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GRAVIMETRIC ANALYSIS

Kimia Analitik
Universitas Pertamina

Objective
• Understand the principles of gravimetric analysis
• Understand the principles of precipitation process
• Perform calculations relating to gravimetric analysis

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TOPICS
1. Definition
2. Precipitation Gravimetry
2.1. Properties of Precipitates and Precipitating
Reagents
2.2. Particle Size and Filterability of Precipitates
2.2. Colloidal Precipitates
2.3. Crystalline Precipitates
2.4. Coprecipitation
2.5. Precipitation from Homogeneous Solution
2.6. Drying and Ignition Precipitates
3. Gravimetric Calculation
4. Application of Gravimetric Method

1. Definition
• Gravimetric Methods are quantitative methods that
are based on determining the mass of a pure
compound to which the analyte is chemically related.
• Analyte: the compound or species to be analyzed in a
sample
• 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 balance

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Classification
Precipitation gravimetry: the analyte is separated from a
solution of the sample as a precipitate and is converted to a
compound of known composition that can be weighed.
Volatilization gravimetry: the analyte is separated from other
constituents of a sample by conversion to a gas of known
chemical composition. The weight of this gas then serves as a
measure of the analyte concentration.
Electrogravimetry: the analyte is separated by deposition on
an electrode by electrical current. The mass of this product
then provides a measure of the analyte concentration.

2. Precipitation Gravimetry
• Precipitation method is most common
• Isolate unkown species via precipitation and filtration
• Dry and mass
 “Heat to constant mass” to ensure all water is gone

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Example
 Determination of lead (Pb+2) in water
Precipitate
Pb2+ + 2Cl-  PbCl2(s)
Analyte Reagent Solid Product

 By adding excess Cl- to the sample, essentially all of the Pb+2

will precipitate as PbCl2.

 Mass of PbCl2 is then determined.

- used to calculate the amount of Pb+2 in original solution

Calculation Example
• Calculate the mass of the solid product formed when 1.5 L
of 0.50 M NaOH is combined with 2.0 L 0.10 M MgCl2.
a) Write a balanced equation
b) Determine what the solid product is (which is
insoluble?)
c) Determine limiting reactant.
d) Calculate mass of solid
• Solution
a) 2 NaOH (aq) + MgCl2(aq)  2 NaCl(aq) + Mg(OH)2(s)
b) Precipitate = Mg(OH)2 (most hydroxides (OH-) are
insoluble)

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Solution
• 1.5 L x 0.50 M = 0.75 mol NaOH
• 2.0 L x 0.10 M = 0.20 mol MgCl2
• NaOH : MgCl2 = 2 : 1 MgCl2 is limiting

• 0.2 mol MgCl2 = 0.2 mol Mg(OH)2 = 11.66 g Mg(OH)2

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Exercise
A 2.00 g sample of limestone was dissolved in hydrochloric
acid and all the calcium present in the sample was
converted to Ca2+(aq). Excess ammonium oxalate solution,
(NH4)2C2O4(aq), was added to the solution to precipitate the
calcium ions as calcium oxalate, CaC2O4(s). The precipitate
was filtered, dried and weighed to a constant mass of 2.43
g. Determine the percentage by mass of calcium in the
limestone sample.
Solution:
• 2.43g / 128g/mol = 0.0190 mol CaC2O4
• Ca2+ : CaC2O4 = 1 : 1
• 0.0190 mol Ca2+ x 40.08 g/mol = 0.762 g Ca2+
• 0.762 g Ca2+ / 2.00 g limestone = 38.1 %

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Exercise
• Calculate the mass of solid MgSO4.7H2O that must be
added to precipitate out all of the PO43- ions in the form of
MgNH4PO4.6H2O from 10.0 mL of a 2.0 M solution of
PO43-(aq)?
• Solution
• 0.01 L x 2.0 M = 0.020 mol PO43-
• Mg2+ : PO43- = 1 : 1
• 0.020 mol MgSO4.7H2O = 4.9 g MgSO4.7H2O

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2.1. Properties of Precipitates and

Precipitating Reagents
Requirements of the ideal product of a
gravimetry analyses:
1) very insoluble, low solubility  preventing losses
during filtration and washing
2) easily filterable : large crystal particle
3) Stable final form (Unreacted)
4) known chemical composition after drying or ignition

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2.2. Particle Size and Filterability of

Precipitates
• Precipitates consisting of large particles are generally
desirable for gravimetric work because these
particles are easy to filter and wash free of impurities.
• In addition, precipitates of this type are usually purer
than other precipitates made up of fine particles.

