Fe(OH)3
by adding NH3. After filtering and rinsing, the
residue was ignited, giving 0.8525 g of pure
Fe2O3. Calculate the % w/w Fe3O4 in the
sample!
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
EXAMPLE
An ore yang mengandung magnetite, Fe
3
O
4
, dianalisis
dengan melarutkan 1,5419 g sampel dalam HCl pekat,
menghasilkan campuran Fe
2+
dan Fe
3+
. Selanjutnya,
Fe
2+
dioksidasi menjadi Fe
3+
, dengan menambahkan
HNO
3
. Hasilnya dilarutkannya dalam air dan dengan
menambahkan NH
3
, Fe
3+
diendapkan sebagai Fe(OH)
3
.
Setelah penyaringan dan pencucian selesai, didapatkan
residu sebesar 0,8525 g Fe
2
O
3
murni.
Hitunglah % (w/w) Fe
3
O
4
dalam sampel!
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Penyelesaian,
Kasus ini merupakan salah satu contoh analysis langsung karena besi dalam analit,
Fe3O4 merupakan bagian dari endapan yang diisolasi, Fe2O3. Dengan, mengacu
pada persamaan reaksi sempurna, maka:
3 mol Fe
3
O
4
= 2 x mol Fe
2
O
3
Menggunakan rumus berat, dengan mengkonversikan mol ke gram didapat:
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Penyelesaian,
3 mol Fe
3
O
4
= 2 x mol Fe
2
O
3
Menggunakan rumus berat, dengan mengkonversikan mol ke gram didapat:
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Penyelesaian,
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Volatilisation Gravimetry
The changes in a samples mass is monitored as an increasing of temperature
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Dry substance (ds) is the mass portion of solid matter in sample which
obtained by the drying process, after the water has been removed and it
is given in percentage (%).
Dry substance (ds)
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Dry substance (ds)
8 g homogeneous samples
(duplicates)
Placed on the weighing dish and
Initial weight was noted
Infrared heater was
adjusted;
output weight was noted
m
a
= initial weight [g]
m
b
= output weight [g]
a
b
m
m
ds
% 100