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Analisis Gravimetri

Universitas Islam Negeri Sunan Kalijaga


Yogyakarta
ANALISIS GRAVIMETRI
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
A Gravimetric analysis is based upon the
measurement of the weight of a substance
that has a KNOWN composition AND IS
chemically related to the analyte.
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Introduction

1.) Gravimetric Analysis:
(i) A technique in which the amount of an analyte in a sample is
determined by converting the analyte to some product
Mass of product can be easily measured

(ii) Analyte: the compound or species to be analyzed in a sample

(iii) Overall, gravimetry sounds simple.
Advantages - when done correctly is highly accurate (most
accurate of all time); requires minimal equipment

Disadvantage - requires skilled operator, slow.


Convert analyte into a solid, filter, weigh, calculate via a mole map


Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Introduction

1.) Gravimetric Analysis:
(iii) Example:

Determination of lead (Pb
+2
) in water

Pb
+2
+ 2Cl
-
PbCl
2
(s)

By adding excess Cl
-
to the sample, essentially all of the
Pb
+2
will precipitate as PbCl
2
.

Mass of PbCl
2
is then determined.
- used to calculate the amount of Pb
+2
in original
solution
Reagent Analyte Solid Product
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Accurate and precise.

Possible sources of errors can be checked.

It is an ABSOLUTE method.

Relatively inexpensive
Gravimetric Analysis
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Type of Gravimetric Analysis
Precipitation methods.

Volatilisation methods.

Electrogravimetry.

Particulate gravimetry.
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Type of Gravimetric Analysis
Precipitation methods : a gravimetric method in which the signal is the
mass of the precipitate ex. Determination of Cl
-
by precipitating AgCl

Volatilisation methods : a gravimetric method in which the loss of
volatile species gives rise to the signal ex. Determination of moisture
content of food, thermal energy vaporizes the H
2
O. The amount of
carbon in an aorganic compound by converting C tp CO
2
.

Electrogravimetry : a gravimetric method in which the s signal is the
mass of an electrodeposit on the cathode or anode in an electrochemical
cell ex. The electrodeposition of Cu on a Pt cathode

Particulate gravimetry : a gravimetric method in which the mass of a
particulate analyte is determined following is separation from its matrix
ex. The determination of suspended solids .
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Conditions:
1. Must be a stoichiometric reaction.
2. A stable product; no oxidation, dehydration
or gelatinous precipitates.
3. Must avoid side reactions which result in
co-precipitates.
Gravimetric Analysis
The stoichiometry indicates how the precipitate relates to the analyte
Moles Pb
2+
= moles PbO
2
(precipitation)
g suspended solid = filters final mass filters initial mass (suspended solid)
g H2O = samples initial mass samples final mass (moisture content)
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
In precipitation methods, the species to
be determined is precipitated by a reagent
that yields a sparingly soluble product that
has a known composition or can be
converted to such a substance.
Precipitation gravimetry is based on the formation of an insoluble
compound following the addition of a precipitating reagent, or precipitant,
to a solution of the analyte
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Requirement of Gravimetric Analysis
1. The analyte precipitate must be low solubility,
high purity, and of known composition if its
mass is to accurately reflect to analytes mass
Zat yg ditentukan hrs dpt diendapkan secara terhitung (99%)
2. The precipitate must be in a form that is easy
to separate from the reaction mixture

Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation methods

Analyte (or chemically related species) isolated as a
sparingly soluble precipitate of known composition.

Analyte (or chemically related species) isolated as a
sparingly soluble precipitate that can be converted by
heat to species of known composition.
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis

1.) Principals:

(i) Reagent + Analyte Solid Product
(collect and measure mass)

(ii) Desired Properties of Solid Product
Should be very insoluble
Easily filterable (i.e., large crystals)
Very Pure
Known and constant composition
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis
2.) Solubility:
(i) The solubility of a precipitate can be decreased by:
Decreasing temperature of solution
Using a different solvent
- usually a less polar or organic solvent (like
dissolves like)
Solubility vs. pH
Solubility vs. Temperature
Solubility vs. Common Ion Effect
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Precipitation Analysis

3.) Gravimetric Analysis:
(i) Governed by equilibrium: AgCl K
sp
= 1.8 x 10
-10


Solubility of AgCl = [Ag
+
] + [AgCl] + [AgCl
2-
]

Cl
-
+ Ag
+
AgCl(ag) ion pair formation


AgCl(aq) AgCl(s) intrinsic solubility


AgCl +Cl
-
AgCl
2-
complex ion formation




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

Dry substance content in manure :


Liquid : up to 10%
Semi-solid : 10 to 20%
Solid : 20% or more
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Example:

The thermogram shows the change in mass for a sample of calcium oxalate
monohydrate, CaC
2
O
4
.H
2
O. The original sample weighed 24.60 mg and was
heated from room temperature to 1000
o
C at rate of 5
o
C per min. The
following changes in mass and corresponding temperature ranges were
observed:

Loss of 3.03 mg from 100 250
o
C
Loss of 4.72 mg from 400 500
o
C
Loss of 7.41 mg from 700 850
o
C

Determine the identities of the volatilization products and the solid
residue at each step of the thermal decomposition.


Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Solution:
a) The loss of 3.03 mg from 100 250
o
C corresponds to a 12.32%
decrease in the original samples mass


(30.3 mg/24.60 mg) x 100 = 12.32%

In term of CaC
2
O
4
.H
2
O this corresponds to a loss of :

0.1232 x 146.11 g/mol = 18 g/mol

The prducts molar mass, coupled with the temperature range, suggests
that this represents the loss of H
2
O. The residue is CaC
2
O
4




Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Solution:
b) The loss of 4.72 mg from 400 500
o
C corresponds to a 19.19%
decrease in the original samples mass


(4.72 mg/24.60 mg) x 100 = 19.19%

In term of CaC
2
O
4
this corresponds to a loss of :

0.1919 x 146.11 g/mol = 28.04 g/mol

The products molar mass, coupled with the temperature range, suggests
that this represents the loss of CO. The residue is CaCO
3




Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Solution:
c) The loss of 7.41 mg from 700 850
o
C corresponds to a 30.12%
decrease in the original samples mass


(7.41 mg/24.60 mg) x 100 = 30.12%

In term of CaC
2
O
4
this corresponds to a loss of :

0.3012 x 146.11 g/mol = 44.01 g/mol

The products molar mass, coupled with the temperature range, suggests
that this represents the loss of CO
2
. The residue is CaO





Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Particulate Gravimetry
Based on precipitation or volatilization reactions require that the analyte,
or some species in the sample, participate in a chemical reaction producing
a change in physical state.

Example:

A 200-mL sample of water was filtered through a preweighed glass fiber
filter. After drying to constant weight at 105
o
C, the filter was found to
have increased in mass by 48,2 mg. Determine the total suspended solids
for the sample in parts per million.

Solution:
Part per million is the same as milligrams of anlyte oer liter of solution;
thus the total suspended solids for the sample is

48.2 mg/0.2000 L = 241 ppm

Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
GRAVIMETRY Procedures

Sample preparation
Precipitation
Dillution
Filtration
Rinsing
Drying/combusting
Weighing
Calculation

Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Applications

Extensive numbers of inorganic ions are
determined with excellent precision and
accuracy.
Routine assays of metallurgical samples.
Relative precision 0.1 to 1%.
Good accuracy
Analisis Gravimetri
Universitas Islam Negeri Sunan Kalijaga
Yogyakarta
Thank you for your attention

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