Want product to be large enough to collect

on filter:
Doesn’t clog filter

Doesn’t pass through filter

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Factors That Determine the Particle Size

of Precipitates
Von Weimarn showed that particle size of
precipitates is inversely proportional to the relative
supersaturation of the solution during precipitation
Rate

Crystal
, growth

where Nucleation
Q = actual concentration of solute
= supersaturation
S = concentration at equilibrium
(Q– S) / S

Increase particle size

when (Q - S)/S is large, the precipitate tends to be colloidal,

when (Q - S)/S is small, a crystalline solid is more likely formed

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Mechanism of Precipitate Formation (1)

• The effect of relative supersaturation on particle size can
be explained if we assume that precipitates form in two
ways: Nucleation – atom-atom in solution come
Crystal Growth together randomly and form small
aggregates molecules

Particle growth – addition of molecules to a

nucleus to form a crystal

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Mechanism of Precipitate Formation (2)

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

Want to

Convert to

Colloidal suspension Crystal formation

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Factors That Determine the Particle Size

of Precipitates
• Colloidal suspensions (worse case)
• 10-7 to 10-4 cm diameter
• Normally remain suspended
• Very difficult to filter

• Crystalline suspensions (best case)

• > tenths of mm diameter
• Normally settle out
spontaneously
• Readily filterable

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2.3. Colloidal Precipitates

• Individual colloidal particles are so small that they are not
retained by ordinary filters.
• Moreover, Brownian motion prevents their settling out of
solution under the influence of gravity.
• Technique used to give a filterable, amorphous mass that
will settle out of solution:
• Coagulation of Colloids  by heating, stirring or adding electrolyte
• Peptization of Colloids  wash with electrolyte to remove colloid
• Digestion  heated in the solution from which it was formed

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Colloidal Precipitates
Silver nitrate is added very slowly to an acidic
solution containing chloride. Silver chloride nuclei
form with a surface layer of ions. The “charged” Silver chloride lattice
AgCl particles (or colloidal particles) repels each (nucleus of AgCl colloid)
other

Primary adsorbed Ag+

Counter ion layer

Electric double layer

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Colloidal Precipitates
• In addition to the primary adsorbed silver ions, some nitrate
ions form an electrostatic layer around the nucleus.
• These counter ions tend to aggregate around the [AgCl:Ag]+
center because these centers have a net positive charge
(Excess Ag+) and additional negative charge is required to
maintain electrical neutrality.
• Counter ions are less tightly held than the primary adsorbed
ions and the counter ion layer is somewhat diffuse and
contains ions other that those of the counter ions.
• These layers of charged ions associated with the surface of
the nuclei are known as the electric double layer.
Coagulation of colloids
• Coagulation, agglomeration 
Suspended colloidal particles coalesce to form larger filterable particles
• Heating decreases adsorption and increase particle’s kinetic energy
• Addition of electrolyte decreases the size of the electric double layer

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Peptization:
a process by which a coagulated colloid returns to its dispersed state.  Re-
dissolution of coagulated colloids by washing and removing inert electrolyte
Digestion :
Heating the precipitate within the mother liquor (or solution from which it
precipitated) for a certain period of time to encourage densification of nuclei
During digestion, small particles dissolve and larger one grow (Ostwald
Ripening). This process helps produce larger crystals that are more easily filtered
from solution.

Mother
liquor
ppt

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2.4. Crystalline Precipitates

• Crystalline precipitates are generally more easily filtered
and purified than are coagulated colloids.
• In addition, the size of individual crystalline particles, and
thus their filterability, can be controlled to some extent.
• Particle size controlled by using more dilute solutions and
slow addition of precipitating reagent
• Digestion – heating of precipitate for an hour or more in
mother liquor – result in larger particles.

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2.5. Coprecipitation
• Is the precipitation of an unwanted species along with
your analyte of interest.
• This process occurs to some degree in every gravimetric
analysis.
• A major factor for precipitations of Barium Sulfate and
those involving hydrous oxides.
• This cannot be avoided, but can be minimized by careful
precipitation and a thorough washing of the precipitate.

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2.6. Precipitation from Homogeneous

Solution
• Precipitation from homogeneous solution is a technique in which a
precipitating agent is generated in a solution of the analyte by a slow
chemical reaction.
• Local reagent excess does not occur because reagent appears
gradually and reacts immediately
• Produces better precipitates for colloidal and crystalline.
• Urea is often used for the homogeneous generation of hydroxide ion.
The reaction can be expressed by the equation

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Example
• 500 mL 0.02 M Fe2(SO4)3 was prepared and 20 mL 12 M NH4OH(aq)
was added to complete the precipitation of Fe(OH)3 (s) according to the
equation
Fe3+ + 3 NH4OH(aq) ---> Fe(OH)3 (s) + 3 NH4+
• The resulting solution is shown in the photograph at the left.
• A second sample of 500 mL 0.02 M Fe2(SO4)3 was prepared and 7.2 g
urea, (NH2)2CO , was dissolved in the ferric sulfate solution. On the
addition of heat the generation of ammonium hydroxide occurs according
to the reaction
(NH2)2CO + 3H2O ---> CO2 + 2 NH4OH.
• After two hours at a temperature just below the boiling point, the resulting
precipitate settles in a thin layer on the bottom (photo at right).

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2.7. Drying and Ignition of Precipitates

• Many precipitates contain
varying amounts of H2O
- adsorbed from the air
(i.e. hygroscopic)
• Precipitates are are heated until
mass becomes constant.
• Precipitates are also ignited to
convert to a given chemical
form.

Effect of temperature on precipitate mass.

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2.7. Drying and Ignition of Precipitates

Precipitate form
Ignition (strong heating) is used to change the chemical form of some
precipitate.
Weighing form

Thermogravimetric curve for calcium salicylate.

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3. Gravimetric Calculation

Calculations of analyte content requires

knowledge of :
• Chemistry
• Stoichiometry
• Composition of precipitate

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Procedure for gravimetry based on

precipitation
1) Preparation of sample solution
2) Precipitation : Gravimetric precipitating agent should react
specifically or at least selectively with the analyte.
rR + aA = RrAa (solid)
3) Filtration and washing
4) Drying, ignition and weighing
5) Computation of results

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3. Gravimetric Calculations
The combined constant factors in a gravimetric calculation are
referred to as the gravimetric factor (GF).
.

.

% 100%

% 100%

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Example
• An iron ore was analyzed by dissolving a 1.1324 g sample in
conc. HCl. The resulting solution was diluted with water, and
the iron(III) was precipitated as the hydrous oxide Fe2O3.xH2O
by addition of NH3. After filtration and washing, the residue
was ignited at high temperature to give 0.5394 g pure Fe2O3
(MM = 159.69 g/mol). Calculate
• (a) % Fe (MM 55.847 g/mol)
(b) % Fe3O4 (MM 231.54 g/mol) in the sample.
.
mol Fe2O3 = . /
3.3778 10

.
% Fe = 100%
mol Fe = 2 x mol Fe2O3 = 2 x 3.3778 10 .
33.32 %
massa Fe =
2 x 3.3778 10 55.847 0.37728

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Solution
1
3 2 3 → 2 3 4 2
2
2
3 4 2 3
3

3 4 3 4 3 4

2
3 4 3 4 2 3
3
2
3 4 231.54 3.3778 10 0.5214
3
0.5214
% 3 4 100% 46.04 %
1.1324

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Solution Using GF
• A) 55.847 2
0.69944
. 2 3 2 3 159.69 1 2 3

2 3
% 100%

0.69944 0.5394
% 100% 33.32 %
1.1324

3 4 3 4 231.54 2 3 4
• B)
.



159.69 3
0.96662

2 3 2 3 2 3

2 3
% 3 4 100%

0.96662 0.5394
% 3 4 100% 46.04 %
1.1324

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Your Turn
The aluminum in a 1.200 g sample of impure ammonium
aluminum sulfate was precipitated with aqueous ammonia
as the hydrous Al2O3ꞏxH2O. The precipitate was filtered and
ignited at 1000°C to give anhydrous Al2O3, which weighed
0.2001 g. Express the result of this analysis in terms of
(a) % NH4Al(SO4)2.
(b) % Al2O3.
(c) % Al.

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